3
United States EPA-600/7-81-142
Environmental Protection
A9encv ' August 1981
v°/EPA Research and
Development
ENVIRONMENTAL ASSESSMENT:
SOURCE TEST AND EVALUATION REPORT—
Lurgi (Kosovo) Medium-Btu Gasification,
Final Report
Prepared for
Effluent Guidelines Division (OWWM)
Office of Air Quality Planning and Standards
Regional Offices 1 - 10
Prepared by
Industrial Environmental Research
Laboratory
Research Triangle Park NC 27711
-------
RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7. Interagency Energy-Environment Research and Development
8. "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the INTERAGENCY ENERGY-ENVIRONMENT
RESEARCH AND DEVELOPMENT series. Reports in this series result from the
effort funded under the 17-agency Federal Energy/Environment Research and
Development Program. These studies relate to EPA's mission to protect the public
health and welfare from adverse effects of pollutants associated with energy sys-
tems. The goal of the Program is to assure the rapid development of domestic
energy supplies in an environmentally-compatible manner by providing the nec-
essary environmental data and control technology. Investigations include analy-
ses of the transport of energy-related pollutants and their health and ecological
effects; assessments of, and development of, control technologies for energy
systems; and integrated assessments of a wide range of energy-related environ-
mental issues.
EPA REVIEW NOTICE
This report has been reviewed by the participating Federal Agencies, and approved
for publication. Approval does not signify that the contents necessarily reflect
the views and policies of the Government, nor does mention of trade names or
commercial products constitute endorsement or recommendation for use.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
-------
EPA-600/7-81-142
August 1981
Environmental Assessment: Source Test and
Evaluation Report • Lurgi (Kosovo) Medium-BTU
Gasification, Final Report
by
K.W. Lee, W.S. Seames, R.V. Collins,
K.J. Bombaugh, and G.C. Page
Radian Corporation
P.O. Box 9948
Austin, Texas 78766
Contract No. 68-02-3137 and 2147
EPA Project Officer: William J. Rhodes
Industrial Environmental Research Laboratory
Office of Environmental Engineering and Technology
Research Triangle Park, NC 27711
Prepared for
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, DC 20460
U.S. Environmental Protection Agency
Region,5, .Library (5PL-16)
£30 S. Dearborn Street, Room 1670
Chicago, IL 60604
-------
ABSTRACT
This report summarizes the results to date of the environmental data
acquisition program which is jointly sponsored by the U.S. Environmental
Protection Agency and the Government of Yugoslavia. The subject of this test
is a commercial-scale, medium-Btu, Lurgi-type gasification facility which is
currently operating in the Kosovo region of Yugoslavia.
The objective of this test program is to characterize potential environmen-
tal problems associated with the gasification of coal in a Lurgi-type gasifi-
cation plant. Since Lurgi plants are being planned for U.S. gasification
facilities, this study provides EPA with an opportunity to test firsthand, the
possible environmental problems which might be encountered.
The Source Analysis Model/lA (SAM/1A) was applied to the best values of
flow rates and concentrations of chemical species from all field tests to
identify and prioritize potentially harmful discharges. This model was also
applied to specific chemical species plantwide in the gaseous discharge
streams.
The primary conclusion of this environmental assessment model is that the
process jghibits a significant potenti£l_Jor__p^^luy_on,,_ All discharge streams
are potential vehicles~~for~p"oriutant transfer from the process to the environ-
ment. The streams with the highest priority for control based on their poten-
tial for adverse health effects in the three discharge media are the l^S-
rich waste gas, phenolic wastewater and heavy tar (solid). When evaluated
using the SAM/1A, sulfur compounds pose the largest potential for adverse
[ health effects plantwide from the gaseous discharges. • A
t- .
The ash from the Kosovo facility has a very low potential for adverse
environmental effects, as evidenced by the results of bioassay of the ash and
leachates from the ash. Trace elements were found to be much less significant
than trace organics in their contribution to the discharge severity of the
waste streams. Levels of trace elements found by the Resources Conservation
Recovery Act method of extraction were greater than an order of magnitude
below levels specified in the Extract Procedure Toxicity Test.
ii
-------
TABLE OF CONTENTS
Section
ABSTRACT ii
TABLE OF CONTENTS ill
LIST OF FIGURES iv
LIST OF TABLES vi
ACKNOWLEDGEMENT viii
1. INTRODUCTION 1
1.2 Plant Description.- . 2
1.3 Rationale for Phase II Testing 3
1.4 Sampling and Analytical Methodology 4
1.5 Results 4
2. PLANT DESCRIPTION 8
2.1 Kosovo Gasification Plant 8
2.2 Gasification Plant Section Descriptions 13
3. RATIONALE FOR PHASE II TESTING 32
3.1 Plant Section Selection 32
3.2 Stream Selection 33
4. TEST METHODOLOGY 39
4.1 Sampling Methods 39
4.2 Analytical Methods 52
4.3 Data Evaluation - Source Analysis Model/lA 71
5. RESULTS AND DISCUSSION 74
5.1 Gaseous Discharge Streams 74
5.2 Aqueous Waste Streams * 89
5.3 Solid Discharges Including a Comparison to
Gaseous and Aqueous Discharges. 92
5.4 Product and By-Product Streams..... 95
5.5 Bioassay Results 95
5.6 Mass Balances 98
5.7 Additional Comments and Summary of Findings 101
BIBLIOGRAPHY 105
APPENDICES
A. Compilation of Result s A-l
B. Level 1 EPA Health Effects Tests on Coal
Gasification Samples B-l
C. Mass Balance Calculations C-l
D. DMEG Values Proposed by Research Triangle Institute D-l
E. Glossary of Terms and Acronyms E-l
ill
-------
LIST OF FIGURES
Figure page
1-1. A comparison of the total weighed discharge severity values
(health) for key Kosovo gaseous, aqueous, and solid streams.... 7
2-1. Regional map of Yugoslavia showing the location of the
Kosovo industrial complex 9
2-2. The Kosovo industrial complex 10
2-3. Design flow rates of key streams in the Kosovo gasification
plant (all values in megagrams/hr. based on 5 gasifiers in
service) 11
2-4. Simplified flow diagram of the Kosovo coal preparation/
gasification plant operations 12
2-5. Process flow diagram showing sampling points in the Kosovo
Coal Drying section 15
2-6. Process flow diagram showing sampling points in the Kosovo
Gas Production section 19
2-7. Process flow diagram showing sampling points in the Kosovo
. Rectisol section 22
2-8. Process flow diagram showing sampling points in the Kosovo
.Tar/Oil separation section 25
2-9. Process flow diagram showing sampling points in the Kosovo
Phenosolvan section 27
2-10. Process flow diagram showing sampling points in the Kosovo
By-Pro duct Storage section 30
4-1. Probe configurations 44
4-2. Probe to port sealing mechanism 45
4-3. Sampling apparatus for tank vent 46
4-4. Condensable organic sampling train...... 48
4-5. Gas sampling and conditioning apparatus. 50
4-6. Flow scheme for on-site gas chromatographic analyses 54
4-7. XAD-2® resin extraction flow scheme 57
iv
-------
LIST OF FIGURES (Continued)
Figure page
4-8. Flow scheme for the preparation of sample train rinses 58
4-9. Flow scheme for the extraction of aqueous liquid samples 59
4-10. Flow scheme for the preparation of by-products 61
4-11. Flow scheme for the preparation and analysis of headspace
samples. 63
4-12. Key Kosovo gaseous pollutants in order of severity (1/DMEG.... 72
5-1. Comparison of mass concentrations to discharge severities
(air-health) in the low pressure coal lock vent discharge
stream (3.2) 82
5-2. Total weighted discharge severities (air-health) of key
Kosovo gaseous discharge streams 83
5-3. A comparison of health and ecology total weighed discharge
severity values in key Kosovo gaseous discharge streams. 84
5-4. The nine worst compounds in gaseous discharge streams on a
plantwide basis in order of descending TWDS (health).......... 86
5-5. The effects of PNA contributions on the total weighted
discharge severity values (health) for four gaseous discharge
streams... 90
5-6. A comparison of the total weighted discharge severity values
(health) for key Kosovo gaseous, aqueous and solid streams.... 94
5-7. Mass balances for carbon, sulfur and nitrogen in Kosovo
process and discharge streams. 100
5-8. Daily variation in the sulfur content of Kosovo lignite 102
-------
LIST OF TABLES
Table page
2-1. FLEISSNER DRYING CYCLE 16
2-2. SIGNIFICANT PROCESS AND DISCHARGE STREAMS IN THE KOSOVO COAL
PREPARATION SECTION 17
2-3. SIGNIFICANT PROCESS AND DISCHARGE STREAMS IN KOSOVO GAS
PRODUCTION SECTION 21
2-4. SIGNIFICANT PROCESS AND DISCHARGE STREAMS IN KOSOVO
RECTISOL SECTION 24
2-5. SIGNIFICANT^PROCESS AND DISCHARGE STREAMS IN KOSOVO TAR/OIL
SEPARATION SECTION 26
2-6. SIGNIFICANT PROCESS AND DISCHARGE STREAMS IN KOSOVO
PHENOSOLVAN SECTION 29
2-7. SIGNIFICANT PROCESS AND DISCHARGE STREAMS IN KOSOVO BY-PRODUCT
STORAGE SECTION ^. ...... 31
3-1. KOSOVO STREAMS SELECTED FOR PHASE II TESTING;..... 34
4-1. SAMPLING AND ANALYTICAL METHODS 40
4-2. PROBE/PORT CONFIGURATION FOR KOSOVO GAS STREAMS 43
4-3. ON-SITE GAS CHROMATOGRAPHIC ANALYSIS - INSTRUMENTS AND
CONDITIONS 55
4-4. ANALYTICAL METHODS USED FOR THE ANALYSIS OF TRACE ELEMENTS 65
4-5. ANALYTICAL PROCEDURES FOR WASTE WATERS 66
4-6. ANALYTICAL PROCEDURES FOR IMPINGER SOLUTIONS 67
4-7. ANALYTICAL PROCEDURES FOR SOLIDS AND BY-PRODUCTS 68
5-1. KOSOVO GASEOUS STREAM COMPOSITION DATA 76
5-2. COMPONENT CONCENTRATIONS IN KOSOVO GASEOUS STREAMS "78
5-3. MOST SIGNIFICANT GASEOUS SPECIES IN ORDER OF MASS DISCHARGE -
PLANTWIDE ...; ' 80
5-4. PARTICULATE CONCENTRATION AND FLOW RATE DATA FOR KOSOVO
GASEOUS STREAMS. 87
vi
-------
LIST OF TABLES.(Continued)
Table page
5-5. HAZARDOUS PNA'S IN KOSOVO LIGHT TAR AND MEDIUM OIL (ug/g) 88
5-6. KOSOVO AQUEOUS STREAM DATA 91
5-7. COMPARISON OF PRODUCT GAS COMPOSITION ENTERING AND LEAVING
THE RECTISOL GAS CLEANING PLANT 96
5-8. COMPARISON OF ULTIMATE ANALYSIS DATA FOR KOSOVO BY-PRODUCT
TARS, OIL AND NAPHTHA 97
5-9. A SUMMARY OF THE BIOASSAY RESULTS 99
vii
-------
ACKNOWLEDGEMENT
The authors wish to express their appreciation to the many individuals who
contributed to this international program. Special expression of gratitude
for their timely and very beneficial contributions to the work described in
this report go to:
W. J. Rhodes and T. K. Janes (United States Environmental
Protection Agency - IERL - Research Triangle Park, North
Carolina)
Mira Mitrovii and Dragon Rehkovic (Rudarski Institute -
Belgrade, Yugoslavia)
Becir Salja, Shani Dugja, Emili Boti, Toma Savid, Stjepan
Rojevic (Kombine Kosovo - Belgrade Yugoslavia)
Slobodan Kopar (Institute for the Use of Nuclear Energy
in Forestry and Agriculture - Belgrade, Yugoslavia)
Rodamir Vitic, Branislav Tomasevic, Mile Miloslavljevii
(Kosovo Institute - Kosovo, Yugoslavia)
C. E. Hudak, Klaus Schwitzgebel, W. E. Corbett, R. A. Magee
D. S. Lewis, and G. M. Crawford (Radian Corporation, Austin,
Texas).
viii
-------
SECTION 1
INTRODUCTION
An international program, sponsored by the Industrial Environmental
Research Laboratory (IERL) of the U.S. Environmental Protection Agency (EPA)
is being conducted in the Kosovo region of Yugoslavia. The program was
designed in response to a need for representative data on environmental prob-
lems associated with the commercial application of Lurgi coal gasification
technology. The program, conducted over a three-year period, is a joint
effort among scientists from the U.S. and Yugoslavia. The participating
organizations, and their roles, are shown below.
Organization
EPA/IERL
Radian Corporation
Rudarski Institute
Kobinat Kosovo
Kosovo Institute
Location
Function
Research Triangle Park, Funding Agency
North Carolina
Austin, Texas
Belgrade, Yugoslavia
Obilic, Yugoslavia
Obilic, Yugoslavia
Institute za Primenu Belgrade, Yugoslavia
Prime Contractor, Coordinator
Sampling/Analyses/Data
Analyses/Overseas Coordination
Plant Operation/ Sampling
Sampling/Trace Element Analyses
On-Site GC Analyses /Organic
Analyses '
The opportunity to make a comprehensive environmental characterization of an
operational, commercial-scale, Lurgi-type coal gasification plant was consi-
dered valuable since a number of U.S. companies have announced plans to con-
struct such plants. Thus, characterization of selected process and discharge
streams from the Kosovo plant provides a valid insight into problems that must
be considered by U.S. designers in developing process modification and/or con-
trol schemes necessary to meet U.S. environmental requirements.
The test program was conducted in four phases, as follows:
Phase Objective
I Identify and measure major and minor pollutants
in discharge streams.
II
Identify and measure trace pollutants in discharge
streams.
-------
Ill Characterize ambient air pollutants in the
vicinity of the plant.
IV Measure fugitive emission rates from leak
sources in the plant.
This report presents information on major, minor, and trace pollutants in the
discharges from the Kosovo plant. The results from'testing in Phases I and II
are combined here to provide a "best value" for use in evaluating the dis-
charges. This report includes not only an assessment of specific discharges
but also an evaluation of discharge severity as determined by EPA/IERL's
Source Analysis Model/lA (SAM/1A) model for prioritizing pollutants on the
basis of their potential for causing adverse health and ecological effects.
1.2 PLANT DESCRIPTION
The Kosovo Gasification Plant is part of a large mine-mouth industrial
complex located near the city of Pristina, in the Kosovo Region of Southern
Yugoslavia. The complex consists of a coal mine, a coal preparation plant,
the gasification plant, a steam and power generation plant, an ammonia plant,
and an air separation plant.
The gasification plant consumes dried coal (lignite) and produces two
primary products: a medium-Btu fuel gas and hydrogen for use in ammonia
synthesis. Several by-products are also produced: tar, medium oil, naphtha,
and crude phenol.
Run-of-mine coal from the Kosovo mine is dried by the Fleissner process
and sized to select particles ranging in diameter from 6 mm to 60 mm. The
coal is then fed to the Lurgi-type gasifiers where it is reacted with oxygen
and steam at 2.5 MPa (25 atm) pressure. The crude product gas is cooled,
cleaned, and transported by pipeline to the utilization site.
As the crude product gas is quenched and cooled, tars, oils and naphtha
are condensed and removed in a penolic water stream. Acid gases (H^S and
C02) are removed by the product gas by sorption with cold methanol (Rectisol
process).
The acid-gas-rich methanol is regenerated, releasing a waste gas rich in
H2S, which is flared, and a CC^-rich waste gas which is vented to the
atmosphere. Tars and oils are removed from the phenolic water stream by de-
cantation, after which the water soluble organics (crude phenols) are r.ecover-
ed by extraction with diisopropyl ether. Four liquid by-products; tar, medium
oil, naphtha, and crude phenol are collected and held in storage tanks for
futher use. Ammonia, removed from the phenolic water by steam-stripping, is
vented to the atmosphere. A more detailed description of the plant and its
operation is presented in Section 2 of this report.
-------
1.3 RATIONALE FOR PHASE II TESTING
The program conducted at Kosovo presented an unusual opportunity to exam-
ine the environmental character of an operational, commercial-scale Lurgi-type
coal gasification plant. Although the control technologies used at Kosovo
would not be considered to be "best available" by current U.S. standards, the
control problems facing U.S. Lurgi facility operators will be similar to those
found at Kosovo. Therefore, a study of the waste streams at Kosovo should aid
U.S. plant designers in developing process modifications and control schemes
to meet U.S. environmental requirements.
As stated in Section 1.1, the objective of Phase II testing was.to iden-
tify and measure trace pollutants in the discharge streams from the plant. The
test plan developed for Phase II, therefore, comprised an examination of the
total gasification plant, including coal preparation, product-gas cleaning and
by-product recovery and storage operations which are integrated with the gas
generation operation. Other facilities in the Kosovo industrial complex,
(ammonia plant, air separation plant, steam and power generation plant, etc.)
were not examined during this program because they were not of primary inter-
est to EPA's synthetic fuel program and/or it was felt that adequate data
existed already on such facilities.
1.3.1 Stream Selection
Process and discharge streams in the plant sections examined were selec-
ted for study if they met one or more of the following criteria:
• high discharge rate,
• significant pollutant concentration,
• trace pollutant characterization, and
• information value.
Streams exhibiting a high discharge rate were selected for study because at
the rates involved (e.g., the (X>2 rich waste gas stream with a design flow
rate of 2400 nrVgasifier-hour), even very low concentrations of moderately
toxic pollutants could result in a significant environmental burden.
Streams exhibiting a moderate to low discharge rate were selected for
study based on their significant pollutant concentration expressed as dis-
charge severity (a research and development prioritization method). Discharge
severity is an expression of the potential for adverse health and ecological
effects exhibited by a component in the stream, and is based not only on the
toxicity of that component but also on its concentration. Thus it may be seen
that highly toxic components at low concentrations and moderately toxic compo-
nents at high concentrations both would exhibit high discharge severities.
Streams (and sampling points) were selected for study based on a need for
information on the fate of trace elements and trace organics throughout the
process. In many cases, streams selected for other reasons were studied also
for trace element and trace organic character.
-------
The final criterion for stream selection was information value. Process
and discharge streams were selected for study if they could be expected to
provide information essential to a better understanding of plant and process
operations or would be useful in determining the fate of important compounds
through the process.
1.3.2 Stream Parameters Selection
Parameters were selected that would provide the data necessary for a
physical and/or chemical characterization of the stream under examination.
With gaseous streams, for example, velocity, temperature, pressure, actual
molecular weight and moisture content (physical parameters) were measured.
Analyses were made for fixed gases, aliphatic and aromatic hydrocarbons, sul-
fur species, and nitrogen species (chemical parameters). These values pro-
vided a basis for the calculation of stream flow rates, compositions, mass
flow rates, mass balances, and other values useful in gas stream characteri-
zation.
Aqueous streams were characterized by determining values for standard
water quality parameters (such as BOD and COD), physical properties (pH,
temperature), trace pollutants, and dissolved and suspended solids.
Solid and organic liquid streams were characterized by proximate, ulti-
mate, and trace pollutant analyses. In addition, leachate studies were per-
formed on solid wastes.
Bioassay screening tests were performed on selected streams to provide
information on their toxic and mutagenic characteristics.
1.4 SAMPLING AND ANALYTICAL METHODOLOGY
Standard EPA-approved sampling methods were used for most of the Phase II
testing. In some cases the standard methods were modified in response to
specific sample or stream conditions found at the Kosovo plant, or other
governing factors such as mechanical configuration of the sampling point or
requirements of the plant's operating schedule. . Detailed descriptions of
sampling methods used during Phase II of the Kosovo program are given in
Section 4 of this report, where any deviations from standard practices, and
the improvements that resulted, also are discussed.
The methods employed in the analyses of samples collected during Phase II
are also described in Section 4. The methods include standardized analytical
procedures approved by EPA, ASTM, DIN (German Institute for Standardization),
and COST (Soviet State Committee on Standards).
1.5 RESULTS
The results of Phase II testing corroborate substantially those obtained
during Phase I of the Kosovo program. In addition, new information obtained
during Phase II about the aqueous and solid discharges from the plant, and
-------
about trace organic and inorganic pollutants gives a more complete under-
standing of the environmental character of this specific gasification plant.
In developing the information contained in this report, all calculations
and interpretations are based on the best values for data obtained during both
Phase I and Phase II of the test program. The best values were selected based
on scientific and engineering judgment, with full consideration for factors
that might influence their selection, such as:
• plant operating conditions at the time the samples were taken,
• precision and reliability of specific analytical techniques, and
• measured or design flow rates.
The "Best value" data were then modeled, using EPA's SAM/1A, to provide an
estimate of the potential health and ecological effects associated with the
plant's discharge streams. Application of SAM/1A to discharge streams gives
values by which streams (and stream components) may be ranked according to
their discharge severity, or potential for adverse environmental effects.
Based on an interpretation of the results from the SAM/1A model, a number of
conclusions can be drawn. The conclusions, presented in the following para-
graphs, may be used as a basis for the selection of control technology suit-
able for application to similar gasification plants planned for construction
in the U.S.
The primary conclusion is that the uncontrolled process exhibits a sig
nificant potential for environmental pollution. All discharge media, air,
water, and land are potential receptors for pollutant transfer from one or '
another of the plant's discharge streams. Most of the major discharge streams
sampled were found to contain pollutants at levels which, if uncontrolled, are
sufficient to cause concern for human health and the ecology. However,
control measures specific to the stream and/or pollutant can be applied and
should reduce absolute pollutant release to levels that are acceptable
environmentally.
The total weighted discharge severity (TWDS) is a means of estimating the
severity of a stream using the SAM/1A. TWDS is the product of the total dis-
charge severity (TDS) for a discharge stream and the stream flow. IDS is the
summation of pollutant concentrations devided by their respective discharge
multimedia environmental goals (DMEG's) for a given stream and discharge med-
ium. The streams with the highest priority for control (greatest total
weighted discharge severity) based on their potential for adverse health
effects, in the three discharge media are:
• H2S-rich waste gas (air),
• phenolic wastewater (water), and
• heavy tar (land).
The greatest potential for adverse environmental effects results from
gaseous discharges, not only as a result of their severity, but also due to
-------
the number of streams that may be significant sources of pollutants. Fourteen
gaseous discharge streams were shown to be major potential sources of pollu-
tants, compared to two each for aqueous and solid streams. Figure 1-1 illus-
trates the ranking of these streams in each medium, according to their TWDS
(
It was found that polynuclear aromatic compounds (PNA's) contribute
greatly to the discharge severity of discharge streams containing tar: i.e.,
the heavy tar solid waste stream and the gaseous discharge from the low pres-
sure (LP) coal lock vent (where tar makes up a large portion of the particu-
late matter discharged in that stream). Benzo(a)pyrene and 7,12-dtmethylbenz-
(a)anthracene were identified as the most significant PNA's in the Kosovo tar.
Trace elements were found to be less significant than trace organics in
their contribution to the discharge severity of the waste streams. However,
mercury was found in the phenolic wastewater at a level exceeding the thres-
hold level at which concern for adverse health effects begins. Evaluation of
the analytical data for the phenolic water also revealed that, while the
Phenosolvan process is effective in removing most of the phenolic material
from the aqueous waste stream and reducing the concentrations of several
important PNA's to undetectable levels, a significant amount of organic mat-
ter, including some phenols, remained in the phenolic water after treatment.
The ash from the Lurgi-type gasification process was found to be of low
concern for adverse health or ecological effects. The results of Resource
Conservation and Recovery Act extraction procedure (RCRA EP) leaching studies
and bioassay on the ash indicated little or no toxicity. The tar streams,
however, as mentioned above, are potentially quite hazardous and probably will
require controlled disposal (e.g., incineration) in U.S. gasification plants.
In summary, Lurgi-type coal gasification technology, as examined at the
Kosovo plant, presents a significant potential for adverse environmental
effects. However, application of the proper control technology, which is cur-
rently available, should permit the commercial operation of such a plant in
the U.S. However, the effectiveness of these controls needs to be determined
once commercial plants are operating in the U.S.
-------
Gaseous Streams
Aqueous Streams
s s 7
Log 10 TDS + Log 10 (g/sec)
Q Log10TOS
^ Log-ioFIow is Negative
TDS = Total Discharge Severity
H2S-Rich Waste Gas (7.1)
Ammonia Stripper Vent (14.5)
CO2-Rich Waste Gas (7.2)
High Pressure Coal Lock Vent (3.6)
Autoclave Vent (1.2)
Tar/Oil Seperation Waste Gas (13.6)
Naptha Storage Tank Vent (15.3)
Low Pressure Coal Lock Vent (3.2)
Phenolic Water Tank Vent (13.7)
Medium Oil Tank Vent (13.3)
Gas Liquor Tank Vent (3.4)
Condensate Tank Vent (13.5)
Cooler Vent (14.6)
Tar Tank Vent (13.1)
Phenosolvan Wastewater (14.11)
Quenched Ash Wastewater
Heavy Tar (13.8)
Dry Gasifier Ash (12.1)
(TDS Based on RCRA Leachate)
a
Figure 1-1. A Comparison of the total weighed discharge severity
values (health) for key Kosovo gaseous, aqueous, and
solid streams. ,
-------
SECTION 2
PLANT DESCRIPTION
The Kosovo Gasification Plant is an integral part of a large mine-mouth
industrial complex. As shown in Figure 2-1, this complex is located near the
city of Pristina, in the Kosovo Region of southern Yugoslavia.
A block diagram of the Kosovo complex is shown in Figure 2-2. The com-
plex consists of a gasification plant, an ammonia plant, an air separation
plant, steam and power generation plants, coal preparation facilities, and a
coal mine. In the coal preparation section, run-of-mine coal is dried,
crushed, and sized. Coal particles between 6 and 60 mm in diameter are routed
to the gasification plant. Fines are used as fuel in the steam and power
plants while particles larger than 60 mm are recycled. The steam and power
plants produce export power as well as the steam and electricity required by
'the -Kosovo complex. The gasification plant produces a medium-Btu fuel gas
having a net heating value of approximately 14 MJ/m^ at 25°C (360 Btu/scf),
hydrogen, and liquid by-products. The hydrogen produced in the gasification
plant is used as an ammonia synthesis feedstock. The liquid by-products are
consumed as fuel in the steam plant. The air separation plant supplies oxygen
to the gasification plant and nitrogen to the ammonia plant.
2.1 KOSOVO GASIFICATION PLANT
The Kosovo gasification plant is a commercial-scale facility employing
Lurgi-type technology to produce a medium-Btu fuel gas from coal. Figure 2-3
shows the design flow rates of the plant's major inlet and outlet streams.
These data indicate that the plant is designed to produce 25 Mg (65,000 m^
at 25°C) of product gas for every 80 Mg of dried coal consumed.
The Kosovo plant is smaller than proposed first generation U.S Lurgi
gasification facilities, but it contains many of the process units which are
likely to be employed in future U.S. Lurgi plants. These units include
oxygen-blown, Lurgi-type gasifiers, a tar/oil separation facility, a Rectisol
acid gas removal unit, a Phenosolvan wastewater treatment unit, and by-product
recovery/storage facilities. For this reason, the plant is felt to be repre-
sentative of many aspects of the Lurgi gasification facilities which are being
considered for commercialization in the U.S.
A simplified process flow sheet of the Coal Preparation and Gasification
plants is shown in Figure 2-4. Run-of-mine coal is crushed, sized, and dried
in the Coal Preparation section. In the Gas Production section, dried coal
particles between 6 and 60 mm in diameter are gasified in one of six oxygen-
blown, Lurgi-type gasifiers. The hot product gases generated in the gasifiers
are cooled and routed to the Rectisol section where acid gases such as C02,
H2S, and HCN are removed. Clean product gas is then routed to a cryogenic
H2 separation unit and/or a Distribtuion system through which it leaves the
-------
Bosnia-
Hercegovina
Monte
Hegro KOSOVOx.pV tlna
X - Kosovo Industrial Complex
—• Product Gas Pipeline
Figure 2-1.
Regional map of Yugoslavia showing
the location of the Kosovo industrial
complex.
-------
Coal
Mine
Run of-
Mine
Coal
Fines
Coal
Preparation
Air
Separation
Steam
and
Power
Generation
Steam
Dried
Coal
02
N
Electric
Power
Liquid
By-products
Gasification
Plant
H2
NH3
Synthesis
BtuFuel
Gas
NH3to
Fertilizer
Plant
Figure 2-2. The Kosovo industrial coipplex.
-------
Rectisol
Acid Gases
(H2S-Rich and CO2-Rich)
(45)
r
Dried Coal (80)
Steam (65)
02(14)
Kosovo
Gasification
Plant
V
GasifierAsh
04)
Heavy Tar
(.05)
Waste-
waters
(68)
Clean
Product
Gas
(25)
Light Tar (2.2)
Medium Oil (1.3)
Naphtha (.07)
Phenols (.04)
Ammonia (1)
Figure 2-3. Design flow rates of key streams in the Kosovo gasification plant
(all values in megagrams/hr. based on 5 gasifiers in service).
-------
Fines to
Steam and Power
Generation
Waste
Oases'
Steam
Flare
Flue Oases
Steam
L
Run-ol-mlne
Coal
Coal
Preparation
Dried.
Sized Coal
Qas
Production
Waslewaler
Crude
Qas
Recllsol
Qas
Liquor
|Naphi
Clean'
Qas
ilha
Tar/011
Separation
Phenolic
Water
Tars*
Oils
Phenosolvan
Purlllcallon
Qas
Distribution
By-Producl
Storage
Phenols
-*> Waslewaler
,H2loNH,
Synthesis
Medium
^ BluQas
to Pipeline
By-Products
Jo Steam and
Power
Generation
Figure 2-4. Simplified flow diagram of the Kosovo coal preparation/
gasification plant operations.
-------
gasification 'plant. Ash generated in the gasifiers is water-quenched and
disposed of in a landfill. Condensed gas liquors generated as a result of
product gas cooling are sent to the Tar/Oil Separation section.
In the Tar/Oil Separation section, organic liquid by-products such as
light tar and medium oil are separated from the plant's condensed gas liquor
streams. These by-products are sent to the By-Product Storage section. A
sludge consisting of heavy tar and dust is also generated in the tar separa-
tion process. This sludge is disposed of in a landfill.
The wastewater leaving the Tar/Oil Separation section is routed to the
Phenosolvan section where volatile inorganics, such as CC>2 and ammonia, are
steam-stripped from the wastewater. Crude phenols are then extracted from the
wastewater using diisopropyl ether and sent to the By-Product Storage section.
The extracted wastewater is supposed to be treated in a biological treatment
unit before being discharged. However, this unit was not in service during
the Phase II test program.
While the process flow scheme at Kosovo is representative of proposed
U.S. Lurgi plant designs, the environmental control practices followed at the
Kosovo plant are not. Many of the plant's waste streams are 'controlled* but
none of the controls employed would be characterized as 'best available* by
current U.S. standards. Thus, while the discharges that enter the environment
at Kosovo are not representative of those that would be encountered in similar
U.S. facilities, the type of control problems facing U.S. Lurgi plant opera-
tors will be similar to those found at Kosovo. A study of the waste streams
generated at Kosovo should aid U.S. plant designers in developing the process
modifications and control schemes necessary to achieve U.S. standards of con-
trols.
2.2 GASIFICATION PLANT SECTION DESCRIPTIONS
The Kosovo gasification plant sections which were selected for testing in
Phase II are those which contain sources of potentially environmentally signi-
ficant discharge streams. These sections include:
Coal Preparation section,
Gas Production section,
Rectisol section,
Tar/Oil Separation section,
By-Product Storage section, and
Flare System.
Each of these sections is described below.
2.2.1 Coal Preparation Section
In the coal preparation section, run-of-mine Kosovo coal is crushed,
sized, and dried. The moisture content of the coal, as mined, is
13
-------
approximately 40-50% by weight. More than 50% of this moisture is removed by
the Fleissner drying process to facilitate efficient operation of the Kosovo
Lurgi-type gasifiers. A simplified flow diagram of the coal drying process is
shown in Figure 2-5. Also shown are the sources of the major discharge
streams generated in this section.
Run-of-mine coal is crushed and particles between 6 and 60 mm are stored
in coal bunkers located above the Fleissner autoclaves. Over the coal bunker
is a hooding system which is used to capture the coal particulates generated
during coal transfer operations. Coal particules entrained in the air stream
which is drawn through this hooding system are captured by a baghouse. The
solids collected by the baghouse are sent to the power plant.
The Fleissner drying process uses saturated steam to heat the coal to a
temperature of about 240°C (464°F) in an autoclave. One advantage of this
process is that considerable quantities of moisture can be removed from the
coal as liquid. This helps preserve the structural integrity of the coal
matrix and minimizes fine generation during drying.
Kosovo Fleissner dryers operate in a batchwise manner. A complete drying
cycle lasts from 160 to 200 minutes. The steps involved in the drying cycle
are shown in Table 2-1. Throughout the drying cycle, small quantities of
noncondensible gases (mostly 002) are bled from the autoclave. Before the
autoclave is emptied, low pressure vent gases (mostly steam) are discharged
through a vent into the atmosphere.
At Kosovo, the Fleissner autoclaves are arranged in groups of four so
that blowdown steam and condensate from autoclaves being depressurized can be
used to preheat the coal entering other autoclaves. Condensate from the dry-
ing process is used to satisfy in-plant water needs. Gases released from the
condensate tank are discharged to the atmosphere.
The amount of moisture remaining in the coal after Fleissner treatment is
primarily a function of the steam pressure used in the process. At Kosovo,
the maximum stream pressure is about 3 MPa (30 atm). The moisture content of
the dried coal is normally about 20-30% by weight.
Because the Fleissner operation is cyclic, discharges vary depending upon
the step in the cycle. This characteristic makes it very difficult to deter-
mine representative discharge stream flow rates and compositions. The signi-
ficant process and discharge streams in the Coal Preparation section are
summarized in Table 2-2. Process wastes generated in this section were char-
acterized by analyzing the autoclave vent and the condensate stream. Some of
the environmental concerns in the Coal Preparation section are the quantity
and composition of the volatile gases generated during the drying cycle and
the character and quantity of pollutants in the condensate.
14
-------
RUN OF MINE
COAL
HIGH PRESSURE
STEAM (3MPa)
INTERMEDIATE PRESSURE
(1MPa) STEAM FROM
OTHER AUTOCLAVES.
HOT AIR (100* Q
USED FOR
FINAL DRYING
TO BAGHOUSE
THIS HOODING SYSTEM
ALSO CAPTURES GASES
RELEASED FROM THE
DRIED COAL BUNKER
STEAM TO
OTHER AUTOCLAVES
(FOR WET COAL
WARMUP)
CONOENSATE
TANKVENT
DRIED COAL
TO SIZING
OPERATION
CONOENSATE
TANK
FLEISSNER
CONDENSATE
Figure 2-5.
Process flow diagram showing sampling points
in the Kosovo Coal Drying section.
15
-------
TABLE 2-1. FLEISSNER DRYING CYCLE
Approximate Duration
Step (minutes)
Coal Charging' 10
1st Preheating (using low pressure, 1 MPa 20
[10 atm] steam)
2nd Preheating (using intermediate pressure 20
steam)
Final Heating (using high pressure, 3 MPa 60
[30 atm] steam)
1st Autoclave Discharge (release of inter— 20
mediate pressure steam)
2nd Autoclave Discharge (release of low 20
pressure steam)
Emptying the Autoclave . 10
TOTAL 160
16
-------
TABLE 2-2. SIGNIFICANT PROCESS AND DISCHARGE STREAMS IN THE KOSOVO COAL PREPARATION SECTION
Stream
Number Stream Description
1.0 Run-of-mine Coal
1.1 A Fleissner Baghouse Gases
1.1 B Fleissner Baghouse Catch
1.3 Fleissner Condensate
1 .4 Condensate Tank Vent
1 s - solid
*q ~ aqueous
g - gaseous
2Dry gas flow rate in m3/gasif ier-hr at 2J«C,
Stream1 Deaign2
Type Flow Rate
a 24.000
g ' Unknown
a Unknown
aq Unknown
a. Unknown
solid flow rate in kg/gaaif ier-hr
Beat Value2'3
Flow Rate Commenta
ND* Sampled in Phase II
ND ' Not sampled in Phase Hi mainly air
ND Sampled in Phase Hi primarily coal
particulate
fixed gaaea, and particulatea
ND Sampled in Phase II
ND Not sampled during Phase Hi composi-
tion similar to that of Stream 1.2
- Not determined
-------
2.2.2 Gas Production Section
In the Gas Production section, the following functions are accomplished:
• the dried coal is gasified to produce crude product gas;
• the crude product gas is cooled and scrubbed to remove
entrained coal fines and heavy organics; and
• the ash is removed from the gasifier and quenched.
A simplified process flow diagram for this section is shown in Figure 2-6.
Also shown are the section's discharge sources.
There are six pressurized fixed-bed, oxygen-blown, Lurgi-type gasifiers
at Kosovo. Dried coal is fed by conveyor belts to coal bunkers located above
each gasifier. Nitrogen is used as a purge gas for each bunker to prevent
spontaneous ignition of the coal. The coal bunker purge gases are collected
in hoods and sent through a scrubber to remove entrained coal dust before
being discharged to the atmosphere. The blowdown liquid from the coal bunker
vent gas is combined with other wastewaters generated in this section prior to
discharge (Stream 12.3).
The operating cycle of a Lurgi-type coal feed lock hopper consists of
four steps:
• filling the hopper with coal,
• pressurizing the coal lock,
• feeding the coal to the gasifier, and
• depressurizing the coal lock.
Coal enters the coal lock from the coal bunker through a transition sec-
tion which is referred to as a coal lock bucket. Gases displaced by the coal
during the charging cycle are vented to the atmosphere through the coal lock
bucket vent (Stream 3.1). When the coal lock bucket vent becomes plugged with
coal dust and tar, as it was during Phases I and II of the test program, these
gases are released through the low pressure coal lock vent (Stream 3.2).
After the coal lock if filled with coal, it is pressurized with crude
product gas. When the coal lock has reached operating pressure, the valve
separating the coal lock from the gasifier is opened and coal enters the
gasifier from the coal lock.
When all the coal in the lock hopper has been added to the gasifier, the
valve separating the coal lock from the gasifier is closed and the coal lock
is depressurized. In the initial stages of coal lock depressurization, high
pressure gas is sent to the flare system (Stream 3.6). Then, after the gas
pressure in the coal lock has been reduced to around 0.2 MPa (2 atm), residual
lock gases are vented directly to the atmosphere (Stream 3.2).
Steam and oxygen injected at the bottom of each gasifier react with the
coal to produce a hot, crude product gas. This gas exits the top of each
18
-------
MDUMlMO
CVClONEVENI
OMEDCOALFBOM.
1UIMG OK RATION*
HIGH FHE8SURE COM.
IOCK CASES AND GASIFIED
MAfltUIXUSESTO
FLARE tVSTEU
GASIIOUOIIIO
lARUPMUIOIIIH
tAMOH. SEMRATION UCIUH
CMJM FflOOUCI GAS
lOMCIISOLUCnON
tfPADATIOHtCCTIOH
lOIARUPAHAIOfl
MPAHAIIONSECflOH
OAtPROOUCIION
SKCf ION WASKWAIEH
Figure 2-6.
Process flow diagram showing sampling points In the Kosovo
Gas Production section.
-------
gasifier and is quenched directly with water. The gas is then cooled further
in a series of indirect heat exchangers. After cooling, the gas is routed to
the Rectisol section for purification. Condensed organic liquids and process
condensate generated during the quenching and cooling processes are sent to
the Tar/Oil Separation section.
Hot ash generated during gasification is collected from the bottom of
each gasifier in a lock hopper. This ash is water-quenched and discharged
(along with power plant ash) to a landfill. Ash quench blowdown water is
combined with the coal bunker scrubber blowdown and discharged (Stream 12.3).
Ash lock expansion gases are routed through a water-washed cyclone to remove
entrained particulate matter. These gases- are then discharged to the atmos-
phere (Stream 3.5). The wastewater and ash discharged from this cyclone are
combined with the two previously mentioned wastewater streams and discharged
(Stream 12.3).
The startup of a gasifier normally requires approximately eight hours.
During the initial stages of startup, the gases generated are vented directly
to the atmosphere (Stream 3.3). Later in the startup sequence, when a com-
bustible gas is being produced, the gas is routed to the flare system (Stream
3.6).
The significant process and discharge streams in the Gas Production sec-
tion are given in Table 2-3. The dedusting cyclone vent (Stream 2.2) contains
particulates which are of concern although the gas itself is primarily- air.
Streams 3.2, 3.3, and 3.6 are all very difficult to characterize because the
coal lock depressurization and gasifier startup processes are periodic and
variable. The coal lock bucket vent (Stream 3.1) was not found to be signi-
ficant due to plugging of the vent. Gases normally vented through this line
were being released through the low pressure coal vent during the Phase II
testing program.
Because of its high flow rate, the ash leaving the gasifier is potential-
ly an environmentally significant discharge stream. The main problem associa-
ted with disposal of the ash is the potential for soluble pollutants to be
leached from the ash in the landfill.
2.2.3 Rectisol Section
In the Rectisol section, acid gases such as I^S, C02, and HCN are re-
moved from the product gas. A process flow diagram for the Rectisol section
is presented in Figure 2-7.
Cooled crude product gas (Stream 7.3) at about 228C (728F) and 2.3 MPa
(23 atm) enters the Rectisol section from the Gas Production section. The gas
is then cooled further by washing with cold water followed by cold methanol.
Condensed liquids generated during this cooling include an organic phase
(naphtha) and an aqueous phase. The naphtha (Stream 7.6) is sent to the By-
Product Storage section while the aqueous stream (Stream 7.5) is sent to the
Tar/Oil Separation section.
20
-------
TABLE 2-3. SIGNIFICANT PROCESS AND DISCHARGE STREAMS IN KOSOVO GAS PRODUCTION SECTION
Stream
Number
2.0
2.1
2.2
3.1
3.2
3.3
3.4
3.S
3.6
12.1
12.2
12.3
1 I-
• 4 -
Stream
Description
Dried Coal
Coal Boom Oaaea
Deduating Cyclone Vent
Coal Lock Bucket Vent
Low Preaaore Coal Lock
Vent
Gaaifier Start-up
Vent
Gaa Liquor Tank Vent
Ash Lock Cyclone Vent
High Pro i Euro Coal Look
Vent
Dry Gaaifier Aah
Wet Gaaifier Ash
Quenched Aah Waatewater
gaaeoua
aqueoaa
aolid
Stream1 Doeign2
Type Flow Bate
a 16 .000
1 Unknown
1 4.400
g 21
1 "
g Unknown
1 Unknown
( >«
g 310
a 2.700
a > 2.700
eq 3
Beat Value2*1
Flow Bate
ND«
ND
7.200
ND
33
Variable
44
71
230
ND
ND
ND
•
Comment a
Sampled in Phaae II
Sampled in Phaae II; Primarily Coal Duat
Sampled in Phaae II; Mainly Air with Coal Particulate
Sampled in Phaae II; Normally Plugged
Sampled in Phaae II; Similar to Crude Product Gaa;
Containa Particulate
Sampled in Phaae III Variea with Time
Not Sampled in Phaae II; Compoaitloa aimilar
of Stream 13.7
Sampled in Phaae II; Mainly Stream, Oj. and
Gaaea
Sampled in Phaae II; Mainly Fixed Gaeea and
late
Sampled in Phaae II
Not Sampled in Phaae II
Not Sampled in Phaae II
to that
Fixed
Particn-
2A11 dry gat flow ratea in m*/gasifier-hr at 2J«Cj aqueoua flow ratea in mj/(aaifler-hr; aolid flow ratea in kg/ga«l(ior-hr
'See Appendix A for diacuaaion of beat value determination
*ND - Not Determined
-------
e
O
CJ
0)
tn
O
co
u
0)
O
O
CO
3
O
a
00
I
co
00
•H
S
o
)-i
00
ca
g
CO
ca
ai
o
o
u
eu
60
22
-------
After cooling, the crude product gas is scrubbed with cold methanol in
the H2& absorber. i^S-rich waste gas (Stream 7.1) is released from the
H2S-rich methanol during the methanol regeneration process and is routed to
the flare system.
The H2S-lean product gas goes to two CO2 absorbers. In these columns
the bulk of the €03 remaining in the product gas is absorbed by a wash of
C(>2-lean methanol. The overhead gas from the first C02 absorber is fed
directly into the fuel gas distribution system. The second C02 absorber is
used to remove additional CC>2 whenever 'pure' product gas is needed for feed
to the cryogenic hydrogen separation unit.
The significant process and environmental discharge streams in the
Rectisol section are given in Table 2-4. The l^S-rich waste gas (Stream
7.1) is particularly significant. The high sulfur species content and high
flow rate of this stream make it a significant control problem. At Kosovo,
the C02~rich waste gas (Stream (7.2) is vented directly to the atmosphere.
U.S. standards will probably require some control of this discharge stream to
restrict the emission of hydrocarbons, carbon monoxide and sulfur species.
2.2.4 Tar/Oil Separation Section
In the Tar/Oil Separation section, heavy tar, light tar, and medium oil
are separated from the plant's condensed gas liquor streams. A series of
phase separators are used to remove these organic fractions from the incoming
condensate streams. A process flow diagram for this section is shown in
Figure 2-8.
The light tar and medium oil by-products separated from the inlet gas
liquor streams are sent to the By-product Storage section, while the aqueous
phase from the phase separators is sent to the Phenosolvan section for further
treatment. A sludge consisting primarily of heavy tar and coal dust is sent
to a landfill (Stream 13.8).
Significant process and discharge streams in the Tar/Oil Separation sec-
tion are given in Table 2-5. There are six tank vents discharging directly to
the atmosphere (Streams 13.1, 13.5, and 13.7). Expansion and waste gases
(Stream 13.6) are sent to the flare system.
2.2.5 Phenosolvan Section
In the Phenosolvan section, phenolic water from the Tar/Oil Separation
section is treated to remove residual tars and oils, dissolved gases (prin-
cipally ammonia), and dissolved organics (principally phenols). A process
flow diagram of the Phenosolvan section is shown in Figure 2-9.
The phenolic water enters the Phenosolvan section through a degassing
cyclone where dissolved gases are released and vented to the atmosphere. The
water is then routed through a storage tank/gravity separator, and a series of
23
-------
TABLE 2-4. SIGNIFICANT PROCESS AND DISCHARGE STREAMS IN KOSOVO RECTISOL SECTION
Streea
Number
7.1
7.2
7.3
7.4
7.S
7.6
7.7
Streta
Deecription
B2S-Rich-Veete Gee
C02-Rich Vent Gee
Crude Product Gee
Cleen Product Gee
Cytnic Weter
By-Product Nepatbe
Internediete Proceee
Gee
Stteea1 Deei|B2
Type Flow Rete
1 2.700
I 2,400
1 18.800
, 13.100
e4 O.I
ol 130
1 1C. 300
Beet Velue2'1
Flow Bete
3.600
3.600
ND<
ND
ND
ND
ND
Stapled
Stapled
Stapled
BCN
Stapled
Seeipled
Stapled
Seeipled
in Pbeee Hi
in Pheee Hi
in Pbeee Hi
in Pbeee Hi
In Pbeee II
in Pbeee II
in Pheee II;
Coaaeutl
Heinly COj. B2S. NHj
Mlluly C0j
Heinly Fixed Geeee With H2S end
Heinly Fixed Geeee
et Staple Point 15. 3B
Heinly Fixed Geeee
1 ( - (eeeoue
to, - tqueoul
ol - orgenia liquid
2A11 dry gee flow retee in a3/getifier-hr et 25>Ci tqueont flow rete in a3/geeifier-hr. orfenio liquid flow retet in kg/geeifier-hr
3Seo Appendix A for dlteueeion of beet velue detentinetioa
4ND - Not determined
-------
N>
Ul
dASCONOENSAIE
HUURECtlSOt
SECIIOH
GASLKUOHfROU
OAE PRODUCTION SECTION
1M STAGE COOLERS
OASUQUOAfHOU
Q*5l>flOOUCIIOH6ECllO«t
IU STAGE COOLERS
WASICOAt
TOfL;
1
It
»
X*
v_.
i
*1
1
*f\ UEWI
11 SEP.,
WAICR
X
EXPANDER
/
MOIL
IAIOR
COAI
CONMNSAU
PUSH—
U
L — (
tJ
CONE
IAH
Q'
'
UNHJRI
TANKV
[
IUNHMI
TAN,
*
IEHSAIE .
KVCNI '
US •|"\
ANK \J Ufa
TAN
OH *\
"» t
•e (I u"
~l>—
MCNOLICWA
, H
/I PHCMOUC
VI t«H«
UGHI
MEOHJUOILTO
• ivraoouci
SIORAOE SECIION
«ANWWAKR ,
FHOMMCtlSOl'
GAS IIOUOH FROM
VCNTUMSCnuWERIN
GAS MOOUCIION SECIION
lAHANDmEHOLIC
WAtERFHOMSUHOEIANK (-
INPHENOSOUAHSCCTON
IAR
SEPAHAIOR
\/
PHENOIICWAIHI
I AH i Aim
VENT
FHENOLICWAIERIO
tf PHENOSOIVAM
HCTKM
(I
1IGHIIARTO
•••VPDODUCI
IIORAQE
_ TAR
tWAIE»/l UHPliatTAK \~\
Figure 2-8. Process flow diagram showing sampling points in the Kosovo
Tar/Oil separation section.
-------
TABLE 2-5. SIGNIFICANT PROCESS AND DISCHARGE STREAMS IN KOSOVO TAR/OIL SEPARATION SECTION
N3
Stream
Number
13.1
13.2
13.3
13.4
13.5
13.6
13.7
13.8
13.9
13.10
13.11
Stream
Description
Tar Tank Vent
Unpnre Tar Tank Vent
Medium Oil Tank Vent
Unpure Oil Tank Vent
Condensate Tank Vent
laate Gas to Flare
Phenolic Vater Tank
Vent
Heavy Tar and Duet
Light Tar By-Product
Medium Oil By-Product
Phenolic Water
Stream1 Design2
Type Flow Sate
g >0.44
g Negligi-
ble
( 0.27
g Negligi-
ble
f Unknown
( 2t
( >1«
a 100
ol 400
ol 2SO
aq ND
Best Value1'3
Flow Bate
0.51
ND«
1.7
ND
3.4
ND
I.S
ND
ND
ND
ND
Comment*
Sampled in Phase 11; Mainly air and fixed gases
Not Sampled in Phase II) Mainly air
Sampled ia Phase II; Mainly Acid Gasea and Methane
Not Sampled In Phase Hi Mainly AU
Sampled in Phase II; Mainly Fixed Gasea
Sampled in Phase Hi Mainly Fixed Oases,
and Snlfur Species
Sampled In Phase II; Mainly later. Fixed
Hydrocarbons
Gasea
Sampled In Phase II for Trace Elements, PNA's
Sampled in Phase II
Sampled In Phase II
Sampled in Phase II at Sample Point 14.0
sq - aqueous
ol - organic liquid
s - solid
2A11 dry gat flow rates in »*/gaaifier-hr at 25«C; aqueous flow rates in m*/gasifier-hr; organic liquid and heavy tar flow ratea In kg/gasifier-hr
3$ee Appendix A for discussion of best value determination
-------
PHCHOtlCWMER
FHOMItHOIL
ro
rOTAASCPAfUtOH
WIAHOM. StPAMIKW SCCIMM
UNO.fAMOII.ro
n raaoucinoiuGf BECIUN
ocOAssma AASIAMK
CVCUWEWNT VEMr
mcuoucwAifn
TANK yCW
QfHINOlIC I
WAtUIAIW I
AUORMMVENI
/•"•>. AUUONU
IIMPTtCI
T
t-e
HHiUCOVEWirarui
NOIINiaMKiWNNa
nnnuauy
JCONOCNUIE
QAUUOMU T
'"" I
\__AMHOMUianmaoucT
1 I" nwuatuciioN
.© J
FHCNOSOLVAN
WACTEWAIC*
aciw* T\_
mtMOtUMK \J
CHUM PHENOl IO
ivraoaucT
•IOHAGCSECIIOH
Figure 2-9. Process flow diagram showing sampling points In the Kosovo Fhenosolvan section.
-------
sand filters to remove residual tars and oils. Oils collected from the sur-
face of the stored wastewater are sent to the By-Product Storage section while
the tars and filter backwash water are returned to the Tar/Oil Separation
section.
After removal of residual tars and oils, the phenolic water is heated and
fed to two degassing columns. In these columns, dissolved gases such as
NH3, C02, and ^S are steam-stripped from the water. According to the
Kosovo process design, the ammonia removed in this process is supposed to be
collected as a by-product and sent to the By-Product Storage section. How-
ever, during the Phase II test program, this ammonia was not being recovered
but was being discharged directly to the atmosphere through the ammonia strip-
per vent (Stream 14.5).
The phenol-rich water leaving the degassing columns is routed through a
series of heat exchangers and then through extraction columns to remove phe- '
nols by extraction with diisopropylether (DIPE). The phenol-rich DIPE is
thermally regenerate by distillation, producing lean DIPE which is recycled to
the Extraction section. The crude phenols which are separated from the DIPE
during the regeneration process are sent to the By-Product Storage section.
Significant process and discharge streams for the Phenoslvan section are
given in Table 2-6. There are twelve gaseous discharge vents in this section.
The vent of primary concern is the ammonia stripper vent (14.5).
2.2.6 By-Product Storage Section
The By-Product Storage section is designed to store the liquid by-
products generated in the Tar/Oil Separation, Phenosolvan, and Rectisol sec-
tions. The by-products stored in this section are light tar, medium oil,
naphtha, crude phenol, and unclean oil. By-product NH^OH is also supposed
to be stored in this section; however, this by-product was not being recovered
during the test program. A process flow diagram of the By—Product Storage
section is shown in Figure 2-10.
There are six discharge sources in the By-Product Storage section. All
of these sources are tank vents discharging vapors to the atmosphere. Table
2-7 shows these By-Product Storage section, discharge streams.
2.2.7 Flare System
The flare system is used to burn some of the gasification plant's most
significant discharge streams. Streams routed to the flare are:
• high pressure coal lock expansion gases from the Gas
Production section (Stream 3.6),
• gasifier startup gases from the Gas Production section
(Stream 3.6),
• H2S-rich waste gas from the Rectisol section (Stream 7.1),
and
• expansion and waste gases generated in the Tar/Oil Separation
section (Stream 13.6).
28
-------
TABLE 2-6. SIGNIFICANT PROCESS AND DISCHARGE STREAMS IN KOSOVO PHENOSOLVAN SECTION
Stream
Number
14.0
14.1
14.2
14.3
14.4
14. 5
14.6
14.7
to 14.8
VD
14.9
14.10
14.11
14.12
14.13
14.14
14.15
14.16
Stream
Description
Phenosolvan Inlet Water
(Phenolic Water)
Degaasing Cyclone Vent
Gaa Tank Vent
Unclean Oil Tank Vent
Phenolic Water Tank
Vent
Ammonia Stripper Vent
Cooler Vent
Second Degassing Vent
Slop Tank Vent
Crude Phenol Tank Vent
DIPE Tank Vent
Waatewater
NHj Abaorber Vent
NH3 Storage Tank Vent
N1I4OII By-Product
Unclean Oil (to
By-Product Storage)
Crude Phenols (to
By-Product Storage)
Stream1
Type
•«
1
I
1
1
1
1
1
1
f
1
•q
1
1
•q
ol
ol
Deaign 2
Flow Rate
>13
2.2
ND
ND
ND
9.8
4.4
0.4
Unknown
0.09
O.I
13
Unknown
• Unknown
200
300
90
Beat Value***
Flow Rate
ND
ND<
ND
ND
ND
260
ND
ND
ND
0.20
ND
ND
ND
ND«
ND
ND
ND
Conmenta
Sampled in Phase II
Not Sampled in Phaae Hi Containa 82$. Acid Gases
Not Sampled in Pbaae Hi Mainly Air
Not Sampled in Phaae Hi Mainly Air
Not Sampled in Phaae Hi Mainly Air
Sampled in Phaae Hi Mainly H^O. 82. N8j C02.
B2S. HCN
Not Sampled in Phase II; High NHj Content: Similar
to 14. I
Not Sampled in Phase Hi Mainly Air
Not Sampled in Phaae II; Mainly Air
Not Sampled in Phaae Hi Mainly Air
Not Sampled in Phaae Hi Mainly Air
Sampled in Phase Hi This Stream is Discharged
Not Uaed During Teat Program
Not Uaed During Teat Program
Not Used During Test Program
Not Sampled In Phase Hi Similar to Medium Oil
Product
Not Sampled in Phaae II
By-
I ~ gaseous
aq - aqueoua
ol - organic liquid
2A11 dry gaa flow rates in n3/g«sifier-hr at 2S«C. aqueoua flow ratea in m*/gaaifier-hr. by-product flow rates in kg/gaeifier-hr
3See Appendix A for a discussion of best value determination
*ND - Not determined
-------
OJ
o
LIGHT TAR
FROM TAR/OIL
SEPARATION
SECTION
MEDIUM OIL
FROM TAR/OIL
SEPARATION
'SECTION
NAPHTHA
FROM
RECTISOL
SECTION
CRUDE PHENOL
FROM
PHENOSOLVAN
SECTION
UNCLEAN
OIL FROM
PHENOSOLVAN
SECTION
NH
-------
TABLE 2-7. SIGNIFICANT PROCESS AND DISCHARGE STREAMS IN KOSOVO BY-PRODUCT STORAGE SECTION
Stream
Number
15.1
15.2
15.3
15.4
15.5
15. £
Stream
Description
Light Tar Storage Tank
Vent
Medina Oil Storage Tank
Vent
Naphtha Storage Tank
Vent
Crude Phenol Storage
Tank Vent
Unclean Oil Storage
Tank Vent
NH^B Storage Tank
Vent
Stream1
Type
1
1
f
I
I
1
Deaign2
Flow Kate
0.55
0.27
0.14
0.09
0.03
0.22
Best Value2'*
Flow Rat*
ND* Not Sampled in Phase
of Stream 13.1
ND Not Sampled in Phase
of Stream 13.3
4.5 Sampled in Phase II;
Hydrocarbons
ND Not Sampled in Phase
ND Not Sampled in Phaae
of Streaa 13.3
Coi
II;
II;
amenta
Composition Similar
Composition Similar
to that
to that
Mainly Air and Aromatic
II;
II;
Mainly Air
Composition Similar
to that
Not in Use During Testing Program
2A11 dry gaa flow rates in B3/gasifier-hr at 25*C
3Sec Appendii A for discussion of best determination
4ND - Not determined
-------
SECTION 3
RATIONALE FOR PHASE II TESTING
The purpose of the Kosovo test program was to obtain representative data
on the potential environmental impacts of uncontrolled Lurgi-type gasification
technology. The data obtained from the Kosovo program may be used to aid in
the design of process modifications and control schemes for U.S. Lurgi faci-
lities. For each phase of the program, a test plan was developed so that the
sampling and analytical work performed could achieve that phase's objectives.
This section presents the rationale used to develop the Phase II test plan.
The primary objectives for this phase of the program were:
• to verify and supplement the Phase I test results, and
• to identify and measure trace pollutants, both organic
and inorganic, in the plant's discharge streams.
3.1 PLANT SECTION SELECTION
The gasification plant sections selected for study were those considered
to be an essential part of Lurgi system and/or those which contained discharge
sources unique to the process of gasifying coal. Based on these criteria, the
following plant sections were included in the Phase II test plan:
Coal Preparation,
Gas Production,
Rectisol (Acid Gas Removal)
Tar/Oil Separation,
Phenosolvan,
By-Product Storage, and
Flare System.
The Kosovo plant sections not studied in Phase II along with reasons for omis-
sions are listed below:
Steam Plant;
Inlet Water Treatment;
Cooling Water System;
Process Wastewater Treatment;
Oxygen Plant;
section contained no waste streams
unique to Lurgi gasification systems.
section contained no waste streams
unique to Lurgi gasification systems.
section contained no waste streams
unique to Lurgi gasification systems.
Facilities not in service.
section was not a direct source of
major discharge or by-product streams,
32
-------
Product Gas Distribution; section was not a direct source of
major discharge or by-product streams.
3.2 STREAM SELECTION
Engineering judgment, pretest screening results, and the Phase I test
results were used to select the streams from which information relevant to the
Phase II objectives could be gathered.
In general, a stream was selected for testing for one or more of the
following four reasons:
• a high discharge rate,
• a significant pollutant concentration,
• contributed to the trace pollutant characterization, or
• provided useful process information.
The streams which were selected for testing in Phase II are shown in Table
3-1.
3.2.1 High Discharge Rate
Discharge and flare feed streams which were found in Phase I or deter-
mined from plant design to have a significant rate of discharge were selected
for testing. For example, the CC^-rich waste gas design flow rate is 2400
m^/gasifier-hr at 25"C. This makes this stream one of the largest in the
plant. Even a low concentration of a pollutant in this stream could be sig-
nificant. Therefore, it was included in the Phase II study. Streams were
also included if the quantities of entrained particulates discharged with the
streams were likely to be significant. The dedusting cyclone vent gas is one
example.
3.2.2 Significant Pollutant Concentration
Some discharge and flare feed streams were likely to impact the environ-
ment even at low discharge rates. This criterion allowed a stream to be
selected based on the 'quality' of its discharge. For the purposes of this
test program, the SAM/1A multimedia environmental goals (see Section 5.0) were
used as a guideline for analyzing severity of a stream component.
An example of a stream selected on this basis is the naphtha storage tank
vent gas. Phase I test results indicated that the concentration of aromatic
hydrocarbons (primarily benzene and toluene) and mereaptans in the Naphtha
storage tank vent gas were high. These compounds are considered to be poten-
tially harmful pollutants.
33
-------
TABLE 3-1. KOSOVO STREAMS SELECTED FOR PHASE II TESTING
Reason for Selection
Sample
Point
Stream Name
Media
Coal Preparation Section
1.2
1.3
1.1
Fleissner Autoclave Vent
Fleisner Condensate
Fleissner Baghouse Catch
gaseous
aqueous
solid
Gas Production Section
2.2
3.2
3.3
3.6
12.3
2.0
2.1
12.1
12.2
De dust ing Cyclone Vent
Low Pressure Coal Lock
Vent
Gasifier Startup Vent
High Pressure Coal Lock .
Vent
Quenched Ash Wastewater
Dried Coal
Coal Room Dust
Dry Gasifier Ash
Wet Gasifier Ash
gaseous
gaseous
gaseous
gaseous
aqueous
solid
solid
solid
solid
4J C« !
3 N rH
r-l -H i CO
f»f 14 \ ^
O CU ! O
PU 4J 1-1
U 4J
-------
TABLE 3-1. (Continued)
Reason for Selection
Sample
Point
Rectisol
7.1
7.2
7.3
7.4
7.7
7.5
7.6
Tar/Oil
13.1
13.3
13.6
13.7
13.8
13.9
13.10
Stream Name
Section
H2S-Rich Waste Gas
C02-Rich Waste Gas
Crude Product Gas
Clean Product Gas
Intexmediate Process
Gas
Cyanic Water
By-Pro duct Naphtha
Separation Section
Tar Tank Vent
Medium Oil Tank Vent
Waste Gas to Flare
Phenolic Water Tank Vent
Heavy Tar
By-Pro duct Light Tar
By-Product Medium Tar
Media
gaseous
gaseous
gaseous
gaseous
gaseous
aqueous
organic liquid
gaseous
gaseous
gaseous
gaseous
solid
organic liquid
r-l
co
c
o
•H
U
CO
o
M-l
C
M
X
X
X
X
X
X
X
(Continued)
35
-------
TABLE 3-1. (Continued)
Sample
Point Stream Name Media
Phenosolvan Section
14.5 Ammonia Stripper Vent gaseous
14.0 Phenosolvan Inlet Water aqueous
14.11 Phenosolvan Wastewater aqueous
By-Product Storage Section
15.3 Naphtha Storage Tank gaseous
Vent
Flare System
20.1 Combined Gas to Flare gaseous
Reason for Selection
0)
4-1
CO
(A
&4 4<^
O
iH
CO
O
•H
4J
crt
g
i-i
O
5
X
36
-------
3.2.3 Trace Pollutant Characterization
Some streams were selected to yield useful information as to the fate of
the inorganic trace elements which enter the plant with the coal. In the
gaseous phase, streams were selected before the water quenching step in the
Gas Production section (low and high pressure coal lock vent gases) where
trace elements could be discharged. Rectisol section gases were also chosen
to determine the extent to which the more volatile trace elements could remain
in the gas after the water quenching and cooling process. Aqueous, by-product
and solid waste streams were selected to determine in which streams the var-
ious elements left the gasification system.
Trace organic characterization was considered to be an essential part of
the Phase II test program. Analyses for trace organics were performed for all
of the streams selected for other reasons. Particular emphasis was given to
the trace organics in the Phenosolvan wastewater, heavy tar, and liquid by-
products.
3.2.4 Informational Value
Some streams were included in the Phase II test plan because they would
provide useful information for understanding the Kosovo plant operation or for
determining the fate of important compounds. For example, the Phenosolvan
inlet water was selected because it would allow the effectiveness of the
Phenosolvan section to be studied. Similarly, the liquid by-products (light
tar, medium oil, and naphtha) were included because many key compounds, inclu-
ding trace organics and inorganics, were likely to end up in these by-products
In addition, the information obtained could aid in assessing the suitability
of these by-products for use as on-site fuels.
3.3 SELECTION OF STREAM PROPERTIES FOR PHASE II TESTING
The stream properties selected for study in Phase II were included for
one of three reasons: flow rate determination, stream composition characteri-
zation, or trace pollutant characterization. The sampling and analytical pro-
cedures used to develop these data are discussed in Section 4.
For gaseous streams, the dry gas mass flow rate was found by determining
total stream volumetric flow rate, temperature, molecular weight, and moisture
content. Gaseous stream compositions were determined by analyzing, for fixed
gases, hydrocarbons, sulfur species, and nitrogen species.
Aqueous stream quality was characterized by water quality parameters,
such as COD and pH. Physical properties, dissolved and suspended solids, tem-
perature, and trace pollutant concentrations were also determined.
For solid and organic liquid streams, Proximate, Ultimate, and trace pol-
lutant analyses were performed. Resource Conservation and Recovery Act
Extraction Procedure (RCRA EP) leachate analyses for trace elements in the
gasifier ash were included to determine if a landfill was an acceptable
37
-------
disposal option for this stream. Information about the vapors from the by-
product storage tanks was obtained by performing head space tests of the
liquid by-product samples.
Bioassay tests were performed using samples from the following seven
streams: dry gasifier ash, heavy tar, light tar, medium oil, naphtha,
Phenosolvan inlet water, and Phenosolvan wastewater. These tests were per-
formed to provide information about potential biological effects from the
Kosovo plant's solid, liquid by-product, and wastewater streams.
38
-------
SECTION 4
TEST METHODOLOGY
The data acquisition task of the Kosovo source test and evaluation
program consisted of extensive sampling and analyses. The sampling and ana-
lytical methods employed in this program are described in this section.
Accepted and publicly documented methods were used where practical. A brief
summary of the sampling and analytical methods is given in Table 4-1.
4.1 SAMPLING METHODS
The descriptions of the sampling methods contained in this subsection are
grouped by stream type (gas, liquid, solid) then within each stream type by
analytical parameter. The majority of the sampling effort at Kosovo was dir-
ected toward gaseous streams. The sampling of these streams was more complex
than the liquid or solid streams. The liquid and solid streams required a
much smaller portion of the sampling effort.
4.1.1 Gas Streams
The descriptions of sampling methods in this program are centered on the
apparatus used to collect the samples. The use of the sampling apparatus is
assumed to be self-evident once the apparatus has been described. For the
purpose of this discussion, the sampling apparatus or train used to collect
samples for further characterization is divided into two parts, 1) that por-
tion of the train to remove the gas to be characterized from the bulk of the
gas stream (nozzle and probe) and 2) that portion of the train which collects
those components of the gas stream to be actually analyzed (impingers, sor-
bents, etc.).
The configuration of the front half of the sampling train which extracts
the gas from the* stream is governed by the physical characteristics of the
stream while the configuration of the back half of the sampling train is
governed by the chemical species being collected for analysis.
The gas streams were grouped as presented in Table 4-2. The groupings
were based on the probe-to-port sealing configuration required to gain access
to the gas stream. Figure 4-1 shows the configuration of the sampling probe
while- the probe-to-port sealing mechanisms are shown in Figure 4-2 (A through
D). Samples were obtained and the total flow rates of gases emitted from tank
vents were measured with the apparatus shown schematically in Figure 4-3.
Even though the port, probe and sealing mechanism for most streams were
similar, the sample collection devices (back half of the train) were varied to
fit the collection requirements for each set of species to be analyzed. A
description of the sampling equipment for each of the parameters listed in
Table 4-1 follows.
39
-------
TABLE 4-1. SAMPLING AND ANALYTICAL METHODS
Parameter
Collection Method
Analytical Method
CONDENSABLE HYDROCARBONS:
Condensable Hydrocarbons
Benzene, Toluene, and
Xylene
Gas stream cooled to 0 C and resul-
ting condensate trapped in impingers.
The remaining condensable hydrocar-
bons trapped on XAD-2 resin
Vapors trapped from gas stream by
activated carbon
Organic material extracted from
condensate and resin with CH2C12
Extract analyzed with gas
chromatograph and gas chroma-
tography/mass spectrometry
Vapors solvent extracted from
carbon and analyzed by GC with
flame ionization detector
GASEOUS SPECIES BY GC:
Fixed Gases (CO, H2, C02,
N2, 02,
Hydrocarbons Cj-C6, C6+
Benzene, Toluene and
Xyelene
Sulfur Species (H2S, COS,
CS2, SO 2, Mer cap tans)
Sample was heated, filtered and
dried then compressed into silan-
ized glass bombs for analyses
Sample was heated, filtered and
dried then compressed into silan-
ized glass bombs for analyses
Sample was heated, filtered and
dried then compressed into silan-
ized glass bombs for analyses
Gas chromatograph with ther-
mal conductivity detector
Gas chromatograph with flame
ionization detector
Gas chromatograph with flame
photometric detector
(Continued)
-------
TABLE 4-1. (CONTINUED)
Parameter
Collection Method
Analytical Method
PARTICULATE:
Suspended Particulate
Suspended Particulate
Plus Condensables
EPA Method 5, gas filtered at
250°F out of stack
EPA Method 17, gas filtered at
duct temperature in stack
Condensation and collection in
a series of water filled impingers
Gravimetric
Gravimetric
Filtration, extraction with
CH2C12, Gravimetric
TRACE ELEMENTS:
Non-Volatile Elements
(Be, Cd, Co, Cr, Cu,
Mo, Ni, Pb, Sr, Te,
V, Zn)
Volatile Elements
(Hg, As, Sb, Se)
Iron and Nickel Carbonyls
2 impingers with 10% HN03 followed
by 2 impingers with 10% NaOH.
2 impingers with 10% HN03 followed
by 2 impingers with 10% NaOH
2 fritted impingers with 3% HC1
Dissolution, AA with graphite
furnace
Dissolution, AA with Hydride
Generation
AA with Graphite Furnace
(Continued)
-------
TABLE 4-1. (Continued)
Parameter
Collection Method
Analytical Method
to
OTHER GASES:
Ammonia
Hydrogen Sulfide
Hydrogen Cyanide
Phenols
2 fritted impingers with 0.1 N
H2SO.,
2 fritted impingers with 0.1 N
cadmium acetate
2 fritted impingers with 0.1 N cad-
mium acetate followed by 2 fritted
impingers with 0.1 N NaOH
2 fritted impingers with 0.1 N
NaOH
Distillation into boric acid
and back titration with
sulfuric acid
Iodine addition and back
titration with thiosulfate
Distillation and titration
with silver nitrate
Spectrophotometric determine
ation by reaction with
4-aminoantipyrine
-------
TABLE 4-2. PROBE/PORT CONFIGURATION FOR KOSOVO GAS STREAMS
Stream Characteristics
A. Atmospheric pressure, non-toxic
components
B. Moderate pressure and/or toxic
components
C. Moderate pressure and/or highly
toxic components
D. High pressure
E. Tank vents to atmosphere
Probe/Port Configuration
Probe sealed at port with fabric
stuffing
Probe sealed at port with packing
gland
Probe sealed at port with packing
gland and isolated from gas
stream with a gate valve
Probe sealed at port with packing
gland and isolated from gas stream
with a gate valve. Mechanical
drive used to insert probe
against stream pressure
Total stream routed through a
calibrated orifice - sample
obtained through Teflon® tube
43
-------
SAMPLE
NOZZLE
THERMOCOUPLE
PITOTTUBE
PROBE TO PORT SEALING MECHANISMS
SHOWN IN FIGURE 4-2 A-D
TO SAMPLING
TRAIN
Figure 4-1. Probe configurations.
-------
PORT
PHOBE
A. ATMOSPHERIC PRESSURE, NON-TOXIC COMPONENTS
GATE VALVE
REDUCER
, I---
J
PORT-
B. MODERATE PRESSURE AND/OR TOXIC COMPONENTS
<=^=3
GATE VALVE
PORT
C. MODERATE PRESSURE AND/OR HIGHLY TOXIC COMPONENTS
PORT
D. HIGH PRESSURE
Figure 4-2. , Probe to port sealing mechanism.
-------
TANK VENT
BAG
ENCLOSURE
TEFLON
SAMPLE LINE
TANK
TEMPERATURE
READOUT
CALIBRATED
ORIFICE
I
K> SAMPLING
TRAIN
Figure 4-3. Sampling apparatus for tank vent.
-------
4.1.2 Mass Flow Rate
The flow rates of the gas streams sampled were determined from the data
collected during sampling. These data included the pressure differential
generated by the pitot attached to the probe and the gas density. The gas
density was calculated from the gas composition, gas temperature, and gas
stream pressure. The S-type pitot and thermocouple are shown in Figure 4-1.
A description of the methods used to determine the gas flow rate for each
stream is contained in EPA Reference Methods 1 through 4 (Ref. 4-1).
An alternate procedure was used to obtain samples and measure flow for
tank vents discharged directly to the atmosphere. Gas from these small vents
was routed through a calibrated orifice as shown in Figure 4-3. The gas flow
rate was calculated from the pressure drop across the orifice and the gas den-
sity. Samples for collection and analysis were extracted through a flexible
Teflon® tube inserted upstream of the orifice.
4.1.3 Condensable Hydrocarbons
Two collection techniques were used to obtain samples for analysis of
condensible hydrocarbons. The less,volatile species were collected by con-
densation following by sorption of any remaining vapor with a porous polymer
resin (XAD-2®). The more volatile species were sorbed by activated carbon
using a different train. In terms of collecting ability, the division between
these two techniques is not sharp. The samples from the XAD-2® collection
technique were analyzed for hydrocarbons having boiling points above that of
naphthalene while the charcoal tubes were analyzed for benzene, toluene, and
xylene.
The higher boiling condensable hydrocarbons were collected by a train, as
shown in Figure 4-4, consisting of impingers as follows:
1st and 2nd - 0.2L distilled water
3rd - 100 g of clean prepared XAD-2® resin
4th - preweighed silica gel
The .impingers were placed in an ice bath during sampling. Gas streams with a
high moisture content, above 50% by volume, were sampled with empty impingers
placed upstream of those shown in Figure 4-2 to remove the excess condensate
and provide additional cooling of the gas sampled.
Remaining hydrocarbons were sorbed by the resin held in a canister made
from a modified impinger. Coarse glass frits were used at the entrance and
exit of the canister to prevent the loss of resin. Pre-weighed silical gel in
the last impinger trapped any remaining water vapor.
Sampling was prformed isokinetically with flow rates of approximately 1.4
E-04 Nm-Vs. Typical sampling volumes were 0.2 to 0.5 Nin^.
47
-------
FRIT
~\
00
ORIFICE
SAMPLE LINE
FROM PROBE
D.I. WATER
PREWEIGHED
SILICA GEL
XAD-2 RESIN
FRIT
k \ VACUUM
' GAUGE
VALVE
I DRY GAS
METER
,
VALVE
PUMP
Figure 4-4. Condensable organic sampling train.
-------
Material for analysis was recovered from the impingers as well as the
nozzle, probe liner, and interconnecting tubing and glassware. Material was
recovered from the probe and sample line with a methylene chloride rinse. The
aqueous portion of the impinger solutions was separated and stored. Remaining
organic material from the impingers and connecting glassware was recovered
with a methylene chloride rinse which was then combined with the probe rinse.
The XAD-2® resin and any sorbed hydrocarbons were transferred to the original
resin container. The silica gel was reweighed to determine its weight in-
crease due to moisture collection, then discarded.
A second technique was used to collect light aromatics (benzene, toluene
and xylene) which were poorly retained by the XAD-2® resin. The activated
charcoal collection tubes used for this technique had a four cubic centimeter
primary collection zone and a one cubic centimeter secondary collection zone.
A large gas tight syringe was used to draw samples through the collection
tubes at 5 E-06 to 8 E-07 NnrVs. Typically, multiple tubes were collected
with the sample volume spanning at least an order of magnitude. The actual
volumes were based on the suspected light hydrocarbon content of the stream
and ranged from 1 E-05 to 2 E-03 Nm-*. After the samples were drawn through
the tubes, the sampling time, location, and volume were recorded, the tube
ends were capped, and the tubes were stored in a refrigerator until analysis.
4.1.4 Gases for Gas Chromatographic Analysis
Samples for gas chromatographie (GC) analysis were collected with the
apparatus shown in Figure 4-5. These samples were analyzed for fixed gases
(N2, 02, H2, CO, C02 and CIfy), hydrocarbons, and sulfur species. The
purpose of the sampling and conditioning system was to remove particulates and
lower the dewpoint of the gas prior to cooling and pressurization into pre-
treated bombs. Particulates were trapped on a silanized glass fiber filter
and the moisture removed by a PermaPure® dryer. The gas was then cooled and
pumped into silonized glass bombs. The 0.5L bombs were purged with 5.0L of
conditioned sample and then pressurized to 50 kPa (0.5 atm). Immediately
after collection, each sample was transferred to the laboratory for analysis.
A fixed gas analysis was performed on each sample to assure that it had
not been contaminated with air prior to performing the more time consuming
hydrocarbon and sulfur species analyses.
4.1.5 Particulates
The particulate concentration of the gas streams was determined by one of
two techniques. In both techniques, the particulate mass collected was
determined gravimetrically. For gas streams with lower levels of condensables
(oils, tars and moisture) the particulate material was collected on a heated
filter. For gas streams with higher levels of condensables, the particulates
were collected in a series of water-filled impingers. The oils and tars were
extracted from the resulting impinger solutions by extraction with methylene
chloride. Particulate matter remaining in the Impinger solutions or in the
oils and tars extract was then removed by filtration.
49
-------
Ol
o
HEATED TEFLON
SAMPLE LINE
SS FILTER
HOLDER
DRY
AIR
FROM GAS
STREAM
ROTOMETER
SILANIZED GLASS
SAMPLE BOMBS
\_
TEFLON 1|
STOPCOCK~X\JL
SEPTUM
Figure 4-5. Gas sampling and conditioning apparatus.
-------
EPA Reference Method 5 (Ref. 4-1) was used to determine particulate con-
centrations in streams with low levels of condensables. Gas was drawn iso-
kinetically from the duct through a stainless steel button-hook nozzle and a
heated stainless steel lined probe. Particulates were then removed by a glass
fiber filter held at 121°C (250°F). The gas exiting the filter was passed
through a series of four impingers for the removal of condensables and water
vapor. Material was recovered from the probe, nozzle, and all connection
glassware prior to the filter using an acetone rinse aided with a brush. The
filter, with any particulates, was transferred to a clean tared petri dish.
The second technique used a series of water filled impingers for parti-
culate collection. The train had the same features and was used in the same
manner as the Method 5 train described in the previous paragraph, however, the
filter was bypassed. This technique allowed the collection of the large mass
of condensables without the filter blockage which would have occurred with a
Method 5 train.
The sample was recovered from the probe nozzle and lined with a methylene
chloride rinse. The weight increase of the impinger solution was determined
before the aqueous phase was transferred to storage containers. Then the
impingers and all interconnecting glassware were rinsed with methylene chlo-
ride to recover condensed oils and tars. This rinse was combined with the
probe and nozzle wash.
The impinger collection technique for particulates was combined with the
condensable hydrocarbon train (Section 4.1.3) when values for both parameters
were desired. Aliquots from each sample fraction prior to the XAD-2® resin
catch were taken for particulate determinations.
The weight increase of the impingers was recorded and the probe and
nozzle rinse (or aliquots) and impinger solution (or aliquots) were stored for
analysis of filterable particulates, condensable oils and tars recovered by
extraction, and dissolved solids recovered from the aqueous phase.
4.1.6 Trace Elements
Trace elements were collected in a series of seven impingers with
contents as follows:
Impingers Content
1 & 2 0.2L 10% HNO3
3 empty
4 & 5 0.2L 10% KOH
- 6 empty
7 preweighed silica gel
Gas was drawn through a nozzle-, probe, and sample line and then the series of
impingers listed above. As much sample as practical was collected to increase
sensitivity. The limiting factor on sample volume was the accumulation of
51
-------
condensable oils and tars or the formation of excessive carbonate precipitate
in the KDH impingers. Typical isokinetic flow rates were 9.4 E-05 to 1.6 E-04
NnrVs. A recovered sample consisted of four impinger solutions with connec-
ting glassware being rinsed into the previous impinger with distilled water,
plus a methylene chloride rinse of the nozzle, probe, sample line, and all
empty glassware.
Samples for analysis of metal carbonyls were collected with a train con-
sisting of two impingers each containing 0.5L of 3% HC1. Typical flow rates
were 3 E-05 NnrVs with sample volumes of 0.2 to 0.3 Nm^. The gas stream
was filtered before entering the impinger and was assumed to be in the vola-
tile carbonyl form. The recovered impinger solutions and glassware rinses
were stored separately for analysis.
4.1.7 Ammonia, Hydrogen Sulfide, Hydrogen Cyanide, and Total Phenols
Ammonia, hydrogen sulfide, hydrogen cyanide and total phenols were col-
lected independently from the gas stream using fritted impingers in series.
The impinger solutions for each run were as follows:
Ammonia
Hydrogen sulfide
Hydrogen cyanide
Phenols
4.1.8 Liquid Samples
No. of Impingers
2
2
2
2
2
Solution
0.05L 0.1N H2S04
0.05L 4% Cadmium acetate
0.05L Cadmium acetate
10% NaOH
0.05L 5% NaOH
Liquid samples were collected either with a dipper from streams with an
open hatchway, or from a spigot. The entrainment of air was avoided where
possible. Sample bottles were filled completely to minimize head space. Sam-
ple containers and preservatives appropriate for each of the planned analyti-
cal techniques were used.
4.1.9 Solid Samples
Most solid samples were collected at the outfall of a conveyor and stored
in appropriate containers. Grab samples of the dry bottom ash were collected
from the transfer line connecting the lower ash lock valve with the ash quench
chambers. Heavy tar was collected as a liquid and allowed to cool and
solidify.
4.2 ANALYTICAL METHODS
The analytical methods used during the Kosovo tests are described in this
subsection. Where applicable, methods accepted and/or documented by recog-
nized organizations were used. These organizations include the U.S.
Environmental Protection Agency, American Society for Testing and Materials
(ASTM), German Institute for Standardization (DIN) and the Soviet State
Committee on Standards (GOST).
52
-------
The analytical procedures discussed in this section address the following
sample types:
• gases,
• aqueous liquids,
• solids, and
• by-products.
Most of the analytical techniques used vary little for the different
sample types after the initial sample preparation has been performed. The
des criptions in this section are thus grouped by method. The preparation
required for each sample type, if required, is described as part of the
method.
4.2.1 On-Site Gas Analysis
Gas chromatographic (GC) techniques were used to analyze fixed gases,
hydrocarbons and vapor phase sulfur species in gas samples collected and con-
tained in pressurized glass bombs. The fixed gases were analyzed prior to the
other gases, thus verifying the sample integrity prior to starting the more
detailed and time consuming gas analyses. A flow scheme for these analyses is
shown in Figure 4-6. Table 4-3 describes the instrument, column, temperature
program, and detector used for each analysis.
4.2.2 Preparation of Samples for Organic Analysis
The scheme presented in this section addresses the preparation of samples
collected as described in Sections 4.1.3 (condensable hydrocarbons), 4.1.8
(liquids), and 4.1.9 (solids). Once prepared or extracted-, the analysis of
each sample type was the same. The types of samples prepared for organic
analysis were:
condensable organics sorbed on XAD-2® resin,
methylene chloride sample train rinses,
aqueous liquids,
by-products, .and
solids.
A sample may have extracts from two or more of the above classifications.
If so, these extracts were prepared individually then composited to form a
single sample for organic analysis. The numerical fraction of each extract
composited was the same for all extracts of a given sample. The extraction
and preparation procedures for each type of sample or matrix are discussed in
this subsection (4.2.2). Descriptions of the analyses of the composited *
extracts follows in subsection 4.2.3.
XAD-2® Resin
A porous polymer resin (XAD-2®) was used to sorb vapor phase organics
from the sample stream. Prior to sampling the resin was cleaned to reduce
53
-------
Collect Sample
in Glass Bomb
Analyze for
Fixed Gases
Reject Data
Resample
No
Yes
Continue Analyses
Sulfur
Species
Use Direct
Injection and
Analyze for
Sulfur Species
No
Light
drocarbons
Analyze for
Hydrocarbons and
Substituted Benzenes
Dilute Sample
for H2S-Analysis
Use Direct Injection
But Vent H2S
to Analyze for
Other Sulfur Species
Figure 4-6. Flow scheme for o'n-site gas chromatographic analyses.
54
-------
TABLE 4-3. ON-SITE GAS CHROMATOGRAPHIC ANALYSIS - INSTRUMENTS AND CONDITIONS
Sulfur Species
(H2S, CS2, COS,
S02, CH3SH,
CH3CH2SH )
Fixed Gases (02>
N2. H2, C02, CO,
CH,,)
Benzene, Toluene,
Xylenes
Hydrocarbons
(CI-GS, C6+) and
Fixed gases (C02,
CO, CHij, H2, 02,
N2)
Hewlett-Packard
Model 5730A with
FPD*
Varian Aerograph
Model 90-P with
TCD*
Varian Aerograph
Model 1400 with
FID*
Hewlett-Packard
Model 5840A with
TCD & FID*
3m x 1/8" O.D. Teflon® packed
with 1% TCEP 0.5% H3POit on 80-
100 mesh Carbopak B
3m x V O.D. Glass packed with
60-80 mesh, 13x molecular
sieve
3m x V O.D. S.S. packed with
10%- Carbowax 20 m on 80-100
mesh Chromosorb W AW
1) 9m x 1/8" O.D. S.S. packed
with 16% Bis-2-(tnethoxy-
ethyl) adipate on 80-100
mesh Chromosorb P AW, 2m
packed with 30% DC-200 on
80-100 mesh Chromosorb P AW
2) 3m x 1/8" O.D. S.S. packed
with 60-80 mesh 13X molecular
sieve
3) 2m x 1/8" O.D. S.S. packed
with 60-80 mesh Poropak Q
Hold 4 mino@ 40°C, 16°C/
min to 110°C, hold 12 min
@ 110°C
Isothermal @ 50 C
Isothermal @ 120 C
Isothermal @ 50 C
*FID = Flame lonization Detector
TCD = Thermal Conductivity Detector
FPD = Flame Photometric Detector
-------
background interferences which would be extracted during sample recovery. The
cleaning process for the resin consisted of a water wash to eliminate fines
followed by a methanol (CI^OH) wash. The resin was then soxhlet extracted
for 24 hours with CI^OH, then pyridine, and finally diethyl ether. After
cleaning, the resin was stored under CE^OH. Just prior to use it was
thoroughly drained and rinsed with clean water. Blanks were used to correct
for any organic material which was extracted from the clean resin during
sample recovery. The organics sorbed (or condensed) during sampling were
recovered from the resin by extraction with methylene chloride (Cl^C^).
The extracted organics were then separated into two fractions, one containing
the acids and the other containing the base/neutrals. The extracts were
separated into these fractions by liquid partitioning between the CH2C12 .
solvent and water (ph adjusted to 12 with NaOH for the base/neutrals). The
aqueous layer containing the acids was then back extracted with CH2C12
after adjusting the pH to 1 with HC1. The resulting acid and base/neutral
fractions were then combined with other like fractions from other portions of
the same sample if appropriate. The extraction flow scheme for the resin is
shown in Figure 4-7.
Sample Train Rinses
Sample recovery from a gas sample collection included a rinse of the
sampling train with CI^C^. This rinse removed organics and particulates
coating the interior walls of the train. The scheme, shown in Figure 4-8,
recovered the material for preparation and eventual combination with the
extracts of the same sample. Acid and base/neutral fractions were separated
by back extraction as done for the resin.
Farticulates contained in the rinse were quantified by gravimetrically
determining the residue after filtration. Condensable tars and oils were
quantified by determining the residue after evaporation. These results were
combined with the filterable and dissolved solids from the aqueous portion of
the impinger solutions to determine the total particulate catch.
Aqueous Liquids
The aqueous and non-aqueous phases of liquid samples were separated if
present. The aqueous phase was then extracted with CE^C^, first at a pH
of 12 then at a pH of 1. This scheme is shown in Figure 4-9. The resulting
base/neutral and acid fractions were carried on to subsequent portions of the
analytical scheme or, if the aqueous liquid was a portion of a sample, they
were combined with other like fractions for subsequent analyses.
If the aqueous liquid was an impinger solution from a particulate sample,
the aqueous phase was reserved and the dissolved solid content was determined
for inclusion in the particulate value.
56
-------
XAD-2® Resin
Sample ~300 cc
Soxhlet Extract
Resin for
24 hrs with
L liter of CH2CL2
Aqueous Phase
(Acids)
Extract CH2C12
3 Times with 330 ml
Water Adjusted
to pH-12
with NaOH
CH2C12 Phase
(Base/Neutrals)
Acidify Water
to pH=l with HC1
CH2C12 Layer
•Label: Dilute
Base/Neutral Fraction
Extract 3 Times
with 300 mlCH2Cl2
CH2C12 Layer
Label: Dilute
Acid Fraction
Combine with
Other Dilute
Base/Neutral
Fractions of
Same Sample
Discard
Aqueous
Layer
Combine CH2C12
Layer with Other
Dilute Acid Frac-
tions of Same
Sample
See Flow Diagram
for Organic Analysis
See Flow Diagram
for Organic Analysis
Figure 4^7. XAD-2® resin extraction flow scheme.
57
-------
ANALYSIS OF RINSES
Special Case: Measurement of Particulates and
Condensables in the Probe and Filter
Probe and
Filter Assembly
Rinses
Measure Volume,
Filter, Weigh Residue
Weigh Filter
from
Sample Train
Weigh Thimble, Combine
Both Residues, Soxhlet
Extract with CH2C12
Reweigh Thimble
Save Residue
Combine Soxhlet
Extract With
Filtered Rinses
Determine
TCO + GRAV
on Liquid
Label Liquid: Probe
and Filter Rinse
See Analysis
of Rinses (General)
for Further Analyses
Figure 4-8. Flow scheme for the preparation of sample train rinses,
58
-------
Aqueous Phase
Liquid Sample
Separate Into
Aqueous and Non-
Aqueous Phases
Take 3 Liters
and Adjust pH to
12 with NaOH
Extract 3 Times
with 330 ml CH2C12
Aqueous
Phase (Acids)
Acidify Water
to pH-1 with HC1
Extract 3 Times
with 330 ml CH2C12
CH2C12 Layer
Label: Dilute
Acid Fraction
Combine CH2C12
Layer with Other
Dilute Acid Frac-
tions of Same
Sample
See Flow Diagram
for Organic Analysis
CH2C12 Phase
(Base/Neutral)
CH2C12 Layer
Label: Dilute
Base/Neutral Fraction
Combine with
Other Dilute Base/
Neutral Fractions
of Same Sample
See Flow Diagram
for Organic Analysis
Figure 4-9. Flow scheme for the extraction of aqueous liquid samples.
59
-------
Solids
A known weight of solid sample was transferred to a soxhlet thimble,
weighed, and extracted with CH2C12 for 24 hours. The extract was then
back extracted to generate base/neutral and acid fractions as was done for the
XAD-2® scheme. Solids remaining after extraction were reweighed to determine
the percent extractables present in the sample. This preparation scheme is
the same as shown in Figure 4-7.
By-Products
The by-products from the Kosovo plant were diluted with a known volume of
CH2C12 and then filtered to remove particulates and insoluble matter. The
CH2C12 was then back extracted to generate the base/neutral and acid frac-
tions for introduction into the remainder of the analytical scheme. This
preparation scheme is shown in Figure 4-10.
4.2.3 Organic Analysis
Following the extraction step, aliquots of each fraction of a given sam-
ple were combined to form a composite sample for analysis and reserved. The
remaining portions of these base/neutral and acid fractions were concentrated
separately using Kuderna-Danish concentrations equipped with 3-stage Snyder
columns. Aliquots of these concentrates were set aside for gas chromatography/
mass spectrometry (GC/MS) analysis and remaining portions were combined and
reserved.
PNA Analysis
Concentrated extracts which were prepared as described in Section 4.2.2
were analyzed for several selected polynuclear aromatics (PNA) by GC/MS.
The compounds analyzed were:
Benz(a)anthracene
7,12-Dimethylbenz(a)anthracene
Benzo(a)pyrene
Benzo(a)fluoranthene
3-Methylcholanthrene
Dibenz(a,h)anthracene
252 molecular weight group (as Benzo(a)pyrene)
A Hewlett-Packard 5982A GC/MS equipped with a liquid crystal column was
used for these analyses. The liquid crystal N,N'bis(p-phenylbenzylidene),
2-2'-bi-p-toluidine (BPhBT) gave the required separation of these compounds
including the 252 molecular weight isomers listed.
The selected ion monitoring (SIM) technique was employed for all analy-
ses. The intensities of key ions were monitored during the chromatographic
separation. Identifications of the selected compounds were based on the
appearance of these key ions at previously established retention times. A
60
-------
By-Products
Dissolve ~2g
in 500 ml CH2C12
Filter and
Weigh Residue
500 ml CH2C12 Phase
Extract CH2C12
3 Times with 165 ml
Water Adjusted
to pH-12
with NaOH
Aqueous
Phase (AcidsJ
CH2C12 Phase
(Base/Neutral)
Acidify Water
to pH-1 with HC1
CH2C12 Layer
Label: Dilute
Base/Neutral Fraction
Extract 3 Times
with 165 ml CH2C12
CH2C12 Layer
Label: Dilute
Acid Fraction
Combine with
Other Dilute Base/
Neutral Fractions
of Same Sample
Discard
Aqueous
Layer
c-bine CiV-la Layer
with Other Dilute
Acid Fractions of
Same Sample
See Flow Diagram
for Organic Analysis
See Flow Diagram
for Organic Analysis
Figure 4-10. Flow scheme for the preparation of by-products.
61
-------
second criterion for identification was the relative intensity of the secon-
dary ion of each compound matching within 20% of the intensity found from the
analysis of a standard. The quantification of these compounds was achieved by
examination of the areas under the intensity profiles of a key ion for each
compound. These were compared to the mass and area under the intensity pro-
file of a series of at least four standards at varying concentrations.
All analyses were performed in duplicate. Positive identification and
quantitation of 7,12-dimethylbenz(a)anthracene and 3-methylcholanthrene were
not possible since standards of these compounds and their isomers were not
available.
Head Space Analysis
Samples of the vapors present in the headspace above by-products (not
extracts) were analyzed for light hydrocarbons, and sulfur species. The ana-
lytical techniques were described in Section 4.2.1, On-Site Gas Analysis. A
flow scheme for these analyses is shown in Figure 4-11.
Charcoal Tubes
Light aromatic hydrocarbons which had been collected by sorption on char-
coal tubes were extracted into carbon disulfide. The aromatics present in the
extract were analyzed using a GC with a flame ionization detector. A 2m x
1/8" O.D. glass column packed with 10% carbowax 20M on Chromosorb W AW was
used in the instrument. The column oven was maintained at 120°C during the
analysis.
4.2.4 Trace Elements
Samples from gas streams obtained for trace element analysis were
recovered in several fractions. These fractions were:
• probe, nozzle, and sample line wash with CI^C^,
• filtered solids or filter catch, and
• four impinger solutions,
- 2 10% HN03 (0.2L)
- 2 10% KDH (0.2L)
Sample fractions collected for metal carbonyl analysis consisted of two impin-
ger solutions of 3% HC1, each approximately 0.5 liters in volume. The
CH2C12 solutions were divided into two equal fractions. One fraction was
analyzed for its particulate content as described previously, the other was
analyzed for its trace element content. The fraction for trace element analy-
sis was evaporated to dryness, then treated with HN03, ~S.2®2* an<* **F as
required to digest the sample. The resulting solutions were diluted to a
known volume.
The impinger solutions were individually diluted to a known volume as
required to take any precipitates back into solution. Solids and by-products
62
-------
HEADSPACE ANALYSIS
Headspace Samples
Grimp-Seal in
10 ml Hypovial 2g
of Solids or 2ml
of Liquids
Heat Samples in
Water Bath at
65-*C for 5
minutes
Sulfur
Species
Use Direct
Injection and
Analyze for
Sulfur Species
Light Hydrocarbons
Analyze for
Hydrocarbons and
Substituted Benzenes
Yes
Dilute Sample
for HaS Analysis
Use Direct Injection
But Vent H2S
to Analyze for
Other Sulfur Species
Figure 4-11.
Flow scheme for the preparation and analysis
of headspace samples.
63
-------
were treated with HNC>3, H2(>2, and HF as required to digest all residue.
The resulting solutions were diluted to a known volume.
The prepared samples in aqueous media were then analyzed according to the
following analytical protocols and for the elements listed in Table 4-4.
4.2.5 Water Quality Parameters
Table 4-5 lists the methods used to determine the water quality para-
meters for aqueous samples. This table also includes the reference for the
method and a brief description.
4.2.6 Analysis of Impinger Solutions for Phenols, Ammonia, Hydrogen
Cyanide, and Hydrogen Sulfide
The analytical methods used for the analysis of Phenol, NH3, HCN, and
H£S from impinger solutions are given in Table 4-6. A brief description and
reference for these methods is also included in this table.
4.2.7 Analysis of Solids and By-Products
Analytical methods for the analysis of solids and by-products are listed
in Table 4-7. A reference for these methods and a brief description are also
included.
Analytical reagent blanks were analyzed and used to adjust the raw analy-
tical results from each sample. National Bureau of Standards (NBS) reference
materials (coal and ash) were also analyzed using the same procedures. The
results were used to assess the accuracy of the analytical results. Duplicate
samples were digested (prepared) and analyzed to assure adequate, precision.
Precision was found to be within 10% for all analyses, and the accuracy, as
determined by comparison of NBS reference material analyses, was found to be
within 20% of the NBS reported values.
4.2.8 Bioassay Test
Bioassay tests were performed to determine the biological activity of the
by-products, solid waste, and solid waste leachates from the Kosovo plant.
The results of these tests indicate the relative level of biological
activity of the samples. The activities cannot be used in the same manner as
quantative analytical results, but do permit the ranking of streams in terms
of their biological activity.
The organic samples that were immiscible with water were extracted with
methylene chloride (CH2Cl2) and exchanged with dimethylsulfide (DMSO) to
prepare them for the in-vitro bioassay tests. The protocol for the extraction
and solvent exchange is'shown below.
64
-------
TABLE 4-4. ANALYTICAL METHODS USED FOR THE ANALYSIS OF TRACE ELEMENTS
Element
As
Be
Cd
Co
Cr
Cu
*Fe
Hg
No
Ni
P
Pb
Sb
Se
Sr
Tl
V
Zn
Method1
206.2
210.2
213.2/213.1
219.2
218.2/218.1
220.1
236.2
245.2
246.2
249.2/249.1
COST
239.2
204.2
.270.2
PE
279.2
286.2
289.1 .
Description
Atomic Absorption,
Atomic Absorption,
Atomic Absorption,
Atomic Absorption,
Atomic Absorption,
Atomic Absorption,
Atomic Absorption,
Atomic Absorption,
Atomic Absorption,
Atomic Absorption,
Colorimetric
Atomic Absorption,
Atomic Absorption,
Atomic Absorption,
Atomic Absorption,
Atomic Absorption,
Atomic Absorption,
Atomic Absorption,
ETA
ETA
ETA/DA
ETA
ETA
DA
ETA
ETA
ETA
ETA /DA
ETA
ETA •
ETA
ETA
ETA
ETA
DA
*For metal carbonyl samples only.
Numerical designations refer to (Ref. 4-2) Methods for Chemical Analysis
of Water and Wastes (EPA 600-479-020).
2ETA - Electro Thermal Atomization
DA - Direct Aspiration
PE - (Ref, 4-3) Analytical Methods for Atomic Absortpion Spectroscopy,
Perkin Elmer.
COST - (Ref. 4-4) Soviet State Standards Committee Method
65
-------
TABLE 4-5. ANALYTICAL PROCEDURES FOR WASTE WATERS
CT>
Component
Waste Haters
NHj(free)
NH 3 (bound)
H2S
F"
Cl~
N0j~
N02~
COD
Permanganate
Phenols (volatile)
Phenols (non-
volatile)
Tars and Oils
Dry Solids
TS (Total Solids)
TDS (Total Dissolved
Solids)
TSS (Total Suspended
Solids)
pH Value
Sulfates
Thlosulfates
Rhodanate
(CNS~)
Method '
Method 418A, 418D
DIN Method E-5
DIN Method G-3
Method 414A..414C
DIN Method D-l
DIN Method D-9
DIN Method D-10
Method 508
DIN Method H-4
Method 510A, 510B,
and 510C
DIN Method H-16
COST Method - Tar
Method 208
Method 424
Method 427C
COST Method - Thlosulfatea
COST Method - "Jiodanate
Description
Distillation into boric acid followed by
back tltratlon
Kjeldahl reaction plus as above for
free NH,
Colorlmetrlc tltratlon of CdS precipitate
Distillation followed by colorlmetric
determination using SPADNS reagent
Titratlon with mercuric or silver nitrate
Colorlmetric method using chromotroplc acid
Colorimetric method using sulfanlllc acid
and naphthylamlne hydrochlorlde
Reflux with ICjCrjO, and HjSOi, and
back titrate with Fe(NH.,),(SOk)2
Acidic and baaic reflux with KMnO,,,
add excess oxalic acid and titrate
with KMnO,,.
Spectrophotometrlc with 4-amlno
antlpyrine
Extraction, convert to phenolates and
tltratlon using iodine
Ether extraction between pH 3 and 4
followed by evaporation and weighing (see text)
Dry to constant weight at 105*C
Filter before drying filtrate
Filter before drying precipitate
Electrometrlcally using a glass-reference
electrode pair
Turbidimetric (Not Used)
lodometrlc tltratlon
Colorlnetrlc determination using pyrldlne
and barbituric acid
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
References
4-5 (418A. 418D)
4-6 (E-5)
4-6 (C-3)
4-5 (414AS 414C)
4-6 (D-l)
4-6 (D-9)
4-6 (D-10)
4-5 (508)
4-6 (H-4)
4-5 (510A, B and C)
4-6 (H-16)
4-4
4-5 (208)
4-5
4-5
4-5 (424)
4-5 (427C)
4-4 (Thlosulfates)
4-4 (Rhodanate)
1DIN-(Ref. 4-6) German Institute for Standardization Method
GOST-(Ref. 4-4) Soviet State Standards Committee Method
-------
TABLE 4-6. ANALYTICAL PROCEDURES FOR IMPINGER SOLUTIONS
Component
Method
Description
References
cr>
Phenols
Ammonia
HCN
Method 510A, 510B, and 510C
Method 418A, 418D
Method 413C
Spectrophotometric with
4-aminoantipyrine dye
Distillation of ammonia
into boric acid solution
with back titration
Distillation followed by
silver nitrate titration
Ref. 4-5 (510)
Ref. 4-5 (418)
Ref. 4-5 (413C)
H?S
ASTM D2035
lodometric titration of
CdS precipitate
Ref. 4-7
-------
TABLE 4-7. ANALYTICAL PROCEDURES FOR SOLIDS AND BY-PRODUCTS
Component
Method
Description
References
CTv
co
Solid Samples
Moisture
Ash Content
Phenols
Total Volatile
Elemental Analysis
(C, H, 0,- N, S)
ASTM D3173
Method 208E
Method 510A,
510B and 510C
ASTM D3176
Dry to constant weight
at' 105°C
Heat at 550°C to constant
weight
Extraction of solid with
acidified water then treat
as waste water sample
Determination of combustion
products
Ref. 4-8
Ref. 4-5 (208)
Ref. 4-5 (510)
Ref. 4-9
-------
Sample
(4.0 mL or 4.0 gm)
I
m]
1
3 i
I
Add 35 mL CH2C12
Shake several hours at room temperature
Shake 1 part CH2C12 phase with 1 part DMSO
I
Evaporate CH2C12 with N2 Stream at 40 C for 7 hours
f
Add DMSO to bring final volume to 40 mL
I
Prepare serial dilution with DMSO as required for
in-vitro bioassays
Salmonella Bacterial Mutagenicity Assay (Ames1)
The Ames1 assay is based on the ability of selected mutant strains of
Salmonella typhimurium to revert from histidine dependence to prototrophy (the
ability to synthesize nutriments, in this case histidine, from inorganic
materials in the medium) upon exposure to various mutagens and carcinogens.
Though the assay does not use mammalian cells it may be adapted to mimic some
mammalian metabolic processes by the addition of mammalian (rat) liver micro-
somes to the system (metabolic activation).
The assay is conducted in a culture medium containing insufficient his-
tidine to allow the tester strains to proliferate. The tester organisms, with
and without the microsome preparation, are mixed with the test materials in
molten top agar and poured on plates over a selective basal medium. The test
plates, with positive, negative, sterility and activation control plates, are
incubated for 48 hours at 37°C.
Mutation is indicated by the appearance of colonies. Results are repor-
ted as the total number of revertants (colonies) per plate. A ratio of. exper-
imental over control (spontaneous) revertants of 2.0 or greater is generally
considered evidence of the mutagenicity of the test material.
In-Vitro Cytotoxicity Assasy (RAM and CHO)
Cytoxicity assays employ mammalian cells in culture to measure quantita-
tively and cellular metabolic impairment and/or death resulting from exposure
69
-------
in-vitro to soluble or particulate toxic material. A primary culture of
rabbit alveolar (lung) macrophages (RAM) was used to determine the in-vitro
toxicity of the solid waste (slag or gasifier ash) from the Kosovo gasifiers.
Chinese hamster ovary (CHO) fibroblasts were used to determine in-vitro toxi-
city by clonal assay of the liquid samples.
Alevolar macrophages constitute the body's first line of pulmonary
defense against particulate matter deposited deep in the lung. Thus, it is
appropriate that such cells be used to assay the acute cellular toxicity of
airborne particulates and associated chemical species.
A primary RAM suspension was collected by lung lavage with five instilla-
tion volumes of 30 cm^ of 37°C sterile 0.9 percent physiological saline
solution (FSS). The cells were washed once by centrifugation and resuspended
in fresh PSS. Cell viability was determined and the cells were recentrifuged,
suspended in culture medium, diluted, combined with the test material, (or
control) and incubated at 37°C (humidified five percent C02 atmosphere) for
20 hours. Following incubation, cell viability, total protein and ATP content
were determined.
CHO fibroblasts were removed from liquid nitrogen storage and maintained
as a monolayer culture for slightly over one month until required for the
assay. In the assay, CHO cells were suspended in medium, dispensed into tis-
sue culture flasks or dishes, and allowed to adhere for six hours. The medium
was then aspirated and replaced with medium containing sample at an appro-
priate dilution. Positive (NaN02 treated), negative (untreated), and
vehicle (DMSO) controls were also prepared.
After incubation for 24 hours, all flasks or dishes were washed with
three aliquots of phosphate buffered saline (PBS) and re-covered with medium.
The cells were'then incubated for six days to allow clones to develop, after
which they were drained, washed, fixed, stained, and the clones counted.
Acute in-Vitro Toxicity in Rodents
Five male and five female mice (Strain DF) of comparable body weights
were selected, from a group held in quarantine, for testing each sample. All
animals selected appeared to be healthy.
Test material (samples) was administered, without dilution, by direct
introduction into the stomach of the animal (gavage) as a single dose. Con-
trol animals were treated by administering doses of material used as vehicles
for the ash (KY lubricant) and heavy tar and dust (trioctanion).
Body weights were recorded at the time of dosing, Day 1, Day 8 and Day
15. Animals were observed daily for signs of poor health. A gross autopsy
was performed on each animal at death or at sacrifice (Day 15). Organ weights
were not obtained.
70
-------
4.3 DATA EVALUATION - SOURCE ANALYSIS MODEL/1A
The Source Analysis Model/1A (SAM/1A) is U.S. EPA-IERL's method for eval-
uation of discharge stream data. Its principle strength is that it makes
possible the reduction of pollutant discharge data to a common numerical base
so that discharges can be ranked or prioritized objectively.
The SAM/LA is based on multimedia environmental goals, or MEGs, which are
used to compute a Discharge Severity (DS). MEG is defined as a "concentration
level below which the discharged component is of low concern for its potential
effects on either human health or the ecology" (Ref. 4-10). In this respect,
it is a "target value" for components in discharge streams. MEGs have been
defined for many substances representing 26 classes of organic compounds (Ref.
4-11). Target levels have been defined in terms of their effect on both human
health and ecology for discharges to the three environmental media: air,
water, and soil. The goals set for discharges are named "Discharge Multimedia
Environmental Goals" or DMEGs. DMEG (Air-Health) values for sixteen compo-
nents whose discharge stream concentrations were measured in this study are
shown graphically in Figure 4-12. A reciprocal of DMEG is plotted since DS is
the product of concentration and 1/DMEG as defined below.
Measured Concentration of a Pollutant
DS - DMEG of that Pollutant
The DMEG, therefore, serves as a common denominator which reduces all compo-
nents to a common base, i.e., "multiples of the target value". ' The DS calcu-
lated in this manner is a dimensionless number (or at least it is reduced to
the common dimension - multiple of target value) which can be summed. Conse-
quently, a stream's discharge severity can be determined by summing the OS's
for all components in that stream to determine the Total Discharge Severity
(TDS):
TDS =• IDS
The TDS value provides a basis for comparing discharge streams, and, there-
fore, provides a basis for identifying the most severe streams.
Discharge severity is a concentration of a composition-based value that
does not define the quantity of mass emitted. Used alone, it cannot define
the environmental effects of a discharge bcause such effects are related to
both quantity and severity. With the SAM/1A Model, the significance of a
pollutant discharge in a given stream is defined by its Weighted Discharge
Severity (WDS):
WDS » mr'DS
where mr * Stream Mass Flow Rate;
and further, the environmental significance of that discharge stream is
defined by its Total Weighted Discharge Severity;
71
-------
, C6H5CH3, C6H4(CH3)2
6 -5 .4
Log™ (Nm3/jjg)
E* « Exponential (E-5
ID'5)
Figure 4-12. Key Kosovo gaseous pollutants
in order of severity (1/DMEG).
72
-------
TWDS » mr ZDS » mr'TDS
By comparing discharge streams within a given medium, such as air, water, or
land, the stream with the highest TWDS value may be selected as the most
significant environmentally.
Major simplifying assumptions implicit in the use of the Source Analysis
Model/lA (SAM/1A) methodology are:
• The substances currently in the Multimedia Environmental Goals (MEG)
lists (Ref. 4-10, 4-11, 4-12 and 4-13) plus the communication in
Appendix D (supercedes all previous values) are the only ones that
must be addressed at this time (the MEGs are currently being updated
to include new data, account for new or revised standards, and new
compounds).
• Transport of the components in the waste streams to the external
environment occurs without chemical or physical transformation
of those components.
• Actual dispersion of the pollutant from a source to a receptor
will be equal to, or exceed that assumed when MEG values are
estimated from acute toxicity data.
• Discharge Multimedia Environmental Goals (DMEG) values (Ref.
4-10, 4-11, 4-12 and 4-13) developed for each substance are
adequate for estimating acute toxicity. A DMEG is a concen-
tration of a substance estimated to cause an adverse effect
in a receptor exposed once or intermi'ttently for short periods.
It relates either to human health or ecological effect.
• The waste stream components are neither synergistic nor
antagonistic.
These assumptions', along with the accuracy of the test data, must be consi-
dered when interpreting test results presented in this report based on the
SAM/1A data evaluation scheme.
73
-------
SECTION 5
RESULTS AND DISCUSSION
The results obtained from this study consist of stream composition and
flow data. All results are contained in Appendix A. In this section, atten-
tion is given to the interpretation of these results. All calculations and
interpretations are based on the "best values" as listed in Appendix A. The
"best values" were selected based on scientific and engineering judgment. For
example, if two sets of composition data exist for a stream, and the plant was
not operating under stable conditions when one set was obtained, the other set
is listed as the best value.
Stream concentration values were obtained on-site during the tests in a
form for rapid interpretation. For example, gas stream composition was ex-
pressed in volume or mole percent so that components could be summed for
accountability. To evaluate streams as discharges, it is more useful to
express the values in terms of mass concentration (e.g., Ug/m^) which is
easily converted into mass flow rate.
The discharges were evaluated in terms of discharge severity according to
the model SAM/1A. The concepts and methods of this model were discussed in
Section 4.
This section is divided into the following subsections:
gaseous discharges,.
aqueous discharges,
•solid discharges, including a comparison to gaseous and
aqueous discharges,
products and by-products,
bioassay results,
mass balances, and
additional comments and summary of findings.
5.1 GASEOUS DISCHARGE STREAMS
Much of the data from the tests at the Kosovo Plant are for components of
gaseous discharge streams. This is due to the large number of gaseous dis-
charge streams and their potential environmental significance. All major and
many minor gaseous components were measured, including particulate loading on
selected streams. The following discussion will show that stream composition
followed a logical pattern through the plant and that all gaseous discharge
streams are of significant environmental concern, according to the results of
SAM/1A modeling.
5.1.1 Composition of the Gaseous Discharges
Each section of the gasification plant has .characteristic concentrations
of components in the discharge streams. In order to easily compare composition
74
-------
data, Table 5-1 contains a summary of best values for selected gaseous dis-
charge streams. The sum of the volume percent at the time of the analyses
gave a rapid method of accounting for the major components. The average of
the sums of the volume percent for the twelve streams in Table 5-1 on which
fixed gases were determined (Stream 14.5 is normalized) is 96%.
Autoclave Vent (1.2) composition data indicate that the Fleissner (steam
drying) Process produces small amounts of gaseous species, such as hydrogen
sulfide, methyl mercaptan, ethyl mercaptan and benzene. The stream has a high
concentration of steam (76% moisture by volume).
The gaseous discharge streams (3.2 and 3.6) from the gas production sec-
tion listed in Table 5-1 show similar compositions except for the high level
of ammonia found in the low pressure coal lock vent (3.2). The ammonia is
probably recovered from this stream by the high pressure coal lock vent scrub-
ber before it is discharged. As expected, the H^S-rich waste gas stream
(7.1) in the Rectisol section has the highest concentrations of I^S of any
gaseous stream at Kosovo. A comparison of H^S levels in 7.1 and 7.2 indi-
cates that the majority of the t^S is removed from the product gas stream in
the first step of the Rectisol process (by a discrimination factor of over
1000 to 1 over the second step).
Even though tank vents have much lower flow rates than such large dis-
charge streams as 7.1 and 7.2, their composition data indicate important
information from an environmental viewpoint. Furthermore, these vents may
pose a difficult control problem due to the large number of vents and the
varying composition of the vent gases. For example, the naphtha storage tank
vent stream (15.3) has about 4% benzene; methyl and ethyl mercaptans were
found at relatively high levels. Internal consistency of composition data for
the gaseous streams is exemplified by the Cg+ value of 5.3% which is slight-
ly greater than benzene plus toluene at 3.9%.
In the Phenosolvan Process, the NILj stripper vent stream (14.5) had an
ammonia concentration of 42% by volume (during this study ammonia was not be-
ing recovered, but was being discharged to the atmosphere). Furthermore, this
stream has relatively high concentrations of HCN, phenols, and
The volume percent data in Table 5-1 is converted to mass concentrations
^) in Table 5-2. From mass concentration, mass discharge rates can be
calculated using flow rates. The sums of the' mass discharges plantwide for
all the gaseous species measured during the tests are listed in Table 5-3.
These discharge rates are based on one gasifier in operation. In Table 5-3,
C02 is the largest discharge based on mass. It's discharge rate is 12,300
kg/gasifier-hr. Most of the C02 leaves the plant in streams 7.1 and 7.2
(Table 5-2). The C^-Cg hydrocarbons and the combined sulfur species have
discharges between 200-400 kg/gasifier-hr. Mass discharge rates for CO and
NH3 fall in the range of approximately 80 kg/gasifier-hr. The discharges of
CO are dominated by gas production section streams 3.2 and 3.6 as listed in
Table 5-2; the Ammonia Stripper Vent (14.5) accounts for 90% of the ammonia
discharged plantwide.
75
-------
TABLE 5-1. KOSOVO GASEOUS STREAM COMPOSITION DATA
PLANT SECTION:
SAMPLE POINT!
Dry Gaa Flow Rate
(n'/gaslfler-hr @25°C)
Temperature (°C)
Moisture Content (Z)
Molecular Wt. of Dry Gas
Composition (Dry Basis)
Fixed Gases (Vol Z)
U2
02
N2
CH,
CO
C02
Sulfur Species (ppmv)
H2S
COS
CH3SU
C2H,SH
Hydrocarbons (Vol Z)
C2H,
CjHi!
C,'s
Ci,'s
Cj's
C6+
Aromatic Hydrocarbons (ppmv)
Benzene
Toluene
Xyleoe & Ethylbenzene
Phenols
Higher Aromatlcs
Nitrogen Species (ppmv)
tnu
HCN
Pleiasner Drier
1.2
Autoclave Vent
57.8
-
76
33.4
Tr
14
56
Tr
Tr
29
2,400
30
3.400
2,100
Tr
NF
0.03 '
0.03
NF
0.011 v
17
6.8
.4.2
-
-
_
~
Gas Production
1 1
3.2 3.4
Low Pressure Gaa Liquor
Coal Lock Vent Tank Vent
21 44
56 60
44
23.5
37 12
0.27 14
0.18 56
8.6
14.6 2.6
36.5
13.000 1.450
110
420
220
0.22
Tr
0.14
0.05
Tr
0.12
760
220
75
5.7 Tr
- -
2,400 690
600
Rectlsol
3.6 |
High Pressure
Coal Lock (Flare
Feed Stream)
230
54
11
24.9
32
0.24
0.14
10.5
12
42
3.500
120
460
210
0.42
Tr
0.25
0.11 '
0.01
0.08
550
100
38
2.5
—
NF
170
1 7.1
H2S-rich
Waste Gas (Flare
Feed Stream)
3600
12
3.9
43.0
0.11
Tr
Tr
4.3
1.1
88
45.400
420
2,100
780
0.82
Tr
0.63
0.32
0.04
0.21
110
8
Tr
NF
_
2,200
200
7.2
C02-rlch Waste
Gas
3600
19
5.1
42.2
Tr
Tr
..It
1.2
Tr
94
39
62
8.5
I 4.4
1.6
Tr
0.28
Tr
Tr
NF
1.0
Tr
Tr
NF
"
4.6
13
Tr - Trace " 0.01 vol Z for fixed gases, 1 ppmv for all others.
NF - Not Found - less than a trace
( Continued)
-------
TABLE 5-1. (Continued)
PLANT SECTION;
SAMPLE POINT;
Dry Gas Flow Rate
(u'/gaalfler-hr 625*0
Temperature (*C)
Moisture Content (X)
Molecular Weight of Dry Gas
Composition (Dry Baals)
Fixed Gases (Vol X)
«2
02
Nj
CH«
CO
C02
Sulfur Species (ppmv)
H2S
COS
CHjSH
C2H5SH
Hydrocarbons-. (Vol I)
C2H6
C,js
Ci, s
Cs's
c«+
Aromatic Hydrocarbons (ppmv)
Benzene
Toluene
Xylene & Ethylbenzene
Phenols
Higher Aromatlcs
Nitrogen Species (ppmv)
Nil 3
HCN
Tank Separation
1
13.1
Tar Tank
Vent
0.55
52
14
29.1
Tr
19
77.5
0.16
Tr
0.86
6900
110
390
240
Tr
0.01
Tr
Tr
0.37
2,000
960
220
57
2.2
2,600
130
13.3
Medium Oil
Tank Vent
1.7
42
8.4
32.5
Tr
0.45
1.1
7.6
5.9
56
26,000 •
96
5200
2100
0.34
Tr
0.30
0.25
0.09
2.4
7,650
1,400
140
110
-
19
57
13.5
Condensate
Tank Vent
3.38
7
-1.0
26.6
14.6
16.6
61.0
1.2
NF
6.2
6,200
-
210
72
"lfl.07
0.05
0.03
0.04
-
5,200
3.000
-
Tr
_
NF
170
13.6
Tar Separation
Waste Gas (Flare
Feed Stream)
28
40
7.7
39.0
11
Tr
Tr
3.5
1.1
77.5
9.000
120
2,500
1.600
0.33
Tr
0.41
0.41
0.09
1.3
9,600
1.200
150
4.2
4.9
19,300
64
1
13.7
Phenolic Water
Tank Vent
5.5
76
42
34.4
Tr
13
39
0.2
NF
35
12,600
41
2.100
7,200
~lo.02
•^ 0.02
0.02
0.006
1.8
11.000
2,300
280
Tr
3.1
12,000
38
Phenoaolvan By-Product
Storage
1 1
14.5 14.6
NUj Stripper Cooler
Vent Vent
260 4.4
91
76
32.7
NF
-
-
Tr
NF
55
19.500 Tr
NF
290
100
I1' :
Tr
Tr
Tr
NF
_
-
Tr
6,200 Tr
- -
418,000 82.000
4,800
"15.3 1
Naphtha
Storage
Tank Vent
4.5
32
5
33.3
NF
2.6
84
NF
NF
0.85
NF
NF
2.600
9.700
Tr
0.01
0.07
0.08
5.3
37,600
1,900
60
Tr
-
NF
1,100
Tr - Trace - 0.01 vol X for fixed gases, 1 ppmv for all others.
NF - Not Found - less than a trace.
-------
TABLE 5-2. COMPONENT CONCENTRATIONS IN KOSOVO GASEOUS STREAMS
-co
PLANT SECTION 1
SAMPLE POINT;
Component (ig/n1 I 25*C)
Fixed Gases
H2
oa
N2
CHi,
CO
C02
Sulfur Species
U2S
COS
CHjSH
C2HSSH
Hydrocarbons
C2H,
C2H\
C 'a
C,,'s
C8'a
C6+
Benzene
Toluene
Xylene & Ethylbenzene
Phenols
Nitrogen Species
Nil 3
HCN
Dry Gas Flow Rate
(o'/gasifier-hr 125*0
NF - Not Found
Tr - Trace
Flelisner Drier
1
1.2
Autoclave Vent
Tr
1.83 £08
6.41 £08
Tc
Tr
5.21 EOS
3.34 £06
7.36 £04
6.68 £06
5.33 E06
Tr
NF
5.40 EOS
7.14 EOS
NF
3.43 EOi
5.44 £04
2.56 £04
1.82 E04
-
_
-
57.8
1 1
3.2
Low Pressure
Gee Production
3.4
Gee Liquor
Coil Lock Vent Tank Vent
3. 05 E07
3.51 E06
. 2.06 £06
S.64 £07
1.67 £08
6.56 £08
1.80 E07
2.70 £05
8.25 £05
5.57 EOS
2.96 E06
Tr
2.52 E06
1.19 £06
Tr
4.22 E06
2.43 £06
8.28 E05
3.25 £05
2.19 £04
1.73 £06
6.62 £05
21
9.74 £06
i.ai EOS
6.35 £08
2.97 £07
2.02 E06
-
-
-
-
-
-
-
-
-
-
-
-
Tr
4.80 E05
-
44
t -
lectlaol
3.6
High Pressure
Coel Lock (Flare
Feed Streaa)
2.64 £07
3.14 E06
1.60 E06
6.88 £07
1.37 £08
7.55 £08
4.87 £06 •
2.95 EOS
9.04 EOS
5.35 EOS
5.16 E06
Tr
4.50 E06
2.61 E06
2.95 EOS
2.82 £06
1.76 E06
1.76 EOS
1.65 EOS
9.61 £03
NF
1.88 £05
230
. . » V
1 1 7.1
HjS-rlch
Wast* Gee (Flare
Peed Streaa)
8.98 £04
Tr
Tr
2.82 £07
1.26 £07
1.58 E09
6.32 £07
1.03 £06
4.13 E06
1.98 E06
1.01 £07
Tr
1.14 £07
7.60 £06
1.18 £06
7.39 £06
3.51 EOS
3.00 E04
NF
Tr
1.53 £06
2.21 £05
3,600
1 ^
7.2
CDs-rich Haste
Gas >
•
Tr
Tr
Tr
7.84 £06
Tr
1.69 £09
5.43 £04
1.52 £05
1.67 E04
1.12 E04
1.97 £07
Tr
5.04 £06
Tr
Tr
NF
3.19 £03
Tr
Tr
NF
3.20 £04
1.44 £04
3.600
(Continued)
-------
TABLE 5-2. (Continued)
PLANT SECTION 1
SAMPLE POINT;
Component (flg/m* 6 2S*C)
Fixed Gases
H2
02
N2
CH\
CO
C02
Sulfur Species
H2S6
COS
CHjSH
C2HSSH
Hydrocarbons
C2H6
C2H,.
C3's
d.'s
Cs1
C6+
Benzene
Toluene
Xylene & Ethylbenzene
Phenols
Nitrogen
NHj
HCN
Dry Gas Flow Rate
(ms/gasifier-hr 1 25°C)
p - Not Found
Tr - Trace
Tank Separation
1
13.1
Tar Tank
Vent
Tr
2.48 EOS
8.87 £08
1.04 E06
Tr
1.55 E07
9.61 E06
2.70 £05-
7.66 EOS
6.09 £05
Tr
1.80 £05
Tr
Tr
1.30 E07
6.38 E06
3.61 E06
9.52 E05
2.19 £05
1.81 E06
1.44 E05
0.55
13.3 13.5
Medlim Oil Condensata
Tank Vent Tank Vent
Tr
5.88 £06
1.26 £07
4.98 £07
6.75 £07
1.01 £09
3.62 £07
2.36 £05
1.02 £07
5.33 106
4.18 £06
Tr
5.40 £06
5.94 £06
2.65 £06
8.45 £07
2.44 £07
5.27 E06
6.06 £05
1.73 E05
1.32 £04
6.28 £04
1.7
1.20 E07
2.16 EOS
6.95 EOS
7.84 E06
NF
1.11 EOS
8.61 E06
-
4.11 E05
1.82 EOS
la. 57 £05
9.01 E05
7.13 E05
1.18 E06
-
1.66 E07
1.13 E07
-
Tr
NF
1.88 E05
3.38
Tar
Haste
Feed
13.6 1
Separation 13.7
Gaa (Flare Phenolic Water
Streaa) Tank Vent
8.98
E06
Tr
Tr
2.
1.
1.
1.
2.
4.
4.
4.
7.
9.
2.
4.
3.
4.
6.
1.
1.
7.
29
26
40
25
94
91
06
05
Tr
39
74
65
58
06
52
51
62
34
05
28
£07
E07
£09
E07
£05
£06
E06
£06
£06
£06
£06
£07
£07
£06
£05
£04
E07
£04
Tr
1.70
4.46
1.31
£08
EOS
£06
NF
6.29
1.75
1.01
4.13
1.83
2.46
3.60
4.75
1.77
6.34
3.51
8.66
1.21
EOS
£07
£05
£06
E07
£05
£05
£05
£05
E07
£07
£06
£06
Tr
8.35
4.20
5.5
£06
£04
Fhenoeolva. *££'
1 I" 15.3 1
14.5 14.6 Naphtha
Mil Stripper Cooler Storage
Vent Vent Tank Vent
NF
-
-
Tr
NF
9.89 EOS
2.72 £07
NF
5.70 E05
2.54 £05
Tr
Tr
Tr
Tr
NF
Tr
-
Tr
2.38 £07
2.91 EOS
5.30 E06
260
-
3
9
-
-
1
NF
-
5
2
-
1
1
2
1
1
7
2
Tr
5.71 £07
— 1
4.4
NF
.40 E07
.61 £08
NF
NF
.53 £07
NF
NF
.11 £06
.46 £07
Tr
.80 £05
.66 E06 .
.36 £06
.87 £08
.20 £08
.15 £06
.60 E05
Tr
NF
.21 £06
4.5
-------
TABLE 5-3. MOST SIGNIFICANT GASEOUS SPECIES IN ORDER OF MASS DISCHARGE - PLANTWIDE
.00
o
Ranking *
1
-
-
2
3
4
5
6
7
8
Species
CO 2
£(Ci-C6)
Z( sulfur
H2S
CM.,
C2H6
CO
NH3
C3's x(as
Ce (as (
Discharge
g/s (kg/hr)**
3420 (12,300)
106 (380)
species) 73 (261)
66 (237)
41 (148)
30 (109)
23 (82.1)
23 (81.8)
C3H8) 17 (60.5)
:6Hm) 8.3 (29.9)
Ranking
9
10
11
12
13
14
15
16
17
18
Species
GH'S (as Ci,H10)
CH3SH
C2HgSH
Phenols
C5's (as C5Hi2)
COS
Benzene
HCN
Toluene
Xylenes and
Ethylbenzene
Discharge
7.9 (28.3)
4.4 (15.8)
2.2 (7.99)
1.7 (6.19)
1.2 (4.42)
1.2 (4.34)
0.94 (3.37)
0.64 (2.29)
0.12 (0.443)
0.026 (0.0938)
^Ranking based on individual species.
**grams/gasifier-second (kg/gasifier-hour).
-------
5.1.2 Discharge Severities of Gaseous Discharges
The mass concentrations of the components of each discharge stream can be
used to calculate a discharge severity following EPA's IERL Source Analysis
Model/lA (SAM/1A) as outlined in Section 4.
The low pressure coal lock vent (3.2) will be used to illustrate the ef-
fects of converting concentrations to discharge severities (OS's). In Figure
5-1 the mass concentration of the major pollutants in the coal lock vent dis-
charge can be compared with their DS values. Note that benzene and mercap-
tans, which are at relatively low concentrations, emerge as pollutants of high
concern. Trace elements listed in Appendix C were considered, but their DS
values were relatively low compared to the compounds listed in Figure 5-1.
This conclusion is true for trace elements in all gaseous streams.
Since the DS values can be summed, a single value can be obtained which
provides a numerical indication of stream severity in terms of concern for
causing adverse health effects. Total discharge severity values of the most
significant gaseous streams are compared in Figure 5-2. The degree of concern
for all the streams listed is two to four orders of magnitude above the level
where concern begins (DS>1) as defined by the SAM/1A model. The fourteen
streams listed in Figure 5-2 include at least one stream from every section in
the plant. The TDS gives an idea of stream severity; however, flow must be
coupled with TDS (=TWDS) to give an indication of environmental burden from
the discharge streams as illustrated in Figure 5-2.
As- an example of what happens when flow is considered, the naphtha stor-
age tank vent (15.3) and the CC^-rich waste gas (7.2) are compared. Since
the values in Figure 5-2 are in exponential form, the addition of logjo flow
to the logio TDS gives the log^o of the Total Weighted Discharge Severity
(TWDS). The TDS of the naphtha storage tank and CC^-rich waste gas are 7.08
E+04 and 2.69 E402 respectively. From this comparison it is evident that the
discharge from the naphtha storage tank is several hundred times more severe
than the discharge from the C02~rich waste gas vent. However, when the flow
rates of the respective streams are taken into consideration, the two streams
are of virtually equal environmental significance.
In Figure 5-2 the streams are ranked according to their environmental
impact on health (SAM/1A). This comparison is illustrated using the height of
each column. The t^S-rich waste gas (7.1) has the highest TWDS, in the
range of E407. The ammonia stripper vent (14.5) is an order of magnitude
below 7.1. The next seven streams in descending order are 7.2, 3.6, 1.2,
13.6, 15.3, 3.2, and 13.7); they have TWDS values in the range of E+05.
Since the SAM/1A treatment can also be used to relate stream composition
and flow rate to ecological effects, the health values cited above can be
compared to the ecology values as they are in Figure 5-3. As shown in the
figure, a reordering of the discharge streams occurs. The ammonia stripper
vent (14.5) has the highest ecological TWDS values, in the range of E+08.
This increase is due primarily to the NH3 content of the stream. The
81
-------
CO
8TX
H2S
COS
CH3SH, CH3CHjSH
C8H5OH-
NH3
HCN
H
E"0123456789
ug/m3
Mass concentration of pollutants in
LP coal lock vent
'Sum of all phenolic species
••Exponential (EOS » 10s)
NSOSI
DS-L.P. Coal lock vent
Figure 5-1. Comparison of mass concentrations to discharge
severities (air-health) in the low pressure coal
lock vent discharge stream (3.2) .
82
-------
Gaaaoua Straams
HjS-Rlch Waata Gaa
(7.1)
Ammonia Slrippar
Vant(14£)
COrRleli Waata Gaa (7.2)
Coal
LockVanKiS)
Autoclava Vant (1.2)
TartOII SapantkMi Waata Gaa (13.6)
Naptha Sloraga Tank Vant (1S.3)
Coal Lock Vant (34
WatarTankVant(13.7)
Madhan ON Tank Vant (113)
Gaa Uquor Tank Vant (&4)
Tank Vam (119
Vant(14«
Tar Tank Vant (13.1)
+ Logio (g/sae)
D U>a10TDS
• Log10Flow
YA Log^oFlow is Negative
Figure 5-2. Total weighted discharge severities (air-health)
of key Kosovo gaseous discharge streams.
83
-------
HjS-Rlch Waste Gas (7.1)
Ammonia Stripper Vant (14.5)
CQyfllch Wasta Gas (7.2)
High Pressure Coal Lock Vent (3.6)
Autoclave Vent (1.2)
Tar/Oil Separation Waste Gas (13.6;
Naptha Storage Tank Vent (15.3)
Low Pressure Coal Lock Vent (12)
Phenolic Water Tank Vent (13.7)
Medium Oil Tank Vent (13J3)
Gas Liquor Tank Vent (3.4)
Condensate Tank Vent (13.5)
Cooler Vent (14.6)
Tar Tank Vent (13.1)
• Health 1
O Ecology
Lag10TWOS(g/sec)
Figure 5-3. A comparison of health and ecology total weighed discharge
severity values in key Kosovo gaseous discharge streams.
84
-------
rich waste gas (7.1) has the second largest ecological TWDS value, 1.3 E+07.
Several streams such as 14.6 and 13.1 also have significantly higher values
for ecological TWDS than for health TWDS. This is caused by a greater concern
for the effects of NHg on the ecology than on health.
The stream having a significantly lower ecological TWDS value than health
TWDS value is the Fleissner autoclave vent. Its value drops from 2.60 E405
(health) to 4.65 E-HD3 (ecology). This reduction is due primarily to the lack
of values for methyl and ethyl mercaptans in the ecology MEG data. base for the
SAM/1A model.
The ranking of individual chemical species on a plantwide basis using the
SAM/1A treatment is of interest. Figure 5-4 shows the nine worst chemical
species in the Kosovo gaseous streams, in order of descending TWDS (health
values). The sulfur species, I^S, CI^SH and C2H5SH, are of highest
concern in order of descending TWDS's. Ammonia and CO are of next highest
concern and are about an order of magnitude less than the 'sulfur species.
COS, benzene, HCN and phenols round out the top nine species of highest
concern.
5.1.3 Particulate Data
Farticulate loadings were obtained for seven gaseous discharge streams.
The parti culate catch was divided into three parts: extractable organics
(tars and oils), filterable solids and dissolved solids. Data for the seven
discharge streams are listed in Table 5-4. This discussion focuses on the
results from particulate catches obtained by the impinger method (see Section
4.1.5) and specifically on the results from particulates found in the low
pressure coal lock vent gases (3.2). This stream is emphasized because of the
potential environmental significance of the particulates that are transported
with the gas discharged through this vent.
A major portion of the Kosovo particulate catch consists of condensed
organics (tar and oil) as tabulated below:
Tars and Oils (wt %)
Autoclave Vent (1.2) 44
LP Coal Lock Vent (3.2) 90
Start-up Gas Vent (3.3) 95
HP Coal Lock Vent (3.6) 69
Tar/Oil Separation Waste Gases (13.6) 72
Combined Gases to Flare (20.1) 76
Analytical results are not yet available from the collections. Therefore, by-
product composition data were used to make judgments about the significance of
these particulates. Particular attention was directed to the LP coal lock
vent gas since it is discharged to the atmosphere at Kosovo and a similar
arrangement is proposed at several conceptual U.S. plants. The LP coal lock
vent discharge contained 8.1 E-H33 mg/m3 of particulates of which 7.8 E403
mg/m3 were tars and oils. Table 5-5 shows the concentrations of several of
85
-------
H2S
CH3SH
C2H5SH
NH3
CO
COS
HCN
CgHgOH*
I
2
I
3
I
4
I
5
Log101WDS (g/sec)
*Sum of All Phenolic Species
Figure 5-4. The nine worst compounds in gaseous discharge streams
on a plantwide basisi in order of descending TWDS (health)
86
-------
TABLE 5-4. PARTICIPATE CONCENTRATION AND FLOW RATE DATA FOR KOSOVO GASEOUS STREAMS
oo
SAMPLE POINTS:
STREAM DESCRIPTION:
Dry Gas Flow Rate
(ma/gasif ier-hr @
25°C)
Total Particulate
(mg/m 3 @ 25° C)
Condensed Organics
(Tars.& Oils)
Dissolved Solids
Filtered Solids
2.2
1.2 Coal
Aucoclave Room
Vent Vent
57.8 7200
1080 90
480
320
280
3.2
Low Pressune
Coal Lock Vent
21
8100
7300
650
220
3.3
Gasifier
Start-Up
Vent
9450
8980
400
61
3.6
High Pressure
Coal Lock Vent
230
960
660
240
61
13.6
Tar /Oil
Separation
Waste Gas
28
920
660
230
29
20.1*
Combined
Gases
To 'Flare
1330
410
310
54
47
*The streams that make up 20.1 are discussed individually since in a U.S. Plant
different streams may be sent to the flare.
-------
TABLE 5-5. HAZARDOUS PNA'S IN KOSOVO LIGHT TAR AND MEDIUM OIL (yg/g)
7 , 12-Dimethylbenz (a) anthracene
Benz (a) anthracene
Benzo (b) f luroanthene
Benzo(a)pyrene (BaP)
Benzo (a, h) anthracene
3-Methylcholanthrene
252 Group
Light
Tar
1100
490
310
210
23
26
950*
Medium
Oil
62
160
120
68
7
NF
280 *
*BaP - 24% of 252 Group in both by-products.
88
-------
the most severe polynuclear aromatics (PNA's) contained in the by-product
light tar and medium oil discharged as an aerosol is the same as that in the
light tar and medium oil by-products, it is reasonable to assume that the PNA
level in the aerosol (particulates) would be in proportion to the amount of
light tar and medium oil found there. Consider the following data:
LP Coal Lock Vent ug/m3 - ug/hr
Particulate Concentration 8.1 E+06 1.7 E+08
Tar and Oil 7.3 E+06 1.5 E+08
Benzo(a)pyrene-based on tar 1.5 E+03 3.2 E+04
Benzo(a)pyrene-based on oil 5.0 E+02 1.0 E+04
These results imply that the level of benzo(a)pyrene in the LP coal lock
vent discharge is in the range of 500 to 1,600 ug/nP. The levels of all
other PNA's may be estimated in the same manner.
The presence of PNA's in the LP coal lock vent discharge increases the
TDS of that stream significantly. The effect of the increase using the aver-
age PNA content of light tar and medium oil is shown in Figure 5-5. Note that
the increase in TDS resulting from the inclusion of PNA data elevates the LP
coal lock vent to almost the same level of significance as the ammonia strip-
per vent (14.5) at 2 E+06. The three other streams in Figure 5-5 are changed
only slightly by the contribution of the PNA's.
5.2 AQUEOUS WASTE STREAMS
All aqueous stream data are listed in Appendix A. The two major aqueous
waste streams in the Kosovo Gasification plant are:
• Gasification section waste water, which is a combination
of the following streams:
- ash quench water,
- coal bunker vent gas scrubber blowdown, and
- ash lock vent gas scrubber blowdown; and
• Phenosolvan wastewater.
Water quality data and concentrations of anions and polynuclear aromatics
are listed in Table 5-6 for the gasification section wastewater and
Phenosolvan inlet and outlet streams. Both wastewaters have high values for
solids, COD and permanganate values. Effluent Guidelines set for Steam
Electric Power Generation (Ref. 5-1) limit the pH of an aqueous discharge to a
range of 6.0 to 9.0 and total suspended solids (TSS) to 100 mg/L maximum dur-
ing any one day. Both limits are exceeded by the phenolic water Phenosolvan
wastewater and the TSS level is exceeded by the gasification section waste-
water. The high pH is due to the alkaline nature'of the Kosovo lignite ash.
For the trace elements measured in the Phenosolvan inlet (14.0) the Effluent
Guidelines are not exceeded (Zn =1.0 mg/L, Cr » 0.2 mg/L and P =5.0 mg/L).
89
-------
High Pressure Coal Lock Vent (3.6)
Autoclave Vent (1.2)
Tar/Oil Separation Waste Gas (13.6)
Low Pressure Coal Lock Vent (3.2)
I
3
I
4
I
5
T
6
Log 10 IDS + Log10 Flow (g/sec) + Log10 2 DS (PNA's)
D IDS
• Flow
PNA Contribution
Figure 5-5. The effects of PNA contributions on the total weighted discharge severity
values (health) for four gaseous discharge streams.
-------
TABLE 5-6. KOSOVO AQUEOUS STREAM DATA
PLANT SECTION; GAS
PRODUCTION
SAMPLE POINT: 1 12.3 | |
———— Gasification Section
Wastewatar
Flow Rate
(m'/gasifier-hr)
Ph
Temperature (*C)
Total Solids
Suspended Solids
Dissolved Solids
Water Quality Parameters
COD (as ag Oj/I.)
Permanganate (mg/L)
BOD, (as mg 02/L)
TOG
Aqueous Composition Data (mg/L)
Total Phenols
Volatile Phenols
Free Ammonia.
Fixed Ammonia
Cyanide
Nitrites
Nitrates
Pyrldines
Chlorides
Fluorides
Total Sulfur
Sulfites
Sulfates
Sulfides
Thiocyanates
Thlosulfates
PNA Analysis (mg/L)
3.0
3.1
«•
10,900
8,760
2,100
1.460
3,060
. 90
-
-
0.17
Tr
1.9
Q.01
0.40
4.3
-
28
0.91
.
Tr
495
Tr
0.26
Tr
Benz (a) anthracene
7 , 12-d±methylbenz (a) anthracene
Benzo(a) f luoranthrene
Benzo(a)pyren*
3-aethylcholanthrene
Olbenz (a , h) anthracene
252 Group (as BaP)
-
PHENOSOLVAN
14.0
Phenolic
Water
>13
9.2
60
2,230
150
2.170
18,900
14,200
9,030
4,970
2,120
-
3,510
250
<1
-
<1
140
-
-
-
—
-
-.
>75
-
0.92
0.23
0.68
0.19
<0.004
0.02
1.3
14.11 t
Phenosolvan
Outlet Water
13
9.6
33
1,350
190
1,160
7,910
4,040
2,350
1,470
230
130
Tr
205
0.019
Tr
11.4
~
60
Tr
34
—
110
—
<75
Tr
NF
NF
NF
NF
NF
0.19
Tr - Trace
NF - Not Found
- - Not Analyzed
91
-------
at a level of 0.14 mg/L. No guidelines
Mercury was found in the phenolic witer at the Phenosolvan inlet (14.0)
ire currently available which can be
applied directly to wastewater effluents. However, an indirect comparison can
be made to the MEG value for mercury (0.01 mg/L) which is defined as that
threshold level at which a concern for adverse health effects begins. Another
indirect comparison can be made to the mercury level of 0.2 mg/L for
Extraction Procedure (EP) toxic wastes (Ref. 5-2) defined in RCRA. This
guideline, which is 100 times the Federal Drinking Water Standard, is not
exceeded.
Phenols and ammonia were not expected in the gasification section waste-
water. It is unlikely that either compound would survive migration through
the fire zone to the ash lock. These compounds also were detected in the ash
lock vent gases, however, confirming their presence at the point of ash
quench. It is expected that their presence may be due to the use of Fleissner
condensate or phenolic water as make-up water in the ash quench process. The
sulfur species in the gasification section wastewater and the phenolic water
were present primarily in the form of sulfate.
The Phenosolvan section wastewater stream data presented in Table 5-6
indicate that a significant reduction in the organic pollutant load is
achieved by the Phenosolvan section. As expected, the phenol level was
reduced significantly (by approximately 90%) by treatment in the Phenosolvan
section. It is also important to note that the concentrations of several
significant PNA's were reduced to undetectable levels. The by-product phenol
stream was probably the vehicle by which the PNA's in the inlet wastewater
left the Phenosolvan section. The Phenosolvan Section lowers the TWDS
(Health) of the phenolic wastewater from 1.12 E+07 to 1.22 E-HD5.
Although a significant portion of the phenolic material was removed from
the Phenosolvan inlet water, a significant amount of organic matter remained
in the discharge. This assertion is supported by the following data:
• TOG in outlet water - 1470 mg/L,
• Phenols in outlet water - 230 mg/L,
• Volatile phenols in outlet water - 130 mg/L.
The level of volatile phenols in the outlet water is still the dominant
concern for reducing the TWDS or level of concern. Since the composition of
the unextracted TOG has not yet been determined, no realistic assessment has
been made of the character of the bulk of this material. However, a relative-
ly large fraction of the inlet TOG (30%) remains in the wastewater after
extraction in the laboratory with diethyl ether and methylene chloride at both
pH » 1 and pH - 12.
5.3 SOLID DISCHARGES INCLUDING A COMPARISON TO GASEOUS AND AQUEOUS DISCHARGES
This section deals with solid discharges at the Kosovo Plant along with
results of leaching studies on the ash. At the end of the section, there is a
comparison of the 3 categories of discharges: gaseous, aqueous and solid.
92
-------
5.3.1 Solid Discharges and Results of Leaching Studies
The two most significant solid discharges are the gasifier ash (12.1) and
heavy tar (13.8). All comparison data from the test program along with the
leaching results on the ash are listed in Appendix A.
The dry gasifier ash (12.1) is composed of a mixture of minerals and
trace elements which are origin-dependent (Kosovo lignite). The results of
the moisture free Ultimate Analyses show a carbon content at 1.78 weight %,
oxygen of 2.3%, and hydrogen of 0.26%, with the rest of the components accoun-
ting for less than 0.2%. The ash does have a positive heating value, but it
is not classified as ignitable and, therefore, would not require special hand-
ling in accordance with current applicable RCRA criteria for ignitable wastes.
Quenched ash is landfilled at the Kosovo plant.
The heavy tar (13.8) is 56.0% carbon, 7.6% hydrogen, 0.87% nitrogen and
0.33% sulfur based on dry weight. It has an ash content of 6.6% and a heating
value of 26.5 kJ/g. Heavy tar contains substances of relatively higher envi-
ronmental concern including phenols and polynuclear aromatics (benzo(a)pyrene
alone is 0.024% by weight). This material is landfilled at the Kosovo plant.
Due to its heating value, this material might be used as a fuel in future U.S.
plants when mixed with other by-products.
Since heavy tar (13.8) in U.S. plants will probably be recycled to the
gasifier or burned as a fuel, the amount and disposition of the gasifier ash
(12.1) dominates the solid discharge picture. The gasifier ash will most
likely be landfilled due to the amount and nature of this discharge. Instead
of concern for the solid, the leaching of substances out of the ash is of
major importance. In order to determine the leaching characteristics of this
material and to predict its classification under RCRA guidelines, a series of
leaching studies were conducted. The results of these tests, which are
reported in Appendix A, indicate that no trace elements are present in the ash
leachate which would cause this material to be classified as hazardous.
5.3.2 Comparison of All Discharge Media
A direct comparison of discharge severity for all media is possible since
it is a unitless value. Figure 5-6 shows the major gaseous, aqueous, and
solid discharge streams from the Kosovo plant along with their corresponding
IDS and TWDS values. These values use the Health-based MEG's and the common
flow unit, g/sec, for all streams.
Only one stream, the quenched ash wastewater, has a TDS less than 1 E+01.
The TDS for the RCRA based ash leachate is over an order of magnitude higher.
This may be due to the alkaline nature of the Kosovo ash versus the acetic
acid used in the RCRA leaching tests to obtain leachable trace elements.
The TDS (health) values for all other streams are significantly greater
than 1 E401, therefore, by the SAM/1A Model, there is a high degree of concern
for these discharges. The TWDS (health) values range from about 1 EH-04 to 1
E+07.
93
-------
Qanoua Streams
QiyGaamarAali
(TDS 8«aad on RCRA Uadiata)
tar (14.11)
Log10F1ow is Negative
Figure 5-6. A comparison of the total weighted discharge severity
values (health) for key Kosovo gaseous, aqueous and
solid streams.
94 .
-------
5.4 PRODUCT AND BY-PRODUCT STREAMS
The composition of the products and by-products impact their final uses
and any environmental problems associated with those intended uses. Composi-
tion data for the lean product gas stream (7.4) and for the naphtha, medium
oil and light tar by-products are presented in Appendix A.
Table 5-7 contains a summary of the compsotion data, excluding trace
elements, for the crude product gas (7.3) and clean product gas (7.4) streams.
The clean product gas (7.4) from the Rectisol section shows a composition of
mostly H2<60% v/v), CO (22% v/v), and 014(16% v/v). The sulfur species
have been reduced to relatively low levels and NH3 was not detected. By
comparing the clean product gas (7.4) to the crude product gas (7.3) in Table
5-7, the efficiency of the Rectisol clean-up can be seen. Furthermore, what
has been taken out of the crude gas must now exit in the Rectisol waste gas
stream (7.1 and 7.2). Large amounts of l^S exit the plant from this
section.
The Ultimate Analyses data for the Lurgi by-products are listed in Table
5-8. When the heavy tar is excluded in a comparison, two trends are evident.
The sulfur content decreases and the nitrogen content increases when going
from the lower boiling fractions to the higher boiling fractions (naphtha—*
medium oil^^light tar). The heavy tar was excluded due to its high water and
particulate content. The ratio of N/S in heavy tar is identical to that in
light tar. If the heavy tar composition was corrected for particulate content
(assuming this material to be coal dust), then the trend would follow that set
by the other by-products for N and S content.
Appendix A contains the trace element data for the by-products. The
organic compounds would overshadow the trace elements on the basis of environ-
mental burden if the by-products were considered discharges. However, on-site
burning appears to be the preferred end use for these by-products in concep-
tual U.S. plants. After mixing with other fuels, most organics in the by-
products will be destroyed in a high efficiency burner. However, the trace
elements may continue to be of concern in the flue gas. For instance, if
medium oil were burned, As could be as high as 680 ug/nr* (25°C). The dis-
charge severity for As in air would be 3.4 E-K)2.
Headspace analyses were performed on the by-products. These data appear
in Appendix A. The concentrations of benzene, toluene, xylenes, and mercap-
tans in the headspace of the lower boiling by-products indicate that the stor-
age tank vents were sources of environmental concern. These sources were
measured in Phase II and were discussed in Section 5.1.
5.5 BIOASSAY RESULTS
Bioassay tests were run on the by-products (except crude phenol), waste-
waters, gasifier ash, and leachates from the gasifier ash and heavy tar. The
leachates were generated using the ASTM procedure (neutral leaching). Appen-
dix B contains a complete report of the bioassay results.
95
-------
TABLE 5-7. COMPARISON OF PRODUCT GAS COMPOSITION ENTERING
AND LEAVING THE RECTISOL GAS CLEANING PLANT
_ . . Crude
Composition
Fixed Gases (vol %)
H2
02
N2.
CH^
CO
C02
Sulfur Species (ppmv)
H2S
COS
CH3SH
C2H5SH
Hydrocarbons
Ethane (vol %)
Ethylene (vol %)
C3 (vol %)
Q, (vol %)
C5 (vol %)
C6+(vol %)
Benzene, (ppmv)
Toluene (ppmv)
Xylene & Ethylbenzene (ppmv)
Phenols (ppmv)
Higher Aromatics (ppmv)
Product Gas
7.3
38.1
0.36
0.64
11.5
15
32
6000
97
590
200
0.47
0.04
0.19
0.074
0.044
0.064
7 SO
/ -f\j
TOO
xwu
Tr
Clean Product Gas
7.4
60
0.44
0.38
16
22
0.02
NF
0.17
1.1
1.0
0.15
Tr
Tr
Tr
Tr
0.03
Tr
Nitrogen Species (ppmv)
NHa 3.3 Tr
HCN 320
NF = Not Found, <0.01 vol % for fixed gases and <1 ppmv for all
other species.
Tr = Trace, - 0.01 vol % for fixed gases and - 1 ppmv for all other
species.
- = No data available.
96
-------
TABLE 5-8. COMPARISON OF ULTIMATE ANALYSIS DATA FOR KOSOVO
BY-PRODUCT TARS, OIL AND NAPHTHA
Light
Heavy Tar*** Tar
C
H
N
S
Ash
0
(by difference)
Moisture
HV*
S02**
56.0
7.6
0.87
0.33
6.6
28.6
26.5
240
81.9
8.4
1.3
0.49
0.22
7.8
1.1
37.3
260
Medium
Oil
81.8
8.9
1.0
0.83
0.03
8.2
0.8
38.3
380
Naphtha
85.7
9.9
0.18
2.2
2.1
41.6
1060
*HV = Heat value expressed as KJ/g.
**Expressed as ng/J assuming 100% conversion of S to S02.
***Moisutre free analysis.
Emission Limitations for Utility Steam Generators (Ref. 5-3):
Solid Fuels 86-520 ng/J (0.2 - 1.2 lb/106 Btu).
Liquid Fuels 340 ng/J (0.8 lb/106 Btu).
97
-------
Table 5-9 contains a summary of the bioassay results. The following
conclusions can be drawn from these results:
• the gasifier ash is not a very toxic substance and all tests
including those on the ASTM leachate show little or no biological
activity;
• the organic by-products (light tar, medium oil and naphtha)
were the most toxic of the samples tested in the rodent tests;
the tars gave a positive response .to the Ames* test, which was
expected from the levels of known carcinogens found in these
materials; and
• the Phenosolvan unit reduced the biological activity of the
wastewaters significantly.
5.6 MASS BALANCES
Mass balance calculations performed on the "best values" of the Kosovo
data for the key elements carbon, nitrogen, and sulfur show that major por-
tions of these elements are discharged in gaseous streams. • The results of
these calculations are shown in Figure 5-7. A detailed discussion of the
methods used to obtain these balances is included in Appendix C. Also inclu-
ded in Appendix C are the mass balance calculations and results around each
section of the Kosovo gasification plant.
In figure 5-7 the dried coal and the oxygen streams are assigned a value
of 100% of the incoming N, S, and C to the gasification plant since they are
the only sources of these elements. The rest of Figure 5-7 shows the amount
of each of these elements in key Kosovo solid, liquid and gaseous streams
expressed as a percentage of these elements entering the gasifier. This fig-
ure shows that the majority of the carbon entering the system with the dried
coal stream leaves in gaseous streams. The three major gaseous streams ac-
counting for the carbon are the clean product gas (7.4), l^S-rich waste gas
(7.1) to flare, and C02-rich waste gas (7.2). Relatively little of the in-
let carbon ends up in the gasifier ash ( 0.7%), aqueous wastewaters ( 0.3%)
and the remaining gaseous discharge streams. The percentage of the carbon in
the coal which is accounted for in the various product and waste streams is
92%.
The major stream accounting for most of the sulfur leaving the plant is
the H2S-rich waste gas (7.1) which is part of the flare feed system in the
Kosovo plant. Much of the remaining sulfur exiting the plant appears in the
by-products - naphtha (2.0%), medium oil (1.5%), and light tar (1.4%) - and
the ammonia stripper vent (4.8%). Some of the sulfur is discharged in the ash
(1.7%), heavy tar (0.2%), and the wastewaters (1.1%). The three major sulfur
species which exit the plant are H^S, CI^SH and C2H5SH. The percen-
tage of the sulfur in the coal accounted for in the product and waste streams
is 180%. The poor accountability of this balance is probably due to varia-
tions in the input coal sulfur content (see Section 5.7) and variations in
flow measurements.
98
-------
TABLE 5-9. A SUMMARY OF THE BIOASSAY RESULTS
Sample
Number
2468
115 2A
2471
2472
2473
2987
2988
2468L
2473L
Description
Ash
Naphtha
Medium Oil
Tar
Heavy Tar
Phenolic Water
Phenosolvan Waste-
Water (Outlet)
ASTM Ash Leachate
ASTM Heavy Tar
Leachate
In Vitro
Cytoxicity **
Ames* EC50t
Negative
Negative
Negative
Positive
Positive
Positive
Negative
Negative
Negative
>1000
0.68
0.11
0.03
0.07
37
98
>600
120
Rodenttt
Test/
Control
1/2
7/2
10/2
7/2
3/1
1/2
0/2
1/0
3/0
* Highest concentration tested varied depending on sample toxicity.
See Appendix B.
**A11 samples tested in CHO assay except the ash sample which was
tested in the RAM assay.
tECso's given in yL/mL or yg/mL (EC= Effective Concentration).
ttNumber of dead mice in test group over control group. Ten
animals were used in each group. See details in Appendix B.
99
-------
180%
o
o
C S N
Dried Coal
and
Ozygen Streams
CSN CSN CSN CSN CSN CSN CSN CSN
Clean Liquid S°l»d« Aqueous Flare COyRlch Ammonia Other
Product By-Products Discharges Discharges Streams Waste Gas Stripper Gaseous
Gas Vent Discharges-
Gas
CSN
Total
Figure 5-7. Mass balances for carbon, sulfur and nitrogen in Kosovo process
and discharge streams.
-------
Nitrogen entering in the dried coal feed is converted primarily to am-
monia, hydrogen cyanide and pyridine-like compounds in the liquid by-products.
Nitrogen entering with the oxygen feed to the gasifiers is in the form of
molecular nitrogen. The major stream accounting for almost half of the exit-
ing nitrogen is the ammonia stripper vent (14.5). In analyzing the gas phase
results, it was difficult to discriminate between molecular nitrogen acutally
present in the gas stream and nitrogen due to sample contamination with air.
Due to this problem and the variability of the nitrogen content in the feed
coal, the accountability was low. The product and waste streams accounted for
51% of the nitrogen entering with the coal and oxygen feed streams to the
gasifiers.
Appendix C" also contains a balance of trace elements around the Kosovo
gasification facility. A trace element balance was not the intent of this
study; however, based on the limited data available, an understanding of the
fate of trace elements was obtained.
As expected, most of the trace elements that entered the plant in the
form of coal left the plant in the form of gasifier ash. Results from trace
element analyses of streams 7.1, 7.2, and 7.4 showed that only a very small
amount of the most volatile elements were discharged in the Rectisol gaseous
streams and/or product gas. Most of the mercury stayed in the aqueous phase
streams and was discharged from the plant in the Phenosolvan section.
5.7 ADDITIONAL COMMENTS AND SUMMARY OF FINDINGS
Comments on how the data was interpreted and what impacts new data will
have on the results are included in this section. The major findings are
summarized in this section.
5.7.1 Variation of Feed Coal
One source of variations in the measured composition of the products and
waste streams is the composition of the feed coal, which was not constant from
day to day. Figure 5-8 illustrates the day-to-day variation in the composi-
tion of the coal. Within a two week period the sulfur content of the coal
varied from approximately 1% to 1.8%. The impacts on the mass balance calcu-
lations and stream composition are obvious since the lignite is the only
source of sulfur. Similar variations could also have affected the nitrogen
mass balances, since carbon is the major component in the coal, the relative
variations in composition should impact the carbon mass balance calculations
to a much lesser.degree.
5.7.2 Comments on SAM/1A
The SAM/LA treatment of the data in this Source Test and Evaluation
Report (STER) has been used on a compound specific basis. Only where com-
pounds or groups of compounds (e.g., total phenols) have been identified and
quantified have their values been used in the calculation of the TDS and TWDS
of the discharges. If this had been a screening test, the "worst case"
101
-------
O
NJ
2.0
CO
O
e
O)
'5
0.5
AvaragaValuaal.36 • * •
1 2 3 4 S 6 7 8 0 10 11 12 13 14 IS 16 17 18 19 20 21 22 23 24 25
November, 1977
Figure 5-8. Daily variation in the sulfur content of Kosovo lignite.
-------
compound in a MEG category would have been used for any unknowns. For exam-
ple, if the tars and oils from a particulate catch had been separated into a
PNA fraction, this total fraction would have been assumed to be benzo(a)pyrene
This was not done in this STER.
The SAM/1A was also used to prioritize the analytical schemes and thus
lower the source assessment cost. Obviously, all species cannot be identified
in all streams. However, if the major components are quantified and the TBS
of the stream is calculated, then the species which can impact the IDS have
been drastically reduced. For example, the light tar was analyzed for the
most hazardous compounds which could be produced by a gasifier, (see the PNA's
in Appendix A). Knowing the IDS calculated from these PNA's, the number of
compounds which could be in the rest of the tar and still impact the IDS was
small. Once the major phenols had been quantified, the number of compounds
which could make up the rest of the tar and which could increase the TDS even
by 10% was less than twenty.
5.7.3 Impact of New Data
This study provides a meaningful measure of environmental concerns within
Lurgi-type technology. However, with any study of this magnitude, cost must
be weighed against the accuracy of the data. New data which is more accurate
than that contained herein may cause the TDS (Total Discharge Severity) of a
stream to go up or down slightly. Drastic changes, however, are not expected.
When the TDS values are in the range of 10^ to 10^ as in most of the gas-
eous discharge streams, more accurate data, which changes the concentration or
flow data by even as large a factor as 2, will not greatly impact these orders
of magnitude of concern.
As stated earlier, only identified and quantified species were used to
calculate TDS values. Quantification of other organic or inorganic species
will only increase the TDS levels. For example, when the polynuclear aromatic
hydrocarbon content of medium oil and light tar was used to estimate the TWOS
of the low pressure coal lock vent (3.2), the TWDS increased by almost a fac-
tor of ten.
5.7.4 Summary of Findings
The Kosovo Phase II data has corroborated the indications from the Phase
I test results and has also added new information about the aqueous and solid
discharges from the Kosovo plant. It has also provided significant informa-
tion about trace pollutants, both organic and inorganic. The following are
some of the more salient findings:
• All discharge streams - gaseous, aqueous and solid, have a
significant potential for polluting the environment.
• Highest priority streams in each medium are:
gaseous - ^S-rich waste gas,
aqueous - phenolic wastewater, and
solid - heavy tar.
103
-------
However, most of the major discharge streams sampled
were found to contain pollutants which may require
emission controls.
PNA's make a significant contribution to the severity of
tar bearing streams, such as:
- LP coal lock vent, and
- heavy tar.
The severity of the LP coal lock vent discharge is increased
significantly by the assumed contribution of PNA's in the tar
aerosol.
Benzo(a)pyrene and 7,12-Dimethylbenz(a)anthracene are the two
most significant pollutants in Kosovo tar.
Trace elements were found to be less significant than trace
organics as pollutants.
Mercury was found in phenolic water at significant levels.
This accounts for most of the mercury entering the system
with the coal.
Ash leaching problems appear to be of low concern. Concentrations
of all trace elements were at least an order of magnitude lower in
the RCRA leaching method than the levels specified in the EPA
toxicity test.
Residual sulfur species and hydrocarbons in the CC^-rich waste
gas will cause control problems due to the energy poor nature
of this stream.
Even after Phenosolvan treatment, the wastewater has high
residual organic material and solids which must be addressed
in controlling discharges.
The high TWOS and high heating values of the heavy tar will
probably require that this solid waste material be disposed of
in a manner diffrent from landfill!ng as done at Kosovo.
No significant concentrations of trace elements were found
in the product gas or Rectisol gas streams; most of the
trace elements volatilized in the gasifier end up in the "heavy
tar, liquid by-products, and the Phenosolvan wastewater.
The Rectisol process is effective in "cleaning up" the product
gas. Its use in the-U.S. will depend on the availability of
satisfactory control technology for the l^S-rich and C02~rich
waste gases produced.
104
-------
BIBLIOGRAPHY
4-1 Code of Federal Regulations, 40; Protection of the Environment
parts 53 to 80, Revised 1 July 1980.
4-2 Methods for Chemical Analysis of Water and Wastes (EPA-600
4-79-020) March 1979.
4-3 Analytical Methods of Atomic Absorption Spectroscopy,
Perkin-Elmer.
4-4 Unified Methods of Water Analysis, Edited by Yu, Luye', "Khimiya",
Moscow.
4-5 Standard Methods for the Examination of Water and Wastewater,
14th Edition, 1975, APHA, AWWA, WPCF.
4-6 Deutsche Einheitsuerfahren zeir Wasser Untersuchung (DIN),
3rd Edition, 1975.
4-7 American Society for Testing and Materials, 1977 Annual Book
of ASTM Standards, Part 31, Water. Philadelphia, PA 1977.
4-8 American Society for Testing and Materials, 1979 Annual Book
c>f_ ASTM Standards, Part 26, Gaseous Fuels; Coal and Core,
Atmospheric Analysis, Philadelphia, PA 1979.
4-9 American Society for Testing and Materials, 1978 Annual Book
of_ ASTM Standards, Part 26, Gaseous Fuels; Coal and Core,
Atmospheric Analysis, Philadelphia, PA 1978.
4-10 Schalit, L.M., and K.J. Wolfe, SAM/1A: A Rapid Screening Method
for Environmental Assessment of Fossil Energy Process Effluents.
EPA-600/7-78-015. Acurex Corporation/Aerotherm Division,
Mountain View, CA, February 1978.
4-11 Cleland, J.G., and G.L. Kingsbury. Multimedia Environmental
Goals for Environmental Assessment, Volumes I & II, Final Report.
EPA-600/7-77-136a, Research Triangle Institute, Research Triangle
Park, North Carolina, November 1977.
4-12 Kingsbury, G.L., and J.B. White. Multimedia Environmental Goals
for Environmental Assessment: Volume III. MEG Charts and
Background Information Summaries (Categories 1-12). EPA-600/
7-79-176a, Research Triangle Institute, Research Triangle Park,
North Carolina, August 1979.
105
-------
Bibliography (Continued)
4-13 Kingsbury, G.L., R.C. Sims, and J.B. White. Multimedia Environmental
Goals for Environmental Assessment: Volume IV. MEG Charts and
Background Information Summaries (Categories 13-26). EPA-600/
7-79-l76b. Research Triangle Institute, Research Triangle Park,
North Carolina, August 1979.
5-1 40 CFR 423 Parts A-D, "Steam Electric Power Generating Point
Source Category".
5-2 40 CFR 261, Appendix II, "RCRA Regulations - EPA Toxicity Test
Procedures", as appears in 45 FR 33127-33129 (May 19, 1980).
5-3 40 CFR 60 Parts D and Da (Standards of Performance of Steam
Generating Units).
106
-------
APPENDIX A
COMPILATION OF RESULTS
TABLE OF CONTENTS
Page
Al .0 INTRODUCTION A-2
A2.0 COMPILATION OF DATA FOR GASEOUS STREAMS A-4
A3.0 COMPILATION OF PARTICULATE DATA FOR GASEOUS STREAMS A-45
A4.0 COMPLATION OF DATA FOR AQUEOUS STREAMS A-49
AS .0 COMPILATION OF DATA FOR SOLID PHASE STREAMS A-60
A6.0 LEACHATE TEST RESULTS FOR KOSOVO GASIFIER ASH A-84
A7.0 HEADSPACE ANALYSES FOR KOSOVO BY-PRODUCTS AND HEAVY TAR.... A-86
A8.0 COMPILATION OF DATA FOR KOSOVO BY-PRODUCTS A-87
-------
KOSOVO SOURCE TEST AND EVALUATION
REPORT (PHASES I AND II)
DATA APPENDIX
Al.O INTRODUCTION
This Appendix presents a compilation of the currently available
data obtained during Phases I and II of the Kosovo test program. For each
sample point, overall characteristic values are given for all species ana-
lyzed. Where multiple data analyses were available, a range of values is
included. This range defines the normal range of the component as best
determined from the process, design, and experimental data available. In
arriving at the overall values, plant conditions, sampling methods, and
sampling conditions were all considered. For sections of the plant where
enough data was available, mass balance calculations were used to ascertain
the validity of the data. These mass balance calculations are discussed in
Appendix C.
The results of Phase I and Phase II gaseous stream analyses are
presented in Section A2.0. Data are presented for 27 direct discharge
sources, five flare feed streams, and three process streams. These streams
were surveyed during Phase I. Based on the Phase I results, nine direct
discharge, five flare feed, and three process streams were selected for a
more thorough analysis in Phase II of the test program.
In compiling the gaseous stream data to arrive at overall charac-
teristic values, preference was given to data obtained during the more
complete Phase II test program. In Phase II, two methods were used to
analyze for HaS in gaseous streams. These were the wet impinger and gas
chromatograph (GC) methods. For streams with low «10 wt%) moisture con-
tent, both methods gave similar results. However, for high moisture content
streams (>10 wt%), the results obtained from the two methods varied con-
siderably for reasons which are discussed in the sampling and analysis
section (Section 4.0) of this report.
The results from particulate sampling/analyses are presented in
Section A3.0. Eight gaseous streams were sampled for entrained
particulates. Whenever possible, each particulate catch was separated into
three fractions: filterable solids, condensed organics (extractable), and
dissolved solids.
Analyses were performed on samples from five aqueous streams
during Phases I and II of the test program. A compilation of the results is
given in Section A4.0. For trace elemental analyses, two methods, Atomic.
Absorption Spectrophotometry (AA) and Spark-Source Mass Spectrometry (SSHS)
were used. Since the accuracy obtained by these methods differs greatly,
results are reported separately. A more complete discussion of these
methods is given in the section discussing analytical methods (Section 4.0).
A-2
-------
Section A5.0 presents a compilation of data obtained from six
solid phase streams. For the gasifier ash. samples of both the hot, dry ash
and the quenched, wet ash were analyzed. RCRA (acid) and ASTH (neutral)
leachate tests were performed on the dry gasifier ash. The results are
shown in Section A6.0.
Headspace analyses were performed for some by-products and for
heavy tar. The by-products analyzed were naphtha, medium oil, light tar,
and crude phenol. The results are given in Section A7.0.
Light tar, medium oil, and naphtha, three of the by-products
generated at the Kosova plant, were also analyzed. A compilation of these
results is shown in Section A8.0.
The compilations in Sections A4.0 through A8.0 are not separated
by the phase in which the analyses were performed as in Sections A2.0 and
A3.0. Instead, one overall value and a range are shown. There were not
enough data in these sections to justify identifying the phases in which the
sampling and analyses were performed.
A-3
-------
A2.0. COMPILATION OF DATA FOR GASEOUS STREAMS
TABLE A.2-1. TEST DATA
FLEISSNER
FOR GAS PHASE SAMPLE POINT 1.2,
AUTOCLAVE VENT
Phase I
Component Value * Range
Dry Gas Flow Rate
(a3 at 25*C/gasifier-hr)
Temperature (*C)
Molecular Vt. of Dry Gas
Moisture Content (wt *)
Composition Data (Drv Gas Basis)
Fixed Gases (vol *)
H2 NO PHASE I DATA
02
N2
CH4
CO
C02
Sulfur Soecies (sumv)
H2S
COS
CH3SH
C2H5SH
Cl-C<+ Hydrocarbons (vol %)
Ethane
Ethylene
C3
C4 ^
C5
Aromatic Soecies (oTmv)
Benzene
Toluene
Xylene + Ethylbenzene
Phenols.
Higher Aroma tics
Nitroaen Soecies (nomv)
NH3
HCN
Phase II
57.8
-
33.4
76
Tr NF-Tr
14 20-21
56 30-79
T*
Tr
29 26-48
2400 740-3600
30
3400 2700-4200
2100 1700-2500
Tr
NF
0.03 0.01-0.04
0.03 0.001-0.03
NF
0.01 0.01-0.39
17 4.5-17
6.8 2.5-6.8
4.2 4.2-22
-
-
Overall
Value * Range
57.8
-
33.4
76
Tr NF-Tr
14 10-21
56 30-79
Tr
Tr
29 26-48
2400 740-360
30
3400 2700-4200
2100 1700-2500
Tr
NF
0.03 0.01-0.04
0.03 0.001-0.03
NF
0.01 0.01-0.39
17 4.5-17
6.8 2.5-6.8
4.2 4.2-22
-
-
NF - Not Found. <0.01 vol % for fixed gases and <1 ppmv for all others (1000 ppmv > 1 vol %)
Tr - Trace, -0.01 vol % for fixed gases and -1 ppmv for all others
- 'No data available
•Values are best values from available data
A-4
-------
TABLE A.2-2. TEST DATA FOR GAS PHASE SAMPLE POINT 2.2.
DEDUSTING CYCLONE VENT
Component
Dry Gee Flow Rate
(mi at 25'C/jasifier-hr)
Temperature CO
Molecular wt. of Dry Gaa
Moisture Content (wt *)
Phesa I Phaae II
Value * Range Vila* * Range
4600 4600-15500 7200
10 10-14 27
28.6
2.4 2.1-2.5 3.0
Value
7200
27
28.6
3.0
Overall
* Range
4600-15500
10-27
2.1-3.0
Composition Data (Drv Gaa Baais)
Fixed Gaaes (vol «)
H2
02
N2
Cfl4
CO
C02
Sulfur Species (opmv)
H2S
COS
CH3SH
C2HSSH
Ci-Co1* Rydrooarbona (vol *)
Ethane
Ethyl one
C3
C4
C5
c«+
Aromatic Soecies (OOBV)
Benzene
Toluene
Xylene + Ethylbenzene
Phenol a
Higher Aronatics
Nitroten Soecies (onmv)
NH3
HCN
NF NF-O.S
20.8 19-21
78.2 78-80
NF NF-Tr
NF NF-Tr
NF
NF
NF Tr
NF NF
NF NF
NF NF-Tr
-
NF NF-Tr
NF NF-Tr
NF NF-Tr
NF NF-Tr
-
-
Tr
-
NF NF-30
NF
NF
20.8
78.2
NF
NF
NF
NF
NF
NF
NF
NF
-
NF
NF
NF
NF
-
-
Tr
-
NF
NF
NF-O.S
19-21
78-79
NF-Tr
NF-Tr
NF-Tr
NF-Tr
NF-Tr
NF-Tr
NF-Tr
NF-Tr
NF-30
NF - Not Found, <0.01 vol % for fixed gaaea and <1 ppmv for all others (1000 ppar - 1 vol %)
Tr - Trace, -0.01 vol % for fixed gaiea and -1 ppnv for all others
- - No data available
Phaae I Ethane data are the total of all Cj Hydrocarbons
•Values are best values from available data
A-5
-------
TABLE A.2-3. TEST DATA FOR GAS PHASE SAMPLE POINT 3.1.
COAL LOCK BUCKET VENT
Component
Phase I
Valae* 8an»a
Piaaa II
Value * 2an|e
Overall
Vain* * Range
Dry Gas Flow Rat*
(n3 at 25"C/ga*ifier-hr)
Temperature (°C)
Molecular Wt. of Dry Gaa -
Moisture Content (»t %> -
Composition Data (Dry Gas Basis)
Fiied Gasea (vol %)
Hj 1.8
02 IS
H2 77
CH4
CO 0.6
COj
Aeid Ga««. (vol «> 2.6
Saturated Hydrocarbons
(vol *) 0.4
Uaaatuated Hydrocarbon*
(vol *) NF
NO PHASE II DATA
1.8
18
77
0.6
2.6
0.6
NF
NF • Not Found. <0.01 vol % for f izad ga«a* and <1 ppmv for all others (1000 ppaiT " 1 vol %)
Tr - Trace. -0.01 vol % for fixed gases and -1 pp»v for all others
- - No data available
•Values are best values froai available data
A-6
-------
TABLE A.2-4.
TEST DATA FOR GAS PHASE SAMPLE POINT 3.2,
LOW PRESSURE COAL LOCK VENT
Component
Dry Gas Flow Rat*
(n3 at 25*C/iasifi*r-hr)
Temperature (*C)
Molecular Wt. of Dry Gas
Moisture Content (»t *)
Phase I
Valu* * Range
—
56 46-65
24.9
44 8 .1-44
Phase
Valu* *
21.0
-
23.3
44
II
Range
30-44
Overall
Valu *
21.0
56
23.5
44
Rang*
8.1-44
Comnositioi^ Data (Drv Gas Basis)
H2
02
N2
CH4
CO
C02
Sulfur Soeeies (DOIBV)
H2S
COS
CH3SH
C2H5SH
Ci-C$+ Hydrocarbons (vol V
Ethane
Ethylene
C3
C4
C5
C6+
Aromatic Soecies (oonv)
Benzene
Toluene
Xylene + Ethylbenzeae
Phenols
Higher Aromatict
Nitrocen Soecies (ovrnv)
NH3
HCN
34 33-44
0.7 0.7-1.5
2.5 2.2-2.6
9.4 9.3-9.4
9.3 9.2-11
42 29-42
3800 2000-9800
170
260
84
0.72 0.72-0.84
0.29 0.29-0.38
0.09 0.09-0.16
0.05 Tr-0.05
0.03 Tr-0.03
_
-
-
Tr Tr-5.4
-
7000 180-7000
48
33
0.27
0.18
8.6
14.6
36.5
13000
110
420
220
0.22
Tr
0.14
0.05
Tr
0.12
760
220
75
S.7
-
2400
600
22-37
0.26-4.3
0.14-18
2.8-8.6
2.4-15
36-52
10000-33000
90-130
400-2500
120-870
Tr-0.72
NF-Tr
0.14-0.64
0.05-0.37
Tr-0.17
0.08-0.19
750-760
190-240
70-85
1000-3700
48-680
37
0.27
0.18
8.6
14.6
36.5
13000
110
420
220
0.22
Tr
0.14
0.05
Tr
0.12
760
220
75
5.7
-
2400
600
22-44
0.26-4.3
0.14-18
2.8-9.4
2.4-15
29-52
2000-33000
90-170
260-2500
84-870
Tr-0.72
NF-Tr
0.14-0.64
0.05-0.37
Tr-0.17
Tr-0.19
750-760
190-240
70-85
Tr-5.7
180-7000
48-680
NF - Not Found. <0.01 vol % for fixed gases and <1 ppmv for all others (1000 ppmv - 1 vol *)
Tr » Traea, -0.01 vol % for fixed gates and -1 ppmv for all others
- - No data available
Phase I Ethane data are the total of all C2 Hydrocarbon*
•V»l»*« are best v«ln*« fro» arnilabl* data
A-7
-------
TABLE A.2-5. ATOMIC ABSORPTION DATA FOR THE LOW PRESSURE
COAL LOCK VENT (3.2)
Component (jig/m3)
As
Be
Cd
Co
Cr
Cu
Hg
Ho
Ni
Pb
Sb
Se
Sr
Tl
V
Zn
Phase II Value
1700
4.0
27
4.9
270
180
S3
45
120
72
NF
NO.
610
NF
9.0
1600
NF = Not found
NO. - Present, but not quantifiable
A-8
-------
TABLE A.2-6.
TEST DATA FOR GAS PHASE SAMPLE POINT 3.3,
GASIFIER START-DP VENT
Phase I
Component Value * Range
Dry Cms Flow Rate
(m3 ft 2S«C/gasifier-hr)
Temperature CO
Holaenlar 1ft. of Dry Gas
Moisture Content (wt %)
Composition Data (Drv Gas Basis)
Fixed Gaies (vol %)
H2 NO PHASE I DATA
02
Ml
CH4
CO
C02
Sulfur Sneeies (nrmv)
H2S
COS
CH3SH
CjHsSH
Cl-Cg-t- Hydroearbona (vol *)
Ethane
Ethylene
C3
C4
C5
c«+
Aromatic Soeeies (nomv)
Beuze&a
Toluene
Xylena + Ethylbenzene
Phenols
Higher Aromatic*
Nitrocen Soecies (onmv)
NH3
HCN
Phase II
Value * Range
-
-
33.1
70
0.09 0.09-0.27
4.5 4.4-18
42 42-«7
1.6 0.8-1.6
14 3.7-14
34 10-34
£300
110 40-120
490 90-520
240 30-250
0.15 0.07-0.15
0.05 0.004-0.05
0.08 0.03-0.08
0.03 Tr-0.04
0.007 Tr-0.009
0.09 0.03-0.09
90 10-90
10 Tr-10
Tr Tr-10
630
11000
2900
Overall
Value *
-
-
33.1
70
0.09
4.5
42
1.6
14
34
6300
110
490
240
0.15
Range
0.09-0.27
4.4-18
42-«7
0.8-1.6
3 .7-14
10-34
40-120
90-520
30-250
0.07-0.15
0.05 0.004-0.05
0.08
0.03
0.007
0.09
90
10
Tr
£30
11000
2900
0.03-0.08
Tr-0.04
Tr-0.009
0.03-0.09
10-90
Tr-10
Tr-10
NF - Not Found, <0.01 vol % for fixed gases and <1 ppmv for all others (1000 ppav - 1 vol «)
Tr * Trace. -0.01 vol % for fixed gases and -1 ppmv for all others
- • No data available
•Values are best values from available data
A-9
-------
TABLE A.2-7. TEST DATA FOR GAS PHASE SAMPLE POINT 3 4
GAS LIQUOR TANK VENT ' '
Component
Paaae I
Valo* * Rani*
Val«»
Phase II
Or.rail
Value * Rani*
Dry Gas Flow Rate
(n3 at 25«C/»asifier-hr> 44
Tenperatnre CO 60
Molecular It. of Dry Gaa
Moisture Content (vt %j
Composition Data (Dry Ga» Basis)
Filed Bases (vol \)
B2 12
02 14
N2 56
CH4
CO 2.6
C02
Sulfur Species
1450
BjS
COS
CB3SH
CzBsSH .
C1-C6* Hydrocarbon! (vol
Ethane
Ethyl ene
C3
C4
C5
C6+
Aromatic Species (nnanr)
Benzene
Tolaen*
Xylene + Ethylbenzen*
Phenols
Higher Aronaties
Nitrogen Species (ppmv)
NH3
HCN
Acid Gases (vol %) 11
Saturated Bydroearbons (vol %) 3 .0
Unsaturated Bydroearbons (TO! %) 0.5
Tr
690
NO PRASE II DATA
1400-1600
Tr-9.5
99-690
10-13
0.4-0.6
60
12
14
56
2.6
1450
Tr
690
10
3.0
0.5
1400-1600
Tr-9.5
99-690
10-13
0.4-0.6
NF » Not Found. <0.01 vol * for filed gases and <1 pp»v for all others (1000 ppmv « 1 vol %)
Tr * Trace. -4.01 vol % for fixed gases and -1 ppmv for all others
- - No data available
•Values are best values from available data
A-10
-------
TABLE A.2-8. TEST DATA FOR GAS PHASE SAMPLE POINT 3.5,
ASH LOCK CYCLONE VENT
Coaponeat
Dry Gas Flow Rate
(m3 at 2S«C/gasifier-hr)
Temperature ( *C)
Molecular Wt. of Dry Gas
Moisture Content (*t %)
CooDosition Data (Drv Gas Basis)
Fixed Gases (vol %)
H2
02
N2
CH4
CO
C02
Sulfur Soecies (ODIBT)
H2S
COS
CH3SH
C2H5SH
Cl-C|j+ Hydrocarbons (vol *)
Ethane
Ethyl ene
C3
C4
cs
Aromatic Species (otnav) '
Benzene
Toluene
Xylene + Ethylbenzene
Phenols
Higher Aroaatica
Nitroaen Soecies (nt>mv)
NH3
UCN
Pk*M I
Valuer * Range
7.1
98 90-98
31.3
85 81-97
NF
48
35
Tr
NF
14
82 NF-82
NF
NF
NF
Tr
Tr
Tr
-
NF NF-Tr
-
-
Tr NF-1S
-
340 130-340
54
Pheee II Overall
Value * R»ge Vain* * Range
32.8 32.8 7.1-32.8
98 90-98
31.3
85 81-97
NO PHASE II COMPOSITION DATA NF
48
35
Tr
NF
14
82 NF-82
NF
NF
NF
Tr
Tr
Tr
-
NF NF-Tr
•
Tr NF-16
-
340 130-340
54
NF - Not Found, <0.01 vol % for fixed gases and <1 ppav for all others (1000 ppnv - 1 vol %)
Tr - Trace, -0.01 vol % for fixed gases and -1 ppmv for all others
- » No data available
Phase I Ethane data are the total of all Cz Hydrocarbons
•Values are best values fro* available data
A-ll
-------
TABLE A.2-9. TEST DATA FOR GAS PHASE SAMPLE POINT 3.6,
HIGH PRESSURE COAL LOCK VENT
Component Vi
Dry Gaa Flow Rate
* Range
230-440
54-60
10-11
23-37
0.22-0.26
0.12-0.16
9.9-11
11.9-14
36-48
1500-3700
95-290
410-510
80-240
0.34-0.50
0.17-0.30
0.02-0.19
0 .006-0 .12
0.05-0.09
510-580
70-130
25-50
1.1-2.5
NF-130
NF - Not Found. <0.01 vol % lor fixed gases and <1 ppnv for all otters (1000 ppmv - 1 vol «>
Tr » Trace, -0.01 vol % for fixed gases and -1 ppnv for all others
- - No data available
Phase I Ethane data are the total of all C2 Hydrocarbons
•Valuej are best values from available data
A-12
-------
TABLE A.2-10. TEST DATA FOR GAS PHASE SAMPLE POINT 7.1,
HaS-RICH WASTE GAS
Component
Dry G»< Flow Rat*
(m3 tt 2S»C/gasifier-hr)
Temperature CO
Molecular Wt. at Dry Gas
Moisture Content (vt %)
Comoosition Data (Drr Gas Basil)
Fixed Gases (vol *)
H2
02
»2
CH4
CO
C02
:
1
Sulfur Snecies (nnmv)
H2S
COS
CH3SH
C2HSSH
Cl~C(+ Hydrocarbons (vol %>
Ethan*
Ethyl en*
C3
C4
C5
C6+
Aromatic Snecies (nvrnv) •
Benzene
Toluene
lyle&e + Ethylbenzene
Phenol i
Higher Aroma tics
Nitroaen Soecies (DDIBT)
NH3
HCN
Phase I
Vmlu * Range
3730
12
41.2
-
0.07 0.02-0.07
0.51 0.23-0.51
1.4 0.59-1.4
4.2 4.1-4.4
2.6 1.6-3.0
86 86-92
23000 16000-27000
<540
4100 3400-4800
710
0.34 0.34-1.5
0.22 0.22-1.1
0.14 0.14-0.58
0.06 0.06-0.21
0.01 0.01-0.12
_
-
-
Tr NF-Tr
-
2200 NF-2200
S3
Phae* II
Vain* * Rang*
3600
-
43.0
3.9
0.11
Tr Tr-0.13
Tr Tr-3 .2
4.3 4.2-4.7
1.1 1.1-3.5
88 85-88
45400 41000-50000
420 360-520
2100 1900-2300
780 670-850
0.82 0.80-0.97
Tr
0.63 0.60-0.66
0.32 0.30-0.44
0.04 0.03-0.08
0.21 0.12-0.22
110 40-110
8 4-8
NF
-
-
_
200
Vain*
3600
12
43.0
3.9
0.11
Tr
Tr
4.3
1.1
88
45400
420
2100
780
0.82
Tr
0.63
0.32
0.04
0.21
110
8
NF
Tr
-
2200
200
Orerail
* Rang*
3600-3730
0.02-0.11
Tr-0,51
Tr-3 .2
4.1-4.7
1.1-3.5
85-92
16000-50000
360-540
1900-4800
670-850
0.34-0.97
0.22-1.1
0.14-0.58
0.03-0.21
0.01-0.22
40-110
4-8
NF-Tr
NF-2200
83-200
NF - Not Found, <0.01 vol % for filed gases and <1 pp>r for all others (1000 ppmv » 1 vol
Tr m Trace, -0.01 vol % for fixed gases and —1 ppmv for all others
- - No data available
Phase I Ethane data are the total of all C2 Hydrocarbons
•Values are best values from available data
A-13
-------
TABLE A. 2-11. ATOMIC ABSORPTION DATA FOR THE
H2S-RICH WASTE GAS (7.1)
Component (|ig/m3) Phase II Value
Fe (as Fe(CO)5) 73
Ni (as Ni(CO)4) 18
Mn (as Mn(CO)5) 21
A-14
-------
TABLE A.2-12. TEST DATA FOR GAS PHASE SAMPLE POINT 7.2,
COa-RICH WASTE GAS
Component
Dry Gmi Flow Rat*
(m3 tt 23'C/gasifier-hr)
Temperature CO
Molecular Wt. of Dry Gaa
Moisture Content (*t %)
Paaa* t
Vain* * Rang*
5100 1200-5100
19
41.9
-
Phaa* II
Vain* * Rang*
3600
-
23.3
5.1
Vain*
3600
19
42.2
5.1
Overall
* Rang.
1200-5100
CoBoosition Data (Drv Ga> Basia)
Fixed Gases (vol *)
H2
02
N2
CH4
CO
C02
Sulfur Soecies (DDVV)
H2S
COS
CH3SH
C2BSSH
Cl-Cj* Hydrocarbons (vol %)
Ethan*
Ethyl en*
CJ
C4
C5
C6+
Aromatic Soecies (omnv)
Benzene
Toluene
Xylene + Ethylbenzene
Phenol i
Higher Aromatic*
Nitrozen Soeeies (oomv)
NB3
HCN
0.8 NF-0.8
Tr Tr-0.62
0.32 0.32-3.7
0.94 0.94-1.8
NP
94 91-95
39 39-90
Tr
8.2
3.4
0.29 0.29-2.2
0.26 0.20-0. 55
Tr NF-0.23
Tr NF-0.17
NF
-
•
MF NF-Tr
4.6 NF-4.6
13
Tr
Tr Tr-1.8
Tr Tr-48
1.2 0.6-1.2
Tr
51 47-54
23 20-25
62 59-62
8.5 8.2-9.7
4.7 3.5-6.1
1.6 0.5-1.6
Tr
0.28 0.17-0.29
Tr
Tr
1.0
Tr
Tr
-
-
Tr
Tr
Tr
1.2
Tr
94
39
62
8.5
4.4
1.6
Tr
0.28
Tr
Tr
NF
1.0
Tr
Tr
NF
4.6
13
NF-0.8
Tr-1.8
Tr-48.
0.6-1.8
NF-Tr
91-95
20-90
Tr-62
8.2-9.7
3.4-6.1
0.29-1.6
0.17-0.55
NF-0.23
NF-0.17
NF-Tr
NF-4.6
NF - Not Found, <0.01 vol % for fixed gases and <1 ppnv for all others (1000 ppmv - 1 vol %)
Tr " Trace, -0.01 vol % for filed gases and -1 pp>v for all others
- - No data available
Phaa* I Ethane data are the total of all C2 Hydrocarbona
•Values are best values from available data
A-15
-------
TABLE A.2-13. ATOMIC ABSORPTION DATA FOR THE
C02-RICH WASTE GAS (7.2)
Component (|ig/m3) Phase II Value
Fe (as Fe(CO)5) 320
Ni (as Ni(CO)4) 7.4
Mn (as Mn(CO)5) 7.3
A-16
-------
TABLE A.2-14. TEST DATA FOR GAS PHASE SAMPLE POINT 7.3.
CRUDE PRODUCT GAS
Component
Dry Ga* Flow Rate
(m3 .t 25*C/sasifier-hr)
Temperature (°C)
Molecular Wt. of Dry Gas
Moisture Content (wt %)
Composition Data (Drv Gas Basis)
Fixed Gases (vol *>
HI
01
N2
CH4
CO
C02
Snlfur Soecies (nnmv)
HIS
COS
CH3SB
C2&SSH
Ci-C«+ Hydrocarbons (vol %)
Ethan*
Ethylene
C3
C4
C5
C6+
Aromatic Soeeies (oomv)
Benzene
Toluene
Xylene + Ethylbenzen*
Phenols
Higher Aromatic*
Nitrogen Soecies (ovrnv)
NH3
HCN
NF - Not Found, <0.01 vol * for
Tr - Trace. -0.01 vol * for fixe
Phase I
Value » Rang*
_
20
22.5
-
36 36-45
0.55 0.20-2.6
1.6 • 0.9-1.6
13 8 .9-13
14 9.6-14
33 21-36
4400 4400-7800
74
540
98
0.65 0.65-1.1
0.35 0.35-0.40
0.15 0.15-0.24
0.04 0.01-0.04
—
_
-
-
Tr
-
3 .3 NF-3 .3
60
fixed gases and <1 ppmv
Phaae II
Vain* ' Kanf*
_
22.3
21.3
2.5
40 36-46
0.34 0.09-0.48
0.52 0.04-1.15
11 9.5-14.5
IS 13-17
31 23-40
5600 4900-6700
97 63-120
590 460-700
200 140-270
0.44 Tr-0.76
0.04 Tr-0.11
0.16 0.07-0.21
0.063 0.02-0.13
0.044 0.02-0.06
0.064 0.02-0.20
750 660-840
230 200-260
100 16-110
-
-
—
320
for all others (1000 ppmv - 1
all others
Valne
_
22.3
21.9
2.5
38.1
0.36
0.64
11.5
15
32
6000
97
590
200
0.47
0.04
0.19
0.074
0.044
0.064
750
230
100
Tr
-
3.3
320
vol *)
Overall
* Range
20-22 .3
36-46
0.09-2.6
0.04-1.6
8.9-14.5
9.6-17
21-40
4400-7800
63-120
460-700
98-270
Tr-0.76
Tr-0.11
0.07-0.40
0.02-0.24
0.01-0.06
0.02-0.20
660-840
200-260
16-110
NF-3 .3
60-320
- - No data available
Phase I Ethane data are the total of all C2 Hydrocarbons
•Values are best values from available data
A-17
-------
TABLE A. 2-15,
ATOMIC ABSORPTION DATA FOR THE
CRUDE PRODUCT GAS (7.3)
Component ( |ig/m3 )
As
Be
Cd
Co
Cr
Cu
Hg
Mo
Ni
Pb
Sb
Se
Sr
Tl
V
Zn
Phase II Value
0.43
0.13
0.48
NF
2.5
4.3
NF
NF
4.8
1.0
NF
NQ
5.6
NF
NF
30
NF - Not found
NQ =" Present, but not quantifiable
A-18
-------
TABLE A.2-16. TEST DATA FOR GAS PHASE SAMPLE POINT 7.4,
CLEAN PRODUCT GAS
Component
Dry Gaa Flo* Rate
(n3 at 25*C/gasifier-hr)
Temperature (*C)
Molecular Wt. of Dry Gas
Moisture Content (wt *)
Comoosition Data (Drv Gas B
Fixed Gases (vol *)
H2
02
»2
CH4
CO
C02
Sulfur Species (npmv)
H2S
COS
C&3SH
C2HSSH
Cl-C$+ Hydrocarbon* (vol V
Ethane
Ethylen*
C3
C4
C5
C6+
Aromatic Soecies (nomv)
Benzene
Toluene
Xylene + Ethylbenzene
Phenols
Higher Aromatica
Nitrocen Snecies (oomv)
NH3
HCN
Phase I Phaa* II
Value * Range Value * Range
_ _
-
10.2 10.2
4.1
lasis)
62 60-67 60 59-62
0.96 0.1-1.7 0.44 0.42-0.46
4.8 0.5-6.8 0.38 0.32-0.43
14 12-18 16 15.9-16.1
17 13-17.5 22 20.7-23
0.23 NF-2.4 0.02 0.004-0.02
NF
NF 0.17 0.1-0.2
Tr 1.1 0.7-1.9
Tr 1.0 0.6-1.7
0.49 Tr-0.79 0.15 0.12-0.18
Tr
Tr Tr-0.09 Tr
Tr NF-Tr
Tr NF-Tr
0.03 NF-0.03
•e. -.
-
-
Tr NF-Tr
-
Tr NF-30
- "
Value
_
-
10.3
4.1
60
0.44
0.38
16
22
0.02
NF
0.17
1.1
1.0
0.15
Tr
Tr
Tr
Tr
0.03
.
-
-
Tr
-
Tr
-
Overall
* Range
59-67
0.1-1.7
0.32-6.8
12-18
13-23
NF-2.4
NF-0.2
Tr-1.9
Tr-1.7
Tr-0.18
Tr-0.09
NF-Tr
NF-Tr
NF-0.03
NF-Tr
NF-30
NF - Not Found. <0.01 vol % for fixed gaaes and <1 ppanr for all other* (1000 ppmv - 1 vol %)
Tr <• Trace, -0.01 vol % for fixed gases and -1 ppmv for all .others
- - No data available
Phase I Ethane data are the total of all Cj Hydrocarbons
•Values are best values from available data
A-19
-------
TABLE A.2-17. ATOMIC ABSORPTION DATA FOR THE
CLEAN PRODUCT GAS (7.4)
Component (|ig/m3) Phase II Value
Fe (as Fe(CO)5) 260
Ni (as Ni(CO)4) 15
Mn (as Mn(CO)5) 44.3
A-20
-------
TABLE A.2-18. TEST DATA FOR GAS PHASE SAMPLE POINT 7.7,
INTERMEDIATE PROCESS GAS STREAM
Component
Ph«se I
V«lu * Range
Phase
Vain* *
II
Range
Overall
Vela* * Range
Dry Gas Flow Rate
(m3 at 25«C/gasifier-hr)
Temperature CO
Molecular Wt. of Dry Gas
Moisture Content (wt V
Composition Data (Dry Gas Basis)
Fixed Gases (vol %)
H2
02
N2
CH4
CO
C02
Sulfur Species (ppmv)
NO PHASE I DATA
H2S
COS
CB3SH
CzHjSH
Cj-C6+ Hydrocarbons (vol *)
Ethane
Ethylene
C3
C4
C5
C6+
Aromat ic Spec iea
Benzene
Toluene
Xylene + Ethylbenzene
Phenols
Higher Aroaatics
Nitrogen Species (pony)
NH3.
HCN
20.0
0.5
0.05
0.26
0.008-1.1
0.18-0.26
20.0
44
0.68
1.4
12.5
8.9
31
1.4
0.4
6.6
11
0.67-0.68
1.4-1.5
11-14
8 .5-12
29-32
0.9-1.4
0.3-3.3
6 .6-25
11-37
44
0.68
1.4
12.5'
8.9
31
1.4
0.4
6.6
11
0.67-0.68
1.4-1.5
11-14
8.5-12
29-32
0.9-1.4
0.3-3.3
6.6-25
11-37
0.5
0.05
0.26
0.008-1.1
0.18-0.26
NF • Not Found, <0.01 vol % for fixed gases and <1 ppsiv for all others (1000 ppmv » 1 vol %)
Tr - Trace. -0.01 vol % for fixed gases and -1 ppmv for all others
- - No data available
•Values are best values from available data
A-21
-------
TABLE A.2-19. TEST DATA FOR GAS PHASE
TAR TANK VENT
SAMPLE POINT 13.1,
Component
Dry G«t Flow Rite
(m3 at 25*C/gssifier-hr>
Temperature («C)
Molecular ft. of Dry Gas
Moisture Content (wt %)
Pk«e« I
Vain. * Raate
0.55
61
29.4
-
Phase II
Vata. * Range
0.7S
52
29.1
14
Vaia.
0.55
52
29.1
14
Orerall
* But*
0.55-0.76
52-61
Coonoiition Data (Drv Gas Basis)
Fixed Gases (vol «>
H2
02
N2
CH4
CO
C02
SnlfTir Soeeies (oomv)
H2S
COS
CH3SH
C2a5SH
Ci-Cg-K Hydrocarbons (vol %)
Ethane
Ethyl ene
C3
C4
<=5 ;
c«+
Aromatic Svecies (ounv)
Benzene
Toluene
lylene + Etnylbenzene
Phenols
Higher Aromatic*
Nitroien Soeeies (nnnv)
NR3
HCN
Tr NF-Tr
20 15 .5-20
72 72-81
0.1 0.08-0.1
NF
3.1 1.1-3.1
13000 1600-13000
NF
610 57-610
240 135-240
Tr
0.004 Tr-0.03
0.005 Tr-0.24
Tr NF-Tr
0.001
4300
100
-
57 5.2-57
-
2600 2000-2600
130
19 14-20
77.5 71-77.5
0.16 0.14-0.18
Tr
0.86 0.76-2.85
6900 3500-13000
110 51-110
390 390-400
240 220-260
Tr
-
0.01 0.008-0.01
Tr
Tr
0.37 0.12-0.42
2000 1800-2100
960 876-1100
220 190-250
-
2.2 2.2-2.25
-
Tr
19
77.5
0.16
Tr
0.86
6900
110
390
240
Tr
-
0.01
Tr
Tr
0.37
2000
960
220
57
2.2
2600
130
NF-Tr
14-20
71-81 •
0.08-0.18
NF-Tr
0.76-3.1
1600-13000
NF-110
57-«10
135-260
Tr-0.03
Tr-0.24
NF-Tr
0.001-0.42
1800-2100
876-1100
190-250
5.2-57
2.2-2.25
2000-2600
NF - Not Found, <0.01 vol % for fixed gases and <1 ppnv for all others (1000 ppmv - 1 vol %)
Tr » Trace. -0.01 vol % for fixed gases and -1 ppmv for all others
- - No data available
Phase I Ethaae data are the total of all C2 Hydrocarbons
•Values are best values fron available data
A-22
-------
TABLE A.2-20. TEST DATA FOR GAS PHASE SAMPLE POINT 13.2,
UNPURE TAR TANK VENT
Component
Pmaee I
Valoe) * Rant*
Phaa* II
Vain* * Kanie
Overall
Value * Kan|c
Dry Gas Flow Rat<
<«3 at 2J"C/gasifier-hr)
Temperature («C)
Molecular »t. of Dry 6aa
Moisture Content (wt *)
Composition Data (Dry Gas Basis)
Fixed Gases (vol %)
02
N2
CH4
CO
C02
Sulfur Species (ppmv)
HjS
COS
CH3SH
CjHsSH
Hydrocarbon! (TO! *)
Ethan*
Ethylane
C3
C4
C5
NF
20.3
78.2
0.2
430
NO PHASE II DATA
NF-430
NF
20.3
78.2
0.2
430
NF-430
Aromatic Species (PPMV)
Benzene -
Toluene
Xylene + Ethylbenzen* -
Phenols Tr
Higher Aromatica —
Nitrogen Species (opmv)
NH3 230
HCN
Acid Gaaes (vol %) 0.7
Saturated Hydrocarbons (vol *) 0.6
Unsaturated Hydrocarbons (vol *) 0.2
NF-Tr
NF-230
0.2-0.7
NF-0.2
Tr
230
0.7
0.6
0.2
NF-Tr
NF-230
0.2-0.7
NF-0.2
NF - Not Found. <0.01 vol % for fixed gases and <1 ppov for all others (1000 ppmv = 1 vol %)
Tr - Trace, -0.01 vol % for fixed gases and -1 ppmv for all others
- - No data available
•Values are best values from available data • A—23
-------
TABLE A.2-21. TEST DATA FOR GAS PHASE SAMPLE POINT 13.3,
MEDIUM OIL TANK VENT
Component
Dry Gas Flow Rat*
(a3 at 25*C/g*sifier-hr)
Temperature CO
Molecular ft. of Dry Ga*
Moisture Content (wt *)
Comoosicion Data (Drv Gaa Basis)
Fixed Gases (vol %)
H2
02
N2
CH4
CO
C02
Snlfur Soecies (oomv)
H2S
COS
CHsSH
C2H5SH
Ci-Cj+ Hydrocarbons (vol %)
Ethan*
Ethylen*
C3
C4
cs
C6+
Aromatic Soecies (mjmv)
Benzene
Toluene
Xylene + Ethylbenzan*
Phenols
Higher Aromaties
Nitroeen Soecies (nomv)
NH3
HCN
Pkaae I
Vain* * Sang*
18.6
48
30.6
-
NF NF-23
0.89 0.6-0.89
3.4 1.1-3.4
7.6 2.7-7.6
5.3 3.1-5.3
51 51-87
35000 32000-41000
NQ
1000
460
0.62 0.37-0.62
0.16 0.16-0.34
0.21 0.21-0.42
0.08 0.08-0.21
4900
1700
-
110 Tr-110
-
19 5.3-19
57
Phaa* II
Vain* * Rang*
1.7
42
32.5
8.4
Tr
0.45 0.29-0.82
1.1 0.5-4.3
7.6 6.8-8.5
5.9 5.6-13.3
56 54-58
26000 26000-26050
96 81-96
5200 4900-5500
2100 1800-2400
0.34 0.33-0.33
Tr
0.30 0.29-0.30
0.25 0.19-0.31
0.09 0.08-0.10
2.4 2.3-2.5
7650 7400-7900
1400 1300-1400
140 130-150
-
-
_
-
V*l»<
1.7
42
32.5
8.4
Tr
0.45
1.1
7.6
5.9
56
26000
96
5200
2100
0.34
Tr
0.30
0.25
0.09
2.4
7650
1400
140
110
-
19
57
Ov.rall
i * Rant*
1.7-18.6
42-48
,
NF-23
0.29-0.89
0.5-4.3
2.7-8.5
3 .1-13 .3
51-87
26000-41000
81-96
1000-5500
460-2400
0.33-0.35
0.16-0.34
0.19-0.42
0.08-0.21
2.3-2.5
7400-7900
1300-1400
130-150
Tr-110
5.3-19
NF " Not Found, <0.01 vol % for fixed gaa*a and <1 ppmv for all others (1000 ppmv - 1 vol %)
Tr * Trace. -0.01 vol % for fixed gaaes and -1 ppmv for all others
- " No data available
Phis* I Ethan* data are the total of all C2 Hydrocarbons
NQ » Present bnt not quantifiable
•Values are best values frost available data
A-24
-------
TABLE A.2-22. TEST DATA FOR GAS PHASE SAMPLE POINT 13.4,
UNPURE OIL TANK VENT
Component
Phase I
Vila* * Ran|«
Pha*a II
Vela* * Raa|*
Orersll
Vain* * Rang*
Dry Gaa Flow Rat*
-------
TABLE A.2-23. TEST DATA FOR GAS PHASE SAMPLE POINT 13.5,
CONDENSATE TANK VENT
Coaponent
Dry Ga* Flow Kate
(m3 at 25'C/gasifier-hr)
Temperature CO
Molecular Wt. of Dry Gaa
Moisture Content (wt %)
Composition Data (Drv Gas Basis)
Fixed Gases (vol *)
H2
02
N2
CH4
CO
C02
OjS
COS
CH3SH
C2H5SH
Ci-Cs+ Hydrocarbons (vol *)
Ethane
Ethyleae
C3
C4
C5
Aromatic Snecies (otsav)
Benzene
Toluene
Xylene + Ethylbenzeae
Phenols
Higher Aromatica
Nitrogen Soeeies (omv)
NH3
HCN
Phase I Phase II
Valne* Rang* Valaa * Range
3.38
7
2fi.fi
-1.0
14.6 13.8-14.fi NO PHASE II DATA
16 .6 15 .1-16 .6
61.0 58.0-fil.O
1.2 1.19-2.1
NF NF-3 .fi
fi.2 6.15-9.1
6200 2400-6900
NO
210
72
0.07 0.07-0.40
0.05 0.02-0.21
0.03 0.02-0.27
0.04 Tr-0.13
3200
3000
-
Tt Tr-12
-
NF NF-820
170
Value
3.38
7
2S.fi
-1.0
14.fi
16.fi
61.0
1.2
NF
6.2
6200
-
210
72
0.07
0.05
0.03
0.04
5200
3000
-
Tr
-
NF
170
Overall
* Range
13.8-14.fi
15 .1-16 .6
58.0-61.0
1.19-2.1
NF-3 .6
6.15-9.1
2400-<900
0.07-0.40
0.02-0.21
0 .02-0 .27
Tr-0.13
Tr-12
NF-820
NF » Not Found. <0.01 vol % for fixed gases and <1 ppmv for all others (1000 ppmv » 1 vol *)
Tr " Trace. -0.01 vol % for fixed gases and -1 ppmv for all others
- m No data available
Phase I Ethane data are the total of all C2 Hydrocarbon*
NO - Present but not quantifiable
•Values are best values froii available data
A-26
-------
TABLE A. 2-24.
TEST DATA FOR GAS PHASE SAMPLE POINT 13.6,
TAR/ OIL SEPARATION SECTION WASTE GAS TO FLARE
Ocr 0«o Plov •«•
TootoMCiro CO
llolonlor ft. of 0••
Noiotizo Comtimt
KF - Not temmt. <0.01 *«1 * (or tl»* !«..« *mt
Tr - Ti.«.. -0.01 TO! » (or fiifi n». u* -1
NO • Pr».omt bmt M« qmaatiflaol..
- ' No d»t> irilllbK
Ph*«. I Etkaao dmtm «ro tbo tot«l af &11 Cj Hydrocarbon*
• V«lao« .ro boot VOJBOO froa .voiloolo doco.
•o <200 •l/to»i
-------
TABLE A.2-25. TEST DATA FOR GAS PHASE SAMPLE POINT 13.7,
PHENOLIC WATER TANK VENT
Component
Dry Gas Flow Rate
(m3 at 25'C/gasifier-hr)
Temperature ( *C)
Molecular ft. of Dry Gaa
Moisture Content (wt %>
• Composition Data (Drv Gas Basis)
Fixed Gases (vol «)
H2
Oj
N2
CH4
CO
OH
Sulfur Soeeies (unmv)
H2S
COS
CH3SH
CjBsSH
Ci-Cfi+ Hydrocarbon* (vol *)
Ethane
Ethylene
C3
C4
C5
C6+
Aroaatic Sneeies (nnrnv) •
Benzene
Toluene,
Xylene + Ethylbenzene
Phenols
Hi (her Aromatic*
Nitrogen Soeeies (oomvl
NH3
HCN
Piaee I
Valmo * Xante
13
76
34.2
-
Tr Tr-0.2
13 10.8-13
53 ' 48.7-53.0
0.2
NF
29 29-39
6400 6400-17000
NF
650
400
0.02 0.01-0.11
0.01 0.01-0.08
0.05 0.02-0.05
0.09 NF-0.09
-
16000
6000
-
Tr NF-34
-
12000 2700-12000
38
Pha*e II
Value * Kanfe Valm
5.5 5.5
76 76
27.4 34.4
42 42
Tr
13 11-13 13
39 38-53 39
0.2
NF
35 26-35 35
12600 4000-13000 12600
41 28-41 41
2100 1200-2100 2100
7200 5200-7200 7200
0.02
0.02 0.01-0.02 0.02
0.02 0.02-0.02 0.02
0.006 0.006-0.06 0.006
1.8 1.6-2.0 1.8
11000 10500-11400 11000
2300 2200-2400 2300
280 200-310 280
- - Tr
3.1 3.1
12000
38
for all other* (1000 ocmv - 1 vol *)
Overall
• * langa
5 .5-13
Tr-0.2
10.8-13
38-53
26-39
4000-17000
NF-41
650-2100
400-7200
0.01-0.11
0.01-O.08
0.02-0.05
NF-0.09
1.6-2.0
10500-11400
2200-2400
200-310
NF-34
2700-12000
Tr " Trace. -0.01 vol % for filed gaaes and -1 pp»v for all other*
- - No data available
Phase I Ethane data are the total of all C2 Hydrocarbon*
•Values are best values froa available data
A-28
-------
TABLE A.2-26. TEST DATA FOR GAS PHASE SAMPLE POINT 14.1.
DEGASSING CYCLONE VENT
Component
Pkaaa I
Vila* * Ranie
Paaaa II
Vela* * Range
Overall
Valna * Range
Dry Gaa Flo* Rata
(»3 at 25'C/gaaifier-ar)
Teaperatara <°C>
Molaenlar Wt. of Dry Gaa
Moisture Content (wt %)
Composition Data (Drv Gaa Basis)
Filed Gasea (vol %)
H2 -
02
N2 -
CH4 -
CO -
C02
Sal far Species (murv)
HjS 2100
COS -
CH3SH
CJH5SH
Cj-Cf* Hydrocarbona (vol %)
Ethana -
Ethylene
C3 -
C4
C5 -
NO PHASE II DATA
2100
Aromatic Species (onmy)
Banzana ~
Tolnana -
Xylaaa + Ethylbanzaae -
Phenols NF
Higher Aroaatiea
Nitrogen Sneciea (gnanr)
NH3 790
HCN -
Acid Gates (vol %) 12
Sataratad Bydroeraboaa (vol %) -
Daaatnrated Hydroearboaa (vol %) 0.4
17-790
NF
790
12
0.4
17-790
NF - Not Found. <0.01 vol % for fixed gases and <1 ppjnv for all others (1000 ppmv - 1 vol %)
Tr » Trace, -0.01 vol % for fixed gaaea and -1 ppmv for all others
- - No data available
•Values are best values from available data
A-29
-------
TABLE A.2-27. TEST DATA FOR GAS PHASE SAMPLE POINT 14.2,
GAS TANK VENT
Component
V»lm» *
Rang*
Pn*s* II
Vtln * Rani*
Ov.rsll
Valo* * Rani*
Dry G»i Flow Rat*
(a* at 25°C/jasifi*r-hr)
Temperature CO
Molecular Vt. of Dry Gai
Moiitnre Content (wt %)
Composition Data (Dry Gas Basil)
Fixed Gasea (yol %)
H2
01
N2
CH4
CO
C02
Sulfnr Sneciet (mmv)
H2S
COS
CH3SH
CjBsSE
1.2
20
74
NF
485
NO PHASE II DATA
430-540
1.2
20
74
NF
485
430-540
Hydrocarfaona (vol %)
Ethan*
Etnylen*
C3
C4
Cj
Aromatic Species (mmv)
Benzen* -
Toluen*
Xylan* + Ethylbenzen* -
Phenols —
Higher Aromatic*
Nitrogen Species (anav)
NH3
HCN
Acid Gaies (vol *) 5.1
Saturated Hydrocarbons (vol %) 1.0
ITnsaturated Hydrocarbons (vol *) 0.2
3.6-4.6
NF-0.2
5.1
1.0
0.2
3.6-6.6
NF-0.2
NF * Not Found. <0.01 vol % for fixed gases and <1 ppmv for all others (1000 ppmv =• 1 vol %)
Tr - Trace, -0.01 vol % for fixed gases and -1 ppmv for all others
- - No data tvailable
•Values are best values from available data
A-30
-------
TABLE A.2-28. TEST DATA FOR GAS PHASE SAMPLE POINT 14.3,
UNCLEAN OIL TANK VENT
Coaponeat
Pkaae I
Vila* * Kant e
Phae« II
Val»« * Raafe
Overall
Vala* * Raag a
Dry Gas Flow Rate
(m3 tt 2i«C/ga«ifier-hr)
Temperature (*C)
Molecular Wt. of Dry Ga*
Moisture Content (wt *)
Composition Pata (Dry Gas Basis)
Filed Gases (vol %)
H2
02
N2
CH4
CO
COJ
Sulfur Snecies (nnmv)
HIS
COS
CH3SH
CjHsSH
Hydroearboas (vol %)
NF
21
79
NF
NO PHASE II DATA
NF
21
79
NF
NF
Ethane
Ethylene
C3
C4
CS
Aromatic Species (nnmv)
Benzene
Tolneaa
lylene + Ethylbeazaao
Phenols
Higher Aromatict
Nitrogen Soocies (ppmv)
Tr
490
NH3
HCN
Acid Gaaes (vol %) 0.6
Saturated Bydroearboas (vol %) NF
Dasatnrated Hydrocarbons (vol %) NF
NF-Tr
Tr
490
0.6
NF
NF
NF-Tr
NF - Not Found, <0.01 vol % for fixed gases and <1 ppsrr for all others (1000 ppmv - 1 vol *>
Tr - Trace, -0.01 vol * for fixed gases and -1 ppmv for all others
- - No data available
•Values are best values from available data
A-3L
-------
TABLE A. 2-2 9. TEST DATA FOR GAS PHASE SAMPLE POINT 14.4,
PHENOLIC WATER TANK VENT
Phaaa I . n,a*« II Or.rall
(.opponent Val» * Rant* Valu. « Range V.la. * Bange
Dry Gaa Flow Rate
(m3 at 25»C/gaiifier-hr)
Temperature («C) - -
Molecular Wt. of Dry Gaa
Hoiature Content (wt %) — —
Composition Data (Dry gaa Baaia)
Flied Gases (vol %)
Hj 0.2 NO PHASE II DATA 0.2
02 20 20
M2 79 79
CH4 - -
CO NF NF
COJ
Sulfur Special (PHUT)
B2S 'NF NF
COS - -
CE3SB - -
Hydrocarbona (vol %)
Ethan* -
Ethylena
C3 -
C4
C5
Cfi+ • -
Aromatic Species (pnaiv)
Banzeii* - -
Toluene — —
Xylene + Ethylbenzene -
Phenol a -
Signer Aromatica - -
Nitrogen Sneeiea (opnv)
NH3
HCN
Acid Gaaea (vol %) 1.1 0.7-1.4 1.1 0.7-1.4
Saturated Bydrocarbona (vol «) 1.0 1.0
Dnaatnrated Bydroearbona (vol V 0.2 NF-0.2 0.2 NF-0.2
NF - Not Found. <0.01 vol % for fixed gaaea and <1 ppmv for all others (1000 ppmv » 1 vol %)
Tr - Trace. -0.01 vol % for fixed gaaea and -1 ppmv for all others
- - No data available
•Valuea are beat values fron available data
A-32
-------
TABLE A.2-30. TEST DATA FOR GAS PHASE SAMPLE POINT 14.5
AMMONIA STRIPPER (1ST DEGASSING) VENT
Component
Dry Gas Flow Rat*
(m3 at i5»C/gasifier-hr)
Temperature CO
Molecular ft. of Dry Ga*
Moisture Content (wt *)
Phase
Vain. *
91
83
28.6
85
I Phase II
Range Valn» * Range
65-133 260
91
47.7
82-88 76
Vain,
260
91
32.7
76
Overall
• * Range
65-260
83-91
76-88
Composition Data (Drv Gas Basis)
Fixed Gases (vol %)
H2
02
N2
CH4
CO
C02
Snlfnr Soecies (onmv)
H2S
COS
CH3SH
C2B5SH
Ci-C<+ Hydrocarbons (vol •*)
Ethan*
Ethylene
C3
C4
C5
C6+
Aromatic Soecies (oomv)
Benzene
Toluene
Xylene + Ethylbenzene
Phenols
Higher Aromatic i
Nitroien Soecies (nomv)
NH3
HCN
NF - Not Fonnd, <0.01 vol *
Tr • Trace, -0.01 vol * for
NF
9.5
61
Tr
NF
35
46000
NF
140
32
Tr
Tr
Tr
Tr
NF
-
-
14500
-
570000
1400
for fixed gases
2.3-16.1 5.5 4.9-6.0
2.0-61 28 26-30
NF-Tr
-
24-91 64 63-64
22000-47000 22700
-
340 270-400
120 100-140
NF-0.02
NF-0.01
NF-0.04 Tr
NF-Tr
Tr
Tr
-
Tr
540-38000 7200
-
2400-570000 486000
250-1400 5600 Tr-5600
and <1 ppmv for all others (1000 ppmv -
-1 ppmv for all others
NF
-
-
Tr
NF
55
19500
NF
290
100
Tr
Tr
Tr
Tr
NF
Tr
-
Tr
6200
-
418000
4800
1 vol *)
NF-16.1
NF-61
NF-Tr
24-91
19500-47000
140-400
32-140
NF-0.02
NF-O.Oi
NF-0.04
NF-Tr
NF-Tr
540-38000
2400-570000
Tr-5600
- - No data available
Phase I Ethane data are the total of all C2 Hydrocarbona
+ Overall values ire normalized to total 100%.
•Values are best values from available data
A-33
-------
TABLE A.2-31. TEST DATA FOR GAS PHASE SAMPLE POINT 14.6.
COOLER VENT
Coanaaeat
P»«ee I
Vala»* Kani*
Phase II
Valuei * Kange
Ov.rall
Value * Range
Dry Ga* Flow Eat*
(•3 at 25°C/gasifier-hr)
Temperature (*C)
Molecular »t. of Dry Gaa
Moisture Content (wt *)
Composition Data (Pry Gaa Basis)
Plied Gases (vol *)
H2
02
N2
CB4
CO
C02
Sulfur Snecies (nnmv)
B2S
COS
CH3SH
C2H5SH
Hydrocarbons (vol %)
NF
4.4
NO PHASE II DATA
NF
Ethane
Etfeyleae
C3
C4
C5
Aroaatle Species {tranir)
Benxene
Toluene
Xylene + Etaylbenzene
Phenol*
Higher Arooatici
Nitrogen Species (pmnv)
Tr
S2000
NH3
HCN
Acid Gases (vol %) 24
Saturated Hydrocarbons (vol %) -
Dnsaturated Hydroearboas (vol 1) 0.8
74000-90000
Tr
82000
24
0.8
74000-90000
NF - Not Found, <0.01 vol % for fixed gases and <1 ppnv for all others (1000 ppmv « 1
Tr - Trace. -0.01 vol % for fixed gases and -1 ppnv for all others
vol *>
- - No data available
•Values are best values from available data
A-34
-------
TABLE A.2-32. TEST DATA FOR GAS PHASE SAMPLE POINT 14.7,
SECOND DEGASSING VENT
Component
Piaa* I
Tain** Ring•
Ph«M II
Valm*) * Rang*
Or.rall
Valu* * Bang*
Dry Gas Flow Rat*
(«3 at 25«C/ga*ifier-hr)
Temperature CO
Molecular Vt. of Dry Ga*
Moisture Contest (wt *>
Composition Data (Dry Gas Basis)
Fixed Gases (vol »)
H2
02
N2
CH4
CO
C02
Sulfur Soecies (ppmv)
H2S
COS
CEsSB
C2H5SH
Cj-Cj* Hydrocarbons (vol %)
Ethan*
Ethylen.
C3
C4
C5
NF
21
78
NF
NF
NO PHASE II DATA
NF
21
78
NF
NF
Aromatic Species (mmv)
Beszea*
Tolnea*
Xylen* + Ethylbenzene
Phenols
Higher Aromatics
Nitrogen Species (ppmv)
NF
200
NH3
HCN
Acid Gases (trol %) 0.5
Saturated Hydrocarbons (vol %) 0.9
Dnsatnrated Hydrocarbons (vol %) NF
NF-200
NF-0.3
NF
200
0.5
0.9
NF
NF-200
NF-0.5
NF - Not Found, <0.01 vol % for fixed gases and <1 ppmv for ill others (1000 ppnv - 1 vol %)
Tr » Trace. -0.01 vol % for fixed gases and -1 ppmr for all others
- - No data available
*Valaes are best values froa available data
A-35
-------
TABLE A.2-33. TEST DATA FOR GAS PHASE SAMPLE POINT 14.8,
SLOP TANK VENT
Cosmonaut
Pha.ee I
Valm** Ran|«
Phase II
Vela* * JUnge
Overall
Valoa * Banga
Dry Gat Flow Rata
(ra3 at 25*C/gasifier-hr)
Temperature ( °C)
Molecular »t. of Dry Gae
Moisture Content (wt *)
Composition Data (Pry Oa» Balis)
Fixed Gases (vol %)
H2
02
N2
CH4
CO
C02
Sulfur Soeciea (anmy^
HIS
COS
CHjSH
C2H5SH
Cl-Cfi* Hydrocarbona (TO! %)
Ethan*
Ethylena
C3
C4
C5
NF
21
77
NF
NF
NO PHASE II DATA
NF
21
77
NF
NF
Aromatic Soacies
Benzene
Toluene
Xylen* + Ethylbenxena
Pbenolf
Higher Aroaatiea
Nitrogen Soeciea (npnv)
Tr
77
NH3
HCN
Acid Gaaea (vol %) NF
Saturated Hydrocarbon* (vo). %) 0.9
Unsatnrated Hydrocarbons (vol %) 1.2
NF-Tr
17-77
NF-1.2
Tr
77
NF
0.9
1.2
NF-Tr
17-77
NF-1.2
NF - Not Fonnd. <0.01 vol % for fixed ga>e> and <1 ppmv for all others (1000 ppmv « 1 vol %)
Tr = Trace, -0.01 vol % for fixed gases and -1 ppmv for all others
- » No data available
•Values are best values froii available data
A-36
-------
TABLE A.2-34. TEST DATA FOR GAS PHASE SAMPLE POINT 14.9,
CRUDE PHENOL TANK VENT
Component
Dry Gal Flow Rat*
(•3 at 25«C/gasifler-hr)
Temperature CO
Molecular Vt. of Dry Gas
Moisture Content (wt %)
Composition Data (Drv 6aa
Fixed Gases (vol 1)
H2
02
N2
CH4
CO
C02
Snlfnr Species (ppmv)
H2S
COS
CH3SH
C2HSSH
Pha>ee I Phase II
Valic * Range Valu * Singe
0.20 0.13-0 .24
11
28.0
-1.3
Basis)
NF
20 18-21
77 76-81
Tr
NF
NF
'
180 NF-7000
NF
NF
NF
Vila
0.20
11
28.0
-1.3
NF
20
77
Tr
NF
NF
180
NF
NF
NF
Overall
• * bag*
0.13-0.26
18-21
76-81
NF-7000
•
C1-C6+ Hydrocarbons (vol *)
Ethane
Ethylene
C3
C4
Cs
C«+
Aromatic Species (pnmv)
Benzene
Toluene
Xyleae + Ethylbeazene
Phenols
Higher Aronatici
Nitrogen Species (npmv)
NH3
HCN
Tr
Tr
Tr
Tr
NF
Tr
Tr
Tr
Tr
NF
22
12
34
22-74
NF-260
22
12
34
22-74
NF-260
NF - Not Found. <0.01 vol % for fixed gases and <1 ppsv for all others (1000 ppnv - 1 vol %)
Tr » Trace, -0.01 vol % for fixed gases and -1 pjmv for all others
- - No data available
Phase I Ethane data are the total of all C2 Hydrocarbons
•Values are best values from available data
A-37
-------
TABLE A. 2-3 5. TEST DATA FOR GAS PHASE SAMPLE POINT 14.10,
DI-ISOPROPYL ETHER TANK VENT
Phase I Phsa« II Or.r.ll
Component Valw * Ran** V«lm« * Ku|« VmlM *
Ethan*
Dry Gas Flow Rat*
(•3 at 25«C/fsiifier-hr>
Temperature CO - -
Molecular ft. of Dry Gas -
Moisture Content (wt %> -
Composition Data (Dry Gai Basis)
Fiied Gases (vol V
HZ NF NO PHASE II DATA NF
02 21 Zl
TO 79 79
CH4 -
CO NF NF
C02
Snlfnr Soaeigs (PPBT)
BlS NF NF
COS -
CHsSH
C2HSSH
Hydrocarbon* (TO! %)
C3
C4
C5
C6+
Aromatic Species
Benzene - ~
Tolnene - -
Xylene + Ethylbeniene -
Phenol i Tr NF-Tr Tx NF-Tr
Higher Aroma tic» -
Nitrogen Species (ppay),
" NHJ 51 31
HCN -
Acid Ga»e« NF NF
Saturated Hydrocarbons (vol «> 0.7 0.7
Unsatnrated Hydcocarboni (vol %) NF Nf
NF =• Not Found, <0.01 vol % for fixed gases and <1 ppmv for all others (1000 ppmv - 1 vol V
Tr * Trace, -0.01 vol % for fixed gases and -1 ppmv for all others
- - No data available
•Values are best values from available data
A-38
-------
TABLE A. 2-3 6. TEST DATA FOR GAS PHASE SAMPLE POINT 15.1,
LIGHT TAR STORAGE TANK VENT
Component
Valo* * Range
Phase II
Vain* * R«af*
Orerall
Vain* * Bange
Dry Gas Flo* Rate
(•3 at 25'C/gaiifier-hr)
Temperature (*C)
Molecular Wt. of Dry Gas
Moisture Content (wt ft)
Composition Data (Dry Gas Basis)
Fixed Gases (vol ft)
H2
02
N2
CH4
CO
C02
Sulfur Species (PPBT)
H2S
COS
CH3SH
CjHsSH
CJ-C6+ Hydrocarbons (vol ft)
NF
19
81
NF
890
NO PHASE II DATA
230-890
0.55
NF
19
81
NF
890
230-890
Ethane
Ethylone
C3
C4
C5
Aromatic Species (ppmv)
Benzene —
Toluene -
Xylene + Ethylbensene -
Phenols Tr
Higher Aronatios —
Nitrogen Species (ppmv)
NH3 100
HCN
Acid Gases (vol ft) 0.4 NF-0.4
Saturated Hydrocarbons (vol ft) NF
Unsaturated Hydrocarbons (vol ft) 1.4 0.2-1.4
Tr
100
0.4
NF
1.4
NF-0.4
0.2-1.4
NF - Not Found. <0.01 vol ft for fixed gases and <1 ppmv for all others (1000 ppmv - 1 vol ft)
Tr - Trace, -0.01 vol ft for fixed gases and -1 ppmv for all others
- - No data available
•Values are best values from available data A—39
-------
TABLE A.2-37. TEST DATA FOR GAS PHASE SAMPLE POINT 15.2,
MEDIUM OIL STORAGE TANK VENT
Coa\poaeat
P»aa« I
Valoa- * Santa
Phaaa II
* Raaie
Overall
Valaa * Rang*
Dry Gas Flow Rata
(»3 «t 25»C/ga«ifi»r-hr)
Temperature (*C)
Molecular Wt. of Dry Gaa
Moistara Coataat (wt %)
Comeositioa Data (Dry Ga» Basia)
Fiied Gases (vol *)
H2
02
N2
CB4
CO
COJ
Sulfur Species (ppmv)
HjS
COS
CH3SH
NF
6.2
88
NF
1S50
NO PHASE II DTA
1500-1600
NF
6.2
88
NF
1500
1500-1600
Hydrocarboaa (TO! »)
Etaaaa
Ethylaaa
C3
C4
C5
Aromatic Smeies (onnv)
Baazaaa
Toluaaa
Xylaaa + Ethylbaazaaa
Phaaola
Higher Aroutica
KitTQgen Sneciea (nnnv)
Tr
75
NH3
HCN
Acid Gaaaa (vol %) 5.0
Saturated Hydroearbona (vol %) 0.4
Unsatarated Hydrocarboaa tvoL %) 1.2
O.fi-5.0
NF-1.2
Tr
75
5.0
0.4
1.2
0.6-5.0
NF-1.2
NF « Not Fooad. <0.01 vol % for fixed gaaaa aad <1 ppmv for all otaerr (1000 ppmv m 1 vol %)
Tr 3 Trace, —0.01 vol % for fixed gaaes aad —1 ppmv for all others
- - No data available
•Values are best values fro* available data A—40
-------
TABLE A.2-38.
TEST DATA FOR GAS PHASE SAMPLE POINT 15.3,
NAPHTHA STORAGE TANK VENT
Component
Dry Gas Flow Rat*
(m3 it 25«C/gasifier-hr)
Temperature <*C)
Molecular ft. of Dry G««
Moisture Content (wt %>
Comoosition Data (Drv Gas Basis)
Fixed Gases (vol %)
HI
02
N2
CH4
CO
C02
Sulfur Sneeies (uomv)
H2S
COS
CH3SH
CjHjSH
Ci-Cg* Hydrocarbons (vol *)
Ethan*
Ethylen*
C3
C4
C5
c«+
Aromatic Soecies (wnv)
Benzene
Toluene
Xylene + Ethylbenzene
Phenols
Higher Aromatic*
Nitroaen Soecies (QDBIV)
NH3
HCN
Phase I Phase II
Valmai * Rang* Vain* * 2aa|*
0.033 4.5
32
29.5 32.4
5.0
NF
3.9 3.9-9.0 2.6 2-5-2.fi
95 91-95 84 84-84
NF
NF
NF 0.85
NF NF-1600
NF
4100 2600 2400-2700
6700 9700 6900-12000
0.009 0.007-0.009 Tr
0.007 0.004-0.10 0.01 0.01-6.01
0.10 0.03-0.10 0.07 0.07-0.07
0.39 0.10-0.39 0.08 0.07-0.08
5.3 5.1-5.4
4000 37SOO 37200-38000
1300 1900 1600-2100
60 57-<3
Tr NF-Tr
-
NF NF-23
1100
Valu
4.5
32
33.3
5.0
NF
2.6
84
NF
NF
0.85
NF
NF
2600
9700
Tr
0.01
0.07
0.08
5.3
37600
1900
60
Tr
-
NF
1100
Overall
* * Range
0.033-4.5
2.5-9.0
84-95
NF-0.8S
NF-1600
2400-4100
6700-12000
Tr-0.009
0.004-0.10
0.03-0.10
0.07-0.39
5.1-5.4
37200-38000
1600-2100
57 -<3
NF-Tr
NF-23
NF • Not Found, <0.01 vol % for fixed gases and <1 ppav for all others (1000 ppmv - 1 vol «)
Tr - Trace, -0.01 vol % for fixed gases and -1 ppmv for all others
- • No data available
Phase I Ethane data are the total of all C£ Hydrocarbons
•Values are best values from available data
A-41
-------
TABLE A. 2-3 9. TEST DATA FOR GAS PHASE SAMPLE POINT 15.4,
^ _ CRUDE PHENOL STORAGE TANK VENT
»••• I Ph.«. II OT.MU
loaponcnt V»lm»* Rang* ValM * Rang* V«lu» * Rang*
Dry Gaa Flow Rat*
(m3 at 25»C/gasifi«r-hr>
Teaperatnr* (°C) - -
Molecular ft. of Dry Gaa - -
Moisture Content (wt *> . -
Composition Data (Drr Gas Basis)
Fixed Gases (vol %)
H2 NF NO PHASE II DATA NF
01 16 16
Ml 84 84
CH4
CO NF NF
C02 -
Snlfur Species (yumr)
H2S NF NF
COS
CH3SH
C2H5SH
Bydrocarfaona (vol *)
Ethan*
Etlrylen.
C3 .
C4 - -
CS -
C<+
Aromatic Species (ncmv)
Benzene - -
Tolnen* - ' -
Xylan* + Ethylbenzcn* - -
Phenol a Tr NF-Tr Tr NF-Tr
Higher Aroaatics - -
Nitrogen Specie s (puny)
NH3 3.7 3.7
HCN -
Acid Gasea (vol *) NF NF
Saturated Hydrocarbona (vol '*) 0.4 0.4
Unaatnrated Hydrocarbona (vol %) NF NF
NF * Not Found. <0.01 vol % for fixed gases and <1 ppmv for all others (1000 ppvv - 1 vol %)
Tr » Trace, -0.01 vol % for fixed gases and -1 ppmv for all others
— * No data available
•Valn*a are beat values frost available data
A-42
-------
TABLE A.2-40.
TEST DATA FOR GAS PHASE SAMPLE POINT 20.1,
COMBINED GAS TO FLARE
Coa*raiat
Or? 0M Flo. hta
(a) it 25*C/|»ifi«-a>)
SUldr
••OiHkaiK
TMamtan CO
feiMaiu rt. of D«r o««
Xaiitin Coauat (wt *>
al si
as
01
MI
04
CO
COJ
ass
cot
aitit
ciua
C1-C4+ ara*«..rftM« (T.I »)
Itkaa.
ItkrUa.
Cl
C4
C]
C4»
&»•«•
Tvlan.
Irl.m. . EtmrU'a»a.
n.uii
Ri(A*r Aroaatie*
mtramam Srtmatmm (BIM-I
N«J
era
Fk..« X PkaM IX
Vila.* Imat. Talaa* l*a|*
3200 1100 ' 1100-3500
230
15 11
41.0 41.7
2.5
Tr IfVT* Tr
Ti Tr-O.i? • 0.13 Ti 3.2C
0.50 0.50-1.1 0.14 Tr-4.19
10 4.3-10 5.2 4.1-4.4
NT 1.4 1.1-3.7
u rt-n u n-40
14000 UOO-19000 10400 10000-13000
-HO 150 240-140
;«e :jc; ::M ssoc
-400 190 140-170
'
1.01 0.1»-1.> 0.77 0.73-0.10
Tr
1.01 0.11-1.3 0.<5 0.41H>.<7
«.3» O.Of-1.1 0.3« 0.32-0.30
0.14 0.04-0.17 0.04 0.02-0. 04
0.04 0.01-0.11
(40 440-130
213 (7-940
33
Tr
- -
»
100
Ora.ll
1100
230
21
41.7
1.5
Tr
3.10
0.21
4.3
l.f '
U
10400
230
:;:s
1M
0.77
Tr
0.<5
0.31
0.04
O.OC
<40
115
33
Tr
—
NF
100
taac.
1100-3500
15-11
l»-Tr
Tr-0.37
T«-l.»
4.1-10
MM .7
n-n
1500-15000
140-1M
1300-2SW
140-400
0.1»-0.30
0.11-1.5
O.Of-1.1
0.01-0.17
0.01-0.12
440- UO
•t-340
NT • Net font, <0.01 vol % for ftz*4 !•••• tmd <1 pyaw for ill othmr* (1000 powr - 1 vol %)
Tr - Tr«««, Ml. 01 TO! * for fix*4 !•••• t«d -1 ppa* for til otkor*
?hM* t Et**a« data *r* tko COCal of til Ct
*T«lu» ««• 9«ac r«lM« fro* ATailafclo data.
••no* nt* drnvimt 4ii«k*uio fro* tM (aaifUc taro««m t*o hie* proaa«*« «oai lock rornt. tlmw »orag*4.
A-43
-------
TABLE A.2-41. ATOMIC ABSORPTION DATA FOR THE
COMBINED GAS TO FLARE (20.1)
Component (|ig/m3)
As
Be
Cd
Co
Cr
Cu
Hg
Mo
Ni
Pb
Sb
Se
Sr
Tl
V
Zn
Phase II Value
1.9
NF
0.24
0.17
NF
5.8
NF
NF
7.5
1.0'
NF
7.2
4.4
NF
NF
31
NF = Not found
A-44
-------
A3.0. COMPILATION OF PARTICUALTE DATA FOR GASEOUS STREAMS
TABLE A.3-1. PARTICULATE DATA FOR GAS PHASE SAMPLE POINT 1.2,
FLEISSNER AUTOCLAVE VENT
Component Phase I Phase II Overall
(mg/m3 at 2S°C) Value Range Value Range Value Range
NO PHASE I DATA
Total Particnlate 1080 1080
Particnlate 280 280
Condensed Organics 480 480
(Extracted)
Dissolved Solids 320 320
TABLE A.3-2. PARTICULATE DATA FOR GAS PHASE SAMPLE POINT 2.2,
DEDUSTING CYCLONE VENT
Component Phase I Phase II Overall
(mg/m3 at 25°C) Value Range Value Range Value Range
Total Particnlate 43 43-50 90 90-175 90 43-175
Particulate - -
Condensed Organics - - -
(Extracted)
Dissolved Solids
.amtJM ' laagFa-*—-T'"tWBasaasBagrraBgr?frril-'.'nrrffTrTgB-.TlB:n:wTr-*M~~~~'^'~~~~~gBsrr''gffarrrr'-— T*"TjSBiBggsg'Tff^asa
- No data available
A-45
\
-------
TABLE A.3-3. PARTICDLATE DATA FOR GAS PHASE SAMPLE POINT 3.2,
LOW PRESSURE COAL LOCK VENT
Component
(mg/m» at 25«C)
Phase I
Value Range
Phase II Overall
Value Range Value Range
Total Particulate
Particulate
13800
Condensed Organics -
(Extracted)
Dissolved Solids -
12700-13800 8100
220
7300
650
8100 8100 8100-13800
220
7300
650
- No data available
TABLE A.3-4. PARTICULATE DATA FOR GAS PHASE SAMPLE POINT 3.3,
GASIFIER START-UP VENT
Component Phase I
(mg/m3 at 25°C) Value Range
Phase II Overall
Value Range Value Range
NO PHASE I DATA
Total Particulate
Particulate
Condensed Organics
(Extracted)
Dissolved Solids
9450
61
8980
400
9450
61
8980
400
A-46
-------
TABLE A.3-5. PARTICDLATE DATA FOR GAS PHASE SAMPLE POINT 3.5.
ASH LOCK CYCLONE VENT
Component
(mg/ms at 25«C)
Phase I
Value Range
Phase II Overall
Value Range Value Range
Total Particulate 10300
Particulate
Condensed Organics -
(Extracted)
Dissolved Solids -
1200-11600 NO PHASE II DATA 10300 120-11600
- No data available
TABLE A.3-6. PARTICDLATE DATA FOR GAS PHASE SAMPLE POINT 3.6,
HIGH PRESSURE COAL LOCK VENT
Component
(mg/mj at 25«C)
Phase I
Value Range
Phase II Overall
Value Range Value Range
Total Particulate
Particulate
970
Condensed Organics —
(Extracted)
Dissolved Solids -
200-1260
960
61
660
240
960
61
660
240
200-1260
- No data available
A-47
-------
TABLE A.3-7. PARTICDLATE DATA FOR GAS PHASE SAMPLE POINT 13.6,
TAR/OIL SEPARATION SECTION WASTE GAS TO FLARE
Component Phase I Phase II Overall
(mg/m3 at 25°C) Value Range Value Range Value Range
NO PHASE I DATA
Total Particulate - 920 920
t
Particulate 29 29
Condensed Organics 660 660
(Extracted)
Dissolved Solids 230 230
TABLE A.3-8. PARTICDLATE DATA FOR GAS PHASE SAMPLE POINT 20.1.
COMBINED GAS TO FLARE
Component Phase I Phase II Overall
(mg/m3 at 2S°C) Value Range Value Range Value Range
NO PHASE I DATA
Total Particulate 410 410
Particulate 47 47
Condensed Organics 310 310
(Extracted)
Dissolved Solids 54 54
A-48
-------
A4.0. COMPILATION OF DATA FOR AQUEOUS STREAMS
TABLE A.4-1. ATOMIC ABSORPTION DATA FOR THE
FLEISSNER CONDENSATE (1.3)
Component (mg/L)
As
Be
Cd
Co
Cr
Cu
Hg
Mo
Ni
Pb
Sb
Se
\
Sr
Tl
V
Zn
Phase II
Value
0.85
0.005
0.0024
0.022
0.25
0.005
0.08
0.031
0.56
0.038
NF
0.016
2.1
NF
0.10
1.2
NF = not found
A-49
-------
TABLEA A. 4-2. WATER QUALITY PARAMETERS FOR THE CYANIC WATER (7.5)
Overall
Component Value* Range
Flow Rate (a^/gasif ier-hr)
Temperature (°C) 80
pfl 11.9 11.4-12.1
Total Solids (mg/L) 730
Total Non-Volatile Solds (mg/L) 560
Total Suspended Solids (mg/L) 140
Total Dissolved Solids (mg/L) 590
Water Quality Parameters
COD (as mg02/L) 205
Permanganate 570
(as mg02/L)
Composition Data (mg/L)
TOC
Tars and Oils
Total Phenols
Volatile Phenols
Other Phenols -
Free Ammonia -
Fixed Ammonia —
Cyanide —
Nitrites
Nitrates
Pyridines -
Chlorides
Florides
Sulfites
Sulfates
Hydrogen Sulfide
Thiocyanate • -
Thiosulfates
Sulfur 60 52-68
- = No data available
"Values are best values from available data
A-50
-------
TABLE A. 4-3. SPARK SOURCE MASS SPECTRAL RATE FOR THE
CYANIC WATER (7.5)
Component (mg/L)
U
Th
Pb
Ce
La
Ba
I
Y
Sr
Rb
Br
Se
As
Ge
Zn
Cu
Ni
Co
Fe
Mn
Cr
V
Ti
Sc
K
Cl
P
Si
Al
Na
F
B
Li
S
Mg
Overall
Value
10.01
10.01
0.008
0.004
0.008
0.02
0.4
0.03
0.01
<0.001
0.1
0.02
0.09
0.02
0.05
0.02
0.007
10.003
4
0.04
0.009
0.001
0.4
10.002
7
4
0.03
1
0.07
>4
±0.3
0.02
0.002
>10
>10
A.-51
-------
TABLE A.4-4.
WATER QUALITY PARAMETERS FOR THE
QUENCHED ASH WASTEWATER (12.3)
Component
Overall
Value*
Range
Flow Rate (m3/gasifier-hr)
Temperature (°C)
pH
Total Solids (mg/L)
Total Non-Volatile Solids (mg/L)
Total Suspended Solids (mg/L)
Total Dissolved Solids (mg/L)
Water Quality Parameters
COD (as mg02/L)
Permanganate (as mg02/L)
BOD5 (as mg02/L)
Composition Data (mg/L)
TOC
Tars and Oils
Total Phenols
Volatile Phenols
Other Phenols
8.1
10900
5700
8760
2100
1460
8060
90
NF
0.17
- = No data available
Tr = Trace
NF = Not found
•Values are best values from available data
8.1-12.1
1300-11500
130-5700
570-8760
760-2600
30-90
0.04-0.3
Free Ammonia
Fixed Ammonia
Cyanide
Nitrites
Nitrates
Pyridines
Chlorides
Florides
Sulfites
Sul fates
Hydrogen Snlfide
Thiocyanate
Thiosnlfates
Tr
1.9
0.01
0.40
4.8
—
28.0
0.91
Tr
495
Tr
0.026
Tr
1.5-2.5
Tr-0.01
0.05-0.82
4.0-5.6
20-37
0.65-1.2
320-670
0.01-0.04
A-52
-------
TABLE A. 4-5.
WATER QUALITY PARAMATERS FOR THE
PHENOSOLVAN INLET WATER (14.0)
Component
Overall
Value*
Range
Flow Rate (m^/gasifier-hr)
Temperature (°C)
pH
Total Solids (mg/L)
Total Non-Volatile Solids (mg/L)
Total Suspended Solids (mg/L)
Total Dissolved Solids (mg/L)
Water duality Parameters
COD (as mg02/L)
Permanganate (as mg02/L)
BOD5 (as mg02/L)
True Color (Pt-Co)
Composition Data (mg/L)
TOC
Tars and Oils
Total Phenols
Volatile Phenols
Other Phenols
Free Ammonia
Fixed Ammonia
Cynide
Nitrites
Nitrates
Pyridines
Chlorides
Florides
Sulfites
Snlfates
Hydrogen Sulfide
Thiocyanate
Thiosulfates
P04
60
9.17
2320
52
150
2170
18900
14200
9030
17500
4970
400
2120
3510
250
>75
<2.5
9.14-9.17
17700-18900
- = No data available
*Values are best values from available data
A-53
-------
TABLE A.4-6,
TRACE ORGANIC SPECIES DATA FOR THE
PHENOSOLVAN INLET WATER (14.0)
Component (mg/L)
Overall
Value
BTX Analysis*
Benzene
Toluene
Xylene
Nitrogen Species Analysis**
Pyridine
2-Methylpyridine
3- and 4-Methylpyridine(s)
Dimethyl- or Ethylpyridine(s)
Dimethyl- or Ethylpyridine(s)
Alfcylpyridine(s)
AlkyIpyridine(s)
Qninoline
AlkyIquino1ine(s)
PNA Analysis***
Benz(a)anthracene
7,12-Dimethylbenz(a)anthracene
Benzo(b)fluoranthrene
Benzo(a)pyrene
3-MethyIcholanthrene
Dibenz(a,h)anthracene
252 Group (as Benzo(a)pyrene)
0.9
0.5
0.8
28
29
13
39
7
16
10
5
12
0.92
0.23
0.68
0.19
<0.004
0.02
1.26
* Analysis by GC/FID
** Analysis by GC/HECD
*** Analysis by GC/MS-Liquid Crystal
A-54
-------
TABLE A.4-7. PHENOL SPECIATION DATA FOR THE
PHENOSOLVAN INLET WATER (14.0)
Overall Retention
Component (mg/g) Value* Time
Phenol 0.69 8.55
o-Cresol (as Phenol) 0.26 9.50
nr-Cresol 0.61 9.70
p-Cresol (as Phenol) 0.10 9.90
2,6-Dimethylphenol 0.013 10.10
2,4-Dimethylphenol 0.13 10.50
3,4-Dimethylphenol 0.19 10.95
1-Naphthol NF 13.20
Unknowns (as Phenol)
0.020 10.35
0.21 10.65
0.21 11.20
0.020 11.30
0.076 11.45
0.010 11.60
0.10 11.70
0.052 12.40
Other Unknowns (as Phenol)** 0.21
* Analysis by GC/FID
** Summation of all other unknown peaks
NF - Not found
A-55
-------
TABLE A.4-8.
ATOMIC ABSORPTION DATA FOR THE
PHENOSOLVAN INLET WATER (14.0)
Component (mg/L)
As
Be
Cd
Co
Cr
Cu
Hg
Ho
Ni
Pb
Sb
Se
Sr
Tl
V
Zn
Overall
Value
0.10
NF
0.0014
NF
0.023
0.011
0.14
NF
0.013
0.014
NF
0.050
0.10
NF
NF
0.28
NF » Not found
A-56
-------
TABLE A. 4-9.
WATER QUALITY PARAMETERS FOR THE
PHENOSOLVAN WASTEWATER (14.11)
Component
Flow Rate (m3/gasif ier-hr)
Temperature (°C)
pH
Total Solids (mg/L)
Total Non-Volatile Solids (mg/L)
Total Suspended Solids (mg/L)
Total Dissolved Solids (mg/L)
Water Quality Parameters
COD (as mg02/D
Permanganate (as mg02/L)
BOD5 (as mg02/L)
True Color (Pt-Co)
Composition Data (mg/L)
TOC
Tars and Oils
Total Phenols
Volatile Phenols
Other Phenols
Free Ammonia
Fixed Ammonia
Cyanide
Nitrites
Nitrtes
Pyridines
Chlorides
Florides
Sulfites
Sul fates
Hydrogen Sulfide
Thiocyanate
Thiosulf ates
Sulfur
P04—
Overall
Value*
-
33
9.6
1350
54
190
1160
7910
4040
2350
13750
1470
<200
230
130
100
Tr
205
0.019
Tr
11.4
—
60
Tr
—
110
—
<75
Tr
84
<2.5
Range
9.0-10.0
960-1520
28-190
880-1490
3130-11130
4040-28920
170-270
89-160
201-209
0.017-0.02
10.9-11.85
16-122
105-112
•
2.8-75
- = No data available
Tr = Trace
•Values are best values from available data
A-57
-------
TABLE A.4-10. POLINUCLEAR AROMATIC HYDROCARBON DATA FOR THE
PHENOSOLVAN WASTEWATER (14.11)
Overall
Component (mg/L) Value*
Benz(a)anthracene NF
7,12-D line thy lbenz(a)anthracene NF
Benzo(b)fluoranthrene NF
Benzo(a)pyrene NF
3-Methylcholanthrene NF
Dibenz(a,h)anthracene NF
252 Group (as Benzo(a)pyrene) 0.19
*Analysis by GC/MS-Liquid Crystal
NF = Not Found
A-58
-------
TABLE A.4-11. SPARK SOURCE MASS SPECTRAL DATA FOR THE
PHENOSOLVAN WASTEWATER (14.11)
Component (mg/L)
U
Th
Pb
Ba
I
Sn
Zr
Y
Sr
Br
Se
As
Ge
Zn
Cu
Ni
Co
Fe
Mn
Cr
V
Ti
Sc
Ca
K
Cl
P
Si
S
Al
Mg
Na
F
B
Li
Overall
Value
10.03
10.04
0.07
0.05
0.02
0.009
0.02
10.03
0.02
0.009
0.03
0.02
0.03
0.07
0.03
0.08
0.003
0.5
0.01
0.005
0.003
0.02
<0.005
6
1
0.08
0.08
1
110
0.1
2
4
H).02
0.1
0.003
A-59
-------
A5.0. COMPILATION OF DATA FOR SOLID PHASE STREAMS
TABLE A. 5-1,
Component
TEST DATA FOR SOLID PHASE SAMPLE POINT 1.1,
FLEISSNER BAGHOUSE CATCH
Overall
Value*
Range
Proximate Analvsis (wt %)
Moisture
Ash
Volatile
Fixed Carbon
Carbon Dioxide
Total Sulfur
Free Sulfur
Fixed Sulfur
Hydrogen
Ni t ro g en/Oxyg en
Chlorine
24
15
35
27
2.9
1.0
0.18
0.82
3.0
15.8
21-27
13-33
33-36
13-27
2.9-14
0.97-1.0
0.17-0.18
0.82-0.83
2.9-3.1
15.3-16.5
Proximate Moisture Free
(wt % drv basis)
Ash
Volatile
Fixed Carbon
Carbon Dioxide
Total Sulfur
Free Sulfur
Fixed Sulfur
Hydrogen
Nitrogen/Oxygen
Chlorine
Heating Value (Real/kg)
Proximate HHV
LHV
Proximate (Moisture Free)
HHV
LHV
19
46
35.0
3.8
1.3
0.23
1.1
4.0
21
3760
3480
4970
4780
17-42
42-48
34.9-35.2
3.7-18
3650-3880
3360-3600
(Continued)
A-60
-------
TABLE A.5-1. (Continued)
Component
Overall
Value*
Range
Proximate Moisture and Ash Free
Analysis (wt %)
Volatile
Fixed Carbon
Carbon Dioxide
Total Sulfur
Free Sulfur
Fixed Sulfur
Hydrogen
Ni tro g en/ Oxyg en
Chlorine
Ash Chemical Composition (wt %)
57
43
1.7
0.29
1.4
5.0
26
56-72
28-44
A1203
CaO
HgO
S03
P205
Na20
K20
MnO
Acidic/Basic Ratio
Other Properties
Specific Gravity (g/ml)
Specific Surface area (cm2/g)
Tar (wt %)
Gas Water (wt %)
Semicoke (wt %)
Gas and Losses (wt %)
Grain Size (mm)
25
6.8
6.7
36
6.3
16
0.34
0.51
1.6
0.40
0.14
0.57
3470
6.3
9.7
67
17
-60 to +6
- = No data available
* Values are best values from available data
A-61
-------
TABLE A. 5-2.
TEST DATA FOR SOLID PHASE SAMPLE POINT 2.0,
DRIED COAL TO GASIFICATION
Component
Proximate Analysis (wt %)
Moisture
Asa
Volatile
Fixed Carbon
Carbon Dioxide
Total Sulfur
Free Sulfur
Fixed Sulfur
Hydrogen
Ni t ro g en/ Oxy g en
Chlorine
Proximate Moisture Free Analysis
(wt % dry basis)
Ash
Volatile
Fixed Carbon
Carbon Dioxide
Total Sulfur
Free Sulfur
Fixed Sulfur
Hydrogen
Nitrogen/ Oxygen
Chlorine
Heating Value (Kcal/kz)
Proximate HHV
LHV
Proximate Moisture Free
HHV
LHV
Overall
Value*
24
14
36
27
2.3
1.2
0.35
0.82
3.4
16.5
0.01
19
46
35
3.4
1.5
0.48 .
1.1
4.4
22
0.01
3900
3700
5000
5050
Range
20-30
20-21
32-39
22-30
1.3-3.7
0.89-1.8
0.16-0.84
0.64-1.1
2.8-3.8
15-19
14-27
35-50
23-39
1.7-5.2
1.1-2.3
0.21-1.3
0.83-1.4
3.8-4.8
20-24
3210-4340
2940-4280
3470-5500
4040-5500
(Continued)
A-62
-------
TABLE A.5-2. (Continued)
Component
Overall
Value*
Range
Ultimate Analysis (wt %)
Moisture
ASA
Volatile
Fixed Carbon
Total Sulfur
Free Sulfur
Fixed Sulfur
Hydrogen
Nitrogen
Oxygen (By Difference)
Chlorine
Proximate Moisture and Ash
Free Analysis (wt %)
Volatile
Fixed Carbon
Carbon Dioxide
Total Sulfur
Free Sulfur
Fixed Sulfur
Hydrogen
Nitrogen/Oxygen
Chlorine
Heating Value (Kcal/ke)
Ultimate HHV
LHV
20
14
45
0.89
3.5
1.1
16
0.01
57
43
4.4
0.59
5.4
27
54-59
41-46
2.0-6.8
0.26-1.5
4.9-5.9
25-33
4110
Proximate Moisture and Ash Free
HHV
LHV
6200
6070
5860-6390
5060-6300
(Continued)
A-63
-------
TABLE A.5-2. (Continued)
Component
Ash Fusibility (°C)
(Proximate Analysis)
Sintering Temperature
Softening Temperature
Hemisphere Temperature
Pouring Temperature
Ash Chemical Composition (wt %)
(Ultimate Analysis)
SiOj
Fe203
CaO
MgO
S03
P2<>5
Na20
K20
MnO
Acidic/Basic Ratio
Other Properties
Specific Gravity (g/ml)
Mi cum Test (+6mm) %
Tar (wt %)
Gas Water (wt %)
Semicoke (wt %)
Gas and Losses (wt %)
Overall
Value*
970
1180
1300
1320
28
7.2
8.3
31
5.6
14
0.15
0.46
1.4
0.32
0.62
0.538
75
5.6
11
67.0
16.5
Range
960-1000
1130-1220
1200-1360
1220-1380
15-40
4.4-12
2.0-22
20-41
0.37-12
6.5-23
Tr-0.34
0.12-0.92
0.82-1.8
0.20-0.46
0.37-0.77
0.5-0.6
70-78
4.9-6.3
9.7-12.0
66.9-67.1
16.1-16.9
- = No data available
*Values are best values from available data
A-64
-------
TABLE A.5-3. PARTICLE SIZE DISTRIBUTION DATA FOR THE
DRIED COAL TO GASIFICATION (2.0)
Particle
0
1
2
3
5
10
15
20
25
30
40
50
to
to
to
to
to
to
to
to
to
to
to
to
>60
Size (mm)
1
2
3
6
10
15
20
25
30
40
50
60
Cumulative
Value (wt %)*
1.
2.
3
8
9
19
35
45
52
73
80
90
100
85
68
.6
.1
.7
.5
.5
.9
.4
.0
.6
.7
.3
Fraction
Value (wt %)*
1.
0.
1
4
1
9
16
10
6
20
7
10
9
85
83
•
•
•
•
.
•
•
•
•
«
•
1
3
6
8
0
4
5
6
6
1
6
Fraction
Range (wt %)
1
0.
0.
1
1
7
8
7
6
16
2
4
3
•
1-2.
56-1.
56-1.
•
*
•
•
•
•
•
•
•
•
1-7.
1-2.
4-12
4-23
4-13
3-6.
8-24
4-7.
5-15
3-15
6
1
6
4
1
.2
.3
.3
7
.4
8
.8
.8
•Values are average values of fraction range.
•A-65
-------
TABLE A.5-4. ATOMIC ABSORPTION DATA FOR THE
DRIED COAL TO GASIFICATION (2.0)
Component (mg/kg)
As
Be
Cd
Co
Cr
Cu
Hg
Mo
Ni
Pb
Sb
Se
Sr
Tl
V
Zn
Overall
Value
59
1.0
4.0
3.4
87
43
0.74
6.4
150
8.2
NF
20
190
NF
14
140
NF = Not found
A-66
-------
TABLE A.5-5. SPARK SOURCE MASS SPECTRAL DATA FOR THE
DRIED COAL TO GASIFICATION (2.0)
Component (mg/kg)
U
Th
Pb
En
Sm
Nd
Pr
Ce
La
Ba
Cs
I
Te
Sn
Cd
Ho
Nb
Zr
Y
Sr
Rb
Br
Se
As
Ge
Ga
Zn
Cu
Ni
Co
Mn
Cr
V
Ti
Sc
Cl
P
F
B
Li
Overall
Value
12
12
2
10.3
1
0.8
0.9
3
2
110
0.1
0.5
0.4
0.5
0.4
6
3
6
2
91
5
2
0.6
2
0.1
2
1
8
23
0.4
230
11
8
660
1
32
780
Z2
21
1
(Continued)
A-6 7
-------
TABLE A.5-5. (Continued)
Overall
Component (mg/kg) Value
Ca >1000
K >1000
S >1000
Si >1000
Al >1000
Mg >1000
Na >1000
Fe >1000
A-68
-------
TABLE A. 5-6.
TEST DATA FOR SOLID
COAL ROOM DUST
PHASE SAMPLE POINT 2.1,
Component
Overall
Value*
Range
Proximate Analysis (wt %)
Moisture
Ash
Volatile
Fixed Carbon
Carbon Dioxide
Total Sulfur
Free Sulfur
Fixed Sulfur
Hydrogen
Nitrogen
Oxygen
Chlorine
Ash Fusibility (°C)
22
23
35
20
8.4
21-24
13-33
33-36
13-27
2.8-14
Sintering Temperature
Softening Temperature
Hemisphere Temperature
Pouring Temperature
Ash Chemical ComDOsition (wt %)
Si 02
A1203
CaO
MgO
S03
Ti02
Na20
K20
MnO
Acidic/Basic Ratio
1000
1200
1300
1320
28.8
6.8
7.9
39
4.5
11.0
0.28
0.44
0.64
0.39
0.72
1180-1220
1230-1360
1250-1380
28.3-29.2
6.3-7.3
6.2-9.6
38-41
4.1-4.8
10.8-11.1
0.25-0.30
0.31-0.56
0.46-0.82
0.38-0.40
0.67-0.77
(Continued)
A-69
-------
TABLE A.5-6. (Continued)
Overall
Component Value* Range
Other Properties
Specific Gravity (g/ml) 0.57
Micum Test (+6mm) %
Tar (wt %)
Gas Water (wt %)
Semicoke (wt %) -
Gas and Losses (wt %) -
Grain Size (mm) -
Specific Surface Area (cm2/g) 3500
- = No data available
*Values are best values from available data
TABLE A.5-7. PARTICLE SIZE DISTRIBUTION DATA FOR THE
COAL ROOM DUST (2.1)
Cumulative Fraction
Particle Size (microns) Value (wt %) Value (wt %)
0 to 63 33.4 33.4
63 to 125 55 21.2
125 to 200 65 10.4
200 to 500 100 35.0
A-70
-------
TABLE A. 5-8. SPARK SOURCE MASS SPECTRAL DATA FOR THE
COAL ROOM DUST (2.1)
Overall
Component (mg/kg) Value
Ba 370
Mn 170
Cr 15
Ni 9
V 16
Cu 3
Co 8
Sr 83
Ti 400
Cd 0.3
A-71
-------
TABLE A.5-9,
TEST DATA FOR SOLID PHASE SAMPLE POINT 12 1
DRY GASIFIER ASH ' '
Component
Overall
Value
Proximate Analvsis (wt %)
Moisture
Ash
Volatile
Fixed Carbon
Coke
Combustibles
Total Carbon
Carbon Dioxide
Total Sulfur
Free Sulfur
Fixed Sulfur
Hydrogen
Nitrogen •
Oxygen
Chlorine
Proximate Moisture Free Analysis
(wt % drv basis)
Ash
Volatile
Fixed Carbon
Coke
Combustibles
Total Carbon
Carbon Dioxide
Total Sulfur
Free Sulfur
Fixed Sulfur
Hydrogen
Nitrogen
Oxygen
Chlorine
Heating Value (Kcal/kz)
Proximate HHV
LHV
Proximate Moisture Free
HHV
LHV
2.1
94
6.5
0.15
95
6.7
0.15
27.8
28.3
A-72
(Continued)
-------
TABLE A.5-9. (Continued)
Overall
Component Value
Ultimate Analysis (wt %)
Moisture 2.1
ASA 94
Volatile
Fixed Carbon 1.7
Carbon Dioxide -
Total Sulfur 0.15
Free Sulfur
Fixed Sulfur
Hydrogen 0.25
Nitrogen 0.03
Oxygen (By Difference) 2.3
Chlorine 0.04
Ultimate Moisture Free Analysis
(wt % dry basis)
Ash
Volatile
Fixed Carbon
Carbon Dioxide
Total Sulfur
Free Sulfur
Fixed Sulfur
Hydrogen
Nitrogen
Oxygen (By Difference)
Chlorine
95
-
1.8
—
0.15
-
-
0.26
0.03
2.3
0.04
- = No data available
A-73
-------
TABLE A. 5-10.
ATOMIC ABSORPTION DATA FOR THE
DRY GASIFIER ASH (12.1)
Component (mg/kg)
As
Be
Cd
Co
Cr
Cu
Hg
Ho
Ni
Pb
Sb
Se
Sr
Tl
V
Zn
Overall
Value
75
2.5
69
17
180
40
0.30
8.9
320
52
NF
24
370
NF
100
2.1
NF « Not found
A-74
-------
TABLE A.5-11. SPARK SOURCE MASS SPECTRAL DATA FOR THE
DRY GASIFIER ASH (12.1)
Component (mg/kg)
B
Ba
Be
Mn
Sb
Pb
Cr
Ga
Ni
Mo
Sn
V
Cu
T
Zn
Zr
Co
Sr
Ti
Ge
La
As
U
Th
Er
Ho
Dy
Tb
Gd
En
Sm
Nd
Pr
Ce
Cs
I
Te
Nb
Rb
Sc
Cl
Overall
Value
190
>1000
4
>1000
2
9
2
17
180
6
0.8
61
27
17
33
33
4
320
>1000
0.5
21
62
2
9
0.5
0.6
2
0.4
2
1
9
10
5
29
3
2
11
10
35
12
45
(Continued)
A-75
-------
TABLE A.5-11. (Continued)
Overall
Component (mg/kg) Value
S 420
F 710
Li 28
Br 17
Se <1
Ca >1000
K >1000
P >1000
Si >1000
Al ' >1000
Mg >1000
Na >1000
Fe >1000
A-76
-------
TABLE A. 5-12.
TEST DATA FOR SOLID PHASE SAMPLE POINT 12.2,
WET GASIFIER ASH
Component
Overall
Value*
Range
Proximate Analysis (wt %)
Moisture
Ash
Volatile
Fixed Carbon
Carbon Dioxide
Total Sulfur
Free Sulfur
Fixed Sulfur
Hydrogen
Nitrogen/Oxygen
Chlorine
Proximate Moisture Free Analysis
(wt % dry basis)
34
59
6.0
1.3
5.7
0.09
0.02
0.07
0.38
4.2
29-37
55-63
4.6-7.2
0.7-2.5
4.6-6.5
0.07-0.12
0.01-0.04
0.06-0.08
0.36-0.40
3.7-4.7
Ash
Volatile
Fixed Carbon
Carbon Dioxide
Total Sulfur
Free Sulfur
Fixed Sulfur
Hydrogen
Nitrogen/ Oxygen
Chlorine
89
9.1
1.9
8.8
0.13
0.03
0.10
0.58
6.5
—
87-91
7 .3-11
1.1-3.5
7 .3-10
0.10-0.18
0.01-0.06
0.09-0.12
0.57-0.61
5.9-6.9
(Continued)
A-77
-------
TABLE A.5-12. (Continued)
Component
Overall
Value*
Range
Proximate Moisture and Ash Free Analysis
(wt %)
Volatile
Fixed Carbon
Carbon Dioxide
Total Sulfur
Free Sulfur
Fixed Sulfur
Hydrogen
Nitrogen/Oxygen
Chlorine
Ash Fusibility (°C)
Sintering Temperature
Softening Temperature
Hemisphere Temperature
Pouring Temperature
Ash Chemical Composition (wt %)
81
19
1120
1220
1240
1250
74-88
12-26 .0
1100-1130
1180-1280
1190-1290
1200-1300
Si02
Fe20g
A1203
CaO
MgO
S03
P2°5
Na20
K20
HnO
Acidic/Basic Ratio
30
6.6
6.6
38
6.7
3.4
0.29
Q.42
1.4
0.57
0.10
0.65
25-36
3.9-11.0
4.1-11.0
29-43
5.1-7.4
0.36-5.8
0.28-0.29
0.27-0.49
1.1-1.8
0.38-0.76
0.59-0.71
- - No data available
*Values are best values from available data
A-78
-------
TABLE A.5-13
SPARK SOURCE MASS SPECTRAL DATA FOR THE
WET GASIFIER ASH (12.1)
Component (mg/kg)
B
Ba
Be
Bi
Mn
Sb
Pb
Cr
Ga
Ni
Mo
Sn
V
Cu
Ag
Y
Zn
Zr
Co
Sr
Ti
Sc
La
Cd
Overall
Value*
630
1670
NF
NF
2700
NF
27
240
37
180
30
NF
140
76
NF
39
56
180
15
4100
2300
20
NF
1.2
Range
1200-2700
NF-2
24-29
90-240
48-76
NF = Not found
* Values are best values from available data
A-79
-------
TABLE A.5-14. TEST DATA FOR SOLID PHASE SAMPLE POINT 13.8,
HEAVY TAR
Overall
Component Value
Ultimate Moisture Free Analysis
(wt % drv basis)
Ash 6.6
Volatile
Fixed Carbon -
Total Sulfur 0.33
Free Sulfur
Fixed Sulfur
Hydrogen 7.6
Nitrogen . 0.87
Oxygen (By Difference) 28.6
Chlorine
Heating Value (Kcal/kg)
Ultimate HHV 6340
LHV
Insoluble Particulates 26
- = No data available
A-80
-------
TABLE A.5-15. POLINUCLEAR AROMATIC DATA FOR THE
HEAVY TAR (13.8)
Overall
Component (mg/kg) Value
Benz(a)anthracene 500
7,12-Dimethylbenz(a)anthracene 1300
Benzo(b)fluoranthrene 320
Benzo(a)pyrene 240
3—Methylcholanthrene NF
Dibenz(a,h)anthracene 14
252 Group (as Benzo(a)pyrene) 1000
NF = Not found
A-81
-------
TABLE A.5-16. PHENOL SPECIATION DATA FOR THE
HEAVY TAR (13.8)
Overall Retention
Component (mg/g) Value* Time
Phenol 3.3 8.55
o-Cresol (as Phenol) 2.4 9.50
m-Cresol 6.7 9.70
p-Cresol (as Phenol) 0.70 9.90
2,6-Dimethylphenol 0.57 10.10
2,4-Dimethylphenol 3.6 10.50
3,4-Dimethylphenol 2.0 10.95
1-Naphthol 0.69 13.20
Unknowns (as Phenol)
0.61
5.4
0.98
1.7
1.9 •
1.4
1.8
1.2
1.2
Other Unknowns (as Phenol)** 81
10.35
10.65
11.20
11.30
11.45
11.60
11.70
12.35
12.40
""
* Analysis by GC/FID
** Summation of all other unknown peaks
A-82
-------
TABLE A. 5-17. ATOMIC ABSORPTION DATA FOR THE
HEAVY TAR (13.8)
Overall
Component (mg/kg) Value
As
Be
Cd
Co
Cr
Cu
Hg
Ho
Ni
Pb
Sb
Se
Sr
Tl
V
Zn
16
0.29
3.7
1.5
30
6.0
0.64
0.85
21
64
3.9
2.6
41
NF
5.7
98
NF = Not found
A-83
-------
A6.0. LEACHATE TEST RESULTS FOR KOSOVO GASIFIER ASH
TABLE A.6-1. SPARK SOURCE MASS SPECTRAL DATA FOR THE
RCRA LEACHATE (ACID LEACHATE) OF THE
DRY GASIFIER ASH (12.1)
Component (mg/L)
U
Th
Pb
Ba
Cs
Sb
Sn
Mo
Zr
Y
Sr
Rb
Br
Se
As
Ge
Zn
Cu
Ni
Co
Fe
Mn
Cr
V
Ti
Sc
Cl
S
P
Si
Al
Mg
Na
F
Li
B
Overall
Value
10.007
10.008
0.008
3
0.004
10.002
10.001
0.1
10.006
0.008
4
0.04
10.008
0.01
10.004
10.001
0.05
0.01
0.04
10.001
10
0.001
0.3
0.07
0.01
10.001
0.05
>6
0.02
8
0.01
2
>2
H).8
0.03
0.09
A-84
-------
TABLE A.6-2. SPARK SOURCE MASS SPECTRAL DATA FOR THE
ASTM LEACHATE (NEUTRAL LEACHATE) OF THE
DRY GASIFIER ASH (12.1)
Component (mg/L)
U
Th
Pb
Ba
I
Mo
Nb
Sr
Rb
Br
Se
As
6e
Ga
Zn
Cu
Ni
Co
Fe
Mn
Cr
V
Ti
Sc
Cl
P
Si
Al
F
B
Li
Overall
Value
10.03
10.04
0.07
0.05
0.005
0.05
0.006
0.3
0.09
0.4
0.007
0.01
0.01
0.02
0.08
0.03
0.02
<0.007
0.1
0.02
0.5
0.004
0.02
10.003
0.7
0.2
7
2
~7
0.1
0.07
A-85
-------
TABLE A.7-1. HEADSPACE RESULTS FOR HEAVY TAR AND LIQUID BY-PRODUCTS
oo
Component
Ambient Conditions
Benzene
Toluene
Ethylbenzene
Xylenes~m,p
Xylenes-o
15.3
Naphtha
72
10
0.31
0.96
0.74
13.10
Medium Oil
7.4
4.2
0.34 .
1.6
1.0
13.9
Light Tar
0.77
0.60
13.8 14.16
Heavy Tar Crude Phenol
NF
At 6S'C (u« i 10«/m»)
Benzene
Toluene
Ethylbenzene
Xylenes-m,p
Xylenes-o
H2S
COS
CII3SII
C2USSQ
Unknowns (as C2I15SH)
S900
1300
51
130
87
Tr
NF
0.38
170
25
22
3.1
11
8.0
Tr
Tr
0.019
1.4
3.0
3.1
1.0
NF
Tr
Tr
0.035
1.3
1.0
NF
NF
0.0064
0.05
NF
NF
Tr
0.0028
Retention Time
14.4
15.7
18.2
20.6
41.2
0.43
5.6
27
6.4
1.9
0.033
0.091
0.99
0.35
0.35
0.041
NF
NF
NF
NF
NF
NF
NF
NF
NF
0.069
0.033
NF
NF
NF
Tr = Trace, ~1 ppmv
NF = Not found, less than 1 ppmv
- = No data available
-------
A8.0. COMPILATION OF DATA FOR KOSOVO BY-PRODUCTS
TABLE A.8-1. TEST DATA FOR BY-PRODUCT SAMPLE POINT 13.9.
LIGHT TAR
Component
Specific Gravity (g/cm3)
High Heating Value (kcal/Kg)
Low Heating Value (kcal/Kg)
mtimate Analysis (wt %)
Carbon
Hydrogen
Nitrogen
Sulfur
Ash
Chlorine
Oxygen (Difference)
Moisture
=___ i
- = No data available
•Values are best values from available data
TABLE A.8-2. POLYNUCLEAR AROMATIC HYDROCARBON DATA FOR THE
LIGHT TAR (13.9)
Overall
Value
1.06
8910
8280
82
8.4
1.3
0.49
0.22
7.8
1.1
Range
8710-9810
72-82
8.1-8.4
0.49-0.75
0.22-0.92
Component (mg/kg)
Overall
Value*
Benz(a)anthracene
7,12-Dimethylbenz(a)anthracene
Benzo(b)fluoranthrene
Benzo(a)pyrene
3-Me thy1chloanthrone
Dibenz(a,h)anthracene
252 Group (as Benzo(a)pyrene)
490
1100
310
210
26
23
950
•Analysis by GC/MS-Liquid Crystal
A-87
-------
TABLE A.8-3. PHENOL SPECIATION DATA FOR THE
LIGHT TAR (13.9)
Overall Retention
Component (mg/g) Value* Time
Phenol 5.9 8.55
o-Cresol (as Phenol) 4.9 9.50
m-Cresol 13 9.70
p-Cresol (as Phenol) 1.4 9.90
2,6-Dimethylphenol 1.2 10.10
3,4-Dimethylphenol 7.5 10.50
3,4-Dimethylphenol 3.9 10.95
1-Naphthol 1.0 13.20
Unknowns (as Phenol)
1.3
10.1
2.1
3.7
3.3
2.8
4.3
2.6
2.7
Other Unknowns (as Phenol)** 94
10.35
10.65
11.20
11.30
11.45
11.60
11.70
12.35
12.40
-
* Analysis by GC/FID
** Summation of all other unknown peaks
A-88
-------
TABLE A. 8-4.
ATOMIC ABSORPTION DATA FOR THE
LIGHT TAR (13.9)
Component (mg/L)
Trace Elements (mg/1) by AA
As
Be
Cd
Co
Cr
Cu
Hg
Mo
Ni
Pb
Sb
Se
Sr
Tl
V
Zn
Overall
Value
18
0.10
0.70
NF
3.2
17
NF
NF
9.5
7.2
NF
1.7
21
0.42
0.53
30
NF = Not found
A-89
-------
TABLE A. 8-5,
TEST DATA FOR BY-PRODUCT SAMPLE POINT 13.10,
MEDIUM OIL
Component
Specific Gravity (g/cm3)
High Heating Value (kcal/Kg)
Low Heating Value (kcal/Kg)
Ultimate Analysis (wt»%)
Carbon
Hydrogen
Nitrogen
Sulfur
Ash
Chlorine
Oxygen (Difference)
Moisture
Overall
Value*
0.97
9500
9400
81.8
8.94
1.00
0.83
0.03
—
8.2
0.8
Range
9100-9900
81.1-82.4
8.91-8.96
0.7-0.95
- = No data available
* Values are best values from available data
TABLE A. 8-6. POLYNUCLEAR AROMATIC HYDROCARBON DATA FOR THE
MEDIUM OIL (13.10)
Component (mg/kg)
Overall
Value
B enz(a)anthra c ene
7,12-Dimethylbenz(a)anthracene
Benzo(b)flnoranthrene
Benzo(a)pyrene
3-Methy1cholanthrene
Dibenz(a,h)anthracene
252 Group (as Benzo(a)pyrene)
160
62
120
68
NF
6.6
280
NF = Not Found
A-90
-------
TABLE A.8-7. PHENOL SPECIATION DATA FOR THE
MEDIUM OIL (13.10)
Overall Retention
Component (mg/g) Value* Time
Phenol 19 8.55
o-Cresol (as Phenol) 19 9.50
m-Cresol 38 9.70
p-Cresol (as Phenol) 5.1 9.90
2,6-Dimethylphenol 4.6 10.10
3,4-Dimethylphenol 22 10.50
3,4-Dimethylphenol 12 10.95
1-Naphthol 0.73 13.20
Unknowns (as Phenol)
4.0 10.35
22 10.65
4.7 11.20
8.3 11.30
6.0 11.45
5.0 11.60
9.2 11.70
3.4 12.35
6.1 12.40
Other Unknowns (as Phenol)** 42
* Analysis by GC/FID
** Summation of all other unknown peaks
A-91
-------
TABLE A. 8-8. ATOMIC ABSORPTION DATA FOR THE
MEDIUM OIL (13.10)
Component
As
Be
Cd
Co
Cr
Cu
Hg
Mo
Ni
Pb
Sb
Se
Sr
Tl
V
Zn
Overall
Value
1.9
NF
0.075
0.19
3.9
1.1
0.20
0.18
' NF
1.4
NF
1.8
8.3
NF
NF
15
NF « Not found
A-92
-------
TABLE A.8-9. SPARK SOURCE MASS SPECTRAL DATA FOR THE
MEDIUM OIL (13.10)
Component (mg/L)
U
Th
Bi
Pb
Ce
Ln
Ba
Sn
Cd
Mo
Zr
Y
Sr
Se
As
Zn
Cu
Ni
Co
Fe
Mn
Cr
• V
Ti
Sc
Ca
K
Cl
S
P
Si
Al
Na
F
B
Li
Mg
Overall
Value
0.07
10.02
0.01
0.09
0.003
10.004
~ 0.09
0.008
0.01
0.005
10.003
0.003
0.008
0.02
0.4
0.3
0.5
0.03
0.004
2
0.02
0.02
0.01
0.09
10.001
5
0.3
0.008
0.6
0.1
2
0.09
0.1
-0.03
~0.07
0.001
>10
A-93
-------
TABLE A.8-10,
TEST DATA FOR BY-PRODUCT SAMPLE POINT 15 .3,
NAPHTHA
Component
Overall
Value*
Range
Specific Gravity (g/cm3)
High Heating Value (kcal/Kg)
Low Heating Value (kcal/Kg)
Ultimate Analysis (wt %)
Carbon
Hydrogen
Nitrogen
Sulfur
Ash
Chlorine
Oxygen (Difference)
0.845
9940
8930
86
9.9
0.18
2.2
2.2
9390-9940
78-86
8.7-9.9
1.4-2.2
- = No data available
* Values are best values from available data
TABLE A.8-11.
POLYNUCLEAR AROMATIC HYDROCARBON DATA FOR THE
NAPTHA (15.3)
Component
Overall
Value*
Benz(a)anthracene
7,12-Dimethylbenz(a)anthracene
Benzo(b)fluoranthrene
Benzo(a)pyrene
3-Hethylcholanthrene
Dibenz(a,h)anthracene
252 Group (as Benzol a)pyrene)
NF
NF
NF
NF
NF
NF
NF
NF = Not found
* Analaysis by GC/MS-Liquid Crystal
A-94
-------
TABLE A.8-12.
ATOMIC ABSORPTION DATA FOR THE
NAPHTHA (15.3)
Component (mg/L)
Overall
Value
As
Be
Cd
Co
Cr
Cu
Hg
Ho
Ni
Pb
Sb
Se
Sr
Tl
V
Zn
0.55
0.0018
0.0008
0.005
0.10
0.15
0.13
0.009
0.14
0.064
0.012
0.73
NF
NF
NF
0.14
NF = Not found
A-95
-------
TABLE A.8-13. TEST DATA FOR BY-PRODUCT SAMPLE POINT 14.16,
CRUDE PHENOL
Overall
Component Value
Specific Gravity (g/cm3)
High Heating Value (kcal/Kg)
Low Heating Value (kcal/Kg) 7790
Ultimate Analysis (wt %)
Carbon -
Hydrogen -
Nitrogen -
Sulfur
Ash
Chlorine
Oxygen (Difference) -
- = No data available
A-96
-------
APPENDIX B
BIOASSAY RESULTS
LEVEL 1 EPA HEALTH EFFECTS TESTS
ON COAL GASIFICATION SAMPLES
Final Report
to
RADIAN CORPORATION
P. 0. Box 9948
Austin, TX 78766
ADL Reference 84625
Subcontract under EPA Prime Contract 68-02-2147
(Task 1, Sub-Task 25)
June 30, 1980 This report is reprinted as
received from Arthur D. Little,
Inc. Therefore, the format
is not consistent with EPA
requirements.
Arthur D Little, Inc
-------
TABLE OF CONTENTS
Page
I. INTRODUCTION 1
II. SUMMARY OF RESULTS 2
III. SAMPLES REQUIRING SPECIAL HANDLING 3
IV. SALMONELLA MUTAGENESIS ASSAY (AMES) 4
Summary 4
Materials 4
Methods 4
Results 6
V. IN VITRO CYTOTOXICITY ASSAYS 14
A. Rabbit Alveolar Macrophage (RAM) Assay 14
Summary 14
Materials 14
Methods 14
Results 15
B. Chinese Hamster Ovary (CHO) Clonal Toxicity Assay . 15
Summary 15
Materials 15
Methods 16
Results 17
VI. ACUTE IN VIVO TOXICOLOGICAL TESTS IN RODENTS 29
Summary 29
Materials 29
Methods 30
Results 30
Conclusions 31
B-2
Arthur D Little Inc
-------
LIST OF TABLES
Table No. Page
IV-1 SUMMARY OF RESULTS OF AMES ASSAY 7
IV-2 AMES ASSAY I
SAMPLE #2988- TREATED WASTEWATER
SAMPLE #2468L - ASTM SLAG LEACHATE 10
IV-3 AMES ASSAY II
SAMPLE #2468 - SLAG
SAMPLE #2987 - WASTEWATER
SAMPLE #2473L - ASTM HEAVY TAR LEACHATE 11
IV-4 AMES ASSAY III
SAMPLE #2471 - MEDIUM OIL
SAMPLE #2472 - TAR ' 12
IV-5 AMES ASSAY IV
SAMPLE #2473 - HEAVY TAR AND DUST
SAMPLE #1152A - LIGHT OIL 13
V-l SUMMARY OF RESULTS OF IN VITRO TOXICITY TESTS 18
V-2 RESULTS OF RAM ASSAY OF RADIAN SAMPLE 2468 19
V-3 CHO CLONAL TOXICITY ASSAY RESULTS
EXPERIMENT NO. 1 22
V-4 CHO CLONAL TOXICITY ASSAY RESULTS
EXPERIMENT NO. 2 25
VI-1 SUMMARY OF RESULTS OF ACUTE ORAL TOXICITY TESTS 32
VI-2 SUMMARY OF SINGLE-DOSE ORAL TOXICITY OF 2468 33
VI-3 SUMMARY OF SINGLE-DOSE ORAL TOXICITY OF 1152A 34
VI-4 SUMMARY OF SINGLE-DOSE ORAL TOXICITY OF 2471 35
VI-5 SUMMARY OF SINGLE-DOSE ORAL TOXICITY OF 2472 36
VI-6 SUMMARY OF SINGLE-DOSE ORAL TOXICITY OF 2473 37
VI-7 SUMMARY OF SINGLE-DOSE ORAL TOXICITY OF 2987 38
VI-8 SUMMARY OF SINGLE-.DOSE ORAL TOXICITY OF 2988 39
VI-9 SUMMARY OF SINGLE-DOSE ORAL TOXICITY OF 2468L 40
VI-10 ' SUMMARY OF SINGLE-DOSE ORAL TOXICITY OF 2473L 41
B-3
Arthur D Little Inc
-------
LIST OF FIGURES
Figure No.
V-l RADIAN RAM ASSAY
SAMPLE 2468 21
V-2 RADIAN CHO CLONAL TOXICITY ASSAY .
EXPERIMENT NO. 1 - 24
V-3 RADIAN"CHO CLONAL TOXICITY ASSAY
EXPERIMENT NO. 2 28
B-4
Arthur D Little Inc
-------
I. INTRODUCTION
Arthur D. Little, Inc., conducted Level 1 EPA Health Effects Tests
on coal gasification process samples for the Radian Corporation. Samples
were received on March 21, 1980.
The Test Matrix conducted is given below.
Test Matrix
Bioassay
Sample No. Description
2468 Slag
1152A* Light Oil
2471* Medium Oil
2472* Tar
2473* Heavy Tar and Dust
2987 Wastewater
COD = 17,700 mg/1
2988 Treated Wastewater
COD = 5,540 mg/1
2468L ASTM Slag Leachate
2473L ASTM Heavy Tar Leachate
Ames
CHO
RAM
Rodent
* Samples extracted with 9 parts methylene chloride and solvent-exchanged
with an equal volume of dimethylsulfoxide (DMSO) before application to
all in vitro tests. See Section III.
B-5
Arthur D Little Inc
-------
II. SUMMARY OF RESULTS
In Vitro
Cytotoxicity**
Rodent
tt
Test/Control
1/2
7/2
10/2
7/2
3/1
1/2
0/2
1/0
3/0
* Highest concentration tested varied depending on sample toxicity.
See Section IV.
** All samples tested in CHO assay except sample 2468 which was
tested in the RAM assay.
t ECeg's given in yl/ml or yg/ml.
tt Number of dead mice in test group over control group. Ten animals
were used in each group. See details in Section V.
Sample No.
2468
1152A
2471
2472
2473
2987
2988
2468L
2473L . -
Ames*
Negative
Negative
Negative
Positive
Positive
Positive
Negative
Negative
Negative
1C f
1Ucn
>1000
0.68
0.11
0.03
0.07
37
. 98
>600
120
B-6
Arthur D Little Inc
-------
III. SAMPLES REQUIRING SPECIAL HANDLING
Samples 1152A, 2471, 2472 and 2473 were organic liquid/solids marked
as particularly volatile and hazardous. Instructions for handling them
included that they should not come in contact with the skin. The use
of a respirator and a hood were strongly recommended. Vapors from 1152A
were reported to cause a severe headache (letter dated March 20, 1980,
from R. V. Collins, Radian Corporation).
An extraction and solvent exchange procedure to prepare these samples
for in vitro bioassays was designed in collaboration with Dr. Collins.
The original samples were immiscible with water and contained extremely
volatile components.
Protocol for Extraction and Solvent Exchange
Sampl e
(4.0 ml or 4.0 gm)
4-
Add 36 ml CH2C12
i
Shake several hours at room temperature
4-
Shake 1 part CH2C12 phase with 1 part DMSO
4-
CH^Cl2 was removed under a stream
of nitrogen gas below 40°C for 7 hours
4-
DMSO was added to bring final volume
to 40 ml
Original sample now diluted 1:10 in DMSO.
Additional serial dilutions were prepared
in DMSO as described in Sections IV and V.
B-7
Arthur D Little Inc
-------
IV. SALMONELLA MUTAGENESIS ASSAY (AMES)
Test Samples:
2988 2471
2468L 2472 -
2468 2473
2987 1152A
2473L
SUMMARY
The above samples were tested in the plate incorporation assay of
Ames against Salmonella typhimurium strains TA-98, TA-100, TA-1535,
TA-1537 and TA-1538 with and without metabolic activation. The solid
sample was tested at four log concentrations, the highest concentration
being 1.0 mg/plate. Liquids were tested at concentrations of 250, 200,
150 and 100 pi/piate unless the consistency (i.e., sample 2473L, ASTM
Heavy Tar Leachate) or toxicity (i.e., samples 1152A, 2471, 2472 and
2473) did not permit this. The highest concentration of sample 2473L
which could be incorporated in the agar plate was 150 yl/plate. The
very volatile and toxic samples 1152A, 2471, 2472 and 2473 were tested
at concentrations of 0.025, 0.02, 0.015 and 0.01 ul/plate after they
had been extracted with methylene chloride and solvent-exchanged with
DMSO.
MATERIALS
Test materials are described in Section I. Methylene chloride ex-
traction and DMSO exchange of samples 1152A, 2471, 2472 and 2473 are
described in Section II.
METHODS
The Salmonella typhimurium strains TA-98, TA-100, TA-1535, TA-1537
and TA-1538 used in this study were obtained-from Dr. Bruce Ames. The
protocol for the assay was as described in the IERL-RTP Procedures Manual,
Level 1, EPA 600/6-77-04, April, 1977. The assay is conducted in a
culture medium which contains insufficient histidine to allow the tester
strains to proliferate sufficiently to give colonies. After incubation
for 48 hours at 37°C, the mutant colonies (formed by his+ revertants)
are counted. Results are reported as total number of revertants per
B-8
Arthur D Little Inc
-------
plate. Briefly, in this assay the test organisms, with or without micro-
somal preparations (S-9) and test material, were mixed in the molten top
agar and poured on duplicate plates at four concentrations.
Solid sample 2468 was tested at four log concentrations, the highest
concentration being 1.0 mg/plate. Liquids 2988 and 2468L were tested at
250, 200, 150 and 100 yl /plate. Samples 2473L (Heavy Tar Leachate) and
2987 (Wastewater) were tested at 150, 100, 50 and 25 yl/plate because of
either viscosity (2473L) or toxicity (2987). The very volatile samples
1152A, 2471, 2472 and 2473 were extracted with methylene chloride and
solvent-exchanged with DMSO (Section II) and tested at concentrations of
0.025, 0.02, 0.015 and 0.01 vl/plate. Each set of plates for each con-
centration of each of these four volatile samples was placed in a Ziploc
bag before being placed in an incubator for the 48-hour incubation period.
Corresponding positive and negative controls for these assays were handled
in the same manner.
Controls which were included in every experiment consisted of negative
controls for the spontaneous reversion rate for each tester strain, and
the positive controls listed below, compounds which do and do not require
metabolic activation.
Tester Strain Positive Control Chemicals
All Strains 2-Anthramine, 10 yg/plate
TA-98 Daunomycin, 10 yg/plate
TA-100 Methylmethane sulfonate, 50 yg/plate
TA-1535 N-methyl-N'-nitro-N-nitrosoguanidine, 50 yg/plate
TA-1537 9-Aminoacridine, 50 yg/plate
TA-1538 2-Nitrofluorene, 10 yg/plate
For all experiments reported in this study, the following sterility
controls (inoculated on Nutrient Agar plates) were negative: solvent,
sample, S-9 mix and histidine/biotin supplement. Uninoculated media con-
trols, which were also negative, included Minimal Glucose Agar, Nutrient
Agar and Nutrient Broth.
All nine samples were tested in four experiments conducted on sepa-
rate days.
B-9
Arthur D Little Inc
-------
RESULTS
The results are summarized in Table IV-1 and individually presented
in Tables IV-2 through IV-5.
Senior Technicians Evaluating Material
T*" kU ^V->WL^_
Eliwfoeth M. Mochen, B.S.
C&ubf*
Carolyn C. fieatty, ASCP fl(MT)
Case Leader, Senior Staff
Section Leader, Bio/Medical Sciences
/jl r. p/
MlTdred G. Broome, Ph.D.
/
Andr*ew'Sl'val<, P/
B-10
Arthur D Little Inc
-------
TABLE IV-1
SUMMARY OF RESULTS OF AMES ASSAY
2468 - Slag
There was no mutagenic activity for any of the strains with or
without metabolic activation at concentrations up to 1 mg/plate.
Some toxicity was evident at the highest concentration tested
with all strains and at 0.1 mg/plate with strains TA-1537,
TA-100 and TA-1535.
2987 - Wastewater
There was a positive response with TA-98 and TA-1538 with meta-
bolic activation at 100 pi/plate. There was toxicity for TA-98,
TA-1538 and TA-1535 at the highest concentration tested
(150 yl/plate).
2988 - Treated Wastewater
There was no mutagenic activity and no toxicity at concentrations
up to 250 pi/plate.
2468L - ASTM Slag Leachate
There was no mutagenic activity and no toxicity at concentrations
up to 250 ul/plate.
2473L - ASTM Heavy Tar Leachate
There was no mutagenic activity and no toxicity at concentrations
up to 150 yl/plate.
B-ll
Arthur D Little Inc
-------
TABLE IV-1
SUMMARY OF RESULTS OF AMES ASSAY
(continued)
2471 - Medium Oil (Solvent-Exchanged with DMSO)*
There was no mutagenic activity at concentrations up to 0.025 yl/
plate. There was slight toxicity for TA-1537 and TA-100 at
0.025 yl/plate.
2472 - Tar (Solvent-Exchanged with DMSO)*
There was a positive response with TA-1538 at 0.02 yl/plate with-
out metabolic activation and beginning with 0.01 yl/plate (the
lowest concentration tested) with metabolic activation. There
was also a positive response with TA-98 with metabolic activation
beginning with 0.015 yl/plate. The' highest concentration tested .
(0.025 yl/plate) caused a slight toxic effect to the lawn of all
the strains.
2473 - Heavy Tar and Dust (Solvent-Exchanged with DMSO)*
There was a positive response with TA-98 with metabolic activation
at 0.02 yl/plate and with TA-1538 with metabolic activation at
0.01 yl/plate.
1152A - Light Oil (Solvent-Exchanged with DMSO)*
There was no mutagenic activity for any of the strains with or
without metabolic activation at concentrations up to 0.025 yl/
plate. There was overall slight toxicity at all concentrations
tested.
B-12
Arthur D Little Inc
-------
TABLE IV-1
SUMMARY OF RESULTS OF AMES ASSAY
(continued)
Footnote:
* Volatile samples 2471, 2472, 2473 and 1152A were solvent-exchanged with
DMSO. Solvent-exchanged samples contained highly volatile components
and were tested in the Ames assay under special handling conditions.
Each set of plates for each concentration tested was placed in a Ziploc
baq before being placed in an incubator for the 48-hour incubation
period. Corresponding positive and negative controls for these assays
were handled in the same manner. All four volatile, solvent-exchanged
samples showed overall slight toxicity at all concentrations and for
all strains. Bacterial colonies in all plates which are held in plastic
bags (including those in control dishes) are smaller than normal due
perhaps to the lack of oxygen under such assay conditions. Additionally,
colonies in dishes treated with volatile samples were smaller than their
corresponding controls. Strain TA-100, treated with all four samples
in the presence of metabolic activation, gave abnormal spreading colonies
indicative of cell membrane disruption.
B-13
Arthur DLittletlnc
-------
TABLE IV-2
Control (DMSO)
2-Anthramlne**
(10 ug/plate)
Daunomycin***
(10 ug/plate)
9-Aminoacridine
(50 ug/plate)
2-Nitrofluorene**
(10 ug/plate)
Methylmethane sulfonate**
(50 ug/plate)
N-Methyl-N'-nitro-N-
nitrosoguanldlne **
(50 ug/plate)
TA-98
-S9 +S9
19*1 24*2
AMES ASSAY I
SAMPLE #2988 - TREATED WASTEWATER
SAMPLE #2468L - ASTM SLAG LEACHATE
Revertants Per Plate*
TA-1537 TA-1538 TA-100 TA-1535
-S9 +S9 -S9 +S9 -S9 +S9 -S9 +S9
7*0 9*1 16*0 17*2 93*4 105*1 14 ± 4 14*3
18*1
845*5
224 * 21
683 * 63
11+2 43*4
18*2
95*11
88 * 2 358 * 2
17*3
34*1
24 * 2 29 ± 5
94*15
57*2
192*8
162*8
2449 ±19? 1970*130
#2988 - Treated Wastewater***
>
i-
C
-t
a
C"
(100 pi/plate)
(150 ul/plate)
(200 ul/plate)
(250 ul/plate)
02468L - ASTM Slag
(100 pi/plate)
(150 ul/plate)
(200 ul/plate)
(250 ul/plate)
* Mean of 2 reol
22*4
18*3
21 * 6
20*3
Leachate***
17±4
17*1
21 ±5
19*3
icate plates * stand
25*2
23*3
34*2
35*2
25*1
20 ±1
19*2
29*7
lard error o
11 + 0
9*0
8*1
8*5
4±2
5*1
4*1
7±2
f the meai
7±0
12±0
7*1
11+2
6*1
8*3
9*4
8*3
~
n.-
11 ±2
18*3
10*3
12*1
11 ±2
10*3
14*4
12±2
20 ±2
30*2
21 *4
23*2
17*5
13*3
22*2
18 + 3
94 ±4
81 ±10
89*0
85 + 10
104 + 1
99 + 2
90 + 1
97 + 1
96 ±4
91+6
100*6
99*7
95*12
97 ±4
103 ±1
99 ±3
13*3
11 *2
12±6
18*0
17 + 2
18 ±8
16*3
18*1
17 + 3
13 + 1
10 + 2
15 + 2
14 + 1
14±0
16 + 2
16±1
** Dissolved and/or suspended In dimethylsulfoxide (DMSO).
*** Dissolved and/or suspended in sterile distilled water.
t Dissolved in 95% ethanol.
-------
TABLE 1V-3
AMES ASSAY II
SAMPLE 12468 - SLAG
SAMPLE 12987 - WASTEWATER .
SAMPLE I2473L - ASTM HEAVY TAR LEACHATE
Revertants Per Plate*
I
t-'
Oi
LT
Control (DHSO)
2-Anthramlne**
(10 pg/plate)
Daunomycin***
(10 pg/plate)
g-Aminoacridine*
(50 pg/plate)
2-N1trofluorene**
(10 iig/plate)
Hethylmethane sulfonate**
(50 pg/plate)
N-Methyl-N'-nitro-N-
nltrosoguanidine**
(50 ng/plate)
TA-98
-S9
+S9
241 4 261 4
27 tO >500
>500 >500
TA-1537
-S9
6iO
9±2
152 t 4
12468 - Slag**
{0.001 mg/plate)
(0.01 mg/plate)
(0.1 mg/plate)
(1.0 mg/plate)
12987 - Wastewater**
25 pi/plate)
50 pi/plate)
100 pi/plate)
150 pi/plate)
I2473L - ASTM Heavy Tar
Leachate**
25 pi/plate)
50 pi/plate)
100 pi/plate)
150 pi/plate)
13 1
24 «
21*
20 i
15*
22'
18*
13'
16*
18*
16 1
18*
1
1
1
2
3
3
1
2
0
0
1
4
19
19
21
14
27
45
+
*
*
£
+
+
60*
40
22
24
21
+
+
*
t
22*
1
1
1
0
5
4
2
1
4
3
7
4
5*
81
3*
2i
7*
6*
5t
3*
Si
8*
7i
6>
1
1
1
1
0
1
0
1
0
3
0
3
+S9
8± 1
1951 3
* Mean of 2 replicate plates i standard error of the mean.
** Dissolved/diluted in dimethylsulfoxide (DMSO).
*** Dissolved In sterile distilled water.
t Dissolved in 95% ethanol.
tt Too numerous to count.
Note: 1.0 ing/plate with all bugs toxic (#2468).
I?QH7 at 150 ul/nlatP tnxlr fnr all strains.
7t 1
5±0
4i 1
4> 1
4i 1
8i 1
6t 1
11 t 2
6i 1
8±0
6t 1
8t2
TA-1538
-S9
15± 1
149i16 13±1
>SOO
13*2
lltl
14 t 5
5- 1
10iO
10t 1
7* 1
5* 1
9i 3
6t 1
12t 1
11 lO
+S9
17tO
>500
>SOO
TA-100
-S9
136 tl
>SOO
+S9
1161 2 121 ±1
>SOO
119±2
TA-1535
-59
14±3
15tl
TNTC+t
10i
12i
14*
8*
18 t
21 t
35 t
',7
13*
17±
13*
16*
2
4
0
1
2
5
3
1
2
2
3
2
107*
123 t
96*
103*
90*
86*
107*
1051
nit
97 ±
103*
110±
4
4
2
4
2
2
5
5
2
0
2
4
104 t
lilt
86*
86*
89*
85*
97*
109 t
114*
82*
104*
97*
11
2
4
1
7
11
4
1
4
17
8
4
16 1
13*
13*
9±
12±
. 13t
13t
7t
12t
16 1
12t
14*
2
3
0
2
2
0
3
1
1
5
1
1
+59
15±4
112±16
TNTC
lltl
9±3
9±3
7±1
lOtl
7±1
7±1
S±2
7*2
lltl
10±1
-------
TABLE IV-4 '
AMES ASSAY III
SAMPLE 12471 - MEDIUM OIL
SAMPLE 12472 - TAR
Revertants Per Plate*
I
M
CT>
TA-98
Control (DHSO)
2-Anthraralne**
(10 pg/plate)
Daunomycln***
(10 pg/plate)
9-Am1noacr1d1net
(50 pg/plate)
2-N1trofluorene**
(10 ug/plate)
Methylmethane sulfonate**
(50 pg/plate)
N-Methyl-N'-nltro-N-
nltrosoguanldlne**
(50 pg/plate)
-S9
15±2
22 ±2
3631 7
»S9
373 ± 40
384 1 10
TA-1537
TA-1538
TA-100
TA-1535
-S9
9tl
+S9
13± 1
-S9
6tl
+S9
lOil
10 ±1 74 ±5
9±0 454 ±33
-S9
69± 1
80 ±4
+59
87 ±4
538 ± 56
11 ±1
441 6
59 ±6
682 ±27 424 ±14
157 ±3
176 ±8
* Mean of 2 replicate plates ± standard error of the mean.
** Dissolved/diluted In dimethylsulfoxide (DMSO).
*** Dissolved In sterile distilled water.
t Dissolved In 95* ethanol.
55 ±3
251 It 48 2219 ±235
#2471 - Medium Oil**
0.01 pl/plate
0.015 pl/plate
0.02 pl/plate
0.025 pl/plate
12± 3
5±0
9±4
14±0
12472 - Tar**
,r4
0.01 pl/plate
0.015 pl/plate
0.02 pl/plate
0.025 pi/plate
12±0
6±2
19±1
18 ±0
c
-t
16t3
11±2
13±1
21 ±1
28 ±4
38 ±1
69 ±0
124 ±3
8±2
7± 1
6±1
4±2
6±1
6±1
4±1
4±1
7±2
10±0
8±1
13±2
9±1
14 ±2
11±3
6±1
6±0
6±2
8±1
7±2
10±2
10± 3
12 ±1
4±1
7±2
11 ±0
13±4
12±2
36 ±2
62 ±2
46 ±4
51 ±0
64 ±1
71 ±7
58 ±5
51 ±3
62 ±1
47 ±5
71 ±16
56 ±1
73 ±10
62 ±2
72 ±1
64 ±5
80 ±11
93 ±3
96 ±5
92 ±2
9±1
12±2
10±0
8±2
8±2
8±1
10±4
8±1
5±1
7±0
8±1
5±1
6±0
5±1
7±1
-------
TABLE IV-5
AMES ASSAY IV
SAMPLE 12473 - HEAVY TAR AND DUST
SAMPLE «1152A - LIGHT OIL
I
M
^J
o
IT
TA-98
Control (DHSO)
2-Anthramine**
(10 ug/plate)
Daunomycin***
(10 yg/plate)
9-Aminoacrldlne
(50 yg/plate)
2-N1trofluorene**
(10 ng/plate)
Methylmethane sulfonate**
(50 ng/plate)
N-Methyl-N'-nitro-N-
nitrosoguanidine**
(50 ug/plate)
-S9
17±3
>500
+S9
21 ±1
256 ± 17
>500
Revertants Per Plate*
.TA-1537
TA-1538
TA-100
TA-1535
-S9
9tO
8tl
-S9
lOil
+S9
141 2
-S9
+S9
96±4 106 ±2
-S9
12±2
461 4
31 ±1
60 ± 1
16 ±5 288 ±31
89±6 541125 lOtl
40±7
2391 7 222 ± 4
2251 8
188 ±6
24451134 2051 ±58
12473 - Heavy Tar and Dust**
0.01 pi/plate
0.015 gl/plate
0.02 pi/plate
0.025 pi/plate
11 tO
24 ±1
8il
9±0
#1152A - Light Oil**
0.01 pi/plate
0.015 ul/plate
0.02 ul/plate
(0.025 pi/plate
lltl
9±1
8±1
10±1
31 ±3
31 ±2
60 ±6
82 ±3
14±1
18 ±1
16±1
11 ±1
5±1
5±1
5±1
5±1
4±1
4iO
6±1
4±1
9±1
11 ±1
8±2
12±1
6±1
5±1
7±1
6± 1
61 1
8±0
9±1
6±1
8±2
7±1
12± 1
61 1
30 ± 1
- 55 ±6
62 ±2
66 ±2
10±1
14 ±2
15±3
10±0
96 ±0
98 ±15
85 ±2
94 ±1
73 ±2
62 ±2
67 ±5
88 ±7
89 ±8
.95 ±1
79 ±3
87 ±2
64 ±1
66 ±1
47 ±1
81 ±11
9±0
lOtl
5±2
3±1
8±1
7±2
10±2
10±2
8±1
11 ±0
8±2
3±0
6tO
7±2
6±0
5±1
* Mean of 2 replicate plates ± standard error of the mean.
** Dissolved/diluted in dimethylsulfoxide (DMSO).
*** Dissolved in sterile distilled water.
t Dissolved in 95X ethanol.
-------
V. IN VITRO CYTOTOXICITY ASSAYS
Summary results for all cytotoxicity assays are given in Table V-l.
A. RABBIT ALVEOLAR MACROPHAGE (RAM) ASSAY
Test Sample: 2468
SUMMARY
Sample 2468 was assayed in triplicate in the RAM assay at 1000, 300,
100, 30 and 10 yg/ml. Determinations of total cell counts, cell viability
(trypan blue exclusion), protein and ATP levels made at 20 hours showed
values for these parameters to be >1000 yg/ml.
MATERIALS
Sample 2468 was described as a Slag sample. See Section I. The sample
as received was tested for bacterial contamination before assay by inocula-
tion into Trypticase Soy Broth, Thioglycollate Broth and Saubouraud Liquid
Broth. Sample 2468 was found to be contaminated, but only after nine days
of incubation both at 37°C and at room temperature. Since the RAM assay
is conducted in Medium 199 supplemented with 100 units of penicillin and
100 yg of streptomycin per ml and the sample is only in the test system
for 20 hours, this sample was considered suitable for bioassay.
METHODS
One New Zealand albino (SPF)
-------
in an appropriate volume of Medium 199. Two ml of cells (1.8 x 10 cells)
were added to each 25 cm^ flask. Two ml of the appropriate dilution of
sample 2468 or of the vehicle control were then added. The flasks were
placed on a rocker platform in a 37°C humidified 5% C02 atmosphere and
incubated for 20 hours. At the end of the 20-hour incubation period, cell
viability, total protein and ATP content were determined.
RESULTS
Sample 2468 gave an ECso value of >1000 yg/ml for total cell counts,
cell viability (trypan blue exclusion), protein and ATP levels at 20 hours.
Detailed results are shown in Table V-2 and Figure V-l.
B. CHINESE HAMSTER OVARY (CHO) CLONAL TOXICITY ASSAY
Test Samples:
2987 1152A
2988 2471
2468L 2472
2473L 2473
SUMMARY
The above samples were assayed in triplicate in the CHO assay at con-
centrations of 600, 200, 60, 20 and 6 ug/ml for solid samples (2987, 2988,
2468L and 2473L) and at 2.0, 0.2, 0.06, 0.02, 0.006, 0.002 and 0.0002 ul/ml
for liquid samples (1152A, 2471, 2472 and 2473). Sample 2468L had no
detectable toxicity. Sample 2473L had low toxicity. Samples 2987 and
2988 had moderate toxicity. Samples 1152A, 2471, 2472 and 2473 had high
toxicity. A summary of these results is shown in Table V-l.
MATERIALS .
Sample identifications are given in Section I. Note that samples
1152A, 2471, 2472 and 2473 were extracted with CH2C12 and solvent-exchanged
with DMSO as described in Section III before use in this bioassay.
The samples, following extraction and solvent exchange, were tested
for bacterial contamination before assay by inoculation into Nutrient Broth
and Nutrient Agar at 25°C and 37°C and were found to be suitable for appli-
cation to the in vitro assay. .
B-19
Arthur D Little Inc
-------
METHODS
Chinese hamster ovary fibroblasts were removed from the liquid nitrogen
frozen tumor bank on April 15, 1980, and maintained as monolayer cultures in
Dulbecco's modified Eagle's Minimum Essential Medium supplemented with 10%
fetal calf serum, 100 U/ml penicillin and 100 ug/ml streptomycin until
May 12, 1980. At that time, the medium was changed to complete Ham's F-12
which was used for all subsequent cell passages and testing.
Liquid samples 2987, 2988, 2468L and 2473L were assayed in a single
experiment on May 20, 1980 (Experiment 1). CHO cells in logarithmic growth
phase from passage 7 were suspended at 50 cells/ml and 4 ml of this cell
suspension were dispensed into each of 60 mm tissue culture dishes. Cells
were allowed to adhere for six hours in a humidified 5% C02 atmosphere at
37°C. The medium was aspirated and 4 ml of the samples appropriately
diluted in 2.5X complete medium were added. Cultures treated with sodium
azide (NaN3, 600 and 100 ug/ml) and untreated cultures were also used.
The dishes were returned to the incubator for an additional 24 hours after
which time all dishes were washed three times with phosphate buffered saline
and refed with 5 ml of complete Ham's F-12 medium. All dishes were returned
to the incubator for an additional six days to allow clones to develop.
At the end of the final incubation period, all dishes were drained, washed
once with phosphate buffered saline, fixed for at least 15 minutes with 100%
methanol and stained 10-15 minutes with 10% Giemsa. Colony counts were
determined on an Artec Colony Counter.
Extracted, solvent-exchanged samples 1152A, 2471, 2472 and 2473 were
assayed in a single experiment on June 12, 1980 (Experiment 2). Because
of the volatility of these samples, even after solvent exchange, the highest
concentrations were assayed in tightly stoppered tissue culture flasks rather
than in tissue culture dishes. The limiting factor in the testing of these
samples was the concentration of the organic solvent dimethylsulfoxide (DMSO)
which has been set at 2% to avoid solvent toxicity. Therefore, the highest
concentration of sample tested was 20 ul/ml of the extracted material, or
2 ul/ml of the original sample.
CHO cells from passage 14 were suspended at 50 cells/ml in Ham's F-12
and flasks and dishes were inoculated with 4 ml of a cell suspension con-
taining 50 cells/ml. The cells were allowed to adhere for six hours in a
humidified 5% C02 atmosphere at 37°C. The medium was then aspirated and
4 ml of the appropriately diluted sample in complete Ham's F-12 was added.
Untreated flask and dish cultures were included as media controls. Cultures
in dishes were treated with sodium azide at 600 and 100 ug/ml (positive con-
trols) and with 20 and 2 ul of DMSO (vehicle controls). The 25 cm2 flasks
which received the highest test sample concentrations were tightly stoppered
and all dishes and flasks were returned to the incubator for an additional
24 hours. The pH of all dilutions of sample 1152A and of all controls was
7. Culture medium containing the highest two concentrations of samples
2471, 2472 and 2473 was very murky although the lower concentrations which
were clear had a pH of 7.
B-20
Arthur D Little Inc
-------
All cultures were drained after 24 hours and washed three times with
phosphate buffered saline. Cultures were refed with complete Ham's F-12.
The cultures treated with 20 yl/ml of samples 2471, 2472 and 2743 (flasks)
showed evidence of sample remaining after the three washes. The pH of
all flasks (controls and samples) was slightly basic; all plates had a pH
of approximately 7.
The media from all cultures were drained after six additional days
of incubation. The colonies were fixed with 100% methanol and stained
with 10% Giemsa. The plates were counted on the Artec Colony Counter
and the flasks were counted manually.
RESULTS
Detailed results for samples 2987, 2988, 2468L and 2473L are shown
in Table V-3 and Figure V-2. The response of CHO" cells to NaNs (ECso =
280 yg/ml) is comparable to that reported by others (Dr. B. Myer, Litton
Bionetics, personal communication). The surviving fraction of CHO cells
treated with 600 yl/ml of sample 2468L was 0.58; thus, the ECso for this
sample is reported as >600 yg/ml. ECcn's for other samples are: 2987,
37 yl/ml; 2988, 98yl/ml and 2473L, 120 yl/ml. According to present EPA
practice, these samples would be classified as having: no detectable toxi-
city, sample 2468L; low toxicity, sample 2473L; and moderate toxicity,
samples 2987 and 2988.
Detailed results for samples 1152A, 2471, 2472 and 2473 are shown in
Table V-4 and in the left panel of Figure V-3. The response of CHO cells
to NaNo is shown in the right panel o.f this figure; the EC50 for NaNs is
260 yg/ml. Cells treated with 20 yl and 2 yl DMSO (solvent control, left
panel) had a mean surviving fraction of 0.98, comparable to media control
dishes. The number of clones formed by untreated control cells cultured
in flasks was slightly lower (mean, 178) than that of cells cultured in
dishes (188). Surviving fractions of cells treated with 20 yl of all
samples and with 2 yl of sample 2472 (which had been tested in flasks due
to their volatility) were calculated with respect to the appropriate
number of clones obtained in flask-cultured control cells. The ECso's
in yl/ml for the test samples are: 1152, 0.68; 2471, 0.11; 2472, 0.034;
and 2473, 0.072. According to present EPA practice, all of these samples
would be classified as having high toxicity.
Senior Technician Evaluating Material
Case Leader, Senior Staff
CTarolyn fl. Creswell, M.A.
L
Section Leader, Bio/Medical Sciences
Andrew Sivak, Ph.D.
B"21 Arthur D Little Inc
-------
TABLE V-l
SUMMARY OF RESULTS OF IN VITRO TOXICITY TESTS
Sample
Description
2468 Slag
2987 Wastewater
2988 Treated wastewater
2468L ASTM Slag leachate
Test System
RAM
CHO
CHO
CHO
Toxicity
2473L ASTM Heavy tar leachate CHO
1.152A Light oil
2471 Medium oil
2472 Tar
2473 Heavy tar and dust
CHO
CHO
CHO
CHO
No detectable toxicity
(>1000 yg/ml)
Moderate toxicity
(37 yl/ml)
Moderate toxicity
(98 ul/ml)
No detectable toxicity
(>600 yl/ml)
Low toxicity
(120 yl/ml)
High toxicity
(0.68 yl/ml)
High toxicity
(0.11 yl/ml)
High toxicity
(0.034 yl/ml)
High toxicity
(0.072 yl/ml)
B-22
Arthur D Little Inc
-------
Concentration
1000 ug/ml
300 ug/ml
100 yg/ml
30
10
Controls
TABLE V-2
RESULTS OF RAM ASSAY OF RADIAN SAMPLE 2468
% Viable
66.9
69.0
66.2
67.4
78.7
83.1
86.9
82.9
85.7
85.9
70.0
80.5
90.2
93.3
90.8
91.4
93.0
94.5
92.9
93.5
94.9
95.1
94.2
88.6
91.3
95.4
89.4
93.3
92.8
Viability
Index
59.4
58.2
56.2
57.9
69.9
75.2
88.8
78.0
84.7
82.1
59.1
75.3
95.7
92.8
84.7
91.1
88.8
96.1
87.7
90.9
Total Protein
yg/ml
101.1
113.1
107.1
101.1
121.8
109.9
110.9
86.2
98.3
91.8
92.1
97.6
_
95.5
96.5
113.8
133.1
128.4
125.1
125.4
114.1
123.3
124.0
130.8
110.1
99.0
102.6
116.2
% T/C
87.0
97.3
92.2
87.0
104.8
94.6
95.5
74.2
84.6
79.0
79.3
84.0
_
82.2
83.1
98.0
114.6
110.5
107.7
6 ATP
fgTTO0 Cells
1.28 x 10?
0.98 x 10^
1.13 x 10y
1.45 x 10?
1.79 x 10y
1.22 x 10n
1.49 x 10*
1.17 x 10?
1.30 x 10y
0.83 x 10y
1.10 x 10*
Q
1.23 x 10y
1.44 x 10y
0.67 x 10y
1.11 x 10y
1.18 x 10?
0.90 x 10y
0.96 x 10s.
1.01 x 10y
1.70 x 10?
1.40 x !OQ-
1.04 x 10y
1.25 x 10y
1.39- x !OQ
1.19 x !OQ
0.94 x 10n
1.20 x 10*
1.26 x 10y
% T/C
101.3
77.5
89.4
114.7
141.6
96.5
117.6
92.6
102.8
65.7
86.9
97.3
113.9
53.0
88.0
93.4
71.2
75.9
80.2
B-23
Arthur D Little Inc
-------
TABLE V-2
RESULTS OF RAM ASSAY OF RADIAN SAMPLE 2468
(continued)
Footnote
Quality Control Data and Results of RAM Assay of Sample 2468:
No. of Rabbits Used
Viability of Macrophages
Total Cell Number Recovered
Dilution Volume
Cells/ml
% Macrophages
Incubation Time
pH of Samples (T )
pH of Samples (T«Q)
Vehcile Used
ED5Q Values
Cell Count
Viability
Viability Index
Protein
ATP
1 (SPF)
96.9%
4.3 x 107
48 ml Medium 199
9.0 x 105
98.5
20 hours
•v.7
^7 except #3 @ 100 ug/ml
Medium 199
>1000 ug/ml
>1000 ug/ml
>1000 ug/ml
>1000 ug/ml
>1000 ug/ml
B-24
Arthur D Little Ii
-------
SZ-9
Relative to Vehicle Control
UJ
O
r>
o
n
ro
o> —>
r+ O
_.. o
O
'.a
oo
O
o
o
o
o
73
O
i—i
3>
CO
oo
US
v v v v |r
o o o O cin
o O O O
o o o o
o>
a-
o>
cr
-o o
rl-
(B
CL
fl>
x
-------
TABLE V-3
CHO CLONAL TOXICITY ASSAY RESULTS - EXPERIMENT NO. 1
Sample
Untreated Control
Mean ± Standard
Deviation
Positive Control
(NaN-J
O
Mean ± Standard
Deviation
NaN,,
O
Mean ± Standard
Deviation
Concentration pH No. of Colonies
7.0 190
154
155
176
149
172
149
155
192
170
174
171
166
168
150
166.1 ± 13.9*
600 ug/ml 7.0 48
64
54
69
64
59.8 ± 8.6*
100 yg/ml 7.0 106
no
121
115
119
114.2 ± 6.2*
Surviving
Fraction
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
0.29
0.39
0.31
0.42
0.39
0.36 ± 0.06**
0.64
0.66
0.74
0.70
0.72
0.69 ± 0.07**
B-26
Arthur D Little Inc
-------
TABLE V-3
CHO CLONAL TOXICITY ASSAY RESULTS - EXPERIMENT NO. 1
(continued)
Colony Counts (uq/ml)
pH
2987 7.0
Mean
Standard Deviation*
Surviving Fraction
Standard Deviation**
2988 7.0
Mean
Standard Deviation*
Surviving Fraction
Standard Deviation**
2468L 7.0
Mean
Standard Deviation*
Surviving Fraction
Standard Deviation**
2473L 7.0
Mean
Standard Deviation*
Surviving Fraction
Standard Deviation**
* Standard Deviation =.J
600
0
0
0
0
0
0
0
0
0
0
0
0
109
128
112
116.3
10.2
0.77
0.09
0
0
0
0
0
0
Yzx2 zx2\
200
0
0
0
0
0
0
0
0
0
0
0
0
144
165
161
156.7
11.2
0.94
0.10
8
4
6
6.0
2.0
0.04
0.01
vJL
60
38
25
22
28.3
8.5
0.17
0.05
135
142
136
137.7
3.8
0.83
0.08
187
180
150
172.3
19.7
1.04
0.15
187
171
169
175.7
9.9
1.06
0.11
20
147
144
168
153.0
13.1
0.92
0.11
173
198
175
182.0
13.9
1.10
0.12
174
164
151
163.0
11.5
0.98
.0.11
188
198
161
182.3
19.1
1.10
0.15
6
178
164
176
172.7
7.6
1.04
0.10
166
172
185
174.3
9.7
1.05
. 0.11
173
195
164
177.3
16.0
1.07
0.13
136
168
167
157.0
18.2-
0.95
0.14
N N* / A N-l
** Standard Deviation
Var
T + ( i ) 2 VarC
\ I 7
B-27
Arthur D Little Inc
-------
FIGURE V-2
RADIAN CHO CLONAL TOXICITY ASSAY
EXPERIMENT NO. 1
Concentration (ul/ml)
B-28
Arthur D Little Inc
-------
TABLE V-4
CHO CLONAL TOXICITY ASSAY RESULTS - EXPERIMENT NO. 2
Sample Concentration
Media Control
(60 mm dishes)
*
Mean ± Standard
Deviation
Media Control
(25 cm2 flasks)
Mean ± Standard
Deviation
Vehicle Control 20 ul/ml
(DMSO)
Mean ± Standard
Deviation
pH No. of Colonies
7.0 190
175
206
179
185
199
194
196
188
188
201
189 .
170
180
195
188
188.3 ± 10.2*
7.2 195
165
189
162
166
203
188
167
178.6 ± 15.8*
7.0 201
199
179
199
159
193
185
168
188.4 ± 15.6*
Surviving
Fraction
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.07
1.06
U96
1.06
0.85
1.03
0.99
0.89
0.98 ± 0.10**
B-29
Arthur D Little Inc
-------
TABLE V-4
CHO
Sampl e
Vehicle Control
(DMSO)
Mean ± Standard
Deviation
Positive Control
(NafU
w
Mean ± Standard
Deviation
NaN.
0
Mean ± Standard
Deviation
CLONAL TOXICITY ASSAY RESULTS - EXPERIMENT NO.
(continued)
Concentration pH No. of Colonies
2 pi/ml 7.0 194
188
178
193
180
187
189
198
188.4 ± 6.8*
600 yg/ml 7.0 14 •
24
28
25
28
23.8 ± 5.8*
100 yg/ml 7.0 100
176
199
148
183
160
173.2 ± 19.9*
2
Surviving
Fraction
1.03
1.00
0.95
1.02
- 0.96
0.99
1.00
1.05
1.00 ± 0.06**
0.07
0.13
0.15
0.14
0.15
0.13 ± 0.03**
0.53
0.93
1.06
0.79
0.98
0.85
0.92 ± 0.12**
B-30
Arthur D Little Inc
-------
TABLE V-4
CHO CLONAL TOXICITY ASSAY RESULTS - EXPERIMENT NO. 2
(continued)
Colony Counts ( yl/ml)
PH
1152A 7.0-7.2
Mean
Standard Deviation*
Surviving Fraction
Standard Deviation**
2471 7.0-7.2
Mean
Standard Deviation*
Surviving Fraction
Standard Deviation**
2472 7.0-7.2
Mean •
Standard Deviation*
Surviving Fraction
Standard Deviation**
2473 7.0-7.2
Mean
Standard Deviation*
Surviving Fraction
Standard Deviation**
* Standard Deviation =-J[
** Standard Deviation ^ I
2.0
13
18
17
16.0
2.7
0.09'
0.02
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
ZX2 I
"N
Var T +|
0.2
190
168
189
182
12
0
0
2
1
8
3
3
0
0
0
0
0
0
0
1
0
0
0
0
0
0
» A
TP
i
.3
.4
.97
.08
.7
.8 .
.02
.02
.33
.58
.002
.003
)"i
0.06
171
154
190
171.
18.
0.
0.
165
185
189
179.
12.
0.
0.
13
29
13
18.
9.
0.
0.
94
123
122
113.
16.
0.
0.
N
7
0
91
11
7
9
95
09
3
2
10
05
0
5
60
09
0.02
177
191
173
180.3
9.5
0.96
0.07
180
174
192
182.0
9.2
0.97
0.07
183
169
167
173.0
8.7
0.92
0.07
147
155
137
146.3
9.0
0.78
0.06
0.006
175
203
172
183
17
0
0
188
206
182
192
12
1
0
170
184
182
178
7
0
0
172
150
150
157
12
0
0
.3
.1
.97
.10
.0
.5
.02
.09
.7
.6
.95
.07
.3
,7
.84
.08
0.002
166
166
166
166
0
0
0
189
193
200
194
5
1
0
184
185
202
193
10
1
0
180
185
168
177
8
0
0
.0
.88
.05
.0
.6
.03
.06
.3
.1
.01
.08
.7
.7
.94
.07
0.0002
166
169
160
165.0
4.9
0.88
0.05
177
191
177
181.7
8.1
0.97
0.07
195A
297*
428A
174
169
173
172.0
2.7
0.91
0.05
[T)2 varc
Many very small colonies possibly due to excessive movement of dishes while
washing at 24 hours or to initial inoculation error.
B-31 Arthur D Little Inc
-------
FIGURE V-3
RADIAN CHQ CLONAL TOXICITY ASSAY
EXPERIMENT NO. 2
T
OJ
c
D
c:
c
o
o>
o
-O
i.
ia
-a
c
ea
CO
+1
c
o
o
(O
CD
C
i-
3
to
1.2
.£ 1.0
0.8
0.6
0.4
0.2
Sample EC™
% DMSO Control
O NaN3 260 u<
A 1152A 0.68 gl/ml
Sample K^Q
2471 0.11 ill/ml
2472 0.034 pi/ml
2473 0.072 ul/ml
0.002
0.006
0.02
0.06
0.2
100
600
-------
VI. ACUTE IN VIVO TOXICOLOGICAL TESTS IN RODENTS
Test Samples:
2468 2473
1152A 2987
2471 2988
2472 2468L
2473L
SUMMARY
Each sample was administered by gavage as a single dose of 10 gm/kg or
10 ml/kg to male and female CDF] mice (5rf, 5?). Animals were observed daily
for signs of poor health. Surviving animals were killed and autopsied on
the 15th day following dosing. Gross autopsy did not reveal any organ changes
which appeared to be related to the test material. More than one-half of
the test animals died following treatment with samples 1152A (7/10), 2471
(10/10) or 2472 (7/10). Three test animals died following administration of
sample 2473. Zero or 1 death occurred after administration of 2468 (1/10),
2987 (1/10), 2988 (0/10), 2468L (1/10), 2473L (1/10). Two animals in the
water control group, 2 animals in the Ky control group and 1 Trioctanoin
control group died.
EPA Level 1 quantitative testing is recommended for 1152A, 2471, 2472
and 2473.
MATERIALS
The materials were received by Ms. Carolyn'Creswell of Arthur D. Little,
Inc., and were identified as follows:
Number Description
2468 Slag
1152A* Light Oil
2471* Medium Oil
2472* Tar
2473* Heavy Tar and Dust
2987 Wastewater, COD = 17,700 mg/1
2988 Treated Wastewater, COD = 5,540 mg/1
2468L ASTM Slag Leachate
2473L ASTM Heavy Tar Leachate
* Handle with caution.
B-33
Arthur D Little Inc
-------
METHODS
A group of male and female CDF-| mice was obtained from Charles River
Breeding Laboratories and placed in quarantine for one week at Arthur D.
Little, Inc., laboratories, 38 Memorial Drive, Cambridge, Massachusetts.
From this group, five males and five females of comparable body weights were
selected for testing of each compound. All selected animals appeared to
be healthy.
Test material was administered by gavage in a single dose to each
animal. The dose employed in each case was 10 gm/kg or 10 ml/kg.
Seven of the samples were used as received. Sample 2468 (Slag) was
mixed with Ky lubricant* for dosing. Sample 2473 was slightly solubilized
with trioctanoin** (6% by volume). Control animals were treated with
10 ml/kg of Ky lubricant or trioctanoin, respectively.
Body weights were recorded on day of dosing (Day 1), Day 8 and Day 15.
Animals were observed daily for signs of poor health. A gross autopsy was
performed on each animal at death or sacrifice. Organ weights were not
obtained. _
RESULTS
The results are summarized in Table VI-1 and individually presented
in Tables VI-2 through VI-10. Mortality exceeding that of appropriate con-
trol groups was observed in groups treated with samples 1152A, 2471, 2472
and 2473. One animal which died was found to have a large axillary mass
(Group 2473L). Deaths occurred in control groups as indicated in
Tables VI-l-VI-10.
At autopsy, no organ changes were observed which appeared to be treat-
ment related. Surviving animals in Group 1152A showed low body weights at
Day 15. It is suspected that the delayed deaths in the control groups were
related to difficulties in sample delivery.
* K-Y^Sterile Lubricant, Water Soluble, Johnson and Johnson, New
Brunswick, New Jersey.
** Trioctanoin (C,7HcnOc) Lot A8B, Eastman Kodak Co., Rochester, New
York. " 50 5
B-34
Arthur D Little Inc
-------
CONCLUSIONS
Testing of acute oral toxicity in rodents has demonstrated Samples
1152A, 2471, 2472 and 2473 to have greater lethal potential than the
appropriate control vehicle.
Senior Technician Evaluating Material
Subcase Leader and Unit Manager,
Toxicology
Case Leader
Vice-President, Section Manager
Bio/Medical Sciences Section
s- -
Peter C. Rachwall
Rosalind C. Anderson, Ph.D.
1
/9-yyyiX—
«iii u*
A
Andrew Sivak, Ph.D.
B-35
ArthurDLittlelnc
-------
TABLE VI-1
SUMMARY OF RESULTS OF ACUTE ORAL TOXICITY TESTS
Compound
#
2468 in Ky
Ky Control
1152A
2471
2472
2987
2988
Water Control
2473 + Trioctanoin
Trioctanoin Control
2468L
2473L
Leachate Control
Mortality
(Day 15)
1/10
2/10
7/10
10/10
7/10
1/10
0/10
2/10
noin 3/10
ntrol 1/10
1/10
1/10
ol 0/10
Day of
Death % Weight Gain
(Day 15)
Day 4
2-Day 4
5-Day 1 , 2 -Day 2
10-Day 1
3-Day 1, 3-Day 2,
1-Day 5
Day 7
1-Day 6, 1-Day 8
1-Day 1, 2-Day 5
1-Day 7
1-Day 6
1-Day 13
_____
9%
9%
0%
—
4%
4%
9%
14%
4%
9%
9%
4%
9%
* Large mass possible cause of death.
B-36
Arthur D Little Irx
-------
TABLE VI-2
SUMMARY OF SINGLE-DOSE ORAL TOXICITY OF 2468
Species: Mouse
Strain: CDF-J
Body Weight Range (gm):
Day 1 19-27
Day 8 21-27
Day 15 22-29
Formulation:
Concentration (gm/ml): 0.54 gram/ml
Approximate Volume Ad-
Mixed with Ky lubricant
ministered:
0.42 ml
Dosage ( gmAg)» Mortality, and Percent Mean Body Weight Gain
of Survivors Post-Treatment
Dosage
Control
Ky 10 gm/kg
2468 in Ky
10 gn/kg
Mortality
Day 8
Day 15
2/10
1/10
2/10
1/10
Numbers rounded to nearest integer
B-37
% Mean Body Weight Gain
Day 8
Day 15
4%
4%
9%
Arthur D Little Inc
-------
TABLE VI-3
SUMMARY OF SINGLE-DOSE ORAL TOXICITY OF 1152A
Species: ' Mouse
Strain: CDF1
Body Weight Range (gm):
Day 1 19-24
Day 8 19-26
Day 15 21-27
Formulation: Used as Received
Concentration (gm/ml): Unknown
Approximate Volume Ad-
ministered: 0.21ml
Dosage ( mVkg), Mortality, and Percent Mean Body Weight Gain
of Survivors Post-Treatment
Dosage Mortality % Mean Body Weight Gain
Day 8 Day 15 Day 8 Day 15
Control 2/10 2/10 9% 14%
Water 10 ml/kg
1152A 7/10 7/10 -10% 0%
10 ml/kg
Numbers rounded to nearest integer
B-38
Arthur D Little Inc
-------
TABLE VI-4
SUMMARY OF SINGLE-DOSE ORAL TOXICITY OF 2471
Species: Mouse
Strain: CDF1
Body Weight Range (gm):
Day 1 19-26
Day 8 19-26
Day 15 21-27
Formulation: Used as Received
Concentration (gm/ml): Unknown
Approximate Volume Ad-
ministered: 0.22ml
Dosage (ml/kg), Mortality, and Percent Mean Body Weight Gain
of Survivors Post-Treatment
Dosage Mortality % Mean Body Weight Gain
Day 8 Day 15 Day 8 Day 15
Control
Water 10 ml/kg 2/10 2/10 9% 14%
2471
10 ml/kg 10/10 10/10
Numbers rounded to nearest integer
B-39
Arthur D Little Inc
-------
TABLE VI-5
SUMMARY OF SINGLE-DOSE ORAL TOXICITY OF 2472
Species:
Strain:
Body Weight Range (gm):
Day 1 19-26
Day 8 19-26
Day-15 21-27
Formulation:
Concentration (gm/ml):
Approximate Volume Ad-
ministered
Mouse
CDF1
Used as Received
Unknown
0.22ml
Dosage (ml/kg), Mortality, and Percent Mean Body Weight Gain
of Survivors Post-Treatment
Dosage
Mortality •
Day 8
Day 15
% Mean Body Weight Gain
Day 8
Day 15
Control 2/10
Water 10 ml/kg
2/10
9%
14%
2472
10 ml/kg
7/10
7/10
0%
4%
Numbers rounded to nearest integer
B-40
Arthur D Little Inc
-------
TABLE VI-6
SUMMARY OF SINGLE-DOSE ORAL TOXICITY OF 2473
Species:
Strain:
Body Weight Range (gm):
Day 1 16-25
Day 8 18-27
Day 15 20-29
Formulation:
Concentration (gm/ml):
Approximate Volume Ad-
ministered
Mouse
CDF
1
Trioctanoin (6% by volume) added to
facilitate delivery
Unknown
0.22 ml
Dosage (ml/kg). Mortality, and Percent Mean Body Weight Gain
of Survivors Post-Treatment
Dosage
Mortality
Day 8
Day 15
% Mean Body Weight Gain
Day 8
Day 15
Control
Trioctanoin
10 ml/kg
0/10
7/10
0%
9%
2473 + 6%
Trioctanoin
10 ml/kg
3/10
3/10
4%
Numbers rounded to nearest integer
B-41
Arthur D Little Inc
-------
TABLE VI-7
SUMMARY OF SINGLE-DOSE ORAL TOXICITY OF 2987
Species:
Strain:
Body Weight Range (gm):
Day 1 19-25
Day 8 19-26
Day 15 19-27
Formulation:
Concentration (gm/ml):
Approximate Volume Ad-
ministered
Mouse
CDF]
Used as Received
Unknown
0.22ml
Dosage (ml/kg). Mortality, and Percent Mean Body Weight Gain
of Survivors Post-Treatment
Dosage
Mortality
Day 8
Day 15
% Mean Body Weight Gain
Day 8
Day 15
Control, 2/10
Water 10 ml/kg
2/10
14%
2987
10 ml/kg
1/10
1/10
Numbers rounded to nearest integer
B-42
Arthur D Little, Inc
-------
. TABLE VI-8
SUMMARY OF SINGLE-DOSE ORAL TOXICITY OF 2988
Species:
Strain:
Body Weight Range (gm):
Day 1 19-23
Day 8 19-26
Day 15 21-28
Formulation:
Concentration (gm/ml):
Approximate Volume Ad-
ministered
Mouse
CDF]
Used as Received
Unknown
0.22 ml
Dosage (ml/kg), Mortality, and Percent Mean Body Weight Gain
of Survivors Post-Treatment
Dosage
Mortality
Day 8
Day 15
% Mean Body Weight Gain
Dav 8
Day 15
Control, 2/10
Water 10 ml/kg
2/10
9%
14%
2988
10 ml/kg
0/10
0/10
9%
Numbers rounded to nearest integer
B-43
Arthur D Little, Inc
-------
TABLE VI-9
SUMMARY OF SINGLE-DOSE ORAL TOXICITY OF 2468L
Species:
Strain
Body Weight Range (gm):
Day 1 19-24
Day 8 . 19-27
Day 15 21-28
Formulation:
Concentration (gm/ml):
Approximate Volume Ad-
ministered
Mouse
CDF]
Used as Received
Unknown
0.22 ml
Dosage (ml/kg), Mortality, and Percent Mean Body Weight Gain
of Survivors Post-Treatment
Dosage
Mortality
Day 8
Day 15
% Mean Body Weight Gain
Day 8
Day 15
Leachate
10 ml/kg
0/10
0/10
9%
2468L
10 ml/kg
1/10
1/10
4%
9%
Numbers rounded to nearest integer
B-44
Arthur D Little, Inc
-------
TABLE VI-10
SUMMARY OF SINGLE-DOSE ORAL TOXICITY OF 2473L
Species:
Strain:
Body Weight Range (gm):
Day 1 19-26
Day 8 19-27
Day 15 20-28
Formulation:
Concentration (gm/ml):
Approximate Volume Ad-
ministered
Mouse
CDF]
Used as Received
Unknown
0.22 ml
Dosage (ml/kg), Mortality, and Percent Mean Body Weight Gain
of Survivors Post-Treatment
Dosage
Mortality
Day 8
Day 15
% Mean Body Weight Gain
Day 8
Da-y 15
Leachate
10 ml/kg
2473L
10 ml/kg
0/10
0/10
0/10
1*/10
Q%
* Autopsy at 13 days showed large axillary mass.
Numbers rounded to nearest integer -
B-45
Arthur D Little Inc
-------
APPENDIX C
MASS BALANCE CALCULATIONS
TABLE OF CONTENTS
Cl.O INTRODUCTION c_2
C2.0 MASS BALANCE CALCULATIONS FOR THE KOSOVO COAL DRYING SECTION c_6
C3.0 MASS BALANCE CALCULATIONS FOR THE KOSOVO GAS PRODUCTION SECTION.. c_13
C4.0 MASS BALANCE CALCULATIONS FOR THE KOSOVO RECTISOL SECTION C-25
C5.0 MASS BALALNCE CALCULATIONS FOR THE KOSOVO PHENOSOLVAN SECTION c-28
C6 .0 KOSOVO FLARE SYSTEM CALCULATIONS C-42
C7.0 OVERALL (PLANT-WIDE) KOSOVO MASS BALANCE CALCULATIONS c-45
C8.0 KOSOVO OVERALL (PLANT-WIDE) TRACE ELEMENT MASS BALANCE
CALCULATIONS ". C-56
-------
APPENDIX C
MASS BALANCE CALCULATIONS
Cl.O INTRODUCTION
This appendix describes the calculations and assumptions used to derive
carbon, sulfur, and nitrogen balances for the Kosovo gasification plant.
Figures C.l-1 to C.l-3 summarize the overall results of these balances. The
calculations used to obtain the results presented in these figures are given 'in
Section C7.0.
Since the derivation of mass balances was not one of the objectives of the
Kosovo test program, the data used to support these calculations are
incomplete. However, the balances are presented to lend insight into the opera-
tion of the Kosovo plant. In performing these calculations, the values for
stream composition and flow rate given as 'overall best values' in Appendix A
were used. When experimental flow rate data were not available, design or
estimated flow rates were used. All calculations are normalized to a
one-gas ifier-in-service basis.
In the carbon balance results presented in Figure C.l-1, the percentage of
the carbon in the coal which is accounted for in the various product and waste
streams is 93%. Most of the carbon entering with the coal was found in the
clean product gas, the combined flare feed gas, and the COa-rich waste gas.
Figure C.1-2 shows the results from the sulfur mass balance calculations.
The percentage of the sulfur in the coal accounted for in the product and waste
streams is 175%. The poor accountability of this balance is probably due to
variations in the input coal sulfur content as well as the use of the design
rather than a measured flow rate value for the input coal. Regardless of the
poor accountability, these results indicate that in this design most of the
sulfur in the coal ends up in the flare feed stream.
Figure C.l-3 summarizes the nitrogen mass balance results. The percentage
of the nitrogen entering with the coal and with the oxygen fed to the gasifiers
accounted for in the product and waste streams is 51%. In analyzing gas phase
results, it was sometimes difficult to discriminate between molecular nitrogen
actually present in the sampled gas stream and nitrogen present due to sample
contamination with air. Nitrogen data were not included in the nitrogen
balances when the Na/Oa ratio in the analysis was similar to the 79/21 Na/Oa
ratio found in air.
. C-2
-------
o
• uw
ao-
60-
Parcent
ol
Inlet
Carbon
40-
20-
2«
M 25
10
U 0.3 I-*
Runol Clean Liquid Solid Aqueous Flan CCyRlch Olher
Mine Coal Product By-Products Discharges Discharges Streams Waste Gaseous
Gas Gas Discharges
Figure C.l-1. A summary of Kosovo carbon mass balalnce results
(93% accountability).
-------
o
100-
88-
Percent
ol
Inlel
Sulfur
20-
too
Runot-
MlnaCoal
ltd
Clean
Pioducl
Gas
Liquid
By Producti
Solid
Olschargai
Aqueous
Discharge*
Flu*
Streams
Ammonia
Slflpper
Vent Gas
Other
Gaseous
Discharges
Figure C.l-2. A summary of Kosovo sulfur mass balance results
(175% accountability).
-------
n
Ol
100-
80-
60-
Parcanl
ol
Inlel
Hlcrogu
40-
20-
22.6
IT
4.7
2» 2.7 i a
1 ' 1 0.« 0.7» II 1 1
1 1 BMMK^BMB •^•^^^V II II
Run-ol- Clean Liquid Solid Aqueou> Flan Ammonia Olhai
Mine Coal Product By Products Dlscharga Dlschacgaa Slraama Shipper Oaiaoua
and Oxygen Gas Vent Gas Discharges
Streams
Figure C.l-3.
A summary of Kosovo nitrogen mass balance results
(51% accountability) .
-------
In addition to the overall mass balances summarized in Figures C.l-1
through C.l-3, carbon, sulfur, and nitrogen balances were performed for the
following plant sections:
• Coal Drying (Section C2.0),
• Gas Production (Section C3.0),
• Rectisol (Section C4.0),
• Phenosolvan (Section C5.0), and
• the Flare System (Section C6.0).
Mass balances were also derived for IS key inorganic trace elements.
These balances are presented in Section C7.0.
C2.0 MASS BALANCE CALCULATIONS FOR THE KOSOVO COAL DRYING SECTION
Mass balances were calculated for carbon, sulfur, and nitrogen for the
Kosovo Coal Drying section. The results are summarized in Table C.2-1.
Composition data were not available for the 'run—of-mine' coal input to
the Coal Drying section. Therefore, these calculations could not be used to
determine component accountabilities in this section.
The major inlet and outlet streams in the coal drying section are:
Inlet Streams:
• Wet 'Run-of-Mine' Coal
• High Pressure (3 MPa) Steam
Outlet Streams;
• Dried Coal
• Fleissner Condensate
• Autoclave Vent Gas
• Condensate Tank Vent Gas
During the Phase II test program, major component analyses were performed
for the dried coal and Fleissner autoclave vent gas streams. The Fleissner
condensate and the condensate tank vent gas were not analyzed.
C-6
-------
TABLE C.2-1. KOSOVO COAL PREPARATION SECTION MASS BALANCE RESULTS
Stream
All values in kg/gasifier—hr
Total Mass
Flow
Carbon
Mass Flow
Sulfur
Mass Flow
Nitrogen
Mass Flow
InletStreams:
Run-of-Mine Coal (s)
Outlet Streams:
Dried Coal (s)
Autoclave Vent (g)
TOTAL OUTLET
2.4 E+04
ND
ND
7.1 E+03
1.4 E+02
ND
1.6 E+04 7.1 E+03 1.4 E+02 1.7 E+02
7.9 E+01 8.5 E+00 6.0 E-01 0*
1.7 E+02
(s) - solid stream
(g)
ND -
gaseous stream
excluding molecular nitrogen
no data available
C-7
-------
Ultimate Analysis data for the dried coal are given in Table C.2-2. The
data are reported in weight percent (wt %) . To convert these data to mass
flows, the following equation is used:
Component Mass __ / Component Concentration in wt % \ /Total Stream Flow |
Flow Rate ^ 100 J \ Rate in kg/hr ) (1)
For example, the dried coal carbon mass flow rate is calculated as follows:
«•««>•« Wte) - 7.1E+03
TABLE C.2-2. KOSOVO COAL PREPARATION SECTION SOLID STREAM DATA
Component Dried Coal
Design Flow Rate (kg/gasifier-hr) 1.6 E+04
Ultimate Analysis (wt %)
Moisture 20.2
Ash 14.3
Carbon 44.5
Sulfur 0.89
Hydrogen 3.51
Nitrogen 1.08
Oxygen 15.5
Chlorine 0.1
Table C.2-3 presents concentration and flow rate data for the autoclave
vent gas. To determine the total carbon content of this gas, the moles of
carbon in carbon-containing species must be summed. The carbon—containing
species identified and quantified for the autoclave vent gas are shown in Table
C.2-4. Also shown is the concentration of carbon contained in each species.
The carbon concentration is found by multiplying the carbon-containing species
concentration by the number of carbon atoms in the species. For example, for
ethyl mercaptan (CaHsSH), the species concentration is 0.21 mole percent of
CiHsSH in the gas. The carbon concentration is twice this value since there
C-8
-------
TABLE C.2-3. KOSOVO COAL PREPARATION SECTION FLEISSNER AUTOCLAVE
VENT FLOW RATE AND COMPOSITION DATA
Component
Value
Dry Gas Flow Rate (m3/gasifier hr at 25"C)
Molecular Weight of Dry Gas
Composition Data (Dry Basis)
Fixed Gases (vol *)
H2
02
CH4
CO
C02
Sulfur Species (ppmv)
H2S
COS
CH3SH
C2H5SH
Hydrocarbons (vol %)
C2H6
C2H4
C3's
C4's
C5's
Aromatic Species (ppmv)
Benzene
Toluene
Xylenes and EtJiylbenzene
Phenols
Nitrogen Species (ppmv)
NH3
HCN
57.8
33.4
Tr
14
56
Tr
Tr
29
2400
30
3400
2100
Tr
NF
0.03
0.03
NF
0.01
17
6.8
4.2
1 vol * = l.OE+04 ppmv
Tr m Trace, -0.01 vol % for fixed gases and -1 ppmv for all other species
NF = Not Found
- » No Data Available
C-9
-------
TABLE C.2-4. KOSOVO COAL PREPARATION SECTION FLEISSNER AUTOCLAVE
VENT CARBON CONTENT DATA
Species
CH4
CO
C02
CH3SH
C2H5SH
C2's (as C2H$)
C3's (as C3H8)
C4's (as C4Hio)
C5's (as C5H12)
Cg+ (as C
-------
are two carbon atoms in each ethyl mercaptan molecule. Summation of the indi-
vidual carbon concentrations in Table C.2-4 yields the autoclave vent gas total
carbon content of 30 g-atoms of carbon per 100 gmoles of gas.
It was assumed that the ideal gas lav was valid for all gaseous streams.
At the moderate (low pressure, usually low temperature) conditions encountered
in the Kosovo plant, errors introduced by this assumption should be well within
the experimental errors of gaseous stream flow rate and composition
measurements. Using the ideal gas law, the volumetric flow rate (m'/hr) given
in Table C.2-3 can be converted to a mass flow rate (kg/hr) using the following
formula:
I k« /1000 _
1000 g] I ' HMW) (2)
_
RTJ I 1000 g] I m'
where: M = mass flow in kg/gasif ier-hr
V = volumetric flow in m3/hr at Temperature T
P = pressure in atmospheres
R = gas constant = 0.0821 atm-
gmol-K
T = absolute temperature in K
MWg = molecular weight of the gas
For the autoclave vent, the mass flow rate found using Equation 2 is:
<57-8)((298)(0.0821) )(33'4) = 7-9E+01 kg/gasif ier-hr
For an ideal gas, the volumetric concentration of a species is the same as
the molar concentration (vol % = mole %) . Using this relationship, the mass
flow rate of a gaseous component can be calculated using the following
equation:
«.
% •» /
where: Mj = mass flow of component i in kg/gasifier-hr
YX = volumetric or molar concentration of component i
(g-atoms i/mole gas)
Mffi = molecular weight of component i
C-ll
-------
MWg = molecular weight of the total gas stream
Mg = mass flow rate of the total gas in kg/gasifier-hr
For example, the carbon mass flow rate of the autoclave vent gas can be found
from the total carbon concentration given in Table C.2-3 and the mass flow of
the total gas stream (calculated above) using Equation 3:
Autoclave Vent
Carbon Mass Flow
(0.30H12)
33.4
(7.9E+01) - 8.5E+00 kg/C gasifier-hr
The total autoclave vent sulfur mass flow rate is also calculated using
Equation 3. Sulfur species data are shown in Table C.2-5. The total sulfur
concentration given in Table C.2-5 is 0.79 g-atoms of sulfur per 100 gmoles of
gas. Therefore, using Equation 3, the sulfur mass flow in the autoclave vent
is:
Autoclave Vent
Sulfur Mass Flow
(0.0079)(32)
•33-^ L (7.9E+01) - 6.0E-01 kg S/gasifier-hr
The ratio of Na to Os given in Table C.2-3 for the autoclave vent is
80/21. This ratio is very close to the 79/21 Na/Oa ratio of air. Therefore,
molecular nitrogen data for the autoclave vent were not used in the nitrogen
species mass balance. Data were not available for NHs and HCN in the autoclave
vent; therefore, this stream was not included in the nitrogen balance mass flow
calculations.
TABLE C.2-5. KOSOVO COAL PREPARATION SECTION FLEISSNER
AUTOCLAVE VENT SULFUR CONTENT DATA
Species
Species Concentration
(mole %)*
Sulfur Concentration*
H2S
COS
CH3SH
C2H5SH
TOTAL
2.4
3.0
3.4
2.1
E-01
E-03
E-01
E-01
2.4
3.0
3.4
2.1
7.9
E-01
E-03
E-01
E-01
E-01
*See notes for Table 2-4.
C-12
-------
C3.0 MASS BALANCE CALCULATIONS FOR THE KOSOVO GAS PRODUCTION SECTION
Mass balances for carbon, sulfur, and nitrogen around the Kosovo Gas
Production section are shown in Table C.3-1. There are three key inlet and
eight key outlet streams in the Gas Production section. These streams are:
Inlet Streams:
• Dried Coal (from Coal Drying)
• Steam
• Oxygen
Outlet Streams:
• Crude Product Gas (to Rectisol)
• Gasifier Ash
• Gas Liquors (to Tar/Oil Separation)
• Coal Lock Bucket Vent Gas
• Low Pressure Coal Lock Vent Gas
• Gasifier Start-up Vent Gas
• Gas Liquor Tank Vent Gas
• Ash Cyclone Vent Gas
• High Pressure Coal Lock Vent Gas (to Flare System)
The gas liquor streams were not included in these calculations because
they were not analyzed during the test program. The coal lock bucket vent was
plugged during most of the test period. When this vent was plugged, the gas
normally vented at this point was discharged through the L.P. coal lock event.
Therefore, data for the coal lock bucket vent were not used. The gasifier
start-up vent was in operation only during the start-up sequence and was
likewise not included in these calculations.
The oxygen fed to the gasifiers normally contains about 96 vol % Oa and 4
vol % Na. The design flow rate of 2160 m3/gasif ier-hr at 25°C was verified
from process data to be representative of the oxygen input stream flow rate.
This flow ra.te was converted from volumetric units (m3/hr) to mass units
(kg/hr) using Equation 2:
(216° »'/to> (298) (.0821) (31'8) = 2'8E+03
C-13
-------
TABLE C.3-1. KOSOVO GAS PRODUCTIN SECTION MASS BALANCE RESULTS
Stream
All values in kg/gasiflet—hr
Total
Mass Flow
Carbon
Mass Flow
Sulfur
Mass Flow
Nitrogen
Mass Flow
Inlet Streams:
Dried Coal (s) (from Coal 1.6 E+04 7.1 E+03 1.4 E+02 1.7 E+02
Preparation)
Oxygen
TOTAL INLET
2.8 E+03
9.9 E+01
7.1 E+03 1.4 E+02 2.8 E+02
Outlet Streams;
Gasifier Ash (s)
Wastewater (aq)
Crude Product Gas (g) (to
Rectisol)
Dedusting Cyclone Vent (g)
L.P. Coal Lock Vent (g)
Gas Liquor Tank Vent (g)
Ash Lock Cyclone Vent (g)
H.P. Coal Lock Vent (g)
(to Flare System)
TOTAL OUTLET
2
2
1
8
2
4
4
2
.7
.6
.7
.4
.0
.5
.2
.3
E+03
E+03
E+04
E+03
E+01
E+01
E+01
E+02
4
5
6
5
2
1
.7
.7
.4
.9
.3
.6
E+01
-
E+03
*
E+00
E-01
E+00
E+02
2
5
1
3
8
3
1
.4
.0
.7
*
.7
.8
.5
.3
E+00
E-01
E+02
E-01
E-01
E-03
E+00
8
8
1
7
1
1
3
.1
.3
.4
*
.9
.9
.3
.9
E-01
E-03
E+02
E-02
E-02
E+01
E-01
5.9 E+03
1.7 E+02
1.5 E+02
Accountability (%)
83
123
55
* — Amounts are negligible in gaseous stream, particulate analysis not
available.
— =« Ho Data Available
(s) - solid stream
(g) - gaseous stream
(aq) — aqueous stream
C-14
-------
TABLE C.3-2. KOSOVO GAS PRODUCTION SECTION GASIFIER ASH DATA
Component
Value
Flow Rate (kg/gasifier-hr)
Ultimate Analysis (wt%)
Moisture
Ash
Carbon
Sulfur
Hydrogen
Nitrogen
Oxygen
Chlorine
2.7 E+03
2.05
93.5
1.74
0.15
0.25
0.03
2.3
0.04
The nitrogen mass flow rate was calculated using Equation 3:
Nitrogen Mass
Flow Rate in
Input Oxygen
(0.04)
28
31.8,
(2.8E+03 kg/hr) - 9.9E+01 kg N/hr
The calculations necessary to define the inputs associated with the dried
coal inlet stream were described in the Coal Drying section discussion. Table
C.3-2 shows the Ultimate Analysis data used for the gasifier ash calculations.
Also shown is the design flow rate of 2.7E+03 kg/gasifier-hr. Using the data
in Table C.3-2, Equation 1 was used to calculate the component (carbon, sulfur,
and nitrogen) flow rates in the gasifier ash discharge stream. The results are
shown in Table C.3-1.
Table C.3-3 shows composition and flow rate data for Gas Production sec-
tion gaseous outlet streams. The total carbon content of each vent is given in
Table C.3-4. As with the Coal Drying section gaseous streams, the concentra-
tion of carbon—containing species is converted to carbon concentration by
multiplying the carbon—containing species concentration by the number of carbon
atoms in the species molecule. Individual carbon concentrations a-re then
summed to yield the total stream carbon content. Gaseous stream flow rate data
C-15
-------
TABLE C.3-3.
FLOW RATE AND COMPOSITION DATA FOR KOSOVO GAS PRODUCTION
SECTION GASEOUS STREAMS
o
i
Dry Gas Flow Rite
(m3/gasifier-hr it 25»C)
Molecular Wt. of Dry Ga>
Composition (Dry Basis)
Flied Oases (vol %)
»2
02
N2
cm
CO
C02
Sulfur Species (ppnv)
II2S
COS
013 sd
C2IISSI1
Hydrocarbons (vol %)
C2II6
C2ll4
C3's
C4's
C5's
C6 +
Aromatic Species
(ppmv)
Benzene
Toluene
Xylene and Ethylbenzene
Phenols
Nitrogen Species (ppmv)
N1I3
IICN
Uedulting
Cyclone
Vent
7200
28.fi
NF
20.8
78.2
NF
NF
NF
NF
NF
NF
NF
NF
-
NF
NF
NF
NF
-
-
-
Tr
NF
NF
Low Pressure
Coal Lock Gas Liquor
Vent Tank Vent
21 44
23.5
37 11.8
0.27 13.8
0.18 55.6
8.6
14. 6 2.6
36.5
12.700 1450
110
420
220
0.22
Tr
0.14
0.05
Tr
0.12
760
220
75
5.7 Tr
2400 690
600
Ash Lock
Cyclone Vent
32.8
31.3
NF
48
35
Tr
NF
14
82
NF
NF
NF
Tr
Tr
Tr
Tr
-
NF
-
-
-
Tr
340
54
High Pressure
Coal Lock
(Flare Feed)
230
24.9
32
0.24
0.14
10.5
12
42
3500
120
460
210
0.42
Tr
0.25
0.11
0.01
0.08
550
100
38
2.5
NF
170
Crude
Product
Gas
18.800
21.9
38.1
0.36
0.64
11.5
15
32
6000
97
590
200
0.47
0.04
0.19
0.074
0.044
0.064
750
230
100
Tr
3.3
320
Tr = Trace. ~0.01 vol % for filed gases and -1 ppnv for all others
NF = Not Found, lets than a trace
- = No Data Available
-------
TABLE C.3-4. KOSOVO GAS PRODUCTION SECTION GASEOUS STREAM CARBON CONTENT DATA
Species
CH4
co
co2
cos
CH3SII
C2II5SII
C2"6
C2H4
C3's (as C3llg)
C4's (as C4II10)
Cj's (as C5Hj2)
C6+ (as C6D14)
C6«6
C7II8
CB»IO
Phenols (as C6H70)
HCN
TOTAL
Low Pressure
Coal Lock
Vent
8.6
15
37
0.011
0.042
0.044
0.44
Tr
0.42
0.20
Tr
0.72
0.46
0.15
0.060
0.003
0.06
• 62
Csrbon Content in >-atoms carbon per
Ash Lock
Gaa Liquor Cyclone
Tank Vent Vent
Tr
2.6 NF
14
-
NF
NF
Tr
Tr
Tr
Tr
-
NF
'
-
-
Tr Tr
0.005
2.6 14
100 moles of itai
High Pressure
Coal Lock
Vent
11
12
42
0.012
0.046
0.042
0.84
Tr
0.75
0.44
0.05
0.48
0.33
0.070
0.030
0.002
0.017
68
Crude
Product
Gas
12
15
32
0.0097
0.059
0.040
0.94
0.08
0.57
0.30
0.22
0.38
0.45
0.16
0.08
Tr
0.032
62
XT - Too*. -0.01 vol % for fixed |aies and ~1 ppsnr for all others
NF - Not Found, less than a trace
- - No Data Available
-------
were converted from volumetric units (m3/hr) to mass units (kg/hr) using Equa-
tion 2. An example of this calculation is given in Section C2.0. The calcula-
tions to convert carbon content to carbon mass flow rate for gaseous streams
were performed using Equation 3. Again, an example of these calculations is
given in Section C2.0.
Table C.3-5 shows the sulfur content data for the Gas Production section
gaseous streams. The sulfur mass flow rate for each stream was calculated
using Equation 3.
Nitrogen content data for gaseous streams are given in Table C.3-6. In
the Gas Production section, it is difficult to segregate molecular nitrogen
(Na) present due to air entrained during sampling from that actually generated
in the process. In the gas liquor tank vent gas the Na/Oa ratio in the analy-
sis is close to the 79/21 Na/Oa ratio for air. For this stream, molecular
nitrogen was not included in these calculations. For all other gaseous
streams, molecular nitrogen was included in the nitrogen mass balance
calculations.
The nitrogen mass flow rate for each stream is calculated from the data in
Table C.3-6 using Equation 3. For example, for the low pressure coal lock
vent, the nitrogen content is 0.66 g-atoms nitrogen per 100 moles of gas and
the nitrogen mass flow rate is:
L.P. Coal Lock Vent . (0,0066?(14,0) (2>OE+01) . 7<9E_02 kg N/gasifier-hr
Nitrogen Mass Flow 23.5
Table C.3-7 shows the computed mass flow rates of nitrogen in the gaseous
streams.
Data for the wastewater generated in the Gas Production section is shown
in Table C.3-8. The flow rate was converted from volumetric units (m3/hr) to
mass units (g/kr) using the following equation:
M - V.p (4)
where: M = mass flow (kg/gas ifier-hr)
V = volumetric flow (m3/hr)
p = density of the stream (kg/m3)
For the gas production wastewater, the density was assumed to be the density of
water at 30°C. Using this assumption and Equation 4, the mass flow rate is:
Wastewater / \ /
Mass = f 3.0 m3 \ (9.9645E+02 kg \ = 3.0E+03 kg/gasifier-hr
Flow Rate \ hr J \ m3 at 30«C 1
Since wastewater carbon data were not available for this stream, it was
not included in the carbon mass balance. Sulfur in the wastewater was found to
be primarily in the form of sulfate (SO.*-*). The conversion from mg of
sulfate/L to mass flow sulfur in kg/hr is found by the following:
C-18
-------
TABLE C.3-5. KOSOVO GAS PRODUCTION SECTION GASEOUS STREAM SULFUR CONTENT DATA
o
Species
H2S
COS
CH3SH
C2H5SH
TOTAL
Low Pressure
Coal Lock
Vent
1.3
0.011
0.042
0.022
1.4
Sulfur Content in g-atoms Sulfur
Ash Lock
Gas Liquor Cyclone
Tank Vent Vent
0.15 0.0082
-
-
-
0.15 0.0082
per 100 moles of gas
High Pressure
Coal Lock
Vent
0.35
0.012
0.046
0.021
0.43
Crude
Product
Gas
0.60
0.0097
0.059
0.020
0.69
- = No Data Available
-------
TABLE C.3-6. KOSOVO GAS PRODUCTOIN SECTION GASEOUS STREAM NITROGEN CONTENT DATA
Nitrogen
Low Pressure
Coal Lock
Species Vent
NH3 0.24
HCN 0.06
TOTAL . 0.30
(Excluding N2)
n
^, N2 0.36
o
TOTAL 0.66
(Including N2)
Content in g-atoms Nitrogen
Ash Lock
Gas Liquor Cyclone
Tank Vent Vent
0.069 0.034
0.0054
0.069 0.039
* 70.00
0.069 70.00
per 100 moles of gas
High Pressure
Coal Lock
Vent
-
0.017
0.017
0.28
0.30
Crude
Product
Gas
0.0002
0.032
0.032
1.3
1.3
*N2/02 ratio in Gas Liquor Tank Vent is 85/20. approximately the 79/21 N2/02 ratio of air;
• therefore, not included.
- = No Data Available
-------
TABLE C.3-7. NITROGEN MASS FLOW RATES IN KOSOVO GAS PRODUCTION
SECTION GASEOUS STREAMS
All values in kg/gasifier-hr
Stream
Excluding N2
(HCN + NH3 Only)
Including N2
(HCN + NH3
Low Pressure Coal Lock Vent
Gas Liquor Tank Vent*
Ash Lock Cyclone Vent
High Pressure Coal Lock Vent
Crude Product Gas
3.6 E-02
1.9 E-02
7.4 E-03
2.2 E-02
3.5 E+03
7.9 E-02
1.9 E-02
1.3 E+01
3.9 E-01
1.4 E+02
*See note for Table C.3-6.
C-21
-------
TABLE C.3-8. FLOW RATE AND COMPOSITION DATA FOR KOSOVO GAS
PRODUCTION SECTION WASTEWATER
Component
Value
Flow Rate (m3/gasifier-hr)
Aqueous Composition Data (mg/L)
Total Phenols
b
Volatile Phenols
Free Ammonia
Fized Ammonia
Cyanide
Nitrites
Nitrates
Pyridines
Chlorides
Fluorides
Sulfites
Sulfates
Sulfides
Thiocyanates
Thiosulfates
3.0
0.17
Tr
1.9
0.01
0.40
4.8
28
0.91
Tr
495
Tr
0.26
Tr
Tr = Trace, <1.0 mg/L
- = No Data Available
C-22
-------
where: Ms = mass flow sulfur in kg/gasifier-hr
Cs(>4-» = concentration of S04"a in mg/L
MWS, MWS04~* = molecular weights of sulfur and
sulfate, respectively
V = volumetric total stream flow in m3/hr
For the wastewater, this calculation is:
Wastewater / . , \/\/\\
Sulfur - (495 me S04-* \ f 32e S/emole S \ I 1 g/mM /1 kg ] /3 m3
Mass Flow \ L 7 I 96S S04/gmole S04-*) \ mg/L } \1000 gJ \"hr"
/* ' \ ' \ '. \ >
» 5.0E-01 kg S/gasifier-hr
Nitrogen—containing species in the gas production wastewater are shown in
Table C.3-9. The conversion from mg N/L to kg/hr is similar to the sulfur
conversion (Equation 5). The nitrogen conversion is:
where: MN = mass flow of nitrogen in kg/gasifier-hr
CN = concentration of nitrogen in mg/L
V = total volumetric stream flow in m3/hr
Using the data in Table C.3-9, the wastewater nitrogen mass flow is:
Wastewater , \ / . . \ / > \
Nitrogen = 2.77 meN ) [1 g/m3 ] / 1 kg ] 3 m3 \
Mass Flow \ L / \ m8/L / \1000 g/ I hr /
\ / \ / \ / \ /
The accountabilities given in Table C.3-1 were calculated using Equation 7:
« » ^ ^.,. S Outlet Streams --_„ ,_»
% Accountability = frr^ S 100% (7)
2 Inlet Streams
C-23
-------
TABLE C.3-9. NITROGEN-CONTAINING SPECIES IN KOSOVO GAS
PRODUCTION SECTION WASTEWATER
Component Nitrogen
Concentration Concentration
Component mg/L mg/L
NH3 1.9 1.56
HCN 0.01 0.005
Nitrites (as N02~) 0.40 0.12
Nitrates (as N03~) 4.8 1.08
TOTAL 2.77
For example, for carbon species in the gas production section, the mass flow of
carbon leaving the section is:
Stream Carbon Mass Flow (kg/hr)
Crude Product 5.7 E+03
Gasifier Ash 4.7 E+01
Wastewater ?
L.P. Coal Lock Vent 6.4 E+00
Gas Liquor Tank Vent 1.6 E+03
Ash Lock Cyclone Vent 2.3 E+00
H.P. Coal Lock Vent 1.6 E+02
TOTAL 5.9 E+03
The total inlet carbon mass flow rate is:
Stream Carbon Mass Flow (kg/hr)
Dried Coal 7.1 E+03
Steam *
Oryg en *
TOTAL 7.1 E+03
•Assumed to be zero.
C-24
-------
Then using Equation 10, the accountability is:
% Accountability of
Carbon in Gas Production = 5.93 E+03 kz/hr 100%
Section 7.12 E+03 kg/hr
- 83%
As Table C.3-1 shows, the accountability of nitrogen in the Gas Pro-
duction section is low. This poor accountability is probably the result of two
major factors:
• the difficulties associated with accounting for molecular
nitrogen generation in the gasifier (as discussed above) and,
• a significant portion of the unaccounted nitrogen may be leav-
ing this section in the gas liquors sent to the Tar/Oil Separa-
tion section (as ammonia or cyanide ions).
C4.0 MASS BALANCE CALCULATIONS FOR THE KOSOVO RECTISOL SECTION
Mass balance calculations for the Kosovo Rectisol section were per-
formed for carbon, nitrogen, and sulfur. The results are shown in Table C.4-1.
The major inlet and outlet streams in the Rectisol section include:
Inlet Streams;
• Crude Product Gas (from Gas Production)
Outlet Streams;
• Clean Product Gas
• By-Product Naphtha (to By-Product Storage)
• Gas Liquor (to Medium Oil Separator in Tar/Oil Separation)
• Cyanic Water (to Tar/Oil Separation)
• HaS-Rich Waste Gas (to Flare System)
• COa-Rich Waste Gas
The gas liquor was not sampled during the test program, so it was not
included in these calculations.
Table C.4-2 shows the flow rate and composition data for the by-product
naphtha stream. Data for carbon, sulfur, and nitrogen were converted from con-
centration (wt %) to mass flow rate (kg/hr) using Equation 1. Cyanic water
data are shown in Table C.4-3. Only a partial analysis was performed on this
C-25
-------
TABLE C.4-1. KOSOVO RECTISOL SECTION MASS BALANCE RESULTS
Stream
All values in kg/gasifier-hr
Total Carbon Sulfur Nitrogen
Mass Flow Mass Flow Mass Flow Mass Flow
Inlet Streams;
Crude Product Gas (g)
(from Gas Production)
TOTAL INLET
1.7 E+04 5.7 E+03 1.7 E+02 1.4 E+02
5.7 E+03 1.7 E+02 1.4 E+02
Outlet Streams;
By-Product Naphtha (ol)
(to By-Product Storage)
Cyanic Water (aq) (to
Tar/Oil Separation)
Clean Product Gas (g)
H2S-Rich Waste Gas (g)
(to Flare System)
C02-Rich Waste Gas (g)
TOTAL OUTLET
1.3 E+02 1.1 E+02 2.8 E+00 2.3 E-01
6.2 E+02
4.8 E-02
4.6 E+03 2.1 E+03 4.3 E-02 4.7 E+01
6.3 E+03 1.8 E+03 2.3 E+02 4.9 E+00
6.2 E+03 1.8 E+03 5.4 E-01 3.7 E-02
5.7 E+03 2.3 E+02 5.2 E+01
Accountability (%)
100
137
37
- = No Data Available
(g) - gaseous stream
(ol) - organic liquid stream
(aq) - aqueous stream
C-26
-------
TABLE C.4-2. KOSOVO RECTISOL SECTION BY-PRODUCT NAPHTHA STREAM DATA
Component Value
Flow Rate (kg/gasifier-hr) 1.3 E+02
Ultimate Analysis (wt%)
Carbon 85.7
Hydrogen 9.9
Nitrogen 0.18
Sulfur 2.15
Oxygen 2.15
TABLE C.4-3. KOSOVO RECTISOL SECTION CYANIC WATER STREAM DATA
Component Value
Flow Rate (m3/gasifier-hr) 0.8
Temperature (°C) 80
Sulfur Content (mg/L) 60
C-27
-------
stream. The flow rate for cyanic water was converted'from volumetric units
(m3/hr) to mass units (kg/hr) using Equation 4.
Gaseous stream data are given in Table C.4-4. The gaseous stream flow
rates were converted from volumetric units (ms/hr) to mass units (kg/hr) using
Equation 2. Carbon content data in Rectisol section gaseous streams are shown
in Table C.4-5. .The total carbon content for each gaseous stream was used to
calculate the carbon mass flow with Equation 3. Sulfur and nitrogen data are
given in Tables C.4-6 and C.4-7 respectively. These data were converted to
mass flow using Equation 3.
In Section C3.0, it was noted that it was not possible, with the data
available, to segregate the Na due to air entrained during sampling from that
due to conversion of bound—nitrogen species in the gasifier or entering with
the oxygen fed to the gasifiers. Since the inlet crude product gas comes from
the Gas Production section, the same problem occurs in evaluating Rectisol gas-
eous streams. The results shown in Table C.4-1 include Nz. When Nz is not
included, the accountability of nitrogen in Rectisol increases from 37 to 150%
(as calculated using Equation 7). However, no nitrogen data was available fox
the cyanic water stream, which should contain a significant amount of HCN and
NHs. Table C.4-8 shows the nitrogen mass.flow rates for all Rectisol gaseous
streams with and without Nz included. The results from these Rectisol
calculations indicate that at least a portion of the fixed nitrogen in the
crude product gas was generated or entrained during the gasification process.
C5.0 MASS BALANCE CALCULATIONS FOR THE KOSOVO PHENOSOLVAN SECTION
Carbon, sulfur, and nitrogen mass balance calculations were performed for
the Phenosolvan section. The results are shown in Table C.5-1. Major inlet
and outlet streams in the Phenosolvan section include:
Inlet Streams;
• Phenolic Inlet Water (from Tar/Oil Separation)
• Steam Condensate
Outlet Streams;
• Wastewater
• Filter Backflush Water (to Tar Separators in the Tar/Oil
Separation Section)
• Crude Phenol (to By-Product Storage)
• By—Product Ammonia (to By—Product Storage)
• Unclean Oil (to By-Product Storage)
C-28
-------
TABLE C.4-4. KOSOVO RECTISOL SECTION GASEOUS STREAM DATA
Dry Gas Flow Rate
(m3/gasifier-hr at 25°C)
Molecular Wt. of Dry Gas
Composition (Dry Basis)
Fixed Gases (vol %)
H2
02
N2
CH4
CO
C02
Sulfur Species (pprav)
H2S
COS
CH3SH
C2H5SH
Hydrocarbons (vol %)
C2H6
C2H4
C3's
C4's
C5's
C6+
Aromatic Species (ppmv)
Benzene
Toluene
Xylene and Ethylbenzene
Phenols
Nitrogen Species (ppmv)
NH3
HCN
HjS-Rich
Waste Gas
(Flare Feed)
3,600
43.0
0.11
Tr
Tr
4.3
1.1
88
45,400
420
2.100
780
0.82
Tr
0.63
0.32
0.04
0.21
110
8
NF
Tr
2,200
200
C02-Rich
Waste Gas
Vent
3,600
42.2
Tr
Tr
Tr
1.2
Tr
94
39
62
8.5
4.4
1.6
Tr
0.28
Tr
Tr
NF
1.0
Tr
Tr
NF
4.6
13
Crude
Product
Gas
18,000
21.9
38.1
0.36
0.64
11.5
15
32
6,000
97
590
200
0.47
0.04
•0.19
0.074
0.044
0.064
750
230
100
Tr
3.3
320
Clean
Product
Gas
10,900
10.3
60
0.44
0.38
16
22
0.02
NF
0.17
1.1
1.0
0.15
Tr
Tr
Tr
Tr
0.03
-
-
-
Tr
Tr
Tr » Trace, -0.01 vol % for fixed gases and ~1 ppmv for all others
NF = Not Found, less than a trace
- = No Data Available
C-29
-------
TABLE C.4-5. KOSOVO RECTISOL SECTION GASEOUS STREAM CARBON CONTENT DATA
Species
CH4
CO
C02
COS
CH3SH
C2H5SH
C2H6
C2H4
Ca's (as CsHg)
C4's (as C4Hio)
Cf's (as C5Hi2)
Cg+ (as CgHi4>
C6H6
C7H8
C8HiO
Phenols (as Cg^O!
HCN
TOTAL
Carbon Content
Waste
Gas
4.3
1.1
88
0.042
0.21
0.156
1.64
Tr
1.89
1.28
0.20
1.26
0.066
0.006
-
H) Tr
0.020
100
in s~atons Carbon
C02-Rich
Waste
Gas
1.2
Tr
94
0.0062
0.0009
0.0009
3.20
Tr
0.84
Tr
Tr
-
0.0006
Tr
Tr
-
0T0013
99
oer 100 moles
Crude
Product
Gas
11.5
15
32.3
0.0097
0.059
0.040
0.94
0.08
0.57
0.296
0.22
0.384
0.45
0.161
0.08
Tr
0.032
62
of
Clean
Product
Gas
16
22
0.02
Tr
Tr
Tr
0.30
Tr
Tr
Tr
Tr
0.18
-
-
-
Tr
39
Tr = Trace, ~ 0.01 g-atoms for fixed gases,
- = No Data Available
~ 0.0001 for all others
C-30
-------
TABLE C.4-6. KOSOVO BECTISOL SECTION GASEOUS STREAM SULFUR CONTENT
Species
H2S
COS
CHsSH
C2H5SH
TOTAL
- = No Data
Tr = Trace,
TABLE C.4-7
Sulfur Content
H2S-Rich
Waste
Gas
4.54
0.042
0.21
0.078
4.87
Available
-0.0001 g-atoms
in g— atoms Sulfur uer 100
C02-Rich
Waste
Gas
0.0039
0.0062
0.0009
0.0004
0.0114
. KOSOVO RECTISOL SECTION GASEOUS
Nitrogen Content in g— atoms
Species
NH3
HCN
N2
TOTAL
H2S-Rich
Waste
Gas
0.22
0.02
Tr
0.24
C02-Rich
Waste
Gas
0.0005
0.0013
Tr
0.0018
Crude
Product
Gas
0.60
0.0097
0.059
0.020
0.689
STREAM NITROGEN
Nitrogen oer 100
Crude
Product
Gas
0.0002
0.032
1.3*
1.3
moles of eas
Clean
Product
Gas
-
Tr
Tr
Tr
0.0003
CONTENT DATA
moles of gas
Clean
Product
Gas
-
-
0.76*
0.76
*See discussion in Section C2.0 on N2 in Gas Production Section Streams.
- = No Data Available
Tr = Trace, ~0.0001 g-atoms
C-31
-------
TABLE C.4-8. NITROGEN MASS FLOW RATES IN KOSOVO RECTISOL
SECTION GASEOUS STREAMS
Stream
All values in kg/gasifier—hr
Excluding N2 Including N2
(HCN + NHs Only) (HCN + NHs +
H2S-Rich Waste Gas
C02~Rich Waste Gas
Crude Product Gas
Clean Product Gas
4.9 E+00
3.7 E-02
3.5 E+00
4.9 E+00
3.7 E-02
1.4 E+02
4.7 E+01
- « No Data Available
C-32
-------
TABLE C.5-1. KOSOVO PHENOSOLVAN SECTION MASS BALANCE RESULTS
All values in kg/gasifier—hr
Stream
Total Carbon Sulfur Nitrogen
Mass Flow Mass Flow Mass Flow Mass Flow
Inlet Streams:
Phenolic Inlet Water (aq)
(from Tar/Oil Separation)
TOTAL INLET
Outlet Streams;
Wastewater (aq)
Crude Phenol (ol) (to
By-Product Storage)
Unclean Oil (ol) (to
By-Product Storage)
1.3 E+04 6.5 E+01
6.5 E+01
* - Excluding molecular Nitrogen (N2)
- = No Data Available
(g) - gaseous stream
(ol) - organic liquid stream
(aq) - aqueous stream
4.1 E+01
4.1 E+01
1.3 E+04 1.9 E+01 1.1 E+00 2.2 E+00
9.0 E+01 -
3.0 E+01 2.5 E+01 2.5 E-01 3.0 E-01
Degassing Cyclone Vent (g)
Ammonia Stripper Vent (g)
Cooler Vent (g)
2nd Degassing Vent (g)
Crude Phenol Tank Vent (g)
DIPE Tank Vent (g)
TOTAL OUTLET
Accountability (%)
2
3
5
5
2
6
.6
.5
.9
.2
.3
.5
E+00 6.0 E-03
E+02 7.6 E+01 6.8 E+00
E+00
E-01
E-01 2.6 E-05 4.7 E-05
E-01 - -
1.2 E+03 8.1 E+00
180
1
6
1
5
1
6
.0
.3
—
.8
.3
.6
.3
E-03*
E+01
E-02
E-06*
E-05*
E+01
155
C-33
-------
• Degassing Cyclone Vent Gas
• Gas Tank Vent Gas
• Unclean Oil Tank Vent Gas
• Phenolic Water Tank Vent Gas
• Ammonia Stripper (First Degassing) Vent Gas
• Cooler Vent Gas
• Second Degassing Vent Gas
• Slop Tank Vent Gas
• Crude Phenol Tank Vent Gas
• Diisopropyl Ether (DIPE) Tank Vent Gas
Inlet steam condensate was not included in these calculations. It is
assumed that any contaminants in the steam are small compared to the inlet
phenolic water. During the test program, by-product ammonia was not being col-
lected, but was being discharged with the ammonia stripper vent gas.
Therefore, the by-product ammonia stream was not included. No data was
available for the filter backflush or the crude phenol streams. Therefore,
these streams were not considered either.
While no analysis of the unclean oil was available, it was assumed that
the composition of the unclean oil was the same as the composition of the
medium oil by-product. Table C.5-2 presents data for the unclean oil. The
concentration data shown (medium oil concentration data) were converted to mass
flows using Equation 1.
Aqueous stream data for the inlet phenolic water and the Phenosolvan
wastewater are given in Table C.5-3. The total organic carbon (TOO values
shown in Table C.5-3 were converted from concentration (mg/L) to carbon mass
flow rate (kg/hr) using the following:
where: MC = mass flow of carbon in kg/gasifier-hr
Cc = concentration of carbon in mg/L
V - volumetric stream flow rate in ms/hr
C-34
-------
TABLE C.5-2. KOSOVO PHENOSOLVAN SECTION UNCLEAN OIL DATA
Component
Value
Flow Rate (kg/gasifier-hr)
Ultimate Analysis of Medium Oil (wt %)
Carbon
Hydrogen
Nitrogen
Sulfur
Ash
Oxygen (by Difference)
3.0 E+01
81.8
8.94
1.00
0.83
0.03
8.2
C-35
-------
TABLE C.5-3, KOSOVO PHENOSOLVAN SECTION AQUEOUS STREAM DATA
Component
Inlet Water
Wastewater
Flow Rate (m^/gasifier-hr)
PH
Temperature (°C)
9.2
60
13
9.6
33
Aaueous Composition Data (me/1)
TOC
Total Phenols
Volatile Phenols
Free Ammonia
Fixed Ammonia
Cyanide
Nitrites
Nitrates
Chlorides
Fluorides
Total Sulfur
Sulfites
Sulfates
Sulfides
Thiocyanates
Thiosulf ates
Pyridine
Methylpyridine ' s
Dimethyl- and Ethylpyri dines
Alky Ipyri dines (as ethylpyridine)
Quinoline
Alky Iquino lines (as ethylquinoline)
4970
2120
-
3510
250
<1
-
<1
-
-
-
-
- -
-
75
-
28
42
46
26
5
12
1470
230
130
Tr
205
0.019
Tr
11.4
60
Tr
84
. -
-
-
3.1
Tr
-
-
-
—
-
"'
Tr = Trace, <1 mg/L for Free Nlfy, Thiosulfate, <0.05 for Fluorides,
<0,01 for Nitrite
- = No Data Available
C-36
-------
For the inlet water, the carbon mass flow is:
Inlet Water / \ /
Carbon Mass = (4970 meC\ /I g/mM / 1 kg
Flow Rate \ L / \ mg/L J I 1000 g 1 hr
= 6.5 E+01 kg/gasifier-hr
The total sulfur concentration in the wastewater is shown in Table 5-3.
This value was converted to sulfur mass flow (kg/hr) using the following:
M, = CS t1 ^VL*8 \ V
s r mg/L JQ.UUU g I
where: Ms = mass flow of sulfur in kg/gasifier-hr
Cs = concentration of sulfur in mg/L
V = volumetric stream flow rate in m3/gasif ier-hr
For the wastewater then, the sulfur mass flow is:
Wastewater = / 84 me S\ /I gmA / 1 kg \ /13 m» \
Sulfur Mass Flow 1 L J I mg/LJ 1 1000 g 1 I hr )
= 1.1 E+00 kg/gasifier=hr
Sulfur data were not available for the inlet water. Therefore, the sulfur mass
balance around the Phenosolvan section is incomplete.
Table C.5-4 shows nitrogen content data for the Phenosolvan aqueous
streams. The concentration data shown were converted to mass flow using
Equation 6 .
Gaseous stream data for the Phenosolvan section are shown in Table C.5-5.
Flow rate data were not available for the gas tank vent, unclean oil tank vent,
phenolic water tank vent, or slop tank vent so these streams were not included
in the mass balance calculations. Carbon content data for gaseous streams are
given in Table C.5-6. Flow rate and carbon species data were only available
for the ammonia stripper vent and crude phenol tank vent streams. The calcula-
tions to obtain carbon mass flow from the concentration data in Table C.5-6
were performed using Equation 3.
Sulfur concentration data for Phenosolvan gaseous streams are given in
Table C.5-7. Three streams were analyzed for both flow rate and sulfur-
containing species. These are the degassing cyclone vent, ammonia stripper
vent, and crude phenol tank vent. Table C.5-8 shows nitrogen concentration
data for the Phenosolvan gaseous streams. Most of the gaseous streams in this
section were analyzed for NHs . In all cases except the ammonia stripper vent,
the Na/Oa ratio for the gaseous data in Table C.5-5 is near the 79/21 Na/Oa
C-37
-------
TABLE C.5-4. KOSOVO PHENOSOLVAN SECTION AQUEOUS STREAM
NITROGEN CONTENT DATA
Species
Nitrogen Content in mg N/L
Inlet Water Wastewater
NH3
Nitrites (as
Nitrates (as
Thiocyanates (as CNS)
Pyridine
Methylpyridine' s
Dimethyl- and Ethylpyridine
Alkylpyridines (as
Qninoline
Alkylquinolines (as
TOTAL
3096
Tr
Tr
18
5
6
6
3
0.5
3140
169
0.01
Tr
2.6
0.75
170
C-38
-------
TABLE C.5-5. KOSOVO PHENOSOLVAN SECTION GASEOUS STREAM DATA
O
I
OJ
v£>
Dry Gas Flow Rate
(m'/gasifier-hr it 25*C)
Molecular Wt. of Dry Gas
Composition (Dry Basis)
Filed Gases (vol %)
112
02
N2
CII4
CO
C02
Sulfur Species (ppmv)
112 S
COS
CI13SI1
C2II5SH
Hydrocarbons (vol %)
C2's
C3's
C4's
C5's
C6 +
Aromatic Species (ppmv)
Benzene
Toluene
Xylene and Ethylbenzeno
Phenols
Nitrogen Species (ppmv)
Nil 3
I1CN
Tr - Trace, -0.01 vol * for
Degassing Ammonia
Cyclone Stripper Cooler
Vent Vent Vent
2.2 260 4.4
32.7
NF -
-
-
Tr
NF -
55
2100 19.500 NF
NF -
290
100
Tr -
Tr -
Tr
Tr -
NF
Tr
-
Tr
NF «,200 Tr
790 418.000 82.000
4.800
fixed gases and ~1 ppmv for all others
2nd
Degassing
Vent
0.44
-
NF
21
78
-
' NF
-
NF
-
-
-
-
-
-
-
-
-
_
_
NF
200
-
Crude Phenol
Tank
Vent
0.20
28.0
NF
20
77
Tr
NF
NF
180
NF
NF
NF
Tr
Tr
Tr
Tr
NF
_
_
_
22
22
34
DU'B
Tank
Vent
0.55
-
NF
21
79
-
NF
-
NF
_
-
_
_
-
-
-
-
_
_
_
Tr
51
-
- = No Data Available
-------
TABLE C.5-6. KOSOVO PHENOSOLVAN SECTION GASEOUS STREAM
CABBON CONTENT DATA
Species
CH4
CO
C02
COS
CH3SH
C2H5SH
C2's (as C2H6)
GS'S (as CsHg)
C4's (as C4H10)
C5's (as C5H12)
C6+ (as C6H14)
C6H6
C7H8
CgHio
Phenols (as CglfrjO)
HCN
TOTAL
Tr = Trace, ~0.01 vol
all others
NF = Not Found, less
Carbon Content in a— atoms
Ammonia
Stripper
Vent
Tr
NF
55
NF
0.029
0.010
Tr
Tr
Tr
Tr
NF
Tr
-
Tr
3.72
0.48
59
% for CH4, CO, C02 and -1
than a trace
Carbon per 100 moles of gas
Crude Phenol
Tank Vent
Tr
NF
NF
-
-
-
Tr
Tr
Tr
Tr
NF
-
-
-
0.013
0.0034
0.027
ppmv (10~4 vol %) for
- = No Data Available
-------
TABLE C.5-7. KOSOVO PHENOSOLVAN SECTION GASEOUS STREAM
SULFUR CONTENT DATA
Species
H2S
COS
CH3SH
f /% TT j* CTT
^2« i Oil
TOTAL
Sulfur Content
Degassing
Cyclone
Vent
0.210
-
-
_Z
0.210
in a-atoms Sulfur
Ammonia
Stripper
Vent
1.95
NF
0.029
0.01
1.99
oer 100 moles of eas
Crude Phenol
Tank
Vent
0.018
-
-
~
0.018
NF = Not Found
- = No Data Available
TABLE C.5-8 KOSOVO PHENOSOLVAN SECTION GASEOUS STREAM
' . BOUND-NITROGEN CONTENT DATA
Species
Nitrogen Content in g-atoms Nitrogen per 100 moles of zas ,
Degassing Ammonia 2nd
Cyclone Stripper Cooler Degassing Crude Phenol DIPE
Vent Vent Vent Vent Tank Vent Tank Vent
HCN
0.079 41.8 8.2 0.02
_T 0.48 - -
0.0012
0.0034
0.0051
TOTAL 0.079
42
8.2
0.02
0.0046
0.0051
No Data Available
C-41
-------
ratio of air. Therefore, Na was not included in these calculations. Sulfur
and nitrogen concentration data were converted to mass flow using Equation 3.
C6.0 KOSOVO FLARE SYSTEM CALCULATIONS
In the Phase II test program both the combined gas to flare (Stream 20.1)
and the individual flare streams (3.6, 7.1, and 13.6) were analyzed. The
combined gas to flare was analyzed to study the stream being combusted in the
flare. Each of the individual flare feed streams were analyzed so that
information about the individual process units could be obtained. The results
obtained for these streams can be used to gain insight into the consistency of
these independently determined measurements of waste gases to the flare.
The high pressure coal lock vent is an intermittent stream. The flow rate
given for this stream is a time-phased average rate for an entire gasifier
cycle. The combined gas-to-flare stream flow rate is also a time-phased
average.
Mass balance results are shown in Table C.6-1. The conversion from
volumetric concentration to mass flow was performed using Equation 3. Flow
rate data were converted to mass flow (kg/hr) using Equation 2. As Table C.6-1
indicates, on a mass basis, the agreement between the individual stream
analyses and the combined gas analysis is not very good. This difference is
probably due to the fluctuation in the mass flow rates. Flow rate measurements
being used in these mass balance calculations were performed on different days
for each stream. Therefore, operational fluctuations at that time probably af-
fected the results.
A more meaningful comparison is provided in Table C.6-2. In In this
table, the component mass rate data' in Table C.6-1 have been summed for the
three individual flare feed streams and converted to concentration data using
the total mass flow rate for three streams. The formula to convert from com-
ponent mass flow to concentration is:
where: Ci = concentration of component i in vol%
MI = mass flow of i in kg/hr
JfT = mass flow of total gas in kg/hr
molecular weight of total gas
molecular weight of i.
C-42
-------
TABLE C.6.1. KOSOVO FLARE SYSTEM COMPARISON OF RESULTS (MASS BASIS)
o
ifier-hr
T.r
Component
Total Dry Gas
Flow Rate
»2
02
N2
CIM
CO
C02
I12S
COS
CH3S1I
C2II5SH
C2H6
C21I4
C3's
C4's
C5's
C6+
C6H6
C?ll6
C8»10
Phenols
N1I3
II CN
•Accountability
H.P.
Lock
2.3
£.0
7.2
3.7
1.6
3.2
1.7
1.1
C.8
2.1
1.2
1.2
2.6
1.0
6.0
6.8
6.5
4.0
8.7
3.8
2.2
NF
4.3
„ Combined fias
Coal
Vent
E+02
E+00
E-01
E-01
E+01
E+01
E+02
E+00
E-02
E-01
E-01
E+00
E-04
E+00
E-01
E-02
E-01
E-01
E-02
E-02
E-03
E-02
to Flare
H2S-Rich
Waste Cat
6.3
3.3
4.7
4.1
1.0
4.5
5.7
2.3
3.7
1.5
7.1
3.6
4.1
4.1
2.7
4.2
2.7
1.3
1.1
E+03
E-01
E-01
E-01
E+02
E+01
E+03
E+02
E+00
E+01
E+00
E+01
E-03
E+01
E+01
E+00
E+01
E+00
E-01
NF
NF
5.5
7.9
100%
E+00
E-01
Separation
Watte Gaa
6.2
3.5
5.1
4.5
9.0
4.9
. 5.5
4.9
1.2
1.9
1.6
1.6
4.5
2.9
3.8
1.0
1.8
1.2
1.8
l.t
6.3
5.3
2.8
E+00
E-02
E-04
E-04
E-02
E-02
E+00
E-02
E-03
E-02
E-02
E-02
E-06
E-02
E-02
E-02
E-01
E-01
E-02
E-03
E-05
E-02
E-04
Total Sum
6.6
6.4
1.2
1.1
1.2
7.7
5.9
2.3
3.8
1.5
7.3
3.7
4.4
4.2
2.8
4.3
2.7
1.8
2.1
4.1
2.3
5.6
8.4
E+03
E+00
E+00
E+00
E+02
E+01
E+03
E+02
E+00
E+01
E+00
E+01
E-03
E+01
E+01
E+00
E+01
E+00
E-01
E-02
E-03
E+00
E-01
Combined Gaa
to Flare
2.3
1.1
1.7
3.2
5.4
2.9
2.1
2.0
8.2
6.5
6.4
1.2
1.5
1.6
1.0
1.6
4.7
2.7
1.1
1.9
5.1
1.5
E+03
E-02
E+00
E+00
E+01
E+01
E+03
E+01
E-01
E+00
E-01
E+01
E-03
E+01
E+01
E+00
E+00
E+00
E+00
E-01
E-03
NF
E-01
Accountability*
%
35
0.17
150
280
47
38
36
7.1
22
44
8.8
32
35
38
36
36
17
150
510
470
230
-
18
Total Sum
NF - Not Found
-------
TABLE C.6-2.
KOSOVO FLARE SYSTEM COMBINED GAS COMPOSITION
COMPARISON OF RESULTS
Species
Calculated*
Measured
Flow Rate (m^/gasifier-hr at 25°C)
Composition (Dry Basis)
3,870
1.330
Fixed Gases (vol %)
H2
02
N2
CH4
CO
C02
Sulfur Species (ppmv)
H2S
COS
CHsSH
C2H5SH
Hydrocarbons (vol %)
C2H6
C2H4
C3's
C4's
C5's
C6+
Aromatic Species (ppmv)
Benzene
Toluene
Xylenes and Ethylbenzene
Phenols
Nitrogen Species (ppmv)
NH
HCN
2.1
0.02
0.03
4.6
1.8
85
42,700
400
2,000
7SO
0.79
Tr
0.50
0.31
0.04
0.20
150
15
2.4
Tr
2,100
200
Tr
0.10
0.21
6.2
1.9
88
10,600
250
2,500
190
0.74
Tr
0.66
0.32
0.04
0.10
640
215
33
Tr
NF
100
•Calculated using Equation 10 from 'Total Sum' column data on Table 6-1.
Tr » Trace. -0.01 vol. % for fixed gases, -1 ppmv for all other species.
C-44
-------
For example, for COa, the total mass flow of COs in the high pressure coal lock
vent gas (1.7 E+02 kg/hr), HaS-rich waste gas (5.7 E+03 kg/hr). and tar
separation waste gas (5.5 E+00 kg/hr) is 5.9 E+03 kg/hr. The conversion to
concentration is:
Examination of the results shown in Table C.6-2 indicates that, for most
species, the concentration data derived from the individual stream data
correlate well with the data derived from measurement of the combined gas to
flare.
C7.0 OVERALL (PLANT-WIDE) KOSOVO MASS BALANCE CALCULATIONS
Overall (plant-wide) mass balances were developed for carbon, sulfur, and
nitrogen. The major inlet and outlet streams considered in performing the
calculations necessary to arrive at overall mass balances are shown in Table
C.7-1. The results from the overall mass balances are shown in Table C.7-2.
Most of the streams shown in Table C.7-1 were discussed in the individual
plant section mass balance sections (C2.0 through C6.0). In this section, only
those streams not discussed previously will be dealt with in detail. As in the
plant section balances, it was assumed that the carbon, nitrogen, and sulfur
entering the system in the steam stream is small compared to the amounts in the
entering coal and oxygen streams. It was also assumed that the amount of
methanol and DIPE not recovered for the stripping processes in which they are
used (makeup requirements) is small. No data was available to verify this
assumption as measurement of these streams was beyond the scope of the test
program.
The two sections which have not been discussed previously are Tar/Oil
Separation and By-Product Storage. One solid stream is generated in these sec-
tions. Data for that stream, heavy tar, are shown in Table C.7-3. Also shown
in Table C.7-3 are data for the by-products which leave the By-Product Storage
section: light tar, medium oil, and naphtha. For the unclean oil, the medium
oil analysis was used. No data were available for the crude phenol, so it was
not included in this balance. By-product ammonia was not being collected
during the test program so it was also excluded. The heavy tar and by-products
concentration data shown in Table C.7—3 were converted to component (carbon,
nitrogen, and sulfur) mass flow rates using Equation 1.
Gaseous stream data for the Tar/Oil Separation and By-Product Storage
sections are shown in Table C.7-4. Flow rate data were not available for the
unpure tar tank and unpure oil tank so they were not included in this balance.
Carbon content data for gaseous streams in the Tar/Oil Separation and By-
Product Storage sections are given in Table C.7-5. The calculations to convert
the concentration data given in Table C.7-5 to carbon mass flow rates were
performed using Equation 3.
C-45
-------
TABLE C.7-1. INLET AND OUTLET STREAMS USED IN OVERALL
MASS BALANCE CALCULATIONS
Plant Section
Stream Description
State
Inlet Streams
Coal Preparation
Gas Production
Outlet Streams
Coal Preparation
Gas Production
Rectisol
Tar/Oil Separation
'Run-of-Mine' Coal
Steam
Oxygen
Fleissner Condensate
Feissner Autoclave Vent Gas
Condensate Tank Vent Gas
Gasifier Ash
Gas Production Wastewater
Dedusting Cyclone Vent Gas
LOT Pressure Coal Lock Vent
Gas
Ash Cylcone Vent Gas
Clean Product Gas
C02-Rich Waste Gas
Heavy Tar
Tar Tank Vent Gas
Medium Oil Tank Vent Gas
Condensate Tank Vent Gas
Phenolic Water Tank Vent Gas
g
g
aq
g
g
s
aq
g
g
g
g
g
s
g
g
g
g
(Continued)
C-46
-------
TABLE C.7-1. (Continued)
Plant Section
Stream Description
State
Outlet Streams
Phenosolvan
By-Product Storage
Phenosolvan Wastewater
Degassing Cyclone Vent Gas
Ammonia Stripper (1st
Degassing) Vent Gas
Cooler Vent Gas
2nd Degassing Vent Gas
Crude Phenol Tank Vent Gas
DIPE Tank Vent Gas
By-Product Light Tar
By-Product Medium Oil
By-Product Naphtha
Crude Phenol
Unclean Oil
Light Tar Storage Tank Vent
Gas
Medium Oil Storage Tank Vent
Gas
Naphtha Storage Tank Vent
Gas
Phenol Storage Tank Vent Gas
aq
g
g
g
g
g
g
ol
ol
ol
ol
ol
g
g
(Continued)
C-47
-------
TABLE C.7-1. (Continued)
Plant Section Stream Description State
Outlet Streams
Flare System Combined Gas to Flare (high
pressure coal lock vent gas,
H2S—rich waste gas, and
tar/oil separation waste
gas)
s - solid
g - gaseous
aq - aqueous
ol - organic liquid
C-48
-------
TABLE C.7-2. KOSOVO OVERALL MASS BALANCE RESULTS
Stream
Inlet Streams;
Run-of-Mine Coal (s)
Oxygen
TOTAL INLET
Outlet Streams;
Autoclave Vent Gas
(g)
Gasifier Ash (s)
Gas Production
Wastewater (aq)
De dust ing Cyclone
Vent Gas (g)
L.P. Coal Lock Vent
Gas (g)
Ash Cyclone Vent Gas
(g)
Gas Liquor Tank Vent
Gas (g)
Clean Product Gas (g)
C02~Rich Waste Gas
(g)
Heavy Tar (s)
All values in ke/sasif ier— hr
Total Carbon Sulfur
Mass Flow Mass Flow Mass Flow
2.4 E+04 7.1 E+03 * 1.4 E+02a
2.8 E+03 -
7.1 E+03 1.4 E+02
7.9 E+01 8.5 E+OOC 6.0 E-Olc
2.7 E+03 4.7 E+01 2.4 E+00
2.6 E+03 - 5.0 E-01
8.4 E+03 O.c.d O.c.d
2.0 E+01 6.4 E+OOC 3.7 E-Olc
4.2 E+01 2.3 E+OOC 3.5 E-03C
4.5 E+01 5.9 E-01 8.8 E-01
4.6 E+03 2.1 E+03 4.3 E-02
6.2 E+03 1.8 E+03 5.4 E-01
1.0 E+02 5.6 E+01 3.3 E-01
Nitrogen
Mass Flow
1.8 E+02 a
9.9 E+01
2 . 8 E+02
-b,c
8.1 E-01
8 .3 E-03
O.c.d
7.9 E-02C
1.3 E+Olc
1.9 E-02e
4.7 E+01
3.7 E-02
8.8 E-01
(Continued)
C-49
-------
TABLE C.7-2. (Continued)
Stream
Outlet Streams:
Tar Tank Vent Gas (g)
Medium Oil Tank Vent
Gas (g)
Condensate Tank Vent
Gas (g)
Phenolic Water Tank
Vent Gas (g)
Phenosolvan
Wastewater (aq)
Degassing Cyclone
Vent (g)
Ammonia Stripper Vent
Gas (g)
Cooler Vent Gas (g)
2nd Degassing Vent
Gas (g)
Crude Phenol Tank
Vent Gas (g)
DIPE Tank Vent Gas
(g)
By-Product Light Tar
(ol)
By-Product Medium Oil
(ol)
All values in ke/easif ier-hr
Total Carbon Sulfur
Mass Flow Mass Flow Mass Flow
6.1
2.3
3.7
7.7
1.3
2.6
3.5
5.9
5.2
2.3
6.5
4.0
2.5
E-01 1.4 E-02 5.1 E-03
E+00 7.8 E-01 7.4 E-02
E+00 2.2 E-01 2.S E-02
E+00 1.5 E+00 1.6 E-01
E+04 1.9 E+01 1.1 E+00
E+00 - 6.0 E-03
E+02 7.6 E+01 6.8 E+00
E+00
E-01
E-01 2.6 E-05 4.7 E-05
E-01
E+02 3.3 E+02 2.0 E+00
E+02 2.1 E+02 2.1 E+00
Nitrogen
Mass Flow
7.9 E-04
7.5 E-05f
3 .3 E-04f
3.8 E-02f
2 .2 E+00
1.0 E-03g
.6.3 E+01
-
1.8 E-028
5.3 E-06g
1.6 E-05g
5 .2 E+00
2.5 E+00
(Continued)
C-50
-------
TABLE C.7-2. (Continued)
Stream
All values in kg/gasifier—hr
Total Carbon Sulfur Nitrogen
Mass Flow Mass Flow Mass Flow Mass Flow
Outlet Streams;
By-Product Naphtha
(ol)
Crude Phenol (ol)
Unclean Oil (ol)
Light Tar Storage (g)
Tank Vent Gas
Medium Oil Storage
(g) Tank Vent Gas
Naphtha Storage (g)
Tank Vent Gas
Phenol Storage (g)
Tank Vent Gas
Combined Gas to Flare
(g)
TOTAL OUTLET
Accountability (%)J
1.3 E+02 1.1 E+02
2.8 E+00
3.2 E-01 8.0 E-07
6.1 E+00 1.3 E+00
1.0 E-01 2.6 E-07
5.7 E-04
0.
2.3 E-01
9.0 E+01 ND ND ND
3.0 E+01 2.5 E+Oli 2.5 E-Oli 3.0 E-Oli
6.5 E-01 1.6 E-05 6.4 E-04 3.1 E-05*
1.2 E-05
7.2 E-02 2.8 E-03f
2.0 E-07*
6.6 E+03 1.8 E+OSJ.c 2.3 E+02J'C 7.5 E+OOJ»c
6.5 E+03 2.5 E+02 1.4 E+02
92 180 51
(Continued)
051
-------
TABLE C.7-2. (Continued)
NOTES:
a C, S, and N values in wet coal were calculated from the Coal
Preparation outlet streams by mass balance.
b Excluding all molecular nitrogen. See Section 2.0 for
discussion.
c Does not include particulate data - no analysis available.
<* Amounts of C, S, and N in Dedusting Cyclone Vent negligible;
this stream has a significant particulate loading.
e Molecular nitrogen in excess of (79/21) x 62 (vol %) included.
See Section 3.0 for discussion.
f All fixed molecular nitrogen excluded. See discussion in this
section.
S Excluding all molecular fixed nitrogen. See Section 5.0 for
discussion.
n Unclean Oil mass flows were calculated using analysis data for
the By-Product Medium Oil. See Section 5.0 for discussion.
i Combined Gas to Flare calculated using Equation 3 and data in
Table 6-2, 'calculated' column See Section 6.0 for discussion.
J Accountabilities calculated using Equation 7. See Section 3.0.
- = No Data Available.
( ) - Stream Type - s = solid, ol = organic liquid, aq = aqueous,
g = gaseous.
C-52
-------
TABLE C.7-3. DATA FOR KOSOVO HEAVY TAR AND BY-PRODUCTS
Component
Heavy
Tar
Light
Tar
Medium
Oil
Naphtha
Flow Rate (kg/gasifier-hr) 1.0 E+02 4.0 E+02 2.5 E+02 1.3 E+02
Ultimate Analysis (wt %)
Carbon 56.0 81.9 81.8 85.7
Hydrogen 7.6 8.4 8.9 9.9
Nitrogen 0.87 1.3 1.0 0.2
Sulfur 0.33 0.49 0.83 2.2
Ash 6.6 0.22 0.03
Oxygen 28.6 7.8 8.2 2.1
- = No Data Available
C-53
-------
TABLE C.7-4. KOSOVO TAR/OIL SEPARATION AND BY-PRODUCT STORAGE SECTIONS
GASEOUS STREAM DATA
o
Ul
CoepoftBal
Bit Gas Flee !a£«
(•'/IBBlllBI-kl >l U'C)
•oUcolBi II. of Di7 OBB
Co.po.1,... CO., ...,.!
Fli.J OBIBB (vol »l
Hi
01
Kl
014
CO
COl
8"BaT "'" *'
COS
CIUSII
C2IIJSU
CJHJ
ca«4
CI'B
C4'B
Cl'B
C«»
AlOHBtle IpBBlBB (ppav)
Be.....
TolBBBB
FbBaoU
Nllcu|BB Sptflloa (ppnv)
Ml
lira
Ti - TCBCB. -0.01 vol ft foi fl
T.ok
0.1!
19.1
Tt
19
77.1
O.K
Ti
O.K
(900
110
110
140
Ti
-
0.01
Ti
Ti
0.17
2000
220
17
1<00
130
T«(/Oil S«B«i«tlo« ft
Tir Oil 01 1
lBl.k tBBk TB Ik
1.7
11. 1
NF Ti NF
10.1 0.41 11. 1
71.1 . 1.1 71
7.4
0.1 J.) NF
"
410 It. 000 1500
9( ' -
1.100
1,100
0.14
Ti
'o.io
0.21
0.09
1.4
7. (10
1.400
_ 140 —
Ti 110 NF
110 19 140
17 -
••4 -1 ppav foi all olkolB
CBBBiB
T.Bk
VflMt
i.i:
!(.<
14. <
K.<
(1.0
1.1
KF
(.1
(200
-
210
72
0.07
-
0.01
0.01
0.04
-
iaoo
1000
Ti
KF
170
Fk.BOllB
TBBk
**"'
!.!
14.4
Ti
11
A
0.1
NF
11
11. (00
41
2.100
7.200
0.02
-
0.01
0.01
0.00*
1.1
11 .000
1.100
210
Ti
11.000
11
Ll|kl HBtllBl
Til Oil H.pkIBB
T.Bk TBBk T.Bk
VB.t VtBt V.Bt
S.ll 0.17 4.S
21.1 21.1 11.1
KF KF ' NF
19 (.2 a..
11 II 14
- - KF
NF NF KF
0.11
190 1110 KF
KF
2.400
9,700
Ti
-
0.01
- , - 0.07
0.01
1.1
17.«00
1.900
- (0
Ti Ti Ti
100 71 KF
1.100
fl.Bol
T.Bk
V..I
0.09
11 .(
NF
1(
•4
-
KF
-
KF
-
-
-
.
-
-
-
-
-
-
-
Ti
1.7
-
-------
TABLE C.7-5. KOSOVO TAR/OIL SEPARATION AND BY-PRODUCT STORAGE SECTIONS
GASEOUS STREAM CARBON CONTENT DATA
Carbon Content in i-atomj Cirbon oer 100 moles of las
Species
CH4
CO
C02
COS
CII3SH
C2HjS]l
C2'a (as C2Hfi)
C3's (as C3Hg)
0
1 C4's (as C4H10)
C5's (as C5H12)
C6+ (as C6H14)
C6»6
C7IIB
C8»10
. Phenols (as C6U70)
I1CN
TOTAL
Tar
Tank
Vent
0.16
0.01
0.86
0.011
0.039
0.048
0.0002
0.03
0.0004
0.0005
2.22
1.20
0.672
0.176
0.034
0^013.
5.5
Medium
Oil
Tank
Vent
7.6
5.9
56
0.0096
0.52
0.42
0.68
0.90
1.00
0.45
14.4
4.59
0.98
0.112
0.066
0,0057
94
Condenaate
Tank
Vent
1.19
NF
6.15
-
0.021
0.0072
0.14
0.15
0.12
•0.20
-
3.12
2.10
-
0.0006
0.017
13
Light
Phenolic Tar
Water Storage
Tank Tank
Vent Vent
0.2
NF NF
35
0.0041
0.21
1.44
0.04
0.06
0.08
0.03
10.8
6.60
1.61
0.224
0.0006 0.0006
0.0038
56 0.0006
Medium
Oil Naphtha
Storage Storage
Tank Tank
Vent Vent
NF
NF NF
0.85
NF
0.26
1.94
0.0002
0.03
0.28
0.40
31.8
22.56
1.33
0.048
0.0006 0.0006
0.11
0.0006 60
Phenol
Storage
Tank
Vent
_
NF
-
NF
-
-
-
-
-
-
-
-
-
0.0006
0.0006
NF = Not Found
- = No Data Available
-------
Sulfur concentration data in gaseous streams for the Tar/Oil Separation
and By-Product Storage sections are presented in Table C.7-6. These data were
converted to sulfur mass flow rates using Equation 3.
Table C.7-7 shows nitrogen concentration data for gaseous streams in the
Tar/Oil Separation and By-Product Storage sections. The total nitrogen values
shown are corrected for air present over the liquid in the tanks. Even with
corrections for air, the molecular nitrogen content in the storage tanks
appears to be high if it is due to conversion of bound nitrogen during
combustion or entrainment. Nowhere else in the plant are molecular nitrogen
concentrations as high as those in the storage tanks. It is assumed that
nitrogen was being used as a blanket for the volatile organic liquids to
prevent combustion. Therefore, the molecular nitrogen values were excluded in
these mass balance calculations. Nitrogen concentration values were converted
to nitrogen mass flow rates using Equation 3.
For the combined gas to flare, the total mass flows calculated from
measurements of the high pressure coal lock vent, HsS-rich waste gas, and tar
separation waste gas were used.
C8.0 KOSOVO OVERALL (PLANT-WIDE) TRACE ELEMENT MASS BALANCE CALCULATIONS
Atomic absorption spectrometry (AA) trace element data were used .in
overall (plant-wide) mass balance calculations for the Kosovo plant. The
streams for which AA trace element data were obtained are:
• Dried Coal,
• Fleissner Condensate,
• Gasifier Ash,
• Heavy Tar,
• Light Tar,
• Medium Oil,
• Naphtha,
• Phenosolvan (Phenolic) inlet Water,
• L.P. Coal Lock Vent Gas, and
• Combined Gas to Flare
No trace element data for the run—of-mine coal were obtained. Therefore, an
overall balance including the coal drying section was not possible. The
results shown in Table C.8-1 are for a balance of the gasification plant
excluding the Coal Drying section. The data used in these mass balance
C-56
-------
n
Ln
TABLE C.7-6. KOSOVO TAR/OIL SEPARATION AND BY-PRODUCT STORAGE SECTIONS
GASEOUS STREAM SULFUR CONTENT DATA
- Sulfur Content in «-atom» Sulfur per 100 molei of aaa
Species
1I2S
COS
ClljSH
C2115SII
TOTAL
Tar
Tank
Vent
0.69
0.011
0.039
0^024
0.764
Medium
Oil
Tank
Vent
2.60
0.0096
0.52
0,21
3.34
1
Condeniate
Tank
Vent
0.62
-
0.0021
0,00072
0.623
Light
Phenolic Tar
Water Storage
Tank Tank
Vent Vent
1.26 0.089
0.0041
0.21
0.72
2.19 0.089
Medium
Oil Naphtha
Storage Storage
Tank Tank
Vent Vent
0.155 NF
NF
0.26
0.97
0.155 1.23
Phenol
Storage
Tank
Vent
NF
-
-
NF
NF - Not Found
- - No Data Available
-------
TABLE C.7-7. KOSOVO TAR/OIL SEPARATION AND BY-PRODUCT STORAGE
SECTIONS GASEOUS STREAM NITROGEN CONTENT DATA
n
00
Tar
Tank
Species Vent
N2 155
N2 12.0
excluding
air*
NH3 . 0.26
HCN 0.013
Total 12
excluding
air
Total 0.27
excluding
Nitrogen Content
Medium
Oil Condensate
Tank Tank
Vent Vent
15.2 122
6.9 0
0.0019 NF
0.0057 0.017
6.9 0.017
0.0076 0.017
in g-atoms Nitrogen per
Light
Phenolic Tar
Water Storage
Tank Tank
Vent Vent
78 162
0 19
1.2 0.01
0.0038
1.2 19
1.2 0.01
100 moles
Medium
Oil
Storage
Tank
Vent
176
129
0.0075
-
130
0.0075
of gas
Naphtha
Storage
Tank
Vent
168
148
NF
0.11
150
0.11
Phenol
Storage
Tank
Vent
168
47.6
0.0004
-
48
0.0004
*N2 excluding air = N2 - 79/21 02.
- = No Data Available
-------
TABLE C.8-1,
o
t_n
MASS BALANCE RESULTS FOR TRACE ELEMENTS IN KEY KOSOVO STREAMS
ANALYZED BY ATOMIC ABSORPTION SPECTROMETRY
Trace
Element
As
Be
Cd
Co
Cr
Cu
Dg
Mo
Ni
Pb
Sb
Se
Sr
Tl
V
Zn
Inlet Stream
Dried Gasifier
Coal Ash
9
1
6
5
1
6
1
1
2
1
3
3
2
2
.4 E-01
.6 E-02
.4 E-02
.4 E-02
.4 E+00
.9 E-01
.2 E-02
.0 E-01
.4 E+00
.3 E-01
NF
.2 E-01
.0 E+00
NF
.2 E-01
.2 E+00
2.0 E-01
6.8 E-03
1.9 E-01
4.6 E-02
4.9 E-01
1.1 E-01
8.2 E-04
2.4 E-02
8.6 E-01
1.4 E-01
NF
6.5 E-02
1.0 E+00
NF
2.7 E-01
5.7 E-03
Heavy
Tar
1.6 E-03
2.9 E-05
3.7 E-04
1.5 E-04
3.0 E-03
6.0 E-04
6.4 E-05
8.5 E-05
2.1 E-03
6.4 E-03
3.9 E-04
2.6 E-04
4.1 E-03
NF
5.7 E-04
9.8 E-03
Light
Tar
6.8 E-03
3.6 E-05
2.6 E-04
NF
1.2 E-03
6.4 E-03
NF
NF
3.6 E-03
2.7 E-03
NF
6.4 E-04
8.0 E-03
NF
NF
1.1 E-02
Outlet Streams
Medium
Oil Naphtha
5.0 E-04
NF
1.9 E-05
NF
1.0 E-03
2.8 E-04
5.2 E-05
4.8 E-05
NF
3.5 E-04
NF
4.8 E-04
2.2 E-03
NF
NF
3.8 E-03
8.5 E-05
2.7 E-07
1.2 E-07
7.7 E-07
1.5 E-05
2.4 E-05
2.0 E-05
1.4 E-06
2.1 E-05
9.8 E-06
1.9 E-06
1.1 E-04
NF
NF
NF
2.1 E-05
Phenosolvan
Inlet
Water
1.3 E-03
NF
1.8 E-05
NF
3.0 E-04
1.4 E-04
1.8 E-03
NF
1.7 E-04
1.8 E-04
NF
6.5 E-04
1.3 E-03
NF
NF
3.6 E-03
L.P. Coal
Lock
Vent
3.6 E-05
8.4 E-08
5.7 E-07
1.0 E-07
5.7 E-06
3.8 E-06
1.1 E-06
9.5 E-07
2.5 E-06
1.5 E-06
NF
-
1.3 E-05
NF
1.9 E-07
3.4 E-05
Percentage of
Amount Found in
Dried Coal
Combined Accounted for in
Gas to the Outlet Streams
Flare Given in this Table
2.5 E-06
2.3 E-07
3.2 E-07
2.3 E-07
NF
7.7 E-06
NF
NF
1.0 E-05
1.3 E-06
NF
9.6 E-06
5.9 E-06
NF
9.0 E-07
4.1 E-05
22
43
298
85
35
17
23
24
36
115
-
21
34
-
123
1.5
NF = Not Found
- - No Data Available
-------
calculations are shown in Table C. 8-2. Trace element mass flows for the
Fleissner condensate were not calculated because flow, rate data were not
available. The concentration data shown in Table C.8-2 were converted to
elemental mass flow rate data. For solid streams (dried coal, gasifier ash,
and heavy tar), the following formula was used:
Mi = Ci
where: MI = mass flow rate of element i in kg/gasifier-hr
Ci = concentration of element i in mg/kg
MT = total stream flow rate in kg/gasifier-hr
For example, for the mass flow rate of As in dried coal, the calculation is
Dried Coal
As Mass = i 59 ma As\ / 1 kg As \ /I. 6 E+04 kg coall
Flow
59 ma As\ / 1 kg As \ 11.6 E+04 kg co
kg coaly 1 10* mg As I I gasifier-hr
9.4E-01 kg As/gasifier
For liquids by-products (light tar, medium oil, and naphtha), the
following was used:
where: Mi = mass flow rate of element i in kg/gasifier-hr
Ci = concentration of element i in mg/L
PT = density of the stream in g/L
MT « total stream flow rate in kg/gasifier-hr
Density data for the by-products are shown in Table C.8— 3. These data
were used for calculations to determine trace element mass flows in by-product
streams. For example, the mass flow of As in light tar is:
Light Tar As = / 8.3E+01 ma\ /la \ /4.0E+02 ka/hr )
Mass Flow I L II 1000 mg) I 1059 g/L/
\ / \ J \ /
-5.0 E-04 kg As/gasifier-hr .
C-60
-------
TABLE C.8-2. DATA FOR TRACE ELEMENTS IN KEY KOSOVO STREAMS
ANALYZED BY ATOMIC ABSORPTION SPECTROMETRY
o
Trace
Element
As
Be
Cd
Co
Cr
Cu
»g
Mo
Ni
Pb
Sb
Se
Sr
Tl
V
Zn
Dried
Coal
(mg/kg)
5.9 E+01
1.0 E+00
4.0 E+00
3.4 E+00
8.7 E+01
4.3 E+01
7.4 E-01
6.4 E+00
1.5 E+02
8.2 E+00
NF
2.0 E+01
1.9 E+02
NF
1.4 E+01
1.4 E+02
Solids
Gasificr
Ash
(mg/k()
7.5 E+01
2.5 E+00
6.9 E+01
1.7 E+01
1.8 E+02
4.0 E+01
3.0 E-01
8.9 E+00
3.2 E+02
5.2 E+01
NF
1 2.4 E+01
3.7 E+02
NF
1.0 E+02
2.1 E+00
.-•^•••.^•j
Heavy
Tar
<*8/kg>
1.6 E+01
2.9 E-01
3.7 E+00
1.5 E+00
3.0 E+01
6.0 E+00
6.4 E-01
8.5 E-01
2.1 E+01
6.4 E+00
3.9 E+00
2.6 E+00
4.1 E+01
NF
5.7 E+00
9.8 E+01
Light
Tar
(mg/1)
1.8 E+01
1.0 E-01
7.0 E-01
NF
3.2 E+00
1.7 E+02
NF
NF
9.5 E+00
7.2 E+00
NF
1.7 E+00
2.1 E+01
4.2 E-01
5.3 E-01
3.0 E+01
Bv-Products
Hediuoi
Oil
(mg/1)
1.9 E+00
NF-02
7.5 E-02
1.9 E-01
3.9 E+00
1.1 E+00
2.0. E-01
1.8 E-01
NF
1.4 E+00
NF
1.8 E+00
8.3 E+00
NF
NF
1.5 E+01
Waters
Naphtha
(mg/1)
5.5 E-01
1.8 E-03
8.0 E-04
5.0 E-03
1.0 E-01
1.5 E-01
1.3 E-01
9.0 E-03
1.4 E-01
6.4 E-02
1.2 E-02
7.3 E-01
NF
NF
NF
1.4 E-01
Phenosolvan
Inlet
Water .
(mg/1)
1.0 E-01
NF
1.4 E-03
NF
2.3 E-02
1.1 E-02
1.4 E-01
NF
1.3 E-02
1.4 E-02
NF
5.0 E-02
1.0 E-01
NF
NF
2.8 E-01
Fleissner
Condensate
(mg/1)
8.5 E-01
5.0 E-03
2.4 E-03
2.2 E-03
2.5 E-01
5.0 E-03
8.0 E-02
3.1 E-02
5.6 E-01
3.8 E-02
NF
1.6 E-02
2.1 E+00
NF
1.0 E-01
1.2 E+00
Gases
L.P. Coal
Lock
Vent
1.7 E+03
4.0 E+00
2.7 E+01
4.9 E+00
2.7 E+02
1.8 E+02
5.3 E+01
4.5 E+01
1.2 E+02
7.2 E+01
NF
NQ
6.1 E+02
NF
9.0 E+00
1.6 E+03
Combined
Gas to
Flare
(Mg/°>3>
1.9 E+00
NF
2.4 E-01
1.7 E-01
NF
5.8 E+00
NF
NF
7.5 E+00
1.0 E+00
NF
7.2 E+00
4.4 E+00
NF
NF
3.1 E+01
NQ - present, but Not Quantifiable
-------
TABLE C.8-3. KOSOVO BY-PRODUCTS DENSITY DATA
By-Product Density (g/L)
Naphtha 345
Medium Oil 972
Light Tar 1059
Aqueous stream trace element mass flow rates are found using Equation 3:
VT
where: Mi = mass flow rate of element i in kg/gasifier-hr
Ci = concentration of element i in mg/L
Vf = volumetric total stream flow in ms/hr.
The following is an example of this calculation for As in the Phenosolvan inlet
water:
Phenosolvan Inlet Water _[1.0E-01 mgYlg/m3V 1 kg Vl3 m3)
As Mass Flow \L /Wg/L y\^.000 J\ hr /
= 1.3E-03 kg/gas ifier-hr
For gaseous streams, elemental mass flow rates were determined by Equation
14:
Mi — Ci I " IVT
where: Mi = mass flow rate of element i in kg/gasifier-hr
Ci = concentration of element i in ng/m3
VT = volumetric total stream flow in m3/hr
For example, the As mass flow in the L.P. coal lock vent gas is:
C-62
-------
The accountabilities reported in Table C.8-1 were calculated using Equa-
tion 7. The dried coal was used as the inlet stream.
C-63
-------
APPENDIX D
TABLE D-l. PROPOSED DMEG VALUES
MEG
Category Constituent
50 Antimony
49 Arsenic
15 Benzene
32 Beryllium
37 Boron
BOD
82 Cadmium
53 Carbon disulfide
53 Carbonyl sulfide
68 Chromium
78 Copper
47 Cyanide (HCN)
1 Ethylene
8 Formic acid
53 Hydrogen sulfide
46 Lead
Proposed DMEG
Value
7.25E2(W,H)l»*
6.0E2(W,E)
2.0EO(W,H)
2.9EKW.E)
1.5E3(W,H)
4.6E3(W,E)
8.7EO(W,H)
8.25E2(W,E)
7.5E2(W,E)
2.0E5(W,E)
5.0EO(W,E)
3.0E3(A.H)
3.8E3(A»H)
8.0E-KW.H)
5.0E1(W,E)
5.0E3(W,H)
3.95EO(W,E)
5.0E3(A,H)
1.0E3(W,H)
7.0EO(W,E)
2.4EKA.E)
1.75E4(W,E)
2.5E4(A,E)
2.5E2(W,H)
2.22E4(W,E)
(Continued)
-------
TABLE D-l. (Continued)
MEG
Category
Constituent
Proposed DMEG
Value
83
76
18
54
79
28
53
53
53
45
15
81
Mercury
Nickel
Oil and Grease
Phenol
Selenium
Silver
Sodium
Sulfide
Sulfate
Thiocyanate
Tin
TDS
Toluene
Zinc
l.OEO(W.H)
3.2E-KW.E)
2.5E2(W,H)
1.1E3(W,E)
5.0E2(W,E)
1.7E4(W,H)
3.0E3(W,E)
2.2EKW.E)
5.0E1(W,H)
4.5E-2(W,E)
1.0E5(W.H)
2.5E2(W,H)
l.OEKW.E)
1.3E6(W,H)
4426E4(W,E)
8.70E3(W,E)
3.0E4(W,H)
1.3E6(W,H)
2.5E6(W,E)
8.7E4(W,H)
5.0E2(W,E)
8.44E4(W,E)
aEb
2 Letters in parentheses indicate applicability of DMEG value;
W,H = Water, health; W,E = Water, ecology; A.H = Air, health;
A,E = Air, ecology.
D-2
-------
APPENDIX E
GLOSSARY OF TERMS AND ACRONYMS
AA - atomic absorption spectrophotometry
AA,ETA/DA - atomic absorption spectrophotometry, electro thermal atomization
(graphite furnace)/deuterium arc
AMES1 - salmonella mutagenesis assay
ASTM - American Society for Testing and Materials
B(a)p - benzo(a)pyrene
BOD - biological oxygen demand
CHO - Chinese hamster ovary clonal toxicity assay
COD - chemical oxygen demand
DIN - Deutsche Einheitsuerfahren zeir Wasser Untersuchung (German
Institute for Standardization)
DMEG - discharge multimedia environmental goal; target value for a
component in a discharge stream (SAM/1A model)
DMSO - dimethylsulfoxide
DS - discharge severity = discharge concentration •=• DMEG
(SAM/LA Model)
E - exponent; aEb = a x 10^
EC5Q - effective concentration of a substance for 50% positive effects
EP — extraction procedure specified by the Resource Conservation and
Recovery Act
GC - gas chromatography
GC/FID - gas chromatography/flame ionization detector
GC/MS - gas chromatography/mass spectrometry
COST - Soviet State Committee on Standards
HHV - higher heating value
IERL - Industrial Environmental Research Laboratory (U.S. Environmental
Protection Agency)
LEV - lower heating value
-------
Mg - megagram = 1 metric ton
MJ - megajoule = -1000 Btu
MPa - megapascal = -10 atm
NBS - National Bureau of Standards
Nm^ - normal cubic meter (25°C & 1 atm)
PNA - polynuclear aromatic hydrocarbon
ppmv - parts per million volume, 1% by volume = 10,000 ppmv
RAM - rabbit alveolar macrophage assay
RCRA - Resource Conservation and Recovery Act
SAM/1A - Source Analysis Model/lA (U.S.-EPA/IERL)
SSMS - spark source mass spectormetry
TA-X - a specific strain of Salmonella typhimurium where x = strain
number (.AMES assay)
IDS - total discharge severity = EDS (SAM/1A model)
TOG - total organic carbon
TWDS - total weighed discharge severity = EWDS (SAM/1A model)
WDS - weighed discharge severity = discharge severity x stream mass
flow rate (SAM/1A model)
XAD-2 - porous polymer resin for sorption of organic vapors
252 Group - 252 molecular weight polynuclear aromatic hydrocarbons
E-2
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1 REPORT NO
EPA-600/7-81-142
3. RECIPIENT'S ACCESSION-NO.
*. T: , LE AND SUBTITLE Environmental Assessment: Source
Test and Evaluation Report—Lurgi (Kosovo) Medium-
Btu Gasification, Final Report
5. REPORT DATE
August 1981
6. PERFORMING ORGANIZATION CODE
7 AUTHOR(S)
K.W.Lee, W.S.Seames,R.V.Collins, K.J.Bombaugh,and
G.C.Page
8. PERFORMING ORGANIZATION REPORT NO.
9 PERFORMING ORGANIZATION NAME AND ADDRESS
Radian Corporation
P.O. Box 9948
Austin, Texas 78766
10. PROGRAM ELEMENT NO.
CCZN1A
11. CONTRACT/GRANT NO.
68-02-3137 and -2147
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
Final: 3/76-3/81
14. SPONSORING AGENCY CODE
EPA/600/13
15. SUPPLEMENTARY NOTES
IERL-RTP project officer is William J. Rhodes, Mail Drop 61,
919/541-2853. EPA-600/7-79-190 (NTIS PB 80-183098) is the Phase I report.
16. ABSTRACT
The report summarizes an environmental data acquisition program invol-
ving a commercial-scale, medium-Btu, Lurgi gasification plant in the Kosovo reg-
ion of Yugoslavia. The program is sponsored jointly by the U.S. EPA and the gover-
nment of Yugoslavia. The objective of the program was to characterize potential
environmental problems associated with coal gasification in a Lurgi plant. Since
Lurgi plants are being planned for U.S. gasifiers, the program enabled the EPA to
study firsthand the possible environmental problems which might be encountered.
The Source Analysis Model/IA (SAM/IA) was applied to the best values of flow rates
and concentrations of chemical species from all field tests to identify and prioritize
potentially harmful discharges. The model was also applied to specific chemical
species plantwide in the gaseous discharge streams. The primary conclusion of this
environmental assessment model is that the process exhibits a significant potential
for pollution. All discharge streams are potential vehicles for pollutant transfer
from the process to the environment. The streams with the highest priority for con-
trol, based on their potential for adverse health effects in the three discharge media,
are the H2S-rich waste gas, phenolic wastewater, and heavy tar (solid). When eval-
uated using SAM/IA, sulfur compounds posed the largest health problem from gases.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
Pollution
Assessments
Coal Gasification
Sulfur
Phenols
Tars
Hydrogen Sulfide
Pollution Control
Stationary Sources
Lurgi Process
Sulfur Compounds
13 B
14 B
13H
07B
07C
3. DISTRIBUTION STATEMENT
Release to Public
19. SECURITY CLASS (This Report)
Unclassified
21. NO. OF PAGES
325
20. SECURITY CLASS (This page/
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
E-3
------- |