X-/EPA
                              United States
                              Environmental Protection
                              Agency
                              Industrial Environmental Researcl
                              Laboratory
                              Research Triangle Park NC 27711
                              Research and Development
                               EPA-600/S7-81-077   July 1982
Project  Summary
                              Environmental Assessment:
                              Source Test  and  Evaluation
                              Report—Exxon  Miniplant
                              Pressurized  Fluidized-Bed
                              Combustor with  Sorbent
                              Regeneration

                              R. J. Kindya, R. R. Hall, G. T. Hunt, W. Piispanen, and P. F. Fennelly
                               The report gives results of a compre-
                              hensive emission sampling and analy-
                              sis  program conducted at the EPA-
                              sponsored Exxon Miniplant, a pres-
                              surized coal-fired fluidized-bed
                              combustor and sorbent regeneration
                              system. The sampling and analysis
                              methods used provide screen ing data
                              on  organic and inorganic pollutants
                              and indications of biological activity;
                              however, in general,  they are  not
                              designed to provide final quantitative
                              results.
                               Air pollutant emissions of trace
                              elements were measured and com-
                              pared to appropriate emissions goals.
                              Seven inorganic trace elements ex-
                              ceeded emissions goals in the com-
                              bustor flue gas, indicating a need for
                              further investigation.
                               Air pollutant emissions of total
                              organics were less than for comparable
                              conventional combustion systems.
                              Limited further analyses for specific
                              polynuclear  aromatic compounds
                              indicated  that emissions of one of
                              these compounds  exceed its emis-
                              sions goal.
                               Analysis of laboratory-generated
                              leachates from solid waste samples
                              revealed trace metal concentrations
                              well below Federal hazardous waste
                              criteria.
                                Positive results for mutagenicity
                              and cytotoxicity screening tests re-
                              quire further investigation. Similar
                              results have been reported for other
                              coal-fired fluidized-bed combustors
                              and conventional combustion systems.
                                This Project Summary was devel-
                              oped by EPA's Industrial Environ-
                              mental Research Laboratory, Research
                              Triangle Park. NC. to announce key
                              findings of the research project that is
                              fully documented in a separate report
                              of the same title (see Project Report
                              ordering information at back).

                              Introduction
                                The development of fluidized-bed
                              combustion (FBC) is being supported by
                              the  Federal government, private
                              industry, and utility groups because of
                              its potential advantages over conven-
                              tional coal combustion methods. Re-
                              duction of S02 during the combustion
                              process is the primary advantage of FBC
                              because it eliminates the need for add-
                              on flue gas desulfurization equipment.
                              Other advantages include a potential
                              reduction in capital costs (compared to a
                              conventional coal-fired boiler) and the
                              capability to burn a wide variety of fuels,
                              including  such low-grade fuels as
                              anthracite culm, coal cleaning wastes,
                              and  industrial wastes. An additional

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advantage of pressurized fluidized bed
technology is the potential to achieve
higher fuel-to-electricity  efficiencies
than conventional systems.
  In fluidized-bed combustion, a mix-
ture of coal and limestone is supported
on  a grid at the bottom  of a  boiler.
Combustion air passes through the grid
at high velocities, typically 1.2 - 2.4 m/s
(4 - 8 ft/s). The upward flow of the air
holds the solids in suspension, creating
a quasi-f lu id that possesses many of the
properties of the  liquid. The  most
important liquid-like  property  to the
boiler designer  is  the  fact that bed
material is exceptionally well mixed and
flows throughout the system without
agitation.  This well-mixed semiliquid
state produces high heat transfer rates
and permits combustion at temperatures
in the 760 - 930°C (1400 - 1700°F)
range.
  The EPA-sponsored  Exxon Miniplant
was a pressurized  fluidized-bed com-
bustor (PFBC) and sorbent regeneration
system with a coal-firing capacity of 1.8
MW (6.3 x 106 Btu/hr). Exxon operated
the Miniplant from  early 1974  to the
summer  of 1979, when the  program
ended. During the several thousand
operating hours,  extensive investiga-
tions of sulfur capture, NOX emissions
and control,  high-pressure/high-tem-
perature particulate control, combustion
efficiencies, and many other aspects of
FBC were completed. Sorbent regener-
ation was demonstrated in 1975  and an
experimental program including sorbent
regeneration was  conducted during the
first half of 1979.
  This report discusses  results  of
comprehensive sampling and analysis
conducted by GCA/Technology Division
at the Exxon Miniplant m May  1979.*
These efforts were based on a phased
approach to environmental assessment
developed by EPA's Process Measure-
ments Branch at the Industrial En-
vironmental  Research  Laboratory  at
Research Triangle Park, NC (IERL-RTP).
The first  phase,  Level  1, involves a
screening approach using sampling and
analytical techniques that sacrifice
accuracy and compound specificity in
order to  identify any possible problem
areas in a cost-effective manner. Level
1 should yield final analytical  results
within a factor of ±3. These results can
be  used to: provide preliminary envi-
 *GCA/Technology Division conducted the field
  measurement program under U S EPA Contract
  68-02-2693, Exxon Research and Engineering
  operated the Miniplant and supported the field
  program under U S EPA Contract 68-02-1312
ronmental assessment data;  identify
problem areas; and formulate the data
needed to rank energy and industrial
processes, streams within a process,
and components within a stream, for
further consideration in the overall
assessment. The second phase. Level 2,
is directed by  Level 1 results  and is
designed  to  provide additional, more
specific,  accurate, and quantitative
information that will confirm and
expand the data gathered in Level 1. The
primary  focus of the sampling and
analysis discussed in this report was at
Level 1.  Some Level 2 analytical work
was conducted.

Facilities Description and
Emission Streams Sampled
  Figure  1 is a simplified schematic
diagram of the Exxon  Miniplant as it
operated  during the Level 1  sampling
program. As indicated, 11 streams were
sampled  for  Level  1  analysis at the
Miniplant. These samples are listed and
described  in  Table 1. Individual com-
ponents  of the  process  are briefly
described  below.

Process Description
  Coal and sorbent are injected pneu-
matically into the combustor  through a
single  port,  28 cm (11 in.)-above the
water-cooled fluidizing grid. The flow of
coal is controlled to maintain constant
temperature in  the combustor.
  The combustor is a 9.75 m (32 ft) high
refractory-lined vessel with an i.d. of 33
cm {13 in.). Heat of  combustion  is
removed  by water-cooled tubes in the
fluidized  bed. Coal feed  rates of 230
kg/hr  (500  Ib/hr) and expanded bed
heights of 6.1 m (20 ft) are possible, but
the unit usually operates at about half
these values. The unit  is water cooled
with both the cooling water temperature
and metal temperature continuously
measured.
  Solids  are rejected  from  the com-
bustor through a port abovethefluidizing
grid. From this port, the solids flow by
gravity through a steel pipe into a pulse
pot.  The solids are then pneumatically
transported  by controlled  nitrogen
pulses to a pressurized lockhopper from
which they are periodically dumped into
metal  drums.  A similar system, not
including  a  pressurized lockhopper, is
used to transfer solids tothe regenerator.
  Combustion  and fluidizing  air are
provided  by a mam air  compressor
(shown in Figure  1).  Pressure in the
combustor is controlled by maintaining
a specified gas flow, across  an appro-
priately sized ceramic-coated orifice, b
dilution of the flue gases with  higl
pressure air as shown in the top c
Figure 1 .
  The sorbent regenerator consists of ;
refractory-lined vessel with an i.d. of 2'.
cm (8.5 in.) and an overall height of 6.'
m (22 ft). Operating temperatures a
high as 1 100°C (2000°F) and pressun
up to 1000kPa (10atm)canbeachievei
in the regenerator.  Typical superficia
velocity is  0.6  m/s (2 ft/s) with ai
expanded bed height of 2.3 m (7.5 ft).
  The regeneration process is based 01
the one-step reductive decomposition o
CaSCU by the reaction:
CaS04

    CaO
                             S02
An  undesirable  competing  reactior
involving  the  formation  of  CaS  als<
occurs:
CaS04 + 4
H2
CO
                   CaS + 4
Therefore, an oxidizing zone is providet
in the regeneration vessel to conver
CaS to CaS04:
       CaS + 202
           CaSO4
                                 (3
  At the  Miniplant, natural gas  is
burned in  the plenum below the
fluidizing grid to achieve the reactior
temperature. Additional fuel is injectec
directly into the bed, just above the
fluidizing grid, to create a reducing zone
in which reaction  (1) occurs. Supple
mentary air  is injected into the fluidizec
bed  to create an  oxidizing  zone  tc
convert CaS to CaSO4 via reaction (3).

Flue Gas and Flue Gas
Particulate Handling
  Flue gas and entrained solids (fly ash
and  sorbent) exit the top of the com-
bustor and enter a  three-stage cyclone
system. Solids separated by the first-
stage  cyclone drop through a  stee
dipleg and enter a pulse pot from whicr
they are pneumatically conveyed bacl<
to the combustor  (100 percent rein
jected). Solids (primarily fly ash) escaping
the primary cyclone enter more efficiem
second- and third-stage cyclones where
finer sizes of solids are captured. The
third-stage cyclone operates at 85 to 94
percent efficiency.  The final flue gases
generally contain 0.03 to 0.15 g/Nm3 o1
particulates  with a mass median diam-
eter  of 1 to  3 /urn.  The collected solids
from these cyclones pass  thr-ougl"
separate diplegs and enter pressurizec

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                                                                                       To ESP
                                                                                               To
                                                                                               Scrubber
                                                                                                       Scrubber
                                                                                                        Slurry
  (£/
  . 'Coal and
   Limestone
   Feed Supply
  A uxiliary
  Air
  Compressor
                     Indicated Stream Sampled
                                 a
    Natural Gas
    Compressor

Main Air
Compressor
Figure 1.    Schematic of the Miniplant PFBC as it operated during the Level 1
            environmental assessment with Level 1 sampling points indicated.
lockhoppers  from which solids are
periodically dumped into metal drums.
  After leaving the third-stage cyclone,
the flue gas expands through a converg-
ing nozzle. A secondary source of high
pressure air is metered through a ball
valve  with  a  pneumatic  actuator and
positioner. Superimposing this sec-
ondary flow of air on the primary flow of
flue gas through the nozzle, maintains
gas pressure  in the combustor at the
desired  level,  typically 950  kPa (9.5
atm).
  During the  Level  1  tests,  the EPA
mobile electrostatic precipitator was
used to remove  additional paniculate
from the  cooled, depressurized flue
gases. This experiment was conducted
because the final paniculate concen-
tration of 0.03 to 0.15 g/Nm3 might be
adequate for process performance, but
emissions  would need to be limited to
13 ng/J (about 0.035  g/Nm3) to meet
Federal New Source Performance
Standards  for utility boilers.
  Hot flue gases from  the regenerator
pass  through a  cyclone  to  remove
entrained particles Next the gases are
cooled from 930°C (1700°F) to about
200°C (390CF) in a water-cooled heat
exchanger. Gases  are depressurized
before entering  a  scrubber for final
cleanup before venting  to the atmos-
phere.


Operating Conditions

  Combustor and regenerator operating
conditions during the EPA tests are
listed in Table 2 Champion coal (with a
sulfur content of 1.7 percent) andGrove
limestone were used. It was necessary
to feed significant  quantities of fresh
limestone to compensate for elutnation
and to maintain  the  bed in the com-
bustor. Because  high sulfur coal was
not available, the resultant Ca/S ratio
was 1.29, much higher  than desirable
for commercial regenerative  operation.
Also, system pressure was 700 kPa (7
atm), instead of the normal 950 kPa (9.5
atm), to  achieve adequate  fluidizing
velocities in the regenerator. Because
the pressure was 30 percent lower than
previous  experimental runs, coal feed
rate was reduced to  maintain  the
desired excess air at the specified
fluidizing velocity.

Sampling and Analytical
Methodology

Sarppling Techniques
  Six solid streams were sampled at the
Miniplant: two feed streams and  four
waste streams. Samples for chemical
and  most biological  analyses were
collected every 2 hours during the flue
gas sampling.  All  solid samples were
split for organic and inorganic analysis.
The  individual organic and inorganic
samples were each composited during
the test run to provide a representative
sample of each solid stream
  To provide samples of the combustor
flue gas and the regenerator offgas for
Level 1  Environmental Assessment
analysis, the Source Assessment
Sampling System (SASS) was used to
collect  samples of the paniculate  and
gaseous components of each indicated
gaseous stream.
  The SASS tram collects particles in a
series of three cyclones with nominal

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Table 1.    Summary of Stream Sample Characteristics
Sample Point
Identification
     No.
       Stream Description
Physical
 State
Collected
   By
Important Characteristics
      1      Diluted combustor flue gas (cooled)    Gas
               (ESP hopper catch)              and solid
      2      Undiluted combustor flue gas (hot)    Gas


      3      Regenerator flue gas (cooled)        Gas


      4      High pressure dilution air            Gas


      5      Solids from regenerator cyclone     Solid

      6      Spent combustion bed solids        Solid
       7     Solids from second combustor
               cyclone
             Solids from third combustor
               cyclone
      9

      10

      11
Cool feed

Sorbent feed

Scrubber slurry
  Solid



  Solid



  Solid

  Solid

 Liquid
  GCA   Fly ash entrained in combustion gases, particle concer
         tration about 0.15 g/Nm3, mass median particle sizi
         below 5 cm. Temperature 175°C (350°F), pressure 13
         kPa (5 psig).

  GCA   Similar to (1) but temperature is 750°C (1500°F) and
         pressure is 700 kPa (7 atm).

  GCA   Sorbent particles entrained in off gases, low particle
         loading, temperature and pressure similar to (1).

  GCA   Compressor output containing organic residue from
         lubricating oil, pressure is 700 kPa (7 atm).

 Exxon  No special characteristics.

 Exxon  Solids stream containing spent sorbent and some botton
         ash, discharge temperature approximately 900° C
         (1700°F).

 Exxon  Stream contains fly ash, particles of mass median
         diameter approximately 17 cm, temperature approxi-
         mately 150 to 300°C (300 to 600°F).

 Exxon  Stream contains fly ash, particles of mass median
         diameter approximately 4 cm, temperature approximatel
         150 to 300°C (300 to 600°F).

 Exxon  No special characteristics.

 Exxon  No special characteristics.

 Exxon  Liquid stream containing fly ash from stream 3 to
         condensed compounds, also ammonia, temperature 25 tc
         40°C (70 to  100°F).
 cut points of 10 /urn, 3/um, and 1 /urn. A
 150-mm filter collects the particles that
 are  less than 1 /urn in  diameter. The
 volatile organics are captured by 150 g
 of XAD-2 resin in a  temperature-
 controlled trap. A series of  impingers
 follows the resin trap to capture volatile
 metals. Setup and performance of the
 SASS train followed Level  1  specifi-
 cations.
  The SASS train samples of the diluted
 combustion flue  gas (stream 1) were
 obtained from a temporary duct leading
 to the mobile  ESP. Samples  were
 collected on May 3 and  4, 1979.
  Because organic contamination of the
 diluted combustor flue gas by the
 compressed air  used for dilution was
 suspected,  additional sampling  was
 conducted before dilution (stream 2).
                           The  SASS train  cyclones,  filter,  and
                           oven  were not used at this sampling
                           location because the Balston filter in the
                           sample treatment system had already
                           collected the particulates. The Balston
                           filter operated at 260°C (500°F).  A
                           SASS train organic module was used to
                           collect volatile and nonvolatile organic
                           species. Sampling was accomplished by
                           connecting a flexible stainless steel line
                           to the existing metering valve.
                             The regenerator flue gases were also
                           sampled with the SASS train. Sampling
                           was  conducted at approximately  iso-
                           kinetic conditions in the center of the
                           6.4cm (2.5 in.) i.d. pipe transporting the
                           regenerator flue gases. Sampling  was
                           conducted on May 2 and 3,  1979.
                             A small resin trap containing 25 g of
                           clean XAD-2  was  used  to  collect
                                   organics in the dilution air. For sample
                                   collection, the resin trap was adapted t<
                                   a glass EPA Method 5 sampling train
                                   The sampling train was attached to ar
                                   existing  tap  on the  compressed  ai
                                   supply line. A metering valve was use<
                                   to control the sample flow rate am
                                   reduce  the pressure to acceptable
                                   levels. The samples were recovered ty
                                   transferring the  XAD-2  to  an ambei
                                   glass jar and then rinsing the resin trap
                                   with  methylene  chloride (distilled-in
                                   glass  grade).
                                     Gaseous components of the Mini
                                   plant flue gas streams were sampled fo
                                   subsequent analysis using a combina
                                   tion of  continuous withdrawal, gral:
                                   sampling, and special impinger  trair
                                   techniques. Analyses  were conductec

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 Table  2.    Summary of Miniplant PFBC Operating Conditions
           Parameter
  Combustor
   Regenerator
 Length of run, hr
 Pressure. kPa
 Average bed temperature, °C

 Expanded bed height, m
 Superficial velocity, m/s

 Ca/S molar ratio
 Coal feed rate, kg/hr
 Coal type (percent S)
 Coal higher heating value, kJ/kg
 Coal size, mesh
 Sorbent feed rate, kg/hr
 Sorbent type
 Sorbent size, mesh
 Excess air, percent
 Flue gas oxygen content, percent
       99
      700
      894

     3.1
      1.5

      1.29
       77
 Champion (1 .7)
    31,400
        81
       705
    1010-1031
(oxidizing-reducing)
       1.9
     0.6-0.8
(oxidizing-reducing)
     5.4
Grove limestone
    8x25
       46
     4.1
  Grove limestone
       0.3
for CO, CO2, 02, N2, SO2, H2S, COS, CS2,
ammonia, and cyanide.
  Grab  samples of the four  gaseous
streams for low-boiling (< 100°C)
organic  analysis  were  obtained in
evacuated 2-liter glass sampling bulbs.
Inorganic  fixed gas samples were
obtained as integrated Tedlar  bag
samples.
  Exxon  personnel  provided  a  single
sample  of scrubber slurry for Level 1
testing.

Analytical Techniques
  Inorganic  constituents  of Miniplant
effluent stream samples were quanti-
fied using a combination of instrumental
and  wet chemical techniques. The
primary Level 1  inorganic analysis
technique is  spark source  mass
spectrometry, which provides sensitive
detection limits for about 70 elements
Interferences, such as variations in the
ion source discharge conditions and the
photoplate interpretation techniques
used  in  Level  1, provide only  semi-
quantitative data accurate to within a
factor of 2 or 3.
  Miniplant bulk solid streams, having
the  potential to be disposed of in a
landfill or another area where leaching
could occur,  were subjected  to inor-
ganic analysis of both the solid material
and laboratory-generated distilled water
leachates. Atomic absorption spectrom-
etry  was  used  to accurately  quantify
selected elements in the leachates.
  The Level 1 test protocol attempts to
identify  the major  organic  compound
classes  within each  sample stream
    tested. Methylene chloride extracts of
    the samples are analyzed.  Qualitative
    and some quantitative data are gener-
    ated, using gravimetry, gas chromatog-
    raphy,  liquid chromatography, infrared
    spectroscopy, and low resolution mass
    spectrometry. These Level 1 techniques,
    in general, do  not provide  data on
    specific compounds. Level  1  methods
    were supplemented with high  per-
    formance liquid chromatography  using
    fluorescence detection for poly nuclear
    aromatic compounds.
      Volatile organics (boiling points below
    100°C) are separated into six boiling
    point ranges by onsite gas chromatog-
    raphy. Moderately volatile organics
    (boiling points  100 - 300°C), in methy-
    lene chloride extracts, are analyzed in
    the laboratory  by gas chromatography.
    Flame  ionization detection  is used in
    both of the above  cases. Nonvolatile
    organics  (boiling points  above 300°C)
    are measured by gravimetric methods in
    methylene chloride extracts. These
    organic  concentration data provide
    some qualitative indication of the types
    of compounds  that may be present.
      Level  1 liquid chromatographic (LC)
    separation was  designed to  separate
    samples  into seven  reasonably distinct
    classes of organic compounds and was
    applied to all samples that contained a
    minimum of 15 mg combined volatile
    and nonvolatile organics. A sample was
    placed on a silica gel liquid chromat-
    ographic column, and a series of eluants
    of sequentially increasing polarity were
    used to  separate the  sample  into
    fractions for further analysis.
  Infrared analysis was used to deter-
mine the functional groups in an organic
sample or liquid chromatography frac-
tion of a  partitioned sample. The
interpreted spectra provide information
on functionality (e.g., carbonyl, aromatic
hydrocarbon,  alcohol, amine, aliphatic
hydrocarbon, and halogenated organic).
  Level 1 bioassays are a cost-effective
initial  screening  tool that  indicates
potential health or ecological effects. As
such, the test results should be used to
point  out areas requiring further  in-
vestigation. Health  effects tests con-
sisted of the Ames test for mutagenicity,
and mammalian cell cytotoxicity assays
using  rabbit alveolar macrophages
(RAM) and Chinese  hamster ovary
(CHO)  cells. Fathead minnows, daph-
nids, and algae were used to  test  for
acute ecological effects.

Results

Data Handling
  Criteria or  standards for air, water,
and solid waste pollutants are needed to
properly determine the implications of
test results. Federal standards exist for
some pollutants, such as total particu-
lates, NOX, and S02 in boiler flue gases.
Federal criteria are also  available to
determine if a solid waste is considered
hazardous. However, emission standards
do  not exist for most of the pollutants
measured in this  and other environ-
mental assessment programs.
  IERL-RTP has  developed a  set of
conservative Discharge Multimedia
Environmental Goals (DMEGs). They
are derived using models incorporating
available exposure or recommendations
data such as  industrial Threshold Limit
Values (TLV),  NIOSH recommendations
for worker exposure, drinking water
criteria, results of toxicity experiments
using animals, and EPA/NIOSH order-
ing numbers or animal data on carcino-
genicity.  These goals are  emission
concentrations that are used in  IERL-
RTP research  programs to provide
perspective on potential environmental
hazards, to provide direction for control
technology 'research programs, and to
rank  emission  streams  for  future
investigation. These conservative goals
are a screening tool to provide focus for
further, more detailed investigation.
  The  simplest model used  to derive
DMEG limits  incorporates  TLVs as  air
pollutant emission goals. Emission
concentrations below the TLV are
assumed to be safe, since dispersion
usually produces ground-level concen-

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trations lower than stack concentra-
tions by a factor of 1000 or more. This
dilution  factor should,  in  general,
provide adequate protection for chronic
exposure of the general population. The
other  goals and models are based on
similar but more complex (and, at times,
more tenuous) extrapolations.
  Measured trace element concentra-
tions for each Miniplant effluent stream
sample were compared  to  their in-
dividual DMEG specific for the media of
interest (air, water,  solid  wastes).
Elements in excess of their goals were
"flagged,"  providing a  mechanism to
estimate potential  hazards associated
with emission  of that stream.  Such
estimates may be  made to reflect both
human health and ecology. Elements in
excess of their DMEG indicate a  need
for further investigation.


Summary of Test Results
  Data generated from Level 1 analyses
of Miniplant samples  were of three
general types: inorganic analysis rely-
ing on spark source mass spectroscopy
(SSMS), atomic absorption spectrometry
(AA),  or wet chemical  techniques;
organic analysis  using gravimetry,
liquid chromatographic separation,
infrared spectrophotometry, or low
resolution mass spectrometry (and
onsite gas chromatography for gaseous
streams);  and bioassay results of
specific  health or ecological effects
testing.
 Inorganic Data
  Table 3 summarizes inorganic ele-
 mental data for Miniplant samples. Data
 are from SSMS or AA for gaseous waste
 stream samples, solid stream samples,
 and laboratory-generated distilled
 water leachates. Measured concentra-
 tions were compared to their respective
 appropriate emission goals (DMEGs).
  Table 3 data  show  seven  elements
 exceeding emissions  goals in com-
 bustor  flue  gas.  Flagging  of these
 elements  indicates a potential area for
 Level 2  investigation. However, Level 2
 efforts would have to be preceded by
 validation of the Level  1 SSMS results.
 Some elemental concen-trations,
 especially Cr, Ni, and Fe, may have been
 high because of contamination from the
 stainless  steel  of  the  sampling train.
 Although  four  elements  exceed  their
 DMEG in  regenerator  flue gas, further
 analyses  of this stream  are unlikely.
 Regenerator flue gas would be treated
Table 3.    Summary of Inorganic Trace Element Data for Miniplant Samples
     Stream Description
Number of Chemical
  Species >DMEG
Identity of Chemical
 Species >DMEG
Gaseous waste streams3
  Regenerator flue gas                 4
  Combuster flue gas6                 7

Solid streams0
  Regenerator cyclone solids           14

  ESP hopper ash                    16

  Second combustor cyclone           14
   solids
  Third combustor cyclone             15
   solids
  Spent combustion bed               4
   material

Laboratory-generated,
distilled water leachatesd
  Regenerator cyclone solids            0
  Second combustor cyclone
   solids                             0
   Third combustor cyclone solids       0
  Spent combustion bed
   material                           0
  Coal feed                           0
  Sorbent feed                        0
                    V, Cr, Ni, Rh
                    P, Ca, V, Cr, Fe, Ni, As
                   Be, Al, P, Ca. Ti, V, Cr, Mn, Fe,
                   Ni, Cu, Zn, As, Cd
                   A I, P, Ca. Ti, V, Cr. Mn, Fe. Ni.
                   Cu, Zn, As, Se, Cd, Ba, Pb
                   Al. P, Ca. Ti, V. Cr, Mn, Fe. Ni,
                   Cu.Zn.As.Cd.Pb
                   Al, P. Ca. Ti, V. Cr. Mn. Fe, Ni.
                   Cu, Zn. As, Se, Cd, Pb
                   Ca, P, Fe, Ni
aAir DMEGs used for comparison.
'"Results represent emissions for the total flue gas stream. Dilution air was not
 analyzed and is assumed not to contribute to the totals of inorganics analyzed.
cLand DMEGs used for comparison.
d Water DMEGs used for comparison.
before venting to the atmosphere and
thus does not represent a true emission
stream.
  Bulk solid waste  streams  from the
Miniplant PFBC were chemically evalu-
ated in two ways. Solid samples were
analyzed for trace elements by SSMS
(AA for Hg and Sb) and compared to land
DMEG emission goals.  In  addition,
distilled water leachates were prepared,
analyzed in a similar manner, and the
results compared to water DMEGs.
  As seen in Table 3, numerous, albeit
similar, trace elements exceeded their
respective land DMEGs in all solids col-
lected  by the various control devices
used  at the  Miniplant. Only  four
elements exceeded one or both land
DMEGs  for  Spent Combustor Bed
Material. When laboratory leachates of
these  bulk solid materials were pre-
pared and  analyzed, however, no
element  in any  sample exceeded any
           discharge goal. In fact, most elemental
           concentrations in the leachates were
           more than  two orders  of  magnitude
           below their goals.  Based on these
           leachate data, leaching of potentially
           toxic species from disposed solid waste
           streams  at  the Miniplant  would not
           appear to be  a problem. Solid waste
           streams would, therefore, be at a lower
           priority for subsequent Level 2 analysis
           than would  flue gas particles.

           Organic Data
             Samples from the Miniplant generally
           contained low levels  of organic com-
           pounds compared to DMEGs and Level
           1 organic analysis criteria.
             The SASS train organic module (XAD-
           2 resin adsorbent extracted with ChfeClz)
           from the regenerator flue gas streams
           and the diluted combustor flue gas
           stream were the only samples analyzed
           that contained sufficient organic mate-

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 Table 4.    Summary of Bioassay Results of Miniplant PFBC Samples
                                     Health Effects Tests
                                          Ecological Effects Tests
Sample
Description
Scrubber slurry
XAD blank
Combustor flue
gas - XAD
Regenerator flue
gas - XAD
Fine SASS
paniculate
Coarse SASS
paniculate
SASS filter-control
ESP hopper ash
Regenerator cyclone
Combustor bed
material
2nd Cyclone catch
3rd Cyclone catch
Ames RAM
Mutagenicity* Cytotoxicity
/V
N

+ N

+ N

+ N

+ N
N
+ Low
Low

Low
Low
Moderate
CHO
Cytotoxicity"
_
-

-

High

N

N
N
N
N

N
N
N
Fish
(96-hour LCso)
High
N

N

N

N

N
N
N
High

High
High
Low
Daphnids
(48-hour LCscJ
High
N

N

N

N

N
N
N
High

High
High
Moderate
Algae
[ECscJ
Moderate
N

N

N

N

N
N
N
High

High
High
High
 *+/- = positive/negative mutagenic response; no detectable toxicity.
 b/V = not run for indicated sample.
 °- = negative CHO cytotoxicity response
rial to  require liquid chromatographic
separation. Because organic concentra-
tions were so low, the infrared spec-
trometry  and low  resolution mass
spectrometry analyses provided only
general results that were of limited use
  Samples analyzed from the Miniplant
generally contained such  low levels of
organic compounds that these data
were interpreted as:
   1. Initial Level 1 organic data were
     compiled,  including totals for
     volatile  species (TCO-total chro-
     matographable organics),  non-
     volatile species (GRAV-gravimet-
     ric), and onsite GC spectra where
     applicable.
   2. A survey was made of all DMEG
     values that have been adopted for
     organic  compounds  or classes of
     compounds (586 to date).
   3  It was assumed that the total
     weight of organics present in the
     sample analyzed was representa-
     tive of one  compound, as a worst
     case, and  all  species  whose
     DMEG was lower than this total
     were listed This exercise resulted
     (for  some  samples)  in a  list of
     compounds of "potential concern "
     In other samples,  this exercise
     resulted in eliminating organic
      compounds as an area of concern
      for future investigation.
   4.  These compounds were then re-
      viewed based on knowledge of
      process chemistry, operating
      conditions,  and the available
      Level  1  bioassay results. This
      review eliminated some species
      that could not possjbly be present
      in these FBC emission streams.
   5  A final list (on a stream-by-stream
      basis)  of  organic compounds of
      potential concern was compiled.
  Organic  compounds of concern in
Miniplant emission streams appear to
be limited to polynucleararomatic(PNA)
species that might be present in SASS
tram samples (particles and XAD) from
combustor and regenerator flue gases.

Bioassay  Data
  Results of testing Miniplant samples
in the Level 1 bioassay screen are sum-
marized in  Table 4. Results are listed
based on qualitative Level 1 bioassay
response criteria, except Ames results,
which are listed as positive/negative.
  Five samples  were  positive  (muta-
genic) in  the Ames test. Except for the
third cyclone catch, all streams exhibited
low toxicity to RAM cells. Regenerator
flue-gas  XAD extract was the only
sample toxic to CHO cells. Regenerator
cyclone catch leachate, spent combus-
tion bed material leachate, and second
cyclone catch leachate all  exhibited
high toxicity  in  all ecological effects
tests Third cyclone catch leachate was
variably toxic in these tests depending
on the organism exposed.  The toxicity.
found in the ecological tests is probably
attributable to high pH.
  The resulting three sets of data from
Level 1 analysis for each tested stream
from the  Miniplant PFBC  were  com-
pared  Inorganic species that  were
flagged as  exceeding  one of  their
emission  goals,  organic  species of
potential concern possibly present in a
sample (as determined above), and the
response of a sample in the Level 1
battery  of biological tests  were  all
considered in making the final evalua-
tion of which streams should receive
priority for level 2 analysis.


Radioassay of Miniplant
Samples
  Multimedia samples collected during
the May 1979 Level 1 sampling program
at the Miniplant were analyzed for
selected radioisotopes. Radioisotope
emissions  data from  FBC are required

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    by the  EPA's Office of Radiation
    Programs to evaluate the need, if any,
    for emissions limitations  or  other
    standards or criteria as instructed by the
    Clean Air Act Amendments. Also, these
    data  serve  as an initial effort toward
    incorporation  of  radioactivity (as an
    environmental pollutant)  into the en-
    vironmental assessment  methodology
    developed by the EPA Office of Research
    and Development through IERL-RTP.
      Seven solid  samples were analyzed.
    Coal and sorbent feedstocks were
    analyzed for isotopic  uranium (234U,
    2351J, 238U) and isotopic thorium  (228Th,
    230Th). ESP hopper ash was not available
    m sufficient quantity to permit analysis
    for thorium isotopes but was  analyzed
    for isotopic  uranium, 226Ra, 228Ac, 210Pb,
    and 210Po. Regenerator cyclone solids,
    solids captured  by second and third
    combustor  cyclones, and  spent  bed
    material were assayed  for  all  nine
    isotopes.
       Data indicate that most of the radio-
    isotopes leave the system as part of the
    second  and third combustor cyclone
    catches. Radioisotopes escaping the
    plant in the Miniplant flue gases or in a
    commercial FBC facility would probably
    be 1  - 20 percent of those measured in
    the ESP hopper catch.
          R. J. Kindya, R. R. Hall. G. T. Hunt, W. Piispanen, and P. F. Fennelly are with
            GGA/Technology Division, Bedford, MA 01730.
          John 'O. Mi/liken is the EPA Project Officer (see below).
          The complete report, entitled "Environmental Assessment: Source Test and
            Evaluation Report—Exxon Miniplant Pressurized Fluidized-Bed Combustor
            with Sorbent Regeneration," (Order No. PB82-196 858; Cost: $ 18.00, subject
            to change) will be available only from:
                  National Technical Information Service
                  5285 Port Royal Road
                  Springfield, VA22161
                  Telephone: 703-487-4650
          The EPA Project Officer can be contacted at:
                  Industrial Environmental Research Laboratory
                  U.S. Environmental Protection Agency
                  Research Triangle Park, NC 27711
United States
Environmental Protection
Agency
Center for Environmental Research
Information
Cincinnati OH 45268
Postage and
Fees Paid
Environmental
Protection
Agency
EPA 335
Official Business
Penalty for Private Use S300

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