«>EPA
United States Industrial EP. il I earcl EPA 600 7 78 1 75
Environment,)! Prou-it.nr L.itm'.i' •. September 1978
Ageru , R< eai I ' • n . • •' r - \.
Environmental
Assessment for
Residual Oil
Utilization -
Second Annual Report
Interagency
Energy/Environment
R&D Program Report
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7. Interagency Energy-Environment Research and Development
8. "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the INTERAGENCY ENERGY-ENVIRONMENT
RESEARCH AND DEVELOPMENT series. Reports in this series result from the
effort funded under the 17-agency Federal Energy/Environment Research and
Development Program. These studies relate to EPA's mission to protect the public
health and welfare from adverse effects of pollutants associated with energy sys-
tems. The goal of the Program is to assure the rapid development of domestic
energy supplies in an environmentally-compatible manner by providing the nec-
essary environmental data and control technology. Investigations include analy-
ses of the transport of energy-related pollutants and their health and ecological
effects; assessments of, and development of, control technologies for energy
systems; and integrated assessments of a wide range of energy-related environ-
mental issues.
REVIEW NOTICE
This report has been reviewed by the participating Federal Agencies, and approved
for publication. Approval does not signify that the contents necessarily reflect the
views and policies of the Government, nor does mention of trade names or commercial
products constitute endorsement or recommendation for use.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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EPA-600/7-78-175
September 1978
Environmental Assessment for
Residual Oil Utilization-
Second Annual Report
by
M.F. Tyndall, F.D. Kodras, J.K. Puckett,
R.A. Symonds, and W.C. Yu
Catalytic, Inc.
P.O. Box 15232
Charlotte, NC 28210
Contract No. 68-02-2155
Program Element No. EHE623A
EPA Project Officer: Samuel L. Rakes
Industrial Environmental Research Laboratory
Office of Energy, Minerals, and Industry
Research Triangle Park, NC 27711
Prepared for
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, DC 20460
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TABLE OF CONTENTS
Secti on page
1 EXECUTIVE SUMMARY 1
1.1 Introduction 1
1.2 Objectives and Scope of Work 2
1.3 Program Overview 3
2 CURRENT PROCESS TECHNOLOGY 10
2.1 Non-regenerable Flue Gas Desulfurization 10
2.2 Regenerable Flue Gas Desulfurization 19
2.3 Hydrodesulfurization/Hydrodenitrogenation 24
2.4 Partial Oxidation 34
2.5 Chemically Active Fluid Bed 40
2.6 Summary 49
3 CURRENT ENVIRONMENTAL BACKGROUND/OBJECTIVES DEVELOPMENT ... 52
3.1 Multimedia Environmental Goals 52
3.1.1 Emission Level Goals 54
3.1.2 Ambient Level Goals 56
3.2 NSPS Support Research Data Base for Emission 57
Standards 57
3.3 Summary 63
4 ENVIRONMENTAL DATA ACQUISITION 64
4.1 Emissions Inventory 64
4.1.1 Theoretical Engineering Analysis 68
4.1.2 Actual Baseline Emissions 94
4.2 Test Program Development 101
4.2.1 Sampling and Analysis Matrix 105
4.3 Summary 125
5' CONTROL TECHNOLOGY ASSESSMENT 127
5.1 Potential Control Techniques 127
5.2 Residual Oil Utilization Technology 134
5.3 Economic Cost Model Development 136
5.4 Summary and Conclusions 144
ii
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TABLE OF CONTENTS (continued)
Section Page
6 ENVIRONMENTAL ALTERNATIVES ANALYSIS 148
6.1 Source Analysis Model 148
6.2 Pollutant Prioritization 150
6.3 Standard Support Plan 155
7 TECHNOLOGY TRANSFER 157
8 FUTURE EFFORTS 161
REFERENCES 163
GLOSSARY 167
iii
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LIST OF ILLUSTRATIONS
Illustration page
1-1 Environmental Assessment/Control Technology
Development Diagram 4
2-1 Flow Diagram for a Typical Limestone FGD Process 14
2-2 Typical Limestone FGD Material Balance for 500 MW
Unit e 16
2-3 Flow Diagram for a Typical MgO Process Scrubber 21
2-4 Material Balance for a 500 MW MgO Process Scrubber .... 23
2-5 Flow Diagram for a Typical HDS Process 26
2-6 Material Balance for a 500 MWg HDS Process 27
2-7 Catalyst Effect on LSFO Properties - Vanadium Removal ... 30
2-8 Catalyst Effect on LSFO Properties - Nickel Removal .... 31
2-9 Flow Diagram for a Typical POX Process 35
2-10 Material Balance for a 500 MWe POX Process 36
2-11 Flow Diagram for a Typical CAFB Process 41
2-12 Material Balance for a 500 MWe CAFB Process 45
4-1 Comparison of Effects of Excess Air on Products of
Oil Combustion 76
4-2 Level 1 Analysis 108
4-3 Sampling Matrix for Oil-Fired Boiler Without Controls ... 109
4-4 Sampling Matrix for MgO Scrubbers Ill
4-5 Sampling Matrix for Limestone Scrubbers 113
4-6 Sampling Matrix for Partial Oxidation Process 115
(continued)
iv
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LIST OF ILLUSTRATIONS (continued)
Illustration Page
4-7 Sampling Matrix for CAFB Process 117
4-8 Sampling Matrix for an HDS Process 119
4-9 Overall Analytical Scheme for Level 1 122
5-1 Typical Economic Evaluation Schemes 138
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LIST OF TABLES
Table Page
2-1 FGD Service in the United States 12
2-2 FGD Service in Japan 13
2-3 Capital Investment and Annual Costs for FGD Processes
in the U. S 17
2-4 Modular Investment Costs for Limestone FGD 18
2-5 Regenerable FGD Installations in Japan 20
2-6 Typical Properties of LSFO Product from HDS Processes 29
2-7 Typical Low-Btu Gas Composition from Partial Oxidation 39
2-8 Typical CAFB Product Gas Composition 43
2-9 Composition of the Limestone Used for the CAFB
Demonstration 46
2-10 Estimated Comparison of Emissions from CAFB 48
3-1 Sample MEG Chart 55
4-1 Average Residual Oil Composite Analysis 66
4-2 Analysis of Limestone Used by ERCA 67
4-3 Equilibrium Calculation Inputs 69
4-4 Planned Computer Run Matrix 73
4-5' Comparison of Typical No. 6 Fuel Oil Compositions 74
4-6 Typical Slag from Boiler Fired With No. 6 Fuel
Oil 78
4-7(a) Equilibrium Calculation - Predicted Emissions 79
4-7(b) Pollutants Having Projected Emissions Less Than One-
Tenth MATE Value 80
(continued)
vi
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LIST OF TABLES (continued)
Table Page
4-7(c) Compounds for Which No MATE'S Have Been Established 81
4-8 Typical FGD Emissions 82
4-9 Projected Composition of FGD Stack Gas 84
4-10 Projected Composition of FGD Limestone Sludge 85
4-11 CAFB Feedstock and Product Gas Analyses 87
4-12 Typical HDS Performance 89
4-13 Projected HDS LSFO-Fired Boiler Combustion Products 90
4-14 Typical POX Product Gas Composition for Residual Oil
Gasification With Air 92
4-15 Projected Trace Emissions for Boiler Burning POX Product
Gas 93
4-16 Projected Trace Contaminants in POX Wastewater 95
4-17 Spark Source Mass Spectrographic Analysis of Japanese
Limestone FGD Sludge 96
4-18 FGD Sludge Pollutant Ranking 97
4-19 SSMS Analysis of Japanese Magnesia-Gypsum FGD Sludge 98
4-20 Magnesia-Gypsum FGD Sludge Pollutant Ranking 99
4-21 SSMS Analysis of Japanese Sodium Sulfite/Weak Acid,
FGD Waste Stream 100
4-22 Sodium Sulfite/Weak Acid FGD Waste Stream Analysis
Pollutant Ranking 102
4-23 SSMS Analysis of Japanese POX Carbon Pelleted Residue 103
4-24 Partial Oxidation Carbon Residue Pollutant Ranking 104
4-25 Level 1 Sampling 107
4-26 Analysis Techniques for Oil-Fired Boiler Without
Controls 110
4-27 Analysis Techniques for FGD-Limestone 112
(continued)
vi i
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LIST OF TABLES (continued)
Table page
4-28 Analysis Techniques for FGD-MgO 114
4-29 Analysis Techniques for POX 116
4-30 Analysis Techniques for CAFB 118
4-31 Analysis Techniques for HDS 120
4-32 Minimal Bioassay Test Matrix 124
5-1 Physical Forms of Multimedia Effluents from Residual
Oil Utilization Processes 128
5-2 Potential Control Technology for Residual Oil Process
Effluents 131
5-3 Standard Procedures of Economic Evaluation for Pollu-
tion Control Operations 139
5-4 Definition and Guidelines of Five Basic Estimation
Types 140
5-5 Information Requirements for Preliminary Cost Estima-
tion 141
vm
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SECTION 1
EXECUTIVE SUMMARY
1.1 INTRODUCTION
Catalytic, Inc. is making a three-year world-wide study for EPA on the use
of residual fuel oil. This study includes environmental evaluation and related
economics, efficiencies, and systems analyses. The processes being studied
are:
Hydrodesulfurization (HDS)/Hydrodenitrogenation (HDN)
Gulf HDS
UOP Residual Desulfurization
Exxon Residfining
Partial Oxidation (POX)
Texaco synthesis gas generation
Shell gasification
Esso Chemically Active Fluid Bed Process (CAFB)
Combined Cycle
Gas turbine on residual fuel oil
Gas turbine on synthesis gas from POX
Flue Gas Desulfurization (FGD)
Non-regenerable
Regenerable
The HDS units produce a clean, low sulfur residual fuel oil. The POX units
give a low sulfur, low Btu fuel gas, consisting mainly of H2 and CO plus some
CXL. They can be operated either with oxygen or air for gasification. The CAFB
pilot unit at Abingdon, England, is being covered, as well as the CAFB unit de-
signed by Foster Wheeler for Central Power and Light in San Bem'to, Texas. In
this process, the residual fuel oil is partially oxidized with air and the re-
sulting low sulfur gas is burned in a boiler. The fluidized limestone bed,
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containing sulfur, metals, and ash, is partially regenerated and returned to
the unit. A combined cycle unit, using POX feed, is being designed by Beard
Engineering of Baton Rouge, La., for the Louisiana Municipal Power Commission
(LAMPCO).
The study of commercial operating units and demonstration units is present-
ed in this second annual report.
1.2 OBJECTIVES AND SCOPE OF WORK
This report summarizes the results of the second year of the "Environment-
al Assessment for Residual Oil Utilization." The "Environmental Assessment for
Residual Oil Utilization" for the production of electricity by utility industry
is a three year program to: (1) review and analyze the existing environmental,
engineering, and cost data; (2) identify important pollutants and project at-
tainable emission levels; (3) identify missing information and design a pro-
gram(s) to develop such information; and (4) design and conduct source sampling,
fugitive emissions, and ambient monitoring program(s). The program covers boil-
er and combined cycle turbine fuel and pipeline gas manufactured from residual
oil. Those flue gas scrubbers operating on residual oil-fired boilers have also
been studied. This is part of a multi-project program directed toward attain-
ing and maintaining current and projected environmental quality standards to the
year 2000.
During the second program year, the apparent need for a consistent evalua-
tion and reliable comparison of combustion fuels and processes led to the ini-
tiation of an environmental assessment methodology by EPA. In support of the
new environmental assessment program methodology, Catalytic has planned exten-
sive additional work for the assessment of residual oil processing and combus-
tion. Examples of the work being planned are: the preparation of interim
assessment documents for program activities, the preparation of interim assess-
ment reports by process types, annual reports of current and planned activities
for standards support, and an expansion of the sampling and analytical efforts
to satisfy the methodology requirements for a consistent data base.
The objective of the work reported here is to define the problems and
justify the environmental goals of residual oil utilization through a compre-
hensive environmental and engineering analysis. The overall emission control
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goals for each process category under study shall, at a minimum, meet the exist-
ing standards of performance for fossil-fired steam generators. The processes
under study are all considered economically feasible, compatible with boiler
design in the utility industry, and environmentally sound. The primary objec-
tive, then, of this environmental assessment program is to assure that an ade-
quate research data base is available to support the development of standards
and guidelines established by EPA. A simplified block flow diagram shown in
Figure 1-1 gives the relationship between the steps of environmental assessment
and control technology development. The environmental assessment goals for
this program are as follows:
1. Determine the emissions loadings for all pollutants in all
media;
2. Determine control costs;
3. Explore all applicable, existing, and future control and
disposal options;
4. Compare emissions loadings with existing standards, es-
timated multimedia environmental goals, and bioassay spe-
cifications; and
5. Rank the control options, evaluate environmental ef-
fectiveness, and determine the problems and needs for re-
search and development.
1.3 PROGRAM OVERVIEW
The body of this report is organized according to the five environmental
assessment elements shown in Figure 1-1. The activities performed by Catalytic,
Inc. in the residual oil study are indicated on the figure. In this environmen-
tal assessment study, Catalytic is coordinating with other EPA contractors who
are providing information on other environmental assessment activities. A
brief description of each of these five steps follows.
Current Process Background
This section includes a brief description of the residual oil utilization
processes, the development schedules and status, the input for developing ac-
quisition of environmental data, and the potential for national and/or regional
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Control Technology
Development
• Engineering enalyses
• Specific proceu develop-
ment end eveliution
Current Proceaa Tech-
nology Background
• Proceu information
e> Schedule*
•Status
• Priorities for further
iludy
• Existing data for each process
• Identity sampling *nd analyti-
cal technique* Including bio-
• Te»t program development
• Oooiprehenelve wwta stream
, rtiaraelerUatlon (Levels I, II
• rnput-ouiput materials ehar-
OiimM EnvHunnientei
Omfcgnniml
• Potentiel pollutenu
end impKB In ell
medli
e Fed/ttete ndi.
crlterie
Envlronmentel Engineering
Envlronmentel Science!
Maybe
ComreJ Teetinrtogy Oeeeeiniini
• Control tytum end dlepoHl
option Informttton ind de-
tlgn principle
• Control prpoee» pollution
•nd Irnpecu
• frooew engineering pollgt-
•nt/cotl MraitMty iiudlei
• FMd letting In releted
ippllMtlont
• Define belt control tech-
nique for each goel
e> Pollutent control lyMtm
itudlaj
• Etubllfh permlnible
media cone, for control
development guidance
• Define decision criteria
for prioritizing wurcei,
problems
Environmental Alternative! Anelysei
•rieatand Apply
Alternative Sets olMulo-
Madia Enrlronmamal Bee*
MIDI
• Baat technotaev
• Minimum acute toxkity
aflluant
Environmental Sciencei
Technology Transfer
Outpun:
e Quentlfied control RftO needs
e Quantified control elternative
e Defined research date base for
standards
Environmental Sciences R&O e>
Media Dagradailon and
Heerth/Ecotoghal
Impacts Artery**)
e Air. vMter. and land
quality
Outputs:
• Quantified effects
alternatives
f, ^J Performed by Catalytic
[ | Performed by other EPA contractors
Figure 1-1 Environmental Assessment/Control Technology Development Diagram
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use. This step will be used to define the current control costs on existing
residual oil processes. Economic cost data will be helpful in assessing the
economic feasibility of existing process control technology for the utility
industry.
The environmental goals for non-regenerable FGD processes must be based
on Japanese units, because all U. S. technology in this area is based on coal.
The most serious problem with non-regenerable FGD processes is related to the
disposal of sulfur containing waste materials. The sludge producing systems
require solids disposal techniques and use large areas of land. In the U. S.,
it is not likely that a cost credit may be taken for gypsum or other sludges
from non-regenerable FGD processes. The regenerate FGD processes generally
require much more auxiliary energy than non-regenerable types, and by-product
sulfur must be recovered in a usable, marketable form. Emissions goals for
auxiliary sulfur recovery processes must be carefully studied because of the
variable feed streams compositions from the regenerable FGD scrubbers. A ser-
ious problem associated with MgO regenerable scrubbers is the fugitive loss of
fine sorbent, which is inherent to this process.
Without serious environmental consequences, catalytic hydrodesulfurization
of residual oil can effectively reduce the sulfur and heavy metal content to
desirable levels required for direct combustion. However, an assessment of the
final disposal and regeneration of spent catalysts is necessary to provide a
total view of the fate of important potential pollutants. These pollutants are
generally thought to be carried from the HDS processes with the spent catalyst.
Economic costs are the major stumbling block which limit the potential for im-
mediate use of HDS processes. The high cost of hydrogen and high initial in-
vestment for HDS processes are limiting its full developmental potential. The
major environmental problem with POX processes is the necessity for purging of
carbon soot by-product which contains a high concentration of the heavy metals
in residual oil. The cost of oxygen needed for making medium Btu (325 Btu/scf)
gas with the POX process limits its development.
The CAFB process in the demonstration stage shows promise for being an ex-
cellent advanced cleanup technique with minimal environmental effluent problems
using residual oil. However, further development is needed to collect sorbent
fines prior to combustion and to assess disposal methods for spent bed materials.
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Current Environmental Background
This environmental assessment step will be used to summarize key regula-
tions and to document existing effluent standards, which will be compared with
emissions loadings. This step will be useful in identifying control needs for
major pollutant problem areas. It is very important that advanced technolo-
gies, when commercially applied, do not possess their own set of environmental
problems. The major reason for summarizing effluent standards is to identify
and help avoid potential environmental problems that may be associated with
promising technologies. Thus, it is necessary to make a complete environmental
characterization of newly-developing technologies.
Environmental objectives development has been used in amplifying goals
for all possible effluents based on health standards. Recently, there has been
a significant expansion in EPA responsibility because of the new Toxic Substan-
ces Control Act. This Act is concerned not only with the effluents from the
manufacture of hazardous chemicals, but also with the processing of all chemi-
cals. The primary efforts in environmental objectives development have been
focused on protecting human health, ecological systems, and minimizing the
associated risks.
Environmental Data Acquisition
This step will be used to determine emissions loadings by projecting pos-
sible emissions of compounds based on theoretical calculations and engineering
considerations. It is anticipated that a comprehensive source sampling program
will be undertaken to develop the emissions data base necessary for supporting
environmental standards and guidelines and to provide the actual emissions in-
formation necessary for comparison with effluent goals. In some cases, an am-
bient monitoring program may also be needed.
In order to compare the projected emissions loadings for each residual oil
utilization process, a composite analysis was developed based on all input
streams, e.g., residual oil and limestone. Theoretical engineering analyses
were then conducted to serve as a check on the empirical data obtained from ac-
tual sampling. Limited baseline emissions data were projected based on analy-
ses of grab samples taken from commercial residual oil units. Finally, a test
program was developed for the sampling and analysis of each residual oil
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utilization process. A sampling/analysis matrix was constructed to ensure col-
lection of all streams based on Level 1 and Level 2 environmental assessment
protocol.
Control Technology Assessment
The Multimedia Environmental Control Engineering Handbook (MECEH) categor-
izes all commercially-available control technologies, provides technical data
for each process, and includes a list of known suppliers that manufacture the
specific equipment or license the technology. The control processes categor-
ized in the MECEH include: (1) gas treatment, (2) liquids treatment, (3) solids
treatment, (4) final disposal, (5) process modifications, (6) combustion modi-
fication, (7) fuel cleaning, (8) fugitive emissions control (to be performed
later), and (9) accidental release technology (to be performed later).
In this step, applicable, existing, and future control/disposal options
for residual oil usage were explored. For the purpose of this environmental
assessment program, environmental control technology options have been divided
into four areas. The numbers in parenthesis below illustrate the specific de-
vice or process describing the classification, generic device, design type, and
each specific device in that category.
Modification of Process Operating and Design Conditions—
(5.0) Process modifications on CAFB
(5.1) Feedstock changes; residual oils, bitumen,
lignite, limestone
(5.3) Process design improvements in CAFB burners
Pretreatment of Input Streams—
(7. ) Fuel cleaning
(7.4) Treatment of liquid fuels
(7.4.1.1) Demex
(7.4.2) Hydrotreating
(7.4.2.4) Resid HDS (Gulf)
(7.4.2.10) HDN (Engelhard)
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(7.4.2.26) Residual oil HDS (Shell)
(7.3.1.5) Krupp, Lurgi; Retort (POX)
Use of Add-on Control Devices--
(1) Gas treatment
(1.4) Liquid scrubbers/contactors
(1.4.1) Absorption processes
(1.4.1.9) Cyclic lime process - FGD
(1.4.1.14) Magnesium oxide absorption
(1.4.6.13) Multiventuri scrubber
(1.7.2.6) Claus/partial combustion
(1.8.1.1) Catalytic removal of NO
A
Minimization of the Impact of Solid Residue Disposal--
(3.0) Solids treatment
(3.1) Fixation
(4.0) Final disposal
(4.3) Burial and landfill
Potential control techniques for residual oil process effluents were
summarized and related to the technical problems and environmental needs based
on discharge stream sources. An economic cost model was developed for use as
a basis for comparing the economic feasibility or cost effectiveness of various
processes.
Environmental Alternatives Analysis
This step shall identify the best combination of control options for re-
sidual oil utilization process variations. As an example, new process technolo-
gies, such as the chemically active fluidized bed process, will be compared with
lime and limestone flue gas desulfurization, hydrodesulfurization and other
gasification processes. In this step, the pollutant removal capabilities will
be compared; and, the possible pollutant control achievable will be compared
with other existing control technologies. Auxiliary power and process water
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requirements will be compared, as well as input fuel variations and control
technology problems. This analysis will be used to rank the control technolo-
gies, to evaluate the environmental effectiveness, and to identify pollution
control problems and needs for further research and development.
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SECTION 2
CURRENT PROCESS TECHNOLOGY
This section presents an update to the "Process Technology Background for
Environmental Assessment/Systems Analysis Utilizing Residual Fuel Oil," which
was prepared for the EPA by Catalytic, Inc., as the first annual report under
this program. The residual oil utilization processes discussed here include
Phase I processes, which are operating or in commercial design, and Phase II
processes, which are in demonstration plant design. Attention has been given
to non-regenerable flue gas desulfurization, regenerable flue gas desulfuriza-
tion, hydrodesulfurization/hydrodenitrification, partial oxidation, and the
chemically active fluid bed process. For each process category, information is
given pertaining to the system description, raw materials, products, and dis-
charge streams. In addition, the process status gives updated costs, energy
efficiencies, applicability, and the size and number of units now planned or in
operation. Priorities for further study are to include Phase III processes,
which are in the pilot plant phase of development, and to update existing pro-
cess information as further sampling and analysis studies are used to develop
missing data.
2.1 NON-REGENERABLE FLUE GAS DESULFURIZATION
Process Information
Flue gas desulfurization processes (FGD) may be classified by end product
as regenerable, whereby sulfur from the oil is recovered in a usable, marketable
form, or non-regenerable, requiring the disposal of the sulfur as a non-recover-
able waste material.
Information from Catalytic1s information-gathering trip to Japan will be
relied upon to arrive at meaningful data to assess the FGD process. There
have been some domestic FGD units using oil in the recent past, but the cur-
rent U. S. technology for flue gas scrubbing is now concerned with coal-
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fired plants (Table 2-1). The technology for coal-fired FGD is very similar to
that for oil fired; but, in general, this discussion is based on Catalytic's
Japanese trip and information from ongoing contact with the Japanese. The great
majority of FGD units in Japan clean the flue gas from residual oil-fired boil-
ers (Table 2-2). Both tables show that lime and limestone systems are by far
the most common types of the operating FGD processes.
The limestone FGD process was selected as most representative of the non-
regenerable FGD chemical process types. A typical flow diagram for this process
is shown on Figure 2-1. Boiler stack gas is washed in a two-stage (venturi and
absorber) scrubber system with a recirculating slurry (pH of 5.8-6.4) of lime-
stone and reacted calcium salts in water. The overall absorption reaction tak-
ing place in the scrubber and the hold tanks produces hydrated calcium sulfite:
CaC03 + S02 + % H20 —^ CaS03 • h H20 + C02
In practice, some of the absorbed SCL is oxidized by oxygen, which is also ab-
sorbed from the flue gas. This shows up in the slurry as either gypsum
(CaSO^ • 2H20) or as a calcium sulfite/sulfate mixed crystal _/~Ca(S03) (SO^) •
zH20_7- Slurry is recycled around the scrubber to obtain the high liquid-to-
gas ratios required.
The desulfurized flue gas passes through a demister and, prior to dis-
charge to the atmosphere, is reheated to achieve buoyancy and raise gas temper-
ature above the dew point. Limestone feed is ground wet prior to addition to
the scrubber effluent hold tank. Calcium sulfite and sulfate salts are with-
drawn to a disposal area for discard.
Process advantages and disadvantages were described in our previous annual
report. A considerable quantity of CaS03/CaS04 solid waste is generated, ap-
proaching as much as four times the weight of the sulfur removed. Wastes dis-
charged to settling ponds often have poor settling properties, which may lead
to difficulty when reclaiming the land for future use. Potential runoff from
the ponding site could lead to additional water pollution problems due to the
high make-up water and high waste water flows. Another disadvantage of the
limestone slurry process has been low operating reliability from slurry plug-
ging of scrubber internals. Also, reheat and high pressure drop cause an in-
crease in the already high energy consumption. One advantage of the process is
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TABLE 2-1. FGD SERVICE IN THE UNITED STATES
FGD Capacity. MW
Process
Limestone
Lime
Lime/limestone
Sodium carbonate
Magnesium oxide
Well man Lord
Double alkali
Aqueous carbonate
Totals (in MW?)
Operational
4,047
4,237
20
375
120
115
0
0
8,914
Construction
6,470
3,773
0
0
0
715
852
0
11,810
Planning
7,486
5,942
0
634
726
180
250
100
15,318
Total
18,003
13,952
20
1,009
846
1,010
1,102
100
36,042
Source: Bernard A. Laseke and Timothy W. Devitt, "Status of Flue Gas
Desulfurization Systems in the United States," Flue Gas
Desulfurization Symposium, Hollywood, Florida, November 8-11,
1977.
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TABLE 2-2. FGD SERVICE IN JAPAN
Process Units in Operation-!977 Flue Gas Rate-1000Nm3/ha
Wet Lime & Limestone 94 40,181
Double Alkali 46 13,392
Sodium Scrubbing 335 19,961
Regenerable 30 11.537
TOTALS 505 84,891
SOOONm /h corresponds roughly to 1 MWe- Approximately one-half of the
capacity is for utility boilers, and the rest from industrial boilers
and other sources such as sulfuric acid and iron ore sintering plants.
Source: Jumpei Ando and B. A. Laseke, S0? Abatement for Stationary Sources
in Japan, EPA-600/7-77-103a, September 1977.
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Boiler Stack Gas
Limestone
Limestone
Preparation
& Storage
Venturi Scrubber
Demister & Absorbe
Closed Sump
Venturi
Recirculation
Tank
Absorber
Recirculation
Tank
Make-Up Water
To
Stack
Thickener
Sludge
Pond
Figure 2-1 - Flow Diagram for a Typical Limestone FGD Process
-------
a high particulate removal; efficiencies of 80% and higher are typical.
A material balance for a limestone slurry FGD system has been scaled up
from typical data to reflect the process for a 500 MW oil-fired unit (Figure
2-2). A heat rate of approximately 10.92 kJ/W-h (10,350 Btu/kW-h) was assumed.
The combustion of residual oil with atmospheric air is used in a conven-
tional boiler to generate steam for power generation. The products of combus-
tion form the boiler stack gas which contains essentially all of the sulfur
from the oil in the form of S09 and SO- gases, sulfate mist, and sulfates in
£ O
the particulate matter. In the FGD system, the boiler stack gas is contacted
by the water-limestone slurry which removes most of the S02/S03 and much of
the particulate. The reheated, S02-reduced, stack gas is then returned to the
boiler stack for release to the atmosphere. Calcium sulfite/sulfate is bled
from the venturi recirculation tank and pumped to a thickener where most of
the water is removed and returned to the absorber recirculation tank. The con-
centrated sludge is transferred to a sludge pond. Make-up water and limestone
are required to balance the sludge effluent and evaporation losses, including
water carried off with the clean stack gas. Detailed descriptions of the
streams mentioned above were included in the first annual report.
Process Status
Updated investment and operating costs from the first annual report are
shown in Table 2-3.
4
A recent detailed study was conducted by Ebasco Services, Inc. Investment
costs for limestone FGD systems are shown in Table 2-4. Operating costs were
derived assuming the following:
1. 600 MW unit burning high sulfur Eastern coal
2. -1977 operation with 30-year levelizing period
3. Fixed Charge Rate of 18% per year
4. $375 per kilowatt capability charge (see glossary)
5. Power cost - 25 mills per kilowatt hour
6. Limestone cost - $12 per ton (997 kg) delivered
7. Maintenance cost - 3% per year on investment.
-15-
-------
o>
I
Residual Oil
130,000kg/h~
Air
2,119,86 5 kg/h
Limestone
15,400kg/ii
Water
95,125kg/h
Treated Flue Gas
2,310,110 kg/h
FLUE GAS
DESULFURIZATION
LIMESTONE
SLURRY SCRUBBING
^ Sludge
«),280 kg^
Figure 2-2 - Typical Limestone FGD Material Balance for 500 MWe Unit
-------
TABLE 2-3. CAPITAL INVESTMENT AND ANNUAL COSTS FOR FGD PROCESSES IN THE U. S.
Power Size: 500 MWg
Residual Oil (No. 6) = 4.0% Sulfur
Mid-1978 Battery Limits Costs
Total Capital Annual Costs
Process Investment $/KM Mills/kNh (No Credits)
1. Limestone/Sludge 103.73 4.87
(CaO, CaC03)
2. Lime/Sludge 98.01 5.06
(Ca(OH)2)
3. Magox/Sulfur * 106.87 5.05
(MgO)
4. Alum/Basic A12(S04)3 142.89 5.58
5. Sodium/Sulfur * 125.58 5.67
(Na2S03, NaOH, Na2C03)
6. Double Alkali/Sludge 98.24 4.48
(Na2S03 + CaC03 or Ca(OH)2,
(NH4)2S04 + CaC03,
A12(S04)3 + CaC03)
7. Ammonia/Sulfur * 117.29 4.56
8. Copper Oxide 156.60 5.99
9. Citrate 117.55 5.68
10. Activated Carbon 174.67 5.70
* Elemental Sulfur is By-product.
Source: Catalytic, Inc., "Process Technology Background for Environmental
Assessment/System Analysis Utilizing Fuel Oil," 68-02-2155, EPA-
600/7-77-081, August, 1977.
-17-
-------
TABLE 2-4. MODULAR INVESTMENT COSTS FOR LIMESTONE FGD
Plant Size
Components 400 MWG 600 MWC
S02 Removal Equipment $94/KW (16.4%) $87/KW (16.4%)
Waste Disposal Ponds $25/KW (4.4%) $14/KW (3.4%)
Waste Disposal Equipment $15/KW (2.6%) $13/KW (2.5%)
Limestone Preparation Equipment $14/KW (2.4%) $10/KW (1.9%)
$148/KW (25.8%) $128/KW (24.2%)
Notes: (1) Percentage of total plant investment is given in paren-
theses. Basis is high sulfur Eastern coal - no preci-
pitator costs included.
(2) Costs are in 1977 U. S. dollars.
Source: R. L. Andrews, "Current Assessment of Flue Gas Desulfuri-
zation Technology," Combustion, XLIX, No. 9 (October 1977),
20-25.
-18-
-------
8. Operator Labor - $18 per hour, including overhead and
supervision
At a capacity factor of 0.6, fixed charges amount to 4.7 mills/Kw-hour, oper-
ation and maintenance are 0.8 mills/Kw-hour, and power and limestone are also
0.8 mills/Kw-hour.
Representative Japanese F6D costs were given in our previous annual re-
port, and no update has been prepared.
2.2 REGENERABLE FLUE GAS DESULFURIZATION
Process Information
Regenerative FGD processes produce sulfur, sulfuric acid, or other sulfur-
containing products which have a potential market value. Currently, such pro-
cesses are less widely applied than the throwaway processes which were quickly
developed during the early days of the Air Quality Act. The throwaway
technologies were generally considered less complicated. Regenerable process-
es currently in use at domestic utilities are magnesium oxide scrubbing and
the Wellman-Lord process (which uses Na0SO^), both being used only for coal-
33
fired boilers at this time. Japan uses these same processes and others for
industrial and utility boilers firing residual oil, as shown in Table 2-5.
The MgO process was selected as the basis for the flow diagram in Figure
2-3, which includes the same venturi-absorber described in Section 2.1. It
was selected because it is the only regenerable process to have been applied
to a residual oil-fired boiler in the United States.
A slurry of MgO or Mg(OH)2 absorbs sulfur dioxide from flue gas in a
scrubber, yielding magnesium sulfite and sulfate. In the scrubbing step, the
following reactions predominate:
• S02 absorption
5H20 + Mg(OH)2
S02 + MgS03 •
• Bisulfite neutralization
Mg(HS03)2 + MgO + 11H20
• Magnesium sulfite oxidation
2MgS03 + 02 *• 2MgS04
-19-
-------
TABLE 2-5. REGENERATE FGD INSTALLATIONS IN JAPAN
Process
Wellman-MKK
Wellman-SCEC
Onahama-Tsukishima
Chemico-Mitsui
Mitsui Mining
Mitsui Mining
Shell
Sumitomo H.I.
Hitachi, Ltd.
Nippon Kokan
Kurabo Engineering
MHI-IFP
TEC-IFP
Absorbent By-Product Total Units3 Flue Gas Rate
5,306,000 Nm3/h
1,289,000 Nm3/h
84,000 Nm3/h
500,000 Nm3/h
80,000 Nm3/h
50,000 Nm3/h
120,000 Nm3/h
160,000 Nm3/h
591,000 Nm3/h
1,900,000 Nm3/h
15,000 Nm3/h
42,000 Nm3/h
6,000 Nm3/h
Na2S03
Na2S03
MgO
MgO
MgO
ZnO
CuO
Carbon
Carbon
(NH4)2S03
(NH4)2S04
(NH4)2S03
(NH4)2S03
H2S04 or S
H2S04 or S
H2S04
S
H2S04
H2S04
S
H2S04
H2S04
(NH4)2S04
(NH4)2S04
S
S
12
6
1
1
1
1
1
1
2
2
1
1
1
a. Four units are for utility boilers, sixteen are for industrial boilers,
and the rest are for acid plants, Claus furnaces, sintering and smelting
plants.
3
b. 3,000 Nm /h corresponds roughly to 1 MW .
Source: Jumpei Ando and B. A. Laseke, $00 Abatement for Stationary Sources in
Japan. EPA-600/7-77-103a, September 1977.
-20-
-------
Absorber
Recirculating
Tank
Figure 2-3 - Flow Diagram for a Typical MgO Process Scrubber
-------
The sulfite as magnesium sulfite hexahydrate crystals is easily filtered
from the slurry, dried, and calcined to regenerate magnesium oxide. The sul-
fur is then recovered as S02 and can be processed in an acid plant to yield
sulfuric acid or in a Claus unit to yield elemental sulfur. The small amount of
magnesium sulfate formed can be recovered for fertilizer use or calcined with
the sulfite using carbon as a reducing agent.
A material balance for a 500 MW unit has been prepared and is presented
in Figure 2-4, scaled up from actual measurements from a smaller installation.
Boiler stack gas, the product of the combustion of residual oil and atmos-
pheric air, enters the scrubber unit for removal of sulfur dioxide. After
being contacted by the recirculating magnesia slurry, the SO^-reduced, stack
gas is reheated and returned to the boiler stack for release to the atmosphere.
Typical S02 removal efficiency is 90-94%; particulate removal at one installa-
tion ranged from 46-70% with outlet particulates varying from 0.122-0.199
g/10 cal (.068-.Ill pounds per million Btu). The SOp absorbing slurry is
centrifuged to remove the slurry water, which is returned to the recirculating
tanks. In a dryer, the water of hydration with the magnesium sulfite is driven
off. A calciner converts the magnesium sulfite and sulfate to magnesium oxide
which is returned to the magnesia slurry tank. Low sulfur fuel oil, combus-
tion air, and coke are required in the calciner which produces a gas containing
approximately 7% SO,, which is of sufficient strength to be used as feed for
24
sulfuric acid manufacture.
In actuality, MgO losses do occur, and make-up magnesia is required. Ac-
tual values from operating experience showed that make-up MgO was required
equal to 3.5 percent of the MgO recirculation rate in the scrubber. This 3.5
percent loss was divided into losses to the stack (35%), losses to scrubber
overflow (38%), and miscellaneous losses (27%),2^ For a 500 MW plant, these
losses could amount to 150 kg/h.
Process Status
In a report describing the MgO system at Boston Edison, fixed investment
and annual operating costs were developed for a 200 MW , new, coal-fired power
plant, regenerative MgO F6D system. Based on 3.5% sulfur in the coal, and
production of 98% sulfuric acid, estimated fixed investment was $17.4 million
-22-
-------
I
no
Residual Oil
130,000 kg/h
Combustion Air
2,120,589 kg/h
Make-Up Water
88,997 kg/h
Fuel Oil
3055 kg/h
Air
92,323 kg/h
Coke
271 kg/h
Stack Gas
2,410,050 kg/h
FLUE GAS
DESULFURIZATION
MAGNESIA
SLURRY SCRUBBING
S02 - Rich Gas
25,185 kg/h
Figure 2-4 - Material Balance for a 500 MWe MgO Process Scrubber
-------
or $87 per kilowatt (1975 dollars). Total annual costs were $2,853,045 or 2.04
mills/kw-hr (80% capacity factor).24 A previous EPA study on a similar basis
(1972 dollars) gave a fixed investment of $11.685 million or $58.43 per kilo-
watt, and an annual manufacturing cost of $1,725,800, or 1.23 mills per kw-hr
(80% capacity factor).27 The cost of the Chemico-Mitsui plant in Japan, exclu-
sive of any processing of sulfur dioxide, was $13 million, or $74/KW in 1974.
Total capital investment presented in Table 2-3 for a 500 MWe, 6% sulfur, oil-
fired, magnesia scrubber producing elemental sulfur (no credit) was $106.87/KW,
and its annual cost was 5.05 mills/kw-hr.
Current domestic application of the MgO FGD process is limited to one,
33
120-MWe installation, using coal, at Philadelphia Electric Company. Japan
has three installations using an MgO process as was shown in Table 2-5.
The MgO process is attractive because solids and wastewater disposal prob-
lems are avoided. The sulfite salt is readily separated from the scrubber li-
quor, and the magnesium is easily regenerated and recycled. A centralized re-
generation-acid unit can be set up financially and operationally separate from
the utility operation. The process is capable of achieving above 90% S02 re-
moval efficiency, and has excellent flexibility for by-product switching from
sulfuric acid to elemental sulfur.
Drawbacks include the energy input required to generate concentrated S02
and the fluctuations in price of sulfuric acid and sulfur which can make the
acid plant regeneration a financial detriment rather than an asset.
2.3 HYDRODESULFURIZATION/HYDRODENITRIFICATION
Process Information
The petroleum refinery process of hydrodesulfurization has become viable
and necessary in providing residual oils because of the utilization of poorer
quality (sour) crudes, more efficient refinery processes in producing gaso-
line and Number 2 oil, and the sulfur control necessary for protection of the
environment. As more gasoline and Number 2 oil are extracted from the crude
barrel, less resid is produced. But what is produced contains undesirable
components, e.g., sulfur compounds, organo-metallic compounds, and high mole-
cular weight hydrocarbons, in a high concentration. As crude oil reserves are
-24-
-------
depleted, more sour crudes are used as refinery feedstock, with the increased
amounts of sulfur and organo-metallics being concentrated in the resid. Final-
ly, to control sulfur dioxide emissions from utility power generation, without
gasification of the oil or post-combustion treatment, a low level of sulfur in
the fuel oil is required.
A typical HDS process is shown in Figure 2-5. Residual oil is heated and
introduced with hydrogen into the fixed-bed HDS reactor containing the catalyst
charge. In the reactor, desulfurization, demetallization, and carbon residue
reduction (and, to a lesser extent, denitrogenation and some hydrocracking) oc-
cur. The sulfur in the reduced crude combines with the hydrogen to form hydro-
gen sulfide (H2S).
Organo-sulfur compound + H2—catalyst^ H2S + LSFO
Most HDS processes utilize fixed-bed reactors with catalysts to lower the opti-
mum operating temperature to reasonable limits. Cobalt molybdenum on an alum-
ina base is a common choice, but a multitude of other catalysts have been and
are being used and studied to solve the problems of catalyst life and consis-
tent sulfur removal efficiency.
Bed temperatures typically range from 300°C to 450°C, and pressures from
2.7 MPa to 21 MPa (400-3000 psig). Hydrogen requirements vary from 500 to
10,000 scf/bbl (84-1680 Nm3/kl) of oil.35 A material balance is shown in Fig-
ure 2-6. Scaled down from typical operating data, it represents production of
low-sulfur fuel oil (LSFO) in the amount required by a 500 MWg power plant.
The reactor effluent enters a series of flash vessels which separate the
stream into liquid, recycle-gas, and sour fuel gas fractions (off-gas). The li-
quid streams pass to a distillation column for fractionation into low-sulfur
fuel oil, middle distillate (or furnace oil), naphtha, and sour fuel gas. The
recycle-gas goes to an amine scrubber where the H2S is removed. It is necessary
to remove the H2S, since its presence in the hydrogen-rich recycle gas would re-
duce the desulfurization rate. This purified recycle gas is either used as
quench gas to moderate the reactor's temperature or mixed with the feed and
make-up hydrogen. An amine regenerator (considered as part of the recycle gas
treatment) separates the recycle amine and hydrogen sulfide.
The amine regenerator represents a potential pollution source. Spillage,
purging, amine disposal, or any other fugitive emissions from the regenerator
-25-
-------
Residual Oil
i
ro
o>
Catalyst
Hydrogen Make-Up Wash Water
Storage &
Pretreatment
Off Gas
m
Reaction
Section
i
Separation
Section
i
Spent Catalyst &
Reactor Waste
Sour Water
Stripper
Treated Water
*
Recycle Gas
Treatment
lf"r
I
Sulfur
Off Gas
i
Naphtha
Fractionation
Section
Low Sulfur Fuel Oil
Stack Gas
Tail Gas
Clean-Up
By-Product
Figure 2-5 - Flow Diagram for a Typical HDS Process
-------
I
ro
-si
Off-Gas
2254 kg/h
Hydrogen Make-Up
2143kg7h
Residual Oil
125,000 *
Steam
2215 kg/h
Water
4285kg7rT
HDS
Acid Gas
3076 kg/h
Low-Sulfur Fuel Oil
112,326kg/h
Naphtha
1155kg/h
Furnace Oil
8112kg/h
Sour Water
6720 kg/h
Figure 2-6 - Material Balance for a 500 MWe-HDS Process
-------
present the possibility for a toxic effluent. Work to date has not explored
this area in great detail.
The H2S-rich off-gas stream from the amine regenerator (96-99% H2S) can be
treated in a Claus unit for recovery of elemental sulfur (approximately 97% con-
version), with the unconverted H2S passing from the unit in the form of sulfur
dioxide. Additional control, tail-gas cleanup, is required for this S02-con-
taining stream. Acid gas from the sour water stripper can also be handled by
the Claus unit.
Hydrogen make-up represents about 10% by weight of the total hydrogen and
recycle gas utilized in the reactors. Hydrogen consumption of HDS units changes
gradually during operation, increasing due to catalyst deactivation in the HDS
reactors.
The major product of concern from HDS processes is low sulfur fuel oil
(LSFO). Depending upon the type of feed, the process variables of the particular
HDS process, the amount of sulfur removed, type of catalyst employed, and number
and type of reactors, the LSFO can have varying properties (Table 2-6). Substan-
tial reductions in sulfur are accompanied by reductions in nitrogen, carbon resi-
due, vanadium, nickel, ash, viscosity, and pour point. Heat of combustion and
hydrogen content are improved. Improved gravity, viscosity, pour point, and
heat of combustion are all desirable to the boiler user. Decreased carbon resi-
due, ash, and metals content prolong boiler life by reducing ash deposition and
corrosion. Typical variations in the amount of vanadium and nickel removed as a
function of the catalyst chosen are shown in Figures 2-7 and 2-8. For a given
catalyst, the percentages of vanadium and nickel removed increase directly with
the percentage of sulfur removed. For a given sulfur removal percentage, the
percentages of vanadium and nickel removed are strongly dependent upon the cata-
lyst selectivity.
The naphtha and furnace oil streams from the fractionator were discussed in
our previous annual report. No update has been made.
The wash water stream also was discussed in our first annual report. Data
are still being studied as input to the environmental assessment.
Off-gases produced in the separation and fractionation sections of the HDS
process are blended together into a single stream rich in hydrogen and containing
-28-
-------
TABLE 2-6. TYPICAL PROPERTIES OF LSFO PRODUCT FROM HDS PROCESSES
Untreated
--
650
16.6
3.8
9.0
0.22
15.0
45.0
250
0.02
44.9
1% S
LSFO
89.4
650
20.0
1.0
5.31
0.13
4.6
8.2
107.3
0.004
0
19,110
12.1
86.7
+60
497
0.3% S
LSFO
97.5
375
23.4
0.3
3.33
0.13
1.3
2.2
52
0.003
0
19,250
12.5
87.1
+35
663
0.1% S
LSFO
97.1
375
24.1
0.1
2.75
0.09
0.4
1.0
45
0.003
0
19,375
12.7
87.1
0
812
Product Yield: Vol. %
Product Properties:
Cut Point: °F
Gravity: °API
Sulfur: Wt. %
Carbon Residue: Wt. %
Nitrogen: Wt. %
Nickel: PPM
Vanadium: PPM
Viscosity: SUV (210°F)
Ash: Wt. %
Salt: PPM *
Heat of Combustion: Btu/Lb
Hydrogen: Wt. %
Carbon: Wt. %
Pour Point: °F
Hydrogen Consumption: SCF/BBL
* Salt refers to all water-soluble cations, determined as halide and report-
ed as NaCl before desalting.
Source: Gulf Research and Development Company
-29-
-------
80
60 -4
^
|
= 40-1
E
3
20 H
0-C
,<
/
•o , «
ID
I
/ .„,/
sr ^/'
^
/ J'
&0 -TOO
Sulfur Removal %
Figure 2-7 - Catalyst Effect on LSFO Properties
Vanadium Removal
Source: Hastings, Kennetf. E.. Lewis C James, and William R. Mounce. "Demetallfzation Cute
"^0.1 and Gas Journal. LXXIII, No. 26 (June 10. 1975)
-30-
-------
as
1
u
50
Sulfur Removal %
100
Figure 2-8 - Catalyst Effect on LSFO Properties
Nickel Removal
Source: Hastings, Kenneth E., Lewis C. James, and William R. Mounce, "Demetaffization Cuts
Desulfurization Costs," The Oil and Gas Journal, LXXIII, No. 26 (June 10, 1975)
pp. 122-130. „
-------
about 15 mole percent hydrogen sulfide. Its eventual end use is determined by
the particular refinery complex, but it is not emitted to the atmosphere.
Acid gas treatment was described in our previous annual report, and a var-
iety of tail gas treatment methods was reviewed, including the Shell Claus Off-
Gas Treater, Institut Francais dePetrole, and Chiyoda Processes. A recent com-
mercial installation employs a Claus unit followed by a Stretford process tail
gas cleanup unit. Effluent from the Stretford solution purge can include vana-
dium, anthraquinone-desulfonic acid (ADA), sodium thiosulfate, sodium thiocya-
nate, and elemental sulfur.
Although spent catalyst is removed only once or twice a year, because of
the concentration of carbon, sulfur, and metals on the catalyst, it represents
an environmental concern. As mentioned above, the most widely-used catalysts
for HDS are composites comprised of cobalt oxide, molybdenum oxide, and alumina,
where alumina is the support carrying the other agents as promoters. Over 250
processes related to the desulfurization of residual oils have been described in
the U. S. patent literature since 1970. Most of the research and development
activity by major oil companies has focused on increasing the efficiency of sul-
fur removal from total feed systems, particularly those resids with high asphal-
tene contents. Coke formation on the catalyst surface and metal deposition at
the pore mouths are the catalyst poisoning mechanisms whose severity increases
32
with the asphaltene content. Such being the case, catalyst information is re-
stricted by the oil companies, and catalysts are being continually improved.
Metal deposits within the catalyst can also make regeneration unattractive, es-
pecially since regeneration converts these metals to deactivating sulfates.
Many catalysts are made sufficiently inexpensive to be used for a single cycle
and then replaced with a new catalyst, generally on an annual or semi-annual
. . 15
basis.
Our study to date has been limited to the point at which the spent cata-
lyst is removed from the process for regeneration or ultimate disposal. It is
felt that an important need exists to assess the multimedia environmental impact
of spent hydrodesulfurization catalysts by regeneration and final disposal and
to provide a total view of the fate of important potential pollutants which may
be reprocessed or disposed of with spent catalysts from the hydrodesulfurization
processes.
-32-
-------
Process Status
The major current commercial, direct hydrodesulfurization facilities were
described in our previous annual report. To that list can be added Exxon's Bay-
town Residfiner 1 with a 75,000 barrel-per-day capacity.
Present estimates for the desulfurization of reduced crude range from $2 to
$4 per barrel. The cost depends on items such as hydrogen cost, site of plant,
raw material costs, and desired amount of sulfur in end product.
In a refinery complex, many of the process units (for example, sour water
strippers, acid gas cleanup) are not dedicated to HDS alone, and the apportion-
ment of costs is difficult to ascertain.
Data obtained on Japanese units are being analyzed, with the ultimate ob-
jective of determining the range of desulfurization for the actual operating
units. Total capital costs were obtained for all seven plants visited, but
problems were encountered in establishing an equal basis for comparison. In
some cases, the cost included sulfur recovery and tail gas treatment, while in
others, this cost was left out. Economic information on the Baytown unit is
just becoming available.
No update on energy efficiency or process applicability was prepared during
this contract year.
Hydrodeni trogenation
Although hydrodenitrogenation (HDN) is of greater importance in lowering
the organo-nitrogen content of synthetic crudes extracted from oil shale, some
coals, and certain low-grade naturally-occurring petroleums, HDS reactions occur
in the HDS process and improve the quality of the low sulfur fuel oil produced
(Table 2-6).
The reactions are similar to those for HDS:
Organo-nitrogen compound + H2 catalyst^ NH3 + LSFO
The HDS and HDN reactions can and do interact with each other, sometimes being
mutually inhibiting, sometimes enhancing each other.
Decreased nitrogen is advantageous in that some of the nitrogen oxide emis-
sions from combustion are reduced. Combustion modification and other techniques
can usually be used to control total NOX within current environmental restrictions,
-33-
-------
2.4 PARTIAL OXIDATION
Process Information
POX or Partial Oxidation processes convert hydrocarbons into a fuel gas
by controlled partial oxidation with air or oxygen. No catalyst is required,
thus a wide range of unusable fuels can be converted to clean gaseous fuels.
Substantial variations in the sulfur, nitrogen, and metals content of the feed-
stock are possible.
A flow diagram for a typical POX process is given in Figure 2-9. An
accompanying material balance for a POX process producing enough low-Btu gas
for 500 MWeis given in Figure 2-10.
Residual oil is often contaminated by salt water during transportation.
To prevent damage to the reactor's ceramic lining, the salt content in the oil
feed should be reduced to 10 pounds per 1,000 barrels or less (approximately
30 ppm Nad or 10 ppm Na). In the fuel preparation section, water washing,
followed by electrostatic precipitation or centrifuging to remove the salt
water, is usually adequate. Filtration and heating are included as part of
the feed preparation.
In producing a low-Btu gas (approximately 5000 kJ/Nm3 or 125 Btu/scf)
for use in a boiler, gas turbine, or combined cycle power plant, air is used
as the oxidant. (The use of pure oxygen results in a higher-Btu gas of approx-
3
imately 12,000 kJ/Nm or 300 Btu/scf, and steam is required as a moderator or
dilutant in the reaction.) Pressurized air and residual feed are intimately
mixed in the POX reactor producing a fuel gas which contains carbon monoxide
and hydrogen. The sulfur in the fuel is converted to hydrogen sulfide in the
gasifier's reducing atmosphere. Much of the metallic ash is sequestered with
the free carbon or soot, which is removed from the product gas in the carbon/
gas separator section. The balance of the ash is deposited in the reactor
and removed during periods when the reactor is shut down for inspection.35
A waste heat exchanger at the outlet of the reactor recovers much of the
reactor heat in the form of steam, adding greatly to the overall process effi-
ciency. Additional heat recovery may be obtained from the product gas after
slurry separation and before gas scrubbing in the carbon/gas separator section.
-34-
-------
Air
Residual
Oil
Water
Fuel
Preparation
GO
tn
i
Make-Up
Carbon Recovery
& Recycle
Low-Btu
LGas
Treated Water
Figure 2-9 - Flow Diagram for a Typical POX Process
-------
I
CO
Residual Oil
164,000
kg/h
Air
984,001
kg/h
Air (Glaus)
19,262kg/h
Flue Gas
31,300 kg/h
A
POX
Sulfur
3862 kg/h
Low Btu Gas
1,102,969 kg/h
Water (from Glaus)
4,125 kg/h
Water (from Carbon Recycle)
25,007 kg/h
Figure 2-10 - Material Balance for a 500MWe - POX Process
-------
In the carbon/gas separator section, the product gas from the reactor
is contacted by water in a spray vessel followed by a carbon slurry separator;
most of the soot is recovered here. The remaining soot is removed from the
product gas in a scrubber. The water wash is designed to remove essentially
all of the product gas contaminants that are soluble in water, plus the carbon
soot and certain ash compounds which remain suspended in the water. These
contaminants are mainly carbon, ash, including vanadium and nickel compounds,
hydrogen cyanide, ammonia, and traces of formic acid. All of these contami-
nants are potential pollutants and should be handled accordingly. By treating
the spent wash water, either directly or after returning the soot to the car-
bon recovery and recycle section, the hydrogen cyanide, formic acid, and am-
monia can be disposed of safely, leaving only the metals and ash.
Two major methods are used in the carbon recovery and recycle section
where soot is separated from the water slurry. A pelletizing system recovers
and agglomerates the soot to carbon pellets with the aid of either a distill-
ate or residual oil. The water is returned to the carbon/gas separator section,
while the soot pellets can be burned in specially-developed pellet combustors
or returned to the reactor feed. The other separation method utilizes an in-
termediate fluid, naphtha, to preferentially wet the carbon, producing a
naphtha-soot agglomerate which can then be separated from the water stream.
The naphtha-carbon agglomerates are then mixed with fresh oil feed (which can
be the residual feed) and flashed into a naphtha stripper for recovery of the
naphtha. The carbon-fuel oil combination is then recycled to the reactor for
conversion into product gas. Some ash, vanadium, and nickel are still retain-
ed by the soot, and thus recycled back through the process for eventual dis-
38
posal either with the wash water or the reactor ash.
The sulfur products are only slightly soluble in water and therefore re-
main in the product gas stream as hydrogen sulfide (H2S), with some carbonyl
sulfide (COS) and a trace of carbon disulfide (CS2).
Several commercial processes are available for removal of up to 99+ per-
cent of the H2S from the product gas. Some absorption processes use solvents
which selectively remove the H2S, leaving much of the C02 in the gas. The
carbon dioxide can be absorbed if another solvent is chosen, yielding a pro-
duct gas with a higher Btu content; but, it is usually retained in the product
-37-
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gas, especially if the product gas is to be used as a fuel for gas turbines
where it has some beneficial effect. High temperature processes which do not
require any cooling of the product gas stream are available; but, few, if any,
have achieved commercial status. The product gas, cleaned of most of the soot,
sulfur, ash, and particulate, exits the H2S removal section and is suitable for
use as a gas turbine, steam boiler, or combined-cycle fuel. A typical analysis
of this low-Btu product gas is given in Table 2-7.
The hydrogen sulfide can be converted into elemental sulfur, leaving an
effluent gas containing some residual sulfur dioxide, a potential pollutant.
However, further processing methods, which will reduce the sulfur dioxide emis-
sion to very low levels, are available.
The water streams can be collected and processed in the water treatment
section. Included in these water streams are soluble and suspended ash compo-
nents, including vanadium and nickel, minor quantities of carbon, hydrogen
cyanide, and ammonia, and trace amounts of formic acid.
Process Status
No update of the POX process status has been prepared for this annual
report- Except for inflation, capital and operating costs previously describ-
ed remain unchanged. No POX installations or new gasifier installations
have become known.
Intensive private and governmental development work in the areas of hot gas
cleaning for the product gas and increased gas turbine operating temperatures
will enhance the future potential of the POX process when integrated with a
combined-cycle power generation unit. The combined-cycle concept is expected to
assume a major role in the production of electricity in the near future. The POX
process and the combined-cycle concept complement each other. The POX gasi-
fier produces clean fuel required by the high temperature gas turbine, and
the gas turbine produces large quantities of compressed air required by the
POX process. Sensible heat carried by the fuel after gasification may be
used to produce steam for the steam turbine. The high quantity of inert gas
in the low-Btu product also reduces NO emissions from the gas turbine. The
A
overall thermal efficiency of a gasification/combined-cycle system has been
estimated at 38 to 40 percent.18' 36' 39
-38-
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TABLE 2-7. TYPICAL LOW-BTU GAS COMPOSITION FROM PARTIAL OXIDATION
Composition
Hydrogen
Carbon Monoxide
Carbon Dioxide
Water
Methane
Nitrogen
Argon
Hydrogen Sulfide ~~1
Carbonyl Sulfide J~~
Total
Average Molecular Weight
Higher Heating Value,
kJ/Nm3
Lower Heating Value
kJ/Nm3
Volume %
14.3
23.7
0.02
0.28
0.26
60.65
0.76
<300ppm
100.00
24.33
4965 (125.5 Btu/SCF)
4668 (118.0 Btu/SCF)
Source: Catalytic, Inc., "Process Technology
Background for Environmental Assess-
ment/System Analysis Utilizing Fuel
Oil," 68-02-2155, EPA-600/7-77-081,
August, 1977.
-39-
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2.5 CHEMICALLY ACTIVE FLUID BED
Process Information
Fluidized-bed combustion includes both atmospheric and pressurized process-
es. Possible variations include steam tubes in the fluidized bed, air tubes, or
no tubes, whereby a hot, low-Btu gas is produced for subsequent generation of
electric power. The burning (or gasification) of oil or coal occurs within a
bed of granular, noncombustible material such as limestone. This bed is sup-
ported on a grid, and air is passed up through the plate, causing the granular
material to become suspended (fluidized).
Process advantages for gasification include:
• in situ removal of SOg by the use of limestone as a bed ma-
terial;
• more fuel flexibility than a conventional boiler, which can
result in reduced fuel costs from the use of cheaper fuels; and
• production of a gaseous fuel usable, with little equipment
modification, in existing oil- and gas-fired boilers which
may be legislatively banned from using low-sulfur fuel oil
or natural gas.
Additional advantages when fluidized-bed combustion is used in place of a
conventional boiler are:
• reduced boiler size and heat transfer surface requirements,
thus, the possibility of modular instead of the more expen-
sive field construction; and
• reduced NO emissions, trace element volatilization, and
X
corrosion due to lower combustion temperature (about 900 C
vs. 1500°C for a conventional boiler).
The Chemically Active Fluidized-Bed (CAFB) is an atmospheric-pressure,
fluidized-bed, residual oil gasification/desulfurization process. Figure 2-11
is a flow diagram for a typical CAFB installation. The basic CAFB process con-
sists of four distinct functions: oil gasification/desulfurization, lime re-
generation, sulfur recovery, and spent stone disposal/processing. High-sulfur
fuel oil is injected into an 870°C bed of limestone fluidized by a mixture
-40-
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Limestone
Limestone
Preparation
&
Storage
Fuel
Air
Combustion Air
Gasifier
Regenerator
Air
Spent
Stone
Coal
Steam •
Figure 2-11- Flow Diagram for a Typical CAFB Process
Boiler
RESOX™ Unit
Sulfur
Condenser
I
Sulfur
Flue Gas
Ash
-------
of flue gas and air. Air is admitted in sub-stoichiometric proportions (approx-
imately 22 percent) to limit the amount of oil combustion and heat release.
The flue gas is used as an inert, heat-absorbing medium to control the overall
gasifier temperature. Limestone (CaC03) sized less than 1/8 in. is injected
into the bed at a rate such that 0.5 to 1.5 times the stoichiometric CaS ratio
is maintained in the bed. At these conditions, the high-sulfur oil is vapor-
ized and undergoes cracking, coking, and oxidation. The organic sulfur in the
oil forms a variety of oxidized sulfur compounds (e.g., SCLj COS, etc.) which
are predominantly reduced to hydrogen sulfide (H2S). Hydrogen sulfide formed
during the partial combustion reacts with the bed material forming calcium sul-
fide and steam. The resulting low-Btu product gas is essentially sulfur free
(sulfur removal efficiencies greater than 90%) and can be burned in a steam
generator with specially-designed low-Btu gas burners (see Table 2-8). Sulfur
is captured in the bed, along with most of the vanadium, nickel, and some of
the sodium from the oil.
The bed material containing the sulfur and metals from the oil can be dis-
carded or regenerated. As the concentration of sulfur on the bed material in-
creases, the lime (from in-situ calcining of the limestone) is less able to
absorb sulfur. This sulfur-laden bed material must be removed from the gasi-
fication zone and replaced with sulfur-free lime. Regeneration consists of
reacting air with the calcium sulfide to yield CaO and a sulfur dioxide gas
of about 8 to 10% S0£. The regenerated sorbent is returned to the gasifier.
Regenerator temperature is maintained at 1050 to 1100°C (1922-2012°F) by the
rate of sorbent circulation. Sulfur absorption efficiency of the regenerated
lime decreases with each regeneration, necessitating the need for eventual dis-
posal of the spent stone and addition of make-up limestone.
Several processes are available for converting sulfur dioxide to sulfur
(e.g., Claus tail gas catalytic process, Bureau of Mines citrate system).22
TM*
Foster Wheeler's RESOX process, which uses coal to convert S02 to sulfur,
will be described in greater detail later.
Spent stone, containing some sulfur and carbon, and most of the metals re-
moved from the oil, presents an environmental disposal problem. This problem
is currently being studied by various persons and agencies and will be described
in other sections of this report.
* RESOX™ is a Foster Wheeler trademark.
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TABLE 2-8. TYPICAL CAFB PRODUCT GAS COMPOSITION
Component Volume Percent
Hydrogen 8.6 + 3.0
Nitrogen 61 +. 5
Methane 6.4 +_ 1.0
Carbon Monoxide 10 +. 3
Carbon Dioxide 9.5 +_ 2.0
Ethylene 4.3^0.6
Ethane 0.12 ^ 0.04
Higher Heating Value 7700 kJ/Nm3 (195 Btu/SCF)
Source: Craig, J. W. T., et al., "Chemically Active
Fluid-Bed Process for Sulphur Removal During
Gasification of Heavy Fuel Oil - Third
Phase," EPA-600/2-76-248, September 1976.
-43-
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The specific installation selected for detailed study is the 17-MWg CAFB
demonstration plant at Central Power and Light Company (Corpus Christi), La
Raima station in San Benito, Texas. Design flow rates for this installation
43
are the basis for the 500 MW£ material balance shown on Figure 2-12. Process
development originated with the gasifier pilot-plant work at Esso Research Cen-
ter Abingdon (ERCA), United Kingdom, in 1966.13 The U. S. EPA has contracted
with Foster Wheeler Energy Corporation (FWEC) the design of the demonstration
plant. FWEC has, in turn, signed a separate contract with Central Power and
Light so that EPA is sponsoring the design and testing and CPL is sponsoring
34
the construction and operation.
The CAFB gasifier/regenerator is a single unit which performs the two
functions of gasification and sorbent regeneration. Transfer of bed material
from the gasifier to the regenerator and return is accomplished in bed material
transfer conduits by the pulsation of high-pressure flue gas admitted to the
conduits. The recirculation rate is determined largely by the sulfide forma-
tion rate in the bed but is affected by the need to circulate bed material
through the regenerator to absorb excess heat and limit the overall regenerator
temperature. Bed material for the CAFB, as for most fluid bed combustion de-
signs which remove sulfur, is limestone.
The limestone to be used in the CAFB demonstration unit is that shown in
Table 2-9.
The RESOX unit mentioned above is a development of FWEC. Regenerator off-
gas, consisting of sulfur dioxide, carbon dioxide, and nitrogen, passes through
a cyclone before entering the RESOX reactor at a temperature of 650°C (1200°F).
(Fines are discarded with the spent stone from the regenerator.) This tempera-
ture is maintained by cooling the off-gas with injected steam which also pro-
duces the required HgO/SOp ratio. Control air is also added to the RESOX inlet
to furnish oxygen to maintain and control the reactor temperature at 760-816°C
(1400-1500°F). The reduction reaction
S02 + C —** C02 + S
is exothermic but cannot maintain the temperature necessary for the high con-
version of S02 to sulfur. Carbon is added to the RESOX reactor in the form of
anthraci te coal.
-44-
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•£»
in
Residual Oil
145,000 kg/h
Limestone
19,076 kg/h
Air-Gasifier
389,119 kg/h
Air-Regenerator
55,731 kg/h ~~
Coal
3990 kg/h
Steam
7480 kg/h
Recycled Flue Gas
135,774 kg/h
CAFB
Ash Sulfur Stone
1871 kg/h 2867 kg/h 7605 kg/h
Product Gas
743,827 kg/h
Figure 2-12 - Material Balance for a 500 MWe CAFB Process
-------
TABLE 2-9. COMPOSITION OF LIMESTONE USED FOR THE CAFB DEMONSTRATION
Concentration,
Component wt. percent*
CaO 53.27%
MgO 0.53%
C02 43.58%
A1203 0.94%
Fe203 0.97%
Si02 1.84%
Na20 0.026%
KgO 0.17%
Cl 0.0032%
Organic C 0.07%
Total 101.4%
* Analysis performed by Research & Develop-
ment Center, Westinghouse Electric Corpor-
ation.
-46-
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75 to 90% of the sulfur dioxide entering the reactor exits as elemental
sulfur after being cooled in a sulfur condensing heat exchanger. The unreacted
S02 is returned to the gasifier.
The major discharge stream and the major reason for existence of the CAFB
is the boiler flue gas. Low-Btu gas output from the CAFB unit, after passing
through a cyclone, enters the low-Btu burners in the existing plant boiler.
Fines are returned from the cyclone to the gasifier. Compared to conventional
combustion, when burning gasified residual oil, sulfur dioxides in the flue gas
are eliminated, nitrogen oxides are greatly reduced, and particulates are con-
trollable.
FWEC air emissions calculated and predicted are given in Table 2-10. NO
J\
emissions are expected to be below the EPA standard for oil and similar to the
standards for natural gas primarily because of the low adiabatic flame tempera-
ture for low-Btu gas and the dilution effect of the great volume of inert gas
in the low-Btu product gas. Sulfur dioxide, of course, is controlled by the re-
moval of sulfur in the gasifier. Particulate emissions are difficult to calcu-
late for the CAFB because of the many variables to be considered, e.g., cyclone
efficiency, ash content of the feedstock, carbon content of the particulate, and
28
velocity through the bed. Test results from ERCA have a wide range above and
42
below the EPA standard for No. 6 oil burning. Verification of CAFB particu-
late emissions must await demonstration unit testing.
Spent bed material from the regenerator will consist primarily of CaO with
small amounts of calcium sulfide and calcium sulfate. The expected output rate
of 0.08 Kg/s or 610 Ib/hr for the demonstration plant is approximately 7605
kg/hr (16,769 Ib/hr) for a scaled 500 MWe plant. Possibly, this material could
be sold in its effluent form, or even processed to be made commercially accept-
able. If no market exists for this material, it must be processed (e.g., by
dead burning) prior to disposal, since CaO and CaS react exothermically with
water. Methods of processing and disposal are currently being investigated.
The RESOX unit produces a solid waste of approximately 75 percent carbon
and 25 percent ash with small amounts of sulfur. This material has a heating
value of approximately 24.4 MJ/Kg (10,500 Btu/lb) and is acceptable for use as
a low-sulfur fuel.
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TABLE 2-10. ESTIMATED COMPARISON OF EMISSIONS FROM CAFB
Steam
Generator
Fuel
Natural Gas
No. 6 Oil
Coal
Low-Btu Gas
From No. 6 Oil
Low-Btu Gas
From Coal
Emissions - lb/106 Btu (mg/MJ)
NO
•x-
0.13
(77)
0.45
(192)
0.72
(307)
0.18
(77)
0.18
(77)
EPA
Std.
0.2
(85)
0.3
(128)
0.7
(299)
SO,
Est.
6.97
(2,982)
0.76
(325)
1.09
(466)
EPA
Std.
2.9 0.8
(1,240) (342)
1.2
(513)
0.1
(43)
0.1
Particulates
Est.
0.076
(33)
10.7
(4,577)
0.1
(43)
0.1
(43)
(43)
Source: McMillan, R. E. and F. D. Zoldak, "A Discussion of the Chemically
Active Fluid Bed Process (CAFB)," Frontiers of Power Technology
Conference, October 26 and 27, 1977.
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Process Status
Current cost figures for the CAFB demonstration unit are somewhat meaning-
less if one is attempting to compare it directly with the other processes discussed
in this report. It is a retrofit, demonstration unit, and the published costs do
not reflect initial engineering required for system design and equipment speci-
fication. Published costs for this unit are in FWEC's preliminary process de-
43
sign manual. Some preliminary capital and operating costs were developed in
1975. Values ranged from $102/kW to $190/kW and from 3.28 mills/kW-h to 6.25
?l
mills/kW-h, dependent upon unit size and other variables. Although these num-
bers are out of date and were generated before the CAFB demonstration design
and construction were begun, they are of the same order of magnitude as the
costs for other processes considered in this report.
FWEC has produced a performance comparison for the CAFB demonstration unit;
calculated boiler efficiency for the La Raima unit fired with natural gas was
84.53% as opposed to 84.03% for a cold CAFB gas. Overall plant efficiency was
23% using natural gas and 21% burning and producing the CAFB gas. Overall
plant efficiencies are low due to the 30-year age of the La Pal ma unit. On a
newer unit, overall efficiencies were calculated as 34% on natural gas and 30%
on CAFB gas.
The CAFB shares the wide fuel flexibility of the fluidized bed type of
combustion. FBC units are now being operated and developed for most classes of
coal. The CAFB pilot plant at ERCA is now being tested on samples of Texas
lignite, which will also be gasified later in the CPL demonstration plant. The
CAFB for power generation from electric utilities is expected to have none of
the feedstock restrictions which other processes such as HDS and POX require.
2.6 SUMMARY
Section 2 has presented updated information on Phase I processes, those
which are operating or in commercial design. The CAFB, a Phase II demonstra-
tion plant design, has been introduced into the discussion. No attempt has been
made to closely compare each process on the basis of economics or environmental
impact. Such a comparative evaluation has not been planned for this past year's
work, but it will be a part of this project's final report. A summary, by pro-
cess, of some of the major environmental problems and areas for further engineer-
ing study follows.
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Japanese units form the basis for the information on non-regenerable FGD
processes. All U. S. units operate on coal-fired boiler stack gas. The non-
regenerable FGD process has solved an air pollution problem but has created a
solids disposal problem. Although the Japanese are able, in some cases, to
use the gypsum output from the lime/limestone scrubbers as a marketable by-
product, in the U. S. it becomes a throwaway sludge which requires a large
amount of land space when dumped into a settling pond. Lined ponds merely
contain the sludge, and leaching of pollutants in unlined ponds continues to
be an environmental problem. The water required can represent use of a scarce
resource in some areas of the U. S. Operating availability of the FGD unit is
still a problem, and the entire installation is an added cost in capital and
operation for the utility.
Regenerable FGD systems, although requiring more energy (for by-product
processing) than non-regenerable FGD systems, offer the potential for lower
overall costs by producing a usable and marketable by-product. This potential
is somewhat elusive due to the changing needs of the by-product sulfur market
and the capital investment required to build a separate processing plant (e.g.,
a sulfuric acid plant) for by-product reclamation. Such a plant would exper-
ience a variable feed composition and flow as the FGD and utility operation
varied with power demand and unit availability.
Fugitive emissions present a potential environmental problem when fine
particle sorbents such as MgO are used. All regenerable FGD systems for resi-
dual oil are in Japan. Even there, the regenerable FGD process systems are not
as well established as the non-regenerable FGD systems are for utility boilers.
Although designed for SO^ removal, both types of FGD processes do well in
removing particulates (40-80%) and NOX (50-90%). Nitrogen oxide scrubbers,
which may be incorporated into FGD units, are currently being developed in Japan.
The environmental hazard , if any, associated with the particulates not remov-
ed, is an area for further study.
HDS processes remove most of the sulfur and heavy metals from the residual
oil. However, the sulfur and heavy metal concentrations on HDS catalysts are
major points of concern. Spent catalyst regeneration and disposal are problems
still to be evaluated. The high initial investment and the cost of hydrogen
-50-
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affect the economics of HDS vis-a-vis the other processes described here. HDS
units are built on a refinery scale, supplying more oil product than most indi-
vidual utility stations require. The development of environmental goals is
difficult because of interconnection of the HDS process with many other refinery
ery streams, and because of the number and complexity of waste streams and
treatment schemes. Operating experience to date has been largely with light
Arabian reduced crude, a relatively easy feedstock to desulfurize.
The POX process is very well developed, especially the gasification phase.
No combined-cycle POX installations exist, however. For electric power gener-
ation, because of the low-Btu output, the POX gasifier must be coupled with a
boiler or, preferably, a gas turbine combined-cycle. Its utilization depends
upon the acceptance of the combined-cycle concept and the development of high
efficiency cycles. Final disposal of the carbon soot by-product and/or reactor
ash and the wash water are major environmental concerns.
The CAFB process appears to be outstanding as a retrofit gasifier to exist-
ing natural gas or oil-fired boilers. For economic reasons, the low-Btu gas
must be used on-site. Fugitive emissions are controlled by designing the bed
material regenerator within the same housing as the gasifier. Spent stone dis-
posal will require further study. Particulate control in the product gas, which
contains bed material, is a problem to be solved. Based on test results from
the demonstration unit, economic and performance data need further attention.
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SECTION 3
CURRENT ENVIRONMENTAL BACKGROUND/OBJECTIVES DEVELOPMENT
Environmental assessment involves the determination of contaminant levels
associated with emissions and effluents from a point source, and the comparison
of those determinations with desirable control levels.
A knowledge of the existing decisions, limits, criteria, and legal re-
strictions pertaining to environmental contaminants is most useful in the pre-
liminary determination of pollutants prioritization and desired goals or range
of limitations in the environment. A thorough review of all recent pertinent
literature, including Federal Register, Environment Reporter, and Code of Fed-
eral Regulations, was made by an EPA contract granted to Research Triangle In-
stitute, Research Triangle Park, North Carolina. Some emphasis has also been
placed on those regulations that are associated with fossil fuels processes,
such as the recommended standards for gasification plants.
3.1 MULTIMEDIA ENVIRONMENTAL GOALS (MEG's)
The establishment of MEG's as estimates of desirable ambient and emission
levels of control is an integral part of EPA's environmental assessment ap-
proach. As a result, Minimum Acute Toxicity Effluent (MATE) values to serve
as MEG's for each chemical substance on the MEG's master list were established
in the absence of existing or proposed federal guidelines. The MATE values are
estimated levels of effluent contaminants considered to be safe for short-term
exposures. The MATE values provide an increasingly useful tool for comparison
in environmental assessment.
The objectives in the use of MEG's are two-fold: (1) to compare environ-
mental pollutant loadings from specific sources to MEG's; and (2) to provide
sufficient information for decision making. The use of MEG's shall include
ranking of waste streams, establishing priorities for sampling and analysis,
control options recommendation, and the provision of a basis for the establish-
ment or revision of standards and regulations.
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The relationship among various functional environmental assessment areas
is depicted in Figure 1-1.
Multimedia Environmental Goals (MEG's) are levels of contaminants or de-
gradants (in ambient air, water, or land or in emissions or effluents conveyed
to ambient media) that are judged to be: (1) appropriate for preventing cer-
tain negative effects in the surrounding populations or ecosystems; or (2) rep-
resentative of the control limits achievable through technology.
A master list of more than 600 chemical substances and physical agents
has been compiled using selection factors prescribed by EPA. Primary emphasis
has been placed on contaminants from fossil fuels processes (particularly coal
gasification and liquefaction), and the master list has been compiled largely
on the basis of the literature pertinent to these processes. Process streams
were characterized both qualitatively and quantitatively, wherever possible, to
provide insight for selecting substances likely to be present but not mentioned
specifically in the process literature.
Three levels of priority were assigned to the selection factors to deter-
mine what substances, of all possible chemical substances and physical agents
that might be described as environmental contaminants, would be entered on the
master list for MEG's. The selection factors were categorized into three
groups - primary, secondary, and tertiary.
The primary group includes pollutants associated with fossil fuels pro-
cesses. All individual substances or classes of substances known or suspected
to be present in the emissions or effluents from fossil fuels processes must
appear on the master list.
Substances receiving secondary consideration include those for which fed-
eral standards exist or have been proposed (ambient, emission, or occupational)
or those for which a Threshold Limit Value (TLV) has been established or an
LD5Q has been reported. Also included in the secondary group are substances
which have been listed as suspected carcinogens or have appeared on the EPA
Consent Decree List. Compounds that meet any one of the four secondary selec-
tion factors and are representative of a class of compounds associated with
fossil fuels processes must appear on the master list.
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If the substance is present as a pollutant in the environment, or if it
has been identified as being highly toxic, it will receive tertiary or option-
al consideration. Consideration for inclusion in the master list is also given
to certain additional pollutants, not necessarily associated with fossil fuels
processes, provided they satisfy either of the tertiary selection factors.
A detailed documentation regarding MEG's and MATE'S was prepared by Re-
search Triangle Institute for EPA. A sample MEG's chart for 2-aminonaphthalene
is included (Table 3-1).
3.1.1 Emission Level Goals
Emission level goals presented in the top half of a MEG's chart pertain
to gaseous emissions to the air, aqueous effluents to water, and solid waste
to be disposed to land. These goals may have technological or ambient factors
as their bases. Technological factors refer to the limitations placed on con-
trol levels by technology, either existing or developing (i.e., equipment ca-
pabilities or process parameters). The standards of performance for new sta-
tionary sources provides an example of promulgated emission level goals based
on technology.
Since there is obviously a relationship between contaminant concentrations
in emissions and the presence of these contaminants in ambient media, it is im-
perative to consider ambient factors when establishing emission level goals.
Ambient factors included in the MEG's chart as criteria for emission level
goals include minimum acute toxicity effluents, ambient level goals, and elim-
ination of discharge. Minimum Acute Toxicity Effluents (MATE's) are concentra-
tions of pollutants in undiluted emission streams that would not adversely af-
fect those persons or ecological systems exposed for short periods of time.
In applying the MEG charts, one problem reported is that, for some poten-
tial pollutants, such as benzo-a-pyrene, the MATE value given is below the
detection limit for the substance. Consequently, it is impossible to deter-
mine whether a sample concentration is above or below the MATE value. Ano-
ther problem is that MATE'S have not yet been established for some species
that may be collected in Level 1 sampling and analysis. Some MATE values for
water and land do not make sense because they are based on the MATE value for
air. An example is calcium, whose MATE value for land, which is based on the
air MATE, seems unrealistically low.
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MULTIMEDIA
ENVIRONMENTAL
GOALS
X
10C
2-AMINONAPHTHALENE
Air, g/m
(ppm Vol)
Water, g/l
(ppm Wt)
Land, g/g
(ppm Wt)
Emission Level Goals
1. Based on Best Technology
A. Existing Standards
NSPS, BPT, BAT
3. Developing Technology
Engineering Estimates
(R&D Goals)
II. Based on Ambient Factors
A. Minimum Acute
Toxicity Effluent
Based on
Health
Effects
1.65E2
2.5E3
5.0 EO
Based on
Ecological
Effects
1.0E2
2.0E-1
B. Ambient Level Goal*
Based on
Health
Effects
0.4
6
0.012
Based on
Ecological
Effects
50
0.1
C. Elimination of
Discharge
Natural Background*
*To be multiplied by dilution factor.
Ambient Level Goals
Air, g/m3
(ppm Vol)
Water, g/l
(ppm Wt)
Land, gfg
(ppm Wt)
I. Current or Proposed Ambient
Standards or Criteria
A. Based on
Health Effects
-
B. Based on
Ecological Effects
II. Toxicity Based Estimated
Permissible Concentration
A. Based on
Health Effects
59
291
0.6
B. Based on
Ecological Effects
50
0.1
II. Zero Threshold
Pollutants Estimated
Permissible Concen-
tration
Based on
Health Effects
0.4
6
0.012
Table 3-1 - Sample MEG Chart
Source: deland, J. G. and G. L Kingsbury, "Summary of Key Federal Regulations and Criteria for Multimedia Environmental Control,"
Draft, 6842-1325, Research Triangle Institute, June, 1977.
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3.1.2 Ambient Level Goals
The ambient level goals are Estimated Permissible Concentrations (EPC's)
of pollutants in emission streams which, after dispersion, will not cause the
level of contamination in the ambient receiving medium to exceed a safe contin-
uous exposure concentration. The Elimination of Discharge (EOD) refers to
concentrations of pollutants in emission streams which, after dilution, will
not cause the level of contamination to exceed levels measured as "natural
background."
Although technology-based emission level goals are highly source speci-
fic, goals based on ambient factors can be considered universally applicable
to discharge streams for any industry. The emission level goals correspond
to the most stringent ambient level goals (dilution factor to be applied)
appearing in the MEG chart, regardless of source of emission.
The lower half of a MEG chart is designed to present three classifica-
tions of ambient level goals; all of these goals describe estimated permissi-
ble concentrations (EPC's) for continuous exposure. The ambient level goals
presented in the chart are those based on current or proposed federal ambient
standards or criteria, toxicity (acute and chronic effects considered), and
carcinogenicity or teratogenicity (for zero threshold pollutants). The term
"zero threshold pollutants" is used to distinguish contaminants demonstrated
to be potentially carcinogenic or teratogenic. The concept of thresholds is
based on the premise that there exists for every chemical substance some de-
fineable concentration below which that chemical will not produce a toxic
response in an exposed subject. The existence of thresholds for carcinogens,
teratogens, and mutagens has been widely debated and is still unresolved.
Existing or proposed federal standards, criteria, or recommendations are
acknowledged as previously established goals and have been utilized wherever
applicable. For those substances not addressed by current guidelines, consid-
eration in arriving at MEG's has been given to: (1) established or estimated
human threshold levels; (2) acceptable risk levels for lifetime exposure to
suspected carcinogens or teratogens; (3) degrees of contamination considered
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reasonable for protection of existing ecosystems; (4) cumulative potential in
aquatic organisms, livestock, and vegetation; and (5) hazards to human health
or to ecology induced by short-term exposure to emissions. It is recognized
that there are several other criteria pertinent to MEG's that have not been
incorporated into the methodology developed thus far (for example, quality of
the receiving media before introduction of the substance, characteristics of
transport and dispersion of emissions, consideration of location and abundance
of sources emitting a given pollutant, numbers of populations affected, syner-
gisms, antagonisms, and other secondary pollutant associations). Research is
needed before more refined models of estimation can be developed to allow in-
clusion of these criteria.
Three distinct aspects of MEG's methodology development have been address-
ed so far. These are:
1. Assembling and collating all existing or proposed federal
guidelines pertinent to each chemical substance on the
master list.
2. Defining models to translate empirical data into EPA's
methodology, e.g., estimated permissible concentrations
for continuous exposure to chemical toxicants in air,
water, and land.
3. Defining models to translate empirical data into values
describing MATE'S (minimum acute toxicity effluents) safe
for short-term exposure; such effluents may be gases,
liquids, or solids.
3.2 NSPS SUPPORT RESEARCH DATA BASE FOR EMISSION STANDARDS
One major product of the environmental assessment effort will be the de-
velopment of a research data base adequate for recommending emission standards
for residual fuel oil utilization systems used in power generation or indus-
trial steam generation. The research data base will include waste stream anal-
ysis data which constitute best current practice, including characterization of
the available control technology, and health/ecology-based (ambient-level-
goals-related) emission level goals.
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An effluent standard is a limit on the amount or concentration of a pollu-
tant emitted from a source. The concentration of pollutant in the effluent may
be stated subjectively, in terms of its appearance to the eye or its odor, or
objectively, in terms of its weight or volume. Emission standards may be de-
rived from ambient quality considerations; process, fuel, and equipment consid-
erations, or both. Effluent standards sometimes reflect economic, sociological,
and political considerations in addition to those which are technological. In
some cases, the technological ability to control certain pollutants is avail-
able but is not implemented for economic, sociological, or political reasons.
However, despite considerable economic, sociological, and political pressure to
more stringently regulate certain emissions, adequate technological ability is
often lacking.
The major rationales for developing effluent standards have been based
upon the following factors: (1) ambient quality; (2) ambient quality standards;
(3) number and location of sources; and (4) meteorology and topography. The
most common rationale for developing effluent limits for stationary sources is
the application of best practicable means for control. Under this rationale,
the degree of emission limitation achievable at the best designed and operated
installation in a category sets the emission limits for all other installations
of that category. The procedures generally being used in setting effluent stan-
dards involve derivations from ambient quality standards, from ambient background
concentration, including the roll-back approach, and from process and equipment
consideration.
There have been no specific regulations or guidelines officially issued
regarding emissions from residual fuel oil utilization processes. Two applica-
ble ones are the "Recommended Standards Support" regarding coal conversion in-
volving Lurgi coal gasification process, and "Recommended Standards of Perform-
ance" for coal gasification process. These informal standards of performance
were recommended by EPA and issued by the Office of Air Quality Planning and
Standards (OAQPS).
To ensure adequate database development in supporting effluent standards
setting, the steps in the environmental assessment methodology developed by
EPA(5) will be followed in our residual fuel oil utilization environmental as-
sessment work. The steps are summarized as follows:
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Step 1. Identification of current technology and environment-
al background, including development of "the universe
of potential pollutants."
Step 2. Development of environmental objectives via the
Multimedia Environmental Goals (MEG's) Chart, which
is preceded by preliminary pollutant prioritization.
Step 3. Analysis of emissions from operating residual fuel
oil utilization processes.
Step 4. Assessment of existing control technology based on
emission stream composition results from Steps 1 and
3.
Step 5. Analysis of environmental control alternatives,
using Source Analysis Models (SAM's).
Step 6. Identification of further data and technology needs,
including review of logical aspects of design of a
control technology development program.
The ambient background information is the backbone of effluent standards
setting, as well as the starting point of any environmental assessment work.
A vast amount of information and data regarding ambient background has been
collected and published over the years. There is more unpublished information
scattered around in research institutes, universities, private industries, and
governmental agencies.
To collect, evaluate, and process data on ambient concentrations in gas-
eous liquid, and solid media for noncriteria chemical substances, EPA initiated
and granted a noncriteria ambient baseline data contract to Research Triangle
Institute, Research Triangle Park, North Carolina.
A computer search of five files has been initiated. Files include: APTIC,
WRA, NTIS, STOREX, and Pollution Abstracts. Over 100 reprints covering 350
chemicals have been ordered. These will serve as the basis for input into the
data base being developed by Research Triangle Institute with assistance from
the Midwest Research Institute.
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Air Pollution
Although no effluent regulations or guidelines have been issued specifical-
ly for residual oil utilization processes, certain general emission guidelines
are applicable. National primary and secondary ambient air quality standards
have been promulgated which set limits on the ambient concentrations of sulfur
oxides, particulate matter, carbon monoxide, photochemical oxidants, hydrocarbons,
and nitrogen dioxide. The regulations call for prevention of significant deter-
ioration (PSD), thus setting a limit on the total pollutant level from all
sources in a given area, including residual oil utilization processes.
New source performance standards (NSPS) have been established for fossil-
fuel fired steam generators for sulfur oxides, nitrogen oxides, and particulate
matter. "Fossil fuel," as defined in the regulations, means natural gas, petro-
leum, coal, and any form of solid, liquid, or gaseous fuel derived from such
materials, and would include residual oil.
State implementation plans (SIP's) are required by law for each state.
SIP's provide the mechanism within each state for meeting national ambient goals,
using reasonable available control technology.
The national emission standards for hazardous air pollutants (NESHAP) apply
to specific industries likely to generate asbestos, beryllium, mercury, and
vinyl chloride. Although NESHAP limits are not legally enforceable standards
for power generation facilities (such as residual oil utilization processes),
they do serve as emission guidelines.
In non-attainment areas, the desired effluent goal for any point source,
including residual oil utilization facilities, is the lowest achievable emission
rate. No standards have been set for some potential air pollutants, such as
oxides and sulfates of trace metals.
Water Pollution
One source of effluent guidelines for water pollutants is the Resource Con-
servation and Recovery Act (RCRA). The National Pollutant Discharge Elimination
System (NPDES) permits, licenses (such as for ocean dumping), pretreatment stan-
dards, and state guidelines also set limits on pollutant discharges in waste-
water.
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The Safe Drinking Water Act provides additional ambient guidelines, and
the new source performance standards for steam electric power generating facil-
ities provide effluent standards for pollutants such as total suspended solids
(TSS) and oil and grease. As in the case of air pollutants, many potential
water-borne pollutants such as heavy metals and organics are presently without
effluent standards.
Controlling waterborne toxic and hazardous chemicals resultant from the
residual fuel utilization processes will be far more complicated than controll-
ing the conventional wastewater parameters, such as BOD, pH, TSS, etc. Based
on EPA's experience in implementing water and hazardous materials programs of
PL 92-500, Best Available Technology (BAT) is still the best approach. BAT
calls for heavy reliance on in-process controls and on advanced technology as
the most appropriate means for dealing with the majority of toxic discharges.
The nature of the toxics problem is so pervasive that the most effective ap-
proach in dealing with it is on an industry-by-industry basis. EPA's studies
over the past two years have identified large numbers of pollutants that have
known or strongly suspected toxic effects. Many are carcinogenic. The most
practical way of solving such a problem is to examine each industry category or
subcategory. In this manner, control options can be developed that deal most
effectively with the entire wastestream of an industry. This is the approach
called for in BAT. As new technology is developed, what was best practicable
means in 1978 may be short of the best attainable in 1980. Since there is a
moving target, emissions goals may have to be set at various time periods; and,
means must be provided administratively to provide adequate incentive for con-
tinued technology development.
Solid Wastes
The Resource Conservation and Recovery Act (RCRA) calls for state plans for
development of solid waste disposal practices which comply with federal guide-
lines. Solid waste criteria, identification methods, and listing of hazardous
wastes are available in the RCRA.
Toxic Substances
Recent EPA actions have officially endorsed toxic effluent standards and
established effluent limitations requirements for selected toxicants. Three
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different kinds of regulations are anticipated for ten classes of industries by
December 1979. These regulations include effluent limitations, pretreatment
standards, and new source performance standards. A permit procedure will be
incorporated into the National Pollutant Discharge Elimination System (NPDES)
for certain toxic effluents. The NPDES permits will have to be reviewed annual-
ly to incorporate new toxic limitations.
The EPA is presently undertaking a major assessment of toxic pollutants
discharged by industrial sources in order to review and revise, if necessary,
the effluent limitations within five years. A criteria has been established
for assigning priority to specific compounds, which in general are thought to
pose a threat to human health as a result of exposure. As a result of the EPA
work, the following regulations will be put into effect:
1) Revised effluent limitations based on the Best Available
Technology Economically Achievable (BATEA) to be met by
1983;
2) Revised New Source Performance Standards (NSPS) based on
the Best Available Demonstrated Control Technology
(BADCT) to be met by new source industrial dischargers;
3) Revised pretreatment standards for existing dischargers
to any publicly-owned treatment facility; and
4) Revised pretreatment standards for new sources for new
dischargers to publicly-owned treatment facilities.
The EPA has scheduled completion dates for development of these regulations on
an industry basis by December 1979. The EPA has recommended that the BATEA
limitations not be regarded as high priority enforcement items until the toxic
effluent guidelines become available after 1979.
The Toxic Substances Control Act (TOSCA) mandates registration and pre-
manufacture notification for new chemical substances, and provides for testing
of potential toxicants. Data on health and/or environmental effects of poten-
tial toxic substances, collected via TOSCA-authorized testing, serves as a basis
for standards support.
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Radiation
Radiation is not foreseen as a major problem with residual oil utilization
processes. Currently, there are no applicable regulations; however, EPA's radia-
tion office is available to provide guidance, should it become necessary.
Noise
Noise from residual oil utilization processes is presently unregulated.
Establishment of a data base for noise regulation is presently underway at
EPA's office of noise.
3.3 SUMMARY
Concern with the current environmental background is focussed on ambient
and emission level goals for pollutants related to residual oil utilization pro-
cesses. Multimedia Environmental Goals (MEG's) have been established as esti-
mates of desirable ambient and emissions levels of control, and Minimum Acute
Toxicity Effluents (MATE's) have been established in the absence of existing or
proposed federal guidelines, and serve as a valuable tool for emissions compar-
isons.
Emission level goals are based on both technological factors and ambient
factors, and are highly source-specific. Ambient level goals are universally
applicable to discharge streams from any industry.
Research is needed for refinement of the MEG's to incorporate important
criteria that are presently not considered in MEG's development.
Effluent guidelines are being developed in the form of a research data
base adequate for recommending emissions standards. The most common rationale
for developing effluent limits for stationary sources is the application of
best practicable control technology. The ultimate basis for effluent standards
setting -is ambient background information.
Toxic effluent standards have recently been endorsed by EPA actions, and
criteria have been established for assigning priority to specific compounds.
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SECTION 4
ENVIRONMENTAL DATA ACQUISITION
The major goal of the Environmental Data Acquisition subtask is a compre-
hensive waste stream characterization for each residual oil utilization pro-
cess. The waste stream characterizations will be used to compare the environ-
mental impacts of each process.
Emissions loadings for each process can be established by two methods:
sampling/analysis and theoretical engineering analysis. Some weighted combina-
tion of both sets of results will most accurately predict the actual emissions.
Sampling and analysis results are valuable because they are taken directly
from operating facilities. However, neither equipment nor methods for sampling
and analysis are entirely accurate. For example, the SASS train is non-
isokinetic and has problems with metal contamination. Inorganics have been
found to dissolve in condensate/water rather than in the impingers, as originally
designed.
Theoretical engineering analysis based on the thermodynamics and kinetics
of the process serves as a check on the sampling/analysis results and as a
source of information for filling data gaps and estimating error in sampling/
analysis results.
4.1 EMISSIONS INVENTORY
In order for projected emissions loadings for each residual oil utiliza-
tion process to be compared with each other, the emissions must be based on
the same feedstock. Actual residual oil compositions, however, vary widely
from oil to oil. For typical residual oils, sulfur concentrations range from
1% to 6% by weight; and, nitrogen varies from 1000 to 6000 ppm by weight.
Trace element concentrations may vary over an even broader range. Of the 60
or so detectable trace species in residual oil, vanadium and nickel are two of
the most important indicators of metal content. Vanadium concentrations are
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found as low as 10 ppm by weight and as high as 300 ppm by weight, typically,
while nickel varies from less than 10 to at least 80 ppm by weight. The wide
variation in residuum constituents is due to the equally wide variation in
crude oils imported into the U.S.A. from sources around the world and the com-
mon refinery practice of blending the bottoms from several different crudes
into one final residual oil.
To maintain comparability between the different residual oil utilization
technologies, a composite oil analysis has been developed, based on a weighted
average of U. S. crudes, which is representative of a "typical" residual oil
feedstock (Table 4-1). By using this composite oil analysis as a basis for
projected emissions loadings, the air, water, and land pollutant removal effi-
ciencies can be readily compared between processes.
It is important to remember that the projected emissions based on the
composite oil analysis will, of course, be average emission rates and that
actual emissions from operating plants will depend on the composition of the
oil being fired. To establish the range of possible emissions, projections
based on dirtier-than-average and cleaner-than-average resids will be defined.
The major variables are sulfur and trace metals content.
For the CAFB and FGD processes, the other major source of potential pol-
lutants is the sorbent used. The non-regenerable or "throwaway" FGD process
under study employs limestone as the sorbent. The assumed limestone composi-
tion to be used for input to FGD emission calculations is taken from the ERCA
(Esso Research Center, Abingdon) analysis of BCR 1359, shown in Table 4-2,
since it is comprehensive, recent, and reliable.
The regenerable FGD process under study employes a magnesium oxide slurry.
The exact nature of MgO impurities as supplied to a magnesium oxide FGD system
has not been defined as of yet. So far, literature search has failed to find
a complete trace element analysis of MgO slurry; thus, sampling and analysis
may be the only source of obtaining this data.
The two viable sorbents for the CAFB process are limestone and dolomite;
thus, emissions based on both options are of concern. The BCR 1359 limestone
used as a basis for FGD emission calculations is also used as a basis for the
CAFB calculations. For CAFB with dolomite as the sorbent, the ERCA analysis
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TABLE 4-1. AVERAGE RESIDUAL OIL COMPOSITE ANALYSIS
(1)
Element
Carbon
Hydrogen
Sulfur
Nitrogen
Vanadium
Nickel
Potassium
Sodi urn
Iron
Silicon
Cal ci urn
Magnesium
Chlorine
Tin
Aluminum
Lead
Copper
Cadmi urn
Cobalt
Rubidium
Titanium
Manganese
Chromi urn
Barium
Zinc
Phosphorus
Molybdenum
Arsenic
Selenium
Concentration
85.1%
11.2%
2.5%
4400 PPM
160 PPM
42.2 PPM
34 PPM
31 PPM
18 PPM
17.5 PPM
14 PPM
13 PPM
12 PPM
6.2 PPM
3.8 PPM
3.5 PPM
2.8 PPM
2.27 PPM
(2)
2.
2
1,
1
1
1
1
.21 PPM
PPM
.8 PPM
.33 PPM
.3 PPM
.26 PPM
.26 PPM
1.1 PPM
0.90 PPM
0.8 PPM
0.7 PPM
Element
Uranium
Antimony
Boron
Gallium
Indium
Silver
Germanium
Thai1i urn
Zirconium
Stronti urn
Bromi ne
Fluorine
Ruthenium
Tellurium
Cesium
Beryl1i urn
Iodine
Lithium
Mercury
Tantalurn
Rhodi urn
Gold
Platinum
Scandi urn
Bi smuth
Cerium
Tungsten
Hafnium
Yttri urn
Niobium
Concentration
0.7 PPM
0.44 PPM
0.41 PPM
(2)
0.4
0.3
0.3
0.2
0.2
0.2
PPM
PPM
PPM
PPM
PPM
PPM
0.15 PPM
0.13 PPM
0.12 PPM
0.10 PPM
0.1 PPM
0.09 PPM
0.08 PPM
0.06 PPM
0.06 PPM
0.04 PPM
0.04 PPM
0.03 PPM
0.02 PPM
0.02 PPM
0.02 PPM
0.01 PPM
0.006 PPM
0.004 PPM
0.003 PPM
0.002 PPM
0.001 PPM
Note:(l) based on U. S. crudes, including imports and domestic sources
(2) concentration by weight
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TABLE 4-2. ANALYSIS OF LIMESTONE USED BY ERCA
1
Element
Ca
Mg*
.2
Si
Al2
Fe2
Sr
Ba'
Cl2
Na2
Ni2
Cd or In*
Mn3
Concentration,
by weight
71.5%
0.2 - 2%
600 - 6000 ppm
200 - 2500 ppm
200 - 2000 ppm
100 - 1000 ppm
100 - 1000 ppm
30 - 300 ppm
10 - 100 ppm
10 - 100 ppm
< 50 ppm
29+6 ppm
22 + 1 ppm
Element
Sb'
I2
Ti2
Te3
Cr3
La2
Co2
V2
Surface
Surface C
Surface Ca
Co3 =/C4
Concentration,
by weight
< 10 ppm
1 - 10 ppm
1-10 ppm
0.6-6 ppm
2 +_ 0.4 ppm
2 + 0.2 ppm
0.3-3 ppm
0.3 + 0.01 ppm
0.06 - 0.6 ppm
49.5%
38.9%
11.6%
0.5
Notes: 1. All results except surface elements and Co~ /C from ERCA
2. Atomic Absorption (AA) spectroscopy
3. Neutron Activation Analysis (NAA) performed by the U.K. Atomic
Energy Establishment, Harwell
4. Electron Spectroscopy for Chemical Analysis (ESCA) by 6CA
Corporati on
Source: Werner, et al., "Preliminary Environmental Assessment of the
CAFB," EPA-600/7-76-017, October, 1976.
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of Tymochtee dolomite is used. Although it does not include all trace elements,
it is the most complete dolomite analysis readily available and does include
all metal oxides above the ppm level, as well as vanadium, nickel, and sodium.
Those trace elements which occur in dolomite in lesser quantities probably
exist at levels nearly equal to their concentration in the BCR 1359 limestone
and will be assumed as such.
The only other major process inputs are the hydrogen and the catalyst for
hydrodesulfurization. The hydrogen feed to HDS, produced in the crude oil
cracking process, is greater than 99% pure. Any contamination is probably in
the form of minute amounts of hydrocarbons. HDS catalysts for desulfurization
of residual oil usually consist of an alumina or silica base, promoted with
catalyst material such as molybdenum, cobalt, nickel, or some combination of
these metals.
4.1.1 Theoretical Engineering Analysis
Computerized equilibrium calculations will be employed to predict trace
species formation during combustion of residual oil. Equilibrium compositions
of trace chemical compounds are determined by the free energy minimization
method, based on the following input data: (1) elemental analysis of all feed
materials (oil, air, and sorbent, where applicable); (2) process conditions
(temperature and pressure); (3) a list of all compounds expected to be formed;
(4) standard free energy of formation for each species at equilibrium condi-
tions; and (5) the phase (solid, liquid, or gas) of each species at equilibrium.
As an aid in determining expected pollutant loadings in FGD effluents,
the equilibrium calculations computer program will be used to determine combus-
tion products from a residual oil-fired boiler, which will serve as input to
the FGD scrubber system. Input to the computer program is based on the pre-
viously completed material balance for a 500MW scrubber system. At 20% ex-
cess combustion air, the resid flow to the boiler is 287,000 Ib/hr, and the
air flow is 4,680,000 Ib/hr. Standard boiler conditions are assumed to be
2000 Kand 1.5 psig (1.1 atm.). The oil and air feeds are broken down by ele-
ments and combined to give the total flow rate for each element into the boil-
er. The results are listed on Table 4-3.
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TABLE 4-3. EQUILIBRIUM CALCULATION INPUTS BASED ON COMPOSITE OIL
Total Mass Flow Rates, g/sec.
Element
Ni trogen
Oxygen
Carbon
Hydrogen
Argon
Sulfur
Vanadi urn
Nickel
Potassium
Sodi urn
Iron
Silicon
Cal ci urn
Magnesium
Chlorine
Tin
Aluminum
Lead
Copper
Cadmi urn
Cobalt
Rubidium
Titanium
Manganese
Chromium
Ban urn
Zinc V
Phosphorous
Molybdenum
Arsenic
CAFB
(Gasifier)
7.98 x 104
2.53 x 104
3.38 x 104
4.56 x 103
1,36 x 103
9.92 x 102
6.35 x 10°
n
1.94 x 10U
4.22 x 10°
1.52 x 10°
6.46 x 10°
1.79 x 101
3.73 x 103
5.79 x 101
7.63 x 10"1
2.46 x 10"1
7.20 x 10°
1.37 x 10"1
1.11 x 10"1
2.42 x 10"1
8.9 x 10"2
7.9 x 10"2
8.9 x 10"2
1.68 x 10"1
6.2 x 10"2
9.12 x 10"1
5.0 x 10"2
7.2 x 10"2
3.6 x 10"2
3.2 x 10"2
FGD
(Boiler)
4.41 x 105
1.40 x 105
3.09 x 104
4.68 x 103
7.55 x 103
9.04 x 102
5.79 x 10°
n
1.53 x 10U
1.23 x 10°
1.12 x 10°
6.51 x 10"1
6.33 x 10"1
5.06 x 10"1
4.70 x 10"1
4.34 x 10"1
2.24 x 10"1
1.38 x 10"1
1.27 x 10"1
1.01 x 10"1
8.2 x 10"2
8.0 x 10"2
7.2 x 10"2
6.5 x 10"2
4.8 x 10"2
4.7 x 10"2
4.6 x 10"2
4.6 x 10"2
4.0 x 10"2
3.3 x 10"2
2.9 x 10"2
(continued)
-69-
POX
(Gasifier)
2.05 x 105
6.50 x 104
3.95 x 104
5.48 x 103
3.50 x 103
1.16 x 103
7.42 x 10°
n
1.96 x 10U
1.58 x 10°
1.44 x 10°
8.34 x 10"1
8.11 x 10"1
6.49 x 10"1
6.03 x 10"!
5.56 x 10"1
2.87 x 10"1
1.76 x 10"1
1.62 x 10"1
1.30 x 10"1
1.05 x 10"1
1.02 x 10"1
9.3 x 10"2
8.3 x 10"2
6.2 x 10"2
6.0 x 10"2
5.8 x 10"2
5.8 x 10"2
5.1 x 10"2
4.2 x 10"2
3.7 x 10"2
HDS
(Boiler)
3.78 x 105
1.04 x 105
2.49 x 104
3.74 x 103
5.61 x 103
2.92 x 101
2.34 x 10"1
_2
6.2 x 10 L
5.0 x 10"2
4.5 x 10"2
2.6 x 10"2
2.6 x 10"2
2.0 x 10"2
1.9 x 10"2
1.8 x 10"2
9.1 x 10"3
5.6 x 10"3
5.1 x 10"3
4.1 x 10"3
3.3 x 10"3
3.2 x 10"3
2.9 x 10"3
2.6 x 10"3
1.9 x 10"3
1.9 x 10"3
o
1.8 x 10" J
M
1.8 x 10'*3
•5
1.6 x 10" J
1.3 x 10"3
1.2 x 10"3
-------
TABLE 4-3 (continued)
Total Mass Flow
Element
Selenium
Uranium
Antimony
Boron
Gallium
Indium
Silver
Germanium
Thallium
Zirconium
Strontium
Bromine
Fluorine
Ruthenium
Tel 1 uri urn
Cesium
Beryl 1 i urn
Iodine
Lithium
Mercury
Tantal urn
Rhodi urn
Gold
Platinum
Scandium
Bismuth
Cerium
Tungsten
Hafnium
Yttrium
Niobium
Lanthanum
CAFB
(Gasifier)
2.8 x 10"2
2.8 x Iff2
7.0 x 10"2
1.6 x 10"2
1.6 x 10"2
1.63 x 10"1
1.2 x 10"2
7.9 x 10"3
7.9 x 10~3
7.9 x 10"3
6.0 x 10"3
5.2 x 10"3
4.8 x 10"3
4.0 x 10"3
1.4 x 10"2
3.6 x 10"3
3.2 x 10"3
3.1 x 10~2
2.4 x 10"3
1.6 x 10"3
1.6 x 10"3
1.2 x 10"3
8 x 10"4
8 x 10"4
8 x 10"4
4 x 10"4
2 x 10"4
2 x 10"4
1 x 10"4
8 x 10"5
4 x TO"5
8.6 x 10"3
FGD
(Boiler)
2.5 x 10"2
2.5 x 10"2
1.6 x 10"2
1.5 x 10"2
1.4 x 10"2
1.1 x 10"2
1.1 x 10"2
7.2 x 10"3
7.2 x 10"3
7.2 x 10"3
5.4 x 10"3
4.7 x 10~3
4.3 x 10"3
3.6 x 10"3
3.6 x 10"3
3.3 x 10"3
2.9 x 10"3
2.2 x 10"3
2.2 x 10"3
1.5 x 10"3
1.5 x 10"3
1.1 x 10"3
7 x 10"4
7 x 10"4
7 x 10"4
4 x TO"4
2 x 10"4
1 x 10"4
1 x 10"4
8 x 10"5
4 x 10"5
*.
POX
(Gasifier)
3.2 x 10"2
3.2 x 10"2
2.0 x 10"2
1.9 x 10"2
1.9 x 10"2
1.4 x 10"2
1.4 x 10"2
9.3 x 10"3
9.3 x 10"3
9.3 x 10"3
7.0 x 10"3
6.0 x 10"3
5.6 x 10"3
4.6 x 10"3
4.6 x 10"3
4.3 x 10"3
3.7 x 10"3
2.8 x 10"3
2.8 x 10"3
1.9 x 10"3
1.9 x 10"3
1.4 x 10"3
9 x 10"4
9 x 10"4
9 x 10"4
5 x 10"4
3 x 10"4
2 x 10"4
1 x 10"4
9 x 10"5
5 x 10"5
HDS
(Boiler)
1.0 x 10"3
1.0 x 10"3
6 x 10~4
6 x 10"4
6 x 10"4
4 x 10"4
4 x 10"4
3 x 10"4
3 x 10"4
3 x 10"4
2 x 10"4
2 x 10"4
2 x 10"4
1 x 10"4
1 x 10"4
1 x 10"4
1 x 10"4
9 x 10"5
9 x 10"5
6 x 10"5
6 x 10"5
4 x 10"5
3 x 10"5
3 x 10"5
3 x 10"5
1 x 10"5
9 x 10"6
6 x 10"6
4 x 10"6
3 x 10~6
1 x TO"6
-70-
-------
Equilibrium calculations are to be performed on the three major unit oper-
ations of the CAFB process: gasification of the resid feed, regeneration of
spent sorbent, and combustion of the clean regenerator product gas in a boil-
er. Inputs to the computer program for gasification based on the material bal-
ance are 315,000 Ib/hr of resid, 41,400 Ib/hr of limestone, and 845,327 Ib/hr
of combustion air (about 22% of stoichiometric combustion air). Gasification
conditions are taken as 1140°Kand 1.5 psig (1.1 atm.).
Results of the equilibrium calculations for the gasifier will be evaluated
using available field data and engineering judgment to determine what fraction
of the generated pollutants are captured in the sorbent (and subsequently
transferred to the regenerator) and what fraction are emitted with the product
gas (which is used as boiler feed). The sorbent composition will then be used
as input to the computerized equilibrium calculations for determination of re-
generator products, and the product gas composition will be used as input to
the boiler equilibrium calculations to determine boiler flue gas pollutant
loadings. Regenerator conditions are 1310 Nand 1.5 psig (1.1 atm.), and boil-
er conditions are 2000 Kand 1.5 psig (1.1 atm.). Inputs for gasifier calcula-
tions are listed by element on the input sheet, but inputs for regenerator and
boiler calculations cannot be determined until the gasifier results are avail-
able. Factors for converting gasifier effluent results to input data for re-
generator and boiler calculations are being developed. Air/fuel ratio in the
boiler is 2.13, and air/sorbent ratio in the gasifier is 0.09. Conditions and
air flows are based on operating experience at the ERCA pilot plant.
Gasifier, regenerator, and boiler calculations will be repeated using do-
lomite, instead of limestone, as the sorbent. Inputs for the dolomite calcula-
tions have not been prepared due to lack of adequate dolomite trace element
analyses.
Emissions from the partial oxidation gasifier will be estimated by compu-
terized equilibrium calculations. Feed rates of 361,590 Ib/hr of resid and
2,169,539 Ib/hr of air (45% of stoichiometric combustion air) will be used, as
established in the material balance for a 500MWe capacity boiler. Typical
operating conditions for the gasification process are 1650 Kand 365 psia (25
atmospheres). However, the computer program is only valid for pressures up to
10 atmospheres, so a run will be made at that pressure; and, engineering
-71-
-------
judgment will be used to estimate pollutant generation at 25 atmospheres.
The gasifier products are split into two streams: cleaned low-Btu gas
and carbon slurry. The composition of the cleaned gas will be established by
subtracting from the equilibrium products the soot and ash expected to be en-
trained in the carbon slurry. The gasifier product gas elemental composition
will then be used as input to equilibrium calculations for the boiler which
follows the gasifier. At present, no data have been found on combustion air
requirements specifically for POX product gas combustion; but, if the gas com-
position can be assumed to be similar to CAFB product gas, then combustion air
is probably about 62% of stoichiometric air. Typical boiler conditions are
taken as 200cPKand 1.5 psig (1.1 atm.).
The elemental composition of HDS-processed residual oil cannot be deter-
mined by the computerized equilibrium calculations because the process temper-
atures are too low. The computer program will be helpful, however, to predict
pollutant formation in a 500MWe boiler fired with hydrodesulfurized resid, pro-
vided the desulfurized resid composition can be estimated. Since no complete
trace element analyses for hydrodesulfurized resid are available, the trace
element concentrations have been estimated by applying a 95% demetallization
factor (taken from actual data for Gulf IV HDS of Light Arabian residuum) to
the input trace element concentrations in the composite residual oil analysis.
Combustion conditions are assumed to be 2000°Kand 1.5 psig (1.1 atm.) with
10% excess air. The desulfurized fuel oil flow to the boiler is 232,078 Ib/hr,
and the combustion air flow is 3,481,170 Ib/hr.
Computerized equilibrium calculations have not yet been performed for the
specific processes under study, but the computer run matrix planned is shown
in Table 4-4. Limited data are available, however, from a previously publish-
23
ed report by Battelle. The data include computer-predicted equilibrium products
for the combustion of No. 6 fuel oil in a boiler. Computerized equilibrium
calculations were performed for a No. 6 fuel oil having the composition shown
in Table 4-5. Also shown is a comparison with the composite No. 6 fuel oil
prepared by Catalytic. This composition indicates that the input oil composi-
tion used in the Battelle predictions is generally higher in trace metals con-
tent for those species considered but does not include all of the species in-
cluded in the composite oil analysis.
-72-
-------
TABLE 4-4. PLANNED COMPUTER RUN MATRIX
Run
No.
1
2
2a
3
4
3a
4a
3b
4b
5
Pro-
cess
FGD
POX
POX
CAFB
CAFB
CAFB
CAFB
CAFB
CAFB
HDS
Unit
Boiler
Gasifier
Boiler
Gasifier
Gasifier
Regenerator
Regenerator
Boiler
Boiler
Boiler
% Stoi-
chiometric
Oil Air
Composite
Composite
Composite
Compos i te
Composite
Composite
Composite
Composite
Composite
Composite
120
45
125
22
22
.091*
.091*
125
125
no
Temper-
ature
2000°
1650°
2000°
1140°
1140°
1310°
1310°
2000°
2000°
2000°
K
K
K
K
K
K
K
K
K
K
Pressure
Sorbent
1.1 atm.
10 atm.
1
1
1
1
1
1
1
1
.1
.1
.1
.1
.1
.1
.1
.1
atm.
atm.
atm.
atm.
atm.
atm.
atm.
atm.
—
Limestone
Dolomite
Limestone
Dolomite
Limestone
Dolomite
--
* Air/Stone Ratio
-73-
-------
TABLE 4-5. A COMPARISON OF TYPICAL NO. 6 FUEL OIL COMPOSITIONS
Species
C
H2
N2
S2
V
Ni
Na
Fe
Al
Si
Mg
Cr
Ca
Co
Ti
Cl
K
Sn
Pb
Cu
Cd
Rb
Others
Battell e
Program Input
% By Weight
85.1
11.2
0.44
2.80
EPjn
225
40
18
262
251
188
20
16
13
12
6
Catalytic
Composite
85.1
11.2
0.44
2.5
160
42.2
31
18
3.8
17.5
13
1.3
14
2.21
1.8
12
34
6.2
3.5
2.8
2.27
2.0
<2
-74-
-------
Published results of Battelle's program runs for No. 6 fuel oil include
equilibrium products of combustion at 1800°K, 800°K, 650°K, and 500°K, for both
10% and 2% excess air, as well as one run at 1800°Kand -2% excess air. Results
for 9 major species are shown in Figure 4-1 over the temperature range consid-
ered, for 10% and 2% excess air.
The amount of excess air makes very little difference in equilibrium pro-
duct formation for the major species shown or for trace metal oxides and sul-
fates. The major effect of increased excess air is increased nitrogen oxide
production and CO reduction.
Combustion temperature has very little effect on the formation of the
major gaseous species N2> C02, H20, and 02; but, some of the compounds' con-
centrations vary dramatically between500°K and 1800°K. Sulfur dioxide, nitro-
gen oxide, and carbon monoxide concentrations are greater by at least six
orders of magnitude at the higher temperature, while SO- and HUSO* formation
is greater at the lower temperature.
Of the most abundant trace metal compounds formed, only Si02 and V205 re-
main constant over the entire temperature range. Aluminum, iron, and magne-
sium tend to form oxides at 800°Kand above and sulfates at 650°K and below.
Nickel and calcium form predominantly oxides at 1800 Nbut form mostly sulfates
at the lower temperatures.
The predominant sodium compound at 1800 Kis Na2SiOo, but sodium tends to
favor sulfates below that temperature. Titanium and chromium, at minor concen-
trations, tend to form oxides across the temperature spectrum. Cobalt follows
the general trend of forming oxides at the higher temperatures and sulfates at
the lower temperatures. The metal sulfate distribution agrees well with the
S02 distribution, which is highest at the higher temperatures where there are
fewer metal sulfates, and lowest at the lower temperatures where there are
more meta-1 sulfates. The sulfur, then, reacts to form predominantly S02 at
1800°K; but, as the combustion temperature decreases, more of the sulfur is
taken up in metal sulfates.
Emissions from Combustion Without Controls
The conditions for which computer data are available and most closely model
actual residual oil-fired utility boiler operating conditions are 1800°K and
-75-
-------
T 1 T
1100 1300
Temperature, °K
1700
10% E.A.
2% E.A.
Figure 4-1 - Comparison of Effects of Excess Air on Products of Oil Combustion
-76-
-------
10% excess combustion air (actual conditions generally vary between 1800-2200°K37
O
and 10-20% excess air). Products of residual oil combustion in a utility boil-
er, then, based on the Battelle oil analysis of Table 4-5, should closely resem-
ble the predicted equilibrium concentrations at those conditions. Solution
chemistry kinetics are not expected to influence primary sulfate formation; and,
in general, once the sulfates and nitrates are formed, they will not be destroy-
ed (although some may be neutralized by adsorption on particulate material).12
Table 4-6 indicates typical slag composition for a residuum-fired boiler.
At least part of each of the most abundant metal oxides appears to be captured
in the boiler deposits. However, since portions of these deposits will be re-
moved periodically via soot blowing, most of the pollutants will reach the at-
mosphere eventually. Thus, it is initially assumed that all of the predicted
combustion products are emitted to the atmosphere.
The Battelle equilibrium calculations predict the emission levels of 74
species in the residual oil-fired boiler flue gas. Of those, the 21 species
predicted to form in concentrations greater than one-tenth of their lowest MATE
value are shown in Table 4-7(a), ranked by concentration/MATE value in order of
their relative degree of potential hazard. Those of primary concern for control
technologies are the 17 species predicted to be formed at concentrations greater
than their MATE value. Table 4-7(b) lists those species predicted to exist in
effluent concentrations less than one-tenth of their MATE values, and which are
thus of secondary importance. Table 4-7(c) lists the 20 species for which no
MATE'S are available or easily estimated from others in the same category, and
whose potential hazard is therefore undefined.
FGD Emissions
The two major effluents from limestone FGD systems are the treated flue
gas and the spent sludge. Definitive trace species concentration data for the
flue gas and the sludge are not yet available, but the major emissions are
shown in Table 4-8.
All of the boiler effluent trace species of Tables 4-7(a), (b), and (c)
exist in the condensed phase. At least 90% of the condensed phase species
should be removed from the gas stream by the FGD mist eliminator. Thus, as a
preliminary indicator of FGD performance with respect to trace species in the
-77-
-------
TABLE 4-6. TYPICAL SLAG FROM BOILER FIRED WITH NO. 6 FUEL
Si02
A12°3
Fe203
CaO
MgO
NiO
V2°5
Na20
S03
Oil Ash
%
1.7
0.3
3.8
1.7
1.1
1.9
7.9
31.8
42.3
Superheater
Deposit
%
7.0
4.1
5.8
4.5
2.5
1.1
0.9
23.7
46.4
Note: (1) from Chemical Engineering Handbook,
5th Edition, J. H. Perry, p. 9-10.
-78-
-------
TABLE 4-7(a). EQUILIBRIUM CALCULATION - PREDICTED EMISSIONS FROM
RESIDUAL OIL-FIRED BOILER WITHOUT CONTROLS^)
V2°5
Cr203
S02 (g)
NiO
24
VO
Cr
V
C02 (g)
c.
CoO
NiS04
CO (g)
Ni(OH)2
Co 0
3 4
Al,0,
2 3
Si02
Ni
CoS04
CoC03
Co(OH)3
Co
Fraction of
Flue Gas (ppm)
23.8
1.3
3.33 x 103
2.9
.054
.039
.030
.026
c
1.85 x 10D
.600
.087
185.0
.052
.142
28.1
20.8
.026
.061
.052
.042
.034
MATE MATE
Health Ecology
ug/m3 ug/np
5 x 102 1.0
1.0
1.3 x 104
15
5 x 102 1.0
5 x 102 1.0
1.0
5 x 102 1.0
p.
9 x 10b
50
15<2>
4 x 104 1.2 x 105
15(2)
50^2^
1 x 104
1 x 104
15
50<2)
50
50
50
Cone. /MATE
19,226
1,052
207
157
43.7
31.6
24.3
21.1
16.7
9.71
4.70
3.74
2.81
2.30
2.27
1.68
1.40
.988
.842
.680
.550
Notes: (1) All species in condensed phase unless otherwise noted.
(2) Estimated from other MATE'S in same category.
-79-
-------
TABLE 4-7(b). POLLUTANTS HAVING PROJECTED EMISSIONS
LESS THAN ONE-TENTH OF THEIR MATE VALUE(l)
MgO
N02 (g)
Ti02
A12(S04)3
Fe
Na2S03
Al
Na2S04
Na2C03
Ti3°5
Na20
Ti2°3
NaOH
N20 (g)
MgS04
Ni(N03)2
TiO
Ti
Co(N03)2
C
Mg
Co(OH)2
Si
Ca
Na
Mg(N03)2
A1(N03)2
H2S04 (g)
HN03 (g)
COS (g)
N204 (g)
N205 (g)
CH4 (g)
Note: (1) All species in condensed phase unless otherwise
noted.
-------
TABLE 4-7(c). COMPOUNDS IN PREDICTED EFFLUENT FOR
WHICH NO MATE'S HAVE BEEN ESTABLISHED (1)
N2(g) Ca(OH)2
H20 (g) NaN02
02 (g) Fe(N03)2
NO (g) Ca(N03)2
H2 (g) Ca(N02)2
S03 (g) NaN03
Fe203 CaC03
Na2Si03 FeS04
CaO H2S03 (g)
CaSO. S2 (g)
Note: (1) All species in condensed phase
unless otherwise noted.
-81-
-------
TABLE 4-8. TYPICAL FGD EMISSIONS
For a 2.5% S residual oil at 10% excess combustion air
Stack Gas Composition
Per kg. #6 Fuel Oil
C02 3.24 kg
H90 .93 kg
so2
°2
Total
Sludge Composition
2H20
2H20
CaSO-
Unreacted Ca(OH)2
Unreacted CaCO.,
Total
.005 kg
11.34 kg
.32 kg
15.835 kg
Per kg. #6 Fuel Oil
.0484 kg
.0658 kg
.0174 kg
.0233 kg
.1549 kg
% Wt.
of Total
20.5%
5.9%
.03%
71.6%
2.0%
% of Total
31.2%
42.5%
11.2%
15.0%
-82-
-------
effluent, it is assumed that 90% of the trace species in the boiler effluent
are removed from the gas stream and taken up by the limestone slurry. Under
steady-state conditions, then, 90% of the trace species are assumed to exit the
system via the sludge.
The projected FGD stack gas trace species distribution of Table 4-9 is
based on the assumption that 10% of the boiler emissions of Table 4-7(a) will
escape the system and employs a factor of .974, which accounts for the increas-
ed flue gas mass due to make-up water evaporative losses, which exit via the
stack. Table 4-9 shows only those trace species predicted to escape the boil-
er in quantities equal to or greater than their MATE values. About half of
those are reduced to concentration/MATE ratios less than one, by the FGD sys-
tem. Of those species which are still projected to exist in concentrations
greater than their MATE value, four are vanadium compounds, two are of chromium,
and one is of nickel. The C02 emission level is 16.3 times its MATE value, but
the potential hazard posed by this amount of excess carbon dioxide is question-
able. As for SOp, its projected concentration in the stack gas exceeds its MATE
value by a factor of twenty, but it still meets the new source performance stan-
dard of 0.8 Ib S02 per million Btu input.* Vanadium pentoxide, V20g, an' cnrom~
ic oxide, Cr^O.,, pose the greatest potential hazard based on the projected con-
centration/MATE ratios of Table 4-9, followed by S02, NiO, V204, VO, and element-
al chromium and vanadium, and the borderline case of C02«
As previously stated, it is assumed for the case of this approximation that
90% of the trace species are accumulated in the limestone slurry. The slurry
composition based on this assumption is shown in Table 4-10. The trace element
g
concentration in micrograms per liter assumes a sludge density of 1.12 x 10
jg/l (sp.gr. = 1.12).8 Again, the major potential hazards are posed by nickel,
vanadium, chromium, and cobalt compounds (oxides and sulfates).
* Based on FGD-limestone material balance:
324.53 ppm x 5,100,000 Ib/hr = 1655 Ib S02 emitted/hr
1655 Ib S03/5166 x 106 Btu = .32 Ib S02/million Btu
hr hr
0.32 Ib SO,, 0.8 Ib $0g (current NSPS)
milliSn Btu mi Hi On Btu
-83-
-------
TABLE 4-9. PROJECTED COMPOSITION OF FGD STACK
Fraction of
V 0
2 5
Cr2°3
S02(g)
C02(g)
NiO
V-A
2 4
VO
Cr
V
CoO
NiS04
C0(g)
Ni(OH)2
C°3°4
A1203
Si02
Ni
CoS04
N2(g)
H20(g)
O2(g)
N0(g)
Flue Gas (ppm)
2.32
.13
325
181,000
.28
.005
.004
.003
.003
.058
.008
18.0
.005
.014
2.7
2.0
.003
.006
731 ,000
60,000
18,400
1,270
Cone. /MATE
1876.5
102.5^
20.2
16.3
15.3
4.26
3.08
2.37
2.06
.946
.458<2>
.364
.274(2)
.224(2)
.221
.164
.136
.096<2>
N
N
N
N
Notes: (1) All species in condensed phase unless otherwise noted.
(2) Based on MATE values estimated from others in same
category. _84_
-------
TABLE 4-10. PROJECTED COMPOSITION OF FGD LIMESTONE SLUDGE
Concentration
CaS04 • 2H20
CaSO, • 2H90
3 2
Ca(OH)2
CaC03
NiO
VoOc
25
NiS04
Cr00.,
2 3
Ni(OH)2
Ni
CoO
COoO*
UU3 4
V2°4
VO
CoS04
Alx,0~
ni2 3
V
Si02
Cr
in Sludge
ug/1
1.4 x 108
1.9 x 108
5.05 x 107
6.76 x 107
1.31 x 105
1.07 x 106
3937
5.85 x 104
2313
1201
2.7 x 104
6362
2425
1713
2714
1.27 x 106
1201
9.38 x 105
1312
MATE
uq/1
—
—
10
150
10*
250
10*
10
250
250*
150
150
250*
1.5 x 105
150
1.5 x 105
250
Cone. /MATE
--
__
—
—
13,124
7,157
394
234
231
120
109
25.4
16.2
11.4
10.9
8.45
8.01
6.26
5.25
* Based on MATE values estimated from others in same category.
-85-
-------
The major factor which determines the actual environmental impact of the
trace metals in the sludge is the propensity of the metals for being leached
into the groundwater. If leaching could be held to zero, that is, no trace
metal compounds escaping the sludge pond, then trace metal content of the
sludge would be of little concern. Plastic sludge pond liners provide a means
for eliminating the leaching problem, providing they do not split or break to
allow seepage into the ground. Most installations, however, use the much
cheaper clay-bottom pond, which does not totally prevent leaching. Chemical
fixing of the sludge does not eliminate leaching, either, so that in most
cases, the concentration and solubility of the sludge trace constituents must
be considered in order to predict the potential environmental impact of sludge
disposal.
Pollutant removal efficiencies for MgO slurry scrubbing are almost iden-
tical to those for limestone slurry scrubbing. Sulfur dioxide removal averages
90%, and condensed trace species removal via the venturi scrubber and the de-
mister is also around 90%. Therefore, the stack gas composition from MgO F6D
should be roughly equivalent to that of limestone FGD. Trace metal compounds
retained by the slurry, however, are not deposited in a sludge pond, as in the
case of non-regenerable slurry processes such as limestone scrubbing. Instead,
the trace constituents must either exit the system via the S02 gas stream from
the calciner or else build up in the magnesia slurry. Data on this area are
incomplete, such that conclusions about the fate of trace compounds in the MgO
system cannot be drawn at this point.
CAFB Emissions
There are three major effluent streams and one by-product stream from the
CAFB process by^which inlet stream pollutants can be emitted. Flue gas from
the CAFB product gas boiler, spent stone from the limestone regenerator, and
ash from the RESOX unit are the major pollutant streams; and, sulfur from
the sulfur condenser is a useful by-product.
A typical CAFB product gas composition is shown in Table 4-11. This pro-
duct gas is the result of fluidized bed residuum combustion with limestone in-
jection, which averages about 70% sulfur removal efficiency (SRE) judging by
pilot plant data and can reduce the S02 emission rate to less than half of the
-86-
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TABLE 4-11. CAFB FEEDSTOCK AND PRODUCT GAS ANALYSES^
Typical CAFB Feedstock Analysis^2)
Properties Values
Specific Gravity 0.957
Kinematic Viscosity
Cs at 140°F (60*0 201
Cs at 210°F (99°C) 41.1
Carbon, percent by weight 85.9
Hydrogen, percent by weight 11.3
Sulfur, percent by weight 2.3
Nitrogen, percent by weight 0.35
Conradson Carbon, percent by weight 11.6
Asphaltene, percent by weight 7.1
Vanadium, ppm 366
Nickel, ppm 43
Sodium, ppm 36
Iron, ppm 3
CAFB Product Gas Composition
Component Vol.. Percent
Hydrogen 8.6+3.0
Nitrogen 61 +_ 5
Methane 6.4+1.0
Carbon Monoxide 10+3
Carbon Dioxide 9.5 +_ 2.0
Ethylene 4.3 +_ 0.6
Ethane 0.12+0.04
Note: (1) Craig, J. W. T., et al., "Chemically Active Fluid-
Bed Process for Sulphur Removal During Gasification
of Heavy Fuel Oil - Third Phase," EPA-600/2-76-248,
September, 1976.
(2) Amuay Atmospheric Residuum
-87-
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EPA standard for S02- Nitrogen oxide production is also reduced. Pilot plant
boiler combustion of CAFB gasifier product generates about 166 ppm NO vs. about
34
263 ppm for direct combustion of fuel oil.
Initial mass balances performed by ERCA indicated near-complete retention
of fuel and limestone trace elements on the gasifier bed. Those results, how-
ever, assumed homogeneous distribution of trace elements on the bed; but, fur-
ther work by ERCA has indicated a preferential agglomeration of trace elements
onto the finer particles in the bed, and volatization from the bed and condensa-
12
tion on the boiler cyclone fines. Thus, it is expected that the boiler flue
gas will be essentially free of trace metals; but, at this time, the distribution
of trace metals between the spent stone and the cyclone fines is unknown. How-
ever, the current design for the Foster Wheeler 250MW plant calls for combina-
tion of the spent solids (bed stone and cyclone fines) in a storage silo and
41
subsequent removal to a disposal site. Thus, regardless of the distribution
of trace elements between the spent stone and the fines, they will end up in the
same place.
HDS Emissions
Typical HDS performance for three feedstocks is shown in Table 4-12. De-
sulfurization averages 96.5%, and demetallization ranges from 95% to 99% for the
examples presented. Vanadium and nickel removal average 99% each for the low
metal feedstocks considered. With higher metal content in the feed, catalyst
poisoning becomes a problem.
The major effluent streams from the HDS process are separator off-gas, sul-
fur recovery unit acid gas ^S), and sour water from the sour water stripper,
as well as the by-products naphtha and furnace oil. At this point, little is
known about the distribution of trace pollutants between these streams.
A rough approximation for emissions from a boiler burning HDS-generated low
sulfur fuel oil (LSFO) can be made by applying the demetallization factor of
95.3% to the products of combustion from a boiler without controls, shown in Ta-
ble 4-7(a). The results, shown in Table 4-13, give a preliminary indication of
potential problem pollutants. The S0« emission rate, based on 96.5% desulfuri-
zation, is seven times the SO, MATE value but still meets the New Source Perform-
11
ance Standard (NSPS) of 0.8 Ib/million Btu. Only seven trace metal compounds
-------
TABLE 4-12. TYPICAL HDS PERFORMANCE
(1)
Charge Stock Properties
API Gravity
Sulfur, wt. %
Nitrogen, wt. %
Carbon Residue, Rams,
Wt. %
Nickel, ppm
Vanadium, ppm
Yields: Run Avg.
Desulfurization, %
API Gravity
Sulfur, wt. %
Nitrogen, wt. %
Carbon Residue, Rams,
wt. %
Nickel, ppm
Vanadium, ppm
Demetallization, %
H2S, wt. %
NH.j, wt. %
wt. %
'F Naphtha, Vol. a
375UF + Fuel Oil, Vol. t
Chem. \\2 Consumption,
SCF/bbl
Kuwait
Atmosphere
Residua
16.6
3.8
.21
8.3
15.0
45.0
97
26
0.1
0.11
2.2
0.
0.
99.
3.
0.
1
3.
98.93
860
.2
1
.2
.94
11
.4
.93
No. 1
Light Arabian
Atmospheric
Residua
17.6
3.0
40 (Ni + V)
96.7
23.2
0.1
2.8
0.1
1.15
3.04
98.15
660
No. 2
Light Arabian
Atmospheric
Residua
18.5
2.93
.16
6.79
7.3
27.0
95.9
25.1
0.12
0.09
2.28
0.5
0.3
95.3
Note: (.1) from "Latest Data on Gulf HDS Process," Gulf Science and Tech-
nology Co., Hydrocarbon Processing. May 1977, pp. 97-104; and,
"The Gulf HDS Process," Gulf Research and Development Co.,
August 16, 1974.
-89-
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TABLE 4-13. PROJECTED HDS LSFO-FIRED BOILER COMBUSTION PRODUCTS
Combustion
Product
so2
co2
CO
V2°5
Cr2°3
NiO
V2°4
VO
Cr
V
CoO
NiS04
Ni(OH)2
Co304
A1203
Fraction of
Flue Gas (ppm)
116.6
185,000
185.0
1.12
.061
.136
.0025
.0018
.0014
.0012
.028
.0041
.0024
.0067
1.32
Cone./
MATE
7.2
16.7
3.74
906
49
7.4
2.1
1.5
1.1
1.0
.46
.22
.13
.11
.11
-90-
-------
are projected to exceed their MATE values. They are all either oxides or ele-
mental forms of V, Ni, and Cr. Lack of adequate engineering information pre-
vents a meaningful projection of the environmental impact of spent catalyst
disposal at this point. Spent catalyst disposal is, however, a major environ-
mental concern associated with HDS, due to the quantities of sulfur, carbon, and
trace metals retained on the catalyst bed.
POX Emissions
The partial oxidation process generates a low-Btu, virtually carbon-free
gas for use as a gas turbine feedstock. The major pollutant streams are flue
gas and wastewater from the sulfur recovery process, wastewater from the carbon/
gas separator, wastewater from the fuel preparation unit, and combustion prod-
ucts from the gas turbine. A typical analysis of gasifier product gas is shown
in Table 4-14.
The water scrubber which follows the reactor removes essentially all water
soluble contaminants in the product gas, as well as the carbon soot, which re-
mains suspended in the water. The contaminants include: trace metals (mostly
vanadium and nickel); hydrogen cyanide (HNC); ammonia (NH3); an trace amounts
of formic acid (HCCLH). The suspended carbon soot is removed by naphtha extrac-
tion or other recovery methods and recycled to the gasifier. Some ash and trace
metals are recycled with the carbon soot; but, most will remain in the wash wa-
ter, which is subsequently treated for removal of hydrogen cyanide, ammonia, and
formic acid. Some trace metals remain in the ash, which collects in the bottom
of the gasifier. Operating experience indicates that perhaps 50% of vanadium,
sodium, and nickel drop out with the ash; and, the rest of these and other trace
metals are removed from the gas stream by the water scrubber. Following the
water scrubber, the gas passes through a contactor containing a sorbent for re-
moval of HoS and minor sulfur compounds, such as carbonyl sulfide and carbon
disulfide, so that the resultant low-Btu gas stream is virtually free of parti-
culate matter and sulfur compounds.
The projected trace emissions of Table 4-15 for a boiler burning POX prod-
uct gas are based on the residual oil combustion products of Table 4-7(a), as-
suming 99% removal of trace metals in the gasifier ash and product gas wash.
Based on this approximation and the MATE values, the only compounds presenting
a potential health or ecological hazard as air pollutants are vanadium pentoxide,
-91-
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TABLE 4-14. TYPICAL POX PRODUCT GAS COMPOSITION
FOR RESIDUAL OIL GASIFICATION WITH AIRUJ
Composition Concentration (% Vol.)
C02 2.36
CO 22.29
H2 16.66
CH4 0.03
N2 57.55
A 0.70
H2S 0.39
COS 0.02
H20
"The Shell Gasification Process,"
Shell Internationale Research
Maatschappij N.V., The Hague,
Holland, January, 1974.
-92-
-------
TABLE 4-15. PROJECTED TRACE EMISSIONS FOR BOILER BURNING POX PRODUCT GAS
V2°5
Cr2°3
NiO
V2°4
VO
Cr
V
CoO
NiS04
Ni(OH),
c°3°4
A1203
Si02
Ni
CoSO.
Fraction of
Flue Gas
(ppm)
.238
.013
.029
.00054
.00039
.00030
.00026
.00600
.00087
.00052
.00142
.281
.208
.00026
.00061
Cone. /MATE
(Air)
192.66
10.52*
1.57
.437
.316
.243
.211
.0971
.0470*
.0281*
.0230*
.0227
.0168
.0140
.00988*
* Based on MATE values estimated from others in the
same category.
-93-
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chromic oxide, and nickel oxide. All other trace compounds have projected emis-
sion levels below their MATE values.
Assuming that 99% of the trace metal compounds are removed from the product
gas stream and that roughly half of that reduction occurs as retention in gasi-
fier ash, then about 50% of the input trace metals will exit the system as con-
taminants in the wash water. Based on that assumption and the residual oil com-
bustion products, the estimated concentration of major trace pollutants in POX
wastewater is as shown in Table 4-16. Comparison of projected pollutant levels
with MATE values indicates that a potential environmental problem exists in the
high levels of trace metal compounds in the wastewater.
4.1.2 Actual Baseline Emissions
This section covers the available chemical and physical properties of waste
streams found in the commercial operations of FGD, POX, and HDS in Japan. The
emissions analyses are based on grab samples taken in Japan in 1977. The spark
source mass spectroscopic (SSMS) analyses were performed by Northrop Services,
Inc., Research Triangle Park, North Carolina. Fugitive emissions and boiler
wastewater blowdown streams were not considered because they are well defined
by other EPA projects specifically addressed to these objectives.
A spark source mass spectrographic analysis is shown in Table 4-17 for the
aluminum sulfate/limestone FGD process in Japan. The elements were retabulated
in Table 4-18 for purposes of ranking the potentially hazardous pollutants by
MATE ratio (Column 1), maximum pollutant concentration range in sludge (Column
2), and comparison with the current concentration goals of the MATE values (for
land). Table 4-18 shows a total of 14 elements above ratio of one, indicating
nickel at the top of the list of suspect toxic elements followed by selenium,
zinc, cobalt, vanadium, and arsenic.
The trace element emissions from the residual fuel oil combustion emissions
from a magnesia-limestone double alkali FGD system are shown in Table 4-19. The
limit of detection for this sample is 0.8 mg/g on the elements not reported.
Table 4-20 tabulates the magnesia-gypsum sludge potentially toxic pollutants in
the order of high MATE ratios to low. In this process, the important pollutants
to observe are selenium, nickel, vanadium, zinc, chromium, and cobalt.
Table 4-21 is a tabulation of the SSMS of trace elements discharge in a
waste stream from the sodium sulfite/weak acid, regenerable FGD process in
-94-
-------
TABLE 4-16. PROJECTED TRACE CONTAMINANTS IN POX WASTEWATER
Pollutant
NiO
V90,
2 5
NiS04
(* v* C\
V/ I f\ \J o
Ni(OH)2
Ni
CoO
Co,0A
6 4
VoOy,
24
VO
CoS04
A12°3
V
Si02
Cr
Ib/hr to
Wastewater
3.30
27.11
.099
1.48
.059
.030
.633
.162
.062
.044
.069
32.01
.030
23.69
.034
Cone, in
Wastewater (ug/1)
51400
422000
1540
23000
920
470
10600
2520
970
690
1070
498000
470
369000
530
Cone. /MATE
5140
2813
154*
92
92*
47
42.4
10.1*
6.5
4.6
4.3*
3.3
3.1
2.5
2.1
* Based on MATE values estimated from others in the same category.
-95-
-------
TABLE 4-17. SPARK SOURCE MASS SPECTROGRAPHIC ANALYSIS OF
JAPANESE LIMESTONE FGD SLUDGE
Concentration,
Element In ug/g
Ba 120.
Sr 230.
Se 8.
As 1.5
Ge 2.6
Zn 190.
Ni 63.
Co 16.
Fe 610.
Mn 36.
v 110.
Ca 110,000.
K 200.
P 5.5
Si 540.
Al 640.
Mg 380.
Na 200.
Ash 74.1
Note: (1) Sample from aluminum sul fate-gyps urn sludge Dowa Basic
Gypsum.
-96-
-------
TABLE 4-18. FGD SLUDGE POLLUTANT RANKING
Maximum Concentration
MATE Concentration Goal in ug/g
Element Ratio in ug/g (MATE-Values)
Ni
Se
Mn
Zn
Co
V
Ba
Al
K
Fe
As
Sr
Mg
P
Ge
Na
Ca
Si
140.0
80.0
72.0
38.0
32.0
22.0
12.0
4.0
3.30
3.05
3.00
2.50
2.24
0.18
0.15
0.13
—
_ _
63.3
<8.0
36.0
<190.0
16.0
110.0
120.0
640.0
200.0
610.0
1.5
230.0
380.0
5.5
2.6
200.0
110,000.0
540.0
0.45
0.1
0.2
5.0
1.5
5.0
10.0
4.0
60.0
200.0
3.0
92.0
170.0
30.0
5.0
1600.0
480.0
300.0
-97-
-------
TABLE 4-19. SSMS ANALYSIS OF JAPANESE MAGNESIA-GYPSUM FGD SLUDGE
Concentration,
Element in ug/g
Ba
Se
Ga
Zn
Cu
Ni
Co
Fe
Cr
V
Ti
Ca
K
Cl
P
Si
Al
Mg
Na
Ash
29.
30.
7.7
300.
17.
45.
48.
1,400.
24.
220.
69.
200,000.
510.
88.
50.
1,300.
27.
770.
100.
78.
-98-
-------
TABLE 4-20. MAGNESIA-GYPSUM FGD SLUDGE POLLUTANT RANKING
Maximum Concentration
Element
Se
Ni
Zn
Cr
V
Co
Cu
K
Fe
Mg
Si
Ba
P
Ti
Al
Na
Ga
Cl
Ca
MATE
Ratio
300.0
100.0
60.0
48.0
44.0
32.0
17.0
8.5
7.0
4.5
4.3
2.9
1.7
0.38
0.17
0.06
0.05
0.034
__
Concentration
in uq/q
< 30.0
< 45.0
< 300.0
24.0
220.0
48.0
17.0
510.0
1,400.0
770.0
1,300.0
29.0
50.0
69.0
27.0
100.0
7.7
88.0
200,000.0
Goal in ug/g
(MATE-Values)
0.1
0.45
5.0
0.5
5.0
1.5
1.0
6
200.0
170.0
300.0
10.0
30.0
180.0
160.0
1,600.0
150.0
2,600.0
480.0
-99-
-------
TABLE 4-21. SSMS ANALYSIS OF JAPANESE SODIUM
SULFITE/WEAK ACID, FGD SLUDGE
Concentration,
Element in ug/g
Pr .52
Ce 2.4
La 1.6
Ba 97.
Zr 16.
Sr 160.
Zn 42.
Cu 25.
Ni 40.
Co 17.
Fe 14,000.
Mn 450.
Cr 1,400.
V 500.
Ti 230.
Sc 9.5
Ca 8,900.
K 13,000.
Cl 42.
P 200.
Si Major
Al 11,000.
Mg 5,100.
Na 16,000.
Ash 56.5
-100-
-------
Japan. The approximate detection limit for elements not reported is 0.06 ug/g.
Table 4-22 shows the pollutant inventory of the sodium sulfite/weak acid FGD
system with very high concentrations and MATE ratios for chromium, manganese,
vanadium, nickel, cobalt, zinc, and strontium.
Table 4-23 is a spark source mass spectrographic analysis of carbon re-
covery effluent from a partial oxidation process burning residual oil. The li-
mit of detection for the elements not reported is 0.01 ug/g. The bulk of (V)
spherical, soft, and black soot pellets were ashed to a trace residue of less
than 1 percent. Thus, most of this material is unburnt carbon with very small
concentrations of the total trace elements.
Table 4-24 indicates very high MATE ratios of nickel and vanadium, which
are typical of residual oil from Arabian crude oils. Most of the bulk quanti-
ties of trace elements are in the wastewater effluent stream from the POX gas-
ifier discharge quench vessel and the water wash tower.
4.2 TEST PROGRAM DEVELOPMENT
The residual oil facilities are complex, multiwaste stream generating sys-
tems. To carry out environmental assessment measurement programs in a manner
suitable to the needs of EPA for the sampling and analysis tasks, one must be
familiar not only with the Level 1 and Level 2 sampling and analysis require-
ments but also with the details of the processes themselves. To facilitate
cost-effectiveness, the specific programs designed for each facility must in-
clude, in addition to Level 1 measurements, limited Level 2 type field measure-
ments for specific pollutants identified through engineering calculations.
Although engineering studies and identification of specific pollutants (for
example, S02, H2S, Ni(CO)4, V205, and NOX) are of concern, the sampling and
analysis should provide input to these decisions and integrate them smoothly
into the basic Level 1 sampling program. Several residual oil processes are to
be sampled in this program, and specific pollutant concentrations from various
waste streams will be estimated beforehand.
In addition to considerations involving plant design and operating condi-
tions, a detailed sampling plan must include logistical considerations such as
power, laboratory space and facilities, water, ports, and scaffolding available
on site. Shipment of sampling equipment and chemicals to a site must be
-101-
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TABLE 4-22. SODIUM SULFITE/WEAK ACID FGD
SLUDGE ANALYSIS POLLUTANT RANKING
Maximum Concentration
Element
Cr*
Mn*
V
Ni
Al*
Fe*
Hg
Cu*
Co
Ba
Zn
Sr
Ti
Zr
Cl
Si
Na
K
Ca
Ce
La
Pr
P
Se
MATE
Ratio
2,800.0
900.0
100.0
80.9
68.8
70.0
30.0
25.0
11.3
9.7
8.4
1.74
1.28
0.94
0.16
—
—
—
—
2.0
0.00050
0.00004
.0059
Concentration
in ug/g
<: 1,400.0
450.0
500.0
< 40.0
11,000.0
14,000.0
5,100.0
25.0
17.0
97.0
42.0
160.0
230.0
16.0
42.0
Major
16,000.0
13,000.0
8,900.0
2.4
1.6
0.52
200.0
9.5
Goal in ug/g
(MATE-Values)
0.5
0.5
5.0
0.45
160.0
200.0
170.0
1.0
1.5
10.0
5.0
92.0
180.0
15.0
2,600.0
1,600.0
60.0
480.0
1,100.0
3,400.0
1,500.0
30.0
1,610.0
* These elements may be erroneously high in concentration as
a result of corrosive action on the scrubber materials of
construct!" on.
-102-
-------
TABLE 4-23. SSMS ANALYSIS OF JAPANESE POX CARBON PELLETED RESIDUE
Concentrati on
Element in ug/g
Pb
Ba
Mo
Zr
Sr
Ga
Ni
Co
Fe
Mn
Cr
V
Ti
Sc
Ca
K
Cl
P
Si
Al
Mg
Na
Ash
.12
1.2
2.6
.04
1.2
.97
480.
2.6
480.
3.6
8.5
540.
2.3
.32
340.
200.
3.0
15.
980.
88.
77.
240.
1.
-103-
-------
TABLE 4-24. PARTIAL OXIDATION CARBON RESIDUE POLLUTANT RANKING
Maximum Concentration
Element
Ni
V
Al
Cr
Mn
Co
K
Ti
Pb
Ba
Mo
Ga
Sr
Zr
Sc
Cl
Si
Fe
Mg
Ca
P
Na
MATE
Ratio
24,000.0
1,800.0
44.0
29.8
18.0
5.2
3.33
1.4
1.2
0.545
0.186
—
0.0130
0.0027
0.0020
0.0012
3.3
2.4
2.1
0.71
0.5
0.15
Concentration
in ug/g
480.0
540.0
88.0
8.5
3.6
2.6
200.0
2.3
0.12
1.2
2.6
0.97
1.2
0.04
0.32
3.0
980.0
480.0
77.0
340.0
15.0
240.0
Goal in ug/g
(MATE-Values)
0.02
0.3
2.0
0.286
0.2
0.5
60.0
1.6
0.10
2.20
14.0
14.9
92.0
15.0
1,600.0
2,600.0
300.0
200.0
36.6
480.0
30.0
1,600.0
Note: (1) Sample from gasifier discharge of carbon recovery
pellets with trace metals acid from residual oil.
-104-
-------
arranged well in advance, particularly when sampling in a foreign country.
The goal of the sampling operation is to complete the Level 1 and 2 re-
quirements in one trip. This is especially true in the case of the Japanese
sites for which a follow-up sampling visit would be extremely expensive. Our
approach to this program would combine a complete Level 1 (SASS, GC, liquid,
solid streams) test with collection of duplicate samples plus special Level 2
tests for those pollutants identified in the engineering assessment.
The laboratory analysis phase of the program is more flexible than the
sampling portion in that decisions to conduct additional Level 2 analyses of-
ten can be made without resampling after Level 1 analyses are completed. To
ensure that sufficient sample quantities will be available for Level 2 analy-
ses, additional (to Level 1) liquid and solid waste samples will be taken at
each facility and duplicate SASS runs will be made when feasible. The overall
analytical plan will cover Level 1, those additional pollutants identified as
a priority by the engineering estimates, and those potential pollutants un-
covered by Level 1.
4.2.1 Sampling and Analysis Matrix
Completion of the environmental data acquisition requires characteriza-
tion of the input/output streams for each process under study. Thus, the sam-
pling and analysis program to obtain the data necessary for stream characteri-
zation is an important element in the environmental assessment effort.
A phased approach to environmental assessment sampling and analysis has
been developed by the EPA, and Catalytic1s intention is to follow the es-
tablished methodology. Level 1 techniques will be employed, but simplifying
Level 1 assumptions will not be allowed to restrict data gathering when very
little additional time and effort will result in substantial additional data
40
col 1ecti on.
A sampling/analysis program has been developed which conforms to EPA
Level 1 guidelines. A sampling/analysis matrix, developed as a tool to aid in
carrying out the sampling/analysis program, has been developed and is present-
ed for the purpose of illustrating, clearly and concisely, the logical proce-
dure being followed to develop the required stream characterization data.
-105-
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A sampling/analysis matrix is presented for a residual oil-fired utility
boiler without controls, as well as for each of the major utilization processes
being considered: hydrodesulfurization, regenerable flue gas desulfurization
(MgO scrubbing), non-regenerable flue gas desulfurization (limestone scrubbing),
partial oxidation, and the chemically active fluid bed process. An example of
the use of the sampling/analysis matrix is given in the interest of clarity.
The sampling program for environmental assessment must be much more exten-
sive than those programs conducted for process or control data collection, since
the total pollution potential of all process waste streams must be identified.
All waste streams must be sampled, and all substances of potential environment-
al insult must be detectable above a minimal level of concern.
The phased approach to environmental assessment involves sampling and
analysis on three levels. Level 1 sampling/analysis is designed for an accuracy
factor of +. 3 (-33% to 300% of the true value), and the resultant data is used
for pollutant stream prioritization. Level 2 involves detailed sampling and
analysis, applied first to those streams of highest priority, as defined by
Level 1; and, Level 3 involves continuous monitoring of indicator substances for
evaluation of long-term process variation.
A generalized sampling matrix for gas, liquid, and solid streams is shown
in Table 4-25. The generalized Level 1 physical, chemical, and biological anal-
ysis scheme is shown in Figure 4-2. Design of a Level 1 sampling/analysis ma-
trix involves answering four basic questions: (1) Where in the system are the
samples to be taken? (2) How are the samples to be taken? (3) What are the
potential pollutants or pollutant categories in each stream? and (4) What method
of analysis is used to determine the level of each potential pollutant in each
stream?
The answers to the first two questions are given in Figures 4-3 through
4-8. The numbered streams on the flow diagrams indicate where in the system
the samples are to be taken, and the accompanying tables indicate the stream
conditions and the techniques to be used in obtaining the desired samples.
The third and fourth questions are answered by Tables 4-26 through 4-31,
which list the potential pollutants in each stream, along with the methods
-106-
-------
TABLE 4-25. LEVEL 1 SAMPLING*
Stream Sample Size Location Sampling Procedure
Gas 30 m3 Ducts, stacks SASS train
Liquid 10 liter Lines or tanks Tap or valve sampling
Open free-flowing Dipper method
streams
Solids 1 kg Storage pile- Coring
Conveyors Full stream cut
* Environmental Assessment Sampling and Analysis: Phased Approach and Tech-
niques for Level 1, EPA-600/2-77-115 (NTIS No. PB 268563/AS), June 1977.
-107-
-------
Field
Samples
PHYSICAL
Solids Morphology
INORGANIC
Elemental Analysis
(Spark Source Mass and
Atomic Absorption Spectrometry)
ORGANIC
Liquid Chromatography
Infrared and Low
Resolution Mass Spectrometry
BIOASSAY
in vitro Cytotoxicity;
Bacterial Mutagenicity;
Ecological Testing;
in vivo Toxicity
Figure 4-2 - Level 1 Analysis*
'Environmental Assessment Sampling and Analysis: Phased Approach and Techniques
for Level 1, EPA-600/2-77-115 (NTIS No. PB 268563/AS), June 1977.
-108-
-------
Fuel
Combustion
Air
Water
2
\~s
I,
Flue
Gas
Boiler
Bottom
Ash
Ash Handling
System
Waste
Water
Steam
Solid Wastes
•©
Stream
1
2
3
4
Description
Residual Oil Feed
Stack Gas
Wastewater from Ash Handling
Bottom Ash
Conditions
Temp.
Ambient
400°F
200°F
200°F
Pressure
Atmospheric
Atmospheric
Atmospheric
Atmospheric
Phase
1
g
1
s
Sampling
Method
Grab
SASS1
Grab2
Grab2
Notes:
1. Additional methods may include EPA Method 5 for inorganics, and the
Controlled Condensation Train for SOX.
2. To be taken between ash handling system emission point and final disposal point.
Time-composite may be desirable to account for process conditions which vary
with time.
Figure 4-3 - Sampling Matrix for Oil-Fired Boiler without Controls
-109-
-------
TABLE 4-26. ANALYSIS TECHNIQUES FOR OIL-FIRED BOILER WITHOUT CONTROLS
Stream
Analysis Techniques
Pollutant 1234
SOV X
X
NOV X
X
CO X
HC XX
H2S X
COS X
NH3 X
HCN X
(CN)2 X
BOD X
COD X
DO X
TDS X
TSS X
Sulfur X
Nitrogen X
Carbon XX X
Hg, As, Sb X X X X
Cl, F X X X X
Other Trace Metals X X X X
Ash/Parti cul ate XX X
Sul fates X
Nitrates X
1. Gas Chroma tog raphy (GC)
2. Liquid Chromatography (LC)
3. Infrared Spectroraetry (IR)
4. Low Resolution Mass Spec-
trometry (LRMS)
5. Spark Source Mass Spectrom-
etry (SSMS)
6. Atomic Absorption (AA)
7. CHoCU Extraction
Gas Liquid Solid
1
8
1
1,2,3,4 7,1,2,3,4 1,2,3,4
1
1
1
1
1
9
9
9
9
9
5
13
555
666
10 10 10
555
555
n
12
8. Chemi luminescence
9. Hach or Bausch and Lomb reagent
test kits
10. Wet Chemical Analysis Techniques
11. Turbidimetric method for sul fates
12. Brucine-nitrate procedure
13. Combustion Titrimetric/Specto-
metric method
-no-
-------
Stream
1
2
3
4
5
Description
Residual Oil Feed
MgO Make-Up
Oil to Dryer/Calciner
Calciner Off-Gas (S02)
Cleaned Stack Gas
Conditions
Temp.
Ambient
Ambient
Ambient
100°F
300°F
Pressure
Atmospheric
Atmospheric
Atmospheric
Atmospheric
Atmospheric
Phase
1
s
I
g
9
Sampling
Method
Grab
Grab
Grab
SASS1
SASS1
Notes:
1. Additional methods may include EPA Method 5 for inorganics and the
Controlled Condensation Train for SOX.
Figure 4-4 - Sampling Matrix for MgO Scrubbers
-111-
-------
TABLE 4-27. ANALYSIS TECHNIQUES FOR MgO SCRUBBERS
Stream
Pollutant 1 2 3
sov
X
NOV
X
CO
HC XX
H2S
COS
NH3
HCN
(CN)2
BOD
COD
DO
TDS
TSS
Sulfur XXX
Nitrogen X X
Carbon X X
Hg, As, Sb XXX
Cl, F XXX
Other Trace Metals XXX
Ash/Pa rticul ate XXX
Sul fates
Nitrates
1. Gas Chromatography (GC)
2. Liquid Chromatography (LC)
3. Infrared Spectrometry (IR)
4. Low Resolution Mass Spec-
trometry (LRMS)
5. Spark Source Mass Spec-
troscopy (SSMS)
6. Atomic Absorption (AA)
7. CH0C10 Extraction
4
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
5
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Analysis Techniques
Gas Liquid Solid
1
8
1
1,2,3*4 7,1,2,3,4 1,2,3,4
1
1
1
1
1
1
5
5
6
10
5
5
8.
9.
10.
11.
12.
13.
13
5
5
6
10
5
5
6
10
5
5
Chemi1uminescence
Hach or Bausch and Lomb
reagent test kits
Wet Chemical Analysis Techni-
ques
Turbidimetric method for sul-
fates
Brucine-nitrate procedure
Combustion Titrimetric/Spec-
tometric method
-112-
-------
Stream
1
2
3
4
Description
Residual Oil Feed
Limestone Feed
Cleaned Stack Gas
Sludge to Disposal Pond
Conditions
Temp.
Ambient
Ambient
300°F
200°F
Pressure
Atmospheric
Atmospheric
Atmospheric
Atmospheric
Phase
1
5
g
1
Sampling
Method
Grab
Grab
SASS1
Grab2
Notes:
1. ' Additional methods may include EPA Method 5 for inorganics and
the Controlled Condensation Train for SOX.
2 To be taken between sludge thickener and disposal pond. Time-composite may
be desirable to account for process conditions which vary with time.
Figure 4-5 -Sampling Matrix for Limestone Scrubbers
-113-
-------
TABLE 4-28. ANALYSIS TECHNIQUES FOR LIMESTONE SCRUBBERS
Stream
Analysis Techniques
Pollutant 1 2
sov
X
N0v
X
CO
HC X
H2S
COS
NH3
HCN
(CN)2
BOD
COD
DO
TDS
TSS
Sulfur X
Nitrogen X
Carbon X X
Hg, As, Sb XX
Cl, F XX
Other Trace Metals X X
Ash/Parti cul ate X
Sul fates
Nitrates
1. Gas Chroma tography (GC)
2. Liquid Chroma tography (
3. Infrared Spectrometry (
3
X
X
X
X
X
X
X
X
X
X
X
X
X
X
LC)
IR)
4
X
X
X
X
X
X
X
X
X
X
X
X
4. Low Resolution Mass Spec-
trometry (LRMS)
5. Spark Source Mass Spectro-
scopy (SSMS)
6. Atomic Absorption (AA)
7. Ch0C19 Extraction
c. c.
Gas
1
8
1
1,2,3
1
1
1
1
1
5
6
10
5
5
8.
9.
10.
11.
12.
13.
Liquid Solid
,4 7,1,2,3,4 1,2,3,4
9
9
9
9
9
5
13
5 5
6 6
10 10
5 5
5 5
11
12
Chemi 1 umi nescence
Hach or Bausch and Lomb
reagent test kits
Wet Chemical Analysis
Techniques
Turbidimetric method for
sul fates
Brucine-nitrate procedure
Combustion Titrimetric/
Spectometric method
-114-
-------
V
Treated Water
Stream
1
2
3
4
5
6
Description
Residual Oil Feed
Heater Flue Gas
Wastewater
Sulfur from Sulfur Recovery
Unit
Flue Gas from Sulfur Recovery
' Off-Gas Treatment
Low-Btu Product Gas
Conditions
Temp.
Ambient
500°F
500°F
500°F
500°F
1000°F
Pressure
Atmospheric
Atmospheric
Atmospheric
Atmospheric
Atmospheric
275 psia
Phase
1
g
I
I
g
g
Sampling
Method
Grab
SASS1
Grab2
Grab2
SASS1
SASS1
Notes:
1. Additional methods may include EPA Method 5 for inorganics
and the Controlled Condensation Train for SOX.
2. Time-composite may be desirable to account for process conditions which
vary with time.
Figure 4-6 - Sampling Matrix for Partial Oxidation Process
-115-
-------
TABLE 4-29. ANALYSIS TECHNIQUES FOR A PARTIAL OXIDATION PROCESS
Stream
Analysis Techniques
Pollutant 1234
sox x
NOX X
CO X
HC XX
tic v
COS X
NH3 X
HCN X X
(CN)2 X
BOD X
COD X
DO X
TDS X
TSS X
Sulfur X X
Ni trogen X
Carbon X X X X
Hg, As, Sb X X X X
Cl, F X X X X
Other Trace Metals X X X X
Ash/Parti cul ate X X X X
Sul fates X
Nitrates X
1. Gas Chroma tography (GC)
2. Liquid Chromatography (LC)
3. Infrared Spectrometry (IR)
4. Low Resolution Mass Spec-
trometry (LRMS)
5. Spark Source Mass Spec-
troscopy (SSMS)
6. Atomic Absorption (AA)
7. CH2C12 Extraction
5
X
X
X
X
X
X
X
X
X
X
X
X
X
X
6
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Gas
1
8
1
1,2,3
1
1
1
1
1
5
6
10
5
5
8.
9.
10.
11.
12.
13.
Liquid Solid
,4 7,1,2,3,4 1,2,3,4
5
9
9
9
9
9
5 5
13
5 5
6 6
10 10
5 5
5 5
11
12
Chemi luminescence
Hach or Bausch and Lomb re
agent test kits
Wet Chemical Analysis Tech
niques
Turbidi metric method for
sul fates
Brucine-nitrate procedure
Combustion Titri metric/
Spectometric method
-116-
-------
Flue Gas
Limestone
©
Limestone
Preparation
&
Storage
Sulfur
Stream
1
2
3
4
5
6
7
8
Description
Limestone Feed
Residual Oil Feed
Boiler Flue Gas
Spent Stone from Regenerator
Ash from Sulfur Recovery Unit
Sulfur from Condenser
Regenerator Cyclone Fines
Coal Feed to Sulfur Recovery
Unit
Conditions
Temp.
Ambient
Ambient
500°F
450°F
(after
cooling)
1400°F
500°F
450°F
(after
cooling)
Ambient
Pressure
Atmospheric
Atmospheric
Atmospheric
Atmospheric
Atmospheric
Atmospheric
Atmospheric
Atmospheric
Phase
s
I
g
s
s
I
s
s
Sampling
Method
Grab
Grab
SASS1
Grab2
Grab3
Grab3
Grab
Grab
Notes:
1. Additional methods may include EPA Method 5 for inorganics
and the Controlled Condensation Train for SOX.
2. Sample to be taken as close as possible to gasif ier outlet. Time-composite may
be desirable to account for process conditions which vary with time.
3. Time-composite may be desirable to account for process conditions which vary
with time.
Figure 4-7 - Sampling Matrix for CAFB Process
-117-
-------
TABLE 4-30. ANALYSIS TECHNIQUES FOR CHEMICALLY ACTIVE FLUID BED PROCESS
Stream
Pollutant 123456
sox x
NOX X
CO X
HC XX
H2S X
COS X
NH3 X
HCN X
(CN)2 X
BOD
COD
DO
TDS
TSS
Sulfur X XXX
Nitrogen X
Carbon X X X X
Hg, As, Sb X X X X X X
Cl, F XXXXXX
Other Trace Metals XXXXXX
Ash/Pa rticul ate X X X X X
Sul fates X
Nitrates
1. Gas Chroma tography (GC)
2. Liquid Chroma tography (LC)
3. Infrared Spectrometry (IR)
4. Low Resolution Mass Spec-
trometry (LSMS)
5. Spark Source Mass Spec-
troscopy (SSMS)
6. Atomic Absorption (AA)
7. CH2C12 Extraction
Analysis Techniques
7 8 Gas Liquid Solid
1
8
1
X 1,2,3,4 7,1,2,3,4 1,2,3,4
1
1
1
1
1
XX 55
X 13 13
X X 5 5 5
X X 6 6 6
X X 10 10 10
X X 5 5 5
X X 5 5 5
5
8. Chemi luminescence
9. Hach or Bausch and Lomb re-
agent test kits
10. Wet Chemical Analysis Tech-
niques
11. Turbidimetric method for sul
fates
12. Brucine-nitrate procedure
13. Combustion Titrimetric/
Spectometric method
-118-
-------
Cittlyit
.—J Spent Catalyst &
(3J Reactor Waste
Stack Gas
Sulfur
Stream
1
2
3
4
5
6
7
8
9
10
11
Description
Residual Oil Feed
Catalyst
Spent Catalyst and Reactor Waste
Separator Off-Gas
Fractionator Off-Gas
Naphtha
Low Sulfur Fuel Oil
Treated Water From Stripper
Sulfur from Sulfur Recovery Unit
Stack Gas from Tail Gas
Cleanup (h^S)
By-product (water from Tail Gas
Cleanup
Conditions
Temp.
Ambient
Ambient
Ambient
300° F
300°F
300°F
200°F
200°F
200°F
500°F
300°F
200°F
Pressure
Atmospheric
Atmospheric
Atmospheric
180 psia
40 psia
40 psia
40 psia
Atmospheric
Atmospheric
Atmospheric
Atmospheric
Atmospheric
Phase
I
s
s
g
g
i
i
i
i
9
a
I
I
Sampling
Method
Grab
Grab
Grab1
SASS2
SASS2
Grab
Grab
Grab3
Grab3
SASS2
Grab3
Grab3
Notes:
1. Taken at end of run or during operation via purge tap if available.
2. Additional methods may include EPA Method 5 fpr inorganics
and the Controlled Condensation Train for SOX.
3. Time-composite may be desirable to account for process conditions which
varv with time.
Figure 4-8 - Sampling Matrix for an HDS Process
-------
TABLE 4-31. ANALYSIS TECHNIQUES FOR A HYDRODESULFURIZATION PROCESS
Stream
Analysis Techniques
Pollutant 1234
S0x
NOX
CO
HC XX
H2S X
COS
NH3
HCN
(CN)2
BOD
COD
DO
TDS
TSS
Sulfur X X
Nitrogen X
Carbon X X
Hg, As, Sb XXX
Cl, F XXX
Other Trace Metals X X X X
Ash/Parti cul ate X X
Sul fates X
Nitrates X
1. Gas Chromatography (GC)
2. Liquid Chromatography (LC)
3. Infrared Spectrometry (IR)
4. Low Resolution Mass Spec-
trometry (LRMS)
5. Spark Source Mass Spec-
troscopy (SSMS)
6. Atomic Absorption (AA)
7. CH2C12 Extraction
56789
XXX
X
X X X X
XXX
X X X X
X X X X X
X X X X X
X X X X X
X X X X
X X
X
8.
9.
10.
11.
12.
13.
10 11 Gas Liquid Solid
X 1
X 8
X 1
Y 1,2, 7,1,2, 1,2,
* 3,4 3,4 3,4
X 1
X 1
X 1
X 1
X 1
X 9
X 9
X 9
X 9
X 9
5 5
13 13
X 55
X X 6 6 6
X X 10 10 10
X X 5 5 5
X X 5 5 5
X 11 5
X 12 5
Chemi 1 umi nescence
Hach or Bausch and Lomb reagent
test kits
Wet Chemical Analysis Techniques
Turbidimetric method for sulfates
Brucine-nitrate procedure
Combustion Titrimetric/
Spectometric method
-120-
-------
of analysis used for detection of each pollutant or pollutant category in each
stream. The overall analysis scheme for gaseous, particulate, solid, and li-
quid samples is shown in Figure 4-9.
Chemical analysis is necessary for identifying the waste stream components;
but, biological analysis, in the form of bioassays, is required to determine the
potential health and ecological hazard presented by the waste stream to the en-
vironment. Bioassays are used to indicate the toxic and mutagenic potential of
a given stream regardless of the amount of synergism and antagonism occurring
within the stream and thus serve to reveal potential hazards that might be miss-
ed by pure chemical analysis. The minimal bioassay test matrix is shown in Table
4-32.
As an example of how the sampling and analysis matrix might be used, sup-
pose that specific information on the sampling/analysis methods for wastewater
from the partial oxidation (POX) process is desired. The block diagram of Fi-
gure 4-6 indicates all sampling points for POX, and the stream in question is
found as an effluent from the water treatment unit, stream 3. The tabular sec-
tion of Figure 4-6 then indicates that stream 3, wastewater, is a hot, atmos-
pheric-pressure, liquid stream. The final column of the table specifies that
a grab sample is to be taken, and the footnote indicates that a time-composite
may be desirable if process conditions are varying with time. The next step is
to proceed to Table 4-29, which lists the pollutants in each stream and their
respective analysis techniques. Thus, stream 3 will be analyzed for HCN, BOD,
COD, DO, TDS, TSS, Carbon, Hg, As, Sb, Cl, F, other trace metals, ash/particu-
late, sulfates, and nitrates. If it were desirable to know the particular anal-
ysis technique for determining BOD in the POX wastewater, then it can be seen
from Table 4-29 that the analysis technique for BOD in a liquid sample is #9,
or, from the notes at the bottom of the page, a Hach or Bausch and Lomb reagent
test kit. If information on the biological testing of the wastewater sample
were desired, it would be found in Table 4-32, which lists the health and eco-
logy effects tests to be performed on all water and liquid samples.
The results of the Level 1 physical, chemical, and biological analyses
will be the characterization of each waste stream with respect to its physical
characteristics, its chemical constituents, and its potential health and
-121-
-------
Gas
Particulates
Organic; > Cg
XAD-2 Adsorber
^-
Extraction
with
CSH12
Column Chromatography
Separation into
8 Fractions
SASS Train
XAD-2 Module
Wet Ashing
SASS Train
Inpingers
>10(». Fraction
3-10|» Fraction
1-3 u Fraction
< 1 p. Fraction
Extraction
with
CH2CI2
Wet Ashing
Column
Chromatography
Separation into
8 Fractions
Inorganics
On-SiteGC
Analysis
Chemilummescent
Analysis
Organ ics Cj-Cg
On-SiteGC
Analysis
Organics C7-C-| 2
GC Analysis
(c)
Organic >C.j 2
IR, MS Analysis
Elemental Analysis
SSMS(b)
Elemental Analysis
SSMS(b)
Selected
Anion Analysis
Field Test Kits
Elemental Analysis
SSMS(b)
Organic Analysis
IR.MS
Morphology:
Polarizing Light
Microscope
• Same as Above
(a) Impinger solutions excluded
(b) Hg, Sb, As are analyzed by wet techniques.
(c) An aliquot from the extraction is used for
these analyses.
Figure 4-9 - Overall Analytical Scheme for Level
""Procedures Manual for Environmental Assessment of Fluidized-Bed Combustion Process,"
EPA-600/7-77-009, January 1977.
-122-
-------
Solid
or
Solids Portion
of Slurry
Physical
Characterization
Wet Ashing
Solvent Extraction
with CH2CI2
Column
Chromatography
Separation into
8 Fractions
Sizing:
Sieving, Air
Elutriation,
Optical Microscope
Morphology:
Polarizing
Light Microscope
(b)
Elemental Analysis
SSMS
Organic Analysis
I R.MS
Leachate
Generation
^.
See Analytical
Scheme for Liquids
Liquid,
Liquid Portion
of Slurry
or
Leachate
Standard Water Analysis
(Aqueous Streams Only)
Includes Selected Anions
Extraction
with
CH2CI2
(a) Impinger solutions excluded.
(b) Hg, Sb, As are analyzed by wet techniques.
(c) An aliquot from the extract is used for
these analyses.
Elemental Analysis
SSMS
Organ ics
-------
TABLE 4-32. LEVEL 1 - MINIMAL BIOASSAY TEST MATRIX*
Sample Type
Health Effects Tests
Ecology Effects Tests
Water and Liquids
Solids (Aqueous Ex-
tract, Feed, Product,
Waste)
Gases (Grab Sample)
Parti culates
Sorbent (Extract)
Microbial
Mutagenesis
Microbial
Mutagenesis
Microbial
Mutagenesis
Mi crobi al
Mutagenesis
Rodent Acute
Toxi ci ty
Rodent Acute
Toxi city
(Rodent Acute
Toxi city)**
Cytotox-
icity
Cytotox-
icity
Algal
Bioassay
Algal
Bioassay
Static
Bioassays
Static
Bioassays
Soil
Microcosm
Soil
Mi crocosm
Plant Stress
Ethyl ene
Soil
Microcosm
* IERL-RTP Procedures Manual: Level 1 Environmental Assessment,
Biological Tests for Pilot Studies, EPA-600/7-77-043 (NTIS No.
PB 2684847AS), April 1977.
** Recommended test not specified because of limited sample avail-
ability of secondary priority.
-------
ecological hazards. This Information is then used to define the Level 2 sampl-
ing/analysis program.
4.3 SUMMARY
Environmental data acquisition in this study involves an emissions inven-
tory and test program development. The emissions inventory defines emissions
loadings based on presently available data and identifies data gaps. The test
program has been developed to define the data needed for assessing effluent
characterization.
Test program development addresses the heart of control technology assess-
ment, which is the actual collection of emissions data and establishment of
pollutant loadings by sampling and analysis. A test program has been developed
with the goal of completing Level 1 and Level 2 sampling requirements in one
trip, so that the option of performing Level 2 analyses in the lab is retained.
A complete sampling and analysis matrix for each process under study has
been developed, which indicates all streams to be sampled, the methods to be
used for gathering the samples, stream conditions at the sampling point, poten-
tial pollutants in each sample, and the analysis techniques for quantifying
pollutants concentrations. It is felt that this innovative sampling/analysis
matrix format presents sufficient information in such a form that it could be
used as the basis for a pre-site survey.
Thus, emissions loadings, as determined by sampling and analyses results
and supplemented by theoretical engineering analysis, form the foundation upon
which control technology assessment is based.
Emissions inventory includes definition of all process inputs and outputs
based on theoretical engineering analysis and available sampling and analysis
results. A composite residual oil has been developed, based on both imports
and domestic sources, which is representative of a typical residual oil utiliza-
tion process feedstock, and will provide a consistent basis for comparison be-
tween control system performances. A complete, reliable limestone analysis has
also been selected to facilitate comparability between processes using a lime-
stone sorbent. A theoretical engineering analysis has been initiated, the goal
of which is to estimate pollutant loadings from residual oil utilization pro-
cesses (utility boiler without controls, regenerate FGD, non-regenerable FGD,
-125-
-------
partial oxidation, hydrodesulfurization, and the CAFB process) based on the oil
and sorbent inputs just mentioned.
Computerized equilibrium calculation-based predictions of combustion pro-
ducts are being used as the foundation for the estimation of inorganic pollu-
tant loadings by theoretical engineering analysis. Due to a lack of thermody-
namic data on organic compounds, only 12 organic species are presently consid-
ered as combustion products by the Battelle computer program being used. Ben-
zene ring and small hydrocarbon predictabilities are good, but the major use of
the program will be for prediction of inorganic species. Preliminary estima-
tions of pollutant loadings have been made for each process by an extrapolation
from previously published computerized equilibrium calculation results for a
residual oil-fired boiler without controls. Computer runs for each process, at
specified conditions, are planned, and some of the inputs have already been pre-
pared. Results of the engineering analysis will supplement Level 1 sampling and
analysis by serving (1) as a check on sampling and analysis results, and (2) as
a source of compound-specific emission information in areas where Level 1 sampling
and analysis results identify only the class, or category, or pollutant in a par-
ticular stream. The preliminary results indicate that, in all probability, only
a few inorganic pollutant compounds, such as those of vanadium, nickel, and chro-
mium, will pose any significant hazard in residual oil process gaseous effluents,
but that most of the potentially hazardous pollutants will be emitted as a com-
ponent of the wastewater or sludge streams.
A very limited amount of actual emissions data is available in the form
of spark source mass spectrographic analyses of grab samples of F6D sludges and
pelleted carbon residue from a partial oxidation unit taken last year in Japan
Obviously, then, the need for additional sampling and analysis for environmental
data acquisition is great.
-126-
-------
SECTION 5
CONTROL TECHNOLOGY ASSESSMENT
In the environmental assessment of residual oil utilization, control tech-
nology background information, which will be used in evaluating the process
techniques under study, has been compiled. Control systems and disposal options
information has been reviewed and compiled based on known potential pollutants
from residual oil combustion and upgrading operations. An economic evaluation
technique has been developed so that the cost effectiveness among various pro-
cesses might be studied. For the common control techniques, pollutant control
system studies have been made in order to compare the applicable concentration
range and removal efficiency of potential control technologies for oil conver-
sion wastestreams.
Although background information can be used to assess the economic and pro-
cess operation studies, results from actual sampling and analysis must be used
to assess the control technologies from an environmental standpoint. Reliable
environmental data is a prerequisite for completion of the control technology
assessment of residual oil processes.
5.1 POTENTIAL CONTROL TECHNIQUES
There are numerous potential multimedia pollutants from residual oil pro-
cessing for which emission control regulations may be developed and implemented
over the next 10 years. Some of the regulations will obviously receive greater
attention and will be implemented earlier than others because of their environ-
mental impact. The potential pollutants from residual oil processing systems
are found in all media, in wide concentrations, and in various forms. Table 5-1
shows the diverse physical forms which the multimedia pollutants take in four
major process categories (FGD, HDS, CAFB, and POX). Some major pollutants in
residual oil, such as sulfur, may appear as different compounds in all phases of
each process category. Others will only be associated with one process or phase.
-127-
-------
TABLE 5-1. PHYSICAL FORMS OF MULTIMEDIA EFFLUENTS FROM
RESIDUAL OIL UTILIZATION PROCESSES
Process
FGD
Air
Stack gas
Particulate
Fugitive
Water
Runoff
SIurry
Solid Waste
Sludge handling
and disposal
Noise
Noise (limestone
preparation)
Heat (stack)
HDS Flue gas
Particulate
Fugitive HC
Vents
Sour water
Filter backwashs
Spills
Catalysts handling
Spent cat. disposal
Filter backwash
disposal
Hydrogen manufacture
Noise (compression)
Heat (flares, fur-
naces)
CAFB Flue gas
Parti cul ate
Fugitive
Vents
Runoff
Ash
Spent stone
Fugitive (coal and
limestone
Noise (solids
transport)
Heat (flares,
furnaces)
POX Flue gas
Particulate
Vents
Fugi ti ve
Sour water
C/gas separation
Ash
Spent catalyst
Noise (compression)
Heat (flare)
-128-
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For the control of pollutants in air (first column of Table 5-1), there
are several effective and widely-used techniques which may be used to attain
the effluent quality desired. Some of the potential control technologies being
considered for the control technology assessment for air are listed below:
• Gravitational/mechanical collector
• Media filtration (e.g., baghouse, fabric filter)
• Adsorption (e.g., carbon)
• Absorption (scrubber)
• Condensation
• Electrostatic precipitation
• Incineration
Pollutants in a water stream are the most common final disposal or treat-
ment problems, because the compounds in air and solids often end up in waste-
water streams from scrubbers or in runoff from solids storage areas. The fol-
lowing treatment steps have been considered for the control technology assess-
ment for water:
• Rainwater run-off collection
• Equalization/Neutralization
• Gravitational (API) oil/water separator
• Dissolved air flotation
• Coagulation/flocculation
• Biological filtration (trickling filter)
• Activated sludge system (including aeration basins, clarifiers, and
sludge recycle)
• Granular media filtration
• Carbon adsorption
• Stripping
The potential solids and sludge treatment techniques generally accepted
-129-
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for residual oil processing systems are listed below:
• Catalyst regeneration
• Sludge thickening
• Vacuum filtration
• Chemical fixation
• Fluid-bed incineration
• Land filling/land farming
Heat recovery, noise, and thermal pollution are generally difficult to
abate. With process modification and source isolation and insulation, however,
the pollution could possibly be reduced to a minimum.
An optimum or cost-effective pollution control strategy is always case
dependent. Source characteristics, desired goal, and best available technology
are the factors which will dictate the most attainable environmental quality.
Cost limitations usually play an important role in setting a most probable en-
vironmental goal; and, consequently, a most practical control strategy is de-
termined by a risk and benefit analysis.
Potential control systems and disposal options for known pollutants from
residual oil combustion and upgrading operations are tabulated in Table 5-2.
In general, the treatment methods listed are commonly practiced in the refinery
and utility industries. For each pollutant listed, a control technology study
has been made to compare the treatment methods and their limitations for use.
For each treatment method, the applicable effluent concentration and expected
removal efficiency are also listed.
Some of the pollutants listed in Table 5-2 are more likely to pose an en-
vironmental problem in certain processes than in others. For example, cyanide
and ammonia are more likely to be major concerns in POX and HDS wastewater,
while vanadium and other heavy metals are of concern in these processes, as
well as FGD and CAFB. Phenols have been noted as a possible problem in POX
wastewater; and pollutants, such as suspended solids and tar and oil, will be
of concern in every residual oil utilization process under study.
Particulate matter in the gaseous emission streams from residual oil
-130-
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TABLE 5-2. POTENTIAL CONTROL TECHNOLOGY FOR RESIDUAL OIL PROCESS EFFLUENTS
Water
Pol1utants
Cyanide
-• Fluoride
to
Tar and
Oil
Treatment Method
(1) Decomposition to C02 and N
via cyanate with chlorine
at pH 8-8.5
(2) Electrolytic decomposition
to C0onand N£ via cyanate
at 200°F
(3) Ozonation
(1) Precipitation with lime as
calcium fluoride at pH 11
(2) Coagulation by alum
(3) Adsorption on hydroxyla-
patite bed
(1) Gravity separation
(2) Centrifugation
(3) Coagulation or demulsifi-
cation with chemicals,
followed by air flotation
or settling
Limitations
Toxic cyanogen chloride may
be liberated, a large ex-
cess of chlorine is required
Interference by sulfate
Only partial decomposition
to C02 and N2
Slow rate of precipitation
Applicable only to low
hardness water
Presence of chlorine in-
creases cost of bed regener-
ation
Does not remove emulsion
Addition of alum forms
sludge which are difficult
to dewater
(continued)
Applicable
Concentration
Range
Removal
Efficiency
100-1000 mg/1 100%
> 1000 mg/1 99.9% after
7-18 days
100-1000 mg/1 100%
720 mg/1
< 20 mg/1
< 20 mg/1
Primary
treatment
Secondary
treatment
Secondary
treatment
97-99%
95%
92-98%
60-99% of
floated oil
50-90%
-------
TABLE 5-2 (Continued)
Mater
Pollutants
Tar & Oil
(cont'd.)
Phenols
co Suspended
• Solids
Ammonia
Chloride
Sulfide
Treatment Method
(4) Biological treatment
(1) Pulsed column extractors
(2) Light oil extraction
(Koppers)
(3) Incineration
(4) Activated carbon bed
(1) Sedimentation
(2) Chemical coagulation
(3) Filtration
(1) Stripping at pH of 10-11
(2) Biological nitrification
(3) Ion exchange
(1) Deep well injection
(2) Evaporation ponds
(1) Biological oxidation to
sulfate
Limitations
Water adsorbs C02-may lead
to scale formation
Nutrient may be required
Limited by geographical
location and land avail-
ability
Applicable
Concentration
Range
Secondary
treatment
> 500 mg/1
> 1500 mg/1
> 7000 mg/1
< 50 mg/1
< 1250 mg/1
>60 g/1
Removal
Efficiency
Removal to
15 mg/1
94%
98-99.3%
100%
> 99%
90-95%
95-99%
95%
50-90%
> 99%
80-95%
Ultimate disposal
100%
100%
(continued)
-------
TABLE 5-2 (Continued)
Water
Pol 1utants
Treatment Method
Vanadium (1) Ferric hydroxide adsorption
Heavy Metals (1) Lime and settle
(Cr, Cu, Ni)
(2) Sulfex™
Air Pollutants
Particulate (1) Cyclone
(2) Tornado
(3) Bed filter
(4) Electrostatic precipitator
Limitations
Reduction is not complete.
Rate depends on pH, reduc-
ing agent, and contact time
High initial investment
High pressure drop (4-40
in. W.G.)
High pressure drop (30
in. W.G.)
High energy consumption
Applicable
Concentration
Range
<. 800 mg/1
100-500 mg/1
1-500 mg/1
Removal
Efficiency
99%
> 99%
95-98%
80-90%
< 30 gr/SCF 93-97%
< 40 gr/SCF 90%
99%
Source; Robson, F. C., and W. A. Blecher (UTRC) and C. B. Colton
(Hittman Associates, Inc.), "Fuel Gas Environmental
Impact," EPA-600/2-76-153, June, 1976.
-------
utilization processes generally contains much of the trace metals present in
the oil feed, as well as acid aerosol emissions such as H2SO« from F6D pro-
cesses, which may be adsorbed by the particulate. Thus, these pollutants are
not listed as separate air pollutants, since the same treatment processes ap-
plicable to particulate control are effective for trace metal and acid aerosol
removal as we!1.
Table 5-2 will be expanded as additional treatment technologies are devel-
oped or additional problem pollutants are revealed, or reduced if potential
pollutants now on the list are found to exist in the effluent in concentrations
too small to present environmental or health hazards.
5.2 RESIDUAL OIL UTILIZATION TECHNOLOGY
As a result of the expected standards setting activities for new and ex-
isting residual oil processes, pollutant control techniques are being develop-
ed and implemented to meet future standards. A large fraction of current pol-
lutant control applications in the utility industry use flue gas scrubbing as
a post-combustion treatment. Other approaches such as upgrading fuels, as
well as more advanced combustion and oil processing, are being evaluated for
more extensive potential future use. The applicability and effectiveness of
residual oil utilization technology depend on the specific equipment and cha-
29
racteristics of the fuel used. The progress made in residual oil utilization
processing is a function of the importance of the source in local and national
pollutant regulatory strategies.
The following paragraphs summarize the technical problems and environment-
al needs of the major residual oil utilization technologies based on the dis-
charge stream sources.
Solids Pretreatment
The crushing, sizing, handling, drying, and storage of limestone and other
solids pretreatment are characterized by fine particulate emissions and some
aqueous effluents from water runoff. The most common dust control technolo-
gies use hoods, cyclones, bag houses, or electrostatic precipitators. Simpler
dust control problems are handled using water sprays followed by primary waste-
water treatment for the aqueous effluents. In some cases where solids drying
results in organic air emissions, hydrocarbon control using afterburners or
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carbon adsorption may be used. In general, for the participate problems in
solids pretreatment, data from cement plants and particulate control devices
should be directly applicable. However, only limited data are available for
the control of hydrocarbon emissions.
Oil Gasification
No data is available on characteristics of vent gas emissions from the
various oil feeding and ash removal devices; but, the applicable control tech-
nologies include particulate collection, incineration, and recycle. There is
a serious need for data on the amounts and types of organics, H2S, COS, SOp,
HCN, NH3, and trace elements for start-up vent streams. The ash from residual
oil gasification may be treated by chemical fixation, used in some by-product
applications, or placed in a landfill. Although limited data are available on
ash solid waste disposal, data on organics, unreacted carbon, and trace ele-
ments, along with leaching tests, are needed. Data is also needed on suspend-
ed and dissolved organics and inorganics for ash quench water recycle and
treatment processes.
Gas Purification
For residual oil processes which have a product gas, there are three
discharge stream sources requiring intermediate pollutant control technology.
(1) Cyclones and electrostatic precipitators are applicable for removing and
collecting particulates. The performance of particulate removal devices is
highly dependent on the loadings, size distribution, and physical characteris-
tics of the collected particulates. Limited data are available on these
streams, but additional data are needed to determine collection efficiencies.
(2) Gas quenching and cooling involves stream characterizations for collected
tar and particulates from the gas and spent quench liquor. Data from spray
towers and exchangers are needed to determine the removal efficiencies for
particulates, tars, oils, and trace elements. Spent quench liquor effluent
may contain suspended organics, inorganics, and trace elements which will af-
fect the loading for recycle and waste water treatment processes. (3) Chemi-
cal or physical sorption and direct conversion processes are used in removing
acid gases. Data are needed to determine the acid gas removal efficiency, the
sorbent or solvent degradation characteristics, and blowdown. Some limited
data have been reported on most acid gas removal processes used to treat low-
-135-
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and medium-Btu gas.
Air Pollution Control
The methods of controlling particulate emissions such as cyclones, elec-
trostatic precipitators, baghouses, and wet scrubbers are currently available;
however, data are needed to determine an effective means of collecting these
emissions so that they may be treated by typical particulate control techni-
ques. Limited data are available on most direct conversions and Claus tail
gas cleanup processes for treating sulfur-laden gases. Hydrocarbon control
data via afterburners and carbon adsorption is not available in enough detail
to project the hydrocarbon removal effectiveness and sorbent and catalyst de-
gradation characteristics.
Water Pollution Control
Numerous discharge stream sources fall into this operational category,
including oil/water separation, suspended solids removal, and dissolved organ-
ics and inorganics removal. Filtration, separation, and flocculation-flotation
are generally used to segregate sludges and oily scum from wastewater streams.
Liquid extraction, oxidation, and carbon adsorption are used to remove dissolved
organics. Acid gas and ammonia may be stripped from sour water, but the by-
product tail gases must be treated further. Other dissolved inorganics may
be removed by forced evaporation.
Solid Waste Control
Ash, sludge, spent sorbents, and spent catalysts must be incinerated,
chemically fixed, and/or used as landfill. Ultimate disposal of these solid
wastes depends to a large extent on the results of leachate tests for trace
elements and dissolved toxics. For example, a major problem associated with
non-regenerable scrubbers is the tremendous amount of waste material that must
be disposed of in an environmentally-acceptable manner. In some cases, credits
may be taken for usable solid wastes to make the control technology more cost
effective; but, in the U. S., most sludge produced from scrubbers requires
disposal.
5.3 ECONOMIC COST MODEL DEVELOPMENT
An economic evaluation of a chemical process can be typically categorized
-136-
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into four major steps. The first step is flow plan preparation; the second
step is equipment sizing; the third step is cost estimation, including direct
cost and indirect cost; and, finally, the fourth step is feasibility measures
evaluation involving calculation of payout time, discounted cash flow, return
on investment and annualized cost in the case of non-profit generating invest-
ment, such as pollution control devices.
Although many methods and procedures currently being used are effective
for costs estimation purposes, they do not provide a common basis for compari-
son as to evaluation of economic feasibility or cost effectiveness among var-
ious processes under investigation. It is necessary that an economic analysis
of pollution control and energy production operations should be conducted uni-
formly based on a standardized procedure and consistent data bases. In fact,
several attempts have been made within government agencies to propose such a
procedure. The criteria used for the procedure selection are based on relia-
bility, uniformity, and acceptability of a method which will allow for ready
comparison among different processes. Figure 5-1 shows several technical
economic evaluation schemes. The first two steps of an economic evaluation,
the flow plan preparation and equipment sizing, are not included in Figure
5-1.
Table 5-3 lists work flow, procedures/guidelines and results of a standard
procedure of economic evaluation selected for pollution control operations.
This scheme will be followed in the environmental assessment of residual fuel
oil utilization study to conduct cost analyses of various modes of oil utiliza-
tion. Work flow in a typical economic evaluation is depicted in the first col-
umn of Table 5-3. Each block represents a major step in the entire evaluation
scheme. The guidelines and procedures needed to perform the work dictated by
each step, together with its data sources, are listed in the second column
(Table 5-3). The third column of Table 5-3 indicates the results or outcomes
of each-major step. Characteristics and information and data requirements of
five basic cost estimation types are given in Table 5-4. Recommended methods
with estimation accuracy range are also included in Table 5-4. Detailed infor-
mation requirements for preliminary cost estimation of major process equipment
are indicated in Table 5-5.
-137-
-------
Cost
&
Economic
Criteria
o
f
Factor
B
Unit-
Process
Definitive
H
Direct
Cost
Indirects
Contingency
Fee
Construction
Interest
Modification
Start-Up
Land
Working
Capital
Total Capital
Investment
Operating Cost
Economic Criteria
Chilton
Guthrie
Lang
Icarus
Unit-
Process
Modules
Definit.
Estim.
Correlation and
Percentage Factors
Return on Investment
Discounted Cash Flow
Annualized Cost
Figure 5-1 Typical Economic Evaluation Schemes
-138-
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TABLE 5-3. STANDARD PROCEDURES OF ECONOMIC EVALUATION FOR POLLUTION CONTROL OPERATIONS
Work Flow Chart
Plant General Info. &
Engineering Specifica-
tions
CO
ID
Procedure
Selection
Rapid Capital
Investment Estimation
Definitive
Capital
Investment
Estimation
Operating Cost
Estimation
Economi c
Evaluation
Guideline, Procedure and Data Source
Process Design
Level of engineering effort
Licensor or vendor information
Unit-price method
Exponential (0.7 power) rule
Lang factor; Chi 1 ton factor
Guthrie Scheme
EPA reports
Vendor information
M. W. Kellogg cost model
Guthrie Scheme
Proprietary data/computer programs
M. S. Kellogg model
Chemical Engineering Handbook
EPA reports
Proprietary data/computer programs
Result
Plant Capacity, M&E Balances,
Flow Plan, Equipment List
Cost model/procedure to use
Total capital investment re-
quired or Major Plant Items (MPI)
cost with accuracy of estimation
Major Plant Items (MPI) cost
with accuracy of estimation
Operating cost and other expenses
Total capital investment re-
quired, Feasibility measures,
i.e., ROI, POT, DCF & UAC
-------
TABLE 5-4. DEFINITION AND GUIDELINES OF FIVE BASIC ESTIMATION TYPES
I
_J
o
Types of Estimates (each
has several designations)
Order-of-Magnitude -
Rapid Estimation Ratio
Study (factored) - Rapid
Estimation
Preliminary
Budget Authorization
Scope - Rapid/Defini-
tive Estimation
Definitive
Project Control - Defi-
nitive Estimation
Detailed
Firm
Contractor's - Defi-
nitive Estimation
Method
Unit price; .7 power
function relationships
Lang, Chi 1 ton, Guthrie
Scheme
Lang, Chilton, Guthrie
Scheme
Detailed item-by-item,
step-by-step estimation
Detailed item-by-item,
step-by-step estimation
Information Requirement/
Estimates Characteristics Accuracy
Based on market survey or rough +. 50%
feasibility study (plant capacity,
unit-price curves), gives prelim-
inary indication of feasibility
Based on study design effort (sim- +_ 40%
plified flow plan with rough M&E
balances), provides guidance for
further considerations and project
studies
Sufficient data (flow plan, equip- +. 20-30%
ment list) are available on which
to base estimate that results can
be used to make budget decision
More complete data are available +_ 10%
but short of completed specifica-
tions and drawings
This estimate is based on complete +_ 5%
specifications, drawings, and site
surveys
-------
TABLE 5-5. INFORMATION REQUIREMENTS FOR PRELIMINARY COST ESTIMATION
Major Process
Equipment
Ib/hr or
GPM or
CFM or
Total Vol.
Fired Heaters &
Boilers
Stacks
Reactors & Inter-
nals (catalysts) X
Towers & Internals
(trays, packing)
Heat Exchange
Equipment
Cooling Towers
(cells, temp.) X
Vessels & Drums X
Pumps & Drivers X
Blowers & Compres-
sors X
Elevators, Convey-
ors, Mat'l. Hand-
ling Equipment X
Tankage X
Filters, Centrifu-
ges, Sep. Equip-
ment X
Agitators & Mixers
Scrubbers & En-
trainment Separa-
tors (Internals) X
Mechanical
Capaci ty/Descri pti on
Btu/hr.
or Head
Surface or
Area MP
X
X
X
X
X
X
X
X
X
Height
or
Type Dia. Length
X
X X
XX X
XX X
X
X
X
X X
XX X
X
X
X
Design
DT,
Design
Temp.
X
X
X
X
X
X
X
X
X
X
DP,
Design
Pres.
X
X
X
X
X
X
X
X
X
X
Material of
Construction
X
X
X
X
X
X
X
X
X
X
X
X
(continued)
-------
Major Process
Equipment
Machine Tools & Ma
chine Shop Equip
ment
H.V.A.C., Dust Con
trol (Process
Only)
TABLE 5-5 (continued)
Capaci ty/Descri pti on
Ib/hr or
GPM or
CFM or
Total Vol.
Btu/hr.
or
Surface
Area
Head
or
HP
Height
or
Type Dia. Length
Mechanical
Design
DT, DP,
Design Design
Temp. Pres.
Material of
Construction
ro
Note: Range of accuracy for preliminary estimation is +_ 25%,
-------
The Lang factor method should be considered only for checking purposes.
The Chi 1 ton method may be the most useful factor method and usually is excel-
lent for checking purposes. The Guthrie scheme is the most involved factor
method and should yield reliable results. The Guthrie scheme could sometimes
be employed as a definitive estimation method, provided that correlated cost
data and good Guthrie factors are available. The ICARUS data manual presents,
in convenient graphical and tabular form, cost information for installed
equipment item modules for pollution control facilities. The unit-process
modules method is appropriate for liquid waste treatment plants, e.g., munici-
pal sewage treatment.
The accuracy associated with a cost estimation is closely related to cost
data availability and the level of process engineering effort. Often, an ade-
quate process engineering work to achieve certain degrees of accuracy of esti-
mation on a process in question might not always be done. Often, it is possi-
ble to develop only a rough estimate. Minimum data required to allow a rapid
estimation are sometimes lacking, especially for pollution control operations.
On the other hand, good engineering work may be available from owners of pro-
cesses, e.g., POX, HDS, and CAFB. In some cases, however, an "isolated" pro-
cess cannot always be found in typical industrial applications; e.g., waste
streams from POX and HDS are generally integrated with a centralized or combin-
ed waste treatment plant. Cost information on this type of process could only
be obtained by flow rate proration.
Hence, potential problem areas in carrying out the entire economic eval-
uation for pollution control operations are:
(1) inadequate engineering work for the accuracy desired,
(2) scarcity of raw cost data, and
(3) lack of readily-usable engineering data/information
resultant from industry's combined waste treating
practice employed in a complex chemical processing
plant, e.g., refinery operations.
Catalytic1s approach to these problems involves the development of stan-
dard procedures of economic evaluation, uniform data bases, and adequate engi-
neering effort.
-143-
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Much effort has been devoted to the development of standard procedures and
uniform cost data bases, and considerable progress has been made. However, pro-
gress on the development of adequate process engineering work regarding some re-
sidual oil utilization processes of interests, e.g., HDS and POX, has been li-
mited. The lack of progress in this area is due to the scarcity of a comprehen-
sive waste streams inventory and characterization, and, to a lesser degree, to
the incompleteness of process information resultant from industry's reluctance
or inability to yield an adequate set of process data and information. Never-
theless, good progress has been made in the development of process information
regarding the commercialized residual oil utilization processes. It is believed
that adequate process engineering work for carrying out the desired economic
analysis could be developed as soon as comprehensive emissions data become avail-
able. This will be a result of the current effort on waste streams characteri-
zation as part of this environmental assessment project.
5.4 SUMMARY AND CONCLUSIONS
In light of the fact that emission control regulations are likely to be
developed in the next ten years for numerous multimedia pollutants from residual
oil utilization processes, it is important that the existing and/or developing
control systems and disposal options be evaluated and compared from both tech-
nological and economic standpoints. Environmental impact of the various control
options will be assessed based on actual sampling and analysis results. Econo-
mic evaluation is to be based on a standardized procedure and consistent data
bases.
Control techniques have been enumerated for air, water, and solids/sludge
effluents, which may vary widely in such important parameters as control effi-
ciency, energy usage, applicable concentration range, and costs; but, an optimum
or cost-effective pollution control strategy is always case dependent.
Large data gaps still exist in many of the control technology assessment
areas. The areas included are listed below:
• Limited data are available for hydrocarbon emissions from
solids pretreatment.
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• No data are available on characteristics of vent gas emis-
sions from the various oil feeding and ash removal devices
in oil gasification.
• Data are needed on organics, unreacted carbon, trace ele-
ments, and leaching tests for ash solid waste disposal
from oil gasification.
• Data are needed on suspended and dissolved organics and
inorganics for ash quench water recycle and treatment pro-
cesses from oil gasification.
• Limited data are available on particulate removal by cy-
clones and electrostatic precipitators for product gas
purification.
• Spray tower and exchanger data are needed to determine
removal efficiencies for spent liquor from gas quenching
and cooling which contains particulates, tars, oils, and
trace elements.
• Limited data have been reported, but more are needed to
determine acid gas removal efficiency, sorbent or solvent
degradation characteristics, and blowdown from gas purifi-
cation.
• Data are limited on most direct conversions and Claus tail
gas cleanup processes for treating high sulfur gaseous
emissions.
In order to develop the data necessary for control technology assessment,
Catalytic shall conduct sampling and analysis activities, incorporating the
Level 1 and Level 2 sampling and analysis methodologies adopted by EPA for
five typical plants representing the following categories: combustion without
controls; combustion with FGD; combustion with POX; HDS; and upgrade and HDS
for low sulfur fuel oil. Development of the necessary data base will involve:
(1) Selecting a preferred plant site and an alternative
site for each category;
-145-
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(2) Obtaining cooperation and entry permission into each
preferred and alternate plant site;
(3) Designing the field sampling experiment;
(4) Conducting a pre-test survey, with participation by
the subcontractor who will conduct the field testing
and laboratory analysis;
(5) Conducting a field test;
(6) Conducting a chemical laboratory analysis; and
(7) Preparing an environmental assessment sampling and
analysis document.
No problems are anticipated beyond the coordination of required auxiliary
services and facilities, which have been costed out in detail based on previous
sampling experience.
Available data indicate that spent catalyst resulting from the conversion
of residual petroleum fuels is a potential source of environmental impact which
should receive further attention. Accordingly, Catalytic shall:
(1) Investigate the current catalyst reprocessing and dis-
posal options;
(2) Characterize the spent catalyst;
(3) Evaluate control/disposal options via thorough engi-
neering and economic analyses; and
(4) Incorporate the results into the environmental assess-
ment report.
In the absence of regulations and standards pertinent to compounds in the
spent catalyst, toxicity information regarding the metallic compounds that could
be formed under hydrodesulfurization conditions will be compiled and used as a
basis for evaluation.
A series of parametric cost studies will be conducted to characterize one
or more of the environmental control process variables having incremental ef-
fects on the direct production costs of the following process categories:
-146-
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combustion with FGD; hydrodesulfurization; and combustion with POX. The proce-
dure will be as follows:
(1) Review existing cost data;
(2) Determine the incremental costs of selected process var-
iables related to environmental control;
(3) Recommend the best technologies economically achiev-
able; and
(4) Prepare a parametric cost study document.
Many methods and procedures are currently available for effective costs
estimation. A standardized procedure is to be selected based on reliability,
uniformity, and acceptability of a method which will allow for ready comparison
among different processes. The Chi 1 ton method may be the most useful factor
method and usually is excellent for checking purposes.
Scarcity of raw cost data and lack of readily-usable engineering informa-
tion are potential problems, but it is anticipated that development of standard
procedures of economic evaluation, uniform data bases, and adequate engineering
effort will alleviate these problems.
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SECTION 6
ENVIRONMENTAL ALTERNATIVES ANALYSIS
6.1 SOURCE ANALYSIS MODEL (SAM)
In conducting environmental assessments, it is necessary to do one or more
of the following tasks: (1) rank individual effluent streams by the expected
toxicity of their discharges; (2) establish sampling priorities; (3) determine
problem pollutants; (4) recommend best multimedia control technology alterna-
tives; and (5) recommend control/disposal technology development programs. An
objective of alternative analysis is, therefore, to compare environmental pol-
lutant loadings from specific sources to Multimedia Environmental Goals (MEG).
Aerotherm Division of Acurex Corporation has prepared for EPA the simplest
member of a sequence of Source Analysis Models (SAM's) of increasing complexity
and thoroughness which can be used as a tool to help with the five tasks men-
tioned above.
The use of a Source Analysis Model (SAM) for screening of control options
provides the environmental assessment community with a workbook or format which
identifies input data requirements and guides the user through a set of calcu-
lations. These calculations provide a quantitative means of assessing the pol-
lution potential of a source and of control options.
The SAM format focuses on each separate effluent stream which arises dur-
ing an energy production or industrial process. Such streams may exist because
of the process itself, for example, flue gas and bottom ash emissions from a
utility boiler, HgS, mercury, and arsenic emissions from certain stream-
dominated geothermal wells, and hydrocarbon emissions at petrochemical refiner-
ies. Streams may arise because of the application of pollution control tech-
nology to a process-generated effluent, such as, hopper ash from baghouses or
electrostatic precipitators, and scrubber-generated sludge.
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Each use of the SAM format assumes a specific set of effluent streams
which exit from the process itself or from the control technology in use. The
format then examines the extent or amount of environmental impact which results
from utilizing information on specific substances of concern determined from
EPA's (Levels 1 and 2) phased approach to comprehensive sampling and analysis.6'7
SAM's can be used to rank effluent streams. In this application, the SAM
is used to compare the toxic-unit rate of discharge into each effluent stream;
these toxic-unit summations can then be ranked by magnitude. Examination of
the relative magnitudes generated by different streams immediately shows the
relative hazard of the different effluent streams.
Another function of SAM's is the establishment of additional Level 2 and
Level 3 sampling and analysis priorities in performing environmental assess-
ments .
Potential problem pollutants and pollutant priorities may be determined by
the SAM format. In this application, use of the SAM can lead to an understand-
ing of the pollutants that are most likely to cause major environmental impact
because they remain poorly controlled under all equipment options currently
available.
SAM's can also determine the most effective control technology options.
In this application, the SAM is used to examine a given process stream with
first one and then another control approach. The impact of alternative control
equipment choices can be compared on the basis of the differing reductions which
can be expected to occur in the original process stream pollutant emissions, and
the ways in which concentration of certain pollutants into particular control
equipment effluent streams will occur.
Still another use of the SAM format is to determine the need for control/
disposal technology development. Straightforward application of the proper
SAM format can, therefore, be used to accomplish a variety of goals.
In the simplest SAM, designated "SAM/1A: A Rapid Screening Method for
Environmental Assessment of Fossil Energy Process Effluents," effluent streams
from any process or applicable controls are not assumed to interact with the
external environment (i.e., transport of the components in the effluent stream
to the external environment occurs without transformation of the components).
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No assumption is made about pollutant-specific dispersion; but, it is assumed
that such dispersion from the source to a receptor would, in almost all cases,
be equal to, or greater than, the safety factors normally applied to acute
(short-term exposure) toxicity data to convert them to estimated safe low-level,
longer-term chronic ambient exposure levels. Furthermore, the premise that the
MATE values are adequate and that no synergistic effects occur should also be
assumed. The validity of these assumptions cannot be established on a case-by-
case basis. In many cases, the assumptions are conservative. However, these
factors should be kept in mind in evaluating the need for more detailed assess-
ment.
Thus, SAM/1A is on an effluent concentration basis and uses only one poten-
tial assessment alternative (the MATE).
The general procedure to be followed when using SAM/1A for a given source
and control option has been described and explained by Aerotherm. Such rapid
screening requires understanding of the assumptions being made.
The user assumes that thes*s 650 substances presently on the MEG list as
potential components of an effluent stream are the only ones which need to be
included and are known accurately enough. Unknown components may be sources
of environmental impact which are modified or modifiable by the control tech-
nology and, therefore, Level 1 bioassay results will be important as a compan-
ion data base for interpretation of SAM/1A results.
Providing sufficient data to determine the need to reduce emissions from
an industrial operation is one of the objectives of alternative analysis. The
development of methodology for source assessment and analysis is still evolving
and is a continuous effort for EPA. It can be expected that suitable models or
methodology will be refined as experiences grow. Some kinds of alternative
analysis (e.g., SAM/1A) to provide information for process ranking regarding
sources/controls, pollutants, and regional siting will be carried out in the
current work of environmental assessment on various residual oil utilization
processes.
6.2 POLLUTANT PRIORITIZATION
Pollutant prioritization is an integral part of the environmental assess-
ment methodology, as it is presently being developed by EPA. Figure 1-1
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illustrates the overall environmental assessment/control technology development
scheme, including pollutant prioritization as it fits into the environmental
objectives development task.
Prioritization can be divided into two parts: preliminary prioritization
and practical prioritization. Preliminary pollutant prioritization involves
the comparison of "worst case" effluent concentrations of each potential pol-
lutant with its respective Minimum Acute Toxicity Effluent (MATE) value and
the ranking of pollutants by the resulting ratios. Practical pollutant prior-
itization consists of ranking potential pollutants by the ratio of their ex-
pected (rather than worst case) effluent concentration to MATE values, based
on a practical engineering analysis of the combustion and control processes.
Practical experience with the prioritization methodology has been gained
by its application to a lime slurry Flue Gas Desulfurization (FGD) system
treating flue gas from a residual oil-fired boiler.
Prioritization is a screening method for determining which pollutants to
examine first. Since time and money prohibit extensive study of the universe
of potential pollutants, prioritization is used to determine priority pollu-
tants for investigation, as the name implies.
Preliminary (worst case) prioritization is valuable as a method for re-
ducing the number of pollutants to be considered in the detailed engineering
analysis which follows as part of the practical prioritization. The expected
effluent concentrations which result from the engineering analysis are used
as input to test program development and identification of sampling and
analytical techniques. Results of practical prioritization serve as a check
list for sampling. Pollutant streams within a process can be prioritized
using the expected effluent concentrations as calculated by the engineering
analysis. Results of the engineering analysis may indicate potential problems
and will supplement Level 1 sampling and analysis with details.
The first step in pollutant prioritization is to obtain detailed analyses
of all system inlet streams. For the lime scrubbing of residual oil-burner
flue gas, those streams are: residual oil, combustion air, lime, and water.
For the worst case effluent concentrations, it is assumed that all inlet
stream pollutants are completely discharged in the effluent and that each
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pollutant compound which could be formed from any combination of inlet stream
constituents is formed to the maximum concentration possible, given the amounts
of constituents available. For example, the worst case concentration of elemen-
tal nickel in the effluent is calculated assuming that all Ni in the inlet
streams exists as elemental nickel. Similarly, the worst case concentration
of nickel chloride in the effluent is calculated assuming that all Ni combines
to form NiClp (if enough Cl is available). Worst case emissions must be cal-
culated for each media (air, water, and land). Obviously, the sum of the
worst case effluents is greater than the amount of actual effluent leaving the
system. Thus, the worst case analysis indicates every possible problem pollu-
tant; but, the results are far from being a realistic description of the sys-
tem effluent. Almost all pollutants indicated in a worst case analysis will
exist in smaller concentrations than their worst case values (none will exist
at higher concentrations), and many may not be detected at all in the actual
effluent.
A ranking of potential pollutants based on the worst case analysis must
include a factor of relative toxicity as well as concentration. MATE'S, devel-
oped at Research Triangle Institute (RTI) from toxicological data such as TLV's,
NIOSH recommendations, LD^'s and LD^'s, LC^'s, TD^'s, TLm, Drinking
Water Regulations, and Water Quality Criteria, are the most comprehensive list
of toxicity indicators available. MATE'S were developed specifically for
those species expected to have a potential for forming in combustion processes.
They have been developed by experts using the available data and can be com-
pared directly with calculated effluent concentrations of potential pollutants.
Although the level of confidence to be associated with MATE'S is admittedly
imprecise, they have been accepted by EPA for use in Source Analysis Models
(SAM's) and can be readily applied to worst case analysis results, with the
only difference being that calculated effluent concentrations rather than
concentrations based on sampling and analysis results are used.
A worst case effluent concentration-to-MATE ratio is determined for each
potential pollutant; organics and inorganics, in elemental and compound form,
and in each media. Pollutants are then ranked according to their concentra-
tion/MATE ratios, from high to low. Any pollutant with a ratio greater than
one is given highest priority and must be considered in the practical analysis
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which follows. In the lime scrubbing example, roughly half of the potential
inorganic^pollutants to air had a ratio greater than one. Ratios ranged from
9.17 x 10 (ozone) to 6 x 10"5 (cesium). Ozone is an example of the unrealis-
tic results of worst case analyses. In an actual lime scrubber effluent, the
oxygen will exist as mostly water vapor and oxides of sulfur, nitrogen, and
trace metals, with very little or none, as Og. Of course, the worst case
analysis also includes the greatest possible concentrations of those oxides
and water vapor formed.
In the lime scrubbing worst case analysis, MATE values have not yet been
developed for many of the potential pollutants. These potential pollutants
could not be ranked with those for which MATE'S had been established but were
set aside. These potential problems should be considered in the practical
analysis.
Once preliminary prioritization has been completed, practical prioritiza-
tion can begin. The first step is to perform an overall material balance for
inlet and outlet streams. Previous experimental results and operating data
can be used to determine the distribution of major constitutents between efflu-
ent streams. Thermodynamic and kinetic data can be used to predict the forma-
tion of trace pollutants in the combustor, given combustor inlet stream compo-
sitions. Catalytic plans to use a computer program based on thermodynamic
equilibrium calculations to determine the formation of pollutants in a residual
oil burner.
The computer program predictions will not be absolutely accurate, since
kinetic phenomena such as residence times and rates of formation are not
considered; but, the equilibrium calculations are the best projection on which
to base the engineering analysis. The species to be considered are limited by
the availability of thermodynamic data, but the program will yield results on
the inorganics of interest and some of the organics (presently two dozen spe-
cies ).-
A practical engineering analysis, including use of computerized equili-
brium calculations, if applicable, will yield the expected distribution of
trace pollutants between effluent streams, i.e., air, water, and land. Prior-
ity I pollutants need to be considered first in the practical analysis. These
probable effluent concentrations can then be ranked by MATE ratios, just as
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the worst case values are.
The result of prioritization is a list of pollutants in order of relative
hazard to health and/or ecology. Preliminary or worst case prioritization
does not reflect existing control technology. Practical prioritization does
reflect existing control technology and indicates the pollutants for which
new control methods are needed.
Prioritization is important to EPA because it indicates potential needs
for further research and development. Prioritization saves time and money by
indicating which pollutants to study first and does so in a much more cost-
effective manner than actual sampling and analysis. In most cases, an engi-
neering analysis for a specific set of conditions can be performed in a frac-
tion of the time it would take to obtain samples at those particular condi-
tions. Level 1 sampling and analysis often indicate only a general class of
compounds present in a stream, but a thorough engineering analysis (paper
study) can determine the probable specific pollutant compounds within that
class of compounds. Engineering analysis can often resolve discrepancies be-
tween conflicting results in separate sets of sampling data. Practical prior-
itization results can be more reliable than sampling data due to the potential
for human error in sampling and analysis and the possibility of faulty data
due to varying process operating conditions. As an indicator of expected re-
sults, practical prioritization can point out areas of faulty data and indi-
cate the need for additional sampling.
There are, however, uncertainties in the reliability of prioritization
results which arise from uncertainties in the data on which prioritization is
based. The uncertainty in the level of confidence associated with MATE'S re-
sults from uncertainties in health/ecological data and from the lack of con-
sideration of additive, synergistic, and antagonistic effects, as well as the
arbitrary assumptions involved in some of the MATE derivations. The lack of
thermodynamic and kinetic information on non-equilibrium processes, as well
as the shortage of basic thermodynamic data for organic compounds, also con-
tributes to uncertainty in prioritization results. Also, variations in feed-
stock analyses and process parameters make generalization from specific studies
difficult.
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Figure 1-1 indicates that pollutant prioritization is a part of environ-
mental objectives development. The preliminary, worst case, prioritization
belongs under environmental objectives development as a direct input to envir-
onmental data acquisition, where practical prioritization is carried out as
part of the comprehensive waste stream characterization and input/output mater-
ials characterization. Practical prioritization places emphasis on emissions
loadings, determined by material balances and thermodynamic calculations and
integrated with sampling results.
Environmental objectives development and environmental data acquisition,
which receive direct input from prioritization, are two of the six major com-
ponents of environmental assessment. Figure 1-1 illustrates the input of en-
vironmental assessment into control technology development and vice versa.
Environmental assessment determines the need for pollution control via the
environmental alternatives analyses, which feeds directly into control technol-
ogy development, where specific processes are developed and evaluated. The
results of control technology development are fed back into the control tech-
nology assessment task of environmental assessment.
6.3 STANDARDS SUPPORT PLAN
At the present time, the concept of a Standards Support Plan (SSP) is
being implemented on specific energy technologies by several of EPA's Indus-
trial Environmental Research Laboratory contractors. The aim of this effort
is to increase the support to the EPA program offices in the area of standards
development. In the future, the SSP for residual oil utilization will define
the activities and schedules for multimedia assessment efforts on advanced oil
processing that relate to standards development. Special reporting formats
will be developed by EPA to conform with the requirements for standards set-
ting. A series of environmental assessment reports will then be prepared for
key technologies. Thereafter, periodic revisions would be made to reflect
changes in policies or technology developments.
The Environmental Assessment Reports (EAR) will summarize background in-
formation on the processes, waste streams, control alternatives, environmental
impacts, and R&D needs. Separate reports will be prepared for advanced oil
processing systems covered in the SSP. For example, environmental assessment
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reports should be prepared for hydrodesulfurization, and the chemically active
fluid bed process, at a minimum. Future environmental assessment reports may
also be needed for partial oxidation.
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SECTION 7
TECHNOLOGY TRANSFER
Catalytic, Inc. has provided general support and coordination to this
environmental assessment program by being a participant in several areas of
technology transfer during the past year. Various presentations have been made
with the permission of EPA on the status of this program for other government
contractors, for process licensors with which Catalytic has entered into secrecy
agreements, for CAFB contractors meetings, and for technical societies. The
following paragraphs include the types of technology transfers in which Catalytic
has participated.
TECHNOLOGY TRANSFER MEETINGS AND ACTIVITIES
To keep abreast of related research and development efforts, Catalytic
attended the Second National Conference on the Interagency Energy/Environment
sponsored by EPA in Washington, D. C. The broad topics discussed were: fuel
processing, utility and industrial power, extraction and benefication, inte-
grated technology assessment, health effects, atmospheric transport and fate,
measurement and monitoring, and ecological effects.
During the year, a task leader attended the Fourth FGD Symposium sponsored
by EPA. Contractors' reports were assembled in our filing system, and this
meeting provided a review and update of the latest FGD methods and control tech-
nology problems.
Last Fall, the entire Catalytic task work team attended the EPA-sponsored
Contractors' Meeting on Environmental Assessment Methodology Development. Con-
tractors' reports of interest included Level 1 Sampling and Analysis and Bio-
assays, Level 2 Organic and Inorganic Analysis, Standards of Practice Manual
Outline, Source Analysis Models, and Source Assessment Methodology. This meet-
ing provided a review and update of the EPA's environmental assessment methods
and problems.
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One task leader attended The Second Pacific Chemical Engineering Congress,
an international exchange of information from Japan, Mexico, and other Pacific
Ocean neighbors. He gathered data on S02 stack gas scrubbing technology, envir-
onmental control technologies, and system designs of several flue gas desulfuri-
zation units. This was an excellent opportunity to update annually both F6D,
HDS, and partial oxidation technologies for the residual oil utilization work
plan.
In September, 1977, the project manager and a team member attended the
lERL/RTP-sponsored Symposium on Environmental Aspects of Fuel Conversion Tech-
nology III in Hollywood, Florida. Of particular interest were R. P. Hangebrauck's
presentation on Environmental Assessment Methodology and RTI's presentation by
Ms. Kingsbury on Multimedia Environmental Goals. Other presentations relevant
to Catalytic1s environmental assessment work concerned testing, sampling, and
analysis of fuel conversion systems and their emissions.
Catalytic, Inc. was given permission by the EPA to make a report at the
fall meeting of the Carolines Air Pollution Control Association (CAPCA). A re-
view of the environmental assessment methodology for residual oil processes was
presented. The technical matter presented was well received due to its appli-
cability to any energy fuel process.
Three task leaders attended the Atlanta Process Measurements Symposium
sponsored by Environmental Research Laboratory of Research Triangle Park. It
was beneficial in defining specific approaches to sampling and analyzing multi-
media effluents specifically applicable to our residual oil usage project. The
program speakers defined uses of environmental assessment data, the techniques
for acquiring data, and users' field experiences, including unsolved problems
for future research in environmental assessment measurement programs useful in
our residual oil usage program. Of most specific benefit to our project were
the field experiences presented by J. W. Hammersma on the "Process Measurements
of Conventional Combustion Systems," whereby a number of sampling and analysis
exclusion criteria were presented that eliminated wasteful expenditure of funds
on unnecessary, existing, available, and unacceptable emission data.
A meeting was held with Dr. W. E. Thompson of Research Triangle Institute
to discuss Catalytic1s input into their survey of conventional Combustion
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Pollutant Assessment (CPA) activities. Dr. Thompson spent one day interviewing
members of this project team to summarize our various project objectives and
current functional activities using a coded computer technique. These CPA ac-
tivities will be reported to EPA.
An exchange of information has been initiated with the Technology Division
of GCA Corporation to develop meaningful test protocol based upon data previously
gathered in Japan and Level 1 sampling experience. Data needs and various as-
pects of Level 1 sampling and analysis were partially defined during September
1977.
The Volatile Organic Compounds (VOC) are under study for proper sampling
and analysis prior to review and coordination with EPA Process Measurements
Branch. The sampling program in Japan is anticipated to commence in the Fall
of 1978. This program is being coordinated with Dr. Ando.
Proposed New Source Performance Standards for Stationary Gas Turbines were
received and reviewed. Modifications were noted to the procedures for sampling
and NOX determination for gas turbines and combined cycles. Our comments were
submitted to the appropriate EPA project director.
A draft "Summary of Key Federal Regulations and Criteria for Multimedia
Environmental Control" by RTI (dated February, 1977) was received for our use
to prevent delays in our prioritization procedures. Also, a draft on "Approach
to Level 2 Analysis Based on Level 1 Results, MEG Categories and Compounds and
Decision Criteria" was received to aid in the prioritization procedures. Ano-
ther draft report, "Minimum Acute Toxicity Effluent (MATE) Values for Organic
and Inorganic Compounds from Fossil Energy Processes," was received to help in
the developing of methodology for setting health/ecological effects objectives.
Another draft report dated 17 August 1977, "Tabulations of Minimum Acute
Toxicity Effluent (MATE) Values for Organic and Inorganic Compounds From Fossil
Energy Processes," was received to help in the developing of methodology for
setting health/ecological effects objectives.
An Aerotherm Project 7250 report entitled "SAM/1 A" A Rapid Screening Me-
thod for Environmental Assessment of Fossil Energy Process Effluents" was re-
ceived to aid in the standardization of the environmental assessment system of
environmental alternatives analyses procedures encompassing SAM/MEG/MATE system
formats.
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Since mid-May of 1977, 347 items have been added to Catalytic1s informa-
tion storage and retrieval system. A new system for abstracting and coding has
been implemented to improve information retrieval. The total number of items
now included in the system is 763.
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SECTION 8
FUTURE EFFORTS
Additional research is needed to insure the assessment of present control
technology now demonstrated and to determine the best available practices and
processes for the effective control of multimedia pollution from residual oil
usage. The results of this work will help to identify those areas requiring
more research and development.
Sufficient information should be generated to completely characterize
effluents and emissions from all processes of interests and their associated
control operations. The information is needed to provide the basis for new
or revised pollutions standards, as well as for engineering design and econo-
mic evaluation of pollution abatement.
It has been known for some time that data deficiency hampers plant design,
and scale-up problems hinder the construction of commercial units. The lack
of data is even more severe in the area of separation technology, which is
the backbone of most pollution control operations. The unavailable data must
be developed to overcome the obstacles. These include development of funda-
mental data in high-temperature and high-pressure operations involving poly-
nuclear aromatic derivatives and the prevalence of \\2> HgS, CO, C02» NH3,
COS, HCN, and H«0 in products of coal gasification and residual oil utiliza-
tion. Thermodynamic and transport properties of key organic compounds and
compounds containing nitrogen, sulfur, and oxygen are urgently needed. Phase
equilibria in mixtures containing water, oil, and raw gas are also needed to
facilitate engineering design. Compounds derived from many trace metals in
coal and residual oil are of particular interest regarding the toxicity and
control technology.
For primary process unit operations such as distillation, design to with-
in 5% is considered routine; but, in the separations field, a factor of two
is not uncommon. Reliable methods of calculation are needed to solve problems
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of important practical interest in the physical separation of heterogeneous
mixtures, such as cake filtration, granular bed and cartridge filtration, cen-
trifugation, dust collection, cycloning, scrubbing, electrostatic precipitation,
thickening, flocculation, and deliquoring of cakes.
Residual oil utilization processes which have high potential for commer-
cialization include regenerate FGD (e.g., double-alkali process and Wellman-
Lord process), H-oil hydrodesulfurization process, Eureka or Dow's new steam
cracking process, and Exxon's flexicoking gasification process. The engineer-
ing and economic evaluation shall include these high-potential processes in the
next phase of environmental assessment work.
One goal of the environmental assessment of these processes is to quantify
aspects such as economics, energy efficiency, applicability, and environmental
impact, so that the processes can be accurately compared. The processes being
considered fall into three major categories: pre-treatment, post-combustion
treatment, and gasification; but, there are considerable differences to be re-
viewed and gathered together into a common basis for comparison.
As examples of the process diversity, the process output can be considered.
HDS produces a low sulfur fuel oil, while CAFB and POX produce low-Btu gases.
Both FGD systems clean up a sulfur dioxide-containing flue gas. Considerable
amounts of water are required for both FGD systems with less being consumed in
the HDS and CAFB processes (including steam), and essentially none in the POX
system. Make-up requirements are relatively simple for the limestone FGD (lime-
stone, water, and fuel oil for reheat), MgO FGD (magnesia, water, and coke),
POX (air), and CAFB (air, coal, and steam); but, a large hydrogen plant is re-
quired for the HDS process. The quality of the resid feedstock has little ef-
fect on the FGD systems, but high metals concentrations can substantially alter
the economic favorability of the HDS and POX systems.
The application of SAM/1A methodology and planned sampling of these differ-
ent processes will be the major segment of the completed environmental assess-
ment. A completed economic analysis and energy efficiency analysis will comple-
ment the environmental assessment and process comparison.
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REFERENCES
1. Acurex Corporation, Aerotherm Division, "SAM/I: An Intermediate Screening
Method for Environmental Assessment of Fossil Energy Process Effluents,"
Draft, 68-02-2160, Technical Directive 4, October, 1977.
2- Air Pollution Engineering Manual. 2nd ed., EPA Publication AP-40, May,
1973, p. 539.
3. Ando, Jumpei and B. A. Laseke, "S0? Abatement for Stationary Sources in
Japan," EPA-600/7-77-103a, September, 1977.
4. Andrews, R. L., "Current Assessment of Flue Gas Desulfurization Technology,"
Combustion. XLIX, No. 9 (October, 1977), 20-25.
5. Battelle, "IERL-RTP Procedures Manual Level 1 Environmental Assessment,
Biological Tests for Pilot Studies," 68-02-2138, PB268-484/AS, EPA-600/
7-77-043, April, 1977.
6. Beimer, R. I., L. E. Ryan, R. A. Maddalone, and M. M. Yamada, "Approach to
Level 2 Analysis Based on Level 1 Results, MEG Categories an:i Compounds
and Decision Criteria," Draft, 68-02-2613, TRW Defense and Space Systems
Group, October, 1977.
7. Borer, T., and J. Sinor, "Development of the Multimedia Environmental Con-
trol Engineering Handbook," Draft, 68-02-2152, Task 13, Cameron Engineers,
Inc., October, 1977.
8. Calvin, E. L., "A Process Cost Estimate for Limestone Slurry Scrubbing of
Flue Gas, Part 1," EPA-R2-73-1480, January, 1973.
9. Catalytic, Inc., "Process Technology Background for Environmental Assess-
ment/System Analysis Utilizing Fuel Oil," 68-02-2155, EPA-600/7-77-081,
August, 1977.
10. Chemical Engineers' Handbook, 5th ed., Perry and Chilton, pp. 9-10.
11. Cleland, J. G. and G. L. Kingsbury, "Summary of Key Federal Regulations
and Criteria for Multimedia Environmental Control," Draft, 68-02-1325,
Research Triangle Institute, June, 1977.
12. Craig, J. W. T., et al., "Chemically Active Fluid-Bed Process for Sulphur
Removal During Gasification of Heavy Fuel Oil - Third Phase, EPA-600/
2-76-248, September, 1976.
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REFERENCES (continued)
13. Craig, J. W. T., et al., "Study of Chemically Active Fluid Bed Gasifier
for Reduction of Sulphur Oxide Emissions," Final Report EPA-R2-72-020,
June, 1972, (NTIS Number PB 211-438).
14. Dorsey, J., L. Johnson, and R. Statnick, "Environmental Assessment Sampl-
ing and Analysis: Phased Approach and Techniques for Level 1," PB 268-
563/AS, EPA-600/2-77-115, IERL-RTP, EPA, June, 1977.
15. Gulf Research and Development Company, "The Gulf HDS Process," August 16,
1974.
16. Harris, T. C. and P. L. Levins, "IERL-RTP Procedures Manual: Level 2 Sam-
pling and Analysis of Organic Materials-Guidelines," Draft, 68-02-2150,
September, 1977.
17. Hastings, Kenneth E., Lewis C. James, and William R. Mounce, "Demetalli-
zation Cuts Desulfurization Costs," The Oil and Gas Journal, OXXIII, No.
26 (June 10, 1975), pp. 122-130.
18. Hauser, T. G. and W. L. Wright, "An Assessment of Oil Gasification Pro-
cesses for Electric Utility Power Generation," American Power Conference,
Chicago, May 1, 1974.
19. "IERL-RTP Procedures Manual Level 1 Environmental Assessment, Biological
Tests for Pilot Studies," 68-02-2138, PB268-484/AS, EPA-600/7-77-043,
April, 1977.
20. Keairns, et al., "Evaluation of the Fluidized-Bed Combustion Process," Vol.
IV, Appendix R, EPA-650/2-73-048d, December, 1973.
21. Keairns, D. L., et al., "Fluidized-Bed Combustion Process Evaluation," Vol.
I, Westinghouse Research Laboratories, EPA-650/2-75-027a, March, 1975.
22. Keairns, D. L., et al., "Fluidized-Bed Combustion Process Evaluation," Vol.
II, Westinghouse Research Laboratories, EPA-650/2-75-027b, March, 1975.
23. Kircher, et al., "A Survey of Sulfate, Nitrate, and Acid Aerosol Emissions
and Their Control," EPA-600/7-77-041, April, 1977.
24. Koehler, George and James A. Bums, "The Magnesia Scrubbing Process As
Applied to an Oil-Fired Power Plant," EPA-600/2-75-057, October, 1975.
25. Laseke, Bernard A. and Timothy W. Devitt, "Status of Flue Gas Desulfuriza-
tion Systems in the United States," Flue Gas Desulfurization Symposium,
Hollywood, Florida, November 8-11, 1977.
26. "Latest Data on Gulf HDS Process," Gulf Science and Technology Co., Hydro-
carbon Processing, May, 1977, pp. 97-104.
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REFERENCES (continued)
27. lamei,RG:7G.. jt '> 'fur °xide Removal from Power Plant Stack
28. McMillan, R. E. and F. D. Zoldak, "A Discussion of the Chemically Active
Fluid Bed Process," Frontiers of Power Technology Conference, October 26
and 27, 1977.
29. May, Bruce and Kenneth Budden, "Process Assessment Criteria," Draft, 68-
02-2162, November, 1977.
30. Mitre, "Environmental Assessment Sampling and Analytical Strategy Program,"
EPA-600/2- 76-093a, May, 1976.
31. Mitre, "Procedures Manual for Environmental Assessment of Fluidized-Bed
Combustion Processes," EPA-600/7-77-009, January, 1977.
32. Montagna, Angelo, Sun Chun, and James Frayer, "Advances in Technology and
Desulfurization of Residual Oils," World Petroleum Congress, May, 1975.
33. PEDCo Environmental, Inc., "Utility Flue Gas Desulfurization Systems -
October-November, 1977," Summary Report, EPA 68-01-4147, November, 1977.
34. Rakes, S. L., "Development of the Chemically Active Fluid Bed Process,
A Status Report and Discussion," P '€ 76-JPGC/FU-4, September, 1976.
35. Robson, F. L., et al., "Technological and Economic Feasibility of Advanced
Power Cycles and Methods of Producing Nonpol luting Fuels for Utility Pow-
er Stations," NAPCA Report APTD-0661 , December, 1970.
36. Robson, F. L. and W. A. Blecher and C. B. Colton, "Fuel Gas Environmental
Impact," EPA-600/2-76-153, June, 1976.
37. Samuel sen, G. Scott, "The Combustion Aspects of Air Pollution," Advances
in Environmental Science and Technology, Pitts, Metcalf, and Lloyd, ed.,
Vol. V, 1975, p. 260.
38. Shell Development Company, "The Shell Gasification Process," Shell Inter-
nationale Research Maatschappij N.V., The Hague, Holland, January, 1974.
39. Truett, J. Bruce, "Gasification/Combined-Cycle System for Electric Power
Generation," EPA-600/2- 76-085, March, 1976.
40. TRW "IERL-RTP Procedures Manual: Level I Environmental Assessment,"
68-02-1412, Task 18, PB 257-850/AS, EPA-600/2-76-160a, June, 1976.
41. Werner, et al., "Preliminary Environmental Assessment of the CAFB," EPA-
600/7-76-017, October, 1976.
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REFERENCES (continued)
42. Werner, A. S., et al., "Preliminary Environmental Assessment of the Fluid-
ized Bed," EPA-68-02-2106, December, 1975.
43. Zoldak, F. D., et al., "CAFB Preliminary Process Design Manual," Contract
Report 68-02-2106, April, 1976.
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GLOSSARY
ambient level goals: Levels of contaminants in air, water, or land which will
not adversely affect human health or the ecology, continuous exposure as-
sumed. K
amine regenerator: A process unit which separates amine from the hydrogen sul-
fide which it has absorbed from the HDS recycle gas.
APTIC: Air Pollution Technical Information Center.
BOD (Biochemical Oxygen Demand): The oxygen required to meet the metabolic
needs of aerobic microorganisms in water rich in organic matter; most of-
ten used to measure the amount of organic matter in wastewater.
calciner: A unit for heating a material (such as lime) to a high temperature
but without fusing in order to drive off volatile matter or to effect
changes (as oxidation or pulverization).
capability cnarge (or demand charge): In the derivation of annual owning and
operating costs for an FGD system, both an energy charge (operating cost)
and a demand charge (fixed or annual owning cost) can be figured. The de-
mand charge (in dollars per kilowatt) represents the cost of the portion of
the total installed capacity which is used by the FGD system. This demand
charge is typically 70% of the total power plant installed cost (dollars
per kilowatt).
capacity factor: For power generation units, the ratio of total hours in which
the unit is generating power divided by the total hours in a year.
chemically active fluid bed: A process for producing a clean gaseous fuel from
high sulfur feedstocks by partially combusting the feedstock in a fluid bed
(usually limestone) which reacts with and retains the sulfur in the feed-
stock.
Chilton method: A method which uses multiplication factors for the approxima-
tion of direct costs; more detailed and accurate than the Lang method.
Chiyoda: As used here, a process which treats the tail gas from a Claus unit.
Claus: A process which converts H2S or mixtures of H2S and S02 to elemental
sulfur.
COD (Chemical Oxygen Demand): The oxygen equivalent of any organic matter sub-
ject to oxidation by a strong chemical oxidant; used as a measurement of
organic pollution in wastewater.
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GLOSSARY (continued)
DCF (Discounted Cash Flow): A method of profitability evaluation where the time
value of money is considered and a rate of return is determined which can
be applied to yearly cash flow so that the original investment is reduced
to zero during the project life.
degree of hazard: A dimensionless value formed by dividing the MATE value for
a given compound or element into the measured or predicted concentration of
the compound or element in an effluent stream.
DO (Dissolved Oxygen): The concentration of dissolved oxygen in water, usually
expressed in parts per million percentage of saturation.
EAR (Environmental Assessment Reports): A part of the SSP which summarizes back-
ground information, waste streams, control alternatives, environmental im-
pact, and R&D needs for specific processes.
effluent gas: A gaseous waste stream leaving any vessel or process and entering
the surrounding media.
effluent stream: Waste discharge material leaving any vessel or process and en-
tering the surrounding media.
emission level goals: Desired levels or contaminants in emissions or effluents
from a point source.
emissions loadings: The concentrations of particular pollutants of concern in a
given effluent stream.
flue gas desulfurization: A process which removes sulfur-containing pollutants
from a flue gas stream via contact with an absorbent slurry (such as lime-
stone or MgO).
fractionation: The separation of a mixture into components by partial vaporiza-
tion and subsequent condensation.
fugitive emissions: Undesirable, uncontrolled non-point source emissions or ef-
fl uents.
hydrocracking: A catalytic, high-pressure petroleum refinery process that in-
volves the adding of hydrogen to petroleum-derived molecules too massive
and complex for gasoline, followed by the cracking of them to the required
fuels, the catalyst is an acidic solid and a hydrogenating metal component.
hydrodenitrogenation: The catalytic reduction of organo-nitrogen compounds to
NH, and low sulfur fuel oil by reaction with hydrogen; occurs along with
desulfurization in the HDS process.
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GLOSSARY (continued)
hydrodesulfunzation: A catalytic process in which the petroleum feedstock is
reacted with hydrogen to reduce the sulfur content of the oil by reducing
the organo-sulfur compounds to H2S and low sulfur fuel oil.
IFF (Institut Francais dePetrole): As used here, a process which treats the
tail-gas from a Claus unit.
Lang method: A method which uses multiplication factors for the approximation
of direct costs.
LC5Q: The calculated concentration of a substance in either air or water (as
separate figures) which will cause the death of 50 percent of an experimen-
tal animal population under controlled conditions and time exposure, most
often 96 hours for aquatic species.
LD2Q: The lethal dose to 20 percent of a population (see LD5Q).
LD5Q: The lethal dose to 50 percent of a population; the calculated dose of a
chemical substance which is expected to cause the death of 50 percent of an
entire population of an experimental animal species as determined from ex-
posure to the substance by any route other than inhalation.
Level 1, Level 2, Level 3: The Process Measurements Branch of IERL/RTP has de-
veloped and recommended the implementation of a phased sampling and analy-
tical strategy for Environmental Assessment programs. The first phase,
Level 1, has as its goal the quantification of mass emissions within a fac-
tor of 2 to 3 for inorganic elements and organic classes. The second phase,
Level 2, has as its goal the quantification and identification of specific
compounds. The third phase, Level 3, has as its goal the continuous moni-
toring of indicator compounds as surrogates for a large number of specific
compounds.
Lurgi process: A fixed-bed coal gasification process.
MATE'S (Minimum Acute Toxicity Effluents): The concentration levels of contami-
nants in air, water, or solid waste effluents that will not evoke signifi-
cant harmful responses in exposed humans or the ecology, provided the expo-
sure is of limited duration (less than 8 hours per day).
MEG's (Multimedia Environmental Goals): Levels of significant contaminants or
degradents (in ambient air, water, or land or in emissions or effluents con-
veyed to the ambient media) that are judged to be: (1) appropriate for pre-
venting certain negative effects in the surrounding populations or ecosys-
tems; or (2) representative of the control limits achievable through tech-
nology.
naphtha: Petroleum fraction with volatility between gasoline and kerosene; used
as a gasoline ingredient, solvent for paints and rubber, and cleaning sol-
vent.
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GLOSSARY (continued)
NIOSH: National Institute for Occupational Safety and Health.
NTIS: National Technical Information Service.
partial oxidation: Partial combustion of a solid, liquid, or gaseous fuel, in
which the degree of combustion is controlled by the amount of combustion
air. The products of partial oxidation can be oxidized further to complete
the combustion.
particulate: Any solid matter, as opposed to a liquid, which is dispersed in a
gas.
pelletizing system: In the POX process, a system which recovers carbon by ag-
glomeration of the soot with a distillate or residual oil, and subsequent
separation from the water slurry.
POT (Payout Time): A method of profitability evaluation which determines the
minimum length of time theoretically necessary to recover the original cap-
ital investment in the form of cash flow.
quench gas: A gas used to control (decrease) the temperature of segments of a
reactor.
recycle gas: Recoverable fraction of a process product gas stream which is of-
ten used as a quench gas or mixed with the feed stream.
residual fuel oil: Combustible, viscous, or semi-liquid petroleum product re-
maining after refinery separation of light fractions of crude oil; high in
sulfur ash and heavy metal content.
residual oil gasification: A general term for any of several processes (such as
POX or CAFB) by which a liquid residual oil feedstock is partially combusted
to generate a product gas suitable for use in power generation via a boiler
or gas turbine.
RESOX: A process which converts dilute S0« from a gas stream into elemental sul-
fur. c
ROI (Return on Investment): A method of profitability evaluation in which the
expected profit is divided by the total initial investment.
SAD: Source Assessment Document.
SAM: Source Analysis Model.
SAM/1A: A rapid screening method for environmental assessment of fossil energy
process effluents.
SASS: Source Assessment Sampling System.
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GLOSSARY (continued)
SCOT (Shell Claus Off-Gas Treatment) unit: A system used to clean up any resi-
dual H2S or S02 emission gas leaving the Claus unit that converts gases into
elemental sulfur.
SELEXOL: Low temperature gas cleanup process using polyethylene glycol ether as
a physical solvent type of absorbent that selectively absorbs hydrogen sul-
fide and carbonyl sulfide.
sludge: Residue left after acid treatment of petroleum oils. Any semi-solid
waste from a chemical process.
slurry: A free-flowing, pumpable suspension of fine solid material in liquid.
sour fuel gas: Natural gas or synthesis gas that contains corrosive, sulfur-
bearing compounds, such as hydrogen sulfide and mercaptans.
SSP: Standards Support Plan.
STOREX: A computer information pollution data retrieval system for various chem-
ical processes located at some specific site.
Stretford: A low-temperature gas cleanup process using sodium carbonate and an-
thraquinone sulfonic acid to direct converted hyd-ogen sulfide into element-
al sulfur.
synthesis gas: A mixture of gases prepared as feedstock for a chemical reaction;
for example, carbon monoxide and hydrogen to make hydrocarbons or organic
chemicals or hydrogen and nitrogen to make ammonia.
tail gas treater: Can imply the use of any FGD system or a flare stack inciner-
ator system for absorption or burning of residual emissions gases.
TD, (Lowest Toxic Dose): The lowest dose reported to induce carcinogenic, tera-
togenic, or other toxic effects in humans or animals when introduced by any
route other than inhalation.
TDS (Total Dissolved Solids): Quantitative analysis value for measuring water
quality.
TLM (TLm) (Medium Tolerance Limit): This measure of aquatic toxicity means that
approximately 50 percent of the fish will die under the conditions of con-
centration and time given.
TSS (Total Suspended Solids): The total content of suspended and dissolved sol-
ids in water.
UAC: Uniform Annual Cost.
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GLOSSARY (continued)
unit process modules: A detailed definition of a basic control technology pro-
cess subdivided into control/disposal options for gaseous emissions, waste-
water effluents, and solid waste disposal methods.
venturi scrubber (Chem. Eng.): A gas-cleaning device in which liquid injected
at the throat of a venturi is used to scrub dust and mist from the gas
flowing through the venturi.
volatilization: The conversion of a chemical substance from a liquid or solid
state to a gaseous or vapor state by the application of heat, by reducing
pressure, or by a combination of these processes. Also known as vaporiza-
tion.
Wellman-Lord sodium sulfite scrubbing process: A process used to remove sulfur
dioxide from flue gases by absorption.
WRA: Water Resource Abstracts.
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,P; TECHNICAL REPORT DATA
{ficase read Inunctions on the reverse before completing)
EPA-600/7-7 8-17 5
2.
3. RECIPIENT'S ACCESSION NO.
». TITLE AND SUBTITLE
Environmental Assessment for Residual Oil Utilization
—Second Annual Report
i. REPORT DATE
September 1978
i. PERFORMING ORGANIZATION CODE
7. AUTHOR(S) "
M.F.Tyndall, F.D.Kodras, J.K.Puckett, R.A.
Symonds , and W. C. Yu
8. PERFORMING ORGANIZATION REPORT NO.
1ING ORGANIZATION NAME AND ADDRESS
Catalytic, Inc.
P.O. Box 15232
Charlotte, North Carolina 28210
10. PROGRAM ELEMENT NO.
EHE623A
11. CONTRACT/GRANT NO.
68-02-2155
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
13. TYPE OF REP.ORT AND PERIOD COVERED
Annual; 5/77-5/78
14. SPONSORING AGENCY CODE
EPA/600/13
is. SUPPLEMENTARY NOTES T£RL-RTP project officer is Samuel L. Rakes, Mail Drop 61, 919/
541-2825. The first annual report was EPA-600/7-77-081.
is. ABSTRACT Tne repOrt describes progress in an environmental assessment of processes
utilizing residual oil for electric power generation. It explains the methodology of
environmental assessment and reports major progress in the areas of: current pro-
gress technology, current environmental background and objectives development, data
acquisition, control technology assessment, and environmental alternatives analysis.
It presents emissions data from the literature and preliminary sampling, with mater-
ial balances and flow diagrams for hydrodesulfurization, flue gas desulfurization,
partial oxidation, and chemically active fluid bed processes. It describes a computer
program for a theoretical engineering analysis that will provide emissions output for
the processes studied. A detailed sampling and analysis matrix has been developed
that specifies sampling points, procedures, and analyses, Including bioassays for all
emissions and effluents. Multimedia Environmental Goals (MEGs) and Minimum
Acute Toxicity Effluents (MATEs) are used to develop pollutant prioritization and
source analysis models. Methods for developing economic cost models are described.
Future plans include sampling of field installations, SAM/IA analysis of emissions
and effluent data, economic and energy efficiency analysis, describing areas for fur-
thur research and development, and databases for standards and engineering design.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
Pollution
Assessments
Residual Oils
Electric Power
Generation
Desulfurization
Flue Gases
Oxidation
Fluidized Bed Pro-
cessing
Computer Programs
Analyzing
Pollution Control
Stationary Sources
Environmental Assess-
ment
Hydrodesulfurization
Partial Oxidation
21B
07B,07C
13B
14B
2 ID
13H
10A 09B
07A,07D
18. DISTRIBUTION STATEMENT
Unlimited
19. SECURITY CLASS (ThisReport}
Unclass if ied
181
20. SECURITY CLASS (This page)
Unclassified
22. PRICE
EPA Form 2220-1 (»-73)
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