EPA-450/3-82-001
Air Oxidation Processes
in Synthetic Organic Chemical
Manufacturing Industry —
Background Information
for Proposed Standards
Emission Standards and Engineering Division
U.S. ENVIRONMENTAL PROTECTION ApENCY
Office of Air, Noise, and Radiation
Office of Air Quality Planning and Standards
Research Triangle Park, North Carolina 27711
October 1983 '
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r
This report has been reviewed by the Emission Standards and Engineering Division of the Office of Air
Quality Planning and Standards, EPA, and approved for publication. Mention of trade names or
commercial products is not intended to constitute endorsement or recommendation for use. Copies of
this report are available through the Library Services Office (MD-35), U.S. Environmental Protection
Agency, Research Triangle Park, North Caorlina 27711; or, for a fee, from the National Technical
Information Services, 5285 Port Royal Road, Springfield, Virginia 22161.
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ENVIRONMENTAL PROTECTION AGENCY
Background Information
and Draft
Environmental Impact Statement
for SOCMI Air Oxidation Unit Processes
Prepared by:
Don R. Goodwin!
Director, Emission Standards and Engineering Division
U.S. Environmental Protection Agency
Research Triangle Park, NC 27711
(Date)
1. The proposed standards of performance, would limit emissions of
..volatile.organic .compounds, from new, modified, and reconstructed
SOCMI air oxidation process. Section 111 of. the Clean Air Act
(42 U.S.C..7411), as amended, directs the Administrator to establish
standards, of performance, for any category of new stationary source
of air pollution that. ". . . causes or contributes significantly to
air pollution which may reasonably be anticipated to endanger
public, health or welfare." The Gulf Coast, and Northeast regions
would.be particularly affected by the proposed standards.
2.,. Copies of this, document, have been sent to, the following Federal
Departments: Labor, Health and Human Services, Defense, Transportation,
Agriculture.,. Commerce, Interior, and Energy; The National Science
Foundation;, the Council, on. Environmental Quality; members of the
State and. Territorial Air Pollution.Program..Administrators; the
Ass.oc.ia.tion of. Local Air Pollution Control Officials.; EPA Regional
Administrators; and other interested parties.
3. The comment period, for review of this document is 60 days.
Ms. Susan. R.. Wyatt. may be. contacted .regarding the date of the
comment period.
4. For additional information contact:
Ms. Susan R. Wyatt
Standards.Development Branch (MD-13)
U.S. Environmental Protection Agency
Research Triangle Park, NC 27711
Telephone: (919) 541-5578
5. Copies, of this document may be obtained from:
U.S... EPA Library (MD-35)
Research Triangle Park, NC 27711
National Technical.Information Service
5285 Port Royal Road
Springfield, VA 22161
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TABLE OF CONTENTS
List of Figures X1-v
Li st, of Tab! es xvi i i
Chapter 1. Summary ] _]
1.1 Regul atory Al ternati ves 1 _T
1.2 Environmental Impact 1_2
1.3 Economic Impact 1_4
Chapter 2. Introduction 2-1
2.1 Background and Authority for Standards 2-1
2.2 Selection of Categories of Stationary Sources 2-4
2.3 Procedures for Development of Standards of
Performance 2-6
2.4 Consideration of Costs 2-8
2.5 Consideration of Environmental Impacts 2-9
2.6 Impact on Existing Sources 2-10
2.7 Revision of Standards of Performance 2-11
Chapter 3. The Air Oxidation Industry 3_1
3.1 General 3_1
3.2 Industry Structure 3_1
3.2.1 Air Oxidation Chemicals 3-1
3.2.2 Uses of Air Oxidation Chemicals 3-1
3.2.3 Companies and Production of Air Oxidation
Chemicals • 3,5
3.2.4 Location of Air Oxidation Plants 3-5
3.3 Air Oxidation Production Processes 3-19
3.3.1 Reaction Types 3-19
3.3.2 Raw Materials... 3_22
3.3.3 Reaction Characteristics 3-25
3.3.3.1 Reaction S to i chi ometry 3-26
3.3.3.2 Reaction Phase 3_26
3.3.3.3 Explosion Hazard 3_29
3.4 Statistical Analysis of Air Oxidation Process 3-31
3.4.1 National Emissions Profile 3-32
3.5 References for Chapter 3 3_38
Chapter 4. Emission Control Techniques ..... 4-1
4.1 Introduction , 4_1
4.2 Adsorption 4_2
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TABLE OF CONTENTS (Continued)
Page
4.2.1 Carbon Adsorption Process 4-5
4.2.2 Carbon Adsorption Emissions Removal Efficiency 4-5
4.2.3 Parameters Affecting VOC Removal Efficiency..... 4-7
4.2.4 Factors Affecting Applicability and Reliability 4-8
4.3 Absorption 4"9
4.3.1 Absorption Process 4-11
4.3.2 Absorption VOC Removal Efficiencies 4-11
4.3.3 Factors Affecting Efficiency and Reliability 4-13
4.4 Condensation 4~13
4.4.2 Condenser VOC Removal Efficiency 4-15
4.4.3 Parameters Affecting Reliability and Efficiency 4-15
4.5 Control By Combustion Techniques 4-17
4.5.1 General Combustion Principles • 4-17
4.5.2 Combustion Control Devices •• 4-17
4.5.3 Thermal Oxidizers 4-18
4.5.3.1 Thermal Oxidation Process 4-18
4.5.3.2 Thermal Oxidizer Design 4-21
4.5.3.3 Thermal Oxidizer Emission Destruction
Effectiveness-. 4-23
4.5.4 Catalytic Oxidizers 4-25
4.5.4.1 Catalytic Oxidation Process 4-25
4.5.4.2 Catalytic Oxidation Emission Reduction
Effectiveness ... 4-28
4.5.4.3 'Parameters Affecting VOC Destruction
Efficiency 4-28
4.5.5 Advantages and Disadvantages of Control By
Combustion 4-28
4.6 Technical Feasibility of Retrofitting Control Devices 4-29
4.7 References for Chapter 4 4-31
Chapter 5. Modification and Reconstruction of Existing Facilities... 5-1
5.1 Types of Modification. , ••• 5~2
5.1.1 Feedstock Substitution 5-3
5.1.2 Reactant Substitution 5-3
5.1.3 Catalyst Substitution 5-6
5.1.4 Process Equipment Changes 5-7
5.1.5 Combination of Modifications 5-7
VI
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TABLE OF CONTENTS (Continued)
5.2 Identified Chemicals . 5-7
5.2.1 Acetaldehyde .1 5-7
5.2.2 Acetic Acid 5-8
5.2.3 Acetone 5.3
5.2.4 Acetophenone 5-8
5.2.5 Acrylic Acid 5-8
5.2.6 Benzaldehyde 5-8
5.2.7 1,3 Butadiene 5.9
5.2.8 n-Butyric Acid , 5-9
5.2.9 Cyclohexanol/Cyclohexanone 5-9
5.2.10 Dimethyl Terephthalate 5-9
5.2.11 Ethylene Oxide 5-10
5.2.12 Formaldehyde 5-10
5.2.13 Formic Acid 5-13
5.2.14 Glyoxal 5-13
5.2.15 Hydrogen Cyanide 5-13
5.2.16 Maleic Anhydride 5-13
5-14
5-14
5-16
5-16
5.3
5.4
5.2.17 Methyl Ethyl Ketqne.
5.2.18 Phenol
5.2.19 Phthalic Anhydride
5.2.20 Styrene
5.2.21 Terephthalic Acid 1 .-. 5-16
Summary 5_18
References for Chapter 5 5-19
Chapter 6. Regulatory Alternatives p 6-1
6.1 Method of Regulatory Analysis { 6-1
6.1.1 Unit Process Approach to NjSPS Development 6-2
6.1.2 Control Techniques j „ 6-3
6.1.3 National Profile 1 6-3
Regulatory Alternatives j 6-6
References for Chapter 6 \ 6-10
6.2
6.3
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TABLE OF CONTENTS (Continued)
Page
Chapter 7. Environmental Impact 7-1
7.1 Air Pollution Impacts.. 7-2
7.1.1 Effects of VOC Control on National Emissions 7-2
7.1.2 Other Effects on Air Quality 7-3
7.2 Water Pollution Impacts 7-5
7.3 Solid Waste Disposal. Impacts 7-7
7.4 Energy Impacts 7-7
7.4.1 Energy Requirements for Thermal Oxidation 7-8
7.4.2 Other Energy Requirements 7-9
7.5 Other Environmental Impacts 7-9
7.5.1 Considerations for Installing Control Equipment 7-9
7.6 Other Environmental Concerns. 7-9
7.6.1 Irreversible and Irretrievable Commitment of
Resources 7-9
7.6.2 Environmental Impact of Delayed Standards 7-10
7.7 References for Chapter 7 7-11
Chapter 8. Costs 8-1
8.1 Cost Analysis of Regulatory Alternatives 8-1
8.1.1 Introduction..., 8-1
8.1.2 Substitution of! National Profile for
Model Plant I 8-1
8.1.3 Thermal Oxidation Design Categories . .... 8-2
8.1.3.1 Categories Al and A2 8-2
8.1.3.2 Category B ........ 8-2
8.1.3.3 Category C 8-4
8.1.3.4 Category D 8-4
8.1.3.5 Category; E 8-4
8.1.3.6 Maximum JEquipment Sizes — 8-4
8.1.4 Offgas Composition Assumptions 8-5
8.1.5 New Facilities.* 8-8
8.1.5.1 Basis fojr Capital Costs 8-8
8.1.5.2 Basis foir Annualized Costs 8-15
8.1.5.3 Emission'Control Costs 8-20
8.1.5.4 Cost-Effectiveness of Control of an
Individual Facility 8-22
vm
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TABLE OF CONTENTS (Continued)
Page
8.1.6 Modified/Reconstructed Facilities 8-27
8.1.7 Regulatory Alternative Impacts 8-28
8.1.8 Chemical Process-Specific Costs 8-28
8.2 Other Cost Considerations 8-31
8.2.1 Control Cost Accumulation for Synthetic
Organic Chemical Manufacturing Industries
Using Air Oxidation Process 8-31
8.2.1.1 Introduction 8-31
8.2.1.2 Data and Assumptions for Accumulating
Costs 8-36
8.2.2 Costs of Regulations Other Than NSPS's
and NESHAP's 8-45
8.2.2.1 Water Pollution Control Regulations 8-45
8.2.2.2 Occupational Safety and Health
Regulations 8-48
8.2.2.3 Toxic Substance Control Regulations. 8-49
8.2.2.4 Solid and Hazardous Waste Regulations 8-51
8.3 References for Chapter 8 8-42
Chapter 9. Economic Impact Analysis 9-1
9.1 Industry Structure 9-1
9.1.1 Industry Definition?? .'. g-i
9.1.2 Air Oxidation Chemical's Supply and Capacity 9-2
9.1.3 Industrial Producers. 9-6
9.1.4 Employment 9-14
9.1.5 Industry Finances 9-14
9.1.6 End Uses 9_ig
9.1.6.1 The Plastics Industry 9-21
9.1.6.2 The Textile Fibers Industry 9-23
9.1.6.3 Other Industries 9-25
9.1.6.4 Growth in End Use Production 9-29
9.1.7 Individual AO Chemicals 9-31
9.1.7.1 Acetaldehyde 9-31
9.1.7.2 Acetic Acid 9-32
9.1.7.3 Acetone g_32
9.1.7.4 Acetonitrile 9-32
9.1.7.5 Acetophenone 9-33
9.1.7.6 Acrolein 9-33
9.1.7.7 Acrylic Acid 9.33
ix
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TABLE OF CONTENTS (Continued)
9.1.7.8 Acrylonitrile. 9-33
9.1.7.9 Anthraquinone 9-33
9.1.7.10 Benzaldehyde 9-33
9.1.7.11 Benzole Acid 9-34
9.1.7.12 1,3-Butadiene... 9-34
9.1.7.13 p-t-Butyl Benzoic Acid 9-35
9.1.7.14 n-Butyric Acid 9-35
9.1.7.15 Crotonic Acid 9-35
9.1.7.16 Cumene Hydroperoxide 9-35
9.1.7.17 Cyclohexanol and Cyclohexanone 9-35
9.1.7.18 Dimethyl Terephthalate (DMT) and
Terephthalic Acid (TPA) 9-36
9.1.7.19 Ethylene Dichloride 9-36
9.1.7.20 Ethylene Oxide 9-36
9.1.7.21 Formaldehyde 9-37
9.1.7.22 Formic Acid 9-37
9.1.7.23 Glyoxal 9-38
9.1.7.24 Hydrogen Cyanide 9-38
9.1.7.25 Isobutyric Acid 9-38
9.1.7.26 Isophthalfcrflcid 9-38
9.1.7.27 Maleic Anhydride 9-38
9.1.7.28 Methyl Ethyl Ketone 9-39
9.1.7.29 Methyl Styrene. 9-39
9.1.7.30 Phenol ..'. 9-39
9.1.7.31 Phthalic Anhydride 9-39
9.1.7.32 Propionic Acid. 9-40
9.1.7.33 Propylene Oxide 9-40
9.1.7.34 Styrene 9-49
9.1.8 Coproducts and Byproducts 9-41
9.1.9 Growth in New Facilities 9-42
9.1.10 Substitution 9-43
9.1.11 Raw materials.. 9-50
9.1.12 Prices 9-52
9.1.12.1 Price of AO Chemicals 9-52
9.1.12.2 Price Determination in the AO
Industry 9-52
9.1.12.3 Competitive Price Structure of the AO
Industry 9-57
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TABLE OF CONTENTS (Continued)
Page
9.1.13 International Considerations 9-60
9.2 Economic Analysis of SOCMI Air Oxidation NSPS 9 68
9.2.1 Summary of the Economic Effects of the
SOCMI Air Oxidation NSPS 9-68
9.2.2 Economic Impact.Analysis of the SOCMI Air
Oxidation NSPS 9-68
9.2.3 Price Increase 9-72
9.2.3.1 Price Increase Methodology., 9-73
9.2.3.2 Results of the Price Increase Screening 9-74
9.2.3.3 Sensitivity Analysis 9-76
9.2.4 Profitability Decline 9-79
9.2.4.1 Profitability Decline Methodology 9-80
9.2.4.2 Results of the Profitability Decline
Screening.. 9-82
9.2.4.3 Profitability Decline Sensitivity
Analysi s 9-87
9.2.5 Capital Constraints 9-87
9.2.6 Foreign Competition 9-88
9.2.6.1 Foreign Competition Methodology 9-88
9.2.6.2 Results of Foreign Competition Screening 9-88
9.2.7 Ranking of Chemicals 9-92
9.2.8 Individual Chemical Industry Analysis 9-98
9.2.8.1 1,3-Butadiene (Capital Constraints) 9-99
9.2 8.2 Maleic Anhydride (Price Increase
and Profitability Decline) 9-103
9.2.8.3 Phthalic Anhydride (Price Increase) 9-107
9.2.8 4 Terephthalic Acid (Profitability Decline) 9-109
9.3 Potential Socioeconomic and Inflationary Impacts 9-110
Appendix A to Chapter 9. Net Present Value Formula 9-123
Appendix A: Evolution of the Proposed Standards..'. A-l
Appendix B: Index to Environmental Considerations B-l
Appendix C: Emission Source Test Data , C-l
C.I VOC Emissions Test Data C-l
C. 1.1 Chemical Company Test Data C-l
C. 1.1.1 Petro-Tex Test Data. C-l
C.I.1.2 Koppers Test Data C-7
C.I.1.3 Monsanto Test Data C-8
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TABLE OF CONTENTS (Continued)
Page
C.I.2 Environmental Protection Agency (EPA)
Test Data : c-'2
C.I.2.1 Denka Test Data C-12
C.I.2.2 Rohm and Haas Test Data C-15
C.I.2.3 Union Carbide (UCC) Test Data C-16
C.I.3 Union Carbide Lab-Scale Test Data , C-19
C.2 Nitrogen Oxides (NOY) Emissions C-19
J\
C.3 Comparison of Test Results and the Technical Basis
of the SOCMI Air Oxidation Emissions Limit C-21
C.4 References for Appendix C. C-28
Appendix D: Monitoring and Performance Test Methods D-l
D.I Introduction • D-l
D.2 VOC Reduction Efficiency Measurement. D-l
D.2.1 Emission Measurement Tests. D-2
D.2.2 Recommended, Test Method D-4
D.3 Measurement of Gaseous Organic Compound Emissions
By Gas Chromatography D-5
D.4 Determination of'Net Heating Value of Exhaust
Gas Streams • °-5
D.5 References for Appendix D-.-^r D-6
Attachment I to Appendix D: Measurement of Gaseous Organic
Compound Emissions By Gas
Chromatographyo D-7
Attachment II to Appendix D: Determination of the Heating Value
of Exhaust Gas Streams..... D-l20
Appendix E: TRE Calculations • E-"1
E.I Introduction E-1
E.2 Total Resource-Effectiveness E-l
E.2.1 Derivation of the TRE Coefficients E-4
E.2.2 Example Calculation of the TRE Index Value
for a Facil ity E-8
E.2.3 Calculation of Cost-Effectiveness for a
Facil ity E-9
Appendix F: Statistical Analysis F-1
F.I Introduction F-1
F.2 Statistical Impact Analysis F-l
xii
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TABLE OF CONTENTS (Continued)
F.2.1 National Statistical Profile Construction F-2
F.2.2 Data Reliability F-6
F.2.3 National Statistical Profile Use F-16
F.2.4 Calculation of Baseline Control Level F-16
F.3 Flow Prediction F-17
Appendix G: Cost Analysis Special Topics G-l
G.I Introduction G-l
G.2 Control Equipment Purchase Costs G-l
G.2 1 Thermal Oxidizer G-l
G.2.2 Recuperative Heat Exchanger ; G-l
G.2.3 Waste Heat Boiler G-2
G.2.4 Fans G-2
G.2.5 Stack G-2
G.2.6 Ducts G-2
G.3 Installation Factors G-3
G.4 Individual Component Installed Costs G-5
G.5 Total Control System Installed Capital Costs G-5
G.6 Chemical Process-Specific Costs.... G-l6
G.7 References for Appendix
G-21
xm
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LIST OF TABLES
Page
1-1 Matrix of Environmental and Economic Impacts for Each
Regulatory Alternative Considered 1-3
3-1 SOCMI Chemicals Produced By Air Oxidation : 3-2
3-2 Major End Use of Each Identified SOCMI Air Oxidation
Chemi cal 3-4
3-3 Companies Producing Synthetic Organic Chemicals Using
Air Oxidation Processes 3-6
3-4 Largest Producers of Identified SOCMI Air Oxidation
Chemi cal s 3-9
3-5 Annual Production Capacity of the Identified SOCMI Air
Oxidation Chemicals 3-11
3-6 Air Oxidation Process Facilities 3-13
3-7 Percentage Production of SOCMI Chemicals By Air Oxidation 3-20
3-8 Air Oxidation Processes with Co-Products(s) and
By Products (s) . 3-23
3-9 Basic Raw Materials for Air Oxidation Chemicals 3-24
3-10 Phase of the Air Oxidation Reaction Step in the Production
of Air Oxidation Chemicals. 3-34
3-11 Chemicals Covered By Houdry Questionnaire 3-35
4-1 Product Recovery and Emission Controls Currently Used in
One or More Plants Employing Major Air Oxidation Processes 4-3
4-2 Selected Air Oxidation ProcesTes Known to Use Carbon;
Adsorption for Product/Raw Material Recovery or Emission
Reduction ...', 4-4
4-3 Selected-Air Oxidation Processes Known to Use Absorption
for Product Raw Material Recovery or Emissions Reduction 4-10
4-4 Selected Air Oxidation Processes Known to Use Condensation
for Product Raw Material Recovery or Emissions Reduction 4-14
4-5 Partial List of Air Oxidation Chemicals Using Thermal
Oxidizer for Controlling VOC Emissions from Offgas Stream 4-19
4-6 Selected Air Oxidation Processes Known to Use Catalytic
Oxidation for Emission Control 4-26
5-1 Possible Feedstock, Reactant, and Catalyst Substituions
in Air Oxidation Processes 5-4
5-2 Possible Reactant Substitutions 5-5
5-3 Vent Gas Composition from Representative Ethylene
Oxi de PI ants ,. 5-11
5-5 Waste Gas Composition from Representative Maleic \
Anhydride Plants i 5-15
5-6 Switch Condenser Offgas Composition from Representative
Phthalic Anhydride Plants ; 5-17
XIV
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LIST OF TABLES (Continued)
6-1 Regulatory Alternatives 6-8
7-1 VOC Emissions and Energy Requirements .for Selected
Control Levels 7-4
8-1 Basic Characteristics of Each Design Category 8-3
8-2 Maximum Offgas Flowrates of Each Design Category 8-6
8-3 Ratio of Flue Gas Flowrate to Offgas Flowrate for Each
Design Category 8-7
8-4 Instal 1 ation Components 8-10
8-5 Total Installed Capital Cost Equations as a Function
of Offgas Flowrate 8-11
8-6 Installed Capital Costs for a Selected Hypothetical Vent
Stream in Each Design Category 8-12
8-7 Annualized Cost Factors. 8-16
8-8 Operating Factors for Each Design Category 8-17
8-9 Annualized Cost Equations 8-18
8-10 Typical Emission Control Costs for Each Design Category 8-21
8-11 Cost Effectiveness for Selected Streams of Each Design
Category 8-23
8-12 Coefficients of the Tota-1 Resource-Effectiveness (TRE)
Index Equation 8-26
8-13 Summary of Environmental, Energy and Economic Impacts of
Each Regulatory Alternative. .TT7 8-29
8-14 Chemical Process-Specific Costs 8-30
8-15 Five Year Projections of New Facilities Utilizing Both
Air Oxidaton and Nonair-Oxidation Porcesses 8-35
8-16 Total Fifth Year Annualized Cost of Control for Each
Chemical Industry that Utilizes the Air Oxidation
Process, Accumulated by Potential Air Regulations 8-37
8-17 Fifth Year Annualized Costs of the NSPS for Air Oxidation
Process, By Specific Industry 8-44
8-18 Statutes That May Be Applicable to Air Oxidation Facilities 8-46
8-19 Air Oxidation Chemicals Regulated By OSHA General Controls 8-50
8-20 Air Oxidation Chemicals Regulated By RCRA 8-52
9-1 Number of Facilities Capacity, Production, Capacity
Utilization, and Value of Production 9-3
9-2 Percentage of Total AO Chemical Production Volume That is
Sold (Non-Captive Consumption) 9-7
9-3 Individual Companies and the AO Chemicals They Produce 9-9
XV
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LIST OF TABLES (Continued)
9-4
9-5
9-6
9-7
9-8
9-9
9-10
9-11
9-12
9-13
9-U
9 15
9-16
9-17
9-18
9-19
9-20
9-21
9-22
9-23
9-24
9-25
9-26
9-27
9-28
9-29
The Largest Producer of Each AO Chemical and the Percent
of the AO Chemical's Total Capacity the Largest
Producer Owns 9-15
Aggregate Cash Flow Statistics (Nominal $), Chemicals
and Allied Products (SIC 28) 9-21
AO Chemicals by Value of Production with Each Chemical's
Major End Use Products • • • 9-22
Consumption of Plastic Materials" and Synthetic .Resins by
End Use Sectors , 9-24
Consumption of Man-Made Fibers by End Use, and the
Percent of Man-Made Fibers Consumption to All Fibers
Consumption by End Use 9~26
Percent of Total Synthetic Rubber Consumed by End Use 9-28
Equations for Projecting AO New Capacity and Facilities 9-44
Projected New AO Chemical Facilities by Chemical for Two
Capacity Utilization Scenarios 9-47
Raw Materials of AO Chemicals 9-63
Market (Spot) Prices for AO Chemicals 9-53
AO Chemical Exports and Imports 9-61
U.S. and European Price Differences for AO Chemicals 9-63
Old, Current, and Proposed Tariffs 9-66
Fifth Year Annualized ControUCosts for Seven Regulatory
Alternatives and National Emission Reductions 9-69
Projected AO Chemical Prices if Expected Increases in
Oil and'Natural Gas Prices Are Passed Through 9-75
Percent AO Chemical Price Increases When Producers Pass
Through Al 1 Control Costs
Net Present Values of Future Facilities, With and
Without Pollution Control 9-83
AO Processes 9-85
Hurdle Rates at Which Net Present Values of Future
Facilities Change from Positive (Without Pollution
Control) to Negative (With Pollution Control) 9-86
Imports and Exports as a Percentage of Production 9-89
1,3-Butadiene Imports by Country of Origin 9-91
Chemical Feedstock Prices • 9-93
Chemicals Ranked by Possible Economic Effects of AO
NSPS 9-95
Capital Control Cost as a Percentage of Capital
Expenditures by Producers 9-100
1,3-Butadiene Capacity, by Producer 9-101
Maleic Anhydride Capacity,.by Producer 9-105
9-77
xvi
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LIST OF TABLES (Continued)
9-30
C-l
C-2
C-3
C-4
0-1
E-l
F-l
F-2
F-3
F-4
F-5
F-6
F-7
F-8
F-9
G-l
Phthalic Anhydride Capacity, by Producer 9-108
Thermal Incinerator Field Test Data C-5
Results of Destruction Efficiency Under Stated Conditions
(Union Carbide Tests) C-20
Summary of Results: NO Data C-22
/\
Result Comparisons of Lab Incinerator vs. ROHM & HAAS
Inci nerator C_24
Emission Measurement Test Results 0-3
Coefficients of The Total Resource Effectiveness (TRE)
Index Equation £_3
List of Chemicals for Which Data Has Been Obtained F-3
Actual Data Base Used To Construct National Statistical
Profile
F-4
Air Oxidation Off gas Components F-9
Distribution of National Statistical Profile Data Vectors F-12
Joint Distribution of Flow and Mass Emissions In
National Profile... - p-13
Joint Distribution of Design Categories and Mass Emissions
In National Statistic Profile F-14
A Comparison of The Eight Considered Forms of The F
Predictor Equation v%fei F-l8
Summary Statistics of The Chose F Predictor Equation F-20
Effectiveness of The F, Predictor F-21
Installation Component Factors (% of Budget Price
of Main Equipment) g_4
G-2 Characteristics of Specific Chemical Processes 6-17
XVll
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LIST OF FIGURES
Page
3-1 Schematic of a Flowsheet for a Liquid
Phase Air Oxidation Process 3-28
3-2 Schematic of a Flowsheet for a Vapor Phase
Air Oxidation Process • 3-30
4-1 Two Stacje Regenerative Adsorption System 4-6
4-2 Generalized Form of the Relationship of Effluent
VOC Concentration to Steam Usage 4-8
4-3 Packed Tower for Gas Absorption 4-12
4-4 Condensation System 4-16
4-5 Discrete Burner, Thermal Oxidizer 4-22
4-6" Distributed Burner, Thermal Oxidizer 4-22
4-7 Catalytic Oxidizer 4-27
9-1 AO Chemical Plant Locations by State 9-8
9-2 After-Tax Earnings as a Percentage of Net Sales 9-17
9-3 Crude Oil and Chemical Market Price and
Price Index Trends 7»... 9-56
9.4 Fifth Year Annualized Control Costs and National
Percent Emissions Reduction... 9-70
C-l Petro-Tex 0X0 Unit Incinerator . C-5
C-2 Off-Gas Incinerator, Monsanto Company,
Chocol ate Bayou PI ant - C-l 0
C-3 Thermal Incinerator Stack Sampling System C-ll
C-4 Incinerator Combustion Chamber C-14
F-l General Air Oxidation Process F-8
6-1 Installed Capital Cost for the Combustion Chamber
with Waste Gas Heat Content - 10 Btu/scf, Residence
Time = 0.75 sec, and Combustion Temperature = 1600 F.. G-6
G-2 Installed Capital Cost for Recuperative - Type
Heat Exchangers with the Waste Gas Heat Content
* 10 Btu/scf 6-7
jcviii.
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LIST OF FIGURES (Continued)
Page
6-3 Installed Capital Costs for Inlet Ducts, Waste
Gas, and Combustion Air Fans and Stack System
With No Heat Recovery , G-8
G-4 Installed. Capital Costs for Inlet Ducts, Waste
Gas, and Combustion Air Fans and Stack for
System With No Heat Recovery G-9
G-5 Installed Capital Cost of Thermal Oxidizer at
1800 and 2200 F Including Incinerator, Two Blowers,
Ducts, and Stack G-l 0
G-6 Installed Capital Cost for Waste Heat Boilers (250 psi)... G-ll
G-7 Flume Flow Through Scrubber G-12
G-8 Installed Capital for Inlet Ducts,, Waste Gas, and
Combustion Air Fans and. Stack With Waste Heat Boilers G-l3
G-9 Total Installed Capital Cost for Thermal Oxidation
Systems With Waste Gas Heat Content = 10 Btu/scf,
Residence Time = 0.75 sec, and Combustion Temperature
= 1600°F
G-l 4
6-10 Total Installed Capital Cost for Thermal Oxidation
Systems With a Scrubber at a Residence Time of
0.5 sec, a Combustion Temperature at 2200 F, and a
Waste Gas Heat Content of 1 Btu/scf G-15
XIX
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1. SUMMARY
Background information on proposed new'source performance standards
for the Synthetic Organic Chemical Manufacturing Industry (SOCMI) air
oxidation processes is contained in this document. New source performance
standards are proposed under authority of Section 111, 301(a) of the
Clean Air Act, as amended.
1.1 REGULATORY ALTERNATIVES
The regulatory alternatives are based upon a single VOC control
technique,, thermal oxidation, which is the most effective control
technology and is demonstrated, for application at all facilities. All
new thermal oxidizers can achieve at least a 98 weight percent VOC
reduction, or VOC reduction to 20 ppmv (by compound). Accordingly, each
alternative would require this degree of VOC emission reduction for
those affected facilities required to reduce emissions. Under each
successive regulatory alternative, an additional percentage of projected
affected facilities would be subjected, to. the standards. Each successive
increment of sources required to meet the standards would have a higher
per unit control cost than, the increment of sources, added, under the
previous alternative.
Alternative.0 represents the. baseline level of control. Under
Alternatives I through VI, the percentages, of all projected facilities
covered by the air oxidation NSPS would be 7, 14, 19, 27, 47, and 100,
respectively.
A maximum or cutoff value of total resource, effectiveness (TRE) is
associated with each regulatory alternative. The TRE value of a facility
is proportional to the cost of incineration, per megagram of VOC destroyed,
for that facility. The TRE value of a facility is an algebraic function
of the vent stream flowrate, heating value, VOC emission rate, and
corrosion properties (presence of chlorinated, compounds). A facility
with a TRE value, below the cutoff TRE value associated with a given
alternative would be required to reduce VOC emissions by 98 percent or
to 20 ppmv under that alternative. However,, the regulatory alternatives
are structured, to allow such a facility to add a product recovery device
or improve an existing product recovery device to change the vent stream
characteristics used for calculating the TRE value. As a result of this
1-1
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change, the TRE value for such a facility would be increased beyond the
cutoff value associated with the given alternative and incineration
would not be required. Such increased product recovery would have the
advantages over incineration of lower cost and. less energy usage.
1.2 ENVIRONMENTAL IMPACT
The environmental impacts of the regulatory alternatives have been
analyzed. A matrix of environmental and economic impacts for each
regulatory alternative considered is given in Table.1-1. As indicated
in Section 1.1, each alternative is based, upon a single VOC control
technqiue, thermal, oxidation, which is universally applicable to air
oxidation processes.
Under Alternative I, projected 1986.national VOC emissions from
new, modified, or reconstructed air oxidation facilities would be
reduced by an estimated 6,500 Mg/yr. This national VOC reduction would
be approximately 31 percent beyond the 22SQOO Mg/yr level that would be
expected under typical State implementation plans (SIP's).
Under Alternative II, projected 1986.national VOC emissions would
be reduced by an estimted 10,000 Mg/yr. This represents a reduction of
about 46.percent from the projected baseline emissions level.
Under Alternative III, projected 1986.national VOC emissions would
be reduced by an estimated 12,500 Mg/yr. This represents a reduction of
about 57 percent from the projected baseline emissions, level.
Under Alternative IV, projected 1986.national VOC emissions would
be reduced by an estimated 14,000 Mg/yr. This represents a reduction of
about 66.percent from, the projected baseline.emissions level.
Under Alternative V, projected 1986.national VOC emissions would be
reduced by-an estimated 17,500 Mg/yr. This represents a reduction of
about 81 percent from the projected baseline emissions level.
Under Alternative VI, projected 1986.national VOC emissions would
be reduced by an estimated 21,000 Mg/yr. This represents a reduction of
98 percent from the projected baseline emissions level.
Any increase in emissions of other air pollutants as a result of
controlling VOC emissions would be negligible., There would be no direct
solid waste impacts under any of the regulatory alternatives, and
impacts on noise, space requirements,.and availability of resources
would be negligible.
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TABLE 1-1. MATRIX OF ENVIRONMENTAL AND ECONOMIC IMPACTS FOR
EACH REGULATORY ALTERNATIVE CONSIDERED
Administrative Action
i,
Regulatory Alternative. 0
(Baseline)
Regulatory Alternative I
Regulatory Alternative II
Regulatory Alternative III
Regulatory Alternative IV
Regulatory Alternative V
Regulatory Alternative VI
Air
Impact
.0
+3
+3
+4
+4
+4.
+4
Water
Impact .
.0
.0
.0
.0
-1
-1
-1
Solid
Waste
Impact
.0
.0
.0
.0
.0
.0
.0
Energy
Impact
.0
-1
-1
-1
-1
-2
-2
Economic
Impact
.0
-1
-1
-1
-1
-1
-1
KEY: .0 No Impact
1 Negligible Impact
2 Small Impact
3 Moderate Impact
4 Large Impact
+ Beneficial Impact
- Adverse Impact
1-3
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No increase In total, plant, wastewater is projected under Alternatives I,
II, or III. There is no organic wastewater effluent, associated with
incineration. Therefore, the only facilities which could have an
associated, water pollution impact are those which might use additional
product recovery to raise a total resource-effectiveness (TRE) value.
Carbon adsorption is the only product recovery technique currently in
use in the industry which has an associated..organic wastewater effluent.
Based on past industry experience, very few. new air oxidation facilities
are expected to employ carbon adsorption. Therefore, the wastewater
generated under the first three alternatives is expected to be minimal.
The few air oxidation facilities which might employ additional carbon
adsorption are projected, to be covered only under Alternatives IV, V,
and/or VI., Therefore, under these alternatives, a small water pollution
impact might result.
The projected, fifth year energy use under Alternative I would be
230 million MJ/yr (110 bbl oil/day). The projected fifth year energy
use under Alternative II would be 520 million MJ/yr (240 bbl oil/day).
The projected fifth year energy use under Alternative III would be
770 million MJ/yr (36Q bbl oil/day). The projected fifth year energy
use under Alternative IV would be 1,0 billion MJ/yr (460 bbl oil/day).
The projected, fifth year energy use under Alternative V would be 2.4 billion
MJ/yr (1,1QO bfal oil/day). The projected fifth year energy use under
Alternative VI would be 6,0 billion MJ/yr (2,800 bbl oil/day).
1.3 ECONOMIC IMPACT
The projected total fifth year capital cost to. the air oxidation
industry under Alternative I would be $6,1 million. The projected total
fifth-year annualized cost to the industry under this alternative would
be $3,0 million/yr.
The projected fifth-year national capital cost under Alternative II
would be $13 million. The projected fifth-year annualized cost under
this alternative would be $7,0 million/yr.
The projected, fifth-year national capital cost under Alternative III
would be $18 million. The projected fifth-year annualized cost under
this alternative would be $10 million/yr.
The projected fifth-year national capital cost under Alternative IV
would be $26.million. The projected fifth-year annualized cost under
this alternative would be $15 million/yr.
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The projected fifth-year national capital cost under Alternative V
would be $42 million. The projected fifth-year annualized cost under
this alternative would be $28 million/yr.
The projected fifth-year- national capital, cost under Alternative VI
would be $87 million. The. projected fifth-year annualized cost under
this, alternative would be $67 million/yr.
The projected capital, and annualized. costs under each, alternative
were judged to be reasonable. An economic .analysis indicated that the
costs of VOC control due to each alternative could be passed on with a
negligible effect on the profitability of the air oxidation industry.
The projected price changes for air oxidation chemicals expected to have
new facilities in the fifth year, assuming that costs of 98 percent VOC
reduction would be passed.through totally, would range from zero to a
3.1 percent increase.
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2. INTRODUCTION
2.1 BACKGROUND AND AUTHORITY FOR STANDARDS
Before standards of performance are proposed as a Federal regulation,
air pollution control methods available to the affected industry and the
associated costs of installing and maintaining the control equipment are
examined in detail. Various levels of control based on different
technologies and degrees of efficiency are expressed as regulatory
alternatives. Each of these alternatives is studied by EPA as a prospective
basis for a standard. The alternatives are investigated in terms of
their impacts on the economics and well-being of the industry, the
impacts on the national economy, and the impacts on the environment.
This document summarizes the information obtained through these studies
so that interested persons will be able to see the information considered
by EPA in the development of the proposed standard.
Standards of performance for new stationary sources are established
under section 111 of the Clean Air Act (42. U.S.C. 7411) as amended,
hereinafter referred to as the Act. Section 111 directs the Administrator
to establish standards of performance.for any category of new stationary
source of air pollution which ". . . causes, or contributes significantly
to air pollution which may reasonably be anticipated to endanger public
health or welfare."
The Act requires that standards of performance for stationary
sources reflect "... the degree of emission reduction achievable which
(taking into consideration the cost of achieving such emission reduction,
and any nonair quality health and environmental impact and energy
requirements) the Administrator determines has been adequately demonstrated
for that category of sources." The standards apply only to stationary
sources, the construction or modification of which commences after
regulations are proposed by publication in the Federal Register.
The 1977 amendments to the Act altered or added numerous provisions
that apply to the process of establishing standards of performance.
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1. EPA is required to list the categories of major stationary
sources that have not already been listed and regulated under standards
of performance. Regulations must be promulgated for these new categories
on the following, schedule: I
a. 25 percent of the listed categories by August 7, 1980. j
b. 75 percent of the listed categories by August 7, 1981. i
c. 100 percent of the listed categories by August 7, 1982. I
A governor of a State may apply to the Administrator to add a category
not on the list or may apply to the Administrator to have a standard of
performance revi sed. •
2. EPA is required to review the standards of performance every
four years and, if appropriate, revise them.
3. EPA is authorized to promulgate a standard based on design,
equipment, work practice, or operational procedures when, a standard
based on emission levels is not feasible. ;
4. The term "standards of performance" is redefined, and a new
term "technological system of continuous emission reduction" is defined.
The new definitions clarify that the control system must be continuous
and may include a low- or non-polluting process or operation. :
5. The time between the proposal and promulgation of a standard
under section 111 of the Act may be extended to six months.
Standards of performance, by themselves, do not guarantee protection
of health or welfare because they are not designed to achieve any
specific air quality levels. Rather, they are designed to reflect the
degree of emission limitation achievable through application of the best
adequately demonstrated technological system of continuous emission
reduction, taking into consideration the cost of achieving such emission
reduction, any non-air-quality health and environmental impacts, and
energy requirements.
Congress had several reasons for including these requirements.
First, standards with a degree of uniformity are needed to avoid situations
where some States may attract industries by relaxing standards relative
to other States. Second, stringent standards enhance the potential for
long-term growth. Third, stringent standards may help achieve long-term
cost savings by avoiding the need for more expensive retrofitting when
pollution ceilings may be reduced in the future. Fourth, certain types
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of standards for coalburning sources can adversely affect the coal •
market by driving up the price of low-sulfur coal or effectively excluding
certain coals from the reserve base because their untreated pollution
potentials are high. Congress does not intend that new source performance
standards contribute to these problems. Fifth, the standard-setting
process should create incentives for improved technology.
Promulgation of standards of performance does not prevent State or
local agencies from adopting more stringent emission limitations for the
same sources. States are free under section 116 of the Act to establish
even more stringent emission limits than those established under section 111
or those necessary to attain or maintain the National Ambient Air
Quality Standards (NAAQS) under section 110. Thus, new sources may in
some cases be subject to limitations more stringent than standards of
performance under section 111, and prospective owners and operators of
new sources should be aware of this possibility in planning for such
facilities.
A similar situation may arise when a major emitting facility is to
be constructed in a geographic area that falls under the prevention of
significant deterioration of air quality provisions of Part C of the
Act. These provisions require, among other things, that major emitting
facilities to be constructed in such areas are to be subject to best
available control technology. The term Best Available Control Technology
(BACT), as defined in the Act, means
... an emission limitation based on the maximum degree of reduction
of each pollutant subject to regulation under this Act emitted
from, or which results from, any major emitting facility, which the
permitting authority, on a case-by-case basis, taking into account
energy, environmental, and economic impacts and other costs,
determines is achievable for such facility through application of
production processes and available methods, systems, and techniques,
including fuel cleaning or treatment or innovative fuel combustion
techniques for control of each such pollutant. In no event shall
application of "best available control technology" result in
emissions of any pollutants which will exceed the emissions allowed
by any applicable standard established pursuant to sections 111 or
112 of this Act. (Section 169(3))
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Although standards of performance are normally structured in terms
of numerical emission limits where feasible, alternative approaches are
sometimes necessary. In some cases physical measurement of emissions
from a new source may be impractical or exorbitantly expensive. Section lll(h)
provides that the Administrator may promulgate a design or equipment
standard in those cases where it is not feasible to prescribe or enforce
a standard of performance. For example, emissions of hydrocarbons from
storage vessels for petroleum liquids are greatest during tank filling.
The nature of the emissions, high concentrations for short periods
during filling and low concentrations for longer periods during storage,
and the configuration of storage tanks make direct emission measurement
impractical. Therefore, a more practical approach to standards of
performance for storage vessels has been equipment specification.
In addition, section lll(i) authorizes the Administrator to grant
waivers of compliance to permit a source to use innovative continuous
emission control technology. In order to grant the waiver, the Administra-
tor must find: (1) a substantial likelihood that the technology will
produce greater emission reductions than the standards require or an
equivalent reduction at lower economic energy or environmental cost; (2)
the proposed system has not been adequately demonstrated; (3) the
technology will not cause or contribute to an unreasonable risk to the
public health, welfare, or safety; (4) the governor of the State where
the source is located consents; and (5) the waiver will not prevent the
attainment or maintenance of any ambient standard. A waiver may have
conditions attached to assure the source will not prevent attainment of
any NAAQS. Any such condition will have the force of a performance
standard. Finally, waivers have definite end dates and may be terminated
earlier if the conditions are not met or if the system fails to perform
as expected. In such a case, the source may be given up to 3 years to
meet the standards with a mandatory progress schedule.
2.2 SELECTION OF CATEGORIES OF STATIONARY SOURCES
Section 111 of the Act directs the Adminstrator to list categories
of stationary sources. The Administrator ". . . shall include a category
of sources in such list if in his judgment it causes, or contributes
significantly to, air pollution which may reasonably be anticipated to
endanger public health or welfare." Proposal and promulgation of
standards of performance are to follow.
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Since passage of the Clean Air Amendments of 1970, considerable
attention has been given to the development of a system for assigning
priorities to various source categories. The approach specifies areas
of interest by considering the broad strategy of the Agency for implementing
the Clean Air Act. Often, these "areas" are actually pollutants emitted
by stationary sources. Source categories that emit these pollutants are
evaluated and ranked by a process involving such factors as (1) the
level of emission control (if any) already required by State regulations,
(2) estimated levels of control that might be required from standards of
performance for the source category, (3) projections of growth and
replacement of existing facilities for the source category, and (4) the
estimated incremental amount of air pollution that could be prevented in
a preselected future year by standards of performance for the source
category. Sources for which new source performance standards were
promulgated or under development during 1977, or earlier, were selected
on these criteria.
The Act amendments of August 1977 establish specific criteria to be
used in determining priorities for all major source categories, not yet
listed by EPA. These are (1) the quantity of.air pollutant emissions
that each such category will emit, or will be designed to emit; (2) the
extent to which each such pollutant may reasonably be anticipated to
endanger public health or welfare; and (3) the mobility and competitive
nature of each such category of sources and the consequent need for
nationally applicable new source standards of performance.
The Administrator is to promulgate standards for these categories
according to the schedule referred to earlier.
In some cases it may not be feasible immediately to develop a
standard for a source category with a high priority. This might happen
when a program of research is needed to develop control techniques or
because techniques for sampling and measuring emissions may require
refinement. In the developing of standards, differences in the time
required to complete the necessary investigation for different source
categories must also be considered. For example, substantially more
time may be necessary if numerous pollutants must be investigated from a
single source category. Further, even late in the development process
the schedule for completion of a standard may change. For example,
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inablility to obtain emission data from well-controlled sources'in time
to pursue the development process in a systematic fashion may force a
change in scheduling. Nevertheless, priority ranking is, and will
continue to be, used to establish the order in which projects are
initiated and resources assigned.
After the source category has been chosen, the types of facilities
within the source category to which the standard will apply must be
determined. A source category may have several facilities that cause
air pollution, and emissions from some of these facilities may vary from
insignificant to very expensive to control. Economic studies of the
source category and of applicable control technology may show that air
pollution control is better served by applying standards to the more
severe pollution sources. For this reason, and because there is no
adequately demonstrated system for controlling emissions from certain
facilities, standards often do not apply to all facilities at a source.
For the same reasons, the standards may not apply to all air pollutants
emitted. Thus, although a source category may be selected to be covered
by a standard of performance, not all pollutants or facilities within
that source category may be covered by the standards.
2.3 PROCEDURE FOR DEVELOPMENT OF STANDARDS OF PERFORMANCE
Standards of performance must (1) realistically reflect best demon-
strated control practice; (2) adequately consider the cost, the non-air-
quality health and environmental impacts, and the energy requirements of
such control; (3) be applicable to existing sources that are modified or
reconstructed as well as new installations; and (4) meet these conditions
for all variations of operating conditions being considered anywhere in
the country.
The objective of a program for developing standards is to identify
the best technological system of continuous emission reduction that has
been adequately demonstrated. The standard-setting process involves
three principal phases of activity: (1) information gathering, (2)
analysis of the information, and (3) development of the standard of
performance.
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During the information-gathering phase, industries are queried
through a telephone survey, letters of inquiry, and plant visits by EPA
representatives. Information is also gathered from many other sources,
and a literature search is conducted. From the knowledge acquired about
the industry, EPA selects certain plants at which emission tests are
conducted to provide reliable data that characterize the pollutant
emissions from well-control!ed existing facilities.
In the second phase of a project, the information about the industry
and the pollutants emitted is used in analytical studies. Hypothetical
"model plants" are defined to provide a common basis for analysis. The
model plant definitions, national pollutant emission data, and existing
State regulations governing emissions from the source .category are then
used in establishing "regulatory alternatives." These regulatory
alternatives are essentially different levels of emission control.
EPA conducts studies to determine the impact of each regulatory
alternative on the economics of the industry and on the national economy,
on the environment, and on energy consumption. From several possibly
applicable alternatives, EPA selects the single most plausible regulatory
alternative as the basis for a standard of performance for the source
category under study-
In the third phase of a project, the selected regulatory alternative
is translated into a standard of performance, which, in turn, is written
in the, form of a Federal regulation. The Federal regulation, when
applied to newly constructed plants, will limit emissions to the levels
indicated in the selected regulatory alternative.
As early as is practical in each standard-setting project, EPA
representatives discuss the possibilities of a standard and the form it
might take with members of the National Air Pollution Control Techniques
Advisory Committee. Industry representatives and other interested
partids also participate in these meetings.
the information acquired in the project is summarized in the
Background Information Document (BID). The BID, the standard, and a
preamble explaining the standard are widely circulated to the industry
being considered for control, environmental groups, other government
agencies, and offices within EPA. Through this extensive review process,
the points of view of expert reviewers are taken into consideration as
changes are made to the documentation.
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A "proposal package" is assembled and sent through the offices of
EPA Assistant Administrators for concurrence before the proposed standard
is officially endorsed by the EPA Administrator. After being approved
by the EPA Administrator, the preamble and the proposed regulation are
published in the Federal Register.
As a part of the Federal Register announcement of the proposed
regulation, the public is invited to participate in the standard-setting
process. EPA invites written comments on the proposal and also holds a
public hearing to discuss the proposed standard with interested parties.
All public comments are summarized and incorporated into a second volume
of the BID. All information reviewed and generated in studies in
support of the standard of performance is available to the public in a
"docket" on file in Washington, D.c.
Comments from the public are evaluated, and the standard of performance
may be-altered in response to the comments.
The significant comments and EPA's position on the issues raised
are included in the "preamble" of a, promulgation package," which also
contains the draft of the final regulation. The regulation is then
subjected to another round of-review and refinement until it is approved
by the EPA Administrator. After the Administrator signs the regulation,
it is published as a "final rule" in the Federal Register.
2.4 CONSIDERATION OF COSTS
Section 317 of the Act requires an economic impact assessment with
respect to any standard of performance established under Section 111 of
the Act. The assessment is required to contain an analysis of: (1) the
costs of compliance with the regulation, including the extent to which
the cost of compliance varies depending on the effective date of the
regulation and the development of less expensive or more efficient
methods of compliance; (2) the potential inflationary or recessionary
effects of the regulation; (3) the effects the regulation might have on
small business with respect to competition; (4) the effects of the
regulation on consumer costs; and (5) the effects of the regulation on
energy use. Section 317 also requires that the economic impact assessment
be as extensive as practicable.
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The economic impact of a proposed standard upon an industry is
usually addressed both in absolute terms and in terms of the control
costs- that would be incurred as a result of compliance with typical,
existing State control regulations. An incremental approach is necessary
because both new and existing plants would be required to comply with
State regulations in the absence.of a Federal standard of performance.
This approach requires a detailed analysis of the economic impact from
the cost differential that would exist between a proposed standard of
performance and the typical State standard.
Air pollutant emissions may cause water pollution problems, and
captured potential air pollutants may pose a solid waste disposal
problem. The total environmental impact of an emission source must,
therefore, be analyzed and the costs determined whenever possible.
A thorough study of the profitability and price-setting mechanisms
of the industry is essential to the analysis so that an accurate estimate
of potential adverse economic.impacts can.be made for proposed standards.
It is also essential to know the capital requirements for pollution
control systems already placed on plants so that the additional capital
requirements necessitated by these Federal standards can be placed in
proper perspective. Finally, it is necessary to assess the availability
of capital to provide the additional control equipment needed to meet
the standards of performance.
2.5 CONSIDERATION OF ENVIRONMENTAL IMPACTS
Section 102(2)(C) of the National Environmental Policy Act (NEPA)
of 1969 requires Federal agencies to prepare detailed environmental
impact statements on proposals for legislation and other major Federal
actions significantly affecting the quality of the human environment.
The objective of NEPA is to build into the decisionmaking process of
Federal agencies a careful consideration of all environmental aspects of
proposed actions.
In a number of legal challenges to standards of performance for
various industries, the United States Court of Appeals for the District
of Columbia Circuit has held that environmental impact statements need
not be prepared by the Agency for proposed actions under section 111 of
the Clean Air Act. Essentially, the Court of Appeals has determined
that the best system of emission reduction requires the Administrator to
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take into account counter-productive environmental effects of. a proposed
standard, as well as economic costs to the industry. On this basis,
therefore, the Court established a narrow exemption from NEPA for EPA
determination under section 111.
In addition to these judicial determinations, the Energy Supply and
Environmental Coordination Act (ESECA) of 1974 (PL-93-319) specifically
exempted proposed actions under the Clean Air Act from NEPA requirements.
According to section 7(c)(l), "No action taken under the Clean Air Act
shall be deemed a major Federal action significantly affecting the
quality of the human environment within the meaning of the National
Environmental Policy Act of 1969." (15 U.S.C. 793(c)(l))
Nevertheless, the Agency has concluded that the preparation of
environmental impact statements could have beneficial effects on certain
regulatory actions. Consequently, although not legally required to do
so by section 102(2)(C) of.NEPA, EPA has adopted a policy requiring that
environmental impact statements be prepared for various regulatory
actions, including standards of performance developed under section 111
of the-Act. This voluntary preparation of environmental impact statements,
however, in no way legally subjects the Agency to NEPA requirements..
To implement this policy, a separate section in this document is
devoted solely to an analysis, of the potential environmental impacts
associated with the proposed standards. Both adverse and beneficial
impacts in such areas as air and water pollution, increased solid waste
disposal, and increased energy consumption are discussed.
2.6 IMPACT ON EXISTING SOURCES
Section 111 of the Act defines a new source as ". . . any stationary
source, the construction or modification-of which is commenced ..."
after the proposed standards are published. An existing source is
redefined as a new source if "modified" or "reconstructed" as defined in
amendments to the general provisions of Subpart A of 40 CFR Part 60,
which were promulgated in the Federal Register on December 16, 1975
(40 FR 58416).
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Promulgation of a standard of performance requires States to
establish standards of performance for existing sources in the same
industry under section 111 (d) of the Act if the standard for new
sources limits emissions of a designated pollutant (i.e., a pollutant
for which air quality criteria have not been issued under section 108 or
which has not been listed as a hazardous pollutant under section 112).
If a State does not act, EPA must establish such standards. General
provisions outlining procedures for control of existing sources under
section lll(d) were promulgated on November 17, 1975, as Subpart B of 40
CFR Part 60 (40 FR 53340).
2.7 REVISION OF STANDARDS OF PERFORMANCE
Congress was aware that the level of air pollution control achievable
by any industry may improve with technological advances. Accordingly,
section 111 of the Act provides that the Administrator ". . . shall, at
least every four years, review and, if appropriate, revise ..." the
standards. Revisions are made to assure that the standards continue to
reflect the best systems that become available in the future. Such
revisions will not be retroactive, but will apply to stationary sources
constructed or modified after the proposal of the revised standards.
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3. THE AIR OXIDATION INDUSTRY
3.1 GENERAL
The unit process of oxidation of organic compounds generally means
the chemical reaction with an oxidizing agent to introduce one or more
oxygen atoms into the compound, or to remove hydrogen or carbon atoms
from the compound, or a combination of the above. This analysis deals
with the subset of the oxidation industry in which air, or air enriched
with oxygen, is the oxidizing agent.
This chapter describes the air oxidation industry structure, its
production processes, and the associated emissions. The air oxidation
industry consists of those facilities that produce chemicals included in
the synthetic organic chemical manufacturing industry (SOCMI) by reacting
one or more chemicals with oxygen supplied as air or air enriched with
oxygen. This industry also includes chemicals produced using a combination
of ammonia and air or of halogens/and air as reactants. Processes that
use pure oxygen as the reactant or'that use an oxidizing agent other
than oxygen are not considered in this study.
3.2 INDUSTRY STRUCTURE
It is difficult to separate the chemicals produced in air oxidation
processes from other SOCMI products since, air oxidation is not the only
process to produce some of these chemicals.1 Several commercial routes
exist for many of these.air oxidation chemicals including variations in
organic feed, oxygen oxidation, or chemical oxidation. Also, many air
oxidation chemicals are produced as. intermediates for the manufacture of
other chemicals. This section discusses the identification of the air
oxidation chemicals, their uses and growth, and their domestic production.
3.2.1 Air Oxidation. Chemicals
Thirty-six SOCMI chemicals have been identified as air oxidation
chemicals. Table 3-1 lists these air oxidation chemicals; however, this
list is not exclusive.
Each air oxidation chemical belongs to one of the following general
chemical groups:
1. Acid anhydrides,
2. Alcohols,
3-1
-------
TABLE 3-1. SOCMI CHEMICALS PRODUCED BY AIR OXIDATION
1.' Acetaldehyde
2. Acetic Acid
3. Acetone
4. Acetonitrile
5. Acetophenone
6. Acrolein
7. Acrylic Acid
8. Acrylonitrile
9. Anthraquinone
10. Benzaldehyde
11. Benzoic Acid
12. 1,3-Butadiene
13. p-t-Butyl Benzoic Acid
14. n-Butyric Acid
15. Crotonic Acid
16. Cumene Hydroperoxide
17. Cyclohexanol
18. Cyclohexanone
19. Ethylene Dichloride
20. Dimethyl Terephthalate
21. Ethylene Oxide
22. Formaldehyde
23. Formic Acid
24o Glyoxal
25. Hydrogen Cyanide
26. Isobutyric Acid
27. Isophthalic Acid
28. Maleic Anhydride
29. Methyl Ethyl Ketone
30. a-Methyl Styrene
31. Phenol
32. Phthalic Anhydride
33. Propionic Acid
34. Propylene Oxide
(tert butyl hydroperoxide)
35. Styrene
36. Terephthalic Acid
3-2
-------
3. Aldehydes,
4. Alkenes,
5. Carboxylic acids,
6. Esters,
7. Ketones,
8. Nitriles,
9. Oxides,
10. Peroxides, or
11. Halogenated alkanes.
Of the 36 air oxidation chemicals identified, 11 are carboxylic
acids. The remaining 25 chemicals include five ketones, five aldehydes,
two alcohols, two acid anhydrides, three alkenes, three nitriles, two
oxides, one ester, one peroxide, and one halogenated alkane.
Thirteen of the 36 chemicals, contain an aromatic ring or rings.
These 13 chemicals belong to each of the 11 groups listed above except
the nitriles, oxides, and halogenated alkanes.
Most of these chemicals are structurally simple, the acid anhydrides,
aldehydes, esters, and ketones, contain a carbonyl group. The alcohols,
2
nitriles, oxides, and peroxides also contain reactive functional groups.
The air oxidation chemicals have widely varying physical and chemical
characteristics. They exist as solids, liquids, or gases at ambient
condition, and most have characteristic odors.
3.2.2 Uses of Air Oxidation Chemicals
Air oxidation, chemicals have many uses. They are used in production
of plastics, textile fibers, rubber, surface coatings, dyes, food additives,
fragrances, adhesives, drugs, and other substances.
There are two important characteristics of the air oxidation chemicals
in general. First, many air oxidation.chemicals serve as intermediate
chemicals in the production of several other chemicals, which in turn
have numerous end uses and final products. Second, while the number of
uses of air oxidation chemicals is large, the major end uses are not
very numerous. Plastics and textile fibers account for the bulk of
production of the air oxidation chemicals studied here.3 Table 3-2
lists the major use of each identified air oxidation chemical.4'5
3-3
-------
TABLE 3-2. MAJOR END USE OF EACH IDENTIFIED SOCMI AIR OXIDATION CHEMICAL
1. Acetaldehyde
2. Acetic Acid
3. Acetone
4. Acetonitrile
5. Acetophenone
6. Acrolein
7. Acrylic Acid
8. Acrylonitrile
9. Anthraquinone
10. Benzaldehyde
11. Benzoic Acid
12. 1,3 Butadiene
13. p-t-Butyl Benzoic Acid
14. n-Butyric Acid
15. Crotonic Acid
16. Cumene Hydroperoxide
17. Cyclohexanol
18. Cyclohexanone
19. Ethylene Dichloride
20. Dimethyl Terephthalate
21. Ethylene Oxide
22. Formaldehyde
23. Formic Acid
24. Glyoxal
25. Hydrogen Cyanide
26. Isobutyric Acid
27. Isophthalic Acid
28. Maleic Anhydride
29. Methyl Ethyl Ketone
30. o-Methyl Styrene
31. Phenol
32. Phthalic Anhydride
33. Propionic Acid
34. Propylene Oxide
35. Styrene
36. Terephthalic Acid
Intermediates - Drugs - Polymers - Paints
Intermediates - Polymers - Drugs - Solvents - Paints
Intermediates - Paints - Drugs - Solvent
Solvent - Intermediates
Solvent - Drugs - Polymers - Paints
Drugs - Intermediates
Polymers Paints
Polymers - Drugs
Paints
Intermediates - Drugs - Paints
Drugs - Polymers - Paints
Intermediate - Polymers
Intermediate
Polymers - Drugs
Polymers - Drugs - Intermediates
Intermedi ate
Intermediate - Solvent
Intermediate - Solvent
Intermediate - Solvent
Polymers
Drug - Intermediate
Intermediate - Polymers - Solvent
Intermedi ate
Intermediate - Polymers
Intermediate - Drugs
Solvent - Drugs
Polymers - Paints
Polymers - Intermediate,
Sol vent
Polymers
Polymers - Intermediate
Polymers - Drugs - Paints
Drug
Intermediate •
Polymer - Intermediate
Polymers - Drugs - Paints
3-4
-------
3.2.3 Companies and Production of Air Oxidation Chemicals
Fifty-nine companies produce one or more of the 36.air oxidation
chemicals using an air oxidation process. Table 3-3 gives a listing of
the companies and the chemicals produced by each company.^^ Of the
59 companies, 43 companies produce one or two chemicals; 14 produce from
three to nine chemicals; and two produce 10 or more. Celanese Corporation
and Monsanto each produce the largest number, 10.
A major share of the organic chemicals partially or fully produced
by air oxidation processes are controlled by large multi-line chemical
companies, chemical divisions, or subsidiaries of major oil companies,
or multi-industry companies with chemical process operations. Table 3-4
gives the single, largest producer for each chemical and the percent of
the chemical's total capacity owned by that company.8'9 Other major
producers are listed if the largest producer does not control a major
share of the chemical's total production. Thirty-nine percent, or 14
out of 36.identified air oxidation chemicals, have an annual production
greater than a billion pounds per year. Table 3-5 lists the annual air
oxidation process production capacities of the identified air oxidation
chemical. • In general, the higher the production volume of the air
oxidation chemical, the less percent of total capacity any one company
will own. Those chemicals that are produced, by only one company are
typically produced in small volumes.
3.2.4 Location of Air Oxidation Plants
There are currently 164 air oxidation process facilities operating
in the United. States. Forty-nine of these are located in ozone national
ambient air quality standards (NAAQS) nonattainment areas. Table 3-6.
gives a listing of the air oxidation manufacturing processes and the
facilities employing each process.12'13 The plant location, capacity,
and major product(s) are given for each facility. Those [facilities
located, in nonattainment areas are so indicated. !
Although air oxidation industries are scattered throughout several
states, many are located near refineries, which are located near domestic
sources of oil or points of entry for imported oil. Some! of the petrochemical
plants border refineries, thus permitting an easy exchange of products.
This results in a heavy concentration of chemical production along the
3-5
-------
TABLE 3-3. COMPANIES PRODUCING SYNTHETIC ORGANIC CHEMICALS USING
AIR OXIDATION PROCESSES
Company
Allied Chemical Co.
American Cyanamid Co.
Amoco
Amoco-Standard Oil
Ashland Oil, Inc.
BASF Wyandotte Corp.
Borden, Inc.
Celanese Corp.
Chembond
Chevron Chemical Co.
Cifaa-Geigy Corp.
Clark Oil & Refining Corp.
Continental Oil Co..
Co-polymer Rubber and
Chemical Corp.
Croinpton & Knowles Corp.
Degussa Corp.
Denka Chemical Co.
Diamond Shamrock
Dow Badische Co.
Dow Chemical, USA
Chemicals
Acetone, Acetophenone, Cumene Hydroperoxide,
a-Methyl Styrene, Phenol, Phthalic Anhydride
Glyoxal
Terephthalic Acid
Isophthalic Acid, Maleic Anhydride
Maleic Anhydride
Phthalic.Anhydride
Formaldehyde
Acetaldehyde, Acetic Acid,, Acrylic Acid,
n-Butyric Acid, Cyclohexanol, Cyclohexanone,
Formaldehyde, Formic Acid, Methyl Ethyl
Ketone, Propionic Acid
Formaldehyde
Acetone, Phenol, Phthalic Anhydride
Hydrogen Cyanide
Acetone, a-Methyl Styrene, Phenol
Ethylene Dichloride
1,3-Butadiene
Benzaldehyde
Hydrogen Cyanide,
!
i
Maleic Anhydride
I
Ethylene Dichloride
Cyclohexanol, Cyclohexanone
Acetone, Ethylene Oxide, Hydrogen Cyanide,
Phenol, Ethylene1Dichloride
3-6
-------
TABLE 3-3 (Continued). COMPANIES PRODUCING SYNTHETIC ORGANIC CHEMICALS
USING AIR OXIDATION PROCESSES
Company
DuPont
Eastman Kodak Co.
Ethyl Corporation
El Paso Natural Gas
Exxon Corp.
Firestone Tire. & Rubber Co.
GAP Corp.
General Electric.
Georgia-Pacific Corp.
Getty Oil Co.
B.F. Goodrich Chemical
Gulf Oil Corp.
Hereofina
Hercules, Inc.
Hocker
ICI Americas Inc.
Inter1! Minerals & Chemical
Corp.
Kalama Chemical, Inc.
Koppers Co., Inc..
Monsanto Co.
Chemicals
Acetonitrile, Acrylonitrile, Cyclohexanol,
Cyclohexanone, Formaldehyde, Hydrogen
Cyanide, Terephthalic Acid
Acetaldehyde, Acetic Acid, n-Butyric Acid,
Crotonic Acid, Isobutyric Acid, Terephthalic
Acid
Ethylene Dichloride
1,3-Butadiene
Phthalic Anhydride
1,3 Butadiene
Formaldehyde
Acetone, Phenol
Acetone, Formaldehyde, a-Methyl Styrene, Phenol
Acetone, Acetophenone, a-Methyl Styrene, Phenol
Ethylene Dichloride
Formaldehyde
Dimethyl Terephthalate, Terephthalic Acid
Formaldehyde, Hydrogen Cyanide
Formaldehyde
Ethylene Dichloride
Formaldehyde
Benzoic Acid, Phenol
Phthalic Anhydride
Acetone, Acrylonitrile, Cyclohexanol,
Cyclohexanone, Formaldehyde, Hydrogen
Cyanide, Maleic Anhydride, Phenol,
Phthalic Anhydride
3-7
-------
TABLE 3-3 (Continued). COMPANIES PRODUCING SYNTHETIC ORGANIC CHEMICALS
USING AIR OXIDATION PROCESSES
Company
Nipro, Inc.
Northwest Indust., Inc.
011n Corp.
Oxirane Corp.
Pacific RC
Pfizer, Inc.
PPG Indust., Inc.
Reichhold Chems., Inc.
Rohm and Haas Co.
Shell Chemical Co.
Standard Oil Co. (OH)
Stauffer Chemi. Co.
Stepan Chemical Co.
Tenneco, Inc.
Toms River Chemical Corp.
UOP, Inc.
Union Carbide Corp.
U.S. Steel Corp.
Vulcan Material Co.
Wright Chemical Corp.
Chemicals
Cyclohexanol, Cyclohexanone
Benzoic Acid
Propylene Oxide
Propylene Oxide, Styrene
Formaldehyde
Benzoic Acid, Maleic Anhydride, Phenol
Ethylene Dichloride
Formaldehyde, Maleic Anhydride
Hydrogen Cyanide, Acrylic Acid
Acetone, p-t-Butyl Benzoic Acid, Phenol,
Ethylene Dichloride
Acetonitrile, Acrylonitrile, Hydrogen Cyanide
Ethylene Dichloride
^Phthalic Anhydride
Benzoic Acid, 1,3-Butadiene, Formaldehyde,
Maleic Anhydride
Anthraquinone
Benzaldehyde
Acetone, Acetophenone, Acrolein, Acrylic Acid
Ethylene Oxide, Phenol, Propionic Acid,
a-Methyl Styrene
Acetone, Cumene Hydroperoxide, Maleic
Anhydride, a-Methyl Styrene, Phenol,
Phthalic Anhydride
Ethylene Dichloride
Formaldehyde
3-8
-------
TABLE 3-4. LARGEST PRODUCERS OF IDENTIFIED SOCMI AIR OXIDATION CHEMICALS
Chemicals
tcetal dehyde
icetic Acid
acetone
tcetonitrile
tcetophenone
Icrolein
tcrylic Acid
Icrylonitrile
Inthraquinone
enzaldehyde
enzoic Acid
,3-Butadiene
-t-Butyl Benzoic
Acid
i-Butyric Acid
)rotonic Acid
umene Hydroperoxide
tyclohexanol/
Cyclohexanone
•thylene Dichloride
imethyl Terephtha-
late
thylene Oxide
ormaldehyde
ormic Acid
lyoxal
Single Largest, Producer
Celanese Corp.
Celanese Corp.
Allied Chemical Corp.
Percent of
Total Capacity
68
74
17
N/A
N/A
Union Carbide Corp
Rohm & Haas Co.
Monsanto Corp.
Toms River Chemical Corp.
N/A
Kalama Chemical, Inc.
Tenneco
Shell Chemical Co.
Eastman Kodak Co.
Eastman Kodak Co.
N/A
E.I. DuPont de Nemours &
Co., Inc. (E.I. DuPont)
Dow Chemical Co.
Hercofina
Union Carbide Corp.
Celanese Corp.
Celanese Corp.
American Cyanamid
N/A
N/A
100
42
49
100
N/A
56
57
100
100
100
N/A
40
35
75
79
20
100
100
Other Major Producers
Union Carbide Corp.
Shell Chemical Co.
Monsanto Co.
Dow Chemical, USA
U.S. Steel Chemicals
N/A
N/A
Celanese Chemical
Union Carbide Corp.
E.I. DuPont
N/A
Northwest Indust., Inc.
El Paso Natural Gas
N/A
Monsanto Co.
Shell Chemical Co.,
PPG Industries, Inc.'
Diamond Shamrock Corp,
Borden, Inc.
E.I. DuPont
Georgia-Pacific Corp.
3-9
-------
TABLE 3-4 (Continued). LARGEST PRODUCERS OF IDENTIFIED SOCMI AIR
OXIDATION CHEMICALS
Chemicals
Hydrogen Cyanide
Isobutyric Acid
Isophthalic Acid
Maleic Anhydride-
Methyl Ethyl Ketone
o-Methyl Styrene
Phenol
Single Largest. Producer
E.I. DuPont
Eastman Kodak Co.
Amoco-Standard Oil Co.
Monsanto Co.
Celanese Corp.
Allied Chemical Corp.
Allied Chemical Corp.
Percent of
Total Capacity
53
100
100
24
100
45
18
Phthalic Anhydride Koppers Co., Inc.
Propionic Acid
Propylene Oxide
Styrene
Terephthalic Acid
Union Carbide Corp.
Oxirane Corp.
Oxirane Corp.
Amoco
N/A s Information not available.
26
100
100
100
58
Other Major Producers^
Rohm and Haas Co.
Ashland Chemical Co.
U.S. Steel Chemicals
Amoco-Chemicals
U.S. Steel Chemicals
Monsanto Co.
Shell Chemical Co.
U.S. Steel Chemicals
Dow Chemical, USA
Union Carbide Corp,
Monsanto Co.
U.S. Steel Corp.
Stepan Chemical Co.
E.I. DuPont
3-10
-------
TABLE 3-5. ANNUAL PRODUCTION CAPACITY OF THE IDENTIFIED SOCMI AIR
OXIDATION CHEMICALS
,f
Chemical
f
1. Acetaldehyde
2. Acetic Acid
3. Acetone
4. Acetonitrile
5. Acetophenone
6, Acrqlein
7. Acrylic Acid
8. Acrylonitrile
9. Anthraquinone
10. Benzaldehyde
11. Benzoic Acid
12. 1 ^Butadiene
13. p-t-Butyl Benzoic Acid
14. n-Butyric Acid
15. Crotonic Acid
16, Cumene Hydroperoxide
17. Cyclohexanol \
18. Cyclohexanone
19. Ethylene Dichloride
20. Dimethyl Terephthalate
21. Ethylene Oxide
22. Formaldehyde
23. Formic Acid :
24. Glyoxal
25. Hydrogen Cyanide
26, Isobutyric Acid
27. Isophthalic Acid
28. Maleic Anhydride
29. Methyl Ethyl Ketone
30. a-Methyl Styrene
31. Phenol
Capacity in
Gigagrams Per Year
630
770
950
N/A
N/A
27
428
880
2a
N/A
145
410
3b'c
6c,d
6.
N/A
e
925e
5888
890
1430
3900
7
N/A
620
5c,d
66.
200
40
24
T492
3-11
-------
TABLE 3-5 (Continued). ANNUAL PRODUCTION CAPACITY OF-THE IDENTIFIED
SOCMI AIR OXIDATION CHEMICALS7
Chemical
32. Phthalic Anhydride
33. Propionic Acid
34. Propylene Oxide.
35. Terephthalic Acid
36, Styrene
Capacity in
Gigagrams Per Year
572
86.
181
2235
635
N/A s Data not available. .
aLetter from Bobsein, W.P., Toms River Chem. Corp., to Evans, L.B.,
EPA, February 11, 1980.
Estimated based on data, given in letter from Haxby, L.P., Shell Oil
Co., to Evans, L.B., EPA, January 9, 1980.
cMemo from Galloway, J., EEA, to SOCMI Air Oxidation File. Estimation
of capacities for p-t-Butylbenzoic Acid, n-Butyric Acid, and Isobutyric
Acid from company data, April 9, 1981.
Estimated based on data, given in letter and attachment from Edwards, J.C.,
Eastman Kodak Co., to Evans., L.B., EPA, February 6, 1980.
Production capacity of cyclohexanol and. cyclohexanone have been reported
together.
fAir oxidation capacity alone is given. Table 9-2 gives the total
production capacity of these chemicals by all processes. Unless
otherwise noted, 1981 data supplied by the Chemical Manufacturers'
Association have been used (Reference 7).
3-12
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Gulf Coast (Texas and Louisiana) and the East Coast, particularly in New
Jersey and Pennsylvania.
Air oxidation plants are located in 27 states; over half of the
164 plants are located in the Gulf Coast and the East Coast. Twenty-
eight of the 36 air oxidation chemicals are produced in Texas. Louisiana
and New Jersey each produce 33 percent or more of the 36 air oxidation
chemi cals.
3.3 AIR OXIDATION PRODUCTION PROCESSES
The only determinant for classification as an air oxidation chemical
is the process by which the chemical is produced. Some chemicals identified
as air oxidation chemicals in Section 3.2.1 can be made by nonair oxidation
processes. " Table 3-7 shows the percentages of air oxidation
production of each of the chemicals.
Despite the large variation in reaction types used to produce air
oxidation chemicals, air oxidation processes can be grouped together
because they have one very important characteristic in common, the need
to vent large quantities of. inert material containing VOC to the atmosphere.
These inerts, predominantly nitrogen, are present because air contains
20.9 percent oxygen and 78.1 percent nitrogen by volume on a dry basis.
The nitrogen in the air passes through the reaction unreacted. The
exact quantity of nitrogen and unreacted oxygen emitted is a function of
the amount of excess air used in the production process. The following
sections present a discussion of the reaction types used for the production
of air oxidation chemicals and the important factors which determine the
amount of excess air used.
3.3.1 Reaction Types
The principal types of oxidation reactions that take place in the
production of air oxidation chemicals are:
1. Dehydrogenati on,
2. Introduction of an oxygen atom,
3. Destruction of carbon-carbon bonds,
4. Use of oxygen carrier,
5. Peroxidation,
6. Ammoxidation,
7. Oxidative condensation, and
8. Oxyhalogenation.
3-19
-------
TABLE 3-7. PERCENTAGE PRODUCTION OF SOCMI CHEMICALS BY AIR OXIDATION
Product
1. Acetaldehyde
2. Acetic Acid
3. Acetone
4. Acetonitrile
5. Acetophenone
6. Acrolein
7. Acrylic Acid
8. Acrylonitrile
9. Anthraquinone
10. Benzaldehyde
11. Benzoic Acid
12. 1,3-Butadiene
13. p-t-8uty1 Benzoic Acid
14. n-8utyric Acid
15. Crotonic Acid
16. Cumene Hydroperoxide
17. Cyclohexanol
18. Cyclohexanone
19. 1,2-Oichloroethane
20. Dimethyl Terephthalate
21. Ethylene Oxide
22. Formaldehyde
23. Formic Acid
24. Glyoxal
25. Hydrogen Cyanide
26. Isobutyric Acid
27. Isophthalic Acid
28. Haleic Anhydride
29. Methyl Ethyl Detone
30. o-Methyl Styrene
31. Phenol
32. Phthalic Anhydride
33. Propionic Acid
34. Propylene Oxide
35. Styrene
36. Terephthalic Acid
t> of Product Manufactured
by Air Oxidation
99.7
40
65
No Data
No Data
52
94
100
No Data
No Data
TOO
23
No Data
No Data
No Data
No Data
81
81
96
. 100
51
100
23
No Data
100
No Data
100
80
100a
98
100
62
20
18
100
a
*Produced by air or oxygen oxidation.
aSRI International 1978 Directory of Chemical Producers,
United States of America.
3-20
-------
Dehydrogenation is illustrated in the transformation of a primary
alcohol to an aldehyde:
C2H5OH + %02 = CHgCHO + HgO
or of a secondary alcohol to a ketone:
CH3CHOHCH3
or of an alkane to alkene:
= CH3COCH3
CH3CH2CH2CH3
2 = CH2CHCHCH2 + 2H20
An atom of oxygen may be introduced into a molecule, as is illustrated
by the oxidation of an aldehyde to an acid:
CH3CHO
= CH3COOH
= CH* — CH
or of a hydrocarbon to an oxide:
CH2CH2 +
A combination of the above may occur, as in the preparation of
aldehydes from hydrocarbons:
CH4 + 02
or of benzoi c acid from toluene:
CgH5CH3 +
CH20 + H20
CgHgCOOH +
A combination of dehydrogenation, oxygen introduction, and destruction
of carbon-carbon bond may all occur in the same process of oxidation,
e.g., in the oxidation of naphthalene to phthalic anhydride:
C10H8
C8H4°3 + 2H2° + 2C02
Oxidation may be accomplished indirectly through the use of intermediate
or oxygen carrier:
2CuCl
PdCl,
H20
CH3CHO + HC1 + 2CuCl
Peroxidation occurs readily under certain conditions. Thus, some
reactions occur directly with air when catalyzed by heavy metal salts:
Cumene + air = Cumene Hydroperoxide
3-21
-------
Ammoxidation is a process for the formation of nitriles by the
action of ammonia, in 'the presence of air or oxygen on olefins, organic
acids, or other alkyl group of-alkylated aromatics:
NH
C3H6
= CH2CHCN * 3H2°
Oxidative condensation occurs when two molecules combine with each
other with the introduction of oxygen atoms and removal of small molecules
like water:
2CH3CHO + 02 = CH3COOOCCH3 + H20
Oxyhalogenation is a. process in which oxygen and a halogen reacts
with an organic compound:
C2H4 + %02 + 2HC1 = C1CH2CH2C1 + H20
In some reactions, several types of oxidation take place at the
same time resulting in. co-products and by-products . A co-product is
formed simultaneously along-.with the desired reaction product and is
primarily marketable. A common example of such a reaction would be air
oxidation of cyclohexane, where cyclohexanol and cycl ohexanone. are
18
produced as co-products.. By-products, on the other hand, result from
competitive side or parallel reactions occurring along with the main
reaction. It is generally a "leftover" of the process, which in some
cases is marketable. For example, in the manufacture of acrylonitrile
by ammoxidation of propylene, acetonitrile and hydrogen cyanide are
19
produced as by-products. Also, in some cases., the product of the air
oxidation reaction is not. the end product of the production process,
such as the production of ethyl benzene hydroperoxide which is used to
make styrene. Table 3-8 lists, co-products and by-products for those air
oxidation processes with more than one product.
3.3.2 Raw Materials
The principal raw materials for the manufacture of air oxidation
chemicals are olefins (ethylene and propylene), C4 fractions (butanes
and butenes) and aromatics. Table 3-9 shows the air oxidation chemicals
divided into these categories. Because of. the vast number of different
synthesis routes available, several of the air oxidation chemicals fall
into more than one classification.
3-22
-------
TABLE 3-8. AIR OXIDATION PROCESSES WITH CO-PRODUCT(S) AND BY-PRODUCT(S)
Process
Co-Products
By-Products
Butane. Oxidation II
Acetic Acid, Methyl Ethyl
Ketone
Cyclohexane Oxidation Cyclohexanol, Cyclohexane
Ethylbenzene Hydro-
peroxidation
Cumene Hydroper-
oxidation
Toluene Oxidation
p-Xylene Oxidation
Propylene Oxidation
Styrene, Propylene Oxide
Acetone, Phenol
Phenol, Benzoic Acid
Dimethyl Terephthai ate,
Terephthalic Acid
Acrylic Acid
Propylene Ammoxidation Acrylonitrile,. Hydrogen
Cyanide
Formic Acid, n-Butyric
Acid, Propionic Acid
Cumene Hydroperoxide,
Acetophenone, a-Methyl
Styrene
Acrolei n
Acetonitrile
3-23
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3-24
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In air oxidation processes, there is a large contribution of feedstock
to overall price of the chemical, and thus, there exists.a strong incentive
to find cheaper (or less refined) or more readily available feedstocks.
This can be seen in the gradual switch to butane feedstock in the manufacture
of maleic anhydride. Originally, maleic anhydride was produced via air
oxidation of benzene. With the increase in benzene costs, many new maleic
anhydride plants have switched.to n-butane feeds.20 Another reason for the
switch from benzene to n-butane feed for maleic anhydride would be the
additional cost to meet the proposed NESHAP regulation on benzene.
;Butanes can be obtained from natural gas, from crude oil, or as a
by-product of olefins production. Aromatics can be obtained, from oil as a
product of catalytic reforming or from coal as a by-product of coking. At
present,.the largest source is from catalytic cracking during oil refining,
however, this may change in the future as more synthetic fuel plants based
on coal are built. Several of the air oxidation chemicals are made from
natural gas-based petrochemicals. Alternative routes to these chemicals
utilizing oil-based feeds are being developed.
3.3.3 Reaction Characteristics
In spite of numerous reaction mechanisms, all air oxidation processes
vent large quantities of inert material containing predominantly nitrogen
from air and some VOC. Therefore,, to. quantify VOC emissions, and to select
the applicable control method, it is necessary to quantify offgas flow and
VOC concentrations. As discussed in Chapter 4, flow and VOC concentrations
are the major process parameters which determine the costs of controlling
VOC emissions by thermal or catalytic incineration. This section discusses
the reaction characteristics which affect the offgas flow from air oxidation
processes. Section 3.4 presents the results of the statistical analysis
from which the national VOC emissions profile were developed.
There are several reaction characteristics which determine the amount
of offgas vented to the atmosphere. They are as follows:
1. Reaction stoichiometry,
2. Reaction .phase, and
3. Explosion hazard.
3-25
-------
3.3.3.1 Reaction Stoichiometry
In air oxidation reactions, oxygen from the air reacts with an
organic reactant to produce the following: (1) product air oxidation
chemical, (2) some carbon dioxide and carbon monoxide due to partial
combustion of the feedstock, and (3) cp-products and by-products. The
total oxygen required is dependent on the extent of each reaction. The
Stoichiometry of the reaction and the catalyst selectivity of a process
determine the theoretical amount of oxygen required for a"'given process.
Catalyst selectivity is defined as the quotient of the amount of reaction
product to the amount of converted feedstock. For example, in the
ethylene oxide process, ethylene reacts with oxygen to produce ethylene
oxide (main reaction) and. carbon dioxide according to the following
equations:
(75%) CH2CH£ + %Q2 = CH2 CH2
0
(25%) CH2CH2
302 '= 2C02
(100%) CH2CH
02 =
C2H40
23
The catalyst selectivity is 75 percent. The molecular oxygen ratio
(MOR), defined as moles of oxygen per mole of product, is 0.5 for the
main reaction. However, considering the oxygen required for the complete
combustion side reaction, and the average catalyst selectivity of 75
percent22, the MOR of the overall reaction becomes 1.5.
Generally, all air oxidation processes require greater than
stoichiometric amount of air to realize optimum conversion, favorable
reaction rates, 'and to prevent explosion hazard.
3.3.3.2 Reaction Phase
Generally, air oxidation reaction can be carried out in either
liquid or gas phase. Table 3-10 shows the division of the various air
oxidation processes between liquid and vapor phase. The processes are
categorized according to the phase of the air oxidation reaction step,
and not according to the phase of the step(s) in which the final product (s)
is/are formed.
3-26
-------
TABLE 3-10.
PHASE OF THE AIR OXIDATION REACTION STEP IN THE
PRODUCTION OF AIR OXIDATION CHEMICALS
Liquid Phase
1. Acetaldehyde
2. Acetic Acid
3. Acetone
5. Acetophenone
6. Benzaldehyde
7. Benzoic Acid
8. p-t-Butyl Benzoic Acid
9. n-Butyric Acid
10. Cumene Hydroperoxide
11. Cyclohexanol
12. Cyclohexanone
13. Dimethyl Terephthaiate
14. Formic Acid
15. Isobutyric Acid
16. Isophthalic Acid
17. Methyl Ethyl Ketone
18. a-Methyl Styrene
19. Phenol
20. Propionic Acid
21. Propylene Oxide (tert butyl
22. Styrene3
23. Terephthalic Acid
Vapor Phase
1. Acetaldehyde
2. Acetonitrile
3. Acrolein
4. Acrylic Acid
5. Acrylonitrile
6. Anthraquinone
7. 1,3-Butadiene
8. Ethylene Dichloride
9. Ethylene Oxide
10. Formaldehyde
11. Glyoxal
12. Hydrogen Cyanide
13- Maleic Anhydride
14. Phthalic Anhydride
hydroperoxide)'
The air oxidation step in styrene/propylene oxide manufacture is the
liquid phase hydroperoxidation of ethyl benzene.
3-27
-------
23
Liquid phase reactions generally utilize high molecular weight
thermally unstable reactants., The reaction temperatures are low or
moderate and. usually require high pressures for optimum reaction rates.
The extent of oxidation is controlled by limiting the duration of operation,
controlling the temperature and using low excess air. Large amounts of
excess air may cause.branching of radical precursors with formation of a
multiplicity of radicals and., consequently, runaway reactions which
could ultimately,result in explosion.
The catalyst used in liquid, phase processes may be either dissolved
or suspended in finely divided form to ensure contact with the bubbles
of gas-containing oxygen.which pass through the liquid undergoing oxidation.
To speed up the production, means must be provided for initially raising
the temperature and for later removing reaction heat. Heat may be
removed and temperature, controlled by circulation of either the liquid
being oxidized or a special cooling fluid through the reaction zone and
then through an external heat exchanger. Where low temperatures and
slow reaction rates are indicated, natural processes of heat flow to the
atmosphere may suffice for. temperature control.
In addition, liquid phase processes require adequate mixing and
contact, of the two immiscible.phases of gaseous oxidizing agent and the
liquid being oxidized. Mixing may be obtained by the use of special
distributor inlets for the air, designed to spread the air throughout
the liquid. Mechanical stirring or frothing of the liquid are the other
methods of providing thorough mixing.
Figure 3-1 represents a schematic flowsheet of a liquid phase air
oxidation process. Liquid feedstock and catalyst are fed into a reactor.
The reaction is carried out by passing air through this liquid mixture
at a controlled temperature and pressure. After completion of the
reaction, two streams come out of the reactor, liquid and gaseous. The
liquid stream usually contains the desired product, which is taken to a
product recovery system consisting of a series of different unit operations
(e.g., distillation, crystallization, evaporation, etc). The gaseous
stream containing nitrogen, unreacted oxygen, CC^* and some VOC is
condensed or cooled and then fed into the gas separator to recover the
condensable compounds before, venting it to the atmosphere.
3-28
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In contrast to liquid phase reactions, vapor phase air oxidation
reactions can be effectively applied only to readily volatile substances
that are of sufficient thermal stability to resist dissociation at
elevated temperatures. The desired product must also be thermally
stable to continued oxidation and must be readily separable from gaseous
product. These various restrictions limit the material capable for
economic processing by vapor phase air oxidation to the simpler aliphatic
24
and aromatic, series of compounds.
In vapor phase air oxidation processes, a solid or vapor phase
catalyst may be employed. The temperatures are usually high. Control
is affected by limiting the time of contact, temperature, proportion of
oxygen, type of catalyst, or.by combinations of these factors.
By their very nature., the vapor phase oxidation processes result in
the concentration of reaction heat in the catalyst zone, from which it
must be removed in large, quantities at high temperature levels. Removal
of heat is essential to prevent destruction of apparatus, catalyst, or
raw material. Maintenance..of temperature at the proper level is necessary
25
to ensure the-correct rate and degree of oxidation. Figure 3-2 represents
a schematic flowsheet.of a vapor phase air oxidation process. The
feedstock which is either in vapor or liquid phase is first vaporized,
if required, and, then, mixed with air in a mixing chamber. The mixture
is then fed at the required temperature and pressure into a reaction
chamber where it comes in contact-with a catalyst. After completion of
the reaction, the mixture of gases coming out of the reactor is passed
through a product recovery system consisting of different unit operations,
which can include condensers, scrubbers, or both. The exhaust gas
coming from the product recovery system containing predominantly nitrogen
and some VOC, is vented to the atmosphere or to a control device.
3.3.3.3 Explosion Hazard
Many organic reactants used in air oxidation processes are inflammable
and require,adequate..means to prevent explosion hazard. When vapors of
aa inflammable, organic compound, are mixed with air in the proper proportion,
ignition can produce an explosion. An increase in temperature of a
mixture of organic vapors with air expands the range of organics concentration
capable of leading to an explosion. Because of the explosion hazard,
3-30
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many insurance regulations limit the inflammable organics concentration
to 25 percent of the lower explosive limit in air. Jn some cases to
maintain reaction conditions below the explosive limit, large quantities
of excess air are used. Alternatively, low inlet concentrations can be
achieved by recycling a portion of the reactor offgas back to the reactor
system. Some processes., however, can operate above the explosive limit.
For example, in the manufacture..of formaldehyde by silver catalyst
process, methanol concentration in the gas stream is maintained above
the explosive limit.26 It is, however, possible that some processes, by
use of fluidized bed reactors,, gas. stream recycle, or utilizing sophisticated
27
heat transfer systems may. operate within the apparent explosive range.
The explosion hazard of an air oxidation process is also dependent
on the autoignition temperature of the reactants and'the product. The
autoignition temperature is defined as that minimum temperature required
to initiate or cause self-sustained combustion independently of the
heating or heated element. Compounds having low autoignition temperature
would require better heat removal. The. use of high excess air again
provides a,method of realizing adequate heat removal!.
3.4 STATISTICAL ANALYSIS OF AIR OXIDATION PROCESSES:
In this section, results of statistical analysis of existing air
oxidation processes are presented. One purpose of the analysis is to
develop a nationwide VOC, emission profile. A second purpose is to
determine a valid predictor for excess air in air oxidation processes.
The analysis was based on the data collected from 59 plants producing 14
SOCMI chemicals by air oxidation processes. The details of the statistical
procedure and the analysis of the data are presented in Appendix F. The
following are the conclusions of the statistical analysis. \
1. Of the 13 SOCMI chemicals included in the data base, one
chemical is produced in both liquid and vapor phase; while of the remaining
12 chemicals, seven are produced in the vapor phase and five in the
liquid phase.
2. The ratio of excess air to the stoichiometric air requirement
for vapor phase oxidation processes range from less than one to 13.
3. All liquid phase reactions examined have the ratio of excess
air to the stoichiometric air requirement of less than three.
3-32
-------
4. Excess air requirement is influenced by reaction stoic biometry,
reaction temperature, autoignition temperatures, and explosive limits.
5. As discussed in Appendix F, the amount of excess air required
for vapor phase air oxidation processes can be. predicted by the equation:
where :
l
C3 * C4
C3 V(TiEL)
Constants •
Reaction temperature (°C).
T.. = Lowest autoignition temperature (°C) of any reaction
reactant or product.
EL = Lower explosive limit (volume percent) of most explosive
reactant or product. (If reaction is run above the
upper explosive limit, then the upper explosive limit
is used.)
Actual Off gas Flow
F =
Stoichiometric Input Air*
6, Of the 44 plants producing SOCMI chemicals in the vapor phase,
the distribution, of flows, VOC, and heat content shows that 35 plants
have streams with less than 1,0 volume, percent VOC;. 38 plants have flows
less than 50,000 scfm and 18.plants have streams with less than 20 Btu/scf
heat content. The maximum VOC content is 2.2 volume percent, the
maximum flow is 126,000 scfm, and the. maximum heat content is 114 Btu/scf.
7. Of the 15 plants producing SOCMI chemicals in.the liquid
phase, the distribution of flows., VOC, and heat content shows that eight
plants have streams with less than.0.1 volume percent VOC, seven plants
have flow less than 10,000 scfm,. and 14 plants have streams with less
than 20 Btu/scf heat content. The maximum VOC content is.0.76.volume
percent, the maximum now is 64,000 .scfm, and the maximum heat content
is 41 Btu/scf.
3.4.1 National Emissions Profile
Air oxidation facilities use 36.types of oxidation processes
(23 principal processes and 13 specialty processes) to manufacture 36.
different organic chemicals.- Because of the number and diversity of
3-33
-------
facilities and processes in the air oxidation industry, the traditional
model plant approach was not used.- Because of the number and diversity of
facilities and manufacturing processes in the air oxidation industry, a
large number of model plants would have been required in order to accurately
determine the environmental, energy, and cost impacts associated with the
regulatory alternatives. However, as discussed in Chapter 4, only a limited
amount of vent stream data is required to-determine incinerator costs and
efficiency. The required data include offgas flowrate, net heating value,
and hourly VOC emissionsy and whether the offgas contains halogenated
compounds. Therefore, although data from many types of processes are still
required in order to adequately represent the air oxidation industry, the
data need not consist of fully designed model plants. Rather, a national
statistical profile of air oxidation processes was constructed. The national
profile characterizes air oxidation processes according to national distributions
of the three critical offgas parameters for halogenated and nonhalogenated
vent streams. The regulatory alternative environmental, energy, and cost
impacts are therefore evaluated as impacts upon the entire population of
affected facilities, as represented by the national profile. The development
and statistical, basis for the-national profile are described in detail in
Appendix F.
The actual use of the national statistical profile assumes that the
distribution of offgas fTowrate, VOC emission rate, corrosion properties,
and stream net heating value is chemical independent. Chemical identities
are not considered in the profile, nor is there claimed to be a one-to-one
correspondence between any one data vector and an existing offgas stream.
It is assumed, however, that the overall proportions and distributions of
the parameter values and data vectors be similar to those of the existing
population of air oxidation facilities. Thus, since the national statistical
profile contains 59 data vectors, each data vector and associated impacts of
population control represents 1/59 of the existing population to be analyzed
for control.
The national emissions profile was constructed using emissions data
29
from the Houdry questionnaire. The questionnaire covered 13 major air
oxidation chemicals. These chemicals are shown in Table 3-11. A total of
59 air oxidation plants are represented by the Houdry data, which is about
36 percent of the total air oxidation plants in existence today.
3-34
-------
TABLE 3-11. CHEMICALS COVERED BY HOUDRY QUESTIONNAIRE
Chemical
Acetaldehyde
Acetic Acid
Acrylonitrile
Cyclohexanone/Cyclohexanol
Dimethyl Terephthalate
Ethylene Di chloride.
Ethylene Oxide
Formaldehyde
Formaldehyde
Hydrogen Cyanide
Maleic Anhydride
Phenol
Phthalic. Anhydride
Terephthalic Acid
Number of
Process Plants
Ethanol 1
Ethylene 1
Butane 1
Propy1ene 4
Cycl ohexane 3
p-Xylene, Methanol 2
Oxychlorination 9
Ethylene 4
Methanol Silver Catalyst 9
Methanol Mixed Metal 4
Ammoxidation Methane 1
Benzene 7
Cumene 6
Naphthalene . 2
o-Xylene 3
p-Xylene 2
3-35
-------
3.5 BASELINE EMISSIONS AND CONTROL LEVEL
Baseline control levels refers to the level of control to which any new
sources would be subject without the new source performance standard (NSPS).
This control level was estimated based on two factors. The first is the
degree of emissions control resulting from air pollution control currently
required under State implementation plans (SIP's) and other existing regulations,
The second factor is the level of control projected to be required under
modified SIP's, in ozone NAAQS nonattainment areas requesting-extension,
which would reflect, the level of control recommended in the SOCMI air
oxidation CTG. The choice of baseline emissions control level has a direct
impact on the magnitude of cost* energy, and environmental impacts of any
NSPS. Because of the large number of chemicals covered by the air oxidation
standard, it is difficult to assess the level of baseline emissions control
attributable to either SIP's or current emissions control practiced by
industry for other reasons, e.g., product recovery, odor abatement, etc.
For the purpose of this analysis,, current SIP's and those projected to be in
force to reflect the air oxidation CTG, are used to define the baseline.
Air oxidation facilities are located all over the United States and are
subject to many different SIP's. Over 90 percent of the total SOCMI production
capacity is located in 14 States, with Louisiana and Texas contributing more
than half the production capacity. Of the 14 States, only'Texas, Louisiana,
New Jersey, and Illinois have VOC emission regulations applicable to SOCMI
air oxidation processes. Texas requires facilities emitting more than
either 100 Ibs/day or 250 Tbs/hr, depending on the true vapor pressure of
the VOC, to "properly" incinerate the waste gas stream at 1300°F. This is
30
equivalent to approximately 85 percent VOC reduction. Louisiana also
requires incineration of VOC at 1300°F, with a 0.3 second residence time, or
control by other acceptable methods;.however, control requirements may be
waived if the offgas is not significant or will not support combustion
31
without auxiliary fuel. New Jersey uses a sliding scale, based on the
degree of difficulty in controlling the VOC emission source, to establish
allowable emission rates for individual sources. Depending on the vapor
pressure, concentration, and amount of the waste stream VOC, the New Jersey
32
regulation requires from 0 to 99.7 percent VOC reduction. Illinois does
not differentiate between organic solvents and organic compounds in an
3-36
-------
applicable regulation that limits VOC emissions to eight Ibs/hr unless these
33
emissions are reduced by 85 percent. The remaining 10 States do not have
regulations for control of air oxidation VOC emissions.
Information concerning air oxidation production capacity and VOC
emissions can be used to select a national baseline emission control level
based on the control requirements under existing and projected CTG-based
regulations. However, only some States currently require VOC control at air
oxidation facilities, so assuming that all States require a similar VOC
reduction (e.g., 85 percent) understates the projected impacts of the NSPS.
Therefore, a weighted average of current control requirements and projected
regulations based on the CT6 provides the closest approximation of VOC
control levels without the NSPS. Analysis shows that the weighted average
VOC emissions reduction attributable to the.existing and projected SIP's is
72 percent. This analysis assumes that the national profile adequately
represents the projected new source population of plants in each State with
an applicable SIP, as well as the total population. The method of estimating
the baseline control fraction is discussed in more detail in Appendix F.
3-37
-------
REFERENCES FOR CHAPTER 3
1.. Morrison, R.T. and R.N. Boyd. Organic Chemistry, Third Edition, Allen
and Bacon, Inc., Boston, January 1975.
2. Ibid.
3. The Kline Guide to the Chemical Industry, 1977. C.H. Kline and Company.
4. Chemical Engineering, June 6, 1977, page 142.
5. Chemical and Engineering News, January 29, 1979, page 13.
6. 1979 Directory of Chemical Producers, USA, Stanford Research Institute
International.
7. Darby, W.P. et. al., Regulation of Air Oxidation Processes Within the
Synthetic Organic Chemical Manufacturing Industry: Background Information
and Analysis. St. Louis, Washington University, 1981. pp. 36, Appendix A.
8. Ibid.
9. Op. cit., see Reference 7.
10. Ibid.
11. Darby, op. cit.
12. Ibid.
13. Op. cit., see Reference 7.
14. Weissermel, K. and H.J. Arpe, Industrial Organic Chemistry, Verlag
Chemie, Weinheim, New York, 1978.
15. Lowenheim, F.A. and M.K. Moran, Faith, Keyes and Clark's Industrial
Chemicals, Fourth Edition. New York, A. Wiley-Interscience Publication.
16. Liepins, R., F. Mixon, C. Hudak, and T.B. Parsons. Industrial Process
Profiles for Environmental Use, Chapter 6, The Industrial Organic Chemicals
Industry. Research Triangle Park, NC. U.S. Environmental Protection
Agency. Cincinnati, Ohio. EPA Contract No. 68-02-1319. February 1977.
17. Darby, op. cit.
18, Bruce, W.D. and J.W. Blackburn. Emissions Control Options for the
Synthetic Organic Chemicals Manufacturing Industry, Cyclohexanol/
Cyclohexanone Product Report. U.S. Environmental Protection Agency.
Research Triangle Park, NC. EPA Contract No. 68-92-2577. September 1978.
19. Hobbs, F.D. and J.A. Key. Emissions Control Options for the Synthetic
Organic Chemicals Manufacturing Industry, Acrylonitrile Product Report.
U.S. Environmental Protection Agency, Research Triangle Park, NC. EPA
Contract No. 68-02-2577. August 1978.
3-38
-------
-------
20. Lawson, J.F. Emissions Control Options for the. Synthetic Organic
Chemicals Manufacturing Industry, Maleic Anhydride - Product Report.
U.S. Environmental Protection'Agency, Research Triangle Park, NC.
EPA Contrac. 68-02-2577. March 1978. ;
21. Op. cit., Reference 8.
22. Weissermel, K. and H.J. Arpe.s Industrial. Organic Chemistry. Weinheim -
New York, Verlag Chemie, 1978. p. 128-131.
23. Groggins, P.M., Unit Processes "in 'Organic Synthesis. Fifth Edition,
p. 486-556, 1958.
24. Ibid.
25. Ibid.
26. Lovell, R.J. Emissions Control Options for the Synthetic Organic
Chemicals Manufacturing Industry, Formaldehyde Product Report.
U.S. Environmental Protection Agency. Research Triangle Park, NC.
EPA Contract No. 68-02-2577. February 1979.
27. Blackburn, J.W., Air Oxidation Generic Standard Support. U.S.
Environmental Protection Agency. Research Triangle Park, NC. EPA
Contract No. 68-02-2577, May 1979.
28. Guide for Safety in the Chemical Laboratory, Manufacturing -Chemists
Association.
29. Survey Reports on Atmospheric Emissions from the Petrochemical Industry,
prepared by Houdry Division of Air Products and Chemical., Inc. (data on
file at EPA, ESED, Research Triangle Park, NC, 1972). I
I
30. Environmental Reporter, State Air Laws, State Index. \
31. Ibid.
32. Personal communication with Lee Ivey, New Jersey Air Pollution
Control Agency, September 11, 1975.
33. Op. cit., Reference 30. I
3-39
-------
4. EMISSION CONTROL TECHNIQUES
4.1 INTRODUCTION
This chapter describes the control techniques and associated
emission reduction effectiveness for air oxidation unit process vents of
the synthetic organic chemical manufacturing industry (SOCMI). The
effectiveness of combustion systems is examined with respect to their
principles of operation, advantages, and disadvantages.
The SOCMI process vent streams show a great variety in volume
flows, chemical compositions, and volatile organic compound (VOC)
concentrations. This chapter concentrates on thermal oxidation since it
is a VOC control method universally applicable to SOCMI air oxidation
vent streams, although it is not necessarily the best for a given
process.
Effectiveness and specificity of condensers, absorbers, adsorbers,
and catalytic oxidizers may be affected by changes in waste stream
conditions. These conditions include flowrate, VOC concentration,
chemical and physical properties of VOC, waste, stream contaminants, and
waste stream temperature. Analysis, of air oxidation VOC emissions
control by these methods would be unwieldy. Also, control systems based
on condensation or absorption are generally used as product recovery
devices, and the removal efficiencies, decrease as the VOC concentrations
decrease.
Thermal oxidation, however, is much less dependent on process and
waste stream conditions than the other control techniques. It is the
only demonstrated VOC control which is applicable to all SOCMI air
oxidation processes. Incinerator cost and efficiency determinations
require a limited amount of vent stream data (volume flow, VOC emission
rate, net heating valve, andcorrosion properties). The choice of
thermal oxidation as the single control technique for analysis yields
conservative estimates of energy, economic, and environmental impacts
since thermal oxidation is relatively expensive and energy-intensive.
All new incinerators, if properly designed, adjusted, maintained,
and operated, can achieve at least a 98 percent VOC reduction or 20 ppmv
exit concentration, whichever is less stringent. This control level can
be achieved by incinerator operation at conditions which include a
maximum of 1600°F and 0.75 second residence time.
4-1
-------
Process modification, improvements in product recovery, and use of
additional control devices are possible routes to lower emission levels.
This chapter discusses the advantages and disadvantages of using product
recovery devices such as absorbers, adsorbers, and condensers alone, or
in conjunction with VOC control devices such as boilers and thermal and
catalytic oxidizers to achieve reduction of VOC emissions. Detailed
descriptions and efficiency data are available in Appendix A and in the
references.
Boilers can be useful as VOC control devices only when the waste
gas stream volume flow 'is not large enough to upset the combustion
process. Furthermore, the waste gas stream must either have sufficient
oxygen to be used as combustion air or have a sufficiently high heating
value to be used as part of the fuel input. Air oxidation processes
which currently employ a boiler or process heater for VOC control
include the Andrussow process for manufacture of hydrogen cyanide,
maleic anhydride from benzene, acrylonitrile, and formaldehyde (silver
catalyst). '
All a.ir oxidation processes use a combination of absorption devices,
condensers, or carbon adsorption units for product recovery (or for re-
covery of unreacted raw material). These devices are usually-designed
to recover only as much of the VOC as is economically feasible and
therefore would not be considered control devices. However, in some
plants, these devices are designed to remove more than that amount which
is economically justified. In this case, the devices operate both for
product recovery and as control devices for emission reduction or to
reduce the pollutant load on some other final control device.
Table 4-1 shows some of the SOCMI air oxidation chemical processes
and the product recovery-VOC emission control methods used.
4.2 ADSORPTION
The main function of vapor-phase carbon adsorption is to contain
and concentrate dilute organic vapors from waste streams where condensers
or absorbers are ineffective or uneconomical. Carbon adsorption in most
cases is used for recovery of expensive, unreacted raw material and not
for VOC emission control. The major application of carbon adsorption in
air oxidation processes is for the recovery of aromatic feedstocks such
as benzene, xylene, and cumene. Selected air oxidation processes known
to employ carbon adsorption are listed in Table 4-2.
4-2
-------
ITABLE 4-1. PRODUCT RECOVERY AND EMISSION CONTROLS CURRENTLY USED IN ONE OR MORE
PLANTS EMPLOYING MAJOR AIR OXIDATION PROCESSES
Chemical
1 dehyde
c Acid
: Acid/Formic
d/Methyl Ethyl
one
ne/Phenol
onitrile
ic Acid
jtadiene
lexanol/
lohexanone
sne Di chloride
:ne Oxide
dehyde
1 dehyde .
jen Cyanide
: Anhydride
: Anhydride
ic Anhydride
lie Anhydride
iene Oxide/
"ene
ithalic Acid/Di-
lyl Terephthalate
idenser
iorber
•bon Adsorber
?rmal Tnrinpva-f-nv
Product or
Process Recovery
Wacker
Wacker
Butane
Cumene Peroxidation
Propene Ammoxidation
Propene
Butene Oxidative
Dehydrogenation
Cyclohexane
Ethyl ene Oxychlori nation
Ethyl ene
Silver Catalyst
Mixed Metal Oxide
Catalyst
Andrussow
Benzene
Butane
Naphthalene
Xylene
Ethyl benzene Peroxidation
Xylene
i
1,
1,
1,
1,
1,
1,
1,
1,
1,
1,
1,
1,
2
1,
1,
1,
1,
1,
1,
Raw Material Emission
Equipment Control Equipment
2
2
2
3
2 5, 6.
2 4B
2 4B
2
2 - . 4B, 5
2 5
2 6.
2
6.
2, 3 4B, 5, 6.
2 4
2 4
2 4B
2
2, 3
rmal Incinerator - Waste Heat Boiler
alytic Incinerator !
cess Heater or Boiler
4-3
-------
TABLE 4-2. SELECTED AIR OXIDATION PROCESSES KNOWN TO USE CARBON ADSORPTION
FOR PRODUCT/RAW MATERIAL RECOVERY OR EMISSION REDUCTION
Chemical
Acetone/Phenol
Maleic Anhydride
Terephthalic Acid/
Dimethyl Terephthalate
Primary Compound Recovered
Cumene
Benzene
Xy1ene
4-4
-------
Adsorption devices work by capturing vapor-phase molecules upon the
surface of a solid. The molecules adhere primarily through two mechanisms:
(1) physical adsorption, in which Van der Waal's forces attract and hold
the gas molecules to the adsorbent surface, and (2) chemical adsorption
(chemisorption), in which the molecules are chemically bonded to the
adsorbent.
Oxygenated adsorbents such as silica gels, fullers, diatomaceous, and
other siliceous earths, synthetic zeolites, and metallic oxides exhibit
greater selectivity than activated carbon. However, due to their affinity
for polar molecules, they have a greater preference for water than organics
and are of little use on the moist air streams from SOCMI air oxidation
2
process vents. Vent stream dehumidification may be possible but will
necessitate more equipment and increase treatment cost.
4.2.1 Carbon Adsorption Process
Material recovery by carbon adsorption may be too difficult or expensive
for some chemicals when their vapor concentrations are below 700 ppmv.
Although carbon adsorption system configurations vary according to the
volume of gas handled and allowable pressure drop, a typical set-up is
shown in Figure 4-1. After filtering and cooling, the waste gas is directed
through a bed of carbon granules (Adsorber 1). In time, traces of organic
vapors appear in the exit air and the removal efficiency rapidlyidecreases
(breakthrough). At this point, the waste gas stream is routed through a
fresh bed, and the saturated bed is regenerated by passing a hot;gas
through it to desorb (strip) the organics from the carbon. Low-pressure
steam is a common regeneration fluid providing a- concentration gradient to
facilitate mass transfer of adsorbate from the carbon bed and supplying the
heat of desorption. The steam and organic vapors are then condensed and
the organics separated from the water by decantation and/or distillation.
The freshly-regenerated bed is cooled, dried, and prepared for ariother
service cycle. j
4.2.2 Carbon Adsorption Emissions Removal Efficiency j
State-of-the-art carbon adsorption systems for VOC recovery; can have
outlet concentrations in the range of 50 to 100 ppmv with concentrations as
low as 10 to 20 ppmv achievable with some compounds. For inlet(concentrations
4-5
-------
YOC-Udw
Vent Steam
VENT TO
ATMOSPHERE
ADSORBER 2
(REGENERATING)
OECANTOR
and/or
DISTILLING TOWER
Recovered
Solvent
Water
Figure 4-1. Two stage regenerative adsorption system.
4-6
-------
from 700 to 5000 pprav, these numbers yield an expected VOC adsorption
removal efficiency range of 86 to 99 percent. Adsorption removal
efficiencies up to 95 percent can be achieved from some chemicals in
well-designed systems.
4.2.3 Parameters Affecting VOC Removal Efficiency
The most important operating parameter affecting continuing VOC
removal efficiency is the amount of steam used for regeneration. The
graph given as Figure 4-2 shows a generalized form of the relationship
of effluent VOC concentration to steam usage. The exact relationship
depends on the type of VOC being removed and on the operating characteristics
of the system. Figure 4-2 shows that reduced effluent concentration is
obtained by increasing the steam ratio and that very low effluent
concentration levels may be obtained with high steam ratio. Figure 4-2
shows that the position of the effluent concentration curve for each
particular compound is a function of the adsorption temperature, regeneration
temperature, and carbon loading capacity. The effluent concentration
curve is relatively independent of inlet VOC concentrations. When the
adsorption temperature increases, the effluent concentration curve
baseline may increase. Higher regeneration temperatures may shift the
effluent outlet concentration curve downward. A different loading
capacity may shift the curve laterally, since different amounts of steam
may be required to-regenerate the carbon.6
VOC with molecular weights below 45 do not adsorb well on carbon;
high (>130) molecular weight VOC are more difficult to remove during
regeneration. Also, during adsorption of. multicomponent gas streams,
the higher boiling point components tend to displace the lower boiling
point components from the adsorption sites on the carbon.8
Adsorption rates decrease sharply for gas streams with temperatures
of 38°C (100°F) and above.9'10 Inlet VOC concentrations may be limited
to 25 percent of LEL (~5000 ppmv) by insurance requirements. Although
some moisture is desirable in the waste gas to provide more uniform bed
temperatures, excessive humidity can adversely affect the VOC removal
efficiency of a carbon adsorption system. Mist in the gas stream can
rapidly saturate an adsorption bed, taking up adsorption sites. Operating
capacity decreases become pronounced at relative humidities over 50 percent.
11
4-7
-------
EFFLUENT VOC"
•f (11( t2, carbon loading capacity,
and type of compound)
ti • adsorption temperature
fa-regeneration temperature
STEAM RATIO
(Ib of steam/lb of carbon)
Figure 4-2. Generalized form of the relationship of effluent
VOC concentration to steam usage.
4-8
-------
4.2.4 Factors Affecting Applicability and Reliability
Although carbon adsorption can be used for product recovery and to
help control VOC emissions, it is not a control method generally applicable
to SOCMI air oxidation processes. The vent streams from some of these
processes are often saturated with moisture. This would result in
serious loss of adsorption capacity due to the water saturating the
adsorbing medium and taking up adsorption sites. Such process vent
streams require dehumidification to lower the water content. Process
upsets which increase vent stream VOC composition are not uncommon in
air oxidation processes., and may result in an excessive temperature rise
due to the accumulated heat of adsorption of the extra VOC loading.
4.3 ABSORPTION
Absorption is one of the two primary methods of product recovery
used in air oxidation processes. Absorbers are also commonly applied as
auxiliary control devices prior to combustion devices. An absorber can
be added to an existing process for the purpose of VOC control, or an
existing absorber could be modified, perhaps by an increase in the size
or a decrease in the operating temperature, for the purpose of VOC
control. Some, of the air. oxidation processes which employ absorption
are'listed in Table 4-3. . .
Gas absorption devices work by dissolving the solubl-e components of
a gaseous mixture in a liquid. Absorption may only entail the physical
phenomenon of solution or may also involve chemical reaction of the
solute with constituents of the solution.12 The absorbing liquids
(solvents) used are chosen for high solute (VOC) solubility and include
liquids such as water, mineral oils, non-volatile hydrocarbon oils, and
aqueous solutions of acid-neutralizing agents like sodium carbonate and
sodium hydroxide. Devices based on absorption principles include
spray towers, venturi scrubbers, packed columns, and plate columns.
Spray towers require high pressure to obtain droplets ranging'in size
from 500 to 1000 ym in order to present a sufficiently large surface
contact area. They can remove particulate matter without plugging,
but have the least effective mass transfer capability and thus, are
restricted to particulate removal and control of high-solubility gases
such as sulfur dioxide and ammonia.15 Venturi scrubbers have a high
degree of gas-liquid mixing and high particulate removal efficiency but
4-9
-------
TABLE 4-3. SELECTED AIR OXIDATION PROCESSES KNOWN TO USE ABSORPTION FOR
PRODUCT RAW MATERIAL RECOVERY OR EMISSIONS REDUCTION
Chemical
Acetaldehyde
Acetic Acid/Formic Acid/MEK
Acrylonitrile
Acrylic Acid
1,3-Butadiene
Cyclohexanol/Cyclohexanone
Ethylene Dichloride
Ethylene Oxide
Formaldehyde
Hydrogen Cyanide
Maleic Anhydride
Phthalic Anhydride
Propylene Oxide/Styrene
Terephthalic Acid/Dimethyl Terephthalate
4-10
-------
require high pressure .and have relatively short contact times, so their use
is also restricted.to high-solubility gases. The choice for gas absorp-
tion is thus between packed and plate columns. Packed columns are mostly
used for handling corrosive materials and liquids with foaming or plugging
tendencies. They are less expensive than plate columns for small-scale or
pilot plant operations where the column diameter is less than 0.6 m (2 ft).
Plate columns are preferable for large-scale operations, where internal
cooling is desired:and where low liquid flowrates would inadequately wet the
packing. \
4.3.1 Absorption Process
The mechanism;of absorption consists of the selective transfer of one
or more components of a gas mixture into a solvent liquid. The transfer
consists of diffusion to the solvent and dissolution into it. For any given
solvent, solute, and set of operating conditions, there exists an equili-
brium ratio of solute concentration in the gas mixture to concentration in
the solvent. The driving force for mass transfer at a given point in the
operating tower is: related to the difference between the actual concentration
i in
ratio and the equilibrium ratio.
A schematic of a packed, gas absorption tower is shown in Figure 4-3.
The waste gas containing VOC enters at the bottom and rises through the
packing, contacting the absorbing liquid on the surface of the packing
material.- The VOC (solute); is dissolved in the absorbent liquid (solvent)
and is discharged at the bottom of the tower for recovery or disposal. The
cleaned gas exits at the top with reduced VOC concentration, ready for
release or final treatment such as incineration.
4.3.2 Absorption VOC Removal Efficiencies
Systems that utilize organic liquids as solvents usually include the
stripping and recycle of the solvent to the absorber. In this case the VOC
removal efficiency of the absorber is dependent on the solvent stripping
efficiency. If, for example, a system achieved a removal efficiency in
excess of 99 percent with once-through solvent usage, it would be expected
that the removal efficiency would drop to about 94 percent with solvent
20
recycling. Once-through solvent usage can create a liquid waste problem
and incur additional treatment costs.
4-11
-------
CLEANED GAS OUT
To Final Control Device
ABSORBING
LIQUID IN
VOC LADEN
GASIH
ABSORBING LIQUID
WITH YOG OUT
To Disposal or VOC/Solvent Recovery
Figure 4-3. Packed tower for gas absorption.
4-12
-------
For a given absorbent and absorbate, an increase in absorber size or a
decrease. in the operating temperature can increase the VOC removal efficiency
of the system. It may be possible in some cases to increase VOC removal
efficiency by a change in the absorbent.
4.3.3 Factors Affecting Efficiency and Reliability
The effectiveness of an absorption tower, which ts the rate of mass
transfer between the two phases, is largely dependent upon the available gas-
liquid contact area. In packed towers, a reduction in the liquid-to-gas
ratio can lead to channeling where some of the packing is not wetted by the
liquid. Excessive gas flowrates can increase the liquid holdup until the
tower floods and liquid exits at the top with the gas.
VOC concentration can affect the operation of absorption equipment.
Excessive VOC loading can raise the temperature of the tower due to increased
rate of release of the heat of solution, resulting in a decreased concentration
gradient. Absorption is usually not considered when the VOC concentration is
21
below 200-300 ppmv.
4.4 CONDENSATION
Condensation is one of the two primary methods of product recovery used
in air oxidation processes. Condensers are also commonly applied as auxiliary
control devices before thermal incinerators, adsorbers, and other control
22
devices. An existing condenser can be modified for improved VOC emission
control by lowering the operating temperature. The suitability of conden-
sation as an emissions control method depends on several parameters. These
include the VOC concentration at the inlet (usually >1 percent), the VOC
removal efficiency required, the VOC recovery value, and the size of the
23
condenser required for handling the gas volume flowrate. Air oxidation
?4
processes which employ condensation are listed in Table 4-4.
Condensation devices are usually surface or contact condensers.
25
Contact condensers spray a cooled liquid directly into the gas stream, also
26
acting as scrubbers in removing normally noncondensabl e vapors. The
27
coolant is usually water or perhaps a process feed stream. Contact
condensers are generally cheaper, more flexible and efficient for VOC
removal. However, the spent coolant can present a secondary emissions
4-13
-------
TABLE 4-4. SELECTED AIR OXIDATION PROCESSES KNOWN TO USE CONDENSATION FOR
PRODUCT RAW MATERIAL RECOVERY OR EMISSIONS REDUCTION
Chemical
Acetaldehyde
Acetic Acid/Formic Acid/MEK
Acetone/Phenol
Acrylonitrile
Acrylic Acid
1,3-Butadiene
Cyclohexanol/Gyclohexanone
Ethylene Dichloride
Ethylene Oxide
Formaldehyde
Maleic Anhydride
Phthalic Anhydride
Propylene Oxide/Styrene
Terephthalic Acid/Dimethyl Terephthalate
4-14
-------
28
source or waste water treatment problem. Surface condensers have more
auxiliary equipment but can recover valuable and marketable VOC. They do
not contaminate the coolant, therefore minimizing waste disposal problems.
Only surface condensers are discussed in this section.
4.4.1 Condensation Process
Condensation occurs when the partial pressure of a condensable component
equals its vapor pressure at that temperature. Most surface condensers are
of the shell-and-tube type and achieve condensation by removing heat from
29
vapors. As the coolant passes over the tubes, the VOC vapors condense
inside the tubes and are recovered. The coolant used depends upon the
saturation temperature (dewpoint) of the VOC. Chilled water can be used
down to 7°C (45°F), brines to -34°C (-30°F), and chlorofluorocarbons below
-34°C (-30°F).30 Temperatures as low as -62°C (-80°F) may be necessary to
obtain the required VOC removal efficiencies. A table of the estimated
operating temperature required to achieve a given VOC removal efficiency is
given in Reference 31. These temperatures were estimated for aliphatic and
halogenated aliphatic hydrocarbons as a function of inlet VOC concentration.
The major pieces of equipment of a condenser system (as shown in
Figure 4-4) are the shell-and-tube heat exchanger (condenser), refrigeration
system (coolant supply), storage tanks, and pumps.
4.4.2 Condenser VOC Removal Efficiency
VOC removal efficiencies of 50 percent are typical of a condenser used
in conjunction with other control devices. The maximum efficiency reported
is close to 95 percent with average efficiencies of 80 percent reported in
32
the literature.
4.4.3 Parameters Affecting Reliability and Efficiency
Condensers used for VOC control often operate at temperatures below the
freezing point of water. This requires that moist vent streams, such as
those found in air oxidation processes, be dehumidified before VOC removal
to prevent the formation of ice in the condenser. Particulate matter must
not be allowed to enter a surface condenser system since it may deposit on
the finned tubes and interfere with .gas flows and heat transfer. Gas
flowrates from 100 to 2000 cfm are representative of the capacity range for
condensers as emission control devices. Vent streams containing less than
one-half percent VOC are generally not considered for control by condensation.
33
4-15
-------
VOCLAOEHGAS-
DEHUM1DIF1CATION
UNIT
To Remove Water
and
Prevent Freezing
in Win Condenser
COOLANT
RETURN
REFRIGERATION
PUNT
CLEANED GAS OUT
To Other Product Recovery
Equipment, Incineration, or the Atmosphere,
COOLANT
TO PROCESS
Or Disposal
Figure 4-4. Condensation system.
4-16
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4.5 CONTROL BY COMBUSTION TECHNIQUES
Combustion control techniques result in the destruction of the raw
material or product present in the offgas. Therefore, they are usually to
be considered add-on emission control techniques. Although the process
material (ban never be recovered, it is possible to recover much of the
thermal energy released by combustion. In the case of offgas with a high
heating value, it may be economically attractive to combust the vent stream
in a boiler or process heater.
4.5.1 General Combustion Principles
Combustion is a rapid, exothermic oxidation process which results in
the complete or incomplete oxidation of VOC. Most fuels and VOC contain
carbon and hydrogen which, when burned to completion with oxygen, form carbon
dioxide and water.
Since air oxidation vent streams generally contain little oxygen,
additional combustion air must be provided. The total gas volume flow is
therefore I relatively larger than that associated with other types of
control. :
4.5.2 Combustion Control Devices
Control devices using combustion principles include furnaces, boilers,
and thermal and catalytic oxidizers. Combustion in thermal and catalytic
oxidizers are the usual control methods for air oxidation processes.
Furnaces and boilers are only occasionally used ;as control devices for
the larger air oxidation vent streams because the fuel requirements of
their firing cycles may not coincide with the availabrility or heating value
of the offgas. Waste streams with large flows and low heating values can
adversely affect the operation of these devices in two ways. By lowering
furnace temperatures, they cause incomplete combustion and diminished steam
production. Furthermore, an increased volume flow of gases can exceed the
handling capabilities of the exhaust system. j
Catalytic oxidizers are not widely used because jthe catalysts can be
poisoned by sulfur- and halogen-containing compounds.' Moreover, increases
of VOC concentration in poorly controlled streams can raise the catalyst
bed temperature excessively to the point of deactivating the catalyst.
4-17
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4.5.3 Thermal Oxidizers
Thermal oxidation is the method of VOC emission control most widely used
for air oxidation processes because it is applicable to a variety of chemicals
and vent streams conditions. Incineration is the usual method of pollution
control for waste streams with combustible concentration below the LEL (about
470 iS£|Ior 53 !£") sucn as those founcj -jn $OCMI air oxidation processes.
Tablim4-5 is a partial listing of chemical processes using thermal oxidation
for VOC control.
Thermal oxidizers can also control halogenated VOC. However, a higher
chamber temperature is required to properly oxidize chlorinated hydrocarbons
and convert the noxious combustion products to a form more readily removable
by flue gas scrubbing.
4.5.3.1 Thermal Oxidation Process
The combustion process is influenced by time, mixing, and temperature.
An efficient thermal oxidizer must provide:
1. A chamber temperature high enough to enable the oxidation reaction
to proceed rapidly to completion,
2. Enough turbulence to obtain good mixing between the hot combustion
products from the burner, combustion air, and VOC, and
3. Sufficient residence time at the chosen temperature for the
oxidation reaction to reach completion. ;
I
Combustion chamber temperature is an important parameter in the design
of a thermal oxidizer since oxidation rates are highly temperature-dependent.
Incineration of low heating value offgas'necessitates the'burning of an
auxiliary fuel to achieve the desired chamber temperature. As discussed in
Appendix C, destruction of most VOC occurs rapidly at temperatures over 760°C
(1400°F). 'However, higher temperatures, on the order of 980°-HOO°C (1800°-
2000°F), may be required when incinerating halogenated VOC.
Mixing is crucial in achieving goodithermal oxidizer performance. A
properly designed incinerator rapidly coinbines the offgas, combustion air,
and hot combustion products from the burner. This ensures that the VOC be
in contact with sufficient oxygen at a temperature high enough to start the
j
oxidation reaction. Improper mixing can;. permit packets of waste gas to
pass through the incinerator intact. Poor mixing can also lead to poor
temperature distributions so that not allj the waste gas stream reaches or
remains at the design combustion temperature.
4-18
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TABLE 4-5. PARTIAL LIST OF AIR OXIDATION CHEMICALS USING
THERMAL OXIDIZER FOR CONTROLLING VOC EMISSIONS
FROM OFFGAS STREAM
Chemical
itadiene
:rylic Acid
:rylonitrile
>rmaldehyde
ithalic Anhydride
ileic Anhydride
ileic Anhydride
Number of
Plants Reported
,a
3b
2C
4d
le
3f
3f
Reported
Operating
Temperature
(5F)
Not Reported
Not Reported
1800
2000
1200
1400
1600
Reported
Ef f i ci ency
Not Reported
Not Reported
>99%c
99.8-100%d
90-95%
93%
99%
>tandifer, R.L. Draft Butadiene Abbreviated Product Report. Hydroscience.
:PA Contract No. 68-02-2577.
Jlackburn, J.W. Draft Acrylic Acid and Ester Product Report. Hydroscience.
:PA Contract No. 68-02-2577.
tobbs, F.D. and Key, J.A. Draft Acrylonitrile Product Report. Hydroscience.
IPA Contract No. 68-02-2577.
.ovell, R.J. Draft Formaldehyde Product Report. Hydroscience. EPA Contract
Jo. 68-02-2577.
iffice of Air and Waste Management. U.S. Environmental Protection Agency.
Research Triangle Park, NC. Control Techniques for Volatile Organic
[missions from Stationary Sources. Publication No. EPA-450/2-78-022.
lay 1978.
.awson, J.F. Draft Maleic Anhydride Product Report. Hydroscience.
IPA Contract No. 68-02-2577.
4-19
-------
Residence time is the time available for the oxidation reaction to
occur within the combustion chamber. Residence times from as low as
,0.3 to several seconds have been used in thermal oxidizer design.
Vendors generally define residence times in one of two ways. Some count
offgas residence time in any of the available volume of the combustion
chamber. Others credit only residence time within that volume in which
the flue gas is at the combustion temperature. It is this volume which
is theoretically related to destruction efficiency. Therefore, incinerator
efficiency data which use the latter definition of residence time are
more easily compared in an analysis of the relationship of destruction
efficiency to residence time. Moreover, according to this definition, a
larger combustion chamber is required to achieve a given residence time.
Therefore, this definition yields more conservative (higher) estimates
of the cost of control.
Other parameters affecting oxidizer performance are offgas heating
value, water content, and excess combustion air. The offgas heating
value is a measure of the heat available from the combustion of the VOC
in the offgas to CO, and H90. The heat of combustion for specific
K1 Rtn
organic compounds can range from 950 -^ (25 |^) for carbon tetrachloride
CCC1/,) to 35,700 |£- (960 f£|) for methane (CM.).36- Incineration of
f ' SCul SCT K1 Btu
offgas with a low heating value (less than 1860 (50 )) may
require the burning of an, auxiliary fuel to maintain the desired com-
bustion temperature. Auxiliary fuel requirements can be lessened or
eliminated by the use of recuperative heat exchangers. Offgas with a
heating value above 1860 -|^- (50 |^) may support combustion but may
need auxiliary fuel for flame stability. Combustion of an offgas with a
K1 R"f*n
heating value over 5200 ~— (140 |^) can result in flame temperatures
in excess of 1200°C (2200 F). Conventional oxidation equipment can only
be used for such streams if the temperature is kept below 12QO°C (2200°F)
by addition of air, water vapor, or liquid water, or circulation of
exhaust gas. If boilers are used, dilution of the streams would not be
necessary.
A thermal oxidizer handling offgas streams with varying heating
values requires adjustment to maintain the proper chamber temperatures
and operating efficiency. Water has a heat of vaporization of
4-20
-------
a
and a heat capacity of about
41 '39°
27'5 kg mo? °C <1] '8 lb mol °F} ** B?°°C 0 WO°F) and 101 kPa
(14.7 psia). -Entrained water droplets in an offgas stream can sub-
stantially increase auxiliary fuel requirements due to the additional
energy needed to vaporize the water and raise it to the combustion
chamber temperature. Combustion devices are operated with some quantity
of excess air to ensure a sufficient supply of oxygen. Too much excess
air causes an increase in auxiliary fuel requirements since the extra
air is heated up to chamber temperature. Too much excess air also
increases the thermal oxidizer's flue gas volume flow rate and, thus,
its size and cost.
4.5.3.2 Thermal Oxidizer Design
A thermal oxidizer is usually a refractory-lined chamber containing
a burner at one end and generally operated at a temperature of
550°-850°C with a residence time of from, 0.3 to one second.38
Discrete dual fuel burner(s) and inlets for the offgas and combustion
air are so arranged in. the chamber to thoroughly mix the hot products
from the burners with the offgas and air streams. The mixture of hot
reacting gases then passes into the reaction section. This section is
sized to allow the mixture enough time at the elevated temperature for
the oxidation reaction to reach completion. Energy can then be recovered
from the hot flue gases in the heat recovery section. - Preheating of
combustion air or offgas are common modes of energy recovery; however,
it is sometimes more economical to generate steam. Insurance regulations
require that if the waste stream is preheated, the VOC concentration be
maintained below 25 percent of LEL to eliminate explosion hazards.
Thermal oxidizers designed specifically for VOC incineration with
natural gas as the auxiliary fuel may use a grid-type (distributed) gas
burner instead of the conventional dual fuel, forward flame, discrete
burners. The tiny gas flame jets on the grid surface ignite the vapors
as they pass through the grid and ensure burning of all the vapors at
lower chamber temperatures using less fuel and allowing for a shorter
reaction chamber. Typical configurations are shown in Figures
4-5 and 4-6,
4-21
-------
Waste Gas
Auxiliary
Fuel Burner
(discrete)
Waste Gas
Stack
Mixing
Section
Combustion
Section
Optional
Heat
Recovery
Figure 4-5. Discrete burner, thermal oxidizer.
Burner Plate-, Flume Jets:
Stack
Optional
Heat
Recovery
. (natural gas)
Auxiliary Fuel
Figure 4-6. Distributed burner, thermal oxidizer.
4-22
-------
Thermal oxidizers for chlorinated VOC control require additional
control equipment. The flue gases are quenched to lower their temperature
and routed through absorption equipment such as towers or liquid jet
scrubbers to remove the noxious combustion, products. A waste-heat
boiler, constructed of a corrosion resistant alloy, is employed for heat
recovery.
Packaged, single unit thermal oxidizers can be built to control
streams with flowrates in the range of a few hundred scfm to about
50,000 scfm. A typical thermal oxidizer built to handle a VOC waste
stream of 850 jjf^ (30,000 scfm) at a temperature of 870°C (1600°F) with
.0.75 second, residence time probably would be a refractory-lined cylinder.
As discussed in Chapter 8, a typical ratio of flue gas to waste gas is
about 2.2, (both flowrates at standard temperature). The chamber volume
necessary to provide the residence time at that temperature would be
about 99 m3 (3500 ft3). If the chamber length'to diameter ratio is two
to one, a typical design, and allowing a 30.5 cm (1 ft) wall thickness,
the thermal oxidizer would measure 8.3 m (27 ft) long by 4.6.m (15 ft)
wide, exclusive of heat exchangers and exhaust equipment.
4.5.3.3 Thermal Oxidizer Emission Destruction Effectiveness
Based on a study of thermal oxidizer efficiency, cost and fuel use,
it is concluded that 98 percent VOC'reduction, or 20 ppmv as compound
exit concentration (whichever is less stringent) is the. highest reasonable
control level achievable by all new incinerators in all air oxidation
processes, considering current technology.^° An analysis assuming
achievement of this efficiency with incinerator operation at 870°C
(1600°F) and.0.75 second residence time yields conservative estimates of
costs and energy use.
The VOC destruction efficiency of an incinerator can be affected by
variations in chamber temperature, residence time, inlet concentration,
compound type, and flow regime (mixing). A combustion chamber temperature
of 870°C (1600°F) was chosen for the analysis on the basis that higher
temperatures, with higher control efficiencies, are preferred. Test
results show that 98 percent destruction efficiency is achievable at
various temperatures (700°C (1300°F) to 800°C (1500°F)) and residence
times (0.5 to 1.5 seconds). Kinetics calculations comparing the test
conditions to 870°C (16QO°F) temperature with.0.75 second residence time
4-23
-------
show that the latter set of conditions is more conducive to complete VOC
destruction. Cost per pound of VOC controlled increases only 5 to 10 percent
with an increase in temperature from 760°C (14pO°F) to 870°C (1600°F)
with the use of 70 percent recuperative heat recovery. Temperature
higher than 870°C (1$QO°F) were not used in this analysis due to the
materials limitations of metallic heat exchangers. Higher temperatures
would require heat exchange surfaces to be made of more expensive
materials.
Variations in inlet concentration can change a thermal oxidizer's
VOC destruction efficiency. Kinetics calculations describing the
complex combustion reaction mechanisms point to much slower reaction
rates at very low compound, concentrations. Available data show that
20 ppmv as compound maximum outlet concentration is a reasonable limit
which allows for the drop in achievable destruction efficiency with
A?
decreasing inlet concentration.
The data also show that the variation of destruction efficiency as
a function of compound identity is greater at temperatures lower than
7§0°C (14QO°F), although precise quantitative relations could not be
determined. The types of compounds in the data include C, to Cg alkanes
and olefins, aromatics such as benzene, toluene, and xylene and oxygenated
compounds such as MEK and isopropanol. Nitrogen-containing species such
as acrylonitrile and ethylamines and chlorinated compounds such as vinyl
chloride are also included in the data.
At temperatures over 7(30°C (1400°F), the oxidation reaction rate is
much faster than the rate at which mixing takes place. Therefore, VOC
destruction becomes more dependent upon the fluid mechanics within the
oxidation chamber. The flow regime should be such that the mixing of
the VOC stream, combustion air, and hot combustion products from the
burner be rapid and, thorough. This enables the VOC to attain the
combustion temperature in the presence of enough oxygen for a sufficient
period of time for the oxidation reaction to reach completion. Chamber
design and burner and baffle configurations provide for turbulent flow
for improved mixing. As discussed in Appendix C, the most practical
manner of achieving good mixing and efficiency is to adjust the installed
equipment to improve performance.
4-24
-------
Thermal oxidation at a control efficiency lower than 98 percent was
not considered as an alternative control technique. VOC control by
combustion at efficiencies of 90 percent or less would result in an
adverse environmental impact. This impact would result because the
remaining 10 percent of VOC emissions would consist of noxious, partially
oxidized organic compounds (particularly for halogenated vent streams).43
4.5.4 Catalytic Oxidizers
Catalytic oxidation is the second major combustion technique for
VOC emissions control. Selected air oxidation processes known to use
catalytic oxidation for emission control are listed in Table 4-6,
A catalyst works by changing the rate of a chemical reaction
without becoming permanently altered itself. Catalysts for catalytic
oxidation cause a higher rate of reaction at a lower energy level
(temperature), allowing oxidation of VOC at lower temperatures than for
thermal oxidation. Combustion catalysts include platinum and platinum
alloys, copper oxide, chromium and cobalt. These are deposited in thin
layers on inert substrates to provide for maximum surface contact area.
For certain processes, catalytic oxidation under pressure is
employed as an essential element in highly integrated air compression/energy
recovery cycles. In such applications, it is. not a terminal control
device (although it is an efficient destruction device) and, therefore,
cannot lend itself well to replacement or supplementation.
4.5.4.1 Catalytic Oxidation Process
In catalytic oxidation, a waste oxidation, a waste stream and air
are contacted with, a catalyst at a temperature sufficiently high to
allow the oxidation reaction to occur. The waste gas is introduced into
a mixing chamber where it is heated to the proper temperature (about
316°C (600°F)) by contact with the hot combustion products of a burner.
The heated mixture is then passed through the catalyst bed as shown in
Figure 4-7. VOC and oxygen are transferred to the catalyst surface by
diffusion from the waste gas and chemisorbed in the pores of the catalyst
to the active sites where the oxidation reaction takes place. The
reaction products are then desorbed from the active sites and transferred
by diffusion back into the waste gas.44 The cleaned gas may then be
passed through a waste heat recovery device before exhausting into the
atmosphere.
4-25
-------
TABLE 4-6. SELECTED AIR OXIDATION PROCESSES KNOWN TO USE CATALYTIC
OXIDATION FOR EMISSION CONTROL
Chemical
Acrylonitrile
Ethylene Dichloride
Ethylene Oxide
Maleic Anhydride
Formaldehyde (Mixed Oxide)
4-26
-------
Stack
\uxiliary
Burners
Waste Gas
Optional
Heat Recovery
Figure 4-7. Catalytic oxidizer.
4-27
-------
4.5.4.2 Catalytic Oxldizer Emission Reduction Effectiveness
Catalytic oxidizers operating at 450°C (840°F) are able to oxidize
waste gases as effectively as thermal oxidizers operating at 750°C
(1380°F).46< Catalytic oxidizer VOC destruction efficiencies of 95 percent
have been reported in various cases and efficiencies of 97.9 to 98.5 percent
47
are attainable in some systems.
4.5.4.3 Parameters Affecting VOC Destruction Efficiency
Catalytic oxidizer destruction efficiency is dependent on catalyst
volume per unit volume gas processed, operating temperature, and waste
gas VOC composition and concentration. A typical catalyst bed contains
about.0,014 to.0,057 m of catalyst bed volume (0.5 to 2,0 ft ) for each
3 48
28 Nm m (1000 scfm) of waste gas flow. Greater efficiencies can be
attained by an increase in the volume ratio; however, the cost of a
larger catalyst bed can become prohibitive.
The operating temperature range of combustion catalysts is usually
from 316°C (6go°F) to 650°C (1200°F). Lower temperatures may result in
slowing down and possibly stopping the oxidation reaction. Higher
temperatures may result in shortened catalyst life and possibly evaporation
of the catalyst from the support substrate.
Accumulation of particulate matter or condensed polymerized material
can block the active sites and reduce effectiveness. Catalysts can also
be deactivated by compounds containing sulphur, bismuth, phosphorous,
49
arsenic, antimony, mercury, lead, zinc, or tin.
Conditions such as those noted above can result in VOC passing
through or incomplete oxidation with the formation of aldehydes, ketones,
and organic acids.
Sensitivity to waste stream flow condition variations and inability
to handle moderate heating value streams limit the application of
catalytic oxidizers as SOCMI air oxidation process vent emission controls.
4.5.5 Advantages and Disadvantages of Control by Combustion
VOC control fay combustion has several advantages: (1) a properly
designed and operated combustion device can- provide destruction of
nearly all VOC; (2) most combustion units are capable of adapting to
moderate changes in effluent flowrate and concentrations; and (3) control
efficiency is insensitive to the specific VOC pollutant relative to
product recovery techniques.
4-28
-------
There are also disadvantages associated with VOC control by combustion:
(1) high capital and operating costs result from thermal oxidation tech-
niques, which could require a plot of land as large as 3QO ft by 300 ft
for installation; (2) since offgas must be collected and ducted to the
afterburner, long duct, runs may lead to condensation of combustibles and
possibly to duct fires; and (3) since thermal oxidizers utilize combustion
with a flame for achieving VOC destruction, the unit must be located at
a safe distance from process equipment in which flammable chemicals are
used. Alternatively, special designs may be employed to minimize the
risk of explosion or fire.
There, are several disadvantages particularly associated with
control of halogenated VOC by combustion: (1) halogen acids produced by
the combustion must be removed by flue gas scrubbing; (2) water and
caustic are required at the site for scrubbing the flue gas; and (3)
proper waste disposal of the salt formed during flue gas scrubbing is
required.
4.6. TECHNICAL FEASIBILITY OF RETROFITTING CONTROL DEVICES52'57
In case of modified or reconstructed facilities, retrofitting of
control equipment might.be required by the NSPS. The difficulties
encountered in. retrofitting control devices are similar: Retrofit
construction can involve demolition, crowded, construction working
conditions, scheduling construction activities with production activities,
and longer interconnecting piping. Utility distribution systems and
load capacities may not be adequate to accommodate the control equipment,
and extra circuit breakers may be required.
Retrofitted control devices are preferably located on the ground
near the process vents, but can be raised on platforms or mounted on the
roof in order to accommodate, other processes. There must be sufficient
room around the units to allow for maintenance, and the exhausts must
not present a hazard to equipment or personnel. Each requires electricity
to operate fans, control and recording equipment. Valves and dampers
may be pneumatically operated, requiring compressed air lines. Adsorption
devices need steam for regeneration. Condensers probably need a refrigeration
plant and coolant lines.
Retrofits may require remodeling of existing structures and coordination
of the construction efforts with process operations.
4-29
-------
Since thermal oxidizer systems require a relatively large land area
and the safety aspects of an open flame are an important factor, the
longer interconnecting piping probably is the most significant retrofit
cost factor. Because offgas containing halogenated VOC requires combustion
temperatures above those for which recuperative heat recovery is feasible,
a waste heat boiler must be used for heat recovery. However, it may not
be practical for all companies to utilize the heat recovery option. In
a retrofit situation, it may be difficult to locate the waste heat
boiler close to the steam-consuming site.
Data on retrofit requirements and costs for thermal oxidizers,
recuperative heat exchangers, and waste heat boilers are given in
Reference 57.
4-30
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4.7 REFERENCES FOR CHAPTER 4
1. Office of Air and Waste Management. U.S. Environmental Protection
Agency. Research Triangle Park, N.C. Control Techniques for Volatile
Organic Emissions from Stationary Sources. Publication No.
EPA-450/2-78-022. May 1978. p. 53.
2. Stern. A.C. Air Pollution. Volume IV, 3rd Edition,. New York, Academic
Press, 1977. p. 336.
3. Ibid., p. 352.
4. Basdekis, H.S. Emissions Control Options for the Synthetic Organic
Chemical Industry. Control Device Evaluation. Carbon Adsorption.
EPA Contract No. 68-02-2577, February 1980. p. 11-15.
5. Stern, op. cit., p. 355.
. 6. Basdekis, op. cit., pp. 11-15 - 11-18.
7. Basdekis, op. cit., p. 1-4.
8. Staff of Research and Education Association. Modern Pollution Control
Technology. Volume I, New York Research and Education Association,
1978. pp. 22-23.
9. Stern, op. cit., p. 356.
/
10. Basdekis, op. cit.
11. Stern, op. city., p. 356.
12. Perry, R.H., Chilton, C.H. Eds. Chemical Engineers Handbook. 5th
Edition. New York. McGraw-Hill. 1973. p. 14-2.
13. Op. cit., see Reference 1, p. 76.
14. Op. cit., see Reference 9, p. 24.
15. Op. cit., see Reference 1, p. 72.
16. Standifer, R.L. Emissions Control Options for the Synthetic Organic
Chemical Industry. Control Device Evaluation. Gas Absorption. EPA
Contract No. 68-02-2577. May 1980. p. II-l.
17. Perry, op. cit., p. 14-1.
18. Hesketh, H.E. Air Pollution Control. Ann Arbor. Ann Arbor Science,
1979. p. 143.
19. Standifer, op. cit., p. III-5.
4-31
-------
20. Ibid.
21. Ibid. p. IT.
22. Op. cit., see Reference 1, p. 83.
23. Erikson, D.G, Emissions Control Options for the Synthetic Organic
Chemical Industry. Control Device Evaluation. Condensation. EPA
Contract No. 68-02-2577, July 1980.
24. Op. cit., see Reference 11, pp. 23-37.
25. Erikson, op. cit., p. II-l.
26. Op. cit., see Reference 1, p. 84.
27. Erikson, op. cit., p. II-l.
28. Ibid., p. II-3.
29. Op. cit., see Reference 1, p. 83.
30. Erikson, op. cit., p. IV-1.
31. Ibid., pp. II-3, III-3.
32. Ibid., p. III-5.
33. Ibid., p. III-5.
34. Stern, op. cit., p. 368.
35. Blackburn, J.W. Emission Control Options for the Synthetic Organic
Chemical Industry. Control Device Evaluation. Thermal Oxidation. EPA
Contact No. 68-02-2577, May 1979. p. II-l.
36. Weast, R.C. Ed., CRC Handbook of Chemistry and Physics. 60th Edition.
Born Raton. 1980. p. D-174.
37. Ibid.
38. Stern, op. cit., p. 368.
39. Reed, R.J. North American Combustion Handbook. Cleveland, North
American Manufacturing Co., 1979. p. 269.
40. Memo and addendum from Mascone, D., EPA, to Farmer, J., EPA.
June 11, 1980.
41. Ibid.
42. Ibid.
4-32
-------
43. Staff of Research and Education Association. Modern Pollution Control
Technology. Volume 1. New York Research and Education Association,
1978, p. 23-6.
44. Op. cit., see Reference 1, p. 32.
45. Key, J.A. Emissions Control Options for the Synthetic Organic Chemicals
• Manufacturing Industry. Control Device Evaluation. Catalytic Oxidation.
EPA Contract No. 68-92-2577. March 1980. p. 1-1.
46. Ibid.
47. Martin, N. Catalytic Incineration of Low Concentration Organic Vapors.
Engelhart. EPA No. 68-02-3133.
48. Kent, R.W. A. Guide to Catalytic Oxidation. West Chester, Pennsylvania.
Oxy-Catalyst, Inc. Research Cotrell, Inc. (In-House Brochure).
49. Key, op. cit., p.. 1-3.
50. Basdekis, op. cit., p. III-2.
51. Blackburn, op. cit., pp. IV-1, V-l.
52. Standifer, op. cit., p. V-l.
53. Eriksqn, op. cit., p. V-l.
54. Key, op. cit., p. III-l.
55. Blackburn, op. cit.,, pp. IV-1, V-l.
56. Basdekis, H.S. Emissions Control Options for the Synthetic Organic
Chemicals Manufacturing Industry. Control Device Evaluation. Thermal
Oxidation Supplement (VOC-Containing Halogens or Sulfur). EPA Contract
No. 68-02-2577, November 1980. pp. IV-1, V-l.
57. Memo from Galloway, J., EEA, to SOCMI Air Oxidation File. August 8,
1980.
4-33
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-------
5. MODIFICATION AND RECONSTRUCTION OF EXISTING FACILITIES
The proposed New Source Performance Standards (NSPS) will apply to all
affected facilities, construction or modification of which commenced after
the date of proposal of the NSPS. Provisions applying to modification and
reconstruction were originally published in the Federal Register (FR) on
December 23, 1971, clarifying amendments were proposed on October 15, 1974
(39 FR 36946), and final regulations were promulgated on December 16, 1975
(40 FR 58416).
A modification is defined as "any physical change in, or change in the
method of operation of, an existing facility which increases the amount of
any air pollutant (to which a standard applies) emitted into the atmosphere
by that facility, or which results in the emission of any air pollutant (to
which a standard applies) into the atmosphere not previously emitted."1
Reconstruction occurs when components of an existing facility are replaced to
such an extent that:
1. The fixed capital cost of the new components exceeds 50 percent of
the fixed capital cost that would be required to construct a comparable
entirely new facility.
2. It is technologically and economically feasible to meet the applicable
standards.
The purpose of this provision is to apply the standards to facilities
that undergo such extensive reconstruction that they are essentially new
sources. Failure to apply NSPS to these facilities would permit owners to
construct such essentially new sources without installing best demonstrated
technology.
"In determining whether either a modification or reconstruction has
occurred, the Agency focuses on the changes made to the piece or pieces of
equipment that the NSPS defines as the "affected facility." If EPA deter-
mines that the "affected facility" has been modified or reconstructed, that
facility alone ~ rather than the whole plant ~ must operate in compliance
with the standards."
Under the following circumstances, an increase in emissions does not
result in a modification:
5-1
-------
1. If a capital expenditure that is less than the most recent
annual asset guideline repair allowance (5.5 percent for chemical
facilities) published by the Internal Revenue Service (Publication 534)
is made to increase the production rate of an existing facility, even if
an increase in emissions results, a modification is not considered to
have occurred.
2. If an increase in hours of operation has occurred.
3. If the type of fuel or raw material has been changed, if this
change does not involve a change in the original design of the facility.
A facility shall be considered to be designed to accommodate an alternative
fuel or raw material if that use could be accomplished under the facility's
construction specifications as amended prior to the change. Conversion
to coal required for energy considerations shall not be considered a
modification.
4. If the increase in emissions results from maintenance, repair,
or replacement which the Administrator determines to be routine for the
source category.
5. If the facility relocates or changes ownership.
6. If the facility adds or uses any system or device whose primary
function is the reduction of air pollutants (except when an emission
control system is removed or is replaced by a system which the Administrator
determines to be less environmentally beneficial).
The air oxidation affected facility is defined as an individual
process/product recovery train. Such a process/product recovery train
would consist of an individual series or train of air oxidation product
recovery equipment along with all air oxidation reactors feeding offgas
into this equipment train. Each air oxidation reactor not feeding
offgas into a product recovery train would constitute a separate affected
facility. Each plant vent emitting any nitrogen which was introduced as
air to the air oxidation reactor(s) would be included in an affected
facility.
This chapter identifies and discusses some possible and/or typical
changes to air oxidation processes of the Synthetic Organic Chemical
Manufacturing Industry (SOCMI) which could be determined as being
modifications or reconstructions. The magnitude of the industry covered
and the complexity of the manufacturing processes permit only a general
qualitative analysis. In addition, the list of modifications identified
is by no means exclusive.
5-2
-------
5.1 TYPES OF MODIFICATION
The 36 chemicals currently identified as being produced by air
oxidation in the SOCMI have been screened to determine which of them are
currently being produced by more than one commercial synthesis.
Table 5-1, which lists these chemicals, was used to identify the following
potential modifications:
1. Feedstock substitution.
2. Reactant substitution.
3. Catalyst substitution.
4. Process equipment changes.
5. Combinations of the above.
Table 5-1 also indicates the percentage of product produced by each
process.
In the following sections, each type of modification is discussed
and the probability of occurrence is delineated.
It is beyond the scope of this study to consider entirely new
technology because of the difficulties in predicting their use.
5.1.1 Feedstock Substitution
A feedstock substitution is dictated by economics and the level of
availability of the-feedstock. Depending upon the specific process, a
change in feedstock may require substantial capital investment to modify
the process to accommodate the change. Table 5-1 shows that 10 chemicals
have the potential for feedstock substitution.
5.1.2 Reactant Substitution
In several cases, the potential exists to substitute air for pure
oxygen or chemical oxidants in the manufacture of SOCMI chemicals, or
vice versa. Table 5-2 lists these chemicals and also indicates the
percentage of product manufactured by each process.
Producing chemicals by air oxidation may have one or both of the
following advantages over chemical and oxygen oxidation:
1. Air as a react&nt is readily available at little or no cost.
2. Less costly construction material for the reactor to resist
corrosion is required as compared to chemical oxidants.
5-3
-------
TABLE 5-1. POSSIBLE FEEDSTOCK, REACTANT, AND CATALYST
SUBSTITUTIONS IN AIR OXIDATION PROCESSES
Product
Acetaldehyde
Acetic Acid
Acetone
1,3 Butadiene
n-8utyrfc Acid
Formaldehyde
Hydrogen Cyanide
Maleic Anhydride
Phenol
Phthalic Anhydride
Feedstock
ethyl ene
ethanol
acet aldehyde
butane
cumene
isopropanol
n-butene
n-butane
butyraldehyde
n-butane
< methanol
methanol
E
propylene
methane
benzene
n-butane
cumene
tol uene
ortho-xyl ene
naphthalene
Reactant
air
air
air or oxygen
air or oxygen
air
air
air
air
air or oxygen
air
air
air
air & ammonia
air & ammonia
air
air
air
air
air
air
Pe
of F
Catalyst
palladium chloride
& cupric chloride
silver
manganese or cobalt
acetate
manganese or cobalt
acetate
sulfuric acid
metallic
mixture of tin, bismuth,
& boron, with phosphoric
acid
chromia-alumina
metallic- si Tver
metal -oxide
70% vanadium pentoxide
on inert carrier
proprietary information
sulfuric acid
cobalt-salt
cobalt acetate
combination of metal
& promoter
rcentage
roducti on
(%}
88
3
33
46
69
29
7
13
67
' 33
77
23
50
50
85
15
93
2
70
30
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In some instances, the reaction rate can be controlled better and thus,
a better selectivity may be achieved by air oxidation. In other cases, •
energy requirements may be lower due to the fact that no separation of
oxygen from nitrogen is required.
However, the major disadvantage of changing from oxygen or chemical
oxidation to air oxidation is a substantial reduction of plant capacity.
The substitution of air for oxygen results in a reduction of partial
pressure in the reactor and, thus, in a lower driving force. In addition,
air is not as strong an oxidizing agent as most chemical agents, resulting
in a lower throughput, slower reaction, or different product mix. For
air oxidation in the vapor phase, the plant capacity theoretically will
be reduced by at least a factor of 4.76, unless the reactor pressure is
increased. Furthermore, air oxidation would require larger equipment
sizes to handle the inert nitrogen. These large equipment sizes would
result in an additional cost for use of air oxidation, compared to
oxygen oxidation.
Most chemical oxidation reactions are carried out in the liquid
phase. When air is substituted for the chemical agent, this substitution
may result in a phase change. In some instances, the catalyst will have
to be changed when oxygen or chemical oxidation processes are converted
into air oxidation processes. The selectivity also may change, resulting
in a different product mix.
5.1.3 Catalyst Substitution
Research in SOCMI is mainly directed towards new catalyst development,
although information on the state of the art in this field is not
readily available. Catalyst changes can be made to improve product mix,
reduce operating costs, or increase conversion rates.
A change in catalysts may cause significant variations in the
quality and quantity of VOC emissions. Such a change may be accomplished
in the existing reactor and may require major modifications in the
reactor system and auxiliary process equipment.
Table 5-1 identifies six chemicals that show the potential for
catalyst substitutions.
5-6
-------
5.1.4 Process Equipment Changes
In the SOCMI air oxidation processes, changes in the process
equipment may constitute a modification. Examples of such modifications
are the replacement of a fixed-bed reactor with a fluidized-bed reactor,
increasing the size of the reactor, and a change in the product recovery
system from an absorber to a condenser or vice versa. These changes can
result in increased VOC emissions, thus constituting a potential modification.
5.1.5 Combination of Modifications
In the majority of cases, a combination of the modifications
described above will be chosen with the decision based on the most
advantageous economics. The most common combination, to date, is a
simultaneous change of feedstock and catalyst, although other combinations
are possible and currently are encountered.
5.2 IDENTIFIED CHEMICALS
This section discusses on a chemical-by-chemical basis the extent
to which the processes identified in Table 5-1 may be modified.
5.2.1 Acetaldehyde
Currently, 88 percent of acetaldehyde is produced by direct liquid
phase oxidation of ethylene using a palladium chloride-cupric catalyst.
In this process, the catalyst is regenerated with air or oxygen. Prior
to the development of this process, acetaldehyde was produced by catalytic
oxidation of ethanol in the vapor phase, which is an air oxidation. No
new ethanol-based plants have been built since the ethylene-based
process was developed and, thus, no conversion of an ethylene-based
plant to an ethanol-based plant will occur.
The conversion of .an ethanol-based plant to an ethylene-based plant
seems highly unlikely because such a conversion would be high in cost,
involving a change in feedstock and catalyst as well as a phase change.
5.2.2 Acetic Acid
Currently, 19 percent of acetic acid is produced by a continuous
liquid phase catalytic reaction of methanol and carbon monoxide, while
46 percent is produced by liquid phase catalytic oxidation of n-butane
with either air or oxygen used as the oxidant and 33 percent is made by
catalytic liquid phase oxidation of acetaldehyde with either air or
oxygen used as the oxidant.
5-7
-------
As emphasized in the general discussion on reactant substitution,
it appears highly unlikely that oxygen will be substituted by air as the
oxidant, because this change would significantly reduce the plant
capacity. A change in feedstock also seems unlikely because the n-
butane-based process requires an absorber while the acetaldehyde-based
process requires a
distillation column.
5.2.3 Acetone
Two major processes compete in the production of acetone:
1) oxidation/dehydrogenation of isopropanol and 2) co-production with
phenol from cumene. Isopropanol accounts for approximately two-thirds
of production, but co-production from cumene tends to control the
price. However, a conversion of an isopropanol-based plant to a cumene
feed is highly unlikely because the production routes involve two
entirely different processes. The isopropanol-based plant produces
acetone by straight oxidation, while acetone is produced as a co-product
from cumene via an intermediate hydroperoxide. In addition, a phase
change and a change in pressure and temperature conditions is involved.
5.2.4 Acetophenone
To date, 60 .percent of acetophenone is produced via air oxidation
of ethyl benzene and 40 percent is made as a by-product in the cumene
oxidation. A change in production methods cannot be expected because
the acetophenone is made as a by-product in the latter process and major
modifications would be involved, in addition to entirely changing the
product mix.
5.2.5 Acrylic Acid
Currently, 90 percent of the acrylic acid is made via air oxidation
from propylene. Approximately 10 percent is produced by either the
high- or low-pressure modified Reppe process, which is not an air
oxidation process. Both modified Reppe processes are expected to be
phased out and replaced by new propylene-based air oxidation facilities.
5.2.6 Benzaldehyde
Benzaldehyde can be produced via air oxidation of toluene or via
1?
hydrolysis of benzyl-chloride. Due to the entirely different processes,
a conversion of a benzyl-chloride-based plant to a toluene-based plant
will not occur.
5-8
-------
5.2.7 1.3 Butadiene :
1,3 Butadiene is predominantly formed .as a by-product from olefins
manufacture (80 percent), with the remaining 20 percent produced by air
oxidation of n-butane (seven percent) and catalytic dehydrogenation of
n-butane (Houdry process, 13 percent). The; Houdry process does not con-
stitute an air oxidation route, although air is utilized to regenerate
the catalyst. ;
I
It cannot be expected that the ethylene manufacturing process, of
which 1,3 butadiene is a by-product, will be converted to a solely 1,3
butadiene manufacturing process. The conversion of the Houdry process
to an air oxidation process does not appear-feasible due to complex
changes necessary in process equipment. This switch would involve a
catalyst and feedstock change as well as the addition of a hydrocarbon
adsorption column.
5.2.8 n-Butyric Acid ;
To date, 67 percent of n-butyric acid is produced by air or oxygen
oxidation of^butyraldehyde and 33 percent i
-------
Due to entirely different systems, no conversion of a C-TPA-based
plant into a para-xylene-based plant is expected. The latter process
would require the addition of a sieries of crystal!izers and a high-
, 16 ;
pressure absorber. j
5.2.11 Ethylene Oxide j
The production of ethylene oxide is an example of the possibility
of a simple reactant substitution. To date, 66 percent is produced by
air oxidation of ethylene while 34 percent is produced by oxygen oxidation
of ethylene. Both processes are carried.out in the vapor phase.
The reasons why substituting air for pure oxygen is unlikely have
been stated under the general discussion of reactant substitution.
Volumetric flow rates arid vent gas compositions are compared in
Table 5-3.
5.2.12 Formaldehyde
Formaldehyde is produced by air oxidation of methanol using a
silver-metal catalyst (77 percent) or by air oxidation of methanol using
a mixed-metal oxide catalyst (23^percent). The silver-metal process
involves a combination of dehydrqgenation and oxidation of methanol.
The metal-oxide process involves :oxidation of methanol. The major
difference between the two processes is the amount of air mixed with the
methanol before conversion. The metallic-silver catalyst process
operates above the upper explosive limit, whereas the metal-oxide-
catalyst process operates below the loweH explosive limit.
The formaldehyde yield from the metal-oxide process is higher than
that from the metallic-silver process andjthe process is simpler because
methanol distillation is not required. However, the equipment costs for
the metal-oxide process are greater because of the larger volume of gas
19
stream. :
Volumetric flow rates of both processes and absorber vent gas
compositions are compared in Table 5-4. If a metallic-silver catalyst
is substituted by a mixed metal-oxide catalyst, VOC emissions will
decrease and, thus, such a substitution would not constitute a problem.
If a metal-oxide-based plant is converted to a metallic-silver-based
plant, VOC emissions will increase and control equipment will be required.
5-10
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different operating conditions. Such a catalyst substitution would
involve a change in the air-to-methanol ratio, the operating temperatures;
and either the addition of a distillation column or a larger absorber
cblumn.
5J2.13 Formic Acid
• To date, 98 percent of the formic acid is produced as a by-product
of acetic acid production by air oxidation of n-butane. The remaining
• 20
two percent is produced by condensation reactions. No conversion of a
condensation facility to an air oxidation plant will occur due to
entirely different operations.
5;2.14 Glyoxal
• Glyoxal is currently manufactured by air or oxygen oxidation of
ethylene glycol. A small percentage is made by chemical oxidation of
21
acetaldehyde with nitric acid which is a relatively new process. In
general, conversion trends are toward new processes; therefore, no
facilities are expected to convert from the new chemical oxidation
process to the older air oxidation method.
5;.2.15 Hydrogen Cyanide
Hydrogen cyanide is either produced by ammoxidation of methane
(50 percent) or as a co-product by ammoxidation of propylene (50 percent)
Due to the; fact that hydrogen cyanide is a co-product in one process and
a single product in the other process, no conversion of facilities is
expected, j
5.2.16 Majleic Anhydride
The manufacture of maleic anhydride is an example of a feedstock
substitution. Currently, 85 percent of maleic anhydride is produced by
vapor phase air oxidation of benzene and 15 percent by butane oxidation.
It has been reported that the benzene feedstock can be replaced by n-
24
butane in an existing facility by simply replacing the catalyst. A
distinct trend has been observed towards utilizing n-butane because this
feedstock is readily available at a lower cost than benzene. Amoco
Chemicals Corporation already produces maleic anhydride by the n-butane
oxidation process. The process and the catalyst used in the plant are
proprietary information; other facilities that have made this feedstock
oc_oc
substitution are cited in the literature.
22
23
5-13
-------
Other reports mention significant differences between the two
processes. The n-butane process is believed to require a longer reaction
27
residence time and, thus, a bigger reactor. Because of this, a higher
capital investment may be required; however, no data are available to
estimate the increase in cost.
Table 5-5 compares the offgas composition of the Amoco Chemicals
Corporation plant with that of a typical plant using the benzene oxidation
process. The offgas flow rates from both processes are approximately
the same. The n-butane process does not emit any benzene; however,
overall VOC emissions are about twice that of the benzene oxidation
process. Thus, any change from benzene to n-butane would constitute a
potential modification.
Due to the observed trend towards utilizing n-butane, the proposal
of the NSPS could.affect existing plants if they choose to convert from
benzene to n-butane. However, a NESHAP for benzene has already been
proposed requiring all existing facilities to control benzene emissions.
Such facilities would probably use a thermal oxidizer to control benzene
emissions. Thus, if a plant converts from the benzene process to the
n-butane process after the NSPS has been proposed, it will already have
a control device to control any additional VOC emissions. No upgrading
of the control equipment will be required because the volumetric flow
rate decreases (see Table 5-5).
5.2.17 Methyl Ethyl Ketone
To date, 25 percent of methyl ethyl ketone is manufactured as a
by-product of air oxidation of butane while 75 percent is made by the
00
dehydrogenation of secondary butanol. Conversion of single-product
processes to co-product processes is highly unlikely.
5.2.18 Phenol
Phenol is predominantly produced by air oxidation of cumene (93
percent). In addition, phenol is a by-product in the benzoic acid
manufacture via air oxidation of toluene and in the manufacture of coal,
29
tar, and petroleum. No conversions are feasible.
5-14
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5.2.19 Phthalic Anhydride
Currently, 70 percent of phthalic anhydride is produced via air
oxidation of ortho-xylene in a fixed-bed reactor, while 30 percent of
phthalic anhydride is produced via air oxidation of naphthalene in a
fluidized-bed reactor. Both processes utilize a vanadium pentoxide
catalyst. The ortho-xylene-based process operates below the lower
explosive limit, and so uses a great excess of air, while the naphthalene-
based process operates within the explosive limits by utilizing a
fluidized-bed reactor.
The ortho-xylene feed process is newer than the naphthalene feed
process and will account for all or nearly all of the future growth in
the industry. However, the older naphthalene feed process will continue
to be operated by those producers who already have an investment in the
process and a ready supply of naphthalene. Some plant conversions might
occur, but it is not likely because the ortho-xylene process employs a
fixed-bed tubular reaction system and the naphthalene process employs a
coil-cooled, fluid-bed reaction system.
Volumetric flow rates and switch condenser offgas compositions are
compared in Table 5-6.
5.2.20 Styrene
To date, 10 percent of styrene is manufactured via air oxidation in
co-production with propylene oxide. The remaining 90 percent is produced
by catalytic dehydrogenation of ethyl benzene. These two routes
represent two completely different processes: the dehydrogenation
process is a one-step operation while the air oxidation process involves
several consecutive steps, each requiring separate reactors.
The conversion of a dehydrogenation process to air oxidation
process is highly improbable because the changes in process equipment
are too costly.
5.2.21 Terephthalic Acid
Terephthalic acid is predominantly produced by p-xylene air oxidation.
In newly developed process, which is not yet commercially available,
terephthalic acid is produced by ammoxidation of p-xylene followed by a
hydrolysis of terephthalamine.34 No emission data from this process are
available yet.
5-16
-------
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5-17
-------
5.3 SUMMARY
From the discussion above, it can be seen that all the changes
described, with the exception of maleic anhydride, involve substantial
changes in catalyst, reactor conditions, and product separation/purification
equipment in addition to a switch i.n feedstock. The magnitude of these
changes will probably make those kinds of potential modifications
economically infeasible.
The substitution of n-butane for benzene in maleic anhydride
manufacture appears to be driven by the rapidly rising price of benzene.
The maleic anhydride NESHAP will require all benzene-based facilities to
achieve a substantial reduction in benzene. The facilities would
probably use a thermal oxidizer to achieve this emission control. If
any benzene-based facilities switch to butane after the air oxidation
standard is proposed, they will already have control and, thus, emissions
should not increase.
Because raw material costs contribute significantly to the total
product cost, much effort will be directed toward the search for cheaper,
more readily available feedstocks (probably based on oil derivatives) in
the next few years, due to the rapidly escalating price of gas and gas
liquids. However, the chemical manufacturers will probably choose to
build new facilities to utilize the cheaper feeds rather than go to the
expense of radically modifying existing facilities.
No existing facilities are expected to undergo sufficient replacement
of components to be considered a reconstructed facility. Any replacements
would be expected to be limited to the reactor alone or to only one
piece of product recovery equipment. The fixed capital cost of such
replacement components would not be expected to exceed 50 percent of the
fixed capital cost that would be required to construct a comparable
entirely new facility.
5-18
-------
5.4 REFERENCES FOR CHAPTER 5 ;
1. Federal Register, Volume 40, Number 242, "Standards of; Performance for
Performance for New Stationary Sources: Modification, Notification, and
Reconstruction"; Support A, 40 CFR 60.14, Tuesday, December 16, 1975.
i
2. Ibid., Support A, 40 CFR 60.15. 1
i
3. Ibid., Reconstruction. !
4. Ibid., Support A, 40 CFR 60.14. :
5. Federal Register, Volume 40, "Air Pollution Control Recommendations of
Alternative Emission Reduction Options for SIP"; 40 CFR 52, January 18,
1979.' :
6. Lovell, R.J. Emissions Control Options for the Synthetic Organic
Chemicals Manufacturing Industry, Acetaldehyde Abbreviated Product
Report. U.S. Environmental Protection Agency. Research Triangle Park,
NC. EPA Contract No. 68-02-2577. January 1979. :
7. Key, J.A. Emissions Control Options for the Synthetic. Organic Chemicals
Manufacturing Industry, Acetic Acid, Formic Acid, Ethyl Acetate, Methyl
Ethyl Ketone Abbreviated Product Report. U.S. Environmental Protection
Agency. Research Triangle Park, NC. EPA Contract No.- 68-02-2577.
March 1979. :
8. Liepins, R., F. Mixon, C. Hudak, T.B. Parsons. Industrial Process
Profiles for Environmental Use, Chapter 6, The Industrial Organic
Chemicals Industry. Research Triangle Institute. Research Triangle
Park, NC. U.S. Environmental Protection Agency. Cincinnati, OH. EPA
Contract No. 68-02-1319. February 1977.
9. Austin, G.T. The Industrially Significant Organic Chemicals - Part 1.
Chemical Engineering, p. 129-130. January 1974. I
10. Liepins, R., F. Mixon, C. Hudak, T.B., Parsons. Industrial Process
Profiles for Environmental Use, Chapter 6, The Industrial Organic
Chemicals Industry. Research Triangle Institute. Research Triangle
Park, NC. U.S. Environmental Protection Agency. Cincinnati, OH.
Contract No. 68-02-1319. February 1977. ;
11. Blackburn, J.W. Emissions Control Options for the Synthetic Organic
Chemicals Manufacturing Industry, Acrylic Acid and Esters Product
Report. U.S. Environmental Protection Agency. Research Triangle Park,
NC. EPA Contract No. 68-02-2577. October 1978.
12. Kirk-Othmer. Encyclopedia of Chemical Technology. .New York, Interscience
Publishers, Vol. Ill (1978). 736 p.
13. Standifer, R.L. Emissions Control Options for the Synthetic Organic
Chemicals Manufacturing Industry, Butadiene Abbreviated Product Report.
U.S. Environmental Protection Agency. Research Triangle Park, NC. EPA
Contract No. 68-02-2577. December 1978.
5-19
-------
14. Liepins, R., F. Mixon, C. Hudak, T.B. Parson;. Industrial Process
Profiles for Environmental Use, Chapter 6, The.Industrial Organic
Chemicals Industry. Research Triangle Institute. Research Triangle
Park, NC. U.S. Environmental Protection Agency. Research Triangle
Park, NC. Contract No. 68-02-1319. February 1977.
15. Bruce, W.D., J.W. Blackburn. Emissions Control Options for the Synthetic
Organic Chemicals Manufacturing Industry, Cyclohexanol/ Cyclohexanone
Product Report. U.S. Environmental Protection Agency. Research Triangle
Park, NC. EPA Contract No. 68-92-2577. September 1978.
16. Dylewski, S.W. Emissions Control Options for the Synthetic Organic
Chemicals Manufacturing Industry, Crude Terephthalic Acid Product Report
Dimethyl Terephthalate and Purified Terephthalic Acid Abbreviated
Report. U.S. Environmental Protection Agency. Research Triangle Park,
NC. EPA Contract No. 68-02-2577. June 1979.
17. Lawson, J.F., V. Kalcevic. Emissions Control Options for the Synthetic
Organic Chemicals Manufacturing Industry, Ethylene Oxide Product Report.
U.S. Environmental Protection Agency. Research Triangle Park, NC. EPA
Contract No. 68-02-2577. November 1978.
18. Lovell, R.J. Emissions Control Options for the Synthetic Organic
Chemicals Manufacturing Industry, Formaldehyde Product Report. U.S.
Environmental Protection Agency. Research Triangle Park, NC. EPA
Contract No. 68-02-2577. February 1979. :
19. Haddeland, G.E., G.K. Chang. Report No. 23,: Formaldehyde, p. 63-95.
A private report by the Process Economics Program. Menlo Park, CA,
Stanford Research Institute. February 1967.
20. Liepins, R., F. Mixon, C. Hudak, T.B. Parsons. Industrial Process
Profiles for Environmental Use, Chapter 6, The Industrial Organic
Chemicals Industry. Research Triangle Institute. Research Triangle
Park, NC. Radian Corporation. Austin, TX. Contract' No. 68-02-1319.
February 1977. I
21. Weissermel, K., H.J. Arpe. Industrial Organic Chemistry. New York,
Weinheim, Verlag Chemie, 1978. p. 321-347.
22. Lowenheim, F.A., M.K. Moran. Faith, Keyes, and Clark's Industrial
Chemicals. Fourth Edition. New York, A Wiley-Interscience Publication.
p. 482-484.
23. Lawson, J.F. Emissions Control Options for the Synthetic Organic
Chemicals Manufacturing Industry, Maleic Anhydride - Product Report.
U.S. Environmental Protection Agency. Research Triangle Park, NC. EPA
Contract No. 68-02-2577. March 1978.
24. Ibid.
25. Lawson, J.F. Trip Report for Visit to Amoco Chemicals Corporation.
Chicago, IL. Hydroscience, Inc. EPA Contract No. 68-02-2577. January
1978.
5-20
-------
26. Ibid.
27. Standard Support Environmental Impact Statement for Control of Benzene
from the Maleic Anhydride Industry. Draft Report. July 1978.
28. Austin, G.T. The Industrially Significant Organic Chemicals - Part 7.
Chemical Engineering, p. 153. January 1974.
29. Ibid. p. 107-108.
30. Chi, C.T., T.W. Huges. Phthalic Anhydride Plant Air Pollution Control.
Monsanto Research Corporation. Dayton, OH. Industrial Environmental
Research Laboratory. Research Triangle Park, NC. Contract No.
68-02-1320. September 1977.
31. W.A. Schwartz. Higgins, Jr., J.A. Lee, R.B. Morris, R. Newirth, J.W.
Pervier. Engineering and Cost Study of Air Pollution Control for the
Petrochemical Industry, Volume 7: Phthalic Anhydride Manufacture from
Ortho-Xylene. U.S. Environmental Protection Agency. Research Triangle
Park, NC. Contract No. 68-02-0255. July 1975.
32. Benzene Emissions from the Ethyl benzene/Styrene Industry. Draft EIS.
U.S. Environmental Protection Agency. Research Triangle Park, NC.
Publication Number EPA-450/3-79-035a. October 1979. 284 p.
33. Liepins, R., F. Mixon, C. Hudak, T.B. Parsons. Industrial Process
Profiles for Environmental Use, Chapter 6, The Industrial Organic
Chemicals Industry. Research Triangle Institute. Research Triangle
Park, NC. U.S. Environmental Protection Agency. Cincinnati, OH.
Contract No. 68-02-1319. February 1977.
34. Lowenheim, F.A., M.K. Moran. Faith, Keyes, and Clark's Industrial
Chemicals. Fourth Edition. New York, A Wiley-Interscience Publication.
p. 808-809.
5-21
-------
-------
6. REGULATORY ALTERNATIVES
This chapter describes the method of regulatory analysis used for
development of the air oxidation ;unit process NSPS and discusses the
regulatory alternatives considered for controlling VOC emissions from
SOCMI air oxidation process vent streams.
Many specific reaction types are used to manufacture the SOCMI air
oxidation chemicals and, consequently, development of regulations for
each chemical would be time-consuming and expensive. However, because
air oxidation processes have many similar characteristics, especially
the need to vent large quantities of inert material containing VOC to
the atmosphere, an alternative approach, the unit process approach, is
feasible. A unit process is a discrete, identifiable chemical reaction,
such as nitration or oxidation, used in organic synthesis. The proposed
air oxidation.NSPS would regulate VOC emissions from all air oxidation
unit processes (including the ammoxidation and oxychlorination processes).
Air oxidation processes are those unit,processes which either use air or
a combination of air and oxygen as an oxygen source in combination with
one or more organic reactants to produce one or more SOCMI chemicals.
The air oxidation affected facility is defined as an individual process/product
recovery train. Such a process/product recovery train would consist of
an individual series or train of |air oxidation product recovery equipment
along with all air oxidation reactors feeding offgas into this equipment
train. Each air oxidation reactor not feeding offgas into a product
recovery train would constitute a separate affected facility. Each
plant vent emitting any nitrogen which was introduced as air to the air
oxidation reactor(s) would be included in an. affected facility. Approximately
30 percent of all new or modified, source SOCMI VOC emissions would be
covered under the.air oxidation unit process NSPS.1'2
6.1 METHOD OF REGULATORY ANALYSES
I
According to the.method of regulatory analysis developed for the
air oxidation unit process NSPS, ja national statistical profile, representing
the air oxidation segment of SOCMI, was used to project the energy,
economic, and environmental impacts associated with VOC control under
several regulatory alternatives. (Projection of these impacts was based
6-1
-------
on the use of a single VOC control technique, thermal oxidation. This
section describes in detail the method of regulatory analysis used in
the development of the air oxidation NSPS.
6.1.1 Unit Process Approach to NSPS Development
Typically, NSPS would be developed on a chemical-by-chemical basis.
The manufacturing processes used by the single chemical-producing industry
covered by such an NSPS would not differ greatly. It therefore would be
possible to design a model plant that can be used to represent the
emissions and control device requirements of typical new sources to be
regulated. This model, along with a projection of the number of new
sources coming on-line in a specified time period, would be used to
analyze the economic, energy, and environmental impacts of control under
several regulatory alternatives. These regulatory alternatives generally
would be based on the use of several applicable control devices that can
have different control efficiencies, costs, and energy requirements.
The results of this analysis allow selection of.the regulatory alternative
that reflects the degree of emission limitation, and the percentage
reduction achievable through application of the best demonstrated technological
system of continuous emission reduction, considering the costs, any
nonair quality health and environmental impacts, and energy requirements.
This regulatory alternative is then used as the basis for selecting a
pollutant emissions limit and formulating the NSPS.
The unit process Approach allows development of a standard that
simultaneously regulates VOC emissions from all SOCMI air oxidation pro-
cesses. Air oxidation facilities use 32 types of oxidation reactions to
manufacture 36 different organic chemicals. Because of the number of
facilities and processes to be covered, a. chemical-by-chemical development
of regulations for air oxidation production processes would require a
considerable amount of time. Conversely, the unit process approach
allows the resource-efficient development of a single, comparably effective
standard that would cover a high percentage of SOCMI VOC emissions. In
addition, this approach allows development of a standard that potentially
would.be applicable to SOCMI chemicals not currently produced by air
oxidation processes, j
6-2
-------
6.1.2 Control Techniques
Industrial experience indicates that many types, of .control devices,
including condensers, absorbers, adsorbers, and incinerators, can be
used to reduce VOC emissions. Selection of the best. VOC. control device
for a particular chemical manufacturing process and determination of the
degree of control achievable depend on the chemical composition of the
vent stream and other process characteristics. The vent stream flow
rate, and VOC concentration, the chemical and physical properties of the
VOC and other contaminants, and the vent stream water content and temperature
may greatly affect the specificity and effectiveness of devices such as
condensers, absorbers, adsorbers, and catalytic incinerators. As a
result, none of these potential control devices is suitable for reduction
of VOC emissions from all air oxidation processes.
However, operation of a thermal oxidizer is much less dependent on
these process and vent stream considerations and, consequently, is the
only demonstrated VOC control technology universally applicable to SOCMI
air oxidation processes. Furthermore, thermal oxidation can achieve the
highest feasible VOC control level of all currently demonstrated technologies.
Consequently, the regulatory analysis for this standard is based on the
use of a single control device, a thermal oxidizer, to project the
energy, economic, and environmental impacts of VOC control. Because
thermal oxidizers are. energy-intensive and relatively costly to operate,
a regulatory analysis based on the use of this device will give conservative
(higher) estimates of the costs and energy impacts associated with
control of VOC emissions from air oxidation processes.
6.1.3 National Profile
One model plant would not have been sufficient for an accurate
projection, of the impacts associated with each regulatory alternative.
Because of the number and diversity of facilities and manufacturing
processes in the air oxidation industry, a large number of model plants
would have been.required. If the use of many model plants had been
necessary, the prospective regulatory alternative analysis would have
been predicted to take so much time that, the unit process approach to
regulation would have had little or no advantage over a chemical-by-
chemical.approach. However, only a limited amount of vent stream data
is required to determine thermal oxidizer costs and efficiency. If it
6-3
-------
is assumed that the offgas contains no oxygen, the required data include
offgas flowrate, net heating value, and VOC emission rate. It must also
be known whether the offgas contains halogenated compounds. Therefore,
although data from many types of processes are still required in order
to adequately represent the air oxidation industry, the data need not
consist of fully designed model plants. Rather, a national statistical
profile of air oxidation processes was constructed. The national
profile characterizes air oxidation processes according to national
distributions of the three critical offgas parameters for halogenated
and nonhalogenated vent streams. The impacts of each regulatory alternative
are therefore evaluated as impacts upon the entire population of affected
facilities, as represented by the national profile. The emission and
production factors used to construct the data base for the statistical
procedure and national profile are from existing air oxidation plants
that represent.about 36 percent of the total air oxidation plant population.
Because there is no recognizable bias involving the four offgas parameters
in this-data sampling, this percentage of plants, provides an adequate
sample size to allow construction of a profile that is. representative of
the entire air oxidation.part of SOCMI. Although the national profile
is biased toward high volume products, correspondence with plants and
EPA product reports indicate that the. small-volume air oxidation chemicals
do not differ significantly in the distribution of the four offgas
parameters. Therefore, it is assumed that the overall distribution of
key vent stream variables for the new air oxidation plants would be the
same as that for the existing population.
The actual use of the national statistical profile assumes that the
distribution of offgas, flow, VOC emission rate, and stream heating value
is chemical-independent. Chemical identities are not considered in the
profile, nor is there claimed to be a one-to-one correspondence between
any one data vector of three offgas parameters and an existing or new
offgas stream. It is assumed, however,. that the overall proportions and
distributions of the parameter values and data vectors are similar to
those of the new population of air oxidation facilities. Thus, since
the national.statistical profile contains 59 data vectors, each data
vector represents 1/59 of the new population. Each data vector represents
6-4
-------
a hypothetical vent stream. .Therefore, the impacts of a given regulatory
alternative., such as annualized cost of control, VOC emission reduction,
and facility cost-effectiveness, can be associated with each data vector.
It is not assumed that such individual impacts on a data vector would
represent impacts on any given new facility, nor are the data vectors
used as individual impact, models. Instead, the impacts of a regulatory
alternative on a data vector represent 1/59 of the overall impact on the
projected.new population of facilities. Due to the wide variation in
processes used and in the.types of control devices present across the
air oxidation industry, only uncontrolled emission factors and vent
stream characteristics are included in the data set. Since uncontrolled
emissions, are subject .to the greatest uncertainty because of the difficulty
in defining what is a pollution control device, all stream data represent
the process stream exiting the primary product recovery device.
The regulatory analysis for the air oxidation unit process NSPS
based the.projection of the impacts of emissions control on a cost- and
energy-intensive.control technique: thermal oxidation. Supplemental
fuel costs and. capital charges, contribute the largest portion of the
total annualized costs for VOC control using this technique. However,
several other components add to the total resource burden that air
oxidation plants would have to bear in controlling VOC emissions. These
other components include, electricity, labor, and.(for offgas containing
halogenated compounds) quench, water, scrubbing water, and sodium hydroxide.
Accordingly, this regulatory analysis focuses on total resource use in
the selection of a regulatory alternative with acceptable energy impacts
and total costs as. well as acceptable emissions reduction. Air oxidation
vent streams, therefore, were characterized further according to total
resource-effectiveness (TRE), an index of the total resources required
to destroy one unit of VOC by thermal oxidation.
The TRE. index incorporates a. measure of all resource requirements
for VOC control. In addition to supplemental fuel and capital, this
index takes into account electricity and labor, as well as quench water,
scrubbing water, and sodium hydroxide, for halogenated streams. The
development of the TRE.index is discussed in detail in Chapter 8, "Costs."
Vent.streams,with higher net heating values and VOC concentrations
have lower supplemental energy requirements and higher achievable reductions
6-5
-------
in VOC emission rates than do more dilute streams. Therefore, TRE is
lower for streams with higher net heating values and VOC concentrations.
For vent streams with similar net heating values and VOC concentrations,
TRE decreases as flowrate increases. This relationship is due to the
linear increase of achievable emission rate reduction with increasing
flowrate, as well as economies of scale in thermal oxidizer capital
costs as flowrate increases.
Use of the national profile to project the national energy, economic,
and environmental impacts for all SOCMI air oxidation processes replaces
the chemical-by-chemical determination of impacts for each chemical-
producing industry covered by this unit process standard. Because the
national profile is based, on information available in a limited sample
and data for some.chemicals covered by the standard are not available,
projection of national impacts was based on conservative assumptions to
prevent understatement of the impacts associated with VOC control.
Appendix F describes the statistical analyses and national profile in
detail.
6.2 REGULATORY ALTERNATIVES
Regulatory analysis considers a variety of impacts associated with
several alternatives for national VOC emissions control. These alternatives
specify a range of control levels expressed as percentage reductions of
national VOC emissions over the baseline level and are based on the use
of a technically feasible control technique that is applicable to all
affected air oxidation facilities. These levels of national VOC reduction
are achieved by varying the percentage of facilities controlling VOC
emissions using, thermal oxidation at one level of control efficiency.
Although the air oxidation NSPS will allow the use of equivalent technology
to achieve the required VOC emission control, the regulatory analysis
only projects energy, economic, and. environmental impacts associated
with the use of a thermal oxidizer.. The operating conditions assumed
included a, temperature of 871°C (1600°F) with a chamber residence time
of 0.75 seconds to. achieve 98 percent VOC removal. For vent streams
containing halogenated compounds, a combustion temperature of 1093°C (2000°F)
with a residence time of one second was assumed. A VOC removal efficiency
of 98 percent (or an incinerator outlet concentration of 20 ppmv) can be
6-6
-------
achieved by all new, properly designed incinerators: operating at these
conditions. < • • '
A standard for control of VOC emissions from air oxidation process
reactors and product recovery vents, must reflect the degree of emission
reduction achievable through application of the best system of continuous
emission reduction considering the associated costs, nonair quality
health and environmental impacts, and energy requirements. Regulatory
analysis.provides.the background information necessary to determine this
degree of emission reduction and. to select the best:alternative for VOC
control with acceptable, energy, economic, and environmental impacts.
The alternative selected, then provides the basis for recommending a VOC
emissions limit, and formulating the air oxidation NSPS. The following
regulatory alternatives for control of VOC emissions from individual air
oxidation facilities are. considered:
1. Require no additional VOC control beyond the baseline level
achieved under current state implementation plans (SIP). This alternative
represents the level of control that would exist in;the absence of any '
NSPS and .is equivalent to about 72 percent national |VOC reduction.
2. Require approximately 31, 46, 57, 66, 81, or 98 percent national
VOC reduction from the baseline level based on the use of a thermal
oxidizer at those..air oxidation facilities required to meet a 98 percent
VOC.reduction requirement. These levels of national emissions reduction
were chosen as convenient, parameters for analysis, I
Only a part of all air oxidation facilities would be required to
control emissions to achieve the national VOC reduction over-the baseline
level specified.under each regulatory alternative. The mostistringent
alternative requires 100 percent of all facilities affected b;y the air
oxidation NSPS to control emissions and results in a 98 percent national
VOC emission reduction from the baseline. The least stringent alternative
requires, 7 percent of all facilities to control emissions and causes a
31 percent national VOC emission reduction from the baseline. To determine
which air oxidation facilities would be required to control VOC emissions
to achieve .the national emission reduction specified under each regulatory
alternative, regulatory, analysis uses levels of total resource-effectiveness
(TRE). A resource-effectiveness cutoff level, which is an index of the
6-7
-------
maximum required total resource use per unit of VOC destroyed using
thermal oxidation at affected individual air oxidation facilities, is
computed for each regulatory alternative.; Air oxidation facilities with
t
total resource requirements which place them below the TRE index cutoff
associated with a particular regulatory alternative would be required to
control VOC emissions. Table 6-1 shows the percentage of facilities
required to control VOC emissions and the TRE index cutoff associated
with each level of national emission reduction. Because vent stream VOC
content and heating value, generally are related inversely to supplemental
energy and capital requirements for VOC cbntrol, those streams containing
the highest levels of VOC would be controlled before lower concentration
streams, until the total amount.of VOC removed gives the percentage
reduction of national emissions required under a particular regulatory
alternative. The TRE index, therefore, is used to achieve a national
VOC emission reduction using the least possible amount of energy, capital,
and other resources, by setting a limit oh the amount of total resources
to be used per unit VOC control by individual air oxidation facilities.
From these considerations and by using the method of regulatory analysis
described, the energy, economic, and environmental impacts of control
were projected for each regulatory alternative.
The applicability to individual new facilities of an NSPS based on
an acceptable regulatory alternative can be determined using the associated
total resource-effectiveness index cutoff.. Use of the TRE concept is
meant to encourage the use of product recovery techniques or process
modifications to reduce emissions. It will be possible for some air
oxidation facilities to use product recovery techniques or process
modifications to keep VOC emissions below levels that would require
control as determined by total resource-effectiveness. Furthermore,
certain facilities required to control VOC emissions are likely to use
VOC control methods such as. catalytic incineration or combustion in
existing boilers and process heaters that are cheaper or less
energy-intensive than thermal oxidation.
6-8
-------
TABLE 6-1. REGULATORY ALTERNATIVES
Regulatory Regulatory Alternative
Alternative (Percent National VOC
Baseline from Baseline)
0 0
I 31
II 46
III 57
IV 66
V 81
VI 98
Percent Facilities Total Resource-
Required to Control Effectiveness
VOC Emissions Index Cutoff
N/A
7
14
19
27
47
100
_
0.74
1.5
2.2
3.1
6.2
6,000
The total resource-effectiveness (TRE) index is the cutoff value that defines facili-
ties which must incinerate. The TRE index value defines the regulatory alternative
that is referred to as the "percent national VOC reduction from baseline," because
the TRE index, value determines how the national emission reduction will be achieved
If the vent stream at an individual facility has a TRE index greater than the TRE
index cutoff for a.particular, regulatory alternative, no VOC control would be re-
quired at that facility. However, if the TRE index is less than or equal to the TRE
index cutoff, 98 percent VOC reduction or VOC reduction to 20 ppmv, whichever is less
stringent, would be required.
6-9
-------
6.3 REFERENCES FOR CHAPTER 6
1.
Blackburn, J.W. Emissions Control Options for the Synthetic Organic
Chemicals Manufacturing Industry — Air Oxidation Generic Standard
Support. Hydroscience, Inc. EPA Contract No..68-02-2577.
May'1979. p. 1-3, Table 1-1.
Patrick, D.R. 2nd Year End Report ~ Synthetic Organic Chemical
Manufacturing Industry Standards Development Program. U.S. Environmental
Protection,Agency. Research Triangle Park, N.C., March 1979. p. 8.
Memorandum from Mascone, D.C., EPArCPB.
incinerator efficiency.
June 11, 1980. Concerning
4. Blackburn, J.W. Emissions Control Options for the Synthetic Organic
Chemicals Manufacturing Industry -- Control Device Evaluation, Thermal
Oxidation. EPA Contract No. 68-02-2577. July 1980.
5. Basdekis, H.S., Emissions Control Options for the Synthetic Organic
Chemicals Manufacturing Industry — Control Device Evaluation, Thermal
Oxidation Supplement. EPA Contract No. 68-02-2577. November 1980.
6-10
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;; 7. ENVIRONMENTAL IMPACT
\
!
This chapter discusses the environmental impacts of each regulatory
alternative presented in Chapter 6. Impacts on air quality, water
quality, sol .id waste, and energy requirements are analyzed. Regulatory
analysis considers both the impacts attributed directly to a control
device (e.g.;, reduced VOC emissions) and the indirect or induced impacts
(e.g., aggravation of another pollutant problem through the use of a
control device). The beneficial and adverse impacts of VOC control are
examined, with emphasis on an accurate assessment of the national
incremental iimpacts of the regulatory alternatives.
A comparison of the-effects associated with each regulatory alternative
on air and water quality, solid waste generation, and energy requirements
provides a basis for selecting the highest degree of emission reduction
achievable with acceptable environmental impact. The following range of
increasingly; stringent alternatives, including not setting a standard,
was analyzed! for controlling VOC emissions from air oxidation process
vents: |
1. Do not set a standard. This alternative assumes that VOC
emissions from air oxidation process vents are controlled adequately to
protect public health and welfare. This alternative represents the
level of control achieved under State implementation plans (SIP's) and
is equivalent to about 72 percent national VOC reduction. In estimating
the baseline control pevel, it was assumed that current SIP's would
;
remain in effect, exciept for areas requesting extension beyond 1982 for
the ozone NAAQS. In these areas, it was assumed that SIP's would be
modified to reflect the RACT recommendation of the air oxidation control
techniques guidelinej(CTG) document. The baseline control fraction is
derived in detail in Chapters 3 and Appendix F.
2. Require different percentages of all new air oxidation facilities
to achieve 98 percent VOC control efficiency or 20 ppm (volume, by
compound) outlet VOC concentration, whichever is less stringent. Based
on increasing the percentages of facilities required to control VOC
emissions, six regulatory alternatives, ranging from 31 to 98 percent
national VOC emissions reduction from baseline, are defined.
7-1
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A total resource-effectiveness (TRE) index associated with each regulatory
alternative is used to determines which air oxidation facilities would
be required to control VOC to achieve the specified national emissions
reduction.
The environmental impacts associated with each level of national
VOC emissions reduction were analyzed and presented. Because of the
number and diversity of facilities and processes to be covered by this
standard, no model plants were used. Rather, a national statistical
profile representing the air oxidation segment of SOCMI, along with
five-year industry growth projections, were used to estimate the 1986
environmental impacts for facilities built from 1982 to 1986. Appendix F
describes the statistical analyses and national profile in detail.
Each regulatory alternative specifies a percent reduction of national
VOC emissions from the baseline level that is achieved by requiring a
percentage of new air oxidation facilities to reduce vent stream VOC
emissions. The environmental impacts associated with each alternative
were estimated assuming the use of a thermal oxidizer capable of achieving
98 percent VOC reduction at those facilities required to control VOC.
The method of regulatory analysis is pesented in detail in Chapter 6,
"Regulatory Alternati ves."
7.1 AIR POLLUTION IMPACTS
This section presents both the beneficial and adverse effects on
air pollution associated with the regulatory alternatives for control of
VOC emissions from air oxidation process vents.
7.1.1 Effects of VOC Control on National Emissions
The primary environmental impacts of this standard would be beneficial
and would consist of reduction in VOC emissions from SOCMI air oxidation
processes. Regulatory analysis considered the projected mass emissions
of VOC from air oxidation process vents. VOC emissions in 1986 from air
oxidation facilities projected to be built during the preceding five
years were estimated using the national statistical profile described in
Appendix F.
The uncontrolled 1986 national VOC emissions from air oxidation
process vents would be 78,000 Mg/yr (86,000 tons/yr). At the projected
7-2
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baseline control level, the national VOC emissions would be 22,000 Mg/yr
(24,000 tons/yr). This baseline level of VOC emissions corresponds to a
national VOC emission reduction of 72 percent from the uncontrolled
level.
Table 7-1 shows the incremental VOC emissions for 1986 associated
with each regulatory alternative. These alternatives are. expressed as
levels of national VOC emissions and national VOC emissions reductions
from the baseline level. The percentage of air oxidation facilities
that would be required to reduce vent stream VOC emissions to achieve
the percent reduction of national VOC emissions from baseline specified
under each regulatory alternative also are presented in Table 7-1.
The regulatory alternatives specify national emissions reductions
that range from 31 to 98 percent VOC reduction from the baseline level.
These control levels are achieved by requiring from 7 to 100 percent of
all new air oxidation facilities to control VOC emissions. The least
stringent regulatory alternative (31 percent national VOC reduction from
baseline) would reduce national VOC emissions by 7,000 Mg/yr from baseline,
resulting in national emissions of 15,000 Mg/yr. The most stringent
regulatory alternative (97 percent give national VOC emission reduction
from baseline) would require all new air oxidation facilities to control
VOC emissions. This alternative would reduce national VOC emissions by
21,500 Mg/yr (48,000 tons/yr) from baseline, resulting national emissions
of 440 Mg/yr.
7.1.2 Other Effects on Air Quality
Some adverse effects on air quality are associated with the use of
a thermal oxidizer to reduce VOC. Pollutants generated by the combustion
process, particularly nitrogen oxides (NO ), may have an unfavorable
X
impact on ambient air quality. The principal factors affecting the rate
of NO formation are the amount of excess air available, the peak flame
A
temperature, the length of time the combustion gases are at peak temperature,
and the cooling rate of the combustion products. The rate of NO
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temperatures and relatively short residence times associated with control
of VOC using thermal oxidation.
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Thermal oxidizer outlet concentrations of NO were measured in
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seven sets of thermal oxidizer tests conducted at three air oxidation
plants. The test results indicate that NOV outlet concentrations range
3
from 8 to 200 ppmv (0.015 to.0.37 g/m ). These values could increase by
several orders of magnitude in a poorly designed or operated unit.
These tests are described and documented in Appendix C.
Although there are conflicting data, some studies report that
incineration of vent streams containing high levels of nitrogeneous
compounds also may cause increases in NO emissions.'
J\
The maximum .
outlet NO concentration of 200 ppmv was measured at an acrylonitrile
/\
plant. The vent stream of this plant contains nitrogeneous compounds.
The NO concentrations measured at the other two plants, whose vent
J\
streams do not contain nitrogeneous compounds, range from 8 to 30 ppm
(0,015 to.0,056.g/m3).
Control of VOC emissions from oxychlorination process vent streams
by thermal oxidation may result in the release of chlorinated combustion
products to the environment. However, flue gas scrubbing can be used to
remove these compounds from the incinerator outlet stream. Incineration
temperatures greater than. 871°C (1600°F) are required for destruction of
halogenated VOC. At temperatures of 980° to 1100°C (1800° to 2000°F),
almost all chlorine present exists in the form of hydrogen chloride
(HC1). The HC1 emissions generated by thermal oxidation at these
temperatures can be removed efficiently by wet scrubbing.
7.2 WATER POLLUTION IMPACTS
Contro.l of VOC emissions using thermal oxidation does not result in
any significant increase in wastewater discharge by air oxidation unit
processes. No water effluents are generated by thermal oxidizers
themselves.
Use of an incinerater/scrubber system for control of VOC emissions
from oxychlorination process vent streams results in increased water
consumption. In this type of control system, water is used to remove
the HC1 contained in the thermal oxidizer outlet stream. The increase
in total plant wastewater would be relatively small and would not affect
plant waste treatment or sewer capacity. However, if the absorbed HC1
is not recoved., it may cause the water leaving the scrubber to have a
low pH. This acidic effluent could lower the pH of the total plant
effluent if it is released into the plant wastewater system.
7-5
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The water effluent guidelines for individual States may require
that industrial sources maintain the pH of water effluent within specified
limits. To meet these guidelines, the water used as a scrubbing agent
must be neutralized prior to discharge to the plant effluent system.
The scrubber effluent can be neutralized by adding sodium hydroxide
(NaOH) to the scrubbing water. The amount of NaOH needed depends on the
amount of HC1 in the waste gas. Approximately 1.09 kilograms (2.4 pounds)
of NaOH are needed to neutralize 1 kilogram (2.2 pounds) of HC1. The
salt formed must be purged from the system and properly disposed of.
Most existing air oxidation facilities with halogenated vent streams
currently incinerate and scrub the streams, and have State permits to
dump the brine. It is projected that any new oxychlorination plants
would be built in the same States that have given these brine-dumping
permits. Acceptable methods of Nad disposal include direct wastewater
A
discharge or deep well disposal. The increased water consumption and
NaOH costs were included in the projected operating costs for those data
vectors in the national profile representing halogenated vent streams.
Costs associated with disposal of Nad were not believed to be significant,
and therefore, were not included in the projected impacts. The makeup
rate for water purged from the system, based on 1 percent dissolved
solids in the water recycle, is.0.033 m /kg (19.2 gal/lb) of chlorine in
the waste gas.
The use of scrubbers to remove HC1 from the incinerator offgas also
could result in small increases in the quantities of organic compounds,
such as ethylene dichloride, released into plant wastewater. Organic
compound emissions into the water and, subsequently, into the air can be
prevented by using a water stripper.
No increase in total plant wastewater is projected for those
facilities which might use additional product recovery to achieve a
total resource-effectiveness (TRE) value (discussed in Appendix E) above
the 2.2 cutoff which corresponds to Regulatory Alternative III. Carbon
adsorption is the only product recovery technique currently in use in
the industry which has an associated organic wastewater effluent. Based
on past industry experience, only three air oxidation chemical manufacturing
processes are expected to employ carbon adsorption. Of these three
processes only the maleic anhydride from benzene feedstock process might
7-6
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have a TRE value below the 2.2 cutoff associated with Alternative III.
(Because of the other two processes, Alternatives IV, V, and VI might
have a small associated water pollution impact-) However, if any new'
maleic anhydride facilities are built, it is projected they will utilize
;
butane feedstock rather than benzene. The maleic anhydride from butane
feedstock process would not use carbon adsorption for product recovery
and therefore would have no additional wastewater.
If an existing benzene-feedstock maleic anhydride facility were ,
modified or reconstructed (which is unlikely), such a facility might ;
have a TRE value below the cutoff. In such an event, and if additional
carbon adsorption were employed in lieu of incineration or some other'
type of product recovery, the adsorption unit of a typical maleic ;
anhydride facility would generate approximately 500 Mg/yr of VOC which
would be sent to wastewater treatment. The organic load of the wastewater
from carbon adsorption would be less than 10 percent of the total liquid
waste from such a facility. This wastewater stream could be treated I
along with the other plant effluent or recycled to the process. No new
wastewater treatment plant or additional sewer capacity would be necessary.
7.3 SOLID WASTE DISPOSAL IMPACTS j
There are no significant solid wastes generated or disposed of as a
result of control by thermal oxidation. A small amount of solid waste
disposal could result if catalytic oxidation were used by a facility,
instead of thermal oxidation, to achieve, an equivalent degree of VOC
control. The solid waste would consist of spent catalyst. If a facility
were to use an additional absorption column for improved product recovery
in order to exceed a total, resource-effectiveness (TRE) cutoff level, a
small amount of solid waste would be generated by cleaning the column.
7.4 ENERGY IMPACTS
This section presents the national energy requirements associated
with the regulatory alternatives for controlling VOC emissions from air
oxidation process vents. Projection of the energy impact of each
regulatory alternative is based on using a thermal oxidizer capable of
98 percent VOG reduction at those individual air oxidation facilities
that would be required to control emissions. The 1986.energy require-
ments for controlling VOC emissions from air oxidation facilities
expected to be built from 1982 to 1986.were estimated using the national
statistical profile described in Appendix F.
7-7
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7.4.1 Energy Requirements for Thermal Oxidation
Maintaining incinerator temperatures as high as 870°C (1600°F) for
,0.75 seconds could be necessary to achieve the required 98 percent
control efficiency. Supplemental fuel, commonly in the fonji of natural
gas, is required to maintain the operating temperature. The amount of
supplemental fuel needed depends on incineration temperature, type and'
amount of heat recovery, as well as offgas temperature, flowrate and
heating value. Depending on the offgas characteristics, several types
and levels of heat recovery assumed was 70 percent of the heat content
of the incinerator outlet stream. Due. to the use of steam-producing
heat recovery techniques, combustion of some air oxidation vent streams
results in a net production of energy even though supplemental fuel is
necessary for flame stability. Facilities whose vent streams contain
halogenated compounds generally employ such heat recovery for net energy
produciton. However, energy-rich streams without halogenated compounds
are not always net energy producers. Only that net production of energy
resulting from control o.f. vent streams containing halogenated compounds
is included in the projection of national, energy use. Supplemental fuel
requirements account for most of the energy use. • :
Table 7-1 shows the incremental energy impacts for 1986.associated
with each regulatory alternative. In addition to the total national
energy requirement and the average energy-effectiveness, the table shows
the highest energy-effectiveness for individual vent streams that would
be subject to control under each alternative.
The energy-effectiveness for VOC control ranges from 33,000 MJ/mg
of Voc destroyed for the 31 percent national VOC reduction alternative
to 278,000 MO/Mg of VOC destroyed for the 98 percent VOC reduction
alternative. The corresponding annual national energy impacts range
from .23 x 109 MO/yr (110 bbl oil/day) to 6,0 x 10^ MJ/yr (2,800 bbl
oil/day) for the 31 percent and 98 percent VOC reduction alternatives,
respectively.
Each maximum energy-effectiveness levels listed in Table 7-1
indicates the maximum projected supplemental, energy, use by a facility,
per megagram of VOC destroyed., for those facilities required to reduce
VOC emissions under the given regulatory alternative. No individual air
oxidation facility required to control VOC under a particular alternative
7-8
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would use a greater amount of supplemental energy than indicated by the
corresponding maximum energy-effectiveness. Maximum energy-effectiveness
increases gradually from 67,400 MJ/Mg of VOC destroyed for 31 percent
national VOC reduction to 724,000 MJ/Mg o.f VOC destroyed for 81 percent
VOC reduction. The remaining 7 percent national VOC reduction beyond
81 percent reduction is increasingly difficult to achieve in terms of
energy requirements, at individual air oxidation facilities. The maximum
energy-effectiveness for 98 percent national VOC reduction would be
463,000,000 MJ/Mg of VOC destroyed. This alternative would require
control at all air oxidation facilities.
7.4.2 Other Energy Requirements
Electricity requirements are approximately five percent of the
total energy requirements included in the projected energy impacts.
Electricity is required to operate the pumps, fans, blowers, and
instrumentation that may be necessary to control VOC using a thermal
oxidizer or a thermal oxidizer/scrubber system. Fans and blowers are
necessary to transport vent streams and combustion air; pumps are
necessary to circulate absorbent for incinerator/scrubber systems.
7.5 OTHER ENVIRONMENTAL IMPACTS
7.5.1 Considerations for Installing Control Equipment
Depending on the volume of offgas to be controlled, thermal oxidizers
may require a site as large as 300 feet by 300 feet for installation.
Because thermal oxidizers use. combustion with a flame to control VOC
emissions, these units must be located at a safe distance from process
equipment using flammable, chemicals, or special .precautions must be
taken to minimize the risk of explosion or fire.
7.6. OTHER ENVIRONMENTAL CONCERNS
7.6,1 Irreversible and Irretrievable Commitment of Resources
The use of thermal oxidation to control VOC emissions from air
oxidation processes usually requires the use of supplemental energy in
the form of natural gas or fuel oil. The adverse effects of using these
non-renewable resources derived from petroleum must be considered when
evaluating the benefits of controlling the release of potentially
harmful air pollutants.
7-9
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Use of the total resource-effectiveness concept to determine which
air oxidation facilities would be required to control VOC is meant to
encourage the use of product recovery techniques or process modifications
to reduce emissions. Control of VOC emissions using product recovery
techniques might be an alternative for some air oxidation facilities.
Since the air oxidation vent streams containing VOC also are derived
ultimately from petroleum, these techniques would result in conservation
of both chemicals and fuels derived from petroleum.
7.6,2 Environmental Impact of Delayed Standards
If the air oxidation standard were delayed, significant adverse
impacts on ambient air quality could result. Based on industry growth
projections, air oxidation facilities controlling VOC emissions at
current baseline levels (i.e., 72 percent national VOC reduction) would
emit 22,000 Mg/yr (24,250 tons/yr) in 1986.compared to emissions of
440 Mg/yr for control under the most stringent regulatory alternative
98 percent national VOC reduction).
As stated in Sections 7.2. and 7.3, there are no significant water
quality or solid waste impacts associated with the regulatory alternative.
Therefore, there are no anticipated impacts in these areas resulting
from delay of the standard.
Reducing VOC emissions from all air oxidation facilities by a
98 percent national reduction from the baseline level would require
6,0 x 10 MJ/yr (2,800 bbl oil/day). Although there is no accurate way
to project the baseline energy impact, the energy use for VOC control if
this standard were delayed would be significiantly less than that
projected for control under the most stringent regulatory alternative.
7-10
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7.7 REFERENCES FOR CHAPTER 7
1.
2.
3.
4.
Blackburn, J.W. Emissions Control Options for the Synthetic Organic
Chemicals Manufacturing Industry. Control Device Evaluation
Thermal Oxidation. EPA Contract #68-02-2577. July 1980. p! V-43.
:
Basdekis, H.S. Emissions Control Options for the Synthetic.Organic
Chemicals Manufacturing Industry. Control Device Evaluation
Thermal Oxidation Supplement (VOC-Containing Halogens or Sulfur) EPA
Contract #68-02-2577. November 1980. pp. II-4, II-6. Ur;'
Basdekis, H.S., op cit
Ibid.
, p. 111-15.
7-n
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8. COSTS
8.1 COST ANALYSIS OF REGULATORY ALTERNATIVES
8.1.1 Introduction
The cost impacts of implementing the seven regulatory alternatives
for control of volatile organic compound (VOC) emissions from SOCMI air
oxidation process vents are presented in this section. Capital costs,
annualized costs, and cost-effectiveness of the regulatory alternatives
are presented.
8.1.2 Substitution of National Profile for Model Plant
The cost impacts of the seven regulatory alternatives were estimated
based on natural gas-fired thermal oxidation as the single control
technique. For offgas that contains halogenated compounds, a design
temperature of 1100°C (2000°F) and a residence time of 1.0 second were
used. For offgas lacking halogenated compounds, a design temperature of
870°C (1600°F) and residence time of 0.75 second were used. A VOC
destruction efficiency of 98 percent was used. The traditional model
plant approach was not used. Because of the number and diversity of
facilities and manufacturing processes in the air oxidation industry, a
large number of model plants would have been required in order to
accurately determine the cost impacts associated with the regulatory
alternatives. However, only a limited amount of vent stream data is
required to determine incinerator costs and efficiency. The required
data include offgas flowrate, net heating value, and VOC emission rate.
It must also be known whether the offgas contains halogenated compounds.
Therefore, although data from many types of processes are still required
in order to adequately represent the air oxidation industry, the data
need not consist of fully designed model plants. Rather, a national
statistical profile of air oxidation processes was constructed. The
national profile characterizes air oxidation processes according to
national distributions of the three critical offgas parameters for
halogenated and nonhalogenated waste streams. The cost impacts of the
regulatory alternatives are therefore evaluated as impacts upon the
entire population of affected facilities, as represented by the national
profile. The development and statistical basis for the national profile
are described in detail in Appendix F.
8-1
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8.1.3 Thermal Oxidation Design Categories
' ' ' The thermal oxidizer system design employed for a particular vent
stream depends upon the offgas net heating value, the design flowrate,
and the presence or absence of halogenated compounds. Sufficient fuel
must be added to permit incineration at 870°C (1600°F). Fuel require-
ments can be reduced by the use of recuperative heat recovery to preheat
the offgas and/or combustion air. Secondary heat recovery in addition
to the heat exchanger is used by some facilities. However, use of
secondary heat recovery was not assumed, in order to project conserva-
tive (higher) control costs. The basic design characteristics of each
category are given in Table 8-1.
8.1.3.1 Categories Al and A2
All vent streams which contain halogenated compounds are included
in Categories Al and A2. Due to the greater difficulty of achieving
complete combustion of chlorinated VOC, an incineration temperature of
11QO°C (2ppO°F) and a one second residence time were assumed. Combustion
temperatures exceeding 870°C (16QO°F) rule out the use of recuperative
heat exchangers because of problems with materials of construction and
with associated problems such as possible precombustion occurring in the
exchangers. However, a waste heat boiler can be used effectively with
temperatures to up to and above 1650°C (3QOO°F). The only air oxidation
process which -has chlorinated offgas is ethylene dichloride manufacture,
which is known to employ waste heat boilers for heat recovery. Therefore,
heat recovery, in a waste heat boiler with steam generation was assumed.
The amount of heat recovery was limited by a minimum outlet flue gas
temperature of about 26p°C (5pO°F), below which, excessive condensation
of corrosive combustion products could occur. The corrosive hydrogen
chloride is then removed by flue gas quenching and scrubbing, and the
resulting solution neutralized with caustic soda. Categories Al and A2
do not differ in control system design, but only in supplementary fuel
requirements.
8.1.3.2 Category B
Design Category B includes offgas with a heating value below
.0.45 MJ/scm (12 Btu/scf), which corresponds to 25 percent of a typical
lower explosive limit (LEL) in air.9 For Category B, 70 percent heat
8-2
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12
recovery was assumed. In this heating value range, the amount of heat
recovery which could be used is only limited by a ceiling of about
550-6QO°C (1000-11QO°F) on the combustion air preheat temperature due to
burner design considerations.
8.1.3.3 Category C
Because of insurance requirements, offgas with a heating value
between.0.45 MJ/scm (12 Btu/scf) and 1.8 MJ/scm (49 Btu/scf), which
constitutes Category C, may not be preheated. This heating value
range corresponds to a range of 25-100 percent of LEL in air for a
typical organic vapor. Because air oxidation vent streams generally
contain little or no oxygen, which is essentially depleted by the
process reaction, offgas in this heating value range need not be diluted.
It was assumed that the combustion air would be preheated, with 34 percent
of the flue gas heat content recovered.
8.1.3.4 Category D
Offgas with a heating value in the range 1.8 MJ/scm (49 Btu/scf) to
3.4 MJ/scm (92 Btu/scf), which constitutes Category D, need not be
preheated and requires only a small amount of auxiliary fuel, for flame
stability. The offgas determines its own combustion temperature, which
in general, exceeds 870°C (16QO°F) and can be as high as 980°C (1800°F).
A design temperature of 980°C (1800°F) was assumed, because of the
larger chamber volume per mole of offgas and greater amount of refractory
required at that temperature.
8.1.3.5 Category E
Design Category E includes offgas with a heating value above
3.4 MJ/scm (92 Btu/scf). Offgas in Category E need not be preheated and
requires only a small amount of auxiliary fuel, for flame stability.
The offgas, which determines its own combustion temperature, will burn
at temperatures of 980° C (1800°F) or greater. Some processes and
facilities with offgas this rich are able to use the steam which would
be generated by employing a waste heat boiler after the thermal incinerator
or by combusting in an existing boiler or process heater. Other facilities,
however, will not be able to use steam and will not employ heat recovery.
A few facilities might choose to dilute the offgas so that the flue gas
temperature does not exceed 980°C (1800°F). In order to give a conservative
estimate of costs, it was assumed that streams in Category E" were
diluted to 3.4 MJ/scm (92 Btu/scf), and that no heat recovery was employed.
8-4
-------
8.1.3.6. Maximum Equipment Sizes
Because of shipping size restrictions, single thermal oxidizer
units larger than about 32 feet by 16.feet would require field fabrication,
which would greatly increase the cost. Therefore, it is assumed that
vent streams which would require larger incinerators would instead
employ multiple sets of control equipment systems. The design standard
temperature vent stream (incinerator inlet) flowrates, for each design
category, which correspond to the maximum equipment size are given in
Table 8-2.15>16'
8.1.4 Offgas Composition Assumptions
Offgas with a flowrate less than 500 scfm are assumed to have a
flowrate of 500 scfm for the purpose of calculating capital costs. In
order to avoid underestimation of the required equipment sizes, all vent
streams were assumed to contain no oxygen. Therefore, combustion air
requirements were maximal. In order to increase the rate of combustion
and avoid incomplete combustion and pyrolysis, it was assumed that
enough excess combustion air was supplied to assure three mole percent
oxygen in the flue gas.
An average VOC molecular weight was calculated for the national
1 ft
profile. Based on additional calculations by Enviroscience, all
nonhalogenated VOC was assumed to consist of a typical model compound
with the empirical formula C2.8H5.700>63.19 All halogenated VOC was
assumed to consist of a typical compound with the empirical formula
2fl
Cl.4H2.4C10.86' Based on an inspection of the national profile, it
was further assumed that each stream contained four moles of methane per
mole of VOC. From these assumed offgas compositions, a typical ratio of
flue gas flow to offgas flow was calculated for each design category and
used to size the control equipment. These ratios are qiven in
21 22
Table 8-3. ' The model nonhalogenated VOC was assumed to have a net
heating value of 71 MJ/scm, while a net heating value of 27 MJ/scm was
assumed for the model halogenated VOC. These values correspond to net
heating values of acetone and methyl chloride, respectively.23'24 An
offgas temperature of 38°C (100°F) was assumed.25 These offgas composition
assumptions were also used to determine the minimum and maximum net
heating values for each design category. However, actual vent stream
8-5
-------
TABLE 8-2. MAXIMUM OFF6AS FLOWRATES
EACH DESIGN CATEGORY15'16
Category
AT
A2
B
C
D
E
Incineration
Temperature
fc)
noo
1100
870
870
980
980
Residence
Time
(Sec)
1.0
1.0
0.75
0.75
0.75
0.75
Maximum
Vent
Stream
(Incinerator
Inlet)
Flowrate
(Thousand
scm/min)
0.79
0.79
1.52
1.52
1.34
1.34
8-6
-------
TABLE 8-3. RATIO OF FLUE GAS FLOWRATE TO OFFGAS
FLOWRATE FOR EACH DESIGN CATEGORY21'22
Category
Alb
A2b
B
C
D
E
Maximum
Net
Heating
Value
(MJ/scm)
3.3
-
0.45
1.8
3.4
-
Incineration
Temperature
( C)
noo
noo
870
870
980
980
Ratio of
Flue Gas
Flow to Off gas
Flowa
2.9
2.9
1.9
2.3
2.5
2.5
Both at standard temperature.
Offgas contains halogenated compounds.
8-7
-------
parameters were used in all other parts of the analysis. Actual offgas
parameters were used in calculations for typical vent streams in each
design category, regulatory'alternative impacts, total resource-effectiveness
projections, and process-specific economic analysis.
4
8.1.5 New Facilities
The installed cost impacts associated with each regulatory alternative
are presented as impacts on the entire population of new facilities, as
represented by the national profile.
8.1.5.1 Basis for Capital Costs
The capital costs for the implementation of the regulatory alternatives
include purchase costs and installation costs for thermal incinerators,
recuperative heat exchangers, ducts, fans, and stacks. For halogenated
streams, the purchase and installation costs of waste heat boilers and
flue gas scrubbers are also included.
The basic capital cost data was provided by the IT Enviroscience
thermal oxidizer evaluation documents and was derived from vendor
quotations.26'27 The IT Enviroscience documents were specifically
designed for air oxidation processes, which have vent streams containing
little or no oxygen. Therefore, they take into account the maximum
combustion air requirements for incineration of such streams. Furthermore,
the Enviroscience documents present costs for a range of offgas heating
values and incineration temperatures. Total installed costs are presented
for two types and several levels of heat recovery. It was necessary to
use a cost source possessing this flexibility to cover the variety of
air oxidation vent stream characteristics. The Enviroscience costs were
based on December 1979. In order to transform'these to December 1978
dollars, an escalation factor of 0.900 was used. This factor is the
ratio of the Chemical Engineering M&S chemical industry equipment cost
index value for the fourth quarter, 1978, to that for the fourth quarter,
1979.28
The relation of the Enviroscience purchase cost estimates to the
original vendor quotations is discussed in Appendix G. Graphs relating
purchase costs to offgas flowrates are also given in Appendix G for each
piece of control equipment. As discussed in that appendix, purchase
cost estimates obtained from two additional vendors agreed well with the
Enviroscience estimates.
8-8
-------
Enviroscience estimates equipment installed costs from equipment
purchase costs by adding factors for each of 10 aspects of installation.
These factors are expressed as percentages of the equipment purchase
cost. The most important factors are those for piping and erection. A
list of the installation components for which factors were developed is
29
given in Table 8-4. A detailed discussion of the derivation and use
of the installation factors is given in Appendix G..
The total installed capital costs represent the total investment,
including all indirect costs such as engineering and contractors' fees
and overheads, required for purchase and installation of all equipment
and material to provide a facility as described. These are battery-
limit costs and do not include the provisions for bringing utilities,
services, or roads to the site, the backup facilities, the land, the
research and development required, or the process piping and instrumentation
interconnections that may be required within the process generating the
30
waste gas feed to the thermal oxidizer.
The basis for the capital costs is further discussed below for each
design category. Total installed capital cost equations as a function
of operating offgas flowrate are given in Table 8-5 for each design
category. It was assumed that a typical operating offgas flowrate would
be 95 percent of the design maximum. Therefore, a design vent size
factor of 0.95 was assumed to avoid an underestimate of control equipment
size and capital cost. These capital cost equations were obtained by
fitting an analytical function of capital cost versus design offgas
flowrate to the data in the Enviroscience tables and graphs. A different
cost curve was fit for each design category.
All three coefficients were estimated for the Category B equation.
The exponent was estimated to be 0.88. This exponent was assumed for
the other design categories, and only the remaining two coefficients
were fit for them. These equations are judged to be reasonably close
fits, and no claim is made that they are the best ones that could have
been statistically determined. Capital cost estimates for a hypothetical
vent stream with characteristics which are average for each design
category are presented in Table 8-6.
Several pieces of control equipment are common to each design
category. These include the thermal oxidizer, ducts, fans, and stack.
8-9
-------
TABLE 8-4. INSTALLATION COMPONENTS
Installation Component
Foundation
Insulation
Structures
Erection
Piping
Painting
Instruments
Electrical
Fire Protection
Engineering, Freight and Taxes
8-10
-------
TABLE 8-5. TOTAL INSTALLED CAPITAL COST EQUATIONS
AS A FUNCTION OF OFFGAS FLOWRATE29'30
Category
Al
A2
B
C
D
Eb
Maximum
FTowrate
Per Unit
(Thousand)
( s cm/mi n)
0.79
0.79
1.52
1.52
1.34
1.34
Fabricated
Equipment
Cost
Escalation
Factor
.900
.900
.900
.900
.900
.900
Design
Vent
Size .
Factor
.95
.95
.95
.95
.95
.95
C1
802 70
802.70
259.89
288.78
242.27
242.27
C2
15. 2a
15. 2a
3.94
2.49
3.11
3.11
C3
0.88
0.88
0.88
0.88
0.88
0.88
Total Installed Capital Cost ($1000) = (# of Units') x (Escalation Factor) x
(Cl + C2 x ((Flowrate (|S^) * Design Vent Size Factor)03))0
aF1owrate Correction Factor of 1.12 = (1.14)'88 Incorporated into Coefficient C2.
Dilution Flowrate is Used in Capital Cost Equation.
Dilution Flowrate = (Design Flowrate) x (Original Heating Value) r (3.5 MJ/scm).
°Flowrate per equipment unit.
8-11
-------
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-------
The thermal oxidizer consists of a refractory-lined carbon steel
mixing chamber and combustion chamber. Discrete burners are assumed.
Enviroscience assumed a 10 percent heat loss from the combustion_chamber
for all combustion temperatures and design categories.
The ducts consist of 150 ft of round-steel inlet with four ells,
32
one expansion joint, and one damper with control. Considerably more
ductwork may be required in some cases. However, ductwork accounts for
only two to eight percent of the total installed capital cost. Therefore,
the total installed capital cost is relatively insensitive to the amount
of ductwork.
33
Fans are included for both offgas and combustion air. Costs for
motors and starters are included. The offgas flowrate, combustion air
flowrate (calculated from the flue gas to offgas flow ratio) and pressure
drop of the thermal oxidizer are used to calculate fan sizes. For vent
streams in Category A, which require flue gas scrubbing, the pressure
drop across the scrubber is also considered.
The stack design height is 80 ft. A superficial linear gas
velocity of 15 m/sec (3000 ft/min) is assumed in calculation of the
cross-sectional area.
Streams in Categories Al and A2 require flue gas quenching and
scrubbing to remove corrosive hydrogen chloride. A waste heat boiler is
employed for heat recovery prior to quenching. An overall heat transfer
coefficent of 0.16 MJ/(hr-m2-°C) (8 Btu/(hr-ft2-°F) is assumed for the
boiler.35 Steam is generated at 120°C (250°F) and a pressure of 1.7
MN/m2 (250 psi). For 60 percent heat recovery, the ratio of heat
exchange surface area to flue gas flowrate is 0.89 m /son (0.27 ft /scfm).
OC
The scrubber column design is based on 36 ft of packing. The liquid-
to-gas ratio is assumed to be 10. A superficial vapor velocity of three
ft/sec was used for determining the column diameter. The quench chamber
design location is the lower part of the scrubber column. It has the
same diameter as the scrubber column. A one second flue gas retention
was assumed. In reducing the flue gas temperature to the adiabatic
saturation temperature of the scrubbing agent, considerable water is
vaporized, increasing the gas flow through the scrubber. The ratio of
quenched to unquenched flue gas (both standard) flowrate is 1.67 at
1100°C (2000°F).
8-13
-------
Vent streams in Category B employ 70 percent recuperative heat
recovery.38 The heat exchanger tubes are constructed of carbon steel,
except for the first few passes. It is necessary to construct the tube
regions which experience a flue gas temperature between 820 and 870 C
(1500 and 1600°F) of heat-resistant nickel alloy. An overall heat
transfer coefficient of 0.08 MJ/(hr-m2-°C) (4 Btu/(hr-ft2-°F)) is
assumed for the heat exchanger. This assumption is deliberately low,
and hence the heat exchanger is deliberately over-designed to some
degree. For 70 percent heat recovery, the ratio of heat exchange
surface area to flue gas flowrate is 2.7 m2/scm (0.83 ft /scfm).
Recuperative heat recovery reduces both the natural gas and combustion
air requirements of the thermal oxidizer. Therefore, the required
combustion chamber volume is reduced. For 70 percent heat recovery, the
combustion chamber size reduction factor is 0.667 (corresponding to a
33 percent reduction in system size relative to no heat recovery).
Vent streams in Category C are assumed to preheat the combustion
air only, due to insurance requirements for safe handling of offgas with
39
VOC concentrations above 25 percent of LEL in air. Thirty-four
percent heat recovery is assumed. Materials of construction and overall
heat transfer coefficient are the same as in Category B. For 34 percent
heat recovery, the ratio of heat exchanger surface area to flue gas
flowrate is 1.2 m2/scm (0.36 ft2/scfm). The combustion chamber size
adjustment factor is 0.81 (corresponding to a 19 percent reduction in
system size relative to no heat recovery).
Due to their high heating value, vent streams in Category D determine
their own combustion temperature. A temperature as high as 980 C
(1800°F) may be reached. Therefore, preheating of the offgas is not
economically advantageous, nor is it technically feasible at temperatures
above 870°C (1600°F). It was not assumed that any process with offgas
in Category D could use generated steam, and therefore no waste heat
boiler was included in the design. The combustion chamber design takes
into account the extra refractory and internal volume required by the
higher incineration temperature.
8-14
-------
Vent streams in Category E are assumed to be sufficiently diluted
prior to combustion that the resultant offgas heating value is 3.6.
MJ/scm (98 Btu/scf), so that the flue gas temperature will not exceed
980°C (1880°F). The correction equations are:
1. New flowrate = (old flowrate) x (old heating value) * (3.6.MJ/scm),
2. New % VOC = (old % VOC) x (old flowrate) ^ (new flowrate), and
3. New heating value = 3,6.MJ/scm.
The same incinerator design is assumed as in Category D.
8.1.5.2 Basis for Annualized Costs40'41
The typical annualized costs consist of the direct expenses for
operating labor, utilities, and maintenance materials and labor plus the
indirect costs for overhead, taxes, insurances, general administration,
and the capital recovery charges. The utilities include natural gas and
electricity. For Category A, scrubbing water, quench makeup water, and
caustic are also included. Return on investment for the control equipment
is not included. All the data required in the estimation of these cost
factors and costs were obtained from References 40 and 41. The annualized
cost factors are given in Table 8-7. Those operating factors which vary
with design category are given in Table 8-8. The equations used to
.calculate annualized costs are given in Table 8-9.
Costs associated with disposal of sodium chloride from the neutralized
scrubbing water of halogenated vent streams (Categories Al and A2) are
not included in the annualized costs. These disposal costs would vary
widely from facility to facility. However, sodium chloride disposal
costs are insignificant in almost all existing plants.
IT Enviroscience developed natural gas use curves and tables from a
fly a o
detailed heat and material balance. ' The Enviroscience work was
checked for vent streams with heating values at the cutoff points
distinguishing design Categories B, C, D, and E, as well as for chlorinated
streams (Categories Al and A2). For these cutoff cases, the heat and
material balance was completely redone, using a slightly different set
44
of assumptions. These different assumptions included that of no
preheating of the offgas for Category C streams. The common assumptions
are presented above in Section 8.1.4. A further discussion of the heat
and material balance calculation is given in Reference 45.
8-15
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The results of the recalculations for the critical cases were
essentially in agreement with the Enviroscience work. Because of the
necessity of calculating fuel requirements and*costs for the entire
national statistical profile of 59 vent streams (discussed in Appendix F),,
detailed heat and mass balances were not done for each stream. Instead,
equations were fit to the Enviroscience tables and graphs of natural gas
use. The coefficients of the fuel-use .equation are given in Table 8-8.
Streams in Categories D and E have sufficient heating value that
they only require a small amount of fuel, for flame stability. The fuel
requirement for these streams was assumed to be equivalent to.0.18 MJ of
natural gas heat per standard cubic meter of offgas, independent of
offgas heating value. This fuel requirement was chosen because it is
equivalent to that calculated according to the Category C fuel use
equation for offgas with a heating value of 1.8 MJ/scm (which is the
cutoff heating value distinguishing Categories C and D). Therefore, a
composite graph of the fuel use equations for Categories C and D versus
offgas heating value would not be discontinuous at the cutoff heating
value.
For the chlorinated streams in Categories Al and A2, Enviroscience
did not develop heat and mass balance calculations for the designated
combustion temperature of 1]QO°C, but only for higher temperatures.
Therefore, the fuel requirements were interpolated from the curves for
980°C and 1200°C. A fuel use equation was fit to this interpolated
curve. This equation indicates that chlorinated offgas with a heating
value greater than 3J3 MJ/scm requires primarily auxiliary fuel, for
flame stability. At this critical heating value, according to the
fuel use equation, the amount of fuel required per normal cubic meter of
offgas is equivalent to ]0 percent of the offgas heating value, which is
a typical auxiliary fuel requirement. This heating value constitutes
the cutoff between design Categories Al and A2. For Category Al, the
fuel use equation discussed above was employed. For Category A2, the
fuel requirement was assumed to be equivalent to.0.33 MJ of natural gas
heat per normal cubic meter of offgas, independent of offgas heating
value.
8-19
-------
The assumption of a maximum heat exchange efficiency of 70 percent
may be conservative for some facilities. A thermal oxidation system
employing regenerative heat recovery could achieve a primary heat
exchange efficiency as high as 85 to 95 percent. Therefore, facilities
able to employ such technology would have substantially lower fuel
requirements.
Several additional conservative assumptions are built into the fuel
use equations. The most important is the assumption of no oxygen in the
offgas. This leads to maximum combustion air requirements and a higher
total incinerator inlet flow to be heated to the combustion temperature.
8.1.5.3 Emission Control Costs
This section discusses the estimated emission control costs associated
with control by thermal oxidation of a typical vent stream for each
design category. These emission control costs are given in Table 8-10.
The control costs are broken down into detailed components, including
all types of operating expenses, capital charges, and heat recovery
credits.
The primary contributors to the annualized costs for the typical
chlorinated, dilute Category Al stream shown in Table 8-10 are capital
charges and caustic costs. These account for about 36 percent and
25 percent, respectively, of the total annualized costs. For the
chlorinated, concentrated Category A2 stream shown in Table 8-10,
capital charges and caustic costs are the primary contributors to total
annualized costs. The sum of the other contributors is negative due to
the very large heat recovery credit. For the dilute Category B streams
which employ 70 percent heat recovery to reduce fuel requirements,
natural gas costs account for 55 percent of the total annualized cost.
Capital charges account for about 30 percent of the total annualized
cost. The moderately dilute streams of Category C, which cannot employ
preheating of the offgas because of safety considerations, have higher
energy requirements, relative to capital charges, than do Category B
streams. For the typical stream shown in Table 8-10, gas costs account
for about 76 percent of the total annualized cost, while capital charges
account for about 14 percent. The VOC-rich streams in Category D
require little fuel, and capital charges account for about 43 percent of
the total annualized cost of the typical stream shown in Table 8-10.
8-20
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The very rich streams of Category E, which are conservatively assumed to
be diluted to avoid exceeding a 980°C combustion temperature, consequently
require a larger incinerator volume per normal cubic meter of offgas.
For this reason and because of the greater gas expansion at the higher
combustion temperature, capital charges account for about 42 percent of
the total annualized cost of the typical stream shown in Table 8-10.
The percentage of the total annualized cost due to capital charges
increases as offgas flowrate decreases due to economies of scale. In
contrast, utilities and operating labor are generally linear functions
of flowrate. For a given chemical manufacturing process, flowrate is
expected to be roughly proportional to capacity. Therefore, the percentage
of total annualized costs due to capital charges is also expected to
increase as capacity decreases.
Total annualized costs, as well as each contributing factor to
them, are expected to be essentially equal for any two given streams
with the same flowrate and heating value, but differing VOC contents.
(Such streams would have counterbalancing differences in non-VOC combustibles
content.)
Total annualized cost (for nonchlorinated streams) is expected to
decrease as heating value increases through Categories B and C, reaching
a minimum at the low-heating value end of Category D. Total annualized
cost is expected to increase with increasing heating value through
Categories D and E, due to greater combustion air and dilution air
requirements and gas expansion at higher combustion temperatures. This
increase is attributable to increased captial charges. For chlorinated
Category Al streams, total annualized cost decreases with increasing
offgas heating value. Annualized costs of Category A2 streams are not
expected to be particularly sensitive to variation in offgas heating
value. Due to higher capital costs attributable largely to the scrubber,
chlorinated streams are in general more costly to control than nonchlorinated
ones.
8.1.5.4 Cost-Effectiveness of Control of an Individual Facility
The cost-effectiveness values for a facility are defined as total
annualized costs per annual Mg of VOC emissions controlled. The cost-
effectiveness is calculated with respect to baseline emissions. Uncontrolled
8-22
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emissions were defined as emissions form the primary absorber vent. The
estimated baseline control fraction of 58 percent is derived in Chapter 3
and Appendix F. The cost effectiveness for selected vent streams of all
design categories and with various offgas characteristics are given in
Table 8-11.
That portion of cost-effectiveness attributable to utilities and
operating labor is generally insensitive to variations in offgas flowrate
or capacity. In contrast, that portion of cost-effectiveness attributable
to capital charges is expected to decrease with increasing flowrate.
This effect is illustrated by the three Category B streams in Table 8-11
which vary only in offgas flowrate. However, vent streams with flowrates
just large enough to require an additional control system unit will have
a correspondingly higher cost-effectiveness. The cost-effectiveness of
a Category B stream with a flowrate of 1,420 scm/min (the assumed
maximum value) is expected to increase about 8 percent if two equipment
units are employed.
Increases in VOC content decrease cost-effectiveness in two ways.
If non-VOC combustible content remains constant, heating value will
increase with increasing VOC content, and that portion of cost-effectiveness
attributable to fuel requirements will in general decrease. Emission
reduction is proportional to VOC content. Therefore, cost-effectiveness
is inversely proportional to VOC content (apart from the relation of
heating value to VOC content). This effect is illustrated in Table 8-11
by the pairs of streams which differ from each other only in VOC content.
Cost-effectiveness has a significant dependence on non-VOC combustible
content, although the relation is weaker than that between cost-effectiveness
and VOC content. Streams which differ in non-VOC combustible content
but not in VOC content must have different heating values. Among vent
streams in the statistical profile (discussed in Appendix F), variations
in non-VOC combustible content are quite pronounced. Cost-effectiveness
generally decreases with an increase in heating value, if the VOC content
is constant. However, cost effectiveness is expected to increase with
increased heating the boundaries of design Categories B and C, due to
the loss of potential heat recovery from the offgas. A cost-effectiveness
increase is also expected with increased heating value through the range
of Category E, due to the increasing dilution air requirements.
8-24
-------
The total resource-effectivenss (TRE) index of a vent stream is
defined as the cost-effectiveness of the stream, multiplied by 100, and
divided by $88.66 .thousand/Mg. The indexing constant of $88.66.thousand/Mg
corresponds to the highest cost-effectiveness of any stream, in the
national profile, with a VOC concentration above the detectable limit.
The TRE index is a convenient, dimensionless measure of the total
resource burden associated with VOC control at a facility. It is
independent of the general inflation rate. However, it does assume
fixed relative costs of the various resources, such as carbon steel and
natural gas.
The TRE index of a process vent stream can be estimated according
to the following equation:
TRE =
C(a
b (Qs°-88)
e (Qs°'88) (HT°-88)
(Qs) + d (Qs) (HT)
f (HT°'88)]
where:
TRE = Total resource-effectiveness index value.
Q = Vent stream design flowrate (scm/min), at a standard temperature
s of 20°C.
HT = Vent stream net heating value (MJ/scm), where the net enthalpy
of per mole of offgas is based on combustion at 25°C and 760 mm Hg,
but the standard temperature for determining the volume corresponding
to one mole is 20 C, as in the definition of Q .,
EVOC = VOC emiss1on rate reported in kg/hr measured at full operating
flowrate.
a, b, c, d, e, and f are coefficients. The set of coefficients
which apply to a process vent stream can be obtained from Table 8-12.
These coefficients were obtained by substituting the numeric values for
all variables, except offgas flowrate, heating value, and VOC content,
in the cost and emissions equations given in Tables 8-5 and 8-9. The
resulting equations were substituted into the cost-effectiveness equation
given in Table 8-9, which was then indexed to a constant cost-effectiveness
value as described above. The TRE index equation simplifies to the six
terms shown above. At least two of the equation terms equal zero for
8-25
-------
TABLE 8-12. COEFFICIENTS OF THE TOTAL RESOURCE-EFFECTIVENESS (TRE) INDEX EQUATION
Al. FOR CHLORINATED PROCESS VENT STREAMS, IF 0 <_ NET HEATING VALUE (HJ/scm) <. 3.3:
Qs * Standard Flowrate (scm/min)
(L < IS
15 < Q. < 790
790 < 0? < 1590
1S90 « Q! ~ 23SO
2380 < 0! ~ 3160
3160 < Q| " 3960
46.21
38.98
77.96
116.9
155.9
194.9
0
0.754
0.819
0.860
0.890
0.915
0.763
0.763
0.763
0.763
0.763
0.763
-0.325
-0.325
-0.325
-0.325
-0.325
-0.325
0
0
0
0
0
0
0
0
0
0
0
0
A2. FOR CHLORINATED PROCESS VENT STREAMS, IF 3.3 < NET HEATING VALUE (MJ/scm):
Qs * Standard Flowrate (scm/m1n) a b c
Q* < is
15 < Qc < 790
790 < Q* ~ 1590
1590 < Q! ~ 2380
2380 < 0! ~ 3160
3160 < Q| £ 3960
B. FOR 'NONCHLORIUATED PROCESS VENT STREAMS,
Qs » Standard Flowrate (sera/rain)
Q. < 15
1§ < Qe < 1520
1520 < Q* ~ 3050
3050 < Q* 7 4570 ,
C. FOR NONCHLORINATED PROCESS VENT STREAMS,
Qs * Standard Flowrate (sera/rain)
Q, < 15
l5 <
-------
vent streams in any design category. The term in the gas use equation
proportional to squared heating value is sufficiently insignificant that
it was ignored in constructing the simplified equation given above and
table of coefficients (Table 8-12).
Table 8-12 is divided into the six design categories for control
equipment. Under each design category listed in the table, there are
several intervals of offgas flowrate. Each fiowrate interval is associated
with a different set of TRE equation coefficients. The first flowrate
interval in each design category applies to vent streams with a flowrate
smaller than that corresponding to the smallest control equipment system
easily available without special custom design. The remaining flowrate
intervals in each design category apply to vent streams which would be
expected to use one, two, three, four, or five sets of control equipment,
respectively.
8.1.6 Modified/Reconstructed Facilities
As discussed in Chapter 5, few modifications or reconstructions are
anticipated for the air oxidation industry. Thus, the costs of control
systems for modified/reconstructed facilities will have a minimal impact
on the air oxidation industry. No costs for modified/reconstructed
facilities were incorporated into the regulatory alternative impact
estimates.
However, if a modification or reconstruction were to occur, the
cost for installing a control system in an existing plant that has been
modified or reconstructed is generally greater than the cost of installing
the control system in a new facility with the same exhaust gas parameters.
Such additional cost might be due to a steel or concrete deck for the
equipment, extra circuit breakers, and extra ducting. Installation
labor costs would also be higher for a retrofit situation. In order to
reflect the additional installation costs due to retrofit, a retrofit
correction ratio of 1.625 was employed. This correction factor is
mutliplied by the new source total installed capital cost of a control
system to give the retrofit total installed capital cost. The retrofit
correction factor is derived in Appendix G.
8-27
-------
8.1.7 Regulatory Alternative Impacts
As discussed in Chapter 6, each regulatory alternative would
specify a level of national VOC emission reduction from the baseline.
It was assumed that the particular facilities required to control
emissions under a given regulatory alternative would be those with the
lowest projected annualized cost of control, per unit of VOC destroyed.
Therefore, in order to project the regulatory alternative impacts, the
data vectors in the national profile were ranked in order of increasing
estimated cost-effectiveness of VOC emission control by thermal oxidation.
Alternative 0 represents the baseline level of control. Alternatives
I through VI would require approximately 31, 46, 57, 66, 81, and 98
percent national VOC reduction, respectively, from the baseline level.
These alternatives are based on the use of a thermal oxidizer operated
at 871°C (1600°F) with a chamber residence time of.0.75 second to
achieve 98 percent VOC control at air oxidation facilities required to
incinerate waste stream VOC.
Only a part of all air oxidation facilities would be required to
control emissions to achieve the national VOC reduction over the baseline
level specified under each regulatory alternative. The percentage of
all facilities covered by the air oxidation NSPS that would actually be
required to control emissions to 98 percent or 2.0 ppmv ranges from
approximately 7 percent for Alternative I to 100 percent for Alternative
VI.
Both capital and annualized operating costs were used to determine
total national costs for each regulatory alternative. These national
impacts are summarized in Table 8-13. The costs are given in December, 1978
dollars. The fifth year total national annualized cost would increase
from $3 million per year for Alternative I to $67 million per year for
Alternative VI. The fifth year'total national installed capital cost
would increase from $6,1 million for Alternative I to $87 million for
Alternative VI.
8.1.8 Chemical Process-Specific Costs
Costs for each specific chemical manufacturing process were developed
for use in the economic analysis presented in Chapter 9. Capital,
annualized, operating, and control costs (cents per kg of product), and
TRE values, for each chemical process are given in Table 8-14 in December, 1978
dollars.
8-28
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TABLE 8-14. CHEMICAL PROCESS-SPECIFIC COSTS
Chemical (Process)3
Acetaldehyde
Acetic Acid (Wacker)
Acetic Acid (Butane)
Formic Acid
Methyl Ethyl Ketone
Propionic Acid
Acetone (Cumene)
Acstophenone
Cuniene Hydroperoxide
Methyl Styrene
Phenol
Acrylic Acid
Acrolein
Acrylonitrile (Propane)
Acetonitrile
Hydrogen Cyanide
Anthraquinone
Benzaldehyde
Benzoic Acid
1 ,3-8utadiene
p.t-Butyl Benzoic Acid
n-Butyric Acid
Crotonic Acid
Cyclohexanol
Cyclohexanone
Dimethyl Terephthalate
Terephthalic Acid
Ethyl ene Oxide
Formaldehyde (Metal Oxide)
Formaldehyde (Silver)
Qlyoxal
Hydrogen Cyanide
Isobutyric Acid
Isophthalic Acid
Haleic Anhydride (Benzene)
Haleic Anhydride (Butane)
Phthalic Anhydride (Xylene)
Phthalic Anhydride (Naphthalene)
Propionic Acid (Propionaldehyde)
Propylene Oxide (Ethyl benzene)
Styrene
Ethylene Oichloride
Capital
Cost
(SI ,000/yr)
2400
1100
4400
4400
4400
4400
480
480
480
480
480
1300
1300
4600
4600
4600
430
280
330
1800
280
360
300
740
740
2700
2700
1100
350
280
290
280
290
2600
1000
2100
1200
1300
440
5200
5200
1700
Annual! zed
Cost
(Sl,000/yr)
2100
680
3700
3700
3700
3700
240
240
240
240
240
1400
1400
1700
1700
1700
210
84
120
860
84
150
no
260
260
2200
2200
460
130
-(71)
100
-(40)
130
1700
440
730
580
860
240
4800
4800
-(63)
Operating
Cost
($1 ,000/yr)
1700
500
3100
3100
3100
3100
170
170
170
170
170
1200
1200
990
990
990
ISO
41
73
580
41
94
63
140
140
1800
1800
300
77
-(114)
56
-(82)
84
1300
280
410
390
660
ISO
4000
4000
-(310)
Control
Cost
(Cents/kg)
1.8
2.8b
1.5
1.5
1.5
1 .5
0.9
0.9
0.7
0.7
0.7
2.0
2.0
1.5
1.5
1.5
15.2
9.0
4.4
4.0
4.0
3.1
2.4
0.7
0.7
1.3
1.3
1.1
2.9
-(1.1)
9.5
-(6,0)
3.8
2.9
5.3
4.0
4.6
2.9
0.7
0.9
0.9
0.2
Projected
TRE
Value0
11
0.9
2.0
2.0
2.0
2.0
0.9
0.9
0.9
0.9
0.9
0.1
0.1
0.1
0.1
0.1
79
42
17
11
21
53
13
0.2
0.2
1.1
1.1
0.2
2.7
-(1.4)
50
-(4.8)
0.6
1.6
0.5
1.8
0.5
0.9
0.5
17.5
17.5
-(0.1)
^Chemicals that are coproducts or byproducts of a particular air oxidation process are
indented.
bl.l kg of acetaldehyde is used to produce 1 kg of-acetic acid in the Uacker process. Hence
1.1 X control cost of acetaldehyde is added to the control cost of acetic acid (Wacker
process).
°These TRE values are for typical facilities. The TRE values for actual facilities would, in general, be
different.
8-30
-------
Several of these processes produce by-products and/or co-products.
For such processes, the by-products and co-products are listed under the
main product in Table 8-14. A single value of capital cost, annualized
cost, and operating cost was projected for such processes. In calculating
the control costs (cents per kg of product) for by-products and co-
products, the total annualized cost for the process was attributed to
each by-product/co-product. Likewise, the total production of all by-
products and co-products was used in calculating the control cost of
each by-product/co-product. Therefore, the control costs of the by-
product(s)/co-product(s) are equal. This method of projecting control
costs is equivalent to sharing the total annualized cost of the process
by weight of product.
The method of calculating chemical process-specific costs differed
from the methods used elsewhere in this chapter in several respects.
These differences, as well as parameters of the individual processes,
are discussed in detail in Appendix G. For those processes employing a
vapor-phase air oxidation reaction (discussed-in Chapter 3), offgas
flowrates were predicted according to the method discussed in Appendix F.
An after-tax discount rate of 8.5 percent was used. The actual offgas
oxygen concentrations were considered in estimating offgas flowrates and
capital costs. Chemical processes with offgas net heating values that
fall in Categories D and E were assumed to have a heat recovery credit
due to use of a waste heat boiler. No dilution of offgas was assumed
for processes with heating values within the Category E range. For
processes with heating values within the range of Category C, offgas
dilution sufficient to permit use of 70 percent recuperative heat
recovery was assumed, if such dilution would result in lower projected
annualized costs. Such processes were assumed to employ an offgas
dilution sufficient to yield a net heating value of.0.48 MJ/Nm3, and
place the process within design Category B.
8.2 OTHER COST CONSIDERATIONS
8.2.1 Control Cost Accumulation for Synthetic Organic Chemical
Manufacturing Industries Using Air Oxidation Processes
8.2.1.1 Introduction
Since passage of the Clean Air Act Amendments of 1977, EPA has
initiated action on eight possible new source performance and hazardous
air pollutant standards that will affect the air oxidation industry.
8-31
-------
None has been promulgated as of the proposal date of the air oxidation
standard. The adjusted accumulated fifth-year annualized cost of these
potential regulations is $21.1 million. The air oxidation standard
comprises $11 million (52 percent) of the total cost resulting from
these potential regulations. About one-half of this cost.will be borne
by the air oxidation industry and its customers and suppliers. The
other half will be paid by the taxpayers in the form of foregone tax
revenues. This cost is judged to be reasonable.
It is necessary that the air oxidation industry be defined in
precise terms before the costs of regulations can be identified and
accumulated. The air oxidation industry, as the term is used in this
discussion, consists of all facilities and activities directly involved
in the production, or storage prior to shipment, of any of 26.air
oxidation chemicals regardless of whether the production is by an air
oxidation process. This definition is broad in the sense that it
includes a large number of facilities that produce air oxidation chemicals
by nonair-oxidation processes, as well as many existing facilities that
will not be affected by a possible air oxidation standard. However, the
definition excludes facilities for the production of nonair-oxidation
chemicals by the same firms that produce air oxidation chemicals,
facilities for the production of about 10 air oxidation chemicals that
are very low volume chemicals or that have no projected growth, and
terminal storage of air oxidation chemicals away from the production
site. Despite these shortcomings, the definition is sufficiently broad
so that cost projections will be conservative (higher than the actual
costs).
Listed below are the relevant potential regulations for cumulative
costs with corresponding Start Action Notice (SAN) numbers:
Benzene Emissions from Benzene Storage Tanks, SAN
Benzene Fugitive Emissions, SAN No. 1126,
Benzene Emissions from the Ethylbenzene/Styrene
1128.
Benzene Emissions from the Maleic Anhydride Industry,
SAN No. 1127.
5. NSPS: VOC Fugitive Emissions in Synthetic Organic Chemicals
Manufacturing Industry, SAN No. 1112.
1.
No. 1593.
2.
3.
Industry,
4.
NESHAP
NESHAP
NESHAP
SAN No
NESHAP
8-32
-------
6, NSPS: VOC Emissions from Volatile Organic Liquid Storage
Tanks, SAN No. 1612.
7. NSPS: VOC Emissions from Air Oxidation Process Vents in the
Synthetic Organic Chemical Manufacturing Industry, SAN No. 1618.
8. NSPS: VOC Emissions from Distillation Process Vents in the
Synthetic Organic Chemical Manufacturing Industry. (No SAN has been
issued at this time.)
The basic methodology employed to generate cumulative annualized
control costs is presented below:
1. All control costs are standardized to mid-1978 dollars.
2. All control costs are annualized using a real, before-tax
interest rate of 10 percent.
3. Only the EPA Administrator's recommended regulatory alternative
is considered when accumulating costs for existing (NESHAP's) and new,
modified, or reconstructed (NESHAP's and NSPS's) facilities. In cases
where development of a regulation has not progressed to a late enough
stage to have a recommended regulatory alternative, a best estimate is
made of the most likely regulatory alternative to be selected.
4. All control costs are incremental and do not include the cost
of pollution control equipment already in place.
5. Costs are tabulated only for the specific chemical industries
that make up the air oxidation industry and are thus directly affected
by the potential air oxidation process NSPS. For example, the potential
VOC Fugitive Emissions NSPS affects a far greater number of chemical
industries than does the potential air. oxidation process NSPS, but the
annualized costs of control of the potential VOC Fugitive Emissions NSPS
are calculated only for the chemical industries that utilize the air
oxidation process.
6, For NESHAP and NSPS regulations, the fifth year total annualized
control costs for new, modified, or reconstructed facilities are used
for accumulation. The fifth year total annualized control costs refer
to the control costs expected to be incurred by the affected industry,
customers, and suppliers in the fifth year following proposal of a
standard in the FEDERAL REGISTER. The fifth year costs are calculated
by multiplying annualized control costs for one facility (in constant
dollars) by the projected number of facilities to be affected by the
8-33
-------
regulation. The fifth year will vary among potential regulations
because the dates of proposal in the FEDERAL REGISTER vary among poten-
tial regulations. The number of new facilities using the air oxidation
process expected to be built between December 1, 1981 and December 1, 1986.
(see Table 9-11, Scenario I) is used to calculate fifth year control
costs for all four of the potential NSPS regulations, even though the
five year period used for air oxidation projections does not correspond
exactly to five year periods of other regulations.
7. When costs are accumulated, a few individual chemical industries
for which projections are made can be grouped together as one industry
because of the existence of coproducts or byproducts. To avoid any
double counting when projecting the number of new facilities, coproducts
are combined as one industry (e.g., propylene oxide is combined with
styrene, terephthalic acid is combined with dimethyl terephthalate,
acetic acid is included with methyl ethyl ketone, acrylonitrile is
combined with hydrogen cyanide, and acetone is included with phenol).
Byproducts are included with their primary product as one industry
(i.e., n-butyric acid, formic acid, and propionic acid are included with
acetic acid and methyl ethyl ketone; acetophenone, cumene hydroperoxide,
and a-methyl styrene are included with acetone and phenol; acetonitrile
is included with acrylonitrile and hydrogen cyanide; and acrolein is
combined with acrylic acid). Refer to Section 9.1.8 and Section 3.3.1
for more information on coproducts and byproducts.
8. Table 9-11 gives a projection only for future facilities using
the air oxidation process. Some of the chemical industries using an air
oxidation process will also utilize nonair-oxidation processes. Cumu-
lative costing here involves the entire industry- so when deriving
control costs for the VOC fugitive emissions, volatile organic liquid
storage tanks and distillation columns NSPS's, both air oxidation and
nonair-oxidation process facilities are examined. In order to project
the total number of facilities for each industry, the projected number
of new air oxidation facilities, as reported in Table 9-11, is divided
by the ratio of estimated production by an air oxidation process to
total production by all processes in 1982 for each of 17 industries (the
projections in Table 9-11 are rounded off; in this excercise the unrounded
projection calculations are used). These ratios are presented in
percentage terms in Table 3-7. The results of this exercise are found
on Table 8-15.
8-34
-------
TABLE 8-15. FIVE YEAR PROJECTIONS OF NEW FACILITIES UTILIZING
BOTH AIR OXIDATION AND NONAIR-OXIDATION PROCESSES
Chemical'
Number of New Facilities
Acetaldehyde
Acetic acid
n-8utyric acid
Formic acid
Methyl ethyl ketone
Propionic acid
Acetone
Acetophenone
Cumene hydroperoxide
a-Methyl styrene
Phenol
Acrylic acid
Acrolein
Acrylonitrile
Acetonitrile
Hydrogen cyanide
Benzoic acid
1,3-8utadiene
Ethylene dichloride
Ethylene oxide
Formaldehyde
Hydrogen cyanidec
Isophthalic acid
Maleic anhydride
Phthalic anhydride
Propionic acid
Propylene oxide
Styrene
Terephthalic acid
Dimethyl terephthalate
3
6
5
1
19
4
1
6
3
0
2
Chemicals that-are coproducts or byproducts of a particular air
oxidation process are indented. The projected number of new
facilities producing these chemicals is zero to avoid double
counting. Refer to Section 9.1.8 for more information on
coproducts and .byproducts.
^hen produced by the propionaldehyde oxidation process, propionic
acid is an only product, but is a byproduct when produced with acetic
acid, n-butyric acid, formic acid, and methyl ethyl ketone
(n-butane oxidation process).
Hydrogen cyanide is principally produced as an only product but is
also produced in the propylene ammoxidation process as a coproduct
with acrylonitrile.
One of the two projected new facilities will utilize an air
oxidation process, and in this case propylene oxide and styrene are
coproducts. The other projected facility will produce only styrene
(a nonair-oxidation process) but is placed-with propylene oxide to
be consistent and avoid confusion. The cost calculations are not
affected.
8-35
-------
9. Table 8-16.lists the costs for 26.of the-36.chemical industries
affected by the potential air oxidation process NSPS. Two chemical
industries, acrylonitrile and propionic acid (propionadehyde oxidation
process), have zero new, modified, or reconstructed facilities projected
and hence do not experience any NSPS costs. The other eight chemical
industries are excluded for lack of information needed to project new
facilities. However, the eight chemical industries omitted represent
only five percent of the total air oxidation process capacity.
The data presented in Table 8-16.are based on the above general
methodology and more specific assumptions. These regulation-specific
assumptions are presented below.
8.2.1.2 Data and Assumptions for Accumulating Costs
1. Benzene Storage NESHAP. Cost data are from the draft Environmental
Impact Statement (EIS) titled "Benzene Emissions from Benzene Storage
Tanks -- Background Information for Proposed Standards," December 1980,
(EPA-450/3-80r034a). Page numbers referencing costs are from this EIS.
Cost data in the EIS are in first quarter 1979 dollars.
The benzene storage NESHAP would affect two chemical industries
that utilize the air oxidation process: maleic anhydride and styrene.
Both of these industries are benzene consumers.
EPA recommends (45 FR 83952) regulatory alternative IV for existing
sources and regulatory alternative III for new sources. Alternative IV
requires that each fixed roof, external floating roof, and internal
floating roof tank be converted to a contact internal floating roof tank
with a liquid-mounted primary seal and a continuous secondary seal.
Alternative III requires that each fixed roof, external floating roof,
and internal floating roof storage tank be converted to a contact
internal floating roof tank with a liquid-mounted primary seal.
The cost to existing styrene and maleic anhydride facilities is
$6,800 per facility (p. 7-45) for Alternative IV. There are 12 styrene
facilities and 10 maleic anhydride facilities presently in existence
(see Table 9-1). Hence, the total cost to all existing styrene and
maleic anhydride facilities is $81,600 and $68,000, respectively.
The control cost for new styrene and maleic anhydride facilities is
$5,700 per facility (p. 7-53) for Alternative III. According to
Table 8-15, six new facilities are projected for maleic anhydride.
8-36
-------
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However, it is believed that all new maleic anhydride sources will use
n-butane instead of benzene as the main feedstock. Hence, benzene
storage costs will be zero for future maleic anhydride facilities. Two
styrene facilities are projected to be constructed, one producing
styrene as a coproduct with propylene oxide by an air oxidation process
and the other producing styrene by a nonair-oxidation process. Total
annualized cost of control for new styrene sources is $11,400.
An aggregation of control costs for existing and new sources
amounts to $93,000 for the styrene industry and $68,000 for the maleic
anhydride industry. The mid-1978 producer's price index is 209.6.and
the first quarter 1979 producer's price index is 226,7. In mid-1978
dollars, the total annualized cost of control is $86,000 for the
styrene/propylene oxide industry and $63,000 for the maleic anhydride
industry.
2. Benzene Fugitives NESHAP. Cost data are from the draft EIS
titled "Benzene Fugitive Emissions-Background Information for Proposed
Standards," November 1980, (EPA-450/3-80T032a). Page numbers referencing
costs are from this EIS.
Cost data in the EIS are in May 1979 dollars.
The benzene fugitive NESHAP would affect two chemical industries
that utilize the air oxidation process: maleic anhydride and styrene.
Both of these industries experience fugitive benzene emissions.
EPA recommends (46.FR 1165) regulatory Alternative III for existing
sources. Regulatory Alternative III requires the installation of
closed-loop sampling systems and rupture disks on gas service safety/relief
values that vent to the atmosphere. Degassing vents on pump seal oil
reservoirs would be required to be vented to a closed system; accumulator
vessels would be required to be vented to a closed system; and open-
ended valves would be required to be sealed with a cap, blind, plug, or
another valve. Monthly monitoring for detection of leaks from pumps,
drain compressors, and valves would also be required. Regulatory
Alternative IV requires double seals on pumps and compressors in addi-
tion to the requirements of regulatory Alternative III. EPA recommends
that Alternative IV be imposed in the case of new sources.
The cost to existing styrene and maleic anhydride facilities is
$8,700 per facility when Alternative III is imposed. This number is
derived from the control costs for three different model facilities.
8-38
-------
The cost of control for model facility A is $7,400, for model facility B,
$9,700, and for model facility C, $15,200 (pp. 8-26.through 8-31). It
is estimated that 62 percent of existing refinery and SOCMI benzene-
related production units would be represented by model A, 31 percent by
model B, and seven percent by model C (p. 6T3). The $8,700 per facility
cost is an average control cost for the three model facilities, weighted
by the estimated current population, of each model facility. There are
12 styrene facilities and 10 maleic anhydride facilities presently in
existence (see Table 9-1). Hence, the total cost to all existing
styrene and maleic anhydride facilities is $104,400 and $87,000, respectively.
The control cost for new styrene and maleic anhydride facilities is
$18,200 per facility when Alternative IV is imposed. This figure is
based on the same model facilities used for existing sources. The cost
of control for a new model facility A is $12,000, for new model facility B
is $25,700, and for new model facility C is $39,900. Because it is
expected that new facilities will follow the same distribution as the
current population, the weighting procedure (i.e., model A-62 percent,
model B-31 percent, model C-7 percent) is implemented to determine the
composite cost. The should be no new maleic anhydride sources using
benzene, so there is no cost. Two styrene facilities (one producing
styrene as a coproduct with propylene oxide by an air oxidation process,
the other producing styrene by a nonair-oxidation process) are projected
to be constructed (refer to air oxidation BID page 8-34, #8). Total
annualized cost of control for new styrene sources is expected to be
$36,400.
Aggregate control costs for existing and new sources amount to
$140,800 for the styrene industry and $87,000 for the maleic anhydride
industry. The mid-1978 producer's price index is 209.6.and the May 1979
producer's price index is 232,0. In mid-1978 dollars the total annualized
cost of control is $127,000 for the styrene industry and $78,000 for the
maleic anhydride industry.
3. Ethylbenzene/Styrene NESHAP. Cost data are from the draft EIS
titled "Benzene Emissions from Ethylbenzene/Styrene Industry-Background
Information for Proposed Standards," August 1980, (EPA-450/3-79-035a).
Page numbers referencing costs are from this EIS.
Cost data in the EIS are in fourth quarter 1978 dollars.
8-39
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The .ethyl benzene/styrene NESHAP would affect one chemical industry
that utilizes the air oxidation process: styrene.
EPA recommends (45 FR 83448) regulatory Alternative C for continuous
emissions and regulatory Alternative I for excess emissions. Alternative C
requires that facilities achieve 99 percent benzene emission reduction
in the main process vents based on the use of a boiler or process
heater. Alternative I would require the use of smokeless flares. Most
styrene facilities have flares in place and only four existing facilities
would be required to install smokeless flares.
The cost to an existing styrene facility is $400,000 if a flare
(Alternative I) is needed, and $229,000 if a flare is presently in
place. The annualized cost per facility to control continuous emissions
is a $460,000 credit (p. 7-41). The analysis assumed that benzene is
recovered in the condenser and scrubber system and is fed back into the
process via the benzene drying column. The value of the benzene recovered
is subtracted from the control cost. In this case the value of the
benzene recovered is greater than the control cost. The cost of controlling
excess emissions is $171,000 per plant and the cost of monitoring is
$68.9,000. Multiplying the $400,000 cost by the four plants that do not
have flares in place results in a $1,600,000 cost. The other eight
existing styrene plants experience an aggregate cost of $1,832,000
($229,000 times eight). Thus, the total control cost to existing
styrene facilities is $3,432,000.
The EIS did not project any new styrene facilities, so costs were
not derived for new sources. It is assumed that new sources producing
styrene will experience the $400,000 control cost. Two styrene facilities
(one producing styrene as a coproduct with propylene oxide fay an air
oxidation process and the other producing styrene by a nonair oxidation
Process) are projected to be constructed (refer to Table 8-15). The
total annuali2ed cost of control for new styrene sources is $800,000.
Aggregate control costs for existing and new sources amount to
$4,232,000 for the styrene industry. The mid-1978 producer's price
index is 209.6.and the fourth quarter 1978 producer's price index is
217.5. In mid-1978 dollars the total annualized cost of control for the
styrene/propylene oxide industry is $4,078,000.
8-40
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4. Maleic Anhydride NESHAP. Cost data are from the draft EIS
titled "Benzene Emissions from the Maleic Anhydride Industry-Background
Information for Proposed Standards," February T980, (EPA-450/3-80T001a).
Page numbers referencing costs are from this EIS. ;
Cost data in the EIS are in second quarter 1979;dollars.
This regulation would affect only the maleic anhydride industry.
EPA recommends (42 FR 26660) a 97 percent efficiency control option
for existing sources. For the 97 percent regulatory option, the total
annualized control costs would be approximately $2,100,000 for the
existing maleic anhydride industry (p. 5-63). The mid-1978 producer's
price index is 209.6.and the second quarter 1979 producer's price index
is 233.5. In mid-1978 dollars the total annualized cost of control is
$1,885,000 for the maleic anhydride industry.
5. VOC Fugitive Emissions NSPS. Cost data are from the draft EIS
titled "VOC Fugitive Emissions in Synthetic Organic Chemicals Manufacturing
Industry - Background Information for Proposed Standards," November 1980,
(EPA-450/3-80T033a). Page numbers referencing costs are from this EIS.
Cost data in the EIS are in fourth quarter 1978 dollars.
The VOC fugitive emissions NSPS would affect all SOCMI chemicals
that are produced using the air oxidation process.
EPA recommends (46.FR 1136) regulatory Alternative IV. Alternative IV
requires: a) the monthly monitoring of all in-line Valves and open-
ended valves in gas and light liquid service, b) the1 installation of
rupture discs upstream of service safety/relief valves that vent to the
atmosphere, c) the installation of closed, vents and control devices for
compressor seal areas and/or degassing vents from compressor barrier
flued reservoirs, d) the installation of dual mechanical seals on pumps
in light liquid service and installation of closed vent control devices
for degassing vents from barrier fluid reservoirs of! all pumps in light
liquid service, e) the installation of closed loop sampling systems, and
f) the installation of caps, blinds, plugs, or seconcl valves to seal all
open-ended lines. . i
The cost of this standard is $13,500 per facility if Alternative IV
is used. This figure is derived from the control costs for three
i
different model facilities. The. cost of control for bode! facility A is
$7,900, for model facility B, $13,300, and for model 'facility C, $33,000 .
8-41
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(pp. 8-14 through 8-16). The EIS estimates that 52 percent of existing
SOCMI plants are similar to model facility A, 33' percent are similar to
B, and 15 percent are similar to C (p. 6T2). It is assumed that this
distribution will hold for the future SOCMI facility population. The
$13,500 per facility cost is an average control for the three model
facilities, weighted by the estimated current SOCMI population of each
model facility.
To arrive at specific chemical industry costs, the $13,500 per
facility control cost is multipled by the projected number of new
sources for each chemical industry that uses air oxidation processes
(refer to Table 8-15). All costs are multiplied by 209.6/217.5, the
ratio of the mid-1978 producer's price index to the fourth quarter 1978
producer's price index, in order to put all costs in mid-1978 dollars.
6, Volatile Organic Liquid Storage Tanks NSPS. Cost data are
from the draft EIS titled "VOC Emissions, from Volatile Organic Liquid
Storage Tanks - Background Information for Proposed Standards," April 1981,
(EPA-450/3-81r003a). Page numbers referencing costs are from this EIS.
Cost data in the EIS are in first quarter 1980 dollars.
The Volatile Organic Liquid Storage Tanks NSPS would affect all
SOCMI chemicals that are produced using the air oxidation process.
As stated in the preamble of the EIS,, EPA recommends regulatory
Alternative IV. This option would require that each storage vessel
storing a VOL with a true vapor pressure less than 76,6.kPa be equipped
with a contact internal floating roof with1 a liquid-mounted primary seal
and a continuous secondary seal. A vapor control system would be
required for all storage vessels storing a VOC with a true vapor pressure
greater than or equal to 76,6.kPa.
The total annualized cost of regulatory Alternative IV for all of
the SOCMI is assumed to be a credit of $5,790,000 (p. 9-48). Product
I
recovery credits are assumed to be 36^/kgj the average value of recovered
i
products. In order to obtain specific che'mical industry costs the
$5,790,000 figure is divided by the total istorage tank population of
47,059 (p. 9-47). This calculation gives !a credit of $123 per storage
tank. The $123 is multiplied by 72, the average number of storage tanks
i
at each facility (p. 9-47). This results in an approximate credit of
$9,000 per facility. :
8-42
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To arrive at specific chemical industry credits, the $9,000 credit
is multiplied by the projected number of new sources for each chemical
industry that uses the air oxidation process (refer to page 8-34, #8 for
projections). All credits are multiplied by 209.6/261.5, the ratio of
the mid-1978 producer's price index to first quarter 1980 dollars, in
order to put all costs in mid-1978 dollars.
7. Air Oxidation Processes NSPS. Cost data are obtained from
Chapter 8 of this document and are in mid-1978 dollars.
For purposes of convenience, it is guessed that Regulatory III will
be the preferred course of action. This alternative requires a 57 percent
national VOC reduction from the baseline level based on the use of a
thermal oxidizer at those air oxidation facilities required to meet a
98 percent VOC reduction requirement.
The national annualized cost is estimated to be $11,000,000 when
regulatory Alternative III is chosen (Table 8-13 of this BID). It is
not possible to determine which future air oxidation facilities would be
required to control VOC emissions to achieve the national emission
reduction under regulatory Alternative III. In order to accumulate
costs on an individual industry basis, it is assumed that the $11,000,000
total cost will be shared based on a specific industry's individual
plant costs and projected number of new sources. Table 9-11 of this
document provides the projected number of new air oxidation facilities
and. Table 8-14 gives chemical process-specific costs. For each industry
the projected number of new facilities is multiplied by each chemical
industry's specific cost. The products are summed to arrive at a total
cost for all industries. Next, the percentage of the total cost attri-
butable to each specific industry is calculated and the $11,000,000
national annualized cost of control is distributed,to each chemical-
specific industry based on these percentages. Table 8-17 presents the
calculations and results.
S. Distillation Columns NSPS. Cost data are obtained from the
most recent ESED contractor memorandum (June 3, 1981). The cost data
obtained are based on worst case assumptions and are in mid-1978 dollars.
The Distillation Columns NSPS would affect all SOCMI chemicals that
are produced using the air oxidation process. No regulatory alternatives
have been defined as of yet.
8-43
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TABLE 8-17. FIFTH YEAR ANNUALIZED COSTS OF THE NSPS FOR AIR
OXIDATION PROCESS, BY SPECIFIC INDUSTRY
26.Chemical Industries
United States
1978
Chemical Industry
Acetaldehyde
Acetic acid
n-8utyr1c add
Formic acid
Methyl ethyl ketone
Propionic acid
Acetone
Acetophenone
Cumene hydroperoxide
o-Methyl styrene
Phenol
Acrylic add
Acroleln
Benzole add
1 ,3-Butadlene
Ethylene dlchlorlde
Ethylene oxide
Formaldehyde
Hydrogen cyanide
Isophthalic add
Maleic anhydride
Phthallc anhydride
Propylene oxide
Styrene
Terephthalic add
Dimethyl terephthalate
Total
Projected
Number
of air
Oxidation
Facilities
0
2
4
1
3
1
2
1
19
4
1
6
3
1
1
Annual ized
Chemical
Process-
Specific
Costs
($1,000)
2,083
2,196a
240
1 ,661
122
895
-16
581.
35b
20
1 ,658 •
590d
713d
4,816
2,213
Total
Projected
Cost per
Industry:
AxB
($1,000)
0
4,392
480
1 ,661
366
895
-32
581
665
80
1 ,658
3,540
2,139
4,816
2,213
23,454
Share of all
Industry' s
Cost: AxB v
Sum of
Column (C)
.000
.187
.020
.071
.016
.038
.000
.025
.028
.003
.071
.151
.091
.205
.094
1 .000
Alternative III
Costs per Industry:
Column D
Multiplied
by
$11 ,000,000
0
2,057,000
220,000
781 ,000
176,000
418,000
0
275,000
308,000
33,000
781 ,000
1 ,661 ,000
1,001,000
' 2,255,000
1 ,034,000
11 ,000,000
The number is based on the assumption that one acetic acid projected facility will use the Wacker process
and the other the n-butane process.
The number Is based on the assumption that 12 of the projected formaldehyde facilities will use a
crystalline silver catalyst, methanol, and air in the air oxidation process and seven will use a mixed
metal catalyst, methanol, and air in the air oxidation process.
The number 1s based on the assumption that all future maleic anhydride facilities will use n-butane as a
Feedstock.
The number is based on the assumption that two of the projected phthalic anhydride facilities will use
xylene as a feedstock and one will use naphthalene as a feedstock.
NOTE: These assumptions are based on current facility distributions or future known trends.
8-44
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The worst case cost (TOO percent control) for each facility with
distillation columns is $354,100. The regulatory alternative chosen for
the air oxidation NSPS represents approximately 16.percent of the cost
associated with the air oxidation NSPS regulatory alternative requiring
100 percent control. It is assumed that the control alternative chosen
for distillation will be on a similar level as the control alternative
for air oxidation processes. Thus $354,]00 is reduced by 84 percent to
$56,700 per facility.
For each chemical industry, the projected number of new facilities
from Table 8-15 is multiplied by $56,700 to approximate the cost per
industry of a distillation column NSPS.
8.2.2 Costs of Regulations Other Than NSPS's and NESHAP's
This section summarizes the costs of all other environmental
regulations, other than new source performance and hazardous air pollutant
standards, impacting SOCMI. Most of these regulations affect the entire
synthetic organic chemical industry, not just air oxidation facilities.
There also are regulations which are applicable only to a specific
chemical within air oxidation. The other regulations SOCMI has to
comply with are water pollution control regulations, worker safety
regulations, and toxic and hazardous waste regulations. Table 8-18
lists all the provisions and requirements of the regulations applicable
to air oxidation facilities. All cost information is in December 1978
dollars,
8-2.2.1 Water Pollution Control Regulations
}- Federal Water Pollution Control Act (FWPCA). SOCMI facilities
are required by the FWPCA to comply with effluent limitation guidelines.
Under the guidelines for the organic chemicals manufacturing industry,
existing sources must apply best practical control technologies avail-
able (BPCTA) and new sources must apply best available demonstrated
control|technology (BADCT),48 Currently, guidelines for organic chemicals
are beiitig revised.
The Clean Water Act of 1977 amended the FWPCA and required that the
best available technology economically achievable (BATEA) be implemented
by 1984jfor non-conventional and toxic pollutants. For conventional
pollutants, best conventional technology (BCT) is required. The guidelines
developed for BCT take different cost considerations into account than
BATEA.
49;
8-45
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TABLE 8-18. STATUTES THAT MAY BE APPLICABLE TO AIR OXIDATION FACILITIES
Statute
Applicable Regulation
or Regulations
Clean Air Act and Amendments
Clean Water Act (Federal Water
Pollution Control Act)
Resource Conservation and Recovery
Act
Toxic Substances Control Act
Occupational Safety and Health
• State implementation plans
« National emission standards for
hazardous air pollutants
• Mew source performance standards
- VOC fugitive emissions
- Volatile organic liquid storage
• PSD construction permits
• Nonattainment construction permits
• Effluent limitations guidelines
• New source performance standards
• Discharge permit (NPDES)
• Control of oil spills and discharges
• Pretreatment requirements
• Monitoring and reporting
• Permitting of industrial projects that
impinge on wetlands or public waters
• Environmental impact statements
• Hazardous wastes
- Permits for treatment, storage, and
disposal of hazardous wastes
- Manifest system to track hazardous
wastes
» Establishes recordkeeping, reporting,
labeling, and monitoring system for
hazardous wastes
• Nonhazardous wastes
- State discharge programs
• Toxicity testing
• Premanufacture notification
• Labeling, recordkeeping
• Reporting requirements
• Occupational health and environmental
control standards
• Hazardous material standards
8-46
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TABLE 8-18 (Continued).
STATUTES THAT MAY BE APPLICABLE TO AIR
OXIDATION FACILITIES
Statute
Applicable Regulation
or Requirements
Occupational Safety and Health
(cont'd)
Comprehensive Environmental Response,
Compensation, and Liability Act
(Superfund)
Safe Drinking Water Act
Marine Protection, Research, and
Sanctuaries Act
•
•
•
•
•
General environmental control standard
Personal protective equipment standards
Building safety and health standards
(unrelated to product)
Medical and first aid standards
Fire protection standards
Walking-working' surface standards
Means of egress standards
Compressed gas and compressed air
equipment
Welding, brazing, and cutting standards
Cleanup costs for dumpsites and spills
Tax to establish post-closure trust fund
• Primary and secondary drinking water
standards for groundwater
• Underground injection control permits
• Ocean dumping permits
• Recordkeeping and reporting
8-47
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EPA has developed water quality criteria documents for 64 toxic
water pollutants or categories of pollutants. These documents contain
recommended maximum permissible pollutant concentrations for the protection
of aquatic organisms, human health, and some recreational activities.
These documents do not consider treatment technology, costs, or other
feasibility factors.50 The air oxidation chemicals listed as toxic
pollutants to be controlled are:
(1) acrolein,
(2) acrylonitrile,
(3) cyanides, and
(4) phenol.
The National Pollution Discharge Elimination System (NPDES) enables
States to issue discharge permits. Eighty-five percent of the chemical
products industry (SIC 28) is in compliance with the Federal water
pollution reporting regulations required under NPDES.
The capital cost to the organic chemical industry of controlling
water pollution was $3.4 billion from 1970 through 1977. The cumulative
capital costs from 1977 to 1986.are expected to be $2.9 billion. The
annual cost for 1977 was $401.6.million and the cumulative costs from
1977 to 1986.are expected to be $6,5 billion.52
2. Safe Drinking Water Act (SDWA). The Safe Drinking Water Act
requires EPA to establish primary and secondary drinking water standards.
Primary regulations are aimed at protecting public health. They establish
maximum allowable contaminant levels in drinking water and provide for
water supply system operation. Secondary regulations are designed to
protect public welfare and control the taste, odor, and appearance of
drinking water. The Act also controls underground injection through
permitting. In establishing maximum control levels (MCL), the technological
and economic feasibility is considered as well as the health effects.
Currently, the MCL for VOC in groundwater is being developed; therefore,
53
control costs are unknown. Since there are very few MCLs at this
time, States have the option of controlling toxic pollutants when a MCL
54
does not exist.
8.2.2.2 Occupational Safety and Health Regulations
The Occupational Safety and Health Administration (OSHA) is responsible
for protecting workers against hazardous materials found in the workplace.
There are two types of regulations established by OSHA which affect the
8-48
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56
air oxidation industry. The first type is general administrate and
engineering controls for hazardous substances. The air oxidation
chemicals that are controlled by these general standards are listed in
55
Table 8-19. If engineering controls and work practice standards are
not feasible to achieve full compliance, protective equipment is to be
used.
A second type of regulation has been developed for the more significant
hazardous air pollutants. These are comprehensive regulations that
establish administrative and engineering controls specific to one
pollutant only. As far as air oxidation chemicals are concerned,
comprehensive standards have been promulgated for acrylonitrile only.1
The average cost of OSHA regulations on the entire chemical industry
is estimated to be $208.40 per worker per year.57 The type of worker
protection is dependent on the chemical produced at each air oxidation
facility. In those facilities where only general controls are required,
the costs would vary with the control method(s) employed by each facility.
OSHA also has specific regulations for chemical facilities which
handle, store, or use flammable and combustible liquids with a flash
point less than 200°F under Section 29 GFR 1910.106,58 Once again, OSHA
bases these standards on toxicity levels and not on cost criteria.
8-2.2.3 Toxic Substance Control Regulations
Toxic Substance Control Act (TSCA) requirements are based on the
need to provide necessary information concerning the toxicity of new and
existing chemicals. TSCA requires reporting of the manufacturing,
importing, or processing of any chemical substance used for a commercial
purpose in order to develop a chemical inventory. Any substance not on
the inventory will be considered new and require premanufacture notice
and testing. Reporting and premanufacture notification (PMN) includes:
(1) the cost of using screening and testing to gain appropriate information
for new chemicals, (2) the cost of testing existing chemicals, and (3)
the cost of the delay caused by the testing/reporting process. PMN
could have a significant impact on the entire chemical industry, with
cost estimates ranging from $78.5 million to $2 billion.59
Small companies will probably suffer more than the larger firms
since small firms have minimal access to the information necessary to
develop a PMN. The impact of PMN also will be greater to the small
8-49
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TABLE 8-19. AIR OXIDATION CHEMICALS REGULATED BY OSHA GENERAL CONTROLS
Acetaldehyde
Acetic Acid
Acetone
Acetonitrile
Acrolein
1,3-Butadiene
Cyclohexanol
Cyclohexanone
Ethylene Dichloride
Ethylene Oxide
• Formaldehyde
Formic Acid
- Hydrogen Cyanide
Maleic Anhydride
Methyl Ethyl Ketone
a-Methyl Styrene
Phenol ,
Phthalic Anhydride
Propylene Oxide
Styrene
8-50
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firms because the cost per product will be higher for low volume, low
revenue chemicals. The cost of preparing notices for new chemicals is
estimated to be between $820 and $7400 per chemical.- •
EPA has been concentrating its efforts on new chemicals being
developed rather than existing ones; therefore, the actual cost to the
SOCMI air oxidation facilities of meeting TSCA is unknown.
8.2.2.4 Solid and Hazardous. Waste Regulations
1. Resource Conservation and Recovery Act (RCRA). RCRA establishes
a national program to improve solid waste management including the
control of hazardous waste, the promotion of resource conservation and
recovery, and the establishment of a solid waste disposal program.
The hazardous waste program regulates wastes from generation to
disposal ("cradle to grave") requiring EPA to produce standards for
generators, transporters, and those who transport, store, and dispose
(TSD facilities). The wastes are identified and listed by industry. At
the time of generation, a manifest system is developed to record the
movement of the wastes from cradle to grave.
The organic chemical industry generates 35 percent of the hazardous
wastes generated annually. The air oxidation chemicals listed in
Table 8-20 are considered hazardous under RCRA and must be controlled if
discarded. Because these chemicals are desired products, they are
usually not discarded. Some air oxidation processes are classified as
specific sources of hazardous waste. These sources are included in the
hazardous waste process listing for organic chemicals.
The management of nonhazardous wastes essentially remains a State
and local function implemented under State and regional solid waste
plans.
As the cost of handling wastes increases, some firms will reduce
their costs by changing their process to eliminate wastes or by recycling
or reclaiming the waste. New plant and equipment expenditures for solid
waste control were $42-$45 million for the entire chemical industry in
en ""
both 1978 and 1979. • The annual cost imposed by RCRA on 45 organic
chemical plants generating hazardous wastes is estimated to be $10.9
million or an average annual cost of $240,000 per plant.6^ These
estimates are based on model plants.
8-51
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TABLE 8-20. AIR OXIDATION CHEMICALS REGULATED BY RCRA
Acetaldehyde
Acetone
Acetonitrile
Acetophenone
Acrylic Acid
Acrylonitrile
Cyclohexanone
Ethylene Dichloride
Ethylene Oxide
Formaldehyde
Formic Acid
Maleic Anhydride
Methyl Ethyl. Ketone
Phenol
Phthalic Anhydride
8-52
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2. Superfund. The Comprehensive Environmental Response, Compensation.
and Liability Act, or Superfund, regulates the cleanup of hazardous
waste dumpsites and chemical spills. Superfund provides adequate
funding, liability, standards, and authority to the government to
recover costs from the responsible parties. Any person in charge of a
facility is required to report any "release" of a specified quantity of
hazardous waste into the environment immediately. The emphasis of the
regulation is to report the release of the wastes and to clean them up
first and then recover costs. The Act also develops a tax on all
hazardous wastes received at a disposal facility in order to develop a
post-closure trust fund. The fee to the chemical industry for this
fC
trust fund is less than two percent of their profits.
8-53
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8.3 REFERENCES FOR CHAPTER 8
1. Basdekis, H.S. Emissions Control Options for the Synthetic Organic
Chemicals Manufacturing Industry. Control Device Evaluation. Thermal
Oxidation Supplement (VOC Containing Halogens or Sulfur). EPA Contract
No. 68-02-2577, November 1980. p. III-ll.
2. Blackburn, J.W. Emissions Control Options for the Synthetic Organic
Chemicals Manufacturing Industry. Air Oxidation Generic Standard
Support. EPA Contract No. 68-02-2577. May 1979. p. III-3.
3. Memo from Desai, T., EEA, to Galloway, J., EEA. April 2, 1981.
4. Blackburn, op. cit., p. III-3.
5. Letter and attachment from McClure, H.H., Texas Chemical Council, to
Patrick, D., EPA. December 13, 1979. p. 7.
6. Memo and attachment from Mulchandani, B., EEA, to Galloway, J., EEA.
October 29, 1980.
7. Blackburn, J.W. Emissions Control Options for the Synthetic Organic
Chemicals Manufacturing Industry. Control Device Evaluation. Thermal
Oxidation. EPA Contract,No. 68-02-2577. July 1980. pp. 1-1, 1-2.
8. Basdekis, op. cit., p. III-ll.
9. Blackburn, Generic Standard Support, op. cit., p. III-3.
10. Desai, op. cit.
11. Blackburn, Generic Standard Support, op. cit., p. III-3.
12. McClure, op. cit., p. 7.
13. Mulchandani, op. cit,
14. Blackburn, Thermal Oxidation, op. cit., pp. 1-1, 1-2.
15. Ibid.
16. Memo from Galloway, J., EEA, to SOCMI Air Oxidation File.
December 31, 1980.
17. Blackburn, Thermal Oxidation, op. cit.
18. Memo from Derway, D., EEA, to Galloway, J., EEA. August 15, 1980.
19. Blackburn, Thermal Oxidation, op. cit., p. 111-13.
20. Basdekis, op. cit., p. 111-12.
8-54
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21. Ibid., p. III-8.
22. Blackburn, Thermal Oxidation, op. cit., p. III-9.
23. Ibid., p. IH-4.
24. Basdekis, op. cit., p. III-4.
25. Blackburn, Thermal Oxidation, op. cit., p. III-l
26. Basdekis, op. cit.
27. Blackburn, Thermal Oxidation, op. cit.
28. Chemical Engineering. January 14, 1980.
29. Memo from Galloway, J., EEA, to SOCMI Air Oxidation File.
August 8, 1980.
30. Blackburn, Thermal Oxidation, op. cit., p. V-l.
31. Ibid., pp. V-3, V-l5.
32. Ibid., p. V-15.
33. Ibid., p. V-22.
34. Ibid., pp. 111-19, 111-22.
35. Basdekis, op. cit., p. 111-14.
36. Ibid., p. 111-15.
37. Ibid., pp. III-ll, 111-15, 111-16.
38. Blackburn, Thermal Oxidation, op. cit., p. 11-12.
39. Mulchandani, op. cit.
40. Blackburn, Thermal Oxidation, op. cit., p. V.-22.
41. Basdekis, op. cit., p. V-16.
42. Blackburn, Thermal Oxidation, op. cit., p. III-8.
43. Baskdekis, op. cit., p. III-6.
44. Memo from Galloway, J., EEA, to SOCMI Air Oxidation File.
September 1, 1980.
45. Memo from Galloway, J., EEA, to SOCMI Air Oxidation File.
February 13, 1981. .
46. Blackburn, Thermal Oxidation, op. cit., p. 11-10.
8-55
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47 Letter from Berres, 0., Reeco, to Don R. Goodwin, EPA.
July 14, 1981.
48 Development Document for Effluent Limitations Guidelines and New
" Source Performance Standards for the Major Organic Products Segment
of the Organic Chemicals Manufacturing Industry.
EPA-440/l-74-009-a. April 1974.
49. Council on Environmental Quality. Environmental Quality: Tenth
Annual Report of the CEQ. Government Printing Office.
Washington, D.C. December 1979. p. 137.
50. Federal Register. Volume 45, page 79318. November 28, 1980.
Washington, D.C. Office of the Federal Register.
51. Council on Environmental Quality. Environmental Quality: Tenth
Annual Report of the CEQ. Government Printing Office.
Washington, D.C. December 1979. p. 138.
52. The Cost of Clean Air and Water: Report to Congress.
EPA-230/3-79-001. Office of Planning and Management. August 1979.
53 Federal Register. Volume 46, page 23723. April 27, 1981.
Washington, D.C. Office of the Federal Register.
54. Federal Register. Volume 46, page 79318. November 28, 1980.
Washington, D.C. Office of the Federal Register.
55 U.S. Department of Labor. Code of Federal Regulations. Title 29,
Chapter 17, part 1910.1000, subpart Z. Washington, D.C. 1980.
Office of the Federal Register.
56 U.S. Department of Labor. Code of Federal Regulations. Title 29,
Chapter 17, part 1910.1045. Washington, D.C. Office of Federal
Register. 1980.
57. Chemical and Engineering News. March 26, 1979. p. 6.
58 U.S. Department of Labor. Code of Federal Regulations. Title 29,
Chapter 17, part 1910.106. Washington, D.C. Office of the Federal
Register. 1980.
59. McRae, A. and L. Whelchel, ed. Toxic Substances Control Source
Book. Aspen Publications. 1978.
60. Chemical Regulation Reporter. Bureau of National Affairs.
November 7, 1980. p. 1011.
61 Wiegele, George C. The State-of-the-Art of Waste Disposal Technology.
Consulting Engineer. September 1980. p. 99.
62. Rutledge, Gary C. and Betsy 0'Conner. Capital Expenditures by
Business for Pollution Abatement 1977, 1978, and Planned 1979.
Survey of Current Business. Department of Commerce. June 1979.
p. 20.
8-56
-------
63. Federal Register. Volume 45, page 33072. May 19, 1980.
Washington, D.C. Office of the Federal Register. .;
i
64. Environment Reporter. Bureau of National Affairs. "
December 19, 1980. • j
I
65. Chemical Marketing Reporter. September 3, 1979.
8-57
-------
-------
9. ECONOMIC IMPACT ANALYSIS
9.1 INDUSTRY STRUCTURE
9.1.1 Industry Definition
There are more than 7,000 organic compounds being produced today. EPA
has identified a number of the higher volume and/or higher volatility
products. For the purpose of conducting an impact analysis of air pollution
regulations, these higher volume chemicals represent the synthetic organic
chemicals manufacturing industry (SOCMI). The SOCMI chemicals are produced
in a number of different ways. 'Air oxidation (AO), one of the major pro-
cesses, uses air rather than oxyjln or chemical oxidants as a reactant.
Thirty-six chemicals are produced-partially or totally by the AO
process. These are listed in Table 3-7 with percentages of total production
carried out by the AO process. As the table indicates, nearly half of the
36 chemicals are expected to be produced totally by AO processes. The
remaining chemicals may be produced by other means, with AO representing
from 5 to 98 percent of the expected 1982 production for any particular
chemical. A weighted-by-capacity average of the AO chemicals indicates
that 65 percent of total production is by the AO process.
Most of the AO chemicals are found under the Department of Commerce's
SIC 2869, Industrial Organic Chemicals, NEC. A few, such as benzaldehyde,
phenol, and maleic anhydride, are found under SIC 2865, Cylic Crudes and
Cyclic Intermediates, Dyes, and Organic Pigments. AO chemicals are an
important part of the U.S. industrial sector:, the AO chemicals' value of
shipments comprises approximately 10 percent of the total synthetic organic
chemical value of shipments; total synthetic organic chemical shipment
value represents 25 percent of the total chemical and allied products (SIC
28) value of shipments; and the chemical and allied products industry is
among the largest industrial sectors of the U.S. economy.1
9-1
-------
For purposes of analysis, the AO industry is defined as producers of
chemicals for each of which there currently is at least one AO facility in
the United States.
Production, capacity, and other relevant statistics are given here as
totals for each AO chemical. The key word is "totals," because a portion
of a chemical's production may be by some other process. For instance,
only one facility, owned by Oxirane, produces styrene by the AO method; the
other 11 styrene-producing facilities use a different process. These 11
firms and the Oxirane facility are intertwined economically (especially
from a price standpoint), and any regulation placed on Oxirane will affect
the others. In addition, in terms of a New Source Performance Standard,
any of the 11 facilities can modify and start producing styrene using AO.
Finally, severe data limitations exist if such items as production and
sales are disaggregated by facility.
9.1.2 Air Oxidation Chemical's Supply and Capacity
Table 9-1 shows the annual nameplate production capacities for each of
the chemicals (in gigagrams). N.ameplate capacities are not actual produc-
tion levels; rather, they represent total production capacity. The total
annual production capacities of-the AO chemicals range from fewer than
three gigagrams for p-t-butyl benzoic acid, a specialty chemical, to 6,508
gigagrams for ethylene dichloride. The six AO chemicals with the largest
production capacities are ethylene dichloride, formaldehyde, styrene,
dimethyl terephthalate-terephthalic acid, ethylene oxide, and 1,3-fautadiene.
Table 9-1 a'lso gives production and capacity utilization figures for
the AO chemicals. Capacity utilization, derived by dividing production by
capacity, indicates the market conditions confronting producers. A facility
is said to be operating at optimal capacity when capacity utilization, in
the long run, is 85 percent of nameplate. A low capacity utilization rate
usually implies that price increases will be harder to achieve, cost in-
creases will be harder to cover, and new facilities will be harder to
justify. Beyond this level, a strain is put on plant equipment.' The
average capacity utilization rate for the AO chemicals is approximately 78
percent (AO production divided by total AO capacity).
Ethylene dichloride has the greatest'production volume of the 36 AO
chemicals. Dimethyl terephthalate-terephthalic acid has the largest value
9-2
-------
TABLE 9-1. NUMBER OF FACILITIES, CAPACITY, PRODUCTION, CAPACITY
UTILIZATION, AND VALUE OF PRODUCTION
I 36 AO Chemicals
! United States
Chemi cal
Acetal dehyde
Acetic acid
Acetone
Acetonitrile
Acetophenone
Acrolein
Acrylic acid
1978
No. of
facilities3
5
10
20
2
4
2
3
Acrylonitrile 6
Anthraquinone 1
Benzal dehyde 5!
Benzoic acid 5j
1,3-Butadiene 19 i
p-t-Butyl benzoic i:
aci d • \
n-Butyric acid 3
Crotonic acid i
Cumene hydroperoxide 5
Cyclohexanol/ 8
cyclohexanone
Dimethyl terephthalate- 6
terephthalic acid
Ethyl ene di chloride 17
Capaci tya
(Gg)
663
1389
1284
26
NA
49
179,
975"
.2f
6 .
143
1916
3
69
6
4
1141h
3386e
6508
b Capacity
Production utilization
(Gg) (%)
591 88.0
1266 91.2
961 74.9
NA
NA
NA
129* 71. 9
796 81. 7
NA
NA
89 / 62.4
1636 85.4
NA
NA
NA
NA
NA
2682e 79.2
4994 76.7
Value of ,
production
(million $)
234.6
421.6
345.0
18.4**
—
26. 7**
91.1
403.6
—
. 7.1**
47.1
703.5
3.3**
-—
7.9**
1.9**
647.6**
1307.5
903.9
9-3
-------
TABLE 9-1 (Continued). NUMBER OF FACILITIES, CAPACITY, PRODUCTION, CAPACITY
UTILIZATION, AND VALUE OF PRODUCTION
36 AO Chemicals
United States
1978
No. of Capacity3 Production
Chemical facilities3 (Gg) (Gg)
Ethyl ene oxide
Formal dehyde
Formic acid
Glyoxal
Hydrogen cyanide
Isobutyric acid
Isophthalic acid
Maleic anhydride
Methyl ethyl ketone
a-Methyl styrene
Phenol
Phthalic anhydride .. .
Propionic acid
Propylene oxide
Styrene
TOTALS
16
53
3
2
12
1
I
10
7
5
13
11
4
7
12
2705
4050
37
NA
396
-59
109S
234^
386
29
1570
605
110
1377
3831
33,122
2199
2924
27
NA
205
NA
59
151
272
25*
1239
451
40
929
3136
^^•^^•B
24,801
Capacity Value .
Utilization of production
(%) (million $)
81.3
72.2
73.2
~
51.6
—
54.3
64.5
70.4
85.9
78.9
74.7
36.2
67.5
81.2
77.8
1081..9
327.5
11.0
—
134.3
—
34.6
77.9
114.0
9.9
456.0
244.4
15.0
442.2
1245.0
9364.5
NA s Information not available.
aSRI International. 1978 Directory of Chemical Producers, United States of
America. Menlo Park, California, 1979.
U.S. International Trade Commission. Synthetic Organic Chemicals, United
States Production and Sales, 1978. USITC Publication 10001. Those production
numbers denoted with an asterisk (*) are 1977 production figures.
Production as a percentage of capacity.
9-4
-------
TABLE 9-1 (Continued). NUMBER OF FACILITIES, CAPACITY, PRODUCTION, CAPACITY
UTILIZATION, AND VALUE OF PRODUCTION
36 AO Chemicals
United States
1978
End 1978 market prices multiplied by production to give value of production
Those chemicals denoted with a double asterisk (**) are estimated based on
an average 78 percent capacity utilization rate.
eIh!uflEures.for d1methy1 terephthalate (DMT)-terephthalic acid (TPA) include
both the acid itself and the dimethyl ester without double counting. In
other words, at some plants, process units can interchange TPA and DMT pro-
duction given the unit's capacity. Individual capacities for DMT and TPA
are presented in data sources such that by combining these capacities there
exists an overstatement of true capacity for DMT-TPA. The interchangeable
process units are identified and the double counting eliminated. The same
situation exists for production so the TPA production figure is multiplied
by^the factor 1.17 (the molecular weight of DMT divided by the molecular
weight of TPA) to convert it to equivalent DMT.
Letter from W.P. Bobsein, Toms Riy.er Chemical Corp., to L.B. Evans EPA
February 11, 1980.
9Estimated based on data given in feltter and attachment from J.C. Edwards
Eastman Kodak Co., to L.B. Evans,"EPA, February 6, 1980.
Production capacity of cyclohexariol and cyclohexanone have been reported
together.
9-5
-------
of production at $1307.5 million. Formaldehyde, with the fourth largest
production volume, is well down on the value of production list because of
its low selling price.
The value of production, because it takes into account captive consump-
tion, is a much more useful figure than value of sales when looking at the
relative "importance" of a chemical. Table 9-2 shows the percentage of
each AQ chemical's production that is sold. Production consumed captively
is used as an intermediate feedstock for downstream processing of other end
products within the same plant. Also, the value of production is not the •
same as value added. Some AO chemicals use other chemicals as raw materials
in the production process and simply make the'raw material more valuable
(useful). Again, however, the value of production is listed because it
reflects the relative importance of individual chemicals.
There are about 165 facilities producing AO chemicals in the United
States and Puerto Rico today. About 110 (65 percent) of these facilities
use some type of AO process; the remainder use other processes to produce
the AO chemicals. Some plants produce more,ihan one AO chemical.
V
Facilities are located in 30 states and Puerto Rico (see Figure 9-1),
and are concentrated along the Gulf Coast (Texas and Louisiana) and the
East Coast (New Jersey, Pennsylvania, and North Carolina). More than half
of the facilities are located in these five states.
The coastal concentrations reflect facility locations near refineries
that site at domestic oil sources or at points of entry for imported oil.
Facilities in the central United States are likely to site along natural
gas pipeline routes and water transportation arteries. Facility locations
in the west may correspond to oil and gas fields.
9.1.3 Industrial Producers
There are 74 companies that produce one or more of the 36 synthetic
organic AO chemicals. Table 9-3 lists the companies and the AO chemicals
they produce. Of the 74 companies, 50 produce one or two AO chemicals, 17
produce from three to nine chemicals, and seven produce 10 or more. Union
Carbide Corporation produces the largest number, 18.
A major share of the organic chemicals partially or fully produced by
AO processes is generated by large multi-line chemical companies, sufcsidi-
aries of major oil companies, and multi-industry companies with chemical
process operations.
. j
9-6
-------
UJ
03
o
I—
o
1— hi; £
5 -J S:
O. Q. S'
^j «s S
O *"* =
LU
O
UJ
Q=
3
C3
9-7
-------
TABLE 9-3. INDIVIDUAL COMPANIES AND THE AO CHEMICALS THEY PRODUCE
36 AO Chemicals
United States
1978
Company
Chemicals
Allied Chemical Co.
American Cyanamid Co.
American Hoechst Corp.
Ashland Oil, Inc.
Atlantic Richfield Co.
BASF Wyandotte-Corp.
B.F. Goodrich
Borden, Inc.
Calcasieu Chemical
Corp.
Celanese Corp.
Ciba-Geigy Corp.
Clark Oil &
Refining Corp.
Continental Oil Co.
Copolymer Rubber" and
Chemical Corp.
Cos-Mar, Inc.
Crompton & Knowles
Corp.
Acetone, acetophenone, cumene hydroperoxide,
cyclohexanol, cyclohexanone, ethylene dichloride,
formaldehyde, a-methyl styrene, phenol, phthalic
anhydri de
Acetone, acrylonitrile, glyoxal, hydrogen cyanide
Dimethyl terephthalate, styrene
Maleic anhydride
1,3-Butadiene, methyl ethyl ketone, styrene
Ethylene glycol, ethylene oxide, phthalic
anhydride, propylene oxide
r
Ethyl eae? dichloride
V
Acetic, acid, formaldehyde
Ethylene oxide
Acetaldehyde, acetic acid, acrylic acid,
n-butyric acid, cyclohexanol, cyclohexanone,
ethylene oxide, formaldehyde, formic acid,
methyl ethyl ketone, propionic acid
Hydrogen cyanide
Acetone, a-methyl styrene, phenol
Ethylene dichloride
1,3-Butadiene
Styrene
Benzaldehyde
9-8
-------
TABLE 9-3 (Continued).
INDIVIDUAL COMPANIES AND THE AO CHEMICALS THEY PRODUCE
36 AO Chemicals
United States
1978
Company
Chemicals
Dart Indust., Inc.
Denka Chemical Co.
Diamond Shamrock
Dow Badische Co.
Dow Chemical, USA
DuPont
Eastman Kodak Co.
El Paso Natural Gas
Ethyl Corp.
Exxon Corp. . •"•"
Firestone Tire &
Rubber Co.
FMC Corp,
GAP Corp.
Georgia-Pacific
Corp.
Getty Oil Co.
Goodyear Tire &
Rubber Co.
Methyl ethyl ketone
Maleic anhydride
Ethylene dichloride
Acrylic acid, cyclohexanol, cyclohexanone
Acetone, ethylene dichloride, ethylene oxide,
hydrogen cyanide, phenol, propylene oxide,
styrene
Acetonitrile, acrylonitrile, cyclohexanol,
cyclohexanone, dimethyl terephthalate,
formaldehyde, hydrogen cyanide
^ •-
Acetaldefiyde,. acetic acid, acetone,
n-butyric acid, crotonic acid, dimethyl
terephthalate, ethylene oxide, isobutyric acid,
propionic acid
1,3-Butadiene, styrene
Ethylene dichloride
Acetone, 1,3-butadiene, methyl ethyl ketone,
phthalic anhydride
1,3-Butadiene
Acetic acid
Formaldehyde
Acetone, formaldehyde, a-methyl styrene, phenol
Acetone, acetophenone, formaldehyde, a-methyl
styrene, phenol
Acetone
9-9
-------
TABLE 9-3 (Continued).
INDIVIDUAL COMPANIES AND THE AO CHEMICALS THEY PRODUCE
36 AO Chemicals
United States
1978
Company
Chemicals
Gulf Oil Corp.
Hereofina
Hercules, Inc.
Inter11 Minerals &
Chemical Corp.
Kalama Chemical, Inc.
Koppers Co., Inc.
Mobil Corp.
Monroe Chemical, Inc.
Monsanto Co.
Neches Butane
Products Co.
Nipro, Inc.
Northern Natural
Gas Co.
Northwest Indust., Inc.
Occidental Petroleum,
Inc.
01 in Corp.
Oxirane Corp.
Pennwalt Corp.
Pfizer, Inc.
Formaldehyde, styrene
Dimethyl terephthalate, terephthalic acid
Cumene hydroperoxide, formaldehyde, hydrogen cyanide
Cumene hydroperoxide, formaldehyde, hydrogen
cyani de
Benzaldehyde, benzoic acid, phenol
Maleic anhydride, phthalic anhydride
1,3-Butadiene
Benzalde&yde
V
Acetic-acid, acetone, acrylonitrile, 1,3-butadiene,
cyclohexanol, cyclohexanone, formaldehyde, hydrogen
cyanide, maleic anhydride, phenol, phthalic
anhydride, styrene
1,3-Butadiene
Cyclohexanol, cyclohexanone
Ethylene oxide
Benzoic acid
Formaldehyde, phthalic anhydride
Ethylene oxide, propylene oxide
Acetone, propylene oxide, styrene
Cumene hydroperoxide
Benzoic acid.
9-10
-------
TABLE 9-3 (Continued).
INDIVIDUAL COMPANIES AND THE AO CHEMICALS THEY PRODUCE
36 AO Chemicals
United States
1978
Company
Chemicals
Phillips Petroleum Co.
PPG Indust., Inc.
Publicker Indust., Inc.
Puerto Rico Olefins Co.
Reichold Chems., Inc.
Rock!and Indust., Inc.
Rohm and Haas Co.
Shell Chemical Co.
Standard Oil
Co. (CA)
Standard Oil
Co. (IN)
Standard Oil
Co. (OH)
Stauffer Chemical Co.
Stephan Chemical
Sun Co., Inc.
Sunolin Chemical Co.
Tenneco, Inc.
Texaco, Inc.
l,3-8utadiene
Ethylene dichloride, ethylene oxide
Acetaldehyde, acetic acid
1,3-Butadiene
Cumene hydroperoxide, formaldehyde, maleic
anhydride, phenol
Formic acid
Hydrogen cyanide
Acetaldehyde, acetone, acrolein, 1,3-
butadiemj, p-t-butyl benzoic acid, ethylene
dichloride, ethylene oxide,, methyl ethyl ketone,
phenol"
Acetone, phenol, phthalic anhydride
1,3-Butadiene, isophthalic acid, maleic
anhydride, styrene, terephthalic acid
Acetonitrile, acrylonitrile, hydrogen cyanide
Ethylene dichloride
Phthalic anhydride
Styrene
Ethylene oxide
Benzaldehyde, benzoic acid, 1,3-butadiene,
maleic anhydride
Ethylene oxide, propylene oxide
9-11
-------
TABLE 9-3 (Continued).
INDIVIDUAL COMPANIES AND THE AO CHEMICALS THEY PRODUCE
36 AO Chemicals
United States
1978
Company
Chemicals
Toms River Chemical
Corp.
UOP, Inc.
Union Carbide Corp.
Univar Corp.
US Steel Corp.
Vulcian Materials Co.
Wright Chemical Corp.
Anthraquinone
Acetophenone, benzaldehyde
Acetic acid, acetone, acetophenone,
acrolein, acrylic acid, 1,3-butadiene,
n-butyric acid, cyclohexanol, cyclo-
hexanone, ethylene dichloride, ethylene
oxide, formic acid, glyoxal, methyl ethyl
ketone, phenol, propionic acid
Formaldehyde
Acetone, cumene hydroperoxide, -maleic anhydride,
a-methylsstyrene, phenol, phthalic anhydride,
styrene ^
Ethyl e'ne di chloride
Formaldehyde
SOURCE: SRI International. 1978 Directory of Chemical Producers, United
States of America. Menlo Park, California, 1979.
9-12
-------
Table 9-4 gives the single, largest producer for each AO chemical and
the percentage of the AO chemical's total capacity owned by that company.
In general, the higher the production volume of the AO chemical, the lower
the percentage of total capacity any one company will own. Those AO chemi-
cals that are produced by only one company typically are produced in small
volumes. The issue of market concentration is discussed further in Section
9.1.12.
9.1.4 Employment
t
Employment in 1978 under SIC 286 (Industrial Organic Chemicals) was
139,000. The production value of SOCMI AO chemicals is approximately 10
percent of the SIC 285 value of production. Thus, about 13,900 employees
(10 percent of 139,000) were employed producing chemicals on the AO list.
9.1.5 Industry Finances
Although it has recently passed through a period of declining profit
margins, the chemicals industry is large, with considerable resources
available for capital investment.-
For the chemicals industry'ajs a whole (including AO process chemical
manufacturers, non-AO process chemical, manufacturers, and a certain amount
of non-chemical business), the"profIt margin (after-tax earnings as per-
centage of net sales) increased" from 1971 through the third quarter ,of 1974
and then plummeted in the fourth quarter of 1974 and throughout 1975! and
1976. The years 1977 and 1978 saw slight increases in the profit margin.3
Despite greater increases in chemical profit margins more recently,4! the
last four or five-years have not brought heavy cash inflows from profits
(see Figure 9-2).
The major reasons for low profitability include the recession (reduced
demand for construction, automobiles, and durable goods reduces demand for
chemicals used in their manufacture), continuing increases in the prices of
energy and feedstocks, and generally low capacity utilization. When! chemi-
cal plants cannot operate at full capacity, high fixed costs must bej spread
over lower volumes. While unit costs increase, reduced demand inhibits
price increases. Profit margins, thus, are squeezed and volumes stagnate
or fall, lowering total profits. Capacity utilization rates exceeded^ 80
percent in the years 1971 through 1974. During the next four years (J1975
through 1978), capacity utilization rates dropped below 80 percent. 'The
9-13
-------
TABLE 9-4. THE LARGEST PRODUCER OF EACH AO CHEMICAL AND THE
PERCENTAGE OF THE AO CHEMICAL'S TOTAL
CAPACITY THE LARGEST PRODUCER OWNS
36 AO Chemicals
United States
1978 ;
Chemical
Acetal dehyde
Acetic acid
Acetone
Acetonitrile
Acetophenone
Acrolein
Acrylic acid
Acrylonitrile
Anthraqui none
Benzal dehyde
Benzoic acid
1,3-Butadiene
p-t-Butyl benzoic
acid
n-Butyric acid
Crotonic acid
Curaene
hydroperoxide
Cyclohexenol/
cyclohexanone
Dimethyl
terephthalate
Ethyl ene
di chloride
Ethyl ene oxide
Formaldehyde
Single largest
producer
Celanese
Celanese
Shell Chemical
NA
NA
NA
Celanese
Monsanto
fo|ns River Chemical
v NA-
Kalama Chemical
Naches Butane
Products
Shell Chemical
NA
Eastman Kodak
NA
DuPont
DuPont
Dow Chemical
Union Carbide
Celanese
Percentage
of total
capacity
61
41
23
NA
NA
NA
54
40
100
NA
49
17
; 100
I NA
100
NA
i 29
j
!
| 42
> 33
j 42
1 19
9-14
-------
TABLE 9-4 (Continued). THE LARGEST PRODUCER OF EACH AO CHEMICAL AND THE
PERCENTAGE OF THE AO CHEMICAL'S TOTAL
CAPACITY THE LARGEST PRODUCER OWNS
36 AO Chemicals
United States
1978
Chemical
Formic acid
Glyoxal
Hydrogen cyanide
Isobutyric acid
Isophthalic acid
Maleic anhydride
Methyl ethyl
ketone
a-Methyl styrene
Phenol
Phthalic anhydride
Propionic acid
Propylene oxide
Styrene
Terephthalic acid
Single largest
producer
Union Carbide
NA
DuPont
Rohm and Haas
Eastman Kodak
Standard Oil (IN)
Monsanto
Shgll Chemical
AT tied -Chemical
"Allied Chemical
Koppers
Union Carbide
Oxi rane
Dow Chemical
Monsanto
Standard Oil (IN)
Percentage
of total
capaci ty
61
NA
33
33
100
100
20
39
45
17
25
62
44
18
18
88
NA = Information on individual company capacities not available.
SOURCE: SRI International. 1978 Directory of Chemical Producers,
United States of America. Menlo Park, California, 1979.'
9-15
-------
PERCENT
1969 1971 1973 1975 1977
YEAR
FIGURE 9-2. AFTER-TAX EARNINGS AS A PERCENTAGE OF NET SALES
(Annual Profit Margins)
CHEMICALS AND ALLIED PRODUCTS (SIC 28)
UNITED STATES
1963-1979
SOURCE: "Earnings Gain Off, But Better Than Expected." Chemical and Engineering News. p.9. February 18. 1980.
9-16
-------
fluctuation in capacity utilization correlates closely with the increasing
profit margins in the earlier years and decreasing profit margins in the
later years. .
Profits are only part; of the picture, however. Internal cas-h flow
comes not only from after-tax profits but also from depreciation charged to
past investments. With a large capital stock already in place, the chemi-
cals industry has a substantial cash flow from depreciation alone. The
cash flow, however, is limited in comparison to inflated capital require-
ments for replacement plants and, in many cases, requirements for plants of
much larger scale needed to adopt the latest efficient technology.
Chemical and Engineering News examined a sample of 20 chemical com-
panies (19 of which produce AO chemicals) and found that the standard
current ratio (current assets divided by current liabilities) dropped to
2.1 at year-end 1978 from 2.3 the previous year. The ratio was 2.1 in
1974,-but was 2.4 in 1975. At the same time, the cash ratio (coverage of
current liabilities with cash and. marketable securities) had deteriorated.
It stood at 0.23 in 1978, compare^ to a high of 0.33 in 1975 and 0.28 in
1974. Thus, the short-term liquidity.of chemical firms has been squeezed
recently.
However, the ability of the industry to raise capital for long-term
investment is based in larjge measure on the yields the industry offers
investors. Returns on common stock have been strong over the last decade
as a whole and, despite some recent difficulties, are still approximately
equal to those of-other industries. These facts, as shown below, indicate
that the chemicals industry continues to offer competitive yields and will
remain competitive in its ability to attract investment capital.
From 1970 to 1980, the chemicals segment of the Fortune 500 company
listing showed an annual rfeturn to investors of 11.97 percent. This was
higher than the 9.44 percent return for all industries. Total return to
investors includes the sum; of stock price appreciation and dividend yield.
Performance has dropped inj recent years but continues to at least approxi-
mate the average among industries. Return on stockholders' equity for the
chemicals segment of the Fortune 500 was 15.2 percent and 13.9 percent,
respectively, in 1979 and iaSO. This is slightly below the median rates
for all industries, which were 15.9 percent and 14.4 percent in the same
years. ;
9-17
-------
Results for the Fortune Second 500, i.e., the next size tier of compa-
nies, showed roughly the same pattern. Chemical companies offered better
than average total return to stockholders over the last decade and approxi-
mately average returns on equity in the last two years.
These facts imply that the chemicals industry remains competitive in
its attractiveness to investors and that the industry should be able to
attract large, sums, given its large size, to finance future investments.
Cash flow from'depreciation allowances on existing assets also will contrib-
ute substantially to funds available for investment.
The debt ratio (Tong-term debt as a percentage of long-term debt plus
equity) increased slightly, from 27.8 percent in 1977 to 27.9 percent in '
1978, but did not increase much more than the ratio for all manufacturing,
which stood at 24.4 percent in 1978, down from 24.6 percent in 1977.
Aggregate industry cash flow from various sources is presented in
Table 9-5, which indicates that, despite problems in profitability, the
industry's cash flow has grown continually. Capital expenditures, a major
use of cash flow, were $5.1 bi!H§n in 1978, down slightly from $5.5 billion
in 1977.7 "I
In summary, the chemicals Industry has gone through a period (1974-1978)
of slow profit growth, but it remains a large generator of cash flow for
new investments.; More important to the investment behavior of the chemicals
industry is that 1979 has shown much stronger profits and, barring a deep
recession, demand should be strong enough to support increased capacity
utilization and higher profit margins. The industry as a whole will be
able to raise necessary cash if it foresees such opportunity for profitable
returns on its investments.
9.1.6 End Uses
This section presents brief surveys of the major AO chemical-using
industries. The: surveys include both AO chemicals and non-AO chemicals to
provide a background on the context in which AO chemicals are used.
AO chemical's have many uses. They are used as plastics, textile
fibers, rubber, purface coatings, dyes, food additives, fragrances, adhe-
sives, drugs, and other substances.
There are two important characteristics o,f the AO chemicals industry
in general. First, many AO chemicals serve as intermediate chemicals in
9-18
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the production of several other chemicals which, in turn, have numerous end
uses and final products. A single organic chemical, thus, can be traced
along many branches that lead to other chemicals and various end uses.
Second, while the uses of AO chemicals are many, the major end uses
are not. Plastics and textile fibers account for the bulk of consumption
of the AO chemicals studied here.
The concentration of AO chemical consumption in relatively few indust-
ries — plastics and fibers — is shown in Table 9-6. Ten chemicals account
for 80 percent of total estimated dollar sales of all AO chemicals studied.
(It should be noted, however, that some of the chemicals are produced
partially by non-AO processes; see Table 3-7.) Nine of the 10 top chemi-
cals are used largely for the manufacture of plastics or textile fibers.
The other, 1,3-butadiene, is used mainly to make synthetic rubber for
automobile tires.
Demand for plastics and fibers is strong because of their structural,
non-structural, and sufastitutional uses. Although AO chemicals have many
specialty uses, the" plastics and fibers markets create considerable demand
for AO chemicals. In a sense, the plastics and fibers uses help to distin-
guish the AO chemicals from myriad other organic chemicals that serve
smaller, less well-known markets.
At the same time, other uses of AO chemicals can be important. Phar-
maceuticals, for example, account for just 6 percent of acetone volume but
are important chemical products. Small uses also may signify potentially
large uses that "have not been developed fully yet. Nonetheless, for this
analysis, the basic characterization of the AO chemicals as primarily
intermediates for the plastics and textile fibers industries is a useful
way to describe the list succinctly.
9.1.6.1 The Plastics Industry. As already noted, the major use of AO
chemicals is in the plastics sector of the chemicals industry. In 1977,
shipments of plastics and resins totaled $11.6 billion. Total plastics
sales equalled 14 percent of all chemicals industry sales.8
Plastics are long-chained molecular substances. In this section, the
term "plastic" is used interchangeably with the term "resin." Technically,
not all resins are plastics. Some resins-.are used as adhesives, for example,
in plywood. Plastics are fairly tough resins that usually can be made into
9-20
-------
TABLE 9-6. AO CHEMICALS BY VALUE OF PRODUCTION WITH EACH
CHEMICAL'S MAJOR END. USE PRODUCTS
14 AO Chemicals
United States
1978
Cumulative
Top 14 AO chemicals percentage
ranked by production Value of total AO
Va1ue ($) . (million $) value* Major end use products
1.
2.
3.
4.
5.
6,
7.
a.
9.
10.
11.
12.
13.
14.
Dimethyl terephthalate-
terephthalic acid
Styrene
Ethyl ene oxide
Ethyl ene di chloride
1,3- Butadiene
Cyclohexanol/
cydohexanone
Phenol
Propylene oxide
Acetic acid
Acrylonitrile
Acetone
Formaldehyde'
Phthalic anhydride
Acetaldehyde
1307.5
1245.0
1081. 9
903.9
703.5
647.6
45^.0
442. 2 . -.
~
421. 6
403.6
345.0
327.5
244.4
234.6
14
27
39
48
56
63
63
72
77
81
85
88
91
94
Polyester fibers, films
Plastics, rubber
Anti-freeze, polyester
Polymers, resins
Rubber
Nylon
Plastics, adhesives
Urethane plastic,
polyester
Vinyl, cellulose
acetates
Acrylic fibers, ABS
and SAN plastics
Cellulose acetate
fibers, plastics
Plasticizers, plastics
polyester
Plastics
Intermediate for
numerous chemicals
j
Total Production Value3
(36 AO Chemicals)
9364.5
Excludes data for 5 AO chemicals under study. Those exluded are small
volume chemicals, however, so the percentages would not change much. Sales
volumes are estimates using 1978 production volumes and 1978 market prices
\ I 3.D 1 3 j""*
9-21
-------
structural shapes. Nonetheless, the term "plastics" is used most frequent-
ly because it is easier to conceptualize in discussing end uses.
In terms of production volume, the largest plastic is polyethylene.
In 1978, 5,100 gigagrams of polyethylene were produced in the United States.
Polyvinylchloride is second, with production of 3,100 gigagrams. Polysty-
rene is third, with 2,000 gigagrams produced. Polypropylene is fourth,
with 1,300 gigagrams produced. Phenolics are fifth, with 900 gigagrams
produced. Other kinds of plastics also have substantial production volumes.
Production of all kinds of plastics totaled 17,100 gigagrams in 1978.10
Within broad classes of plastics, it may be noted, there are many varieties
that differ only slightly in molecular composition but that have different
end-use properties.
The plastics industry has grown rapidly and has penetrated many end-use
markets. The fact that AO chemicals are used in the manufacture of plastics
means'that AO chemicals are used extensively throughout the economy. Even
the service sectors, which use relatively few materials, rely upon some
amount of plastics indirectly io ttheir equipment and accessories.
V
Plastics have various properties -that make them suitable for different
end uses. Each plastic is unique in terms of its combination of functional
properties -- flexibility, solubility, resistance to heat and sun, behavior
under stress, clarity, and so on. Plastics also differ in price: styrene,
for example, is inexpensive, while fluorocarbon plastics are very expensive.
Finally, plastics differ in terms of processability ~ moldability, extrud-
ability, and so on. Consequently, each kind of plastic is used in certain
end uses, although in many end uses there is competition among plastics and
between plastics and other materials. Table 9-7 shows a breakdown of the
major plastics and ultimate end-use markets.
9.1.6.2 The Textile Fibers Industry. The textile fibers industry is
related to the plastics industry in that many plastics and fibers share
common resins. A fiber is similar to its related plastic except that the
molecules in a fiber may be longer and are aligned in the production pror
cess so that the filament structure has"considerable strength.
There are three major classes of fibers — natural, inorganic, and
synthetic organic. Natural fibers are made from plant or animal sources
directly, without chemical conversion. These include cotton, wool, and
9-22
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flax. Inorganic fibers are filament-shaped inorganic substances. Examples
are steel wool and asbestos insulation material.
Synthetic organic fibers are derived from organic materials and are
produced through either regeneration or substantial chemical conversion.
One major class of synthetics is the cellulosic class, which includes rayon
and acetates. Cellulosics are said to be-semi-synthetics because their
process uses regenerated cellulose obtained from high-purity wood pulp or
cotton. Pure synthetics are the other major class of synthetics. Examples
of these are polyester, nylon, and acrylics. These are manufactured via
chemical processes that involve substantial chemical conversion to produce
the final molecules. All synthetic organic fibers, like natural fibers,
contain carbon. Carbon atoms provide the basis for the linkages that allow
long polymer molecules to form.
The largest volume synthetic fiber is polyester. Polyester accounts
for 45 percent of all synthetic..fibers. Nylon is second, with 28 percent.
Acrylics, polyo.lefins, and rayon, each account for about 8 percent of the
• 11 • z
synthetics total. Table 9-8-iJlustrates the end-uses of synthetic
fibers as a group.
9.1.6.3 Other Industries.: As noted earlier, AO chemicals are used in
other industries, including the rubber, surface coating, adhesive, food
additive, dye, fragrance, solvent, and drug industries.
The rubber industry, which includes both natural and synthetic rubber,
is fairly large. _0f synthetic rubber (or elastomers, as the term is used
generically), styrene-fautadiene rubber (SBR) is the largest industry,
accounting for'50 percent of the 3,000 gigagrams of synthetic elastomers
12
produced in 1978. Table 9-9 shows the consumption of synthetic elastomers
by end use.
The surface coating industries include paints, lacquers, finishes, and
sealants. The main use of AO chemical derivatives is in the base vehicle
to hold pigments in paints. AO chemicals are useful as vehicles because
they form large polymer sheets over the surfaces of other substances.
Adhesives are another use for AO chemicals. As noted earlier, resins
are used as bonding agents in many applications. In 1972, synthetic resins
accounted for 69 percent of the $833 million in adhesives shipments; natural
base adhesives accounted for 14 percent.
9-24
-------
TABLE 9-8. CONSUMPTION OF MAN-MADE FIBERS BY END USE, AND AS A
PERCENTAGE OF ALL FIBERS CONSUMPTION BY END USE
United States
1970 and 1975
End Use
Consumption
(gigagrams)
1970 1975
Percentage of
all fibers
1975
Home Furnishings
Carpets and rugs
Draperies and upholstery
Sheets
Blankets
Curtai ns
Bedspreads -and quilts
Towels
Other
Subtotal
Apparel
Men's suits, slacks,
and coats
Women's dresses
Women's suits, slacks,
and coats
Shirts
Women's blouses
Women ' s under- and
nightwear
Apparel linings'"
Uniforms and work clothes
Anklets and socks
Sweaters
Men's under- and nightwear
Robes and loungewear
Hosiery
Swimwear and other
recreational wear
Other
Subtotal
499
145
50
41
11
12
1
505
1,264
»
,^ •_
V
136
185
105
88
41
81
83
37
30
35
15
21
30
14
80
980
723
144
89
47
20
15
6
735
1,780
231
184
175
113
100
70
52
50
39
35
28
27
' 24
14
80
1,223
98.1
57.8
41 7
T *!• * /
88 0
WW • W
75 9
/ w • «/
31.4
5 1
w • JL
96.6
80.2
59.5
80.5
64.7
57.8
75.9
73 2
' *J • £•
60.2
46.0
71 7
l A* /
77.2
22.0
73.4
100 0
J*w W • W
36.9
54.0
64'. 5
9-25
-------
TABLE 9-8 (Continued). CONSUMPTION OF MAN-MADE FIBERS BY END USE,
AND AS A PERCENTAGE OF ALL FIBERS CONSUMPTION BY END USE
United States
1970 and 1975
End Use
Consumption
(gigagrams)
1970 1975
Percentage of
all fibers
1975
Industrial and Other
Goods
i
Tires
Reinforced plastics
Retail piece goods
Medical, surgical,
sanitary products
Rope, cordage, and
Coated fabrics
Sewing thread
Other
Subtotal
TOTAL
SOURCE: C.H. Kline
Consumer
254
111
91
and
38
tape 35
9
11
175
"^ ' 723
- 12,967
& Co. The- Kline Guide
232
169
186
59
58
35
20
262
1,021
4,024
to the Chemical I
100.0
93.7
73.9
60.8
78.5
55.4
39.1
67.6
77.0
73.3
ndustry.
Fairfield, New Jersey; C.H. Kline & Co., 1977. Table 3-10,
P. 174.
9-26
-------
TABLE 9-9. PERCENTAGE OF TOTAL SYNTHETIC RUBBER CONSUMED BY END USE
United States
1975
End use
Percentage of
total weight consumed
Tires, tubes and tire products
Molded goods
Industrial rubber
Automotive
Footwear
Plastic impact modifiers
Belting, hoses and gaskets, etc.
Wire and cable
Adhesives
Coati ngs
Other
Total
57.7
11.0
4.7
3.0
1.8
1.8
1.4
1.2
1.1
16.3
100.0
SOURCE: C. H. Kline & Co. The Kline Guide to the Chemical Industry
Fairfield, New Jersey, C.H. Kline & Co., 1977. Table 3-17,
p. 106.
9-27
-------
Many AO chemicals are used in small amounts as food additives. They
help to ensure freshness and moisture or to give color and tartness. AO
chemicals also are used as flavorings, fragrances, and perfumes. These
products, in turn, are used in many consumer goods.
Dyes consume a substantial amount of AO chemicals, particularly anthr-
aquinone. In 1976, 116 million kilograms of dyes were produced.
Substantial amounts of AO chemicals are used as solvents. Methyl
ethyl ketone is a good example. Organic solvents are used in a wide number
of products, as well as in many industrial processes.
The drug industry uses some AO chemicals. While drugs account for
small quantities of AO chemicals, their value in the economy is high. Many
other industries use AO chemicals to some degree (see Section 9.1.7), but
the industries mentioned in this section are the largest users.
9.1.6.4 Growth in End Use Production. The chemical processing indus-
try (CPI) recently has experienced a slowdown in its production growth
rate. Historically, CPI growth-usually has exceeded the growth of the
overall economy: from 1954 to I9f9, the CPI grew at an average annual rate
-< -
of 7.8 percent compared with a rate of. 4.6 percent for all manufacturing.
Merrill Lynch, Pierce, Fenner &•Smith, Inc. projects that, in 1985, the
growth in chemical output will slow to 5.8 percent.16 This would still be
greater than the annual growth rate in GNP, but the gap would be narrowed.
Although many sources believe that the growth rate will remain at its
slower pace, there are a few optimistic forecasters: Arthur D. Little,
Inc. projects growth in petrochemicals will run 7 to 8 percent a year in
real dollar terms over the next five years. Recently, growth projections
for the chemicals industry have been toned down. The May 12, 1980 issue of
Chemical Marketing Reporter projects only a 4 percent growth rate through
the 1980's.
The CPI's spectacular growth has been due to substitution of synthetic
chemicals for natural products. Elastomers have been substituted for
natural rubber, plastics for paper and metals, and synthetic fibers for
cotton, wool, and silk. Now this penetration is seen as leveling off.
Charles H. Kline & Co., Inc. has projections to 1983 for specific
18 19
plastic types and elastomers. The projected growth rates for some end
uses mentioned in the preceding section are given below, and they are
assumed to apply through 1986.
9-28
-------
The markets for low-density polyethylene will start to mature, espe-
cially in food packaging. Polyethylene production should grow at an average
rate of 6 percent a year through 1983, down from the 1968 to 1978 average
rate of 8.1 percent.
High-density polyethylene production will do better, expanding at an
average rate of 7 percent through 1983. The market will expand with auto- '
mobile producers replacing metal with this plastic in fuel tanks to reduce
weight in automobiles. Industrial containers, corrugated drain pipes, and
consumer packaging all will be expanding markets for high-density poly-
ethylene.
The average annual growth rate for polyvinylchloride (PVC) is pre-
dicted to increase over its historical rate of 8 percent to 9 percent
through 1983. There will be increased usage of PVC in bottles, as well as
in pipe, conduit, and other construction materials.
Polystyrene will show good growth in the disposable and packaging
markets. It should increase by "an average rate of 6 percent per year.
However, a current study underwajf at EPA states that polystyrene growth
probably will show no growth in t*he next five years.
Phenolics represent a mature market. They will follow the general
growth of the U.S. economy and "grow approximately 3.5 percent per year.
Polyurethane has had a very successful 11.2 percent per year historical
growth rate. From now to 1984, this rate should drop to an average of 8.7
percent per year. This will be caused by the maturing of the furniture and
transportation markets which represent 75 percent of polyurethane sales.
However, the other quarter of polyurethane demand, rigid foam, should grow
at 13 percent per year due'to a large increase in the installation of
insulation in industrial buildings. Rigid urethane foam is said to have
better cost performance than such traditional materials as fiberglass.
Acrylonitrile-butadiene-styrene should increase at an average annual
rate of 7 percent, due mostly to the replacement of metal parts in auto-
mobiles with these resins.
Reduced land vehicle weight again is the reason for a large demand in
certain plastics. Unsaturated polyesters are expected to increase an
average of 8.5 percent per year for this reason.
-9-29
-------
U.S. demand for acrylics is projected to grow at an average of 6
percent per year. The growth in alkyds is projected to be only 2 percent
per year through 1983. Consumers will be substituting alkyds for acrylic
and epoxy coatings. Cellulosics will grow at an average rate of only 2
percent per year due to competition from other plastics, especially poly-
propylene in film applications. With increased demand for rust-proof
coatings as the driving force, epoxies sales should grow at an average
annual rate of 10 percent per year.
C. H. Kline & Co. estimates that the plastics, materials, and resins
industry as a whole will experience an average annual growth rate of 7
percent through 1983. If this proves to be true, it will be good news for
the many AO chemical producers who supply the materials for producing
plastics.
The elastomers market will not fare as well as plastics. C. H. Kline
& Co. has projected an average annual growth rate of 3.1 percent through
1983. SBR, which represents half-of the elastomers total production, will
increase at a rate of only 1 to "21 percent a year. This is because SBR is
-* -
tied so closely to the automotivevindustry, with 65 percent of SBR used in
passenger car tires. With radial tires and smaller automobiles (hence,
smaller tires) becoming more popular, the growth prospects for SBR are dim.
The other major end use of AO chemicals, fabrics, should experience
moderate growth. With the industry maturing, growth through 1986 is not
?Q
expected to be much greater than the overall growth in GNP. Nylon will
show the strongest growth due to increasing demand, and polyester growth
should be steady.
9.1.7 Individual AO Chemicals
The following individual profiles indicate the chemical users as well
as the projected average annual growth rates for the larger volume chemicals.
Published sources give growth rate projections through 1983, and these are
assumed to be true through 1986. Overall growth for AO chemicals, using a
weighted-by-capacity average, is projected to be 4.7 percent.
9.1.7.1 Acetaldehyde. Acetaldehyde is used as an intermediate in the
production of a number of chemicals. Half of total acetaldehyde consumption
is for the production of acetic acid and acetic anhydride which, in turn,
are used in large part to make plastics. Other substances derived from
9-30
-------
acetaldehyde are pentaerythritol, pyri dines, peracetic acid, crotonaldehyde,
chloral, 1,3-butanediol, glycol, lactic acid, and glyoxal. Acetaldehyde is
expected to have an average annual growth rate in production of 4 percent
through 1986.21
9-1-7-2 Acetic Acid. Acetic acid is used to manufacture a number of
plastics and other substances. Forty percent of acetic acid is used in the
production of vinyl acetate monomer. Twenty-three percent is used in
making cellulose acetate. Acetic esters, such as ethyl acetate and butyl
acetate, account for 13 percent. Terephthalic acid and dimethyl terephthal-
ate, which are used to manufacture polyester, account for 10 percent.
Miscellaneous textile industry processes, such as wool dyeing, silk
cleaning, printing, finishing, and laundering, use 3 percent of all acetic
acid.
Chloroacetic acid, which is used in food, drug, cosmetic, and denti-
frice products, synthetic detergents, and oil well drilling mud, accounts
for 2 percent. Other substances',-including grain fumigants, Pharmaceuticals,
rubber chemicals, and photographifc chemicals, use 9 percent.
Acetic acid is expected to have an average annual growth rate of 4.6
percent through 1986.22
9.1.7.3 Acetone. Acetone"is used to manufacture several plastics,
solvents, and other substances. Methyl methacrylate accounts for 25 percent
of all acetone consumption. Methyl isobutyl ketone accounts for 14 percent.
Solvents for protective coatings use another 10 percent.
Pharmaceuticals use 6 percent of the acetone total. Use as a chemical
processing solvent accounts for another 5 percent of acetone volume.
Methacrylic acid and higher methacrylates use 5 percent. Bisphenol A, used
in making epoxy resins, consumes another 5 percent.
Additional uses of acetone include cellulose acetate spinning solvent
(4 percent), hexylene glycol (3 percent), diacetone. alcohol (2 percent),
methyl isobutyl carbinol (2 percent), isophorone (2 percent), mesityl oxide
(1 percent), and other substances (16 percent).
The projection for acetone is a 4 percent average annual increase in
production through 1986.23
9.1.7.4 Acetonitrile. Acetonitrile ,is used as a solvent, as a chemi-
cal intermediate for vitamin B, and in pyrimidines and pharmaceutical uses.
9-31
-------
This chemical is a byproduct from the production of acrylonitrile; the
plants that produce acetonitrile are the same plants that produce acrylom'-
trile. It is assumed that acetonitrile and acrylonitrile have similar
growth projections (4 percent).
9.1.7.5 Acetophenone. Acetophenone is used in the production of
solvents, drugs, polymers, and paints.
9.1.7.6 Acrolein. Acrolein is used primarily as an intermediate
chemical in the production of glycerin and acrylic acid. It is used also
in the manufacture of methionine hydroxy analogue.
9.1.7.7 Acrylic Acid. Acrylic acid is used in the manufacture of
acrylates, which are used in emulsion and solution polymers, in coatings,
finishes, binders, paints, floor polishes, and adhesives. The projected
25
annual average growth rate for acrylic acid is 5 percent.
9.1.7.8 Acrylonitrile. Approximately half (52 percent) of acrylonitrile
use is in the production of acrylic and modacrylic fibers. These are used
mainly in making sweaters, handcraft yarn, pile, and fleece, as well as carpet
static, blankets, draperies, ancTaphoTstery.
ABS and SAN plastics accountvfor another 22 percent. ABS plastics are
used in pipes, pipe fittings, automobile components, and other uses. SAN
plastics are used in drinking tumblers, automotive dashboards, and other
items.
Additional uses of acrylonitrile include the production of adiponitrile
(11 percent) used in the manufacture of nylon 6,6, nitrile elastomers (4
percent), acrylamfde (4 percent) used in secondary and tertiary oil recovery
and waste treatment, nitrile barrier resins (1 percent) for packaging, and
other substances (5 percent).
Acrylonitrile is projected to have an average annual growth rate of 4
Og
percent through 1986.
9.1.7.9 Anthraquinone. Anthraquinone is produced primarily for the
manufacture of dyes and dye intermediates for use in the textile industry.
There is a family of anthraquinone dyes.
9.1.7.10 Benzaldehyde. Benzaldehyde, which has an almond scent, is used
largely in the manufacture of perfumes, flavor chemicals, dyes, and Pharmaceu-
ticals.
9-32
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9.1.7.11 Benzole Acid. Thirty-five percent of benzoic acid is used
in plasticizers, such as stabilizers used in vinyl plastics. Eighteen
percent is used to make sodium benzoate, which is used as a food preserva-
tive to prevent the growth of molds, yeast, and bacteria.
Benzoyl chloride accounts for 24 percent. It is an intermediate in
the manufacture of benzoyl peroxide, a curing agent. Butyl benzoate, a dye
carrier, accounts for another 8 percent. Alkyd resins, used in surface
coatings, particularly on automobiles, account for 5 percent. Other sub-
stances, including food additives, drilling mud additives, medicines,
flavors, and perfumes, account for the remaining 10 percent of
consumption.
Benzoic acid is expected to have an average annual growth
27
benzoic acid
rate of
between 6 and 8 percent.
9-1"7-12 1,3-Butadiene. Seventy-six percent of butadiene consumption
is in the production of elastomers. Styrene-butadiene rubber (SBR) accounts
for 45 percent of the total consumption of butadiene. SBR, in turn, is
used primarily for automobile aty^ light truck tires as well as for hoses
^_ 5
belts, adhesives, and dipped goods.
Polybutadiene accounts for-'20 percent of butadiene use. It also is
used primarily (85 percent) in the manufacture of tires. Non-tire uses of
polybutadiene include the production of polybutadiene-modified impact
polystyrene.
Chloroprene/neoprene accounts for 8 percent of the butadiene total
Chloroprene is used to make neoprene, which is able to withstand consider-
able exposure to oil, heat, air, weather, and abrasion. Neoprene's mai
uses are in industrial and automotive items like hoses, belts, weather
stripping, seals, gaskets, wire and cable coverings, construction, and
adhesives.
Nine percent of butadiene use is in the manufacture of adiponitrile/
hexamethylenediamine for the production of nylon 6,6 and nylon 6,12. Nylon
6,6 fibers are used in carpets, home furnishings, apparel, tire 'cord, and
other uses. Nylon 6,6 plastics are used in injection molded gears and
mechanical parts, including automotive parts. Nylon 6,12 plastics are used
primarily in bristles and monofilament uses.
9-33
-------
Seven percent of butadiene use is for styrene-butadiene co'polymer
latexes, especially for carpet-back coatings and paper coatings. Other
uses include ABS plastics (6 percent) and various other uses including
other polymers (2 percent). ;
Butadiene is projected to have an average annual growth rate of 2.5
28
percent through 1986.
9.1.7.13 p-t-Butyl Benzoic Acid. p-t-Butyl benzoic acid is used in
the manufacture of alkyd and other plastics and as an intermediate in the
production of specialty chemicals. -
9.1.7.14 n-6utyric Acid. n-Butyric acid is used in the manufacture
of lacquers and plastics. It also is used in flavorings, plasticizers,
Pharmaceuticals, and leather tanning.
9.1.7.15 Crotonic Acid. Crotonic acid is used to produce a hot melt
adhesive, in a copolymer with vinyl acetate, for bookbinding. It is used
also in sizing, wood sealers, fungicides, butyric acids, and plasticizers.
9.1.7.16 Cumene Hydroperoxide. Cumene hydroperoxide is used primarily
as an intermediate in the production of acetone and: phenol. It is used
v . :
also in peroxide catalyst applications-and as a curing agent for vulcanizing
rubber products.
Because cumene hydroperoxide is related directly to the production of
acetone and phenol, it is assumed that it will have a similar average
annual growth rate. This rate is between 4.0 percent (acetone) and 4.5
percent (phenol) (weighted by the amount of cumene hydroperoxide used for
acetone and for phenol, the growth rate is computed to be 4.3 percent).
9.1.7.17 Cyclohexanol and Cyclohexanone. Ninety percent of cyclo-
hexanol is used to produce adipic acid for the manufacture of nylon 6,6.
The remaining 10 percent is used, to a large extent, for dyeing in the
textile industry and producing cyclohexyl esters like dicyclohexyl phthalate.
The phthalate esters are used primarily as plasticizers, particularly in
heat-sealing coatings.
Forty percent of cyclohexanone is used to make caprolactam for the
manufacture of nylon 6. Fifty-five percent is oxidized as mixed oil to
manufacture adipic acid, which, as noted above, is used to manufacture
nylon 6,6. The remaining volume of cyclohexanone is used mainly as a
solvent for lacquers and crude rubber, spot removal, leather degreasing,
and other solvent applications.
9-34
-------
The average annual growth rate through 1986 should be tied to adipic
acid, its main consumer, at a rate of 2.5 percent.29
9-1.7.18 Dimethyl Terephthalate (DMT) and Terephthalic Acid CTPAL
DMT and TPA are used primarily in the manufacture of polyester fibers and
film.
Polyester fibers account for 89 percent of DMT consumption and 95
percent of TPA consumption. Polyester film accounts for an additional 9
percent of DMT and 4- percent of TPA. Lesser uses of DMT include polybuty-
lene terephthalate plastics.
Of the polyester fiber produced, apparel accounts for 62 percent, home
furnishings for 17 percent, and other uses for the remainder. The manufac-
ture of tire cord is a large use. Photographic film is the major use of
polyester film. Polybutylene terephthalate plastics are used to replace
automotive metal parts, often with glass fibers or mineral fillers. Poly-
ethylene terephthalate barrier plastics are another use, as in carbonated
beverage bottles.
DMT and TPA are projected to»have an average annual growth rate of 7..5
percent through 1986.30
9-1.7.19 Ethylene Pichloride. Most ethylene dichloride is converted
in nearby facilities to vinyl chloride, the raw material for polyvinylchlo-
ride.
Polyvinylchloride's largest market is construction. The polymer is
used mostly for pipes and fittings; vinyl siding and home furnishings are
additional uses.
Ethylene dichloride production is expected to grow at an average
annual rate of 5.5 percent through 1986.31
9-1-7.20 Ethylene Oxide. Ethylene oxide is used in a number of
applications. Sixty-four percent of ethylene oxide is used to make ethylene
glycol, which is used as anti-freeze in automobiles and in making polyester
fibers and films and other substances. Eleven percent of ethylene oxide is
used for non-ionic surface active agents. Solvents like glycol ethers
account for another 6 percent. Ethanolamines, which comprise 5 percent,
are used in acid gas scrubbing, soaps, and detergents.
Diethylene glycol (5 percent of ethylene oxide consumption) is used to
produce unsaturated polyester resins,' textile lubricants and conditioners,
9-35
-------
plasticizers, and several other items. Triethylene glycol (accounting for
2 percent of ethylene oxide use) and diethylene glycol are used in natural
gas dehydration. Triethylene glycol also is used as a humectant and in the
manufacture of vinyl plasticizers.
Polyethylene glycol is used mainly in surface active agents and accounts
for 2 percent of ethylene oxide use. The remaining 5 percent of ethylene
oxide use is accounted for by miscellaneous uses.
The predicted average annual growth rate through 1986 for ethylene
32
oxide is 3.5 percent.
9.1.7.21 Formaldehyde. The majority of formaldehyde use involves the
production of various plastics. Urea resins (25 percent), phenolic resins
(24 percent), and melami/ie resins (4 percent) account collectively for more
than half the total use of formaldehyde.
Other uses include pentaerythritol (6 percent), hexamethylenetetramine
(4 percent), butanediol (8 percent), acetal plastics (7 percent), urea-for-
maldehyde concentrates (4 percent-), chelating agents (4 percent), 4-4'-methyl-
enedianile and 4-4'-methylenediphpanyl isocyanate (3 percent), textile
-* ~
treating (2 percent), pyridine chemicals (1 percent), trimethylol-propane
(1 percent); and other substances (7 percent) including nitroparaffin
derivatives.
The largest uses of urea resins from formaldehyde are as adhesives in
particleboards and fiberboards, as adhesives in other uses, and in molded
plastic parts. Urea resins also are used in paper treating, coatings, and
laminates.
Phenol-formaldehyde resins are used in bonding plywood and in binding
various kinds of glass and mineral insulation. Acetal resins are used in
automotive and appliance parts, plumbing hardware, and other items. Mela-
mine-formaldehyde resins are thermosetting resins. Butanediol is used in
making acetylenic chemicals, solvents, urethanes, polyesters, plasticizers,
and elastomers.
The projected average annual growth rate through 1985 for formaldehyde
33
is 4 percent.
9.1.7.22 Formic Acid. Formic acid is used to dye exhausting agents
for textiles, as a deliming agent and neutralizer for the leather industry,
and as a chemical intermediate for various substances.
9-36
-------
Formic acid is'expected to have an average annual growth in production
of 4 percent. ,
9.1.7.23 Glyoxal. Glyoxal is used in the cross-linking of protein
materials and in hydroxal-containing polymers. It also is used for shrink-
proofing rayon and tanning leather and as a reducing agent in dyeing tex-
tiles. !
9.1.7.24 Hydrogen Cyanide. The majority (62 percent) of hydrogen
cyanide use is in the manufacture of methyl methacrylate. NTA and other
chelates account for an additional 21 percent. Sodium cyanide, used mainly
in the treating and-electroplating of metals, accounts for 10 percent.
Miscellaneous uses are involved in the remaining 8 percent.
The growth rate through 1986 for hydrogen cyanide is expected to be 6
percent per year.
9-1-7.25 Isobutvric Acid. Isobutyric acid is used as a mercaptan
solubilizing promoter in sweetening gasoline and in the manufacture of
flavoring and perfume.
9-1-7.26 Isophthalic Acid. *Isoohthalic acid is used in making iso-
phthalic polyester plastics (54 percent), which are used especially in
glass fiber reinforced plastics: such as corrosion-resistant equipment and
pipe. It also is used in the manufacture of alkyd resins (26 percent) and
other substances (24 percent)), including dioctyl isophthalate plasticizer,
polyester fibers and film, pqlyamide fibers, high-temperature-resistant
polymers, electrical insulation resins, and hot melt adhesives. It also
serves as a receptor in arimijd fibers.
Isophthalic acid production is expected to increase at 7 percent per
year through 1986.36 ]
9-1-7-27 Maleic Anhydride. Fifty percent of the production of maleic
anhydride is used in the manufacture of polyester plastics. Of the poly-
ester plastics produced, three fourths are used in reinforced applications
such as building panels, marine craft, marine accessories, and automobiles.
The other fourth is used in casting plastics, putty resins, and clay pipe
seals.
Fifteen percent of maleic anhydride is consumed in the production of
fumaric acid. Ten percent is used in agricultural pesticides, including
malathion, captan, and maleic hydrazide. Use in alkyd resins accounts for
5 percent. Miscellaneous applications account for the remaining 20 percent.
9-37
-------
Maleic anhydride is expected to have an average annual growth in
production of 5 to 6 percent through 1.986.37
9.1.J7.28 Methyl Ethyl Ketone. Methyl ethyl ketone is used primarily
as a solvent. Its solvent applications account for the bulk of total
use — vinyl coatings solvent (34 percent), nitrocellulose coatings solvent
(14 percent), adhesives solvent (14 percent), and acrylic coatings solvent
(12 percent). Miscellaneous coatings account for 7 percent.
Lube oil dewaxing, by solvent extraction, uses 7 percent of all methyl
ethyl ketone. Miscellaneous uses account for the remaining 6 percent,
including solvent extraction in hardwood pulping and ink manufacture.
Methyl ethyl ketone is expected to have an average annual growth in
3S
production of 4 percent.
9.1.7.29 Methyl Styrene. Methyl styrene is used in modified polyester
and alkytf resin formulations. It also is used in food applications, paints,
waxes, adhesives, and various plastics.
Methyl styrene is expected to have an average annual growth in produc-
39 - -
tion of 6 percent. ^ |
9.1.7.30 Phenol. Forty-nine percent of phenol consumption is in the
production of phenolic resins. .'The largest use for phenolic resins is in
the plywood industry, where it is used to bond sheets of wood in producing
plywood. Bisphenol A accounts for 14 percent of pheno.1 use. The largest
use of bisphenol A. is the production of epoxy resins. Caprolactam accounts
for 14 percent of phenol use and is used primarily to produce fibers and
plastics. '"''
Lesser uses of phenol include the manufacture of methylated phenol (4
percent), plasticizers (3 percent), adipic acid (3 percent), salicylic acid
(2 percent), nonylphenol (2 percent), dodecylphenol (1 percent), other
alkylphenols (3 percent), 2,4-0 (1 percent), pentachlorophenol (1 percent),
other chlorophenols (2 percent), petroleum refining (1 percent), and mis-
cellaneous uses.
The predicted average annual growth rate through 1986 for phenol is
40
4.5 percent.
9.1.7.31 Phthalic Anhydride. Phthalic anhydride use is oriented
toward the plastic industry. Plasticizers, which account for 52 percent,
are used mainly for polyvinylchloride. Dioctyl phthalates are the largest
plasticizers.
9-38
-------
Unsaturated polyester resins account for 22 percent of phthalic anhy-
dride use. These are used as general purpose resins, particularly in the
construction, marine, and synthetic marble fields.
Alkyd resins account for 21 percent of phthalic anhydride use. These
resins are used as surface coatings. Phthalic anhydride is used to produce
80 percent of all alkyd resins.
Phthalic anhydride is expected to have an average annual growth in
production of 3.8 percent.41
9<1"7-32 Prop-Ionic Acid. Propionic acid is used to a large degree in
the agricultural sector. Its use as a grain preservative accounts for 38
percent of all propionic acid use. Calcium and sodium propionates, used as
food preservatives, account for 26 percent. Propionic acid also is used to
make herbicides. This use accounts for 13 percent. Ten percent of propi-
onic acid is used in the manufacture of cellulosic plastics. Other uses,
including Pharmaceuticals, account for 13 percent.
Propionic acid is expected;to have an average annual growth in produc-
tion of 5 percent.42 -~
»
9-1-7-33 Propylene Oxide." iPronvTana oxide is used primarily in the
manufacture of plastics. Fifty-four percent of propylene oxide is used to
manufacture polyurethane polyols. These are used to make polyurethane
foams, which are used particularly in furniture and automobile seats, and
non-foam plastics like surface coatings, elastomers, microcellular polyure-
thanes, and sealants.
Nineteen percent of propylene oxide is used to make propylene glycol,
an intermediate in the production of unsaturated polyester resins. Three
percent is used to make dipropylene glycol, also used in plasticizers and
to make unsaturated polyester resins.
Two percent is used to make glycol ethers, which are used as solvents
in the coatings industry. The remaining 22 percent of propylene oxide use
involves miscellaneous substances, including non-urethane polyether polyols,
glycerin, isopropanolamines, and other chemicals.
The predicted average annual growth rate through 1986 for propylene
oxide is 5.5 percent.43
9.1.7.34 Styrene. Styrene is a high-volume plastic that has many end
uses because of its relatively low cost and light weight. Eighty-one
9-39
-------
percent of styrene use is as polystyrene and styrene copolymers. These are
broken down as follows: polystyrene, 62 percent; ABS and SAN resin, 10
percent; styrene-fautadiene copolymer latexes, 7 percent; and other copoly-
mers, 2 percent. In addition, 11 percent of styrene use is in the manufac-
ture of SBR elastomers. Seven percent is used in unsaturated polyester
resins; 1 percent is accounted for by miscellaneous uses.
Styrene's derivatives are, in turn, used in various functions. Poly-
styrene is used in packaging and construction markets. ABS resins are used
in pipes, automobiles, and appliances. SAN resins, which are transparent
rigid thermoplastics, are used in automobile instrument panel windows and
lenses, clear housewares, and appliances. Styrene-butadiene copolymer
latexes are used primarily as carpet back coatings and paper coatings. SBR
elastomers account for the majority of elastomer use in passenger car and
lightweight truck tires. Rubber products, such as industrial hoses and
belts, and latexes for dipped products and adhesives are other uses of SBR
elastomers. Unsaturated polyester resins and thermosetting resins are used
mainly in fiberglass-reinforced"pflastics for marine, construction, and
-* -
transportation items. v
The ultimate uses of styrene and its derivatives are as follows:
packaging, 22 percent; construction, 16 percent; electrical, appliance,
television, communication, and office machines, 12 percent; households, 12
percent; transportation, 10 percent; recreation, 8 percent; disposable
serviceware, 4 percent; exports, 5 percent; and miscellaneous uses, 11
percent.
The projected average annual growth rate through 1986 for styrene is 5
44
percent.
9.1.8 Coproducts and Byproducts
A coproduct is essentially a chemical that is produced in conjunction
with one or more other chemicals and is readily marketable; a byproduct is
the "leftover" of the process, which, although in some cases is marketable,
often is consumed captively. The concept of coproducts and byproducts is
important because any cost of pollution control on the process would not be
borne totally by an individual chemical.
If, for example, the cost of the cumene oxidation process increases,
it may be passed on to the consumer in several ways. The coproducts of
9-40
-------
cumene oxidation are acetone and phenol. The increased costs may be passed
on to acetone consumers and phenol consumers equally or if, say, the phenol
market is stronger, 75 percent of the cost can be passed on to phenol con-
sumers and 25 percent to acetone consumers. Conceivably, any combination
is possible, but the exact ratio would depend on market conditions for the
coproducts. Table 3-8 presents the AO chemicals that can be classified as
coproducts.
The AO chemical byproducts, also listed' in Table 3-8, all are recovered
and used as intermediates in the production of other chemicals. They are
not, however, the main end products of the process and any increase in
production costs probably would be passed on (if market conditions allow
it) solely through the primary chemical product. However, in the individual
AO chemical economic analysis (Section 9.2), coproducts and byproducts are
treated similarly. First, the cost of control is determined for an AO
process, then all individual coproducts and/or byproducts produced by that
process pass through the total cost of control (based on the primary chemi-
cal's smallest plant size) to demonstrate price inflation effects.
9.1.9 Growth in New Facilities"*-
Forty-nine air oxidation chemical plant facilities are projected to be
built between December 1, 1981 and December 1, 1986. The projection makes
.the critical assumption (Scenario I) that the capacity utilization rate in
1986 for each chemical will be equal to that chemical's average historical
capacity utilization rate for the seven years preceding January 1, 1979.
The average historical capacity utilization rate is a weighted average,
with 1978 carrying the most weight and 1972 the least weight. Ideally,
each chemical facility would operate at 85 percent of nameplate capacity
over the long run. Many chemical industry sources state that, in the long
run, 85 percent is about the maximum capacity achievable without putting a
strain on plants. If all chemical facilities operated at 85 percent (Sce-
nario II), the number of new facilities to be built would be 15. Given
growth projections, present unused capacity, and the desire to operate at
85 percent capacity, there is not much room for new capacity (facilities).
The methodology for computing capacity increases and number of new
facilities makes several key assumptions. First, all facilities have a
life of 20 years, so that any new capacity built or added on to existing
9-41
-------
facilities between December 1, 1961 and December 1, 1966 would be retired
during the five-year period examined in the analysis. The retired capacity
would be replaced in order to satisfy existing and future demand and would
fall under the category of modifications and reconstruction of existing
facilities (see Section 5). Of course, all future modifications and recon-
structions cannot be projected plausibly. Second, the size of the facility
to be built for each chemical will be the same as the average size of
present facilities used to produce that chemical. Finally, growth projec-
tions made through 1983 or 1984 are asfsumed to apply through 1986. Table
9-10 presents the equations for projecting the new capacity (facilities).
Results of the calculations are given in Table 9-11. As explained in
the footnotes, byproducts and-some coproducts are projected to have zero
new facilities built because these chemicals are always produced in conjunc-
tion with other AO chemicals at the same facility. If acetone (a coproduct
with phenol) was projected to have a certain number of new facilities based
on the methodology given in Table-9-10 and if phenol also were projected to
build new facilities, double counting would exist because phenol and acetone
will be produced at the same new facility. The same situation exists for
byproducts.
Of the two scenarios presented, Scenario I is the more realistic. An
85 percent capacity utilization rate (Scenario II) would be ideal economi-
cally for the producers but highly improbable. The average AO chemical
capacity utilization rate has never reached 85 percent in the last 30
years. Historica-lly, the capacity utilization rate usually has been around
80 percent for any given year, although the rate has fallen below 80 percent
in the past few years. Unless demand makes an unusual and sharp increase,
an 85 percent capacity utilization rate will not occur and a projection of
15 new facilities probably is too low. The best estimate is that 49 plants
will be built between December 1, 1981 and December 1, 1986.
9.1.10 Substitution
Substitution is a prime variable when demand elasticity of an AO
chemical is examined. If demand for a chemical is elastic because of
substitute products, it is difficult to pass on increased costs to cus-
tomers.
9-42
-------
TABLE 9-10. EQUATIONS FOR PROJECTNG AO NEW CAPACITY AND FACILITIES
23 AO Chemicals
United States
Dec. 1, 1981 - Dec. 1, 1986
1) [FP
- CC + RC - 1C] x AOP = NC
2) NC -T FS = NF
where:
FP =
CU =
"Future Production." For each individual chemical, the 1978 pro-
duction figure is converted into a 1986 production figure based
on a growth projection (see Section 9.1.7, "Individual AO
Chemicals," for these growth projections).
"Capacity Utilization." 1986 capacity utilization rates are
expressed as a fraction.. When Scenario I is used, the 1986
capacity utilization rate is based on the individual chemical's
weighted average historical capacity utilization rate. These
rates are listed below:v
Acetaldehyde 0.74
Acetic acid 0.89
Acetone 0.73
Acrylic acid 0.71
Acrylonitrile 0.87
Benzoic acid 0.69
1,3-Butadiene 0.79
Dimethyl terephthalate 0.79
Ethylene dichloride 0.73
Ethylene oxide 0.84
Formaldehyde 0.69
Formic acid 0.73
Hydrogen cyanide
Isophthalic acid
Maleic anhydride
Methyl ethyl ketone
a-Methyl styrene
Phenol
Phthalic anhydride
Propionic acid
Propylene oxide -
Styrene
Terephthalic acid
0.
0.
0.58
0.54
0.69
.76
,81
0.78
0.76
0.44
0.76
0.83
0.79
Weighted capacity utilization rates are calculated by dividing
the individual AO chemical's production by its capacity for each
of the years 1972 through 1978. The 1978 capacity utilization
rate is multiplied by 7, the 1977 rate by 6, the 1976 rate by 5,
and so on down to the 1972 rate which is multiplied by 1. The
products are added and then divided by 28 to arrive at the
weighted capacity utilization rate. Production data are taken
from U.S. International Trade Commision. Synthetic Organic
Chemicals. US ITC Publication 10001. It is published each year.
Capacity data are from SRI International, Directory of Chemical'
Producers and it is updated and published every year.
9-43
-------
TABLE 9-10 (Continued). EQUATIONS FOR PROJECTING AO
NEW CAPACITY AND FACILITIES
23 AO Chemicals
United States
Dec. 1, 1981 - Dec. 1, 1986
Scenario II presents the case where each individual chemical
facility has an 85 percent capacity utilization rate in 1986.
CC * Current Capacity." See Table 9-2 for the 1978 total capacity for
each chemical.
RC = "Retired Capacity." The useful life of an air oxidation facility
is assumed to be 20 years such that the "retired capacity" figure
represents capacity built between December 1, 1961 and December
1, 1966 and then rendered unproductive between December 1, 1981
and December 1, 1986. The 1961-1966 April and October issues of
Chemical Engineering give a "Construction Alert" for all chemical
facilities during that period that came on-line. Listed below
are the individual chemical replacement capacity figures, which
represents capacity added on in the years 1961-1966.
Acetaldehyde 45 Gg
Acetic acid 159 Gg
Acetone 75 Gg
Acrylic acid 0 Gg
Acrylonitrile 23 Gg
Benzoic acid 8 Gg
1,3-Butadiene 15 Gg
Dimethyl terephthalate 45 Gg
Ethylene dichloride 45 Gg
Ethylene oxide 179 Gg
Formaldehyde ...- 205 Gg
Formic acid 0 Gg
Hydrogen cyanide 0 Gg
Isophthalic acid 27 Gg
Maleic anhydride 52 Gg
Methyl ethyl ketone 68 Gg
a-Methyl styrene 0 Gg
Phenol 150 Gg
Phthalic anhydride 107 Gg
Propionic acid 0 Gg
Propylene oxide 53 Gg
Styrene 204 Gg
Terephthalic acid 45 Gg
1C = "Interim Capacity." This represents capacity that is known to
have come onstream or that is planned to come onstream after 1978
and before the date of proposal. The interim capacity informa-
tion is found in in the 1978-1981 April and October issues of
Chemical Engineering's "Construction Alert."
AOP = "Air Oxidation Proportion." This figure can be found in Table
3-7. In essence, it gives the probability (percent chance) that
a new facility will be an AO facility.
NC = "New Capacity." This represents the estimated amount of new
capacity in gigagrams that will be built between December 1, 1981
and December 1, 1986. This figure is rounded off to the nearest
gigagram.
9-44
-------
TABLE 9-10 (Continued). EQUATIONS FOR PROJECTING AO
NEW CAPACITY AND FACILITIES
23 AO Chemicals
United States
Dec. 1, 1981 - Dec. 1, 1986
FS =•
NF =
"Facility Size." This represents the average facility size for
each AO chemical. It is total capacity for the chemical divided
by the number of facilities producing that chemical. Chemical
capacities and facilities are given in Table 9-1.
"New Facilities." This represents the number of new facilities
to be built for each chemical during the first five years of the
regulation. When the calculation is done, the number of new
facilities is rounded of to the nearest whole number.
9-45
-------
TABLE 9-11. PROJECTED NEW AO CHEMICAL FACILITIES BY CHEMICAL FOR
TWO CAPACITY UTILIZATION SCENARIOS
23 AO Chemicals
United States
Dec. 1, 1981 - Dec. 1, 1986
Chemical3
Acetal dehyde
Acetic acid
Acetone
Acrylic acid
Acrylonitrile
Benzoic acid
1,3-Butadiene
Dimethyl terephthalate
Ethyl ene di chloride
Ethyl ene oxide
Formal dehyde
Formic acid
Hydrogen cyanide
Isophthalic acid
Maleic anhydride
Methyl ethyl ketone
a-Methyl styrene
Phenol d
Phthalic anhydride
Propionic acid
Propylene oxide
Styrene
Terephthalic acid
TOTAL
Projected number of
new facilities
(scenario I)
0
2
4
1
0
3
1
:'" 0
J 2
_ " 1-
19
0
4
1
6
0
0
0
3
0
1
0
1
49
Projected number of
new facilities
(scenario II)
0
1
2
0
1
1
1
0
0
0
5
0
0
0
3
0
0
0
1
0
0
0
0
15
9-46
-------
TABLE 9-11. (Continued). PROJECTED NEW AO CHEMICAL FACILITIES BY CHEMICAL
FOR TWO CAPACITY UTILIZATION SCENARIOS
23 AO Chemicals
United States
Dec. 1, 1981 - Dec. 1, 1986
This list of 23 chemicals represents only those chemicals for which projected
growth rates, historical and current capacity and production data, and number
of facilities are available. The other 13 chemicals are excluded for lack of
such information and, in addition, are not especially essential to the new
facilities projection. The 23 chemicals listed above represent approximately
95 percent of the total capacity that uses the AO process.
Scenario I: The capacity utilization rate in 1986 for each chemical will be
equal to the weighted average historical capacity utilization rate for that
particular chemical
cScenario II: The capacity utilization rate in 1986 for each chemical will
be 85 percent of nameplate capacity. This is how full effective capacity
utilization is defined.
DMT_is a coproduct of the TPA• production process, methyl ethyl ketone and
formic acid are byproducts of the acetic acid production process, a-Methyl
styrene is a coproduct of the acetone production process, phenol is a co-
product of the acetone production process, and styrene is a coproduct of
the^propylene oxide process. -The projected number of new facilities pro-
ducing these chemicals is zero:to avoid double counting.
9-47
-------
AO chemicals are used ultimately as solvents, specialty chemicals
such as flavors, fragrances, etc., or precursors in polymer or drug manu-
facture. For solvents, drugs, and specialty chemicals, chemical properties
are most important. For polymers, precursors are chosen for a variety of
mechanical, optical, electrical, and chemical properties.
When one characteristic is of predominant importance, a substitute
usually can be found. This is the case with products used to produce
drugs, solvents, or specialty chemicals. When a specific combination of
properties is required, substitution is more difficult and sometimes impos-
sible. This is the case for polymers used in plastics, rubbers, synthetic
fibers, surface finishes, and adhesives.
Substitutes for the following AO chemicals conceivably could be found
outside the AO industry:
• Acetaldehyde
• Acetonitrile
• Acrolein ^ .
• p-t-Butyl benzoic acid - ^
• n-Butyric acid
• Crotonic acid \
t Formic acid
• Glyoxal
• Hydroquinone
t Isobutyric acid.
Each of these chemicals, however, is used for several different purposes
and there is no easily identifiable non-AO chemical that can be substituted
for all of them. For example, acetaldehyde is used in the production of
acetic acid, perfumes, plastics, and synthetic rubbers. It would be diffi-
cult to find one chemical that could serve as a substitute for acetaldehyde
in all four uses.
The AO process may, in some cases, be substituted for by other types
of processes. Table 3-7 demonstrates that 15 AO chemicals are known to be
produced by non-AO processes. A few chemicals such as 1,3-butadiene,
propionic acid, and styrene are produced mostly from non-AO processes.
Economics and applicability determine whether one process, such as the
chlorohydrin process, is competitive with the AO process.
9-48
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9.1.11 Raw Materials
Raw materials represent the largest production cost for AO chemical
producers. Table 9-12 gives the different raw materials used in.producing
AO chemicals. Note that AO chemicals acetaldehyde and acetic acid also are
used as feedstocks. In addition, some raw materials are used to make more
than one AO chemical. For more of a discussion of raw materials refer to
• Section 3.3.2.
The raw materials (listed in Table 9-12) are formed originally from
either petroleum oil or natural gas, with oil the primary precursor of AO
chemicals. Coal is not as yet a significant precursor. Compounds such as
ethane, propane, naphtha, butane, and other single bond compounds are
distilled from natural gas liquids and crude oil. Then, cracking the single
bonded compounds yields some of the raw materials listed in Table 9-12 such
as ethylene, the petrochemical produced in the largest volume, propylene,
toluene and xylene. The remaining raw materials listed are formed either
from the cracking of single bonded compounds or by the combination of two
or more chemical compounds. ~e
Almost all basic raw materials are interchangeable with each other and
the choice of one particular compound as a'raw material depends on econ-
omics. For instance, petrochemical producers presently are substituting
propane and butane for high cost naphtha. Future raw materials prices are
a major concern. The safest thing that can be said is that the prices of
substitutable raw materials will alternate over the years. Thus, even
though it is more--expensive, new plants will be built with much greater raw
material flexibility.
The current trend is toward using more crude oil and other heavy raw
materials, which will favor oil companies that have refineries. Also,
there is an increasing interest in forming joint ventures between petroleum
and chemical companies to produce large commodity chemicals. In such an
arrangement, chemical companies are ensured a raw materials supply and
large amounts of capital from the petroleum firms which, in turn,, gain an
outlet for their refinery products as well as an established marketing
network.
Raw material prices will escalate substantially through 1986 due to
rapidly rising oil and natural gas prices. The Department of Energy's
9-49
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TABLE 9-12. RAW MATERIALS OF AO CHEMICALS
25 Raw Materials
United States
1978
Acetaldehyde
Acetic acid
Ammonia
Anthracene
Benzoin
n-Butane
n-Butyl alcohol
p-t-Butyl toluene
n-Butyraldehyde
Crotonaldehyde
Cumene
Cyclohexane
Di i sopropy1 benzene
p-di i sopropy1benzene
Ethyl alcohol
Ethyl benzene
Ethylene
Ethylene dichloride
Ethylene glycol
Isobutyraldehyde
Methanol .
Naphthalene
Propylene
Toluene
o-Xylene
p-Xylene
9-50
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projections from the Midrange Energy Forecasting System show that the price
of crude oil in 1986 will be $5.03 per gigajoule in 1978 dollars ($30.80
per barrel). This represents an average real annual increase of more than
20 percent. It is a substantial increase above and beyond general inflation
and should mean large boosts in the price of downstream AO intermediate
chemicals and their end products.
9.1.12 Prices
9.1.12.1 Price of AO Chemicals. The market prices for SOCMI chemicals
produced by an AO process are given on Table 9-13. Anthraquinone, which is
used to manufacture dyes, is the most expensive with a market price of
206.8 cents per kilogram. Formaldehyde is the least expensive of the SOCMI
AO chemicals, with a market price of 11.2 cents per kilogram.
In chemical journals and periodicals, a list price is posted as the ,
cost of a chemical. The list price is not the same as the selling price
and is used only as a focal point around which actual selling prices are
formed. Chemicals are sold on a"-contract price basis or a spot price
basis, and chemical prices, may 65 either greater or less than the current
list price. Buying a chemical 'off contract guarantees the customer a supply
for a predetermined price; this-price usually has an escalator clause
attached to account for .inflation. The customer initially pays more than a
market price for the guarantee of supply but may end up paying less if the
chemical price outpaces inflation.
A spot price, or current market price, is determined by the market
situation. Conventional supply and demand interaction is reflected when
spot prices are quoted. The situation is similar to the sale of an auto-
mobile. The manufacturer sets a list price but the automobile usually is
sold for less. The margin between what the car is sold for and the list
price varies with the supply and demand situation. Most chemicals have a
spot price that is below the list price; however, at times the spot price
is greater than the list price because time is needed to set a list price
(usually it is announced a month in advance) and a sudden tight .supply
situation may drive the spot market price above the list price.
9-1-12.2 Price Determination in the AQ Industry. Given a specific
demand for an AO chemical, different supply scenarios affect the selling
price. If feedstocks are in short supply or are used for other priorities
9-51
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TABLE 9-13. MARKET (SPOT) PRICES FOR AO CHEMICALS
36 AO Chemicals
United States
December, 1978
Chemical
Price
(cents per
kilogram)
Chemical
Price
(cents per
kilogram)
Acetaldehyde 39.7
Acetic acid 33.3a
Acetone 35.9a
Acetonitrile 91.3
Acetophenone 79.4
Acrolein 70.3
Acrylic acid 70.6a
Acrylonitrile 50.7a
Anthraquinone • 206.S.
Benzaldehyde 152.8.^
Benzoic acid 52..9a
1,3-Butadiene 43. Oa
p-t-Butyl benzoic acid 140.9
n-Butyric acid 64.4
Crotonic acid 170.4
Cumene hydroperoxide 61.3
Cyclohexanol/cyclohexanone 73.4/72.8e
Dimethyl terephthalate 47.0
Ethylene dichloride 18.la
Ethylene oxide 49.2a
Formaldehyde 11.2a
Formic acid 40.6
Glyoxal 73.4
Hydrogen cyanide 65.5
Isobutyric acid 148.8
Isophthalic acid 58.7
Maleic anhydride 51.6a
Methyl ethyl ketone 41.9a
a-methyl styrene 39.7a
Phenol 36.8a
Phthalic anhydride 54.2a
Propionic acid 37.5a
Propylene oxide 47.6
Styrene 39.7a
Terephthalic acid 50.5
This price is taken from U.S. International Trade Commission. Synthetic
Organic Chemicals, United States Production and Sales, 1978. USITC Publica-
tion 10001. It represents an average unit value for the year 1978. It was
assumed that this average unit value reflected an actual value for June 1978.
This price was then made a December 1978 price by using the Bureau of Labor
Statistics, Producer Prices and Price Indexes, December 1978. All other
prices were calculated as 10 percent below their list price (the weighted-
by-production-volume average of known market-list price differences). Prices
are free on board (f.o.b.) plant or warehouse.
9-52
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such as gasoline, then the selling price of the AO chemical should rise.
This was the case during the Arab oil embargo that began in October 1973.
If a large amount of new capacity comes on line, then price may be forced
down; if an accident or strike should cause a plant to halt production,
price should increase.
All AO chemicals are intermediate goods used in producing other goods
and there may be a string of downstream products that build upon each other
until a final end product is produced. Demand for an AO end product de-
termines the demand for the AO chemical. Butadiene is used to produce
styrene-butadiene-rubber (SBR), which is used in the production of tires,
primarily, for automobiles. Hence, the demand for automobiles and all the
factors that determine this demand have repercussions all the way upstream,
influencing the demand for butadiene.
The intersection of supply and demand curves represents the quantity
purchased and sold at one price. The capacity utilization rate (production
divided by total nameplate capacity) usually provides a good indication of
the present interaction of supply^and demand. For example, a low capacity
utilization rate would mean that either too much had been supplied, or a
slack in demand existed, or some combination of both. In other words, the
price is too high to clear the market.
It would be difficult for a chemical producer to post a list price
based on demand functions and elasticities. This is especially true with
the AO chemicals since they are intermediate goods and all downstream
demand functions' must be considered. The AO chemical producers typically
base their list prices on a full-cost, or cost-plus method. The full-cost
pricing method involves adding a desired profit margin to estimated unit
costs for a product price. Cost-plus pricing uses a percentage return on,
invested capital instead of a profit margin when calculating product price.
This does not mean that demand elasticities are ignored. On the contrary,
a lower margin is set if demand generally is thought to be elastic. Rigid
profit margins are not the rule-.
Historically, the price of AO chemicals has increased along with most
everything else. The "real" price of these chemicals has been dependent
upon the price of their main feedstocks. A "real" price is one that has
been deflated by a general cost index (consumer's or producer's price
9-53
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index) and is given in nominal 196.7 dollars. The real price of the AO
chemicals increased greatly in 1974 as a result of the Arab oil embargo.
From 1974 to the beginning of 1979, the "real" price generally declined for
most of the AO chemicals, which means that prices increased at a slower
pace than the general rate of inflation. During 1979, there were increases
in the "real" price due to large increases in the cost of feedstocks. With
recent deregulation of oil prices and deregulation of gas prices a probable
future reality, the days of inexpensive feedstocks are numbered. AO chemi-
cals should show rapidly rising "real" prices, at least through 1985.
The use of full-cost and cost-plus pricing implies that as costs
increase, the price should increase at about the same rate. Because feed-
stocks comprise most of the production costs for AO chemicals, their prices
should track very closely, as indicated by Figure 9-3. The figure shows
price trends for various classifications of chemicals and for crude oil,
the primary raw material feedstock in the production of AO chemicals. The
aromatic (characterized by the pnesence of at least one benzene ring) and
aliphatic (an open-chain structures consisting of paraffin, olefin, and
acetylene hydrocarbons and their derivatives) trend lines represent changes
in the list price. Since the end of 1978, it can be seen that producers
have posted list prices that have either kept up with or exceeded the crude
petroleum price increases. From December 1978 to March 1980, the cost of
crude petroleum increased 67 percent. During the same time, the average
list price for aromatics rose 100 percent, and for aliphatics, 67 percent.
Market prices, or the actual prices producers receive, as reflected in
the "intermediate" trend line, also have matched the oil price increases
(rising 75 percent between December 1978 and March 1980). However, AO
chemicals included in the "other organic chemicals" category have risen
relatively slowly. The composite market price for "other organic chemicals"
<«
has increased only 29 percent from December 1978 to March 1980.
If a severe economic slowdown does not come about, all chemical pro-
ducers will be able to match raw material costs in the early 1980's.46
This will be true if predictions of increasing capacity utilization for the
chemical industry are accurate. Also, oil decontrol and gasoline conserva-
tion should ease the pressure on petroleum supplies and make feedstocks
more readily available. This again confirms that the price of AO chemicals
9-54
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DOLLAR INDEX3
MARKET PRICES
ORGANIC CHEMICALS
INTERMEDIATES OTHER
Aerylonitnle Acetic Acid
Elhylene Oxide Acetone
Formaldehyde Etltylene Oichlonde
Phenol Maleic Anhydride
Plithalic Anhydnde Methyl Ethyl Ketone
Stytene .
SOUXCZt Sumu at L«0or 3utUtic». Producer
Prtee [odex. June l977-M«reli t^fO.
UST PRICES
ALIPHATICS AROMATICS
Acetic Acid Senzoi'c Acid
Acetone Cyclohexanone
Aciylonitnle Maleic Anhydride
1.3-8uladien* Phenol
Etnylene Oichlonde Phthalic Anhydnde
Formaldehyde Styiene
Methyl Ethyl Ketone Tarenhthalic Acid
Propylene Oxide
SOUSCCs Altpliaiie Pvie* Ch«a««st AramaUe
Prie* C]Mfic«*. Ot«ueat Mark* tine
Reporter. Jw» 1977— U«Kh 1410.
an
-------
should increase more quickly than the general rate of inflation during the
early 1980's.
9.1.12.3 Competitive Price Structure of the AQ Industry. The market
structure for most AO chemicals is oligopolistic because the products are
homogeneous and the producers are not numerous. Five of the chemicals —
anthraquinone, p-t-fautyl benzoic acid, crotonic acid, isobutyric acid, and
isophthalic acid — are exceptions in that they have only one producing
company, a situation that may exist for one of two reasons. First, a
chemical, its process, or its use may be patented, protecting the producer
from competitors for 17 years. The second and more probable reason is that
the five chemicals are specialty chemicals used captively or by a very
select group of producers. Therefore, they yield little or no profit in
the marketplace.
Each of the large volume AO chemical products is manufactured by five
or more companies, with no one company owning more than 50 percent of the
capacity. Pricing in this sort';of competitive environment is difficult to
label for the AO chemicals, although one term that can be used to charac-
~* *. 47
terize competitive price decisions is -barometric price leadership. The
two relevant points to remember: about barometric price leadership are that
the identity of the price leader often changes; and that leaders are not
always followed. The producer who decides to raise or lower the list price
first acts as a barometer of market conditions by making known through
formal list price announcements that demand and cost conditions have changed.
This new list prtce may be a confirmation of current spot prices that have
departed significantly from the old list price. The leaders may not always
be followed, particularly if they lack the market power to force the other
producers into accepting their price decisions;. Also, the other companies
may adopt a "wait-and-see" strategy when one fjirm decides to change the
list price. |
Some chemical markets are more competitive than others. Acrylonitrile,
which is produced by four companies that all h'ave similarly sized plants,
has a recent history of intense price competition. Price discounting has
characterized the acrylonitrile market for some time. Price discounts, or
temporary voluntary allowances (TVA) as they are known in the chemical
business, usually amount to a 2.4 cents to 10 cents per kilogram undercut
9-56
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of the list price. Acrylonitrile producers, have made numerous attempts in
the past couple of years to eliminate these discounts and return prices to
their list level. These attempts have failed due to the competitive nature
of the acrylonitrile industry. During the summer of 1979, the list price
of acrylonitrile was raised by approximately 4.5 cents per kilogram because
of increasing demand and jumps in the price of the main feedstock, propylene.
This constituted the first major price increase by acrylonitrile producers
since the winter of 1976.
With full-cost pricing practices, oligopolistic coordination is enhanced
because it makes the competitors' decisions more predictable. Such prac-
tices also provide common guidelines concerning what constitutes appro-
priate price levels. This is especially true if both the same costs pervade
throughout AO chemicals production plants and the same full cost pricing
rules are used.
A good example of pricing under barometric price leadership is the
case of phenol, which is produced-by 12 firms. Allied Chemical owns the
largest single share of capacity,! but only 17 percent of the total. The
chronology of events below exemplifies, the oligopolistic uncertainties of
price setting.
Dow Chemical, which owns 14 percent of the total phenol capacity, an-
nounced in early September 1979 that it would raise its price 7.7 cents per
AQ
kilogram on October I, bringing the list price to 83.6 cents per kilogram.
Dow cited increased costs as the reason for raising its phenol price.
Union Carbide had'" just boosted its price on phenol's feedstock, cumene,
because of cost pressure from its feedstock, propylene.
The other chemical producers of phenol did not raise their prices
immediately, taking the "wait-and-see" approach. Most suppliers need to
notify customers of price changes only 15 days in advance.
By the end of September, all but two domestic phenol producers (Getty
and Shell, 17 percent-of total capacity combined) said they would post a
list price of 83.6 cents per kilogram on October 1 in accordance with Dow's
initial move. The week before, a large phenol seller said that it would
post a TVA of 4.4 cents, making for an effective listing of 79.2 cents per
kilogram, but by the end of the week had reconsidered and set a straight
price of 83.6 cents per kilogram.49
9-57
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Since Shell and Getty held back on increasing the price on October 1,
the new 83.6 cents per kilogram price, which was implemented by the other
producers, did not stick. All producers discounted the price to remain
competitive. Then, in the middle of October, Shell and Getty notified
their customers that they would boost the price of phenol to 83.6 cents per
kilogram on November 1.
Meanwhile, phenol buyers said that the 83.6 cents per kilogram price
was too high and would not survive. They pointed out that the downstream
users of phenol (it is mainly used as a resin) never experienced the tight
markets that phenol sellers enjoyed earlier in the year and were never able
to pass on the price hikes that took place at that time. Further, the
83.6 cents per kilogram price was considered unrealistic because an addi-
tional 302 gigagrams of phenol capacity (a 20 percent increase) were due to
come onstream in the near future. Given the inability to pass on phenol
price increases, the excess phenol capacity, and the raising of interest
rates by the Federal Reserve Board that might adversely affect the important
end-use markets of automobiles atid housing, the price increase appeared not
*
to have a chance. _" v
By the end of October, Dow, which initiated the original price increase,
was first to officially acknowledge the weakness of the phenol market and
post a TVA. On November 1, the company's list price was discounted 4.4 cents
per kilogram. The other phenol producers soon followed Dow's lead.
The phenol example exemplifies a number of characteristics of baro-
metric price leadership and how AO chemical prices are set. First, the
producer with the most production capacity is not necessarily the one that
initiates a price increase or decrease. Second, price increases usually
are based on costs, with the producer attempting to maintain a full-cost or
cost-plus margin. Third, some producers may not follow a price leader's
direction immediately, taking a "wait-and-see" strategy. Fourth, the use
3 • l
of temporary voluntary allowances is common and the list price usually is
not the selling price. Fifth, supply situations (e.g., overcapacity) and
downstream market demand conditions have an important effect on selling
price and, at times, overrule the producer's full-cost or cost-plus pricing
decision. Finally, the large volume AO chemical producers set prices
non-collusively, but usually end up selling the product for the same price.
9-58
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9-1-13 International Considerations
In 1978, the United States experienced a total trade deficit of $28.5
billion, primarily because of the large amount of imported oil. Even
though the oil; import costs were reduced by $2.84- billion over 1977 costs,
they still accounted for a $39.5 billion cash outflow in 1978.52 Other
sectors of the economy had a dismal international trade year in 1978 as
well. The manufacturing sector ran a balance of trade deficit that was the
largest in recent years. Automobiles, textile goods, and tires all had
record deficits.
The biggest bright spot with regard to the United States manufacturing
balance of trade is the chemical industry. With exports valued at $14.6
billion and imports at $7.1 billion, the chemical industry showed a net
balance of trade surplus of $7.5 billion.53 Exports in 1978 increased by
$2.06 billion over 1977 exports. Imports also were on the rise, showing a
$1.04 billion increase.54 It is interesting to note that, since 1975, the
U.S. balance of trade has shown-;a continual increase in its deficit (imports
are rising at a faster rate thaftpports), while the chemical industry has •
experienced a continual increasS Sn its trade surplus (exports are increasing
at a faster rate than imports).-.
The International Trade Commission places individual chemical products
into groups according to the Standard International Tariff Classification
(SITC). All of the AO chemicals fall under SITC No. 512, entitled "Organic
Chemicals." Organic chemicals make up about 25 percent of the total chemical
industry's exports and imports. In 1978, $3.37 billion worth of organic
chemicals were exported and $1.73 billion were imported for a total surplus
of $1.64 billion. This was a slight decline from the 1977 balance of
trade surplus valued at $1.79 billion.
Table 9-14 shows imports and exports for major AO chemicals. 1,3-Buta-
diene is the largest valued import, representing 36 percent of the total
dollar amount j>f organic imports. Styrene is the largest valued export,
representing 2$ percent of the total dollar amount of organic exports.
Most commodities produced by the chemical industry that use AO chemi-
cals as production materials also experienced balance of trade surplus.
Plastics and resins (SITC No. 581), a large customer for AO chemicals, had
a surplus of $ll57 billion.56
9-59
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TABLE 9-14. AO CHEMICAL EXPORTS AND IMPORTS
19 AO Chemicals
United States
1978
Chemical
Acetal dehyde
Acetic acid
Acetone
Acrylic acid
Acrylonitrile
1,3-Butadiene
Dimethyl terephthal ate
Ethyl ene di chloride • ''•* f
Ethyl ene oxide v
Formal dehyde
Formic acid
Isophthalic acid
Maleic anhydride
Methyl ethyl ketone
Phenol
Phthalic anhydride
i Propylene oxide
s
1 Styrene
Exports
(Megagrams )
NA
7,730
54,710
4,605
135,036
NA
90,594
310,582
34,719
10,448
3,200
1,985
1,309
15,517
104,077
420
34,219
358,045
Imports
(Megagrams)
4
25,637
630
NA
1,501
282,202
NA
NA ,
427
1,107
NA
NA
3,535
24,773
83
18,315
15,920
13,982
; NA = Information is not available.
".SOURCE: U.S. Department of Commerce.
Publication FT410. 1978.
U.S. Exports.
9-60
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Still, the United States ranked second to West Germany in 1978 as a
chemical exporting nation, but this may change soon. U.S. chemical exports
in 1979 are expected to have their best year yet, reaching from $16 billion
to $17 billion. With imports estimated at $5 billion or less, the chemical
industry may have a remarkable $12 billion trade surplus.57
The main reason for the large success of SOCMI exporters is the cost
of feedstocks. In 1974, the Organization of Petroleum Exporting Countries
restructured world oil prices in such a way that U.S. chemical producers
have a large feedstock cost advantage over their foreign counterparts.
More important, U.S. government oil and gas price controls serve as an
indirect subsidy to American chemical producers and contribute heavily to
the differences in international chemical prices.
The European Community is the hardest hit by feedstock cost differences.
Europe is an important market, accounting for 28 percent of all chemical
exports. Petrochemicals constitute a large portion of this total and they
include SOCMI organic intermediates. In the United States, producers are
able to sell these chemicals for»|two thirds the price of comparable European
products. Table 9-15 shows prieel comparisons for some major AO chemicals.
U.S. chemical companies contend that government energy price regula-
tions are not the main reason for the differences in chemical prices ~
that better technology, economies of scale, and a better inter-plant distri-
bution network all contribute to lower costs. The weakness of the dollar
in the European market also contributes to the large price differences. In
addition, chemica-1 producers are quick to point out that the United States
has an advantage due to feedstock flexibility. European producers have
been dependent upon naphtha as their main feedstock. A severe shortage of
naphtha resulted when Iranian oil supplies were cut off and the spot price
of naphtha more than doubled within a year, causing the price of downstream
chemicals to skyrocket. The Europeans particularly were hurt because Iran
supplied 14 percent of their crude oil last year. However, it is hard to
dispute the fact that the U.S. advantage in crude oil price, which is about
$18.87 per cubic meter ($3.00 per barrel), is the main reason for chemical
price differences.
The future, however, should improve for European chemical producers.
Naphtha should become more available and European refineries are installing
9-61
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TABLE 9-15. U.S. AND EUROPEAN PRICE DIFFERENCES
FOR AO CHEMICALS
4 AO Chemicals
1979
Chemical
Styrene
Phenol
Terephthalic acid
Butadiene
Relative
($ per
U.S.
495
540
460
460
prices
Mq)
Europe
605 - 620
680 '
620
530
First-quarter 1979 dollars.
SOURCE: Chemical Industry Girds to Defend Exports. Chemical
& Engineering News. P. 14. October 22, 1979.
9-62
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additional capacity that has feedstock flexibility. The dollar should
become stronger relative to European currencies, but this is difficult to
predict. The big factor will be the deregulation of U.S. oil and gas
prices, which should narrow considerably the chemical price difference
between the United States and Europe.
Even though U.S. chemical exports to Europe may have reached the high
water mark, the total amount exported still should remain fairly high for
the next five years. Deregulation of U.S. oil and gas prices will be
phased in and exports to other areas of the world should remain strong.
The United States is well protected from SOCMI imports by protective
tariffs. This is especially true with regard to the benzenoid imports
category, which contains many of the AO chemicals. Benzenoid includes any
chemical whose molecular structure has one or more six-membered carbocyclic
or heterocyclic rings with conjugated double bonds (e.g., the benzene ring
or the pyridine ring). Until recently, tariff valuation for benzenoid
chemicals was extremely protective under the American Selling Price (ASP)
system. The ASP customs valuatkyi system was implemented in 1922 and is
applied only to those benzenoid "imports that are labeled "competitive" with
similar products made in the United States.
The ASP included both a specific duty (so many cents per kilogram) and
an ad valorem duty (a percentage of the domestic price). For example,
maleic anhydride in 1978 had a specific duty of 3.7 cents per kilogram and
an ad valorem rate of 12.5 percent.58 With a domestic price of 61.6 cents
per kilogram, the.-tariff would amount to. 11.4 cents per kilogram. This
means that foreign competitors would face a tariff cost representing approxi-
mately 20 percent or more of their selling price, making it difficult for
foreign producers to make a profit.
Recent multilateral trade negotiations conducted in Tokyo and Geneva
have scrapped the ASP system and replaced it with a new set of tariffs that
became effective on January 1, 1980. However, many benzenoid chemicals
will be exempt from the new duty rates, having been withdrawn from trade
negotiations. These benzenoid chemicals represented a $226 million portion
of the $688 million in dutiable benzenoid imports during 1976.59 The other
benzenoid imports classified as "competitive" no longer would be dutied
using the ASP system. Instead of applying an ad valorem tariff rate on the
9-63
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domestic price of the chemical, the rate is computed using the foreign
invoice price. It was shown that maleic anhydride under the ASP system
would have a tariff duty of 11.4 cents per kilogram. If the foreign invoice
price was 11 cents per kilogram less than the U.S. price, the tariff duty
would drop to 10.1 cents per kilogram. However, new tariff rates have been
drawn up that protect these benzenoid chemicals almost as much as under the
ASP system.
A tariff-cutting formula was implemented on chemicals other than
benzenoids that cut high existing tariffs by a greater percentage than low
existing rates. The average U.S. duty rate on dutiable chemical imports
from non-communist countries was about 10.5 percent of domestic price
before the trade negotiations were completed. This percentage has been
lowered to slightly less than 7 percent of domestic price, representing an
average reduction of 34 percent. The average duty rate on imports from
the European Community and Canada is now 7 percent, and from Japan, 7.5
percent. This is a reduction from the former average duty rate of 11
percent for European and Japanese^imports and 13.5 percent for Canadian
»
imports. " v
One of the major uses for "the AO chemicals, resin and plastics, had
import duties averaging 9 percent ad valorem before the trade pact. Now
the average duty rate has been reduced to slightly more than 5 percent.
Table 9-16 shows new tariff duty rates decided during the trade negotia-
tions for some AO chemicals and some of the resin types that are produced
using AO chemica.ls. The rates did not change substantially from the previ-
ous system.
Even though tariffs have been decreased in some instances by the
recent trade pact, the AO chemical intermediates and their end-use chemical
products are still very well protected. This is especially true.for chemi-
cals classified as benzenoid products. Chemical producers have lost very
little ground in the recent trade negotiations, although certain concerns
remain. One of these, price inflation., has been remedied by the tariff
negotiations. Formerly, the tariff duty as a percentage of domestic price
varied inversely with an increase in price, due to the use of a specific
duty. For example, acetaldehyde had a specific duty of 3.3 cents per
kilogram plus an ad valorem duty of 7.5 percent. In 1972, it sold for
9-64
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TABLE 9-16. OLD, CURRENT, AND PROPOSED TARIFFS
6 Chemical Commodities
United States
Commodity
Acetaldehyde
Ethyl ene glycol
Propylene glycol
Polyethylene
resins
Acrylic resins
Mel ami ne resins
Effective January
ad valorem rate).
Converted
rate
Old rate (%)
3.3
-------
about 19.8 cents per kilogram and the tariff duty amounted to 4.8 cents per
kilogram (or 24 percent of the price). In 1978, acetaldehyde sold for
44 cents per kilogram. -The tariff duty rose to 6.6 cents per kilogram, but
this represented a much smaller percentage of the price (15 percent).
Increasing prices mean smaller tariffs (in percentage terms); obviously,
producers were concerned.
The new agreements have done away with specific duties. With only ad
valorem rates, domestic price increases will not affect tariff incidence,
which is a relief to chemical producers, especially in light of the rapid
increases in oil prices recently.
Another problem that chemical producers face — one that was not
corrected by the trade agreement — is the growing competition from govern-
ment-operated plants. For example, 13 percent of the total world ethylene
oxide capacity in 1976 was controlled by foreign governments. This share
is expected to increase to 24 percent by 1983 based on known expansion
plans. The concern is that government-subsidized plants may not conduct
business with a profit incentive*jn mind, but may instead consider full
employment or a healthy balance-o^F trade to be the prime objective.
On the export side, U.S. chemical" companies have complained about the
use of health and safety regulations to prevent imports from entering
foreign countries. The new trade agreement has countries pledging not to
use such regulations for the sole purpose of blocking imports. Violators
of this pledge would face retaliatory trade bans.
Finally, and_of particular relevance to this study, exporters are con-
cerned with meeting environmental costs that their foreign competitors do
not face. Although no specifics are available, Rep. Kenneth L. Holland
(D, S.C.)j a member of the House Ways and Means Committee, is suggesting "a
delicately fashioned tax-relief code" that would not be labeled an export-
go
subsidy measure to help chemical exporters.
These problems do not seem major, however. Given the exclusion of
many benzenoid products from the new trade pact, the relatively small
decreases in most tariff rates, and the strong cost advantages AO chemical
producers have over European competitors, the balance of trade for the
chemical industry surplus should remain large through the next five years.
9-66
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9.2 ECONOMIC ANALYSIS OF SOCMI AIR OXIDATION NSPS
9-2-1 Summary of the Economic Effects of the SOCMI Air Oxidation NSPS
Thirty-six air oxidation industries are examined for possible adverse
economic effects due to the NSPS. It is estimated that if all new AO
facilities are controlled, the maximum total annualized costs would be $67
million (before-tax 1978 $) in 1986. Also, it has been determined that no
AO chemical price would increase by 5 percent or more due to the NSPS, that
the decline in profitability would be insignificant, that chemical firms
should be able to raise the needed capital to finance pollution control
expenditures, and that any changes in foreign trade due to the standard
would be minimal.
9.2.2 Economic Impact Analysis of the SOCMI Air Oxidation NSPS
The analysis of regulatory alternatives is based on the use of a
single Volatile Organic Compound (VOC) control technique, thermal oxida-
tion. Each regulatory alternative specifies a percentage reduction of
national VOC emissions. Reductions will be achieved by requiring that a
percentage of AO facilities use Dermal oxidation to reduce waste stream
•^ ^*
VOC emissions. The regulatory alternatives range from a national VOC
reduction of approximately 72 percent (the current baseline level) to a VOC
reduction of approximately 99.4'percent from uncontrolled emissions (the
.highest level achievable using thermal oxidation at all AO facilities).
The 1986 total annualized control costs for eight levels of national control
are presented in Table 9-17; Figure 9-4 presents the calculations in graphic
form.
The regulatory alternatives are established based on the concept of a
total-resource-effectiveness (TRE) floor. Information concerning 59 existing
facilities producing AO chemicals was used to construct a national statis-
tical profile, which then was used to compute a TRE index. The index
serves to distinguish between those affected facilities that would have to
install controls and those that would not. An owner or operator of an
affected facility with a TRE index below the chosen value (following final
product recovery) would have to reduce VOC emissions by 98 percent or to 20
parts .per million by volume (ppmv) by compound (measured by molecule instead
of by atom), whichever is less stringent. TRE is a measure of the total
resource requirement per unit VOC reduction associated with VOC control by
9-67
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9-68
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PERCENT REDUCTION IN
EMISSIONS OVER BASELINE
100
10
15
55 SO 65 70
COST
Millions at Collars in m« Fifth Yaw
FIGURE 9-4. FIFTH YEAR ANNUALJZED CONTROL COSTS AND NATIONAL
PERCENT EMISSIONS REDUCTION
TOTAL RESOURCE-EFFECTIVENESS APPROACH
UNITED STATES
DECEMBER 1,1986
9-69
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thermal oxidation. The TRE index of an affected facility is proportional
to its projected annualized cost per unit VOC reduction (facility cost-
effectiveness) associated with thermal oxidation at 98 percent control
efficiency. The TRE index of a facility is equivalent to the facility
cost-effectiveness, multiplied by 100, and divided by $88.7 thousand per
megagram. The $88.7 thousand per megagram value represents the highest
facility cost-effectiveness of any vent stream in the national profile with
a VOC concentration above the detectable limit. (A more detailed discussion
of how the regulatory alternatives are established is in Chapter 6.)
A detailed microeconomic analysis is not performed on each regulatory
alternative because of the number of alternatives (seven) from which to
choose and the number of different industries affected (36). Instead, the
most stringent regulatory alternative is evaluated; hence, it is assumed
that all future sources using the AO process will have to comply with the
standard and reduce emissions by 98 percent or to 20 ppm by compound,
whichever is less stringent. An. economic screening analysis is conducted
using four microeconomic criteriX to ascertain whether any individual
chemical industries would suffer* Adverse economic consequences. A "worst-
case" approach defines the numerical thresholds that are used to screen out
those industries that would not; be affected significantly by the NSPS. If
any one of the four screening criteria is triggered, the individual chemical
industry is studied, in more detail. The economic areas for which criteria
are established include:
• Price increase
• Profitability decline
• Capital constraints
• Foreign competition.
The screening results are combined quantitatively to provide an overall
ranking of the chemical industries. The ranking shows those chemical
industries having the greatest potential for adverse economic effects from
the NSPS.
The remainder of Section 9.2 describes the methodology used to imple-
ment the screening analysis, then presents both the results of the screening
and the ranking of the 36 chemical industries in order of their potential
9-70
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for experiencing an adverse economic effect. Section 9.2 also examines
more closely those chemical industries having the greatest potential for
adverse economic effects. Section 9.3 describes aggregate and socioeconomic
effects: total annualized cost, employment impacts, inflation resulting
from the standard, and small business impacts.
The major conclusion reached is that there is little chance of major
economic consequence for any of the 36 AO chemical industries due to the
NSPS. The results indicate that, based on reduced profitability, a phenol
facility might be built if the NSPS did not exist, but would not be built
if the NSPS is imposed and if capacity utilization for the industry is low.
However, the phenol industry impact due to the NSPS should not be over-
stated. The maximum price increase is projected to be only 0.9 percent in
1986 and the return on investment for the phenol producing process drops
only 0.5 percent when control costs are imposed. Also, the only AO process
producing phenol, the cumene hydroperoxide process, delivers acetone as a
coproduct. Thus, control costs imposed on phenol may be shared with ace-
tone.
9.2.3 Price Increase . T!
This section attempts to estimate, for each of the 36 chemicals, the
highest possible price increase:" caused directly by the AO NSPS. The price
criterion states that if the worst-case annualized control cost in 1986 as
a percentage of the projected 1986 price is greater than 5 percent for any
chemical, that chemical industry should be scrutinized on a more detailed
level. In many past government analyses, the 5 percent figure has been
used as a generally accepted criterion for determining if a price rise is
significant.
Certain conditions must be made explicit. Control costs are assumed
to be passed through totally, without any decline in the quantity of the
chemical demanded (i.e., the demand curve is assumed to be totally inelastic).
It also is assumed that, in some cases, a return on the investment in
control equipment exists due to heat recovery. Energy credits from the
operation of the control equipment, expressed in monetary terms, are de-
ducted from the control operating expenditures. When these conditions are
met, control costs per unit produced, as a percentage of price per unit
sold, are equivalent to a percentage increase in price due to the NSPS.
9-71
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Any chemical industry whose maximum price increase is less than 5
percent is noted but not examined in depth in the price increase analysis.
It is assumed that, given the worst-case parameters and a maximum price
increase of less than 5 percent, the chemical's price rise would not cause
any economic hardship downstream.
9.2.3.1 Price Increase Methodology. The cost of control is annualized
using a capital recovery factor of 0.152, which represents an 8.5 percent
after-tax interest rate and a 10-year life for the control equipment (con-
trol costs are presented in Chapter 8). The 8.5 percent after-tax interest
rate is a real rate — a 15.0 percent nominal after-tax rate adjusted by an
assumed inflation rate of 6.0 percent.* An after-tax rate is used because
it represents the actual opportunity cost to the investor.
In order to put the annualized control cost on a per kilogram product
basis, the smallest existing facility size for a given chemical industry is
used. This is equivalent to saying that any new-facility built would be
the same size as the smallest existing facility; this is a worst-case
assumption because new facilities usually are larger on average than their
predecessors and almost always arfe larger than the smallest existing facil-
ity. Where facility size data .are not" available, a 1.4 gigagrams per year
production rate is used, representing the size of the smallest AO facility
for which data are available (a hydrogen cyanide facility).
Projected 1986 market prices are used to compare the unit cost of
control with unit price. Mid-year 1978 market selling prices (which may be
found in Table 9-13) are used as the base from which 1986 prices are pro-
jected. The rise in the prices of SOCMI chemicals is expected to exceed
the general rate of inflation. The use of full-cost and cost-plus pricing
implies that prices should increase at about the same rate as costs.
Because raw materials comprise most of the production costs for SOCMI
chemicals, the price of the chemical and the raw material should track very
closely.
The raw material most often used in the production process (either oil
or gas) is determined for each chemical. Chemical prices are derived by
To convert a nominal interest rate to a real interest rate, one plus the
nominal rate is divided by one plus the expected rate of inflation, and the
result is subtracted from one.
9-72
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. escalating the 1978 market price by the projected percentage increase (in
real terms) of each chemical's major raw material. In real terms, the
price of crude oil is projected to increase by 146 percent from $2.04 per
gigajoule ($12.50 per barrel) in 1978 to $5.03 per gigajoule ($30.80 per
barrel) in 1986 (in 1978 dollars).63 Gas prices are expected to increase
206 percent from $1.56 per gigajoule in 1978 to $4.74 per gigajoule in 1986
(in 1978 dollars). 4 The 1986 projected chemical prices are given in
Table 9-18.
9-2.3.2 Results of the Price Increase Screening. The price increase
screening is carried out in three steps. First, an initial tabulation of
control costs is generated using some worst-case assumptions. Two chemi-
cals, made by three AO processes, experience price increases of greater
than 5 percent: maleic anhydride via the benzene process (5.9 percent),
maleic anhydride via the n-butane process (5.5 percent), and phthalic
anhydride via the xylene process (5.3 percent).
The second step involves calculating a "rolling" cost. One of the 36
chemicals produced by an AO proems, acetaldehyde, is used as feedstock for
another AO chemical, acetic acid;!5 thus, the control cost per kilogram
should be accumulated and divided by the price per kilogram of the down-
stream chemical. Accordingly, the downstream chemical's price should
increase by more than its own control cost because it is passing on, in
addition to its cost of control, the increased cost of feedstocks. A
rolling cost is used in this instance to calculate the total effective
percentage price,increase of acetic acid resulting from its own VOC control
plus the increased cost of acetaldehyde. A rolling cost does not force the
acetic acid price over the 5 percent threshold. Results after the two
steps are used as inputs for a ranking of the 36 AO chemical industries
according to potential adverse economic effects (see Section 9.2.7).
The third step examines in more detail those chemicals that are found
to have price increases of greater than 5 percent as determined in steps
one and two. For maleic anhydride via the benzene process, maleic anhydride
via the n-butane process, and phthalic anhydride via the xylene process,
worst-case assumptions are replaced by more realistic assumptions and the
price effects are reevaluated. Using more realistic control costs, maleic
anhydride via the benzene process has a 4.2 percent price rise, maleic
9-73
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TABLE 9-18. PROJECTED AO CHEMICAL PRICES IF
EXPECTED INCREASES IN OIL AND
NATURAL GAS PRICES ARE PASSED
THROUGH
36 AO Chemicals
United States
December 1, 1986
Chemical
Price
(4Ag)
(1978 S)
Acetaldehyde
Acetic acid
Acetone
Acetonitrile
Acetophenone
Acrolein
Acrylic acid
Acrylonitrile
Anthraquinone
Senzaldehyde
Senzoic acid
l,3-3utad1ane
p-t-8utyl benzole acid
n-3utyr1c acid
Crotonic acid • -^
Curene hydroperoxide . _
Cyclohexanol
Cyclohexanone
Dimethyl terephthalate ~
Ethylene dichloride
Ethylene oxide
Formaldehyde (lOOt solution)3
Formic acid •
Glyoxal (100S solution)15
Hydrogen -"cyanide
Isobutyric acid
Isoplrthalic acid
Maleic anhydride
Methyl ethyl ketone
a-Methyl styrene
Phenol
Phthalic anhydride
Propionic acid
Propylene oxide
Styrene
Terephthalic acid
97.7
81.9
38.3
224.6
195.3
172.9
173.7
124.7
308,7
467.6
161.9
10S.3
346.6
158.4
419.2
150.3
130.6
179.1
115.6
44.5
121.0
92.6
124.2
451.4
200.4
366.0
144.4
126.9
103.1
97.7-
90.5
133.3
92.3
117.1
97.7
124.2
Usually formaldehyde is sold as a 37% solution (37% formaldehyde, 53%
water and irethanol). The price of the solution is divided by 0.37 to
obtain a 100? solution (pure fornaldehyd'e) price because control costs
are calculated on a 1005 solution basis.'
Usually glyoxal is sold as a 40S solution (40% glyoxal, 505 water and
methanol). The price of the diluted solution is divided by 0.40 to
obtain a 100% solution (pure glyoxal) price because control costs are
calculated based on a 100% solution basis.
9-74
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anhydride via the n-butane process, 3.1 percent, and phthalic anhydride via
the xylene process, 3.5 percent. The third step calculations are reiterated
in Section 9.2.8 (Individual Chemical Analysis). JTable 9-19 presents the
results of the price increase calculations for all 36 chemicals that use"
various AO processes. ;
9-2.3.3 Sensitivity Analysis. The value of '• each of three control
cost parameters is increased independently to determine if a chemical's
percentage price change is sensitive to the individual parameter. The
three parameters include: the interest rate used[for discounting, the
natural gas price in 1986, and the F value used to predict the actual
offgas flow rate. In conducting the sensitivity analysis, two parameters
are held constant while the third is being tested. As a result, this
analysis only evaluates the sensitivity of the control cost to each para-
meter individually, and does not examine the combined influence of altering
two or more of these factors simultaneously.
real interest rate of 8.5
after-tax real interest
In the price increase analysis, an after-tax
percent is used. For the sensifii/ity analysis, an
rate of 10.8 percent is used. This is. equivalent:to a nominal after-tax
interest rate of 23 percent divided by an inflation rate of 11 percent —
the approximate situation in late 1980 when the prime interest rate reached
21 percent, the highest level ever reached in the United States. When an-
nual izing control costs using the 10.8 percent after-tax real interest rate,
no significant increase in any chemical's price results when these control
costs are passed'-through totally, nor do additional chemicals have price
increases greater than 5 percent. \
The price of natural gas is the main operating cost of control.
However, the natural gas cost represents only a portion of ^the total annual-
ized cost of control. The price of natural gas may prove to be less than
the 1986 projected $4.74 per gigajoule (1978 $) used in the analysis.
Also, because a few chemical prices are'based on natural gas and because
the price of gas is not totally independent of the oil price, the prices of
all chemicals are linked to the gas price. If chemical prices also are
lowered by the same rate as the natural gas price, control cost as a per-
centage of price (price increases) for all AO chemicals will be greater
than the results provided in Table 9-19. A 1986 gas price of $4.12 per
9-75
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TABLE 9-19. PERCENTAGE AO CHEMICAL PRICE INCREASES WHEN PRODUCERS
PASS THROUGH ALL'CONTROL COSTS
36 AO Chemicals, 2,9 AO Processes,
United States
December 1,: 1986
Chemical'
Price Increase
(X)
Acetaldehyde
Acetic acid (Wacker process) j
Acetic acid (n-butane oxidation process1)
n-Butyric acid (byproduct)
Formic acid (byproduct)
Methyl ethyl ketone (coproduct)
Propionic acid (byproduct)
Acetone (cumene hydroperoxide process) ;
Acetophenone (byproduct) ;
Cumene hydroperoxide (byproduct) ;
a-Methyl styrene (byproduct) '•* t ;
Phenol (coproduct) - * ;
Acrylic acid . ':
Acrolein (byproduct)
Acrylonitrile
Acetonitrile (byproduct)
Hydrogen cyanide (coproduct)
Anthraqui none
Benzaldehyde
Benzoic acid
* X
1,3-Butadiene
p-t-Butyl benzoic acid
n-Butyric acid
Crotonic acid
Cyclohexanol
Cyclohexanone (coproduct)
Dimethyl terephthalate
Terephthalic acid (coproduct)
Ethylene dichloride
Ethylene oxide
Formaldehyde (mixed metal catalyst process)
1.8
3.2b
2.0
1.9
1.3
1.6
1.8
0.8
0.4
0.5
0.8
0.9
1.1
1.1
1.3
0.7
0.8
3.0
1.9
2.7
3.8
1.2
1.9
0.6
0.4
0.4
1.1
1.0
(0.3)
1.0
3.0
9-76
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TABLE 9-19 (Continued). PERCENTAGE AO CHEMICAL PRICE INCREASES WHEN
PRODUCERS PASS THROUGH ALL CONTROL COSTS
36 AO Chemicals, 29 AO Processes,
United States
December 1, 1986
Chemical'
Price Increase
Formaldehyde (silver catalyst process)
Glyoxal
Hydrogen cyanide (Andrussow process)
Isobutyric acid
Isophthalic acid
Maleic anhydride (benzene oxidation process)
Maleic anhydride (n-butane oxidation process)
Phthalic anhydride (xylene oxidation process)
Phthalic anhydride (napthalene oxidation process)
7* f
Propionic acid (propionaldehyde ^oxidation process)
Propylene oxide (ethylbenzene oxidation process)
Styrene (coproduct)
(1.4)
2.1
(2.9)
1.0
2.0
4.2
3.1
3.5
2.2
0.7
0.8
0.9
( ) = price decrease
Chemicals that are coproducts or byproducts of a particular AO process
are indented. A single value of capital cost, annualized cost, and
operating cost is projected for such a process. In calculating the
control costs for byproducts and coproducts, the total annualized cost
for the process is attributed to each byproduct/ coproduct. Likewise,
the_total production of all byproducts and coproducts is used in calcu-
lating the control cost of each byproduct/ coproduct. Therefore, the
control costs of the byproduct(s)/coproduct(s) are equal. Usually a
pollution control cost will be passed on through the primary product
and the price of the byproduct will remain the same and in the case of
coproducts the price increase will be shared more or less equally. By
using the above method, for calculating control costs very conservative
price increase results occur for byproducts and coproducts.
Some chemicals are produced by more than one AO process and thus have
multiple price increases. Price rise differences may be a preliminary
indication of possible process substitutions. Chapter 5 (Modification
and Reconstruction of Existing Facilities) gives a current account of
the types of AO processes used to make a.chemical.
1.1 kg of acetaldehyde is used to produce 1 kg of acetic acid in the
Wacker process. Hence 1.1 x control cost of acetaldehyde is added to
the control cost of acetic acid to compute price increase.
9-77
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gigajoule (1978 $) is used to determine if the chemical price increase
would be substantially greater than that determined in the normal analysis.
(The $4.12 per gigajoule 1986 gas price represents approximately the lowest
Department of Energy projection.) The net result, when the $4.12 per
gigajoule natural gas price is used, is no significant additional price
increases when control costs are passed through totally. No additional
chemicals have price increases greater than 5 percent, and it is concluded
that the price increase is not very sensitive to changes in the price of
natural gas.
The one parameter that produces the greatest disruption in the price
increase conclusions is the F value. Because the actual flow rates for
some chemicals are confidential, a statistical prediction formula for F is
developed. The formula is-the ratio of actual offgas flow rate to stoichi-
ometric offgas flow rate. The screening methodology relies on control
costs developed using the central predicted values of F. When a high value
of F, based on the upper 95 percent confidence limit, is used to calculate
control costs, the price'increasesdue to the cost of control is significant-
' -< *-
ly higher. Two additional chemicals experience a price rise of greater
than 5 percent: anthraquinone"(5.4 percent), and formaldehyde (metal oxide
catalyst) (6.5 percent). Further economic examination of these two chemi-
cals is not conducted in Section 9.2.8 due to the extremely conservative
assumptions used when calculating the upper F value. The chance of the
upper F value occurring is too small to warrant a detailed economic analy-
sis for anthraquifione and formaldehyde. A detailed description of the F
predictor is included in Chapter 8.
To summarize, the price increase screening analysis results are insen-
sitive to the 1986 projected price of natural gas as well as the interest
rate used to discount future prices. However, when an F value based on an
upper 95 percent confidence limit is applied, price increases due to the
cost of control become much greater than when a central value of F is used.
9.2.4 Profitability Decline
The key factor in the decision to build a new facility is whether the
investment will be profitable. Profitability may be estimated by calculating
the net present value (NPV) of future returns. Future returns are defined
as the net income after taxes, plus depreciation, that result from an
9-78
-------
investment in a facility, and are discounted at the appropriate interest
rate to-calculate the NPV. If the NPV of a proposed facility is positive,
the facility should be profitable; if negative, the facility would not be
profitable. To determine if the additional costs of pollution control
equipment will have adverse effects on investment decisions for SOCMI,
NPV's are calculated for facilities with and without the control technology
required by the regulatory alternative currently under consideration.
9-2.4.1 Profitability Decline Methodology. NPV calculations for
SOCMI chemicals are based upon facility cost and sales estimates developed
by Stanford Research Institute's (SRI) Process Economics Program. The
facility data cover 12 AO processes representing an estimated 75 percent of
the total number of AO processes to be used in projected new facilities
from 1981 through 1986.* The data are considered proprietary.
The SRI facility cost data include the following estimates:
« Fixed investment — the capital requirement for the facility and
equipment in a new facility-.
• Total investment — the sum if fixed investment plus inventory
'. v
• Product cost ~ the cost of production (including depreciation) after
deducting credits for byproducts. SRI's product cost assumes 100
percent capacity utilization; it has been adjusted to represent a
facility running at a weighted average capacity utilization rate (see
Section 9.1;for a discussion of how weighted average capacity utiliza-
tion rates are figured).
The NPV formula for determining profitability, as well as a detailed
explanation of h4w it Works, is presented in Appendix A. Cash outflows are
estimated on the'basis of these three items and are stated in 1978 dollars.
(All cost data were updated to 1978 using cost indices provided by SRI.)
By using SRI facilities, a conservative assumption probably is made about
profitability. Newly constructed AO process facilities should be more
cost-efficient per unit produced than the existing facilities on which SRI
bases its facilities. Also, the facility sizes used in calculating NPVs
are at the smaller end of actual facility size range, while new plants are
usually on the larger end of the range because firms try to capture econo-
mies of scale.
The 75 percent figure is obtained by dividing the number of new facilities
projected to be built (see Section 9.1) using AO processes that the SRI
data cover by the total number of projected new facilities
9-79
-------
Theoretically, depreciation is not treated correctly in the NPV calcu-
lation because of some simplifying assumptions that are made. In the NPV
formula, SRI production quantities and costs are reduced to reflect histori-
cal capacity utilization rates for individual chemical facilities. In
reducing costs, the depreciation included in costs also is reduced; this is
not appropriate because depreciation is a fixed cost that does not vary
with production volume. Thus, costs are understated and NPV's are over-
stated.
However, this simplification will not affect the NPV results signifi-
cantly for two reasons. First, for many chemicals it is estimated from SRI
data that depreciation is only about 10- percent of net production costs.
This means that costs, when reduced to conform with historical capacity
utilization rates, are understated by only to 2 to 4 percent. Second, all
cost components, some of which include depreciation, are inflated annually
at 13.2 percent in the NPV formula. This results in overstated costs and
an understated NPV, more than offsetting the overstated NPV caused by the
previously discussed cost-reducing simplification. The 13.2 percent over-
statement of depreciable costs 6*uiweighs the 10 percent understatement of
depreciable costs. Neither error makes a significant difference in the NPV
result.
Cash inflows primarily are sales revenues estimated by multiplying the
average unit price by the average annual production volume. 1978 prices
are obtained from the International Trade Commission (see Table 9-13).
Production volume.-is derived by assuming that a facility will run at the
chemical's weighted average capacity utilization rate.
All NPV estimates are in 1978 dollars and assume that 1978 is the year
in which an investment is made. Prices and costs are escalated from 1978
for 20 years (the life of the facility) at an annual rate of 13.2 percent.
The total inflation rate chosen is based on a combined 6.0 percent annual
general rate of inflation and a 6.8 percent annual real escalation rate
derived from the DOE oil price projection to 1995. While it is impossible
to forecast future inflation precisely, parallel indexing of both costs and
prices in the NPV analysis will minimize any error from this factor.
Using the formula for the NPV calculations found in Appendix A to
Chapter 9, two groups of NPV's are calculated: the baseline NPV's that
9-80
-------
reflect no additional investment requirements due to pollution control and
NPV's for plants under the worst-case assumption that additional investment
requirements and production costs imposed by the regulatory alternatives
cannot be passed on to consumers of the product. Also assumed is that the
quantity demanded of the product will not change. In the NPV formula, the
control technology is replaced after 10 years.
The profitability screening criterion compares the NPV with and without
control technology. A facility that maintains a positive NPV with emission
controls remains an attractive investment to firms such that the NSPS would
not negatively affect future construction of facilities. Also, a facility
that has a negative baseline NPV would not undertake a new investment,
thereby experiencing no major effect due to control costs. However, any
facility with a positive NPV before controls and a negative NPV after
controls is affected adversely and should be analyzed at a more detailed
level for a better assessment of economic impact.
The NPV's are calculated Initially at a 15 percent nominal after-tax
interest (hurdle) rate. If an wwestment shows a positive NPV at 15 per-
cent, any realistic interest ratal used that is less than 15 percent also
will give a positive NPV. This.is true because the NPV is related inversely
to the interest rate. A 15 percent nominal after-tax interest rate is
fairly conservative when the general inflation rate is assumed to be 6
percent. One source of data on the cost of capital to industry stalled that
the real after-tax hurdle rate for organic intermediates ranged from 11.2
percent to 14.1 .percent. A more recent source, collecting data from a
sample of 100 chemical manufacturing firms for 1977 and 1978, found that
the mean real after-tax cost of capital is 10.8 percent with a minimum cost
of capital of 8.1 percent and a maximum cost of capital of 12.8 percent.57
For any chemical process that has a negative baseline NPV using 15
percent, additional NPV's are computed using discount rates of 13.5 percent,
12 percent, 10.5 percent, and 9 percent. This is done to determine the
rate at which the investment might change from a positive NPV without
control costs to a negative NPV with control costs and to gauge the sensi-
tivity of NPV to changes in the interest rate.
9.2.4.2 Results of the Profitability Decline Screening. Table 9-20
lists the NPV's for 12 AO processes used to produce nine SOCMI chemicals.
9-81
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TABLE 9-20. NET PRESENT VALUES OF FUTURE FACILITIES, WITH
AND WITHOUT POLLUTION CONTROL
9 AO Chemicals, 12 AO Processes, 15 Percent Interest Rate
United States
1986
Chemical3
Acetic acid
i
Acetone
1,3-Butadiene
Ethyl ene oxide
Formaldehyde
Maleic anhydride
Phenol
Phthalic anhydride
Terephthalic acid
Process
A)
B)
A)
A)
A)
A)
B)
A) •:-
B) *f
A) ^
A) -'
A)
NPV without controls
(103 $)
•• 9,125.6
41,967.3
91,890.0
76,089.3
33,432.4
64,716.2
58,697.8
- 6,304.7
16,720.8
-.43,224.3
19,492.6
- 35,349.8
NPV with. controls
(1
-------
(See Table 9-21 for a list of process descriptions.) As Table 9-20 shows,
eight processes remain profitable at a 15 percent interest rate when pro-
ducers fully absorb the cost of the pollution control equipment. Acetic
acid (Wacker process), maleic anhydride (benzene oxidation process), phenol
(curaene hydroperoxide process), and terephthalic acid (p-xylene oxidation
process) all have negative NPV's with and without controls at a 15 percent
interest rate. Table 9-22 gives a range of after-tax discount rates that
change a profitable investment into an unprofitable investment when control
costs are imposed.
Acetic acid (Wacker process) has a negative NPV without control costs
at the lowest interest rate used, 9 percent. This implies that the facility
is an unprofitable investment, even without control costs added, and would
not be built. The formaldehyde facility using the silver catalyst process
experiences a control cost credit because of heat recovery; thus control
costs raise the net present value of the investment. Maleic anhydride
(benzene oxidation process) is affected adversely by the additional costs
of control at certain interest £a~tes. By interpolation, at some point
between a rate of approximately.^ percent and just below 9.0 percent, a
profitable investment becomes unprofitable due to control costs.*
Phenol (produced by the cumene process) also has a negative NPV with-
out control costs at the lowest interest rate used, 9 percent. This implies
that the facility is an unprofitable investment, even without control costs
added, and would not be built. Terephthalic acid (produced by the oxida-
tion of p-xylene) also is affected. For a future terephthalic acid facility,
*With the higher interest rate we equate the NPV without controls to zero
and at the lower range of the interest rate we equate the NPV with controls
to zero. For example, take the case of terephthalic acid A:
Interest Rate NPV without Controls NPV with Controls
12.0%
10.5%
9.9%
9.0%
<9.0%
Range: 9.9%
-18,095.7
- 5,938.2
0
9,539.9
-36,457.6
-27,143.4
- 15,171.8
0
- <9.0%
9-83
-------
TABLE 9-21. AO PROCESSES
9 AO Chemicals
United States
1978
Acetic acid
Acetone
1,3-Butadiene
Ethyl ene oxide
Formal dehyde
- .
Maleic anhydride
-
Phenol
Phthalic anhydride
Terephthalic acid
(A)
(B)
(A)
(A)
(A)
(A)
(B)
(A)
(B)
(A)
(A)
(A)
Process:
Inputs:
Process:
Inputs:
Process:
Inputs:
Process:
Inputs:
Process-:-
•f.
Inputs i, *
Process:
Inputs:
Process:
Inputs:
Process:
Inputs:
Process:
Inputs:
Process:
Inputs:
Process:
Inputs:
Process:
Inputs:
Wacker (catalytic oxidation of acetal-
dehyde)
acetal dehyde, catalyst, air
oxidation of n-butane
n-butane, air
cumene peroxidation
cumene hydroperoxide, sulfuric acid,
air
Phillips (oxidative dehydrogenation
of n-butenes)
n-tautenes, air, water, hydrogen,
furfural or acetonitrile
direct vapor-phase oxidation of
ethyl ene over silver oxide catalyst
silver, air, ethyl ene, steam, water
vapor, phase catalytic air oxidation
of methanol
mixed metal catalyst, methanol, air
vapor phase catalytic air oxidation
of methanol
crystalline silver catalyst, methanol,
air
oxidation of benzene
air, benzene, sodium perborate,
demineralized water
oxidation of n-butane
n-butane, air, catalyst
cumene peroxidation
cumene hydroperoxide, sulfuric acid, air
air oxidation of o-xylene in a fixed
catalyst bed reactor
o-xylene, air
air oxidation of p-xylene in the
liquid phase
p-xylene, air, acetic acid
9-84
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TABLE 9-22. HURDLE RATES AT WHICH NET PRESENT VALUES
OF FUTURE FACILITIES CHANGE FROM POSITIVE
(WITHOUT POLLUTION CONTROL) TO NEGATIVE
(WITH POLLUTION CONTROL)
4 AO Chemical Processes
United States
1986
Chemical process
After-tax nominal
hurdle rate (%)
Acetic acid A:
Maleic anhydride A:
Phenol A:
Terephthalic acid A:
<9b
<9-9.6
<9b
<9-9.9
See Table 9-21. for a list of process descriptions.
Acetic acid (Wacker process) add phenol (cumene process) show a
negative baseline NPV when a 9£fafter-tax interest rate is employed.
9-85
-------
an interest rate between 9.9 percent and less than 9 percent results in an
unprofitable investment.
9.2.4.3 Profitability Decline Sensitivity Analysis. When a sensi-
tivity analysis is done on those processes listed in Table 9-21, raising
the values of the natural gas price and the F ratio independently, no
additional chemical processes are affected under the profitability decline
criterion. A sensitivity analysis on the interest rate used for discounting
is included in the NPV screening analysis presented in Section 9.2.4.1 with
results given in Section 9.2.4.2.
9.2.5 Capital Constraints
The ability of a firm to raise capital to finance incremental control
costs is an important consideration in determining the economic impact of a
SOCMI NSPS. It is conceivable that a firm would find a new facility invest-
ment profitable, even with control costs added, but may not be able to
raise the extra capital needed to purchase pollution control equipment.
This is one of the most difficult impacts to measure because there are few
direct data upon which to draw.^fTo identify potential problems, the magni-
tude of the capital costs of the control technology relative to the fixed
investment costs without control is examined. There is no screening mech-
anism for readily identifying chemical industries that may have trouble
raising capital. Of the 12 model processes examined, the one with the
highest capital control cost-to-fixed facility investment ratio is analyzed
further for adverse economic effects. A 1,3-butadiene facility has the
highest ratio. It also is the only one with capital costs of control
exceeding 20 percent of the facility's fixed investment costs. The 20
percent figure should not be construed as either an absolute or relatively
significant threshold, but a cost analysis manual states that contingency
costs — the excess account set up to deal with uncertainties in the cost
estimate, including unforeseen escalation in prices, malfunctions, equip-
ment design alterations, and similar sources — are about 20 percent of
68
total direct and indirect costs. This implies that firms are either
prepared or already possess the ability to finance costs that range 20 .
percent above any investment they choose to undertake.
The 1986 estimated capital cost of control converted to 1978 dollars
(refer to Chapter 8) is divided by the fixed investment costs taken from
9-86
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SRI'S Process Economics proprietary information. It is assumed that a
replacement incinerator is not considered when a firm decides to make an
up-front capital outlay and that the capital control cost of the first
incinerator should not be added to the NPV of a second incinerator and then
divided by the fixed investment.
9.2.6 Foreign Competition
9-2.6.1 Foreign Competition Methodology. Imports and exports are
important variables to examine in this analysis because the emission stan-
dard is placed only on domestic plants. If domestic producers raise their
prices because of the extra cost of controlling pollution, they may be at a
competitive disadvantage with their foreign counterparts. Chemical exports
may suffer a decline if foreign customers substitute organic chemicals from
other countries. Also, imports from foreign countries into the United
States may increase, causing an adverse effect on our balance of trade.
The foreign competition criterion is defined such that any chemical
industry having imports and/or exports exceeding 10 percent o.f its total
U.S. production is examined furfur. The 10 percent figure is fairly
conservative when considering thVimportance of the foreign market as part
of the total market.
Fifteen chemical industries having import data available are examined
to see if imports in 1978, as a percentage of 1978 domestic production,
exceed the screening threshold figure of 10 percent (see Table 9-23). Only
two chemical industries, 1,3-butadiene and methyl ethyl ketone, fail the
screen and are examined further for possible adverse international economic
impacts. Of the 17 AO chemical industries that have export information
available, three fail the screen: acrylonitrile, styrene, and formic acid.
9-2.6.2 Results of the Foreign Competition Screening. It is important
to note that increases in costs due to emissions control do not 'influence
changes in the future balance of trade. Other overriding factors will
influence the SOCMI AO chemicals' position in the world market. As the
United States phases out oil and gas price controls, U.S. companies will
face higher feedstock prices that reflect the higher world oil price.
Therefore, the U.S. feedstock cost advantage will be eliminated, causing a
decline in the net balance of trade surplus. The chemical industries that
have significant levels of foreign trade (greater than 10 percent of domes-
9-87
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TABLE 9-23. IMPORTS AND EXPORTS AS A PERCENTAGE OF PRODUCTION*
19 AO Chemicals
United States
1978
Chemical
Acetal dehyde
Acetic acid
Acetone
Acrylic acid
Acrylonitrile
1,3-Butadiene
Cycl ohexanol/Cycl ohexanone
Dimethyl terephthalate/
Terephthalic acid
Ethyl ene di chloride
Ethyl ene oxide
Formaldehyde
Formic acid
Isophthalic acid
Maleic anhydride
Methyl ethyl ketone
Phenol
Phthalic anhydride
Propylene oxide
Styrene
Imports
. b
2.0C
0.8C
NA
0.2C
17.3a'c
b,c
b,d
:," NA
H b,c
- b,e
NA
NA
2.7C
10. 8a
0.2C
5.7C
b,f
0.5C
Exports
NA
0.6C
5.7C
3.5C
17.0a'c
2.9f
b,d
3.4C
6.2C
1.6C
0.4C
11.7a'C
3.2C
0.9C
5.7C
8.4C
NA
3.7C
11.4a'c
*Quantities are by volume; percentages are of total production by each chemical
NA ~ Not available
Affected chemical industries
Less than 0.05 percent
CU.S. Department of Commerce. Import Information was taken from "Benzenoid
Chemicals - Imports 1978"; Export information was from Publication FT410,
Schedule B.
Chemical and Engineering News. P. 11. March 26, 1979.
eChemical and Engineering News. P. 14. January 22, 1979.
Chemical and Engineering News. P. 13. July 24, 1978.
9-88
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tic production) all have a small cost of control relative to their 1986
projected price (less than 5 percent). These chemical industries are
discussed below in more detail. ;
l,3-6utadiene. In 1978, the amount of imported 1,3-butadiene equalled
17.3 percent of domestic production. The United States has been a net
importer of 1,3-butadiene since 1968.69 The quantity of imported 1,3-buta-
diene is tied closely to the demand for rubber and, therefore, the demand
for tires. In 1976, the rubber workers' strike resulted in decreased
demand for 1,3-butadiene and the closing of older facilities. Also, smaller
cars and radial tires have had an adverse effect on demand. These factors
have led producers to undertake new investments cautiously with the result
that the United States is unable to produce sufficient quantities to meet
domestic demand. In 1978, while U.S. facilities averaged 85 percent capa-
city utilization (full capacity for this industry) the United States im-
ported 282 gigagrams of 1,3-butadiene.
The origin, quantity, and varlue of 1978 1,3-butadiene imports are
listed in Table 9-24. The larg^si exporters to the United States were the
Netherlands and the United Kingdom, wtvich together accounted for more than
two thirds of total imports. There is no duty on 1,3-butadiene imports;
therefore, the United States is'expected to remain a net importer of 1,3-
butadiene. !
The cost of control for 1,3-butadiene is estimated to add a maximum
4.0 cents per kilogram, representing 3.8 percent of the 1986 projected
price. Growth rnrdemand is expected to be slow (2.5 percent per year);
therefore, a 3,8 percent or smaller increase in after-tax cost will not
affect significantly the U.S. position in the international 1,3-butadiene
market.
Methyl Ethyl Ketone. Import levels of methyl ethyl ketonejin 1978
reflect the tight supply that characterized the market in that year. New
capacity has come onstream since 1978 and has resulted in an export volume
that appears to be well above imports in 1979.70 The cost of cbntrol for
methyl ethyl ketone is estimated to be 1.5 cents per kilogram. I Although
the quantity of imports is decreasing, the standard's cost is insignificant
(1.6 percent of 1986 selling price) and will not influence trends in foreign
trade. '
9-89
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TABLE 9-24. 1,3-BUTADIENE IMPORTS BY COUNTRY OF ORIGIN
United States
1978
Country
Nether! ands
United Kingdom
France
Italy
Japan
West Germany
Norway
Brazil
Belgium
Taiwan
All Others
TOTAL
Quantity
(Gg)
123. 7
70.6
30.3
17.1
13.7
12.3
4.3
'^ 3.1
~v .1.8
1.0
3.0
282.0
Value
(10B $)
53.4
30.0
12.6
7.0
5.9
5.2
1.6
1.5
30.8
0.4
1.4
119.8
SOURCE: U.S. Department of Commerce. United States General Imports Schedule
A Commodity'"By Country FT/1351. December, 1978.
9-90
-------
Acrylonitrile. In 1978, exports of acrylonitrile exceeded 15 percent
of total U.S. acrylonitrile production. The quantity of exports was approxi-
mately 134.7 gigagrams, valued at over $60 million.71 More than one third
of these exports went to Canada and Mexico; western hemisphere countries
accounted for more than 60 percent of the. total exported volume.
United States acrylonitrile producers have done well in foreign trade
due to their feedstock cost advantage. The contract price for propylene in
the first quarter of 1979 was one third greater in Europe than in the
United States (see Table 9-25). The cost of control for acrylonitrile is
estimated to be, at most, 1.5 cents per kilogram, representing 1.3 percent
of the 1986 projected price. This small increase in cost, due to control,
should not affect significantly the ability of U.S. producers to compete in
the world market.
Styrene. In 1978, the United States exported approximately 357.3
gigagrams of styrene valued at $127 million. Styrene, a benzenoid deriva-
tive, still is protected.by tariffs despite recent tariff reductions. The
feedstock price advantage held by^U.S. producers explains the magnitude of
exports. Benzene and ethylene^ the feedstocks for styrene, are priced 17
percent and 65 percent greater,; respectively,, in Europe than in the United
States (see Table 9-25).
The cost of control is estimated to be 0.9 percent of the projected
1986 price of styrene; this increment should not affect the ability of U.S.
manufacturers to compete in foreign markets given the small percentage in-
crease in total cost and the large raw material advantage.
Formic Acid. Exports account for 12 percent of total domestic produc-
tion of formic acid. Compared to acrylonitrile and styrene, formic acid is
a low volume chemical. U.S. producers exported only three gigagrams of
this chemical.
The cost of control for formic acid is estimated to be 1.3 percent of
the projected 1986 price. This Is a small cost increase and would not
effect the level of exports of this chemical severely.
9.2.7 Ranking of Chemicals
A ranking scheme is developed to combine the various effects of the
NSPS on the SOCMI AO chemicals. The chemical industries ranked highest are
examined in more detail in Section 9.2.8 of the analysis for potential
9-91
-------
TABLE 9-25. CHEMICAL FEEDSTOCK PRICES
3 Feedstocks
United States vs. Europe
1978
Feedstock
Relative prices5
($/metric ton)
U.S.
Europe
Benzene (contract)
285-330
360
Ethylene (contract)
285
470
Propylene (contract)
200
300
First Quarter 1979
SOURCE: Chemical"Industry Girds to- Defend Exports. Chemical and Engineering
News. P. 14. October 22£'1979.
9-92
-------
adverse economic effects. The scheme assigns values to the AO chemical
industries based on their criterion test results.
• Inflation criterion (price, P)
Let P =4 times the inflation calculation (inflation calculated
after after steps 1 and 2 of the price increase screening
see Section 9.2.3.2)
• Profitability criterion (net present value, NPV)
Let 0 = the percentage decrease (or increase) in the net present
value due to control*
Let
Let
Let
Let
Let
Let
Let
NPV
NPV
NPV
NPV
NPV
NPV
NPV
=
=
=
=
=
=
= '
1.
1.
2.
2.
3.
3.
4.
0
5
0
5
0
5
0
if
if
if
if
if
if
if
0
10
20
30
40
50
60
S D <
S D <
^ D <
S D <
^ 0 <
S 0 <
S-...D
c 10
J 20
c 30
: 40
c 50
: 60
If there is an increase inr&ie net present value due to the control,
the value assigned NPV was->mliltiplied by -1. An increase in net
present value is a positive effect of the standard and appears as a
credit in ranking.
t Capital Availability Criterion (C)
Let C =0.5 jof the capital availability calculation (capital cost
of control divided by the facility's fixed investment,
multiplied by 100; data used in this calculation are
prop'ri etary)
• Foreign competition (F)
Let F = 0 if the inflation calculation is less than 5
Let F = 0.3 of foreign competition calculation if the chemical
fails the price screen
• RANKING SCORE = JP + NPV + C + F.
Table 9-26 presents the ranking of the AQ chemicals. The values
assigned to the tests; reflect their importance in the screening study used
*The percentage decrease (increase) in the net present value =
100 [(Decrease (or Increase) in net present value due to control)
I net present value before control
Numbers for the calculation are obtained from Table 9-20.
9-93
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TABLE 9-26. CHEMICALS RANKED BY POSSIBLE ECONOMIC
EFFECTS OF AO NSPS*
36 AO Chemicals, 29 AO Processes
United States
1978
Rank
1
2
3
4
5
6
7
8
10
11
12
13
16
18
«•
* * «
Chemical
1,3-Butadiene
Maleic anhydride (benzene oxidation process)
Phthalic anhydride (xylene oxidation process)
Formaldehyde (mixed metal catalyst process)
Maleic anhydride (n-butane oxidation process)
Acetic acid (Wacker process)
Anthraquinone
Acetic acid (coproduct wftdi methyl ethyl ketone via
n-butane oxidation process;)
n-Benzoic acid
Phthalic anhydride (naphthalene oxidation process)
Glyoxal
Isophthalic acid
n-Butyric"acid (byproduct of acetic acid via n-butane
oxidation process)
Benzaldehyde
Phenol (coproduct wth acetone via cumene hydroperoxide
process)
Propiom'c acid (byproduct of acetic acid via n-butane
oxidation process)
Acetaldehyde (Wacker process)
Terdphthal i c acid (coproduct with dimethyl terephthalate)
I
Ethy;lene oxide
f
! 9-94
Score
27.7
24.2
22.8
21.2
21.0
12.8
12.0
10.8
10.8
8.8
8.4
8.0
7.6
7.6
7.6
7.2
7.2
6.8
6.8
-------
24
25
28
29
30
33
35
36
TABLE 9-26 (Continued). CHEMICALS RANKED BY POSSIBLE ECONOMIC
EFFECTS OF AO NSPS*
36 AO Chemicals, 29 AO Processes
United States
1978
Rank
20
21
22
Chemical
Methyl ethyl ketone (coproduct with acetic acid via
n-butane process)
, Acetone (coproduct with phenol via cumene hydroperoxide
process)
Acrylonitrile (coproduct with hydrogen cyanide)
Formic acid (byproduct of acetic acid via n-butane
Score
6.4
5.6
5.2
5.2
p-t Butyl benzoic acid
Dimethyl terephthalate (ogproduct with terephthalic acid)
Acrylic acid ~ *_
Acrolein (byproduct of acrylic acid process)
Isobutyric acid
I
Styrene (coproduct with propylene oxide via ethyl-
benzene oxidation process)
Propylene oxide (coproduct with styrene via ethyl-
benzene oxidation process)
a-Methyl styrene (byprduct of acetone via cumene
hydroperoxide process)
Hydrogen cyanide (coproduct with acrylonitrile)
Propionic acid (propionaldehyde oxidation process)
Acetonitrile (byproduct of acrylonitrile process)
Crotonic acid
Cumene hydroperoxide (byproduct of acetone via cumene
hydroperoxide process)
4,8
4.4
4.4
4.4
4.0
3.6
3.2
3.2
3.2
2.8
2.8
2.4
2.0
9-95
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TABLE 9-26 (Continued). CHEMICALS RANKED BY POSSIBLE ECONOMIC
EFFECTS OF AO NSPS*
36 AO Chemicals, 29 AO Processes
United States
1978
Rank
Chemical
Score
37 Acetophenone (byproduct of acetone via cumene hydro-
peroxide process)
Cyclohexanol (coproduct with cyclohexanone)
Cyclohexanone (coproduct with cyclohexanol)
40 Ethylene dichloride
41 Formaldehyde (silver catalyst process)
42 Hydrogen cyanide (Andrussow process)
1.6
1.6
1.6
-1.2
-3.4
•11.6
*The larger the possible economic effects are, measured by a combination of
the screening criteria results, thef higher a chemical-process association
appears on the list. " *.
9-96
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in the analysis. Price increases that might arise from the NSPS are perhaps
the most important consideration in this analysis, and all AO chemical
industries are examined for price impacts. Therefore, this criterion is
weighted most heavily in the ranking scheme. Both profitability and capital
availability are assigned values less than the inflation criterion as these
tests cannot be performed on all chemical industries; chemical industries
that can be considered under the profitability and capital availability
criteria are ranked higher simply by their inclusion under these criteria.
The reduced weight attempts to counteract this bias. The last criterion,
foreign competition, is weighted only if the chemical industry fails the
inflation criterion. If a chemical industry experiences no significant
price rise, there is no justification for foreign competition impacts.
9-2.8 Individual Chemical Industry Analysis
Individual chemical industries are analyzed further in this section if
1) the chemical industry is not screened out with regard to one or more of
the criteria or 2) the chemical::industry is found at either of the top
three positions on the ranking Hst. Results of the sensitivity studies
are not included in the ranking"scheme. As it turns out, most of the
chemicals failing a criterion are ranked at the top of the list.
Maleic anhydride (benzene/ n-butane) and phthalic anhydride (xylene)
are two large volume chemical industries that are not screened out in the
first two steps of the price increase analysis; they are examined further
in this section to be certain there are no adverse economic effects from
pollution contro-1--requirements. Worst-case control cost assumptions are
relaxed for these two chemicals in order to obtain a more realistic idea of
price increase due to the cost of control. Also, the competitive structure
of both industries is examined to determine the ability to pass on the
incremental control costs if a new facility is built.
Maleic anhydride (benzene) and terephthalic acid are two SOCMI AO
chemical industries that are not screened out in the profitability decline
analysis; they also are examined further in this section to be certain
there are no adverse economic effects from pollution control requirements.
The ability to pass through incremental costs is a key element in the indi-
vidual chemical profitability analysis. The better the ability to pass
through incremental process costs, the less harm is done to the firm's
9-97
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\
profits, assuming quantity demanded does not decrease with the additional
price hike. Also, because the standard is imposed only on new sources, the
facilities and processes are scrutinized as to the possibility of their
being built in the future.
The 1,3-butadiene industry is examined because it is ranked at the top
of the list. Special attention is given to capital expenditures because of
all the industries examined it is the one that has the highest ratio of
capital control investment cost to fixed plant incremental cost.
9.2.8.1 l,3-6utadiene (Capital Constraints). 1,3-butadiene is-pro-
duced predominantly by recovery from coproduct streams of ethylene-
producing steam crackers (80 percent). The remaining 20 percent is produced
by air oxidation of n-butane (7 percent) and catalytic dehydrogenation of
n-butane (Houdry process, 13 percent). The 1,3-butadiene industry is the
number one ranked industry with regard to potential adverse economic effects
from the air oxidation NSPS. The industry also has the highest ratio of
capital control investment cost^o fixed plant incremental cost of all AO
industries examined. *f
-e "*"•
Financial information presented in Section 9.1 indicates that AO
parent companies should have little difficulty with either debt or equity
financing. Table 9-27 lists the 15 firms that produce 1,3-butadiene, their
total capital expenditures in 1978, capital expenditures for chemical
operations (only for diversified firms if available), and the percentage of
company capital expenditures that fall within the scope of normal spending.
Copolymer Rubber"and Chemical Company has the highest cost of control as a
percentage of capital expenditures, almost 25 percent. Copolymer Rubber
and Chemical Company is a firm jointly owned by four other companies (see
Footnote C, Table 9-27). If these four companies pool their capital, the
cost of control, as a percentage of capital expenditures, is reduced by
half.
9.2.8.1.1 Supply-side considerations. There are 14 firms producing
1,3-butadiene (see Table 9-28). The majority of capacity is owned by
Neches Butane but amounts to only 16.7 percent of the total industry's
1,3-butadiene capacity. Also, Neches Butane has announced plans that it
will close its facility. Other immediate .future plans include the shutdown
of the Phillips facility, an 88 Gg facility to be constructed by El Paso,
9-98
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9-99
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TABLE 9-28. 1,3-BUTADIENE CAPACITY, BY PRODUCER
United States
1978
Firm
Amoco
Arco
Copolymer
Dow
El Paso
Exxon
Firestone
Mobil
Monsanto
Heches Butane
Petro-Tex
Phillips .
Shell
Union Carbide
TOTAL
Annual capacity
CGg)
72
240
64
34
80
228
96
~*Y 20
•< ~
-40
320
300
124
200
98
1916
Percentage of
total capacity
3.8
12.5
3.3
1.8
4.2
11.9
5.0
1.0
2.1
16.7
15.7
6.5
10.4
5.1
100.0
SOURCE: SRI International.
States of America.
1978 Directory of Chemical Producers, United
9-100
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and a 200 Gg facility to be built by Shell. The net result in terms of
market concentration is that Shell will own the most 1,3-butadiene capacity,
equalling 23 percent of the total capacity.
With the relatively large number of firms producing 1,3-butadiene and
capacity spread fairly equally among four or five firms, the industry can
be termed price-competitive. An additional 1,3-butadiene facility is
expected to be built from 1981 through 1986. Even if Shell should build
this new facility (which is doubtful given that they are just completing
one), Shell would still not possess the market power to dictate prices.
The domestic 1,3-butadiene industry also faces significant competition from
foreign imports (17 percent of domestic 1,3-butadiene consumption is im-
ported), making it difficult for one firm to set higher prices.
A tight supply condition in the future may be conducive to the indus-
try's ability to raise 1,3-butadiene price. The supply condition would
evolve from raw material economics. Most 1,3-butadiene facilities are
dependent on cqproduct extraction, from ethylene-producing steam crackers
and are built to use naphtha or*p oil as the major raw material. Because
light hydrocarbons such as ethane^ propane, and butane are less expensive
than naphtha and gas oil, raw material substitution is presently occurring.
The result of using the lighter-hydrocarbons is that the 1,3-butadiene
content of feed streams from ethylene units will drop.
9.2.8.1.2 Demand-side considerations. The major end use of 1,3-
butadiene is related primarily to the automotive industry. Forty-five
percent of the 1,.3-butadiene produced is used to make styrene-butadiene
rubber (SBR) which goes into tires. Unfortunately for 1,3-butadiene pro-
ducers, the tire business has been a leading casualty of the energy crisis.
Smaller cars, radial tires, and a general decline in automobile production
have hurt the tire industry. A significant resurgence of demand in this
area seems unlikely. Demand for SBR will decline or, at best, remain flat.
Output of other types of rubber such as polybutadiene rubber and neoprene
that need 1,3-butadiene may not decline, but neither will they grow very
much in the near future. The one bright spot for 1,3-butadiene use is
acrylonitrile-butadiene-styrene (ABS). Growth in demand for ABS is pro-
jected to be 5 to 7 percent annually, but-because ABS consumes only 6
percent of 1,3-butadiene production, ABS will be of little help in increasing
the overall 1,3-butadiene demand.
9-101
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The price of 1,3-butadiene certainly will not increase due to demand
pressures. Prices will rise as raw material costs increase. Producers may
have a difficult time totally passing through pollution control costs
because of poor demand conditions. As a result, profitability decline due
to pollution control costs will be minor when compared to the profitability
repercussions caused by a flat demand situation.
9.2.8.2 Maleic Anhydride (Price Increase and Profitability Decline).
Maleic anhydride is made using an AO process and either benzene or n-butane
as the main feedstock. The chemical shows a price increase due to the
incremental costs of control greater than 5 percent when these control
costs are tabulated initially. When the worst-case control cost assump-
tions are relaxed, maleic anhydride made from benzene experiences a price
rise of 4.2 percent and maleic anhydride produced using n-butane shows a
price increase of 3.1 percent.
Also, the maleic anhydride (via benzene) facility is found to have
unfavorable profitability when pollution costs are added, while the maleic
anhydride (via n-butane) facilinexperienced no such adverse effect. The
failure of benzene-feedstock maleic anhydride under the profitability cri-
terion may be discounted becaus'e it is likely that any new maleic anhydride
sources will use n-butane as their only feedstock. Monsanto's new facility
will use n-butane, and it is presently planning to convert its St. Louis
plant to n-fautane feedstock. Ashland and Denka will change over to an
n-butane feed and Koppers is considering replacing its benzene feedstock
7?
facility with one--using n-butane.
n-Butane appears to have some clear economic advantages over benzene
as a feedstock. There are two important reasons why the n-butane process
is more profitable than the benzene process and why new maleic anhydride
facilities will more than likely use an n-butane feed. First, the cost of
n-fautane is substantially less than the cost of benzene. Contract n-butane
currently sells for about 20 cents per kilogram while benzene costs approxi-
mately 46 cents per kilogram. The difference is tempered somewhat by the
fact that a kilogram of benzene yields slightly more maleic anhydride than
a kilogram of n-butane and that the price of n-butane increases by approxi-
mately 40 percent during the winter months; however, unlike other petro-
chemical feedstocks, the price of n-butane may decrease in the future as
9-102
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supply increases. The second reason is availability: market forecasts
indicate large surpluses of n-butane for the 1980's,73 n-Sutane also comes
from two sources, oil and natural gas, providing better insurance against
supply interruptions.
9-2-8-2-1 Supply-side considerations. The maleic anhydride industry
is very competitive. Market shares are not concentrated; no one firm owns
more than 21 percent,of the total capacity (see Table 9-29). The major
areas of competitive pricing involve the merchant market rather than the
captive market. Merchant sales comprised 75 percent of the maleic anhydride
consumed in 1977 with captive consumption at 20 percent and imports at 5
percent. While cost may be passed through both the merchant and captive
markets, the greatest effect is seen in the highly competitive merchant
market.
The captive market price increments emerge in the final product,
having been diluted by costs of other constituents also necessary to pro-
duce the final product. The eftect of this "dilution" is substantial: for
example, approximately 15 percei^f of the wholesale price of unsaturated
polyester resins is attributed tovmale.ic anhydr.ide.
On the supply side, it app'ears that the incremental cost of pollution"
controls would not raise the price of maleic anhydride substantially, if at
all, because the industry is competitive in its pricing practices. Monsanto
is slated to build a new facility with a capacity of 60 gigagrams in the
first quarter of 1981. (If started on schedule, the Monsanto plant would
not be affected-by the NSPS.) Monsanto, with this new facility, would own
almost 50 percent of total maleic anhydride capacity. Monsanto then could
become the industry price leader. However, it has been estimated that the
amount of maximum additional maleic anhydride capacity that will be built
from 1981 through 1986 is 138 gigagrams. This additional capacity, if
built by one or more different firms, would dilute Monsanto1s market advan-
tage and no firm would have the market power to raise price based on its
incremental control costs alone.
9.2.8.2.2 Demand-side considerations. While there appears to be
fairly intense competition among manufacturers of maleic anhydride, little
import competition exists. Also, the competition from similar products
that may serve as substitutes is not great. This situation usually results
9-103
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TABLE 9-29. MALEIC ANHYDRIDE CAPACITY, BY PRODUCER
United States
1978
Firm
Ashland Oil
Denka Chemical
Koppers
Monsanto Company
Reicnold Chemicals
Standard Oil Company of
Indiana
Tenneco
United States Steel
TOTAL
Annual capacity
(Gg)
27.2
22.7
20.0
47.6
40.8
27.2
.11.8
"4s 3
-Jp» O
_233.6 -
Percentage of
total capacity
11.5
9.7
8.6
20.4
17.5
11.6
5.1
J.5.5
100.0
SOURCE: SRI International. 1978 Directory of Chemical Producers,
United States of America.
9-104
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in an incremental cost pass-through ability in times of high demand for the
product and the inability to pass through all or part of an additional cost
increase during periods of low demand.
Substitutes may exist for maleic anhydride itself as well as for the
products that use maleic anhydride as an input material, depending on the
end use. The predominant end use of maleic anhydride is in the production-
of unsaturated polyester resins. Of the 151 gigagrams of maleic anhydride
produced in 1978, polyester resins, consumed 54 percent or 82 gigagrams.
Polyester resins go into reinforced plastic applications such as marinecraft,
building panels, automobiles, tanks, and pipes. Maleic anhydride, unlike
most of the other input materials used to make unsaturated polyester, is a
necessary input because it is the source of unsaturation and is necessary
to cross-link the polyester with the reactive dilutent.
The-agricultural chemicals market is the second largest market for
maleic anhydride (10 percent of total demand). Although other chemicals
can substitute for maleic anhydride as an agricultural chemical, it is
highly competitive in this marksJEL Unsaturated polyester resins and agri-
cultural chemicals have the potential to be high- growth products in the
future and may provide the necessary demand conditions to pass through
fully any pollution control costs. Other markets, such as lubricants,
maleic anhydride copolymers, fumaric acid, and reactive plasticizers, are
mostly mature with little possibility of additional market penetration by
maleic anhydride.
The maleic anhydride industry has indicated that it would not raise
prices under low demand market conditions but rather, because manufacturers
of maleic anhydride are a small part of large parent firms, would pass
through pollution control costs partially or totally to other products.
Recently, sellers, buyers, and dealers of maleic anhydride have agreed that
pricing for the product has been extremely weak because capacity utiliza-
tion has been low, approximately 10 percentage points below the industry
average.
In addition, the presently weak pricing situation is predicted to
continue. Unsaturated polyester resins seem to be a guiding factor and are
heavily dependent on construction and automotive needs, two areas that may
continue to stall. As a result of the inability to pass through the cost
74
9-105
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increase, the impact of the standard will be greater on profitability than
on inflation.
9.2.8.3 Phthalic Anhydride (Price Increase). Phthalic anhydride is
produced using an AO process and either xylene or naphthalene as the main
feedstock. Phthalic anhydride using xylene initially has a price increase
of greater than 5 percent; after the worst-case control costs are modified,
its 1986 price impact decreases to 3.5 percent when xylene is the feedstock
and 2.2 percent when naphthalene is the feedstock. The two feedstock
materials are fiercely competitive; approximately 50 percent of phthalic
anhydride is produced from xylene and 50 percent from naphthalene. The
similar percentage price increases point out that possible competitive
disadvantages for either feedstock can be discounted when pollution control
requirements are imposed on new phthalic anhydride facilities.
The phthalic anhydride industry is similar to the maleic anhydride
industry in terms of market competition. Phthalic anhydride has a large
merchant market (60 percent of the phthalic anhydride sold), little compe-
tition from imports, few substitutes for the product itself or its end
•« -
uses, and a highly competitive intra-Industry atmosphere.
9.2.8.3.1 Supply-side considerations. There are nine chemical firms
producing phthalic anhydride, none of which owns more than 26 percent of
the total capacity CSee Table 9-30). Recently, Exxon raised its capacity
from 59 to 95 gigagrams in the fourth quarter of 1980.75 Also, United
States Steel and Tenneco Chemicals, in a joint effort, broke ground early
in 1981 on,a 95-gigagram xylene-based phthalic anhydride operation. These
two facilities-will not be affected by the AO NSPS because they will be
started before the standard is proposed. The addition of this capacity
will not change the competitive nature of the phthalic anhydride industry.
United States Steel would own the most capacity — also 26 percent of the
total capacity. Additional phthalic anhydride capacity to be built and
replaced from 1981 through 1986 is projected to be 165 gigagrams (three
projected plants multiplied by an average capacity of 55 gigagrams each).
If an existing company with a substantial stake in .the phthalic market
(such as Koppers or United States Steel) builds a new facility and gains a
greater market share, then, in the role of price leader, it may be able to
pass on the incremental costs of control. Again, this would be possible
9-106.
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TABLE 9-30. PHTHALIC ANHYDRIDE CAPACITY, BY PRODUCER
United States
1978
Firm
Allied Chemical
BASF Wyandotte
Exxon
Koppers
Monsanto
Occidental Petroleum
Standard Oil Company of
California
Stephan Chemical
United States Steel
TOTAL
Annual capacity
(Gg)
18.1
68.0
59.0
152.0
99.8
45.4
22.6
14 45.4
- 93.0
603.3
Percentage of
total capacity
3.0
11.3
9.8
25.3
16.5
7,5
3.7
7.5
15.4
100.0
SOURCE: SRI International. 1978 Directory of Chemical Producers
United States of America.
9-107
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only if the general economy and overall demand are healthy so that the
automobile and housing sectors have a few strong years.
9.2.8.3.2 Demand-side considerations. Fifty percent of the phthalic
anhydride produced is used in phthalate plasticizers, 24 percent in unsatu-
rated polyester resins, 19 percent in alkyd resins, and the remaining 7
percent in miscellaneous uses. The main use of phthalate plasticizers is in
polyvinylchloride. The phthalic anhydride used to produce unsaturated
polyester resins is not a substitute for maleic anhydride, but rather a
complementary input.
Two phthalic acids — terephthalic and isophthalic — are substitutes
for phthalic anhydride but usually will not compete because of their higher
process costs. There are a few cases of resin use in which the higher
prices of terephthalic and isophthalic acids might be justified.
The end uses of phthalic anhydride are related predominantly to the
automotive and housing markets. Thus, the ability to increase prices
depends mainly on the general level of the-economy. In a time of reces-
sion, phthalic anhydride•producers find it difficult to increase price.
Phthalic anhydride does have one Cutlet (alkyd resins) that is not depen-
dent on-the state of the economy.- Phthalic anhydride, polyhydric alcohol,
and fatty oils combine to produce alkyd resins that serve as the bases of
various industrial paints. Sales of alkyd resins have remained constant
through the current recession.
Overall, because of an indifferent market and competitive pressures,
the price of phthalic anhydride currently has been termed "weak" and pro-
fitability has suffered. Phthalic producers have had trouble passing
through the rising costs of xylene. This inability to raise price origi-
nates from the competitive pressure of naphthalene-based producers and from
slow automotive sales and below-normal housing starts.
9.2.8.4 Terephthalic Acid (Profitability Decline). Almost the entire
amount of terephthalic acid (TPA) consumed is used in the production of
polyethylene terephthalate, the polymer used in the manufacture of poly-
ester fibers and polyester films. Polyester fibers account for 91 percent
of the polyethylene terephthalate consumed; polyester films, for 7 percent.
TPA can be substituted easily by dimethyl -terephthalate (DMT) in the pro-
duction of polyethylene terephthalate; DMT is produced as a coproduct with
TPA and would have similar control costs imposed upon it.
9-108
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TPA has been experiencing a greater growth in production than has OMT
for two reasons. First, at equal prices, TPA has a cost; advantage over DMT
on the basis of material requirement per pound of polymerf manufactured
(about 14 percent less TPA is needed than DMT). Second, jsomewhat shorter
reaction times are required if TPA is used, although DMT-based processes
are more economical for batch operations (important when ;a large number of
different fiber grades are being produced) and for the production of fibers
with more consistent dyeing properties. It appears that TPA producers
should not have a problem passing through control costs from fear of substi-
tutes because DMT also experiences the incremental cost of control and, in
general, because TPA has process economic advantages over DMT. In addition,
there is little chance of a non-AO process being substituted to produce
TPA, because a more economical one does not yet exist.
Intra-industry competition does not appear to be very intense. There
are only two firms producing TPA: Standard Oil Company-Indiana (Amoco
Chemicals Corporation) owns 88 percent of the total capacity and Hereofina
owns the remainder. It appears ^)at these two firms are iable to boost
their prices when costs increase".I Recently, the price of the basic raw
material, p-xylene, rose dramatically, pressured by demand for mixed xylenes
in gasoline. The two TPA producers were able to increase the price of
their monomer equivalently. In turn, there has been pressure on polyester
prices to increase even though, traditionally, the textile industry has
strongly resisted price increases.
The primary.,substitute for polyesters is cotton. The historically
strong growth rate for TPA ~ 16 percent per year, 1968-1978 — has been
due to the replacement of cotton by polyesters in the textile industry.
However, if polyester fiber prices increase, cotton might retrieve! some of
its lost market share.
With a strong growth rate projected (7.5 percent annually), and the
apparent ability to pass on increased cos.ts of production, the profita-
bility of the TPA process should face no significant setbacks due to pollu-
tion control.
9.3 POTENTIAL SOCIOECONOMIC AND INFLATIONARY IMPACTS
If all new SOCMI sources that use an .air oxidation process are re-
quired to purchase and operate an incinerator, the socioeconomic impacts
can be summarized as follows:
9-109
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Annualized Costs. Annualized costs in the fifth year following propo-
sal are expected to be $67 million (1978 $) if all 49 projected new AO
sources are controlled. The annual ized controjl costs are before-tax,
projecting the total dollar costs of control not just to industry, but to
society as a whole. The 49 projected new sources represent facilities to
be constructed because of additional growth in demand as well as new facili-
ties needed to replace obsolete existing capacity.
Price Impacts (Inflation). All of the 36 chemicals produced using the
AO process have price increases of less than 5, percent. Because all of the
chemicals are intermediates, downstream products will have even smaller
price increases due to the NSPS. The effect on the consumer price index
appears negligible.
Employment Impacts. Adverse impacts on employment can be discounted
because an NSPS on AO processes has no affect on current demand. The
amount of labor required to operate a thermal incinerator is estimated to
be one person. Therefore, with-49 new facilities projected to be built, 49
workers would be hired as a result of the imposition of an NSPS on SOCMI.
'* ? *
Distributional Impacts. TRet-standard is worded such that some new
facilities will be exempt from "installing control equipment because they
will be above a defined total resource effectiveness (TRE) floor (see
Chapter 6). New facilities that fall below the floor would be required to
make a pollution control expenditure. A national profihe of AO facilities
as defined in Chapter 6 has 11 of 59 existing facilities falling below the
TRE floor when regulatory alternative III is examined, j Regulatory alterna-
tive III represents an estimate of the most practical approach for imple-
menting the standard. The 11 facilities are examples from a current sample.
It is impossible to predict that new facilities complying with the standard
will be similar to the 11 facilities from the national profile. In any
case, the 11 existing facilities are used to examine whether the standard
causes disproportionate burdens on various segments such as specific chemi-
cal industries, specific companies, geographical areas, small versus large
facilities, and end use types.
Of the 11 facilities that fall below the TRE floor, 4 produce acrylo-
nitrile, 3 produce ethylene oxide,' 2 produce ethylene dichloride, 1 produces
cyclohexanol/cyclohexanone, and 1 produces maleic anhydride. The acrylo-
9-110
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nitrile industry not only has the largest number of facilities being con-
trolled in absolute terms, but also has the highest percentage of existing
facilities using an air oxidation process being controlled — 4 of 5 ex-
isting acrylonitrile facilities fall below the TRE floor.
The 11 facilities are owned by 10 separate firms. Only Dow owns more
than one of the facilities that requires additional pollution control
expenditures. Hence, the distributional burden of the standard is shared
almost equally among firms that must comply with regulatory alternative
III. Also, all firms that own the 11 facilities below the TRE floor are
large, diversified, and financially strong entities. The small, marginal
companies are not affected.
Eight of the 11 facilities are located in Texas and Louisiana. Only
40 percent of all facilities that produce air oxidation chemicals are
located in Texas and Louisiana. Facilities affected appear to be larger in
capacity than the norm. The size of the 11 facilities ranges from a capa-
city of 14 gigagrams to a capacity of 726 gigagrams. The average capacity
is 153.6 gigagrams and this compares to an average capacity of 119.1. giga-
grams for all facilities producTng air oxidation chemicals. Finally, all
of the chemicals falling below "the TRE floor are used in the production of
polymers and resins.
Regulatory Flexibility Act Considerations. The Regulatory Flexibility
Act (RFA) became effective on January 1, 1981, and requires agencies to
consider flexible regulatory approaches that minimize the economic impact
of regulations orv small entities. Specifically, the RFA states that a
thorough impact analysis be undertaken if the proposed standard has a
significant economic impact on a substantial number of small entities.
Entities such as not-for-profit organizations and small governmental juris-
dictions do not experience any perceivable effects from the SOCMI AO NSPS.
Only small businesses are affected by the AO standard. To determine if the
AO NSPS merits a detailed analysis, a small business for the AO industry
must be defined.
Under Section 121-3-lb of the Small Business Administration Rules and
Regulations, a small business concern is defined by an employment size
standard for each four-digit Standard Industrial Classification (SIC) code.
This is the measure used to determine a small business concern for the
9-111
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purpose of pollution control guarantee assistance. Also, a business is con-
sidered small only if it is owned and operated independently. AO chemicals
are included in SIC 2865 and SIC 2869 and their size standards are 750 and
1,000 employees, respectively. The definition of a small business for SIC
2865 is applied to all AO chemical manufacturers because it is more conser-
vative.
There are 75 companies that produce AO chemicals (listed in Table 9-4).
More than half of the companies using the AO pro'cess are ranked in the top
50 chemical-producing companies based on value of chemical sales in 1979.
A survey of the number of employees per company from Standard and Poor's
Register of Corporations, Directors and Executives, 1981 reveals that only
three companies, Kalama Chemicals, Inc., Wright Chemical Company, and Co-
polymer Rubber and Chemical Corporation, have fewer than 1,000 employees
and qualify as small businesses. Therefore, less than 3 percent of the
affected companies are small businesses. A brief discussion of the effect
of the NSPS on"small businesses -follows.
Since this standard'appliesVprimarily to new sources, it is difficult
• *>
to estimate its specific adverse Effect on projects that will be undertaken
by small businesses entering the industry. In general, if a company has the
capital available to enter the industry, the NSPS will require only a small
percentage increase in the capital required for the project. Furthermore,
the price impact screening results suggest that producers of AO chemicals,
under a worst-case scenario, are able to pass through NSPS compliance costs
to their customers while keeping the price increase of their product under
5 percent. Most importantly, however, the economies of scale that exist in
this industry hinder the entrance of small businesses. Therefore, even
without the NSPS, the AO industry is not conducive to small businesses. In
the five years following proposal of the NSPS, small businesses should not
constitute a greater share of AO producers than they currently do, i.e.,
3 percent of AO firms.
Costs and Benefits. Executive Order 12291 specifies that a regulatory
action, to the extent permitted by law, must not be undertaken unless the
potential benefits to society from the regulation outweigh the potential
costs to society. An exhaustive benefit-cost analysis is not appropriate
here because the potential air oxidation emissions standards will not
constitute a major rule within the meaning of the Executive Order because
9-112
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.--_™—4J_...
the cost of the standards and their overall impact on the economy are not
expected to be significant.
The costsj of the potential standard are not exorbitant, especially
when the signijfleant benefits that will accrue due to the standards are
examined. Estimated net annualized costs for the most stringent standard
as well as the regulatory alternative most apt to be chosen are small in
comparison with industry output. The cost analysis focused on the potential
costs of the standards, and the impact of these costs on producers of SOCMI
chemicals. Based on these costs and the impacts of the costs, the costs of
the standards are considered feasible. The benefits of the standards,'as
discussed below, may be compared subjectively with the costs.
Because environmental quality is a public good, it is necessary to use
an indirect approach to valuing the changes in environmental quality.
These approaches generally use market data and attempt by regression analy-
sis to infer values for improvements in air quality from individuals'
behavior or toj solicit such values by directly questioning the affected
individuals. 'EPA is at the forefront of benefits estimation, both in the
knowledge of various methodologfe^ and in the practical application of
these methodologies to various-standards given data constraints. These
benefit analyses involve a substantial investment of time and resources and
they have limitations, i EPA does not think that a full benefits analysis is
warranted for the potential air oxidation emissions standards, given that
the net costs that EPA has estimated for the most stringent standard are
relatively small..and this expected improvements in environmental quality are
significant. I
These standards wifll reduce the rate of VOC emission to the atmos-
phere. VOC are precursors of photochemical oxidants, particularly ozone.
The EPA publication, Air quality Criteria for Ozone and Other Photochemical
Oxidants (EPA-600/8-78-004, April 1978), explains the effects of exposure
to elevated ambient concentrations of oxidants. (The problem of ozone
depletion of the upper atmosphere and its relation to this standard are not
addressed here.) These effects include:
• Human health effects - ozone exposure has been shown to cause in-
creased rates of respiratory symptoms such as coughing, wheezing
sneezing, and short-breath; increased rates of headache, eye-
irritation, and throat irritation; and increases in the'number of
9-113
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red blood cells (changes in erythrocytes). One experiment links
ozone exposure to human cell damages known as chromosomal aber-
rations.
Vegetation effects - reduced crop yields as a result of damages to
leaves and/or plants have been shown for several crops including
citrus, grapes, and cotton. The reduction in crop yields was
shown to be linked to the level and duration of ozone exposure.
• Materials effects - ozone exposure has been shown to accelerate
the deterioration of organic materials such as plastics and rubber
(elastomers), textile dyes, fibers, and certain paints and coat-
. ings.
• • Ecosystem effects - continued ozone exposure has been shown to be
linked to structural changes of forests such as the disappearance
of certain tree species (Ponderosa and Jeffrey pines) and death of
predominant vegetation. Hence, continued ozone exposure causes
stress to the ecosystem.
; In addition to the evidence of the physical and biological effects
enumerated above, reduction of VOC emissions is likely to improve the
aesthetic and economic value of Jhe environment through: 1) beautification
of natural forests and undeveloped land through increased vegetation; 2)
increased visibility; 3) reduced Tncidence of noxious odors; 4) increased
life for works of art, including paintings, sculpture, architecturally
important buildings, and historic monuments; 5) improved appearance of
structures, sculptures, and paintings, and 6) improved productivity of
workers, especially farm laborers.
Also, the potential air oxidation NSPS provides other direct public
goods to society"including: 1) improvement of business decision making;
2) optimization of industrial location; and 3) acceleration of technological
innovation. The nature of each' of these benefits is discussed below:
• Decision making - the collection of data, evaluation of control
technologies on specific processes, and the publication of this
information in the form of control technique guidelines, back-
ground information documents, and other reports represent benefits
to many businesses (in particular small businesses) that do not
have the resources to implement such an exhaustive information
processing system.
• Industrial location - a nationwide standard of performance for VOC
emissions is likely to remove the incentives for possibly sub-
optimal plant locations in states with relatively weak State
Implementation Plan (SIP) emissions standards, as opposed to
states with relatively stringent SIP emissions standards.
9-114
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• Technological innovation - the information generated through the
regulatory process may accelerate the development of new technolo-
gies by businesses.
9-115
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FOOTNOTES
1. The value of shipments for SIC 28 in 1978 is $130,000,000,000 and for
SIC 286 is $31,800,000,000 (from U.S. Department of Commerce. 1979
U.S. Industrial Outlook). The AO chemicals' value of shipments was
found using Tables 9-1 and 9-2. Production was multiplied by percen-
tage sold and this was multiplied by market price for each particular
chemical. The products were summed to give a value of shipments for
the chemicals listed in Table 9-2. This amount was extrapolated based
on capacity to include all 36 chemicals. The value of shipments for
all air oxidation chemicals is estimated to be $3,188,100,000 for
1978.
2. U.S. Department of Commerce. 1979 U.S. Industrial Outlook. January
1979.
3. Chemical Profitability Nears Turnaround. Chemical & Engineering News.
P. 8. May 8, 1978.
4. Earnings Gain Off, but Better than Expected. Chemical & Engineering
News. P. 8. February 18, 1980.
5. Ibid. P. 10.
6. Facts and Figures for the tk|. Chemical Industry. Chemical & Engineer-
ing News. P. 49. June 11, 1979.-
7. Ibid. P. 55.
8. C.H. Kline & Company. The Kline Guide to the Chemical Industry.
Fairfield, New Jersey, C.H. Kline & Co., 1977.
9. Ibid. P. 86.
10. C.H. Kline "&" Company. Plastics and Resins, Forecast to 1983. Fair-
field, New Jersey, Centcom, Ltd., 1979. P. 1.
11. C.H. Kline & Company. The Kline Guide to the Chemical Industry. P.
97.
12. C.H. Kline & Company. Elastomers, A Forecast to 1983. Fairfield, New
Jersey, Centcom, Ltd., 1979. P. 1.
13. C.H. Kline & Company. The Kline Guide to the Chemical Industry. P.
133.
14. Ibid. P. 157.
15. Facts and Figures for the U.S. Chemical Industry. Chemical & Engineer-
ing News. P. 35. June 11, 1979.
9-116
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16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
Sources of Capital for Growth of Process Plants. Chemical Engineering.
P. 142. June 6, 1977.
Slower Growth Clouds Chemicals Outlook. Chemical & Engineering News
P. 13. January 29, 1979.
C.H. Kline & Company. Plastics and Resins, Forecast to 1983.
C.H. Kline & Company. Elastomers, A Forecast to 1983.
U.S. Department of Commerce. 1979 U.S. Industrial Outlook. U S
G.P.O. 1977. P. 367.
Chemical Profile. Chemical Marketing Reporter. P. 9. March 5, 1979.
Chemical Profile. Chemical Marketing Reporter. P. 9. April 7, 1980.
C.H. Kline & Company. Organic Chemicals: Basic and Intermediate
. Forecast to 1983. Fairfield, New Jersey, Centcom, Ltd., 1979.
Ibid.
Chemical Profile. Chemical-Marketing Reporter. P. 9. April 28
1980. • ;/. '
C.H. Kline & Company. Organic Chemicals: Basic and Intermediate,
Forecast to 1983.
Chemical Profile. Chemical Marketing Reporter. P. 9. December 11,
1378. *
Chemical Profile. Chemical Marketing Reporter. P. 9. March 17, 1980.
C.H. Kline & Company. Organic Chemicals: Basic and Intermediate
Forecast to_.1983.
Ibid.
Ibid.
Ibid.
Ibid.
Chemical Profile. Chemical Marketing Reporter. P. 9. December 17,
Chemical Profile. Chemical Marketing Reporter. P. 9. October 22,
i-3 / .7 *
C.H. Kline & Company. Organic Chemicals: Basic and Intermediate,
Forecast to 1983.
9-117
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37. Maleic: Looking Beyond Slowdown. Chemical Week. P. 42-43. January
9, 1980.
38. C.H. Kline & Company. Organic Chemicals: Basic and Intermediate,
Forecast to 1983.
39. Chemical- Profile. Chemical Marketing Reporter. P. 9. August 18,
1980.
40. C.H. Kline & Company. Organic Chemicals: Basic and Intermediate,
Forecast to 1983.
41. Chemical Profile. Chemical Marketing Reporter. P. 9. .December 31,
1979.
42. Chemical Profile. Chemical Marketing Reporter. P. 9. January 29,
1979.
43. C.H. Kline & Company. Organic Chemicals: Basic and Intermediate,
Forecast to 1983.
44. Ibid.
45. Uncertainties Plague Ethyle&e Industry. Chemical & Engineering News.
P. 11. May 28, 1979. >|
i,-
46. Ibid. P. 12. .
47. Scherer, P.M. Industrial Market Structure and Economic Performance.
Chicago, Rand McNally College Publishing Company, 1970. P. 170.
48. Aromatic Organics. Chemical Marketing Reporter. P. 11. September 3,
1979.
49. Aromatic Or-ganics. Chemical Marketing Reporter. P. 11. October 1,
1979.
50. Aromatic Organics. Chemical Marketing Reporter. P. 11. October 15,
1979.
51. Communication with International Trade Commission, Bureau of Economic
Analysis. October 29, 1979.
52. Chemicals Strike a Better Balance in World Trade. Chemical Week. P.
31. February 21, 1979.
53. Ibid.
54. Ibid.
55. Ibid.
9-118
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56. Ibid.
57. Chemical Industry Girds to Defend Exports. Chemical & Engineering
News. P. 14. October 22, 1979.
58. Trade Pact Poll: The "Ayes" Have It. Chemical Week. P. 16. June
13, 1979.
59. Ibid.
60. Ibid. P. 17.
61. Industry Steps Up Trade Policy Efforts. Chemical & Engineering News.
P. 10. February 27, 1978.
62. Trade Pact Polls: The "Ayes" Have It. Chemical Week. P. 17. June
13, 1979.
63. The end 1978 prices for oil and gas were obtained from U.S. Department
of Energy. Monthly Energy Review. Washington, D.C., DOE/EIA. December
1979. P. 77, 90. The projected 1986 price of oil was derived from
estimates in U.S. Department of Energy, Annual Report to Congress 1979.
(Volume 3) OOE/EIA-0173(79)/3. P. 84.
64. The projected 1986 price offjas was derived from estimates in U.S.
Department of Energy. "Technical Staff Analysis in Response to Notice
of Proposed Rulemaking on .Phase IT of Incremental Price." February 9,
1980. Found in Federal Energy Regulatory Commission, Office of Pipe-
line and Producer Regulation. Environmental Assessment of Incremental
Pricing, Phase II. Docket No. RM80-10. Washington, D.C., April 1980.
P. 28.
65. U.S. Environmental Protection Agency, Industrial Environmental
Research Laboratory, Office of Research and Development. Industrial
Process Prattles for Environmental Use: Chapter 6, The Industrial
Organic Chemicals Industry. EPA-600/2-77-023F. Cincinnati, Ohio,
February 1979. P. 6-272.
66. U.S. Environmental Protection Agency. Estimation of the Cost of Capi-
tal for Major United States Industries with Application to Pollution
Control Investments. EPA-230/3-72-001. Washington, D.C. , November
1975. P. 4-56.
67. U.S. Environmental Protection Agency, Office of Air Quality Planning
and Standards. VOC Fugitive Emissions in Synthetic Organic Chemicals
Manufacturing Industry — Background Information for Proposed Standards
Research Triangle Park, N.C., March 1980. P. 9-19.
68. PEDCo Environmental Inc. Cost Analysis Manual for Standards Support
Document. Prepared for U.S. EPA. November 1978. P. 29.
9-119
-------
69. U.S. Department of Commerce. United States Export and Import Schedules,
1968-1978.
70. Chemical Marketing Reporter. P. 9. September 10, 1979.
71. U.S. Department of Commerce. United States Exports Schedule of Com-
modity by Country. FT/410. Washington, D.C., December 1978.
72. Ibid. P. 9. December 15, 1980.
73. Ibid. P. 13. August 11, 1980.
74. Telecon. Epstein, E.A., Energy and Environmental Analysis, Inc., and
Magnusson, F., U.S. Department of Commerce, March 3, 1978. In U.S.
Environmental Protection Agency, Office of Air Quality Planning and
Standards. Benzene Emissions from Maleic Anhydride Industry — Back-
ground Information for Proposed Standards. EPA-450/3-8-001a. Research
Triangle Park, N.C., February 1980. P. 5-49.
75. Chemical Marketing Reporter. P. 3. July 28, 1980.
76. Facts and Figures for the U.S. Chemical Industry. Chemical and Engi-
neering News. P. 44. June 9, 1980.
9-120
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APPENDIX A TO CHAPTER 9
9-121
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APPENDIX A
NET PRESENT VALUE FORMULA
The formula for net present value (NPV) is designed to measure the
cash flows that account for the profitability of investments in new facil-
ities to manufacture synthetic organic chemicals. Table A-l presents the
formula in equation form. The formula is complex but is based on simple
concepts. The NPV formula reflects the sum of cash outflows and inflows,
discounted each year to their equivalent values in the base year. A discount
factor, (1-H3)"1, appears often thfthe formula. This reflects the fact that
cash flows in future years (i) .are worth less than current cash flows with
the same nominal value. D is the hurdle rate that new projects must meet
to overcome this time value difference and be competitive with other poten-
tial uses of firms' capital. Cash outflows are: investments in fixed
facilities and equipment, F, and incinerators for emissions control, X;
additions to working capital (the excess of total investment, T, over fixed
investment, F); annual operating costs; and taxes on profits. Cash inflows
are: revenues on production sold each year (price, P, times quantity, Q);
and receipts after taxes from liquidation of working capital at the end of
the equipment's useful life.
There are some complexities in the formula and some simplifications.
One area of complexity reflects the fact that costs and prices are inflat-
ing each year. A factor is used for general price inflation, G, and in
some cases an additional factor for real escalation, R, for items that are
oil-based. Because organic chemicals are petrochemical derivatives, they
escalate in cost at rates in excess of the inflation rate for consumer
goods in general. At the same time, some-items do not inflate at all.
Depreciation allowances do not change with inflation, necessitating special
treatment in formula terms.
9-122
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TABLE A-l. NET PRESENT VALUE FORMULA
Line 3
Line 4
Line 5
Line 6
Line 1 NPV = - (1 + D)~°'5(l + G)°'5F
Line 2 - (1 + D)~°-5(l + G)°'5X
- (i + D)"
20
R)(l -f G)(T - F)
2 (1 + Or(1+0'S>{0.5[(l + R)1+0-5(l
(P-Q - C - Y)] + 0.05 F]
G)10'5X
Z 0.1
0.1
G)10'5X
Line 7
where:
(1 + D)"^1 0.5 [(1
»21
R)(l + G)](T - F)
F = Fixed investment in facilities (does not include incinerator
costs)
T = Total investment (does not include incinerator costs)
D = Hurdle rate used in discount factor
R = Rate of real escalation in prices
G = Rate of general price inflation
P = Price of chemicals
Q = Production quantity
C = Cost of production, excluding-costs for emission controls
X = Investment costs for incinerator
Y = Incinerator operating costs
i = Year
Note: Figures are in 1978 dollars.
9-123
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Lines 1 and 2 of the equation in Table A-l show investments in equip-
ment. Fixed investment in the facility and equipment is shown as F.
Purchase of the first incinerator for emission control is shown as X. Each
cash flow takes place at a certain point or period along a time line.
Investment in the basic facilities and equipment is assumed to take place
over the course of year 0. It is therefore allocated as a lump sum to the
middle of year 0 and is adjusted accordingly with one half year's inflation
and discounted at one half year's discount rate. The incinerator is assumed
to be purchased at mid-year in year 0 also. Hence, the first two terms,
respectively, are (1 + 0)~°-5(1 + G)°'5F and (1 + D)"°-5(1-K3)°-5X. (A
negative exponent denotes "the reciprocal of" while a fractional exponent
denotes a fraction of one year.)
Line 3 shows the initial working capital investment. Working capital
(mainly product inventory) is the excess of total investment, T, over fixed
investment, F. Working capital is produced and stored at the beginning of
year 1, so the cash flows must reflect some inflation and must be discounted
by one year's discount factor. tlflike the investments mentioned above,
working capital also escalates in\alue by a real escalation factor that
reflects the above-average rate;of increase assumed for oil derivatives.
Hence, an extra term, 1 + R, where R is the rate of real escalation for oil
and petrochemical prices, is applied in a compound fashion. Line 3 is
therefore (1 + D)"1(l + R)(l + G) (T - F).
Line 4 is complex and will be explained later. Moving ahead in the
formula, line 5 S'h'ows the purchase of a second incinerator. Unlike general
facilties and equipment, which are assumed to last for 20 years of produc-
tion, incinerators are assumed to last 10 years. A second incinerator is
purchased at mid-year in year 10 to be used at the beginning of year 11 and
last through the end of year 20. The outlay for the second incinerator is
(1 H- D)~10-5(l + G)1CL5X.
Line 6 will also be explained later. Line 7 shows the recovery of
working capital when product inventory, accumulated earlier in year 1, is
sold off as the facility finishes operations at the outset of year 21. The
value of inventory will have risen with inflation in general, G, and with
real escalation in the value of oil-based chemicals, R. The appreciation
in value over 20 years will produce profits that are taxable, such that 50
9-124
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percent of the increase will be deducted for taxes. The whole expression
for the liquidation of working capital is (1 + D)~210.5 [(1 + R)21 (1 +
21
G) +(1 + R)(l -t- G)] (T-F). The figures in brackets represent the increase
in the value of working capital, T - F.
Returning to line 4, the cash flows involved in production and sales
are depicted. Essentially, for each year from 1 through 20, a project will
earn revenues (price, P, times production quantity, Q) and pay costs (pro-
duction costs, C, and control costs, Y, reflecting operating costs of
incinerators). The term (P-Q-C-Y) indicates accounting profits, which are
taxable at a 50 percent rate. Inflation is reflected in the terms (1 +
R) (1 + G)1 ' used as coefficients. Half years were used because
costs and revenues are annual streams, such that their weighted averages
lie roughly at the mid-year points in each year. The term i refers to each
year from 1 through 20.
Depreciation is an. unusual cost item. It is actually a cost allowance
for an annual share of investments made in previous years, not a cash flow.
There is no cash flow for depreciation, but depreciation charges reduce
accounting profits and, therefore^ reduce firms' taxable incomes and tax
payments (which are cash flows).' To correct for the inclusion of depreci-
ation in production costs, C, depreciation is added back as the term 0.05 F.
The depreciation term reflects straight-line depreciation of the fixed
investments over 20 years.
Line 6 presents the depreciation on the incinerators. The first
incinerator is depreciated from year 1 through 10. The second incinerator
is depreciated.from year 11 through 20. Because incinerators last 10
years, a factor of 0.1 is applied to investment costs, X. The investment
cost for the second incinerator reflects inflation over 10.5 years and
hence is multiplied by (1 +-G)10'5. Both expressions for depreciation
include a discount factor (1 + D)"^1""1"0-5).
Not shown in the formula is the assumption that the facility shutdown
costs equal scrap value in year 20. These net out to zero and, therefore,
need not be shown. Land costs, which are not included in fixed investment,
also are assumed to be a neutral factor over the life of a project; resale
value is assumed to allow the original investment to be recouped with an
appropriate return to cover the discount factor.
9-125
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Other simplifications have been made. Depreciation is calculated on a
straight-line basis. Actual depreciation rates would be more accelerated,
so the use of straight-line accounting understates NPV slightly. Another
simplification is the use of variables as entities even though each cost or
revenue item involves subcomponents whose behavior over 20 years may vary
from the average. Finally, the timing of cash flows is necessarily approxi-
mate. The goal in constructing a time line is to approximate the timing of
major cash flows so that the proper inflation and discount factors can be
applied.
The baseline NPV is calculated by setting incinerator investments, X,
and the incinerator operating costs, Y, equal to zero. When emissions
standards must be met, proper values for X and Y are applied with the
assumption that there is no pass-through of control costs in the price of
the chemicals.
*•
9-126
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APPENDIX A: EVOLUTION OF THE PROPOSED STANDARDS
-------
-------
APPENDIX A
EVOLUTION OF THE PROPOSED STANDARDS
The purpose of this study was to develop New Source Performance
Standards for Air Oxidation Unit Processes of the Synthetic Organic
Chemical Industry (SOCMI). Work on the study was begun in March 1979 by
Energy and Environmental Analysis, Inc. under the direction of the
Office of Air Quality Planning and Standards (OAQPS), Emission Standards
and Engineering Division (ESED). The decision to develop this standard
was made on the recommendation of Hydroscience (now I.T. Enviroscience,
Inc.) based upon information compiled under their contract to develop a
technical data base for NSPS's for SOCMI. In performing the standard
development, EEA used product reports and background technical documents
prepared by Hydroscience.
The chronology which follows lists the important events, which have
occurred in the development of background information for the New Source
Performance Standards for air oxidation unit processes of SOCMI.
A-l
-------
Date
May, 1979
August, 1979
August, 1979
October 25, 1979
January 9, 1980
February 6, 1980
March 30, 1980
*
May 5 and 6, 1980
August 18, 1980
August 19, 1980
January, 1981
January, 1981
April 30, 1981
June 30, 1981
July 6, 1981
August 8, 1981
August 18, 1981
September 23, 1981
Activity
Statistical analysis of air oxidation industry and
process emissions initiated.
Draft industry wide statistical profile submitted to
EPA by EEA.
Cost analysis submitted to EPA by EEA.
Meeting with CMA, EAB, SDB, CPB, and EEA to introduce
CMA to the generic approach and method of analysis.
Meeting with CMA, EPA and EEA to bring industry up to
date on the proposed method of analysis and to
elicit industry comments.
Meeting with CMA, EPA,, and EEA to discuss progress
of unit process standard.
Meeting with CMA, EPA, and EEA to brief CMA on the
status of SOCMI projects.
Meeting with CMA, EPA, and EEA to brief CMA on the
flow predictor analysis, national impact analysis,
and affordability screening criteria.
Meeting with CMA, EPA, and EEA to discuss issues
raised on EEA analysis of affordability screening.
Meeting with CMA, EPA, and EEA to brief CMA on the
status of the project.
BID Chapters 3-6 sent out for review by industry
and environmental groups.
Final revised affordability screening, national
impact, and sensitivity analyses provided to
EAB contractor.
Meeting with CMA to discuss their final report on
Air Oxidation Regulatory Development.
Working group package mailed.
Meeting with CMA to discuss Working Group Package.
Package transmitted to NAPCTAC/Steering Committee.
Docket transmitted to Washington, D.C.
NAPCTAC Meeting.
A-2
-------
APPENDIX B: INDEX TO ENVIRONMENTAL CONSIDERATIONS
-------
-------
APPENDIX B
INDEX TO ENVIRONMENTAL CONSIDERATIONS
This appendix consists of a reference system which is cross indexed
with the October 21, 1974 Federal Register (39 FR37419) containing EPA
guidelines for the preparation of Environmental Impact Statements. This
index can be used to identify sections of the document which contain
data and information germane to any portion of the Federal Register
guidelines.
B-l
-------
APPENDIX B
INDEX TO ENVIRONMENTAL IMPACT CONSIDERATIONS
Agency Guidelines for Preparing
Regulatory Action Environmental
Impact Statements (39 FR 37419)
Location Within the Background
Information Document (BID)
1. Background and Description
of proposed Action
Summary of Regulatory
Alternatives
Statutory basis for the
Standard
Facilities Affected
Process Affected
Availability of Control
Technology
Existing Regulations at
State or Local Level
2. Alternatives to the Proposed
Action
Alternatives 0, I, II, III,
IV, V, and VI
Definition of alternatives
The regulatory alternatives are
summarized in Chapter 1,
Section 1.1.
The statutory basis for the
standard is given in Chapter 1,
Section 1.1.
A description of the facilities to
be affected is given in Chapter 6.
A description of the processes to
be affected is given in Chapter 3,
Section 3.3.
Information on the availability
of control technology is given in
Chapter 4.
A dscussion of existing regulations
on the industry to be affected by
the standards is included in
Chapter 3, Section 3.5.
The definitions of alternatives
0, I, II, III, IV, V, and VI are
presented in Chapter 6, Section 6.2,
B-2
-------
APPENDIX B
INDEX TO ENVIRONMENTAL IMPACT CONSIDERATIONS
(CONTINUED)
Agency Guidelines for Preparing
Regulatory Action Environmental
Impact Statements (39 FR 37419)
Location Within the Background
Information Document (BID)
Environmental Impacts
Air Pollution
Water Pollution
Solid Waste Disposal
Energy
Other Impacts
Costs
The air pollution impact of the
control alternatives are considered
in Chapter 7, Section 7.1.
The impact of the control alterna-
tives on water pollution are
considered in Chapter 7, Section 7.2.
The impact of the control alterna-
tives on solid waste disposal are
considered in Chapter 7, Section 7.3.
The impact of the control alterna-
tives on energy use are considered
in Chapter 7, Section 7.4.
Other impacts associated with the
control alternatives are evaluated
in Chapter 7, Sections 7.5 and 7.6.
The impact of the control alterna-
tives on costs are considered in
Chapter 8, Section 8.1.
B-3
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APPENDIX C: EMISSION SOURCE TEST DATA
-------
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APPENDIX C: EMISSION SOURCE TEST DATA
The purpose of this appendix is to describe results of tests of volatile
organic compound (VOC) emissions reduction by thermal incineration. These test
results were used in the development of the background information document
(BID) for air oxidation processes of the synthetic organic chemicals manufacturing
industry (SOCMI). Background data and detailed information which support the
emission levels achievable are included.
Section C.I of this appendix presents the VOC emissions test data including
individual test descriptions. Section C.2 provides a summary of NO emissions
A
from some of the tests. Section C.3 consists of comparisons of various test
results and a discussion exploring and evaluating the similarities and differences
of these results.
C.I VOC EMISSIONS TEST DATA
The tests were aimed at evaluating the performance of thermal incinerators
when used under varied, conditions on the air oxidation process waste streams.
The results of this study indicate that 98 weight percent VOC reduction or
20 ppmv by compound exit concentration, whichever is less stringent, is the
highest control level currently achievable by all new incinerators, considering
available technology, cost, and energy use. This level is expressed in both
percent reduction and ppmv to account for the leveling off of exit concentra-
tions as inlet concentrations drop. This level can be achieved by incinerator
operation at conditions which include a maximum of 1600°F and 0.75 second
residence time. The 98 percent level can frequently be achieved at lower
combustion temperatures.
Three sets of test data are available. These sets consist of field unit
data from tests conducted by EPA and by chemical companies and of lab-sca.le
incinerator data from tests by Union Carbide.
C.I.I Chemical Company Test .Data
These data are from tests performed by chemical companies on incinerators
at three air oxidation units: the Petro-tex oxidative butadiene unit at
Houston, Texas, the Koppers maleic anhydride unit at Bridgeville, Pennsylvania,
and the Monsanto acrylonitrile unit at Alvin, Texas.
C-l
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Stack Gas
The stack gas samples are collected via a tee on a long stainless
steel probe which can be inserted into the stack at nine different
locations. 'These gas samples are collected in 30-50 cc syringes.
The gas samples are then transferred to a smaller 1 cc syringe via
a small glass coupling device sealed at both ends with a rubber grommet.
The 1-cc samples can then be injected into a chromatograph for hydro-
carbon analysis. -A Varian 1700 chromatograph is used, having a 1/8-in.
x 6-ft column packed with 5A molecular sieves and a 1/4-in. x 4-ft
column packed with glass beads connected in series with a bypass before
and after the molecular sieve column, controlled by a needle valve to
split the sample. The data are reported as ppm total HC, ppm methane,
and ppm non-methane hydrocarbons (NMHC). The CO content in the stack is
determined by using a Kitagawa sampling probe. The 02 content in the
stack is determined via a Teledyne 02/combustible analyzer.
3. Test Results - Petro-tex has been involved in a modification
plan for its 'Oxo1 incinerator unit after startup. The facility was
tested by the company after each major modification was made to determine
the impact of these changes on the VOC destruction efficiency. The
incinerator showed improved performance after each modification and the
destruction efficiency increased from 70 percent to well above 98 percent.
Table C-l provides a summary of these test results. The type of modifications
made in the incinerator were as follows:
November 1977
Test data prior to these changes showed the incinerator was not
destroying hydrocarbons as well as it should (VOC destruction efficiency
as low as 70 percent), so the following changes were made:
1. Moved the duct burner baffles from back of the burner to the
front.
2. Installed spacers to create a continuous slot for supplemental
air to reduce the air flow through the burner pods.
3. Installed plates upstream of the burners so that ductwork
matches burner dimensions.
4. Cut slots in recycle duct to reduce exit velocities and improve
mixing with Oxo waste gas.
C-2
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C.I.1.1 Petro-Tex Test Data
1. Facility and Control Device - The Petro-tex incinerator for the
'Oxo1 butadiene process is designed to treat 48,000 scfm waste gas containing
about 4000 ppm hydrocarbon and 7000 ppm carbon dioxide. The use of the term
hydrocarbon in this discussion indicates that besides VOC, it may include non-
VOC such as methane. The waste gas treated in this system results from air
used to oxidize butene to butadiene. The waste gas, after butadiene has been
recovered in an oil absorption system, is combined with other process waste
gas and fed to the incinerator. The waste gas enters the incinerator between
seven vertical Coen duct burner assemblies. The incinerator design incor-
porates flue gas recirculation and a waste heat boiler. The benefit achieved
by recirculating flue gas is to incorporate the ability to generate a constant
100,000 Ibs/hr of 750 psi steam with variable waste gas flow. The waste gas
flow can range from 10 percent to 100 percent of design production rate.
The incinerator measures 72 feet by 20 feet by 8 feet, with an average
firebox cross-sectional area of 111 square feet. The installed capital cost
was $2.5 million.
The waste gas stream contains essentially no oxygen; therefore, significant
combustion air must be supplied. This incinerator is fired with natural gas
which supplies 84 percent of the firing energy. The additional required
energy is supplied by the hydrocarbon contamination of the waste gas stream.
Figure C-l gives a rough sketch of this unit.
2. Sampling and Analytical Techniques
Waste Gas
The waste gas sampling was performed with integrated bags. The analysis
was done on a Carle analytical gas chromatograph having the following columns:
1. 6-ft OPN/PORASILR (80/100).
2. 40-ft 20 percent SEBACONITRILER on gas chrom. RA 42/60.
3. 4-ft PORAPAKR N 80/100.
4. 6-ft molecular sieve bx 80/100.
C-4
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Augmenting
(Supplemental)
Air Duct
WASTE
GAS
Recirculation
Air Duct
RECIRCULATION
AIR FAN
Figure C-1. Petro-Tex oxo unit incinerator.
C-5
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5. Installed balancing dampers in augmenting (supplemental) air
plenums, top and bottom.
6. Installed balancing dampers in three of the five sections of
the recycle duct transition.
7. Cut opening in the recirculation duct to reduce the outlet
velocities.
March 1978
After the November changes were made, a field test was made in
December 1977, which revealed that the incinerator VOC destruction
efficiency increased from 70.3 percent to 94.1 percent. However, it
still needed improvement. After much discussion and study the following
changes were made in March 1978:
1. Took the recirculation fan out of service and diverted the
excess forced draft air into the recirculation duct.
2. Sealed off the 5-1/2-in. wide slots adjacent to the burner
pods and removed the 1/2-in. spacers which were installed in
November 1977.
3. Installed vertical baffles between the bottom row of burner
pads to improve mixing.
4. Installed perforated plates between the five recirculation
ducts for better Oxo waste gas distribution.
5. Cut seven 3-in. wide slots in the recycle duct for better
secondary air distribution.
July 1978
After the March 1978 changes, a survey in April 1978, showed the
Oxo incinerator to be performing very well (VOC destruction efficiency
of 99.6 percent) but with a high superheat temperature of ~850°F. So,
in July 1978, some stainless steel shields were installed over the
superheater elements to help lower the superheat temperature. A subsequent
survey in September 1978, showed the incinerator to still be destructing
99.6 percent VOC and with a lower superheat temperature (~750°F).
This study pointed out that mixing is a critical factor in efficiency
and that incinerator adjustment after startup is the most feasible and
efficient means of improving mixing and thus, the destruction efficiency.
C-6
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C.I.1.2 Koppers Test Data
1. Facility and Control Device - The Koppers incinerator is
actually a boiler adapted to burn gaseous wastes from maleic anhydride
unit. The boiler is designed to operate at a temperature of 2000°F and
a residence time of 0.6 second.. Current operating parameters have not
been measured, but it is the company's judgement that the boiler now
operates somewhat below 2000°F. The flowrate of waste gas to the boiler
is usually 32,000 scfm and contains 350 Ibs/hr benzene, 2850 Ibs/hr
carbon monoxide, 22,100 Ibs/hr oxygen, 6434 Ibs/hr water, and 105,104
Ibs/hr nitrogen. While these values are typical for the system, they
vary throughout the production cycle. The boiler is fired with natural
gas.
2. Sampling and Analytical Techniques - Different methods were
used for inlet and outlet sampling. Although integrated samples were
used for the outlet, gas bottle samples were used for the inlet. Such a
sampling technique would likely give a low bias to the measured inlet
VOC concentration.
The inlet concentration was taken to be the average of all maleic
reactor offgas measurements made. There were four samples taken, and
the results were 600 ppmv, 1172 ppmv, 600 ppmv, and 964 ppmv for an
average of 834 ppmv benzene. (These values are not boiler inlet values
since they were collected prior to the introduction of the additional
combustion air.) This wide range of benzene values indicates the great
deal of variability inherent in efficiency calculations employing such a
sampling technique.
For the June 1978 tests, samples of stack gas were taken in glass
bottles by plant chemists and analyzed at Koppers' Monroeville Research
Center by direct injection to a gas chromatograph with flame ionization
detector. The November 1977, method used specially-designed charcoal
adsorption tubes, instead of impingers, in a United States Environmental
Protection Agency-type sampling train. The charcoal was eluted with CS2
and the eluent analyzed by gas chromatography.
3. Test Results - One test run of the Koppers data indicates 97.2
percent efficiency at 1800°F. However, the entire Koppers test is
disregarded as not demonstrably accurate because of the poor sampling
C-7
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technique. Grab samples employed in obtaining inlet gas could give a
low bias to the measured inlet VOC concentration. Therefore, the calculated
VOC destruction efficiency would be artificially low. Table C-l provides
a summary of these test results.
C.I.1.3 Monsanto Test Data
1. Facility and Control Device - The Monsanto incinerator burns
both liquid and gaseous wastes from the acrylonitrile unit and is termed
an absorber vent thermal oxidizer. Two identical oxidizers are employed.
The primary purpose of the absorber vent thermal oxidizers is hydrocarbon
emission abatement.
Acrylonitrile is produced by feeding propylene, ammonia, and excess
air through a fluidized, catalytic bed reactor. In the process, acrylonitrile,
acetonitrile, hydrogen cyanide, carbon dioxide, carbon monoxide, water,
and other miscellaneous organic compounds are produced in the reactor.
The columns in the recovery section separate water and crude acetonitrile
as liquids. Propane, unreacted propylene, unreacted air components,
some unabsorbed organic products,- and water are emitted as a vapor from
the absorber column overhead. The crude acrylonitrile product is further
refined in the purification section to remove hydrogen cyanide and the
remaining hydrocarbon impurities.
The organic waste streams from this process are incinerated in the
absorber vent thermal oxidizer at a temperature and residence time
sufficient to reduce stack emissions below the required levels. The
incinerated streams include (1) the absorber vent vapor (propane, propylene,
CO, unreacted air components, unabsorbed hydrocarbons), (2) liquid waste
acetonitrile (acetonitrile, hydrogen cyanide, acrylonitrile), (3) liquid
waste hydrogen cyanide, and (4) product column bottoms purge (acrylonitrile,
some organic heavies). The two separate acrylonitrile plants at Chocolate
Bayou, employ identical thermal oxidizers.
Each thermal oxidizer is a horizontal, cylindrical, saddle-supported,
end-fired unit consisting of a primary burner vestibule attached to the
main incinerator shell. Each oxidizer measures 18 feet in diameter by
36 feet in length.
The thermal oxidizer is provided with special burners and burner
guns. Each burner is a combination fuel-waste liquid unit. The absorber
C-8
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vent stream is introduced separately into the top of the burner vestibule.
The flows of all waste streams are metered and sufficient air is added
for complete combustion. Supplemental natural gas is used to maintain
the operating temperature required to combust the organics and to maintain
a stable flame on the burners during minimum gas usage. Figure C-2
gives a plan view of the incinerator.
2. Sampling and Analytical Techniques
Feed Stream and Effluent
The vapor feed streams (absorber vent) to the thermal oxidizer and
the effluent gas stream are sampled and analyzed using a modified analytical
reactor recovery run method. The primary recovery run methods are Sohio
Analytical Laboratory Procedures.
The modified method involves passing a measured amount of sample
gas through three scrubber flasks containing water and catching the
scrubbed gas in a gas sampling bomb. The samples are then analyzed with
a gas chromatograph and the weight percent of the components is determined.
Stack Gas
Figure C-3 shows the apparatus and configuration used to sample the
stack gas. It consists of a line of the sample valve to the small
water-cooled heat exchanger. The exchanger is then connected to a
250 ml sample bomb used to collect the unscrubbed sample. The bomb is
then connected to a pair of 250 ml bubblers, each with 165 ml of water
in it. The scrubbers, in turn, are connected to another 250 ml sample
bomb used to collect the scrubbed gas sample which is connected to a
portable compressor. The compressor discharge then is connected to a
wet test meter that vents to the atmosphere.
After assembling the apparatus, the compressor is turned on and it
3
draws gas from the stack and through the system at a rate of ~0.2 ft /min.
Sample is drawn until at least 10 ft have passed through the scrubbers.
3
After 10 ft has been scrubbed, the compressor is shutdown and the
unscrubbed bomb is analyzed for Cl-L, C^'s, CJHg, and CJ-lo, the scrubbed
bomb is analyzed for Ng* air, Op, COp* and CO, and the bubbler liquid is
analyzed for acrylonitrile, acetonitrile, hydrogen cyanide, and total
organic carbon. The gas samples are analyzed by gas chromatography.
C-9
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For the liquid samples, acrylonitrile and acetonitrile are analyzed by gas
chromatography; hydrogen cyanide (HCN) is by titration; and total organic
carbon (TOC) is by a carbon analysis instrument.
3.. Test Results - Monsanto's test results show efficiencies well
above 98 percent, however, the parameters at which it is achieved are
confidential. All other known conditions are presented in Table C-l.
C.I.2 Environmental Protection Agency (EPA) Test Data
The EPA test study represents the most in-depth work available.
These data show the combustion efficiencies for full-scale incinerators
on air oxidation vents at three chemical plants. Data includes inlet/outlet
tests on large incinerators, two at acrylic acid plants, and one at a
maleic anhydride plant. The tests measured inlet and outlet VOC by
compound at different temperatures, and the reports include complete
test results, process rates, and test method descriptions. The three
plants tested are the Denka, Houston, Texas, maleic anhydride unit and
the Rohm and Haas, Deer Park, Texas,'and Union Carbide, Taft, Louisiana,
acrylic acid units. The data from Union Carbide include test results
based on two different incinerator temperatures. The data from Rohm and
Haas include results for three temperatures. In all tests, bags were
used for collecting integrated samples and a GC/FID was used for organic
analysis.
C.I.2.1 Denka Test Data6
1. Facility and Control Device - The Denka maleic anhydride
facility has a nameplate capacity of 23,000 Mg/yr (50 million Ibs/yr).
The plant was operating at about 70 percent of capacity when the sampling
was conducted. The plant personnel did not think that the lower production
rate would seriously affect the validity of the results.
Maleic anhydride is produced by vapor-phase catalytic oxidation of
benzene. The liquid effluent from the absorber, after undergoing recovery
operations, is about 40 weight percent aqueous solution of maleic acid.
The absorber vent is directed to the incinerator. The thermal incinerator
uses a heat recovery system to generate process steam and uses natural
2
gas as supplemental fuel. The size of the combustion chamber is 2195 ft .
There are three thermocouples used to sense the flame temperature, and
C-l 2
-------
these are averaged to give the temperature recorded in the control room. A
rough sketch of the combustion chamber is provided in Figure C-4.
2. Sampling and Analytical Techniques
THC, Benzene, Methane, and Ethane
The gas samples were obtained according to the September 27, 1977,
R
EPA draft benzene method. Seventy-liter aluminized Mylar bags were used
with sample times of two to three hours. The sample box and bag were
heated to approximately 66°C (150°F) using an electric drum heater and
insulation. During Run 1-Inlet, the variac used to control the temperature
malfunctioned so the box was not heated for this run. A stainless steel
probe was inserted into the single port at the inlet and connected to
the gas bag through a "tee". The other leg of the "tee" went to the
n
total organic acid (TOA) train. A Teflon line connected the bag and
the "tee". A stainless steel probe was connected directly to the bag at
the outlet. The lines were kept as short as possible and not heated.
The boxes were transported to the field lab immediately upon completion
of sampling. They were heated until the GC analyses were completed.
A Varian model 2440 gas chromatograph with a Carle gas sampling valve,
3
equipped with two cm matched loops, was used for the integrated
bag analysis. The SP-1200/Bentone 34 column was operated at 80°C. The
instrument has a switching circuit which allows a bypass around the
column through a capillary tube for THC response. The response cuh/e
was measured daily for benzene (5, 10, and 50 ppm standards) with the
column and in the bypass (THC) mode. The THC mode was also calibrated
daily with propane (20, 100, and 2000 ppm standards). The calibration
plots showed moderate nonlinearity. For sample readings which fell
within the range of the calibration standards, an interpolated response
factor was used from a smooth curve drawn through the calibration points.
For samples above or below the standards, the response factor of the
nearest standard was assumed. THC readings used peak height and ciolumn
readings used area integration measured with an electronic "disc"
integrator.
CO
Analysis for these constituents was done on samples drawn froip the
integrated gas bag used in THC, benzene, methane, and ethane. Carb.on
C-13
-------
12ft
FLOW
SIDE VIEW
(Inlet)
23H-3Jin —
There are Three Thermocouples Spaced Evenly Across the Top of the Firebox.
The Width of the Firebox is 6ft-6in.
Figure C-4. Incinerator combustion chamber.
17ft-Sin
(Outlet)
C-14
-------
monoxide analysis was done following the GC analyses using EPA Reference
Method 10 (Federal Register, Vol. 39, No. 47, March 8, 1974). A Beckman
Model 215 NDIR analyzer was used to analyze both the inlet and outlet
samples.
Duct Temperature, Pressure,, and Velocity
Duct temperature and pressure values were obtained from the existing
inlet port. A thermocouple was inserted into the gas sample probe for
the temperature while a water manometer was used for the pressure readings.
These values were obtained at the conclusion of the sampling period.
Temperature, pressure, and velocity values were obtained for the
outlet stack. Temperature values were obtained by thermocouple during
the gas sampling. Pressure and velocity measurements were taken according
to EPA Reference Method 2 (Federal Register, Vol. 42, No. 160,
August 18, 1977). These values also were obtained at the conclusion of
the sampling period.
2. Test Results - The Denka inc-inerator achieves greater than 98
percent reduction at 1400°F and 0.6 second residence time. These results
suggest that the recommended 98 percent control level is achievable by
properly maintained and operated new incinerators, for which the operating
conditions are less stringent than 1600°F and 0.75 second. Table C-l
provides a summary of these test results.
C.I.2.2 Rohm and Haas Test Data7
1- Facility and Control Device - The Rohm and Haas plant in Deer
Park, Texas, produces acrylic acid and ester. The capacity of this
facility has been listed at 400 million Ibs/yr of acrylic monomers.
Acrylic esters are produced using propylene, air, and alcohols, with
acrylic acid produced as an intermediate. Acrylic acid is produced
directly from propylene by a vapor-phase catalytic air oxidation process.
The reaction product is purified in subsequent refining operations.
Excess alcohol is recovered and heavy end by-products are incinerated.
This waste incinerator is designed to burn offgas from the two absorbers.
In addition, all process vents (from extractors, vent condensers, and
tanks) which might be a potential source of gaseous emissions are collected
in a suction vent system and normally sent to the incinerator. An
C-15
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organic liquid stream generated in the process is also burned, thereby
providing part of the fuel requirement. The remainder is provided by
natural gas. Combustion air is added in an amount to produce six percent
oxygen in the effluent. Waste gases are flared during maintenance
shutdowns and severe process upsets. The incinerator unit was tested
because it operates at relatively shorter residence times (0.75-1.0
seconds) and higher combustion temperatures (1200°-1560°F) than most
existing incinerators.
The total installed capital cost of the incinerator was $4.7 million.
The estimated operating cost due to supplemental natural gas use is $0.9
million per year.
2. Sampling and Analytical Techniques - Samples were taken
simultaneously at a time when propylene oxidations, separations, and
esterifications were operating smoothly and the combustion temperature
was at a steady state. Adequate time was allowed between the tests
conducted at different temperatures for the incinerator to achieve
steady state. Bags were used to collect integrated samples and a 6C/FID
was used for organic analysis.
3. Test Results - VOC destruction efficiency was determined at
three different temperatures: 1425°F, 1510°F, and 1545°F. Efficiency
is found to increase with temperature and, except for 1425°F, it is
above 98 percent. Test results are summarized in Table C-l. These
tests were for residence times greater than 0.75 second. However,
theoretical calculations show that greater efficiency would be achieved
at 1600°F and 0.75 second than at the longer residence times, but lower
temperatures represented in these tests.
C.I.2.3 Union Carbide (UCC) Test Data8
1. Facility and Control Device - The capacities for the UCC
acrylates facilities are about 200 million Ibs/yr of acrolein, acrylic
acid, and esters. Acrylic acid comprises 130 million Ibs/yr of this
total. Ethyl acrylate capacity is 90 million Ibs/yr. Total heavy ester
capacities (such as 2-ethyl-hexyl acrylate) are 110 million Ibs/yr. UCC
considers butyl acrylate a heavy ester.
The facility was originally built in 1969 and utilized British
Petroleum technology for acrylic acid production. In 1976 the plant was
converted to a technology obtained under license from Sohio.
C-l 6
-------
The thermal incinerator is one of the two major control devices
used in acrylic acid and acrylate ester manufacture. The UCC incinerator
was installed in 1975 to jdestroy acrylic acid and acrolein vapors. This
unit was constructed by John Zink Company for an installed cost of $3
million and incorporates ;a heat recovery unit to produce process steam
at 600 psig. The unit operates at a relatively constant feed input and
supplements the varying flow and fuel value of the streams fed to it
with inversely varying amounts of fuel gas. Energy consumption averages
52.8 million Btu/hr instead of the designed level of 36-51 million
Btu/hr. The operating cost in 1976, excluding capital depreciation, was
$287,000. The unit is run with nine percent excess oxygen instead of
the designed three to five percent excess oxygen. The combustor is
designed to handle a maximum of four percent propane in the oxidation
feed.
Materials of construction of a non-return block valve in the
600 psig steam line from the boiler section requires that the incinerator
be operated at 1200°F instead of the designed 1800°F. The residence
time is three to four seconds.
2. Sampling and Analytical Procedures - The integrated gas samples
were obtained according to the September 27, 1977, EPA draft benzene
method. I
Each integrated gasUample was analyzed on a Varian Model 2400 gas
chromatograph with FID, and a heated Carle gas sampling valve with
matched 2 cm sample loop!s. A valved capillary bypass is used for total
hydrocarbon (THC) analyses and a 2 m, 1/8-in., OD nickel column with
PORAPAK P-S, 80-100 mesh packing is used for component analyses.
Peak area measurements were used for the individual component
analyses. A Tandy TRS-80, 48K floppy disc computer interfaced via the
integrator pulse output of a Linear Instruments Model 252A recorder
acquired, stored, and analyzed the chromatograms.
The integrated gas samples were .analyzed for oxygen and carbon
dioxide by duplicate Fyrjite readings. Carbon monoxide concentrations
were obtained using a Betkman Model 215A nondispersive infrared (IR)
analyzer using the integrated samples. A three-point calibration (1000,
3000, and 10,000 ppm CO standards) was used with a linear-log curve fit.
C-17
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Stack traverses for outlet flowrate were made using EPA Methods 1
through 4 (midget impingers) and NOV was sampled at the outlet using EPA
X
Method 7.
3. Test Results - VOC destruction efficiency was determined at
two different temperatures. Table C-l provides a summary of these test
results. Efficiency was found to increase with temperature. At 1475°F,
the efficiency was well above 99 percent. These tests were, again, for
residence times greater than 0.75 second. However, theoretical calculations
show that greater efficiency would be achieved at 1600°F and 0.75 second
than at the longer residence times but lower temperatures represented in
these tests.
All actual measurements were made as parts per million (ppm) of
propane with the other units reported derived from the equivalent values.
The values were measured by digital integration.
The incinerator combustion temperature for the first six runs was
about 1160°F. Runs 7 through 9 were made at an incinerator temperature
of about 1475°F. Only during Run 3 was the acrolein process operating.
The higher temperature caused most of the compounds heavier than propane
to drop below the detection limit due to the wide range of attenuations
used, nearby obscuring peaks, and baseline noise variations. The detection
limit ranges from about 10 ppb to 10 ppm, generally increasing during
the chromatogram, and especially near large peaks. Several of the minor
peaks were difficult to measure. However, the compounds of interest,
methane, ethane, ethylene, propane, propylene, acetaldehyde, acetone,
acrolein, and acrylic acid, dominate the chromatograms. Only acetic
acid was never detected in any sample.
The probable reason for negative destruction efficiencies for
several light components is generation by pyrolysis from other components.
For instance,; the primary pyrolysis products of acrolein are carbon
monoxide and jsthylene. Except for methane and, to a much lesser extent,
ethane and pr'ppane, the fuel gas cannot contribute hydrocarbons to the
outlet samples.
j
A sample'taken from the inlet line knockout trap showed 6 pg/g of
acetaldehyde,\25 ug/g of butenes, and 100 yg/g of acetone when analyzed
by gas chroma^ography/f1ame ionization detection (GC/FID).
C-l 8
-------
C.I.3 Union Carbide Lab-Scale Test Data
Union Carbide test data show the combustion efficiencies achieved
on 15 organic compounds in a lab-scale incinerator operating between 800°
and 1500 F and .1 to 2 seconds residence time. The incinerator consisted.
of a 130 cm, thin bore tube, in a bench-size tube furnace.; Outlet
analyzers were done by direct routing of the incinerator outlet to a FID
and GC. All inlet gases were set at 1000 ppmv.
In order to study the impact of incinerator variables on efficiency,
mixing must first be separated from the other parameters. Mixing cannot
be measured and thus, its impact on efficiency cannot be readily separated
when studying the impact of other variables. The Union Carbide lab work
was chosen since its small size and careful design best assured consistent
and proper mixing.
The results of this study are shown in Table C-2. These results
show moderate increases in efficiency with temperature, residence time,
and type of compound. The results also show the impact of flow regime
on efficiency.
Flow regime is important in interpreting the Union Carbide lab unit
results. These results are significant since the lab unit was designed
for optimum mixing and thus, the results represent the upper limit of
incinerator efficiency. As seen in Table C-2, the Union Carbide results
vary by flow regime. Though some large-scale incinerators! may achieve
good mixing and plug flow, the worst cases will likely require flow
patterns similar to complete backmixing. Thus, the result! of complete
backmixing would be, relatively, more comparable to those obtained from
large-scale units.
C.2 NITROGEN OXIDES (NO ) EMISSIONS
A
Nitrogen oxides are derived mainly from two sources: ;(1) from
nitrogen contained in the combustion air called thermal NOL, and (2)
from nitrogen chemically combined in the fuel, called fuel! NO . In
addition, combustion of waste gas containing high levels of nitrogen-
containing compounds also may cause increases in NO emissions. For
fuels containing low amounts of nitrogen, such as natural ^as and light
distillate oils, thermal NOX is by far the larger component, of total NO
i X
C-19
-------
TABLE C-2. RESULTS OF DESTRUCTION EFFICIENCY UNDER STATED
CONDITIONS (UNION CARBIDE TESTS'1)
Residence Time/ Compound
0.75 second
Flow u Temperature
Regime5 (SF)
Two-stage
Backmixing
Compl ete
Backmixing
Plug Flow
1300
1400
1500
1600
1300
1400
1500
1600
1300
1400
1500
1600
Ethyl
Acrylate
99.9
99.9
99.9
99.9
98.9
99.7
99.9
99.9
99.9
99.9
99.9
99.9
Ethanol
94.6
99.6
99.9
99.9
86.8
96.8
99.0
99.7
99.9
99.9
99.9
99.9
Ethyl ene
92.6
99.3
99.9
99.9
84.4
95.6
98.7
99.6
99.5
99.9
.99.9
199.9
1
Vinyl
Chloride
78.6
99.0
99.9
99.9
69.9
93.1
98.4
99.6
90.2
99.9
99.9
99.9
.5 & 1.5 sec
Ethyl ene
87.2/27.6
98.6/99.8
99.9/99.9
99.9/99.9
78.2/91.5
93.7/97.8
98.0/99.0
99.4/99.8
97.3/99.9
99.9/99.9
99.9/99.9
99.9/99.9
aThe results of the Union Carbide work are presented as a series of equations. These
equations relate destruction efficiency to temperature, residence time, and flow
regime for each of 15 compounds. The efficiencies in this table were calculated
from these equations.
^Three flow regimes are presented: two-stage backmixing, complete backmixing, and
plug flow. Two-stage backmixing is considered a reasonable approximation of actual
field units, with complete backmixing and plug flow representing the extremes.
C-20
-------
emissions. By contrast, fuel NOX predominates for heavy oils, coal, and
other high-nitrogen fuels such as coal-derived fuels and shale oils.
Thermal oxidizer outlet concentrations of NO were measured in
seven sets of thermal oxidizer tests conducted at three air oxidation
plants. Table C-3 provides a summary of the test results. The test
results indicate that NOX outlet concentrations range from 8 to 200 ppmv
(0.015 to 0.37 g/m ). These values could increase by several orders of
magnitude in a poorly designed or operated unft. NO samples were
obtained according to EPA Reference Method 7.
The maximum outlet NO concentration of 200 ppmv was measured at an
/\
acrylonitrile plant. The vent stream of this plant contains nitrogeneous
compounds. The NOX concentrations measured at the other two plants,
whose vent, streams do not contain nitrogeneous compounds, range from 8
to 30 ppmv (0.015 to 0.056 g/m3).
C.3 COMPARISON OF TEST RESULTS AND THE TECHNICAL BASIS OF THE SOCMI
AIR OXIDATION EMISSIONS LIMIT
This section compares.various, test results, discusses data and
findings on incinerator efficiency, and presents the logic and the
technical basis behind, the choice of the above control level,
A consideration of VOC.combustion kinetics leads to the conclusion
that at'1600°F and 0.75 second residence time, mixing is the crucial
design parameter.. Published literature indicates that any VOC can be
oxidized to carbon dioxide and water if held at sufficiently high temperatures
in the presence of oxygen for a sufficient time. However, the temperature
at which a given level of VOC reduction is achieved is unique for each
VOC compound. Kinetic studies indicate that there are two slow or rate-
determining steps in the oxidation of a compound. The first is the
initial reaction in which the original compound disappears. It has been
determined that the initial reaction of methane (CH4) is slower than,
that of any other nonhalogenated organic compound. Kinetic calculations
show that, at 1600°F, 98 percent of the original methane will react in
0.3 seconds. Therefore, any .nonhalogenated VOC will undergo an initial
reaction step within this time. After the initial step, extremely rapid
free radical reactions occur. Finally, each carbon atom will exist as
carbon monoxide (CO) before oxidation is complete. The oxidation of CO
is the second slow step. Calculations show that, at 1600°F, 98 percent
C-21
-------
TABLE C-3. SUMMARY OF RESULTS: NOV DATA
A
Company
Number of Sets
and/or
Number of Runs
Outlet NO
in Flue Gas
(ppmv)
Union Carbide
Set 1
(6)
Set 2
(3)
27
30
Denka
Set 1
Set 2
Set 3
9.3
10.2
8.0
Monsanto
Unit 1
Unit 2
200
8
C-22
-------
of an original .concentration of CO will react in 0.05 second. Therefore,
98 percent of any VOC would be expected to undergo the initial and final
slow reaction steps at 1600°F in about 0.35 second. It is very unlikely
that the intermediate free radical reactions would take nearly as long
as 0.4 seconds :to convert. 98 percent of the organic molecules to CO.
Therefore, from a theoretical viewpoint, any VOC should undergo complete
combustion at 1600°F in 0.75 second. The calculations on which this
conclusion is based have taken into account the low mole fractions of
VOC and oxygen which would be found in the actual system. They have
also provided for the great.decrease in concentration per unit volume
due to the elevated temperature. But the calculations assume perfect
mixing of the offgas and combustion air. Mixing is therefore identified
from a theoretical viewpoint as the crucial design parameter.
The test results, both indicate an achievable control level of 98
percent at or below 1600°F and illustrate the importance of mixing.
Union Carbide results, on lab-scale incinerators indicated a minimum of
98.6 percent efficiency at 1400°F. Since lab-scale incinerators primarily
differ from field units in their excellent mixing, these results verified
the theoretical calculations. The tests cited in Table C-l are documented
as being conducted on full-scale incinerators controlling offgas from
air oxidation process vents of a variety of types of plants. To focus
on mixing, industrial .units...were selected where all variables except
mixing were hel;d constant or accounted for in other ways. It was then
assumed any changes in efficiency would be due to changes in mixing.
The case most directly showing the effect of mixing is that of
Petro-tex incinerator. The Petro-tex data show the efficiency changes
due to modifications on the incinerator at.two times after startup.
These modifications included (1) repositioning baffles, (2) adjusting
duct slots andjopenings in the mixing zone to improve exit velocity, (3)
installing newjdampers, baffles and perforated plates, and (4) rerouting
inlet combustiqn air. These, modifications increased efficiency from 70
percent to overj 99 percent, with no significant change in temperature.
A comparison indirectly showing the effect of mixing is that of the
Rohm and Haas- tipst versus the Union Carbide lab test as presented in
Table C-4. The^e data compare the efficiency of the Rohm and Haas (R&H)
C-23
-------
TABLE C-4. RESULT COMPARISONS OF LAB INCINERATOR vs. ROHM & HAAS
INCINERATOR
Compound
Propane
Propyl ene
Ethane
Ethyl ene
TOTAL
Rohm & Haas
Inlet
(Ibs/hr)
900
1800b
10
30
2740
Incinerator
Outlet
(Ibs/hr)
150
150b
375
190
865
Union Carbide
Inlet
(Ibs/hr)
71.4
142.9
0.8
_2_.4
217.5
Lab Incinerator
Outlet
(Ibs/hr)
0.64
5.6
3.9
• J3J-,
13.54
% VOC Destruction:
68.4%
93.8%
aTable shows the destruction efficiency of the four listed compounds for the
Rohm & Haas (R&H) field and Union Carbide (UC) lab incinerators. The R&H
results are measured; the UC results are calculated. Both sets of results
are based on 1425 F combustion temperature and one second residence time.
In addition, the UC results are based on complete backmixing and a four-step
combustion sequence consisting of propane to propylene to ethane to ethylene
to C02 and H20. These last two items are worst case assumptions.
bAre not actual values. Actual values are confidential. Calculations with
actual values give similar results.
C-24
-------
incinerator in combusting four specific compounds with that of the Union
Carbide lab unit. The lab unit clearly outperforms the R&H unit. The
data from both units are based on the same temperature, residence time,
and inlet stream conditions. The more complete mixing of the lab unit
is judged the cause of the differing efficiencies. The six tests of in-
place incinerators do not, of course, cover every feedstock. However,
the theoretical discussion given above indicates that any VOC compound
should be sufficiently destroyed at 1600°F. More critical than the type
of VOC is the VOC concentration in the offgas. This is true because the
kinetics of combustion are not exactly first-order at low VOC concen-
trations. The Petro-tex results are for a butadiene plant, and butadiene
offgas tends to be lean in VOC. Therefore, test results support the
validity of the standard for lean streams.
The EPA, Union Carbide, and Rohm and Haas tests were for residence
times greater than.0.75 second. However, theoretical calculations show
that greater efficiency would be achieved at 1600°F and.0.75 second than
at the longer residence times but lower temperatures represented in
these two tests. The data on which the standard is based is test data
for similar control systems: thermal incineration at various residence
times and. temperatures. If 98 percent VOC reduction can be achieved at
a lower temperature, then according to kinetic theory it can certainly
be achieved at 1600°F, other conditions being equal.
A control efficiency of 98 percent VOC reduction, or 20 ppmv by
compound, whichever is less stringent, represents the highest acheivable
control level for all new incinerators, considering available technology,
cost and energy use. This is based on incinerator operation at 16QO°F
and on adjustment of the incinerator after start-up. The 20 ppmv (by
compound) level was chosen after three different incinerator outlet VOC
concentrations, 10 ppmv, 20 ppmv, and 30 ppmv, were analyzed. In
addition to the incinerator tests cited earlier in this Appendix, data
from over 200 tests by Los Angeles County (L.A.) on various waste gas
incinerators were considered in choosing the 20 ppmv level. However,
the usefulness of the L.A. data was limited by three factors: (1) the
incinerators tested are small units designed over a decade ago; (2) the
units were designed, primarily, for use on coating operations; and
(3) the units were designed to meet a regulation requiring only 90 percent
VOC reduction.
C-25
-------
The 10 ppmv level was judged to be too stringent. Two of the six
non-L.A. tests and 65 percent of the L.A. tests fail this criteria.
Consideration was given to the fact that many of the units tested were
below 1600°F and did not have good mixing. However, due to the large
percent that failed, it is judged that even with higher temperatures and
moderate adjustment, a large number of units would still not meet the
10 ppmv level.
The 20 ppmv level was judged to be, attainable. All of the non-L.A.
and the majority of the L.A. units met this criteria. There was concern
over the large number of L.A. tests that failed, i.e. 43 percent.
However, two factors outweighed this concern.
First, all of the non-L.A. units met the criteria. This is significant
since, though the L.A. units represent many tests, they represent the
same basic design. They all are small units designed over a decade ago
to meet a rule for 90 percent reduction. They are for similar applications
for the same geographic region designed in many cases by the same
vendor. Thus, though many failed, they likely did so due to common
factors and do not represent a wide spread inability to meet 20 ppmv.
Second, the difference between 65 percent failing 10 ppmv and
43 percent failing 20 ppmv is larger than a direct comparison of the
percentages would reveal. At 20 ppmv, not only did fewer units fail,
but those that did miss the criteria did so by a smaller margin and
would require less adjustment.. Dropping the criteria from 10 ppmv to
20 ppmv drops the failure rate by 20 percent, but is judged to drop the
overall time and cost for adjustment by over 50 percent.
The difference between the two levels is even greater when the
adjustment effort for the worst case is considered. The crucial point
is how close a 10 ppm level pushes actual field unit efficiencies to
those of the lab unit. Lab unit results for complete backmixing indicate
that a 10 ppmv level would force field units to almost match lab unit
mixing. A less stringent 20 ppmv level increases the margin allowed for
nonideal incinerator operation, especially for the worst cases. Given
that exponential increase may occur in costs to improve mixing as field
units approach lab unit efficiencies, a drop from 10 ppmv to 20 ppmv may
decrease costs to improve mixing in the worst case by an order of
magnitude.
C-26
-------
The 30 ppmv level was judged too lenient. The only data indicating
such a low efficiency was from L.A. All other data showed 20 ppmv. The
non-L.A. data and lab data meet 20 ppmv and the Petro-tex experience
showed that moderate adjustment can increase efficiency. In addition,
the L.A. units were judged to have poor mixing. The mixing deficiencies
were large enough to mask the effect of increasing temperature. Thus,
it is judged that 20 ppmv could be reached with moderate adjustment and
that a 30 ppmv level would represent a criteria not based on the best
available units, considering cost, energy, and environmental impact.
C-27
-------
C.4 REFERENCES FOR APPENDIX C
1. Mascone, D.C.., EPA, Memorandum concerning incinerator efficiency,
June 11, 1980.
2. Letter from Towe, R., Petro-Tex Chemical Corporation, to Farmer, J.,
EPA, August 15, 1979.
3. Broz, L.D. and Pruessner, R.D., "Hydrocarbon Emission Reduction
Systems Utilized by Petro-Tex", paper presented at 83rd National
Meeting of AIChE, 9th Petrochemical and Refining Exposition,
Houston, Texas, March 1977.
4. Letter from Lawrence, A., Koppers Company, Inc., to Goodwin, D.,
EPA, January 17, 1979.
5. Letter from Weishaar, M., Monsanto Chemical Intermediates Co., to
Fanner, J., EPA, November 8, 1979.
6, Maxwell, W., and Scheil, 6., "Stationary Source Testing of a Maleic
Anhydride Plant at the Denka Chemical Corporation, Houston, Texas,"
EPA Contract No. 68702-32814, March 1978.
7. Blackburn, J., Emission Control Options for the Synthetic Organic
Chemicals Manufacturing Industry, Trip Report, EPA Contract No.
68702-2577, November 1977.
8. Scheil, 6., Emission Control Options for the Synthetic Organic
Chemicals Manufacturing Industry, Trip Report, EPA Contract No.
68702-2577, November 1977.
9. Lee, K., Hansen, J., and Macau!ey, D., "Thermal Oxidation Kinetics
of Selected Organic Compounds", paper presented at the 71st Annual
Meeting of the APCA, Houston, Texas, June 1978.
C-28
-------
APPENDIX D: MONITORING AND PEFORMANCE TEST METHODS
-------
-------
APPENDIX D: MONITORING AND PERFORMANCE TEST METHODS
D.I INTRODUCTION
The proposed air oxidation New Source Performance Standard (NSPS)
divides air oxidation processes into two groups. One group of facilities
is required under the proposed standard, to reduce VOC emissions by
98 weight percent or to 20 ppm (volume, by compound), whichever is less
stringent. Standard measurement methods should be used to determine the
VOC reduction. The second group is not required to reduce VOC emissions
under the proposed standard. As discussed in Chapter 8 and Appendix E,
the two groups of facilities are distinguished by a cutoff level of
total resource-effectiveness (TRE). An index value of TRE can be associated
with each air oxidation vent stream for which the offgas characteristics
of flowrate, hourly VOC emissions, and net heating value are known. The
proposed standard would require that measurements be made to determine
whether a source has a TRE index value above or below the cutoff level.
In this case, measurements are needed to determine the flowrate, hourly
VOC emissions, and net heating value of each air oxidation process vent
stream.
The purpose of this appendix is to discuss and present measurement
methods acceptable for determination of (1) VOC reduction efficiency,
(2) hourly VOC emissions, and (3) stream net heating value.
D.2 VOC REDUCTION EFFICIENCY MEASUREMENT
Numerous methods exist for the measurement of organic emissions.
Among these methods are gas chromatograph (GC), direct flame ionization
detection (FID), and EPA Reference Method 25 (EPA 25) -- Determination
of Total Gaseous Non-Methane Organic Emissions as Carbon. Each method
has advantages and disadvantages. Of the three procedures, GC has the
distinct advantage of identifying, and quantifying the individual compounds
are that GC systems are expensive and determination of the column required
and analysis of samples can be time consuming.
The FID technique is the simplest procedure. However, the FID
responds differently to various organic compounds and can yield highly
biased results depending upon the compounds involved. Another disadvantage
of the FID is that a separate methane measurement is required to determine
D-l
-------
non-methane organics. The direct FID procedure does not identify or
quantify individual compounds.
Method 25 sampling and analysis provides a single non-methane
organic measurement on a carbon basis; this is convenient for establishing
control device efficiencies on a consistent basis. However, EPA 25 does
not provide any qualitative or quantitative information on individual
compounds present.
D.2.1 Emission Measurement Tests
Emission tests1'2 using these three methods were conducted for the
Office of Air Quality Planning and Standards (OAQPS) at two air oxidation
facilities (acrylic acid production). In addition, a laboratory study
was conducted by Midwest Research Institute (MRI) under EPA contract to
investigate the applicability of Method 25 to measurement of emissions
from air oxidation processes.
Table D-l summarizes the data obtained at the two field tests. For
each test method, the calculated (average) control device efficiencies
are presented; the average inlet and outlet concentrations (ppm volume
as carbon) are also presented. Note that the control device efficiencies
are calculated from mass emission rates (not presented in Table D-l)
since the addition of significant amounts of combustion air at these
sources effectively reduces the outlet concentrations. The inlet and
outlet concentrations are presented in Table D-l only to provide the
reader with an idea of the concentration levels involved.
In Table D-l, four basic data sets are provided - data for two
incincerator operating conditions at each of two different facilities.
In general, the calculated efficiencies for the different test methods
are very similar and are in the 94-99 percent range. However, this
range is significant when dealing with a standard of 98 percent control
efficiency. One notable deviation from this general conclusion is Plant A,
Condition 1, where the FID yielded a calculated efficiency of 93 percent;
this was significantly higher than either the GC or EPA 25 which yielded
efficiencies of 71 and 77 percent, respectively. The higher calculated
efficiency for the FID was a result of lower outlet emission rates
measured by the FID. EPA 25 usually gave the lowest calculated efficiencies,
followed by the GC, and then the FID procedures. Although Method 25,
D-2
-------
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yielded efficiency results only slightly less than GC, in two cases the
outlet concentration measured by EPA 25 was significantly higher than
those measured by GC (Condition 2, Plants A andjB). The higher (.In one
case, 100 times) emission data at the outlet dojnot significantly
affect the calculated control device efficiencies because the inlet
concentration is quite high (30,000 ppm); consequently, outlet measurements
of 3 ppm and 300 ppm result in efficiencies of 99.9 and 99.0 percent,
respectively. In a situation of lower inlet concentration (1000 ppm
range, for example) the higher results obtained.by EPA 25 at the outlet
could significantly affect the calculated control device efficiency.
The phenomenon of high (relative to GC or FID) EPA 25 result has been
experienced at other test locations and appears;to occur particularly as
the outlet concentration decreases below the 100 ppm level. It is
believed that this phenomenon is related to contamination in the sampling
equipment and/or analytical system. EPA is currently investigating the
possible causes of this problem and is looking at appropriate solutions
(e.g., increased laboratory quality assurance and larger sample volumes).
One other point related to the test data warrants mention. EPA 25 data
at the Plant B inlet (no EPA 25 data were obtained at the Plant A inlet)
are consistently about 20 percent lower than the GC or FID data. Based
on recent results of a laboratory study conducted by MRIj , it is believed
that these low results are due to the presence of highly polar compounds
in the inlet stream. It is suspected that the GC column, currently
specified in EPA 25, although adequate for the compounds1 (solvents)
normally used in the surface coating industries, is not adequate for
analysis of some of the polar compounds found in the air1 oxidation
process effluent. Further work is planned in this area Ito determine if
the EPA 25 GC column is indeed the problem, and, if so, how it may be
improved.
D.2.2 Recommended Test Method
The CG/FID is the recommended test procedure for determining control
device efficiency for air oxidation processes. A general .GC procedure
is discussed in the OAQPS publication, "Measurement of Gaseous Organic
Compound Emissions by Gas Chromatography," presented as Attachment I to
this appendix.
D-4
-------
Method 25 can be used as an alternative procedure, but is likely to
yield slightly lower calculated efficiencies. Method 25 can be expected
to yield higher results than the GC method at the. emission outlet when
the outlet concentration is less than 100 ppm, volume, therefore, at
this time, Method 25 is particularly not recommended for performance
tests to measure compliance with the 98 percent or 20 ppm VOC reduction
provision of the proposed standard when the outlet emissions are expected
to be below this level.
D.3 MEASUREMENT OF GASEOUS ORGANIC COMPOUND EMISSIONS BY GAS CHROMATOGRAPHY
In order to determine the. volume percent VOC concentration and
stream net heating value for air oxidation sources, both identification
and quantification of the substances being emitted are necessary. The
generalized gas chromatography method described in Attachment I to this
appendix can be used to (1) determine hourly VOC emissions from the
control device outlet, (2) determine VOC reduction efficiency of the
control device, and (3) provide data required to determine whether a
source has a TRE index value above or below the cutoff level specified
in the proposed standard.
D.4 DETERMINATION OF NET HEATING VALUE AND VOC EMISSION RATE OF
EXHAUST GAS STREAMS
These methods describe the calculation of the net heating value and
VOC emission rate of gas samples. They specify methods the organic
compound content, carbon monoxide content, hydrogen content, and moisture
content of the gas sample. These compositional data are used along with
published or measured values for the net heats of combustion and molecular
weights to calculate the heating value and VOC emission rate of the gas
sample. The complete methods for heating value and VOC emission rate
determination determination are included as Attachment II to this
appendix.
D-5
-------
D.5 REFERENCES FOR APPENDIX D
1. Emission Test Report: Union Carbide Corporation; Taft, Louisiana.
OAQPS, Emission Measurement Branch Report No. 78-OCM-8,
September 1980.
2. Emission Test Report: Rohm and Haas Company; Deer Park, Texas.
OAQPS, Emission Measurement Branch Report No. 78-OCM-9,
August 1980.
3 Evaluation of Method 25 for Air Oxidation Processes. Midwest
Research Institute, Contract No. 68-02-2814, Task 36 (report not
yet available).
4. Measurement of Gaseous Organic Compound Emissions by Gas Chromatography.
OAQPS, Emission Measurement Branch.
D-6
-------
ATTACHMENT I TO APPENDIX D:
MEASUREMENT OF GASEOUS ORGANIC COMPOUND
EMISSIONS BY GAS CHROMATOGRAPHY
D-7
-------
MEASUREMENT OF GASEOUS ORGANIC COMPOUND EMISSIONS BY GAS CHROMATOGRAPHY
DISCLAIMER
Mention of trade names or specific products in this method does not
constitute endorsement by the Environmental Protection Agency.
D-8
-------
TABLE OF CONTENTS
Page
Li st of Fi gures D-ll
Li st of Tables D-l 2
Chapter 1. Introduction D-l 3
1.1 Purpose D-l 3
1.2 Source Types and Expected Sampling Conditions D-l4
1.3 Sampling Procedures : D-l9
1.3.1 Adsorption Tube Sampling D-19
1.3.2 Instantaneous Grab Sampling D-19
1.3.3 Integrated Bag Sampling D-21
1.3.4 Integrated Solvent Sampling D-25
1.3.5 Porous Polymers D-25
1.3.6 Direct Coupling and Interfacing D-26
1.4 Review of Analytical Techniques D-31
1.4.1 Instrument Design Considerations D-31
1.4.1.1 Portable Gas Chromatographs D-31
1.4.1.2 Laboratory Gas Chromatographs D-32
1.4.2 Gas Chromatographic Column Selection D-33
1.4.2.1 Multiple Columns D-34
1.4.2.2 Preconditioning Columns ! D-34
1.4.3 Data Presentation i D-35
1.4.3.1 Recorder Options i D-35
1.4.3.2 Peak Integration \ D-35
1.5 Safety Considerations i D-36
Chapter 2. Details of Methodology : D-38
2.1 Applicability and Principle D-38
2.1.1 Range of Applicability D-39
2.1.2 Precision and Accuracy D-39
2.2 Presurvey of Source D-40
2.2.1 Collection of Grab Samples - Glass
Samp! ing Fl asks D-40
2.2.1.1 Evacuated Flask Procedure D-44
2.2.1.2 Suction Bulb Procedure D-45
D-9
-------
TABLE OF CONTENTS (Continued)
Page
2.2.2 Collection of Grab Samples - Flexible Bags D-45
2.2.3 Determination of Moisture Content D-45
2.2.4 Determination of Static Pressure D-46
2.2.5 Grab Sample Analysis... °-46
2.3 Preliminary Method Development Evaluation D-46
2.3.1 Choice of GC Conditions D-46
2,3.2 Calibration Gases....... D"47
2.3.2.1 Preparation of Standards From
Volatile Materials D'49
2.3.2.1.1 Bag Technique. D-49
2.3.2.1.2 Cylinder. Approach D-51
2.3.2.2 Preparation of Standards from
Less Volatile Liquid Materials W-
2.3.3 Evaluation of Calibration and Analysis
Procedure j • U"M
2.4 Sampling and Analysis'Procedure °-66
2.4.1 Adsorption Tube Method. D'66
2.4.2 Integrated Bag Sampling and Analysis D-68
2.4.2.1 Evacuated Container Method D-68
2.4.2.2 Direct Pump Method ; D-"71
2.4.2.3 Analysis of Bag Samples.; D-71
2.4.3 Direct Interface Sampling and Analysis D-79
2.4.4 Dilution Interface Sampling j °-82
245 Modified Procedures Using a Bag Collected
Sample ; °-87
2.4.6 Reporting of Results D'88
2.5 Total Volatile Organic Mass Content of the Source
Gas •
...D-96
Bibliography •
n QQ
Supplement I-A: Column Selection u~y
Supplement I-B: Determination of Adequate Chromatographic
v Peak Resolution •• u-"1
Supplement I-C: Procedure for Field Auditing GC Analysis D-115
D-10
-------
LIST OF FIGURES
Paqe
D-l Integrated gas sampling train. Solid lines indicate
normal arrangements. Dotted lines show alternate
arrangement with evacuating chamber around bag D-22
D-2 Sampling system for analysis of undiluted source gas D-29
D-3 Preliminary survey data sheet D-41
D-4 Chromatographic conditions for gaseous organic analysis D-48
D-5 Calibration curve data sheet - injection of volatile
sample into Tedlar bag D-52
D-6 Rotameter calibration data sheet D-55
D-7 Single-stage calibration gas dilution system D-56
D-8 Two-stage dilution apparatus D-58
D-9 Calibration curve data sheet - dilution method D-60
D-10 Apparatus for the preparation of liquid materials D-63
D-ll Integrated bag sampling train D-70
D-12 Field sample data sheet - Tedlar bag collection method D-72
D-l3 Gas sampling valve operation D-73
D-14 Field analysis data sheets D-75
D-l5 Di rect interface sampl ing system D-81
D-l6 Schematic diagram of the heated box required for
di 1 uti on of sampl e gas D-85
D-l 7 Report data sheets D-89
D-ll
-------
LIST OF TABLES
1 Characteristics of Potential Organic Emission Sources D-15
1-1 Conmonly Employed Liquid Stationary Phases D-101
1-2 Conmonly Empl oyed Sol id Stationary Phases D-l 04
D-12
-------
! SECTION 1
i
| INTRODUCTION
1.1 PURPOSE
Characterizing emissions from industrial sources requires
both identification and quantification of the substances being
emitted. This method provides a methodology for sampling and
analyzing gaseous organic emissions from stationary industrial
sources to verify the existence of compounds thought to be
present and to quantify their emission levels.
The procedures described in this manual are intended to be
used by persons skilled in placing and executing sampling
efforts using Federal Register methods. Enough background
information is provided so that"such persons can: (1) characterize
the organic gaseous emissions using gas chromatography/flame
ionization detector (GC/FID), (2) verify the operation of the
j
instrumentation! and collection devices by means of audit samples
and quality control procedures, and (3) report the results in
terms of the concentration of major pollutants from the source.
Subsequent sections of this method discuss various aspects
of the sampling system, conditions that may be encountered in
source sampling, and options that must be considered to analyze
gaseous organics successfully.
D-13
-------
1.2 SOURCE TYPES AND EXPECTED SAMPLING CONDITIONS
Although organic chemical production involves many
different types of raw materials, processes, and products,
many of the unit operations are the same, e.g., distillation
columns, dryers, scrubbers, and mixing equipment. The
expected gaseous emissions, temperatures, velocities,
pressures, and humidities from these operations are given
in Table 1.
Temperatures in organic emission sources normally range
from ambient to 300°C (570°F). Paint spray booths and similar
hood-type operations operate at or above the plant ambient
temperatures. Operations that involve heating have emissions
££"
at 400°C (700°F). Sources with Tigher temperatures typically
emit gases of low molecular weigiit (CO, C02» H20, CH^, etc.)
because of thermal decomposition of all but the most thermally
stable organic compounds. Flare stacks and most high-
temperature incinerators fall into this latter category.
(Organic analysis for incinerator emissions generally involves
particulate and high-molecular-weight organic vapors, such as
polycyclic organic materials (POM's) and other less volatile
compounds.)
As seen in Table 1, the amount of moisture present in
organic emissions varies over a wide range. The effluent from
vents, tanks, or similar process lines may contain little or
D-14
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D-17
-------
no moisture or may be saturated with water vapor. The selected
procedures for sampling must normally prevent the condensation
of water in order to avoid the generation of unrepresentative
samples. However, if the organics of interest are water misicible,
then collection in water-filled impingers may be satisfactory.
Pressures encountered in organic sources are important because:
(1) the sampling system must be able to withstand the expected
source pressures and (2) the source pressure defines the pumping
requirements of the sampling system. Typically, gauge pressures
range from slightly negative to several pounds per square inch
positive.
CO, NO , SO , and particulate compositions are presented in
X "
Table 1 because they are potential interferents. Because some
acid gases vary the structure of some organic compounds and
cause false data, the components of the sampling system must
be made of corrosion-resistant materials. Particulates in
the source gases must be selectively excluded from the sampling
train for two reasons: (1) the surface of the particulates may
adsorb organic components and (2) high particulate levels can clog
portions of the gas sampling system and the chromatograph.
The concentrations of organic components in the source effluent
can vary between 10 and several thousand ppm. At the lower end of
the concentration range the FID sensitivity is quite adequate. At
the higher concentration levels, however, dilution of the source
gases may be required.
D-18
-------
1.3 SAMPLING PROCEDURES
Techniques used to collect samples for organic analysis
include: adsorption tube sampling, instantaneous flask sampling,
integrated bag sampling, integrated solvent sampling, porous
polymer collection and concentration, and direct interfacing.
These methods are described below, and their advantages and
disadvantages are discussed.
1.3.1 Adsorption Tube Sampling
In this procedure, volatile organic vapors are collected on
suitable adsorption media contained in glass tubes. The method
closely follows volatile organic methods contained in the NIOSH
Analytical Methods series. Desorption recovery efficiency must be
j?
determined for the organic species present and must .be at least
50 percent.
1.3.2 Instantaneous Flask Sampling
Instantaneous grab sampling, as the name implies, consists of
collecting a sample in glass sample bulbs, cylinders, or syringes
in a few seconds. If repeated on a frequent schedule, this
technique can indicate short-time variations in the emission
concentrations.
The source is sampled in one of two ways. The first way
is to evacuate the cylinder to low pressures typical of a good
quality vacuum pump and to connect it to a sample probe and a tee
connector. One leg of the tee is connected to a mercury manometer;
the other leg is used to purge the sample line with source gas
D-19
-------
using a rubber suction bulb. Then the stopcock in the cylinder is
opened to admit a sample. The procedure is very similar to EPA
Method 7 for withdrawing NOX samples.
The second approach is to use a flow-through system. The
source gas is drawn through the sampling cylinder by a pump or
rubber suction bulb until the gas has been purged from the cylinder
three or four times. After the cylinder has been purged, the
stopcocks are closed to contain the gas for analysis.
There are several problems associated with this technique. If
the sample gas is hot during the collection operation, condensation
and adsorption will most likely occur as the gas cools to ambient
temperature;- therefore, the container should be heated before
^
analysis. If pressure is not a problem, the container should be
heated before analysis to ia-20°C above the source temperature to
revaporize the condensed organic compounds.
Another problem involves the cleaning of sampling vessels. For
a glass vessel, organic contamination can be removed from the
interior by heating at a temperature just below the annealing point
of the glass. This treatment is generally sufficient to remove
any condensed or adsorbed materials, but it will not remove those
that can chemically bond to glass. After heating, the vessel is
cooled under a flowing stream of inert gas (high-purity nitrogen
or helium), which is retained in the flask after cooling.
Background data are obtained ay analyzing this gas by GC/FID or
D-2C)
-------
GC/mass spectrometric (GC/MS) methods. The least complicated
approach is to use a FID without a GC column to obtain a relative
measure of total organic content. The GC/MS method, if used,
would identify any contamination and indicate its origin.
1.3.3 Integrated Bag Sampling
Integrated bag sampling provides time-averaged samples. The
sampling may, therefore, be designed to represent average source
conditions over given time periods, such as complete cycles of
a batch operation.
In this approach the sample is withdrawn from the source into
an inert bag through an optional cooling condenser and a leak-free
pump (see Figure 1). One problem with this technique occurs when
condensation takes place, in which case the condensate must be analyzed,
A second problem is the procurement of a satisfactory leak-free,
corrosion-resistant and organic-contaminant-free pump.
A better arrangement is shown by the dotted line portion of
Figure 1. The gas is filtered by an in-stack glass wool plug in
the probe system to minimize condensation of water and organic
compounds. The gas is then directed from the probe into a plastic
bag by evacuating the airtight chamber around the bag. As a result,
the sample is not contaminated by passage through needle valves,
flow meters, or the pump. This arrangement has been used on paint
spray booths and bake ovens to sample individual stacks and, by
using a manifold system, to sample several stacks simultaneously.
D-21
-------
AIR-COOLED !
CONDENSER
PROBE
RIGID
CONTAINER
Figure 1.
Integrated gas sampling train. Solid lines indicate
normal arrangements. Dotted lines show alternate
arrangement with evacuating chamber around bag.
D-22
-------
The same arrangement is used in Method 106 for sampling vinyl
chloride in stationary sources.
If condensation occurs, the problem may be overcome by heating
the bag containing the sample to source temperature prior to
\
analysis, or by maintaining the temperature at source levels during
collection, transport, and analysis. Dilution of the gas in the
bag could also solve the condensation problem, and, in addition,
reduce highly concentrated gas streams to a measurable level.
The source gas can be diluted prior to collection in the bag
by metering both the gas and charcoal-cleaned ambient air (or clean
inert gas) through calibrated flow meters with micrometer valves.
A dilution ratio between 5:1 and 30:1 would be used, depending on
the concentrations required by;the analytical instrument. An
alternative method for diluting"the source gas would be to prefill
the bag partially with a known quantity of inert gas and then meter
in a known quantity of the source gas.
The choice of a bag material is an important consideration.
Possibly acceptable bag materials are Tedlar,1 Teflon, and aluminized
Mylar. Mylar, polyethylene, or Saran bags suffer from reduced
recovery of known concentrations of sample gases. Tedlar provides
slightly better recovery than Teflon, but over short time periods
the difference is not significant. The actual recovery of samples
collected in the Tedlar or Teflon bags depends on the nature of
the organic emissions. The higher the source temperature and the
more polar the organic compounds being studied, the greater the
Mention of trade names or specific products does not consitute
endorsement by the U.S. Environmental Protection Agency.
D-23
-------
losses of material observed during storage periods up to several
days. Most of the loss appears to occur in the first few minutes.
After this initial period, the loss rate is relatively small over
the next several days.
Reusing Tedlar or Teflon bags can also cause some problems.
In one case, a Teflon bag had been used to collect samples of
source gas containing cumene (isopropyl benzene) at a level of
about 1100 ppm. After the analysis was completed, this bag was
flushed with nitrogen and evacuated three times. After the third
evacuation, the bag was filled with nitrogen and analyzed. The
analysis indicated less than 0.01 ppm of cumene. One week later,
the gas was analyzed again and 64jpm of cumene was found. This
indicates very clearly that this material is absorbed into the bag
and diffuses very slowly from the plastic material. Since this
effect could be fairly common, it is strongly suggested that new
sample bags be used whenever possible, and that they definitely be
used when samples are to be stored more than an hour or two.
Since the loss of material in the bag depends on several factors
(temperature, concentration, and polarity of the material), the
amount of loss to be expected will vary greatly from site to site.
Known standards of the components in a pseudo-stack gas can be
prepared at several concentration levels and collected in a bag
identical to the one to be used for the source sampling. The contents
D-24
-------
of this bag may then be used to calibrate the GC instruments or,
if other calibration gases are available, to evaluate the sample
recovery efficiency.
1.3.4 Integrated Solvent Sampling
If the organic emissions are water misicible, then sampling with
water-filled impingers may be a feasible approach. Other solvents
might also be used.
1.3.5 Porous Polymers
Organic vapors and hydrocarbons are frequently trapped on a
porous polymer compound substrate such as Tenax GC, XAD-2, Chromosorb
Century Series, or Porapak resins. This approach is useful for
concentrating trace amounts of organic compounds and for
materials of molecular weights /§¥ Cg and greater. It is being
employed in the collection of hfgh molecular weight organic
compounds (POM's) and in source assessment sampling systems.
The major problem is that low molecular weight compounds are
not efficiently collected, and therefore it would be necessary
to carry out collection and desorption efficiency studies on
many of the compounds of interest. Another problem results
when some of the porous polymer organic resins react with certain
oxidants (i.e., N02, inorganic acids, etc.). These resins
decompose and yield organic materials that will contaminate the
sample.
D-25
-------
There may be several advantages to porous polymers in certain
situations. First, the polymers do not tend to trap water, and so
it is possible to collect the organic compounds and let the water
vapor pass through. Second, collected samples are easy to
transport. Third, the container can be capped and then stored at
0°C until analyzed. In the closed and cooled condition, the tubes
can be held several weeks prior to analysis. The adsorbed compounds
can be removed from the tube either by heating it while passing
an inert gas (usually the GC carrier gas) through it, or by passing
a suitable solvent through the tube. Solvent desorption, if a
suitable solvent is found, provides sufficient material for several
analyses on the same sample, whereas the thermal desorption is
£.
a one-time approach. . .
However, the porous polymer approach is not suggested for routine
sampling because of the loss of low-molecular-weight compounds, which
are of major interest, and because of the lack of a need to
concentrate the sample to reach the desired detection limits. In
certain situations and when collection efficiency data are available,
porous polymer collection may be a viable option.
1.3.6 Direct Coupling and Interfacing
The most accurate method for sampling and analysis is to couple
the gas chromatograph directly to the source. Its use depends on
the similarity of the source gas (temperature, pressure, composition)
to the requirements of the gas sampling system of the GC instrument.
D-26
-------
The problems to be considered are the materials of construction,
the presence of particlate and water vapor, the temperatures of
the gases and of the sample valving system of the GC, the concentration
of the gaseous organic species in the gas stream, and the
accessibility of the location of the stack vent being sampled.
The presence of particulate in the source gas can present a
severe problem for the GC operation. The simplest solution is to
use an in-stack filter with an enlarged probe at the gas inlet end
and a plug of glass wool inserted in this enlarged area. The probe
itself can be made of 0.25-inch stainless steel tubing, and
connectors can be used to enlarge the diameter of the probe to
accommodate 0.5-inch tubing to contain the glass wool filter. Since
^?
the filter can be in the stack., it can in a short time reach the
stack temperature, and condensation of water and organic compounds
can be minimized. The filter should be replaced each time a new
site is sampled.
The problem of water vapor condensation is not so simply solved.
Water dissolves polar organic compounds, and large quantities restrict
the flow in the sample lines.
To prevent condensation, (1) the sample lines may be heat-traced
to maintain the sample gas temperature above the dew point or at
stack temperature, or (2) the source gases may be diluted as close
to the source as possible. The choice depends on the source
temperature and the concentration of the organic compounds in the
source. If the concentration of organic compounds is so high that
D-27
-------
the FID will be saturated, the obvious answer is to dilute the
source gas.
The sample gas can also be dried, or the water can deliberately
be condensed. Procedures for determining low-molecular-weight
hydrocarbons sometimes include the use of condensers held at 0°C
to remove water, and drying agents such as Ascarite or silica gel.
These methods are useful in those situations where in the emissions
of interest are low-molecular-weight (Oj to Cg) alkanes and alkenes.
They are not applicable, however, for polar compounds and materials
with low vapor pressures at 0°C unless the condensate can be
analyzed. This approach obviously could not be used on all source
emissions.
The major restraints on ^e design of the interface are the
source gas and SC temperaturesi~ The sample lines from the probe to
the instrument must be heat-traced with electrical resistance heating,
The probe should contain a Type K thermocouple for monitoring and/or
regulating the temperature. The temperature of the source gases
should also be monitored with a second Type K thermocouple attached
to the outside of the probe. The sample lines should be as short as
possible, consistent with the physical requirements of the site.
!
A diagram of the apparatus is shown in Figure 2.
Situations will likely occur in which the source gas must be
diluted because of the higher source temperature, water vapor, and/or
high organic compound concentrations. This dilution should be
performed with inert gas or charcoal-cleaned ambient air. It can
D-28
-------
en
nj
cn
-------
be accomplished by installing a tee fitting between the sample
line and the probe. The diluent gas is then added through this
tee. The flows of both the stack gas and diluent gas must be
measured with calibrated flow-meters and micrometer valves to
determine the dilution ratio. Dilution ratios in the range of
1:5 to T:30 are desirable. For this approach a larger-than-normal
pumping rate is required in the sampling line, with the rate varying
with the required dilution factor.
The calibration of the GC with either interface system will
depend on the substitution of calibration gas for the source gas.
A Tedlar bag containing a standard gas mixture should be connected
to the filter end of the probe, and the same pumping rate and
££
dilution used for source gas should be used to obtain the calibration
data. Ideally, the flow rateslind gas sampling pressures will be
identical. This will make accurate calibration of each flow meter
and gas sampling valve unnecessary since these factors will cancel.
The standard gas concentrations are used to prepare a calibration
curve, and the source gas concentrations can be read directly from
the curve. During sampling, corrections will have to be made for
the pressure differences between the standard mixtures (atmospheric)
and the source pressure. The source pressure is easily determined
with a pitot tube and manometer prior to the start of the test.
For the most part, the sources to be tested will be close to
atmospheric pressure, varying by several inches of water plus or
D-30
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minus; and this pressure difference will have little effect on the
results. This will not be true for process gas streams, and pressure
corrections must be made or the sample must be collected by•one of
the methods discussed in Sections 1.3.2, 1.3.3, or 1.3.4.
1.4 REVIEW OF ANALYTICAL TECHNIQUES
1.4.1 Instrument Design Considerations
The analytical instrumentation must be designed to withstand
field use. The gas chromatograph must be capable of producing
accurate data, but a fully equipped research-quality instrument is
not normally required. The instrument must be rugged enough that
it will not be rendered inoperable by transportation from one sampling
site to another. It must afford good temperature control for the
analytical column, the injection port, the gas sampling valve, the
%-
sample loop, and the detector.-. "The gas sampling system must provide
reproducible injections into t|| chromatograph and maintain the
integrity of the sample from the stack to the detector. Temperature
programming is a desirable option in view of the wide variety
of compounds likely to be encountered. An intrinsically safe
(explosion proof) chromatograph is a definite asset to the
program. In some situations, constant-voltage or constant-phase
transformers may be required in the line prior to the electronics
for the FID and the electrometer.
1.4.1.1 Portable Gas Chromatoqraphs
These commercially available instruments are completely
self-contained. Rechargeable lecture-bottle-size cylinders contain
D-31
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the necessary gases, and rechargeable nickel-cadmium batteries
supply the power. They do not require large gas cylinders or
electrical service.
However, these portable chromatographs do have certain
disadvantages. Typically, more time is required for temperature
equilibration than with nonportable instruments. In addition, the
supply of the gases in the small cylinders limits the length of
time the instrument may be used for actual analysis. Since these
cylinders must be periodically recharged, large cylinders may still
be necessary when one sampling trip is to cover several plants
in different cities before returning to a "home base." The most
severe problem with portable instruments is that most are not
temperature programmable. ^
1.4.1.2 Laboratory Gas Chromatngraphs
For the above reasons, the use of a temperature-programmable
laboratory chromatograph is advisable; but an extremely sensitive,
research quality instrument replete with accessories and options
such as automatic oven door openers, subambient capability, and
multiple detectors is not necessary. However, a certain degree
of durability is necessary to withstand transport. The major
disadvantages of a laboratory chromatograph are the handling of
the necessary gases and the availability of, electrical power in
the field.
D-32
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1.4.2 Gas Chromatoqraphic Column Selection
Information pertinent to column selection must be available
prior to actual field analysis. Background information is
generally available for various processes, including typical
components of the stack gases for a given process, the approximate
concentration levels of these components, and information regarding
temperatures and flow rates of the stack gases. This information
is quite helpful in selecting not only the proper column or columns,
but also GC operating conditions such as column temperature,
injection port temperature, flow rates, etc. Analysis of a sample
that is collected during a pretest site survey provides the only
reliable information regarding^mpounds present, approximate
levels, quantity of water vapor present, etc., upon which decisions
can be based concerning column "type, prediction, and GC conditions.
When the organic portion of the stack emissions contains compounds
with widely varying molecular weights and volatilities, multiple
columns must be used.
The types of columns from which final selections can be made
include: (1) the Porapak series, (2) one of the Chromosorfa Century
series, and (3) Carbosieve B for the low-molecular-weight, highly
volatile compounds, and (4) Tenax GO or one of the Dexsils for the
higher-molecular-weight compounds. A summary of some of the column
materials, their properties, and their usefulness is given in
Supplement I-A.
D-33
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1.4.2.1 Multiple Columns
When no single column can provide efficient separation of a
complex mixture of compounds having widely varying molecular weights
and boiling points, multiple columns may be employed. Using either
two individual GC units, each possessing a different column, or
one GC with a change of columns is expensive and time consuming.
Two or more columns in a single GC operation is more advantageous.
For the latter, the most convenient method requires each of the
two individual column outlets to enter separate detector cells.
However, if the GC unit is not equipped with or cannot be modified
to accommodate this type of ancillary equipment, two or more columns
may be connected either in series or in parallel. When multiple
columns are connected in seriesY'the sample enters each column
successively; when parallel conjiection is used, the sample and carrier
gas stream is split into individual fractions, and one portion of
the sample enters each column.
1.4.2.2 Preconditioning Columns
Every new GC column requires conditioning prior to its initial
use. Conditioning is ordinarily achieved by heating the packed
column in a stream of carrier gas to the maximum operating temperature
anticipated for a period of time ranging from a few hours to a few
days, depending on the column materials chosen. To avoid
contaminating the detector, the column outlet should not be connected
to it until the final stages of conditioning. When a stable baseline
is achieved, conditioning can be assumed to be essentially complete.
D-34
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Conditioning the column removes volatile impurities, water,
and any solvent remaining from the deposition of the liquid phase
on the support and provides a more uniform distribution of liquid
phase on the solid support. In addition, conditioning serves to
activate ' (or, in the case of some special-purpose stationary
phases, to deactivate) the solid stationary phase.
1.4.3 Data Presentation
1.4.3.1 Recorder Options
Desirable features on both portable and laboratory recorders
include multiple voltage range (1 millivolt to 1 volt), variable
chart speed, a reliable pen assembly, and a chart width adequate for
accurate peak determination. The recorder must remain fairly
-' - ':<* i.
stable, must not drift excessively, and must not contribute
significantly to the "noise""transferred to the pen.
1.4.3.2 Peak Integration
An excellent alternative to the typical recorder is an
integrator. The integrator obviates calculations of the peak
heights or peak height times width at half the peak height. An
integrator such as the Hewlett-Packard Model 3380A not only provides
a traced chromatogram, as does a conventional recorder, but it also
provides a display of the retention time of the components or
absolute quantity calculations based on programmed internal or
external standards. The integrators greatly facilitate GC analyses,
including those performed in the field.
' D-35
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1.5 SAFETY CONSIDERATIONS
The tester must be aware of all existing and potential hazards
with respect to emission testing and comply with existing OSHA and
specific plant requirements. Although the dangers associated with
source sampling are well known to anyone who has been active in
this area, there are some unique features of organic vapor sampling
that should be considered.
Cylinders of hydrogen, air, and helium (or nitrogen) are
required for the operation of the chromatograph. All connections
should be leak checked using soap solution or one of the commercial
leak-check solutions. Cylinders of these gases should not be
transported in a closed vehicle. The safest approach is to ship all
cylinders of the gases to the sampling site by suitable commercial
carriers. " -,^
Before samples are collected, sampling lines must be purged
in a manner that will eliminate exposure of any personnel to the
gases. All gases should be assumed to be toxic. Similarly, the
gas used to flush the sampling loop and any gas evacuated from
sampling bags should be trapped to prevent personnel exposure.
Charcoal tubes can be used for this purpose.
Audit samples of the source gas components required to verify
the analysis procedures will contain gases with concentrations
between 10 and 10,000 ppm. These gas samples should also be treated
as if they were extremely toxic to avoid exposure of any person
handling them.
D-36
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Electrical power supply sources should be checked prior to
use to be sure receptacles have been wired to code specifications.
Circuit checkers are commercially available for this purpose.
The test team must be aware of plant restrictions regarding
flame detectors, locations of safety showers, eye wash fountains,
first aid stations and medical help, evacuation alarms, and paths
of egress. Each tester must also be equipped with the required
personal safety equipment (hard hats, safety glasses, ear protection,
respirators or air packs, safety shoes, etc.). Safety indoctrinations
are required at many plant sites before work can begin; and even at
those locations where safety checkouts are not formally required,
they should be considered as essential for the test team. The safety
aspects must not be compromised "for any reason
D-37
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SECTION 2
DETAILS OF THE METHOD
2.1 APPLICABILITY AND PRINCIPLE
This method provides concentration data on approximately
90 percent of the total gaseous organic mass emitted from an
industrial source. It does not include techniques to identify
and measure trace amounts of organic compounds, such as those
found in building air and fugitive air emission sources.
This method is based on separating the components of a gas
mixture in a gas chromatographic (GC) column and measuring the
separated components with a flame ionization detector (FID). This
method will not determine compounds that (1) are polymeric (high
molecular weight), (2) can polymerize (such as formaldehyde),-
(3) have very low vapor pressures at stack or instrument conditions
or (4) exhibit poor response with the FID.
The method also depends on comparing the retention times of
each separated component with those of known compounds under identical
conditions. Therefore, the analyst must suspect the identity and,
approximate concentration of the organic emission components before-
hand. With this information, the analyst can prepare standard
mixtures to calibrate the GC under conditions identical to those
that the samples will exhibit. The analyst can also determine the
need for sample dilution to avoid FID saturation, gas stream
filtration to eliminate particulate matter, and moisture condensation
prevention. This method cannot be applied without this prior
information.
D-38
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2.1.1 Range of Applicability
The sensitivity of this method is about 10 parts per billion.
The upper end is limited by detector saturation or column
overloading. It can be extended by diluting the stack gases with
an inert gas or by using smaller gas sampling loops.
2.1.2 Precision and Accuracy
GC techniques typically provide a precision of +_ 5 to 10
percent relative standard deviation (RSD), but an experienced
GC operator and a reliable GC/FID instrument can readily achieve
a +_ 5 percent RSD. For this method, the following combined
GC/operator values shall be met:
(1) Repeatability. Duplicate results by the same operator
will be rejected if they differ "by more than £5 percent.
C2) Accuracy. The result's.of prepared audit sample analyses
"'-'—. 3
will be considered deficient if "they differ by more than +_ 10 percent
from the preparation values.
The accuracy of the sampling and analytical procedure on stack
gases cannot be defined since the actual emission values are not known.
However, the accuracy and the validity of the sampling and analysis
will be evaluated by using both on-site calibration with known mixtures
and prepared audit samples.
Based on the precision and accuracy of the GC method, analysis of
industrial sources is estimated to be within +_ 10 percent of the actual
values.
D-39
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2.2 PRESURVEY OF SOURCE
The purpose of the presurvey is to obtain all information
necessary to design the emission test. The most important presurvey
data are the average stack temperature and temperature range,
approximate particulate concentration, static pressure, water vapor
content, and identity and expected concentration of each organic
compound to be analyzed. Some of this information can be obtained
from literature surveys, direct knowledge, or plant personnel.' However,
grab samples of the gas must be obtained for analysis to confirm the
identity and approximate concentrations of the specific compounds.
A moisture determination should also be made. A suggested presurvey
form is given in Figure 3,
2.2.1 Collection of Grab stmp.les - Glass Sampling Flasks
Grab samples can be collected in precleaned 250-ml double-ended
glass sampling flasks. Teflon stopcocks, without grease, are preferred.
Flasks having glass stopcocks with grease should be cleaned as follows.
Remove the stopcocks from both ends of the flask, and wipe the
parts to remove any grease. Clean the stopcocks, barrels, and
receivers with chloroform. Clean all glass ports with Micro Cleaning
Solution, then rinse with tap and distilled water. Place the flask
in a cool glass annealing furnace and apply heat up to 550°C.
Maintain at this temperature for 1 hour. After this time period, shut
off and open the furnace to allow the flask to cool. Grease the
stopcocks with Spectavac grease and return them to the flask receivers.
D-40
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PRELIMINARY SURVEY DATA SHEETS
GASEOUS ORGANIC ANALYSIS-GC METHOD
I. Name of Company
Address
Contacts
Process to be Sampled
Date
Phone
Duct or Vent to be Sampled
II. Process Description
Raw Material
Products
Operating Cycle
Check: Batch
Continuous
Cyclic
Timing of Batch or Cycle
Best Time to Test
Figure 3. Preliminary survey data sheet.
D-41
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PRELIMINARY SURVEY DATA SHEETS
GASEOUS. ORGANIC ANALYSIS-GC METHOD
III. Sampling Site
A. Description
Site Description
Duct Shape and Si26
Material
Wall Thickness
inches
Upstream Distance __
Downstream Distance_
Size of Port
inches
diameter
inches
diameter
Size of Access Area
Hazards
Ambient Temp.
Properties of Gas Stream
Temperature °C
Velocity
'F, Data Source
, Data Source
Static Pressure Caches H20, Data Source
Moisture Content %, Data Source
Particulate Content -1- , Data Source
Gaseous Components
N« % Hydrocarbons
2
CO
CO,
so!
ppm
Hydrocarbon Components
ppm
ppm
ppm
ppm
ppm
ppm
Figure S(Continued). Preliminary survey data sheet.
D-42
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PRELIMINARY SURVEY DATA SHEETS
GASEOUS ORGANIC ANALYSIS-GC METHOD
C. Sampling Considerations
Location to Set Up GC
Special Hazards to be Considered
Power Available at Duct __
Power Available for GC
Plant Safety Requirements
Vehicle Traffic Rules
Plant Entry Requirements
Security Agreements
Potential Problems
D. Site Diagrams. (Attach Additional Sheets if Required)
. Figure 3(Continued). Preliminary survey data sheet.
D-43
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Purge the assembly with high-purity nitrogen for 2 to 5 minutes.
Close off the stopcocks after purging to maintain a slight positive
nitrogen pressure. Secure the stopcocks with tape and take into
the field.
The grab samples can be obtained either (1) by drawing the
gases into an evacuated flask or (2) by drawing the gases into and
purging the flask with a rubber suction bulb. The procedures are
discussed below.
2.2.1.1 Evacuated Flask Procedure
With a high-vacuum pump, evacuate the flask to the capacity of
the pump; then close off the stopcock leading to the pump. Attach
a 6-mm-OD glass tee to the flask inlet with a short piece of Teflon
tubing. Select a 6-mm-OD Pyrex sampling probe, enlarged at one end
to a 12-mm OD and of sufficient length to reach the centroid of the
i.*
duct to be sampled. Insert a glass wool plug in the enlarged end
of the probe to remove particulate matter. Attach the other end of
the probe to the tee with a short piece of Teflon tubing. Connect
a rubber suction bulb to the third leg of the tee. Place the filter
end of the probe at the centroid of the duct, and purge the probe
with the rubber suction bulb. After the probe is completely purged
and filled with duct gases, open the stopcock to the grab flask until
the pressure in the flask reaches duct pressure. Close off the
stopcock and remove the probe from the duct. Remove the tee from the
flask and tape the stopcocks to prevent movement during shipment.
Measure and record the duct temperature and pressure.
'D-44
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2.2.1.2 Gas Collecting Tube Procedure
Attach one end of the gas collecting tube to a rubber suction
bulb. Attach the other end to a 6-mm-OD glass probe as described
in Section 2.2.1.1. Place the particulate filter end of the probe
at the centroid of the duct and apply suction with the bulb to
completely purge the probe and gas collecting tube. After the
gas collecting tube has been purged, close off the stopcock near
the suction bulb and then close the stopcock near the probe. Remove
the probe from the duct and disconnect both the probe and suction
bulb. Tape the stopcocks to prevent movement during shipment.
Measure and record the duct temperature and pressure.
2.2.2 Collection of Grab Samples - Flexible Bags
Tedlar or aluminized Mylar bags can also be used to obtain the
presurvey grab sample. Use new.bags and leak check them before field
use. In addition, check the bag before use for contamination by
filling it with nitrogen or air,, and analyzing the gas by GC at high
sensitivity. Experience indicates that it is desirable to allow
the inert gas to remain in the bag about 24 hours or longer to check
for desorption of organics from the bag. Details of the leak check
and the bag collection procedures are given in Section 2.4.2.
2.2.3 Determination of Moisture Content
For combustion or water-controlled processes, obtain the moisture
content from plant personnel or by measurement during the presurvey.
If the source is below 50°C, measure the wet bulb and dry bulb
D-45
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temperatures and calculate the moisture content using a psychrometric
chart. At higher temperatures, determine the moisture content using
EPA Method 4.
2.2.4 Determination of Static Pressure
Obtain the static pressure from the plant personnel or measure
it. If a type S pitot tube and an inclined manometer are used,
position the pitot tube 90 degrees from the flow in the source.
Disconnect one of the tubes connecting the pitot tube to the manometer
and read the static pressure. Note which leg of the pitot is
disconnected in order to determine the correct sign (positive or
negative).
2.2.5 Grab Sample Analysis
Before analysis, heat the grab sample to the duct temperature
to vaporize any condensed material. Analyze the samples by the
v
GC/FID procedure and compare the retention times against the artificial
samples containing the components expected to be in the stream. If any
compounds cannot be identified with certainty by this procedure,
identify them by other means such as GC/MS or GC/infrared technique.
If a GC/MS system is available, this method is recommended.
2.3 PRELIMINARY METHOD DEVELOPMENT EVALUATION
Once the stack temperature, static pressure, moisture content,
approximate particulate concentration, and the identify and approximate
concentration of the components are known, one can determine the
sampling system, GC column, and approximate analytical conditions
(flow rate and ignition port, column, and detector temperatures).
D-46
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2.3.1 Choice of GC Conditions
Using the expected source gas composition from the pretest
survey and basic chromatography knowledge (see Appendix A),
select possible GC columns that will provide the necessary peak
resolution and shape consistent with good GC techniques. Record
the chosen GC conditions on a data sheet such as shown in Figure 4.
Since emissions from organic sources vary widely in composition,
details of an analytical scheme that is suitable for every source
cannot be provided here. Generally, if the GC is used in an
isothermal mode, the column temperature should provide good peak
resolution and a reasonable time for the total analysis. Column flow
rates of 20 to 40 ml/min are typical at head pressures of 20 to 40 psig.
Analysis of aliphatic hydrocarbons (Cj to C4) using a 1.8-ra by 3.13-mm
hromosorb 102 column can be_carried out at column temperature
•»~
between 80° and 120°C. Aromatic hydrocarbons, including benzene,
toluene, and xylenes, can be successfully chromatographed at 80°C
using a 1.8-m by 3.13-mm 10 percent DC-200 on Chromosorb WHP column.
Some other recommended columns include: 1.8-m by 3.13-mm
Chromosorb 102 for low molecular weight hydrocarcons, 1.8-m by
3.13-mm 10 percent DC-200 silicone oil on 80 to 100 mesh Chromosorb
WHP for aromatic and chlorinated compounds, and 1.8-m by 3.13-mm
Tenax GC or 1.8-m by 3.13-mm Dexsil 400 for a variety of nonpolar
and polar compounds.
Verify the choice of column, temperature, and other instrument
parameters in the laboratory before any field sampling as follows:
D-47
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Gaseous Organic Analysis - Chromatog.raphic Conditions
Gas Chromatographic Conditions
Components to be Analyzed Expected Concantraticn
Suggested Chromatographic Column
Column flow rate ml/min Head pressure psig
Column temperature:
Isothermal '- °C
Programmed from °C to °C at _°C/min
Injection port/sample "loop temperature °C
Detector temperature °C
Detector flow rates: Hydrogen
ml/min.
Chart speed
Compound data:
Compound
head pressure_
Air/Oxygen ml/min,
head pressure^
inches/minute
_psig
>sig
Retention Time
Attenuation
Figure 4. Chromatographic conditions for
gaseous organic analysis.
D-48
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Compare the chromatograms from the pretest grab sample and a
synthetic mixture of the expected components. Use this mixture
also to refine the instrument conditions and establish a calibration
curve. If dilution is required, determine the dilution factor
and assemble the sampling apparatus to provide the required dilution.
2.3.2 Calibration Gases
If available, use NBS reference gases or commercial gas mixtures
certified through direct analysis for the calibration curves.
Aliphatic hydrocarbons in an inert gas matrix are available. If
commercial mixtures are not available, then prepare and verify
standards both internally in the laboratory and through an external
source in order to provide a quality control check.
2.3,2.1 Preparation of Standards-From Volatile Materials
The following technique for;-preparing standards, which is an
adaptation of EPA Method 106 for vinyl chloride, is recommended:
2.3.2.1.1 Bag Technique
Evacuate a 16-inch square Tedlar bag that has passed a leak
check (see Section 2.4.2), and meter in 5.0 liters of nitrogen
through a 0.5-liter/revolution dry test meter. While the bag is
filling, use a 0.5-ml syringe to inject a known quantity of the
material of interest through the wall of the bag or through a
septum-capped tee at the bag inlet. Upon withdrawing the syringe
needle, immediately cover the resulting hole with a piece of
masking tape. In a like manner, prepare dilutions having other
concentrations. Prepare a minimum of three concentrations.
D-49
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Place each bag on smooth surface and alternately depress opposite
sides of the bag 50 times to mix the gases. Record the average
meter temperature, gas volume, liquid volume, barometric pressure,
and meter pressure.
Set the electrometer attenuator to the XI position. Flush
the sampling loop with zero helium or nitrogen and activate the
sample valve. Record the injection time, sample loop temperature,
column temperature, carrier gas flow rate, chart speed, and
attenuator setting. Record peaks and detector responses that occur
in the absence of any sample. Maintain conditions. Flush the
sample loop for 30 seconds at the rate of 100 ml/min with one of
the calibration mixtures, and open the sample valve. Record the
injection time! Select the pea'k-that corresponds to the compound
of interest. Measure the distance on the chart from the injection
time to the time at which the peak maximum occurs. This quantity,
divided by the chart speed, is defined and recorded as the retention
time.
To prepare the GC calibration curve, make a GC measurement of
each of the standard gas mixtures described above. Record the
concentrations injected, the attenuator setting, chart speed, peak
area, sample-loop temperature, column temperature, carrier-gas
flow rate, and retention time. Record the laboratory pressure.
Calibrate the peak area multiplied by the attenuator setting.
Repeat until the area of two consecutive sample injects agree
within 5 percent, then plot the average versus the concentration.
D-50
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When the other concentrations have been plotted, draw a line
through the points derived by the least squares method. Perform
the calibration daily, or before and after each set of bag
samples,' whichever is more frequent. Record all data as shown
on the example data sheet in Figure 5.
2.3.2.1.2 Cylinder Approach
As an alternative procedure, maintain high and low calibration
standards. Use the high-concentration (50 to 100 ppm) standard to
prepare a three-point calibration curve using an appropriate dilution
technique. Then use the low-concentration standard to verify the
dilution technique. Use this same approach also to verify the
dilution techniques for high-concentration source gases.
To prepare the diluted calibration samples, use calibrated
rotameters to meter both the h^h-concentration calibration gas and
the diluent gas. Adjust the flow rates through the rotameters with
micrometer valves to obtain the desired dilutions. A positive
displacement pump or other metering technique may be used in place
of the rotameter to provide a fixed flow of high-concentration gas.
To calibrate the rotameters, connect each rotameter between
the diluent gas supply and a suitably sized bubble meter, spirometer,
or wet test meter. While it is desirable to calibrate the calibration
gas flow meter with the calibration gas, generally the available
amount of this gas will preclude it. The error introduced by using
the diluent gas is insignificant for gas mixtures of up to 1000 to
2000 ppm of each component. Record the temperature and atmospheric
D-51
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Calibration Curve Data - Volatile and
Liquid Samples Collected in a Tedlar Bag
Mixture
Blank.. 1
Mixture
2
Mixture
. ' 3
Size of Tedlar bag (inches)
Dilution gas (name)
Vol. of dilution gas (liters)
Component (name)
Volume of component (ml)
Average meter temp. (°C)
Average meter pressure (nm)
Atmospheric pressure (nm)
Density of liquid component
(g/ml)
Sample loop volume (ml)
Sample loop temp. (°C)
Carrier gas flow rate (ml/min)
Column temperature
initial (°C) "
program rate (°C/min) _ [
final (°C) -^
Injection time (24 hr. basis)
Distance to peak (inches)
Chart speed (inch/min)
Retention time (min)
Concentration of component (ppm)
Attenuator setting
Peak height (mn) _
Peak area (mm2)
Area x attenuation
Plot peak area x attenuation against concentration to obtain cal-
ibration curve.
Figure 5.
Calibration curve data sheet - injection
of volatile sample into Tedlar bag.
D-52
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t Samples
-tention time (min)
.jection time (24-hr basis)
:tenuation factor
>ak height (mm)
»ak area (mm2)
;ak area x attenuation factor
sasured concentration (ppm)
ata reported on (date)
ata reported by (initial)
ertified Concentration (ppm)
eviation (%)
Samole 1
Samnle 2
gure 5 (continued).
Calibration curve data sheet - injection
of volatile sample into Tedlar, bag.
D-53
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pressures during calibration. Calibrate the rotameter over the
entire flow range with a minimum of 5 flow rates. Plot the
rotameter readings against the actual flow rate and record the
temperature and atmospheric pressure on each calibration curve.
Record all data on a data sheet as shown in Figure 6.
Correct the flow rate to different temperatures and atmospheric
pressures as follows:
1/2
Where:
Q_ D s Flow rate at new absolute temperature (T?} and
'2*2
new absolute pressure (?«)•
QTP
TV1
Flow rate at calibration absolute temperature
(T-j) and absolute pressure (P^).
Connect the rotameters to the calibration and diluent gas supplies
using 6-mm Teflon tubing. Connect the outlet side of the rotameters
through a connector to a leak-free Tedlar bag as shown in Figure 7.
(See Section 2.4.2 for leak check procedure.) Adjust the gas flows
to provide the desired dilution and fill the bag with sufficient
gas for calibration, being careful not to fill to the point where
it applies additional pressure on the gas. Record the flow rates
D-54
-------
Rotameter .Calibration Data
Rotameter number
Gas used
Method: Bubble meter__
Rotameter construction
Float type
Spirometer
Wet test meter
Laboratory temperature (T obs.)
Laboratory pressure CP obs.)
in Hg
mm Hg
1. Flow Meter Reading Time (min) Gas Volume9 (Lab Conditions)13
Vol. of gas may be measured "In milliliters, liters or cubic feet
Convert to Standard Conditions (20°C and 760 mm Hg)
760 x T obs.
P obs. x 20
1/2
Flow Meter Reading
Flow Rate (STD Conditions)
Plot meter reading against flow rate (std) and draw smooth curve.
Figure 6. Rotameter calibration data sheet.
D-55
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O
<
CO
en
>i
en
en
(TJ
o
CP
cn
i
o
rH
CP
tu cn
5 < g
2= o 2
D-56
-------
of both rotameters, the ambient temperature, and atmospheric
pressure. Calculate the concentration of diluted gas as follows:
. I06xlqa
Where:
Ca - Concentration of component a in ppm.
q^ = Flow rate of component a at measured temperature and
pressure.
qQ = Diluent gas flow at measured temperature and pressure.
X = Mole fraction of component in the calibration gas to be
diluted.
Use single-stage dilutions to prepare calibration mixtures up to
about 1:20 dilution factor. For greater dilutions, use a double
dilution system. Assemble therat>paratus as shown in Figure 8,
using calibrated flow meters of suitable range. Adjust the control
valves so that about 90 percent of the diluted gas from the first
stage is exhausted and 10 percent goes to the second stage flow
meter. Fill the Tedlar bag with the dilute gas from the second stage.
Record the temperature, ambient pressure, and water manometer
pressure readings. Correct the flow reading in the first stage as
D-57
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indicated by the water manometer reading. Calculate the-
concentration of the component in the final gas mixture as follows:
io6 r
Where:
= Concentration of component "a" in ppm.
X = Mole fraction of component "a" in original gas.
qa-j « Flow rate of component "a" in stage 1.
qa2 = Flow rate of component "a" in stage 2.
q0.j = Flow rate of diluent gas in stage 1.
qD2 = Flow rate of diluent gas in stage 2.
Prepare three calibration -gas mixtures, one at the approximate
concentration expected to be fdund in the source, and one higher
and one lower than this concentration. Analyze the calibration gas
mixtures using the specified column and conditions with tjhe FID.
Plot the peak heights (or peak area) against the concentration and
draw a straight line through the points derived by the least squares
method. Analyze the low-concentration standard using the same
instrument conditions, and read the value from the curve. The
analyzed value and the known concentration should agree to within
5 percent. If this agreement is not obtained, run additional
!
dilutions to obtain this agreement. Record all data on a; data
i
sheet as shown in Figure 9. I
D-59
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Calibration Curve Data - Dilution Method
1. High Concentration Gas Mixture
Component
Diluent gas
Concentration
ppm
Date
Mixture 1 Mixture 2 Mixture 3
2. Dilution and Analysis Data
Stage 1
Component gas-rotameter reading
Diluent gas-rotameter reading ___
Ambient temp. (°C)
Manometer reading, inches H2O
Flow rate component gas (ml/min) __
Flow rate diluent gas (ml/min)
Stage 2
Component gas-rotameter reading
Diluent gas-rotameter reading"' .,
Flow rate component gas (ml/m£n) __
Flow rate diluent gas (ml/min _-_
Calculated concentration (ppmIV ___
Analysis
Sample loop volume (ml) ___
Sample loop temp. (°C)
Carrier gas flow rate (ml/min)
Column temperature
initial (°C)
program rate (°C/min)
final (°C) ' mUZI
Injection time (24-hr basis) ___
Distance to peak (inches)
Chart speed (inch/min)
Retention time (min)
Attenuator factor
Peak height (mm) __
Peak area (mm2) '
Area x attenuation factor (mm2)
Plot peak area x attenuator factor against concentration to ob-
tain calibration curve.
Figure 9.
Calibration curve data sheet -
dilution method.
D-60
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Low Concentration Standard
Known concentration (ppm)
.Retention time (min)
Injection time { 24-hr basis)
Attenuation factor
Peak height (mm)
2
Peak area (mm )
2
Peak area x attenuation (mm )
Calculated concentration (ppm)
Deviation (%)
Audit Samples
Retention time (min)
Injection time ( 24-hr basis)
Attenuation factor
Peak height (mm)
Peak area
Sanrole 1 Samale 2
(mm2)
Peak area x attenuation factor
Measured concentration ;
Data reported on (date) -.:
Data reported by (initial)
Certified concentration (ppm)
Deviation (%)
If a pump is used instead of a rotameter for component gas
flow, substitute pump delivery rate for rotameter readings)
Figure 9 (continued).
Calibration curve data sheet -
dilution method.
0-61
-------
Further details of the calibration methods for rotameters and
the dilution system can be found in Nelson's "Controlled Test
Atmospheres, Principles and Techniques."
As previously mentioned, a positive displacement pump can be
used to control the flow rate of the high-concentration calibration
gas, with a rotameter to measure the flow of the diluent gas. This
procedure can be used for both one- and two-stage dilutions following
the method outlined above.
Check the relative peak area of the calibration standards daily
to guard against degradation. If the relative peak areas on
successive days differ by more than 5 percent, remake the standards
before proceeding to the field -analysis.
2.3.2.2 Preparation of Standards. From Less Volatile Liquid Materials
Use the equipment shown iti Figure 10. Calibrate the dry gas
meter with a wet test meter or a spirometer. Use a water manometer
for the pressure gauge and glass, Teflon, brass, or stainless steel
for all connections. Connect a valve to the inlet of the 50-liter
Tedlar bag.
To prepare the standards, assemble the equipment as shown in
Figure 10 without the bag and leak check the system. Completely
evacuate the bag. Fill the bag with hydrocarbon-free air, and
evacuate the bag again. Close the inlet valve.
Turn on the hot plate and allow the water to reach boiling.
Connect the bag to the impinger outlet. Record the initial meter
reading, open the bag inlet valve, and open the cylinder. Adjust
D-62
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the rate so that the bag would be completely filled in approximately
15 minutes. Record meter pressure, temperature, and local barometric
pressure.
Fill the syringe to the desired liquid volume with the material
to be evaluated. Place the syringe needle into the impinger inlet
using the septum provided, and inject the liquid into the flowing
air stream. Use a needle of sufficient length to permit injection
i
of the liquid below the air inlet branch of the tee. Remove the
syringe.
Complete filling of the bag; note and record the meter pressure
and temperature at regular intervals, preferably 1 minute.
When the bag is filled, stop the pump and close the bag inlet
valve. Record the final meter readang.
Disconnect the bag from the impinger outlet, and set it aside
for at least 1 hour to equilibrate."' Analyze the sample within the
proven life period of its preparation.
Average the meter temperature (Tm) and pressure (Pm) readings
over the bag filling process.
Measure the solvent liquid density at room temperature by
accurately weighing a known volume of the material on an analytical
balance to the nearest 1.0 milligram. Take care during the weighing
to minimize evaporation of the material. A ground-glass stoppered
25-ml volumetric flask or a glass-stoppered specific gravity bottle
is suitable for weighing. Calculate the result in terms of g/ml.
D-64
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As an alternative, literature values of the density of the liquid
at 20°C may be used.
Calculate the concentration of material in the sample in
mg/liter at standard conditions as follows:
2593 (Ly) (p) (293 + Tj
std sol ~ (Mf - M.) TP7 •+• P j
Where:
Cstd sol = standard solvent concentration, mg/std liter.
P = Liquid density at room temperature, g/ml.
Ly = Liquid volume inected, ml.
= Meter temperature, °C.
= Meter pressureJ(gauge), mm Hg.
= Local barometric pressure (absolute), mm Hg.
Mf, M. = Final and initta3 meter reading, liters.
Continue the procedure as described in preparing the volatile standard
(.Section 2.3.2.1), and record all data on the sheets shown in
Figure 5.
2.3.3 Evaluation of Calibration and Analysis Procedure
Immediately after the preparation of the calibration curve and
prior to the sample analyses, perform the analysis audit described in
Supplement B: "Procedure for Field Auditing GC Analysis." The
information required to document the analysis of the audit samples
has been included on the example data sheets shown in Figures 5 and 9
m
m
bar
D-65
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and Supplement P-B. The audit analyses must agree with the audit
concentrations within +_ 10 percent. Testers may obtain audit
cylinders by contacting: Environmental Protection Agency,
Environmental Monitoring Monitoring Systems Laboratory, Quality
Assurance Division (MD-77), Research Triangle Park, North Carolina
27711. If audit cylinders are not available at the Environmental
Protection Agency, the tester must secure them from an alternative
source.
2.4 SAMPLING AND ANALYSIS PROCEDURE
Considering safety (flame hazards) and the source conditions,
select an appropriate sampling method. In situations where a hydrogen
flame is a hazard and no intrinsically safe GC is available, use the
bag collection technique or one of the adsorption techniques. If no
prohibitions against the hydrog^p flame exist, the source temperature
is below 100°C, and the organic concentrations are low enough to
prevent detector saturation, use the direct interface method. If the
source gases require dilution, use either the bag sample or adsorption
tubes with the dilution interface. The choice between these two
techniques will depend on the physical layout of the site, the source
temperature, and the storage stability of the compounds if collected
in the bag. Sample polar compounds by direct interfacing or dilution
interfacing to prevent loss by adsorption on the bag.
2.4.1 Adsorption Tube Method
Refer to the National Institute for Occupational Safety and
Health (NIOSH) method for the particular organics to be sampled.
D-66
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The principal interferent will be water vapor. If water vapor is
present at concentrations above 3 percent, silica gel must be
used in front of the charcoal. Where more than one compound is
present in the emissions, then relative adsorptive capacity
information must be developed.
Refer to the NIOSH method to determine the equipment required
for the particular organic(s) to be sampled. The following items
are also required.
Probe. Borosilicate glass, stainless steel, or Teflon,
approximately 6-mm ID, with a heating system if water condensation
could be a problem, and a filter (either in-stack or heated out-stack)
to remove particulate matter if.it is present. A plug of glass wool
is a satisfactory filter.
Sample Pump. Positive displacement type, with flow totalizer,
pumping rate approximately 10-100 cc/min with a set of limiting
orifices, MDA Scientific Model 808, or equivalent. j
Adsorption Tubes. Similar to ones specified by NIOSH, except \
I
adsorbent per section 200/800 mg for charcoal tubes and 260/1040 mg j
for silica gel tubes. i
Barometer. Accurate to 5 mm Hg, to measure a atmospheric
pressure during sampling and pump calibration.
Follow the sampling and analysis portions of the NIOSH method
section entitled "Procedure." Use a sample probe, if required.
The gas to be sampled must be provided at atmospheric pressure, or
slightly above it. Record the total volume of gas sampled, or the
D-67
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number of pump strokes, and the barometric pressure. Obtain a
i
total sample volume commensurate with the expected Concentration^)
i
i
of the volatile organic(s) present. Laboratory tests prior to
!
actual sampling may be necessary to accurately predetermine this
number. :
Operate the gas chromatograph according to the manufacturer's
instructions. After establishing optimum conditions, verify and
document these conditions during all operations. Repeat the analysis
until two consecutive injections do not deviate in area more than
2 percent from their average.
Standards shall be prepared according to the respective NIOSH
method. A minimum of three different standards shall be used,
and they shall bracket the expected sample concentration. Calibration
is to be performed before and £f;ter each day's sample analysis
T"iT
work. Prepare a calibration curve derived by the least square method.
Either before or after actual sampling, determine the i
desorption efficiency of each batch of adsorption media according
to the respective NIOSH method. Use an internal standard, j
Immediately before the sample analyses, perform analyses on
the two audits in accordance with Supplement I-B. The audit
analysis must agree with the audit concentration within + 10 percent.
2.4.2 Integrated Bag Sampling and Analysis
2.4.2.1 Evacuated Container Method
In this method, the bags are filled by evacuating the rigid
air-tight container holding the bags. As a result, both the bags
D-68
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and the container must be checked for leaks before and after use,
as follows: Connect a water manometer using a tee connector
between the bag or rigid container and a pressure source.
Pressurize the bag or container to 5 to 10 cm H20 (2 to 4 in.
H20), and allow it to stand overnight. A deflated bag indicates
a leak.
The following equipment is required for the evacuated container
method:
Probe - stainless steel, Pyrex glass, or Teflon tubing according
to the duct temperature, 6.4-mm-OD tubing of sufficient length to
connect to the sample bag. Use stainless or Teflon unions to
connect probe and sample line.
Quick connects - male (2) and female (2) of stainless steel
construction. ::
sT1
Needle valve - to control gas flow.
Pump - leak!ess Teflon-coated diaphragm-type pump or equivalent
to deliver at least 1 liter/min.
Charcoal- adsorption tube - tube filled with activated charcoal
and glass wool plugs at each end to adsorb organic vapors.
Flow meter - 0 to 500-ml flow range; manufacturer's calibration
curve is adequate.
To obtain a sample, assemble the sample train as shown in Figure 11.
Leak check both the bag and the container. Connect the vacuum line
from the needle valve to the Teflon sample line from the probe. Place
the end of the probe at the centroid of the stack and start the pump
D-69
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D-70
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with the needle valve adjusted to yield a flow of 0.5 liter/minute.
After allowing sufficient time to purge the line several times,
i
connect the vacuum line to the bag and evacuate until the rotameter
i
indicates no flow.; Then reposition the sample and vacuum lines,
and begin the actual sampling, keeping the rate proportional to
the stack velocity. Direct the gas exiting the rotameter away from
sampling personnel. At the end of the sample period, shut off the
pump, disconnect the sample line from the bag, and disconnect the
vacuum line from the bag container. Record the source temperature,
batometric pressure, ambient temperature, sampling flow rate, and
initial and final ^sampling time on the data sheet shown in Figure 12.
Protect the Tedlar bag and its container from sunlight. When possible,
perform the analysis within 8-hours of sample collection.
2.4.2.2 Direct Pump Method:-
" s-~
Follow 2.4.2.1, except place the pump and needle valve between
the probe and the bag. The pump and needle valve must be constructed
of stainless steel or some;other material that is not affected by
the stack gas. The system! must De adequately leak checked and then
purged with stack gas before the connection to the previously
evacuated bag is made. \
2.4.2.3 Analysis of Bag Samples
Connect the needle valve, pump, charcoal tube, and flow meter
to draw gas samples through the gas sampling valve. The operation
of the gas sampling valve is shown in Figure 13. Flush the sample
loop with gas from one of the three Tedlar bags containing
D-71
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Plant.
Site
Date
Sample 1
Sample 2
Sample 3
Source temperature (°C)
Barometric pressure (mm)
Ambient temperature (°C)
Sample flow rate
Bag number
Start time
Finish time
Figure 12. Field" sample data sheet - Tedlar
bag collection method.
D-72
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calibration mixture, and analyze the sample. Obtain at least two
chromatograms for the sample. The results are acceptable if the
peak areas agree to within 5 percent. If they do not agree, run
additional samples until consistent area data are obtained. If
this agreement is not obtained, correct the instrument technique
problems before proceeding. If the results are acceptable, analyze
the other two calibration gas mixtures in the same manner.
Calculate and draw the calibration line.
Analyze the two field audit samples (see Supplement I-B) by
connecting each Tedlar bag containing an audit gas mixture to the
sampling valve, following the guidelines used for the calibration
gases. Calculate the results; record and report the data to the
audit supervisor. If the results, are acceptable, proceed with the
analysis of the source samples.:-.
Analyze the source gas samples by connecting each bag to the
sampling valve with a piece of Teflon tubing identified with that
bag. Follow the restrictions on replicate samples specified for
the calibration gases. Record the data. Analyze the other two
bag samples of source gas in the same manner. After all three bag
samples have been analyzed, repeat the analysis of the calibration
gas mixtures.
An example field analytical data[sheet is shown in Figure 14.
The sheet has been designed to tabulate information from the bag
collection, direct interface, and dilution interface systems; as a
D-74
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Gaseous Organic Sampling and Analysis Data
Plant
Date
Location
General Information
Source temperature (°C)
Probe temperature (°C)
Ambient temperature (°C)
Atmospheric pressure (mm)
Source pressure ("Kg)
Absolute source pressure (mm)
Sampling rate (liter/rain)
Sample loop volume (ml)
Sample loop temperature (°C)
Columnar temperature.:
Initial (ac)/Tijne (rain)
Program Rate (°C/min)
Final (°C)/Time (min)
Carrier gas flow rate (ml/min)
Detector temperature (°C)
Injection time (24 hr. basis)
Chart speed (mm/min)
Dilution gas flow rate (ml/min)
Dilution Gas used (symbol)
Dilution ratio
Figure 14. Field analysis data sheets,
D-75
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2. Field Analysis Data - Calibration Gas
Run No. ' Time
Components Area Attenuation A x A Factor Cone, (pom)
Run No.
Time
Components Area Attenuation A x A Factor Cone, (pom)
Run No.
Time
Components Area AttenuatiSYi A x A Factor Cone, (ppm)
Figure 14 (continued). Field analysis data sheets .
D-76
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3. Field Analysis Data - Audit Samples ' Cylinder No.
Run No.
Time
Components Area Attenuation A x A Factor Cone,
(oom)
Run No.
Time
Components Area Attenuation A x A Factor Cone, (pom)
Run No.
Time: 1
Components Area Attenuation A x A Factor Cone, (pom)
Figure 14 (continued). Field analysis data sheets
D-77
-------
|4. Field Analysis Data - Source Gas
Run No. Time
Components Area Attenuation A x A Factor Cone, (pom)
Run No.
Time
Components Area Attenuation Ax A Factor Cone, (ppm)
Run No.
Time
Components Area Attenuation A x A Factor Cone, (opm)
Figure 14 (continued). Field analysis data sheets
D-78
-------
result, not all of the requested information will apply to any
single method. Note the data that do not apply with the notation
"N.A."
2.4.3 Direct Interface Sampling and Analysis
Use the direct interface sampling method whenever possible,
provided that the moisture content of the gas will not interfere
with the analytical method, the physical requirements of the
equipment can be met at the site, and the source gas concentration
is low enough that detector saturation is not a problem. The
equipment required for this method is as follows:
Probe - stainless steel, Pyrex glass, or Teflon tubing as
required by,duct temperature, 6.4-mm OD enlarged at duct end to
contain glass wool plug. Probe, should be heated with heating tape
or a special heating unit capable of maintaining duct temperature.
The heating unit can be controlled with a variable transformer or
with a temperature controller/readout device.
Sample lines - 6.4-mm-OD Teflon lines, heat-traced to prevent
condensation of material.
Quick connects - to connect sample line to gas sampling valve
on GC instrument and to pump unit used to withdraw source gas.
A quick connect should also be provided on the cylinder or bag
containing calibration gas to allow connection of the calibration gas
to the gas sampling valve.
Thermocouple readout device - potentiometer or digital
thermometer to measure source temperature and probe temperature.
D-79
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Heated gas sampling valve - of two-position, six-port design,
as shown in Figure 13, to allow sample loop to be purged with
source gas or to direct source gas into the GC.
Needle valve - to control gas sampling rate from the source.
Pump - leakless Teflon-coated diaphragm-type pump or equivalent,
capable of at least 1 liter/minute sampling rate.
Flow meter - of suitable range to measure sampling rate.
Charcoal adsorber - to adsorb organic vapor collected from
the source to prevent exposure of personnel to source gas.
Gas cylinders - of carrier gas (helium or nitrogen), oxygen,
and hydrogen for the FID.
Gas chromatograph - instrument capable of being moved into the
field with a FID, heated gas sampling valve, column required to
complete separation of desired-.-components, and option for temperature
—%.
programming. Other dectors can be used for problem analyses.
Recorder/Integrator - to record and/or calculate results.
To obtain a sample, assemble the sampling system as shown in
Figure 15. Make sure all connections are tight. Turn on the probe
and sample line heaters. As the temperature of the probe and heated
line approaches the source temperature as indicated on the
thermocouple readout device, control the heating to maintain a
temperature of 0-3°C above the source temperature. While the probe
and heated line are being heated, disconnect the sample line from
D-80
-------
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the gas sampling valve and attach the line from the calibration
gas mixture. Flush the sample loop with calibration gas and
analyze a portion of that gas. Record the results. After the
calibration gas sample has been flushed into the GC instrument,
turn the gas sampling valve to flush position, then reconnect the
probe sample line to the valve. Move the probe to the sampling
position and draw source gas into the probe, heated line, and sample
loop. After thorough flushing, analyze the sample using the same
conditions as for the calibration gas mixture. Repeat the analysis
on two additional samples. Measure the peak areas in the three
samples and if they do not agree to within 5 percent, analyze
additional samples. Record the-data. After consistent results are
obtained, remove the probe from..the source and analyze a second
calibration gas mixture. Record this calibration data and the other
~r
required data on the data sheet shown in Figure 14, deleting the
dilution gas information.
In addition, reanalyze the field audit samples by connecting the
audit sample cylinders to the gas sampling valve. Use the same
instrument conditions as were used for the source samples. Record
the data and report the results of these reanalyses to the audit
supervisor.
2.4.4 Dilution Interface Sampling
The sampling of sources containing a high concentration of
organic materials will require dilution of the source gas so that
the GC detector will not become saturated. The apparatus required
D-82
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for this direct- interface procedure is basically the same as that
described in the previous section, except that a dilution system
is added between the heated sample line and the gas sampling valve.
The apparatus is arranged so that either a 10:1 or 100:1 dilution
of the source gas can be directed to the chromatograph. A pump
of larger capacity is also required, and this pump must be heated
and placed in the system between the sample line and the dilution
apparatus.
The equipment required in addition to that specified for the
direct interface system is as follows:
Sample pump - leakless Teflon-coated diaphragm-type that can
withstand being heated to 120!*C and deliver 1.5 liters/minute.
Dilution pumps - two pumps are required such as the Model A-150
Komhyr Teflon positive displacement type delivering 150 cc/minute.
.-•*
As an option, calibrated flow meters could be used in conjunction
with Teflon-coated diaphragm pumps.
Valves - two valves of a three-way Teflon type suitable for
connecting to 6.4-mm-OD Teflon tubing.
Flow meters - two flow meters for measurement of diluent gas,
expected delivery flow rate to be 1350 cc/min.
Diluent gas - cylinders and regulators of the diluent gas are
required. Gas can be nitrogen or clean dry air, depending on the
nature of the source gases.
D-83
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Heated box - a box suitable for being heated to 120°C is
required to contain the three pumps, three-way valves, and
associated connections. The box should be equipped with quick
connect fittings to permit connection of: (1) the heated sample
line from the probe, C2) the gas sampling valve, (3) the calibration
gas mixtures, and (4) diluent gas lines. A schematic diagram of
the components and connections is shown in Figure 16.
The heated box shown in Figure 16 is designed to receive a
heated line from the probe. An optional design is to build a
probe unit that attaches directly to the heated box. In this way,
the heated box contains the controls for the probe heaters, or, if
the box is placed against the duet being sampled, the probe heaters
are completely eliminated. In either case, a heated Teflon line
is used to connect the heated box to the gas sampling valve on the
chromatograph.
The procedure for sampling and analysis using the dilution
interface system is as follows:
Assemble the apparatus by connecting the heated box, shown in
Figure 16, between the heated sample line from the probe and the
gas sampling valve on the chromatograph. Vent the source gas from
the gas sampling valve directly to the charcoal filter, eliminating
the pump and rotameter. Heat the sample probe, sample line, and
heated box. Insert the probe and source thermocouple at the centroid
of the duct. Measure the source temperature and adjust all heating
units to a temperature 0-3°C above this temperature. If this
D-84
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-------
temperature is above the safe operating temperature of the Teflon
components, adjust the heating to maintain a temperature high
enough to prevent condensation of water and/or organic compounds.
Verify the operation of the dilution system by analyzing a high
concentration gas of known composition through either the 10:1 or
100:1 dilution stages, as appropriate. (If necessary, vary the
flow of the diluent gas to obtain other dilution" ratios.) Determine
the concentration of the diluted calibration gas using the dilution
factor and the calibration curves prepared in the laboratory. Record
the pertinent data on the data sheet shown in Figure 14. If the
data on the diluted calibration gas are not within 5 percent of the
expected values, it will be necessary to determine whether the
chromatograph or the dilution system is in error. Verify the GC
operation using a low concentration standard by diverting the gas
into the sample loop, bypassingrthe dilution system. If these
analyses are within acceptable limits, the dilution system must
be corrected to provide the desired dilution factors. This correction
is made using a high-concentration standard gas mixture.
Once the dilution system and GC operation are satisfactory,
proceed with the analysis of source gas, maintaining the same dilution
settings as used for the standards. Analyze three separate samples.
If the analyses do not agree withint 'the accepted limits, collect
and analyze additional samples.
Repeat the analysis of the calibration gas mixtures to verify
equipment operation. Analyze the two field audit samples using
D-86
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either the dilution gas or direct connect to the gas sampling valve
as required. Record all data and report the results to the audit
supervisor.
2.4.5 Modified Procedures Using a Bag Collected Sample
In the event that condensation is observed in the bag collected
sample and a direct interface system cannot be used, heat the bag
during collection and maintain it at a suitably elevated temperature
during all subsequent operations. As an alternate, collect the
sample gas and simultaneously dilute it in the Tedlar bag.
In the first procedure, the box containing the sample bag is
heated to the source temperature, provided the components of the
bag and the surrounding box can withstand this temperature. The
bag is then transported as rapid.! y as possible to the analytical "
area while maintaining the heat-ing, or by covering the box with an
insulating blanket. In the analytical area, the box is kept heated
to source temperature until analysis. The method of heating the
box and the control for the heating circuit must be compatible with
the safety restrictions required in each area. In many cases, the
restrictions that prohibit the use of the FID may also eliminate
electrical heating elements.
The second procedure involves pre-filling the Tedlar bag with
a known quantity of inert gas. The inert gas is metered into the
bag by following the procedure for the preparation of gas concentration
standards of volatile liquid materials, but eliminating the midget
impinger section. This partly filled bag is taken to the source and
D-87
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the source gas is metered into the bag through heated sampling
lines and a heated flow meter or Teflon-positive displacement pump.
The dilution factors should be periodically verified by using known
concentration gases.
2.4.6 Reporting of Results
At the completion of the field analysis portion of the study,
the data sheets shown in Figure 14 must have been completed.
Summarize this data on the data sheets shown in Figure 17.
All data indicated on the table shown in this figure must be
filled in. The team leader or other person with the responsibility
of determining the validity of the data must sign the data sheets.
The signing of the data sheets.will confirm that (1) the data was
obtained as specified in the manual, (2) any deviations must be
specified and (3) the analysis.^ the audit samples was conducted
as required by the audit sample specification {Supptemerit'i-te;
The general information portion is filled out for each bag
sample or direct interface sample collected at a site. If the source
gas was collected using the bag sampling method, the data on each
bag sample must be averaged for the component analysis section. If
the direct interface method was used, then the data from each sample
analyzed must be separately summarized.
Additional sheets of this page are used for additional compounds,
The results of the audit sample analyses are presented on page 4 of
the report data sheet.
D-88
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cn
a
Gaseous Organic Sampling and Analysis Check List
•(Respond with! initials or number as appropriate)
Presurvey Data
A. Grab sample collected
B. Grab sample analyzed for composition
Method GC
GC/MS
Other
C. :GC-FID analysis performed
Laboratory Calibration Data
A. Calibration curves prepared
Number of components
Number of-concentrations/
component (3 required)
B. Audit samples (optional)
Analysis Icompleted
Verified for concentration
OK obtained for field work
Sampling Procedures
A. Method
Bag sample
Direct interface
Dilution interface
B. Number of samples collected
Field Analysis
A. Total hydrocarbon analysis performed
B. Calibration curve prepared
Number of components
Number of concentrations per
component (3 required)
Figure 17. Report data sheets.
en
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Date
•0-89
-------
Field Analysis (Continued)
C. Audit samples (Required)
Analysis completed
Verified for concentration
OK obtained to proceed [
D. Source samples [
Number of samples collected [
Number of replicates per sample
Agreement on replicates (%)
Deviations from Method — Specify
Figure 17 (continued)."'* Report data sheets,
D-90
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2.5 TOTAL VOLATILE ORGANIC MASS; CONTENT OF THE SOURCE GAS
This method is expected to provide information on approximately
I
90 percent of the total organic mass content of the source emissions.
j
To verify this (has been accomplished), an approximate total organic
mass measurement of the source gas must be made with an FID. A
second approach is to examine the source gas chromatograms. If
there is no more than a trace of unidentified compounds, it may be
assumed that 90 percent by mass of the organic components have been
measured. The major problem with these two approaches is that the
detector or column may not be suitable for revealing additional
organic materials. In either event, engineering judgment must be
exercised to decide whether undetected organic compounds possibly
exist in the stream being studied.
The referee approach is t©.-pbtain a total organic mass analysis
~
by GC/MS.
The total FID response data is expressed in terms of propane or
carbon equivalents. Standard samples of;propane in nitrogen (or air)
are used to calibrate the instrument. For this type of study,
commercial propane standard gas mixtures will provide the required
accuracy. In order to relate the source gas data to the total FID
response data, it is necessary to know the composition of the source
gas and the relative FID response of each of the components. Approximate
values can be obtained from literature sources. However, since
response values do vary between individual detectors, more precise
values can be found for the detector in use by measuring the response
of known concentrations of the components of the source gas relative
D-94
-------
to propane. A comparison of the total FID response of the source
gas (as propane) and the concentration of the identified compounds,
each referenced to propane, is then used to determine whether
90 percent of the source gas components have been identified and
quantified.
D-95
-------
BIBLIOGRAPHY
1. Federal Register, 41(111) :23076-23083, 1976.
2. Federal Register. 41(111) :23083-23085 and 23087-23090, 1976.
3. Federal Register, 41(111) :23085-23087, 1976.
4. Federal Register, 39(47) :9321-9323, 1974.
5. Federal Register, 39(47) :9319-9321, 1974.
6. Federal Register. 39(177) :32857-32860, 1974.
7. Tentative Method for Continuous Analysis of Total Hydrocarbons
in the Atmosphere. Intersociety Committee, American Public Health
Association, Washington, D.C., 1972. pp. 184-186.
8. Snyder, A.D., F.N. Hodgson, M.A. Kemmer and J.R. McKendree,
Utility of Solid Sorbents for Sampling Organic Emissions from
Stationary Sources, EPA 600/2-76.r201, U.S. Environmental Protection
Agency, Research Triangle Parki-N.C., July 1976, 71 pp.
9. Dravnieks, A., B.K. Krotoszynski, J. Whitfield, A. O'Donnell,
and T. Burgwald. Environmental Science and Technology, 5(12) :1200-1222,
1971.
10. NIOSH Manual of Analytical Methods, Volumes 1, 2, 3, 4.
U.S. DHEW, National Institute for Occupational Safety and Health,
Center for Disease Control, Cincinnati, Ohio. April 1977 - August
1978. Available from the Superintendent of Documents, Government
Printing Office, Washington, D.C. 20402. Stock « Volume 1 -
017-033-00267-3/$8.75, Volume 2 - 017-033-00260-6/$9.75, Volume 3 -
017-033-00261-4/$9.00, and Volume 4 - 017-033-00317-3/$7.25.
D-96
-------
11. Federal Register, 41(111) :23069-23072, 1976.
I 12. Schuetzle, D., T.J. Prater, and S.R. Ruddell. Sampling
i
arid Analysis of Emissions from Stationary Sources; I. Odor and
I
Total Hydrocarbons. Journal of the Air Pollution Control
Association, 25(9) :925-932, 1975.
! 13.. Federal Register, 41(205) :46569-46571, 1976.
', 14. Feairheller, W.R., P.J. Marn, D.H. Harris, and D.L. Harris.
Technical Manual for Process Sampling Strategies for Organic Materials.
EPA 600/2-76-122, U.S. Environmental Protection Agency, Research
Triangle Park, N.C., April 1976. 172 pp.
15. Jones, P.W., R.O. Grammar, P.E. Strup, and T.B. Stanford.
Environmental Science and Technology, 10(8) :806-810, 1976.
16. Hamersma, J.W., S.L.- Reynolds, and R.F. Maddalone.
EPA/IERL-RTP Procedures Manualt^ Level 1 Environmental Assessment.
V €
EPA-600/2-76-160a, U.S. Environmental Protection Agency, Research
Triangle Park, N.C., June 1976. 130 pp.
17. IHarris, J.C., M.J. Hayes, P.L. Levins, and D.B. Lindsay.
I
EPA/IERL-RTP Procedures for Level 2 Sampling and Analysis of Organic
Materials! EPA-600/7-79-033, U.S. Environmental Protection Agency,
Research triangle Park, N.C., February 1979. 154 pp.
18. C-| Through C$ Hydrocarbons in the Atmosphere by Gas
Chromatography. ASTM D 2820-72, Part 23, American Society for
Testing and Materials, Philadelphia, Pa., 23:950_958, 1973.
19. Eggertsen, F.T., and F.M. Nelsen. Gas Chromatographic
Analysis of Engine Exhaust and Atmosphere. Analytical Chemistry,
30(6) : 10.40-1043, 1958.
D-97
-------
20. Federal Register. 42(160) :41771-41776, 1977.
21. Nelson, G.O. Controlled Test Atmospheres, Principles
and Techniques. Ann Arbor Science Publishers, Ann Arbor, Michigan,
1971. 247 pp.
D-98
-------
SUPPLEMENT I-A TO ATTACHMENT I
COLUMN SELECTION
The success or failure of any GC analysis depends on the
suitablility of the column employed. To effect an adequate
chromatographic separation, it is necessary to choose a stationary
phase whose separation characteristics closely parallel the nature
of the samples to be analyzed. Three basic types of stationary
phases possess the capability of"adequately separating the classes
of compounds commonly encountered in sampling stack gas emissions.
LIQUID PHASE DEPOSITED ON A SOLID SUPPORT
The selection of a suitable solid support requires several
considerations. The solid support must have a large surface area
and a high porosity, and must be chemically and physically inert,
mechanically resistant, and thermally stable at the anticipated
operating temperatures. The corresponding liquid stationary phase
must also be carefully chosen for efficient separation. Numerous
types of liquid phases are comrnercially available in a broad range
of polarities; hydrogen-bonding and several special-purpose phases
are available also. The liquid phase selected should have sufficient
resolving capabilities for the components to be analyzed, should be
D-99
-------
fairly selective for the compounds to be encountered, and must be
stable on the support at the expected operating temperatures
(column bleeding should be minimal).
Liquid phases are manufactured under a variety of trade names,
and a survey of any recent chromatographic supplies catalog provides
several options suitable to achieve a desired separation. Most
liquid phases are relatively limited in the range of compounds they
can effectively separate, however., and most complex mixtures require
that two or more stationary phases be employed to yield complete
and efficient separation. Table A-l presents a selected listing
of liquid phases, their separation capabilities, and their optimum
operating temperature ranges-. _
In addition to the liquid phcises shown in Table A-l, the
Dexsi ^series of liquid phljes is sufficiently effective in the
<'?
general-purpose analysis of high temperature compounds to warrant
further discussion.
DEXSIL®
The 01 in Corporation's Dexsil High Temperature GC phases are
among the most useful of the high-temperature GC column packings
available. The structures of this series of three polymeric
packings consist of meta-carborane units connected by siloxane
units, giving unique separating capabilities. All three polymeric
phases are soluble in ether, dichloromethane, chloroform, and
aromatic solvents; insoluble in water and alcohols; and stable to
most chemicals with the exception of strong bases.
D-100
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D-101
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DEXSIL 300 GC
Dexsil 300 GC, a carborane/methyl silicone polymer, provides
effective separation for most organic: compounds. Dexsil 300 GC
exhibits extremely low bleed characteristics and is the most
thermally stable (maximum operating temperature, 450°C) of the
stationary phases, adequately separating mixtures of components
at high operating temperatures. It is the least polar of this
low polarity series.
DEXSIL 400 GC
Dexsil 400 GC, a carborane/methyl phenyl silicone polymer,
is only slightly more polar and less viscous than Dexsil 300 GC.
Dexsil 400 GC (maximum operating temperature, 375°C) is more
efficient in general separations, than Dexsil 300 GC, and it is
relatively stable over long perjods of time. Dexsil 400 GC provides
particularly effective separation for mixtures of polynuclear
aromatic compounds, and for compounds containing secondary amine
groups.
DEXSIL 410 GC
Dexsil 410 GC, a carborane/methyl cyanoethyl silicone polymer,
is the most polar of the stationary phases. The 2-cyanoethyl group
in the polymer provides unique selectivities for high-temperature
(maximum operating temperature, 360°C) separations of compounds
containing pi electrons, such as esters, ketones, and the
aeromatic compounds.
D-102
-------
SOLID STATIONARY PHASE
The solid stationary phase is the second type commonly
employed in GC analysis. Columns prepared with solid adsorbing
stationary phase packings require no liquid phase and give good
chromatographic separations of gases and relatively small organic
modules. Several types of solid adsorbents are available
comrnercially; the separation characteristics of a few of these
solid phases are delineated in Table A-2.
POROUS POLYMER RESINS
The third principal type of stationary phase employed in the
definitive analysis of stack gas emissions is the porous polymer
resin, the porous polymers can be used directly in GC columns
with, no liquid chromatographic phase required. Porous polymer
^* -
resins are available commercia^y in a wide variety of polarities
and with several different functional groups incorporated in the
various copyolymer units. These unique characteristics provide
efficient separations for several diverse classes of compounds.
With so many of these different polymer options available, it is
difficult to present a generalized list of their separation
capabilities. Instead, an abbreviated discussion delineating the
major applications of a few of the more commonly employed polymeric
resins follows.
D-103
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D-104
-------
PORAPAK®
Porapak is the register trademark for a series of porous
polymer resins manufactured by Waters Associates, Inc. These resins
are available in eight different types identified, in order of
increasing polarity, as P, P-S, Q, Q-S, R, S, N, and T. The first
six Porapak resins have a maximum operating temperature of 250°C;
Porapak N and T have a maximum operating temperature of 190°C.
PORAPAK P—
Porapak P, the least polar of the series, is a styrene-divinyl-
benzene-acopolymer used to separate a wide variety of carbonyl
compounds, glycols, and alcohols.
PORAPAK P-S—
Porapak P-S is the surface-silanized version of Porapak P,
which minimizes tailing. Its primary applications are in the
analysis of aldehydes and glycols.
PORAPAK Q~
Porapak Q, an ethylvinylbenzene-divinyl benzene polymer, the
most versatile and commonly employed resin in the series, is
particularly effective in the separation of hydrocarbons, organic
compounds in water, and oxides of nitrogen.
PORAPAK Q-S—
Porapak Q-S is the surface-silanized version of Porapak Q,
which eliminates tailing. It is commonly used to separate organic
acids and other polar compounds.
D-105
-------
PORAPAK R~
Porapak R, a vinyl pyrollidone polymer of moderate polarity,
is employed in the chromatographic analysis of ethers and esters,
and in the separation of water from C12 and HC1.
PORAPAK S—
Porapak S, a vinyl pyridine polymer, is applied primarily
to the separation of normal and branched chain alcohols.
PORAPAK N~
Porapak N, another vinyl pyrollidone resin, is utilized in
the separation of C02, NH3, and H20, and in separating acetylene
from other C2 hydrocarbons. This particular resin possesses a
high capacity for water retention.
PORAPAK T~ ~ri
»t
Porapak T, an ethylene glycol-dimethacrylate polymeric resin,
exhibits the greatest polarity and the highest water retention
capability in the series. It is used primarily in the determination
of formaldehyde in aqueous solutions.
CHROMOSORB®CENTURY SERIES
The Chromosorb Century Series, manufactured commercially by
Johns-Manville, is available in a series of eight porous polymer
resins. All resins in the series are designed for a maximum
operating temperature of 250°C.
D-106
-------
CHROMOSORB 101--
Chromosorb 101, a styrene-divinyl benzene polymer, is
particularly effective in the separation of hydrocarbons, alcohols,
fatty acids, esters, aldehydes, ketones, ethers, and glycols. Due
to its surface characteristics, Chrotnosorb 101 eliminates tailing
with oxygenated compounds, especially hydroxyl compounds (alcohols,
glycols, phenols) and carboxylic acids.
CHROMOSORB 102—
Chromosorb 102, another styrene-divinyl benzene polymer, has
an extremely high surface area, causing its behavior to resemble
that of a conventional column possessing a high liquid phase
loading, and a resulting in restively long column retention times.
It is used in the separation of light and permanent gases, as well
as in the analysis of low molecular weight compounds; i.e., acids,
alcohols, esters, glycols, ketones, hydrocarbons, etc.
CHROMOSORB 103—
Chromosorb 103, a cross!inked polystyrene polymer, yields fast
and efficient analysis of basic compounds such as amines. This
resin is also employed in the separation of a wide variety of
of compounds including alcohols, aldehydes, hydrazines, amides,
and ketones. Gylcols will be completely adsorbed by the resin,
and some tailing of water will occur at operating temperatures
below 150C.
D-107
-------
CHROMOSORB 104—
Chromosorb 104, an acrylonitrile-divinylbenzene polymer,
possesses the highest polarity in the Century series. Chromosorb
104 is a multipurpose resin, particularly effective in the
separation of nitriles, nitroparaffins, aqueous hydrogen sulfide,
xylenols, ammonia, oxides of nitrogen, sulfur, and carbon.
CHROMOSORB 105—
Chromosorb 105, a polyaromatic polymer, is employed primarily
for the separation of formaldehyde from water and methanol, the
isolation of acetylene from lower hydrocarbon compounds, and the
separation of most other organic compounds possessing different
polarities and boiling points less than 200°C.
CHROMOSORB 106— :r
c™. ~
* {
Chromosorfa 106, a cross!inked polystyrene polymer, has its
primary utility in the retention of benzene and nonpolar organic
compounds in relation to polar compounds, and in the separation
of Cg to Cg fatty acids from the corresponding alcohols.
CHROMOSORB 107—
*
Chromosorb 107, a crosslinked acrylic ester polymer, is a
resin of intermediate polarity. It is a good general purpose
column packing, especially efficient in the separation of
formaldehyde.
D-108
-------
and inorganic gases and volatile organic compounds. XAD-1, XAD-2,
and XAD-4 are all crosslinked polystyrene-divinyl benzene
copolymers of varying mesh sizes. These nonpolar resins have
been used to successfully separate many organic compounds, including
phenol, substituted chlorophenols, fatty acids, and amino acids.
They also provide adequate separation of permanent and inert gases.
XAD-7 and XAD-8, crosslinked acrylic ester polymeric resins of
intermediate polarity, can be applied in the analysis of many
permanent gases, C-, to Cy alcohols, and volatile organic compounds.
XAD-9, a sulfoxide, XAD-11, an amide, and XAD-12, another very
polar material, are utilized primarily in the separation of highly
polar compounds. __
D-109
-------
CHROMOSORB 108—
Chromosorb 108, another cross! inked acrylic ester polymer,
is generally applied to the separation of gases and polar materials,
such as water, alcohols, aldehydes, ketones, glycols, etc.
TENAX-GC
Tenax-GC, registered trademark of Tenax B.V., Arnhem, The
Netherlands, and commercially available in the U.S., is a porous
polymer column packing material based on 2,6-dipenyl-p-phenylene
oxide. Tenax-GC exhibits a lower polarity than any of the porous
polymers in the Porapak or Chromosorb Century series; compared to
these resins, Tenax-GC provides comparable separation of polar
compounds with relatively sfiorter retention times at lower operating
temperatures. Two outstanding' features of Tenax-GC are its maximum
operating temperature of 375SC and very stable baseline after only
a short conditioning period.
Tenax-GC has been shown to successfully separate a wide variety
of polar high-boiling compounds including alkyl ha! ides,
nitroani lines, alcohols, aldehydes, amides, monoamines, diamines,
diols, ethanol amines, ketones, methyl esters of dicarboxylic acids,
phenols, and polyethylene glycol compounds.
XAD® RESINS
The XAD resins, manufactured by Rohm and Haas, are a series of
macroporous cation exchange polymeric resins with well characterized
properties for the gas chromatographic separations of organic
D-110
-------
SUPPLEMENT I-B TO ATTACHMENT I
DETERMINATION OF ADEQUATE CHROMATOGRAPHIC PEAK RESOLUTION
In this method of dealing with resolution, the extent to which
one chromatographic peak overlaps another is determined.
For convenience, consider the range of the elution curve of
each compound as running from -20 to +2a. This range is used in
other resolution criteria, and it contains 95.45 percent of the
area of a normal curve. If two peaks are separated by a known
distance, b, one can determine the fraction of the area of one
curve that lies within the range of the other. The extent to which
the elution curve of a contaminant compounds overlaps the curve
of a compound that is under analysis is found by integrating the
contaminant curve over the limits b-2o to b+20 . where a is the
standard deviation of the sample curve.
There are several ways th'ts calculation can be simplified.
Overlap can be determined for curves of unit area and then actual
areas can be introduced. The desired integration can be resolved
into two integrals of the normal distribution function for which
there are convenient calculation programs and tables. An example
would be Program 15 in Texas Instruments Program Manual ST1, 1975,
Texas Instruments Inc., Dallas, Texas 75222.
b+2a
dt -
b-2a.
x2
T~
dx -
D-m
-------
The following calculation steps are required:*
1. 2as = ts//2 In 2
2.
3.
4.
t /2/2 in 2
w
3 (b-2as)/ac
= (b+2os)/ac
5.
_ X
e 2 dx
xl
6.
-
x
- 2
dx
7. I.
- Q(x2),
8. AQ =I0AC/AS
9. % overlap = AQ x 100
* (Note: In most instances, Q(x2) is very small and may be
neglected.)
D-112
-------
Where:
A.
= The area of the sample peak of interest determined
by electronic integration, or by the formula
Q(x,)
Q(x2)
= The area of the contaminant peak, determined in the
same manner as A .
= The distance on the chromatographic chart that
separates the maxima of the two peaks.
= The peak height of the sample compound of interest,
measured from the average value of the baseline to
the maximum of the curve.
« The width of the_ sample peak of interest at 1/2 of
peak height.
= The width of the-contaminant peak at 1/2 of peak
height.
= The standard deviation of the sample compound of
interest elution curve.
= The standard deviation of the contaminant elution
curve.
= The integral of the normal distribution function from
x-| to infinity.
= The integral of the normal distribution function from
x2 to infinity.
= The overlap integral.
= The area overlap fraction.
D-113
-------
In judging the suitability of alternate gas chromatographic
columns, or the effects of altering chromatographic conditions,
one can employ the area overlap as the resolution parameter with
a specific maximum permissible value.
The use of Gaussian functions to describe chromatographic
elution curves is widespread. However, some elution curves are
highly asymetric. In those cases where the sample peak is
followed by a contaminant that has a leading edge that rises
sharply but the curve then tails off, it may be possible to
define an effective width for t as "twice the distance from the
leading edge to a perpendicular line through the maxim of the
contaminant curve, measured along a perpendicular bisection of
that line."
D-114
-------
SUPPLEMENT I-C TO ATTACHMENT I
PROCEDURE FOR FIELD AUDITING GC ANALYSIS
Responsibilities of audit supervisor and analyst at the
source sampling site include the following:
1. To prevent vandalism, check that audit cylinders are
stored in a safe location both before and after the audit.
2. At the beginning and conclusion of the audit, record
each cylinder number and cylinder pressure. Never analyze an
audit cylinder when the pressure drops below 200 psi.
3. During the audit, the analyst is to perform a minimum
of two consecutive analyses of each audit cylinder gas. The
audit must be conducted to coincide with the analysis of source
test samples. Normally, it will" be conducted immediately after
the GC calibration and prior to the sample analyses.
4. At the end of the audTt analyses, the audit supervisor
requests the calculated concentrations from the analyst, and then
compares the results with the actual audit concentrations. If
each measured concentration agrees with the respective actual
concentration within +_ 10 percent, he then directs the analyst
to begin the analysis of source samples. Audit supervisor
judgment and/or supervisory policy determines course of action
when agreement is not within +_10 percent. Where a consistent
bias in excess of 10 percent is found, it may be possible to proceed
with the sample analyses, with a corrective factor to be applied
D-115
-------
to the results at a later time. However, every attempt should
be made to locate the cause of the discrepancy. The audit
supervisor is to record each cylinder number, cylinder pressure
Cat the end of the audit), and all calculated concentrations. The
individual being audited must not under any circumstance be told
the actual audit concentrations until the calculated concentrations
have been submitted to the audit supervisor.
D-116
-------
FIELD AUDIT REPORT
PART A - To be filled out by organization supplying audit
cylinders
1. Organization supplying audit sample(s) and shipping address
2. Audit supervisor, organization, and phone number
3. Shipping instructions - Name, Address, Attention
4. Guaranteed arrival date for cylinders^
5. Planned shipping date for cylinders
6. Details on audit cylinders from last analysis
Low Cone.
a. Date of last analysis
b. Cylinder number
c. Cylinder pressure,
d. Audit gas(es)/balance gas ;
e. Audit gas(es), ppm
f. Cylinder construction
High Cone.
D-117
-------
PART B - To be filled out by audit supervisor
1. Process sampl ed
2. Location of audit
3. Name of individual audited_
4. Audit date
5. Audit results
a. Cylinder number
b. Cylinder pressure^_before
audit, psi
c. Cylinder pressure-.-after
•* r
audit, psi
d. Measured concentration, ppm
Injection No. 1
Injection No. 2
Average3
Low Cone.
Cylinder
High Cone.
Cylinder
Results of two consecutive injections that meet the sample
analysis criteria of the test method.
D-118
-------
f. Audit accuracy
Low Cone. Cylinder
High Cone. Cylinder
Measured Cone. - Actual Cone.
Percent accuracy
Actual Cone.
x 100
g. Problems detected (if any)
D-119
-------
ATTACHMENT II TO APPENDIX D:
DETERMINATION OF THE HEATING VALUE AND
VOC EMISSION RATE OF EXHAUST GAS STREAMS
D-T20
-------
DETERMINATION OF THE HEATING VALUE AND VOC
EMISSION RATE OF EXHAUST GAS STREAMS
1. Principle and Applicability
1.1 Principle. This method describes the calculation of the net
heating value and VOC emission rate of gas samples. It specifies
methods to measure the organic compound content, carbon monoxide content,
hydrogen content, and moisture content of the gas sample. These compositional
data are used along with published or measured values, for the heats of
combustion and molecular weights to calculate the heating value and VOC
emission rate of the gas sample.
1.2 Applicability. The procedure is applicable to the measurement
of the heating value and VOC emission rate of gas streams from synthetic
organic chemical manufacturing industries, air oxidation processes.
2. Applicable Procedures
2.1 Measurement of Gaseous Organic Emissions by Gas Chromatography
(Appendix D, Attachment I).
2.2 Method 10. Determination of Carbon Monoxide Emissions from
Stationary Sources.
2.3 ASTM D 2504-67 (Reapproved 1977). Noncondensable Gases in C-,
and Lighter Hydrocarbon Products by Gas Chromatography.
2.4 ASTM D 2383-76. Standard Test Method for Heat of Combustion
of Hydrocarbons by Bomb Calorimeter.
2.5 Method 4. Determination of Moisture. Content in Stack Gases.
2.6 Method 2. Determination of Offgas Flowrate.
3. Analysis
3.1 Gas Composition. Determine the molar composition of the gas
using the procedures specified in Section 2 above. Measure all components
(including water vapor present) in amounts of 10 ppm or greater.
3.2 Heat of Combustion. If any of the components measured in
Section 3.1 do not have published heats of combustion, the heat of
combustion may be determined experimentally using the procedure in
Section 2.4. Alternatively, the heat of combustion may be calculated
from the published heats of formation if these are available.
4. Calculation
4.1 Calculate the concentration of the carbon monoxide from
Section 2.2 on a wet basis using Equation 1.
D-121
-------
Cwco • Cco
- Bw)
Eq. 1
where:
C
wco
Cco
Concentration of carbon monoxide, wet basis, ppm.
Concentration of carbon monoxide from Section 2.2., ppm,
dry.
B - Water vapor in the gas sample, proportion by volume.
4.2 Calculate the net heating value of the sample gas (25°C,
760 mm) using Equation 2.
where:
Ci
Hi
HCQ)
Eq. 2
= Net heating value of the sample, MJ/scm, where the net
enthalpy per mole of off gas is based on combustion at
25 C and 760 mm Hg, but the standard temperature for
determining the volume corresponding to one mole is
20 C, as in the definition of Q (offgas flowrate).
= Constant, 1.740 x 10
temperature for (
'7
'ppm' v
> is 20°C.
. where .standard
wco
H
CO
= Concentration of sample component i, ppm.
- Net heat of combustion of sample component i, kcal/g-mole.
The. heats of combustion of process vent stream components
would be determined using ASTM D2382-76.if published values
are not available or cannot be calculated.
= Concentration of carbon monoxide', wet basis, ppm.
* Net heat of combustion of carbon monoxide, kcal/g-mole.
4.3 Calculate the VOC emission rate of the sample gas using
Equation 3.
Eq. 3
D-122
-------
where:
E
VOC
= VOC emission rate of the sample, kg/hr.
K = Constant, 2.494 x 10~6-(1/ppm) (g-mole/scm) (kg/g) (min/hr)
where standard temperature for (g-mole/scm) is 20 C. ;
M.J = Molecular weight of sample component i, g/g-mole. !
Q = Vent stream flowrate (scm/min), at a standard temperature
s of 20°C.
D-123
-------
5. Bibliography
5.1 Noncondensable Gases in C3 and Lighter Hydrocarbon Products by
Gas Chromatography. In: 1980 Book of ASTM Standards, Part 24. Philadelphia,
Pennsylvania. ASTM Designation D 2504-67. 1980.
5.2 Standard Test Method for Heat of Combustion by:Hydrocarbons by
Bomb Calorimeter. In: 1980 Book of ASTM Standards, Part 24. Philadelphia,
Pennsylvania. ASTM Designation D 2382-76. 1980.
5.3 Perry, J.H. Chemical Engineers Handbook. New York. McGraw-
Hill Book Co., Inc. 3rd Edition. 1950. p. 236246.
D-124
-------
APPENDIX E: TRE CALCULATIONS
-------
-------
APPENDIX E: TRE CALCULATIONS
E.I INTRODUCTION
This appendix presents calculations and derivations related to the
definition and implementation of regulatory alternatives. Details of the
tests and analytical methods involved in the implementation of regulatory
alternatives are presented in Appendix D.
E.2 TOTAL RESOURCE-EFFECTIVENESS
Best demonstrated technology (BDT) is based on incineration of certain
process vent streams discharged to the atmosphere. The streams for which
BDT involves this VOC reduction are those for which the associated total
resource-effectiveness (TRE) index value is less than 2.2. Thermal
oxidation can reduce VOC emissions by 98 weight percent or to 20 ppm
(volume, by compound), whichever is less stringent. An index value of TRE
can be associated with each air oxidation vent stream for which the offgas
characteristics of flowrate, hourly" emissions and net heating value are
known. For facilities with a process vent stream or combination of process
vent streams having a TRE index value which exceeds the cutoff level of 2.2,
the removal of VOC using thermal incineration is not reasonable.
TRE is a measure of the supplemental total resource requirement per
unit VOC reduction, associated.with VOC control by thermal oxidation. All
resources which are expected to be used in VOC control by thermal oxidation
are taken into account in the TRE index. The primary resources used are
supplemental natural gas, capital, and (for offgas containing halogenated
compounds) caustic. Other resources used include labor, electricity, and
(for offgas containing halogenated compounds) scrubbing and quench makeup
water. I
i
The TRE index is derived from the cost-effectiveness associated with
VOC control by thermal oxidation. The calculation of cost-effectiveness and
derivation of the TRE ind^x are given in detail in Chapter 5. The total
resource-effectiveness (Ifa) index of a vent stream is defined as the
cost-effectivenesss value 'of the stream, multiplied by 100, and divided by a
cost-effectiveness value of $88.66 thousand/Mg. This value is the
E-l
-------
cost-effectiveness associated with incineration of that stream in the
national statistical profile (described in Appendix F) which is most
expensive to control per pound of VOC.* The TRE index is a convenient,
dimensionless measure of the total resource burden associated with VOC
control at a facility. It is independent of the general inflation rate.
However, it does assume fixed relative costs of the various resources, such
as carbon steel and natural gas.
The distinction in BDT, between facilities with a TRE index value above
the cutoff'level and those with a value below it, is meant to encourage the
use of product recovery techniques or process modifications to reduce
emissions. The values of offgas flowrate, hourly emissions, and net heating
value used to calculate the TRE value for a given facility are measured at
the outlet of the final piece of product recovery equipment. Use of
additional product recovery is expected to decrease VOC emissions and
increase the total resource-effectiveness associated with thermal inciner-
ation of a vent stream.
The TRE index cutoff level associated with BDT has the value 2.2. The
TRE index of a process vent stream is calculated according to the following
equation:
TRE
(a + b (Qs)0.88 +
e (Qs)0'88 (H/-88
f (HT)0'88)
where:
TRE = Total resource-effectiveness index value.
Q =jVent stream flowrate (scm/min), at a standard
5 [temperature of 20°C.
i
l
HT =| Vent stream net heating value (MJ/scm), where the net
ienthalpy of per mole of offgas is based on combustion at
',25 C and 760 mm Hg, but the standard temperature for
•determining the volume corresponding to one mole is 20 C,
;as in the definition of Q .
Excluding four profile vent streams with a reported VOC concentration
below the detectable limit.
E-2
-------
EVOC = VOC ei7n"ssi°n rate reported in kg/hr measured at full
operating flowrate.
a, b, c, d, e, and f are coefficients. The set of coefficients which
apply to a process vent stream can be obtained from Table E-l.
Table E-l is divided into the six design categories for control
equipment. These design categories differ in the amount of heat recovery
achieved, in the type of heat recovery equipment used, and in the use of
flue gas scrubbing for offgas containing chlorinated compounds. The amount
and type of heat recovery used depends upon the offgas heating value. These
design categories are defined and discussed in detail in Chapter 5. Under
each design category listed in Table E-l, there are several intervals of
offgas flowrate. Each flowrate interval is associated with a different set
of coefficients. The first flowrate interval in each design category
applies to vent streams with a flowrate smaller than that corresponding to
the smallest control equipment system easily available without special
custom design. The remaining flowrate intervals in each design 'category
apply to vent streams which would be expected to use one, two, three, four,
or five sets of control equipment, respectively. These flowrate intervals
are distinguished from one another because of limits to prefabricated
equipment sizes. The flowrate intervals and maximum offgas flowrate for
each design category are presented and discussed in Chapter 8.
An air oxidation vent stream of an affected facility was considered to
be "chlorinated" if it contained a concentration of 20 ppmv (by compound) or
greater of chlorinated compounds. This low'20 ppmv chlorination cutoff was
chosen to avoid control cost and TRE underestimates. Even small amounts of
chlorinated compunds may be corrosive, as well as difficult enough to
incinerate that a temperature greater than 870°C is necessary to achieve
98 percent control. Therefore, it was judged essential to set a low cutoff,
so that control cost and TRE would not be underestimated for any facility.
Because the ethylene dichloride process may have affected facilities subject
to the proposed standards, the chlorination cutoff was set at 10 percent of
the lowest known total chlorinated compound concentration for any existing
ethylene dichloride facility, or 20 ppmv.
E-3
-------
TABLE E-l. COEFFICIENTS'OF THE TOTAL RESOURCE EFFECTIVENESS (TRE) INDEX EQUATION
Al. FOR CHLORINATED PROCESS VENT STREAMS, IF
H « Design Standard Flowrate (Nm3/m1n)
U < 14
14 < w < 740
740 < V < 1480
1480 < V < 2220
2220 < I < 2950
2950 < W < 3S90
A2. FOR CHLORINATED PROCESS VENT STREAMS, IF
W - Design Standard Flowrate (Nm3/min)
W < 14
14 < W < 740
740 < V ~ 1480
1490 < W < 2220
2220 < V < 2950
2950 < W 7 3690
B. FOR NONCHLORINATED PROCESS VENT STREAMS,
H » Design Standard Howrate (Nra /m1n)
W < 14
14 < W < 1420
1420 < U < 2840
2840 < W < 4260
C. FOR HOJiCHLORINATED PROCESS VENT STREAMS,
W » Design Standard Flowrate (Nm /min)
W < 14
14 < W < 1420
1420 < W < 2840
2840 < W < 4260
D. FOR HONCHLORINATED PROCESS VENT STREAMS,
W » Design Standard Flowrate (Nm /min)
W < 14
14 < W < 1250
1250 < W < 2500
2500 < W < 3750
E. FOR NONCHLORINATED PROCESS VENT STREAMS,
W - Design Standard F1owrate (Nra /min)
W < 14
14 < W < 1250
1250 < U < 2500
2500 < W < 3750
0 < NET HEATING VALUE (MJ/Nm3) <. 3.5:
a b c
45.68 0 0.369
38.04 0.749 0.369
76.09 0.815 0.369
114.13 0.853 0.369
152.17 0.885 0.369
190.21 0.909 0.369
3.5 > NET HEATING VALUE (MJ/Nm3):
a b c
45.68 0 -0.0418
38.04 0.749 -0.0418
76.09 0.815 -0.0418
114.13 0.853 -0.0418
152.17 0.885 -0.0418
190.21 0.909 " -0.0418
IF 0 ^ NET HEATING VALUE (MJ/Nffl3) < 0.48:
a b c
16.10 0 0.0697
13.78 0.227 0.0697
27.57 0.247 0.0697
41.35 0.252 . Q.0697
IF 0.48 < NET HEATING VALUE (MJ/Nm3) < 1.9:
a b c
16.27 0 0.240
15.01 0.123 0.240
30.03 0.134 0.240
45.04 • 0.140 0-240
IF 1.9 < NET HEATING VALUE (MJ/Nm3) < 3.6:
a b c
13.54 0 0.021
11.98 0.153 0.021
23.96 0.166 0.021
35.94 0.175 0.021
IF 3.6 < NET HEATING VALUE (MJ/Nm3):
a b c
13.54 0 0
11.98 0 0
23.96 0 0
35.94 0 0
d
-0.0906
-0.0906
-0.0906
-0.0906
-0.0906
-0.0906
d
0
0
0
0
0
0
d
-0.118
-0.118
-0.118
-0.118
d
-0.112
-0.112
-0.112
-0.112
d
0
0
0
0
d
0.0059
0.0059
0.0059
0.0059
e
0
0
0
0
0
0
e
0
0
0
0
0
0
e
0
0
0
0
e
0
0
0
0
e
0
0
0
0
e
0
0.0495
0.0540
0.0564
f
0
0
0
0
0
0
f
0
0
0
0
0
0
f
0
0
0
0
f
0
0
0
0
f
0
0
0
0
f
0.505
0
0
0
E-4
-------
E.2.1 Derivation of the TRE Coefficients
The Total Resource Effectiveness (TRE) of an offgas stream is defined
as the cost effectiveness of incinerating the VOC stream under consideration
divided by the cost effectiveness of incinerating a reference stream,
multiplied by 100. The reference stream is chosen to be 'that stream in the
national profile which proved most expensive to control. The cost
effectiveness of treating an offgas stream,is determined by developing
equations for the various annual cost components of the incineration system.
These components include annualized capital costs, supplemental gas costs,
labor costs, electricity costs, quench water costs, scrub water costs,
neutralization costs, and heat recovery credit. The development of each of
the cost component equations is summarized in Table E-2.
The parameters that are used in Table E-2 or are required in the
derivation of the TRE equation are defined as follows:
C —
Flow
f/o
HT
HRF
AP
i « Go
uncontrolled VOC emission rate, [kg/hr]
number of incinerator units, [-]
total design offgas flow rate, [Mm /min]
flue gas: off gas flow rate, [-]
heating value of offgas stream [106J/Nm3]
heat recovery factor of offgas stream, [106J/Nm3]
scrubber pressure drop, [inches H^O]
coefficients in the supplemental natural gas
equation with units as follows:
GQ [106J/min]
G [106J/Nm3l
Substituting the cost expressions of Table E-2 into the TRE equation
definition yields the following derivation:
E-5
-------
TABLE E-2. MATHEMATICAL FORMULATION OF ANNUAL
INCINERATOR COST COMPONENTS
Component
Annualized Cost (10 $/yr)
1. Annualized Capital
Cost, Taxes, and
Maintenance
2. Supplemental Natural
Gas
3. Labor Cost
4. Electricity Cost
(number of equipment units) x (escalation factor)
x (retrofit correction factor) x (capital re-
covery factor + taxes and maintenance factor) x
(capital cost per unit)
= N x 1.056 x 1.625 x (0.163 + 0.11)
x (Cj + C2(Flow/N/0.95)°'88)
(gas price) x (supplemental gas required per
minute, per unit) x (number of minutes per year)
x (number of units)
= 2.40[$/109J] x (6 + (0.77 x Flow/N) x
(G1 + 62 x HT))[106J/min] x
0.5256[106min/yr] x N
(labor wage) x (labor factor per unit) x
(number of units)
= 11.10/1000[103$/man-hr] x
(labor factor)[man-hr/yr] x N
(electricity price) x (pressure drop) x (average
offgas flow rate) x (flue gas:offgas ratio)
x (fan equation conversion factor) x (number of
hours per year) * (fan efficiency)
= 0.049/1000[103$/kW-hr] x AP[in H20] x
0.77 x Flow[Nm3/min] x f/o[-] x
0.004136[kW/Nm3-in H20] x 8760[hr/yr] * 0.6
= (0.0604) x ($.049) x AP x 0.77 x Flow x f/o
E-6
-------
TABLE E-2. (CONTINUED) MATHEMATICAL FORMULATION OF
ANNUAL INCINERATOR COST COMPONENTS
Component
Annualized Cost (103$/yr)
5. Quench Water Cost
(water cost) x (average offgas flow rate)
x (flue gas:offgas ratio) x (water required
per unit flue gas flow rate) x (number of
minutes per year)
= $0.79[$/103gal] x 0.77 x Flow[Nm3/min] x
f/o[-] x 1.68 x 10"5[103gal/Nm3] x 0.5256
x 106[min/yr] x l/1000[103$/$]
= $0.79 x (0.77 x Flow) x f/o x 0.00883
6. Scrub Water Cost
(water cost) x (average offgas flow rate) x
(flue gas:offgas ratio) x (chlorine content
of flue gas) x (water required per unit
chlorine) x (number of hours per year)
= 0.79[$/103gal] x 0.77 x Flow[Nm3/min]
x 35.314scf/Nm3 x f/o[-] x
0.0487[ 1b/hr Ch1or1ne ]
scf/min flue gas
x 0.0192[103gal/lb chlorine]
x 8760 hr/yr x l/1000[103$/$]
= ($0.79) x (0.77 x Flow) x f/o x (0.289)
: E-7
-------
TABLE E-2. (CONTINUED) MATHEMATICAL FORMULATION OF
ANNUAL INCINERATOR COST COMPONENTS
Component
Annualized Cost (10 $/yr)
7. Neutralization Cost (caustic cost) x (average offgas flow rate)
x (flue gas: offgas ratio) x (chlorine
content of flue gas) x (caustic requirement
per unit chlorine) x (number of hours per
year)
= $0.0563[$/lb NaOH] x 0.77 x Flow[Nm3/min]
x 35.314 scf/Nm3 x f/o[-]
x 0.0487C 1b/hr chlorine ]
scf/min flue gas
x 1.14[lb NaOH/lb chlorine] x 8760[hr/yr]
x l/1000[103$/$]
= ($0.0563) x (0.77 x Flow) x f/o x (17.17)
8. Heat Recovery Credit (gas price) x (average offgas flow rate) x
(energy recovery per unit offgas flow rate)
x (number of minutes per year)
= $2.40[$/109J] x 0.77 x Flow[Nm3min]
x HRF[106J/Nm3] x 0.5256[106min/yr]
= ($2.40) x (0.77 x Flow) x (0.5256) x HRF
E-8
-------
TRE EQUATION DERIVATION
Equation 1:
TRE = Total Resource = cost effectiveness of stream
Effectiveness cost effectiveness of reference stream x 10°
= annualized cost of stream [103$/yr] v emissions reduction [Mg/vrl
~55.73 x 103$/Mg
Equation 2:
annualized cost _ /annualized capital^ /annual supplemental,,
of stream [103$/yr] l cost ' + ( gas cost '
+ /annual laborv /annual electricity^
. v cost ; { cost '
+ /annual quencfu /annual scrub>
v water cost ' *• water cost '
x 100
/annual neutralization
\ _ / annual heat \
' ~ ^recovery credit'
cost
= N x 1.056 x 1.625 x (0.163 + 0.11)
x (C, + C«
Flow -^0.88^
u N x 0.95
+ $2.40 x (GQ + 0.77 x Flow x (Gx + G2 x HT))
x 0.5256
+ $11.10/1000 x (labor factor)
+ $0.049 x (0.0604) x AP x (0.77 x Flow)
+ $0.79 x (0.77 x Flow) x f/o x (0.00883) Category A
only.
+ $0.79 x (0.77 x Flow) x f/o x (0.289) Category A
only
+ $0.0563 x (0.77 x Flow) x f/o x (17.17) Category A
only
- $2.40 x (0.77 x Flow) x 0.5256 x HRF Category A
only
E-9
-------
Equation 3:
emissions reduction
[Mg/yr]
/hourly uncontrolled^ /number of days>
^ emissions ' ^ per year '
/ number of hours> / capacity %
x ( per day ' x ^utilization'
x (VOC destruction efficiency)
= E [kg/hr] x 10~3[Mg/kgl x 365 [days/year]
x 24 [hours/day] x 0.77 x 0.98
Equation 4:
TRE - (annual ized cost of stream) [103$/yr]
(55.73)[103$/Mg] x E [kg/hr] x 6.610
kg-yr
x 100 = 0.2714 x (annualized cost of stream) [103$/yr]
E Lkg/hrJ
= (0.2714/E) x {N x 1.056Qx 1.625 x (0.163 + 0.11) x
(G + C (flow/N/0.95)u'0b
+ N x (2.40 x (GQ + 0.77 x Flow/N x
+ G2 x Hy))
x 0.5256) + N x 11.10/1000 x (labor factor)
+ 0.049 x (0.0604) x AP x (0.77 x flow x f/o)
+ [0.79 x (0.77 x Flow) x f/o x (0.00883)
+ 0.79 x (0.77 x Flow) x f/o (0.289) + 0.00563 x f/o
x (0.77 x Flow) x (17.17)
- 2.40 x (0.77 x Flow) x 0.5256 x HRF]}
Note: The terms contained in brackets [ ] apply to category A only.
Next, the TRE equation is rearranged in the form:
Equation 5:, n Rp
TRE = - ( a + b(flow)U
-------
Coefficients a^ through f_ are derived by substituting numeric values for
all quantities except flow, HT, and E, and then collecting like algebraic
terms. Design categories B, C, and D always have the same expressions for
the coefficients, while design categories A and E must be considered indi-
vidually for some of the coefficients. Category A has costs associated with
chlorine removal that are unique among the design categories. Category E is
unique because the offgas flow is diluted prior to incineration such that
the variable "flow" is replaced everywhere in Equations 2, 3, and 4 by "flow
x H-J-/3.6." These special features of categories A and E lead to
variations in the expressions for coefficients a_ through f_.
The term in the TRE equation involving coefficient a_ is independent of
flow. The expression for coefficient a_ is identical for all design cat-
egories, and it consists of terms involving Cl, G . and a labor factor.
o 0
If the operating flow rate is less than 14 Nm /min, then the expression
also includes a term involving C2 because in this case the fixed value flow
3
= 14 Nm /min is used in the annualized capital cost expression.
- For design categories A, B, C, D, and E:
3
• when flow <14 Nm /min
a = 0.2714 x 1.056 x 1.625 x 0.273 x N x Cl + 0.2714 x 2.40 x
0.5256 x GQ x N + N x 0.0111 x 0.2714 x (labor factor)
+ 0.2714 x N x 1.056 x 1.625 x 0.273 x C2 x (14/0.95)0'88
= 0.1271 x N x Cl + 0.3424 x G x N + 0.003 x N x (labor factor)
+ 0.1271 x N x C2 x (14/0.95)
3
• when flow >14 Nm /min
'0.88
a = 0.2714 x 1.056 x 1.625 x 0.273 x N x Cl +0.2714 x 2.40 x 0.5256
x GQ x N + N x 0.111 x 0.2714 x (labor factor)
= 0.1271 x N x Cl + 0.3424 x GQ x N + 0.003 x N x (labor factor)
The term in the TRE equation involving coefficient b^ depends on
(flow)
0.88
For design categories A, B, C, and D, the expression for
E-ll
-------
coefficient b^ includes just one term that depends on C2, and therefore,
coefficient b is non-zero only when coefficient a does not include the C2
3
term (i.e., coefficient b_ is non-zero only when flow >14 Mm /min).
Coefficient £• equals zero regardless of the value of flow for category E.
- For design categories A, B, C, and D:
3
• when flow <14 Nm /min
b = 0
3
• when flow >14 Mm /min
b = 0.2714 x N x 1.056 x 1.625 x 0.273 x C2 x 0.950'88 x N"°'88
= N°'12 x 0.133 x C2
- For design category E:
b = 0 (all flow values)
The term in the TRE equation involving coefficient c_ depends on (flow).
For design category A, the expression for coefficient £ includes terms that
depend on 61, AP, f/o, (f/o) x (AP), and HRF. For design categories B, C,
and D, HRF = 0 and the corresponding term does not appear in the expression
for £. Coefficient £ is zero for design category E.
- For design category A:
c = 0.77[0.2714 x 2.4 x 0.5256(G1-HRF) + 0.2714 x 0.0604 x 0.049
x AP x f/o + 0.2714(0.79 x 0.00883 + 0.79 x 0.289 + 0.0563
x 17.17) f/o]
= 0.77[0.3424(G1-HRF) + .000803(AP)f/o + 0.327 f/o]
- For design categories B, C, and D:
c = 0.77[0.2714 x 2.4 x 0.5256 x 61 + 0.2714 x 0.0604
x 0.049 x AP x f/o]
= 0.77[0.3424 x 61 + 0.000803(AP)f/o]
- For design category E:
c = 0
E-12
-------
The term in the TRE equation involving coefficient d^ depends on the
(flow) x (HT) product. For design categories A, B, C, and D, the
expression for coefficient d^ consists of just one term that depends on 62,
For design category E, the expression for coefficient d_ consists of terms
depending on 61 and the (AP) x (f/o) product.
- For design categories A, B, C, and D:
d = 0.77 x 0.2714 x 2.4 x 0.5256 x 62
= 0.77 x 0.3424 x 62
- For design category E:
d = 0.77/3.6 x 0.2714[2.40 x 0.5256 x 61 +.0.049 x 0.0604
x AP x f/o]
= 0.77/3.6[0.3424 x 61 + 0.000803 x AP x f/o]
The term 'in the TRE equation involving coefficient e depends on the
0 RR fl RR —
(flow) • x (HT) * product. This product arises only in the TRE
expression for-category E.
- For design categories A, B, C, and D:
e = 0 (all values of flow)
- For design category E:
• when flow <14 Mm /m'in
t when flow >14 Nm3/min
e = 0.2714 x N x 1.056 x 1.625 x 0.273 x C2 x 3.6~°'88 x 0.95~°'88
= N°-12 x 0.1271 x C2/3.6°'88/0.95°-88
E-13
-------
The term in the TRE equation involving coefficient f_ depends on
(HT)°*88. Coefficient f is zero for design categories A, B, C, and D.
3
The value of coefficient jf is non-zero only if flow <14 Mm /min for design
category E.
- For design categories A, B, C, and D:
f = 0 (all values of flow)
- For design category E
• when flow <14 Nm /min
f = 0.2714 x 1 x 1.056 x 1.625 x 0.273 x C2 x 3.6
x 0.95-0-88 x 14°-88 x I"0'88
= 0.1271 x C2 x 3.6-°'88 x 0.95-°'88 x 14°'88
3
t when flow >14 Nm /min
-0.88
E.2.2 Example Calculation of the TRE Index Value for a Facility
This section presents an example of use of the TRE index equation for
determination of the design category applicable to an individual air
oxidation facility. It has been determined that the air oxidation process
vent stream has the following characteristics:
1. Qs = 284 scm/min (10,000 scfm).
2. HT = 0.37 MJ/scm (10 Btu/scf).
3. Hourly Emissions (EVOC) = 76''' k9/nr<
4. No chlorinated compounds in the offgas.
Because there are no chlorinated compounds in the offgas, design Category A
is not the applicable one. Categories Bs C, D, and E all correspond to
nonchlorinated vent streams. Because the offgas net heating value is
0.37 scm/min, Category B is the applicable one. The offgas flowrate is 284
scm/min, and therefore the second flowrate interval under Category B is the
applicable one. The coefficients for Category B, flow interval #2 are:
E-14
-------
1.
2.
3.
4.
5.
6.
a = 15.83
b = 0.215
c = 0.240
d = -0.426
e = 0
f = 0
The TRE equation is:
TRE = (1/76.1)05.83 + 0.215 (284)0'88 + (0.240)(284)-0.426
(284)(.37) +0+0)
TRE = 0.21 + 0.41 + 0.89 - 0.59 +0+0
TRE = 0.9
Since the calculated total resource-effectiveness (TRE) index value of
0.9 is less than the cutoff value of 2.2, the applicable BDT for this
facility would be 98 percent VOC reduction or reduction to 20 ppm. If
process modifications or increased product recovery were introduced, the
product recovery vent offgas percent VOC and heating value might be
sufficiently decreased that the resulting TRE value would exceed the 2.2
cutoff.
E.2.3 Calculation of Cost-effectiveness for a Facility
Because the TRE index is a cost-effectiveness ratio, it is possible to
calculate cost-effectiveness for any vent stream given its TRE index value.
The TRE index value of the facility is divided by 100 (since TRE is a
percentage), multiplied by the indexing constant $88.66 thousand/Mg, and
finally multiplied by 1000 (to convert the units to $/Mg). For the stream
used in the example above, the cost-effectiveness is found as follows:
TRE =0.9
Indexing constant = $88.66 thousand/Mg
Cost effectiveness = (0.9)(88.66)(1000)/100 = $800/Mg.
E-15
-------
-------
APPENDIX F: STATISTICAL ANALYSIS
-------
-------
APPENDIX F: STATISTICAL ANALYSIS
F.I INTRODUCTION
The purpose of this appendix is to describe the methods of statistical
analysis used in the development of the air oxidation unit process new
source performance standard (NSPS). The method of regulatory analysis
developed for this NSPS uses a national statistical profile, representing
the air oxidation segment of SOCMI to project the energy, cost, and
environmental impacts associated with VOC control using several regulatory
alternatives. A method for statistically estimating offgas flowrates
for air oxidation processes is also described.
F.2 STATISTICAL IMPACT ANALYSIS
Typically, an NSPS would be developed on a chemical-by-chemical
basis. Because the processes used by a single chemical-producing industry
to manufacture a specific product do not differ greatly, it is possible
to design a model plant that can be used to represent the emissions and
control device requirements of typical new, modified, or reconstructed
sources covered in the NSPS.. This model, along with projectsions regarding
the population of new sources, would be used to determine the environmental,
energy, and cost impacts associated with several regulatory alternatives.
Air oxidation facilities, however, use 36 types of oxidation processes
(23 principal processes and 13 specialty processes) to manufacture 36
different organic chemicals. Because of the number and diversity of
facilities and processes in the air oxidation industry, a chemical-by-
chemical development of NSPS's would require large amounts of time,
effort, and money. The unit process approach, on the other hand, allows
development of an NSPS that provides for regulatory alternative development
for VOC emissions from all SOCMI air oxidation processes. This unit
process approach allows the resource-efficient statistical estimation of
the impacts associated with VOC emissions control from all air oxidation
processes under several regulatory alternatives.
In the unit process approach, no model plants are used for impact
analysis. Rather, the information concerning existing air oxidation
facilities is analyzed statistically and used to construct a national
profile. This national profile replaces the traditional model plant and
F-l
-------
can be considered a statistical model of new SOCMI air oxidation processes
and facilities. The national profile characterizes air oxidation processes
according to national distributions of key variables (e.g.,.. waste gas
stream flow, heating value, and VOC content) that can be used to determine
VOC emissions and the cost and energy impacts associated with the regulatory
alternatives. Each alternative is therefore recommended as a national
percent reduction in annual VOC emissions based on. thermal oxidation as
the single control technique. The regulatory alternative impacts are
evaluated as impacts upon the entire population of affected facilities.
F.2.1 National Statistical Profile Construction
The overall success of the statistical analysis depends on the
availability of an adequate sample size and dependable data. Thirty-six
chemicals are produced by air oxidation processes nationwide. The
results of the EPA Houdry Questionnaires contain data on 13 chemicals.
These data consist of emission and production factors for 59 chemical
plants, representing 36 percent of the total existing population and 120
percent of the projected new population for 1982-1987. These results,
along with the physical properties of the chemicals involved, form the
basis of the analysis. Table F-l lists the chemicals that are included
in the data base.
As noted, the data base for NSPS analysis has been derived from EPA
Houdry Questionnaires. The Houdry Division of Air Products and Chemicals,
Inc., conducted an extensive survey of the petrochemical industry to
provide data for EPA to use in their fulfillment of their obligations
under the terms of the Clean Air Amendments of 1970. The scope of that
study included most petrochemicals which fell into one or more of the
classifications of (1) large production, (2) high growth rate, and (3)
significant air pollution. The information sought included industry
descriptions, air emission control problems, sources of air emissions,
statistics on quantities and types of emissions, and descriptions of
emission control devices then in use. The principal source for that
data was the industry questionnaire current as of 1972. The data base
was updated in 1979.
F-2
-------
TABLE F-l. LIST OF CHEMICALS FOR WHICH DATA HAS BEEN OBTAINED
Ethylehe Oxide
Hydrogen Cyanide
Aceti c;Aci d
Acetaldehyde
Phthalic Anhydride
Dimethyl Terephthalate
Phenol
Ethylene Dichloride
Acrylonitrile
Cyclohexanone
Terephthalic Acid
Maleic Anhydride
Formaldehyde
F-3
-------
TABLE F-2. ACTUAL DATA .BASE USED TO CONSTRUCT NATIONAL STATISTICAL PROFILE
Company
Rohm & Haas
Badische
Badische
Nipro
Clark
Dow
Georgia Pacific
Monsanto
Shell
USS
DuPont
DuPont
Eastman
Amoco/Standard
Exxon
Monsanto
Stepan
Conoco
Diamond Shamrock
Dow
Ethyl
Goodri ch
ICI
Shell
Stauffer
Vul can
Dow
Locati on
Deer Park, TX
Freeport, TX
Freeport, TX
Augusta, GA
Blue Island, IL
Oyster Creek, TX
Plaquemine, LA
Choc. Bayou, TX
Deer Park, TX
Haverhill, OH
Wilmington, MC
Old Hickory, TN
Kings port, TN
Decatur, AL
Baton Rouge, LA
Texas City, TX
Millsdale, IL.
Covenant, LA
Deer Park, TX
Freeport, TX
Baton Rouge, LA
Calvert City, KY
Baton Rouge, LA
Deer Park, TX
Long Beach, CA
Grismar, LA
Freeport, TX
\
Process
Methane/Ammonia Oxidation
Cyclohexane Oxidation
Cyclohexane Oxidation
Cyclohexane Oxidation
Cumene Hydroperoxidation
Cumene Hydroperoxidation
Cumene Hydroperoxidation
Cumene Hydroperoxidation
Cumene Hydroperoxidation
Cumene Hydroperoxi dati on
DMT p-Xylene Oxidation
DMT p-Xylene Oxidation
TPA p-Xylene Oxidation
TPA p-Xylene Oxidation
o-Xylene Oxidation
o-Xylene Oxidation
o-Xylene Oxidation
Ethyl ene Oxychlorination
Ethyl ene Oxychlorination
Ethyl ene Oxychlorination
Ethyl ene Oxychlorination
Ethyl ene Oxychlorination
Ethyl ene Oxychlorination
Ethyl ene Oxychlorination
Ethyl ene Oxychlorination
Ethyl ene Oxychlorination
Ethyl ene Oxidation I
F-4
-------
TABLE F-2 (Continued). ACTUAL DATA BASE USED TO CONSTRUCT NATIONAL
STATISTICAL PROFILE
Company
Location
Process
Koch
UCC
PPG
Eastman
American Cyanamid
DuPont
Monsanto
Vistron
Denka
Monsanto
Koppers
Reichhold
Reichhold
Tenneco
USS
USS
UCC
Gulf
Reichhold
GAP
Reichhold
Borden
Celanese
DuPont
Georgia Pacific
Monsanto
Georgia Pacific
Orange, TX
Seadrift, TX
Beaumont, TX
Longview, TX
New Orleans, LA
Beaumont, TX
Alvin, TX
Lima, OH
Houston, TX
St. Louis, MO
Bridgeville, PA
Morris, IL
Elizabeth, NJ
Fords, NJ •
Neville Island, PA
Neville Island, PA
Charleston, WV
Vicksburg, MS
Houston, TX
Calvert City, KY
Moncure, NC
Fayetteville, NC
Bishop, TX
Belle, WV
Vienna, GA
Choc. Bayou, TX
Crossett, AR
Ethylene Oxidation I
Ethylene Oxidation I
Ethylene Oxidation I
Ethylene Oxidation II
Propylene Ammoxidation
Propylene Ammoxidation
Propylene Ammoxidation
Propylene Ammoxidation
Benzene Oxidation
Benzene Oxidation
Benzene Oxidation
Benzene Oxidation
Benzene Oxidation
Benzene Oxidation
Benzene Oxidation
Naphthalene Oxidation
Naphthalene Oxidation
Methanol Oxidation I
Methanol Oxidation I
Methanol Oxidation I
Methanol Oxidation I
Methanol Oxidation II
Methanol Oxidation II
Methanol Oxidation II
Methanol Oxidation II
Methanol Oxidation II
Methanol Oxidation II
F-5
-------
TABLE F-2 (Continued). ACTUAL DATA BASE USED TO CONSTRUCT NATIONAL
STATISTICAL PROFILE
Company
Locati on
Process
Hercules
Reichhold
Tenneco
Eastman
Wilmington, NC
Kansas City, KS
Garfield, NJ
Kingsport, TN
Methanol Oxidation II
Methanol Oxidation II
Methanol Oxidation II
Acetaldehyde Oxidation
F-6
-------
Table F-2 -shows the actual data base used to construct the national
statistical profile. Twenty-three different processes are represented
in the data set. Due to the wide variation in processes used and in the
types of control devices present across the air oxidation industry, only
uncontrolled emission factors and vent stream characteristics are included
in the data set. Since uncontrolled emissions are subject to the greatest
uncertainty because of the difficulty in defining what is a pollution
control device, all stream data represent the process stream exiting the
primary product recovery device. Figure F-l shows the reference point
for data collection within the air oxidation process. Since many air
oxidation facilities may have additional control equipment in place,
these data are overstated estimates of the current emission factors.
Table F-3 shows-the air oxidation offgas components specific to each
chemical represented in the data base VOC. Table F-4 shows the data
vectors contained in the national statistical profile. Tables F-5 and
F-6 show tabular representations of the vector distribution.
F.2.2 Data Reliability
From the Houdry data, two assumptions mus.t be made regarding the
Houdry data reliability for this NSPS analysis. First, the data contains
a bias toward large-volume chemicals or those chemicals with significant
air pollution. This is. not considered to be a serious drawback to the
NSPS analysis. Second, because the chemical industry as a whole is
dynamic, the age of the Houdry data presented a second source of bias.
In a study prepared for the Chemical Manufacturers Association (CMA),
the 1972 Houdry data (updated in 1979) was compared to a 1980 data base
developed from recent industry contacts. Twenty-two plants are represented
in both the CMA data base and the data base used for this NSPS analysis.
Hypothetical uncontrolled emission factors were calculated for each data
vector representing a plant for which data exists in both data bases.
Two sets of 22 emission factors each, one set for each data base, were
thereby obtained. These two sets were statistically compared using the
Wilcoxon signed-rank procedure. The results of the Wilcoxon signed-rank
procedure to test the significance of the differences between the overlapping
portions of the two data bases show that the differences are not significant
at the 0.05 level.
F-7
-------
r
I «
CO
CO
-------
TABLE F-3. AIR OXIDATION OFFGAS COMPONENTS
ACRYLONITRILE
CYCLOHEXANONE
Nitrogen
Oxygen
Carbon Dioxide
Carbon Monoxide
Water (vapor)
Ammonia*
Methane
Ethane
Ethylene
Propane
Propylene*
Acetaldehyde
Acetone (vapor)
Acrolein (propenal) (vapor)
Hydrogen Cyanide
Acrylonitrile (vapor)*
Acetonitrile (vapor)
HYDROGEN CYANIDE
"Air"
Hydrogen Cyanide*
Nitrogen
Carbon Monoxide
Cyclohexane (vapor)*
Cyclohexanol (vapor)
Cyclohexanone (vapor)*
"Unknown Organics (C2+)"
ACETALDEHYDE
Nitrogen
Oxygen
Carbon Dioxide
Carbon Monoxide
Water (vapor)
Hydrogen
Methane
Methyl Chloride
Ethyl Chloride
Ethanol (vapor)*
Acetic Acid (vapor)
Acetaldehyde (vapor)*
Argon
F-9
-------
TABLE F-3 (Continued). AIR OXIDATION OFFGAS COMPONENTS
ACETIC ACID
Nitrogen
Oxygen
Carbon Dioxide
Water (vapor)
Carbon Monoxide*
Argon
Hydrogen
Methane
Ethane
Butane*
"Cg* Hydrocarbons"
Methyl Iodide
Ethanol*
Acetaldehyde*
Methyl Acetate
Ethyl Acetate
ACETIC ANHYDRIDE
Ni trogen
Oxygen
Carbon Dioxide
Carbon Monoxide
Hydrogen
Methane
Ethane
Ethylene
Propane
Propadiene
Acetic Acid (vapor)*
Diketene (vapor) "(CH2=C=0)2"
Acetic Anhydride (vapor)*
MALEIC ANHYDRIDE
Nitrogen
Oxygen
Carbon Dioxide
Water (vapor)
Carbon Monoxide
Formaldehyde
Formic Acid (vapor)
Maleic Acid (vapor)
Maleic Anhydride (vapor*)
Benzene (vapor)*
Xylene (vapor)
"Other Organics (Est. Mol. Wt. 50)"
F-10
-------
TABLE F-3 (Continued). AIR OXIDATION OFFGAS COMPONENTS
PHTHALIC ANHYDRIDE
Nitrogen
Oxygen
Water (vapor)
Carbon Monoxide
Carbon Dioxide
Argon
Sulfur Dioxide*
Inorganic Salts (Magnesium and Calcium
Carbonates) (parti oil ate)
"Hydrocarbons"
Maleic Acid (vapor)
Maleie Anhydride (vapor)
Benzoic Acid (vapor)
Phthalic Anhydride*
1,2-Naphthoquinone.(particulate, vapor)
TEREPHTHALIC ACID & DIMETHYL TEREPHTHALATE
Ni trogen
Oxygen
Water (vapor)
Carbon Dioxide
Carbon Monoxide
Methane
Methanol*
Dimethyl Ether
Methyl Ethyl Ketone (vapor)*
Methyl Acetate (vapor)
Acetic Acid (vapor)*
Acetaldehyde*
p-Xylene (vapor)*
*Product or Feedstock
PHENOL
Nitrogen
Oxygen
Water (vapor)
Carbon Dioxide
Sodium Carbonate (particulate)
Formaldehyde
Acetaldehyde
Acetone (vapor)
Acetone (vapor)
Mesityl Oxide (4-Methyl-3-Penten-2-One)
(vapor)
Benzene (vapor)
Phenol (vapor)*
Cumene (vapor)*
Cumene Hydroperoxide.(vapor)
a-Methyl Styrene (vapor)
a,a-Dimethyl Benzyl Alcohol (2-Phenyl-
2-Propanol) (vapor)
Acetophenone
"Other Organics", "Oxidized Organics
(various)" (vapor)
ETHYLENE OXIDE
Nitrogen
Oxygen .
Carbon Dioxide
"Oxides of Nitrogen"
Argon
Methane
Ethane
Ethylene*
Ethylene Oxide*
"Particulate (Primarily Carbon, small
amounts of Iron, Chlorine)"
F-ll
-------
TABLE F-4.
Plant ID Number
1303
1305
1306
1307
1601
205
2301
2302
2303
2305
2308
5101
5102
5103
5104
102
1004
1007
2203
2204
2205
2206
2207
2208
902
903
904
1001
1005
1801
1802
1803
1804
1805
1806
1807
1403
1404
1407
1408
1409
1410
1411
1418
1416
1421
1423
1422
1420
1601
S202
5203
5204
5205
5206
5207
5208
5209
5201
DISTRIBUTION OF NATIONAL STATISTICAL PROFILE DATA VECTORS
Hourly Emissions (kg/hr)
326
666
115
2.12
55.0
75.0
117
203
617
340
219
1370
2150
095
1210
13.7
323
223
• 155
26.4
27.9
36.0
13.7
14.6
80.2
103
407
78.7
188
529
211
205
136
14.1
135
355
15.1
20.3
33.7
14.6
0.0250
15.8
357
0.0205
39.6
16.0
19.5
23.3
31.4
0.217
80.2
433
348
228
125
464
371
78.9
616
Net Heating Value (MJ/scm)
0.592
1.05
0.499
0.001
3.31
0.234
0.140
0.144
0.093
0.090
0.146
1.04
1.S9
0.728
0.676
0.009
0.269
0.154
0.217
0.062
0.065
0.087
0.065
0.109
0.440
0.433
1.52
0.366
0.143
0.391
0.336
0.387
0.450
0.205
0.335
0.753
2.63
2.45
2.63
2.54
2.75
2.53
2.84
2.39
0.106
0.138
0.137
0.299
2.57
1.71
0.752
1.99
2.65
2.00
0.722
0.769
0.769
0.769
4.25
Off gas Flowrate (scm/min)
461
529
194
3037
1631
152
790
1212
3552
2307
1320
1427
1373
1524
2092
365
1524
565
516
456
310
231
152
97
182
182
252
1642
979
2264
1341
1277
516
1309
912
607
24
73
61
76
33
173
547
27
175
118
118
100
61
197
182
121
216
647
143
304
242
52
289
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F.2.3 National Statistical Profile Use
The actual use of the national statistical profile assumes that the
distribution of offgas flow, VOC emission rate, and stream net heating
value is chemical independent.. Chemical identities are not considered
in the profile, nor is there claimed to be a one-to-one correspondence
between any one data vector and an existing offgas stream. It is
assumed, however, that the overall proportions and distributions of the
parameter values and data vectors are similar to those of the existing
population of air oxidation facilities. Thus, since the national
statistical profile contains 59 data vectors, each data vector and
associated impacts of population control represents 1/59 of the existing
population to be analyzed for control.
F.2.4 Calculation of Baseline Control Level
As mentioned earlier, the data base was constructed from uncontrolled
emission sources. However, some control is currently being applied to
the sources as required by current State implementation plans (SIP's) or
other regulations. Furthermore, modified SIP's are projected to be in
effect in ozone NAAQS nonattainment areas requesting extension. These
modified SIP's would reflect the level of control recommended in the
SOCMI air oxidation Control Techniques Guideline (CT6) document. In
order to modify the collection of data vectors to account for projected
baseline control, an analysis of the SIP requirements and an adjustment
of the profile is required.
A weighted average of current control requirements appears to
provide the closest approximation of current VOC control levels. The
baseline analysis assumes that the statistical profile of data vectors
adequately represents the population of existing air oxidation processes
within each State. An annual emissions value was calculated for each
data vector from its hourly emissions value. These values were summed
to give a total annual emissions value for the profile. Each data
vector was analyzed in order to estimate whether a plant with such
offgas characteristics would be required to reduce VOC emissions by a
given SIP. For each data vector determined to be subject to SIP control,
the annual emission reduction under SIP was calculated. The total
annual emission reduction associated with the given SIP was calculated
F-15
-------
as the sum of these individual vector values. This emission reduction
value was divided by the total emissions value for the profile. The
result was an estimated percent reduction of emissions for a given State
or for the group, of nonattainment areas. The national baseline was then
calculated as a weighted average of the baselines for each State and for
the nonattainment areas as a separate group. In calculating the national
weighted average, each individual State baseline control value was
weighted by the percent of all new source VOC emissions projected to
come from the given State. These emission percentages were estimated in
the following way: for each new facility projected to be built in a
given State, the projected plant capacity was multiplied by the estimated
1 2
average emission factor for the given process. The resulting plant
emissions, estimates were summed according to State, and percentages
calculated for each State to give the weighting factors. The nonattainment
areas requesting extension were taken as a unit, were treated in the
same manner. Analysis shows that the estimated baseline control level
attributable to the SIP's is 72 percent. Consequently, a 72 percent VOC
reduction from the uncontrolled level is used as the baseline level for
3
analysis of the regulatory alternative impacts.
F.3 FLOW PREDICTION
Because information on offgas flowrates was unavailable for some
small-volume air oxidation chemicals, a method for estimation of offgas
flowrate has been developed. Offgas flowrate is the major determinant
of thermal oxidizer size and capital cost.
Operation of a thermal oxidizer is less dependent on many process
and waste stream considerations than other control devices and, consequently,
is the only demonstrated VOC control technology universally applicable
to SOCMI air oxidation processes. Furthermore, thermal oxidation can
•achieve a high level of VOC control and requires only a limited amount
of vent stream data (i.e., corrosion propertieis, emission rate, flow,
and heat content) to determine incinerator costs and associated emission
reduction.
The main factor for capital cost evaluation of a thermal oxidizer
is the total offgas flpwrate. Since the total offgas flowrate is not an
easily obtainable parameter, a statistical estimation procedure has been
developed.
F-16
-------
As described in Chapter 3 of this document, the only determinant
for classification as an air oxidation chemical is the process by which
the chemical is manufactured. Despite the large variation in reaction
types used to produce air oxidation chemicals, all air oxidation processes
have one characteristic in common: the requirement that oxygen from the
air be mixed with certain organic compounds. As a result, large quantities
of inerts, mainly nitrogen and unreacted oxygen, must be vented from the
process. This stream flowrate determines the thermal oxidizer size and
cost. Thus, the amount of air introduced into the reaction system
determines to a large extent the capital cost of thermal oxidation.
There are several reaction characteristics that determine the amount of
offgas vented to the atmopshere, including:
1. Reaction stoichiometry,
2. Reaction phase, and
3. Explosion hazard.
A theoretical discussion of the contribution of each of these
factors to the excess air requirements is contained in Chapter 3.
The effect of reaction stoichiometry on offgas flowrate can be
calculated for each air oxidation process based on available data regarding
the overall, balanced production reaction. If an accurate overall
reaction is developed which includes all significant side reactions, a
"stoichiometric flowrate" can be calculated. This stoichiometric flowrate
is the flowrate. necessary to provide the exact amount of oxygen required
to give the annual production. Therefore, a ratio of actual flowrate to
stoichiometric flowrate (flow ratio) can be defined as a measure of the
amount of excess air used.
In order to quantify the effects of reaction phase and explosion
hazard on the flow ratio, multiple linear regression techniques were
employed.
Because explosion hazards are very different for liquid-phase
reactions than for vapor-phase reactions, the statistical profile was
divided in two according to reaction phase. Actual values of the flow
ratio were calculated for each data vector. For liquid-phase 'data
vectors, multiple linear regression showed no correlation between flow
ratio and parameters related to explosion hazard. However, a clearly
defined ceiling value of three was observed for the actual flow ratios.
F-17
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The composite parameters considered in the vapor-phase regression
analysis were all functions of four explosion hazard-related offgas !
parameters. These were reaction temperature, global heat of reaction •
explosive limit of the most expensive component, and autoignition j
temperature of the most explosive component. Ten composite parameters!
were constructed. Eight model equations were developed, each of which
contained from one to five of the composite parameters. A comparison of
the linear regression results for these eight equations is given in
Table F-7.
Equation 8 was chosen as the best flow ratio predictor on the basis
of its high model F-statistic value and coefficient of determination R2
value). Each of the four parameters in the chosen equation were significant
at the 0.0001 level. The chosen equation is:
FLOW RATIO = -4.98 (TR/TI) -7.04 (1/EL) + 17.2 (TR/TI) - (1/EL) + 1.13
where:
TR
TI
EL
reaction temperature (°C).
autoignition temperature (°C).
explosive limit (volume percent)
(EL),
Some summary statistics of the chosen equation are given in Table F-8.
A comparison of actual and predicted flow ratios is given in Table F-9.
F-19
-------
TABLE F-8. SUMMARY STATISTICS OF THE CHOSEN F PREDICTOR EQUATION
Parameter
Estimate
Standard Error;
of Estimate i
Significance
Probability
TR/TI
1/EL
(TR/TD-0/EL)
EL
Model F Value
Coefficient of Determination
Coefficient of Variation
Significance Probability of
-4.98
-7.04
17.2
1.13
= 896
(R2) = 0,989
= 15.8
Model = 0.0001
0.31 I
0.47 :
0.63
0.09 !
:
:
0.0001
0.0001
0.0001 .
0.0001
Key:
EL = Lower explosive limit.
TR = Reaction temperature (°C).
TI = Autoignition temperature (°C).
F-20
-------
TABLE F-9. EFFECTIVENESS OF THE
F3 PREDICTOR
OBS
1
2
3
4
5
6
7
8
9
10
n
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
Actual
1.65
0.75
1.55
1.92
1.19
2.81
12.7
12.0
12.7
3.38
1.30
0.98
1.83
2.04
1.58
0.98
0.91
0.95
1.19
1.99
2.26
2.51
2.74
2.40
2.96
3.56
2.88
3.31
2.99
2.96
2.77
2.28
2.00
1.30
1.57
1.55
2.09
2.29
1.93
1.87
1.87
1.58
1.91
Predicted
1.29
1.29
1.29
1.29
1.24
3.28
12.4
12.4
12.4
3.28
1.28
1.28
1.28
1.28
1.28
1.28
1.28
1.28
1.28
2.16
2.16
2.16
2.16
3.05
3.05
3.05
3.05
3.05
3.05
3.05
1.64
1.64
1.64
1.64
1.64
1.64
1.64
1.64
2.16
2.16
2.16
2.16
1.60
Relative Error
0.27
0.42
0.20
0.49
0.04
0.15
0.02
0.04
0.02
0.03
0.01
0.24
0.43
0.60
0.24
0.24
0.29
0.25
0.07
0.08
0.05
0.16
0.27
0.21
0.03
0.17
0.06
0.09
0.02
0.03
0.53
0.40
0.22
0.20
0.04
0.05
0.27
0.40
0.11
0.13
0.13
0.27
0.33
MEAN: 0.19
MEDIAN: 0.16
Upper 90%
Confidence Limit
2.02
2.02
2.02
2.02
1.98
4.07
13.2
13.2
13.2
4.07
2.00
2.00
2.00
2.00
2.00
2.00
2.00
2.00
2.00
2.87
2.87
2.87
2.87
3.78
3.78
3.78
3.78
3.78
3.78
3.78
2.37
2.37
2.37
2.37
2.37
2.37
2.37
2.37
2.90
2.90
2.90
2.90
2.42
F-21
-------
F.4 REFERENCES FOR APPENDIX F
1. Darby, W.P. et. al., Regulation of Air Oxidation Processes Within
the Synthetic Organic Chemical Manufacturing Industry: Background
Information and Analysis. St. Louis, Washington University, 1981.
Appendix A.
2. Control of Volatile Organic Compound Emissions from Air Oxidation
Processes in Synthetic Organic Chemical Manufacturing Industry.
Draft Control Techniques Guideline Document. July 1981. Appendix D.
3. Memo from Galloway, J., EEA, to SOCMI Air Oxidation File. July 29, 1981
F-22
-------
APPENDIX G:
COST ANALYSIS SPECIAL TOPICS
-------
-------
APPENDIX G: COST ANALYSIS SPECIAL TOPICS
G.I INTRODUCTION1'2
The purchase cost estimates for individual pieces of control equipment
are discussed in this appendix in relation to the raw vendor data on which
the estimates are based. Independent vendor estimates are also compared
with the purchase costs. The method of estimating installed costs from
component installation factors is discussed. Graphs of the installed costs
for several types of control equipment, as a function of flowrate, are
presented. Graphs are also presented for total installed capital costs for
the control systems, and the derivations of capital cost equations from
these graphs are discussed. Details of the chemical process-specific
costing methodology are given.
G.2 CONTROL EQUIPMENT PURCHASE COSTS
G.2.1 Thermal Oxidizer
EEA obtained data from the three vendors which provided combustion
chamber cost data to Enviroscience. The three sets of vendor quotations
agreed with each other well. The Enviroscience purchase cost curve repre-
sents a conservative "envelope" that is higher than the vendor data for all
equipment sizes.
Vendor A quoted costs for four equipment sizes for each of six different
incineration temperatures. Vendor B quoted costs for 14 equipment sizes
for each of four different temperatures. Vendor C quoted costs for six
equipment sizes for each of two different temperatures. These data constitute
an abundance of observations for derivation of reasonably accurate equations
for the relation of capital cost to offgas flowrate.
EEA independently obtained data from two additional vendors. Each of
these quoted costs for two equipment sizes at one temperature. Their
quotations essentially agreed with those of the vendors contacted by
Enviroscience.
G.2.2 Recuperative Heat Exchanger
EEA obtained data from the two vendors which provided heat exchanger
costs to Enviroscience. The two sets of vendor quotations agreed with each
other well. The Enviroscience purchase cost curve represents an average
that is roughly equivalent to the vendor curves.
G-l
-------
Vendor A quoted costs for four offgas flowrates for each of two levels
of heat recovery. Vendor C quoted costs for three offgas flowrates for each
of two levels of heat recovery. Because heat exchanger costs were quoted as
functions of heat exchange surface area, these data actually represent eight
and six different equipment sizes, respectively. These data constitute an
adequate number of observations for derivation of reasonably accurate
equations for the relation of capital cost to offgas flowrate.
EEA independently obtained data, from two additional vendors. One
quoted costs for two offgas flowrates. The other quoted costs for two
offgas flowrates for each of two temperatures. Their quotations essentially
agreed with those of the vendors contacted by Enviroscience.
G.2.3 Waste Heat Boiler
EEA obtained data from one vendor which provided waste heat boiler
costs to Enviroscience. The Enviroscience purchase cost curve represents
this data well.
The vendor quoted costs for 10 offgas flowrates for each of three
different temperatures. These data actually represent 30 different equip-
ment sizes, and therefore constitute an abundance of observations for
derivation of reasonably accurate equations for the relation of capital cost
to offgas flowrate.
G.2.4 Fans
One vendor quoted costs for 13 sizes of fans. These data constitute an
abundant number of observations for derivation of reasonably accurate
capital cost equations.
G.2.5 Stack
One vendor quoted costs for four sizes of stacks. While these data
constitute a minimal number of observations for accurate interpolation
between given stack sizes, the relatively low cost of stacks compared to the
rest of the control system makes extra accuracy unnecessary.
G.2.6 Ducts
Enviroscience used EPA 450/5-80-002 (The "GARD" Manual) as its source
for duct costs.
6-2
-------
6.3 INSTALLATION FACTORS
The Env.iroscience method of estimating installed costs of combustion
chamber, recuperative heat exchanger, and waste heat boiler from the ori-
ginal vendor cost quotations is discussed below and summarized'in Table G-l.
The component purchase costs represent interpolations of vendor quotations
and are graphed as continuous functions of offgas flowrate. A factor of
20 percent for "unspecified equipment" was added to the budget prices of the
combustion chamber and waste heat boiler. This factor was omitted for the
heat exchanger. Factors were then added for 10 aspects of installation,
such as insulation and.piping. These factors were expressed as percentages
of the budget price of the equipment in question. The overall sum of these
factors plus the factor of one for the original equipment and, in two cases,
the factor of 0.2 for unspecified equipment was multiplied by a factor of
1.35, which represented the impact of contingencies, fees, site development,
and vendor assistance. Because the original costs seemed low, several cases
were vigorously recosted. It was decided by Enviroscience that the overall
installation factor would be multiplied by 1.33 to achieve a better esti-
mate. However, Enviroscience assumed that this factor of 1.33 was due
entirely to underestimates of the factors for the 10 aspects of installa-
tion. An alternative correction factor was therefore calculated which, when
multiplied by the sum of the 10 installation component factors, would
result.in the values of the same overall installation factor as given by the
1.33 estimate. The values of this correction factor were 1.7 for the
combustion chamber, 2.1 for the heat exchanger, and 1.9 for the boiler. The
values of the final, overall new source installation factor were 4.0, 2.5, and
3.5 for the combustion chamber, heat exchanger, and waste heat boiler, '
respectively.
In order to estimate total installed capital costs in the case of
modified or reconstructed facilities, retrofit installation factors were
then developed from the new source factors. Because cramped plant condi-
tions will make a longer time of installation necessary, the installation
labor cost will increase. For each of the nine aspects of installation
other than engineering, freight, and taxes, it is assumed that 50 percent of
the component installation factor represents labor costs. These labor costs
were assumed to double in each case. Therefore,, each of the nine component
6-3
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factors was assumed to increase by 50 percent due to labor. Added expense
was expected for four of the factors: structures, piping, erection, and
electrical. Such expense might be due to a steel or concrete deck for the
equipment, extra circuit breakers, and about 500 feet of extra ducting.
The factors for erection, piping, and electrical, after inclusion of the
labor increase, were doubled. The factor for structures for the combustion
chamber and heat exchanger was assumed to increase to 10 percent. The
overall retrofit installation factors, calculated as above, for the combustion
chamber, heat exchanger, and boiler were 6.5, 3.5, and 5.3, respectively.
In order that the Enviroscience total installed cost curves could be
used directly, one overall retrofit-to-new source correction factor was
developed. The individual correction factors for the combustion chamber,
heat exchanger, and boiler were 1.625, 1.4, and 1.514, respectively. In
order to give a conservative estimate of total installed costs, the value
of 1.625 was used for the retrofit-to-new source correction factor.
6.4 INDIVIDUAL COMPONENT INSTALLED COSTS
Installed capital costs for a thermal oxidizer designed for a
870°C (1600°F) combustion temperature and 0.75 second residence time are
given in Figure 6-1- Recuperative heat exchanger installed capital costs
are given in Figure 6-2. Installed capital costs for inlet ducts, fans, and
stack, for systems with and without heat recovery, are given in
Figure 6-3 and 6-4, respectively. The above equipment unite constitute the
components of a control system for nonchlorinated vent streams.
Figures 6-5 and 6-6 give the installed capital costs fqr a thermal
oxidizer at 1200°C (2200°F) and 0.75 second residence time and for a waste
heat boiler, respectively. The installed capital costs of a scrubber
including quench chamber are given in Figure 6-7. Figure 6-8 gives installed
capital costs for ducts, fans, and stack for a system employing a waste heat
boiler. I
6.5 TOTAL CONTROL SYSTEM INSTALLED CAPITAL COSTS j
Total installed capital costs of a thermal oxidation system for control
of nonchlorinated vent streams are given in Figure 6-9. Thp design condi-
tions are 870°C (1600°F) and a 0.75 second residence time, jFigure 6-10 gives
the total installed capital costs of a thermal oxidation system for control
of chlorinated vent streams at 1200°C (2200°F). These conditions were
6-5
-------
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DUCTS, FANS, AND STACK INSTALLED CAPITAL
No Heat Recovery
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2. 1OO Blu/scf, 0.5 or 0.75 sec., 1875 °F
3. 200 Btu/scf, 0.5 or 0.75 sec., 2200 °F
0.5 1.0 5.0 10.O
WASTE GAS FLOW (1,000 SCFM)
50.0
100.0
Figure G-3. Installed capital costs for inlet ducts, waste gas, and combustion
air fans and stack for system with no heat recovery.
6-8
-------
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Recuperative Heat Recovery
10B»u/scf 0.5 or 0.75 sec., 1400°F 8 1600 °F
10
1. 30% Recup. Heat Recovery
2. 50% Recup. Heat Recovery
3. 70% Recup. Heat Recovery
5.0 1O.O
WASTE GAS FLOW (1,000 SCFM)
50.0
100.0
Figure G.-4. Installed capital costs for inlet ducts, waste gas, and combustion
air fans and stack for system with no heat recovery.
G-9
-------
10,000
o
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Combustion Temperatures
a- 1800°F In 1/2-sec residence time
b-180O°F in 3/4-sec residence time
c- 2200°F In 1/2-sec residence time
residence time
d - 2200°F in
- sec
1.O
100
Waste-Gas Flow (lOOO scfm)
Figure Q-5. Installed capital cost of thermal oxidizer at 1800 and 2200 F
; including incinerator, two blowers, ducts, and stack.
6-10
-------
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WASTE HEAT BOILERS (250 PSD INSTALLED CAPITAL
1. 10 Btu/scf, 0.5 or 0.75 sec., 1400 °F
2. 10 Btu/scf, 0.5 or 0.75 sec., 1600 °F
3. 100 Btu/scf, 0.5 or 0.75 sec., 1875 °F
4. 200 Btu/scf, 0.5 or 0.75 sec., 2200 °F
i i i
0.5 1.0 5.0 10.0 50.0 100.0
WASTE GAS FLOW (1,000 SCFM)
Figure G-6. Installed capital cost for waste heat boiles (250 psi).
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6-12
-------
1000
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o
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DUCTS, FANS, AND STACK INSTALLED CAPITAL
Waste Heat Boilers
1. '10 Btu/scf, 0.5 or 0.75 sec., 1400°F a 1600°F
100 Btu/scf, 0.5 or 0,75 sec., 1875°F
2.
3. 200 Blu/scf, 0.5 or 0.75 sec., 2200
1.0
5.0 10.0
WASTE GAS FLOW (1,000 SCFM)
50.0
100.0
Figure G-8. Installed capital for inlet ducts, waste gas, and combustion
air fans and stack with waste heat boilers.
G-13
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Figure G-10. Total installed capital cost for thermal oxidation systems with a
scrubber at a residence time of 0.5 sec, a combustion temperature
at 2200 F, and a waste gas heat content of 1 Btu/scf.
6-15
-------
corrected to 1090°C (2000°F) and a one second residence time. The combustion
chamber volume correction factor of 1.14 represents the product of a temperature
correction, combustion air flowrate correction, and residence time correction.
The development of the total installed capital cost equations for each
design from the Enviroscience cost curves is discussed in Reference 3.
G.6 CHEMICAL PROCESS-SPECIFIC COSTS
As discussed in Chapter 8, costs for each specific chemical manufacturing
process were developed for use in the economic analysis presented in
Chapter 9. Capital, annualized, operating, and control costs (cents per kg
of product) were projected for each chemical process. This section presents
details of the costing methodology and the process-specific parameters,
which are given in Table G-2.
Several of these processes, as discussed in Chapter 8, produce
by-products and/or co-products. A single value of capital cost, annualized
cost, and operating cost was projected for such processes. In calculating
the control costs (cents per kg of product) for by-products and co-products,
the total annualized cost for the process was attributed to each
by-product/co-product. Likewise, the total production of all by-products
and co-products was used in calculating the control cost of each
by-product/co-product. Therefore, the control costs of the
by-product(s)/co-product(s) are equal. This method of projecting contol
costs is equivalent to sharing the total annualized cost of the process by
weight of product.
The method of calculating chemical process-specific costs differed
from the methods used in Chapter 8 in several respects. For those processes
employing a vapor-phase air oxidation reaction (discussed in Chapter 3),
offgas flowrates were predicted according to the method discussed in
Appendix F. An after-tax discount rate of 8.5 percent was used. The
actual offgas oxygen concentrations were considered in estimating offgas
flowrates and capital costs. Chemical processes with offgas net heating
values that fall in Categories D and E were assumed to have a heat recovery
credit due to use of a waste heat boiler. No diluttion of offgas was
assumed for processes with heating values within the Category E range. For
processes with heating values within the range of Category C, offgas
dilution sufficient to permit use of 70 percent recuperative heat recovery
6-16
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was assumed, if such dilution would result in lower projected annualized
costs. Such processes were assumed to employ an offgas dilution sufficient
to yield a net heating value of 0.48. MJ/scm and place the process within
design Category B. Such a dilution was assumed for acrylonitrile (propylene
ammoxidation process) and its by-products.
The ratios of actual flowrate to stoichiometric flowrate (F values)
for vapor-phase processes were calculated according to the following
equation, which was statistically developed in Appendix F:
F = -4.98 (TR/TI) -7.04 (1/EL) + 17.2 (TR/TI) • (1/EL) + 1.13 (EL)
Where:
TR = reaction temperature (°C).
TI = autoignition temperature (°C) of most explosive organic compound
present.
EL = lower explosive limit (volume percent) of most explosive organic
compound present.
For liquid-phase processes, an F value of three was assumed, except
for acetic acid (butane oxidation) and dimethyl terephthalate/terephthalic
acid, where the actual F values were known to be lower.4
Flowrates were predicted from the F values and process parameters
according to the following equation:
Flow = 203.5 • Capacity • MOR • F
Where:
Flow = offgas flowrate (scm/min).
Capacity = plant capacity (thousand Mg/yr)
MOR = molar oxygen to product ratio for the global air oxidation
reaction.
F = ratio of actual flowrate to stoichiometric flowrate.
MW = product molecular weight.
The 203.5 conversion factor has the units (scm/g-mole) (yr/MM min).
For those processes with by-products, the plant capacity is a total capacity
for all products The molar oxygen ratios for such processes represent
G-19
-------
moles of oxygen per total moles of all products, according to the balanced
global reaction. The product molecular weight given in Table G-2 for such
processes is an average of by-product/co-product molecular weights. This
average is weighted according to the number of moles of each
by-product/co-product produced in the global reaction.
In order to yield conservative (higher) estimates of the control costs
(cents per kg product) the typical plant capacity chosen for each process
was the smallest known to exist. Use of the smallest plant capacity yields
a higher estimate of control cost because control equipment capital cost
does not decrease in a linear manner as flowrate decreases, due to certain
fixed capital costs. Since the estimated flowrates are proportional to
plant capacity, capital costs do not decrease in a linear manner as plant
capacity decreases. However, plant production is proportional to plant
capacity, and control cost is inversely related to plant production.
Therefore, control cost increases slightly as plant capacity decreases.
Several processes contain oxygen in the offgas, and the estimated
F values were decreased according to the following equation:
F (Corrected) = F • (1-4.76 • Volume Percent 02 * Flue-gas to Offgas Ratio)
where the flue-gas to offgas ratios are given in Chapter 8, Table 8-8. The
oxygen contents for the chemical processes are given in Reference 6. The
purpose of this flowrate correction is to decrease the estimated flue-gas
flowrate, because of a lower combustion air requirement. As a result,
supplementary fuel requirements, heat recovery credits, control equipment
sizes, and capital costs will be lower.
The F values of several processes were adjusted further, as a result
of rigorous process-specific heat and mass balance calculations, which
indicated lower combustion air requirements.
6-20
-------
G.7 REFERENCES FOR APPENDIX G
1. Basdekis, H.S. Emissions Control Options for the Synthetic Organic
Chemicals Manufacturing Industry. Control Device Evaluation.
Thermal Oxidation Supplement (VOC Containing Halogens or Sulfur).
EPA Contract No. 68-02-2577, November 1980. p. 111-11.
2. Blackburn, J.W. Emissions Control Options for the Synthetic
Organic Chemicals Manufacturing Industry. Air Oxidation Generic
Standard Support. EPA Contract No. 68-02-2577. May 1979.
p. III-3. .
3. Memo from Galloway, J., EEA, to SOCMI Air Oxidation File.
April 17, 1981.
4. Memo from Galloway, J., EEA, to SOCMI Air Oxidation File.
February 13, 1981.
5. Ibid.
6. Ibid.
7. Ibid.
G-21
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1, REPORT NO.
EPA-450/3-82-001a
3. RECIPIENT'S ACCESSION NO.
, TITTLE AND SUBTITLE
Air Oxidation Processes in Synthetic Organic Chemical
Manufacturing Industry - Background Information
for Proposed Standards
5. REPORT DATE
October 1983
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
8. PERFORMING ORGANIZATION REPORT NO
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Office of Air Quality Planning and Standards
Environmental Protection Agency
Research Triangle Park, North Carolina 27711
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
DU-78-C132
12. SPONSORING AGENCY NAME AND ADDRESS
DDA for Air Quality Planning and Standards
Office of Air, Noise, and Radiation
U.S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
13. TYPE OF REPORT AND PERIOD COVERED
Interim Final
14. SPONSORING AGENCY CODE
EPA/200/04
15. SUPPLEMENTARY NOTES
Standards of Performance for the control of emissions from air oxidation processes
in the synthetic organic chemical manufacturing industry are being proposed under
the authority of Section 111 of the Clean Air Act. These standards would apply to
new, modified, and reconstructed air oxidation facilities. This document contains
background information and environmental.and economic impact assessments of the
regulatory alternatives considered in developing proposed standards.
7.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTlFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
Air pollution
Pollution control
Standards of performance
Air oxidation processes
Volatile organic compounds
Synthetic Organic Chemical Manufacturing
Industry
Air pollution control
13B
S. DISTRIBUTION STATEMENT
Unlimited
19. SECURITY CLASS (TinsReport}
Unclassified
20. SECURITY CLASS (This page/
Unclassified
21. NO. OF PAGES
547
22. PRICE
EPA Form 2220-1 (Rev. 4-77) PREVIOUS EDITION is OBSOLETE
------- |