United States
Environmental Protection
Agency
Industrial Environmental Research
Laboratory
Research Triangle Park NC 27711
EPA-600/2-80-082
May 1980
Research and Development
&EPA
Environmental
Assessment of a
Coal Preheater
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7. Interagency Energy-Environment Research and Development
8. "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the ENVIRONMENTAL PROTECTION TECH-
NOLOGY series. This series describes research performed to develop and dem-
onstrate instrumentation, equipment, and methodology to repair or prevent en-
vironmental degradation from point and non-point sources of pollution. This work
provides the new or improved technology required for the control and treatment
of pollution sources to meet environmental quality standards.
EPA REVIEW NOTICE
This report has been reviewed by the U.S. Environmental Protection Agency, and
approved for publication. Approval does not signify that the contents necessarily
reflect the views and policy of the Agency, nor does mention of trade names or
commercial products constitute endorsement or recommendation for use.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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EPA-600/2-80-082
May 1980
Environmental Assessment of
a Coal Preheater
by
T.K. Sutherland, J.P. Bilotti, and E.M. Whitlock
York Research Corporation
One Research Drive
Stamford, Connecticut 06906
Contract No. 68-02-2819
Task No. 4
Program Element No. 1AB604C
EPA Project Officer: Robert C. McCrillis
Industrial Environmental Research Laboratory
Office of Environmental Engineering and Technology
Research Triangle Park, NC 27711
Prepared for
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, DC 20460
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TABLE OF CONTENTS
List of Figures
List of Tables
1.0 Summary 1
1.1 Particulate Emissions 2
1.2 Organic Emissions 3
1.2.1 Polycyclic Organic Material (POM) 3
1.2.2 Benzene and Total Hydrocarbon 4
2.0 Conclusions 6
3.0 Recommendations 7
3.1 Program Design 7
3.2 Test Program 7
3.3 Sampling Trains 8
4.0 Introduction 12
5.0 Process Description 13
5.1 Coking Process 13
5.2 Charging System 14
5.3 Scrubber Water System 17
6.0 Test Procedures 19
6.1 Test Program 19
6.2 Sampling Point Determinations 22
6.3 Gas Velocity 23
6.4 Gas Composition 23
6.5 Moisture in Stack Gas 25
6.6 Particulate Method 27
6.6.1 Test Data 29
6.6.2 Sample Recovery for Particulate and 30
Chloroform Soluble Organics
6.7 POM Sampling Method 31
6.7.1 POM Sample Recovery 33
6.8 Benzene Soluble Organics Method 34
6.8.1 BSO Sample Recovery 34
6.9 Determination of Sulfer in Impinger Catches 35
6.10 Benzene and Total Hydrocarbons 36
6.11 Coal Samples 36
6.12 Scrubber Water 37
6.13 Sampling Problems 38
7.0 Analytical Procedures 43
7.1 POM Analytical Procedures 43
7.1.1 Particulates 43
7.1.2 Organic Analyses 43
11
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TABLE OF CONTENTS (cont.)
Page
7.2 Particulate and Chloroform Soluble Analysis 47
7,3 Benzene Soluble Organics Analysis ^y
7.4 Determination of Sulfur in Impinger Catches 51
7.5 Benzene and Total Hydrocarbon Analysis 52
7.6 Scrubber Water Analysis ^
7.7 Coal Analysis 5Z
8.0 Results 55
8.1 Particulate Results from POM Trains 55
8.2 Gas Chromatography/Mass Spectrometry Analysis 58
8.2.1 Identification of POMs 58
8.2.2 Detection Limits 62
8.2.3 Total POM 64
8.2.4 Selected POM 6'7
8.2.5 Selected vs. Total POM 8Q
8.2.6 Toxicity Level of Coal Preheater 85
Emissions
8.3 EPA-5 Train Test Results 9Q
8.4 Results of Benzene Soluble Organic Analysis 92
8.5 Results of EPA Level 1 Organic Analysis 100
8.6 Benzene and Total Hydrocarbons in Stack 108
Gas Grab Samples
8.7 Benzene Content in Water Grab Samples 108
8.8 Sulfur in Impinger Catches 109
8.9 Coal Analysis 111
9.0 Discussion of Results 125
9.1 Particulate Emissions 125
9.2 Chloroform and non-Chloroform Soluble Emissions 129
9.3 Benzene and Total Hydrocarbons 136
9.4 POM Analysis Discussion 13g
10.0 Effect of Process Conditions 142
10.1 Particulate Emissions 142
10.2 Organic Emissions 142
10.3 POM Emissions 143
111
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LIST OF FIGURES
FIGURE
5-1 Coaltek Charging System with Cerchar 15
Coal Preheater 18
5-2 Scrubber Water Treatment System 18
6-1 Preliminary Velocity Train 24
6-2 Tedlar Bag Sampling Train 24
6-3 Preliminary Moisture Train 26
6-4 Particulate Sampling Train 28
6-5 POM Train 32
7-1 POM Sampling Train Particulate 44
Analysis Methodology
7-2 GC/MS Analysis Methodology 46
7-3 EPA Level 1 Organic Analysis Methodology 48
7-4 EPA-5 Sampling Train Methodology forChloroform 50
and Non-chloroform soluble Particulate
7-5 Coal Analysis Methodology 54
8-1 Ion Chromatogram of mw 252 and 2.54 g.Q
8-2 Ion Chromatogram of mw 256 g-g
8-3 Ion Chromatogram of mw 266 and 267 g-]_
Effect of Coal Feed Rate and Preheater Outlet
Temperatures on....
10-1 Total Particulate at Scrubber Inlet (PA-DER Method) 144
10-2 Total Particulate at Scrubber Outlet (PA-DER Method) 145
10-3 Total Particulate Scrubber Efficiency 146
(PA-DER Method)
10-4 POM Train Particulate at Scrubber Inlet 147
10-5 POM Train Particulate at Scrubber Outlet 143
10-6 Scrubber Efficiency (POM Particulate) 149
10-7 Benzene Soluble Organic Concentrations 150
10-8 Concentration of Chloroform Soluble Organics 151
(PA-DER Method) at Scrubber Inlet
10-9 Concentration of Chloroform Soluble Organics
(PA-DER Method) at Scrubber Outlet
10-10 Chloroform Soluble Organics Scrubber Efficiency 153
10-11 Total POM Concentration at Scrubber Inlet 1,54
10-12 Total POM Concentration at Scrubber Outlet 155
10-13 Total POM Concentration Scrubber Efficiency 155
IV
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LIST OF TABLES
TABLE
1-1 Summary of Particulate Emissions (EPA-5 Method) 9
1-2 Summary of Particulate Emissions (BSD Train) 10
1-3 Summary of Chloroform Soluble Organic Emissions n
(EPA-5 Method)
1-4 Summary of Benzene Soluble Organic Emissions n
i
6-1 Summary of YRC Testing 21
6-2 Test Conditions: % Moisture, % Isokinetic, Flow Rate 41
8-1 Summary of Particulate Emissions (POM-Train) 56
8-2 Particulate Loadings by Sampling Train 57
Components (POM-Train)
8-3 Detection Limits of GC/MS Analysis 63
8-4 Summary of Total POM Concentration in Coal 65
Preheater Samples
8-5 POM Analysis of Coal Preheater Stack Samples 68
thru Individuals Tests thru
8-15 78
8-16 POM Analysis of Water Samples 79
8-17 Comparison of 3-ring and Higher POMs to 82
Total Sample Extract
8-18 Analysis of Aromatic Fractions of Coal 83
Preheater Samples
8-19 Gravimetric Analysis of Coal Preheater Samples 84
8-20 POM DMEG Values Based on Health Effects 86
8-21 Discharge Severity Calculated for POM in Coal 87
Preheater Samples, Scrubber Outlet, Tests 1 thru 6
8-22 Discharge Severity Calculated for POM in Coal 88
Preheater Samples, Scrubber Outlet, Tests 7 thru 11
8-23 Discharge Severity Calculated for POM in Coal 89
Preheater, Scrubber Outlet, Water Samples
8-24 Chloroform & Non-chloroform soluble Particulates 91
8-25 Summary of Benzene Soluble Test Results 93
8-26 BSO Test Results, No. 1 - inlet 94
8-27 BSO Test Results, No. 1 - outlet 95
8-28 BSO Test Results, No. 2 - inlet 96
8-29 BSO Test Results, No. 2 - outlet 97
8-30 BSO Test Results, No. 3 - inlet 98
8-31 BSO Test Results, No. 3 - outlet 100.
8-32 EPA Level 1 Organic Extract Summaries - 101
thru Individual Tests thru
8-37 106
8-38 Summary of EPA Level 1 Organic Analysis 107
8-39 Benzene and Total Hydrocarbons in Grab Samples 10P
8-40 Sulfur in Impinger Catches 110
8-41 Size and Moisture Analysis of Coal Samples 117
8-42 Coal Analysis Results, Inlet Samples 118
v
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LIST OF TABLES, (cont.)
TABLE Fag.
1] 9
8-43 Coal Analysis Results, Outlet Samples ;*•--•
8-44 Spark Source Mass Spetrometry Results -
thru Individual Tests
8_47
8-48 Summary of Trace Elements in Coal Samples 124
9-1 Comparison of YRC and B.E.E. 126
EPA-5 Particulate Data
9-2 Comparison of YRC and B.E.E. 127
Particulate Data - PA-DER Method
9-3 Comparison of Particulate Data from POM and 128
BSO Samples (front half)
9-4 Comparison of YRC and B.E.E. Chloroform 130
Soluble Organic Data
9-5 Comparison of YRC and B.E.E. Data - Percent 131
Chloroform Soluble Particulate
9-6 Breakdown of Betz Chloroform Soluble Data 132
by Sampling Train Components - Scrubber Inlet
9-7 Breakdown of Betz Chloroform Soluble Data 133
by Sampling Train Components - Scrubber Outlet
9-8 Breakdown of Betz Non-Chloroform Soluble Data 134
by Sampling Train Components - Scrubber Inlet
9-9 Breakdown of Betz Non-chloroform Soluble Data 135
by Sampling Train Components - Scrubber Outlet
VI
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1.0 Summary
York Research Corporation (YRC) contracted by the Environmental
Protection Agency to undertake a research study which would
evaluate emissions associated with a coal preheater system.
Testing was conducted in July and August of 1978 on a system
installed at the Jones and Laughlin (J&L) Steel Corporation's
Aliquippa Works, Aliquippa, Pennsylvania.
The primary objectives of the study were to:
o Characterize particulate and organic emissions from
the coal preheater system
o Identify and quantify polycyclic organic materials
(POM) which may be present in the emissions
o Relate emission characteristics to the processing
conditions of the preheater system.
The testing program centered around the north unit scrubber of
the preheater system. Gas stream inlet and outlet testing was
as follows:
o Samples for chloroform and non-chloroform soluble
particulate were taken using a standard EPA-5 sampling
train
o Samples for POM analysis were taken using a POM train
which is essentially an EPA-5 train with an adsorber
located downstream of the filter.
o Samples for benzene soluble organics (BSO) were taken
using a POM train
The following grab samples were also obtained:
o Scrubber gas inlet and outlet - analyzed for benzene
and total hydrocarbon content
o Scrubber water inlet and outlet -analyzed for POM's
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o Preheater inlet and outlet coal samples - analyzed for
ash, volatiles, carbon, hydrogen, sulfur, and moisture
The results of an emission study conducted on this same preheater
system, done by Betz Environmental Engineers, Inc. for (B.E.E.)
for J&L Steel Corp., have been incorporated into this report in
order to expand the data base. B.E.E. testing was done in March
and April of 1977; however, the physical and operational aspects
appear to have been the same as during the YRC test period.
1.1 Particulate Emissions
A summary of EPA-5 particulate emissions is given in Table 1-1.
These results are based on a total of 40 tests (36 B.E.E./4 YRC)
and show the effect of process changes. Generally, inlet parti-
culate concentration is unaffected by preheater outlet temperature and
is lowest for a coal feed rate of 95 M-ton/hr. Outlet concentration
tends to increase with increasing preheater outlet temperature,
especially at higher coal feed rates, and with higher feed rates.
Scrubber efficiency decreases with increasing feed rate and also
decreases with outlet temperatures at higher feed rates.
PA-DER method particulate concentration shows the same trend (see
Figures 10-1, 10-2, and 10-3).
POM train particulate concentration at the scrubber inlet was highly
variable and shows no substantial trend with process conditions.
Outlet concentration increases with both coal feed rate and outlet
temperature; consequently, scrubber efficiency decreases. Inlet
concentrations ranged from 4.398 to 21.26 mg/Nm , outlet concen-
trations from .287 to 1.764 mg/Nm , and scrubber efficiency from
98.9 to 83%.
BSO train particulate concentration is summarized in Table 1-2. No
effect of process conditions can be discerned on the basis of
only three tests.
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1.2 Organic Emissions
Table 1-3 presents a summary of chloroform soluble emissions based
on the 36 tests conducted by B.E.E. and 4 by YRC. Below a coal
feed rate of 95 M-ton/hr, scrubber inlet concentrations increase
primarily with increasing preheater outlet temperature. Above
this point, inlet concentrations also increase strongly with
increasing coal feed rate. Outlet concentrations increase with
both process conditions but the effect of preheater outlet
temperature appears to be dominant. Scrubber efficiency ranges
between 41 and 65% and is higher at the lower temperature.
Benzene soluble emissions are given in Table 1-4. Process
characterization is not possible on the basis of three tests;
however, scrubber efficiency is lower than for the chloroform
solubles.
An EPA Level 1 organic analysis was run on 2 stack, samples, 2
water samples, and 2 blanks. Aliphatic hydrocarbons, fused
aromatic hydrocarbons, phenols, and esters were the major
components in the stack air samples. Aliphatic hydrocarbons,
carbazoles, and phenols were the major components in the water
samples.
1.2.1 Polycyclic Organic Material, (POM)
Twenty-two stack air samples were analyzed by GC/MS for 25 POM
species. Only 22 species were found. Concentrations of individual
species were highly variable and were not consistent from test to
test. This could be due to natural variations in the coal processed
or in the coke oven gas as produced or burned. Among the compounds
analyzed, the most prevalent species found were napthalene, anthra-
cene, and phenanthrene. Lesser amounts of fluorene, pyrene,
fluoranthene, benzanthracene, chrysene, and benzopyrenes were
also found.
Gravimetric analysis showed that total POM concentration was
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3 to 14% of the aromatic fraction which was 23 to 67% of the total
organic sample extract. Total POM emissions are summarized in
Table 8-4. Total POM concentrations at the scrubber outlet were
strongly dependent on coal feed rate, increasing with higher feed
rates. The effect of preheater outlet temperature was much less.
Scrubber inlet concentrations increased with both preheater outlet
temperature and coal feed rate.
Total POM scrubber efficiency increased with higher coal feed
rates and ranged from 17.8 to 71.6%.
Six water samples were analyzed by GC/MS for POM's. Only the
lightest molecular weight species were found. Total POM concen-
tration was significantly lower than was expected in the scrubber
outlet water. It is possible that the high concentration of
particulate matter (which a high percentage of carbon) in the
outlet samples adsorbed a large portion of POM material.
In order to estimate the toxicity level of the POM emissions,
these emissions were compared to their corresponding Discharge
Multimedia Environmental Goal (DMEG) levels. This comparison showed
that, for most of the air samples, the following species exceed their
DMEG levels. Phenanthrene, Benz(a)anthracene , Benzo(a)pyrene,
7 ,12-dimethylbenz(a)anthracene, and 3-methyl cholanthrene. None
of the POM species found in the water samples exceeded their
DMEG levels,
1.2.2 Benzene and Total Hydrocarbons
Eight inlet and outlet stack gas grab samples were analyzed for
benzene and total hydrocarbon concentrations. Significantly
higher concentrations were found in the outlet samples. Six
water samples were also analyzed for benzene and none was found.
It is possible that any light hydrocarbons in the water samples
volitilized before the samples were analyzed. The evidence,
however, indicates that the benzene and light hydrocarbons were
introduced by the water stream. The scrubber water system, as
it existed during testing, was open to possible sources of
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accidental contamination. Condensate from the charging bin vent
condenser was also led to the scrubber pumping- tank. This is
another possible source of light hydrocarbons.
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2.0 Conclusions
Scrubber removal efficiency for particulate ranged from 86 to
93%. Emissions at the scrubber outlet ranged from 95 to 468
g/M-ton of coal. This is based on combined EPA-5 method results
obtained by York Research and Betz Environmental Engineers.
Process conditions had a significant effect on particulate
emissions. In general, outlet loadings increased with coal feed
rate which decreased scrubber efficiency. However, a significant
improvement in scrubber efficiency was obtained at the lower
preheater outlet temperature (271°C).
Particulate results obtained from POM and BSO tests follow the
same trends noted for EPA-5 particulate.
At the scrubber outlet chloroform soluble organic emissions ranged
from 11 to 414 g/M-ton coal and benzene soluble organic emissions
from 186 to 397 g/M-ton coal. Total POM emissions ranged from
4.7 to 23.4 g/M-ton. Scrubber efficiency for removal of organics
was lower than for particulate removal and increased with in-
creasing coal feed rate. Preheater outlet temperature increased
both inlet and outlet concentrations, but did not affect scrubber
efficiency.
GC/MS analysis showed extreme variability in POM specie concen-
traions. The following POM species exceeded their Discharge
Multimedia Environmental Goal (DMEG) levels: phenanthrene,
benz (a)anthracene, benzo(a)pyrene, 7,12-dimethylbenz(a)anthracene,
and 3-methyl cholanthrene.
-6-
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3.0 Recommendations
3.1 Program Design
A unified systems approach should be taken to any future studies;
i.e., engineering, testing, and analytical personnel should be
involved in all phases of the program.
Design of an appropriate test program depends on a clear under-
standing of program objectives, process characteristics and
conditions, and analytical requirements and objectives. Thus,
the input of engineering and analytical expertise is required
at the very start so that sampling techniques and methodology
can be taylored in advance to the specific situation. Program
objectives, in turn must be established using a knowledge of
analytical and sampling problems which may arise.
3.2 Test Program
In light of the rapid process fluctuations and frequent inter-
ruptions experienced, future sampling procedures must be designed
to accommodate these characteristics of the coal preheater system.
Strict simultaneity between inlet and outlet samples must be
observed. Short sampling periods are necessary to establish
the range of process variation while very long periods are
required to establish typical emission rates. In addition,
simultaneous sampling of the water stream is required in order
to provide a mass balance and a check on test results, especially
for organic emissions. Analysis of all samples must be done as
quickly as possible in order to avoid loss of volatiles and
particulate matter in the water samples must be desorbed of
organic material.
To determine the source of particulate and organic emission
variation, testing of the coal and coke oven gas is also required.
-------
This report provides information on a coal preheater system
operating under a limited number of conditions; i.e., coal
feed rate and preheater outlet temprature. Total characterisation
of coal preheater emissions would also require the study of the
effect of:
o various liquid to gas ratios in the scrubber
o recycle water quality
o different coal mixes and sizing
o various scrubber pressure drops
3.3 Sampling Trains
The high particulate loading found in the scrubber inlet gas
stream required that many filter changes be made during sampling.
One modification to the standard test train which would reduce
this problem would be to install a cyclone at the probe tip.
This would reduce the size of particulate reaching the filter.
A velocity meter/recorder should be used in place of the usual
manometer in order to improve sampling accuracy with changing
stack gas velocity.
-8-
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TABLE 1-1
SUMMARY OF PARTICULATE EMISSIONS
(EPA-5 METHOD)
Process
Conditions *
82/271
95/271
109/271
76/278
82/288
95/288
109/288
Inlet
mg/Nm
18586
15366
15528
18267
12981
15116
Kg/Hr
395.4
295.6
314.2
361.4
257.9
288.7
g/M-Ton
4822
3111
2882
4407
2714
2649
Outlet
mg/Nm
1334
1347
1791
953
1357
1814
2020
Kg/Hr
20.0
21.3
28.5
7.3
21.9
30.2
51.0
g/M-Ton
244
224
353
95
266
318
468
93
91
88
93
86
87
* (M-Tons Coal/Hr)/(Preheater Outlet Temp., C)
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TABLE 1-2
SUMMARY OF PARTICULATE EMISSIONS
(BSD-TRAIN)
Process
Conditions *
82/271
109/271
55/288
Inlet
mg/Nm
10362.6
8266.2
17285
Kg/Hr g/M-Ton
291
308
337
3547
2827
6133
mg/Nm'
982.6
3262.7
1664.8
Outlet
Kg/Hr g/M-Ton _%_
18.7 228
95.3 875
25.5 463
91
61
90
o
I
* (M-Tons Coal/Hr)/(Preheater Outlet Temp., C)
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Process
Conditions
Process
Conditions *
TABLE 1-3
SUMMARY OF CHLOROFORM SOLUBLE ORGANIC EMISSIONS
(EPA-5 METHOD)
Inlet
Outlet
(PA-DER METHOD)
Inlet
Outlet
82/271
95/271
109/271
76/278
82/288
95/288
109/288
i
— I
, j>
\
mg/Nm
1235
1144
3146
—
1398
1688
3347
CT
Kg/Hr
26.3
22.0
63.7
—
27.7
33.5
63.9
•TMMTV r> v rvtn
g/M-Ton mg/Nm
321
232
584
--
338
352
586
D'n'KT'7'n>»
492
675
1086
110
789
1000
1787
TABLE 1-4
.IT? c?r\r TTDT IP /ID/** AMI
Kg/Hr
7.4
10.7
17.3
0.8
12.7
16.6
45.1
f/"« TP1UITC7OT
g/H-Ton
90
113
159
11
155
175
414
ntvTo
%
60
41
65
—
44
41
47
82/271
109/271
55/288
mg/Nm
1157
2741
1279
- Kg/Hr
35.5
106.3
25.0
g/M-Ton
435
970
458
mg/Nm
783
1930
1344
Kg/Hr
14.9
55.4
21.8
g/M-Ton
186
534
397
%
32
30
—
* (M-Tons Coal/Hr/(Preheater Outlet Temp., C)
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4.0 Introduction
The concept of using a closed charging system to reduce emissions
during coking processes along with a coal preheater to improve
coke throughput and economy is an attractive idea. Typical practice
in the steel industry has been to charge coke ovens through openings
in the oven tops with wet coal. This practice results in a large
amount of pollutants. The installation of a closed charging system
offers the potential of greatly reducing the quantity of emissions
and confines them to a single source.
In an effort to better understnad the character of emissions associated
with such a system, the EPA sponsored York Research Corp to undertake
a research study. Testing was done in July and August, 1978,around
the north unit scrubber of a coal preheater system installed at Jones
and Laughlin Steel Corp.'s Aliquippa steel mill in Aliquippa,
Pennsylvania.
Special attention was given to the detection and analysis of polycyclic
organic materials (POM's). A modified EPA-5 particulate train was
used during the sampling to be sure any POM's would be captured.
Testing was conducted at several levels of preheater operation so
that emissions could be related to system operation.
-12-
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5.0 Process Description
Modern integrated steel mills incorporate all the facilities needed
to produce finished steel products from basic raw materials. Part
of this process is the reduction of iron ore to metallic iron which
is done in blast furnaces. Carbon, which is provided as coke, has
been found to be the best reduction agent. A charge of iron ore
coke, and limestone is put in the top of a blast furnace. Hot
blast air entering near the bottom of the furnace passes through
the charge and forms a gas with the coke which reduces the oxides
in the ore to metallic iron. Impurities react with the limestone
to form slag.
The coke necessary to this process is produced by heating coal at
900 to 1100°C for a period of 10 to 20 hours to drive off all volatile
materials.
5.1 Coking Process
Essentially all the coke in this country is produced using the by-
product recovery process. Coal is heated in the absence of oxygen
in closed ovens. The volatiles driven off are recovered and partially
offset the cost of making coke.
The ovens are typically 18m long, 6.5m high but only 50cm wide and
alternate, in a structure called a battery which may contain 80 to
120 ovens, with heating chambers in which coke oven (and/or blast
furnace) gas is burned. The heating chambers provide the heat
required for distillation by conduction through the oven walls.
The volatiles given off during the coking process include tars,
light oils, vaporized hydrocarbons, napthalene, and coke oven gas.
-13-
-------
At the end of the coking period, doors at both sides of the oven
are opened. A ramming device on one side pushes the hot coke into
a quench car located on the other side of the oven. The quench
car takes the coke to a quench tower where the coke is cooled
with water sprays. The coke is then stored for use in the blast
furnaces. The oven is meanwhile given a new charge of coal. Each
oven in the battery is at a different stage of the coking process
at any given moment so that production is continuous for the battery,
The typical uncontrolled oven charging process gives off 60% of
the atmospheric emissions associated with, this coking process.
Wet coal, blended and weighed, is loaded into the hoppers of a
larry car which moves along the top of the battery. The larry
car is positioned over an oven requiring a charge and the coal
is dumped through open charging ports at the top of the oven.
Hot gases in the oven are displaced and pollutants such as hydro-
carbons, graphite, tars, char, and coal dust are emitted. The
charging ports of the oven are then closed and the distallation
process begins.
There are several modifications of this system which are aimed
at reducing emissions. They include aspiration systems, which
attempt to increase the draft in the oven; larry mounted scrubbers;
and closed charging systems.
5.2 Charging System
The emissions test program reported herein was conducted at coking
facilities which used a Coalteck Pipeline charging system with a
Cerchar coal preheater. A schematic drawing of this system is
given in Figure 5-1. This is a closed system which, substantially
improves coke quality and has the potential for reducing emissions.
-14-
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TO ATMOSPHERE
WET SCRUBBER
TO WATER
TREATMENT
WET COAL
VENTUHI
PREHEATER
\ /
FEED HOPPER
A\\\\ FEEDER
COKE-OVEN GAS
AIR
COMBUSTION CHAMBER
SECONDARY
CYCLONE
PRIMARY CYCLONE
XX
DISTRIBUTION HOPPER
CHARGE BINS
II I Ml
RECYCLE BLOWER
PIPELINES TO OVENS
FIGURE 1
CERCHAR COAL PREHEATER WITH COALTEK PIPELINE CHARGING SYSTEM
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In this system, wet coal is withdrawn by screw conveyor from
existing coal storage facilities. It is sized and fed to the
Cerchar preheater by a variable speed screw conveyor. The wet
coal is fed into a flash drying entrainment section where it comes
into contact with a stream of hot oxygen-free gas. The gas carries
the partly dried, entrained coal up through the preheater. In the
combustion chamber, low-sulfur coke oven gas is burned nearly
stoichiometrically with air for complete combustion with low residual
oxygen. The hot gases leaving the combustion chamber are a mixture
of freshly burned gas and recycled products of combustion. The
mixed gases leave the combustion chamber at a temperature of 385
to 650°C, and pass through the venturi section of the preheater.
The wet coal is pushed into this high velocity gas stream by the feed
screw. Temperature at the upper end of the flash drying section is
in the 260 C range. The preheated coal passes overhead and is re-
covered in primary and secondary conventional cyclone separators.
Hot coal from the bottom of the cyclones feeds to a distribution bin.
From the distribution bin, coal is distributed to one of six charging
bins. Coal is discharged from the charging bins through a pipeline
system which feeds the oven being charged.
Gas from the outlet of the secondary cyclones is split into two
streams. Gas volumes equivalent to the combustion gases and moisture
driven off the coal go to a venturi scrubber for cleaning before
being exhausted, to the atmosphere. The remaining gas volume is
boosted in pressure by means of a recycle fan and then returned
to the combustion chamber where it is used to temper and add to the
flow of the combustion gases passing up through the preheater.
Automatic controls adjust the pressure differential across the secondary
-16-
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cyclones to maintain the desired flow of gases through the preheater.
5.3 Scrubber Water System
Of particular interest in this report is the scrubber water treatment
system. A schematic diagram of the system is shown in Figure 5-2.
It should be noted that this was the system used at the time of
testing and that major modifications have since been made.
Scrubber effluent is piped to a splitter tank where heavy particulate
matter is settled out. The scrubber water, less the heavy particulate,
flows to a flotation cell where buoyant materials are skimmed out
and removed. The clarified water flows to the venturi scrubber
pumping tank from which it is pumped back to the scrubber.
Preheated coal is moved from the distribution and charging bins by
pressurizing these bins with steam. When coal is discharged from a
bin, the coal discharge valve opens and the coal is forced out of
the bin and along the appropriate pipeline by the steam pressure
in the bin. The bins are then depressurized by venting to the
distribution bin vent condenser tank. A small quantity of clarifier
scrubber water by-passes the scrubber and is used in the condenser.
The condensate is drained to the splitter tank.
The vented steam from each of the six charging bins is condensed
in a single charging bin vent condenser tank. Make-up water is
used to condense this steam. The condensate from this tank flows
directly into the scrubber pumping tank.
-17-
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ceiL
oo
I
s'rcttr
—,
iC ooJ—L
OtSTJR
J3J 6 KH.
annr. a/v
KfVtUT
1
S3S 6 KM. f
r
*>AJfZ&
&=&-]
FIGURE 5-2
SCRUBBER WATER TREATMENT SYSTEM
,— TO OlHCK SCttM9f*
-------
6.0 TEST PROCEDURES
6.1 Test Program
The test program was conducted around the north scrubber
unit of the Jones and Laughlin Steel Corporation's Aliquippa
coal preheater in July and August of 1978. A summary of the
testing accomplished is given in Table 6-1.
For the gas stream sampling; velocity, temperature, gas
analysis, and other parameters required for particulate
and polycyclic organic material (POM) sampling were re-
corded and isokinetic sampling maintained as specified by
the following E.P.A. Methods:
o Method #1 - Sampling and velocity traversed for
stationary sources.
o Method #2 - Determination of stack gas velocity
and volumetric flow rate (type S
pitot tube).
o Method #3 - Gas analysis for C02, 0~, CO and dry
molecular weight using an Orsat unit.
o Method #4 - Determination of moisture content in
stack gas, derived from actual sampling
train.
o Method #5 - Determination of particulate in the inlet
and outlet of the scrubber.
In addition to the above, gas stream sampling was also per-
formed for the following parameters by the methods noted:
o Polycyclic organic materials (POM) in the inlet and
-19-
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outlet of the scrubber with particulate weight reported.
(POM Method).
o Benzene soluable organics (BSO) in the inlet and outlet
of the scrubber with particulate weight reported.
(POM Method).
o Benzene and total hydrocarbon (THC) concentrations in
the inlet and outlet of the scrubber. (Grab flask
method).
o Chloroform soluble organics (CSO) in the inlet and
outlet of this scrubber. (Using EPA-5 particulate
samples).
o Sulfur content in the impinger catches of the inlet
and outlet sampling trains. (Using POM test samples).
Scrubber inlet and outlet water was sampled by the grab flask method
to determine POM levels.
Coal samples were collected for each test period. These samples were
analyzed for ash, volatiles, hydrogen, and sulfur for fractions
larger and smaller than 100 mesh. In addition, 2 coal samples were
analyzed for trace metals.
-20-
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TABLE 6-1
SUMMARY OF YRC TESTING
PARAMETER
POM
NO. OF
TESTS SAMPLING METHOD
22
POM Train
ANALYTICAL METHOD
IR, LRMS,
Combined GC/MS
SAMPLING LOCATION
(Across Scrubber Unless Noted)
10 Inlet
12 Outlet
Level 1
Organics
(2) Gas (POM Train)
(2) Water (Grab Flask)
(2) Blank
EPA-1
Organics
Gas: POM Test #2
(Inlet & Outlet)
Particulate
and CSO
EPA-5 Train
EPA-5 for Particulate
PA-DER for CSO
1 Inlet
3 Outlet
BSO
POM Train
EPA-5
Modified
3 Inlet
3 Outlet
Sulfur in
Impinger
Catches
POM Train
Grav. Method
w/ignition of residue
POM Test #1
(Inlet & Outlet)
Benzene S 15
THC
Grab Flask
GC
POM in
Scrubber
Water
Grab Flask
Combined GC/MS
3 Inlet
3 Outlet
Coal
Analysis
21
Grab Sample
All: ASTM for Volatiles,
Ash, C, H , S, Size
(2) : Spark Source for
trace metals
9 Inlet
10 Outlet
(Sampling done across coal preheater
-------
6.2 Sampling Point Determinations
EPA Method 1 was used to determine the location of a representative
sampling point within both the 45" I.D. Inlet duct and the 44"
I.D. Outlet Duct. The Inlet Duct sampling location was downstream
of the recycle loop branch. The outlet sampling location was the
scrubber stack. Each test run was conducted until a minimum of
one (1) cu. meter (at meter conditions) was obtained.
The Inlet scrubber water samples were taken at the blowdown Inlet
line on Level 3. The Outlet samples were taken from the return
line upstream of the connection with the return line from the
south scrubber unit. This was at Level 7 .just upstream of the
splitter tank.
-22-
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6.3 Gas Velocity
The gas velocity was determined in accordance with guidelines
outlined in EPA Method 2 (Determination of Stack Gas Velocity and
Volumetric Flow Rate).
A precalibrated type S pitot tube and thermocouple attached to
the sampling probe were used to measure the velocity pressure
on an inclined manometer, (see Figure 6-1)
6.4 Gas Composition
i
The gas composition was determined in accordance with guidelines
outlined in EPA Method 3 (Gas Analysis for Carbon Dioxide, Oxygen,
Excess Air and Dry Molecular Weight).
A sample line was attached to the sampling probe and sample
drawn by a vacuum pump into an evacuated Tedlar bag. The contents
of the bag were then analyzed for 02, CC>2 and CO with an Orsat Analyser.
(see Figure 6-2)
-23-
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POTSNTIOM6TSR
MANOMETER
FIGURE 6-1
PRELIMINARY VELOCITY TRAIN
GiAss-i.;:reo JSOBE—•
57SS1
tCZ 3A7H
FIGURE 6-2
TEDLAR BAG SAMPLING TRAIN
SVACSA7S3
T2DLA3-
3AG
-24-
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6.5 Moisture in Stack Gas
Preliminary determination of the stack gas moisture content
was performed in accordance with EPA Method 4 (Determination of
Moisture in Stack Gases). The method employs condensation and
adsorption techniques. The sampling apparatuses shown in Figure 6-3,
includes a heated probe with glass wool packing in a tube
connected to the probe outlet, tygon tubing, four impingers,
gas pump and a dry gas meter.
The sample is drawn through the heated probe to prevent condensa-
tion and then through the glass wool to catch any solid parti-
culate matter. The sample is then condensed in the first two
impingers, which are filled with 100 ml of distilled water each
and submerged in an ice bath. The third impinger serves as an
extra container for carry-over, should the moisture condensation
be appreciable. The gas then passes through the fourth impinger
which contains 300 gms. of silica gel for adsorbing any additional
moisture. The sample gas finally passes through the gas pump
and the dry gas meter where volumetric measurement of the sampled
gas is taken.
Moisture determinations were also made concurrently with all EPA Method
5 particulate and organic tests.
-25-
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PROBE
CZI
•t'j?t»
GLASS WOOL
I
to
cr>
I
¥ ~
IMPINGER TRAIN
AIR PUMP
oriv GAS METER
FIGURE 6-3
PRELIMINARY MOISTURE TRAIN
-------
6.6 Particulate Method
The particulate and chloroform soluble organic concentrations
were determined in accordance with guidelines outlined in EPA
Method 5 (Determination of Particulate Emissions from Stationary
Sources).
The sampling apparatus consisted of a probe, cyclone bypass, filter,
four impingers, dry gas meter, vacuum pump and flow meter
(see Figure 6-4). The probe was 5 ft. in length and glass lined.
The stainless steel button-hook type probe tip was connected by
a stainless steel coupling with Teflon packing to the probe.
The probe consisted of 5/8 inch outside diameter tube with a
ground balljoint on one end. The probe was logarithmically wound
from the entrance end with 26-gauge nickel-chromium wire. During
sampling, the wire was connected to a variable transformer to
maintain a gas temperature of'250°F in the probe. The wire wound
tube was wrapped with fiberglass tape and encased in a 1-inch-OD
stainless steel casing for protection. The nozzle was attached
to the end of the probe casing.
The probe connected to a cyclone bypass which connected to a very
coarse fritted glass filter holder which contained a tared glass
fiber filter. The filter was contained in an electrically heated
enclosed box which was thermostatically maintained at a temperature
of 250°F to prevent condensation.
Attached to the heated box was an ice -bath containing four impingers
connected in series with glass balljoints. The first impinger re-
ceived the gas stream from the filter. This impinger was of the
Greenburg-Smith design modified by replacing the tip with a 1/2
inch ID glass tube extending to 0.5 inches from the bottom of the
flask. This impinger was initially filled with 100 milliliters of
distilled water. The second impinger was of the Greenburg-Smith
design and, like the first, was initially filled with 100 milliliters
of distilled water. The third impinger, which was left dry, was
a Greenburg-Smith impinger modified like the first. The fourth
-27-
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Inclined Manometer
I
NJ
00
1
Stack
Wall
Pitot
Tube
Sampling
Nozzle
Stack
Thermocouple ~
Coarse Control
Valve
Thermometer
Impinger
Train
Air Tight
Pump
Vacuum Gauge
Pyrometer
Thermometer
Dry Gas
Meter
Inclined
Manometer
FIGURE 6-4
PARTICULATE SAMPLING TRAIN
-------
impinger was also a Greenburg-Smith impinger modified like the
first and contained dry silica gel.
From the fourth impinger the effluent stream flowed through a
check valve; flexible rubber vacuum tubing; vacuum gauge; a
needle valve; a leakless vacuum pump rated at 4 cubic feet per
minute at 0 inches of mercury gauge pressure and 0 cubic feet per
minute at 26 inches of mercury gauge pressure and connected in
parallel with a bypass valve; and a dry gas meter rated at 0.1
cubic foot per revolution. A calibrated orifice completed the
train and was used to measure instantaneous flow rates. The
three thermometers were dial type with a range of 25° to 125°F.
A fourth thermometer in the heated portion of the box has a range
up to 500°F. The dual manometer across the calibrated orifice
is an inclined-vertical type graduated in hundredths of an inch
of water from 0 to 1.0 inch and in tenths from 1 to 10 inches.
Once completely assembled, the sampling train was leak-checked to
insure collection of a representative flue gas sample. To per-
form the leak-check, the vacuum pump was started and the nozzle
orifice covered to insure an air-tight seal. After bringing the
vacuum pressure up to 15 psi, the dry gas meter was checked for
any air leaks. Once the required leak check was performed, the
probe was inserted into the duct at the specific sampling point.
Velocity and temperature measurements of the flue gas at the pitot
head were recorded and a sampling rate determined for isokinetic
sampling.
6.6.1 Test Data
During each run the following readings were obtained at each
point:
1. Point designation
2. Clock time
3. Dry gas meter reading (CF)
4. Velocity head (AP in inches water)
5. Desired pressure drop across orifice
AH in inches water)
-29-
-------
6. Actual pressure drop across orifice
AH in inches water)
7. Dry gas temperature (°F) gas meter inlet
8. Dry gas temperature (°F) gas meter outlet
9. Vacuum pump gauge reading (in. Gh)
10. Filter box temperature ( F)
11. Dry gas temperature (°F) at the discharge of last
impinger
12. Stack temperature (°F)
13. Stack pressure (inches water)
The relationship of AP reading with the AH reading is a function
of the following variables:
1. Orifice calibration factor
2. Gas meter temperature
3. % moisture in the flue gas
4. Ratio of flue gas pressure to barometric pressure
5. Stack temperature
6. Sampling nozzle diameter
A nomograph was.used to correlate all the above variables such
that a direct relationship between AP and AH was determined
by the sampler within fifteen seconds and isokinetic conditions
maintained throughout the test.
6.6.2 Sample Recovery for Particulate and Chloroform SoluableOrganics
The Particulate and chloroform soluble organic test trains
generated the following samples:
1. Acetone wash of the nozzle, probe and front half
filter holder in sealed, labeled containers.
2. Filter sealed and labeled in a petri dish.
3. Acetone wash of the back half filter holder, impinger
lines and impinger in sealed labeled containers.
4. Water solutions from the impingers placed in sealed,
labeled containers.
-30-
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6.7 POM Sampling Method
The POM sampling train was utilized for the collection of
polycyclic organic material in the flue gas, before and after the
particulate scrubber. The POM sampling train, as shown in Figure 6-5
consisted of a Method 5 train with an XAD-2 adsorbent module
located downstream of the filter and condenser and upstream of
the impingers. Utilizing this arrangement, POM emissions could be
determined by analysis of the probe wash, filter catch, condensate,
and adsorbent sampler catch. The impingers were only used to
cool and dry the stack gases before they entered the dry gas
meter.
The POM train used in the field consisted of a heated glass-
lined probe with a stainless steel nozzle at the -probe head, a
heated filter assembly, one Greenburg-Smith type condenser
impinger, the adsorbent sampler and four additional impingers.
In order to insure adequate POM collection efficiency in the
adsorbent sampler, the flue gas temperature had to be kept as low
as possible without condensing large quantities of water vapor.
For this reason, a condenser (Greenburg-Smith impinger) was used
between the filter and the adsorbent sampler. Connected to the
impinger assembly was an umbilical, vacuum pump, dry gas meter
and an orifice. All connections in the filter, adsorber and
impinger assemblies were glass. Thermal control at the probe
and the filter assembly was maintained in a heated mode at 325 F
(versus 250 F when using the EPA Method 5 sampling train).
Maintaining the probe and filter at the higher temperature prevent-
ed condensation and/or adsorption of SO., and POM (followed by the
destructive reaction of SO, with POM) in these components.
Thermocouple connections at the probe head, the inlet to the
filter assembly, the inlet to the adsorber, the fourth impinger
outlet and the inlet-outlet of the' dry gas meter, allowed for
monitoring sampled flue gas temperatures throughout the sampling
train. Once completely assembled, the sampling train was leak-checked
to insure collection of a renrescntative flue ga.s sample.
-31-
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I
u>
Inclined wanoinular
(A I')
.TlUM IIHH;IHI|iii(/ur
I jnln
Chock
VilJ VU
Vacuum
Ice
lui IU
Ini.-l I nod
mammii-icir
(A I.)
FIGURE 6-5
POM TRAIN
-------
6.7.1 Pom Sample Recovery
Recovery of samples from the four separate sections of the POM
sampling train included:
1. Methylene chloride wash of nozzle, probe and front
half filter holder, sealed and labeled.
2. Acetone wash of nozzle, probe and front half filter
holder, sealed and labeled.
3. Filter placed in sealed, labeled petri dish.
4. Collected condensate and methylene chloride rinse,
sealed and labeled.
5. Adsorbent module, sealed and labeled.
The samples from each train were placed in sealed and labeled
containers and kept in darkness to insure against photo-oxidation
prior to analysis.
-33-
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6.8 Benzene Soluble Organics Method
An EPA Method 5 sampling train was modified similar to the POM
sampling train by insertion of an XAD-2 adsorbent module down-
stream of the filter and first impinger and upstream of the last
four impingers.
Assembly and preliminary procedures such as leak checks were per-
formed as per normal procedures. Velocity and temperature measure-
ments at the flue gas at the pitot head were recorded and a sampling
rate determined for isokinetic sampling.
t
The following tests were performed for determination of benzene
soluble residue:
Test Location Date
1 inlet 7-16
1 outlet 7-16
2 inlet 7-17
2 outlet 7-17
3 inlet 7-30
3 outlet 7-30
6.8.1 BSO Sample Recovery
The nozzle, probe and front half filter holder were first washed
with benzene, samples were labeled and sealed in light proof contain-
ers. The nozzle, probe and front half filter holder were then
washed with acetone with samples labeled and sealed in appropriate
containers. The filter and the adsorbent module were placed in
separate, sealed and labeled containers. The back half (which
includes the impingers downstream of the adsorber as well as the
additional condenser) of the train was cleaned up separately with
both benzene and acetone washes. These samples were labeled, sealed,
and placed in light proof containers. Each train generated the
following samples:
-34-
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1. Front half benzene wash
2. Front half acetone wash
3. Filter
4. Adsorber
5. Back half benzene wash
6. Back half acetone wash
6.9 Determination of Sulfur in Impinger Catches
An analysis for sulfur was performed on the impinger catches of the
following tests:
POM Test 1 Inlet
POM Test 1 Outlet
Previously described, modified EPA Method 5 sampling trains with
XAD-2 adsorbers after the first impinger were used for the POM
tests.
The samples generated for sulfur analysis from each test were:
1. Impinger water
2. Methylene chloride impinger wash
-35-
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6.10 Benzene and Total Hydrocarbons
Fifteen grab samples taken with gas sampling flasks at the inlet
and outlet to the coal preheater scrubber were analysed using a
gas chromatograph for benzene and total hydrocarbons (THC).
Benzene and THC samples were taken for the following tests:
Date Location
7/26/78 Inlet
;j Outlet
7/27/78 Inlet
Outlet
7/28/78 Inlet
Outlet
7/29/78 Inlet
Outlet
7/30/78 Inlet
Outlet
7/31/78 Outlet only
8/2/78 Inlet
Outlet
8/3/78 Inlet
" Outlet
Prior to actual sampling, these flasks were purged with flue gas
Once a sample was entrapped in the flask, the flask was wrapped
with aluminum foil to prevent photo oxidation, then kept cool on
ice for a short time before being transported to an on-site gas
chromatograph for analysis.
6.11 Coal Samples
21 coal samples were collected for each test period of the inlet
and outlet preheater process. All samples were analyzed for volatile
material, ash, carbon, hydrogen, and sulfur for fractions greater
than 100 mesh and smaller than 100 mesh. Each coal sample was
also examined by microscopy. In addition, the coal samples from
Test #2 inlet and outlet were analysed by spark source
-36-
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mass spectrometer (SSMS) for trace metals.
6.12 Scrubber Water
22 water samples from the inlet and outlet of the coal preheater
scrubber were obtained and analyzed for Polyciclic Organic Materials.
Due to funding restrictions, only six samples were actually analyzed.
-37-
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6.13 Sampling Problems
Inherent to any stack test is the margin of error due to
poor sampling conditions, namely; the physical arrangement
of sampling locations, the characteristics of the
sampled gas, and the specific industrial process involved.
For the sampling of the J & L coal preheater, all of the
above presented some problems.
The outlet sampling location was in the scrubber stack
where temporary scaffolding had been erected to accommodate
the test crew. Due to the poor quality of this scaffolding,
at least one particulate test had to be scrapped.
Gas stream moisture presented a difficult problem both
because it represented approximately 1/3 to 1/2 of the
gas stream and because it was nearly impossible to
predict moisture level in advance. The moisture content
in the gas stream was directly due to the coal being
processed. However, there was about a day's delay bet-
ween the actual blending of the coal (prior to test) and
the results of the lab's moisture analysis. Therefore,
the prediction of moisture content was really based on
guesswork. The assumed vs. actual moisture content for
each test is shown in Table 6-1.
The prediction of moisture content is essential in order to
-38-
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maintain isokinectic sampling rates. The effects of
poor moisture prediction is reflected in the percent
isokinetic values given for each test in Table 6-1.
Occasional shortcuts of heater boxes allowed appreciable
moisture collection on filters, thus hampering train
collection efficiency. The high moisture also affected
the manometer pitot lines. Condensed moisture and flue
gas grit were forced up into the pitot tubes by the high
pressure existing at the scrubber inlet (static pressures
up to 11" W.C.). This condition could not be remedied
by simply blowing the lines out with a pump, instead the
entire pitot assembly had to be removed out of the gas
stream, purged, and cleaned.
Process conditions, which are inherent to the operation of
the coal preheater system, also presented major problems.
Frequently sampling was interrupted by a shutdown of the
system. The most typical causes of this were clogging
of either the battery, feeder or preheater systems. In
addition, normal process fluctuations encountered during
test periods caused inconsistant flows and puffs of grit
in the system. These transient effects, coupled with the
high particulate and moisture loadings to begin with, were
most pronounced at the scrubber inlet where frequent
filter changes were required. As many as 5 and 6 filter
changes were reported for some tests.
-39-
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The time delays associated with the frequent filter
changes at the inlet caused the inlet sampling periods
to last longer than the outlet sampling periods so that it
is questionable as to whether the inlet and outlet tests
are actually simultaneous.
In addition, it is doubtful that fluctuations in process
conditions would have the same effect on both the inlet
and outlet sampling trains, i.e., puffs of grit would
most likely introduce a greater error at the inlet.
Finally, it is strongly suggested that uniform, fully
developed flow did not exist at the sampling locations.
This could have been caused by the sampling locations
themselves or, more probably, by process fluctuations.
The test averages for gas velocity at the inlet range from
14 to 27 M/S. Fluctuations of a similar magnitude are
conceivable during a particular test.
The errors introduced by these factors, i.e., a skewed
velocity component and fluctuations in velocity, would
most likely show up in the stack flowrate measurement.
The inlet and outlet flowrates, in terms of dry, std.
Nm /M should be equal. These rates are presented for each
test in Table 6.2. The fact that they are not equal
is evidence of the magnitude of the problems encountered.
-40-
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TABLE 6-2
TEST CONDITIONS
Test
POM 1
POM 2
POM 3
POM 4
POM 5
POM 6
POM 7
POM 8
POM 9
POM 10
POM 11
% Moisture
Assumed/Actual
Stack Flow
Rate ,
% Isokinectic Dry, STD, Nm /m
Inlet
Outlet
Inlet
Outlet
Inlet
Outlet
Inlet
Outlet
Inlet
Outlet
Inlet
Outlet
Inlet
Outlet
Inlet
Outlet
Inlet
Outlet
Inlet
Outlet
Inlet
Outlet
35.0/40.6
50.0/53.2
35.0/36.4
50.0/34.5
35.0/49.6
50.0/34.5
35.0/53.7
50.0/51.9
35.0/45.8
50.0/50.4
35.0/44.4
50.0/53.0
35.0/46.6
50.0/53.5
35.0/44.3
50.0/53/0
50.0/56.7
40.0/46.6
50.0/53.0
40.0/53.9
50.0/53.0
106.3
92.7
99.5
90.1
88.3
94.0
148.6
106.9
135.0
108.7
189.4
101.3
124.0
112.5
115.3
108.7
127.7
101.1
113.2
114.4
103.2
279
201
416
476
275
402
347
342
488
406
492
369
262
337
465
361
181
363
236
178
261
-41-
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TABLE 6-2 (con't)
Test
% Moisture
As s ume d/Act i ve
% Isokinetic,
Stack Flow
Rate
Dry, STD. Nm /m
Particulate
1 Inlet
Outlet
2 Inlet
Outlet
3 Inlet
Outlet
35:0/53.2
35.0/53.5
35.0/52.0
50.0/58.1
125.2
103.6
154.7
117.3
283
303
247
312
BSO- 1
2
3
Inlet
Outlet
Inlet
Outlet
Inlet
Outlet
50.0/26.4
50.0/44.5
45.0/24.0
50.0/47.3
35.0/35.0
50.0/50.0
79.4
95.9
80.7
91.4
110.6
112.4
462
317
609
498
325
270
-42-
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7.0 ANALYTICAL PROCEDURES
7.1 POM Analytic Procedure
7.1.1 Particulates
Particulate emission results were analyzed using the P.O.M.
Sampling Train "Particulate" methodology (gravimetrically) .
The procedure involved the separate analysis of two portions of
the sampling train (Front Half):
1. Nozzle, Probe, Front Half Filter Holder
2. Filter
Portion 1 apparatus was first washed with methylene chloride and
the resulting samples placed in sealed, labeled sample bottles.
Portion 1 apparatus was then washed with acetone and the resulting
samples placed in sealed, labeled bottles. These samples were
then dried to constant weight at room temperature.
The filter (portion 2) was placed in a sealed, labeled Petri Dish
and then also dried to constant weight at room temperature. The
combined weights of the filter catch and wash residue were in turn
used in the determination of particulate loading. The POM particulate
methodology is summarized in Figure 7-1.
7.1.2 Organic Analyses
In addition to particulate loading determinations from the POM
sampling train, two sets of organic analyses were performed on
the samples obtained from source tests utilizing the POM train.
The two organic analyses performed were Gas Chromatography/Mass
Spectrometry (GC/MS) Analysis and EPA Level 1 Organic Analysis.
o Gas Chromatography/Mass Spectrometry (GC/MS) Analysis
Twenty-two (22) POM stack samples and six (6) water samples
(Tests 1, 2, and 3, both inlet and outlet) were analyzed by GC/MS
analysis for twenty five organic (P.O.M.) species.
-43-
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FIGURE 7-1
POM SAMPLING TRAIN PARTICULATE
ANALYSIS METHODOLOGY
Nozzle,
Probe,
Front Half Filter Holder
Methylene
Chloride
Wash
Sealed Labeled
Sample Bottles
Sealed/Labeled
Sample Bottles
Sealed/Labeled
Petri Dishes
Dry to Constant
Weight at Room
Temperature
Dry to Constant
Weight at Room
Temperature
Dry to Constant
Weight at Room
Temperature
-44-
-------
The methylene chloride wash of the front half was filtered and
the solid filtered substance dried in a desiccator at room
temperature to constant weight. The acetone washes from the
front and back halves and the filter were dried in the same manner to
constant weight. These constant weight samples were then combined and
Soxhlet extracted using high purity methylene chloride for a
period of 24 hours.
The XAD-2 adsorber was also soxhlet extracted for 24 hours using
about 500 ml of methylene chloride. The condensate from the back
half was liquid extracted using methylene chloride in separatory
funnels fitted with Teflon stopcocks. The pH of the aqueous
sample was adjusted first to 2.0 with HC1 and subsequently to 12.0
with NaOH. The resulting methylene chloride extracts from all
of the soxhlet and liquid extractions along with the filtrate
from the Front half (CJ^Cl-) probe wash filtration were combined
and concentrated to 10-25 ml using a KudernaDanish apparatus.
The amounts of organic material with boiling points higher than
300°C were then determined by the gravimetric analysis method
(GRAV). Next, from each concentrated extract using the Kuderna
apparatus, 0.5 - 8 ml aliquots were subjected to three consecutive
solvent exchanges with cyclopentane. The resulting cyclopentane
solutions were chromatographed (LC) on a silica gel column,
collecting seven fractions by elution with solvent mixtures
(pentane-methylene chloride-methanol) of increasing polarity.
Gravimetric analysis was performed on the aromatic fraction
(fractions 2, 3, 4) to determine species having a molecular weight
(MW) less than 252 and greater than 252 due to the different
detection limits used for the MS analysis. A portion of fractions
2, 3, 4 were combined for GC/MS analysis and were analyzed for
25 POM species. An OV-17 glass capillary GC column and a Finnigan
Model 4023 Mass Spectrometer/Data System performed the GC/MS
analysis.
A graphical representation of the GC/MS analytic procedure is shown
in Figure 7.2.
-45-
-------
Procedure
Sample
Component
Probe Hash, Front
Half (CH2C12)
Acetone Wash, Front
and Back Half
Filter
Condensate, Back
Half (CH2C12)
XAD-2 Adsorber
Water Sample
FIGURE 7-2
GC/MS Analysis
-------
o EPA Level 1 Organic Analysis
Six samples (inlet and outlet air samples from Test No. 2,
inlet and outlet, water samples from Test No. 2, stack blank, and
water blank) were carried through the EPA Level 1 organic analysis,
The concentrated extract of each of the six samples were analyzed
by Gas Chromatography (TCO) using a flame ionization detector to
determine the quantity of organic material with boiling points
in the range of 100-300°C. The amount of organic material with
boiling points higher than 300°C were next determined by the
gravimetric analysis method (GRAY). The IR spectra of all samples
as potassium bromide micro-pellets were obtained on a Perkin-
Elmer 521 grating spectrometer. Each sample was then subjected
to liquid Chromatography using cyclopentane solutions on a
silica gel column. Seven fractions were collected by elution
with solvent mixtures (pentane-methylene chloride-Methanol) of in-
creasing polarity. All seven fractions were then individually
subjected to total chromatographable organics analysis, gravi-
metric analysis, liquid Chromatography and I.R. spectroscopy
using the same methods as just described. Finally, Low Resolution
Mass Spectroscopy (LRMS) analysis was carried out on a Dupont
21-110B sprctrometer. Sample sizes varied from 20 y to 50 y.
A graphical representation of this analysis is given in Figure 7-3.
7.2 Particulate and Chloroform Soluble Organic Analysis
Particulate emission results were analyzed and characterized as
either chloroform soluble or non-chloroform soluble using the
State of Pennsylvania D.E.R. "Particulate" Methodology.
The procedure involved the separate analysis of the four portions
of the sampling train:
1. Nozzle, Probe, Front Half Filter Holder (Acetone Wash)
2. Filter
3. Back Half, Filter Holder, Impinger lines, Impingers (Acetone
Wash)
4. Impinger solutions (water)
-47-
-------
i
*=.
oo
Sample Mo.
2, Inlet
2, OuLlet
UyO, 2, Inlet
H2O, 2, Outlet
Stack Blank
11,0 Blank
-4--
i
o
tj
H
M
I
*J
U i
cd i
*•"
M
g
i-t
4J
U
-------
Samples from portions 1 and 3 were placed in sealed, labeled
sample bottles and kept in a dark, refrigerated place. After
refrigeration, the samples were evaporated to dryness at room
temperature whereby the residue was thoroughly extracted using
chloroform. The extracted samples were then divided into two
separate layers of chloroform-soluble particulate and non-
chloroform-soluble particulate.
The filter sample was placed in a sealed, labeled Petri Dish
and stored in a dark, refrigerated place. After refrigeration
the sample was thoroughly extracted using chloroform and divided
into two separate layers of chloroform - soluble particulate
and non-chlorofo/rjm-soluble particulate.
Samples from the Impinger solutions were also placed in sealed,
labeled sample bottles and stored in a dark, refrigerated place.
After refrigeration, the samples were not dried but were immediately
extracted using chloroform. The extracted samples were also
divided into two separate layers of chloroform-soluble particulate
and non-chloroform-soluble particulate.
It should be noted that the EPA Method 5 "Particulate" Analysis
involved the same procedure, but only for the front half (i.e.
Portions 1 and 2) . See Figure 7-4" for a graphical representation
of methodology previously described.
7.3 Benzene Soluble Organics Analytic Procedures
Each of the six (6) samples generated from the six (6) simultaneous
modified EPA Method 5 BSO tests were analyzed for benzene soluble
residue and particulate residue in the following manner:
1. The benzene wash was filtered. The filter was dried and
weighed, yielding particulate weight. The benzene wash
was then evaporated at room temperature and the remaining
residue weighed for benzene solubles.
-49-
-------
TABLE 2A
EPA-5 SAMPLING TRAIN ANALYTICAL METHODOLOGY FOR
EVALUATION OF CHLOROFORM-SOLUBLE AND NON-CHLOROFORM SOLUBLE! PARTICULATE
I
Ul
o
Nozzle,
Probe,
Front Half
Filter Holder
(Acetone Wash)
Filter
Sealed/Labeled
Sample Dottles
Sealed/Labeled
Petri Dishes
Evaporate to
Dryness at Room
Temperature
Chloroform
extraction
Chloroform
Extraction
Ichloroform-j
(Soluble
{particulatoj
Non-
Chloroform-
Soluble
Particulate
Chloroform-
Soluble
Particulate
Back Half Filter
Holder, Impinger
Lines, Impingers
(Acetone Wash)
Impinger
Solutions
(Hater)
Silica 1
Gel I
Sealed/Labeled
Sample Bottles
Sealed/Labeled
Sample Bottles
Evaporate to
Dryness at Room
Temperature
Chloroform
Extraction
Sealed/Labeled
Sample Bottles
Chloroform
Extraction
Chloroform
Extraction
Non-
Cli lorof o cm-
Soluble
Particulate
Chloroform-
Soluble
Particulate
Non-
Chloroform
Soluble
Particulate
Chloroform-
Soluble
Particulate
Non-
Chloroform
Soluble
Particulate
Chloroform
Soluble
Particulate
"Front Half Catch".-
-4*
"Back Half Catch"
•EPA Method 5 "Particulate" ->«|
State of Pennsylvania DER "Particulate"
FIGURE 7-4
-------
2. Benzene was added to the acetone wash. This mixture was
filtered, the filter was dried and weighed for particulate
weight. The acetone-benzene mixture was evaporated at room temperature
and the remaining residue weighed. Acetone and benzene are miscible
so the residue weight reflected not only the benzene solubles,
but acetone solubles as well.
3. The filter was dried and weighed for particulate weight.
Then, a soxhlet extraction with benzene was performed, the
benzene was evaporated at roan temperature and remaining residue
reported as benzene soluble residue.
4. A soxhlet extraction with benzene was performed on the XAD-2
adsorbent resin. The benzene was evaporated at room temperature, the
residue weighed and reported as benzene soluble residue.
5. The water sample from the back half benzene wash was extracted
with benzene. The water-benzene mixture was filtered, and the
filter dried and weighed. The water fraction was evaporated and
the residue weighed. Residue from both the filter and water
fraction are added to give particulate weight. The benzene
fraction was evaporated and the residue weighed to yield benzene
solubles.
6. 'The acetone wash was analyzed in the same manner as procedure
No. 2.
7.4 Determination of Sulfur in Impinger Catches
Impinger catches from POM Test #1 inlet and outlet were analyzed
for sulfur using Method 427A "Gravimetric Method with Ignition
of Residue", Standard Methods for the Analysis of Water and
Wastewater, 14th Edition, 1975.
The analysis involved the addition of Barium Chloride to the
sample to precipitate Sulfate as Barium Sulfate. The precipitation
was carried out near the boiling temperature, and after a period
of digestion the precipitate was filtered, washed with water until
free of chlorides, dried, and weighed as BaS04-
-51-
-------
7. 5 Benzene and Total Hydrocarbons Analytical Techniques
Fifteen (15) Grab samples taken with gas sampling flasks at the
inlet and outlet to the coal preheater scrubber were analyzed
for benzene and total hydrocarbons (THC). Samples were analyzed
by an Analytical Instrument Division gas chromatograph that was
set up in the on-site trailer. A carbopak C, 0-1% SP 1000 column
at 125°C was used for determination of benzene and a sample loop
was used for THC.
7. 6 Scrubber Water Analysis
Of twenty-two (22) scrubber water samples taken, only six (6)
were analyzed for POM's by the GC/MS technique described previously
in Section 7.L2. The samples from the scrubber inlet and outlet
were liquid extracted, combined and concentrated, placed through
gravimetric analysis, liquid chromatography (GRAY of aromatic
fraction) and finally subjected to GC/MS analysis. A graphical
representation of the GC/MS analytic procedure for scrubber water
samples is shown in Figure 7.2.
7. 7 Coal Analysis
Twenty-one (21) inlet and outlet coal samples were sieved through
a 100 mesh screen and analyzed for moisture, volatile matter, ash,
sulfur and carbon contents according to ASTM methods (D3173, 3174,
3175, 3177, and 3178). Table 8-41 shows the sieving and moisture
analyses results. For most of the coal samples, the fraction
smaller than 100 mesh was found to be ^10% for the Inlet samples and
^20% for the Outlet samples. The moisture contents for all samples
was ' around 1%. The results, of volatile, ash, sulfur, and carbon
analyses are summarized in Tables §.42 and 8-43. Slightly higher
ash contents were observed for the Inlet samples than the corres-
ponding Outlet samples. No substantial differences in volatile,
carbon, hydrogen, and sulfur contents were observed between the
-52-
-------
Inlet and Outlet samples.
The coal samples from Test No. 2 Inlet and Outlet were also
analyzed for trace elements. The results are given in Tables 8-44 thru 8-47
A summary table with the elements over 5 mg/kg concentration for
the four samples is also presented (Table 8-48). All the coal
samples were also examined by stereo microscope at magnifications
from 7 to 30 times. Each sample was subsequently documented with
a photomacrograph taken at 6X magnification. Figure 7-5 depicts
a graphic representation of the analyses performed on the coal
samples.
-53-
-------
I
t_n
N\
" Analysis
Coal from
2 Inlet and
2 Outlet
Coal from
al I' other
Tests
P.
o
u
0)
o
M
u
•
0
-------
8.0 RESULTS
8.1 Particulate Results from POM Trains
The particulate results (front half only with probe and
filter at 163°C) of each of the twenty-two POM tests are
given in Table 8-1, listed by sampling train components.
The corresponding concentration data at the source are
given in Table 8-2. The major portion of the particulate
was found on the filters for both inlet and outlet samples.
However, substantial amounts of particulates were recovered
from the probe washings for the inlet samples.
The average loading of particulates in these coal preheater
effluents before the scrubber was 15.2 g/m , and after the
scrubber was 0.84 g/m , i.e., about 95% of the particulates
were removed by the scrubber. The actual particulate con-
3 3
centrations varied from 10 g/m to 24 g/m among tests at
the inlet of the scrubber, and they varied from 0.1 g/m to
1.7 g/m among tests at the outlet of the scrubber. The
scrubber efficiency for removing particulates in these tests
varied from 99% to 83%.
-55-
-------
TABLE 8-1
SUMMARY OF PARTICULATE EMISSIONS FROM COAL PREHEATERS (POM TRAIN)
Test
1
2
2B
3
4
5
6
7
8
9
10
11
Sample
Inlet
Outlet
Inlet
Outlet**
Outlet
Inlet
Inlet*
Outlet
Inlet
Outlet
Inlet***
Outlet
Inlet*
Outlet
Inlet
Outlet
Outlet*
Inlet
Outlet
Inlet
Outlet
Total
Particulate
g-
15.
0.
13.
0.
0.
1.
13.
0.
8.
1.
6.
0.
16.
1.
10.
1.
0.
5.
0.
12.
1.
9200
3738
4845
1479
3195
9878
6761
8584
8325
4285
5252
8555
6043
1885
8699
3547
2472
0819
2790
9479
0016
Particulate
Cone. .,
g/m
12.
0.
10.
0.
0.
4.
14.
0.
10.
1.
14.
1.
16.
1.
13.
1.
0.
21.
0.
15.
1.
92
452
52
114
287
398
41
805
31
751
12
764
04
166
11
381
299
26
425
13
309
% Particulate
Removed
96
98
97
91
94
83
87
92
89
98
91
.5
.9
.3
.3
.4
.0
.5
.7
.5
.0
.4
* Questionable data due to moisture
** Test invalid due to train leak
*** Test invalid due to insufficient sample
-56-
-------
TABLE 8-2
PARTICULATE LOADINGS BY SAMPLING TRAIN COMPONENTS(POM TRAIN)
Test No.
1 Inlet
1 Outlet
21. Inlet
2A Outlet**
2B Outlet
3 Inlet
3 Outlet
4 Inlet*
4 Outlet
5 Inlet
5 Outlet
6 Inlet***
6 Outlet
7 Inlet*
7 Outlet
8 Inlet
8 Outlet
9 Outlet*
10 Inlet
10 Outlet
11 Inlet
11 Outlet
Probe Wash,
Front Half
(CH2C12)
3.8149 g
0.0885
3.8279
0.0764
0.1482
1.6649
0.0402
3.3402
0.0227
3.9592
0,0374
2.1526
0.0244
3.4242
0.0653
2.8087
0-0441
0.0618
1.9898
0.0459
3.9317
0.0542
Probe Wash,
Front Half
(Acetone)
0.0629 g
0.0422
0.1260
0.0271
0.0423
0.0332
0.0314
0.2425
0.0521
0.5202
0.0420
0.0906
0.0454
0.1600
0.0767
0.0368
0.1040
0.0444
0.0657
0.0315
0.1353
0.0413
Filter
12.0422 g
0.2431
9.5306
0.0444
0.1290
0.2897
0.3374
10.0934
0.7836
4.3441
1.3491
4.2820
0.7857
13.0201
1.0465
8.0244
1.2066
0.1410
3.0264
0.2016
8.8809
0.9061
* Questionable data due to moisture
** Test invalid due to train leak
*** Test invalid due to insufficient sample
-57-
-------
8.2 Gas Chromatography/Mass Spectrometry (GC/MS) Analysis
8.2.1 Identification of POMs
The concentrations determined for the POMs analyzed for each
sample are tabulated in Tables 8-5 through 8-15. The total
ion chromatographs for the aromatic fractions of each sample
are given in Appendix B. These concentrations were computed
from calibration data by the methods described previously.
For those compounds which are present in the mixture, the
calibration data obtained directly are used.. For the
Benzofluoranthene isomers, the calibration data for Benzo-(a)
pyrene were used for the reasons discussed previously. The
remaining compounds have estimated calibration curves based
on their molecular weight. The use of this estimation procedure
had a minimal impact on the results obtained since most of
compounds for which it was used were not found in any of the
samples. The POMs not found include cholanthrene, dibenzcarbazole,
and dibenzacridines. The following discussion presents the
efforts made to verify the absence of these compounds.
Cholanthrene (mw 254) was not detected in any of the samples.
Some of the inlet and outlet samples show the presence of
several 254 POMs in the proper retention time region for
cholanthrene, but the spectra and the relative elution order
are those of binaphthyls. The concentration of the binaphthyls
is low, on the order of 0.1 to 0.2 ug/mL in the most concentrated
stack sample. Sample 8, inlet, was examined before liquid
chromatography separation to look for the presence of other
mw 254 POMs. Figure 8-1 shows the ion chromatograph for mw 252
-58-
-------
and 254 for the #8 inlet sample prior to LC separation. The
three peaks marked with arrows on the mw 254 ion chromatograph
are the same as those seen in the samples after LC and their
spectra best fit the various binaphthyls. Several additional
mw 254 POMs are seen, but at levels below that of the binaphthyls.
Extrapolation of those levels to the samples examined gives
a concentration level at or below the detection limit. Thus, no
concentration values are given in the tables for cholanthrene.
The analysis of 7,12-dimethyl benz(a)anthracene is complicated
by the large number of unresolved isomers of dimethyl and
ethyl isomers present, such as dimethyl chrysenes, etc.- Figure
8-2 shows the two major ions in the mass spectra of the dimethyl
benzanthracene and dimethyl chrysene isomers, with the arrows
on the mw 256 ion chromatogram indicating the location of the
C20 H16 isomers- Tests where small amounts of 7,12-dimethyl
benz (a) anthracene (the C20H16 isomer of interest) were added to
one of the samples (#B inlet after LC) were unsuccessful at
pinpointing the location of this isomer within the cluster of
C20H16 POMs- To 9ive an estimate of the level of these POMs
present, the area for each of the isomers noted in Figure 8-2 were
summed and the concentration computed using the approximate
response/ng value based on the molecular weight dependence of
POM response factors.
Neither dibenzacridine nor dibenzocarbazole were found in any of
the samples. It may have been possible that dibenzocarbazole,
which has its molecular weight ion at mw 257, may be present in
these samples but was obscured by the abundance of methyl-
benzopyrenes and methyl perylenes (mw 266). The methyl
-59-
-------
180.0-1
232 _
3.1-1
254 _
asa
28:28
BaP
3«azo fluoranchenes
JU
aee
39:09
330
31:43
1000
33: 3d
Figure 8-1
1350 SCAN
35:19 TIME
-d .
Ion Chromatogram of-mw 252 and 25 in sample #8-Inlet
Whole Extract
30.9-1
233 _
100.
256 _
1980 SCAN
33s30 TIME
Figure 8-2
Ion Chromatogram of mw 256 in Sample #8-Inlet,
Whole Extract
-60-
-------
100.3-1
2SS _
25.3-n
2S7 _
V _ 1 . .A ^ A
I ' ' ' ' I • • •
33:38
1059
35: 10
use
36:51
lisa
33:31
1208 SCAN
40s12 TIME
Figure 8-3
Ion Chromatogram of mw 266 and 267 in Sample
#8-Inlet, Whole Extract
-61-
-------
benzopyrenes elute in the same retention time region as
dibenzocarbazole with the C containing of isotope of the
molecular ion at mw 267. This amounts to 23% of the molecular
ion at mw 266 so that the potential interferences on the
dibenzocarbazole measurement are quite great. In the region
where the dibenzocarbazole should elute, all of the mw 267
peaks correlate with isotope peaks from mw 266 POMs as shown in
Figure 8-3, for the #8-inlet sample without LC separation. Thus
there is no evidence to indicate the presence of dibenzocarbazole
in these samples.
Dibenzacridine with molecular ion at mw 279 was also not found
in any of the samples. An evaluation of the f8-inlet sample
before the LC fractionation and dilution carried out as described
above, showed that all mw 279 peaks could be accounted for by
other species and no evidence of dibenzacridine could be found.
«
8.2.2 Detection Limits
The limits of detection vary depending upon the species, the sample
preparation, and the definition of the limit of detection. The
instrumental detection limits for the subject POM species range
from 30 to 200 picograms injected onto the column. The limit
of detection is defined as the lowest level permitting MS
confirmation from the mass spectra. In more appropriate terms,
the limit of detection should be defined with respect to the
original sample. For example; one could compute the detection
limits in the gas using the instrumental detection limits above
and standard analytical conditions, such as 1 m of the gas
sampled, volume of combined extract reduced to 15 mL of which
1 ml is fractionated by LC (resulting in 30 mL eluent) and 2 y.L
-62-
-------
TABLE 8-3
DETECTION LIMITS OF GC/MC ANALYSIS
Detection Limit (mg/m3)
Sample No.
1,
1,
2,
2,
2B
3,
3,
4,
4,
5,
5,
6,
6,
7,
7,
8,
8,
9,
10,
10,
'11,
11,
Inlet
Outlet
Inlet
Outlet
, Outlet
Inlet
Outlet
Inlet
Outlet
Inlet
Outlet
Inlet
Outlet
Inlet
Outlet
Inlet
Outlet
Outlet
Inlet
Outlet
Inlet
Outlet
Species <252 m/e
.004
.003
.004
.001
.002
.010
.004
.009
.011
.011
.013
.018
.012
.010
.008
.012
.010
.005
.009
.007
.005
.006
Species >252 m/e
.030
.018
.023
.006
.013
.070
.028
.063
.070
.070
.088
.120
.077
.064
.053
.077
.064
.036
.063
.046
.036
.039
-63-
-------
is injected into the GC/MS for analysis. For a 30 pg limit and
a 2 y.L injection, the concentration would be 15 pg/yL or 15 ng/inL
in the LC eluent. The total LC eluent would contain 450 ng which
is 1/15 of that in the extract (i.e., 6.75 yg is in the extract).
Thus, the limit of detection in the gas phase would be about 7 yg/m .
The detection limits thus calculated for the stack air samples
range from 0.8 y.g/m3 to 18 y.g/m3 for POM species having a mw <252
and from 6 y.g/m to 120 y.g/m for species having a mw >252,
depending on the volume of concentrated extract and the volume
of air sampled. Table 8-3 shows the detection limit values for
each sample computed in the manner described above.
8.2.3 Total POM (128< mw.<302)
Total POM concentrations (128< mw <302) 6f the 22 POM-train tests
are summerized in Table 8-4. Inlet concentrations ranged from
33 3
170 mg/Nm to 22 mg/Nm with an average of 64 mg/Nm . Outlet
concentrations ranged from 104 mg/Nm to 3.2 mg/Nm with an
average of 37 mg/Nm . Scrubber efficiency based on total POM
concentration ranged from 17.8 to 71.6. The average scrubber
efficiency was 40%.
Total POM concentrations for each of the six water samples are also
summarized in Table 8-4. Inlet concentrations ranged from 0.54 mg/L
to 0.30 mg/L with the average being 0.40 mg/1. Outlet concentrations
ranged from 0.12 mg/L to 0.04 mg/L with the average being 0.08
mg/L.
-64-
-------
TABLE 8-4
SUMMARY OF TOTAL POM (123< IWK302) CONCENTRATION IN
COAL PREHEATER SAMPLES
Test
1
9
10
11
STACK SAMPLES
Sample
Inlet
Outlet
Inlet
Outlet- B
Inlet
Outlet
*
Inlet
Outlet
Inlet
Outlet
***
Inlet
Outlet
it
Inlet
Outlet
Inlet
Outlet
Outlet
Inlet
Outlet
Inlet
Outlet
mg/Nm
26.73
21.98
21.96
17.80
66.86
18.96
144.58
61.36
68.69
103.95
71.61
31.95
52.82
40.04
169.22
63.47
80.994
45.71
37.51
37.94
27.27
g/Hr
447.69
264.94
548.12
637.00
1104.67
457.67
3005.94
1260.07
2009.86
2534.34
2114.18
707.33
829.16
809.66
4717.3
1375.28
883.14
995.18
530.70
405.37
426.83
g/M-ton
8.243
4.683
6.694
7.794
13.238
5.495
27.575
11.565
18.533
23.379
19.582
6.544
10.141
9.891
43.31
12.639
30.348
12.189
6.494
4.9605
5.245
* Questionable data due to moisture
*** Test invalid due to insufficient sample
-65-
-------
TABLE 8-4
(continued)
WATER SAMPLES
Test Samples mg/L
1 Inlet 0.38
Outlet 0.09
2 Inlet 0.55
Outlet 0.04
3 Inlet 0.30
Outlet 0.11
-66-
-------
8.2.4 Selected POM
Among the compounds found in the coal preheater air and water
samples, the most abundant species were naphalene, anthracene,
and phenanthrene. Lesser amounts of fluorene, pyrene,
benzanthracene, chrysene, and benzopyrenes were also found in all
the air samples. In the water samples, only the low molecular
weight species, such as napthacene and anthracene, were found,
with concentrations below the PPM level.
Tables 8-5 through 8-15 summarize the POM concentrations found in
the air samples, while the water sample concentrations are
presented in Table 8-16.
-67-
-------
TABLE 8-5
COAL PREHEATER SAMPLES
POM Analysis
Test No.: 1
Description: POM #1
Process Conditions: 54/277
Date: 7/18/78
INLET
OUTLET
Speciea
Naphthalene
Fluorene
Anthracene /Phenanthrene
Fluoranthene
Pyrene
Benz(a)anthracene/(c)phenanthrene ,
Chryaene/Triphenylene
Benzo(b or k) f luoranthene
Benzo ( J ) f luor anthene
Benzo (e)pyrene
Benzo(a)pyrene
Cholanthrene
Diaiethyl benzanthracene iaomera*
Dibenzo(c,g)carbazole
3-Methylcholanthrene
Indeno(l, 2 , 3-cd)pyrene
Benzo (ghi)perylene
Dlbenz(ah or aj) anthracenes
Dlbenzacrldlnea
Coronene
Dlbenzo(a,h)pyrene
Dibenzo(a,i)pyrene
mw
128
166
178
202
202
228
228
252
252
252
252
254
256
267
268
276
276
278
279
300
302
302
TOTAL
mg/m
19.6
0.5
3.5
0.34
0.35
0.25
0.42
0.32
___
0.26
0.18
0.57
___
0.17
0.09
0.09
0.09
___
___
26.73
q/
328.4
8.39
58.5
5.72
5.85
4.19
7.03
5.35
___
4.35
3.02
9.57
___
2.85
1.51
1.51
1.51
447.69
g/M ton
6.04
0.154
1.074
0.104
0.108
0.077
0.129
0.099
___
0.080
0.055
0.176
_ __
0.052
0.028
0.028
0.028
_
8.243
mg/m
14.1
1.3
5.2
0.37
0.38
0.11
0.19
0.07
___
0.08
0.06
0.12
_
__ _
«._
___
21.98
170.0
15.65
62.69
4.45
4.58
1.32
2.29
0.84
___
0.966
0.721
1.447
_«..».
w » _
_ __
.»__
_«.«
264.94
g/M tor
3.120
0.288
1.150
0.0820
0.0839
0.0243
0.0421
0.0155
___
0.0177
0.0133
0.0265
_ _ _
_ _ _
__ _ _
M _.».
_~ —
— _H
4.683
^
28.1
__ _
„.
56.0
54.8
78.1
___
69.2
66.7
78.9
— _ _
__ _
™
„, _ _
_
_ _ _
17.8
* Includes dimethyl- and ethyl-chrysenea,
benzanthracenea.
benzophenanthrenea, and ** Process conditions reported in tons/hr
coal feed rate/°F of preheater outlet
-------
TABLE 8-6
COAL PREHEATER SAMPLES
POM Analysis
Test No. 2
Description: POM #2
Process Cond.: 82/271
Date: 7/19/78
INLET
OUTLET
Species
Naphthalene
Fluorane
Anthracene/Phenanthrene
Fluoranthene
Pyrene
Benz(a)anthracene/(c)phananthrene .
Chryaene/Trlphenylene
Benzo(b or k) fluoranthene
Benzo ( J ) fluoranthene
Benzo (e)pyrene
Benzo (a) pyr ene
Cholanthrene
Dimethyl benzanthracene iaomera
Dibenzo (c . g) carbazole
3-Methylcholanthrene
Indeno (1,2, 3-cd) pyr ene
Benzo (ghi)perylene
Dibenz(ah or aj) anthracenes
Dihenzacridinea
Coronene
Dibenzo ( a, h) pyr ene
Dibenzo (a, i)pyrene
mw
128
166
178
202
202
228
228
252
252
252
252
254
256
267
268
276
276
278
279
300
302
302
TOTAL
mg/M
10.1
1.14
6.4
0.59
0.52
0.39
0.79
0.42
0.36
0.14
1.0
_____
0.03
0.02
0.06
21.96
q/hr
252.1
28.45
159. 6
14.74
12.97
9.75
19.73
10.48
8.98
3.49
24.95
_— _
0.748
0.499
1.497
548.12
g/M Ton
3.085
0.3482
1.9547
0.1803
0.1589
0.1189
0.2413
0.1099
0.0428
0.3052
___
.009142
.006094
.01833
6.694
mg/m
13.000
0.700
2.800
0.250
0.140
0.260
0.350
0.120
0.073
___
17.800
g/hr
468
25.2
100.8
9.0
5.04
9.36
12.6
4.32
2.63
637.0
g/M ton
5.727
0.308
1.233
0.1101
0.0617
0.1145
0.154
0.0529
0.0322
7.794
xf%
61.4
43.8
42.4
26.9
66.7
44.3
33.3
52.1
18.9
* Includes dimethyl- and ethyl-chrysenea, benzophenanthrenea, and
benzanthracenea.
-------
TABLE 8-7
COAL PREHEATER SAMPLES
POM Analysis
Test No. 3
Description: POM #3
process Conditions: 83/271
Date: 7/24/78
INLET
OUTLET
Species
Naphthalene
Fluorene
Anthracene/Phenanthrene
Pluoranthene
Pyrene
Benz (a) anthracene/ (c)phenanthrene .
Chryaene/Trlphenylene
Benzo(b ot k)fluoranthene
Benzo ( j ) f luoranthene
Benzo(e)pyrene
Benzo (a) pyrene
Cholanthrene
Dimethyl benzanthracene iaomera
Dlbenzo (c , g) carbazole
3-Methylcholanthrene
Indeno (1,2, 3-cd) pyrene
Benzo (ghl ) pery lene
Dlbenz(ah or aj) anthracenes
Dibeuzacridinea
Coronene
Dibenzo (a , h) pyrene
Dlbenzo(a,l)pyrene
mw
128
166
178
202
202
228
228
252
252
252
252
254
256
267
268
276
276
278
279
300
302
302
TOTAL
mg/m
33
4.6
17.8
1.3
1.4
0.96
2.1
1.3
1.1
0.67
2.3
0.08
0.25
66.86
g/M ton
545.2
76.02
294.1
21.50
23.13
15.87
34.70
21.50
18.19
11.07
38.01
-.
4
1.320
4.132
1104.67
mg/T ton
6.53
0.9092
3.52
0.2573
0.2768
0.1898
0.4151
0.2573
0.2178
0.1324
0.4551
0.01584
0,04946
13.238
mg/m
14.6
0.67
2.6
0.17
0.19
0.16
0.50
0.07
«.—_
18.96
g/hr
352.44
16.19
62.78
4.105
4.586
3.865
12.065
1.678
457.67
g/M ton
4.221
0.1938
0.7493
0.04896
0.05496
0.04621
0.1449
0.0202
— __
5.495
^*
55.8
85.4
85.4
86.9
86.4
83.3
76.2
93.6
71.6
Includes dimethyl- and ethyl-chrysenes, benzophenanthrenea. and
-------
TABLE 8-8
COAL PREHEATER SAMPLES
POM Analysis
Test No. 4
Description: POM #4
Process Conditions: 1O9-260
Date: 7/25/78
INLET
OUTLET
Species
Naphthalene
Fluorene
Anthrac ene /Phenan thr ene
Fluoranthene
Pyrene
Benz (a) anthracene/ (c)phenanthrene .
Chryaene/Triphenylene
Benzo(b or k) fluorantheoe
Benzo ( j ) f luoranthene
Benzo (e) pyr ene
Benzo (a) pyr ene
Cholanthrene
Dimethyl benzanthracene isomera*
Dlbenzo (c , g) carbazole
3-Methylcholanthrene
Indeno (1,2, 3-cd) pyr ene
Benzo(ghi)perylene
Dlbenz(ah or aj) anthracenes
Dlbenzacrldines
Coronene
Olbenzo ( a , h) pyr ene
Dlbenzo (a , 1) pyrene
mw
128
166
178
202
202
228
228
252
252
252
252
254
256
267
268
276
276
278
279
300
302
302
TOTAL
>
mg/m
80
11.5
40
2.7
2.4
1.2
2.3
0.99
___
0.8
0.29
2.4
144.58
g/hr
1663.3
239.1
831,4
56.15
49.89
24.95
47.81
20.59
___
16.65
6.033
49.89
3005.94
g/M ton
15.29
2.198
7.643
0.5145
0.4596
0.2298
0.4391
0.1883
___
0.1529
0.0555
0.45958
27.575
mg/m
43
3.5
8.4
0.9
0.82
0.45
0.90
0.43
0.39
0.17
2.4
61.36
g/hr
883.1
71.85
172.5
18.46
16.83
9.253
18.46
8.831
8.029
3.493
49.26
260.07
g/M ton
8.093
0.6594
1.5836
0.1698
0.1549
0.0849
0.1698
0.0809
0.7343
0.03202
0.4521
11.565
/%
46.3
69.6
79
66.7
65.8
62.5
60.9
56.6
51.3
41.4
57.6
I
-J
Includes dimethyl- and ethyl-chryaenes, benzophenanthrenea, and
benzanthracenes.
-------
TABLE 8-9
COAL PREHEATER SAMPLES
POM Analysis
INLET
Test No. 5
Description:
Process Conditions;
Date: 7/26/78
POM #5
109/288
OUTLET
Species
Naphthalene
Fluorene
Anthracene/Phenanthrene
Fluoranthene
Pyrene
Benz (a) anthracene/ (c)phenanthrene .
Chryaene/Triphenylene
Benzo (b or k) £ luoranthene
Benzo ( j ) f luoranthene
Benzo (e) pyrene
Benzo (a) pyrene
Cholanthrene
Dimethyl benzanthracene laomera*
Dibenzo (c , g) carbazole
3-Me thy 1 cholanthrene
Indeno (1,2, 3-cd) pyrene
Benzo ( ghl ) pecy lene
Dlbenz(ah or aj) anthracenes
Dlbenzacridines
Coronene
Dibenzo(a,h)pyrene
Dlbenzo(a,l)pyrene
mw
128
166
178
202
202
228
228
252
252
252
252
254
256
267
268
276
276
278
279
300
302
302
TOTAL
mg/m
41
4.9
14
1.1
0.97
0.66
1.5
1.2
— __
9.98
0.58
1.8
— —
68.69
g/hr
1199.7
143.38
409.64
32.20
283.95
19.323
43.908
35.108
___
28.667
16.964
52.66
___
2009186
g/M ton
10.99
1.324
3.777
0.2967
0.2618
0.1778
0.4046
0.3237
___
0.2643
0.1564
0.4856
18.533
mg/m
69
4.1
20
1.7
1.5
1.2
2.3
1.1
0.45
2.6
^» ••»««•
<«p ««••
•H ^m ^
103 . 95
g/hr
1682.4
99.97
487.6
41.46
36.56
29.26
56.06
26.81
___
10.977
63.389
___
2534.34
g/M ton
15.486
0.9192
4.496
0.3822
0.3367
0.2698
0.5145
0.2473
— __
0.1009
0.5845
___
-ni. [LL „
23.379
•?*
_
16.3
-
-
_
_
_
8.3
___
54.1
___
___
___
* Includes diwetHyl- and ethyl-chryaenea. benzophenanthrenea, and
-------
TABLE 8-10
COAL PREHEATER SAMPLES
POM Analysis
Test No. 6
Description: POM #6
Process Conditions: 108/288
Date: 7/27/78
INLET
OUTLET
Species
Naphthalene
Fluorene
Anthracene/Phenanthrene
Fluoranthene
Pyrene
Benz (a) anthracene/ (c)phenanthrene .
Chrysene/Triphenylene
Benzo(b or k) f luoranthene
Benzo(j) fluoranthene
Beuzo(e)pyrene
Banzo (a) pyr ene
Cholan throne
Dimethyl benzanthracene Isomers*
Dlbenzo (c , g) carbazole
3-Methylcholanthrene
Indeno (1 , 2 , 3-cd) pyr ene
Benzo(ghi)perylene
Diben£(ah or aj) anthracenes
Dibenzacridlnes
Coronene
Dibenzo(a,h)pyrene
Dlbenzo(a,l)pyrene
mw
128
166
178
202
202
228
228
252
2S2
252
252
25A
256
267
268
276
276
278
279
300
302
302
TOTAL
. 3
mg/m
40
4.3
15
1.1
1.2
0.88
2.3
1.2
1.5
0.53
3.1
0.29
0.21
— __
71.61
g/hr
1180.7
126.51
442.8
32.48
35.43
25.99
67.90
35.43
44.28
15.65
91.53
8.573
6.214
__—
2114.18
g/M ton
10.94
1.174
4.097
0.3007
0.3277
0.2403
0.6294
0.3277
0.4096
0.1499
0.8492
0.6794
0.05745
19.582
mg/m
13
1.7
8.1
0.8
0.91
0.63
1.7
0.97
0.88
0.37
2.8
0.09
_— —
31.95
g/hr
287.8
37.65
179.30
17.71
20.14
13.95
37.65
21.45
19.46
8.192
61.988
1.991
707.33
g/M ton
2.663
0.3482
1.6585
0.1639
0.1863
0.1291
0.3482
0.1988
0.1803
0.0759
0.5735
0.01848
— _ _
___
6.544
^*
67.5
60.5
46.0
27.3
24.2
28.4
26.1
19.2
41.3
30.2
9.7
57.1
— — .-
55.4
Includes dimethyl- and ethyl-chrysenes, benzophenanthrenea, and
benzanthraceneu.
-------
TABLE 8-11
COAL PREHEATER SAMPLES
POM Analysis
Test No. 7
Description: POM #7
Processs Conditions: 82/288
Date: 7/28/78
INLET
OUTLET
Species
Naphthalene
Fluorene
Anthracene/Phenanthrene
Fluoranthene
Pyrene
Benz ( a ) anthracene/ ( c ) phenanthr ene .
Chryaene/Triphenylene
Benzo(b or k) £ luoranthene
Benzo ( j ) f luoranthene
Benzo (e) pyrene
Benzo (a)pyr ene
Cholanthrene
Dimethyl benzanthracene iaomera*
Dlbenzo (c , g) carbazol e
3-Methylcholanthrene
Indeno(l, 2, 3-cd) pyrene
Benzo (ghl ) pery lene
Dlbenz(ah or aj) anthracenes
Dlbenzacridlnea
Coronene
Dlbenzo (a , h) pyrene
Dlbenzo (a . 1) pyrene
mw
128
166
178
202
202
228
228
252
252
252
252
254
256
267
268
276
276
278
279
300
302
302
TOTAL
mg/m
27
3
13
1.4
1.3
0.95
2.0
1.0
___
1.0
0.27
1.9
___
52.82
g/hr
423.8
47.08
204.1
21.999
20.41
14.92
31.39
15.69
— _ —
15.69
4.237
29.846
_——
—__
___
-.__
829.16
g/M ton
5.195
0.5745
2.498
0.2688
0.2498
0.1823
0.3842
0.1923
— ._—
0.1923
0.05195
0.3647
___
_ —
10.141
mg/m
15
3.9
13
0.66
0.74
0.74
1.5
1.1
0.06
0.88
0.47
1.7
0.11
0.18
40.04
g/hr
303.36
78.88
262.9
13.335
14.968
14.968
30.336
22.226
1.2156
17.781
9.525
34.382
2.2226
— _
3.6423
809.66
g/M ton
3.7116
0.9641
3.2171
0.1634
0.1833
0.1833
0.3712
0.2723
0.0148
0.2178
0.1164
0.4206
0.02723
0.04456
9.891
?%
44.4%
52.9%
43.1
22.1
25.0
12.0
10.5
___
___
— —
23.5
Includes dimethyl- and ethyl-chrysenes. bcmzophenanthrenea. and
-------
TABLE 8-12
COAL PKEHEATER SAMPLES
POM Analysis
Test No. 8
Description: POM #8
Process Conditionss 1O9/271
Date: 7/29/78
INLET
OUTLET
Species
Naphthalene
Fluorene
Anthracene /Phenan thr ene
Fluoranthene
Pyrene
Benz (a) anthracene/ (c)phenanthrene .
Chryaene/Triphenylene
Benzo(b or k) f luoranthene
Benzo ( J ) fluoranthene
Benzo(e)pyrene
Banzo (a) pyr ene
Cholanthrene
Dimethyl benzanthracene iaomera*
Dlbenzo (c , g) carbazole
3-Methylcholanthrene
Indeno ( 1 , 2 , 3-cd) pyr ene
Benzo ( ghl ) pery lene
Dlbenz(ah or aj) anthracenes
Dibenzacridines
Coronene
Dibenzo(a,h)pyrene
Dlbenzo (a, Dpyrene
mw
128
166
178
202
202
228
228
252
252
252
252
254
256
267
268
276
276
278
279
300
302
302
TOTAL
mg/m
96
11
35
4.9
4.3
2.7
4.3
2.9
0.33
2.2
1.3
3.7
0.14
0.45
-.__
164.22
g/hr
2676.2
306.63
975.67
136.58
119.84
75.25
119.84
80.83
9.199
61.33
36.24
103.15
_— _
3.9087
12.542
___
___
4717.3
g/M ton
24.578
2.8125
8.9419
1.2539
1.099
0.6894
1.099
0.7443
0.08442
0.5645
0.3327
0.9441
0.03582
0.1149
_ — —
43.31
mg/m
31
4
15
1.7
1.5
1.1
1.7
1.6
0.09
0.87
0.62
3.8
___
0.15
0.09
0.18
0.07
— _
_ —
63.47
g/hr
671.77
86.68
325.00
36.83
32.500
23.813
36.832
34.654
1.9504
18.85
13.426
82.327
3.2522
1.9504
3.9009
1.4968
___
1375.28
g/M ton
6.1444
0.7943
2.9823
0.3382
0.2982
0.2188
0.3381
0.3182
0.01789
0.17299
0.12329
0.75432
— . — _
0.02982
0.1789
0.03582
0.01394
_ _ _
12.639
^%
67.7
63.6
57.1
65.3
65.1
59.3
60.5
44.8
72.7
60.5
52.3
— — —
35.7
60.0
62.5
* Includes dimethyl- and ethyl-chrysenea, benzophenanthrenea, and
benzanthracenes.
-------
TABLE 8-13
COAL PREHEATER SAMPLES
POM Analysis
Test No. 9
Description: POM #9
Process Conditions: 29/260
Date: 7/31/78
INLET
OUTLET
Species
Naphthalene
Fluor ene
Anthracene/Phenanthrene
Fluoranthene
Pyrene
Benz (a) anthracene/ (c)phenanthrene .
Chrysene/Trlphenylene
Benzo(b or k) fluoranthene
Benzo ( j ) f luoranthene
Benzo(e)pyrene
Benzo (a)pyr ene
Cholanthrene
Dimethyl benzanthracene laouers*
Dlbenzo (c , g) carbazole
3-Methylcholanthrene
Indeno(l,2,3~cd)pyrene
Benzo (ghl ) pery lene
Dlbenz(ah or aj) anthracenes
Dlbenzacrldlnes
Coronene
Dlbenzo ( a , h) pyr ene
Dlbenzo (a, Dpyrene
mw
128
166
178
202
202
228
228
252
252
252
252
254
256
26?
268
276
276
278
279
300
302
302
TOTAL
mg/m
g/hr
g/M ton
mg/m
52
5.8
21
9.91
0.82
0.084
0.22
0.047
0.091
0.022
80.994
g/hr
586.99
63.05
228.61
9.93
8.94
0.916
2.399
0.513
0.9934
0.2399
— __
— — —
883.14
g/M ton
19.48
2.173
7.893
0.3412
0.3077
0.03147
0.08243
0.01758
0.03412
0.00824
—__
— __
30.348
/*
_— —
— — _
* Includes dimethyl- and ethyl-chrysenes. benzophenanthrenea, and
-------
TABLE 8-14
COAL PREHEATER SAMPLES
POM Analysis
INLET
Test No. 1O
Description: POM ttlO
Process
Conditions: 82/271
Date: 8/2/78 8/2/79
OUTLET
Species
Naphthalene
Fluor ene
Anthracene/Phenanthrene
Fluoranchene
Pyrene
Benz (a) anthracene/ (c)phenanthrene .
Chcyaene/Triphenylene
Benzo(b or k) f luoranthene
Benzo ( J ) f luoranthene
Benzo(e)pyrene
Benzo (a) pyr ene
Cholanthrene
Dimethyl benzanthracene laomera*
Dibenzo (c , g) carbazole
3-Methylcholanthrene
Indeno(l,2,3-cd)pyrene
Benzo ( ghl ) pery lene
Dlbeuz(ah or aj) anthracenes
Dlbenzacrldinea
Coronene
Dlbenzo(a,h)pyrene
Dibenzo (a, Dpyrene
me
128
166
178
202
202
228
228
252
252
252
252
254
256
267
268
276
276
278
279
300
302
302
TOTAL
mq/m
18
2.5
17
1.2
1.2
0.73
1.7
0.71
0.04
0.63
0.24
«.«.«.
1.7
0.06
— «_
45.71
9/hr
391.85
54.43
370.08
26.13
26.13
15.
37.01
15.46
0.8709
13.698
5.216
37.008
1.306
995.18
g/M ton
4.796
0.6494
4.531
0.3197
0.3197
0.1948
0.4531
0.1893
0.0106
0.1678
0.06394
0.4531
0.01599
— _
___
12.189
mg/m
23
3.6
8.6
0.43
0.45
0.19
0.47
0.26
0.03
0.07
__ —
0.41
___
— «—
37.51
g/hr
325.46
50.94
121.70
6.078
6.350
2.690
6.668
3.679
0.4246
0.9906
___
5.806
— —
— __
530.7
g/M ton
3.982
0.6234
1.489
0.0744
0.07793
0.03292
0.08143
0.04501
0.00519E
0.01214
_ _ _
0.07094
___
_„_
6.494
-------
TABLE 8-15
COAL PREHEATER SAMPLES
POM Analysis
Test No. 11
Description: POM #11
Process Conditions: 82/260
Date: 8/3/78
INLET
OUTLET
Species
Naphthalene
Fluorane
Anthracene /Phenaothrene
Pluoranthene
Pyrene
Benz(a)anthracene/(c)phenanthrene .
Chry sene/Tr iphenyl ene
Benzo(b or k) f luoranthene
Beozo (J ) f luoranthene
Benzo (e) pyrene
Benzo (a) pyr ene
Cholanthrene
Dimethyl benzanthracene iaomers*
Dlbenzo (c , g) carbazole
3-Methylcholanthrene
Indeno (1 , 2 , 3-cd) pyrene
Benzo (ghl ) perylene
Dlbenz(ah or aj) anthracenes
Dibenzacridlnea
Coronene
Dlbunzo (a, h) pyrene
Dlbenzo(a,l)pyrene
mw
128
166
178
202
202
228
228
252
252
252
252
254
256
267
268
276
276
278
279
300
302
302
TOTAL
mg/m
18
2.3
"'I 1 •" " |
12
1.1
0.97
0.51
1.2
0.4
0.35
0.11
0.96
0.04
37.94
g/hr
192.32
24.58
WBVHHIMBBHIfeHHBBBBBHHBHAHVB^l4
128.23
11.748
10.342
5.443
12.837
4.264
3.738
1.175
10.251
0.4273
405.37
g/M ton
2.348
0.300
1.569
0.1439
0.1269
0.0664
0.1569
0.05245
0.04576
0.01439
0.12539
0.005245
_ „
4.9605
—
mg/m
11
2.6
1-WHBH^^^flhiHVHIViVIBi^^
9.5
0.71
0.65
0.37
0.73
0.35
0.02
0.28
0.13
0.88
0.05
„. ,„,
27.27
g/hr
172.14
40.69
»HIMalHllm*MIMWI*MMM>V*
148.69
11.113
10.160
5.792
11.4259
0.06940
0.003946
0.05534
0.02576
0.1746
0.009934
__ —
426.83
g/M ton
2.108
0.498
••••••••••^^•••••••••iii ••'• i"
1.818
0.1359
0.1244
0.0709
0.1399
0.06694
0.003847
0.05345
0.02498
0.1683
0.009591
«__«
5.245
^
38.9
MW^H^BBMHMM— «^VI«B
20.8
35.5
33
27.5
39.2
12.5
20
8.3
_
28.1
Includes dimethyl- and ethyl-chrysenes, benzophenanthrenes, and
benzanthracenea.
-------
TABLE 8-16
SCRUBBER WATER ISLET-OUTLET
ANALYSIS
CONCENTRATION
(mg/L)
Component Test No. 1 Test No. 2
Inlet Outlet Inlet Outlet
Naphthalene 0.27 0.05 0.28 0.01
Fluorene 0.02 — 0.07 0.01
Anthracene/
Phenanthrene 0.06 0.04 0.17 0.02
Fiuoranthene 0.01 0.01
Pyrene 0.02 0.02
3enz (a) anthra-
cene/ (c) phenan-
threne -— • ~~~
Ciaysene Tripheny-
lene - — ~ — """
Benzo(e)pyrene — —
Dimethyl Benzan-
thra_cene isoroers — — ""
Test
Inlet
0.03
0.01
0.16
0.02
0:.02
0.01
0.02
0.01
0.02
•
No. 3
Outlet
0.05
0.01
0.04
—.-
0.01
—
Totals
0.38
0.09
0.55
0.04
0.30
0.11
-79-
-------
8.2.5 Selected vs. Total POM
Since the GC/MS Data System requires a great deal of
data to acquire a narrow, specific, list of POM species,
it is possible to estimate the relative weight of the
POM's compared to the total aromatic fraction of the ex-
tracted sample.
The original mass spectral data are acquired over a mass
scan range of mw 125-310. Integration of this entire
mass range provides a measure of the total aromatic content.
It is then possible to extract the abundance of only those
species with 3 or more rings (m/e > 178) from this total as
a measure of total POM. Finally, a summation of the selected
mass POM profiles (178, 202, 228, etc) gives a measure of
total selected POM.
Table 8-17 tabulates the results for three typical samples,
#8 inlet before and after LC and #8 outlet after LC. These
results may be summerized by two statements:
1. The specific POMs of interest represent 3-10% of the
sample.
2. The outlet sample has reduced amounts of the lighter
species (that is, 3 ring and higher POMs represent
50% of the inlet samples compared to 90% of
the outlet sample).
The percentage of the aromatic fraction of each sample
represented by the specific POMs can also be estimated
from the gravimetric analysis data. Table 8-18 shows
that these values range from 3 to 14% for all the stack
-80-
-------
samples (except No. 9 Outlet sample which is unexplainably
high), and less than 1% for the water samples from test
No. 3. Since the aromatic fraction represents about half
of the total extract for most of these samples, the specific
POMs analyzed by GC/MS represent 2-7% of the total sample.
See Table 8-19.
-81-
-------
TABLE 8-17
Comparison of 3-Ring and Higher POMs
to Total Sample Extract
8 Inlet 8 Inlet 8 Outlet
w/o LC w LC w LC
Ratio of ion areas
178 thru 310 to
total ion area 0.54 0.53 0.94
Ratio of area for
sum of the ions of
interest to the
total ion area 0.06 0.10 0.03
-82-
-------
TABLE 8-18
ANALYSIS OF AROMATIC FRACTIONS (mg/m )
Sample No.
1, Inlet
1, Outlet
2, Inlet
2, Outlet
2B, Outlet
3, Inlet
3, Outlet
4, Inlet
4, Outlet
5, Inlet
5, Outlet
6, Inlet
6, Outlet
7, Inlet
7, Outlet
8, Inlet
8, Outlet
9, Outlet
10, Inlet
10, Outlet
11, Inlet
11, Outlet
H20, 3 Inlet
H20, 3 Outlet
OF COAL
QSAV
394
154
359
93
146
1450
323
1230
549
977
1410
1610
1190
1310
1130
1370
1040
1961
770
371
593
269
38
22
PREHEATER SAMPLES
POM
27
22
22
3.2
18
67
19
150
61.
69
104
72
32
53
40
170
64
81
45
38
37
27
.3
.12
% POM/G3AV
6.9
14
•6.1
3.4
12
4.6
5.9
12
11
7.1
7.4
4.5
2.7
4.1
3.5
12
6.1
41
5.8
10
6.2
10
.9
.5
-83-
-------
TABLE 8-19
GRAVIMETRIC ANALYSIS OF COAL PREHEATER SAMPLES
Aromatic Fractions
Sample No.
1, Inlet
1, Outlet
2A, Inlet
2A, Outlet
2B, Outlet
3, Inlet
3, Outlet
4, Inlet
4, Outlet
5, Inlet
5, Outlet
6, Inlet
6, Outlet
7, Inlet
7, Outlet
3, Inlet
8, Outlet
9, Outlet
10, Inlet
10, Outlet
11, Inlet
11, Outlet
H20, 3 Inlet
foO, 3 Outlet
(mg/m3)
394
154
359
93
146
1450
323
1230
549
977
1410
1610
1190
1310
1130
1370
1040
196
770
371
593
269
38
22
Total Aromatic Total
(mg/m3)
66B
603
807
175
439
2580
807
2680
1520
2080
2740
3610
2730
1950
2040
2960
2340
843
2140
1130
1290
840
59
92
(%)
59
26
44
53
33
56
40
46
36
47
51
45
44
67
55
46
44
23
36
33
46
32
64
24
-84-
-------
8.2.6 Toxicity Level of Coal Preheater Emissions
One. basis for estimating the toxicity level of the coal preheater
emissions is to compare the concentrations of the various POM
species found in the effluent stream to the corresponding Dis-
charge Multimedia Environmental Goal CDMEG) levels. Table 8-20
lists the available DMEG values of interest. Using the Source
Analysis Models (SAMS) developed by EPA a quality called "Discharge
Severity" (.DS) can be obtained for each pollutant species by
taking the ratio of the pollutant concentration to the correspond-
ing DMEG value for that species. Tables 8-21 and 8-22 summarize
these values for all the air samples taken at the outlet of the
scrubber and Table 8-23 summarizes the DS values for the three
outlet water samples analyzed. In cases where two or more com-
pounds of the same modecular weight are not resolved in the GC/MS
analysis, the assumption is made for the worst case, i.e., assuming
all the concentration is due to the species having the lowest
DMEG value. For example, to get the Discharge Severity value
for benz(.a)anthracene/benz(.c)phenanthrene, the concentration
found is divided by the DMEG of benz (a) anthracene 145 yg/m in
air) . Data thus obtained show that in most of the air samples,
the following species exceed the DMEG level: phenanthrene, benz(a)
anthracene, benzo (.a) pyrene, 7 ,12-dimethyl benz (a)-anthracene, and
3-methyl cholanthrene when present. None of the species found
in the water samples exceed their DMEG values.
-85-
-------
TABLE 8-20
POM DMEG Values Based on Health Effects
Species
Naphthalene
Fluorene
Anthracene
Phenanthrene
Fluoranthene
Pyrene
Benz (a) anthracene
Benzo(c)phenanthrene
Chrysene
Triphenylene
Benzo (b) f luoranthene
Benzo (k) f luoranthene
Benzo (j ) f luoranthene
Benz o ( e ) pyr ene
Benzo(a)pyrene
Cholanthrene
12-Dimethyl benz (a) anthracene
Dibenzo (c , g) carbazole
3-Methylcholanthrene
Indeno (1,2, 3-cd) pyrene
Benzo (ghi) perylene
Diben z ( ah) ant hr a cene
Dibenz (a , h) acridine
Dibenz (a , j ) acridine
Coronene
Dibenzo (a , h) pyrene
Dibenzo (a, i) pyrene
m/e
128
166
178
178
202
202
228
228
228
228
252
252
252
252
252
254
256
267
268
276
276
278
279
279
300
302
302
Air, ug/m3
5 x 10*
*
5.6 x 10*
1.6 x 103
9 x 10*
2.3 x 10s
45
2.7 x 10*
2.2 x 103
900
1.6 x 103
6.5 x 103
3 x 103
0.02
0.26
3.8
1.6 x 103
0.093
220
250
3.7 x 103
43
Water, yg/L
7.5 x 10s
8.4 x 10s
2.4 x 10*
1.4 x 106
3.5 x 105
670
4.1 x 105
3.3 x 10*
1.3 :: 10*
2.5 x 10*
9.2 x 10*
4.6 x 10*
0.3
3.9
.56
2.4 x 10*
1.4
3.4 x 103
3.7 x 103
5.6 x 10*
650
* All blanks are data not available
-86-
-------
TABLE 8-21
DISCHARGE SEVERITY CALCULATED FOR POM IN
COAL PREHEATER SAMPLES, OUTLET
Discharge Severity (DS)
Specie*
naphthalene
Fluorene
Anthracene /Fhenanchrene
Fluoranchene .
Pyrene
Benz (a) anthracene/ (c)phenanthrene .
Chryaene/ triphenyl eae
Senzo(b or k) f luoranthene
Benzo Cj ) f luoranthene
Benzo < e) pyrene
3enzo
-------
TABLE 8-22
DISCHARGE SEVERITY CALCULATED FOR POM IN
COAL PREHEATER SAMPLES, OUTLET
Discharge Severity (DS)
Species
Naphthalene
Jluorene
Anthracene /?hen*nthr ene
?luoranthene
Pyreue
Benz (a) anthracene/ (c)phenanthrene .
Chrysene/Triphenyleae
Benzo ("b or 1c) fluoranthene
Benzo (J ) f luoranthene
Benzo ( e ) pyr ene
Benzo (a ) pyrene
Cholanthrene
Dimethyl benzanchracene iaomers*
Oibenzo (c, g) carbazole
3-Mechylcholancfar ene
Indeno ( 1 , 2 , 3-cd) pyr ene
Benzo (gai) perylene
Dibenz(ah or a}) anthracenes
Dibenzacridinea
Coronene
Dibenzo(a,h}pyrene
Dibenzo < a, i) pyr ene
»/e
128
166
178
202
202
228
228
252
252
252
252
25A
256
267
263
276
276
278
279
300
302
302
Test ft
7
0.3
-
8a
0.007
0.003
20b
0.8C
!<*
0.01
0.3
20000
7000e
30
-
8
0.6 .
-
9*
0.02
0.007
30b
0.9C
2d
0.01
0,3
30000
10000e
40
0.06
_
800f
.
9
1
-
10a
0.01
0.004
2b
O.lc
0.03d
0.03
1000
umber
in
0.5
-
5a
0.005
0.002
4b
0.3C
0.3d
0.004
0.02
2000e
11
0.2
-
6a
0.008
0.003
8b
0.4C
0.4d
0.004
0.09
7000
3000e
_
•
2H
0.3
-
2a
0.003
0.0006
6b
0.2C
0.04
4000
* Includes- dimethyl'-- and ethyl-^-cnrysenes, bcnzo
phenanthrenes bcnzathracenes,
** All blanks are items below detection, limit.
- DMEG values are not available..
a... Based on DMEG of Phenanthrene.
b. Based on DMEG of Benz(a)anthracene.
c, Based on DMEG of Chrysene.
d. Based on DMEG of Benzo(b)fluoranthene .
e. Based on DMEG of 7,12-Dimethyl benzCa) anthracene.
f. Based on DMEG of Dibenz(ah)anthracene.
-88-
-------
TABLE 8-23
DISCHARGE SEVERITY CALCULATED FOR POM IN
COAL PREHEATER SAMPLES, OUTLET
Discharge Severity
Species
Naphthalene
Fluor ene
Anthrac ene /Phenant hr ene
Fluoranthene
Pyrene
Benz (a) anthracene/ (c)phenanthrene
Chrysene/Triphenylene
Benzo(b or k)fluoranthene
Benzo ( j ) f luoranthene
Benzo(e)pyrene
Benzo (a)pyrene
Cholanthr ene
Dimethyl benzanthracene isotners"
Dibenzo (c , g) carbazole
3-Methylcholanthrene
Indeno (1,2, 3-cd) pyrene
Benzo (ghi)perylene
Dibenz(ah or aj) anthracenes
Dibenzacridines
Coronene
Dibenzo (a, h)pyrene
Dibenzo (a, i) pyrene
m/e
128
166
178
202
202
228
228
252
252
252
252
254
256
267
263
276
276
278
279
300
302
302
Test Number
1, H?0
7 x 10-5
2 x 10-3
1 x 10~6
2, H?0
2 x 10~s
-
9 x 10"*
3, H?0
7 x 10-5
-
2 x 10-3
3 x 10~6
2 x 10-6
* Includes dimethy- and othyl-chryscnes, benzophenanthrenes, and
benzanthrscenes.
** All blanks are items below detection limit.
- DMEG values are not available.
-89-
-------
8.3 EPA-5 Train Test Results
Particulate emissions analyzed in accordance with EPA
Method 5 are summerized in Table 8-24. Results are pre-
sented in terms of chloroform soluble and non-chloroform
soluble emissions. On the basis of one test, the total
scrubber inlet concentration (chloroform and non-chloroform
soluble particulate in the front and back half catches, but
not including the silica gel) was 9014.7 mg/Nm . Outlet
concentrations ranged from 951.8 to 1635.9 mg/Nm .
-90-
-------
TABLE 8-24
Chloroform Suluble & Non-Chloroform Soluble Particulates
A. Non-Chloroform Soluble Particulate
Nozzle, Probe,
Front Half
Test No. Location Filter Holder
B.
1
2
2
3
Outlet
Inlet
Outlet
Outlet
Chloroform Soluble
mg/Nm
90.6
922.1
59.5
75.5
%WT.
14.2
11.2
7.2
13.1
Particulate
Test No. Location
Nozzle, Probe,
Front Half
Filter Holder
Filter
mg/Nm3 %WT.
228.8 36.4
6763.3 82.0
572.0 69.4
391.2 68.1
Filter
Back Half Filter Holder,
Impinger Lines, Impingers,
Impinger Solutions
mg/Nm
311.2
562.8
192.2
107.2
%WT.
49.2
- 6.8
23.4
18.8
Back Half Filter Holder,
Impinger Lines, Impingers,
Impinger Solutions
1
2
2
3
C. Total
Test
1
2
2
3
Outlet
Inlet
Outlet
Outlet
Particulate
No. Location
Outlet
Inlet
Outlet
Outlet
mg/Nm %WT. mg/Nm
9.8 1.3 100.0
93.4 9.2 416.9
7.5 1.1 402.0
2.5 0.2 140.9
%WT.
12.5
41.0
58.2
11.8
mg/Nm %WT .
213.0 26.7
266.6 26.2
197.2 28.6
918.4 76.9
(Chloroform Soluble + Non-Chloroform Soluble)
EPA- 5
mg/Nm g/M-Ton
429.2 95.5
8195.7 1563.9
1041.0 161.6
610.1 140.3
PA-DER
mg/Nm g/M-Ton
953.4 2l2.2
9025.1 1722.3
1430.4 222.2
1635.7 376.1
Silica Gel
mg/Nm %WT.
Silica Gel
mg/Nm
475.4
239.6
83.5
132.9
3
%WT.
59.5
23.6
12.1
11.1
Total
mg/Nm
630.6
8248.2
823.7
573.9
mg/Nm
798.2
1016.5
690.0
1194.7
g/'M-Ton
139.9
1574.0
127.9
132.0
Total
g/M-Ton
178.0
194.0
107.5
274.5
%WT.
100
100
100
100
%WT .
100
100
100
100
-------
8.4 Results of Benzine Soluble Organic Analysis
The particulate loadings and benzine soluble organic
residue loadings are summarized in Table 8-25 for the six
BSD Tests.
Particulate loadings at the ^scrubber inlet range from 1600.5
to 9205.0 mg/Nm . Outlet loadings range from 199.3 to
1332.4 mg/Nm3.
Benzine soluble organic concentration at the scrubber inlet
ranged from 1157.3 to 2741.4 mg/Nm . Concentration at the
outlet ranged from 783.3 to 1930.3 mg/Nm .
Individual test results are given in Tables 8-26 through 8~31
which also provide concentrations by sampling train com-
ponent for both particulates and benzine soluble organics.
-92-
-------
TABLE 8-25
SUMMARY OF BENZENE SOLUBLE TESTS
These tests were conducted for determination of benzene soluble residue in the inlet and
outlet to the coal preheater scrubber. Particulate weight is also reported.
Benzene Soluble Residue
Test No.
Process Conditions*
mg/m"
q/hr
tons of Coal
1 inlet
1 outlet
2 inlet
2 outlet
3 inlet
3 outlet
i
vo
i Test No.
1 inlet
1 outlet
2 inlet
2 outlet
3 inlet
3 outlet
* Coal
** Does
82/271
82/271
109/271
109/271
55/288
55/288
1157.3
783.3
2741.4
1930.3
1279.4
1343.7
Particulate Residue**
Process Conditions* mg/m
82/271
82/271
109/271
109/271
55/288
55/288
feed rate in (M-Tons per hour)
not include weight of benzene
9205.0
199.3
5524.8
1332.4
1605.5
227.8
/(temperature, C)
soluble residue.
35489
14900
106340
55460
24971
21763
g/hr
255371
3787.5
201838
39862
312355
3687
435
186.3
970
533.7
457.7
397.2
g/M tons of coal
3143
45.5
1882.5
365.9
5739.8
66
-------
TABLE 8-26
Benzene Soluble Test No. 1 Inlet
Process Conditions: coal feed rate =90 tons/hr
temperature = 520°F
Benzene Soluble Residue
Sampling Train
Component
1.
2.
3.
4.
5.
6.
Front half Benzene wash
Front half Acetone wash
Filter
Adsorber
Back half Benzene wash
Back half Acetone wash
Total
mg/m
820.0
47.6
133.1
135.4
119.0
24.2
1157.3
g/hr
22748
1320
3692
3756
3302
671
35489
g/M tons of coal
280.0
16.0
45.0
46.0
40.0
8.0
435.0
Particulate Residue
Sampling Train
Component
1.
2.
3.
4.
5.
6.
Front half Benzene wash
Front half Acetone wash
Filter
Adsorber
Back half Benzene wash
Back half Acetone wash
Total
mg/m
5590.0
80.5
3497.0
Q.O
1.89
35.5
9204.9
g/hr
155082
2236
97023
0
54
984
255371
g/M tons of coal
1898.0
27.0
1199.0
0.0
6.5
12.0
3143.0
-94-
-------
TABLE 8-27
Benzene Soluble Test No. 1 Outlet
Process Conditions: coal feed rate = 90 tons per hour
temperature =
Benzene
Sampling Train
Component
1. Front half Benzene wash
2. Front half Acetone wash
3. Filter
4. Adsorber
5. Back half Benzene wash
6. Back half Acetone wash
Total
Soluble
520°F
Residue
3
mg/m g/hr
26.7
12.9
40.9
271.
402.2
28.8
783.3
508
245
780
5171
7648
549
14900
g/M tons of coal
5.99
3.00
9.49
64.94
94.41
6.49
186.33
Particulate Residue
Sampling Train
Component
1. Front half Benzene wash
2. Front half Acetone wash
3. Filter
4 . Adsorber
5. Back half Benzene wash
6. Back half Acetone wash
Total
mg/m
21.1
21.4
144.8
0.0
10.6
1.4
199.3
3 g/hr
399.2
408.2
2753.3
0.0
27.2
199.6
3787.5
q/M tons of coal
4.90
5.00
33.50
0.0
0.33
1.85
45.55
-95-
-------
TABLE 8-28
Benzene Soluble Test No. 2 Inlet
Process Conditions: coal feed rate = 120 tons/hr
temperature = 520°F
Benzene Soluble Residue
Sampling Train
Component
1.
2.
3.
4.
5.
6.
Front half Benzene wash
Front half Acetone wash
Filter
Adsorber
Back half Benzene wash
Back half Acetone wash
Total
Particulate
Sampling Train
Component
1.
2.
3.
4.
5.
6.
Front half Benzene wash
Front half Acetone wash
Filter
Adsorber
Back half Benzene wash
Back half Acetone wash
Total
mg/m
2097.0
18.9
177.3
103.9
312.6
31.6
2741.4
Residue
mg/m
2631.0
89.4
2791.0
0.0
9.4
3.9
5524.7
g/hr
76611
694
12664
3797
11417
1157
106340
g/hr
46116
3270
101967
0
340
145
201838
g/M tons of coal
699.0
6.0
115.0
34.5
105.0
10.5
970.0
g/M tons of coal
899.0
-30.0
949.0
0.0
3.15
1.35
1882.5
-96-
-------
TABLE 8-29
Benzene Sellable Test No. 2 Outlet
Process Conditions: coal feed rate =120 tons/hr
temperature = 520°F
Benzene
Sampling Train
Component
1. Front half Benzene wash
2. Front half Acetone wash
3. Filter
4 . Adsorber
5. Back half Benzene wash
6. Back half Acetone wash
Total
Soluble
mg/m
197.6
11.5
831.8
322.4
565.0
1.9
1930.3
Residue
g/hr
5910
345
24875
9643
14628
59
55460
g/M tons of coal
55.0
3.15
230.0
90.0
155.0
0.55
533.7
Particulate Residue
Sampling Train
Component
1. Front half Benzene wash
2. Front half Acetone wash
3. Filter
4. Adsorber
5. Back half Benzene wash
6. Back half Acetone wash
Total
mg/m
128.7
21.5
1145.0
0.0
66.1
30.5.
1332,4
g/hr
3851
644
34255
0
200
912
39862
g/M tons of coal
35.0
6.0
315.0
0.0
1.9
8.0
365.9
-97-
-------
TABLE 8-30
Benzene Soluble Test No. 3 Inlet
Process Conditions: coal feed rate = 60 tons/hr
temperature = 550°F
Benzene
Sampling Train
Component
1. Front half Benzene wash
2. Front half Acetone wash
3. Filter
4 . Adsorber
5. Back half Benzene wash
6. Back half Acetone wash
Total
Soluble Residue
3
mg/m
279.7
36.2
277.7
187.9
489.7
13.2
1279.4
g/hr
5457
708
5420
3570
9557
259
24971
g/M tons of coal
100.0
13.0
100.0
65.0
175.0
4.7
457.7
Particulate Residue
Sampling Train
Component
1. Front half Benzene wash
2. Front half Acetone wash
3. Filter
4 . Adsorber
5. Back half Ben»ene wash
6. Back half Acetone wash
Total
mg/m
3176.0
207.4
12420.0
0.0
189.4
12.7
16005.5
g/hr
62006
4050
242353
0
3697
249
312355
g/M tons of coal
1149.0
75.0
4446.0
0.0
65.0
4.8
5739.8
-98-
-------
TABLE 8-31
Benzene Soluble Test No. 3 Outlet
Process Conditions:
Sampling Train
Component
1. Front half
2. Front half
3. Filter
4 . Adsorber
5. Back half
Benzene
Benzene wash
Acetone wash
Benzene wash
6. Back half Acetone wash
Total
coal feed rate
temperature =
= 60
550°F
tons/hr
Soluble Residue
3
mg/m
7.5
21.0
72.1
155.3
143.1
944.7
1343.7
g/hr
122
340
1170
2513
3318
15300
21763
g/M tons of coal
2.2
6.0
21.0
46.0
42.0
280.0
397.2
Particulate Residue
Sampling Train
Component
1. Front half
2. Front half
3. Filter
4 . Adsorber
5. Back half
6. Back half
Total
Benzene wash
Acetone wash
Benzene wash
Acetone wash
mg/m
66.2
26.3
86.3
0.0
18.1
30.2
227.7
/hr
1070
426
1397
0
295
499
3687
g/M tons of coal
19.0
7.5
25.0
0.0
5-5
9.0
66.0
-99-
-------
8.5 Results EPA Level 1 Organic Analysis
The Level 1 Organic Analysis results for the two stack
samples, two water samples, and the blanks are shown in
Tables 8-32 through 8-37. The organic species found in
each sample extract were classified into compound categories
based on the LC, IR, and LRMS data. The concentration of
each category was estimated using the method described
in the EPA Level 1 procedure manual. These data are further
summarized in Table 8-38. Aliphatic hydrocarbons, fused
aromatics, phenols, and esters were found to be the major
components for both inlet and outlet stack samples, with
lower concentrations for the inlet sample. Aliphatic
hydrocarbons, carbazoles, and phenols were found in the
water samples. The alkyl benzenes and dibutyl phthalate
which were found in the outlet water sample but not in
the inlet water sample T^ould be attributed to contaminants
in the sample.
-100-
-------
TABLE 8-32
Organic Extract Summary
Sample 2A Inlet. Stack Sample
Total Organics. mgla3
TCO, mg
GRAV, mg
LCI
188
111
130
LC2
520
305
360
LC3
87
34
78
LC4
23
7.7
22
LC5
33
12
30
LCfl
213
43
230
LC7
40
13
38
£
1100
530
890
Category
Int/mg/nr
l
M
O
M
I
Aliphatic Hydrocarbons
Fused Aroma tics, <216 m/e
Fused Aroraatics, >216 in/e
Heterocyclic N Compounds
Esters
Phenols
Unclassified
10/188
-
100/260
100/260
100/73
10/7.3
10/7.3
100/5.6
100/5.6
100/5.6
100/5.6
10/0.6
10/214
10/2.4
10/2.4
100/24
10/2.4
10/9.7
100/97
100/97
10/9.7
10/1.9
100/19
100/19
1/0.2
188
341
275
20
146
116
20
-------
TABLE 8-33
Organic Extract Summary
Sample 2A Outlet. Stack Sample
Total Organics. mg/m^
TCO. mg
GRAV, m§
LCI
63
45
37
LC2
94
49
73
LC3
35
1.6
43
LC4
5.8
2.1
5.5
LC5
5.8
1.1
6.5
tee
7.7
2.9
7.3
LC7
15
7.2
12
E
230
109
184
Category
Int/mg/m
Aliphatic Hydrocarbons
Fused Aroma tics, m/e <216
Fused Aroma tics, m/e >216
Heterocyclic N Compounds
Esters
Unclassified
i
100/57
10/5.7
100/31
100/31
100/31
100/17
100/17
100/1.7
10/0.4
10/0.4
10/0.4
100/4.4
1/0.1
100/5.7
1/0.6
";- -
100/7.7
100/15
1/1.5
74
7.7
48
33
31
J3
o
N)
I
-------
TABLE 8-34
Organic Extract Summary
SamplB 2 Inlett Water Sample
Total Organic*, nig/ L
TCO, mg
GRAV, mg
LCI
76
8.4
30
LC2
22
4.1
6.7
LC3
3.4
0.9
0.8
LC4
4.4
1.2
1.0
LC5
5.2
1.3
1.3
LC6
26
1.3
12
LC7
13
3.6
3.1
r
150
21
55
Category
Int/mg/L
Aliphatic Hydrocarbons
Fused Aromatics, m/e <216
Fused Aromatlcs, m/e >2l6
Heterocyclic N Compounds
Phenols
Esters
Ketones and Aldehydes
Unclassified
100/69
10/6.9
-
100/11
100/11
10/1
100/1.1
100/1.1
100/1.1
10/0.1
100/1.5
100/1.5
100/1.5
100/1
100/1
100/1
100/1
100/1
100/8.4
100/8.4
100/8.4
10/0.8
..
100/4.2
100/4.2
100/4.2
10/0.4
69
13
13
16
14
1.0
14
10
o
U)
I
-------
TABLE 8-35
Organic Extract Summary
Sample 2 Outlet. Water Sample
1
Total Organic*, mg/L
TCO, mg
GRAV. mg
LCI
40
1.2
19
LC2
24
0.4
12
LC3
28
0.7
13
LC4
42
0.7
20
LC5
4.6
1.0
1.3
LC6
36
2.1
16
LC7
9.2
1.3
3.3
Z
184
7.3
85
Category
Int/mg/ L
Aliphatic Hydrocarbons
Aromatic Hydrocarbons
Heterocyclic N Compounds
Ke tones
Phenols
Esters
Carboxylic Acids
Unclassified
-
100/36
10/3.6
-
10/1.1
100/11
100/11
*
100/13
100/13
10/1.3
10/3.5
10/3.5
i .
100/35
10/0.5*
100/2.3*
10/0.5*
10/0.5*
100/12
100/12
100/12
10/1.2
100/3
100/3
100/3
10/0.3
54
28
15
14
15
48
3.0
5.1
I
M
o
I
Estimated from I.C and IK data, with LRMS data of adjacent fractions
-------
TABLE 8-36
Organic Extract Summary
Sample
Stack Blank
Total Organic*, mg/m3
TCO, ma
GRAV, mg
LCI
28
ND
14
LC2
2.6
0.3
1.0
LC3
22
0.6
10
LC4
2.6
0.8
0.5
LC6
3.2
0.8
0.8- -
LC6
8.8
3.6
0.8
LC7
11
3.9
1.8
£
78
10
29
Category
iliphatlc Hydrocarbons
lnt/mg/4n3
10/0.3
10/1.0
1.3
|Aromatic Hydrocarbons
100/10
10
o
Ul
I
I Esters
100/10
100/1.3
1/3.2
100/4.4
1/11
30
[unclassified
10/28
28
Estimated from L.C and IR data, with LRMS data of adjacent fractions
-------
TABLE 8-37
Organic Extract Summary
Sample Water Blank
Total Organic*. mg/L
TCO, mg
GRAV. mg
LCI
40
2.7
17
LC2
3.0
0.7
0.8
LC3
3.0
0.2
1.3
LC4
2.6
0.8
0.5
LC5
2.6
0.5
0.8
LC6
1.6
0.8
ND
LC7
3.0
1.0
0.5
r
56
Category
Int/mg/L
I
M
Q
Aliphatic Hydrocarbons
Esters
Unclassified
100/36
10/4.0
-
10/0.3*
* *
10/0.3
**
10/0.3
10/0.3*
1/1.6
*
,
10/0.3*
36-
2.8
4.0
**
Estimated from L.C and IR Data, with LRMS data of adjacent fractions
Estimated from l.C and IR Data.
-------
TABLE 8-38
SUMMARY OF EPA LEVEL 1 ORGANIC ANALYSIS
Compound Categories
\ j
i
Aliphatic Hydrocarbons 190
Aromatic Hydrocarbons
Fused Aromatics, m/e 216 280
Heterocyclic N Compounds 20
Aldehydes & Ketones
Alcohols, Phenols 120
Esters 150
Carboxylie Acids
•Stack Samples (me/tn3)
2A Inlet 2A Outlet
Water Samples (ng/L)
2 Inlet 2 Outlet
74
8
48
33
31
69
13
13
16
14
14
1
54
28
15
14
15
48
3
-107-
-------
8.6 Benzene and Total Hydrocarbons in Stack Gas Grab Samples
The results of the GC analysis on the grab samples are
given in Table 8-39. Both benzine and total hydrocarbons
(measured as methane) appear to significantly increase
across the scrubber.
TABLE 8-39
Benzine
in
Process*
Conditions
and Total Hydrocarbons
Grab Samples :
Benzene (PPM)
Inlet Outlet
108.4/287.8 42.0 57.1
108.0/287.8 0.8*** 12.1
81.6/287.8 0.8 3.7
108.9/271.1 8.1 8.1
54.4/287.8 0.8 15.1
29.0/260.0 no sample 9.9 no
81.6/271.1 0.8 1.8
81.6/260.0 0.8 23.0
Total
Inlet
708.9
249.5
353.6
195.4
112.1
sample
317.7
26.6
Hydrocarbons**
Outlet
266.5
1942.1
242.6
1605.0
2718.3
732.2
2190.2
399.4
Test Date
7/26/78
7/27/78
7/28/78
7/29/78
7/30/78
7/31/78
8/2/78
8/3/78
* (Coal feed rate, M-Ton/Hr}/(Temperature, C)
** Total Hydrocarbons determined as methane
*** The detection limit for benzene was 0.8 ppm.
8.7 Benzene Content in Water Grab Samples
No benzene was detected in the six water samples (Test 1,
2 and 3, inlet and outlet) when they were analyzed on a
Porapak Q column with a Varian 2700 FID GC. The detection
limit was 5 ppm. It is possible that trace amounts of benzene
originally present in the samples were lost before the samples
were analyzed.
-108-
-------
8. 8 Sulfur in Impinger Catches
The results of the sulfer analysis conducted on the impinger
catches of POM tests II, inlet and outlet, are presented in
Table 8-40.
-109-
-------
TABLE 8-40
Sulfur in Impinger Catches
Process Conditions: coal feed rate = 54 Microns/Hr
temperature = 276.6 °"C
Test Number
POM Test 1 inlet
Impinger water
Methylene Chloride wash
Total
mg/nr
j/hr g/M ton of coal
74.90
0.974
75.9
1251.9
16.33
1270.05
22.979
0.2997
23.479
POM Test 1 Outlet
Impinger Water
Methylene Chloride wash
Total
9.440
0.822
10.300
113.85
9.888
123.83
2.098
0.180
2.298
-110-
-------
8.9 Coal Analysis
All the coal samples were sieved through a 100 mesh screen
and analyzed for moisture, volatile matter, ash, sulfur and
carbon contents according to ASTM methods (D3173, 3174,
3175, 3177, and 3178). Table 8-41 shows the sieving and
moisture analyses results. For most of the coal samples,
the fraction smaller than 100 mesh was found to be 10%
for the Inlst samples and 20% for the Outlet samples.
The moisture contents for all samples were Ca 1%. The
results of volatile, ash, sulfur, and carbon analyses are
summarized in Tables 8.42 and 8.43. slightly higher ash contents
were observed for the Inlet samples than the corresponding
Outlet samples. No substantial differences in volatile,
carbon, hydrogen, and sulfur contents were observed between
the Inlet and Outlet samples.
The coal samples from Test No. 2 Inlet and Outlet were also
analyzed for trace elements. The results are given in Tables
8-44 through 8-47. A summary table with the elements over
5 mg/kg concentration for the four samples is also presented
(Table 8-48). All the coal samples were also examined by
stereo microscope at magnifications from 7 to 30 times.
Each sample was subsequently documented with a photomacrograph
/
taken at 6X magnification. The general observations are as
follows for the "inlet" or "outlet" samples: •
1. Most of the inlet samples exist as coarser and non-uniform
particle sizes.
-Ill-
-------
2. Most of the outlet samples exist as smaller, more
uniform sizes.
3. The inlet samples which were furnished in a can
exhibit an acidic activity which corroded the
interior of the can. Two inlet samples were packaged
in glass where this corrosion was precluded.
4. The outlet samples did not corrod the interior of
the can indicating the absence of acidity.
5. Many of the outlet samples have an oily odor similar to
kerosene. This odor is not detected in any of the inlet
samples.
6. All samples appear to be coal with almost no extraneous
matter.
7. The particles are all irregular in shape.
8. There appears to be two basic forms of coal fragment.
One exhibits smooth, glassy fracture faces while the
other form has a dull matte surface presumably from a
fine-grained microstrueture.
The following comments and observations are pertinent to each
of the specific coal samples examined by microscopy:
Sample No. Observations
1 Inlet Dull, brown-black color for most of material.
There are a few shiney, highly-reflective
surfaces which appear blacker than the rest
of the material. No extraneous material
noted. Some moisture is present, but which
dries rapidly. Particle size range 2-3 mm
and smaller.
-112-
-------
1 Outlet
2 Inlet
2 Outlet
3 Inlet
3 Outlet
Sample appears blacker than fl inlet,
possibly because of more broken particles
with shiney black surfaces apparent.
Noted one small stone (silicate mineral).
The fines on this sample tend to be
aggregated, whereas No. 1 inlet tended
to be dispersed.
Similar size range. Probably more of
the larger particles 2-5 mm size. Smaller
sizes tend to aggregate. No extraneous
matter noted.
Sizes of particles up to approximately
5 mm. Smaller particles do not tend to
aggregate. No extraneous matter noted.
Sample is in quart can. Previous samples
were in glass. Indicate that acidic
moisture is present which reacted with
metal can to produce rusty scale. Some of
these rust fragments are apparent in the
sample.
Sample now appears dry—non-aggregated
and brownish in color. There are more of
larger particles greater than 5 mm.
Noticeable kerosene odor upon opening the
can. No corrosion noted on inner can wall.
Finer particles (>5 mm). No obvious
extraneous material.
-113-
-------
4 Inlet
4 Outlet
5 Inlet
5 Outlet
(No 6 Inlet)
6 Outlet
This sample consists of the dry,
separated particulates. The color is
brownish black. A sizable fraction
consists of larger particle sizes >5 mm.
Container wall is corroded from acid
water attack. No extraneous matter noted
in coal dust.
Sample is slightly contaminated with corro-
sion (rust flakes) from inner walls of
container. Particles are separate.
Fairly large percentage of particles are
larger than 2-3 mm.
Sample is slightly contaminated with
corrosion (rust flakes) from inner walls
of container. Particles are separate.
Fairly large percentage of particles are
larger than 2-3 mm. •>
Distinct kerosene odor noted upon opening
the can. Particles tend to agglomerate.
Note two different textures to larger
particles; one is fine-grained while the
other is more glassy. Most larger particles
throughout these samples are flat plate-
like.
Very strong kerosene odor. Particles tend
to aggregate. Particle size is largely
below 3 mm. Color appearance is more jet
black.
-114-
-------
7 Inlet
7 Outlet
8 Inlet
8 Outlet
9 Inlet
Corrosion of can interior indicates
probable acidic water content. Par-
ticles appear more of a gray black.
Some aggregation is apparent. No extran-
eous material noted. Contents of can
more irregular in particle size, several
larger lumps 5-50 mm.
Sample is more uniformly pulverized.
Maximum size appears to be 3-5 mm. Parti-
cles appear dry-free flowing. Some of the
larger (3-5 mm) particles are fine-grained
in contrast to the usual glassy fragrants.
Considerable corrosion to inside of can.
Note that larger particles tend to aggre-
ate. Some larger particles appear fine-
grained instead of glassy. Some contami-
nation noted due to corrosion products
from side of can. Moisture present dries
readily in room atmosphere.
Faint oily odor noted. Can inside is not
corroded. Fairly large amount of particles
in 3-10 mm range. Some tendency for small
particles to aggregate. No noticeable
contamination.
Interior of can is badly corroded. Parti-
cle size is non-uniform with larger parti-
cles up to 2-3 cm in diameter. Particles
-115-
-------
9 Outlet
10 Inlet
10 Outlet
11 Inlet
12 Outlet
are non-aggregated. Some contamination
from corrosion products from can. Some
fine-grained particles in addition to
the usual glassy type.
No corrosion noted. Some aggregation of
small particles. Faint oily odor noted.
Sample is well pulverized. Few particles
in 3-5 mm range.
Some minor corrosion of can. Sample is
well aggregated. Note 2 or 3 large parti-
cles in the 2 to 3 cm range. No extraneous
material noted. Coal appears blacker due
to whatever causes particles to aggregate.
No corrosion noted. Sample is well pul-
verized. Largest particles less than 1 cm.
No extraneous material. No aggregation
apparent.
Considerable corrosion to interior of can.
Particle size of material is non-uniform.
Many larger particles 1-3 cm. No aggrega-
tion. No extraneous matter.
No corrosion noted. Particle size of
material is in the small size range.
Most under 5-10 mm. No aggregation noted.
No extraneous material.
- 116-
-------
TABLE 8-41
SIZE AND MOISTURE ANALYSIS OF COAL SAMPLES
(Based on Sample Weights as Received at the Lab)
Sample
No.
Inlet
1
2
3
4
5
7
8
9
10
11
Outlet
1
2
3
4
5
6
7
8
' 9
10-
11
% <100 Mesh
(A)
12.6
12.6
10.4
20.3
10.1
8.7
12.1
9.2
12.1
11.9
28.6
17.1
18.1
16.2
15.0
12.4
18.2
15.3
27.3
19.2
23.2
% >100 Mesh
(E)
87.4
87.4
89.6
79.7
89.9
91.3
87.9
90.8
87.9
88.1
71.4
82.9
81.9
83.8
85.0
87.6
81.8
84.7
72.7
80.8
76.8
35
A
1.20
1.19
1.33
1.21
1.43
1.52
1.62
1.81
1.28
1.49
A
1.24
1.03
2.55
0.65
1.44
6.74
O.S2
0.82
0.82
0.84
0.83
Moisture
B
1.08
1.19
1.38
1.28
1.20
1.36
1.36
1.49
1.19
1.10
B
1.11
0.79
1.12
1.03
1.30
5.23
1.00
1.04
0.87
1.21
0.92
-117-
-------
TABLE 8-42'
COAL ANALYSIS RESULTS
Inlet Samples, Based on Dry Coal Weight
Sample
A
1 B
2 A
B
A
3 B
4 A
B
5 A
B
7 A
B
A
8 B
A
9 B
10 A
B
11 \
B
Avg. A
B
Ash
8.89
7.11
8.94
9.54
9.50
8.22
9.66
7.67
9.36
7.54
8.41
7.64
9.29
8.54
9-61
6.74
9.70
6.42
8.13
7.73
9.15
7.72
Volatile
29.06
31.69
28.54
32.37
28.02
31.87
28.70
30.86
28.16
32.15
29.18
31.35
28.83
32.72
27.95
31.43
27.44
32.66
28.07
31.44
28.40
31.85
Carbon
79.26
80.15
78.94
80.51
77.30
78.77
77.76
79.55
77.67
'80.08
78.40
80.41
76.83
77.85
77.18
80.66
78.36
80.30
79.42
79.59
78.11
79.79
Hydrogen
4,95
5.07
4.79
Oxygen 4- Un-
determined
6.90
7.67
7.33
5.30 4.65
i
4.78 8.42
5.00 8.01
Sulfur
1.24
1.13
1.23
1.09
1.26
1.11
! i
4.80 7.78
5.03 7.75
4.82
5.08
4.87
5.26
4.71
5.06
4.76
5.15
4.32
5.15
4.85
5.03
4.82
5.11
8.15
7.30
8.32
6.69
9.17
8.55
8.45
7.45
7.12
8.13
7.60
7.65
7.92
7.39
1.23
0.99
1.35
1.11
1.18
1.03
1.42
1.21
1.39
1.04
1.33
1.17
1.38
1.14
1.30
1.10
* A: Fraction of the coal samples smaller than 100 mesh.
B: Fraction of the coal samples greater than 100 mesh.
-118-
-------
TABLE 8-43
COAL ANALYSIS RESULTS
Outlet Samples. Based on Dry Coal Weight
Sample
No.
1 A*
B
2 A
B
3 A
B
4 A
B
5 A
B
6 A
B
7 A
B
8 A
B
9 A
B
10 A
B
A
B
Avg.
B
Ash
6.40
6.25
6.18
7.57
6.05
6.80
6.66
7.56
6.37
6.37
8.35
7.63
6.27
6.96
6.83
7.82
6.37
6.44
Volatile
28.88
32.22
28.20
32.92
28.98
32.68
27.79
30.97
28.03
32.54
29.63
31.55
28.75
31.90
20.01
33.46
28.28
33.49
6.61 • 27.67
6.36 '' 31.72
5.98
6.34
6.55
6.92
27.74
32.24
1 -
27.63
32.34
Carbon
81.70
80.77
81.75
79.89
83.27
79.91
80.39
79.59
81.80
79.92
83.85
82.84
80.59
79.67
80.51
78.56
81.44
80.15
80.93
81.00
81.53
80.42
81.61
80.25
i—..—™.— *—— •— ••
Hydrogen
4.97
5.16
4.97
5.13
5.00
5.09
4.87
4.96
5.04
5.07
4.95
5.08
4.91
5.07
4.83
5.04
9.05
5.13
4.83
5.26
4.80
5.15
5.29
5.10
. ._ .
Oxygen + Un-
determined
6.93
7.82
7.10
7.41
5.68
8.20
8.08
7.89
6.79
8.64
2.85
4.45
8.23
8.30
7.83
8.58
3.14
8.28
7.63
7.38
7.69
8.09
6.54
7.73
••- — '
Sulfur
1.12
1.15
1.13
1.19
1.17
1.24
0.92
1.22
1.29
1.16
1.24
1.13
1.26
1.21
1.22
1.31
1.17
1.13
1.26
1.16
1.24
1.21
1.18
1.19
— • . ..P.
* A: Fraction of the coal samples smaller than 100 mesh.
B: Fraction of the coal samples greater than 100 mesh.
-119-
-------
TABLE 8-44
SPARK SOURCE MASS SPECTROMETRY DATA
Sample No: 2, Inlet. <100 mesh, Sample was Parr Oxygen Bombed
Concentration in mg/kg
Element
Aluminum
Antimony
Arsenic
Barium
Beryllium
Bismuth
Boron
Bromine
Cadmium
Calcium
Carbon
Cerium
Cesium
Chlorine
Chromium
Cobalt
Copper
Dysposium
Erbium
Europium
Fluorine
Gadolinium
Gallium
Germanium
Gold
Hafnium
Cone.
2
31
0.2
0.6
0.3
0.1
MC
NR
3
3
0.9
8
0.8
25
0.2
0.1
Element
Holmium
Hydrogen
Indium
Iodine
Iridium
Iron
Lanthanum
Lead
Lithium
Lutetium
Magnesium
Manganese
Mercury
Molybdenum
Neodymium
Nickel
Niobium
Nitrogen
Osmium
Oxygen
Palladium
Phosphorus
Platinum
Potassium
Praseodymium
Rhenium
Cone.
NR
0.08
700
2
2
8
4
NR
0.4
0.8
0.8
1
NR
NR
110
>900
0.4
Element
Rhodium
Rubidium
Ruthenium
Samarium
Scandium
Selenium
Silicon
Silver
Sodium
Strontium
Sulfur
Tantalum
Tellurium
Terbium
Thallium
Thorium
Thulium
Tin
Titanium
Tungsten
Uranium
Vanadium
Ytterbium
Yttrium
Zinc
Zirconium
Cone
0.9
0.7
1
0.8
MC
50
6
>430
0.6
0.7
350
0.1
5
2
7
4
NR - Not reported.
All elements not reported < 0.06 ppm weight,
MC - Major component,>1 g/kg
-120-
-------
Sample No.:
TABLE 8-45
SPARK SOURCE MASS SPECTROMETRY DATA
2, Inlet, >100 Mesh, Sample was Parr Oxygen Bombed
Concentration in ma/ :kg
Element
Aluminum
Antimony
Arsenic
Barium
Beryllium
Bismuth
Boron
Bromine
Cadmium
Calcium
Carbon
Cerium
Cesium
Chlorine
Chromium
Cobalt
Copper
Dysp'osium
Erbium
Europium
Fluorine
Gadolinium
Gallium
Germanium
Gold
Hafnium
Cone.
0.3
- 110
0.2
0.8
0.7
0.2
MC
NR
12
2
4
0.1
9
3
0.1
Element
Holmium
Hydrogen
Indium
Iodine
Iridium
Iron
Lanthanum
Lead
Lithium
Lutetium
Magnesium
Manganese
Mercury
Molybdenum
Neodymium
Nickel'
Niobium
Nitrogen
Osmium
Oxygen
Palladium
Phosphorus
Platinum
Potassium
Praseodymium
Rhenium
Cone.
NR
STD
MC
7
1
6
5
NR
0.4
0.3
0.2
2
NR
NR
50 •
2
MC
0.3
Element
Rhodium
Rubidium
Ruthenium
Samarium
Scandium
Selenium
Silicon
Silver
Sodium
Strontium
Sulfur
Tantalum
Tellurium
Terbium
Thallium
Thorium
Thulium
Tin
Titanium
Tungsten
Uranium
Vanadium
Ytterbium
Yttrium
Zinc
Zirconium
Cone
2
0.8
3
0.9
MC
MC
60
>620
3
460
2
8
8
4
15
NR - Not reported.
All elements not reported < 0.09 ppm weight.
MC - Major component, >1 g/kg
-121-
-------
Sample No.
TABLE 8-46
SPARK SOURCE MASS SPECTROMETRY DATA
2, Outlet, <100 Mesh, Sample was Parr Oxygen Bombed
Concentration in mg/kg
Element
Aluminum
Antimony
Arsenic
Barium
Beryllium
Bismuth
Boron
Bromine
Cadmium
Calcium
Carbon
Cerium
Cesium
Chlorine
Chromium
Cobalt
Copper
Dysp'osiura
Erbium
Europium
Fluorine
Gadolinium
Gallium
Germanium
Gold
Hafnium
Cone.
3
170
0.1
0.7
1
0.3
MC
NR
8
0.2
1
8
0.2
23
0.5
2
0.3
Element
Holmium
Hydrogen
Indium
Iodine
Iridium
Iron
Lanthanum
Lead
Lithium
Lutetium
Magnesium
Manganese
Mercury
Molybdenum
Neodymium
Nickel
Niobium
Nitrogen
Osmium
Oxygen
Palladium
Phosphorus
Platinum
Potassium
Praseodymium
Rhenium
Cone.
NR
STD
MC
7
6
6
220
7
NR
0.5
2
1
•4
NR
NR
91 -
1
MC
2
Element
Rhodium
Rubidium
Ruthenium
Samarium
Scandium
Selenium
Silicon
Silver
Sodium
Strontium
Sulfur
Tantalum
Tellurium
Terbium
Thallium
Thorium
Thulium
Tin
Titanium
Tungsten
Uranium
Vanadium
Ytterbium
Yttrium
Zinc
Zirconium
Cone.
3
3
4
5
MC
400
59
MC
0.2
2
0.7
190
1
10
5
8
11
NR - Not reported.
All elements not reported < 0.1 ppm weight
MC - Major component, >1 g/kg
-122-
-------
TABLE 8-47
SPARK SOURCE MASS SPECTROMETRY DATA
Sample No.: 2, Outlet, >100 mesh, Sample was Parr Oxygen Bombed
Concentration in mg/ kg
Element
Aluminum
Antimony
Arsenic
Barium
Beryllium
Bismuth
Boron
Bromine
Cadmium
Calcium
Carbon
Cerium
Cesium
Chlorine
Chromium
Cobalt
Copper
Dysposium
Erbium
Europium
Fluorine
Gadolinium
Gallium
Germanium
Gold
Hafnium
Cone.
0.5
190
0.5
3
0.7
0.1
MC
NR
10
1
4
0.1
220
0.2
2
0.3
Element
Holmium
Hydrogen
Indium
Iodine
Iridium
Iron
Lanthanum
Lead
Lithium
Lutetium
Magnesium
Manganese
Mercury
Molybdenum
Neodymium
Nickel
Niobium
Nitrogen
Osmium
Oxygen
Palladium
Phosphorus
Platinum
Potassium
Praseodymium
Rhenium
Cone.
NR
STD
400
7
0.2
27
2
NR
2
2
NR
NR
110
1
MC
1
Element Cone.
Rhodium
Rubidium °-7
Ruthenium
Samarium °'7
Scandium *
Selenium °'4
Silicon MC
Silver
Sodium MC
Strontium 10°
Sulfur 49°
Tantalum
Tellurium
Terbium °'1
Thallium
Thorium 1
Thulium
Tin °-3
Titanium 370
Tungsten
Uranium °«5
Vanadium 5
Ytterbium
Yttrium 6
Zinc A
Zirconium 13
NR - Not reported.
All elements not reported < 0.07 ppm weight.
MC - Major component, >1 g/kg
-123-
-------
TABLE 8-48
TRACE ELEMENTS IN COAL SAMPLES
(mg/kg)
Sample No.
Element
Barium
Calcium
Cerium
Copper
Flourine
Iron
Lanthanum
Lithium
Phosphorus
Potassium
Silicon
Sodium
Strontium
Sulfur
Titanium
Vanadium
Yttrium
Zinc
Zirconium
2, Inlet
<100 Mesh
31
>1000
3
8
25
700
2
8
110
>1000
>1000
50
6
430
350
5
1 2
7
4
2, Inlet
>100 Mesh
110
>1000
12
4
9
>1000
7
6
50
>1000
>1000
>1000
60
620
460
8
8
4
15
2, Outlet
<100 Mesh
170
>1000
8
8
23
>1000
7
6
91
>1000
>1000
400
59
>1000
190
10
5
8
11
2, Outlet
>100 Mesh
190
>1000
10
4
220
400
7
27
110
>1000
>1000
>1000
100
490
370
5
6
4
13
-124-
-------
9.0 Discussion of Results
9.1 Particulate Emissions
YRC EPA-5 particulate results (section 8.3) are compared to
results obtained by Betz Engineering in Tables 9-1 and 9-2.
Outlet particulate loadings are consistent for the two test
programs. The single YRC inlet test appears to be low in
comparison with Betz data. A review of the sampling
and analytical techniques used in the two test programs
reveals no significant reason for this discrepancy. Betz
analysis was aimed at obtaining total particulate weight
before chloroform extraction. YRC particulate is reported
as chloroform and non-chlorform soluables and no weighing
was done before chloroform extraction.
Particulate loadings obtained from the POM and BSO analysis
(section 8.1 and 8.4) are compared in Table 9-3. BSO results
have been adjusted to reflect front half and filter loadings
only. The particulate loadings for the two sets of tests are
consistent, given the variability of the results. POM parti-
culate weight was obtained after methylene chloride and acetone
washes of the front half (Section 7.1). BSO particulate weight
was obtained after benzene and acetone washes of the front
half (Section 7.3). A significantly greater proportion of
the POM particulate was contributed by the filter catch than
'was the case with the BSO results.
In general, the particulate loadings given by these two sets of
tests are consistent with the Betz data in Table 9-1.
-125-
-------
TABLE 9-1
COMPARISON OF YRC AND B.E.E.
EPA-5 PARTICULATE DATA
Inlet
Process Conditions* mg/Nm
82/271
18510
19379
16291
95/271 17091
16085
17778
8196
109/271 15216
13110
16359
Outlet
mg/Nm
610
888
764
1329
895
1114
892
1564
1588
1252
1311
Source **/Test No.
YRC
YRC
3
15
16
18
13
14
17
2
8
10
11
76/278
82/288
13980
16794
21850
429
1360
760
748
YRC
1
2
12
95/288
14896
9770
11989
1448
2045
529
4
5
9
109/288
14597
11737
16016
1890
2274
2620
3
6
7
* (M-Tons Coal/Hr.)/(Preheater Oultet Temp., C)
** Source is B.E.E. unless noted.
-126-
-------
TABLE 9-2
COMPARISON OF YRC AND B.E.E.
PARTICULATE DATA - PA-DER METHOD
Process Conditions*
82/271
95/271
109/271
76/278
82/288
95/288
109/288
Inlet
mg/Nm3
18968
19723
17068
17457
16336
18647
9025
16222
13339
17023
-
14529
18212
22056
15947
10571
12424
15764
12241
17342
Outlet
mg/Nm^
1636
1085
924
1691
1202
1608
1146
1430
1878
1764
1732
953
1531
898
1643
2218
2558
666
2103
2622
3224
Source** /Test No.
YRC
YRC
YRC
3
15
16
18
13
14
17
2
8
10
11
1
2
12
4
5
9
3
6
7
* (M-tons Coal/hr)/(Preheater Outlet Temp.
** Source is B.E.E. unless noted
-127-
-------
TABLE 9-3
COMPARISON OF PARTICULATE DATA
FROM POM AND BSO SAMPLES
(FRONT HALF)
Process Conditions*
82/260
109/260
82/271
83/271
109/271
55/288
82/288
108/288
Inlet
mg/Nm3
14973
-
20986
10424
10046
4322
13060
7804.7
16392.4
-
-
-
Outlet
mg/Nm3
1256
755
375
94
269
355
1274
2277
280
1091
1668
1700
Test
POM- 11
POM- 4
POM- 10
POM- 2
BOS-1
POM- 3
POM- 8
BSO-2
BSO-3
POM- 7
POM- 6
POM- 5
(M-Tons Coal/Hr)/ (Preheater Outlet Temp., °C)
-128-
-------
9-2 Chloroform and Non-Chloroform Soluable Emissions
YRC and Betz chloroform soluable organic results are compared
in Table 9-4. YRC results appear to be low in comparison with
Betz data. Table 9-5 gives the percent chloroform solubles for
YRC and Betz Data. This shows that Betz obtained a larger per-
centage of chloroform soluable material in the front half of
their train than did YRC. A comparison of the PA-DER results
shows that YRC obtained a higher percentage of chloroform solu-
ables in the back half.
Tables 9-6 to 9-9 list Betz chloroform and non-chloroform soluables
by sampling train components.
-129-
-------
TABLE 9-4
COMPARISON OF YRC AND BETZ
CHLOROFORM SOLUABLE ORGANIC DATA
(EPA METHOD 5)
Process
Conditions*
82/271
95/271
109/271
76/278 •
82/288
95/288
109/288
Inlet
mg/Nm3
—
1964
938
803
510
817
1899
1352
2551
2606
4281
-
984
1071
2139
952
1405
2707
1830
4249
3867
Outlet
tng/Nm3
143
380
604
840
410
709
817
764
1151
1036
1071
110
1144
659
565
849
1750
403
1636
1931
1794
Source** / Test No.
YRC 3
15
16
18
YRC 2
13
14
17
8
10
11
YRC 1
1
2
12
4
5
9
3
6
7
* (M-Tons Coal/Hr)/(Preheater Outlet Temp. °C)
** Source is B.E.E. unless noted.
-130-
-------
TABLE 9-5
COMPARISON OF YRC AND B.E.E. DATA
PERCENT CHLOROFORM SOLUABLE PARTICULATE
Process
Conditions*
Inlet , Outlet ,
E.P.A. PA-DER E.P.A. PA-DER Source**/Test No,
82/271
95/271
109/271
76/278
82/288
95/288
109/288
mm
7.04
6.37
9.79
6.49
14.38
22.59
6.22
12.55
36.17
24.13
-
10.29
4.85
4.88
4.78
11.81
7.61
16.76
19.89
26.20
.
7.42
7.59
10.13
9.53
17.37
22.76
11.26
13.93
35.93
23.63
-
10.40
6.75
5.47
5.16
11.92
8.19
16.67
20.19
25.92
23.50
83.64
86.80
75.41
58.55
85.63
76.31
39.33
86.63
84.94
68.50
25.58
42.92
79.06
63.26
79.17
73.33
85.80
72.47
82.81
81.65
73.04
78.56
82.53
52.50
57.69
79.62
73.20
48.23
81.34
77.77
67.27
83.72
48.82
74.56
55.94
61.44
67.44
79.58
69.33
67.88
63.42
YRC -3
15
16
18
13
14
17
YRC -2
8
10
11
YRC-1
1
2
12
4
5
9
3
6
7
* (M-Tons Coal/Hr)/(Preheater Outlet Temp., C)
** Source is B.E.E. unless noted.
included silica gel.
-131-
-------
TABLE 9-6
BREAKDOWN OF BETZ CHLOROFORM SOLUABLE DATA
BY SAMPLING TRAIN COMPONENTS
SCRUBBER INLET
Process
Conditions*
FH
BH
SG
Test No,
82/271
95/271
109/271
82/288
95/288
109/288
306
357
479
520
308
301
567
544
414
155
192
341
214
331
924
655
976
1471
1603
584
326
299
1595
1053
1987
2070
3884
832
880
1803
752
1076
1790
1181
3278
2401
68
53
130
83
50
176
154
85
128
95
313
96
555
431
121
367
148
230
99
339
19
113
21
24
245
40
25
303
84
459
589
182
17
331
995
357
2076
1334
954
1015
1974
1554
2953
2739
4451
1385
1471
2698
2110
2020
2851
2534
5398
2946
15
16
18
13
14
17
8
10
11
1
2
12
4
5
9
3
6
7
* (M-Tons Coal/Hr)/(Preheater Outlet Temp. °C)
FH = Nozzle, Probe, Front Half Filter Holder
F = Filter
BH = Back Half Filter Holder, Impinger Lines, Impiners, Impinger Solutions
SG = Silica Gel
T = Total
-132-
-------
TABLE 9-7
BREAKDOWN OF BETZ CHLOROFORM SOLUABLE DATA
BY SAMPLING TRAIN COMPONENTS
SCRUBBER OUTLET
Process
Conditions*
FH
BH
SG
Test No.
82/271
95/271
109/271
82/288
95/288
109/288
6
195
796
233
295
394
303
327
300
119
71
305
389
294
197
92
316
346
376
411
47
476
523
373
851
711
723
1028
590
262
461
1459
206
1545
1619
1454
149
86
106
31
269
146
151
161
29
58
83
298
549
286
86
74
108
374
32
354
1754
222
40
73
44
537
424
111
362
271
263
227
405
78
367
165
562
1045
2703
963
1127
985
1349
1737
1526
1316
1106
1135
1545
2267
894
1793
2411
2338
15
16
18
13
14
17
8
10
11
1
2
12
4
5
9
3
6
7
* (M-Tons Coal/Hr)/(Preheater Outlet Temp., C)
FH = Nozzle, Probe, Front Half Filter Holder
F = Filter
BH = Back Half Filter Holder, Impinger Lines, Impingers, Impinger Solutions
SG = Silica Gel
T = Total
-133-
-------
TABLE 9-8
BREAKDOWN OF BETZ NON-CHLOROFORM SOLUABLE DATA
(TOTAL LESS CHLOROFORM SOLUABLES)
. SCRUBBER INLET
Process
Conditions*
FH
BH
T
Test No.
82/271
95/271
109/271
83/288
95/288
109/288
4641
4654
2047
4642
6171
4803
3254
4421
8422
2187
3490
6964
3128
3128
4550
3967
4410
4649
12005
13825
13629
11662
8027
11644
8138
6110
3641
10838
12266
12791
10797
5248
4764
8824
3097
7523
305
291
481
274
219
710
844
139
538
460
1113
110
507
372
320
821
346
1087
16675
18770
16156
16578
14423
17157
13535
10671
12601
13485
16869
19867
14434
8749
9619
13613
7853
13259
15
16
18
13
14
17
8
10
11
1
2
12
4
5
9
3
6
7
* (M-Tons Coal/Hr)/(Preheater Outlet Temp., C)
FH = Nozzle, Probe, Front Half Filter Holder
F = Filter
BH = Back Half Filter Holder, Impinger Lines, Impingers, Impinger Solutions
T = Total
-134-
-------
TABLE 9-9
BREAKDOWN OF BETZ NON-CHLOROFORM SOLUABLE DATA
(TOTAL LESS CHLOROFORM SOLUABLES)
SCRUBBER OUTLET
Process
Conditions*
82/271
95/271
109/271
82/288
95/288
109/288
FH
461
136
481
113
168
108
149
90
95
107
45
100
175
128
98
63
172
218
F
47
25
8
74
130
18
289
125
146
117
56
85
427
166
28
190
171
610
BH
49
74
257
278
228
107
139
352
394
105
57
598
221
228
54
140
241
232
T
556
235
747
465
525
234
577
568
635
329
157
782
823
522
179
274
584
1060
Test No.
15
16
18
13
14
17
8
10
11
1
2
12
4
5
9
3
6
7
(M
-Tons Coal/Hr)/(Preheater Outlet Temp., °C)
-135-
-------
9.3 Benzine and Total Hydrocarbons in Grab Samples
The results of the benzene and total hydrocarbon analysis
(Table 8-39) show that, for the gas stream, the concentrations
of these materials increases across the scrubber (that is,
from inlet to outlet). In five of the eight tests, the
benzene concentration was below the detection limit (O.Sppm)
at the scrubber inlet and yet was as high as 23.0 ppm at the out-
let for one of these tests. Some samples show a similar increase
in total hydrocarbon content. However, there appears to be
no correlation between benzene concentration and total
hydrocarbon concentration in the individual tests.
Of the six water grab samples, none showed a benzene
concentration above the detection limit of 5 ppm. However,
it seems likely that the source of the benzene in the gas
samples was indeed the water stream. As noted in section 8.7,
it is possible that the benzene content of the water samples
was lost prior to analysis. The gas samples were analyzed
soon after testing with an on site GC. When benzene was
found, it was decided to analyze the water grab samples,
which had already been taken for the POM GC/MS analysis,
for benzene also. Hence, there was a substantial delay in
the water sample analysis.
The scrubber water treatment system is described in section 5.3
The flotation cells and disc filter are open tanks and,as
such, are possible sources of accidental water system con-
tamination. However, the consistency of the data over the
-136-
-------
nine day testing period does not suggest this.
The coal distribution and charging bins are pressurized at
appropriate times with steam. The steam is vented during
depressurization into either the distribution bin vent conden-
ser or the charging bin vent condenser. The condensate
from each of these tanks flows to the scrubber water pumping
tank. It may be possible that light hydrocarbons, including
benzene, are volatalized from the coal during bin pressuri-
zation. They would then be vented and ultimately condensed
or absorbed into the scrubber water. In the scrubber, the
benzine and light hydrocarbons could again be volatilized
by the combined effects of spraying and increasing water
temperature. This would account for the higher gas outlet
concentrations of both the benzene and the total organics.
The above is presented only as a possible explanation of the
testing results and there is no real evidence to support
such a possibility. Other sources of benzene and light
hydrocarbons are unknown. Further testing would be required,
especially on the inlet water, to determine the correct
explanations.
-137-
-------
9.4 POM Analysis Discussion
In reviewing the large amount of POM data collected by GC/MS
analysis, two major observations can be made:
1. The concentrations of individual POM species vary over
an extremely wide range from test to test and do not
appear to consistently increase or decrease across the
scrubber from inlet to outlet.
2. The total POM concentration for both the gas and water
streams decrease across the scrubber; i.e., from inlet
to outlet.
In addressing the first observation above, it is first noted
that sampling difficulties were encountered, as explained in
Section 6.12, which limited the simultaneity of the inlet and
outlet gas stream tests. These included process shutdowns,
process fluctuations, and high moisture and grain loadings
which necessitated many filter changes, especially at the inlet.
This lack of strict simultaneity may have affected the inlet vs.
outlet results significantly if changes in specific POM concent-
rations occur very rapidly. In support of this, it is shown
in Tables 8-5 through 8-15 that the concentrations of specific
POMs vary by as much as a factor of 10 from test to test. While
the total POM concentration is more consistent, it also may range
between 3 and 11% of the aromatic fraction which, in turn,
represents between 3 and 14% of the total organic extract. This
is shown in Section 8.2.5. The total organic fraction is shown
to vary from sample to sample in Table 8-19.
-138-
-------
These variations are probably due to natural variations in the
quantity and composition of the coal being processed. Further,
one of the by-products of the coking process, coke oven gas, is
used as fuel for the preheater. Since the coke oven gas is
composed of the volatile gas driven from the coal during coking,
a large amount of POM material should be expected in this gas.
In general,POM and other hydrocarbons should be completely con-
sumed during combustion; however, the composition and heat content
of C.O.G. is highly variable. Since the C.O.G. is burned at very
low percent excess air, it is likely that, at times, slugs of
high heat content C.O.G. will not have sufficient combustion air
with the result that quantities of unburned hydrocarbons will
be released into the preheater gas stream. This would cause high
concentrations of very short duration which would affect the
sampling results. The inlet samples would tend to be the most
affected because of the inertia effect of the scrubber.
The problem, then, may be in the nature and duration of the sampling,
Very long test periods would tend to even out the effects of pulses
of organic material. Very short, simultaneous tests would give
an indication of the response of the scrubber system to hydrocarbon
pulses. In either case, sampling of the C.O.G. should be carried
out in order to ascertain if this is indeed a source of hydrocarbon
variation.
The second observation noted above is concerned with the fact
that the total POM concentration of. both the gas and water streams
decreases across the scrubber (from inlet to outlet). It should
be expected that one stream would increase in concentration at
-139-
-------
at expense of the other stream.
Raoult's Law relates the liquid/gas phase concentrations of a
component in an ideal solution at equilibrium conditions. The
solutions in the scrubber are neither ideal nor at equilibrium
but an "order of magnitude" analysis based on Raoult's Law will
indicate whether POM's should be absorbed or released by the
water stream.
Raoult's Law is
yPT = xPv
where y = the mole fraction (POM.) in the gas stream.
x = the mole fraction (POM) in the water stream.
P = the total pressure of the gas
Pv= the vapor pressure of the particular POM in
the water stream.
Napthalene is the most easily volatilized of the POM species tested
for and has a vapor pressure of 0.123 mm Hg at 20°C. The vapor
pressures of the other POM's are less than this by a factor of 10
to 1000 depending on their molecular weight. Hence, their con-
centration in water should be greater than Napthalene, at equilibrium
The Naphthalene concentration is on the order of 1 mg/Nm which
is equivalent to 7.8 x 10 moles per Nm . The mole fraction,
-7 3
y, is 1.75 x 10 (based on 44.7 moles of air per Nm ). Assuming
the total pressure, P , in the scrubber to be 720 mm Hg, the
mole fraction, x, of napthalene in water is calculated by Raoult's
Law to be 1.02 x 10~ . This represents about 60 moles of
4 3
napthalene (assuming 5.56 x 10 moles of water per m ) or a
concentration of about 8000 mg/1. This is about 1000 times higher
than the observed concentration in the water and is a good indica-
-140-
-------
tion that POM's should be absorbed by the water stream as it
•
flows through the scrubber.
A possible explanation of the POM concentrations in the scrubber
water is suggested by the higher particulate loading in the
outlet water. Carbon is an excellent adsorber of organic com-
pounds. The particulate matter in the water stream has a high
percentage of coal particles which are essentially carbon. There-
fore, if the carbon particles were adsorbing POM's, the outlet water
POM concentration would appear to be lower than the inlet concen-
tration because of the large amount of particulate matter in the
outlet sample.
In order to determine if this explanation is correct, the particulate
matter in the outlet and inlet samples would have to have been
desorbed during analysis. Unfortunately, only the liquid extract
was analyzed after the samples had been stored for quite some
time.
Analysis of the liquid extract and filtered material is suggested
for future sampling.
-141-
-------
10.0 -Effects of Process-Condition
10.1 Particulate.Emissions
Total particulate (PA-DER Method) at the scrubber inlet is rela-
tively unaffected by preheater outlet temperature, as shown in
Figure 10-1. Lowest concentrations occur at a coal feed rate of
95 M-ton/hr.
Scrubber outlet total particulate concentrations rise with both
increasing preheater outlet temperature and increasing coal feed
rate, as shown in Figure 10-2. Consequently, scrubber efficiency
decreases as the coal feed rate and preheater outlet temperature
is increased.
Particulate loadings obtained from POM samples also show no trends
with changing process conditions at the scrubber inlet (Figure 10-4)
but increase at the outlet with both increasing preheater outlet
temperature and coal feed rate (Figure 10-5)
Again, scrubber efficiency decreases with increasing process con-
ditions. (Figure 10-5)
1°•2 Organic Emissions
Benzine soluable organic concentrations increase primarily with
increasing coal feed rate as shown in Figure 10-6. Scrubber
efficiency for the benzine soluables is low; 30% at 271°C, zero
at 288°C. Chloroform soluable organic concentrations at the
scrubber inlet increase mostly with increasing preheater outlet
temperature at coal feed rates below 95 M-ton/hr but show a
strong increase with increasing coal feed rates above this (see
Figure 10-7). Outlet concentrations of chloroform soluables shown
essentially a linear increase with increasing process conditions
but the effect of preheater outlet temperature appears to be
slightly greater as shown in Figure 10-8. Scrubber efficiency
is generally lowest at a coal feed rate of 95 M-tons/hr and
increases to a maximum of approximately 55% at a feed rate of
109 M-ton/hr. (See Figure 10-9)
-142-
-------
10.3 POM Emissions
At the scrubber inlet, total POM concentrations are increased
substantially with increasing coal feed rate as shown in Figure
10-10. The effect of preheater outlet temperature in not clear;
at a feed rate of 82 M-ton/hr, the lowest total POM concentration
is at a temperature of 271°C. At temperatures above and below
this, there is an increase in concentration. The effect of
temperature at higher feed rates becomes less.
Figure 10-11 shows total POM concentrations at the scrubber out-
let. At the high preheater outlet temperature of 288°C, increas-
ing feed rate has very little effect. At lower temperatures,
concentrations rise sharply with increasing feed rate.
In general, scrubber efficiency for total POM increases from
approximately 20% at a feed rate of 82 M-tons/hr to approximately
60% at 109 M-tons/hr. Preheater outlet temperature has little
effect.
-143-
-------
FIGURE
EFFECT OF COAL FEED RATE AND 'PREHEATER OUTLET TEMPERATURE
ON TOTAL PARTICULATE (PA-DER METHOD) AT SCRUBBER INLET
24.0
22.0!
20.0
18.0
o
3
H
Q
g
W
s
J
D
O
H
16.0
14.0!:
12.0!
10.01:
-^- - -mf— \ -
8.0
6.0|
4.0t
2.0
82
(90)
95
(105)
109
(120)
COAL FEED RATE M-TON (TON/HR)
LEGEND
O
AVE BETZ @ 271°C (520°)
AVE BETZ @ 288°C (550°)
YRC @ 271° (520°)
-144-
-------
FIGURE 10-2
EFFECT OF COAL FEED RATE AND PREHEATER OUTLET TEMPERATURE ON
TOTAL PARTICULATE (PA-DER METHOD) AT SCRUBBER OUTLET
£
3
c
z
H
Q
I
w
u
H
E-*
K
6.0 ;
2.0
1.0
COAL FEED RATE, M-TON/HR (.TOM/HR)
LEGEND
A^/E. BETZ @ 271°C C52Q Fl
AVE. BETZ @ 288°C C550°Fl
YRC @ 271°C (520°F)
-145-
-------
FIGURE 10-3
EFFECT OF COAL FEED RATE AND PREHEATER OUTLET TEKPERATURE ON
TOTAL PARTICULATE SCRUBBER EFFICIENCY (PA-DER METHOD)
100
U
B
ta
H
CJ
H
W
K
ca
D
cs
u
en
90
80
70
COAL FEED RATE, M-TON/HR, (TONS/HR)
LEGEND
AVE. BETZ @ 271°C (520°F)
AVE. BETZ @ 288°C (.550°F)
YRC § 271°C (520°F)
-146-
-------
g
z
\
01
0
z
H
Q
FIGURE 10-4
EFFECT OF COAL FEED RATE AND PREHEATER OUTLET TEMPERATURE
ON POM-TRAIN PARTICULATE AT SCRUBBER INLET
24.0-
22. 0-
20.0-
18.0-
16.0-
14.0- ;
12.0-
•£=-
10.0- ;:
a
a
u
H
8.0- H
6.0-
4.0-
2.0- ;
COAL FEED RATE, M-TONS/GRM (TONS/HR)
LEGEND:
Q YRC @ 260°C (500°F)
O YRC @ 271°C (520°F)
• YRC @ 288°C (550°F)
-147-
-------
e
^
in
FIGURE •
EFFECT OF COAL FEED RATE AND PREHEATER OUTLET TEMPERATURE
ON POM-TRAIN PARTICULATE AT SCRUBBER OUTLET
2.0-
H
a
g
w
D
U
H
g
<
Oi
1.0- =
—+•
82
(90)
95
(105)
109
(120)
COAL FEED RATE, M-TONS/HR, (TONS/HR)
LEGEND;
D
O
YRC
YRC @ 271C
(500°F)
(520°F)
YRC @ 288°C (550°F)
-148-
-------
2
W
W
&
><
u
z
w
H
u
H
En
fa
w
03
03
3
OS
U
cn
FIGURE 10-6
EFFECT OF COAL FEED RATE AND PREHEATER OUTLET TEMPERATURE ON
SCRUBBER EFFICIENCY (POM PARTICULATE)
100
90 f
80
70 I
60
50
40 t
30
20
10
109
(120)
COAL FEED RATE, M-TONS/HR, (TONS/HR)
LEGEND
a
o
YRC (§ 260°C (500°F)
YRC @ 271°C (520°F)
YRC @ 288°C (550°F)
-149-
-------
FIGURE 10-7
EFFECT OF COAL FEED RATE AND PREHEATER OUTLET TEMPERATURE ON
BENZENE SOLUABLE ORGANIC CONCENTRATIONS
u
M
05
o
w
J
CO
O
en
2
H
OD
2
O
M
s
U
I
U
LEGEND
COAL FEED RATE, M-TONS/HR, (TONS/HR)
YRC @ 271°C (520°F); O = INLET, •= OUTLET
YRC @-288°C (550°F); D = INLET, •= OUTLET
-150-
-------
g
z
u
H
o
OS
o
o
<
3
o
o
OS
o
u
fc,
o
1
H
EH
2
H
O
2
O
u
FIGURE 10-8
EFFECT OF COAL FEED RATE AND PREHEATER OUTLET TEMPERATURE
ON THE CONCENTRATION OF CHLOROFORM SOLUABLE ORGANICS
(PA-DER METHOD) AT THE SCRUBBER INLET
4.0
3.0 P
2.0
1.0
COAL FEED RATE, M-TONS/HR, (TONS/HR)
LEGEND
O AVE. YRC @ 271°C, (520°F)
^ AVE. BETZ @ 271°C, (520°F)
AVE. BETZ <§ 288°C, (550°F)
-151-
-------
g
z
CO
u
OS
O
Ed
J
03
<
D
J
O
§
O
u
g
S
H
U
3
O
U
FIGURE 3,0-9
EFFECT OF COAL FEED RATE AND PREHEATER OUTLET TEMPERATURE
ON THE CONCENTRATION OF CHLOROFORM SOLUABLE ORGANICS
(PA-DER METHOD) AT THE SCRUBBER OUTLET
3.00-
2.00-
1.00- =
±±
82
(90)
95
(105)
109
(120)
LEGEND
COAL FEED RATE, M-TONS/HR (TONS/HR)
AVE. YRC @ 271°C, (520°1
AVE. BETZ @ 271°C, (520°F)
AVE. BETZ @ 288°C, (550°F)
-152-
-------
FIGURE 10-10
EFFECT OF COAL FEED RATE AND PREHEATER OUTLET TEMPERATURE ON
CHLOROFORM SOLUABLE ORGANIC SCRUBBER EFFICIENCY
<#>
u
z
H
H
H
CQ
G
U
Cfl
COAL FEED RATE, M-TONS/HR, (TONS/HR)
LEGEND
YRC § 271°C (520°F)
AVE. BETZ § 271°C (520^F)
AVE. BETZ « 288°C (550 F)
-153-
-------
e
2
S
o
cu
EH
O
EH
FIGURE 10-11
EFFECT OF COAL FEED RATE AND PREHEATER OUTLET TEMPERATURE ON
TOTAL POLYCYCLIC ORGANIC MATERIAL (POM) CONCENTRATION
AT SCRUBBER INLET
0.150
0.100
0.050
0.040
0.030
0.020
0.010
! I
82
(90)
.wr 1 I - - ' Jf-
if-i --- -<
95
(105)
109
(120)
COAL FEED RATE, M-TONS/HR, (TONS/HR)
LEGEND
D
O
YRC @ 260°C, (500°F)
YRC @ 271°C, (520°F)
YRC @ 288°C, (550°F)
-154-
-------
E
Z
\
I
2
0
FIGURE 10-12
EFFECT OF COAL FEED RATE AND PREHEATER OUTLET TEMPERATURE ON
TOTAL POLYCYCLIC ORGANIC MATERIAL (POM) CONCENTRATION
AT SCRUBBER OUTLET
0.120
0.110
0.100
0.090
0.080
0.070 ;
0.060 i-
0.060
0.040
0.030
0.020
0.010;
COAL FEED RATE, M-TONS/HR, (TONS/HR)
LEGEND
Q YRC @ 260°C, (500°F)
O YRC @ 2710C, (520°F)
• YRC @ 288°C, (550°F)
-155-
-------
3
K
U ->'
« SS
W O-
U £•••
2 S
W fu
H U
U 2
M O
fa O
fa
w 2;
O
M
O <
S E-i
K C
O O
&
D
(X W
cd cn
cc
-------
— .
TECHNICAL REPORT DATA
. REPORTNO — ' | read I***ructi°™ o» ^e reverse before comp
EPA- 600/2 -80- 082
Environmental Assessment of a Coal Preheater
T.K.Sutherland, J.P.Bilotti, and E.M.Whitlock
9. PERFORMING ORGANIZATION NAME AND ADDRESS '
York Research Corporation
One Research Drive
Stamford, Connecticut 06906
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
leting)
3. RECIPIENT'S ACCESSION NO.
5. REPORT DATE 1
May 1980
6. PERFORMING ORGANIZATION CODE
8. PERFORMING ORGANIZATION REPORT NO.
10. PROGRAM ELEMENT NO.
1AB604C
11. CONTRACT/GRANT NO.
68-02-2819, Task 4
13. TYPE OF REPORT AND PERIOD COVERED
Task Final; 3/78-3/80
14. SPONSORING AGENCY CODE
EPA/600/13
ia. SUPPLEMENTARY NOTES ffiRL-RTP project officer is Robert C. McCrillis, Mail Drop 62, 1
919/541-2733.
is. ABSTRACT The repOrj- gjves results of a. program to determine particulate and organic
emissions from a Cerchar coal preheater at Jones and Laughlin Steel Corp. 's
Alirmirmn Works. Scrubber removal p.ffir.ipnrv for nnrricnlntp mpasnrprl hv P1PA
Method 5, ranged from 86 to 93%. Emissions at the scrubber outlet ranged from
95 to 468 g/M-ton of coal and increased with coal feed rate. Lower preheat temper-
ature improved scrubber efficiency. At the scrubber outlet, chloroform-soluble
organic emissions ranged from 11 to 414 g/M-ton coal; benzene-soluble organic emis
sions ranged from 186 to 397 g/M-ton coal. Total POM emissions ranged from 4.7
to 23.4 g/M-ton coal. Scrubber efficiency for removal of organics was lower than
for particulate removal and increased with increasing coal feed rate. Preheater out-
let temperature increased both inlet and outlet concentrations, but did not affect
scrubber efficiency. GC/MS analysis showed extreme variability in POM specie con-
centrations. POM species exceeding their Discharge Multimedia Environmental
Goal (DMEG) values in the scrubber outlet were: phenanthrene, benz(a)anthracene,
benzo(a)pyrene, 7,12-dimethylbenz(a)anthracene, and 3-methyl cholanthrene.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
COSATI Field/Group
Pollution
Assessments
Coal
Heating Equipment
Scrubbers
Dust
Poly cyclic Com-
pounds
Organic Compounds
Pollution Control
Stationary Sources
Environmental Assess-
ment
Coal Preheaters
Particulate
13B
14B
21D
13A
07A,13I
11G
07C
13. DISTRIBUTION STATEMENT
Release to Public
19. SECURITY CLASS (This Report)
Unclassified
163
20. SECURITY CLASS (Thispagej
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
157
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