&EPA
United Stales Industrial Environmental Research EPA 600 7 79 048
Environmental Protection Laboratory February 1979
Agency Research Triangle Park NC 27711
Preliminary Environmental
Assessment of the
Lignite-Fired CAFB
Interagency
Energy/Environment
R&D Program Report
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EPA-600/7-79-048
February 1979
Preliminary Environmental
Assessment of the
Lignite-Fired CAFB
by
A.S. Werner, C.W. Young, William Piispanen, and B.M. Myatt
GCA Corporation
GCA/Technology Division
Bedford, Massachusetts 01730
Contract No. 68-02-2632
Program Element No. EHE623
EPA Project Officer: Samuel L Rakes
Industrial Environmental Research Laboratory
Office of Energy, Minerals, and Industry
Research Triangle Park, NC 27711
Prepared for
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, DC 20460
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ABSTRACT
This document presents the results of a preliminary environmental
assessment of the lignite-fired Chemically Active Fluid Bed (CAFB) process.
This report is a follow-on to an earlier environmental assessment of the
oil-fired CAFB. Waste streams contributing air and solid waste pollutants
were evaluated in terms of emission rates and potential environmental effects.
Particular emphasis is placed on flue gas emissions. As part of this investi-
gation, a field sampling and laboratory analysis program was carried out to
compile an emissions inventory of the CAFB pilot plant at the Esso Research
Centre, Abingdon (ERCA), England. In addition to the environmental assess-
ment, an economic evaluation of the oil-fired CAFB relative to alternative
residual oil utilization techniques is presented. Finally, recommendations
are made for further control needs and emissions testing to be carried out
in conjunction with the CAFB demonstration plant in San Benito, Texas.
Particulate emissions were less than those from direct combustion of
lignite using multiclones as a control. NOjj emissions were quite low with
0.09 lb/106 Btu being the highest measured. Light organics were equal to
those from conventional units, while heavy (>Cg) organic emissions were lower.
SOX emissions were one-half the NSPS for coal-fired boilers.
iii
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IV
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CONTENTS
Abstract iii
List of Figures vii
List of Tables x
Acknowledgments xiv
1. Executive Summary . 1
Overview 1
Conclusions 2
References 5
2. Introduction 6
The Chemically Active Fluid Bed (CAFB) Process 6
Background 6
Program Objectives 8
References 9
3. Process Description 10
Introduction 10
Overview 10
ESSO Pilot Plant 12
Foster-Wheeler Demonstration Plant 12
References 18
4. Measurement Program 19
Introduction 19
Field Tests 19
Laboratory Analysis 30
References . 74
5. Environmental Assessment 75
Introduction 75
Gaseous Emissions 77
Trace Element Air Emissions 79
Organic Emissions ... 95
Emissions from Oil-fired HDS and FGD Processes 97
References 104
Appendices
A. Process Descriptions and Economics of Residual Oil Desulfur-
ization Techniques • • A-l
The General Hydrodesulfurization Process A-2
Economic Forecast A-2
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CONTENTS (continued)
Autofining A-4
Gulfining A-6
Hydrofining (Exxon) A-ll
Hydrofining (BP) A-13
Ultrafining A-14
Unicracking/HDS A-14
Unionfining A-19
Summary A—23
References A-26
B. Economic Comparison of Residual Oil Utilization:
CAFB, FGD, HDS B-l
Introduction B-l
Basis of Cost Estimates B-3
Summary B-4
Coal Utilization B-10
References B-ll
C. Raw Data from Field Measurements C-l
D. Data from Laboratory Analyses of CAFB Samples D-l
vi
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FIGURES
Number Page
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
A-l
A-2
A-3
Gasif ier-regenerator schematic
Unit operations flow diagram of the ESSO pilot plant
Unit operations flow diagram of the Foster-Wheeler CAFB
demonstration plant
Adsorbent sampling system
Particulate size distributions measured by SASS train
Particulate size distributions measured by in-stack impactor . .
IR spectrum of XAD-2 resin from SASS-1
IR spectrum of XAD-2 resin from SASS-2
Broadband ESCA spectrum of SASS-1 filter particulate
Broadband ESCA spectrum of SASS-2 filter particulate
Carbon Is spectrum of SASS-1 filter particulate
Carbon Is spectrum of SASS-2 ly cyclone particulate
Carbon Is spectrum of RAC-1 filter particulate
Carbon Is spectrum of RAC-5 filter particulate
Sulfur 2p spectrum of SASS-2 filter particulate
Sulfur 2p spectrum of SASS-2 particulate filter with argon ion
etching: after 2 minutes of etching
Sulfur 2p spectrum of SASS-2 particulate filter with argon ion
etching: after 18 minutes of etching
Depth profile of sulfur in SASS-1 filter particulate
Depth profile of sulfur in SASS-2 filter particulate
Carbon Is spectrum of gasifier bed sample collected during
SASS-2
Flexicoking unit
Generalized schematic hydrodesulfurization flow diagram ....
Autofining process
11
13
15
21
26
27
43
43
61
62
64
65
67
68
69
70
71
72
72
73
101
A-3
A-5
A-7
vii
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Number
FIGURES (continued)
Pace
A-4 Shell residual oil hydrodesulfurization A~1
A-5 Exxon Hydrofining process A-12
A-6 BP Hydrofining process • • A~15
A-7 Ultrafining process A-1^
A-8 Unicracking/HDS process A~20
A-9 Unionfining process A-22
B-l Application of CAFB, HDS, and FGD systems at conventional
power plants ^~2
D-l IR spectrum of lOp cyclone catch from SASS-1 D-34
D-2 IR spectrum of 3y cyclone catch from SASS-1 D-34
D-3 IR spectrum of lp cyclone catch from SASS-1 D-35
D-4 IR spectrum of particulate filter from SASS-1 D-35
D-5 IR spectrum of condensate extract from SASS-1 D-36
D-6 IR spectrum of XAD-2 resin from SASS-1 D-36
D-7 IR spectrum of module rinse from SASS-1 D-37
D-8 IR spectrum of probe rinse from SASS-1 D-37
D-9 IR spectrum of lOy cyclone catch from SASS-2 D-38
D-10 IR spectrum of 3v cyclone catch from SASS-2 D-38
D-ll IR spectrum of ly cyclone catch from SASS-2 D-39
D-12 IR spectrum of particulate filter from SASS-2 D-39
D-13 IR spectrum of probe rinse from SASS-2 D-40
D-14 IR spectrum of XAD-2 resin from SASS-2 D-40
D-15 IR spectrum of XAD-2 resin from SASS-2, LC fraction 1 .... D-41
D-16 IR spectrum of XAD-2 resin from SASS-2, LC fraction 2 .... D-41
D-17 IR spectrum of XAD-2 resin from SASS-2, LC fraction 3 .... D-42
D-18 IR spectrum of XAD-2 resin from SASS-2, LC fraction 4 .... D-42
D-19 IR spectrum of XAD-2 resin from SASS-2, LC fraction 5 .... D-43
D-20 IR spectrum of XAD-2 resin from SASS-2, LC fraction 6 .... D-43
D-21 IR spectrum of XAD-2 resin from SASS-2, LC fraction 7 .... D-44
D-22 IR spectrum of module rinse from SASS-2 D-M
D-23 IR spectrum of module rinse from SASS-2, LC fraction 1 .... D-45
D-24 IR spectrum of module rinse from SASS-2, LC fraction 2 .... 0-45
viii
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FIGURES (continued)
Number Page
D-25 IR spectrum of module rinse from SASS-2, LC fraction 3 .... D-46
D-26 IR spectrum of module rinse from SASS-2, LC fraction 4 .... D-46
D-27 IR spectrum of module rinse from SASS-2, LC fraction 5 .... D-47
D-28 IR spectrum of module rinse from SASS-2, LC fraction 6 .... D-47
D-29 IR spectrum of module rinse from SASS-2, LC fraction 7 .... D-48
D-30 IR spectrum of condensate extract from SASS-2 D-48
D-31 IR spectrum of Tenax resin from RAC-2 D-49
D-32 IR spectrum of Tenax resin from RAC-4 D-49
D-33 IR spectrum of Tenax resin from RAC-4, LC fraction 1 D-50
D-34 IR spectrum of Tenax resin from RAC-4, LC fraction 2 D-50
D-35 IR spectrum of Tenax resin from RAC-4, LC fraction 3 D-51
D-36 IR spectrum of Tenax resin from RAC-4, LC fraction 4 D-51
D-37 IR spectrum of Tenax resin from RAC-4, LC fraction 5 D-52
D-38 IR spectrum of Tenax resin from RAC-4, LC fraction 6 D-52
D-39 IR spectrum of Tenax resin from RAC-4, LC fraction 7 D-53
D-40 IR spectrum of RAC 1-5 particulate sample D-53
D-41 IR spectrum of regenerator bed sample D-54
D-42 IR spectrum of limestone, total methylene chloride extract . . D-54
D-43 IR spectrum of lignite, total methylene chloride extract . . . D-55
D-44 IR spectrum of lignite, LC fraction 1 D-55
D-45 IR spectrum of lignite, LC fraction 2 D-56
D-46 IR spectrum of lignite, LC fraction 3 D-56
D-47 IR spectrum of lignite, LC fraction 4 D-57
D-48 IR spectrum of lignite, LC fraction 5 D-57
D-49 IR spectrum of lignite, LC fraction 6 D-58
D-50 IR spectrum of lignite, LC fraction 7 D-58
ix
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TABLES
Number
1 ESSO Pilot Plant Mass Flow Rates ................
2 Mass Flow Rates for Foster-Wheeler 22 MW CAFB Demonstration
Plant .......... . ................. 16
3 CAFB Particulate Test Data ................... *
ft CAFB Particulate Mass and Size Emissions Data Measured By
SASS Train .......................... 25
5 CAFB Gas Analysis ....................... 28
6 Laboratory Analysis Plan for CAFB-Lignite Study ........ 31
7 Solvents Used for Liquid Chromatography ............ 33
8 Inorganic Sample Preparation Scheme .............. 34
9 Total >Cg Organic Emissions .................. 36
10 Organic Emissions in CAFB SASS Samples, Run No. 1 ....... 38
11 Organic Emissions in CAFB SASS Samples, Run No. 2 ....... 39
12 Organic Emissions in CAFB RAC Samples ............. 40
13 Interpretation of IR Spectra from Gravimetric Residues of
Unfractionated Samples, SASS Run No. 1 ............ 41
14 Interpretation of IR Spectra from Gravimetric Residues of
Unfractionated Samples, SASS Run No. 2 ............ 42
15 Interpretation of IR Spectra from Gravimetric Residues of
RAC Sample Extracts Without LC Fractions ........... 44
16 Interpretation of IR Spectra from Gravimetric Residues of
XAD-2 Resin Extract and Its LC Fractions, SASS Run No. 2 ... 45
17 Interpretation of IR Spectra from Gravimetric Residues of
Module Rinse and Its LC Fractions, SASS Run No. 2 ...... 46
18 Interpretation of IR Spectra from Gravimetric Residues of
Tenax Resin Extract and Its LC Fractions, RAC Run No. 4 ... 47
19 Organic Composition of Spent Stone ............... 48
20 SSMS Analysis of CAFB Lignite ................. 49
21 SSMS Analysis of CAFB Limestone Feed .............. 50
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TABLES (continued)
Number Page
22 Trace Element Emissions in SASS Samples, Run No. 1 51
23 Trace Element Emissions in SASS Samples, Run No. 2 53
24 RAC-1 Trace Element Emissions 56
25 RAC-2 Trace Element Emissions 57
26 Concentrations of Selected Inorganic Species in SASS Samples
from the CAFB-Lignite Process 58
27 Concentrations of Selected Inorganic Species in Solid Samples
Collected for the CAFB-Lignite Study 59
28 Quantification Data from ESCA Analysis of RAC Train Particulate
Filters 60
29 Elemental Quantification Data for SASS Particulate Samples from
ESCA Analysis 63
30 SAM/IA Worksheet for Level I - ESSO, England, CAFB Pilot Plant . 78
31 SAM/IA Worksheet for Level I - ESSO, England, CAFB Pilot Plant,
SASS-1 80
32 SAM/IA Worksheet for Level I - ESSO, England, CAFB Pilot Plant,
SASS-2 83
33 SAM/IA Worksheet for Level I - Conventional Lignite Boiler with
Multiclone - Site A 87
34 SAM/IA Worksheet for Level I - Conventional Lignite Boiler with
ESP - Site B 91
35 Summary of Trace Element Data 94
36 Total CAFB Organic Emissions 95
37 Organic Emissions from Conventional Lignite-Fired Utility
Boilers 96
38 Range of Concentrations of Chemical Constituents in FGD Sludges. 98
39 Phase Composition of FGD Waste Solids in Weight Percent .... 99
40 Properties of Coke Products from West Texas Sour Asphalt
Operation 102
41 Prototype Flexicoker Disposition of Vanadium Among Products . . 103
A-l Estimated Cost of Autofining, 1980 A-6
A-2 Yields from Gulfining Process A-8
A-3 Estimated Cost of Gulfining, 1980 A-8
A-4 Typical Operating Parameters Shell Residual Oil
Hydrodesulfurization A-9
xi
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TABLES (continued)
Number
A-5 Estimated Operating Cost of the Shell Residual Oil
Hydrodesulfurization Process, 1980 .............. A-ll
A-6 Estimated Cost of EXXON Hydrofining, 1980 ........... A-13
A-7 Estimated Cost of BP Hydrofining, 1980 ............. A-16
A-8 Estimated Cost of Ultrafining, 1980 .............. A-18
A-9 Estimated Cost of Unicracking/HDS, 1980 ............ A-19
A-10 Estimated Cost of Unionfining, 1980 .............. A-21
A-ll Summary of Estimated 1980 Capital and Operating Costs Associated
with Alternative Hydrodesulfurization Processes ....... A-24
B-l Basis of Cost Comparison ... ................. B-5
B-2 Estimated 1980 Capital Costs for Regenerable and Nonregenerable
CAFB and FGD Systems, 250 MW Oil-Fired Power Plants ..... B-8
B-3 Estimated 1980 Operating Costs for CAFB, FGD and HDS Systems,
250 MW Oil-Fired Power Plants ................ B-9
D-l Sample Abbreviation Code .................... D-2
D-2 SSMS Analysis of 10p Cyclone Catch from SASS-1 ......... D-3
D-3 SSMS Analysis of 3p Cyclone Catch from SASS-1 ......... D-4
D-4 SSMS Analysis of ly Cyclone Catch from SASS-1 ...... ... D-5
D-5 SSMS Analysis of Particulate Filter from SASS-1 ........ D-6
D-6 SSMS Analysis of Particulate Filter Blank for SASS-1 and SASS-2. D-7
D-7 SSMS Analysis of XAD-2 Resin from SASS-1 ............ D-8
D-8 SSMS Analysis of XAD-2 Resin Blank for SASS-1 and SASS-2 .... D-9
D-9 SSMS Analysis of Composite Sample (CH) from SASS-1 ....... D-10
D-10 SSMS Analysis of Composite Sample Blank (CHB) from SASS-1 . . . D-ll
D-ll SSMS Analysis of lOp Cyclone Catch from SASS-2 ......... D-12
D-12 SSMS Analysis of 3p Cyclone Catch from SASS-2 ......... D-13
D-13 SSMS Analysis of ly Cyclone Catch from SASS-2 ......... D-14
D-14 SSMS Analysis of Particulate Filter from SASS-2 ........ D-15
D-15 SSMS Analysis of XAD-2 Resin from SASS-2 ............ D.^
D-16 SSMS Analysis of Composite Sample (CH) from SASS-2 ....... D_17
D-17 SSMS Analysis of Composite Sample Blank (CHB) from SASS-2 . . D-18
D-18 SSMS Analysis of Cyclone Catch from RAC-1 .......... D_19
xii
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TABLES (continued)
Number Page
D-19 SSMS Analysis of Neat Filter Particulate from RAC-1 D-20
I>-20 SSMS Analysis of Neat Filter Particulate from RAC-3 D-21
D-21 SSMS Analysis of CAFB Lignite D-22
D-22 SSMS Analysis of CAFB Limestone D-23
D-23 SSMS Analysis of CAFB Fines Return D-24
D-24 SSMS Analysis of CAFB Boiler Back D-25
D-25 SSMS Analysis of CAFB Boiler Sides D-26
D-26 SSMS Analysis of CAFB Stack Knockout D-27
D-27 SSMS Analysis of CAFB Stack Cyclone D-28
D-28 SSMS Analysis of CAFB Regenerator Cyclone D-29
D-29 SSMS Analysis of CAFB Gasifier Bed D-30
D-30 SSMS Analysis of CAFB Regenerator Bed . D-31
D-31 SSMS Analysis of CAFB Oil Feed D-32
D-32 SSMS Analysis of CAFB Bitumen D-33
xiii
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ACKNOWLEDGMENT
The authors gratefully acknowledge the guidance and support provided by
the Project Officer, Mr. Samuel Rakes, We thank Dr. Graham Johnes, Mr, Z,
Kowszun, Mr. Bert Ramsden and their coworkers at the Esso Research Centre,
Abingdon (ERCA), for their cooperation during the field test program and
Mr. Richard McMillan and Mr, Frank Zoldak of the Foster-rWheeler Energy Cor-
poration (FW) for helpful discussions. Finally, the authors acknowledge the
following GCA/Technology Division staff members; Mr, Robert Bradway,
Mr. Richard Graziano, and Ms, Verne Shortell for assistance with the field
test program; Dr. Kenneth McGregor, Dr. Carolyn Mayers, Ms, Mary Anne
Chillingworth, Ms. Mary Kozik, Ms. Patrice Svetaka, Mr. Charles Rutkowski,
Ms. Elyse Hoffmann, Ms. Denise Johnson and Ms. Sandra Sandberg for conducting
the laboratory analyses; and Ms. Ester Steele for typing the manuscript and
Ms. Dorothy Sheahan for preparing the figures.
xiv
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SECTION 1
EXECUTIVE SUMMARY
OVERVIEW
The Chemically Active Fluid Bed (CAFB) process is a technique whereby
high sulfur, high metal residual oil or coal is vaporized in a fluidized bed
of lime to produce a low Btu, low sulfur product gas which is then burned in
a conventional boiler to generate electrical energy. Most of the sulfur and
metals contained in the feed are captured by the lime. This spent lime is
subsequently processed to recover sulfur.
At present, the only operating CAFB unit is a 2.93 MW pilot plant at the
Esso Research Centre, Abingdon (ERCA), England facility.1 Foster-Wheeler Energy
Corporation (FW) is in the final construction stage of a 10 MW retrofit demon-
stration plant being installed in San Benito, Texas, at the La Palma Power
Station of the Central Power and Light Company. This unit is scheduled for
startup in early 1979.
The present study is an environmental assessment of the CAFB process for
lignite gasification/combustion. This document is an update of GCA/Technology
Division's 1976 environmental assessment of the oil-fired CAFB.2
The CAFB generates air, water and solid waste pollutants. The principal
source of air emissions is the boiler stack which is equipped with a cyclone
at both the pilot and demonstration plants. Fugitive emissions are produced by
feed and waste handling and storage. At the demonstration plant these sources
are contained by baghouses and, thus, will be minor contributors to total air
emissions. Water effluents, such as boiler blowdown and cooling tower outputs,
are similar to those produced by conventional combustion systems. Disposal of
sulfided limestone with high metals content is an important environmental prob-
lem. In view of the extensive efforts3 being conducted to develop environmentally
sound methods of spent stone treatment and disposal, the program reported upon
here was directed primarily toward the characterization and assessment of air
emissions from the CAFB,
The data needed for the environmental assessment were acquired during an
extensive sampling and analysis program of the emissions from the ERCA pilot
plant. Measurement techniques included Level I of EPA's Phased Approach,**
standard compliance methods and others selected to provide comparability of
the results of this program to those of the oil-fired study.2
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The evaluation of the results of the measurement program was accomplished
by use of the Source Analysis Model SAM/IA,5 comparison with standards of per-
formance for coal-fired boilers and comparison with analogous results obtained
by GCA for conventional lignite-fired combustion systems. Additional control
requirements are noted and recommendations for additional testing at the CAFB
demonstration plant are made.
In addition to the environmental analysis of the CAFB, the economic com-
parison between the oil-fired CAFB and alternate oil-fired energy production
techniques has also been updated from the 1976 report. Eight new HDS processes
are identified and described. Although the retrofit and fuel switching capa-
bility of the CAFB are not directly matched by HDS or FGD, the economic data
are instructive for evaluating the marketability of the CAFB process.
CONCLUSIONS
Particulate Emissions
The most pressing environmental concern facing the CAFB is the need for
additional control of particulate emissions. Particulate emission values
determined at the ERCA pilot plant and reported here represent essentially
uncontrolled emissions. The cyclone employed on the boiler stack was not
designed for the CAFB and consequently cannot be assumed to have a collection
efficiency of greater than 50 percent for total particulate nor greater than
negligible reduction capability for particulate in the respirable size range.
Emission values ranged from 2 to 4 lb/106 Btu, which represent a factor of
20 to 40 times higher than the New Source Performance Standard (NSPS) for
coal-fired boilers. Ten to thirty percent of the total particulate emissions
were in the respirable size range.
The CAFB particulate emission rate was about a factor of 3 lower than
that measured for a conventional lignite-fired utility boiler employing multi-
clones for particulate control, but a factor of 2,000 higher than a boiler
controlled by an ESP. To meet the current NSPS for coal-fired boilers and to
comply with any potential standard for small particulate emissions, controls
over and above the cyclones planned for the demonstration plant will be required.
Trace Element Emissions
Trace element emissions can be correlated directly with particulate emis-
sions. From a SAM/IA evaluation of these emissions, 14 elements (Ba, As, Ni,
Cr, Ti, P, Si, Mg, B, Be, Cd, Sr, Cu, Li) were identified which exceeded their
health MATE. For these elements, the ratios of emission rate to MATE ranged
from 1 to 500. Because almost all trace elements were found in particulate
samples, reduction of CAFB particulate emissions by 99.8 percent would have
the concommitant effect of lowering all trace element emissions to levels below
their MATE values. However, because of the uncertainty of the MATE values
employed in the SAM/IA analyses and the level of precision of +3 of the trace
element emission values, such a stringent level of control may7 in fact not
be required. *
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Trace element emissions from the conventional lignite-fired boiler are
such that MATE values are exceeded by 12 elements by as much as a factor of
800. A comparison of actual emission rates with worst case values derived
from lignite feed elemental composition for both the CAFB and conventional
boilers supports the observation made for oil-fired CAFB operation that gas-
ifier bed stone selectively adsorbs certain trace elements contained in the
CAFB fuel.
Gaseous Emissions
As observed in the oil-fired CAFB study, NOX emissions are significantly
lower than the NSPS. The highest measured NOX emission rate for lignite-firing
was 0.09 lb/106 Btu. Although this value may be low by a factor of 2 (due to
possible sample degradation) the NSPS value of 0.7 lb/106 Btu is well in excess
of the actual emission rate.
The measured S02 emission rate corresponds to 0.55 lb/106 Btu, roughly
half the NSPS requirement. Sulfur recovery efficiency (SRE) ranged from 30
to 80 percent for the 0.5 percent sulfur lignite fired. At the lower SRE,
the S02 emission rate was equal to about the NSPS value. Clearly, if the CAFB
process is to be capable of using high sulfur fuel, the conditions favoring
capture of fuel sulfur by bed stone must be optimized.
Emissions of Cj and G£ hydrocarbons (the only gaseous hydrocarbons present
at levels above the detection limit) were well below their respective health-
based MATE values.
Organic Emissions
Organic emissions varied widely as a function of gasifier operating con-
ditions. The principal conclusion which can be drawn from a comparison between
CAFB emissions and those from six conventional lignite-fired boilers is that
when operated efficiently, gaseous (Ci - Cg) organic emissions from the CAFB
are equivalent to those from conventional systems and emissions of heavier
organics are lower than the average of those from conventional boilers.
Functional groups found in condensible CAFB air samples are esters, hydro-
carbons, ketones, and amides. Other compounds provisionally identified are
alcohols, phenols, amines, nitrocompounds, ethers, substituted aromatics, and
organosilicon compounds. No SAM/LA analysis was performed for the organic
emissions. Level II analysis of emissions from the demonstration plant will
be required to generate the type of data necessary to perform a meaningful
environmental assessment of organic emissions.
Economic Comparison of Oil-Fired CAFB, FGD and HDS
The CAFB is unique as a retrofit application to natural gas-fired boilers
because the process can accept a wide variety of liquid and solid fuels including
those with high sulfur and high metals contents. Although flue gas desulfur-
ization (FGD) and hydrodesulfurization (HDS) are capable of providing desulfur-
ization equivalent to the CAFB, they are in general less capable of demetal-
lization and reduction of NO., emissions. Consequently, any strict economic
-------
comparison of the three oil-fired systems must be qualified by considering
the attendant differences in technical capabilities of CAFB, FGD and HDS.
Regenerable CAFB and FGD systems are more expensive than their once-
through counterparts. Projected capital costs for the CAFB are double those
of the other two processes. Estimated operating costs are also significantly
higher for CAFB, as compared to flue gas desulfurization systems. In order
to operate the CAFB on a competitive basis with flue gas desulfurization
systems, high sulfur, high metals crudes must be $2 to $3 per barrel cheaper
than low metals, medium sulfur content residual or distillate oils. At present,
this per barrel differential requirement is roughly twice the market situation.
-------
REFERENCES
1. Craig, J. W. T., et al. Chemically Active Fluid Bed Process for Sulphur
Removal During Gasification of Heavy Fuel Oil - Third Phase. Office of
Research and Development, U.S. Environmental Protection Agency, Washing-
ton, D.C. Publication No. EPA-600/2-76-248. September 1976. (NTIS No.
PB 268-492/AS).
2. Werner, A. S., C. W. Young, M. I. Bornstein, R. M. Bradway, M. T. Mills,
and D. F. Durocher. Preliminary Environmental Assessment of the CAFB.
GCA/Technology Division, Bedford, Massachusetts. Prepared for the U.S.
Environmental Protection Agency, Research Triangle Park, North Carolina.
Publication No. EPA-600/7-76-017. October 1976. 324 pp. (NTIS No.
PB 262-001/AS).
3. Rakes, S. L. A Synoptic Review of the EPA Chemically Active Fluid Bed
Program. Energy Spectrum 21:130-133. May 1978.
4. Dorsey, J. A., L. D. Johnson, R. M. Statnick, and C. H. Lochmuller.
Environmental Assessment Sampling and Analysis: Phased Approach and
Techniques for Level I. U.S. Environmental Protection Agency, Research
Triangle Park, North Carolina. Publication No. EPA-600/2-77-115.
June 1977. 38 pp.
5. Schalit, L. M., and K. J. Wolfe. SAM/IA: A Rapid Screening Method for
Environmental Assessment of Fossil Energy Process Effluents. Prepared
for the U.S. Environmental Protection Agency, Office of Research and
Development, by Acurex Corporation. Publication No. EPA-600/7-78-015.
February 1978.
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SECTION 2
INTRODUCTION
THE CHEMICALLY ACTIVE FLUID BED (CAFB) PROCESS
The Chemically Active Fluid Bed (CAFB) process was developed in the late
1960's by the Esso Research Centre, Abingdon (ERCA), England as a means to
generate electrical energy from high sulfur, high metal heavy fuel oil.
During the early and mid 1970's, the process was demonstrated at the pilot
plant stage to be capable of providing energy effectively while simultaneously
limiting sulfur oxide, nitrogen oxide, vanadium and nickel air emissions to
levels lower than those produced by conventional oil-firing techniques. With
the realization that the supply of oil and natural gas available to the United
States might soon be restricted, and that, consequently, coal would be the in-
creasingly dominant fossil fuel source of energy in the coming decades, a de-
cision was made to investigate the efficacy of the CAFB using coal as a retro-
fit for existing natural gas-fired boilers. To this end, a pilot plant test
employing a Texas lignite was carried out at ERCA in early 1978.
In the CAFB process, oil or coal is fed continuously into a fluidized
bed of limestone maintained at 850°C +70°C by preheated substoichiometric air.
In this gasification unit fuel is successively vaporized, oxidized, cracked
and reduced. Sulfur in the fuel forms various gaseous species which in turn
react with the bed stone to form calcium sulfide coated lime. Some of the
fuel bound trace elements are also bound to the lime particles. The low Btu,
low sulfur product gas generated in the gasifier is passed through cyclones to
a conventional natural gas boiler where it undergoes combustion. The sulfided
stone left in the gasifier is cycled to a regenerator unit in which it is
oxidized to produce lime which is returned to the gasifier and sulfur dioxide
which is sent to a sulfur recovery unit.
The ERCA pilot plant is a 2.9 MW unit. Foster-Wheeler Energy Corporation
is constructing a 10 MW retrofit demonstration plant in San Benito, Texas at
the La Palma Power Station of Central Power and Light Company.2 This unit is
scheduled for startup in early 1979.
BACKGROUND
In 1976 GCA/Technology Division prepared for EPA a report entitled
"Preliminary Environmental Assessment of the CAFB."3 The major part of that
volume was devoted to an evaluation of the emission rates and potential en-
vironmental effects of the pollutants comprising all air, water and solid
waste streams. This evaluation centered around a field sampling program
-------
carried out at the ERCA pilot plant during oil gasification and subsequent
laboratory analysis of samples collected during testing. Because this program
was performed during the period in which EPA was developing the Phased Approach
to Environmental Assessments, the sampling and analytical procedures employed
included both standard EPA enforcement methods and elements from the evolving
Level I procedures. In addition to the experimental measurement activities,
the preliminary assessment included: an engineering evaluation of potential
fugitive emissions from storage and handling of feedstocks and spent material;
estimates of emissions associated with cooling and boiler water; and an air
quality impact assessment for the oil-fired CAFB La Palma retrofit.
The major conclusions of the environmental assessment of the oil-fired
CAFB are summarized below:
• Reduction of Stack Particulate Emissions - Total stack particulate
emissions from oil-fired operation of the pilot plant, 30 percent
of which are in the respirable size range, were only slightly lower
than the New Source Performance Standard (NSPS) for oil-fired
boilers. During stone feed-startup these emissions considerably
exceeded the NSPS. The vanadium concentration of these particulates
is such that the vanadium emission rate is only slightly lower than
the Multi-Media Environmental Goal (MEG) for this element. Under
coal-fired operation of the CAFB, proposed for the demonstration
plant, the particulate emission problems nay be even more pro-
nounced. Foster-Wheeler is designing more efficient cyclones than
were installed at the pilot plant. Extensive particulate emission
rate measurements at the demonstration plant should be undertaken
for all operating modes and for all fuels.
• Reduction of SOg Emissions During Abnormal Operating Conditions -
Blockage of the gasifier-regenerator transfer duct causes satura-
tion of gasifier bed stone and a resultant increase in SO? emis-
sions. Operation of the CAFB in this mode for extended time
periods should be avoided. Continuous SO? monitoring is
recommended.
• N0y Stack Emissions - Measurements of NOX emissions for three
separate runs were about 25 percent of the NSPS for oil-fired
boilers.
• Trace Elements Other Than Vanadium - Stack emission rates of no
element other than vanadium approached creating ambient levels on
the order of the MEG for that element.
• Environmentally Acceptable Disposal of Spent Stone - The demonstra-
tion plant will generate 6000 kg/day (13,000 Ib/day) and a 250 MM
commercial size unit 79,000 kg/day (173,000 Ib/day) of sulfided,
metal-contaminated lime which must be treated before being dis-
posed of by selling, landfilling, or ocean dumping.
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* Detailed Investigation of Organic Stack Emissions - Flue gas
analyses indicated the possible presence of quinone, carbonyl
compounds and aliphatic hydrocarbons in sufficient quantities
to produce ambient concentrations in the neighborhood of the
MEG's for these species. Organic emissions are highly depen-
dent on gasifier and boiler operating conditions and should
be analyzed with greater specificity than was possible in the
present study.
The 1976 report included an overview of other desulfurization technologies
(hydrodesulfurization (HDS) and flue gas desulfurization (FGD)) and a compara-
tive economic evaluation of CAFB, FGD and HDS. Sixteen HDS processes were iden-
tified as actual or potential commercial systems. The unit operations of each
process were identified and the attendant environmental impacts of each unit
operation were discussed.
PROGRAM OBJECTIVES
The goals of this program are to: evaluate the potential environmental
impact of a lignite-fired CAFB; identify additional control needs for this
process; provide recommendations for further environmental assessment of the
CAFB; and update (from our 1976 report) capital and operating costs for the
oil-fired CAFB and alternative oil-fired energy systems.
To collect the data necessary to the environmental assessment, an exten-
sive sampling and analysis program of the emissions from the ERCA pilot plant
was conducted. The measurement protocols closely followed Level I of EPA's
Phased Approach to Environmental Assessments.11 Additional measurements were
conducted to ensure comparability of the results of this study with those of
the oil-fired assessment and to provide specific data known to be required
from the previous program and necessary for a clearer understanding of the
CAFB process itself. Because of the extensive work on the environmental and
economic implications of various solid waste disposal options being per-
formed by other contractors,5'6 in parallel with this study, this assessment
focused primarily upon flue gas emissions from the CAFB.
The assessment of the environmental impact of the CAFB utilizes the re-
sults of the measurement program in conjunction with standards of performance
for coal-fired power plants and the Source Analysis Model,7 a scheme for ranking
the relative hazards of pollutant emissions and waste streams. The output of
this environmental assessment consists of the identification of control require-
ments for the CAFB and recommendations for follow-on assessment activities to
be conducted at the demonstration plant.
In addition to the environmental analysis of the CAFB, the economic com-
parison between the oil-fired CAFB and alternate oil-fired energy production
techniques has also been updated from the 1976 report. Eight new HDS processes
are identified and described. Although the retrofit and fuel switching capa-
bility of the CAFB are not directly matched by HDS or FGD, the economic data
are instructive for evaluating the marketability of the CAFB process.
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REFERENCES
1. Craig, J. W. T., et al. Chemically Active Fluid Bed Process for Sulphur
Removal During Gasification of Heavy Fuel Oil - Third Phase. Office of
Research and Development, U.S. Environmental Protection Agency, Washing-
ton, D.C. Publication No. EPA-600/2-76-248. September 1976. (NTIS No.
PB 268-492/AS).
2. Foster-Wheeler Energy Corporation. Chemically Active Fluid Bed Process
(CAFB). Preliminary Process Design Manual. U.S. Environmental Protec-
tion Agency, Research Triangle Park, North Carolina. U.S. EPA Contract
No. 68-02-2106. December 1975.
3. Werner, A. S., C. W. Young, M. I. Bornstein, R. M. Bradway, M. T. Mills,
and D. F. Durocher. Preliminary Environmental Assessment of the CAFB.
GCA/Technology Division, Bedford, Massachusetts. Prepared for the U.S.
Environmental Protection Agency, Research Triangle Park, North Carolina.
Publication No. EPA-600/7-76-017. October 1976. 324 pp. (NTIS No.
PB 262-001/AS).
4. Dorsey, J. A., L. D. Johnson, R. M. Statnick, and C. H. Lochmuller.
Environmental Assessment Sampling and Analysis: Phased Approach and
Techniques for Level I. U.S. Environmental Protection Agency, Research
Triangle Park, North Carolina. Publication No. EPA-600/2-77-115.
June 1977. 38 pp.
5. Keairns, D. L., et al. Fluidized Bed Combustion Process Evaluation
(Phase I - Residual Oil Gasification/Desulfurization Demonstration
at Atmospheric Pressure). Volume I - Summary. Prepared for the U.S.
Environmental Protection Agency, Office of Research and Development.
Publication No. EPA-650/2-75-027a. March 1975. (NTIS No. PB 241-834/AS) .
6. Stone, R., and R. Kahle. Environmental Assessment of Solid Residues
from Fluidized-Bed Fuel Processing: Final Report. U.S. Environmental
Protection Agency. Publication No. EPA-600/7-78-107. June 1978. 339 pp.
7. Schalit, L. M., and K. J. Wolfe. SAM/IA: A Rapid Screening Method for
Environmental Assessment of Fossil Energy Process Effluents. Prepared
for the U.S. Environmental Protection Agency, Office of Research and
Development, by Acurex Corporation. Publication No. EPA-600/7-78-015.
February 1978.
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SECTION 3
PROCESS DESCRIPTION
INTRODUCTION
A description of three development stages of the CAFB process, as applied
to residual oil gasification, is provided in GCA's preliminary environmental
assessment of the CAFB.1 These include the 2.93 MW pilot plant constructed at
the Esso Research Center, Abingdon (ERCA), England, the 22 MW demonstration
plant currently in the final stages of construction at Central Power and Light's
La Palma, Texas, facility (a joint effort by Foster-Wheeler Equipment Corpo-
ration and Central Power and Light), and a conceptual full scale commercial
unit based on the Foster-Wheeler design. Operating parameters noted in this
section are based on the results of GCA's sampling effort conducted at the
ESSO pilot plant during lignite gasification, data supplied by Foster-Wheeler,
and simple mass balance calculations.
OVERVIEW
In the CAFB process, lignite is consecutively vaporized, oxidized, cracked
and reduced in a fluidized bed of lime to produce a low Btu gas. This gas,
from which a large portion of the sulfur has been removed by the lime, travels
from the gasifier through cyclones for particulate removal and then into a
conventional boiler for combustion. At the ESSO pilot plant the boiler flue
gas encounters a knockout baffle and another cyclone before entering the stack.
Under normal operating conditions, lime is continuously cycled between, the
gasifier and the regenerator where lime sulfided in the gasifier is oxidized
to CaO. Sulfur dioxide produced in the regenerator is fed to the boiler stack
(in the case of the pilot plant) or chemically treated to recover sulfur (for
demonstration and larger designs). Spent lime is withdrawn from the regenerator
for disposal on an intermittent or continuous basis. To maintain sulfur removal
efficiency, an equivalent amount of limestone is added to the gasifier.
GeneralDescription and Chemistry of Gasification
The basic components of the CAFB process are the gasifier and regenerator.
Figure 1 schematically illustrates the materials fed to and withdrawn from
these unit operations. The quantity of limestone added to the gasifier is de-
termined by the Ca/S molar feed ratio necessary to provide the desired level
of S02 control. Air is fed into the gasifier at about 30 percent stoichiometric
in order to partially oxidize the fuel oil and produce a temperature 871°C (1600°F)
10
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suitable for vaporization and cracking of the fuel. Flue gas from the boiler
at approximately 17l°C (340°F) is recirculated to the gasifier for temperature
control. A low Btu product gas is circulated from the gasifier to the boiler.
The predominant reactions taking place in the gasifier are as follows:
Fuel thermal cracking •* C + H2 + hydrocarbons + H2S •«• CS2 + COS
CaO + H2S
CaO + COS
CaO + 1/2CS2
CaS + H20
CaS + CO;
± CaS + 1/2C02
The equilibria for these reactions are well to the right. Approximately 5 per-
cent of the input limestone as calcium oxide is reduced to calcium sulfide on
each pass of stone through the gasifier.
DESULFURIZED
PRODUCT GAS
REACTED STONE
REGENERATED STONE
OFF GAS
REGENERATOR
SPENT MATERIAL
AIR
RECYCLED
FLUE OAS
AIR
Figure 1. Gasifier-regenerator schematic.
General Description and Chemistry of Regeneration
The regeneration step is accomplished in a reaction vessel adjacent to
the gasifier. Bed material comprised of CaO, CaS, carbon and ash is fed to
the regenerator where it reacts with a stoichiometric quantity of air by the
reactions:
11
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Carbon deposited on the stone during gasification is oxidized to C02- Regen-
erator solids analyzed by ESSO during the GCA sampling run ranged between 0.1
to 2.8 percent carbon.
The off-gas from the regenerator contains SC>2, COa and N£ derived from
the influent air. Spent solid material consists of CaO, CaSOi^, CaS and ash.
In the Foster-Wheeler demonstration plant and 250 MW unit, off-gas will be
transported to the RESOX™ system for recovery of elemental sulfur, and spent
solids will be conveyed to a solids cooler and storage bin. At the ESSO
pilot plant regenerator off-gas passes through a cyclone and then into the
boiler stack.
ESSO PILOT PLANT
Figure 2 is a schematic diagram of the ESSO pilot plant. Some physical
modifications have been made since our first investigation to allow for solid
fuel gasification. Input and output streams to and from each unit operation
are labelled and their mass flow and characteristics are given in Table 1.
The quantities listed in this table are those projected at steady-state con-
ditions, based on recorded operating characteristics during the lignite sam-
pling run. Parameters will vary during startup, shutdown, and atypical operat-
ing modes.
FOSTER-WHEELER DEMONSTRATION PLANT
The Foster-Wheeler demonstration plant shown schematically in Figure 3
contains, in addition to the basic gasifier and regenerator units, a RESOX™
system for sulfur recovery from the regenerator off-gas, a spent solids hand-
ling system and a coal storage and feed system for lignite gasification. Mass
flows and stream conditions listed in Table 2 are based on FW design param-
eters and mass balance calculations by GCA. The extent of operations of the
RESOX™ unit will depend upon fuel sulfur concentration. This sulfur recovery
system is designed for maximal performance with 7 to 8 percent S02 input; thus,
for CAFB gasification of low sulfur fuel the RESOX™ may be operated inter-
mittently to allow for S02 buildup in the regenerator.
In GCA's oil-fired assessment report, auxiliary handling and storage unit
operations were discussed in depth for both oil and coal-firing. Because
these operations do not appear to present appreciable environmental problems
and because they are similar to facilities used in conventional boilers, we
have not updated the earlier treatment.
12
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U)
IFIER AIR BLOWERS
Figure 2. Unit operations flow diagram of the ESSO pilot plant.
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TABLE 1. ESSO PILOT PLANT MASS FLOW RATES
Mass flow race
Temperature
Process stream
kg/sec
Ib/hr
°C
I. Lignite feed to gasifier
2. Limestone feed to gasifier
3. Gasifier to regenerator stone transfer
4. Regenerator to gasifier stone transfer
5. Product gas to cyclones
6. Cyclone solids return to gasifier
7. N< gas to solids transfer lines
8. I'roduct gas to boiler
9. Air to regenerator
10. Spent solids from regenerator
11. Regenerator off-gas to cyclone
12. Hi-j-oniTntor off-gait, cyclone to stack
I'l. I'liic ga» from boiler
14. Flue gas recirculated to gasifier
15. Flue gas to Tuyere Blower
16. Recycled flue gas from cyclone
17. Air to gasifier
IB. Kliip gas to stack
19. Solids from boiler flue gas cyclone
20. Solidn from recycled flue gas cyclone
21. Solids from regenerator off-gas cyclone
22. Solids from gasifier cyclones
23. Stack emissions
24. Solids from high efficiency cyclone
0.04-0.07 (350-550)
0.001-0.003 (10-20)
,Intermittent
0.09-0.18
Intermittent
(700-1,400)
792-913 (1,458-1,675)
0.006-0.015 (45-115)
Intermittent grab samples 1,055 (1,931)
1,055 (1,931)
0.05-0.10 (400-800)
0.66-0.71 '5,200-5,600)
14
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•MHOMC
IWMt BHTBIIVTIm I ' yq- Pi
\\\@ 77/
9ULFUR MECIKUlATIMI
TANK
Figure 3. Unit operations flow diagram of the Foster-Wheeler CAFB demonstration plant,
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TABLE 2. MASS FLOW RATES FOR FOSTER-WHEELER 22 MW CAFB
DEMONSTRATION PLANT
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
21.
24.
25.
26.
Process stream
Limestone to gasifier
Product gas to boiler
Gasifier to regenerator stone transfer
Regenerator to gasifier stone transfer
Regenerator off-gas: total
S0?
C02
Cyclone HO lids from regenerator to spent
lime cooler baghousc
Water and steam to off-gas cooler
Off-gas from cooler to RESOX™
Air to inert gas generator
Natural gas to inert gas generator
Cooling water for inert gas generator
Air to RESOX™
TM
Combined gas to RESOX
TM
Anthracite coal to RESOX
RESOX™ ash to storage
TM
Elemental sulfur from RESOX to
sulfur tower
Drainage from sulfur tower
Steam to sulfur tower
Water to steam drum
Startup steam to sulfur cooler and steam drum
Steam purge from steam drum
(Slowdown from steam drum and sulfur cooler
Sulfur discharge
RESOX™ tail gas
Spent solids from regenerator to cooler
Air to spent lime cooler
Mass flow rate Temperature
kg/sec Ib/hr °C °F
0.06-0.11 (450-900)
10.1-11.4 (80,000-90,000)* 871 (1,600)
3.15-4.41 (25,000-35,000)
3.15-4.41 (25,000-35,000)
0.50-0.57 (4,500-4,500) 1,038 (1,900)
649 ( 1 , 200)
0.67* (5,300)
0.05f (360)
22. 7f (180,000)
538f (1,000)
154f (HO)
I60f (320)
0.02f (122) i,038f (1,900)
(Continued)
16
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TABLE 2 (continued).
Mass flow race
Process stream
kg/sec
Ib/hr
Temperature
°C °F
27. Spent lime cooler vent to baghouse
28. Spent lime from cooler to hopper baghouse
29. Spent lime from baghouse to spent lime hopper
30. Air emissions from spent lime hopper baghouse
31. Recycle flue gas and tail gas to gasifier
and regenerator
32. Air to gasifier and regenerator
33. Combined air/flue/tail gas to gasifier
34. Combined air/flue/tail gas to regenerator
35. Fuel oil to gasifier (if used)
36. Air emissions from limestone storage baghouse
37. Fugitive emissions from limestone handling
38. Air emissions from limestone surge
hopper baghouse
39. Air emissions from coal storage silo
baghouse
40. Fugitive emission!) tram coal handling
41. Air emissions from coal surge hopper baghouse
42. Lignite feed to gasifier
43. Air emissions from RESOX coal storage
baghouse
44. Air emissions from main stack
6.52-6.58 C> I, 700-52,200)
7.94 (63,000)
3.15
(25,000)
Assuming flue gas recirculation to gasifier.
Design capacity quantities baaed on Foster-Wheeler CAFB demonstration plant design drawings.
17
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REFERENCES
1. Werner, A. S., C. W. Young, M. I. Bornstein, R. M. Bradway, M. T. Mills,
and D. F. Durocher. Preliminary Environmental Assessment of the CAFB.
GCA/Technology Division, Bedford, Massachusetts. Prepared for the U.S.
Environmental Protection Agency, Research Triangle Park, North Carolina.
Publication No. EPA-600/7-76-017. October 1976. 324 pp. (NTIS No.
PB 262-001/AS).
18
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SECTION 4
MEASUREMENT PROGRAM
INTRODUCTION
The experimental phase of the CAFB Environmental Assessment was designed
to conform to the data and procedural requirements of an environmental assess-
ment as defined by Level I of EPA's Phased Approach1 and to provide data com-
parable to those acquired for the oil-fired study. Data on some internal process
streams were also collected to assist in control design and implementation.
As noted previously, the measurement program emphasized emissions from the
flue gas, although samples from the fuels, solid waste and process cyclones were
also collected. The flue gas was sampled with SASS,* modified RAC, and in-stack
impactor trains. The use of these three systems allowed comparison of total
particulate collected by SASS and Method 52 RAC trains, and particle size dis-
tribution as determined by SASS and impactor. Tenax resin, used in a module
incorporated into the Method 5 train, provided a measure of gaseous organic
emissions in addition to those collected by XAD-2 resin in the SASS.
Organic analyses of SASS, Tenax, and solid samples followed the Level I
procedures based on gas chromatography, liquid chromatography, and infrared
spectroscopy. Level I inorganic analyses were based on spark source mass
spectrometry, atomic absorption spectroscopy, and wet chemistry. Additional
particulate analyses were performed with X-ray photoelectron spectroscopy.
This section presents the sampling and analytical procedures used in the
measurement program and summarizes the field and laboratory results. Detailed
field results are tabulated in Appendix C and laboratory results in Appendix D.
FIELD TESTS
Protocol
Field sampling of the ERCA CAFB pilot operation was conducted from
January 24 through January 27, 1978. Testing was designed as a Level I Environ-
mental Assessment of the flue gas and particulate emissions. Additionally,
solid waste effluents, coal and limestone feeds and internal particulate and
solid samples were collected for laboratory analysis. The principal purpose
of the testing was to characterize the physical and chemical parameters of the
stack emission through onsite analysis of specific chemical species and by the
collection of flue gas samples for further laboratory analysis.
SASS - Source Assessment Sampling System.
19
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The flue gas was sampled In the stack through the three ports installed
approximately 6 diameters upstream from the flue gas entry into the stack.
The ports were spaced 120 degrees apart and included two with a 3-inch BSP
and one with a 5-inch BSP fitting. Multiple ports were necessary to allow
simultaneous testing.
In-stack testing was by SASS train, Andersen impactor, modified RAC
train, and integrated bag sampler. In addition to trains used for the chemical
and particulate emissions testing, the physical parameters of the flue gas
were measured by initial pitot traverses. In-stack thermocouples were used to
monitor flue gas temperatures, and the flue gas moisture was determined by
gravimetric analysis of moisture gain in the sampling trains. The results of
the calculated physical parameters were used to determine the required nozzle
sizes and sampling rates for the subsequent in-stack tests.
Particulate sampling was accomplished using a Method 5 train and a SASS
train. The Method 5 train was also used to test simultaneously for S02/SC>3 by
Method 83 in three of the five RAC train tests. The other two RAC tests used
modified trains for the purpose of collecting gaseous organic species as well
as total particulate.
Gaseous organic species were collected by the addition of a gas adsorbent
column, shown in Figure 4, to the RAC train. This column contained precon-
ditioned Tenax-GC, a porous polymer compound with the ability to adsorb organ-
ics heavier than Cg. In the modified RAC train the flue gas, after passing
through the particulate filter, was cooled to slightly above its dewpoint by
means of a thermostated cooling bath and water jacket. The gas then passed
through the adsorbent cell which collected the organic constituents. Any con-
densate which filters through the cell was collected in a glass receiver (not
shown). After completion of the sampling, the complete adsorbent column was
capped and returned to the laboratory for extraction and analysis. Any con-
densed liquid can also be extracted and analyzed for organics. This modified
train thus provided a sampling method for both organics and total particulate.
The SASS train, which is the train specified in the Level I assessment,
also provides both particulate and organic testing of flue gas emissions.
In addition, the SASS train allows determination of the particulate size dis-
tributions and also provides samples for inorganic analyses of volatiles in
the flue gas emissions. For this program, two tests by SASS train were con-
ducted. The methods used were according to those specified by the Level I
Manual. A description of the SASS train and its operation may be found in
that document. All SASS samples were recovered in the field laboratory
provided by ERCA and then prepared for shipment to GCA's laboratory for
analysis.
It was necessary to perform in-field analyses of the volatile gases. The
tests for these included the Method 8 testing for S02/S03, gas chromatography
analysis of hydrocarbons (Ci-Cg) and fixed inorganic gases, and chemilumin-
escent analysis of NO-NOX emissions.
The Method 8 sampling was included with three of the particulate tests by
modification of the standard RAC train. All solutions and standardizations
20
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FLOW DIRECTION
8-MM GLASS
COOLING COIL
GLASS WATER
JACKET
RETAINING SPRING -i
GLASS FRITTED
DISC
FRITTED STAINLESS STEEL DISC
15 MM SOLV SEAL JOINT
Figure 4. Adsorbent sampling system.
-------
were performed in the field laboratory. Samples were analyzed after the com-
pletion of each test in order to prevent any degradation of samples.
Tests for C]-C6 hydrocarbons, fixed inorganic gases and NO-NOx were per-
formed in the field laboratory from integrated bag samples of the flue gas.
Bag samples were taken with an integrated gaseous sampling train as described
in the Level I Manual. Tedlar bags were used for samples. The bags were
transported to the field laboratory, located approximately 100 yards from the
stack, for analysis at the completion of the test.
Field testing for Ci~C6 hydrocarbons was by gas chromatography. A Model
511 AID gas chromatograph equipped with FID detector, 6-ft stainless steel
Poropak Q column, and heated l-m£ gas sampling valve was used for analysis.
A recorder with an integrator was used to record the results of the analysis.
Samples were compared against standard gas mixtures for qualitative and
quantitative analysis.
The analysis of fixed inorganic gases, specifically C02, 02, N£ and CO,
was by gas chromatography. The Model 511 AID equipped with a TCD detector
and a l-m£ sampling valve was used for analysis of these components. The
columns used in this instrument were a 2-ft chromosorb 102 with a 4-ft 13X
molecular sieve. Samples were compared against standard gas mixtures for
qualitative and quantitative analysis.
The bag sample was also used for NO-NOx analysis. A Thermo Electron
Model 10AR Chemiluminescent gas analyzer provided immediate analysis of the
flue gas for both NO and NOX.
It was intended that gas chromatography analysis of H2S, S02, and COS
by a flame photometric detector would also be used. This instrument was
inoperative during this testing program.
When possible, analysis was performed on site to minimize transportation
losses. These analyses included gravimetric analysis of filters and washes.
The S02/S03 analyses were performed in the field laboratory with standard
solutions prepared in the field. As described previously, the bag samples
were analyzed in the field laboratory for gaseous components. Samples requir-
ing more complex treatment and analysis were shipped to the home laboratory
along with suitable blanks.
In addition to flue gas, samples of lignite, limestone, spent stone,
gasifier bed, and cyclone catches were collected by ERCA at 6-hour intervals
and provided to GCA for analysis.
Results
The field testing program was designed to provide an evaluation of the
particulate and gaseous emissions from the CAFB unit. The results obtained
from the field analysis include the particulate loading rates, the particulate
size distributions, the physical parameters of the flue gas, and the gas
analysis.
22
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The data shown in Table 3 provide results of physical parameters from
the two tests with the SASS train and the five tests with the modified RAC
trains. The moisture determinations were obtained from gravimetric analysis
of the moisture gain of each train. The reason for the variation in these
values is unknown, but it should be noted that the exact temperature control
and high volume of the SASS train would possibly provide a more representa-
tive value than the RAC values.
Particulate loadings as obtained from gravimetric analysis of the filter,
cyclones, and washes of each test are also included in Table 3. There is
some variation in the comparison of these results between trains which would
be expected since each train was a single point sample. Also, it should be
noted that while RAC train tests and SASS train tests were run simultaneously
when possible, the test time duration and volume of gas sampled were signifi-
cantly different. The results of these tests do provide an indication of the
particulate loadings for the CAFB unit. The values obtained translate into
2 to 4 lb/106 Btu for total emissions.
The results of the particulate sampling by SASS train also provide a
characterization of the particle size distributions. The results of this
breakdown, along with the other measured parameters for each test, are
included in Table 4.
The SASS train particle size distribution results are shown graphically
in Figure 5. These graphs were obtained using the calculated cut diameters
FA
for each cyclone as determined by the cyclone equation D = Dp /——
where Dpj is calibrated aerodynamic particle diameter for Q1 = 6.41 acfm at
400°F and PJ = 0.026 centipoise. The values for the percent weight were
obtained from the values reported in Table 4, as calculated from the total
particulate for each cyclone.
The results of the particle size distribution calculations indicate that
98 percent of the particulate was greater than 1 pm, with the mean particle
diameter between 6 and 7 pm. These results show good correlation to the
results of the three in-stack Andersen impactor runs which are presented by
the conventional log normal plots of the particle size distributions shown
in Figure 6.
Field analyses were also performed for gaseous species in the flue gas.
As described previously, the RAC train was modified to provide determinations
of S02 and 803. The measured parameters for these three tests are found in
Table 3, and the results of the field analyses are included in Table 5.
Table 5 also includes the results of the field analyses of the bag
samples. The bag samples were taken simultaneously with the train sampling
on 3 of the 4 test days. The results of the fixed gas analysis show a large
degree of variation presumably due to changes in operating conditions. The
value for 02 reported on January 27 appears abnormally low, but a check of
calculations shows closed deviation of less than 3 percent.
23
-------
TABLE 3. CAFB PARTICULATE TEST DATA
N3
Test No.
RAC-1
SASS-1
RAC-2
SASS-2
RAC-3
RAC-4
RAC-5
Date
1/24
1/24
1/25
1/26
1/26
1/27
1/27
Qs*
(dscfm)
1200.7
1100.3
1388.1
1271.6
1346.7
1422.7
1053.8
Qaf
(acftn)
1463.3
1590.0
1891.6
1878.0
1844.6
1972.8
1536.0
Moisture E.A.*
(%) (%)
7.1
10.0
6.6
12.1
9.0
4.5
9.4
39.9
53.6
67.1
53.6
53.6
29.4
28.0
Part.
loading
(gr/dscf)
1.
0.
1.
1.
0.
0.
0.
0381
9632
5291
1994
9906
8520
7917
Vmstd§
(dscf)
29
919
32
266
32
26
24
.525
.167
.740
.291
.876
.318
.630
Test design
Part. ;
SASS
Part. ;
SASS
Part. ;
Part. ;
Part. ;
S02/S03
organics
S02/S03
organics
S02/S03
Qs - Stack flow rate at dry standard conditions.
^Qa - Stack flow rate at actual stack conditions.
*E.A. - Calculated excess air.
vmstd ~ Volume of flue gas sampled at dry standard conditions.
-------
TABLE 4. CAFB PARTICULATE MASS AND SIZE EMISSIONS
DATA MEASURED BY SASS TRAIN
SASS-1
Parameter
Rate or value
Flue gas flow rate
Temperature at sampling port
Flue gas moisture
Total particulate loading
1100.3 dscfm
214°F
10.0%
0.9632 gr/dscf
Particle size fraction collected Percent of total particulates
< 1 ym (filter)
> 1 ym
> 3 ym
> 10 ym
1.
26.
50.
21.
2%
9%
3%
6%
SASS-2
Parameter
Rate or value
Flue gas flow rate
Temperature at sampling port
Flue gas moisture
Total particulate loading
1271.6 dscfm
214°F
12.0%
1.1994 gr/dscf
Particle size fraction collected Percent of total particulates
< 1 ym (filter)
> 1 ym
> 3 ym
> 10 ym
1.8%
31.8%
44.1%
22.4%
25
-------
100
90
80
70
60
30
40
30
>
UJ
<
5
10
9
8
7
6
5
2
a
o
a:
u
4 -
3 -
Z -
i
02
SASS
I
5 10 20 SO 70 90 95 96 99
PERCENT BY WEIGHT LESS THAN STATED DIAMETER
99.8 9395
Figure 5. Particulate size distributions measured by SASS train.
26
-------
N)
10
9
8
7
6
S
4
o
UJ
I-
UJ
UJ
_j
o
u
o
bJ
0.9
o.e
0.7
0.6
O.S
0.4
O.S
0.2
O.I
i l T
RUN NO. 2
RUN NO. I
NO. 3
_L
JL
J—I I—I—I L
_L
J—L
0.01 O.I as I 2 5 10 20 30 50 70 60 90 98 98 99 99.9 99.99
NUMBER PERCENT LESS THAN OR EQUAL TO STATED SIZE
Figure 6. Particulate size distributions measured by in-stack impactor.
-------
TABLE 5. CAFB GAS ANALYSIS
Test date C°2 °2 C0 N0 N0x S02 S03 Cj C2"
/«x /«\ /*\ (ppmv) (ppmv) (ppmv) (ppmv) (ppmv) (ppmv)
00
1/24 10.1 9.1 <0.05 28 33 101.9 0.8 21.4 2.8
1/25 6.1 9.0 <0.05 14.5 15.7 - - 6.5 <0.5
1/26 - - - - - 299.7 1.3 - -
1/27 6.4 5.3 <0.05 26 42 185.0 0.9 <0.5 <0.5
No hydrocarbons above C2 detected, MDL 0.5 ppmv.
-------
The results of hydrocarbon analysis on January 24 showed detectable hydro-
carbons in the C\ and G£ boiling point range as determined according to the
Level I method. The values of detectable hydrocarbon appeared to decrease
during the testing, with no hydrocarbons detected above the 0.5 ppmv detecta-
bility limit of the instrument for the third bag sample taken January 27.
The values for NO and NOX reported in Table 5 were obtained from analysis
of bag samples by chemiluminescent instrument. The instrument was standardized
against a standard NO gas and checked for standardization after being returned
to the home laboratory. The results shown for the test on January 25 are ab-
normally low and may be the result of sample degradation due to a long holding
time between sampling and analysis. Recent data gathered by other EPA contrac-
tors indicate that NO and NOX collected in aluminized bags from streams con-
taining air and moisture can degrade by a factor of 2 after a few hours. The
runs completed on January 24 and January 27 were each analyzed within 2 hours
of collection. Although Tedlar, not aluminized, bags were used in this study,
it is possible that the NO/NOjj values reported in Table 5 could be low by as
much as a factor of 2.
Discussion
The testing program was designed to comply with the EPA definition of an
environmental assessment for the CAFB operation. In addition to the defined
Level I environmental assessment, a number of other testing methods were in-
cluded in this program to provide additional information on the physical and
chemical properties of the emissions from the process.
Field tests with the RAC train and the SASS train were conducted simulta-
neously so that measurements could be compared. The results of the reported
particulate loadings showed a variance of 4 percent and 12 percent for the
tests No. 1 and No. 2. This variation is possibly due to the fact that SASS
sampling was at a single point while RAC test No. 1 was traversed over 12
points. It was not possible to traverse with RAC test No. 2 since the addition
of the organic sampling column prohibited the movement of the train. Sampling
for RAC test No. 2 was thus at a single point.
The organic sampling column which was adapted to the RAC train used
Tenax-GC as the organic adsorbent. The SASS train which is also designed to
collect organic emissions used XAD-2 resin as the collection medium. This
design allowed the comparison of the efficiencies of the two organic collect-
ing resins. The result of this comparison is discussed in the Laboratory
Analysis discussion of this report.
In addition to the organic emissions and total particulate emissions
testing, the SASS train provided particle size information analysis of the
three cyclone catches. These results, which are reported in the field analysis
section, were compared to the particle size information which was obtained
using Andersen impactore. The results of the two test designs showed good
agreement with regard to size distributions and mean particle diameter.
The test program had been designed to provide comparison of sulfur
species analysis methods. Unfortunately, the flame photometric gas
29
-------
chromatograph was inoperative, and the results reported for S02 and S03 species
were derived solely from the modified RAC train sampling.
There were other problems during the sampling program which required the
alteration of the original plan. A principal problem was the sporadic opera-
tion of the CAFB unit, which resulted in schedule changes and shorter than
specified SASS train sampling run time. The number of intended RAC train runs
was reduced due to the changes in unit run schedule.
Other problems which were independent of the CAFB operation also caused
delays and alteration of the intended schedule. Primary among these was the
problem of power supply for the test equipment and laboratory instruments.
Power for all of these instruments was provided by gasoline-powered generators.
During testing one of the four generators was inoperative due to a short in
the generator windings. As a result, the power supply for the laboratory was
available only when one of the other three generators was not needed for the
sampling equipment. This problem resulted in delays in some analyses per-
formed by gas chromatography and NOX analyzer.
Other problems were encountered during the test program, but on-site
modifications and the cooperation of CAFB personnel remedied these situations
to the satisfaction of the intent of the test program. The overall goals of
program design were completed and the results reported are considered repre-
sentative of the CAFB unit at the conditions tested.
LABORATORY ANALYSIS
Analysis Protocol
The laboratory analysis program was designed to characterize particulate
and gaseous emissions from the CAFB pilot plant during operations with lignite.
Using the Level I procedures for an environmental assessment as the framework
for the analytical scheme, a program was developed which provided information
on the CAFB process as well as information for an environmental assessment.
The types of sample analyses carried out are summarized in Table 6. SASS
samples were analyzed for organics and inorganics by Level I methods with the
exception that particulate samples were not combined (i.e., filter with lu
cyclone, 3v cyclone with lOu cyclone). This provided a more complete analysis
of the particulate size fractions which it was hoped would reveal information
on their origin. Bulk samples were also analyzed by Level I methods to deter-
mine the composition of solid wastes generated by the CAFB and to provide in-
formation on the process which may aid in the design of controls.
Samples collected using the modified RAC train, in which particulate on
a filter and gaseous organics on Tenax-GC resin were collected, were analyzed
as shown. Because our experience has shown that most organic emissions are
found on the resin samples, the particulate catches from RAC runs 1 to 5
were combined separately for organic compounds; therefore, a composite sample
was made. Similarly, no inorganic analyses were performed on the Tenax resin
Two particulate samples were analyzed separately for bulk elemental composition.
30
-------
TABLE 6. LABORATORY ANALYSIS PLAN FOR CAFB-LIGNITE STUDY
Organic Analysis
• SASS samples
Particulate
Resin (XAD-2)
Condensate
Rinses
• RAC samples
Particulate (composite of probe rinses; runs 1 to 5)
Tenax (runs 2 and 4)
• Bulk samples
Spent solids
Inorganic Analysis
• SASS samples
Particulate
Resin (XAD-2)
Condensate
Impingers
Rinses
• RAC samples
Particulate (runs 1, 3 and 5)
• Bulk samples
Lignite
Limestone
Spent solids
Cyclone fines
Gasifier bed
Surface Analysis
• SASS samples
Particulate
• RAC samples
Particulate
• Impactor substrates
31
-------
Organic Analyses—
Level I organic analysis is designed to provide a semiquantitative (± 3*)
determination of the classes and concentrations of organic substances con-
tained in waste streams emitted by stationary energy and industrial processes.
In this study, particulate, flue gas and solid waste were analyzed for
organics.
In general, three categories of organic compounds are defined by Level I:
gaseous, volatile and nonvolatile. Volatile organics are defined as those
which boil between 90° and 300°C; nonvolatile organics boil above 300°C, and
gaseous organics boil below 90°C. Gaseous organics which are measured in the
field have been discussed earlier. Organic analyses were performed on all SASS
train components except the impingers. All stainless steel components were
rinsed with methylene chloride or a 50-50 (v/v) mixture of methylene chloride
with acetone to recover organics. Organics in the condensate, particulate and
XAD-2 resin were recovered by methylene chloride extraction. Tenax resin was
extracted with pentane.
Because the extracts, in general, are too dilute to detect organic compounds
using almost any instrumental technique available, all organic liquid and sol-
vent extracts were concentrated to 10 m£ via a Kuderna-Danish (K-D) concentrator.
(The Kuderna-Danish concentrator is a glass apparatus which removes most of the
solvent while minimizing the loss of the other volatile components.)
The concentrated samples were analyzed in two stages. The first stage of
the analysis consists of four different methods. A sample aliquot is evapo-
rated to dryness and weighed. The residue is then transferred to KBr plates
and analyzed by a grating infrared spectrophotometer. The output of these
steps is a measure of the amount of nonvolatile organic matter present in each
sample and an indication of the functional groups which are present.
Another sample aliquot is injected into a gas chromatograph (GC). The
instrument is calibrated so that the organic compounds boiling between 90° and
300°C (i.e., the total chromatographic organics or TCO) are quantified relative
to n-decane. If the TCO is greater than 75 vg/m3, the quantity of organics
boiling within certain ranges is also determined. The volatile organics boiling
within the ranges 90° to 110°, 110° to 140°, 140° to 160°, 160° to 180°, 180°
to 200°, 200° to 220°, 220° to 240°, 240° to 260°, 260° to 280°, and 280° to
300°C were quantified relative to n-decane and reported as €7, Cg, Cg, Cjp • GH,
Ci2» Ci3, Cin, Cjs and Cig alkane equivalents. The difference in the response
of the GC detector between decane and the other hydrocarbons has been shown to
be +5 percent, which is well within the accuracy requirements of Level I anal-
ysis. The samples were not analyzed further if the total quantity of volatile
and nonvolatile organic emissions (the sum of the TCO emissions and the gravi-
metric components) was less than 0.50 mg/m3.
In the second stage of analysis, those samples with organic emission fac-
tors larger than 0.50 mg/m3 were fractionated by liquid chromatography (LC).
(The LC method used provides some separation of components according to po-
larity.) A sample aliquot was transferred to the top of a liquid chromato-
graphic column packed with 6.5 gm silica gel in pentane. The column was
32
-------
developed by gradient elution using the solvents given in Table 7, and seven
fractions were collected. The fractions were analyzed by the gravimetric and
infrared methods described previously. If the unfractionated sample contained
more than 10 percent volatile organic material, each fraction was also analyzed
by the gas chromatographic method discussed above.
TABLE 7. SOLVENTS USED FOR LIQUID
CHROMATOGRAPHY
Fraction
Solvent
1
2
3
4
5
6
7
25 m*
10 mH
10 m£
10 m£
10 m£
10 m£
10 m£
pentane
20% CH2C12/ pentane
50% CH2Cl2 /pentane
CH2C12
5% CH3OH/CH2C12
20% CH3OH/CH2C12
50% CH3OH/CH2C12
Inorganic Analysis—
Level I inorganic analysis consisted of a Spark Source Mass Spectrographic
(SSMS) elemental survey along with specific analyses for mercury, fluoride,
chloride, and sulfate. Both liquid and solid samples were received in the lab-
oratory for analysis. Organic materials, both liquid and solid, were combusted
in a Parr oxygen bomb to destroy the organic matrix. Solids that were primarily
inorganic (with the exception of glass fiber particulate filters) were analyzed
directly by SSMS, but were digested with aqua regia for mercury and fluoride
analyses. Particulate filters were generally acid digested for the SSMS analysis
as well, because of the cohesion and sparking problems that are associated with
having glass filters in the graphite electrodes. All particulate samples for
SSMS were run neat whenever possible. Samples for chloride and sulfate analysis
were prepared by extraction with hot water. Table 8 summarizes the inorganic
sample preparation scheme.
Mercury was analyzed by a cold vapor AA technique. The sulfate determi-
nation was a turbidimetric procedure and specific ion electrodes were used to
analyze both fluoride and chloride. These analyses are described further in
the following paragraphs.
Spark Source Mass Spectrography (SSMS)—SSMS was used to perform a semi-
quantitative elemental survey analysis on the Level I samples taken. The
analysis was performed using a JEOL Analytical Instruments, Inc. Model
JMS-01BM-2 Mass Spectrograph. The JMS-01BM-2 is a high resolution, double
focusing mass spectrometer with Mattauch-Herzog ion optics. The instrument
is specially designed to carry out high sensitivity trace element analysis
with the aid of an RF spark ion source and photoplate detection. An aliquot
of each sample to be analyzed is incorporated into two electrodes which are
33
-------
TABLE 8. INORGANIC SAMPLE PREPARATION SCHEME
Sample
Preparation
Analysis
Particulate filters
Cyclone catches
Composite
XAD-2 resin
Impinger composite
Bulk samples
Lignite
Others
Aqua regia extraction SSMS, Hg, F
Hot water extraction SOif, Cl
Neat SSMS
Aqua regia extraction Hg, F
as
Hot water extraction SOi,,Cl
None required
Parr bomb
None required
SSMS, Hg, F", Cl"
SSMS, Hg, F", Cl"
Hg
SOj,
Parr bomb SSMS, Hg, F , Cl~,
Aqua regia extraction SSMS, Hg, F~
Hot water extraction SO^, Cl~
Composite of peroxide impinger, condensate, and acid module rinse.
Composite of second and third impingers.
34
-------
then mounted in the ion source of the mass spectrometer. These electrodes
are "sparked" with a high voltage discharge which decomposes and ionizes
the electrode material. Because of the high energy of the electrical dis-
charge, most of the material is reduced to its elemental form. The ions
formed are collected with focusing plates and subsequently measured in the
mass spectrometer. Spark source mass spectrometry can be used to detect
elemental concentrations down to 10~9 g (one nanogram). Although the sensi-
tivity may vary somewhat from sample to sample, practically all elements
(except H, C, N, 0, and the inert gases) in the periodic table can be detected.
Interferences can result from the formation of multiply charged ions, ion
clusters and molecular ions such as oxides, hydrides, hydroxides, and carbides.
These interferences, coupled with the fact that the discharge conditions in
the ion source are not easily reproduced, limit the accuracy of the technique.
Spark source mass spectrometry, however, is very useful as a survey tool, and
is capable of providing semiquantitative results (i.e., accurate to within a
factor of 2 or 3).
Mercury - cold vapor—The cold vapor mercury analysis is based on the
reduction of mercury species in acid solution with stannous chloride and the
subsequent sparging of elemental mercury, with nitrogen, through a quartz
cell where its absorption at 253.7 run is monitored.
Sulfate - turbidimetric—The basis of the analysis is the formation of a
barium sulfate precipitate in a hydrochloric acid medium with barium chloride
in such manner as to form barium sulfate crystals of uniform size. The ab-
sorbance of the barium sulfate suspension was measured by a transmission
photometer and the sulfate ion concentration determined by comparison of the
reading with a standard curve.
Fluoride—Fluoride was determined potentiometrically using a selective
ion fluoride electrode in conjunction with a standard single junction sleeve-
type reference electrode and a pH meter having an expanded millivolt scale.
Sample pH was between 5 and 9. Polyvalent cations of Si"1"1*, Fe"1"3 and Al+3
interfere by forming complexes with fluoride. The addition of a pH 5 total
ionic strength adjuster buffer (TISAB II) containing a strong, chelating agent
preferentially complexes aluminum (the most common interference), silicon,
and iron and eliminates the pH problem.
The addition of TISAB II also provides a high total ionic strength back-
ground to help mask the difference in total ionic strengths between samples
and standards. However, the TISAB II cannot entirely compensate for this dif-
ference due to the very high and variable level of ionic strength in the
Level I SASS samples. Thus, a known addition technique is employed to elim-
inate the necessity of drawing different calibration curves for different types
of samples.
Chloride—Chloride was determined potentiometrically using a solid state
selective ion chloride electrode in conjunction with a double junction refer-
ence electrode and a pH meter having an expanded millivolt scale. The solid
state electrode is used because it is not sensitive to the higher levels of
nitrate, sulfate or bicarbonate which could be present in many of the samples.
35
-------
This method does require that the sample and standards have the same total
ionic strength. Because samples can have a very high and variable level total
ionic strength, a known addition technique is employed to eliminate the neces-
sity of drawing different calibration curves for different types of samples.
Surface analyses—Included as part of the analytical scheme of this study
is surface analysis by X-ray photoelectron spectroscopy, or ESCA, which is not
part of Level I. ESCA is capable of surface (<_ 20& depth) elemental analysis
of solid and particulate samples, with relative amounts of each element being
reported as percent atomic. ESCA can also give information on the oxidation
states of a number of elements, a capability which was applied to the study
of carbon and sulfur species in this program. Coupled with the use of argon
ion etching to remove surface layers, ESCA can provide profiling to supplement
surface and SSMS bulk analyses. Further information on the technique is pro-
vided in the report of the CAFB-fuel oil study.1*
Results of Laboratory Analyses
Organic Results—
To determine organic flue gas emissions, samples collected by both SASS
and RAC trains were analyzed. Table 9 summarizes the volatile, nonvolatile
and total organic emissions determined for SASS runs 1 and 2, Tenax RAC runs 2
and 4, and the aggregate content of the five particulate catches from RAC runs
1 to 5. As noted in Table 3, the runs represented by the first four columns
in Table 9 were performed on different days, thus precluding any direct com-
parison between the SASS and RAC-Tenax collection efficiencies;
TABLE 9. TOTAL >C6 ORGANIC EMISSIONS (yg/m3)
PA™ M i o»™« i Tenax Tenax Particulate
SASS No.l SASS No. 2
TCO*
Gravimetric
Total
221
565
786
307
21,725
22,032
290
5,050
5,340
1,070
17,200
18,270
360
2,540
2,900
Total Chromatographable Organics (Cy-Cjg B.P. Equivalents).
The low total organic emissions found in SASS No. 1, relative to the other
runs, may be attributable to recycle of fines from the gasifier cyclone to the
gasifier. This recycle operation was suspended after SASS No. 1 to alleviate
particulate accumulation in the boiler. Although the excess air values for
SASS 1 and 2 were identical, the factor of three difference between the S02
emissions (see Table 5) during these runs indicates that during SASS No. 1
the CAFB was more "chemically active" than during SASS No. 2. The high GI
and C2 emissions determined by gas chromatography during SASS No. 1 may be
indicative of more efficient gasification and pyrolysis of heavy lignite
organic matter during that run.
36
-------
Tables 10 and II display the distribution of organic emissions among the
SASS components for runs 1 and 2. Emissions called individual alkane equiva-
lents refer to compounds boiling in the ranges Cy-Cig. As can also be noted
in Table 9, SASS No. 1 has a high proportion of TCO material. Again, this is
consistent with the relatively large Cj and 62 values and with the inference
that the gasifier was particularly effective during SASS No. 1. Consistent
with the oil-fired results, most of the capturable organics are found in the
resin module (XAD-2, module rinse and condensate).
Table 12 contains a similar summary of individual alkane equivalents
(lAE's), TCO and gravimetric weights for Tenax RAC 2 and 4 and the particulate
composite RAC 1-5 samples. As with the SASS samples, a peak in the IAE region
occurs around Cg. The sizable quantity of extractable organics found in the
RAC particulate is somewhat surprising. The composite nature of this sample
precludes assignment of high organic emissions to any one run. These results
do suggest, however, that higher total organic emissions may have occurred
during RAC runs 1, 3 or 4 than during either SASS or Tenax runs.
Infrared spectra of all samples listed in Tables 9 to 12 were obtained to
discern the functional groups contained in each sample. All spectra are con-
tained in Appendix D. Tables 13 and 14 contain interpretations of spectra
taken of samples comprising SASS 1 and 2. Figures 7 and 8 are spectra of XAD-2
resin extracts from SASS 1 and 2, respectively. The resin extract from SASS
No. 1 contains a significant contribution from saturated hydrocarbons while
the spectrum contained in Figure 8 is dominated by oxygenated compounds.
Summary Tables 13 and 14 show a wide variety of hydrocarbons and heteroatom
groups. The inability to obtain meaningful spectra from some particulate ex-
tracts may be due to evaporation losses occurring as a result of heat lamp
drying of KBr plates. The use of a heat lamp for rapid evaporation of methylene
chloride solvent was instituted to prevent condensation of water vapor on the
IR plates which would result in masking the spectrum.
Table 15 summarizes the IR interpretations of RAC Tenax and particulate
extracts. The groups identified in these samples are similar to those found
in the SASS samples. The indication of major amide emissions in the Tenax
samples may indicate a higher collection efficiency for these compounds by this
resin over XAD-2. Additional experimental work needs to be carried out to
determine if this is in fact the case or if amides may be present as impurities
in Tenax, more easily extracted by pentane (used with Tenax) than by methylene
chloride (used with XAD-2) or formed in secondary reactions.
Three samples met the Level I weight criterion (gravimetric plus TCO) for
liquid chromatography (LC) separation: XAD and module rinse from SASS No. 2
and Tenax from RAC No. 4. Tables 16, 17 and 18 list the distribution of ma-
terial in the seven fractions and the functional groups found by IR in each
fraction. From the fractional distributions and functional group identifica-
tions shown in these tables it is apparent that esters, ketones and aliphatic
hydrocarbons are the principal organic emissions from the CAFB. Following in
importance are substituted aromatics and possibly amines, ethers, amides, al-
cohols, phenols and nitrosubstituted compounds.
37
-------
TABLE 10. ORGANIC EMISSIONS IN CAFB SASS SAMPLES, RUN No. 1 (ug/m3)
oo
IAE* l°V
cyclone
7
8
9 2.49
10 1.07
11
12
13
14
15
16
TOO 3.56
Grav. b.r.'''
TO 3.56
3y ly
cyclone cyclone
-
-
7.44 - 5.78
1.90 2.98
_
-
0.624
-
_
_
9.34 9.38
b.r.1" b.r.1"
9.34 9.38
Particulate Probe XAD-2 Module
filter rinse resin rinse
-
-
-
-
-
0.599
2.66
-
5.39
4.69
13.3
28.7
42.0
_ _
4.66 11.2 8.95
2.00
22.5
b.r.1"
22.8
4.57
7.06
0.131 1.26
3.60
4.79 75.0 8.95
b.r.1" 467 69.3
4.79 542 78.3
Condensate
-
4.88
91.4
-
-
0.232
-
-
-
-
96.5
b.r.f
96.5
Individual alkane equivalents.
b.r. - blank removes; sample less than or equal to blank.
-------
TABLE 11. ORGANIC EMISSIONS IN CAFB SASS SAMPLES, RUN No. 2 (yg/m3)
u>
vo
IAE
7
8
9
10
11
12
13
14
15
16
TCO
Grav.
TO
10y 3y Ip Particulate Probe
cyclone cyclone cyclone filter rinse
-
-
6.31 31.1 6.24
- 0.659
0.838
_
_
_ _ _ _ _
14.6 - 2.86
_ _ _ _ -
6.31 31.1 20.8 - 4.35
80.1 303 102 b.r.t b.r.f
86.4 334 123 b.r.1" 4.35
XAD-2
resin
-
-
-
b.r.*
b.r.f
b.r.f
-
-
b.r.
-
b.r.f
3240*
3240*
Module
rinse
19.4
6.20
-
—
_
-
4.12
-
28.3
-
58.0
18000*
18100*
Condensate
-
9.62
158
_
_
-
-
-
18.4
_
186
b.r.*
186
Individual alkane equivalents.
b.r. - blank removes; sample less than or equal to blank.
'Only the first three digits are significant.
-------
TABLE 12. ORGANIC EMISSIONS IN
CAFB RAC SAMPLES
(Wg/m3)
IAE*
7
8
9
10
11
12
13
14
15
16
TCO
Grav.
TO
Tenax :
RAC-2
-
-
41.8
115
-
32.4
8.53
12.7
82.7
-
290
5050
5340
Tenax: Particulate:
RAC-4 RAC 1-5
5.53
28.8
230 324
731
13.4 7.17
17.4
-
-
60.7
10.5
1070 360
17200 2540
18300 2900
Individual alkane equivalents.
40
-------
TABLE 13. INTERPRETATION OF IR SPECTRA FROM GRAVIMETRIC RESIDUES OF UNFRACTIONATED
SAMPLES, SASS RUN No. 1
Sample code
Medium
Minor
Trace
XAD-2 resin
Condensate
Esters,
saturated
hydrocarbons
Aliphatic
hydrocarbons
Module rinse
Probe rinse
Particulate filter
lp cyclone
3y cyclone
10y cyclone
Possible
nitrosubstituted
compounds,
ethers
Esters, ketones;
possible: ethers,*
organos i1icon compound s,
nitrocompounds, substi-
tuted aromatics
Esters*
Saturated esters,
saturated hydrocarbons
Possible: aliphatic
ethers
Possible: aryl or
unsaturated esters
or ethers
Saturated esters;
possible: aryl or
unsaturated esters or
ethers, organosilicon
compounds
May be saturated, unsaturated, aryl.
Blank removes IR spectrum.
-------
KJ
TABLE 14. INTERPRETATION OF IR SPECTRA FROM GRAVIMETRIC RESIDUES OF UNFRACTIONATED
SAMPLES, SASS RUN No. 2
Sample code
Medium
Minor
Trace
XAD-2 resin
Module rinse
Condensate
Probe rinse
Particulate filter*
ly cyclone
3u cyclone
lOy cyclone
Aryl or unsaturated
esters; ketones*
hydrocarbons
Saturated hydrocarbons,
saturated esters
Possible:
nitrocompounds,
ethers
Aliphatic hydrocarbons
esters;* possible:
aromatic hydrocarbons
Aryl esters;
possible:
substituted
aromatics,
aliphatic ethers
Saturated ketones;
possible ethers
Aliphatic ethers
May be saturated, unsaturated and/or aryl,
Blank removes IR spectrum.
-------
WAVELENGTH, *icro«t
25
8 9 10 12 IS 20 3040
4000 3500 3000 2500 2000 I BOO 1600 1400 1200 1000 BOO 600 400 200
FREQUENCY ,c»-'
Figure 7. IR spectrum of XAD-2 resin from SASS-1. Major peaks
indicate esters, saturated hydrocarbons; possible
ethers and nitrosubstituted compounds.
2.5
WAVELENGTH, •icroit
5 6 7^ 8
9 10
IS 20 30 40
4000 3500 3000 2500 2000 1800 1600 1400 1200 1000 800 600 400 200
FREQUENCY, c»-'
Figure 8. IR spectrum of XAD-2 resin from SASS-2. Major peaks
indicate aryl or unsaturated esters, ketones, hydro-
carbons; possible ethers and nitrocompounds.
-------
TABLE 15. INTERPRETATION OF IR SPECTRA FROM GRAVIMETRIC RESIDUES OF RAC SAMPLE EXTRACTS
WITHOUT LC FRACTIONS
Sample code
Major
Medium
Minor
Trace
RAC-2, Tenax Amides*
(primary,
secondary)
RAC-4, Tenax Hydrocarbons,*
esters,* ketones;*
possible: alcohols/
phenols, amines,
amides
RAC 1-5,
Partlculate
Ethers, hydrocarbons;
possible: amines,*
alcohols/phenols
Esters, ketones
saturated hydrocarbons;
possible: ethers,*
organosilicon compounds,
substituted aromatica
Possible:
organo-
silicon compounds
Possible: ethers
Possible:
esters, ketones*
May be saturated, unsaturated, aryl.
-------
TABLE 16. INTERPRETATION OF IR SPECTRA FROM GRAVIMETRIC RESIDUES OF XAD-2 RESIN
EXTRACT AND ITS LC FRACTIONS, SASS RUN No. 2
Sample code Major
XAD-2 resin*
LC-1
Median
Aryl or unsaturated
esters; ketones,
hydrocarbons
Aliphatic hydrocarbons
Minor
Possible: nitro-
coapounds, ethers
Aromatic
hydrocarbons
Trace
Esters (aryl
or unsaturated) ;
Weight
distribution
(percent)
100*
6.2
LC-2
LC-3
LC-4
LC-5
LC-6
LC-7
Esters'
possible; ethers
Hydrocarbons;'
possible: saturated
ethers
Possible:
saturated
hydrocarbons,
ethers
Esters, ketones
Possible:
amines, alcohols/phenols,
ethers.* nitrocompounda,
amines'
Unsaturated
esters; saturated
and unsaturated
ketones
Possible:
ethers, nitro-
compounds
0.4
3.8
20.8
6.7
54.9
7.3
The spectra of some fractions are stronger than the spectrur. of the unfractionated sample. Therefore, some
compounds may show up in the spectrum of a fraction, but not in the spectrum of the unfractionated sample.
k.
May be saturated, unsaturated, and/or aryl.
Column percent recovery: 91 percent.
'Blank removes 1R spectra.
-------
TABLE 17. INTERPRETATION OF IR SPECTRA FROM GRAVIMETRIC RESIDUES OF MODULE RINSE
AND ITS LC FRACTIONS, SASS RUN No. 2
Scode6 Maj°r Medium Minor
2-MR
LC-1
LC-2*
LC-3*
LC-4
LC-5
LC-6
LC-7
Aliphatic hydrocarbons
esters (saturated,
unsaturated, aryl);
possible: aromatic
hydrocarbons
Esters (saturated) Esters
(unsaturated,
aryl)
Esters (saturated)
Esters (saturated)
Weight
Trace distribution
(percent)
Saturated
ketones ;
possible:
ethers
Aliphatic hydrocarbons
Possible: ethers
Esters (unsaturated,
aryl)
Esters (unsaturated,
aryl)
Ethers (saturated)
lOO"1"
46.9
13.5
5.1
16.4
1.6
14.4
3.0
*
Blank removes IR spectrum.
Column percent recovery: 51 percent.
-------
TABLE 18. INTERPRETATION OF IR SPECTRA FROM
EXTRACT AND ITS LC FRACTIONS, RAC
GRAVIMETRIC RESIDUES OF TENAX RESIN
RUN No. 4
Sample
code
RAC, Ten ax
LC-1
LC-2
LC-3
LC-4
LC-5
l.C-6
LC-7
Major Medium
'Hydrocarbons,*
esLcrK,* ketones;*
possible: alcohols/
phenols, amines,*
amides,* ethers
Saturated hydrocarbons
Saturated hydrocarbons
Substituted aromatics,
eatera; poaaible: amines,*
amides,41 ethers,* unaaturated
alcohol a
Eatera; poaaible:
amides, amines, ethers*
Esters,* ketones;*
possible: amides,*''
Amines,*''' ethers,*'*
alcohols/phenolst
KtUc'rH, kctiinpK:
A r
poMulblu: ainlui'H, >
amines,*'* ethers,*''''
alcohols/phenols*
Weight
Minor Trace distribution
(percent)
Aromatic Aryl or vinyl
hydrocarbons ethers
Unsaturated
hydrocarbons
Possible:
nitro-
subetituted
compounds ,
phenols
Possible:
unaaturated
alcohols,
nitroaubatituted
compounds
Ketones, esters;
poaaible: ethers,
phenols, amines ,*•'
100f
8.8
0.2
11.4
21.6
36.6
18.3
3.0
Hay be saturated, unsaturated, and/or aryl.
Column percent recovery: 114 percent.
TMay posaeBS an isopropyl group attached to N or 0.
-------
These data indicate that XAD-2 used in the SASS train and Tenax used in a
modified RAC train produce qualitatively similar results. Differences in
operating conditions over the several days of testing preclude quantitative
comparison of the organic emissions data. In Section 5 the organic emissions
data from the CAFB are compared with emissions from conventional lignite-fired
boilers and with CAFB emissions during oil-firing.
Table 19 summarizes the organic composition of spent stone withdrawn from
the regenerator. Over 99 percent of extractable material is nonvolatile.
The esters and ethers contained in the material reflect the highly oxidizing
nature of the regenerator. It is not unreasonable to assume that high molecular
weight tars also remain on the stone; however, these compounds are probably
insoluble in methylene chloride and, hence, undetectable in the Level I scheme.
TABLE 19. ORGANIC COMPOSITION OF
SPENT STONE (mg/kg)
TCO Gravimetric^" Total
0.80 195 196
*
Individual Alkane Equivalents:
Cllt = 0.60 Gig = 0.2
.i,
Infrared analysis shows minor
amounts of aryl and unsaturated
esters and ethers.
Inorganic and Trace Element Results—
The inorganic analysis program centered upon Spark Source Mass Spectro-
graphic (SSMS) analysis of stack particulate, bed material, internal solids
and vapor species collected on resin and in solution. Appendix D contains
tabulations of the elemental compositions of each sample analyzed. In addition
to SSMS, wet chemical methods and X-ray photoelectron spectroscopy (ESCA) were
used to determine mercury, sulfate, fluoride, chloride and particulate surface
species. The elemental compositions of lignite and limestone feeds are reported
in Tables 20 and 21. Elements present in appreciable concentrations in one
feed are also present in the other, thus no indicator elements are apparent.
Tables 22 and 23 contain trace element amounts and emission factors, de-
termined by SSMS, for all SASS fractions for runs 1 and 2. The emission fac-
tors listed in the last column of each table are compared with MATE values and
with emissions from conventional lignite-fired sources in Section 5. The
milligram quantities tabulated under each sample designation refer to the total
number of milligrams of each element determined to be in each sample. Ranges
of values reported under "Total SASS" have as minima the sum of all real
48
-------
TABLE 20. SSMS ANALYSIS OF CAFB LIGNITE*
Element
U
Th
Bi
Pb
Tl
Au
Pt
Ir
Os
Re
W
Hf
Lu
Yb
Tm
Er
Ho
Dy
Tb
Gd
Eu
Sm
Nd
Value
(ppm)
1.2
3.8
< 0.33
13
< 0.47
< 0.23
<- 0.64
< 0.35
< 0.40
*. 0.25
< 0.60
< 0.75
< 0.17
< 0.27
< 0.16
< 0.25
< 0.15
< 0.26
< 0.16
< 0.43
< 0.12
< 0.73
1.1
Element
Pr
Ce
La
Ba
Cs
I
Te
Sb
Sn
In
Cd
Pd
Rh
Ru
Mo
Nb
Zr
Y
Sr
Rb
Br
Se
As
Value
(ppm)
1.4
3.4
10
320
0.86
0.16
4.9
0.38
1.9
IS*
0.69
< 0.18
< 0.064
< 0.23
0.73
6.9
65
8.2
230
7.8
11
< 9.3
< 57
Element
Ge
Ga
Zn
Cu
Ni
Co
Fe
Mn
Cr
V
Ti
Ca
K
S
P
Si
Al
Mg
Na
F
B
Be
Value
(ppm)
< 3.0
14
11
19
10
2.2
0.57%
100
13
28
0.14%
MC*
0.49%
0.86%
76
MC
MC
0.44%
80
92
88
0.55
Concentrations based on "as received" lignite weight.
IS - Internal Standard.
rMC - Major Component.
49
-------
TABLE 21. SSMS ANALYSIS OF CAFB LIMESTONE FEED
Element
U
Th
Bi
Pb
Tl
Au
Pt
Ir
Os
Re
w
Hf
Lu
Yb
Tm
Er
Ho
Dy
Tb
Gd
Eu
Sm
Nd
Value
(ppm)
< 0.63
< 0.63
< 0.28
8.3
< 0.33
< 0.43
< 1.2
< 0.65
< 0.74
< 0.46
< 0.61
< 0.75
< 0.17
< 0.27
< 0.16
< 0.46
< 0.15
< 0.26
< 0.07
< 0.28
< 0.12
< 0.48
< 0.50
Element
Pr
Ce
La
Ba
Cs
I
Te
Sb
Sn
In
Pd
Rh
Ru
Mo
Nb
Zr
Y
Sr
Rb
Br
Se
As
Ge
Value
(ppm)
0.21
0.43
0.95
160
0.06
19
< 0.35
0.95
5.5
IS*
< 0.34
< 0.12
< 0.43
0.87
< 0.05
0.55
0.24
210
1.7
< 21
< 4.4
< 328
< 0.17
Element
Ga •
Zn
Cu
Ni
Co
Fe
Mn
Cr
V
Ti
Ca
K
S
P
Si
Al
Mg
Na
F
B
Be
Li
Value
(ppm)
< 0.07
< 1.4
3.8
4.4
0.23
590
7.5
0.63
3.6
40
MC+
230
400
27
400
150
0.36%
110
150
5.5
0.003
0.09
IS - Internal Standard.
MC - Major Component.
50
-------
TABLE 22. TRACE ELEMENT EMISSIONS IN SASS SAMPLES, RUN No. 1
U- -t Sf-.-l.ti =
LSC-
twE'
U
TH
el
Pft
ft
61,
IR
uS
wt
A
MF
LU
YB
TH
ER
HO
0»
TH
GO
EU
SM
TO
MR
CE
L«
B*
CS
I
U
S*
SN
CO
PO
w
1 1 i ... j .•
C»CU"
•J.003B
0,00-U
",U(l2b
0,014
o,uo2
0.025
n.Uj-7
0.0075
0,027
< >1 ,'0"05I""
* 0,072
< o.onni
< 0,036
0,013
0,075
0.17
0,051
O.UU
0,56
H.I
0.021
3,032
< u.OiV
j ,u2e
0.072
u.019
< 0.042
< O.OOT8
in-'
6
U.OOUi
< 0.0001
< 0.0027
0.0010
O.OOUB
0.013
0,0040
0.060
0.033
o|o031
< O.OOn?
< ti.0o53
0.0050
< 0.0?5
0.027
< 0,0016
< 0.0012
Ail)
C'T,)
< n . o i «
< 0.026
< 0.0061
< y , 2h
< 0 . 0 I 0 0
< u.OJU
< 0.021
< 0.023
< O.Olu
< 0,019
< O.OC«
< 0,0056
< O.OOB2
< 0,0050
< 0.015
* 0,0008
< U.006U
< 0.0023
< 0,0063
< 0.0016
< 0.015
< 0.018
< 0.0012
< O.OOul
< 0.0007
< 0,076
< 0,0006
< 0,013
< I) , 0 1 1
t 0.0071
0,039
< 0.011
< 0.0100
< 0,0037
C°S»«Ktrt
(vG)
< II . 0 | J
< ii 02>l
< u. OUOl
< i..07o
< u , o o 7 o
< U , 0 1 0"
< 0.016
< 0,017
< 0.011
< o.oia
< 0.018
< u.0012
< 0,0061
< 0.0037
< 0.011
< 0.0036
< 0.0062
< 0.0017
< 0.0062
< 0.002B
< 0.011
< o.oia
< 0.0024
< 0.0012
< 0.0035
0.013
< u.0006
< 0.0093
< o . o o / e
< u,005«
1.3
0.029
< U.007B
< 0.0027
1UHL
(-U
O.an
1.1
0.0 1« lu O.B5
U ,6
< u.obl
< o.OSo
< 0.077
< O.OtJu
< 0.053
< 0.15
< O.S/
< 0,15
< 0,11
< O.U26
< '.0.1?
O.OOOB TO 0.055
0.0041 1(1 0.23
< 0.007C1
<- o.ii
0,0)4 TU 0,062
O.oBfl' TO 0.39
- 0.76
0.25
it U
4. a
69.
0.0911
0 . 0 J2
< 0.21
0.17
1.7
0,11
< 0.19
< 0,022
t"ISSlli»«
FUUND
("G/PSC")
0.017
0.043
O.OOOb 10
fl.lt*
< 0.0020
< 0,0019
< 0.0030
< 0.0032
< 0,0020
< 0.0056
< 0.022
< 0.0u5tt
« 0.0055
< 0,0010
< 0.0061
< 0,0001 TO
0.0002 Tu
< 0.0001
€ 0,0042
0,0005 ro
0.0031 TO
0.029
0.009*
0.091
0.18
2.6
0,0011
0.0012
« o. oOtU
t.i'Oo/
0,066
0.0050
< d.0074
-------
>l-Ltl-
TABLE 22 (continued)
htSIN
roi»L
S*3S
(»&>
Pu
MJ
*8
is
1
SB
RB
8H
St
*S
ce
GA
7fc
cu
M
C'~l
Ft
MS
f
V
TI
"£X
K
s
~p
SI
*l
M^
N»
e
BE
< Or, 0621
0.030
0.33
1 .9
'1.67
It.
0.23
1.0
« O.e7
?«J
u.lb
u,J9
~ 8,?
1.2
0,5?
a.Jb "
«c
2",
0,50"
1.1
79.
"- "BIO.
2i.
"i
2.7
830.
"C
u!
•t.2
• o.oan
< O.OOdV
o.oau
0 , 7^
5."
l .1
3'-.
O.Sb
l.o
« U.39
5,9
< 0,17
I./
6.8
0,93
2,u
O.«0"
ut)0.
1",
-0.73
2.6
100.
"«« '
l«u.
^6U.
2t »
*•
SOU
7TD ! ~
69.
31.
< O.OII
0,079
0.69
5.U
1.3
2v.
O.UM
t.M
< U.66
" " 7.J
* 0,30
1.9
- 5,3
1.6
<;, 1
0,09 " "
350,
v.o
"1,0 ~
3,4
li°!
99.
u5u.
10. " "
790.
29v.
"Tni. •- - •-
25,
09,
< 0.0002 <
0.012 <
0.0026 <
O.OW <
y.O l i <
U.S3 <
0.015 «
< 0,025 <
< 0.02V <
0 . 565 " ~
< 0,0066 <
0,100 <
<• 0.66 «
< 0.25 <
< 0.13 <
" 0.012 *
5.«
0,25 «
~ 0.15 <
0.063 <
'.» <
a.u <
17.
0.013 10 I.B
16.
U.15 10 0,79
M.I
' 21.
, a. 3
. 5.5
" 1.2
-
Ml.
- 2.T
,7.1
HO.
' ' it
860.
-
"38,
,••
« "*
3io. -- -
•
100.
~9 , 35
< 0.0018
0.0077
0.075
0,47
0.12
c."
O.OU6
0.15
0,0005 TO
0,60
0.0056 1U
u. 16
0.80
0.17
0.21
0.005
•
1.6
0.100
0.28
12.
190.
10,
-
1.5
210.
•
14,
•
. ct^pi^tM
- I\r-U»TrS t«<.T T>-F T..T4L ^ C
.Cl UF Al.
lUN.
-------
«2S
TABLE 23. TRACE ELEMENT EMISSIONS IN SASS SAMPLES, RUN No. 2
OSC"
Ul
u>
EUE«tNT
U
TH
HI
pa
a
Ag .
1R <
OS «
HE «
n •
HF •
LU «
YB <
TM .
ER <
HO «
DY «
TB <
CD «
EU <
SM «
ND <
PR
ce
L»
BA
C3
I
TE <
SB
Sh
CO
PC «
HH <
I0U*
CYCLONE
(••U)
0.029
0.001
: 0,035 «
0,21
E O.OOM <
= 0.0022 «
: 0.0034
: 0,0037
: 0.0023
c O.OOA7
t 0.11
' 0.031
' 0.011
t 0.0045
( 0,016
' 0.0032
s 0.022
0.0003
0,016
• 0.011
0.055
• 0.20
0,024
0,55
0.35
6.5
0.0078
0.021 «
0.017 «
0.037
0.035
0.0036
0,019 <
0.0033 «
JljM
CYCLONE
(M(j)
0.050
0. lu
t n.12
1.0
0 . u 'J 1 1>
• a . 0 U 1 •»
0,0029
0.0032
0.0020
0.022
0.071
0.027
0.020
0.0007
0.014
0,0079
0.039
0.0002
0.023
0,021
0.062
0.089
0.029
0.15
0.86
21.
0.0093
0.0032
0.018
0.032
0.043
0.0070
0.016
0.0005
1L'"
CYCLONE
C"G)
O.OIH
0.035
< 0.0026
1.0
U.022
0.0009
0.001S
0.0016
0,0010
0,0079
0.024
< 0.0046
< 0.0053
< 0,0041
< 0.0072
< 0.0020
< 0,020
< 0.0001
< 0.0068
< 0,0037
0.0072
0,032
0.026
0,21
0.31
11.
0.0093
< 0.0023
< 0,0090
0,061
0,060
0,0044
< 0.012
< 0.0003
FIL'th
CATCH
(WG)
0.0923
0.0033
O.OOS9
0.046
< 0.0915
< 0.0001
< 0.0002
< 0.0002
< 0.0010
< 0.0012
< 0.0013
< 0.0001
0.0007
0,0002
0.0009
0.0006
0.0067
0.0003
0.0012
0.0002
0.0013
0.0074
0.001 1
O.OU
0.0089
< 0.69
< 0.0020
< 0.0002
0.0010
0.0052
< 0.037
< 0,017
< 0.0007
< 0.0002
-------
TABLE 23 (continued)
CAI-b Ml
j«-JUl> s 7,541 DSC*
in
*•
U*t'
•u
"0
NH
IH
1
SH
HH
BM
SE
AS
GE
GA
in
cu
NI
CO
FE
MN
CB
V
TI
CA
K
3
P
S!
A I.
MG
NA
8
BE
LI
* t 1 ou*
CtCUONt
<«G)
« 0,0018
0.019
U.15
1 .4
0.21
20.
0.21
0.65
< 0.42
l.e
< 0.11
0.14
11.
O.S3
0.25
0.082
MC
12.
0.24
1.0
38.
240.
22.
69U.
4.3
MC
MC
46.
N.
11.
0.0070
0.25
ju-
C»CUUNt
("til
« O.OOle
0.021
O.I-J
1 .**
0.19
9.9
0.18
0.57
< 0.52
1.1
0.081
0.60
i.r
0,06
0.44
O.f«
160.
1.8
6. IS '
0.87
11.
620.
25.
200.
2.1
400.
120.
" 21."'
9,9
5.5
0.0065
0.12
CKLUNE
!«(,)
< 0.0008
0.016
0.26
1.1
0,26
7.2
0.090
0.19
< 0.26
2.9
0.21
0.97
1.2
0.46
0.32
o.roo'
140.
It*
1.1
11.
12.
55.
5.6
120.
MC
46.
14.
5.0
0.012
0,062
FRU*
t"G)
< 0.0015
0,0061
O.OOM
0,011
0.0045
0.4}
< 0.011
< 0.0091
0.029
0.024
0.0009
0,064
< 0,27
« 0,19
< 0.033
< o.oole
1.1
0.055
0.052
0.014
0.53
24.
< 0.92
8.5
0,074
< 1.7
11.
1.4
< 26.
< o.ie
< 0.0004
< 0.0037
ISO
MfcSIN
t»G>
< 0.076
< 0.070
< 0.0088
< fl.0«l
< 0.014
« 0.28
« 0.046
« 1.7
< 0.040
< 0.016
« 0,028
« 0.012
< 2.0
< 2.6
« 4,3
< 0,032
« 6.5
< 0,22
« 0,11
< 0.014
« 0.19
< 17.
« 10,
560.
< 4.5
< 9.9
< 3.9
« 6.2
< 76,
0.40
0.0012
0.018
CC"PUSITI
SAMPLt
(«G>
< 0,016
0.010
0.0026
< O.on/i)
< 0.0029
o.onso
0.0009
c 0.062
0,077
0.0031
< 0,0060
< 0,0024
< 0.47
0.26
« 0.46
0.0070
€ 1.9
< 0,095
0,14
< 0.0057
< 0,098
< 2.2
< 0.76
160.
< 6.4
< 1.5
< 0.56
« 0.70
< 5,4
0.97
< 0.0001
< 0.011
rum
stss
0.11
1.0
38,
1.2
4.8
0.098
0,09u
0.59
".1
0.66
0.4R
1.4
TO
7,6
0.11
2.0
14.
I."
TO
0.13
*
15.
2,5
3.2
100,
58.
12.
110,
TU 110.
21.
0.029
0,46
EMISSION
FUUNO
("G/OSC")
< 0,011
0.012
0,079
0,088
5.0
0.061
0,19
0,014 TU
1.0
0.041
0.26
1.9
0.26
TO
0.11
0.16
0.64
0.044
2.0
0.11
0.41
7.7
220.
1.6
15.
5,0 10
l.l
0.0038
0.060
14.
J*c INDICATES • MAJOR COMPONENT OF THE SAMPLE.
• INDICATES TnAT T*t TUTAl A'<0 b"lSSlU'< VALUES ofcRt NUT
CALCUL»rtO OftlM, TO THE PHtSEtCE l> AN MC CONCENTHAr ION,
•• INDICA1LS
VALUt t'CttOlSG O'.l
-------
quantities. Upper limits are sums of real values and "less thans." Quantities
reported as "less than" mean that either an element was not present at values
above its detection limit (in which case the detection limit is the "less than"
value employed) or that the elemental value did not exceed its value in the
appropriate blank (in which case the blank value is the "less than"). "Major
component" is used for concentrations exceeding a few percent.
The bulk of the trace elements are found in the stack particulate, with
only a few elements present at greater than their blank values after the fil-
ter. The composite sample is a combination of the first impinger, a nitric
acid module rinse and the module condensate.
Tables 24 and 25 list trace element totals and emission factors determined
from cyclone and filter catches from RAG runs 1 and 2. Although neither Tenax
nor impingers were analyzed for trace elements, the distribution found in SASS
samples (see Tables 22 and 23) indicates that most trace elements are found in
the particulate catches. In general, the emission factors from the RAC and
SASS samples agree within the factor of 3 noted earlier, although the RAC values
are consistently lower. There is no evidence for contamination of SASS col-
lected samples by iron, chromium or manganese from the stainless steel probe or
cyclones. One major difference between the SASS and RAC emission factors is
arsenic, with the RAC values for this element lower by a factor of 20 to 40.
The higher oven temperature of the SASS would suggest that the volatile element
arsenic would be more readily collected on RAC particulates; however, the
opposite is true.
Analysis of SASS train samples for mercury, fluoride, chloride, and sul-
fate resulted in the sample concentrations displayed in Table 26. As with the
SSMS data, these results show that most of the inorganic substances are in the
particulate rather than the gaseous portions of the CAFB emissions even for
the volatile element mercury.
Mercury emission rates for SASS runs 1 and 2 are 2.02 vg/m3 and 4.00 ug/m3
which represent 10.5 percent and 24.1 percent, respectively, of the mercury in
the lignite. Fluoride emission rates are 1.01 mg/m3 and 2.35 mg/m3 correspond-
ing to 9.2 percent and 24.8 percent, respectively, of the fluoride in the lig-
nite. Chloride emission rates are 0.53 mg/m3 and 3.25 mg/m3 which correspond
to 0.2 percent and 1.8 percent, respectively, of the chloride in the lignite.
A combination of laboratory and field data (SC^-SOa emissions) is neces-
sary for a complete evaluation of sulfur emissions. Such a combination shows:
• The SOX emissions measured corresponding to the SASS-1 run are
SOa, 101.9 ppmv, or 407.3 mg/m3 sulfate, and SOa, 0.8 ppmv, or
3.1 mg/m3 sulfate. Combined with the SASS-1 measurements, these
total 470 mg/m3 or 21.5 percent of the total sulfur in the lignite.
* The SOX emissions corresponding to SASS-2 were S02, 299.7 ppmv,
or 1197.9 mg/m3 of sulfate, and SOa, 1.3 ppmv, or 5.1 mg/m3 of
55
-------
TABLE 24. RAC-1 TRACE ELEMENT EMISSIONS
LEMENT CYCLONE
CATC«
u
TH
81
PR
TL
AU
IR
09
"E
H
NF
LU
TB
TN
ER
NO
01
TB
GO
EU
SM
NO
PR
CE
L*
BA
CS
I
TE
SB
SN
CO
PO
RH
HU
"0
NR
ZR
¥
3R
RB
BR
3E
A3
GE
CA
IN
CU
NI
CO
FE
"N
CM
V
TI
CA
K
s
f
31
AL
"G
NA
B
BE
LI
0
0
0
0
0
« 0
< 0
< 0
0
0
< 0
0
0
.0012
.006)
.0005
.017
.0065
.000?
.000)
.000)
.0005
.0002
.0030
.0008
.001)
0.0005
0
0
0
0
0
0
0
0
0
0
0
0
n
0
< 0
0
0
0
* 0
< 0
< 0
.001)
.0001
.0009
.0002
.0006
.0006
.001)
.0028
.0009
.0095
.013
.19
.000)
FILTER
CATC*
0.0088
0.018
0.005)
0.040
0.0003
0.0003
o.ooos
0.0006
0.0029
0.0028
0.0060
0.00)0
0.0017
ft. 0007
0.00)0
0.0010
0.0078
0.0001
0.0020
0.00)6
0.0036
0.012
0.0051
0.027
0.0)6
0.71
0.0012
.0016 < 0.0011
.001) < 0.0025
.0007
.0012
.0002
0.0015
0.0068
0.0008
.0010 < 0.0019
.0002 «
0.0001
.0001 < 0.000)
0.0009
0
0
0
0
0
o
.0057
.065
.012
aa
.0057
012 «
0.0004 <
0
< 0
0
0
n
0
0,
25
0
0
0
1
1)
1
?">
0.
IS.
2.
1.
0.
0.
0.
0.
014
0075 «
012 «
56
QiO
.79
0044
S3
.018
004
6
3
033
5
2
100
15
oooo
0060
0.0018
0.016
0.22
0.016
0.61
0.016
0.0093
0.0086
0.0070
0.0077
0.066
0.09)
0.000
0.015
0.004)
15.
1.1 6
V.OlS
0.086
11.
no.
1.1
A. 1
0.20
9n.
«c
o.2
1.2
0.96
0.0007
0.0065
ior*t
ate
EMISSION
FOUND
0.00)2
0.006)
0.0005
0
0
< 0
< 0
< 0
o.ooos
0.0002
< 0
< 0
< 0
< 0
< 0
< 0
< 0
< 0
< 0
< 0
0
0
0
0
0
0
0
0
< 0
0
0
0
< 0
< 0
TO 0.0088
TU 1.018
TO 0.005)
.056
.0065
.0005
.0008
.0008
TO 0.0029
TO 0.0028
.0090
.000?
.0029
.0012
.0002
.0011
.0087
.000)
.0043
.0049
.014
.0060
.016
.051
.89
.0015
.001*
.00)8
.0022
.0080
.0011
.00)4
.0003
0
0
0
0
0
.00)8 TO
.0075 TO
.0006 TO
0.067
0.007*
< 0.0006
< 0.0009
< 0.0010
.0006 TO
.000) TO
< O.OII
€ 0.0050
< 0.0035
< 0.0010
< 0.0051
< 0.0013
< 0.0100
< 0.0003
< 0.0031
< P. 0051
0.0058
0.017
0.0071
0.003
0.061
1.1
0.0018
0.0019
< 0.0046
0.0027
0.0095
0.0013
0.011
0.021
0.006)
0.00)5
0.00)3
< 0.0004
0.0027
0.022
0.29
0.028
l.O
0.022
0.012
0.0044
0.021
< 0.015
0.012 TO 0.068
0.66
0.061
0.82
0.0087
«0.
0.7J
0.0)1
0.1)
12.
140.
5.6
17.
0.2)
100.
5.4
1.)
1.1
0.0011
O.Ot)
<
0.015
n.ooo)
0.0005
0.00)2
0.026
0.)4
0.0))
I.P
0.026
0.015
0.0052
0.025
0.018
TO
0.78
0.072
0.98
0.0100
08.
0.80
0.039
0.15
15.
170.
6.6
08.
0.27
120.
6.0
1.5
I.S
0.0011
0.015
0.081
MC l"OIC*TfS i MAJOR COMPONENT OF T»E SAMPLE.
- INDICATES TM4T TM{ TOTAL AND E»ISS!C« VAIUCS WERE NOT
CALCULATED 0*1NC 10 THE PRESENCE CF AN -C CONCENTRATION.
56
-------
TABLE 25, RAC-2 TRACE ELEMENT EMISSIONS
U
tM
HI
PB
TU
»u
IB
OS
BE
N
MF
LU
T"
£B
HO
OY
TB
GO
EU
SM
NO
PR
C£
L»
a*
cs
i
TE
SB
9H
CD
PD
RN
BU
"0
NB
SB
BB
BB
3E
«S
GE
G*
CU
NI
CO
FE
CB
V
TI
C*
K
S
P
31
»L
*G
B
RE
LI
CtCUONE
CMCH
0.0026
0.0058
0.0005
0.009
; 1 A 1 06
: oioOOl
: 0.000?
: 0.000?
O.OOOS
0.0000
: 0.000)
: 0.0001
: 0.0006
: 0.0001
: O.OOA7
! 0.000)
E 0.0006
0.0001
E 0.0000
0.000?
0.0009
0.00)5
0.0010
".010
0.0069
0.2«
0.0000
0.0020
E 0.0005
0.0011
0.0010
0.0008
i 0.0001
E 0.0001
' 0.0001
0.0008
0.0011
°.036
c 0.000]
0.0036
0.0079
0.0001
0.0070
0.011
0.009?
0.16
0.051
0.0051
0.00?!
9.0
0.20
0.0059
o.oai
0.05
5).
0.36
07.
0.002
6.9
1.1
0.50
O.I)
0.006
0.0002
0.0020
f IL TEB
C1TCH
0.0050
0.015
n.0006
0.085
< ft . fl 0 3 3
< 0.0005
€ 0.0007
« O.OOOA
< o.oooo
n.ootfi
« O.OOOfl
< 0.0005
< 0.00)0
< 0.0010
< 0.0051
« 0.0027
< 0.0011
< 0.0026
< 0.0128
0.0008
0.0008
0.0)0
0.0069
0.051
O.OuO
1.5
0.0016
0.0025
< 0.0005
0.011
0.016
0.0099
< 0.0020
€ 0.0002
< 0.000"
0.0087
0.0092
0.10
0.020
o!o?0
0.0100
0.018
O.OU7
0.01 )
0.12
0.16
0. 16
0.012
0.008)
12.
o.ui
0.062
0.20
7.9
110.
1.2
11.
O.U9
67.
1?.
28.
n.uu
0.)7
0.0012
0.027
TOT4L
H»C
("&)
0.0076
0.010
0.0050
0.13
< 0.00)9
< 0.0006
< 0.0009
< o.ooio
0.000) to 0.0000
0.002?
« O.OOlt
« 0.0007
< 0.00)6
« 0.0015
< 0.0057
< 0.00)0
< 0.0018
0.0001 TO 0.0026
< 0.0032
0.00)0
0.0057
0.0)7
0.0079
0.065
0.007
1.8
0.0021
o.oooo
< 0.0009
0.012
0.017
0.011
< 0.0021
< O.OOOS
< 0.0006
0.0095
0.012
0.17
0.020
2.2
0.0?K
0.01(1
0.022
0.05«
0.020
0.1)
O.S2
0.20
0.017
0.0100
21.
0.61
0.066
0.24
8.)
100.
58!
0.5)
1)1
0.97
0.0010
0.029
F-1SSICA
FOUND
f1&/OSC*!
ft.0079
O.OOS2
0. lu
n.ooai
0.0006
« o.noio
o.ooo) rn o.ooa?
0.0023
0.0011
0.0007
0.0050
0.0016
0.0060
0.00)1
0.0(118
0.0001 TO 0.0027
< 0.00)0
0.0010
0.0059
0.019
0.0082
0.068
0.009
1.1
0.0021
0.4006
< 0.0051
0.01)
o.oie
0.011
< 0.0022
< 0.0003
< 0.0006
0.0099
0.013
0.021
2.2
0.0?0
0.019
0.02)
0.057
0.02S
0. iu
0.5«
0.20
0.018
0.01 I
21.
0.63
0.071
0.25
15ol
60.'
0.55
77.
29!
1.0
0.0)
0.0015
0.0)1
57
-------
TABLE 26. CONCENTRATIONS OF SELECTED INORGANIC |PECIES IN SASS
SAMPLES FROM THE CAFB-LIGNITE PROCESS
Sample
SASS Run No. 1
filter
Ip cyclone
3y cyclone
10y cyclone
XAD
CHt
i4
SASS Run No. 2
filter
Iji cyclone
3y cyclone
lOy cyclone
XAD
CH1"
id
Mercury
(vg/g)
1.24
0.80
0.70
1.12
< 0.072
0.014 yg/m£
0.003 wg/mfc
12.67
1.87
1.19
0.79
< 0.081
0.034 vg/mfc
0.003 pg/m£
Sulfate
(mg/g)
59
8.2
7.4
75
1.8
-
-
110
22
21
74
0.32
_
Fluoride
(mg/g)
0.59
0.42
0.09
0.35
0.02
0.05 mg/m£
-
1.06
0.50
0.23
1.30
-
-
Chloride
(mg/g)
ND
0.005
0.10
-
ND
0.008 rag/m£
-
ND
0.38
0.38
0.77
0.14
0.015 mg/m£,
*A11 values blank corrected.
Combination of first impinger, condensate, and acid module rinse.
'Combination of second and third impingers.
ND
none detected; sample is less than or equal to blank.
58
-------
sulfate. Added to the SASS train catch, this results in 1297
mg/m3 sulfate or 68.6 percent of the sulfur in the lignite.
These sulfur balances point out the extremely poor sulfur removal efficiency
of the gasifier bed during SASS No. 2 and the relatively better performance
during SASS No. 1. These conclusions are consistent with the observations
made concerning the organic emissions data that the CAFB was more "chemically
active" during SASS No. 1 than during SASS No. 2.
Table 27 lists concentrations of mercury, sulfate, fluoride and chloride
for various nonstack samples collected during SASS No. 2. In general, fly ash
and bed material from the same unit operation (regenerator bed and cyclone;
gasifier bed and main cyclone) have similar concentrations of these species
indicating that fly ash is representative of the bed material. The mercury
and sulfate concentrations in the stack cyclone and knockout baffle pass
readily through the hot gasifier and boiler and condense in the cooler stack
region.
TABLE 27. CONCENTRATIONS OF SELECTED INORGANIC SPECIES
IN SOLID SAMPLES COLLECTED FOR THE CAFB-
LIGNITE STUDY
Sample
Mercury Sulfate Fluoride Chloride
(ug/g) (mg/g) (mg/g) (mg/g)
Gasifier bed
Main cyclone
Regenerator bed
Regenerator cyclone
Stack cyclone
Stack knockout baffle
Lignite
0.037
0.029
0.029
0.054
0.129
0.833
0.158
1.2
1.0
2.2
1.8
2.0
3.4
18.0
0.08
0.13
0.09
0.21
0.15
0.19
0.09
2.0
0.78
0.14
2.0
0.054
0.2
1.75
Surface analysis of particulate samples was performed using ESCA. For
SASS samples, these samples included cyclone and filter catches and for the
RAC train, the particulate filter. Filter samples were analyzed by placing
a small piece of the filter into the instrument's sample holder. Cyclone and
other particulate were crushed, if necessary, and spread onto sintered steel
substrates for subsequent analysis. Data were discarded if the resultant
spectra displayed peaks characteristic of the substrate material. Regenerator
bed material was also analyzed as a "particulate" sample to determine the fluid
bed's effectiveness in removing sulfur from the coal. Lignite and limestone
feed samples were also crushed and analyzed by ESCA. Analysis of impactor
substrates was attempted, but due to the light particulate covering, no spectra
could be obtained.
59
-------
All samples analyzed by ESCA in this study were first scanned over the
entire electron binding energy range (broadband scan) to identify those ele-
ments present in concentrations greater than 0.1 to 1 percent (the sensitivity
of ESCA to any one element is a function of the photoionization cross-section
of the most intense core electron emission of that element). These broadband
spectra were then analyzed to yield surface concentrations of all identifiable
elements. Representative broadband spectra appear in Figures 9 and 10.
Quantification data for RAG particulate appear in Table 28; those for SASS
samples in Table 29.
TABLE 28. QUANTIFICATION DATA FROM ESCA ANALYSES OF
RAC TRAIN PARTICULATE FILTERS (RESULTS IN
PERCENT ATOMIC)
Element RAC-1 RAC-2 RAC-3 RAC-4 RAC-5
0
c
Ca
Na
S
Si
Al
55.5
19.3
5.3
-
4.1
6.8
9.0
49.1
24.1
4.8
1.3
3.9
5.9
10.9
54.6
23.4
4.2
-
4.9
5.4
7.5
51.9
23.9
3.5
-
3.5
7.9
9.3
51.4
27.4
5.0
-
3.2
6.6
6.3
As can be seen from the quantification data, the particulate samples have
very similar surface compositions, with oxygen and carbon being particularly
abundant. Substantial portions of this carbon, which the carbon Is short scans
showed to be mostly hydrocarbon, and oxygen are due to unavoidable adsorption
of these ubiquitous species on the sample surfaces. Such contamination is a
common problem in surface analysis and makes absolute (rather than relative)
quantification of the samples impossible.
The composition of particulate from lignite firing is quite different
from that found in the oil-fired CAFB. Samples collected during oil runs
contained no detectable aluminum or silicon; they had more sulfur and sodium
and also contained vanadium due to the different compositions of the fuels.
Analysis of fuel oil showed 20 ppm silicon and 2.1 ppm aluminum, while in
lignite these elements are listed as major components of greater than 1 per-
cent (10,000 ppm). Vanadium is present in lignite at 28 ppm and in fuel oil
at 307 ppm.
Short scans over the binding energy range of the carbon Is electron showed
several distinct carbon species. Figures 11 and 12 are Cjs spectra of SASS
No. 1 filter and SASS No. 2 ly particulate, respectively. Hydrocarbons are the
dominant carbon species in both samples, and both show small amounts of surface
carbonate. The tailing between the hydrocarbon and carbonate binding energies,
60
-------
i r
CAFB
SASS- I-PF
3
>»
k
O
k.
«••
!o
o
uJ
O
O
CM
O
O
1000
BINDING ENERGY, eV
Figure 9. Broadband ESCA spectrum of SASS-1 filter particulate.
-------
ON
ho
UJ
S
It
o
u
1000
V)
d"
CAFB
SASS-2-PF
CO
cJ
eg
D
O
u
|^^
BINDING ENERGY, eV
Figure 10. Broadband ESCA spectrum of SASS-2 filter particulate.
-------
TABLE 29. ELEMENTAL QUANTIFICATION DATA FOR SASS PARTICULATE SAMPLES FROM ESCA ANALYSIS;
RESULTS IN PERCENT ATOMIC
SASS run No. 1
Element
0
C
Ca
Na
S
Si
Al
Particulate
filter J
43.1
26.9
12.8
0.6
4.7
5.7
6.3
Lp cyclone
44.5
28.9
9.2
0.7
6.9
4.8
5.0
3y cyclone
47.3
29.4
4.3
0.8
6.1
6.1
6.0
lOp cyclone
48.6
30.0
3.3
0.6
7.7
4.4
5.4
Particulate
filter
33.0
52.3
2.8
1.0
3.7
2.5
4.6
SASS run No. 2
lp cyclone 3p cyclone
* 55.0
* 25.8
* 3.3
* 0.8
* 6.3
* 4.2
* 4.7
10p cyclone
53.9
24.4
4.8
-
10.5
2.4
4.0
Calculations were not made due to high background in spectrum attributed to substrate.
-------
>»
O
O
UJ
O
U
295
275
BINDING ENERGY, cV
Figure 11. Carbon Is spectrum of SASS-1 filter particulate.
-------
in
'£
.o
fe
o
UJ
<
tr
z
o
o
i r
CAFB
SASS-2-l/t
C.s
-1
395
275
BINDING ENERGY, eV
Figure 12. Carbon Is spectrum of SASS-2 ly cyclone partlculate.
-------
particularly evident in Figure 12, could be attributable to carbonyl or alcohol.
Tin' (:1K spectra of RAG 1 and 5 filters displayed in Figures 13 and U show, in
addition to hydrocarbon and carbonate, the presence of reduced carbon species,
possibly coke. No reduced carbon species were found on RAC filters collected
during CAFB oil-firing.
Sulfur found in all particulate samples analyzed was, for the most part,
sulfate with only the SASS-2 filter showing any sulfide (Figure 15). In this
sample the sulfide was approximately 10 percent of the surface sulfur; the
rest, sulfate. The depth profile of sulfur on the two SASS filters was de-
termined by measuring the sulfur-calcium ratio after argon ion etching the
samples for successive periods of time up to 20 minutes. Changes in the
spectra with depth are shown in Figures 15 to 17. These figures show the ten-
dency of etching to reduce the sample surface. Calcium was chosen as the in-
ternal standard or constant by which to measure sulfur because there is no
evidence that its concentration changes with depth. For SASS-1 the S/Ca ratio
decreased by a factor of 4.5 between the surface and a depth of approximately
200 8. The S/Ca ratio for SASS-2 decreased at roughly half that rate. Both
depth profiles are plotted in Figures 18 and 19 as S/Ca versus depth as minutes
etched. This depth profile shows a surface enhancement of sulfur on the par-
ticulate which is probably due to condensation of moisture onto particulate
in the cooler stack region.
ESCA analysis of the gasifier bed material collected during SASS No. 2
revealed only carbon, oxygen, and calcium in detectable quantities. If the
system were working efficiently, we would expect to see detectable quantities
of sulfur in the bed. A failure to see sulfur may, however, be partially
attributable to particle size. When received, the bed particles were perhaps
as large as 1 mm in diameter. Crushing these to a powder for ESCA analysis
would expose a large amount of previously unexposed area. Since any expected
sulfur would be that adsorbed on the surface, this pulverizing could make the
sulfur undetectable.
Carbon in the bed sample (Figure 20) was in three distinct forms: hydro-
carbon, carbonate and an unidentified reduced species, possibly coke. Hydro-
carbons are due to unburned fuel and ambient surface contamination; carbonate
is limestone bed material; and the coke is a deposit from pyrolysis.
66
-------
w
"c
3
O
'Jo
o
UJ
cr
O
O
295
275
BINDING ENERGY, eV
Figure 13, Carbon Is spectrum of RAC-1 filter particulate.
-------
a*
CO
XI
o
uT
-------
T 1
CAFB
SASS- a-P
u.
-I
I \
VO
o
UJ*
o
o
180
BINDING ENERGY, eV
160
Figure l'>. Sulfur 2p spectrum of SASS-2 filter particulate.
-------
O
u
Ul
(0
1 1 I—
CAFB
SASS-2-PF
S2p AFTER 2min ETCHING
ISO-
160
BINDING ENERGY, eV
Figure 16. Sulfur 2p spectrum of SASS-2 particulate filter
with argon ion etching: after 2 minutes of
etching.
-------
I I I
CAFB
SASS-2-PF
S2p AFTER 18 mm ETCHING
UJ
Q
O
UJ
oc
H-
z
O
O
180
160
BINDING ENERGY, eV
Figure 17. Sulfur 2p spectrum of SASS-2 particulate filter
with argon ion etching: after 18 minutes of
etching.
-------
z.o
0.3
0.4
—•—
o.s
O * 4
• • IO It 14
DEPTH (iilMttl ITCMtD)
1C !• 10
Figure 18. Depth profile of sulfur in SASS-1 filter particulate.
|O.M>
OS)
0 Z 4 « ,
OCPTWlmlnuttt ETCHED)
10
Figure 19. Depth profile of sulfur in SASS-2 filter particulate.
72
-------
c
3
o
UJ
U)
O
u
i r~
GASIFIER BED
C,,
JL
_L
J_
295
2T5
BINDING ENERGY, eV
Figure 20. Carbon Is spectrum of gasifier bed sample collected during SASS-2.
-------
REFERENCES
1. Dorsey, J. A., L. D. Johnson, R. M. Statnick, and C. H. Lochmuller.
Environmental Assessment Sampling and Analysis: Phased Approach and
Techniques for Level I. U.S. Environmental Protection Agency, Research
Triangle Park, North Carolina. Publication No. EPA-600/2-77-115.
June 1977. 38 pp.
2. 40 CFR 60, Appendix A (42 FR 41754-41782), 1977.
3. 40 CFR 60, Appendix A (42 FR 41786-41789). 1977.
4. Werner, A. S., C. W. Young, M. I. Bornstein, R. M. Bradway, M. T. Mills,
and D. F. Durocher. Preliminary Environmental Assessment of the CAFB.
GCA/Technology Division, Bedford, Massachusetts. Prepared for the U.S.
Environmental Protection Agency, Research Triangle Park, North Carolina.
Publication No. EPA-600/7-76-017. October 1976. 324 pp. (NTIS No.
PB 262-001/AS).
74
-------
SECTION 5
ENVIRONMENTAL ASSESSMENT
INTRODUCTION
The Industrial Environmental Research Laboratory (IERL) of EPA is currently
involved in formalizing and standardizing environmental assessment methods to
allow for comparison of environmental impact associated with different energy
and industrial processes. Source Analysis Models (SAM) have been developed by
Acurex for EPA as a systematic procedure for investigating environmental
impact.
In conducting environmental assessments, it is necessary to perform one or
more of the following tasks:
1. rank individual effluent streams by the expected toxicity of
their discharges,
2. establish sampling priorities,
3. determine problem pollutants,
4. recommend best multimedia control technology alternatives,
5. recommend control/disposal technology development programs.
Three Source Analysis Models (SAM/IA, SAM/I, SAM/II) have been developed
as a series of methods to aid in accomplishing these five tasks. GCA has
employed the simplest method of the sequence, SAM/LA, to provide a rapid
screening of flue gas emissions from the lignite-fired CAFB. SAM/IA compares
actual emission and effluent concentrations with a series of Minimum Acute
Toxicity Effluent (MATE) values established by EPA. The model is appropriate
for analysis of Level I and Level II data and provides some input to each of
the five elements above; most specifically: identification of further sampling
needs, problem pollutants, and recommendations for applicable control tech-
nology. The objective in evaluating the CAFB by this procedure is to compare
results with similar data derived for six conventional lignite-fired boilers
located in the western U.S. The final goal is to recommend sampling procedures
and control technology that would be appropriate for operation of the CAFB
demonstration plant in San Benito, Texas.
SAM/IA is implemented by use of a tabular format for simple comparison of
estimated pollutant discharge rates with effluent and emission goals. The
emission goal used with SAM/IA is the MATE, with values established for most
75
-------
of the 650 substances on the Multimedia Environmental Goal (MEG) list based
upon health or ecological effects reference data. The assumption is made that
the concentrations of pollutants in gas, liquid or solid effluent streams
should not exceed MATE values which are estimated to minimize acute (short-
term exposure) toxic effects.
MATE's describe very approximate concentrations of components or species
in air, water or land effluents which may evoke significant damage response
in exposed humans or the ecology from limited duration exposures (i.e., less
than 8 hours per day).
MATE's are derived from TLV's, NIOSH recommendations, LDso's, LD 's,
LC5o's, TD 's, TLM's, Water Quality Criteria and Drinking Water Regulations.
LiU
As many as six MATE's can be listed for each pollutant species or sample
fraction in the worksheets:
• Air (health and ecology based)
• Water (health and ecology based)
• Land (health and ecology based).
This allows for comparison of emissions to MATE's for air, water or land
for studies of health or ecological effects.
The steps included in the SAM/IA approach are:
1. Identify specific sources within the overall system or
process.
2. Identify the various effluent streams from that source.
For complete analysis, each gas, liquid or solid waste
discharge is included as a separate effluent stream.
3. Determine the concentration of each sample fraction (Level I)
or specific pollutant species (Level II) to be considered in
each effluent stream. In Level I assessments, the set of
species potentially present which would lead to environmental
hazard is established at this point for each sample fraction.
4. Each sample fraction or specific pollutant concentration in
a given effluent stream is then divided by its corresponding
health-based MATE. This quantity is, henceforth, called a
"degree of hazard" (H). A second quotient is formed using
the corresponding ecological MATE.
5. At this point, flags (i.e., checkmarks) are noted on the
form for each pollutant entry whose health or ecological
degree of hazard (H) is greater than unity. This provides
for ease in spotting potential problem pollutants. Their
presence should be noted and assessed in any report.
76
-------
6. The final calculation for each pollutant species or sample
fraction in each stream utilizes the product of its degree
of hazard (H) and the effluent stream flow rate to establish
health (or ecological) toxic unit discharge rates (TUDR) .
7. The total stream degree of hazard is then calculated as the
sum of the H's for each pollutant. Further, the total stream
TUDR is calculated by summing the individual pollutant entry
toxic unit discharge rates.
8. Degrees of Hazard and Toxic Unit Discharge Rates are then
grouped and summed by discharge media (i.e., the H's and TUDR's
for all gaseous, water and solid effluent streams are listed
and summed for each medium).
GASEOUS EMISSIONS
SAM/IA is being used to assess air emissions from the CAFB as compared to
several conventionally-fired lignite boilers in the Western U.S. Particulate
and trace element and anion species are compared based on sampling by SASS and
RAC train methods and analysis by spark source mass spectroscopy (SSMS) , atomic
absorption spectroscopy (AAS) , and wet chemical techniques. Other air emis-
sions which are assessed in the SAM/IA model include: C^-Cg hydrocarbons,
S02 and S03.
Table 30 illustrates the format of the SAM/IA procedure and an analysis
of gaseous emissions measured during lignite gasification and combustion.
No hydrocarbons with higher boiling points than C2 were detected, and hydro-
carbons which did exist were in very low concentrations. Comparison of actual
hydrocarbon concentrations with health MATE values shows degrees of hazard
significantly less than 1. However, the ecological degree of hazard for Cj
hydrocarbons, 9,000, indicates that flue gas ethylene concentrations may
have an adverse effect on vegetation. The ecological C\ hydrocarbon MATE
value was probably set at 1 yg/m3 due to the reported harmful effect of ethyl-
ene on plants at relatively low concentrations. The SAM/IA analysis indicates
that €2 hydrocarbons (acetylene, ethane, propylene) emitted from the CAFB
during lignite gasification are low and of minor significance in producing
adverse health or ecological impacts.
The health hazard factors associated with NO and NOX emissions range from
3.1 to 4.1, respectively. This indicates a somewhat excessive emission of
nitrogen oxides, however, on a fuel-related basis NOX emissions are well below
the new source performance standards (NSPS) for coal-fired steam generators
> 250 * 106 Btu/hr capacity. The actual NOX emission rate is 0.09 lb/106 Btu
as compared to the standard of 0.7 lb/106 Btu, lower by a factor of 10. This
suggests that the health MATE value for NOX may require revision to make it
more representative of existing standards.
77
-------
TABLE 30. SAM/IA.WORKSHEET FOR LEVEL 1 - ESSO, ENGLAND, CAFB PILOT PLANT
SAM/IA WORKSHEET FOR LEVEL 1 Form IA02 Uvri 1
00
1 SOURCE/CONTROL OPTION p,,, , ,
ESSO, England, CAFB Pilot Plant
2 EFFLUENT STREAM 3 EFFLUENT STREAM FLOW RATE
101 Fl»- r.tf «,. 0.6 mVsec
COW • NAME (I« • m'/MC - ItquiO • I/WC - tOIKJ wtlte • f/MC)
4 COMPLETE THE FOLLOWING TABLE FOR THE EFFLUENT STREAM OF LINE 2 (USE BACK OF FORM FOR SCRATCH WORK)
A
S*UF\( nUCTDN
UNITS
<=1
C2
NO
NO
S02
SO,
CO
CO;
B
flUCIlON
CONCIN
TMTON
ug/m3
9.0E3
2.0E3
2.8E4
3.7E4
5.1E5
3.2E3
<5.7E5
1.4E8
C
MCJklTH
UATt
CONCCN
t HATCH
ug/ra3
3.3E5
5.3E6
9.0E3
9.0E3
1.3E4
N
4.0E4
9.0E6
0
[COtOGKAl
HATt
COMCCN
TRATKM
Wg/n>3
1.0
1.1E5
N
N
N
N
1.2ES
N
E
MCICC Of
HA2UO
(MtAUMI
(B'Cl
-
0.03
0.0004
3.1
4.1
39.2
<14.3
15.6
F
OROINM.
K»itlON IN
MEAllM UATt
TABU
-
-
_
G
01GKCI or
M*IHH>
itCCKO&CAU
IB-Di
-
9,000
0.02
4.75
H
OMNNAl
rmnion IN
ICCX UAH
TASli
-
2
2
1
\' IF
HCJM.TM
U>IC
ciuioca
-
/
/
/
/
/
j
V If
tea
UATC
CICfCOfO
-
/
/
K
L
tO«< UNIT OiiCxADCI *Att
(HCAITM
BAMOl
it • UNt )l
0.02
0.0002
1.84
2.44
23.52
8.51
9.28
iCCCKOCKAl
BAUOi
1C • UNC ))
5.355
0.01
2.81
» tan tMct a NCUXD utt A CONTIHUATMM IHIET
5 EFFLUENT STREAM DEGREE OF HAZARD
HEALTH MATE BASED fl COL E) 5. 76 • 3
ECOLOGICAL MATE BASED (I COL G) 5b 9.005
(ENTER HERE AND AT LINE 8. FORM IA01)
6 NUMBEI
COMPAfl
HEALTH 6l
ECOLOGlCI
» OF ENTRIES 7 T(
€0 TO MATES H
7 E(
kL 66 3 (J
3XIC UNIT DISCHARGE SUM
EALTH MATE BASED a COt K)
:OLOGICAL MATE BASED (I COl
NTER HERE AND AT LINE 8. FO
,, 45.6
,,^ 5.358 '
RM IAOI)
-------
The same argument holds for the SAM/IA results for S02 emissions. Although
the health hazard factor is 39,2, the total S(>2 emission was found to be
0.55 lb/106 Btu or less than half of the NSPS (1.2 lb/106 Btu) for large steam
generators. The emission of CC>2 and attendant hazard factor is fairly meaning-
less because high C(>2 flue gas concentrations are indicative of high combustion
efficiency.
TRACE ELEMENT AIR EMISSIONS
The SAM/IA procedure was used to assess the impact of trace element emis-
sions measured during the lignite run at the ESSO pilot plant. Tables 31 and
32 present a listing of trace element concentrations measured by spark source
mass spectrometry (SSMS) from particulate samples collected during the two SASS
runs. As for the gaseous emission analysis, emissions and MATE values are
presented in yg/m - A check mark is placed in column I or J if the Health or
Ecology MATE value is exceeded by the actual emission. For the first SASS run
(SASS-1), the emissions of concern, according to the SAM/IA analysis, include
Ba, As, Ni, Cr, V (Ecology MATE exceeded), Ti, P, Si, Mg, B, and Be. Except
for Ti, Si, Mg, and B, these emissions may have severe effects. RTI's research
of background information for MEG (multimedia environmental goal) development
reports the following potential effects associated with the aforementioned
hazardous trace elements:2
• Barium - soluble barium compounds are highly toxic when ingested;
0.8 to 0.9 g of BaCl2 is reported as a lethal dose; BaO and BaCOa
have caused respiratory damage in man.
• Arsenic - trivalent species is most toxic; compounds absorbed
by inhalation, ingestion, and through skin; cumulative poison
producing chronic effects in mammals.
• Nickel - nickel absorbed through inhalation may be associated
with nasal, sinus, and lung cancer; dietary intake of nickel
apparently not harmful; nickel salts may be highly toxic.
• Chromium - all chromium compounds are considered poisonous, with
hexavalent chromium considered more hazardous than trivalent form;
inhalation may cause injury or cancer in the respiratory tract;
laboratory tests have shown carcinogenic response in rats and
mice with lowest dosage of 1 mg/kg.
• Vanadium - toxic to humans by all routes of absorption, with pen-
tavalent species being most highly toxic; inhalation causes respi-
ratory system effects, including tracheitis, pulmonary edema, and
bronchial pneumonia; 0.2 to 0.5 mg/m3 has caused effects on
respiratory systems; 0.5 to 1.0 ug/m3 has produced noticeable
effects in plants.
• Phosphorus - white phosphorus is most hazardous allotropic form;
chronic effects include liver injury, necrosis of jaw bone, anemia,
brittle bones, and tooth and eye damage; may be absorbed by all
79
-------
TABLE 31. SAM/IA WORKSHEET FOR LEVEL I - ESSO, ENGLAND, CAFB PILOT PLANT, SASS-1
8AM/IA WORKSHEET FOR LEVEL 1 Form IA02 Ural 1
oo
o
> SOURCE/CONTROL OPTION p,^ | /
ESSO, England, CAFB Pilot Plant, SASS-1
2 EFFLUENT STREAM 3 EFFLUENT STREAM FLOW RATE
mi, PI... E.. t). 0.5_2 a- /tec
OOK* KAMI (*•» * m'/i«c — iiguia * i/s«c — folia w«tt » f/uc)
4 COMPLETE THE FOLLOWING TABLE FOR THE EFFLUENT STREAM OF LINE 2 (USE BACK OF FORM FOR SCRATCH WORK)
A
IAM1I nuCTION
UNITS
U
Th
Bi
Pb
Tl
Au
Ir
Os
Re
W
Hf
Lu
Yb
Tm
8
riUCIION
CONCIN
riuiioN
Vg/nr
18
46
0.6-35
200
< 2.1
< 2.1
< 3.2
< 3.5
< 2.2
< 6.1
<24
< 6.2
< 5.9
< 1.1
C
HEALTH
UATC
CONCCN
T«ATWN
4.1E2
1.5E2
N
1.0E3
D
CCOtOGlCXl
UAH
CONCCN
t RATON
N
N
N
N
f.
OCGMt Of
MAMftO
(HUl'MI
IB'CI
-
001 -.085
<0.014
<0.006
F
OROINAl
(OSlTIONlN
HEALTH UATC
TABU
-
G
OCGDCC OF
HMARO
(ECOlOGICAl)
(B'D)
-
H
onoiNAi
POSITION IN
teen lure
TABU
-
1
\ if
Ht«UM
HAIC
CiCCIOCO
-
J
V II
CCOl
MATC
CICICOCO
-
K
L
TOXIC UNIT DISCHARGE HATE
(HCAITH
IASCO)
1C . LINE Jl
0005-.04
<0.01
<0.003
ICCOLOGKAI
BASED)
1C • UNI )>
* M0*f SMCC IS MEEUCD. UK * CONTINUATION WEET
5 EFFLUENT STREAM DEGREE OF HAZARD
HEALTH MATE BASED a COL F) 5* "513
ECOLOGICAL MATE BASED {£ COt G) 5t> 310
(ENTER HERE AND AT LINE 8. FORM IA01)
6 NUMBEI
COMPAR
HEALTH 6
ECOLOGIC'
» OF ENTRIES 7 T
ED TO MATES H
31 E
11 fih 1 (I
MIC UNIT DISCHARGE SUM
EALTH MATE BASED (I COL K)
COLOGICAL MATE BASED G. COt
NTER HERE AND AT LINE S. FO
7, - 267
,,7K 161
RM IA01)
-------
TABLE 31 (continued). SAM/IA WORKSHEET FOR LEVEL I - ESSO, ENGLAND, CAFB PILOT PLANT, SASS-1
CONTINUATION SHOT FOR ITW NO. 4 FO«M IA02. OWL 1
oo
SOURCE, CONTROL OPTION ESSO, England, CAFB Pilot Plant, SASS-1 EFfLUENT STBFAU vr> 101
A
MMfU FRACTION
UNITS
Er
Ho
Dv
Tb
Cd
Eu
Sm
Nd
Pr
Ce
La
Ba
Cs
1
Te
Sb
Sn
Cd
Pd
Rh
Ru
Mo
Nb
Zr
Y
B
FRACTION
CONCCN
TRATION
Ug/m3
< 6.9
<0.1-2.3
0.2-9.4
< 0.3
< 4.6
0.6-3.4
3.3-16.0
31
10
98
200
2,800
3.7
1.3
8.8
7.2
71
5.4
7.9
0.9
< 1.9
8.4
81
510
120
C
HCAlTH
HATE
CONCCN
TRAtlON
9.3E3
5.3E4
N
5.1E4
3.7E4
1.1E5
5.0E2
1.0E2
5.0E2
N
1.0E1
5.0E3
0
ECOUXCAl.
HATE
CONCCN
T RATION
N
N
N
N
N
N
N
N
N
N
N
N
E
OCGMCOT
HA2AHO
{HEALTH)
(•/O
—
<0.001
< 0.0003
D.0002
D.0026
).0018
5.6
i 08 S
1.014
).54
)."|1?
F
OKOINAt.
|^»S1IIOK IN
HtAlTH UATt
I*8U
G
DCG»U or
HA2ADO
(CCOIOCICAU
(B'O)
H
OHOIHAt.
POSITION id
CCOL MAtt
TABU
1
\ if
HtAt'-
KA'E
WCtEDCO
—
.'
J
\ 'F
CCOl
UATC
ocecotD
_
« 1 i
TOIIC JNit OiSCMAJKt RAU
(HtAlTH
BASQ1I
S i LINE 11
<" 000 T
< 0.00002
0.0001
p. 0014
0.0009
2.91
0.046
0.007
0.281
0.001
iECXXOClCH
BASCO)
1C > UNC )'
-------
TABLE 31 (continued). SAM/IA WORKSHEET FOR LEVEL I - ESSO, ENGLAND, CAFB PILOT PLANT, SASS-1
00
NJ
CONTINUATION SMUT FOR ITEM NO. 4. FOUII 1*02. UVU 1
Pitt
<^ni»rf,rni«tooi npTinw ESSO, England. CAFB Pilot Plant. SASS-1 EFFLUENT STBFAU n.n 101
A
SAMU nucno*
UNITS
Sr
Rb
Br
Se
As
Ge
Ga
Zn
Cu
Ni
[ Co
Fe
Mn
Cr
V
Ti
Ca
K
S
P
Si
Al
>'g
Ka
B
Be
B
nucnoN
CONCCN
THA1BN
UR/m3
2.600
50
160
0.6-75
650
6.2-33
170
860
180
230
48
_
1,700
110
310
13,000
210,000
11,000
-
1.600
230,000
_
16,000
_
4,300
14
C
HEALTH
tun
CONCfN
TRATION
3.1E3
2.0E2
:.o
5.6E2
5.0E3
4.0E3
2.0E2
1.5E1
5.0E1
5.0E3
1
5.0E2
6.0E3
N
1.0E2
1.0E4
5.2E3
6.0E3
5.3E4
3.1E3
2.0
0
[CtKO&CAi
HATE
CONCCN
! RAICH
N
N
N
N
N
N
N
N
N
N
N
1
N
N
N
N
K
N
N
N
N
E
DEGIKC Of
HAMIO
(HtAlTMl
(B/O
—
0.839
.003-. 371
325
.011-.05<
0.034
0.215
0.90
15.33
0.96
0.34
110
0.62
2.17
16
23
2.67
1.387
7
F
OKOINAL
POSITION IN
HCAITH UAtC
TABU
G
EXGTCC Of
HAZARD
(tCOCOGlCAl.)
(B/OI
310
H
0*01 NAt
POSITION IN
ICO. MATt
TA8l£
1
I/ If
MtAlTM
UATC
ucccoco
—
1
/
,•'
/
/
/
I'
/
.'
J
V If
tea.
MAT!
fKOOCO
—
/
K 1 I
TOIC UNIT DlSCMADGI Mn
(HEALTH
BASED)
1C i UNI 3)
0.436
<0.195
169
<0.031
0.018
0.112
0.468
7.97
0.50
0.177
57.2
0.322
1.128
8.32
11.96
1.388
0.721
3.64
(ECOLOCCAl
BASIC)
1C > LINE ))
161
-------
TABLE 32. SAM/IA WORKSHEET FOR LEVEL I - ESSO, ENGLAND, CAFB PILOT PLANT, SASS-2
SAM/IA WORKSHEET FOt LEVEL 1 Form IA02 Ltv«rt 1
00
1 SOURCE/CONTROL OPTION pigf i
ESSO, England, CAFB Pilot Plant, SASS-2
2 EFFLUENT STR£AM 3 £FFLUENT STREAM FLOW RATE
101 Flue gas 0- °'60 m>ec
COM* NAME (gas * m /sec — noun: » i/sec — SONO waste * g lea
4 COMPLETE THE FOLLOWING TABLE FOR THE EFFLUENT STREAM OF LINE 2 (USE BACK OF FORM FOR SCRATCH WORK)
A
bu»U IBACTKX
UNITS
u
Th
Bi
Pb
Tl
Au
Ir
08
Re
U
Hf
Lu
Yb
•fia ___
B
flUClKX
CONCIN
TIUTIOH
ug/m3
13
35
0.5-28
310
< 13
< 13
< 20
< 22
< 14
< 23
< 49
< 13
< 12
< 5.8
C
HEALTH
UATE
CONCCh
TRADON
4.1E2
1.5E2
N
1.0E3
0
CCOlOGlCAt
MATE
CONCEN
IRAI1ON
K
N
N
N
E
DEGOEE Of
HA2ABO
(HEALIHI
IB/C)
-
.001-. 066
<0.087
<0.023
F
OBOIhAi
POSITION IN
HEALtH MATE
TABLE
-
G
OlG»f( T
MA;A«D
.KO'.-XliCAt.
•B Oi
-
H
OTOIXAl
POSITION IN
(COl MATE
TABU
-
1
\ If
MCAlTx
MAIi
ElCEEOEO
-
J
\ if
ECOl.
UAtE
EICECOCD
-
K I L
tOllC UNIt O'SC-AOCl »AIE
IMCALTH
BAStDl
it I LINE )l
<0.041
<0.052
<0.014
lECCXOCKAi
BA»Ol
iu • UNI )l
9 MOM SPOCt H NEEUCD IHt A CONTINUATION «fn
5 EFFLUENT STREAM DEGREE C
HEALTH MATE BASED a COL
ECOLOGICAL MATE BASED a
(ENTER HERE AND AT LINE 6
F HAZARD
F) Sa -92°
M){ tt) Sb '•'O
FORM IA01)
6 NUMBEI
COMPAR
HEALTH 6
ECOlOGiC
) OF ENTRIES
EO TO MATE
, 31
>L or. 1
7 TOXIC UNIT DISCHARGE SUM
5 HEALTH MATE BASED (i COL K)
ECOLOGICAL MATE BASED (1 COL
(ENTER HERE AND AT LINE 8 FO
-551
,,«. 258
RM IA01)
-------
00
TABLE 32 (continued). SAM/IA WORKSHEET FOR LEVEL
CONTINUATION INUT FOR ITEM NO. 4. fO».M IA02. UWl 1
I - ESSO, ENGLAND, CAFB PILOT PLANT, SASS-2
?•*
«nM«-f,rn»iTQni npyin* ESSO, England, CAFB Pilot Plant, SASS-2 uruitui <;m*M NO 101
A
(tutu nucno*
UNITS
Er
Ho
DV
Tb
Cd
Eu
Sm
Nd
Pr
Ce
La
Ba
Ca
I
Tc
Sb
Sn
Cd
Pd
Rh
Ru
Mo
Nb
Zr
Y
Sr
B
RUCTION
CONGIN
HUTCH
Ug/m3
< 18
< 6.2
< 19
< 2,2
< 14
<0. 1-8.1
1.1-31
17-44
11
97
200
5,100
3.5
2.7-12
0.1-15
18
18-400
2.0-27
< 16
< 3.9
< 13
12
78
540
87
5,000
C
HIAITW
UATt
CONCCH
nUTIOM
9.3E3
5.3E4
N
5.1E4
3.7E4
1.1E5
5.0E2
1.0E2
5.0E2
N
1.0E1
5.0E3
3.1E3
0
CCOIOGICAL
MATt
CONCtN
TUT ON
N
N
N
N
N
N
N
N
N
N
N
N
N
E
DCGfttcor
HUMD
mCAiim
(8/Cl
—
^0.002
<0.001
0.0002
0.003
0.002
10.2
.001-. 15
0.036
0.2-2.7
0.002
1.613
r
OSOlHAl
POV'ION IN
HtAirx y«rc
TABU
_
G
txcutc y
HAURO
(CCCKOGICIU
(8/0)
H
00011*1.
POWTION IK
ceot ««n
TABLE
—
1
\ If
HEALTH
U*TC
OCCCMD
/
,'
/ '
J
\ if
IC
-------
TABLE 32 (continued). SAM/IA WORKSHEET FOR LEVEL I - ESSO, ENGLAND, CAFB PILOT PLANT, SASS-2
CONTINUATION UitET CO* ITEM NO. 4. tout IA02. UVU 1 "tie
00
SOURCE CONTROL OPTION ESSOr England. CAFB Pilot Plant. SASS-2 EffLUENT ST»f»M Nr 101
A
UuvunucTOH
UNITS
Rb
Br
Se
As
Ce
Ca
Zn
Cu
Ni
Co
Fe
Hn
Cr
V
Ti
Ca
K
S
P
Si
Al
*g
Na
B
Be
Li
B
nuctioN
CCMCCN
TMTOt
Ug/m3
63
190
16-160
1,000
41
260
1,900
260
130-630
44
-
2,000
330
430
14,000
_
7,700
220,000
1,600
-
-
15,000
000-14,000
1,100
3.8
60
c
MtMTM
nun
CONCCN
THATCH
2.0E2
2.0
5.6E2
5.0E3
4.0E3
2.0E2
1.5E1
5.0E1
5.0E3
1
5.0E2
6.0E3
N
1.0E2
1.0E4
5.2E3
6.0E3
5.3E4
3.1E3
2.0
2.2E1
D
(COtOOCAl
KATE
CONCCN
TMTION
N
N
N
N
N
N
N
N
N
N
1
N
N
N
N
N
N
N
N
N
N
E
OCCMfZ OF
HAZARD
(HCAITH)
(B/O
—
.07-0.80
500
0.052
0.475
1.30
8.67-42
0.88
0.4
330
0.86
2.33
16
2.5
094-.264
1
1 .9
2.73
f
OfUXHAl
POSITION IN
HEALTH UAU
TMU
G
Ofooccor
HA2AIO
(ECOtOQCAl)
ia/o>
—
430
H
OKXNAl
POSITION IN
KOI MATt
TABU
1
V If
HtA4.TH
MAT[
OCCCOCD
,'
/
j
J
/
,•'
,••'
,
,
•
J
\ ir
ICOt
IUTC
cictcoeo
—
K
TO»IC UNIT 01
(HCA4.T"
BASCDl
1C • UNC )l
<0.48
300
0.031
0.285
0.78
<25.2
0.528
0.24
198
0.516
1.398
9.6
1.5
<0.158
0.6
1.14
1.638
I
X**Kt HATl
{EOXOCICAl
8ASID1
1C • LINf 1)
258
-------
routes; lowest reported lethal dose to humans is 1.4 mg/kg admin-
istered orally.
• Beryllium - toxic through all routes of absorption, with major
health hazard via inhalation; chronic exposure causes berylliosis,
with particle size being critical factor; lowest toxic concentra-
tion reported for humans is 0.1 mg/m3; beryllium and 5 beryllium
compounds reported to cause cancer in animals with lowest dose
producing carcinogenic response being 35 pg/m3 as BeSOi* • 41^0 in
laboratory testing.
Because the toxicities of the elements reported are high, it is important
to assure highly efficient control in actual commercial CAFB systems. It is
expected that these trace elements are emitted in particulate form, but fur-
ther Level II testing is required to identify actual compounds and the prob-
ability of escape in the vapor phase.
Using the SAM/IA procedure, analysis of particulate emitted during the
second SASS run (SASS-2), during which emissions exceeded SASS-1 values by
25 percent, indicates some additional trace elements with health hazard factors
greater than 1; namely, Cd, Sr, Cu, and Li. The naturally occurring isotope
of Sr is not highly toxic, but the other three elements are, giving further
support to the need for appropriate emission control in commercial systems.
The health hazard factors for the trace elements discussed above range from
approximately 1 to 500 (covering SASS-1 and SASS-2); the highest value is for
arsenic. The only trace element compared with an ecology MATE is vanadium,
with ecology hazard factors of 310 and 430 for SASS-1 and SASS-2, respectively.
These high hazard factors indicate that particulate control efficiency of 99.8
percent is required to lower the arsenic hazard factor to 1. Due to inconsis-
tencies between MATE values and standards (e.g., the previous discussion of
NOX and 802), it would be inappropriate to base control efficiency objectives
solely on the results of the SAM/IA analysis. Therefore, we have evaluated
(through application of the SAM/IA method) trace element emission data repre-
senting lignite-fired conventional boilers controlled with multiclones or elec-
trostatic precipitators to compare conventional systems with the CAFB. These
sites are located in the midwest and were recently monitored as part of another
EPA contract.3
Site A is a conventional lignite-fired boiler using multiclones for par-
ticulate control. The total measured particulate emission at Site A is
~8.5 gm/m3 as compared to~2.5 gm/m at the ESSO pilot plant. The results
of the SAM/IA analysis of trace element emissions from the boiler are itemized
in Table 33. The trace elements with hazard factors greater than 1 are the
same as those noted during the SASS-1 and SASS-2 sampling runs at the ESSO
pilot plant. Cobalt and manganese are also shown as having health hazard fac-
tors greater than 1. Overall, the hazard factors for these important elements
range between 1 and 800, which is very similar to the CAFB results. It is
important to note that the accuracy of the SSMS technique is within a factor
of 2 or 3 so that differences of an order of magnitude are necessary to be
significant. Overall, the ESSO pilot plant trace element emissions present no
86
-------
00
TABLE 33. SAM/1A WORKSHEET FOR LEVEL I - CONVENTIONAL LIGNITE BOILER WITH MULTICLONE
SITE A
MM/U WORKSHEET FOR LEVEL 1 Form IA02 Uwi 1
1 SOURCE/CONTROL OPTION p<(( , .
Conventional Lignite Boiler With Multiclone _ site A
2 EFFLUENT STREAM J EFFLUENT STREAM FLOW RATE
,„, r, 0- 27.9 m3/sec
CCM I NAH( ((11 * m 'SFC - IIQUlO • 1 ' «C — MHO • »»(» • |/MC)
4 COMPUTE THE FOLLOWING TABLE FOR THE EFFLUENT STREAM OF LINE 2 (USE BACK OF FORM FOR SCRATCH WORK)
A
MWIC AUCTION
UNITS
U
Th
Bl
Pb
Tl
Au
Ir
Os
Re
W
Hf
Lv
Yb
Tm
e
COHCIN
TMtKW
ug/mJ
56
76
2.6
320
< 8.3
< 4.1
< 6.3
< 7.0
<4.5
6.2-33
<13
< 3
< 3.2
< 2.5
C
M[Al!M
HATC
CONCCN
1 Ml ION
ug/mJ
4.1E2
1.5E2
H
1.0E3
0
[COlOGiCAL
u«rc
CONCIK
TUIlON
N
N
N
N
E
OCGSEl 01
•M£AllM,
iB'Cl
-
D.006
<.055
.OC6-.C33,
f
<%£!£•*
-
G
OtCKlf '•»
MA/ARO
.[COlOCH-Av
-
H
oooifuu
POSITION IN
CCCX U*I[
-
1
MAT!
ClCECOCD
-
J
V If
tea
MAtE
tirnoio
-
« 1 1
IOK j>.'l DiSCnlKI "AH
tHCAtTM
BJVID
.( t LINE J>
.167
<1.535
< .921
itCOtOO'Oll
0 . UNC )!
» mm IMCI it MUUCD inc * CONTINUATION win
% EFFLUENT STREAM DEGREE C
HEALTH MATE BASED a COL
ECOLOGICAL MATE BASED (I
(ENTER HERE AND AT LINE 8
F HAZARD
E) 5. < 2032
cm a, Sb 47°
FORM IAOU
6 NUMBEF
COMPAR
HEALTH 61
ECOLOCiC'
I OF ENTRIES
ED TO MATE<
30
1 bC
7 TOXIC UNIT DISCHARGE SUM
' HEALTH MATE BASED (I COL *>
ECOLOGICAL MATE BASED (1 COl
(ENTER HERE AND AT LINE e FOI
< 56,700
LI'S IV13
tM lAOH
-------
TABLE 33 (continued).
00
oo
SAM/1A WORKSHEET FOR LEVEL I
WITH MULTICLONE - SITE A
- CONVENTIONAL LIGNITE BOILER
CONTmUATMN SMIET ft* ITtM NO. 4. FORM IU2. UWl I
SOu"CI'CONTfl
Ru
Mo
Mb
Zr
Y
Sr
8
nuctiON
CtWCIN
T*AT«N
ug/m
< 4.8
< 1.1
< 3.2
< 0.7
< J.2
< 1.8
< 5.4
13
29
240
320
200,000
M
3.3
< 3.3
40
91
33
< 6.7
d f>
< 3.6
38
67
1300
190
41,000
C
HUtTH
UATl
CONCtH
nUTHH
iig/m
9.3E3
5.3E4
N
S.1E4
3.7E4
1.1E5
S.OE2
1.0E2
S.OE2
N
1.0E1
5.0E3
3.1B3
0
tCOUXUCAl
MAT!
CONCtH
THATCH
N
N
N
N
N
N
N
N
N
H
N
N
N
E
ocoMlor
KMATO
(HtAlTM)
(•/O
—
.0003
<.0001
.0006
.0065
.0029
400
<.033
.08
3.3
.0076
13.23
F
-------
TABLE 33 (continued).
oo
SAM/1A WORKSHEET FOR LEVEL I
WITH MULTICLOKE - SITE A
- CONVENTIONAL LIGNITE BOILER
CONTINUATION SHUT FM fTEM NO. 4. FOftM IA02. LfVU 1
SOURCE cc'-'soi OPTION Conventional Lignite Boiler With Multlclone EFFLUENT STRFAM M0 l°l
A
SAAVU nucroH
UNITS
Rb
Br j
Se
As
Ge
Ga
Zn
Cu
Nl
Co
Fe
Hn
Cr
V
Tl
Ca
K
S
P
SI
Al
Mo
Na
B
Be
Li i
B
nucnoN
CQHCCN
THATCH
290
210
S3
1,600
7.2
240
880
470
1,400
100
27,000
470
470
28,000
39,000
160,000
16.000
m _ _
...
140,000
10
570
c
MtAltX
MAT*
CONCCN
TRATION
2.0E2
2.0
5.6E2
5.0E3
4.0E3
2.0E2
1.5E1
5.0E1
5.0E3
1
5.0E2
6.0E3
N
1.0E2
I.OE4
5.2E3
6.0E3
5.3E4
3.1E3
2.0
2.2E1
0
CCOtOGlCAl
MATE
COHCCN
TUITION
N
N
N
N
N
N
N
N
N
N
1
N
N
N
N
N
N
N
N
K
N
E
OCOKU V
HAZARD
IHtALTM)
CB/O
—
.415
800
.0129
.048
.220
2.35
93.33
2.0
5.4
470
.94
4.67
160
45.16
5.0
25.91
F
ORDINAL
FO&TIOM IN
HCALTH fcUTC
TABU
0
OCGOCE 0>
HAZARO
([COlOOCAL
IB/D)
470
H
CXttXNM
POSITION IN
[CM MATt
TABU
1
\ If
MUl.T>.
MAT[
UCUQCD
/
/
/
>/
/
/
y
,/
/
,/
^
j
* *
(COi
U4^C
eicttwo
—
K
l
TOIC UNIT OiSCnAKU UTC
(HCAlTM
BASCDl
1C • UNt 1)
11.58
22,320
.360
1.14
6.138
65.57
2604
si ft
150.7
n in
26.23
130.3
4,464
1 ,260
139 ^
722 •'
>E
-------
greater ambient hazard than the emissions from Site A. This indicates that
the gasifier cyclones and boiler cyclone in use at ERCA have a combined per-
formance at least equal to the multiclones in use at Site A.
Site B is a lignite-fired conventional power plant boiler using an ESP
for particulate control. The measured emission at the stack is 0.0012 gm/m3,
a factor of 2000 less than the total particulate emissions indicated by the
two SASS runs at the ESSO pilot plant. Table 34 indicates the results of the
SAM/IA analysis of trace element emissions from this site. The only elements
with hazard factors greater than 1 are arsenic, nickel, chromium, and vanadium
(ecology); and these values are all reported as upper limits. The accuracy of
the SSMS analysis in this case is quite low because of the very small amount
of material collected in the sampling train. The data are presented to dem-
onstrate the capability of an available control device to lower trace element
emissions to acceptable levels.
A summary of trace element emission data representing the two conventional
sites and the ESSO pilot plant is presented in Table 35. All elements with
hazard factors > 1 at any of the three sites are included. In addition, some
other trace elements (namely, Pb, Sb, Zr, Br, Zn) and sulfur are included for
the purpose of discussion. Lignite trace element concentrations are presented
to indicate comparative amounts processed by each of the three systems. One
immediately apparent feature is that the trace element emissions measured at
the CAFB and Site A are very similar, considering the accuracy of the SSMS
analysis technique. This seems to be true regardless of the input quantity of
each trace element. The most striking differences in feed quantities between
CAFB and Site A exist for the elements Zr, Cr, V, Ti, Mg, Be, and Co. The
feed concentration to the CAFB is at least an order of magnitude higher than
the feed concentration at Site A for these six elements. However, the flue
gas emissions of these elements are all higher at Site A than the CAFB, except
for beryllium. This is partially explained by the fact that total particulate
emissions at Site A are higher than at the ESSO pilot plant by a factor of 3.4
(8.5 gm/m3 versus 2.5 gm/m3). This being the case, there must be some factor
that explains why emissions of these elements from the CAFB pilot plant are
generally lower than measured at Site A by a factor of about 1.5 to 2 instead
of being higher by a factor of > 10/3.4. Apparently, as noted for residual
oil gasification, there is significant adsorption of these trace elements by
the bed material. Trace elements may also be retained in the system in asso-
ciation with nonelutriated ash particles.
Trace element emission concentrations noted for Site B, where an ESP is
used for final particulate control, are generally about two orders of magnitude
less than emissions from the pilot plant and Site A. Since trace element feed
concentrations are similar for Sites A and B, it is projected that application
of a high efficiency control device at a commercial CAFB installation would
provide very adequate control of trace element emissions.
90
-------
TABLE 34. SAM/1A WORKSHEET FOR LEVEL I - CONVENTIONAL LIGNITE BOILER WITH ESP -
SITE B
SAM/IA WORKSHEET FOR LEVEL 1
Form IA02 Lwtl 1
1 SOURCE/CONTROL OPTION
Conventional Lignite Boiler With ESP - Site B
2 EFFLUENT STREAM
101 Flue Gas
COOf • NAU(
Page 1
3 EFFLUENT STREAM FLOW RATE
Q . 40.5 m /sec
(go • mVjec — liquid - ' «c — »iiO *»«* « g'«c)
4 COMPLETE THE FOLLOWING TABLE FOR THE EFFLUENT STREAM OF LINE 2 (USE BACK OF FORM FOR SCRATCH WORK)
A
SUtfU nuctON
UNITS
u
Th
Bl
Pb
Tl
Au
Ir
Os
Re
W
Hf
Lv
Yb
Tm
B
nUflOM
COMQN
TUTION
< 1.2
< I./
< .5
I.I - 8.5
< .7
< .9
< 1.4
< 1.5
< .9
< 1.3
< 1.6
< .it
< -5
< .3
C
NEAUH
MATE
CONCEM
TltAIION
6.1E2
1.5E2
N
1.0E3
0
CCOIOOCM
KATE
CONCEN
'RATION
N
N •
N
N
E
OCCMI Of
HAZARD
IHEAltH)
(B'Cl
_
< .0012
<. 0047
<.0013
F
ORDINAL
FOSlTiON IN
HUL'M MATE
TABU
-
* MOW IMCC 15 NtlUtO. Wt * CONTINUATION MEET
5 EFFLUENT STREAM DEGREE C
HEALTH MATE BASED a COL
ECOLOGICAL MATE BASED (I
(ENTER HERE AND AT LINE 8
f HAZARD
E) 5. '• 12-1
COL r.t 5b < 1 . 1
FORM'iAOli
G
OlG»l( 0<
M»/»»a
ItCOlOCICAu
IB-D.
-
H
OKNNAl
posnion IN
ECOl UATE
TABU
-
1
~e»i'-
U«T(
EiCEtQCO
-
J
V 1'
(CO
MATE
EiCEEDEO
-
K
L
tQllC UNit OiSC""Ct RAH
(Nt«ltM
BASED)
lE • UNE ll
<.049
<.190
<.053
lECOlOC'CAi
BAS(Ol
IG • UNI )l
6 NUMBER OF ENTRIES 7 TOXIC UNIT DISCHARGE SUM
COMPARED TO MATCS HEALTH MATE BASED 11 COL K)
HEALTH 6« J^ ECOLOGICAL MATE BASED (1 COL
ECOLOGKAt frt ' (ENTER HERE AND AT LINE 8 fO
7. <-'-^.«.- -
L) 7bf_ "!!'-_
RM IA01)
-------
TABLE 34 (continued).
VO
N>
SAM/1A WORKSHEET FOR LEVEL I - CONVENTIONAL LIGNITE
BOILER WITH ESP - SITE B
CONTmUATKM IMltl f W I1UI NO *. KMM IMS. UVU 1
cmiMVjrnMTont OPTION Conventional URnlte Boiler With ESP EFFLUENI ST«»U NO 101
A
uuounucroi
UNITS
Er
Ho
Dy
Tr
Gd
K«
Sm
Nd
Pr
Ce
La
R>
Cs
I
Te
Sb
Sn
Cd
Pd
Rh
Ru
Mo
Nb
Zr
y
Sr
B
RUCTION
CONCIN
TUMON
< 1
< .3
< .5
< .1
< .5
< .2
< .9
< 1.2
< .2
< -3
< .3
< ?fl
< .1
< .8
< .7
< .5
1.3-16
.9-2.1
< -7
< .2
< .9
.8
< -1
.3
< .l-.l
<10
C
NUtfVI
MAfI
CONCCN
TMTKW
9.3E3
5.3E4
N
5.1EA
3.7E4
1.1E5
5.QE2
1.0E2
5.0E2
N
1.0E1
5.0E3
3.1E3
0
DXPtOOlCAl
HATt
COMCtN
TTWTION
N
N
N
N
N
N
N
N
N
N
N
N
N
E
ouwaor
MAZAIO
(MCALTM)
mm
—
.00005
.00002
<. 00001
<. 00001
<. 00001
.056
<.007
<.001
.09-. 21
.o66J
<.0032
f
OMMML
rosriON IN
H(MTM IUTC
UBU
—
G
MCMU OF
HA2AIO
(ECOLOGICAL)
m/m
—
H
MMNM
KOSITION is
ICOl MATE
tAMJE
1
s'lf
HLM.TM
MATE
aCXEOCD
—
J
tea
MATt
CICtCDCO
—
K
L
10»C UNIT OUCHAJKt MT(
(ICALTH
MSB))
(E . UHI I)
.002
.001
< .0004
< .0004
< .0004
<2 2flfl
< .284
< .041
<8.505
.008
< .130
tECOtOGCAl
BAJtO)
1C > UNI })
-------
TABLE 34 (continued).
vo
u>
SAM/1A WORKSHEET FOR LEVEL I
BOILER WITH ESP - SITE 8
- CONVENTIONAL LIGNITE
CONTMUATKM SHCET rot in* NO 4. rOMH 1*02. UVU I
SOuPtt/eoNTHOi OPTION Conventional Lignite Boiler With ESP ErauENT STBF AM NO 101
A
MMunucnoN
UNITS
Rb
Br
Se
As
Ce
G«
Zn
Cu
"^
Co
Fe
Mn
Cr
V
Tl
Cc
K
s
t>
SI
Al
MS
Na
B
Be
Li
B
nUCTKM
CONCIM
TMTON
< .1-.4
<43
9.7
< A. 2
< .1-.3
< .l-.l
13-31
< 36
<69
< .8
<170
< 7.8
< 4.2
< 1.1
< 3.5
40-390
560
1400-7700
< Ld
180
36-88
160
680
64
.2
< .3
C
HCAITH
MAT!
CONCCft
TRATION
2.0E2
2.0
5.6E2
5.0E3
4.0E3
2.0E2
1.5E1
5.0EI
5.0B3
I
5.0E2
6.0E3
N
1 . (IE?
1.0E4
5.2E3
6.0E3
5.3E4
3.1E3
2.0
2.2E1
0
ICOUXOL
UATt
CONCtN
nurioN
N
N
N
N
N
N
N
N
N
N
1
N
N
N
N
N
N
N
N
N
N
E
ocoMtor
HAZARD
(MIAITH)
tt'Cl
—
.0485
<2.1
<-0005
C. 00002
<-0078
<.18
< 4.6
<.016
C0016
e4.2
C.0022
C.0006
C.46
.0180
c.0169
.0267
.0128
.0206
.1
.0136
f
ODOlNAl
POSITION IN
MEA1TH UAT[
TAflU
G
MG»u or
HAZARO
(CCOLOUCAU
(B/OI
1 . 1
H
OUfXNAL
POSITION IN
[CM MATt
TASK
1
\ If
"CAlTH
MATt
oaeocD
—
/
/
,/
j
v a
cca.
lUTt
ciauxo
—
/
K
T01IC UNIT l>
IHCALTM
IASO))
It I LINE 11
1.964
<85.05
< .02
< nni
< .316
< 7.29
< 186.6
< .646
< .065
<170.1
< .089
< .024
< 18.63
.7J9"
< .684
1.081
.518
.834
4.05
.551
I
SCHAJIGf MT(
xcoioaCAi.
B*SU»
1C 1 UMC 3i
< 44.55
-------
TABLE 35. SUMMARY OF TRACE ELEMENT DATA
vo
Trace
element
Pb
Ba
Sb
Cd
Zr
Sr
Br
As
Zn
Cu
Ni
Cr
V
Ti
S
P
Si
Mg
B
Be
Li
Co
Mn
Lignite
CAFB
1197
9.6
38
0.30
0.17
5.9
37
0.23
1.5
13
15
23
2.7
14
230
0.23Z
42
MC
130Z
21
0.03
0.82
0.50
22
fuel feed data
(ppm)
Site
A
1.7
110
0.055
0.28
0.37
38
3.3
2.6
10
62
4
0.48
0.56
9.3
0.23Z
14
Site
B
2.3
7.0
<0.22
<0.39
0.35
46
3.2
0.48
15.0
7.1
48
0.61
0.87
15.0
1.4*
8.6
170 420
420 840
6.3
0.018
0.26
0.089
11.0
8.9
0.037
0.17
13.0
Flue gas emissions (-g/m')
CAFB
SASS-1
200
2,800
7.
5.
510
2,600
160
650
860
180
230
110
310
13,000
-
1,600
230,000
16,000
4,300
14
KD
48
1,700
SASS-2
310
5,100
2 18
4 15
540
5,000
190
1,000
1,900
260
380
330
430
14,000
220,000
1,600
-
15,000
3,100
3.8
60
44
2,000
Site
A
320 1
200,000
40
33 0
1.300
41,000
210
1,600
880
470
1.400
470
470
28,000
Site
B
.1 to 8.5
<28
< 0.5
.9 to 2.1
0.3
<10
<43
< 4.2
13 to 31
<36
<69
< 4.2
< 1.1
< 3.5
160,000 1400 to 7700
16,000
-
MC
140,000
10
570
100
27,000
<46
180
160
64
0.2
<0.3
<0.8
<7.8
Solid
CAFB
basis
SASS-l SASS-2
90.5
1,268 1
3.3
2.4
231
1,177 1
72.4
294
389
81.5
104
49.8
140
5,885 5
80
724
104,100
7,243 5
1,946 1
6.3
113
,018
2.6
2.0
196
,818
69.1
364
651
94.6
138
120
156
,091
,000
582
-
,455
,127
1.4
21. a
(ppm)
Site
A
37.
23,585
4.
3.
153
4,835
24.
189
104
55.
165
55.
55.
3,302
18,868
1,887
-
-
16,509
1.
7
7
9
8
4
t
4
,2
67.2
Note: ND » not determined; MC * major component.
-------
ORGANIC EMISSIONS
The variability of the distribution of organic emissions among the gaseous,
volatile and condensable samples collected during the two SASS and two Tenax
RAC runs is demonstrated by the emissions summary presented in Table 36. As
noted in Section 4, SASS No. 1 measurements were made during reinjection of
gasifier fines with the apparent result that lignite gasification efficiency
was higher than during subsequent runs.
To establish a basis for evaluation of the potential environmental impact
of organic emissions from the CAFB, Table 37 summarizes emissions determined by
GCA from six conventional lignite-fired boilers. Comparison between the data
in Tables 36 and 37 shows that the total organic emissions from the CAFB fall in
the middle of the range found for conventional systems. The > Cg emissions
from the CAFB during SASS No. 1 is on the low end of the distribution, while
the emissions from SASS No. 2 and RAC No. 4 are higher than any found from con-
ventional systems.
The principal conclusions which can be drawn from a comparison between
CAFB and conventional organic emissions is that when operated efficiently,
gaseous (Ci - Cg) organic emissions from the CAFB are equivalent to those from
conventional systems and emissions of heavier organlcs are lower than the aver-
age from conventional boilers. The large number of organic functional groups
identified by infrared spectroscopy indicates that Level II organic analyses
should be performed to definitize the specific compound nature of the organic
emissions.
TABLE 36. TOTAL CAFB ORGANIC EMISSIONS (yg/m3)
SASS No. 1 SASS No. 2 RAC No. 2 RAC No. 4
Cj - Cg
C? ~ Cl6
> Ci6
17,770-
23,192
221
565
No data
307
21,725
4,337-
10,384
*
650
7,590*
< 6,380
1,430*
19,740*
Total 18,556- > 21,725 12,577- 21,170-
23,978 18,624 27,550
*
Average RAC 1-5 particulate emissions plus Tenax
captured emissions.
95
-------
TABLE 37. ORGANIC EMISSIONS FROM CONVENTIONAL
LIGNITE-FIRED UTILITY BOILERS
Boiler type
Pulverized dry bottom
(front fired)
Pulverized dry bottom
(front fired)
Pulverized dry bottom
(front fired)
Cyclone
Spreader stoker
Spreader stoker
Organic emissions
(yg/m3)
GI - Cg Cy - Gig > Gig
39,020- 434 9,800
44,520
5,340- 936 6,930
17,430
4,000- 558 64
13,000
10,680- 382 2,410
22,770
1,780- 643 1,745
13,870
No data 27 332
rotal organic
emissions
(yg/m3)
49,300-
54,800
13,200-
25,300
4,600-
13,600
13,500-
25,600
4,200-
16,300
> 359
96
-------
EMISSIONS FROM OIL-FIRED HDS AND FGD PROCESSES
Potential emissions from these sources have been discussed in an earlier
report. Pollutant streams emanating from limestone FGD and Flexicoking HDS
will be specified here.
Limestone FGD
This is a "throwaway" FGD method which uses a circulating CaCO^ scrubbing
solution for S02 removal by the following reactions:1*
CaC03 + S02 + h H20 -" CaS03 • k H20 I C02
CaS03 • h H20 + 3/2 H20 + ^ 02 + 2 H20 +
The calcium sulfite/sulfate solid waste generated amounts to approximately
four times the weight of sulfur removed from the flue gas stream.5 The waste
slurry is generally discharged to a large pond for solids separation or it can
be dewatered by mechanical means such as centrifugation or filtration. The
chemical pollutants in FGD sludges originate from process ingredients, fuel,
combustion products, absorbents, and process makeup water. Trace elements
exist in the slurry liquor in the range of 0.01 to 1.0 mg/J, and in the solid
phase at a concentration approximately two orders of magnitude higher.6 (See
Table 38.) The limestone scrubbing system operates at the lowest pH in com-
parison to other FGD systems and, therefore, has the highest distribution of
trace elements in liquor. Typically, trace element distribution will be 1 to 2
percent in liquid and 98 to 99 percent in the solids. The low pH in the lime-
stone process apparently causes a greater degree of trace element leaching
from the fly ash. Table 39 illustrates the chemical characteristics of lime-
stone FGD solids at a number of coal-fired plants.
It is reported that the most persistent pollution potential associated
with limestone FGD waste disposal is by water percolation through the sludge
and subsoil into the subterranean water table. Three methods of reducing the
environmental impact of limestone FGD waste disposal are:1*
• decreasing the permeability of solid wastes to reduce water
seepage
• reducing leachability through a reduction of solubility
• managing seepage and runoff to limit the excess of waste
constituents to ground-water or surface-water
An effective embodiment of these ideas is sluicing of waste sludge to an under-
drained pond so that excess liquor can be returned to the scrubber while re-
ducing seepage and overflow by minimizing supernatant hydraulic head.
97
-------
TABLE 38. RANGE OF CONCENTRATIONS OF CHEMICAL
CONSTITUENTS IN FGD SLUDGES
Scrubber
constituent
Aluminum
Arsenic
Beryllium
Cadmium
Calcium
Chromium
Copper
Lead
Magnesium
Mercury
Potassium
Selenium
Sodium
Zinc
Chloride
Fluoride
Sulfate
Sulfite
Chemical oxy-
Sludge concentration range
Liquor
(mg/£, except pH)*
0.03
<0.004
<0.002
0.004
180
0.015
<0.002
0.01
4.0
0.0004
5.9
< 0.0006
10.0
0.01
420
0.6
600
0.9
<1
- 2.0
- 1.8
- 0.18
- 0.11
- 2600
- 0.5
- 0.56
- 0.52
- 2750
- 0.07
- 100
- 2.7
- 29,000
- 0.59
- 33,000
- 58
- 35,000
- 3500
- 390
Solid (ppm)f
-
0.6
0.05
0.08
105,000 -
10
8
0.23
-
0.001
-
2
-
45
_
-
35,000 -
1600
—
-
52
6
4
268,000
250
76
21
-
5
-
17
(4.8)
430
(0.9)
-
473,000
302,000
_
gen demand
Total dissolved 2800 - 92,500
solids
pH 4.3 - 12.7
Liquor analyses were conducted on 13 samples from seven
power plants burning eastern or western coal and using
lime, limestone, or double-alkali absorbents.
Solids analyses were conducted on six samples from six
power plants burning eastern or western coal and using
lime, limestone, or double alkali.
98
-------
TABLE 39. PHASE COMPOSITION OF FGD WASTE SOLIDS IN WEIGHT PERCENT6
Atomic
formula
TVA Shawnee TVA Shawnee TVA Shawnee SCE Mohave APS Choila
limestone, limestone, limestone, limestone, limestone,
2/1/73 7/12/73 6/15/74 3/30/73 4/1/74
CaSOt, •
CaS03 •
CaC03
MgSOi, •
NaCl
Fly ash
2H20
1/2H20
6H20
21.9
18.5
38.7
4.6
-
20.1
15.4
21.4
20.2
3.7
-
40.9
31.2
21.8
4.5
1.9
-
40.1
84.6
8.0
6.3
-
1.5
3.0
17.3
10.8
2.5
-
-
58.7
Total
103.8
101.6
99.5
103.4
89.3
99
-------
Flexicoking
This process was developed by EXXON Research and Engineering Company as a
method of producing low sulfur fuel oil blendstocks from a wide range of resid-
ual feedstocks.3 A schematic process diagram is shown in Figure 21. The
major pollutant sources include the purge coke, the venturi scrubber and
cyclones fines, and the fractionator wastewater. Minor fugitive emissions may
escape from equipment and piping joints. The coke purge quantity ranges
between 1 and 2 percent of the total feed weight. Approximately 99 percent
of the trace metals in the feedstock are concentrated in the coke purge, cy-
clone fines and venturi scrubber fines.7 Table 40 illustrates the chemical
characteristics of these three streams during processing of West Texas sour
asphalt, and documents the system's capability for trace metal removal.8
Table 41 shows a materials balance for vanadium based on a feedstock concen-
tration of 160 ppm.
The Flexicoking system is also efficient in generating a coke gas with
low nitrogen content typically less than 3 ppm. This minimizes the formation
of nitrogen compounds during combustion of the product gas.
Fractionator scrubber wastewater is the major source of liquid waste
within the Flexicoking process. In general, this stream will contain organics,
solids, trace elements, and sulfur compounds. A recent publication8 indicates
that conventional biological treatment or some form of activated carbon fil-
tration would be suitable for producing a water stream with effluent quality
within the limits of current regulations.
Fugitive leakage at pipe joints or other equipment connections would
discharge a minor quantity of hydrocarbon compounds.
100
-------
SCRUBBER
FRACTIONATOR
HEATER GASIFIER
VENTURI
SCRUBBER
JSAS
FRACTIONATOR
WASTE WATER
CYCLONE
LOW SULFUR
COKE
WITHDRAWAL FINES
REMOVAL
PURGE |[
COKE W
Figure 21. Flexicoking Unit.8
-------
TABLE 40. PROPERTIES OF COKE PRODUCTS FROM WEST TEXAS
SOUR ASPHALT OPERATION*6
Coke product
Percent of reactor product
coke
Weight average particle
size, microns
Sulfur, weight percent
Vanadium, wppm
Nickel, wppm
Ash, weight percent
Bed purge
1
105
2.08
4,990
380
2.0
Tertiary fines
2
25
2.60
5,400
295
2.6
Venturi fines
2
5
3.15
10,800
590
5.2
95 percent gasification operation without fines recycle.
102
-------
TABLE 41. PROTOTYPE FLEXICOKER DISPOSITION OF VANADIUM
AMONG PRODUCTS*
Vanadium
concentration
(wppm)
Fresh feed 160
Reactor liquid product
Bed coke purge 5,800
Tertiary cyclone fines 9,000
Venturi scrubber fines 11,000
Total output
Vanadium Percent
rate of feed
(Ibs/day) vanadium
37
0.5
6.1
14.0
18.7
39.3
100
1.3
16.5
37.8
50.5
106.1^
Vanadium balance obtained during the West Texas resid/
asphalt operation.
Percent of feed vanadium as total output indicative of
vanadium balance closure.
103
-------
REFERENCES
1. Schalit, L. M., and K. J. Wolfe. SAM/IA: A Rapid Screening Method for
Environmental Assessment of Fossil Energy Process Effluents. Prepared
for the U.S. Environmental Protection Agency, Office of Research and
Development, by Acurex Corporation. Publication No. EPA-600/7-78-015.
February 1978.
2. Cleland, J. G., and G. L. Kingsbury. Multimedia Environmental Goals for
Environmental Assessment - Volumes I and II. Prepared for the U.S.
Environmental Protection Agency by Research Triangle Institute. Publi-
cation No. EPA-600/7-77-136a. November 1977.
3. Werner, A. S., C. W. Young, M. I. Bornstein, R. M. Bradway, M. T. Mills,
and D. F. Durocher. Preliminary Environmental Assessment of the CAFB.
GCA/Technology Division, Bedford, Massachusetts. Prepared for the U.S.
Environmental Protection Agency, Research Triangle Park, North Carolina.
Publication No. EPA-600/7-76-017. October 1976. 324 pp. (NTIS No.
PB 262-001/AS).
4. Engdahl, R. B., J. M. Genco, and H. S. Rosenberg. State of the Art for
S02 Control for Coal-Fired Power Plants. Battelle Memorial Institute.
5. Foster, R. E., et al. Process Technology Background for Environmental
Assessment/Systems Analysis Utilizing Residual Fuel Oil. Catalytic, Inc.
Prepared for the U.S. Environmental Protection Agency. U.S. EPA Contract
No. 68-02-2155.
6. Rossoff, J., et al. Disposal of By-Products from Nonregenerable Flue
Gas Desulfurization Systems: Second Progress Report. The Aerospace
Corporation. Prepared for the U.S. Environmental Protection Agency.
U.S. EPA Contract No. 68-02-1010.
7. Matula, J. P., B. V. Molstedt, and D. F. Ryan. Flexicoker Prototype
Demonstrates Successful Operation. EXXON Research and Engineering
Company. 40th Midyear Meeting of the Division of Refining, American
Petroleum Institute. May 13, 1975.
8. Griffel, J., G. E. Phillips, and G. C. Spry. Flexicoking Clean Products
from Dirty Fuels. EXXON Research and Engineering Company. May 13, 1976.
104
-------
APPENDIX A
PROCESS DESCRIPTIONS AND ECONOMICS OF
RESIDUAL OIL DESULFURIZATION TECHNIQUES
Several refinery processes exist for the desulfurization of fuel feedstock.
A number of these systems have been discussed in an earlier report, and include
the following:*
• Flexicoking
• Gulf HDS
• RCD Isomax
• Residue Desuifurization (BP)
• Resid Hydroprocessing (Standard Oil)
• LC Fining
• Resid Ultrafining
• Go Fining
• Residfining
• Residue Hydrodesulfurization
• Hydrodesulfurization, Trickle Flow
• IFF Resid and VGO Hydrodesulfurization
• Demetallization/Desulfurization
• Delayed Coking
• VGO/VRDS Isomax
• Shell Gasification
The purpose of this discussion is to update the technical and economic informa-
tion which was presented for these processes and to report upon new processes
which have been identified since the initial study. These additional processes
include:
• Autofining • BP Hydrofining
• Gulfining • Ultrafining
• Shell Residual Oil Hydrodesulfurization • Unicracking/HDS
• Exxon Hydrofining • Unionfining
A-l
-------
Literature review and correspondence with developers have indicated that
technical modifications instituted since the initial report1 have little
economic impact. The major point of technical advance seems to be catalyst
improvement, which enhances demetallization and desulfurization, extends
catalyst life, and reduces catalyst replacement cost.
THE GENERAL HYDRODESULFURIZATION PROCESS
The hydrodesulfurization process is used to remove sulfur, nitrogen and
metals from petroleum feedstocks. In most cases, the feedstock is mixed with
hydrogen-rich gas, preheated, and sent to a fixed bed reactor where the mixture
comes into contact with a cobalt or nickel-molybdenum catalyst. Fuel sulfur is
converted to H2S, nitrogen to NH3, and metals are picked up by the catalyst.
The reactor products are cooled and travel to a separator where t^S
and hydrogen are removed. Hydrogen is recycled to the head of the process and
H2S is treated further for sulfur recovery. The liquid product is steam-
stripped to remove residual contaminants and may be fractionated depending
upon the desired end products. A typical schematic process flow diagram ap-
pears in Figure A-l.
In some cases, an ebullating bed or continuous catalyst feed and withdrawal
system is used. The design and operation of each system is dependent upon
the feedstock and desired end products.
ECONOMIC FORECAST
In order to develop a basis of cost comparison among the various hydro-
desulfurization processes, all economic data has been forecasted to the year
1980. Published capital and operating costs were updated by use of the Nelson
Refinery Inflation Index and the Nelson Refinery Operating Index. In addition,
1980 unit operating costs were estimated by reference to literature concerning
refinery processes .2~t* The 1980 Nelson Refinery Index values and the unit
operating costs used for the analysis are as follows:
• Nelson Refinery Inflation Index 760
• Nelson Refinery Operating Index 295
1980 Unit Operating Costs:
• Electricity $0.03/kWh
• Supplemental fuel $3.25/MMBtu
• Cooling water $0.05/Mgal
• High pressure steam $4.50/Mlbs
• Medium pressure steam $3.25/Mlbs
• Low pressure steam $2.00/Mlbs
• Process (boiler feed)
water $1.50/Mgal
• Hydrogen $1.00/Mscf
A-2
-------
MAKE -UP
HYDROGEN
HYDROGEN RICH RECYCLE GAS
FIXED BED
REACTOR
HEATER
CATALYST
SPENT
CATALYST"
HYDROGEN
DESULFURIZED
PRODUCTS
RICH GAS
SEPARATOR)
LIQUID
PRODUCT
•H2S
SEPARATOR
RESIDUAL
CONTAMINANTS
STRIPPER
FRACTIONATOR
Figure A-l. Generalized schematic hydrodesulfurization flow diagram.
A-3
-------
These unit operating costs are identified here for use below, because, in most
cases, actual utility requirements are published by licensors, rather than
total operating costs for a given year. A discussion of the engineering and
economic aspects of the newly identified residual oil desulfurization systems
follows.
AUTOFINING5
This process is licensed by British Petroleum Trading Limited and is used
to desulfurize distillate stocks, such as feed to SNG plants, without an ex-
ternal source of hydrogen.
Process Description
The process flow diagram is shown in Figure A-2. The system operates in the
temperature range of 730 to 760 F and at a pressure of approximately 300 psig.
The catalyst is regenerated through contact with air/steam or inert gas/air
mixtures. The advantages of the system are:
• No external source of hydrogen required
• High desulfurization capacity
• Easily regenerable catalyst.
Stage of Development
Four units have been installed as follows:
*
Location Capacity (bpsd)
Wales 3,500
Aden 3,500
Scotland 500
France 2,300
Thirteen other BP hydrotreaters have been operated as Autofiners in the
absence of process hydrogen.
Economic Forecast
The economic data given in Table A-l are based on estimates for March 1976.
The estimated 1980 investment cost was projected through the use of a Nelson
Refinery Inflation Index of 760. Electricity and fuel coats were calculated
based on estimated 1980 unit costs of $0.03/kWh and $3.25/MMBtu, respectively.
The catalyst replacement cost was projected by use of a 1980 Nelson Refinery
Operating Index of 295.
* j
Barrels per stream day.
A-4
-------
SEPARATOR
HEATER REACTOR HjS STRIPPER
FEED
DESULFURIZED
PRODUCT
Figure A-2. Autofining process.
A-5
-------
TABLE A-l. ESTIMATED COST OF AUTOFINING, 1980
Cost, $ per bpsd
Investment:
Basis: 45,000 bpsd unit, estimated
erected cost, excluding
initial catalyst charge. 95
Operating Requirements, per bbl of feed Cost, c per bbl feed
Electricity 1.2 kWh 3.6
Fuel 45.5 MBtu 14.8
Catalyst replacement 0.3
Steam 2.0
Cooling water 1.0
Annualized capital 4.3
Maintenance 0.9
Property tax and insurance 0.6
Operating labor and supervision 4.5
Administration, misc. supply, and overhead 0.9
Total operating cost, c/bbl 32.9
GULFINING6
This system is used for hydrodesulfurization of heavy distillate gas oils
including vacuum distillate.
Process Description
The feedstock gas oil is mixed with fresh and recirculating hydrogen and
heated prior to entering the Gulfining reactor, where sulfur compounds are
converted to hydrogen sulfide. Cooled reactor effluent is sent to a flash
drum where liquid oil is withdrawn from the bottom. High pressure flash drum
liquid passes to the low pressure flash drum where hydrogen sulfide and addi-
tional fuel gas is flashed off. Liquid from the low pressure separator passes
to the stripper tower where the desulfurized gas oil is stabilized. Figure A-3
shows the process diagram of the system.
Typical yields for Gulfining Middle East vacuum gas oil at 90 percent
desulfurization are presented in Table A-2.
A-6
-------
REACTOR H.P. SCRUBBER L.P. JCRUBBER
SEPARATOR SEPARATOR STRIPPER
HYDROGEN
MAKE-UP
RECYCLE
FUEL GAS
w
FRESH
FEED
f^\ i
• r
(STAHv |
v\
A . ..
(
1
c
FUEL GAS
r
OESULFURIZEO
GAS OIL
Figure A-3. Gulfining process.
A-7
-------
TABLE A-2. YIELDS FROM GULFINING PROCESS
Characteristic
Gravity, °API
ASTM Distillation, °F
1 BP
10%
50%
90%
EP
Sulfur, wt. %
Carbon residue, wt. %
Nickel and vanadium, ppm
Viscosity, cs at 122°F
Feedstock
24.0
410
622
870
1,020
1,090
2.20
0.7
2
20
Product
29.0
0.2
0.2
—
16
TABLE A-3. ESTIMATED COST
OF GULFINING, 1980
Investment
Basis: 35,000 bpsd
Utilities
Requirement Unit Cost
Cost, $ per bpsd
416
Cost,
C per bbl feed
Electricity
Fuel
Steam
Cooling Water
Hydrogen
Catalyst replacement
Annualized capital
Maintenance
Property tax and insurance
Operating labor and
supervision
Administration, misc. supply,
and overhead
Total operating cost, c/bbl
1.7 kWh/bbl
55 MBtu/bbl
6 Ibs/bbl
160 gal/bbl
350 scf/bbl
$0.03/kWh
$3.25/MMBtu
$3.25/Mlbs
$0.05/1000 gal
$1.00/1000 scf
5.1
17.9
2.0
0.8
35.0
0.3
19.0
3.8
2.6
3.5
3.8
93.8
A-8
-------
Economic Forecast
The economics of the Gulfinlng Process are illustrated in Table A-3 and
are based on the operating parameters shown in Table A-2.
HYDRODESULFURIZATION, RESIDUAL OIL (SHELL DEVELOPMENT CO.)7
The process is used to improve the quality of residual oils by removing
sulfur, metals, and asphaltenes. Use of various catalysts makes the system
capable of treating a wide range of feedstocks, including those which are high
in metals and/or asphaltenes.
Process Description
Feedstock is combined with hydrogen rich makeup and recycle gas and heated
in heat exchangers and a furnace and then passes through the reactor in trickle
flow. Reactor products are cooled and separated into a desulfurized product,
a sour gas, and a hydrogen rich gas which is recirculated after H2S removal.
A bunker reactor can be used for catalyst addition and withdrawal and is es-
pecially suited to treating high metals feedstocks. A process flow diagram
appears in Figure A-4.
Stage of Development
As of 1976, two units were in operation, one demonstration plant of
3,000 bpsd capacity and one commercial facility of 47,000 bpsd capacity.
Economic Forecast
The economics of the process are based on the operating parameters shown
in Table A-4.
TABLE A-4. TYPICAL OPERATING PARAMETERS SHELL RESIDUAL OIL
HYDRODESULFURIZATION
Properties Feed (660°F+) Product (330°F+)
Specific gravity, d 15/40°F
Viscosity, cs at 122°F
Sulfur, wt. %
Vanadium, ppm wt .
Cy asphaltenes, % wt .
0.967
580
4.18
50
2.5
0.917
61
0.50
12
1.2
Chemical H2 consumption: 1.2% wt. on feed
Breakdown of products, % wt. on feed:
H2S 3.9
G!-C^ 0.9
C5-165°C 1.0
165V 95.4
A-9
-------
FILTER
CATALYST
r-Jt-
v!
SMEMT
CATALYST
H,S
REMOVAL
UPO OTF-6A8
1 •"
, )
\
~KJ-9\
(
IX)
)
n
c
)
-*1
(
•
/
S
PRODUC
rRACTK
^
Figure A-4. Shell residual oil hydrodesulfurization.
A-10
-------
The estimated cost of utility requirements for this Shell hydrodesulfuriza-
tion process are given in Table A-5. The catalyst cost has been forecasted
through use of a Nelson Refinery Operating Index of 295 for the year 1980.
TABLE A-5. ESTIMATED OPERATING COST OF THE SHELL
RESIDUAL OIL HYDRODESULFURIZATION PROCESS, 1980
„_.,... Requirement, per .. . Cost,
Utilities M ... , I Unit cost ' , ,
bbl feed c per bbl feed
Hydrogen
Electricity
Fuel
Steam, med. pres.
Cooling water
Catalyst
1020 scf
6 kWh
65.5 MBtu
15 Ibs
225 gal
$1.00/Mscf
$0.03/kWh
$3.25/MMBtu
$3.25/Mlbs
$0.05/1000 gal
102
18
21.3
4.9
1.1
21.0
HYDROFINING (EXXON)8
This system improves the quality of a wide variety of petroleum feedstocks
by catalytic treatment with hydrogen. The process can be used to remove sulfur
and nitrogen as well as improve the odor, color, stability, and burning charac-
teristics of feeds ranging from light ends to heavy distillate gas oil and
lube stocks.
Process Description
The petroleum feedstock is heated to a temperature between 400 and 700 F,
and then passed to a fixed bed reactor along with hydrogen rich gas. The
feedstock is treated at pressures between 200 to 500 psig in the presence of
a regenerable metal oxide catalyst. The reactor effluent is cooled and the
hydrogen rich gas is separated for use in other operations. After separation,
the product is stripped for removal of residual hydrogen sulfide. The process
flow diagram is shown in Figure A-5.
Stage of Development
Approximately 225 units are in operation or are being designed with a
total capacity of 4,000,000 bpsd.
Economic Forecast
The economics of the Exxon Hydrofining Process are given In Table A-6.
A-ll
-------
MCACTOft
COOLLA
STftIF
fMEMCAT
MOOMCT
GOOL0
Figure A-5. Exxon Hydrofining Process.
A-12
-------
TABLE A-6. ESTIMATED COST OF EXXON HYDROFINING, 1980
Investment
Basis: Direct material and labor
Utilities
Requirements
Cost, $ per bpsd
102 - 384
Unit Cost Cost,
C per bbl feed
Electricity
Steam, low pressure
Fuel
Cooling water
Catalyst replacement
Hydrogen
Annualized capital
Maintenance
Property tax and insurance
Operating labor and
supervision
Administration, misc. supply,
and overhead
Total operating cost,
c/bbl
0.3 to 1.0 kWh/bbl
5 to 12 Ib/bbl
0 to 30 MBtu/bbl
0 to 70 gal/bbl
$0.03/kWh
$2.00/Mlbs
$3.25/MMBtu
$0.05/Mgal
0.9 to 3
1 to 2.4
0 to 9.8
0 to 0.4
0.3
60.0
4.6 to 17.6
0.9 to 3.5
0.6 to 2.4
3.0 to 4.0
0.9 to 3.5
78.4 to 105.9
Wide range of investment cost due to variety of applications; large virgin
feed units tend to be in the lower cost range while small cracked stock
feed units are covered by the higher cost range.
HYDROFINING (BP)9
The system is used to remove sulfur from a wide range of distillate feed-
stocks by catalytic hydrogenation. Feedstock can range from light gasolines
to vacuum gas oils up to 1020°F end point, including catalytic cracker cycle
oil or coke gas oil components.
Process Description
Feedstock is mixed with hydrogen rich gas, heated, and passed through a
fixed bed desulfurization catalyst reactor. The hot reactor effluent is cooled
and separated into liquid and gaseous streams at high pressure. The separated
gas stream is recycled to minimize makeup hydrogen requirements. The liquid
product stream passes to a low pressure separator for dissolved gas removal
prior to entering a stripper column where hydrogen sulfide and light ends are
removed. The advantages of the process include:
A-13
-------
• Easily regenerable catalyst
• Low operating cost
• High yield
A schematic process diagram is shown in Figure A-6.
Stage of Development
A total of 49 units are in operation or under construction, with a cumula-
tive capacity of 720,000 bpsd.
Economic Forecast
Economic figures for 1980, considering four different feedstocks, are given
in Table A-7. The catalyst cost was updated by using a Nelson Refinery Operat-
ing Index of 295.
ULTRAFINING10
The system is used to desulfurize, denitrogenate, and hydrogenate various
oils. Typical charges are virgin and cracked stocks including naphthas,
kerosene and diesel fractions, and heavy gas oils including vacuum gas oils,
decanted oils and lubricating oils.
Process Description
The process utilizes cobalt-molybdenum or nickel-molybdenum on alumina
catalysts for hydrogenation. The catalyst can be regenerated with a cycle
life of approximately 1 year. Desulfurization occurs in a single reactor
section, followed by fractionation into the desired product streams. A pro-
cess flow diagram appears in Figure A-7.
Stage ofDevelopment
A total of approximately 550,000 bpsd of capacity is operating or under
construction by Standard Oil, and its affiliates and licensees.
Economic Forecast
Economic data for the Ultrafining Process is given in Table A-8.
UNICRACKING/HDS1l»12
The process is used to treat atmospheric and vacuum resids. It is a fixed
bed catalytic system which removes sulfur, nitrogen, and metals.
Process De s c r i p tion*1
Feedstock and hydrogen rich gas are mixed and heated and sent to a guard
chamber for removal of particulate matter and residual salt content. The mix-
ture then enters the main reactors for contact with the catalyst. Reactor
A-14
-------
run.
Figure A-6. BP Hydrofining Process.
A-15
-------
TABLE A-7. ESTIMATED COST OF BP HYDROFINING, 1980
Type of feedstock
Investment , erected
cost excluding initial catalyst
$ per bpsd
Utilities
Cost, C per bbl
Electricity
Steam (25 psig)
Cooling water
Fuel
Catalyst replacement
Hydrogen
Annualized capital
Maintenance
Property tax and insurance
Operating labor and
supervision
Administration, misc.
supply and overhead
Total operating cost,
c/bbl
Naphtha
27
1.6
-
-
9.1
0.15
60.0
5.8
1.2
0.8
3.0
1.2
82.9
Kerosene
146
1.8
-
-
9.8
0.15
60.0
6.7
1.3
0.9
3.0
1.3
85.0
Gas oil
171
2.8
-
0.2
15.0
0.2
60.0
7.8
1.6
1.1
3.0
1.6
93.3
Vacuum
gas oil
191
4.2
1.6
0.1
24.0
1.0
60.0
8.7
1.7
1.1
3.0
1.7
107.1
A-16
-------
MttMCAT
COMPRESSOK ruftMCt
STRIPPCK
M»ti«CM f
JllCM r,t:
RCCYCLE C»S
TO FUEL
}
Y
T0
—vv/v—
1
L - ------ 1
WIOOuCT
»•
Figure A-7. Ultrafining process.
A-17
-------
TABLE A-8. ESTIMATED COST OF ULTRAFINING, 1980
Investment
Basis:
10,000 to 30,000 bpsd
distillate ultrafiner
Utilities
Requirements
Cost, $ per bpsd
192 - 294
Unit cost Cost, $ bbl feed
Electricity
Fuel
Cooling water
Catalyst
Hydrogen
Steam
Annualized capital
Maintenance
Property tax and
insurance
Operating labor and
supervision
1.3 kWh/bbl $0.03/kWh
70 MBtu/bbl $3.25/MMBtu
215 gal /bbl $0.05/Mgal
0.004 Ibs/bbl
125 scf/bbl $1.00/Mscf
3.9
22.8
1.1
0.3
12.5
2.0
8.8 to 13.4
1.8 to 2.7
1.2 to 1.8
1.0 to 3.0
Administration, misc.
supply and overhead
Total operating cost
C/bbl
1.8 to 2.7
57.2 to 66.2
A-18
-------
product is cooled, separated from recycle gas, and stripped to provide th>;
proper flash point. The recycle gas is treated for H2S removal and combined
with the makeup gas. The schematic process flow diagram is shown in Figure A-8
Stage of Development
This process is Union Oil's successor to the Residfining system. One
60,000 bpsd Unicracking HDS facility is in operation.
Economics
Table A-9 lists the investment and operating costs forecasted to 1980.
These figures are updated from a recent article which appeared in Hydrogen
Processing.12 The per barrel utility costs were increased from the original
publication to reflect the fact that the authors used a cost of S2.00/MMBtu
for fuel as opposed to our projected unit cost of $3.25/MMBtu in 1980.
TABLE A-9. ESTIMATED COST OF UNICRACKING/HDS, 198012
Cost Basis: 40,000 bpsd North Slope crude charge
Capital Investment, onsite including initial catalyst $61.8 * 10G
$ per bpsd 1545
Direct Operating Costs, c/bbl feed
Operating labor and supervision 4.0
Maintenance 16.0
Utilities and catalyst 83.0
Property tax and insurance 8.0
Annualized capital 71.0
Administration, misc. supply, and overhead 16.0
Total operating cost, c/bbl 198.0
*Increased from $0.74 to reflect estimated 1980 fuel cost of $3.25/MMBtu.
UNIONFINING13
This process is used to accomplish hydrodesulfurization, hydrodenitro-
genation, and hydrogenation of a wide variety of petroleum stocks. It is used
for upgrading naphthas, kerosene, turbine fuel, and diesel fuel and for
desulfurization of vacuum gas oils.
A-19
-------
MEMO rMOOUCTS
NYMUMEN
Figure A-8. Unicracking/HDS process.
A-20
-------
Process Description
Feedstock and hydrogen rich gas are mixed, heated, and sent to a fixed
bed reactor where the mixture is contacted with a high activity catalyst.
The catalyst is regenerable with mixtures of air and steam or inert gas.
Effluent from the reactor is cooled and passes to a separator where hydrogen
rich gas is withdrawn for recycling. Liquid product passes to a stripper for
removal of light components and residual hydrogen sulfide, or to a fractionator
for splitting into multiple products. A schematic diagram of the process
appears in Figure A-9.
Stage of Development
The process is based on 35 years of hydrotreating experience including
more than 75 units in Union Oil and licensee refineries.
Economic Forecast
The economics of the Unionfining process are given in Table A-10. Catalyst
cost is based upon a 1980 Nelson Refinery Operating Index of 295.
TABLE A-10. ESTIMATED COST OF UNIONFINING, 1980
Investment
Utilities
Requirement
Cost. $ per bpsd
224 to 544
Unit Cost Cost, c per bbl feed
'Electricity
Fuel
Catalyst
Cooling water
Low pressure steam
Hydrogen
Annualized capital
Maintenance
Property tax and
insurance
Operating labor,
and supervision
Administration, misc.
supply and overhead
Total operating cost,
C/bbl
0.5 to 1.5 kWh/bbl $0.03/kWh
40 to 100 MBtu/bbl $3.25/MMBtu
1.5 to 4.5
13 to 32.5
0.3 to 3.0
1.0
2.0
60.0
10.2 to 24.8
2.0 to 5.0
1.3 to 3.4
2.0 to 4.0
2.0 to 5.0
95.3 to 145.2
A-21
-------
NCACTOH WMMATM STUIPKII
^HrOROGCN^
FEED
tan
^
^~— -
i
fl
V7
A
/ >
C — !3
T
y /
Q
c
j
)
lc
1
t j
T
L_
LISHT
OMKHorn
PHOOUCT
*
Figure A-9. Unionfining process.
A-22
-------
SUMMARY
Table A-ll summarizes 1980 capital and operating costs for the HDS processes
previously outlined and for systems discussed in the aforementioned environ-
mental assessment.1 The capital costs presented in Table A-ll have been updated
based on information provided in various publications. The basis of individual
capital estimates is variable and, in some instances, undefined. In most cases,
the published values are battery limit figures. The total annualized costs
presented for Flexicoking and LC Fining include allowances for the following
additional capital costs; construction management and overhead, engineering and
procurement, contingency, fee, new burner cost allowance, startup, and interest
during construction. This allows for economic comparison of these two HDS sys-
tems with FGD and CAFB systems, as discussed in Appendix B. Therefore, the
Flexicoking and LC Fining costs are not on a comparable basis with other HDS
systems presented in Table A-ll. Finally, some of the operating costs have
been estimated by GCA as shown in the footnotes to the table.
A-23
-------
TABLE A-ll. SUMMARY OF ESTIMATED 1980 CAPITAL AND OPERATING COSTS
ASSOCIATED WITH ALTERNATIVE HYDRODESULFURIZATION
PROCESSES
l>T*e*M
4.C0.1.1*.
CklCUUl
fetfrolUUl
•HrofUUf
01cr.fl«io§
loicrockioi/no
•tuorbi..
flwlcokUf
•MI***
BoMiforUociM
t**H OUr*fiol*«
If PUUt
te*U. Oil
tefc.*i..ir.il.iiio.
mBita.
0>lf kM-IIl
0>lf •*-!»
tn> PMI
%or*OOMlC*rl»otlM
••11
OMltlcoriM
OoMUtluMl**/
•OMltoriMtloo
te*i'fUu«
*M-fimlmt
•Ml*
•coflul c«ou or* oroj
u*» (nc) •< no OM
•t.c.1 .tUlty c*K« m*
*OM*«I»4* CMC tev oop
%*r*cu« CMC tm U.
IOr«T.tl*( CMC (*r o*
>D*n.tl*( CMC 1** fee
Llc*u*r tyit> F***»co«»
IF 45.0OO li.clll.u
0.11 U.OOO to**? dl.t.
M* oil.
•Mil crocked luck
V K 000 upkch*
» 000 k«i
M 000 (M oil
30 OOP »oa» t" oil
Oil 40.000 ».rTli ml*** crote
Ihloo Oil
tm 10.700 ••*_
mU
4.B * rnx.
>r so.ooo i.oz ( •»«.
O.JI S **»*.
«ooco 40.000 Ho»c tmrnmrn mam*
Ct Uoou 10. MO Cock hro»
C1CU. .0. o*U.
toKrle* O.U I >ra*.
•tell
y^y 30.000 K*o«lc
Odf 50. OOP 531 looBic
Omit U.OOO S3! loomlc
t**ite*l
I»» M.OOO foctecock*
-r- —
m*ll 5».OOO miteo
«tio. Tn.n.1.
•.rrlc. ».000 oottoB wrnlml*
.Co, r**U.
15.000 crate, BOOM*
too. 40.000* kOTT rwite
tmmm 4O.OOO* T..i« «o lt.M/1000 «*1.
Oomciw »•" - .U «•!•« U e/kkl of e«o*«ott _
. MUCUI CMU
«*«c I..I.OMO* «••» CMllM* rroc*».»
'•»• toul .UUtT ^.c __._« Lo_.
CMU »•«•» W»"
,S 14.1 J-0* 1.0*
4U !'•» 2.0 O.I
5S J:!1 S:! !:J
I" «•« :
In «•» \ °-j
191 24.0 t-» O.I
JS H:J £ W
1.5*5 (1.0
o»* . •'
224 »>•» ;-?r ;-jr
5H 32.) 2*" ^*"
J.500 10.0 n.O 14. t 0.1 4.1
5*5 21.5 11.5 0.7 O.I
570 10.2 20.5 O.I 0.1
533 31.3
2.113 32.3
21.3 *.« 1.1
1 02J
1.100 27.0 23.0 0.9 0.2
l.MO 17.0 14. » 1.1 0.1
1.120 11.9 10. 1 2.4 1.1
9.400
1,331 W.O 1.0* 1.0*
1.2*4 20.0* 2.0* 1.0'
l.MO 32.} 1.0* 1.5
420 l«.3 :.o* 0.5
1 »O5O 21.0 0.3 O.I 0.4
no*l *rcicl** *r 4ir*ec •mtmit. * MUoo teHorr* C«1C«1 CMC
o. P^UMW uf«ojaiMi ...M kr on.
T*Ci«t c«*c f*r
i.tlir— ~t CMU ~r.
Sp.r.lU| CMI (•
o* U *>rc**c *l uul
*B I Mrc**t ft util c.ritil
a* 2 pvrcMit •( t*ul c**U«l
<* I.Oc/lO.OOO k*** ccfccltr.
o* } f*re**t *f coc*t c«viCfll
i **Ho*iT OonrocUi CMC IOOM of ») U 19K.
*• f 1.00/1 .cf.
A-24
-------
TABLE A-ll (continued)
1 vitMi in c/bhl of fMlitoafc
IUt*rt«t eo*t*
Totcl op*r«ting
lUetrUltr*1
3.6
5.1
0.9
3,0
1.
1.
2.
4.
).
3.
1.5
4.3
45.0
10.2
15.6
Cst«lyit
0.3
0.3r
0.3'
0.3'
0.13
0.13
0.2
1.0
0.3
0.3
0.3
3.0
0.3
16.0
27.0
12.0
49.1
Hrdrotm*
-
35.0
60.0'
60.0'
60.0*
60,0'
60.0'
60.0'
12.5
12.5
60.0'
60.0'
60.0r
60.0'
60.2
140.0
Cipital ,
4.3
19.0
4.6
17.6
5.8
6.7
7.8
8.7
8.8
13.4
71.0
10.2
24.8
114.0
24.9
26.0
24.4
101.0
Haintraino*
0.9
3.8
0.9
3.5
1.2
1.3
1.6
1,7
1.8
2.7
16.0
2.0
3.0
23.0
5.0
5.2
4.9
20.2
*n4 iniuiraac**
0.6
2.6
0.6
2.6
0.8
0.9
1.1
l.l
1.2
1.8
1.0
1.3
3.4
13.0
3.4
3.5
3.3
13.3
4.5
3.5
4.0'
3.0'
3.0
3.0
3.0
3.0
1.0
3.0
4.0
2.0'
4.0'
7.0'
3.0
3.0
4.0
7.0'
•lie. curoly
0.9
3.1
0.9
3.3
1.2
1.3
1.6
1.7
1.8
2.7
16.0
2.0
5.0
23.0
5.0
5.2
4.9
20.2
Ic/bM )
32.9
93.8
76.4
105.9
82.9
85.0
93.3
107.1
57.2
66.2
191.0
95.3
145.2
343.0
170.3
189.1
146.0
384.0
13.0
29.3
10.!
10. Or
21.6
26.9
34.6
11.0
20.0
13.0
66.3
11.0
61.0
46.6
50.2
63.0
>l. t
413.00
60.1
9.4
10.0
12.6
10.2
13.0
12.2
6.3
6.7
«.4
6.1
53.6
1.2
5.0
5.0
5.0
4.5
5.9
2.5
9.4
10.0
12.6
10.2
13.0
12.2
209.6
249.2
321.4
200.0
» 500.0'
216.S
17.0
43.0
4.3
103.0
60.0'
60.0'
57.7
77.2
19.2
11.5
13.4
3.1
7.7
10.3
2.6
2.5
4.0
4.0
11.3
15.4
3.1
243.9
271.1
122.3
9.6
A-25
-------
REFERENCES
1. Werner, A. S., C. W. Young, M. I. Bernstein, R. M. Bradway, M. T. Mills,
and D. F. Durocher. Preliminary Environmental Assessment of the CAFB.
GCA/Technology Division, Bedford, Massachusetts. Prepared for the U.S.
Environmental Protection Agency, Research Triangle Park, North Carolina.
Publication No. EPA-600/7-76-017. October 1976. 324 pp. (NTIS No.
PB 262-001/AS).
2. Petersen, W. C., and T. A. Wells. Energy Saving Schemes in Distillation.
Chemical Engineering, September 26, 1977, p. 78.
3. Personal communication with Mr. G. Ruling of Gulf Research and Develop-
ment Company. October 7, 1977.
4. Kuhre, C. J., and C. L. Reed. The Shell Gasification Process for
Synthesis Gas for SNG Manufacture. Contributed by the Fuels Division of
the ASME for presentation at the Winter Annual Meeting. November 1975.
5. Autofining, 1976 Refining Process Handbook. Hydrocarbon Processing,
p. 132. September 1976.
6. Gulfining, 1976 Refining Process Handbook. Hydrocarbon Processing,
p. 140. September 1976.
7. Hydrodesulfurization, Residual Oil. 1976 Refining Process Handbook.
Hydrocarbon Processing, p. 145. September 1976.
8. Hydrofining, 1976 Refining Process Handbook. Hydrocarbon Processing,
p. 149. September 1976.
9. Hydrofining, 1976 Refining Process Handbook. Hydrocarbon Processing,
p. 148. September 1976.
10. Ultrafining, 1976 Refining Process Handbook. Hydrocarbon Processing,
p. 165. September 1976.
11. Unicracking/HDS, 1976 Refining Process Handbook. Hydrocarbon Processing,
September 1976.
12. Young, B. J., and R. L. Richardson. Resid Desulfurizer a Year Later.
Hydrocarbon Processing. September 1977.
13. Unionfining, 1976 Refining Process Handbook. Hydrocarbon Processing,
p. 168. September 1976.
A-26
-------
APPENDIX B
ECONOMIC COMPARISON OF RESIDUAL OIL UTILIZATION: CAFB, FGD, HDS
INTRODUCTION
The CAFB is unique as a retrofit application to a natural gas-fired
utility. The process can desulfurize and gasify a wide variety of fuels,
including high sulfur, high metals, crude oils and high sulfur coals, and pro-
duce a low Btu gas suitable for combustion in a conventional gas-fired boiler.
One objective of this study is to update the economic comparison of
residual oil desulfurization processes presented in our earlier report.1
The processes include the emerging technology of chemically active fluid
bed (CAFB) gasification, and the existing technologies of flue gas desulfur-
ization (FGD), and hydrodesulfurization (HDS). By comparing CAFB with exist-
ing systems, some idea of potential marketability can be determined as
compared to conventional systems. Although the conventional systems are
capable of providing equivalent desulfurization, they are somewhat limited in
matching other inherent capabilities of CAFB, such as demetalization, and
reduction of NO emissions. Figure B-l illustrates how the three systems
would interface with a conventional utility for combustion of a residual
oil feed.
Emissions of NOX are lower from CAFB, partially due to lower flame temp-
eratures and potentially due to some catalytic fixation of nitrogen in the
fuel. The use of HDS and FGD will provide minimal reduction of NOX emissions
because they are associated with conventional combustion temperatures, but
will provide S02 reduction comparable to CAFB. Some HDS systems are capable
of demetalizing, but FGD is inferior to both HDS and CAFB in this respect.
A workable total cost comparison of these three systems is difficult to
generate due to wide variation in published budget cost estimates. For
instance, a recent reference reported unit capital costs for regenerable FGD
ranging between $50 and $240/kW capacity.2 Determining representative HDS
costs is open to question due to uncertainty in design of the HDS processes.
These processes are rarely used to produce only one uniform liquid product
so that a larger system might be necessary to produce the same heat input of
low sulfur fuel being processed by CAFB. However, the three systems have
been compared on the basis of processing 10,700 bpsd of 2.5 to 3.0 percent S
residual feed, or the amount required to generate 250 MW of power.
In summary, the utility of the following cost comparison must be assessed
on the following basis.
B-l
-------
RESDFEEDB
HEAVY, HIGH
SULFUR CRUDES
j
}
u —
CAFB
{ RETROFIT)
DESULFURIZATIOI
DEMETALIZATW
LOW BTU 6AS
FEED
HEWX HI«H
SULFUR {
CRUDES { |
HOS
111
jeSULFUWZATlON/
)EMETALIZATION
PRODUCT, LOW SULFUR
LOW METALS FUEL OIL
SHIPMENT FEED
CONVENTIONAL
OIL FIRED
BOILER
FLUE
GAS LOWS02
EMISSIONS
INTERMEDIATE
SULFUR AND
METALS CONTEH
CONVENTION Al
OIL FIREO
BOILER
IT
FLUE
GAS
°
FGO
ESULFURIZATON
FLUE GAS
EMISSIONS
!
LOWSO2
Figure B-l. Application of CAFB, HDS, and FGD systems at conventional power plants.
-------
Items which arc comparable:
• All three systems have equivalent desulfurization capacity.
• All three systems process residual feed at the same rate. (In
many HDS applications, it may be desirable to produce other than
one end product. Any limitation of production of low sulfur
residual oil would necessarily require a larger system to main-
tain production of 10,700 bpsd of low sulfur fuel. This would
increase capital and operating costs.)
Items which are not comparable:
• CAFB generates very low NOX emissions as compared to equivalent
applications of HDS and FGD.
• CAFB and certain HDS systems are equivalent in demetalization
capacity; i.e., limitation of trace element air emissions.
However, FGD has no demonstrated flue gas demetalizing capacity.
• A wide variety of fuels can be gasified by the CAFB.
• CAFB is a prototype system as opposed to FGD and HDS which are
commercially proven.
Another critical factor which complicates an economic comparison based
on residual oil utilization is that CAFB and FGD are more aptly suited to
coal processing. Considering the current national emphasis on coal utiliza-
tion as opposed to use of residual and distillate oil, CAFB and FGD are po-
tentially important options for environmentally suitable combustion of coal.
Finally, comparing the three systems exclusively, without considering
the cost of the power production train, obscures any cost advantage that gas-
firing may have over oil-firing. Gas-firing has negligible requirements for
soot blowing and ash handling. In the 250 MW category, this advantage may
amount to 5 or 10 percent of the total capital cost.
BASIS OF COST ESTIMATES
Cost figures were developed for regenerable and nonregenerable (once-
through) CAFB and FGD systems. In regenerable systems, sulfur is recovered
in elemental or other useful form (such as ^80%) and sorbent material is
regenerated for reuse, with attendant reduction in solid waste quantities.
Regenerable systems require additional processing equipment which add to
total capital and operating cost.
The Foster Wheeler Equipment Corporation's design of the CAFB incorpor-
ates a RESOX™ processing system which reduces S02 formed in the regenerator
to elemental sulfur. This system is shown in Figure 2 in the main body of
the text. It is compared economically with a regenerable magnesium oxide
(MgO) FGD scrubbing system. This is currently the only known regenerable
FGU system applied at a conventional oil-fired power plant.
B-3
-------
A recirculating slurry of MgO or Mg(OH)2 absorbs sulfur dioxide from the
flue gas yielding a solution of magnesium sulfite, magnesium sulfate, and
unreacted magnesium oxide. The sulfite and sulfate crystals are filtered
from the slurry and dried and calcined to regenerate magnesium oxide. Coke
is added to reduce the residual magnesium sulfate to MgO and 802- The
recovered SOj can be processed in an acid plant to yield sulfuric acid or in
a Claus unit to produce elemental sulfur. The regenerated MgO is then used
as makeup in the FGD system.
The once-through CAFB system is based on use of a dry sulfation tech-
nique developed by Westinghouse. In this process, S02 from the regenerator
is contacted with spent stone and boiler cyclone fines to produce a highly
sulfated byproduct stone. No byproduct stone regeneration is practiced. A
low concentration of S02 is circulated from the dry sulfation reactor to the
gasifier.
The CAFB system with dry sulfation is compared with once-through lime-
stone flue gas desulfurization. A recirculating slurry of limestone is used
to scrub S0£ from the flue gas. A waste slurry of calcium sulfate and sulfite
is produced and can be dried or disposed of in a liquid state. The costs for
limestone FGD include solid waste disposal by discharge to settling ponds.
HDS economics are based on construction and operation of an LC Fining or
Flexicoking refining process. These units are licensed by Cities Service and
EXXON, respectively. The two processes are representative of demonstrated
refinery systems which are capable of desulfurizing and dernetalizing petroleum
crudes and heavy residual oil. The HDS cost figures presented here are on a
once-through nonregenerable basis, although certain HDS processes can operate
in a regenerable mode. For instance, a Claus reactor could be added to a
Flexicoking installation to convert H2S to elemental sulfur. Complete oper-
ating information on the LC Fining and Flexicoking processes is presented in
our initial assessment of the CAFB.1
The basis of the cost estimates and final comparison is presented in
Table B-l. Some of the background references presented gross costs such as
capital costs in terms of $/bpsd, or operating costs without any indication
of quantitative material requirements. Such costs were projected to 1980 by
use of the Nelson Refinery Construction Cost Index and the Nelson Refinery
Operating Cost Index.3
SUMMARY
The comparative costs for the six systems are presented in Tables B-2
and B-3. The overall format used for presenting capital and operating costs
is based on that presented by Westinghouse in their evaluation of fluidized
bed combustion.14
It is important to note that cost information on these different pro-
cesses is very limited, and published data tend to vary greatly. The com-
parison given here may have quantitative inconsistencies based on differing
B-4
-------
TABLE B-l. BASIS OF COST COMPARISON
General
1. All costs represent projections to the year 1980.
2. CAFB and FGD costs are based on battery limits retrofit, and HDS
systems are battery limits new.
3. Each system processes liquid fuel at 10,700 bpsd (equivalent to
250 MW capacity).
Capital Costs
1. Direct costs (equipment and labor).
2. Distributable costs (construction management and overhead) at
15 percent of direct costs.
3. Indirect costs (engineering and procurement) at 13.5 percent of
direct costs.
4. Contingencies at 7.7 percent of total directs, indirects, and
distributables.
5. Fee at 50 percent of contingency.
6. Startup at 8 percent of total investment.
7. Interest during construction at 8 percent of total investment.
Operating Costs
1. Limestone at S25/ton, FOB works.
2. Hydrogen at $1.00/1000 scf.
3. Supplemental fuel at $3.25/MM Btu.
4. Steam, high pressure at $3.25/1000 Ibs.
low pressure at $2.00/1000 Ibs.
5. Cooling water at 5C/1000 gal.
6. Process water at $1.50/1000 gal.
7. Power at 3c/kWh.
8. Annualized capital at 15 percent/year of total capital investment.
9. Maintenance at 3 percent/year of total capital investment.
10. Property tax and insurance at 2 percent/year of total capital
investment.
11. Labor and supervision at 7c/bbl processed.
12. Administration, miscellaneous supply, and overhead at 3 percent/year
of total investment.
(continued)
B-5
-------
TABLE B-l (continued).
CAFB and RESOX™
1. Capital costs based on mid-1975 equipment costs developed by
Foster Wheeler.3
2. Operating costs are based on:
• Limestone at 6.3 ton/hour.
TM
• Anthracite coal to RESOX at 2 ton/hour and $50/ton.
• Electricity at 3c/kWh, assumed equal to electricity require-
ments noted for CAFB and dry sulfation, updated from
Westinghouse study.
CAFB and Dry Sulfation, Limestone FGD
• Capital and Operating costs interpolated and updated directly from
the Westinghouse study.
MgO FGD
Capital and Operating costs based on latest FGD cost study
prepared by McGlamery and Torstrick of TVA.C
Flexicoking
• Capital and Operating costs based on published data and additional
information provided by EXXON.d»e»f
LC Fining
• Capital and Operating costs based on published data and additional
information provided by Cities Service.8»™
Chemically Active Fluid Bed Process. Preliminary Process Design Manual.
Foster-Wheeler Energy Corp., Livingston, New Jersey. U.S. Environmental
Protection Agency, Research Triangle Park, North Carolina. Contract No.
68-02-2106. 185 p. December 1975.
Realms, D. L., et al. Fluidized Bed Combustion Process Evaluation (Phase 1-
Residual Oil Gasification/Desulfurization Demonstration at Atmospheric Pres-
sure). Volume I - Summary. Prepared for the U.S. Environmental Protection
Agency, Office of Research and Development. Publication No. EPA-650/2-75-027a.
March 1975. (NTIS No. PB 241-834/AS).
McGlamery, G. G., et al. Flue Gas Desulfurization Economics. Office of
Agricultural and Chemical Development, Tennessee Valley Authority.
Proceedings: Symposium on Flue Gas Desulfurization, New Orleans, March 1976.
Volume I. U.S. Environmental Protection Agency. Publication No. EPA-600/
2-76-136a. May 1976.
(continued)
B-6
-------
TABLE B-l (continued).
Flexicoking Passes Major Test. The Oil and Gas Journal. March 10, 1975.
pp. 53-56.
Flexicoking. Hydrocarbon Processing. September 1976.
Correspondence with Mr. Lament E. Hill, EXXON Research and Engineering
Company. October 26, 1977.
'Correspondence with Mr. Edw<
Development Company. February 27, 1976.
"Correspondence with Mr. Edward D. Wysocki, Cities Service Research and
LC Fining. Hydrocarbon Processing. September 1976.
B-7
-------
TABLE B-2. ESTIMATED 1980 CAPITAL COSTS FOR REGENERABLE AND NONREGENERABLE
CAFB AND FGD SYSTEMS, 250 MW OIL-FIRED POWER PLANTS
Cost items
Regenerable
CAFB and FGD systems
Nonregenerable
CAFB and FGD systems
Nonregenerable
HDS systems
CAFB and
RESOXTM
FGD
CAFB and
Dry sulfation
Limestone
FGD
Flexicoking LC Fining
w
oo
Process equipment in place
Process materials and labor
Total directs
Distributables (15% directs)
Subtotal
Indirects (13.5% directs)
Subtotal base costs
Contingency (7.7% base
costs)
Fee (50% contingency)
Subtotal process
investment
New ID fan
Burner costs
Subtotal investment
Startup (8% investment)
Interest during construction
(8% investment)
Total
$/kW
23,044,300 6,916,250
15,439,700 6,916,250
38,484,000 13,832,500
5,772,600 2,074,900
44,256,600 15,907,400
5,195,300 1,867,300
49,451,900 17,774,700
3,840,900 1,368,600
1,920,500 684,300
55,213,300 19,827,600
342,000
477,000
56,032,300 19,827,600
4,482,600 1,586,200
4,482,600 1,586,200
64,997,500 23,000,000
260 92
11,815,600
15,893,600
27,709,200
4,156,400
31,865,600
3,740,700
35,606,300
2,741,700
1,370,900
39,718,900
342,000
477,000
40,537,900
3,243,000
5,162,500
6,898,600
12,061,100
1,829,200
13,890,300
1,649,800
15,540,100
7,918,000
7,918,000
15,836,000
2,375,000
18,211,000
2,137,900
20,348,900
7,008,500
7,008,500
14,017,000
2,102,600
16,119,600
1,892,300
18,011,900
1,210,500 1,580,300 1,386,900
605,900 790,200 693,500
17,356,500 22,719,400 20,092,300
330,000 330,000
17,356,500 23,049,400 20,422,300
1,392,600 1,844,000 1,633,800
3,243,000 1,392,600 1,844,000 1,633,800
47,023,900 20,141,700 26,737,000 23,689,900
188 81 107 95
-------
TABLE B-3. ESTIMATED 1980 OPERATING COSTS FOR CAFB, FGD AND HDS SYSTEMS, 250 MW OIL-FIRED POWER PLANTS
Cost items
Limestone
Catalyst
Hydrogen
Supplemental Fuel
Steam
Cooling Water
Process Water
J, Power
Annual ized capital
Maintenance
Property tax and insurance
Labor and supervision
Administration, miscellaneous
supply, and overhead
Total
$/bbl
Regenerable
CAFB and FGD systems
CAFB and
RESOX™
1,242,800
-
-
l,180,000a
-
-
3,100,000
9,747,200
1,949,400
1,306,100
250,000
1,949,400
20,724,900
5,90
MgO FGD
3,715,000
3,450,000
690,000
462,300
250,000
690,000
9,257,300
2.63
Nonr egenerab le
CAFB and FGD systems
CAFB and Limestone
Dry sulfation FGD
1,242,800 1,562,500
_
-
800 , 900
-
17,500
3,100,000 1,181,200
7,053,600 3,021,300
1,410,700 604,300
945,900 404,900
250,000 250,000
1,410,700 604,300
15,410,800 8,446,900
4.38 2.40
Nonregenerable
HDS systems
Flexicoking LC Fining
-
11,000 1,732,900
4,920,900
703,000
3,163,500
11,000 1,135,300
239,000
1,581,700
4,010,600 3,553,500
802,100 710,700
537,400 473,800
250,000 250,000
802,100 710,700
12,111,400 13,487,800
3.45 3.84
Anthracite coal for RESOX™ system.
-------
basic assumptions in the references cited. However, the more important
inconsistencies are technical differences with respect to system compara-
bility as pointed out in the introductory section of this Appendix.
This cost summary indicates that regenerable CAFB and FGD systems are
more expensive than their once-through counterparts. The CAFB with RESOX™
has the highest capital and operating cost, at $260/kW and $5.90/bbl,
respectively. These values are more than double the equivalent MgO FGD
control costs. CAFB with dry sulfation is a more cost effective CAFB oper-
ation, with operating costs only slightly higher than those associated with
the Flexicoking and LC Fining HDS processes. However, capital costs for
CAFB, whether regenerable or once-through, are double any other system.
Estimated operating costs are also significantly higher for CAFB, as
compared to flue gas desulfurization systems. The CAFB with RESOX is
$3/bbl more expensive than MgO FGD. CAFB with dry sulfation has an attendant
operating cost $2/bbl higher than limestone FGD. In order to operate the
CAFB on a competitive basis with flue gas desulfurization systems, high
sulfur, high metals crudes must be $2 to $3 per barrel cheaper than low
metals, medium sulfur content residual or distillate oils. At present this
per barrel differential requirement is roughly twice the market situation.
COAL UTILIZATION
The total capital cost (design, equipment, and construction) of a 250 MW
coal-fired regenerable CAFB is estimated to be approximately 8 to 10 percent
greater than an equivalent oil-fired regenerable CAFB system.5 The additional
cost is due to the coal handling system, which adds about 15 percent to the
total equipment cost. Similar incremental costs would be applicable for a
coal-fired conventional boiler with flue gas desulfurization, so that the
overall cost comparison of the two technologies is unchanged. Operating costs
for the two systems would also be somewhat higher because of added electricity
needs for coal handling. Conventional pulverized coal boilers would have a
slightly higher additional operating cost than the coal-fired CAFB system due
to greater coal crushing needs.
B-10
-------
REFERENCES
1. Werner, A. S., C. W. Young, M. I. Bornstein, R. M. Bradway, M. T. Mills,
and D. F. Durocher. Preliminary Environmental Assessment of the CAFB.
GCA/Technology Division, Bedford, Massachusetts. Prepared for the U.S.
Environmental Protection Agency, Research Triangle Park, North Carolina.
Publication No. EPA-600/7-76-017. October 1976. 324 pp. (NTIS No.
PB 262-001/AS).
2. Princiotta, F. T. Advances in S02 Stack Gas Scrubbing. Chemical
Engineering Progress. 74(2):58-64. February 1978.
3. Nelson, W. L. , Technical Editor and Petroleum Consultant. Nelson Indexes.
The Oil and Gas Journal. Published Weekly.
4. Keairns, D. L., et al. Fluidized Bed Combustion Process Evaluation
(Phase I - Residual Oil Gasification/Desulfurization Demonstration
at Atmospheric Pressure). Volume I - Summary. Prepared for the U.S.
Environmental Protection Agency, Office of Research and Development.
Publication No. EPA-650/2-75-027a. March 1975. (NTIS No. PB 241-834/AS) ,
5. Letter correspondence from Mr. Frank D. Zoldak, Foster-Wheeler Energy
Corporation, to Mr. Samuel L. Rakes, U.S. Environmental Protection
Agency. December 13, 1978.
B-ll
-------
APPENDIX C
RAW DATA FROM FIELD MEASUREMENTS
C-l
-------
Sample Control No.
ANALYTICAL TRAVELER
Inorganic Cases
(Special Instructions Attached )
Sample Site_
car*
Type of Source
Test Number
Sample Number
Sample Description_
Responsible Analyst
Date Taken
Date Analyzed_
Analyst Signature_
1.
3.
5.
7.
9.
11.
Workup
Column flow rate (ml/min) / M 2. Recorder speed_
Full scale (mv)
Electrometer set (A/mv)
Sample size (mi) i
Attenuation
4. Column pressure (psi)_
6. Calibration date
8. Oven temperature
_ 10. Range
Observations
-rep
f
Results
12. Pa ram
02
C02
CO
N2
13. Sum of peak areas
«
14. Concentration (7.)
?.•/%
fafa
15. Q.
C-2
-------
Sample Control No.
ANALYTICAL TRAVELER
Inorganic Gases
(Special Instructions Attached )
Sample Site
C4EJ&
Type of Source
Test Number w
Sample Description
Responsible Analyst
Dace Taken
Analyst Signature
I.
3.
5.
7.
9.
11.
Column flow rate
Full scale (mv)
Electrometer set (A/mv)
Sample size (ml) /ujJC
Attenuation /Lcx^r S /_/?>
Observations
/ ( /_/
Sample Number
Date Analyzed
Workup
2. Recorder speed
4. Column pressure (psi)
6. Calibration date
8. Oven temperature "f*l,7 / L/ /
10. Range
Results
12. Pa ram
02
C02
CO
N2
13. Sum of peak areas
14. Concentration (7.)
fU%
/A/%
vti.
15. Q. A.
C-3
Page 1 of 1
-------
Sample Control No
ANALYTICAL TRAVELER
(Special Instructions Attached )
Sample Site
Type of Source
Test Number
Sample Number
Sample Description
Responsible Analyst
Date Taken
Date Analyzed^
Analyst Signature_
Workup
1.
3.
5.
7.
9.
10.
12.
Column flow rate (m£/min)_
Full scale (mv)
2. Recorder speed
Electrometer set (A/mv)
Sample size (ml) I flu
4. Column pressure
6. Calibration date
Flame flow rates (ml/min):
Attenuation
8. Oven temperature (°C)
Air
11. Range
Observations
FID
Results
^D/om/i/c
/
13. Pa ram
Cl
C2
C3
C4
C5
C6
14. Sum of peak areas
Y •
15. Concentration Jn&fa4}-
/J3.&
16. Q. A.
Page 1 of
C-4
-------
Sample Control No.
ANALYTICAL TRAVELER
C1~C6
(Special Instructions Attached )
Sample Site
Type of Soufce
Test Number
Sample Number
Sample Description_
Responsible Analyst
Date
Date Analyzed
Analyst Signature
1.
3.
5.
7.
9.
10.
12.
Workup
Column flow rate (ml/min) f_%X r/////)U/L- 2.
Full scale (mv)_ _ 4. Column pressure (psi) ^'ju
Recorder speed
Electrometer set (A/mv)_
Sample size (m^) /
6. Calibration date
.
8. Oven temperature (°C) /U
Flame flow rates (m^/rain):
Attenuation
Air
11. Range_
Observations
Results
13. Param
Cl
C2
C3
C4
C5
C6
' 14. Sum of peak areas
'•
i/BJ/Ti"
^1.4
j.a
16. Q. A.
C-5
Page 1 of 1
-------
Sample Control No.
ANALYTICAL TRAVELER
Inorganic Gases
(Special Instructions Attached )
Sample Site
Type of Source_
Test Number
Sample Number_
Sample Description_
J**
Responsible Analyst
Date Taken
..f
j-)p
Date Analyzed
Analyst Signature_
1.
3.
5.
7.
9.
11.
Workup
Column flow rate (ml/min) f C) 2. Recorder speed
Full scale (mv)
Electrometer set (A/mv)
Sample size (m^) f t^\
Attenuation
4. Column pressure (psi)
6. Calibration date { /?? /g
r/J
8. Oven temperature (°C)_
10. Range
Observations
Results
12. Pararo
02
C02
CO
N2
13. Sum of peak areas
-
«
14. Concentration (%)
5.3
c.i
6
t>-l
IS. Q.
C-6
Page
-------
Sample Control No.
ANALYTICAL TRAVELER
(Special Instructions Attached )
Sample Site C fl
Type of Source_
Test Number
Sample Number
Sample Description
r?<-
Responsible Analyst
Date Taken
^_JL
Date Analyzed_
Analyst Signature
Workup
1. Column flow rate (ml/min)t "$0 2, Recorder speed_
3. Full scale (mv)
4. Column pressure
5. Electrometer set (A/mv)_
7. Sample size (ml) y »y
6. Calibration date /
9. Flame flow rates (m^/min):
10. AttenuationX
8. Oven temperature (°C) fo
Air
11. Range
12. Observations
Results
•7(3
7&
13. Pa ram
cl
C2
C3
C4
C5
C6
' 14. Sum of peak areas
o
a
d '
d
0
6
15. Concentration (ug/u£)
0
O
o
d
• o
V
16. Q. A.
Page 1 of 1
C-7
-------
ANDERSEN IMPACTOR FIELD DATA
PLAMT <- /9 r-ff TIME
LOCATION HIM NO.
BOILER IMPACTOR LOCATION
DAT! /A/; ."/ ORIFICE
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'STAGE NO. 012 3 4
SUBSTRATE NO. /$ ^6 Qj £-<-/ //?
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_• • , _"." • . . •• .
• ;.*.,.;. ;.,
'. -;' ' ' <"'
• . ./
.ZLE DIA.
5 6
yt r^
ORIFICE ;
t^ <£)
-3 S v^5r
38- 3f
•
• • ' • - 1 . • .
'•: •-""•: "•..••/ '
•I-'-'.".'..-;,.' "••"./':
•/ . :•• ;;;4-;r-
.v;^.:-./:'.-
• . • '« *
T •• • ;'•••• '•: •'•'•' ."
•:'. i '••. •'• ' •-,'-i • -'••'
•'• :•'•'-'•'. •"•'•'''•'V>.i-:>
. " : * . " • * " *
• ' '
* ' V
. . ......
7 *
V7 ^
•
, ORIFICE
S.P. - "Hg
v flr '
XL 2.
;..• '.'• '.,
" , .-'•'"•*
• ' '
• ' i • '•;' ;•'. :
••'•• •;.''.'. • ' . • • . .
'•.•."''
. ' '. . '
' •
.'.,.
. ,• ' •
' •>;
•
*
y^/4/;— • '*7.
C-B
-------
ANDERSEN IMPACTOR FIELD DATA
PLANT <- /7 A ' J
LOCATION •
BOILER
DATE /-.^y-rT
/ _• /•/ -y
x— * . # • X
STAGE NO. 0 1
SUBSTRATE NO. ^7 «g
' • / ' ,
-• . .1 ,. x'-t . x.' .•_, v. -
TRAVERSE ELAPSED
POINT TIME
TIME /5~.Y
RUN NO. 3V*v*v r /rv /t.-, ^-J
IMPACTOR LOCATION
ORIFICE
NOZ
234
7-^ ^^ 5~r
ZLE DLA.
5 6 7 e
s" 7*' ai* 30
".-/• v - : •'"•''/- ' •• "-
ORIFICE
A h "H-0
ORIFICE ORIFICE
3-T °F. S.P. - "Kg
TRAVERSE
POINT
•
ELAPSED
TIME
0
2.S
5
a.
•
ORIFICE
A h "H20
,yy
,7'S
,?•'
• :•''' :' ' ' ' '•
'• • •"
• *• .
.''*.,
...... .... . .,
' •
ORIFICE
-?8 *-Z
^z •/<--
s >' yx
•
ORIFICE
S.P. - "Kg
'
/, /
^
*
C-9
-------
ANDERSEN IMPACTOR FIELD DATA
FLAMT 'C / r /^
LOCATION
BOILER
DATE xAf/77
*{ir •
STAGS NO. 0 1
SUBSTRATE NO. $1 gc)
••***«**•: :<°*
TRAVERSE ELAPSED
POINT TIME
TIME '
RUN NO. /
IMPACTOR LOCATION
ORIFICE ;>£/:•• £>><"'.•}
NO?
234
75 ^5 W
Ci ^>/^
ORIFICE
A h %0
ZLE DIA. ,
5 6
7^ W
3.0.
ORIFICE
7 t
76 J^
ORIFICE
S.P. - "Hg
TRAVERSE
POINT
.:'•.•
'-.
*
ELAPSED
TIME
0
&s
•'"& ' '•
'• . ,
..... •• • •
m
. r . " . ..«i>
'• • . «• v«. .
. . •
.
* •
ORIFICE
A h "H20
.-?-;
,77
.77
<
•'•'• • . - .
.-••'• : •; • • ••' •. •'•'*'•
• •; " •• .
;...-.' ,''-•••,,' •;. ..)».•.
•;.'••' '"''••• ^ ' '• •
..,-", ' . >• ' •
f. ' •" !
' •' • ••.':' •••"(,. • . \
•• ••. . • • • i .
••:•' -v :. '•'.<'£.,'.
"'..:.••' 'V •>•;•"•.• r- ':**•
•' , * ' ,«*.•-.
• ' • • ' ' ' .' '
'• . ••;-":-
* * " t '.
; •". -
ORIFICE
** F
JSb 49
49 4
-------
Location
Date
. /.<, .t~,
__L'3l /
INPUT
OUTPUT
AH (H20)
Vw
Std
„
Std
pb
M. W. (Wet)
z co
5
D (""'/Ft3)
.6 It A
zoo
(fpB>
Q8
-------
SASS ANALYTICAL DATA
PLANT ;
DATE
SAMPLING LOCATION
COMMENTS:
RUN NUMBER
RECOVERY BY
RECORDED
FILTER // X3/3Q
FIRST IMPJNGER
SECOND .'MPINGER
THIRD IMPINGER
TOTAL
INITIAL
101 f. C
CYCLONES USED:
VOLUME
INITIAL FINAL
/.*/*
SILICA GEL
WEIGHT
ADDITIONAL COMMENTS:
'9
9
.9
9
TOTAL
GAIN-
CONDENSATE - TRAP GAIN-
FINAL
I
> -
g
: 9
—9
9 GAIN-
TOTAL-
C-12
-------
IMS F U ID D*T»
i.e..
Mi XMtl _
l III
c MHMML
mile Mcisvm. (»i>
rum
wim i.e. /-.'
•XMWD IWa'aHf. I
US-2 "OOUU •»«(•_
i«t[« w> m*an
t »«e»o«
nan nun* uiiin*
OViH IITTIM
KHCIUTIC 0» TMttllE Mini U'OUT
«(AO MD MCO*0 W.L MT» CVUT : "IHVIU
-------
nun
«!»
umiH LOOT i w
tuftt i.e.
KM IMVII _____
OftMtO* ______
mint
S * :
tTMIC Mt»CTIt.
•ami i.o.
MIIMO »ll'l«l, I.
IAS-? HXXJU luaci.
Kin MI mrmit.
••in j»k_
c i
rMu Nun* untM .
ovtn Mn IM _______
•minuet „»
•CHIMT1C Of IIUVt«M Kill! LATOUT
MM UOI KCMD *U MT* tvl«T _ RlmjIII
ruvtiM
fOWT
•wan
(ft°S
i TI«
M CLOC«)
o
tOW.
MltMt
-------
Location
Run # ^
Date JJ/l/CJrjf
INPUT
OUTPUT
„
Vw
Std
Vm
Std
9r/DSCF
PbrH8)
% CO
7..W
D (Lb8VFt3)
% o
D
TS
Q8(ft)
PST ('
Wp (lbs'part/hr)
A ^
.//f
XT (rain)
A (ft)
431
C-15
-------
SASS ANALYTICAL DATA
PLANT JL
DATE
SAMPLING LOCATION
COMMENTS I
l-\&
RUN NUMBER
RECOVERY BY
RECORDED
FILTER // '.
FIRST IMPINGER
SECOND IMPINGER
THIRD IMPINGER
TOTAL
INITIAL
TOTAL
CYCLONES USED:
VQLUMF
INITIAL FINAL
—ml-
-ml
-ml
—ml
-ml-*
•ml —
SILICA GEL
HEIGHT
-ml
FINAL
ADDITIONAL COMMENTS:
g
g
9
TOTAL 77.
•9
•9
•9
•9
GAIN-
CONDENSATE - TRAP GAIN
GAIN*
TOTAL
C-16
-------
run
tun
lANPUM LOCATION _
SOUKC '•»•
iw Dunn 8
orturoi
AICIUT TEMrcunm_
IAMMTIIC Mf!tUK._
STATIC I
>IUU I
S « S S FICtC D * T »
HOU UWrx UD TT>C _
i.o.__2L£
Aiswtc >«un«if, I B
IAB-2 KXNA.C HIMII
HTH SOI mrafl nvm (j
c f ACTMI
'•Oil
OW
•tnimcf or.
n m*n* UITIIH *
• j|m»« +00
«Stf
*vr>
"C^.,l
:-'•- ',7
tCHtiwm or n»ni» roinr LATOUT
MAO AMI HICOUD AU. DATA tVtlt
J7
TOTAL
»VtMC£
Mi CI.OC«>
tf
2£
fl
^3d.
/5
/>LH:
^sag.
CAS nrrti »tu>iiic
WIFICC
DIH[«
(u<). III H?0
/Z£
/.Ifl
^
^2i
^2^.
/7ft
^Zo
^£.
CM* fiAi Wt(«
rtnmuTiwe
I«L(T
. )»
"m
10
!
outm
""ouA
(fl
VACUUM
1* H,
mf»
rexrturuit
f(2L
&L
IWIMCI
TCIMIATUIt
SOUMI
mr
TElVtRATURf
2o_
J£L
<&£L
ZS7
-------
Location
Run # 1
Date
It
INPUT
OUTPUT
AH (HjO)
Vw
Std
„
Std
M
7.
Pb
I Dr, Gas
Mg.
% CO
D
PST
("H^O)
Wp (Ib8'part/hr)
TT (min)
A (ft)
C-18
-------
Run Dete:
Run Mo.:
il&J-,->
PARTICULATE CLEAR UP AND REPORT SHEET
t/lrtf
"? AC.
Sample Box No.
Operator:
Clieot:
W. 0. «o..
Plant!
Saavllng Location:
FROHT HALF
Hoitle and Probe (Cyclone Bypaaa)-Acetone Uaah, Ub Ho.
Cyclone and Plaak-Acetone Waah Ub Ho.
Filter Mo. Ub Ho. Weight Reeulte
Laboratory Reaulta
Realdue
Reeldue
G ~
Cyck
e,* *
-t
BACKHALF
laiplnger Content and Water Waah of laplngera
Connactore and Beck Half of Filter Holder
"~-''i n- : f>3 )V*( *Qt' (? . ; r > t,
Inplnger, Connector* and Back Half of
Filter Holder - Acetone Waah
InBlngere
z
S07.4* c' < c
*&?.**,
: f??. '
final Voltoe
Initial Vol
Net Volu««
Filter particulate weight
FRONT HALF Sub Total
Ub Ho.
Silica Gel
Weight after teat: f_
Weight before teat: «*• "* f
Hat Weight frtaVf
Container Ho.. 1. 2.
TOTAL VEICHT-Slllce Gel
TOTAL VOLOME-Iaplogere
TOTAL MOISTURE
Collected on 0.22u Filter
Aqueoua Raaldue
Ub Mo. Reeldue
BACK HALF Sub Total
TOTAL WEIGHT
•g
•g
•R
«R
•g
3.
rmawnte:
UB: DATE RECEIVED
DATE REPORTED
HFS/5/77
ANALTTICAL CHEMIST
C-19
-------
PLANT
DATE £ 3 * /'
RON NO. _J_
STACK DIAMETER, in. £9,
BAROMETRIC PRESSURE, In.He. 23. 2a
STATIC PRESSURE IN STACK(P ), In. He.
O
OPERATORS
SCHEMATIC OF STACK
CROSS SECTION
Traverse
point number
Velocity head,
in. BJD
I/, -
/ft
,001
.ol
.01
.01
AVERAGE:
4
t
Stack Temper-
ature (T), F
1
hti-
II
Iff
IIT
lit
a*
, 7 .._*/"!•.
C-20
-------
Sheet 1 o.
Client *
W. o. No.
Plant
PARTICVLATE FIELD DATA
VERY IMPORTANT - FILL IN ALL BLANKS
Read and record at the start of each
test point .. ,•_
. _ . > SKETCH
Run No. /
Location
Date / - 24-' V*
Pltot Nuaber & Side
Plloc tube CP
Filter No.
Anblent Temp. °F
Bar. Press. "Hg 0-3t2^O
Assumed Moisture J I O
Operator
Savple Box No.
Meter Box No. 2. 2 5 "9~
MaterAH
C Factor
O
1
»— •
POINT
/
S
3
5
1
4!
^
(°
it
DISTANCi
IN
INCHES
/
CU
TD
wrruAL
/fJi
Meter leak check:
Before test: CF
JCK
IE
RUN
f)
5
SB
2.<
s#
fo
}f
4o
4*
•*<£
DRY CAS
METER CF
t/Z.AL 7
H4.i4>f
/l(.t^f
/Z-7./&-
tlt. V/5
/Sf.fSA
TOTAL
Sec In
After test: CF Sec In
Static Pressure (PST)
oc3£tf'Q '''e' ''' ' f I Heater Box Sc
^t^^ , ff£ j C * f
>ae Nozzle l/Dla
1 1x^"^*»w Probe Length
1 , j i Probe Heater
i ^ J Avg.AP
' " * — rf*^^t***
\ *^a , _. , i
PITOT
IN. H20
,()/
• a/
,,/
• *l
•a/
• *l
.0 '
/ /
.V.
•Hg
.Hg
Port In.HjO
_____
ORIFICE A H
IN.H9 0
npiTRFn
-6°
4 J~
tf
, ?i
,*J'
/fJ
. ry~
f-J
z
COMMENTS.:
l**f
""(,
A.CTUAI.
^^
, fif-
,*r
> 9
xiy
>/3
.•» i
.> '
/r1"
• ^7
, ft
DRY GAS TEMP.
OF
JH1,ET
?4
76
f-^
ft.
*^
ft
fc,
OUTLET
^4
^ f
if
ti
Af
6f •
a ~
y&
70 -
v&
PUMP
VACUUM
IN. Hg
GAUGE
-?
jf.
41
•4'
& . ^
fr±~
.5
•ttlng. OF
.. In. '12.
3
Setting 3OO
Avg. AH
BOX
TEMP.
°F
Zfs
JDS'
Hfi '
z.±z
Z 7 "7
2.2 S
'J-C1 i
t / »
/? •
IHPINCER
TEMP.
°F
w
_**'
J4
3*
2 'f-
3 S
j (
-rf
£«•£. | pf"^-- i "• i-.'-
.,yr3*S
-------
Client
PARTICULAR P1SLD DATA
Sheet
N.O. NO.
Plant S±'£o
Run No. /
--'-""™ (concioued)
Location
Date /- £ J - 7 ?
POIBT
DISTANCE
IN
INCHES
/I-
at
Tl
ACTUAI
/r*#l
75
KK.
IE
RUN
S*
b*
4<«<.
Mt i-
,*<' *
Meter leak check during test:
DRY CAS
KETKR.CT
&y<-
•'43.C4{
TO,^"J9
. J
i». ^ 7^
TOTAL
Meter Rea
stop at
PITOT
IN. B20
AP
.a/
.a 1
ding
art
ORIFICE
IN.E
DESIRED
.9i
(9*8^
*
CP Sec In.Hg'a
CT Sec in.Hg's
Static Pressure
Port
In.HjO
AH
,0
ACTUAL
,**?
A 89
DRY CAS TEMP.
INLET
?<*
9&tL?
"*£•
OUTLET
^*
**.£
POMP
VACUUM
IN. Bg
GAUGE
&f
BOX
TEMP
Op
20J
2 ^t
TMPINGER
TEMP
°F
?%-
tjf
STACK
PRESS
UN. Hg
STACK
TEMP.
°F
/^o
/£SJt3
COMMENTS:
M
to
-------
GASEOUS SAMPLING
IMPINGER TRAIN
Client:
Personnel:
Location:
W.O. No.
Sample location:
Date:
Barometric Pressure:
Pollutant and Run No.
F.
Time S.
T.
P.
Gas Meter s.
Total ft.3
P.
Vacuum s .
In. Hg. Av
Inlet p.
Dry Gas Meter
Temp. S.
F. Av,
Outlet F;
Dry Gas Meter
Temp. S
°F Av
Impinger F
Volumes Sol'n A S
Net.
Impinger F
Volumes Sol'n B S
Net.
Silca Gel F
gms S
N
Filter or Thimble
f
SCTi/Sfcr?
£0*/A>
«
It 0 /H't*
J AS, 04&
//2..0L1
30'7/r
s.*
3.o
+.15
?*
7L
«3
9$
tt
I*
l£4.t> t
2+£.+
X.L1
MOTES.
C-23
-------
Location
Run #
Date
INPUT
OUTPUT
-------
O
NJ
U1
Sheet 1 01
Client f 1
W. 0. NO.
Plant />/// / C^^-.
PARTICULATE FIELO DATA
VERY IMPORTANT - FILL IN ALL BLANKS
Read and record at the start of each
test point
SKETCH
Pitot Number & Side
Pilot tube CP
Filter No.
tun No.
Location
Ambient Temp. °F
Bar. Press. "Hg
Date /- 2*r
Assumed Moisture I
Operator
Saaple Box No.
Mater Box Ho. £Z £" 7
MeterAH
C Factor
POINT
/"
I
f
J
f
9
9
7
9
f
J
DISTANCE
INCHES
CU
TD
ICTUAL
S730
'8LO
Meter leak check:
Before test: CF
•xx.
ffi
RUN
O
/?
/£
s-a
i_5"
?0
1.4"
+9
+S
6*
DRY GAS
METER £F
/ tf.oto
/6 5, i t <
/S/,J~o
/y&4ai*
TOTAL
Sec In
After test: CF Sec In
Static Pressure (PST)
Port in.Ha
Heater Box Settin
Nozzle l/Dla., I
a
Probe Length
Prob
Avg.
PITOT
IN. H20
flP
,ff -«'
,'i
•Hg
•Hg
0
ORIFICE A H
IN.H? 0
npSTPFD
/.z
S, /
/.z.
/,!_
/. 2
/.Z.
/Z-
y <-
/ 2-
/,&
/£.
ACTIJAI
/Z,
/. r-
X. i.
At-
/. z
/- *"
y. «.
// t
t. E.
/. t.
DRY GAS TEMP.
op
IMl FT
^6»
So
««•
9*
/z
?<*
f ^.
; ^>
?¥
?<
?^
oim ET
tr
ii
b»
+ %-
"&
yo
?te
7/
f*.
•71,
7He
PUMP
VACUUM
IN. Hg
GAUGE
7
ye,
/0
/'. .5
// J"
X £ O
J*-t0
Jl.£>
/£.£
/i. £
^
ing
/
BOX
TEMP.
°F
m
$&J
2,-Ji
^ &C
tSit~
£ 7 f
i$i
161.
1,9 -L,
*?*
Z.8S-
IMPINGER
TEMP.
13
ft
ff
4r>
f *
*Q
ta
6a
6<9
^? e-
/& £_
^?T^.
/ ?
/ TC.
y^^
ivg. AH
STACK
PRESS
IN. Hg
STACK
TEMP.
°F
?-((.
^.af
•z*>f>
Z.e>7
ifL
X.a-9
1*1
/14-
/? +
S91*
• -
COMMENTS: , ^ <•'•••,/ ^0'^
^^4 j^.^C- "^Lfr*»J ^i /-Wi-'4 ^ /- >^ fc f; /
£t***4J A'&' 7**u**f-£ //AC^*^CV ^tv_ir ^'*/« . ^.i *. tj . l ^ u
— -^ r- » >~ >v^« ^.^-^ <.,!(,
-------
Client
PARTICULAR FIELD DATA
(continued)
Shut
of
W.O. No.
Plant
bin Ho.
Location
Data
O
S3
POINT
?
DISTANCE
IN
INCHES
cue.
T»
ACTUAl
ST*f
XX
IE
RUN
fS
t»
Meter leak check during test:
DRY GAS
HETER.CF
/SZ.Z94-
•\\ Sni +
TOTAL
Meter Rea
atop at
PITOT
IN. H20
AP
»/jT
.111
ding
art
ORIFICE A B
IH.H,0
DESIRED
S,3
/ z~o9
CF Sec In.Hg'a
CF Sec li
Static Preasure: Port
In.HaO
i.Hg's
ACTUAL
/,3
DRY CAS TEKP.
°F
INLET
9s
7°
79. S
OUTLET
7*.
1,161.1
sj
PUMP
VACUUM
IN. Ug
GAUGE
/*•
BOX
TEKP
Of
t?j
TKPIH
TE
0
^/
CER
>9«M
r
y* e.
STACK
PRESS
:N. Hg
STACK
TEMP.
°F
/?*-
2.0 3 5
COMMENTS:
-------
PLANT
DATE /- Zj5 - 7 -
RUN NO. -2-
STACK DIAMETER, in.
BAROMETRIC PRESSURE, in.Hg. Z?
STATIC PRESSURE IN STACK(P ), in.
OPERATORS
**t,
*>*
'><-,
SCHEMATIC OF STACK
CROSS SECTION
1 Traverse
point number
/
2.
3
^
£
>+
JT/x///>
7
%
?
/e
//
/2-
Velocity head,
in. H_0
.£>/
.0 /
,ol
.£>/
.01
.o/
,c*>
,0/3
.n; S
tr>/S
,0/S
,0/7
. 020
AVERAGE:
^
,/:d
• /OC
ify
• liir,
.!(': ,1-
• .' i, ['.
•
.//4
./^>
/>>
/2x;-
• /.VJ
.Ml
-//*
Stack Temper-
ature (T,,), °F
///
y^
/9+
/9t
;9?
/j'S
/**
/9S
/9£
/*&
J is
/'*/
/tf
/9d.*
\
\
\
\
C-27
-------
PARTICULATB CLEAN UP AMD KBPORT SHUT
Run Data: tl"\9l 7$
lf-t.fl C^.-.
Run No. . P f} ( ~ >•
Sample Box No.
Operator:
FRONT HALF
Nossle and Probe (Cyclone Bypaea) -Acetone Uaah,
Cyclone and Plaak-Aceton. Waah
Filter No. Lab Mo. Weight ieaulta
Client :
W. 0. Ho. i
Plant:
Sanllnc Location: _£"/^-/^*r-<
*~~*^
Laboratory Reeulte
Lab No. Raeldue _i
Lab No. Residue at
G.
BACK HALF
lapInger Content and Water Waah of laplngera
Connector* and Back Half of Filter Holder
Taplngar, Connactora and Back Half of
Filter Holder - Acetone Uaah
MOISTURE
/oo - 1
1 to
Final Volume
Initial Volu
Net VoluM
o
3
FUtar partleulata Might
HALF Sub Total
Lab No.
Collected on 0.22p Filter
Aqueoua Residue __________
Lab No.
BACK HALF Sub Total
TOTAL WEIGHT
Raaldue
Silica Gel
Weight after teat: Z£r3,'j£
Weight before teet: «£5*.-V
Het Weight
Container No.: 1.
2.
3.
TOTAL VEICHT-Sllica Gel
TOTAL VOLUME-laplngers
TOTAL MOISTURE
IAB: DATE RECEIVED
DATE REPORTED
HFS/S/77
ANALYTICAL CHEMIST
C-28
-------
Location
Run #
Date
INPUT
OUTPUT
AH (H20)
Vw
Std
Vw (ml)
„
Std
vm
g3.77
9r/Dscp
Tm
Pb ("Hg)
Q.44
7. Dry Gas
Q \
Mg. Partic.
"'
% co
7.51
% CO
o
Vs (fpm)
TS
PST
.ex
Qs (ft)
Cp
TT (min)
A (ft)
noz
AST (ft )
C-29
-------
o
o
Sheet 1 0-
Client
Mf. 0. Ho.
Plant
PAKTICIJLATE PIELb DATA
VERY IMPORTANT - FILL IM ALL BLAHC
Read and record at the atari of each
teat point •
SKETCH
Pltot Nunfeer 6 Side
Pilot tube CP
Filter Ho. !-, Iffy
Location
Date
Operator
Sample Bos Ho.
Meter Box Bo.
MeterAH
C Factor
Ambient leap. "F
Bar. Preaa. "Hg
Assumed Holature Z _
Heater Box Setting,
Nozxle f/Dla., In.
Probe Length 3
Probe Beater Setting
Avg.AP Avg. "AB
DISTAMC1
DI
CLOCK
TIME
UTTUAL BUM
DRY GAS
PITOT
IN. B20
AP
ORIFICE A H
IH.H, 0
DRY GAS TEMP.
Tin.ET OIITLET
PUMP
VACUUM
IM. Hg
GAUGE
BOX
TEMP.
DfflHGER
TEMP.
°F
STACK
PRESS
IM, Hg,
STACK
TEMP.
°r
t,
(
"*"
rf
~tU-
f.u
'**>
n-
L 7
*&
•so
W 9
oi-
±£
*£
71
26V
*9-
96
•» V
7V
r-re/
Mater leak check;
Before test:
After test:
Static Pressure (PST) Port
;OHH£HTS:
-------
Client
PAKIICULAIE FIELD DATA
(continued)
Sheet
W.O. No.
Plant _ /-
Run No. t v/"
Location
Date
Av / 7
POINT
TV
1 1
r -a.
•S-r i
'
DISTANCE
IN
INCHES
CL(
Tit
ACTUAI
?:->7
,'f -fl
/ f • i./'X.
/ (
XX
tE
RUN
yffif
£0
tfi
£<3
7~Al
Meter leak cheek during test :
CF See in.Hg's
DRY GAS
METER, CF
3#- •?
2''. '/
*?- ' ; '. •'
3/7 i/CQ-
6-ifr.rf-
3*^. /-3o
- 340
llJffl
TOTAL
Meter Rea
stop at
PITOT
IN. H20
AP
0 : • •• .n
C ' '" ,/i
6 ,- • * .Of
../jfy
ding
art
ORIFICE A B
DESIRED
I ~»
/. JT
- -*
/,/ZZ.
CF Sec in.Rg's
Static
Pressure
Port
ln.H20
ACTUAL
7 6-
/. T
» ?~'
DRY GAS TEMP.
°P
INLET
•>P-
"«
1 *
Sil^iJ
^^
>tf "
OUTLET
^ ^
T" 1? .
r "'
f
j&Msff^.
j
'&¥
(t l\ ^Sf
PUMP
VACUUM
IN. Bg
GAUGE
+
7
c-
BOX
TEMP
°F
:S7
1^3
: -
DCPINGER
TEMP
°F
f£
'"'"'/
. ,'
&&&#'
STACK
PRESS
IN. HR
STACK
TEMP.
Op
i'3
/u
i •- .
JS%.67 7
COMMENTS:
• 3^7 ^/r/.. /•„ ^ • /; -^ ^
n
w
-------
PASTICOLATI CLEAH UP AND UPORT SBItT
Run Date:
Run No.:
Client:
Sample Box No.
Operator: _^^
W. 0. No.i
Plant:
SaaDllnm Location:
FRONT HAL?
Noicle »d Probe (Cyclone Bypeee) -Acetone HMD,
Cyclon* and Fleck-Acetone Ween
Filter No. Ub Ho. Weight Reeulte
Lab No.
Lab No.
Laboratory Reeulte
Reeldue
Reeidue
GfoQ
C/xr fc*.
fcJfMt?
BACK HALF
I»plng«r Content and Weter
Connectora and Beck Half
vti'M fis> PUrifV>i> &
[•pingar. Connectora and Bi
Filter Holder - Acetone V
MOISTURE 7"
lapingara ,
•M 6%%'l
#j &a. k
#4 5»$,V/2?£ •«
> (M l/flO ••
^ 1 / 4 (P W •* nicer partlculate weltht (JO "J f f
nOKT HALF Sub total
Waah of Ivplngera Lab No.
of Filter Holder
Collected on 0.22u Filter
Jrf \V\F^ "^ Aqueoue Raeldue
ck Half of
la ah Lab No. Reeidue
BACK HALF Sub Total
TOTAL WEIGHT
F
Silica Cel '•
h ^77,($Q Weight after teet: ^73.^lP
JP &•*>/ td^ Weight before teat i c(^*$ $*$
f £*f\^ Cmt / H«r Iblnlit- 1 *7 r/&\
TOTAL WBICHT-Slllca Cel //, ^^
>vj • ** * /i /n *r
a") . , TOTAL VOLUME- iMplngera OC. W J
sL«/
•£
««
•«
. •«
a«
a»
•1
J1
•i
I
3*
ANALYTICAL CHEMIST
HFS/S/77
C-32
-------
Location
Run #
Date
INPUT
OUTPUT
AH (H20)
Vw (ml)
„
Std
it* 3 ft
Vta
'r/DSCF
Tm
4.47
Pb ("Hg)
^ Dry 0..
Mg. Partlc.
«.». (Wet,
co
D
CO
ft
V8 (£pm>
TS
PST
("H20)
14
Cp
TT (mln)
m.
A (ft)
noz v '
AST (ft )
C-33
-------
O
Sheet 1 o-
Client
PAXTICCLATE FULI* DATA
VERY IMPORTANT - FILL IK ALL
N. O. Mo.
Plant
^•A R«ad and n
V test poin
ecord at the start of
point
Bo.
A/?
Location
Operator
Saaple Box Bo.
Matar Bos Ho. _
leterAfl
C Factor .
Pitbt ihoiber & Side
tot tube CP
Filter No. j "/*/
Ambient Teftp. °P
Bar. Preas. "Hg _
Molatura Z
Beater Box Setting,
Nozzle f/Dla.,
Probe Length
Probe Beater Sett
Avg.AP
Avg. AH
DISTANC!
IN
IMCHKS
CLOCK
TDffi
LCTOAL BOM
DRY GAS
PITOT
IN. B20
M
ORIFICE A B
IK.H-) 0
BKSTPm
ACTUAT,
DRY GAS TEMP.
OF
PUMP
VACUUM
IN. Bg
CADGE
BOX
TEMP.
°F
IMPING ER
TEMP,
STACK
PRESS
IN. Hg
;TACK
tEKP.
Op
4
. S3L
..V
fs
7 if
Z.Z.A
•$±
Al 7.
•"•*
',7
A a
LJL
m.
3o
2.1.
f
zz.
.6JT
S
34
"72,
.-3
It-
7?
2 1
Hater leak check;
Before test:
After test:
Static Pressure (PST) Port
.-3
Z.71,
-------
Run Date:
Run No..
Sample Box No.
Operator:
PARTICULATS CLEAN UP AM) REPORT SHEET
, ?7 / ?
Client:
W. 0. Ho.;
Plane:
Saapllng Location:
FRONT HALF
Nozzle and Probe (Cyclone Bypass)-Acetone Hash,
Cyclone and Flask-Acetone Wash
Filter No.
Lab No.
Weight Reaults
jng
BACK HALF
InplnKer Content and Water Wash of Inplngers
Connectors and Back Half of Filter Holder
Inplnger, Connectors and Back Half of
Filter Holder - Acetone Wash
MOISTURE
tnplngers
Final Volume Z- /
in I tin I Volurap _£»
Nft Volume
Lab Mo.
Lab No.
Laboratory Results
Residue
Residue
_»g
Dg
Filter paniculate might
FRONT HALF Sub Total
Lab No.
Collected on 0.22y Filter
Aqueous Residue
J»K
__og
Lab No.
BACK HALF Sub Total
TOTAL WEIGHT
Residue
jug
Silica Gel
Weight after test:
Weight before test:
Net Weight
Container No.:
8. /
1. _ Z._
3.
4.
TOTAL WEIGHT-Silica Gel
TOTAL VOLOME-Implngers
TOTAL HOISTUTIE
IJiB: DATE RECEIVED
DATE REPORTED
JIFS/5/77
/
ANALYTICAL CHEMIST
C-35
-------
NOMOGRAPH SETUP DATA SHEET
CLIENT
GCA WORK ORDER NO.
PLANT
DATE:
SAMPLING LOCATION
METER BOX AH@ ^f/*
METER BOX NO __
MOISTURE vm •/. 8 /& BAR. PRESSURE (PB)(PM) ??t**f"\n. Hfl
STATIC PRESSURE SAMPLING POINT (PST)-fi££ - in. HgO >^?35 ='
PRESSURE STACK CPS) PBt(PST) * _ ^ - * <^£3o!n. Hg
PS/PM » - » /r/^/P PI TOT TUBE NO. -
£— ; (Cp/0.85)2 = (/,
Ap LOW_i^L_; Ap AVERAGE
NOZZLE DIAMETER _J^£_ in.
; Ap MICH
high
/7/
K FACTOR CHART
K FACTOR REFERENCE
ON Ap SCALE
C-36
-------
LocaLLon
Run 1i
INPUT
OUTHJT
it />
Std
\y s
Std
'r/DSCF
Pb("H8)
%DryGas
„.„. (Wet)
7U CO
^L
7, CO
&
va (fp.)
TS
93 (")
PST ("H00)
2
Wp (lbs
-------
o
00
Sheet 1 ot.
Client
)
W. O. NO.
Plant
PARTICDLATI FOLD DATA
VERT mPORTAMT - FILL « ALL BUMS
Read and record at the start of each
teat point
SKETCH
PI tot Ruaiber & Side
Pilot tube CP
Filter Mo. /
tun Ho.
Location
Date
Operator
Saaple Box Ho.
Meter Box Ho.
HeterAH
Aablent Teep. OF
Bar. Press. "Hg
Aasuaed Moisture X _
Beater Box Setting,
Nozzle l/Dla., In.
Probe Length r
Probe Heater Setting
Avg.AP Avg. AH
OISTAMC1
CLOCK
TIME
kCTUAL 10
J7&S
to
DRY GAS
PITOT
IN. B20
ORIFICE A «
IH.H? o
nRSTBvn
.SJ
.70
.ts
."JO
.70
DRY CAS TEMP.
op
73
jfcfi-
I*"
PUMP
VACUUM
IN. Hg
GAUGE
BOX
TB1P.
°F
-xi
IMP ING ER
TBMP.
°F
•7*9
STACK
PRESS
IN. Ha
STACK
FEW.
°F
SLJL&-
tM J-
33
^
. frf
i i
.£9
». -3
so
76
.01
4-. a
+ J
/*•/
Meterleak check; TOTXL
Before test: CT Sec 1
After test: CP Sec_
Static Pressure (PST) Port ln.H20
t»f»
no
XIKMENTS:
in.Hg
^13589. '8
-------
o
u>
vO
Client +): .'.,
PAITICULATE P
(continued)
Meter Reading
Meter leak check during test: stop start
CF
~CF~
_Sec
Sec"
Jn.Hg'B
In.Hg's
. Pressure: Port
* ln.H20
COMMENTS :
-------
FAKTICDLATE CLEAN UP ADD UPOtT SHEET
Run Date:
Run No. ••
l<iR
W. 0. *>.!
Sample Box No.
Operatori
SuolinB Location:
FRONT HALF
Noult and Probe (Cyclone Byp*aa)-Acetone Kaah.
Cyclone end Flaak-Acetone Vaah
Filter No. Lab No. Height Raaulta
6g7
BACK HALF
I«ptng«r Content and Water Waah of Ivplngtra
Conoactora and Back Half of Filter Holder
foplnger. Connectors and Back Half of
Filter Holder - Acetone Uaeh
Final Volume
Initial Volu
Net Voluae
Laboratory Raaulci
Lab Ho.
Lab Ho.
ftialdua
Filter partlculate weight
F10NT HALF Sub Total
M.J
Lab No.
Collected on 0.22u Filter
Aqueoua Raaidue ________
Lab No.
BACK HALF Sub Total
TOTAL WEIGHT
flealdue
Silica Gel
Weight aftar teat:
Weight before teat:
*5
Net Height
Container No.:
!.__&__ 2.;
TOTAL mien-Silica Gel
TOTAL VOLUME-lBpingeri _
TOTAL HOISTURE
3.
4.
1AB: DATE RECEIVED
DATE REPOTTED
HFS/5W
ANALYTICAL CHEMIST
C-40
-------
APPENDIX D
DATA FROM LABORATORY ANALYSES OF CAFB SAMPLES
D-l
-------
TABLE D-l. SAMPLE ABBREVIATION CODE
Sample code Sample description
PF Particulate filter
Ic, 1 yc 1 micron cyclone
3c, 3 yc 3 micron cyclone
lOc, 10 yc 10 micron cyclone
PR Solvent probe rinse
XR XAD-2 resin
MR Solvent module rinse
CD Module condensate
CH Composite of acid module rinse, condensate, and first impinger
1C Composite of second and third impingers
RB Regenerator bed
GB Gasifier bed
FR Fines return
RC Regenerator cyclone
MC Main cyclone
SC Stack cyclone
KO Knockout
BB Boiler back
BS Boiler sides
CF, Lig. Coal feed (Lignite)
Lim. Limestone
D-2
-------
TABLE D-2. SSMS ANALYSIS OF lOy CYCLONE CATCH FROM SASS-1
101 C»fB»l-10C-0-l O.IOS8G
v»tutc PPM )
4
<
<
«
<
C
<
<
<
<
<
«
<
<
<
5.J
15.
2.S
oise
0.099
0.15
0.17
o.n
0.56
2.5
1.0
0.76
0.30
1.1
0.21
oloi2
l.«
1.1
6.0
13.
u
TH
BI
p«
TL
*U
ID
OS
RE
»
MF
LU
YB
T*
ER
MO
Of
tH
CO
EU
SM
ND
PR «.l
CE 3Z.
t* «5.
8* 660.
CS 1.9
1 2.6
TE < 1.6
SH 1.6
SH 5.7
IN I l«0.
CO l.S
PO « 1.7
RH < O.Jl
RU < O.OBi
MO ?.«
N8 i7.
7R 150.
Y 5«.
S« 650.
RB 19.
BR 61.
SE « H.
»S 200.
Ct 12.
C* il.
ZN 660.
CO »7.
Nl 06.
CO 21.
FE MC
HN 0.19 (S)
CB «0.
V 91.
TI 0.64 (X)
C* O.S (X)
K 0.17 (X)
S MC
P 210.
SI 6.7 (X)
*L MC
MC 0.46 (X)
N* 850.
B 1*0.
BE J.fc
D-3
-------
TABLE D-3. SSMS ANALYSIS OF 3ja CYCLONE CATCH FROM SASS-1
jot CAFB*1-3C»0»1 0.10036
ELEMENT
VALUE< PPM )
u
TM
61
Pit
Tt
AU
IB
OS
RE
H
HF
LU
TB
TM
ER
MO
Of
TB
6D
EU
SM
ND
PR
Ct
LA
BA
C8
I
TE
SB
8N
IN
CD
PO
RM
RU
MO
Nb
I*
Y
SB
KB
BK
3E
AS
GE
6A
ZN
CU
NI
CO
f£
MN
CR
V
Tl
CA
K
8
P
81
AL
MR
NA
H
Be
u
«
<
<
s
<
<
c
«
<
20
8
&A
*»
0
0
0
0
0
0
2
0
0
0
0
0
0
0
0
0
2
12
M
30
A3
*C
720
1
0
0
2
S
1*0
0
1
0
0
2
25
1«0
36
0
17
CM
71
6
210
8
58
230
32
85
la
1
3*0
25
O*
~o
0
9
0
0
7*0
13
I
0
0
0
2
t
•
•
t
*
*
*
*
t
i>
t
•
*
•
*
•
•
*
*
t
*
*
*
*
•
•
*
•
*
•
•
«
t
*
*
*
•
*
•
•
•
•
•
•
*
•
i
•
»
*
•
*
•
»
•
«
*
•
»
•
*
•
*
•
•
4
15
IS
20
31
20
73
3
89
95
068
20
38
tt
022
11
71
0
3
a«
S3
3
3
98
6
050
IS
8
100
S
1
7
36
0
«7
90
9
74
31
11
4
(X)
(X)
(X)
CX)
(X)
(X)
CX)
(X)
-------
TABLE D-A. SSMS ANALYSIS OF lp CYCLONE CATCH FROM SASS-1
IDl C*FB*l»IC-0-| 0.10JUC
V»LUt< *>«•" )
I)
TM
HI
PB
u
»u
1R
03
RE
•
HF
UU
TB
TM
ER
HO
01
TB
CD
EU
$M
NO
PH
Ct
L*
a*
cs
i
u
SB
SN
IN
CO
PO
RH
RU
HO
NB
ZR
T
SR
RB
BM
St
»S
Ct
c*
ZN
cu
Hi
cu
FE
MN
CR
V
Tl
C»
K
a
f
si
*L
MG
N*
B
BE
LI
5.6
9^7
160.
0.3S
olfcS
0.71
0.05
1.7
11.
2.1
o!l6
S.Z
0.6?
a.3
0.051
1.7
1.1
6.a
68.
I«0.
0.2% (t)
1.6
5.1
8.6
> HO.
I.S
< 1.2
< 0.11
< o.is
S.I
57.
iiO.
«3.
0.13 (X)
« iZ.
«70.
« 9.8
uo.
Jno.
100.
ISO.
(S)
Z.Z
«50.
65.
^^o.
0.81 (X)
9.3 (X)
0.64 (X)
2.9 (X)
910.
5.1
1.9
0.61
(S)
(X)
(X)
0.16 (X)
0.46 CX)
»5.
*5.
D-5
-------
TABLE D-5. SSMS ANALYSIS OF PARTICULATE FILTER FROM SASS-1
SANPtt IDI CAPB»I-PF»A-I 0.07J9S (10.961)
CLEMENT
VALUE( UC )
U
TH
Bl
PB
Tt
AU
IR
08
RE
N
HF
LU
Y»
TM
ER
HO
OY
TB
60
EU
SM
NO
PR
CE
L*
HA
CS
I
Tt
SB
SN
IN
CO
PO
AH
RU
MO
MB
ZR
T
8R
R8
BR
3E
AS
6E
C*
ZN
cu
NI
CO
Ft
MN
CR
V
Tl
C»
K
a
p
si
AL
MC
NA
B
•E
LI
0.93
1.0
1.5
d22
0.010
0.016
O.OIB
0.011
0.17
0.19
0.017
0.11
0.032
0.12
0.061
0.45
0.002
0.15
0.11
0.53
1.5
0.44
6,6
3.6
TO.
0.41
0.010
0.29
0.71
1.4
j!s
0.098
0.066
0.010
1.6
0.30
U3
2.0
1.3
< I.I
< 0.36
U.
36.
7*0
l.S
680,
31.
17.
200!
510.
2.1
1.6
1000.
MC
33.
0.16
0.6«
(M6)
(M6>
D-6
-------
TABLE D-6. SSMS ANALYSIS OF PARTICULATE FILTER BLANK FOR SASS-1 AND SASS-2
101 CAFB-PFb-A-l ll.56t
UG )
U
TM
Bl
PB
TL
• U
IB
OS
RE
N
MF
LU
YB
T*
ER
MO
OY
T8
CO
cu
3*
NO
PR
CE
L»
B«
cs
I
n
SB
an
IN
CO
PO
RH
RU
MO
NB
IH
T
SR
RH
BR
se
»s
GE
C*
ZN
CU
NI
CO
FE
MN
CR
V
TI
CA
K
s
p
SI
»l
MG
N*
a
BE
II
0.025
0.036
0.011
2.1
O.OI«
O.Olb
0.028
0.031
0.020
0.026
0.033
o.ooa
0.011
0.007
0.020
0.007
0.011
0.003
0.011
0.005
0.020
0.025
0.000
0.009
0.006
J2.
0.069
0.096
0.010
0.16
0.50
< 0.010
€ 0.005
« o.oia
0.20
0.012
0.50
0.009
1.0
0.35
1.2
0.25
0.67
< 0.056
« 0.100
S7.
11.
11.
0.24
92.
J.5
0.70
0.21
0.68
73.
16.
230.
0.0
170.
16.
35.
1.7
J2.
0.050
0.13
(*b)
D-7
-------
TABLE D-7. SSMS ANALYSIS OF XAD-2 RESIN FROM SASS-1
SAMPLE lOt CMB*l»X*»P»l 0.69286
ELEMENT
VALUE! PPM )
U
TM
Bi
PB
TL
AU
IR
OS
RE
H
MF
LU
YB
TM
ER
HO
DV
T»
GO
EU
SM
NO
PR
CE
L*
RA
CS
I
TE
SB
8N
IN
CD
PO
PM
RU
•40
NB
ZR
V
9R
RB
BR
Sf
AS
CE
6A
JN
CU
NI
CO
FF
MM
C»
V
TI
C*
K
a
p
91
«L
MG
NA
B
•E
LI
0,084
0.12
0.036
1.3
0.047
0.063
0,097
0.11
0.067
0.090
0.11
0.026
0.036
0.023
0.066
0.022
0.039
0.011
0.039
0.016
0.066
0.065
0.015
0.020
0.022
0.35
0.003
0.056
0.049
0.034
0.37
21.
0.061
0.049
0.017
0.063
0.056
0.007
0.027
0.011
0.96
0.026
o.l
I 0.26
0.052
t 0,023
I 0,009
7.3
7^1
0.22
0^70
0.42
0.094
0.31
"3.
22.
570.
7.5
65.
9.4
29.
no.
0.006
0.040
D-8
-------
TABLE D-8. SSMS ANALYSIS OF XAD-2 RESIN BLANK FOR SASS-1 AND SASS-2
SAMPLE IDl C»FB-»RB-P-1 0.667116 FROM a.10
V*LUE ( PPM )
U < 0.25
TM < O.Jb
HI < 0.11
PM 1.5
Tl < O.ja
«U < 0.18
IB < 0.26
OS « 0.31
Bf « 0.20
M < 0.26
MF < 0.11
LU « 0.077
YB < 0.11
TM < 0.066
EH < 0.20
MO « 0.066
DV < 0.11
TB « 0.031
CO < 0.11
EU « 0.052
SM < 0.20
SO « 0.25
PR < O.Oua
C£ < 0.059
L» < 0.060
B» < 2.1
CS < 0.010
I « 0.17
TE < 0.1«
SB < 0,100
SN < 0.14
IN S 21.
CD < 0.18
PD < o.ia
HM < O.OSO
»U « 0,18
MO < 0.17
"B « 0.021
ZM < 0.080
* « 0.033
3* 1.1
RB 0.12
BR 12.
SE 0.82
*S « 0.038
CE < 0.06<>
C» < 0.026
in 6.6
CU 6.7
NI 11.
CO 0.16
FE 16.
MN 2.0
CB 0.2<>
V 0.097
TI 0.91
C» 120.
K 120.
S 500.
P 22.
SI «6.
»L 16.
MG 15.
N* 180.
H 0.36
BF < 0.001
LI 0.060
D-9
-------
TABLE D-9. SSMS ANALYSIS OF COMPOSITE SAMPLE (CH) FROM SASS-1
SAMPLE IDI CAFMI-CM-O-I 2o*L
VALUE( PPM )
U < 0,003
IH < 0,004
HI < 0.001
PR 0.016
TL < 0,002
AU € 0.002
IR « 0.001
OS < 0.008
RE < 0.002
H « 0.003
HF < 0.004
LU < 0.001
VB < 0.001
T« « 0.001
ER < 0.002
HO < 0.001
or < o.ooi
TB < 0.001
60 < 0.001
eu < o.ooi
S* < 0.002
NO < 0.003
PR < O.OOI
Ct < 0.001
LA < O.OOI
BA 0.006
CS c 0.001
1 < 0.002
TE < 0.002
SB < 0.001
SN 0.80
IN s i.e
CD 0.018
PD < 0.002
RH < 0.001
»U « 0.802
NR < 0.002
NB « Oe00|
/* < 0.001
I < o.ooi
*J 0.006
RB O.OOI
BR o.017
8f 0.010
*8 0.003
GE < o.OOl
6A < 0.001
X! "•"
£V °'JO
NI 0.18
CO 0>C06
Ff 2,0
MN 0,073
CJ 0.15
* 0.005
TJ o.ooa
* 6|.
2 0.16
I 5T-
«? 0.92
f,1 0.30
tr °'15
MG o.ia
NA Oi?7
_? 0.050
?' 0.000
LI 0.001
-------
TABLE D-10. SSMS ANALYSIS OF COMPOSITE SAMPLE BLANK (CHB) FROM SASS-1
101 C»FR
-------
TABLE D-ll. SSMS ANALYSIS OF lOy CYCLONE CATCH FROM SASS-2
IDI C*FB«-IOC-O-I 0.102*6
fLE«lN1 VALUE! PP» )
U 6.2
TH 17.
BI < 1.7
PB 06.
TL < 0.19
AU < 0.23
IB < 0.36
OS < 0.39
Re < 0.25
* < 0.9J
Hf < 12.
LU « 3.J
YB < 1.2
TM < 0,18
ER < 1.8
HO < 0.3«
DV < 2,«
TB < 0.028
GD < 1.7
EU < 1.2
SM < 5.9
ND < 22.
PB 5.2
Cl 75.
LA 76.
BA 0.1 a It)
CS 1.7
1 «.5
U < 1.8
SB 8.0
SN 7.5
IN S 100.
CO 0.62
PD « 2.0
RH < 0,35
RU « o 20
"0 fl.0
NB »2.
'* 220.
* «6.
!? 0,«3 (1J
"f a«.
BR |,o.
se < «5.
*S 780.
6E c 1«.
6* 7«.
'J1 0.2« (*>
C« 110.
"I 53.
CO 18.
" MC
T
!' 0.82 (X)
C* 5.1 UJ
? 0.06 (X)
| »5. (X)
s? 9JO>
81 MC
•L MC
H* 0.9B (X)
Nf 0.30 (X)
| 0.25 (X)
D-12
-------
TABLE D-12. SSMS ANALYSIS OF 3y CYCLONE CATCH FROM SASS-2
101 C*FB*2-3C-0-1 0.100SG
ELEMENT
V*LUM
U
TH
RI
PB
TL
»u
t«
OS
BE
w
HF
LU
re
IM
EC
HO
0»
T6
CO
EU
SM
NO
PR
CE
L»
B*
CS
I
Tf
SB
SM
IN
CO
PD
RH
PI)
MO
NB
ZB
Y
SB
PB
BB
Sf
»s
GE
C*
Zn
cu
NI
CO
Ff
MM
CP-
V
Tl
C»
H
s
p
S!
»L
MG
N*
H
BE
LI
U.
6.7
I 10.
O.OBb
0.100
0.16
0.17
O.lt
1.2
J.9
l.S
1.1
0.019
0.79
0.13
?.2
0.013
1.3
t.l
17.
CX)
1.0
< 0. 17
« 0.98
3.6
S l*o!
0.77
< 0.69
« 0.020
< 0.067
2o!
190.
20.
0.11
20.
< 2e!
120.
8.9
66.
190.
(X)
16.
1.7
200.
U.
(X)
0.37 (X)
9.0 (X)
0.27 (X)
2.2
230.
4. a
1.3
(I)
(X)
(X)
0.21 (X)
O.II (XI
600.
0.9fl
14.
D-13
-------
TABLE D-13. SSMS ANALYSIS OF ly CYCLONE CATCH FROM SASS-2
101 C»F6«2-1C-0-1 0.1007G
ELfMENt
VALUE< PPM )
U
TM
HI
PB
TL
AU
IP.
OS
RE
M
MF
LU
»8
TM
EP
HO
OY
TB
GO
EU
SM
NO
PR
CE
LA
BA
CS
I
TE
38
SN
IN
CO
PC
RW
RU
MO
MB
ZR
»
SR
RB
BR
se
AS
CE
C*
ZN
cu
NI
CO
n
MN
CR
V
TI
CA
K
s
p
81
AL
MC
NA
B
BE
LI
3.9
7.7
< 0.26
220.
o.ioo
0.16
0.17
0.11
O.B6
2.6
o.so
o.se
o.as
0.7B
0.22
2.2
0.012
0.75
O.flO
1.6
7.0
6.1
«7.
67.
0,23 (X)
2.0
< 0.2S
< 0.9B
13.
13.
S tao,
0.95
« 1.3
< 0,026
< 0.087
3.*
56.
270.
57.
0.16 CX)
20.
28.
630.
50.
210.
260.
100.
70.
22.
3.1
370.
«20.
(X)
0.67 (XJ
MC
0.27 (X)
1.2 (X)
0.12 tX)
7.0 (X)
MC
0.99 (X)
0.30 (X)
0.11
2.*
14.
(S)
D-14
-------
TABLE D-14. SSMS ANALYSIS OF PARTICULATE FILTER FROM SASS-2
101 CAFR*2*PF-A>1 O.OU160
VALUE< UC )
U
TH
HI
PH
TL
«U
IB
OS
BF
ft
Hf
iu
re
no
o»
TB
GO
eo
s*
Kb
PR
CE
LA
BA
CS
I
TE
SB
SN
IN
CO
CD
RH
BU
MO
NB
0.27
0.00
0.07
7.7
0.091
0.006
0.009
0.010
O.Obt
0.072
0.079
0.007
O.OUI
0.013
0.055
0.036
O.UO
0.017
0.07(1
0.022
0.15
0.89
0.1U
2.0
1.1
oll2
0.011
0.12
0.79
2.2
11.
1.0
O.OJ9
0.009
0.09S
0.99
0.18
1.9
OH
BP
SE
AS
Gt
G*
7N
CU
NI
CO
Ft
MN
CR
V
TI
C*
K
s
p
SI
*L
MG
NA
B
BE
LI
0.66
O.Sa
J.7
o!ll
7.7
16.
II.
2.0
0.2J
220.
9.9
6.9
i.e
61.
2.9
I.)
11.
100.
1.)
200.
1.5 (MG)
11.
0.02«
0.22
(MG)
D-15
-------
TABLE D-15. SSMS ANALYSIS OF XAD-2 RESIN FROM SASS-2
IDl CWB12-XR-P*! 0.6787G FORM
ELEMENT
VALUE( PPM )
u
TH
BI
P8
TL
AU
I«
OS
RE
N
HF
LU
VB
TM
ER
HO
or
TB
GO
ru
3M
HO
PR
CE
LA
8*
CS
1
TE
SB
SN
IN
CO
PO
RM
RU
MO
NB
ZR
¥
SR
RB
RR
SE
AS
GE
GA
ZN
cu
HI
CO
ft
MN
CR
V
TI
CA
K
S
P
91
AL
MG
NA
B
SE
LI
0.09
0.70
0.22
1.3
0.27
O.J6
0.56
0.61
0. J8
O.SJ
0.6Q
0.15
O.il
0.11
O.J9
0.1S
o.?a
0.061
0.22
0.100
0.39
o.a<>
O.OS6
0.12
0.13
o.«a
0.020
o.ja
0.28
0.20
0.26
-------
TABLE D-16. SSMS ANALYSIS OF COMPOSITE SAMPLE (CH) FROM SASS-2
S»MI»L( 101 C»f B'i-gM-0
U
TH
Bl
PR
TL
»U
IB
09
RE
H
HF
LU
tB
HO
or
TB
GD
EU
S«
NO
PR
CE
L»
8»
CS
I
If.
SB
SN
IN
CD
PD
BH
RU
MO
NB
P.B
B»
SF
»S
Gt
G*
ZN
CU
NI
CO
FE
MN
c»
V
Tt
CA
K
s
p
at
*L
MG
m>
B
Bf
Li
VALUE! PPM )
<
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
<
4
4
4
<
4
4
4
4
4
t
4
4
4
<
4
4
4
4
0.000
0.012
0.004
o.ooe
0.005
0.006
0.009
0.010
0.007
0.009
0.011
0.003
O.OOU
0.002
0.007
0.002
0.004
0.001
O.OOU
0.002
0.007
o.ooe
0.001
0.002
0.002
O.OOfl
0.001
0.006
0.005
0.00)
1.1
0.72
o.oas
0.005
0.002
0.006
0.02i
0.00,?
O.OOi
0.001
0.004
0.001
0.0?4
0.059
0.002
0.002
0.001
0.18
0.29
0.19
0.005
0.74
0.036
0.12
0.002
O.OJS
0.84
0.29
110.
2. a
0.59
0.22
0.27
2.1
0.77
0.001
0.005
D-17
-------
TABLE D-17. SSMS ANALYSIS OF COMPOSITE SAMPLE BLANK (CHB) FROM SASS-2
S»»»Ptl 101 C»Ffl»2-CHB-0-l 20NL
VALUE( PPM )
U
TM
61
PB
Tl
»U
Ifi
OS
BF
H
HF
LU
YB
TN
EC
HO
0*
TB
GO
EU
SM
ND
PR
CE
L»
a*
cs
i
TE
SB
3N
I"
CD
PD
RH
RU
MO
SB
7R
V
SR
RB
BR
St
AS
6t
6*
ZN
cu
NI
CO
PI
MN
CR
V
TI
C*
K
s
p
St
»L
MC
N»
6
HE
tl
0.030
O.OII
0.022
0.013
0.018
0.027
0.030
0.019
0.02S
0.031
0.007
0.011
0.006
0.019
0.006
0,011
0.003
0.011
0.005
0.019
O.OIU
O.OOo
0.006
0.006
0.008
0.001
0.016
O.Ola
0.009
1.3
0.72
0.039
0.010
0.005
0.018
0.016
0.002
O.OOn
0.003
0.004
0.001
0.13
0.009
0,000
0.006
0.003
1.0
0.076
0.38
0.001
0.53
0.026
0.009
0.002
0.021
0.85
0.16
9.6
2.1
2.J
0.22
0.21
5.9
0.025
0.000
0.003
D-18
-------
TABLE D-18. SSMS ANALYSIS OF CYCLONE CATCH FROM RAC-1
SAMP).) |l)l CAKt-t-Al | CTCLUNk
t L f "I
VALUt t HPM }
II
in
HI
PH
Tl
All
Ik
IIS
Hf
LU
YH
HI)
DY
IB
ct
I A
IU
rs
i
rt
SH
( D
f()
HH
kit
HH
Sb
AS
Gf
CM
I»J
CU
FE
MN
C"
v
I 1
CA
SI
AL
Ml,
NA
H
Mt
LI
«. J
fl.S
o.n
0.1H
0.1<»
0.67
». 4*3
O.H6
0.057
O.bu
0.16
O.J9
0,««
1.7
^.8
1.3
U.
?.2
O.t>7
1.0
1.6
68.
0. 55
0.<»7
0.12
O.OtS
1.2
7.7
87.
IS.
590.
7.7
17.
S.9
»•».
S.O
17.
760.
28.
0.11
6.0
S.I
710.
2S.
(X)
(X)
ii.22 (XJ
«.a (X)
0.17 (X)
i.9 (X)
US.
2.0 (X)
U.J1 (X)
0.16 (X)
ISO.
220.
O.S1
D-19
-------
TABLE D-19. SSMS ANALYSIS OF NEAT FILTER PARTICULATE FROM RAC-1
i
101 CA^H-HAC 1-0-1 O.I101U
V»k.Ut( ^t»« )
<
<
<
«
<
' <
c
<
<
<
«
<
c
<
c
<
<
<
«
<
«
M . 6
**.6
2.9
olis
0.18
U ,£A
O.iU
1.6
l.S
l.i
1.8
0.90
O.i/
1.6
O.SJ
4.2
0,022
1.1
,i:°
760,
1.3
0.60
1.4
1.6
u
IH
HI
PB
1L
AU
1«
US
U>
VB
I*
tH
MO
OY
7M
GO
tu
SM
NO
PR
Ct
LA
BA
C9
1
U
SH
3N
IN
PO « |.o
MH < 0,049
Ml/ < U.lb
MU 1.9
NH II.
IN 240,
» 17.
S» 660.
KH I/.
3t < u)b
GE < 11)2
GA < J7,
Z* 100.
Cu «a.
Nl 41.
CO 4.7
Ft 1,6 (X)
«K 190,
C« 17.
V 91.
U 1.2 (X)
CA 12. (XJ
K 0.46 (X)
S 0.88 CX)
P 210.
31 4.7 (X)
AL MC
Ht 0.46 (X)
N* 0.1J (X)
B O.IOO(X)
Bf 0.61
LI 7.1
D-20
-------
TABLE D-20. SSMS ANALYSIS OF NEAT FILTER PARTICULATE FROM RAC-3
tin c^H-t.»t j-o-i H
V»LUM
U < I.I
I" < b.I
HI < <>.,>
*B 6S.
U < O.I,
nil < «.<>,
I w * M . U«
* <;. i
Hf 0.« i>. I no
n*
St < lb.
*5 44.
(if « I*.
(,« < 7B.
;N 110.
cu «".
M au.
en i.t
n ua (xi
MN a<)o.
CM 1*>.
v i«o.
Tl 0.11 (X)
C* 6.0 (X)
K 0.01 (X)
CL < O.OfcP
S 1.1 t*>
P b'O.
SI '
»u «c
MU o.ai
-------
TABLE D-21. SSMS ANALYSIS OF CAFB LIGNITE
• AMPLE lOt (.10 ft lit (S/NbOOlO/77) 0.67S7U
VALUU PPM )
U
TM
HI
PH
TL
AU
IH
OS
Kt
MF
LU
YH
TM
tH
HI)
DV
TB
CD
EU
SM
NO
PR
Ct
LA
HA
cs
I
Tt
SB
3N
1*
CO
PO
RN
HU
MO
NH
IR
»
SR
HH
HR
3t
AS
Ct
GA
lt»
CD
Nl
CO
Ff
MN
CM
V
H
CA
K
s
p
SI
At
M6
NA
B
Bt
1.1
0.32
0.20
«.*
0.029
0.036
o.oss
n.060
0.038
0.100
0.12
0.0)1
0.090
0.01)
0.0)9
0.006
0.20
0.020
0.061
0.015
o.ia
0.60
o.ta
1.1
1.5
0.006
0.000
0.075
0.30
2.1
21.
0.17
0.037
0.010
0.050
o.a)
0,64
5.9
0.65
o!59
0.2)
2.8
1.5
0.20
2.6
13.
15.
also
0.19 (X)
22.
2.r
2301
0.17 (X)
"»a.
0.23 (X)
l!i (X)
0.23 (X)
130.
tea.
21.
0.030
0.02
D-22
-------
TABLE D-22. SSMS ANALYSIS OF CAFB LIMESTONE
101
*H
V»LUt(
< 0.57
< O.SJ
< 0.2i
12.
OS < O.SS
>-k « O.ib
LU
HU « O.Ob'J
DY < o.^o
rn < o.oio
i.o < o.^o
tu < o. la
SM < O.ui
NO < 0.10
PB o.ii
CE 0.42
L» 1.8
HA 160.
CS 0.0«
1 «,">
TF < 0,i$
3D 0.96
S»« u.7
IN » 110.
CU < 0.05<>
PD < 0.5«
BH « 0,089
MU < 0.^8
"i O.u»
NH < 0,1 \
I* t.c!
Y 0.52
SH 210.
MH ^.1
hw < 18.
8t « u.S
*S « 0.079
Gt < 0.11
(.* < O.Ottft
7N
-------
TABLE D-23. SSMS ANALYSIS OF CAFB FINES RETURN
SAMPLE 1DI CAP* /.lNl|_R!L_*jL°Jr.**6
VALUE( PPM }
u
TH
Bl
PB
TL
AU
1R
OS
RE
M
MF
LU
VB
T*
ER
HO
01
TB
CO
EU
SH
NO
PR
CE
LA
B*
C8
I
TE
SB
SN
IN
CD
PD
RM
RU
MO
NB
ZR
»
8R
RB
BR
8E
AS
Of
GA
ZN
CU
Nl
CO
re
MN
CR
V
TI
CA
K
»
P
SI
AL
MC
NA
B
BE
LI
S.i
o!o«3
27.
0.11
0)21
0.21
o.ia
o.sa
2.5
olio
O.I*
1.0
0.20
o!fll6
0.«8
0.92
0.«5
< 0.7a
J.I
5.5
I 1*0.
« 0^7«
< 0.21
« O.tl
2.9
« 17.
180.
2*.
'00.
no.'
270,
2U
0.0(11
2l!
10.
a.i
260.
(S)
120.
0.87 (X)
MC
O.SS (%)
5«ol
MC
MC
0.50 (I)
6«0.
olso
J.I
D-24
-------
TABLE D-24. SSMS ANALYSIS OF CAFB BOILER BACK
101 CAFB BujLtw BACK o.o«6ii>
VAUUE< PPM 1
U u.l
TM 16,
BI < 0.07«
PH 29.
Tl < 0,65
AU < 0.11
IS « 0.17
03 < 0.18
Rf < 0.12
H < 0.90
HF < 5.U
LU « 0.77
YB < o.a]
TM « 0.))
E» < 1.7
HO < 0.45
OY < 2.2
TB « 0.011
CD < 0.67
EU « 0.77
JM < a.7
NO 15.
PR 0.5
CE J5.
LA «9.
BA 4)0.
CS J.O
I « 0.12
Tt « O.BJ
SB l.»
3N 6.}
IN * 1^0.
CO 0.77
PO « 1.1
(JH < 0.029
RU < o.o^i
MO 1.9
NH ^9.
I* 200.
Y JO.
JR 0.11 (X)
KB ^1.
BP «»•
SE < >*•
*S I^O.
CE « «•«
GA J«.
ZN **•
CU 1^'
NI *0.
CO *'T
FE i.J (X)
MN ^«0.
CR «.
v too.
T] 0.5«* (X)
CA 7.« <*J
K 0.51 (X)
S 0.7S (S)
P 210.
41 MC
AL "C
MG 0.15 C»)
NA »»«.
B "0.
Bt 0,a9
LI lfl-
D-25
-------
TABLE D-25. SSMS ANALYSIS OF CAFB BOILER SIDES
101 CAFB 80IUR 31DE8 0,09826
V»LUF( PPM )
u
TM
Bl
PB
TL
»U
IR
OS
»e
M
HF
LU
VB
TM
e»
HO '
OY
T8
60
eu
SM
HO
PR
Cf
L*
BA
CS
1
TE
SB
9N
l»
CD
PD
AH
RU
HO
NB
70
»
SR
R8
BR
tt
A3
CE
CA
ZN
cu
NI
CO
re
MN
CR
V
Tl
CA
K
9
f
at
AL
MG
NA
8
BE
LI
20.
7l!
o!l9
0.29
O.J1
0.20
1.6
39.
1.3
I.a
0.069
2.1
0.78
5.4
0.023
1.9
1.0
5.7
s!7
60.
as.
0.11 (X)
5.3
0.63
6^8
ISO.
0.0
6.7
0.59
0.16
31.
73.
6«0.
SI.
O.lt
36.
« 9.7
370.
< *S.
59.
100.
(S)
o.ta (X)
0.20 CO
120.
290.
2.1 (»)
MC
0.48 (X)
0.70 (X)
aio.
MC
«C
0.70 (X)
eso.
280.
0.59
D-26
-------
TABLE D-Z6. SSMS ANALYSIS OF CAFB STACK KNOCKOUT
101 CAFB STACK HO o.oseou
HI
PH
TL
ill
IS
ns
MF
LU
YH
TM
ER
HI)
0'
TH
CO
EU
SM
NO
PR
Ct
LA
«A
CS
I
Tf
SB
SN
IN
CD
PD
RH
RU
MO
NB
3»
BH
HR
5t
»3
GE
GA
IH
CO
Nl
CO
ft
MN
C«
V
TI
CA
K
3
P
SI
AL
MG
MA
B
Rf
LI
17.
< 0.67
120.
O.SO
0.17
1 .«
15.
1.7
2.1
1.1
1.1
1.0
7.b
0.04?
1.8
1.8
7.S
J«.
II.
160.
110.
O.lb (X)
6.8
1.2
2.7
o.a
la.
160.
2.6
2.0
0.09S
0.29
0.2
«7.
110.
B8.
0.11 (X)
66.
100.
i6.
120.
79.
100.
120.
220.
18.
I .8
170.
62.
120.
1.1
(X)
(X)
(X)
(X)
(X)
1.6
1.7
760.
MC
MC
0.«3 (X)
O.IOO(X)
0.12 (S)
1.6
81.
D-27
-------
TABLE D-27. SSMS ANALYSIS OF CAFB STACK CYCLONE
c*re
CTLCONI o.«o»ac
tLE*ENT
V*LUtC PP*
u
TH
Bl
PB
TL
»U
IB
OS
Rt
*
Hf
LU
ra
TM
en
HO
or
TB
GO
EU
SM
NO
PR
Ct
LA
B*
C3
1
te
SB
SM
IN
CO
PO
RH
RU
MO
NO
ZH
Y
SB
R8
RR
se
*s
GE
6*
IN
CU
NI
CO
Ft
MN
CR
V
TI
C»
K
3
P
81
»L
MC
N*
B
BE
LI
6.6
l<».
2.0
la.
<
<
1
<
«
<
0
0
0
0
1
1
I
0
2
0
5
0
2
0
8
17
7
56
110
6BO
1
0
0
3
3
110
1
1
0
0
2
47
210
68
0
.14
.17
.27
'.18
.0
IB
.4
.75
.7
.51
.3
.021
.5
.95
.9
*
.2
•
•
•
.2
.81
.95
.1
.5
t
.0
.0
.19
.15
.6
•
•
•
.12 (X)
(X)
71.
< 18.
190.
< 5.6
19.
< 59.
561
11.
2.B
620.
II.
160.
1.1 (X)
6.7 (X)
0.62 (XI
0.41 (X)
690.
MC
MC
0.64
0.27 (X)
590.
t.l
68.
D-28
-------
TABLE D-28. SSMS ANALYSIS OF CAFB REGENERATOR CYCLONE
SAMPLE IDl CAffl MtG CVCLONf 0.0666G
tLFMENT V«LUt( PPM )
U 8.9
TH ^a,
HI « 0,u<*
P8 SJ.
TL < |.J
»u < o.ja
IB
OS
HF
CU
YB
tM
TB
HO
0V
TB
CD
FU
3«
NO
PH
Ct
I*
B»
CS
I
Tf
SB
SN
IN
CD
PD
OH
RU
MO
NH
RB
BW
SE < .
AS »>«.
GE < 6 . 8
G» %2.
2N 67.
CU 57.
NI 5«.
CO 12.
Ft »•* <*'
HN 210.
CR a».
V 180.
TI O.Q1 (t)
C» T.7 <«>
K O.IOO(X)
S 8.5 <*>
P aso.
si T.9 m
»L «C
MC 0.56 (I)
«A O.IOO(X)
B 400'
8fc I'l
LI ••«
D-29
<
<
c
<
<
<
<
<
<
<
4
<
<
S
<
<
<
0.16
o.ao
01 3
»le
0.17
8.7
1.7
0,92
0. 56
1.8
0.9«
1.6
O.OIH
1.7
1.2
6.0
16.
6.9
SJ.
16.
O.tfl (X)
p t
c » a
i.f
0.90
J.O
J.7
160.
l.i
I.S
O.J7
0.098
c.6
*
510.
b«.
O.IOO(X)
16.
70.
-------
TABLE D-29. SSMS ANALYSIS OF CAFB GASIFIER BED
•AMPLE 101 CMS 6A8 (»10 «1179 0.0*498
ELEMENT
VALUE( PPM }
U
TH
81
PB
11
AU
1«
09
RE
N
HF
LU
YB
TM
EP.
HO
OY
TB
CO
EU
SM
HO
PR
ce
LA
B*
CS
I
TE
SB
9N
IN
CD
KM
P.U
MO
NB
I"
1
8»
KB
0R
BE
AS
6E
6A
ZN
cu
NI
CO
FE
MN
Cft
V
TI
CA
K
5
P
81
AL
M6
NA
B
BE
LI
0.7«
1.0
O.aa
2.B
0.5«
0.65
1.0
1.1
0.60
0.46
2.3
0.56
0.41
0.24
0.70
0.12
0.40
0.07B
0.40
0,28
0.84
0.58
0.86
14.
ISO.
0.60
« 0,11
« 0.49
21.
i ise!
< 0.12
< 0.18
* 0.54
< O.JJ
12.
110.
29o!
IS.
72.
< 48.
720.
< IS.
40.
16.
(I)
2.S
180.
11.
100.
0.18 («)
MC
0.56 (X)
260.
MC
0.41
1.4
J90.
(S)
«)
(I)
0.77
25.
D-30
-------
TABLE D-30. SSMS ANALYSIS OF CAFB REGENERATOR BED
IDl CMB HfC BtO *liei 0,086SC
V»LUEC PPM )
U
TH
BI
PB
TL
»U
IB
09
RE
N
HF
LU
YB
TM
e*
HO
DY
TB
CO
ru
s*
NO
PR
Cf
L*
B*
cs
i
t£
SB
SN
IN
CO
PO
RH
RU
MO
NB
i*
Y
SR
RB
SR
Sf
AS
GE
C»
IH
cu
Nl
CO
n
MN
CR
V
TI
C*
K
s
p
S!
»L
MG
N*
B
RE
Li
I.I
2.3
< 0.083
0.100
0.1?
O.I9
o.ao
O.IS
o.aa
1.5
0.100
0.077
0.25
0.13
0.12
O.a«
0.015
0.«2
O.OS2
0.16
2.0
O.OT
6.8
7.3
130.
0.05
0.20
0.091
6.1
9.8
170.
O.oai
1.0
o.ia
0.100
1.3
8.2
3%.
220.
29.
36.
6.2
240.
S.3
3.2
0.36 (X)
76.
a. 2
J8.
0.23 (X)
«C
0.31 (X)
0.30 (X)
85.
3.2 (X)
3.0 (X)
0.48 (X)
0.11 (X)
140.
0.20
I*.
D-31
-------
TABLE D-31. SSMS ANALYSIS OF CAFB OIL FEED
SAKPLT
UK
Kl
¥*LUt( PPM )
U
IM
01
PB
TU
AU
IN
US
HF
LU
Vt)
TM
m
MO
1>Y
TB
GD
tu
SM
Nl)
PR
CF
LA
h*
cs
1
It
SB
5N
IN
CD
PD
RM
NH
7M
»
SB
WH
HN
at
AS
Gt
GA
IH
Cl'
NI
CD
Ft
MN
CM
V
tl
CA
K
9
P
31
AL
MG
N»
H
(»f
L)
<
c
<
<
<
<
<
<
S
«
«
<
«
«
C
c
0.009
U.OM
II.
0.028
0.017
0.057
0.062
fl!o52
0.065
U.OI5
0.022
o.oia
0.000
0.013
0.023
0.006
0.023
0.010
0.000
o.oso
0.009
0.012
O.Oli
o.ai
0.006
0.067
0.029
0.15
0.45
17.
0.82
0.029
0.23
O.OS7
0.79
0.021
o|o07
0.38
o!2B
0.019
1.3
0.010
0.006
an.
«I
0.67
33.
o!«»B
a9.
0.32
•3.
99.
0,«2 (X)
IS.
110.
3t.
II.
ISO.
O.ll
0.001
0.30
D-32
-------
TABLE D-32. SSMS ANALYSIS OF CAFB BITUMEN
Elt»t*l v»LUCt
U < 0.06^
1H < O.OH7
HI < O.U27
PH i.7
IL < 0.0)0
All < 0.01",
IH < 0.069
US < 0.0/b
Ht < 0,017
ft < 0.061
Hf < 0.079
HI « 0.019
YH « 0.027
IM < 0.016
m < O.OttH
HI) < 0.016
DV < 0.026
IH « 0.007
I.I) < 0.02H
ni < 0.012
s" < o,oa8
NO < 0.060
PH < 0.011
cf o.oflo
L» < 0.016
»A I ."
Ci U.007
1 < 0.041
n < a.OK
SH 0.091
SN 0.76
1« * IS.
CU <».2«
PR « 0.01S
MH < 0.012
uu < 0.OflU
MII 0.23
MM 0.01"
tH * 0.019
V < 0.008
SR 0.13
MH 0.056
BH < 0.059
St 1.3
AS «. *
(,(• < 0.017
G« O.OS6
ZN 110.
Cu 20.
Nl 110,
CU 0.58
Fl 00,
MM 2.0
CR 1.2
V liO.
II O.J9
C» S9.
n 2a.
3 0.28 (X)
t> 18.
SI 1«0.
*t U.
MC 29.
NA |9.
8 I.«
HI 0.016
U <>.*»
D-33
-------
1.5
too F
W*VELEN6TN,micf»n
3 (?8
9 10 12 19 20 3040
4000 3900 3000 2900 2000 I BOO 1600 1400 1200 1000 800 600 400 200
FREQUENCY, M-l
Figure D-l. IR spectrum of lOy cyclone catch from SASS-1.
Content of spectrum is less than or equal to
that of blank.
WAVELENCTH,*ic»Mi
9 6 7 8
20 3040
I I I I I 11 I I I'll I I I I I I I I 1 I I I I I I I I III I II I 1 . • I
4000 3500 3000 2900 2000 1800 1600 1400 1200 1000 800 600 400 200
FREQUENCY,«-'
Figure D-2.
IR spectrum of 3y cyclone catch from SASS-1.
Peaks indicate saturated esters; possible
aryl or unsaturated esters or ethers,
organosilicon compounds.
D-34
-------
IS 20 30 40
..„ ...... . I I I I I I I I | i I I I ' I I | 11 I | I 1 1 i I I I | I I I | i 1 I fTT.
4000 J500 3000 2500 2000 1800 1600 1400 (200 1000 800 600 400 200
FREQUENCY,cn-t
Figure D-3. IR spectrum of lp cyclone catch from SASS-1.
Peaks indicate saturated esters and hydro-
carbons; possible aryl or unsaturated esters
or ethers.
WAVELENGTH,
45 6
7 8 9 10 12 IS 20 3040
4000 JSOO 3000 2900 2000 1800 1600 1400 1200 1000 800 600 400 200
FREQUENCY, c*-'
Figure D-4. IR spectrum of particulate filter from SASS-1
Content of spectrum is less than or equal to
that of blank.
D-35
-------
2
_ 100
I io
yj
I"
I 40
WAVELENGTH, micro**
9 6 7 S 9 10 12 19 20 3040
4000 3900 3000 2900 2000 1800 1600 1400 1200 1000 BOO 600 400 200
FREQUENCY, wH
Figure D-5. IR spectrum of condensate extract from SASS-1.
Major peaks Indicate aliphatic hydrocarbons,
esters, ketones; possible ethers, substituted
aromatics, nitrocompounds and organosilicon
compounds.
WAVELEN6TH, Micron
9 67 6 9 10 12 19 20 3040
°r
4000 3500 3000 2900 2000 1800 1600 1400 1200 1000 800 600 400 200
FREQUENCY, e«-'
Figure D-6.
IR spectrum of XAD-2 resin from SASS-1. Major
peaks indicate esters, saturated hydrocarbons;
possible ethers and nitrosubstituted compounds.
D-36
-------
WAVELENGTH,,™,,,,,
5 6789
20 3040
. - - - - "i i i i f i "i i i i r i | ii i i it i | i i t i i n T i i rt i i -
4000 3500 3000 2500 2000 1800 1600 1400 1200 1000 800 600 400 200
FREQUENCY ,em-I
Figure D-7. IR spectrum of module rinse from SASS-1. Peaks
indicate esters and aliphatic ethers.
25
100
I 80
L.
! 60
40
WAVELENGTH, micro**
6
8 9 10
IS 20 30 40
t-
in
5 20
^'Virvsfr^^
T
T
i i i 11 i i i i i r» i i i i i i 11 i i i ' » M ' < i I'"
4000 3500 3000 2500 2000 1800 1600 1400 1200 1000 800 600 400 200
FREQUENCY, c«-'
Figure D-8.
IR spectrum of probe rinse from SASS-1. Content
of spectrum is less than or equal to that of
blank.
D-37
-------
2.9
100
• 9 10 12 19 20 3040
4000 3900 3000 2900 2000 1800 1600 1400 1200 1000 800 600 400 200
FREQUENCY, c«-l
Figure D-9. IR spectrum of lOy cyclone catch from SASS-2.
Content of spectrum is less than or equal to
that of blank.
WAVELENGTH, ulerwi
6 7 8 9 10 12 19 20 3040
4000 3900 3000 2900 2000 1800 1600 1400 1200 1000 800 600 400 200
FREQUENCY, c»-'
Figure D-10.
IR spectrum of 3y cyclone catch from SASS-2.
Content of spectrum is less than or equal to
that of blank.
D-38
-------
•AVELEM6TM,
8 9 10 12 15 20 3040
I I I I I | I I I | I i I | I I I | I i i | i I I | I I I I i I I | I I I f ' I T
4000 JSOO 3000 2500 2000 1800 1600 1400 1200 1000 800 600 400 200
FREQUENCY,e«-'
Figure D-ll. IR spectrum of lp cyclone catch from SASS-2.
Content of spectrum is less than or equal to
that of blank.
29
100
5 80
«M>
£ 60
fc «0
31
•n
Z 20
WAVELENGTH, Micron
5 6 7 8 9 10 12 15 20 3040
T
T
I I 1 11 \ I I I I I I I I I I I I 11 I I I ' ' ' I 11 I I ' I ' I I I I I
4000 3900 3000 2 SCO 2000 1800 1600 1400 1200 1000 800 600 400 200
FREQUENCY, c*-'
Figure D-12.
IR spectrum of particulate filter from SASS-2.
Content of spectrum is less than or equal to
that of blank.
D-39
-------
Z.5
WAVE LENGTH. mic.OM
5 6 7 I 9 10 II 15 20 30 40
100
I*
uT
|K
5 40
| zo
4000 3500 3000 2900 2000 1800 1(00 1400 1200 1000 BOO 600 400 200
FREQUENCY, c»-l
Figure D-13.
IR spectrum of probe rinse from SASS-2. Major
peaks indicate saturated hydrocarbons, esters
and aryl esters; possible substituted aromat-
ics and aliphatic ethers.
8 9 K) 12 19 20 3040
°r
4000 3500 3000 2500 2000 1800 1600 1400 1200 1000 800 600 400 200
FREQUENCY, «•-•
Figure D-14. IR spectrum of XAD-2 resin from SASS-2. Major
peaks indicate aryl or unsaturated esters,
ketones, hydrocarbons; possible ethers and
nitrocompounds.
D-40
-------
2.5
_ 100
I 80
60
40
20
WAVELENGTH, micro.1
5 678
9 10 12 15 20 3040
T
4000
T
T
• '"" I ' I I | I I I I I I I | I I l | I I I | I I I | I I I | I I I | i I i
3500 3000 2500 2000 1800 1600 1400 1200 1000 600 600 400 200
FREQUENCY, c«-'
Figure D-15. IR spectrum of XAD-2 resin from SASS-2, LC fraction 1,
Peaks indicate aliphatic and aromatic hydrocarbons;
trace esters and ethers.
25
100
1
5 80
«P
Cfc
S 60
x
t 40
at
at
5 20
WAVELENGTH, nicrott
5 6
1 8 9 10 12 15 20 30 40
I t III i I II
I I I I I I I i i i I ' ' ' I I ' I I ' I i I I I I I i i » I I l ' I ' ' M ' '
2500 2000 1800 1600 1400 1200 1000 800 600 400 200
FREQUENCY, e»-'
' i f i » M I I » I ' '
4000 3500 3000
Figure D-16.
IR spectrum of XAD-2 resin from SASS-2, LC fraction 2.
Peaks indicate hydrocarbons and possible ethers.
D-41
-------
2.9
WAVELEH6TH,miCroM
3 6 7 8 9 10 12 19 20 30 40
100
1,0
Ui
I"
I 40
i zo
4000 3900 3000 2900 2000 1800 1600 1400 1200 1000 800 600 400 200
FREQUENCY, C»-'
Figure D-17. IR spectrum of XAD-2 resin from SASS-2, LC fraction 3.
Peaks indicate esters and trace saturated hydrocarbons
and ethers.
7 8 9 10 12 19 20 3040
I I i i I i I M i i i I ' ' ' I I I 'I ' i i I ' i i
4000 3500 3000 2900 2000 1800 1600 1400 1200 1000 800 600 400 200
FREQUENCY, CM'1
Figure D-18.
IR spectrum of XAD-2 resin from SASS-2, LC fraction 4,
Content of spectrum is less than or equal to that of
blank.
D-42
-------
25
1001
WAVELENGTH,
5 67
10 1.2 15 20 JO 40
| 80
ut
Sf 60
>•
I 40
m
2 20
I I • I I 1
4000 3500 3000 2500 2000 1800 1600 1400 1200 1000 800 600 400 ZOO
FREQUENCY, «-<
Figure D-19. IR spectrum of XAD-2 resin from SASS-2, LC fraction 5.
Content of spectrum is less than or equal to that of
blank.
WAVELENGTH,
7 8 9 10 12 IS 20 30 40
100
I 80
A
3 60
t 40
m
at
5 20
4000 3500 3000 2500 2000 1800 1600 1400 1200 1000 800 600 400 200
FREQUENCY, c»-'
Figure D-20.
IR spectrum of XAD-2 resin from SASS-2, LC fraction 6.
Major peaks indicate esters, ketones; possible amines,
alcohols, phenols, ethers and nitrocompounds.
D-43
-------
2.5
WAVELENGTH.
5 6
10
15 20 30 40
I I L_
100
1.0
u/
S 60
i 40
VI
* 20
4000 3900 3000 2500
2000 1000 1600 1400 1200 1000 800 600 400 200
FREQUENCY, c«-'
Figure D-21. IR spectrum of XAD-2 resin from SASS-2, LC fraction 7.
Major peaks indicate unsaturated esters, saturated and
unsaturated ketones; possible ethers and nitrocompounds,
WAVELENGTH, •itrwi
5 678
20 3040
I 1 I i I ' I i I I I I I i i i I I I .
4000 3500 3000 2500 2000 1800 1600 1400 1200 1000 BOO 600 400 200
FREQUENCY, c»-I
Figure D-22.
IR spectrum of module rinse from SASS-2. Major
peaks indicate aliphatic and aromatic hydro-
carbons; saturated, unsaturated and aryl esters;
possible ethers and saturated ketones.
D-44
-------
2.5
_ 100
*
W
i BO
uf
i *°
*-
i 40
v*
tt
* 20
Oi
WAVELENGTH,
5 67
9 10 12 15 20 3040
' ' ' ' I I 1 I I I I | I I I I 1 I I I | I I I | I I I I I I I I I I I | I I I I ' I I | I I I | I I .
4000 3500 3000 2500 2000 1800 1600 1400 1200 1000 800 600 400 200
FREQUENCY ,c»-l
Figure D-23. IR spectrum of module rinse from SASS-2, LC fraction 1.
Content of spectrum is less than or equal to that of
blank.
25
100
I BO
«r
a
8 60
z
£ 40
m
V*
5 20
WAVELENGTH.
5 6 7 8 9 10 12 IS 20 3040
~T
T
T
T
T
I I I i I I I I I 'I I I I I I > I 1 I I
4000 3500 3000 2500 2000 1800 1600 1400 1200 1000 BOO 600 400 200
FREOUENCY.cn-'
Figure D-24.
IR spectrum of module rinse from SASS-2, LC fraction 2,
Spectrum indicates aliphatic hydrocarbons.
D-45
-------
»»VELENGTH,1Bier8M
5 678
9 10 12 15 20 3040
I I I I I I M I I I I I II I 1 I I I I I I I I I I1| I I I | I I I
4000 3500 3000 2500 2000 1800 1600 1400 1200 1000 800 600 400 200
FREQUENCY,•«-!
Figure D-25. IR spectrum of module rinse from SASS-2, LC fraction 3.
Content of spectrum is less than or equal to that of
blank.
2.5
WAVELENGTH,
9 10
12
i
IS
.£.
J040
100
I 80
•*
a
S 60
I 40
a
-------
4000
WAVELENGTH,r
6
9 10 12 15 20 3040
"I i i i i | i i i | i i i | 11 r i 11 i | i i i | 11 i I M i | i i i | M i
5500 3000 2500 2000 1800 1600 1400 1200 1000 800 600 400 200
FREQUENCY, e*-'
Figure D-27. IR spectrum of module rinse from SASS-2, LC fraction 5.
Peaks indicate saturated, unsaturated and aryl esters.
WAVELENGTH, *itfet»
TT
4000
T I I ( ' ' I I I I I I II ' I T' I I I I I I I I I I I I I I I I I
3500 3000 2500 2000 1800 1600 1400 1200 1000 800 600 400 200
FREQUENCY, c*-'
Figure D-28. IR spectrum of module rinse from SASS-2, LC fraction 6,
Peaks indicate saturated, unsaturated and aryl esters.
D-47
-------
WAVELENGTH, micro.,
2.5
4 5 6 7 B 9 10 12 19 20 3040
100
60
40
4000 3900 3000 2900 2000 1800 1600 1400 1200 1000 800 600 400 200
FREQUENCY, C«-'
Figure D-29. IR spectrum of module rinse from SASS-2, LC fraction 7.
Spectrum indicates saturated ethers.
6 7 8 9 10 12 15 20 JO 40
4000 3500 3000 2900 2000 1800 1600 1400 1200 1000 800 600 400 200
FREQUENCY, e«-'
Figure D-30.
IR spectrum of condensate extract from SASS-2.
Peajcs indicate trace aliphatic ethers.
D-48
-------
WAVELENGTH.nMuem
6 ? 6
9 10 12 13 20 3040
I ' ' 'T i i I ' i iiii |Mi | i i i | 11 i | ir i | i i i | i i i | i i r | ti i
4000 3500 3000 2500 2000 1800 1600 1400 1200 1000 800 600 400 200
FREQUENCY, c*-l
Figure D-31.
IR spectrum of Tenax resin from RAC-2. Major
peaks indicate primary and secondary amides,
ethers, hydrocarbons; possible amines, alco-
hols and phenols.
25
WAVELENGTH, i
6
9 10 12
IS
20 30 »0
100
' 80
h
! 60
40
I
20
I I I M I I ' 1 I I
T
T
T
4000 JSOO
i I i I I i I i I I I I I i i I i '"«'"
3000 2500 2000 1800 1600 1400 1200 1000 BOO 600 400 200
FREOUENCY.cn-'
Figure D-32.
IR spectrum of Tenax resin from RAC-4. Major
peaks indicate hydrocarbons, esters, ketones;
possible phenols and alcohols, amines, amides
and ethers.
D-49
-------
8 9 10 12 13 20 3040
4000 3500 3000 2500 2000 I BOO 1600 1400 1200 1000 BOO 600 400 200
FREQUENCY,en-'
Figure D-33. IR spectrum of Tenax resin from RAC-4, LC fraction 1.
Spectrum indicates saturated and aromatic hydrocarbons.
23
100
> ao
t
! 60
40
20
WAVELENGTH, ni
5 6
789 10 12 15 20 3040
4000 3500 3000 2500 2000 1800 1600 1400 1200 1000 800 600 400 200
FREQUENCY, »•-'
Figure D-34.
IR spectrum of Tenax resin from RAC-4, LC fraction 2.
Peaks indicate saturated and unsaturated hydrocarbons.
D-50
-------
2.5
WAVEU*6TH,mie,eM
6 7 8
9 10 12 15 20 10 40
4000 J500 5000
I I I I I i i i I I l I | I l l t l l l |- l i i | i i i i ii i
2500 2000 1800 1600 1400 1200 1000 800 600 400 200
FREQUENCY, CB-I
Figure D-35.
IR spectrum of Tenax resin from RAC-4, LC fraction 3,
Major peaks indicate substituted aromatics, esters;
possible amines, amides, ethers and unsaturated
alcohols.
25
TT
4000
WAVE LENGTH, Mi cr««»
l i i i i I i i i i I i i l i I i i i I '»• I l i i i i i ' I i i ' I ' ' ' I in M i i I
3500 3000 2500 2000 1800 1600 1400 1200 1000 BOO 600 400 200
FREQUENCY, c«H
Figure D-36.
IR spectrum of Tenax resin from RAC-4, LC fraction 4,
Peaks indicate esters, ethers, amines and amides;
possible unsaturated alcohols and nitrosubstituted
compounds.
D-51
-------
2.5
WAVELENGTH, mJt,OM
5 6 7 8 9 10 12 15 30 10 40
4000 3500 3000 2500 2000 1800 1600 1400 1200 1000 600 600 400 200
FREQUENCY, «-l
Figure D-37. IR spectrum of Tenax resin from RAC-4, LC fraction 5.
Spectrum indicates esters, ketones; possible amides,
amines, ethers, alcohols and phenols.
WAVELENGTH ,«lcroi»
5 6 7 6 9 10 12 IS 20 3040
4000 3900 3000 2500 2000 1800 1600 1400 1200 1000 800 600 400 200
FREQUENCY, (•-I
Figure D-38.
IR spectrum of Tenax resin from RAC-4, LC fraction 6.
Peaks indicate esters and ketones; possible amides,
amines, ethers, alcohols and phenols.
D-52
-------
WAVE LENGTH. micIOM
5 6 7
9 10 12 IS 20 30 40
i' iii1111 11 i f i ir 11 111 i 1111 11 i r111 i i i M
4000 J500 3000 2500 2000 1800 1600 1400 1200 1000 800 600 400 ZOO
FREQUENCY. e»-«
Figure D-39. IR spectrum of Tenax resin from RAC-4, LC fraction 7,
Spectrum indicates ketones and esters; possible
ethers, phenols, amines and amides.
WAVELENGTH. Mi
7 8 9 10 12 15 20 50 40
IT i l i I l l I rI i i i I ' ' ' I
4000 3500 3000 2500 2000 1800 1600 1400 1200 1000 800 600 400 200
FREQUENCY ,c»-'
Figure D-40.
IR spectrum of RAC 1-5 particulate sample. Major
peaks indicate esters, ketones, saturated hydro-
carbons; possible ethers, substituted aromatics
and organosilicon compounds.
D-53
-------
WAVELENGTH, micron
2.5
100
M 60
»-
I *°
« 20
6 7 8 9 10 12 15 20 3040
i I | | ti I I j |
4000 J500 3000 ZSOO 2000 (800 1(00 1400 1200 1000 800 600 400 200
FREQUENCY,e»-<
Figure D-41. IR spectrum of regenerator bed sample. Spectrum
indicates aryl and unsaturated esters and ethers.
VAVELENtTH, Micron
4 5
6 7 • 9 10 12 IS 20 3040
4000 3500 3000 2900 2000 1800 MOO 1400 1200 1000 BOO 600 400 200
FREQUENCY, (•-'
Figure D-42.
IR spectrum of limestone, total methylene chloride
extract. Functional groups present include methyl
and methylene, carbonyl, and aromatic esters.
D-54
-------
2.5
100
*AVELENCTHtlljcr.M
6 7
9 10 12 13 20 3040
I"
i 40
20
0
LIO.
4000 3500 3000 2500" 2000' •.tOo'Voo' MM' '.200 ' I'oOO ' 800 ' 600 ' 400 ' 200
FREQUENCY, »-t
Figure D-43.
IR spectrum of lignite, total methylene chloride
extract. Spectrum indicates presence of alcohols
and/or amines, methyl and methylene groups, car-
bonyls and aromatics.
2.5
•AVELEN6TH,
3 6
7 8 9 10 12 13 20 3040
i i i i i i i i i
100
I 80
I 40
I
« 20
FRACTION I
LIGNITE
11 l I l i l I i l i | i i l I
4000 3500 3000 2500 2000 1800 1600 1400 1200 1000 800 600 400 200
FREQUENCY, «• "I
Figure D-44.
IR spectrum of lignite, LC fraction 1. Groups
found are aliphatics and possibly phenols.
D-55
-------
VAVELENCTH.Mcron
4 9
8 9 10 12 15 20 3040
100
1 80
g 60
t 40
§20
FRACTION 2
LIGNITE
4000 3900 3000 2900 2000 1800 1600 1400 1200 1000 800 600 400 200
FREQUENCY, ca-<
Figure D-45. IR spectrum of lignite, LC fraction 2. Presence
of polycyclic organic hydrocarbon is indicated.
2.9
100
! 80
uT
I"
i 40
WAVELEN6TH,«ici«M
9 6 7 8 9 10 12 IS 20 3040
FRACTION 3
LIGNITE
4000 3900 3000 2900 2000 1800 1600 1400 1200 1000 800 600 400 200
FREQUENCY, M-l
Figure D-46.
IR spectrum of lignite, LC fraction 3. Spectrum
indicates that halo substituted aromatics,
amines and carbonyl functional groups are
present.
D-56
-------
•AVEUN6TH, •icr«it
8 9 K) 12 15 20 30 40
0 i
FRACTION 4
LIGNITE
4000 3500 3000 2500 ZOOO 1800 1600 1400 1200 1000 100 600 400 200
FREQUENCY, c*-'
Figure D-47. IR spectrum of lignite, LC fraction 4. Presence
of carbonyls detected.
WAVELENGTH, micron
71? 10 12 15 20 3040
,io",6bo ,4'00 •,206-,000 ,00 600 400 200
FREQUENCY, C*'1
Figure D-48.
IR spectrum of lignite, LC fraction 5,
of carbonyls detected.
Presence
D-57
-------
WAVElENCTH.fttcrMi
2-5
_L
? t 9 10 IZ 15 20 3040
' l_l 1 1 1 1—L_
100
I 00
360
20
4000 3500 3000 2900 2000 1800 1600 1400 1200 1000 100 600 400 200
FREQUENCY, c*-'
Figure D-49. IR spectrum of lignite, LC fraction 6. Aliphatic
amines and possibly phenols present.
2.5
9 10 12 15 20 50 40
I I I I I I I 1 I I I I I | I I I | II I | I I I | I I I | i M | I I I I . . -
4000 3900 3000 2900 2000 1800 1600 1400 1200 1000 100 600 400 200
FREQUENCY,ۥ-!
Figure D-50.
IR spectrum of lignite, LC fraction 7.
Carbonyls are indicated.
D-58
-------
TECHNICAL REPORT DATA
(Pleate reed liutnictiotu on she revene before completing)
iREPORT NO,
EPA-600/7-79-048
2.
3. RECIPIENT'S ACCESSION-NO.
TLE AND SUBTITLE
Preliminary Environmental Assessment of the
Lignite-Fired CAFB
6. REPORT DATE
February 1979
6. PERFORMING ORGANIZATION CODE
fTAUTHOH(S)
A.S.Werner, C.W.Young, William Piispanen, and
B. M. Mvatt
8. PERFORMING ORGANIZATION REPORT NO.
GCA-TR-78-34-G
i. PERFORMING ORGANIZATION NAME AND ADDRESS
GCA Corporation
GCA/Technology Division
Bedford, Massachusetts 01730
10. PROGRAM ELEMENT NO.
EHE623
11. CONTRACT/GRANT NO.
68-02-2632
2. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
Final; 1/77 - 10/78
14. SPONSORING AGENCY CODE
EPA/600/13
B. SUPPLEMENTARY NOTES IERL-RTP project officer is Samuel L. Rakes, MD-61, 919/541-
2825.
6 ABS n The report gives results of a preliminary environmental assessment (EA)
of the lignite-fired Chemically Active Fluid-Bed (CAFB) process. It follows an ear-
lier EA of the oil-fired CAFB. Waste streams contributing air and solid waste pol-
lutants were evaluated in terms of emission rates and potential environmental
effects. Emphasis is placed on flue gas emissions. As part of the investigation, a
field sampling and laboratory analysis program was carried out to compile an emis-
sions inventory of the CAFB pilot plant at the Esso Research Centre in Abingdon,
England. In addition to the EA, an economic evaluation of the oil-fired CAFB is
presented relative to alternative residual oil utilization techniques. Finally, recom-
mendations are made for further control needs and emissions testing to be carried
out in conjunction with the CAFB demonstration plant in San Benito, Texas. Particu-
late emissions were less than those from direct combustion of lignite using multi-
clones as a control. NOx emissions were quite low: 0.09 Ib/million Btu was the
highest measured. Light organics were equal to those from conventional units;
heavy O C6) emissions were lower. SOx emissions were half the New Source Per-
formance Standard for coal-fired boilers.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
Pollution Fuel Oil
Assessments Residual Oils
Lignite Coal
Combustion Sulfur Oxides
Fluidized Bed Processing
Flue Gases Organic Compounds
Pollution Control
Stationary Sources
Environmental Assess-
ment
CAFB Process
Fluidized-Bed Combus-
tion
13B
14B
21D,08G
21B
13H,07A
11H
07B
07C
18. DISTRIBUTION STATEMENT
Unlimited
19. SECURITY CLASS (Thit Report/
Unclassified
21. NO. OF PAGES
257
20. SECURITY CLASS (Thispage)
Unclassified
22. PRICE
Form 2220.1 <»-73)
D-59
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