AEPA
United States
Environmental Protection
Agency
Environmental Sciences Researc
Laboratory
Research Triangle Park NC 2771
Research and Development
EPA-600/S7-80-177 Apr. 1981
Project Summary
Aerosol Characterization of
Ambient Air Near a
Commercial Lurgi Coal
Gasification Plant
Kosovo Region, Yugoslavia
K. J. Brombaugh, G. C. Page, C. H. Williams, L 0. Edwards, W. D. Balfour,
D. S. Lewis, and K. W. Lee
An atmospheric sampling and anal-
ysis program was conducted to: 1)
determine if the emissions from a
Lurgi coal gasification plant could be
identified in the ambient air in the
vicinity of the facility and to 2) deter-
mine if these emissions could be dis-
tinguished from the other emission
sources in the immediate area that
also contributed to the atmospheric
mixture of pollutants.
Physical and inorganic analyses
were carried out on the collected
particulate matter using gravimetric
analyses, ion chromatography, and
scanning electron microscopy. Ele-
ments were analyzed using induc-
tively coupled argon plasma emission
spectroscopy, proton-induced x-ray
emission analysis, and combustion
analysis. Both particle catches and
vapors trapped on Tenax® resins were
subjected to organic analysis using
gas chromatography. Flame ionization
detection and sulfur- and nitrogen-
specific detectors were employed in ad-
dition to the GC/MS method in organic
compound identification and quanti-
tation.
The results of these analyses showed
that the total atmospheric particle
loading was higher immediately down-
wind of the Kosovo industrial complex,
which includes the gasification plant.
Coal dust resulting from the handling,
grinding, and transporting of the coal
was probably a major contributor to
the particle burden.
A very complex organic mixture was
found in the vapor phase and adsorbed
on the particulate matter. Maximum
individual concentrations were 8
/jg/m3 for naphthalene in the vapor
and 0.08 fjg/m3 for the benzopyrene
isomer group adsorbed on the particles.
The naphthalene loadings were found
to correlate positively with the percent
of downwind sampling time. The
GC/MS profiles of organic compounds
found in the ambient air samples
correlated well with those observed
from emission sources at the gasifica-
tion plant (represented by middle oil,
one of the coal gasif ier's by-products).
Thus the compounds found can be
considered characteristic of the emis-
sions from the Kosovo Lurgi coal
gasification plant.
This Project Summary was devel-
oped by EPA's Environmental Sci-
ences Research Laboratory, Research
Triangle Park, NC, to announce key
-------
.**
findings of the research project which
is fully documented in a separate
report of the same title (see Project
Report ordering information at back).
Introduction
This program was aimed at assessing
the impact on ambient air quality of the
emissions from a Lurgi-process coal
gasification plant. The plant chosen for
study is located in the Kosovo region of
Yugoslavia. The Lurgi process of coal
gasification was selected for study
because it is currently being proposed
for demonstration in the United States
as a commercially feasible technology
for indirect coal liquefaction and syn-
thetic natural gas (SNG)production. The
flow scheme for the Lurgi gasification
plant at Kosovo is depicted in Figure 1
and its design data are presented in
Table 1.
The objectives of the program were
threefold:
• to sample and identify pollutants in
the ground level ambient air in the
vicinity of the Kosovo industrial
complex
• to determine if the specific pollutants
detected in this study could be
identified with the Lurgi coal gasi-
fication plant
• to evaluate the effect of the Lurgi
gasification process on the air
quality in the immediate vicinity of
the plant.
The program was designed to meet
these objectives by providing chemical
and physical data on the ambient air
samples. Species believed to be emitted
from the Kosovo gasification plant were
of special concern.
Table 1. Kosovo Gasification Plant
Design Data
Inputs:
Lignite coal
Steam
Oxygen (96 Vol %)
Outputs:
Products:
Clean gas
By-Products:
Tar
Oils
Gasoline
NH4OH
Crude phenols
80 Mg/hr
65 Mg/hr
9,900 Nrrf/hr
60,000 Nm3/hr
2.2 Mg/hr
1.3 Mg/hr
0.65 Mg/hr
0.96 Mg/hr
0.36 Mg/hr
Assessment of the environmental
effects associated with the Lurgi process
is desirable before Lurgi-based plants
are constructed in the United States. A
study of the gasification plant at Kosovo,
Yugoslavia, represented a unique oppor-
tunity to evaluate the potential environ-
mental problems associated with a full-
scale, operating, Lurgi-process plant.
Sampling Strategy
The objective of the sampling program
was to collect ambient atmospheric
samples at upwind, downwind, and
crosswind locations from the coal gasi-
fication plant in order to identify the
effect of the plant's emissions on local
air quality. This involved collecting
samples at multiple sites to distinguish
the contribution of the gasification plant
from that resulting from other sources
within the Kosovo industrial complex
and the surrounding area. The sampling
of the gasification plant's emissions
was complicated by the proximity of
other potential pollution sources: a coal
processing unit; fertilizer plant, steam
plant, and coal-burning electric-gener-
ating plant, as well as steam and diesel
trains and farming activity in the area.
To Gas
Vent
To Gas
Vent
The emission sources in each sectior
of the gasification plant are summarizec
in Table 2. The distinguishing charac-
teristics shown in this summary were
used to differentiate gasifier emission
sources from other sources in Kosovc
industrial complex and the surrounding
area. The emission streams generated
in coal or lignite gasification contain the
following mixture of substances:
• aromatic hydrocarbons and hetero-
cyclics including benzene, toluene,
xylenes, and possibly heavier or-
ganics such as PNAs
• phenols and other oxygenated
organics
• sulfur species (HzS, mercaptans,
COS, thiophenes)
• nitrogen species (pyridines)
• tar and oil aerosols.
These stream characteristics were used
to design the analytical strategy for the
ambient air samples collected around
the Kosovo industrial complex.
Five sampling stations were deployed
outside the perimeter of the industrial
complex according to prevailing wind
patterns (Figure 2). Atmospheric sam-
ples were collected over a 16-day period
from May 14 to May 29, 1979. Each
sampling station was equipped to collect
To Gas
Flare
To Gas
Vent
To Gas
Flare
I I I
Raw _
Coal
Coal
Preparation
To
Water Recycle
Pond
Dry
Co
al
1
— »
3as Generation
and
. Cooling
Ash
Raw
Gas
To
Water Recycle
Pond
~o Gas To Gas
Vent Flare
Tar
Separation
Gas
Cleaning
To Gas
Vent
By-Product
Tanks
1
To Gas
Vent
*
Water
Extraction
Product
Gas
m Liquid
By-Products
Heavy
Tar
To
Water Recycle
Pond
NOTE: Data assumes five generators
in service; one on standby.
Figure 1. Overall flow scheme of the Kosovo Lurgi gasification plant.
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total particles for organic analysis; total
(<15 fim) and fine (<2 ^m) particles for
gravimetric, inorganic, and elemental
analysis; size-fractionated particles for
elemental analysis; and organic vapors.
The sampling equipment and the char-
acteristic daily sampling periods were
as follows:
• a high-volume (hi-vol) aerosol
sampler with a Tenax® resin organ-
ic vapor trap assembly (24-hour
sample)
• a low-volume (lo-vol) aerosol sam-
pler collecting total and fine frac-
tions (6-hour samples, 4 per day)
• a cascade impactor (6-hour sam-
ples, 4 per day)
• a time-phased paniculate sampler
(streaker) (7-day sample).
Two of the stations were also equipped
to provide continuous records of wind
speed and direction. One station also
monitored temperature, solar flux,
atmospheric pressure, and time.
Quality assurance audits covering the
sampling program were conducted
daily. These included sampling media
preparation, equipment calibration and
operation, initial and final gravimetric
measurements, sample storage and
transport, and sample documentation.
Analysis Strategy
The objective of the analysis program
was to analyze the particle and vapor
catches collected in the vicinity of the
Kosovo industrial complex and to com-
pare identified organic species and
inorganic concentrations found with
similar data obtained from the analysis
of the gasification plant's emissions and
by-product streams. To this end, three
integrated courses of analysis were
followed:
• physical characterization of the
paniculate matter
• inorganic analysis of the panicu-
late matter
• organic analysis of species in the
vapor and adsorbed on the panicu-
late matter.
Physical Characterization
Particulate matter in the ambient air
surrounding the Kosovo industrial com-
plex was characterized by:
• determining the sub-15 and sub-2
micrometer mass loadings at each
site for each time interval and then
comparing them
©
(15°)
Sample
Sitettt
Sample
Site #5
Fertilizer •. Center \'
\ Plant '-.Reference \
\ .•'"''• Point ..•'"•.
Figure 2.
(150°) ©
Sample
Site #3
Schematic of the Kosovo complex with the five sampling sites indicated.
3
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Table 2. Summary of Air Emission Sources from the Coal Gasification Plant
Gasification Section Emission Source Emission Source Characteristics
Fleissner Process:
Coal Bunker Vent (1.1)
Autoclave Vent (1.2)
Condensate Tank Vent (1.4)
Lurgi Gasification Process:
Coal Bunker Vent (2.2)
Coal Bucket Vent (3.1)
Low-Pressure Lock Vent (3.2)
Quench Liquor Tank Vent (3.4)
Ash Lock Vent (3.5)
Rectisol Process:
COZ Vent Gas (7.2)
Tar Separation:
Tar Tank Vent (13.1)
Impure Tar Tank Vent (13.2)
Medium Oil Tank Vent (13.3)
Impure Medium Oil Tank Vent (13.4)
Condensate Tank Vent (13.5)
Phenolic Water Tank Vent (13.7)
Phenosolvan:
Cyclone Vent (14.1)
Phenolic Water Tank Vent (14.2)
Unclean Oil Tank Vent (14.3)
Filtered Water Tank Vent (14.4)
Degassing Column Vent (14.5)
Ammonia Stripper Cooler Vent (14.6)
Degassing Column Vent (14.7)
Slop Tank Vent (14.8)
Phenol Storage Tank Vent (14.9)
DIPE Tank Vent (14.10)
Ammonia Absorber Vent (14.12)
Ammonia Storage Tank Vent (14.13)
By-Product Storage:
Tar Tank Vent (15.1)
Medium Oil Tank Vent (15.2)
Gasoline Tank Vent (15.3)
Raw Phenol Tank Vent (15.4)
Unclean Oil Tank Vent (15.5)
NHAOH Tank Vent (15.6)
Flare:
Coal Dust
Coal Dust, Organics. Sulfur Species,
Nitrogen Species
Organics, Sulfur Species, Nitrogen Species
Coal Dust
Coal Dust, Raw Gas Components
(Tars, Oils Phenols, Sulfur Species,
Nitrogen Species)
Raw Gas Components
Steam, Ash Dust
COz. Sulfur Species, Organics
Organics, Sulfur Species, Nitrogen
Species, CO, Phenols
Organics, Phenols, Ammonia, Sulfur
Species, Nitrogen Species, CO
Organics, Sulfur Species, Nitrogen
Species, Phenols
Combustion Products (COz, HzO, SOz,
NO*}, Organics, CO, Tar, Sulfur Species,
Nitrogen Species.
Input streams to the flare (high pressure
lock gases, HzS-rich gas and tar
separation expansion gas) contain tars,
oils, sulfur species, nitrogen species,
and other compounds found in the
raw gas.
• plotting mass loadings as a func
tion of the site's time-percentag
downwind
• viewing and photographing seled
ed paniculate catches using
scanning electron microscope (SEM
The objective of these analyses was t
determine the ambient aerosol burde
and to distinguish the types of aerosol
present (that is, dust, coal dust, fly ash
and organic material).
Inorganic Analysis
The following analytical scheme wa
employed to quantify the elemental an
inorganic components associated wit
the aerosols:
• Specific water-soluble ions asso
ciated with the particles wer
quantified by ion chromatograph
(Na+, NH4+, Cr, N03~, SO4=)
• Total elemental concentrations o
15 metals in the paniculate matte
were determined by inductive!
coupled argon plasma (ICAP)emis
sion spectroscopy
• Total elemental concentrations o
carbon, nitrogen, hydrogen, am
sulfur in the particulate matte
were determined using combus
tion analysis
• The relative amounts of the princi
pal chemical forms of carbon wen
determined: graphitic, carbonate
and organic
• Multi-element analysis of partick
catches in various size range;
(between 0.25 - 10m) and of thi
particulate matter collected contin
uously by the streaker sample
were determined by proton-induce*
x-ray emission (PIXE) spectroscopy
When plotted against the percentage o
time that a sampling site was down wine
from the gasifier, the data derived frorr
this analytical scheme identified th<
pollutants that correlated with down
wind collection. Some of the physica
and inorganic data were useful ir
attempting to identify sources of th<
particles.
Organic Analysis
The organic analysis strategy was
designed to identify and determine
relative amounts of the organic com
pounds released from the gasifier to thi
atmosphere. A program in quality assur
ance, to validate this characterizatior
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was developed and adhered to. The
strategy employed was as follows:
• Methods appropriate for the anal-
ysis of organic species (for example,
aromatics, organic sulfur and nitro-
gen species) on the Tenax® resin
and hi-vol filter samples were
developed and validated
• Two independent means of separa-
ting the vapor-phase sample from
the collection matrix were used:
solvent extraction and thermal
desorption
• Packed-column gas chromatography
(GC) was used, followed by four
complementary means of detection
to achieve a detailed chemical
speciation and quantitation: flame
ionization detection (FID), mass
spectrometry (MS), and Hall-Sulfur
and Hall-Nitrogen specific detectors
• The GC profile of the ambient
organic catch was compared with
the GC profile of the gasifier by-
products analyzed by the same
methods.
Results
Physical Characterization
Data on the physical characterization
of the emissions indicated that the
aerosol loadings (both total and fine)
were significantly greater in the samples
collected downwind of the Kosovo
industrial complex. The increase was
greater for the coarse aerosol loading
than for the fine particles. The panicu-
late matter collected downwind appear-
ed to be of mineral origin. Only small
amounts (<1 percent) of typically spher-
ical fly ash were found.
Inorganic Analyses
Correlations between concentration
(fjg/m3) and percent downwind were
not found for any chemical or elemental
species except total carbon. That is, the
total carbon content of the aerosol mass
was greater for the downwind sites.
Furthermore, the percentage increase
was larger for the coarse aerosol fraction
than for the fine fraction.
Organic Analyses
Several improved analytical methods
developed by Radian Corporation were
validated in the characterization of the
air samples and gasification plant prod-
ucts. These improved methods were the
homogenization and quantitative all-
quoting of large Tenax® resin samples
to achieve a greater dynamic range in its
analysis; thermal desorption of sorbed
vapors from the Tenax® resin yielding
quantitative recoveries of aromatics in a
volatility range that extended from
benzene (boiling point [b.p.] = 80°C) to
pyrene (b.p. = 404°C); and organic
speciation using sulfur- and nitrogen-
specific detectors following the same
GC column to yield profiles of the sulfur-
and nitrogen-containing compounds
against the much higher hydrocarbon
background.
The Tenax® resin vapor traps collect-
ed organic species in the volatility range
from benzene to pyrene. Benzene and
toluene were determined to have not
been collected quantitatively; that is,
breakthrough occurred for both Tenax®
traps (connected in series). Breakthrough
may have occurred for other volatile
species, but the xylenes and all heavier
compounds were collected quantitatively.
There was a clear distinction (although
some overlap) between organic com-
pounds adsorbed on the particulate
matter caught on the hi-vol filter and the
vapors sorbed on the Tenax® resin. The
aromatic vapors ranged from benzene
(molecular weight [MW] = 78) to pyrene
(MW = 202). The filter samples contain-
ed polynuclear aromatics (PNAs) from
naphthalene (MW = 128) through the
benzopyrene isomeric group (MW =
252):
Mass spectrometric analysis tenta-
tively identified more than 50 organic
compounds and isomeric groups (distri-
buted over 12 categories defined in the
Multimedia Environmental Goals) pre-
sent in the atmospheric samples. The
list of identified compounds included:
alkylated benzenes through at least C4
substitution, PNAs and alkylated PNAs
through benzopyrenes, linear and het-
erocyclic hydrocarbons, phenols, ke-
tones, quinones, alkylated pyridines and
quinolines, alkylated thiophenes, and
dibenzofuran.
Quantitation by MS and FID places
the maximum individual species con-
centration in the ambient samples at 8
//g/m3 for naphthalene in the vapor
phase and ~0.08 /ug/m3 for the benzo-
pyrene isomer group adsorbed on the
particulate matter when extrapolated to
100 percent downwind (Table 3). Mini-
mum detected concentrations were two
to three orders of magnitude, less than
these maximum values. Comparison of
measured concentrations with AMEG
(Ambient Multimedia Environmental
Goal) values indicates that certain
species (that is, benzopyrene isomers)
may cause harmful health effects (Table
3).
Overall, the organic compounds de-
tected in the air samples were almost
identical to the compounds found in
certain emissions from the coal gasifi-
cation plant.
Conclusions
It was concluded that the increase in
particulate matter collected downwind
of the Kosovo industrial complex can
probably be attributed to mechanical
sources, such as coal crushing, sizing,
and transporting in the area of the
complex. Moreover, there appears to be
a strong positive correlation between
the organic compounds found in the
downwind ambient air samples and
those observed from the analysis of
emission sources at the gasification
plant (represented by the middle oil).
This correlation suggests that it is
possible to differentiate between the
emissions from the gasification plant
and those from other sources within the
Kosovo industrial complex.
It was also concluded that the mea-
sured ambient concentrations of certain
organic species, such as benzopyrene
Table 3-. Comparison of Compounds in the Ambient Air to Ambient Air Goals
Ambient Levels
Chemical Species at 10O% DW fjg/m3 AMEG Goats fjg/m3
1. Benzene
2. Naphthalene
3. Benzofajpyrene
4. Phenol
5. Methyl thiophene
6. Pyridine
6.8*
7.5
O.OSf
6.0
0.3
0.08
7.1
100
0.00005
3.8
41
36
* Minimum benzene concentrations because of breakthrough.
^Quantitation of all mass 252 isomers.
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isomers and organic sulfur- and nitrogen-
containing compounds, emitted from
the Kosovo coal gasification plant may
be sufficient to cause harmful health
effects based on EPA's Ambient Multi-
media Environmental Goals.
• Assessment of the atmospheric
chemistry associated with the
compounds identified in the Lurgi
plant's emissions (that is, mercap-
tans, benzene, H2S, COS, NH3, and
others).
Recommendations
From the results and conclusions
reached in this program and from the
results of source testing at the gasifica-
tion plant, a comprehensive ambient
sampling and analysis program around
the Kosovo Lurgi plant is recommended.
Specific elements of this proposed
program would include:
• Determination of the transport and
fate of the major and minor pollu-
tants that were identified in this
study as being emitted from the
Lurgi gasification plant. These
pollutants include vapors (benzene),
sulfur gases (H2S, COS, methyl and
ethyl mercaptans, thiophenes),
nitrogen-containing species (am-
monia and pyridines), and PNAs
(benzopyrene isomers)
• Additional elemental and mineral
analyses of collected particulate
matter and coal dust to identify the
actual contribution of the gasifica-
tion plant to the ambient aerosol
burden
• Development and validation of
improved sampling and analysis
techniques for quantitative collec-
tion of low molecular weight gases
and organic vapors (that is, ben-
zene, mercaptans, ammonia, pyri-
dine, and others)
• Correlation of ambient air pollutants
to point sources in the gasification
plant.
It is also recommended that any further
sampling efforts should resolve the
wind corridors into twenty-two 1/2°
segments for a better definition of
"downwind"; this is particularly neces-
sary at greater distances (>2 km) from
the source.
Other specific recommendations from
this study include:
• Identification and quantitation of
heavy organics (that is, 5-, 6-ring
PNAs) by alternative analytical
techniques such as high-pressure
liquid chromatography
• Identification and quantitation of
organic compounds in the lignite to
determine if the coal is a source of
heavy organics
This Project Summary was authored by Anton M. Fackelmann, WAPORA, Inc.,
Cincinnati. OH 45233.
K. J. Bombaugh. G. C. Page. C. H. Willilams. L O. Edwards. W. D. Balfour, D. S.
Lewis, and K. W. Lee are with Radian Corporation, Austin, TX 78766 and
authored the Final Report upon which this Summary is based.
Ronald K. Patterson is the EPA Project Officer (see below).
The complete report, entitled "Aerosol Characterization of Ambient Air Near a
Commercial Lurgi Coal Gasification Plant—Kosovo Region, Yugoslavia."
/Order No. PBS1-120 776; Cost: $12.50, subject to change) will be available
only from:
National Technical Information Service
5285 Port Royal Road
Springfield, VA 22161
Telephone: 703-487-4650
The EPA Project Officer can be contacted at:
Environmental Sciences Research Laboratory
U.S. Environmental Protection Agency
Research Triangle Park, NC 27711
US. GOVERNMENT PfllNnNO OFFICE H61-757-01Z/7041
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United States Center for Environmental Research
Environmental Protection Information
Agency Cincinnat. OH 45268 Prote«io
Agency
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Penalty for Private Use $300
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