SERA
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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
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The nine series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
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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
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This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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EPA-600/2-79-016
January 1979
Environmental Assessment of
Coke By-product Recovery Plants
by
D.W. VanOsdell, D. Marsland, B.H. Carpenter,
C. Sparacino, and R. Jablin
Research Triangle Institute
P.O. Box 12194
Research Triangle Park, North Carolina 27709
Contract No. 68-02-2630
Task No. 1
Program Element No. 1AB604C and 1BB610C
EPA Project Officer: Robert V. Hendriks
Industrial Environmental Research Laboratory
Office of Energy, Minerals, and Industry
Research Triangle Park, NC 27711
Prepared for
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, DC 20460
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PREFACE
This report was prepared for the Environmental Protection Agency to present the
results of work performed under Contract No. 68-02-2630, phase 1. Mr. Robert V.
Hendriks served as EPA Project Officer.
The research was conducted in the Energy and Environmental Research Division and
the Analytical Sciences Division of the Research Triangle Institute. Mr. Ben H.
Carpenter, Head, Industrial Process Studies Section, served as Program Manager. Mr.
Douglas W. Van Osdell was the principal investigator. Dr. Charles Sparacino directed
the chemical analysis effort. Mr. Richard Jablin, Jablin Associates, provided engineer-
ing assessment effort. Dr. David Marsland provided state-of-the-art process
technology appraisal. Mr. Walter S. Smith, Entropy Environmentalists, directed the
plant sampling effort. Dr. Denny Wagoner directed Level 1 field chemical analyses.
1 i 1
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ABSTRACT
The objective of this work was to perform a multimedia environmental
assessment of coke by-product recovery plants in the United States. The
project included both gathering and analyzing existing data and the develop-
ment of needed information through a sampling and analysis program based on
the EPA Level 1 protocol.
Existing sources were searched and process data concerning design and
operation of existing plants and processes were examined. Many variations
of all process types exist, forcing an examination of the industry ,to deter-
mine the more common processes. No data were available on many sources and
a sampling plan was developed.
The sampling and analysis program was a basic EPA Level 1 format tai-
lored for organic vapor sampling. In addition, specific samples were ana-
lyzed for cyanide. The samples were mostly of the vapor above storage
tanks, with additional samples at the locations deemed most important.
Rates were determined where measurable. Storage tank emissions could not be
quantified, with one possible exception. With respect to air emissions, the
single largest source was the final cooler cooling tower; both aromatics at
greater than 50 g/Mg coke and cyanide at 278 g/Mg coke were significant.
PNA's were not quantified, but were indicated. Concentrations of pollutants
in the vapor above storage tanks were measured, but actual emission rates
were not determined because of the difficulty of measuring or estimating
working (due to changing product levels) and breathing (due to atmospheric
pressure changes, temperature changes, etc.) losses for the tanks sampled.
Water sampling data from the same plant, developed by EPA's Effluent Guide-
lines Division, were included in the overall study analysis.
This report was submitted in fulfillment of Contract No. 68-02-2630 by
Research Triangle Institute under the sponsorship of the U.S. Environmental
Protection Agency, and covers the period March 1, 1977, to June 30, 1978.
iv
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CONTENTS
Preface. . . ............ ................ 1]"'
Abstract ................. ............. tv.
Tables ........... .................... vn
1.0 Summary ..... . • ..................... 1f|
2.0 Conclusions and Recommendations ................ ^
3.0 Introduction .................. ;-,'!*''"' 10
4.0 Process Descriptions: Coke By-product Recovery Plants .... id
4.1 Overview of Components and Processes ........... 13
4.2 Tar Separation and Processing ............... 25
4.3 Ammonia Handling ....... .............. *'
4.4 Tar Acid (Phenol) Removal /Recovery . . .......... **
4.5 Final Cooler and Naphthalene Processing ........ • • 38
4.6 Light Oil Recovery ..... . .............. ^1
4.7 Sulfur Handling ...................... ^
4.8 Cyanide Treatment ...... ... ............ j?4
4.9 Wastewater Processing ......... ' ' ' ,'. ' / rl 1 ' ' CA
.5.0 Status of By-product Recovery Technology in the United States . t>4
5.1 Introduction ................... • • • • °^
5.2 Tar Processing .... .................. °'
5.3 Ammonia Handling . . . ..... ............. °°
5.4 Phenol Recovery From Ammonia Liquor ........... o^
5.5 Final Cooler and Naphthalene Recovery ........... ^
5.6 Light Oil Recovery .................... ^
5.7 Desulfurization Technology ...... .......... ^
5.8 Status of Wastewater Treatment .............. 'J-
6.0 Environmental Effects of Coke By-product Recovery ....... /&
6.1 Summary ................. • • • • .....
6.2 Environmental Effects of Coal Tar Collection and
Processing ........................ ^
6.3 Environmental Effects of Ammonia Processing ....... yu
6.4 Environmental Effects of Dephenolization Process ..... 92
6.5 Final Cooler and Naphthalene Handling ......... • • 93
6.6 Environmental Effects of Light Oil Recovery. . . ..... 99
6.7 Desulfurization - Environmental Assessment ........ 100
6.8 Environmental Effects of Wastewater Process ...... . . 104
6.9 Ambient Air Analysis - By-product Plant ...... .... 109
7.0 Preferred Technology and Problems Outstanding ......... lib
7.1 Introduction ....................... 115
References .............................
Appendix A - Sampling and Analysis Program ............. JJ'i
Appendix B - Cost Estimates for By-product Recovery Plants ..... B-l
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FIGURES
Number
1 Flowplan and material balance of a representative coke
by-product recovery plant 23
2 Tar separation 26
3 Tar refining outline 28
4 Ammonia stills 31
5 Ammonium sulfate recovery with vacuum crystal!izers
(Wilputte) 34
6 Ammonia recovery by "Phosam" process. . . 35
7 Dephenolization 37
8 Final, cooler with naphthalene separation 40
9 Tar-bottom final cooler 42
10 Wash oil absorption of light oil with light oil
rectification (derived from Wilson and Wells) 44
11 Koppers1 two-stage vacuum carbonate process 48
12 Dravo/Still processing 51
13 Coke by-product plant wastewater treatment options. ... 62
14 Complete wastewater treatment scenario. 63
15 Pollutants from by-product recovery 77
VI
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TABLES
Number
1 Coke By-product Recovery Plants Pollutant Sources .... 2
2 Estimated Pollutant Emissions Rates, Based on
Indicated and Confirmed Species Found in Samples
Taken at One Coke By-Product Plant 4
3 Normalized Relative Hazard of By-product Coke Plant
Pollutant Sources . . . 8
4 Coking Production Statistics-By-product Coke Plants,
1975 14
5 Average Amounts of Important Components, Coke Oven
Tars • 16
6 Representative Compounds in Coke Oven Light Oil
and Average Compositions 17
7 Representative Coke Oven Gas 1°
8 Sulfur and Nitrogen in Coal and Coke • 19
9 Fate of Coke Oven By-products 24
10 Major Components of Weak Ammonia Liquor 60
11 Use of Coke By-product Recovery Technologies
in the United States. 65
12 Coke Oven Gas Desulfurization Plants in the
United States . . 71
13 Status of By-product Plant Wastewater Treatment
Processes • • • • 7~
14 Pollutants from By-product Recovery Plant .. /°
15 Summary of Organic Analysis, Tar Decanter Vapor 84
16 Summary of Organic Analysis, Primary Cooler
Condensate Tank Vent. ...... 86
17 Summary of Organic Analysis, Vapor Above Tar Storage
Tank 88
18 Summary of Organic Analysis, Vapor Above Chemical
Oil Tank 91
19 Summary of Organic Analysis, Froth Flotation
Separator 94
20 Summary of Organic Analysis, Final Cooler Cooling
Tower Vapor 96
21 Organic Extract Summary, Final Cooler Cooling Tower -
Hot and Cold Wells 98
22 Summary of Organic Analysis, Light Oil Storage 101
23 Organic Extract Summary, Ammonia Liquor - 105
24 SSMS Analysis of Biological Plant Sludge Sample 106
25 Summary of Organic Analysis, Biological Treatment .
Plant Sludge 107
vii
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TABLES (con.)
Number Pagj
26 Biological Treatment Plant Testing - Selected Results 108
27 Ambient Cyanide Analysis UQ
28 Summary of Organic Analysis, Upwind Ambient .'.'.'.'.'.'. Ill
29 Summary of Organic Analysis, Downwind Ambient . . 112
30 Estimated Relative Hazard of Coke By-product
Plant Sources -Q4
vm
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1.0 SUMMARY
This report discusses the findings of a screening study of the multi-
media environmental effects of U.S. coke by-product recovery plants and their
related pollution control technologies. The purpose of the study was to
analyze relevant background data, to acquire new data by sampling and testing,
and to draw conclusions concerning the environmental acceptability of the
process.
There are 60 coke by-product plants in the country; these processed
gases from an estimated 75 million metric tonnes of coal in 1975, the latest
year of record. Table 1 lists 42 pollutant sources for the by-product recov-
ery plant. These are related to eight major operations; tar processing,
ammonia processing, dephenolization, final cool ing-naphthalene handling,
light oil recovery, desulfurization, cyanide handling, and water handling.
For each operation there are alternative technologies and existing plants
employ only a few of the thousands of combinations of operations available.
The table identifies the scope of pollutant emissions information
developed during the study, by indicating whether sampling was done (x);
sampling was not done, but data are available (y); or sampling was not done
and data are not available (z). Types of pollutants to air, land, and water
are indicated.
Except for still vents and forced drafts (e.g., final cooler cooling
tower), emissions to air are fugitives—tank breathing and working losses,
open decanters, and basins. Fugitives are also due to faulty equipment,
such as pump seal leaks and flange leaks, but these are not addressed.
Pollutants identified include light aromatics (LA), polynuclear aromatics
positively identified (P), and polynuclear aromatics indicated (PI).
Light aromatics were predominantly benzene and its homologs. Estimated
emission factors for these pollutants, derived from sample data from one
plant, are given in Table 2. This table is based on 1 tonne (1000 kg) of
coal fed to the ovens. Nine sources were investigated, seven by sampling.
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TABLE 1. COKE BY-PRODUCT RECOVERY PLANTS POLLUTANT SOURCES
Operation
Emissions Source
Pollutants to:
Water
Land
Tar Processing
tar decanter
prim, cooler condensate
tank
tar dewatering and
storage
tar topping (distillation)
tar distillation-product
tar distillation pitch
Ammonia Processing
excess liquor tank
excess ammonia liquor
phenol extraction
ammonia stills
fixed still
sulfate crystal!izer-
dryer
sulfuric acid storage
tank
ammonium sulfate
storage
Dephenolization
Final Cooler, Naphthalene
Handling
cooling tower, for con-
tact cooler
hot and cold wells
naphthalene separator
(froth floatation)
naphthalene dryer
Light Oil Recovery
wastewater
wash oil sludge
(x),f,P,LA,H2S
(x),f,NO,LA,H2S
(x),f,P,LA
(y),f
(x),f,PI,LA
(z), f
(x),P,LA
(z),f
(z),vent
(z),f
(z),f
(z),f
(y),f if
vented to
gas main
(x),P,HCN,LA
(x),f,PI,LA
(y), vent
(z),bar
cond.
(z)
(x),P,LA
(z),water
decanted
(y)
(y),sludge
(z),tar
product
(y),pitch
product
(z),sludge
(y),sludge
(y)
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TABLE 1. (continued)
Operation
Emissions Source
Air
Pollutants to:
Water
Land
wash-oil storage
wash-oil decanters
light-oil storage
light-oil condenser
vent
Desulfurization
by absorption
by wet oxidation
Cyanide Handling
catalytic destruction
waterwork
regenerate or blown air
ammonium polysulfide
Coke Oven Gas, After Tar
Removal
Biological Treatment Plant
Feed
effluent
sludge
Plant Atmosphere
Downwind-Upwind, concen-
tration increase
(z),f
(z),f
(x),f,LA,H2S
(z)
(z)
(y)
(x)
(y),absorption
purge
(y),absorption
purge
(z)
(x),C1-C6,LA,H2S
(x),Ph,P,LA,CN,
C1,S04,SCN
(x),Ph,P,LA,SCN,
CN,C1,S04
(x),Fe,Cl,
Mg,F,
S1.A1,
etc.
present
(x),alipha-
tics,
pheno-
1 ics,
sat.
HC
present
(x),HCN:0.05-0.06
vppm
Ph = phenols
LA = light aromatics (benzene, etc.)
NO = no organics sample
PI = polynuclear aromatic compounds
may be present
P = polynuclear aromatic compounds
present
f = fugitive
S = sludge
(x) = sample taken
(y) = sample not taken, but data
. available
(z) = sample not taken, data
not available
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TABLE 2. ESTIMATED POLLUTANT EMISSIONS RATES, BASED ON INDICATED AND CONFIRMED SPECIES
FOUND IN SAMPLES TAKEN AT ONE COKE BY-PRODUCT PLANT
Operation
Emission Source
Tar Processing
decanter
sludge, pitch'
dewater ing-storage
prim, cooler condensate tank
topper (distillation)'
distillation product storage
Ammonia Processing
excess liquor tanks'
excess ammonia liquor
bar. conden. water, sulfate dryer1
lime-leg sludge
other sources'
Oephenolization1
Final Cooler, Naphthalene Handling
cooling tower for contact cooler
naphthalene separator™
naphthalene dryer
Light Oil Recovery
wastewater (wash oil, sludge)'
wash oil storage and decanter1
light oil storage
wash oil sludge1
Wastewater
bi i) treat meni plant effluent
biotreatment plant sludge
Total, all sampled sources
Rate: Analyas Emission Rates, gAonne of coal'
sun/tonne Temp. Live! SuHm
of coal °C 1 2 Benzene Toluene Xyleneb PNAC Specific PWA's quantified compounds'!
1.6(3)' 76 x x 15.6 1.1 0.3 4.1d Biphnnyl, 0.03; quinoline 006 91
0.07K
°-"6> 29 * >< 0.006 0.002 0.0016 0.003 Biphenyl, 0.002; quinoline, NTD
0.0006
'•2(3) 62 a 6.3 0.8 0.3 NO None" 3.9
0.02 50 x 0.004 0.003 0.002 0.011 N0
102 I/tonne Amounts of organic* are counted in the wastewater
0.5 kg/tonne
2306 Ambient 35.9 NTD NTD 6.4 Biphenyl, 0.06; quinoline, 0.32 7.6
Not known Ambient x
2.1 101 Grab sample results not satisfactory for estimates
70-360
11.1 50 o 11.6 0.4 NTD rj5
335
9001/tonne 0.12-0.13 0.3-fl.7q
1.2 kg/tonne fl 007
B/tonne 69.5 2.3 0.6 11.2 21.1
kg/day, for
5,142 tonne coal 357 11.8 3.1 57.6 108.5
Effluent
Cyanides NH3 Phenol Lt. oil state
~ — — ~
NDe Vapor
Liquid
NO Vapor
ND Vapor
ND Vapor
6.l' 611 148 Liquid^
2'2 Vapnr
Vapoi
Vapor
0.4-0.7 0.4-1.1 0.6-1.9 2.1 kg/t Liquid*1
Vapor
H 66 1.1 7.8 a/tonne
226 65 11 78
1162 334 5.6 40.1
b Xylene plus ethylbenzene
c Polynuclear aromatics are assumed to be equal to the G RAV content of the effluent
d Major component = naphthalene
e ND-not determined
f Tonne = 1,000 kilograms coal
g Sulfur compounds, as HjS
h Cyanides as HCN
i Not sampled
j NTD = not detected
k Liters per tonne of coal
I From Dunlop and McMichael
m Emission rates are unknown. Toxicity data are shown in Table 3
o Level 1 sampling, in part. No XAO-2 resin sample
p Stream is processed in the biotreatment plant
q Estimate based on identified PNAs
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For the sources investigated, the daily total emissions from processing 1.8
million cubic meters' per day of coke oven gas are estimated to be:
Light aromatics (mostly benzene), 372 kg/day
Polynuclear and high boiling aromatics (PNA) 57.6 kg/day
Sulfur compounds 108 kg/day
Cyanides 1,162 kg/day
Ammonia 334 kg/day
Phenols 5.6 kg/day
Light oils 40.1 kg/day
These data were developed utilizing methodologies based on the Environ-
mental Protection Agency's Level 1 protocols,58 with limited gas chromato-
graph-mass spectrometer identification of specific pollutants. These quanti-
ties are subject only to uncertainties in emission rate estimates, sampling
and testing areas. The PNA's shown are the quantities of residual organics
obtained upon evaporation of the solvent used for extraction, which are
nominally those organics with boiling points above 300°C. The PNA's emission
factors are subject to the additional uncertainty inherent in this method of
estimation. Specific PNA's were not identified except for three sources
considered most likely to involve them: the tar decanter, the dewatering
and storage tanks, and final cooler cooling tower. Sulfur compounds are
reported as hydrogen sulfide; cyanides, as hydrogen cyanide.
Light aromatics, the predominant emissions, were found in the highest
concentration in emissions from the tar decanter, the primary cooler conden-
sate tank, the naphthalene separator, the light oil storage tanks, and the
distillation product storage tanks. PNA's (as total non-evaporables) concen-
trations were highest at the following sources: wastewater treatment sludge
tar decanter, tar dewatering and storage, tar distillation products, naphtha-
lene separator, final cooler cooling tower, and water from the biological
treatment plant. Cyanide concentrations were highest at the final cooler
cooling tower and in the effluent from the biological treatment plant.
Sulfur compound concentrations were highest at the tar decanter, the primary
cooler condensate tank, the naphthalene separator, the light oil storage
tanks, and in the plant wastewater effluent.
The data suggest that the PNA's accumulate as a concentrate in the
liquid streams (tars, flushing liquor, tar products, wash and wastewaters).
PNA's accumulated in the water from the final cooler reentered the air as
the recycled water passed through the open cooling tower.
5
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Ambient air samples, taken upwind and downwind of the by-product plant,
showed increases in both benzene and cyanide concentrations. The following
results were obtained:
Hydrogen Cyanide Benzene
(volume ppm) (volume ppm)
Downwind 0.062 08
Upwind 0.006 0*6
Gain _ 0.056 0.2
Toxic units/son toxic units/scm toxic units/scm
Downwind 0.0062 0 9
Upwind 0.0006 0^7
These results indicate that cyanide concentrations downwind of the
by-product plant were well below the environmental goal. Cyanides of this
plant were more a problem in wastewaters than in the air. Downwind benzene
concentrations, on the other hand, were close to the goals.
Of the 42 pollutant sources listed, all but fifteen (marked z in Table
1) have been examined. Six of the fifteen were in the ammonia processing
operations, which the plant studied considered to be proprietary. The
sludge from the lime leg of an ammonia still would be produced at an esti-
mated 0.35 kg/Mg of coke. The extent to which PNA's are entrained in this
sludge has not been reported. The acid storage and ammonium sulfate drying
and transport operations are expected to have very low pollutant discharges
to any medium.
The remaining nine unstudied sources are the wash oil storage, decan-
ters, and condenser vents of the light oil recovery operations, the decanted
water from the naphthalene dryer, the wastewaters from dephenolization, the
tar-topping barometric condenser, and the cyanide handling processes, some
of which are an inherent part of desulfurization operations. The wastewater
streams involved in these operations were sent to a combined wastewater
treatment plant at the study site.
Alternatives to the removal of ammonia as ammonium sulfate include the
production of anhydrous ammonia and incineration of the separated ammonia.
Cost comparisons for the handling of 1.4 million cubic meters of gas per day
indicate that incineration is the alternative with the lowest annualized
cost even after credits are taken for the sale of products obtained using
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the other processes. However, the environmental effect of ammonia inciner-
ation has not been determined. The production of anhydrous ammonia can be
economically attractive, however, if the coke plant is large enough and the
entire by-product plant is designed to favor this product.
Dephenolization of ammonia liquor by coke oven light oil, followed by
reaction with sodium hydroxide to produce sodium phenol ate for sale appears
to be more costly than dephenolization by activated sludges. The latter
treatment may be necessary in either case in order to meet effluent pollu-
tant limitations.
A great deal of research, development and regulatory effort is being
expended on desulfurization processes. Those in use include Bravo/Still,
Sulfiban, Vacuum Carbonate, Stretford, Cryogenic, and Takahax. Compared
with the first three, the Stretford process has the lowest annualized cost
at $1.97/1,000 son of gas treated, although the Dravo/Still process at
$2.05/1,000 son is only slightly more expensive.
Certain pollutant-control technologies appear to have potentially broad
application within coke by-product plants. The blanketing of holding tanks
with coke oven gas originally used in the light oil recovery process to
exclude air and prevent the buildup of sludges, eliminates the tank vents as
an emissions source. The blanketing gas is vented back into the main gas
stream. This technique could perhaps be applied to many sources even to
refined benzene tanks, if the gases were first desulfurized to prevent
deterioration of the product. Problems to be addressed in considering the
broader use of blanketing include making provision to admit the flammable
gas into the various operating areas, and to prevent the condensation of
naphthalene.
The collection of napthalene in open vessels inherently causes emis-
sions of naphthalene along with other organic pollutants contained in the
process streams at this stage. Tar bottom final coolers should keep much of
the organics in the tar. This combined with a closed cooling cycle, should
reduce substantially the emissions from the final cooler.
The relative environmental impact of some of the pollutant sources
within the by-product coke plant is addressed in Table 3. The biological
treatment plant effluent is the most significant of the by-product plant
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TABLE 3. NORMALIZED RELATIVE HAZARD OF BY-PRODUCT COKE PLANT
POLLUTANT SOURCES
Normalized Relative Hazard
Tar Decanter Vapor
Tar Dewatering/Storage Vapor
Primary Cooler Condensate
Tank Vapor
Distillation Product Storage
Cooling Tower for Contact
Final Cooler
Light Oil Storage Vapor
Biotreatment Plant Effluent
Biotreatment Plant Sludge
0.036
«0
0.017
0.001
0.349
0.028
0.434
0.135
8
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sources. This was due to a combination of a large effluent rate and the
sensitivity of the impact measurement to organic pollutant concentrations.
The other major sources are the cooling tower for the contact final cooler
and the biological treatment plant sludge.
The procedure used to arrive at Table 3 uses a weighting process which
considers pollutant concentration, hazard in the proper media, and emission
rate. For the by-product plant, the weighting factors reflecting the great
hazard of certain PNA's essentially controlled the results. The procedure
is explained fully in Section 6.10. Weighting factors were obtained from
the Multimedia Environmental Goals.60
This study is a limited-scope first look at the by-product plant from
the environmental point of view. As such, it points to a need for control
of light aromatics and PNA's. Control may be most likely achieved through
techniques that essentially eliminate the sources: venting tanks back to
the gas mains; blanketing with coke oven gas. The potential for application
of venting and coke oven gas blanketing should be determined by further
study. Alternative technologies for dephenolization, cyanide handling, and
desulfurization should be further studied with respect to their relative
environmental impacts. Solid wastes present hazards in disposal that require
further investigation. Wastewater treatment capabilities and effects need
further delineation. Economic models of the annualized costs of alternative
processes should be further developed to permit delineation of most cost
effective technologies.
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2.0 CONCLUSIONS AND RECOMMENDATIONS
As this study was a Level 1 assessment, the conclusions offered are all
of a preliminary nature, based on grab samples of single sources at one plant.
Several areas of potential concern were identified, however, as enumerated
below:
1. Emissions from the final cooler cooling tower exceeded the MATE
values for hydrogen cyanide and benzene and the emissions rate was
3,200 smVMg coke.
2. Emissions from the various hydrocarbon storage tanks in the by-product
plant exceeded the MATE values for benzene in all cases sampled,
although the emissions rate was low in comparison to the final
cooler cooling tower.
3. Naphthalene is qualitatively the PNA emitted in the greatest quan-
tity from by-product plant sources, although it was not quantified.
The quantity of high boiling PNA's emitted from sampled sources was
around 16 g/Mg coke, assuming all organics adsorbed on the resin
with boiling points above 300°C to be PNA's.
4. Four hour integrated samples upwind and downwind of the by-product
plant did not detect a significant change in benzene or light hydro-
carbon concentration across the plant. The average of two 24-hour
integrated upwind-downwind samples for hydrogen cyanide detected an
increase across the plant from 0.006 vppm to 0.06 vppm (MATE value
for HCN is 10 vppm).
5. Organic analysis of the biological plant sludge indicated that
several compound classes exceeded the lowest MATE value for that
class.
The recommendations offered as a result of this study are basically a
call for more detailed examination of the sources identified as potential
problem areas followed by a search for control technology if problems are
confirmed. The technique used in this study to identify problem areas is
conservative; detailed study of an emission which showed that an especially
toxic pollutant was not actually present in that emission could eliminate it
as a source of concern.
The high aromatics—particularly benzene—emissions from storage tanks
are not figments of the procedure, and research into control techniques is
10
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needed. Several approaches to vapor recovery are common in the petroleum
industry; their applicability to this napthalene-rich emission is not known
and will probably have to be field tested. A vapor recovery system plugged
with naphthalene will be of little value.
Potential vapor emissions from the aeration basins and holding ponds of
wastewater treatment systems are not adequately treated in the literature.
Work on this potential problem is recommended.
The final cooler cooling tower was found to be the greatest single emis-
sion source in the plant. Resolving this problem will require careful and
detailed study, as the emissions from the final cooler cooling tower are
linked to effluent quality, at least with respect to cyanide. Cyanide must be
removed from the coke oven gas, especially if it is to be desulfurized, but no
highly specific, inexpensive cyanide removal process is available.
Turning to sampling and analysis procedures, three problems with the
Level 1 protocol became apparent as this study progressed:
1. Sources with very high organic concentrations cause sampling problems
(plugging and resin overloading) and analysis problems (bleed through
between GRAV and TCO and in the LC cuts). A modified procedure for
high concentration sampling should be developed.
2. The analysis is fairly extensive on the GRAV mass, but inadequate
with respect to TCO. This is important for samples with more TCO
than GRAV.
3. Solvent interference for the heated inlet LRMS runs degraded severely
the value of the LRMS, and without the LRMS, analysis of the IR is
very difficult.
11
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3.0 INTRODUCTION
The by-product coking industry in the United States is large—about 60
plants—and well-established. The plants often date back to the 1920's or
earlier, and were designed and built with the object of profitably recover-
ing by-product chemicals. As might be expected, the industry is diverse,
with two or more proven ways to do most of the processing operations.
Plants built more recently show the impact of changing chemical markets, as
none of the coal chemicals are now profitable to recover. The shift has
been toward using the by-product plant to clean coke oven gas for fuel,
recovering those materials that can be used, and economically disposing of
the rest. Today, with the increase in petroleum prices, the new posture for
by-product plants has not fully developed.
The preponderance of older facilities in the by-product industry means
that pollution control as mandated today was not built in. The pollution
control facilities have been added to existing plants piecemeal, and no
single approach has surfaced as a best choice. Most of the past study of
by-product coking was directed at its potential as an industrial process, not
its effect on the environment. What has been done generally emphasized a
particular pollutant or medium, and did not give polynuclear aromatic com-
pounds (PNA's) the attention we now think they deserve.
This study is intended to evaluate the environmental impact of by-
product coking by utilizing available information and by developing addi-
tional data where required. Screening type (Level 1) sampling and analysis
procedures have been used on what are thought to be the most significant
potential sources. The results of all the work are presented in this report
to provide an overview of the environmental effects of the by-product coking
industry.
12
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4.0 PROCESS DESCRIPTIONS: COKE BY-PRODUCT RECOVERY PLANTS
4.1 OVERVIEW OF COMPONENTS AND PROCESSES
Many processes have been developed over the past 100 years or so which
transform coal into a variety of useful products. This discussion, is limited
to the high temperature (around 1000°C) carbonization of "coking" coals with
the primary object of producing metallurgical coke. The purpose of the by-
product recovery plant is to separate and concentrate the volatile compounds
produced and vented from the coke ovens. This report deals with the common
industrial practices for recoverying by-products. The initial subject of
this introductory discussion is the composition of the raw gas leaving the
coke oven, followed by an overview of the process. The major processing
options are discussed more fully in succeeding sections.
Components
The operation of a coke oven is cyclic over a 16-20 hour period, and
the gas composition and rate from a given oven changes as the coking opera-
tion progresses. As 50-60 ovens are often built into a single coke battery,
the overall gas rate and composition are nearly constant in the short term.
An overall look at the major gas components from coke plants in the United
States in 1975 is given in Table 4.1 The fraction of the coal accounted for
specifically in Table 4 is 94.6 percent; the balance is mostly the water
driven off or formed during coking.
Coke Breeze--
Coke breeze as identified in Table 4 is simply the fines (roughly less
than 2 cm) which are separated from the coke at the coke screening stations.
"Breeze" is not part of the feed to a by-product recovery plant.
Coal Tar--
Coal tar is a complex mixture of organic compounds most of which con-
dense in the gas mains leading from the battery to the recovery plant. This
13
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TABLE 4. COKING PRODUCTION STATISTICS-BY-PRODUCT COKE PLANTS, 19751
Coal Carbonized (coked)
Average volatile content
Average sulfur content
Range of sulfur contents
Coke Produced
Coke yield, based on coal
Range
Coke Breeze Recovered
Average yield, based on coal
Range
Crude Tar Produced3
Average yield, based on coal
Range
Sulfate gquivalent of all ammonia
products (NH3 content is 25.8%)
Average yield, based on coal
Range
Crude Light Oilc
Average yield, based on coal
Range
Coke Oven Gas Produced0*
Average yield, based on coal
Range
74,804,000 Mg '(82,284,000 tons)
30.7 %
0.9 %
0.7-1.2 %
51,242,000 Mg (62,003,000 tons)
68.5 %
62.3-72.8 %
3,883,000 Mg (4,271,000 tons)
5.2 %
2.8-8.1 %
2,860,000 Mg (3,146,000 tons)
3.8 % (7.8 gal/ton coal)
2.9-4.7%
598,000 Mg (658,000 tons)
(4.1 Ib NH3/ton coal)
0.8 %
0.7-0.9 %
634,000 Mg (697,000 tons)
0.9 % (2.4 gal/ton coal)
' 0.6-1.1%
11,967,000 Mg (13,164,000 tons)
16.0 % (10,860 ftVton coal)
14.3-20.3 ~
3 —^=
Based on an average density of 1.17 g/ml (Rhodes2).
Ammonia yields may be understated due to problems in reporting procedures.
^Based on an average density of 0.86 g/ml (Glowacki3 and hydrocarbon densities),
Based on gas density of 0.472 g/1; calculated from composition by McGannon4.
14
-------
Is by no means a rigorous definition, and various high boiling organic
streams throughout a by-product plant may be combined with the coal tar. In
appearance tar is a heavy oil, fluid at ambient temperature and with a
specific gravity of about 1.2. The composition varies considerably from
plant to plant, as would be expected. Table 5 gives the average amounts of
some important components of American coal tars.
Ammonia—
Ammonia is reported in Table 4 as the sulfate equivalent because most
coke oven ammonia is ultimately recovered and sold as ammonium sulfate.
Other forms of by-product ammonia made in the U.S. include anhydrous ammonia
and diammonium phosphate.
Light Oil —
Light oil is a clear yellow-brown oil with a specific gravity of around
0.86. It is the coal gas components with boiling points between roughly 0
and 200°C. Over a hundred components have been identified, with benzene
being the primary constituent at 60 to 85 percent. Other major components
are toluene (6 to 17 percent), xylenes (1 to 7 percent), and solvent naphtha
(0.5 to 3 percent). Table 6 presents a representative list of compounds in
light oil and some composition data.
Coke-Oven Gas-
Coke-oven gas is the gas which does not condense during the by-products
processing. A representative analysis has been presented by McGannon,4 and
is included here as Table 7. The heating value of coke oven gas is gener-
ally around 20 MJ/m3 (500-600 Btu/scf).
The components discussed above are the major components of a coke oven
gas after by-product removal without desulfurization; many minor compounds
are also present. Consideration of these is not straightforward, as data
are scarce and wide variations exist. Compounds such as H2S, C02, HCN, and
HC1 are frequently removed to some extent in processing the gas.
Sulfur Compounds—
The estimation of H2S concentrations might seem to be straightforward,
but it is not because an uncertain fraction of the sulfur originally
15
-------
TABLE 5. AVERAGE AMOUNTS OF IMPORTANT COMPONENTS COKE
OVEN TARS 5
Components
Wt. % of Dry Tar
Benzene
Toluene
crXylene
m-Xylene
p-Xylene
Ethyl benzene
Styrene
Phenol
o-Cresol
m-Cresol
p-Cresol
Xylenols
High boiling tar acids
Naphtha
Naphthalene
orMethyl naphthalene
p-Methyl naphthalene
Acenaphthene
Fluorene
Diphenylene oxide
Anthracene
Phenanthrene
Carbazole
Tar bases
Medium-soft pitch
SUBTOTAL
NOT SPECIFIED
0.12
0.25
0.04
0.07
0.03
0.02
0.02
0.61
0.25
0.45
0.27
0.36
0.83
0.97
8.80
0.68
1.23
1.06
0.84
0.75
2.66
0.60
2.08
63.5
86.46%
13.54%
16
-------
Compound
Concentration by Volume %
Compound
Concentration by Volume %
AROMATICS
Benzene
Toluene
Xylenes
Ethylbenzene
Naphthalene
Other C9& Cjo Aromatics
PARAFFINS
n-Pentane
n-Heptane
n-Octane
n-Nonane
n-Decane
NAPHTHENES
Cyclopentane
Cyclohexane
Substituted Cyclohexanes
UNSATURATES
1-Butene
Butadiene
Amylenes
Cyclopentadiene
1-Hexene
2-Hexene
Hexadiene
Cyclohexene
1 -Heptene
Styrene
Indene
Coumarone
Others
56.5
16.5
5.2
0.5
1.0
0.2
0.2
0.1
0.4
0.7
3.0
0.8
3.0
SULFUR COMPOUNDS
Hydrogen Suitide
Carbonyl Sulfide
Carbon Disulfide
Thiophene
Mercaptans
NITROGEN COMPOUNDS
Hydrogen Cyanide
Acetonitrile
Pyridines
OXYGEN COMPOUNDS
Phenols
Cresols
OTHERS
Wash Oil
Solvent Oils
Pitch Residue
0.3
0.2
4.0
1.0
-------
TABLE 7. REPRESENTATIVE
Component
C02
H2S
02
N2
CO
H2
CH4
C2H4
C2H6
Illuminants*
TOTAL
COKE OVEN
GAS
Volume %
1.4
0.6
0.4
4.3
5.6
55.4
28.4
2.5
0.8
0.6
100.0
Treated as propylene
present in the coal is retained in the coke. A statistical analysis of the
Bureau of Mines-AGA tests revealed a good correlation which would give 60
percent of the sulfur going to the coke.? Table 8 presents a selection of
these data from a more recent publication of results from this continuing
effort.8 The seven counties shown together supplied close to half of the
coal carbonized in 1975. Furthermore, although most of the sulfur volatil-
ized is found as .H2S, that component splits between the raw gas and the weak
ammonia liquor in a complex fashion. We will assume that, of the nine units
of sulfur in 1000 units of air-dried coal, six emerge with the coke and
three with the products. Arbitrarily, let two of these three go with the
raw gas, one temporarily with the weak liquor.
Not all the sulfur in the raw gas is present as H2S. The compounds
CS2, COS, CH3SH and still others can be identified. Since CS2 is the princi-
pal sulfurous contaminant other than H2S, it will be loosely quantified. At
a rate of 1 to 2 percent of the sulfur in the coal,9 the amount in the raw
18
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TABLE 8. SULFUR AND NITROGEN IN COAL AND COKE8
Source
Jefferson Co. , AL
Pike Co., KYe
Cambria Co. , PA
Greene Co. , PA
Washington Co. , PA
Logan Co. , WVf
McDowell Co. , WV
S in Coal
0.7-0.9
0.5-1.4
0.8-2.3
1.0-1.3
0.5-0.8
0.5-1.4
Nitrogen
in coal
1.4-1.6
1.3-1.7
1.2-1.4
1.5-1.6
1.2-1.6
1.3-1.8
1.1-1.6
Coke Yield
69.8-75.6
63.3-77.8
64.8-90.1
68.0-70.2
63.7-72.5
65.5-79.3
63.4-90.8
S in Cokec
0.7-0.8
0.5-0.7
0.7-1.7
0.9-1.4
0.5-0.7
0.6-0.8
Nitrogen
in Coke
1.1-1.5
1.1-1.6
1.1-1.5
1.0-1.6
1.0-1.8
h
0.6-1.2
c
aCounties supplying more than 4 million short tons, 1975.*
bThis result and another at 0.9 are exceptional.
Omitting analyses of blends, components of which are usually from other mines,
counties, or even states.
Excluding Terminal No. 9, Westland, and Twilight mines, all high sulfur coals.
Excluding Borderland mine, a high-sulfur coal.
Excluding Big Creek, Winisle No. 1, Elk Creek No. 3, Paragon, Cedar Grove
No. 7, and Upper Cedar Grove No. 15 mines, all high sulfur coals.
coal gas is on the outside about 0.2 units per 1000 units of coal. It is
perhaps not out of place here to observe that the ratio of CS2 to H2S in
coke oven gas, about one in twenty, is conspicuously higher than in petro-
leum refinery fuel gases. This fact influences the choice among desulfuriza-
tion processes.
Nitrogen Compounds—
Nitrogen compounds of interest, in addition to ammonia, include hydro-
gen cyanide and the tar bases. We will first discuss the source of the
nitrogen and then the compounds. Table 8 includes data indicating the
amount of nitrogen in some coals. The data in Table 8 suggest that the
nitrogen originally present divides almost pro rata between the coke and the
volatiles, i.e., some 65-75 percent of the nitrogen in the coal is fixed in
the coke. (This can be compared with a rule-of-thumb of 50 percent published
19
-------
in 1924.10) On this basis gaseous nitrogen should amount to about 0.3 percent
of the coal charged. The data in Table 5, converted to weight percent, give
a gaseous nitrogen content of 1.8 percent based on the coal. It is probable
that much of this unaccounted-for nitrogen is a consequence of air introduced
at charging or infiltrating into the negative pressure gas main. The free
oxygen in coke oven gas is another indicator of air infiltration.
Ammonia is the most important of the nitrogen compounds, representing
about 0.20 percent of the coal carbonized in 1975. The nitrogen content of
the ammonia, compared to a'representative 1.4 percent nitrogen in the coal
suggests that about 12 percent of the coal nitrogen emerges as ammonia.
This is somewhat below the classical rule-of-thumb, 18 percent,10 reflecting
the higher coking temperatures and coking rates of modern industrial prac-
tice,11 with consequent decomposition of some primary ammonia.*
Tar bases are also important nitrogenous by-products. The label "tar
bases" properly embraces pyridine (C5H5N) and its substituted homologs
(picolines, lutidines), quinoline (C9H7N) and its homologs, acridine
(C13H9N), etc. The customary nomenclature can be stretched to include the
cyclic secondary amines pyrrole (C4H5N) and its homologs, indole (C8H7N),
carbazole (C12H9N), and even primary amines such as aniline (C6H7N) and
toluidines (C7H9N).
Kirner12 summarizes Bureau of Mines findings through 1939 by stating
that "The quantity of nitrogen bases obtained in the distillation of Ameri-
can coals over the temperature range 500-1100°C does not vary appreciably."
Since the coals and the carbonization process have changed little since
those findings, we will assume that they still pertain. Kirner goes on to
say that the unrefined light oil contains 1-3 percent pyridine and its
*It can be shown with the aid of standard thermodynamic data that equilib-
rium in the dissociation reaction
2NH3 ? N2 + 3H2
is far to the right at all temperatures of interest. The effect of tempera-
ture and the catalytic influence of certain solids, especially iron, on
reactions rates is reviewed by Hill.10 The so-called protective action of
steam mentioned by Hill is probably competitive chemisorption on the cata-
lytic surfaces.
20
-------
lighter homologs, and the tar contains 2.3 percent tar bases and a like
amount of carbazoles. Using these rough figures with the gross split of
Table 8, the nitrogen bases in the light oil amount to perhaps 0.02 percent
of the coal, those in the tar to about 0.2 percent. If these amounts were
all pyridine, which is about 18 percent nitrogen, the total of nitrogen
bases would account for about 3 percent of the nitrogen in the coal, con-
sistent with an old rule-df-thumb.10
Hydrocyanic acid (hydrogen cyanide, loosely called cyanogen in the
industry) is important not only because its cyanide ion emerges as a water
pollutant but because it interferes with sulfur recovery. The formation of
HCN according to the reaction
CH4 + NH3 * HCN + 3H2
is thermodynamically favorable above about 800°C. But the reaction is
evidently slow in coke ovens. The cyanogen content of a typical American
coke oven gas is 1.37 g/m3 13 compared to about 7.6 g/m3 of H2S for the 0.9
percent sulfur in 1975 coking coal.14 (Nothing like this much cyanogen is
found in the desulfurization of fuel gases in petroleum refineries.) On a
weight basis, the cyanogen is 0.003 g per gram of gas, or 0.5 g per kilogram
of coal; since cyanogen is about half nitrogen, this means that about 2
percent of the coal nitrogen emerges as HCN, as has been traditionally
observed.10
Chlorine Compounds--
Chlorine in coal is so little a problem in this country that it is not
reported in so-called "ultimate" analyses.15 Moreover, it occurs primarily
as the water-soluble minerals halite (NaCl) and sylvine (KC1), and is large-
ly removed in the wet processes by which most coking coals are cleaned.4
What remains is usually assumed to distill during carbonization, primarily
as HC1.
Oxygen Compounds™
As has been noted, there is some oxygen in coke oven gas which is
unlikely to have come from the coal. That in the coal is found primarily as
C02, CO, and H20. The important oxygen compounds for present purposes,
21
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however, are the "tar acids": phenol (C6H60) and its homologs, naphthols
(C10H80) and their homologs, catechols (C6H602), etc. These are toxic to
biota in receiving waters and, when chlorinated during water treatment, even
a few parts per billion impart an unacceptable taste to drinking water.16
Coal with the national average volatile content, 30 percent, carbonized
at 900-1000°C as is typical in this country, should give a tar containing
2-3 percent tar acids.*7 Thus 1000 units of coal produce 38 units of tar
containing 1 unit of tar acids.
Process Overview
This process description section describes the mainstream of U.S. coke
by-product recovery operations. An overview is presented below, and more
complete descriptions in the following sections. There are generally two or
three ways, more or less widely used, to do any of the recovery operations.
Section 5 of this report discusses the prevalence of the various processes
in the United States.
The flowplan and material balance of a representative coke by-product
recovery plant is given as Figure 1. More detailed information is included
in later sections. Table 9 summarizes the fate of the major coke oven
by-products in a representative plant.
The gases leaving a coke oven are generally at around 700°C and of
course contain all of the material to be processed in the by-product plant.
Coke ovens are maintained at a slight positive pressure (1 mm water) to
prevent air infiltration. As the gas leaves the oven it is subjected to
spray cooling^immediately, both to cool the gas and to introduce a collect-
ing medium for the tar as it condenses. After a short duct run the gas
passes through a valve and enters a suction main, remaining below atmos-
pheric pressure. At this point, the gas has generally been cooled to the
100°C range; much of the water, tar, and ammonia, along with other compounds,
have been condensed. Further removal by condensation is accomplished in the
primary cooler and tar removal process steps. The tar and the water soluble
compounds are separated by decantation. The tar is generally further dewa-
tered before sale. If phenol is recovered from the ammonia liquor, it is
often absorbed in an organic solvent before the ammonia recovery step. The
ammonia liquor is traditionally steam-stripped to put the ammonia back into
22
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RECYCLED COOLING WATER
ISJ
00
DEBENZOLIZED COG
FLUSHING LIQUOR
WASTE WATER
PHENOLATE
CRUDE LIGHT
OIL
FIXED
NH3
STILL
WASTE AMMONIA
LIQUOR
LIME
SLUDGE
COAL
TAR
KG /DAY
CARBON SOLIDS
WATER
CARBON DIOXIDE
HYDROGEN SULFIDE
AMMONIA NITROGEN
CYANIDE
CHLORIDE
GASES :H2, CO, CH4,N2,O2,HC
CARBON DISULFIDE
LIGHT OILS
TAR ACIDS
TAR BASES
POLYCYCLICS
OTHER
TOTALS
TEMPERATURE *C
PRESSURE, tart
COAL
0,000°
3OO
O,5OO
COKE
7370
737O
RAW
GAS
IOO
89
29
15
4
I5OO
2
90
2
1
IB4O
60
I.I
W
NH
LIQUOR
9OO
1
1
S
1
1
1
9IO
3O
TAR
e
8
IO
10
34 O
380
JO
STRIP
no
I
I
5
1
I2O
95
I.I
VWSTE
LIQUOR
IO4O
TRACE
1
TRACE
Co. 1
IO4O
IO5
w
STEAM
2 SO
Z5O
130
2.7
V
SALT
2O
SO4> 53
73
V
COG
24 O
9O
30
5
I5OO
2
90
2
1
I960
45
I.O5
COG
14 O
90
3O
3
I5OO
2
9O
2
I860
3O
I.O4
COG
13O
85
30
3
I50O
5
I76O
30
1.02
CRUDE
LO
2
BS
2
9O
COG
I3O
80
2
I50O
5
17 2O
3O
I.O
o. BASIS: THE SCALE FACTOR TO DUNLOP AND McMICHAEL (36) IS 55O
b. ROUNDED
Figure 1. Flowplan and material balance of a representative coke by-product recovery plant.
-------
TABLE 9. FATE OF COKE OVEN BY-PRODUCTS
Component
Route
H2, CH4, and light hydrocarbons,
N2, 02, CO, and C02
Ammonia
Water
H2S, HCN
Benzene, Toluene, Xylene
HC1
Tar bases (C5H5N, etc.)
Tar acids (phenol etc.)
Naphthalenes
Heavy organics (boiling point
>200°C)
Remain in gas; used as fuel gas
Via gas to ammonia scrubber, or via
liquor to ammonia still, then back to
gas and thence to ammonia scrubber.
Most ammonia converted to ammonium
sulfate.
Via liquor to ammonia still, remains
as waste ammonia liquor.
Via gas or liquor to free ammonia still,
thence into gas to desulfurizer
Via gas to light oil scrubbers
Via liquor to waste ammonia liquor
as CaCl2 (lime still)
Condensed into tar, or via gas to
ammonia scrubber.
Via liquor to dephenolizor, or con-
densed as tar.
Condensed in tar, or via gas and con-
densed in final cooler.
Condensed as tar (small fraction to
light oil).
the gas stream, as shown. The waste ammonia liquor requires addition of a
base to release some chemically bound ammonia.
Looking again at the gas stream, the exhauster is the fan which pro-
vides motive power for the gas. Tar removal effects nearly complete recovery
of the tar remaining in the gas, generally as participate; both scrubbers
and electrostatic precipitators are used in the industry. After the ammonia
stripped from the waste ammonia liquor rejoins the gas stream, the ammonia
can be scrubbed from the gas with a dilute sulfuric acid solution. Ammonium
sulfate crystals form and are separated from the saturated liquor. The
final cooler is a pretreatment step for light oil (benzene) recovery. In
the process, generally contact cooling with water, naphthalene is condensed
from the gas. The naphthalene may be removed from the water by absorption
24
-------
in organics or by flotation. Light oil is usually recovered by absorption
in a petroleum fraction (wash oil). The light oil is steam stripped from
the wash oil and recovered and the wash oil recirculated. Desulfurization,
if practiced, is intended to make coke oven gas a more acceptable fuel. No
process is in widespread use today; only a few larger plants practice desul-
furization.
The following sections of this report deal with the individual processes
in more detail. Further information is available from sources listed in the
references. A good first selection would be the coke and coal chemicals
chapter of The Making. Shaping, and Treating of Steel, published by the U.S.
Steel Corporation. The reader should remain aware that at least three
powerful influences militate against any single process description being
widely applicable: (1) today's by-product plants have often evolved over
20-50 years of maintenance, design, and operational changes, (2) the tech-
nology is mature and there are many proven alternate ways to recover chemi-
cals, and (3) the market for coal chemicals is uncertain, and economic
pressure has led to changes in operating philosophy.
4.2 TAR SEPARATION AND PROCESSING
Coal tar is produced in a coke oven at a rate of around 30 1/Mg coke
(8 gal/ton). Figure 2 outlines the primary tar separation operations. The
condensation of tar initially takes place under direct contact with flushing
liquor in the collecting mains and suction mains. The gas mains are sprayed
and vigorously flushed with recycled liquor both to quench the gas and avoid
buildup of tarry deposits. Around 70 percent of the tar is separated from
the gas in the mains and is flushed to the flushing liquor decanter. Another
20 percent of the total is condensed and collected in the primary cooler,
along with a significant amount of water. Tar continues to be removed from
the gas in the exhausters, and a final tar removal step (often precipitators,
sometimes scrubbers) removes the last of the entrained tar particulate.
Each of these tar/ammonia liquor streams is traditionally separated by
gravity, generally in more than one separation device. These decanters are
commonly vented to the atmosphere; they may or may not have tops. The level
of separation achieved by decantation is highly variable. Typical residence
times are about-10 minutes for the liquor and 40 hours for tar.19 A common
25
-------
FLUSHING LIQUOR
COAL
ro
en
FINAL TAR
REMOVAL
FLUSHING
LIQUOR
DECANTER
PRIMARY
COOLER
DECANTER
WEAK
LIQUOR
DECANTER
40C
COKE OVEN GAS
'TO SEPARATOR
TAR
DEHYDRATOR
EXCESS AMMONIA
LIQUOR
COAL TAR
*This flow/plan includes a direct contact primary cooler. Indirect primary
coolers utilizing noncontact cooling water are also fairly common.
Figure 2. Tar separation.
-------
target for water in coal tar is around 2 percent;6 multiple decanting stages
may be used with final dewatering by centrifugal separator or heating in
storage. Chemical emulsion breakers are sometimes used.
Processing
Coal tar can be refined to produce a number of chemicals. Considine20
has outlined a complete process route for coal tar, which is presented in
Figure 3. The precise state of tar refining in the United States is somewhat
uncertain today. The coke/coal tar industry was once the exclusive source
of such chemicals as naphthalene, pyridine, phenol, and their derivatives.
Competition from petroleum based chemicals has made serious inroads into the
coal chemicals market. Bureau of Mines reports,21 confirmed by annual AISI
directories,22 indicate that only a few (4-8*) coke producers practice
on-site tar refining. The refining that is done on-site need not include
all the separations shown in Figure 3. Each tar refining plant was built
and operated to meet specific market conditions, and the plant may respond
to changing conditions by abandoning a process step (as CF&I did), rearrang-
ing the process to add an extra step, or pressing old hardware into new
kinds of service. Local markets occasionally allow profitable operation for
independent tar distillers who collect tar from several producers. In
today's market, it is unlikely that coal tar would be refined at the site of
a new coke battery. Some existing equipment has been shut down at various
by-product plants. The value of coal tar as a fuel has risen considerably,
and smaller producers often burn this tar. Storage of tar is generally in
vented, cylindrical tanks at above ambient temperature (perhaps 50-80°C), to
permit easy transfer.
4.3 AMMONIA HANDLING
The ammonia produced in a coke oven amounts to around 0.2 weight percent
of the coal fed to the ovens. Flushing liquor sprayed into the collecting
mains to cool the gas absorbs some of the ammonia, and more is absorbed in
the water condensed in the primary cooler (Figure 1). Flushing liquor con-
*The data on number of producers have been concealed by USBM to avoid
disclosing company data.*
27
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CRUDE TAR
CHEMICAL
OIL
PITCH
oo
ISTILLATION
ISTILLATION
CAUSTIC
TREATMENT
ACID-FREE
CREOSOTE
ACENAPHTHENE
PHENANTHRENE,
ANTHRACENE,
FLUORENE,
MANY OTHERS
ACIDIFICATION
ACID SALTS
ACIDIFICATION
OF
TAR BASES
DISTILLATION
CAUSTIC
TREATMENT
SOLVENT
NAPHTHA
TAR ACIDS
(PHENOL,
CRESOL,
HIGH-BOILING
PHENOLS)
NAPHTHALENE
(PICOLINE,
LUTIDINES,
QUINOLINES,
PYRIDINE)
SALT SOLUTIONS
TAR BASES
Figure 3. Tar refining outline.2 °
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tains around 5-6 g NH3 per liter. Along with ammonia, compounds such as
hdyrogen sulfide, phenolic compounds (tar acids), and cyanides dissolve in
the flushing liquor. The distribution of ammonia between the gas and liquid
phases depends on operating conditions and the coal composition. Figure 1
uses a representative split with 75 percent of the ammonia remaining in the
gas phase.
Ammonia handling then is a problem of removing the ammonia from both
the gas and ammonia liquor streams and achieving satisfactory disposal of
any waste. Whatever the scheme for removing ammonia from the coke oven gas,
there will always be an aqueous waste because the carbonization of coal
produces water.
Several processing options have been developed to recover the ammonia.
The cyanide and phenol generated in the coking process must also be dealt
with, and are discussed in separate sections of this report. The ammonia
handling route shown in Figure 1 is known as the "semi-direct" process, and
is the option most common in the United States. All of the ammonia is
eventually recovered from the gas stream, but a portion enters the flushing
liquor first and is later stripped out. (The "direct" process involves
controlling the quenching in the gas mains such that no aqueous waste is
condensed. The gas phase, containing practically all the ammonia, is then
scrubbed with sulfuric acid to recover the ammonia. This process has many
drawbacks and is not practiced in the United States.6 The indirect process
option requires additional water scrubbing to get essentially all the ammonia
into the liquid phase, where it is concentrated by distillation. A very few
American producers follow this route, producing only aqueous ammonia.21)
The remainder of this discussion of ammonia handling will deal with the
semidirect processing route and its requirements.
Ammonia Liquor Treatment
As was discussed under tar separation, aqueous ammonia solutions are
decanted from the tar in a variety of processing vessels. Much of this is
recycled as flushing liquor; a portion is constantly drawn off as weak
(sometimes excess, crude, or waste) ammonia liquor. The ammonia in the weak
ammonia liquor (WAL) must be put into the gas phase for recovery via the
acid contactor. The traditional removal technique is steam stripping as
29
-------
shown in Figure 4. The ammonia in the weak ammonia liquor can be thought of
as being present in two forms: "free" and "fixed". Free ammonia compounds
are those which can be dissociated with heat (ammonium carbonates, sulfides,
cyanide, etc.). "Fixed" ammonia compounds are those associated with strong'
acids (ammonium chloride) which must be dissociated by the addition of a
strong base (generally lime or sodium hydroxide).
The actual design and operation of ammonia stills is not as straight-
forward as it might appear based on the discussion above.' The chemical
complexity of ammonia liquor requires that designers consider several simul-
taneous ionic equilibria as well as vapor-liquid equilibria for water and
volatile solutes. H2S and NH3 might be considered the primary solutes, but
also present and interacting are dissolved C02, HCN, phenol and various
homologs, pyridine and its homologs, and chloride ion. Dealing-satisfacto-
rily with all these equilibria has only been practical with the advent of
computers, and the results will still be no better than the available data.
Most existing ammonia stills were necessarily designed in a somewhat empiri-
cal way to meet specific goals with respect to ammonia concentrations; the
other components pretty well go along for the ride. Along with ammonia,
HCN, H2S, and phenol can be stripped from ammonia liquor by steam. As shown
in Figure 4, the ammonia stripping is commonly accomplished in two more or
less separate stills. Free ammonia is stripped in the top (free) still by
the steam and ammonia vapor rising from the lower still. A basic solution
is added near the center of the tower. Any phenol and cyanides which are
not stripped out in the free still are chemically bound by the base and are
not removed in the fixed still. The steam injected in the bottom of the
lower (fixed) still strips out the ammonia released due to reactions by the
change in pH.
The conventional approach to pH adjustment has been the addition of
dissolved lime (5-10 percent) to the partially stripped liquor in the "lime
leg". The liquor, with a pH of around 11 here, is then exposed to the
stripping steam in the fixed still. Caustic solutions are coming into favor
for pH adjustment in fixed stills because they allow better pH control,
reduce total water usage and eliminate scaling and precipitate problems
along with some suspended solids in the effluent from the stills. In addi-
tion, the efficiency of the stills is better. Caustic is more expensive,
30
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^ AMMONIA TO
GAS STREAM
COOLING WATER
DEPHLEGMATOR (PARTIAL CONDENSER)
100° C VAPOR
WEAK AMMONIA
LIQUOR
FREE
AMMONIA
STILL
LIME
LEG
(DISSOLVER)
. LIME WATER
IF NaOH USED \
NO DISSQLVER NEEDED/
FIXED
AMMONIA
STILL
LIME
SLUDGE
STEAM
WASTE WATER
Figure 4. Ammonia stills.
31
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but apparently the overall operating costs just about break even when com-
pared to lime addition.23
The efficiency of removal of ammonia/H2S/HCN/phenol and others in the
ammonia stills is a function of still design and operation. Most existing
stills utilize tray-type columns with about 10 trays in the fixed still and
5-6 in the free stills. Bubble-cap trays appear to be common.* Liquor
leaving the still contains about 0.15 g/1 of ammonia. In traditional designs
the vapor leaving the ammonia still is partially condensed in a "dephlegmator"
to reduce the water content of the vapor. The condensate is refluxed to the
still. The ammonia rich vapor leaving the top of the still is then combined
with the coke oven gas stream for recovery of the ammonia. Another possi-
bility24 is to incinerate the ammonia.stripped in the ammonia stills.
Another approach to stripping ammonia from ammonia liquor is to use air
rather than steam, thus reducing the volume of water in the process and
improving overall ammonia removal.. The use of air has been investigated on
a pilot scale.23 One disadvantage to the use of air stripping is that the
stripped ammonia cannot be combined with the coke oven gas (because air is
in the stream) for recovery via the normal route. A separate ammonia pro-
cessing step (sulfate or equivalent) or incineration must be provided.
Ammonia Recovery from the Gas
Ammonia removal from the coke oven gas has traditionally been by contact
with sulfuric acid and recovery of crystalline ammonium sulfate. In the
classical (roughtly pre-19304) form of the saturated the raw gas was
forced to bubble up through a pool of dilute sulfuric acid saturated with
(NH4)2S04. Crystallization occurred in the saturator. The burden of forc-
ing the gas and liquid into contact was thus imposed on the exhauster. The
crystals were separated by gravity and the acid solution recycled with make-up
acid added as required. The crystals were further dried by centrifuge,
washed, and dried again.
In the Otto System,4 the acid is lifted and sprayed into the top of a
short column through which the gas is rising. Better contact (interfacial
area per unit of saturator volume) is achieved for less energy. The crystal-
lizer is a separate vessel, but the absorber and crystallizer still interact.
32
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The Wilputte System4 (Figure 5) divorces the two, achieving better
control of crystal size. Here the spray is not saturated with salt and the
separate crystallizer is operated by evaporative cooling under sub-atmospheric
pressure. Water vapor with entrained impurities passes to two or three
steam-jet ejectors in cascade. Barometric condensers exhaust the hot conden-
sate to a sump. The condensate is of a quality which permits the operation
of a cooling tower to serve the condensers, but the blowdown is a necessary
process discharge.
The ammonium sulfate produced in the semi-direct process has found a
progressively poorer reception in the fertilizer market as anhydrous ammonia
has gained in popularity. Its marketability was further depressed by rapid
growth in.the production of caprolactam, a nylon intermediate,..which also
has ammonium sulfate as a by-product. One possible remedy has been to
substitute phosphoric acid for sulfuric; the hardware is the same and operating
conditions only slightly different. The by-product is the more marketable
di-ammonium phosphate, containing two important plant nutrients instead of
one, but at a higher price for the acid. Only two producers chose this
route in 1973.21
Another remedy, growing out of the foregoing, is the absorption of
ammonia in circulating aqueous (NH4)H2P04,25 the stripping of ammonia from
this medium, and the condensation of the concentrated ammonia (Figure 6).
Distillation of the product, either with refrigeration or under pressure,
yields a substantially pure ammonia which is more readily marketable than
are the salts. It appears that the entire coke by-product ammonia output of
U.S. Steel's Clairton Works, the largest coke plant in the world, is in the
anhydrous form produced by this technology.
Still another remedy to the ammonia disposal problem is the incineration
of the ammonia stripped from the scrubbing medium.26 Noting that the commer-
cial production of nitric acid starts the same way, we can be sure that this
thermal destruction of NH3 must be carefully managed to minimize N0x produc-
tion. Low temperatures, low excess air, and slow cooling are recommended.
-This technology is being practiced by Inland Steel at East Chicago.
4.4 TAR ACID (PHENOL) REMOVAL/RECOVERY
Phenol is one of the minor constituents of coke oven gas, highly vari-
33
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COKE OVEN GAS
AMMONIA
SCRUBBER
AMMONIA-RICH
GAS FROM STILLS
AMMONIA-FREE
COKE OVEN GAS
CONDENSER
STEAM
^—.
CRYSTAL'R
SLURRY
WATER,
SULFURICACID
WASTEWATER
LIQUOR
CENTRIFUGE
AMMONIUM SULFATE
Figure 5. Ammonium sulfate recovery with vacuum crystallizers (Wilputte).
34
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LEAN ABSORBENT
COKE OVEN GAS
AMMONIA-FREE COKE OVEN GAS
AMMONIA-RICH
GAS FROM
STILLS
ANHYDROUS AMMONIA
STEAM WASTE
Figure 6. Ammonia recovery by "Phosam" process
25
35
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able in concentration as coking practice and coals vary. Most of the phenol
in the gas phase is scrubbed into the flushing liquor. One operator has
reported phenol concentrations in the excess ammonia liquor between 500 and
4,500 ppm over 20 years of operation and coking times of 13 and 22 hours ^
The term "phenol" is often used, as was done above, to refer to all the tar
acids in the waste stream. Tar acids are actually made up of roughly 60 to
80 percent phenol, the remainder being mostly cresol with small amounts of
some higher homologs of phenol."" The phenol concentrations in WAL commonly
cited as design values are 1,000 to 2,000 parts per million.
Several phenol removal/recovery techniques are practiced or have been
tried. The traditional process types are solvent extraction and steam
stripping. In both cases the phenol-rich phase, once extracted, is treated
with caustic to make sodium phenolate. Carbon adsorption is a process which
has been considered but is not yet in full scale use. In addition to the
above, some sort of final wastewater treatment (perhaps biological) is
probably necessary to make the waste acceptable for discharge.
The widely used solvent extraction dephenolization process generally
utilizes light oil or benzene to extract phenol from the waste ammonia
liquor. In addition, several proprietary solvents have been used over the
years. These solvents are generally more expensive than light oil and
require additional effort to recover the solvent in order to be economical.
They have not been widely used in the United States. The efficiency of the
solvent extraction process is generally around 95 percent phenol removal,
although some plants have done better and by increasing the solvent rate'or
improving the contactor efficiency better removal can be effected. Solvent
extraction removes all of the tar acids with good efficiency. Figure 7
includes a flow diagram of a solvent extraction dephenolization process.
The flow of weak ammonia liquor is into and down through an absorber column.
This absorber column may be a packed tower, a tray tower, a mechanically
agitated column, or a series of mixer-settlers. The solvent rate is gen-
erally on the order of 1.2 volumes of solvent per volume of weak ammonia
liquor, although wide variations in practice are to be expected.
The purpose of the caustic contactor is to remove the phenol from the
light oil by converting it to sodium phenolate. Again, the contactor may be
either a packed tower or mixer-settler. Consumption of caustic is in the
36
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SOLVENT EXTRACTION
"SPRINGING'
PHENOLIZED LIGHT OIL
EXCESS
AMMONIA
LIQUOR
DEPHENOLIZED
AMMONIA
LIQUOR
WASTE GAS
10% CAUSTIC
TAR ACID PRODUCT
WASTE (Na2,C03, WATER, PHENOL, ETC.)
HIGH C02 GAS
STEAM STRIPPING DEPHENOLIZATION (VAPOR RECIRCULATION)
EXCESS
AA/in/innti A fel
LIQUOR
I
DEPHENOLIZED
AMMONIA
LIQUOR
STEAM -»
/K
x
2 t
X
vJ
4 f
~£
^ CAUSTIC, 10%
'
1
k. SODIUM
> SODIUM PHENOLATE (TO PROCESSING AS ABOVE)
Figure 7. Dephenolization.
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range of twice stochiometric, although better results have been obtained.
Caustic is often added as a 10 percent solution; the caustic operation is
usually batch orJsemi-batch. In today's operation the phenol removal proc-
ess usually stops at this point; that is, with the separation of the sodium
phenolate solution. When it is desirable to recover the phenol itself, the
phenol is removed from the sodium phenolate solution by contact with an acid
gas. This operation is called "springing", and it leads to the release of
phenol as a liquid on top of the aqueous phase and an aqueous waste of
sodium carbonate and bicarbonate in water, along with some residual phenol.
The acid gas used in the "springing" operation has generally been a combus-
tion gas with a high C02 content.
Dephenolization by steam stripping is the second traditional process.
It is sometimes called vapor recirculation dephenolization. Steam stripping
of phenol must follow removal of free ammonia, as the ammonia is more vola-
tile than the phenol. Figure 7 includes a flow plan of a vapor recircula-
tion contacting device. The stripping steam is run in a loop which includes
a stripping contractor in which the phenol is removed from the waste ammonia
liquor, and a caustic tower in which the phenol-laden steam contacts an
aqueous caustic solution. Sodium phenolate is formed in the caustic tower.
The phenol stripper and the caustic contactor may be both physically in one
column with appropriate internals, or they may be in two separate vessels.
Under normal operating conditions, this process removes most of the phenol,
but not the heavy homologs such as cresols. Thus its overall efficiency for
tar acid removal is limited. The absorber is generally run a bit above
atmospheric pressure. The steam recirculation rate is on the order of a
kilogram of steam per kilogram of ammonia liquor.
As discussed previously, carbon absorption has not been reported as
being used in the United States for phenol removal from waste ammonia liquor,
although its use has been piloted by Republic Steel as part of the wastewater
treatment process (not phenol recovery). Carbon absorption does have the
potential of removing essentially all of the phenols in the waste stream.
4.5 FINAL COOLER AND NAPHTHALENE PROCESSING
The basic function of the final cooler is to cool the coke oven gas
from around 60°C to about 25°C in order to improve light oil absorption in
38
-------
the light oil scrubber.. As the gas is cooled, some water and most of the
naphthalene which is still in the coke oven gas is condensed into the cool-
ing medium. Both must be removed 'from the gas to prevent problems down-
stream.
The final cooler itself is often a simple spray tower. Packed towers
can be used but condensed naphthalene may plug the tower. Spray towers
require higher liquid rates or taller towers due to a lower contacting
efficiency than is possible in packed towers.
The cooling medium has traditionally been water, but wash oils can also
be used. If wash oil is the cooling medium, naphthalene will dissolve along
with some light oil. The water which is condensed must be removed in a
decanter and the wash oil recirculated and cooled. A slipstream of the rich
wash oil is routed to the light oil plant for removal of the light oil and
naphthalene. A lean wash oil make-up stream is provided to the final cooler
circuit.
Final cooler cooling water may be either recirculating or once-through.
Recent practice tends towards recirculation due to water pollution constraints.
Naphthalene can be removed from the final cooler cooling water as a solid or
it may be dissolved in tar in a sump and the water allowed to separate by
gravity. Figure 8 is a flow diagram of a final cooler and recirculating
water circuit with the naphthalene collected by physical separation. After
contacting the coke oven gas in the final cooler, the water is pumped to a
separation device prior to the cooling tower. Water soluble compounds such
as chlorides and cyanide accumulate in the water. Naphthalene will separate
by gravity in a sump, or the separation may be enhanced with a froth flota-
tion separator or similar equipment. The naphthalene may then be skimmed
from the surface of the water.
After separation of the naphthalene, the water is commonly cooled in an
atmospheric cooling tower and then recirculated to the final cooler. The
use of a cooling tower ties the conditions in a final cooler to weather
conditions at the plant site, and during hot, humid summer weather 30°C
would be difficult to maintain. During the winter a cooling system designed
for summer conditions is oversize, and the cooling tower will be lightly
loaded. The operation of the cooling tower is of interest because the cool-
ing tower will strip out the light components dissolved in the recirculating
39
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RECIRCULATING WATER
COKE OVEN GAS
50-60°C
FINAL
COOLER
20-30°C
NAPHTHALENE
SEPARATION
CRUDE NAPHTHALENE TO
FURTHER PROCESSING
COOLED COKE OVEN
GAS TO LIGHT OIL
SCRUBBER
SATURATED AIR
ATMOSPHERIC
COOLING
TOWER
WATER
SLOWDOWN
T
AMBIENT AIR
Figure 8. Final cooler with naphthalene separation.
40
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water. The extent to which these are dissolved in the water and then stripped
into the air is dependent on the operation of the final cooler and cooling
tower. A blowdown stream is taken from the recirculating water to dispose
pf water condensed from the coke oven gas and not evaporated or entrained in
the cooling tower. Some blowdown is necessary to dispose of chlorides.
Naphthalene collected by physical separation is impure, having a dirty
brown appearance and containing a good bit of water (perhaps 50-60 percent).
This naphthalene slurry is commonly dewatered by gravity separation as much
as possible. Further processing may include drying/melting with non-contact
steam for sale as crude naphthalene or refining into a better grade of
naphthalene.
The second common way of handling the final cooler water is to pass the
water through tar in the bottom of the final cooler and allow the naphtha-
lene to dissolve in the tar. The naphthalene is then included with the tar
in any additional refining operations. The tar, of course, contained con-
siderable naphthalene before including the final cooler naphthalene. Figure
9 is a flow diagram of a tar bottom final cooler. There must be sufficient
water above the tar bottom to force the water through the distributer and
into the tar. The water then separates by gravity and is decanted. The tar
is recirculated back to the tar storage tanks continuously. Obviously, the
same operation could be conducted in separate vessels of various designs.
The efficiency with which naphthalene is removed by the tar was not avail-
able in the literature although it is apparently fairly high. The final
cooler water is cooled in a cooling tower and recirculated to the top of the
tower. Again, air stripping of light components in the water occurs to some
extent in the cooling tower. A significant water blowdown is again neces-
sary.
4.6 LIGHT OIL RECOVERY
Light oil is a clear yellow-brown oil, with a specific gravity of about
0.86. It is the coke oven gas fraction in which the more than 100 constit-
uents with boiling points between 0°C and 200°C or so reside. Benzene is
generally 60 to 85 percent of light oil, with toluene (6 to 17 percent),
xylene (1 to 7 percent), and solvent naphtha (0.5 to 3 percent) being the
more important of the lesser constituents. Crude light oil production
41
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RECIRCULATING COOLING WATER
NAPHTHALENE
RICH TAR
20-30°C
COOLED
COKE OVEN GAS
SATURATED AIR
•NAPHTHALENE
RICH WATER
NAPHTHALENE
LEAN WATER
ATMOSPHERIC
COOLING TOWER
AMBIENT
AIR
Figure 9. Tar-bottom final cooler.
42
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averages slightly less than one mass percent of the coal carbonized, or
14.4 1/Mg coke.
There are basically three available collection processes for light oil:
1. absorption in a liquor (wash oil), followed by steam stripping to
separate the light oil;
2. refrigeration followed by compression at conditions of -70°C and
10 atmospheres;
3. adsorption on solids (such as carbon), followed by regeneration.
After separation light oil may be sold as crude light oil or it may be
further fractionated on-site into various light oil fractions.
The absorption of light oil into wash oil is prevalent in the United
States. Figure 10 is a flow plan of a fairly typical process. Wash oil
towers may be operated singly, or as two or more in series with countercur-
rent flow. They may be tray or packed towers or of the gravity spray type.
The spray towers are less likely to plug, but are less efficient for a given
tower height and oil rate. Wash oil is kept above the coke oven gas tempera-
ture to prevent condensation of water (which emulsifies). At about 30°C a
traditional .light oil scrubber will remove around 95 percent of the light
oil from coke oven gas. Wash oil is circulated at around 1.5-2.5 1/m3 coke
oven gas through the contacting stages.
The benzolized wash oil is steam stripped to recover the light oil.
Live steam is injected into the bottom of a plate tower and the more vola-
tile light oil is stripped overhead. One of the main criteria for selection
of a wash oil is that a good separation be achieved with minimal degradation
of the wash oil. The flow plan in Figure 10 shows light oil recovery and
subsequent rectification to separate a benzene-toluene-xylene (BTX) fraction
from the heavier components. A simpler flow scheme would leave out the
rectifier, collecting a crude light oil fraction.
Further refining of light oil into high purity fractions such as benzene,
toluene, and xylenes is practiced at some plants. The light oil is fairly
valuable, but the adverse economics of small-scale refining have forced many
plants to shut down or not replace light oil fractionation equipment. In
addition to the fractionation, the light oil fractions must be desulfurized
before sale on the open market. Treatment with sulfuric acid is the accepted
43
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LIGHT
OIL
SCRUBBER
COKE
OVEN
GAS
15-30 C
DEBENZOLIZEO
WASH OIL
1
DEBENZOLIZED
COKE OVEN GAS
LIGHT OIL VAPOR 113° C
WASH
OIL
STILL
1
| OPEN STEAM
J0.07 0.00 ka/l
VAPOR-TO-OIL
HEAT EXCHANGER
NONCONOENSABLES
CONDENSER f
+ ~*|
+
1
*
j SEPARATOR
| PRIMARY
LIGHT OIL
SEPARATOR
STEAM
COIL
\ ' _g
_,J^_ -
3 I ^
i >
WASTEWATER
- 4
LIGHT OIL
RECTIFIER
SEPARATOR
SEPARATOR
*
LIGHT OIL: MOSTLY WASH OIL.
SOME HIGH BOILING LIGHT OIL
INTERMEDIATE LIGHT OIL: COMPONENTS
WITH BOILING POINTS ABOVE XYLENES
SECONDARY LIGHT OIL: XYLENE AND BELOW
BOILING POINTS, MOSTLY BENZENE AND
TOLUENE
INTERMEDIATE
LIGHT OIL TANK
/ ^ ___
/ 11.6-2.5 tfm3 GAS
/ U2-0.3H LIGHT OIL j
TEMPERATURE^ 2" > GAS «-
SECONDARY
LIGHT OIL
TANK
WASH OIL COOLER
DECANTED WASTEWATER
TO INTERCEPTING SUMP
WASH OIL
DECANTER
MUCK
(PERIODICALLY)
•Ql
DEBENZOLIZEO
I WASH OIL TANK
Figure 10. Wash oil absorption of light oil with light oil rectification
(derived from Wilson and Wells6).
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process. After the acid wash, caustic is used to neutralize the acid and
the oil is separated from the aqueous waste.
Light oil refining on-site is often batch or semi-continuous, as the
practice reduces cost and increases the unit's flexibility. Products include
the forerunnings, benzene of various purities, as well as toluene and xylene,
washed solvent naphtha, and crude solvent naphtha.
Catalytic refining and/or hydrodesulfurization have been utilized at a
number of plants to produce very high purity benzene. The processes were
apparently successful but have not become widespread, possibly for economic
reasons.
4.7 SULFUR HANDLING
The sulfur in coke oven gas exists as H2S and the organic sulfur com-
pounds (primarily carbon disulfide, CS2, and carbonyl sulfide, COS). A
fairly typical coking coal might contain about I percent sulfur, and about
half the sulfur remains in the coke after carbonization. Perhaps 95 percent
by volume of the sulfur in the coke oven gas is in the form of H2S; of the
remainder, CS2 accounts for 3.5 percent and COS for 1.5 percent.
Sulfur is of concern in coke oven gas because it is emitted as S02 when
the coke oven gas is burned. Desulfurization has a long history, as sulfur
was once removed from gas for residential use by contact with iron oxide.
With the advent of natural gas in the 1950's, desulfurization became much
less common. Industrial fuel gas has not commonly been desulfurized, but
the recent natural gas shortages and price increases are causing reevalua-
tion.29 Desulfurized coke oven gas could serve as the primary sulfur-free
fuel source, at a price controlled by the steel producer. National stand-
ards for sulfur emissions due to coke oven gas combustion have not been
issued. The desulfurization facilities commissioned in this decade have
been in response to state or local standards.
On the surface coke oven gas desulfurization appears to be very similar
to desulfurization of some oil refinery streams, the technology for which is
well developed. Coke oven gas contains hydrogen cyanide, however, which is
a serious obstacle; many processes cannot be used. Cyanide is mentioned
below, but most of the relevant comments on cyanide have been gathered in a
later section.
45
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The distinction between organic sulfur and hydrogen sulfide is of some
interest because the desulfurization of coke oven gas rarely removes organic
sulfur. (The Sulfiban process is an exception.) Thus, the more completely
H2S is removed the more organic sulfur dominates what remains.
Process Alternatives
Leaving aside the outmoded use of iron oxide, there are essentially two
categories of process steps to achieve desulfurization of coke oven gas:
absorption of acidic gases in a basic solution, or absorption of reducing
gases in an oxidizing solution. Hydrogen sulfide is acidic, but so also are
HCN and C02. HCN is less completely absorbed because it is a weaker acid
and C02 absorption is impeded by slow reactions.30'31 Co-sorption of C02
merely increases the amount of base which must be circulated and the heat
required to regenerate it, but the unavoidable absorption of HCN creates
problems for downstream sulfur processing.
Hydrogen sulfide is a reducing agent but so are HCN, CO, COS, and CS2.
The last three are only sparingly soluble, so that these components of the
gas have little access to the oxidizing agent in the liquor phase. Future
catalyst developments may solve the problem of HCN interference, but it is
this nuisance which prevents the easy adaptation of technology originally
developed for sweetening natural gas and later applied to refinery gas.
Whatever the technique for removing sulfur from the coke oven gas, the
eventual disposal of the sulfur compounds is important. All of the modern
processes involve a regeneration step to recover process chemicals in which
the sulfur is separated again from the absorbent. In many cases a concen-
trated acid gas stream containing H2S is formed. The preferred way of
handling this stream is generally a Claus sulfur plant or production of
sulfuric acid by the contact process. Other processes regenerate by forming
elemental sulfur. Emissions from the regeneration step may be important and
must be examined.
Absorption in Basic Solutions
Three fully commercial processes for desulfurizing with a basic agent
are the vacuum carbonate process, developed by Koppers about 194030; the
Sulfiban process employing ethanolamine, adapted for present purposes by
46
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Bethlehem Steel and Black, Si vails, and Bryson early in this decade; and the
ammonia absorption process of Firma Carl Still.32
Vacuum Carbonate--
Koppers1 vacuum carbonate process enjoyed practically a monopoly in
U.S. plants until Sulfiban, according to a 1974 inventory.33 Dravo/Still is
a more recent entry in the race. Not to be outdone by the superior perform-
ance claimed for Sulfiban units, Koppers has recently responded with a
"two-stage" version of a vacuum carbonate,34 based perhaps on Shoeld's
patent,35 as shown in Figure 11. The classical, one-stage, version can be
identified with those portions of the absorber and stripper (traditionally
called an "actifier") labeled "primary". The circulating carbonate trickles
down through the packed absorber, removing H2S from the gas. It is then
pumped up and trickles down through the stripper, losing H2S to steam, and
is returned to the absorber. The acid gas is routed to a Glaus plant or
sulfuric acid plant for recovery of the sulfur. In the new version a por-
tion of the circulating carbonate leaving the primary stripper is returned,
to trickle down through a secondary stripper for more vigorous regeneration.
This doubly stripped absorbent then is pumped to the top of the secondary
absorber, where it contacts coke oven gas already treated in the primary
absorber.
Ammonia, tar, and naphthalene removal must be completed ahead of the
carbonate plant. Ammonia must be kept below 200 ppm, or it will cause prob-
lems in the Glaus plant after passing through the vacuum carbonate process.36
Tar and naphthalene will accumulate and foul the carbonate plant.
The stripper is operated at a high vacuum (10 cm Hg absolute). Contact
condensers are generally used on the stripper vapor to reduce fouling prob-
lems. Secondary reactions occur in the absorber, making a purge necessary
to remove thiocyanate and thiosulfate salts.
The performance of the absorber in this service is governed by the
choice of packing, its depth, the absorbent temperature, and composition,
the ratio of absorbent flow to gas flow, and the column cross-section per
unit of gas flow. These factors can be broken down into two sets: those
determining the local driving force for mass transfer (temperature, composi-
tion, and flow rates), and those determining the resistance to mass transfer
47
-------
"SWEET" COKE
OVEN GAS
VAPOR TO STEAM
JETS DRAWING
VACUUM
"SOUR" COKE
OVEN GAS
500
HEAT
SOURCES
ABSORBER
VACUUM STRIPPER
Figure 11. Koppers' two-stage vacuum carbonate process.
-------
(packing, depth, flow per unit area). Cooling and a high ratio of liquid to
gas improve the driving force in the absorber. Thus, if the primary absorber
were in all respects a duplicate of the single classical absorber, the
addition of more packing served with leaner absorbent (even though with
somewhat less absorbent) is bound to improve collection efficiency. The
same goal could have been accomplished, without resort to double staging, by
increasing the depths of both absorber and stripper and supplying more steam
to the latter. There is a presumption, however, that the two-stage arrange-
ment is more economical.
Certainly one feature of the new version is steam economy. Instead of
using fresh steam for the stripper, steam is derived by boiling the lean
absorbent. Since the absorber is under vacuum, the heat sources can be at a
relatively low temperature. Koppers recommends that the flushing liquor and
the steam from the ejectors serving the vacuum absorber be used as heat
sources.
Sulfiban—
The Sulfiban process and its antecedents have been adequately described
in the literature30'32'37'38 and will only be summarized here. Improved
basic data have recently been published.39 One could wish, however, for
reports from the two operators (Shenango, Jones and Laughlin) who have less
of a stake in the commercial success of this technology.
The Sulfiban process employs the conventional arrangement of an absorber
and a rebelled stripper. The absorbent is 13-18 percent mono-ethanolamine
(MEA) in water. Vapor for stripping at atmospheric pressure is generated in
a steam-heated reboiler. (It has never been made plain why the carbonate
absorbent is regenerated under.vacuum, while MEA is not. The arguments
concerning utilities consumption apply as well, qualitatively, to both.)
Again, the acid gas must be treated to recover the sulfur. The buildup of
stable by-products in the absorbent requires that about two percent of the
absorbent inventory be purged daily to a "reclaimer"; similarly, the buildup
of ammonium salts in the stripper condensate, which is normally refluxed to
the stripper to prevent amine losses, is controlled by purging to the weak
ammonia liquor.38
49
-------
The older literature14'30 contains repeated assertions that alkanola-
mines are degraded by the HCN and COS in coke oven gas. The proponents of
Sulfiban claim that this reputation is undeserved,37 and have been supported
by experience at the full scale unit of Bethlehem Steel.40 .Indeed, among
processes for absorption in basic reagents only Sulfiban absorbs significant
fractions of the COS and CS2 in the gas. Since these also form S02 when the
gas is burned, a process which removes them from the gas need not absorb as
much of the H2S to meet a standard which, like Pennsylvania's, limits total
sulfur emissions.
Dravo/Stlll--
A rule of thumb in chemical process synthesis is to avoid introducing
extraneous agents. Consistent with that philosophy, one might explore the
removal of H2S with ammonia liquor,30 and in fact this is the basis of a
range of process options offered by Firma Carl Still 22 and marketed in this
country by Dravo. Let us examine the process variant, shown in Figure 12,
which Dravo has installed for Armco at its Middletown, Ohio, plant. Anhyd-
rous ammonia and sulfuric acid are the products and as described, this is a
combination of two processes (USS PHOSAM and Dravo/Still) which could be
considered independently for ammonia and sulfur removal respectively. (The
description is based primarily on vendors' brochures and it is in part
conjectural.)
The coke oven gas is treated to remove acid gases (H2S, HCN, and inevi-
tably some C02) and ammonia in that order. The absorbent in the H2S scrubber
is aqueous ammonia, in such volume and strength as will lower the sulfur
content to the desired range. (COS and CS2 are little affected.) As shown
in Figure 12, the ammonia content of the absorbent derives from condensing a
wet ammonia vapor elsewhere in the system; but water from various sources
could be added to this stream.
When sodium carbonate is used to scrub coke oven gas, the acid con-
stituents removed from the gas are replaced by a comparable amount of innoc-
uous C02. Here the raw gas is enriched in NH3, which is normally removed by
H2S. The remedy is to reverse the order, to remove NH3 after H2S. The
agent of choice is phosphoric acid with a relatively small amount of ammonia
left in it after regeneration; it can be thought of as aqueous (NH4)H2P04.
50
-------
(Ji
H2S
ABSORBER
RAW COKE
OVEN GAS
DEPHENOLIZED
AMMONIA LIQUOR
CLEAN
COKE OVEN GAS
1
NH3
ABSORBER I
ABSORBER II
FREE
STILL
VAPOR FROM LIQUOR TO
FIXED STILL FIXED STILL
H2S1 HCN, C02TO
ACID PLANT
ANHYDROUS
RICH
PHOSAM
STEAM
W
AMMONIA
AMMONIA LIQUOR
PHOSAM
STRIPPER
LEAN PHOSAM
AMMONIA
STILL
STEAM
Figure 12. Dravo/Still processing.
-------
This is the so-called "Phosam" absorbent developed by U. S. Steel and first
commercialized by them at the Clairton Works in 1968. Since modest amounts
of NH3 are tolerable in the cleaned gas, the degree of recovery is set by
the economics of the process.
The rich absorbent leaving the H2S absorber could be steam-stripped in
a dedicated column, but this function can reasonably be combined in a new
plant with that of the "free still" which treats the crude ammonia liquor.
The vapors rising from the free still, containing most of the sulfur
and considerable ammonia, meet the Phosam solution descending from the NH3
absorber in a second absorber. Here the ammonia is removed to a degree
which satisfies the requirements of the sulfuric acid plant.
The rich Phosam absorbent passes to a stripper, where direct steam
removes the accumulated ammonia. The stripped or lean Phosam is recirculated
to the absorbers. The wet ammonia vapor goes to a condenser, from which is
derived the ammonia content of the absorbent used to remove H2S from the
gas.
The Phosam circuit processes all the ammonia used for absorption, as
well as a net make of ammonia from the raw gas and crude liquor. This net
is forwarded to an ammonia still, operated at about 12 bars (180 psia) to
permit the condensation of anhydrous ammonia against cooling water.
With the possible exception of the ammonia still, the optimal design of
all these units requires explicit recognition and management of the several
simultaneous ionic equilibria in the liquids being processed.
Cryogenic Sulfur Recovery--
A dramatic departure from the kind of technology described above was
announced in 1972 by U. S. Steel.^ A cryogenic desulfurization process was
installed at their Clairton Works. Hydrogen sulfide freezes at -82.9°C
(-117.2°F), and has a vapor pressure of about 0.2 bar (150 mm) there. But
since there is much less H2S than this in the coke oven gas, the process
cools' the gas to -130°C (-220°F) where the vapor pressure of H2S is below
0.004 bar (3 mm). Certain other constituents of the gas not earlier removed,
especially C02, may also condense in this process.
Absorption of H?S in Oxidizing Solutions
The solubility of H2S in water is quite small. The aim of absorption
52
—|-r
-------
in basic solutions is to convert the dissolved H2S to the hydrosulfide ion,
HS", making room for more H2S. By contrast, the aim of oxidizing systems is
to convert H2S to elemental sulfur or to sulfite, thiosulfate, or sulfate
ions. Various processes dating back to the turn of the century42 sought not
merely to desulfurize the gas but often to make the sulfuric acid required
in the ammonia saturators.
Thylox—
Perhaps the most important of these forerunners is the Thylox process,
first commercialized by Koppers in 1926. The process, as described by one
of the inventors,14 involves the displacement of oxygen from a thio-arsenate
moiety by H2S in a nearly neutral solution:
Na4As2S502 + H2S -»• Na4As2S60 + H20.
This is followed by the regeneration and simultaneous froth flotation of
sulfur product upon blowing with air:
Na4As2S60 + 1/202 -> Na4As2S502 + S.
The finely divided sulfur product, with unobjectionable levels of arsenic
for the purpose, found a market as an insecticide. The subsequent invention
of more powerful and specific insecticides has foreclosed this market.
Since arsenic contamination is a liability in other end uses for sulfur,
Thylox and an analogous modern process (Giammarco-Vetrocoke) have lost
ground.
Stretford—
Many of the same principles are found in the Stretford process, which
has been commercialized in this decade at a Canadian coke plant.43 The
chemistry, while not thoroughly understood, employs vanadium in a higher
valence state to oxidize H2S to elemental sulfur. In a separate device, air
blowing re-oxidizes the vanadium, with the help of an organic oxygen carrier,
and makes a froth of the fine sulfur.
Takahax—
A family of processes pioneered in Japan by Nippon Steel, and recently
commercialized in this country by Ford, Bacon and Davis—Texas, is called
53
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Takahax. Here the organic oxygen carrier dissolved in a basic absorbent
becomes the main oxidant; the metal salts are dispensed with. In the ver-
sion to be operated at Kaiser Steel, called Takahax-A,« ammonia is the base
and the chosen carrier is l,4-naphthoquinone-2-sulfonic acid. It appears
that this carrier was chosen deliberately for its greater oxidizing power,
the object being to form not elemental sulfur but soluble sulfur-bearing
anions which may feasibly build up in the circulating absorbent. A portion
of this strong solution is purged to wet-air oxidation, at conditions of 60
bars (880 psia) and 200°C or above. Here the catalyst is destroyed, the
sulfur species are converted to sulfuric acid, and any nitrogen emerges as a
gas or as ammonium ion. This product is sent to the saturator to be used in
ammonia recovery.
4.8 CYANIDE TREATMENT
Hydrogen cyanide, commonly called cyanogen in the coking industry, is a
minor but troublesome component of coke oven gas. No attempt is made to
collect it as a by-product, but the disposition of HCN and its salts in a
by-product plant is important both environmentally and with respect to
desulfurization processes. The mode of cyanide formation during coking is
obscure; indeed there is probably more than one route. Whatever the route,
HCN appears in the collection mains and is quenched. It is a weak acid, so
that some dissolves in the ammonia liquor, but most of it stays with the
gas.^ Most of that which dissolves is stripped out in the free ammonia still
and is returned to the gas. Normal operation of the free still does not
remove cyanide aggressively; some reaches the fixed still (if present and
operating) where it becomes fixed as calcium or sodium cyanide in the waste
ammonia liquor. From there it goes to wastewater treatment or to the receiv-
ing waters.
The PH of the excess ammonia liquor is mildly basic, say 9, but HCN is
such a weak acid that little of it is ionized at this pH. Thus, it would be
relatively easy to strip out in the free still if it were not so very polar.
(Liquid HCN boils at 26°C and is miscible in all proportions with water.45)
The motivation for operating the free still, and more especially the fixed
still, has traditionally been the value of recovered ammonia. The fate of
HCN was not important. In the base case considered in developing the effluent
54
-------
guidelines (Table 44 in Reference 46), conventional practice leads to a
cyanide level of 90 mg/1 (90 ppm) in the combined effluent of 730 1/kkg (175
gal/ton). Only 55 percent of the cyanogen is stripped out in the free still
and scarcely any in the fixed still.' Dunlap and McMichael assume only 40
percent removal.47 Clearly it is not important which of these control
efficiencies is more nearly correct;1 what matters is that neither is accept-
able. It is just as clear that redesign of the free and fixed stills, with
more plates, more steam, pH adjustment, or some combination of these,48
could reduce NH3, H2S, and HCN in the waste ammonia liquor to any desired
level. Other approaches may be preferable, to be sure.
The bulk of the cyanide, then, is found in the gas stream. Its fate
there depends upon processing options. It is preferable that it should be
deliberately destroyed, otherwise it may become an air pollutant.
Process Alternatives
Traditional Processing, with Ammonium Sulfate Production and No Desulfurization--
The coke oven gas passes through the tar removal step and a reheater;
is blended with wet ammonia vapor (containing some HCN) from the free still,
and passes to the saturator. Here ammonia is absorbed in sulfuric acid.
There may be some hydrolysis of HCN; most of the cyanide, however, evidently
passes through the saturator.
The next process unit, customarily, is the final cooler. The purpose
is to cool and dehumidify the gas before it goes to light-oil scrubbing, and
incidentally to remove naphthalene. The final cooler was historically
served by once-through cooling water in direct contact with gas. Pressures
from regulatory authorities have tended to reduce the volume and/or strength
of effluents. One of the responses by the coking industry has been to shift
from once-through water to recirculated water, with a cooling tower in the
circuit. Some HCN dissolves in the water in this arrangement; data for
Bethlehem's Lackawanna plant49 attest that on the order of 50 percent enters
the water. Other versions have usect water and tar jointly (so that the
!
naphthalene is returned to the tar)| wash oil,49 or indirect cooling. The
inlet water temperature varies seasonally, and the water rate is adjusted
with the season, less being required in the winter. The absorption of HCN
is inevitable but is not a criterion of performance. The amount absorbed
i
varies seasonally and is difficult to anticipate.
,55
-------
We may gain some quantitative grasp of the problem from published
analyses of waste loadings in coke plants. "Plant D" in the EPA Development
Document46 employed once-through cooling water, which was evidently the
largest component of total raw waste load of 19,200 liters per 1000 kg of
coke. The cyanide content was 7.7 mg/1, for an aggregate cyanide output of
150 g/kkg or 0.015 percent. Comparable numbers for Plants A, B, and C are
0.006, 0.006, and 0.002 percent. Not all of these amounts come from the
final cooler, of course, The circumstances of Plant D, direct cooling with
once-through water, suggest that this is the most cyanide which will be
removed from the gas (discounting seasonal variations). Previously it was
shown that domestic coking coals are remarkably uniform in their nitrogen
content, and that a nearly invariant fraction of this nitrogen emerges with
the coke. The ammonia production and the coking conditions thus lead us to
anticipate that HCN production is fairly uniform at 0.05 percent. Clearly
Plant D does not remove even the bulk of it, and the other three plants not
as much, by this route.
What is the situation if the final cooler is served with recirculated
water derived from a cooling tower, possibly dedicated to this service?
If only the water is considered, there are evaporative and drift losses
and a blowdown to control hardness and/or corrosion. But from the stand-
point of cyanide we now see an absorber (the gas cooler) and a stripper (the
water cooler); most of the cyanide picked up by the cooling water will be
discharged to the air. The temperature of recirculated cooling water cannot
be below the dew point of the ambient air, and operating policy may restrict
the temperature to, say, 15 to 30°C. But the point is that this temperature
varies seasonally and is not unlike that of once-through water at the same
site, so that the water rate and cyanide content will be comparable to those
at Plant D. We conclude that a direct final cooler using recirculated water
could easily emit HCN to the ambient air in the amount of 0.1-0.2 kg per Mg
of coal.
What of the light-oil plant? Recall that the coke oven gas is contacted
with a lean wash oil which, upon leaving the absorber loaded with light oil
and containing some HCN13, is routed to a stripping column. Where that
column is served with open steam, the condensate separates into two layers:
light oil and a sour water containing some HCN.47 We must conclude that
56
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some HCN is not condensed and becomes an air pollutant at that point, but
the amount is much more difficult to quantify. Since HCN is a polar mole-
cule, much more soluble in water than in oil, we may guess that this source
is small compared to that from the kind of cooling tower described earlier.
In many plants the gas leaving light-oil recovery is distributed to the
coke-oven burners and other fuel consumers in the plant. Cyanogen is a
nuisance in distribution systems, gas meters, gas holders, and burners13
because it forms a corrosive acid at the dewpoint:
18HCN(aq) + 7Fe(s) - Fe7(CN)18(s) + 9H2(g).
The salt, prussian blue, precipitates; it can also happen that when the line
warms up and dries out the salt is carried along with the gas to where it
blocks burner orifices, especially pilot lights.
Processing with Sulfur Recovery-
When desulfurization is practiced, HCN again makes its presence felt.
This acid gas is almost completely absorbed by basic solutions, as in vacuum
carbonate, Sulfiban, or Dravo/Still. (See Section 4.4.) When the absorbent
is regenerated or "actified" the HCN joins the H2S, to create problems in
the Claus plant49 or in the burners of a sulfuric acid plant.
Cyanogen is also a reducing gas. In Stretford and Takahax chemistry it
dissolves and reacts with elemental sulfur to form thiocyanate ion:
HCN(aq) * S(S) * °H(aq) * SCN(aq)+H*°-
The alkalinity can be restored, but sodium or ammonium thiocyanate builds up
until it must be purged. Even though Dominion Foundries and Steel (Dofasco)
at its Hamilton, Ontario, plant practices water washing to remove HCN ahead
of their Stretford plant, the necessity for purging remains.43 Dofasco has
recently attached a purge-treatment process devised by Holmes of U.K. and
marketed in this country by Wilputte. Similar systems are offered by Woodall-
Duckham, by Nittetsu Chemical50 and, for the Takahax process, Nippon Steel.44
The first three are essentially incineration processes which recover sodium
and/or vanadium values as solids and recycle sulfur as H2S to the inlet of
the sulfur recovery system. The last employs wet-air oxidation to ammonium
sulfate/bisulfate, which is recycled to the ammonia-recovery system.
57
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Since a purge- treatment system seems to be required in order to cope
with the buildup of thiosulfate (Section 4.4), it is problematical whether
it is worthwhile to try to exclude HCN from the H2S absorber. If HCN pre-
treatment is by water washing, as at Bethlehem's Sparrows Point Plant,49
regeneration with air would create air pollution. If ammonium polysulfide
scrubbing is practiced,51 this absorbent must be purged; there is no known
regeneration technique.
When finally the rich H2S stream is to be made into something useful,
there are two principal choices: elemental sulfur by Claus or other chemis-
try, or sulfuric acid by the contact process.
Since hydrogen cyanide is detrimental to the sulfuric acid process, the
practice at Sparrows Point is to cool the acid gas and pass it through an
absorber served with water. Some 90 percent of the HCN is removed, and the
water is heated and stripped with sweet coke-oven gas destined to be burned
under the coke ovens.52 Although Sparrows Point has gone to the Claus
process for sulfur recovery, this water wash is still operated.49
Cyanogen causes corrosion and blockage in Claus plants,49 so Bethlehem
has demonstrated a remedy: the acid gas from its vacuum carbonate units at
Burns Harbor and Lackawanna is passed over a "destruct reactor," an extra
bed of Claus catalyst installed before the Claus burner. Here, in a series
of reactions which are jointly exothermic, HCN and oxygen disappear; and
ammonia, carbon monoxide, carbonyl sulfide, and carbon disulfide appear in
the outlet.49 Probable reactions are as follows, all compounds being gas-
eous:
HCN
2CO
CO
C02
COS
+ H20 -»•
+ 02 -
+ H20 ->
+ H2S •*
+ H2S ->
NH3 +
2C02
C02 +
COS +
CS2 +
CO
H2
H20
H20.
The first two reactions have a favorable free-energy change at all
relevant temperatures. The last two reactions have weakly unfavorable
equilibrium constants, but they can be driven by the excess of H2S and the
absence of organic sulfur in the feed. No one pretends that these are the
58
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elementary reactions. Rather, these reactants are chemi-sorbed on the Claus
catalyst, dissociated in one or more stages to adsorbed free radicals such
as HCO and HS«, rearranged, and desorbed.
4.9 WASTEWATER PROCESSING
Wastewater treatment is a necessary part of the coking operations, as
raw coke oven gas contains water vapor driven from the coal in the coke
oven. This water vapor is due to both surface moisture on the coal and
bound water. Depending on coal type and coking practice, the flow of waste-
water originating in the coke is around 100 to 200 1/Mg coke. Most of the
water initially in the coke oven gas is condensed into the flushing liquor
circuit described earlier. The blowdown from the flushing liquor circuit is
known as weak ammonia liquor, and is the primary wastewater stream. Ammonia
and phenols may be recovered from this stream. Once past the recovery
sections, the water stream is waste ammonia liquor.
Wastewaters from other sources within the by-product plant are often
combined with the waste ammonia liquor for treatment. These waste streams
are highly dependent upon the processes used in the by-product plant. Some
of them are unavoidable; others can be either greatly reduced or eliminated
by proper choice of process technique. The major secondary sources of
wastewater are:
1. barometric condenser water from steam jets used to draw vacuum
on the ammonia crystal!izer;
2. steam stripping waste from wash oil and light oil decanters;
3. blowdown from the final cooler.
In one sense, ammonia and phenol recovery from weak ammonia liquor are
wastewater cleanup operations. However, they are being treated as by-product
recovery processes, and this section deals only with operations downstream
of ammonia and phenol recovery if these processes are used.
Weak (Waste) Ammonia Liquor
Flushing liquor contains tar, phenol, ammonia, and cyanide along with
chlorides, sulfur compounds, and a host of hydrocarbons. Tar decanting re-
moves most of the tar. As has been described, the blowdown from flushing
liquor, excess ammonia liquor, goes through additional separation steps
59
-------
before phenol and ammonia are recovered. Table 10 presents a major compon-
ent analysis of weak ammonia liquor prior to any recovery or clean-up process.
Following the decanters, weak ammonia liquor may be processed to recover
phenols and ammonia. These operations have been discussed. Conventional
phenol removal is 90-95 percent effective, and a free and fixed still combi-
nation can drop ammonia levels to around 150 mg/1, as well as stripping out
most of the cyanide in the free still. In spite of these fairly high levels
of removal, waste ammonia liquor requires additional treatment before being
discharged to receiving waters.
Barometric Condenser Water
Barometric condenser water from vacuum ammonia crystal!izers is a high
volume wastewater (1000 1/Mg coke). The waste can be greatly reduced in
volume by using surface condensers rather than barometric condensers. This
step has led23 to an order of magnitude reduction in rate. No literature
reference has been found to the use of vacuum pumps to draw the low pressure
on the crystallizer as a way of nearly eliminating this waste. Presumably
the service is thought to be too severe. An attempt has been made to use
recycled water in a cooling tower, but this system had problems with corro-
sion and pH control.
Intercepting Sump Water
Decanted water from the light oil plant is another large volume source
of wastewater (300 1/Mg coke). This waste is primarily due to steam strip-
ping of light oil from wash oil. The waste could be avoided by using reboil-
ers for non-contact heating with steam. Extra attention would probably be
TABLE 10. MAJOR COMPONENTS OF WEAK AMMONIA LIQUOR18'23
Ammonia
Phenol
Cyanide
Oils
(mg/1)
5,000-6,000
1,500-2,000
20-60
1,000
60
-------
required to keep the reboilers clean. One firm has published.plans to put
their light oil separator water into the final cooler makeup.53 This waste-
water can also be blended with ammonia liquor, then treated at the plant
wastewater treatment facility.
Final Cooler Slowdown
Another significant source of wastewater in the by-product plant is the
final cooler blowdown, necessary to control buildup of chlorides in the
cooling water. A tightly recycled system is needed to keep the volume of
this waste to the lowest possible level. The final cooler blowdown is
generally combined with the ammonia liquor and other wastewaters for a one
step treatment.
Treatment Options
Wastewater treatment options abound, and the methods tend to overlap
and interact with respect to the results. Figure 13 outlines many of the
more or less traditional options and their effectiveness. Another approach23
which has been tested at pilot scale is a completely integrated wastewater
treatment scenario developed by Republic Steel and shown in Figure 14.
61
-------
rvj
INTERCEPTING SUMP WASTEWATER
BAROMETRIC CONDENSER WASTEWATER
o
SO-2003
f
0.5
0.13
|
0.25
2.3
§
E
1974 BPCTA
DUNLAP
46
O.t 0.05 10 SCHROEUER
,23
60200" 1-2 40
50-200"
1-2
150
20-30
40
1015 1974 BPCTA
100 DUNLAP1
46
NOTE: a. Can reduce to 50 mg/l using caustic, 100-200 mj/1 with lime.23
Figure 13. Coke by-product plant wastewater treatment options.
-------
en
COKE PLANT
WASTEWATER
SPENT
PICKLE
LIQUOR
POLYMER
FILTER
SLUDGE
T
SLUDGE TO FURTHER DEWATERING
AND COKE OVEN FEED
MIXER
LOW 0,
GAS
FLOTATION
AMMONIA
CAUSTIC
STEAM
FILTRATE
CLARIFIED
LIQUOR
CLEAN CARBON
VENT
AFTERBURNER
GAS OR STEAM
SPENT CARBON
_J
TREATED EFFLUENT
AMMONIA STILLS
CARBON ADSORBERS
(DEPHENOLIZATION)
CARBON
REGENERATOR
Figure 14. Complete wastewater treatment scenario
23
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5.0 STATUS OF BY-PRODUCT RECOVERY TECHNOLOGY IN THE UNITED STATES
5.1 INTRODUCTION
Slightly more than half the by-product coke plants in operation today
began coke production prior to 1930. Construction was apparently deferred
through the 30's, with new plants again being built in the early 40's and
50's. Only a few plants have started production in the 60's and 70's. The
point of this is that many by-product plants were built when coal was the
primary source of many important chemicals and by-product recovery was a
profitable business. Today, chemicals from petroleum are available in large
volumes, at relatively low prices, and with high purity. Chemicals from
coal make up a much smaller share of the market and the prices are con-
trolled by the petroleum based chemicals. Coal chemicals were becoming
progressively less competitive through the 1960's, and by-product plant
operators were losing money on ammonia, for instance.26 Existing facilities
for tar refining and light oil refining were sometimes decommissioned,
sometimes not repaired, as small-scale refining wasn't profitable. Today,
with the price of all energy sources rising, the economic situation with
respect to by-product plants is not clear, but has improved somewhat.
The precise status of by-product plant technology was not determined
during this study and is not directly available in the literature. It is
possible to get a reasonable picture of the major processing technologies in
use today from the 1977 AISI Directory.54 Table 11 presents a summary of
the information obtained from the directory. It should be pointed out that
Table 8 rests heavily on the assumptions listed in the notes, and there are
almost sure to be some inaccuracies, particularly with regard to the pro-
cessing of excess ammonia liquor and the final cooler/naphthalene processing
routes. The AISI directory lists those coke plants associated directly with
the steel industry, providing a short list of products and an abbreviated
list of processes for each plant. Those coke plants not listed are gener-
ally smaller plants, the omissions being the plants of Allied Chemical Com-
64
-------
TABLE 11. USE OF COKE BY-PRODUCT RECOVERY TECHNOLOGIES IN THE UNITED STATES
PLANTS
Alan Wood Steel Company, Swedeland, PA
Armco - Houston Works, TX
Armco - Middleton, OH
Armco — Hamilton, OH
Bethlehem - Bethlehem, PA
Bethlehem - Sparrows Point, MO
Bethlehem - Lackawanna, NY
Bethlehem - Johnstown, PA
Bethlehem - Burns Harbor, ID
C, F & 1 - Pueblo, CO
Crucible, Inc. - Midland, PA
Cyclops Corp. - Portsmouth, OH
Ford Motor Co. - Dearborn, Ml
Inland Steel - E. Chicago, ID
Interlake, Inc. - S. Chicago, IL
Interlake, Inc. - Erie, PA
Interlake, Inc. - Toledo, OH
International Harvester - S. Chicago, IL
Jim Walter Resources - N. Birmingham, AL
Jones & Laughlin - Aliquippa, PA
Jones & Laughlin - Pittsburgh, PA
Kaiser Steel - Fontana, CA
Lone Star Steel - Lone Star, TX
National, Great Lakes - River Rouge, Ml
National, Weirton - Weirton, W V
i
0
o
E
a
Z
110
62
iau
11!)
364
751
494
315
164
143
113
70
205
502
100
58
57
45
240
327
315
315
78
233
336
"s
1
X
i
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
TAR
1
o
•f
fe
X
X
J
X
1
M
"8
S
X
PRIMARY
COOLER
I
a
X
X
X
X
X
X
X
X
X
X
X
Nl
X
X
X
X
X
X
k
1
X
X
X
X
X
X
Nl
X
X
AMMONIA
HANDLING
1
a
i
o
•9
a
.a
X
Nl
X
X
X
X
X
X
X
X
X
X
X
X
Nl
X
X
X
X
X
X
X
X
1
S
a.
2
i
e
e
'&
1
Nl
X
Nl
X
"1
I
S
1
?
?
Nl
X
e
o
S
?
o.
o
X
X
X
?
X
X
FINAL
COOLER
o *"
II
o S
Nl
X
X
X
X
X
Nl
X
|
|
! i
X
Nl
?
X
X
X
X
X
X
X
X
X
Nl
X
X
X
X
X
5
1
r
0)
O
Nl
?
?
X
X
Nl
f
1
1
Nl
X
X
X
X
X
Nl
X
LIGHT
OIL
1
o
S.
G
X
Nl
X
X
X
X
X
X
Nl
X
X
X
X
X
X
Nl
X
X
X
X
X
X
X
X
X
*"=
I
c
G
X
Nl
X
X
X
X
X
X
Nl
X
X
X
SULFUR
c
S
a
Q
Dravo/Stil
Sulfiban
X
X
X
VC
VC?
VC
O)
B
S
•s
i
1
55
55
55
5551
5553
65,51
55
56
COMMENTS
Status of Company Uncertain
Koppers Benzol Plant; Coke Oven Gas Incinerated
Wilputte Benzol; Phosam Process
Otto Benzene Plant, Claus Sulfur
Koppers Benzene Plant, Claus Sulfur
Otto Benzene Plant
Koppers Benzene Plant
Also Produce Pyridine
Tar Distillation Available - Use Uncertain
Koppers Benzene Plant; Only Tar Produced
Koppers Benzene Plant
Semet-Solvey & Koppers Benzene Plant(s)
Koppers Benzene Plant & Badger Hydrofiner Plant
Produces Tar Acids
Ammonia Destruction
o>
tn
See footnotes and legend at end of table.
-------
TABLE 11 (continued)
PLANTS
National, Granite City - Granite City, IL
Republic Steel - Youngstown, OH
Republic Steel -Warren, OH
Republic Steel - Massillon, OH
Republic Steel - Cleveland, OH
Republic Steel - S. Chicago, IL
Republic Steel - Gadsden, AL
Republic Steel - Birmingham, AL
Sharon Steel - Fairmont, WV
Shenango, Inc., - Neville Island, PA
U.S. Steel Corp. - Clairton, PA
U.S. Steel Corp. - Fairtess Hills, PA
U.S. Steel Corp. - Lorain, OH
U.S. Steel Corp.- Duluth.MN
U.S. Steel Corp. - Gary, ID
U.S. Steel Corp. - Geneva, UT
U.S. Steel Corp. - Fairfield, AL
Wheeling-Pittsburgh - E. Steubenville. WV
Wheeling-Pittsburgh - Monessen, PA
Youngstown S & T - Campbell, OH
Youngstown S & T - E. Chicago, ID
in
O
O
S
e
a
2
137
162
80
31
330
75
130
65
60
105
1,314
174
413
115
584
252
489
224
93
228
237
TAR
f
ar Hand
*
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
1
O
1-
£
n
X
X
Nl
X
Nl
X
X
LIGHT
OIL
6
1
cc
„
.5*
X
X
X
X
X
X
X
X
X
X
X
X
X
Nl
X
X
X
X
X
X
X
».
'£
•fi
c
o
X
X
X
X
Nl
X
X
SULFUR
O
•I
"3
0)
a
Carbonate
Claus
SCOT
a
o
g
&
55
-
55
COMMENTS
Produce Solvent Naphtha & Naphthalene
Handles Some Chemicals From Other USS Plants
Wide Range of Processing Facilities
Wilputte Vacuum (NH4 1, S04 Crystallization
Anhydrous NH, Plant
Koppers Benzene Plant
Semet-Solvey Plant
Sell Ammonia Liquor, No Sulfate
CD
CT>
Vacuum Carbonate Desulfurization
No information sufficient to make a decision.
: Reason for question; lack of conclusive data.
LEGEND
VC
Nl
?
NOTES
a Assumed true for all byproduct plants.
b Assumed true if tar not listed among byproducts.
'includes Phosam, Anhydrous ammonia processes, Ammonia destruction, etc.
dTar bottom final cooler assumed if naphthalene not listed among byproducts.
'Assumed if naphthalene listed among products unless tar refining practiced.
'Assumed if light oil products, i.e, Benzene, toluene, xylene, etc., listed separately.
9Sources other than 1977 AISI Directory, Reference 54 & 1974 AISI Directory, Reference 22.
-------
pany, Koppers Company, Donner-Hanna Coke Corporation, Alabama By-products
Company, and several small gas and chemical producers. The information
developed in Table 11 is discussed more fully in the following sections.
Information presented concerning the economics of by-product recovery
processes was developed by Wilputte Corporation by factoring and escalating
designs which had been developed for their customers. All costs are based
on the third quarter of 1977. Details are presented in Appendix B.
5.2 TAR PROCESSING
Coal tar production is unavoidable, and all by-product plants have to
deal with it. The tar is initially contained in flushing liquor or a con-
densed water phase and is physically separated from the aqueous phase in
decanters. Emulsion breakers may or may not be used.
Dewatering of tar beyond decantation is described in the literature,
but no information as to frequency of use is available. Two types of de-
watering equipment could be used: (1) mechanical, such as centrifuges, or
(2) heating to elevated temperatures to drive off the water. The use of
dewatering equipment depends on the requirements of the tar end-use.
Tar storage may be at elevated temperatures (80° C) to facilitate
handling this moderately viscous material. The storage vessels are used for
additional decanting at some plants.
The large number of useful chemicals contained in coal tar were once
recovered profitably by refining. Table 11 indicates that only six to eight
coke plants still have tar refining equipment and it is likely that not all
the tar plants listed are operated. According to a Bureau of Mines report,1
the disposition of crude coal tar in 1975 was roughly 25 percent refined in
some degree by the four to eight plants, 25 percent burned by the producer,
and the remainder sold to tar distillers.
Coal tar as fuel has risen in favor as the price of fuel has increased.
It is possible to burn "cut-back pitch" (tar refining residue diluted with
crude tar) as a replacement for Bunker C fuel oil, and it is probable that
some tar refiners burn a portion of their tar in this way.
Tar refining can range from simple "topping" to fairly elaborate distil-
lation equipment and sulfur removal capability. Clairton Works of US Steel
appears to have the most elaborate tar processing plant among the plants
67
-------
listed by the AISI, producing pitch, pitch-tar mixtures, creosotes, desul-
furized naphthalene, and tar acids. Gary Works of US Steel also apparently
makes more than one distillate from tar. The other plants included in
Table 8 are thought to practice only "topping," a single stage distillation
separating pitch and chemical (creosote) oil.
5.3 AMMONIA HANDLING
Most U.S. by-product plants operate in a semi-direct mode with respect
to ammonia; that is, the ammonia is distributed between the flushing liquor
•
and the coke oven gas stream. A couple of plants scrub the coke oven gas
with water to remove the remaining ammonia and thus put all the ammonia into
the liquor; the product of this (indirect) process is aqueous ammonia.
The majority of plants using the semi-direct process must decide what
to do with the ammonia in the gas and that in the liquor. Three alternatives
are used to treat the liquor: no treatment, free still ammonia stripping,
and free and fixed still ammonia stripping. Based on a recent EPA survey55
of the by-product coking industry, all three alternatives are in use. Out of
the 52 plants 33 (63 percent) utilized or were planning both free and fixed
stills, four of the plants (8 percent) utilized only free stills, and the
remainder apparently did not attempt to recover ammonia from excess ammonia
liquor. Once stripped from the liquor, the ammonia is generally routed to
the coke oven gas for recovery. Ammonia destruction by incineration is
practiced in a few plants. Recovery of ammonia from the coke oven gas is
practiced in all the plants that burn coke oven gas as fuel. Only Armco,
Houston, is known to incinerate coke oven gas. As shown in Table 11, the
majority of plants recover ammonia in some type of scrubber, producing
ammonium sulfate in most cases (87 percent) and a phosphate salt in others
(4 percent). One plant incinerated its entire ammonia stream. Clairton
®
Works of US Steel produces anhydrous ammonia, utilizing the Phosam process,
and the Geneva Works of US Steel apparently has an ammonium nitrate fertil-
izer plant on-site.
As shown by the cost estimates presented in Appendix B, ammonia
recovery plants are not moneymakers. Ammonia stills to remove ammonia from
excess ammonia liquor (6 g/1 to 0.015 g/1) have a total operating cost of
around $0.23/100 1 of ammonia liquor ($383 per 1,000 kg of recovered ammonia).
68
-------
An ammonium sulfate recovery unit operates at a net loss of about $140 per
1,000 kg of ammonia recovered as ammonium sulfate. An existing plant which
could be considered fully depreciated, eliminating capital charges, would
just about break even.
®
A Phosam type anhydrous ammonia plant loses nearly $160 per 1,000 kg
of recovered ammonia when capital charges are included.
Of course, the ammonia needs to be removed as a gas purification step,
so ammonia recovery of some type is a necessary cost.
5.4 PHENOL RECOVERY FROM AMMONIA LIQUOR
Phenol recovery at by-product plants is uneconomical, and must be looked
on as a step in the wastewater treatment. As is shown in more detail in
Appendix B, straightforward biological treatment of ammonia liquor for
phenol removal is a bit less expensive than building and operating a light
oil phenol recovery system, and does a better job of removing phenol. If
the dephenolization equipment is in place, operating it is not as expensive
as the biological treatment, although some form of additional treatment will
be required. About 25 percent of the existing by-product plants use tradi-
tional phenol recovery,55 generally as sodium phenolate. Light oil absorp-
tion is apparently a more popular process than vapor recirculation, perhaps
due to the tar acids removal effected in a light oil absorber.
5.5 FINAL COOLER AND NAPHTHALENE RECOVERY
Three forms of final cooler and naphthalene recovery technology are in
use:
(1) cooling with water and naphthalene recovery by physical separa-
tion; or
(2) cooling with water and naphthalene recovery into tar in a tar
bottom final cooler; or
(3) cooling with a wash oil which also absorbs naphthalene.
The data in Table 11, above, indicate that about 25 percent of the plants
utilize direct water cooling and physical naphthalene recovery, 60 percent
utilize tar bottom final coolers, a couple of plants utilize wash oil cool-
ing, and technology at the other plants is not available. The assumptions
used in developing Table 11 tend to put uncertain choices in the tar bottom
69
-------
category, however, and thus these numbers should be considered only rough
estimates. No information was located concerning the frequency of use of
recirculated versus once-through water in the contact final cooler.
The status of naphthalene handling technology after physical separation
is not known. The water in the slurry must be decanted or otherwise removed
before the naphthalene can be shipped, so some additional handling is needed
if water contacts the naphthalene. One variation55 is to dissolve the
naphthalene in coal tar after physical separation.
The choice of final cooler type will have a significant impact on the
distribution of some pollutants in a by-product plant, cyanide being a good
example. If the cyanide is not removed in the final cooler water, it re-
mains in the gas and causes problems downstream. If it is not stripped out
of recirculating cooling water, the blowdown will be high in cyanide and the
wastewater plant will be more heavily loaded.
5.6 LIGHT OIL RECOVERY
With few exceptions, light oil is recovered from coke oven gas by wash
oil absorption in the United States. Light oil refining capability is
present at about 35 percent of the plants listed in Table 11, mostly, but
not exclusively, at larger plants. As many of the by-product plants not
listed in Table 11 are associated with chemical companies, the fraction
refining light oil may well be higher in that group. The products of the
refining operations are mostly benzene, toluene, xylene, and solvent naphtha.
No data are available to indicate the prevalence of desulfurization of the
light oil, although desulfurization is necessary if the light oil products
are to compete in the marketplace.
5.7 DESULFURIZATION TECHNOLOGY
The existing U.S. coke oven gas desulfurization plants have been listed
in Table 12. No desulfurization technology has proven clearly superior, and
all the options appear to be under consideration. Massey and Dunlap29'32
have presented net amortized capital and operating costs for vacuum carbonate,
Sulfiban, Firma Carl Still, and Stretford (with effluent treatment) desulfur-
ization. The Stretford process was the least expensive ($0.0557/Mscf gas) of
the high efficiency processes (vacuum carbonate-$0.0717, Sulfiban $0.0825/Mscf),
70
-------
TABLE 12. COKE OVEN GAS DESULFURIZATION PLANTS IN THE UNITED STATES32 54 55
Plant
H2S Removal From
Coke Oven Gas
Sulfur
Recovery
Armco Steel, Middletown Coke Plant Firma Carl Still/Dravo Sulfuric Acid
Bethlehem Steel Company
Bethlehem, PA
Sparrows Point, MD
*Johnstown, PA
*Lackawanna, N.Y.
Burns Harbor, ID
Donner Hanna Coke Corp.,
Buffalo, N.Y.
Inland Steel Co., Indiana
Harbor, ID
J & L, Pittsburgh, PA
National Steel, Weirton, WV
Shenango, Inc., Pittsburgh, PA
U.S. Steel, Clairton, PA
Wheeling-Pittsburgh Steel,
Follansbee, WV
Sulfiban
Vacuum Carbonate
Vacuum Carbonate
Vacuum Carbonate
Vacuum Carbonate
Vacuum Carbonate
Vacuum Carbonate
Sulfiban
Vacuum Carbonate
Sulfiban
Vacuum Carbonate
Firma Carl Still/Dravo
Claus Plant
Claus Plant
Claus Plant
Claus 'Plant.
Claus Plant
Claus Plant
Claus Plant
Claus Plant
Claus Plant
Sulfuric Acid
*May switch to Sulfiban.57
but it is also the system with the most limited experience in the United
States. For the same degree of removal (99 percent) and plant size, Sulfiban
was estimated to be more expensive than vacuum carbonate systems by $0.01
per 1,000 scf of coke oven gas. At the lower efficiency levels (90-93
percent) Sulfiban, Firma Carl Still, and vacuum carbonate were all about the
same in cost. Economics of scale were found to be important with costs per
volume of gas being $0.02-$0.03/Mscf gas less for 60,000,000 scfd plants
than for 20,000,000 scfd plants. Sulfuric acid production costs $0.005 to
$0.015/Mscf more than Claus plant sulfur production. High efficiency desul-
71
-------
furization (99 percent) costs around $0.02/Mscf more than does low effi-
ciency (90-93 percent).
The estimates by Massey and Dun!op do not include by-product credits.
Most plants recover the sulfur in a CVaus plant, although some of the newer
plants recover sulfuric acid. A three- to four-year payout for sulfuric
acid plants was estimated in 1975 for acid prices of around $40/ton. Dis-
counting inflation, acid prices were at about that level in the third quarter
of 1977, so acid recovery might be a reasonable investment.
5.8 STATUS OF WASTEWATER TREATMENT
The available data on the status of wastewater treatment are presented
in Table 13. As has been described in earlier sections, excess (waste)
ammonia liquor is usually partially treated separately, then combined with
the other wastewater streams for final treatment and disposition. About 70
percent of the plants utilize ammonia stills and 25 percent dephenolize
ammonia liquor. Wastewater treatment scenarios from this point in the flow
plan are diverse. Thirteen plants use or plan biological oxidation as part
of their treatment scheme; four use or plan chemical oxidation.
As to the ultimate disposition of the wastewater:
14 plants (27 percent) discharge to receiving waters following the
by-product plant wastewater treatment;
11 plants (21 percent) discharge to public treatment facilities;
14 plants (27 percent) use part of the coke plant wastewater as
quench make-up and discharge the remainder to receiving waters (9
plants), public facilities (3 plants), central treatment (1 plant),
or deepwell injection (1 plant);
9 plants (17 percent) quench by-product plant wastewater to extinc-
ti on;
the remaining 4 plants utilize incineration, reuse, central treat-
ment, and impoundment.
Tight control of the amount of water blowdown is another way to reduce
wastewater loadings. Dunlop and McMichae!18 have estimated that plants with
tight recycle systems discharge a total of about 480 1/Mg coke (115 gal/ton
coke) and that loose recycle systems discharge 1200 1/Mg coke (290 gal/ton).
Table 13 indicates that 6 plants recycle barometric condenser water from
vacuum crystal!izers; unfortunately, the number of vacuum crystal!izers was
72
-------
TABLE 13. STATUS OF BY-PRODUCT PLANT WASTEWATER TREATMENT PROCESSES
1 . Alabama Byproducts - Tarrant, AL
2. Alan Wood - Conshohocken, PA
3. Armco - Middletown, OH
4. Armco - Hamilton, OH
5. Armco - Houston, TX
6. Bethlehem, - Bethlehem, PA
7. Bethlehem - Sparrows Point, MO
8. Bethlehem - Lackawanna, NY
9. Bethlehem - Johnstown, PA
10. Bethlehem - Chesterton, IN
11. Citz. Gas & Coke - Indianapolis, IN
12. Cyclops -Portsmouth, OH
13. Donner-Hanna - Buffalo, NY
14. Philadelphia Coke - Philadelphia, PA
15. Ford Motor- Dearborn, Ml
16. Missouri Coke & Chem. - St. Louis, MO
17. Inland Steel -E.Chicago, IN
18. Interlake -Chicago, I L
19. Interlake -Toledo, OH
20. International Harv. - Chicago, IL
21. J& L - Aliquippa, PA
22. J & L - Pittsburgh, PA
23. Kaiser - Fontana, CA
24. Koppers -St. Paul, MN
25. Koppers - Erie, PA
26. Koppers — Bessemer, A L
27. Lone Star - Lone Star, TX
28. National, Great Lakes - River Rouge, Ml
29. National -Granite City, IL
30. National - Weirton, WV
31. Milwaukee Solvay -Milwaukee, Wl
Coke
Production
Mg/day
(tons/day)
Typical
1.945 (2,140)
1,114 (1,225)
1,285 (1,414)
1,646 (1,811)
763 (840)
4,599 (5,059)
8,330 (9,163)
6,280 (6,908)
3,660 (4,026)
4,708 (5,179)
911 (1,002)
1,041 (1,145)
1,500 (1,650)
800 (880)
3,586 (3,945)
727 (800)
6,547 (7,202)
1,327 11,460)
638 (702)
636 (700)
4,094 (4,504)
4,754 (5,230)
3,454 (3,800)
454 (500)
545 (600)
1,156 (1,272)
627 (690)
4,727 (5,200)
1,584 (1,743)
7,075 (7,783)
536 (590)
USE OF PARTICULAR PROCESS COMPONENTS1
Carbon Treatment
Free Still
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
Fixed Still
N
N
N
F
F
N
F
N
N
N
N
N
N
N
N
N
N
N
N
a
a
°o
c
01
a
N
N
N
N
N
N
N
N
N
Bio-Oxidation
F
OS
F
N
F
F
F
N
c
Chemical Oxidatio
OS
N
N
F
Recycle Baro.
Cond. Water
N'
N
N
Byproduct
Plant Waters
Used For
Quench
(Note 2)
FC
FC, BC
EAL, BzP, FC
FC.BC.DS
EAL
FC
BzP. FC
EAL, BzP, FC
EAL, BzP, FC
FC
EAL, FC
BzP, FC
— ^=""^=
Process
Outfall
Flows l/Mg
(gal/ton) Additional Data-l/Mg (gal/ton)
Typical And Comments
629 (151)
366 (88)
237 (67) To POT
271 (65)
none Incinerated
495 (119)
unknown
unknown
none To quench
none 179 (43) deepwell injection
1,066 (256) To POT alter settling & skimming
391 (94) Plus 982 (236) to quench
216 (52) Process. 19,186 (4,608) total
333 (80) To POT
1,678 (403) To POT
unknown
299 (72) To POT
2,873 (690) To POT
5,808 (1,395) ToPOT.nopretreatment
1,516 (364) ToPOT.nopretreatment
658 (158)
400 (96)
none 137 (33) to quench
3,414 (800) To POT
137 (33) To POT
982 (236)
1,869 (449) Reused
none All to quench
none 179 (43) to quench
572 (137)
566 (136) To POT, no pretreatment
to
See footnotes at end of Table.
-------
II
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larbon Treatment
Free Still
Fixed Still
Dephenolization
Bio-Oxidation
Chemical Oxidation
Recycle Baro.
Cond. Water
mil
tuft
— "**
ffi. as--
Additional Data-l/Mg (gal/ton)
And Comments
c
en
m
O
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m
z
>
00
CO
f
='
B
-------
not determined by the survey. Effluent flows given in Table 13 range from
about 80 to 5,800 1/Mg coke. The low end of this reflects use of wastewater
for quenching and the high end presumably includes some once-through cooling
water.
Disregarding plants with effluent rates above 2,500 1/Mg coke (to
eliminate large-scale once-through cooling water use) and those that waste-
water quench leaves us with effluent rates between 96 and 1,932 1/Mg coke
(23-468 gal/ton), with an average of 838 1/Mg coke.
75
-------
6.0 ENVIRONMENTAL EFFECTS OF COKE BY-PRODUCT RECOVERY
6.1 SUMMARY
The purpose of a Level 1 environmental assessment is to provide a screen-
ing or survey look at emissions from an industry, highlighting potential
problem areas for further work if justified.58 Within these limits, the
environmental effects of a by-product coke plant are assessed in this Section.
The test work was done at the Fairfield Works of U.S. Steel Corporation, near
Birmingham, Alabama. Other information was available in the literature and is
presented when appropriate.
The Level I assessment protocol recommends that all identified emissions
to all media be sampled and analyzed, as well as the feeds to and products
from the process. All of the samples are grab samples, and the intended
accuracy is to be within a factor of 2 or 3 of the actual emissions. Pro-
cedures and equipment are specified for a Level 1 assessment; these are dis-
cussed in detail in Appendix A.
Examination of the process flow of a by-product plant showed that most
air emissions were fugitive, and primarily composed of organic compounds. The
potential for these fugitive emissions to contain significant amounts of
aromatics and high molecular weight polynuclear aromatics (PNA's) was apparent,
and was important in the development of the analysis program. Hydrogen cya-
nide was also identified as a potentially significant component.
Liquid by-product plant wastes were and are presently a subject of de-
tailed study by the Effluent Guidelines Division of EPA. The analyses done by
the Effluent Guidelines Division were more extensive than possible with the
Level I methods used in this project. Their sampling was also being done at
Fairfield Works and in view of this fact, liquid sampling was limited in this
study. The Effluent Guidelines data have been included in this report. The
literature indicated a single major solid waste, the biological plant sludge,
which was sampled.
76
-------
PRIMARY COOLER TAR REMOVAL
EXHAUSTER REHEATER
AMMONIA
ABSORBER
FINAL
COOLER
LIGHT OIL
SCRUBBER
DESUIFURIZATION
(VACUUM CARBONATE)
FUGITIVE
LIGHT OIL PLANT
WASTEWATER
(INTERCEPTING SUMP)
(5)
TAR
STORAGE
1
TAR
REFINING
i
STORAGE
COMBINED
WASTEWATEH
FUGITIVE
SUJJ
TAR PRODUCT
PITCH
BIOLOGICAL TREATMENT PLANT
]
FINAL
EFFLUENT
Figure 15. Pollutants from by-product recovery.
-------
Stream
Number
TABLE 14. POLLUTANTS FROM BY-PRODUCT RECOVERY PLANT
Stream Identification
Rate: Constituents Based on 1 Mg Coke Production
-vl
CO
1 Coal
2 . Coke
3 Tar Decanter-Fugitive
4 Tar Sludge
5 Tar Dewatering-Fugitive
6 Tar Storage-Fugitive
7 Primary Cooler'Condensate
Fugitive
8 Tar Refining-Vapor
9 Chemical Oil Storage-Fugitive
10 Excess Liquor Tanks-Fugitive
11 Sulfate Drying
12 Acid Storage-Fugitive
13 Lime Leg Sludge
14 Barometric Condenser Water
15 Excess Ammonia Liquor
16 Naphthalene Separation
17 Naphthalene Drying
18 Final-Cooler Cooling Tower
19 Cooling Tower Slowdown
20 Light Oil Plant Wastewater
21 Wash Oil Tanks-Fugitive
22 Light Oil Decanter-Fugitive
23 Light Oil Storage-Fugitive
24 Wash Oil Sludge
25 Desulfurization Wastewater
26 Desulfurization Sludge
27 Wastewater Plant Fugitive
28 Wastewater Plant Sludge
29 Final Effluent
1.4 Mg
2.15 sm3/Mg: benzene, 15.6 g/Mg; H2S 12.7 g/Mg; XAD-2 sample primarily LC cut #2*
0.1 1/Mg (very rough estimate): contains tar, coal, and coke fines; no Level 1 analysis
Included in 6 below
0.14 sm3/Mg (working loss only): low rate benzene, toluene; XAD-2 sample primarily LC cut #/
1.7 snrVMg: benzene, 9 g/Mg coke; H2S 5.7 g/Mg; XAD-2 sample not collected
Not sampled.
.024 smVMg (working loss only): low rate benzene, toluene; XAD-2 sample mostly LC cut ffz
and #3
Not sampled: at lower temperature than 7 above, but roughly same composition
Not sampled
No measurable vent: not sampled
0.35 kg/Mg: primarily calcium salts
143 1/Mg: cyanide, 2 g/Mg; ammonia, 1.6 g/Mg; phenol, 0.5 g/Mg (Dunlap and McMichael;
143 1/Mg: cyanide, 8.6 g/Mg; ammonia, 857 g/Mg; phenol, 208 g/Mg (Dunlap and McMichael)
No measurable vent rate: vapor high in benzene and homologs, H2S; XAD-2 sample mostly
LC cuts #2* and #3
2.9 smVMg: Naphthalene emissions as high as 533 g/sm3, but an average must be considerably lower.
3,230 smVMg: benzene, 51.6 g/Mg; H2S, 11 g/Mg; XAD-2 sample mostly LC cuts #2* and #3
43-430 1/Mg: cyanide, 22-43 g/Mg; ammonia, 8-17 g/Mg; phenol, 10-16 g/Mg (Dunlap and
McMichael)
100-500 1/Mg: cyanide, 0.5-1 g/Mg; ammonia, 0.5-1.5 g/Mg; phenol, 0.8-26 g/Mg (Dunlap and
and McMichael); 3 kg/Mg oil (Schroeder)
No measurable vent: not sampled
Inaccessible: not measured or observed
0.013 snrVMg working loss, 15.6 smVMg breathing loss (crude estimate95): benzene, I/.4 g/Mg;
toluene, 0.6 g/Mg; H2S, 0.5 g/Mg
Not sampled and rate not available.
40-60 1/Mg vacuum carbonate plant: cyanide, 64 g/Mg (Dunlap and McMichael)
Not quantified
No measurable rate
1.7 kg/Mg: high phenolic levels
470-1,260 1/Mg coke: BPCTCA gives 730 1/Mg; cyanide, 20 g/Mg; ammonia, 91 g/Mg; phenol,
1.5 g/Mg; oil, 11 g/Mg
*LC Cut #2 expected to contain aromatic hydrocarbons, fused polycyclics, fused nonalternant polycyclics, and possibly halogenated aromatics.
-------
The sampling program developed for this study was centered on organic
vapor emissions from tank vents and a cooling tower. Appendix A contains a
more complete description than that given below. Three types of sampling were
used for the organic vapors: (1) glass bulb grab samples, (2) evacuated
canister grab samples, and (3) 1 to 4 hour samples drawing the gas through an
adsorbant resin, XAD-2. The glass bulbs were analyzed for light (Cj-C?)
hydrocarbons and volatile sulfur species using an on-site gas chromatograph
(GC). Benzene and toluene were also quantitated with this GC. The evacuated
canister samples were returned to the laboratory for analysis to identify and
quantitate benzene, toluene, the xylenes, and ethylbenzene. The adsorbant
resin was intented to adsorb hydrocarbons with carbon numbers greater than 7,
or boiling points above about 100° C. The resin was extracted with a solvent
and the extract analyzed in three ways:
(1) Total Chromatographable Organics (TCO), which is nominally the
mass o^organic compounds with boiling points between 200° C
and 300 Cj
(2) Gravimetric Analysis (GRAV), which is nominally the mass of
orgamcs with boiling points above 300° C; and
(3) Liquid Ghromatography, LC, which is used to divide an extract
into seven fractions (or cuts) which are graded by their
polarity.
The analysis generally proceeds with a TCO and GRAV analysis of the
original sample extract (preliminary), a concentration step to achieve a
specified organic concentration (GRAV and TCO are also run on this concen-
trate), and then the LC work, with a GRAV and TCO determination on each LC
cut.
Liquid and solid samples were handled in much the same way, the liquids
being extracted with a solvent at pH 2 and at pH 12, the solid sample was
extracted at pH 7. This extract was then treated in the same way as the
adsorbant resin extracts.
Further analysis of the Level 1 samples included infrared spectroscopy
(IR) and low resolution mass spectroscopy (LRMS). Unfortunately, solvent
interference prevented the extraction of much useful information from the
LRMS, which forced reliance on the IR data for compound identification and
rough quantisation, as described later in this summary.
79
-------
In addition to the Level 1 sampling and analysis, samples for hydrogen
cyanide were taken at the final cooler cooling tower and 24-hour integrated
samples were collected at three points around the plant boundary. The gas
was bubbled through a sodium hydroxide solution for cyanide absorption and
analyzed by wet chemistry.
The results of this sampling and analysis are presented in two ways. A
generalized, hybrid plant was developed (Figure 15) and used as a basis to
present the available data. This hybrid plant is thought to be close to a
widely used, relatively complete plant. The emission rates given in Table
14 are based on the sample work done at Fairfield or on the literature. A
brief description—amplified later in this Section—is also given for the
identified emissions. Excluded from the table are the pump seal leaks,
flange leaks, and other similar problems which plague chemical plants. Also
not addressed are certain periodic cleaning operations which are necessary
for some pieces of equipment. Standard conditions are 20° C and 760 mm Hg
throughout this report.
The emissions are discussed further in sections on each emission. The
majority of the Level 1 data is presented in these discussions. The pre-
sentation of the LC work demands special explanation. These LC separations,
with identification supported by IR, were summarized using a modification of
the Harris format.59 All organic compounds were assigned to one of 17
compound classes, these based on categories developed in the Multimedia
Environmental Goals (MEG's) publication.60 These compound classes have
chemical properties which lead one, two, or perhaps three of the LC cuts,
but not in all cuts.59 The LC and IR data was summarized as follows:
(1) If any compound class or member of a class was tentatively iden-
tified by the IR of an LC cut, it was assumed that that compound
class was present in the LC cut in the amount of the GRAV mass
(IR's were run only on the GRAV samples, per Level 1).
(2) A compound class which was considered possible in a LC cut, but
which was not identified by IR, (but could not be excluded on IR
evidence) was assumed to be present in the LC cut in the amount of
10 percent of the GRAV mass of the LC cut.
(3) The values derived in (1) and (2) above were divided by the sample
volume and are called MATE comparison values, with concentration
80
-------
units. The MATE comparison values presented in this chapter have
been summed across all the LC cuts to arrive at a total sample MATE
comparison value for each compound class.
These MATE comparison values, unlike the pollutant concentrations derived
from the GC work, are admittedly synthetic. In most cases the MATE comparison
values for a LC cut total more than the GRAY mass from which they were derived.
On the other hand, the MATE comparison values cannot be called "maximum possible,"
as the TCO mass was excluded from consideration. Fortunately, the results of
gas chromatograph/mass spectrometer (GC/MS) analysis of three of the samples
serves to clarify the situation, identifying those compounds which are actually
present.
To assist in the interpretation of the pollutant concentrations (from the
GC work) and MATE comparison values (from the LC and IR work), yardsticks are
derived from the MEG's charts.60 For the sake of conservatism, the most toxic
compound in each of the 17 compound classes was identified and its Minimum
Acute Toxicity Effluent (MATE) concentration was used for comparison (for many
compounds for which "Threshold Limit Values," TLV's, have been cited, the MATE
concentration is the TLV). The yardstick used was the ratio formed between
the MATE comparison value and the lowest MATE concentration for a compound
class.
It must be kept in mind that the resulting ratio is biased. If it is
well below unity there would appear to be no concern for compounds in this
class; if, however, the ratio is above unity, it is merely a signal for more
research. Level 1 assessment only illuminates the areas where more research
will be profitable. Due to the wide variation in MATE concentrations within a
compound class, the verification that one especially toxic compound cannot
reasonably be present in the emission could easily carry the ratio from well
above to well below unity—from a source of concern to its opposite.
One further comment concerning the organic data is needed. Naphthalene
was present in large amounts in many of the organic vapor samples. Indeed, it
condensed and plugged the sample train on several occasions. The naphthalene
in these very high concentrations to some extent defied both the TCO-GRAV
split into heavy and light organics and the LC split by polarity. The aromatic
concentrations given, in many cases, are primarily contaminated naphthalene.
81
-------
The total GRAV and TCO concentrations in the sample are presented, indi-
cating the relative amounts of high boiling (b.p. > 300° C for GRAV) and low
boiling compounds. The IR work used on the LC cuts was done entirely on GRAV
samples, so only GRAV masses are reflected in the MATE value comparison con-
centrations.
Three of the samples were further examined by GC/MS, and the actual
compounds identified in these samples are listed in a continuation of the
organic summary table.
6.2 ENVIRONMENTAL EFFECTS OF COAL TAR COLLECTION AND PROCESSING
The emissions from tar processing are essentially all fugitive in nature.
The primary sources are:
emissions From Tar Decanters
primary Cooler Condensate Holding Tank
emissions From Tar Dewatering/Storage
tar "Topping" Emissions
tar Distillation Products Storage.
Emissions From Tar Decanters
As has been described, tar decanters are often elongated, multi-compart-
ment, rectangular tanks, the tar collecting on the bottom of the tank and
flushing liquor being removed at the top, In addition to these two primary
streams, a sludge accumulates in the initial compartment, or may be collected
by a drag conveyor from the bottom of the decanter. As the temperature of the
flushing liquor in the decanters is around 80° C, vaporous emissions may be
visible from the vent pipes of a covered decanter. In addition, open or
warped hatches allow additional emissions.
The sludge from a tar decanter was not analyzed. The sumps at the sam-
pled plant were cleaned on the order of once a week (rough estimate 0.1 1 of
sludge/Mg coke). The sludge consists of coal and coke fines mixed with coal
tar and resins. Thus, the full range of tar components is present. Disposal
at the plant visited was to an on-site dumping location (unspecified). However,
disposal on the coke pile or coal pile for recycle to the ovens should be
possible.
82
-------
Vapor emissions were determined from three tar decanters serving four
batteries. The results of the sampling and analysis are presented in Table
15. The overall emission rate from the three decanters was about 2.15
smVMg coke produced. The emission rate as given is the total emission
divided by the production rate at the plant during the sampling week, 3600
Mg coke/day. This is a reasonable first approximation; but the emission
rate varied considerably from decanter to decanter, and is probably more
dependant on the design and number of decanters than on production.
As can be seen in Table 15, the benzene and hydrogen sulfide concentra-
tions in this source are well above the MATE values, and some possible
problem areas were identified by the liquid chromatography work. The GC/MS
work presented on the continuation page of Table 15 shows that several of
the compound classes possible from the IR are not actually present. Aroma-
tic hydrocarbons as a class remain above the MATE value.
Primary Cooler Condensate Holding Tanks
At the sampled plant the primary cooler condensate holding tanks (which
also served to decant additional tar) were tall cylindrical tanks (height to
diameter of about 3:1) around 15 feet in diameter. The tanks were vented
through short pipes. Gas temperature in the vent was 62° C with a measur-
able emission. The vent rate was estimated at 1.7 smVMg coke by extrapo-
lating one measured rate to two other tanks in the same service (assumed
same vent rate) for a combined total emission. Emissions from this source
are summarized in Table 16. As above, benzene and H2S are present in con-
centrations well above the MATE values.
Emission from Tar Dewatering/Storage
The emissions from a separate tar dewatering step were not directly
determined during this study. The plant visited utilized heated (80° C) tar
storage, the emissions from which should be similar in composition to
dewatering by steam heat. Dewatering by centrifuge should result in reduced
emissions in comparison to heated tanks, although the overall effect would
be lessened if heated tar storage tanks were also used in the same plant.
83
-------
TABLE 15. SUMMARY OF ORGANIC ANALYSIS, TAR DECANTER VAPOR
Emission rate: 2.15 sm3/Mg coke
Compounds Identified
by GC
Ci-Cy HC(Avg. MWa22)
Benzene
Toluene
Xylenes and ethyl benzene
Sulfur compounds (as H2S)
0
Liquid Chromatography
Aliphatic hydrocarbons
Halogenated aliphatics
Aromatic hydrocarbons
Halogenated aromatics
Heterocyclic N, 0, S
compounds
Sul fides, disul fides
Nitriles
Ethers
Aldehydes, ketones
Nitroaromatics
Alcohols
Ami nes
Phenols
Esters, amides
Me reap tans
Carboxylic acids
Sulfoxides
Concentration,
mg/sm3
4,550
7,283
745
186
5,914
MATE
Comparison
Value, mg/sm3
141.8
3.2
519
43.0
0.95
0.95
0.95
185
82.8
3.33
6.4
8.16
5.9
157
2.95
24.2
2.96
MEGS3
Category
Number
MATEb
Values,
mg/sm3
1 min. = 32
15
15
15
53
MEGs3
Category
Number
lc
2c
25,22^22
16?
23, 24, 25
13b
9C
3C,4C
7C
17C
5C,6C
10C,11C,12
18, 19°, 20°
8C,8DC
13AC
8A,8BC
14C
3
375
435
15
Min. MATE5
Value in
Category
32
0.1
1.0
0.7
0.1[9}d
20
1.1
0.01
0.2
1.0
10
c 0.001
0.1\_10]d
1.0
1.0
0.3
1.0
Ratio
/Cone. FoundX
\ MATE )
142
2,430
2.0
0.43
394
Ratio
4.4C
32C
519
61. 4C
9.5°{0.1]d
0.04C
0.86C
18,500C
414C
3. 33C
0.64C
8,160C
c Q i r\ ^o 1
tJi/ \UftJi3\
157C
2.95C
81C
2.96C
GRAV cone, in sampled gas
TCO cone, in sampled gas
2,720-3,550 mg/sm3
5,110 mg/sm3
MEG = Multimedia Environmental Goals
MATE = Minimum Acute Toxicity Effluent
Not indicated by GC/MS work
Reflects compounds found by GC/MS work
Italics highlight categories found by
GC/MS.
84
-------
CD
cn
TABLE 15. (continued)
Elution
Temperature
/00\
( c)
70
70
101.2
107.9,113.1
118.5
123.0
124.6
131.0
134.8
140.6
143.5
174.4
149.2
153.1
156.3
156.9
158.8
Compound
Benzene
Toulene (?)
Phenol
Indene
Cresols
Pi vinyl benzene (?)
Naphthalene
Benxothiophene
Quinoline or isoquinoline
Methyl indene
Methyl naphthalene
Methyl naphthalene
Indole
Methyl -quinoline
Biphenyl
C2 -naphthalene
C2 -naphthalene
C2 -naphthalene
IDENTIFICATION
Elution
Temperature
(°C)
161.7
162.3
167.1
167.7
172.3
178.3
180.3
183.5
185.7
186.3
187.9
201.4
204.6
205.5
206.2
220.3
236.3
241.7
Compound
Ca-naphthalene
Biphenyl ene
Acenaphthene
Me thy! -biphenyl
Dibenzofuran
Methyl -acenaphthene
Fl uorene
Carbazole (?)
Hydroxyfl uorene isomer
Methyl acenaphthene isomer (?)
Hydroxyfl uorene isomer
Dibenzothiophene
Phenanthrene
d10-anthracene^
Anthracene (?)
4 ,5-Methylenephenanthrene
Fluoranthene
Pyrene
QUANT I TAT I ON
Compound
Of those compounds identified, only quinoline and biphenyl were quantitated.
Subjectively, naphthalene appeared to be the prevalent compound.
Wt. of Compound
In XAD Extract
Wt. of Compound
in Canister Rinse
(mg)
Total Wt.
Concentration (mg/sm3)
in Gas Sample
Biphenyl
Quinoline
144.3
294.2
14.9
29.1
159.2
323.3
19.6
39.7
Often an artifact from sample contact with plastics.
Internal standard.
-------
00
o»
TABLE 16. SUMMARY OF ORGANIC ANALYSIS, PRIMARY COOLER CONDENSATE TANK VENT
Emission Rate: 1.7 sm3/Mg coke
Compounds Identified by GC
Cx-C7 HC (Average MW=£3.6)
Benzene
Toluene
Xylenes and ethyl benzene
Sulfur compounds (as H2S)
Concentration
mg/sm3
1,883
5,230
649
215
3,324
MEG's Category3
Number
1
15
15
15
53
MATE Valueb
(mg/sm3)
min. = 32
3
375
435
15
Ratio
/ Found \
\~MATE;
59
1,740
1.7
0,5
222
aMEG = Multi-Media Environmental Goals.
3MATE = Minimum Acute Toxicity Effluent.
-------
Emissions from Tar Storage Tanks
Tar is commonly stored in heated tanks in order to facilitate handling.
A single tar storage tank was sampled, and the results were extrapolated to
all the tar storage tanks. Storage was at approximately 80° C. Naphthalene
condensation was evident at all vents and hatches on the tank. The emissions
are summarized in Table 17. Again, benzene and the aromatic hydrocarbons
class were present in amounts above the MATE values. The emission rate could
not be measured, and that given was estimated strictly as working loss. Some
problem areas were identified by the LC work.
Two aspects of this estimate deserve special comment. The tar storage
tanks at the plant visited were cone roof cylindrical tanks with a vent pipe
in the center of the roof. In addition, the tanks were vented by slits roughly
20 cm high spaced around the perimeter of the tank directly below the roof
junction. As wind must enter the tank through these vents, emissions from
these tanks are probably at a higher rate and lower concentration than might
otherwise be expected.
The second comment is that it was not possible to estimate breathing loss
for the tanks, as predictive equations are not available for this situation.
The common breathing loss equation cannot cope with a tank of coal tar covered
with a layer of water (contaminated with various hydrocarbons). Thus, the
emissions estimate for tar storage tanks is probably low.
Emissions from Tar Refining (Topping)
Tar topping at the tested plant was accomplished with a single flash
distillation with vacuum provided by steam jets. Chemical oil and an aqueous
stream were condensed by indirect cooling in separate exchangers before a
barometric condenser final stage. No measurements of this system were made.
Evidence that hydrocarbons did get into the water was provided by naphthalene
condensation around the vent pipe on the barometric condenser. The rates
appeared to be low compared to other emissions in the area.
Tar Distillation Products Storage
The products of the plant's one-stage flash distillation of tar were
pitch and chemical oil. No emissions were noted from the pitch handling
87
-------
TABLE 17. SUMMARY OF ORGANIC ANALYSIS, VAPOR ABOVE TAR STORAGE TANK
Emission rate: 0.14 sm3/Mg coke
Compounds Identified
by GC
Ci-C7 HC(Avg. MWsl9)
Benzene
Toluene
Xylenes and ethyl benzene
Sulfur compounds (as H2S)
Concentration,
mg/sm3
3.75
65.6
21.1
16.3
not detected
MEGsa
Category
Number
1
15
15
15
53
MATE5
Values,
mg/sm3
min. = 32
3
375
435
15
Ratio
/Cone. Found\
( MATE )
0.12
22
0.06
0.04
~
Liquid Chromatography
MATE
Comparison
Value, mg/sm3
MEGsd Min. MATEL
Category Value in
Number Category
Ratio
Aliphatic hydrocarbons
Halogenated aliphatics
Aromatic hydrocarbons
Haloqenated aromatics
Heterocyalic ft, 0, S
compounds
Sulfides, disulfides
Nitrites
Ethers
Aldehydes, ketones
Nitroaromatics
Alcohols
Amines
Phenols
Esters, amides
Mercaptans
Carboxylic acids
Sulfoxides
1.6
0.16
32. 1
1.45
1.11
1.11
1.11
19.5
28.5
0.71
8.1
1.79
6.7
30.1
1.1
1.1
1.1
lc
2c
15,21A,22
16C
23, 24, 25
13BC
9
3,4C
7C
17C
5,6C
10C,11C,12C
18 ,19° ,20°
8C,8DC
13 AC
8AC,8BC
14c
32
0.1
1.0
0.7
0.1
20
1.1130]
0.01
0.2
1.0
10
0.001
O.l[l0l
1.0
1.0
0.3
1.0
0.05C
1.6C
32. i
2.1C
11.1
0.06C
d 1.0°l0.04ld
1,950C
143C
0.71C
0.81C
1,770C
d 67°t0.7]d
30. 1C
l.lc
3.7C
1.1C
GRAV cone, in sample
TCO cone, in sample
37.0-582 mg/snr
1,450 mg/sm3
aMEG = Multimedia Environmental Goals
bMATE = Minimum Acute Toxicity Effluent
cNot indicated by GC/MS work
dReflects compounds found by GC/MS work
Italics highlight categories found
by GC/MS
88
-------
TABLE 17. (continued)
00
Elution
Temperature
(°C)
70.0
70.0
70.0
77.2
79.5
80.1
90.7
92.6
93.9 '
94.5
98.7
101.5
104.4
107.3
1AQ Q
iuo. y
112.7
113.1
Compound
Benzene
Toluene
Pyridine
m- and p-Xylenes
Styrene3
p-Xylene
Benzofuran
Methylpyridines
Benzofuran
C3-benzenes
Phenol
Indene
C4-benzenes
Cresol
C10Hi2 isoraer
Cresol
Methyl indene
IDENTIFICATION
Elution
Temperature
(°C)
122.0
122.7
124.9
131.6
141.2
143.5
153.4
157.5
159.8
163.3
168.1
173.2
181.9
190.5
190.5
205.9
207.5
Compound
C2-phenol (?)
Naphthalene
Benzothiophene
Quinoline
Methyl naphthalene
Methyl naphthalene
Biphenyl
C2-naphthalene
C2-naphthalene
Biphenylene or acenaphthylene (?)
Acenaphthene
Dibenzofuran
Fluorene
X-methyl acenaphthylene
Ami noethy 1 carbazol e
Phenanthrene
dio-anthracene
QUANTITATION
Compound
Of those compounds identified, only quinoline and biphenyl were quantitated.
Subjectively, naphthalene appeared to be the prevalent compound.
Wt. of Compound
In XAD Extract
(mg)
Wt. of Compound
In Canister Rinse
(mg)
Total Wt.
Concentration (mg/sm3)
in Gas Sample
Biphenyl
Quinoline
10.4
31.1
" "* • - ~ -...-. ; . . - — .
0.5
1.4
====================================
10.9
32.5
1.9
5.8
Often an artifact from sample contact with plastics.
Internal standard.
-------
operations; a chemical oil storage tank was sampled. As with the tar storage,
the chemical oil tank was a vented, fixed roof tank with additional vents near
the top of the tank sidewalls. Naphthalene was condensed on the hatch covers
and vents. The tank was maintained above ambient temperature, in the range of
50° C.
The problems associated with estimating breathing loss from this tank
include inadequate vapor pressure data and the effect of wind blowing through
the side vents. The results of the sampling and analysis are summarized in
Table 18. Based on the GC/MS work done on other vapor samples, we might
expect that only compounds in MEGs categories 2, 9, 15, 18, 21, and 22 are
actually present.
.6.3 ENVIRONMENTAL EFFECTS OF AMMONIA PROCESSING
Again, most of the emissions from this processing segment are fugitive.
All flushing liquor decanters and tar decanters were included under the "Tar
Processing" section above. The company at which the sampling was conducted
considered their wastewater treatment plant, including the ammonia recovery
portion, to be proprietary, and thus no samples were collected in this portion
of the plant. This section will consider ammonia stills (both free and fixed)
and ammonium sulfate production. The pollutant sources are:
(1) sulfate drying
(2) sulfuric acid vapor
(3) lime leg muck, and
(4) process fugitives.
Also discussed are emissions from ammonia destruction by incineration. The
treatment of waste ammonia liquor in a water treatment plant is discussed in a
separate section.
Ammonium Sulfate Drying and Acid Storage
At the tested plant, ammonium sulfate crystals were washed, then centri-
fuged. The dewatered crystals were then entrained in a heated air conveying
system and transported to a storage pile. Emissions (if present, presumably
S02 and NH3) from this operation were not determined. The available data are
inadequate to predict the emissions from drying ammonium sulfate. The same
considerations apply to the acid storage tanks. There was no measurable
emission.
-------
TABLE 18. SUMMARY OF ORGANIC ANALYSIS, VAPOR ABOVE CHEMICAL OIL TANK
Emission rate: 0.024sm3/Mg coke
Compounds Identified
by GC
Cj-Cy HC(Avg. MWS16)
Benzene
Toluene
Xylenes and ethyl benzene
Sulfur compounds
(as H2S)
Liquid Chromatography
Aliphatic hydrocarbons
Halogenated aliphatics
Aromatic hydrocarbons
Halogenated aromatics
Heterocyalic N, 0, S
compounds
Sul fides, disul fides
Nitrites
Ethers
Aldehydes, ketones
Nitroaromatics
Alcohols
Amines
Pheno Is
Esters, amides
Mercaptans
Carboxylic acids
Sulfoxides
GRAV cone, in sample
TCO cone, in sample
MEGsa
Concentration, Category
mg/sm3 number
1.86
327
266
200
not
detected
MATE
Comparison
Value
mg/sm3
(34.8)
(3. 48)
(640)
(57.7)
(8.64)
(8.64)
(8. 64)
(186)
(165)
(4.2)
(6.3)
(6. 3)
(4.9)
(165)
(4.9)
(4.9)
(4.9)
860-1,950
2,050
1
15
15
15
53
MEGS3
Category
Number
1
2
15,21A,22
16
23., 24, 25
13B
9
3,4
7
17
5,6
10,11,12
18,19,20
8C,8D
13A
8A, 8B
14
mg/sm3
mg/sm3
MATEb
Values,
mg/sm3
min. = 32
3
375
435
15
Min. MATEb
Value in
Category
32
0.1
1.0
0.7
0.1
20
1.1
0.01
0.2
1.0
10
0.001
0.1
1.0
1.0
0.3
1.0
Ratio
/Cone. Found \
V MATE /
0.06
109
0.709
0.46
-
Ratio
1.1
5
640
82
86
0.43
7.8
18,600
825
4.2
0.63
6,300
49
165
4.9
16. 3
4.9
MEG = Multimedia Environmental Goals
MATE = Minimum Acute Toxicity Effluent
Values in parentheses are partially based on GRAV mass before subtraction
of blank.
Italics highlight categories found by GC/MS in other samples.
91
-------
Lime Leg Muck
The use of lime to reduce the pH of ammoniacal liquor in a fixed still of
conventional design coincidentally causes a sludge to form in the dissolver at
a rate of around 0.35 kg/Mg coke.61 The sludge was not sampled during this
study. The majority of the sludge is composed of precipitates (calcium salts)
formed within the ammonia stills.62 The extent to which organic pollutants
are entrained in the sludge has not been reported. The use of NaOH for pH
control does not cause a sludge to form. The method of disposal of this
sludge was not determined.
Process Fugitives
There are few opportunities for fugitive emissions from this processing
sector. None were identified during the visit other than the acid "odor"
mentioned above. There are certainly emissions from ammonium sulfate storage,
but these are apparently at a very low level.
6.4 ENVIRONMENTAL EFFECTS OF DEPHENOLIZATION PROCESS
A dephenolization process was not sampled during this study, so all
comments made are based on the literature. The primary process wastes are the
wastewater after "springing" the tar acids from the sodium salts and the
waste/springing gas. If excess ammonia liquor (including 0.14 kg tar acid/Mg
coke) contacts light oil which then contacts a 10 percent caustic solution,
the water becomes a waste stream once the tar acid is released. At a consump-
tion rate of 1 kg caustic per kg phenol,62 about 1.26 1 of wastewater are
produced per Mg coke (0.3 gal/ton). The composition of this wastewater was
not available; the expected composition would be primarily sodium salts of the
springing gas such as sodium carbonate, bicarbonate, and sulfide.63 Perhaps 5
percent of the tar acids would remain as phenolic salts. Secondary treatment
options have been described in the literature for the recovery of most of
these residual phenolics,60 but their prevalence is not known.
The utilization of an acid gas to release tar acids from the caustic
solution is described in the literature.27 62 63 The rate of emission is not
known, nor is the composition. If blast furnace gas at 30 percent CI3 is used
to spring the tar acids, and all C02 combines with the sodium, the waste gas
92
-------
rate would be about 0.32 mVMg coke. The rate of organics stripping which
would occur is not known. The gases can be vented back to the suction mains.62
Emissions from tank vents and separator were not quantified in the liter-
ature. As described above, these have been vented back to the suction main.
The springing wastes are not included on Figure 15 because "springing" is a
seldom used unit process.
6.5 FINAL COOLER AND NAPHTHALENE HANDLING
The plant at which the sampling was done utilized a contact, water type
final cooler. Naphthalene separation was by froth flotation with separation
in open basins. A package cooling tower was utilized to cool the recircu-
lating water. Other techniques, thought to produce significantly different
results, are discussed separately.
The emission sources identified for the contact, recirculating water type
final cooler are those associated with the naphthalene separation from the
water and emissions from the cooling tower. Naphthalene handling by melting/
drying in vented tanks was another significant emission source. The use of
tar bottom final coolers and wash oil final coolers was not observed, and only
qualitative comments are offered.
Naphthalene Separation
Naphthalene condenses in the final cooler water and is collected as a
dirty brown slurry. The plant visited began the separation with a froth
flotation operation. Agitators submerged in the liquid drew air into the
vortex and dispensed it in the water. The vessel was loosely covered with a
series of hatches. No vent stream was at a rate sufficient to be measured,
although there were visible wisps of vapor. The vapor directly above this
liquid surface was sampled and the results are presented in Table 19. As
before, many of the MEGs categories may not be present. The aromatic hydro-
carbons are again above the MATE values. The naphthalene slurry which floated
to the top of the water was skimmed and collected in open sumps, and the water
was passed through a series of small basins to allow additional naphthalene
separation.
The rate of emissions from this naphthalene collection operation could
not be determined. The total superficial exposed surface area was about
93
-------
TABLE 19. SUMMARY OF ORGANIC ANALYSIS, FROTH FLOTATION SEPARATOR
Emission rate: unknown
Compounds Identified
by GC
q-Cy HCCAvg. MWs24)
Benzene
Toluene
Xylenes and ethyl benzene
Sulfur compounds (as HaS)
MEGsa
Concentration, Category
mg/sm3 Number
2,051
4,700
488
82.1
2,125
MATE
1
15
15
15
53
MEGsa
Comparison Category
Liquid Chromatography
Aliphatic hydrocarbons
Halogenated aliphatics
Aromatic hydrocarbons
Halogenated aromatics
Value, mg/sm3 Number
M
(I.18f
(33.8)
(1.69
\
Heterocyclic N, 0, S compounds (1.07
Sulfides, disulfides
Nitrites
Ethers
Aldehydes, ketones
Nitroaromatics
Alcohols
Amines
Phenols
Esters, amides
Mercaptans
Carboxy lie acids
Sulfoxides
GRAV cone, in sample
TCO cone, in sample
(1.07
y
(l.07
(\ \
22.2)
(39.9)
1
) ^
15,21A,22
16
23, 24, 25
13B
)
3,4
7
(0.96) 17
K
H
(43.5)
(l.2J
(1.2)
^.2}
) 5,6
10,11,12
18,19,20
8C,8D
13A
8A,8B
14
MATE5
Values,
mg/sm3
min. = 32
3
375
435
15
Min. MATEb
Value in
Category
32
0.1
1.0
0.7
0.1
20
1.1
0.01
0.2
1.0
10
0.001
0.1
1.0
1.0
0.3
1.0
Ratio
/Cone. Founds
V MATE /
64
1,570
1.3
0.2
140
Ratio
0.36
11.8
33.8
2.41
10.7
0.05
1.0
2,220
200
1.0
1.28
3,400
58
43.5
1.2
4
1.2
18.9-19.9 mg/sm3
660 mg/sm3
aMEG = Multimedia Environmental Goals
bMATE = Minimum Acute Toxicity Effluent
Values in parentheses are based on GRAV mass before subtraction
of blank.
Italics highlight categories found by GC/MS in other samples.
94
-------
1,000 ft2. The actual surface exposed to the wind by the crystalline slurry
is not known. The rate of entrained air flow in the froth flotation vessel
was not available from the plant. Subjectively, the odor of naphthalene was
quite strong in this area of the plant.
Final Cooler Cooling Tower Emissions
The final cooler cooling tower has for some time been recognized as a
potential source of cyanide emissions, and was sampled both for cyanide and
organics. The level of cyanide in the water depends on the degree of cyanide
stripping which is accomplished in the ammonia stills, along with final cooler
operations and coal composition. At the site sampled, hydrogen cyanide was
present in the gas leaving the cooling tower at an average concentration of
76.5 ppm, which corresponds to a mass emission of 0.28 kg/Mg coke (0.56 Ib/ton)
Based on the literature values of hydrogen cyanide production given in Chapter
4, 0.71 kg/Mg coke (0.5 kg/Mg coal), this source accounts for about half the
cyanogen generated. The gas flow rate was estimated by assuming that the gas
mass flow was equal to the known liquid circulation rate. Organic emissions
were also measured and are presented in Table 20. Again, several categories
were not indicated by the GC/MS work. Based on the MATE values, emissions of
significance from this source are benzene and hydrogen cyanide. In addition
to the vapor phase measurements, liquid samples were collected from both the
hot and cold wells of the cooling tower. These were subjected to the Level 1
organic analysis protocol, and the results are summarized in Table 21.
Naphthalene Processing
Naphthalene collected as described above is impure and in roughly a 60
percent water slurry. This naphthalene slurry was pumped into a horizontal
cylindrical tank. Once the tank was full, the water was decanted. Steam
coils within the vessel were then utilized to dry and melt the naphthalene.
This operation continued for one to two days. There was not a suitable samp-
ling point for the vapor emission from this process; scaffolding would have
been required. The vent rate was estimated to be 2.9 sm3 vapor/Mg coke (93.4
scf/ton) by measuring the rate of air entering the vessel due to the chimney
effect. The temperature in the tank was 101° C. Naphthalene was sampled at a
concentration of 533 g/sm3, which amounts to 1.56 kg naphthalene per Mg coke
95
-------
TABLE 20. SUMMARY OF ORGANIC ANALYSIS, FINAL COOLER COOLING TOWER VAPOR
Emission rate: 3,230 sm3/Mg coke
Compounds Identified
by GC
C!-C7 HC (Avg. MWS16)
Benzene
Toluene
Xylenes and ethyl benzene
Sulfur compounds (as H2S)
Liquid Chromatography
Aliphatic hydrocarbons
Halogenated aliphatias
Aromatic hydrocarbons
Halogenated aromatics
Eeterocyclic N, 0, S
Compounds
Sul fides, disul fides
Nitrites
Ethers
Aldehydes, ketones
Ni troaroma t ias
Alcohols
Amines
Phenols
Esters, amides
Mercaptans
Carboxylic acids
Sul f oxides
GRAV cone, in sample
TCO cone, in sample
Concentration,
mg/sm3
1.89
15.8
not detected
not detected
3.3
MATE
Comparison
Value, mg/sm3
(1.90)
(o.os)
(4.78)
(0.21)
(o.os)
(0.09)
(0.08)
(2.38)
(3.68)
(O.IT)
(1.42)
(0. 25)
(0. 21)
(3.68)
(0.21)
(0.21}
(0.21)
2.75-10.6 mg/sm3
226 mg/sm3
MEG's
Category
Number
1
15
15
15
53
MEG's3
Category
Number
1
2
1S,21A,22
16C
23, 24, 25
13BC
9
3C,4C
7C
17
5C,6C
10,11°, 12°
18, 19°, 20°
8CC,8DC
13AC
8A,8B
14C
MATEb
Values,
mg/sm3
min. = 32
3
375
435
15
Min. MATEb
Value in
Category
22
0.1
1.0
0.7
0.1
20
1.1
0.01
0.2
1.0
10
0.001\_19~\
o.ilwf
1.0
1.0
0.2
1.0
Ratio
/Cone. Found \
V MATE /
0.06
5.3
-
-
0.2
0
Ratio
0.06
0.8
4.76
f*
0.3C
0.8
0.004C
0.07
238
18. 4C
0.17
0.14C
j i
d 2SO\.0.01T
2.1°\.0.02ld
3.68C
0.21C
0.7
r*
0.21L
aMEG = Multimedia Environmental Goals
bMATE = Minimum Acute Toxicity Effluent
Values in parentheses are based on GRAV
mass before substraction of blank.
cNot indicated by GC/MS work
dRef1ects compounds found by GC/MS work
Italics highlight categories found
by GC/MS.
96
-------
TABLE 20. (continued)
UD
IDENTIFICATION
Elution
Temperature
(°C)
100.0
100.0
100.0
100.0
100.0
100.0
100.0
100.0
100.0
100.0
102.1
105.6
106.9
107.9
108.8
109.8
112. 7
115.5
116.2
118. 1
Compound
1,1, 1-Trichloroethane
Benzene
Cyclohexene
Pyridine
Toluene
X-me thy Ipyri dines
Xylenes
Phenyl acetylene (?)
C2-pyridines
Styrene
C2-pyridine
Benzonitrile
Aniline
Benzofuran
C2-pyridine (?)
Phenol
Indene
C7H9N isomer
Cresols
C10H12 isomer
Elution
Temperature
(°C)
125.1
128.3
129.3
137.0
144.0
145.3
147.5
151.7
156.8
161.3,163.2
166.7
171.5,171.9
172.9
176.3
186.3
193.9,198.1
210.3
210.6
265.0
265.0
Compound
Methyl indenes
C2-phenols
Naphthalene
Quinoline
Methyl benzothiophene isomer
Methyl naphthalene
Methyl naphthalene
Indole
Biphenyl
C2-naphthalene isomers
Biphenylene
C13H12 and C14H14 isomers,
acenaphthene
Dibenzofuran
Fluorene
Ami no ethyl carbazole (?)
Phenanthrene
D10-anthracene
a phthalate
a phthalate
QUANTITATION
Of those compounds identified, only quinoline and biphenyl were quantitated.
Compound
Biphenyl
Quinoline
Subjectively, naphthalene appeared
Wt. of Compound Wt. of Compound
In XAD Extract in Canister Rinse
(nig) (nig)
1.7 0
10.2 0
to be the prevalent
Total Wt.
1.7
10.2
compound.
Concentration (mg/sm3)
in Gas Sample
0.06
0.37
'Often an artifact from sample contact with plastics.
Internal standard.
-------
TABLE 21. ORGANIC EXTRACT SUMMARY, FINAL COOLER COOLING TOWER - HOT AND COLD WELLS
UD
CO
Preliminary
Hot Well
pH 2 extract
Total organics, mg/1
TCO, mg/1
GRAV, mg/1
pH 12 extract
Total organics, mg/1
TCO, mg/1
GRAV, mg/1
Hot Well Total
Organics, mg/1
Cold Well
pH 2 extract
Total organics, mg/1
TCO, mg/1
GRAV, mg/1
pH 12 extract
Total organics, mg/1
TCO, mg/1
GRAV, mg/1
Cold Well Total
Organics, mg/1
311
2,160
192
106
720
80
417
201
1,360
160
84.5
480
160
286
Concentrate
241
1,463
362
121
660
258
362
161
863
358
51
356
29
212
LCI
3.
0.
3.
0.
0.
0.
3.
2.
0.
2.
0.
0.
0.
2.
3
0
3
0
0
0
3
0
0
0
0
0
0
0
LC2
81
79
2.1
3.8
3.8
0.0
84.8
27.0
27.0
0.0
0.07
0.07
0.0
27.1
LC3
0.53
0.0
0.53
0.26
0.0
0.26
0.79
1.0
0.0
1.0
0.13
0.0
0.13
1.13
LC4
12.6
11
1.6
•
4.6
3.8
0.80
17.2
4.2
3.2
1.0
1.4
1.0
0.40
5.6
LC5
2.9
2.9
0.0
1.
1.
0.
4.
10.
9.
1.
0.
0.
0.
11.
3
3
0
2
6
0
6
72
59
13
3
LC6
84.4
76
8.4
74.4
55.1
19.3
159
90.4
74
16.4
34.9
31.6
3.3
125
LC7
1.4
0.0
1.6
0.0
0.0
0.0
1.6
0.53
0.0
0.53
0.0
0.0
0.0
0.53
-------
(3.13 Ibs/ton), or about twice the plant's total naphthalene production. The
sample is obviously not representative of the average emission rate, and
emissions from this source cannot be quantitated on the basis of the available
data.
Once-Through Cooling Water
A plant which utilized once-through cooling water in the final cooler
would produce an aqueous waste very similar to that described as the cooling
tower hot well, above.
Tar Bottom Final Cooler
No sampling was conducted at a tar bottom final cooler. The emissions
from naphthalene handling would be absent in this case, and cooling tower
emissions should be similar to those discussed above. A blowdown will still
be required for the recirculating water.
Wash Oil Final Cooler
Emissions from a wash oil final cooler were not determined. Qualita-
tively, wash oil coolers provided the wash oil is itself in noncontact heat
exchangers and that naphthalene is processed in closed vessels, should have
very low emission rates. A wastewater stream will be condensed as the cooler
oven gas is cooled, and this will require treatment. In addition, the distri-
bution of HCN in the plant will probably be different (higher HCN in the gas)
than it would be in a water type final cooler, and this may cause problems
downstream.
6.6 ENVIRONMENTAL EFFECTS OF LIGHT OIL RECOVERY
The emissions identified with light oil recovery include a sludge,
several decanted water streams, fugitive tank emissions, and a vent from the
light oil condenser.
Wastewater Streams
Several wastewater streams are decanted in the light oil plant. The
primary source of the water is the line steam used to strip light oil from
wash oil, and water must be separated from all the hydrocarbon liquids con-
densed from the still vapor as well as from wash oil. None of these water
99
-------
streams were analyzed. They are commonly collected in the "intercepting sump"
and treated in the combined wastewater treatment plant. The rate has been
estimated at between 100 and 500 1/Mg coke depending on the ability of the
operator to tightly recycle the water.
Wash Oil Sludge
A sludge forms in wash oil as it is used over and over again. The sludge
was not analyzed and the rate of formation was not determined. The muck
consists of polymers formed by the interaction of organic mercaptans, disul-
fides, heterocyclic sulfur compounds, and unsaturated hydrocarbons, along with
oils, dirt, and water.16 Other reactions also form sludges. Disposal can be
to landfill or on to the coal pile for recycle to the ovens.
Fugitive Tank Emissions
Fugitive emissions occur from wash oil storage, wash oil decanters, and
light oil storage. Only the light oil storage tank was sampled, as it was
amenable to data reduction by the tank breathing loss equation. No emissions
with measurable rates were present. Results of the samples from the light oil
storage tank are presented in Table 22.
Light Oil Condenser Vent
The noncondensibles vent off the light oil condenser was not accessible
under Level 1 constraints and was not sampled. No data are available in the
literature. This stream probably consists of the fraction of the coke oven
gas which dissolved in the wash oil, as well as light oil vapor. This stream
is thought to be quite small, appropriate for the 2-inch pipe used to vent the
condenser.
6.7 DESULFURIZATION - ENVIRONMENTAL ASSESSMENT
A great deal of research, development, engineering, and regulatory effort
is presently being expended on the desulfurization of coke oven gas. In the
interest of making the best use of available resources and to avoid duplica-
tion, no samples of desulfurization plant streams were taken. This section is
a review of the extensive literature on desulfurization.
The intent of desulfurization of coke oven gas is to reduce the emissions
of SO into the ambient air when the coke oven gas is burned. As has been
f\
100
-------
TABLE 22. SUMMARY OF ORGANIC ANALYSIS, LIGHT OIL STORAGE
Emission Rate: 15.6 sm3/Mg coke
Compounds Identified
by GC
Ci-C7 HC (Average MWs46)
Benzene
Toluene
Xylenes and ethyl benzene
Sulfur compounds (as H2S)
Concentration
mg/sm3
225
1,040
36.8
not detected
37-44
MEG's Category3
Number
1
15
15
15
53
MATE Valueb
(mg/sm3)
min. = 32
3
375
435
15
Ratio
/Found\
\MATE )
7
347
0.1
—
2.5-2.9
S b
MEG = Multimedia Environmental Goals.
MATE = Minimum Acute Toxicity Effluent.
-------
stated, the common techniques convert the sulfur to either the elemental form
or to sulfuric acid. With respect to overall removal then, both the effi-
ciency of removal of sulfur from coke oven gas and the efficiency of convert-
ing this sulfur to the desired product must be considered. In addition, the
desulfurization processes themselves are not without environmental impact.
Vacuum Carbonate System
The Koppers1 Vacuum carbonate system, as offered in the mid-I9601s, had a
H2S removal efficiency of about 90 percent. Changes in the processing rates
allowed an increase in efficiency to about 93 percent at the cost of increased
utilities consumption. A further process modification has given the new
two-stage vacuum carbonate process an H2S removal of around 98 percent without
a further increase in utilities consumption.
Recognition that organic sulfur not removed by the vacuum carbonate
system accounts for about 5 percent of the sulfur in coke oven gas requires
that the overall efficiencies be reduced to 86 to 93 percent.
Spent absorbing solution from vacuum carbonate plants must be periodi-
cally replaced. The rate is variable; one plant has run three years before
replacing the solution, while another has had to replace the solution every 8
months. Thiocyanate and thiosulfate salts, as well as iron-sulfur-cyanide
compounds are the major contaminants. Further quantification of this stream
was not available in the literature. Reduced contamination of the carbonate
solution is claimed if oxygen and ammonia in the gas and absorbent solution
are minimized.
Ejector jet condensate is the second major vacuum carbonate system dis-
charge. The volume of this waste (roughly 40 1/Mg coal charged64) could be
greatly reduced or eliminated by the use of mechanical ejectors rather than
steam jets, as was once standard.14
Sulfiban System
The Sulfiban system can be operated up to about 98 percent efficiency,
and is the only common desulfurization technique that removes both organic and
inorganic sulfur from coke oven gas. The major liquid waste from the Sulfiban
system is spent absorbing solution; the rate of purge is around 140 I/day in a
5,000 Mg coal/day coke plant. The purge is a sludge containing FeS, Prussian
102
-------
Blue, thiourea,64 and a gummy material apparently formed by reaction between
HCN and the amine. It has been reported that this sludge can be disposed of
in the sinter plant.64
Dravo/Still Process
The Dravo/Still H2S removal system is offered in two versions which
reduce the H2S content of the coke oven gas to 35-50 gr H2S/100 scf (90-93
percent efficiency for 500 gr H2S loading) and 10 gr H2S/100 scf (98 percent
removal), respectively. Organic sulfur is not removed. H2S removal then
ranges from 90 to 98 percent, and overall desulfurization from around 86 to 93
percent. No secondary environmental effects have been reported for the Dravo/
Still process.
Stretford Process
The Stretford process is another H2S absorber with a very high (99+
percent) H2S removal efficiency. The process produces elemental sulfur
directly, so no auxiliary acid gas treatment (Glaus Plant or acid plant) is
required. The Stretford process has a significant secondary effluent problem
with the by-product thiocyanates and thiosulfates formed by the reaction of
HCN with the absorbing solution. Some treatment processes produce a purge
stream eventually while another incinerates portions of the waste. Present
emphasis is on the incinerator approach. No data or emissions from the incin-
erator were available in the literature.
Glaus Sulfur Plants
Claus sulfur plants convert the incoming acid gas to elemental sulfur
with efficiencies of roughly 95 to 98 percent. Tail gas from a Claus plant
can be treated in one of several available tail gas treatment systems, giving
overall efficiencies of 99 percent. Documented Claus plant performance at
by-product plants has been more like 95 percent efficiency. Following tail
gas treatment, the gas stream is usually incinerated, converting any residual
sulfur to S02.
Sulfuric Acid Plants
The overall efficiency of single-stage sulfuric acid plants is around 97
percent. Double stage plants or plants with tail gas treatment can exceed 99
percent efficiency.
103
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6.8 ENVIRONMENTAL EFFECTS OF WASTEWATER .PROCESS
As has been discussed, wastewater treatment in the by-product coke indus-
try varies considerably. The principal effluent, of course, depends on the
process. The primary source of water to the treatment plant is excess ammonia
liquor, a Level 1 analysis of which is presented in Table 23. The pollutants
from a biological treatment plant are vapor off the holding tanks and aeration
basins, the biological sludge, and whatever is left in the effluent water.
Biological Sludge
The sludge from the sampled plant was analyzed for both elemental and
organic components as directed by the Level 1 protocol. The elemental anal-
ysis is presented in Table 24. Organic analysis results are presented in
Table 25. The sludge was produced at a rate of 1.7 kg/Mg coke, and was re-
moved from the plant by a contractor. Some potential problem areas are identi-
fied by the Level 1 analysis.
Vapor off the Holding Tanks and Aeration Basins
Vapor emissions from these sources were not measured. The only source of
information located65 documented batch stripping of coke plant wastewater with
air for 10 days. The results were a 15 percent reduction in organic carbon
and a 30 percent reduction in cyanide. The authors felt that this was higher
than would be encountered in a biological plant, and concluded that stripping
would not be significant. Ammonia was not stripped to a measurable degree in
this test.
Effluent from Biological Plant
The feed and effluent of a biological treatment plant was analyzed by the
Cyrus Rice Corporation for the U.S. EPA under a separate contract.66 All .
contaminated coke plant wastewater was fed to the biological plant. The
samples were 24 hour integrated samples taken on 3 consecutive days. Prelimi-
nary results of this analysis are presented in Table 26. The data are still
being analyzed and some values may change.
104
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TABLE 23. ORGANIC EXTRACT SUMMARY, AMMONIA LIQUOR
Preliminary
Concentrate
LCI
LC2
LC3
LC4
LC5
LC6
LC7
I
TCO
(nig)
10,700
5,950
730
4,300
315
260
70
3,180
0
8,855
GRAV
(mg)
7,720
6,420
1,890
900
740
320
0
1,190
130
5,170
Total Organics
(mg/1)
2,420
1,630
346
687
139
77
9.2
577
17
1,850
Comments
pH 2 extract: The pH 2 extract contained about 80 percent of the ammonia
liquor organics. Specific coal tar PNA's identified by LRMS at relative intensi-
ties of 100 and 10; these included pyrene, perylene, benzpyrene, chrysene, anthra-
cene and others. Other compounds found were polycyclic amines and substituted
phenol.
pH 12 extract: Most of this sample was found in LC cut 6, which was complex
and difficult to analyze. Aromatic and aliphatic character was detected along
with hydroxyl and ketone/ester bands.
105
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TABLE 24. SSMS* ANALYSIS.OF BIOLOGICAL PLANT SLUDGE SAMPLE
Element
u
Th
Bi
Pb
Tl
Au
Ir
Os
Re
W
Hf
Lu
Yb
Tm
Er
Ho
DY
Tb
Gd
Eu
Sm
Nd
Pr
Value (ppm)
< 0.025
< 0.023
< 0.021
0.18
< 0.020
< 0.020
< 0.019
< 0.019
< 0.019
< 0.018
< 0.018
< 0.017
< 0.017
< 0.017
< 0.017
< 0.016
< 0.016
< 0.016
< 0.016
< 0.015
< 0.015
< 0.014
< 0.014
Element
Ce
La
Ba
Cs
I
Te
Sb
Sn
In
Cd
Pd
Rh
Ru
Mo
Nb
Zr
Y
Sr
Rb
Br
Se
As
Ge
Value (ppm)
0.011
< 0.014
0.27
0.004
< 0.03
< 0.013
0.014
0.10
ISt
0.19
< 0.011
< 0.010
< 0.010
0.065
0.003
0.030
0.006
0.95
0.090
3.0
6.4
2.5
0.81
Element
Ga
Zn
Cu
Ni
Co
Fe
Mn
Cr
V
Ti
Ca
K
Cl
S
P
Si
Al
Mg
Na
F
B
Be
Li
Value (ppm)
< 0.021
2.0
1.3
14.
0.16
210.
5.2
0.071
0.025
0.30
0.21 %
12.
270.
0.13 %
27.
32.
24.
96.
0.10 %
26.
0.69
0.006
0.23
*SSSMS - Spark Source Mass Spectrometer
tIS - Internal Standard
106
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TABLE 25. SUMMARY OF ORGANIC ANALYSES, BIOLOGICAL TREATMENT PLANT SLUDGE
Liquid Chromatography
Aliphatic hydrocarbons
Halogenated aliphatics
Aromatic hydrocarbons
Halogenated aromatics
Heterocyclic N, 0, S compounds
Sulfide, disul fides
Nitri les
Ethers
Aldehydes, ketones
Nitroaromatics
Alcohols
Amines
Phenols
Esters, amides
Mercaptans
Carboxylic acids
Sulfoxides
GRAV cone.
TCO cone.
MATE
Comparison
Value
mg/kg
2.1
0.2
6.45
0.13
0.025
0.025
0.025
3.32
3.5
0.3
3.00
0.30
3.2
3.5
0.33
2.73
0.03
5.9 - 7.4 mg/kg
0.4 - 17.8 mg/kg
MEG's
Category
Number
1
2
15.21A.22
16
23,24,25
13B
9
3,4
7
17
5,6
10,11,12
18,19,20
8C.8D
13A
8A.8B
14
Min. MATE
Value in
Category
None
published
20
0.003
0. 00001
3.0
None
published
2.0
20
0.2
2.0
2.0
0.04
0.01
0.003
30
2.0
1,200
Ratio
None
published
0.01
2,150
13,000
0.008
-
0.012
0.17
17.5
0.15
1.5
7.5
320
1,170
0.01
1.4
0.00002
MEG = Multimedia Environmental Goals.
MATE - Minimum Acute Toxicity Effluent.
"Sludge density assumed to be 1 g/ml.
-------
TABLE 26. BIOLOGICAL TREATMENT PLANT TESTING-SELECTED RESULTS
1
COMPONENT
Ammonia
Organic carbon
Chloride (diss.)
Cyanide Amenable to Chlorination
Total cyanide
Cyanide (AISI)
Nitrogen (Kjeldahl)
Suspended solids
Solvent extract (oil) EPA method
Sulfate (diss.)
Sulfide
Thiocyanate (SCN)
Cyanate (CNO)
Phenolic compounds (phenol)
PH
2
Organic compounds
acenaphthene
benzene
carbon tetrachloride
chlorobenzene
hexachloro benzene
1,1,2,2-tetrachloroethane
2-chloronaphthalene
2,4,6-trichlorophenol
parachlorometa cresol
chloroform
2-chlorophenol
1,1-dichloroethylene
2,4-dichlorophenol
2,4-dinitrotoluene
2,6-dinitro toluene
1,2-diphenylhydrazine
ethylbenzene
fluoranthene
2-nitrophenol
4-nitrophenol
2,4-dinitrophenol
4,6-dinitro-o-cresol
pentachlorophenpl
phenol
bis(2-ethylhexyl)phthalate
butyl benzyl phthalate
di-n-butyl phthalate
di-h-octyl phthalate
dimethyl phthalate
benzofalanthracene
benzo(a)pyrene
3,4-benzofluoranthene
benzo(k)fluoranthene
chrysene
acenaphthylene
• anthracene
benzo(gni)perylene
fluorene
phenanthrene
dibenzo(a,h)anthracene
indene(1,2,3-cd)pyrene
pyrene
tetrachloroethylene
toluene
trichloroethylene
UNITS
mg/l
mg/l
mg/l
mg/l
mg/l
mg/l
mg/l
mg/l
mg/l
mg/l
mg/l
mg/l
mg/l
mg/l
PPb
ppb
ppb
ppb
ppb
ppb
ppb
PPb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
PPb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
PPb
ppb
ppb
ppb
PPb
PPb
ppb
ppb
ppb
PPb
ppb
ppb
ppb
AVERAGE OF
FEED
28
383
371
0.48
2.74
0.18
102
79
20
202
153
197
3.6
231
11.2
Range from
0
0<3SO
0
0 to 250
0 to 17,1 00
OOOO
Oto 160
NO
NO to 2,130
0 to < 3,800
NO
0 to <4,600
NO to 4,500
0
0 to 29,700
0
Oto 100
Oto 190
NO
NO
NO
NO
NO
11 2,000 to 13 1,500
0 to 29,000
200 to 8, 600
40 to 12,100
0 to 350
0
0 to 2,270
0 to 330
Oto<140
Oto<14Q
0 to 3,800
90 to 34,900
< 200 to < 1,000
0
0 to < 1,000
<200 to < 1,000
0
0
0 to 280
0 to <650
Oto 120
Oto<100
3 SAMPLES
EFFLUENT
0.73
53
202
0.33
2.34
0.07
10.9
39
4.3
342
<0.3
0.73
0.35
0.028
7.4
3 Samples
1-6
<1to<371
Oto 9
159 to 264
46 to 82
<3 to <820
0
NO
10 to 168
9 to <990
NO
0 to < 1,205
NO
<7to 10
Oto<7
0 to 137
Oto 12
NO
NO
NO
NO
NO to 93
NO to 35
Oto 39
2 to 85
14 to 22
0 to 320
Oto 53
Oto 24
Oto 44
Oto<6
0 to<6
Oto 14
Oto 6
0 to < 239
Oto<1
5 to 9
0 to <239
Oto<1
Oto<1
16 to 38
0 to <580
0 to 100
0 to < 1,148
NOTES: Vhese are preliminary data released by the Effluent Guidelines Division, U.S. EPA.
2NO indicates not detected in one of the three samples. "0" indicates that no evidence was found,
but that noise in the spectrum prevents a clear NO.
108
-------
6.9 AMBIENT AIR ANALYSIS - BY-PRODUCT PLANT
Upwind-downwind ambient sampling was conducted at the plant in two separ-
ate programs. Hydrogen cyanide was collected in 24-hour integrated samples
and 4-hour Level 1 organic runs were made on one day.
Cyanide Analysis
The results of the cyanide analysis are summarized in Table 27, which
also shows the orientation of the samples and the daily wind roses. On the
two days in which the wind blew across the plant from a roughly constant
direction, the cyanide in the air increased roughly one order of magnitude,
from an average of 0.006 vppm upwind to an average of 0.062 vppm downwind.
Ambient Organic Vapor Analysis
Ambient organic vapor samples were taken for 4 hours, the downwind sample
first and the upwind second. The results are summarized in Tables 28 and 29.
The GC results show a slight increase in the ambient benzene concentration,
from 0.6 to 0.8 vppm across the plant but the downwind samples were 0.3 and
1.3 vppm--inconsistent. The downwind sample had inadequate organic mass for
the liquid chromatography. As can be seen, more organics were collected on
the XAD resin upwind of the plant than downwind. The upwind sample point was
close to a railroad, which may have had some impact.
6.10 RELATIVE HAZARD OF BY-PRODUCT PLANT SOURCES
The large amount of data relating to emissions to the three media are
difficult to evaluate. In this section the relative hazard of the sources
(i.e., relative to each other) is developed. The procedure used is essen-
tially a continuation of the techniques used earlier. The ratios of the MATE
values for a source were first totalled by category. These ratios were defined
as hazard units. The hazard units were then summed across the categories to
arrive at a total of hazard units for the source emission (based on a volume
or mass). Each source for which these provided sufficient data was treated in
this way. For the "Heavy Organics" category, only compounds confirmed by GCMS
were included. The data base was incomplete in one or more categories for all
of the sources.
109
-------
TABLE 27. AMBIENT CYANIDE ANALYSIS
SAMflE STATION 1
- ""'"'
DD
o
1 1 r-
1 BVPROIIUCT PLANT |
DO O COOLEU SUIFATE EXHAUSTERS
0 STORAGE SAIOHATOBS
NAPHTHALENE
n^P "~" a
1 ID a "">"•" S
0 0 °°°/^\^^
0 O | 1 V I (1
0 O i 1 s — ' ^-^ GASHOLDERS
•J O LIGHT ^-^
IIIHI OH .ICIVERY ™,*ltB M«UiM U
AWHOXIMATE SCALE. FT
100 200 300 4M MO
GENERAL ARRANGEMENT Of PLANT.
O O OO
TAR PROCESSING
=3 D o O O
© SAMPLE STAHON 2
Relative duration of wind from indicated direction.
1500 12/13/77 to 1500 12/14/77
Station 1 Downwind -0.069 vppm
Station 3 Upwind -0.008 vppm
1500 12/12/77 to 1500 12/13/77
W
Station 1 (Downwind) -0.056 vppm
Station 3 (Upwind) -0.004 vppm
-------
TABLE 28. SUMMARY OF ORGANIC ANALYSIS, UPWIND AMBIENT
Compounds Identified
i /"»/"*
by GC
C!-C7 HC (Avg. MW = 16)
Benzene
Toluene
Xylenes and ethyl benzene
Sulfur compounds (as H2S)
Liquid Chromotography
Aliphatic hydrocarbons
Halogenated aliphatics
Aromatic hydrocarbons
Halogenated aromatics
Heterocyclic N, 0, S
compounds
Sul fides, disul fides
Nitrites
Ethers
Aldehydes, ketones
Ni troaromatics
Alcohols
Amines
Phenols
Esters, amides
Mercaptans
Carboxylic acids
Sulfoxides
GRAV cone, in sampled gas
TCO cone, in sampled gas
Concentration,
mg/sm3
1.9
1.95
not detected
not detected
not detected
MATE
Comparison
Value
mg/sm3
0.12
--
0.32
0.02
— _
--
__
0.33
0.20
0.01
0.03
0.03
0.03
0.33
0.03
0. 03
0.03
0.8--1.4 mg/sm3
3,6 mg/sm3
MEGsa
Category
Number
1
15
15
15
53
MEGsa
Category
Number
1
2
15, 21A, 22
16
23, 24, 25
13B
9
3, 4
7
17
5, 6
10, 11, 12
18, 19, 20
8C, 8D
13A
8A, 8B
14
MATEb
Value,
mg/sm3
min. = 32
3
375
435
15
Min. MATE
Value in
Category
32
0.1
1.0
0.7
0.1
20
1.1
0.01
0.2
l.o
10
Ratio
/Cone. FoundX
\ MATE )
0.06
0.65
» »
—
b
Ratio
0.004
0.32
0.03
_w
-._
m
33
1.0
0.01
0.003
0.001 30
0.1
1.0
1.0
0.3
1.0
0.3
0.33
0.03
0.1
0.03
MEG = Multimedia Environmental Goals.
MATE = Minimum Acute Toxitity Effluent.
Italics highlight categories found by GC/MS in some samples.
Ill
-------
TABLE 29. SUMMARY OF ORGANIC ANALYSIS, DOWNWIND AMBIENT
Emission Rate
Compounds Identified
by GC
C!-C7 HC (Avg. MW s 16)
Benzene
Toluene
Xylenes and ethyl benzene
Sulfur compounds (as H2S)
Liquid Chromotography
Concentration,
mg/sm3
2.2
2.4
not detected
not detected
not detected
MATE
Comparison
Value
mg/sm3
MEGsa
Category
Number
1
15
15
15
53
MEGsa
Category
Number
u
MATE0
Value,
mg/sm3
min. = 32
3
375
435
15
Min. MATE
Value in
Category
Ratio
/Cone. Found\
\ MATE /
0.07
0.8
—
— —
""
Rati o
Aliphatic hydrocarbons
Halogenated aliphatics
Aromatic hydrocarbons
Halogenated aromatics
Heterocyclic N, 0, S
compounds
Sulfides, disulfides
Nitriles
Ethers
Aldehydes, ketones
Nitroaromatics
Alcohols
Ami nes
Phenols
Esters, amides
Mercaptans
Carboxylic acids
Sulfoxides
GRAV cone, in sampled gas
TCO cone, in sampled gas
INSUFFICIENT
ORGANIC MASS
NO
LIQUID
CHROMATOGRAPHY
1.2—2.2 mg/sm3
0—0.1 mg/sm3
MEG = Multimedia Environmental Goals.
3MATE = Minimum Acute Toxicity Effluent.
112
-------
The emission rate for the source was then taken into account by multi-
plying the total of hazard units per scm, £, or kg by the emission rate in
scm/Mg, A/Mg, or kg/Mg to arrive at the weighted total hazard units per Mg of
coal fed to the ovens.
The results of this procedure are presented in Table 30. As with the
other data manipulations which are based on the MATE values, this procedure is
very sensitive to the presence of certain compounds (primarily PNA's) which
have very low MATE values (i.e., are considered to be very hazardous). For
instance, benzo(a)pyrene, at a median concentration of 22 parts per billion,
accounts for nearly 75 percent of the total hazard units attributed to the
biological treatment plant effluent. Similar impact for the PNA's is present
for several other sources.
113
-------
TABLE 30. ESTIMATED RELATIVE HAZARD OF COKE BY-PRODUCT PLANT SOURCES
Source Emission
Rate Per Hg
Coal Fed
Operation Emission
Source
Tar processing
decanter vapor 1.5 scm
dewatering/
storage vapor 0. 1 scm
primary cooler
condensate
tank vapor 1.2 scm
distillation
product storage
vapor 0.02 scm
Ammonia processing
excess ammonia
liquor 102 SL
Final cooler and
napthalene handl-
ing
cooling tower for
contact cooler,
gas 2,307 scm
napthalene sepa- rate too low to
rator vapor measure
napthalene dryer
vapor 2.1 scm
Light oil recovery
wastewater (wash
oil, sludge) 70-360 I
light oil
storage vapor 11.1 scm
Wastewater
biotreatment
plant
effluent 335-900 t
biotreatment
plant
sludge 1.2 kg
TOTAL
Total Total
Hazard Hazard Normal-
Units Units ized
Ratios of Concentrations3 to HATE Values Per scm, Per Mg Relative
(Defined as Hazard Units, HU) S., or kg Coal Hazard
Light Aromatics Heavy Organics Gaseous S Biphenyl &
(BTX) including PNA's NH3 Compounds Cyanides Phenols Quinoline
2,430 519 NO 394 NO 0.6 22.1 3,366 5,050 0.036
22.1 43 NO NTO NTD 0.7 2.3 68 6.8 =0
1,745 NO ND 222 NTD ND ND 1,967 2,400 0.017
110 7,056 ND ND NTD 49 ND 7,215 140 0.001
Not an emission - treated in biotreatment plant
5.3 7.4 «ND 0.02 8.4 0.02 0.08 21.2 49,000 0.349
1,567 3,462 ND 142 ND 58 ND 5,229 •
Sample results unreasonable and not representative
Not an emission - treated in biotreatment plant
346 ND ND 2.6 ND ND ND 349 3,900 0.028
0.2 77 NA ND NA 21.4 NO 98.6 61,000 0.434
ND 15,350 NO ND ND 320 ND 15,670 19,000 0.135
140,497
ND: Not determined; NTD: Not detected; NA: Either concentration or MATE value not available
a: For concentration ranges, the median was used
b: Relative Hazard = Total hazard units per Mg coal/140,497
-------
-------
7.0 PREFERRED TECHNOLOGY AND PROBLEMS OUTSTANDING
7.1 INTRODUCTION
Three topics appear to deserve mention in this section:
1. Vents from storage tanks and vessels,
2. Naphthalene handling and final coolers, and
3. Cyanide handling.
This discussion is qualitative, as the data are insufficient to support a
solid quantitative discussion.
It should be mentioned here that Dun!op and McMichael47 have discussed
in detail one approach to determining optimum treatment methods for a coke
plant. Dunlop and McMichael concluded that overall, wastewater quenching
was better than wastewater discharge regardless of treatment level. In
addition, they concluded that some treatment levels produced adverse overall
results. The reader should refer to the cited paper47 for the complete
discussion.
Vents from Tanks and Process Vessels
A large proportion of the emissions from a by-product plant originate in
the various vents in the plant. Recovery of vapor from these sources will
generally be complicated by the presence of naphthalene. Wilputte Corpora-
tion19 has installed water sprays on some tar decanters, and the techniques
might be extended to other vents. Vapor recovery from these sources to the
suction side of the exhausters, probably ahead of the primary coolers, might
be possible. Naphthalene condensation would require that the vents be heated,
and the corrosive nature of the vapor (perhaps including chlorides) would
cause materials problems. The system might be designed to float on coke oven
gas at slightly above atmospheric pressure.
Naphthalene and Final Coolers
Naphthalene collection in open vessels inherently causes naphthalene
emissions. Avoidance of exposed naphthalene by the use of a tar bottom
115
-------
final cooler and keeping the naphthalene in the tar are proven and should
be preferable. A wash oil final cooler also collects naphthalene, but the
naphthalene must eventually be removed from the wash oil. The final cooler
cooling tower with a tar bottom final cooler would still have about the same
level of cyanide emissions, although hydrocarbons emissions might be down.
A wash oil final cooler should avoid the cyanide emissions, although the
cyanide must go somewhere.
Cyanide Handling
A significant proportion of the cyanide is collected in the ammonia
liquor, and some is stripped out in the ammonia stills. Essentially all
could be stripped from the liquor. The final cooler will collect some and
it may be emitted in the cooling tower. Cyanide in the gas will complicate
life for a desulfurization unit. The point is that the complete cyanide
distribution must be considered before one can be comfortable with any
particular treatment scheme.
116
-------
REFERENCES
1. U.S. Department of Interior, Bureau of Mines, Coke and Coal Chemicals
in 1975, Washington, D.C., 1976.
2. Rhodes, E. 0., "The Chemical Nature of Coal Tar," Chap. 31 in H. H.
Lowry, ed., Chemisty of Coal Utilization, New York: Wiley, 1945.
o
3. Glowacki, W. L., "Light Oil from Coke-Oven Gas," Chap. 28 in H. H.
Lowry, ed., Chemistry of Coal Utilization, New York: Wiley, 1945.
4. McGannon, H. E., ed., The Making, Shaping and Treating of Steel, 9th
ed., Section 4, U.S. Steel, Pittsburgh, 1971.
5. McNeil, D., Coal Carbonization Products, New York: Pergamon Press,
1966.
6. Wilson, P. J., Jr., and J. H. Wells, Coal, Coke, and Coal Chemicals,
New York: McGraw-Hill, 1950.
7. Thiessen, G., "Forms of Sulfur in Coal," Chap. 12 in H. H. Lowry, ed.,
Chemistry of Coal Utilization, New York: Wiley, 1945.
8. Ortuglio, C., J. G. Walters, and W. L. Krobot, "Carbonization Yields,
Analyses, and Physical Characteristics of Cokes from American Coals,"
Report PERC/B-75/1, U.S. Energy Research and Development Administra-
tion, Washington, D.C., 1975.
9. Powell, A. R., "Gas from Coal Carbonization," Chap. 25 in H. H. Lowry,
ed., Chemistry of Coal Utilization, New York: Wiley, 1945.
10. Porter, H. C., Coal Carbonization, New York: Chemical Catalog Co.,
1924. Cited by Hill, Chap. 27 in H. H. Lowry, ed., Chemistry of Coal
Utilization, New York: Wiley, 1945.
11. Davis, J. D., "Dependence of Yields of Products on Temperature and Rate
of Heating," Chap. 22 in H. H. Lowry, ed., Chemistry of Coal Utilization,
New York: Wiley, 1945.
12. Kirner, W. R., "The Occurrence of Nitrogen in Coal," Chap. 13 in H. H.
Lowry, ed., Chemistry of Coal Utilization, New York: Wiley, 1945.
13. Hill, W. H., "Recovery of Ammonia, Cyanogen, Pyridine, and Other Nitrog-
enous Compounds from Industrial Gases," Chap. 27 in H. H. Lowry, ed.,
Chemistry of Coal Utilization, New York: Wiley, 1945.
117
-------
14. Gollmar, H. A. , "Removal of Sulfur Compounds from Coal Gas," Chap. 26
in H. H. Lowry, ed., Chemistry of Coal Utilization. New York: Wiley
1945.
15. Ode, W. H., "Coal Analysis and Mineral Matter," Chapter 5 in H. H.
Lowry, ed., Chemistry of Coal Utilization, supplementary volume New
York: Wiley, 1963.
16. Muder, R. E., "Light Oil and Other Products of Coal Carbonization,"
Chap. 15 in H. H. Lowry, ed., Chemistry of Coal Utilization, supple-
mentary volume, New York: Wiley, 1963.
17. Weiler, J. F., "High-Temperature Tar," Chap. 14 in H. H. Lowry, ed.,
Chemistry of Coal Utilization, supplementary volume, New York: Wiley,
1963.
18. Dunlap, R. W., and F. C. McMichael, "Reducing Coke-Plant Effluent "
Env. Sci. Tech. 10:654 (1976).
19. Private communication with John Crosby, Wilputte Corporation.
20. Considine, D. M., ed., Chemical and Process Technology Encyclopedia,
New York: McGraw-Hill, 1974, p. 597. —
21. U.S. Department of Interior, Bureau of Mines, Coke Producers in the
United States in 1975, Washington, D.C., 1976.
22. American Iron and Steel Institute, Directory of Iron and Steel Works of
the United States and Canada. 33rd ed., Washington, D.C., 1974.
23. Schroeder, J. W., and A. C. Naso, "A New Method of Treating Coke Plant
Wastewater," Iron and Steel Engineer, 53(12):60 (1976).
24. Traubert, R. M., "Weirton Steel Div.—Brown's Island Coke Plant," Iron
and Steel Engineer. January 1978, pp. 61-64.
25. USS Engineers and Consultants, Inc. (a subsidiary of U.S. Steel), "USS
Phosam Process," Bulletin 2-01, no date.
26. Grosick, H. A., "Ammonia Disposal—Coke Plants," Blast Furnace and Steel
Plant. 59:217 (1971).
27. Wilks, F., "Phenol Recovery from Byproduct Coke Waste," Sewage and Indus-
trial Waste. 22(2):196 (1950).
28. Nicklin, T. et al., U.S. 3,035,889 of May 22, 1962, assigned to Clayton
Aniline Co., Ltd., U.K.
29. Massey, M., and R. W. Dunlap, "Assessment of Technologies for the
Desulfurization of Coke Oven Gas," AIME Ironmaking Proc., 36:583 (1975).
118
-------
30. Kohl, A. L., and F. C. Reisenfeld, Gas Purification, Chaps. 2-5, New
York: McGraw-Hill, 1960.
31. Danckwerts, P. V., Gas-Li quid Reactions, Chap. 10, New York: McGraw-
Hill, 1970.
32. Laufhuette, D., "Hydrogen-Sulfide/Ammonia Removal from Coke-Oven Gas,"
AIME Ironmaking Proc., 33:142 (1974).
33. Massey, M. J., and R. W. Dunlap, "Economics and for Sulfur Removal from
Coke-Oven Gas," JAPCA, 25:1019 (1975).
34. Anon., Process Description of Koppers Two-Stage Vacuum Carbonate System,
Pittsburgh: Koppers Co., 1976.
35. Shoeld, M. , US 1,971,798 (1934) to Koppers Co., cited in A. L. Kohl
and F. C. Riesenfeld, Gas Purification, Chaps. 2-5, New York: McGraw-
Hill, 1960.
36. Maddalene, F. L., "Desulfurization of Coke Oven Gas by the Vacuum
Carbonate Process," in W.-K. Lu, ed., Proceedings of symposium on treat-
ment of coke-oven gas, McMaster Symposium on Iron and Steel making No.
5, May 6 and 7, 1977, McMaster University Press, Hamilton, Ontario.
37. Singleton, A. H., and G. Batterton, "Coke-Oven Gas Desulfurization using
the Sulfiban Process," AIME Ironmaking Proc.. 34:604 (1975).
38. Williams, J. A., and Homberg, 0. A., "Coke-Oven Gas Desulfurization and
Sulfur Recovery Utilizing the Sulfiban Process," AIME Ironmaking Proc.,
35:98 (1976).
39. Kent, R. L., and B. Eisenberg, "Better Data for Amine Treating," Hydro-
carbon Processing. 55(2):87 (1976).
40. Williams, J. A., and 0. A. Homberg, "Coke-Oven Gas Desulfurization
Utilizing the Sulfiban Process," in W.-K. Lu, ed. , Proceedings of Sym-
posium on Treatment of Coke-Oven Gas, McMaster Symposium of Iron and
Steelmaking No. 5, May 6 and 7, 1977, McMaster University Press,
Hamilton, Ontario.
41. Ananymous, "Annual Review of Developments in the Iron and Steel Industry
During 1972," Iron and Steel Engineer, 50(1):D1 (1973).
42. Kohl, A. L., and F. C. Riesenfeld, Gas Purification, Chap. 9, New York:
McGraw-Hill, 1960.
43. Ludberg, J. E., "Removal of Hydrogen Sulfide from Coke-Oven Gas by the
Stretford Process," Paper 74-185, Denver Meeting of the APCA, 1974.
44. Ozaki, Si, et al., "Development of New Coke-Oven Gas Desulfurization
Process," Chem. Econ. Eng. Rev., 8(3):22 (1976).
119
-------
45. Weast, R. C., ed., Handbook of Chemistry and Physics. 49th ed pp
D87-92; Cleveland: Chemical Rubber Co. , 1968.
46. U.S. Environmental Protection Agency, "Development Document for Effluent
Limitations Guidelines and New Source Performance Standards for the
Steel Making Segment of the Iron and Steel Manufacturing Point Source
Category," Report EPA-440/l-74-024-a, Washington, June 1974.
47. Dunlap, R. W., and F. C. McMichael, "Air, Land, or Water: The Dilemma
of Coke Plant Wastewater Disposal," presented at AISI Meeting, New
York, May 1975.
48. Melin, G. A., J. L. Niedzwiecki, and A. M. Goldstein, "Optimum Design of
Sour-Water Strippers," Chem. Eng. Progress. 71(6):78 (1975).
49. Homberg, 0. A., and A. H. Singleton, "Performance and Problems of Claus
Plant Operation on Coke-Oven Acid Gases," JAPCA 25:375 (1975).
50. Mitachi, K., "Cleaning Sodium Absorbents in Tailgas Recovery Circuits "
Chem. Eng.. 80(21):78 (1973).
51. U.S. Environmental Protection Agency, "Technical Support Document for
S02 Emissions from Coke-Oven Gas Combustion," Washington, January 1977.
52. Kurtz, J. K. , "Recovery and Utilization of Sulfur from Coke-Oven Gas,"
in F. S. Mallette, ed., Problems and Control of Air Pollution, New
York: Reinhold, 1955. ~~~
53. Pearson, E. F., "Research Study of Coal Preparation Plant and Byproduct
Coke Plant Effluents," EPA-660/2-74-050, NTIS PB 252 950, April 1974.
54. American Iron & Steel Institute, Directory of Iron and Steel Works of
the United States and Canada. 34th ed., Washington, D.C., 1977.
55. Survey conducted for Effluent Guidelines Division of the U.S. Environ-
mental Protection Agency.
56. Anonymous, "Last Gasp Desulfurization for Coke-Oven Gas Taking off as
States Start Cracking Down," 33 Magazine. October 1976.
57. Lu, W.-K., ed., "Proceedings of Symposium on Treatment of Coke-Oven Gas,
McMaster Symposium of Iron and Steelmaking No, 5," May 6 and 7, 1977,
McMaster University Press, Hamilton, Ontario.
58. Hamersma, J. W., S. L. Reynolds, and R. F. Maddalone, "IERL-RTP Proce-
dures Mannual: Level I Environmental Assessment," EPA-600/2-76-160a,
NTIS PB 257 850.
59. Harris, J. L., "Suggested Report Format for Level I Organic Analysis
Data," ADL Report No. 79347-16-4, October 21, 1977.
120
-------
60. Cleland, J. G. and G. L. Kingsbury, "Multimedia Environmental Goals for
Environmental Assessment," EPA-600/7-77-136a and EPA-600/7-77-136b,
November 1977.
61. Rudzki, E. M., K. R. Burcaw, and R. J. Horst, "An Improved Process for
the Removal of Ammonia from Coke Plant Weak Ammonia Liquor," AIME
Ironmaking Proc., 36:525 (1977).
62. Carbone, W. E., "Dephenolization of byproduct coke plant ammonical
liquor," Journal Water Pollution Control Federation, 33:834, (1963).
63. Carbone, W. E., "Phenol Recovery from Coke Wastes," Sewage and Indus-
trial Waste. 22(2):200 (1950).
64. Massey, M., Environmental Control of Sulfur in Iron and Steelmaking,
Carnegie-Mellon University, Ph.D. Dissertation, 1974 University Micro-
films International, Ann Arbor, Michigan.
65. Adamrs, C. E., Jr., R. M. Stein, and W. E. Eckenfelder, Jr., "Treatment
of Two Coke Plant Wastewaters to Meet Guideline Criteria," Proceedings:
29th Industrial Waste Conference. Purdue University, May 1974, pp.
864-81.
66. Plant Visit Report, C. W. Rice Corp. for Effluent Guidelines Division
of the U.S. Environmental Protection Agency, Plant No. 003, Visit dates
Dec. 5-8, 1977.
67. "Methods for Chemical Analysis of Water and Wastes," EPA 625/6-74-003,
1974.
68. Perry, R. H., and C. H. Chilton, Chemical Engineers' Handbook, 5th ed.,
New York: McGraw-Hill, 1973.
69. Ball, D. A., A. A. Putman, and R. G. Lace, "Evaluation of Controlling
Hydrocarbon Emissions from Petroleum Storage Tanks," EPA 450/3-76-036,
NTIS PB 262 789, November 1976.
70. Chemical Marketing Reporter, September 12, 1977, Schnell Publishing
Company.
121
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APPENDIX A
SAMPLING AND ANALYSIS PROGRAM
A-l
-------
APPENDIX A
SAMPLING AND ANALYSIS PROGRAM
DESCRIPTION OF BY-PRODUCT PLANT SAMPLED
A flow plan of the coke by-product recovery plant at which the sampling
was done (Fairfield Works, U.S. Steel Corporation) is presented as Figure
A-l. Salient features are:
indirect primary coolers with recirculating cooling water;
*
scrubber type tar extractors;
saturated ammonium sulfate crystallizers with centrifugal
dewatering;
contact recirculating water final cooler with froth flotation
naphthalene separator and integral cooling tower;
naphthalene dried by steam heating;
light oil recovery in multiple scrubbers and rectification to
secondary light oil and the light oil stream;
no desulfurization;
flash distillation of tar into chemical oil and pitch;
Further descriptive information is provided where appropriate in the
work-up of individual samples and emission rates.
SAMPLING
The sampling and analysis performed during this project was based on
the EPA Level 1 protocol.58 The Level 1 protocol recommends that all identi-
fied emissions to all media be sampled and analyzed, as well as the feeds to
and products of the process. Level I samples are short-term integrated
samples for the gases, and grab samples for solids and liquids. The Source
Assessment Sampling System (SASS) is the primary sampling apparatus for
gaseous samples. The SASS consists of a heated probe, three cyclones and a
filter to collect and size particulate (all enclosed in an oven), an adsorbant
A-2
-------
FLUSHING LIQUOR
FLUSHING LIQUOR
COKE OVEN PRIMARY
GAS (COG) / COOLER
COG
MAKE-UP
FLUSHING
LIQUOR
FLUSHING
COKE OVEN GAS (COG)
TAR EXTRACTORS
EXHAUSTERS
T.
1
WAS
r
TK
105
TEWAT
4
ER AM
/
TK
10?
MO Ml
i
WASTEWATER TREATMENT
(INCLUDING NH, STILLS)
^ KV7-77-771 -1
TAR TAR
h "
A LIQUOR
- — * — — ~
COG
TO TK106
a
» *
ANHYDROUS NH3
AMMONIA LIQUOR
&TAR
WASTEWATER
COG TO-*
FUEL
VENT
CO
EC
O
o
si
rl
SATURATORS
k ^i
\y
V
AMMONIUM SULFATE
WET NAPHTHALENE
WATER
TO WASTE
TREATMENT
BAROMETRIC
CONDENSER
CRUDE NAPHTHALENE
WATER
STEAM
Figure A-1. Flow diagram: Coke by-product recovery plant at USS Fairfield works.
-------
module (XAD-2 resin) to collect C7 and heavier organics, and a series of
impingers to collect inorganic vapors. Light (Ci-Cy) organic vapors and
sulfur species are collected as grab samples using glass bulbs and are
analyzed on-site by gas chromatography (GC). Samples were collected at only
one plant. Considerations important in the development of the sampling
program follow:
1. There is an extensive data base concerning the process operations
at coke by-product recovery plants. The data do not often include
effluents or emissions, but do provide important background informa-
tion on the process itself.
2. The proximity of the coke batteries to the by-product recovery
plants made isolation of the by-product plant a formidable challenge,
particularly with respect to ambient sampling.
3. Most sampling locations were in explosion hazard areas in which
standard SASS train heaters and pumps could not be used. The long
suction lines between sample canister and pumps led to reduced
flow rates if the complete train was operated. As the cyclones
and filter were not used, samples could be collected at reasonable
rates.
4. The pollutants of primary interest were aromatics, polycyclic
aromatics, and cyanide. Specific tests were run for cyanide and
the adsorbant module was run for the SASS train.
5. The Effluent Guidelines Division of EPA is sponsoring test work on
wastewater streams at by-product plants, and sampling at this plant
took place the week prior to RTI's sampling visit. This work was
not duplicated. The subject plant considered portions of their
wastewater treatment facilities to be proprietary, and did not
allow sampling at those points.
6. One desired sample point, the noncondensable vent in the light oil
recovery process, was not accessible and was not sampled.
7. Nearly all emissions from a coke byproduct plant are fugitive and
at rates too low to measure. Under this restriction, only major
storage tanks or tanks with measurable vent rates were sampled
directly. Explosion hazards limited flow measurement to the use of
a vane anemometer.
Based on the considerations discussed above, as well as resource limitations,
a modified Level 1 sampling program was developed. This program is summarized
in Table A-l. As can be seen, the program emphasizes organic vapor emissions.
A-4
-------
TABLE A-1. SAMPLING PROGRAM-BY-PRODUCT PLANT ASSESSMENT
Sample
Naphthalene Flotation Separator
Final Cooler Cooling Tower
Tar Storage Tank
Tar Decanter
Light Oil Tank
33 Naphthalene Drying Tank
i
in
Chemical Oil Tank
Excess Ammonia Liquor
Coke Oven Gas
Sludge-WWTP
Ambient Upwind
Ambient Downwind
24-hr Integrated Ambient
Samples
Ammonia Flushing Liquor Tank
Gas Grab
Sample
Glass Evac
Date Bulb Canister
12/12/77 X X
12/13/77 X X
12/13/77 X X
12/14/77 X X
12/14/77 X X
12/15/77
12/15/77 X X
12/14/77
12/14/77 X X
12/15/77
12/16/77 X X
12/16/77 X X
12/12-
12/16/77
12/16/77 X X
Liquid Solid SASS
Grab Grab NaOH Organic Emission
Sample Sample Bubblers Module Rate Comments
X Unknown
X X X — Got liquid samples from
hot well & cold well
X See comment Calculated from breathing
loss equation
X See comment Calculated from breathing
loss equation
Bulbs extracted and
analyzed
X See comment Calculated from
breathing loss
equation
X
X
X
X
X
-------
Six types of samples were collected during the visit, and these are discussed
below. Specific sample data sheets and work-ups are presented later in this
appendix.
Gas Bulbs
The gas bulb sampling technique used was to purge at least three bulb
volumes through the bulb and collect the fourth. Either a squeeze bulb or
mechanical pump was used. The bulbs were 500 ml glass with Teflon® stopcocks.
Two bulbs were filled at most sample sites for the on-site gas chromatograph
analysis for lower boiling (<100° C) hydrocarbons.
Stainless Canisters
Grab samples of vapor were also collected in evacuated stainless steel
cans for more extensive analysis of aromatics at RTI. The cans were approx-
imately one liter in volume, evacuated to about I millibar absolute pressure.
The cans were connected to the purged probe used for the gas samples and the
valve opened to draw in the samples.
XAD-2 Resin Module
Samples of C7-C12 organics were collected in the SASS train XAD-2
module. The probe and cyclones from the SASS train were not used. The
probe used was a 13 mm (0.5 in.) Teflon® tube encased in a larger hose for
protection. The probe was 10 feet long and connected directly to the SASS
organic module. The SASS impinger train was used with the specified solu-
tions, but the solutions have not been analyzed. The circulating cooling
water systems could not be used without electricity, so cooling was provided
by manual addition of ice to the impinger bath and cooling water well in the
organic module. As the samples were generally at ambient temperature, this
was not a serious handicap. The XAD-2 resin was prepared and the canister
filled per Level 1 protocol. SASS run length varied from 1 to 4 hours, or
5.64 m3 to 28.64 m3 (200 to 1,011 ft3) at standard conditions. Run volume was
a nominal 28.00 m3 or a measured 10 percent mass loading of benzene and homologs
on the XAD-2 resin as determined by the aromatics concentration measured by
on-site gas chromatography. Use of the SASS gave the XAD-2 resin samples,
rinses of the resin modules, and in one case an aqueous condensate.
A-6
-------
Liquid and Solid Samples
Liquid samples were collected as grab samples into amber glass bottles
as specified in the Level I Procedures Manual, as was the sludge sample.
Cyanide in Gas
Sampling specifically for cyanide was done with sodium hydroxide bub-
blers. The bubbler containers held 60 ml of 0.5 m sodium hydroxide. Ambient
samples were collected for 24 hours, from 3:00 p.m. of one day to 3:00 p.m.
of the next. The ambient sample rate was 10 1/hr. The final cooler cooling
tower sample collected at 60 1/hr for a total volume of 21 liters.
ANALYSIS PROCEDURES
Overview of Level 1 Organic Analysis Methodology
An overview of the methodology used for the Level 1 organic analysis is
shown in Figure A-2. This methodology deals with the preparation of the
samples to provide a form suitable for analysis, and with their subsequent
analysis.
As indicated in Figure A-2, the extent of the sample preparation required
varies with sample type. The low molecular weight, volatile species (Ci-Cy
or boiling point <110° C) are determined by gas chromatography on site and
require no preparation. The majority of the samples, including the SASS
train components, aqueous solutions and bulk solids require extraction with
solvent prior to analysis. This extraction separates the organic portion of
the samples from the inorganic species. The analysis of organic extracts or
organic liquids then proceeds to initial quantitative analyses of volatile
(total chromatographable organics, TCO) and nonvolatile (gravimetric, (GRAV)
organic material and a preliminary infrared (IR) spectral analysis. The IR
spectrum provides an indication of the types of functional groups present in
the GRAV sample.
The sample extract or organic liquid is separated by silica gel liquid
chromatography (LC), using a solvent gradient series, into seven fractions
of varying polarity. TCO and gravimetric analyses of each fraction are done
to determine the distribution of the sample by the various class types. An IR
A-7
-------
SAMPLES FOR ORGANIC ANALYSIS
Gas
CO
I
Aqueous Solutions
Except Impingers
Solids
Methylene
Chloride
Extraction
On Site GC
For
b.p.<110°C
Range
XAD-2
Sorbent Trap
Methylene
Chloride
Extraction
1.TCO/Grav.
2. Total Sample
-IR
3. LC Fractionated
Sample —
IR/LRMS;
TCO/Grav.
SASS Train
Rinses
Homogenize
And Divide
Extraction In
Soxhlet, Methylene
Chloride
- TCO
GRAV
Evaporate To
Dryness
Portion For
Inorganic
Analysis
2g
1. TCO/Grav.
2. Total Sample
-IR
3. LC Fractionated
Sample —
IR/LRMS;
TCO/Grav.
1. TCO/Grav.
2. Total Sample
-IR of Grav.
3. LC Fractionated
Sample—
IR/LRMS;
TCO/Grav.
Preparation
Analysis
1. Grav.
2. Total Sample
-IR of Grav.
3. LC Fractionated
Sample-
IB/L RMS; Grav,
Figure A-2. Organic analysis flowsheet — Level 1 Methodology.
-------
spectrum is then obtained on the GRAY portion of each LC fraction for
determination of the types of functional groups present. A low resolution
mass spectrum (LRMS) is prescribed for all fractions which exceed the concen-
tration threshold in order to determine the principal compound types present
in each fraction. For the sample streams identified in the Level 1 scheme,
these concentration thresholds are:
Gas streams sampled with the SASS system — 0.5 mg/m3 computed at
the source or 15 mg per LC fraction for a 30 m3 sample.
Liquid or solid streams — 1 mg/Kg extracted or 1 mg per LC frac-
tion, whichever was larger.
The decision is based on the sum of the TCO and GRAV analysis for each
fraction. Unfortunately, problems in the analysis procedure, discussed
further below, prevented successful LRMS of many samples.
On-site GC Analysis of Gas Samples
The on-site GC analysis was based on the EPA Level 1 methodology, with
some variations in instrument conditions where required to improve perform-
ance.
As described above, grab samples were collected by flushing a 500 ml
glass sampling bulb with the sample gas. Samples were removed from the bulb
with a 10 ml Pressure-Lok gas tight syringe and then injected into the
appropriate six port sampling valve equipped with a 1 ml sample loop.
The low molecular weight Ci-Cy hydrocarbons and benzene were quanti-
tated using the conditions given below:
Column: Durapak N-Octane, in S.S. 1/8" x 190.5 cm;
conditioned at 120° C overnight
Detector: Flame lonization
Temperature Program: Isothermal at 30° C for 4 minutes
30°-100° C at 4°/minute
Hold at 100° C until cleared
Helium Flow Rate: 20 ml/min
To minimize adsorption on the sampler surfaces during the quantitation
of the sulfur species, the sampling valve used was constructed of Carpenter-
20 steel (a high nickel content alloy), the sample lines as well as the
A-9
-------
column itself were FEP Teflon tubing and the interface between the column
and the detector was replaced with glass-lined stainless steel tubing. In
addition, the sampling valve was mounted inside the column oven and maintained
at the temperature of the column.
The conditions for the sulfur analyses are given below:
Column: Polyphenylether on Chromosorb T; 36' x 1/8"
Teflon tube; conditioned at 100° C overnight
Detector: Flame photometric
Temperature Program: Isothermal @60° C
Helium Flow Rate: 20 ml Ann
For the GC analysis of permanent gases, all columns, restrictors, and
valves were enclosed in a single valve oven to minimize space requirements
and to insure that all components were heated to the same isothermal tempera-
ture. The conditions for the permanent gas analysis are given below:
Column: Molecular sieve 5A, 6' x 1/8" S.S. and Porapak
N, 8' x 1/8" S.S. with column switching
Detector: Thermal conductivity
Temperature Program: Isothermal at 100° C
Carrier Flowrate: 30 ml/min
Analysis of Evacuated Canister Gas Samples
Grab samples were also collected in specially designed and prepared 2-
liter stainless steel sampling containers. These containers were evacuated
and shipped to the field.
Samples were collected by attaching a sampling probe and momentarily
opening the shut-off valve until atmospheric pressure was reached. The
containers were returned to the RTI labs for the subsequent analysis of
benzene and substituted benzene compounds. Samples were removed from the
containers using an in-house designed and built sampling device which utilized
a Heise gauge and the principle of pressure differentiation. The conditions
for the analysis are given below:
A-10
-------
Column: 10%, l,2,3-tris(2-cyanoethoxy) propane on
100/120 mesh Chromosorb PAW, 8' x 1/8" S.S.
Detector: Flame lonization
Temperature Program: Isothermal at 80° C
Helium Flow Rate: 20 ml/min
Calibration for the analyses was peformed initially on all compounds,
(Ci through C7 normal parafins, benzene and homologs, and sulfurs) to determine
their retention time and area count. Subsequent calibration was performed
daily by checking the retention time and area count of methane, benzene, and
sulfurs only.
Preparation of Sample Extracts
Aqueous Solutions—
Extraction of aqueous solutions was carried out with methylene chloride
using a standard separatory funnel fitted with a ground glass stopcock (no
grease was used). The pH of the aqueous phase was adjusted first to 2.0 ±
0.5 with hydrochloric acid and subsequently to 12.0 ±0.5 with sodium hydrox-
ide, using multi-range pH paper for indication. Two extractions were done
at each pH, using a 500-ml portion of methylene chloride for each of the
four extractions of an approximately 10-liter sample.
For the SASS train sorbent module condensate, the volume of aqueous
solution was measured and the quantity of methylene chloride adjusted pro-
portionately. The extractions were done on-site to avoid the necessity of
shipping large quantities of water.
Solids—
The sludge sample was extracted for 24 hours with methylene chloride in
a Soxhlet apparatus. The Soxhlet thimble was glass with an extra coarse
fritted disc and was previously extracted in order to avoid contamination.
The sample is covered with a plug of glass wool during the extraction to
avoid carryover of the sample. Solids separation was difficult to achieve
with this biological plant sludge.
A-ll
-------
Sorbent Trap—
The XAD-2 resin from the sorbent trap was removed from the SASS train
cartridge in the field and stored in an amber glass bottle with a Teflon®
top liner. At RTI, the resin was homogenized, and a 2-g portion removed for
the inorganic analysis. The inorganic analysis was not run as part of this
study, although the sample is being retained. The balance of the resin
(about 130 grams) was extracted with methylene chloride to remove the organic
material in a large Soxhlet extraction apparatus. The resin was transferred
to a previously cleaned glass extraction thimble and secured with a glass
wool plug. Approximately 2 liters of methylene chloride were added to the
3-liter reflux flask. The resin was extracted for 24 hours. The boiling
solvent in the flask was examined periodically to determine whether additional
methylene chloride was needed to replace that lost by volatization.
SASS Train Rinses--
For each SASS train run there was a sample from the rinse of the sorbent
module. The solvent mixture for this rinse was 1:1 (v:v) methylene chlor.ide:
methanol. The SASS sorbent module rinses were analyzed for TGO prior to
concentration. Then the rinses were dried to constant weight by nitrogen
blowing at ambient conditions to remove the methanol solvent prior to LC
separation.
Analysis of Samples of Organics C« to C,R
The analysis of each of the prepared or isolated samples for organic
compounds followed the scheme introduced in Figure A-2.
Quantitative analysis of moderately volatile materials (b.p. 100° C-3000 C
equivalent to the C8 to C16 normal hydrocarbon range) was achieved by a gas
chromatographic procedure (TCO) applied to various organic solvent extracts,
liquids, and SASS sorbent module rinses. Nonvolatile organic sample components
(b.p. >300° C) were measured by evaporating an aliquot of the extract to
dryness and weighing the residue (GRAV procedure).
In summary, a TCO analysis of each extract, organic liquid, and sorbent
module rinse was performed prior to any concentration step. It was then
A-12
-------
necessary to do a gravimetric analysis on an aliquot of the extract, to obtain
an IR on the GRAV portion from this extract, and to concentrate the extract
for the LC separation. The appropriate stage at which to conduct each of
these steps (gravimetric analysis, IR, concentrate) depended on the quantity
and solubility of the sample. For all samples, quantitative analyses (TCO and
GRAV) were required both before and after concentration.
Total Chromatographable Organics (TCO)—
Samples supplied for TCO analysis were in the liquid form originating
either as a SASS rinse or an extract. Generally, nine separate TCO analyses
were performed on each sample; a preliminary, a concentrate, and 7 LC fractions.
This excludes the standard which was verified daily and numerous blanks corre-
sponding to the 9 analyses per sample. The standard mixture was prepared in
methylene chloride using the normal alkanes, octane, dodecane, and hexadecane.
The concentration of the standard was typically in the range of 5-10 mg/ml
representing the combined weight of all compounds per ml. Typically, 1.5 to
2 ul of all samples were injected onto the column with peak integration cover-
ing only the time span between the retention times of n-heptane and n-heptade-
cane. The results were reported as a total weight of organic material after
the appropriate blank value had been subtracted. The analyses were performed
using the conditions given below:
Column: 10% OV-101 on 100/120 mesh Supelcoport
6' x 1/8" S.S.
Detector: Flame lonization
Temperature Program: Isothermal @30° C for 4 minutes
30°-250° C @16° /min
250° C until cleared
Helium Flow Rate: 20 ml/min
Gravimetric (GRAV) Analysis--
The Level 1 GRAV analysis is used to quantitate the highest boiling
(roughly greater than 300° C) organic compounds collected by the sampling
procedure. The GRAV residue is also the portion of the sample on which an IR
A-13
-------
spectrum is obtained. Where possible, at least 10 mg of sample was weighed in
a GRAV analysis. Weighing was to a precision of ± 0.1 mg. Level 1 procedures
require that not more than 5 ml of the sample extract or one-half the total
sample, whichever is smaller, be subjected to GRAV analysis.
The procedure used to dry the GRAV samples is described below:
1. Label vials with permanent marker and desiccate for 20 hours. Caps
not desiccated.
2. Allow vials to stand exposed to air for 4 hours.
3. Weigh vial and cap together.
4. Add sample aliquot and blow down with dry N2(g).
5. Desiccate 20 hours (vials only) and again weigh vials and caps.
6. Repeat above procedure two additional times or until change in
weight is ±0.1 mg.
Preliminary Versus Concentrate Data—
GRAV and TCO analyses were performed on both the original sample (prelim-
inary) and on the concentrated sample. In most cases the TCO data were
fairly consistent between the preliminary and concentrated samples—the TCO
mass of the concentrate was 70 to 140 percent of that in the original sample,
with an average of 90 percent. Considerably more variation existed between
the GRAV of the concentrated sample and that of the original sample. The
error cannot be conclusively attributed to any single source. As the original
samples often had only a few tenths of a milligram of GRAV material in the
aliquot which was taken to dryness, the use of a balance with a 0.1 mg
precision (as prescribed by the Level 1 procedure) introduced some error
(tare weight of the vials was around 2.7 g). In addition, the fact that
some samples had not achieved constant weight after 3 days desiccation and
blowing down with N2 indicates problems in the determination of GRAVs to
within a few milligrams. GRAV determinations for the concentrated samples
were made on larger masses and thus suffer less from balance error.
Liquid Chromatographic (LC) Separation-
All sample extracts, neat organic liquids, and SASS train rinse residues
(after drying to remove methanol) were subjected to LC separation if sample
quantity was adequate. A 100 mg portion of the sample was preferred for the
A-14
-------
LC, but smaller quantities down to a lower limit of about 15 mg were allowed.
The sample was separated into compound classes on silica gel using a gradient
elution technique. The column and adsorbent were as described below:
®
Column: 200 mm x 10.5 mm ID, glass with Teflon stopcock, water-
jacketed with inlet water temperature in the range of
18°-22° C.
Adsorbent: Davison, Silica Gel, 60-200 mesh, Grade 950 (Fisher
Scientific Company). This adsorbent was activated at
110° C for at least two hours just prior to use, and
cooled in a desiccator. No preclaiming was required by
the Level I protocol.
Table A-2 shows the sequence for the chromatographic elution. In order
to ensure adequate resolution and reproducibility, the column elution rate
was maintained at 1 ml per minute.
TABLE A-2. LIQUID CHROMATOGRAPHY ELUTION SEQUENCE
Fraction
1
2
3
4
5
6
7
Solvent Composition
Pentane
20% Methyl ene chloride in pentane
50% Methyl ene chloride in pentane
Methyl ene chloride
5% Methanol in methyl ene chloride
20% Methanol in methyl ene chloride
50% Methanol in methyl ene chloride
Volume
25 ml
10 ml
10 ml
10 ml
10 ml
10 ml
10 ml
EPA Level 1 procedures were followed for the LC work. A bank of 4 LC
columns allowed the use of a single solvent blank for each 3 samples. In many
cases the GRAV mass of the blanks was significant. GRAV mass for the LC cuts
is given both before and after subtraction of the blank mass. The silica gel
was apparently the source of the spurious GRAV mass.
Spectroscopy—
Infrared (IR) analysis of the total sample (preliminary), concentrate,
and LC cuts was performed on the GRAV residue whenever there was adequate
sample mass. The instrumentation used was a Nicolet Model 7199 Fourier Trans-
form IR, which allowed resolution beyond that required by the Level 1 proto-
col. Samples which were below the Level 1 criteria for IR work by organic
A-15
-------
mass, but on which IR spectrum were obtained are so indicated. The GRAV
residue was dissolved in methylene chloride, placed on a KBr salt plate, and
allowed to dry before running. The spectra were interpreted and the results
and data sheets are included in this appendix.
Low resolution mass spectroscopy (LRMS) was used on the samples when
indicated by sample quantity per the Level 1 protocol. Problems were encoun-
tered with the LRMS due to interference from the solvents and inability to
perform solvent exchange without losing significant amounts of TCO material.
Level 1 protocol stipulates that, for LC samples with greater than 2 mg
of TCO material when referenced back to the source, LRMS analysis be carried
out using the batch inlet. Some question regarding the efficacy of this
approach were raised because of the overwhelming quantities of solvent (methyl
ene chloride) molecules present compared to solute molecules. Liquid chro-
matographic fraction Number 6 of the XAD-2 module rinse for the chemical oil
tank was analyzed using the batch inlet system. No peaks other than those
associated with methylene chloride were present. The solution was concen-
trated by a factor of 2.5 and analyzed again. Aside from methylene chloride,
3-4 additional components were noted. Further concentration by a factor of
2 followed by a batch inlet run produced a spectrum with 4-5 compounds other
than methylene chloride. Further concentration is of dubious value since
TCO material is too readily lost.
This approach, i.e., the detection of small amounts of solute in the
presence of gross amounts of solvent, is being reexamined at RTI under a
separate EPA contract to determine the concentration levels at which known
amounts of known semi-volatile materials can be adequately detected. With
this information the criterion for LRMS analysis of TCO material via the
batch inlet may be altered. For this reason the samples analyzed under this
contract that meet the Level 1 TCO LRMS criterion (some 60 samples) have not
yet been analyzed. These samples have been stored. LRMS work that did not
suffer from this interference problem was completed and the results are
included in this appendix.
Gas chromatography/high resolution mass spectroscopy (GC/MS) work was
done on three samples to check for the presence of high molecular weight
PNA's in the vapor samples. The instrumentation was an LKB Model #2091
A-16
-------
GC/MS. The column used was a 1 percent SE 30/bariurn carbonate wall coated
open tubular column (WCOT) 16.8 m long. Following injection, the column
temperature was held at 70° C (100° C in one case) for 2 minutes, then
advanced at 8° C per minute to 240° C. The scan rate for the GC/MS was 2
seconds per scan over the range from 50 mass units to 490 mass units.
Limits of detectability for polynuclear aromatics was in the range of 15-100
ug/ul, which for these samples was 16-106 weight parts per billion (wppb)
for the tar decanter, 2.4-16 wppb for the tar storage vapor, and 0.01-0.06
wppb for the final cooler cooling tower. The above calculations assumed a
compound with a molecular weight of 250.
Analysis for Cyanide—
The method used to determine the cyanide concentrations in the NaOH
bubblers was a titrimetric procedure67 using silver nitrate and a silver
sensitive indicator (p-dimethylamino-benzal-rhodamine).
Work-Up and Presentation of Data--
The data collected during this test work are presented in several
different formats depending on the type of sampling and analysis utilized.
The bulk of the results are from the Level 1 analyses, including the Ci~C7
on-site GC work, the analysis of the XAD-2 module sample and the GC work
for aromatics identification. Samples collected at the froth flotation
separator, final cooler cooling tower, tar storage tank, tar decanter, light
oil tank, chemical oil tank, and from the ambient air are all treated in
essentially the same way. The first data sheet presented for a given emission
source is the SASS data sheet. The second data sheet presents the results
of the GC analyses, both on- and offsite, Level 1 as well as specific compound
quantisation. The third table presented is the organic extract summary, a
work-up of the Level I data. At the top of the table is the total organics
concentration (sum of the original sample TCO and GRAV divided by the SASS
sample volume). The GRAV and TCO analyses were rationed back to the original
extract on a volumetric basis:
GRAV or TCO in _ GRAV or TCO x Volume of Extract
original extract measured in aliquot Volume of Aliquot
The next two lines of the table present the TCO and GRAV masses, respec-
tively, ratioed back to the total sample for the preliminary, concentrate,
A-17
-------
and GC cuts. The GRAV and TCO values are on a net basis, the blanks having
been subtracted (negative weights are reported as zero in this table).
In a few cases the GRAV mass after subtraction of blanks was zero for
all LC cuts in spite of a significant GRAV mass in the concentrate and prelim-
inary GRAV's. In these cases the GRAV mass before blank subtraction is
presented in parentheses in the table.
The complete XAD-2 canister rinse samples were taken to dryness after a
preliminary TCO and GRAV analysis. The total sample GRAV then is straight-
forward-the mass of the dry residue. A portion of the dry residue was
weighed, dissolved in a small amount of methylerie chloride, and put on the
LC column. The GRAV of the LC cut was then ratioed back up to the original
sample by the formula:
GRAV LC cut mass on total _ total GRAV mass GRAV mass
sample basis GRAV mass put on LC column x in LC cut
The TCO mass was ratioed up on the same basis, although the fact that the
sample had been dried opens the question of what fraction of the TCO had
been lost.
The remainder of the table is devoted to interpretation of the Level 1
LC and IR results. The basic quantity used in this interpretation is the
MATE (minimum acute toxicity concentration) Comparison Value, a synthetic
number with concentration units (mg/sm3). The intent of this portion of the
table is to present a structured and uniform (with respect to the other
samples) interpretation of this part of the Level 1 analysis. MATE Compar-
ison Values were only prepared for streams discharged to the environment.
Thus, excess ammonia liquor and the final cooler liquid sample are not so
treated. MATE Comparison Values were calculated as follows:
1. The GRAV mass for a given LC fraction was ratioed back to the
original sample and divided by the SASS sample volume to obtain
the GRAV concentration for the LC fraction.
2. The IR spectrum interpretation for the given LC cut was then
evaluated in the light of the compound classes expected in the LC
cut based on work presented by Harris59 as shown below:
A-18
-------
aliphatic hydrocarbons LC cut 1
halogenated aliphatics LC cut 1
aromatic hydrocarbons LC cuts 2, 3 or 4
halogenated aromatics LC cuts 2, 3 or 4
heterocyclic N, 0, S compounds LC cuts 4 or 5
sulfides, disulfides LC cuts 4 or 5
nitriles LC cuts 4 or 5
ethers LC cuts 4 or 5
aldehydes, ketones LC cuts 5 or 6
nitroaromatics LC cuts 5 or 6
alcohols LC cuts 5 or 6
amines LC cuts 5 or 6
phenols; halo and nitrophenols LC cuts 6 or 7
esters, amides LC cuts 6 or 7
mercaptans LC cuts 6 or 7
carboxylic acids LC cuts 6 or 7
sulfoxides LC cuts 6 or 7
A compound type which was identified in the IR spectrum of an LC cut
was entered in the. Summary Table as having a MATE Comparison Value
equal to the total GRAV concentration for that fraction. Compound
classes which would be expected in an LC cut if present, but not
indicated by IR, were entered in the table at 10 percent of the
total GRAV concentration. This procedure is a modified version of
that presented by Harris.59
The MATE Comparison Values then are not emission factors for a compound
class, and for a given LC cut total more than the GRAV mass of that LC cut.
They do, however, assist in the comparison of various sources within the
by-product plant. The reader should note that TCO mass is not included in
this procedure, as the TCO material was not present in the samples analyzed
by IR or if TCO was present it was included in the GRAV mass reported. For
several sources, TCO material is the majority of the organics present.
The chosen compound classes generally follow the classification scheme
used in the Multimedia Environmental Goals (MEG's) list.60
The other data sheets for a given source are the IR interpretation
sheets and, where applicable, the LRMS interpretation. The analyses are
arranged with the preliminary IR first, followed by the concentrate and then
the LC cuts.
INDIVIDUAL SAMPLES AND WORK-UP
Froth Flotation Separator
Naphthalene collected in the final cooler was separated in a froth
flotation chamber. The separator was a WEMCO design, roughly 25 feet long,
A-19
-------
10 feet wide, and 10 feet deep. Hatches, presumably for cleaning, were
present in the top. The sample was taken by placing the probe in the vapor
space through one of the hatches and closing the hatch over it. No measur-
able emission was present from the separator.
The samples collected at the separator were two glass bulbs, an evac-
uated cylinder, and a SASS organic module. The SASS run collected 28.6 sm3
(1010 scf) of vapor at a temperature of 12° C at the XAD-2 resin. Tables A-3
through A-24 are the complete data sheets and analysis work-ups on this sample.
Final Cooler Cooling Tower
The gas and vapor in the airstream directly above the final cooler
cooling tower were sampled. All the Level 1 samples were collected using a
30-foot Teflon probe suspended above the tower. Two glass bulb grab sam-
ples, an evacuated canister and a SASS XAD-2 resin sample were collected for
hydrocarbon analysis. The XAD-2 resin was exposed to 27.6 sm3 (975 scf).
The temperature at the XAD-2 resin was 14° C.
Sampling for cyanide in the gas was conducted at this site. A 0.64 cm
®
Teflon line was suspended above one cell of the cooling tower as above and
the cyanide collected in 0.5 m sodium hydroxide bubblers. Around 0.02 m3
gas was sampled in each of two runs.
The design gas rate for the cooling tower was not available. The water
rate was known, and the gas rate was estimated to be equal on a mass basis.68
On this basis, the gas flow rate was 3,230 sm3/Mg coke (104,000 scf/ton).
Sample and analysis data sheets are presented as Tables A-25 through
A-42.
Liquid samples were collected from both the hot and cold wells of the
cooling tower. These were grab samples, extracted on-site per Level 1
procedures. Analysis of the sample produced the results given in Tables
A-43 through A-85.
Tar Storage Tank
The coal tar storage tanks at the sampled plant were maintained at
around 90° C. A total of five tanks function for tar storage, one 250,000
gal, one 500,000 gal, and three 1,000,000 gal tanks. All are cylindrical
tanks with cone roofs; with one exception diameter to height is approximately
A-20
-------
1:1. Ventilation slots were cut around the sides of the tanks just under
the roof junction. A vent was also provided at the top of the cone.
Tar was pumped first to the tank which was sampled, and water (10
percent by volume) was decanted from this tank. The "dry" tar was then
stored in a second tank. The other two large tanks were not in use, al-
though they were used at times. The small tank (250,000 gal) was used for
storage at the pitch plant.
"Working" losses from these tanks were estimated for filling the various
tanks in order as the tar production was moved from place to place; a given
volume of tar was pumped to three tanks. During the week we sampled, tar
production averaged 46.3 1/Mg coke (11.1 gal/ton coke), so working losses from
the three transfers were about 0.14 smVMg coke (4.5 scf/ton coke).
Breathing loss for these tanks could not be estimated, both because of a
lack of basic data (vapor pressure of the tar/water mixture) and the ventila-
tion slits around the tank which allow wind to blow through the tank. The
available correlations are not adequate for this purpose.
The sampling was done through a hatch in the top of the tank. The
probe was simply lowered about 2 m into the tank, around a meter below the
ventilation slits. Glass bulbs, an evacuated canister, and a SASS run were
done at this site. The SASS train plugged with naphthalene after about an
hour; the total sample volume was 5.6 m3 (199 scf); the sampled vapor was at
about 30° C, as was the XAD-2 resin.
Results of the analyses are presented in Tables A-86 through A-107.
Tar Decanter Tanks
Three tar decanter tanks were in use at the sampled plant, handling
3,626 1 flushing liquor per Mg coke produced (871 gal/ton). Each decanter
was vented through standpipes in the roof, some of which had measurable
emissions. The emission rates were measured by restricting the vent, and
forcing the gas through a vane anemometer. The gas temperatures ranged from
74° to 82° C. The three decanters had a total of 18 vents, eight of which
were venting at measurable rates. In addition, one decanter had a poorly
sealed hatch which was venting; the rate was estimated to be three times the
A-21
-------
pipe vent rate on that decanter. The total estimated tar decanter vent
emission rate was 2.15 snrVMg coke produced (68.2 scf/ton).
The samples collected were two glass bulbs, one evacuated canister, and a
SASS XAD-2 resin sample. The SASS sample was of 8.14 sm3 (287.4 scf), terminated
due to the high aromatics content of the stream. Data and analysis sheets are
presented as Tables A-108 through A-149.
Light Oil Storage Tank
Light oil production during the sampling visit averaged 13.7 1/Mg coke
(3.3 gal/ton), stored in a single 3,785,000 1 (1,000,000 gal) tank of conven-
tional cone roof design. Working loss emissions amount then to an estimated
0.03 smVMg coke (0.45 scf/ton).
Breathing losses were crudely calculated for a hypothetical light oil
with a vapor pressure of 50 mm Hg at storage conditions. As light oil
composition was not determined, a better estimate is not possible, and in
fact may not be warranted for the quality of the correlation.69 The estimated
loss rate was 18 g light oil/Mg coke (0.035 Ibs/ton). At the measured gas
concentrations for light oil constituents, this would require an emission rate
of 15.6 mVMg coke (500 ftVton). The breathing loss is much more significant
than is the working loss.
The samples collected were glass bulbs. A Teflon® probe was lowered
about 2 m into the vapor space of the tank and connected to an evacuated
canister. A SASS XAD-2 module sample was not collected due to sampling
difficulties.
Analysis results from this sample are provided in Table A-150.
Chemical Oil Storage Tank
The volatile product of tar distillation, chemical oil, was stored in
two tanks, each 10.2 m (33.5 ft) in diameter and 11.9 m (39 ft) high. The
production rate of chemical oil was 23.1 1/Mg (5.6 gal/ton) coke during the
sampling visit. Working loss was then 0.024 smVMg coke (0.75 scf/ton).
Breathing loss could not be calculated.
Sampling was done by lowering a probe in through a hatch in the top of
the tank. Glass bulbs, an evacuated canister, and a SASS XAD-2 module were
collected. Naphthalene condensed in the module and had to be scraped off in
order to collect the 14.3 sm3 sample.
A-22
-------
Data sheets and analysis results are presented in Tables A-151 through
A-172.
Coke Oven Gas
A sample of coke oven gas downstream of the tar scrubbers but before
ammonia removal was collected. Two glass bulbs and an evacuated canister
were collected. The results are given in Table A-173.
Primary Cooler Condensate Tank
Condensate from the primary coolers were collected in two tanks, and was
then combined and put in a third tank. The most accessible of these tanks
was sampled, using a glass bulb and an evacuated canister. The rate of
emission was estimated by putting a vane anemometer in the vapor stream.
The combined total emission rate from the three tanks was 1.7 sm3/Mg coke
(55.3 scf/ton). The gas temperature leaving the tank was 63° C. The on-
site GC analysis of the samples is described in Table A-174.
Naphthalene Drying Emissions
Naphthalene slurry was dewatered by decanting and then heating. The
drying tanks included two 41,600 1 (11,000 gal) horizontal cylindrical tanks
and three 83,200 1 (22,000 gal) tanks. Each tank was fitted with steam
coils and a vent stack which extended about 5 m (16 ft) above the tank. The
naphthalene slurry (60 percent water) was pumped into the tank, and the
water allowed to separate. After draining, the steam was turned on and the
naphthalene melted.
Drying time was generally 24 to 48 hours. The emission rate was esti-
mated by measuring the rate at which air was being drawn into a hatch of a
tank by the chimney effect. The vapor within the tank was sampled by lower-
ing .glass bulbs into the tank, allowing them to warm, then aspirating through
them as described above. The liquid temperature in the tank was 101° C.
For an average drying time of 36 hrs, with 16,600 1 of liquid naphthalene in
the tank at a production rate of 0.74 1 naphtha!ene/Mg coke (0.18 gal/ton
coke), the emission rate was 2.94 sm3/Mg coke (93.4 scf/ton). The naphtha-
lene concentration in the samples was measured by GC and found to be 533 g/sm3
vapor. This amounts to 1.56 kg napthalene emitted per Mg coke (3.13 Ib/ton).
A-23
-------
As this is about twice the total naphthalene production of the plant, the
sample taken must not be representative in some way.
Ambient Samples for Cyanide
Ambient bubblers were run for 24 hours on each of 4 days. The data
were presented earlier in Section 6 of this report and will not be repeated
here. Three sample stations were available, only two of which operated on
two days. The data sheets for the four days are attached as Tables A-175 •
through A-178.
Upwind-Downwind Ambient Organic Sampling
Ambient organic samples were collected both upwind and downwind of the
plant. Glass bulbs, evacuated canisters, and SASS XAD-2 modules were col-
lected at both sites. The sampling was conducted sequentially, the downwind
sample first, followed by the upwind sample. Data sheets and analysis
results are presented in Tables A-179 through A-199.
Ammonia Liquor Samples
Grab samples of excess ammonia liquor were collected and analyzed by
Level 1 methodology. The sample was collected just before the liquor entered
the wastewater treatment plant. The analysis results are given in Tables
A-200 through A-230.
Biological Treatment Plant Sludge
A grab sample of sludge was collected and analyzed for organics and by
taking a pH 7 extract and subjecting it to Level 1 analysis. The results on
this sample were presented in the body of the report. Tables A-23 through
A-240 give the analytical results.
RAW GRAV AND TCP Data
The TCO and GRAV data are presented in Tables A-241 and A-242, respec-
tively. The TCO data for the LC cuts is the total mass in the LC aliquot, the
blank having been subtracted. The GRAV mass for the LC cuts presented in
Table A-242 is the GRAV mass found in the aliquot from the LC procedure. That
A-24
-------
is, 25 ml of pentane was the first of the solvents put on the loaded LC
column. After the pentane had passed through the silica gel, 10 ml was taken
as a GRAV aliquot and the value presented in the table is the GRAV mass in
that 10 ml aliquot. The total GRAV mass in the LC sample is then 2.5 times
the mass in Table A-242. The other LC cuts are collected with 10 ml of solvent,
and 5 ml was taken for GRAV determination. Thus these cuts are ratioed to the
total GRAV mass in the LC sample by multiplying by 2.0.
Once the total TCO or GRAV mass in an LC sample is known, the TCO or GRAV
in the original sample can be calculated as from the ratio of concentrated
sample volume to the volume of sample put on the LC column.
A-25
-------
TABLE A-3. FROTH FLOTATION SEPARATOR SAMPLE
Plant Name: United States Steel—Coke By-Product Plant
Location: Birmingham, Alabama
Date: 12/12/77
Test Performed By: F. J. Phoenix, E. E. Stevenson
Run Number: 1
Sampling Location: Wemco Separator
Pre Leak Test: 0.04
Post Leak Test: 0.04
Test Time:
Start: 10:15
Finish: 14:25
Meter Volume (c.f.):
Start: 630,59
Finish: 1680.24
Volume of Gas Sampled: 1049.65 c.f.
1011.29 scf
Average Gas Temperature (°F)
Ambient: 54°
Sampling Location: 54°
XAD-2 Resin: 54°
Meter Box: 85°
Comments:
1. No condensate collected.
2. Sampling performed in one of sixteen 8" x 50" openings in
top of separator.
A-26
-------
TABLE A-4. FROTH FLOTATION SEPARATOR SAMPLE
GC ANALYSIS
Sample Date: 12/12/77
Analysis Date: 12/12/77
Cj-Cy HYDROCARBONS
Bulb #1
Range
GC
1
2
3
4
5
6
7
# Peaks
1
1
4
1
5
4
0
ppm
(v/v)
1425
441
155
0.1
13
30
AROMATICS (ppm , V/V)
On-Site
Benzene
Toluene
Ethyl Benzene
m & p Xylene
o Xylene
Bulb 1 Bulb 2
1814.8 1612.9
162.9 136.1
NA NA
NA NA
NA NA
RTI
SS Can
914.7
82.9
0.5
14.4
3.7
SULFURS (ppm, V/VJ
Range
GC
1
2
3
4
5
6
7
Bulb #2
# Peaks
1
1
4
0
2
1
1
ppm
(v/v)
1291
373
132
—
37
212
3
H2S (COS)
so2
cs2
NA = No Analysi
On-Site
Bulb 1 Bulb 2
1504 NA
— NA
— NA
s.
— = Compound Not Detected.
A-27
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TABLE A-5. ORGANIC EXTRACT SUMMARY, FROTH FLOTATION SEPARATOR, XAD-2 RESIN
oo
Preliminary
Total organics mg/sm3 649
TCO, mg 18,538
GRAV, mg 40
Category
Aliphatic hydrocarbons
Halogenated aliphatics
Aromatic hydrocarbons
Halogenated aromatics
Heterocyclic N, 0, S
compounds
Sulfides, disulfides
Nitriles
Ethers
Aldehydes, ke tones
Nitroaromatics
Alcohols
Amines
Phenols, halo and nitrophenols
Esters, amides
Mercaptans
Carboxylic acids
Sulf oxides
Concentrate LCI
474 0.0
13,175 0.0
394.5 0.0
LC2
(10.9) 419 (423)
12,000
(312) 0.0 (100)
LC3
7.0 (14)
200
0.0 (200)
LC4
0.87
25
0.0
LC5
(6.1) 42 (47)
1,200
(150) 0.0 (150)
LC6
0.0
0.0
0.0
LC7
(3.5) 0.0 (7.0)
0.0
(100) 0.0 (200)
i
469 (512)
13,425
0.0 (1,212)
MATE comparison value, mg/sm3*
(10.9)
(1.1)
(10.9)
(10.9)
(3.49)
(0.35)
(3.49)
(3.49)
(7.00)
(0.70)
(7.00)
(7.00)
(7.00)
(5.24)
(0.52)
(0.52)
(0.52)
(0.52)
(0.52)
(5.24)
(5.24)
(5.24)
(0.52)
(0.52)
(0.52)
(0.52)
(5.24)
(0.52)
(5.24)
(0.52)
(5.24)
(5.24)
(3.49)
(3.49)
(3.49)
(0.35)
(0.35)
(0.35)
(0.35)
(3.49)
(0.35)
(0.35)
(0.35)
(7.00)
(7.00)
(7.00)
(7.00)
(0.70)
(7.00)
(0.70)
(0.70)
(0.70)
0.0 (10.9)
0.0 (1.1)
0.0 (31.5)
0.0 (1.57)
0.0 (1.04)
0.0 (1.04)
0.0 (1.04)
0.0 (22.0)
0.0 (38.9)
0.0 (0.87)
0.0 (12.6)
0.0 (2.09)
0.0 (5.59)
0.0 (42.4)
0.0 (1.05)
0.0 (1.05)
0.0 (1.05)
NOTE: Values in parentheses are GRAV mass before subtraction of blank. The presence of GRAV mass in the original sample is shown by the Preliminary
and Concentrate samples. The MATE Comparison Value is based on the GRAV mass in the LC cut divided by the gas sample volume. For compound classes
indicated by IR, the MATE comparison value is 100 percent of the GRAV concentration. For compound classes expected65 but not identified by IR, the MATE
Comparison Value is 10 percent of the GRAV concentration.
-------
2.
3.
TABLE A-6. FROTH FLOTATION SEPARATOR: XAD-2 RESIN,
PRELIMINARY IR ANALYSIS
1. Major peaks and assignments
v (cm~ )
3054
2956, 2926, 2854
1723
1601
1495
1454
1262, 1069
78
I
W
S
M
M
W
W
W
M
As s i qnments/ Comments
aromatic or olefinic
aliphatic CH stretch
ketone or ester
conj. olefine and/or
aromatic C^-^C
aliphatic CH bend
aromatic ester 0-CO-O
substituted aromatic
CH stretch
aromatic C-^^C
stretch
compds
1713, 1693, 1182, 1022, 824 cm"1
Unassigned weak bands:
Other remarks:
This sample possesses less mass than that required by Level 1 criteria
for IR analysis. A spectrum of acceptable quality was obtained, however, since
Fourier Transform IR techniques were utilized.
Sample appeared to contain principally aliphatic and aromatic ketones
and esters. Also, large peak at 1602 cm indicates significant amounts
of conjugated olefins.
A-29
-------
TABLE A-7. FROTH FLOTATION SEPARATOR, XAD RESIN,
IR ON SAMPLE CONCENTRATE
1. Major peaks and assignments
v (cm ) l_ Assignments/Comments
3072, 3054, 3007 W aromatic and olefinic CH
1956-1674 W aromatic overtones/combinations
1592, 1387 W,M a-substituted naphthalene, or
conjugated vinyl C^^-C stretch
1269-1005 W aromatic fingerprint region
958 M vinyl CH bend, or aromatic in-plane
bend
782-700 S-M substituted aromatic compds
2. Unassigned weak bands: 1504, 847, 618 cm'1
3. Other remarks:
Sample contains substituted aromatic and/or unsat, hydrocarbons.
Large band at 782 cm" suggests that sample is predominantly naphthalene,
i_.e_., band at 782 cm" is the resultant of CH out-of-plane bending of 4
adj. aromatic H.
TABLE A-8, FROTH FLOTATION SEPARATOR, XAD RESIN,
LC CUT #1 IR
1. Major peaks and assignments
v (cm ) I_ Assignments/Comments
2954, 2932, 2856 S aliphatic CH stretch
1740 M ester or aliphatic ketone
1459 M
1438, 1376 W aliphatic CH bend
2. Unassigned weak bands:
3. Other remarks:
A-30
-------
TABLE A-9. FROTH FLOTATION SEPARATOR, XAD RESIN,
LC CUT #2 IR
1, Major peaks and assignments
v (cm"1)
I
2958, 2927, 2857 S
1741 W
1464, 1378 M,W
1261 S
1078, 1041 S
863, 749, 702 W
802 S
Assignments/Comments
aliphatic CH stretch
ester
aliphatic CH bend
ester of aromatic or a,0-unsaturated
acids
aliphatic ethers, or esters
substituted aromatic
substituted aromatic—predominantly
a-substituted naphthalene or m-sub.
benzene
2, linassigned weak bands: 1613, 1604
3. Other remarks:
This sample possessed less mass than that required by bend 1 criteria
for IR analysis. A spectrum of acceptable quality was obtained by using
Fourier Transform IR techniques.
Sample predominantly esters of aromatic and/or a,e-unsaturated
acids and/or aromatic and aliphatic ethers.
A-31
-------
TABLE A-10. FROTH FLOTATION SEPARATOR, XAD RESIN,
LC CUT #3 IR
1. Major peaks and assignments
v (cm"1) I
2955-2854
1745-1730
1465, 1381
1262, 1162, 1080
801, 719
S
W
W
w
H
Assignments/Comments
aliphatic CH stretch
ester or aliphatic ketone
aliphatic CH bend
aromatic ester or ether, al
ether
sub, aromatic compds
iphatic
2. Unassigned weak bands: 1481, 1038, 668 cm"1
3. Other remarks;
This sample possessed less mass than that required by the Level 1
criteria for IR analysis. A spectrum of acceptable quality was obtained
by using Fourier Transform IR techniques. Spectrum inculdes peaks of
KIntensity of blanks. Sample appears to contain only aliphatic esters
of aromatic acids, or aliphatic ketones.
A-32
-------
TABLE A-ll. FROTH FLOTATION SEPARATOR, XAD RESIN,
LC CUT #4, IR
1. Major peaks and assignments
v (cm ) ! Assignments/Comments
2955-2854 S aliphatic CH stretch
1756-1715 W ketone or ester
1462, 1453 W aliphatic CH bend
1380, 1368 W gem,-dimethyl bend
746 W sub benzene
2. Unassigned weak bands: 1271, 1163, 1072
3. Other remarks:
This sample possessed less mass than that required by the Level 1
criteria for IR analysis. A spectrum of acceptable quality was obtained
by using Fourier Transform IR techniques.
Spectrum appears to contain predominantly alkylated aromatic hydro-
carbons and aliphatic ketones or esters of aromatic acids.
A-33
-------
TABLE A-12.
FROTH FLOTATION SEPARATOR, XAD RESIN,
LC CUT #5, IR
1, Major peaks and assi
v (cm"1)
3350
3062
2959, 2932, 2856
1726
1602
1465, 1376
1287, 1253
1123, 1075
753, 698
gnments
I
broad
W
s
M
M
M,W
M
W
W
Assignments/Comments
alcohol or phenol OH
aromatic CH stretch
aliphatic CH stretch
aliphatic ketone, or ester
aromatic C~-^C stretch
aliphatic CH bend
ester of aromatic acid, or alcoholic
or phenolic C-0
ester of 10 and/or 20 ale.
mono-sub, benzene
1513, 1
cm
Unassigned
Other remarks:
Sample contains primarily sat. hydrocarbons, aliphatic esters of
aromatic acids, predominantly benzoates, and alcohols or phenols.
A-34
-------
TABLE A-13.
FROTH FLOTATION SEPARATOR, XAD RESIN
LC CUT #6, IR
1. Major peaks and assignments
v (cm" )
2956, 2927, 2854
1729
1452
1380, 1371
758, 743
1258, 1244
S
S
W
w
W
W
M
Assi gnments/Comments
aliphatic CH stretch
ketone or ester
aliphatic CH bend
geminal-dimethyl CH bend
substituted aromatic
ester of aromatic acid, or
aromatic and/or aliphatic ethers
1601, 1464 cm'
1077, 1032
2. Unassigned weak bands:
3. Other remarks:
This sample possessed less mass than that required by the Level 1
criteria for IR analysis. A spectrum of acceptable quality was obtained
by using Fourier Transform IR techniques.
Sample contains predominantly alkylated aromatic esters and/or ethers.
A-35
-------
TABLE A-14. FROTH FLOTATION SEPARATOR, XAD RESIN,
LC CUT #7, IR
1. Major peaks and assignments
v (ctn ) 1 Assignments/Comments
2962, 2930, 2854 S aliphatic CH
1744, 1732 S aliphatic ketone, or ester
1451, 1380 W aliphatic CH bend
1258, 1076, 1032 acetates of primary or secondary
alcohols, or aromatic ethers
758, 743, 723 W sub. aromatic cmpds
2. Unassigned weak bands: 3367, 3091, 1604, 1553, 1121
3. Other remarks:
This sample possessed less mass than that required by the Level 1
criteria for IR analysis. A spectrum of acceptable quality was obtained
by using Fourier Transform IR techniques.
Sample appears to contain predominantly aliphatic esters (acetates),
cyclic saturated ketones, and some aromatic material.
A-36
-------
TABLE A-15. ORGANIC EXTRACT SUMMARY, FROTH FLOTATION SEPARATOR, CANISTER RINSE
Preliminary
Total organics mg/sm3 29.8
TCO, mg 360
GRAV, mg 493
Category
Aliphatic hydrocarbons
Halogenated aliphatics
Aromatic hydrocarbons
Halogenated aromatics
^ Heterocyclic N.O.S
«£> compounds
Sulfides, disulfides
Nitriles
Ethers
Aldehydes, ketones
Nitroaromatics
Alcohols
Amines
Phenols, halo and nitrophenols
Esters, amides
Mercaptans
Carboxylic acids
Sulf oxides
Concentrate LCI LC2 LC3 LC4
6.1 0.82 0.53 0.53 0.17
0.0 2.0 0.4 0.0
174 23.4 15.1 14.7 4.9
MATE comparison value,
0.82
0.08
0.53 0.51 0.17
0.05 0.05 0.02
0.02
0.02
0.02
0.02
0.17
LC5
0.13
0.0
3.7
mg/sm3*
0.13
0.01
0.01
0.01
0.13
0.01
0.01
0.13
0.13
0.13
0.13
LC6
0.86
1.4
23.2
0.81
0.81
0.08
0.08
0.81
0.08
0.81
0.08
0.08
0.08
LC7
0.18
0.0
5.3
0.18
0.18
0.02
0.18
0.02
0.18
0.02
0.02
0.02
Z
3.22
3.8
90.3
0.82
0.08
2.33
0.12
0.03
0.03
0.03
0.15
1.00
0.09
0.23
1.29
0.23
1.12
0.10
0.10
0.10
NOTES: The MATE Comparison Value is based on the GRAV mass in the LC cut divided by the gas sample volume. For
compound classes indicated by IR, the MATE comparison value is 100 percent of the GRAV concentration. For compound
classes expected 6S but not identified by IR, the MATE Comparison Value is 10 percent of the GRAV concentration.
-------
TABLE A-16.
FROTH FLOTATION SEPARATOR, CANISTER RINSE:
PRELIMINARY IR
SAMPLE:
1
1XR-P
2.
3.
Major peaks and assignments
v (cm~ )
3050
2970, 2925, 2848
1720, 1712
1640, 1595
1440, 1420, 1375
1265
1140-1125, 1070
890
860-700
700-650
Unassigned weak bands
Other remarks:
W
w
W
w
M,M,W
S
W
W
W
W
Assi gnments/Comments
aromatic CH stretch
aliphatic CH stretch
aliphatic ketone and esters
aromatic C-^^^-C
aliphatic CH bend
ester of a,g-unsat. or aromatic
acid or aromatic ester
aromatic and/or aliphatic ethers
or aromatic esters
substituted aromatic cmpds
2550, 2540, 2400, 1070-970 (series of weak bands)
Sample contains predominantly unsat.and/or aromatic ethers and esters
of aromatic acids or aroatic ethers. Bands at 1712, 1440, and 1420 cm'1
suggest that aliphatic ketones or esters of saturated acids are present:
[-CH2-(C=0)- absorbs at 1420] spectrum dominated by band at 1265 cm"1
suggesting sample predominantly aromatic ethers.
A-38
-------
TABLE A-17.
FROTH FLOTATION SEPARATOR, CANISTER RINSE:
CONCENTRATE IR
SAMPLE: 1XR-C
1. Major peaks and assignments
v (cm"1) I
3043, 3007 W
2959, 2946, 2856 S
1737 M
2061-1936 W
1598 M
1452, 1380 M,W
1259 M
1096, 1023 M,W
842, 812, 751 W,W,M
Unassigned weak bands:
Assignments/Comments
aromatic or olefinic CH
aliphatic CH
ester or aliphatic ketone
aromatic overtones/combinations
aromatic C-^^-C
aliphatic CH bend
ester of aromatic or a,e-unsat. acid
ester, aliphatic ether
2.
3.
sub. aromatic cmpds
2366, 878, 751 cm"1
Other remarks:
This sample possessed less mass than that required by the Level 1 cri-
teria for IR analysis. A spectrum of acceptable quality was obtained by using
Fourier Transform IR techniques.
Sample appears to contain primarily esters of aromatic or a,3-unsat. acids
and 1° and/or 2° alcohols. Peak at 1598 cnf due to org. nitrates or substituted
aromatic cmpds. which occasionally show a large, broad unresolved peak in this
region.
A-39
-------
TABLE A-18.
FROTH FLOTATION SEPARATOR, CANISTER RINSE:
LC CUT #1 IR
SAMPLE: 1XR-LC1
1. Major peaks and assignments
v (cm"1) l_
2959, 2931, 2856 S
1465 M
1376 w
718 o W
Unassigned weak bands: 1739, 670
2.
3.
Assi gnments/Comments
aliphatic, CH stretch
aliphatic, CH bend
isolated methyl, CH bend
K- rocking
Other remarks:
Sample predominantly sat. hydrocarbons, containg a trace of ketone,
TABLE A-19. FROTH FLOTATION SEPARATOR, CANISTER RINSE:
LC CUT #2 IR
SAMPLE: 1XR-LC2
1. Major peaks and assignments
v
2.
3.
(cm"1)
.3048 M
2925, 2852 M
1602 M
1452 M
842-705 S
Unassigned weak bands: 1925, 1301,
Other remarks:
High concentration of aromatic material.
1 Assignments/Comments
aromatic C-H
aliphatic C-H
aromatic
aromatic, methyl
aromatic aliphatic
1246, 1185, 1136, 1034
A-40
-------
TABLE A-20. FROTH FLOTATION SEPARATOR, CANISTER RINSE:
LC CUT #3 IR
SAMPLE: 1XR-LC3
1. Major peaks and assignments
v (cm ) I_ Assignments/Comments
3052 S aromatic or olefinic CH
2957, 2926, 2857 aliphatic CH
1927, 1000, 1780 aromatic combinations and overtones
1599 aromatic or olefinic C-C
1456, 1440 aliphatic CH
1382 methyl CH
1195-1025 fingerprint region-aromatics
880, 843, 811, 744, 748 S substituted aromatic cmpds
2, Unassigned weak bands: 1731, 949, 711, and 690 cm"1
3. Other remarks:
Sample contains significant amounts of aromatic hydrocarbons.
A-41
-------
TABLE A-21, FROTH FLOTATION SEPARATOR, CANISTER RINSE:
LC CUT #4 IR
SAMPLE: 1XR-LC4
1. Major peaks and assignments
v (cm-1) I
3502 S
3055 M
2959, 2925, 2856 S
1925-1712 W
1602 M
1459, 1451 S
1376 W
1263-1017 M-W
804, 746, 725 M-S
2. Unassigned weak bands: 2226, 1492,
566 cm"1
3. Other remarks:
Probable alkylated aromatic amines.
Assignments/Comments
2° amine
aromatic or olefinic CH stretch
aliphatic CH stretch
aromatic combination/overtones
aromatic or olefinic C-1-^
aliphatic CH bend
methyl CH bend
fingerprint region aromatic
substituted aromatic cmpds.
1326, 867, 842, 700, 616 and
A-42
-------
TABLE A-22,
FROTH FLOTATION SEPARATOR, CANISTER RINSE:
LC CUT #5 IR
SAMPLE: 1XR-LC5
1. Major peaks and assignments
v (cm )
2.
3.
3357
3055
2959, 2932, 2856
2226, 2075
1733
1602
1458, 1376
1260
1095, 1027
I_ Assignments/Comments
W (broad) alcoholic or phenolic OH or amine
W
S
W
M
M
M,W
M
M
aromatic CH
aliphatic CH
conjugated CnN, or unsymmetric
disub. acetylenic -CsC-
ester or aliphatic ketone
aromatic C^-^-C
aliphatic CH bend
phenolic C-0 aromatic ether, ester
or aromatic amine
ester, alchohol, phenol, 2° aromatic
ami ne
substituted aromatic CH bend
-1
801, 753 M,W
Unassigned weak bands: 1177, 876, 690 cm
Other remarks:
Shape peak at 1260 possibly due to 0-NH-R absorption.
Sample predominantly alkylated phenols or secondary aromatic amines,
or aromatic esters.
A-43
-------
TABLE A-23. FROTH FLOTATION SEPARATOR, CANISTER RINSE:
LC CUT #6 IR
SAMPLE: 1XR-LC6
1. Major peaks and assignments
v_
3062
2.
3.
(cm'1}
2959, 2932, 2856
2062
1740
1650
1602
1452, 1376
1267-1177
828, 752
Unassigned weak bands:
1
W
S
M
M
M
M
M
M
W,M
aromatic CH stretch
aliphatic CH stretch
ketene or ketenimine, or keazoketone
ketene, ester or aliphatic ketone
aliphatic diazoketone
aromatic C-^-^-C
aliphatic CH
aliphatic or aromatic C-0
substituted aromatic
1109, 1020 and 704 cm
-1
Other remarks:
Sample predominantly aromatic and saturated and/or unsaturated hydro-
carbons but does appear to contain some aliphatic esters and aliphatic
diazoketones.
A-44
-------
TABLE A-24.
FORTH FLOTATION SEPARATOR, CANISTER RINSE:
LC CUT #7 IR
SAMPLE: 1XR-LC7
1, Major peaks and assignments
v (cm"1)
2.
3.
3055
2959, 2932, 2856
2062
1746
1465, 1383
1074
821, 753
Unassigned weak bands
Other remarks:
-1
! Assignments/Comments
W aromatic CH stretch
S aliphatic CH stretch
S ketene or ketenimine
(C=C=0) (>C=C=N-)
M ketene, ester or aliphatic ketone
M,W aliphatic CH bend
M aromatic ester ethyl or n-propyl
C-C
W substituted aromatic or ethyl or
n-propyl C-C
1644, 1609, 1348, 1314, 1178, 952 and 691 cm"1
Band at 3261 cm A believed to be due to presence of H«0 in IR cell.
-1 -1
No strong bands in region 1300-1000 cm except at 1074 cm suggest
that absorption at 1746 cm"1 due to ester of saturated acid.
Sample predominantly saturated esters, ketenes, or ketenimines.
A-45
-------
TABLE A-25. CYANIDE GAS TRAIN DATA
Run #
Sampling Location
Volume Metered
(scf)
Catch (CN~)
(mgms)
Concentration
ppm
ygms/scm
1
Final Cooler
Cooling Tower
0.732
1.92
82.4
92,618
Final Cooler
Cooling Tower
0.962
2.16
70.5
70,284
A-46
-------
TABLE A-26. GAS TRAIN DATA SHEET
Run #1
Plant Name: U.S. Steel
Location: Birmingham, Alabama
Sampling Location: Final cooling tower
Operator: B. Hawks
Date: 13 December 1977
Test Time:
Start: 0915.00
Finish: 0945.00
Meter Volume:
Start: 066.560
Finish: 067.286
Volume Sampled: 0.732 scf
AH Setting: 2 scfh
Gas Temperature at Meter Box:
Start: 56
Finish: 56
Ambient Temperature:
Start: 52
Finish: 52
Barometric Pressure: 29.50
Comments:
Gas train bubbling through 0.5M NaOH - 60 ml total volume NaOH
A-47
-------
TABLE A-27. GAS TRAIN DATA SHEET
Run #2
Plant Name: U.S. Steel
Location: Birmingham, Alabama
Sampling Location: Final cooling tower
Operator: B. Hawks
13 December 1977
Date:
Test Time:
Start:
Finish:
Meter Volume:
Start:
Finish:
Volume sampled:
1015.00
1045.00
067.700
068.646
0.962 scf
AH Setting: 2 scfh
Gas Temperature at Meter Box:
Start: 56°
Finish: 60°
Ambient Temperature:
Start: 52°
Finish: 52°
Barometric Pressure: 29.50
Comments:
Gas train bubbling through 60 ml, 0.5M NaOH
A-48
-------
Sample Name:
Sample Date:
Analysis Date:
TABLE A-28. ON-SITE GC OF FINAL COOLER COOLING TOWER
Final Cooling Tower
12/13/77
12/13/77
Range
GC
Range
GC
C.-C
1
1
2
3
4
5
6
7
1
2
3
4
5
p.
O
7
, HYDROCARBONS
7
Bulb #1
ppm
# Peaks (V/V)
1 2.9
0 —
0 —
0 —
0 —
0 —
Q
Bulb #2
ppm
# Peaks (V/V)
1 2.8
0 —
o —
0 —
0 —
n - -
u
0 —
AROMATICS (ppm, V/V)
0
On-Site RTI
Bulb 1 Bulb 2 SS Can
Benzene 5.3 4.7 4.6
Toluene — — —
Ethyl Benzene NA NA —
m & p Xylene NA NA —
o Xylene NA NA —
SULFURS (ppm, V/V)
On-Site
Bulb 1 Bulb 2
H2S (COS) 2.3 2.4
SOp
cs2 — —
NA = No Analysis
— = Compound Not Detected
A-49
-------
TABLE A-29. SASS TRAIN DATA SHEET
Plant Name: U.S. Steel
Location: Birmingham, Alabama
Date: 12/13/77
Test Performed By: F. H. Phoenix, E. E. Stevenson
Run Number: 2
Sampling Location: Final Cooler Cooling Tower
Pre Leak Test: 0.00
Post Leak Test: 0.02
Test Time:
Start: 9:00
Finish: 12:45
Meter Volume (c.f.):
Start: 682.58
Finish: 1683.15
Volume of Gas Sampled: 1000.57 c.f.
974.75 scf.
Average Gas Temperature (°F)
Ambient: 58°
Sampling Location: -
XAD-2 Resin: 57°
Meter Box: 79°
Comments:
1. No condensate collected
2. Used 30' Teflon line as probe, ran from top of tower to XAD-2
module
3. Sampling performed in 1 of 2 ~8' diameter outlets - velocity
taken from fan data
4. Also ran two gas train runs and took hot well and cold well water
samples
A-50
-------
TABLE A-30. ORGANIC EXTRACT SUMMARY, FINAL COOLER COOLING TOWER, XAD-2 RESIN
cn
Preliminary
Total organics mg/sm3 222
TCO, mg 6,066
GRAV, rag 60
Category
Aliphatic hydrocarbons
Halogenated aliphatics
Aromatic hydrocarbons
Halogenated aromatics
Heterocyctic N, 0, S
compounds
Sulfides, disulfides
Nitriles
Ethers
Aldehydes, ketones
Nitroaromatics
Alcohols
Amines
Phenols, halo and nitrophenols
Esters, amides
Mercaptans
Carboxylic acids
Sulfoxides
Concentrate LCI LC2 LC3
61 0.0 (0.82) 37.0 (38.0) 0.76
1,410 0.0 1,020 21
282 0.0 (22.5) 0.0 (30.0) 0.0
LC4
(1.41) 1.20
33
(18.0) 0.0
LC5
(1.63) 0.98 (1
27
(12.0) 0.0 (2.
LC6
.41) 6.74 (8
186
12) 0.0 (36
MATE comparison value,
(0.82) (1.08)
(0.08)
(1.08) (0.65)
(0.11) (0.06)
(0.65)
(0.65)
(0.65)
(0.43)
(0.04)
(0.04)
(0.04)
(0.04)
(0.43)
(0.43)
(0.43)
(0.43)
(0.04)
(0.04)
(0.04)
(0.43)
(0.43)
(0.04)
(0.04)
(0.04)
(0.43)
(1.30)
(1.30)
(0.13)
(1.30)
(0.13)
(0.13)
(1.30)
(0.13)
(0.13)
(0.13)
LC7
.04) 0.0 (0.87)
0.0
.0) 0.0 (24.0)
mg/sm3*
(0.87)
(0.87)
(0.87)
(0.08)
(0.08)
(0.08)
(0.87)
(0.08)
(0.08)
(0.08)
£
46.7 (52.2)
1,287
0.0 (154)
0.0 (1.90)
0.0 (0.08)
0.0 (4.76)
0.0 (0.21)
0.0 (0.08)
0.0 (0.08)
0.0 (0.08)
0.0 (2.38)
0.0 (3.68)
0.0 (0.17)
0.0 1.42)
0.0 (1.42)
0.0 (0.21)
0.0 (3.68)
0.0 (0.21)
0.0 (0.21)
0.0 (0.21)
NOTES: The MATE Comparison Value is based on the GRAV mass in the LC cut divided by the gas sample volume. For compound
classes indicated by IR, the MATE Comparison Value is 100 percent of the GRAV concentration. For compound classes expected65
but not identified by IR, the MATE Comparison Value is 10 percent of the GRAV concentration.
Values in parentheses are GRAV mass before subtraction of blank. The presence of GRAV mass in the original sample is
shown by the Preliminary and Concentrate samples.
-------
TABLE A-31, FINAL COOLER COOLING TOWER VAPOR, XAD-2 RESIN:
PRELIMINARY IR
SAMPLE: 2X-P
1. Major peaks and assignments
v (cm"1) I_
3034 W
2966, 2932, 2875, 2864 S
1723 S
1604, 1491 M, W
1456, 1377 M, W
1269, 1110, 1076 M, S, M
798, 753, 702 W, W, M
Assignments/Comments
aromatic or olefinic CH
aliphatic CH stretch
ketone or ester
aromatic or olefinic C-:-:-:-C
aliphatic CH
ester or aromatic acid, or
aromatic and/or aliphatic
ethers
sub. aromatic cmpds-2 and
5 adj. hydrogens
2. Unassigned weak bands: 1025 cm
3. Other remarks:
Sample contains predominantly aromatic and ali
ethers. Bands in aromatic CH out-of-plane region
and p-disubstituted benzenes are predominant.
phatic esters and/or
suggest monos instituted
A-52
-------
TABLE A-32.
FINAL COOLER COOLING TOWER VAPOR, XAD-2 RESIN:
CONCENTRATE IR
SAMPLE:
1
2X-C
Major peaks and assignments
v (cm" )
3094, 3053, 3006
2965, 2934, 2865
1674-1955
1597 , 1426
781-699
957
I
W,M,W
W
W
M
S-M
M
Assignments/Comments
aromatic or olefinic CH stretch
aliphatic CH stretch
aromatic overtones/combinations
condensed aromatic C^-^C, a-sub,
naphthalenes, conj. vinyl
substituted aromatic cmpds
vinyl CH out-of-plane bend
or aromatic in-plane bend
2. Unassigned weak bands: 1568, 1509, 1456, 1391, 1274, 1245
3. Other remarks:
Sample contains predominantly aromatic hydrocarbons. Bands at 1597,
1426, and 781 cm"1 highly suggestive of a-substituted naphthyl derivatives.
Some saturated hydrocarbons are present as evidenced by weak bands at
2965-2865 cm
vinyl group.
-1
Strong band at 950 cm characteristic of conjugated
A-53
-------
TABLE A-33, FINAL COOLER COOLING TOWER VAPOR, XAD-2 RESIN:
LC CUT #1 IR
SAMPLE: 2X-LC1
1, Major peaks and assignments
v (cm" ) l_ Assignments/Comments
2961, 2972, 2859 S aliphatic CH stretch
1460, 1375 M, W aliphatic CH bend
2. Unassigned weak bands:
3. Other remarks:
This sample possessed less mass than that required by the Level 1 criteria
for IR analysis, A spectrum of acceptable quality was obtained by using
Fourier Transfer IR Techniques.
Sample contains only saturated hydrocarbons.
TABLE A-34. FINAL COOLER COOLING TOWER VAPOR, XAD-2 RESIN:
LC CUT #2 IR
SAMPLE: 2X-LC2
1. Major peaks and assignments
v (cm" ) I_ Assignments/Comments
3062, 3024, 3006 W aromatic or olefinic CH
2962, 2924, 2871 S aliphatic CH stretch
1604, 1514, 1494 W aromatic CH bend
1455, 1375 M,W aliphatic CH bend
800, 755, 735, 699 W,W,W, substituted aromatic cmpds predomi-
M nantly mono-sub, benzene
2. Unassigned weak bands: 1261, 1089, 1029, 886, 868 cm"1
3. Other remarks:
Sample predominantly saturated hydrocarbons containing some substituted
aromatic cmpds.
A-54
-------
TABLE A-35.
FINAL COOLER COOLING TOWER VAPOR, XAD-2 RESIN:
LC CUT #3 IR
SAMPLE: 2X-LC3
1. Major peaks and assignments
v (cm"1)
2.
3.
3030
2965, 2930, 2859
1738
1456, 1380
1263, 1151, 1028
|_ Assi gnments/Comments
W aromatic or olefinic CH
S aliphatic CH stretch
W ketone or ester
M aliphatic CH bend
W ester of aromatic acid, aromatic
ether, aliphatic ether
W,W,W,M substituted aromatic CH bend
1603, 1492, 893
799, 775, 751, 699
Unassigned weak bands
Other remarks:
Sample predominantly saturated and aromatic hydorcarbons, with some
aromatic and aliphatic esters and/or aromatic and aliphatic ethers present.
A-55
-------
TABLE A-36,
FINAL COOLER COOLING TOWER VAPOR, XAD-2 RESIN:
LC CUT #4 IR
SAMPLE: 2X-LC4
1. Major peaks and assignments
v (cm"1)
2959, 2929, 2859
1738
1462, 1380
1268, 1116, 1028
! Assi gnments/Comments
S aliphatic CH stretch
M ketone or ester
M aliphatic CH bend
M,W,W ester of aromatic acid (0-CO-O)
aliphatic or aromatic ether (C-O-C)
1661, 1603, 1069 cm
substituted aromatic cmpds
-1
799, 752, 711
2. Unassigned weak bands:
3. Other remarks:
Sample predominantly aliphatic and aromatic hydrocarbons, containing
some esters of aromatic acids, and/or aromatic or aliphatic ethers.
A-56
-------
TABLE A-37,
FINAL COOLER COOLING TOWER VAPOR, XAD-2 RESIN:
LC CUT #5 IR
SAMPLE: 2X-LC5
1. Major peaks and assignments
v (cm"1)
2959, 2930, 2859
1732
1603
1462, 1380
1280, 1128
I_ Assi gnments/Comments
S Aliphatic CH stretch
S Ester or aliphatic ketone
W Aromatic or olefinic C-^-^^C
M,W Aliphatic CH bend
S,M Aliphatic ester of aromatic acid,
aromatic or aliphatic ether
Substituted aromatic
2,
3.
W
1075 cm
-1
740, 711
Unassigned weak bands:
Other remarks:
This sample possessed less mass than that required by the Level 1 criteria
for IR analysis, A spectrum of acceptable quality was obtained by using
Fourier Transform IR techniques.
Sample appears to contain predominantly aliphatic esters of aromatic
acids and/or aromatic or aliphatic ethers.
A-57
-------
TABLE A-38, FINAL COOLER COOLING TOWER VAPOR, XAD-2 RESIN:
LC CUT #6 IR
SAMPLE: 2X-LC6
1. Major peaks and assignments
v (cm"1)
3063
2959, 2930, 2859
1726
1603
1462, 1380
1274, 1116
I_ Assi gnments/Comments
W aromatic or olefinic CH
S aliphatic CH stretch
S ester or aliphatic ketone
M aromatic or olefinic C-L^-C
M,W aliphatic CH
M,M ester of aromatic ora,e-unsaturated
acids
subsituted aromatic cmpds
M-W
1497 cm"
752, 711, 693
2. Unassigned weak bands
3. Other remarks:
Sample predominantly esters of aromatic or a,g -unsaturated acids and
primary alcohols,
A-58
-------
TABLE A-39, FINAL COOLER COOLING TOWER VAPOR, XAD-2 RESIN:
LC CUT #7 IR
SAMPLE: 2X-LC7
1. Major peaks and assignments
v (cm"1) I
2953, 2930, 2859
1726
1603
1450, 1374
1274, 1045
1110
722
S
M
M
M
M
S
W
Assignments/Comments
aliphatic CH stretch
ester of aliphatic ketone
aromatic of olefinic C-^-^C
aliphatic CH bend
ester of aromatic or a,B -unsat. aci
aliphatic ether
Sub. aromatic, predominantly 4 adj.
d
H
2. Unassigned weak bands: 3323, 3096, 1668, 1556, 940 cm"1
3. Other remarks:
Sample contains predominantly aliphatic ethers with evidence of esters
of aromatic or a,3-unsaturated acids.
TABLE A-40. FINAL COOLER COOLING TOWER VAPOR, CANISTER
RINSE: MASS OF SAMPLE AND CONCENTRATE
Equivalent Total Sample Quantities
Fraction TCO, mg
Preliminary 138
Concentrate 0.0
LCI
LC2
LC3
LC4
LC5
LC6
LC7
3
GRAV, mg Total , mg Total , mg/m
16.0 154.0 5.6
11.0 11.0 0.40
(TCO + GRAV <15 mg, no LC)
A-59
-------
TABLE A-41,
FINAL COOLER COOLING TOWER VAPOR, CANISTER
RINSE: PRELIMINARY IR
SAMPLE: 2XR-P
XAD Canister Rinse No.
Final Cooler
1, Major peaks and assignments
v
3.
(cm"1)
3060
2963, 2927, 2862
1733
1603
1461, 1378
1414
1260
} preliminary sample
I_ Assi gnments/Comments
W aromatic or olefinic CH
S aliphatic CH
S ester or aliphatic ketone
M aromatic C—C
S,M aliphatic CH
M a-naphthalene, aliphatic CH
S aromatic and aliphatic ethers and
esters
aromatic fingerprint region
Substituted aromatic CH bend
S
M
2064, 1946 cm
i
1088 and 1023
805
864 and 698
Unassigned weak bands:
Other remarks:
Bands at 2363-2340 cm" are due to presence of C02 in cell.
Probable aliphatic esters of aromatic acids, and alkylated aromatic
hydrocarbons,
A-60
-------
TABLE A-42,
FINAL COOLER COOLING TOWER VAPOR, CANISTER
RINSE: CONCENTRATE IR
SAMPLE: 2XR-C
1.
2.
Major peaks and
v (cm )
3070
2966-2856
1740
1667
1600
1465
1410
1380
1264
1093-1020
867-800, 697
Unassigned weak
assignments
I
W
S
M
M
W
S
M
M
S
S
S,M
bands: 2082, 1947,
Assignments/Comments
aromatic or olefinic CH
aliphatic CH
aliphatic ketone or ester
aromatic ketone or olefinic C=C
aromatic or conj. olefinic C=C
aliphatic ( methyl ene) or aromatic C-C
a-naphhalene, olefine, or paraffin
methyl and a-naphthalene
aromatic ethers, or esters
aliphatic ethers, aromatic C-C
subsittuted aromatic CH bend
666 cm"1
-1
3. Other remarks:
Peaks at 2365-2340 cm~x due to presence of C02
Bands at 867, 800, and 697 are suggestive of symmetrically substituted
aromatic rings, e_. £., 1,3,5-trisubstituted benzene.
Probable aromatic hydrocarbons and alkylated derivatives and unsatu-
rated hydrocarbons.
A-61
-------
TABLE A-43. FINAL COOLER COOLING TOWER HOT WELL, pH 2 EXTRACT-
MASS OF SAMPLE, CONCENTRATE, AND LC CUTS
Equivalent Total Sample Quantities
Fraction
Preliminary
Concentrate °
LCI
LC2
LC3
LC4
LC5
LC6
LC7
Z
TCO, mg
2,160.0
1,463.0
0
600
0
84
22
574
0
1,280
GRAV, mg
192.0
362.0
25
16
4
12
0
64
'12
133
Total , mg
2,352.0
1,825.0
25
616
4
96
22
638
12
1,413
TABLE A-44. FINAL COOLER COOLING TOWER HOT WELL, PH2
EXTRACT, PRELIMINARY IR
Insufficient sample before concentration to run IR.
A-62
-------
TABLE A-45. FINAL COOLER COOLING TOWER HOT WELL, pH 2 EXTRACT:
CONCENTRATE IR
SAMPLE: 9A-C
1. Major peaks and assignments
2.
3.
v (cm"1)
3600, 3470
3300-3100
3030, 3005
2920, 2960
1720
1615
1595, 1500, 1495
1455, 1375
1280-1200
1150, 1110, 1035
I
S
(broad)
S
S,M
S
S
S
S,W
M-W
S,W,W
S,M
Assignments/Comments
"Free" alcoholic OH, aromatic amines
"free" NH
NH stretch of H-bonded amine or OH
stretch of H-bonded ale.
Aryl or vinyl CH stretch
Alky! CH stretch
Aliphatic ketone or ester
NH banding of 1° amines
NH banding of 2 amines + aryl or vinyl
Al kyl , CH bend
Aromatic CH bends or ester of a,e
unsat acids or aromatic acids,
aromatic CN stretch, or aryl ether
Aliphatic or aromatic ester,
aliphatic ether, or amine C-N
Substituted aromatic CH
1415, 1320, 1175, 930, 880, 690 cm"
835, 730
Unassigned weak bands
Other remarks:
Sample predominantly amines, diphatic ketones or esters of aromatic
acids, and some alcoholic compounds.
A-63
-------
TABLE A-46. FINAL COOLER COOLING TOWER HOT WELL, pH 2 EXTRACT:
LC CUT #1 IR
SAMPLE: 9A-LC1
1, Major peaks and assignments
v (cm"1) ]
2964, 2916, 2821
1494
1462
1412, 1377
1333
863, 670
W
S
S
M
S
M
1749, 1723, 995 cm
Assignments/Comments
Aliphatic CH Stretch
Aromatic O^^C
Aliphatic CH bend, or aromatic
Aliphatic CH band
C-N of teriart amine
Substituted aromatic CH band,
alkane, or C-C1
-1
2. Unassigned weak bands;
3. Other remarks:
This sample possessed less mass than that required by the Level 1 criteria
for IR analysis. A spectrum of acceptable quality was obtained by using
Fourier Transform IR techniques.
Sample appears to contain predominantly aliphatic and aromatic tertiary
amines.
A-64
-------
TABLE A-47. FINAL COOLER COOLING TOWER HOT WELL, pH 2 EXTRACT:
LC CUT #2 IR
SAMPLE: 9A-LC2
1. Major peaks and assignments
(cm"1)
3055
2925, 2856
1725
1602
1453
1376
841, 814
739
Unassigned weak bands:
W
S
W
W
M
W
M
S
1191.
1034.
Assi gnments/Comments
Aromatic C-H, ^CH2-halogen
Aliphatic C-H
Ketone, ester
Aromatic C-^^-C
Aromatic, aliphatic
Methyl CH bend
Aromatic
Aromatic, C-C1
3. Other remarks:
This sample possessed less mass than that required by the Level 1 criteria
for IR analysis. A spectrum of acceptable quality was obtained by using
Fourier Transform IR techniques.
A-65
-------
TABLE A-48. FINAL COOLER COOLING TOWER HOT WELL, PH 2 EXTRACT-
LC CUT #2 LRMS
SAMPLE: 9A-LC2
1. Categories Present
Intensity
100
2, Subcategories
Intensity
100
100
100
100
100
100
3. Other
Intensity
100
10
100
Category
PNA's
Specific Compounds
Subcategory/Compounds
Naphthalene, M/e 128
Phenanthrene, anthracene, M/e 178
Pyrene, M/e 202
Chrysene, triphenylene, M/e 252
Perylene, benzpyrene, M/e 252
Anthanthrene, M/e 276
Comments
M+/e 152
M/e 368. No significant features at M/e
greater than 368.
Acenaphthyliden.e?, M/e 152 PNA assignments
supported by IR.
A-66
-------
TABLE A-49. FINAL COOLER COOLING TOWER HOT WELL, pH 2 EXTRACT:
LC CUT #3 IR
SAMPLE: 9A-LC3
1.
Major peaks
v (cm" )
3048
2927
2858
1727
1601
1450
1380
1264
942
882
812
745
and assignments
I
M
S
M
W
M
M
W
W
W
M
M
S
Assignments/Comments
Aromatic C-H, -CH2-halogen
Aliphatic C-H
Aliphatic C-H
Ketone, ester
Aromatic C-^-C
Aliphatic CH bend
Methyl CH bend
Ester, ether
Aliphatic, aromatic
Aliphatic, aromatic
Aliphatic, Aromatic, C-C1
Unassigned weak bands: 1184, 1163, 1033
Other remarks:
This sample possessed less mass than that required by the Level 1
criteria for IR analysis. A spectrum of acceptable quality was obtained
by using Fourier Transform IR techniques.
Probable PNA hydrocarbon.
A-67
-------
TABLE A-50. FINAL COOLER COOLING TOWER HOT WELL, pH 2 EXTRACT:
LC CUT #4 IR
SAMPLE: 9A-LC4
1. Major peaks
v (cnf )
3418
3062
2959, 2933
1719
1459
1434
1095
746
and assignments
I
S
w
, 2856 W
W
S
M
M
S
Assignments/Comments
OH, NH
Aromatic C-H
Aliphatic C-H
Ketone, ester
Aromatic, aliphatic CH bend
Aromatic, methyl, methylene
Aromatic
Multiplet - aromatic, C-C1
2. Unassigned weak bands:
3. Other remarks:
2363 and 2336 due to CO,
A-68
-------
TABLE A-51. FINAL COOLER COOLING TOWER HOT WELL, pH 2 EXTRACT:
LC CUT #5 IR
SAMPLE: 9A-LC5
1
2.
3.
Major peaks and assignments
-1
v (cm" )
3418
2932, 2856
1719
1458
746
670
W
S
W
M
M
S
Assignments/Comments
OH, NH
Aliphatic C-H
Ketone, ester
Aromatic, methyl, methylene
Aromatic, C-C1
Aromatic, C-C1
1287, 1095, 1013
Unassigned weak bands
Other remarks:
This sample possessed less mass than that required by the Level 1
criteria for IR analysis. A spectrum of acceptable quality was obtained
by using Fourier Transform IR techniques.
2363 and 2336 due to C02. Probable aromatic alcohol or amine.
A-69
-------
TABLE A-52. FINAL COOLER COOLING TOWER HOT WELL, pH 2 EXTRACT:
LC CUT #6 IR
SAMPLE: 9A-LC6
1. Major peaks and
v (cm )
3363
3041
2925
2856
1705
1596, 1506
1459
1376
1287
assignments
I
M
M
S
M
S
S
S
M
S
As s i gnmen ts/Comments
OH
Aromatic C-H
Aliphatic C-H
Aliphatic C-H
Ketone, ester
Aromatic C-^-C
Aliphatic CH bend
Methyl CH bend
Ether ester of aromatic acid,
753
alcohol, or phenol
Substituted aromatic CH bend
2. Unassigned weak bands:
3. Other remarks:
Probable alcohols or alkylated phenols.
A-70
-------
TABLE A-53. FINAL COOLER COOLING TOWER HOT WELL, pH 2 EXTRACT:
LC CUT #6 LRMS
SAMPLE: 9A-LC6
1. Categories Present
Intensity
NONE
2. Subcategories, Specific Compounds
Intensity
NONE
3. Other
Intensity
10
100
Category
Subcategory/Compounds
Comments
No significant ion intensity
> ^ 420 amu
Prominent ions (70eV) at M/e 414,
410, 386, 368, 349, 337, 280, 263
M/e 195, 149, 123, 109
149 possible phthalate.
A-71
-------
TABLE A-54. FINAL COOLER COOLING TOWER HOT WELL, pH 2 EXTRACT:
LC CUT #7 IR
SAMPLE: 9A-LC7
1. Major peaks and
v (cnf )
3287
2927
2856
1738
1693
1597, 1558
1455, 1417
assignments
I
W
S
M
S
M
M
M
Assignments/Comments
alcoholic, phenolic, or
acidic OH
aliphatic C-H
aliphatic C-H
ketone, ester
ketone, acid
aromatic C^^-C
aromatic, methyl ,
methyl ene
2.
3.
749
Unassigned weak bands:
Other remarks:
This sample possessed less mass than that required by the Level 1
criteria for IR analysis. A spectrum of acceptable quality was obtained
by using Fourier Transform IR techniques.
Probable alkylated phenols, ketones or carboxylic acids.
A-72
-------
TABLE A-55. FINAL COOLER COOLING TOWER HOT WELL, pH 12 EXTRACT:
MASS OF SAMPLE, CONCENTRATE, AND LC CUTS
Equivalent Total Sample Quantities
Fraction
TCO, mg
GRAV, mg
Total, mg
Preliminary
Concentrate
LCI
LC2
LC3
LC4
LC5
LC6
LC7
720.0
660.0
0.0
29
0.0
26
10
417
0.0
482
80.0
258.0
0.0
0.0
2.0
6.0
0.0
146
0.0
154
800.0
918.0
0
29
2.0
32.0
10.0
563
0
~636
A-73
-------
TABLE A-56. FINAL COOLER COOLING TOWER HOT WELL, pH 12 EXTRACT:
PRELIMINARY IR
SAMPLE: 9B-P
1.
Major peaks and
v (cm"1)
3300, 3100
3058
2928, 2857
1727
1597
1502
1455, 1178
1106, 1059
746
assignments
I
M(broad)
W
S, M
S
S
M
S
M
S(b)
Assignments /Comments
alcoholic OH or amine or amide NH
aromatic or olefinic CH
aliphatic CH
ester or aliphatic ketone
aromatic C-^^-C, amine NH bend
aromatic C-^-C
aliphatic CH bend, ester, aromatic
amine C-N
ether, ester, aliphatic amine
substituted aromatic CH bend and
2.
3.
NH bend of 1 amines.
834, 811 cm
-1
Unassigned weak bands:
Other remarks:
This sample possessed less mass than that required by the Level 1
criteria for IR analysis. A spectrum of acceptable quality was obtained
by using Fourier Transform IR techniques.
Doubled at 1242 and 1172 cm highly suggestive of CN stretching of
aromatic amines. Probable alkylated aromatic amines, and esters of
aromatic acids.
A-74
-------
TABLE A-57. FINAL COOLER COOLING TOWER HOT WELL, pH 12 EXTRACT:
CONCENTRATE IR
SAMPLE: 9B-C
1. Major peaks and assignments
^ ) 1 Assignments/Comments
3620 M alcoholic free OH stretch
3600, 2900 (broad) alcoholic OH, amide or amine NH
3070, 3006 S aromatic or olefinic CH stretch
2990, 2959, 2890 S, S aliphatic CH stretch
1630, 1610 S 1° amine-NH bend, or amide
1590, 1515 M, S aromatic
1580, 1480 S aromatic
1450, 1380, 1350 W.M.W gem-dimethyl CH vibration
1295 M aromatic amine CH
1260 M( broad) aliphatic amine CH or alcohol
1190, 1010 M-W aromatic fingerprint region,
ether, alcohol, aliphatic amine
or amide.
850, 680 S( broad) 1° and/or 2° amine NH wagging and
CH bend of aromatic compounds,
including heterocyclic amines
760, 700 M substituted benzene
2. Unassigned weak bands: 1325, 958, 950, 940 and 895 cm"
3. Other remarks:
Sample predominantly alcohols, aniline, and alkylated anilines
(both N- and ring substituted). Bands at 1380 cm" and 1350 cm"
suggest that alkylated derivatives are primarily i-pr or t-bu compounds.
Also, the series of bands in region of 1630 - 1450 may arise from
heterocyclic aromatic amines such as pyridine and quinoline, as well as
from the carbon homologs.
A-75
-------
TABLE A-58. FINAL COOLER COOLING TOWER HOT WELL, pH 12 EXTRACT:
LC CUT #1 IR
SAMPLE: 9B-LC1
1. Major peaks and assignments
v (cm ) l_ Assignments/Comments
2956, 2926, 2859 S aliphatic CH stretch
1743 W ester, or aliphatic ketone
1464 „ M aromatic C-^-^C stretch, or
aliphatic CH bend
1452, 1379 W aliphatic CH bend
723 W -(CHpK - rocking or substituted
aromatic CH bend
2. Unassigned weak bands: 1258, 1021
3. Other remarks:
Sample contains predominantly saturated hydrocarbons and saturated
ketones. Possibly small amounts of saturated esters.
A-76
-------
TABLE A-59. FINAL COOLER COOLING TOWER HOT WELL, pH 12 EXTRACT:
LC CUT #2 IR
SAMPLE: 9B-LC2
1.
Major peaks and
v (cm" )
assignments
I
2954, 2926, 2858 S
2.
1462, 1450
1377
809
Unassigned weak
M
W
W
bands: 1193,
Assignments/Comments
aliphatic CM stretch
aliphatic CH bend
methyl CH bend
substituted aromatic CH bend
1143, 1119
3. Other remarks:
This sample possessed less mass than that required by the Level 1
criteria for IR analysis. A spectrum of acceptable quality was obtained
by using Fourier Transform IR techniques.
Sample contains only saturated hydrocarbons with trace amounts of
aromatic compounds.
A-77
-------
TABLE A-60. FINAL COOLER COOLING TOWER HOT WELL, pH 12 EXTRACT:
LC CUT 13 IR
SAMPLE: 9B-LC3
1. Major peaks and assignments
(cm"1)
2957, 2928, 2853
1733
1456, 1375
751
S
M
M
W
Assignments/Comments
aliphatic-CH
ester or aliphatic ketone
aliphatic CH bend
(-CHp)4 - or substituted aromatic
2. Unassigned weak bands: 1687, 1288, 1265
3. Other remarks:
Probable saturated hydrocarbons.
TABLE A-61. FINAL COOLER COOLING TOWER HOT WELL, pH 12 EXTRACT-
LC CUT #3 IR
SAMPLE: 9B-LC3
1.
Major peaks and
v (cm"1)
assignments
I
2959, 2929, 2859 S
2.
1456
1379
1262
752
Unassigned weak
M
W
W
W
bands: 1738,
Ass i gnments/Commen ts
aliphatic CH stretch
aliphatic CH bend
methyl CH bend
t-butyl
substituted aromatic CH bend
1597, 1380, 1280, 1021
3. Other remarks:
Probable saturated and alkylated aromatic hydrocarbons.
A-78
-------
TABLE A-62. FINAL COOLER COOLING TOWER HOT WELL, pH 12 EXTRACT:
LC CUT #4 IR
SAMPLE: 9B-LC4
1. Major peaks and assignments
2.
3.
(cm"1)
2856
2956, 2927,
1735
1604, 1496
1455, 1377
1276, 1121
745, 698
Unassigned weak bands;
S
M
W
M,
W
W
W
Assignments/Comments
aliphatic CH stretch
aliphatic ketone or ester
aromatic C-^^-C stretch
aliphatic CH bend Q
ii
aromatic ester 0-C-O stretch
substituted aromatic CH or C-C1
-1
1216, 1073 and 1020 cm
Other remarks:
Sample appears to be predominantly aliphatic ketones, with some
aromatic esters of considerable aliphatic character present.
Shape spike @ 668 cm" remains unidentified.
A-79
-------
TABLE A-63. FINAL COOLER COOLING TOWER HOT WELL, pH 12 EXTRACT:
LC CUT #5 IR
SAMPLE: 9B-LC5
1. Major peaks and assignments
v (cm ) J^ Assignments/Comments
2959,2932,2856 S aliphatic CH
1733 S ester or aliphatic ketone
1465 M aliphatic CH bend
1287, 1274 S ester of aromatic acid,
aromatic ether
1123, 1075 M ester or ether
746, 695 W substituted aromatic CH bend,
C-C1
2. Unassigned weak bands: 3244, 1602, 1582, 1383, 952, 876
3. Other remarks:
Probable aliphatic esters of aromatic acids.
A-80
-------
TABLE A-64. FINAL COOLER COOLING TOWER HOT WELL, pH 12 EXTRACT:
LC CUT #6 IR
SAMPLE: 9B-LC6
1. Major peaks and assignments
v (cm"1) 1 Assi qnments/Comments
3500- 2500 broad 1° or 2° amines and l°or 2° amides
3055 S aromatic CH
2924, 2856 S aliphatic CH
1595, 1506 S aromatic C-^^C, amide I and
II bands
1460, 1376 M aliphatic CH bend
1246 S aliphatic or aromatic C-N
807, 699 S substituted aromatic compounds
2. Unassigned weak bands: 2068, 1924, 1314, 1157, 1040, 944 cm"1
3. Other remarks:
Sample appears to be predominantly aromatic and aliphatic amines or
amides.
A-81
-------
TABLE A-65.
FINAL COOLER COOLIE
LC CUT
, PH 12 EXTRACT:
SAMPLE: 9B-LC7
1. Major peaks and assignments
(cm"1)
2953, 2930, 2854
2061
1603
S
S
Assignments/Comments
alkyl CH stretch
isothiocyanate or keterimines
(-N=C=S) ( C=C=N)
unresolved C-^-C stretch of sub.
aromatic compound
alkyl CH bend
substituted aromatic CH bend
1656, 1497, 1280 .
1462 M
756, 699 M
2. Unassigned weak bands:
3. Other remarks:
This sample possessed less mass than that required by the Level 1
criteria for IR analysis. A spectrum of acceptable quality was obtained
by using Fourier Transform IR techniques.
Sample contains alkylated aromatic compounds and/or alkyl or aryl
isothiocyanates or keterimines.
A-82
-------
TABLE A-66. FINAL COOLER COOLING TOWER COLD WELL, pH 2 EXTRACT:
MASS OF SAMPLE, CONCENTRATE, AND LC CUTS
Equivalent Total Sample Quantities
Fraction
TCO, mg
6RAV, mg
Total, mg
Preliminary
Concentrate
LCI
LC2
LC3
LC4
LC5
LC6
LC7
1,360.0
862.0
0.0
204
0.0
24
68
562
0.0
858
160
358
15
0.0
8
8
12
124
4
171
1,520.0
1,220.0
15
204
8
32
80
686
4
T7029
A-83
-------
TABLE A-67. FINAL COOLER COOLING TOWER COLD WELL, pH 2 EXTRACT:
PRELIMINARY IR
SAMPLE: 10A-P
1
2.
3.
Major peaks and assignments
v (cm"1) X
W (broad)
W
M,S,S
3500 - 3200
3056
2959, 2918, 2849
1712
1689 - 1644
1603, 1495
1461, 1380
1243
809, 741, 698
Assignments/Comments
alcoholic or phenolic OH
aromatic or olefinic CH
aliphatic CH stretch
ketone, ester
ketone, acid
aromatic C-^-C
aliphatic CH bend
phenol, alcohol, acid, ester
sub. aromatic CH bend
M
M, W
S (broad)
M,S,M
Unassigned weak bands: 1724, 1432, 1123, 1009, 837 cm
Other remarks:
Probable alkylated phenols and carboxylic acids.
-1
A-84
-------
TABLE A-68. FINAL COOLER COOLING TOWER COLD WELL, pH 2 EXTRACT:
CONCENTRATE IR
SAMPLE: 10A-C
1. Major peaks and assignments
2.
3.
(cm"1)
3620, 3500
3500 - 2900
(2 broad
bands)
Assi qnments/Comments
free alcoholic or phenolic OH
banded OH-alcohol or phenol
aromatic or olefinic CH stretch
aliphatic CH stretch
ketone or ester
substituted aromatic
aromatic or olefinic
aliphatic CH bend
alcoholic or phenolic C-0, or
aliphatic ethers
substituted aromatic CH
1330, 1320, 1290, 1275, 1040, 945 cm"
3030 S
2950, 2890 S
1712 W
1630, 1610 S (broad)
1520, 1500 S
1465, 1390, 1365 S,M.M
1190-1160,1115 S, M
890, 845, 695 W,M,W
Unassigned weak bands: 1422.
Other remarks:
Sample predominantly alcohols, and alkylated phenols. Small peak at 1712
cm"1 suggests that small quantities of carboxylic acids, ketones, and/or
esters might be present.
A-85
-------
TABLE A-69. FINAL COOLER COOLING TOWER COLD WELL, pH 2 EXTRACT:
LC CUT #1 IR
SAMPLE: 10A-LC1
v
(cm"1)
Major peaks and assignments
I
S
W
w
2949, 2923, 2854
1748, 1711
1463, 1379
1154, 1107 cm
Assignments/Comments
alky! CH stretch
ester and/or ketone
alky! CH bend
-1
Unassigned weak bands:
Other remarks:
This sample possessed less mass than that required by the Level 1
criteria for IR analysis. A spectrum of acceptable quality was obtained
by using Fourier Transform IR techniques.
Sample appears to contain only aliphatic hydrocarbons, esters, and
ketones.
A-86
-------
TABLE A-70. FINAL COOLER COOLING TOWER COLD WELL, pH 2 EXTRACT:
LC CUT #2 IR
SAMPLE: 10A-LC2
1. Major peaks and assignments
(cm"1)
3045
2954,2926,2857
1726
1459, 1378
1261
841 - 699
W
S
W
M,W
W
W
1039, 876 cm
Ass i gnments/Comments
aromatic or olefinic CH
aliphatic CH stretch
ketone or ester
aliphatic CH bend
aromatic ester C-CO-0 stretch
aromatic CH bending (substituted)
-1
Unassigned weak bands
Other remarks:
This sample possessed less mass than that required by the Level 1
criteria for IR analysis. A spectrum of acceptable quality was obtained
by using Fourier Transform IR techniques.
Sample predominantly saturated and aromatic hydrocarbons, with some
aromatic and/or alkyl esters.
A-87
-------
TABLE A-71. FINAL COOLER COOLING TOWER COLD WELL, pH 2 EXTRACT:
LC CUT #3 IR
SAMPLE: 10A-LC3
1.
Major peaks and assi
v (crrf )
2942, 2930, 2859
1462
0 840
746
gnments
I
S
M
M
S
Assignments/Comments
aliphatic CH stretch
aliphatic CH bend
aromatic, unsaturated
aromatic CH bend
CH bend
2. Unassigned weak bands: 881
3. Other remarks:
This sample possessed less mass than that required by the Level 1
criteria for IR analysis. A spectrum of acceptable quality was obtained
by using Fourier Transform IR techniques.
Probably alkylated aromatics.
A-88
-------
TABLE A-72. FINAL COOLER COOLING TOWER COLD WELL, pH 2 EXTRACT:
LC CUT #4 IR
SAMPLE: 10A-LC4
1. Major peaks
v (cm" )
3398
2952, 2932
1719
1452
1027
746, 725
and assignments
I
S
, 2863 S
S
S
M
S
Assignments/Comments
phenolic or alcoholic OH
aliphatic CH stretch
ketone/ester
aliphatic CH bend
ether, aliphatic ester
(-Q-L), or substituted
aromatic CH bend
2. Unassigned weak bands:
3. Other remarks:
Probable aliphatic ketones, esters, or ethers and/or alkylated
phenols.
A-89
-------
TABLE A-73. FINAL COOLER COOLING TOWER COLD WELL, pH 2 EXTRACT:
LC CUT #5 IR
SAMPLE: 10A-LC5
1. Major peaks and assignments
(cm"1)
3411
3336
2959, 2932, 2856
1712
1602, 1589
1452, 1342
1090, 1013
739
1
S
M
S
M
W
S
M
Assignments/Comments
alcoholic or phenolic OH
alcoholic or phenolic OH
aliphatic CH
ketone or ester
aromatic or olefinic C^-C
aliphatic CH bend
phenolic or alcoholic CO
stretch, aliphatic ether or
ester
substituted aromatic CH bend
or C-C1
2. Unassigned weak bands: 1280, 1218, 3055, 698
3. Other remarks:
Probable alkylated phenols and some aliphatic ketones and/or
esters.
A-90
-------
TABLE A-74 FINAL COOLER COOLING TOWER COLD WELL, pH 2 EXTRACT:
LC CUT #6 IR
SAMPLE: 10A-6
1. Major peaks and assignments
v (cm" ) !
3300 - 2500 S(broad)
3034 S
2959, 2924, 2863 S
1698 S
1595 S
1500 - 1600 M
1458, 1376 M,W
1266, 1157, 1026 M
Assignments/Comments
carboxylic acid OH phenolic
OH stretch
aromatic CH stretch
aliphatic CH stretch
asym. C=0 stretch for saturated
and unsatura ted/aromatic
carboxylic isomer
aromatic
aromatic
aliphatic CH
C-0 of carboxylic acids and
phenols
aromatic compounds - substituted
-1
835, 773, 752, 691 M
2. Unassigned weak bands: 2068, 1869, 931 cm"
3. Other remarks:
Sample predominantly aromatic and aliphatic carboxylic acids and/or
alkylated phenols.
A-91
-------
TABLE A-75. FINAL COOLER COOLING TOWER COLD WELL, pH 2 EXTRACT:
LC CUT #7 IR
SAMPLE: 10A-LC7
1. Major peaks and assignments
v (cm"1) J_
M
M
S
M
M
2962, 2920, 2852
1738
1703
1618, 1439 (?)
1104, 1042
2.
3.
Assignments/Comments
alkyl CH stretch
ester, or aliphatic ketone
ketone or ester
aromatic or olefinic Cr-^C
aliphatic ethers, or 2° alcohol
-1
1676, 863, 834 cm
Unassigned weak bands:
Other remarks:
This sample possessed less mass than that required by the Level 1
criteria for IR analysis. A spectrum of acceptable quality was obtained
by using Fourier Transform IR techniques.
Sample appears to contain only residual aliphatic ketones and esters.
A-92
-------
TABLE A-76. FINAL COOLER COOLNG TOWER COLD WELL, pH 12 EXTRACT:
MASS OF SAMPLE, CONCENTRATE, AND LC CUTS
Equivalent Total Sample Quantities
Fraction
Preliminary
Concentrate
LCI
LC2
LC3
LC4
LC5
LC6
LC7
Z
TCO, mg
480.0
356.0
0.0
0.5
0.0
7.5
4.5
239
0.0
252
GRAY, mg
160.0
29.0
0.0
0.0
1.0
3.0
1.0
25
0.0
30.0
Total , mg
640.0
385.0
0.0
0.5
1.0
10.5
5.5
264
0.0
282
TABLE A-77. FINAL COOLER COOLING TOWER COLD WELL, PH 12 EXTRACT:
PRELIMINARY IR
Insufficient sample before concentration to run IR.
A-93
-------
TABLE A-78. FINAL COOLER COOLING TOWER COLD WELL, pH 12 EXTRACT:
CONCENTRATE IR
SAMPLE: 10B-C
1. Major peaks and
v (cm" )
3400 - 3000
3062
2954, 2870
2151, 2055
1705, 1664
1604, 1515
1500
1445
1376
1322
1267 - 1034
900 - 800
746, 691
2. Unassigned weak
assignments
1
S( broad) .
S
M
W
S
S
S
S
M
W
M( broad)
S,M
bands: 1548
Assignments/Comments
amine or amide NH stretch
aromatic or olefinic CH stretch
aliphatic CH stretch
ketenes ( C=C=0) and
isothiocyanates
amide I bands ( N=C=S)
( C=0 stretch)
amide II bands (N-H bend) or
amine NH bend, or aromatic C^-^C
aromatic C-^^C
aliphatic CH or saturated
1° amide
aliphatic CH bend
aromatic amine C-N
aromatic fingerprint region and/or
ami no C-N stretching
amine and/or amide NH bend
monosubstituted benzene
en,'1.
3. Other remarks:
Sample predominantly aryl and/or alky! amines and amides; bands at 3062,
1664, 1604, 815, 746 and 691+1 strongly suggesting that appreciable
amounts of aniline, N-alkylated aniline, and/or amides of benzoic acid are
present.
A-94
-------
TABLE A-79. FINAL COOLER COOLING TOWER COLD WELL, pH 12 EXTRACT:
LC CUT #1 IR
SAMPLE: 1 OB-LCI
1. Major peaks and assignments
v (cm ) J_ Assignments/Comments
2957, 2928, 2853 S aliphatic CH stretch
1750 W ketone or ester
1462, 1375 M, W aliphatic CH bend
2. Unassigned weak bands: 1467, 722 cm"
3. Other remarks:
Sample contains predominantly saturated hydrocarbons.
TABLE A-80. FINAL COOLER COOLING TOWER COLD WELL, pH 12 EXTRACT:
LC CUT #2 IR
SAMPLE: 10B-LC2
1. Major peaks and assignments
v (cm" ) !_ Assignments/Comments
2854, 2956, 2947,
2424 S aliphatic CH stretch
1457, 1463, 1380 M aliphatic CH bend
1261, 1161 W aromatic or aliphatic ether
1015, 1038 W aromatic or aliphatic ether
810, 804 W substituted aromatic CH
bend or C-C1
2. Unassigned weak bands: 1600, 1586
3. Other remarks:
This sample possessed less mass than that required by the Level 1
criteria for IR analysis. A spectrum of acceptable quality was obtained
by using Fourier Transform IR techniques.
Probable saturated hydrocarbons, with some aromatic or aliphatic
ethers.
A-95
-------
TABLE A-81. FINAL COOLER COOLING TOWER COLD WELL, pH 12 EXTRACT:
LC CUT #3 IR
SAMPLE: 10B-LC3
1. Major peaks and assignments
2.
3.
(cm"1)
2959, 2929, 2859
1738
1462, 1380
1262
1028
746, 722
J_
S
W
W
w
w
w
Assignments/Comments
aliphatic CH stretch
ester or aliphatic ketone
aliphatic CH bend
alkane, aromatic, aromatic
ether, ester of aromatic acid
aromatic or aliphetic ether
ester of aromatic acid
). - rocking or substituted
aromatic CH bend
Unassigned weak bands:
Other remarks:
This sample possessed less mass than that required by the Level 1
criteria for IR analysis. A spectrum of acceptable quality was obtained
by using Fourier Transform IR techniques.
Probable diaphatic esters of aromatic acids, or aliphatic or
aromatic ethers.
A-96
-------
TABLE A-82. FINAL COOLER COOLING TOWER COLD WELL, pH 12 EXTRACT:
LC CUT #4 IR
SAMPLE: 10B-LC4
1. Major peaks and assignments
2.
3.
(cm"1)
2959, 2929, 2859
1730
1456, 1380
o
1116
746, 711
S
M
M,
W
W
W
Assignments/Comments
aliphatic CH stretch
ester or aliphatic ketone
aliphatic CH bend
saturated ester and/or ether
substituted aromatic CH bend
Unassigned weak bands: 1439
Other remarks:
This sample possessed less mass than that required by the Level 1
criteria for IR analysis. A spectrum of acceptable quality was obtained
by using Fourier Transform IR techniques.
Sample contains predominantly aliphatic hydrocarbons and/or esters,
with some substituted aromatic compounds.
A-97
-------
TABLE A-83. FINAL COOLER COOLING TOWER COLD WELL, pH 12 EXTRACT:
LC CUT #5 IR
SAMPLE: 10B-LC5
1. Major peaks and assignments
v (cm" ) _!_
2962, 2923, 2853 W
1648 M
1508 M
1460 M
680 M
Assignments/Comments
aliphatic CH stretch
term vinyl, NH2 in plane bending
-NH-, aromatic
aliphatic CH, aromatic or
olefinic C^-C
-NFL- out of plane bending or
aromatic CH bend
2. Unassigned weak bands: 1750
3. Other remarks:
Probable saturated and unsaturated hydrocarbons, or alkylated
aromatic derivatives.
A-98
-------
TABLE A-84. FINAL COOLER COOLING TOWER COLD WELL, pH 12 EXTRACT:
LC CUT #6 IR
SAMPLE: 10B-LC6
1. Major peaks and assignments
v (cm" )
3671 - 3165
3062
2925, 2856
2733, 2603
1678
1596, 1507
1465, 1376
1267 - 1246
I
S
S
S
M
M
S
S, W
S
Assignments/Comments
alcohol, amine, amide
aromatic CH stretch
aliphatic CH stretch
saturated amine
amide I band
aromatic C-^-^C, NH bending of 1°
amide or amine
aliphatic CH bend
alcohol, aromatic ether,
1157, 1122, 1040
808, 787, 752,
691
M
aromatic amine
ether, alcohol, phenol, amide NH
bend or amine CN
S sub. aromatic CH bend
2. Unassigned weak bands: 1314, 945
3. Other remarks:
Probable alkylated aromatic amines.
A-99
-------
TABLE A-85. FINAL COOLER COOLING TOWER COLD WELL, pH 12 EXTRACT:
LC CUT #7 IR
SAMPLE: 10B-LC7
1. Major peaks and
v (cm" )
* 3569
3267
2925, 2856
2062
1657
1602
1541 - 1507
1459, 1376
1287
1123 - 1075
753 - 698
assignments
I
S
S( broad)
S
M
S
S
M
M
M
M
M
Assignments/Comments
alcoholic OH, ami no NH stretch
alcoholic OH, amine or amide
aliphatic CH stretch
isothiocyanate
conj. olefinic C-1-^, amide
I band or amine NH bend
aromatic C-1-^, amine or 1°
amide NH
aromatic <—£, 2° amide NH
aliphatic CH bend
aromatic amine CN stretch,
aromatic ether
alcohol, ether, amine C-N
substituted aromatic CH bend
NH
0
2.
3.
828 cm"
Unassigned weak bands:
Other remarks:
This sample possessed less mass than that required by the Level 1
criteria for IR analysis. A spectrum of acceptable quality was obtained
by using Fourier Transform IR techniques.
Probable alkylated aromatic amides and amines.
A-100
-------
TABLE A-86. SASS TRAIN DATA SHEET
Plant Name: U.S. Steel
Location: Birmingham, Alabama
Date: 12/13/77
Test Performed By: F. J. Phoenix, E. E. Stevenson
Run Number 3
Sampling Location: Tar Storage Tank
Pre Leak Test: 0.02
Post Leak Test: 0.05
Test Time:
Start: 14:55
Finish: 15:44
Meter Volume (c.f.):
Start: 685.67
Finish: 889.97
Volume of Gas Sampled: 202.28 c.f. *
199.06 scf.
Average Gas Temperature (°F)
Ambient: 60°
Sampling Location: 85°
XAD-2 Resin: 80°
Meter Box: 70°
Comments:
1. Naphthalene condensed on XAD-2 Module.
We had to take module apart and clean off Naphthalene during
run.
* 2.02 c.f. was subtracted from sample volume due to leak check
during run.
A-101
-------
TABLE A-87. TAR STORAGE TANK
Sample Name: Tar Storage Tank
Sample Date: 12/13/77
Analysis Date: 12/13/77
crc?
Range
GC 1
2
3
4
5
6
7
Range
GC 1
2
3
4
5
6
7
HYDROCARBONS
Bulb #1
# Peaks
1
2
1
0
0
0
0
Bulb #2
# Peaks
1
2
1
n
n
0
0
ppm
(V/V)
6.6
0.9
0.1
—
—
—
—
ppm
0//V)
1.0
0.8
0.1
—
—
AROMATICS (ppm, V/V)
On-Site RTI
Bulb 1 Bulb 2 SS Can
Benzene 20.6 20.0 20.0
Toluene 5.6 5.5 5.4
Ethyl Benzene NA NA —
m & p Xylene NA NA 2.5
o Xylene NA NA 1.2
SULFURS (ppm, V/V)
On-Site
Bulb 1 Bulb 2
H2S (COS) — —
so2 — —
vsOQ """"•
NA = No Analysis
— = Compound Not Detected
A-102
-------
TABLE A-88. ORGANIC EXTRACT SUMMARY, VAPOR ABOVE TAR STORAGE TANK, XAD-2 RESIN
Preliminary
Total organics mg/sm3
TCO, mg
GRAV, mg
1
6
,192
,620
100
Concentrate LCI
1,530
6,090
2,540
76.3
430
0.0
LC2
1,780
10,040
20
LC3
148
836
0.0
LC4
37.4
191
20
LC5
24.11
96
40
LC6
192
1,080
0.0
LC7
10.63
0.0
60
Z
2,270
12,700
140
Category
MATE comparison value, mg/sm3*
o
co
Aliphatic hydrocarbons
Halogenated aliphatics
Aromatic hydrocarbons
Halogenated aromatics
Heterocyclic N, 0, S
compounds
SuTfides, disulfides
Nitriles
Ethers
Aldehydes, ketones
Nitroaromatics
Alcohols
Ami nes
Phenols, halo and nitrophenols
Esters, amides
Mercaptans
Carboxylic acids
Sulfoxides
0.0
0.0
3.55 0.0 3.55
0.36 0.0 0.36
0.36
0.36
0.36
3.55
3.55
3.55
7.09
0.71
0.71 •
0.71
7.09
7.09
0.71
0.71
0.71
7.09
10.6
10.6
1.06
1.06
1.06
10.6
1.06
1.06
1.06
0.0
0.0
24.8
0.72
1.07
1.07
1.07
10.6
21.2
0.71
1.77
1.77
1.06
21.2
1.06
1.06
1.06
NOTE: The MATE Comparison Value is based on the GRAV mass in the LC cut divided by the gas sample volume. For compound
classes indicated by IR, the MATE comparison value is 100 percent of the GRAV concentration. For compound classes
expected65 but not identified by IR, the MATE Comparison Value is 10 percent of the GRAV concentration.
-------
TABLE A-89. VAPOR ABOVE TAR STORAGE TANK, XAD-2 RESIN:
PRELIMINARY IR
SAMPLE: 3X-P
1. Major peaks and assi
v (cm'1)
3060, 3031
2964, 2930, 2874
1725
1602, 1495
1455, 1376
1275, 1106, 1067
gnments
I
W
S
M
M
M,W
M
Assignments/Comments
aromatic or olefinic CH
aliphatic CH stretch
ketone or ester
aromatic CH bend
aliphatic CH bend
ester of aromatic acid, aromatic
2.
3.
802, 751, 701
and/or aliphatic ether
sub. aromatic CH bend
-1
W,W,M
Unassigned weak bands: 1027, 892, 830 cm"
Other remarks:
Sample predominantly aliphatic and aromatic esters and ethers. IR
spectrum suggests that sample is predominantly esters of aromatic acids
and alkyl ethers.
A-104
-------
TABLE A-90. VAPOR ABOVE TAR STORAGE TANK, XAD-2 RESIN:
CONCENTRATE IR
SAMPLE: 3X-C
1. Major peaks and assignments
v (cm ) I_ Assignments/Comments
3071, 3054, 3007 W,M,W aromatic and/or olefinic CH
2967-2863 W aliphatic CH stretch
1954-1676 W aromatic overtone region
1595, 1387 M aromatic or conjugated
olefinic
1213-1011 W aromatic fingerprint region
958 M conjugated vinyl CH bend, or
aromatic in-plane bend
785-698 S-W substituted aromatic CH bend
2. Unassigned weak bands: 1566, 1508, 1364, 843 cm" .
3. Other remarks:
Sample predominantly aromatic and unsaturated hydrocarbons.
A-105
-------
TABLE A-91. VAPOR ABOVE TAR STORAGE TANK, XAD-2 RESIN-
LC CUT #1 IR
SAMPLE: 3X-LCl-sub H20
1. Major peaks and assignments
v (cm"1)
2975, 2936, 2859 S
1513, 1464 M
1282, 1216, 970 M
Assignments/Comments
aliphatic CH
aliphatic stretch
aliphatic stretch
2. Unassigned weak bands:
3. Other remarks:
This sample possessed less mass than that required by the Level 1 criteria
for IR analysis. A spectrum of acceptable quality was obtained by using Fouriei
Transform IR techniques.
Probable aliphatic hydrocarbons.
A-106
-------
TABLE A-92. VAPOR ABOVE TAR STORAGE TANK, XAD-2 RESIN:
LC CUT #2 IR
SAMPLE: 3X-LC2
1. Major peaks and assignments
v (cm ) J_ Assi gnments/Comments
3060, 3025 W aromatic CH stretch
2963, 2924, 2857 S aliphatic CH stretch
1604, 1494 W aromatic C--C stretch
1455, 1375 M,W aliphatic CH bend
800, 752 W sub. aromatic CH bend
752, 699 W,M sub. aromatic CH bend
2. Unassigned weak bands: 1589, 1535, 1261, 1029, 889.
3. Other remarks:
Sample predominantly saturated hydrocarbons and mono-substituted
benzene.
A-107
-------
TABLE A-93. VAPOR ABOVE TAR STORAGE TANK, XAD-2 RESIN:
LC CUT #3 IR
SAMPLE: 3X-LC3
1. Major peaks and assignments
v (cm"1)
3025 W
2961, 2926, 2854 S
1741, 1732 W
1603, 1588, 1494 W
1462, 1453, 1377 W
799, 758, 705 W,W,M
Assignments/Comments
aromatic CH stretch
aliphatic CH stretch
ester of aromatic acid,
0-CO-O
aromatic C-1-^ stretch
aliphatic CH bend
sub. aromatic cmpds,
primarily monosub. benzene
-1
2. Unassigned weak bands: 1263, 1072, 1031, 893 cm"1.
3. Other remarks:
Sample predominantly saturated hydrocarbons, sat. ketones or ester,
containing trace of aromatic cmpds.
A-108
-------
TABLE A-94. VAPOR ABOVE TAR STORAGE TANK, XAD-2 RESIN:
LC CUT #4 IR
SAMPLE: 3X-LC4
1. Major peaks and assignments
2.
3.
v (cm"1)
2959, 2930, 2859
1726
1462
1456, 1380
1268, 1110, 1028
L Assignments/Comments
S aliphatic CM stretch
M ester, or aliphatic ketone
M aromatic C-^C
M,W aliphatic CH bend
M,W,W ester of aromatic acid,
aromatic and/or aliphatic
ether
W,W,M substituted aromatic
1585, 1069 cm
-1
799, 752, 711
Unassigned weak bands:
Other remarks:
This sample possessed less mass than that required by the Level 1 criteria
for IR analysis. A spectrum of acceptable quality was obtained by using
Fourier Transform IR techniques.
Sample contains predominantly alkylated esters of aromatic acids,
and/or saturated hydrocarbons.
A-109
-------
TABLE A-95. VAPOR ABOVE TAR STORAGE TANK, XAD-2 RESIN:
LC CUT #5 IR
SAMPLE: 3X-LC5
1. Major peaks and assignments
v (cm ) _!_ Assignments/Comments
2959, 2932, 2856 S aliphatic CH stretch
1726 S ester, or aliphatic ketone
1459, 1376 M,W aliphatic CH bend
1274, 1116, 1075 S,W ester of aromatic acid, aromatic
or aliphatic ether
801, 746, 712 W substituted aromatic
2. Unassigned weak bands: 1027 cm"1.
3. Other remarks:
This sample possessed less mas than that required by the Level 1 criteria
for IR analysis. A spectrum of acceptable quality was obtained by using
Fourier Transform IR techniques.
Sample predominantly saturated hydrocarbons and alky! esters of aromatic
acids and/or alkyl and aryl ethers.
A-110
-------
TABLE A-96. VAPOR ABOVE TAR STORAGE TANK, XAD-2 RESIN:
LC CUT #6 IR
SAMPLE: 3X-LC6
1. Major peaks and assignments
v (cm )
3600-3200
3065, 3029
2959, 2928, 2883
1726
1604, 1514, 1497
1464, 1456
1378, 1357
1273, 1113
1220-1080
749, 711, 699
1
W(broad)
W
S
S
M,W,M
S
M
M
W-M
Assignments/Comments
alcoholic or phenolic OH
aromatic or olefinic CH
stretch
aliphatic CH stretch
ester or aliphatic
ketone
aromatic or conj. ole-
finic
aliphatic CH bend
gem-dimethyl CH bend
ester of aromatic acid
aromatic fingerprint
region
substituted aromatic CH
bend
-1
2. Unassigned weak bands: 1681, 1312, 1029, 1022, 824, 800 cm
3. Other remarks:
Sample predominantly alkylated esters of aromatic acids and alcohols.
A-111
-------
TABLE A-97. VAPOR ABOVE TAR STORAGE TANK, XAD-2 RESIN:
LC CUT #7 IR
SAMPLE: 3X-LC7
1. Major peaks and assignments
v
2.
3.
(cm"1)
3082, 2065, 3030
2957, 2927, 2854
1746
1604, 1586, 1497
1455, 1357
1220, 1148
752, 732, 699
W
S
M
M,W,S
S,M
S,M
Assi gnments/Comments
aromatic or olefinic CH
aliphatic CH stretch
ester or aliphatic ketone
aromatic C-^^^C
aliphatic CH bend
aliphatic ester of aromatic
acid
M,M,S
1080, 1029, 988, 934, 886
sub. aromatic, predominantly
monosub benzene
Unassigned weak bands:
Other remarks:
Sample predominantly ester of aromatic or a,$-unsaturated acid and
primary alcohols.
A-112
-------
TABLE A-98. ORGANIC EXTRACT SUMMARY, VAPOR ABOVE TAR STORAGE TANK, CANISTER RINSE
Preliminary Concentrate
Total organics mg/sm3 293 132
TCO, mg 1,545
GRAV, mg 109 (spill) 743
Category
Aliphatic hydrocarbons
Halogenated aliphatics
Aromatic hydrocarbons
Halogenated aromatics
Heterocyclic N,0,S
compounds
Sulfides, disulfides
Nitriles
Ethers
Aldehydes, ketones
Nitroaromatics
Alcohols
Amines
Phenols, halo and nitrophenols
Esters, amides
Mercaptans
Carboxylic acids
Sulfoxides
LCI LC2
5.90 70.1
24.2 364
9.10 31.5
MATE
1.6
0.16
5.6
0.56
1.6 5.6
5.6
5.6
5.6
1.6 5.6
LC3
81.6
453
7.28
comparison
1.3
0.13
1.3
1.3
1.3
LC4 LC5 LC6
0.86 0 4.3
2.42 0.0 24.2
2.42 0.0 0.0
value, mg/sm3*
0.43
0.04
0.04
0.04
0.04
0.43
0.43
0.43
LC7 £
0.0 162
0.0 868
0.0 50.3
1.6
01 a
. ID
7.33
0-7 f\
.73
Or\/i
.04
0.04
0.04
8.93
7.33
Or*
.U
5.6
0.0
5.6
8r\
.y
0.0
On
.U
Or\
.U
NOTE: The MATE Comparison Value is based on the GRAV mass in the LC cut divided by the gas sample volume. For com-
pound classes indicated by IR, the MATE comparison value is 100 percent of the GRAV concentration. For compound
classes expected65 but not identified by IR, the MATE Comparison Value is 10 percent of the GRAV concentration.
-------
TABLE A-99.
VAPOR ABOVE TAR STORAGE TANK: CANISTER RINSE:
PRELIMINARY IR
Insufficient sample before concentration to run IR.
TABLE A-100. VAPOR ABOVE TAR STORAGE TANK, CANISTER RINSE:
CONCENTRATE IR
SAMPLE: 3XR-C
XAD Canister Rinse No. 3
Tar Storage Rinse
1. Major peaks and assignments
concentrate of no. 9
v (cm"1)
3071, 3053, 3035
2980
1595-1502
1388
1354
960
846
780
W,M,W
W
W
M
W
M
W
S
Unassigned weak bands: 1274, 1127, 1007 cm
Assignments/Comments
aromatic or olefinic CH
stretch
aliphatic CH stretch
aromatic C C stretch
a-naphthalenes
methyl CH
H-C=C-H trans or aromatic
CH
aromatic or olefinic CH
substituted aromatic CH
-1
Other remarks:
Inverted peaks at 2365-2340 cm are due to presence of COp.
This sample was known to contain significant amounts of naphthalene
(which crystallized out upon concentration), and the above unassigned weak
bands are believed to be due to the presence of these aromatic cmpds, which
give rise to several bands in the region 950-1200 cm" ; the fingerprint region
for aromatic cmpds.
A-114
-------
TABLE A-101. VAPOR ABOVE TAR STORAGE TANK, CANISTER RINSE:
LC CUT #1 IR
SAMPLE: 3XR-LC1
1. Major peaks and assignments
2.
3.
v (cm )
2959, 2924, 2856 S
1733 M
1459 M
1376 VI
1274 W
Assignments/Comments
aliphatic CH stretch
ester or aliphatic ketone
aliphatic CH
methyl CH
conjugated ester or ether C-0
or Si-C
Unassigned weak bands: 1561, 1123, 1068, 718, 671.
Other remarks:
Probable saturated hydrocarbons with trace of aromatic ether or ester
of aromatic acid.
A-115
-------
TABLE A-102. VAPOR ABOVE TAR STORAGE TANK, CANISTER RINSE:
LC CUT #2 IR
SAMPLE: 3XR-LC2
1. Major peaks and assignments
v (cm"1)
3600-3000
3048
2959, 2931, 2856
1719
1452, 1376
1260
1095, 1034
810
739
I
M(broad)
S
S
M
M
M
M!
M \
Assignments /Comments
alcoholic or phenolic
aromatic CH
aliphatic CH
ketone, ester
aliphatic CH bend
ether, ester, alcohol,
ether, alcohol, phenol
of aromatic acid
OH
phenol
, ester
monosubstituted benzene
2. Unassigned weak bands: 1630, 1239, 1164, 864 cm'1.
3. Other remarks:
Probable aliphatic esters of aromatic acids and alcohols.
A-116
-------
TABLE A-103. VAPOR ABOVE TAR STORAGE TANK, CANISTER RINSE:
LC CUT 13 IR
SAMPLE: 3XR-LC3
1. Major peaks and assignments
2.
3.
v (cm )
3055, 3041 M
2959, 2932, 2856 S
1925 M
1732, 1718 M
1459, 1376 S
1260, 1089, 1020, M
958
Assignments/Comments
aromatic CH stretch
aliphatic CH stretch
aromatic sub.
ketone, ester
aliphatic CH bend
ester or ether, aromatic CH bend
substituted aromatic CH bend
1390, 671, 670, 1616.
780, 746, 712
Unassigned weak bands:
Other remarks:
This sample possessed less mass than that required by the Level 1 criteria
for IR analysis. A spectrum of acceptable quality was obtained by using
Fourier Transform IR techniques.
Probable alkylated aromatic ethers and alkylated aromatic hydrocarbons.
A-117
-------
TABLE A-104. VAPOR ABOVE TAR STORAGE TANK, CANISTER RINSE:
LC CUT #4 IR
SAMPLE: 3XR-LC4
1. Major peaks and assignments
v (cm ) l_ Assignments/Comments
2959, 2932, 2856 S aliphatic CH stretch
1733 S ester or aliphatic ketone
1459, 1376 M.W aliphatic CH bend
1287, 1123, 1075 S.H.W ester of aromatic acid and/
or aryl and alky! ethers
739, 660 M monosubstituted benzene
2. Unassigned weak bands:
3. This sample possessed less mass than that required by the Level 1
criteria for IR analysis. A spectrum of acceptable quality was obtained by
using Fourier Transform IR techniques.
Spectrum strongly suggests that sample is predominantly benzoates
of 1° and 2° alcohols.
A-118
-------
TABLE A-105. VAPOR ABOVE TAR STORAGE TANK, CANISTER RINSE:
LC CUT #5 IR
SAMPLE: 3XR-LC5
1. Major peaks and assignments
v (cm"1)
2961, 2929, 2861 S
1733 S
1457 M
1376 W
1276, 1126 M
1075, 744 W,M
744, 701 M
Unassigned weak bands: 1038 cm
2.
3.
-1
Assignments/Comments
aliphatic CH
ester or aliphatic ketone
aliphatic CH bend
methyl CH bend
aliphatic ester of aromatic acid
substituted aromatic CH or ethyl
C-C
substituted aromatic CH
Other remarks:
Sample predominantly aliphatic esters and/or sat. hydrocarbons but bands
-1
at 1075, 1038, 744, and 701 cm suggest presence of same aromatic cmpds.
A-119
-------
TABLE A-106. VAPOR ABOVE TAR STORAGE TANK, CANISTER RINSE:
LC CUT #6 IR
SAMPLE: 3XR-LC6
1. Major peaks and assignments
v (cm )
3215 w
3055 W
2959, 2432, 2856 S
1739 S
1602 M
1465, 1383 M
1267, 1 M
1178, 1143, 1130 W
1025
M
746
2. Unassigned weak bands: 1026, 965, 835, 761, 698.
3. Other remarks:
A slight amount of aromatic character.
Assignments/Comments
alcoholic or phenolic OH
aromatic CH stretch
aliphatic CH stretch
ester or aliphatic ketone
aromatic C-L^-C
aliphatic CH bend
ester of aromatic acid or
aliphatic or aromatic ethers
substituted aromatic CH bend
A-120
-------
TABLE A-107. VAPOR ABOVE TAR STORAGE TANK, CANISTER RINSE:
LC CUT #7 IR
SAMPLE: 3XR-LC7
1. Major peaks and assignments
2.
3.
v (cm )
3600-3200
2959, 2932, 2856
1740
1459, 1376
1259, 1164, 1075
746
W (broad)
S
S
M,W
M
W
Unassigned weak bands: 1671, 1602, 1561, 1034, 671 cm
Other remarks:
Probable alcohols and saturated esters.
Assignments/Comments
alcoholic or phenolic OH
aliphatic CH stretch
ester or aliphatic ketone
aliphatic CH bend
ester of aromatic acid,
ether, alcohol, phenol
substituted aromatic CH
bend
-1
A-121
-------
TABLE A-108. SASS TRAIN DATA SHEET
Plant Name: U.S. Steel
Location: Birmingham, Alabama
Date: 12/14/77
Test Performed By: F. J. Phoenix, E. E. Stevenson
Run Number: 4
Sampling Location: Tar Decanter Tank 0
Pre Leak Test: 0.00
Post Leak Test: 0.02
Test Time:
Start: 9:00
Finish: 10:40
Meter Volume (c.f.):
Start: 893.59
Finish: 1191.67
Volume of Gas Sampled: 298.08 c.f.
287.41 scf.
Average Gas Temperature (°F)
Ambient: 61°
Sampling Location: 170°
XAD-2 Resin: 100°
Meter Box: 80°
Comments:
1. Used ice bath at sampling location to cool gases before passing
through XAD-2 Resin.
2. Ran for ~ 3-4 minutes when reaction took place in first impinger
Ammonia reacted with hydrogen peroxide - We decided to continue
test without first impinger.
3. Sampling performed in one of 4 vents. Tank was leaking vapor in
front.
A-122
-------
TABLE A-109. TAR DECANTER TANK
Sample Name:
Sample Date:
Analysis Date:
Tar Decanter Tank
12/14/77
12/14/77
C1-Cy HYDROCARBONS
Bulb #1
Range
GC 1
2
3
4
5
6
7
Range
GC 1
2
3
4
5
6
7
# Peaks
1
1
4
1
5
3
1
Bulb #2
# Peaks
1
1
4
1
5
4
1
ppm
(V/V)
3643
880
260
0.1
14.1
31.5
79
ppm
(V/V)
3640
879
257
0.1
14
144
97
AROMATIC (ppm, V/V) .
On-Site RTI
Bulb 1 Bulb 2 SS Can
Benzene 2190.7 2139.1 2395.6
Toluene 191.5 177.9 214.7
Ethyl Benzene NA NA 1.4
m & p Xylene NA NA 33.3
o Xylene NA NA 7.4
SULFURS (ppm, V/V)
On-Site
Bulb 1 Bulb 2
H2S (COS) 3792 4571
so2 — —
cs« —
NA = No Analysis
— = Compound Not Detected
A-123
-------
TABLE A-110. ORGANIC EXTRACT SUMMARY, TAR DECANTER VAPOR, XAD-2 RESIN
Preliminary
Total organics mg/sm3 6,340
TCO, mg 31,520
GRAV, mg 20,080
Category
Aliphatic hydrocarbons
Halogenated aliphatics
Aromatic hydrocarbons
Halogenated aromatics
Heterocyclic N,0,S
compounds
Sulfides, disulfides
Nitriles
Ethers
Aldehydes, ketones
Nitroaromatics
Alcohols
Amines
Phenols, halo and nitrophenols
Esters, amides
Mercaptans
Carboxylic acids
Sulfoxides
Concentrate LCI LC2 LC3 LC4 LC5 LC6
6,820 23.1 1,470 1,370 74 9.2 129
33,680 0.0 11,025 11,175 600 75 600
21,840 188 900 0.0 0.0 0.0 450
MATE comparison value, mg/sm3*
23.1 11.0
2.3
11.0 55.2
11.0
11.0 55.2
55.2
23.1 11.0 55.2
LC7 £
0.0 3,080
0.0 23,475
0.0 1,540
133
2.3
165
11
0.0
0.0
0.0
165
55.2
0.0
0.0
0.0
0.0
188
0.0
0.0
0.0
NOTE: The MATE Comparison Value is based on the GRAV mass in the LC cut divided by the gas sample volume. For com-
pound classes indicated by IR, the MATE comparison value is 100 percent of the GRAV concentration. For compound
classes expected65 but not identified by IR, the MATE Comparison Value is 10 percent of the GRAV concentration.
-------
TABLE A-111. TAR DECANTER VAPOR, XAD-2 RESIN:
PRELIMINARY IR
SAMPLE: 4X-P
1. Major peaks and assignments
v (cm )
3068, 3056
2966, 2931, 2856
1671, 1958, 1924,
1842, 1787, 1739
1595, 1390
1273-1006
958
780, 739
M
W
W
M
W
M
S,M
Assignments /Comments
aromatic or olefim'c CH
aliphatic CH
aromati c combi nati ons/overtones
or
aromatic or olefinic
monosub. naphthalene
aromatic fingerprint region
aromatic or olefinic CH bend
substituted aromatic CH bend
2294, 1821, 1622, 828, 615
Unassigned weak bands:
Other remarks:
Sample predominantly unsaturated and aromatic hydrocarbons. IR spectrum
suggests that aromatic hydrocarbons are predominantly a- and 3-substituted
naphthalenes.
A-125
-------
TABLE A-112. TAR DECANTER VAPOR, XAD-2 RESIN:
CONCENTRATE IR
SAMPLE: 4X-C
1. Major peaks and assignments
v (cm )
2.
3.
3088, 3071, 3054,
3007
2967-2863
1948-1624
1595, 1387
1271-1010
958
779, 739, 698
Unassigned weak bands:
W,M,S,W
W
W
M
Assignments/Comments
aromatic or olefinic CH
aliphatic CH
aromatic overtones/combina-
tions
condensed aromatic, a-sub.
naphthyl, or conj. vinyl
ft « « * f*
W aromatic fingerprint region
M conj. olefinic or aromatic CH
S,M,W substituted aromatic cmpds.
2290, 1508, 1427, 831, 617.
Other remarks:
Sample predominantly naphthalene, substituted aromatic cmpds, and un-
saturated hydrocarbons with some aliphatic groups present.
A-126
-------
TABLE A-113. TAR DECANTER VAPOR, XAD-2 RESIN:
LC CUT #1 IR
SAMPLE: 4X-LC1
1. Major peaks and assignments
v (cm )
2959, 2930, 2859 S
1739 W
1005 W
1457, 1381 M,W
2.
3.
Unassigned weak bands: 1686, 1645, 668 cm
Assignments/Comments
aliphatic CH stretch
ester or aliphatic ketone
aliphatic ester
aliphatic CH bend
-1
Other remarks:
This sample possessed less mass than that required by the Level 1
criteria for IR analysis. A spectrum of acceptable quality was obtained by
using Fourier Transform IR techniques.
Sample predominantly saturated hydrocarbons with a trace of aliphatic
ketones and/or saturated esters.
A-127
-------
TABLE A-114. TAR DECANTER VAPOR, XAD-2 RESIN:
LC CUT #2 IR
SAMPLE: 4X-LC2
1. Major peaks and assignments
v (cm"1) I_
2959, 2930, 2854 S
1744 u
1603 VI
1462, 1380 M,W
1034 W
746 W
Assignments/Comments
aliphatic CH stretch
ester
aromatic C-1^
aliphatic CH bend
aliphatic ester or ether
substituted aromatic CH bend
-1
2. Unassigned weak bands: 1675, 1151, 816 cm
3. Other remarks:
This sample possessed less mass than that required by the Level 1
criteria for IR analysis. A spectrum of acceptable quality was obtained by
using Fourier Transform IR.techniques.
Sample predominantly aliphatic hydrocarbons, esters and/or ethers.
Bands at 1603 and 746 cm~ suggest aromatic cmpds are predominantly mono-
substituted benzene.
A-128
-------
TABLE A-115. TAR DECANTER VAPOR, XAD-2 RESIN:
LC CUT #3 IR
SAMPLE: 4X-LC3
1. Major peaks and assignments
v (cm"1) I
3072, 3052, 3030 W
2927, 2860 W
1449 W
1261-1040 W
886, 869 W ^
818 M >
732 S '
2. Unassigned weak bands: 1398, 1301,
3. Other remarks:
Assignments/Comments
aromatic CH stretch
aliphatic CH stretch
aliphatic CH bend
aromatic fingerprint region
substituted aromatic CH bend
954 cm"1.
Sample predominantly aromatic hydrocarbons and alkylated derivatives;
e.g., a- and 3-substituted naphthalenes.
A-129
-------
TABLE A-116. TAR DECANTER VAPOR, XAD-2 RESIN:
LC CUT #4 IR
SAMPLE: 4X-LC4
1. Major peaks and assignments
v (cm" )
3.
3421, 3395
2955, 2921, 2854
1723
1462, 1450, 1380
1263
1098, 1086, 1034
805, 749, 725
Unassigned weak bands:
M,W
S
W
W,M,W
W
W
W,M,S
1336, 1327, 1239, 1207.
Assignments/Comments
1° amine, pyrrole or indole N-H
aliphatic CH stretch
ketone or ester
aliphatic CH bend
ester of aromatic acid
aliphatic C-N, aromatic ester,
aromatic or aliphatic ethers
sub. aromatics CH bend
Other remarks:
This sample possessed less mass than that required by the Level 1
criteria for IR analysis. A spectrum of acceptable quality was obtained by
Fourier Transform IR techniques.
Sample predominantly aromatic and aliphatic hydrocarbons with some
aromatic and aliphatic esters and ethers and some 1° amino-cmpds or deri-
vatives of pyrrole and/or indole.
A-130
-------
TABLE A-117. TAR DECANTER VAPOR, XAD-2 RESIN:
LC CUT #5 IR
SAMPLE: 4X-LC5
1. Major peaks and assignments
2.
3.
v (cm)
2959, 2930, 2854
1728
1462, 1380
1280
S
W
W
W
Assignments/Comments
aliphatic CH
ketone or ester.
aliphatic CH
acetate, sat. ester
Unassigned weak bands: 1034, 740, 670.
Other remarks:
This sample possessed less mass than that required by the Level 1
criteria for IR analyais. A spectrum of acceptable quality was obtained
by Fourier Transform IR techniques.
Sample appears to contain only saturated hydrocarbons and saturated
esters.
A-131
-------
TABLE A-118. TAR DECANTER VAPOR, XAD-2 RESIN:
LC CUT #6 IR
SAMPLE: 4X-LC6
1. Major peaks and assignments
v (cm )
2953, 2930, 2859
1720
1609
1462, 1374
1245, 1110
1028, 1010
752
S
M
M
M,W
VJ
W
W
2. Unassigned weak bands: 1674, 1292 cm"1,
Assignments/Comments
aliphatic CH stretch
ketone or ester
aromatic or conj. olefinic
aliphatic CH bend
ester of aromatic acid,
or aliphatic and/or aromatic
ethers
aromatic fingerprint region
sub. aromatic CH bend
3. Other remarks:
Sample predominantly aliphatic esters of aromatic acids; i.e., benzoates,
phthalates, etc.
A-132
-------
TABLE A-119. TAR DECANTER VAPOR, XAD-2 RESIN:
LC CUT #7 IR
SAMPLE: 4X-7
Major peaks and assignments
I
v
(cm"1)
2959, 2929, 2859
1744
1668, 1603, 1556
1462, 1380
1169, 1110
1075, 1034
722, 828
S
M
M
M
W,M
W
W
Assignments/Comments
aliphatic CH stretch
ester or aliphatic ketone
aromatic or olefinic C-^^-C
aliphatic CH bend
aliphatic ester or ether
aromatic fingerprint
substituted aromatic CH bend
Unassigned weak bands: 1415 cm
-1
Other remarks:
IR spectrum suggests that sample predominantly aromatic or aliphatic
esters of saturated carboxylic acids and aliphatic ethers.
A-133
-------
TABLE A-120. ORGANIC EXTRACT SUMMARY, TAR DECANTER VAPOR, CANISTER RINSE
3>
M
Co
Preliminary
Total organics mg/sm3 1,220
TCO, mg 8,190
GRAV, mg 1,760
Category
Aliphatic hydrocarbons
Halogenated aliphatics
Aromatic hydrocarbons
Halogenated aromatics
Heterocyclic N,0,S
compounds
Sulfides, disulfides
Nitriles
Ethers
Aldehydes, ketones
Nitroaromatics
Alcohols
Amines
Phenols, halo and nitrophenols
Esters, amides
Mercaptans
Carboxylic acids
Sulfoxides
Concentrate LCI
800 7.
0.
6,500 62.
68
0
5
LC2 LC3
972 10.
5,520 62.
2,390 25.
7
3
0
MATE comparison
7.
0.
7.
7.
7.
7.
68
77
68
68
68
68
294 3.
29.4 0.
3.
3.
3.
07
31
07
07
07
LC4
1.
0.
12.
54
0
5
value,
1.
0.
0.
0.
0.
1.
1.
1.
54
15
15
15
15
54
54
54
LC5
4.61
0.0
37.5
mg/sm3*
4.61
0.46
0.46
0.46
4.6
4.6
0.46
0.46
0.46
4.6
LC6
40.
31.
12.
1.
1.
1.
0.
0.
0.
0.
1.
0.
0.
0.
7
9
5
54
54
54
15
15
15
15
54
15
15
15
LC7
3.07
0.0
25.0
3.07
3.07
3.07
0.31
0.31
0.31
3.07
0.31
0.31
0.31
£
1,040
5,900
2,565
7.68
0.77
308
29.9
0.61
0.61
0.61
18.4
21.5
0.61
0.92
3.99
0.46
21.5
0.46
0.46
0.46
NOTE: The MATE Comparison Value is based on the GRAV mass in the LC cut divided by the gas sample volume. For com-
pound classes indicated by IR, the MATE comparison value is 100 percent of the GRAV concentration. For compound
classes expected65 but not identified by IR, the MATE Comparison Value is 10 percent of the GRAV concentration.
-------
TABLE A-121. TAR DECANTER VAPOR, CANISTER RINSE:
PRELIMINARY IR
SAMPLE: 4XR-P
1. Major peaks and assignments
v (cm )
3058
2964-2852
1601
1495
1447
1265-1023
952-864
816
781
734
2. Unassigned weak
3. Other remarks:
2340 & 2370 cm"1
Probable aromati
I
M
W
M
M
S
M
M
II
bands: 2339,
due to COp.
c hydrocarbons
Assignments/Comments
aromatic CH stretch
aliphatic CH stretch
conj. DBL-bond, nitroso, aromatic
aromatic, nitroso
aliphatic CH bend
aromatic or vinyl ether, ketal
or acetal , C-N stretching, C-0
stretching, alkane
epoxy, N-H bending
aromatic CH bend
1689-2079 cm"1.
and some aromatic ethers.
A-135
-------
TABLE A-122.
TAR DECANTER VAPOR, CANISTER RINSE:
CONCENTRATE IR
SAMPLE: 4XR-C
Major peaks and assignments
v
(cm"1)
3090, 3050
2980-2880
1950-1650
1595, 1509
1455
1390, 1360
1270-960
835-700
I
S(broad)
W
W
s
W
W
s
S(broad)
Assignments/Comments
aromatic CH stretch
aliphatic CH stretch
aromatic overtones/
combinations
aromatic C^-^-C stretch
aliphatic CH bend
gem-dimethyl CH bend
aromatic fingerprint region
substituted aromatic CH bend
Unassigned weak bands: 1425, 1320, 865 cm
3. Other remarks:
-1
Bands at 1390, 1360,
Sample predominantly substituted hydrocarbons.
865 cm" . Strongly suggest that sample contains significant amounts of ct-
and 3- i-pr and t-bu naphthalenes.
A-136
-------
TABLE A-123. TAR DECANTER VAPOR, CANISTER RINSE:
LC CUT #1 IR
SAMPLE: 4XR-LC1
1.
2.
3.
Major peaks and
v (cm)
2959, 2925, 2856
1733
1465
1376
1123 & 1068
719
Unassigned weak
Other remarks:
assignments
S
W
M
W
W
W
I Assignments/Comments
aliphatic CH
ester, or aliphatic ketone
aliphatic CH
aliphatic CH
ester or aliphatic ether
-(CHp)" rocking for _> 4
bands: 1274 cm"1.
Bands at 1733 cm"1 and 1123
trace amounts of esters. Sample
and 1068 cm. Suggests the presence of
predominantly saturated hydrocarbons.
A-137
-------
TABLE A-124. TAR DECANTER VAPOR, CANISTER RINSE:
LC CUT #2 IR
SAMPLE:
1. Major
4XR-LC2
peaks and assignments
v (cm )
3071, 3053 M
2000-1600 W
1507 M
1392 M
1200-1000 M
957 M
828 M
781 S
740 S
I Assignments/Comments
aromatic or olefinic
-CH
aromatic combinations/over-
tones
aromatic C-^^C
a-naphthalenes C-^-1-^
aromatic fingerprint
olefinic C-H (trans)
substituted aromatic
carbons
region
hydro-
2.
3.
Unassigned weak bands: 1456, 1445, 1427, 1245, 699, 617 cm"
Other remarks:
Sample contained virtually no aliphatic hydrocarbons, but appeared to
consist almost entirely of aromatic hydrocarbons. Bands at 781 and 740 cm"
highly suggestive of a-naphthalenes, i.e., 3 adjacent hydrogens on a ring
or monosubstituted benzene.
A-138
-------
TABLE A-125. TAR DECANTER VAPOR, CANISTER RINSE:
LC CUT #3 IR
SAMPLE: 4XR-U3
1. Major peaks and assignments
v (cm" )
3425
3055
2966, 2925, 2856
1718
1452
1260-1027
M
VI
M
W
S
W-M
M,S,S
1424, 1335, 993, 931, 890 cm
Assignments/Comments
aliphatic 2° amine
aromatic or olefinic CH stretch
aliphatic CH stretch
ketone or ester
aliphatic CH bend
C-N stretching of aromatic and
aliphatic amine
substituted aromatic CH bend
-1
801, 746, 725, 698
Unassigned weak bands:
Other remarks:
This sample possessed less mass than that required by the Level 1
criteria for IR analysis. A spectrum of acceptable quality was obtained
by using Fourier Transform IR techniques.
The sample seemed to contain predominantly aliphatic 2° amines. The
lack of a medium-to-strong band in the region 1650-1580 cnf arising from
1° amine NH wagging supports the idea that aliphatic 2° amines are pre-
dominant. Strong bands in region 890-700 cnf suggests appreciable amounts
of aromatic hydrocarbons.
A-139
-------
TABLE A-126. TAR DECANTER VAPOR, CANISTER RINSE:
LC CUT #4 IR
SAMPLE: 4XR-LC4
1. Major peaks and assignments
v (cm"1)
2595, 2932, 2877, 2963
733
1459, 1383
1280, 1274
1123, 1075
739
M
S
M
S
S
M
Assignments/Comments
aliphatic CH stretch
ester or aliphatic ketone
aliphatic CH bend
aromatic ether or ester of
aromatic acid
aliphatic or aromatic ether
or ester of aromatic acid
substituted aromatic CH bend
2. Unassigned weak bands: 1041, 965, 831, 671.
3. Other remarks:
This sample possessed less mass than that required by the Level 1
criteria for IR analysis, A spectrum of acceptable quality was obtained
by using Fourier Transform IR techniques.
3398 due to uneven sample.
671 & 739 may be due to MeCl2.
Probable aliphatic esters of aromatic acids and alkylated aromatic
hydrocarbons.
A-140
-------
TABLE A-127. TAR DECANTER VAPOR, CANISTER RINSE:
LC CUT #5 IR
SAMPLE: 4XR-LC5
1. Major peaks and assignments
2.
3.
v (cm" )
3078
2963, 2933, 2878, 2866
1732
1599, 1581
1465, 1380
1280
1126, 1071
744, 701
Unassigned weak bands:
W
S
S
W
M,W
S
M.W
1041, 956, 762 and 653 cm
Assignments/Comments
aromatic or olefinic CH
aliphatic CH
ester or aliphatic ketone
aromatic or olefinic C—C
aliphatic CH bend
ester of aromatic acid or
aromatic ether
ester of aromatic acid, ali-
phatic or aromatic ether
substituted aromatic CH bend
-1
Other remarks:
Sample predominantly aliphatic esters, ethers and/or saturated hydro-
carbons, but does contain some aromatic compounds; possibly esters of aro-
matic acids.
A-141
-------
TABLE A-128. TAR DECANTER VAPOR, CANISTER RINSE:
LC CUT #6 IR
SAMPLE: 4XR-LC6
1. Major peaks and assignments
v (cm" )
2.
3.
3062
2966, 2932, 2856
1740
1609, 1596
1465
1130, 1074, 1027
835
780, 753
W
S
S
M
M
W
W
Assignments/Comments
aromatic or olefinic CH
aliphatic CH
ester, or aliphatic ketone
aromatic or olefinic C=C
stretch
aliphatic CH bend or aro-
matic C-^-H: stretch
aromatic C-^^-C stretch,
aliphatic ether or ester
)I rocking or sub-
stituted aromatic
substituted aromatic CH bend
-1
-1
Unassigned weak bands: 3302, 1643, 1513 cm"
Other remarks:
- Splitting pattern about 750 cnf'L suggests a monosubstituted aromatic
compounds are predominant.
- Carbonyl group most likely a keto group due to absence of strong
absorption bands @ 1300-1050 cm which accompany an ester.
Sample predominantly aliphatic ketones and alkylated aromatic hydro-
carbons.
A-142
-------
TABLE A-129. TAR DECANTER VAPOR, CANISTER RINSE:
LC CUT #7 IR
SAMPLE: 4XR-LC7
1. Major peaks and assignments
2.
3.
v (cm" )
3076
2959, 2932, 2856
1240
2082, 1002
1465, 1376
1247, 1239
I
W
S
S
w
w
S
M
Assignments/Comments
aromatic CH
aliphatic CH
ester or aliphatic ketone
cyanide
aliphatic CH bend
ester of aromatic acid, or aromatic
ether
ester of aromatic acid, or aromatic
or aliphatic ether
substituted aromatic CH bend
1212, 1123, 1026
746, 615 W
Unassigned weak bands: 1582, 1438, 1081, 965, 835, 780, 698.
Other remarks:
746, 615, 698 possibly due to MeCl2.
Sample predominantly aliphatic esters of aromatic acids.
A-143
-------
TABLE A-130. ORGANIC EXTRACT SUMMARY, TAR DECANTER VAPOR, CONDENSATE EXTRACT pH 2
Preliminary
Total organics mg/sm3 207
TCO, mg 1,545
GRAV, mg 138
Category
Aliphatic hydrocarbons
Halogenated aliphatics
Aromatic hydrocarbons
Halogenated aromatics
Heterocyclic N,0,S
compounds
Sulfides, disulfides
Nitriles
Ethers
Aldehydes, ketones
Nitroaromatics
Alcohols
Ami nes
Phenols, halo and nitrophenols
Esters, amides
Mercaptans
Carboxylic acids
Sulfoxides
Concentrate LCI LC2 LC3 LC4
176 0.61 20.6 19.4 5.65
923 0.0 108 74 38
507 5.0 60 84 8.0
MATE comparison value,
0.61
0.06
7.37 10.3 0.98 „
0.74 1.03 0.10
0.10
0.10
0.10
0.10
0.98
0.98
0.98
0.98
LC5
7.12
42
16
mg/sm3*
1.96
0.20
0.20
0.20
0.20
0.20
1.96
0.20
1.96
0.20
1.96
1.96
LC6
96.8
596
192
23.6
2.36
2.36
2.36
2.36
23.6
2.36
2.36
23.6
2.36
LC7 Z
0.0 150
0.0 858
0.0 365
0.61
0.06
44.2
2.07
0.30
0.30
0.30
0.30
5.3
2.56
5.3
2.56
5.3
5.3
2.36
23.6
2.36
NOTE: The MATE Comparison Value is based on the GRAV mass in the LC cut divided by the gas sample volume. For com-
pound classes indicated by IR, the MATE comparison value is 100 percent of the GRAV concentration. For compound
classes expected65 but not identified by IR, the MATE Comparison Value is 10 percent of the GRAV concentration.
-------
TABLE A-131. TAR DECANTER VAPOR, CONDENSATE EXTRACT pH 2:
PRELIMINARY IR
SAMPLE: 11A-P
1. Major peaks and assignments
v (cm" )
3300 - 2500 M
3058 M
2924, 2856 W
1691 M
1594, 1502 M
1453, 1380 W
1246 " M
886, 813, 782
740, 691 W-S-W
Assignments/Comments
broad 0-H stretch of car-
boxy! ic acid, alcohol or
phenol
aromatic CH stretch
aliphatic CH stretch
carboxylic acid dimer-asym.
-CO-0 stretch, aromatic or
conj. acid
aromatic or olefinic C-1-^
aliphatic CH bend
C-0 stretch of carboxylic
acid or phenol
substituted aromatic com-
pounds
~ L
2. Unassigned weak bands: 1929, 953, 867 cm
3. Other remarks:
1191 - 1039 cm aromatic fingerprint region.
Sample predominantly aromatic acids and phenolic derivatives.
A-145
-------
TABLE A-132. TAR DECANTER VAPOR, CONDENSATE EXTRACT pH 2:
CONCENTRATE IR
SAMPLE: 11A-C
1. Major peaks and assignments
v
(cm"1)
Assignments/Comments
alcoholic or phenolic free
OH
alcoholic or phenolic OH
H-bonded
aromatic or conj. olefinic
CH stretch
aliphatic CH stretch
aromatic C-^-C
aliphatic CH bend
aromatic fingerprint region
alcoholic or phenolic C-0
alcoholic or phenolic OH
bend, substituted aromatic
CH bend
2. Unassigned weak bands: 1410, 1345, 1315, 1120, 1035, 1000, 930 cm"1.
3. Other remarks:
Sample appears to contain predominantly alcohols and alkylated phenols.
Broad, unresolved band at 1595 cm strongly suggest that considerable phenolic
compounds are present.
3590, 3475
3500 - 2800
3060-3040, 3005
2975, 2960, 2880
1620, 1595, 1510, 1500
1455, 1375
1285-1200
1150
830-750
(2 broad bands)
M,S
M
M,S
S,W
M-W
S
broad
A-146
-------
TABLE A-133. TAR DECANTER VAPOR, CONDENSATE EXTRACT pH 2:
LC CUT #1 IR
SAMPLE: 11A-LC1
1. Major peaks and assignments
v (cm ) l_ Assignments/Comments
2959 S aliphatic CH stretch
2925, 2856 S aliphatic CH stretch
1465 M aliphatic CH bend
2. Unassigned weak bands: 1376, 1274.
3. Other remarks:
2340 and 2370 cm"1 due to C02-
Only saturated hydrocarbons.
TABLE A-134. TAR DECANTER VAPOR, CONDENSATE EXTRACT pH 2:
LC CUT #2 IR
SAMPLE: 11A-LC2
1. Major peaks and assignments
v (cm" ) I_ Assignments/Comments
3044 W aromatic CH stretch
2960-2900 W aliphatic CH stretch
1602 W aromatic C^-^C
1445 W aliphatic CH bend
815, 732 S substituted aromatic CH
bend
2. Unassigned weak bands: 1623, 1026, 951, 890, 712 cm"1.
3. Other remarks:
Sample predominantly aromatic.
A-147
-------
TABLE A-135. TAR DECANTER VAPOR, CONDENSATE EXTRACT pH 2:
LC CUT #3 IR
SAMPLE: 11A-LC3
1. Major peaks and assignments
2.
3.
v
(cm"1)
3048
2952 - 2850
1925 - 1602
1445
1246 - 951
814, 732
W
VI
VI
M
W
S
Assignments/Comments
aromatic or olefinic CH
stretch
aliphatic CH stretch
aromatic combination/over-
tone
aromatic or olefinic
fingerprint region-aromatic
substituted aromatic C-H
bend
1396, 1301, 883, 869, 712 and 698 cm
-1 •
Unassigned weak bands:
Other remarks:
Sample contained only traces of saturated hydrocarbons - almost entirely
aromatic and/or unsaturated hydrocarbons.
A-148
-------
TABLE A-136. TAR DECANTER VAPOR, COMPENSATE EXTRACT pH 2:
LC CUT #4 IR
SAMPLE: 11A-LC4
1. Major peaks and assignments
v (cm"1) I_
3423 S
3047 W
2924, 2854 M
1703 W
1603, 1497 M,W
1450 S
1239, 1886, 1010 M,W,M
822, 775, 746, 722,
698
Assignments/Comments
alcoholic or phenolic OH,
H-bonded
aromatic or olefinic CH
stretch
aliphatic CH stretch
ketone, ester
aromatic C-^-C
aliphatic CH bend
alcohol, phenol, ester
of aromatic acid
M,S,S,S,W substituted aromatic CH
2. Unassigned weak bands: 1656, 1627, 1339, 1263, 1203, 928 .
3. Other remarks:
Sample contains predominantly phenolic compounds, and some aliphatic
esters of aromatic acids.
This sample possessed less mass than that required by the Level 1
criteria for IR analysis. A spectrum of acceptable quality was obtained
by using Fourier Transform IR techniques.
A-149
-------
TABLE A-137.
TAR DECANTER VAPOR, CONDENSATE EXTRACT pH 2:
LC CUT #5 IR
SAMPLE: 11A-LC5
1. Major peaks and assignments
v (cm"1)
2.
3.
3425
3055
2959, 2931, 2863
1726
1452
1280, 1133
1075, 1006
746, 725
Unassigned weak bands:
Other remarks:
Probable alkylated phenols,
alcohols.
1 Assignments/Comments
S phenolic or alcoholic OH
W aromatic or olefinic CH
S aliphatic CH
S ketone or ester
S aliphatic CH bend
S,M phenol, alcohol, ester or ether
M phenol, alcohol, ester or ether
S substituted aromatic CH (sugges-
tive of monosubstituted benzene-
phenol?)
diaphatic esters of aromatic acids, ethers,
A-150
-------
TABLE A-138. TAR DECANTER VAPOR, CONDENSATE EXTRACT pH 2:
LC CUT #6 IR
SAMPLE: 11A-LC6
1. Major peaks and assignments
v (cm)
3300-2500
2959, 2931, 2863
1596, 1506
1465, 1376
1376
1246
1000-1200
691-807
S
S
S,M
M
S
W-M
M-S
Assignments/Comments
carboxylic acid or phenolic
derivatives
aliphatic CH stretch
Qj_i_i£ ring stretches
aliphatic CH bend
phenolic OH bend
phenolic C-0 stretch
aromatic fingerprint region
substituted aromatic CH
-1
2. Unassigned weak bands: 1924, 1623, 1314, 951, 931, and 623 cm
3. Other remarks:
Probable alkylated phenols.
A-151
-------
TABLE A-139. TAR DECANTER VAPOR, CONDENSATE EXTRACT pH 2:
LC CUT #7 IR
SAMPLE: 11A-LC7
1, Major peaks and assignments
v (cm"1)
1956, 2929, 2856
2064
1731, 1711
1597, 1484
1465
1278
1125, 1072
746
j_ Assignments/Comments
S aliphatic CH stretch
M isothiocyanate
S ketone, ester
S, M aromatic or conj. olefinic C-^^-H
M aliphatic CH bend
S ester, ether
W ester, ether
M alkene, substituted aromatic CH
bend
1551, 1451.
Unassigned weak bands:
Other remarks:
This sample possessed less mass than that required by Level 1
criteria for IR analysis. A spectrum of acceptable quality was obtained
by using Fourier Transform IR techniques.
Probable aliphatic esters of aromatic acids.
A-152
-------
TABLE A-140. ORGANIC EXTRACT SUMMARY, TAR DECANTER VAPOR, CONDENSATE EXTRACT, pH 12
01
co
Preliminary Concentrate
Total organics mg/sm3 59 45
TCO, mg 345 338
GRAV, mg 138 26
Category
Aliphatic hydrocarbons
Halogenated aliphatics
Aromatic hydrocarbons
Halogenated aromatics
Heterocyclic N,0,S
compounds
Sulfides, disulfides
Nitriles
Ethers
Aldehydes, ketones
Nitroaromatics
Alcohols
Amines
Phenols, halo and nitrophenols
Esters, amides
Mercaptans
Carboxylic acids
Sulf oxides
LCI LC2 LC3
0.46 0.80 0.61
0.0 6.5 3.0
3.75 0.0 2.0
' MATE comparison
0.46
0.05
0.24
0.02
0.24
0.24
0.24
LC4 LC5
0.43 2.27
3.5 15.5
0.0 3.0
value, mg/sm3*
° 0.37
0.04
0.04
0.04
0.04
0.37
0.04
0.04
0.37
0.37
LC6
26.8
208
10.0
1.23
1.23
0.12
0.12
0.12
1.23
0.12
1.23
0.12
0.12
0.12
LC7
0.12
0.0
1.0
0.12
0.12
0.12
0.01
0.01
0.01
0.12
0.01
0.01
0.01
E
31.5
236
16.8
0.46
0.05
1.96
0.02
0.04
0.04
0.04
1.63
0.85
0.16
0.17
1.61
0.13
1.96
0.13
0.13
0.13
NOTE: The MATE Comparison Value is based on the GRAV mass in the LC cut divided by the gas sample volume. For com-
pound classes indicated by IR, the MATE comparison value is 100 percent of the GRAV concentration. For compound
classes expected65 but not identified by IR, the MATE Comparison Value is 10 percent of the GRAV concentration.
-------
TABLE A-141. TAR DECANTER VAPOR, CONDENSATE EXTRACT pH 12:
PRELIMINARY IR
SAMPLE: 11B-P
1.
2.
3.
Major peaks and assignments
v (cm'1)
3500 - 3200
2954, 2930, 2859
1743, 1732
1701
1462, 1380
1262 - 1074
799, 740
Unassigned weak bands:
Other remarks:
Sample predominantly aliphatic
amides. May contain some esters of
I
W(broad)
S
M
W
M,W
W
W
ketones ,
aromatic
Assignments/Comments
amine or amide NH, H-bonded
aliphatic CH stretch
ester, or possibly aliphatic
ketone
amide I band of 1° amides,
ketone, ester
aliphatic CH bend
ami no C-N stretch, esters of
aromatic acids, aromatic and/
or aliphatic ethers
amine or amide NH bend, sub.
aromatic NH bend
and aryl alkyl amines and/or
acids.
A-154
-------
TABLE A-142.
TAR DECANTER VAPOR, COMPENSATE EXTRACT pH 12:
CONCENTRATE IR
SAMPLE: 11B-C
1. Major peaks and assignments
v (cm" )
3545, 3585
3500-3100
3050-3030, 3006
2980, 2920, 2865
2064
1720
1660, 1620, 1590, 1580
1455, 1375
1410
1265, 1255, 1155-1090
830-730
2.
3.
J_
S,W
(broad)
S
M,M,W
M
M
S,W
M
M
Assignments/Comments
alcoholic OH stretch
amines or amides NH stretch
aromatic CH stretch
aliphatic CH stretch
isothiocyanate (-N=C=S)
aliphatic ketones or esters
1° amines, amide I (-C=0)
and amide II (NH bend) bands,
or aromatic
Unassigned weak bands:
Other remarks:
aliphatic CH bend
1° amide C-N stretch
esters of aromatic acids,
C-N stretch of 1°, 2°, and/
or 3° amines and 2° amides
or alcoholic C-0
amines and 1° amide NH
wag or substituted aromatic
CH bend
i
2560, 2400, 1500, 1480, 1010, 840 cm
Sample appears to contain predominantly aryl and alkyl amines or amides.
-1
The broad unresolved peak about 1600 cm is typical of monosubstituted
benzene, suggesting the presence of aniline and N-alkylated derivatives.
A-155
-------
TABLE A-143. TAR DECANTER VAPOR, CONDENSATE EXTRACT pH 12:
LC CUT #1 IR
SAMPLE: 11B-LC1
1. Major peaks and assignments
v (cm ) l_ Assignments/Comments
2959 S aliphatic CH stretch
2925, 2856 S aliphatic CH stretch
1465 M aliphatic CH bend
2. Unassigned weak bands: 1739, 1376, 1287.
3. Other remarks:
2340 and 2370 <
Only saturated hydrocarbons present.
2340 and 2370 cm"1 due to C02-
A-156
-------
TABLE A-144. TAR DECANTER VAPOR, CONDENSATE EXTRACT pH 12:
LC CUT #2 IR
SAMPLE: 11B-LC2
1. Major peaks and assignments
v_
3053
2.
3.
(cm"1)
2951, 2931, 2846
1570, 1472
1450
872
810, 739, 692
Unassigned weak bands:
1014 cm
W
M,S,M
W,M
M
W
M,S,S
-1
Assignments/Comments
aromatic or olefinic CH
stretch
aliphatic CH stretch
aromatic C-1-^
aliphatic CH bend
isolated aromatic CH bend
substituted aromatic CH bend
Other remarks:
This sample possessed less mass than that required by the Level 1
criteria for IR analysis. A spectrum of acceptable quality was obtained
by using Fourier Transform IR techniques.
Sample contained saturated and unsaturated or aromatic hydrocarbons.
A-157
-------
TABLE A-145. TAR DECANTER VAPOR, COMPENSATE EXTRACT pH 12:
LC CUT #3 IR
SAMPLE: 11B-LC3
1. Major peaks and assignments
v (cm"1)
2.
3.
3056, 3044, 3017
2950, 2923, 2855
1730
1600, 1583, 1492, 1477
1462, 1459, 1442
1374, 1365
1263, 1092, 1064, 1025
822, 813, 799, 778, 737
J_
W
S
M
W,W,W,M
M
W
M-S
M,S,M,S
1201, 1177, 699 cm
Assignments/Comments
aromatic or olefinic CH
stretch
aliphatic CH stretch
aliphatic ketone or ester
aromatic C-^^-C stretch
aliphatic CH bend
methyl CH bend, possibly
gem-dimethyl
ester of aromatic acid or
aromatic or aliphatic ether
substituted aromatic isolated
H substituted aromatic CH
bend
-1
Unassigned weak bands:
Other remarks:
This sample possessed less mass than that required by the Level 1
criteria for IR analysis. A spectrum of acceptable quality was obtained by
Fourier Transform IR techniques.
Sample appears to contain predominantly aromatic compounds and ester
of aromatic acids or aryl ethers.
A-158
-------
TABLE A-146. TAR DECANTER VAPOR, CONDENSATE EXTRACT pH 12:
LC CUT #4 IR
SAMPLE: 11B-LC4
1. Major peaks and assignments
v (cm"1) I
3411 S
3062 W
2959, 2931, 2856 S
1718 M
1459 M
1280, 1239 M
1095, 1013 M
739 S
691 M
Assignments/Comments
2°amine or amide NH stretch
aromatic CH stretch
aliphatic CH stretch
ketone, formate or conjug-
ated ester or amide
aliphatic CH or amide C-N
amide or aryl alkyl ether
ester, ether
substituted benzene
substituted benzene
-1
2. Unassigned weak bands: 1342, 1123, 1075 and 808 cm
3. Other remarks:
IR spectrum suggests sample contains appreciable amounts of aromatic
and aliphatic 2° amines. Lack of strong absorption at 1718 cm suggests
that absorption at 3411 cm due to 2° amine not amide.
A-159
-------
TABLE A-147. TAR DECANTER VAPOR, CONDENSATE EXTRACT pH 12:
LC CUT #5 IR
SAMPLE: 11B-LC5
1. Major peaks and assignments
°v (cm"1)
3391
3055
2959, 2911, 2863
1726
1602, 1581
1465, 1388
1280, 1123
1075, 952
734, 691
2. Unassigned weak bands:
952, and 780 cm"1.
3. Other remarks:
Carboryl absorption too high for amide, and lack of doublet in region
3400 - 3100 cm leads to conclusion that compounds are secondary amino deri-
vatives. Sample contains aryl and alky! 2° amines and aryl and/or alky!
esters.
! Assignments/Comments
M 2° amine or 2° amide
W aromatic or olefinic CH
S aliphatic CH
S ketone or ester
W aromatic C-:-^:-C
M,W aliphatic CH, methyl CH bend
S,M aliphatic ester of aromatic
acid
M,W aromatic fingerprint region
S,W substituted benzene, probably
ortho-di substi tuted
1581 (probably-N-H bending), 1410, 1239,
A-160
-------
TABLE A-148. TAR DECANTER VAPOR, CONDENSATE EXTRACT pH 12:
LC CUT #6 IR
SAMPLE: 11B-LC6
1. Major peaks and assignments
v (cm" )
3329
3150, 3068
2954, 2931, 2863
2068
1725
1610, 1595, 1506
1459, 1390
1287-1246
944, 849, 807-691
1
M (broad)
S
W
M
S,M
S
W,W,M
Assignments/Comments
alcoholic OH or amide or
amine NH
aromatic or olefinic CH
stretch
aliphatic CH stretch
isothiocyanate or ketenimine
ester and/or aliphatic
ketone
aromatic C-^-C and/or amine
or amide NH bend
aliphatic CH bend
ester of aromatic acid, aryl
ether of C-N stretch of aryl
or alkyl amines
sharp bands in aromatic
fingerprint region, substi-
tuted aromatic CH bend
2. Unassigned weak bands: 2733, 2698, 2575, 1321 .
3. Other remarks:
Sample predominantly alkylated derivatives of aniline or polynuclear
aromatic amine, and saturated ketones. The lack of a broad band in region
1250-100 cm" corresponding to an ethereal or alcoholic C-0 stretch suggests
that the sharp, strong band in this region is likely due to C-N stretch of
amines.
A-161
-------
TABLE A-149. TAR DECANTER VAPOR, CONDENSATE EXTRACT pH 12:
LC CUT #7 IR
SAMPLE: 11B-LC7
1. Major peaks and assignments
2.
3.
(cm"1)
2954, 2931, 2856
2061
1732
1465
1240
1122, 1074
739
Unassigned weak bands:
Other remarks:
Probable aliphatic esters of aromatic acids.
S
M
S
M
S
w
M
1664.
1602.
Assi gnments/Comments
Aliphatic CH stretch
Isothiocyanate or ketenimine
Ester or aliphatic ketone
Aliphatic CH bend
Ester of aromatic acid, aromatic
ether
Ether, ester of aromatic acid
Aromatic
1581, 1383, 759, 691
A-162
-------
Sample Name:
Sample Date:
Analysis Date:
TABLE A-150. LIGHT OIL STORAGE TANK
Light Oil Storage Tank
12/14/77
12/14/77
CX-C7 HYDROCARBONS
Bulb #1
Range
# Peaks
ppm
(V/V)
AROMATIC
(Ppm, V/V)
On-Site
RTI
Bulb 1 Bulb 2 SS Can
GC
Range
GC
1
2
3
4
5
fa
7
1
2
3
4
5
fa
7
1
2
4
1
6
6
0
Bulb #2
# Peaks
1
2
4
1
6
6
1
20
35
25
1
15
25
—
ppm
(V/V)
20
34
25
1
17
17
0.1
Benzene 306.
Toluene NA
Ethyl Benzene NA
m & p Xylene NA
o Xylene NA
SULFURS
1 296.3
8.5
NA
NA
NA
(ppm, V/V).
358.3
10.6
—
—
—
On-Site
H2S (COS)
so2
cs2
NA = No Analysis
Bulb 1
22
—
5-10 ppm
Bulb 2
20
—
(estimate)
— = Compound Not Detected
A-163
-------
TABLE A-151. SASS TRAIN DATA SHEET
Plant Name: U.S. Steel
Location: Birmingham, Alabama
Date: 12/15/77
Test Performed By: F. H. Phoenix, E. E. Stevenson, T. Allen
Run Number: 5
Sampling Location: Chemical Oil Storage Tank
Pre Leak Test: 0.00
Post Leak Test: 0.08
Test Time:
Start: 8:41
Finish: 11:50
Meter Volume (c.f.):
Start: 361.52
Finish: 870.40
Volume of Gas Sampled: 505.48 c.f.*
503.86 scf.
Average Gas Temperature (°F)
Ambient: 50°
Sampling Location: 110°
XAD-2 Resin: 80°
Meter Box: 65°
Comments:
1. Naphthalene was condensing on inside of XAD-2 Module and probe.
* 3.40 cf subtracted due to leak test.
A-164
-------
TABLE A-152. CHEMICAL OIL STORAGE TANK
Sample Name:
Sample Date:
Analysis Date:
Crc7
Range
GC 1
2
3
4
5
6
7
Range
GC 1
2
3
4
5
6
7
Chemical Storage
12/15/77
12/15/77
HYDROCARBONS
Bulb #1
# Peaks
1
0
0
0
0
0
0
Bulb #2
# Peaks
1
0
0
0
0
0
0
ppm
(V/V)
2.8
—
—
—
—
• —
—
ppm
(V/V)
2.8
—
—
—
—
—
—
Tank
AROMATICS (ppm, V/V)
On-Site RTI
Bulb 1 Bulb 2 SS Can
Benzene 97.4 104.9 99.5
Toluene 68.5 69.0 70.5
Ethyl Benzene NA NA 5.3
m & p Xylene NA NA 40.0
o Xylene NA NA 10.8
SULFURS (ppm, V/V)
On-Site
Bulb 1 Bulb 2
H2S (COS) — —
^y — — — —
CS9 — —
L.
NA = No Analysis
— = Compound Not Detected
A-165
-------
TABLE A-153. ORGANIC EXTRACT SUMMARY, VAPOR ABOVE CHEMICAL OIL TANK, XAD-2 RESIN
01
Preliminary
Total organics mg/sm3 2,110
TCO, mg 26,730
GRAV, mg 3,360
Category
Aliphatic hydrocarbons
Halogenated aliphatics
Aromatic hydrocarbons
Halogenated aromatics
Heterocyclic N, 0, S
compounds
Sulfides, disulfides
Nitriles
Ethers
Aldehydes, ketones
Nitroaromatics
Alcohols
Amines
Phenols, halo and nitrophenols
Esters, amides
Mercaptans
Carboxylic acids
Sulfoxides
Concentrate LCI LC2 LC3
2,420 10.5 (36.8) 522 (543) 620 (641)
28,800 150 7,450 8,850
5,730 0.0 (375) 0.0 (300) 0.0 (300)
LC4
0.0
0.0
0.0
LC5
(21.0) 7.01
100
(300) 0.0
LC6
(21.0) 210 (238)
3,000
(200) 0.0 (200)
LC7
0.0
0.0
0.0
Y,
(21.0) 1,370 (1,520)
19,550
(300) 0.0 (2,175)
MATE comparison value, mg/sm3*
(26.3)
(2.63)
(21.0) (21.0)
(2.1) (2.10)
(21.0) (21.0)
(21.0)
(21.0)
(21.0)
(2.10)
(2.10)
(2.10)
(2.10)
(21.0)
(21.0)
(21.0)
(14.0)
(1.4)
(1.4)
(1.4)
(14.0)
(14.0)
(1.4)
(1.4)
(1-4)
(14.0)
(28.0)
(28.0)
(28.0)
(2.8)
(2.8)
(2.8)
(2.8)
(28.0)
(2.8)
(2.8)
(2.8)
(21.0)
(21.0)
(21.0)
(2.10)
(2.10)
(2.10)
(21.0)
(2.10)
(2.10)
(2.10)
0.0 (26.3)
0.0 (2.63)
0.0 (126)
0.0 (6.3)
0.0 (3.5)
0.0 (3.5)
0.0 (3.5)
0.0 (126)
0.0 (105)
0.0 (4.2)
0.0 (6.3)
0.0 (6.3)
0.0 (4.9)
0.0 (105)
0.0 (4.9)
0.0 (4.9)
0.0 (4.9)
NOTE: Values in parentheses are GRAV mass before subtraction of blank. The presence of GRAV mass in the original sample is shown by the Preliminary
and Concentrate samples. The MATE Comparison Value is based on the GRAV mass in the LC cut divided by the gas sample volume. For compound classes
indicated by IR, the MATE comparison value is 100 percent of the GRAV concentration. For compound classes expected65 but not identified by IR, the MATE
Comparison Value is 10 percent of the GRAV concentration.
-------
TABLE A-154. VAPOR ABOVE CHEMICAL OIL TANK, XAD-2 RESIN:
PRELIMINARY IR
SAMPLE: 5X-P
2.
3.
Major peaks and assignments
v
W,M,W
W
W
(cm"1)
3069, 3055, 3007
2959, 2932, 2856
1950, 1924, 1842
1732
1596, 1506
1390, 1363
M
M
Assignments/Comments
Aromatic CH stretch
Aliphatic CH stretch
Aromatic combinations/overtones
o
Aromatic C-^-C
Highly sub. aromatic or gemdimethyl CH
bend
Aromatic or aliphatic ethers
1274, 1173, 1123
958
841, 780, 648
Unassigned weak bands:
Other remarks:
Sample appears to contain predominant aromatic hydrocarbons and methylated
and/or other alkylated derivatives.
W
M
W,S,W Substituted aromatic CH Bend
1671, 1568, 1246, 1006, 616
A-167
-------
TABLE A-155. VAPOR ABOVE CHEMICAL OIL TANK, XAD-2 RESIN:
CONCENTRATE IR
SAMPLE:
1
5X-C
Major peaks and assignments
v (cm" ) I_
3068, 3051, 3004 W,M,W
2952-2850 W
1957-1671 W
1596, 1508 M,W
1392 M
961, 780, 746
Assignments/Comments
Aromatic or olefinic CH
Aliphatic CH stretch
Aromati c overtones/combi nations
Aromatic C^-^C
Highly substituted aromatics
Substituted aromatic cmpds
-1
M,S,M,M
2, Unassigned weak bands: 2298, 1270, 1124, 1008, 845, 816 cm"
3. Other remarks:
Sample comprised almost entirely of aromatic hydrocarbons with very few
saturated or oxygen-containing cmpds present.
TABLE A-156. VAPOR ABOVE CHEMICAL OIL TANK, XAD-2 RESIN:
LC CUT #1 IR
SAMPLE: 5X-LC1
1. Major peaks and assignments
2.
3.
v (cm"1)
S
M
W
1746.
2960, 2926, 2858
1462
1377
Unassigned weak bands:
Other remarks:
Sample contains predominantly saturated hydrocarbons.
Assi gnments/Comments
Aliphatic C-H stretch
Aliphatic CH Bend
Isolated methyl CH bend
1604.
A-168
-------
TABLE A-157.
VAPOR ABOVE CHEMICAL OIL TANK, XAD-2 RESIN:
LC CUT #2 IR
SAMPLE: 5X-LC2
1. Major peaks and assignments
v (cm"1) I
2959, 2926, 2856 M,S,M,
1462, 1452 W
1380 W
1262 S
1098, 1040 S
802 S
Unassigned weak bands: 863,
Assignments/Comments
Aliphatic CH stretch
Aliphatic CH bend
Methyl CH bend
Aromatic ether
Aromatic and/or aliphatic ether
Substituted aromatic CH bend
2.
3.
750, 701 cm
-1
Other remarks:
This sample possessed less mass than that required by the Level 1 criteria
for IR analysis. A spectrum of acceptable quality was obtained by using
Fourier Transform IR Techniques.
Sample predominantly aliphatic and aromatic ethers. Absorption bands in
CH out-of-plane bending region for aromatics suggests that para-substituted
benzene is predominant but some monosub. benzene is present.
A-169
-------
TABLE A-158.
VAPOR ABOVE CHEMICAL OIL TANK, XAD-2 RESIN:
LC CUT #3 IR
SAMPLE: 5X-LC3
1.
2.
3.
Major peaks and assignments
v(cnT )
2965, 2930, 2859
1738
1462, 1380
1263
1098, 1039
1
S
W
M,W
S
S
As s 1 gnments/ Commen ts
Aliphatic CH stretch
Ester or aliphatic ketone
Aliphatic CH bend
Aromatic ether or ester of aromatic acid
Aromatic and/or aliphatic ethers or
alkanes
W.S.W
1656, 670 cm
Substituted aromatic
-1
869, 805, 699
Unassigned weak bands:
Other remarks:
Sample seems to consist primarily of vinyl or aromatic ethers, and a small
amount of aromatic or aliphatic esters.
A-170
-------
TABLE A-159, VAPOR ABOVE CHEMICAL OIL TANK, XAD-2 RESIN:
LC CUT #4 IR
SAMPLE: 5X-LC4
1. Major peaks and assignments
v (cm" ) J_ Asslgnments/Comments
2960, 2920, 2850 S Aliphatic CH Stretch
1706 W Ketone or ester
1593 W Aromatic C^£
1460, 1375 W Aliphatic CH bend
1020 W Aliphatic ester or ether
726 W Substituted aromatic CH bend
2. Unassigned weak bands:
3. Other remarks:
This sample possessed less mass than that required by the Level 1 criteria
for IR analysis. A spectrum of acceptable quality was obtained by using Fourier
Transform IR techniques.
Sample appears to contain predominantly saturated hydrocarbons and a trace
amount of aromatic compounds.
A-171
-------
TABLE A-160, VAPOR ABOVE CHEMICAL OIL TANK, XAD-2 RESIN:
LC CUT #5 IR
SAMPLE: 5X-LC5
1. Major peaks and assignments
v (cm"1) I
2959, 2924, 2859
1726
1468, 1450
1380
1286, 1130
740
2. Unas signed weak bands:
S
M
M, W
W
M, W
W
1661,
Assignments/Conments
Aliphatic CH stretch
Ketone or ester
Aliphatic CH bend
Isolated methyl CH bend
Aliphatic or aromatic ester or ether
Substituted aromatic CH bend
1632, 1603, 1074 cm"1.
3. Other remarks:
Sample predominantly saturated hydrocarbons and aliphatic esters.
Bands
in region 1660-1600 and at 1074 and 740 cm"1 suggest presence of aromatic cmpds,
possibly alkylated derivatives or aromatic esters.
A-172
-------
TABLE A-161, VAPOR ABOVE CHEMICAL OIL TANK, XAD-2 RESIN:
LC CUT #6 IR
SAMPLE: 5X-LC6
1. Major peaks and assignments
2.
3,
v (cm" )
3063
2956, 2927, 2856
1727
1603, 1460
1454, 1380
1280, 1125
J_
W
S
s
M
M,W
M,W
Assignments/Comments
Aromatic or olefinic CH
Aliphatic CH stretch
Ketone or ester
Aromatic C-^-C
Aliphatic CH bend
Ester of aromatic acid or aromatic
and/or aliphatic ether
1040, 618 cm
748, 694 M,W
Unassigned weak bands: 1075.
Other remarks:
Sample predominantly aromatic esters of 1°
Substituted aromatic CH bend
-1
alcohols (i.e., benzoates, etc.)
A-173
-------
TABLE A-162. VAPOR ABOVE CHEMICAL OIL TANK, XAD-2 RESIN:
LC CUT #7 IR
SAMPLE: 5X-LC7
1. Major peaks and assignments
v (cm )
2964, 2962, 2859
1738
1562
1456
1286, 1268, 1122
! Assignments/Comments
S Aliphatic CH stretch
M Ester or aliphatic ketone
M Aromatic C2-^ stretch
M Aliphatic CH bend
W Esters of aromatic acids or
aromatic or aliphatic ethers
Substituted aromatic CH bend
2.
3.
740 W
Unassigned weak bands: 1074, 669 cm"1.
Other remarks:
This sample possessed less mass than that required by the Level 1 criteria
for IR analysis. A spectrum of acceptable quality was obtained by using
Fourier Transform IR techniques.
Sample predominantly saturated ethers or saturated ethers and/or esters
of aromatic acids.
A-174
-------
TABLE A-163. ORGANIC EXTRACT SUMMARY, VAPOR ABOVE CHEMICAL OIL TANK, CANISTER RINSE
Total
organics mg/sm3
TCO, mg
GRAV, mg
Preliminary
802
2,480
8,960
Concentrate
1,550
22,120
LCI
27
3,740
122
LC2
1,584
16,000
6,610
LC3
298
4,260
0.0
LC4
51.4
0.0
734
LC5
0.0
0.0
0,0
LC6
72.2
1,030
0.0
LC7
0.0
0.0
0.0
£
2,280
25,030
7,470
Category
MATE comparison value, mg/sm3*
M
-vj
en
Aliphatic hydrocarbons
Halogenated aliphatics
Aromatic hydrocarbons
Halogenated aromatics
Heterocyclic N, 0, S
compounds
Sulfides, disulfides
Nitriles
Ethers
Aldehydes, ketones
Nitroaromatics
Alcohols
Amines
Phenols, halo and nitrophenols
Esters, amides
Mercaptans
Carboxylic acids
Sulfoxides
8.54
0.85
463 51.4
46.3 5.14
5.14
5.14
5.14
8.54 51.4
8.54 51.4
8.54 51.4
8.54
0.85
514
51.4
5.14
5.14
5.14
59.9
59.9
59.9
NOTE: The MATE Comparison Value is based on the GRAV mass in the LC cut divided by the gas sample volume. For compound
classes indicated by IR, the MATE comparison value is 100 percent of the GRAV concentration. For compound classes
expected65 but not identified by IR, the MATE Comparison Value is 10 percent of the GRAV concentration.
-------
TABLE A-164,
VAPOR ABOVE CHEMICAL OIL TANK, CANISTER RINSE:
PRELIMINARY IR
SAMPLE: 5XR-P
1. Major peaks and assignments
v
2.
3.
(cm"1)
3085, 3045, 3010
2960, 2950, 2920
1950-1650
1595, 1500
1390, 1360
1270-960
840-770
725
Unassigned weak bands:
Other remarks:
S
W
W
S
s,w
S (sharp)
M (broad)
620 cm
-1
Assignments/Comments
Aromatic CH stretch
Aliphatic CH stretch
Aromatic overtones and combinations
Aliphatic C-^^C stretch
Gem-dimethyl CH bend Or highly
substituted aromatic cmpds
Aromatic fingerprint region
Substituted aromatic CH bend
Sample predominantly-aromatic hydrocarbons. Bands at 1390, 1360 and 840-
-1
770 cm x strongly suggest that alkylated derivatives are i-propyl or t-butyl
a- and 6-substituted naphthalenes.
A-176
-------
TABLE A-165. VAPOR ABOVE CHEMICAL OIL TANK, CANISTER RINSE:
CONCENTRATE IR
SAMPLE: 5XR-C
1. Major peaks and assignments
v (cm )
2.
3.
3090, 3060-3000
2980, 2960, 2870
1945-1665
1598, 1555, 1500
1450
1390, 1360
1270-960
825, 720
Unassigned weak bands
Other remarks:
1 Assignments/Comments
S Aromatic CH stretch
M,W Aliphatic CH stretch
M Aromatic overtones/combinations
S,W,S Aromatic C^-^C Stretch
W Aliphatic CH bend
S Gem-dimethyl or t-butyl CH
S (sharp) Aromatic fingerprint region
S,M Sub, aromatic CH bend
2290 cm"1 (nitrile?)
Sample contains primarily aromatic hydrocarbons and alkylated derivatives.
Bands at 1390, 1360, 825 and 720 cm"1 strongly suggest that these alkylated
derivatives are almost entirely i-propyl or t-butyl derivatives of a- and 3-
sub. naphtalenes.
1177
-------
TABLE A-166,
VAPOR ABOVE CHEMICAL OIL TANK, CANISTER RINSE:
LC CUT #1 IR
SAMPLE: 5XR-LC1
1.
-
Major peaks and assignments
v (cnf )
2959, 2925, 2856
1733
1457
1376
1123, 1075
739
1718, 1280, 1274
I
S
M
M
W
W
W
Assi gnments/Comments
Aliphatic CH
Ester or oliphatic ketone
Aliphatic CH
Methyl C-H
Ester or ether C-0
-(CHp) -» n>4 rocking or substitu-
ted aromatic
CH bend
2, Unassigned weak bands:
3. Other remarks:
1718, 1280, 1274
-1
Bands at 1733, 1123 and 1075 cm very likely due to esters that are present.
i
Bands at 1280, 1274 and 739 cm" possible due to aromatic ether.
Sample appears to consist predominantly of saturated hydrocarbons and/or
aliphatic esters or ketones.
A-178
-------
TABLE A-167. VAPOR ABOVE CHEMICAL OIL TANK, CANISTER RINSE:
LC CUT #2 IR
SAMPLE: 5XR-LC2
1. Major peaks and assignments
v (cm ) _!_ Assignments/Comments
3050 W Aromatic CH stretch
1956-1785 W Aromatic combination and overtone
region
1593, 1505 W Aromatic C^^C Stretch
842 W
-,on _ } Substituted aromatic CH bend
/oU o
2. Unasstgned weak bands: 1391, 1272, 1210, 1127, 1008 ,. and 961 cm"1
(Peak at 961 cm"1 is of medium intensity)
3. Other remarks:
Bands in region 1956-1785 cm and single bands at 842 and 780 cnf
highly suggestive of meta- or ortho-disubstituted benzene, i.e., 3 or 4
adjacent hydrogen atoms. Sample is primarily aromatic hydrocarbons, containing
few aliphatic hydrocarbons. This sample probably contains significant amounts
of naphthalene.
A-179
-------
TABLE A-168. VAPOR ABOVE CHEMICAL OIL TANK, CANISTER RINSE:
LC CUT #3 IR
SAMPLE: 5XR-LC3
1. Major peaks and assignments
v (cm ) _!_ Assignments/Comments
2959, 2952, 2856 S Aliphatic CH stretch
1733 S Esters or aliphatic ketones
1459, 1376 M,W Aliphatic CH bend
1274, 1123, 1075 M,W,W Aromatic ester of 1° and 2°
alcohols or aromatic or aliphatic
ethers
808, 746 W Substituted aromatic CH bend
2. Unassigned weak bands: 1541, 1034.
3. Other remarks:
This sample possessed less mass than that required by the Level 1 criteria
for IR analysis. A spectrum of acceptable quality was obtained by using Fourier
Transform IR techniques.
This sample appears to be predominantly aromatic esters of 1° and/or
2° alcohols.
A-180
-------
TABLE A-169. VAPOR ABOVE CHEMICAL OIL TANK, CANISTER RINSE:
LC CUT #4 IR
SAMPLE: 5XR-LC4
1. Major peaks and assignments
v (cm ) l_ Assi gnments/Comments
- 2962, 2931, 2874, 2861 S Aliphatic CH stretch
1733 S Ester or aliphatic ketone
1462, 1381 M Aliphatic CH bend
1292, 1273 S Aromatic ether or ester of aromatic
acid
1122, 1071 M Aromatic or aliphatic ether or
ester of aromatic acid
744, 700 M,M Substituted aromatic CH bend
2, Unassigned weak bands: 945, 669.
3. Other remarks:
This sample possessed less mass than that required by the Level 1
criteria for IR analysis. A spectrum of acceptable quality was obtained by
using Fourier Transform IR techniques.
Sample appeared to contain predominantly saturated hydrocarbons and
aliphatic esters of aromatic acids.
A-181
-------
TABLE A-170, VAPOR ABOVE CHEMICAL OIL TANK, CANISTER RINSE:
LC CUT #5 IR
SAMPLE: 5SR-LC5
1. Major peaks and assignments
v (cm" ) J_ Assignments/Comments
2963, 2931, 2878 S Aliphatic CH
1731 S Ester or aliphatic ketone
1488, 1456 M Aliphatic CH bend
1377 W Methyl CH bend
1280, 1123 S,M Aromatic or aliphatic esters or
ethers
1076 M Ester or ether
743, 700 M,W ~(CIVn~' n-4 rock''n9 or sub~
stituted aromatic CH bend
2. Unassigned weak bands: 1440, 1224, and 1038 cm"1.
3. Other remarks:
Sample predominantly aliphatic esters of aromatic and aliphatic acids
or aliphatic ethers.
A-182
-------
TABLE A-171.
VAPOR ABOVE CHEMICAL OIL TANK, CANISTER RINSE:
LC CUT #6 IR
SAMPLE: 5XR-LC6
1.
2.
Major peaks and assignments
v (cm"1)
3335
3068
2959, 2931, 2856
1732
1684
1602
1465
1383, 1273
746
Unassigned weak bands: 1224
I
M( broad)
W
S
S
M
M
M
M
w
, 1129,
Assignments/Comments
Alcoholic or phenolic OH or
Aromatic CH stretch
Aliphatic CH stretch
Ester or aliphatic ketone
Ketone or amide
Aromatic CJ-L-=-C stretch
Aliphatic CH bend
Alcohol, phenol or aromatic
or amide CN stretch
Substituted aromatic CH bend
1074, 1026, 965, 821, 698, 615
ami de
ether
3. Other remarks:
Sample consists predominantly of aliphatic alcohols, amides or esters
or alkylated derivatives of phenol.
TABLE A-172.
VAPOR ABOVE CHEMICAL OIL TANK, CANISTER RINSE:
LC CUT #7 IR
SAMPLE: 5XR-LC7
1, Major peaks and assignments
v
2,
3.
(cm"1)
2959, 2932, 2856
1739
1459
1264, 1164, 1075
Unassigned weak bands:
Other remarks:
J_ Assignments/Comments
S Aliphatic CH stretch
S Ester or aliphatic
M Aliphatic
W Ester or ether
1678, 1602, 1561, 1376, 821, 739, 698.
A-183
-------
TABLE A-173. COKE OVEN GAS
Sample Name: Coke Oven Gas
Sample Date: 12/15/77
Analysis Date: 12/15/77
C1-C7 HYDROCARBONS
Bulb #1
Range
GC
Range
GC
1
2
3
4
5
6
7
1
2
3
4
5
6
7
ppm
# Peaks (V/V)
1 66,190
1 11,110
3 1,093
1 1
6 43
4 124
0 —
Bulb #2
ppm
# Peaks (V/V)
1 66,992
1 11,598
3 1,159
1 1
6 44
4 168
0 —
AROMATICS (ppm, V/V)
On-Site RTI
Bulb 1 Bulb 2 SS Can
Benzene 6195.5 6421.0 1667.2
Toluene 437.0 248.0 67.8
Ethyl Benzene NA NA 0.3
m & p Xylene NA NA 4.4
o Xylene NA NA 0.7
SULFURS (ppm, V/V)
On-Site
Bulb 1 Bulb 2
H2S (COS) 4229 5020
so2
Cjo
NA = No Analysis
— = Compound Not Detected
A-184
-------
TABLE A-174. PRIMARY COOLER CONDENSATE TANK SAMPLES
Sample Date: 12/16/77
Analysis Date: 12/16/77
(Bulb #1 Only)
(Bulb #1 Only)
Range
GC
Range
GC
crc7
1
2
3
4
5
6
7
1
2
4
K
6
7
HYDROCARBONS
Bulb #1
# Peaks
1
1
4
0
3
2
1
Bulb #2
# Peaks
ppm
(V/V)
1,357
349
139
—
7
13
53
ppm
(V/V)
AROMATICS (ppm, V/V)
On-Site RTI
Bulb 1 Bulb 2 SS Can
Benzene 1565.6 1653.4
Toluene 160.8 178.1
Ethyl Benzene NA 1.2
m & p Xylene NA 37.7
o Xylene NA 9.7
SULFURS (ppm, V/V)
On-Site
Bulb 1 Bulb 2
H2S (COS) 2350
SO- —
CS, —
2
NA = No Analysis
— = Compound Not Detected
A-185
-------
TABLE A-175. AMBIENT DATA SHEET
Plant Name: U.S. Steel
Location: Birmingham, Alabama
Operator: Tom Allen
Time of Sample: 15:00 12/12 to 15:00 12/13
Station Number: 1 2 3
Metered Volume cu. meter 0.258 0.275
Cyanide Catch (CN~) ygms 16.3 1.1
Concentration ppm 0.056 0.004
ygms/std m 62.6 4.0
Wind Direction:
Wind came out of the southeast for the 24 hour sample period at
approximately 5 mph.
Comments:
Station 1 - Chemical Lab.
2 - Mule Barn
3 - Railroad tracks
Station 2 was not in operation due to power problems at sample
location.
A-186
-------
TABLE A-176. AMBIENT DATA SHEET
Plant Name: U.S. Steel
Location: Birmingham, Alabama
Operator: Tom Allen
Time of Sample: 15:00 12/13 to 15:00 12/14
Station Number 123
Metered Volume cu. meter 0.280 0.280
Cyanide Catch (CN~) ugms 22.0 2.5
Concentration ppm 0.069 0.008
ygms/std m3 78.1 8.9
Wind Direction:
Wind out of Southeast for ~ 10 hours at = 9 mph.
Wind out of Southwest for ~ 5% hours at ~ 6 mph.
Wind out of Northwest for * 8% hours at ~ 5 mph.
Comments:
Station #2 down due to power problems at sampling location.
ppm calculated assuming total cyanides (CN~) as HCN.
A-187
-------
TABLE A-177. AMBIENT DATA SHEET
Plant Name: U.S. Steel
Location: Birmingham, Alabama
Operator: Tom Allen
Time of Sample: 15:00 12/14 to 15:00 12/15
Station Number: 123
Metered Volume cu. meter 0.289 0.215 0.289
Cyanide Catch (CN~) ygms 4.3 0.5 2.5
Concentration ppm 0.013 0.002 0.008
ygms/std m3 14.8 2.3 8.6
Wind Direction:
Wind from Northwest for 13 h. at = 5 mph.
North for 4 h. at * 3 mph; N.E. for 3 h. at * 3 mph; E for 7h h.
at ~ 3 mph; W for lh h.
Comments:
Wind direction varied during run: See Met. Station data sheet.
A-188
-------
TABLE A-178. AMBIENT DATA SHEET
Plant Name: U.S. Steel
Location: Birmingham, Alabama
Operator: Tom Allen
Time of Sample: 15:00 12/15 to 12/16
Station Number: 123
Metered Volume cu. meter 0.289 0.215 0.289
Cyanide Catch (CN~) ugms 5.8 1.0 1.5
Concentration ppm 0.018 0.004 0.005
uigms/std m3 20.0 4.6 5.2
Wind Direction:
Wind from West for 7 hours at ~ mph.
Wind from North for 9 hours at ~ 2 mph.
Wind from Southwest for 8 hours at * 7 mph.
Comments:
Ambient stations were taken down at 18:00 on 12/16 - 3 hour samples
were not analyzed.
A-189
-------
TABLE A-179. SASS TRAIN DATA SHEET
Plant Name: U.S. Steel
Location: Birmingham, Alabama
Date: 12/16/77
Test Performed By: F. J. Phoenix
Run Number: 7
Sampling Location: Upwind Ambient-Station #3 Railroad tracks
Pre Leak Test: 0.01
Post Leak Test: 0.02
Test Time:
Start: 19:30
Finish: 22:36
Meter Volume (c.f.):
Start: 882.05
Finish: 1883.44
Volume of Gas Sampled 1001.39
978.06 scf.
Average Gas Temperature (°F)
Ambient 57°
Sampling Location: 57°
XAD-2 Resin: 57°
Meter Box: 74°
Comments:
1. Wind out of the Southwest.
A-190
-------
TABLE A-180. UPWIND AMBIENT TRAILER LOCATION
Sample Name:
Sample Date:
Analysis Date:
Upwind Ambient Trailer Location
12/16/77
12/21/77 (at RTI)
(Bulb #1 Only)
(Bulb #1 Only)
Range
GC
Range
GC
crc7
1
2
3
4
5
6
7
1
2
3
4
5
6
7
HYDROCARBONS
Bulb #1
ppm
# Peaks (V/V)
1 2.9
0 —
0 —
0 —
0 —
0 —
0 —
Bulb #2
ppm
# Peaks (V/V)
AROMATICS (ppm, V/V)
On- Site RTI
Bulb 1 Bulb 2 SS Can
Benzene 0.6 0.7
Toluene — —
Ethyl Benzene NA —
m & p Xylene NA —
o Xylene NA —
SULFURS (ppm, V/V)
On-Site
Bulb 1 Bulb 2
H2S (COS) 0
so2 o
cs2 o
NA = No Analysis
— = Compound Not Detected
A-191
-------
TABLE A-181. ORGANIC EXTRACT SUMMARY, UPWIND AMBIENT, XAD-2 RESIN
Total
organics mg/sm3
TCO, mg
GRAV, mg
Preliminary
5.0
100
40
Concentrate
2.6
48
23
LCI
0.07
2.0
0.0
LC2
1.01
24.8
3.2
LC3
0.32
7.2
1.6
LC4
0.0
0.0
0.0
LC5
0.06
1.8
0.0
LC6
0.30
4.2
4.0
LC7
0.19
0.0
5.2
£
1.95
40.0
14.0
Category
MATE comparison value, mg/sm3*
VD
Aliphatic hydrocarbons
Halogenated aliphatics
Aromatic hydrocarbons
Halogenated aromatics
Heterocyclic N, 0, S
compounds
Sulfides, disulfides
Nitriles
Ethers
Aldehydes, ketones
Nitroaromatics
Alcohols
Amines
Phenols, halo and nitrophenols
Esters, amides
Mercaptans
Carboxylic acids
Sulfoxides
0.12
0.12 0.06 0.14
0.01 0.006
0.14
0.01
0.01
0.01
0.01
0.01
0.14
0.01
0.01
0.01
0.19
0.19
0.02
0.02
0.02
0.19
0.02
0.02
0.02
0.12
0.0
0.32
0.07
0.0
0.0
0.0
0.33
0.20
0.01
0.03
0.03
0.03
0.33
0.03
0.03
0.03
NOTE: The MATE Comparison Value is based on the GRAV mass in the LC cut divided by the gas sample volume. For compound
classes indicated by IR, the MATE comparison value is 100 percent of the GRAV concentration. For compound classes
expected65 but not identified by IR, the MATE Comparison Value is 10 percent of the GRAV concentration.
-------
TABLE A-182. UPWIND AMBIENT, XAD-2 RESIN:
PRELIMINARY IR
SAMPLE: 7X-P
1. Major peaks and assignments
v (cm" ) J^ Assignments/Comments
2966, 2932, 2858 S Aliphatic CH stretch
1740, 1729 - S Ester and/or aliphatic ketone
1451, 1377 M,W Aliphatic CH bend
1266, 1116, 1099 S Ester or atomatic ether
1076, 1029 M Aromatic fingerprint region
798, 713 M Substituted aromatic
2. Unassigned weak bands: 1604 cm
3. Other remarks:
This sample possessed less mass than that required by the Level 1
criteria for IR analysis. A spectrum of acceptable quality was obtained by
using Fourier Transform IR techniques.
Sample predominantly aliphatic esters of aromatic acids.
A-193
-------
TABLE A-183,
UPWIND AMBIENT, XAD-2 RESIN:
CONCENTRATE IR
SAMPLE: 7X-C
1. Major peaks and assignments
v (cm -1) I
3065, 3032 W
2966, 2928, 2873, 2862 S
1727 M
1705 M
1607, 1492 M
1453, 1376 M
1261, 1113 M,W
M
Assignments/Comments
Aromatic or olefinic CH stretch
Aliphatic CH stretch
Saturated ketone or ester
Aryl ketone or ester
Aromatic O^-C stretch
Aliphatic CH bend
Ester of aromatic acid, aromatic
or aliphatic ether
Substituted aromatic CH bend
-1
1316, 1179, 1097, 1069, 1026 cm
801, 757, 708, 702
2. Unassigned weak bands:
3. Other remarks:
Sample contains predominantly alkylated aromatic esters (e.g. benzoates),
saturated and aromatic hydrocarbons and possibly some saturated ketones and/or
esters.
A-194
-------
TABLE A-184, UPWIND AMBIENT, XAD-2 RESIN:
LC CUT #1 IR
SAMPLE: 7X-LC1
1. Major peaks and assignments
v (cm ) l_ Assi gnments/Comments
2959, 2924, 2856 S Aliphatic CH stretch
1458 M Aliphatic CH bend
1376 w Isolated methyl CH bend
752, 698 W Mono-substituted benzene
2. Unassigned weak bands: 1746, 1610 cm"1.
3. Other remarks:
Sample predominantly saturated hydrocarbons. However, bend @ 1746
suggests presence of small amounts of aliphatic ketones or esters, and bends
at 1610, 752 and 698 cm~ suggest presence of small amounts of substituted
benzene.
A-195
-------
TABLE A-185. UPWIND AMBIENT, XAD-2 RESIN:
LC CUT #2 IR
SAMPLE: 7X-LC2
1. Major peaks and assignments
2.
3.
(cm"1)
3065, 3030
2965, 2924, 2871
1601, 1492
1456
1374
752, 699
Unassigned weak bands:
I_ Assi gnments/Comments
M Aromatic or olefinic CH
S Aliphatic CH stretch
W,M Aromatic C^-C
M Aliphatic CH bend
W Isolated methyl CH bend
M,S Substituted aromatic CH bend
1515, 1263, 1029, 887, 834
Other remarks;
Bands in C-H out-of-plane bending region for aromatics.
of mono-substituted benzene.
Sample contains only aliphatic and aromatic hydrocarbons.
Characteristic
A-196
-------
TABLE A-186. UPWIND AMBIENT, XAD-2 RESIN:
LC CUT #3 IR
SAMPLE: 7X-LC3
1.
2.
3.
Major peaks and assignments
v
(cm"1)
3084, 3062, 3026, 3001 M
2965, 2925, 2871, 2856 S
1591, 1515 W
1494, 1453 M
1374 W
890, 833, 778, 754 W,M,M,S
Unassigned weak bands: 1729, 1263j
Other remarks:
Assignments/Comments
Aromatic or olefinic CH
Aliphatic CH Stretch
Aromatic C^-^-C ring mode
Aliphatic CH bend
Isolated methyl CH bend
Substituted aromatic
1098, 1031
Sample predominantly aliphatic and aromatic hydrocarbons with a trace
of ketone or ester as evidenced by very weak absorption at 1728 cm .
A-197
-------
TABLE A-187. UPWIND AMBIENT, XAD-2 RESIN;
LC CUT #4 IR
SAMPLE: 7X-LC4
1,
Major peaks and assignments
v
(cm"1)
3063
2959, 2929, 2856
1738, 1729
1603, 1494, 1465
1453, 1380
1265, 1116
I
W
S
S
W
M,W
S,M
Assignments/Comments
Aromatic or olefinic CH stretch
Aliphatic CH stretch
Ester or aliphatic ketone
Aromatic C-:-L^C stretch
Aliphatic CH bending
Ester of aromatic acid, aromatic
or aliphatic ether
Substituted aromatic CH bend
1380, 1315, 1177, 1098, 1069, 1025
794, 754, 708 W,W,S
2. Unassigned weak bands: 1662, 1588.
3. Other remarks:
Bands at 1098, 1069, 1025, 754, and 708 cm"
substituted benzene.
Sample predominantly aromatic esters of considerable aliphatic character.
-1
Suggestive of mono-
A-198
-------
TABLE A-188.
UPWIND AMBIENT, XAD-2 RESIN:
LC CUT #5 IR
SAMPLE: 7X-LC5
1.
2.
Major peaks and assignments
_i
v (cm )
3020
2959, 2926, 2856
1725
1602, 1584
1462, 1454
1380
1273, 1122
798, 742, 710
Unassigned weak bands: 1175
I
W
S
S
w
M
W
S,M
W,W,S
, 1071,
Assi gnments/Comments
Aromatic or olefinic CH
Aliphatic CH stretch
Ester or aliphatic ketone
Aromatic C-1-^
0
Aliphatic CH bend
Methyl CH bend
Aliphatic or aromatic C-0
Substituted aromatic
1026 cm"1.
3. Other remarks:
Sample predominantly aliphatic and/or aryl esters. Bands for C C=0 and
C-0 frequencies are highly suggestive or aromatic esters.
A-199
-------
TABLE A-189,
UPWIND AMBIENT, XAD-2 RESIN:
LC CUT #6 IR
SAMPLE: 7X-LC6
1.
2.
Major peaks and
v (cm"1)
3065, 3036
1726
1603, 1585
1456
1380
1274, 1116
758, 711
Unassigned weak
assignments
I
• W
S
M,W
M
W
S,M
M,S
bands: 1515, 1174,
Assi gnments/Comments
Aromatic or aliphatic CH
Ester or aliphatic ketone
Aromatic or olefinic C-^^-^C
Aliphatic CH bend
Methyl CH bend
Aromatic or aliphatic ether or
ester or aromatic acid
Substituted aromatic CH bend
1069, 1028, 981 .
3. Other remarks:
Broad band at 3341 cm
-1
due to H20 in cell,
Sample composed primarily of aliphatic esters of aromatic acids with
bands at 758 and 741 cm being characteristic of mono-sub, benzene.
A-200
-------
TABLE A-190.
UPWIND AMBIENT, XAD-2 RESIN:
LC CUT #7 IR
SAMPLE: 7X-LC7
1.
Major peaks and assignments
v (cm"1)
2965, 2930, 2859
1726
1603
1450
1403
1374
1274, 1109
716
I
S
S
M
M
M
M
M,S
Assignments/Comments
Aliphatic CH stretch
Ester or aliphatic ketone
Olefinic or aromatic C-^-^-C
Aliphatic CH bend
Olefinic CH bend
Methyl CH bend
Aromatic ester or aromatic ether
and aliphatic ester
Olefinic C-H bend
2. Unassigned weak bands:
3. Other remarks:
1556, 1027, 940 cm
-1
Spectrum indicates sample is predominantly unsaturated esters,
such as acrylates, maleates, etc. Bands at 1603, 1403 and 716 cm"
suggests that vinyl group is cj^-disubstituted.
A-201
-------
TABLE A-191. UPWIND AMBIENT, CANISTER RINSE:
MASS OF SAMPLE AND CONCENTRATE
Equivalent total sample quantities
Fraction
TCO, mg
GRAY, mg
Total, mg
Total, mg/Sm"
Preliminary
Concentrate
(data not
available)
-data not available-—-)
6.7
0.24
LCI
LC2
LC3
LC4
LC5
LC6
LC7
(TCO + GRAV <15 mg, No LC)
*Standard conditions of 20° C and 760 mmHg.
A-202
-------
TABLE A-192. UPWIND AMBIENT, CANISTER RINSE:
CONCENTRATE IR
SAMPLE: 7XR-C
1. Major peaks and assignments
v (cm ) J_ Assi gnments/Comments
3030 W Aromatic CH stretch
2950, 2930, 2855 S Aliphatic CH stretch
1725, 1715 S Aliphatic ketone or ester
1600, 1575 W Aromatic C^-C stretch
1460, 1380 S,M Aliphatic CH bend
1295, 1280 S Ester of aromatic or a,0-unsat-
urated acids or aromatic ethers
1130, 1075 S Ester of aromatic or a,B-unsat-
urated acids, aromatic or aliphatic
ethers,
2, Unassigned weak bands: 1650, 820-760 (series of weak bands).
3. Other remarks:
This sample contains predominantly saturated and aromatic compounds.
Spectrum also indicates that sample contains aliphatic esters of
aromatic acids and saturated ethers.
A-203
-------
TABLE A-193. SASS TRAIN DATA SHEET
Plant Name: U.S. Steel
Location: Birmingham, Alabama
Date: 12/16/77
Test Performed By: F. J. Phoenix
Run Number: 6
Sampling Location: Downwind Ambient-Station #1 Chem. Lab.
Pre Leak Test: 0.02
Post Leak Test: 0.02
Test Time:
Start: 14:40
Finish: 18:30
Meter Volume (c.f.):
Start: 872.52
Finish: 1876.65
Volume of Gas Sampled: 1004.13 c.f.
972.27 scf.
Average Gas Temperature (°F)
Ambient: 55°
Sampling Location: 55°
XAD-2 Resin: 55°
Meter Box: 75°
Comments:
1. Wind out of the Southeast.
A-204
-------
TABLE A-194. DOWNWIND AMBIENT CHEM LAB SITE
Sample Name:
Sample Date:
Analysis Date:
Downwind Ambient Chem Lab Site
12/16/77
12/21/77 (All Analyses at RTI)
16:25
(Bulb #1 Only)
(Bulb #1 Only)
Crc7
Range
GC 1
2
3
4
5
6
7
Range
GC 1
2
3
4
5
6
7
HYDROCARBONS AROMATICS (ppm, V/V)
Bulb #1
jin .1 Ppm un~5ite RTI
# reaks (V/V)
Bulb 1 Bulb 2 SS Can
1 3.4 Benzene 1.3 0.3 —
0 — Toluene — — —
0 — Ethyl Benzene NA NA —
0 — m & p Xylene NA NA —
0 — o Xylene NA NA —
0 —
0 —
SULFURS (ppm, V/V)
Bulb #2
ppm On-Site
# Peaks (V/V)
Bulb 1 Bulb 2
1 3.1 H2S (COS) 0 0
o — so2 o o
o — cs2 o o
U —
g NA = No Analysis
0 —
0 .. —
A-205
-------
TABLE A-195. DOWNWIND AMBIENT, XAD-2 RESIN:
MASS OF SAMPLE AND CONCENTRATE
Equivalent total sample quantities
Fraction
TCO, mg
GRAV, mg
Total, mg
Total, mg/Snf
Preliminary
Concentrate
LCI
LC2
LC3
LC4
LC5
LC6
LC7
0
3.0
60.0
33.5
(TCO + GRAV <15 mg, No LC)
60.0
36.15
2,2
1.3
*Standard conditions of 20° C and 760 mmHg.
A-206
-------
TABLE A-196. DOWNWIND AMBIENT, XAD-2 RESIN:
PRELIMINARY IR
SAMPLE:
1
6X-P
2.
3.
Major peaks, and assignments
v (cm" )
2972-2856
1726
1602
1445
1260
794
699
Unassigned weak bands:
J_
M
W
W
W
S
S
Assignments/Comments
Aliphatic CH stretch
Ketone or ester
Conj, olefine and/or aromatic
Aliphatic CH bend
Ester of aromatic acid
Substituted aromatic cmpds
1089, 1020, 986.
Other remarks:
This sample possessed less mass than that required by the Level 1 criteria
for IR analysis. A spectrum of acceptable quality was obtained by using
Fourier Transform IR technology.
Sample contains some saturated hydrocarbons and aromatic esters. Two sharp
bands at 794 and 699 cm suggest that aromatic cmpds are substituted such that
1,3, and 5 adjacent hydrogens are present.
A-207
-------
TABLE A-197,
DOWNWIND AMBIENT, XAD-2 RESIN:
CONCENTRATE IR
SAMPLE: 6X-C
1.
2.
Major peaks
v (cm
3063
2963, 2926,
1731
1604, 1463
1455, 1377
1262, 1095,
and assignments
li
2856
1020
801, 711
Unassigned weak bands: 1586
!
W
S
S
W,M
M,W
S
S,M
, 1176,
Assignments/Comments
Aromatic or olefinic CH
Aliphatic CH stretch
stretch
Ester or aliphatic ketone
Aromatic C-1-^
Aliphatic CH bend
Ester of aromatic acid
Substituted aromatic CH
864, 749 cm"1 .
bend
3. Other remarks:
Sample contains aromatic and aliphatic esters or ethers and possibly
some aliphatic ketones.
A-208
-------
TABLE A-198, DOWNWIND AMBIENT, CANISTER RINSE:
MASS OF SAMPLE AND CONCENTRATE
Equivalent total sample quantities
Fraction TCO, tng GRAV, mg Total 5 mg Total, mg/Sm3
Preliminary 225.0 4.0 229.0 8,3
Total GRAV 8.2 0.30
LCI
LC2
LC3
LC4 (TCO + GRAV <15 mg, No LC)
LC5
LC6
LC7
*Standard conditions of 20° C and 760 mmHg.
A-209
-------
TABLE A-199. DOWNWIND AMBIENT, CANISTER RINSE:
CONCENTRATE IR
SAMPLE: 6XR-C
16XAD
1.
Major peaks
V
2962-2858
1729
1599- 1584
1465
1378
1288, 1273
can Rinse #6 - downwind
and assignments
(cm'1) I
S
S
W
M
W
M,S
ambient
Assi gnments/Comments
Aliphatic CH
Ester or aliphatic ketone
Aromatic C^^C
Aliphatic CH bend
Methyl CH bend
Ester of aromatic acid or aromatic
ether
1123, 1071 M Aromatic ester or aromatic or
aliphatic ether
739 M Substituted aromatic CH bend
2. Unassigned weak bands: 1071, 1066, 962, 812
3. Other remarks:
Bands at 2366 and 2340 cnf^due to C02
Bands at 677 cm~ due to residual methylene chloride on salt plate.
Bands at 1288 and 1273 cm highly suggestive of an ester of aromatic acid.
Sample is predominantly aliphatic esters of aromatic acids, or possibly
aromatic and/or aliphatic ethers.
A-210
-------
TABLE A-200. AMMONIA LIQUOR, pH 2 EXTRACT:
MASS OF SAMPLE, CONCENTRATE, AND LC CUTS
Equivalent Total Sample Quantities
Fraction
TCO, mg
GRAV, mg
Total, mg
Preliminary
Concentrate
LCI
LC2
LC3
LC4
LC5
LC6
LC7
8,720
4,670
730
3,460
140
210
70
1,860
0.0
6,470
6,560
5,030
1,750
880
680
260
0.0
500
80
4,150
15,280
9,700
2,480
4,340
820
470
70
2,360
80
10,620
A-211
-------
TABLE A-201. AMMONIA LIQUOR, pH 2 EXTRACT:
PRELIMINARY IR
SAMPLE: 8A-P
1.
Major peaks and assignments
-1
v cm" )
3590, 3470
3600-3000
3040, 3000
2955, 2938, 2850
1660-1650
1455, 1380
845-800
I
W
W( broad)
W
s
M
M,W
W
Assi gnments/Comments
Free and dimeric OH stretch of
phenols
Alcohol or phenolic OH stretch
(polymeric)
Aromatic CH stretch
Aliphatic CH stretch
Diary 1 ketones, carboxylate ion,
or aromatic or highly conj.
carboxylic acid
Alky! CH bend
Sub. aromatic CH bend
1330 cm
-1
2, Unassigned weak bands:
3, Other remarks:
Spectrum indicates that sample is predominantly alkylated phenols or
alkylated derivatives of highly unsaturated or aromatic acids.
A-212
-------
TABLE A-202, AMMONIA LIQUOR, pH 2 EXTRACT;
CONCENTRATE IR
SAMPLE: 8A-C
1. Major peaks and assignments
v (cm"1)
2.
3.
3418
3055
2959, 2925, 2856
1650
1602
1459
1376
814
746
Unassigned weak bands: 1240.
Other remarks:
2363 and 2342 due to COg,
Sample appears to contain predominantly alkylated phenols,
Assi gnments/Comments
Alcoholic or phenolic OH
Aromatic C-H
Aliphatic C-H
B-diketone, diary! ketone
Aromatic
Aromatic, methyl, methylene
Aromatic, methyl, methylene
Aromatic, methyl, methylene
Aromatic, C-C1, aliphatic
TABLE A-203. AMMONIA LIQUOR, pH 2 EXTRACT:
LC CUT #1 IR
SAMPLE: 8A-LC1
1. Major peaks and assignments
v (cm"1) !_
2959, 2932, 2856 S
1465, 1376 M
2. Unassigned weak bands: 725.
3. Other remarks:
Probable saturated hydrocarbon, LRMS indicative of some PNAs.as well
as saturated chains.
Assignments/Comments
Aliphatic C-H
Aliphatic CH bend
A-213
-------
TABLE A-204. AMMONIA LIQUOR, pH 2 EXTRACT:
LC CUT #1 LRMS
SAMPLE: 8A-LC1
1, Categories Present
Intensity
10
100
2. Subcategories
Category
PNAs
Aliphatic
Specific compounds
Intensity Subcategory/Compounds
10 perylene, benzpyrene, m/e 252
10 chrysene, triphenylene, m/e 228
10 anthracene, phenanthracene, m/3 178
3. Other
Intensity
100
Comments
Clusters to high intensity peaks every
14 amu. From vL25 amu to
^55amu. Suggestive of saturated chains
A-214
-------
TABLE A-205. AMMONIA LIQUOR, pH 2 EXTRACT:
LC CUT #2 IR
SAMPLE: 8A-LC2
1. Major peaks and assignments
v (cm" ) I_ Assignments/Comments
3055 S Aromatic'C-H, -CH^-halogen
2959, 2925, 2870 S Aliphatic C-H
1931 W Aromatic
1808 W Aromatic
1733 W Aromatic
1602 M Aromatic
1458 S Aliphatic CH bend
1376 M Methyl CH bend
1315 M Aromatic
1246 M Aromatic
1911 M Aromatic
1081, 1033, 958 M Aromatic
833, 732 S Aromatic, C-C1, aliphatic
2. Unassigned weak bands:
3. Other remarks:
Probable mono-substituted alkyl aromatic.
A-215
-------
TABLE A-206,
AMMONIA LIQUOR, pH 2 EXTRACT:
LC CUT # 2 LRMS
SAMPLE: 8A-LC2
1. Categories Present
Intensity
100
10
2. Subcategories, Specific Compounds
Intensity
100
10
10
10
10
1
3, Other
Intensity
Category
PNAs
PNAs
Subcategory/Compounds
Pyrene, m/e 202
Perylene, benzpyrene, m/e 252
Chrysene, triphenylene, m/e 228
Anthracene, phenanthrene, m/e 178
Acenaphthylene ? m/e 152
Anthracene ? m/e 276
Comments
A-216
-------
TABLE A~207, AMMONIA LIQUOR, PH 2 EXTRACT;
LC CUT #3 IR
SAMPLE: 8A-LC3
1. Major peaks and assignments
v (cm" ) I_ Assignments/Comments
3055 S Aromatic C-H, -CH2-ha1ogen
2925 W Aliphatic C-H
1650 W Unsaturated aromatic
1602 M Aromatic
1452 S Aromatic
1191 M Aromatic
883 M Aromatic
842 S Aromatic
815 S Aromatic
773 S Aromatic
746 S Aromatic
2. Unassigned weak bands: 1924, 1801.
3. Other remarks:
PNA hydrocarbons; confirmed by LRMS
A-217
-------
TABLE A-208. AMMONIA LIQUOR, pH 2 EXTRACT:
LC CUT #3 LRMS
SAMPLE: 8A-LC3
1. Categories present
Intensity
100
2. Subcategories, Specific Compounds
Intensity
100
100
100
10
3. Other
Intensity
100
Category
PNAs
Subcategory/Compounds
Perylene, benzpyrene, m/e 252
Chrysene, triphenylene, m/e 228
Pyrene, m/e 202
Anthracene, phenanthrene, m/e 178
Comments
High molecular weight PNAs @ m/e 404,
378, 352, 326, 302, 276, Compatible
with IR,
A-218
-------
TABLE A-209. AMMONIA LIQUOR, PH 2 EXTRACT:
LC CUT #4 IR
SAMPLE: 8A-LC4
1. Major peaks and assignments
v .(cm"1) i
3425 M
3055 W
1650 W
1452 S
1328 M
1239 M
746 S
725 S
2. Unassigned weak bands:
3. Other remarks:
2390, 2370, due to C00.
Assignments/Comments
Alcoholic or phenolic OH
Aromatic C-H
B-diketone unstaurated C-H carboxylic
acid, diar/1 ketone
Aliphatic C-H
Aliphatic C-H, phenol, acid
Aliphatic C-H, phenol, acid or alcohol
CH3, C-C1 , Aromatic
CH-, C-C1, aromatic
TABLE A-210, AMMONIA LIQUOR, pH 2 EXTRACT:
LC CUT #4 LRMS
SAMPLE: 8A-LC4
1. Categories present
Intensity Category
100-10 Amines
2, Subcategories, Specific Compounds
Intensity Subcategory/Compounds
10-100 Polyaromatic amines, m/e 341, 317
291, 267, 241, 217
3, Other
Intensity Comments
A-219
-------
TABLE A-211, AMMONIA LIQUOR, pH 2 EXTRACT
LC CUT #5 IR
SAMPLE: 8A-LC5
1.
Major peaks and
v (cm"1)
3384
3055
2932
2856
1719
1602
1458
1376
1273
assignments
I
M
M
S
M
W
M
S
M
M
Assignments/Comments
OH
Aromatic C-H
Aliphatic C-H
Aliphatic C-H
Ketone, ester
Aromatic
Aromatic
Aromatic
CH3-
2.
3.
S
2226.
Phenyl, C-C1, aliphatic
1917,
821
746
Unassigned weak bands
Other remarks:1
This sample possessed less mass than that required by the Level 1
criteria for IR analysis. A spectrum of acceptable quality was obtained by
using Fourier Transform IR techniques.
Substituted phenol probable.
to C02.
Bands at 2363 cm"1 and 2239 cm"1 due
A-220
-------
TABLE A-212. AMMONIA LIQUOR, pH 2 EXTRACT:
LC CUT #6 IR
SAMPLE: 8A-LC6
1. Major peaks and
v (cm'1)
3280
3199
3055
2925
2863
1650
1596
1459
1280
835
752
2. Unassigned weak
assignments
I
S
S
S
S
M
S
S
S
S
M
S
bands : 2226 .
Assignments/Comments
Aromatic C-H
Aromatic C-H
Aromatic C-H
Aliphatic C-H
Aliphatic C-H
B-diketone, carboxylate, diary!
ketone
Substituted phenyl
Substituted phenyl
Ester, ether
Aromatic C-H
C-C1 , aromatic C-H, al
iphatic
3. Other remarks:
LRMS supports aromatic nature of compounds responsible for this spec-
trum. Probably heterocyclic amines.
A-221
-------
TABLE A-213, AMMONIA LIQUOR, pH 2 EXTRACT:
LC CUT #6 LRMS
SAMPLE: 8A-LC6
1. Categories present
Intensity
10-100
2. Subcategon'es, Specific Compounds
Intensity
10-100
Other:
Intensity
10-100
Category
Amines
Subcategory/Compounds
Amines, m/e 303, 279, 253, 229, 203
195, 179, 159, 145. These materials
show ion characteristic of condensed
aromatic rings.
Comments
m/e 184, 122
A-222
-------
TABLE A-214. AMMONIA LIQUOR, pH 2 EXTRACT:
LC CUT #7 IR
SAMPLE: 8A-LC7
1.
2.
3.
Major peaks and
v (cm~ )
2970
2925
2875
1740
1431
1376
1239
1123
1082
1027
739
698
616
Unassigned weak
Other remarks:
Probable ester.
assignments
I
S
S
M
S
M
M
S
M
M
M
M
M
M
bands:
Assignments/Comments
Aliphatic C-H (stretching)
Aliphatic C-H (stretching)
Aliphatic C-H (stretching)
Ester or aliphatic ketone
Aliphatic C-H (bending)
Aliphatic C-H (bending)
Ester C-0
Ester C-0
Ester C-0
Ester C-0
C-C1 , aromatic C-H, aliphatic
C-C1 , aromatic C-H, aliphatic
C-C1 , aromatic C-H, aliphatic
A-223
-------
TABLE A-215, AMMONIA LIQUOR, pH 2 EXTRACT:
LC CUT #5 LRMS
SAMPLE: 8A-LC7
1. Categories Present
Intensity Category
10 PNAs
2. Subcategories, Specific Compounds
Intensity
10
3. Other
Intensity
100
Subcategory/Compounds
perylene, benzpyrene, m/e° 252
triphenylene, chrysene, m/e 228
pyrene, m/e 202
anthracene, phenathrene, m/3 178
Comments
m/e 256?
No significant ion intensity
A-224
-------
TABLE A-216. AMMONIA LIQOUR, pH 12 EXTRACT:
MASS OF SAMPLE, CONCENTRATE, AND LC CUTS
Equivalent Total Sample Quantities
Fraction
TCO, mg
GRAV, mg
Total, mg
Preliminary
Concentrate
LCI
LC2
LC3
LC4
LC5
LC6
LC7
I
2,000
1,278
0
105
175
50
0
1,320
0
1,156
1,385
138
20
60
60
0
690
50
3,156
2,663
138
125
235
110
0
2,010
50
2,670
A-225
-------
TABLE A-217. AMMONIA LIQUOR, pH 12 EXTRACT:
PRELIMINARY IR
SAMPLE: 8B-P
1. Major peaks and assignments
v (cm"1) ! Assignments/Comments
3500 - 3150 Broad Unresolved band due to NH stretch
of amines and anides
3090, 3020 M Aromatic or olefinic CH stretch
2920, 2918, 2860 M Diphatic CH stretch
1725 S Ester or diphatic ketone
1650 S Amide I band
1615 - 1590 S (broad) Substituted aromatic C-C or NH
bend of 1° amine
1370 W Aliphatic CH bend
1240, 1120 S Ester of aromatic acid, CN stretch
of amines or anides, alcohol or
aromatic ether
690, 640 M Substituted aromatic CH bend
2. Unassigned weak bands: 920 cm~ .
3. Other remarks:
Sample appears to be predominantly aliphatic amides and ketones, but
only some substituted benzene compounds.
A-226
-------
TABLE A-218,
AMMONIA LIQUOR, pH 12 EXTRACT:
CONCENTRATE IR
SAMPLE: 8B-C
1. Major peaks and assignments
v (cnf1)
2,
3,
3600
3500-2900
3030, 3000
2955, 2930, 2875, 2850
1725
1660
1595, 1500
1470, 1385
1250-1080
840- 730
810
! Assignments/Comments
"Free" OH of alcohol or phenol
(broad) OH and/or NH stretch of alcohols,
amines, and anides
Aromatic or olefinic CH stretch
Diphatic CH stretch
Ester or aliphatic ketone
Amide I band
Aromatic C-C and ami no NH bend
Aliphatic CH bend
CH stretch for amines and anides,
C-0 stretch of alcohol, C-C-0
stretch of aromatic esters, or
C-O-C stretch of ethers
(broad) Amine and anide NH bend
Substituted aromatic CH bend
Unassfgned weak bands: 1510, 1340, 1000, 950 cm'1 .
-1
Other remarks:
Bands at 1610, 1605, 1595, and 1510 cm"1 probably arising from NH
stretching of 1° and 2° amides and amines.
Sample predominantly aromatic and aliphatic amines and amides, but
also containing some alcohols aliphatic ketones, esters of aromatic acids,
and/or aromatic or aliphatic ethers.
A-227
-------
TABLE A-219. AMMONIA LIQUOR, pH 12 EXTRACT:
LC CUT #1 IR
SAMPLE: 8B-LC1
1. Major peaks and assignments
v (cm) JL Assi gnments/Comrnents
2960, 2926, 2852 S Alkane
1462, 1377, 1281 M Alkane
1037 . M Alkane
2. Unassigned weak bands: 1735.
3. Other remarks:
This sample possessed less mass than that required by the Level 1
criteria for IR analysis. A spectrum of acceptable quality was obtained
by using Fourier Transform IR techniques.
Sample consisted of saturated hydrocarbons and saturated ethers.
A-228
-------
TABLE A-220. AMMONIA LIQUOR, pH 12 EXTRACT:
LC CUT #2 IR
SAMPLE: 8B-LC2
1.
Major peaks and assignments
v
(cm"1)
3055
2959, 2925, 2856
1452
1376
833, 842, 815, 773
732
Unassigned weak bands:
1938.
M
S
M
W
M
S
1726.
Assignments/Comments
Aromatic C-H, -CH^-halogen
Aliphatic C-H
Aromatic, aliphatic
Aliphatic
Aliphatic
Aliphatic, C-C1, aliphatic
3. Other remarks:
This sample possessed less mass than that required by the Level 1
criteria for IR analysis, A spectrum of acceptable quality was obtained by
using Fourier Transform IR techniques,
2362 and 2342 due to C02- Probable PNA hydrocarbon. Sample contains
alkylated aromatic hydrocarbons.
A-229
-------
TABLE A-221. AMMONIA LIQUOR, pH 12 EXTRACT:
LC CUT #3 IR
SAMPLE: 8B-LC3
1.
2.
Major peaks and assignments
v (cm"1)
3053
2926, 2853
1728
1668
1456
1238
815
749
Unassigned weak bands: 1377,
I
W
S
W
W
M
W
M
M
881,
Assignments /Comments
Aromatic C-H, -CF^-halogen
Aliphatic C-H
Ester or aliphatic ketone
Al kene
Aromatic, methyl, methyl ene
Ester, ether
Aromatic, C-C1
Aromatic, C-C1
640.
3. Other remarks:
This sample possessed less mass than that required by the Level 1
criteria for IR analysis. A spectrum of acceptable quality was obtained
by using Fourier Transform IR techniques.
2363 and 2339 due to C02. Specific PNA's identified by LRMS,
A-230
-------
TABLE A-222, AMMONIA LIQUOR, pH 12 EXTRACT:
LC CUT #3 LRMS
SAMPLE: 8B-LC3
1. Categories present
Intensity Category
100 PNA's
2, Subcategories, specific compounds
3. Other
Intensity
100
10
10
10
100
100
Intensity
100 @ high probe
temperatures
Subcategory/Compounds
Naphthalene, M/e 128'
Anthracene, phenanthrene M/e 178
Pyrene M/e 202
Chrysene, triphenylene M/e 228
Perylene, benzpyrene M/e 252
Anthanthrene, M/e 276
Comments
Ions at M/e 476, 474, 450, 426, 424, 400
376, 374, 352, 350, 326, 302. Overall
ms pattern strongly indicative of high
molecular weight PNA's.
PNA assignments supported by IR.
A-231
-------
TABLE A-223, AMMONIA LIQUOR, pH 12 EXTRACT;
LC CUT #4 IR
SAMPLE: 8B-LC4
1.
2.
Major peaks and assignments
v (cm" )
3459
3062
2973, 2918
2856
1725
1602
1431, 1335
1239
1095
965
746, 615
Unassigned weak bands: 1198,
I
M
M
S
M
W
W
S
S
M
M
S
698 .
Assi gnments/Comments
OH/NH
Aromatic C-H,-CH2-halogen
Aliphatic C-H
Aliphatic C-H
Ester, ketone
Aromati c
Aromatic, methyl
Ester, ether, amine
Aromatic
Aromati c
Aromatic, C-C1 , aliphatic
3. Other remarks:
This sample possessed less mass than
criteria for IR analysis. A spectrum of
using Fourier Transform IR techniques.
Probable aromatic amine or alcohol.
taht required by the Level 1
acceptable quality was obtained by
LRMS more consistent with amines.
A-232
-------
TABLE A-224, AMMONIA LIQUOR, pH 12 EXTRACT:
LC CUT #4 LRMS
SAMPLE: 8B-LC4
1. Categories present
Intensity Category
2. Subcategories, Specific Compounds
Intensity Subcategory/Compounds
3, Other
Intensity Comments
No significant ion intensity >«\420
amu (70 eV), Many prominent ions throughout
spectra of odd M/e (70 eV and 20 eV).
Consistent with amine structures as indi-
cated by IR, No PNA's present.
A-233
-------
TABLE A-225. AMMONIA LIQUOR, pH 12 EXTRACT:
LC CUT #5 IR
SAMPLE: 8B-LC5
1. Major peaks and assignments
v (cm" )
3600-3200
2959, 2932, 2856
1733
1602
1459, 1438
1249, 1102
I_ Assignments/Comments
W(broad) Alcohol or phenolic OH
S Aliphatic CH stretch
M Ester or aliphatic ketone
W Aromatic C-C
M Aliphatic CH bend, aromatic
M Ester or aromatic acid, alcohol,
ether
Substituted aromatic CH bend
-1
746, 698 W
2. Unassigned weak bands: 972, 855 cm
3. Other remarks:
This sample possessed less mass than that required by the Level 1
criteria for IR analysis, A spectrum of acceptable quality was obtained
by using Fourier Transform IR techniques.
Probable alcohols and esters of aromatic acids.
A-234
-------
TABLE A-226, AMMONIA LIQUOR, pH 12 EXTRACT:
LC CUT #5 LRMS
SAMPLE: 8B-LC5
1, Major peaks and assignments
v (cm"1) 1
2959, 2932, 2856 S
1733 M
1602 W
1459, 1328 M
1438, 1246 S
1328, 1102 M
972 M
835 W
746 W
2. Unassigned weak bands: 698
3, Other remarks:
Assignments/Comments
Aliphatic C-H
Ketone/ester
-CH2-
Alkane
Alkane
Aromatic fingerpoint
Aromatic
Aromatic
A-235
-------
TABLE A-227,
AMMONIA LIQUOR, pH 12 EXTRACT:
LC CUT #6 IR
SAMPLE: 8B-LC6
1. Major peaks and assignments
v (cnf1) I
3343, 3144
3062
2932
2863
2713, 2610
1733
1595
1507, 1472
1376
1239
M
S
S
M
M
M
S
S
M
S
Assignments/Comments
OH, NH
Aromatic C-H
Aliphatic C-H
Aliphatic C-H
H-bonded OH, NH
Ketone, ester
Aromatic, C^^C
Aromatic, methyl
Methyl CH bend
Ester, ether, CN
aromatic amine
, methyl ene
stretch of
787 S
2. Unassigned weak bands:
3. Other remarks:
Sample predominantly aromatic amines, esters of aromatic acids, or
diphatic or aromatic ethers.
A-236
-------
TABLE A-228. AMMONIA LIQUOR, pH 12 EXTRACT:
LC CUT #6 LRMS
SAMPLE: 8B-LC6
Categories Present
Intensity
100
Category
Amines? M/e 401 (possibly halogenated),
377 [ionizing voltage = 20 eV]
Subcategories, Specific Compounds
Other
Intensity
Intensity
Subcategory/Compounds
Comments
M/e 327, 303, 277, 168, 149, 129
[ionizing voltage = 70 eV ]
Data not sufficient for subcategory
or compound assignment.
TABLE A-229. AMMONIA LIQUOR, pH 12 EXTRACT:
LC CUT #7 IR
SAMPLE: 8B-LC7
1,
2,
3,
Major peaks and assignments
v
(cm"1)
2932
2856
1733
1616
1459
1383
1246
1171
746
S
M
S
M
M
M
M
M
W
Unassfgned weak bands: 3596 broad .
Other remarks:
Probable ester.
Assi gnments/Comments
Aliphatic C-H
Aliphatic C-H
Ketone, ester
Aromatic C-^-C
Aromatic, methyl, methylene
Methyl CH bend
Ester, ether
Ester, ether
Aromatic, C-C1 , diphatic
A-237
-------
TABLE A-230, AMMONIA LIQUOR, pH 12 EXTRACT:
LC CUT #7 LRMS
SAMPLE: 8B-LC7
1. Categories Present
Intensity
1-10
2. Subcategories, Specific Compounds
Intensity
10
10
Other
10
Intensity
100
10
Category
PNA's
Subcategory/Compounds
Perylene, benzpyrene, M/e 252
Chrysene, triphenylene, M/e 228
Pyrene, M/e 202
Comments
No significant ion intensity
>^M/e 300 with exception of one
ion at M/e 368.
M/e 168, 144, 130, 118 (?)
M/e 182
A-238
-------
TABLE A-231. ORGANIC EXTRACT SUMMARY, BIOLOGICAL TREATMENT PLANT SLUDGE, pH 7 EXTRACT
ro
co
Total Organics, mg/1
TCO, mg
GRAV, mg
Category
Aliphatic hydrocarbons
Halogenated aliphatics
Aromatic hydrocarbons
Halogenated aromatics
Heterocyclic N, 0, S compounds
Sulfides, disulfides
Nitriles
Ethers
Aldehydes, ketones
Nitroaromatics
Alcohols
Amines
Phenols, halo and nitrophenols
Esters, amides
Mercaptans
Carboxylic acids
Sul fox ides
Preliminary Concentrate LC] LC2 LC3
23.8 7.8 2.1 0.50 0.60
135 3.0 000
45 56.0 16.0 3.6 4.4
MATE
2.1
0.2
2.1 0.5 0.6
0.05 0.06
0.6
0.6
0.6
LC4
0.2
0
1.6
Comparison
0.2
0.02
0.02
0.02
0.02
0.02
0.2
0.2
0.2
LC5
0.05
0
0.4
Value,
0.05
0.005
0.005
0.005
0.005
0.005
0.005
0.005
0.005
LC5
2.7
0
2C.8
mg/1
2.7
2.7
2.7
0.3
2.7
0.3
2.7
2.7
0.3
2.7
LC7
0.3
0
2.4
0.3
0.3
0.3
0.03
0.03
0.03
0 03
z
6.5
0
49.2
2.1
0.2
6.45
0.13
0.025
0.025
0.025
3.32
3.5
0.30
3.00
0.30
3.2
3.5
0.33
2.73
0.03
Note: The MATE Comparison Value is based on the GRAV mass in the LC cut divided by the sample volume. For compound classes indicated by IR, the
MATE comparison value is 100 percent of the GRAV concentration. For compound clases expected but not indicated by IR, the MATE comparison value is
10 percent of the GRAV concentration.
-------
TABLE A-232. BIOLOGICAL TREATMENT PLANT SLUDGE, pH 7 EXTRACT:
PRELIMINARY IR
SAMPLE: 12P biological sludge; preliminary
1. Major peaks and assignments
v
2,
3,
(cm"1)
3058 W
2960-2930 S
2857 S
1709 W
1642-1550 M
1465 M
1380 W
1282-1240 W
752 W
Unassigned weak bands: 831, 787,
Other remarks:
Inverted bands at 2370-2340 cm'1
-1
Assignments/Comments
Aromatic CH or olefinic CH
Aliphatic CH
Aliphatic and/or aldehydic CH
Ketone, ester, aldehyde
Aromatic or olefinic C=C
Aliphatic CH (methylene) or
aromatic C=C
Aliphatic CH (methylene) or
a-naphthalene
Aromatic ether or ester C-0
Aromatic CH
-1
697 cm
due to CO^. Bands around
700-850 cm" suggestive of 3-, 4-, and 5- adjacent aromatic CH_.
A-240
-------
TABLE A-233, BIOLOGICAL TREATMENT PLANT SLUDGE, pH 7 EXTRACT:
CONCENTRATE IR
SAMPLE: 12-C biological sludge,
1.
Major peaks and assignments
v (cm"1)
3055
2959-2856
1712
1657
1595
1458
1376
1273 - 1239
752
PH
I
W
S
M
M
M
M
M
W
M
7.0 extract concentrated sample
Assignments/Comments
Aromatic CH
Aliphatic and aldehydic CH
Ketone, ester
Olefine (conj.) or aromatic C=C
Aromatic ring (C=C)
Aliphatic or aromatic CH
Aliphatic CH (methyl)
Aromatic ether, or ester
4CH,,} rocking for n>4 or
aromatic CH
821, 787, 691 cnrl
-1
2. Uassigned weak bands
3. Other remarks:
Bands at 2363 and 2342 cm"1are due to presence of COp in cell
inadequate purging.
Probable compounds and alkylated derivatives.
A-241
-------
TABLE A-234. BIOLOGICAL TREATMENT PLANT SLUDGE, pH 7 EXTRACT
LC CUT #1 IR
SAMPLE: 12-LC1
1.
2,
Major peaks and assignments
v (cm"1)
2959, 2927, 2857
1463
1377
720, 677
Uassigned weak bands: 2724,
I
S
M
W
W
1150 cm'1
Assignments/Comments
Aliphatic CH stretch
Aliphatic CH methyl and
Aliphatic C-C methyl
Aromatic CH bend
methyl ene
3. Other remarks;
Bands at 2363 and 2342 cnf1 due to C02, Band at 676 cnf1 likely due to
residual CH2C12 left on plate.
Probable saturated hydrocarbons, with trace amounts of aromatic compounds.
A-242
-------
TABLE A-235. BIOLOGICAL TREATMENT PLANT SLUDGE, pH 7 EXTRACT:
LC CUT #2 IR
SAMPLE: 12-LC2
1.
2.
3.
Major peaks and
v (cm"1)
3013
2959 - 2863
1602
1458
1376
814, 746
Unassigned weak
Other remarks:
assignments
W
S
W
0 M .
M
W
bands:
Assignments/Comments
aromatic or olefinic CH
aliphatic CH
aromatic C-C
aliphatic C-H bend
methyl CH bend
substituted aromatic
Bands at 2365 and 2340 cm"1 due to C05. Splitting pattern at 846, 814
--\ *•
and 746 cm highly suggestive of meta-substituted benzene.
Probable alkylated aromatic hydrocarbons.
A-243
-------
TABLE A-236. BIOLOGICAL TREATMENT PLANT SLUDGE, pH 7 EXTRACT:
LC CUT #3 IR
SAMPLE: 12-LC3
I. Major peaks and
v (cm"1)
3048
2952 - 2924
2856
1725
1602
1445, 1376
1259
1184, 1150
883, 842, 814,
741
2. Unassigned weak
3. Other remarks:
assignments
I
S
S
S
W
S
S,M
M
M
I
S
bands: 1917,
Assignments/Comments
aromatic or olefinic CH stretch
aliphatic C-H stretch
aliphatic C-H stretch
ketones, esters
aromatic or olefinic C-C
aliphatic CH bend
aromatic ether or ester
ether, ester
substituted aromatic CH bend
1026, 951
Broad weak band at 3400 - 3200 cm"1 suggests alcohols or phenols.
Probable alkylated aromatic hydrocarbons.
A-244
-------
TABLE A-237. BIOLOGICAL TREATMENT PLANT SLUDGE, pH 7 EXTRACT:
LC CUT #4 IR
SAMPLE: 12-LC4 Biological Sludge, pH 7.0 extract
1.
2.
3.
v (cm"1)
Major peaks and assignments
I
M
M
3418
3048
2959, 2856
1718
1595
1458, 1438
1376
876, 828, 807
746
S
M
M
S
M
M
S
Assignments/Comments
OH or NH stretch (broad)
aromatic C-H
aliphatic C-H
ketone, ester
aromatic or olefin C=C
methylene (doublet)
-CH3
aromatic C-H
aromatic C-H
Unassigned weak bands: 1328, 1266, 1239, 1177, 1033, 951
Other remarks:
Bands at 2363 - 2340 cm are due to presence of C02 in cell.
Spikes about 1600 - 1800 are due to presence of water vapor in cell
Probable alkylated aromatic hydrocarbons.
A-245
-------
TABLE A-238. BIOLOGICAL TREATMENT PLANT SLUDGE, pH 7 EXTRACT-
LC CUT #5 IR
SAMPLE: 12-LC5
1. Major peaks and assignments
v (cm ) I Assignments/Comments
3048 W aromatic or olefinic CH
2959, 2924, 2856 S aliphatic CH
1602 M aromatic C-^-C stretch
1451 M aliphatic CH bend
1375 W methyl CH bend
883, 821, 752 W,W,S substituted aromatic
2. Unassigned weak bands: 2219, 1280, 1184 cm'1
3. Other remarks:
This sample possessed less mass than that required by the Level 1
criteria for IR analysis. A spectrum of acceptable quality was obtained
by using Fourier Transform IR techniques.
Sample contains only saturated, unsaturated and/or aromatic hydro-
carbons. Possibly some ketones or esters present as evidenced by small
absorption at 1712 cm .
A-246
-------
TABLE A-239. BIOLOGICAL TREATMENT PLANT SLUDGE, pH 7 EXTRACT:
LC CUT #6 IR
SAMPLE: 12-LC6
1.
Major peaks and
v (cm"1)
3281
3055
assignments
I
broad (M)
2959, 2931, 2856 S
2.
3.
1712
1657
1602
1451, 1376
1280
1191
810, 752
Unassigned weak
Other remarks:
S
S
S
W
M
M
M
bands: 1081,
Assignments/Comments
alcoholic, phenolic or acid OH
aromatic OR olefinic CH
aliphatic CH
ketone or ester
carboxylic acid or ketone
aromatic or olefinic C-:-:-:-C
aliphatic CH bend
acid, ester of aromatic acid
ether, alcohol or phenol
substituted aromatic CH
1033, 835, 615 cm"1
Sample predominantly phenolic compounds, or carboxylic acids.
A-247
-------
TABLE A-240. BIOLOGICAL TREATMENT PLANT SLUDGE, pH 7 EXTRACT-
LC CUT #7 IR
SAMPLE: 12-LC7
1. Major peaks and assignments
v (cm ) 1 Ass i gnments/Comments
3550 - 3000 broad phenol or alcoholic OH stretch
3061 S aromatic or olefinic
2931, 2856 S aliphatic CH stretch
16°2 S aromatic or olefinic C-1-1-^
1280, 1122, 1040 M alcohol or phenol
828» 76° W substituted aromatic CH bend
2. Unassigned weak bands: 1664, 1726 cm"1
3. Other remarks:
Sample predominantly alcohol or phenolic compounds.
A-248
-------
TABLE A-241. TOTAL CHROMATOGRAPHABLE ORGANICS (TCO) ANALYSIS OF SAMPLES
UD
Sample
Froth Flotation Separator, XAD Resin
Final Cooler CT, XAD Resin
Tar Storage Tank, XAD Resin
Tar Decanter Vapor, XAD Resin
Chemical Oil Tank, XAD Resin
Downwind Ambient, XAO Resin
Upwind Ambient, XAD Resin
Froth Flotation separator, Can. Rinse
Final Cooler Ct. Can. Rinse
Tar Storage Tank, Can. Rinse
Tar Decanter Vapor, Can Rinse
Chemical Oil Tank, Can. Rinse
Downwind Ambient, Can. Rinse
Upwind Ambient, Can. Rinse
Ammonia Liquor, pH2
Ammonia Liquor, pH12
Final Cooler CT hot well, pH2
Final Cooler CT hot well, pH12
Final Cooler CT cold well, pH2
Final Cooler CT cold well, pH12
Tar Decanter condensate, pH2
Tar Decanter condensate, pH12
Bio. plant sludge, pH7
Preliminary
Sample
Volume TCO
(ml) (mg)
2,990 18,538
3,370 6,066
3,310 6,620
3,090 31,518
3,220 26,726
2,750 0
1,000 100
150 360
60 138
150 1,545
210 8,190
200 2,480
75 225
not
800 8,720
800 2,000
800 2,160
800 720
800 1,360
800 480
150 1,545
150 345
450 135
Concentrate
Sample
Volume TCO
(ml) (mg)
250
60
100
750
500
5.0
5.0
b
b
b
b
b
b
available
100
25
10
10
10
10
10
10
10
13,175
1,410
6,090
33,675
28,800
3.0
4.8
b
b
b
b
b
b
4,670
1,278
1,463
660
862
356
923
338
3
Volume
put on LC
Column,
ml
1.0
2.0'
1.0
1.0
1.0
-
2.5
174. 5/85. 5^
743.4/61.3°.
6,500/103.9°
22,120/90.4°
0
0
-
1.0
0.5
0.5
1.0
0.5
2.0
0.5
2.0
5.0
LC 1
0.0
0.0
1.8
0.0
0.3
-
1.0
0.0
-
2.0
0.0
15.3
-
-
7.3
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
LC 2
48.0
34.0
42.0
14.7
14.9
-
12.4
1.0
-
30.0
88.3
65.6
-
-
34.6
2.1
30.0
2.9
10.2
0.1
5.4
1.3
0.0
Total
LC 3
0.8
0.7
3.5
14.9
17.7
-
3.6
0.2
-
37.4
1.0
17.4
-
-
1.4
3.5
0.0
0.0
0.0
0.0
3.7
0.6
0.0
TCO mass in LC cuts, mqa
LC 4 LC 5 LC 6
0.1
1.1
0.8
0.8
0.0
INSUFFICIENT
0.0
0.0
INSUFFICIENT
0.2
0.0
0.0
INSUFFICIENT
INSUFFICIENT
2.1
1.0
4.2
2.6
1.2
1.5
1.9
0.7
0.0
4.8 0.0
0.9 6.2
0.4 4.5
0.1 0.8
0.2 6.0
MASS- -NO LC
0.9 2.1
0.0 0.7
MASS— NO LC
0.0 2.0
0.0 5.1
0.0 4.2
MASS--NO LC
MASS--NO LC
0.7 18.6
0.0 26.4
1.1 28.7
1.0 41.7
3.4 28.1
0.9 47.8
2.1 29.8
3.1 41.5
0.0 0.0
LC 7
0.0
0.0
0.0
0.0
0.0
-
0.0
0.0
-
0.0
0.0
0.0
-
-
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
Total
53.7
42.9
53.0
31.3
39.1
-
20.0
1.9
~
71.6
94.4
102.5
-
-
64.7
33.0
64.0
48.2
42.9
50.3
42.9
47.2
0.0
aTCO mass is ratioed back to original sample by multiplying TCO mass in an LC cut by (Concentrate Volume/Volume put on column). Blanks have been
subtracted from this data.
Total canister rinse samples taken to dryness after preliminary analysis. Sample placed on LC column was a weighed fraction of this dry sample. The
ratio total sample/sample on column is given in the column titled "Volume put on LC column." The TCO mass in an LC cut can be ratioed back to the
original sample by multiplying by the above ratio.
-------
TABLE A-242. RAW GRAV ANALYSIS DATA
^^
-^j
o
Samp 1 e
Froth Flotation Sepa-
rator, XAD Resin
XAD Resin
XAD Resin
Tar Decanter Vapor,
XAD Resin
Chemical Oil Tank,
XAD Resin
XAD Resin
XAD Resin
Froth Flotation Sepa-
rator, Can. Rinse
Final Cooler CT
Can. Rinse
Can. Rinse
Can Rinse
Chemical Oil Tank,
Can. Rinse
Downwind Ambient,
Upwind Ambient,
Can. Rinse
pH2
Ammonia Liquor,
pH12
Final Cooler CT
hot well, pH2
Final Cooler CT
hot well, pH12
Final Cooler CT
cold well, pH2
Final Cooler CT
cold well, pH12
Ta Decanter
ondensate, pH2
Ta Decanter
ondensate, pH12
Bi . plant
ludge, pH7
Prel iminary
Sample
Volume GRAV
(ml) (mg)
2,990
3,370
3.310
3,090
3,220
2,750
1,000
60
150
210
200
75
800
800
800
800
800
800
150
150
450
40
60
100
20,080
3,360
60
40
16
109C
1,764
8,960
4
6.560
1,156
192
80
160
160
138
138
45
Concentrate
Sample
Volume GRAV
(ml) (mg)
250
60
100
750
500
5.0
5.0
0
0
0
0
0
100
25
10
10
10
10
10
10
10
394.5
282
2,540
21,840
5,730
33.5
23
(b)
5.2
743.4
6,500
22,120
8.2
5,030
1,385
362
258
358
29
507
26
56
Liquid ChromatoaraDhv Work (mass in mq)'3'
Volume
on Column
ml
1.0
2.0
1.0
1.0
1.0
GRAV
0.5
0.3
0.1
0.4
0.3
1C 1
Blank
0.5
0.5
0.5
0.3
0.3
.C 2
Cor- Cor-
rected GRAV Blank rected
0.0
-0.2
-0.4
0.1
0.0
0.2
0.5
0.6
0.9
0.3
0.5 -0.3
0.5 0.0
0.5 0.1
0.3 0.6
0.3 0.0
GRAV
0.4
0.3
0.2
0.5
0.3
LC 3
Blank
0.4
0.4
0.4
0.5
0.5
LC 4
Cor-
rected GRAV Blank
0.0 0.3
-0.1 0.2
-0.2 0.4
0.0 0.1
-0.2 0.3
0.3
0.3
0.3
0.5
0.5
INSUFFICIENT MASS--NO
2.5
(b)
61.3 mg
103.9 mg
90.4 rag
1.0
0.5
0.5
1.0
0.5
2.0
0.5
2.0
5.0
0.3
0.3
0.4
0.2
7.0
1.1
0.5
0.1
0.5
0.2
0.1
0.3
3.2
0.3
0.0
0.0
0.0
-0.2
0.2
-0.2
0.2
0.2
0.2
0.0
0.0
0.0
0.0
0.3
0.4
0.2
NOT
7.0
1.1
0.5
-0.1
0.3
0.0
0.1
0.3
3.2
1.1
1.5
19.3
13.7
0.3 0.8
0.2 1.3
0.2 19.1
0.2 13.5
0.9
0.7
0.6
0.3
0.5
0.4
0.4
0.4
0.4 0.3
INSUFFICIENT
0.3 0.2
0.2 0.2
-0.1 1.6
INSUFFICIENT
0.5
Cor-
rected
0.0
-0.1
0.1
-0.4
-0.2
LC
-0.2
GRAV
0.3
0.2
0.5
0.3
0.2
0.2
1'
LC 5
Blank
0.3
0.3
0.3
0.3
0.3
0.3
Cor-
rected
0.0
-0.1
0.2
0.0
-0.1
-0. 1
'
GRAV
0.2
0.6
0.3
0.7
0.4
1.4
'
LC 6
Blank
0.6
0.6
0.6
0.4
0.4
0.4
'
Cor-
rected
-0.4
0.0
-0.3
0.3
0.0
1.0
GRAV
0.4
0.4
0.8
0.2
0.3
1.1
'
LC 7
Blank
0.5
0.5
0.5
0.4
0.4
0.4
Cor-
rected
-0.1
-0 1
0.3
-0.2
-0 1
1.3
'
MASS--NO LC
0.1
0.1
0.1
MASS-
0.1
0.1
1.5
NO LC
0.3
0.6
0.3
0.3
0.3
0.3
0.0
0.3
0.0
0.6
0.8
0.3
0.7
0.7
0.7
-0.1
0. 1
-0.4
0.2
0.5
0.1
0.3
U.3
0.3
-0.1
02
-0.2
AVAILABLE--SAMPLE COST
4.6
0.4
0.6
0.2
0.0
0.2
1.7
0.1
0.9
0.2 4.4
0.2 0.2
0.2 0.4
0.4 -0.2
0.4 -0.4
0.4 -0.2
0.2 1.5
0.2 -0.1
0.0 0.9
3.6
0.8
0.3
0.3
0.4
0.3
2.4
0.5
1.1
0.2
0.2
0.2
0.2
0.2
0.2
0.3
0.3
0.0
3.4 1.3
0.6 0.6
0.1 0.3
0.1 0.3
0.2 0.2
0.1 0.3
2.1 0.5
0.2 0.3
1.1 0.4
0.0
0.0
0.0
0.0
0.0
0.0
0.3
0.3
0.0
1.3
0.6
0.3
0.3
0.2
0.3
0.2
0.0
0.4
0.4
0.2
0.2
0. 1
0.4
0.2
0.5
0.4
0.1
0.. 4
0.4
0.4
0. 1
0.1
0.1
0.1
0.1
0.0
0.0
-0.2
-0.2
0.0
0.3
0. 1
0.4
0.3
0.1
j.4
7.8
2.5
7. 7
3.5
2.9
5.2
1.4
5.3
0.9
0.9
0.9
0.4
0.4
0.4
0.4
0.4
0.1
2.5
69
1.6
7.3
3.1
2.5
4.8
1.0
5.2
0.6
0.7
0 b
0. 1
0.3
U.2
0.2
0.4
0.6
IJ.2
0.2
0 2
0.2
U.2
U 2
0.3
0 1
-U. 1
0.4
0.5
U.3
-U. 1
0. 1
0 U
-0.1
0.1
0.6
(b)
'Total GRAV mass in an LC cut = [Corrected Grav mass] x [2.5
mass in an LC cut by (Concentrate volume/Volume put on
Total canister rinse samples taken to dryness and GRAV detei
presented in "Volume on column" column in table.
Sample spi1 led.
for LCI (2.0 for LC2-LC7)]. GRAV mass is ratioed back to original sample by multiplying
column).
rmined (Concentrate GRAV). Sample placed on column was weighed amount of GRAV material
-------
APPENDIX B
COST ESTIMATES FOR BYPRODUCT RECOVERY PLANTS
B-l
-------
APPENDIX 8
COST ESTIMATES FOR BY-PRODUCT RECOVERY PLANTS
Under subcontract to the Research Triangle Institute, The Wilputte
Corporation, Murray Hill, N.J., prepared capital cost estimates for selected
by-product plant processes, also providing utilities, manpower, and chemical
utilization estimates. The Wilputte estimates are for turnkey projects in
third quarter 1977 dollars, and do not include working capital. They are
factored from plants built or estimated by Wilputte Corporation over the
past few years. All of these by-product plant processes are based on a coke
oven gas flow of 1,416,000 mVday (50,000,000 scf/day), which corresponds to
roughly 4,160 Mg coke/day (4,580 tons/day). Limited (factor of 2) extrapola-
tion of the capital costs to different capacities, using a 0.6 factor, is
considered reasonably valid by Wilputte. An exception is the anhydrous
ammonia plant, which has such a small capacity that doubling or halving its
capacity would not significantly change the capital cost.
Costs of the utilities, chemicals, and manpower were estimated by RTI.
Chemical prices were obtained from the Chemical Marketing Reporter.70 Where
the prices of by-product plant grades were not available, as for phenol, the
petroleum-based prices were discounted by 50 percent.
Utilities costs were escalated to the third quarter of 1977 from those
presented by Massey and Dunlop.33 Twenty percent escalation was assumed.
Operator manpower was estimated at $9.00/hr, with benefits at 30 percent
of salary, which totals to $102,500/yr per working post.
Capital costs were put on an annual basis by amortizing over a 20-year
life at 9 percent interest.
(1) PHENOL REMOVAL PLANT
Phenol extraction from ammonia liquor with coke oven light oil,
followed by reaction with sodium hydroxide to produce sodium phenol ate for
sale
Capacity: approximately 433,400 I/day (114,500 gal/day) ammonia
liquor, producing 1,400 I/day (370 gal/day) of sodium
phenol ate _
-------
Design Removal: 3,500 ppm phenol incoming to 5- ppm
Factored From: Plant handling 250,000 gal/day, built in 1969
Capital Cost of Plant: $1,600,000
Operating Costs, Single Day Basis $/day
Daily Cost of Capital 430
Electricity [728 kwhr/day @ $.025/kwhr] 18
Steam (150 psig) [41,678 Ibs/day @ $4.25/1,000 Ibs] 177
Cooling Water [158,285 gal/day @ $0.03/1,000 gal] 5
Caustic Soda, 100% [2,519 Ibs/day @ $315/ton] 397
Labor [0.25 man @ $102,500/yr per post] 70
Maintenance [3 percent of capital cost annually] 132
Total Operating Cost $1,279
Phenol Credit [370 gal/day x 8.9 Ib/gal x $.105/lb] 346
(2) ALTERNATE PHENOL REMOVAL PLANT
Activated Sludge treatment and clarifier-thickener.
Capacity: approximately 433,400 I/day (114,500 gal/day) ammonia
liquor
Design Removal: 3,500 ppm phenol incoming to less than 1 ppm
Factored From: Plant of 230,000 gal/day, estimated in 1975
Capital Cost of Plant $1,900,000
Operating Costs, Single Day Basis $/day
Daily Cost of Capital $570
Electricity [44 kwhr/day] i
Steam - 150 psig [13,333 Ibs/day] 5
Steam - 15 psig [5,370 Ibs/day @ $2.12/1,000 Ibs] n
Make-up water [116,665 gal/day @ $.06/1,000 gal] 7
Phosphoric Acid, 75% [14 gal/day @ $1.50/gal] 21
Labor [0.1 man/shift] 28
Maintenance [3 percent of capital cost annually] 155
Total Operating Cost $851/day
(3) AMMONIA STILLS
+--M T F?C!1lty 1nc1udes botn free and fixed stills, using lime in fixed
still, ^ncluded are dephlegmator, lime handling, storage, and slaking
facilities, concrete lime settling basin, two ammonia liquor storage tanks
(24 hrs each), pumps and auxiliaries.
B-3
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Capacity: 18,200 1/hr (4,800 gal/hr) to 27,200 1/hr (7,200
gal/hr to allow for peaks.
Design Removal: 6 g/1 total ammonia to 0.015 g/1 in effluent. Plant
"recovers" 1,020 kg ammonia per hour.
Factored From: 5,000 to 7,500 gal/hr plant estimated in 1976.
Capital Cost of Plant: $2,280,000
Operating Costs, Single Day Basis $/day
Daily Cost of Capital 684
Steam - 18 psig [231,264 Ibs/day @ $2.12/1000 Ib] 490 0
Make-up Cooling Water [751,680 gal/day @ $.06/1000 gal] 45
Labor [0.1 man/shift] _ 28
Total $l,247/day
(4) AMMONIUM SULFATE PLANT WITH VACUUM CRYSTALLIZER
Absorption of NH3 in sulfuric acid, vacuum crystal! izer, salt
drying, and storage facilities.
Capacity: 1,416,000 mVday (50,000,000 scf/day) coke oven
gas (say 64 tons/day sulfate)
Design Removal: 10.6 g/m3 of ammonia on inlet, 0.11 g ammonia/m3
coke oven gas on outlet.
Factored From: 95 ton/day plant (74,000,000 scfd gas) estimated
Capital Cost of Plant: $8,050,000
Operating Cost on Daily Basis $/day
Daily Cost of Capital 2>416
Electricity [3,526 kwhr/day] °8
Steam - 160 psig [78,840 Ibs/day] 335
Steam - 18 psig [105,120 Ibs/day] 223
Sulfuric Acid, 100% [99,782 Ibs/day @ $50.00/ton] 2,494
Labor [0.1 man/shift] 28
Maintenance [3 percent of capital cost annually] _ DO/
Total $6,246/day
Credit for Ammonium Sulfate
[64 tons/day @ $65/ton] $4,160.
B-4
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(5) ANHYDROUS AMMONIA PLANT
Facility using U.S. Steel Phosam process for production of anhydrous
ammonia.
Capacity: 12 tons/day anhydrous ammonia
Design Removal: 7.8 g ammonia/m3 coke oven gas to 0.1 g ammonia/m3
gas (1,416,000 m3/day gas)
Factored From: Plant sold in 1973 for 100,000,000 scfd gas (24 tons/
day ammonia). Checked against facility handling
45,000,000 scfd gas estimated in 1976.
Capital Cost of Plant: $2 740 000
Operating Costs, Single Day Basis: $/day
Daily Cost of Capital 322
Electricity [2,930 kwhr/day] 73
Steam - 250 psig [280,000 Ibs/day @ 5.00/1,000 Ibs] 1 400
Steam - 18 psig [280,000 Ibs/day] '594
Make-up Cooling Water [1,108,800 gal/day] 67
Phosphoric Acid (100%) [185 Ibs/day @ $20.67/100 Ibs] 38
Caustic Soda (100%) [241 Ibs/day] 33
Labor [0.1 man/shift] 28
Maintenance [3 percent of capital cost annually] 225
Total $3,285/day
Credit for Anhydrous Ammonia
12 tons/day @ $130/ton $l,560/day
(6) INCINERATION OF WET AMMONIA VAPOR OR ANHYDROUS AMMONIA
Capacity: Sized to add to anhydrous ammonia process above;
i.e., 12 tons/day anhydrous ammonia
Capital Cost of Plant: $200,000
Operating Costs, Single Day Basis: $/day
Daily Cost of Capital 60
Electricity [358 kwhr/day] 9
Coke Oven Gas [1,370,182 scf/day @ $1.00/1000 scf] 1 370
Labor [0.1 man/shift] * 28
Maintenance [3 percent of capital cost annually] 16
Tota1 $l,483/day+Air
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(7) WASH OIL TYPE FINAL GAS COOLER
Final gas cooling and naphthalene removal using petroleum wash
oil, with bleed-off of naphthalene rich oil to light oil recovery plant.
Capacity: 1,416,000 m3 gas/day (50,000,000 scf/day)
Design Removal of Naphthalene: to 45-90 mg/m3
Factored From: 74 MM Scfd gas plant estimated in 1976.
Capital Cost of Plant: $2,360,000
Operating Costs. Single Day Basis $/day
Daily Cost of Capital
Electricity [3,629 kwhr/day] 91
Wash Oil [variable]
Labor [0.25 man/shift] 70
Maintenance [3 percent of capital cost annually] 194
Total $l,063/day
(8) VACUUM CARBONATE PLANT
Vacuum carbonate plant for H2S removal with HCN stripping and
Claus Sulfur Recovery Unit.
Capacity: 1,416,000 m3 gas/day (50,000,000 scfd gas)
H,S Removal: to 1.12 g/m3 (50 gr/100 scf)
Factored From: Plant handling 100 MM Scfd gas estimated in 1973.
Capital Cost of Plant: $5,040,000
Operating Costs, Single Day Basis $/day
Annual Cost of Capital
Electricity [4,854 kwhr/day]
Steam - 160 psig [178,704 Ibs/day]
Steam - 18 psig [394,200 Ibs/day] 835
Make-up Water [146,800 gal/day] *
Sodium Carbonate (100%) [18,835 Ibs/day] 1,039
Labor [0.1 man/shift] f
Maintenance [3 percent of capital cost annually] 414
$4, /lo/day
(9) HOLMES-STRETFORD PLANT FOR H2S REMOVAL INCLUDING FIXED SALTS RECOVERY
UNIT
Capacity: 1,416,000 m3 gas/day (50,000,000 scfd gas)
B-6
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Design. Gas In: 10.1 g H2S/m3 and 0.45 g/m3 organic sulfur expressed
as H2S.
Design. Gas Out: total sulfur expressed as H2S, less than 35 qrains/
100 scf.
0.79 g/m3 (35 gr/100 scf)
Capital Cost of Plant: $9,000 000
Operating Costs, Single Day Basis: $/day
Daily Cost of Capital • £ 701
Electricity [27,315 kwhr/day] '533
Steam - 180 psig [34,793°Ibs/day] 148
Steam - 15 psig [573,248 Ibs/day] 155
Make-up Water [329,616 gal/day] 20
Coke Oven Gas [380,889 scfd] 3»i
ADA [175 Ibs/day] ,
Vanadium [1.5 Ibs/day] ?
Citric Acid [175 Ibs/day @ $.58/lb] 102
Labor [1.25 man/shift] 351
Maintenance [3 percent of capital cost annually] 740
Tota] $5,281/day
B-7
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
EPA-600/2-79-016
3. RECIPIENT'S ACCESSIONING.
4. TITLE AND SUBTITLE
Environmental Assessment of Coke By-product
Recovery Plants
5. REPORT DATE
January 1979
6. PERFORMING ORGANIZATION CODE
AUTHORS D.W.VanOsdell, D.Marsland, B.H.Car-
penter, C.Sparacino, andR.Jablin
8. PERFORMING ORGANIZATION REPORT NO.
PERFORMING ORGANIZATION NAME AND ADDRESS
Research Triangle Institute
P.O. Box 12194
Research Triangle Park, North Carolina 27709
10. PROGRAM ELEMENT NO.
1AB604C and 1BB610C
11. CONTRACT/GRANT NO.
68-02-2630, Task 1
AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
Task Final; 3/77 - 6/78
14. SPONSORING AGENCY CODE
EPA/600/13
project officer is Robert V. Hendriks, Mail Drop 62,
The report gives results of an initial screening study, initiating a multi-
media environmental assessment of coke by-product recovery plants in the U.S. The
study included both the gathering and analysis of existing data and sampling and
analysis at one plant based on EPA's Industrial Environmental Research Laboratory.
RTP Level 1 protocol. Process data concerning design and operation of existing
plants and processes were examined. Many variations of all process types exist
forcing an examination of the industry to determine the commoner processes. Sam-
pling and analysis utilized a basic EPA Level 1 format, tailored for organic vapor
sampling. Specific samples were also analyzed for cyanide. Air was sampled at all
suspected pollution sources, most of them storage tanks. The largest single source
was the final cooler cooling tower: aromatics at > 50 g/Mg coke and cyanide at 278
g/Mg coke were both significant. Polynuclear aromatic hydrocarbon (PAH) com-
pounds were indicated, but not quantified. Concentrations of pollutants in the vapor
above storage tanks were measured, but actual emission rates were not determined
because of the difficulty in measuring working and breathing losses for the tanks
sampled. Water sampling data from the same plant, developed by EPA's Effluent
Guidelines Division, were included in the overall study analysis.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Grout
Pollution
Coking
Sampling
Analyzing
Assessments
Organic Compounds
Cyanides
Aromatic Poly cyc-
lic Hydrocarbons
Pollution Control
Stationary Sources
Organic Vapors
13 B
13H
14B
07C
07B
18. DISTRIBUTION STATEMENT
Unlimited
19. SECURITY CLASS (This Report/
Unclassified
21. NO. OF PAGES
387
20. SECURITY CLASS (Thispage)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
379
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