United States
Environmental Protection
Agency
Office of Water
WH-552
Washington, DC 20460
July 1986
Water
vvEPA
Low BTU
Gasifier Wastewater
Technical Support Document
-------
LOW-BTU GASIFICATION WASTEWATER
TECHNICAL SUPPORT DOCUMENT
Lee M. Thomas
Administrator
Lawrence J. Jensen
Assistant Administrator
for the Office of Water
William Whittington
Director for the
Office of Water Regulations and Standards
Deveraux Barnes
Acting Director
Industrial Technology Division
William Telliard
Energy and Mining Branch
July 1986
U.S. Environmental Protection Agency
Washington, D.C. 20460
-------
DISCLAIMER
This Technical Support Document was primarily based on the EPA
Office of Water sampling and analysis program. No proprietary or
confidential data have been used in the preparation of this
document. Although this document addresses various wastewater
treatment technologies, no process developer or process licensee
was involved in the development of this manual. Mention of trade
names or commercial products does not constitute endorsement or
recommendation for use.
1,1
-------
FOREWORD
This Technical Support Document is an assimilation of process and
effluent data on the low-Btu coal gasificatin industry that were
collected and analyzed by the EPA from 1979 to 1981. This
document presents the data in summarized form for the use of
permit writers, developers, and other interested parties.
Examples of applicable wastewater pollution control technologies
are also presented, both as individual process units and as
integrated control systems. None of the examples are intended to
convey an Agency endorsement or recommendation but rather are
presented for informational purposes. The selection of control
technologies for application to specific plants is the exclusive
function of the designers and permitters who have the flexibility
to utilize the lowest cost and/or most effective approaches. It
is hoped that the readers will be able to relate their waste
streams to those presented in this document to enable them to
better understand the extent to which various technologies may
control specific waste streams and utilize the information in
making control technology selections for their specific needs.
The reader should be aware that this document contains no legally
binding requirements or guidance and that nothing contained in
this document relieves a facility from compliance with existing
or future environmental regulations or permit requirements.
iii
-------
TABLE OF CONTENTS
Disclaimer ...
Foreword . . .
List of Figures
List of Tables
Section 1 - Introduction
1.1 General
1.2 Technology Overview
1.3 Regulatory Background
1.4 Industry Overview . .
1.5 Data Collection Methodology . . . .
1.6 Document Organization
Section 2 - Industry Profile
2.1 Process Description and Definition .
2.2 Process History
2.3 Industry Status
2.4 Coal Preparation
2.5 Gasification
2.6 Gas Purification
2.7 Commercially Available Technologies
2.8 General Process Chemistry
2.9 Product
2.10 Uses
Section 3 - Sampling and Analysis Program
3.1 Purpose ........
3.2 Scope
3.3 Site Selection Criteria
3.4 Plants Sampled ..
3.5 Pollutants Analyzed
3.6 Sampling Episodes .
Section 4 - Wastewater Characterization
4.1 General
4.2 Gas Quench Water
4.3 Ash Sluice Water
4.4 Acid Gas Removal
Section 5 - Treatment Technology
5.1 Scope of the EPA Treatability Study
5.2 The EPA Treatability Study Site . ,
5.3 Pilot Plant Description
5.4 Sampling and Analysis .
5.5 Results
1
1
2
4
7
7
8
9
9
11
12
12
12
21
23
26
29
29
32
32
32
33
35
35
45
48
48
48
62
73
74
74
75
75
81
84
v
-------
TABLE OF CONTENTS (Continued)
Page
Section 5 - Treatment Technology (Continued)
5.6 Problems Encountered 88
5.7 Treatability Study Conclusions .... 90
5.8 Other Studies 90
Section 6 - Conclusions 99
Bibliography 100
Appendix A - Descriptions of Plants SAmpled and
Summaries of SAmpling Data A-l
Appendix B - Sections 4 and 6 of Low-Btu Gasification
Generic Sampling Program for Multimedia
Development of Regulatory Support Data . . B-l
VI
-------
LIST OF FIGURES
Figure Page
2-1 Basic Features of Low-Btu Gasification
Processes 10
2-2 Four Basic Designs of Coal Gasifiers 18
2-3 Pyrolysis of Coal 27
3-1 Liquid Waste Streams Generated at a Typical
Low-Btu Gasification Facility 36
5-1 Schematic Flow Diagram . * 77
5-2 Roughing Section Filter 78
5-3 Dephenolizer 79
5-4 Ammonia Still 80
5-5 Activated Sludge 82
5-6 Effluent Polishing 83
5-7 Performance of Pretreatment Units 85
5-8 Percent Reduction in BOD, TOC & COD Across
Bio-Units @ 50% Gasifier Dilution 86
5-9 Block Diagram of GFETC Wastewater Sludge
Generation System (Phase 1) 91
5-10 GFETC Gasifier Wastewater Pretreatment Train
(Phase 2) 92
VII
-------
LIST OF TABLES
Table Page
1-1 The Clean Water Act Amendments of 1977 .... 6
2-1 U.S. Commercial and Pilot Low-Btu Gasification
Facilities 13
2-2 Typical Composition of Low-Btu Gas from
Bituminous Coals and Lignite ,30
2-3 Past Users of Gas Produced 31
3-1 Operating Characteristics of Gasifiers Sampled 37
3-2 Gas Purification Processes of Gasifiers
Sampled 38
3-3 Pollutant Parameters to be Analyzed in
Wastewater Samples 40
3-4 Annotated Outline for Sampling Plan 46
4-1 Priority Organic Pollutants in Gas Quench
Wastewater (ug/1) Found in More Than One Sample 50
4-2 Priority Organic Pollutants Detected Only Once
in Gas Quench Water 51
4-3 Priority Organic Pollutants Not Detected in
Gas Quench Water 52
4-4 Synfuels Nonconventional Organic Pollutants
and Appendix C Compounds in Gas Quench Water
(ug/1) 53
4-5 Priority Metals in Low-Btu Gas Quench Waste-
water (ug/1) 54
4-6 Conventional Pollutants in Gas Quench Waste-
water (mg/1) 55
4-7 Nonconventional Pollutants in Low-Btu Gas
Quench Wastewater (mg/1) 57
4-8 Water Quality Parameters for Three Coal
Conversion Aqueous Process Wastewaters .... 59
4-9 Comparison of High Pressure and Low Pressure
Pollution Levels 61
V11Z
-------
LIST OF TABLES (Continued)
Table Page
4-10 Priority Organic Pollutants Detected in the
Ash Sluice Water (ug/1) 63
4-11 Priority Metals Detected in the Ash Sluice
Water (ug/1) 64
4-12 Nonconventional Organic and Appendix C
Pollutants Detected in the Ash Sluice Water
(ug/1) 65
4-13 Nonconventional Pollutants Detected in the
Ash Sluice Water (mg/1) 66
4-14 Conventional Pollutants Detected in the Ash
Sluice Water (mg/1) .... 67
4-15 Priority Organic Pollutants Detected in the
Cyclone Quench Water (ug/1) 68
4-16 Priority Metals Detected in the Cyclone Quench
Water (ug/1) 69
4-17 Nonconventional Organic and Appendix C
Pollutants Detected in the Cyclone Quench
Water (ug/1) 70
4-18 Conventional Pollutants Detected in the
Cyclone Quench Water (mg/1) 71
4-19 Nonconventional Pollutants Detected in the
Cyclone Quench Water (mg/1) 72
5-1 Effect of Overall Treatment System 88
IX
-------
SECTION 1
INTRODUCTION
1.1 GENERAL
The purpose of this document is to present the process and
effluent data that were collected and analyzed by the EPA from
1979 to 1981 on the low-Btu gasification industry. It is hoped
that this information will be useful to permit writers, industry,
and the general public when determining appropriate wastewater
pollution control systems for the low-Btu gasification industry.
Information is provided on the status of the low-Btu gasification
industry, wastewater characterization, production process
descriptions, and wastewater treatment technologies.
The term low-Btu gasification in this document concerns air blown
gasifiers using coal as the primary feedstock and producing a gas
with a heating value of approximately 150 Btu/SCF. In the United
States, gasification of coal originated in 1816, many years
before natural gas production was com- mercialized. The gas
product was used principally as a fuel source for space heating
and for streetlights. Gasification was in widespread use by the
turn of the century. By the 1930's, almost 12 million tons per
year of coal were gasified in some 14,000 producer gas units.
However, as World War II opened, synthetic gas production was
diminishing rapidly because of the increased use of natural gas.
Some gasifiers continued to operate after World War II; all of
these are small and located in northern Appalachia.
The energy shortages and imbalances of the 1970's brought a
renewed interest in domestic energy production. Government
agencies, trade associations, and private industry were actively
pursuing synthetic fuels technology development. Coal
gasification in foreign countries has been developed also. In
fact, at least 95 commercial coal gasification plants were
operating in over 27 different countries as of 1981.
In 1979 the Environmental Protection Agency (EPA) began gathering
data to determine the need for environmental regulations on the
synthetic fuels industries. Tn January 1981, the Federal
government cut back on financial assistance for these industries.
This action, along with a more stable supply of petroleum
resources, resulted in a steep cutback of synthetic fuel research
and production. In early 1982, EPA decided not to issue formal
-------
regulations on pollutant discharges in the low-Btu gasification
industry.
Thus, this document presents the data obtained by EPA on the
low-Btu industry for informational purposes. In no way does it
contain legally binding requirements or regulatory standards, nor
does it include preferences for process technologies or controls.
Nothing within this document binds a facility to accept the
example control technology(ies) nor relieves a facility from
compliance with existing or future environmental regulations or
permits.
1.2 TECHNOLOGY OVERVIEW
1.2.1 GENERAL DESCRIPTION
Low-Btu gas production involves the reaction of coal with air
and steam at high temperatures to produce a gaseous product that
can be used as a fuel source. The temperature of the gasifier
is maintained by partial combustion of the coal with air. De-
pending upon the pressure, temperature, air/coal ratio, coal
rank, and the reactor configuration, the resulting gas will have
varying amounts of hydrogen (H^)/ carbon monoxide (CO), carbon
dioxide (CO2), methane (CH4), water (H20), and nitrogen
(No) and the heating value will range from 100 to 200 Btu/std
ft*. The presence of high levels of nitrogen, introduced as a
component in the air and the presence of CO2/ makes the gas
from air fired processes low-Btu gas.
The major processing steps required for low-Btu gas production
are:
o Coal Preparation: crushing and/or grinding, drying, and
size classification.
o Gasification: reaction of the coal carbon with steam and
oxygen to form ^2' co' CO2' an^ CH-4.
o Gas Purification: quench and clean up involving cooling
and removal of particulates, oils, and tars. In some
cases, removal of hydrogen sulfide (H2S), carbonyl
sulfide (COS), and other sulfur compounds from the gas.
In addition to these operations, supporting services and
utilities are required. These include steam generation, cooling
water supplies, water and wastewater treatment, solid waste
disposal, and sulfur recovery (conversion of H2S to sulfur for
sale or disposal).
-------
1.2.2 COAL PREPARATION
Run-of-mine coal is cleaned to remove unwanted constituents by
screening or other separation processes. The coal is crushed or
ground to meet the requirements of the gasifier.
1.2.3 GASIFICATION
The gasification process is relatively simple. Coal falls by
gravity feed from an overhead storage bunker into the upright
cylindrical gasifier. There it reacts with roughly one-sixth of
the air required for complete combustion. This partial com-
bustion generates heat and converts the solid coal to a gaseous
stream rich in carbon monoxide and hydrogen. Steam is added to
the air entering the gasifier to control the temperature of this
partial combustion process and to produce a product with greater
quantities of hydrogen.
Because the air and steam are fed to the gasifier countercurrent
to the coal, conversion of the coal is essentially complete, and
thermal efficiencies of the process can exceed 90 percent.
The product streams from the gasifier consist of a solid ash for
disposal and a product gas having a higher heating value of about
150 Btu/cubic foot. The ash is removed from the bottom of the
gasifier and is transported for disposal. Some applications can
use the hot product gas directly from the gasifier. However,
applications requiring gas compression and distribution require
further gas treatment to remove condensible hydrocarbons derived
from the volatile matter in the original coal.
1.2.4 GAS PURIFICATION
The gas stream leaving a gasifier can contain components that
make it unsuitable as a final product or for further proces-
sing. These undesirable constituents include water vapor,
ammonia, oil, tar, and particules as well as hydrogen sulfide.
Depending on the concentrations of these constituents, product
gas specifications, and/or in-process constraints, any or all of
these constituents may be removed from the gasifier exit gas. A
typical process scheme consists of particulate removal and
quenching.
Particulate removal is generally achieved using some combination
of cyclones, wet scrubbers, or electrostatic precipitators.
Cyclones placed at the end of the gasifier can remove partic-
ulates in the hot exit gas from the reactor. These units are
commonly operated at high temperature and/or high pressure
conditions.
-------
Gas quenching is the first cleanup step after particulate
removal. This process removes many of the volatiles, such as
tars, oils, and phenolics, that are released from the coal. The
gas is cooled by direct contact or indirect cooling with water.
The condensed wastewater stream (called gas quench liquor or
process condensate) contains toxic pollutants at high levels
relative to other wastewater streams from these facilities.
Quenching also removes particulates, and a specific particulate
removal set is sometimes omitted where quenching is used.
1.3 REGULATORY BACKGROUND
1.3.1 WASTEWATER REGULATIONS
The Federal Water Pollution Control Act of 1972 established a
comprehensive program to "restore and maintain the chemical,
physical, and biological integrity of the Nation's waters"
[Section 101(a)]. By 1 July 1977, existing point source
industrial dischargers were required to achieve "effluent
limitations requiring the application of the best practicable
control technology currently available" (BPT) [Section 301(b)
(A)]. Further, by 1 July 1983, these dischargers were required
to achieve "effluent limitations requiring the application of the
best available technology economically achievable (BAT) which
will result in reasonable further progress toward the national
goal of eliminating the discharge of all pollutants" [Section
301(b)(2) (A)]. New industrial direct dischargers were required
to comply with Section 306 new source performance standards
(NSPS), based . on best available demonstrated technology (BAD),
and new and existing dischargers to publicly owned treatment
works (POTWs) were subject to pretreatment standards under
Sections 307(b) and (c) of the Act. While the requirements for
direct dischargers were to be incorporated into National
Pollution Discharge Elimination System (NPDES) permits issued
under Secion 402 of the Act, pretreatment standards were made
enforceable directly against dischargers to POTWs (indirect
dischargers).
Although Section 402(a)(l) of the 1972 Act authorized the
setting of requirements for first dischargers on a case-by-case
basis, Congress intended that, for the most part, control
requirements would be based on regulations promulgated by the
Administrator of the EPA. Section 304(b) of the Act required the
Administrator to promulgate regulations providing guidelines for
effluent limitations setting forth the degree of effluent reduc-
tion attainable through the application of BPT and BAT. Moreover,
Sections 304(c) and 306 of the Act required promulgation of
regulations for NSPS, and Sections 304(f), 307(b), and 307(c)
required promulgation of regulations for pretreatment standards.
In addition to these regulations for designated industry
-------
categories, Section 307(a) of the Act required the Administrator
to promulgate effluent standards applicable to all dischargers of
toxic pollutants. Finally, Section 501(a) of the Act authorized
the Administrator to prescribe any additional regulations
"necessary to carry out his functions" under the Act.
On 27 December 1977, the President signed into law the Clean
Water Act of 1977 (P.L. 95-217). Although this law makes
several important changes in the Federal water pollution control
program, most significantly it incorporates several of the basic
elements of the Settlement Agreement program for toxic pollution
control into the Act. Sections 301(b) (2)(A) and 301(b)(2)(C) of
the Act now require the achievement, by 1 July 1984, of effluent
limitations requiring application of BAT for toxic pollutants
which Congress declared toxic under Section 307(a) of the Act.
Likewise, the EPA's programs for new source performance standards
and pretreatment standards are now aimed principally at toxic
pollutant controls. Section 306(b) includes a list of industrial
categories for which these performance standards should be
developed. Moreover, to strengthen the toxics control program,
Congress added Section 304(e) to the Act, authorizing the
Administrator to prescribe "best management practices" (BMPs) to
prevent the release of toxic and hazardous pollutants from plant
site runoff, spillage or leaks, sludge or waste disposal, and
drainage from raw material storage associated with, or ancillary
to, the manufacturing or treatment process.
In keeping with its emphasis on toxic pollutants, the Clean Water
Act of 1977 also revised the control program for nontoxi-
pollutants. Instead of BAT for "conventional" pollutants
identified under Section 304 (a)(4) (including biochemical oxygen
demand, total suspended solids, fecal coliform, pH, and oil and
grease), the new Seqtion 301(b)(2)(3) requires achievement, by 1
July 1984, of "effluent limitations requiring the application of
the best conventional pollutent control technology" (BCT). The
factors considered in assessing BCT for an industry include the
costs of attaining a reduction in effluents and the effluent
reduction benefits derived compared to the costs and effluent
reduction benefits from the discharge of publicly owned treat-
ment works [Section 304(b)(4)(B) ] . For nontoxic, nonconven-
tional pollutants, Sections 301(b)(2)(A) and (b)(2)(F) require
achievement of BAT effluent limitations within three years after
their establishment or 1 July 1984, whichever is later, but not
later than 1 July 1987. Table 1-1 summarizes these levels of
technologies, sources affected, and deadlines for promulgation
and compliance.
BCT, BAT, and NSPS have not been developed for the low-Btu
gasification industry. This industrial category was not listed
in Sectio.n 306{b) of the Clean Water Act. Yet in 1979, when it
appeared that the industry was growing at a rate requiring
-------
Table 1-1
THE CLEAN WATER ACT AMENDMENTS OF 1977
Level of Technology Section of Act
BPT
BAT
BCT
BADT
301
301
301
, 304
, 304
, 304
306
PSES
PSNS
307
307
Sources Affected
Existing sources
Existing sources
Existing sources
New sources
Existing sources
discharging to
POTW
New sources dis-
charging to POTW
Deadline for EPA
for Promulgation
1 yr. after passage
1 yr. after passage
1 yr. after passage
1-1/3 yrs. after
passage
270 days after
passage
1-1/3 yrs. after
passage
Deadline for Operator
Compliance
1 July 1977
1 July 1983
1 July 1984
Effective upon promul-
gation
No later than 3 years
after promulgation
Effective upon promul-
gation
-------
regulatory control, the Agency initiated a regulation development
program. However, by 1981, when projected growth of the industry
substantially declined, the Agency decided not to develop
regulations. Thus, this document simply provides information on
EPA's data collection effort that permit writers and industrial
developers can use (among other sources) in their determination
of appropriate pollution control measures.
1.4 INDUSTRY OVERVIEW
Most commercial low-Btu gas facilities produce gas for con-
sumption on the site. Typically, the gas is used in process
heating where solid fuel is not suitable, as in the case of brick
kilns. The low-Btu gas industry over the period from 1975 to
1985 has consisted of 32 facilities: 16 commercial and 16 pilot
plants or process development units. Many of the commercial
facilities employ fixed bed, atmospheric pressure gasifiers.
1.5 DATA COLLECTION METHODOLOGY
Wastewater characterization data for the low-Btu gasification
industry were primarily obtained from seven sampling visits at
four operating low-Btu gasifiers (one plant was sampled twice,
and another three times) . Individual wastewater streams produced
at these facilities were sampled in order to determine raw
wastewater pollutant loadings.
The data were analyzed to determine concentrations of priority
pollutants, Appendix C compounds, nonconventional and conven-
tional pollutants, and a number of. organic pollutants
specifically for the synfuels industry.
Following wastewater characterization, methods to treat the
wastewater were investigated. This investigation consisted of
the following procedures:
o A comparison of raw wastewater characteristics of
low-Btu gasification to those of other analogous
industries (such as petroleum refining and coke
plants) to determine applicable wastewater treat-
ment technologies.
o An on-site pilot scale wastewater treatability
study at a commercially operating low-Btu gasifier.
o A review of other studies and literature pertaining
to wastewater treatability for gasification processes.
-------
1.6 DOCUMENT ORGANIZATION
This Technical Support Document is presented in six sections and
two appendices. Following this introductory section are:
Section 2 - Industry Profile - The industry profile
contains information on the history of low-Btu gas pro-
duction, process descriptions, and developmental status
of the low-Btu gasification industry.
Section 3 - Sampling and Analysis Program - Selection
of plants for sampling and selection of parameters for
analysis is reviewed in Section 3.
Section 4 - Waste Stream Characterization - The data
collected on the levels of pollutants in wastewaters from
low-Btu gas facilities is summarized and evaluated.
Included are the test results from seven EPA sampling
programs. Also included is a discussion of the
major sources of effluents.
Section 5 - Wastewater Treatment and Control Technology -
This section discusses applicable in-plant and end-of-pipe
technologies that can be used to reduce or eliminate the
pollutants of concern. The achievable effluent pollutant
reductions are discussed using treatability information
from a pilot-plant treatability study, and information
collected from available literature.
Section 6 - Conclusions - A brief discussion of the
information presented in this document.
References
Appendix A - Plant and Data Summaries - This appendix describes
the plants sampled, discusses the sampling locations and pro-
cedures, and gives the results of sample analysis.
Appendix B - Sampling and Analytical Methods - This appendix
gives information on methods used to provide quality control on
sampling and sample analysis.
8
-------
SECTION 2
INDUSTRY PROFILE
2.1 PROCESS DESCRIPTION AND DEFINITION
The processes considered in this report are for the production of
low-Btu gas from coal or other solid fuels. Coal gasification is
the process whereby coal, in the presence of steam and air or
oxygen, is heated and undergoes a series of reactions (gasifica-
tion followed by devolatization of volatile matter) to produce a
gas consisting primarily of carbon monoxide and hydrogen. For
the purpose of this report, low-Btu gasification uses air with
steam in the reaction to produce a product gas that usually
ranges from 100 to 200 Btu/scf. Medium- to high-Btu gases
(300-1000 Btu/scf) are produced using oxygen instead of air.
Depending upon the pressure, temperature, use of air or oxygen,
coal rank, and the reactor configuration, the resulting gas will
have varying amounts of hydrogen (^2^' carbon monoxide (CO),
carbon dioxide (CO2), methane (CH4), water (H2O) and
nitrogen (N2) and the heating value will range from 100 to 200
Btu/std ft3. in practice the composition of synthetic gas from
any process would vary over some range as a result of the factors
previously mentioned. The presence of high levels of nitrogen,
introduced as a component in the air and the presence of C02»
makes the gas from'air fired processes low-Btu gas.
The gaseous product from the gasifier has a higher hydrogen to
carbon ratio than that in the coal itself, and to achieve this,
hydrogen must be added. Hydrogen is supplied by steam.
Different methods of contacting solid coal with the gaseous
streams (or gasifier bed type) are used.
A general schematic is shown in Figure 2-1. Each process (both
commercially available and under development) has specific
variations that affect the composition and heating value of the
product, and the applicability of the process to individual uses.
Coal rank and preparation requirements, supporting services and
utilities, and equipment capacities are also affected. Several
low- and medium-Btu processes can be used to produce high-Btu gas
by using oxygen instead of air and including additional
operations.
-------
COAL
PREPARATION
GASIFIER
STEAM
GENERATION
AIR
GAS
QUENCH
(Optional)
SULFUR
REMOVAL
(Optional)
ASH/SLAG
DISPOSAL
COOLING 6
DEHYDRA
(Optional)
FUEL USE
OR
CHEMICAL
SYNTHESIS
SULFUR
RECOVERY
Figure 2-1. Basic Features of Low-Btu Gasification Processes
-------
The major processing steps required for low-Btu gas production
are:
o Coal Preparation: crushing and/or grinding, drying, and
size classification
o Gasification: reaction of the coal carbon with steam and
oxygen to form H2* CO, CC-2/ and methane (CH4>
o Gas Purification: quench and clean up involving cooling
and removal of particulates, oils, and tars. In some
cases, removal of hydrogen sulfide (f^S), carbonyl
sulfide (COS), and other sulfur compounds from the gas.
In addition to these operations, supporting services and
utilities are required. These include steam generation, cooling
water supplies, water and wastewater treatment, solid waste
disposal, and sulfur recovery (conversion of H2S to sulfur for
sale or disposal).
EPA's data collection program focused on the actual gasification
process and the wastewaters produced from it. Auxiliary
processes such as coal handling, coal preparation, steam
generation, and cooling tower operation are processes used common
to other industries as well and information on them can be
obtained from other sources.
2.2 PROCESS HISTORY
In the United States, gasification of coal originated in 1816,
many years before natural gas production was commercialized.
Principal uses of the gas product were as fuel sources for space
heating and for streetlights. Gasification was in widespread use
by the turn of the century. By the 1930" s, almost 12 million
tons per year of coal were gasified in some 14,000 producer gas
units. However, as World War II opened, synthetic gas production
diminished rapidly due to increased use of natural gas. Some
gasifiers continued to operate after World War II, although all
of these are small and located in one geographic region (northern
Appalachia).
The energy shortages and imbalances of the 1970's brought a
renewed interest in domestic energy production. Government
agencies, trade associations, and private industry are pursuing
synthetic fuels technology development but commercialization has
been limited. In contrast to fluctuating development of the
American synfuels industry, coal gasification in foreign
countries has been consistently pursued. At least 95 commercial
coal gasification plants are operating in over 27 different
countries.
11
-------
2.3 INDUSTRY STATUS
All commercial low-Btu gas facilities produce gas for con-
sumption on the site. Typically, the gas is used in process
heating where solid fuel is not suitable, such as in the case of
brick kilns. The low-Btu gas industry over the period from 1975
to 1985 has consisted of 32 facilities—16 commercial and 16
pilot/development units. At the end of 1985 the industry was
canvassed.* In commercial facilities, 3 were in operation, 9
shut down, and 4 in stand-by condition. In pilot/development
facilities, 4 were in operation, 7 shut down, 3 dismantled, and 2
in stand-by condition. Table 2-1 gives a listing of units as
developed in 1979 and updated as of early 1986. There are
currently no units known to be under construction or in the
planning stages. Many of the commercial facilities employ fixed
bed, atmospheric pressure gasifiers.
2.4 COAL PREPARATION
Run-of-mine coal is washed using water and/or chemicals to remove
unwanted constituents. This process also sizes the coal by crush-
ing and grinding to meet user specifications of the gasifier.
2.5 GASIFICATION
This step is the principal focus of low-Btu gas production. Coal
gasifiers can be classified according to:
o Bed Type
o Temperature
o Pressure
o Number of stages
o Oxidant
o Ash removal process
2.5.1 BED TYPE
Coal feed is the principal characteristic used to classify
gasifiers. Gasifiers are categorized according to this parameter
as fixed-bed, fluidized bed, entrained bed, or molten media.
These are depicted in Figure 2-2. The typical fixed-bed reactor
*Data collection on this industry was completed in 1981. How-
ever, prior to publication of this document in early 1986, an
update of the industry status was performed and included in
this section. Based upon this new information, a reevaluation
of the 1981 data was not deemed necessary.
12
-------
Table 2-1
U.S. Commercial and Pilot Low-Btu Gasification Facilities
u>
Technology
Vfestinghouse
Molten Salt
Process
Slagging Fixed
Bed Gasifier
Bell Aerospace
High Mass Flux
BCR
Kilngas
Combustion
Engineering
Fund i ng/Qwner
DOE; Westing-
house Corpora-
tion
Atomics Inter-
national-
Rockwell
DOE; Grand Forks
Energy Technol-
ogy Center;
Steams-Rogers ,
Inc.
Bell Aerospace
DOE, BCRI
Al 1 i s-Chalmers ;
State of IL
Combustion
Engineering
Location
Waltz Mill,
PA
Santa Susana,
CA
Grand Forks,
ND
Buffalo, NY
Monroeville,
PA
Wood River,
IL (East
Lake Charles,
LA
Type Status of Gas
of Coal Size Technology Cleanup
Illinois 15 TPD PDU o Cyclone
#6 1 MMSCF/hr o Scrubber
Illinois 24 TPD PDU
#6
Lignite PDU o Wash
Cooler
PDU
o Bituminous, 1.2 TPD PDU
o Subbitumin-
ous
o Illinois #6
Bituminous 820 TPD Demon- o Quench
(460-575 stration o Sulfur
MM SCF/D Plant Removal
design) (Stretford)
120 TPD Demon-
Coal stration
Plant
Status/
Age
o Operating
o Start-up
1975
o Start-up
1978
o Dismantled
o Not oper-
ating
o Not oper-
ating
o Start-up
Oct. 1977
o Operation
through
Oct. 1980
o Not oper-
ating
o Opera-
tional
o Not oper-
ating
-------
Table 2-1 (Continued)
U.S. Commercial and Pilot Low-Btu Gasification Facilities
Technology
In-Situ
Gasification
Riley Morgan
Mvanced Fixed
Bed Coal Gasi-
fier with Air
Oxidant
Kilngas
Funding/Owner
DOE - Laramie
Energy Technol-
ogy Center
Riley Stoker
Co.
General Electric
and DOE
All is Chalmers
State of 3L,
Gi Iber t/Common-
wealth Asso-
ciates, Inc.,
and numerous
facilities
Location
Hanna, WY
Wbrchester,
MA
Schenectady ,
NY
Oak Creek,
WI
Type Status of Gas
of Coal Size Technology Cleanup
Low-Rank Pilot
Coal
Bituminous (1 unit) Demonstra- o Cyclone
Lignite tion Plant
Illinois 2.8 MMSCF/D Pilot
f 6 25 TPD Coal
o Illinois 6.9 MMSCF/D Pilot
No. 6 60 TPD Coal
o Pittsburgh
Status/
Age
Field Tests
since 1972
Last test
1983
o Dismantled
o Test runs
began in
1976
o Periodic
Operation
o In Opera-
tion since
1975
o Shut down
1983
Fast Flu id i zed
Bed Gasifica-
tion
DOE Hydrocarbon
Research, Inc.
Lawrence Town-
ship, NJ
Bituminous
Anthracite
0.6 MMSCF/D Pilot
9 TPD Coal
o Start-up in
June 1981
o Shut down
1983
-------
Table 2-1 (Continued)
U.S. Commercial and Pilot Low-Btu Gasification Facilities
Technology
Chemically
Active Fluid
Bed (Exxon)
Combustion
Engineering
METC (Mvanced
Pressurized
Wellman-
Galusha)
Wellman-Galusha
We 1 Iman-Ga lusha
We 1 Iman-Ga lusha
Wilputte
(Chapman)
Funding/Owner
EPA-funded
Central and
Southwest
Corporation
Combustion
Engineering,
EPRI; DOE
Morgantown
Energy Tech-
nology Center
Can-Do, Inc.,
DOE Funded
Howmet Aluminum
Corporation
Binghamton
Brick Co.
Hols ton Army
Ammunition Plant
Location
San Benito,
TX
Windsor, CT
Morgantown,
WV
Hazelton, PA
Lancaster, PA
Bingharnton,
NY
Kingsport, TN
Type
of Coal
Lignite
Pittsburgh
Seam Coal
Subbitu-
minous
Bituminous
Anthracite,
Low Sulfur
Anthracite
Low Sulfur
Anthracite
Low Sulfur
Bituminous,
Low Sulfur
Size
33 MSCF/D
Status of
Technology
Pilot
120 TPD Pilot
0.6 MMSCF/hr
(2 units)
50 TPD
85 TPD
(2 units)
720 TPD
(design)
PDU
Commer-
cial
Commer-
cial
Commer-
cial
Conmer-
cial
(12 units)
Gas
Cleanup
o Cyclone
o Quench
o Sulfur
Removal
(Stretford)
o Wash
cooler
o Sulfur
removal
(Stretford)
o Cyclone
o Gas
Quench
o Cyclone
o Cyclone
o Cyclone
o Gas Quench
Status/
Age
o Startup in
Spring 1979
o Shut down
o Start-up
June 1978
Disman-
tled 1985
o Periodic
Operation
o Start-up
1981
o Operating
o Gasifier
Installed
9uimier 1980
o Standby
o Not oper-
ating
o Operating
o Start-up
1940
-------
U.S.
Table 2-1 (Continued)
Commercial and Pilot Low-Btu Gasification Facilities
Technology
Wellman Incan-
descent
Foster-VJheeler
Stoic
Poster-Wheeler
Stoic
Car-Mox
Gasifier
WeiIman-Galusha
WeiIman-Galusha
WeiIraan-Galusha
Funding/Owner
Caterpillar
Tractor, Inc.
University of
Minnesota (50%
DOE funding)
General Motors
Pike Chemicals
National Lime
and Stone Co.
Hazelton Brick
Co., Webster
Brick Co.,
Itoanoke, VA
01 in Chemical
New Jersey
Zinc
Location
York, PA
Duluth, MN
Saginaw, MI
Nitro, VA
Carey, OH
Hazelton, PA
Ashtabula,
OH
Type
of Coal
Bituminous
Bituminous,
Low Sulfur
(WY)
Various
Bituminous,
Low Sulfur
Anthracite
Low Sulfur
Coke
Status of
Size Technology
130 TPD
8.3 MMSCF/D
72 TPD
3 TPD Coal
2.3 - 3.5
MMSCF/D
25 TPD Coal
24 TPD
20 TPD
170 TPD
Commer-
cial
( 2 units)
Commer-
cial
Demon-
stration
Plant
Commer-
cial
Plant
Commer-
cial
( 2 units)
Commer-
cial
(4 units)
Commer-
cial
(2 units)
Gas
Cleanup
o Cyclone
o ESP
o Sulfur
removal
(Stretford)
o Cyclone
0 ESP
o Cyclone
o Quench
o Cyclone
o Cyclone
o Cyclone
Status/
Age
o Start-up
August 1979
o Shut down
o Start-up
Oct. 1978
o Standby
o Start-up
1979
o Shut down
o Start-up
Sept. 1979
o Shut down
o Start-up
in 1955
o Presently
shutdown
o Start-up
1940 's
o Shut down
o Installed
in 1963
o Standby
-------
U.S.
Table 2-1 (Continued)
Commercial and Pilot Low-Btu Gasification Facilities
Technology
Wei Ima n-Ga lusha
Wellinan-Galusha
Wellman-Galusha
Wellman-Galusha
Wellman-Galusha
Wellman-Galusha
Funding/Owner
Glen-Gery
Corp.
Glen-Gery
Corp.
Glen-Gery
Corp.
Glen-Gery
Brick Co.
50% Aerotherm
Corp. , 50%
DOE - Operated
by Glen-Gery
Corp.
Bureau of Mines
DOE; American
Natural Resources
and 17 other in-
dustrial partners
Location
Iteading, PA
Shoemakers-
ville, PA
Watsontown ,
PA
New Oxford,
PA
York, PA
Fort Snelling,
MM
Type
of Coal
Anthracite
Low Sulfur
Anthracite
Low Sulfur
Anthracite
Anthracite
Low Sulfur
Anthracite
Low Sulfur
o Bituminous
(KY)
o Subbitumi-
nous (CO)
o Lignite
(MD)(TX)
o Simplex
briquettes
Status of
Size Technology
3.65 MSCFD
24 TPD Coal
3.65 MSCFD
24 TPD Coal
(per unit)
7.3 MSCFD
48 TPD
(per unit)
3.65 MSCFD
24 TPD
(per unit)
48 TPD
Commer-
cial
Commer-
cial
(2 units)
Commer-
cial
(2 units)
Commer-
cial
Commer-
cial
(2 units)
Commer-
cial
Gas
Cleanup
o Cyclone
o Cyclone
o Cyclone
o Cyclone
o Cyclone
o Cyclone
o Temporary
Gas Quench
Unit
o Electro-
static pre-
cipitation
to be
installed
Status/
Age
o Shut down
o Operating
o Shut down
o Shut down
o Start-up
Oct. 1977
o Shut down
o Standby
-------
Air or 02
Feed Coal
Steam
Feed Coal
(and Soil i urn
Carbonate)
Raw
Product Gas
Air ^
or O,
Ash or Slag
Entrained Bed
' .'„ • «
•. . Halt
Raw
Product Ga»
Ash, Sulfur,
and Sodium
Carbonate
Hoiten Media
Dry Ash
fixed Bed
Raw
Product Gam
Feed Coal
Air or O]
Steam
Dry Ash
Fluldlied Bed
Figure 2-2
FOUR BASIC DESIGNS OF COAL GASIFIERS
-------
feeds coal from the top of the gasifier where it contacts rising
hot product gas. The lowest temperature of the gasifier is in
this region. There a majority of the volatile matter is driven
off (devolatilization). The volatile matter consists of
aliphatic (straight or branched chain hydrocarbons), alicyclic
(cyclic hydrocarbons), and aromatic compounds (cyclic
hydrocarbons with at least one benzene ring). The devolatilized
coal particles then descend into the gasification zone where
reaction occurs with the steam to produce a mixture of gases
containing primarily carbon monoxide and hydrogen. The third and
lowest zone in a fixed-bed gasifier is the combustion zone, where
the coal and oxygen react to produce heat for the gasification
and devolatilization.
In a fluidized bed gasifier, coal is ground more finely prior to
injection through nozzles usually located in the walls of the
reactor. Gases flow upward in the bed, concurrent with the coal
feed, maintaining a steady state suspension of the solids in a
turbulent condition. Very rapid mass and heat transfer occur in
the fluidized bed; therefore, little temperature variation
occurs. The volatile matter is driven off but is broken down
(reformed) into primarily carbon monoxide and hydrogen. Com-
bustion occurs near the injection ports, and gasification occurs
throughout the bed.
In an entrained bed gasifier, the coal particles travel through
the reactor at roughly the same velocity as the gaseous reactants
and products. Coal can be fed from under the gasifier or from
the top. Because temperatures are much higher in this gasifier
(3,200°F in the combustion zone), shorter reaction times are
required. Thus, residence time is short in this reactor, and
devolatilization and gasification occur rapidly, such that at the
gasifier exhaust port, all reactions are complete and the gas
exits at approximately 1,700°F.
In a molten media gasifier, crushed coal is blended with the
molten medium (e.g., -sodium carbonate) and introduced into a
molten melt which acts as a heat source for the process. These
gasifiers are generally operated at approximately 1,800°F and
slightly elevated pressure.
2.5.2 TEMPERATURE
Fixed bed gasifiers have the lowest average temperature, en-
trained bed the highest, with fluidized beds and molten media in
between. The temperature is an important factor in reaction
rates, energy consumption, and ash removal techniques.
19
-------
2.5.3 PRESSURE
Gasifiers can be operated at atmospheric or pressurized con-
ditions. The operating pressure is an important factor in a
product gas that is piped significant distances from the gasi-
fier. Gaseous reaction rates are also a sensitive function of
pressure. Any of the reactor designs can be operated at
atmospheric pressure or greater.
2.5.4 NUMBER OF STAGES
In fixed bed reactors, the devolatilization zone and the
gasification zone produce different gaseous products. Multiple
stages can be utilized in a gasifier to withdraw these gases at
different locations, thus reducing the cost of gas cleanup. The
stages are all part of the same reactor vessel, but simply define
multiple exhaust ports.
2.5.5 OXIDANT
Only air is used for oxidation in low-Btu gas production. Either
air or oxygen can be injected into the gasifier to produce
medium- or high-Btu gas. This reactant combusts with the coal to
provide process heat for gasification. Because air is
approximately 79 percent nitrogen, a product gas from an air
blown gasifier will contain large quantities of nitrogen,
consequently reducing the thermal content of the product gas.
Oxygen injection permits a higher Btu content of the product gas
than an air blown process. However, oxygen must be cryogeni-
cally separated from air for use in the gasifier; this is a
significant contributor to plant capital and operating costs.
Air blown gasifiers produce a low-Btu gas containing a heating
value of 100 to 200 Btu/stdft3. Oxygen blow gasifiers produce
a medium-Btu gas containing approximately 300 Btu/stdft^ which
can be upgraded by reactions called shift conversion and
methanation to a high-Btu gas of approximately 1,000
Btu/stdft^. This high-Btu gas is also called synthetic natural
gas (SNG) or pipeline gas.
2.5.6 ASH REMOVAL MECHANISM
The temperature at which the ash fuses or becomes molten is
referred to as the ash fusion temperature (this temperature, even
for one type of coal, actually represents a melting range). For
many coals, melting begins to occur betwen 1,800 to 1,900°F.
Those gasifiers that operate at higher temperatures are called
slagging gasifiers because of the removal of the molten slag from
20
-------
the bottom of the reactor. Below this temperature, the gasifier
is termed a dry-bottom (except in the case when a molten medium
is used), and the ash is removed as a solid.
2.6 GAS PURIFICATION
2.6.1 GENERAL
The gas stream leaving a gasifier contains components that in
some cases make it unsuitable as a final product or for further
processing. These undesirable constituents include water vapor,
ammonia, oil, tar, and particulates as well as hydrogen sulfide.
Depending on the concentrations of these constituents, product
gas specifications, and/or in-process constraints, any or all of
these constituents may be removed from the gasifier exit gas.
A typical process scheme consists of particulate removal and
quenching with acid gas removal added in some cases. Gas
purification is what ultimately results in this industry's
principal wastewater stream.
2.6.2 PARTICULATE REMOVAL
Product gas from the gasifier is first routed to a particulate
removal device for removal of elutriated (carried over) un-
reacted coal and ash particles. The collected solids are then
disposed of or reinjected into the gasifier for additional
efficiency. After the gas is essentially free of particulates,
it may be used as a fuel gas or feedstock material. This is
often the case for current commercial low-Btu gas.
Particulate removal is generally achieved using some combination
of cyclones, wet scrubbers, or electrostatic precipitators.
Cyclones placed at the end of the gasifier can remove particu-
lates in the hot exit-gas from the reactor. These units are
commonly operated at high temperature and/or high pressure
conditions. A cyclone is essentially a settling chamber in which
gravitational acceleration is replaced by centrifugal
acceleration. The particulate-laden gas generally enters the
cyclone tangentially at one or more points and leaves through a
central opening at the top of the cylindrical or conical chamber
of the unit. The dust particles move toward the outside wall
from which they are dropped to a collection bin. Cyclone dust is
generally collected dry but is transported in quench water for
cooling and ease of transport.
21
-------
2.6.3 QUENCHING
Gas quenching is the first cleanup step after particulate
removal. This process removes many of the volatiles, such as
tars, oils, and phenolics, that are released from the coal. This
is effected by direct or indirect cooling with water. This
condensed wastewater stream (called gas quench liquor or process
condensate) contains toxic pollutants at high levels relative to
other wastewater streams from these facilities. Quenching also
can be used to remove particulates.
2.6.4 ACID-GAS REMOVAL (SULFUR REMOVAL)
In all current acid gas removal processes, the acid gases are
selectively dissolved in a liquid passed countercurrent to the
gas. This absorption process is generally coupled with a
stripping process that regenerates the absorbent. Many of the
absorption processes used commercially operate at high pressure
and low temperature conditions. A variety of chemical and
physical absorption systems are available.
Regeneration of the absorbent is generally accomplished through
thermal action. The (acid gas removal process has a significant
effect on the overall efficiency of energy conversion because of
the energy requirements of boiling during the regeneration of the
solvent. Between 5.5 to 6 percent of the heating value of the
coal can be lost in this process.
Gas production units employing carbon dioxide removal from gas
have been classified in ; this work as producing medium- or high-
Btu gas; thus, this processing step is not considered here. In
such systems, carbon dioxide and hydrogen sulfide are removed in
the same processing step. However, processes to remove sulfur
containing gas are usually only employed to make low-Btu gas.
The systems currently available for acid gas removal may be
classified in five groups:
o Chemical absorption processes using amines as solvents
o Chemical absorption processes using alkali salts as
solvents
o Physical absorption processes
o Specialized combinations of physical and chemical
absorption processes
o Adsorption processes
22
-------
These processes have limited use in low-Btu gas manufacturing as
they are applied for removal of sulfur containing gases only.
Chemical absorption using alkali salts and adsorption processes
can be used for removal of sulfur containing gases only.
Processes are available for recovery of the removed sulfur as
elemental sulfur.
2.7 COMMERCIALLY AVAILABLE TECHNOLOGIES
These gasifiers include the following technologies:
Single Stage Dual Stage
o Wellman-Galusha o Woodall-Duckham
o Wilputte (Chapman) o Wellman Incandescent
o Riley Morgan o Foster-Wheeler
2.7.1 SINGLE STAGE
Wellman-Galusha
The Wellman-Galusha process was developed initially in 1896 and
is the most prevalent type of gasifier in use in America as of
1979. The process has been commercialized for over 35 years.
Approximately 150 such gasifiers have been operated worldwide in
many different industrial applications.
The gasification step can be carried out in one of two types of
Wellman-Galusha gasifiers: standard or agitated. The latter
process employs an agitator that maintains uniformity in the
combustion zone of the fixed bed. Use of the agitator also
permits the processing of more volatile, caking bituminous coals
and increased gasifier capacity. Coal is continuously fed from
the top of the water jacketed gasifier and enters the devola-
tilization zone. Product gas flowing upward (countercurrent)
contacts the coal particles and volatilizes organic compounds
known collectively as tars and oils, which then exit the
gasifier. As the devolatilized coal particles descend further,
gasification occurs according to the endothermic reactions
discussed under General Process Chemistry. Steam for the
reactor is produced by vaporization of cooling water in the
jacket of the reactor and is consumed in a typical Wellman-
Galusha gasifier at approximately 0.4 to 0.7 pound of steam per
pound of coal feed. The lowest zone is the combustion zone where
inlet air exothermicly combines with carbon in the coal to
produce the heat required for gasification. This air, used at a
rate of approximately 3.5 pounds per pound of coal feed, is
preheated by passage over the water jacket; the resulting
23
-------
steam/air mixture is then injected from beneath the ash grate.
The residence time for bituminous coal in this gasifier is about
four hours. The sole liquid/solid effluent from gasification is
ash, which may be handled wet or dry.
Product gas purification for Wellman-Galusha facilities consists
of particulate removal with a number of subsequent, optional
treatment steps. The raw flue gas exits from one outlet port at
the top of the gasifier at approximately lf!00°F. The gas
leaving the gasifier is passed through a cyclone where the
devolatilized coal dust and ash particles are removed and
reinjected or wasted. After solids are removed, many facilities
route the gas directly to furnaces for combustion and process
heat. Other facilities further treat the gas by quenching
(cooling) to remove tars, oils, and some ammonia. The methods
used to accomplish this include direct injection of 'water into
product gas mains and gas cooling in spray or packed towers. The
temperature of the outlet gas from quenching operatings is
typically 110°F. Depending on the tar/oil content., the sensible
heat from the product gas can be recovered in a waste heat
boiler. Sixty to seventy percent of the tars and oils are
removed by wet scrubbing systems. Further cleanup of residual
tars can be accomplished by collection in an electrostatic
precipitator. The waste stream from this purification step is
called quench liquor. Typically, this stream undergoes gravity
separation; the tars are often combusted and the aqueous phase is
reused or routed to biological treatment. The tars produced from
Wellman-Galusha gasifiers amount to approximately 120 pounds per
ton of coal feed.
Wilputte (Chapman) and Riley-Morgan
These gasifiers are similar to Wellman-Galusha except for
differences in steam feed and ash removal. Steam is fed to these
gasifiers and metered into the air stream. In the
Wellman-Galusha gasifier air is blown through the jacket-boiler
and carries the desired steam with it. Ash removal in these
units is via a pan where the ash is dampened and carried by a
plow to overflow into an ash hopper.
2.7.2 DUAL STAGE
The primary difference between the single- and two-staged
gasifiers is in the number of product gas outlets. Each of the
above systems provides for the withdrawal of the main product gas
stream from a port located at the top of the gasification zone,
and volatile-containing gas outlet port near the top of the
gasifier. This design permits an initial separation of tars and
oils from the main product gas. The overhead gas is called
24
-------
top gas, while the main product stream is more commonly called
clear gas.
Woodall-Duckham
Woodall-Duckham technology was developed by 11 Gas Integrale in
Milan, Italy. The process has been operated for over 30 years
producing principally industrial fuel gases. Although over 100
commercial Woodall-Duckham gasifiers have been installed
worldwide, no commercial or pilot facilities are operating in the
United States.
The gasifier is composed of a lower gasification zone and an
upper distillation and drying zone. Sized coal is fed to the
drying zone at the top of the gasifier where surface and most
inherent moisture in the coal is evaporated by heat transfer from
upward moving hot (approximately 250°F) gases. The coal is then
gradually heated and volatiles driven off in the distillation
zone. The water vapor, hot gases, and volatiles constitute the
top gas withdrawn from the head of the gasifier. Caking coals
will exhibit extremely viscous fluid behavior in this zone,
presenting potential problems in operation. In the gasification
zone, steam and air are reacted at approximately 2,200°F with the
descending coal to produce the clear gas withdrawn from this
zone. Ash is removed via lock hopper beneath the distribution
grate.
Steam is supplied at 0.52 pounds per pound of coal by passage of
the hot inlet air over the gasifier jacket cooling water.
Gas processing differs slightly from single stage technologies.
The clear gas is routed to a cyclone where entrained coal and ash
particles are removed as cyclone dust. The cleaned gas is then
cooled before final use. The top gas is ducted to an
electrostatic precipitator where some of the tars and oils are
removed along with any particulates. The gas is cooled for
additional organics removal prior to blending with the clean gas
for final use.
Wellman Incandescent and Foster Wheeler/Stoic
The Wellman Incandescent and Foster Wheeler/Stoic gasifiers are
very similar to the Woodall-Duckham design. All three produce
top and clear gases of similar quality, and remove ash with a
plow mechanism. Therefore, additional detail will not be
elucidated here. One commercial facility exists in the United
States for each of these technologies; the Wellman Incandescent
in Pennsylvania and the Foster Wheeler/Stoic in Minnesota.
25
-------
2.8 GENERAL PROCESS CHEMISTRY
Coal gasification involves the reaction of coal with air or
oxygen and steam to produce a gaseous product that can be used as
an energy source or a feedstock material for subsequent chemical
processing .
The first step in gasification is pyrolysis or carbonization. The
pyrolysis step may be represented by:
Heat + Coal -> CO, CO2, CH4 , other hydrocarbons
The chemical theory of coal pyrolysis indicates that the coal
decomposes according to the following steps (shown in Figure
2-3) :
(1) As the temperature is raised, the carbon-to-carbon
bonds break first.
(2) Carbon to hydrogen bonds sever as the temperature
then rises and exceeds 600°C (1,100°F).
(3) The heterocyclic structures decompose as a result
of steps 1 and 2 and result in compounds with
increased aromaticity.
(4) The average molecular weights of the intermediate
products decreases as the temperature rises. This
results in evolution of water, carbon monoxide,
hydrogen, methane, and other hydrocarbons.
(5) Final decompositions are at a maximum between 600 and
800°C (1,100 and 1,470°F).
These steps take place without the influence of air, oxygen, or
steam in a short time frame. These steps are essentially the
same as those that occur in coke production, and as discussed in
the wastewater characterization sections, one would expect to
find many of the same contaminants in water used in gasification
as found in coke production.
The subsequent chemistry of gasification is quite complex but may
be represented by the following five reactions:
Combustion
C + nO2 -> (2-2n) CO + (2n-l) CO2
Carbon-Steam Reaction
C + H2O (steam) -> CO + H2
26
-------
0-CH
i
CH4+CO
C« 84.76%
M- 4.l47o
0« 9.68%
N« 1.42%
Figure 2-3
PYROLYSIS OF COAL
27
-------
Carbon-Hydrogen or Hydrogasification Reaction
C -I- 2H2 -> CH4
Water-Gas Shift Reaction
CO + H2O (steam) -> H2 + CO2
Methanation Reaction
CO + 3H2 -> CH4 + H2O
The composition of the gas leaving the gasifier is a function of
the relative contribution of each reaction to the overall
process. Thus, the rate of each reaction, the residence time of
the reactants, and ratios of reactants are the controlling
factors. The rate of the pyrolysis reaction is controlled by
temperature and the manner in which the coal is fed into the
gasifier relative to the steam and air or oxygen. If the coal is
fed into the gasifier such that it is exposed to high tem-
peratures for a period of time prior to exposure to steam and
oxygen or air then the pyrolytic reaction will have a longer
relative contribution to the overall product blend than if the
coal, steam, and air or oxygen were fed into the gasifier
together.
The combustion reaction« is the only reaction which goes to
completion; all the other reactions reach equilibria above
2,000°F with short residence times. The carbon-steam reaction is
endothermic; all the other reactions are exothermic. In
addition, the reaction rates may be increased by increasing the
amounts of reactants in the feed. For example, increasing the
amount of steam in the feed shifts the equilibrium of the carbon
steam reaction.
Temperature affects the reaction rates of the reactions subse-
quent to pyrolysis. At low temperatures, the value of n in the
combustion reaction approaches one, so that CO2 is the
principal product. When higher temperatures are utilized, n
approaches a value of 1/2, and CO is the principal product.
Fluidized and entrained bed gasifiers operate at higher
temperatures, thus, carbon monoxide is the favored product.
Also, very few devolatilized organic compounds survive the high
temperature conditions; they are rapidly pyrolyzed to carbon
oxides and methane. In general, reaction rates increase
exponentially with temperature as long as the reactants are
capable of diffusing to the reaction sites such that the
reactants are present in stoichometric quantities.
28
-------
2.9 PRODUCT
The major components of low-Btu gas are nitrogen, carbon
monoxide, hydrogen, and carbon dioxide. Methane is generally
present at 1 to 3 percent with higher organic compounds totaling
less than 1 percent. The composition depends on coal used and
the processing conditions. A general range of composition is
shown in Table 2-2.
Other significant components in low-Btu gas include sulfur com-
pounds and ammonia. Sulfur compounds include hydrogen sulfide,
carbon oxysulfide, and carbon disulfide. Their content depends
on the sulfur content of the coal and, of course, on any removal
process.
Low-Btu gas is produced at a quantity of about 130,000 std
ft3/t of coal consumed with considerable variation depending on
coal type and process.
2.10 USES
Since low-Btu gas has been produced for many years, it has been
used for many purposes. In general, low-Btu gas has been used
where natural gas was not available and a gaseous fuel is re-
quired. A list of processes which have used low-Btu gas is shown
in Table 2-3. Most of these uses involve heat treating as in
brick manufacture or ore processing. Boiler firing for steam
production also has been a major use. Low-Btu gas also has been
used for ammonia (fertilizer) production with further processing
in the ammonia plant operation.
A potential future use of low-Btu gas is in the direct manu-
facture of electricity by the use of fuel cells. Such systems
can use both medium and low-Btu gas.
Other future uses of low-Btu gas facilities are envisioned to
include central gas generation facilities for a group of
manufacturing processes located near the gas production site.
Such facilities would provide steam and fuel gas to a group of
processors, which might include a number of heat treating type
operations. Such arrangements would produce the economy of scale
needed for the gas production operation and at the same time
allow the sizing of the consuming plants based on an optimum for
that industry.
29
-------
Table 2-2
Typical Composition of
Low-Btu Gas
From Bituminous Coals and Lignite
Component Volume Percent/ dry basis
N2 40-55
CO 20-35
H2 15-20
CO2 3-10
CH4 1-3
C2T 0.1-0.5
Btu/scf 100-200
Source: 16 and 28
30
-------
o Chemical plants
o Glass plants
o Steel mills
o Magnesium plants
o Silk mills
o Bakeries
o Wire mills
o Foundries
o Potteries
Table 2-3
Past Users of Gas Produced
o Aluminum and stainless steel plants
o Ordnance plants
o Tin plate mills
o Lime plants
o Brick plants
o Zinc smelters
o Iron ore processors
o Fertilizer plants
31
-------
SECTION 3
SAMPLING AND ANALYSIS PROGRAM
3.1 PURPOSE
The objective of the low-Btu gas on-site sampling and analysis
program was to develop a wastewater characterization data base as
widely applicable to the industry as possible. Operating
conditions of low-Btu technology, such as pressure, bed type,
coal feed, and gas cleanup systems, can vary considerably from
one facility to another. These are factors that may sub-
sequently have an influence on the characteristics of the
wastewater produced. Therefore, the sampling program attempted
to cover a broad range of these operating conditions.
Individual wastewater streams produced at low-Btu gas facilities
were sampled in order to determine pollutant loadings expected
prior to wastewater treatment. Typically, in wastewater sampling
programs such as this, pollutant concentrations are also analyzed
for samples taken between treatment steps (in addition to
untreated wastewater) to determine treatment performance. Yet,
this industry did not employ treatment technologies (other than
evaporation or recycle) at the time of sampling.
Thus, in addition to obtaining an industry-wide representation of
raw wastewater characterization, it was hoped that the data could
provide information necessary to determine appropriate treatment
technologies.
Because of the small number of commercially operating facili-
ties, pilot plants were included in the sampling program. Pilot
plants are constructed for the purpose of developing data for the
final design of commercial facilities and thus were deemed
appropriate for sampling in this program. Pilot plant equipment
is designed and built at a size that can be scaled-up to com-
mercial scale with a high degree of confidence.
3.2 SCOPE
The low-Btu gas process can be broken down into basically four
areas:
32
-------
o Ancillary Processes
- Coal storage, handling, and preparation
- Steam and power production
o Gas Production
- Gasification
- Ash handling
o Gas Purification
- Quenching
- Acid gas removal
o End Use.
This sampling and analysis program characterized only those
wastewaters associated with the gas production and purification
processes. Ancillary operations, such as those listed above, are
processes that may be similar to other industrial operations that
are regulated by the Environmental Protection Agency's existing
effluent limitations guidelines. Wastewaters produced by the end
use applications of low-Btu gas are not addressed in this study.
No wastewater treatment existed at these facilities. Therefore,
effluent samples from treatment units were not obtainable.
3.3 SITE SELECTION CRITERIA
As of 1981 (as opposed to the more updated industry status
presented in Section 2), the low-Btu gasification industry was
composed of approximately 12 commercially operating facilities,
three commercial facilities in indefinite shutdown, six opera-
tional pilot plants, two pilot plants in shutdown, and six pro-
cess development units. In addition to accessibility, these
facilities were compared with respect to the following charac-
teristics to determine which were the most appropriate for
sampling:
o Coal feed type
o Process technology
- Pressure
- Pressure
- Temperature
- Bed type (fixed, fluidized, entrained)
- Ash handling mechanism
o Gas purification process
o Effluent sources
o Industrial application
33
-------
The selection of facilities sought to provide variations in each
of these factors. These factors can influence the characteriza-
tion of wastewater sources as described below.
3.3.1 COAL TYPE
All major ranks of coal (lignite, subbituminous, bituminous, and
anthracite) have been gasified by at least one facility in the
U.S. It can be anticipated that a fully developed coal gasifi-
cation industry will use a wide variety of coal types. These
coals differ widely in composition, with commensurate variation
in gasifier operation, and ultimately in the flow and composi-
tion of wastewater and solid waste streams. Of particular
significance is the volatile matter content of the feed coal.
For instance, a fixed-bed gasifier utilizing anthracite will
generate a quench water containing less organic material than a
bituminous coal. Also important is the trace element concentra-
tions in the coal. This will have a substantial impact on the
gasifier ash composition and thus potentially affect the metals
content of water used to handle the ash.
3.3.2 PROCESS TECHNOLOGY
Three basic types of bed geometries are employed in commercial
gasifiers (molten-media gasifiers are not commercialized in the
U.S.):
o Fixed
o Fluidized
o Entrained
Associated with each of these is a characteristic operating
temperature and pressure that effects product gas composition.
In turn, this will cause variation in the characteristics of the
wastewater streams generated by cleaning the gas and in
combustion products of the gas.
Entrained bed and fluid bed systems are in general run at higher
temperatures than fixed bed systems. Fixed bed gasification
produces a raw gas that is laden with elutriated ash, unburned
coal particulates, volatile' matter, ammonia, and sulfur
compounds. For fluidized and entrained beds, the raw gas will
contain relatively lower amounts of tars and oils because these
substances are reacted within the gasifier at higher
temperatures.
34
-------
3.3.3 GAS PURIFICATION
Quenching of the gas for particulate removal and for removal of
oils and tars produces a highly contaminated wastewater stream.
While overall concentration of materials in the stream may be a
function of the quenching process, the contaminants present are
primarily a function of the gasification conditions and the coal
used. If sulfur is removed from the raw gas, then an additional
wastewater stream may be produced. Ash from the gasifier may be
removed dry or carried in a suspension of water (slurry or
sluice) which will also cause an additional wastewater stream.
3.3.4 EFFLUENT SOURCES
The major sources of wastewater from the production of low-Btu
gas are:
o Ash or dust sluice/quench water
o Gas quench/cooling condensate
o Sulfur removal condensate blowdown
Not all facilities generate all of these sources of waste
streams. The selection of facilities for sampling sought to find
those with at least one or more of these sources. Figure 3-1 is
a generic diagram of wastewater sources sampled during the
program.
3.3.5 INDUSTRIAL APPLICATION
Low-Btu gas can be used for a number of different purposes such
as chemical feedstocks, power supply, and fertilizer production.
Associated with each end use may be different production proc-
esses which in turn may produce different wastewater streams.
3.4 PLANTS SAMPLED
After consideration of the above factors, four low-Btu gas
facilities were determined good candidates for sampling. These
four facilities and their operating characteristics are shown in
Tables 3-1 and 3-2. Appendix A describes each facility in
detail, including their operating characteristics, waste streams,
and sample points.
3.5 POLLUTANTS ANALYZED
The following classes of pollutants were analyzed in wastewater
samples taken from low-Btu facilities:
35
-------
RAW PRODUCT CAS
COAL
QUENCH LIQUOR
RECYCLE
STEAM
AIR
GASIFICATION
PARTICULATE
REMOVAL
u>
cr\
ASH /SLAG
I
t
ASM QUENCH WATER*
*LIQUID WASTE SYSTEMS
GAS
QUENCH/
COOLING
GAS.
CONDENSATE
OR
QUENCH LIQUOR
DUST/TARS
I
I
I
I
DECANTER
DUST QUENCH
WATER*
T
CLEAN
LOW-BTU
PRODUCT
GAS
ACID GAS
REMOVAL
SULFUR
SULFUR REMOVAL
CAKE SLOWDOWN*
QUENCH
• LIQUOR
SLOWDOWN*
TARS
Figure 3-1. Liquid Waste Streams Generated
at a Typical Low-Btu Gasification Facility
-------
Table 3-1
Operating Characteristics of Gasifiers Sampled
Coal Feed
Gasifier
Technology
Pressurized, advanced,
mechanically stirred
fixed bed
(General Electric)
Single stage, fixed
bed**
(Wilputie-Chapman)
Single stage, fixed
bed***
(Wellman-Galusha)
Pressurized single
stage, fixed bed
(Wellman-Galusha)
Type
Ill#6
bituminous
Virginia
bituminous
ND lignite
Texas lignite
Colorado
subbituminous
Pittsburgh
no. 8
bituminous
Rate
TPD*
24
22
Temp+
°F
Pressure
psig
1100
300
1050-1250 attn
12-24
14-34
15-44
22
1000-1000
850-1200
850-1200
1000-1100
atm
atm
atm
200
**
TPD = Tons per day of coal.
This facility sampled twice but operating conditions
remained the same.
*** This facility sampled three times during test runs using
different coal types.
+ The off-gas temperature from the gasifier - this tempera-
ture is relatively close to the devolatization temperature
which, in the case of fixed bed gasifiers, has an effect on
the amount of organics present in the off gas.
37
-------
Table 3-2
Gas Purification Processes of Gasifiers
Sampled
Technology
Location
Gas Use
Purification Process
Pressurized, advanced,
mechanically stirred,
fixed bed
General Electric
Research Center
Schenectady, NY
Test Water quench —> Venturi scrubber
Burning Benfield —> Saturator
oo
Single stage, fixed
bed
Single stage, fixed
, j
bed
Holston Army
Ammunition Plant
Kingsport, TN
Fort Snelling
Minnesota
Process Cyclone(hot)—> Tray scrubbers—>
Furnaces Spray scrubbers
Pelletizing Dry cyclone —> Water scrubbers
Kiln
Pressurized, single
stage, fixed bed
Morgantown Energy
Technology Center
Morgantown, WVA
Process Cyclone —> Humidifier —>Cyclone
Testing Venturi scrubber --> Cooler -->
Stretford unit
-------
o Priority pollutants
o Appendix C pollutants
o Conventional pollutants
o Noncoventional pollutants
Conventional Pollutants
The conventional pollutants, listed in Table 3-3, were defined in
Section 304(b)(4) of the 1977 Amendments to the Clean Water Act
and at 44. FR 44501 (30 July 1978). Fecal coliform was not
selected for this list since there is no reason to believe that
any fecal matter would be present in synfuels wastewater
samples.
Priority Pollutants
The priority pollutants, also presented by category in Table 3-3,
are a list of toxic organics and metals that are defined in the
Clean Water Act (see Table 1 of Section 301) as well as the 1979
Settlement Agreement.* The specific compounds were selected by
reviewing the Organic Chemical Producers Data Base, reviewing the
frequency of occurrence of the compounds in water, and deter-
mining whether or not a standard was commercially,; available. The
data base used for these determinations is found in an Agency
publication entitled, Frequency of Organic Compounds Identified
in Water by Shackelford and Keith (Environmental Research
Laboratory, EPA-600/4-76-062, Athens, Georgia, 1976).
Appendix C Compounds
The same data base was used for selection of the Appendix C
compounds, which also are listed in Table 3-3. This set of
pollutants derives its name from Appendix C of the 1976
Settlement Agreement. As with the priority pollutants, the
specific compounds in Table 3-3 are actually representatives of
broad classes of pollutants. For example, a-terpineol and
camphor represent the class of compounds called aliphatic
terpenes. The same criteria were used to determine the specific
Appendix C pollutants as were exercised in the selection of the
priority pollutants. These are summarized below:**
*Natural Resources Defense Council, Inc. vs. Train (1979).
**Rational for Synfuel Protocol, preliminary draft, Radian
Corporation, EPA Contract No. 68-01-5163, June 1981.
39
-------
Table 3-3
Pollutant Parameters to be Analyzed in Wastewater Samples
CONVENTIONAL POLLUTANTS
Biochemical Oxygen Demand (8005)*
pH1
Oil and Grease
Total Suspended Solids (TSS)
*Total and Dissolved 8005
PRIORITY POLLUTANTS
Pesticides
Aldrin
Dieldrin
Chlordane
4,4'-DDT
4,4'-DDE
4,4'-ODD
-Endosulfan
-Endosulfan
Endosulfan sulfate
Endrin
Endrin aldehyde
Heptachlor
Heptachlor epoxide
-BHC
-BHC
-BHC
-BHC
PCB-1242
PCB-1254
PCB-1221
PCB-1232
PCB-1248
PCB-1260
PCB-1016
Toxaphene
Volatiles
Acrolein
Acrylonitrile
Benzene
Carbon tetrachloride
Chlorobenzene
1,2-Dichloroethane
1,1,1-Trichloroethane
1,1-Dichloroethane
1,1,2-Trichloroethane
1,1,2,2-Tetrachloroethane
Chloroethane
bis (Chloromethyl) ether*
2-Chloroethylvinyl ether
Chloroform
1,1-Dichloroethylene
1,2-trans-Dichloroethylene
1,2-Dichloropropane
1,2-Dichloropropylene
Ethylbenzene
Methylene chloride
Methyl chloride
Methyl bromide
Bromoform
Dichlorobromomethane
Trichlorofluoromethane*
Dichlorodi fluoromethane*
Chlorodibromomethane
Tetrachloroethylene
Toluene
Trichloroethylene
Vinyl chloride
40
-------
Table 3-3 (Continued)
Pollutant Parameters to be Analyzed in Wastewater Samples
PRIORITY POLLUTANTS
Base/Neutral Compounds
Acenaphthene
Benzidine
1,2,3-Tr ichlorobenzene
Hexachlorobenzene
Hexachloroethane
bis (2-Chloroethyl) ether
1,2-Dichlorobenzene
2-Chloronaphthalene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
3, 3'-Dichlorobenzidine
2,4-Dinitrotoluene
2,6-Dinitrotoluene
1,2-Diphenylhydrazine
(as azobenzene)
Fluoranthene
4-Chlorophenyl phenyl ether
4-Bromophenyl phenyl ether
bis (2-Chloroisopropyl) ether
bis (2-chloroethoxy) methane
Hexachlorocyclopentadiene
Isophorone
Acid Compounds
2,4,6-Trichlorophenol
p-Chloro-m-cresol
2-Chlorophenol
1,4-Dichlorophenol
2,4-Dimethylphenol
2-Nitrophenol
4-Nitrophenol
2,4-Dinitrophenol
4,5-Dinitro-o-cresol
Pentachlorophenol
Phenol
Naphthalene
Nitrobenzene
N-Nitrosodimethylamine
N-Nitrosodiphenylamine
N-Nitrosodi-n-propylamine
bis (2-Ethylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Di-n-octyl phthalate
Diethyl phthalate
Dimethyl phthalate
Benzo(a)anthracene
Benzo(a) pyrene
3,4-Benzofluoranthene
Benzo(k)fluoranthene
Chrysene
Acenaphthylene
Anthracene
Benzo (g,h,i)perylene
Fluorene
Phenanthrene
Dibenzo(a,h)anthracene
Indeno(1,2,3-c,d)pyrene
Pyrene
2,3,7,8-Tetrachlorodibenzo-
p-dioxin
Metals
Antimony
Arsenic
Beryllium
Chromium
Cadmium
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Other
Cyanide
*These compounds have been recently removed
from the priority pollutant list
(see 46 PR 2266 and 46 PR 10723).
41
-------
Table 3-3 (Continued)
Pollutant Parameters to be Analyzed in Wastewater Samples
APPENDIX C COMPOUNDS
1. Acetone
2-21. n-Alkanes (Cio-C30)
22. Biphenyl
23. Camp nor* t
24. Chlorine1
25. Cumene*
26. Dibenzof uran*
27. Di-n-butylaminet
28. Diethylamine*t
29. Diethyl ethert
30. Dimethylaminet
31. Diphenylamine*t
32. Diphenyl ether*
33. Methyl ethyl ketone
34. Nitrites
35. Styrene
36. -Terpineol*t
*Candidate for Stable Label Standards.
tTentatively chosen compounds to repre-
sent general classes.
SYNFUELS GENERAL NONCONVENTIONAL
WASTEWATER POLLUTANTS
Acidity
Alkalinity
Total Solids (TS)
Total Volatile Solids (TVS)
Total Dissolved Solids (TDS)
Chemical Oxygen Demand (COD)
Ammonia
Total Kieldahl Nitrogen
Total Phosphorus
Total Organic Carbon (TOC)
Total Phenolics (4AAP)
Settleable Solids (SS)1
Thiocyanate
Sulfate
Sulfite
Sulfide
Nitrates
Dissolved Oxygen (DO)1
Temperaturel
Volatile Dissolved Solids (VDS)
lOn-site analysis.
Aluminum
Barium
Bismuth
Boron
Calcium
Cobalt
Gold
Indium
Iron
Lithium
Magnesium
Molybdenum
Platinum
Potassium
Silicon
Sod i um
Strontium
Tellurium
Tin
Titanium
Tungsten
Uranium
Vanadium
Yttrium
42
-------
Table 3-3 (Continued)
Pollutant Parameters to be Analyzed in Wastewater Samples
SYNFUELS ORGANIC NONCONVENTIONAL
Benzoic Acid
Hexanoic Acid
-Naphthylamine
-Picoline
Dibenzothiophene
Formates
43
-------
o The compound chosen had to have been identified in water
with a frequency of 5 percent or more with respect to
other members of that chemical class that had been
identified in water.
o The compound chosen had to have a source of commercially
available standards. The standards furthermore had to be
available in reasonable purity (>90 percent) and at
reasonable prices.
o To help prioritize choices with a chemical class, the
"Organic Chemical Producers Data Base" was checked. An
updated 28 November 1979 version was used for the present
criteria choices.
o To further help prioritize choices within a chemical
class, the U.S. EPA Toxic Substances Control Act
Chemical Substances Inventory, Volumes II and III (May
1979), were also used. This information was not avail-
able in 1976, but was used now because of its relation-
ship to the Agency's interest in toxic chemicals and its
data on what toxic chemicals are being manufactured or
imported in the U.S.
Nonconventional Pollutants
Existing information on the low-Btu industry was screened to
determine what other pollutants could appear at concentrations
warranting potential concern. As a result, six organic pol-
lutants and a more extensive list of inorganic pollutants and
water quality parameters were selected for analysis. The organic
nonconventionals, listed in Table 3-3, were selected after review
of results from several synthetic fuels industry environmental
assessments and a review of the current literature in the area of
synthetic fuels wastewater analysis. From these classes,
specific compounds were selected to be representative of the
class. The individual selections were based on: (1) repre-
sentativity of class, (2) frequency of occurrence in synthetic
fuels related wastewater, (3) availability of pure standards, and
(4) detection using existing screening protocols (EPA Methods 624
and 625). Additional detail is provided in the previously cited
Rational for Synfuel Protocol.
The remaining nonconventional pollutants also are listed in Table
3-3. The compounds in the list from acidity to total phenolics
(4AAP) are often referred to as water quality parameters. They
are indicators of the presence of general classes of compounds
(e.g., total phenolics - indicates the presence of phenolic-type
compounds) and general properties of streams (e.g., alkalinity -
44
-------
is the capacity of water to neutralize a strong acid to a
designated pH).
The measurement of settleable solids (SS) is an indicator of the
amount of solid material that will settle in a relatively short
period of time (i.e., approximately one hour). It is a
particularly useful parameter for streams representing runoff
from storage and disposal areas.
Sulfur and nitrogen compounds are gasification products that can
appear in wastewater and solid waste streams associated with
synfuels processing. Formation of sulfate, thiosulfate, carbonyl
sulfide, and thiocyanate during synfuels processing is important
to operation of sulfur recovery technologies. As these compounds
accumulate in a sulfur recovery liquor, the effectiveness of
sulfur removal and recovery is reduced. As such, a periodic
release (blowdown) of the liquor is required. Knowledge of the
levels of these inhibitors in liquid streams from facilities
without sulfur recovery will provide input for design of sulfur
recovery units and estimation of blowdown quantity and quality.
The nonconventional metal wastewater pollutants listed in Table
3-3 are those (exclusive of the priority metal pollutants) that
are capable of quantitative determination by Inductively-Coupled
Argon Plasma Emission Spectroscopy (ICAPES). Although many of
these are not likely to be found in low-Btu gasification waste
streams, both the nature of this study and the economics of
ICAPES analysis provided incentive for determination of these
elements.
3.6 SAMPLING EPISODES
Sampling of the individual gasifier facilities was based on a
sample plan for each site. The creation of the sampling plan
came from procedures developed in a generic sampling program.
The annotated outline of the sampling plan is shown in Table 3-4.
Generally, each sampling visit lasted about three days. The
Holston Army Ammunition Plant facility was sampled twice and the
Ft. Snelling facility was sampled three times. Together with the
other two gasifiers (each sampled once), this totalled seven
individual sampling episodes.
Measures were incorporated to ensure quality sampling in
compliance with the procedures documented by EPA. Whenever
possible, established protocols were used to perform the
sampling. When situations existed where estabished protocols
could not be used, a detailed description of the sampling
procedure was documented in a bound, paginated field or
laboratory notebook. In these cases, guidance will be provided
by the ASTM manual for water and wastewater sampling.
45
-------
Table 3-4
Annotated Outline for Sampling Plan
1.0 Introduction
o Background, including EPA's mandate for sampling
o Purpose of effort
o Brief summary of planned activities on site
o Brief summary of any needed cooperation of facility
personnel
o Planned schedule for major activities
2.0 Sample Plan
o Flow diagram and discussion of processes at site with
energy and material flows where applicable
o Plant operting conditions—discuss operating schedule
and number of plant conditions to be characterized
o Brief explanation of process variabilities including
how these affect sample timing and how to interpret
resulting data
o Sampling point selection
- Water
- Solids and slurries
o Summary matrix of sampling location, type, frequency,
and volume
o Summary table of number and preservation of samples
o Expected conditions at each sample point and definition
of special equipment or procedures to be used
o Chain-of-custody documentation
o Summary table of pollutants to be analyzed
3.0 Sample Team Organization
o Identification of sample crew chief
o Identification of sample crew size
o Listing of sample crew
4.0 Quality Control/Quality Assurance Program
o Approach which includes assignment of responsibility
for QC/QA
o Sampling collection program
o Sampling transportation QC program
o Sample analyses QC program
Addendum
o Reason site was selected under this program
-------
The sampling and analytical procedures used were based on the EPA
Manual, Sampling and Analysis Procedures for Screening of Indus-
trial Effluents for Priority Pollutants, April 1979. Additional
information is found in the 3 December 1979 and 18 December 1979
issues of the Federal Register.
47
-------
SECTION 4
WASTEWATER CHARACTERIZATION
4.1 GENERAL
The data that were gathered during the sampling of the four
low-Btu gas plants are summarized and discussed in this section.
These data are believed to be applicable to raw wastewater
streams for the low-Btu gas industry in general because of the
different operating characteristics represented by each of the
four plants (see Section 3). Since no wastewater treatment
processes were being used, there are no data in this section on
treated effluents from these plants.
In most cases, there will be only one effluent from a coal
gasifier although there may be one, two, or three sources of
wastewater. The largest stream is quench liquor from cooling or
scrubbing the low-Btu gas. There also can be ash sluice (or ash
quench) water. Quench liquor can be used for ash sluice and
recycled or if fresh makeup water is used, it can be put into the
quench liquor. Also there are effluents from acid gas removal
processes. During the testing of the four plants, however, there
was no effluent from the sulfur removal or recovery units.
The information presented in this section is a summary of the
wastewaster data for all four plants by waste stream. The data
for each sampling episode are in Appendix A along with a
description of the processes and of the sampling activities. The
general methods of sampling are described in Section 3.
4.2 GAS QUENCH WATER
All four facilities produced a gas quench condensate. Samples
from the Ft. Snelling facility were taken from the gas scrubber
water, which was not recycled. The METC facility produced a
scrubber recycle and a direct cooler recycle, both of which were
sampled. The GE facility produced a quench recycle and the
Holston facility produced a scrubber recycle, both of which were
sampled also. The data from all these streams are presented
individually by facility in Appendix A but are combined here and
presented in the following sections.
48
-------
4.2.1 PRIORITY ORGANIC POLLUTANTS
Twenty priority organics were detected in more than one sample.
The data on these materials are summarized in Table 4-1. Since
eleven of these compounds were found in samples from all four of
the facilities, these materials are likely to be present in any
low-Btu gas raw wastewater. The compounds present are cyclic and
heterocyclic compounds of the type frequently associated with
coal processing operations, such as coking. Phenol and
2,4-dimethylphenol are the compounds present in the highest
concentration.
There were 25 other priority organic pollutants which were
detected in only one sample. These are listed in Table 4-2.
Another 57 priority organic pollutants were not detected in any
samples and are listed in Table 4-3. These compounds will
probably not be significant in raw wastewater from low-Btu gas
production. The data from the analysis of one sample has been
rejected because the sample appeared to have been contaminated
with laboratory organic solvents and plasticizers.
Analyses also were performed for Synfuels Organic Nonconven-
tional Pollutants and for Appendix C compounds. The results of
these analyses are shown in Table 4-4. Ten compounds were
detected and of these three were found in only one sample. Since
the other seven compounds were detected in a number of samples,
they are likely to be present in low-Btu gas raw wastewater. The
highest concentrations were benzoic acid and hexanoic acid.
4.2.2 PRIORITY METALS
Significant amounts of the metals present in the coal are carried
over into the quench water. Nineteen samples were analyzed for
13 priority metals. The analytical results are summarized in
Table 4-5. Most of the priority metals were present in
detectable levels. Those present at the highest concentration
were arsenic, selenium, and zinc. These metals are present in
sufficient concentration that they should be considered in the
treatment and disposal of the raw wastewaters from low-Btu gas
production.
4.2.3 CONVENTIONAL POLLUTANTS
The conventional pollutants analyses are shown in Table 4-6. Of
these, the most significant is the 6005 which ranged as high as
25,000 ppm with 8 samples reported as greater than 2,000 ppm.
With -the high organic content of the streams as shown by total
organic carbon analysis and by analyses of priority organic
pollutants, high 6005 analyses would be expected. The oil and
49
-------
Table 4-1
Priority Organic Pollutants in
Gas Quench Wastewater (ug/1)
Found in More Than One Sample
Acenaphthene
Benzene
2,4-Dimethylphenol
2,4-Dinitrotoluene
2,6-Dinitrotoluene
1,2-Diphenylhydrazine
Ethylbenzene
Fluoranthene
Naphthalene
N-nitrosophenylarnine
Phenol
Benzo(a)anthracene
Benzo(a)pyrene
Chrysene
Acenaphthaline
Anthracene
Fluorene
Phenanthrene
Pyrene
Toluene
No. of
Samples
20
20
19
20
20
20
20
20
20
20
19
20
20
20
20
20
20
20
20
20
No. of
Detects
11
9
16
2
2
4
6
13
16
7
19
10
4
9
10
16
7
16
9
8
Min
4
288
34
257
2
1
21
26
378
62
3220
13
5
9
122
14
10
28
17
135
Mean Median
547
1240
24900
76
2570
2180
16400
242
161000
8870
20
9680
1230
560
316
1780
1180
698
Max
2580
2780
197400
1570
124
214
14900
3490
82400
504
754000
88000
54
86600
2820
2830
936
10300
9540
1350
50
-------
Table 4-2
Priority Organic Pollutants Detected Only Once
In Gas Quench Water
AeryIonitrile
Carbontetrachloride
1,2,4-Trichlorobenzene
Hexachlorobenzene
Hexachloroethane
1,1,2,2-Tetrachloroethane
Chloroethane
2-chloro ethyl vinyl ether
2-chloronaphthalene
Chloroform
1,3-Dichlorobenzene
1,1-Dichloroethylene
1,2-trans-dichloroethylene
1,3-dichloropropylene
4-Bromophenyl phenyl ether
Bis(2-chloroethoxy)methane
Methyl bromide
Bromoform
DichlorobromoTne thane
Trichlorofluoromethane
Chlorod ibromomethane
Pentachlorophenol
Tetrachloroethylene
Trichloroethylene
Vinyl chloride
51
-------
Table 4-3
Priority Organic Pollutants Not Detected
In Gas Quench Water
Acrolein
Benzidine
1,2-dichloroethane
1,1,1-trichloroethane
1,1-dichloroethane
If IF2-trichloroethane
Bis(chloromethyl)ether
Bis(2-chloroethyl)ether
2,4,6-trichlorophenol
2-chlorophenol
1,2-dichlorobenzene
1,4-dichlorobenzene
3,3-dichlorobenzidine
2,4-dichloro phenol
1,2-dichloro propane
4-chlorophenyl phenyl ether
Bis(2-chloroisopropyl)ether
Dichlorod i fluoromethane
Hexachlorobutadiene
Hexachlorocyclopentadiene
Isophorone
2-nitrophenol
2,4-d initrophenol
4,6-dinitro-o-cresol
N-nitrosodimethylamine
N-nitroso-n-propylamine
Dimethyl phthalate
3,4-Benzofluoranthene
Benzo(k)fluoranthene
Benzo(ghi)perylene
Dibenzo(a,h)anthracene
Indeno(1,2,3-Cd)pyrene
Aldrin
Dieldrin
Chlordane
4,4'-DDT
4r4'-DDE
4,4'-ODD
-endosulfan
-endosulfan
endosulfan sulfate
endrin
endrin aldehyde
heptachlor
heptachlor epoxide
-BHC
-BHC
-BHC
-BHC
PCB-1242
PCB-1254
PCB-1221
PCB-1232
PCB-1248
PCB-1260
PCB-1016
Toxaphene
52
-------
Table 4-4
Synfuels Nonconventional Organic Pollutants
and Appendix C Compounds
In Gas Quench Vfeter (ug/1)
No. of No. of
Samples Detects Min
Mean
Median
Max
Methyl ethyl ketone
Acetone
Diethyl ether
Benzoic Acid
Hexanoic Acid
Dibenzofuran
n-Dodecane
-lerpinol
Dibenzo thiophene
Biphenyl
19
19
19
19
19
19
19
19
19
19
13
14
1
8
7
11
5
1
1
9
41
166
10900
7590
10200
38
914
26
309
30
1574
8550
10900
19700
13100
4350
2270
26
309
508
5860
10300
10900
32500
14600
16600
3210
26
309
2090
53
-------
Table 4-5
Priority Metals in Low-Btu Gas Quench Wastewater (ug/1)
No. of No. of
Samples Detects Min Mean Median Max
Sb
AS
Be
Cr
Cd
Cu
Pb
Hg
Ni
Se
Ag
T TL
Zn
19
19
19
19
19
19
19
19
19
19
19
19
19
14
19
9
16
15
14
4
10
13
17
5
11
18
5
8
11
6
3
6
8
0.4
7
10
3
2
25
148
3128
12
177
22
89
92
13
206
6690
14
98
637
1100
35500
14
2250
100
301
200
21
391
51900
45
200
6600
54
-------
Table 4-6
Conventional Pollutants in Gas Quench Wastewater (mg/1)
No. of tfo. of
Samples Detects Min Mean Median Max
PH
BOE>5
Oil and Grease
TSS
20
20
19
20
20
20
19
20
6.8
340
142
11.6
8.2
*
796
534
9.3
25000
1490
5060
"8 values reported as >2000.
55
-------
grease content of the stream also is expected based on the nature
of the waste streams where tars and organics are reported by
decantation. The raw wastewater appears to be a significant
source of 8005.
The total suspended solids which averaged 534 mg/1 and the pH
which ranged from 6.8 to 9.3 should not present any problems for
handling or treating of the raw wastewater.
4.2.4 NONCONVENTIONAL POLLUTANTS
The results of the nonconventional pollutants analyses are sum-
marized in Table 4-7. The results in general are as expected
based on comparison to similar tests in coke manufacture and in
high-Btu gas manufacture. Most of the analyses can be related to
the source of the wastewater.
Since the gas being quenched contains 3 to 10 percent carbon
dioxide, the concentrations of carbonates and bicarbonates found
are to. be expected. These materials also are largely respon-
sible for the acidity and alkalinity present. The total organic
carbon and chemical oxygen demand reflect the carbon compounds
which are being removed from the gas stream in the quench
process. This large content of organic compounds is, of course,
a major factor which must be considered in the treatment and
disposal of the raw wastewater.
Phenolics average 927 mg/1 in the samples. Since phenol and
2,4-dimethylphenol were found to be the highest concentration of
priority organic pollutants, high levels of phenolics are to be
expected. Phenolics are present in sufficient concentrations
that they must be considered in the treatment and disposal of the
wastewater.
The analysis of total solids, total volatile solids, total
volatile suspended solids, and total dissolved solids all reflect
the organic material present in the samples.
Ammonia averaged 8960 mg/1 which is in sufficient concentration
to warrant its removal from the wastewater. The Kjeldahl
nitrogen includes both ammonia nitrogen and nitrogen present in
organic nitrogen compounds. The difference between the Kjeldahl
nitrogen and ammonia analyses indicates that significant quanti-
ties of nitrogen containing organic compounds are present.
Thiocyanates and chlorine are high, which probably contributes to
the difficulty in treating this wastewater by biological
oxidation (see Section 5).
The presence of sulfur compounds is expected because of the
sulfur content of the coal.
56
-------
Table 4-7
Nonconventional Pollutants in tow-Btu Gas (Xiench Wastewater (mg/1)
No. of No. of
Samples Detects Min
Mean
Max
Acidity
Alkalinity
HCO3
C03
TOC
COD
Phenol ics
Pn
GI-
F-
TS
TVS
TVSS
TDS
CN
SCN
CN/C12
Kjeldahl Nitrogen
NH3
NC>3
NO2
P04
S04
303
S=
Total Organic
Nitrogen
Ca
Mg
Na
Al
Mn
V
B
Ba
Mo
Sn
y
Co
Fe
Ti
20
20
19
19
18
19
20
18
17
19
20
19
19
20
19
19
17
19
19
17
18
20
19
19
20
18
17
17
18
17
18
17
17
17
17
17
17
17
18
17
9
20
19
12
18
19
20
1
15
19
20
19
19
20
16
19
15
19
19
12
5
18
17
19
19
18
17
17
18
17
15
12
17
14
4
9
1
8
18
15
1590 4220
1140 16600
754 15200
7 3490
207 12800
11500 62300
0.66 927
0.46
26.3 10300
1.78 1030
1220 41800
89 33400
11.2 267
578 38300
0.16 106
18 1440
0.02 309
978 9830
37 8960
1.43 132
0.56 1.4
0.051 10
49 3610
25 545
3 243
50 1460
2.22 12.6
0.175 6.8
1.51 31.2
0.261 13.6
0.007 0.64
0.003 0.08
0.63 132
0.046 0.23
0.036 0.10
0.05 0.64
0.01
0.01 0.06
0.146 74.2
0.004 0.23
10200
37500
32000
9810
34900
88000
6330
24000
3000
82300
72800
980
81700
269
3340
1130
15800
13700
357
3.5
100
15100
4300
924
5600
66.9
35.1
73.3
36.1
2.59
0.21
374
0.4
0.143
1.63
0.08
230
0.52
57
-------
4.2.5 COMPARISON TO OTHER SOURCES
The average data on general quality parameters from effluents in
this study are compared to effluents from other processes in
Table 4-8. Data on the Chapman, the synthetic process which is
similar to low-Btu gas production, have similar effluents. The
Lurgi process also is similar but somewhat lower in concentra-
tion. Coke oven operation is lower as would be expected because
of low volatile coal and higher air usage.
4.2.6 EFFECT OF OPERATING PARAMETERS
As discussed in Section 3, operating parameters such as
temperature, pressure, bed type, steam/air ratio, air/coal ratio,
and coal type will effect the constituents in the raw product gas
and thus the quench/scrubbing waters and ash sluice waters. In
general, these parameters will not have a significant enough
effect on the wastewater quality so as to change the general
treatment requirements. It would not be expected, for example,
that phenol concentrations could be reduced to the point that
dephenolization was not necessary or that ammonia concentration
could be reduced so that ammonia removal was not needed, although
there might be considerable variation in concentration.
Since operating variables interact, they can be fully discussed
by mathematical modeling of the reaction system. However, some
trends are generally accepted and are discussed here along with
observation from the sampling data.
Temperature
As temperature is increased, the rate of decomposition of high
molecular weight materials is increased and lower concentration
of these constituents can be expected. The operating tempera-
ture range of most is not sufficient to have a major effect.
Pressure^
High pressure favors the formation of hydrogen cyanide. Also,
high pressure should improve t-he efficiency of the quench
scrubbing system removing a high percentage of high boiling
organics from the gas resulting in slightly higher concentrations
in the wastewater.
The low-Btu gas effluent sampling program was set up to obtain
data from gasifiers operating at atmospheric pressure and at
elevated pressures. Two gasifiers tested were at atmospheric
pressure and two at 100-300 Ib/in2g.
58
-------
TABLE 4-8
WATER QUALITY PARAMETERS FOR THREE COAL CONVERSION
AQUEOUS PROCESS WASTEWATERS
Water Quality Parameters
Aqueous Process Wastewaters
Ul
(mq/1)
BOD
COD
TOC
NH3~ Ni troyen
Total Kjeldahl Nitrogen
Phenol
Oil and Grease
Cyanide
Thiocyanate
Sulf ide
TDS
Lurgi*
12,200
20,200
6,490
4,340
4,010
3,030
917
<0.02
83
2,010
Chapman*
15,900
28,500
9,430
8,130
9,420
2,130
540
59
1,450
207
48,600
Synthane**
15,000
8,100
2,600
152
— —
Coke Oven*
3,420
4,860
6,160
2,850
3,160
1,140
700
69
570
241
4,870
Low-Btu
25,000-2
62,300
12,800
8,960
9,830
927
1,490
106
1,440
243
38,300
Gas
,000
*Source: Reference No. 3
**Source: Reference No. 24
-------
The quantity of data and the variability preclude making a
definitive comparison of the wastewaters from the two pressures.
However, comparison of the data does indicate that low pressure
gasifiers may have more dilute wastewaters. Table 4-9 compares
the data for selected parameters for high and low pressure
gasifiers. For a number of parameters the low pressure samples
are less concentrated. It is probable that this reflects
operation of the low pressure systems at higher steam-to-carbon
ratios thus producing a greater quantity of condensate which
would have lower concentrations. It also appears possible that
pressurized systems will condense a greater percentage of the
organics present.
Air/Coal Ratio
The increased addition of air will result in a higher combustion
of organics resulting in a lower concentration of high molecular
weight materials in the wastewater.
Steam/Air Ratio
Excess steam is condensed in the quench water so that steam/air
ratio has a significant effect on the concentration of pollutants
in the quench water.
Bed Type
The bed type can have a significant effect on wastewater. In
fixed bed gasifiers, volatile components are driven off of the
coal before oxidation takes place. Thus, little of these
materials are oxidized and they largely go into the wastewater in
the quench step. In fluid bed or entrained bed gasifiers, the
coal is dispersed and more volatile materials are burned in the
gasifier resulting in lower quantities in the quench water.
Coal Feedstock
In general, coals with lower volatiles will result in lower
levels of pollutants; anthracite coal pollutants are less than
bituminous, bituminous is less than subbituminous, and
subbituminous is less than lignite. Data from the Fort Snelling
gasifier for two lignite coals and one subbituminous coal support
this general relationship.
60
-------
Table 4-9
Comparison of High Pressure and Low Pressure
Pollutant Levels
High Pressure
Range (rag/I)
Low Pressure
Range (mg/1)
Minimum
BOD
Oil and Grease
TSS
TOC
COD
Phenol ics
Cl
TS
TVS
TEE
CN
NH3
S=
Benzene
2 , 4-Ditnethylphenol
Naphthalene
Phenol
Anthracene
Phenanthrene
340
145
28
6000
25000
20
6280
48200
6720
46000
7
402
101
2130
1820
514
44400
123
329
Maximum
72000
1355
5130
28200
124000
6330
24300
83900
72800
83000
6970
23800
305
2780
12600
82700
355000
2830
10300
Minimum
1300
275
17
207
11500
0.7
26
2310
89
978
0.2
37
4
288
32
378
322
14
28
Maximum
25000
1490
1030
10100
78200
1900
2200
67600
56900
61800
35
10300
924
1050
16700
36300
90000
310
824
61
-------
4.3 ASH SLUICE WATER
Ash sluice or ash quench water is the overflow liquid from
wetting the ash which has been removed from the gasifier as a
solid. This stream usually has a high level of total and
dissolved solids from the large amount of inorganic salts in the
ash. Metals concentrations, in general, reflect the metals
content of the coal. The volume of water generated is low.
The only facility that quenched the ash was Ft. Snelling. Here
ash from the gasifier is sluiced for disposal. Also, the dust
collected by a cyclone was removed in a water bath below the
cyclone. Both waste streams were sampled during all three sample
episodes. Data are presented in Tables 4-10 through 4-19.
The Ft. Snelling sluice waters are much lower in organics than
the gas quench waters - generally by a factor of 103 or 104.
Mean values are generally less than the detection limit.*
Organic concentrations in the cyclone quench water are somewhat
higher than the ash sluice waters but still generally lower than
the gas quench liquor - generally by a factor of 10 .
Metals are not much different in concentration between the ash
sluice and the gas quench waters. Cyclone quench waters are
lower (by a factor of 10) in metals concentration than either of
the other waste streams.
BOD is much lower (close to that of domestic sewage) in both the
ash sluice and cyclone quench waters than in the gas quench
liquor.
While the pH's of all waste streams tend to be slightly basic,
the ash sluice water is more so - averaging 11.4 units. TSS of
course is much higher for the ash sluice waters - ranging from
281-15,700 mg/1.
Other nonconventional concentrations for the cyclone quench and
the ash sluice are somewhat similar. These wastewaters are
generally lower in the organic parameters (such as COD,
phenolics, and TVS) than are the quench waters. These
wastewaters are also low in nitrogen.
*The detection limit for organic priority pollutants is 10 mg/1.
This level is the minimum concentration below which the
signal-to-noise ratio was of sufficient magnitude to give a
quantifiable value for the specie concentration.
62
-------
Table 4-10
Priority Organic Pollutants Detected
In the Ash Sluice Water (ug/1)
Pollutant
2,4,6 Trichlorophenal
p-chloro-m-cresol
2,4,Dimethyl Phenol
2,4,Dimitrotolnone
Fluoranthene
Methylene Chloride
Isophorone
Naphtalene
2-Nitrophenol
4Hflitrophenol
4,6-Dinitro-o-cresol
N-n i trosophenylami ne
Pentachlorophenol
Phenol
Bis (2-ethylhexyl) phthalate
Di-n-butyl phthalate
Di-n-octyl phthalate
Diethyl phthalate
Benzo(a)anthracene
Chrysene
Anthracene
Phenonthrene
Pyrene
Trichloroethylene
Tetrachloroethylene
No. of ND. of
Samples Detects Min Mean Max
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
2
4
4
3
1
13
1
2
2
1
2
2
2
11
2
4
3
3
3
1
2
3
1
1
10
1
1
1
1
1
3
18
3
4
1
2
2
1
1
1
1
2
2
10
1
1
79
1
2
38
2
26
1
5
2
1
1
1
1
1
50
10
5
30
1
317
4
38
19
171
373
2
10
2
2
1
1
21
63
-------
Table 4-11
Priority Metals Detected in the Ash Sluice Water (ug/1)
Pollutant
Sb
AS
Be
Cr
Cd
Cu
Pb
Hg
Ni
Se
Ag
Tl
Zn
No. of
Samples
14
14
14
14
14
14
14
14
14
14
14
14
14
No. of
Detects
6
13
12
11
8
14
10
7
12
8
8
3
14
Min
2
3
1
33
7
30
3
0.1
5
2
1
1
23
Mean
48
898
17
212
19
353
122
0.6
520
51
2
2
410
Max
250
3500
50
890
41
972
350
2
1750
144
4
3
1110
64
-------
Table 4-12
Nonconventional Organic and Appendix C Pollutants
Detected in the Ash Sluice Water (ug/1)
Pollutant
No. of
Samples
No. of
Detects
Min
Mean
Max
Methyl ethyl
Acetone
Benzoic Acid
n-Dodecand
x-picoline
Biphenyl
ketone
14
14
14
14
14
14
6
9
1
2
1
2
1
9
19
43
3
23
15
2
65
-------
Table 4-13
Nonconventional Pollutants Detected in the
Ash Sluice Water (mg/1)
Pollutant
Acidity
Alkalinity
HC03
COS
TOC
COD
Phenolics
Br
Cl
F
Total Solids
Total Volatile
Solids
Total Volatile
Susp. Solids
Total Dissolved
Solids
CN
SCN
CN/C12
Kjeldahl Nitrogen
NH3
NO3
NO2
PO4
S04
SO3
S
Total Organic
Nitrogen
Ca
Mg
j
Na
Al
Mn
V
B
Ba
Mo
Sn
Y
Co
Fe
Ti
No. of
Samples
14
14
14
14
14
13
12
14
13
14
14
14
14
14
14
14
12
14
14
13
13
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
No. of
Detects Min
5
14
3
14
12
13
1
1
13
14
14
14
14
14
2
9
6
13
11
8
9
13
14
11
13
11
14
14
14
14
14
14
14
14
9
8
9
7
14
14
75
151
24
111
2
32
3
0
2520
129
26
272
0
1
0
1
1
0
0
0
52
7
3
.8
.2
.6
Mean
550
1570
462
346
12.5
276
2.8
0.2
30
1
.3
25900
930
351
18000
.02
.02
.02
.03
.09
0
3
0
5
3
1
0
11
.02
.6
.03
.5
.7
.05
.4
23400
0.1
104
5.
10.
7.
0.
0.
1.
0.
0.
0.
0.
0.
7.
0.
8
7
5
062
012
97
3
15
14
007
069
7
32
297
36
4
8
.3
45
156
4800
282
1.
0.
16.
1.
1.
0.
0.
0.
293
11.
Max
1520
3270
1310
1860
30.6
1010
112
239
77400
3700
930
60590
0.0
8.4
0.1
11
6
5.9
2
0.12
101
85000
870
139
11
1790
753
15700
1100
55 4.
48 1.
8 50.
65 4.
80 5.
39 0.
103 0.
157 0.
1340
8 32.
09
07
6
77
27
73
30
30
7
66
-------
Table 4-14
Conventional Pollutants Detected in the Ash Sluice Water (mg/1)
Pollutant
pH
BODS
Oil and Grease
TSS
No. of
Samples
14
14
14
14
No. of
Detects
14
14
14
14
Min
9.6
<1
<1
281
Mean
11.4
150
17
4820
Max
12.5
570
91.8
15700
67
-------
Table 4-15
Priority Organic Pollutants Detected
In the Cyclone Quench Water (ug/1)
Pollutant
Acenaphthene
Benezene
2,4,6-Tr ichlorophenol
p-chloro-m-cre sol
Chloroform
2,4-Dichlorophenol
2,4, Dimethylphenol
2,4, Dinitrotoluene
2,6-Dinitrotoluene
1,2-Diphenylhydrazine
Ethylbenzene
Fluoranthene
Methylene chloride
Methyl chloride
Isophorone
Naphtalene
4-Nitrophenol
2,4-Dinitrophenol
4,6-Dinitro-o-cresol
N-nitrosophenylamine
Pentachlorophenol
Phenol
Bis (2-ethylhexyl) phthalate
Di-n-butyl phthalate
Di-n-octyl phthalate
Diethyl phthalate
Benzo(a)anthracene
Benzo(a)pyrene
Chrysene
Anthracene
Fluorene
Phenanthrene
Pyrene
Ibluene
No. of No. of
Samples Detects Min Mean Max
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
7
3
2
5
1
1
16
3
1
3
6
9
15
1
3
15
4
1
4
6
4
16
3
9
3
4
5
3
6
11
14
12
12
3
<1
60
<1
6
34
<1
5
<1
<1
5
9
10
<1
<1
4
<1
170
<1
<1
31
2
<1
<1
<1
2
2
2
<1
<1
1
121
15
21
11
483
4
2
11
4
77
116
24
15
139
1
41
16
11
42
2570
2
6
66
5
4
2
2
7
11
11
4
20
4
162
49
31
1540
8
19
8
655
1020
18
1550
3
55
23
152
5760
4
23
86
9
10
4
5
36
34
41
2
59
68
-------
Table 4-16
Priority Metals Detected in the
Cyclone Quench Water (ug/1)
No. of No. of
Pollutant Samples Detects Min Mean Max
Sb 16 7 1 1
As 16 15 4 24 4
Cr 16 15 3 14 100
Od 16 8 2 27 23
Cu 16 12 6 18 100
Pb 16 10 7 48 30
Hg 16 4 0.1 0.1 164
Ni 16 5 8 36 0.2
Se 16 15 1 28 76
Ag 16 10 1 2 150
Zn 16 13 39 72 3
69
-------
Table 4-17
ISbnconventional Organic and Appendix C
Pollutants Efetected in the Cyclone
(Xiench Water (ug/1)
No. of No. of
Pollutant Samples Detects Min Mean Max
Methy ethyl ketone 15 15 7 100 533
Acetone 15 15 76 320 3600
Dibensofuran 15 15 4 67 180
n-Dodecane 15 15 7 19
-Terpinol 15 15 8 10
-Picoline 15 15 19 88 347
Biphenyl 15 15 2 13 70
Hexanoic Acid 15 15 1
70
-------
Table 4-18
Conventional Pollutants Dectected in the
Cyclone Quench Water (mg/1)
No. of ND. of
Pollutant Samples Detects Min Mean Max
pH 16 16 6.4 7.3 8.6
BOD 16 13 46 160 540
Oil & Grease 16 7 2.9 20 59
TSS 16 16 16 309 1468
71
-------
Table 4-19
Nonconventional Pollutants Detected
In the Cyclone Quench Water (rog/1)
Pollutant
No. of No. of
Samples Detects
Min Mean Max
Acidity
Alkalinity
HC03
C03
TOG
COD
phenolics
Br
Cl
F
Total Solids
Total -\folatile Solids
Total Volatile Susp. Solids
Total Dissolved Solids
CN
SCN
CN/C12
Kjeldahl Nitrogen
NH3
NO3
NO2
P04
SO4
S03
S=
Total Organic Nitrogen
Ca
Mg
Ha
Al
Mn
V
B
Ba
MO
Sn
y
C3o
Fe
Ti
16
16
16
16
16
16
16
16
16
16
15
15
16
15
16
16
16
15
15
15
14
16
13
16
16
15
16
16
16
16
16
16
16
16
16
16
16
16
16
16
6
16
16
2
16
16
13
1
15
16
15
15
16
15
12
8
16
15
15
11
8
16
13
6
16
15
16
16
16
16
16
14
14
15
4
10
1
0
16
16
8
35
35
16
3
32
0.006
1.32
1.2
248
35
10
156
0.03
1
0.02
8
1
0.15
0.02
0.04
17
1.1
2
2
19.8
3.69
5.13
0.6
0.042
0.003
0.144
0.075
0.036
0.035
1.48
0.009
72
141
136
67
250
1.96
1.03
10.5
2.22
728
352
214
338
0.09
4.2
0.1
18
8.3
1.3
0.09
0.74
70
3.8
5.7
9
31.2
6.89
35.2
5.55
0.072
0.013
0.546
0.842
0.16
0.056
0.007
7.22
0.177
150
392
392
41
258
506
22.7
47
7.3
2656
1032
964
784
0.34
8.6
0.265
38
25
2.7
0.45
3.68
182
14
32
23
89.1
18.2
104
23.2
0.216
0.038
1.2
3.8
0.5
0.082
30.8
0.472
72
-------
4.4 ACID GAS REMOVAL
Operation of the four gasifiers sampled did not generate efflu-
ents appropriate for sampling from the acid gas removal systems
as these operations were not purged on a steady state basis.
Pollutants from acid gas removal systems largely depend on the
degree of gas clean-up before entering the acid gas removal
system and on the type of system used. In general, if a clean
gas is used, there is no effluent from the process (8).
73
-------
SECTION 5
TREATMENT TECHNOLOGY
Low-Btu gasification wastewaters present treatment problems not
routinely encountered by normal wastewater treatment plants. As
shown by the four g'asifiers sampled and presented in Section 4,
low-Btu gasifier wastwaters contain high concentrations of
phenolics, ammonia, sulfur compounds, and organics (some of which
are priority pollutants) as well as high solids and trace
concentrations of heavy metals.
This section describes the treatment of low-Btu gasification
gas quench waters. The information is based primarily on the
results from an EPA wastewater treatability study performed
on-site at a low-Btu gasifier. After a complete literature
search, bench scale study, and application of information from
other industries, the treatment units in this study were
designed, constructed, and operated.
This section also lists those studies that have been or are being
performed on low-Btu gasification wastewaters after completion of
this treatability study (after 1981).
5.1 SCOPE OF THE EPA TREATABILITY STUDY
The low-Btu gasifier wastewater treatability study was conducted
in three phases. Phase I was a comparison of low-Btu wastewater
characteristics with those of analogous industries to determine
applicable treatment technologies (12). Phase II was a six-week
operation of a bench-scale system, the results of which were used
to derive design and operating specifications for the pilot-scale
unit (48).
Phase III was the construction and operation of an on-site
pilot-scale wastewater treatment plant at a commercial low-Btu
gasifier (30). Operation of this plant was for two months. An
extensive sampling and analysis program was conducted during the
pilot plant operation in order to monitor pollution removal
efficiencies of each treatment unit. The data from Phase III
confirmed the position, developed during the study of analogous
industries, that low-Btu gasifier wastewater is similar to that
produced at coke plants and the basis for the treatment of the
two is similar.
74
-------
Certainly all treatment technologies have not been explored and
others may be applied with equal or better success. The purpose
of using the selected treatments is to demonstrate the levels of
removal that can be achieved by technologies proven in
commercially operating industries.
5.2 THE EPA TREATABILITY STUDY SITE
The pilot plant treatability study was performed at the Holston
Army Ammunitions Plant low-Btu gasifier (described in Appendix
A). This facility was commercially operating at the time the
study was perfomed and employed the Wilputte-Chapman gasification
technology. it is also one of the four gasifiers sampled and
discussed in Section 3. The wastewater for this study was
recycled quench liquor from a series of three gas scrubbers. The
scrubber water was collected in a decanter tank where tars settle
to the bottom of the tank and are removed periodically. Excess
quench liquor is periodically sent to an evaporator for disposal.
However, during the treatability study, ths excess (which
amounted to approximately 300-1,000 gpd) was routed to the
wastewater pilot plant for treatment.
5.3 PILOT PLANT DESCRIPTION
The treatment systems were sized for the minimum daily volume of
water that would be available from the gasifier during the study
period (about 300 gpd). Consequently, those units to be operated
continuously were sized for a flow of 300 gpd or 0.2 gpm. Units
that could operate on a batch basis were sized larger to more
closely reflect larger commercially operating systems. These
units, described below, were the ammonia columns and
dephenolization units sized at 3 gpm.
The processes selected for use in the pilot plant were:
Pretreatment
o Roughing Filter
o Dephenolization
o Ammonia Stripping
Secondary/Tertiary Treatment
o Biological Oxidation
o Multi-Media Filtration
o Carbon Adsorption Polishing
Each of these treatments is described in detail in Reference No.
30: Low-Btu Gasifier Wastewater Treatability; Phase III Pilot
75
-------
Plant Study at Holston Army Ammunitions Plant. The treatment
processes are described here briefly. The schematic flow is
shown in Figure 5-1.
5.3.1 ROUGHING FILTER
The roughing filter consisted of a cylindrical bed of coal used
primarily to remove globules of tar and or pitch. The raw
wastewater is passed through the bed. When the bed ceases to
remove material from the stream (due to clogging by the tar), it
is removed and disposed of by feeding the coal into the gasifi-
cation process. Thus, the advantage to this treatment step is
that there is no secondary waste created. The operation is shown
in Figure 5-2.
5.3.2 DEPHENOLIZATION
Phenols were removed using a solvent extraction process. In the
first stage the phenol laden wastewater comes in contact with a
countercurrent flow of solvent, benzol in this case. The sol-
vent extracts most of the phenol and some other organics. In the
second stage the phenol-laden solvent comes in contact with a
caustic solution which extracts the phenols so that the solvent
can be recycled. Other solvents can be used besides benzol. The
system is shown schematically in Figure 5-3.
5.3.3 AMMONIA STRIPPING
Ammonia stripping removes ammonia from the wastewater by vapori-
zation. The wastewater is passed through a column counter-
current to a stream of steam. Ammonia is stripped from the
liquid and taken off with the vapor. In the pilot plant the
vapors were condensed forming a concentrated ammonia solution.
Some organic material is also volatilized and removed with the
ammonia.
In water, ammonia exists both as free ammonia and as ammonium ion
(fixed ammonia). The ratio of free ammonia to ammonium ion is
determined by the pH. At low pH, essentially all of the ammonia
is present as ammonium ion (fixed ammonia.) At high pH (above
9.8), essentially all of the ammonia is present as free ammonia.
Only the free ammonia can be removed by stripping which is why
the pH must be raised.
In the pilot plant, ammonia stripping was done in two stages as
shown in Figure 5-4. The first stage stripped the wastewater
without adjustment of the pH. This free ammonia still removed
that portion of the ammonia that was free in the wastewater
76
-------
INFLUENT
HOUGHING
FILTER
FRESH BENZOL
FRESH tOt CAUSTIC
SOLUTION.
DEPHENOLIZATION
COLUMN
BENZOL
REMOVAL
COLUMN
STEAM
FREE LEG
AMMONIA STILL
PH ADJUST.
TANK
FREE LEG
AMMONIA STILL
CAUSTIC SOLUTION 501
DILUTION MATER
PHOSPHORIC ACID
PRETREATMENT
MASTEHATER
STORAGE TANK
EFFLUENT -4-
I
CONOENSATE
BIO-AERATION
TANK
BIO-CLARIfIER
RECYCLED SLUDGE
CARBON
ADSORPTION
FILTRATION
&OLIUS
Figure 5-1. Schematic Flow Diagram
-------
WASTEWATER
PROM EXISTING
DECANTER =
TANK.
TO
DEPHENOL1ZATION)
WASTEWATLR
PROM EXISTING.
DE.CANJTEK.
TANK.
TO
PEPMENOHZAT1QN
SYSTEM
PL.AN
INPLUBNT STORAGE.
ROUGHING PILTER
INFLUENT STORAGE
TANK
RECYCLE. LINE
DEPMENOLIZER
SUPPLX
ROUGHING PILTER
GASIPIER COAL
RECYCLE LINE
DEPMENOLIZER.
SUPPLY PUMP
ELEVATION
Figure 5-2. Roughing Section Filter
78
-------
SOLVENT
TO RETURN
EFFLUENT
SOLVENT
PRETREATED
INFLUENT
WASTEWATER
PHENOL
SOLVENT
RECOVERY
INFLUENT
SOLVENT
PHENOL TO
DISPOSAL OR
RESALE
EFFLUENT
WASTEWATER
Figure 5-3. Dephenolizer
79
-------
1,
INFLUENT-
AMMONIA
STILL
FREE LEG
oo
o
AMMONIA
STILL
FIXED LEG
BOILER
STEAM
r
AMMONIA
CONDENSATE
TO DISPOSAL
OR AMMONIA
RECOVERY
CAUSTIC
FEED SYSTEM
EFFLUENT
WASTEWATER
Figure 5-4. Ammonia Still
-------
before pH adjustment. The pH of the wastewater was then raised
releasing the fixed ammonia. A second stripping was then
performed removing the fixed ammonia.
5.3.4 BIOLOGICAL OXIDATION
The biological oxidation unit was an activated sludge unit
consisting of an aeration tank and a settler. The wastewater is
brought into the aeration tank where the biomass digests
biologically oxidizable organic matter. The settled solids from
the settler are recycled to the aeration tank with any excesses
purged. The unit is shown schematically in Figure 5-5. The raw
wastewater was introduced into the "seed" sludge at 10 percent
dilution intervals until a 50 percent dilution was reached. This
was done in an attempt to slowly stabilize the system.
5.3.5 GRANULAR - MEDIA FILTRATION
Granular media filtration consisted of a filter column filled
with gravel, sand, and anthracite coal in three separate layers.
The wastewater was passed through the filter to remove suspended
solids that existed after settling from biological oxidation.
When flow rates reduced, the filter was backwashed and agitated
with compressed air. The backwash was collected and recycled to
the feed. The unit is shown in Figure 5-6.
5.3.6 CARBON ADSORPTION
The carbon adsorption unit, used to remove residual organic
pollutants, consisted of a column filled with activated carbon.
When the activity of the carbon is reduced, it is replaced with
reactivated material. Absorption resin was also tested instead
of activated carbon. The activated carbon unit is shown in
Figure 5-6 with the multimedia filtration.
5.4 SAMPLING AND ANALYSIS
Sample points were established before and after each treatment
step. On-site analyses for process control included pH,
alkalinity, TSS, TDS, settleable solids, phenol, ammonia, TOC,
COD, and chlorides. These were taken daily. In addition to
these, the priority pollutants, and other parameters such as TVS,
TKN, nitrate, phosphorus, TCN, SCN, sulphates, and sulphites,
were collected twice a week and sent off-site to EPA contract
laboratories for analysis.
81
-------
WASTE WATER
NUTRIENT
ADDITION
CO
to
AIR SUPPLY FOR
SURFACE AERATION
OR
SUBMERGED AERATION
USING AIR COMPRESSORS
SLUDGE
TREATMENT
SOLIDS TO
DISPOSAL
INFLUENT
V
AERATION BASIN
SLUDGE RECYCLE
FINAL
CLARIFIER
-»• EFFLUENT
Figure 5-5. Activated Sludge
-------
UELGE.ND
00
CO
C.OI.UMIM
AIK
-tXJ—h
pfl
BA.CKV4A3M
ePPUUCNT TO
OISCHARCC AND
MAIN WA.STEWATE.ft
PL.OW LtMfc
FILTER PEE.C7
Figure 5-6. Effluent Polishing
-------
5.5 RESULTS
The effect of the pretreatment system is evaluated in terms of
chemical oxygen demand (COD), total organic carbon (TOG), ammonia
and phenols. The secondary treatment system is evaluated in
terms of biochemical oxygen demand (BOD), TOC, and COD.
5.5.1 PRETREATMENT
The effect of the pretreatment operations is shown graphically in
Figure 5-7 which shows the average effect of each step and the
overall effect of the combined treatment. Overall, the
pretreatment train was quite successful.
5.5.2 BIOLOGICAL OXIDATION
A graphical presentation of pollutant removals across the bio
unit is shown in Figure 5-8. Considerable reduction in BOD and
other .parameters was obtained, yet full stabilization was not
achieved, even at 50 percent dilution. However, as shown by
Figure 5-8, BOD reductions began to increase with time,
indicating that stabilization might have been achieved with
additional operation time.
Phenols were reduced by an average of 88 percent and thiocyanate
was reduced by an average of 52 percent. COD and TOC removals
were very erratic, ranging from no removal to 44 percent and 64
percent reduction, and averaging 35 percent and 24 percent
reduction, respectively. Ammonia concentrations increased
across the system in 42 percent of the analyses. This may be
partially attributable to the breakdown of cyanide compounds,
including thiocyanate, which is typical in the treatment of this
type of wastewater.
Average suspended solids in the effluent (after reaching 50
percent dilution) were 265 mg/1 and the average suspended solids
in the effluent were 674 mg/1. This was due to poor settling in
the clarifier, primarily a result of the suspended colloidal
nature of the solids as discussed in Section 5.6, entitled
"Problems Encountered."
MLSS in the aeration tank ranged from 490 mg/1 (on December 29)
to 6280 mg/1 (on November 27), averaging 2774 mg/1. This average
solids concentration was less than the target level of 5000 mg/1
due to the lack of proper solids settling in the clarifier,
which, consequently, produced insufficeint solids in the recycled
sludge. Average sludge age was 21 days based on the equation:
Sludge aqe = MLSS x Aeration Period (days)
Influent SS
84
-------
100,000
10.000
0
z
n
n
z
H
Q
Z
Gl
fOOO
IOO
R AW i Ni I
2) RC'_)iSM(N3 P!\_TtR EFFLUENT
CTREE. L.E.G NHaSTMl_L_
EPPl_UE_N~T
PtXED LEG NM3 ŁTl\
E.PPLUE.NJT
AVERAGE OVERALI-
% REDUCTION
REDUCTION
SI %
REDUCTION
REDUCTION
RETDUCTIOM
Figure 5-7. Performance of Pretreatment Units
85
-------
Figure 5-8.
00
en
IOO-
30
2
g
u
D
Q
uJ
DC
Z
U
u
DC
U
a
PERCENT REDUCTION IN BOD. TOG 4 COD
ACROSS BIO-UN IT e 50% GASIFIER DILUTION
I I
LEGEND:
D BOD
• TOC
A COD _
+ INCREASE IN PARAMETER
DASHED LINE INDICATES
MORE: THAN ONE DAY
INTERVAL. BETWEEN"
ANALYSES
DATE
-------
When considering this parameter, it should be noted that problems
occurred with the sludge used for seed and with foaming, which
affected the MLSS concentrations.. These problems, their causes
and possible solutions, are also presented in Section 5.6.
5.5.3 GRANULAR-MEDIA FILTRATION
The granular-media filter was not effective in reducing total
suspended solids to less than 20 mg/1, the target level. Average
filter effluent TSS were 304 mg/1, which is a 43 percent
reduction. TOC and COD reductions averaged 30 percent and 14
percent, respectively.
The difficulty in filtering the solids also was attributed to the
nature of the influent suspended particles rather than problems
with the operation of the filter.
5.5.4 ADSORPTION
The carbon and resin coolums were both effective in further
reduction of the TSS remaining in suspension after filtration by
41 percent and 61 percent, respectively. However, the removal of
TSS is not the function of adsorption units and the presence of
high TSS in the influent to these units normally interferes with
their proper operation.
The color of the wastewater was not noticeably affected by the
adsorption system and remained the same brownish/black color of
the influent wastewater. This was attributed to the colloidal
suspended material remaining in the effluent.
Overall, the activated carbon was slightly more effective in
reducing TOC and COD than the resin.
5.5.5 OVERALL TREATMENT EFFICIENCY
The color of the treated wastewater was not significantly
different from the raw Holston wastewater and remained a dark
brownish/black. Average suspended solids had increased in the
treated water, presumably due to the poor settleability of the
wastewater discharging the biological unit. Since the solids did
not settle in the biological system clarifier, they were of a
nature that precluded their effective removal in the granular-
media filter. However, the concentration of dissolved solids in
the final effluent was reduced by about 77 percent.
87
-------
Table 5-1 shows parameter reductions across the entire pilot
plant. They do not represent either minimum, maximum, or average
treatment levels that should be expected, but are a presentation
of the actual performance obtained during the treatability study.
Table 5-1
Effect of Overall Treatment System
Parameter % Reduction(l)
TSS 72 (increase)
TDS 77
TOC 88
COD 92
Ammonia 99
Phenols 99.8
(1) Reduction in parameter concentration, feed concentration
less final effluent concentration divided by feed con-
centration times 100.
5.6 PROBLEMS ENCOUNTERED
Several problems were encounterted during the operation of the
pilot plant which impaired the removal of pollutants. These
problems are summarized below:
o TSS increased across the roughing filter - This increase
may have been due to the breakdown of the media (coal)
used for the filter. However, bench scale tests performed
to investigate this problem were inconclusive. Attempts
to correct this problem for commercial operation may be
either to use a different filter medium or to install a
settling tank or clarifier after the filter.
o Tar deposited on the media in the dephenolizer columns -
Apparently, tar remaining even after rough filtration was
enough to agglomerate on the dephenolization columns.
While the build-up was not enough to impair efficiency of
the columns during its operation, it may cause difficul-
ties in longer operating commercial operations. Scheduled
backwashing may be necessary or cooling of the raw waste-
88
-------
water before or after rough filtration followed by
precipitation of additional tar-like substances may be
performed.
Foaming in the ammonia still - This caused a carryover of
wastewater in the steam condensate, particularly in the
free leg. This problem only occurred when the pH was high
from the dephenolization units. Proper pH control should
eliminate this problem.
Biological oxidation stabilization - The most perplexing
difficulty encountered during operation of this pilot
plant was the stabilization of the biological oxidation
units. Due to problems with several of the sludges used
for seed, the unit had to be restarted twice during the
pilot plant period. Sufficient time to completely
stabilize the unit was not available as a result.
The adaptability of the final sludge used for seed was
evidenced by the increased BOD removal at the end of the
pilot plant operation. In future operations, much more
time should be allocated to stabilizing the units.
Foaming - Foaming was a consistent problem throughout the
pilot plant operations. Aside from the pH problems in the
ammonia stills, it is believed to be due to various
foaming compounds in the wastewater such as naphthalene.
Foaming was present in the biological oxidation aeration
tank, the ammonia stills, the final clarifier, and the
holding tanks. Future operations should include provision
for a continuous fine spray to be applied over the tanks
to suppress the foam (which worked in the pilot plant
operations), or research should be done to investigate
possible removal of foam-causing agents in the
wastewater.
Bio-unit solids carryover - Large quantities of suspended
solids were present in the effluent from the bio-unit. It
was determined by passing the wastewster through a
Millipore filter that the solids were of a colloidal
nature, which would not settle and could not be removed by
normal filtration. These solids severely interferred with
proper operation of the resin and activated carbon
adsorbents because they clogged the media. This, in turn,
impaired proper operation of the tertiary treatment units.
By using jar tests, it was determined that these colloidal
solids could be removed via polyelectolytes in combination
with 'chemical addition (such as lime, ferrous sulfate, or
alum). Further research on this is needed.
89
-------
Sludge produced from the bioreactors may contain
polycyclic aromatic hydrocarbons and heterocyclic
compounds (49). The sludge should be disposed of, and two
possible methods are incineration and wet oxidation. Due
to the high moisture content of the sludge, incineration
may be very expensive. Wet oxidation is investigated
further in Reference No. 49.
5.7 TREATABILITY STUDY CONCLUSIONS
The pretreatment units in the pilot plant worked quite
successfully in removing certain precursors to the biological
treatment units. Recovery of ammonia from the ammonia strippers,
and phenol from the dephenolizers, are a secondary benefit from
these systems. Also, the spent roughing fiter media, in this
case coal and tar and pitch, can be reused in the gasifier.
The biological oxidation unit needed more time for stabilization,
yet problems that arose from its operation have revealed specific
research needs and/or operational corrections that can lead to
highly successful future technologies.
5.8 OTHER STUDIES
In addition to studies listed in EPA's original literature search
on coal gasification (29), and studies listed in the bibliography
of this report, this section lists more recent reports or ongoing
studies since the completion of the treatability study in 1981.
There are many studies on the treatability of gasification
wastewaters but few specifically limited to those of low-Btu
gasifiers. Most of the work performed on low-Btu gasification
wastewaters in recent years has been funded by the Department of
Energy and performed by various universities or DOE's Energy
Technology Centers. In particular, much work has been performed
at DOE's Grand Forks Energy Technology Center, which operates a
small slagging fixed-bed, low-Btu gasifier for research purposes.
Information on the treatability of wastewaters from this study is
reported in Reference No. 22 and briefly summarized below.
5.8.1 SLAGGING FIXED-BED GASIFIERS
Two combinations of treatments were examined. The system used in
Phase I is shown in Figure 5-9 and that in Phase II in Figure
5-10. The steps involved are compared below:
90
-------
Ca(OH).
GASIFIER
HASTE
FEED
FREE1
STRIPPER
filtpr
FIXED NH,
V
STRIPPER
LIME
SLUDGE
Na-(C03) AlUM (If needed)
"C" Sludge
containing
CaCO, A
organks "A" Sludge
alum with
organlcs
Sludge
Wasted
Figure 5-9. Block Diagram of GFETC Wastewater
Sludge Generation System (Phase 1)
-------
Row
WW.
Solvtnt
Mixing
ond
Solv tnf
Strp
LImt
Mining
vo
NJ
Fixed
NH_ Strip
3
Mixing
Pr«tr«ofed
WW.
Figure 5-10. GFETC Gasifier Wastewater Pretreatment Train (Phase 2)
-------
Phase I
Free Ammonia Stripping
Lime Addition
Sludge Removal
Fixed Ammonia Stripping
Sodium Carbonate Addition
Sludge Removal
Alum Addition
Filtration
Biological Treatment
Phase II
Solvent Extraction
Free Ammonia Stripping
Lime Addition
Sludge Removal
Fixed Ammonia Stripping
Sodium Carbonate Addition
Sludge Removal
Biological Treatment
The biological treatment unit removed 98 percent of the BOD and
80 percent of the TOC. Such removals reflect the careful control
conditions of the study and not commercial operation. Ammonia
removal was about 83 percent in the combined sripping operations.
The ammonia stripping was done with air at 170°F rather than
steam in a countercurrent stripping column.
The effect of solvent extraction with methylisobutylketone (MIBK)
at a ratio of one volume MIBK to 25 volumes of waste as used in
Phase II. In the extraction step, 53 percent of the phenol was
removed. Combined free and fixed ammonia stripping removed 91
percent of the ammonia. Biological oxidation of Phase II
wastewater was similar to that in Phase I.
The advantage of using lime instead of sodium hydroxide to raise
the pH for ammonia stripping is that dissolved inorganic salts
are not increased significantly. In addition to avoiding the
discharge of the dissolved sodium, it is believed that the lower
inorganic solids content improved the settleability of the sludge
in the biological operation.
Other more recent studies (as of May, 1986) pertaining to
wastewater treatment from this gasifier are listed below along
with their abstracts.
o Hendrikson, J. G. , and G. G. Mayer, "Gasification Waste-
water Treatment and Reuses," August, 1984, Low Rank Coal
Research Quarterly Technical Progress Report, April-June,
1984.
ABSTRACT: Results from the Phase II test showed that
aqueous gasifier effluent treated by solvent extraction,
steam stripping, AS processing, GAG adsorption, and
multimedia filtration was not suitable as feed to a
cooling tower operated at 10 cycles of concentration.
This water was high corrosive to carbon steel, with
corrosion rates of 19 to 65 mpy measured during this test.
This water caused severe fouling of carbon steel,
93
-------
resulting in large pressure drop increases and decreases
in heat transfer coefficients for carbon steel heat
exchanger tubes. These results indicate that for this
water to be used successfully as makeup to a cooling
tower, the addition of chemicals for the control of
corrosion and the associated fouling will be necessary, or
substitution of stainless steel or some other corrosion
resistant material for all carbon steel will be required.
This water did not appear to support any substantial level
of biological activity. Exhaust air from the tower was
free from organics, but a substantial amount of ammonia
was stripped from in the tower (65 percent of the influent
quantities). Adsorption geotherm studies have been
completed for the biologically treated and dual-media
filtered SGL to determine the feasibility, of using GAC to
adsorb nonbiodegradable substances, such as hydantoins. A
batch kinetic experiment was performed to determine the
equilibrium time. Fourteen figures and 18 tables.
o Paulson, L. E., et al., "Utilization of Powdered Activated
Carbon in Activated Sludge Process in Treating Coal
Gasification Wastewater," AIChE Summer Nat. Mtg., Detroit,
MI, Paper No. 386, August 16-19, 1981.
ABSTRACT: A laboratory study was conducted to examine the
biological treatability of wastewaters produced from the
slagging fixed-bed gasification of North Dakota lignite
using powdered activated carbon (PAC) activated sludge
process. Four bench-scale continuous completely mixed
activated sludge reactors were monitored for contaminant
removal efficiencies and kinetic coefficient determina-
ation. At a hydraulic detention time of one day, effluent
COD concentration decreased with the increasing level of
PAC in the reactors up to 34 percent decrease at 6 g/1 PAC
concentration.
o Turner, C., and T. Towers, "Installation, Operation, and
Analysis of Gasification Wastewater Treatment PDU's,"
University of North Dakota, project currently in progress.
ABSTRACT: The objective of this research is to model the
wastewater treatment scheme ^planned for the GPGA gasifi-
cation plant being constructed in western North Dakota.
To model GPGA's wastewater treatment process, the follow-
ing approach was planned: (1) a pilot-plant scale (1 GPM)
wastewater treatment train borrowed from the EPA and
installed at the Grand Forks Energy Technology Center, as
well as a cooling tower leased by DOE from Resources
Conservation Co. and also installed at Grand Forks Energy
Technology Center; (2) wastewater produced in the Grand
Forks Energy Technology Center fixed-bed slagging gasifier
94
-------
processed through the treatment train, solvent extracted
and ammonia stripped; (3) pretreated wastewater was to be
used as the cooling water in a test cooling tower loop.
Wastewater was successfully treated as a result to achieve
phenol (150 mg/1) and ammonia (500-600 mg/1) concentra-
tions similar to thbse expected in GPGA's cooling tower
make-up water.
5.8.2 OTHER LOW-BTU GASIFICATION PROCESS WASTEWATERS
Two studies have recently been completed concerning the
Westinghouse gasification process (low-Btuf ash agglomerating
fluidized-bed coal gasification). These are listed below:
o Winton, S. L. , et al., "Process Wastewater Treatability
Study for Westinghouse Fluidized-Bed Coal Gasification,"
July, 1985 (available through NTIS—PC A02/MF A01).
ABSTRACT: The paper discusses a joint program (U.S. DOE,
The Gas Research Institute, and U.S. EPA) to develop
performance data, design parameters, conceptual designs,
and cost estimates for treating wastewaters from a
fluidized-bed coal gasification plant. Preliminary
results indicate that wastewater can be effectively
treated by current technology. At this time the unit
operations being evaluated are performing according to
expectations. Results from bench-scale studies represent
a first step in the development of a basis of design for
treating these wastewaters. These data will also be used
to develop conceptual designs from which cost estimates
for wastewater treatment for a commercial-scale fluidized-
bed coal gasification facility will be prepared.
o Winton, S. C. , et al., "Treatment of Aqueous Waste
Streams from KRW Energy Systems Coal Gasification
Technology," 'International Gas Research Conference,
Washington, D.C., Sept. 10, 1984.
ABSTRACT: Ash agglomerating fluidized-bed coal
gasification technology has developed to the point where
commercial-scale systems are being planned. The KRW
Energy Systems (KRW) coal gasification process (formerly
called the Westinghouse gasification process) is
representative of this technology and has been the subject
of extensive environmental, health, and safety
evaluations. The Department of Energy (Morgantown Energy
Technology Center), The Gas Research Institute, and the
Environmental Protection Agency (Industrial Environmental
Research Laboratory, Research Triangle Park, North
Carolina) have sponsored a bench-scale evaluation to
95
-------
determine the extent to which process wastewaters from the
KRW gasification process are treatable using commercially
proven wastewater treatment technology. The program was
conducted in cooperation with KRW which provided waste-
water samples, process information, and technical review.
The treatment processes considered in this evaluation were
suspended solids removal, steam stripping, cyanide con-
version, and biological oxidation.
Further research is currently being performed on the Morgantown
Energy Technology's gasifier wastewaters. (This gasifier is one
of the four sampled in EPA's study.) The study is listed below:
o French, W. E., "Anaerobic Wastewater Treatment," U.S. DOE,
Morgantown Energy Technology Center, Morgantown, WV, study
currently in progress.
ABSTRACT: The project objective is to evaluate the per-
formance of the completely mixed, expanded-bed, granular
activated carbon anaerobic filter in treating coal
gasification wastewater. Activities are (1) to study
treatability of low-Btu, elevated pressure, fluid-bed
Wellman-Galusha gasifier wastewater with the completely
mixed, expanded-bed, granular activated carbon (GAC)
anaerobic filter; (2) to determine the interactions
between the feed wastewater strength, process loading, GAC
replacement sched- ule, and process performance; (3) to
identify major contributors to microbial inhibition
through the use of a chemically synthe- sized coal
gasification wastewater; and (4) to evaluate the loading
potential of the GAC anaerobic filter during the treat-
ment of a simulated wastewater monohydric phenols.
Three other studies that apply to wastewater treatment for
gasifiers in general (not necessarily to low-Btu gasifiers) are
listed below also:
o
Castaldi, F. J. , and S. L. Winton, "Treatment-System
Design for Process Wastewaters from Non-Tar-Producing Coal
Gasification Technology," June 1985 (available through
NTIS, PCA10/MF A01).
ABSTRACT: The report documents a study of the treatment
of wastewaters from non-tar-producing coal-gasification
processes and indicates that the aqueous wastes are
treatable with conventional technology. Wastewater-
management scenarios for treated-effluent discharge and
wastewater reuse as cooling tower makeup were examined. A
technology evaluation incorporating wastewater character-
ization and treatability data for the treatment of waste-
waters from non-tar-producing coal gasifiers established a
96
-------
single wastewater treatment system to meet both the
discharge and reuse water-management scenarios. The
example treatment system includes steam stripping,
equalization, cyanide/thiocyanate conversion for treatment
of stripper overheat condensates, biooxidation, and final
effluent filtration. This study was performed to expand
the existing wastewater data base to include characteriza-
tion, treatability, and basis-of-design information. The
results of laboratory and desk-top evaluations of alter-
native wastewater-treatraent technologies produced con-
ceptual designs for wastewater-treating facilities to meet
discharge and water-reuse needs at non-tar-producing coal-
gasification plants.
Donaldson, T. L. , et al., "Fixed-film, Fluidized-bed
Bioreactors for Biooxidation of Coal Gasification
Wastewaters," 1984, Am. Inst. Chem. Eng., Spring National
Meeting, Anaheim, CA, 20 May 1984.
ABSTRACT: Fixed-film, fluidized-bed bioreactors have been
used successfullly to treat dilute synthetic wastewaters
on a continuous basis for more than 1 year and dilute
actual coal conversion wastewaters for 9 months. The
bioreactors have exhibited stable biological activity, and
no difficult operating problems have been encountered.
Effluent phenol concentrations of less than or equal to 1
mg/1' have been obtained using synthetic wastewater
containing 30 to 40 mg/1 of phenol. Volumetric reaction
rates in the bioreactors are substantially higher than
those in suspended growth systems because of the high
concentration of retained cells on the support particles.
Bioreactor 'performance, batch kinetic studies, and
development, characterizaton, and preservation of the
microbial culture are described.
King, C. J. , "Condensate Wastewater Treatment," Lawrence
Berkeley Laboratory, University of California, study
currently in progress.
ABSTRACT: Large volumes of condensate water are formed
when reactor effleunts from coal gasification are cooled.
The project objective is to provide basic understanding so
as to develop improved physiochemical processing methods
for these condensate waters. Particular attention has
been given to solvent-extraction and stripping processes
and the determination of the chemical make-up of real
water samples. Research is focused on (1) determination
of individaul components contributing to the measured
c-hemical oxygen demand (COD) and total organic carbon
(TOO; (2) extraction, with both conventional and novel
chemically associating solvents, which enables effective
97
-------
removal of COD and TOG with low energy consumption; (3)
fractionation and removal of solutes by evaporation and
sorption processes; (4) combining extraction of ammonia
with stripping of acid gases in an innovative process that
can recover ammonia as an isolated product, and (5)
hydantoin-formation chemistry.
98
-------
SECTION 6
CONCLUSIONS
As shown by Section 4, the raw wastewaters from low-Btu gasifiers
contain a vast array of pollutants ranging from priority pollu-
tants, Appendix C pollutants, nonconventional pollutants and
metals, to conventional pollutants. Ammonia, a nonconventional
pollutant, is present in significant quantities as are phenols.
The raw wastewater contains materials that inhibit biological
treatment.
Pretreatment of the raw wastewater is necessary to remove tars
and oils, pheonols, and ammonia primarily to make the wastewater
suitable for biological treatment. Phenol removal by solvent
extraction, when combined with ammonia stripping, removes a major
portion of the organic compounds and 'has been demonstrated to
produce a wastewater that can be biologically treated. How-
ever, it is most likely that bilogical treatment of gasifier
quench waters will require dilution. Further research, primarily
on biological oxidation stabilization and t^e solids formation
and/or removal after biological oxidation, is necessary.
Many additional methods of treatment used in similar industries,
such as coking and medium-Btu or high-Btu gasification, would
appear to be usable as the raw wastewater is of similar quality.
In practice, numerous combinations of treatments can be expected.
99
-------
BIBLIOGRAPHY
1. ANR Technology Company, Performance of a Quench/ESP Tar
Scrubber on Producer Gasf D.O.E. Project Report, January
1983.
2. Buividas, L. J.f "Coal to Ammonia: Its Status", Chemical
Engineering Progress, v.77, N.5, May 1981, pp 44-53.
3. Collins, Robert V., Kenneth W. Lee and D. Scott Lewis,
Comparison of Coal Conversion Wastewaters, Radian Corp,
no date.
4. Electric Power Research Institute, Coal Gasification Systems
A Guide to Status, Applications and Economics, Palo Alto,
California, June 1983. (AP-3109).
5. Felder, R. M., et.al., "How clean Gas is Made from Coal,"
Environmental Science and Technology, v. 14, n. 6, June
1980, pp 658-666.
7. Foster, David H., Richard D. Noble and O. T. Abudu, "PACT
Treatment of Synfuel Retort Waters. I. Influence of Process
Water Components on Oxygen Uptake Rates", in Industrial Waste,
Proceedings of the Thirteenth Mid-Atlantic Conference, Newark,
Delaware, June 29-30, 1981, Ann Arbor Science Publishers, 1981,
pp. 217-227.
8. Ghassemi, M., et.al., Applicability of Petroleum Refinery
Control Technologies to Coal Conversion, Washington, D.C.,
U.S. Environmental Protection Agency, October 1978, (EPA-
600/7-78-190).
9. Green, C. R., "Synfuels: What's Economical?", Hydrocarbon
Processing, v. 61, N. 6, June 1982, pp. 77-82.
10. Hicks, R. E., et.al., Wastewater Treatment in Coal Conversion,
Washington, DC, U.S. Environmental Protection Agency, June
1979 (EPA-600/7-79-133).
11. Hung, Yung - Tse, et.al., "Assessment of Activated Sludge
Process in Treating Solvent - Extracted Coal Gasification
Wastewaters", in Industrial Waste, Proceedings of the
Thirteenth Hid-Atlant^ic^ Conference, Newark, Delaware, June
29-30, 1981, Ann Arbor Science Publishers, 1981, pp. 228-238.
12. Hydrotechnic Corporation, Technical Memorandum; Synfuels
Industry, Analogous Industries Wastewater Treatment, New
York, January 21, 1981.
100
-------
13. Iglar, Albert F., Final Report; Study of the Treatability of
Wastewater from a Coal Gasification Plant, Pittsburgh Energy
Technology Center, U.S. Department of Energy, 1980. (DOE/
ET/00234/31).
14. Jones, Fred L.f "Low BTU Coal Gasification: Bringing
Back an Old Workhorse," presented at Joint Power Generation
Conference, ASME-IEEE, Denver, Colorado, October 17-21, 1982.
15. Jones, Fred L., "Low BTU Coal Gasification, Yesterday's
Industrial Fuel for Tomorrow," Presented at 1983 Energy-
Sources Technology Conference, Houston, TX, January 30 -
February 3, 1983.
16. Jones, Fred L., "Low BTU Gas - A Fuel for Industry,"
presented at 10th Energy Technology Conference, Washington,
DC, February 28 - March 2, 1983.
17. Jones, Fred L. , "Performance of a Baffle Plate Burner on
Low BTU Gas from Coal," presented at International Con-
ference on Combustion of Tomorrow's Fuels, Santa Barbara,
California, November 7-12, 1982.,
18. Luthy, Richard G. and James T. Fallon, "Biological Treat-
ment of a Coal Gasification Process Wastewater," Water
Research, v. 14, 1980, pp. 1269-1282.
19. Luthy, Richard G. , et.al., "Cyanide and Thiocyanate in
Coal Gasification Wastewaters," Water Pollution Control
Federation Journal, v. 51, n. 9, September 1979, pp.
2267-2281.
20. Luthy, Richard G. , "Treatment of Coal Coking and Coal
Gasification Wastewaters," Water Pollution Control Federa-
ation Journal, v. 53, n. 3, March 1981, pp. 325-339.
21. Neufeld, Ronald D. , L. Mattson and P. Lubon, Bio-oxidation
of Thiocyanates Typical of Coal Conversion Effluents,
Pittsburgh, PA, Univ. of Pittsburgh, Jan. 8, 1981 (DOE/ET/
04502-7).
22. Neufeld, Ronald D. , et.al., GFETC Lignite Coal Gasification
Wastewater Treatment Techniques and Sludges; Chemical and
Health Effects, Grand Forks Energy Technology Center, U.S.
Department of Energy, April 15, 1982 (DOE/ET/10299-2).
23. Neufeld, Ronald D., et.al., Influence of Solvent Extraction
on Fixed Bed Gas Producer Wastewater, Morgantown Energy
Technology Center, U.S. Department of Energy, April 15, 1982,
(DOE/ET/16528-2).
101
-------
24. Neufeld, Ronald D. , et.al., Pretreatment and Biological
Digestion of METC Stiirred Fixed Bed Gas Producer Wastewaters,
Morgantown Energy Technology Center, U.S. Department of
Energy, Sept. 30, 1981, (DOE/ET/14372-7).
25. Neufeld, Ronald D., The Treatment of Wastes from Synthetic
Fuels, Pittsburgh, PA, Univ. of Pittsburgh, Jan. 15, 1982,
(SETEC-CE-81-027).
26. Patterson, R. D. and S. L. Darling, "A Low BTU Coal Gasi-
fication Scheme," Chemical Engineering Progress, v. 76, n. 3,
March 1980, pp. 55-60.
27. Radian Corporation, Background Docuemnt for Environmental
Performance Goals; High BTU Gasification, Washington, DC,
U.S. Environmental Protection Agency, March 12, 1980.
28. Radian Corporation and Burns and Roe Industrial Services
Corporation, Industry Profile; Synfuels Industrial Category
(Draft), Washington, DC, U.S. Environmental Protection
Agency, Dec. 1980.
29. Radian Corporation, Literature Review Report; Synfuels
and Related Industries, Washington, DC, U.S. Environmental
Protection Agency, Sept. 1980.
30. Ruggiero, Dominick D. and Harold J. Kohlman, Low-BTU Gasi-
fier Wastewater Treatability; Phase III, Pilot Plant Study
at Holston Army Ammunition Plant, U.S. Environmental
Protection Agency, Dec. 1983.
31. Synfuels Handbook, by the Editors of Coal Week, New York,
McGraw-Hill, 1980.
32. U.S. Department of Energy, Environmental Control Technology
Division, Processing Needs and Methodology for Wastewaters
from the Conversion of Coal, Oil Shale and Biomass to
Synfuels, Washington, DC, May 1980, (DOE/EV-0081).
33. U.S. Environmental Protection Agency, Estimated Theoretical
Treatability of Organic Priority Pollutants; The Relation-
ship with Solubility Parameters (Part E), Draft, Washington,
DC, May 1979 (EPA 440/1-79/100).
34. U.S. Environmental Protection Agency, Pollution Control
Technical Manual: Lurgi-Based Indirect Coal Liquefaction
and SNG, Washington, DC, April 1983 (EPA-600/8-83-006).
35. U.S. Environmental Protection Agency, Pollution Control
Technical Manual; Lurgi Oil Shale Retroting With Open
Pit Mining, Washington, DC, April 1983 (EPA-600/8-83-005).
102
-------
36. U.S. Environmental Protection Agency, Pollution Control
Technical Manual; Modified In-Situ Oil Shale Retorting
Combined with Lurgi Surface Retorting, Washington,'DC,
April 1983 (EPA-600/8-83-004).
37. U.S. Environmental Protection Agency, Pollution Control
Technical Manual; TOSCO II Oil Shale Retorting With
Underground Mining, Washington, DC, Spril 1983 (EPA-600/
8-83-003) .
38. Willson, Warrack G. , et.al.f "Pilot Plant Wastewater Treat-
ment Project Status at the Univ. of N. Dakota Energy Research
Ctr," presented at 12th Biennial Lignite Symposium, May 18-19,
1983, Univ. of N. Dakota, Grand Forks, No. Dakota.
39. Winton, S. L. and M. D. Matson, Lurgi Process Wastewaters
Projected Characteristics and Treatment Alternatives,
Radian Corporation, Austin, TX, Technical Note 218-001-15-
02, June 13, 1980.
40. UOP/SDC,. Technical Analysis of Advanced Wastewater
Systems for Coal Gasification Plants, Preliminary Print
(D-TR-80/041-001).
41. Benson, J. M. , et.al., "Toxicological and Chemical
Characterization of Process and Waste Streams of a Low
Btu Gasifier," Annual Report, Inhalation Toxicology
Research Institute, October 1, 1981 - September 30,
1982, pp. 125-128.
42. Booz, Allen and Hamilton, Inc., Markets Jior Low- and
Medium-Btu Coal Gasification; An Analysis of 13 Site
Specific Studies, September 1981, (DOE/RA/02625-T1).
43. Newton, G. J., et.al., Editors, "Physicochemical
Characteristics of Process Streams of an Experimental
Low Btu Gasifier," Annual Report, Inhalation Toxicology
Research Institute, October 1, 1979 - September 30,
1980, pp. 375-383.
44. Royer, R. E., et.al., Editors, "Chemical and Toxi-
cological Characterization of Waste Stream Effluents
of an Experimental Low-Btu Gasifier,"Annual Report,
Inhalation Toxicology Research Institute, October 1,
1979 - September 30, 1980, pp. 429-431.
45. Singh, S.P.N., J. F. Fisher and G. R. Peterson,
Evaluation of Eight Environmental Control Systems
for Low-Btu Coal Gasification Plants, Washington,
D.C., U.S. Department-of Energy, March 1980, (ORNL-
5481).
103
-------
46. Witmer, F. E. and C. D. Livengood, Pollution Control
Costs; A Status Report, Washington, D.C., U.S.
Department of Energy, May 1982, (CONF-8205161-1) «-
47. Radian Corporation, Low-Btu Gasification Generic
Sampling Program for Multimedia Development of
Regulatory Support Data, Washington, DC, U.S.
Environmental Protection Agency, 11 June 1981.
48. Hydrotechnic Corporation, Phase II - Bench Scale Treat-
ment Program for Holston Army Ammunition Plant; Low-Btu
Gasifier Wastewater, Washington, D.C., U.S. Environmental
Protection Agency, August 1981.
49. Harris, M. T., et.al., Wet Oxidation of Phenol and
Naphthalene (As a Surrogate PAH) in Aqueous and Sludge
Solution; Application to Coal Conversion Wastewater and
Sludge Treatment,Oak Ridge National Laboratory, Oak
Ridge, TN, May 1983.
104
-------
APPENDIX A
DESCRIPTIONS OF PLANTS SAMPLED AND SUMMARIES
OF SAMPLING DATA
-------
TABLE OF CONTENTS
INTRODUCTION A-l
FORT SWELLING LOW-BTU GASIFICATION FACILITY A-2
MORGANTOWN ENERGY TECHNOLOGY CENTER A-48
GENERAL ELECTRIC CORPORATE RESEARCH AND DEVELOPMENT
CENTER A-61
HOLSTON ARMY AMMUNITION PLANT A-75
A-ii
-------
INTRODUCTION
This Appendix describes the four low-Btu gasification facilities
that were sampled.* The following lists the items included in
the descriptions:
A) Selection Rationale - Reasons for selection of the
facility for sampling
B) Process Description - A description of the gasification
process unique to each facility
C) Sample Episodes - A description of sample points and
sampling procedures
D) Operating Parameters - A detailed description of
operating conditions at the time of sampling
E) Pollutant Data - A listing of analytical data obtained
from the sampling at each sample point
*As discussed in this appendix, samples were taken both for the
Office of Solid Waste and for the Office of Water (particularly
the Effluent Guidelines Division or EGD). For the reader's
information, EGD is currently entitled the Industrial Technology
Division but references to EGD are left, as is, in the text.
Also note that while sample points for both the Office of Solid
Waste and for the Office of Water are described, only analytical
data for samples taken for the Office of Water are presented in
this report.
A-1
-------
FORT SNELLING LOW-BTU GASIFICATION FACILITY
SELECTION RATIONALE
The Fort Snelling low-Btu gasification facility was selected for
sampling for the following reasons:
o The gasifier is a commercial sized unit.
o It provides the ability to evaluate the effects of
various feed coals and coal sizes.
o Both gas quench and ash quench wastewaters can be
sampled.
PROCESS DESCRIPTION
The gasification facility includes a single-stage, 6.5-foot,
fixed-bed atmospheric gasifier with a water cooled agitator. The
U.S. Bureau of Mines attempts to operate the gasifier at maximum
capacity.
Coal fed to the gasifier is first transported by conveyor belt to
a vibrating screen where coal fines less than 3/4 inch are
removed for disposal. From the screen, the coal is transported
to the top of the gasifier facility via a bucket elevator to a
10-ton storage bin. The storage bin is supported on precision
load cells to determine the coal feed rate. Coal from the
storage bin gravity flows through two pipes to a 3-ton feed bin.
Two sliding disc valves, one valve per pipe, control the flow of
coal to the feed bin. The valves are opened only when the feed
bin is low in coal. The feed bin is divided into two chambers
each of which simultaneously gravity feeds the gasifier via two
10-inch feed pipes. Each feed pipe has two sliding rotary
valves, one located just below the feed bin and one located, just
above the gasifier. The valves are opened alternately allowing
for a continuous feed of coal and to reduce the quantity of
emissions escaping through the feeding system. The valves below
the feed bin are opened to fill the feed pipes only when the
pipes are empty of coal and the valves above the gasifier are
closed.
The ash produced by the gasification process falls through the
grate openings into an ash bin where it is sluiced by water into
a truck for landfilling.
The low-Btu gas produced by the gasifier is passed through a
refractory-lined, dry cyclone to remove most of the particulate
carryover which consists of approximatley 90 percent carbon.
These carbon particles are sluiced with water out of the cyclone
A-2
-------
and trucked for storage. After passing through the cyclone, the
low-Btu gas is transmitted by a 24-inch I.D. duct to a combustion
chamber and an 8-inch I.D. duct to the pelletizing kiln. The
8-inch duct exists off the 24-inch duct that leaves the cyclone.
Both ducts are lines with 4 inches of refractory.
The combustion chamber is designed to utilize the full capacity
of the gasifier because at maximum output the pelletizing kiln
would use only 3.5 to 4 million Btu or 10 to 15 percent of the
product gas. Exhaust gas from the combustion chamber is cleaned
with an impingement tray-type scrubber before entering the
combustion stack. The exhaust gas from the kiln is also passed
through a venturi scrubber before entering the stack. An
incinerator is installed on the gasifier vent stack to ignite
gases during startup and banking.
There are venturi orifices located in the pipelines to the
combustion chamber and the kiln to determine gas flow rates. The
feed bin and ash bin are on load cells to determine the amount of
coal fed and ash removed respectively.
A flow diagram of the U. S. Bureau of Mines coal gasification
facility is illustrated in Figure A-l. Table A-l lists all of
the sample points for both OSW and EGD sampling.
SAMPLE EPISODES
The Fort Snelling facility was sampled on three separate
occasions:
o June 17-June 24, 1981 - North Dakota Lignite;
o July .22-July 31, 1981 - Texas Lignite; and
o August 12-August 21, 1981 - Colorado Subbituminous.
The three visits allowed for sampling of the gasifier during
utilization of three separate feedstocks. Each feedstock was
also fed using at least two different sizes. Wastewater
characteristics were impacted by the different coal types but did
not exhibit appreciable differences due to changes in feed size.
As discussed in more detail later in the section on wastewater
characteristics, the primary differences in the wastewaters were
related to the foreign matter in the coals, i.e..TSS and metals
content. The organic material in the wastewaters from the three
episodes did not show significant differences related to feed
material.
SAMPLE EPJSODE NO. 1—NORTH DAKOTA LIGNITE
The test burn of North Dakota "Indianhead" Lignite ran as
scheduled from June 16 through June 25, 1981. Table A-2 lists
A-3
-------
COAL VINT * FLARE
SLUCE WATER
PALLET PRODUCT
MAKE UP WATER
Figure A-l. Process Flow Diagram of U.S. Bureau of Mines
Gasification Facility and Pelletizing Plant
-------
Table A-l
Sample Points at the Fort Snelling Gasification Facility
Source
Coal Feed
Gasifier Sluice Water
Gasifier Ash
Cyclone Quench Water
Cyclone Dust
Gas Scrubber Water
Scrubber Float Tar
Scrubber Sink Tar
Coal Pile Runoff
Tailings Pond
Make-Up Water
Sample Point
S2
v->
MMM
S3
S4
A-5
-------
TABLE A-2
SUMMARY OF KNOWN OPERATIONAL EVENTS DURING SAMPLING
6/17
6/18
6/19
6/20
6/21
6/22
6/23
0000-0800*
1415
1530-1545*
0800
0830
0930
1000
1300*
0700
0714-0750
1200*
1330
1930
2300
0000-0500*
1845
1900-1915
1920
10263
0500*
0930
0945-1000
1100
1400
1545
0300
Description
Startup with charcoal and kerosene, gasifier
burning coke and produced gas vented
Gas to combustor.
Feed switched to 2 x 3/4 inch lignite
EGD/OSW coal feed sample taken
Gasifier sluice water and ash samples taken.
Rate=l.l ton/h of 2 x 3/4 inch lignite
Scrubber water samples taken
Cyclone quench water sample taken
Cyclone dust sample taken
Rate=2.0 ton/h of 2 x 3/4 inch lignite.
Rate=2.0 ton/h of 2 x 3/4 inch lignite
Samples of gasifier sluice water and ash, and
cyclone quench water
Feed switched to 2 x 1/2 inch lignite
Scrubber water, scrubber float and sink tars
samples taken
Gasifier sluice water and ash samples taken
Samples taken of cyclone quench water and
dust, and scrubber water, float and sink
tars.
Feed switched to 2 x 1/4 inch lignite
Scrubber water, tars samples taken
Gasifier sluice water and ash samples taken
Cyclone quench water sample taken.
Coal pile runoff sample was taken.
inches of rain fell.
0.35
6/24 0730-0740
0800
0830-0845
*Approximate times
Feed switched to 3/4 x 1/4 inch lignite.
Rate=1.3 ton/h
Rate dropped to 1 ton/h - unstable bed
Cyclone quench water and dust samples taken
Gasifier sluice water and ash samples taken
Scrubber fan went down, scrubber shut off
5 tons of lignite (3/4 x 1/4 inch) will be
burned then coke added to stabilize the bed.
Feed switched to 2 x 3/4 inch lignite
Agitator down. No coal was loaded until 0700
2 x 3/4 inch feed from 2 year old stockpile
of North Dakota lignite.
Samples of cyclone quench water and dust
taken
Intake water sample taken
Gasifier sluice water and ash samples taken.
A-6
-------
information on gasifier operations. This information was
obtained through informal discussions with gasifier operators and
on observations of the field crew. Tables A-3 and A-4 list the
samples taken during the North Dakota Lignite test burn for
wastewater samples and solid waste samples respectively.
The ash from the gasifier was removed after approximately 500
pounds had accumulated in the hopper. Water was added for 30
seconds, and the slurry was dropped into a portable bin. The ash
settled out immediately. The ash consistency ranged from fine
particles through large chunks of unburned lignite.
Samples of the sluice water were taken immediately after the
slurry was dropped into the bin. If the water depth permitted,
all fraction bottles were filled directly except the VOAs, which
were filled via a stainless steel beaker. If the water depth was
not sufficient, a stainless steel beaker was used to fill the
fraction bottles.
The ash samples were taken after the sluice water was decanted
off. Samples were grabbed with a stainless steel beaker and
deposited into a clean one gallon jug.
The product gas passed through the cyclone dust collector after
exiting the gasifier. Particulate material was removed and col-
lected in a water bath below the cyclone. The level of the
quench water controlled by a float was maintained above the dust
discharge oriface. The water overflowed through a screen and was
discharged. The dust settled to the bottom of the bin and was
manually scraped out whenever the operators felt it was
necessary. The dust scraped out of the bin fell through a chute
to a 55-gallon drum on the floor below.
Samples of the quench water were taken directly from the bin. A
stainless steel beaker was used to fill the VOA vials. The
quench water samples were taken near the time of the gasifier
sluice water/ash sampling.
The cyclone dust samples were taken from the 55-gallon drum in
which the dust collected after it was scraped out of the bin.
Very little dust accumulated in the bin during the first days of
the burn. The dust accumulation increased as the lignite feed
size decreased. Dust particles taken for the last grab sample
(6/24) had the consistency of moist concrete whereas the dust on
the first grab (6/18) sample contained larger and drier solids.
The blowdown of the scrub water and sink tar was scheduled on an
hourly basis while the float tar was scheduled four times per
day. The blow down aliquots were wasted to 55-gallon drums
except for the 0700 and 1900 aliquots which were saved for
analyses.
A-7
-------
TABLE A-3
SUMMARY OF EGD - WASTEWATER SAMPLES
Date - Time (Hr.)
SCC Code
Points
6/17 -
1415
1530
SO482
10240/86569*
Coal Feed
Sluice Water
6/18 -
0930
0830
10241/86570
10242/86571
Quench Water
Scrubber Water
6/19 -
0715
0750
1330
1930
2330
2300
10243/86572
10244/86573
10245/86574
10246/86575
10247/86576
10248/86577
Sluice Water
Quench Water
Scrubber Water
Sluice Water
Quench Water
Scrubber Water
6/20 -
1900
1920
1845
10249/86578
10250/86579
10251/86580
Sluice Water
Quench Water
Scrubber Water
6/21 - 1530
6/22 - 1100
- 0945
10263/86592
10252/86581
10253/86582
Coal Pile Runoff
Sluice Water
Quench Water
6/24 -
0830
0730
0850
10255/86584
10256/86585
10261/86590
Sluice Water
Quench Water
Plant Intake Water
* Sample Control Center Sample Codes for Dissolved Metals
A-8
-------
TABLE A-4
SUMMARY OF OSW - SOLID WASTE SAMPLES
Date - Time (Hr.)
Sample Codes
Points
6/17 -
6/18 -
6/19 -
1415
1530
1545
0930
1000
0830
0715
0730
1330
1330
1330
1930
1935
2300
2300
2300
1900
1915
1845
1845
1845
6/21 - 1530
6/22 - 1100
- 1110
- 0945
- 1000
6/20 -
6/24 -
0830
0835
0730
0740
S0482
10240
99001
10241
99002
10242
10243
99003
10245
99003
99004
10246
99008
10247
99006
99007
10249
99011
10251
99009
99010
10261
10252
99014
10253
99015
10255
99018
10256
99019
Coal Feed
Sluice Water
Ash
Quench Water
Dust
Scrubber Water
Sluice Water
Ash
Scrubber Water
Float Tar
Sink Tar
Sluice Water
Ash
Scrubber H20
Float Tar
Sink Tar
Sluice H20
Ash
Scrubber Water
Float Tar
Sink Tar
Coal Pile Runoff
Sluice Water
Ash
Quench Water
Dust
Sluice Water
Ash
Quench Water
Dust
-------
EGD/OSW samples were originally scheduled to be taken beginning
at 1300 on the days that the gasifier ash and sluice water were
taken. The scheduled time was selected as not to interfere with
the facility's own sampling schedule. EGD/OSW grab samples were
to be taken from the blowdown aliquots taken by the scrubber
operators.
The field crew discovered that they were able to draw samples
directly from the scrubber since the blowdown schedule was not
being strictly followed.
Solid waste samples were not taken for the flot and sink tars for
Grab No. 1 (6/18) since there was no accumulation in the
reservoir. No samples (scrub water or tar) were taken on 6/22 or
6/24 due to operational difficulties with the scrubber.
Grab samples of the scrub water were tapped off the side of the
reservoir. The fraction containers were filled directly.
Samples of the float tar were skimmed off the top of the
reservoir using a pan supplied and used by scrubber operators.
The sink tar was taken from the sampling tap at the bottom of the
reservoir.
A grab sample of the coal feed was taken from the feed bin above
the gasifier. A 10-pound container was filled from both the
north and south feed chute. The sample was taken on 6/17 at 1415
hours.
On 6/21, 1530 hours, a grab sample was taken of the coal pile
runoff. The runoff was collected in one-gallon containers at the
end of the concrete pad. The sample was then transferred to
individual fraction containers. It was discovered after the
sample was taken that caustic being used in an adjacent area was
spilled and may have contaminated the runoff.
No samples were taken of the tailings pond since the plant
discharge was not contained but continuously ran off the
property.
SAMPLE EPISODE NO. 2—TEXAS LIGNITE
The test burn of the Texas Elgin/Butler Brick Co. lignite ran as
scheduled from July 22 through July 31, 1981. The test plan
proved too ambitious as the operators experienced problems
controlling the burn characteristics in the gasifier. They found
this lignite too friable which caused the fine bed in the
gasifier to become unstable. On Friday, July 24, officials of
the BOM and represented companies revised the plan .to as
follows:
A-10
-------
o Hold rate (1.1 ton/hr) until Sunday, 7/26.
o Then increase rate to 1.3 to 1.4 tons/per hr and
hold there until Tuesday, 7/28.
o Decide on Tuesday whether to switch to 2 x 1/4
inch feed.
As it turned out, this schedule could not be followed either.
Table A-5 summarizes, chronologically, gasifier operating
conditions, difficulties, and failures as well as sampling times.
Table A-5 shows that the saturation air flow and lignite feed
rate to the gasifier fluctuated throughout the 10 day burn as the
operators tried to control the burn. Early Thursday, 7/30, the
gasifier switched to coke to stabilize the fine bed. The coke
was burned until Friday morning when 2 x 1/4 inch lignite was
burned until the end of the test at noon.
In addition to the instability in the gasifier bed, the operators
had to contend with problems with the boiler and combustor.
Twice during the 10 day period (7/23, 0130-0345 and 7/26, 2030 to
2230) the gasifier was banked as personnel worked on the boiler.
The combustor shut down and gas had to be flared twice during the
burn on 7/29 at 0730 and 7/30 at-1900. The crew waited to take
samples only after it was determined that the operating
conditions were relatively stable and the produced gas was
flowing through the cyclone to the combustor long enough for the
samples to be representative of the operating conditions.
Mechanical problems with the gas scrubber prevented the operators
from running the unit during much of the periods of gas flow to
the combustor. As outlined in Table A-5, the scrubber was down
7/24 with fan problems and 7/27 through 7/30 with broken fan
housing gaskets. Consequently, only one set of samples could be
grabbed from the scrubber unit during the 10 day period. Tables
A-6 and A-7 list the samples taken for the Texas Lignite test for
wastewater samples and solid waste samples respectively.
It was apparent during the June burn that the scrubber entrain-
ment water temperature was too high. This caused much of the tar
to be carried over and condensed out in the fan housing or pass
through the unit completely. The operators decided that the
scrubber would work more efficiently if the temperature remained
between 75-100°F. To accomplish this during the July burn, the
operators maintained a continuous blowdown of the water while
they constructed a cooling coil. The coil was not installed
until 7/30. While the continuous blowdown of the scrubber water
reduced the water temperature and improved the tar removal, the
water was discharged to a drain and eventually to the tailings
pond.
A-11
-------
TABLE A-5
SUMMARY OF OPERATIONAL EVENTS DURING SAMPLING
7/23
7/24
7/25
7/26
7/27
Time
0930
1420
2400
0130-0345
0800
1030*
1430
1600
1600-2400*
0000-0800*
0700
0730
0745
1025
1030
0930-1100*
1600
1600-2400*
0830
0850
0930
1200
0730
2230
1030
1530
1700
1800-2400*
Event
Banked on coke.
Fired up gasifier, burning coke, gas to vent.
Loaded 2 x 3/4" lignite.
Began burning lignite, gas to vent. Rate:
123 ton/hr; saturation air flow: 608 cfm.
Boiler trouble, gasifier banked.
Rate=l.l ton/hr, saturation air flow=700 cfm,
gas to vent.
Fire on top of bed in gasifier, rate less
than 1 ton/hr, saturated air flow = 450 cfm,
gas vented.
Gas to combustor. Rate=0.9 ton/hr, saturation
air flow = 400 cfm.
Coal feed sample taken.
Scrubber started.
Scrubber down - fan not balanced.
Rate=l.l ton/hr, saturation air flow=450 cfm.
Gasifier ash sample taken. Ash absorbed 40
sec. flush of sluice water.
Cyclone quench water and dust sampled.
Sluice water sample taken 60 sec. flush used.
Rate=l.l, saturation air flow=499 cfm.
Meeting held to adjust test plan.
Coal pile runoff sample, moderate to heavy
rain for 3/4 hr.
Scrubber restarted.
Rate=1.3 ton/hr. Saturation air flow=450 cfm.
Cyclone quench water sampled.
Scrubber water and float tar samples taken.
Gasifier sluice water sampled, 90 sec flush
used. Rate = 1.22 ton/hr, saturation air
flow = 450 cfm.
Rate=0.67 ton/hr, saturation air flow = 200
cfm. Rate reduced since 0430 due to uneven
burning of bed. No samples taken 7/26.
Gasifier banked, boiler trouble, gas to vent.
Rate=.7 ton/hr, saturation air flow = 200
cfm, gas to vent.
Combustor restarted. Rate = 1.0 ton/hr,
saturation air flow = 320 cfm.
Scrubber restarted.
Scrubber d"own - gasket on fan housing
slipped.
A-12
-------
TABLE A-5
SUMMARY OF OPERATIONAL EVENTS DURING SAMPLING (cont'd)
Date
7/28
7/29
7/30
7/31
Time
0800
0840
0905
1500
0730
0800
1800
0200
0900
1600
1900
0000-0300*
0700
0730
Event.
Rate=1.15 ton/hr, saturation air flow =
390 cfm.
Cyclone quench water sampled.
Gasifier sluice water and ash samples taken,
90 sec. flush used.
Rate=1.3 ton/hr, saturation air flow = 390
cfm., scrubber still down.
Combustor down, gas to vent.
Rate=0.57 ton/hr, saturation air flow = 206
cfm.
Plan to run out 2 x 3/4" lignite, switch to
coke, then to 2 x 1/4" lignite.
Rate=0.57 ton/hr (coke) gas to vent.
Rate=.75 ton/hr, saturation air flow, 500
cfm, burning coke, gas to vent.
Combustor restarted.
Combustor down.
Switched to 2 x 1/4" lignite, gas to vent.
Rate=1.01 ton/hr, saturation air flow = 392
cfm, gas to vent.
Intake water sample taken.
*Approximate times
A-13
-------
TABLE A-6
SUMMARY OF EGD - WASTEWATER SAMPLES
Date - Time (Hr.) SCC Code Point
7/23 - 1600 S0553 Coal Feed
7/24 - 1025 10355/86640* Sluice Water
- 0745 10356/86641 Quench Water
- 1600 10377/86662 Coal Pile Runoff
7/25 - 0930 10357/86642 Scrubber Water
- 1200 10358/86643 Sluice Water
- 0850 10359/86644 Quench Water
7/28 - 0905 10361/86646 Sluice Water
- 0840 10362/86647 Quench Water
7/31 - 0730 10376/86661 Tap Water
*Sample Control Cente.r sample Codes for Dissolved Metals
A-14
-------
TABLE A-7
SUMMARY OF OWS - SOLID WASTE SAMPLES
Date - Time (Hr)
SCC Code
Point
7/23
7/24
S0553
10355
99026
10356
99027
10377
Coal Feed
Sluice Water
Gasifier Ash
Quench Water
Cyclone Dust
Coal Pile Runoff
7/25
10357
99028
10358
99030
Scrubber Water
Float Tar
Sluice Water
Gasifier Ash
7/28
10361
99033
Sluice Water
Gasifier Ash
A-15
-------
Due to the operating and mechanical difficulties, only three of
the seven planned sets of gasifier sluice/ash and cyclone
quench/dust samples were taken. Sluice water could only be taken
after 7/24 when more water was used in sluicing the ash.
Previous to 7/24 all of the sluice water was absorbed into the
ash. Only one sample was taken of the scrubber water and the
float tar. Since the scrubber was continuously blown down, no
sink tar was collected and consequencly no sink tar samples were
taken.
SAMPLE EPISODE NO. 3—COLORADO SUBBITUMINOUS
The test burn of Colorado subbituminous coal ran as scheduled
from August 12 through August 21, 1981. During the 10-day burn,
the scheduled rates were reached, and the operators experienced
no major operating problems in the gasifier. Table A-8
summarizes, chronologically, gasifier operating conditions,
difficulties and failures of auxiliary equipment in relationship
to sampling times. Table A-9 lists the samples taken during the
Colorado subbituminous test for wastewater samples. No solid
waste samples were taken during this operating period.
The operators were able to increase the saturation air flow to
above 1500 cfm on 8/18 using 2 x 3/4-inch subbituminous feed and
to 1200 cfm with 2 x 1/4-inch feed on 8/21. The gasifier was
banked twice during the burn - 8/15, 2100 to 2315, to grease the
agitator and from 8/20, 2330 to 8/21, 0130. In general, the
operators were pleased with the operation of the gasifier.
o A leak in the gasifier water jacket caused addi-
tional water to be mixed with the ash. This will
affect the accuracy of the sluice water samples.
o The scrubber was scheduled to operate only from
0800 to 2400 each day due to a manpower shortage.
Operating and mechanical problems with the
scrubber caused down times during operational
periods. The cooling coal, constructed and in-
stalled by the scrubber crew at the end of the
July burn, was used until it broke down. The
scrubber then was run without water temperature
adjustments or blowdowns. The operators found
the high gas temperatures raised the water
temperature too much for the coils to be
effective.
o The scrubber operators had to contend with tar
passing through the venturi and dropping out in
the fan housing. No solution to this problem was
determined. On July 20, during the daily scrubber
A-16
-------
TABLE A-8
SUMMARY OF OPERATIONAL EVENTS DURING SAMPLING
Date
8/12
8/13
8/14
8/15
8/16
8/17
Time
0930
1430
1930
2130
0930
1230
1340
1350
1445
2OOO*
2230-2250
0930
1030
1330
1440
1540
0900
1020
1015
2100-2315
2315
0530-1300
0830
0830
0930
1040
1100
1600
Event
Start-up burning Coke, gas to vent.
Loaded 2 x 3/4" subbiturninous coal.
Gas to combustor.
Began burning subbituminous coal.
Rate 0.62 ton/hr, Sat. Air Flow=600 cfm.
Coal Feed sample taken.
Scrubber started.
Cyclone Quench Water sampled.
Gasifier Sluice Water samples taken.
Gasifier water jacket leaking - adding
unknown amount of water. Rate = 0.72 ton/hr
Sat. Air Flow = 650 cfm.
Scrubber down, not removing tar.
Combustor down, gas to vent.
Rate=0.92 ton/hr, Sat. Air Flow=800 cfm.
Scrubber still down.
Coal Pile Runoff sample taken.
Scrubber restarted.
Cyclone Quench Watrer sampled.
Gasifier Sluice Water sample taken, water
jacket still leaking. Rate=0.98 ton/hr,
Sat. Air Flow = 809 cfm.
Rate=1.03, Sat. Air Flow = 1000 cfm.
Cyclone Quench Water sampled.
Gasifier Sluice Water sample taken, 30 sec.
of water added. Rate=1.05, Sat Air Flow =
1000 cfm.
Gasifier banked to grease agitator, gas
vented.
Combustor restarted.
Combustor down, gas vented.
Rate=1.06 ton/hr, Sat. Air Flow = 824 cfm.
No samples taken today.
Rate=1.30 ton/hr. Sat. Air Flow=1200 cfm.
Gasifier Sluice Water sample taken, 60 sec
of water added to ash.
Scrubber Water sample taken.
Cyclone Quench Water sample taken
Rate=1.05 ton/hr, Sat. Air Flow-1200 cfm.
*Approximate times.
A-17
-------
TABLE A-8
SUMMARY OF OPERATIONAL EVENTS DURING SAMPLING (cont'd)
8/19
8/20
8/21
Time
0830
0930
1030
1050
2400
0830
1220
1230-1330
1530
1600
0830
0945
1110
1600
2330
0130*
0900
0915
1200*
Event
Rate=1.83 ton/hr, Sat. Air Flow=1400 cfm.
Scrubber shut down immediately after morning
restart, watch glasses in venturi cracked.
Cyclone Quench Water sampled.
Gasifier Sluice Water sampled, 45 sec. of
water added. Rate=1.84 ton/hr, Sat. Air
Flow - 1410 cfm.
Rate=1.78 ton/hr, Sat. Air Flow=1550 cfm.
Rate=1.65 ton/hr, Sat. Air Flow=1400 cfm.
Start loading 2 x 1/4 inch subbituminous
coal.
Combustor down, gas to vent.
Rate=1.0 ton/hr. Sat. Air Flow=850 cfm.
Scrubber restarted after replacing watch
glasses. No samples taken today.
Rate=1.05 ton/hr, Sat. Air Flow=1000 cfm.
Cyclone Quench Water sampled.
Scrubber Water sampled. No Sluice Water
sample, ash absorbed all the water.
Rates=1.37 ton/hr, Sat. Air Flow=1120 cfm.
Gasifier banked.
Gasifier start-up.
Rate=1.39 ton/hr, Sat. Air Flow=1200 cfm
Cyclone Quench Water sampled.
Intake Water sample taken.
Gasifier shut down.
*Approximate times.
A-18
-------
TABLE A-9
SUMMARY OF WASTEWATER SAMPLES
Date - Time (Hr.)
SCC Code
Description
8/13
8/14
8/15
8/17
8/18
8/20
8/21
1230
1445
1350
1030
1540
1440
1115
1120
1150
1040
0930
1100
1130
1030
1110
0945
0900
SO560
10487/86666
10488/86667
10509/86688
10490/86669
10491/86670
10489/86668
10493/86672
10494/86673
10492/86671
10496/86675
10497/86676
10499/86678
10500/86679
10495/86674
10503/86682
10508/86685
10508/86687
Coal Feed
Sluice Water
Quench Water
Coal Pile Runoff
Sluice Water
Quench Water
Scrubber Water
Sluice Water
Quench Water
Scrubber Water
Sluice Water
Quench Water
Sluice Water
Quench Water
Scrubber Water
Quench Water
Quench Water
Intake Water
A-19
-------
start-up at 0930, it was discovered that the watch
glasses on the venturi had cracked and caused a
negative pressure to be drawn. The scrubber was
shut down until 8/19, 1600 when the glass was re-
placed.
POLLUTANT DATA
The samples collected during each of the three episodes at Fort
Snelling were analyzed as described in the sampling plan. A
summary of the results of these analyses are given in Tables A-10
through A-24. Grab samples and composite sample analytical data
are treated alike in the summaries.
A-20
-------
TABLE A-10
PRIORITY ORGANIC POLLUTANTS DETECTED IN THE ASH SLUICE WATER (uy/1)
NORTH DAKOTA LIGNITE
TEXAS LIGNITE
Ni
Pollutant
2,4,6 Trichlorophenal
p-chloro-m-cresol
2,4,Dimethyl Phenol
2,4, Dimitrotolnone
Fluoranthene
Methylene Chloride
Isophorone
Naphtalene
2-Nitrophenol
4-Nitrophenol
4,6-Dinitro-o-cresol
N-nitrosophenylamine
Pentachlorophenol
Phenol
Bis (2-ethylhexyl) phthalate
Di-n-butyl phthalate
Di-n-octyl phthalate
Diethyl phthalate
Benzo(a)anthracene
Chrysene
Anthracene
Phenonthrene
Pyrene
Tr ichloroethylene
Te trachloroe thylene
Intake
200
22
No. of
Samples
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
No. of
Detects
1
4
4
3
1
5
1
2
0
1
2
0
1
5
2
3
2
3
2
1
2
3
1
1
4
Min
1
1
1
1
1
3
6
4
1
2
2
1
1
1
2
Mean Med
2
2 1
10
1 1
1
65
1
38
19
13
1 1
2 2
1
1 1
1 1
1
50
4
Max
5
30
4
276
4
38
32
373
2
4
2
2
1
1
8
NO. Of
Intake Samples
3
3
3
3
3
35 3
3
3
3
3
3
3
3
2 3
3
3
3
3
3
3
3
3
3
3
3
No. of
Detects Min
0
0
0
0
0
3 14
0
0
2
0
0
2
0
3 3
0
2 1
0
0
0
0
0
0
0
0
3 13
Mean Med Max
36 69
2
2
10 23
1
17 21
-------
TABLE A-10 (Continued)
PRIORITY ORGANIC POLLUTANTS DETECTED IN THE ASH SLUICE WATER ( g/1)
COLORADO SUBBITUMINOUS
ALL SAMPLES
to
Pollutant
2,4,6 Trichlorophenal
p-chloro-m-cresol
2,4, Dimethyl Phenol
2,4, Dimi trotolnone
Fluoranthene
Methylene Chloride
Isophorone
Naphtalene
2HSIitrophenol
ro 4-Nitrophenol
4,6, Dinitro-o-cresol
N-n i trosophe ny1amine
Pentachlorophenol
Phenol
Bis (2-ethylhexyl) phthalate
Di-n-butyl phthalate
Di-n-octyl phthalate
Diethyl phthalate
Benzo(a)anthracene
Chrysene
Anthracene
Phenonthrene
Pyrene.
Tr ichlbroethylene
Tetrachloroethylene
Intake
50
6
35
No. of
Samples
5
5'
5
5
5
5
5
5
5
5
5
5
5
5
5
5
6
6
5
5
5
5
5
5
5
No. of
Detects Min
1
0
0
0
0
5 20
0
0
0
0
0
0
1
3 6
0
0
1
0
1
0
0
0
0
0
3 1
Mean Med Max
2
117 317
18
65 171
10
1
10 16
NO. Of
Intake Samples
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
No. of
Detects
2
4
4
3
1
13
1
2
2
1
2
2
2
11
2
4
3
3
3
1
2
3
1
1
10
Min
1
1
1
1
1
3
18
3
4
1
2
2
1
1
1
1
Mean Med
2
2
10
1 1
1
79
1
2
38
2
26
1 1
5
2 2
1 1
1
1 1
1 1
1
50
10
Max
5
30
1
317
4
38
19
171
373
2
10
2
2
1
1
21
-------
TABLE A-11
NONCONVENTIONAL ORGANIC AND APPENDIX C POLLUTANTS DETECTED
IN THE ASH SLUICE WATER (ug/1)
NORTH DAKOTA LIGNITE
to
Pollutant
Methyl ethyl ketone
Acetone
Benzole Acid
n-Dodecane
x-picoline
Biphenyl
Pollutant
Methyl ethyl ketone
Acetone
Benzole Acid
n-Dodecane
x-picoline
Biphenyl
to. of to. of
Intake Sanples Detects Min Mean Med Max
TEXAS LIGNITE
2
6 5 <
6 5 <
6 1
6 0
6 0
6 2 <
Cl <1
ci 5
19
Cl
2
12
2
COLORADO SUBBITUMINOUS
to. of to. of
Intake Sanples Detects Min Mean Med Max
183
3
3
3
3
3
3
0
3 4 16
0
1 15
0
0
ALL SAMPLES
23
No. of No. of No. of No. of
Intake Sanples Detects Min Mean Med Max Intake Sanples Detects Min Mean Med Max
5
5
5
5
5
5
1
1
0
1
1
0
3
7
1
43
14
14
14
14
14
14
6
9
1
2
1
2
1
9
19
43
<1 3
23
15
-------
TABLE A-12
PRIORITY METALS DETECTED IN THE ASH SLUICE WATER (ug/1)
NORTH DAKOTA LIGNITE
TEXAS LIGNITE
to
Pollutant
Sb
As
Be
Cr
Cd
Cu
Fb
Hg
Ni
Se
Ag
Th
Zn
Pollutant
Sb
As
Be
Cr
Cd
Cu
Fb
Hg
Ni
Se
Ag
Th
Zn
Intake
<5
<1
<10
<10
100
<10
<50
<0.1
<30
<1
5
<3
20
No. of
Sanples
6
6
6
6
6
6
6
6
6
6
6
6
6
No. of
Detects Min
1
5
4
3
0
6
2
4
6
0
0
0
6
Mean
250
950 2220
10
40
30
300
0.1
120
50
33
63
385
0.2
935
730
Med Max
3500
50
90
580
350
0.2
1750
1110
Intake
<1
2
<1
2
<2
<2
<5
<1
<5
9
2
<1
20
COLORADO SUBBITUNINOUS
Intake
<1
<1
<1
<1
<2
2
<5
<0.5
12
<1
4
<1
<20
No. of
Sanples
5
5
5
5
5
5
5
5
5
5
5
5
5
No. of
Detects Min
2
5
5
5
5
5
5
3
3
5
5
0
5
2
8
1
33
7
47
7
0.5
5
2
1
23
Mean
23
3
212
10
77
14
1.3
28
8
2
64
Med Max
2
34
6
890
13
150
24
2.1
54
14
4
121
Intake
No. of
Sanples
3
3
3
3
3
3
3
3
3
3
3
3
3
No. of
Detects
3
3
3
3
3
3
3
0
3
3
3
3
3
Min
7
88
12
240
26
462
108
111
105
2
1
330
Mean
155
19
363
36
750
168
181
123
3
2
347
Med Max
16
219
25
495
41
972
221
248
144
4
3
520
ALL SAMPLES
NO. Of
Sanples
14
14
14
14
14
14
14
14
14
14
14
14
14
No. of
Detects
6
13
12
11
8
14
10
7
12
8
8
3
14
Min
2
3
1
33
7
30
3
0.1
5
2
1
1
23
Mean
48
898
17
212
19
353
122
0.6
520
51
2
2
410
Med Max
250
3500
50
890
41
972
350
2.1
1750
144
4
3
1110
-------
TABLE A-13
CONVENTIONAL POLLUTANTS DETECTED IN THE ASH SLUICE WATER fag/1)
Pollutant
NORTH DAKOTA LIGNITE
TEXAS LIGNITE
ND. of No. of No. of No. of
Intake Sanples Detects Min Mean Med Max Intake Sanples Detects Min Mean Med Max
pH
BODS
Oil and Grease
TSS
7.8
1.8
7.8
2
6
6
6
6
6
6
6
6
10.5 11.4
12 360
11.4 36.3
448 5170
12.5
570
91.8
8908
7.2
1.8
3
3
3
3
3
3
3
3
12.3 12.4
5.6 7.6
2940 8030
12.5
L <1
9.5
15700
to
ui
Pollutant
BODS
Oil and Grease
TSS
COLORADO SUBBITUMINOUS
ALL SAMPLES
No. of No. of M3. of No. of
Intake Sanples Detects Min Mean Med Max Intake Sanples Detects Min Mean Med Max
6.99
2
17
5
5
5
5
5
5
5
5
9.6 10.8
281 2470
11.8
<1 1
5710
14 14 9.6 11.4 12.5
14 14 <1 150 <1 570
14 14 <1 17 91.8
14 14 281 4820 15700
-------
TABLE A-14
NONCONVENTIONAL POLLUTANTS DETECTED IN THE ASH SLUICE WATER (mg/1)
NORTH DAKOTA LIGNITE
TEXAS LIGNITE
Pollutant
Acidity
Alkalinity
HC03
C03
TOC
COD
Phenol ics
Br
Cl
F
Total Solids
Total Volatile Solids
Total Volatile Susp. Solids
Total Dissolved Solids
CN
SCN
CN /C12
Kjeldahl Nitrogen
NH3
N03
N02
PO4
SO4
S03
S=
Total Organic Nitrogen
No. of
Intake Samples
-------
TABLE A-14 (continued)
NONCONVENTIONAL POLLUTANTS DETECTED IN THE ASH SLUICE WATER (mg/1)
NORTH DAKOTA LIGNITE TEXAS LIGNITE
Nc
Pollutant
Ca
Mg
Na
Al
Mn
V
B
Ba
Mo
Sn
Y
Co
Fe
Ti
No. of
Intake Samples
25.5
3.21
3.2
<0.2
0.006
<0.005
0.13
<0.01
0.4
<0.06
<0.01
<0.05
0.175
<0.004
6
6
6
6
6
6
6
6
6
6
6
6
6
6
No. of
Detects Win
6
6
6
6
6
6
6
6
1
0
1
4
6
6
403
48
1130
14.8
0.33
0.012
4.39
0.3
0.1
14.3
0.32
No
. of
No.
of
Mean Med Max Intake Samples Detects Min Mean Med Max
979
326
11050
541
2.36
0.62
31.1
1.13
1.4
0.02
0.18
653
8.95
1790
753
15700
1100
4.09
1.04
50.6
2.3
0.30
1340
21.1
21.1
3.32
7.3
0.575
0.015
<0.001
0.143
0.013
<0.035
<0.025
<0.003
<0.05
0.051
0.002
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
1310
26
43
95
1.54
0.56
7.6
1.21
3.09
0.59
0.17
0.069
28.3
22.7
1470
47
124
153
2.33
0.82
11.4
1.78
4.30
0.67
0.24
0.125
45.5
32.7
1630
74
278
215
3.70
1.07
13.7
2.08
5.27
0.73
0.30
0.15'
61.9
42
-------
TABLE A-14 (Continued)
NONCONVENTIONAL POLLUTANfS DETECTED IN THE ASH SLUICE WATER (mg/1)
COLORADO SUBBITUMINOUS
ALL SAMPLES
Pollutant
Acidity
Alkalinity
HC03
C03
TOC
COD
Phenol ics
Br
Cl
F
Total Solids
Total \folatile Solids
P Total Volatile Susp. Solids
i Total Dissolved Solids
w CN
SCN
CN /C12
Kjeldahl Nitrogen
NH3
N03
NO2
P04
SO4
SO3
S=
Total Organic Nitrogen
No. of
Intake Samples
-------
TABtB A-14 (contlnuertj
NONCDNVENTIONAL POLLUTANTS DETECTED IN THE ASH SLUICE WATER (mg/1)
COLORADO SUBBITUMINOUS
ALL SAMPLES
Pollutant
Ca
Mg
Ma
Al
Mn
V
B
Ba
MO
Sn
Co
Fe
> Ti
KJ
No. Of
Intake Samples
19.6
3.5
5.05
0.702
0.016
0.002
0.062
0.004
<0.035
<0.025
<0.03
<0.05
,0.035
<0.002
5
5
5
5
5
5
5
5
5
5
5
5
5
5
No. of
Detects Min
5
5
5
5
5
5
5
5
5
5
5
0
5
5
104
5.8
10.7
7.5
0.062
0.024
1.97
0.64
0.15
0.141
0.007
7.7
0.36
No. of
No. of
Mean Med Max Intake Samples Detects Min Mean Med Max
309
16.4
103
49
0.11
0.10
3.04
2.17
0.38
0.22
0.038
11.6
2.61
533
36
294
89
0.192
0.13
4.52
4.77
0.648
0.291
0.076
20.1
4.79
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
9
8
9
7
14
14
104
5
10
7
0
0
1
0
0
0
0
0
7
0
.8
.7
.5
.062
.012
.97
.3
.15
.14
.007
.069
.7
.32
845
156
4800
282
1.55
0.48
16.8
1.65
1.80
0.39
0.103
0.157
293
11.8
1790
753
15700
1100
4.09
1.07
50.6
4.77
5.27
0.73
0.30
0.30
1340
32.7
-------
TABLE A-15
PRIORITY ORGANIC POLLUTANTS DETECTED IN THE CYCLONE QUENCH WATER (Ug/1)
NORTH DAKOTA LIGNITE
TEXAS LIGNITE
to
o
Pollutant
Acenaphthene
Benezene
2,4,6-Trichlorophenol
p-chlor o-m-cre sol
Chlorpfonn
2f 4-Dichlorophenol
2,4, Dimethylphenol
2,4, Dinitrotoluene
2,6-Din i trotoluene
1,2-Diphenylhydrazine
Ethylbenzene
Fluoranthene
Methylene chloride
Methyl chloride
Isophorone
Naphtalene
4-Nitrophenol
2,4-Dinitrophenol
4,6-Din i tro-c-cresol
N-ni trosophenylamine
Pentachlorophenol
Phenol
Bis (2-ethylhexyl) phthalate
Di-n-butyl phthalate
Di-n-octyl phthalate
Diethyl phthalate
Benzo(a)anthracene
Benzo(a) pyrene
Chrysene
Anthracene
Fluorene
Phenanthrene
Pyrene
Toluene
No. Of
Intake Samples
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
No. of
Detects Min Mean
5
1
2
4
1
1
6
3
1
3
1
6
6
1
2
6
4
1
4
2
3
6
2
4
0
3
2
1
3
6
6
6
6
2
<1 1
60
<1
6 17
21
11
243 608
<1 4
2
5 11
<1
<1 111
5 195
24
9 14
14 310
<1 1
41
<1 16
8
<1 52
170 584
<1
<1
2 6
3
3
<1 2
2 11
4 18
4 18
<1 5
<1
No. of
Med Max Intake Samples
2
49
31
1180
8
19
655
1020
18
1550
<1 3
55
16
152
1080
4
6
9
10
5
36
34
41
11
2
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
No. of
Detects Min Mean Med Max
2
1
0
1
0
0
3
0
0
0
1
3
2
0
1
3
0
0
0
3
0
3
0
2
3
1
1
1
1
3
2
3
3
1
1
34
2
10
32
4
780
2
31
2
8
2
1
142
6
76
2
8
17
36
6
2720
66
2
2
<1
2
3
4
2
59
4
110
18
37
40
8
5760
21
86
4
11
6
2 2
-------
TABLE A-15 (Continued)
PRIORITY ORGANIC POLLUTANTS DETECTED IN THE CYCLONE QUENCH WATER { g/1)
COLORADO SUBBITUMINOUS
u>
Pollutant
Acenaphthene
Benezene
2,4,6-Trichlorophenol
p-chloro-rn-cre sol
Chloroform
2,4-Dichlorophenol
2,4, DimethyIphenol
2,4, Din itrotoluene
2,6-Dinitrotoluene
1,2-Diphenylhydrazine
Ethylbenzene
Fluoranthene
Methylene chloride
Methyl chloride
Isophorone
Naphtalene
4-Ni trophenol
2,4-Dinitrophenol
4,6-Dinitro-o-cresol
N-n itrosophenyl ami ne
Pentachlorophenol
Phenol
Bis (2-ethylhexyl) phthalate
Di-n-butyl phthalate
Di-n-octyl phthalate
Diethyl phthalate
Benzo(a)anthracene
Benzo{a)pyrene
Chrysene
Anthracene
Fluorehe
Phenanthrene
Pyrene
Toluene
NO. Of
Intake Samples
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
No. of
Detects Min Mean Med Max
0
1
0
0
0
0
7
0
0
0
4
0
7
0
0
6
0
0
0
1
1
7
1
3
0
0
2
1
2
2
6
3
3
0
104
3
23
10
710
1
<1
2
2
3
3
2
162
551 1541
4 1
76 11!
21 4:
23
13
547(
3
9 2:
4
5 :
5 •
5 '
2 2 :
ALL SAMPLES
NO. Of
Intake Samples
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
No. of
Detects
7
3
2
5
1
1
16
3
1
3
6
9
15
1
3
15
4
1
4
6
4
16
3
9
3
4
5
3
6
11
14
12
12
3
Min
<1
60
<1
6
34
<1
5
<1
<1
5
9
10
<1
<1
4
<1
170
<1
<1
31
2
<1
<1
<1
2
2
2
<1
<1
Mean Med
1
121
15
21
11
483
4
2
11
4
77
116
24
15
139
1 <1
41
16
11
42
2570
2
6
66
5
4
2
2
7
11
11
4
20
Max
4
162
49
31
1540
8
19
8
655
1020
18
1550
3
55
23
152
5760
4
23
86
9
10
4
5
36
34
41
2
59
-------
TABLE A-16
NONCONVENTIONAL ORGANIC AND APPENDIX C POLLUTANTS DETECTED
IN THE CYCLONE QUENCH WATER (ug/1)
NORTH DAKOTA LIGNITE
TEXAS LIGNITE
>
to
Pollutant
Methy ethyl ketone
Acetone
Dibenzofuran
n-Dodecane
-Terpinol
Picoline
Biphenyl
Hexanoic Acid
Pollutants
Methy ethyl ketone
Acetone
Dibensofuran
n-Dodecane
-Tterpinol
-Picoline
Biphenyl
Hexanoic Acid
tto. of
Intake Samples
6
6
6
6
6
6
6
6
tto. of
Detects
6
6
6
0
1
1
6
1
Min
28
712
4
4
Mean Ned
146
2240
18
10
20
19
1
Max
533
3600
23
70
tto, of
Intake Samples
2
2
3
3
3
3
3
3
COLORADO SUBBITUMINOUS
No. of
Intake Samples
7
7
7
7
7
7
7
7
K>. of
Detects
7
7
0
1
0
5
1
0
Min
25
83
19
Mean Med
80
7
101
2
Max
141
557
No. of
Intake Samples
15
15
15
15
15
15
15
15
No. of
Detects
2
2
3
1
1
0
3
0
Min
7
76
150
2
Mean
167
19
8
3
Med Max
64
384
180
2 4
ALL SAMPLES
No. of
Detects
15
15
15
15
15
15
15
15
Min
7
76
4
7
8
19
2
Mean
100
320
67
88
13
1
Med Max
533
3600
180
19
10
347
70
-------
TABLE A-17
PRIORITY METALS DETECTED IN THE CYCLONE QUENCH WATER (ug/1)
NORTH DAKOTA LIGNITE
TEXAS LIGNITE
u>
Pollutant
sb
As
Be
Cr
Od
Cu
Fb
Hg
Ni
Se
fQ
Th
An
Pollutants
Sb
As
Be
Cr
Od
Cu
Fb
Hg
Ni
Se
Ag
Th
Zn
No. of No. of
Intake Samples Detects
6
6
6
6
6
6
6
6
6
6
6
6
6
0
5
0
5
2
2
1
4
1
5
0
0
6
Min
20
10
100
30
0.1
60
40
45
Mean
60
16
100
30
50
0.1
74
68
Med Max
100
20
100 100
30 30
0.1 0.2
150
105
NO. of NO. of
Intake Samples Detects
3
3
3
3
3
3
3
3
3
3
3
3
3
COLORADO SUBBITUMINOUS
No. of
Intake Samples
7
7
7
7
7
7
7
7
7
7
7
7
7
No. of
Detects
5
7
0
7
4
7
7
0
4
7
7
0
7
Nin
1
4
10
2
6
20
8
1
1
39
Mean
2
6
17
2
17
59
30
3
2
76
Med Max
4
9
23
2 3
29
164
76
6
2 3
154
No.
of
Intake Samples
16
16
16
16
16
16
16
16
16
16
16
16
16
2
3
0
3
2
3
2
0
0
3
3
0
0
Min
1
4
2
2
12
7
4
1
Mean Med
1 1
9
6
2 2
13
7 7
8
2 2
Max
1
17
10
2
15
7
12
2
ALL SAMPLES
No. of
Detects
7
15
0
15
8
12
10
4
5
15
10
0
13
Min
1
4
3
2
6
7
0.1
8
1
1
39
Mean Med
1 1
24
14
27 2
18
48
0.1 0.1
36
28
2 2
72
Max
4
100
23
100
30
164
0.2
76
150
3
154
-------
TABLE A-18
CONVENTIONAL POLLUTANTS DETECTED IN THE CYCLONE QUENCH WATER (mg/1)
NORTH DAKOTA LIGNITE
TEXAS LIGNITE
u>
*»>
Pollutant
BOP
Oil & Grease
TSS
Pollutants
pH
BOD
Oil & Grease
TSS
Intake
No. of
Samples
6
6
6
6
No. of
Detects
6
6
5
6
NO. Of
Min
7.5
68
2.9
18
Mean
8.0
135
27
430
Med Max
8.6
230
59
1468
Intake Samples
3
3
3
3
COLORADO SUBBITUNINOUS
Intake
No. of
Samples
7
7
7
7
to. of
Detects
7
4
0
7
Min
6.4
46
35
Mean
6.8
114
292
Med Max
7.4
155
958
No.
of
Intake Samples
16
16
16
16
No. of
Detects
3
3
2
3
Min
6.8
120
2.9
16
Mean
7.3
271
105
Med Max
7.7
540
5.8
264
ALL SAMPLES
NO. Of
Detects
16
13
7
16
Min
6.4
46
2.9
16
Mean
7.3
160
20
309
Med Max
8.6
540
59
1468
-------
TABLE A-19
NONCONVENTIONAL POLLUTANTS DETECTED IN THE CYCLONE QUENCH WATER (rag/1)
NORTH DAKOTA LIGNITE
TEXAS LIGNITE
T
to
Pollutant
Acidity
Alkalinity
HC03
C03
TOC
COD
Phenolics
Br
Cl
F
Total Solids
Total Volatile Solids
Total Volatile Susp. Solids
Total Dissolved Solids
CN
SCN
CN /C12
Kjeldahl Nitrogen
NH3
N03
N02
PO4
SO4
S03
S=
Total Organic Nitrogen
NO. Of NO. Of
Intake Sanples Detects Min
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
2
6
6
5
0
6
6
6
6
6
6
3
6
6
6
5
4
2
6
5
3
6
6
8
67
67
16
42
234
0.02
2.9
1.4
260
62
10
296
0.04
2.7
0.02
9
1
0.15
0.03
0.04
84
2.1
2
7
Mean
72
172
160
93
421
4.57
4.8
1.55
1164
465
279
541
0.05
5.3
0.07
23
10
0.35
0.68
132
6.4
10.6
14
No. of No. of
Med Max Intake Sanples Detects Min
150
279
237
41
127
506
22.7
10
1.77
2656
1032
964
784
0.05 0.05
8.6
0.13
38
25
0.8
0.45
2.7
182
14
32
23
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
2
2
3
3
3
2
3
3
2
0
3
3
0
3
3
1
1
3
3
3
3
3
3
3
1
3
2
2
2
2
3
2
3
3
2
41
41
28
62
1.32
1.32
1248
76
10
156
0.03
0.067
10.7
6.3
2.0
0.03
0.046
41
1.1
2
4.3
Mean Med Max
52
52
118
102
2.55
1.03
5.68
1.34
282
146
19
199
0.07
1
0.14
6.3 6.3
0.055
1.3
3.1
58
58
258
130
13.1
1.35
314
268
24
254
0.1
0.265
16.4
6.3
2.7
0.04
0.06
75
1.6
5.2
10.1
-------
TABLE A-19 (continued)
NONCONVENTIONAL POLLUTANTS DETECTED IN THE CYCLONE QUENCH WATER Gmg/1)
NORTH DAKOTA LIGNITE
TEXAS LIGNITE
Pollutant
Ca
Mg
Ma
Al
Mn
V
B
Ba
Mo
Sn
Y
Co
Fe
No. Of
Intake Sanples
6
6
6
6
6
6
6
6
6
6
6
6
6
6
No. of
Detects Min
6
6
6
6
6
5
6
5
1
0
0
0
6
6
19.8
4.7
17
0.6
0.043
0.007
0.15
0.8
2
0.009
No. of No. of
Mean Med Max Intake Sanples Detects Min
41.1
10.2
78.2
10.4
0.073
0.025
0.66
1.83
0.5
14.9
0.206
89.
18.
1
2
104
23.
0.
0.
1.
3.
30.
0.
2
216
038
15
8
8
433
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
2
3
3
0
3
0
0
3
3
26
3.69
7.65
0.806
0.042
0.003
0.144
0.075
0.035
1.79
0.024
Mean Med Max
27.
4.
11.
1.
0.
0.
0.
0.
0.
2.
0.
9 30.8
28
6
27
051
003 0.003
188
185
039
05
045
4.68
15
2
0.065
0.003
0.21
0.343
0.044
2.33
0.06
to
a\
-------
TABLE A-19 (Continued)
NONCONVENTIONAL POLLUTANTS DETECTED IN THE CYCIDNE QUENCH WATER (mg/1)
COLORADO SUBBITUMINOUS
ALL SAMPLES
u>
-j
Pollutant
Acidity
Alkalinity
HCO3
C03
TOC
COD
Phenolics
Br
Cl
F
Total Solids
Total \folatile Solids
Total Volatile Susp. Solids
Total Dissolved Solids
CM
SCN
CM /C12
Kjeldahl Nitrogen
NH3
NO3
N02
P04
SO4
SO3
S=
Total Organic Nitrogen
NO. Of
Intake Samples
7
7
7
7
7
7
7
7
7
7
*6
*6
7
*6
7
7
7
7
7
6
5
7
5
7
7
7
No. of No. of
Detects Min Mean Med Max Intake Samples
0
7
7
0
7
7
7
0
6
7
6
6
7
6
6
1
7
7
7
5
4
7
5
0
7
7
35
35
3
32
0.006
7
1.2
234
35
10
156
0.04
0.03
8
4
1.3
0.02
0.23
17
2
2
153
153
23
165
0.017
18.7
3.1
516
342
241
204
0.13
1
0.10
15
9
1.6
0.05
1.08
27
2.7
6
392
392
35
288
0.023
47
73
994
958
838
258
0.34
0.15
21
14
1.9
0.07
3.68
40
4
9
16
16
16
16
16
16
16
16
16
16
15
15
16
15
16
16
16
15
15
15
14
16
13
16
16
15
No. of
Detects Min
6
16
16
2
16
16
13
1
15
16
15
15
16
15
12
8
16
15
15
11
8
16
13
6
16
15
8
35
35
16
3
32
0.006
1.32
1.2
248
35
10
156
0.03
1
0.02
8
1
0.15
0.02
0.04
17
1.1
2
2
Mean Med Max
72
141
136
67
250
1.96
1.03
10.5
2.22
728
352
214
338
0.09
4.2
0.10
18
8.3
1.3
0.09
0.74
70
3.8
5.7
9
150
392
392
41
258
506
22.7
47
7.3
2656
1032
964
784
0.34
8.6
0.265
38
25
2.7
0.45
3.68
182
14
32
23
-------
TABLE A-19 (continued)
NONCONVENTIONAL POLLUTANTS DETECTED IN THE CYCLONE QUENCH WATER (mg/1)
COLORADO SUBBITUMINOUS
ALL SAMPLES
Pollutant
Ca
Mg
Na
Al
Mn
V
B
Ba
MO
Sn
Y
CO
Fe
Ti
No. of
Intake Samples
7
7
7
7
7
7
7
7
7
7
7
7
7
7
No. of
Detects Min
7
7
7
7
7
7
5
7
3
7
1
0
7
7
21.3
4.44
5.13
1.28
0.047
0.004
0.266
0.211
0.036
0.038
1.48
0.072
No. of
No. of
Mean Med Max Intake Samples Detects Min
24.0
5.16
8.41
3.23
0.064
0.007
0.624
0.415
0.047
0.064
0.007
2.85
0.208
29.3
6.36
13.8
7.04
0.076
0.013
1.2
0.904
0.058
0.082
5.9
0.472
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
14
14
15
4
10
1
0
16
16
19.8
3.69
5.13
0.6
0.042
0.003
0.144
0.075
0.036
0.035
1.48
0.009
Mean Med Max
31.2
6.89
35.2
5.55
0.072
0.013
0.546
0.842
0.16
0.056
0.007
7.22
0.177
89.1
18.2
104
23.2
0.216
0.038
1.2
3.8
0.5
0.082
30.8
0.472
s
-------
TABLE A-20
PRIORITY ORGANIC POLLUTANTS DETECTED IN THE SCRUBBER VCVTER (ug/1)
NORTH DAKOTA LIGNITE
TEXAS LIGNITE
vo
Pollutant
Acenaphthene
Benezene
p-chloro-m-cresol
2f4-Dimethyl phenol
2,4-Dinitrotoluene
2,5-Dinitrotoluene
1,2-Diphonylhydrazine
Ethylbenzene
Methylene chloride
Methyl chloride
Naphtalene
Nitrobenzene
4-Nitrophenol
N-Nitrosodiphenylamine
Phenol
Bis(2-ethylhexyl)phthalate
Butylbenzyl phthalate
Di-n-Butyl phthalate
Di-n-Octyl phthalate
Di ethyl phthalate
Benzo(a)anthracene
Benzo(a)pyrene
Chrysene
Acenaphthalene
Anthracene
Fluorene
Phemanthrene
Pyrene
Toluene
NO. Of
Intake Samples
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
No. of No. of ND. of
Detects Min Mean Med Max Intake Samples Detects
0
0
1
4
2
1
3
1
4
1
4
1
1
2
4
2
1
3
3
2
1
0
1
3
4
1
4
1
0
84
1130 55300
257
2
1 32
14880
53 216
36
378 559
737
33
286
3220 93000
48
7
78 118
560 ,1080
4
399
284
146 479
69 152
378
171 296
180
197000
1570
50
531
836
482
286000
269
151
1850
31
1010
280
570
1
0
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
0
1
0
0
0
0
1
0
1
0
0
1
1
0
0
0
1
0
1
0
1
1
0
0
0
0
1
Min Mean Med M<
55
288
1140
122
998
75
34200
5
29
59
168
292
-------
TABLE A-20 (Continued)
PRIORITY ORGANIC POLLUTANTS DETECTED IN THE SCRUBBER WATER (ug/1)
COLORADO SUBBITUMINOUS
ALL SAMPLES
jx
I
Pollutant
Acenaphthene
Benezene
p-chloro-m-cresol
2,4-Dimethyl phenol
2,4-Dinitrotoluene
2,5-Dinitrotoluene
1,2-Diphonylhydrazine
Ethylbenzene
Methylene chloride
Methyl chloride
Naphtalene
Nitrobenzene
4-Nitrophenol
N-Nitrosodiphenylamine
Phenol
Bis(2-ethylhexyl)phthalate
Butylbenzyl phthalate
Di-n-Butyl phthalate
Di-n-Cctyl phthalate
Diethyl phthalate
Benzo(a)anthracene
Benzo(a)pyrene
Chrysene
Acenaphthalene
Anthracene
Fluorene
Phemanthrene
Pyrene
Toluene
No. Of
Intake Samples
3
3
3
2
3
3
3
3
3
3
3
3
3
3
2
3
3
3
3
3
3
3
3
3
3
3
3
3
3
No. of
Detects Min
0 567
3
0 12300
2
0
0
0
0
3 32
0
0
0
0
0
2 34000
0
0
0
0
0
0
1
0
1
1
1
1
1
3 398
Mean Med
738
48
<50
<50
1810
1310
394
473
179
448
No. of
Max Intake Samples
896 8
8
130000 8
8
8
8
8
8
70 8
8
8
8
8
8
754000 8
8
8
8
8
8
8
8
8
8
8
8
8
8
490 8
ND. of
Detects
1
4
1
7
2
1
3
1
8
1
5
1
1
3
7
2
1
3
4
2
2
1
2
5
6
2
5
2
4
Min
288
1130
257
1
32
378
75
3320
48
78
5
4
29
59
146
69
378
171
179
292
Mean Med Max
55
625
84
52100
2
32
14880
141
36
669
737
33
281
214000
7
118
812
<50
683
374
272
409
896
197000
1570
50
531
998
482
754000
269
151
1850
31
399
284
1810
1310
394
570
180
490
-------
TABLE A-21
NONCONVENTIONAL ORGANICS DETECTED IN THE SCRUBBER WATER (ug/1)
NORTH DAKOTA LIGNITE
TEXAS LIGNITE
Pollutant
Methyl ethyl ketone
Acetone
Dibensofuran
n-Dodecane
_-Tarpinol
33, Pollutant
^ Methyl ethyl ketone
Acetone
Dibensofuran
n-Dodecane
_-Terpinol
NO. Of
Intake Sanples
4
4
4
4
4
No. of
Detects Min Mean Med
4 929 1240
4 10200 14000
1 33
0
1 <20
Max
1590
17400
NO. of
No. of
Intake Sanples Detects Min
1
1
1
1
1
COLORADO SUBBITUMINOUS
No. of
No. of
Intake Samples Detects Min Mean Med
3
3
3
3
3
3 279 2650
3 1060 12500
0
0
0
Max
4400
21700
l*>. of
Intake Sanples
8
8
8
8
8
1
1
1
1
0
ALL SAMPLES
NO. of
Detects Min
8 279
8 1060
2 33
1
1
Mean
1730
3570
400
3060
Mean
1670
12200
3060
<20
Med Max
Med Max
4400
21700
400
-------
TABLE A-2 2
PRIORITY METALS DETECTED IN THE SCRUBBER WATER (ug/1)
NORTH DAKOTA LIGNITE
TEXAS LIGNITE
fe
to
Pollutant
Sb
As
Be
Cr
Cd
Cu
Pb
Hg
Ni
Se
Ag
Th
Zn
Pollutant
Sb
As
Be
Cr
Cd
Cu
Pb
»3
Ni
Se
AQ
Th
Zn
No. of No. of
Intake Sanples Detects
i
a
No. of No. of
Nin Mean Ned Max Intake Sanples Detects
I 0
4 47 55 64
0
4 20 35 50
0
0
0
0
4 40 40 40 40
2 10 120
0
0
4 40 49 65
3LORADO SUBBITUMINOUS
NO. Of
No. Of
Intake Samples Detects
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
0
3
2
3
3
3
1
3
2
1
3
1
1
1
1
1
1
1
1
1
1
1
1
1
No. of
Min Mean Med Max Intake Sanples
5
8
16
3
29
36
0.7
52
3
73
30
35
28
3
107
57
2.4
9
216
2
187
74
80
38
3 3
260
69
5.4
422
4
360
8
8
8
8
8
8
8
8
8
8
8
8
8
Min Mean Med Max
0
1
0
1
0
1
0
0
0
1
1
0
0
ALL SAMPLES
NO. of
Detects Min
3
8
0
8
2
4
3
3
5
6
3
1
7
5
8
6
3
6
3.6
0.7
9
10
3
40
8
6
6
170
5
Mean Med Max
30
42
29
3
81
57
2.4
34
159
4
2
108
74
80
50
3 3
260
96
5.4
40
422
5
360
-------
TABLE A-23
Conventional Pollutants Detected in the Scrubber Water (mg/1)
NORTH DAKOTA LIGNITE
TEXAS LIGNITE
Pollutant
pH
BOO
Oil fc Grease
TSS
Pollutant
BOD
Oil & Grease
TSS
NO. Of
Intake Sanples
No. of
Detects Min
ND. of ND. of
Mean Ned Max Intake Sanples Detects Min
4 4 8.3 8.3
4 4 1300 3000
3 3 576 1110
4 4 46 576
COLORADO SUBBITUMINOUS
No. of
Intake Samples
3
3
3
3
8.4
4100
1375
1030
No. of
Detects Min
3
3
3
3
8.4
9450
418
17
1
1
1
1
ND. of
Mean Ned Max Intake Sanples
8.5
15800
846
76
8.7
25000
1490
186
8
8
7
8
1
1
1
ALL SAMPLES
Mean Med Max
6.8
2240
1000
240
NO. Of
Detects Min
8
8
7
8
6.8
1300
418
17
Mean Med Max
8.2
7710
980
346
8.7
25000
1490
1030
u>
-------
TABLE A-24
NONCONVENTIONAL POLLUTANTS DETECTED IN THE SCRUBBER WATER (mg/1)
NORTH DAKOTA LIGNITE
TEXAS LIGNITE
Pollutant
Acidity
Alkalinity
HC03
C03
TOC
COD
Phenolics
Br
Cl
F
Total Solids
Total Volatile Solids
Total Volatile Susp. Solids
Total Dissolved Solids
CN
SCN
CN /C12
Kjeldahl Nitrogen
NH3
NO3
N02
P04
S04
SO3
S=
Total Organic Nitrogen
No. of
Intake Samples
4
4
4
4
3
4
4
4
3
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
No.
of
Detects Min
0
4
4
0
3
4
4
0
3
4
4
4
4
4
4
4
4
4
4
4
3
4
2
4
3
4
2400
2400
315
12500
28.7
100
7.3
9440
89
39
5112
0.49
590
0.02
9509
37
1.43
0.56
0.17
880
190
250
70
Mean
3140
3140
6080
55800
35.5
423
19.5
12300
6430
518
7410
0.88
1150
0.74
1210
1060
11.2
2.02
0.67
210
303
152
Med Max
3550
3550
10100
78200
43
1070
33.6
18600
9127
980
12000
1.4
1900
1.5
1630
1560
36
3.5
1.08
4400
210 230
340
358
No. of No.
Intake Samples
1
1
1
1
1
0
1
1
1
1
1
1
1
1
1
1
1
0
0
1
1
1
1
1
1
0
of
Detects
0
1
1
1
1
0
1
0
1
1
1
1
1
1
1
I
I
0
0
0
0
1
1
1
1
0
Min Mean Med Max
1160
754
315
207
0.66
26.3
1.78
2310
2220
235
978
35
18
1.98
0.157
1310
400
220
-------
TABLE A-24 (continued)
NONCONVENTIONAL POLLUTANTS DETECTED IN THE SCRUBBER WATER (mg/1)
NORTH DAKOTA LIGNITE
TEXAS LIGNITE
Pollutant
Ca
Mg
Na
Al
Mn
V
B
Ba
Mo
Sn
y
Co
Fe
Ti
NO. Of
Intake Samples
4
4
4
4
4
4
4
4
4
4
4
4
4
4
No. of
Detects Min
4 10500
4 10500
4 8500
4 2800
4 46
0
4 630
4 200
0
0
0
0
4 6600
2 4
Mean Med
15800
12700
19500
3850
75
762
300
7160
Max
23200
17100
31400
5200
106
930
400
8100
9
No. of
Intake Samples
1
1
1
1
1
1
1
1
1
1
1
1
1
1
No. of
Detects Min
1
1
1
1
0
1
1
1
1
1
0
0
1
1
Mean Med Max
' 21100
3300
8600
2200
9
725
114
36
50
146
434
-------
TABLE A-24 (Continued)
NCWTONVENTIONAL POLLUTANTS DETECTED IN THE SCRUBBER WATER (mg/1)
COLORADO SUBBITUMINOUS
ALL SAMPLES
No. Of
Pollutant Intake Samples
Acidity
Alkalinity
HCO3
COS
TOC
COD
Phenol ics
Br
Cl
F
> Total Solids
*> Total Volatile Solids
01 Total Volatile Susp. Solids
Total Dissolved Solids
CN
SCN
CN /C12
Kjeldahl Nitrogen
NH3
NO3
NO2
P04
SO4
SO3
S=
Total Organic Nitrogen
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
No. of
Detects Min
0
3
3
3
3
3
3
0
1
3
3
3
3
3
3
3
3
3
3
2
0
1
3
3
3
3
2210
1830
7
1150
24000
17.8
276
4300
3490
14
4110
0.16
440
0.19
987
932
75
811
25
4
55
No. of
Mean Med Max Intake Samples
2550
2190
383
4130
35200
23.2
75
971
4900
3710
69
4810
5.2
857
0.35
1370
1300
1.12
1280
267
14
72
2740
2730
672
6570
49600
29.8
1740
5970
4140
170
5480
8.09
1070
0.56
1860
1770
80
1770
575
23
100
8
8
8
8
7
7
8
8
7
8
8
8
8
8
8
8
8
7
7
8
8
8
8
8
8
7
No. of
Detects Min
0
8
8
4
7
7
8
0
5
8
8
8
8
8
8
8
8
7
7
6
3
6
6
8
7
7
1160
754
7
207
12500
0.66
26.3
1.78
2310
89
14
978
0.16
18
0.02
987
37
1.43
0.56
0.157
811
25
4
55
Mean Med Max
2670
2480
366
4380
46900
26.5
274
374
8260
4880
314
5630
6.77
896
0.75
1280
1160
33.3
2.02
0.66
1740
255
130
118
3550
3550
672
10100
78200
43
1070
1740
18600
9127
980
12000
35
1900
1.98
1860
1770
80
3.5
1.12
4400
575
340
358
-------
TABLE A-24 (continued)
NONCONVENTIONAL POLLUTANTS DETECTED IN THE SCRUBBER WATER (nvg/1)
COLORADO SUBBITUMINOUS
ALL SAMPLES
Pollutant
Ca
Mg
Na
Al
Mn
V
B
Ba
MO
Sn
•> Co
^Fe
Ti
No. Of
Intake Samples
3
3
3
3
3
3
3
3
3
3
3
3
3
3
No. of
Detects Min
3
3
3
3
1
3
3
0
0
3
0
0
3
3
6830
5130
33400
1530
3
4480
55
190
35
No. of No. of
Mean Med Max Intake Samples Detects Min
29100
16700
40400
4610
12
7
17800
110
358
61
66900
35100
51000
8420
10
35500
155
515
102
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
5
4
8
5
1
4
0
0
8
6
6830
5130
8500
1530
0.012
0.003
630
114
50
146
4
Mean Med
21400
13000
25900
3930
62
0.008
7140
263
36
95
3730
105
Max
66900
35100
51000
8420
106
10
35500
400
155
8100
434
-------
MORGANTOWN ENERGY TECHNOLOGY CENTER (METC) LOW-Btu GASIFICATION
SELECTION RATIONALE
The METC low-Btu gasification facility was selected for sampling
for the following reasons:
o The rtETC low-Btu gasifier is a pilot unit; however,
the gasificaiton process, gas cleanup, and the waste
streams are representative of those to be used in
future combined cycle applications;
o It is one of the few low-Btu gasification facilities
which has a sulfur removal train; and
o It utilizes pressurized (200 psig) fixed bed gasifi-
cation technology.
PROCESS DESCRIPTION
The low-Btu gasification facility at METC consists of an elevated
pressure (200 psig), fixed-bed Wellman-Galusha gasifier operated
with a mechanical stirrer. This pilot unit has been producing a
desulfurized product gas ( 150 Btu/scf) using agglomerating high
swelling bituminous coals. A flow diagram of the gas production
and cleanup system is shown in Figure A-2. The gasifier is of
1967 vintage/ while the full flow gas cleanup system is
approximately one year old. The product gas if flared or
combusted in an erosion/corrosion test facility.
Coal is transported from storage piles to silos via a vibrating
feeder, conveyor belt, and bucket elevator. It is discharged
from silos to overhead hoppers before routing to the gasifier.
Coal passes from the coal hoppers to a screw type feeder which
introduces the coal into the gasifier. Ash is collected wet from
the bottom of the gasifier and conveyed from an ash hopper to
drums for final disposal.
The product gas flows out the top of the gasifier into a cyclone
to remove fines and particulates. The gas is cooled and tars are
condensed and removed in the humidifier (spraytower). In
addition, there are cyclones and a venturi scrubber just down-
stream of the humidifier for removing additional tar. There is
an electrostatic precipitator downstream of the venturi scrub-
ber, however, it has not been successfully operated to date. The
direct cooler provides final cooling and condensing of any higher
boiling po;Lnt residual tars and oils.
METC has a Holmes-Stretford system for removing and recovering
sulfur from the product gas stream. Residual hydrogen sulfide
A-48
-------
TO flABI
TO COMmiWOK/MOSION t
•AMFIE
* SAHrLCt RECEIVCO BY MADIAM
-T»B/OUiT
Figure A-2. Sample Locations and Numbering System
METC Gasification Facility Run 98
-------
concentrations of less than 10 ppm in the product gas have been
achieved; however, long-terra stabilized operation has not been
achieved. Prior to introducing the product gas into the
combustor in the corrosion/erosion facility or to the flare, the
gas flows through alkali scrubbers, a knock-out drum, and a
muffler as final cleanup.
SAMPLING EPISODES
The sampling locations are indicated in Figure A-2 by numbered
circles and squares. Sample points designated by numbered
circles indicate samples were taken for the Effluent Guidelines
Division under authority of the Clean Water Act. Sample points
designated by numbered squares indicate samples taken for the
Office of Solid Waste under the authority of the Resource
Conversation and Recovey Act (RCRA). A list of all the sample
points and the numbered samples which were planned to be taken
each day is presented in Table A-25. METC personnel limited the
sampling effort to sampling points listed below:
o Source water (SO)
o Feed Coal (SI)
o Gasifier Ash (S2)
o Venturi Scrubber (S10)
Recycle Water (S36/S37)
o Direct Cooler
Recyle Water
Because plant personnel advised the sampling crew that the
gasifier would only be operated for 24 hours, the above schedule
was modified.
In addition to the 24-hour composite samples of the aqueous
streams (S-10 and S-37) for Day 1, additional grab samples of
these streams would be collected at 4-hour intervals. This
decision was based on the concern for obtaining samples during
steady-state operation. The original intent was to sample the
system at steady state; however, the quality of the water in the
recirculating gas cooling and scrubbing system might not be in a
steady-state condition at the beginning of the 24-hour com-
positing period (because of the shutdown). The additional grab
samples would help to document changes in the quality of the
recirculating water over the 24-hour period if steady state was
not achieved.
The grab samples which were collected in addition to the four
hour aliquots for the 24-hour composites and the regular four
A-50
-------
TABLE A-25
SAMPLE POINTS AT THE METC GASIFICATION FACILITY
SOURCE
Source Water
Feed Coal
Gasifier Ash
Cyclone Dust
Humidifier Tar
Cyclone Tar
Venturi Scrubber
Recycle Water
Venturi Scrubber Tar
Direct Cooler Recirculating
Decanter Oil
Decanter Oil
Direct Cooler Recycle Water
SAMPLE POINT
O
SOLID WASTE SAMPLES
WATER SAMPLES
* The sample point labeled S-36 on the flow diagram
was changed to S-37 by METC. These two points are
synonymous.
A-51
-------
hour grab samples for volatile organics are listed in Table A-26.
These samples were not included in the original sampling schedule
outlined in the test plan. Additional grab samples were not
collected at 5:00 a.m. in an effort to conserve glassware. Also,
no additional grab samples were collected for dissolved metals,
and additional grabs for total metals analysis were collected
only at S-10 (venturi scrubber recycle liquor) and only at
eight-hour intervals (5:00 p.m., 1:00 a.m., and 9:00 a.m.).
At the end of the first 24-hour sampling period, the gasifier was
still running and a second 24-hour compositing period was
initiated. At this time the gasifier was scheduled to run for 48
additional hours because personnel were being reassigned to work
at the gasification area on the evening and night shifts. An
inventory of glasswre indicated that there were enough bottles
for two more 24-hour composites from each of the two process
water sample points (S-10 and S-37), as well as the source water
sample (S-0); however, it would not be possible to collect the
duplicate sample of the direct cooler recyle liquor (S-37) which
was originally planned during the second 24-hour compositing
period for quality control purposes. The gasifier continued to
run through Friday and three 24-hour composite samples were
obtained from S-10 and S-37.
The source water sample was collected on Day 2 rather than Day 1
as originally planned. The collection of this sample on Day 2
rather than Day 1 should have no significant effect on the data.
The source water which is used as makeup water was collected from
a tap. EG&G personnel explained that this was not potable water
but was part of a recirculating utility water system which
includes the plant's cooling water with added corrosion
inhibitors, and 'recycled water from a pond which receives
intermittent discharges from the gasification area.
OPERATION DATA
Operating data was obtained periodically during the sampling
visit in the form of graphic printouts from the facility's
on-line computer systems. This data is summarized in Table
A-27.
POLLUTANT DATA
The samples collected were analyzed as described in the sampling
plan. A summary of the results of these analyses are given in
Tables A-28 through A-37. Grab samples and composite sample
analytical data are treated alike in the summary. Source
problems are suspected in the 4AAP Phenol analyses.
A-52
-------
TABLE A-26
MATRIX OF ADDITIONAL FOUR HOUR GRAB SAMPLES OF AQUEOUS STREAMS
COLLECTED FOR EGD AND OSW AT METC DURING FIRST 24 HOUR SAMPLING PERIOD
Ul
u>
Date
Time
Sample Point: S-10
SCC Number
8/4/81
5:00 pm
8/4/81
9:00 pm
8/5/81
1:00 am
8/5/81
5:00 am
Extractable
Organics
Pesticides
Group 1
Group 2
Phenolics
Cyanides
Oil & Grease
Sulfide
Total Metals
8/5/81
9:00 am
S-10
10273
X
X
X
X
X
X
X
X
X
S-27
10271
X
X
X
X
X
X
X
X
S-10
10274
X
X
X
X
X
X
X
X
S-37
10278
X
X
X
X
X
X
X
X
S-10
10275
X
X
X
X
X
X
X
X
X
S-37 S-10 S-37
10279
X
X
X
X
X
X
X
X
S-10
10276
X
X
X
X
X
X
X
X
X
S-37
10512
X
X
X
X
X
X
X
X
-------
TABLE A-27
PROCESS DATA COLLECTED AT THE METC LOW-Btu GASIFICATION FACILITY
4 August 1981 - 6 August 1981
Date: 8/4/81 8/4/81 8/5/81 8/5/81 8/5/81 8/5/81 8/5/81
Time 1848 2304 0049 1144 1149 2239 0137
Air Flow (SCFH) 48703 50341 48846 50017 48465 53695 50400
Steam Flow (t/1 hr) 808 806 808 818 813 745 746
Exit Gas Press. (PSIG) 125 123 125 126 125 123 124
Exit Gas Temp 1099 1000 1029 1061 1042 1024 1076
Venturi Recycle Flow 5.0 4.9 4.8 4.9 5.0 5.0 4.9
(GPM)
Venturi Recycle Temp 257 252 250 255 250 249 252
Venturi Recycle Press. 99 100 100 101 100 99 101
(PSIG)
Direct Cooler Flow 133 137 133 135 131 140 137
(GPM)
Direct Cooler Temp 110 106 104 109 109 98 96
Direct Cooler Press. 100 100 101 100 100 99 100
(PSIG)
Gas Composition
H2 % 17.7 17.6 17.3 17.5 17.5 17.7 16.7
CO % 21.9 22.5 22.9 23.0 21.5 22.2 20.9
C02 % 9.1 7.5 8.1 8.2 8.0 7.8 8.4
N2 % 46.0 46.1 45.7 45.5 47.0 46.4 48.7
Heating Value 156 162 161 163 158 163 151
(BTU)
A-54
-------
Table A-28
Priority Organic Pollutants Detected in
the Direct Cooler Recycle (ug/1)
ND. of ND. of
Samples Detects Min Mean Median
Acenaphthene
Benzene
2,4-Dimethylphenol
Ethylbenzene
Fluoranthene
Methylene chloride
Naphthalene
Phenol
Bis(2-ethylhexyl)phthalate
Di-n-butyl phthalate
Acenaphthalene
Anthracene
Fluorene
Phenanthrene
Pyrene
Toluene
7
7
7
7
7
7
7
7
ite 7
7
7
7
7
7
7
7
7
3*
5
3*
1
1
6
7
1
1
3
6
7
7
2
3*
157
2130
584
65
15000
25500
127
253
891
891
110
1150
817
2430
2837
67
469
13
36000
70300
91
52
325
1020
3730
3580
1270
Max
2580
2780
7670
70
82400
133000
465
2830
11200
10300
176
1350
Table A-29
Nonconventional Organic Pollutants Detected
in the Direct Cooler Recycle (yg/1)
Methyl ethyl ketone
Acetone
Hexanoic Acid
Dibenzofuran
n-Dodecane
Dibenzo thiophene
Biphenyl
ND. of No. of
Samples Detects Min
Mean Median
Max
7
7
7
7
7
7
7
3*
3*
3
7
4
1
7
54
1340
2210
2220
914
111
97
2100
2470
6710
2070
309
640
183
3430
2650
16600
3210
2090
A-55
-------
Table A-30
Priority Organic Pollutants Detected in
the \fenturi Scrubber Recycle (yg/1)
Acenaphthene
2,4-Dimethylphenol
Naphthalene
N-n itrosodiphenylamine
Pentachlorophenol
Phenol
No. of No. of
Sanples Detects Min
7
7
7
7
7
7
Bis(2-ethylhexyl)phthalate 7
Benzo(1)anthracene 7
Acenaphthalene 7
Chrysene 7
Fluorene 7
Phenanthrene 7
1
5
3
1
1
7
1
3
3
2
1
1
139
99
150
857
18900
65
2190
12
Mean Median
130
3000
247
79300
127
75
2550
220
771
Max
12000
324
302000
90
2820
25
Table A-31
Nonconventional Organic Pollutants Detected
in the ^nturi Scrubber Recycle (yg/1)
No. of No. of
Sanples Detects Min
Methyl ethyl ketone
Acetone
Benzoic Acid
Hexanoic Acid
7
7
7
7
2
2
7
7
41
166
7590
10200
Mean Median
21300
12000
Max
392
2330
32500
14600
A-56
-------
Table A-32
Sb
As
Be
Cr
Cd
Cu
Pb
Hg
Ni
Se
Ag
Th
Zn
Priority Metals Detected in the
Venturi Scrubber Recycle (yg/1)
No. of No. of
Samples Detects Min
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
0
6
6
6
0
6
6
Mean Median
40
1800
11
33
16
46
8
284
487
76
90
76
2390
12
48
20
59
12
362
10900
96
1510
21
Max
142
3320
14
91
21
71
18
391
51900
115
6600
Intake
Water
<0.002
<0.008
<0.010
0.021
<0.04
<0.004
0.014
<0.004
<0.005
<0.063
0.027
Table A-33
Priority Metals Detected in the
Direct Cooler Recycle (yg/1)
No. of No. of
Sanples Detects Min
Mean Median
Max
Intake
Water
Sb
As
Be
Cr
Cd
Cu
Pb
Hg
Ni
Se
Ag
Th
Zn
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
0
3
0
3
0
3
3
3
0
2
3
8
117
11
12
11
7
810
65
112
9
206
18
24
17
33
1290
140
12
291
40
35
21
50
1540
73
193
<0.004
<0.003
<0.002
<0.008
<0.010
0.021
<0.04
<0.004
0.014
<0.004
<0.005
<0.063
0.027
A-57
-------
Table A-34
Conventional Pollutants Detected in the
Venturi Scrubber Recycle (mg/1)
Kb. of No. of
Samples Detects
Min
Mean Median
Max
Intake
Water
BODS
Oil and Grease
TSS
7
7
6
7
7
7
6
7
7.55
<2000
155
11.6
8.13
<2000
271
752
8.9
<2000
398
5060
7.99
<1
<0.002
<0.008
Table A-35
Conventional Pollutants Detected in the
Direct Cooler Recycle (mg/1)
No. of No. of
Samples Detects Min Mean
Median
Max
Intake
Water
BOD5
Oil and Grease
TSS
7
7
6
7
7
7
6
7
8.53
340
549
18.8
8.65
841
46.7
8.71
<2000
1200
77.3
7.99
<1
3.69
6
A-5 8
-------
Table A-36
NONCONVENTIONAL POLLUTANTS DETECTED IN THE
VENTURI SCRUBBER RECYCLE (mg/1)
Pollutant
Acidity
Alkalinity
HC03
C03
TOC
COD
Phenolics
Br
Cl
F
Total Solids
Total Volatile Solids
Total Volatile Susp. Solids
Total Dissolved Solids
CN~
SCN
CN /C12
Kjeldahl Nitrogen
NH3
N03
N02
P04
S04
S03
S=
Total Organic Nitrogen
Ca
Mg
Na
Al
Mn
V
B
Ba
MD
Su
Y
Co
Fe
Tte
No. of No. of
Samples Detects Min Mean Med
Max
Intake
5
7
7
0
7
7
7
3
7
7
6
5
6
6
7
6
6
7
6
6
7
7
1
7
7
7
6
6
6
6
6
6
6
6
6
6
6
6
6
6
5
7
7
7
7
7
1
7
7
6
-5
6
6
7
6
6
7
6
6
0
7
1
7
7
7
6
6
6
6
6
6
6
6
0
3
1
6
6
6
1590
5310
5310
15500
19800
0.77
18000
379
59600
50500
11.2
58300
2360
304
2080
8840
29
0.17
110
3
50
2.22
0.89
13.6
25.8
0.58
0.08
270
0.18
1.49
0.06
154
0.39
5270
7820
7820
17800
71100
1630
1.16
20000
2190
68500
62000
31.4
66400
2610
344
10700
10900
166
2.08
1420
270
13.5
1230
3.24
1.31
47.8
29.8
1.47
0.13
321
0.20
1.55
0.01
0.07
202
0.43
10200
-9480
9480
22600
88000
6330
24000
3000
82300
72800
60
81700
3340
412
15800
13700
357
9.1
361
27
2200
4.22
1.64
73.3
36.1
2.59
0.21
374
0.22
1.63
0.08
230
0.52
<1
41
41
<5
3.5
<0.005
0.18
16.4
1.3
196
15.3
<0.5
188
0.56
<1
0.37
229
152
<1
<0.01
0.45
44
<0.5
1.9
77
25.5
4.94
15.5
0.315
0.013
<0.01
1.1
0.035
<0.015
<0.020
<0.010
<0.009
0.407
<0.005
A-59
-------
Table A-37
Nonconventional Pollutants Detected in the
Direct Cooler Recycle (mg/1)
Pollutants
Acidity
Alkalinity
HC03
C03
TOC
COD
Phenolics
Br
Cl
F
Total Solids
No. of
Samples
7
7
7
7
7
6
7
6
6
7
7
Total Volatile Solids 6
Total ^folatile
Suspended Solids
Total Dissolved
Solids
CN
SCN
CN/C12
Kjeldahl Nitrogen
NH3
N03
N02
PO4
SO4
503
S
Total Organic
Nitrogen
Ca
Mg
Na
Al
Mn
V
B
Ba
Mo
Sn
Y
Co
Fe
Ti
7
7
6
6
6
7
7
6
7
7
7
7
7
7
3
3
3
3
3
3
3
3
3
3
3
3
3
3
No. of
Detects
0
7
7
7
7
6
7
1
6
7
7
6
7
7
6
6
6
7
7
5
2
6
7
7
7
7
3
3
3
3
3
0
3
3
0
0
0
1
3
1
Min
31200
27500
2580
5590
19700
0.99
250
7.8
1120
1180
13.6
578
112
240
24
7590
3200
53.3
0.59
.051
49
111
98
100
2.23
0.175
1.51
0.261
0.086
4.63
0.046
13.5
Mean
338UO
28900
4990
6190
31500
713
0.46
362
19.0
1590
1490
31.4
1000
200
405
357
9770
7810
65.8
0.301
539
172
144
1960
3.40
0.377
2.32
0.308
0.133
5.78
0.076
0.01
20.7
0.04
Median
Max
Intake
Water
<1
37500
32000
7460
6720
69100
4420
575
33
1960
1800
56
1530
269
500
1130
13100
11600
87.3
0.78
0.948
865
220
295
5600
4.1
0.609
3.20
0.377
0.218
7.77
0.117
33.3
<5
3.5
<0.005
0.18
16.4
1.3
19.6
15.3
<0.5
188
0.56
<1
0.37
229
152
<1
<0.01
0.45
44
<0.5
1.9
77
25.5
4.94
15.5
0.315
0.013
<0.01
1.1
0.035
<0.015
<0.020
<0.010
<0.009
0.407
<0.005
A-60
-------
GENERAL ELECTRIC CORPORATE RESEARCH AND DEVELOPMENT CENTER
SELECTION RATIONALE
The GE low-Btu gasification facility was selected for sampling
for the following reasons:
o While the GE system is a pilot unit, the gasifica-
tion process, gas cleanup and resultant condensates
and waste streams are representative of those ex-
pected in future commercial combined cycle applica-
tions; and
o The gas cleanup train is extensive and provides
an opportunity to evaluate potential solid and
aqueous wastes from several stages of gas cleanup.
PROCESS DESCRIPTION
Figure A-3 is a schematic diagram of the Gasifier and Gas Cleanup
System. The GE gasifier is a pressurized fixed bed refractory
lined gasifier which produces a low-Btu gas of 150 to 180
Btu/scf. The gasifier typically runs at a pressure of approxi-
mately 300 psig. The present feedstock to the gasifier is
Illinois #6 coal with an average sulfur content of two percent.
The coal is sized (1/4 inch to 2 inches) and delivered to the
site by truck. Coal is fed to the top of the gasifier at a rate
of 24 tons per day by an auger feeder and steam and air are
injected into the bottom of the gasifier. Ash is discharged from
the bottom of the gasifier through an ash lock hopper.
The hot raw gas exits the top of the gasifier at 1,100°F and
enters a water quench where tars and particulates are knocked out
and the gas is cooled to 3300p. The quench liquor then passes
through a cartridge filter and is recycled back to the quenching
operation. The solids which are retained in the filter are
removed through a sludge lock and discharged to a drum. These
solids consist primarily of condensed organics and coal fines.
The gas is then scrubbed in a venturi scrubber to remove
particulates and tars carried over from the quench step. The
scrubber liquor flows to a separator from which tars are manually
removed. The decanted scrubber -liquor flows to an underground
tank and is eventually used as makeup to the initial gas
quenching step.
The cleaned gas passes through two shell and tube heat exchangers
in series labeled EI and Ł2 where the gas is cooled to
180°F. The condensate stream from EI flows to a separator
labeled V2 where tar is separated from the water and light oil
phases. The combined condensate and low-Btu gas stream exiting
A-61
-------
COAL
•TIAH
J>
1
to
€
/Al
i)
H
>1
OAB
-^O1
'C
Fill
•>
S
\
I
UNO
,
IROR<
TANK
j-
>ll
FH
m
.T
1
1
M
ILU
_^
ou
001
IK
CM
»*<
••
»'F
VIN1
•CRU
••PAD
1
ruRi
*MR
f
V
ATOR
h,
><
.4
DICAI
7>v
»•>
III
•
O
(
V
M
(Oi
1
•1
V
^•N
10
•h^i
1C
r)
h
*
•AH
v*
AN
•
J
a
X
1
A
T
'
TOR
1
—
•
1
UFA
TAR
'
,.
O
"
1
'1
RATO
r
— 1
*
It
1
J
100
•INI
AMO
>p
'If
Rl
1
LO
•R
IBM
»t*»
!•
TKJI
DHIN
»'F
«
1
•NALIZ
OAt
fATIR
fO WAI
WASH
»O
(
•M
•r
iJ
HCAT
^
^C_
TO TitT
_, J
"* i
t
i
i
)
EH y
o
X
•URNIR
{
»
|
i
•
t
O
•AMM.I FOR O«W
•AMPLB FOR BOD
Figure A-3. Schematic Diagram of General Electric Low-Btu Gasification
and Gas Cleanup Train Showing Proposed Sample Locations
-------
E2 enter a separator labeled V^ where the gas, tar, and water
and light oil phases are separated. Both of -the separators (V2
and Vi) are equipped with a tar boot from which tar is
periodically withdrawn.
The cooled gas exiting the Vi separator is scrubbed with a
potassium carbonate solution in a Benfield H2S absorber. The
gas is then washed with demineralized water to remove any alkali
metals which might be present in the gas and cause corro'sion
problems in a gas turbine. The demineralized water from the gas
washer is used as makeup water to the Benfield solution
regeneration process. The low-Btu gas which exists the washer is
reheated and saturated with water and light hydrocarbons
(decanted water and light oils from separators V"i and V2) in
a resaturator. The liquor from the resaturator is routed to an
underground tank and eventually used as makeup water to the
initial quenching operation. The final saturated low-Btu gas is
then combusted in the test burner.
SAMPLING EPISODES
Table A-38 lists all of the sample points selected for either
water or solid waste sampling. Samples were collected at sample
points 00 through 05, however, the operator and DOE did not grant
permission to sample the other points. At the time of sampling,
the quench liquor sample which was planned to be collected at
sample point 05 was changed to the quench liquor filtrate at
sample point 06. The quench liquor filtrate is a more
representative sample because it is collected directly downstream
of the intiial gas quench step.
Also, the sampling episode for the GE facility was restricted for
GE only one 24-hour compositing period rather than the three
which had been planned.
The 24-hour sampling period began at 2:00 a.m., 21 October 1981.
Time composites were collected of the quench liquor (sample point
06) and quench liquor duplicate, gasifier ash (sample point 02),
and quench blowdown sludge (sample point 03) and quench blowdown
sludge duplicate. Aliquots for these composites were collected
at four-hour intervals at the following times on 21 October 1981:
2:00 a.m.
6:00 a.m.
10:00 a.m.
2:00 p.m.
6:00 p.m.
10:00 p.m.
Grab samples for volatile organics were also collected at these
times. Grab samples of the source water, feed coal, and
A-63
-------
Table A-38
Sample Points and Rationale for Selection for Aqueous and Solid Stream
Characterization at General Electric
Sample
Point
Number
Sample Point Description
Rationale for Selection
Makeup Water
Feed Coal
Gasifier Ash
Quench Slowdown Sludge
By-Product Tar
Quench Liquor Recycle
The source water was chosen for sampling to provide
background characteristics for comparison with data from
other streams.
The feed coal was chosen to provide background charactertics
for comparison with data frort other streams.
This source was selected because it is representative of the
ash that would be disposed of from a commercial facility.
This stream was selected because it represents a solid waste
stream which would require disposal at a commercial low-Btu
facility.
This stream was selected because it is believed to be repre-
sentative of tar streams which would be found at a commercial
facility. It also represents a stream which may be stored
on-site prior to combustion which may require combustion
which may require compliance with certain Office of Solid
Waste regulations depending on the chemical nature of the
material.
This stream was selected for sampling because it represents
the sole wastewater discharge to treatment and is
representative of wastewater discharges which would be
expected from commercial low-Btu gasification facilities.
-------
Table A-38 (continued)
Sample Points and Rationale for Selection for Aqueous and Solid stream
Characterization at General Electric
Sample
Point
Nunber
Sample Point Description
Rationale for Selection
CTl
Ul
07
09
Quench Liquor Filtrate
Scrubber Liquor Decant
EI Heat Exchanger
Gondensate Liquor
EI Heat Exchanger
Gondensate Tar
Ł2 Heat Exchanger
Cbndensate Liquor
Ł2 Heat Exchanger
Gondensate Tar
Saturator Liquor
The remaining streams were selected in ordr to determine the
origin and fate of pollutants in the gasification and gas
cleanup train. In a generic sense, it is also possible that
certain of these streams could be representative of effluent
streams from a cormercial facility.
- Samples for EPA/EGD
- Samples for EPA/OSW
-------
by-product tar were also collected on 21 October 1981. Table
A-39 lists the samples collected for EPA/EGD along with the
corresponding Sample Control Center identification numbers.
Table A-40 lists the samples collected for EPA/OSW.
The by-product tar (sample point (04)) samples was originally
planned to be a time composite with aliquots collected every four
hours. The GE personnel indicated, however, that they would
rather collect this sample all at once sometime near the end of
the 24-hour sampling period because the tar needed to be heated
before it could be pumped from the tank where it accumulated.
At the time of sampling, the sample crew was informed that the
system would be operated at set points which were unique to any
operating conditions utilized to date. These unique set points
were (1) a steam/air ratio of approximatly 0.6 and (2) a coal
throughput of approximately 1,800 pounds per hour. The sample'
crew was informed that the normal operation parameters which
would demonstrate potentially more commercial representation of
the GE process are (1) steam/air of 0.2 and (2) coal throughput
of 2,000 pounds per hour. The effect that this change may have
resulted in was a potentially more dilute water sample in regard
to the pollutant species of interest.
OPERATING DATA
Operating data was obtained periodically during the sampling
visit in the form of printouts from the facility's on-line
computer system. This data is presented in Table A-41.
POLLUTANT DATA
The samples collected were analyzed as described in Appendix B.
The results of these analyses are presented in Tables A-42
through A-45. No statistical evaluations were performed on the
GE data because of the single sampling episode.
A-66
-------
Table A-3 9
ERA/BCD SAMPLE MATRIX
GENERAL ELECTRIC LOW-BTU GASIFICATION FACILITY
Parroeter
Cl-Base/Neutral , Acid
C2-Pesticides
Mi-Metals (AA)
Itta!
Dissolved
M2-Metals (ICAP)
Total
Dissolved
I - Group I Water
Quality Parameters
II - Group II Water
Quality Parameters
V1-V4 - VGA Preserved
V1R-V4R - VDA Unpreserved
Repl icates
VB - VCJA Trip Blank
P-PH - Phenolics
O/G - Oil and Grease
SS - Sulf ide
CM - Cyanide/Thiocyanate
Residual Waste Sample
EPA/EGD Residual
Waste Analyses
SP 00
Source
Water
10646
10646
10646
10647
10646
10647
10646
10646
10646
10646
10646
10646
10646
10646
10646
SP 05
Quench
Kecycle
Liquor
10648
10648
10648
10649
10648
10649
10648
10648
10648
10648
10648
10648
10648
10648
10648
SP 01
Feed Coal
S0623
S0623
SP 05
Quench
Recycle
Liquor
Duplicate
10648
10648
10648
10649
10648
10649
10648
10648
10648
10648
10648
10648
10648
10648
10648
A-67
-------
Table A-40
EPA/OSW SAMPLE MATRIX
GENERAL ELECTRIC LOW-BTU GASIFICATION FACILITY
Sample Point
01 Feed Coal
Sample Identification
Number
Main
Sample
01
Duplicate
Sample
02 Gasifier Ash
03 Quench Slowdown Sludge
04 By-Product Tar
05 Quench Recycle Liquor
02
03
04
05
03D
04D
A-68
-------
Table A-41
PROCESS DATA COLLECTED AT GENERAL ELECTRIC
LOW-BTU GASIFICATION FACILITY
21 OCTOBER 1981
2:40 am
6:07 am
2:29 pm
6:23 pm
Air Flow
Steam Flow
Blast Temp.
Vessel Pres.
Hot Gas Temp.
QU Exit Temp.
Bed Level
Air Flow
Steam Flow
Blast Temp.
Vessel Pres.
Hot Gas Temp.
QU Exit Temp.
Bed Level
Air Flow
Steam Flow
Blast Temp.
Vessle Pres.
Hot Gas Temp.
QU Exit Temp.
Bed Level
Air Flow
Steam Flow
Blast Temp.
Vessel Pres.
Hot Gas Temp.
QU Exit Temp.
Bed Level
Air Flow,
Steam Flow
Blast Temp.
Vessel Pres.
Hot Gas Temp.
QU Exit Temp.
Bed Level
Process Data
(PPS)
(PPS)
(°F)
(PSI)
(FT)
(PPS)
(PPS)
<°F)
(PSI)
(FT)
(PPS)
(PPS)
<°F)
(PSI)
(FT)
(PPS)
(PPS)
(°F)
(PSI)
(FT)
(PPS)
(PPS)
(°F)
(PSI)
(FT)
1.228
.71333
374.26
287.67
1196.9
365.63
10.409
1.2243
.66662
374.39
298.93
1205.8
363.15
10.021
1.2121
.72638
375.14
298.03
1162.7
362.84
10.017
1.2028
.74602
377.22
301.12
1174.2
373.51
10.619
1.2173
.7119
376.87
306.69
1176.5
367.26
10.663
A-69
-------
Table A- 41 (Continued)
PROCESS DATA COLLECTED AT GENERAL ELECTRIC
LOW-BTU GASIFICATION FACILITY
21 OCTOBER 1981
Process Data
Air Flow (PPS) 1.2736
Steam Flow (PPS) .72563
Blast Temp. (°F) 375.32
Vessel Pres. (PSI) 302.91
Hot Gas Temp. (°F) 1207.1
QU Exit Temp. (°F) 365.01
Bed Level (FT) 10.465
A-70
-------
Table A-42
PRIORITY ORGANIC POLLUTANTS
DETECTED IN THE QUENCH LIQUOR FILTRATE
Pollutant ug/1
Acenaphthene 24
2,4 - Dimenthyl Phenol 4850
Fluoranthene 248
Naphthalene 514
Phenol 335000
Di-n-butyl phthlate 69
Benzo(a) anthracene 43
Chrysene 15
Acenaphthalene 131
Anthracene 123
Fluorene 117
Phenanthrene 329
Pyrene 159
No organics found in intake water
A-71
-------
Table A-43
PRIORITY METALS DETECTED
IN THE QUENCH LIQUOR FILTRATE (ug/1)
No. Of
Samples
No. of
Detects
Mean
Intake
Water
Sb
As
Be
Cr
Cd
Cu
Pb
Hg
Ni
Se
Ag
Tl
Zn
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
200
2200
10
2250
100
10
<200
0.1
30
100
12
200
25
800
<100
<10
<10
100
960
<50
<0
<30
<100
4
100
15
A-72
-------
Table A-44
CONVENTIONAL POLLUTANTS DETECTED IN THE
QUENCH LIQUOR FILTRATE (mg/1)
Quench Liquor
Intake Water Filtrate
(Duplicate)
pH 7.8 9.4 9.2
BODs <1 >2000 >2000
Oil and Grease 4 142 148
TSS <1 389 445
A-73
-------
TABLE A-45
NONCONVENTIONAL POLLUTANTS DETECTED IN
THE QUENCH LIQUOR FILTRATE (mg/1)
Intake Water
Quench Liquor
Filtrate
Acidity
Alkalinity
HC03
C03
TOC
COD
Phenolics
Cl
F
Total Solids
Total Volatile Solids
Total Volatile
Suspended Solids
Total Dissolved Solids
CN
SCN
CN/C12
Kjeldahl Nitrogen
NO3
NO2
P04
804
SO3
S
154
154
21
<0.005
14.2
2.3
276
65
282
<0.02
<0.02
0.3
0.02
0.02
30
<2
2
12280
6430
5840
5880
28200
19.
6440
430
48612
6906
271
46173
434
404
424
587
383
<0.
. 300
135
(Duplicat*
11500
6390
5110
6120
21800
3 25.5
6130
195
47930
6531
298
45680
380
485
424
555
422
05 0.4
350
132
A-74
-------
HOLSTON ARMY AMMUNITION PLANT
SELECTION RATIONALE
The Holston facility was selected because it represents one of
the three commercially operating facilities that practice gas
quenching for product gas cleanup. It also generates by-products
and solid waste streams that are typical of current and projected
fixed bed gasifiers. Finally, it is the only U.S. facility that
employs Wilputte gasification technology.
PROCESS DESCRIPTION
A schematic diagram of the Holston gasification facility is
presented in Figure A-4. The various samples which will be taken
during the visit are listed in Table A-46. Results from the
samples collected under this program will fulfill the data base
requirements for both the Office of Solid Waste and the Effluent
Guidelines Division. As indicated in Figure A-4 and Table A-46,
some of the samples were collected for analysis by both offices
(denoted by a circle within a square). This is in keeping with
the different objectives of the Clean Water Act and the Resource
Conservation and Recovery Act.
The gas producers are single-stage, atmospheric, fixed-bed,
air-blown Chapman gasifiers. The coal feedstock enters the top
of each gasifier through a rotating feeder and is spread across
the bed by a distribution arm. Steam and air are introduced into
the bottom of the gasifier and pass through a grate which
distributes these gases evenly and also supports the coal bed.
Ash from the gasifier is collected in a water-sealed ash pan and
removed from the unit using an ash plow. The ash plowed from the
pan falls into a hopper and then into a drag chain trough. The
ash is conveyed to a storage silo and is hauled from the site
daily by truck. The hot raw gas exits the top of the gasifier at
1,050 to 1,250°F and enters a cyclone.
Particulate matter is removed from the hot, raw, low-Btu gas in
refractory-lined cyclones that operate at a temperature slightly
lower than the gasifier overhead temperature. Each gasifier at
the Holston facility is equipped with a cyclone. The par-
ticulates removed by the cyclones consist of devolatilized coal
dust, ash, and tar entrained in the raw gas. The particulates
collect at the bottom of the cyclones. The dust is emptied once
per shift into the same hopper used for the gasifier ash.
The hot gas leaving the cyclones is quenched by spraying water
into the exit lines from each cyclone. Excess quench water is
collected in a pitch trap (one trap for each gasif ier/cyclone).
Pitch (a lighter-than-water, tarry material) and agglomerated
A-75
-------
HCTCLI OVINCH LtaUOM
FMD COAL
tTCAM/AIN
o
SAMPLE* FOB 0*W
•AMPLE* FOB COD
IT-PRODUCT TAM
TO UTILITY iOILMi
BOTTOM*
Figure A-4. Process Flow Diagram of the Holston Gasification
Facility Showing Sample Points
-------
Table A-46
Sample Points at Holston Low-Btu Gasification Facility
Source
Gasifier Ash
Cyclone Dust
By-Product Pitch
By-Product Tars
Slurry Solids
Sample Point
Water
Decanter Recycle Liquor
Coal Feed and Makeup Water
A sample of the coal feed Kgj{ and of makeup water
the Holston gasification system were obtained.
S7
to
A-77
-------
particulates which accumulate in the pitch traps are collected
for periodic off-site disposal. After the initial quenching
step, the gas is cooled further with water in two primary tray
scrubbers which are operated in parallel. Here, most of the
tars and particulates are scrubbed from the gas as it is cooled
to approximately 135°F.
The gases exiting the tray scrubbers are recombined and com-
pressed before entering a spray scrubber. In the spray scrubber,
residual tars and particulates are removed as the gas is further
cooled to about 120°F. The effluent scrubbing liquor from both
the spray and tray scrubbers is sent to the decanter.
The decanter at Holston is a large concrete tank (16 x 40 x 6
feet). Process condensate from the pitch trap and the condensed
tars from the quenching/scrubbing steps enter at one end of the
tank. A series of baffles minimizes the turbulence caused by the
incoming liquor. The tars settle to the bottom of the decanter
and are removed periodically for use as an auxilliary fuel in a
coal-fired boiler. A portion of the water from the liquor
separator is cooled in a set of heat exchangers before being
reused in the spray scrubber. The remainder of the water is
recirculated to the other quenching and scrubbing steps. Excess
quench liquor which accumulates in the decanter is periodically
sent to an evaporator for disposal.
SAMPLING EPISODES
The HAAP was sampled on two occasions. The first was a 1-day
sampling episode which occurred on 25 March 1981 and was combined
with an engineering visit to gather information for costing and
to explore the site as a potential site for a treatability study.
The second sampling visit was conducted between 29 June and 2
July 1981; it was a 3-day effort with wastewater samples taken on
each day.
The streams sampled at Holston include the following: (the
numbers in parenthesis refer to Figure A-4).
Process Water
o Decanter recycle liquor (S6)
Solid Waste
o Cyclone dust (S3)
o Gasifier ash (S2)
A-78
-------
By-Product Streams
o Pitch from pitch trap (S4)
o Tars from liquor separator underflow (S5)
Other
o Feed coal (SI)
o Source intake water (S7)
On the 25 March visit all samples taken were instantaneous grab
samples. The feed coal, make-up water and by-product pitch were
not sampled on this visit.
On the second visit the recycle decanter liquor was manually
composited by collecting samples every six hours for a 24-hour
period. The final grab sample for the previous days composite
was taken simultaneously with the first grab for the next 24-hour
composite. This procedure resulted in five six-hour grab samples
going into each composite. Duplicate samples were taken of the
cyclone dust, the by-product pitch, the by-product tar and the
decanter recycle liquor.
OPERATIONAL DATA
Operating data at HAAP is sparse due to the lack of instrumenta-
tion. The operating data available are presented in Table A-47.
POLLUTANT DATA
The samples collected during these two sampling episodes were
analyzed as described in Appendix B. A summary of the results of
these analyses are given in Tables A-48 through A-52. Each
sampling episode is listed separately even though operating
conditions at the facility were essentially the same during both
visits. The sampling procedures were different as noted above.
The duplicate samples results were averaged and treated as a
single data entry. The HAAP Phenolics data is suspect.
A-79
-------
Table A-47
Operating Data Collected at Holston Army Ammunition Plant
Parameter
Coal Feed rate
(each gasifier)
Value
11 tons/day
Pressures
-No. 2 raw gas
-No. 3 raw gas
-No. 2 steam inlet
-No. 3 steam inlet
-No. 1A scrubber outlet
-No. IB scrubber outlet
-No. 1C scrubber outlet
-No. 1 collector main
0.2" H20
0.2" H20
6"
5.4"
H20
H20
1.2" H20
0.6" H20
2.2" H20
1.6" H20
Temperatures
-No. 2 raw gas
-No. 3 raw gas
-No. 2 steam inlet
-No. 3 steam inlet
-No. 1A scrubber outlet
-No. IB scrubber outlet
-No. 1C scrubber outlet
-No. 1 collector main
1,200°F
1,200°F
145°F
145°F
141°F
145°F
122°F
159°F
NOTES: No. 2 = Number 2 gasifier
No. 3 = Number 3 gasifier
No. 1A = First of two parallel tray scrubbers
No. IB = Second of two parallel tray scrubbers
No. 1C = Spray scrubber
A-80
-------
Table A-48
Priority Organic Pollutants Detected in the Decanter Itecycle Liquor (ug/1)
29 June - 2 July Sample
Pollutant
Acemaphthene
Acrylonitrite
Benzene
Carbon-Tetrachloride
Chlorobenzene
1,2,4-Tr ichlorobenzene
Hexachlorobenzene
1,2-Dichloroethane
1,1,1-lrichloroethane
1,1,2-Trichloroethane
1,1,2,2-Tetrachloroethane
Chloroethane
2-Chloroethylvinyl ether
Chloroform
1,1-Dichloroethylene
1,2-trans-Dichloroethylene
1,3-Dichloropropylene
2,4-Demethylphenol
2,6-Denitrotoluene
1,2-Diphenylhydraz ine
Ethylbenzene
Fluoranthene
4-Bromophenylphenyl ether
Bis(2-chloroethoxy)methane
Methylene chloride
Methyl chloride
Methyl bromide
Bromoform
Dichlorobromomethane
Trichlorofluoronethane
Chlorodibronioine thane
Naphthalene
-Nitrosophenylaraine
Phenol
Ptylbenzyl phthalate
?-n-Butyl phthlate
?-n-Octyl phthalate
Pethyl phthalate
?anzo(a)anthracene
? ?uzo(a}pyrene
Chrysene
Acenaphthalene
Anthracene
Fluorene
Phenanthrene
Intake 25 March
Water Sample
1050
<1
36
5
<1
<1
30
180
<1
1
136
3490
k
1050
120
36300
73200
12200
88000
86600
No. of
Samples
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
Ito. of
Defects Min
Mean Median Max
2
1
1
1
1
1
1
0
0
0
0
1
1
0
1
1
1
3
0
1
1
3
1
1
3
1
1
1
1
1
1
3
3
2
2
3
2
3
2
3
1
3
3
3
6
32
26
16
513
62
6300
27
5
509
150
13
5
9
14
32
28
16
314
82
282
746
232
23100
4810
134
9320
7380
147
208
224
195
201
211
26
900
29200
11300
14500
7020
2050
234
32000
850
45
40
124
157
367
324
84
250
416
42
3940
504
90,000
43
44
1170
205
94
14
99
394
936
824
A-81
-------
Table A-48 (Continued)
Priority Organic Pollutants Detected in the Decanter Recycle Liquor (ug/1)
29 June - 2 July Sample
Intake 25 March No. of No. of
Pollutant Water Sample Samples Defects Min Mean Median Max
Pyrene 9540 3 3 17 96 259
Tetrachloroethylene 3 1 6560
•toluene <1 3 1 135
Trichloroethylene 3 1 121
Vinyl chloride 3 1 16700
Hexachloroethane 3 1 202
?chloronaphthalene 3 1 216
3-Dichlorobenzene 3 1 154
?-Dinitrotoluene 3 1 124
A-82
-------
Table A-49
Non-Conventional Organic Pollutants
Detected in the Decanter Recycle Lignoi, (yg/1)
29 June - 2 July Samples
Pollutant
Methylethyl ketone
Acetone
Diethylether
Benzole Acid
Dibensofuran
-lerpinol
Biphenyl
Intake
Water
25 Mar.
Sample
ND
ND
ND
ND
ND
ND
ND
NO. Of
Samples
3
3
3
3
3
3
3
No. of
Detects
2
3
1
1
2
1
2
Min
222
2340
30
30
Mean Median
4425
10900
8800
26
Max
5860
10300
385
60
Table A-5C
Priority Metals Detected in the Decanter Recycle Lignor.
29 June - 2 July Samples
(ng/1)
Pollutant
Sb
As
Be
Cr
Od
Cu
Pb
*i
Ni
Se
Ag
Th
Zn
Intake
Water
<4
<3
<2
<10
44
39
<40
<1
125
<4
<4
<63
40
25 Mar.
Sample
1100
35500
<1.0
<40
<10
<30
<40
0.4
<30
27900
<2
<3
50
No. of
Samples
3
3
3
3
3
3
3
3
3
3
3
3
3
NO. Of
Detects
3
3
3
1
1
3
0
0
2
3
1
3
3
Min
57
1350
11
53
59
3450
9
240
Mean Median
68
2150
12
9
57
152
121
4950
45
55
381
Max
80
2550
13
301
183
7620
78
560
A-83
-------
Table A-51
Conventional Pollutants Detected in the Decanter Recycle Lignon (mg/1)
29 June - 2 July Sanples
Pollutants
pH
Bod5
Oil & Grease
TSS
Intake
Vtoter
7.94
<1
<0.005
1
25 Mar.
Sample
7.3
4410
450
42
No. of
Samples
3
3
3
3
No. of
Detects
3
3
3
3
Min.
7.57
2100
275
543
Mean Median
7.7
2170
333
639
Max
7.83
2300
422
800
A-84
-------
Table A" 5 2
Nonconventional Pollutants in the
Decanter Recycle Liquor (mg/1)
-29 June - 2 July Samples-
Intake 25 March
No. of
Pollutants Water Saitple Samples
Acidity
Alkalinity
H003
CDs
TOC
COD
Phenolics
Be
Cl
F
Total Solids
Total \folatile Solids
Total Volatile
Suspended Solids
Total Dissolved
Solids
CN
SCN
CN/O.2
Kjeldahl Nitrogen
NHj
N03
NO2
P04
S04
303
S
Total Organic
Nitrogen
Ca
MQ
Na
Al
Mn
V
B
Ba
Mo
Sn
y
Co
Fte
Ti
51 4080
57 1140
57
<1
<1 7130
23 11500
<0.005 1900
0.1
<0.01
0.2
148 56200
6 53600
0
138 52000
<0.02 33
<1
7 2100
2 1100
<0.01
0.02 100
46 4300
<2
7.2 4.6
5 1000
23.8
5.3
5.78 13
0.257
0.024 0.063
0.032
0.121
0.031
0.018
0.017
<0.01
<0.01
0.09 13.3
0.005
3
3
3
3
2
3
3
3
2
3
3
3
3
3
3
3
2
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
No. of
Detects
3
3
3
0
2
3
3
0
2
3
3
3
3
3
0
3
0
3
3
0
0
3
3
3
3
3
3
3
3
3
3
2
3
3
3
2
0
2
3
3
Min
1700
1530
1530
8780
31500
1.86
2200
143
51700
45600
501
43800
330
9780
9310
18.8
12700
1560
710
470
3.42
0.95
6.27
4.16
0.007
0.032
71.1
0.149
0.086
0.328
0.015
5.6
0.021
Mean Median
2530
1800
1800
9040
33300
3.6
2200 2200
285
58200
51400
611
50700
560
10600
9900
20
13700
1630
822
707
4.35
1.07
15.6
6.76
0.016
0.081
79.8
0.162
0.122
0.332
0.026
6.18
0.053
Max
4075
1990
1990
9810
34900
8.4
2200
331
67600
56900
780
61800
700
11200
10300
23.2
15100
1690
924
1100
4.89
1.24
27.9
11.1
0.031
0.13
93.8
0.182
0.143
0.336
0.036
7.28
0.109
A-85
-------
APPENDIX B
SECTIONS 4 AND 6
OF
LOW-BTU GASIFICATION GENERIC
SAMPLING PROGRAM FOR MULTIMEDIA
DEVELOPMENT OF REGULATORY SUPPORT DATA
11 June 1981
-------
4.0 VASTEWATER SAMPLING AND ANALYTICAL PROTOCOLS
This section presents the rationale for the selection
of pollutant parameters, the details of the sampling procedures
and the analytical procedures to be used for water samples.
4.1 Vastewater Pollutant Parameter Selection Rationale
The objectives of this subsection are to identify and
present the rationale for the selection of pollutant parameters
to be analyzed in LBG vastevater samples. In general, pollutants
were selected based on provisions set forth in the Federal Water
Pollution Control Act of 1972, the 1977 Amendments and the
Settlement Agreement in Natural Resources Defense Council, Inc.
vs. Train (1979). Certain nonconventional pollutants were
selected after reviewing analytical results collected under
previous studies.
4.1.1 Vastewater Pollutant Parameters
Using the criteria described above, a tentative list of
wastewater parameters and compounds of interest has been devel-
oped. These are expected to cover the entire LBG industry; how-
ever, some revisions may be necessary during the course of the
program as unforeseen situations arise. The list will undergo
constant scrutiny to ensure that all reasonable and prudent con-
cerns .are taken into account. The list is currently categorized
as follows:
• Conventional pollutants
• Priority pollutants
• Appendix C pollutants
• Nonconventional pollutants
B-1
-------
Conventional Pollutants
The conventional pollutants, listed in Table 4-1, were
defined in Section 304(b)(4) of the 1977 Amendments to the Clean
Water Act and at 44 FR 44501 (30 July 1978). Fecal coliform was
not selected for this list since there is no reason to believe
that there will be any fecal matter present in any synfuels
wastewater samples.
Priority Pollutants
The priority pollutants, listed by category in Table
4-1, were also defined in the Clean Water Act (see Table 1 of
Section 301) as well as the 1979 Settlement Agreement. The
specific compounds were selected by reviewing the Organic Chemi-
cal Producers Data Base, reviewing the frequency of occurrence of
the compounds in water, and determining whether or not a standard
was commercially available. The data base used for these deter-
minations is found in an Agency publication entitled, "Frequency
of Organic Compounds Identified in Water" by Shackelford and
Keith (Environmental Research Laboratory, EPA-600/4-76-062,
Athens, Georgia, 1976).
Appendix C Compounds
The same data base was used for selection of the
Appendix C compounds, which are listed in Table 4-1. This set of
pollutants derives its name from Appendix C of the 1976 Settle-
ment Agreement. As with the priority pollutants, the specific
compounds in Table 4-1 are actually representatives of broad
classes of pollutants. For example, a-terpineol and camphor
represent the class of compounds called aliphatic terpenes. The
same criteria were used to determine the specific Appendix C
B-2
-------
Table 4-1
POLLUTANT PARAMETERS TO BE ANALYZED IN WASTEWATER SAMPLES
CONVENTIONAL POLLUTANTS
Biochemical Oxygen Demand (BOtK)*
pHl
Oil and Grease
Total Suspended Solids (TSS)
*Total and Dissolved BOOs
PRIORITY POLLUTANTS
PRIORITY POLLUTANTS
Ban/Neutral Compounds
Pesticides
Aldrln
Dleldrln
Chlordane
4,4'-DDT
4.4'-DDE
4.4'-ODD
W o-Endoaulfan
' B-Endosulfan
Endosulfan aulfate
EndrIn
Endrln aldehyde
Heptachlor
Hepcachlor epoxlde
a-BHC
B-BHC
T-BHC
4-BHC
PCB-1242
PCB-1254
PCB-1221
PCB-1232
PCB-1248
PCB-1260
PCS-1016
toxaphene
Volatllet
Acroleln
Acrylonlcrtle
Benzene
Carbon taCrachlorlda
Chlorobenzene
1,2-Dlchloro«thana
1,1,1-Trlchloroethane
1,1-Olchloroethene
1,1,2-Trlchloroethana
1,1,2,2-Tetrachloroethane
Chloroethane
bis (Chloromethyl) ether*
2-Chloroethylvlnyl ether
Chloroform
1 ,l-0lchloroethylen«
1,2-trans-Dlchloroethylene
1,2-Dlchloropropane
1,2-Dlchloropropylene
Echylbenzene
Methylene chloride
Methyl chloride
Methyl bromide
Bromoform
Dlchlorobronomethane
Trlchlorofluoroaethane*
Dtchlorod1fluoromethane*
Chlorodibromonethane
Tetrachloroethylene
Toluene
Trlchloroethylene
Vinyl chloride
SYNFUELS ORGANIC NONCONVEN-
TIOHAL WASTEWATER POLLUTANTS
Benzole Acid
llexanolc Acid
B-Naphthylaalne
a-Plcollne
Dlbenzothlophene
Formates
Acanaphthene
Benzldlne
1,2,3-Tr tchlorobanzene
Hexachlorobenzene
Haxachloroethane
bl« (2-Chloroethyl) ether
1,2-Dlehlorobenzene
2-Chloronaphthalene
1,3-Dlchlorobenzene
1,4-Dichlorobenzene
3,3'-Dtchlorobenzldlne
2,4-Dlnltrotoluene
2,6-DlnlCrotoluena
1,2-Dlphenylhydrazlne
(as azobeniene)
Fluoranthene
4-Chlorophenyl phenyl ether
4-BrOBOphenyl phenyl ether
bis (2-Chlorolsopropyl) ether
bla (2-Chloroethoxy) methane
Hexachlorocyclopentadlene
laophorone
Naphthalene
Nitrobenzene
N-NLtrotodlaethylaalne
N-Nltroaodiphenylaalne
N-Nltroaodl-n-propylaaine
bis (2-Ethylhexyl) phthalate
Butyl benzyl phthalate
Dl-n-butyl phthalate
Dl-n-octyl phthalate
Dlethyl phthalate
Dimethyl phthalate
Benzo(a)anthracene
Banzo(a) pyrene
3,4-Benzofluoranthene
Benzo(k)flooranthene
Chryaene
Acenaphthylene
Anthracene
Benzo (g,h,l)perylene
Fluorene
Phenanthrene
Dlbenzo(a,h)anthracene
Indeno(l,2,3-c,d)pyrena
Pyrene
2,3,7,8-TetrachlorodIbenzo-
p-dloxln
APPENDIX C COMPOUNDS
1. Acetone
2-21. n-Alkanea (Cjo-Cjo)(Cj2*)
22. Blphenyl
23. Camphor*f
24. Chlorine^
25. Cuaene*
26. Dlbenzofuran*
27. Dl-n-butylanlnet
28. Dlethyl«i»lne*t
29. Dtethyl ethert
30. Dlaethylaalnet
31. DlphenylaaineM
32. Dlphenyl ether*
33. Methyl ethyl ketone
34. Nitrites
35. Styrene
36. o-Terplneol*t
*Candldate for Stable Label Standard:
tTentatlvely chosen compounds to repi
tent general classes.
SYNFUELS GENERAL NONCONVENTIONAL
WASTEWATER POLLUTANTS
PRIORITY POLLUTANTS
Acidity
Alkalinity
Total Solids (TS)
Total Volatile Solids (TVS)
Total Dissolved Solids (TDS)
Chenlcal Oxygen Demand (COD)
Annonla
Total Kjeldahl Nitrogen
Total Phosphorus
Total Organic Carbon (TOC)
Total Phenollcs (4AAP)
Settleable Solids (SS)1
Thlocyanate
Sulfate
Sulflte
Sulfide
Nitrates
Dissolved Oxygen (DO)1
Temperature'
Volatile Dissolved Solids (VDS)
iQn-slte analysis.
Alualnua
Barlu*
Blsauth
Boron
Calclusi
Cobalt
Cold
Indian
Iron
Lithium
Magneslusi
Molybdenum
Platlnun
Po tea alum
Silicon
Sodlim
Strontlua
Tellurlun
Tin
Titanium
tungsten
Uranium
Vanadium
Yttrium
Ac Id Coamounda
2,4,6-Trichlorophenol
p-Chloro-«-cresol
2-Chlorophenol
1,4-Dlchlorophenol
2,4-DlnMthy Iphenol
2-Nltrophenol
4-Nltrophenol
2,4-Dlnltrophenol
4,5-DLnltro-o-cresol
Pentachlorophenol
Phenol
Other
Cyanide
Metals
Antimony
Arsenic
Beryllium
Chromium
Cadmium
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
*The»e compounds have been recently
removed from the priority pollutant
list (see 46 FR 2266 and 46 FR 10723)
-------
pollutants as were exercised in the selection of the priority
pollutants. These are summarized below and discussed at length
elsewhere:*
(1) The compound chosen had to have been identified in
water with a frequency of five percent or more
with respect to other members of that chemical
class that had been identified in water.
(2) The compound chosen had to have a source of com-
mercially available standards. The standards
furthermore had to be available in reasonable
purity (>90 percent) and at reasonable prices.
(3) To help prioritize choices with a chemical class,
the "Organic Chemical Producers Data Base"
was checked. An updated 28 November 1979 version
was used for the present criteria choices.
(4) To further help prioritize choices within a
chemical class, the U.S. EPA "Toxic Substances
Control Act Chemical Substances Inventory,"
Volumes II and III (May 1979), were also used.
This information was not available in 1976, but
was used now because of its relationship to
the Agency's interest in toxic chemicals and its
data on what toxic chemicals are being manufac-
tured or imported in the U.S.
Nonconventional Pollutants
The potential set of nonconventional pollutants repre-
sents all compounds that are neither conventional or priority
pollutants. Each industrial category is screened to determine
which of the nonconventional pollutants would appear at concen-
trations warranting potential concern. For the LBG segment of
the synfuels industry, this includes a brief list of six organic
pollutants and a more extensive list of inorganic pollutants and
*Rational for Synfuel Protocol, preliminary draft, Radian
Corporation, EPA Contract No. 68-01-5163, June 1981.
B-4
-------
water quality parameters. The organic nonconventionals, listed
in Table 4-1, were selected after review of results from several
synthetic fuels industry environmental assessments and a review
of the current literature in the area of synthetic fuels waste-
water analysis. From these classes, specific compounds were
selected to be representative of the class. The individual
selections were based on: (1) representativity of class, (2)
frequency of occurrence in synthetic fuels related wastewater,
(3) availability of pure standards, and (A) detection using
existing screening protocols (EPA Methods 624 and 625). Addi-
tional detail is provided in the previously cited Rational for
Synfuel Protocol.
The remaining nonconventional pollutants are also
listed in Table 4-1. The compounds in the list from acidity to
total phenolics (4AAP) are often referred to as water quality
parameters. They are indicators of the presence of general
classes of compounds (e.g., total phenolics - indicates the
presence of phenolic-type compounds) and general properties of
streams (e.g., alkalinity - is the capacity of water to
neutralize a strong acid to a designated pH).
The measurement of settleable solids (SS) is an indi-
cator of the amount of solid material that will settle in a
relatively short period of time (i.e., approximately one hour).
It is a particularly useful parameter for streams representing
runoff from storage and disposal areas.
Sulfur and nitrogen compounds are gasification products
that can appear in wastewater and solid waste streams associated
with synfuels processing. Formation of sulfate, thiosulfate,
carbonyl sulfide, and thiocyanate during synfuels processing is
important to operation of sulfur recovery technologies. As these
B-5
-------
compounds accumulate in a sulfur recovery liquor, the effective-
ness of sulfur removal and recovery is reduced.. As such, a peri-
odic release (blowdown) of the liquor is required. Knowledge of
the levels of these inhibitors in liquid streams from facilities
without sulfur recovery will provide input for design of sulfur
recovery units and estimation of blowdown quantity and quality.
The nonconventional metal wastewater pollutants listed
in Table 4-1 are those (exclusive of the priority metal pollu-
tants) that are capable of quantitative determination by
Inductively-Coupled Argon Plasma Emission Spectroscopy (ICAPES).
Although many of these are not likely to be found in LBG waste
streams, both the nature of the current study and the economics
of ICAPES analysis provide incentive for determination of these
elements. A principal objective of the current study is to fill
many of the data gaps identified thus far in the LBG wastewater
and solid waste data base. This suggests that more complete
characterization of samples that might specifically be required
for development of environmental regulations is warranted. Also,
the cost of analyzing additional elements by ICAPES does not
increase linearly, i.e., running a few elements or all of the
elements does not result in a substantial cost difference.
4.2 Wastewater Sampling Procedures
The collection of representative samples is essential
in obtaining quality data. Improper sampling techniques can
result in contamination of the samples and inaccurate results.
Therefore, measures have been incorporated to ensure quality
sampling in compliance with the procedures documented by EPA.
Whenever possible, established protocols will be used to perform
the sampling. When situations arise where established protocols
cannot be used, a detailed description of the sampling procedure
B-6
-------
will be documented in a bound, paginated field or laboratory
notebook. In these cases, guidance will be provided by the ASTM
manual for water and wastewater sampling.
The primary EPA reference for sampling effluent streams
is in "Sampling and Analysis Procedures for Screening of Indus-
trial Effluents for Priority Pollutants," April 1979. Additional
information is found in the 3 December 1979 and 18 December 1979
issues of the Federal Register. The sampling procedures
described below are based on these three references.
Each water sample consists of a number of blank, grab,
and composite sub-samples as illustrated in Table 4-2. Depending
on which parameters are determined at each site, and on the
effluent stream composition some of these sub-samples may not be
collected. Additional parameters such as pH, temperature, dis-
solved oxygen, and settleable solids are performed on-site.
4.2.1 Composite Samples
For composite samples, compositing time is typically 24
hours. Samples will be composited automatically utilizing ISCO
Model 1580 Automatic Samplers using the guidelines listed below:
• Maximum time interval between aliquot samples is
30 minutes;
• Minimum aliquot size is 100 ml;
• Minimum composite volume is 9.5 liters
(approximately two and one-half gallons);
• A single composite jug is used;
• The composite sample is stored in an iced
bottle during collection (4UC);
• All parts of the sampling system are cleaned with
hot detergent water and rinsed with blank water;
B-'-?
-------
Table 4-2
COMPOSITION OF A WASTEWATER SAMPLE SET
Parameter
C/G Extractahle Organlca
Ci - Base/Neutrals,
Acids
C2 - Pesticides
CB - Composite Blank'
M-l - Metals, Task 1
Total
Dissolved
M-2 - Mctala, Task 2
Total
Dissolved
CO I - Crouo I Para-
> meters5
00
II - Croup II
Parameters4
VI -V4 - VOA Preserved
VB - VOA Trip Blank2
VRj-VR^, VOA unpreserved
replicates
P-OII - Phenol tea (6AAP)
CN-Cyantde, Thlocyanate
Sample Type
Composite /Grab
Composite /Grab
Blank
Composite/Grab
Composite/Grab
Compos Ite /Crab
Composite/Grab
Grab
Blank
Grab
Grab
Crab
Sample Container
Class Bottle
Teflon Lid Liner
Glasa Bottle
Teflon Lid Liner
Glass Bottle
Teflon Lid Liner
Plastic Bottle
Plastic Bottle
Plastic Bottle
Amber Clans Bottle
Class vial with
Teflon aeptum
Class vial with
Teflon aeptum
Class vial with
Teflon aeptum
Amber Glass Bottle
Plant Ic Bottle
Sample
Volume
1000 ml
1000 ml
3000 ml
1000 ml
500 ml
1000 Hi
500 ml
1 liter
1 quart
40 ml
each
40 ml
40 ml
each
1 quart
500 ml
On-Slte
Preservative
Stable label
isotopes, 4*C
4"C
4'C
UNO], to pH < 2
HN03, to pll < 2
HN03, to pH <2
IIN03, to pH <2
4°C
II 2 SO*, to pll < 2,
4 C
Na2S203 to
remove Cl2, 4°C
4°C
4'C
H?S04 to pH < 2,
4*C
PbNO2, Filter,
Laboratory
Organ lea- I FB
Organlcs-IFB
Organlcs-IFB
Metala-IFB
Metals-IFB
Metala-IFB
Metala-IFB
Radian
Radian
Organlcs-IFB
Organlcs-IFB
Organlcs-IFB
Radian
Radian
Frequency
of Collection
24 hour composite
24 hour composite
flrat day of
sampling
24 hour composite
24 hour composite
24 hour composite
24 hour composite
24 hour composite
24 hour composite
every 6 hours
one per day
every 6 hours
1 grab per day
1 grab per day
0/G - Oil and Crease Crab
Sulflde/Sulflte Crab
Wide-mouth Class 1 quart
Bottles, Teflon
Lid Liner
PlantIc Bottle 500 ml
Ascorbic Acid to
remove Cl2, NaOII
to pll >12, 4"C
HiSOA to pll < 2, Radian
4*C
Zinc acetate, 4"C Radian
1 grab per day
1 grab per day
'fllnnk wnter run through sampler prior to Initiating snmple collection.
2Blank water transported to and from situ.
^Alkalinity, Acidity, BOD, TS, TDS, TSS, TVS, stilfate, nitrite, nitrate.
''COD, Total Nitrogen, Nil3, Total Phosphorus, TOO.
-------
• New tubing is used for each sampling line and for
each pump at each individual outfall or sample
location;
• A field compositer blank is taken the first day
at 'each site by pumping five liters of blank
water through the ISCO sampling system before
collecting any samples, (the last three liters
pumped are analyzed as a blank); and
• When sampling raw discharges, the minimum intake
velocity of the sampler is 0.6 m/second (two feet/
second).
The composite is blended to a homogeneous state before transfer
to the various sample containers.
A portion of the composite sample is transferred to two
one liter and two 500 ml plastic bottles for metals analyses.
Samples for dissolved metals analysis are filtered, while total
metals samples are not. In each case, the sample is preserved by
nitric acid addition to a pH of less than two. An additional
1,000 ml is transferred into a graduated cylinder for the acid
and base/neutral extractables sample. An amount sufficient to
fill a 1,000 ml glass bottle to a level of approximately 1/2 inch
is poured from the graduated cylinder. The two glass ampules
containing the acid and base/neutral stable lable cocktails are
then introduced into the 1,000 ml bottle and crushed with a
stainless steel rod. The remaining portion of the sample is then
poured over the rod into the 1,000 ml bottle.
The remaining water quality parameters which are deter-
mined from the composite sample are collected in two sample con-
tainers. A one liter sample in a plastic bottle is collected for
those parameters which do not require preservation. A separate
one liter sample in a glass bottle is acidified with sulfuric
acid (H2S04) for the remaining parameters.
B-9
-------
With the exception of the metal samples, all samples
are kept at 4°C until analyses are initiated. All glass bottles
have Teflon-lined caps.
4.2.2 Grab Samples
Some of the parameters listed in Table 4-2 must be col-
lected as grab samples. Grab samples are obtained at the mid-
point of the compositing period in a turbulent, well-mixed sec-
tion of the effluent stream. Grab sampling is conducted because
of rapid change in the parameter of interest (e.g., volatile
organics, phenolics, cyanides).
Duplicate purgeable samples (VOAs) are obtained in 40
ml vials with Teflon septa caps. The vial is carefully filled
from the water source to be sampled without aeration or over-
filling the bottle. A small amount of this water is added until
the meniscus is visible above the lip of the vial. The cap with
the Teflon septum is screwed on the vial in such a way as to
leave no visible bubbles of air when the bottle is inverted.
Sodium thiosulfate (Na2S203) is used to stabilize
VOA samples containing residual chlorine. The production of
haloforms continues in such samples if they are not stabilized.
Waste streams that have been treated with chlorine are tested
on-site to determine whether or not preservation is needed. No
such streams are known to exist jLn the LEG industry. If preser-
vation is needed, both preserved and non-preserved samples are
collected.
A one-liter grab samples is collected for cyanide.
Oxidizing agents, such as chlorine, may result in the decomposi-
tion of many cyanides. At the time of collection, the sample is
tested for these agents with orthotoluidine. If needed, ascorbic
B-10
-------
acid is added to eliminate the residual chlorine. Then, two ml
of 10 N sodium hydroxide is added per liter of sample or until
the pH is greater than 12.
A one-quart grab sample is collected in an amber glass
bottle for phenolics. Preservation of the sample is accomplished
by addition of H2S04 to a pH of less than two.
A one-quart sample is collected for oil and grease
analysis. A wide-mouth glass bottle with a Teflon cap liner is
employed to collect the sample which is preserved by addition of
H2S04 to a pH of less than two. Oil tends to form a film on
top of water in quiescent streams. To obtain a representative
sample, the sample should be collected in an area of complete
mixing.
4.2.3 Bottle Preparation
Organic-free, deionized blank water is prepared at
Radian for use in sampling activities. The water is prepared by
passing tap water through commercial ion-exchange resin beds,
placed in an all-glass still with caustic KMn04, and distilled
at a slow rate (six liters/day) into a closed-glass recipient
purged with zero-grade helium.
No organic solvents or materials ever enter this dis-
tilling system. The organic-free blank water produced is further
treated for volatile organic analysis (VOA) by purging it with
zero-grade helium to remove any volatile organic compounds
remaining.
In general, bottle preparation consists of washing with
detergent and water and rinsing with organic-free deionized
B-11
-------
water. However, additional preparation is required for volatile
organics and asbestos.
Radian's bottle preparation for volatile organics is as
follows. The 40 ml vials for volatile organic samples are washed
with detergent and water, rinsed in blank water and placed in a
100°C oven for 30 minutes. The Teflon-lined caps are washed and
rinsed and allowed to air dry. The vials are tightly capped and
are ready for packing.
Sample containers for asbestos are supplied by EPA's
Sample Control Center. These bottles have been rinsed with
filtered water to insure no fibers are present. The bottles are
not to be opened until the time of collection.
4.2.4 Logbook Recording Procedures
Prior to actual sampling at each of the facilities,
pertinent information will be documented in a bound, paginated
laboratory notebook. This information will include the name and
location of the facility as well as the name and telephone number
of key personnel at the facility. Additional information con-
cerning each individual stream sampled will also be documented in
the notebook. This additional information will consist of:
• A detailed diagram and description of each
sample stream,
• A description of the sampling technique used to
collect the sample,
• Documentation of obstacles encountered during
sampling,
• Amount and type of preservation chemicals used,
• The date and time samples are collected, and
• The names of individuals comprising the sampling
team.
B-12
-------
All samples will be given a unique identification
number to help with sample traffic control. The numbers will be
assigned by the EPA Sample Control Center (SCC). All ensuing
references to the .sample will be by the SCC sample number. The
samples will also be labeled and the following information will
be placed on the label:
• Type of sample and facility name,
• Date and time the sample is taken, and
• The initials of the samplers.
The unique identification number will also be documented in the
laboratory notebook for cross-referencing purposes. Any mistake
made in recording data into the laboratory notebook will be
crossed out with a single line and initialed.
4.3 Wastewater Analyses
The purpos'e of an analytical method is to provide qual-
itative and/or quantitative data for the analytical parameters
identified in the test plan. To achieve this purpose, a wide
range of analytical tools, ranging from classical "wet-chemical"
techniques to sophisticated instrumental tools must be employed.
In the following paragraphs, a brief account of the analytical
methods chosen and preliminary treatments or preparations
required for the test effort is presented.
Wastewater samples collected at the various facilities
will be analyzed for the conventional, 129 priority, Appendix C,
and nonconventional pollutants. All priority pollutant analyses
are performed by EPA (IFB lab) contract laboratories. These
laboratories should follow the protocol outline in "Sampling and
Analysis Procedures for Screening of Industrial Effluents for
B-13
-------
Priority Pollutants," April 1979 and in the 3 December 1979
Federal Register. Radian is scheduled to perform the remaining
conventional and nonconventional analyses. Brief summaries of
the analytical methods are presented below by pollutant
categories.
4.3.1 Methods of Analysis for Conventional Pollutants
The analysis of samples for the conventional pollutant
parameters will be the methods specified in "Methods for Chemical
Analysis of Water and Wastes," EPA-600/4-79-020 (March 1979). A
summary of the methods and the EPA Method Number are detailed in
the following paragraphs.
Biochemical Oxygen Demand, BOD (EPA 405.1)
BOD is a measure of the change in the amount of dis-
solved oxygen in a sample when incubated in the dark at 20°C for
five days. This change in dissolved oxygen is related to the
amount of organic matter which is assimilated and oxidized by
microorganisms. An initial dissolved oxygen concentration is
determined and after five days a final concentration is
determined.
pH Value (EPA 150.1)
Hydrogen ion activity is determined on-site and in the
lab electrometrically using a glass-referenced electrode pair or
a combination glass electrode. This analysis will be performed
onsite.
B-14
-------
Oil and Grease (EPA 413.2)
Oil and grease is determined by an extraction of an
acidified sample with fluorocarbon-113. The oil and grease is
determined by comparison of infrared absorbance of the sample
extract with standards. This method is particularly applicable
to samples with elemental sulfur.
Total Suspended Solids (EPA 160.2)
Total suspended solids are determined by a gravimetric
procedure in which an aliquot of sample is filtered through a
fine glass fiber filter. The filter and retained solids are
dried to a constant weight at 103° to 105UC.
4.3.2 Methods of Analysis for Organic Pollutants
Wastewater samples collected at the various facilities
will be analyzed for the 129 priority, organic nonconventional,
and Appendix C pollutants. Analyses for the priority pollutant
volatiles, base/neutrals, and acid compounds, as well as the
organic nonconventional pollutants, will be conducted by the
established EPA Methods 1624 and 1625.
Pesticide priority pollutants are to be analyzed by
Electron Capture-Gas Chromatography (EC-GC) using the EPA method
published in the Federal Register, Vol. 38, Number 125, Part II,
pp. 17318-17323.
The Appendix C pollutants will be analyzed by the
analytical methods presented in Table 4-3. Except for the
colorimetric methods for chlorine and nitrite measurements, the
proposed methods for the Appendix C compounds follow the
established EPA Methods 1624 and 1625.
B-15
-------
Table 4-3
APPENDIX C ANALYTICAL PROTOCOL
Pollutant(s)
Acetone
n-alkanes
Biphenyl
Chlorine
Dialkyl Ethers
Dimethyl Ether
Diethyl Ether
Dibenzofuran
Diphenyl Ether
Methylethyl Retone
Nitrites
Secondary Amines
Dibutyl
Diethyl
Diphenyl
Dimethyl
Styrene
Terpenes
Camphor
Cumene
a-Terpineol
Analytical Method
VOA
Base/Neutral
Base/Neutral
Colorimetric
VOA
Base/Neutral
Base/Neutral
VOA
Colorimetric
Base/Neutral
EPA Method Number
1624
1625
1625
Standard Methods
14th Edition, 1975
Method 409D, p 325
1624
1625
1625
1624
Standard Methods
14th Edition, 1975
Method 424, p 434
1625
VOA
Base/Neutral or Acids
1624
1625
B-16
-------
4.3.3 Priority Pollutant Metals
Priority metal pollutants (with the exception of
mercury) are to be analyzed by Atomic Absorption (AA)
Spectroscopy and Inductively-Coupled Argon Plasma Emission
Spectroscopy (ICAPES). The former is described in 40 CFR Part
136 and the latter can be found in the amendments proposed in the
3 December 1979 Federal Register, page 69559.
Mercury (EPA 245.2)
Mercury analysis is performed by automated cold vapor
atomic absorption. This physical method is based on the absorp-
tion of radiation at 253.7 nm by mercury vapor. Mercury is
reduced to the elemental state and aerated from solution.
s
Absorbance is measured as a function of mercury concentration.
4.3.4 Other Priority Pollutants
Cyanide (EPA 335.2)
Total cyanide is analyzed by a distillation procedure
in which the cyanide is removed and concentrated by refluxing the
sample with sulfuric acid and magnesium chloride. The liberated
hydrogen cyanide is collected in a sodium hydroxide absorbing
solution. The concentration of cyanide in the absorbing solution
is measured by titration for cyanide concentrations greater than
one milligram per liter and by colorimetry for cyanide concen-
trations less than one milligram per liter.
In the colormetric procedure the cyanide is converted
to a cyanogen chloride by the addition of chloromine-T. Cyanogen
chloride forms a red-blue dye with the pyridine barbituric acid
B-17
-------
reagent. The absorbance of the dye is read at 578 nm and com-
pared to a set of standards.
Cyanide, Amenable to Chlorinatlon [Cyanide-A] (335.1)
Cyanide-A is not a priority pollutant; however, it
provides a useful measure of cyanide treatable by chlorine or
similar oxidizing agents. Cyanide-A is analyzed by taking two
portions of the sample and adding calcium hypochlorite to one
portion of the sample. The two portions are then analyzed for
cyanide as described above, and cyanide-A is calculated by
difference.
4.3.5 Methods of Analysis for Nonconventional Pollutants
The analysis of samples for the nonconventional pollu-
tant parameters will be performed using methods specified in
"Methods for Chemical Analysis of Water and Wastes,"
EPA-600/4-79-020 (March 1979) and "Standard Methods for the
Examination of Water and Wastewater," 14th Edition (1975). A
brief summary of the methods and the EPA Method Number are
detailed in the following paragraphs.
Acidity (EPA 305.1)
Acidity is determined by titration using a dilute
sodium hydroxide standard with a pH meter for end point detection
at pH 8.2. Acidity is reported in mg/1 of calcium carbonate.
Alkalinity (EPA 310.1)
Alkalinity is determined by titration using a dilute
sulfuric or hydrochloric acid standard with a pH meter for end
point detection at pH 4.5. This measures the acid neutralizing
B-18
-------
capacity of the sample and is reported in mg/1 of calcium
carbonate.
Total Solids (EPA 160.3)
Total solids are determined by a gravimetric method in
which an aliquot of the sample is placed in a tared container and
evaporated to dryness at 103° to 105UC.
Total Volatile Solids (EPA 160.4)
Total volatile solids are determined by a gravimetric
procedure in which the residue from the determination of total
solids is ignited in a muffle furnace at 550UC for 15 minutes.
The weight loss after heating at 550°C represents the volatile
solids.
Total Dissolved Solids (EPA 160.1)
Total dissolved solids are determined by a gravimetric
method in which a portion of the sample is filtered through a
fine glass fiber filter. A measured aliquot of the filtrate is
placed in a tared container and evaporated to dryness at 180°C.
Chemical Oxygen Demand (COD) (EPA 410.1)
Chemical oxygen demand is determined by refluxing the
sample with potassium dichromate and sulfuric acid for two hours.
After cooling, the excess dichromate is titrated with ferrous
ammonium sulfate. The amount of potassium dichromate consumed is
proportional to the amount of oxidizable organic matter in the
sample.
B-19
-------
Ammonia (NH^-N) (EPA 350.1)
Ammonia is determined by distilling the sample with
sodium thiosulfate to remove interfering species, followed by the
reaction of alkaline phenol and hypochlorite to form indophenol
blue that is measured colorimetrically.
Nitrogen, Total Kjeldahl (EPA 351.3)
Nitrogen which is organically bound in the trinegative
state is determined by the Kjeldahl method. Amino nitrogen is
digested to ammonium sulfate in the presence of sulfuric acid,
potassium sulfate, and a mercuric sulfate catalyst. The digested
sample is 'decomposed by sodium thiosulfate and the ammonia is
distilled under alkaline conditions into a boric acid solution.
The ammonia in the distillate is titrated with a dilute sulfuric
acid standard to the lavender end point of the mixed indicator
for concentrations greater than one mg NH3-N/1 or by nessleri-
zation for concentrations less than one mg NH3-N/1.
Phosphorus, Total (EPA 365.2)
Total phosphorus in water is digested to the orthophos-
phate form by boiling with sulfuric acid and ammonium persulfate.
The pH is adjusted up to pH 7.0 +0.2 with sodium hydroxide and
the orthophosphate is determined using a colorimetric method.
Orthosphosphate reacts with ammonium molybdate and potassium
antimony tartrate in an acidic medium to form a heteropoly acid,
phosphomolybdic acid, which is reduced by ascorbic acid to the
highly colored molybdenum blue. The absorbance of the sample is
measured at 880 nm and compared to a set of standards.
B-20
-------
Total Organic Carbon. TOC (EPA 415.1)
Total organic carbon is determined by injection of a
small aliquot of .sample into an Oceanography International carbon
analyzer. The organic matter is oxidized to CC>2 and is
measured by means of a nondispersive infrared analyzer. A set of
standards is also injected into the analyzer to determine the
concentration versus response relationship.
For low-level TOC concentrations, a Dorhmann Model 512D
organic carbon analyzer is used. This instrument utilizes a
flame ionization detector to provide a linear response up to 10
mg/1 carbon concentration.
Total Phenolics (EPA 420.1)
Total phenolics are determined by a distillation pro-
cedure to remove interferences followed by a colorimetric
measurement. Phenolics in the distillate react with four amino
antipyrine at pH 10 in the presence of potassium ferricyanide to
form a colored antipyrine dye. The absorbance is read in a
spectrophotometer at 510 nm and compared to a set of standards.
For phenolic concentrations less than 50 ug/1, the antipyrine dye
is extracted into chloroform and the absorbance read at 460 nm.
This absorbance is compared to a set of standards.
Settleable Solids (EPA 160.5)
Settleable solids are measured volumetrically with an
Imhoff Cone. In samples where separation of settleable and
floatable solids occurs, the floating materials are not measured.
This analysis will be performed onsite.
B-21
-------
Thiocyanate (Standard Methods 413 K)
Thiocyanate analysis is performed spectrophotometri-
cally. At an acidic pH, ferric iron forms an intense red color
with thiocyanate. The amount of thiocyanate is proportional to
the intensity of the color.
Sulfate (EPA 375.2)
Sulfate analysis is performed by a colorimetric method.
The sample is passed through a sodium form cation-exchange col-
umn to remove multivalent metal ions. The sample is reacted with
an alcohol solution of barium chloride and methylthymol blue
(MTB) to form barium sulfate. The pH is raised to react any
excess barium with MTB. The amount of uncomplexed MTB is equal
to the sulfate present.
Sulfide (EPA 376.2)
Sulfide analysis is performed by titrating an acidified
sample containing a starch indicator with a standard potassium
iodide-iodate titrant.
Nitrates (EPA 353.3)
Nitrate analysis is performed spectrophotometrically.
A filtered sample is passed through a column containing granu-
lated copper-cadmium to reduce the nitrate to nitrite. The
nitrite is determined by diazotizing with sulfanilamide and
coupling with N-(l-naphthyl)-ethylenediamine dihydrochloride to
form a highly colored azo dye which is measured with a spectro-
photometer. Separate nitrate-nitrite values are obtained.by
performing the procedure twice; with and without the Cu-Cd
reduction step.
B-22
-------
4.3.6 Nonconventional Metals
Wastewater samples will be analyzed for nonconventional
metal pollutants by atomic absorption (AA) and inductively-
coupled argon plasma emission spectroscopy (ICAPES). The former
is described in 40 CFR Part 136 and the latter can be found in
the amendments proposed in the 3 December 1979 Federal Register,
page 69559.
B-23
-------
6.0 PROGRAM QUALITY ASSURANCE/QUALITY CONTROL
The objectives of the quality assurance procedures for
this program are to assure, assess, and document the precision,
accuracy, and adequacy of data developed during the program and
to assure the accuracy of the technical work performed by Radian
on the tasks. A well-designed quality assurance/quality control
(QA/QC) program is an integral part of this data gathering
effort. The QA/QC program can be categorized into three areas:
• Sample collection,
• Sample transportation, and
• Sample analysis.
In addition, quality control for data reporting and review is
also necessary to ensure accurate results. The project Technical
Director is the QC coordinator for this program. He is responsi-
ble for the development and implementation of all phases of the
QC activities. The QC coordinator schedules all QC activities,
and coordinates the reporting, recordkeeping, and QC data
analysis. He is responsible for maintaining mechanisms for
problem detection, reporting, and correction of any analytical
problems. A QC coordinator in each Radian laboratory will also
assist in the implementation of quality control procedures.
6.1 Quality Control for Sample Collection
The objectives of a field quality control program are
to:
Evaluate all aspects of the sampling methodology
which affect the quality of the data produced, and
Identify problems in all areas of the program as
they occur.
3-24
-------
Specific quality control programs for each sample medium include
considerations in the following areas:
• Experimental design review of each site-specific
sampling plan to ensure that the samples collected
will yield the information required from the visit.
This statistical review should include selection
of sampling locations, adequate numbers of replicate
and control samples, and evaluation of representa-
tiveness of samples, and sample allocation to
laboratories.
• Training and standardized instructions which ensure
the proper implementation of the experimental
design, correct use of all equipment, and adherence
to the sampling protocols.
• Forms developed for each specific sampling activity
to aid in sample documentation and recordkeeping
and minimize recording errors and ensure complete
data.
• Quality control tests to evaluate sampling,
including:
--blank or control samples to check for inter-
ferences and contamination,
--field spiking of stable label compounds to
evaluate recoveries,
--replicate samples to evaluate sampling varia-
tions by parallel sample compositions, and
--inter-sampling team checks for standardization
of equipment and personnel.
• Quality control checks to evaluate calculations
and monitor sampling equipment (e.g., flow audits
of sampling pumps).
Detailed records of all aspects of the sampling strat-
egy and its implementation will be kept, as well as documentation
of the chain-of-custody of all samples collected. Logbooks will
be used .as a convenient means of permanently recording informa-
tion on pumps, calibration, source and lot number of sampling
media and reagents, sampling sites and times.
B-25
-------
Quality control samples included with the samples
collected during the site visit will provide the data necessary
to evaluate accuracy and precision. Each set of samples col-
lected at each site should include the following minimum QC
samples and tests:
• A field blank appropriately handled to simulate
sample handling.
• A standard or control sample handled in the same
manner as the blank. This control sample should
contain known amounts of the parameters of interest
in the field samples.
• One or more duplicate samples (sample splits).
After analysis, these quality control samples will be
combined with laboratory QC results to provide estimates of back-
ground contamination, recoveries, interferences, and variability,
and accuracy of the field sample concentrations.
Each field sample is coded with a sample number (field
number) and sets of samples will be identified as a group by a
sequence number. Samples and sample containers will be identi-
fied with the individual field numbers. Copies of the sample
documentation sheets will accompany the samples in shipment while
the original will remain with the sampling personnel.
6.2 Quality Control for Sample Transportation
An important aspect of- quality control for programs
with a large number of samples is a system to manage samples col-
lected and analyzed during the various tasks. Detailed record-
keeping and control of samples are essential to a successful
laboratory program. The following sample control procedures are
modeled after the procedures currently used in Radian's
laboratories.
B-26
-------
All sampling activities are documented by the use of
EPA Traffic Reports. The EPA Sample Control Center issues sepa-
rate reports for organics, metals, and asbestos. The organics
traffic report is employed by the sampling crew to document all
additional samples collected. Supplemental information is
recorded in a laboratory notebook. Copies of the traffic report
are mailed to the Sample Control Center, to the laboratory
receiving samples, and a copy is retained by the sampling crew
chief. With the exception of metals, all samples are shipped in
insulated containers by air express on the day they are col-
lected. The shipping container is labeled:
EFFLUENT WATER SAMPLES
NONHAZARDOUS MATERIALS
EXEMPT FROM DOT REGULATIONS
label
Information regarding sample shipment is forwarded to the Sample
Control Center for distribution to the various laboratories. The
metal samples are shipped at the completion of sampling at each
site.
Several laboratories are scheduled to conduct the
analyses. Laboratories under contract to EPA (IFB labs) will
conduct analyses for the priority pollutants excluding total
cyanide. Radian Corporation will perform all other analyses
which included total phenolics, total cyanides, conventionals,
and nonconventionals pollutants.
To ensure that the integrity of the samples is main-
tained, a special pressure-sensitive label is placed across all
sample container lids. Access to the sample within the bottle
B-27
-------
cannot be obtained without destroying the label. Any visible
means of tampering with the sample bottles, detected by the indi-
vidual laboratories, is documented and the analytical results
from the container are noted to be suspect.
When chain-of-custody documentation is required, addi-
tional documentation will be necessary. The primary objective of
chain-of-custody is to create an accurate written record that can
be used to trace the possession of the sample from the moment of
its collection through its introduction into evidence. A sample
is in custody if it is in any of the following states:
a. In actual physical possession,
b. In view, after being in physical possession,
c. In physical possession and locked up so that
no one can tamper with it, or
d. In a secured area, restricted to authorized
personnel.
EPA's Handbook for Analytical Quality Control in Water
and Wastewater Laboratories (1979, p. 12-3 through 12-10) discus-
ses the detailed requirements for a complete chain-of-custody
protocol. This reference should be used if these requirements
are imposed on any of the site visits.
6.3 Quality Control for the Laboratory
Sample control, begun in the field, is the responsi-
bility of the laboratory on the day the samples are received.
As each sample is received, it is assigned a unique number and
logged into the master log book. This log includes date of
receipt, sample description (from label), and sample type (i.e.,
amber gallon jug-water, sealed five-mi ampule, etc.). A labora-
tory routing sheet (see Figure 6-1) is prepared which includes
B-28
-------
SAMPLE ROUTING FOR EPISODE
PARTIAL COMPLETE
CONTRACT NO. DATE RECEIVED
CLIENT: NOTEBOOK REFERENCE
SAMPLE CHARACTERISTICS:
BACKGROUND INFORMATION:
SPECIAL INSTRUCTIONS:
ANALYSES REQUIRED:
LABORATORY: RECEIVED BY: DATE:
ANALYSIS SCHEDULE NORMAL LAB ROUTINE WITHIN
^^3 IMMEDIATE
PROGRAM MANAGEMENT: PM PD IL
SAMPLE INVENTORY
SAMPLE NO.
CLIENT I.D.
•
DATE
TO LAB
DATE
RETURNED
COMMENT
Figure 6-1
SAMPLE CONTROL ROUTING SHEET
-------
such additional information as special handling instructions,
extraction procedures, cleanup and/or special preparation needs,
analyses required, time limits, and route (i.e., Extractions
Laboratory, Trace Metals Laboratory, Water Laboratory, etc.). An
advance copy of this form is forwarded to each of the laborator-
ies that eventually will analyze the sample. This aids the
laboratory supervisor in scheduling the workload for maximum
efficiency.
The original of this sheet is kept in the master file
by sample control. When all analyses are complete, the sample
returned, and the analysis request sheets returned, the sample is
logged out of the system. Concurrently, the routing sheet is
completed, appropriate paperwork filed in the completed master
file, and the sample stored or discarded, whichever is
appropriate.
Each person working with a sample maintains a bound
notebook in which all work done on a sample is recorded. Since
this reference is listed on each of the request sheets returned
to sample control, a complete history of a sample is thus
maintained.
6.4 Quality Control for Analytical Procedures
Routine laboratory quality control procedures will be
blended with the specific QA/QC requirements for this program to
provide an effective and efficient laboratory protocol capable of
defining the quality of the sample concentrations for each set of
samples. Standard analytical methods will be used in all cases.
Any deviations will have to be approved prior to analysis. The
QA/QC program utilized in each laboratory program includes con-
sideration of the following areas:
$-30
-------
• Training and method validation;
• Equipment and supplies;
• Calibration and standards;
• Quality control test samples:
--blanks,
--replicate extractions and analysis,
--blind standards, and
—spiked samples;
• Data handling and reporting;
• Participation in EPA and other check sample
programs; and
• Quality assurance audits.
Quality control for the conventional and nonconven-
tional pollutant analyses will include the following:
• Ten percent of each analysis will consist of
duplicate and spiked samples.
• For each distillation procedure used, daily
distillations of standards for recovery will
be made.
• EPA quality-control standards and/or independent
"blind" standards will be analyzed.
As quality control measures, 10 percent of the solids
will be digested in duplicate and 10 percent of the extractions
will be done in duplicate. Certifiable standards of organic
material are to be digested alongside the solid samples and
analyzed alongside the digested solids. Aqueous standards are to
be analyzed alongside the extractions. If the results of these
analyses do not fall within the expected limits of concentration,
the problem will be resolved and the samples reanalyzed. Blanks
will be analyzed alongside samples to provide data as to possible
contamination of samples.
B-31
-------
The exact QA/QC protocol will depend on the individual
laboratory and the particular analytical method. One critical
requirement is that the QA/QC procedures in the lab be thoroughly
documented. Laboratory QC manuals or instructions from each IFB
and subcontractor lab will be appended with the site-specific
plan for each plant visit.
6.5 Quality Control for Data Reporting and Review
Data forms as shown in Figures 7-1 to 7-5 will be
prepared for each type of analysis performed during a site visit.
These forms will be used in each laboratory performing analyses.
Specific reporting requirements will be stated on the
form for each parameter requiring analysis. Detection limits
will be required for all compounds not detected. Space for
comments will be included to document any observations, problems,
or deviations from protocol. The laboratory QC Coordinator will
review each data form, and will note the review with his/her
signature.
When all analyses are complete for a particular sample
episode (or a particular site visit) the set of results will be
reviewed by a chemist familiar with each of the analyses per-
formed. All QA/QC samples and procedures will be summarized at
this time. Percent differences between replicate samples,
replicate extracts, and replicate analyses will be computed to
evaluate the precision of the analytical results and the impor-
tant sources of variability. Percent recoveries will be computed
for all spikes (including surrogates) to evaluate accuracy of the
sampling/analysis protocol. Standard runs will be summarized to
estimate analytical accuracy. Blank concentrations will be
summarized to estimate sample contamination.
B-32
-------
All field sampling forms, sample control forms, and
analytical results forms will be reviewed for completeness and
unusual comments. All analytical results will be evaluated for
reasonableness. For example, a comparison of influent and efflu-
ent data from the same time period can be used as a reasonable-
ness check. Any unusual results will be checked back through the
analytical laboratory.
*U. S. GOVERNMENT PRINTING OFFICE 1986; 491-191/52938 B~33
------- |