EPA-650/2-75-038
April  1975
Environmental Protection Technology Series

                                                            II


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                                           EPA-650/2-75-038
   POTENTIALLY  HAZARDOUS EMISSIONS
FROM  THE  EXTRACTION  AND  PROCESSING
                OF COAL  AND  OIL
                           by

           G. Cavanaugh, C. E. Burklm. and J. C. Dickerson

                      Radian Corporation

                           and

                   H. E. Lebowitz. S  S. Tarn,
            G. R. Smithson, Jr., H. Nack , and J. H  Oxley

                  Battelle, Columbus Laboratories
                       505 King Avenue
                     Columbus, Ohio 43201
                 Contract No. 68-02-1323. Task 30
                     ROAP No. 21AFH-025
                   Program Element No. 1AB015
                EPA Project Officer: Irvin A. Jefcoat

                   Control Systems Laboratory
               National Environmental Research Center
             Research Triangle Park, North Carolina 27711
                        Prepared for

             U.S. ENVIRONMENTAL PROTECTION AGENCY
              OFFICE OF RESEARCH AND DEVELOPMENT
                   WASHINGTON, D.C. 20460

                         April 1975

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                       EPA REVIEW NOTICE

This report has been reviewed by the National Environmental Research
Center - Research Triangle Park, Office of Research and Development,
EPA, and approved for publication.  Approval does not signify that the
contents necessarily reflect the views and policies of the Environmental
Protection Agency, nor does mention of trade names or commercial
products constitute endorsement or recommendation for use.
                   RESEARCH REPORTING SERIES

Research reports of the Office of Research and Development, U.S. Environ-
mental Protection Agency, have'been grouped into series.  These broad
categories were established to facilitate further development and applica-
tion of environmental technology.  Elimination of traditional grouping was
consciously planned to foster technology transfer and maximum interface
in related fields. These series are:

          1.  ENVIRONMENTAL HEALTH EFFECTS RESEARCH

          2.  ENVIRONMENTAL PROTECTION TECHNOLOGY

          3.  ECOLOGICAL RESEARCH

          4.  ENVIRONMENTAL MONITORING

          5.  SOCIOECONOM1C ENVIRONMENTAL STUDIES
          6.  SCIENTIFIC AND TECHNICAL ASSESSMENT REPORTS

          9.  MISCELLANEOUS

This report has been assigned to the ENVIRONMENTAL PROTECTION
TECHNOLOGY series.  This series describes research performed to
develop and demonstrate instrumentation, equipment and methodology
to repair or prevent environmental degradation from point and non-
point sources of pollution.  This work provides the new or improved
technology required for the control and treatment of pollution sources
to meet environmental quality standards.
This document is available to the public for sale through the National
Technical Information Service, Springfield, Virginia 22161.

                Publication No. EPA-650/2-75-038
                                11

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                               ABSTRACT

           In this task,  a list of specifically identified,  poten-
 tially hazardous materials which may be associated with the air,
 water, and solid waste from a refinery, a coke plant,  a Lurgi-high-
 Btu gas process, and the solvent refined coal process  was compiled.
 This task was completed  essentially in  one month in order to provide
 information to EPA for future program planning.   Thus,  the  list of  the
 potentially hazardous emission sources  and their components were
 developed with the best  engineering judgment  and from  the readily
 available published documents.
           Fugitive losses were identified as  the major  source of
 emissions in the refinery.   The compositions  of  the fugitive emissions
 are difficult to quantify.   Among the four assessed coal  and oil
 processes,  coking is the most  offensive one.   Coal  gasification is
 likely to produce equally dangerous materials  as the coke plant,  but
 they will probably be somewhat  more contained  than  coke oven emis-
 sion.   The  environmental impact  of coal  liquefaction is not  well
 defined.   However,  the liquefaction products will probably be more
 hazardous  than crude  oil products, and  their refining and utilization
 will be worse offenders  than the  corresponding petroleum  operations.
          This study  indicated  that available documents were not
 adequate  to develop accurately a  list of potentially hazardous
 emissions from these processes.  A detailed assessment of the pro-
 cesses, field sampling, and analysis are needed to identify  the
potentially hazardous emissions.
                                iii

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                            CONTENTS
                                                               Page
Abstract      ........................
List of Figures .......................   v
List of Tables    ......................   vi
Acknowledgments .......................   vii
Sections
I      Executive Summary  ..................    1
                 Introduction ................    1
                 Objective  .................    1
                 Approach ..................    2
                 Conclusions and Recommendations  ......    A
II     Methodology  .....................    5
III    Discussion of Results  ................   10
                 Petroleum Process Module ..........   10
                      Conclusions ..............   11
                 Conventional Coal Process Module ......   62
                      Conclusions ..............   62
                 Advanced Coal Process Module ........   84
                      Conclusions ..............   87
                 Recommendations  ..............  109
IV     Summary of Results ..................  Ill
V      Appendixes ......................  120
                                   iv

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                              FIGURES
No.                                                             Page
3-1    Field Separation  	    13
3-2    Natural Gas Processing	    14
3-3    Refinery-Crude Separation 	    15
3-4    Refinery-Light Hydrocarbon Processing 	    16
3-5    Refinery-Intermediate Hydrocarbon Processing  	    1?
3-6    Refinery-Heavy Hydrocarbons Processing  	    18
3-7    Coal Preparation	    64
3-8    Conventional Coal Process Module  	    65
3-9    Liquefaction Process Module 	    85
3-10   Gasification Process Module 	    86

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                               TABLES
No._                                                             lage
2-1    The Modular Classification for Potentially
         Hazardous Materials Proposed by EPA 	    7
2-2    Summary of the Toxicity Scales for Air and Water
         Pollutants  	    9
3-1    List of Process Modules in the Petroleum Process
       Flow sheets	   19
3-2    Process Stream Classification 	   21
3-3    Potentially Hazardous Emissions from the Identified
         Streams and Processes (Petroleum) 	   25
3-4    Potential for Fugitive Emissions from Petroleum
         Process Submodules  	
3-5    Process Modules of Coal Usage (Conventional)  	   66
3-6    Process Stream Classification (Conventional Coal) ...   67
3-7    Potentially Hazardous Emissions from Classified Streams
         and Processes (Conventional Coal) 	   68
3-8    Potential for Fugitive Emissions from Conventional
         Coal Process Module	   83
3-9    Process Modules of Coal Usage  (Advanced)   .......   88
3-10   Process Stream Classification  (Advanced Coal)  .....   89
3-11   Potentially Hazardous Emissions from Classified
         Streams and Processes  (Advanced Coal) ........   91
3-12   Potential for Fugitive Emissions from Advanced
         Coal Process Module .................  107
4-1    Potentially Hazardous Chemical Classes in  Classified
         Streams of Petroleum Process Module  .........  112
4-2    Potentially Hazardous Chemical Classes in  the
         Classified Streams of Conventional Coal
         Process Modules  ...................
 4-3    Potentially Hazardous Chemical Classes in the
         Classified  Streams of Advanced Coal Process Modules  . 115
 4-4    List  of Potentially Hazardous Chemicals  ........ 116

                                 vi

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                         ACKNOWLEDGMENTS

          The authors wish to acknowledge the assistance of
Dr. Irvin A. Jefcoat, Task Officer, under whose guidance this
program was carried out.  We also wish to thank Mr. Paul Spaite who
is the coordinator of this joint project of Battelle's Columbus
Laboratories and Radian Corporation.
          We are also indebted to Dr. G. A. Lutz of Battelle's
Columbus Laboratories and Professor L. R. Babcock, Jr. of
University  of Illinois, Chicago, Illinois 60680 for their comments
on this  report.
                               vii

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                              SECTION I
                          EXECUTIVE SUMMARY

INTRODUCTION
          The U.S. is in the process of making substantial increases
in its domestic capability for extraction and processing of crude oil
and coal to produce useful fuel products.  Quantities to be dealt
with at specific sites will greatly exceed those now handled; in
addition, new potentially "dirty" processes are to be employed,
especially in the case of coal.  The products and emissions from
present day systems involving thermal and catalytic processing of
fossil fuels are known to contain potentially harmful substances.  The
potential harmful impact from certain processes which may be employed
in the immediate future is well established in that the streams con-
tain known carcinogenic materials.  On the other hand, little is known
about whether the emissions, which can be anticipated, are in fact
economically controllable to levels which will permit elimination of
all potential environmental threat.  This study is a first step in
development of specific information on potentially harmful emissions
from fossil fuel processes.  It was designed to provide information
needed to plan programs necessary for full definition of problems
which we need to anticipate in future energy programs.

OBJECTIVE
          It was intended that the study should develop a list of
specifically identified, potentially hazardous materials which might
be associated with the air, water, and solid waste from processes used
to separate coal or crude oil into useful products.  It was agreed that
the list should be developed in the shortest possible time and that

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materials  readily available  to EPA and  the contractors would serve as
a data base.  Best engineering judgment was  to be applied in develop-
ment  of  the first specific recommendations for materials to be con-
sidered  in future environmental assessment programs concerned with
advanced processing of fossil fuels.

APPROACH
           Because the project was to be essentially complete in 2-3
weeks, a two-pronged approach was developed.  Battelie-Columbus was
commissioned to collect information on materials known to be poten-
tially hazardous to human health and identify those which might be
associated with emissions from processes extracting useful fuels from
crude oil  and coal.  Radian Corporation was commissioned to identify
present-day processes which might be expected to produce potentially
hazardous materials and develop an approach to identify specific
emissions which should be anticipated.  After an initial phase in
which the  two organizations completed preliminary studies a meeting to
develop a detailed plan for completion of the project was held.  The
overall program decided upon involved the following basic steps:
           (1)  The present-day processes utilizing crude oil and coal
were  identified and classified.  A modular approach was used to
divide the technologies concerned with extraction, processing, or
consumption of crude oil or coal into modular segments for purposes of
analyses of environmental impacts.
           (2)  After definition of process modules for analysis of
present-day emissions, all points of emission for air, water, and
solid waste (including fugitive emissions) were identified and
individual streams were assessed from the standpoint of specific
potentially hazardous emissions believed to be present.  Where it
appeared that emission streams from various processes could, because
of their similar character, be combined for purposes of analysis, this
was done.
           (3)  A list of twenty-five classes of chemical species which
might be potentially toxic, carcinogenic, or otherwise potentially
hazardous was developed to provide a system for cataloging materials

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identified as potentially hazardous emissions.  This list was provided
by EPA.
          (4)  A system for classification of pollutants according to
what is known about their potential for harmful impact was defined.
Three classes of pollutants were defined; Status 1 included all
materials which were known to be present, and known to be potentially
hazardous.  This class included carcinogenic compounds present in any
amount and toxic substances present in concentrations exceeding the
TLV.  The TLV is the list of threshold limit values of airborne con-
taminants published by the American Conference of Governmental and
Industrial Hygienists (A-10).  Status 2 pollutants were those known to
be present and suspected to be potentially hazardous.  This status
was mainly comprised of toxic materials known to be present in
emission streams but in undefined concentration.  Status 3 pollutants
were those potentially harmful materials which from indirect analysis
of process conditions were suspected to be present in emission streams
in concentrations exceeding the TLV.  Suspected emission of carcino-
genic material was placed in this class.
          (5)  A data sheet was developed for each process emission
stream and, after assessment of all available information on poten-
tially hazardous emissions, all were classified as Status 1, 2, or 3
and identified both by class of compound and specific compounds.
          (6)  After identification of all compounds and chemical
classes of compounds present, or suspected present in potentially
hazardous emissions from present-day processes, an assessment was made
of the degree to which the emissions would be representative of those
which could be anticipated from future fossil fuel technologies.
          (7)  Recommendations for future action were developed.
These recommendations and conclusions on which they are based are
discussed briefly in the following section.  Additional background is
incorporated in Section III—Discussion of Results.

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CONCLUSIONS AND RECOMMENDATIONS

          (1)  Over 200 compounds (or classes of compounds) have been
tentatively identified as potentially hazardous emissions from
processes which presently extract commercial fuels from coal and oil.
There is evidence to suggest that these and similar materials may be
emitted by processes which will be employed to meet future energy
needs.
          (2)  These potentially hazardous emissions have been associ-
ated with about 50 present-day processes which should be considered as
candidates for comprehensive testing to confirm and quantify levels of
emissions for potentially hazardous materials.  The first requirement
for a test program will be development of a sampling and analytical
strategy which can be integrated with the methodology that has been
developed for the assessment of emissions expected to be present.
          (3)  The present exercise to tentatively assess potentially
hazardous emissions from processing of oil and gas has developed a data
base for planning near-term activities.  Also it has resulted in
demonstration of a methodology which can and should be utilized to
further refine the list of materials which will be used for general
assessment of energy processes.
          (4)  The linking of emissions associated with present-day
processes with potential impacts from advanced energy systems was made
by making time-limited comparisons of present and projected energy
technologies.  There is little question that potential for hazardous
emissions will be similar for present and projected processes in a
qualitative sense, e.g., coke ovens are known to be serious sources of
carcinogenic materials.  The planned processes involving liquefaction
employ similar technology, and could have similar impacts if proper
precautions are not taken.  The difficulty of control for massive
plants of the future, and the  likelihood of serious environmental impact,
should be the subject of further assessment.  Proposed processes would
be better evaluated in light of what we know or can determine now about
the toxic nature of materials  such as residual oils, coal  tars,
asphalt, which now are being handled in refineries, coke plants, and
the like.
                                  4

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                            SECTION II
                            METHODOLOGY

          A modular approach was employed to identify the potentially
hazardous emissions.  The extraction and processing of crude oil and
coal were put into three classes of process flow sheets, namely,
petroleum, conventional coal, and advanced coal process flow sheets.
A complete description of each type of process flow sheet and the
identification of the potentially hazardous emission sources will be
presented in the next section—Discussion of Results.  The basic
approach and the definitions of toxicity will be outlined in this
section.
          A list of 25 potentially hazardous chemical emission classes
was provided by EPA as characteristic of the materials processed in
the modules being investigated.  This list is shown in Table 2-1.
Under many of these classes are listed examples of specific potentially
hazardous components.  There are also some potentially hazardous
chemicals involved which can be classified into more than one of the
25 classes.  It is felt that the classes suggested generally include
most of the components currently considered hazardous and provide a
consistent pattern to categorize the components.
          Every potentially hazardous chemical was assessed for its
importance, its physical state, and its concentration in the specific
process stream.  Some of this information was obtained from the
published literature, by material balances on the process module, and
by engineering estimate.  Three classes of status were set up and they
were intended to demonstrate the relative standings of the potentially
hazardous materials.
          •  Status 1—Known to be present, known to be
                       hazardous

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          •  Status 2—Known to be present,  suspected of being
                       hazardous
          •  Status 3—Suspected of being present, known to be
                       hazardous.
For known carcinogens, presence alone qualified them in a Status 1
category.  For toxic chemicals, presence in concentrations that appear
to be potentially hazardous at the point of contact was required before
a Status 1 was assigned.  When toxic chemicals fell into Status 2,
their emissions were usually determined by material balance on the
module or from published literature.  However, in most instances, the
quantities of these chemicals which can cause harmful effects are not
well defined.  The toxic chemicals in Status 2 may also indicate that
their toxic properties are uncertain.  Status 3 was assigned to the
toxic chemicals whose emission levels in the process stream was
possible but uncertain either because of their physical properties,
such as solubility, vapor pressure, etc., or because of the lack of in-
formation on existing commercial processes.  However, the toxic effects
of these chemicals have been studied or reported in published literature.
          An attempt has been made to compare the toxicities of the
potentially hazardous chemicals.  There are two scales  (T and C) for
the potentially hazardous air pollutants and one for hazardous water
pollutants  (W).  The first scale for air (T) is based on the allowable
emission limits from the TLV list.  The second scale  (C) is basically
for carcinogenic materials in air.  This scale is only  applied to the
materials whose carcinogenic effects have been tested in animals.  In
many cases,  the chemicals are put  into this category because of  the
similarities of their chemical  structures with those of the known
carcinogens.  There  is  only one collective scale  (W)  for the water
pollutants.  The units  on this  scale are the Lethal Dose Fifty,  LD5Q»
and the  threshold  limit of the  corresponding pollutant.  The Lethal
Dose Fifty  is defined as the calculated dose of a  chemical  substance
which  is expected  to cause the  death of  50 percent  of  the  entire
population  of an experimental  animal species,  as  determined from the
exposure to the substance, by  any  route  other  than inhalation,  of  a
significant number from the population.  The  designation  numbers of
these  three scales are  summarized  in Table  2-2.

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Table 2-1.  THE MODULAR CLASSIFICATION FOR POTENTIALLY HAZARDOUS
            MATERIALS PROPOSED BY EPA
 1.  Acids and Anhydrides
       Aliphatic (maleic anhydride)
       Aromatic (benzoic acid)
       Inorganic (sulfuric acid)

 2.  Alcohols

 3.  Amines

       Ammonia
       Aliphatic
       Aromatic (anilines,
         naphthylamines)

 4.  Inorganic Salts

 5.  Carbonyl Compounds

       Aldehydes
       Ketones (phenylvinyl
         ketone)

 6.  Combustion Gases
       (SOX, NOX>  CO, etc.)

 7.  Epoxides
       (styrene oxide, 1,2-
          epoxyhexadecane)

 8.  Ethers

       (o>Chloroalkyl ethers)

 9.  Halocarbons
       (Freons, CC1,, CHC1 ,  etc.)

10.  Heterocyclic  (monocyclic)

       Imino Heterocyclic
         (aziridines, ethyleneimine)
       Oxa (furan)
       Pyridines
       Pyrroles
       Thiophene

11.  Hydrocarbons
       Aliphatic (saturated)
       Olefins
       Aromatics (monocyclic-
         benzene,  toluene, xylene)

12.  Hydroperoxides
       Cyclohexene Hydroperoxide
13.  Lactones
       (3-propiolactone,
         butyrolactone, para-
         sorb ic acid, vinylene
         carbonate)
14.  Nitre Compounds
       (PAN, methylethyl
          nitrites)
15.  Nitrosamines
       (dimethyInitrosamine)
16.  Ozonides
17.  Peroxides
       (Lauroyl peroxide)
18.  Phenols
19.  Polychlorinated Polynuclear
       (polychlorobiphenyl,
         polychlorotripheny1,
         polychlorodibenzylfuran,
         polychlorodibenzo-p-
         dioxin)

20.  Polynuclear
       Aromatic Hydrocarbons
         (pyrenes, anthracene,
         chrysene)
       Aza arenes (acradene)
       Imino Arenes (carbazole)
       Oxa Arenes (dibenzofuran)
       Ring-carbonyl Arenes
         (anthraquinone)
       Thio Arenes (dibenzo-
         thiophene)
21.  Sulfur Compounds
       H_S, Mercaptans
       Sulfates (diethyl sulfate,
         ethylene sulfate)
       Sulfides
       Sulfites
       Sulfonates (ethyImethane
         sulfonate)
       Sultones (propane sultone)

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TABLE 2-1 (continued).  PROPOSED CLASSIFICATIONS FOR POTENTIALLY
                        HAZARDOUS MATERIALS FROM FUELS
22.  Trace Elements
       Metals
       Nonmetals
23.  Organometallics
24.  Fine Participates
25.  Cyanides

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Table 2-2.  SUMMARY OF THE TOXICITY SCALES FOR AIR AND WATER POLLUTANTS

Designation   _ Description --
    T-0       Emission limit in TLV < 1
    T-l       1 mg/M3 ^ Emission limit in TLV < 10 rag/M^
    T-2       Emission limit in TLV > 10 ing AT

    C-l       Identified primary procarcinogen (in humans)
    C-2       Definite high tumor -promo ting effect in animal tests
    C-3       Evidence of tumor -promoting effect in animal tests
    C-4       Suspected procarcinogen by structure

    W-0       LD   < 50 mg/Kg, Threshold limit < 1 ppm
    W-l       50 < LD5Q ^ 5000 mg/Kg, 1 < Threshold limit < 1000 ppm
    W-2       LD    >5000 mg/Kg, Threshold limit >1000 ppm

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                              SECTION III
                         DISCUSSION OF RESULTS

PETROLEUM PROCESS MODULES
           The first step of the approach to analyze the potentially
hazardous emission from the extraction and processing of crude oil was
to identify the representative major operations.  All operations were
described in terms of process "modules".  These identified operations
were grouped into six process flow sheets.  These process flow sheets
and the flow of materials through them are shown in Figures 3-1 to 3-6.
A list of 42 modules is shown in Table 3-1.
           The second step of the approach was to identify and to assess
all potentially hazardous emission streams by one or a  combination of
the following steps:
            (1)  Information from published literature
            (2)  Material balance on the  process module
            (3)  Experience in similar existing commercial operations
            (4)  Prediction through group discussion.
Emissions streams which were essentially the same were  classified for
further  detailed analysis.  The 25 classes of emission  streams which
cover  all the potentially hazardous emission from petroleum  operations
are shown in Table  3-2.
            For the  detailed assessment,  all published  information on
emission stream  composition was sought  and the emissions which might be
expected on the basis of process  conditions were estimated.   The
potentially hazardous chemicals were  identified and assigned status
numbers  as  described in  the previous  section.  Some identified
chemicals were assigned  toxicity  numbers whenever sufficient

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information was available.  The definitions of these toxicity numbers
have been discussed in the previous section.  In this detailed assess-
ment, each of the 25 compound classes (Table 2-1) was considered for
each stream.  A data sheet was made up for the results of the detailed
assessment of every identified emission stream from the modules.  The
data sheets of all the emission streams as described in Table 3-2 are
shown in Table 3-3.  Table 3-4 summarizes the assessment of the fugitive
emission streams.  Fugitive losses are by far the largest source of
emissions from petroleum processing.  They are also difficult to quantify.
Each process module was assessed on the basis of the operating
pressure and temperature, concentration of potentially hazardous
volatiles, corrosiveness, and general housekeeping.  The extent of fugitive
losses will vary with respect to these factors.  However, it is difficult
to quantify the degree of dependence.  The classification and rating were
made essentially by engineering judgment.
           A fact sheet was made for each module from which potentially
hazardous emissions would be expected.  These fact sheets are included
in Appendix A.

Conclusions
           On the basis of a 3-week assessment of process flowsheets and
modules, streams, and chemicals encountered in the petroleum industry, the
classifications of process streams and modules concerning their
potential for emitting hazardous chemicals were made.
           (1)  Among the process streams known to contain known hazard-
ous components are Glaus plant tailgas, catalyst regeneration off gas from
catalytic reformers, catalytic hydrocrackers, HDS units, and moving bed
catalytic crackers.  Off gases from fluid cokers, asphalt air blowing,
decoking, and oil-fired process heaters are also in the known/known
category.
           (2)  Literature information on specific carcinogens in
refinery process streams was sparse, although specific published data
on polynuclears [benzo(a)pyrene and others] indicate these to be known
hazards in catalytic cracker regeneration off gas and asphalt blowing
streams.
                                11

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           (3)  The process streams with the greatest number of
 compounds  in  the known/known, known/suspected, and suspected/known
 categories were moving bed catalyst regeneration, fluid coker off
 gas,  asphalt  air blowing, spent acid sludge, and brine water streams.
 Sour  aqueous  condensates, cooling water systems, and fugitive
 emissions  come from all  parts of the refinery and thus contain many of
 the suspected categories.
           (4)  Potentially hazardous fugitive emissions were judged
 to be the  most likely from gas and oil wells and field separation
 units, visbreakers, cokers, and lube oil processing units.  Waste-
 water systems (open sewers) and oil-fired heaters were also considered
 high  potential emitters.  Process modules judged to have medium to
 high  hazardous fugitive  losses are acid gas removal, sulfur recovery,
 atmospheric distillation, catalytic crackers, lube oil HDS, and asphalt
 blowing.
           (5)  It is generally difficult to characterize fugitive
 losses as  to  chemical class or specific component.  These should be
 similar  in nature to the  fluids being processed in the module rather
 than  that  of  a specific  stream leaving the module.  The matrix entries
 therefore  indicate that  all potentially hazardous emissions are only
 suspected  of  being present in the fugitive losses, but that all such
 hazardous  chemicals previously mentioned in connection with stream
 classes  could be present.
           (6)  There was  no evidence that epoxides, hydroperoxides,
 nitro compounds, ozonides, peroxides, ana polychlorinated polynuclears
 are among  the components  to be classified on any level.
           (7)  The  25  chemical  classes  suggested by  EPA  appear  to  be
representative of the hazardous  chemicals  that might  be found  in petroleum
streams.
                               12

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U>
                                               CRUDE SEPARATION!
                                               -        *|
                                                                                   FIGURE 3-1.  FIELD SEPARATION

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c
FROM FIELD
SEPARATION
C
FROM FIELD
SEPARATION
                                                                                                                                   UTILITY STEM
                                                                                                                                     TO SALES
DISPOSAL
                                                                                                                                     TO SALES
                                                                                                                                     HTO SALES   "I   -,
                                                                                                                                    OR REFINERY J   "
             FIGURE  3-2.    NATURAL  GAS  PROCESSING
                                                                                                                                     TO SALES
                                                                                                                                    OR REFIHERY.

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                                                            _T  TO MOOLC
                                                            "LplSTILUTI mOSSIK
                                                            •h-o
FIGURE  3-3.   REFINERY - CRUDE  SEPARATION

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ON
                                                                     FIGURE 3-4.  REFINERY-LIGHT HYDROCARBON
                                                                                  PROCESSING

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FIGURE 3-5.  REFINERY-INTERMEDIATE
             HYDROCARBON PROCESSING

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oo
                     FIGURE 3-6.  REFINERY - HEAVY HYDROCARBONS  PROCESSING

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Table 3-1.   LIST OF PROCESS MODULES IN THE  PETROLEUM PROCESS FLOW SHEETS
        Module	Name
           1         Gas Well
           2         Oil Well
           3         Field Separations (a, b, and c)
           4         Condensate Storage and Loading
           5         Crude Storage (field)
           6         Acid Gas Removal (field)
           7         Sulfur Recovery (field)
           8         Dehydration
           9         Gas Separation
          10         Low Pressure Gas (LPG) Storage and Loading
          11         Gasoline Storage and Loading
          12         Crude Storage (refinery)
          13         Desalting
          14         Atmospheric Distillation
          15         Acid Gas Removal (refinery)
          16         Sulfur Recovery (refinery)
          17         Gas Processing
          18         Vacuum Distillation
          19         Hydrogen Production
          20         Polymerization
          21         Alkylation
          22         Isomerization
          23         Naphtha Hydrodesulfurization  (HDS)
          24         Catalytic Reforming
          25         Light Hydrocarbon Storage and Blending
          26         Chemical Sweetening
          27         Kerosene HDS
          28         Gas Oil HDS
          29         Fluid Bed Catalytic Cracker
          30         Moving Bed  Catalytic  Cracker
          31         Catalytic Hydrocracker
          32         Intermediate Hydrocarbon Storage and
                        Blending
                                19

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Table 3-1 (continued).   LIST OF PROCESS MODULES  IN THE
                        PETROLEUM PROCESS  FLOW SHEETS
    Module	Name	
      33          Lube Oil  HDS
      34          Deasphalting
      35          Residual  Oil HDS
      36          Visbreaking
      37          Coking
      38          Steam Boiler
      39          Lube Oil  Processing
      40          Asphalt Blowing
      41          Heavy Hydrocarbon Storage and Blending
      42          Oil/Gas Well
                          20

-------
 Table 3-2.  PROCESS STREAM CIASSIFICATION

 A.  Brine Water Systems
     Module
     Number                      Unit  Name
        3        Field Separations
        4        Condensate Storage  and  Loading
        5        Crude Storage (Field)
       12        Crude Storage (Refinery)
       13        Desalting
 B.  Sour Aqueous Condensates
       14        Atmospheric Distillation
       18        Vacuum Distillation
       27        Kerosene HDS
       28        Gas Oil  HDS
       29        Fluid Bed Catalytic Cracker
       30        Moving Bed Catalytic  Cracker
       31        Catalytic Hydrocracking
       33        Lube Oil HDS
       34        Deasphalting
       35        Residual Oil  HDS
       36        Visbreaking
       37        Coking
       39        Lube Oil Processing
C.  Acid Gas Solvent Regeneration
        6        Acid Gas Removal (Field)
       15        Acid Gas Removal (Refinery)
D.  Glaus Plant Tail Gas
        7        Sulfur Recovery (Field)
       16        Sulfur Recovery (Refinery)
E.  Fixed-Bed Catalyst Regeneration  (Group  I)
       20        Polymerization
       22        Isomerization
                     21

-------
Table 3-2  (continued).  PROCESS STREAM CIASSIFICATION

F.  Fixed-Bed Catalyst Regeneration (Group II)
    Module
    Number                       Unit Name
       24        Catalytic Reforming
G   Fixed-Bed Catalyst Regeneration (Group III)
       23        Naphtha HDS
       27        Kerosene HDS
       28        Gas Oil HDS
       31        Catalytic Hydrocracking
       33        Lube Oil HDS
       35        Residual Oil HDS
       39        Lube Oil Processing (Clay)
H.  Fixed-Bed Catalyst Regeneration (Group IV)
       26        Chemical Sweetening
I.  Moving-Bed Catalyst Regeneration
       29        Fluidized-Bed Catalytic Cracker
       30        Moving-Bed Catalytic Cracker
J.  Barometric Condenser Off Gas
       18        Vacuum Distillation
       36        Visbreaking
K.  Fluid Coker Off Gas
       37        Coking
L.  Asphalt Air Blowing
       40        Asphalt Blowing
M.  Spent Acid Sludge
       39        Lube Oil Processing
N.  Decoking
       36        Visbreaking
0.  Oil-Fired Process Heaters
     3b^and      pield Separation

       14        Atmospheric Distillation
       18        Vacuum Distillation
       19        Hydrogen Production
                     -_

-------
Table 3-2 (continued).   PROCESS STREAM CLASSIFICATION

0.  Oil-Fired Process Heaters (continued)
    Module
    Number                        Unit Name
      20         Polymerization
      21         Alkylation
      22         Isomerization
      23         Naphtha HDS
      24         Catalytic Reforming
      27         Kerosene HDS
      28         Gas Oil HDS
      29         Fluid Bed Catalytic Cracker
      30         Moving Bed Catalytic Cracker
      31         Catalytic Hydrocracking
      33         Lube Oil HDS
      34         Deasphalting
      35         Residual Oil HDS
      36         Visbreaking
      37         Coking
      39         Lube Oil Processing
      40         Asphalt Blowing
P.  Cooling Water Systems
                 Cooling Towers
Q.  Storage and  Blending  (Group I)
        4         Condensate  Storage and Loading
        5         Crude Storage  (Field)
        6         Crude Storage  (Refinery)
R.  Storage and  Blending  (Group II)
      25         Light Hydrocarbons Storage and Blending
      32         Intermediate  Hydrocarbon  Storage and
                    Blending
S.  Storage and  Blending  (Group III)
      41         Heavy Hydrocarbon Storage and Blending
T.  Fugitive  Sources
                 Total Petroleum  Industry
                      23

-------
Table 3-2 (continued).  PROCESS STREAM CIASSIFICATION

U.  Flares
V.  API Grit Chambers
W.  Biological Sludges
X.  Spent Catalysts
                     24

-------
                  Table 3-3.  POTENTIALLY HAZARDOUS EMISSIONS FROM THE IDENTIFIED STREAMS AND PROCESSES




                                             (A)  Brine Water Systems
ro
Chemical Potentially Present
Emission
Status Class
Known Present/ 13. Lactones
Known Hazardous
Known Present/ 1. Acids and
Suspected Hazardous Anhydrides
4. Inorganic Salts
5. Carbonyl Compounds
10. Heterocyclic
11. Hydrocarbons
18. Phenols
21. Sulfur Compounds
Specific
Components

Maleic Anhydride
Benzole Acid
Chlorides
Ketones
Aldehydes
Pyridines
Pyrroles
Benzene
Toluene
Xylene
Phenol
Dimethyl Phenol
Cresol
Sulfides
Sulfites
Sulfonates
Su If ones
Mercaptans
Phase Toxicity Reference
Aqueous C-l, 2, 3
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous W-2 A-8
Aqueous
Aqueous W-l A-8
Aqueous W-l A-8
Aqueous W-l A-8
Aqueous W-l A-5, 7
Aqueous W-l A-5, 7
Aqueous W-l/C-3 A-5
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous

-------
                                Table 3-3 (Continued).   (A)   Brine Water Systems
ISJ
Chemical Potentially Present
Status
Suspected Present/
Known Hazardous



Emission
Class
10. Heterocyclic
20. Polynuclear
21. Sulfur Compounds
22. Trace Elements
Specific
Components
Dibenzofuran
Qu inclines
Carbazoles
Anthracenes
Thiophenes
Vanadium
Nickel
Zinc
Lead
Phase
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Toxicity Reference



W-2 A-7, 8, 9
W-l A-8
                          23.  Organometallics
Metalloporphyr ins
Aqueous

-------
                              Table 3-3 (continued).   (B)  Sour Aqueous Condensates
ISJ
Chemical Potentially Present
Emission
Status Class
Known Present/ 1. Acid and Anhydride
Suspected Hazardous
2. Alcohols
3. Amines
5. Carbonyls
10. Heterocyclic
11. Hydrocarbons
18. Phenols
21. Sulfur Compounds
Specific
Components
Cresylic Acid
Maleic Acid
Alkyl Alcohols
Aromatic Alcohols
Ammonia
Aldehydes
Ke tones
Pyridines
Pyrroles
Benzene
Toluene
Xylene
Cresols
Xylenols
Phenol s
Hydrogen Sulfide
Methyl Mercaptan
Sulfides
Sulfonates
Thiophenes
Phase
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Toxic ity


W-l
W-l
W-2
W-l
W-l
W-l
W-l
W-l
W-0
Reference


A-5
A-8
A-8
A-8
A-8
A-8
A-5
A-5, 7
A-5, 6, 7

-------
                          Table 3-3 (continued).  (B)  Sour Aqueous Condensates
Status
Known Present/
Known Hazardous
Suspected Present/
Known Hazardous

Chemical Potentially Present
Emission Specific
Class Components
25. Cyanides*
20. Polynuclear**
22. Trace Elements
23. Or ganome tallies**

Phase Toxic ity Reference
Aqueous
Aqueous
Aqueous
Aqueous
 *  Predominate in effluent from catalytic  cracking units.
**  Predominate in deasphalting and lube oil processing unit effluents.

-------
                           Table 3-3 (continued).  (C)  Acid Gas Solvent Regeneration
N)
\O
Chemical Potentially Present
Emission
Status Class
Known Present/ 1. Acids and
Suspected Hazardous Anhydrides
3. Amines
21. Sulfur Compounds
25. Cyanides
Specific
Components
Acetic
Formic
Maleic
Methylethylamine
Diethylamine
Carbon disulfide
Carbonyl sulfide
Methyl Mercaptan
Thiosulfide

Phase Toxicity Reference
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
   *  From refinery  off  gas  treatment  only.

-------
                            Table 3-3  (continued).  (D)  Claus Plant Tail Gas
Chemical Potentially Present
Status
Known Present/
Known Hazardous
Known Present/
Suspected Hazardous


Suspected Present/
Emission
Class
21. Sulfur Compounds
3. Amines
6. Combustion Gases
24. Fine Particulates
25 . Cyanide
Specific
Components
Hydrogen Sulfide
Carbonyl Sulfide
Carbon Disulfide
Diethylamine
Methyl ethylamine
Ammonia
Carbon Monoxide
Sulfur Dioxide
Sulfur Particulates

Phase
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Toxicity
T-2
T-2
T-2
T-2
T-l

Reference
C-4
C-4
C-4




Known Hazardous

-------
                     Table 3-3  (continued).   (E)   Fixed Bed Catalyst  Regeneration (Group I)
Chemical Potentially Present
Status
Known Present/
Suspected Hazardous
Emission
Class
6. Combustion Gases
24. Fine Particulates
Specific
Components
Carbon Monoxide
Carbon Compounds
Catalyst Fines
Phase
Gas
Gas
Gas
Toxic ity
T-2
T-0
Reference

u>

-------
                  Table 3-3  (continued).   (F)  Fixed  Bed  Catalyst  Regeneration (Group II)
Chemical Potentially Present
Status
Known Present/
Known Hazardous
Known Present/
Suspected Hazardous


Suspected Present/
Emission
Class
21. Sulfur Compounds
6. Combustion Gases
11. Hydrocarbons
24. Fine Particulates
20. Polynuclear
Specific
Components
Hydrogen Sulfide
Carbonyl Sulfide
Carbon Monoxide
Sulfur Dioxide
Benzene
Toluene
Xylene


Phase
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Toxic it y
T-2
T-l
T-2
T-2
T-2
T-2


Reference
C-4
C-4

A-2


Known Hazardous

-------
                      Table  3-3  (continued).   (G)   Fixed Bed Catalyst Regeneration (Group III)
u>
UJ
Chemical Potentially Present
Status
Known Present/
Known Hazardous
Known Present/
Suspected Hazardous



Suspected Present/
Known Hazardous

Emission
Class
21. Sulfur Compounds
6. Combustion Gases
11. Hydrocarbons
22. Trace Elements
24. Fine Particulates
10. Heterocyclic
20. Polynuclear
23. Organometallics
Specific
Components
Hydrogen Sulfide
Carbonyl Sulfide
Carbon Bisulfide
Mercaptans
Carbon Monoxide
Sulfur Dioxide
Benzene
Toluene
Xylene
Vanad ium
Nickel
Cobalt
Molybdenum
Catalyst
Coke

Nickel Carbonyl
Cobalt Carbonyl
Phase
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Toxic ity
T-2
T-0
T-l
T-2
T-2
T-2
T-2
T-0
T-0
T-l

T-0
Reference
C-4
C-4
C-4

A-2
A-4
C-l




-------
                     Table 3-3 (continued).  (H)  Fixed Bed Catalyst Regeneration  (Group  IV)
Chemical Potentially Present
Emission
Status Class
Known Present/ 21. Sulfur Compounds
Suspected Hazardous


Specific
Components
Hydrogen Sulfide
Sulfides
Mercaptans
Phase
Gas and
Aqueous
Gas and
Aqueous
Gas and
Aqueous
Toxicity Reference
T-2/W-0 A-5, 6, 7

T-0
LO

-------
Table 3-3 (continued).  (I)  Moving Bed Catalyst Regeneration
Chemical Potentially Present
Emission
Status Class
Known Present/ 20. Polynuclear
Known Hazardous







21. Sulfur Compounds


22. Trace Elements



24. Fine Particulates
Known Present/ 3. Amines
Suspected Hazardous
6. Combustion Gases

Specific
Components
Benzo(a)pyrene
Pyrene
Benzo(e)pyrene
Perylene
Benzo(ghi)perylene
Coronene
Anthracene
Phenanthrene
Fluoranthene
Hydrogen Sulfide
Carbonyl Sulfide
Carbon Disulfide
Vanad ium
Nickel
Copper
Zinc

Ammonia
Aromatic Amines
Sulfur Dioxide
Carbon Monoxide
Phase
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Toxicity
T-l/C-1
T-O/C-3
T-l/C-2
T-l/C-4
C-4
T-l
T-O/C-4
T-O/C-4

T-2


T-0
T-0
T-0
T-l
T-0
T-2

T-2
T-l
Reference
A-l, D-4
A-l, D-4
A-l, D-4
A-l, D-4
A-l, D-4

A-l, D-4
A-l

C-4
C-4
C-4
C-l
C-l
C-l
C-l
C-6.D-4





-------
Table 3-3 (continued).   (I)  Moving Bed Catalyst  Regeneration
Chemical
Emission
Status Class
11. Hydrocarbons
18. Phenols
25. Cyanides
Suspected Present/ 5. Carbonyl Compounds
Known Hazardous
10. Heterocyclic
15. Nitrosamines
21. Sulfur Compounds
Potentially Present
Specific
Components
Benzene
Toluene
Xylene
Phenol
Cresol

Aldehydes
Formaldehyde
Acetaldehyde
Pyridines
Pyrroles
Indoles

Thiophenes

Phase
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Toxicity
T-2
T-2
T-2
T-l
T-l

T-l
T-l
T-2
T-l
C-3

Reference
A-2



A-l



-------
                             Table 3-3  (continued).   (J)   Barometric  Condenser Off Gas
u>
Chemical Potentially Present
Emission
Status Class
Known Present/ 5. Carbonyl Compounds
Suspected Hazardous
10. Heterocyclic
1 1 . Hyd roca rbons

18. Phenols
21. Sulfur Compounds
Specific
Components
Aldehydes
Ketones
Pyrroles
Pyridines
Benzene
Toluene
Xylene
Cresols
Xylenols
Phenol s
Hydrogen Sulfide
Methyl Mercaptan
Thiophenes
Phase
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Toxic ity Reference
T-l
T-l
T-2 A-2
T-2
T-2
T-l
T-l
T-l
T-2

-------
                                Table 3-3  (continued).   (K)   Fluid  Coker Off Gas
oo
Chemical Potentially Present
Status
Known Present/
Known Hazardous


Known Present/
Suspected Hazardous





Emission
Class
21. Sulfur Compounds
22. Trace Elements
24. Fine Particulates
3. Amines
6. Combustion Gases
11. Hydrocarbons
18. Phenols
23. Organometallics
25. Cyanides
Specific
Components
Hydrogen Sulfide
Mercaptans
Carbonyl Sulfide
Carbon Disulfide
Vanadium
Copper
Nickel
Zinc

Ammonia
Aromatic Amines
Sulfur Oxides
Carbon Monoxide
Benzene
Toluene
Xylene
Phenol
Xylenol
Thiophenols


Phase
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Toxic ity
T-2
T-0
T-0
T-0
T-0
T-2
T-2
T-l
T-2
T-2
T-2
T-l
T-l
T-l


Reference

C-l
C-l
C-l
C-l
C-6.U-4


A-2




-------
                                  Table 3-3  (continued).  (K)  Fluid Coker Off Gas
UJ
Chemical Potentially Present
Emission
Status Class
Suspected Present/ 5. Carbonyl Compounds
Known Hazardous
10. Heterocyclic


13. Lactones
15. Nitrosamines
20. Polynuclear






Specific
Components
Formaldehyde
Acetaldehyde
Pyridines
Pyrroles
Indoles


Benzo(a)pyrene
Pyrene
Benzo(e)pyrene
Perylene
Coronene
Anthracene
Phenanthrene
Fluoranthene
Phase
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Toxic ity
T-l
T-2
T-l




T-l/C-1
T-O/C-3
T-l/C-2
T-l/C-4
T-l
T-O/C-4
T-O/C-4
C-4
Reference







A-l
A-l
A-l
A-l
A-l
A-l
A-l
A-l
                             21.   Sulfur Compounds
Thiophenes
Gas

-------
                               Table 3-3  (continued).   (L)  Asphalt Air  Blowing
•e-
o
Chemical Potentially Present
Emission Specific
Status Class Components
Known Present/ 10. Heterocyclic Pyrroles
Known Hazardous
Pyridines
Dibenzofuran
Furans
Quinolines
20. Polynuclear Carbazoles
Anthracene
Benzo(a)pyrene
21. Sulfur Compounds Dibenzo Thiophene
Thiophenes

Phase Toxicity
Aqueous T-l
and Gas
Aqueous T-l
and Gas
Aqueous T-l
and Gas
Aqueous
and Gas
Aqueous T-0
and Gas
Aqueous C-3
and Gas
Aqueous T-O/C-4
and Gas
Aqueous T-l/C-1
and Gas
Aqueous
and Gas
Aqueous T-2
and Gas
Reference
C-l, 5
C-l, 5
D-4
C-l, 5
C-l, 5
A-2, D-4
A-l, D-4
A-l, D-4
D-4
C-l, 5

-------
Table 3-3 (continued).   (L)  Asphalt Air Blowing
Chemical Potentially Present
Emission Specific
Status Class Components
Known Present/ 1. Acids and Cresylic
Suspected Hazardous Anhydrides
Maleic
5. Carbonyl Compounds Aldehydes
Ketones
11. Hydrocarbons Benzene
Toluene
Xylene
18. Phenols Cresols
Xylenols
Phenol s
Phase Toxicity Reference
Aqueous
and Gas
Aqueous
and Gas
Aqueous
and Gas
Aqueous
and Gas
Aqueous W-l/T-2 A-2, 8
and Gas
Aqueous W-l/T-2 A-8
and Gas
Aqueous W-l/T-2 A-8
and Gas
Aqueous W-l/C-3/ A-5
and Gas T-l
Aqueous
and Gas
Aqueous W-l/T-1 A-5, 7
and Gas

-------
Table 3-3 (continued).   (L)   Asphalt Air Blowing
Chemical Potentially Present
Emission Specific
Status Class Components
21. Sulfur Compounds Alkyl Sulfides
Sulfonates
22. Trace Elements Vanadium
Nickel
Zinc
Copper
Strontium
Barium
24. Fine Particulates
Suspected Present/ 13. Lac tones
Known Hazardous
23. Organometallics
Phase Toxicity Reference
Aqueous
and Gas
Aqueous
and Gas
Aqueous W-2/T-0
and Gas
Aqueous — /T-0
and Gas
Aqueous — /T-l
and Gas
Aqueous --/T-0
and Gas
Aqueous W-2/--
and Gas
Aqueous W-2/T-0
and Gas
Gas
Aqueous
and Gas
Aqueous
and Gas

-------
                                 Table 3-3 (continued).   (M)  Spent Acid Sludge
10
Chemical Potentially Present
Emission
Status Class
Known Present/ 1. Acids and
Suspected Hazardous Anhydrides
2. Alcohols
4. Inorganic Salts
5. Carbonyl Compounds
10. Heterocyclic
11 . Hydrocarbons
18. Phenols
21. Sulfur Compounds
Specific
Components
Sulfuric Acid

Sulfates
Aldehydes
Ketones
Pyridines
Pyrroles
Furan
Benzene
Toluene
Xylene
Cresols
Xylenols
D imethy Iphenol
Sulfides
Sulfonates
Phase
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Toxic ity Reference
W-l A-8


W-l A-8
W-2 A-8
W-l A-8
W-l A-8
W-l A-8
W-l/C-3 A-5

                          23.  Organometallics
Aqueous

-------
Table 3-3 (continued).   (M)  Spent Acid Sludge
Status
Suspected Present/
Known Hazardous

Chemical
Emission
Class
13. Lactones
10. Heterocyclic
22. Trace Elements
Potentially Present
Specific
Components
Quinolines


Phase Toxic ity Reference
Aqueous
Aqueous W-l
Aqueous

-------
                                          Table 3-3  (continued).   (N)  Decoking
Ln
Chemical Potentially Present
Status
Known Present/
Known Hazardous
Known Present/
Suspected Hazardous



Suspected Present/
Emission
Class
21. Sulfur Compounds
6. Combustion Gases
11. Hydrocarbons
22. Trace Elements
24. Fine Particulates
20. Polynuclears
Specific
Components
Hydrogen Sulfide
Carbonyl Sulfide
Carbon Bisulfide
Methyl Mercaptans
Carbon Monoxide
Sulfur Dioxide
Benzene
Toluene
Xylene
Vanadium
Nickel
Copper
Zinc
Coke

Phase
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Toxic ity Reference
T-2
T-0
T-l
T-2
T-2 A-2
T-2
T-2
T-0
T-0
T-0
T-0
T-l

        Known Hazardous

-------
                          Table 3-3 (continued).   (0)   Oil Fired Process Heaters
Chemical Potentially Present
Status
Known Present/
Known Hazardous

Known Present/
Suspected Hazardous












Emission
Class
20. Polynuclear

24. Fine Particulates
5. Carbonyl Compounds

6. Combustion Gases


20. Polynuclear





22. Trace Elements


Specific
Components
Benzo (a) pyrene


Aldehydes

Sulfur Oxides
Nitrogen Oxides
Carbon Monoxide
Benzoperylene
Coronene
Anthracene
Phenanthene
Fluoranthene
Benzopyrenes
Vanadium
Nickel
Lead
Phase
Gas

Gas
Gas

Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Toxic ity
T-l/C-1

T-0
T-2

T-2
T-2
T-l
T-l/C-4
T-l
T-O/C-4
T-O/C-4
C-4
T-0
T-0
T-0
T-0
Reference
A-l, D-4

D-4





A-l

A-l
A-l
A-l



A-4
Suspected Present/
Known Hazardous
10.  Heterocyclic
Gas

-------
                             Table  3-3  (continued).   (P)  Cooling Water System
Chemical
Emission
Status Class
Known Present/ 1. Acids and
Suspected Hazardous Anhydrides
4. Inorganic Salts
11. Hydrocarbons

18. Phenols
21. Sulfur Compounds
Potentially Present
Specific
Components
Sulfuric Acid
Chlorides
Chromates
Alkyl
Aromatic
Phenol
Sulfides
Sulfates

Phase Toxicity Reference
Aqueous W-l A-8
Aqueous
Aqueous
Gas and
Aqueous
Gas and
Aqueous
Aqueous W-l A-5, 7
Aqueous
Aqueous
Suspected Present/
Known Hazardous
1.
Acids and
Anhydrides
Sulfuric Acid
                        2.   Alcohols
                        3.   Amines
                        5.   Carbonyl  Compounds     Aldehydes and
                                                  Ketones
Gas
                                                  Gas and
                                                  Aqueous

                                                  Gas and
                                                  Aqueous

                                                  Gas and
                                                  Aqueous
T-0

-------
                                 Table 3-3 (continued).   (P)   Cooling Water  Systems
          Status
       Emission
        Class
                                          Chemical  Potentially  Present
 Specific
Components
                                                                               Phase
                                                              Toxicity
Reference
oo
    Suspected Present/
    Known Hazardous
 8.  Ethers


10.  Heterocyclic


13.  Lactones


15.  Nitrosoamines


18.  Phenols

20.  Polynuclear


21.  Sulfur Compounds

22.  Trace Elements


23.  Organometallics


25.  Cyanides
                    Gas and
                    Aqueous

                    Gas and
                    Aqueous

                    Gas and
                    Aqueous

                    Gas and
                    Aqueous

                    Gas

                    Gas and
                    Aqueous

                    Gas

                    Gas and
                    Aqueous

                    Gas and
                    Aqueous

                    Gas and
                    Aqueous

-------
                       Table 3-3 (continued).   (Q)   Storage  and  Blending (Group I)1
Chemical Potentially Present
Status
Known Present/
Suspected Hazardous





Emission
Class
5. Carbonyl Compounds

11. Hydrocarbons


21. Sulfur Compounds

Specific
Components
Aldehydes
Ketones
Benzene
Toluene
Xylene
Hydrogen Sulfide
Mercaptans
Phase
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Toxic ity


T-2
T-2
T-2
T-2
T-0
Reference


A-2




*  Aqueous streams covered on sheet A, brine water systems.

-------
                           Table 3-3 (continued).   (R)   Storage and Blending (Group II)
Ul
o
Status
Known Present/
Suspected Hazardous








Suspected Present/
Chemical
Emission
Class
3. Amines


11. Hydrocarbons





18. Phenols
23. Or ganome tallies
Potentially Present
Specific
Components
Ammon ia
Aliphatic Amines
Aromatic Amines
Benzene

Toluene

Xylene


Tetraethyl lead

Phase Toxicity Reference
Aqueous W-l A-5
Aqueous
Aqueous
Gas and T-2/W-1 A-2, 8
Aqueous
Gas and T-2/W-1 A-8
Aqueous
Gas and T-2/W-1 A-8
Aqueous
Aqueous W-l A-5, 7
Aqueous
   Known Hazardous

-------
Table 3-3 (continued).  (S)  Storage and Blending (Group III)
Chemical Potentially Present
Status
Known Present/
Suspected Hazardous
Suspected Present/
Known Hazardous
Emission
Class
1. Acids and Anhydrides
5. Carbonyl Compounds
11. Hydrocarbons
18. Phenols
21. Sulfur Compounds
22. Trace Elements
10. Heterocyclic
20. Polynuclear
Specific
Components
Aldehydes
Ketones
Benzene
Toluene
Xylene
Sulfides
Sulfonates
Phase Toxicity Reference
Aqueous
Gas and
Aqueous
Gas and
Aqueous
Gas and T-2/W-1 A-2, 8
Aqueous
Gas and T-2/W-1 A-8
Aqueous
Gas and T-2/W-1 A-8
Aqueous
Aqueous W-l A-5, 7
Aqueous
Aqueous
Aqueous
Gas and
Aqueous
Gas and
Aqueous
 23.  Organometallics
Aqueous

-------
                                   Table 3-3 (continued).   (U)  Flares
Chemical Potentially Present
Emission
Status Class
Known Present/ 3. Amines
Suspected Hazardous
5 . Carbonyl Compounds
6. Combustion Gases


11. Hydrocarbon


21. Sulfur Compounds



Specific
Components
Ammonia

Aldehydes
Carbon Monoxide
Sulfur Oxides
Nitrogen Oxides
Benzene
Toluene
Xylene
Carbonyl Sulfide
Carbon Bisulfide
Mercaptans
Hydrogen Sulfide
Phase
Gas

Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Toxic ity Reference



T-l
T-2
T-l
T-2 A-2
T-2
T-2
T-l
T-l
T-l
T-2
Suspected Present/
Known Hazardous
24.  Fine Particulates


25.  Cyanides

10.  Heterocyclics
                                                   Carboniferous
                                                     Compounds
Pyridines
Pyrroles
Indoles
                        Gas
Gas

Gas
Gas
Gas
T-l
A-l

-------
                                       Table 3-3  (continued).   (U)  Flares
Chemical
Emission
Status Class
20. Polynuclear
Potentially Present
Specific
Components
Pyrenes
Perylenes
Anthracenes

Phase
Gas
Gas
Gas
Toxic ity
T-O/C-3
T-l/C-4
T-O/C-4
Reference
A-l, 2,
A-l
A-l
3
                            21.   Sulfur  Compounds
Thiophenes
Gas
UJ

-------
                                 Table 3-3  (continued).   (V)  API Grit Chambers
Ln
Chemical Potentially Present
Emission
Status Class
Suspected Present/ 1. Acids and
Known Hazardous Anhydrides
2. Alcohols
3. Amines
4. Inorganic Salts
5. Carbonyl Compounds
10. Heterocyclics


11. Hydrocarbons

13. Lactones
15. Nitrosamines
Specific
Components
Cresylic
Maleic

Diethylamine
Methylethylamine
Aromatic Amines

Ketones
Aldehydes
Pyridines
Pyrroles
Indoles
Furans
Quinolines
Benzene
Toluene
Xylene


Phase Toxic ity Reference
Solid
Solid
Solid
Solid
Solid
Solid
Solid
Solid
Solid
Solid
Solid
Solid
Solid
Solid
Solid
Solid
Solid
Solid
Solid

-------
                                 Table 3-3  (continued).   (V)  API Grit Chambers
in
Chemical Potentially Present
Emission Specific
Status Class Components
18. Phenols Cresols
Xylenols
Phenols
Thiophenols
20. Polynuclear Pyrenes
Perylenes
Anthracenes
Carbazoles
21. Sulfur Compounds Sulfides
Sulfites
Sulfonates
Sulfones
Mercaptans
Thiophenes
22. Trace Elements Vanadium
Nickel
Zinc
Copper
23. Organometallics Metalloporphyrins
25. Cyanides
Phase Toxic ity Reference
Solid
Solid
Solid
Solid
Solid
Solid
Solid
Solid
Solid
Solid
Solid
Solid
Solid
Solid
Solid
Solid
Solid
Solid
Solid
Solid

-------
                                 Table 3-3 (continued).  (W)  Biological Sludge
Chemical Potentially Present
Status
Suspected Present/
Known Hazardous
Emission
Class
22. Trace Elements
Specific
Components
Vanadium
Nickel
Zinc
Copper
Phase
Solid
Solid
Solid
Solid
Toxicity Reference

                           23.  Organometallics                                Solid
Ln

-------
                                   Table  3-3  (continued).   (X)  Spent Catalysts
t-n
Chemical Potentially Present
Status
Known Present/
Suspected Hazardous




Suspected Present/
Known Hazardous
Emission
Class
3. Amines
4. Inorganic Salts
5. Carbonyl Compounds
11 . Hydrocarbons
21. Sulfur Compounds
22. Trace Elements
10. Heterocyclic
Specific
Components

Aldehydes
Aromatic
Sulfides
Sulfites
Sulfonates
Sulfones
Mercaptans
Vanadium
Nickel
Zinc
Copper
Pyridines
Pyrroles
Indoles
Furans
Qu inclines
Phase Toxicity Reference
Solid
Solid
Solid
Solid
Solid
Solid
Solid
Solid
Solid
Solid
Solid
Solid
Solid
Solid
Solid
Solid
Solid
Solid
                             15.   Nitrosatnines
Solid

-------
                                  Table  3-3  (continued).   (X)   Spent Catalysts
Chemical
Emission
Status Class
20. Polynuclear
21. Sulfur Compounds
23. Organometallics
Potentially Present
Specific
Components
Pyrenes
Perylenes
Anthracenes
Carbazoles
Thiophenes
Metalloporphyrins

Phase Toxicity Reference
Solid
Solid
Solid
Solid
Solid
Solid
Ln
00

-------
                                        Table 3-4.  POTENTIAL FOR FUGITIVE EMISSIONS FROM
                                                    PETROLEUM PROCESS SUBMODULES
Ln
SO
Module
No.
Process Name
Pressure
Temp.(b)
Potentially
Hazardous
Vo la tiles
Corrosive-
ness
General
House-
keeping
Potential For
Hazard ous
Fugitive
Emissions
I. PROCESSING EQUIPMENT
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
Gas Well
Oil Well
Field Separations
Condensate Storage & Loading
Crude Storage (field)
Acid Gas Removal (field)
Sulfur Recovery (field)
Dehydration
Gas Separation
LPG Storage & Loading
Gasoline Storage & Loading
Crude Storage (refinery)
Desalting
Atmospheric Distillation
Acid Gas Removal (refinery)
Sulfur Recovery (refinery)
Gas Processing
Vacuum Distillation
Hydrogen Production
Polymerization
A Iky la t ion
High
High
High
Low
Low
Low
Low
Low
Med.
Med.
Low
Low
Low
Low
Low
Low
Med.
Low
High
High
Med.
Low
Low
Low
Low
Low
Low
High
Low-Med .
Low
Low
Low
Low
Med.
Med.
Low
High
Low
High
High
High
Low
High
High
High
Low
Med.
High
High
Low
Low
Low
Low
Med.
Low-Med .
High
High
High
Low
High
Low
Low
Low
Low
Low
Low
Low
Low
Med.
Med.
Low
Low
Low
Low
Low
Low
Med.
Med.
Med.
Los
Med.
Low
Med.
High
Poor
Poor
Poor
Poor
Poor
Med.
Med.
Med.
Med.
Med.
Med.
Poor
Med.
Med.
Med.
Med:
Med.
Low-Med.
Good
Good
Good
High
High
High
Med.
Med.
Med. -High
Med . -High
Low
Low
Low
Med.
Med.
Low
High
Med . -High
Med . -High
Low
Med.
Low
Low
Low

-------
Table 3-4.  (continued)
Module
No.
22
23
24
25

26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42

Isomerization
Naptha HDS
Catalytic Reforming
Light Hydrocarbon Storage
and Blending
Chemical Sweetening
Kerosene HDS
Gas Oil HDS
Fluid Bed Cat. Cracker
Moving Bed Cat. Cracker
Catalytic Hydrocracking
Int. HC Storage & Blending
Lube Oil HDS
Deasphalting
Resid. Oil HDS
Visbreaking
Coking
Steam Boiler
Lube Oil Processing
Asphalt Blowing
Heavy HC Storage & Blending
Gas/Oil Well
Pressure
High
High
Med.
Low

Low
High
High
Low
Low
High
Low
High
Low
High
Low
Low
Low
Low
Low
Low
High
Temp.
-------
Table 3-4.  (continued)
Module
No. Process Name
II.



(a)
(b)
AUXILIARY EQUIPMENT
Wastewater Systems
Oil Fired Heaters
Sour Water Stripper
Low Med .
(PSIG) > 50 50-150
(°F) >150 150-300
Potentially
, . ... Hazardous
Pressure ^ ' Temp. l ' Volatiles

Low Low High
Low/High High High
Low Med. High
High
<150
<300
Corroslve-
ness

High
Low
High

General
House-
keeping

Poor
Poor
Med.

Potential For
Hazardous
Fugitive
Emissions

High
High
High


-------
CONVENTIONAL COAL PROCESS MODULE
          The same approach to analyze the potentially hazardous
emission from the extraction and processing of crude oil was used to
analyze the potentially hazardous emission from coal mining and
processing.  The identified operations were grouped into three process
flow sheets.  These process flow sheets and the flow of materials
through them are shown in Figures 3-7 and 3-8.  A list of 16 process
modules is also shown in Table 3-5.
          The identification and the assessment of all the potentially
hazardous emission streams were conducted in a fashion similar to that
employed for the petroleum process modules.  Seven classes of
emission streams were defined.  They are listed in Table 3-6.
          The data sheets of the emission streams were made with a
similar approach.  The assessment of the emission streams was made
with the published information on emission stream compositions and
with the consideration of the process  conditions.  The data sheets
showing the results of the analysis of the emission streams, as
described in Table 3-6, are shown in Table 3-7.
          The assessment of fugitive losses from each coal conventional
process module  is summarized in Table  3-8.  The fact sheets of some of
the modules from which potentially hazardous  emissions are expected
are included in Appendix B.

Conclusions
           (1)   Among  the conventional  coal processes, coking is  the
most offensive  technology because of the high toxic materials  emitted,
such as known carcinogens.  Although the combustion of coal  is the
cleanest process per  unit of coal processed,  it is probably  the  most
significant due to the massive  tonnages  involved.
           (2)   The coke oven and the coal  tar storage areas  have been
identified  as the major sources of  potentially hazardous emissions  in
a coke plant.   The potentially  hazardous materials are  emitted from the
                                 62

-------
coke oven primarily during the charging, pushing, and coking
operations.
          (3)  Coke quenching and cooling is the major source of
fugitive loss in the coke plant.
          (4)  Some known carcinogens, such as benzo(a)pyrene, chrysene,
Dibenzo(a,h)anthracene and Dibenzo(a,g)fluorene have been identified
in the coal tar volatiles and in the atmosphere surrounding the coke
oven.
           (5)  The emission  streams with the  greatest  numbers of
compounds in the known/known status are coke  oven  off  gas and coke
quenching and cooling.
                                  63

-------
   Coal
extraction
Coal
Crushing and
Grinding


  Froth
flotation
Thermal
drying
                                     Coarse
                                      coal
                                    Gravity
                                   separation
                                            FIGURE  3-7.   COAL PREPARATION

-------
            Volatile collection
               and cooling
\^
industrial
boilers
16
                                         FIGURE  3-8.   CONVENTIONAL COAL PROCESS MODULE

-------
Table 3-5.  PROCESS MODULES OF COAL USAGE (CONVENTIONAL)
Module
             Name
   1
   2
   3
   4
   5
   6
   7
   8
   9
  10
  11
  12
  13
  14
  15
  16
Coal Extraction
Crushing and Grinding
Gravity Separation
Froth Flotation
Thermal Drying
Slot Type Coke Oven
Volatile Collection and Cooling
Tar Liquor Decantation
Ammonia Recovery
Pyridine Recovery
Phenol Recovery
Coke Quenching
Light Oil Recovery
Storage
Utility Boilers (Coal)
Industrial Boilers (Coal)
                            66

-------
Table 3-6.  PROCESS STREAM CIASSIFICATION (CONVENTIONAL COAL)

(A)  Coal Preparation
       1.  Coal Extraction
       2.  Crushing and Grinding
       3.  Gravity Separation
       4.  Froth Flotation
       5.  Thermal Drying
(B)  Coke Oven Off Gas
       6.  Slot Type Coke Oven (including charging and
             pushing)
(C)  Quenching and Direct Cooling Operations
       7.  Volatile Collection and Cooling
       8.  Tar Liquor Decantation
      12.  Coke Quenching
(D)  Boiler Off Gas
      15.  Utility Boiler (Coal)
      16.  Industrial Boiler (Coal)
(E)  Storage and Blending (Group II)
      14.  Storage (Light Oil, Coal Tars)
(F)  Ash
      15.  Utility Boiler (Coal)
      16.  Industrial Boiler  (Coal)
(G)  Fugitive Sources
       •   Total Conventional Coal and Residual Oil Usage Module
                              67

-------
              TABLE 3-7.  POTENTIALLY HAZARDOUS EMISSIONS FROM CLASSIFIED STREAMS AND PROCESSES
                          (CONVENTIONAL COAL)

                                             (A)  Coal Preparation
00

Status
Known Present/ 24.
Known Hazardous
Suspected Present/ 1.
Known Hazardous
22.
Chemicals
Emission
Class
Fine Particulates
Acid and
Anhydrides
Trace Elements
Potentially Present
Specific
Components
Respirable Coal Dust
Sulfuric Acid
Beryllium
Selenium
Arsenic
Lead
Cadmium

Phase
Gas
Aqueous
Solid
Solid
Solid
Solid
Solid
Toxicity Reference
T-0

T-0
T-0
T-0
T-0
T-0

-------
Table 3-7 (continued).  (B)  Coke Oven Off-Gas
Status
Known Present/
Known Hazardous







Known Present/
Suspected Hazar-
dous


Chemica Is
Emission
Class
3. Amines
6. Combustion Gases
20. Polynuclear

23. Organome tallies
24. Fine Particulates

25. Cyanides
1. Acid & Anhydrides
3. Amines

Potentially Present
Specific
Components
01 + 3 Naphthyl amine
4-aminobiphenyl
Carbon monoxide
Pyrene
Chrysene
Benzo(a)pyrene
Benzo (e ) pyrene
Dibenzo(a,h)-
• anthracene
Dibenzo (a , g) f luorene
Nickel carbonyl
Tar
Soot
Hydrogen cyanide
Benzoic acid
Hydroxybenzoic acid
Hydrochloric acid
Ammonia
Aniline
Methylaniline

Phase
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas

Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Toxicity
C-l
C-l
T-l
T-O/C-3
T-O/C-3
T-l/C-1
T-l/C-2
T-l/C-1
T-l/C-1
T-O/C-1
C-l
C-2
T-l
T-l
T-l
T-l
T-2
C-3
T-l
Reference
A-2;B-1
B-l

A-1;B-1,3,4
A-1,2,3; B-l, 3
A-1;B-1,2,3,4
A-l; B-l, 3
A-l; B-l
A-l; B-l



B-l
B-l
B-l
B-l
B-l
A-2; B-l
B-l

-------
                              Table 3-7 (continued).   (B)  Coke  Oven Off-Gas
•vj
o
Chemicals Potentially Present
Emission Specific
Status Class Components
5. Carbonyl Compounds Formaldehyde
Ace t aldehyde
Par aldehyde
20. Polynuclear Methylchrysene
Benzo(a)anthracene
Dime thy Ibenzanthracenes
21. Sulfur Compounds Methyl mercaptan
Ethyl mercaptan
22. Trace Elements Beryllium
Silver metals and
soluble compounds
Mercury
Vanadium
Lead
Cadmium
Antimony
Arsenic
Barium
Suspected Present/ 10. Heterocyclics Pyridine
Known Hazardous Alkyl pyridine
Phenyl pyridine
(Mono) Benzofurans
Quinoline
Alkyl quinoline

Phase
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas

Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Toxicity
T-l
T-2
T-2
T-l/C-3
T-l/C-3
T-l/C-2
T-0
T-0
T-0
T-2

T-0
T-0
T-0
T-0
T-0
T-0
T-0
T-l
T-l
T-l
T-2
T-0
T-0
Reference
B-l
B-l
B-l
A-1,2; B-l
A-1,2; B-l, 3
A-l; B-l




A-4; E-4
A-4; E-4
E-4, 5
A-4; E-4
A-4; E-4
E-4
A-4; E-4, 5
E-5
A-l; B-l
B-l
B-l
B-l
B-l


-------
Table 3-7 (continued).   (B)  Coke Oven Off-Gas
Chemicals Potentially Present
Emission Specific
Status Class Components
Suspected Present/ 11. Hydrocarbons Aliphatics
Known Hazardous Olefins
Benzene
Toluene
Xylene
Alkylbenzenes
18. Phenols Phenol
o,m,p-cresols
Phenyl phenol
Xylenols
Alkyl phenols
Alkyl cresols
20. Polynuclear Biphenyl
Naphthalene
Alkyl naphthalene
Phenyl naphthalene
Tetralin
Methyl tetralin
A ce na ph thy le ne
Acenaphthene
Fluorene
Anthracene
Alkyl anthracenes
Phenanthrenes
Alkyl phenanthrenes
Cor one ne

Phase
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Toxic ity
T-2
T-2
T-2
T-2
T-2
T-2
T-l
T-l
T-l
T-l
T-l
T-l
T-l/C-4
T-2
T-2
T-2
T-2
T-2
T-2
T-2
T-l/C-4
T-O/C-4
T-l/C-4
T-O/C-4
T-l/C-4
T-l
Reference
B-l
B-l
A-2; B-l
B-l
B-l
B-l
B-l
B-l
B-l
B-l
B-l
B-l
B-l
B-l
B-l
B-l
B-l
B-l
B-l
B-l
A-l; B-l
A-l; B-l, 4
A-l; B-l
A-l; B-l
A-l
B-l, 3,4

-------
Table 3-7 (continued).  (B)  Coke Oven Off-Gas
Chemicals Potentially Present
Emission Specific
Status Class Components
Carbazole
Acrid ine
Benzocarbazoles
Aklylacridines
Benzo (a) anthrone
Perylene
21. Sulfur Compounds Hydrogen sulfide
Thiophenes
Methyl thiophene
Carbon disulfide
Carbonyl sulfide
22. Trace Elements Selenium
24. Fine Particulates Coke
Coal
25. Cyanides Ammonium cyanide
Naphthyl cyanide

Phase
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Toxicity
C-3
T-0
C-3
T-0
C-2
T-l/C-4
T-2


T-l
T-l

Reference
A-2;
A-l;
A-l;
A-2;
A-l;
E-5
B-l;
B-l;

A-4;

B-l
B-l
B-l
B-l
B-3
B-l, 3
E-5
E-5

E-4



-------
                       Table 3-7 (continued).   (C)  Quenching and  Direct Cooling Operation
OJ
Chemicals Potentially Present
Status
Known Present/
Known Hazardous






Known Present/
Suspected Hazar-
dous
Emission
Class
3. Amines
6. Combustion Gases
18. Phenols
20. Polynuclear
23. Organomfe tallies
24. Fine Particulates
25. Cyanides
1. Acid and
Anhydrides
Specific
Components
a + p Nap thy 1 amine
4-aminobiphenyl
Carbon monoxide
Phenol
Pyrene
Chrysene
Benzo(a)pyrene
Benzo(e)pyrene
Dibenzo (a ,h) anthracene
Dibenzo (a , g ) t luor ene
Nickel carbonyl
Tar
Soot
Hydrogen cyanide
Benzoic acid
Hydroxybenzoic acid
Hydrochloric acid
Sulfuric acid
Phase
Gas
Gas
Gas
Aqueous
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Aqueous
Toxic ity
C-l
C-l
T-l
W-l
T-O/C-3
T-O/C-3
T-l/C-1
T-l/C-2
T-l/C-1
T-l/C-1
T-O/C-1
C-l
C-2
T-l
T-l
T-l
T-l
W-l
Reference
A-2; B-l
B-l

A-5,7
A-1;B-1,3,4
A-1,2,3;B-1,3
A-1;B-1,2,3,4
A-l; B-l, 3
A-l; B-l
A-l; B-l


B-l
B-l
B-l
B-l
A-8

-------
Table 3-7 (continued).   (C)  Quenching and Direct  Cooling Operation
Chemicals
Emission
Status Class
3. Amines
Known Present/ 4. Inorganic Salts
Suspected Hazard-
ous 5. Carbonyl Compounds
10. Heterocyclics
11. Hydrocarbon
18. Phenols
20. Polynuclear
21. Sulfur Compounds
Potentially Present
Specific
Components
Ammonia
Aniline
Methylanilines
Ammonia
Ammonium sulfate
Formaldehyde
Acetaldehyde
Paraldehyde
Pyridine
Benzene
Toluene
Xylene
o,m,p-Cresol
Methylchrysenes
Benzo(a)anthracene
Dime thy Ibenzanthracene
Methyl mercaptan
Ethyl mercaptan
Thiophenes

Phase
Gas
Gas
Gas
Aqueous
Aqueous
Gas /Aqueous
Gas /Aqueous
Gas
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Gas
Gas
Gas
Gas
Gas
Aqueous
Toxic ity
T-2
C-3
T-l
W-l
W-2
T-l/W-1
T-2/W-1
T-2
W-2
W-l
W-l
W-l
W-l/C-3
T-l/C-3
T-l/C-3
T-l/C-2
T-0
T-0
W-l
Reference
B-l
A-2; B-l
B-l
A-5
A-2
A-8; B-l
A-8; B-l
B-l
A-8
A-8
A-8
A-8
A-5
A-1,2; B-l
A-1,2; B-l,:
A-l; B-l
A-8

-------
Table 3-7 (continued).  (C)  Quenching and  Direct Cooling Operation
Chemicals Potentially Present
Emission Specific
Status Class Components
22. Trace Elements Beryllium
Silver metals and
soluble compounds
Mercury
Vanad ium
Lead
Cadmium
Antimony
Arsenic
Barium
Selenium
23. Organometallics Nickel carbonyl
25. Cyanides Hydrogen Cyanide
Ammonium Cyanide
Ammonium Thiocyanate
Suspected Present/ 10. Heterocyclics Pyridine
Known Hazardous Alkyl pyridines
Phenyl pyridine
(Mono) Benzofurans
Qunioline
Alkyl qu inclines

Phase
Gas
Gas

Gas/Aqueous
Gas
Gas /Aqueous
Gas
Gas
Gas
Gas
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Gas
Gas
Gas
Gas
Gas
Gas
Toxicity
T-0
T-2

T-O/W-1
T-0
T-O/W-1
T-0
T-0
T-0
T-0
W-l
W-l/C-1
W-l
W-l
W-l
T-l
T-l
T-l
T-2
T-0
T-0
Reference
A-4; E-4


A-8; E-4
E-4, 5
A-8; E-4
A-4; E-4
E-4
A-4; E-4, 5
E-4
A-8
A-6
A-5
A-8
A-8
A-l; B-l
B-l
B-l
B-l
B-l


-------
Table 3-7 (continued).   (C)  Quenching and Direct Cooling  Operation
Chemicals Potentially Present
Emission Specific
Status Class Components
Dibenzofuran
Alkyldibenzofurans
Suspected Present/ 11. Hydrocarbons Aliphatics
Known Hazardous Olefins
Benzene
Toluene
Xylene
Alkylbenzenes
18. Phenols Phenol
o,m,p-Cresols
Phenyl phenol
Xylenols
Alkyl phenols
Alkyl cresols
20. Polynuclear Biphenyl
Naphthalene
Alkyl naphthalenes
Phenyl naphthalenes
Tetralin
Methyl tetralins
Acenaphthylene
Acenaphthene
Fluorene
Anthracene
Alkyl anthracenes
Phenanthrenes

Phase
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Toxic ity
T-l
T-l
T-2
T-2
T-2
T-2
T-2
T-2
T-l
T-l
T-l
T-l
T-l
T-l
T-l/C-4
T-2
T-2
T-2
T-2
T-2
T-2
T-2
T-l/C-4
T-O/C-4
T-l/C-4
T-O/C-4
Reference


B-l
B-l
A-2; B-l
B-l
B-l
B-l
B-l
B-l
B-l
B-l
B-l
B-l
B-l
B-l
B-l
B-l
B-l
B-l
B-l
B-l
A-l; B-l
A-l; B-l, 4
A-l; B-l
A-l; B-l

-------
Table 3-7 (continued).   (C)  Quenching and  Direct  Cooling  Operation
Chemicals Potentially Present
Emission Specific
Status Class Components
Alkyl phenanthrenes
Coronene
Carbazole
Acridine
Benzocarbazoles
Alkylacridines
Benzo (a)anthrone
Perylene
21. Sulfur Compounds Hydrogen sulfide
Thiophenes
Methyl thiophenes
Carbon disulfide
Carbonyl sulfide
22. Trace Elements Selenium
Arsenic (arsenic tri-
oxide, sodium arsenate,
sodium arsenite)
Barium (acetate,
chloride, nitrate)
Cadmium (chloride,
nitrate, sulfate)
24. Fine Particulates Coke
Coal
25. Cyanides Ammonium cyanide
Naphthyl cyanide

Phase
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Aqueous


Aqueous

Aqueous

Gas
Gas
Gas
Gas
Toxic ity
T-l/C-4
T-l
C-3
T-0
C-3
T-0
C-2
T-l/C-4
T-2





W-l/C-4


W-2

W-l

T-l
T-l


Reference
A-l
B-1,3,4
A-2; B-l
A-l; B-l
A-l; B-l

A-2; B-3
A-l; B-1,3
E-5
B-l; E-5
B-l; E-5


A-4; E-4
A-8


A-8

A-8



B-l


-------
                                    Table  3-7  (continued).   (D)  Boiler Off-Gas
00
Status
Known Present/
Known Hazardous












Known Present/
Suspected Hazard-
ous





Chemicals
Emission
Class
4. Inorganic Salts

6. Combustion Gases

10. Heterocyclics

20. Polynuclears





24. Fine Particulates

1. Acid and
Anhydrides

3. Amines


5. Carbonyl
Compounds
Potentially Present
Specific
Components
Chromium CrCl_, CrS

Sulfur oxides
Nitrogen oxides
Benzo(f )qu incline
Benzo(h) quinoline
Benzo (a)pyrene
Benzo(e)pyrene
Pyrene
Chrysene
Benzo (a)anthracene
Phenanthrene
Soot
Ash
Sulfuric acid
Nitric acid
Hydrogen chloride
Of + p Naphthylamines
4 -Aminob iphe ny 1
Benzidine
Formaldehyde


Phase
Gas

Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas

Toxic ity
T-0

T-2
T-2
T-0
T-0
C-l
C-l
C-3/T-0
C-2/T-0
C-3/T-1
T-O/C-4
C-2
T-l
T-l
T-l
T-l
C-l/T-0
C-l/T-0
C-l/T-0
T-2

Reference
D-5



D-6
D-6
A-l;D-2,3,4
A-l
A-l; D-4
A-l, 2, 3
A-l, 2, 3
A-l; D-4




D-l






-------
Table 3-7 (continued).  (D)  Boiler Off-Gas
Chemicals
Emission
Status Class
6. Combustion Gases
10. Heterocyclic

20. Polynuclear








22. Trace Elements












Potentially Present
Specific
Components
Carbon monoxide
Indeno (1,2,3-ij)
isoquinoline
Perylene
Coronene
Anthracene
Acridine
Benzo(a)acridine
Benzo(c)acridine
Fluoranthene
Dibenzo(a,h)acridine
Phenanthridine
Mercury
Beryllium
Se lenium/Se lenium
oxides (Se02,SeO,)
Ar-senic/As_6_, As~S.,
Lead
Barium
Fluorine
Uranium
Vanadium
Copper
Cadmium/Cadmium oxide
(CdO)

Phase
Gas
Gas

Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas

Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas

Toxicity
T-2


C-4/T-1
T-l

T-0
T-0
T-0

T-0

T-0
T-0
T-0

T-0
T-0
T-0
T-l
T-0
T-0
T-0
T-0

Reference

D-6

A-l; D-4
D-4
D-4
D-4
D-6
D-6
D-4
D-6
D-3
A-4
A-4
A-4; D-5

A-4; D-5
A-4
D-5




D-5


-------
                                   Table 3-7 (continued).  (D)  Boiler Off-Gas
oo
o
Chemicals Potentially Present
Emission
Status Class

Suspected Present/ 3. Amines
Known Hazardous
5. Carbonyl
Compounds
10. Heterocyclic
18. Phenols
20. Poly nuclear
21. Sulfur
Compounds
Specific
Components
Thallium/Thallium Oxide
Antimony/Sb?0«
Zinc
Aniline
Cr(CO)6
Pyridine
Phenol
Dibenzo (a , g) f luorene
Thiophene
Benzothiophenes
Dibenzothiophenes
Phase
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Toxicity
T-0
T-0
T-l
C-3/T-2
T-0
T-l
T-l
C-l/T-1
T-2
Reference
D-5
D-5
D-5



A-l


-------
                       Table  3-7  (continued).   (E)   Storage  and  Blending
00
Chemicals Potentially Present
Status
Known Present/
Suspected Hazardous


Suspected Present/
Emission
Class
3. Amines
11. Hydrocarbons
18. Phenols
23. Organometallics
Specific
Components
Ammonia
Aliphatic amines
Aromatic amines
Benzene
Toluene
Xylene

Tetraethyl lead
Phase Toxicity
Aqueous
Aqueous
Aqueous
Gas & Aqueous T-2/W-1
Gas & Aqueous T-2/W-1
Gas & Aqueous T-2/W-1
Aqueous
Aqueous
Reference

A-2,8
A- 8
A-8


   Known Hazardous

-------
                                        Table 3-7  (continued).   (F)  Ash
oo
NJ
Chemical Potentially Present
Emission Specific
Status Class Components
Suspected Emission/ 22. Trace Elements Mercury
Known Hazardous Beryllium
Selenium
Arsenic
Lead
Barium
Fluorine
Uranium
Vanad ium
Copper
Cadmium
Thallium
Antimony
Zinc

Phase
Solid
Solid
Solid
Solid
Solid
Solid
Solid
Solid
Solid
Solid
Solid
Solid
Solid
Solid
Toxicity Reference
T-0
T-0
T-0
T-0
T-0
T-0
T-0
T-0
T-0
T-0
T-0
T-0
T-0
T-l
                        24.   Fine  Particulates    Respirable  dust
Solid
T-0

-------
             Table 3-8.  POTENTIAL FOR FUGITIVE EMISSIONS FROM CONVENTIONAL COAL PROCESS MODULE
00
00

Module
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16

(a)
(b)
Process Name
Coal Extraction
Crushing and Grinding
Gravity Separation
Froth Floatation
Thermal Drying
Slot Type Coke Oven
Volatiles Collection and Cooling
Tar Liquor Decantation
Ammonia Recovery
Pyridine Recovery
Phenol Recovery
Coke Quenching
Light Oil Recovery
Storage
Utility Boilers (Coal)
Industrial Boilers (Coal)
Low Med High
PSIG <50 50-150 >150
°F <150 150-300 >300
Pres-
low
low
low
low
low
low
low
low
low
low
low
low
low
low





Tempera-
ture 
-------
ADVANCED COAL PROCESS MODULE

          A gasification process and a liquefaction process were
selected for the advanced coal process flow sheets.  A high-Btu gas
Lurgi-type process and the solvent refined coal process were chosen
for the gasification process flow sheet and the liquefaction process
flow sheet, respectively.  The major operations and the flow of
materials through them are identified and shown in Figures 3-9 and 3-10
by similar procedures described in the petroleum and conventional coal
process flow sheets.  A list of 25 modules is shown in Table 3-9.
          Each module was assessed and the potentially hazardous
emission streams were identified.  The emission streams from the water-
oil separation, fractionation, hydrotreating, and hydrocracking
modules are similar to those in the refinery process flow sheet.  Thus,
the discussion and the detailed assessment of the potentially hazardous
emission streams were not repeated in this section.  Ten classes of
emission streams were defined and listed in Table 3-10.
          A data sheet was prepared for each class of emission stream.
However, the assessment was heavily dependent on the experience from
the similar operations of other conventional processes.  There is very
little published information about the composition of the process
streams in the gasification and liquefaction plants.  The data sheets
of these classes of emission streams are shown in Table 3-11.  The
"ash" emission stream is similar to the one in the conventional coal
process flow sheet and its data sheet is not included in this section.
          The assessment of the fugitive losses from these advanced
coal processes are difficult because there is no commercial scale
operating experience of these plants.  There are some Lurgi gasifica-
tion plants outside the United States.  However, these plants are
old.   They were initially designed to produce low-Btu gas.  Through
experience from other similar operations of the conventional
processes,  an assessment was made in a similar fashion as in the
refinery and the conventional coal process flow sheets.  Table 3-12
                                  84

-------




H* Separation
Z 1?

	 1

                                                      To Plant Fuel
                                                       ro Vent
FIGURE  3-9.  LIQUEFACTION PROCESS MODULE

-------
00
        _J  tlr-bliwi
     S-*.    \  blirictlloo
     0	1        . "
                                          FIGURE 3-10.   GASIFICATION PROCESS MODULE

-------
 summarizes  the results of  the analysis.  The fact sheets of the
 process modules as  listed  in Table 3-9 are included in Appendix A.
 Conclusions
          The published information of the composition of the emis-
 sion streams are sparse because there is no existing commercial
 Lurgi nor solvent refined  coal plant in the United States.  On the
 basis of the information from some European operations and the
 similarities with the other conventional processes, the following
 conclusions are made.
          (1)  Coal gasification is likely to produce equally
 dangerous substances as the coke plant, but they will probably be
 somewhat more contained than coke oven emission.
          (2)  The quenching and cooling of gasifier off gas and
 the tar separation unit are the most important potential sources of
 toxic materials emissions  in a gasification plant.
          (3)  Coal liquefaction will probably also produce
 extremely dangerous products but they may be more contained than
 those from a gasification  operation.
          (4)  The primary potentially hazardous emission sources
 in a liquefaction plant are the slurry preparation and fugitive
 losses from leaks and equipment failures.
          (5)  Liquefaction products will probably be more hazard-
ous than crude oil products, and their refining and utilization
will be worse offenders than the corresponding petroleum operations.
                             87

-------
Table 3-9.  PROCESS MODULES OF COAL USAGE (ADVANCED)

Module                         Name
   1                 Slurry Preparation
   2                 Reac tor
   3                 Reactor Separator
   4                 Condenser
   5                 Filtration
   6                 Water-oil Separation
   7                 Fractionation
   g                 Hydrotreating
   9                 Hydrocracking
  10                 Storage
  11                 Acid Gas Treatment
  12'                 Hydrogen Separation
  13                 Sulfur Plant
  14                 Coal Preparation
  15                 Oxygen Blown  Gasification
  16                 Quenching and Cooling
  17                 Tar Separation
  1£                 Shift Conversion
  ig                 Phenol Recovery (Phenosolvan
                       Process
  20                 Acid Gas Removal (Rectisol Wash)
  21                 Methanation
  22                 Further Gas Purification
                       (Rectisol Wash)
  23                 Sulfur Recovery (Stretford
                       Process)
  24                 Air Blown Gasification
  25                 Storage
                         88

-------
Table 3-10.  PROCESS STREAM CLASSIFICATION (ADVANCED COAL)

(A)  Coal Preparation
        1.  Slurry Preparation
       14.  Coal Preparation
(B)  Quenching and Direct Cooling Operations
        3.  Reactor Separator
       16.  Quenching and Cooling
(C)  Sour Aqueous Condensate
        4.  Fractionation
        5.  Hydrocracking
        9.  Condenser
       19.  Phenol Recovery
(D)  Fixed-Bed Catalyst Regeneration
        8.  Hydrotreating
        9.  Hydrocracking
(E)  Barometric Condenser Off Gas
        7.  Fractionation
(F)  Storage and Blending
       10.  Storage (Fuel Oil, Naphthas)
       25.  Storage (Tar, Oil, Naphthas,  Phenol)
(G)  Sulfur Plant
       13.  Sulfur Recovery (Claus Plant)
       23.  Sulfur Recovery (Stretford Process)
(H)  Reactor Off Gas
        2.  Reactor^*)
       15.  Oxygen Blower Gasifier
       21.  Methanation
       24.  Air-Blown Gasifier
(I)  Tar Separation
       17.  Tar Separation
                         89

-------
Table 3-10 (continued).  PROCESS STREAM CLASSIFICATION
                         (ADVANCED COAL)
(J)  Ash
       15 •   Oxygen-Blown Gasifier
       24 .   Air-Blown Gasifier
(K)  Fugitive Sources
        •   Liquefaction Processing Module
        •   Gasification Processing Module
(a)  The gas emission of the coal liquefaction reactor
     occurs most often during reactor accident or
     reactor clean-up.
                           90

-------
              Table 3-11.  POTENTIALLY HAZARDOUS EMISSIONS FROM CLASSIFIED STREAMS AND PROCESSES
                           (ADVANCED COAL)

                                 (A)  Coal Preparation
Chemicals Potentially Present
Status
Known Present/
Known Hazardous
Suspected Present/
Known Hazardous








Emission Class
24. Particulates

1. Acid & Anhydride

11. Hydrocarbons*
18. Phenols*
21. Sulfur Compounds
24. Particulates




Specific Components
Respirable Coal Dust

Sulfuric Acid




Beryllium
Selenium
Arsenic
Lead
Cadmium
Phase Toxicity Reference
Gas

Aqueous

Gas/Aqueous
Gas /Aqueous
Gas
Solid
Solid
Solid
Solid
Solid
T-0

W-l A-8




T-0.
T-0
T-0
T-0
T-0
*The presence of these conpounds depends on the  type  of  solvent  used  in  coal  slurry  preparation.

-------
vo
ro
                 Table 3-11.   POTENTIALLY  HAZARDOUS EMISSIONS FROM  CLASSIFIED STREAMS AND PROCESSES
                              (ADVANCED COAL)

                                    (B)  Quenching and Direct-Cooling  Operations

Chemicals Potentially Present
Status Emission Class Specific Components
Known Present/ 18. Phenols
Known Hazardous


2.
3,
2,
2
, 5-Dimethylphenol
, 4-Dimethylphenol
, 4-Dimethylphenol
, 6-Dimethylphenol
Phase
Aqueous
Aqueous
Aqueous
Aqueous
Toxicity
W-l
W-l
W-l
W-l
Reference
A-5,
A-5,
A-5,
A-5,
7,
7,
7,
7,
E-7
E-7
E-7
E-7
Known Present/       3.  Amines
Suspected Hazardous
                         21.  Sulfur Compounds   Hydrogen  sulfide

                                               Ammonia
Gas and Aqueous  T-2/W-0

Gas and Aqueous  T-2/W-1
A-5, 6, 7, E-5

    A-l
                         11.  Hydrocarbons
                         18. Phenols


                         21. Trace Elements

                         25. Cyanides

    Suspected Present/   10. Heterocyclic
    Known Hazardous
                                           Benzene
                                           Toluene
                                           Aliphatic
                                           Olefins

                                           o-Cresol
                                           m-Cresol

                                           Selenium

                                           Hydrogen  Cyanide

                                           Dibenzofurans
Gas
Gas
Gas
Gas
Aqueous
Aqueous
Aqueous
Aqueous
Gas
T-2
T-2
T-2
T-2
W-l/C-3
W-l/C-3
W-l
W-l
T-2
A-2



A-5, E-7
A-5, E-7
A-8, E-7
A-5
E-5

-------
                       Table  3-11  (continued).   (B)  Quenching and Direct-Cooling  Operations
u>
Chemicals Potentially Present
Status Emission Class Specific Components
18. Phenols Phenol
o,m,p-Cresols
Phenyl Phenol
Alkyl Phenol
Alkyl Cresols
19. Polynuclear Benzo(a) pyrene
Dibenzo (a , 1) pyrene
Dibenzo (a ,h) pyrene
Dibenzo (a , i) pyrene
Methylpyrenes
Indeno (l,2,3-c,d)
Pyrene
Benzo(e) pyrene
Benzo(a) anthracene
Dibenzoanthracene
Anthracene
Chrysene
Benzo(g,h, i)perylene
Fluoranthene
Perylene
Coronene
Benzoacridine
Benzoanthrone
Acridine
Phenanthrene

Phase
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas

Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas

Toxicity
T-l
T-l
T-l
T-l
T-l
T-0
C-3
C-2
C-2

C-3

T-l/C-2
C-3
C-2
T-0
T-O/C-3
C-4
C-4
T-l/C-4
T-l
C-2
C-2
T-0
T-O/C-4
Reference





A-l






A-l




A-l
A-l
A-l

A-l
A-2
A-l
A-l

-------
                     Table 3-11 (continued).  (B)  Quenching and Direct-Cooling Operations
VO
Chemicals Potentially Present
Status Emission Class Specific Components
21. Sulfur Compounds Thiophene
Methyl Thiophene
Dimethyl Thiophene
Methyl Mercaptan
22. Trace Elements Mercury
Selenium
Arsenic
Lead
Cadmium
Antimony
Vanadium
Nickel
Beryllium
Cobalt
Phosphorus
Manganese
Arsenic (arsenic
trioxides, sodium
arsenate, sodium
arsenite)
Chromium (hexavalent,
trivalent)
Phosphorus (phosphate)
Strontium (nitrate)
Vanadium (pentoxide,
vanadyl sulfate)
25. Cyanides Thiocyanate (ammonium,
potassium, sodium)
Phase
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Aqueous



Aqueous

Aqueous
Aqueous
Aqueous

Aqueous

Toxicity



T-l
T-0
T-0
T-0
T-l
T-0
T-0
T-0
T-l
T-0
T-0
T-0
T-l
W-l/C-4



W-l

W-2
W-2
W-2

W-l

Reference
E-5
E-5
E-5
E-5
E-3, 4
E-3, 4, 5
E-3, 4, 5
E-3, 4
E-3, 4
E-3, 4
E-4, 5
E-3, 4, 5
E-4
E-5
E-5
E-7



A-8, E-7

A-8, E-7
A-8, E-7
A-7, 8, 9, E-7

A-8


-------
Table 3-11 (continued).  (C)  Sour Aqueous Condensate
Chemicals Potentially Present
Status
Known Present/
Suspected Hazardous







Suspected Present/
Known Hazardous
Emission Class
1. Acid and
Anhydrides
2. Alcohols
3 . Amines
5. Carbonyls
10. Heterocyclics
11. Hydrocarbons
18. Phenols
21. Sulfur Compounds
22. Trace Elements
Specific Components
Cresylic Acid
Maleic Acid
Aliphatic Alcohols
Aromatic Alcohols
Ammonia
Aldehydes
Ketone
Pyridines
Pyrroles
Benzene
Toluene
Xylene
Cresols
Xylenols
Phenol
Hydrogen sulfide
Methyl Mercaptan
Sulfides
Sulfonates
Thiophenes

Phase Toxicity Reference
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous W-l A-5
Aqueous W-l A-8
Aqueous
Aqueous W-2 A-8
Aqueous
Aqueous W-l A-8
Aqueous W-l A-8
Aqueous W-l A-8
Aqueous W-l A-5
Aqueous
Aqueous W-l A-5, 7
Aqueous W-0 A-5, 6, 7
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous

-------
                         Table 3-11 (continued).   (D)  Fixed Bed  Catalyst  Regeneration
SC
Status
Known Present/
Known Hazardous


Known Present/
Suspected Hazardous









Chemicals Potentially Present
Emission Class Specific Components
21. Sulfur Compounds Hydrogen Sulfide
Carbonyl Sulfide
Carbon Disulfide
Mercaptans
6. Combustion Gases Carbon Monoxide
Sulfur Oxide
11. Hydrocarbons Benzene
Toluene
Xylene
22. Trace Elements Vanadium
Nickel
Cobalt
Molybdenum
24. Fine Particulates Catalyst
Coke

Phase
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas

Toxicity
T-2


T-0
T-l
T-2
T-2
T-2
T-2
T-0
T-0



T-l
Reference
C-4
C-4

C-4


A-2


A-4
C-l




  Suspected Present/
  Known Hazardous
10.  Heterocyclics


20.  Polynuclear

23.  Organometallics
                                             Nickel Carbonyl
                                             Cobalt Carbonyl
                                                   Gas
Gas

Gas
Gas
T-0

-------
                           Table 3-11  (continued).   (E)   Barometric  Condenser Off Gas
VO
Chemicals Potentially Present
Status Emission Class
Known Present/ 5. Carbonyl
Suspected Hazardous Compounds
10. Heterocyclic
11. Hydrocarbons
18. Phenols
21. Sulfur
Compounds
Specific Components
Aldehydes
Ketones
Pyrroles
Pyridines
Benzene
Toluene
Xylene
Cresols
Xylenols
Phenol
Hydrogen Sulfide
Methyl Mercaptans
Thiophenes
Phase
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Toxicity Reference
T-l
T-l
T-2 A-2
T-2
T-2
T-l
T-l
T-l
T-2

-------
                               Table  3-11  (continued).   (F)   Storage and Blending
>o
oo
Chemicals Potentially Present
Status Emission Class
Known Present/ 3. Amines
Suspected Hazardous
11. Hydrocarbons



18. Phenols
Suspected Present/ 18. Phenols
Known Hazardous



20. Polynuclear




Specific Components
Ammonia

Benzene
Toluene
Aliphatic
Olefins
o,m-Cresols
Phenol
o,m,p-Cresols
Phenyl Phenol
Alkyl Phenol
Alkyl Cresols
Benzo (a) pyrene
Dibenzo (a , 1) pyrene
Dibenzo (a ,h) pyrene
Dibenzo (a , i) pyrene
Methyl Pyrene
Phase
Gas /Aqueous

Gas
Gas
Gas
Gas
Aqueous
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Indeno (l,2,3-c,d) Pyrene Gas







Benzo(e) pyrene
Benzo (a) anthracene
Dibenzoanthracene
Anthracene
Chrysene
Benzo (g , h , i) pery lene
Fluoranthene
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Toxicity
T-2/W-1

T-2
T-2
T-2
T-2
W-l/C-3
T-l
T-l
T-l
T-l
T-l
T-0
C-3
C-2
C-2

C-3
T-l/C-2
C-3
C-2
T-0
T-O/C-3
C-4
C-4
Reference
A-5

A-2



A-5, E-7





A-l





A-l




A-l
A-l

-------
                              Table  3-11  (continued).   (F)   Storage and Blending
\o
VO
Chemicals Potentially Present
Status Emission Class Specific Components
Perylene"
Coronene
Benzoacridine
Benzoanthrone
Acrid ine
Phenanthrene
22. Trace Elements Arsenic (arsenic
trioxides, sodium
arsenate, sodium
arsenite)
Chromium (hexavalent,
trivalent)
Phosphorus (phosphate)
Strontium (nitrate)
Vanadium (pentoxide,
vanadyl sulfate)

Phase
Gas
Gas
Gas
Gas
Gas
Gas
Aqueous



Aqueous

Aqueous
Aqueous
Aqueous


Toxicity
T-l/C-4
T-l
C-2
C-2
T-0
T-O/C-4
W-l/C-4



W-l

W-2
W-2
W-2

Reference
A-l

A-l
A-2
A-l
A-l
E-7



A-8, E-7

A-8, E-7
A-8, E-7
A-7, 8, 9, E-7

                       25.  Cyanides
Thiocyanate (ammonium,      Aqueous

  potassium, sodium)
                                                                                         W-l
A-8

-------
                                   Table 3-11 (continued).   
-------
Table 3-11 (continued).  (G)  Sulfur Plant
Chemicals Potentially Present
Status Emission Class Specific Components
Benzo (g , h , i) pery lene
Fluoranthene
Perylene
Coronene
Benzoacridine
Benzoanthrone
Acridine
Phenanthrene
22. Trace Elements Mercury
Selenium
Arsenic
Lead
Cadmium
Antimony
Vanadium
Nickel
Beryllium
Cobalt
Phosphorus
Manganese

Phase
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas

Toxicity
C-4
C-4
T-l/C-4
T-l
C-2
C-2
T-0
T-O/C-4
T-0
T-0
T-0
T-l
T-0
T-0
T-0
T-l
T-0
T-0
T-0
T-l
Reference
A-l
A-l
A-l

A-l
A-2
A-l
A-l
E-3, 4
E-3, 4, 5
E-3, 4, 5
E-3, 4
E-3, 4
E-3, 4
E-4, 5
E-3, 4, 5
E-4
E-5
E-5


-------
                                  Table 3-11 (continued).  (H)  Reactor Off Gas
o
NS
Chemicals Potentially Present
Status
Known Present/
Known Hazardous

Known Present/
Suspected Hazardous


Suspected Present/
Known Hazardous


Emission Class
5. Carbonyl
Compounds
21. Sulfur
Compounds
3 . Amines

6. Combustion Gases
11. Hydrocarbon
10. Heterocyclic
18. Phenols
20. Polynuclear
Specific Components
Nickel Carbonyl*
Carbonyl Sulfide
Carbon Disulfide
Hydrogen Sulfide
Ammonia

Carbon Monoxide
Nitrogen Oxides
Benzene
Toluene
Dibenzofurans
Phenol
o,m,p-Cresols
Phenyl Phenol
Alkyl Phenol
Alkyl Cresols
Benzo(a)pyrene
Dibenzo (a , 1) pyrene
Dibenzo(a ,h) pyrene
Phase
Gas
Gas
Gas
Gas
Gas

Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Toxicity
T-0
T-l
T-l
T-2
T-2

T-3
T-l
T-2
T-2
T-2
T-l
T-l
T-l
T-l
T-l
T-0
C-3
C-2
Reference
E-l
E-5



A-2
E-5

A-l

-------
                                  Table 3-11  (continued).   (H)  Reactor  Off Gas
o
u>
Chemicals Potentially Present
Status Emission Class Specific Components
Dibenzo (a , i) pyrene
Methyl Pyrene
Indeno (l,2,3-c,d) Pyrene
Benzo(e) pyrene
Benzo (a) anthracene
Dibenzoanthracene
Anthracene
Chrysene
Benzo (g ,h , i) perylene
Fluoranthene
Perylene
Coronene
Benzoacridine
Benzoanthrone
Acridine
Phenanthrene
Suspected Present/ 21. Sulfur Thiophene
Known Hazardous Compounds Methyl Thiophene
Dimethyl Thiophene
Methyl Mercaptan
22. Trace Elements Mercury
Selenium
Arsenic
Lead
Cadmium

Phase
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas
Gas

Toxicity
C-2

C-3
T-l/C-2
C-3
C-2
T-0
T-O/C-3
C-4
C-4
T-l/C-4
T-l
C-2
C-2
T-0
T-O/C-4



T-l
T-0
T-0
T-0
T-l
T-0
Reference



A-l




A-l
A-l
A-l

A-l
A-2
A-l
A-l
E-5
E-5
E-5
E-5
E-3, 4
E-3, 4, 5
E-3, 4, 5
E-3, 4
E-3, 4

-------
                                  Table 3-11 (continued).  (H)  Reactor Off Gas
Chemicals Potentially Present
Status Emission Class Specific Components
Ant imony
Vanadium
Nickel
Beryllium
Cobalt
Phosphorus
Manganese

Phase
Gas
Gas
Gas
Gas
Gas
Gas
Gas

Toxicity
T-0
T-0
T-l
T-0
T-0
T-0
T-l
Reference
E-3, 4
E-4, 5
E-3, 4,
E-4
E-5
E-5



5




  *
o
    This  is  found  only  in  the methanation unit,

-------
Table 3-11 (continued).  (I)  Tar Separation
Chemicals Potentially Present
Status
Known Present/
Known Hazardous
Known Present/
Suspected Hazardous









18
1.
3.
4.
5.
10
11
18
21
22
Emission Class
. Phenols
Acids and
Anhydrides
Amines
Inorganic Salts
Carbonyl
Compounds
. Heterocyclics
. Hydrocarbons
. Phenols
. Sulfur
Compounds
. Trace Elements
Specific Components
Phenol
Sulfuric Acid
Ammonia
Ammonium Sulfate
Formaldehyde
Acetaldehyde
Pyridines
Benzene
Toluene
Xylene
o,m,p-Cresol
Thiophenes
Lead
Mercury
Selenium
Phase
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Toxicity
W-l
W-l
W-l
W-2
W-l
W-l
W-2
W-l
W-l
W-l
W-l/C-3
W-l
W-l
W-l
W-l
Reference
A-5, 7
A-8
A-5
A-8
A-8
A-8
A-8
A-8
A-8
A-8
A-5
A-8
A-8
A-8
A-8

-------
Table 3-11 (continued).  (I)  Tar Separation
Chemicals Potentially Present
Status Emission Class Specific Components
23. Organometallics Nickel Carbonyl
25. Cyanides Hydrogen Cyanide
Ammonium Cyanide
Ammonium Thiocyanate
Suspected Present/ 22. Trace Elements Arsenic (arsenic
Known Hazardous tr iodide, sodium
arsenate, sodium
arsenite)
Barium (acetate,
chloride, nitrate)
Cadmium (chloride,
nitrate, sulfate)
Vanadium (pentoxide,
vanadyl sulfate)

Phase
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous



Aqueous

Aqueous

Aqueous


Toxicity
W-l/C-1
W-l
W-l
W-l
W-l/C-4



W-2

W-l

W-2

Reference
A-6
A-5
A-8
A-8
A-8



A-8

A-8

A-7, 8,













9


-------
Table 3-12.  POTENTIAL FOR FUGITIVE  EMISSIONS FROM ADVANCED COAL PROCESS MODULE

Module
No. Process Name
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
Slurry Preparation
Reactor
Reactor Separator
Condenser
Filtration
Water-Oil Separation
Fractionation
Hydrotreating
Hydrocracking
Storage
Acid Gas Treatment
Hydrogen Separation
Sulfur Plant
Coal Preparation
Oxygen Blown Gasification
Quenching and Cooling
Tar Separation
Pres-
sure
low
high
med-high
low
low
med
low
high
high
low
low
high
low
low
high
low
low
Potentially
Tempera- Hazardous Corrosive-
ture Volatiles ness
low
high
high
med
med
low
med
high
high
low
low
high
high
low
high
med-high
low
med
high
high
med
high
high
high
high
high
med
high
low
high
med
high
high
high
low
med
med
high
med
low
med
med
med
low
med
med
med
low
med-high
high
med
General
House-
keeping
med
med
med
med
med
poor
med
med
med
med
med
med
med
poor
med
med
poor
Potential
for Hazardous
Fugitive
Emissions
med
high
high
high
med
high
high
high
med-high
med
med-high
low
med-high
med
med-high
med-high
high

-------
                    Table 3-12 (continued).  POTENTIAL FOR FUGITIVE EMISSIONS FROM ADVANCED

                                            COAL PROCESS MODULE
o
oo


Module
No. Process
18
19
20
21
; 22
1
23
24
25
Shift Conversion
Phenol Recovery
Acid Gas Removal
Methanation


Pres-
Name sure

(Phenosolvan Process)
(Rectisol Wash)

Further Gas Purification (Rectisol
Wash)
Sulfur Recovery
(Stretford Process)
Air Blown Gasification
Storage

high
low
low
high
low
low
high
low

Tempera-
ture
high
med
low
high
low
low
high
low


Potentially
Hazardous Corrosive-
Volatiles ness
low
high
high
low
med
med
high
med
low
med
low
low
low
low
med-high
low

General
House-
keeping
good
med
med
good
med
med
med
med
Potential
for Hazardous
Fugitive
Emissions
low-med
med
med
low
med
low-med
med-high
med

-------
RECOMMENDATIONS

          Because of the short-term nature of this study, it was
necessary to accumulate process and chemical data from known and
readily available sources.  There was little time for follow-up
and confirmation work on the data sources.  The final assessments
concerning the degree of potential hazards involved with the emis-
sions was not sharp.  Most of the classifications were in the
suspected range.  The following recommendations are aimed at
confirming,  expanding, and sharpening the data base in anticipation
of subsequent test programs.
          (1)  Confirmation and expansion of the data base,
especially as it relates to Class 1 emissions, should be performed
in the following manner:
          •  Additional literature searches should be made to
             increase the data base on compositions of all process
             flow streams in the three primary process modules.
             This would include accumulating examples of all
             stream components, both hazardous and nonhazardous,
             contained in flow streams, plus operating tempera-
             tures, pressures, and material balances.
          •  Additional literature searches and investigation of
             industrial experience regarding analyses performed
             on operating plant streams should be made.  In the
             case of advanced coal processes, these studies can
             be initiated in the existing pilot plants located
             in the United States.  In addition to specific
             chemical analysis (mostly by GC), boiling point
             curves, carbon residues, tests for aromaticity,
             nitrogen and sulfur analyses could be helpful in
             better r.har.icterizing the streams.
          •  The disposition of all components within each process
             module should be assessed.  For separations, the
             distribution of primary, trace, and hazardous
             components should be predicted.  For reactions,
             molecular rearrangements should be estimated.
                              109

-------
           •  The assessment  as  performed in this  report  should
              be repeated but with improved input  on process
              modules and chemicals.
          (2)  The compatibility of the classes used for  process
assessment with classes that  would be best from the standpoint of
a long-range analytical strategy should be evaluated.
          •  The suitability  and completeness of the chemical
             classifications  suggested by EPA in light of more
             detailed analyses of plant streams should be assessed.
             Classes for hazardous components not presently
             detected should  be added.  Regrouping or expansion of
             classes may also be indicated.
          (3)  A better grading of the toxic and the carcinogenic
compounds should be made through a more organized and thorough
study of the health effects of the concerned compounds.
          (A)  A methodology for selecting the best sampling
points for hazardous emissions should be developed, including a
          •  Compilation of a list of locations within petroleum
             process modules, conventional coal process modules,
             and advanced coal process modules where future sam-
             pling should be performed, and an
          •  Outline of a program for determining the level of
             hazardous emissions from fugitive sources.  This could
             include tests at specific points within the process
              (such as pump seals and valves).
                               110

-------
                           SECTION IV
                       SUMMARY OF RESULTS

          A summary of all emission classes from the stream classes
specified are included in Table 4-1 and Table 4-2.  These tables
indicate the status of the potentially hazardous chemical classes
from the specific emission sources.  The 25 chemical classes are
described in Table 2-1, and the specific emission sources or streams
are described in Tables 3-2, 3-5, and 3-10 for the petroleum, conven-
tional coal, and advanced coal process modules, respectively.  The
gaseous, aqueous, and solid phases of the chemical classes are
designated by "a", V, and "s", respectively.  The status numbers,
as described in Section II are also incorporated into these matrices.
Table 4-3 lists the potentially hazardous chemicals which have been
included in this study.

-------
Table U-l.   POTENTIALLY HAZARDOUS  CHEMICAL GLASSES IN CLASSIFIED  STREAMS  OF PETROLEUM PROCESS MODULE

*. Erne Varer Systt'.s
B. SCUT .">qi.eous Cor.dersates
C. ^Cid Gas Solvent Regeneration
D. Claris Plant Tail Cas
l-i E. Fved Bad Catsl/st Regeneration
f° Croi.p I
F. r i>.ad Bed Catalyst Regeneration
Croup TI
C. :"ixcJ Bed Cardlyst Rcgereration
Cr.iup III
H. Fixer Bed Catalyst Pejjeneral ion
Cro ip IV
I. Movirg Bed Catalyst Rcgcreration
J. Burorcrnc Condenser Off Cas
K. Fluid Coker Off Gas
L. Abplialt Air Blowing
M. Spert Acid Sludge
X. Dccoking
srmixcAii.w + saiov
2v
2w
2w








2a
w
2w

ALCOHOLS
1

2w










2w

AMINES
« 1

2w
2w
2a




2a

2a



INORGANIC SAL'J'S
c> 1
2w











2w

CO
a
S
V
8
0 •>
2w
2u






3a
2a
3a
2a
w
2u

CO.-IBUSTION GASES
ON



2s
2a
2a
2&

2a

2a


2a
EPOXIDES
-











i


ETHERS
00














HALOCARBONS
* 1














^HETEROCYCLIC
o \
2w
2w




3a

3a
2a
3a
la
w
2u

^HYDROCARBONS
!-• 1
2w
2w



2a
2a

2a
2a
23
2a
w
2w
2a
_HYDROPEROXIDH:S
M J














^LACTONES
u.
Iw









3a
3a
w
3u

^NITRO COMPOUNDS
*• 1














^NITROSAMINES
1








3a





C/l
Ed
a
§














^PliROXIDES
•>j 1














CO
J
1
L
18
2w
2u






2a
2a
2a
2a
w
2u

_POLYatLORINATED
^POLYNUCLEAR |














^POLYNUCLEAR
P 1
3w
3w



3a
3a

la

3a
la
3w
3a
MSULFUR COMPOUNDS
1""* 1
2w
2u
2w
la

la
la
w
la

la
2a
V
2w
la
^TRACE ELLMLNTS
1
3w
3w




2a

la
2a
la
2w
3w
2a
WORCANOMI:TALLICS
|w |
3u
3w




3a



2^
w
2v,

L/INi: PARI'ICULAILS
r



2a
2a
2a
2a

la

la
2a

2a
en
j
i

2'.7
2w
3a




2a

2a




-------
Table 4-1.  (Continued)   POTENTIALLY HAZARDOUS  CHEMICAL  GLASSES  IN CLASSIFIED STREAMS OF  PETROLEUM PROCESS MODULE






0. Oil Fired Process Haaters
P. Cooling Water Systc-s
Q. Storaije & Bii-rdin^;
Crcup I
R. Storage & Blend Lng
C.roup 11
S. Storage Ci olcnding
Grji? Ill
T. I'ucjiclve Fnissions

U. Flares
V. API Crit Cha-.bers
W. Biolobical Sludges
X. Spont Catalysts
V.
r^


a
l-l
u
1

2w
3a




2w

?w
a

3s


	



ALCOHOLS
2

,a
w






?w
a

3s






AMINES
3

w


2w



1W
a
2a
3s

2s


fi~~I
•a.

r_i 1 0
INORGANIC SAL
4

2w






3w


3s

2s
CARBONYL COJ1P
•j
2a
3a
w
2a



?w
a

V.
u

COMBUSTION CA
6
2a







3W
a
2a
3s

2s

2a







E VOX IDES
7


















ETIICRS
8

3a
w






w
a








HALOCARBONS
9


















HliTEROCYCLIC
10
3a
3a
w




V
a
1W
a
3a
3s

3s




HYDROCARBONS
11

w
2a

?w
a
?w
a
?"
a
2a
3s

2s



tfl
HYDROPCROXIDE
12


















I.ACTONES
13

3a
w






1W
a

3s





Q
NITRO COMPOUN
14


















NITROS AMINES
15

3a
w






„
a

3s

3s




OZONIDES
16


















PEROXIDES
17


















PHENOLS
18

2w
3a


2w

2w

?w
a

3s




9
U
POLYCHLORINAT
POLYNUCLEAR
19


















POLYNUCLCAR
20
la
3a
w




i"
a
1U
a
3a
3s

3s

y>

z
1
S
21

2w
3a




2u

1"
a
2a
3s

2s



!A
z
LJ
U
S
H
22
2a
3iv
2a



2w

1"
a

3s
3s
2s



u
ORGANOMCTALLI
23

3a
w


3w

3w

3W
a

3s
3s
3s
CO
UJ


FINI: PARTICUF
24
la







3a

2a







CYANIDES
25

3a
w






,«
ai
2a
3s



-------
              Table 4-2.  POTENTIALLY HAZARDOUS CHEMICAL CLASSES IN THE CLASSIFIED STREAMS OF
                          CONVENTIONAL COAL PROCESS MODULES








A. Coal Preparation
B. Coke Oven Off Gas
C. Quenching & Direct
Cooling Operation
D. Boiler Off Gas
E. Storage & Blending
Group II
F. Ash





w
ACID AND
ANHYDRIDE
1
3w
2a


2a









AMINES
3

l,2a*
l,2a*
2w
2,3a*
Iw


CO
H

5
CO

INORGANIC
4


2w

la









CO
5

2a
2a

2,3a*








z
COMBUSTIO
GASES
6

la
la

l,2a*





CO
u
M
l-l
U
10

3a
2w
3a
l,2,3a*






VJ
fe^
Q
1
11

3a
2w
3a

la
w







PHENOLS
18

3a
l,2w
3a
3a
Iw






et
a
POLYNUCLE
20

l,2,3a*
l,2,3a*

l,2,3a*









SULFUR
COMPOUNDS
21

2,3a*
2,3a*
2w
3a




CO

55
W
JQ
|
22
3s
2,3a*
2,3a*
2,3w*
2a


3s






ORGANO
METALLICS
23

la
la
2w

3w





CO
w

PARTICULA
24
la
l,3a*
l,3a*

la


3s






CYANIDES
25

l,3a*
l,3a*
2w





*Potentially hazardous chemicals in this chemical class were found in more than one status.

-------
           Table 4-3.  POTENTIALLY HAZARDOUS CHEMICAL CLASSES  IN THE CLASSIFIED  STREAMS
                       OF ADVANCED COAL PROCESS MODULES





A. Coal Preparation
B. Quenching Direct
Cooling Operations
C. Sour Aqueous Condensate
D. Fixed-Bed Catalyst
Regeneration
E Barometric Condenser
Off Gas
F. Storage and Blending
G. Sulfur Plant
H. Reactor Off Gas
I. Tar Separation
i


ACIDS AND
ANHYDRIDES
1
3w


2w





2w

2w



ALCOHOLS
2



2w




w






AMINES
3

Oa
w
2w





2a
2a
2w

CO
H
3
INORGANIC S
4











2w



CARBONYLS
5



2w


3a



La
2w



COMBUSTION
GASES
6




2a




2a
2a



CO
u
HETEROCYCLI
10

3a

2w
3a

3a



3a
2w


CO
HYDROCARBON
11
3*
2a

2w
2a

3a

2a

2a
2w



PHENOLS
18
<
l,2w*
2w
2w


3a

3a
2w j

3a
l,2w*



POLYNUCLEAE
20

3a


3a



3a
3a
3a




SULFUR
COMPOUNDS
21
3a
l,3a*
l,2w*
2w
la

3a


la
l,3a*
2w

CO

a
w
H
22

3a
w
3w
2a



3w
3a
3a
2w



ORGANO
METALLICS
23




3a






2w


CO
r*l
PARTICULATI
24
l,3a*



2a




2a

3w



CYANIDES
25

2,3w*






3w


2w
*Potentially  hazardous  chemicals  in  this  chemical  class were found in more than one  status.

-------
        Table  4-4.  LIST OF POTENTIALLY HAZARDOUS CHEMICALS
Chemical
Classification
(1) Acid and
Anhydrides



(2) Alcohols
(3) Amines



Compounds
Maleic Anhydride
Benzoic Acid
Carboxylic Acids
Cresylic Acid
Acetic Acids
Formic Acids
Su If uric Acid
Hydroxybenzoic Acid
Hydrochloric Acid
Nitric Acid
Anthraquinone Disulfonic
Acid
Aliphatic alcohols
Aromatic alcohols
Diethylamines
Methylethylamines
Aromatic Amines
Ammonia
Aliphatic Amines
Aromatic Amines
crf$ Naphthyl Amine
4-aminobiphenyl
Aniline
Methyaniline
Benzidine

Petro-
leum
w
w
w
w
w
w
w/a


w
w
w/a/s
w/a/s
s
w/a
w
w/a


Phases
Conven-
tional
Coal
w
a
w
w
a
a
a


w/a
w
w
a
a
a
a
a

Advanced
Coal
w
w
w

w
w
w
a
a
w/a



(4)  Inorganic
    salts
(5)  Carbonyl
    Compounds
(6)
Combustion
Gases
            Ammonium sulfate
            Chromium/CrCl-.CrS
            Chlorides
            Sulfates
            Chromates
Ketones
Aldehydes
Formaldehyde
Acetaldehyde
Paraldehyde

Carbon Monoxide
Sulfur Oxides
Nitrogen Oxides
                                                w
w
w
w

w/a/s
w/a/s
  a
  a
  a
  a
  a
                                                            w/a
                                                            w/a
w/a
w/a
  a

  a
  a
  a
a
a
a
                                 116

-------
Table 4-4'(continued).  LIST OF POTENTIALLY HAZARDOUS CHEMICALS
Phases
Chemical
Classification
(10) Hetero-
cyclics











(11) Hydrocar-
bons




(13) Lactones
(18) Phenols







(20) Polynu-
clears












Compounds
Pyridines
Pyrroles
Qu inclines
Indoles
Furans
Alkyl Pyridine
Phenyl Pyridine
(Mono) Benzofurans
Alkyl Quinolines
Benzo(f )quinoline
Benao(h)qu incline
Indeno( 1 , 2 ,3- i j) isoquinoline
11 H-Indeno(l,2-b)quinoline
Benzene
Toluene
Xylene
Aliphatics
Olefins
Alkylbenzene

Phenol
Dimethyl Phenol
Cresols
Xylanols
Thiophenols
Phenyl Phenols
Alkyl Phenols
Alkyl Cresols
Carbazoles
Anthracenes
Benzo(a)pyrene
Pyrene
Benzo(e)pyrene
Perylene
Benzo(ghi)perylene
Coronene
Anthracene
Phenanthrene
Fluoranthene
Chrysene
Dibenzo (a ,h) anthracene
Dibenzo(a,g)f luorene
Petro-
leum
w/a/s
w/a/s
w/a/s
a/s
w/a/s


w/a





w/a/s
w/a/s
w/a/s



w
w/a/s
w
w/a/s
w/a/s
a/s



w/a/s
w/a/s
w/a
a/s
a
a/s
a
a
a
a
a



Conven-
tional
Coal
w/a

a


a
a
a
a
a
a
a
a
w/a
w/a
w/a
a
a
a

w/a

w/a
a

a
a
a
a
a
a
a
a
a

a
a
a

a
a
a
Advanced
Coal
vila
w/a





a





w/a
w/a
w/a
a
a


w/a
w
w/a
w/a

a
a
a

a
a

a
a
a
a

a
a
a


                                  117

-------
Table 4-4 (continued).  LIST OF POTENTIALLY HAZARDOUS CHEMICALS
Chemical
Classification
(20) Polynu-
clears
(Continued)





















(21) Sulfur
Compounds












(22) Trace
\ *
Elements


Compounds
Methylchrysene
Benzo(a) anthracene
Dimethylbenzoanthracene
Biphenyl
Naphthalene
Alkyl Naphthalene
Phenyl Naphthalene
Tetralin
Methyltetralin
Acenaphthylene
Acenaphthene
Fluorene
Alkyl Anthracenes
Alkyl Phenanthrene
Acr id ine
Benzocarbazoles
Alkyl Acridines
Benzo(a) anthrone
Dibenzo(a, l)pyrene
Dibenzo(a.n) pyrene
Dibenzo (a , i) pyrene
Methyl Pyrene
Indeno( 1 , 2 , 3-c ,d) Pyrene
Benzoacridine
Sulfides
Sulfites
Sulfonates
Sulfones
Mercaptans
Thiophenes
Hydrogen sulfides
Methyl Mercaptans
Carbon Disulfides
Carbonyl Sulfide
Thiosulfide
Dibenzo Thiophene
Alkyl Sulfide
Ethyl Mercaptans
Methyl Thiophene
Vanad ium
Nickel
Zinc
Lead

Phases

Conven-
Petro- tional Advanced
leum Coal Coal
























w/a/s
w/ /s
w/a/s
w/ /s
w/a/s
w/a/s
w/a
w
w/a
w/a
w
w/a
w/a


w/a/s
w/a/s
w/a/s
w
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a










w/a
a
a
a
a



a
a
a/s

s
a/s

a












a


a
a
a
a
a
a
a
w

w

a
w/a
a
a
a
a




a
w/a
a

a
                                   118

-------
Table 4-4 (continued).  LIST OF POTENTIALLY HAZARDOUS CHEMICALS
Phases
Chemical
Classification
(22) Trace
Elements
(Continued)


















(23) Organo-
metallics


(24) Fine
particu-
lates





(25) Cyanides




Compounds
Cobalt
Molybdenum
Copper
Strontium
Barium
Beryllium
Selenium
Arsenic
Cadmium
Silver metals & soluble
compounds
Mercury
Ant imony
Arsenic (arsenic trioxide,
sodium arsenate, sodium
arsenite)
Fluorine
Uranium
Thallium /Thallium Oxide
Phosphorous
Manganese
Metal loporphyr ins
Nickel Carbonyl
Cobalt Carbonyl
Tetraethyl lead
Sulfur Particulates
Carbon Compounds
Catalyst Fines
Coke
Carboniferous Compounds
Respirable Coal Dusts
Tar
Soot
__
Hydrogen Cyanide
Ammonium Cyanide
Naphthyl Cyanide
Ammonium Thiocyanate
Conven-
Petro- tional
leum Coal
a
a
a/s s
w/a
w/a w/a/s
a/s
a/s
a/s
w/a/s
a

a/s
a/s
w


a/s
a/s
a/s


w /s
a a
a
w w
a
a
a
a a
a
a/s
a
a
w/a
a
a
a
a
Advanced
Coal
a
a

w

a
w/a

a


a
a
w





w/a
a

a
a

a

a
a





w


w
                                 119

-------
                           SECTION V
                           APPENDIXES
                                                               Page
A.  Fact Sheets of Petroleum Process Modules ........
B.  Fact Sheets of Conventional and Advanced Coal
      Process Modules  ...................    135
C.  Bibliography ......................    148

-------
                             APPENDIX A
               FACT SHEETS OF PETROLEUM PROCESS MODULES

                             Production
                              1.  Gas Wells
                              2.  Oil Wells
                             42.  Gas/Oil Wells

•  Wells generally produce a wide variety of hydrocarbon compounds
   ranging from methane through very heavy oils.

•  Crude and natural gas is often produced under high pressures and
   temperatures.

•  Remoteness of wells results in poor housekeeping and maintenance.

•  Acidic crudes and brines are corrosive.

•  Fugitive emissions and spills, attributable to poor housekeeping,
   high pressures and corrosive environment, contain small quantities
   of the hazardous components found in crude and gas.

•  Effluent waste streams are limited to fugitive emissions and spills.
•  H_S found in many natural gases and crudes is very toxic.

-------
                          Field Separations
                          3a.  Gas-Condensate Separation
                          3b.  Gas-Oil Separation
                          3c.  Crude Separation

•  Primary function is to physically separate the gas, crude oil, and
   aqueous brine phases.

•  Emulsion breaking operations are included if necessary.

•  Intermediate temperatures are encountered if thermal emulsion
   breaking is employed.

•  High pressures are involved if the well pressures are high.

•  Primary effluent waste stream is oily brine which has been in
   contact with crude and possibly will leach out some toxic compounds.

•  Remoteness of some field separation units lead to poor house-
   keeping and maintenance which result in fugitive emissions and
   leaks.

•  Acidic crudes and brines are corrosive, and contribute to leaks
   and fugitive emissions.
                                   122

-------
                   Raw Products Storage Facilities
                    4.  Condensate storage and loading
                    5.  Crude storage (field)
                   11.  Gasoline storage and loading (field)
                   12.  Crude storage (refinery)

•  Field storage facilities are used to store raw petroleum products
   prior to shipment.

•  Most raw products are shipped by pipeline.

•  Field storage facilities often include loading facilities for
   transporting low volume products by rail or truck.

•  Major emission streams are aqueous wastes decanted from storage
   tanks, and volatile products evaporating from vented tanks and
   loading facilities.

•  Hazardous compounds present in the product may leach into the
   decanted aqueous wastes.

•  Volatile hazardous compounds are suspected present in vented
   vapors.
                                 123

-------
                          Acid Gas Removal
                           6.  Acid Gas Removal (field units)
                          15.  Acid Gas Removal (refinery units)

•  Employed for the removal of acid gas species from gaseous hydrocarbon
   streams.

•  Commonly absorbs the acid gas species in an amine solution.

•  Operating pressures and temperatures are low.

•  The corrosive environment is conducive to leaks and spills.

•  Effluent acid gas stream contains hazardous compounds including
   H2S, COS, CS2, CH3SH, CO, and HCN.

•  Regeneration of spent amine solution is expected to release amines,
   acid gas species and any other hazardous compounds existing in
   gaseous hydrocarbon streams.
                        Sulfur Recovery Units
                         7.  Sulfur Recovery (field)
                        16.  Sulfur Recovery (refinery)

•  Purpose is conversion of acid gases to salable elemental sulfur.

•  Commonly employ the Claus process which involves high reaction
   temperatures in a relatively corrosive environment.

•  The major effluent stream is the tailgas which may contain
   unreacted sulfur compounds and other hazardous compounds which
   enter with the acid gases.

•  The corrosive environment is conducive to leaks and spills, and
   consequently fugitive emissions.
                                  124

-------
                           8.  Dehydration

•  Employed for the dehydration of gaseous hydrocarbon streams.

•  Most common processes involve glycol absorption, silica gel
   adsorption, or molecular sieve adsorption of the water vapor.

•  Pressures are low and temperatures are moderate.

•  Primary effluent stream is the recovered water which may contain
   glycols and traces of sulfur compounds not removed by the acid
   gas removal system.
                        Light Ends Separation
                          9.  Gas  Separation
                        17.  Gas  Processing

 •   Separates  desulfurized light hydrocarbon  streams  into  their  primary
    compounds  (predominantly  C,, C^,  C^,  C^,  and  C^+).

 •   Separation processes include compression,  refrigeration,  absorption,
    adsorption,  or a combination of these.

 •   Temperatures are low and  pressures are  intermediate.

 •   Hazardous  compounds are rarely present  in these units  in significant
    quantities.

 •   Generally  considered one  of  the cleaner petroleum processes.
                                 125

-------
                    10.  LPG Storage and Loading

•  LPG is stored and  loaded under moderate and high pressures.

•  Temperatures involved are low.

•  Although the elevated pressures are conducive to fugitive
   emissions, hazardous compounds are generally not found in LPG
   streams.
                           13.  Desalting

•  For the removal of inorganic salts and brines from incoming crude.
   These salts lead to fouling, corrosion, and catalyst poisoning.

•  Crude is heated to lower its viscosity and contacted with process
   water to absorb impurities from the crude.

•  Electrostatic charges are commonly employed to deemulsify the
   organic and aqueous phases.

•  Chemical deemulsifying is a little used alternative.

•  Primary effluent stream is a gritty brine containing small
   quantities of hazardous compounds in the crude, especially trace
   metal salts.

•  Housekeeping is fair and fugitive emissions are not expected to be
   a problem.
                                126

-------
                          Crude Separation
                          14.  Atmospheric Distillation
                          18.  Vacuum Distillation

•  Atmospheric and vacuum distillation are used to separate the
   components of crude into various boiling point fractions.

•  Stripping steam and vacuums are used to depress the boiling points
   of heavier fractions.

•  High temperatures are involved in the process.

•  Sour condensates are the primary effluent stream and due to their
   intimate contact with the crude, contain small quantities of the
   hazardous compounds found in crude oil.

•  High temperatures, corrosive environments, poor maintenance, and
   the presence of hazardous compounds combine to make these units
   prime sources of potentially hazardous fugitive emissions.
                      19.  Hydrogen Production

•  Commonly employ  steam reforming of a clean hydrocarbon feedstock.

•  Hydrocarbons and steam are reduced to CO- and E^.

•  Processing  temperatures and  pressures are both high.

•  No direct effluent waste  streams.

•  Fugitive emissions can be high because of high operating
   temperatures and pressures;  however, the presence of hazardous
   compounds is dependent on the hydrocarbon source selected.

                                 127

-------
                    20.  Catalytic Polymerization

•  Feed is light olefins.

•  Produces a gasoline blending stock.

•  High temperature.

•  High pressure.

•  Being phased out as feedstocks are in demand for petrochemical
   production.

•  Main emissions from heaters and regeneration of fixed bed
   catalyst.
                           21.  Alkylation

•  Feed is light isoparaffins and olefins.

•  Produces high octane, branched paraffin gasoline blending stock.

•  Low temperature.

•  Intermediate pressure.

•  Catalysts are highly concentrated sulfuric and hydrofluric acids,

•  Main emissions are from the process heater.
                                  128

-------
                         22.  Isomerization

•  Rearranges straight chain paraffins to branched chain for octane
   improvement.

•  Catalyzed by platinum-aluminum oxide catalyst.

•  High temperature.

•  High pressure.

•  Main emissions from heaters and catalyst regenerations.
                       24.  Catalytic Reforming

 •   Produces  a high  octane  aromatic  blending stock.

 •   High temperature.

 •   Intermediate-to-high pressure.

 •   High interest in recent years caused by no-lead gasoline
    requirements.

 •   Main emissions result from process heaters and regeneration of
    fixed bed catalyst.
                                   129

-------
                      26.  Chemical Sweetening

•  Converts mercaptans to sulfides in liquid petroleum streams.

•  Low temperature.

•  Low pressure.

•  In limited use with advent of chemical inhibitors for product
   sweetening.

•  Main emissions from the regeneration of the fixed bed catalyst,
                        Hvdrodesulfurization
                        23.  Naphtha HDS
                        27.  Kerosene HDS
                        28.  Gas Oil HDS
                        33.  Lube  Oil HDS
                        35.  Residual Oil HDS

 •  Removes  sulfur  and nitrogen  from liquid  feeds.

 •  Produces tUS  and  NH« which are  steam stripped and sent  to Acid
   Gas  Removal.

 •  High temperature.

 •  High pressure.

 •  Emission streams:
    (1)   Aqueous  condensate
    (2)   Catalyst regeneration flue gas
    (3)   Process  heater flue gas.

                                 130

-------
                         Catalytic Cracking
                         29.  Fluid Bed
                         30.  Moving Bed

•  Converts heavy distillates into lighter components.

•  High temperature.

•  Low pressure.

•  Emission streams:
   (1)  Aqueous condensate
   (2)  Regenerator flue gas
   (3)  Process heater flue gas.

•  Benzo(a)pyrene measured on catalyst emitted from regenerator.


                         31.  Hydrocracking

•  Converts heavy gas oils into desulfurized gasolines and light
   hydrocarbon  fractions.

•  High temperatures.

•  High pressures.
•  Produces H-S and NH, which are steam stripped and sent to Acid
   Gas Removal.
9  Emission Streams:
   (1)  Aqueous condensate
   (2)  Catalyst regeneration flue gas
   (3)  Process heater flue gas.

•  Generally not among the processes being included in new refineries.
                                  131

-------
                         34.  Deasphalting

•  Separates asphalts from vacuum resids by extraction vith propane
   or light hydrocarbon solvent.

•  High temperature.

•  Low pressure.

•  Emissions result from an aqueous condensate stream and process
   heater flue gases.
                          36.  Visbreaking

•  Produces a maximum amount of fuel oil (minimizes gasoline) from
   topped crude.

•  Thermalcracking.

•  High temperature.

•  Low pressure.

•  Emission Sources:
   (1)  Process Heater Flue Gas
   (2)  Aqueous Condensate
   (3)  Barometric Off Gas
   (4)  Decoking.

•  Sulfur compounds  (H»S, COS) are emitted during decoking operations,

•  Not being considered in current refinery design plans.
                                  132

-------
                             37.  Coking

•  Converts residual oil to coke and to wide range of gaseous and
   liquid fuel products.

•  High temperature.

•  Low pressure.

•  Emission sources:
   (1)  Aqueous Condensate
   (2)  Process Heater
   (3)  Coking Off Gas.

•  Fine coke particles emitted in the off gas will contain trace
   elements and possibly some polynuclear components.
                      39.  Lube Oil Processing

•  Converts desulfurized lube oils into marketable lube stocks,

•  Medium temperatures.

•  Low pressure.

•  Main Emission Streams:
   (1)  Aqueous Condensate
   (2)  Process Heater Flue Gas
   (3)  Catalyst Regeneration Gases
   (4)  Spent Acid Sludge.
                                  13J

-------
                      40.  Asphalt Air Blowing

•  Polymerizes raw asphalts to a more viscous product asphalt.

•  High temperature.

•  Low pressure.

•  Emissions are found in the process heater flue gases and the
   off gases from air blowing.

•  Polynuclear and heterocyclic compounds have been found in the
   off gas from this unit.
                                  134

-------
                          APPENDIX B

                 FACT SHEETS OF CONVENTIONAL
               AND ADVANCED COAL PROCESS MODULES
                     1.  Coal Extraction

Two major types of coal extraction:
(1)  Underground mining
(2)  Surface mining.

In underground mining, the mining machines (giant saws and
mechanical "moles") are used.  In surface mining, giant
mechanical shovels are used to remove the overburden and to
dig up the coal.

Major hazardous emission is the respirable coal dust.  The modern
mechanized mining methods have increased the emission.
                              135

-------
                          Coal Preparation
                           2.   Crushing and Grinding
                           3.   Gravity Separation
                           4.   Froth  Flotation
                           5.   Thermal Drying
                          19.   Slurry Preparation

•  The purposes of the gravity separation and froth  flotation are
   to remove partially the ash and some pyritic sulfur of coal.

•  Grind coal to various sizes according to its application.  Ball
   mills are commonly employed to prepare coal for the utility
   furnaces.

•  Two major emission sources:
   (1)  Respirable coal dust in handling and transporting coal
   (2)  Tailings from the physical separation of coal.
                                 136

-------
                       6.  Slot Type Coke Oven

•  The slot type coke oven consists essentially of three main parts:
   coking chamber, heating chamber, and the regenerative chamber.

•  The coal is charged through openings in the top of the oven.  The
   coke is pushed out from one end by a power-driven ram or pusher,
   acting through the other end.

•  The coking time depends on the depth of coal and usually ranges
   from 16 to 20 hours.

•  The coking temperature is from 1700 to 2700 F.

•  In the coking period, the volatile materials of coal are released.
   Some known carcinogens have been identified in this gas stream.

•  The potentially hazardous materials are emitted during the charging,
   coking, and pushing operations.
                                 137

-------
                 7.  Volatile Collection and Cooling

•  The volatile products are carried through the ducts in each oven
   top and are collected in the main.

•  A liquid spray is installed in the main to cool the gas.

•  This flushing liquid which contains the condensate from the volatile
   products is collected for further chemical recovery processes.

•  The gas stream passes through an electrostatic precipitator to
   further remove the tar from raw coke-oven gases before it enters
   the ammonia recovery unit.

•  The gas stream contains many potentially hazardous materials and
   fugitive emission is high.
                                  138

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                            Tar  Treatment
                             8.   Tar  Liquor Decantation
                            35.   Tar  Separation

•   The  primary  objective  is to  separate the condensed  tar from
    the  liquor.

•   The  tar  settles  in the flush-liquor decanter tank because  of its
    high density.

•   The  overflow is  recycled back to  the volatile collection and
    cooling  unit.

•   Operating  temperature  and pressure are  low.
                        9.  Ammo.nia Recovery

•  Three different methods are currently used to recover ammonia from
   the coke-oven gases as ammonium sulfate:
   (1) Direct process — the tar-free coke-oven gases are passed
       through a saturator containing a solution of  sulfuric  acid
   (2) Indirect process — ammonia is scrubbed off the coke-oven
       gases by water and is recovered from water by distillation
       and alkaline treatment.  Then, the ammonia is passed through
       a sulfuric acid saturator
   (3) Semi-direct process -- ammonia is removed from the flush
       liquor by distillation and alkaline treatment and then is
       passed through the sulfuric acid saturator.

•  The operating temperature is medium.
                                 139

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                       10.  Pyridine Recovery

•  The primary function is to recover the pyridine bases from the
   coke-oven gases.  These bases include pyridine, picolines (methyl
   pyridines), lutidines  (dimethyl pyridines), etc.

•  There are two types of recovery processes:
   (1)  Continuous -- the saturator liquor from the ammonia recovery
        unit is passed to a neutralizing still where the pyridine
        bases, ammonia, carbon dioxide and water, are given out as
        overhead gases.  These gases are condensed and the pyridine
        bases are  separated from this ammonium carbonate solution
        as a top liquid layer
   (2)  Batch-type -- the pyridine bases are  recovered by distillation
        of the saturator  liquor and are purified  by a series of
        cooling and  fractionation operations.

•  Operation temperature  is medium.
                                   140

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                         11.  Phenol Recovery

•  Phenol is recovered from the liquor in the ammonia recovery unit.

•  Two methods are available to recover phenol from the ammonium
   liquor:
   (1)  Vapor-Recirculation Process — Phenol is steam-stripped off
        the liquor which contains phenol, ammonia and other soluble
        carbonization products.  The phenol is extracted from the
        water-phenol mixture by caustic soda to form sodium phenolate.
   (2)  Solvent Extraction Process -- The phenol is extracted out
        from the liquor by benzene or light oil in which phenol
        is more soluble than water.  The extraction is a counter-
        current flow process.  The phenol is then removed from the
        solvent by reacting with caustic soda to form sodium
        phenolate.

•  Operating temperature is medium and the pressure is low.

•  The degree of corrosiveness depends on the concentration of
   sodium hydroxide.
                                 141

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                         12.  Coke Quenching

•  The purpose of coke quenching is to stop the further combustion.

•  There are two methods of quenching:
   (1)  Wet Quenching — the coke is loaded in the quenching cars
        which are carried to the quenching station by an electric
        locomotive, where the coke is quenched with water
   (2)  Dry Quenching -- the coke is put in a closed system in
        which air is circulated to pick up the sensible heat from
        the coke.  The hot air is used to generate low pressure
        steam.

•  Overall operating temperature is medium to high.

•  High fugitive emission of volatile matters from coke is expected.

                        13.  Light Oil Recovery

•  To recover the  light hydrocarbons  from the coke-oven gases.

•  Three major constituents to be recovered are benzene, toluene
   and xylene.

•  Three methods are available for  light oil recovery:
    (1)  A  series of refrigeration  (-70 C) and compression  (10  atm)
    (2)  Adsorption by activated carbon which is regenerated by
        direct or  indirect  heating  of steam
    (3)  Absorption by a liquor solvent which is recovered  by
        steam distillation.

•  Temperature ranges from  low to medium and pressure  from low to  high.

•  No corrosive environment exists  in this  section.  Oil spill and
   housekeeping will be major factor  in fugitive  emission.

                                 142

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                               Storage
                               14.  Storage (Coking)
                               28.  Storage (Liquefaction)
                               43.  Storage (Gasification)

•  A large variety of hydrocarbons are stored as end-products or
   intermediate products.

•  The coal tar is usually piled up on the open ground.  Hazardous
   volatile materials are involved in this storage  area of coal tar,

•  Temperatures involved are low.

•  The hydrocarbons are stored under moderate and high pressure.


                     20.  Reactor  (SRC Process)

•  Dissolve the coal in a solvent with hydrogen.

•  Temperature and pressure  involved are high  (825  F  and  1000  psi).

•  No continuous  emission from the  pressurized  vessel.  Fugitive
   emission from  the high pressure  pump and valves  is expected.

•  Reactor accident  such as  rupture of  safety  head  will emit the
   potentially hazardous materials.

                       21.  Reactor  Separator

•  Separate the gases  from the reaction products.

•  Separation is  done  by flashing the reaction products.

•  Temperature is high and pressure  is moderate.

                                  143

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                            Gas Treatment
                            22.  Condenser
                            24.  Water Oil Separator

   Cool the gases from the flash tank and separate the oil from the
   condensate.

   Temperature  and pressure involved ranges from low to moderate.
                       Gasifier (Lurgi Process)
                       33.  Oxygen Blown Gasification
                       42.  Air Blown Gasification

•  Combustion of coal to produce methane.

•  Methane is produced from coal in the gasifier through a 3-stage
   process, namely, devolatilization and drying, gasification, and
   partial combustion.

•  Temperature and pressure are high (1400 F and 400 psig).

•  Most of the potentially hazardous materials are produced in the
   gasifiers, but there is no direct continuous atmospheric emission
   of these materials from the gasifier.

•  Coal ash is the only direct waste discharge from the gasifiers
   to the atmosphere.
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                      34.  Quenching and Cooling

•  Cool the product gases and separate the coal tar and other
   condensates from the product gases.

•  A scrubbing and cooling tower is used to remove the tar from the
   gas stream.

•  Temperature is high and pressure is low.

•  Potentially hazardous materials present in the system and
   housekeeping is a key factor to reduce the fugitive emission of
   these materials.
                       High-BTU Gas Production
                       36.  Shift Conversion
                       39.  Methanation

•  Produce hydrogen in the shift converter from the reaction of
   carbon monoxide and water.

•  Produce more methane in the methanator from the catalytic reaction
   of carbon monoxide and hydrogen.

•  Temperature in shift converter is very high (700 to 1000 F).
   Temperature and pressure in methanator are high (800 F and  225 psi)

•  Nickel carbonyl, a carcinogen, is emitted from the methanator
   in which nickel is used as a catalyst.

•  Fugitive emission from leaks of pump seals and valves is likely
   in these systems.
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                            Gas Cleaning
                            38.  Acid Gas Removal (Rectisol Wash)
                            40.  Further Gas Purification (Reactisol
                                   Wash)

•  Remove acid gases such as hydrogen sulfide, carbonyl sulfur and
   carbon dioxide down to a level of about 0.1 ppmv.

•  The acid gases are washed out by methanol at low temperature.
   Methanol is recovered in a flash tank and a methanol-water
   separator.  The acid gases are regenerated in a multi-stage
   operation.

•  Temperature and pressure are low (-50 F and 1 psi).
                                 146

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                           Sulfur Removal
                           31.  Sulfur Recovery  (Glaus Process)
                           41.  Sulfur Recovery  (Stretford Process)

•  Glaus process removes sulfur from gas stream  in a catalytic
   reaction of sulfur dioxide and hydrogen sulfide.

•  Stretford process removes hydrogen sulfide from the gas stream
   by a counter-current liquid-gas absorption column.

•  The end product is the salable elemental sulfur.

•  Both processes involve corrosive and hazardous materials.

•  Major effluent stream of the Glaus process is the tail gas
   which contains sulfur compounds and may also contain other
   hazardous compounds.

•  There are two major effluent streams for the Stretford process:
   (1)  Tail gas which contains unreacted sulfur
   (2)  Purge stream from the absorption column.
             37.  Phenol Recovery  (Phenosolvan Process)

•  Recover phenol from the water-effluent stream.

•  Phenol is extracted by isopropyl ether which is regenerated
   in a distillation column.

•  Temperature involved is moderate.

•  Only major effluent stream is the slightly phenolic water to
   bio-water treatment.

                                 147

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                             APPENDIX C

                            BIBLIOGRAPHY

                        Reference A.  Toxicity
A-l.  Particulate polycyclic Organic Matter, Committee on Biologic
      Effects of Atmospheric Pollutants, Division of Medical
      Sciences, National Research Council, 1972.

A-2.  Hartwell, J. L., ed., "Survey of Compounds Which Have Been
      Tested for Carcinogenic Activity", Public Health Service
      Publication No. 149, Second Edition, 1951.

A-3.  Hartwell, J. L. and Shubik, P., "Survey of Compounds Which
      Have Been Tested for Carcinogenic Activity", Public Health
      Service Publication No. 149, Supplemental, 1957.

A-4.  Magee, E. M., Hall, H. J. and Varga, Jr., G. M., "Potential
      Pollutants in Fossil Fuel", Environmental Protection Technology
      Series, EPA-R2-73-249 (June 1973).

A-5.  "Evaluation of the Hazard of Bulk Water Transportation of
      Industrial Chemicals", 1970 Edition with additions to July 30,
      1973, Report prepared by the Evaluation Panel of the Committee
      on Hazardous Materials, Div. of Chemistry & Chemical Technology,
      National Research Council, under Contract No. CG-11,775-A,
      DOT-OS-00035, Task Order 13, for the U.S. Coast Guard
      (January 1974).

A-6.  Baskin, David A., Editor, "Handling Guide for Potentially
      Hazardous Commodities, Railway Systems and Management Assn.,
      Chicago, Copyright 1972.

A-7.  Stechey, Paul G., Editor, "Merck Index", 8th Edition, Merck
      & Co., Inc., 1968.

A-8.  McKee, J. E. and Wolf, H. W., "Water Quality Criteria", Second
      Edition, Publication 3-A, California State Water Resources
      Control Board, Revised 1963.

A-9.  "Water Quality Criteria Data Book", Volume 3, "Effects of
      Chemical on Aquatic Life", Water Pollution Control Research
      Series 180506WV05/71, U.S. EPA Office of Research and Monitoring
      (May 1971).
                                 148

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A-10.  "Threshold Limit Values of Airborne Contaminants and Intended
       Changes Adapted by ACGIH for 1970", American Conference of
       Governmental and Industrial Hygienists, 1970.
                                  149

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                         Reference B, Coking
B-l.  Anderson, H. C. and Wu, W.R.K.,  "Properties of Compounds in Coal-
      Carbonization Products", U.S. Dept. of Interior, Bureau of Mines,
      Bulletin 606.

B-2.  Jackson, J. 0., Warner, P. 0., and Mooney, Jr., T. F., "Profiles
      of Benzo(a)pyrene and Coal Tar Pitch Volatiles at and in the
      Immediate Vicinity of a Coke Oven Battery", American Industrial
      Hygiene Assoc. Journal, 35 (5),  276-81 (May 1974).

B-3.  Smith, W. M., "Evaluation of Coke Oven Emission", J. Occupational
      Medicine, 13 (2), 69-74 (February 1971).

B-4.  Von Lehmden, D. J., Hangebrauck, R. P., and Meeker, J. E.,
      "Polynuclear Hydrocarbon Emission from Selected Industrial
      Processes", J. Air Pollution Control Association, JL5 (7),
      306-12 (July 1965).

B-5.  Dancy, T. E., "Control of Coke-Oven Emission", Iron and Steel
      Engineer, 65-75 (July 1970).

B-6.  Gunter, B. J. and Rune, R. L., "Health Hazard Evaluation/Toxicity
      Determination: Empire Detroit Steel Company, New Boston, Ohio",
      NTIS Report PB229 083/1W3 (August 1972).

B-7.  Flesch, J. P., Ramos, H. and Ruhe, R. L., "Health Hazard
      Evaluation/Toxicity Determination:  Ford Motor Company, Rouge
      Plant, Dearborn, Michigan", NTIS Report PB 229 073/2WP.
                                 150

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                        Reference C. PETROLEUM
C-l.  Gruse, W. A., and Stevens, D. R., Chemical Technology of
      Petroleum, 3rd ed., N.Y., McGraw-Hill (1960).

C-2.  Kim, B. C., Murthy, K. and Jenkins, D. M., "Pollutants from
      Residual Oil Combustion", Preliminary Report to EPA Contract
      No. 68-02-1323 (Task 4), Battelle-Columbus Laboratories
      (December 1973).

C-3.  Handbook of Chemistry & Physics. 55th ed., Chemical Rubber Co.,
      Cleveland, Ohio, CRC (1973).

C-4.  "A Program to Investigate Various Factors in Refinery Siting",
      Final Report with map inserts, Radian Corporation, Austin,
      Texas  (1974).

C-5.  Encyclopedia of Chemical Technology. 2nd ed., Kirk-Othmer,
      Vol. 1-22, N.Y. Wiley (1963-70).

C-6.  Environmental Protection Agency, "Compilation of Air Pollutants
      Emission Factors", 2nd ed., AP42, Research Triangle Park, N.C.
             (1973).
                                 151

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                       Reference D. Combustion
D-l.  Geostle, R. W., et al. , "Chrome and Hydrogen Chloride Emission
      and Their Control", APCA 64th Annual Meeting, Paper 71-25
      (June 27, 1971).

D-2.  Sawicki, E., "Airborne Carcinogens and Allied Compounds", Arch
      Envision Health, 14, 46-63 (January 1967).

D-3.  Sawicki, E., Meeker, J. E., and Morgan, M. J., "The Quantitative
      Composition of Air Pollution Source Effluents in Terms of Aza
      Heterocyc'lic Compounds and Polynuclear Aromatic Hydrocarbons",
      Intern. J. Air Water Pollution, 9, 291-98 (1965).

D-4.  Hangebrauck, R. P., Von Lehmden, D. J., and Meeker, J. E.,
      "Source of Polynuclear Hydrocarbons in the Atmosphere", U.S.
      Dept. of Health, Education and Welfare, Public Health Service
      Publication No. 999-AP-33  (1967).

D-5.  Davison, R. L., Natusch, F. S., Wallace, J. R. and Evans, Jr.,
      C. A., "Trace Elements in Fly Ash Dependence of Concentration
      on Particle Size", Environmental Science and Technology, 8  (13),
      1107-13  (December  1974).

D-6.  Air Pollution. Edited by A. C. Stern, Academic Press, N.Y.
      (1968), "Chemical  Analysis and Carcinogenic Bioassays of
      Organic Particulate Pollutants",  (Hoffmann, D. and Wynder,
      E. L.), 2  (20), 187-247.
                                  152

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                      Reference E, Gasification
E-l.  Ricketts, T. S., "The Operation of the Westfield Lurgi Plant and
      the High Pressure Grid System", IGE J., 563-83 (October 1963).

E-2.  Kalfadelis, C. D., Magee, E. M., "Evaluation of Pollution
      Control in Fossil Fuel Conversion Process.  Gasification
      Section 1: Synthane Process", Office of Research and Development,
      U.S. EPA-650/2-74-009-6  (June 1974).

E-3.  Shaw, H. and Magee, E. M., "Evaluation of Pollution Control in
      Fossil Fuel Conversion Process Gasification; Section 1:  Lurgi
      Process", Office of Research and Development, U.S. EPA-
      650/2-74-009-C (June 1974).

E-4.  Attan, A., "Fate of Trace Constituents of Coal During Gasifi-
      cation", Office of Research and Development, U.S. EPA-650-2-
      73-0004, PB-223 001 (August 1973).

E-5.  Forney, A. J., et al., "Analysis of Tars, Chars, Gases, and
      Water Found in Effluents from Synthane Process", U.S. Bureau of
      Mines Technical Progress Report 75 (January 1974).

E-6.  Moe, J. M., "SNG from Coal Via the Lurgi Gasification Process".

E-7.  "Environmental Applications of Advanced Instrumental Analyses:
      Assistance Projects, FY  '73", Environmental Protection
      Technology Series, U.S. EPA-660/2-74-078 (August 1974).

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                                 TECHNICAL REPORT DATA
                          (Please read Instructions on the reverse before completing)
 1. REPORT NO.
  EPA-650/2-75-038
                            2.
                                                       3. RECIPIENT'S ACCESSION-NO.
 4. TITLE ANOSUBTITLE
 Potentially Hazardous Emissions from the Extraction
    and Processing of Coal and Oil
                                 S. REPORT DATE
                                 April 1975
                                 6. PERFORMING ORGANIZATION CODE
 7.AUTHOR
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