xvEPA
        •
Air Emissions from
Combustion of Solvent
Refined Coal

Interagency
Energy/Environment
R&D Program Report

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Research reports of the Office of Research and Development, U.S. Environmental
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                                       EPA-600/7-79-004

                                            January 1979
Air Emissions from Combustion
       of  Solvent  Refined  Coal
                          by

                Kenneth G. Budden and Subhash S. Patel

                     Hittman Associates, Inc.
                     9190 Red Branch Road
                    Columbia, Maryland 21045
                    Contract No. 68-02-2162
                  Program Element No. EHE623A
                 EPA Project Officer: William J. Rhodes

               Industrial Environmental Research Laboratory
                Office of Energy, Minerals, and Industry
                  Research Triangle Park, NC 27711
                        Prepared for

              U.S. ENVIRONMENTAL PROTECTION AGENCY
                 Office of Research and Development
                    Washington, DC 20460

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                          ABSTRACT
     This report details the air emissions associated with
the Solvent Refined Coal (SRC) combustion test, conducted at
Georgia Power Company's Plant Mitchell, during the months of
March, May, and June, 1977.  A larger study and evaluation
of SRC combustion test is being done by the Department of
Energy and its contractors.  The purpose of the test was to
determine whether SRC is an acceptable substitute for coal,
and to demonstrate the assumed advantages of SRC.  The test
was conducted in three phases, with coal being fired during
the first and second phases, and SRC during the third.  Flue
gas samples were collected for modified U.S. Environmental
Protection Agency (EPA) Level I analysis, and analytical
results are reported.  Air emissions from the combustion of
coal and SRC are compared for various organic and inorganic
constituents, and SOo and NOX.  Finally, the impact of the
air emissions from the combustion of SRC is assessed by
comparison with EPA's Multimedia Environmental Goals and
existing New Source Performance Standards.

     Air quality emissions test data indicated that SRC S02
and NOX emissions were 0.46 and 0.19 kg/GJ  (1.06 and 0.43
Ib/lO^ Btu) respectively.  This is about 12 and 39 percent
under the existing New Source Performance Standards (NSPS)
of 0.52 kg/GJ (1.2 lbs/100 Btu) for SOX and 0.30 kg/GJ (0.7
lbs/106 Btu).  If the S02 standard is reduced to 0.26 kg/GJ
(0.6 lbs/10° Btu), SRC derived from high sulfur coal may not
meet this standard.  The low NOX emissions may be a result
of abnormally high excess air that was used during the
combustion test and additional testing at normal conditions
is required.

     Particulate emissions can be controlled well below the
EPA standard of 0.04 kg/GJ (0.1 Ibs/lO^ Btu) by installing a
modern precipitator having a particulate collection effi-
ciency of approximately 95 percent.
                              ii

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                          CONTENTS

Abstract	 ii
Figures and Tables	 iv
List of Abbreviations and Symbols	 vi
Acknowledgement 	 vii

     1.   Introduction	 1
     2.   Conclusions and Recommendations	  4
     3.   Combustion Test	  5
               Sample collection	  6
               Sampling locations	  7
               Sampling schedule	  8
     4.   Analyses	 10
               Grab samples	 10
               SASS train samples	 10
     5.   Comparison of Air Emissions	 27
               Organics	 27
               Inorganics	 28
               S02 and NOX	 29
     6.   Assessment of Air Emissions	 32
               Organics	 32
               Inorganics	 32
               S02 and N0x	 34

Bibliography	 37
                             iii

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                     FIGURES AND TABLES
Figure
Number                                                    Page
  1     SASS Train Flowsheet	     6
  2     Diagram of Sampling Locations	     8
  3     Analytical Procedures Followed in SASS Train
          Run Analysis	    15
  4     MEG Chart, November 1977 Version	    33
Table
Number                                                    Page
  1     Phase II - Coal Combustion Test Sampling
          Schedule 	     9
  2     Phase III - SRC Coal Combustion Test Sampling
          Schedule 	     9
  3     On-Site Analysis of Grab Samples, Phase II -
          Coal Combustion	    11
  4     On-Site Analysis of Grab Samples, Phase III -
          SRC Combustion	12
  5     Combustion Test, Phase II - Coal Samples ....    13
  6     Combustion Test, Phase III - SRC Samples ....    13
  7     Process Information  	    14
  8     GC Analysis for Cj through C-,, Hydrocarbons  .  .    16
  9     IR Examination of Nonvolatile Hydrocarbons,
          June 16, 1977	    18
 10     IR Examination of Nonvolatile Hydrocarbons,
          June 19, 1977	    18
                               IV

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Table
Number                                                    Page

 11     Total Hg, As,  and Sb in Particulates and
          XAD-2 Resin Samples	    19

 12     SSMS Elemental Analysis of SASS Train Samples.  .    20

 13     SSMS Analysis of SRC Sample	    22

 14     Elements Selected for Part II Inorganic
          Analysis	    23

 15     Process Information	    24

 16     GC Analysis for Cy through C-,« Hydrocarbons  .  .    25

 17     AA Analysis for Inorganics	    26

 18     Organic Air Emissions for Coal and SRC	    28

 19     Inorganic Air Emissions for Coal and SRC ....    29

 20     S09 and NC-  Emissions for Coal and SRC	    30
          fc       2x
 21     Comparison of SRC Air Emissions with MEG's ...    35

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                LIST OF ABBREVIATIONS AND SYMBOLS
MW
ABBREVIATIONS

AA      -- atomic absorption spectrophotometry
Btu     -- british thermal unit
CFM     -- cubic feet per minute
DSCF    -- dry standard cubic feet
EOD     -- elimination of discharge
EPC     -- estimated permissible concentrations
ESP     -- electrostatic precipitator
GC      -- gas chroma tography
GC/MS   -- gas chromatography/mass spectrometry
IR      -- infrared spectra     «
kg/GJ   -- kilogram per giga (10 ) joules
LRMS    -- low resolution mass spectrometry
MATE    -- minimum acute toxicity effluents
MC      -- mass constituent
MEG     -- multimedia environmental goals
MJ/kg   -- mega joules per kilogram
        -- megawatt
        -- cubic meter
mg      -- milligram
ml      -- milliliter
mg/m3   -- milligram per cubic meter
nm      -- nanometer
PAH     -- polynuclear aromatic hydrocarbon
ppb     — parts per billion
ppm     -- parts per million
SASS    -- source assessment sampling system
SRC     — solvent refined coal
SSMS    -- spark source mass spectrometry

SYMBOLS

As      -- arsenic
C       - - carbon
CH2C12  — methylene chloride  '
CO      -- carbon monoxide
C0£     -- carbon dioxide
Hg      -- mercury
NOX     -- nitrogen oxides
Sb      -- antimony
S02     -- sulfur dioxide
M       — micron
Mg/g    -- microgram per gram
Mg/m3   — microgram per cubic meter

                             vi

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                       ACKNOWLEDGMENT
     We gratefully acknowledge the contributions made to
this report by the following individuals:   Richard McRanie
and Robert Gehri of Southern Company Services;  Walter Dixon
of Southern Research Institute;  Richard Corey of Department
of Energy; and Mike Hartman, Arnie Grant and Carol Zee of
TRW.
                             vxx

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                           SECTION 1

                         INTRODUCTION
      The  U.S.  has  more energy available in the form of coal
 than in the combined resources of petroleum,  natural gas,
 oil  shale,  and tar sands.   In light of nationwide energy
 shortages,  the increased use of our abundant  coal reserves
 is vital  to the nation's total supply of clean energy.
 Consequently,  converting coal to liquid and gaseous fuels is
 fundamental to ensuring the availability of fuel as these
 alternate sources  become less certain.

      The  primary users of  coal are the electric utilities,
 which mechanically clean,  pulverize and burn  coal in solid
 form.   Coal combustion, however, is a major source of air
 pollution,  i.e., sulfur oxides, nitrogen oxides, and partic-
 ulate matter.   The combustion of coal by electric utilities
 is also a potential source of water and land  pollution.

      To minimize air pollution from the combustion of coal
 by electric utilities, the Solvent Refined Coal Process is
 being developed.   This process cleans coal prior to its
 firing in boilers  by the removal of sulfur and mineral
 matter, for the purpose of eliminating the need for stack
 gas  cleaning.   The product, Solvent Refined Coal (SRC),  is
 lower in  sulfur and ash, and has a higher heating value than
 the  original coal.

      In 1972 an all-industry group, presently consisting of
•Electric  Power Research Institute and Southern Company Ser-
 vices,  .initiated a pilot plant project to study the tech-
 nological feasibility of the SRC process.  Operating infor-
 mation from this pilot plant was used to design and build a
 45 metric ton per  day pilot plant in Fort Lewis, Washington.
 This project funded by the U.S. Department of Energy (DOE)
 is developed by Pittsburgh & Midway Coal Mining Company, a
 subsidiary of Gulf Oil Corporation.  The pilot plant has
 been in operation  since October 1974 and has  produced 2,720
 metric tons of SRC for the functional product testing in a
 boiler.

      With the company's involvement in developing the SRC
 process,  Southern  Company  Services was awarded a separate

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contract by DOE to evaluate the shipping, handling, and
burning characteristics of SRC.  To determine whether SRC
can be an acceptable substitute for coal and to demonstrate
the assumed advantages of SRC a combustion test was performed
in March, May and June of 1977 at Georgia Power Company's
Plant Mitchell.  The test was conducted in three phases and
marked the first time SRC had been burned, on a large scale,
in a conventional utility boiler.

     In Phase I, low sulfur Kentucky coal was burned in an
existing, unmodified 22.5 MW pulverized coal boiler.  In
Phase II, following replacement of the original burners with
dual register burners and accompanying modifications, the
boiler was again fired with low sulfur Kentucky coal.  In
Phase III, following adjustment of the burners and pulver-
izers, SRC was burned.  The SRC had been produced at the
Fort Lewis pilot plant from western Kentucky coals having a
sulfur content of approximately 4 percent and an ash content
of 10 to 12 percent.  Sulfur and ash in the SRC were nomi-
nally 0.7 and 0.6 percent respectively.  In each of the
three phases, the boiler was operated at full (~21 MW),
medium (~14 MW) , and low (~7 MW) load conditions.  Phases II
and III are discussed in detail in this report.

     During Phases II and III, flue gas sampling was con-
ducted using a Source Assessment Sampling System (SASS)
train to collect samples for modified EPA Level 1 laboratory
analysis.  Grab samples were also obtained for on-site
analysis of GI through C^ hydrocarbons, S02, N£, CO, C02 and
02.   Sampling and analysis are discussed in detail in later
sections of this report.

     Participants in the combustion test included:

     •    Southern Company Services - co-sponsor and owner

     •    DOE (formerly ERDA) - co-sponsor and supplier of
          SRC

     •    Southern Research Institute (SRI) - SASS train
          sampling and resistivity tests

     •    TRW - grab sampling and on-site analysis for CO,
          C02» SO^, N£, Q£ and C^ through Cg hydrocarbons

     •    York Research - EPA-5 and ASME trains, gaseous
          emissions, and precipitator efficiency

     •    Babcock & Wilcox - boiler efficiency

     •    Rust Engineering (a subsidiary of Wheelabrator-
          Frye) - resistivity tests

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     •    Wheelabrator-Frye - precipitator modeling for
          control of SRC combustion particulates

     •    Hittman Associates, Inc. - development and coor-
          dination of SASS train and grab sampling plan,
          sample analysis, and interpretation

     The results of the tests concerning resistivity, and
precipitator and boiler efficiencies, are not discussed in
this report.  The EPA sponsored precipitator evaluation as a
supplement to the DOE plan is presented in "Evaluation of
Electrostatic Precipitator During SRC Combustion Tests,"
EPA-600/7-78-129, June 1978.

     The results of the emissions measurement work performed
by York Research Corporation under contract to Southern Com-
pany Services, Inc., will be incorporated in a report being
prepared by Southern Company Services, Inc.

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                          SECTION 2

               CONCLUSIONS AND RECOMMENDATIONS
     The results of the combustion test at Plant Mitchell
indicated that SRC can be combusted in place of coal to fuel
today's utility boilers.  No major operational problems
were encountered during the firing of SRC.

     Significant reductions in S0£, NOX, and inorganic
emissions were observed.  During combustion of SRC, S0£
emissions were reduced to compliance with the existing New
Source Performance Standards (NSPS) of 0.52 kg/GJ  (1.2
lbs/106 Btu) input.  If, however, this standard is reduced
to 0.26 kg/GJ (0.6 lb/106) Btu, as is currently being con-
templated by the U.S. Environmental Protection Agency (EPA),
compliance is doubtful.

     NOX emissions were well below the NSPS of 0.3 kg/GJ
(0.7 lbs/10° Btu).  NOX concentrations increase with in-
crease in excess air but use of abnormally high excess air
has an effect of lowering NOX emissions.  During the combus-
tion test abnormally high excess air was used, and it is
therefore recommended that additional testing should be
conducted at normal conditions.

     The electrostatic precipitator used throughout the test
was an old (1946) Research Cottrell unit which was inef-
ficient for SRC flyash collection (16.89 to 45.68 percent).
When a more modern precipitator was briefly tested, collec-
tion efficiency increased to approximately 95 percent.  It
is therefore recommended that additional testing be con-
ducted, using a more efficient precipitator, to provide a
more accurate account of actual atmospheric particulate
emissions associated with the combustion of SRC.

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                          SECTION 3

                       COMBUSTION TEST
     One of the primary purposes of the combustion test was
to demonstrate the assumed advantages of SRC as a boiler
fuel.  This was attempted by retrofitting a small utility
boiler and burning approximately 2,722 metric tons of SRC
under carefully measured conditions.  The work was regarded
as a significant milestone in the objective of qualifying
coal-derived fuels for future energy needs.

     The unit selected for the test, Boiler No. 1, is
located at Georgia Power Company's Plant Mitchell, near
Albany, Georgia, and has a nameplate rating of 22.5 MW.  The
Babcock & Wilcox (B&W) natural circulation pulverized coal-
fired boiler is rated at 104,320 kilograms of steam per hour
at 58 atmospheres and 480 C.  The unit is equipped with B&W
E-35 pulverizers and a Research Cottrell perforated plate
electrostatic precipitator.  Turbines and generators were
manufactured by General Electric.

     The test was conducted in a three-phase program.
During Phase I, low sulfur (~1 percent) Kentucky coal was
burned in the unmodified boiler.  The purpose of this phase
was to provide a data base to isolate the effects of the
changed boiler configuration used during Phase II.  All
pulverizers, burners, and controls were operated normally.
SASS train samples were not collected during this phase.

     Once again burning low sulfur  (~1 percent) Kentucky
coal, Phase II was initiated May 24, 1977 and concluded June
6, 1977.  The original burners were replaced prior to this
phase with dual register burners and accompanying modifica-
tions.  This phase was to establish a base-line of operation
for later comparison with Phase III results.  The pulver-
izers and controls were operated normally.  SASS train and
grab samples were collected throughout this phase.

     Phase III began June 10, 1977 and continued through
June 25, 1977.  Solvent Refined Coal I, which had been
produced at the Fort Lewis pilot plant in Washington, was
fired.  The SRC had been produced from western Kentucky
coals having a sulfur content of approximately 4 percent and
an ash content of 10 to. 12 percent.  Minor modifications

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were made  to the pulverizers  and dual register  burners.  The
purpose  of this phase was  to  demonstrate the  assumed advan-
tages of SRC as a boiler fuel.   SASS train and  grab samples
were also  collected during this phase.
SAMPLE  COLLECTION

SASS Train

     During Phases II and III,  flue gas sampling was con-
ducted  using SASS train and  grab samples for modified EPA
Level I laboratory analysis.   Grab samples were obtained for
on-site analysis of C-, through C,. hydrocarbons, S09, N9, CO,
C02 and 02>           L           b                  z   z

     A  diagram of the SASS train is shown in Figure 1.  This
sampling device includes cyclones and a filter to collect
particulates,  a sorbent trap to collect organic constitu-
ents, impingers, and associated temperature controls, pumps,
and meters.   The sample is obtained from the flue gas duct
by means of a probe inserted through the duct  work and
positioned to intersect the  gas flow at a point having flow
characteristics representative of the bulk flow.
    STACK T.C.
                        CONVECTION
                      / OVEN
         FILTER
                                                 GAS COOLER
                  -*	ft
                          XAD-2
                          CARTRIDGE
       DRY GAS METER ORIFICE METER
        CENTRALIZED TEMPERATURE
        AND PRESSURE READOUT
           CONTROL MODULE
              IMP/COOLER
              TRACE ELEMENT
              COLLECTOR
                                    CONDENSATE
                                    COLLECTOR
H>W

 X_X10 CFM VACUUM PUMP
                Figure  1.   SASS Train Flowsheet

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     Particulates were removed from the sample flue gas
first, when the gas passed through a series of cyclones
maintained at 205°C.  Particulates were collected in three
size ranges, >10y, 3 to 10U, and 1 to 3u.  A standard fiber-
glass filter following the cyclones collected a fourth size
range, 
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                INLET SAMPLING
                  PORT
                   A
                      PRECIPITATOR NO. 1
  CONTINUOUS
X  SAMPLER
                      PRECIPITATOR NO. 2
                                       OUTLET
                                     B SAMPLING
                                       PORT
                                                  OUTLET SAMPLING
                                                  PORT
                                 DAMPER
    PRECIPITATOR NO. 3
                      PRECIPITATOR NO. 4
          Figure 2.   Diagram of Sampling  Locations


     Since precipitator No. 1 is a vintage Research Cottrell
unit, it was  requested that additional  tests be performed on
precipitator  No.  3,  a newer unit, for modeling purposes.
To facilitate these  tests, boiler No. 2 and precipitators
No. 1 and No.  2  were shut down, and SASS  train and grab
samples were  collected at outlet port C.


SAMPLING SCHEDULE

     The schedules for test Phases II and III were developed
by Southern Company  Services after consultation with the
participants.  The boiler load condition  and test precipi-
tator were designated for each day of the test.  Tables 1
and 2 indicate these schedules as well  as the location for
SASS train and grab  samples.

     Because  only one SASS train was available, it was
impossible to simultaneously collect samples at both the
inlet and outlet ports of the precipitator.   During each
phase the SASS train location was varied  to permit sampling
at both ports A  and  B.  SASS train and  grab samples were
collected from the same locations.
                               8

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TABLE  1.   PHASE II  -  COAL COMBUSTION TEST SAMPLING SCHEDULE
       Date
Load Condition
   SASS Train
Sampling Location
.May 24
May 25
May 26
May 27
May 28
May 29
May 30
May 31
June 1
June 5
June 6
Full
Medium
Low
Full
Full
Medium
Medium
Low
Low
Full
Full
Outlet ESP #1
Outlet ESP #1
Outlet ESP #1
Outlet ESP #1
Inlet ESP #1
Inlet ESP #1
Outlet ESP #1
Outlet ESP #1
Inlet ESP #1
Outlet ESP #3
Outlet ESP #3
 TABLE 2.   PHASE  III - SRC  COAL COMBUSTION  TEST SAMPLING
                         SCHEDULE
       Date
Load Condition
   SASS Train
 Sampling Location
June 13
June 14
June 15
June 16
June 17
June 18
June 19
June 20
June 21
June 22
June 23
June 24
Full
Medium
Low
Full
Full
Low
Low
Medium
Medium
Full
Full
"wide open"
Outlet ESP #1
Outlet ESP #1
Outlet ESP #1
Outlet ESP #1
Inlet ,ESP #1
Inlet ESP #1
Outlet ESP #1
Inlet ESP #1
Outlet ESP #1
Outlet ESP #3
Outlet ESP #3
Outlet ESP #1

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                          SECTION 4

                          ANALYSES
GRAB SAMPLES

     Flue gas grab samples were analyzed for GI through
hydrocarbons, S02, N£, CO, C02, and 02, usually within 30
minutes after sample collection.  The GI through Cg hydro-
carbons were determined by means of a flame ionization
detector in a Perkin-Elmer gas chromatograph.  During the
first three days of Phase II, the detection limit was 5 ppm
due to improper grounding of the instrument.  During the
remainder of Phases II and III, the detection limit was 0.5
ppm.

     The 02, N2* CO, C02, and S02 levels were measured with
a thermal conductivity detector in an A.I.D. portable gas
chromatograph.  The accuracy of this instrument was + 2
percent of the reading taken.

     York Research also continuously monitored NOX and S02
levels in the flue gases.  Thermo Electron analyzers (Model
10 for NOX and Model 40 for S02) with a reported accuracy of
+ 10 ppm, were used for this purpose.  The emissions mea-
surement results will be included in a report being prepared
by Southern Services, Incorporated.

     Flue gas grab sample analytical results are reported in
Tables 3 and 4.  For comparison, typical SOX and NOX concen-
trations obtained from continuous analyzers are also given.
Analytical results for coal and SRC grab samples were pro-
vided by Southern Services, Inc., and are shown in Tables 5
and 6.  The coal and SRC analyses were performed by Commer-
cial Testing and Engineering Co. of Golden, Colorado.


SASS TRAIN SAMPLES

     The analysis of the SASS train samples was conducted in
two parts.
                              10

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       TABLE 3.    ON-SITE  ANALYSIS OF GRAB SAMPLES,  PHASE  II -  COAL  COMBUSTION

                                        May  24  to  June  6,  1977
On-Site Gas
Date
5/26
5/31
6/02
5/25
5/29
5/30
5/24
5/27
5/28
6/05
6/06
ND
ND
ND
ND
ND
ND
—
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
—
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
—
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
—
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
—
ND
ND
ND
ND
Chromatography Analysis
ND
ND
ND
ND
ND
ND
—
ND
ND
ND
ND
C0<3>
ND
ND
ND
ND
ND
ND
--
ND
ND
ND
ND
13.31Z
14.24Z
14.91Z
15.73Z
13.70Z
12.602
	
13.78Z
11.25*
12.14*
11.16*
co.,'1'
7.40Z
7.50Z
6.56Z
5.51Z
7.59Z
7.35Z
	
6.65Z
9.86Z
9.31Z
9.69Z
„ (1)
N2
79.29Z
78.26Z
78.53Z
78.76Z
78.71Z
80.05Z
	
79.66Z
78.89Z
78.55Z
79.15Z
254
329
174
413
209
413
	
311
381
214
210
Continuous
Sampler
S0y<2>
260
360
200
500
220
400
745
330
330
200
180
110
110
100
170
160
150
225
215
220
170
110
Time
1500
1140
0300
1400
1400
1240
1200
1530
1420
1330
1030
Load
Condition
Low
Low
Low
Med
Med
Med
Full
Full
Full
Full
Full
Sample
Location
0-1
0-1
1-1
0-1
1-1
0-1
0-1
0-1
1-1
0-3
0-3
ND - None Detected



SO and NO  values are in ppm
  X      X


1-1 - Inlet to precipitator 01



0-1 - Outlet to precipitator 01



0-3 - Outlet to precipitator #3



(1) - + 2Z of total concentration



(2) - + 10 ppm



(3) - 40 ppm detectable limit




(4) - 5 ppm detectable limit 5/25, 5/26, and 5/27, 0.5 ppm detectable limit 5/28 through 6/06

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        TABLE  4.   ON-SITE  ANALYSIS  OF  GRAB SAMPLES,  PHASE III -  SRC COMBUSTION
                                      June 13 to  June  24,  1977
On-Site Gas Chromatography Analysis
Date
6/15
6/18
6/19
6/14
6/20
6/21
6/13
6/16
6/17
6/22
6/23
6/24
ND
ND
ND
ND
—
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
—
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND-
ND
ND
ND
ND
ND
ND
ND .
ND
—
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
—
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
—
ND
ND
ND
ND
ND
ND
C0<3>
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
14.79Z
13.25Z
14.00Z
13.65Z
	
11.39Z
10.62Z
11. HZ
11.20Z
10.75Z
10.76Z
5.88Z
6.73Z
6.26Z
7.53Z
	
9.86Z
9.12Z
9.15Z
9.25Z
t
8.90Z
9.29Z
N2 X
79.33Z
80.02Z
79.74Z
78.82Z
	
78.75Z
80.26Z
79.74Z
79.55Z
80.35Z
79.95Z
198
216
218
248
371
410
404
400
393
449
Continuous
Sampler
225
220
235
260
	
325
335
345
345
325
380
125
120
125
160
	
190
190
190
200
220
260
Time
1030
1200
1230
1200
	
1300
1145
1100
1030
1000
1100
Load
Condition
Low
Low
Low
Med
Med
Med
Full
Full
Full
Full
Full
23.5
Sample
Location
0-1
1-1
0-1
0-1
0-1
1-1
0-1
0-1
1-1
0-3
0-3
0-1
ND - None Detected

SO and NO values are in ppm

1-1 - Inlet to precipitator II

0-1 - Outlet to precipitator II

0-3 - Outlet to precipitator 13

(1) - + 2Z of total concentration

(2) - + 10 ppm

(3) - 40 ppm detectable limit

(4) - 0.5 ppm detectable limit

-------
      TABLE 5.   COMBUSTION TEST, PHASE II - COAL SAMPLES
Proximate Analysis

Date
5/26
5/31
6/2
5/25
5/29
5/30
5/24
5/27
5/28
6/5
6/6

% Sulfur
0.64
1.05
NA
1.09
0.62
1.15
1.34
0.73
0.72
0.66
0.64

% Nitrogen
1.38
1.81
NA
1.29
1.82
1.82
1.19
1.51
1.45
1.60
1.81
Heating*
Value, MJ/kg
7.144
7.043
NA
7.007
7.139
7.139
7.042
7.081
7.079
NA
7.143
NA - Not Available
*Moisture and Ash Free Basis
      TABLE 6.   COMBUSTION TEST, PHASE III  -  SRC SAMPLES
          Date
% Sulfur
                               Proximate Analysis
% Nitrogen
 Heating*
Value, MJ/kg

6/15
6/18
6/19
6/14
6/13
6/16
6/17
6/22
6/23
6/24
0.70
0.74
0.66
0.72
0.73
0.73
0.72
0.70
0.64
0.66
1.54
1.80
1.82
1.62
2.02
1.77
1.47
1.37
1.37
1.71
7.530
NA
7.496
7.525
7.459
7.464
7.546
7.485
7.431
7.418
NA - Not Available
*Moisture and Ash Free Basis
                                13

-------
Part  I
      In Fart  I,  two complete SASS train  runs were analyzed
by TRW.   Samples selected for analysis were SRC  runs of  June
16 and, June 19,  1977.   Relevant  process  information per-
taining to these runs  is given in Table  7.   Organic and
inorganic analyses were conducted separately.  Figure 3
shows the analytical procedures  followed.
                   TABLE  7-   PROCESS INFORMATION
    Date:  June 16,  1977
        Load:
        Fuel Flow:
        Heating Value:
        Stack Gas Temperature:
        Sample Volume:
        Precipitator:
        Sample Port:
        Precipitator Efficiency:
        Gas Flow, ESP #1 Outlet:
21 MW
8,063 kg SRC/hr (17,775 Ib/hr)
7.464 MJ/kg SRC (15,602 Btu/lb)
166°C (331°F)
28,46 m3 (1,005 DSCF)
#1
B (Outlet #1)
16.89%
3,620 m3/minute (127,858 ACFM)
    Date:  June 19,  1977
        Load:
        Fuel Flow:
        Heating Value:
        Stack Gas Temperature:
        Sample Volume:
        Precipitator:
        Sample Port:
        Precipitator Efficiency:
        Gas Flow,. ESP #1 Outlet:
7.5 MW
3,379 kg SRC/hr (7,450  Ib/hr)
7.496 MJ/kg SRC (15,668 Btu/lb)
147°C (296°F)
30.16 m3 (1,065 DSCF)
#1
B (Outlet #1)
45.68%
2,005 m3/minute (70,793 ACFM)
                                  14

-------
                              o    •—   z     o
                                   —I   O Z   —•
                              a    a.   1-1 t3   (_
                              z    c/i wi  I— 3   i/j

                              (/)    Z O-  S Z S «-^
                              a  =  •*!  fc •- -1 °
                              <  O  <9 tn  uj  rs. i  o
             SAMPLE
GRAB SAMPLE

10 CYCLONE

3 CYCLONE



FILTER 	
                       COMBINE
                        COMBINE
PROBE HASH, etc.

XAD-Z CARTRIDGE

FIRST IHPINGER -
                         SPLIT
                                              °-°
                        L
           AQUEOUS CONDENSATE
           ORGANIC RINSE
                     COMBINED
           SECOND AND THIRD
             IHPINGERS
           SRC OR COAL
                                              -O—O
           Figure 3.  Analytical Procedures Followed
                  in SASS Train Run Analysis
Organic Analysis —
     Samples requiring solvent extraction for organic analy-
ses were  the XAD-2 resins  and the cyclone and filter par-
ticulate  samples.  For XAD-2  resins, virtually  all  of the
sample material was taken  for extraction.  A small  portion
of each XAD-2 resins was removed for inorganic  analysis.
Two composite particulate  samples for each run  were pre-
pared, one by combining small portions of lOy sample and 3u
sample, and the second by  combining lu sample and filter
sample.   Methylene chloride was the solvent used  in all
extractions.  Other required  sample preparations  included
filtering the solids out of the probe rinses and  concentra-
ting all  samples to 10 ml  volumes .
     C?  through Cifi gas chromatography — The gas  chroma-
tography was performed using  the parameters and  procedures
specified  by EPA for Level  1  analysis.  On the instrument
used, these parameters provided a lower detectable  limit of
approximately 0.2 ug/m3-  Analytical results are expressed
in terms of the quantity of n-alkanes boiling in the fol-
lowing temperature ranges:
                               15

-------
C7
C8
C9
CIO
Cll
90-110°C
110-140°C
140- 160 °C
160-180°C
180-200°C
C12
CIS
C14
CIS
C16
200-220°C
220-240°C
240-260°C
260-280°C
280-300°C
     To calibrate the instrument for  these  Cy  through
boiling point ranges, chromatograms of n-alkane  mixtures
were obtained and a plot of normal boiling  points  versus
retention times was constructed.  The retention  times cor-
responding to the appropriate boiling ranges were  summed
within each retention time interval in order to  convert to
quantities of components designated as n-alkanes.   The
results of these analyses are given in Table 8.
    TABLE 8.  GC ANALYSIS FOR C? THROUGH  C16  HYDROCARBONS

June 16, 1977
June 19, 1977
C7
nig** mg/m
0* 0
0 0
C8
3
mg mg/m
3.73 0.12
2.52 0.09
C9
3
mg mg/m
0 0 z
1.51 0.05
C10
3
mg mg/m
0.53 0.20
0.80 0.03
Cll
3
mg mg/m
1.82 0.06
2.68 0.09


June 16, 1977
June 19, 1977
C12
3
mg mg/m

0.85 0.03
1.29 0.05
C13
3
mg mg/m

0 0
0 0
cu
3
mg mg/m

0.11 0.004
1.08 0.04
C15
3
mg mg/m

0 0
0 0
C16
3
mg mg/m

0 0
0 0
* Zero values represent a detection limit of 0.007 mg.
**Total amount of compound detected in the samples.
     For the particulate samples,  all  data for Cg through
    appeared to be significant, whereas  for the probe rinse
and XAD-2 module condensate extract  plus module rinse samples
probably none of the sample values were  significant because
of the high blank values.

     Grayimetry and infrared  spectrometry—To determine the
nonvolatile contents of the samples,1 ml aliquots were
taken from each of the 10 ml  concentrates and evaporated to
dryness.  The primary tool for understanding the signifi-
cance of Level 1 gravimetry data  is  the  infrared spectra
                               16

-------
(IR),  because the spectra can show qualitative differences
between samples and blanks.  The nonvolatile residues from
the gravimetric procedure were scanned by an IR spectro-
meter, with the exception of the particulate extract sam-
ples,  which all produced insufficient residues to be able to
perform the IR analysis.  The classes of compounds iden-
tified are listed in Tables 9 and 10.  Due to the high blank
values, none of the values appear significant.

     Polynuclear aromatic hydrocarbons (PAH's) by combined
     gas chromatography/mass spectrometry (GC/MS;--For the
GC/MS analysis,1 ml aliquots of the 10 ml concentrated
sample volumes were evaporated under a stream of inert gas
and then brought up to a total volume of 2 ml, with 1 ml
internal standard and 1 ml of benzene.  The resulting solu-
tions were analyzed with a Finnigan Model 4023 automated
GC/MS instrument.  The compounds in each sample were sep-
arated on a 1.8 meter x 2 millimeter ID glass column packed
with three percent Dexsil 300 on 100-120 Chromosorb WHP.
This column is operated from 100° to 295°C, programmed at
4°/min.  The detection limit for this work was 0.1 g in
the aliquots analyzed.  The only polycyclic compound iden-
tified is most likely naphthalene (CioH8) or azulene (also
CioHo)•  Because the naphthalene was also present in the
blank, and because the blank also contained some of the
styrenes, benzoates, and other compounds typically found as
residual materials even in pre-cleaned XAD-2 resins; it was
concluded that the samples did not contain organic materials
significantly different from, or above, the blank materials.

Inorganic Analysis--
     Two types of sample preparation were required for the
inorganic analyses.  The first was the Parr bomb combustion
of the XAD-2 resin and SRC samples.  For each of these
samples, a 1-gram aliquot was combusted for Spark Source
Mass Spectrometry (SSMS) and a 2-gram aliquot was combusted
for the antimony, arsenic, and mercury analyses.  All
combustion solutions were made to a  100 ml volume.  The Parr
bomb combustion procedure utilized a quartz bomb liner and
platinum electrodes and firing wire  in order to minimize
contamination of the samples from the stainless steel bomb.

     The second type of preparation was the aqua regia
digestion of particulate samples.  Two composite particulate
samples for each run were prepared,  one by combining small
portions of 10U sample and 3P sample, and the second by
combining lu sample and filter sample.  The samples were
refluxed with constant-boiling aqua regia for six hours,
filtered, and made up to 100 ml for antimony, arsenic, and
mercury analyses.  Because of their negligible organic
content, the particulate samples did not require any


                              17

-------
     TABLE  9.   IR EXAMINATION OF  NONVOLATILE HYDROCARBONS
                               June 16, 1977
Sample
Classes of Compounds Identified
Probe Rinse
XAD-2 Module Condensate
Extract plus Module Rinse

XAD-2 Resin
Methylene Chloride Blank
Methanol Blank
Methylene Chloride-Methanol
Blank (50%-50%)
XAD-2 Resin Blank
Esters of benzoic acid and other carboxylic
acids, glycol, and phenolic resin (640  ppm)

Phthalic acid ester,  other carxobylic acid
esters, and phenolic resin (1,600 ppm)

Aliphatic carboxylates, glycol;  minor-
benzene derivatives (1,100 ppm)

Esters of benzoic acid and other carboxylic
acids, and phenolic resin (3,700 ppm)

Phthalic acid ester,  salt of carboxylic
acid, and phenolic resin (500 ppm)

Esters of benzoic acid and other carboxylic
acids, glycol, and phenolic resin (1,200
ppm)

Trace of benzene derivatives (680 ppm)
     TABLE  10.   IR EXAMINATION OF NONVOLATILE HYDROCARBONS
                            June 19,  1977
Sample
Classes of Compounds Identified
Probe Rinse
XAD-2 Module Condensate
Extract plus Module Rinse
XAD-2 Resin
Methylene Chloride Blank
Methanol Blank
Methylene Chloride - Methanol
Blank (50%-50%)

XAD-2 Resin Blank
Esters of benzoic acid and other carboxylic
acids, glycol, and phenolic resin (660 ppm)

Major - aliphatic carboxylates;  minor -
phthalates, benzoates, and phenolic resin
(1,700 ppm)

Esters of aliphatic carboxylic acid and ben-
zoic acid, glycol, and traces of benzene
derivatives (700 ppm)

Esters of benzoic acid and other carboxylic
acids, and phenolic resin (3,700 ppm)

Phthalic acid ester, salt of carboxylic acid,
and phenolic resin (500 ppm)

Esters of benzoic acid and other, carboxylic
acids, glycol, and phenolic resin (1,200 ppm)

Trace of benzene derivatives (680 ppm)
    _.

-------
preparation for  the  SSMS analysis.  The condensates  and
impingers also required no preparation.

     Antimony, arsenic,  and mercury elemental analyses—The
specific elemental analyses were performed using  the ex-
panded and modified  Level 1 procedures compiled by Research
Triangle Institute at EPA's direction.  Briefly,  these
methods are as follows:

     •    Mercury -  reduction to elemental mercury with
          stannous chloride, sparging through a detection
          cell and measurement of the mercury at  253.7 nm.

     •    Arsenic -  reduction to the hydride with stannous
          chloride and metallic zinc, sparging into  an
          argon-hydrogen flame in an atomic absorption
          spectrophotometry (AA) instrument and measurement
          of  the arsenic at 193.7 nm.

     •    Antimony - reaction with a series of reagants to
          form stibine,  sparging into a hydrogen  diffusion
          flame  in an AA instrument, and measurement of the
          antimony at 217.6 nm.

The results obtained by analyzing the particulate and XAD-2
resin samples are reported in Table 11.
       TABLE  11.   TOTAL HG, AS, AND SB IN PARTICULATES
                        AND XAD-2 RESIN
June 16, 1977


June 19, 1977


SRC Sample
                      Hg
                     As
  191.53 yg*
(6.73 yg/m3)

  351.61 yg
(11.66 yg/m3)

  45 ppb
  2,240 yg
(78.72 yg/m3)

   650 yg
(21.55 yg/m3)

    14 ppm
                     Sb
yg
   ^ ys 0
(1.89 yg/m3)

   53 yg
(1.76 yg/m3)

     ND**
*   - Total amount of element detected in the samples.
**ND - None detected, antimony detection limit is 0.005 ppm.
     Spark  source  mass spectrometry--The SSMS  analysis  was
performed by  Commercial Testing and Engineering  Co.  of
Golden, Colorado.   The results for the SASS train  and SRC
samples are presented in Tables 12 and 13.  During the  SSMS
analysis, several  of the elements were found to  be mass
constituents,  and  had too high a concentration to  be
                              19

-------
TABLE 12.  SSMS ELEMENTAL ANALYSIS OF SASS TRAIN SAMPLES
Constituent
Uranium
Thorium
Lead
Thallium
Platinum
Rhenium
Tungsten
Tantalum
Hafnium
Lutetium
Ytterbium
Thulium
Erbium
Holmium
Dysprosium
Terbium
Gadolinium
Europium
Samarium
Neodymium
Praseodymium
Cerium
Lanthanum
Barium
Cesium
Iodine
Tellurium
Antimony
Tin
Cadmium
Silver
Molybdenum
Niobium
June 16,
ng*
958
674
141
13
5
5
73
30
73
16
121
15
96
121
212
48
129
65
322
468
138
584
485
22,200**
52
16
11
66
230
38
6
772
1,790
1977
Hg/m
34
24
5
0.5
0.2
0.2
3
1
3
0.6
4
0.5
3
4
7
2
5
2
11
16
5
21
17
780
2
0.6
0.4
2
8
1
0.2
27
63
June 19,
ug*
581
250
78
15
7
4
36
31
31
9
47
5
15
31
47
10
31
14
64
68
36
233
176
1,333
6
31
7
47
97
32
123**
505
904
1977
ug/m3
19
8
3
0.5
0.2
0.1
1
1
1
0.3
2
0.2
0.5
1.
2
0.3
1
0.5
2
2
1
8
6
44
0.2
1
0.2
2
3
1
4
17
~30
                       (continued)
                            20

-------
                         TABLE 12.   (continued)
                            June 16,  1977
June  19, 1977

Zirconium
Yttrium
Strontium
Rubidium
Bromine
Selenium
Arsenic
Germanium
Gallium
Zinc
Copper
Nickel
Cobalt
Iron
Manganese
Chromium
Vanadium
Titanium
Scandium
Calcium
Potassium
Chlorine
Sulfur
Phosphorus
Silicon
Sodium
Fluorine
Boron
Beryllium
Lithium
Aluminum
Magnesium
Ug*
8,400**
3,355
4,254**
115
80
296
1,611
218
803
1,111
1,252
2,654
525
2,002,018**
8,859
2,004,011**
1,008,338**
1,302,045**
852
4,008,022**
1,000,084**
447
620,000**
1,030,252**
600,506**
9,420**
541
7,300
394
141
6 , 008**
. 600,506**
u.g/m
295
118
149
4
3
10
57
8
28
39
44
93
18
70,345
311
70,415
35,430
45,750
30
140,830
35,140
16
21,785
36,200
21,100
331
19
257
14
5
211
21,100
ug*
3,416
1,258
2,054
43
890
15
1,303
352
881
2,636
1,230**
1,137
243
1,201,866**
4,830**
11,200**
7,260**
400,826**
601
1,502,873**
24,060**
2,130**
22,020**
20,100**
330,252**
11,010**
719
8,727
300
159
4,403**
330,252**
|ig/m
113
42
68
1
30
2
43
12
29
87
41
38
8
39,850
160
371
241
13,290
20
49,830
798
71
730
666
10,950
365
24
289
10
5
146
10,950
* Total amount of element detected in  the samples of particulates.
**Mass Constituent (MC)  - too  high in  concentration to be quantified.
  reported represent the lower estimated limit.

                                     21
               Values

-------
            TABLE 13.   SSMS  ANALYSIS OF  SRC SAMPLE
Element
Uranium
Lead
Platinum
Cerium
Lanthanum
Barium
Cesium
Silver
Molybdenum
Niobium
Zirconium
Yttrium
Strontium
Rubidium
Selenium
Arsenic
Germanium
Gallium
Zinc
Copper

Concentration
yg/g**
1
5
0.9
0.2
0.3
4
0.5*
0.2
6
0.3
2
0.9
2
0.5
0.6
0.5
0.1
0.4
8
4

Element
Nickel
Cobalt
Iron
Manganese
Chromium
Vanadium
Titanium
Scandium
Calcium
Potassium
Chlorine
Sulfur
Phosphorus
Silicon
Aluminum
Magnesium
Sodium
Fluorine
Boron
Beryllium
Lithium
Concentration
Ug/g**
5
0.2
30
3
3
2
30
0.1
200
20
3
30
9
300
10
40
30
40
10
0.2
0.2
* Elements  designated as "_<" were identified, but because of their low
  concentrations, could not be quantified as accurately.
^^Concentration of element in yg per  gram of SRC sample.
                                  22

-------
quantified.  For these  elements,  the lower estimated limits
are reported.

Interpretation of Results--
     Additional analyses,  based on the results of Part I,
were to be performed under Part II to provide a comparison
of coal and SRC flue gases.   The analytical results from the
organic analysis indicated that only volatile Cy through Ci2
hydrocarbons were present  in appreciable quantities.
Nonvolatile hydrocarbons and polynuclear aromatic hydrocar-
bons were not found in  significant quantities above the
blank values.  It was therefore decided to analyze two
additional SASS train runs,  one SRC and one coal, for Cy
through Ci2 hydrocarbons to  provide a comparison of the
organic content of the  respective flue gases.

     Based upon the SSMS results, 17 elements were selected
to be analyzed by Atomic Absorption Spectrophotometry for
the two additional SASS train runs.  Elements selected
included several of the MC elements, and other elements of
interest present in significant quantities.  Table 14 lists
the 17 elements selected for analysis.


 TABLE 14.  ELEMENTS SELECTED FOR PART II INORGANIC ANALYSIS

                  Mass                  Elements of
              Constituents  (MC)           Interest

                Aluminum                Antimony
                Barium                   Arsenic
                Chromium                Boron
                Copper                   Lead
                Iron                    Mercury
                Magnesium                Nickel
                Manganese                Thorium
                Vanadium      ,          Uranium
                                        Zinc
Part II

     In. Part II,  two  additional SASS train runs were analy-
zed by the Hittman  laboratory.   Samples selected for analy-
sis included a coal run of May 25,  1977,  an SRC run of June
14, 1977, and respective coal and SRC grab samples.  Rele-
vant process information is given in Table 15.
                               23

-------
                   TABLE 15.   PROCESS INFORMATION
Date:  May 25, 1977
    Load:
    Fuel Flow:

    Heating Value:
    Stack Gas Temperature:
    Sample Volume:
    Precipitator:
    Sample Port:
    Precipitator Efficiency:
    Gas Flow, ESP #1 Outlet:
           14 MW
           6,940 kg coal/hr
           (15,300 Ib/hr)
           7.007 MJ/kg (14,648 Btu/lb)
           147°C (296°F)
           29.65 m3 (1,047 DSCF)
           11
           B (Outlet #1)
           94.81%
           3,002 m3/minute (105,997 ACFM)
Date:  June 14, 1977
    Load:
    Fuel Flow:

    Heating Value:
    Stack Gas Temperature:
    Sample Volume:
    Precipitator:
    Sample Port:
    Precipitator Efficiency:
    Gas Flow, ESP //I Outlet:
           14 MW
           5,460 kg SRC/hr
           (12,038 Ib/hr)
           7.525 MJ/kg (15,729  Btu/lb)
           144°C (291°F)
           28.60 m3 (1,010 DSCF)
           #1
           B (Outlet II)
           21.96%
           3,076 m3/minute (108,632 ACFM)
Organic Analysis—
      Samples were prepared as in  Part I, Organic Analysis,
and  run on the Packard Model 419  Becker gas chromatograph.
Analytical results are again expressed in  terms of the
quantity of n-alkanes boiling in  the following temperature
ranges:
           C9
 90-110°C
110-140°C
140-160°C
Cll
Cl2
160-180°C
180-200°C
200-220°C
The  results of these analyses are given  in Table  16.
                                 24

-------
                 TABLE 16.  GC ANALYSIS FOR
                 C? THROUGH C12 HYDROCARBONS

Coal-May 25, 1977
SRC-June 14, 1977
C7
/ 3
nig* mg/m
17.34 0.58
ND 	
C8
3
mg mg/m
j> 	
3.09 0.11
C9
3
mg mg/m
10.21 0.34
8.60 0.30


Coal-May 25, 1977
SRC-June 14, 1977
ND - None Detected
T - Trace (<1 ppm)
C10
mg mg/m

2.45 0.08
5.36 0.19
Cll
mg mg/m

15.30 0.52
23.97 0.84
C12
/ 3
mg mg/m

16.83 0.57
; 14.10 0.49
* -  Amount of compound detected.
Inorganic Analysis--
     Samples were prepared as  in  Part  I,  Inorganic Analysis,
and run on the Perkin Elmer Model 603  Atomic Absorption
Spectrophotometer.  The results of these  analyses are
reported in Table 17.
                              25

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                                TABLE 17.   AA ANALYSIS  FOR INORGANICS

Constituent

Aluminum
Antimony
Arsenic
Barium
Boron
Chromium
Copper
Lead
Iron
Magnesium
Manganese
Mercury
Nickel
Thorium
Uranium
Vanadium
Zinc
Coal SASS
train
May 25,
yg*
run
1977
3
yg/m

24,016
135
69
1,430
7
1,694
246
185
37,624
4,096
884
17
2,441
236
6
364
382
809.98
4.55
2.32
48.23
0.24
57.13
8.30
6.24
1,268.94
138.15
29.81
0.57
82.33
7.96
0.20
12.28
12.88
SRC
train
June 14
yg*
SASS
run
, 1977
3
yg/m

6,150
102
41
335
56
475
18
40
22,869
1,656
1,789
59
385
31
101
1,269
258
215.03
3.57
1.42
11.71
1.95
16.61
0.63
1.40
799.62
57.90
62.55
2.06
13.46
1.08
3.53
5.91
9.02
Coal grab
May
Sample
yg/g**
samples
25, 1977
I Sample II
yg/g**

5,223.0
1.7
2.9
58.0
ND
13.0
16.0
9.0
3,352.0
340.0
21.0
0.3
12.0
4.7
1.3
24.1
12.5
4,506.0
—
—
—
—
4.5
14.0
7.5
2,503.0
370.0
21.0
—
10.5
4.2
1.4
20.0
50.0
SRC
grab
samples
June 14, 1977
Sample I
yg/g**
Sample II
yg/g**

60.0
0.1
1.8
2.0
0.2
4.0
1.2
0.5
187.0
8.0
14.5
0.8
2.0
5.0
0.8
11.4
6.5
95.0
—
—
—
0.5
6.0
1.5
ND
250.0
12.0
18.0
—
2.3
3.7
1.3
10.9
7.5
to
ON
    ND - None Detected
    *  - Total amount of element  detected in sample
    ** - Concentration of element per gram of sample

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                            SECTION 5

                   COMPARISON OF AIR EMISSIONS
     Prior to attempting to compare the emissions resulting
from the combustion of SRC and coal at Plant Mitchell,
several factors must be considered.  First, the results
obtained from the SRC analyses conducted under Part I should
not be used for comparison purposes.  The load conditions
during the period of sampling (7.5 MW and 21 MW) do not
compare with the load conditions of the coal run analyzed
under Part II (14 MW).   Also, the difficulty in quantifying
the MC elements poses serious questions about the accuracy
of the SSMS results.  Results obtained from Part I analyses
were used only to provide an indication of the presence or
absence of constituents in SRC flue gas streams.  Only
analytical results from Part II should be used for the
comparison of SRC and coal air emissions.

     The second factor which must be considered is the
difference in the efficiency of precipitator #1 between
when SRC and coal are fired.  For the coal run of May 25,
1977 and the SRC run of June 14, 1977, precipitator effi-
ciencies were 94.81 and 21.96 percent respectively.  Pre-
cipitator #1 is an old (1946) Research Cottrell unit.
During the latter part of Phase III, precipitator #3 was
used, and the collection efficiency for SRC increased to
approximately 95 percent.  Therefore, it should be noted
that the particulate air emissions given in this report
resulting from the combustion of SRC may be assumed to
represent maximum values.  The precipitator efficiency had
no impact on gaseous emissions (organics, SOX, NOv, etc.).
For further information concerning precipitator efficiency
during the combustion test, readers are referred to a report
by Southern Research Institute, Evaluation of Electrostatic
Precipitator at Plant Mitchell, January 19757 under EPA Con-
tract No. 68-02-2610.
ORGANICS

     Table 18 shows the comparison of the Cy through C^2
hydrocarbons present in the combustion flue gases for SRC
and coal.  Detectable quantities of all Cy through C]_2
hydrocarbons were present in both coal and SRC flue gases.

                             27

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However, during combustion of SRC, Cy, Cg and C^2 hydro-
carbon emissions decreased, while Cg, CIQ and C]^ emissions
increased.  The comparison of coal and SRC emissions offers
no clear indication of the effects on Cj through C]9 emis-
sions by the substitution of SRC for low sulfur coal.
      TABLE 18.  ORGANIC AIR EMISSIONS FOR COAL AND SRC

                             Coal              SRC
                           May 25. 1977       June 14. 1977
     Hydrocarbon

c_
7
C.
8
C_
9
C10
Cll
C12
0.58

T

0.34

0.08
0.52
0.57
ND

0.11

0.30

0.19
0.84
0.49
ND - None Detected
T  - Trace
INORGANICS

     The resulting air emissions from the combustion  of  coal
on May 25, 1977 and SRC on June 14, 1977 at Plant Mitchell,
are shown in Table 19.  The coal used to produce the  SRC was
not from the same source as the coal fired on May 25,  1977.
The quantity of minerals present in the respective  coal  have
a direct impact on the resulting air emissions.  During  coal
combustion highly volatile trace elements may appear  in  com-
bustion gases.  During solvent refining along with  sulfur  and
ash reduction some highly volatile trace elements may also be
removed from coal.  Due to this reason when SRC is  burned
lower concentrations of trace elements generally appear  in
the combustion gases.  As shown in Table 19 concentrations
of most of the trace elements in combustion gases from SRC
derived from high sulfur coal are lower than those  resulting
from direct combustion of low sulfur coal.
                              28

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     TABLE  19.   INORGANIC AIR EMISSIONS FOR COAL AND SRC
Constituent
Aluminum
Antimony
Arsenic
Barium
Boron
Chromium
Copper
Lead
Iron
Magnesium
Manganese
Mercury
Nickel
Thorium
Uranium
Vanadium
Zinc
Coal
May 25. 1977
/ig/m3*
809.98
4.55
2.32
48.23
0.24
57.13
8.30
6.24
1,268.94
138.15
29.81
0.57
82.33
7.96
0.20
12.28
12.88
SRC
June 14. 1977
pg/m3*
215.03
3.57
1.42
11.71
1.95
16.61
0.63
1.40
799.62
57.60
62.55
2.06
13.46
1.08
3.53
5.91
9.02
*The concentrations are based on amount of a constituent detected in the
 total particulates collected.
S09 AND N0v
  *•        2t
     The values of S02 and NOX  in the SRC and coal  combus-
tion gases obtained from continuous analyzers are shown in
Table 20.   The emission of S0£  is reduced approximately 37
percent, and NOX by 12 percent, when SRC is fired.   These


                              29

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TABLE 20.   SO,
                                           AND NOV  EMISSIONS FOR COAL AND SRC
                                                  X
Load Condition
Low ( 7.5 MW)
Low
Low
Average
Medium ( 14 MW)
Medium
Medium
Average
Full ( 21 MW)
Full
Full
Average
Total Average
Date
5/26/77
5/31/77
6/01/77
5/25/77
5/29/77
5/30/77
5/24/77
5/27/77
5/28/77

0.645
1.023
0.598
0.757
0.800
0.791
0.791
0.796
1.002
0.443
0.456
0.727
Coal
so2*
(1.50)
(2.38)
(1.39)
(1.76)
(1.86)
(1.84)
(1.84)
(1.85)
(2.33)
(1.03)
(1.06)
(1.47)
1.69

0.198
0.224
0.215
0.211
0.194
0.215
0.215
0.201
0.215
0.201
0.220
0.215
0.211
NO *
X
(0.46)
(0.52)
(0.50)
(0.49)
(0.45)
(0.50)
(0.50)
(0.48)
(0.50)
(0.48)
(0.51)
(0.50)
0.49
Date
6/15/77
6/18/77
6/19/77
6/14/77
6/20/77
6/21/77
6/13/77
6/16/77
6/17/77

0.520
0.452
0.486
0.486
0.439
0.477
0.447
0.456
0.426
0.412
0.434
0.426
SRC
(1.21) 0.201
(1.05) 0.176
(1.13) 0.176
(1.13) 0.185
(1.02) 0.194
(1.11) 0.211
(1.04) 0.194
(1.06) 0.198
(0.99) 0.176
(0.97) 0.168
(1.01) 0.172
(0.99) 0.172
(1.06) 0.185
it
(0.48)
(0.41)
(0.41)
(0.43)
(0.45)
(0.49)
(0.45)
(0.46)
(0.41)
(0.39)
(0.40)
(0.40)
(0.43)
Z Reduction
S02 N0x
19.33
55.88
18.71
35.80
45.16
39.67
43.48
42.70
57.51
5.83
4.72
32.65
37.28
-4.35
21.15
18.00
12.24
0.00
2.00
10.00
4.17
18.00
18.75
21.57
20.00
12.24
OJ
o
    *Values are in kg/GJ and (lb/10 Etu)

-------
values represent substantial reductions in total S02 and
NOX emissions.  However, during the combustion test abnor-
mally high excess air was used, which would have an effect
of lowering NOX.  The combustion test should therefore be
run under normal conditions to obtain the NO  emissions
data.                                       x
                               31

-------
                          SECTION 6

                 ASSESSMENT OF AIR EMISSIONS
ORGANICS
     The release of organic constituents to the air via the
combustion of SRC is not an area of major environmental con-
cern.  The objective of the combustion process is to convert
all carbon present in the feedstock to carbon dioxide.
Therefore, significant quantities of organic constituents
will only be discharged during incomplete combustion.  This
is not the case with today's sophisticated boiler opera-
tions.  The emissions of Cy through C^2 hydrocarbons during
the combustion of SRC do not appear to differ significantly
from the direct combustion of coal.  Therefore, these emis-
sions are not at present an area of major environmental
concern.  Also, no carcinogenic PAH's were found in the SRC
flue gases.
INORGANICS

     The method used to assess the impact of the inorganic
air emissions resulting from the combustion of SRC will be
the Multimedia Environmental Goals (MEG's).  MEG's, cur-
rently being developed by EPA, are levels of significant
contaminants or degradents (in ambient air, water, or land,
or in emissions or effluents conveyed to the ambient media)
that are judged to be (1) appropriate for preventing certain
negative effects in the surrounding populations or ecosys-
tems, and (2) representative of the control limits achiev-
able through technology.  MEG's are divided into two dis-
tinct sections, Ambient Level Goals and Emission Level
Goals, and have been published for more than 200 compounds.
The November 1977 version of the MEG's chart is shown in
Figure 4.

     Emission Level Goals presented in the top half of the
MEG's chart pertain to gaseous emissions to the air, aqueous
effluents to water, and solid waste to be disposed to land.
Only the gaseous emissions to the air are addressed by this
report.
                              32

-------
MULTIMEDIA
ENVIRONMENTAL
GOALS
                                 EMISSION LEVEL GOALS
 Mr.mfat3
 (PPMVott
  IppmWt)
  Und.dB/l
  (ppmWt)
                   anBMTtdMoloir
           Mfft.irr.iAT
                           (MOO**)
II. B«»d on
                                         ToMty IMOTN
                                      HMl«ttffM«l
 •To ta imHliplM by dflution tetor
AMBIENT LEVEL GOALS
Air.OT/m3
(ppmVoll
Ippm'wtt
(ppmWO
1* Cmwit or PrapoMo Anbimt
H^-tXl



•JIJTi^o,




^•miiHiow ConoHivnton
ttalAHtaai



•!££.



III. ZwoTNMhofelPoautinti
Ettfcnmd Paii^ifcli Commmmimi
M.M..M.



          Figure  4.   MEG  Chart, November  1977 Version

                                   33

-------
     Emission Level Goals based on best technology have not
as yet been developed.  Emission Level Goals based on
ambient factors have been developed for more than 200
compounds and include consideration of:

     (1)  Minimum Acute Toxicity Effluents (MATE's) - con-
          centrations of pollutants in undiluted emission
          streams that will not adversely affect those
          persons or ecological systems exposed for short
          periods of time.

     (2)  Ambient Level Goals, i.e., Estimated Permissible
          Concentrations (EPC's) - concentrations of pol-
          lutants in emission streams which,  after dis-
          persion, will not cause the level of contamination
          in the ambient media to exceed a safe continuous
          exposure concentration.

     (3)  Elimination of Discharge (EOD) - concentrations of
          pollutants in emission streams which, after
          dilution, will not cause the level of contamina-
          tion to exceed levels measured as "natural back-
          ground."

Columns are provided on the MEG chart under Emission Level
Goals for each of these.  For additional information con-
cerning MEG's, readers are referred to Multimedia Environ-
mental Goals for Environmental Assessment. Volumes 1 and 2,
(EPA-600/ 7-7 7rTl6a and b) .
     Table 21 provides a comparison of SRC air emissions
with the MEG values for the inorganic elements analyzed in
Part II.  Chromium is the only element which fails to meet
the MATE value.  Zinc and boron are the only elements which
meet the ambient level goal values.  However, as shown in
the table, the MEG value for zinc is not much lower than
ambient level and if sampling and analytical uncertainties
were added, zinc would not meet the goal.  None of the
elements meets the elimination of discharge values.


S09 AND NO
  te       2£

     One method of assessing the environmental impact of S02
and NOX emissions from the combustion of SRC is by com-
parison with existing New Source Performance Standards
(NSPS).  The existing NSPS for S0£ and NOX are 0.52 and 0.30
kg/GJ  (1.2 and 0.7 lb/106 Btu) input, respectively.  The
average emission rates for SOo and NOX during the combustion
of SRC at Plant Mitchell were 0.46 and 0.19 kg/GJ (1.06 and
0.43 lb/106 Btu) respectively, well within the existing
standards.  However, EPA is currently considering reducing

                              34

-------
                              TABLE  21.   COMPARISON OF SRC AIR EMISSIONS WITH MEG's
Constituent
Aluminum
Antimony
Arsenic
Barium
Boron
Chromium
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Thorium
Uranium
Vanadium
Zinc
Minimum Acute
Toxicity Effluent
Based on
Health
Effects*
5,200
500
2
500
3,100
1
200
150
6,000
5,000
50
15
	
9
500
4,000
Based on
Ecological
Effects*
	
	
	
	
	
	
	
— — —
	
	
10
	
	
	
1
	
Ambient Level Goal
Based on
Health
Effects*
12.6
1.2
0.005
1
74
0.002
0.5
0.36
14
12
0.01
0.035
	
0.5
1.2
9.5
Based on
Ecological
Effects*
	
	
	
	
	
	
	
___
	
	
1
	
	
	
0.1
	
Elimination
of Discharge
Natural
Background*
	
0.007
0.00005
0
	
0.012-0.001
0.01-0.41

0.002-0.47
1.4-800
0.005-0.047
	
0.0006-0.021
	
	
0.005-0.024
0.013-0.2
SRC
June 14, 1977*
215.03
3.57
1.42
11.71
1.95
16.61
0.63
799.62
1.40
57.90
62.55
2.06
13.46
1.08
3.53
5.91
9.02
GJ
Ul
     *   Values are in yg/m

     	 Values have not yet been developed

-------
the S02 NSPS to 0.26 kg/GJ (0.6 lb/106 Btu).  It is ques-
tionable whether SRC can meet this standard.

     As discussed earlier abnormally high excess air was
used during the combustion test.  Table 4 shows high concen-
trations (10.6 to 14.8%) of free oxygen in the flue gas.
This high oxygen content is equivalent to about 240 to 100%
excess air.  The combination of molecular No and Oo by ther-
mal fixation is an equilibrium reaction with 'the final con-
centration of NO primarily dependent on the reaction tem-
perature.  The higher the temperature the higher the equili-
brium concentration of NO in presence of excess air.  How-
ever, at very high excess air the temperature decreases and
so does the concentration of NO.
                              36

-------
                        BIBLIOGRAPHY
Cleland, J.G. and G.L. Kingsbury.  1977.  Multimedia Envi-
     ronmental Goals for Environmental Assessment, Volumes I
     and II.  EPA-600/7-77-136a and b.  U.S. Environmental •
     Protection Agency, Washington, D.C.  148 pp.

Hamersma,  J.W., S. L. Reynolds,  and R.F. Maddalone.  1976.
     IERL-RTP Procedures Manual:  Level 1 Environmental
     Assessment.  EPA-600/2-76-160a.  U.S. Environmental
     Protection Agency, Washington, D.C.  131 pp.

Koralek, C.S. and V.B. May.  Flue Gas Sampling during the
     Combustion of Solvent Refined Coal in a Utility Boiler.
     Paper presented at Third Symposium on Environmental
     Aspects of Fuel Conversion Technology, III.  EPA-600/7-
     78-063.  Hollywood, Florida, September 13, 1977.

Nichols, G.B., S.M. Banks, J.R. McDonald, W.J. Barrett,
     W.R.  Dickson, and J.E. Paul.  1978. Evaluation of
     Electrostatic Precipitator at Plant Mitchell.  Contract
     No. 68-02-2610.  EPA-609/7-78-129.  U.S. Environmental
     Protection Agency, Washington, D.C.  48 pp.

Rubin, E.S. and F.C. McMichael.  Impact of Regulations on
     Coal Conversion Plants.  Environmental Science and Tech-
     nology, Vol. 9, No. 2, February 1975.  112-117 pp.
                              37

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                                TECHNICAL REPORT DATA
                         (Please read Instructions on the reverse before completing)
 1. REPORT NO.
  EPA-600/7-79-004
         2.
                                                     3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
Air Emissions from Combustion of Solvent
 Refined Coal
                                   5. REPORT DATE
                                    January 1979
                                   6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)

Kenneth G. Budden and Subhash S. Patel
                                   8. PERFORMING ORGANIZATION REPORT NO.

                                   H1T-C165/860-78-733D2
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Hittman Associates,  Inc.
9190 Red Branch Road
Columbia, Maryland 21045
                                   10. PROGRAM ELEMENT NO.
                                   EHE623A
                                   11. CONTRACT/GRANT NO.

                                   68-02-2162
12. SPONSORING AGENCY NAME AND ADDRESS
 EPA, Office of Research and Development
 Industrial Environmental Research Laboratory
 Research Triangle Park, NC  27711
                                   13. TYPE OF REPORT AND PERIOD CO
                                   Task Final; ^/77 - 9/78
                                                           VERED
                                   14. SPONSORING AGENCY CODE
                                     EPA/600/13
IS. SUPPLEMENTARY NOTES

2851.
IERL-RTP project officer is William J.  Rhodes, MD-61, 919/541-
  . ABSTRACT
                                 of & Solvent Refined Coal (SRC) combustion test at
 Georgia Power Company's Plant Mitchell, March, May, and June 1977. Flue gas
 samples were collected for modified EPA Level 1 analysis; analytical results  are
 reported. Air emissions from the combustion of coal and SRC are compared for
 various organic and inorganic constituents , and SO2  and NOx.  The impact of the
 air emissions from the combustion of SRC is assessed by comparison with EPA's
 Multimedia Environmental Goals and existing New Source Performance Standards.
 Air quality emissions test data indicated that SRC SO2 and NOx emissions were 1. 06
 and 0.43 Ib/million Btu, respectively; or about 12 and 39% under the existing NSPS
 of 1.2 Ib/million Btu for SOx  and 0. 7 Ib/million Btu for  NOx. If the SO2 standard is
 reduced, SRC derived from high sulfur coal may not meet the new standard. The low
 NOx  emissions  may be a result of the abnormally high excess air that was used du-
 ring the test: additional testing at normal conditions  is required. Particulate emis-
 sions can probably be controlled well below the EPA standard of 0. 1 Ib/million Btu
 by installing a modern ESP, with a particulate collection efficiency of about 95%.
17.
                             KEY WORDS AND DOCUMENT ANALYSIS
                DESCRIPTORS
                       b.IDENTIFIERS/OPEN ENDED TERMS
                        c. COSATI Field/Group
Air Pollution
Coal
Liquefaction
Combustion
Flue Gases
Analyzing
   Nitrogen Oxides
   Sulfur Oxides
   Dust
Air Pollution Control
Stationary Sources
Solvent Refined Coal
Particulate
13B
21D
07D
21B

14B
07B

11G
18. DISTRIBUTION STATEMENT

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                        21. NO. OF PAGES
                              45
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EPA Form 2220-1 (9-73)
                                       38

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