oEPA
United States
Environmental Protection
Agency
Air Pollution Training Institute
MD20
Environmental Research Center
Research Triangle Park NC 27711
Air
APTI
Course 482
Sources and Control
of Volatile Organic
Air Pollutants
EPA 450/2-81-011
March 1981
Student Workbook
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United States
Environmental Protection
Agency
Air Pollution Training institute
MD20
Environmental Research Center
Research Triangle Park NC 27711
EPA 450/2-81-011
March 1981
Air
APTI
Course 482
Sources and Control
of Volatile Organic
Air Pollutants
Student Workbook
Technical Content By:
J.A. Jahnke, PhD.
D.S. Beachler
J.T. Joseph
J.E. Maroney
Northrop Services, Inc.
P.O. Box 12313
Research Triangle Park. !\!C 27709
Under EPA Contract No.
68-02-2374
EPA Project Officer
R.E. Townsend
United States Environmental Protect'on Agency
Manpower and Technical Infoimation Branch
Office of Air Quality Planning and Standards
Research Triangle ParK, NC 27711
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Notice
This is not an official policy and standards document. The opinions and selections are
those of the authors and not necessarily those of the Environmental Protection
Agency. Every attempt has been made to represent the present state of the art as well
as subject areas still under evaluation. Any mention of products or organizations does
not constitute endorsement by the United States Environmental Protection Agency.
Availability
This document is issued by the Manpower and Technical Information Branch, Con-
trol Programs Development Division, Office of Air Quality Planning and Standards,
USEPA. It was developed for use in training courses presented by the EPA Air Pollu-
tion Training Institute and oth r Deceiving contractual or grant support from the
Institute. Other organizations are welcome to use the document.
This publication is available, free of charge, to schools or governmental ail pollution
control agencies intending to conduct a training course on the subject covered. Submit
a written request to the Air Pollution Training Institute. USEPA, MD-?0, Research
Triangle Park, NC 27711.
Others may obtain copies, for a fee, from the National Technical Information Service
(NTIS), 5825 Port Royal Road, Springfield, VA 22161.
Sets of slides and films designed for use in the training course of which this publication
is a part may be borrowed from the Air Pollution Training Institute upon written
request. The slides may be freely copied. Some films may be copied; others must be
purchased from the commercial distributor.
it
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Course Description
This course is designed for engineers and other technical personnel who are respon-
sible for the development and implementation of programs dealing with the control
of organic air pollutants. The course emphasis is focused on the source categories
contributing major amounts of volatile organic pollutants into the atmosphere.
Details of process operation and methods of controlling these emissions through
process, or design changes such as alternate uses of materials, will be discussed.
The specific application of techniques such as scrubbing, condensation and
incineration, used to control organic emissions, will also be reviewed. The relation-
ship between organic materials and the problem of photochemical oxidants will be
discussed with regard to regulatory programs. The development of emission inven-
tories for sources of organic air pollutants and examples of control plans developed
for inclusion in State Implementation Plans will be examined within the context of
the other subject matter of the course.
EPA technical guidance documents for the control of VOC emissions from
specific source categories will be discussed. Approximately one-third of the course
will deal with the regulatory problems of emission inventories, measurement, and
surveillance. One-third of the course will concern the description of VOC problems
associated with source categories addressed in the EPA technical guidance
documents for VOC control. The remaining third of the course will address control
methods for VOCs through the application of design or process changes or the use
of control equipment.
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How to Use This Workbook
This workbook is to be used during the course offering. It contains a chapter cor
responding to each of the eighteen lessons and a chapter containing two problem
sets.
Each chapier contains a listing of the lesson goal, the lesson objectives, and any
special references that might be helpful to you. Each chapter also contains several
pages of black-and-white line-art reproductions of selected lecture slides. These
reproductions are intended to generally follow the slide presentations ^iven in the
lecture. However, the instructor may on occasion change the order or present new
material not included in the workbook. It is therefore recommended that the stu
dent take notes throughout the course and not rely on the graphic reproductions as
representing the total course cc.ui.~-nt.
Space is provided for note-taking in each chapter of the workbook.
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Table of Contents
Page
Chapter 1
Introduction
Course Objectives and Overview 1-1
Chapter 2
Regulatory Review 2-1
Chapter 3
Organic Chemistry Review 3-1
Chapter 4
VOC Emission Measuring Techniques 4-1
Chapter 5
VOC Emissions from Industrial Surface Coating Operations 5-1
Chapter 6
VOC Emissions from Coil Coating Operations 6-1
Chapter 7
VOCs and Photochemical Oxidants 7-1
Chapter 8
VOC Emissions from Degreasing Operations 8-1
Chapter 9
VOC Emissions from Petroleum Refineries 9-1
Chapter 10
Operation-Maintenance-Inspection—Petroleum Refinery Leaks 10-1
Chapter 11
VOC Emissions from Storage of Petroleum Products 11-1
Chapter 12
VOC Emissions from Gasoline Marketing Operations 12-1
Chapter 13
The Regulatory Approach to VOC Control — I 13-1
Chapter 14
Liquid Asphalt 14-1
Chapter 15
The Regulatory Approach to VOC Control —II 15-1
Chapter 16
Methods of VOC Emission Control— Incineration 16-1
Chapter 17
Methods of VOC Emission Control — Adsorption 17-1
Chapter 18
The State VOC Control Program —an Example 18-1
Chapter 19
Homework Problems 19-1
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Chapter 1
Introduction
The goal of this course is to provide you with the necessary background needed to
develop, implement and enforce the federal, state, and local volatile organic emis-
sion control programs. You will learn about organic emissions problems of the
major sources of such air pollutants and the common methods used to control these
emissions from each source category. Associated topics such as emission inventories,
emission estimation and measurement methods, and inspection programs are also
included to provide a thorough ground in the topic of organic emissions control.
Course Objectives
Upon completion of this course, you should be able to:
• Identify by name the symbols and acronyms commonly used when describing
VOC emissions and the control of such emissions from stationary sources.
• Describe the relationships between volatile organic air pollutants and the
photochemical air pollution problem.
• Identify the various regulatory requirements dealing with sources of organic air
pollutants; describe the methods of preparing emission inventories and the types
of volatile organic emission control regulations developed for inclusion in the
SIPs.
• List and describe the common methods used to estimate and measure volatile
organic emissions, including methods of material balance, loss estimation, sam-
ple collection, and analysis by chromatography and spectroscopy.
• Sketch flow diagrams which illustrate the working principles of typical control
systems used for reducing the emission of volatile organic air pollutants. You
should be able to give examples of the application of such devices as adsorbers,
incinerators, and condensers.
• Describe the common methods of material and process modification used to
reduce organic emissions for each of the major source categories discussed in the
course.
1-1
-------
Identify the types of organic emissions and emission points for each of the source
categories listed below.
— petroleum refining
— petroleum storage, transportation, and marketing
— degreasing operations
— cutback asphalt processes
— industrial surface coating operations
Describe the inspection procedures which can be used for checking a VOC
emission source.
Describe key aspects of equipment appearance and process operations which
should be observed in order to determine that organic emissions are being
properly controlled, including evaluation of data from processes and emission
monitoring instrumentation.
Explain the use of EPA's control technique guidelines in the development and
implementation of a State V oo control strategy.
1-2
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Chapter 2
Regulatory Review
Lesson Goal: To provide a technical and regulatory vocabulary which
will enable you to understand the detailed course material
to be presented in subsequent lectures.
Lesson Objectives: Upon completion of this lesson, you should be able to:
• Identify all of the following acronyms: AQCR, SIP,
CTG, VOC, RFP, RACT, BACT, LAER, I/M, PSD,
NSPS, OAQPS, ESED, O/M, NSR, RM, TGNMO.
• Explain how states are required to include VOC control
plans in their SIPs for nonattainment AQCRs.
• Describe the role of CTGs in the development of SIPs.
• Define RACT
• Explain how EPA concepts such as BACT, RACT,
PSD, etc., apply to new and existing sources in attain-
ment and nonattainment areas.
• Locate information on VOC control.
• Explain how State air pollution agencies can use EPA
Control Technique Guideline Documents in the
development of State VOC programs.
References: Environmental Protection Agency (EPA). 1980. Office of
Air Quality Planning and Standards (OAQPS). Guidance
for the Control of Volatile Organic Compounds Emitted
by 10 Selected Source Categories.
Environmental Protection Agency (EPA). 1978. Summary
of Group 1 Control Technique Guideline Documents for
Control of Volatile Organic Emissions from Existing Sta-
tionary Sources. EPA-450/3-78-120.
Environmental Protection Agency (EPA). 1978.
Regulatory Guidance for Control of VOC Emissions from
15 categories of Stationary Sources. EPA-905/2-78-001.
Environmental Protection Agency (EPA). 1979. Summary
of Group II Control Technique Guideline Documents for
Control of Volatile Organic Emissions from Existing Sta-
tionary Sources. EPA-450/2-80-001.
2-1
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Environmental Protection Agency (EPA). 1979. 44 Fed.
Reg. 53761 (September 17, 1979). State Implementation
Plans: General Preamble for Proposed Rulemaking on
Approval of Plan Revisions for Nonattainment
Areas—Supplement on Control Technique Guidelines.
Environmental Protection Agency (EPA). 1979. Guidance
for Lowest Achievable Emission Rate from 18 Major
Stationary Sources of Particulate, Nitrogen Oxides, Sulfur
Dioxide, or Volatile Organic Compounds.
EPA-450/3-79-024.
The Clean Air Act (as Amended August 1977). Serial No.
95-11. November 1977.
Proceedings: Mid-Atlantic States Section APCA Semi-
Ann
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6O%
All Other
Sources
VOC Problem - 3O million tons
AIR QUALITY
CONTROL REGIONS
nONATTAINMENT OF PHOTOCHEMICAL
OXIDAPITS. AUGUST 1977
Primary NAAQS
not attained
i part of county
Qroup I
CTG Source Categories
• gasoline loading terminals
• gasoline bulk plants
• service stations • Stage I
• fixed roof petroleum tanks
• miscellaneous refinery sources
• cutback asphalt
• solvent metal cleaning
Group 1
CTG Source Categories
(continued)
•urface coating oft
• can* • aatOBMbilea and
• metal coll* llobt track.
fabric*
paper
prodMcU
«eUU f«™l*»re
larac appUajKca
2-3
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Group II
CTG Source Categories
• leaks from petroleum refineries
• miscellaneous metal parts
surface coating
• surface coating of flat wood
paneling
• syntactic pharmaceutical
manufacture
Group II
CTG Source Categories
(continued)
• rubber tire manufacture
• external floating roof petroleum
tanks
• graphic arts
• perchloroethylene dry cleaning
• gasoline truck leaks and vapor
collection
GROUP 111= CONTROL TECHNIQUES
GUIDELINES SOURCE
CATEGORIES"
• Storage, Transportation and Marketing
of VCX
• Oil ond 6as Production one) Practising
• Fuglovt VOC Ott at* Go» frodunlan
• Fuptiv* VOC Ntnunn On and GaMfcw harming flgmi
• Bulk Ttminols - Volotll. Oigonlc UquW
Uxxftng Into Hollcors
• WkPtanti-Volottl* Organic Liquid
Storoot
GROUP III1 CONTROL TECHNIQUES
GUIDELINES SOURCE
CATEGORIES0
(continued)
• Industrial Processes
• Organic Chwnkal Manufacture
• FugHlv* VOC. SOCMJ
• All OOOoUon. SOCMI
• SOR Monufaauf*
• Pofymn and Resins Manufacturing
GROUP III' CONTROL TECHNIQUES
GUIDELINES SOURCE
CATEGORIES0
(continued)
• Industrial Surface Coating
• rOOnC PnfrtiOQ
• Honlndostriol Jurfoc* Coating
• Architectural Coatings
2-4
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GROUP III' CONTROL TECHNIQUES
GUIDELINES SOURCE
CATEGORIES"
(continued)
• Oth*f Solvent Us*
• Drydeaning • Petroleum Solvent System
• Graphic Arts • Letterpress Printing 6 Offset
Lithography
• Other Mrsc«tlo«*ous Sources
• Wast* Solvent Recovery Processes'1
REGULATIONS AFFECTING
EXISTING SOURCES
Examples:
• SIP - RACT
• Federal, state and
Local Permit Systems
RACT
Reasonably Available
Control Technology
• reasonably available
technology
• considers cost
REGULATIONS
AFFECTING HEW SOURCE
CONSTRUCTION
New Source Review (HSR)
• process for reviewing new sources
NSPS
New Source
Performance Standards
• promulgated for various source
categories
• specify emission limitations
• can be found in CFR
2-5
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BACT
Best Available
Control Technology
• best technology available
• considers cost and energy
requirements
LAER
Lowest Achievable
Emission Rate
control devices to achieve
lowest possible emission r.*t<
required for sources in
nonattainment areas
PSD
Prevention of
Significant Deterioration
• EPA policy applied to
new sources in an
attainment area
RFP
Reasonable
Further
Progress
I/M
Inspection / Maintenance
2-6
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Controlled Trading
• Off set Policy
• Bubble Policy
• Banking Emissions
Offset Policy
• required for new sources
in nonattainment areas
• "trade-off" of emissions
42O Ihs/hr
3OO Ibs/hr
VOC
1OO Ibs/hr
VOC
Offset
Existing Source
new Source
Bubble
Policy
Banking
Emissions
2-7
-------
DIRECT IMPACT OF FEDERAL
POLICIES OPI STATIONARY SOURCES
Existing Source Policies —
Unmodified
Don- ^^*=^~~~-.
attainment
/
RFP
IBUBBLB
/ Attainment
OFFSET '-/ Area
DIRECT IMPACT OF FEDERAL
POLICIES OH STATIONARY SOURCES
Source Policies
IXSR
DSPS
•ACT
PM>
Attainment Area
DIRECT IMPACT OF FEDERAL
POLICIES OPI STATIONARY SOURC
Existing Source Policies -
attainment,
Area "V "»T
BACT
\ OFFSET '/ PSD
Attainment Area
2-8
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Chapter 3
Organic Chemistry Review
Lesson Goal:
Lesson Objectives:
References:
l/Vt
To review the basic concepts and terminology of organic
chemistry so that you will have a referent for the more
detailed course material.
Upon completion of this lesson, you should be able to:
• Identify organic compounds in terms of their chemical
classification, for compounds in the following classes:
— Hydrocarbons — (alkanes-alkenes-alkynes)
—Hydrocarbons
— Oxygenated Compounds—(ethanols-ethers
ketones- aldehydes
esters-acid)
— Amines
• Discuss reactivity in terms of Rule 66 and EPA's cur-
rent policy of positive emission reduction.
Brewster and McEwen. 1962. Organic Chemistry.
Prentice-Hall, Inc. New Jersey.
National Academy of Science. 1976. Vapor-Phase
Organic Pollutants— Volatile Hydrocarbons and Oxida-
tion Products. Washington, DC.
Environmental Protection Agency (EPA). 1977. Recom-
mended Policy on Control of Volatile Organic Com-
pounds. 44 Fed. Reg. 35314 (July 8, 1977).
Environmental Protection Agency (EPA). 1978. Memo:
Clarification of EPA Policy on Emissions of Methyl
Chloroform, from Walt Barber to Regional
Administrators. August 24, 1978.
Environmental Protection Agency (EPA). 1978. Memo:
Definition of Volatile Organic Compound from Vera
Gallagher to James C. Berry. October 26, 1978.
3-1
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voc
"A volatile organic compound (VOC) to
any organic compound that, when
released to the atmosphere, can remain
long enough to participate in
photochemical reactions .... almost all
organics which can be considered VOC/ ^t-^JU-t^-r
have vapor pressures greater than s *
s^^^^n^^r ^
HC Hydrocarbon
THC Total
Hydrocarbon
NonMcthanc
Hydrocarbon
HYDROCARBONS
i
I I
Aliphatic Aromatic
AlkwMs Alkene* Alkynes f\
CHjCHs CH'CH2 HC1CH benaene
ethane ethylenc ethyne ' x^/CH3
(acetylene) C^J
• 1»V toluene
NOMENCLATURE
1 carbon CH4 nMthan*
•th- 2carfaoa* CjH6 ethaoe
prop- 3carbon* CjHg propane
but- 4carbon* C^y, butane
pent- 5carbon* CjHu pratane
ha- 6carbon* C(HM hoxane
hcpt- 7carbon* C?H16 heptane
oct- 8carbon* CgHu octane
3-2
-------
Alcohols Aldehydes
9
Ketones
H-OH R-C-H R,- C-R2
Esters Acids Ethers
9 9
R-C-O-R R-C-OH R-O-R
HALOCARBONS
a a
X
a a
H a
H-,c-cra
H a
perchloroethylene trkhoroethane
(methyl chloroform)
NITROGEN COMPOUNDS
Nitroparafflns
9
CHj-CH2-O-N=O
A*k>il •.!*••.*.»
•tnin atiMw
o
nltroethane
AmlMM >x- t^^1-"
r
R-NH2
CCH
NH2
2-propylamine
NASTIES
Cl
Cl
C=C-C-H
beiuopyran pdychlortnated
blphmyl
a o "a CH3-c-o-o-N02
dioxln (TCDD) pmnucctyl nHraM
3-3
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oi
RULE 66
high reactive HC's
replaced with
low reactive HC's
EPA REVIEW OF RULE 66
• little reduction of oxidant levels
• few low reactivity organic*
• manyVOC: suspected mutagens,
carcinogens, or teratogens
• ozone layer problems
• low reactivity compounds
have limited applications
3-4
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Chapter 4
YOG Emission Measuring Techniques
Lesson Goal:
Lesson Objectives:
References:
To familiarize you with methods used to measure organic
emissions quantitatively.
Upon completion of this course, you should be able to:
• Describe the operating principles of instruments used to
measure VOC emissions:
-Non Dispersive Infrared Spectrometer (NDIR)
— Gas Chromatograph (GC)
— Flame lonization Detector (FID)
• Describe the difference between gas-liquid and gas-solid
chromatography
• Recognize the components of a typical gas
chromatographic system
• Describe the following VOC measurement/sampling
schemes:
—material balance
— activated carbon adsorption
— universal collector (carbon and Tenax GC)
— cold trap/evacuated cylinder
— syringe or purged flask
— collapsible Tedlar bags
— direct sampling with an FID (Total Hydrocarbon
Analyzer)
-GC and NDIR
• Recognize Reference Method 25 —TGNMO sampling
• Describe the sampling equipment set-up for RM 25
• Name the components analyzed in RM 25
Environmental Protection Agency (EPA). 1978. Measure-
ment of Volatile Organic Compounds. OAQPS No.
1.2-115. RTF, NC. EPA-450/2-78-041.
McNair, H. M., Bonelli, E. J. 1968. Basic Gas
Chromatography. 5th edition. Walnut Creek, CA: Varian
Aerograph.
Environmental Protection Agency (EPA). 1979. Method
25—Determination of Total Gaseous Nonmethane
Organic Emissions as Carbon: Manual Sampling and
Analysis Procedure. 44 Fed. Reg. 57808-57822 (October
5, 1979).
4-1
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MATERIAL BALANCE
AMOUNT
SAMPLING
APPARATUS
I
ACTIVATED CARBON ADSORPTION
Filter
Activated Carbon Section
Pump
UNIVERSAL COLLECTOR
SAMPLE M
OUTLET
CLOSED
SAMPLE COLLECTION
UNIVERSAL COLLECTOR
ACT. CHARCOAL
SAMPLE RECOVERY
4-2
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AND
SYRINGE SAMPLE
BAG SAMPLE
FLOW METER
I
COLD TRAP-
EVACUATED CYLINDER
VACUUM
GAUGE
LABORATORY
ANALYSIS
NDIR ANALYZER
INFRARED BEAM SAMPLE SAMPLE
CHOPPER, IN EXHAUST lOETECTOR
SENSOR
4-3
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GAS-SOLID
OOQ
ooo
GAS-LIQUID
OOO
GAS CHROAAATOGRAPHIC SYSTEM
Injection
Port
mm
ilisH-Sij
Detector
Column
Carrier
Gas
Bottle
Chromatogrom
>uAUU
Recorder
Injection
Port
Carrier
Gas
Bottle
Column
4-4
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GAS-LIQUID
COO
coo
Detector
THERMAL CONDUCTIVITY CELL
Electric Leads.
FLAME IONIZATION DETECTOR
Exhaust
I
J_
Sample H2 Air
Chromatogram
Recorder
4-5
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Thermostats
-"T
GAS CHROAAATOGRAPHIC SYSTEM
Recorder
BYRON ORGANIC ANALYZER
Somp).
AUTOAAATIC
PROGRAMMED ANALYSIS
4-6
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FID
Used as a Total
Hydrocarbon Analyzer
METHOD 25 SAMPLING TRAINS
METHOD 25 ANALYSIS
• Condensate
• Tank
METHOD 25 LAB ANALYSIS
1 Step 1: Condensate Trap
METHOD 25 LAB ANALYSIS
Step 2: Sample and Intermediate
Tanks
4-7
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METHOD 25
COMPONENTS ANALYZED
• NonmethaneOrganics
•CO,CO2,andCH4
EMISSION VALUES
(ppm equivalents)
Carbon
• FID calibrated using
methane
Propane
• FID calibrated using
propane
VOC CONCENTRATION
CALCULATION
ppm ppm
propane ^ 3 = carbon
equivalent equivalent
value value
Example:
100 ppm x 3 — 300 ppm
prooanp carbon
equivalent equivalent
value value
4-8
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Chapter 5
VOC Emissions from Industrial
Surface Coating Operations
Lesson Goal:
Lesson Objectives:
To familiarize you with the impact of surface coating
operations as a source of VOCs. To provide for you a
basis for understanding the types of coating processes,
problems, and control operations that are available.
Upon completion of this lesson, you should be able to:
• Recognize the relationship between VOC emission and
the quantity and types of organic solvents within the
coating material.
• Define in general terms:
— paint
— transfer efficiency
-flash off
— powder coating
— electrodeposition
• Describe three processes that may be used for drying
common coating materials, giving an example of each:
— evaporation—lacquer
— oxidation — enamel
— polymerization — epoxide
• List and describe the five applications commonly used to
apply surface coatings.
— spray
— dip
— flow
— roller
—knife
• Describe the relative transfer efficiencies for the five
application methods listed above.
• Identify the industrial uses of each of the five applica-
tion methods listed above.
• For each application method, describe the relative emis-
sion quantities for each step of the process:
— application
— pre-drying
— curing
5-1
-------
• List and describe five methods for controlling VOC
emission from surface coating operations which can be
considered RACT.
— formula change
— radiation method
— powder application
— process changes
— add-on control
• Describe the advantages and disadvantages of each of
the above five RACT methods.
• Describe the terms in which the recommended VOC
standards for surface coating are given.
• Calculate the VOC emissions for a coating containing
both organic solvents and water, given the percentages
of each in the coating.
• Using the graph found in EPA-450/2-77-008, page 1-4,
calculate the emissions reduction obtained by using a
coating with a higher solids content.
References Environmental Protection Agency (EPA). Control
Technology Guideline Documents.
November 1976. Control of Volatile Organic Emissions
from Existing Stationary Sources— Volume I: Control
Methods for Surface-Coating Operations. OAQPS No.
1.2-067. EPA-450/2-76-028.
May 1977. Control of Volatile Organic Emissions from
Existing Stationary Sources— Volume II: Surface
Coating of Cans, Coils, Paper, Fabrics, Automobiles
and Light-Duty Trucks. OAQPS No. 1.2-073.
EPA-450/2-77-008.
December 1977. Control of Volatile Organic Emissions
from Existing Stationary Sources— Volume HI: Surface
Coating of Metal Furniture. OAQPS No. 1.2-086.
EPA-450/2-77-032.
December 1977. Control of Volatile Organic Emissions
from Existing Stationary Sources— Volume IV: Surface
Coating for Insulation of Magnetic Wire. OAQPS No.
1.2-087. EPA-450/2-77-033.
December 1977. Control of Volatile Organic Emissions
from Existing Stationary Sources— Volume V: Surface
Coating of Large Appliances. OAQPS No. 1.2-088.
EPA-450/2-77-034.
5-2
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June 1978. Control of Volatile Organic Emissions from
Existing Stationary Sources— Volume VI: Surface
Coating of Miscellaneous Metal Parts and Products.
OAQPS No. 1.2-101. EPA-450/2-78-015.
June 1978. Control of Volatile Organic Emissions from
Existing Stationary Sources— Volume VII: Factory Sur-
face Coating of Flat Wood Paneling. OAQPS No.
1.2-112. EPA-450/2-78-032.
December 1978. Control of Volatile Organic Emissions
from Existing Stationary Sources— Volume VII:
Rotogravure and Flexography. OAQPS No. 1.2-109.
EPA-450/2-78-033.
Environmental Protection Agency (EPA). 1977. Con-
trolling Pollution from the Manufacturing and Coating
of Metal Products. Environmental Research Center,
Cincinnati, OH. EPA-625/S-77-009.
5-3
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many different types
of materials used for
decoration and
protective coating
of various surfaces
1,020,000 Metric Tons
Industrial Surface Coating
14,660,000
METRIC
TONS/YR
FACTORS AFFECTING EMISSIONS
NON - PROCESS FACTORS PROCESS FACTORS
TYPICAL OIL BASE WHITE HOUSEPAINT
% BY WEIGHT
HEAT BODIED LINSEED OIL'"''""''
THINNER »«miHHi..u,.mi.i..H.H,u,HM.Mm.i.,,..m,
«», i2\
mm I",
mm 1 91
5.4
-------
RULE 66 FORMULATIONS
3.5% ALCOHOLS
6.7% AROMATICS
47 % SATURATED
ALIPHATICS
42.8% NON-
VOLATILE
PORTION
FORMAT FOR EMISSION
LIMITATIONS
tbs. organic volatile*
gallon coating (-water)
RACT RECOMMENDED EMISSION
2.55 Ibs solvent
gallon (-water)
Coil Coating
1.89 Ibs solvent . . 0 .
gallon (-water) Auto Pnmer Coating
2.96 Ibs solvent
gallon (-water) Metal Furniture Coating
Paints
EVAPORATION
Lacquers
Shellac
Varnishes
OXIDATION
Enamels
Acrylics
POLYMERIZATION
Epoxies
Latex
Urethanes
5-5
-------
CO
•o
1
ALTERNATIVE TOPCOATS
Lacquer
Dispersion Lacquer
-Current Enamel
-Nonaqueous Enamel
Urethane
Cathodic E-Coat
odic E-Coat-
Powder Coating
2030405060708090100
Percent Solids by Volume, excluding water
(0
40 Transfer Efficiency
50
20 30 40 50 60 70 80
Percent Solids by Volume, excluding water
I _L 1 1 1 1 ,
60S 518 432 395 259
Solvent Content, grams per liter
5-6
-------
PROCESSING FACTORS
APPLICATION
PRE-DRYING
CURING
AMOUNT APPLIED
TRANSFER EFFICIENCY
> .} THICKNESS
AREA TO COAT
PAINT
% SOLVENT
THINNER
1GAL.
SURFACE COATING = SOLIDS + SOLVENT
20% SOLIDS •
80% SOLVENT
t
.2 mil
5-7
-------
Estimation of Solvent Emissions
.
ef=
VSQ
1 -ws
In units of Ib VOC/lgal - H20)
PROCESSING
FACTORS
COATING
PROCESSES
FLOW
SPRAY
ROLL
DIP
KNIFE
SPRAY
TECHNIQUES
SPRAYING
SPRAY
BOOTH
Transfer
Efficiency
30%-60%
5-8
-------
DIP
COATING /
Transfer Efficiency 75% - 95%
FLOW COATING
ROLLER COATING
TOP COi
TO OVEN
BOTTOM COAT
TRANSFER
EFFICIENCY 95%
Sheet-ted offset press.
COATING
KNIFE COATING
TRANSFER
EFFICIENCY 95%
5-9
-------
FLASH OFF
• quantity of solvent
evaporated from the
coated surface during
a specific time
DRYING: Removal of Volatiles
BAKING: Curing of the Coating
OVEN DESIGN
Sufficient Pre-dry Time
Initial Low Temperature Zone
Sufficient Curing Time & Temperature
Cool Down
Emission Removal
Adequate Air
HEAT SOURCES
DIRECT FIREO
GAS HEAT
INDIRECT FIREO
GAS HEAT
ELECTRICAL
HEAT
> OF TOTAL EMISSIONS
SPRAY
FLOW
DIP
ROLLER
APPLICATION
30-50
30-50
5-10
0-5
PREDRY
10-30
20-40
10-30
10-20
CURING
20-40
10-30
50-70
60-80
Source: Foster D. Snell Inc.
5-10
-------
METHODS OF CONTROL
• Formula Changes
* Radiation Methods
• Powder Coats
• Process Changes
• Add-on Control Equipment
WATER BORNE PAINTS
ADVANTAGES
DISADVANTAGES
• Reduced Flammability
• Wide Range
of Formulations
* Higher Solid Content'
Viscosity
• Reduced Emissions
• Lower Materials Cost
* Ease of Cleanup
• Untried Technology
• Higher Energy
Requirements
• Corrosion
• Increased Treatment
• Humidity Problems
HIGH SOLIDS COATING
ADVANTAGES
DISADVANTAGES
• Reduced Inventory Space
• Reduced Drum Handling
• Reduced Solvent
Removal Energy
• Increased Compliance
Potential
• Reduced Freight Colt
• Higher Coaling Viscotrty
• Reduced Storage Stability
• Fewer Formulations
RADIATION CURING SYSTEMS
uv
or Electron Beam
RADIATION CURING
ADVANTAGES
DISADVANTAGES
• Emissions Reduction
• Highspeed
• low Operating Coil
• Reduced Floor Span
• High Formula Coil
• Limit Formula Selection
• Need for Radiation Protection
• Equipment Coats
5-11
-------
POWDER COATS
POWDER COATS
ADVANTAGES
DISADVANTAGES
> Very Low
Emissions
> Reduced Energy
Needs
Higher Cost
Limited Selection
• Variable Adhesion
Incompatible with
Existing Equipment
Uniformity Problems
Color Changes
PROCESS CHANGES
• Improved Application Efficiency
• Use of Prefinished Roll Stock
• Use of Metalized Coating
• Increase Vapor Concentration
5-12
-------
Chapter 6
VOC Emissions from
Coil Coating Operations
Lesson Goal:
Lesson Objectives:
References:
The purpose of this lecture is to give you an example of
the type of information that is needed when developing
RACT guidelines for State Implementation Plans for a
typical coatings industry.
Upon completion of this lesson, you should be able to:
• Diagram the coil coating process.
• Point out the VOC emission points of a coil coating
operation.
• List at least two RACT methods appropriate for coil
coating operations.
• Recognize the fuel saving aspect of incineration when
applied to coil coating.
• Develop an analysis of the type of control options
available to another industry emitting volatile organic
compounds.
Environmental Protection Agency (EPA). 1977. Control
of Volatile Organic Emissions from Existing Stationary
Sources— Volume II: Surface Coating of Cans, Coils,
Paper, Fabrics, Automobiles, and Light Duty Trucks.
OAQPS No. 1.2-073. EPA-450/2-77-008 (May 1977).
U.S. Department of Energy. 1978. Oven Curing: Energy
Conservation and Emission Control in Coil
Coating—Technical Briefing Report—Technology
Transfer TID-28705.
6-1
-------
TYPICAL COATING MATERIALS
Coating
Acrylics
Epoxies
Phenolics
Polyesters
Silicones
Volatile
(weight percent)
40 - 45
45 70
45 - 5O
45 • 5O
35 - 5O
HYDROCARBON
SOLVENTS
• Xylene
• Toluene
• NEK
• Other Alcohols
and Ketones
A,"
DIAGRAM OF COIL
COATiriO LINE WITH »£• **• ,!•»
EMISSION POINTS
TYPICAL REVERSE ROLL COATER
into oven
applicator roll
N-
flow of metal
into coaler
6-2
-------
APPLICABLE
SYSTEMS OF EMISSION REDUCTION
Electro-Deposition — primer use
Radiation Cure — lack of monomers
Powder Coating — uniformity problems
Water • borne — limited range of paints
— flexibility problems
High Solids — viscosity too high
Adsorption — limited because of
effluent temperatures
Incineration — energy problem?
INCINERATION
ECONOMICS
Retrofit — justifiable with
8O% energy savings
Solvent VOC's - BTU's
RACT
2.6lb. solvent
gallon — H2O
Based upon incineration of
organic solvent-borne coating
containing 25% solids by volume.
6-3
-------
Chapter 7
VOCs and Photochemical Oxidants
Lesson Goal:
Lesson Objectives:
References:
To give you an understanding of the role of volatile
organic compounds in the development of photochemical
smog.
Upon completion of this lesson, you should be able to:
• Diagram the photostationary state for Os production.
• Describe how peroxy radicals affect the photostationary
state to produce a net increase in ozone.
• Explain why ambient NOT levels are a significant factor
in the development of photochemical smog.
• Tell what effect high, low, and intermediate values of
the VOC/NO, ratio have on the photochemical oxidant
cycle.
• Use the EKMA graphs to determine ozone levels given
different oxidant precursor conditions.
• Discuss the effect of natural sources of volatile organic
compounds in the photochemical cycle.
Williamson, S. J. 1973. Fundamentals of Air Pollution.
Addison-Wesley Publishing Co. Mass. Chp. 10, pp.
296-305.
Environmental Protection Agency (EPA). 1977. Effec-
tiveness of Organic Emission Control Programs as a Func-
tion of Geographic Location. January 1977. CPDD,
OAQPS, EPA. EPA paper in support of ANPR for 41 FR
55558 December 21, 1976.
Environmental Protection Agency (EPA). 1978. Questions
and Answers Concerning the Basis for the Agency's Posi-
tion on Controlling Hydrocarbons to Reduce Oxidant.
Memo from David G. Hawkins (EPA-OANR) to
Regional Administrators. July 28, 1978.
Anderson, L. G. "Effects of Nighttime Chemistry upon
the Transport of Ozone and Ozone Precursors."/. Air
Pollut. Control Assoc. Vol 29: 970-973. September 1979.
Dimitriades, B. Issues Regarding the Role of Natural
Organics in Photochemical Air Pollution. Paper 80-69.1
presented at 73rd Annual Meeting of Air Pollut. Control
Assoc., June 22-27, 1980 Montreal, Quebec.
7-1
-------
Environmental Protection Agency (EPA). 1977. Uses,
Limitations and Technical Basis of Procedures for Quan-
tifying Relationships Between Photochemical Oxidants
and Precursors. EPA-450/2-77-021a, November 1977.
Environmental Protection Agency (EPA). Procedures for
Quantifying Relationships Between Photochemical
Oxidants and Precursors: Supporting Documentation.
EPA-450/2-77-021b.
Environmental Protection Agency (EPA). Relation of
Oxidant Levels to Precursor Emissions and Meteorological
Features.
Vol. I: Analysis and Findings, EPA-450/3-77-022a.
Vol. II: Review of Available Research Results and
FPA-450/3-77-022b.
Vol. Ill Monitoring Data; tr^ o.,
Seinfeld, J. H. 1975. Air Pollution— Physical and
Chemical Fundamentals. New York: McGraw Hill.
Stevens, P. K. 1980. "Characterization of the Aerosol in
the Great Smoky Mountains", , . . _ „
Assoc. 14:1491-1498. J An Pollut' Contr°l
7-2
-------
fln oc PHOTOCHEMICAL
VOCs AND
HEMICAL
OXIDANTS
NO CONVERTS TO N<>2
2NO + O2
NO + O3
2NO2
NO2 + O2
~ compounds
new organic
compounds
increases,
O3 increases.
Where:
k = reaction rate constant
7-S
-------
ROv or R-O-O-
Rtl -t- HO»=t R'O2- + R"CHO
7-4
-------
0.50
0.40
f C.30
3O: I
7-5
-------
THE EMPIRICAL KINETIC MODELING APPROACH: EKMA
0.28
0.12
0.08
0.2
0.4
0.6
0.8 1.0 1.2
NHMC, ppm C
1.4
1.8
NATURAL VOCs
• Areas with high values of
natural VOCs generally have
low NOji values; therefore.
levels of oxidant
'A position: natural sources
jof VOCs do not contribute to
smog formation
7-6
-------
Chapter 8
VOC Emissions
from Degreasing Operations
Lesson Goal:
Lesson Objectives:
References:
To familiarize the students with the operation of vapor
and liquid degreasing processes, the VOC emissions
generated by them and the types of emission controls
available for degreasing operations.
The student should be able to:
• Identify the typical solvents used in degreasing
operations.
• Describe three types of degreasers and the typical emis-
sion points for each.
• Recognize the control methods for each type of
degreaser.
• Recognize inspection procedures and EPA RACT
guidelines for degreasers.
Environmental Protection Agency (EPA). 1977. Control
of Volatile Organic Emissions from Solvent Metal
Cleaning. OAQPS No. 1.2-079. RTP, NC.
EPA-450/2-77-002.
Environmental Protection Agency (EPA). 1977. Con-
trolling Pollution from the Manufacturing and Coating of
Metal Products, Solvent Metal Cleaning Air Pollution
Control—II. Technology Transfer Seminar Publication.
EPA-625/3-77-009.
Environmental Protection Agency (EPA). 1979. Solvent
Metal Cleaning, Inspection—Source Test Manual.
Washington, B.C. EPA 340/1-79-008.
Environmental Protection Agency (EPA). 1980. "Organic
Solvent Cleaners; Standards of Performance for New
Stationary Sources; Proposed Rule and Notice of Public
Hearing". 45 Fed. Reg. No. 114, 39766-39784 (June 11,
1980).
8-1
-------
voc
EMISSIONS
FROM
DECREASING
OPERATIONS
Used to clean
SOLVENTS
• Aliphatics
• kerosene
• heptane
• Aromatics
• toluene
• turpentine
• Keytones, Alcohols, Ethers
• Halogenated Organics
HALOGENATED
ORGANICS
• trichloroethylene
• 1,1,1 trichloroethane
• perchJoroethylene
• methylene chloride
• trichlorotrifluoroethane
8-2
-------
TYPES OF
DEGREASERS
• Cold Cleaner
• Open Top
• Conveyorized
COLD CLEANER
DEGREASER
, , X^XX COLD CLEANER
«poJ^ X^-X*.'*.''' DEGREASER
6.V.'!. * .,«• EMISSION
POINTS
'carry-out
OPEN TOP
condensing coils DEGREASER
heating elements
„„,,. \ REFRIGERATED
X FREEBOARD
CHILLER
8-S
-------
OPEN TOP
DEGREASER
exhaust WITH LIP
EXHAUST
TWO
COMPARTMENT
OPEN TOP
DEGREASER
offset solvent
boiling chamber
warm solvent
immersion chamber
roofvent^ diffusion and
convection OPEN TOP
\ -L DEGREASER
_. ~ — 'J** ^ EMISSION
adsor&er' n ^.i-i.iii*:.?.. POINTS
waste
MONORAIL
CONVEYORIZED,
DEGREASER
boiling chamber
CROSS-ROD
CONVEYORIZED DEGREASER
8-4
-------
MESH BELT
CONVEYORIZED
DEGREASER
CONVEYORIZED DEGREASER
EMISSION POINTS
carry-out
bcr
FIELD INSPECTION
carbon
adsorption
svstem
SOURCE MEASUREMENT
METHOD 23
Ted la r or
aluminiyed
Mylar bag
rigid leak-proof
container
METHOD 23
LAB ANALYSIS
8-5
-------
GUIDELINES FOR RACT
• Control System A
• operating and working practices
• inexpensive control
• Control System B
• all of Control System A plus
more control
EPAs POLICY
ON EXEMPTIONS
• Cold Cleaners in rural
nonattainment areas with
emissions < 100 tons per year
• Open Top Degreascrs with open
area < 1.0 m2
• Conveyorized units with air/vapor
interface < 2.0 m2
8-6
-------
EPA's Policy on RACT Regulations for Degreasers
EPA's guidelines for RACT as applied to degreasers are divided into separate
guidelines for cold cleaners, open top vapor degreasers, and conveyorized
degreasers. Each guideline is divided into two levels of control. Control System A
consists of operating practices and simple, inexpensive control equipment. Control
System B consists of System A plus additional requirements to improve the effec-
tiveness of control.
Application of Control Systems A and B
An approvable State Implementation Plan (SIP) must require the application of
Control System B throughout urban nonattainment areas (> 200,000 population)
seeking an extension and to all facilities emitting VOCs in excess of 100 tons per
year in other nonattainment areas. Facilities emitting 100 tons per year or less of
VOCs in other nonattainment areas must apply Control System A as a minimum.
However, EPA encourages States to control all degreasers in nonattainment areas
to the Control System B level.
Control Systems for Cold Cleaning
Control System A—(work practices)
Control Equipment
1. Cover
2. Facility for draining cleaned parts
3. Permanent, conspicuous label, summarizing the operating requirements.
Operating Requirements
1. Do not dispose of waste solvent or transfer it to another party, such that
greater than 20 percent of the waste (by weight) can evaporate into the
atmosphere.* Store waste solvent only in covered containers.
2. Close degreaser cover whenever not handling parts in the cleaner.
3. Drain cleaned parts for at least 15 seconds or until dripping ceases.
*Water and solid waste regulations must also be complied with.
8-7
-------
Control System B—(includes all of Control System A)
Control Equipment
1. Cover: Same as in System A, except if (a) solvent volatility is greater than
2 kPa (15 mm Hg or 0.3 psi) measured at 38°C (100°F),* (b) solvent is
agitated, or (c) solvent is heated, then the cover must be designed so that it
can be easily operated with one hand. (Covers for larger degreasers may
require mechanical assistance, by spring loading, counterweighing or powered
systems.)
2. Drainage facility: Same as in System A, except that if solvent volatility is
greater than about 4.3 kPa (32 mm Hg or 0.6 psi) measured at 38°C (100°F),
then the drainage facility must be internal, so that parts are enclosed under
the cover while draining. The drainage facility may be external for applica-
tions where an internal type cannot fit into the cleaning system.
3. Label: Same as in System A.
4. If used, the solvent spray must be a solid, fluid stream (not a fine, atomized or
shower type spray) and at a pressure which does not cause excessive splashing.
5. Major control device for highly volatile solvents: If the solvent volatility is
>4.3 kPa (33 mm Hg or 0.6 psi) measured at 38°C (100°F), or if solvent is
heated above 50°C (120°F), then one of the following control devices must be
used:
a. Freeboard that gives a freeboard ratio** >0.7
b. Water cover (solvent must be insoluble in and heavier than water)
c. Other systems of equivalent control, such as a refrigerated chiller or carbon
adsorption.
Operating Requirements
Same as in System A
Complete Control Systems
for Open Top Vapor Degreasers
Control System A
Control Equipment
1. Cover that can be opened and closed easily without disturbing the vapor zone.
Operating Requirements
1. Keep cover closed at all times except when processing work loads through the
degreaser.
'Generally solvents consisting primarily of mineral spirits (Stoddard) have volatilities <2 kPa.
**Freeboard ratio is defined as the freeboard height divided by the width of the degreaser.
f8-~8
-------
2. Minimize solvent carry-out by the following measures:
a. Rack parts to allow full drainage.
b. Move parts in and out of the degreaser at less than 3.3 m/sec (11 ft/min).
c. Degrease the work load in the vapor zone at least 30 sec or until condensa-
tion ceases.
d. Tip out any pools of solvent on the cleaned parts before removal.
e. Allow parts to dry within the degreaser for at least 15 sec or until visually
dry.
3. Do not degrease porous or absorbent materials, such as cloth, leather, wood or
rope.
4. Work loads should not occupy more than half of the degreaser's open top area.
5. Never spray above the vapor level.
6. Repair solvent leaks immediately, or shut down the degreaser.
7. Do not dispose of waste solvent or transfer it to another party such that greater
than 20 percent of the waste (by weight) will evaporate into the atmosphere.
Store waste solvent only in closed containers.
8. Exhaust ventilation should not exceed 20 mVmin per m2 (65 cfm per ft2) of
degreaser open area, unless necessary to meet OSHA requirements. Ventilation
fans should not be used near the degreaser opening.
9. Water should not be visually detectable in solvent exiting the water separator.
Control System B
Control Equipment
1. Cover (same as in System A).
2. Safety switches
a. Condenser flow switch and thermostat — (shuts off sump heat if condenser
coolant is either not circulating or too warm).
b. Spray safety switch — (shuts off spray pump if the vapor level drops
excessively, about 10 cm (4 in.).
3. Major Control Device:
Either:
a. Freeboard ratio greater than or equal to 0.75, and if the degreaser opening
is >1 m2 (10 ft2), the cover must be powered,
b. Refrigerated chiller,
c. Enclosed design (cover on door opens only when the dry part is actually
entering or exiting the degreaser),
d. Carbon adsorption system, with ventilation >15 mVmin per m*
(50 cfm/ft*) of air/vapor area (when cover is open), and exhausting
<25 ppm solvent averaged over one complete adsorption cycle, or
e. Control system, demonstrated to have control efficiency, equivalent to or
better than any of the above.
4. Permanent, conspicuous label, summarizing operating procedures #1 to #6.
Operating Requirements
Same as in System A.
8-9
-------
Control Systems for Conveyorized Degreasers
Control System A
Control Equipment: None
Operating Requirements
1. Exhaust ventilation should not exceed 20 mVmin per m2 (65 cfm per ft2) of
degreaser opening, unless necessary to meet OSHA requirements. Work place
fans should not be used near the degreaser opening.
2. Minimize carry-out emissions by:
a. Racking parts for best drainage.
b. Maintaining vertical conveyor speed at <3.3 m/min (11 ft/min).
3. Do not dispo:•» " waste solvent or transfer it to another party such that greater
than 20 percent of the waste (by weight) can evaporate into the atmosphere.
Store waste solvent only in covered containers.
4. Repair solvent leaks immediately, or shutdown the degreaser.
5. Water should not be visibly detectable in the solvent exiting the waste
separator.
Control System B
Control Equipment
1. Major control devices; the degreaser must be controlled by either:
a. Refrigerated chiller.
b. Carbon adsorption system, with ventilation > 15 mVmin per m2
(50 cfm/ft2) of air/vapor area (when down-time covers are open), and
exhausting < 25 ppm of solvent by volume averaged over a complete
adsorption cycle, or
c. System demonstrated to have control efficiency equivalent to or better than
either of the above.
2. Either a drying tunnel, or another means such as rotating (tumbling) basket,
sufficient to prevent cleaned parts from carrying out solvent liquid or vapor.
3. Safety switches:
a. Condenser flow switch and thermostat —(shuts off sump heat if coolant is
either not circulating or too warm).
b. Spray safety switch — (shuts off spray pump or conveyor if the vapor level
drops excessively, e.g. > 10 cm (4 in.).
c. Vapor level control thermostat —(shuts off sump heat when vapor level rises
too high).
4. Minimized openings: Entrances and exits should silhouette work loads so that
the average clearance (between parts and the edge of the degreaser opening) is
either < 10 cm (4 in.) or < 10 percent of the width of the opening.
5. Down-time covers: Covers should be provided for closing off the entrance and
exit during shutdown hours.
8-10
-------
Operating Requirements
1. to 5. Same as for System A.
6. Down-time cover must be placed over entrances and exits of conveyorized
degreasers immediately after the conveyor and exhaust are shutdown and
removed just before they are started up.
8-11
-------
Chapter 9
VOC Emissions from Petroleum
Refineries
Lesson Goal:
Lesson Objectives:
References:
To describe the operation of a typical refinery and iden-
tify the potential sources of VOC emissions from these
operations.
Upon completion of this lesson, you should be able to:
• Recall the magnitude of VOC emissions from a refinery
compared to the total from stationary sources in the
USA.
• List and describe the three major steps in refining:
— separation
— conversion
— treatment
• List at least three sources of emissions from a refinery
and recall methods for their control.
— vacuum producing systems
— wastewater treatment
— process turn arounds
Environmental Protection Agency (EPA). 1973. Air Pollu-
tion Engineering Manual, Second Edition. AP-40.
Environmental Protection Agency (EPA). 1977. Control
of Refinery Vacuum Producing Systems, Wastewater
Separators, and Process Unit Turnarounds, Guideline
Series. EPA-450/2-77-025.
American Petroleum Institute (API). 1973. Hydrocarbon
Emissions from Refineries. Bulletin 928.
Film: "Refining". Peckham Productions. New York. Film
#4879.
9-1
-------
STATIONARY SOURCES
OFVOC
lOfog*. tronipoMQtion
ond morH«img of
petroleum product!
PETROLEUM REFINERY
separot
processes
crude
•urn
products
treatment processes
VACUUM
UNIT
light gases
light gas oils
gas oils
lube oils
residuums
light product!
»
-------
accumulator
CC*»f
gosolln*
COKING
UNIT
TREATMENT PROCESSES
• Hydrotreoting
• Sweetening
• Acid Treating
• Solvent Treating
• Blending
• Asphalt Blowing
toracovwy
ASPHALT AIR
BLOWING
- inlduum fMd
VACUUM
PRODUCING
SYSTEM
9-3
-------
TYPES OF VACUUM
PRODUCING SYSTEMS (VPS)
• Steam Ejector with Contact
Condenser
• Steam Ejector with Surface
Condenser
• Mechanical Pump
Incoming _
non-eondensables
- jet st*am
• exhaust
•mission!
hot well
TWO STAGE
CONTACT CONDENSER
water
vapor
I SHELL-AND-TUDE t
CONDENSER
non-condensate
coodensote
CONTROL METHODS
FOR VACUUM PRODUCING SYSTEM
Source
Nan-
CoodensoWes
Hot W«ll
Control
incinerate,
compress, or
send to fuel
gas/firebox
cover and
Incinerate
vapors
Emission Factor
(uncontrolled)
145 kg/100 m'
or
51 lb/10'bbl
_
voc
WASTE-
WATER
TREATMENT
9-4
-------
TYPES OF
WASTEWATER SEPARATORS
• API Separator
• Corrugated Plate
Interceptors (CPI)
• Flocculation
• Air Flotation
API SEPARATOR
skimmer
T
underflow baffle
DISSOLVED-AIR FLOTATION
aerated
water
oil and
water
COVERED API SEPARATOR
floating cover
underflow t sffle
vent emissions
PROCESS
TURNAROUNDS
9-5
-------
PROCESS
TURNAROUND
EMISSION FACTOR
uncontrolled 860 kg/103 m3
refinery feed
HYDROCARBON EMISSION
SOURCES IN PETROLEUM REFINERIES
Uncontrolled Controlled
-------
Chapter 10
Operation-Maintenance-Inspection
—Petroleum Refinery Leaks
Lesson Goal:
Lesson Objectives:
References:
To describe the need for an operation-maintenance-and
inspection program for organic emission control equip-
ment and describe the benefits gained by initiating such a
program.
Upon completion of this lesson, you should be able to:
• Define what an operation—maintenance —inspection
program is and list three major reasons why such a pro-
gram should be implemented.
• Recognize the U.S. EPA, CARB, and Illinois
Environmental Protection Agency documents dealing
with O-M-I programs.
• Recognize a typical O-M-I program for oil refineries
and identify the important features of the program.
• Identify two data reporting needs of an O-M-I program
and give examples of each.
Environmental Protection Agency (EPA). 1978. Control
of Volatile Organic Compound Leaks from Petroleum
Refinery Equipment. Emissions Standards and Engineer-
ing Division. OAQPS No. 1.2-111. EPA 450/2-78-036.
State of California Air Resources Board. 1975. Emissions
from Leaking Valves, Flanges, Pump and Compressor
Seals, and Other Equipment at Oil Refineries. The Legal
Affairs and Enforcement and the Stationary Source Con-
trol Divisions, Report No. LE—78-011, Sacramento, CA,
April 1978.
Cross, Frank L., Jr.; Hesketh, Howard E., editors. 1975.
Handbook for the Operation and Maintenance of Air
Pollution Control Equipment. Westport, CT: Technomic
Publishing Co. Inc. 1975.
Wallace, Michael J. 1979. Controlling Fugitive Emissions.
Chemical Engineering. August 27, 1979. 78-92.
Morgester, J. J. et al. 1979. Control of Emissions from
Refinery. . .Valves and Flanges. Chemical Engineering
Progress. August 1979. 40-45.
10-1
-------
Hughes, T. W., Tierney, D. R., and Kahn, Z. S. 1979.
Measuring Fugitive Emissions from Petrochemical Plants.
Chemical Engineering Progress. August 1979. 35-39.
10-2
-------
OPERATION MAINTENANCE
STAGE - Continued Surveillance
CONTROL STAGE- Installation Of
Equipment
MONITORING STAGE- Detection Of Pollutants
And Sources
AN O/M/I PROGRAM IS
» Training
* Administration
• Inspection
* Preventive Maintenance
• Corrective Action Procedures
* Spare Parts
WHY O/M/I ?
1. Legal Requirementi
2 IniureNAAQSandSIP
In-plant Benefits
IN-PLANT BENEFITS OF O/M/I
1. Reduced Operating Cost
2. Compliance
3. Extended Equipment Life
4. Equipment Failure Detection/Prediction
5. Equipment Damage Prevention
6. Sustained Emissions Compliance
7. Product Recovery
8. Safety
10-3
-------
INSPECTIONS
ANNUALLY QUARTERLY
WEEKLY
INSPECT
VOC Detector
• Pump seals
•Pipeline valves
- liquid
•Process drains
INSPECT
VOC Detector
•Compressor seals
•Pipeline valves -
gas
•Pressure relief
valves - gas
INSPECT
Visually
• Pump seals
LEAKING COMPONENT
7
10,000 ppm
1,000 ppm @ 5 cm
GLOBE
VALVE
Possible
Leak
Areas
VISUAL INSPECTION
"SNOOP BUBBLES
10-4
-------
BAG TECHNIQUES • *"•*"'
HIGH LEAK RATE
BAG TECHNIQUES
LOW LEAK RATE
Aitalynr
SIMPLE MECHANICAL SEAL
Product
Being Pumped
Possible
Leak
Areas
TYPICAL AVERAGE LEAKS
Valves
Compressor
Seals
Pump Seals
0.2 kg/day
0.7 kg/day
1.1 kg/day
ESTIMATING COSTS-ANNUAL
TOTAL .
$115,000
4.9 Capital
25.2 Inspection
31.7 Administrative
and Support
53.2 Repair and
Maintenance
10-5
-------
BLACK GOLD REFINERY
Estimated
Emissions
1000 METRIC
TON/YEAR
Emissions
Reduced
with O/M/I
500 METRIC
TON PER YEAR
Savings
Per Ton
Reduced
J 150 PER
METRIC TON
iiHiHHimMiiiiiiiniiiniinNi
Annual
Savings
$75.000
TOTAL
ANNUALIZED
COST
O/M/I
$115,000
—
ANNUAL
SAVINGS
$75,000
_
NET
REFINERY
COST FOR
O/M/I
$40,000
10-6
-------
Chapter 11
VOC Emissions from Storage
of Petroleum Products
Lesson Goal:
Lesson Objectives:
References:
To examine the types of vessels used to store petroleum
liquids, their potential emissions, and their control as
outlined in the CTG Documents.
Upon completion of this lesson, you should be able to:
• List the factors affecting emissions from fixed-roof
tanks.
• Describe the RACT requirements for fixed-roof tanks
and their control efficiency.
• Describe three types of floating roofs.
• Describe the RACT requirement for external floating
roofs.
• Describe the difference between RACT requirements
for welded tanks and riveted tanks.
Environmental Protection Agency (EPA). 1978. Control
of VOC from Petroleum Storage in External Floating
Roof Tanks. Guideline Series. EPA-450/2-78-047.
Environmental Protection Agency (EPA). 1977. Control
of VOC from Petroleum Storage in Fixed Roof Tank.
Guideline Series. EPA-450/2-77-036.
American Petroleum Institute. 1980. Evaporation Loss
from External Floating Roof Tanks. Washington, DC.
API Publication 2517.
11-1
-------
RACT
All Tanks > 40,000 gal @ v.p.> 1.5 psla
STORAGE TANKS
Fixed Roof Floating Roof Pressure
PETROLEUM STORAGE
Product
Crude.
Lub Oils
Kerosene.
Gasoline,
Fuel Oils
Butane,
Propane
Volatility
Low
Intermediate
High
v.p. Range
< 1.5 psio
1.5 - 11.2
psio
> 11. 2 psio
Tank Type
Fixed
Float
Pressure
Inspection hatch
rrwnhol*
Breathing Losses Working Losses
11-2
-------
FACTORS AFFECTING VOC LOSSES
• true vapor pressure
• temperature changes
• tank diameter
• turnaround
• condition of P/V valves
• color and condition tank
• height of vapor space
FIXED ROOF TANK WITH
INTERNAL FLOATING COVER
wlp*r-s*ol
loom-filled coated fabric wol
buoyant pantl
,- jtn
foom-flll*d coot*d fabric s*ol
**l pan
INTERNAL
FLOATING
ROOFS
EXTERNAL FLOATING ROOF TANK
(drain
Pan
Pontoon
Double-Deck
TYPES OF
EXTERNAL
FLOATING
ROOFS
11-3
-------
MECHANICAL
SHOE SEAL
RESILIENT FOAM AND LIQUID SEALS
Liquid-Mounted Vapor-Mounted
RACT
(for External Floating Roofs)
• secondary rim-mounted
seal covering the primary
seal
SECONDARY SEALS
secondary seat
secondary seal
SECONDARY SEAL REQUIRED
Riveted
Tank
When.
•«>»v.p.>1Jpila
11-4
-------
SECONDARY SEAL REQUIRED
Welded
Tank
When took equipped with,
• vapor mourned i«al
ana t»u« v.p _; l.Spjia
or
• shew s«al
• licm'd mounted t*al
1 and iiu* v.p _^ 4 0 piia
-gap area
- i*cor>dofy rim seal
seal fabric
gpp area
area
secondary rim seal
HSPS
Gap Measurements
Shoe
or Liquid
Mounted
Primary Seals
10.0 in.' per foot
of tank dtomttK
no gop • 1 '/i In.
Secondary Seals
• 1.0 in.1 p»f foot
ot tank dlanrt*t»(
• no oop > V7 in.
Vopor
Mounted
1 0 In.' p*r foot
of tank dtom»t«<
• no gopi
VARIABLE SPACE TANKS
Liftei
Roof Tank
Flexible
Diaphragm Tank
11-5
-------
VAPOR
RECOVERY SYSTEM
11-6
-------
Chapter 12
VOC Emissions from Gasoline
Marketing Operations
Lesson Goal:
Lesson Objectives:
References:
To introduce you to hydrocarbon control strategies for
gasoline marketing operations, as outlined in the EPA
guideline series.
Upon completion of this lesson, you should be able to:
• Distinguish between and describe the causes of VOC
emissions from
— bulk plants
— bulk terminals
• Describe the RACT requirements for bulk plants and
bulk terminals.
• Describe three types of vapor recovery systems
applicable to bulk terminals
— carbon adsorption
— refrigeration
— incineration
• Distinguish between and discuss Stage I and Stage II
controls for service stations.
• Describe three types of Stage II control systems
— balance
— vacuum
— hybrid
Environmental Protection Agency (EPA). 1977. Control
of Hydrocarbons from Tank Truck Gasoline Loading
Terminals. Guideline Series. EPA-450/2-77-OS6.
Environmental Protection Agency (EPA). 1977. Control
of VOC from Bulk Gasoline Plants. Guideline Series.
EPA-450/2-77-035.
Environmental Protection Agency (EPA). 1978.
Hydrocarbon Control Strategies for Gasoline Marketing
Operation. EPA-450/3-78-017.
12-1
-------
imported B***1*
GASOUNE MARKETING
Bulk Terminal
• daily throughput > 20,000 gal
Bulk Plant
• daily throughput < 20,000 gal
Service Station
EMISSIONS FROM GASOUNE MARKETING
Terminals
Plants
Service
Stations
Number
1,925
23367
184,000
Typical
Capacity
250,000 gal/day
5,000 gjl/day
1300 gal/day
10,000 gal /tank
HC Emissions
(total)
690,000 ton, year
200,000 ton year
530,000 ton/year
TYPES OF LOADING
• Splash Loading
• Submerged Loading
• Bottom Loading
SPLASH LOADING
Vapor Emissions
12.0 lb/103 gal
or
1.4 kg/1031
12-2
-------
SUBMERGED FILL PIPE
V . '.'.
• •' ' •
'•.'/.'
'/.-;/;
L-
~~ , •
',' t /.'••''••*•
>•«*.•;:•:.•:•;
i. •.'. ' •• .-•> '
: \' • • \ - .•
Vapor Emissions
ao lb/103 gal
balanced
or
5.0 lb/103 gal
normal
BOTTOM LOADING
Vapor Emissions
8.0 lb/103 gal
balanced
or
| 5.0 lb/103 gal
1 -j normal
RACT
(for Bulk Terminals)
Vapor Recovery/Control System
• emission limit of 0.67 fc/10' gal
• no leaks in vapor collection system
during operation
12-3
-------
TYPES OF VAPOR CONTROL SYSTEMS
• Carbon Adsorption
• Compression - Refrigeration - Absorption
• Refrigeration
• Compression - Refrigeration - Condensation
• Thermal Oxidizer
£$•:,.. Splash
1331 fb/gal 10s ..>£.*•;... 1X0 lb/103 gal
•'*••'•
ALTERNATIVE I .^jV^vV-
Submerged Fill ':--.'£&?'
f.-W:
WV*:
^ j> >x
Total Reduction = 27%
ALTERNATIVE II ..>;..;.-.
Submerged •W-y'/'.'i':':.
ft* i . •»•.*.;•.•
nil plus partial ••-••;'-'•-'••
Vapor Balance ''^l
Total Reduction = 64%
ALTERNATIVE III
Submeiged fill plus Complete Vapor Balance
/^V^
SB—u^ ,.>j
Total Reduction = 92%
12-4
-------
STAGE
COAXIAL
CONNECTOR
VAPOR
BALANCE
SYSTEM
STAGE II
12-5
-------
VAPOR RECOVERY NOZZLE
VACUUM
ASSIST SYSTEM
STAGE II
ASPIRATOR ' '
ASSIST
SYSTEM
(to underground tank
12-6
-------
Chapter 13
The Regulatory Approach
to VOC Control—I
Lesson Goal:
Lesson Objectives:
References:
Emission Inventory
To acquaint you with emission inventory preparation, its
importance in preparing VOC control plans, and the general
methods of preparing VOC emission inventories.
Upon completion of this lesson, you should be able to:
• State the purpose of preparing VOC emission
inventories.
• Identify sources for required or acceptable emission
inventory formats.
• Describe the relationship of the emission inventory to
VOC strategy preparation and Reasonable Further Pro-
gress (RFP) planning and tracking.
Environmental Protection Agency (EPA). 1980. Pro-
cedures for the Preparation of Emission Inventories for
Volatile Organic Compounds. Vol. I, 2nd ed. Research
Triangle Park, NC: U.S. EPA (OAQJPS, MDAD).
EPA-450/2-77-028.
Environmental Protection Agency (EPA). 1979. Pro-
cedures for the Preparation of Emission Inventories for
Volatile Organic Compounds. Vol. II. Research Triangle
Park, NC: U.S. EPA (OAQPS, MDAD).
EPA-450/4-79-018.
Environmental Protection Agency (EPA). 1978. Develop-
ment of an Emission Inventory Quality Assurance Pro-
gram. Research Triangle Park, NC: U.S. EPA (OAQPS).
EPA-450/4-79-006.
Environmental Protection Agency (EPA). 1980. Final
Emission Inventory Requirements for 1982 Ozone State
Implementation Plans. Research Triangle Park, NC: U.S.
EPA (OAQPS, MDAD). EPA-450/4-80-016.
13-1
-------
EMISSION
INVENTORIES
What are the Clean
Air Act requirements
for emission
inventories?
REQUIREMENTS
• Clean Air Act §172(b)(4)
• comprehensive, accurate,
current inventory
What are the
purposes of an
emission
inventory ?
PURPOSES
• plan development
• reasonable further
progress evaluation
13-2
-------
What areas
need to be
inventoried?
AREAS
• nonattaintnent
areas
• significant
sources
All sources must have
emissions quantified.
1] ^^-T^-*: ^_/
^ngClP
Nonattainment
Significant sources must
have emissions quantified.
Attainment
What sources
of emissions
should be
inventoried?
13-3
-------
SOURCES
• sources with potential
for emitting more than
1OO tons/year
• aggregate of sources with
significant total emissions
(accurate accounting is
important)
What information
needs to be
included?
INFORMATION REQUIRED
• enough to be useful in
development of plan
• usually:
• emission points
• type of process
• type and quantity of
emissions
• stack parameters
What year
should the
inventory
be for?
YEAR OF INVENTORY
• consistent with AQ
data used for
development of plan
• usually will be 1977
13-4
-------
What format
should the
inventory be in?
is-re;:-
:&.',"•"
-~^, — •
Diy^ IMXI
--
— —
^
El
f|
-• ^
--^
_-=-T-
- . ^
._ ^JL^IH
±ttJ
FORMAT
• designed for
nonreactive
pollutants
• important
differences
for VOCs
ACTUAL EMISSIONS
Those emissions
(determined by source
test, emission factor.
etc.) which are
physically emitted to
the atmosphere
Allowable
emissions
are the most
stringent of
these three.
VOC SUMMARIES
SOURCE
•tnneRlE&
TMAntrOHIATlOn
II IHMIM.T1TWJ
or rrTHOLEu*
inutSlKIAL
race uses
, " x
~^~~~^
TOTAL VOC tmsAI
»TATIOn*«V *OU«
oos r*on
cts
TOTAL voc emissions tpiow
rtOBILt MJUBCtS
emissions
BAM VC4II
[missions
^-— ;
rROJtCTEO
ALLOWABLE
rnrssions
~ <
..
13-5
-------
EXEMPTED VOCs
42 Federal Register
35314-35316
(July 8,1977)
EXEMPTED VOCs
Negligible Photochemical
Reactivity:
• methane
• ethane
• 1,1,1- trichloroethane
• trichlorotrifluoroethane
Separate inventory for
each nonattainment
pollutant
Regulatory Requirements
• 4OCFR§§51.321-324
• ACROS Users Manual on NEDS
SUMMARY
• CAA § 172 (b)(4) requires
inventories
• comprehensive
• accurate
• current
• Inventory purpose must
be clearly stated
• plan development
• RFP tracking
13-6
-------
Inventory area must
be clearly defined
• nonattainment areas
for Part D purposes
All sources having
significant impact
must be taken into
account
• Year of inventory
must be clearly
associated with data
• Formats
• required by law
and regulation
• should be useful
Expect to read and
ask questions before
applying any
technique on your own
13-7
-------
Federal Register / Vol. 45, No. 142 / Tuesday, July 22, 1980 / Notices
48941
ENVIRONMENTAL PROTECTION
AGENCY
[FRL 1545-7]
Air Quality; Clarification of Agency
Policy Concerning Ozone SIP
Revisions and Solvent Reactivities
AGENCV: Environmental Protection
.Agency [EPA).
ACTION: Notice.
BACKGROUND: This notice is published
under the authority of section 10l(b) and
section 103 of the Clean Air Act. The
notice provides further clarification of a
policy announced in EPA's
"Recommended Policy on the Control of
Volatile Organic Compounds," 42 FR
35314 (July 8,1977) and "Clarification of
Agency Policy Concerning Ozone SiP
Revisions and Solvent Reactivities," 44
FR 32042 (June 4,1979) and 45 FR 32424
(May 18.1980).
DISCUSSION: The previous policy
statements on the control of volatile
organic compounds (VOCs) noted that
despite concerns about their potential
toxicity 1,1,1-trichloroethane (methyl
chloroform) and methylene chloride are
negligibly photochemically reactive and
do not appreciably contribute to the
formation of ozone. Today's statement
expands the list (45 FR 32424) of organic
compounds (VOCs) of negligible
photochemical reactivity to include the
following chlorofluorocarbons (CFC) or
fluorocarbons (FC):
trichlorofluoromethane (CFC-H):
dichlorodifluoromethane (CFC-12);
chlorodifluoromethane (CFC-22);
trifluoromethane (FC-23):
trichlorotrifluoroethane (CFC-113):
dichlorotetrafluoroethane (CFC-114);
and chloropentafluoroethane (CFC-115).
EPA has determined that these
halogenated compounds are no more
photochemically reactive than methyl
chloroform and methylene chloride and
do not appreciably contribute to the
formation of ambient ozone.
Consequently, controls on emissions of
these compounds would not contribute
to the attainment and maintenance of
the national ambient air quality
standards for ozone. EPA cannot
approve or enforce controls on thtse
compounds as part of a Federally
enforceable ozone Stale Implementation
Plan (SIP). EPA will take no action on
any measures specifically controlling
emissions of these compounds which
are submitted by the States as ozone SIP
measures for EPA approval. (See 45 FR
32424.)
However, EPA would like to reiterate
its continuing concern over the possible
environmental effects from emissions of
these compounds. As such, EPA is not
precluding the possible future regulation
of these compounds.
It should be recognized that the two
halogenated compounds, methyl
chloroform and CFC-113. stated to be of
negligible photochemical reactivity in
the July 8,1977 Federal Register, have
been implicated in the depletion of the
stratospheric ozone layer. This layer is a
region of the upper atmosphere which
shields the earth from harmful
wavelengths of ultraviolet radiation that
increase the risk of skin cancer in
humans. /
In response to this concern, the
Agency promulgated oji March 17,1978
(43 FR 11318), rules under the Toxic
Substances Control Act (TSCA) to
prohibit the nonessential use of fully
halogenated chlorofluoroalkanes as
aerosol propellants. Restrictions were
applied to all members of this class,
including CFC-113, since they are
potential substitutes for CFC-11, CFC-
12, CFC-114, and CFC-115. which are
currently used as aerosol propellants.
The Agency is investigating control
options and substitutes for
nonpropellant uses.
EPA has proposed new source
performance standards under Section
111 for organic solvent cleaners (45 FR
39766, June 11,1980). These proposed
standards would limit emissions of the
reactive volatile organic compounds
trichloroethylene and perchloroethylene
as well as methyl chloroform, methylene
chloride, and trichlorotrifluoroethane
(CFC-113) from new, modified, or
reconstructed organic solvent
degreasers. If these standards are
promulgated, EPA will develop a
guideline document for States to ust hi
developing regulations required under
Section lll(d) for existing organic
solvent cleaners that use any of the
designated compounds.
Whether, and to what extent, methyl
chloroform and melhylene chloride are
human carcinogens or have other toxic
effects, and to what extent methyl
chloroform. CFC-113, and other CFCs
deplete the ozone layer, are issues of
considerable debate. Detailed health
assessments of methyl chloroform,
methylene chloride, and CFC-113 are
being prepared by EPA's Office of
48942
Research and Development. These
assessments will be submitted for
external review, including a review by
the Science Advisory Board, prior to
promulgation of the regulations and the
proposal of EPA guidance to States for
developing existing source control
measures. The extent to which the
preliminary findings are affirmed by the
review process may affect the final
rulemaking for new as well as existing
sources.
Until these issue»of environmental
impact are fully resolved, EPA remains
concerned that if these chemicals are
exempted from regulation, the
substitution of exempt for nonexempt
solvents cculd result in large increases
of emissions of pollutants that may have
adverse health impacts.
The emissions of CFC-22 and FC-23,
also of relatively low photochemical
reactivity, are of continuing concern
with regard to possible environmental
effects. Consequently, EPA is not
precluding the possible future regulation
of these compounds as well.
Finally, EPA wishes to point out that
this notice addresses only the Agency's
lack of authority to include in Federally
approved SIPs controls on substances
whose emissions do not contribute,
either directly or indirectly, to
concentrations of pollutants for which
NAAQS have been established under
Section 109 of the Act. This policy notice
does not address the question of SIP
measures which, control substances
contributing to concentrations.of
pollutants for which NAAQS have been
established, but which are contended to
be more strict than absolutely necessary
to attain and maintain the NAAQS. EPA
has no authority to exclude such
measures from SiPs.
FOR FURTHER INFORMATION CONTACT:
C. T. Helms, Chief, Control Programs
Operations Branch (MD-15). Research
Triangle Park, North Carolina 27711,
(919) 541-5226, FTS 629-5228.
Dated: July 16.1980.
David G. Hawkins.
Assistant Administrator for Air. Noise, and
Radiation.
(FR Doe. 60-219*1 Filed 7-Z1-ME £43 am)
BILUNO CODE &MO-01-M
13-8
-------
SUMMARY FORMAT FOR VOC
tOURCE
PETROLEUM REFINERIES
STORAGE TRANWyRTATIpN
• MARKEtlNC OF PETROLEUM
PRODUCTS
INDUSTRIAL PROCESSES
INDUSTRIAL SURFACE
iOATING
NON-INDUSTRIAL SURFACE
COATINGS
OTHER SOLVENT USE
OTHER MISCELLANEOUS
REFINERY FUGITIVES Illlkll
MISCELLANEOUS SOURCES
•I Proctu Drami «nd Witu
b] Vacuum Producing Sv»t«ms
cl Proc*H Unit Slowdown
OTHER
OIL t GAS PRODUCTION FIELDS
NATURAL GAS AND NATURAL
GASOLINE PROCESSING
PLANTS
GASOLINE & CRUDE OIL STORAGE*
SHIP AND BARGE TRANSFER OF
GASOLINE & CRUDE OIL
BULK GASOLINE TERMINALS J
GASOLINE BULK PLANTS3
SERVICE STATION LOADING llUOI II
SERVICE STATION UNLOADING (ttag* II)
OTHER
ORGANIC CHEMICAL MANUFACTURE
PAINT MANUFACTURE
VEGETABLE OIL PROCESSING
PHARMACEUTICAL MANUFACTURE
PLASTIC PRODUCTS MANUFACTURE
RUBBER PRODUCTS MANUFACTURE
TEXTILE POLYMERS MANUFACTURE
OTHERS
LARGE APPLIANCES
MAGNET WIRE
AUTOMOBILES
CANS
METAL COILS
PAPER
FABRIC
METAL FURNITURE
WOOD FURNITURE
FLAT WOOD PRODUCTS
OTHER METAL PRODUCTS
OTHERS
ARCHITECTURAL COATINGS
AUTO REFINISHING
OTHERS
DECREASING
ORY CLEANING
GRAPHIC ARTS
AOHESIVES
CUTBACK ASPHALT
OTHER SOLVENT USE
FUEL COMBUSTION
SOLID WASTE DISPOSAL
FOREST. AGRICULTURAL, AND OTHER
OPEN BURNING
TOTAL VOC EMISSIONS FROM STATIONARY SOURCES
HIGHWAY VEHICLES
•) Li0tt Duty Automobiles
bl Lilht Duty Truck!
«> Huvy Duty Onolliw Truck!
<) Hwry Duty DMMl Truck!
•) MotorcyclM
OFF-HIGHWAY VEHICLES
RAIL
AIRCRAFT
VESSELS
TOTAL VOC EMISSIONS FROM MOBILE SOURCES
TOTAL VOIATM.E ORGANIC (MISSIONS
BASE VEAR
EMISSIONS
•77
IM2 IIM7I PROJECTED ALLOWABLE EMISSIONS
EMISSIONS FROM
SOURCES EXISTING
INIS77
GROWTH SINCE
1*77
OTAL
J
i ««clMtto! ««pt tarn M HNIM ttrtgm and bulk plum.
13-9
-------
Chapter 14
Liquid Asphalt
Lesson Goal:
Lesson Objectives:
References:
To illustrate the reductions in VOC emissions that result
from changing from cutback asphalt to water-emulsified
asphalt.
Upon completion of this lesson, you should be able to:
• Define cutback asphalt.
• List three types of cutback asphalt.
• Describe how an emulsified asphalt is produced.
• Recall the VOC emissions from solvent-based cutback
asphalt.
• Recall the VOC emissions from emulsified asphalt.
• Recall the relative costs of producing cutback and
emulsified asphalt.
Environmental Protection Agency (EPA). 1977. Control
of Volatile Organic Compounds from the Use of Cutback
Asphalt. EPA-450/2-77-037.
The Asphalt Institute. 1979. A Basic Asphalt Emulsion
Manual. College Park, MD: Manual Series No. 19
(MS-19).
14-1
-------
LIQUID ASPHALT
Binder
CUTBACK ASPHALT
Asphalt
RAPID CURE MEDIUM CURE SLOW CURE
14-2
-------
LIQUID ASPHALT USES
Prime Coat
Tack Coat
Pavement Sealers
Surface Treatment
Road Mixing in Place
Blade Mixing
Cold Mix - Patch
Mulch Treatment
Pavement Sealers
SURFACE TREATMENT
Aggregate ^
Spreader/
ROAD MIXING IN PLACE
Travel Plant
14-3
-------
BLADE MIXING
COLD MIX - PATCH
MULCH TREATMENT
EMISSION FACTOR -
SOLVENT EVAPORATED
Average
Rapid Cure 80%
Medium Cure 70%
Slow Cure
25%
EXCEPTIONS
• cold weather < 50' f
• stockpile storage longer than
one month
• prime coat
• demonstration of no VOCs
from cutback
14-4
-------
Chapter 15
The Regulatory Approach
to VOC Control—II
Regulatory Strategies for NAAQS Attainment
Lesson Goal:
Lesson Objectives:
References:
To describe the function of VOC regulations in plans for
meeting the oxidant standard in nonattainment areas.
Upon completion of this lesson, you should be able to:
• Describe in general terms the process for developing
emission control regulations for a nonattainment area
from ambient air quality data and emission
information.
• Identify the role of the New Source Review (NSR) pro-
cess in attaining and maintaining the ozone standard.
• Explain the relation of Reasonable Further Progress
(RFP) tracking to the other elements of the nonattain-
ment area SIP.
• State the authoritative sources of guidance concerning
Reasonably Available Control Technology (RACT).
Environmental Protection Agency (EPA). 1979. Guideline
for Interpretation of Ozone Air Quality Standards.
EPA-450/4-79-OOS.
Environmental Protection Agency (EPA). 1979. Example
Control Strategy for Ozone, Volume 1: General Guidance
for Nonattainment Areas. EPA-450/2-79-001a.
Environmental Protection Agency (EPA). 1979. Example
Control Strategy for Ozone, Volume 2: Case Study of the
San Francisco Bay Region. 1976-1978.
EPA-450/2-79-001b.
Environmental Protection Agency (EPA). 1977. Uses,
Limitations, and Technical Bases for Procedures for
Quantifying Relationships Between Photochemical
Oxidants and Precursors. EPA-450/2-77-021a.
15-1
-------
200,000
90,000
1979
REGULATORY
STRATEGIES
FOR NAAQS
ATTAINMENT
1987
DETERMINING REQUIRED
EMISSION REDUCTIONS
1. Establish baseline air quality
X Establish baseline emission
inventory
3. Apply models
4. Calculate required reductions
1. Establish baseline air quality
Averaging Tune:
• inherent in all measurement
methods and models
• must be compatible
1. Establish baseline air quality
Design value:
• concentration that should be
reduced to standard
• ozone — expected exceedances
equal to 1
• from current, consistent, reliable
AQdata
2. Estabish baselne emission inventory
1977 or
most recent
inventory
HC
H.I.K .—1 i*. ,«.(..
alt elements
in consistent
measurements
15-2
-------
• do not "grow"
inventory
credit reductions
in El
Emission Inventory
200,000
90,000
Air Quality
28ppm
.12ppm
1979 1987
• target will be % reduction
3. Apply models
Bask Principles
• select best model for specific
pollutant
• select best model consistent with
available resources
• apply model accurately
• model cannot be more accurate
than available data
SELECTING BEST MODEL
m
Photochemical
Dispersion
EKMA
Rollback
• data • money/ • levels of
personnel analysis
SaECTlNC CONSISTENT MODEL
Sophisticated Models
• extensive • money/ • detailed
computer personnel input data
time
15-3
-------
Agency Resource Limitations
little access • limited • uncertain or
to advanced personnel, aggregated
computer money, time data
APPLYING MODEL ACCURATELY
• Overestimation
Underestimation
MODELING POINTS
• critical computational step
• potentially expensive
• results are no better than quality
and control of data
4. Calculate required reductions
AQ.,,i, - •
24 - 5 (.04)
.12
— =»•
Emission Inventory
90,0001
Air QuaEty
28ppm
12ppm
W79 1987
• target will be % reduction
15-4
-------
Control H»°-12 PPm ^3
1. Determine design AQ value
2. Adjust for background and transport
3. Enter AQ data into rollback equation
4. Calculate overall required reductions
1. Determine design AQ value
2. Adjust for background and transport
• Additiviry (A) 20% - 70%
• Natural Background .02 - .06 ppm
• Manmade Background
• Reducible Transport (TR)
• Adjusted Air Quality (AQjdj)
• Calculating reducible transport
TR = TO •" TF
• Calculating adjusted air quality
AQadj = AQdes - A' TR
15-5
-------
AQdes-A-TR =AQadj
28 -5 (.12-.04) = 24
3. Enter AQ data into rollback equation
- A-T
34 - .12
24 - 3 (04)
'•= = 55% reduction
4. Calculate overall required reductions
baseline
200,000
R
-------
I. REQUIREMENTS
A. SECTION 172 (b) (2) OF THE CLEAN AIR ACT
11. APPLICABILITY OF DISCUSSION
A. RACT
B. STRINGENT BUT REASONABLE MEASURES
RACT
"THE LOWEST EMISSION LIMIT THAT A
PARTICULAR SOURCE IS CAPABLE OF
MEETING BY THE APPLICATION OF
CONTROL TECHNOLOGY THAT IS
REASONABLY AVAILABLE CONSIDERING
TECHNOLOGICAL AND ECONOMIC FEASIBILITY-
MI. DEFINITION OF RACT
A. TECHNICALLY FEASIBLE
B. ECONOMICALLY FEASIBLE
C. APPENDIX B, 40 CFR PART 51
DOES NOT REPRESENT RACT
IV. TECHNOLOGICAL FEASIBILITY
A.STRINGENT.EVEN
"TECHNOLOGY FORCING"
B.SIMILARITY OF SOURCES
V. ECONOMIC FEASIBILITY
A. SOURCE SPECIFIC
B. ECONOMIC WEIGHING OF BENEFITS
C. PRESENT VALUE ANALYSIS
15-7
-------
REVIEW
NSR
* COMPLEMENTARY DRIVING FORCE
ADDITIONAL CLEAN UP
NEW TECHNOLOGY DEVELOPMENT
* CONSISTENT WITH RFP
* INSTANTANEOUS "WATCHDOG"
RFP AND ATTAINMENT
PART D NSR REQUIREMENTS
1979 PLAN MUST:
1. ATTAIN ON TIME - AVOIDS SANCTIONS
2. IDENTIFY ALLOWABLE GROWTH
3. CONTAIN NSR REGULATIONS
*LAER (as defined)
^STATEWIDE COMPLIANCE
*2 OPTIONS ~ un-by-cnt offsets
accomodative SIP
*SIP CARRIED OUT
POST '82 ATTAINMENT
4. CONTAIN NSR EVALUATION PROGRAM
REGULATORY NSR REQUIREMENTS
LOWEST ALLOWABLE EMISSION RATE (LAER)
#171 Dfffinition
* tat SIP
* In Practice
* NSPS Minimum
STATEWIDE COMPLIANCE
-A1 COMPLIANCE BY APPROVAL
* APPLICABILITY
Existing SIP Limits
* MAJOR EXISTING SOURCES
15-8
-------
NEW SOURCE REVIEW OPTION
(ose-by-cos*
offsets
J
occoModative
SIP
REASONABLE
FURTHER
PROGRESS
RFP
Part D Requirements
171(1) Definition
• Annual Incremental Reductions
• Substantial Early Reductions — Regular thereafter
• Provides for Attainment
172(b)(3) Plan Requirements
• Require RFP including RACT
MSI '12 SIP'S / ItCKUTE IFF
!•?» M SI I!
• I •• «7 M
RFP TRACKING
3 MECHANISMS
• annual emission trends
•Ad trends qualitative
• NSR Instantaneous
15-9
-------
AFP SCHEDULES
I "
'Linear Prismption
1979 Submittals optimal
Later revision as necissarj
1912 tttiiMMts
{all
I|PI ll IIF IcIlUll
SUMMARY
• need for attainment
plans for nonattainmenl
areas
• Determining required emission
reductions
• baseline air quality
• baseline emission inventory
• air quality modeling
• calculation of reductions
Obtaining emission
reductions
• RACT — existing sources
• NSR — new or modified sources
• LAER
15-10
-------
• Reasonable further
progress requirements
• annual incremental reductions
• annual tracking reports
Bask goal
• attaining and maintaining
the ozone NAAQS
15-11
-------
Chapter 16
Methods of VOC Emission
Control—Incineration
Lesson Goal:
Lesson Objectives:
References:
To provide you with an understanding of the basic con-
cepts of incineration and heat recovery as they apply to
VOC control.
Upon completion of this lesson, you should be able to:
• List three methods used to incinerate VOCs
• Identify the conditions necessary for efficient combus-
tion of organic materials in a direct flame
incinerator—including the effect of gas conditioning,
temperature, and residence time.
• Explain the operation of at least two types of direct
flame incinerators—including the purpose of baffles,
multijets, and distributed burners.
• Identify the conditions necessary for the efficient com-
bustion of organic materials in catalytic incinerators—
including the effect of catalysts, temperature, residence
time, etc.
• Discuss the advantages and disadvantages associated
with catalytic incineration.
• Discuss the problems inherent hi using process boilers
for incineration.
• Diagram at least two types of methods used for heat
recovery.
• Discuss the advantages, problems, and limitations
associated with primary and secondary heat recovery.
• Discuss the factors (including relative cost) to consider
when determining what type of heat recovery system to
use.
• List several sources of VOC emissions that would most
likely use incineration as a method of VOC control.
National Technical Information Services (NTIS). 1972.
Afterburner Systems Study. PB-212 560.
Environmental Protection Agency (EPA). 1977. Con-
trolling Pollution from the Manufacturing and Coating of
Metal Products. Metal Coating Air Pollution Control.
Technology Transfer Publication. EPA-625/S-77-009.
16-1
-------
DIRECT FLAME INCINERATION
Fum*
Fuel
Exhouit
"
o
i
EFFECTS OF
TEMPERATURE AND
TIME ON RATE OF
POLLUTANT OXIDATION
400 tOO 1000 1200 1400 1600 1400 2000
Increasing T»mp»ratur«
TYPICAL AFTERBURNER
OPERATING TEMPERATURES
1200°-1500°F
'H000-1500°F
1300°-2000°F
1300°-1500°F
Wire Enameling 1300°- 1400°F
Coil
Paint Dake Ovens
Petroleum Refining
DESIGN RANGES
Temperature 1300 ° - 1500° F
Detention 0.3 - 0.5 seconds
Time
THERMAL DESIGN FACTORS
Efficiency increases withi
• operating temperature
• detention time
• Initial hydrocarbon concentration
• flame/solvent contact
• good mixing
• CO removal
(at temperatures >1000°F)
16-2
-------
CATALYTIC INCINERATION
Diffusion
(bi
Adsorption
PRINCIPLES OF
OPERATION
Reaction
Desorption
Diffusion and
Mixing
ADVANTAGES OF
CATALYTIC INCINERATION
• lower operotingjemperotures
• lower ouxilory fuel needs
• lower construction materials cost
DISADVANTAGES OF
CATALYTIC INCINERATION
• partlculate fouling
• thermal aging
• catalyst poisoning
• suppressants
PLATINUM
CATALYST POISONS
Fast
P
Dl
As
Sb
Hg
Slow
Zn
Pb
Sn
High Temp.
( >1100°F)
Fe
Cu
16-3
-------
PLATINUM
CATALYST SUPPRESSANTS
•Sulfur
• Halogens
action is reversible
PROCESS
BOILERS
CONDITIONS FOR INCINERATION USE
• sufficient residence time
• no dependency
• low fuel/oxygen rat*
• unaltered flame and radiation patterns
• non-fouling or add fumes
Catalyst. If any
Contaminated Vaste Gat
To
^Atmosphere
Afterburner
I Process
AFTERBURNER CONFIGURATION
WITHOUT HEAT RECOVERY
AFTERDURNER CONFIGURATION
WITH PRIMARY HEAT RECOVERY
16-4
-------
Afterburner
Recycle Heoi Recovery
To Atmosphere
AFTERBURNER CONFIGURATION WITH
PRIMARY HEAT RECOVERY
AND DIRECT RECYCLE HEAT RECOVERY
Primary Heat
Recovery
^^^^^ I Afterburner
•Processi I AFTERBURNER CONFIGURATION
VHBf I WITH PRIMARY AND SECONDAP
^^^ Y HEAT RECOVERY
Sccondar
H«ot Recovery
To Atmosphere
RECUPERATIVE
HEAT
RECOVERY
DEVICE
REGENERATIVE
HEAT
RECOVERY
DEVICE
(Reeco)
Hmtocavwy
Fum*s From
TUDULAR HEAT EXCHANGER SYSTEMS
' Effectiveness ratio, E
1. Stage SOX mox.
2. Stag* 62 X max.
3. Stage 83X mox
Limitation
Easily fouled
Structural failures
Cherrtcol Interactions with fume components
Corrosion
16-5
-------
AFTERBURNER PROCESS HEAT RECOVERY
-1JOO°f
I..
MOTE, Final T»mp»ratur»
of Hu» 001 = 350° F
Fum* strcom used for
oxygen supply
12,000
4.000 EOOO 12,000 16.000
Aft»rborn«r Capacity,tcfm
CAPITAL COST OF INCINERATION
• Thermal • Catalytic
-Vlthoul (xchangif
10 13 20
Flow, 5cfm x 10a
30
ANNUAL VARIABLE COST OF INCINERATION
243 I
Thermal • Catalytic
• Without Mttlionon
.—— Vlth (xlmoiy <
._._._ vith pamaiy and.
10 19 20
Flow.srfm x 10 a
16-6
-------
Chapter 17
Methods of VOC Emission
Control—Adsorption
Lesson Goal:
Lesson Objectives:
References:
To provide an understanding of the basic concepts of car-
bon adsorption as applied to VOC control.
Upon completion of this lesson, you should be able to:
• Define the following terms as they apply to the adsorp-
tion process: adsorption, adsorbent, adsorbate, activa-
tion, build-up, retentivity, regeneration and
breakthrough.
• Explain, with the aide of suitable diagrams, the
dynamics of the adsorption process.
• Explain the relative effects of temperature, gas velocity,
preferential adsorption, concentration, bed depth,
pressure, and paniculate matter on the adsorption
process.
• Diagram a regenerative adsorption system and list three
problems associated with the recovery process.
• Summarize the exhaust gas stream conditions under
which effective adsorption occurs.
Bethea, R. Air Pollution Control Technology. 1978.
Chapter 13. New York. Van Nostrand Reinhold Co.
Environmental Protection Agency (EPA). 1973. Packing
Sorption Device System Study. Washington, DC. EPA-
RZ-73-202.
Parmele, C. S., O'Connell, W. L. and Basdekis, H. S. 1979.
Vapor Phase Adsorption Cuts Pollution Recovers Solvent,
Chemical Engineering. 82:58-71.
17-1
-------
ADSORPTION
~rasatw-~~
TYPES OF
ADSORBENTS
• activated carbon
• molecular sieves
• silica gels
&/)
VAN DER
WAAL
FORCE
molecule
adsorbate V
molecules in
adsorbent
wall
wall of
absorbent
;-V-7Y CU
v/ ^ / r
17-2
-------
RETENTIVITY
Temperature
TYPICAL ADSORPTION
M ISOTHERM
i100
1
20
77 op
0.001 0.01 0.1 1.0
Partial Pressure, psla
»>
I
I
Surface Area
Molecular Weight of Solvent
17-3
-------
Adtorbtion Zone Saturated Bed
BED
GEOMETRY
EFFECT OF GAS VELOCITY
EFFECT OF BED DEPTH
0 10 20 30 40 50
Bed Depth, inches
MULTIPLE SOLVENTS
Decreasing ^^^^^^^ ~ , A
Muy ^^^^^^H Compound A
•^^H^^B^^^B^^^^ml
Compound B
Compound C
I
17-4
-------
HUMIDITY
/OC
45% - maximum relative humidity
'
-------
REGENERATIVE CYCLE
Condenser
Solvent
ADSORPTION CYCLE
Condenser
V - SHAPED
BED
—— Housing
— Carbon
-------
ROTARY BED
Steam And Vapor Out
REGENERABLE
Fluidized Bed
APPLICATIONS
• Coating Operations
• Degreasing Operations
• Gasoline Marketing
• Odor Control
ADSORPTION
• 90%+ efficiency
• Handles high VOC concentrations
• Humidity > 45% decreases efficiency
' Design problems with VOC mixtures
• Higher MW compounds adsorbed
more readily
17-7
-------
Chapter 18
The State VOC Control
Program—an Example
18-1
-------
18-2
-------
18-3
-------
Chapter 19
Homework Problems
19-1
-------
U1
Problem Set 1—Coating Calculations
A captive can coater roller-coats sheet stock to prepare cans for a food processing
plant. As a result of recent changes in the State Implementation Plan (SIP), he is
now required to meet RACT emission limits of 2:/79Jbs VOCs/gallon of coating
(minus water) for the interior base coat.
Part A
If the coater presently uses a rosin ester containing 35% by volume of solids
(remaining content organic volatiles) for the interior base coat, compute the
following: ^fYo
1. the present-emissions (Ibs VOCs/gallon coating (less water)).
2. the emissions (Ibs VOCs/gallon coating (less water)) if the coating formulation
for the interior base coat was changed to a water borne coating containing
50% solids with an 80:20 (80% water, 20% organics) water borne solvent.
3. the percent VOC reduction realized.
Assume a VOC solvent density of 7.36 Ibs/gallon.
Hint: Use Figure 1 and Figure 2 for this part of the problem.
Answer #1 = ^ ' / 1h«/ga11on
Answer #2 = Ibs/gallon
Answer #3 =.
19-2
-------
-77%
PartB
If a can coater presently uses a tt% so]ids hy vnlnmp polyester resin for an exterior
base coat with a 60^40 water borne solvent (60% water, 40% organics), compute
the following:
1. the present emissions (Ibs VOCs/gallon coating (less water)), (assume solvent
density to be 7.36 Ibs/gallon).
2. the emissions (Ibs VOCs/gallon coating (less water)) if the coating formulation
for the exterior base coat was changed to 80% solids in a 70:30 water borne
solvent (70% water, 30% organics). In this case, the density of the organic
solvent was not 7.36 Ibs/gallon, but had a value of Tjt&Jbs/gallon.
3. the percent VOC reduction realized.
Hint: Use the calculation methods given in the "Coating Calculations" discussion
which follows.
, /
w" •
Answer #1 /«£/
Answer #2.
Answer #3
VOC/gal coating (less HZO)
Ihs VOC/gal coating (less H2O)
-------
20 40 60 80
Volume % solids in coating
Figure 1. Weight of organic solvent per gallon for 3 coatings as a function of solids content.
Solvent content of
oriemai coating
1234567
*7 Aw ^e>Vi€*vC' Pounds of solvent per gallon of replacement coating (less water)
Figure 2. Percent VOC emission reduction using replacement coatings.
(Solvent density a 7.36 Ib/gal)
19-4
-------
Coating Calculations
This discussion provides assistance in working Problem Set 1 . It reviews methods of
farforg for coatings in terms of the RACT units: Ibs
VOC/(gallon coating applied— H20). The purpose of excluding water is to avoid
the problem of achieving compliance merely by diluting the paint. Another method
of describing VOC emissions from a coating formulation is on the basis of Ibs
VOC/gallon solids. If the surfajcp ?rea of the material being coated is koQwji and if
the dry coating thickness can be determined, the amount of VOCs emitted can
easily be determined by finding fhe flum,ber pf gallons of solids that would give the
a^y fflYfjagf— The analytical methods of measuring the volume ot cured
coating can be complex. As an alternative, the RACT limits were developed in
terms of Ihs J/OCjej gallpn of uncured solvents and organic solvent less water.
Two methods for calculating emissions in terms of RACT units (Ibs
VOCs/ (gallon coating— HZ0)) are presented in Problem Set 1. The first method
uses Figure 1 . Figure 2 enables you to calculate percent reductions realized by
changing coatings. Figure 1 assumes that the organic solvent of the coating has a
density of 7.36 Ib/gal (note: this is the density only of the organic solvent, not the
total solvent or the total paint composition). The figure gives only information for
paints of three solvent compositions— an organic borne coating, an 80:20 water
borne coating (80% HZ0) and a 70:30 waterborne coating.
To use the graph, locate the volume % of solids on the x-axis. Draw a vertical
line to the curve which describes the solvent composition (you would have to inter-
polate or develop other curves for compositions differing from the three given).
Draw a horizontal line to the y-axis and read the solvent emissions in terms of Ibs
solvent/(gal— HZ0). Do this for both the presently used coating and the replace-
ment coating.
Figure 2 is used to determine the percent reduction in emissions which will be
realized by going to the replacement coating. To use Figure 2, find the curve cor-
responding to the solvent content of the original coating (you may have to inter-
polate between curves). Next, locate the solvent content in lbs/(gal — H20) of the
replacement coating on the x-axis. Draw a vertical line up to the curve corres-
ponding to the original coating. Locate the point of intersection and then draw a
horizontal line from that point to the y-axis. Read the percent reduction from the
y-axis.
This graphical procedure is given in the CTG: "Control of Volatile Organic
Emissions from Existing Stationary Sources— Volume II," EPA-450/2-77-008, May
1977. The graphs can give you a quick way of determining emission levels and
emission reductions. The graphs were developed from simple mathematical calcula-
tions and are not empirical in nature. In cases where the organic solvent density is
not 7.36 Ibs/ gal, or where it is desired not to interpolate, the mathematical pro-
cedures which follow can be used.
19-5
-------
-v , .- |; A
t *f,c<$ f ^ ^
Part B of Problem I can be solved by using the following expressions:
• Emission factor in RACT units Ibs VOC/(gal-H20).
ef=
1— ws
Where: ef = emission factor Ibs VOC/(gal-H20)
_ % organic volatiles in solvent
v —-
% H20 in solvent
100
% solvent in the paint
s= *•
100
QV = density organic volatiles ( — j.
\ga1-/
• Emission factor on a solids' basis (Ibs VOC/gal solids)
r» Vs6v
et = ——
l-s
Where: ef' = emission factor Ibs VOC/gal solids
• Percent emission reduction
% reduction = ef°'"'~ ef~" iQO
Where: ef^, = emission factor on a solids' basis for original coating
efr'.p = emission factor on a solids' basis for replacement coating
The following examples illustrate the use of these equations:
Example 1: Determine the emission factors, ef and ef', for an organic solvent-
borne coating which contains 40% organic solvent having a density of 7.36 Ibs/gal.
IX.40x7.36
ibs/(gal_H,0)
-ws - V6 '
c, vsgv IX. 40x7. 36
ef ' = — m. = - =
l-s 1-.40
n», ,.,
4.90 Ibs/Wl solids
DT?o.(flU'.c. -Sois^va r *1
u
19-6
-------
Example 2^_Determine the emission factors ef and ef ' , for a waterborne coating
containing fiFffi solvent with 80% of the solvent being water. The density of the
organic portion of the solvent is 7.36 Ibs/gal.
ef=J.gJL=(.20)(.65)(7.36)=_:957_ ^ lbs/(gal_Hj0)
1-ws 1-(.80)(.65) 1-.52
., vsov (.20)(.65)7.36 .957 _ __ „ . , r ,
ef ' = — ^L = .i - ii - L - = - =2.73 Ibs/gal solids
1-s 1-.65 .35
Note here that vs= .20X .65= .13 is the volume fraction of organic solvent in the
gallon of paint and .80 X .65 = .52 is the volume fraction of water in the gallon of
paint.
^B: Calculate the percent reduction in volatile organic emissions
achieved by switching from the coating given in Example 1 to that given in
Example 2.
% reduction =
, 4.90- 2.73
4.90
= 44.3%
Note: This calculation is performed using the emission factor computed on a
solids ' basis. This is done so that we are comparing the same things. A gallon of
paint with 60% solids will cover more surface area (1 mil thick) than will a 35%
solids paint. [If the calculation was performed using the other emission factors
(Ibs/gal— H20), we would just be comparing the reduction of volatiles between
buckets of paint (with water removed). That is, to cover a given surface area 1 mil
thick, we might need 1 bucket of one coating, but using another, 1 Vi buckets. This
factor does not appear in doing the % reduction using ef values.]
19-7
-------
(D
Qtr
'1J-
6
(.A 2,0
0
o. ^ s
<2JUL
-------
Problem Set l__rvi ,
v '-Calculation Sheet
J9-9
-------
Problem Set 1—Coating Calculations
Name.
Date _
Hand in Answer Sheet (to be handed in Wednesday morning)
Part A
Answer #1 =.
Answer #2 =.
Answer #3 =.
Jbs/gallon coating (less H2O)
Jbs/gallon coating (less H2O)
Part B
Answer #1 =.
Answer #2 =.
Answer #3 =.
Jbs/gallon coating (less HZO)
Jbs/gallon coating (less H2O)
19-11
-------
Problem Set 2—Storage Tank Calculations
Problem 2.1
A petroleum refinery has a 60,000 bbl external floating roof tank, equipped with
only a primary shoe seal. The tank is of welded construction.
Compute the following:
1. Present VOC emissions from the tank.
2. VOC emissions after applying RACT (secondary seal).
3. Dollar savings per year (gasoline 90
-------
b. Withdrawal losses
0.943
n
[NOTE: Constant 0.943 has units of (1000 ft3 X gal/bbl2)
Substituting in the given data
, _(0.943)(450,000)(0.0015)(5.6)
*->W — " — — ---- - ,.,..- ---
100
L,v= 36 Ib/yr
c. Total emissions from the tank
LT = Lfc+ Lw
LT= 39,400 + 36
Lr= 39,436 Ib/yr
2. VOC emissions after applying RACT (secondary rim mounted seal)
a. Standing losses
L, = KsV"P*DMKcEf
Now K, is reduced to .2 and n is 1 from Table 2.
U = 2072 Ib/yr
b. Withdrawal loss
Lw=36 Ib/yr
Same as 1-b since the annual throughput doesn't change
c. Total emissions
L,;- = L.J 4- LW
Lr=2072 + 36
Lr=2108 Ib/yr
3. Money saved by applying RACT
39,436 Ib/yr before controls
2,108 Ib/yr after controls
37,328 Ib/yr reduction
37,328 Ib/yr ( J2L V ^^\ = $6000/yr
' \5.6 IbA gal / y
19-14
-------
1
l
Problem 2.2
A chemical plant uses benzene in the manufacture of styrene. They store the
benzene in a small 25,000 gal fixed roof tank. The company plans to install an
internal floating roof with a secondry seal system to reduce the benzene losses.
ComputeThe following. t^oul YYuxMr^ rt£iU«rA M V>«(
1. Present benzene emissions from the tank.
2. The emissions after installing the floating roof.
3. The dollars saved per year assuming benzene is wo.
Data
Tank capacity = 25,000 gal
Tank diameter (D)= 12 ft
Tank height = 36 ft
Annual throughput = 800,000 gal/yr (approx. 19,000 bbl/yr)
Tank i§jaenilally •H iull,"assume a flat roof
painted white
lolecular weight of benzene (M) = 78^b./lb mole
Jensity (Wf)= 7.4 Ib/gal ;
Average wind speed (V) = 8 mph
Cling factor (C) = 0.0015 bbl/1000 ft2
Average daily temperature change (AT)= 18°F
v\
o.M
1
1.2/14.1
0,0
19-15
-------
Problem Set 2—Calculation Sheet
19-16
-------
Problem Set 2—Calculation Sheet, continued
19-17
-------
Lfl=6.19xl(r5 M
Where: LB = Fixed roof breathing loss (Ib/day)
M = Molecular weight of vapor in storage tank (Ib/lb mole)
P = True vapor pressure at bulk liquid conditions (psia)
D = Tank diameter (ft)
H= Average vapor space height, including roof volume correction
(ft); see note (1)
AT = Average ambient temperature change from day to night (°F)
Fp — Paint factor (dimensionless); see Table 1
A = Adjustment factor for small diameter tanks (dimensionless);
see Figure 5
Kc = Crude oil factor (dimensionless); see note (2)
Note: (1) The vapor space in a cone roof is equivalent in volume to a
cylinder which has the same base diameter as the cone and is
one-third the height of the cone.
(2) Kc = (0.65) for crude oil, Kf-(l. 0) for gasoline and all
other liquids.
Figure 3. Fixed roof breathing loss equation.
Lw= 2.40 X l(T2MPrvvKc
Where: Lw = Fixed roof working loss (lb/103 gal throughput)
M = Molecular weight of vapor in storage tank (Ib/lb mole)
P = True vapor pressure at bulk liquid conditions (psia)
K^ = Turnover factor (dimensionless); see Figure 6
Kc = Same as Figure 3
Figure 4. Fixed roof working loss equation.
From: U.S. Environmental Protection Agency. 1977. Compilation of Air Pollution Emission tutors.
Third Edition. AP-42.
19-19
-------
Table 1. Paint factors for fixed roof tanks
Tank
Roof
White
Aluminum (specular)
White
Aluminum (specular)
White
Aluminum (diffuse)
White
Light gray
Medium gray
color
Shell
White
White
Aluminum (specular)
Aluminum (specular)
Aluminum (diffuse)
Aluminum (diffuse)
Gray
Light gray
Medium gray
Paint factors (Fp)
Paint condition
Good Poor
1.00 .15
1.04 .18
1.16 .24
1.20 .29
1.30 .38
1.39 .46
1.30 .38
1.33 .44"
1.40 1.58"
"Estimated from the ratios of the seven preceding paint factors.
1.00
u
a
i
•o
.20
10 20
Tank diameter in feet
Figure 5. Adjustment factor (A) for small diameter tanks.
19-20
-------
1.0
I
u
-------
Where: Lj = standing storage loss (Ib/yr)
Ks = seal factor (Ib mole/[ft(mi/hr)"yr]) See Table 2
V = average wind speed (mi/hr)
n = seal-related wind speed exponent (dimensionless) See Table 2
P* = vapor pressure function (dimensionless)
P
(K)
1+1
P = true vapor pressure at average stock storage temperature (psia)
P,, - average atmospheric pressure at tank location (psia)
D = tank diameter (ft)
M = average molecular weight of stock vapor (Ib Ib mole)
Kc = product factor (dimensionless) see Note 1
Ef = Secondary seal factor dimensionless see Note 2
Note: (1) Petroleum liquids are defined as mixtures of chemicals having dissimilar
true vapor pressures (gasoline or crude oil). Volatile organic liquids are
defined as mixture of chemicals with similar true vapor pressures
(benzene or a mixture of isopropyl and butyl alcohols).
Kc = (0.4) for crude oil
Kc = (1.0) for all other petroleum liquids
Kc = (10.0) for volatile organic liquids
(2) EF = (1.0) for all petroleum liquids, E/=(1.0) for all (volitilejorganic
liquids with only a primary seal, V-
Ef = (0.25) for volatile organic liquids with a primary and secondary seal
system. However when selecting values of K5 and n from Table 2, one
must use the primary only values.
Figure 7. Standing losses from external floating roof tank.
19-22
-------
L,= K.V"P*DMKeEjr
Where: the terms are defined the same as Figure 7, except:
K,= 0.7 for all seal systems
Kc = same as Figure 7
n = 0.4 for all seal systems
EF = 1.0 for the storage of any liquid that has only a primary seal system on the
tank
Ejr= 0.25 for storage of any liquid that has both a primary and secondary
seal system on the tank
Figure 8. Standing losses from an internal floating roof tank.
D
Where: Lw = withdrawal loss (Ib/yr)
Q= average throughput (bbl/yr)
C = shell clingage factor (bbl/1000 ft2) see Table 3.
Wf = average stock liquid density (Ib/gal)
D = tank diameter (ft)
[NOTE: Constant 0.943 has units of (1000 ft3Xgal/bbl2)
Figure 9. Withdrawal losses from both internal and external floating roof tanks.
From: American Petroleum Institute (API). 1980. Evaporative Losses from External Floating Roof
Tanks. Second Edition. API 2517.
19-23
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Table 2—Summary of average seal factor (KJ and wind speed exponents (n)
Tank/seal type
K
Welded tanks
1. Mechanical shoe seal
a. Primary only
b. Shoe-mounted secondary
c. Rim-mounted secondary
2. Liquid-mounted resilient filled seal
a. Primary only
b. Weather shield
c. Rim-mounted secondary
3. Vapor-mounted resilient "filled seal
a. Primary only
b. Weather shield
c. Rim-mounted secondary
Riveted tanks
a. Mechanical shoe primary only
b. Shoe-mounted secondary
c. Rim-mounted secondary
1.2
0.8
0.2
1.1
0.8
0.7
1.2
0.9
0.2
1.3
1.4
0.2
Table 3. Average cling factors (C)
(bbl/1000 ft,)
Product
Gasoline
Crude Oil
Shell conditions
Shell Conditions
Light rust
0.0015
0.0060
Dense Rust
0.0075
0.030
Gunite-lined
0.15
0.60
19-24
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Problem Set 2.2—Storage Tank Calculations
Name_
Date
Hand in Answer Sheet (to be handed in Thursday morning)
VOC emissions from fixed roof tank
VOC emissions from fixed roof tank after installing internal
floating roof
Money saved
19-25
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA 450/2-81-011
3. RECIPIENT'S ACCESSION>NO.
4. TITLE AND SUBTITLE
APTI Course 482
Sources and Control of Volatile Organic Air Pollutants
Student Workbook
5. REPORT DATE
Ma-rrVi 1 Qftl
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
D.S. Beachler, J,A. Jahnke, J.T. Joseph
J.E. Maroney
8. PERFORMING ORGANIZATION REPORT NO
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Northrop Services, Inc.
P.O, Box 12313
Research Triangle Park, NC 27709
10. PROGRAM ELEMENT NO.
B18A2C
11. CONTRACT/GRANT NO.
68-02-2374
12. SPONSORING AGENCY NAME AND ADDRESS
U.S. Environmental Protection Agency
Manpower and Technical Information Branch
Air Pollution Training Institute
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
14. SPONSORING AGENCY CODE
EPA - OANR-OAQPS
15. SUPPLEMENTARY NOTES
Project Officer for this workbook is R,E, Townsend, EPA-ERC, MDr-17, RTF, NC 27711
16. ABSTRACT
The Student Workbook is to be used for the Air Pollution Training Institute
Course 482, "Sources and Control of Volatile Organic Air Pollutants", This publica-
tion contains chapters corresponding to each of the eighteen lessons and a chapter
containing two problem sets. Each chapter contains a lesson goal, lesson objectives
and any special reference that would provide helpful background material for the
subject area covered in the chapter. Each chapter contains important black and white
reproductions of selected slides used in the training course. This publication is
designed to be used as a student aid for the training course.
This publication is intended for use in conjunction with the Instructor's Guide
(EPA 450/2r*81-01Q) and the Regulatory Documents (EPA 450/2^81-012) for APTI Course
482,
7.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b. IDENTIFIERS/OPEN ENDED TERMS |c. COSATI Field/GfOUp
Air Pollution Training
Control of Volatile Organic Compounds
Training Course
Student Workbook
13B
51
68A
8. DISTRIBUTION STATEMENT
National Technical Information Service
5285 Port Royal Road
finrlngfteld. VA 22161
19. SECURITY CLASS (ThisReportf
unclassified
21. NO. OF PAGES
153
20. SECURITY CLASS (This page)
unclassified
22. PRICE
EPA Form 2220-1 (>-73)
19-27
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