United States
            Environmental Protection
            Agency
            Office of Water
            WH-552
            Washington, DC 20460
July 1986
            Water
vvEPA
Low BTU
Gasifier Wastewater
            Technical Support Document

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     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

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                            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

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                             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

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                        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

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                  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

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                         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

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                         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

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                   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

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                             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

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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).

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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.

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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

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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

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                                           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

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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.

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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

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                             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

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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

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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

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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

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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

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                           0-CH

                             i
CH4+CO
            C« 84.76%
            M- 4.l47o
            0« 9.68%
            N« 1.42%
   Figure 2-3
PYROLYSIS  OF COAL
         27

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    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

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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

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                   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

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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

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                           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

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     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

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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

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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

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                                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

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                               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

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                                          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

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                            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

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                  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

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                      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

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    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

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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

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                            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

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                            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

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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

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                                  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

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                   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

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                            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

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                                 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

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                       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

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                                 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

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                                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

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                                 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

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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

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                             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

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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

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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

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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

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       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

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                            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)

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     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

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   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

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       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

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       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

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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

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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

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                             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

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     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

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                 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

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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

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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

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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

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              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

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                       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

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                          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

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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

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                            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

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                             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

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                               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

-------




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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

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                           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

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                                           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

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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-'-?

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                                                     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.

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          •  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

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          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

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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

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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.
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          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

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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.
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          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

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                            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

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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

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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

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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

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          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

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          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

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          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.
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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.
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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.
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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.
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          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.
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          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

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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
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         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

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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:
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          •  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.
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           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.
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            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

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