Jrtice of Research and Development Laboratory
Research Triangle Park, North Carolina 27711
EPA-600/7-77-139
_ u n Q7T
DeCemDef 1977
ENVIRONMENTAL ASSESSMENT
OF SOLID RESIDUES FROM
FLUIDIZED-BED FUEL PROCESSING
Interagency
Energy-Environment
Research and Development
Program Report
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S.
Environmental Protection Agency, have been grouped into seven series.
These seven broad categories were established to facilitate further
development and application of environmental technology. Elimination
of traditional grouping was consciously planned to foster technology
transfer and a maximum interface in related fields. The seven series
are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7. Interagency Energy-Environment Research and Development
This report has been assigned to the INTERAGENCY ENERGY-ENVIRONMENT
RESEARCH AND DEVELOPMENT series. Reports in this series result from
the effort funded under the 17-agehcy Federal Energy/Environment
Research and Development Program. These studies relate to EPA's
mission to protect the public health and welfare from adverse effects
of pollutants associated with energy systems. The goal of the Program
is to assure the rapid development of domestic energy supplies in an
environmentally—compatible manner by providing the necessary
environmental data and control technology. Investigations include
analyses of the transport of energy-related pollutants and their health
and ecological effects; assessments of, and development of, control
technologies for energy systems; and integrated assessments of a wide
range of energy-related environmental issues.
REVIEW NOTICE
This report has been reviewed by the participating Federal
Agencies, and approved for publication. Approval does not
signify that the contents necessarily reflect the views and
policies of the Government, nor does mention of trade names
or commercial products constitute endorsement or recommen-
dation for use.
This document is available to the public through the National Technical
Information Service, Springfield, Virginia 22161.
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EPA-600/7-77-139
December 1977
ENVIRONMENTAL ASSESSMENT OF SOLID
RESIDUES FROM FLUIDIZED-BED
FUEL PROCESSING
by
Ralph Stone and Richard Kahle
Ralph Stone and Co., Inc.
10954 Santa Monica Boulevard
Los Angeles, California 90025
Contract No. 68-03-2347
Program Element No. EHB536
EPA Project Officer: Waiter B. Steen
Industrial Environmental Research Laboratory
Office of Energy, Minerals, and Industry
Research Triangle Park, N.C. 27711
Prepared for
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, D.C. 20460
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ABSTRACT
This report presents results for the first 15 months of an environmental assessment of
the solid residues generated by flufdized-bed coal combustion and oil gasification. Tasks
included a literature search, chemical and physical residue characterization, laboratory
leaching studies, and testing of residues in various materials and agricultural applications.
The literature search reviewed current fluidized-bed combustion technology, identi-
fied products in which residues might be used, and provided data on typical soil and
geologic conditions at the disposal sites being evaluated. Laboratory tests included total
chemical characterization, composition of acid-, base-, and water-soluble fractions,
cation exchanged capacity, BOD, temperature change from water addition, particle size
distribution, dry density, specific gravity, permeability, water-holding capacity, moisture
content, and small-scale column leaching studies.
Pilot-scale columns simulated abandoned coal mines, dolomite and limestone quarries,
sanitary landfills, soils ,and the ocean. Water was added to columns on a prescribed
schedule and the resulting leachate was collected and analyzed for chemical constituents.
The data were used to assess the potential for impact on water quality, and the capacity
of the disposal environment to attenuate degradation.
Product tests and preliminary market analyses were conducted for residue use in
concrete, asphalt, soil cement> and lime/fly ash aggregate. Uses as acid mine drainage
neutralizer and agricultural soil conditioner/ fertilizer were also evaluated.
This annual report was submitted in partial fulfillment of Contract No. 68-03-2347
by Ralph Stone and Company, Inc., under the sponsorship of the U.S. Environmental
Protection Agency. This report covers the period from November 5, 1975 to December
31, 1976. Further work continues to be performed and will be summarized in future
reports.
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CONTENTS
Page
Abstract
Figures
Tables
Acknowl edgments
1. Introduction 1
Background 1
Objectives 5
Scope of Work 5
2. Summary 8
Introduction 8
Discussion 8
Continuing Investigations 9
3. Preliminary Results 10
4. Fluidized-Bed Coal Combustion 14
Introduction 14
Process Descriptions 14
Once Through Operation 16
5. Residue Characterization 20
Purpose 20
Residue Characteristics 20
Chemical Composition 24
Chemical Properties Tests 27
Physical Properties 27
Results 37
6. Pilot Column Studies of Residue Disposal 55
Purpose 55
Simulated Sedimentary Environment Columns 55
Column Test Procedures 69
ill
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CONTENTS (Cont.)
Page
7. Reuse Potential for Fluidized-Bed Residues 149
Introduction 149
Overall Reuse Prospects 149
Types of Coal Ash 153
Coal Ash Utilization 153
Specific Applications for Coal Ash 159
Specific Applications of Lime/Limestone Wet Scrubber Residues 182
Potential Structural Materials Applications: Test Results 186
Potential Agricultural Application of FBC Residues 201
Marketing Analysis Methodology 226
Economic Analysis of Specific Applications 229
References 235
Appendices 252
A. Laboratory Analytical Methods 252
B. Sample Data Sheet 256
C. Column Leachate Concentrations 259
D. Characterization of Similar Residues 297
E. Description of FBC Units - Providing Residues 307
F. Fluidized-Bed Oil Gasification 320
IV
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FIGURES
Number Page
1 Direct contact fluidized-bed stream generator 15
2 Once through pressurized fluidized-bed boiler power plant 17
3 Laboratory-scale column leaching 25
4 Temperature change from water addition to dry. residues 29
5 Temperature change from water addition to dry residues 30
6 Particle size analyses: coal combustion residues 32
7 Particle size analyses: oil gasification residues 33
8 Particle size analysis: pea gravel, granite bedrock, and large gravel 34
9 Particle size analysis: silica sand and decomposed granite 35
10 Particle size analysis: coal,dolomite,and limestone 36
11 BOD from residue water extracts 44
12 Leaching characteristics of VFA and VSBM 52
13 Leaching characteristics of NJFA and NJSBM 53
14 Leaching characteristics of EFA and ESBM 54
15 Simulated sedimentary environment: sea water 56
16 Legend for test column disposal environments 57
17 Sanitary landfill test column 58
18 Abandoned limestone quarry test columns 62
19 Simulated sedimentary environment: dolomite quarry 63
20 Stratigraphic section of a typical coal mine 65
21 Abandoned coal mine test column 66
22 Lysimeter construction and test column placement 72
23 Original location of representative soil samples 77
24 Typical test column leachate collection system schematic 82
25 Outdoor columns leachate sampling apparatus 84
26 Drainage through limestone quarry columns 85
27 Drainage through dolomite quarry columns 86
28 Drainage through sanitary landfill columns 87
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FIGURES (Cont.)
Number
29 Drainage through coal mine columns 8°
30 Drainage through ocean disposal columns 89
31 Legend of typical columns for Figures 32 through 176 103
32-47 Test column leachate cumulative balances: chloride 104
48 - 63 Test column leachate cumulative balances: iron 108
64-83 Test column leachate cumulative balances: lead 112
84-103 Test column leachate cumulative balances: nickel 117
104-123 Test column leachate cumulative balances: sulfate 122
124 - 143 Test column leachate cumulative balances: zinc 127
144 - 159 Specific conductivity and total dissolved solid of leachate from
columns 2 through 17 132
160-176 pH of leachate from columns 1-17 140
177 Effect of freeze-thaw cycles on LCFA compressive strength 164
178 Change of length with temperature for cured LFA specimen 165
179 Effect of curing time and temperature on LFA compressive strength 167
180 Effect of curing time and temperature on LCFA compressive strength 168
181 Effect of lime content and curing conditions on LFA strength 170
182 Effect of fly ash on LFA density 171
183 LFA moisture correlation chart 174
184 pH leachate for acid mine drainage 176
185 Aerated or foamed cellular concrete production flow diagram 184
186 Formed concrete production flow sheet 185
187 CS brick production flow diagram 187
188 Concrete compressive strength tests: NJFA/VFA/ SBM after seven
day cure 195
189 Concrete compressive strength tests: NJFA, VFA, VSBM after
28-day cure 196
190 Concrete compressive strength tests: NJSBM,ESBM,EFA after
7-day cure 197
191 Concrete compressive strength tests: NJSBM,EFA,ESBM after
28-day cure 198
vi
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FIGURES (Cont.)
Number Page
192 Result of reaction between residues and emulsified asphalt 200
193 Asphalt compressive strength tests: VSBM,NJSBM,ESBM after
29-hour cure 202
194 Asphalt campressive strength tests: VSBM,NJSBM,ESBM after
7-day cure 203
195 Asphalt comressive strength tests: NJFA, EFA after 29-hour cure 204
196 Asphalt compressive strength tests: NJFA7EFA after seven day cure 205
197 Experiment 1 tomato plant growth: Exxon, New Jersey 208
198 Experiment 1 tomato plant growth: PER,Virginia 209
199 Experiment 2-A tomato plant growth 211
200 Mean tomato plant height, experiment 2: VFA,FSFA,CFA 214
201 Mean tomato plant height, experiment 2: NJSBM,VSBM,NJFA 215
202 Tomato plant growth vs. soil pH,experiment 2 218
203 Calcium content in digested tomato plant tissue: experiment 2 220
204 Magnesium content in digested tomato plant tissue: experiment 2 221
205 Iron content in digested tomato plant tissue: experiment 2 222
206 Manganese content in digested tomato plant tissue: experiment 2 223
207 Sulfate content in digested tomato plant tissue: experiment 2 224
208 Zinc content in digested tomato plant tissue: experiment 2 225
209 Distance to U.S. coal-fired power plants 227
C-l-C-16 Chloride leached from Columns 2 through 17 260
C-17-C-32 Iron leached from Columns 1 through 20 264
C-33-C-£2 Lead leached from Columns 1 through 20 268
C-53-C-72 Nickel leached from Columns 1 through 20 273
C-73-C-92 Sulfate leached from Columns 1 through 20 278
C-93-C-112 Zinc leached from Column 1 through 20 283
C-113-C-130 pH of leachate from Column 1 through 20 288
D-l
Concentration range and average of U.S. fly ash constituents
vii
301
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FIGURES (Cont.)
Number Pqae
E-l FBC construction detail (side view) 309
E-2 FBC construction detail (front view) 310
E-3 Fluidized bed module: internal construction 311
E-4 FBM and regenerator flow diagram 312
E-5 Section view of the integrated BVM/CBC unit 314
E-6 Bed material flow paths FBM,CBC regenerator 315
E-7 Pressurized FBC pilot plant, Linden,New Jersey 316
E-8 Exxon FBC unit 319
F-l Low pressure fluidized bed oil gasification for power generation 321
F-2 High pressure fluidized bed oil gasification for power generation 322
F-3 Modes of operation,fluidized bed oil gasification plant 323
F-4 Energy balances flow diagram 327
F-5 Regenerative high-pressure oil gasification process 328
F-6 Esso,England oil gasification system 335
F-7 Batch reactor 336
viii
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TABLES
Number Page
1 U.S. Electric Generating Capacity 2
2 U.S. Electricity Generation by Type of Fuel: 1970-1990 2
3 Projected Annual Fuel Requirements: Steam Electric Power Plants 3
4 Potential U.S. Sulfur Dioxide Pollution with No Abatement 3
5 Sulfur Dioxide Abatement Processes 4
6 Identification of Residues 6
7 Environmental Impact Comparison of FBC Processes 18
8 Pilot Plant Operation for Characterized Residues 21
9 Characterization of Pope,Evans,and Robbins Bituminous Coal Samples 22
10 Characterization of Pope,Evans, and Robbins Calcined Limestone
Samples 23
11 Characterization of Exxon Miniplant Coal Samples 23
12 Stratigraphic Materials Simulated in Leaching Tests 26
13 Residue Cation Exchange Capacity 28
14 Residue Acid Neutralization Capacity 28
15 Residue Physical Properties 38
16 Permeability of Residues and Column Materials 39
17 Laboratory Characterization of Residues 1. Exxon Miniplant,
Linden,New Jersey 40
18 Laboratory Characterization of Residues II. Pope,Evans, and Robbins,
Alexandria,Virginia 41
19 Laboratory Characterization of Residues III. Esso,England 42
20 Laboratory Characterization of Residues IV. Esso,England 43
21 Laboratory Leaching Tests: Granite Bedrock 45
22 Laboratory Leaching Tests: Bituminous Coal 46
23 Laboratory Leaching Tests: Dolomite 47
24 Laboratory Leaching Tests: Limestone 48
25 Laboratory Leaching Tests: "oO Silica Sand 49
26 Laboratory Leaching Tests: *16 Silica Sand 50
ix
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TABLES (Cont.)
Number
27 Laboratory Leaching Tests: Claystone 51
28 Representative Thickness Sanitary Landfill Simulated in Test Columns 59
29 Representative Thickness of Limestone and Dolomite Simulation
Test Columns 61
30 Representative Thickness of Coal Mine Simulation Test Column 64
31 Material Densities of Field Strata and Test Columns 67
32 Material Densities of Natural Strata and Test Columns 68
33 Average Field Densities of Materials 68
34 Column and Residue Identification 70
35 Criteria Definition for Grading Analysis 73
36 Column Materials Grading Analysis 74
37 Test Column Soils Characteristics 76
38 Estimated Residential and Commercial Solid Waste Generation
by Kind of Material and Product Source Category, 1971 78
39 Sanitary Landfill - As Mixed Test Column 80
40 Materials in Test Column Layers by Weight 81
41 Complete Analysis of Los Angeles Owens River Aqueduct (Fresh Water)
Columns Test 90
42 Sea Water Analysis 91
43 Residues Added to Columns 92
44 Procedures for Sampling and Filling the Flooded Ocean Water Test
Columns 94
45 Constituent Removal by Ocean Disposal Column Strata 95
46 Constituent Removal by Limestone Quarry Column Strata 96
47 Constituent Removal by Dolomite Quarry Column Strata 97
48 Constituent Removal by Sanitary Landfill Column Strata 98
49 Constituent Removal by Coal Mine Column Strata 99
50 EPA Proposed Regulations on Interim Primary Drinking Water
Standards, 1975 10Q
51 Surface Water Criteria for Public Water Supplies 101
52 Estimated Ash Utilization Potential
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TABLES (Cont.)
Number Page
53 Comparison of Ash Compositions 152
54 Comparison of FBC Residue Compositions 152
55 Comparative Ash Production and Utilization, 1966 through 1972 154
56 Ash Collection and Utilization, 1971 156
57 Known Miscellaneous Uses for Ash and Slag 157
58 Known Uses for Ash Removed from Plant at No Cost to Utility, 1971 158
59 Development of Ash Production and Use in the Economic Commission
for Europe Region 160
60 Density of Fly Ash Compared with Traditional Fills 161
61 Effect of Fly Ash Content on LFA Strength and Durability 169
62 Average Cement Requirements of Miscellaneous Materials 179
63 Normal Range of Cement Requirements for B and C Horizon Soil 179
64 Effect of Adding Zn and Varying the pH in the Soil on Zn Content
and Yield Reduction of Chard Leaves 181
65 Effects of Soil pH on Soybean Plants' Mineral Uptake 181
66 Potential Structural Materials Applications: Tests Performed 188
67 Composition of Concrete Test Cylinders 189
68 Diameter and Area of Concrete Test Cylinders: Seven-Day Cure 190
69 Diameter and Area of Concrete Test Cylinders: Twenty-eight
Day Cure . 192
70 Results of Compressive Concrete Strength Test After Seven Days 193
71 Results of Compressive Concrete Strength Test After Twenty-Eight
Days 194
72 Asphalt Sample Compositions 199
73 Planting Schedule for Agricultural Tests 206
74 Experiment 2-A: Tomato Plant Growth Results 212
75 pH of Soil Residue Mixture 216
76 pH of Soil Residue Mixture After Crop 2 Harvest 217
77 Tomato Plant Digestion Analytical Results 219
78 Sludge Fixation Costing Estimates 230
XI
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TABLES (Cont.)
Number
79 Residue Value for Use in Concrete 23°
80 Imputed Value of Residues in Asphalt Applications 231
81 Fluidized-Bed Residues as a Substitute for Calcium Carbonate in
Peanut Growing 233
A*-l Soil Preparatory Methods 253
A-2 Analytical Methods 254
C-l Variation in Coal Mine Column Leachate Constituents 292
C-2 Variation in Sanitary Landfill Column Leachate Constituents 293
C-3 Variation in Dolomite Quarry Column Leachate Constituents 294
C-4 Variation in Limestone Quarry Column Leachate Constituents 295
C-5 Variation in Sea Water Column Leachate Constituents 296
D-l Common Minerals in U.S. Coals 298
D-2 Chemical Constituents of Coal Ash 298
D-3 Coal Ash Solubility in Distilled Water 299
D-4 Mineral Phases Found in Coal Ash 299
D-5 Physical Properties of Fly Ash from Pulverized Coal Fired Plants 300
D-6 Oxide Analyses of Incinerator Fly Ash from Typical Refuse 302
D-7 Elemental Head Sample Analyses of Municipal Incinerator Fly Ashes 303
D-8 Wet Chemical Analysis of Sludge Standards 304
D-9 Identification of APCS Sludge Standards 305
D-10 X-ray Analysis of APCS Sludges 306
E-l Design Parameters: Exxon Miniplant 319
F-l Atmospheric Pressure Oil Gasification Specifications 324
F-2 Specifications for Fluidized Bed Operation 326-
F-3 Gasification Product Compositions 329
F-4 Environmental Impact Comparison 33T
F-5 Advantages of Atmospheric Pressure Oil Gasification Over Stack
Gas Wet Scrubbers 332
F-6 Summary of Experimental Results 334
xii
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ACKNOWLEDGMENTS
The excellent support and direction provided by Mr. D. Bruce Henschel, Program
Manager, representing the U.S. EPA Industrial Environmental Research Laboratory,
Research Triangle Park, North Carolina, is gratefully acknowledged. We are equally
grateful to Mr. Richard A. Chapman under whose direction the work was performed.
Because Mr. Chapman is no longer with the program, the work is continuing under the
direction of IERL/RTP.
We also acknowledge the information and close cooperation provided by Mr. William
T. Harvey and other Office of Fossil Energy officials of ERDA, Washington,D.C.; Mr.
Orus L. Bennett of the U.S. Department of Agriculture, Agricultural Research Service,
Morgantown, West Virginia; Dr. Stephen K. Seale of the Division of Chemical Products,
Tennessee Valley Authority, Muscle Shoals, Alabamapand Mr. Jerome Mahoch of the
U.S. Army Waterways Experiment Station, Vicksburg, Mississippi.
We appreciate the excellent cooperation, information and residue samples provided
by the following fluidized-bed pilot plant and Rivesville facility contractors; Messrs.
Robert Reid, Manager, Pope, Evans, and Robbins,lnc., Alexandria, Va.;Dr. Ronald C.
Hoke, Exxon Research and Engineering Co., Linden,New Jersey; Dr. G.L. Johnes, Esso
Research Centre, Abingdon, England; and Mr. H.f. McCarthy, Allegheny Power Services
Corp., Greensburg, Pa.
Technical review coordination for the contracted U.S. EPA fluidized-bed program
was provided by Mr. Karl Landstrom with assistance from Messrs. David Sharp and K. T. Liu
of Battelle, Columbus, Ohio. Program review and data was provided by Dr. Harvey Abelson
of the Mitre Corp.
xili
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CHAPTER 1
INTRODUCTION
Background
Total electricity consumption in the United States is projected to increase at an
annual rate of 7 to 8 percent over 1970-1990. The relative shares of coal, oil, gas,
and hydroelectric generation are expected to decrease as nuclear sources come to
predominate. These trends are shown in Tables 1 and 2. However, the absolute
quantities of coal and oil used should increase along with total consumption. Projected
fuel usage requirements are shown in Table 3.
Combustion of more coal and oil implies increased sulfur oxides generation, as
shown in Table 4. This may be aggravated by a projected increase in the average
sulfur content of coal burned, from the current 2.7 percent to 3.5 percent by the
year 2000. Airborne sulfur compounds are associated with damage to human health,
vegetation, and materials. There are many ways being researched to reduce sulfur
oxide emissions, as shown in Table 5.
One approach to alleviating the problem is to develop ways of burning high sulfur
fuels without high-sulfur oxide emissions. Among the options being researched are
fluidized-bed combustion of high sulfur coal and fluidized-bed gasification of high
sulfur residual oils. The EPA is evaluating two high sulfur coal fluidized-bed combustion
pilot plants. The U.S. Energy Research and Development Administration (ERDA) is
supporting one small scale and one large scale pilot plant. One high sulfur residual oil
fluidized-bed reactor pilot plant is being operated in England under an EPA international
agreement. In these plants, either pulverized limestone or dolomite bed material is
admixed to the coal or oil being burned. The sulfur in the fuels reacts with the bed
material to form calcium and magnesium su I fates and,to some degree, sulfites and sul-
fides. Gaseous sulfur emissions are thus greatly reduced, but solid residues are increased,
These residues consist of calcium and magnesium oxides (from unreacted portions of
dolomite and limestone), calcium and magnesium sulfur compounds, traces of unburned
coal and oil and their stack and bottom ash, and inert matter originated from natural
dolomite or limestone.
The disposal of these residues is a matter of concern. For example, toxic substances
might be leached from the residues into ground or surface waters. This study was initi-
ated because there had been no extensive research into the environmental impacts of
the disposal of these solid residues or the feasibility of their recovery.
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IMDLC 1 . U . -> . L
Type of Plant
Fossil steam
Nuclear steam
Steam subtotal
Hydroelectric - conventional
Hydroelectric - pumped storage
Gas turbine and diesel
Totals
Source: 159 .
TABLE 2. U.S. ELECTRICITY
Year Coal Oil
1970 46.4 11.8
1980 36.5 12.4
1990 26.7 8.0
1970(Actual)
%of
Capacity 7oj-a[
flO^Mw)
260 76
6 2
266 78
52 15
4 1
19 6
341 1 00
1980 (Projected) 1990 (Projected)
%of %°f
393 59
147 22
540 81
68 10
27 4
31 5
666 100
GENERATION BY TYPE OF FUFJ
Percent of Total
Gas
24.2
12.4
7.2
Generation
Nuclear
1.4
27.6
47.3
557 44
500 40
1 ,057 84
82 6
71 6
51 4
1,261 100
.1970-1990
Hydroejecfric
16.2
11.1
10.8
Source: 159,
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TABLE 3. PROJECTED ANNUAL FUEL REQUIREMENTS:
STEAM ELECTRIC POWER PLANTS
Fuel
Coal
Natural gas
Residual fuel oil
Uranium ore
Unit
106 kkg
9
10 cu m
106 bbl
kkg°
1970
292
185
331
6,800
1980
454
106
640
37,000
1990
635
118
800
115,000
kkg of UgOn required to supply feed for diffusion plants without plutonium recycle.
Source: 158.
TABLE 4. POTENTIAL U. S. SULFUR DIOXIDE POLLUTION
WITH NO ABATEMENT
Source
Annual Emission of SO2
-
Power plant operation (coal and oil)
Other combustion of coal
Combustion of petroleum products
(excluding power plant oil)
Smelting of metallic ores
Petroleum refinery operation
Miscellaneous sources
Total
1967
13.6
4.6
2.5
3.4
1.9
1.8
27.9
1970
18.1
4.4
3.1
3.6
2.2
1.8
22.2
1980
37.3
3.6
3.5
4.8
3.6
2.4
55.2
1990
56.2
2.8
3.9
6.4
5.9
3.1
78.4
2000
85.7
1.5
4.6
8.7
9.5
4.1
114.1
a Includes coke processing, HLSO, plants, coal refuse banks, refuse incineration, and
pulp and paper manufacturing.
Source; 160.
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. TABLE 5, SULFUR DIOXIDE ABATEMENT PROCESSES
1. Precombustion processes
a. Coal and oil cleaning
b. Coal and oil gasification
c. Fluldized bed gasification
2. Combustion processes
a. Fluidized bed combustion
b. Black, Sivalls, and Bryson
3. Limestone processes
a. Wet scrubbing
b. Dry removal
4. Processes for sulfur recovery from stack gases
a. Cat - Ox
b. WeUman-Lord
c. Esso-Babcock & Wilcox adsorbent
d. Formate scrubbing
e. Ammonia scrubbing
f. Westvaco char
g. Molten carbonate
h. Sodium bicarbonate adsorption
i. Modified Claus
k. Catalytic chamber
I. Ionics/Stone & Webster
m. Alkalized alumina
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Objectives
The general objective of this project was to assess the environmental impact of the
disposal or the recovery of the residues which would be generated with widespread commercial
use of the fluidized-bed process for high sulfur coal combustion and gasification of high
sulfur residual oil. Specific objectives were to:
« Determine the chemical and physical characteristics of the residues from the
fluid!zed bed process applied to coal and oil.
• Identify the leachate water pollution constituents and quantities resulting from
land disposal of residues.
• Evaluate the potential effects of disposing the residues into different soi! and
sedimentary environments and into the ocean.
• Investigate the potential for recovery of the solid residues.
• Determine the needs for treating the residues and establishing methods for the
disposal of such wastes.
Scope of Work ^
Literature reviews, laboratory studies, and pilot test columns were used during Year 01
to determine the potential environmental impacts from disposal of solid residues from
fluidized-bed operations. Residues from both the fluidized-bed combustion of high sulfur
coaiand fiuidized bed gasification of high sulfur residual oils were tested. Residues
are being obtained from three pilot plants. The residues received are identified in Table
6; the symbol abbreviations shown will be used throughout the report in reference to the
three pilot plants.
In general, the literature search provided information on the disposal and environ-
mental impacts of similar residues such as coal ash or limestone SOX scrubber wastes.
Information on similar types of waste residues were obtained in laboratory and pilot test
reports. From available sources, estimates were made of the conditions for and the levels
of pollutants anticipated from the residue wastes in various environments. Process descrip-
tions of material flows for plants generating residues were obtained. Typical natural
conditions were selected for our study work. The results of the literature search were of
value in designing the specific limits and goals on the laboratory and column tests.
The laboratory studies were used to duplicate a range of theoretical disposal environ-
ments on a small scale. Residues were tested under controlled conditions; environmental
variables were controlled to duplicate many real conditions that could affect the behavior
of the residues in natural environments. All leachate was collected and analyzed.
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TABIF6. lOFNTlFirATIONJ OFRFSIDL1ES.
Symbol
Residue
Source
Nome of Residue
Riot Plant
location
CFA
FSFA
VFA
VSBM
NJFA
NJSBM
EFA
ESBM
Oil
Oil
Coal
Coal
Coal
Coal
Oil
Oil
Cyclone fly ash Esso; Abingdon, England
Fines,stack,regenerator, Esso; Abingdon, England
gasifier, fly ash
Virginia fly ash
Virginia spent bed
material
New Jersey fly ash
New Jersey spent bed
material
English fly ash
English spent bed
material
Pope, Evans,and Robbins;
Alexandria, Virginia
Pope, Evans,and Robbins;
Alexandria, Virginia
Exxon; Linden, New Jersey
Exxon; Linden, New Jersey
Esso; Abingdon, England
Esso; Abingdon, England
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Profiles of the residues for different disposal methods have been determined. The results
of the laboratory studies were used to design the test columns. Table 44 presents infor-
mation on the residues used in the laboratory and test column studies.
The field work will attempt to verify the results of the laboratory and column studies
in natural environments. To do so, test plots will be constructed in the natural environ-
ments, and leachate monitoring probes and wells will be installed. Records will be kept
of environmental conditions, and leachate and groundwater quality will be monitored.
Analyses will be conducted to determine those disposal site factors which can minimize
adverse environmental impacts.
Studies were also undertaken to determine the possibility of recovering and market-
ing the residues instead of disposing of them. Laboratory tests are being conducted to
determine the feasibility of using these residues for commercial products. These tests
compare the properties of materials produced using residues with those made with conven-
tional raw materials. A preliminary market study was initiated to determine the market
potentials for the residues and their finished products.
Concurrent with the product feasibility task, an evaluation of requirements for treat-
ing residues was initiated to establish whether treatment can enhance product use or is
required for disposal. The disposal needs for liquid wastes was also investigated in terms of
environmental impacts.
The Rivesvilie,West Virginia field test area was selected by first identifying potential
sites from literature, from our company knowledge, and from the EPA. Mail and telephone
contacts were used to help screen candidate sites for local conditions and cooperation. A
preliminary two-day visit was made to the Rivesville area. The preliminary visit reviewed
available facilities and transportation requirements.
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CHAPTER 2
SUMMARY
Introduction
The overall purpose of the proposed work is to determine the environmental impact of
the disposal of residues from the fluidized-bed combustion of high sulfur coal, and fluidized-
bed gasification of high sulfur residual oil. The specific objectives to be achieved are to
determine:
1 . The characteristics of the solid, sludge, and liquid residues from the fluidized-bed
processes applied to coal and oil.
2. The leachate constituents and quantities from land and ocean site disposal of the
residues.
3. Other potential environmental effects from disposing the residues into alternative land
and water sites.
4. The potential for utilizing solid residues for manufacture of commercial products and for
other
5. Pretreatment requirements for the residues, prior to their disposal.
Discussion
Literature reviews, laboratory tests, and field studies are being used to determine the
environmental impacts of disposal of solid and liquid residues from fluidized-bed operations.
Residues from fluidized-bed combustion of high-sulfur coal and fluidized-bed gasification
of high-suffur residual oils are being tested. Residues were obtained from three pilot plants;
two ere supported by the EPA, and one Is supported by ERDA. The three plants
-------
A comprehensive program of residue characterization was initiated to determine the
chemical and physical properties of the six residues. The resultant physical property data
was used to hydraulically design 36-plus pilot test columns.for leachate studies. The resul-
tant chemical property data was used as a baseline for the leachate tests and also to identify
constituents for which the test column leachate would be analyzed.
The laboratory studies were used to duplicate, on a small scale, eight disposal environ-
menlv toal mine, dolomite and limestone quarries, ocean, sanitary landfill, and sand,clay
and sHt soils. Environmental variables were controlled to duplicate as many
real world conditions as possible that would affect the behavior of the residues in natural
environtnentE. All leachate was collected, and analyzed. rVecise analytical profiles of
the residues and their disposal conditions were established.
Large scale field test programs were postponed when it proved impossible to obtain
sufficient quantities of residues. To compensate, an expanded program of pilot scale test
columns, laboratory columns, and product testing was initiated. When additional residues
became available, the data obtained from the aforementioned studies will be used to design
and monitor the large scale field leachate tests.
Studies were undertaken to determine the possibility of recovering and marketing the
residues instead of disposing of them. Bench tests investigated using residues in the manufac-
ture of certain commercial products. Work is in progress using residues in soil cement, lime-
fly ash-aggregate and Iime--fly ash-cement-aggregate mixtures, and as load bearing fill.
Tests were completed using residues in concrete and asphalt. These tests compared the pro-
perties of the recovered product with that produced using conventional raw materials. A
preliminary market study was performed to establish the market potentials for the residues
and their finished products.
Concurrent with the product feasibility task, an evaluation of requirements for treating
residues was made to see if pretreatment can enhance product use or is required for disposal.
Potential use of the spent residues as soil conditioners for agricultural purposes was
investigated. Mixtures of fly ash and bed material with soil have produced a variety of
crops (tomato, spinach, lettuce, corn, and sorghum). Acidic soils may contain high levels
of aluminum and manganese which are easily soluble and sometimes believed to be toxic
to crops; however, it has been known for a long time that an increase in pH will decrease
the uptake of heavy metals. Lime is presently used to help increase the pH but the residues
would presumably replace the lime.
Continuing Investigations
The work planned for the second and third years includes continuing the following:
long-term leaching in the 36 test columns, and completion of product testing of residue use
as a cement substitute and as a soil conditioner.
-------
CHAPTER 3
PRELIMINARY RESULTS
The fly ash and fluidized-bed residue materials used in the study were from pilot plants
operated by Exxon, Linden, New Jersey; Pope, Evans, and Robbins,Alexandria,Virgin!a;
and Esso, in England. For brevity they are referred to in this chapter as Exxon, PER, and
Esso.
The following results are based on partial information and may change when the work,
which is still in progress, is completed:
. 1. A comprehensive review of literature indicated that no historical environmental
data existed on coal fluidized-bed combustion and oil gasification, other than progress re-
ports on the various pilot plants and technologies currently under development.
2. No full-scale commercial fluidieed-bed power plant is at present operating in the
world.
3. Extensive literature describing oonventioncrl coal and oil combustion residue,
physical and chemical characteristics, their ultimate disposal, and recovery alternatives was
found. Similarly, considerable literature on lime and magnesium sludge residues and
their reuse in various applications was found.
4. The literature review and data developed from over 200 different sources during
the first year for this project report indicated the following differences between fly ash
from fluidized-bed combustion and conventional coal and oil-fired combustion*.
• Residues from fluidized-bed combustion (FBC) are derived from spent stone and
fly ash, and differ from conventional coal combustion dolomite or lime scrubber
sludges and fly/bottom ashes.
• Fluidized-bed combustion normally produces solid residues, whereas conventional
combustion scrubbers produce liquid sludges as well as some bottom ash solids.
• Test fluidized-bed fly and bottom ash samples wece dry, whereas conventional
combustion plant ashes are wetted to quench burning coals and to cool the residues.
• The FBC residue samples had higher specific gravities (weights) than conventional
fly ash, and thus would not be as suitable for use in lightweight concrete and
structural fills.
• The FBC fly/bed test residues had been recirculated and hence contain less organic
material compared to conventional unrecirculated residues.
10
-------
5. Results of laboratory mixing/leaching tests for residue characterization showed water
soluble fractions in Exxon fly ash were higher than acid soluble fractions for boron and mag-
nesium, and higher than base soluble fractions for nitrate. Water soluble fractions in Exxon
spent bed material were higher than acid soluble fractions for sulfate, boron, lead, magnesium,
and sodium, and higher than base soluble fractions for nitrate, aluminum, calcium, copper,
manganese, and molybdenum.
Water soluble fractions in PER fly ash were higher than acid soluble fractions for sulfate,
boron, lead, and sodium, and higher than base soluble fractions for nitrate, calcium, copper,
magnesium, manganese, molybdenum, and nickel. For PER spent bed materials, the water
soluble fractions exceeded acid soluble fractions for sulfate, boron, and sodium, and exceeded
base soluble fractions for nitrate, aluminum, boron, calcium, copper, magnesium, manganese,
and molybdenum.
All the constituents in the Esso fly ash except chloride, nitrate, and phosphate were
less in the water soluble fraction than in the acid soluble fractions. The water soluble
fraction exceeded the base soluble fraction for chloride, nitrate, phosphate, aluminum,
calcium, chromium, iron, lead, manganese, mercury, molybdenum, silver, and zinc Ions.
For the Esso spent bed material, the acid soluble fractions exceeded the water soluble frac-
tions for all the constituents except sulfate, boron, mercury, and molybdenum, and the
water soluble fractions exceeded the base soluble fractions for all the constituents except
sulfate, aluminum, arsenic, beryllium, magnesium, and zinc.
Cyclone fly ash water soluble fractions were less than acid soluble fractions for all
constituents and exceeded base soluble fractions for nitrate, aluminum, calcium, iron,
magnesium, manganese, molybdenum, silver, and zinc. Esso fines, stack fly ash water solu-
ble fractions exceeded acid soluble fractions for chloride,"boron, and molybdenum, and ex-
ceeded base soluble fractions for nitrate, arsenic, boron, cadmium, calcium, kon, lead, mag-
nesium, molybdenum, and silver. Due to a shortage of residues for analysis, some acid and
base soluble fractions were not determined.
6. BOD tests to determine the biochemical rate of decomposition of residue water
soluble extracts in a standard solution of glucose and peptones were compared with a control
standard solution. The solutions with added residues showed a lag time of two days during
which BOD was inhibited, and the BOD increased so that the 5-day oxygen demand samples
were nearly as high as the control sample. The results indicated that the leachates contain
constituents which can act as temporary inhibitors to microorganism growth in the wastewater
containing biodegradable organic compounds.
7. Laboratory bench-scale leaching tests run in 6 1/2 cm diameter x 21 cm length
vessels to evaluate column strata granular materials indicated the following principle
dissolved constituents:
• Granite bedrock: sulfate, sodium, and traces of arsenic.
• Bituminous coal: sulfate, arsenic, calcium, and sodium.
11
-------
• Dolomite: sulfate, arsenic, sodium, and traces of boron and potassium.
• Limestone: sulfate, sodium and traces of arsenic, cadmium, potassium and lead.
• Silica sand (number 60): sulfate, sodium, chloride, and traces of potassium.
• Silica sand (number 16): sulfate, sodium, chloride, potassium, and traces of
magnesium, lead and calcium.
• Claystone: sulfate, sodium, arsenic, chloride, and traces of calcium, lead, and
magnesium.
8. High rate leaching tests were developed for the laboratory bench-scale residue vessels
and provided the following principle dissolved constituents:
• Fluidized bed sample residues leached sulfate and chloride anlons, and calcium,
magnesium, iron, sodium, and potassium cations in significant concentrations.
Many trace elements were also leached in relatively low concentrations.
• Chloride, sodium, and potassium were nearly completely extracted from the sample
residues after six times the residues' weight in water had leached through the residue.
« Calcium and sulfate were leached at relatively constant high concentrations after
residues had received six times their weight in water.
• Residue feachate contained nickel, lead and iron compounds concentrations ex-
ceeding the U.S. EPA recommended permissable levels for drinking water supplies.
• Sulfate content in the residue leachate exceeded the noted recommended standard.
However, sulfate may combine with calcium to form gypsum, or with lead to form
lead sulfate. Both of these sulfate compounds are relatively insoluble and thus will
reduce the leaching of calcium and lead.
• Acid water increased the leaching of heavy metals.
9. Cation exchange capacities (CEC) of the Esso and Exxon spent bed materials were
equal at 1.9 CEC meq per 100 grams of residue. PER fly ash and spent bed materials were
2.4 CEC meq per 100 grams of residue. Exxon fly ash was 0.5 and Esso fly ash was 13.6
CEC meq per 100 grams of residue.
10. Acid neutralization capacities varied from 2.6 equivalents per kg for PER spent bed
material to 78.1 for Esso fly ash, probably due to different ratios of calcium to sulfur in
these materials, as received.
11. Exothermal reactions occurred after wetting all of the "as received" residues except
Exxon fly ash. The exothermal reactions were attributed largely to lime slaking upon addi-
tion of water. Residue slaking temperatures were measured as high as 240°C(Exxon spent
bed material).
12. The fluidized bed fly ash particle sizes were fine (similar to a type of sandy silt) and
the composition was unchanged by slaking. The spent bed material particle s?zes,as received,
12
-------
were similar to sand and became even finer after slaking. Oil gasification residue particle
analyses.fell within a narrow band corresponding to a typical sand with fines. The exception
was unslaked Esso spent bed materials whose particle size distribution corresponded to a
typical sand.
13. The specific gravity values for Exxon and PER fly ashes (2.6 - 2.8) were in the range
for normal soils. Esso fly ash specific gravity at 2.02 was less than for normal soils. The
spent bed residues partly entered into solution after water was added; thus, their specific
gravity was difficult to determine accurately.
14. The residues "as received" had zero moisture content.
15. Water addition will likely change the dry densities of all the residues tested except
the PER fly ash. Esso residue densities decreased significantly in dry density (by 37 - 49 per-
cent dry weight) and Exxon spent bed material increased significantly (by 48 percent) after
water addition.
16. The ability of dry residues to hold moisture, termed their water holding capacity,
ranges between 0.44 and 0.98 grams of water per gram of dry sample.
17. Pilot test column simulation indicated that the residue leachate had the following
characteristics i
• A highly alkaline leachate resulted from coal mine, dolomite quarry, limestone
quarry,and ocean environments.
• A neutral leachate resulted from the landfill environments due to the neutralization
of alkaline residue leachate by acidic landfill leachate.
• High initial peak concentrations of sulfate occurred in all environments.
• Soluble chlorides in residues were readily leached without attenuation in all of the
column strata materials.
• Concentrations of mercury in sea water leachate may be an order of magnitude
higher than concentrations found in leachate from other land-type conditions.
• Sea water leached iron from the residues more rapidly than fresh water did.
• Slight attenuation of zinc in residue leachate may occur in the column strata.
• Total dissolved solids were leached in decreasing quantities with the increasing
passage of water.
18. Residues can be used as a conditioner for soils that are acidic, high in heavy metals,
or deficient in trace metals. Residues are a marketable source of calcium or magnesium and
are a substitute for lime or gypsum to raise soil pH.
19. Substitution of residues in portland cement concrete mixtures could save about $0.50
per kkg of equivalent strength concrete.
13
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CHAPTER 4
FLUIDIZED-BED COAL COMBUSTION
Introduction
In fluid! zed-bed combustion, a granulated bed material (limestone or dolomite) en-
compasses the pulverized burning coal. The bed and fuel are fluidized by combustion air.
The calcareous bed materials absorb sulfur oxides, reducing their emission into the environ-
ment. The process generates large quantities of dolomite or limestone materials, magnesium
or calcium sulfate, ash and some unburned coal. This sorbent material may be either re-
generated for repeated SO removal, or removed from the plant for disposal.
J{
There have been two approaches to steam generation using fluidized-bed boilers. One
method uses direct contact between the inert fluidized, heated stone particle bed and the
heat transfer surfaces (boiler tubes) to produce steam. An example of a fluidized-bed
steam generator with direct contact heat transfer is shown in Figure 1. The hot flue gas,
after ash removal, can generate additional heat. In boilers without direct fluidized-bed
contact, hot off-gases generate all the steam by conventional fashion.
The start-up of an atmospheric fluidized-bed boiler requires heating a portion of the
bed to 400 C to ignite the injected coal. After ignition, the temperature of the bed rises
unfil the energy released in the bed equals the energy absorbed by the boiler tubes plus
that in the hot gases leaving the bed, and the system achieves thermal equilibrium.
Excellent heat transfer and high heat capacity is maintained in a fluidized-bed boiler at
uniform temperature, typically in the range of 800 to 900 C.
High heat-transfer coefficients between the fluidized-bed and immersed steam genera-
tion surfaces reduce the steam tubing requirements, and also permit operation at tower and
more uniform bed temperatures. The lower temperatures reduce NO emissions and slag,
and decrease equipment corrosion. x
Process Descriptions
There are two fluidized-bed combustion modes, with either complete or partial com-
bustion of the fuel. In the complete combustion mode (also called one-step or excess
oxygen combustion), oxygen in excess of the stoichiometric quantity required to burn the
fuel is fed to the fluidized bed. The oxygen reacts with sulfur, forming sulfur dioxide,
which in turn reacts with the calcium or magnesium in limestone or dolomite (hereafter
simplified to refer only to the calcium):
CaCO3 + S + 3/2 O2 —* CaSO4 + CO2.
In the second mode (called two-step or oxygen deficient combustion), I ess than the
stoichiometric amount of oxygen is added to the fluidized bed. This results in the formation
of calcium sulfide (CaS) which can be converted to SO_ and CaO by roasting it in air or in
14
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Flue
Fuel Injection Pipes
Fluidized Bed
Air Distribution Grid
Boiler Tubes
Figure 1. Direct contact fluidized-bed steam generator.
Source: 104.
-------
oxygervor to CoCCL and H S by reaction with water and CO,. SO2 or HjS can be
converted to sulfur fn a Claus plant) or to r^SO . (in an acidplant).
The three basic types of plant operation tor the fluidized-bed combustion of coal are:
0) once-through (high or low pressure), (2) one-step regeneration (high or low pressure),
and(3) two-step regeneration (high-pressureonly).
Once-Through Operation^
Once-through operation with pressurized fluid-bed combustion (Figure 2) is quite
simple. Calcium sulfate and other compounds are produced in the bed in a stable form
which requires disposal. The cost of the process is minimized by operating with maximum
sorbent utilization.
Table 7 compares possible alternative fluidized bed combustion plant sorbent processes.
The once-through use of limestone or dolomite sorbent results in greater amounts of
waste residues than if these residues were regenerated and recycled; however, with the
present state-of-the-art, residues regeneration appears to be uneconomical. Approximately
7 times, by-weight, of raw crushed dolomite is needed for each unit of coal burned in
a fluidized bed unit. Table 7 indicates that the fluidized bed process generate^ by
weight, about 3 times as much spent bed residue as fly ash, and the total quantity of
fluidized bed residues represents the total of the original dolomite or limestone sorbant
plus the solid ashes from the burned coal and the chemical combination of sulfur and
other reaative materials. The total weight of residues from the fluidized bed combustion
process noted in Table 9 is estimated to be 1,958 kkg/day versus the total input of 195
plus 1,410 kkg/ 1 hour of coal and dolomite respectively.
16
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Source: 104.
Electrical
Generator
Particulate
Removal
Waste
Residue
Steam
Turbine
Fluidized Bed
Boiler
Heat Recovery
(Boiler Feed Water)
Condensor
Stack
Electrical
Generator
11 Boiler Feed
Water
=i Circula-
tion
Water
Heat Recovery
(Flue Gas)
Circulation Water
Discharge
Figure 2. Once-through pressurized fluidized bed boiler power plant.
-------
_IAPLE 7: COMPARISON .OF FBC SORBENT PRQCEilEL
One Step - 10 atm One Step-
!mpact 1% S02 2%S02 10%S02 Tw°Step Once Through
Ab Bb Ab Bb Ab Bb Ab Bb Ac Bd
Energy e
Plant heat rate (kcalAwhr) 2,600 2,700 2,470 2,550 2,360 2,390 2,460 2,520 2,330 2,290
Plant energy cost (milIs/kwhr) 13.88 14.61 13.21 13.67 13.13 13.59 13.94 14.67 13.45 12.30
Raw materials
Total coal input (kkg/nr) 221 229 211 216 202 205 212 218 195 195
Dolomite input (kkgAr) 940 940 940 940 940 940 940 940 2,830 1,410
Methane input (103 cum /day)at STP 790 103 75 97 69 90 0 0 0 0
oo Plant residues
Spent bed material (kkg/day) 807 698 807 698 807 698 980 970 2,450 1,490
Ash output9 531 549 508 518 485 492 510 522 468 468
Sulfur output (kkg/day) 143 149 137 141 124 125 139 141 0 0
Sulfur removal efficiency11 (%) 90 90 90 90 85 85 90 90 94 94
Increase in U.S. coal production relative
to once through operation for total con-
version to regenerative FBC processes (%) 13«3 17.3 8.1 10.5 3.8 4.9 9.0 11.7
U.S. limestone/dolomite production re-
quired for complete conversion to fluid-
ized bed combustion (%of present total) 10 10 10 10 10 10 10 10 30 15
(continued)
-------
TABLE 7
a
Bases For analysis:
195,000 kg/hr coal feed to boilers
4.6% sulfur by weight in coal
boiler sulfur removal efficiency = 95%
dolomite utilization in boiler = 30% (regenerative systems)
dolomite utilization after regeneration = 10%
dolomite make up rate = 1 moleCa/moleS (regenerative systems)
dolomite cost = $ll/kkg
coal at $1.79/106 kcal
methane at $3.17/106 kcal
.sulfur recovery efficiency = 90%
Column A for disposal before regeneration, Column B for disposal after regeneration.
^ At 3.0 moles Ca mole S dolomite make up rate and 31.6% utilization in boiler.
-o At 1,5moles Co/mole S dolomite make up rate and 63.3% utilization in boiler.
- Includes methane input.
Other materials for regeneration processes include process water, chemicals, and/catalysts.
? 1.0% ash in coal.
Sulfur removal efficiency is lower for the one-step process at 1 atmosphere pressure because the process tail gas is
incinerated rather than recycled to the boiler.
-------
CHAPTER 5
RESIDUE CHARACTERIZATION
Purpose
The purpose of this subtask was to determine the chemical and physical properties of
FBC residue samples and the materials used in pilot-scale column studies. This provided a
preliminary screening of potential environmental effects and direction of subsequent efforts.
Results were used in planning and conducting the pilot-scale column studies of residue
disposal, and in testing residue commercial and agricultural applications.
Residue Characteristics
The chemical composition of ash and spent bed material is dictated, to a large
extent, by the composition of the bed material and the fuel. Natural materials are largely
impure, and both coal and oil as well as limestone and dolomite contain traces of most
metals. Concentrations will vary depending on local sources. Combustion and other high
temperature reactions produce ashes and spent bed material containing many of these trace
metals. The specific chemical composition of a given ash or spent bed material is depen-
dent on the combustion parameters, the fuel,and the bed material; and as a result, the
composition of ash and bed material varies widely.
All of the residue samples available to us were from the pilot plant test runs and
may not be representative of future production runs. Where possible, we have attempted
to determine the actual pilot plant test operating conditions and acquired analyses of the
raw fuel and sorbent feeds. Given this latter information, it should be possible to relate
our test results to future production conditions. Table 8 lists the residues analyzed in the
laboratory and their test run conditions.
Tables9through 11 give available analyses of coal and limestone feeds provided
by some of the experimental plants. The composition of fossil fuels used in these experi-
ments varied widely. The percentages of sulfur in the coal ranged from 0.75 to 4.46, and
in the coke about 1.28 (on a dry basis). Venezuelan No. 6 oil was used in the Esso gasi-
fier; and the sulfur content was about 2.5 percent. Unfortunately, not all the experimen-
tal plants providing residues were able to provide complete chemical analysis or other des-
scriptive information about the raw materials that were used.
The composition of the limestone used for the fluid!zed-bed combustion tests varied.
The percentage of calcium in the PER limestone was 36, and 47.5 for Greer and Germany
Valley, respectively. Available data showed that the sulfur content of the limestones was
0.3 percent for Greer and 0.15 percent for the Germany Valley limestones. Magnesium,
iron, aluminum and silicon were other important constituents in the limestones. Probably
both limestone and coal contained several trace metals, but available data showed only
Titanium (0.89 percent in the coal used for the PER plant).
20
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TABLE 8.
PILOT PLANT OPERATION FOR THARACTERI7ED RESIDUES
Residue Source
Pope, Evans &
Robbins
Alexandria, Va.
Fly ash
Spent bed material
Exxon Miniplant
Linden, N. J.
Fly ash
Spent bed material
Esso CAFB
Abingdon, England
Cyclone fly ash
Fines, stack fly ash
Spent bed material
Run Temp.
No. C
N.A* 815 to
870
30.4 835
(avg.)
10 860 to
950
Excess Air _ , T
Vol.% Fu6lType
High sulfur
bituminous
18 coal
Sewickley,
Pa.
16.1 Illinois
N6
No. 2
N.A,a heating oil
Venezuela
Sulfur _ , e , . Ca/S molar Flue SOo
... Bed Sorbent r , .. „__ *•
% feed ratio ppm
Calcined
limestone
4 to 4.5 Germany Valley Variable Variable
& Greer,
W. Va.
42 to 4.8 Grove 3.7 894
limestone
2.5 LimeBCRl359 1 (avg.) 200
U.S.A.
a N, A. = Not Avail able.
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TABLE 9. CHARACTERIZATION OF POPE, EVANS, AND ROBBINS
Constituent
Ash
Volatiles
Fixed carbon
Pyritic sulfur
Sulfate sulfur
Organic sulfur
Total sulfur
Carbon
Hydrogen
Nitrogen
Sulfur
Silicon
Iron
Aluminum
Calcium
Magnesium
Potassium
Sodium
Titanium
Oxygen
Coal
17.44
37.31
45.25
100.00
3.04
0.18
1.24
^736
67.56
4.80
0.93
4.46
4.08
2.48
1,80
0.63
0.10
0.38
0.10
0.09
12.59
100.00
*
Coke
27.82
0.00
72.18
100.00
0.00
0.29
0.99
1.28"
76.18
0.00
0.00
1.28
6.51
3,96
2.87
1.00
0.16
0.61
0.16
0.14
11.3
100.00
Ash
100.0
0.0
0.0
_ , - x
100.0
0.0
1.0
0.0
1.0
0.0
0.0
0.0
1.0
23.4
14.2
10.3
3.6
0.6
2.2
0.6
0.5
43.6
100.0
*
Calculated values.
Source; 186.
22
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TABLE 10. CHARACTERIZATION OF POPE, EVANS, AND ROBBINS
LIMESTONE SAMPLES (percentage bv weiahrt
Constituent Greer Limestone Germany Valley Limestone
Calcium carbonate 75.0 98.3
(CaCO )
o
Magnesium carbonate 4.0 0.5
(MgC03)
Ferric oxide (Fe0O«)
t. O
Alumina (ALO«)
Silica (SiO2)
Sulfur (S)
0.75
3.3
9.5
0.3
0.2
0.5
0.6
0.15
Source: 186.
TABLE 11. CHARACTERIZATION OF EXXON MINIPLANT COAL SAMPLES
Constituent
Moisture
Ash
Volatiles
Carbon
Hydrogen
Nitrogen
Oxygen
Chlorine
Sulfur
xt. — _ — _
As Analyzed
3 3
9.95
10.00
67.71
4.77
1.17
9.19
0.05
4.20
w- —T — -—• v™ r— — —
Dry
„_
10.26
10.31
69.81
4.92
1.21
9.47
0.05
4.33
After ignition
__
__
77.79
5.48
1.34
10.55
0.06
4.83
Source; 187.
23
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Chemical Composition
The preliminary chemical tests of the residue samples consisted of: 1) characteriz-
ation after hydrofluoric acid digestion; 2) determination of their water, basic, and acid
soluble fractions, and 3) determination of their sequential water leaching characteristics.
Total Residue Characterization. The total chemical compositions of the residue
samples were determined after hydrofluoric acid digestion placed appropriate constituents
into solution. One gram residue samples were digested according to the procedure out-
lined in the American Society of Agronomy's Methods of Soil Analysis, 1965, p. 1019.
The only significant departure from this procedure was the use of nickel instead of platin-
um utensils; therefore, total nickel analysis was not performed. The digestate was diluted
to 100 ml. All analyses of the digestate were conducted according to EPA Methods for
Chemical Analysis of Water and Wastes and Standard Methods, (14th ed.). Appendix A
of this report gives methods and references for each analysis. Analytical results are pre-
sentedjJiereiriafter,in the report.
Soluble Fraction Analysis, The solutions to be analyzed were prepared by placing
100 g samples of each type of residue^as received/in a flask and adding either 250 ml of
distilled water, 1.0 N NaOH, or 1.0 N HNOg in accordance with EPA-recommended
procedures as further described in Appendix A. After mixing for twenty-four hours, the
solutions were filtered and the filtrate analyzed to determine the acid, base and water
soluble fractions of the residues, as well as pH, COD, BOD, and TDS0 All analyses were
conducted as for the total characterization procedure, and are cited in Appendix A.
The BOD5 analyses were performed on the water extracts and on distilled water
samples. The extract and distilled water samples contained 6.5 percent of a nutrient
solution of glucose, peptone, calcium chloride, magnesium sulfate, ammonium chloride,
sodium phosphate, potassium phosphate, and ferric chloride.
Bench-Scale Leaching Tests. Preliminary bench-scale leaching tests were conducted
on residue samples prior to the construction of the pilot-scale test columns. The purpose of
these tests was to estimate the long-term leaching characteristics of the residues. Two
hundred and fifty gram samples of each residue were placed in 30.48-cm high, 5.08-cm
ID plastic columns. Figure 3 . illustrates the column operations. The water was added at
the rate of 250 ml per leaching cycle. Leachate was collected by gravity percolation
once a week for six weeks. Analyses were performed on the leachate by the methods in-
dicated in Appendix A.
Laboratory-scale leaching studies were oho con ducted on the various stratal materials
used in the large-scale test columns. Table 12 lists the types and quantities of materials
tested. Three 250 ml leaching cycles were done using the procedures described above.
Chemical analyses were conducted to determine the quantities of various constituents
leached out of these materials over time. These values were then used to help establish
background or baseline concentrations of leachate constituents analyzed in the pilot-scale
columns. Accelerated small-scale column leaching was also developed to simulate 52
24
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Figure 3. Laboratory-scale column leaching,
25
-------
TABLE 12. STRATIGRAPHIC MATERIALS SIMULATED IN LEACHING TESTS
Stratigrophic
Unit
Sandstone
Sandstone
Claystone
Dolomite
Limestone
Granite bedrock
Simulant
Material
*16 Silica sand
#60 Silica sand
#60 Silica sand
clayr (kaolin)
Coarse meal grade dolomite
Coarse meal grade limestone
Granitic pea - gravel
Decomposed granite
Quantity (g)
300
300
240
60
300
300
225
75
• Bituminous coal
Coarse ground lump
bituminous coal
100
26
-------
separate 250 ml leaching cycles in a period of several weeks. The results of these tests
were not available at the time that this interim report was prepared.
Chemical Properties Tests
Cation Exchange Capacity
The cation exchange capacities of the residues and column materials were measured to
indicate the amount of interchange that could occur as a result of leachate water moving
through the various solids in the test columns. The existing cations were replaced with
sodium ions in an acetate solution. The sodium ions were then replaced by ammonium ions
in the acetate solution. The concentration of sodium ions in the ammonium acetate was
measured next and converted to cation exchange capacity in milliequivalents per 100 g of
original dry material. A detailed outline of the procedure is given in Appendix A. The
residue cation exchange capacity data are shown in Table 13„
Acid Neutralization Capacity
The test involved dissolving a weighted amount of residue in distilled, deionized
water. As measured quantities of 12N HCL were added, the pH was monitored until the
neutral value was reached. The results were calculated to equivalents of 1 N HCL
required to neutralize one kg of residue. These results are presented in Table 14 .
Heat Release
One feature of some of the pilot plant residues, as received, has been their extreme
exothermal activity upon addition of water. The apparent cause was lime slaking:
CaO + H2O —>• Ca(OH)2 + heat.
Slaking of the sodium, potassium and magnesium oxides also probably contribute some heat
release, as well. Temperature changes were recorded for the addition of 3.8 I water to
13.6 kg, and are shown in Figures 4 and 5 •
Physical Properties
Residue Preparation
Residue samples to be slaked were covered with water and allowed to react. When
all activity had ceased, the slaked samples were dried in an oven at approximately 103 C
for 24 hours. Unslaked residue samples were used as received without further drying, since
moisture content was already about zero.
27
-------
CO LUMNMATERj AL jgAILQJJ^£MM
Material ° CEC meq/lOOg residue
EFA 13.6
ESBM 1 .9
VFA 2 .4
VSBM 2 .4
NJFA 0.5
NJSBM 1 .9
Limestone 0.6
Dolomite 1 .9
Bituminous Coal 2.7
Claystone/Sand, 4:1 7.2
Decomposed Granite 26.6
#1 6 Silica Sand 1.4
#60 Silica Sand 2.8
Residues were slaked before determining CEC.
Residue
Source
Exxon Miniplant
Pope, Evans, and
Robbins
Esso, England
Type
Fly Ash
Spent Bed Material
Fly Ash
Spent Bed Material
Fly Ash
Spent Bed Material
Neutralization Capacity
(equivalentsAg)
17.5
26.0
8.8
2.6
78.1
35.5
28
-------
220 C after 1000 sec
Time (min)
Figure 4. Temperature change frorn water addition to dry residues.
-------
CJ
o
60
55
50
45
§
lu
55^35
30
25
20
10
4812 1620
40
EFA
100
120
60 80
Time (min.)
Figure 5 . Temperature change from water addition to dry residues.
-------
Parti cl e Si ze An al ysi s
The procedure used complied with ASTM D422. A 500 gm sample of each slaked
and unslaked residue was sieved, using fhe number 4, 10, 20, 40, 80, TOO, and 200
sieves. No hydrometer analyses were performed on spent bed materials because some portion
of the residue was soluble, which would substantially alter the results. Hydrometer
analyses were conducted on slaked samples only for the fly ashes. The results from the
hydrometer and the sieve analyses were plotted together, and are presented in Figures
6 and 7 . Additionally, the sieve analyses for column strata material are shown in
Figures 8 through 10.
Specific Gravity
Specific gravity measurements were made for test residues to establish their physical
characteristics for aggregate or other possible uses. The method used was that shown in
ASTM D854, except that step 6.2 was changed from a period of partial vacuum to a period
of vigorous shaking. This did not affect the results. Specific gravity values were not
obtained for the spent bed materials, as some portions were soluble and this phenomenon
interfered with the ASTM D654 type analysis.
Moisture Content
Procedures in ASTM D2216 were followed, using the residues as received (see
Table?,).
Degree of Saturation
Degree of saturation was obtained by substituting into the formula:
_ _ _ WG _ , where
~
W = moisture content V = ™it weight of water
w
G = specific gravity , _ . . , -
r ' I/ - unit weight of residue
Results are shown in Table 7 . ' d
Loose Dry Density
The dry density of each residue, both slaked and unslaked, was determined by pour-
ing the dried residue into a 100-ml beaker. The difference between the empty and filled
weights of the container was divided by the known volume to yield the loose dry density
value, which is shown in Table 7 .
31
-------
Legend
o NJFA, unslaked
O NJFA, slaked
A NJSBM, unslaked
A NJSBM, slaked
D VFA, unslaked
D VFA, slaked
O VSBM, unslaked
O VSBM, slaked
1.0
0.1
Diameter (mm)
0.001
Figure 6 . Particle size analyses: coal combustion residues.
-------
co
100
90
80
70
2oO
•4-
| 50
_£-
fo 40
^c
30
2Q
10
0
Legend
O CFA, unslaked
O CFA, slaked
A EFA, unslaked
A EFA, slaked
D ESBM, unsld«jd
D ESBM, slaked
O FSFA, unslaked
o FSFA, slaked
1.0
0.1
Diameter (mm)
0.01
.001
Figure 7 . Particle size analyses « oil gasification residues.
-------
o>
"5
100
90
80
70
60
50
140
30
20
10
0
Legend
o Granitic Pea Gravel—Composite Sample
D Granite Bedrock (pea gravel to decomposed granite in a 3:1 ratio)
O Granite Bedrock (small gravel to decomposed granite in a 1:1 ratio)
O Large Gravel—Composite Sample
Figure 8
Diameter (mm)
Particle size analysis: pea gravel, granite bedrock, and large gravel.
-------
Legend
o Silicasand1 (#60)
A Silica sand (#16)
O Decomposed granite
1.0 0.1
Diameter (mm)
Figure 9 . Particle size analysis:silica sand and decomposed granite.
0.01
-------
CO
O*
Legend
o Bituminous Coalu-Composite Sample
D Wiite Marble (Dolomite)—Composite Sample
A Limestone—Composite Sample
0.01
Diameter (mm)
Figure 10 « Particle size analysis? coal, dolomite, and limestone.
-------
Water-holding Capacity
Water-holding capacity was determined for the slaked residues only. A sample of slaked
and dried residue was placed in a funnel lined with filter paper, covered with water, and
allowed to drain under the force of gravity. The sample was covered to prevent evaporation,
and allowed to stand until there was no further water drainage for a five-minute period. Then
the wet sample was weighed, dried at approximately 103° C for 24 hours, and reweighed.
The difference between the wet and dry weights was equal to the water held in the sample.
This was divided by the dry weight of the sample to give the water-holding capacity of the
residue. Results of the water-holding capacity tests are presented in Table 15.
Permeability
Data was obtained following the procedure described in the Standard Method of Test for
Permeability of Granular Soils (Constant Head). The results of the tests for residue perme-
ability are shown on Table 16.
Results
Chemical Composition
Laboratory mixing tests wherein residue was added to water to characterize their total
soluble fractions are presented in Tables 17 through 20. BOD results are also shown graphically
in Figure 11. Results of the laboratory bench-scale leaching tests are given in Tables 20
through 26 and Figures 12 through 14.
The procedures followed in these tests do not give absolute values, but rather data for com-
parison of residues. The molecular states (types of compounds) of the analyzed elements were
not determined. Comparison of the laboratory mixing test characterization analyses and bench-
scale small column leaching tests was a basis for planning the longer-term pilot-scale tests
(Chapter 6) which simulated field conditions more closely. The laboratory tests indicated that
major leachate constituents of the residues were high in total dissolved salts consisting of sulfate
and chloride onions, and calcium, magnesium, iron, sodium, and potassium cations. Many
trace metals were also present in low concentration, which would nevertheless be high enough
to cause concern if they were leached into the environment.
Comparison of results for soluble fractions showed that pH will undoubtedly influence the
quality of the leachate. In the bench-scale experiment, some elements (chloride, sodium,
potassium) were leached readily, and were almost completely extracted by the time tap water
equivalent to six times the weight of the residues had leached through. On the other hand,
calcium and sulfate were leached in relatively constant, high concentrations which had not
diminished by the end of six water addition cycles.
Sulfate content in leachate exceeded the recommended maximum for drinking water supply.
Sulfate is also of interest as it may combine with calcium to form gypsum or with lead as lead
sulfate. Both of these compounds are relatively insoluble, and so leaching of calcium and lead
may be reduced.
-------
CO
00
Residue Specific
Type Gravity0
(g/cc)
VFA 2.65
VSBM c
NJFA 2.71
NJSBM c
EFA 2.02
ESBM c
CFA 2.72
FSFA 3.11
Moisture
Content13
(%drywt.)
0
0
0
0
0
0
0
0
Degree of
Saturation"
(%dry wt.)
0
o
0
0
0
0
0
0
Dry Density
Before After
1 Slaking*3 Slaking
(g/cc) (g/cc)
0.76
0.92
0,74
0.73
1.46
1,36
1.09
1.18
0.76
0,97
0,65
1,08
0.83
0^7
0.78
0./6
»
Water- holding
Capacity
IB H2o \
y g Residue /
0.66
0.50
0.74
0.44
0.70
0.98
0.76
0.78
, Alter slaking.
As received.
c Not obtainable/ as some portion of the material in question enters into solution.
-------
TABLE 16 . PERMEABILITY OF RESIDUES AND COLUMN MATERIALS
~ Hydraulic Conductivity K
Description (cm/sec)
Residue ^
PER Virginia fly ash 1.9xlO~3
PER Virginia spent bed material (slaked) 1.9 x 10~4
Exxon New Jersey fly ash 6.4 x 10_2
Exxon New Jersey spent bed material (slaked) 3.7 x I0_g
Esso, England fly ash (slaked) 1.6 x 10_ «•
Esso, England spent bed material (slaked) 6.8 x 10
Column Material -
Limestone (granular) 1.0xlO_2
Dolomite (granular) 5.9 x 10 «
Bituminous Coal (granular) 6.1 x 10 „
Sanitary landfill 7.0 x 10~_3
Claystone (4:1, #60 sand to clay)* 1.64 x 10~
Sandstone (#60 sand) 3.2 x 10~2
Sandstone ^16 sand) 7.4 x 10,,
Clayey loam (3:1 #60 sand to soM)* 1.1 x 10~2
Silty loam (3:1 #60 sand to soil) * 1.0 x 10[4
Sandy loam 1.6x10_o
Granite bedrock (3:1 p-gravel to decomposed granite)* 5.2 x 10_9
Gravel 8.2 x 10"
*
By weight
39
-------
TABLE 17. LABORATORY CHARACTERIZATION OF RESIDUES
1. EXXON MINIPLANT, LINDEN, NEW JERSEY
Constituent
pH
Total dissolved solids
COD
BOD
Chloride
Nitrate
Phosphate
Sulfate
Aluminum
Arsenic
Beryllium
Boron
Cadmium
Calcium
Chromium
Copper
Iron
Lead
Magnesium
Manganese
Molybdenum
Nickel
Potassium
Silver
Sodium
Zinc
Water
Soluble
9.3
2,124
45.6
f
— i
NDd
27
4
1,190
— _
ND
—
0.61
ND
1,805
— -
—
ND
2.5
10
—
ND
~
24
ND
22
ND
Fly Ash
Acidb
Soluble
j-*
e
_—
— _
ND
--
182
5,300
—
62.5
ND
0.2
34,600
__
—
78.4
7.7
ND
—
69
—
440
0.2
400
8.0
Basec
Soluble
13.0
—
--
__
5.76
3
6.3
26,000
—
22.5
—
0.88
0.2
ND
—
—
1.6
6.0
2,360
—
ND
—
__
0.4
—
0.5
Spent Bed Material
Water Acid Base°
Soluble Soluble Soluble
12.2
4,188
51.4
-J
ND
26
ND
1,900
0.06
5.0
ND
0.64
ND
6,017
—
0.5
ND
2.4
95
0.025
12
0.5
32
0.02
89
ND
6.6
—
—
—
ND
—
1.5
1,000
0.26
30.0
ND
ND
0.5
96,754
—
K07
7.6
1.4
ND
0.95
278
7.7
248
0.6
ND
1.0
13.0
— —
—
—
8.42
ND
ND
17,400
ND
18.7
ND
0.97
0.2
ND
— •
0.12
1.8
5.9
3,200
ND
ND
0.75
—
0.3
—
0.2
, All concentrations in mg constituent/kg residue, dry weight after shaker test.
b
l.ON
* 1.0 N NaOH.
None detected = ND.
f — Analysis not performed.
See Figure 11.
40
-------
TABLE 18. LABORATORY CHARACTERIZATION OF RESIDUES4
POPE, EVANS, & ROBBINS, ALEXANDRIA, VIRGINIA
Constituent
PH
Total dissolved solids
COD
BOD
Chloride
Nitrate
Phosphate
Sulfate
Aluminum
Arsenic
Beryllium
Boron
Cadmium
Calcium
Chromium
Copper
Iron
Lead
Magnesium
Manganese
Molybdenum
Nickel
Potassium
Silver
Sodium
Zinc
Water
Soluble
12.2
4,212
104.6
t
NDd
2
ND
1,600
ND
2.5
ND
0.5
ND
540
—
0.025
0.5
1.6
96
0.025
10
0.25
33
0.08
145
0.08
Fly Ash
Acidb
Soluble
4.1
e
—
__
ND
—
2
1,050
1.2
32.5
ND
ND
0.5
32,000
—
0.92
11.0
1.3
1,940
0.87
247
7.7
276
0.7
ND
1.1
Base
Soluble
12.9
—
—
_M
6.21
ND
ND
17,400
ND
20.0
ND
0.83
0.2
ND
—
ND
1.7
7.1
10
ND
ND
ND
—
0.3
—
1.0
Spent Bed Material
Water Acidb BaseC
Soluble Soluble Soluble
12.2
4,064
57,8
T
ND
28
ND
1,640
0.06
5.0
ND
0.82
ND
750
—
0.5
0.1
1.1
22
0.025
11
0.5
63
0.08
178
ND
6.1
—
—
__
ND
~
ND
1,050
0.26
32.5
ND
ND
0.5
32,000
—
1.07
6.6
1.5
22
0.95
272
7.7
276
0.8
100
0.3
12.9
—
—
__
22.83
7
ND
32,500
ND
17.5
ND
0.72
0.3
ND
—
0.12
2.2
7.6
ND
ND
7
0.75
—
0.4
—
0.4
, All concentration in mg constituent/kg residue, dry weight after shaker test.
b l.ON HNO3.
j 1.0 N NaOH.
None detected = ND.
® — Analysis not performed.
See Figure 11.
41
-------
TABLE 19. LABORATORY CHARACTERIZATION OF RESIDUES
III. ESSO, ENGLAND
Constituent
pH
Total dissolved solids
COD
BOD
Chloride
Nitrate
Phosphate
Sulfate
Aluminum
Arsenic
Berry Ilium
Boron
Cadmium
Calcium
Chromium
Copper
Iron
Lead
Magnesium
Manganese
Molybdenum
Nickel
Potassium
Silver
Sodium
Zinc
Water
Soluble
12.2
5,266
132
f
11,200
24.5
6.0
4,380
0.25
ND
ND
ND
ND
4,500
1.75
ND
1.0
0.075
1.0
0.075
81
1.25
52
0.20
245
0.15
Fly Ash
Acid1*
Soluble
2.4
e
116
—
5,000
2.0
2,625
1.75
0.05
ND
0.325
0.075
70,000
14.2
2.25
7.0
ND
1.3
0.75
180
8.0
232
0.68
270
0.3
BaseC
Soluble
12.9
—
98
—
10,000
NDd
1.0
24,310
ND
ND
42
ND
0.05
316
ND
ND
0.25
ND
1.0
0.025
NO
1.5
~
0.15
—
0.025
Spent Bed Material
Water Acic^ BaseC
Soluble Soluble Soluble
12.1
6,214
68
f
8,200
12
1.9
3,380
0.25
ND
ND
0.63
0.05
4,750
1.5
0.5
1.7
0.17
1.0
0.1
0.8
0.25
ND
0.08
40
0.15
10.8
—
68
~
12,500
__
1.9
250
1.25
0.1
50
ND
0.28
75,000
13.5
2.0
6.0
ND
1.3
0.6
ND
7.5
ND
0.72
45
0.30
12.9
—
59
—
10,280
9.4
0.6
4,625
1.0
ND
114
0.52
ND
60
ND
ND
ND
ND
1.0
ND
ND
ND
—
ND
—
ND
, All concentrations in mg constituent/kg residue, dry weight after shaker test.
&1.0NHNO3.
d
1.0 N NaOH.
None detected = ND.
f —Analysis not performed.
f See Figure 11.
42
-------
TABLE 20. LABORATORY CHARACTERIZATION OF RESIDUES
IV. ESSO, ENGLAND
Constituent
pH
Total dissolved solids
COD
BOD
Chloride
Nitrate
Phosphate
Sulfate
Aluminum
Arsenic
Beryllium
Boron
Cadmium
Calcium
Chromium
Copper
Iron
Lead
Magnesium
Manganese
Molybdenum
Nickel
Potassium
Silver
Sodium
Zinc
Water
Soluble
12.1
3,808
197.6
—
199.5
11.8
1.87
1,280
0.25
0.1
ND
ND
ND
510
—
ND
0.46
0.5
7
0.075
17
1.25
56
0.04
300
0.03
Fly Ash3
Acid Base
Soluble Soluble
6.T
g
—
—
210.6
-_
—
2,000
1.75
3.7
ND
ND
0.18
32,000
—
2.25
5.23
5.2
16
0.75
229
8
356
0.53
800
0.13
12.9
—
—
—
354.6
NDf
—
11,300
ND
0.3
42
0.13
0.01
ND
—
ND
0.25
0.7
ND
0.025
ND
1.5
f
ND
—
ND
Water
Soluble
12.0'
4,380
ocO *5
^w^ • O
—
160.7
10.6
0.35
1,680
—
0.1
—
0.43
OjOl
520
—
—
0.43
0.6
5
—
12
—
62
0.03
200
ND
FlyAsh6
Acidb
Soluble
1 6.4 "
—
—
—
77.6
~
—
2,190
—
3.4
—
ND
0.18
32,000
—
—
4.78
5.3
13
—
2.7
—
276
0.50
200
0.10
Base0
Soluble
13.0
—
—
—
388.0
2.6
—
3,260
—
ND
—
0.07
ND
ND
—
—
ND
0.1
ND
—
ND
—
—
ND
—
ND
? All concentrations in mg constituentAg residue, dry weight after shaker test.
b 1.0NHNQ3.
d
l.ON NaOH.
Cyclone fly ash.
Fines, stack fly ash.
f None detected = ND.
? — Analysis not performed.
See Figure 11.
43
-------
0)
1
O
o
CO
300
285
270
255
240
225
210
195
180
165
150
135J
120
105
90
75
60 -
45 ~
30 -
15 -.
0
Legend
* Standard (Control)
* NJSBM
* VSBM
o CFA
o NJFA
o FSFA
• VFA
1
See Table 6 for explanation of
letter code. Rgure
Day
BOD from Residue water ejctracf;.
-------
TABLE 21. , LABORATORY LEACHINGbTESTS: GRANITE BEDROCK
M
Constituent
pH
Chloride
Nitrate
Sulfate
Arsenic
Boron
Cadmium
Cblcium
Iron
Lead
Magnesium
Mercury
Potassium
Sodium
Zinc
250
9.2
NDa
ND
34.0
2.5
—
ND
1.0
ND
ND
ND
—
ND
72.0
ND
Total Volume of Leachate (ml)
500
8.8
ND
ND
10.0
ND
—
ND
ND
ND
ND
ND
ND
60.0
ND
750
8.9
ND
—
2.5
0.8
ND
ND
ND
ND
ND
ND
ND
ND
64.0
ND
a ND - None detected.
Water percolated through the bench scale residue sample.
Mg/l except as noted.
45
-------
TABLE 22. LABORATORY LEACHING TESTSfa: BITUMINOUS COAL
Constituent
pH
Chloride
Nitrate
Sulfate
Arsenic
Boron
Cadmium
Calcium
Iron
Lead
Magnesium
Mercury
Potassium
Sodium
Zinc
250
9.0
ND°
ND
232.0
2.5
—
ND
3.6
ND
ND
ND
ND
4.0
80.0
ND
Total Volume of Leachate
500
8.8
ND
ND
42.0
5.0
—
—
0.3
ND
ND
ND
ND
ND
56.0
ND
(ml)
750
8.8
ND
—
10.0
2.5
ND
ND
0.9
ND
ND
ND
ND
1.0
64.0
ND
ND - None detected.
Water percolated through the bench scale residue sample.
c Mg/l except as noted.
46
-------
Constituent
PH
Chloride
Nitrate
Sulfate
Arsenic
Boron
Cadmium
Calcium
Iron
Lead
Magnesium
Mercury
Potassium
Sodium
Zinc
250
9.6
NDa
ND
9.0
0.8
—
ND
2.2
ND
0.1
ND
ND
8.0
103.0
ND
Total Volume of Leachate (ml)
500
8.8
ND
ND
3.0
0.8
—
—
0.1
ND
ND
ND
ND
ND
61.0
ND
750
9.2
ND
ND
ND
0.8
0.6
ND
ND
ND
ND
ND
ND
ND
60.0
ND
ND - None detected.
Water percolated through the bench scale residue sample.
Mg/l except as noted.
47
-------
TABLE 24. LABORATORY LEACHING*3 TESTS; LIMESTONE
Constituent
PH
Chloride
Nitrate
Sulfate
Arsenic
Boron
Cadmium
Calcium
Iron
Lead
Magnesium
Mercury
Potassium
Sodium
Zinc
250
9.5
NDa
ND
10.0
ND
—
0.01
ND
ND
0.6
ND
ND
3.0
74.0
ND
Total Volume of Leachate
500
8.8
ND
ND
19.0
1.6
—
—
ND
ND
ND
ND
ND
ND
68.0
ND
(ml)
750
8.9
ND
—
6.0
1.6
0.7
0.01
ND
ND
ND
ND
ND
1.0
63.0
ND
a ND - None detected.
Water percolated through the bench scale residue sample.
Mg/l except as noted.
48
-------
TABLE 25, LABORATORY LEACHINGb TESTS; *60 SILICA SAND
Constituent
pH
Chloride
Nitrate
Sulfate
Arsenic
Boron
Cadmium
Calcium
Iron
Lead
Magnesium
Mercury
Potassium
Sodium
Zinc
250
9.0
75.0
ND
123.0
ND
—
0.01
ND
ND
ND
ND
ND
3.0
168.0
ND
Total Volume of Leachate (ml)
500
8.8
NDa
ND
30.0 .
ND
—
—
ND
ND
ND
ND
ND
ND
77.0
ND
750
9.1
ND
—
5.0
1.6
ND
ND
ND
ND
ND
0.7
ND
2.0
70.0
ND
-. - ._ „ . - - i
ND - None detected.
Water percolated through the bench scale residue sample.
Mg/l except as noted.
49
-------
•• ""— •- — — '
Constituent
pH
Chloride
Nitrate
Sulfate
Arsenic
Boron
Cadmium
Calcium
Iron
Lead
Magnesium
Mercury
Potassium
Sodium
Zinc
250
10.0
9.0
ND
103.0
0.8
—
ND
3.7
ND
0.2
ND
ND
50.0
245.0
ND
Total Volume of Leachate (ml)
500
8.8
NDa
ND
12.0
ND
—
—
ND
ND
ND
0.03
ND
ND
68.0
ND
750
8.8
ND
—
7.0
ND
0.025
ND
ND
ND
ND
ND
ND
ND
62.0
ND
ND - None detected.
Water percolated through the bench scale residue sample.
Mg/l except as ioted.
50
-------
TABLE 27. LABORATORY LEACHING*3 TESTS; CLAYSTONE
Constituent
pH
Chloride
Nitrate
Sulfate
Arsenic
Boron
Cadmium
Calcium
Iron
Lead
Magnesium
Mercury
Potassium
Sodium
Zinc
250
9.2
65
ND
141.0
0.8
__
ND
0.4
0.1
ND
0.1
ND
ND
161.0
ND
Total Volume of Leachate
500
8.8
ND°
ND
9.0
1.6
ND
—
ND
ND
ND
ND
ND
ND
97.0
ND
(ml)
750
9.0
ND
—
2.5
1.6
ND
ND
ND
ND
ND
ND
ND
ND
71.0
ND
ND - None detected.
Water percolated through the bench scale residue sample.
C Mg/l except as noted.
51
-------
X
4-
§2 1,000
>£
1 "g 500
I °
D a\
U —
Cl
- - lt0
x'X'
- / ^-. — — 0.5
/ ,-•
- / ^ *
. .»*
iiiiifi
Fe
x
t/'
^ —
/* ^^,*^*
x*" ^••*"^P
»^«^*
^•T 1 1 L I J S
0246 0246
Leachate ratio (I/kg) Leachate ratio (I/kg)
£
O O)
0) i> ^
> ,5,
*" _ j
| "o 2
u <»
Hg
100
50
-
__. —1 . =^~^=- vt= I 1
Ni*
- . ^
/'
/-/
- ^"^
^ i i i i i it
0246 0 50 100 200 300
Leachate ratio (I/kg) Leachate ratio (I/kg)
£
o 'ro 20
3^
1 •§ i-.o
i-5 0.5
D 0
Pb
12,000
^ 9,000
s>^ 6,000
* ^^
- sfS^ 3,000
^* : i t i ! i L
S04
,S'
'•?'"''
.•^"'^
i ^"**
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0246 0246
x
£
|| 0.2
([} C
'S "S O-1
i 8
u
Leachate ratio (I/kg) Leachate ratio (I/kg)
Zn
Legend
x£ — — VFA
^f' VSBM
S' Notes
>r Leachate ratio = Water : Residue
0 2 4 6
Leachate ratio (I/kg)
Figure 12. Leaching characteristics of VFA and VSBM.
52
-------
JX
|| 300
5l
.0 ~° 200
11 100
u .£
Cl
-
^---" 0.15
' ^"*" ^. 0.10
V^.-"""^ 0.05
Fe
_
-
rt«T"-"-T "T " T" " T~ i i
o
D _C
U j>
2.0
246
Leachate ratio (I/kg)
Hg
0
246
Leachatt ratio (I/kg)
100
50
0246
Leachate ratio (I/kg)
#>\
"100"' 200 ' 300 '
Leachate ratio (I/kg)
£.
"^
!"
•j-
D
U
.z-
4-
C
O
T^
Cumulative c
^2.0
> 1.5
:f i-o
-i 0.5
D
(D
(
|o.08
Jo. 06
J 0.04
§0.02
Pb
12,000
9,000
.^'^ 6/ooo
.<^^^ 3,000
s
^
&
^
- s'
s*\ i i it i i
D24'6 0246
Leachate ratio (I/kg) Leachate ratio (I/kg)
Zn Legend
^_ NJFA
x^ NJSBM
/
/ Notes
/ _. — • . . . Leachate ratio = Water :
^«— *f 1 1 1 I II
S04
Residue
0246
Leachate ratio (I/kg)
Figure 13 . Leaching characteristics of NJFA and NJSBM.
53
-------
c
o
3
15
10
5
CI
/ 15
/
• / 10
V^'"" 5
(s i i i t i i t
x
X
•/.'-'
^- "1 i f r !
Fe
J !
0 50 100 150
Leachate ratio (I/kg)
50 100 150
Leachate ratio (I/kg)
50 100 150
Leachate ratio (I/kg)
x
o "TO
% j? 300
1^ 2°°
i-S 100
§ o
u "
Hg
200
150
100
Ni
-
. *
- / .'*
X1 i i i i t it
0 50 100 150 0 50 150 250
Leachate ratio (I/kg) Leachate ratio (I/kg)
£
«*••
§5 20
§n is
1 "S 10
e-C
_ D 5
-* <1>
Pb
200
150
" X"''^'-" 100
-/^•"' 50
4*'\ iii> I i
so4
-
; /' ' ^
^*\ ii ttii
0 50 100 150 0 50 100 150
•^
g 1? 4.0
^ 3.0
12 2*°
|1 i.o
u ">
Leachate ratio (I/kg) Leachate ratio (I/kg)
Zn
Legend
EFA
/ ^> ESBM
/ ,'' Note
- *'£'' Leachate ratio = Water : Residue
/>
JS 1 1 I t 1 II
Figure 14, Leaching characteristics of EFA and ESBM.
54
-------
CHAPTER 6
PILOT COLUMN STUDIES OF RESIDUE DISPOSAL
Purpose
One purpose of this sludy was to evaluate the possible impacts of residue disposal
into different locations. The first step in this evaluation was to simulate likely disposal
locations on a pilot scale. This allowed testing under defined conditions and control of
physical variables which might affect the behavior of the residues in natural environments.
The following section discusses the real world and simulated disposal locations that were
evaluated.
Simulated Sedimentary Environment Columns
Ocean Disposal
Actual location. Residue wastes could be disposed into the ocean in many ways
which include dumping the wastes into the open ocean, piping the wastes in the form of a
slurry onto the ocean floor (or a submarine canyon), or using the residues to build land or
islands.
Test Column. The ocean disposal test column is more representative of a filled land
type disposal in the ocean where only the tidal portion of the residue would be flushed by
sea wafer for an extended period of time (also waves and land drainage can cause some
flushing). The *60 sand used in the test column represents the deposited sandy base over
which the residues might be placed when filling begins (see Figure 15; for legend see
Figure 16).
Sanitary Landfills
Actual Location. Sanitary landfills are made of materials (a mix of ash residues and
solid waste) and lifts of soil placed on natural ground or other inert material. Sanitary
landfills may be built with 3m of mixed refuse to 003m of soil fill/lift), i.e.
~ 90 percent solid waste and ~ 10 percent cover soil. The residue to trash percentage
combination may vary. Both residues and refuse landfills can generate leachate when
saturated with water.
Test Column. The test column simulated an arbitrarily selected real world landfill
environment where a brown municipal type solid waste mixture was placed on a sequence
of sedimentary strata overlying granite bedrock (see Figure 1 8). Organic solid waste and
ash residues were separated for residue reclamation after leaching tests. Assuming a depth
of 30m below the land surface for the water table, each column represented the conversion
factors for the thicknesses of the replicated real world strata materials as shown in Table 28
The scale coefficients of approximately 1:12 were chosen to conveniently replicate the
strata in the test column assuming a 30.5 m depth to groundwater. Relatively impermeable
55
-------
20 cm
oo
E
o
£
u
£
o
u
00
•III
Collection
Lysi meter
Freeboard
Residues
Sandstone (#60 sand)
Sandstone (*16 sand)
Gravel
Figure 15 » Simulated sedimenj-ary environment: sea water test column.
56
-------
BITUMINOUS COAL
(coarse ground lump bituminous coal)
CLAY STONE
(clay and "oO silica sand)
DOLOMITE
(coarse meal grade dolomite)
GRANITE BEDROCK
(granitic P-gravel and decomposed granite)
SOIL HORIZON A
(sand, silt and clay loams)
SOIL HORIZON B
(sand, silt and clay loams)
LIMESTONE
(coarse meal grade limestone)
SANDSTONE
mesh silica sand)
SANDSTONE
(^60 mesh silica sand)
SANITARY LANDFILL
(solid waste)
Figure 16 . Legend for test column disposal environments.
57
-------
20cm
Freeboard
Residues
Sandstone (^ 16 sand)
Sanitary landfill
Claystone
ol lection
Lysimeter
Sandstone (#60 sand)
Sandstone pi 6 sand)
Granite bedrock
Sandstone (#16 sand)
Gravel
Figure 17. Sanitary landfill test column.
58
-------
TABLE 28. REPRESENTATIVE THICKNESS SANITARY LANDFILL
SIMULATED IN TEST COLUMNS
Material
Residue
Solid Waste0
Claystone
Sandstone
Granite Bedrock
Representative
Stratum
Thickness (m)
5.79
7.62
0.91
8.54
7.62
Column Layer
Thickness (m)
0.46
0.61
0.29
0.67
0.61
Scale ,
Coefficient
1:12.6
1:12.5
1: 3.1
1:12.8
1:12.5
, No decomposition before leaching began in first 20 columns, "fresh" solid waste used.
Excludes admixed *60 sand.
, Includes admixed *60 sand from claystone layer.
Thickness of strata in field to thickness of simulated strata in test column (a ratio).
Source: Ralph Stone and Company, Inc. files.
59
-------
materials, such as claystone, were "diluted" with sand to increase their permeability, thus
resulting in reduced scale coefficients. Obviously, standard claystone is so impervious
that without the increase in permeability provided by the standard Ottawa sand, there would
have been no significant column leachate. In nature, however, there is slow water move-
ment and leaching through the claystone. Hence, the test columns replicated an accelerated-
type leachate test of what could occur in nature.
Limestone and Dolomite Quarries
Actual Location. An abandoned limestone quarry might contain 20 to 40 percent
limestone; the remaining unquarried limestone could normally be left because it was of
poor quality, had a high cost of mining, or for other reasons. The sedimentary sequence
which would be associated with the quarry would probably consist of a series of limestone,
shale, and sandstone beds. This type of strata occurs in varying percentages relative to
each other. No "typical" section below a limestone or dolomite quarry exists. It might
be all sandstone, all shale, or a combination of any of the three types of strata. For this
reason,an arbitrary "topical" sequence was selected from a real world quarry as shown in
Table 29.
Test Column. The test columns represent a configuration in which residues would
be deposited in an abandoned quarry pit and underlain by the thickness of strata shown in
Table; 28 (assuming a depth to groundwater table of 30 m). In this 30 m section, below
the residues there would be 14.2 m of limestone, 1.6 m of claystone, and 14.2 m of
sandstone. (See Figures 18 and 19.) Again, claystone was admixed with sand to increase
permeability, thus, resulting in lower scale coefficients.
Coal Mine.
Actual Location. An abandoned coal mine would be underlain by a sequence of
shale, sandstone, limestone, and minor coal seams - the sequence being predominantly
shale (see Figure,20). Disposal of residues would be in an abandoned mine underlain by
similar strata.
Test Column. The test column represent an abandoned coal mine which is underlain
by the thicknesses of strata, 'as shown in Table 30 and Figure 21 (assuming a 30 m depth to
groundwater).
Ratios of Densities
Ratios of densities shown in Table 31 are calculated by comparing the densities of
materials as they exist in the columns with densities of materials as they could exist in the
field. The densities of materials in the test columns were calculated using the actual
weights of materials added, divided by the amount (height) of column filled up (see
Table 32). Densities of typical earth materials in the field were determined from various
sources (see Table 33.. Comparison of Tables 31 and 32 indicate that the actual densities
of materials placed in the columns were less than may exist under field conditions.
60
-------
TABLE 29. REPRESENTATIVE THICKNESSES OF LIMESTONE. &
DOLOMITE SIMULATION TEST COLUMNS
Material
Limestone
Claystone
Sandstone
Limestone Quarry
Representa-
tive Stratum ^
Thicknesses (m)
14.2
1.4
14.2
Dolomite Quarry
Scale (a)
Coefficient
15.7
3.9C
15.7
Material
Dolomite
Claystone
Sandstone
Representa-
tive Stratum
Thicknesses (m)
14.2
1.4
14.2
Scale (a)
Coefficient
15.7
3.9<=
15.7
a Thickness of layer in field to thickness of simulated layer in column.
Excludes odd-mixed *6X) sand.
, As mixed, includes sand with clay in column, for increased permeability.
Includes add -mixed *60 sand from claystone layer.
Source: 30, 49, 106.
61
-------
20cm
u
o
CO
o
o
"t
E
u
E
y
o*
-
-------
E
u
o
CO
E
o
E
u
E
u
20 cm
IS
IS
Freeboard
Residue
Sandstone (^60 sand)
in
•M
itm,
Dolomite
wm
Claystone
Collection
Lysimeters
Sandstone (*^60 sand)
Sandstone
san
d)
Gravel
Figure ¥9. Simulated sedimentary environment: dolomite quarry test column,
63
-------
TABLE 30, REPRESENTATIVE THICKNESS OF COAL
MINE SIMULATION TEST COLUMNS
Mr,ter; I Representative Stratum Column Layer _ . a
Material TL- i / \ TL- i / \ Scale Coefficient
Thickness (m) Thickness (m)
Bituminous Coal
Limestonei
Claystone
Sandstone
9.45
7.32
2.13
11.58
0.611
10.46
0.551
10.73
15.5
15.8
3.9
15.8
k Thickness of layer in field to thickness of simulated layer In column.
Excludes odd-mixed $60 sand.
Includes odd-mixed ^60 sand from claystone layer.
Source: 106.
64
-------
Limestone
Coal
=£=£• Meters
^f 1.83
•^x-^-
X tK
HE
,=£?!
§s^=-
} 1 I _L
0.3
0.6
"0.46
0.15
1:P
v/.o
0.-6
1-^. _T
1 .52
0.76
,0.3
0.18
1.40
gfe. 0.02
0.15
fe-§:8§
^^f^ 0.015
S °»92
0.30
1.83
Shale
Limestone
Shale
Ugend
Lim»»ton»
Siltsloneor
sondstone
Coal
•J- R«d and grt«n
._ shole
Black shale
Figure 20: Stratigraphic section of a typical coal mine.
Source: 106.
65
-------
20cm
£
u
£
u
E
u
E
u
o-
E
o
•SK£^
*$$*£>
',£.•'•&.! y
F reeboard
Residue
Sandstone (# 16 sand)
Bituminous coal
Claystone
Sandstone (#60 sand)
Collection
Lysimeters
Limestone
Sandstone (#60 sand)
Sandstone (#16 sand)
Gravel
Figure 21.. Abandoned coal mine test column,
66
-------
ON
XI
'" " L" J - ' -• - - - ~
Material
In Column
Limestone
Dolomite
P-Gravel
#16 Silica
#60 Silica
Claystone
Granite Bedrock
Solid Waste
Bituminous Coal
Density
(g/cc)
1.76
1.51
2.16
1.56
1.56
1.44°
1.82
0.63
0.89
Material
in Field
Limestone
Dolomite
Granodiorite
'Sandstone
Sandstone
Shale
Granodiorite
Sanitary Landfill
Bituminous Coal
Density
(g/cc)
2.71
2.85
2.72
2.32
2.32
2.42
2.72
0.594
1.25
Ratio
Column: Field
1 ;54: 1
1.89:1
1 .26: 1
1 .49: 1
1 .49: 1
1 .68: 1
1 .49: 1
1 .06:1
0.71:1
of Densities
Field: Column
1:0.65
1:0.53
1:<0.79
1:0.67
lrO.67
1:0.60
1:0.67
1:0.94
1 :1 .40
Includes admixed #60 sand.
-------
TABLE 3 2.
Material
P-Gravel
#16 Silica Sand
# 60 Silica Sand
Clay: Sandb
Limestone
Dolomite
Granite Bedrock
Solid Waste
Coal
Clay w/out Sand
.Sandstone
1 :3 by weight
Granodiorite
eNot available
MATERIAL
Wt. Added
(Kg)
12.2
5.4
6.4
27.2
97.7
22.2
23.6
50.3
25.9
43.1
34.9
12.2
17.2
5.55
TABLE 33
DENSITII
Height
(cm)
18
6
9
55
200
49
52
91
46
91
61
61
61
12.25
ES OF NA1
IURAL bIKAIA
Test Column
Area Volume
(cu cm)
314.16
314.16
314.16
314.16
314.16
314.16
314.16
314.16
314.16
314.16
314.16
314.16
314.16
314.16
*. AVERAGE FIELD
Material
Granite
Granodiorite
Sandstone
Shale
Limestone
Dolomite
Sanitary Landfill
5,654.88
1,884.96
2,827.44
17,278.8
62,832.0
15,393.8
16,336.3
28,588.6
14,451 .4
28,588.6
19,163.76
19,163.76
19,163.8
3,848.5
, AINU ICil v-v
Density
(a/cc)
2.16
2.86
2.26
1.57
1.55
1.44
1.44
1.76
1.93
1.51
1.82
0.63
0.89
1.44
^LU/VIINJ
Density of
Field Rocks
(a/cc)
N.A.e
2.32°
2.32
2.32
2.32
2.42°
2.42
2.71
2.71
2.85
2.72d
0.594
1.25
2.42C
DENSITIES OF MATERIALS
Average
2
2
2
2
2
2
0
Field Densities
(g/cc)
.667°
.716°
.32°
.42°
.71b
.85b
.594
Source: 51.
Source: 98.
68
-------
The materials in the test columns were prepared by granulation and hence have
greater surface area exposed for chemical reactions than the natural rocks. In the field the
natural rocky materials would have less surface area exposed to water percolating through
the strata. The amount of surface area exposed in the field per meter of strata is a variable
depending on porosity, capilarity and the extent of fractures and/or permeability for each
material. No simple comparison can therefore be made of surface area exposed per meter
of column material versus the surface area exposed per meter of sfraium in the field.
Column Test Procedures
Column Construction
The test columns were made from plastic PVC pipe (20.3 cm ID) cut to 3.05 m lengths.
For each simulated disposal environment^tratigraphic configurations were developed during
the literature search and scaled to fit the columns. Table 34 identifies the columns con-
structed by number code, environment, and residue type tested. The simulated environment
was marked on the column, as were locations for layer interfaces, observation ports and
soil moisture (lysimeter) ports. The lysimeter and observation ports (2.54 cm diameter)
were drilled in the column sides. A 1,59-cm port was drilled in the center of the PVC
bottom cap for each column and a plastic drain spout was glued in place. The columns
were washed clean, dried, and the bottom cap was glued to the pipe; finally/the columns
were bracketed to the wall in a vertical position.
Filter paper (20.3 cm diameter, *1 qualitative) with a plastic screen above (20.3 cm
diameter) was placed in the bottom of the column. These items were installed from the
top and their location adjusted with a long pole to obtain their correct position. The
columns were then ready for partial filling.
Lysimeter Assembly
A porous ceramic cup (1-bar) was attached to a 30.5 cm length of polyethylene
tubing (1.27 cm ID). The ceramic cup and 3 to 5 cm of the tubing were then covered with
a 0.64 cm layer of *200-mesh silica sand, applied in a thick slurry. The Iysimeters used
an absorbent cotton sock to hold the fine sand during and after placement in the test
columns. Figure22 illustrates the lysimeter assembly and its placement in the columns.
Column Material Preparation
Standard particle size analyses were performed on all materials added to the columns
(see Figures 6 through 10). Detailed grading analyses were employed in the column design:
1) to prevent erosion and clogging (piping of finer material through coarser
materials); 2) to provide sufficient permeability to allow leaching; and 3) to assure
classified reproducible grain sizes and materials. Table 35 presents the criteria used, and
Table 36 summarizes the results of the grading analysis.
69
-------
TABLE 33. COLUMN AND RESIDUE IDENTIFICATION
Column
No. Environment
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
Ocean
Limestone
Limestone
Limestone
Limestone
Dolomite
Dolomite
Dolomite
Dolomite
Landfill
Landfill
Landfill
Landfill
Coal mine
Coal mine
Coal mine
Coal mine
Ocean
Ocean
Ocean
Operating Conditions of Test Runa
Residue
VSBM
NJSBM
VSBM
NJFA
VFA
VSBM
NJSBM
NJFA
VFA
VFA
VSBM
NJFA
NJSBM
VSBM
NJSBM
NJFA
VFA
NJFA
NJSBM
VFA
No. Date
NAb NA "
19.7 8-28-75
NA
19.7 8-28-75
19.7 8-28-75
19.7 8-28-75
NA NA
19.7 8-28-75
19.7 8-28-75
19.7 8-28-75
19.7 8-28-75
19.7 8-28-75
19.7 8-28-75
Average
Temperature Fuel Type
843 Sewickley
coal
905-910 Champion
coal
(eastern)
843 Sewickley
coal
Excess Bed
Air Sorbent
18 Germany
Valley
limestone
9.4 Grove
limestone
18 Germany
Valley
limestone
Ca/S Average
mfr Flue SO2
(ppm)
Variable Variable
2.5 360
Variable Variable
(continued)
-------
TABLE 33 (Cont.)
Operating Conditions of Test Runa
Column Average Excess Bed Ca/5 Average
No. Environment Residue No. Date Temperature Fuel Type Air Sorbent mfr Flue SO~
(°C) (%) (PPm)
21 Ocean EFA NA 11-10-75 890 #2 oil 5-10 BCR 1359 lime 1 200
22 Ocean ESBM
23 Limestone EFA
24 Limestone ESBM
25 Dolomite EFA
26 Dolomite ESBM
27 Landfill EFA
28 Landfill ESBM
29 Coal mine EFA
30 Coal mine ESBM
31 Sandy loam EFA
32 Sandy loam ESBM
33 Clay loam EFA
34 Clay loam ESBM
35 Silty loam EFA
36 Silty loam ESBM I
i
i
i
1 \
\
a
, Operating conditions at the pilot plant test site.
NA - Not available.
-------
Porous Ceramic Cup
#200Mesh Silica Sand
Cotton Cover
Column Material
Test
Column Wall
Rubber Stopper
Polyethelene Tubing
Figure 22. . Lysimeter construction and test column placement.
72
-------
., TABLE 35. CRITERIA DEFINITION FOR GRADING ANALYSIS
Objective Criteria °'b
1) Prevention of erosion and clogging t> (filter)
(piping of finer material through — ,—^— < 4 to 5
coarser material) D85 (SOll)
2) Permeability sufficient to prevent the D (filter)
buildup of large seepage forces - •>—qr— >4 to 5
L>15 isoii;
D
3) Approximately parallel grain size 50 filter) ^5
curves D^ri feoil) ~
D = diameter such that x percent of material is finer.
b X
filter = layer above, soil = layer below.
Source: 25,154.
73
-------
^\FIIter
Soil ^v.
Limestone
Dolomite
#16 Silica
Sand
#60 Silica
Sand
P-Gravel
Coal
Claystone 4:1
Granite
Bedrock 1:1
Granite
Bedrock 3:1
#16
Limestone Dolomite Silica
Sand
2 Marg.0' b
2Marg.
2 2
2 2Marg. 2Marg.
222
2 2Marg.
2Marg.
2
#60
Silica
Sand
2
2
2
2
2
o.k.
2
2
n /-. i ,~i /-i i. Granite Granite
P-Gravel Coal Cloystone _ , _ , ,
4.^ Bedrock Bedrock
1:1 3:1
2 Marg. 2
1 2
o.k. 2 22
1,3 2 Marg. 2Marg. 3
2
o.k. 2
o.k.
o.k.
,a Numbers indicate grading analysis criteria definition shown in Table 34 .
b
Marg. = Marginal.
-------
Most of the column fill materials were usable when delivered. However, due to the
impervious characteristics of the extremely fine-grained claystone, it appeared that a
100 percent claystone layer would not permit leachate drainage. Permeability tests were
performed on several different sand to clay mixtures. The mix that provided a reasonable
permeability check had about a 3:1 by weight ratio of *60 mesh silica sand to clay.
Homogeneous mixing was done in 5 to 10 kg quantities which were more easily handled.
The granite material also required mixing in a ratio of 3;1 granitic pea gravel to decom-
posed granite by weight to achieve the desired permeability.
The top soils used in the soil columns represented common agricultural disposal en-
vironments; sampJes were obtained in the field according to the desired classification and
the local in-situ locations were established from the USDA-Soil Conservation Service
report Soils of the Malibu Area. Silty clay loam from the Castaic series was selected for
the silty loam test soil type. Clay from the Cropley series was used for the clay loam test
soil, and very fine sandy loam from the Huerhuero series for the sandy loam test soil.
Table 37 shows the soil characteristics and Figure 23 indicates the locations from which
these representative soil samples were obtained.
The silty and clay loams were admixed with *60 mesh silica sand to achieve satis-
factory leachate drainage. A 4:1 sand-to-soil mixture by weight was used. The clean
silica sand admixtures were used as a permeable, relatively inert "filler," which allowed
leachate movement through the simulated sub-surface environment.
The sanitary landfill materials were mixed according to the refuse percentages shown
in Table 38, following typical "as disposed " quantities. The "as mixed" percentages
varied slightly, and are shown in Table 39.
Column Filling
The columns were filled with materials to simulate various strata in the quantities
shown in Table 40 and according to the depths established during the literature search
(Figures 15 to 21). Care was taken to add the bottom pea gravel layer slowly to avoid
damage to the columns' bottom filter and screen. Column interface level depths were
measured with a weighted string held from the top or through an observation port. The
placed layers were checked to ensure that there was a level thickness from the center of
the column to the circumference.
During column filling the leachate collection lysimeters were placed as shown in
Figure24, with the lysimeter generally located in the layer above the collection tube open-
ing. Filling of material was stopped just below the opening and the lysimeter lowered on a
nylon string. The tube was threaded through the hole, and a rubber stopper was placed on
the tube and secured in the hole. The height of the lysimeter was adjusted with the string
which was then tied to a bar across the top of the column. Column filling was then
resumed. When the lysimeters were covered to a depth of 15 cm or more, the string was
cut.
75
-------
TABLE 37. TEST COLUMN SOILS CHARACTERISTICS
Series
Horizon (cm)
Characteristics
Castaic A Dry color grayish-brown or light brownish-gray to
Clay 0-25 light yellowish-brown or light olive-brown.
Loam Textures are silty clay loam. Noncalcareous with
Soil reactions from slightly acid to moderately alkaline.
Moderate fine granular structure; hard, sticky,
and plastic.
B Dry color very pale brown or pale yellow to yellow
25-71 and light olive brown. Textures similar to horizon
A with up to 30 percent (by volume) shale fragments.
Calcereous with reactions from neutral to moderately
alkaline. Weak fine granular structure; hard, sticky,
and plastic.
Cropley A Dry color of dark gray and very dark gray. Tex-
Silty loam 0-36 tures of clay to silty clay. Reaction is neutral to
Soil mildly alkaline. Medium angular blocky structure;
very hard, very sticky, and very plastic.
B Colors are dark gray, gray, dark grayish-brown,
36 - 96 grayish-brown, olive-brown, and yellowish-brown.
Texture ranges from clay to clay loam. Calcareous
in the lower section, with reaction from mildly to
moderately alkaline. Coarse angular Wocky struc*
ture; very hard, very sticky, and very plastic.
Huerhuero
Sandy loam
Soil
A Colors are grayish-brown, light brownish-gray,
0-10 pale brown, and brown. Textures are fine sandy
loam to loam. Reaction is medium acid to neutral.
Fine granular massive structure; slightly hard, non-
sticky and non-plastic.
B Colors are dark brown, dark yellowish-brown, brown
10-64 and strong brown. Texture is sandy clay to clay,
with up to 15 percent gravels in the lower portion.
Reaction is neutral to moderately alkaline and cal-
careous in the lower portion. Medium to coarse
angular blocky structure; very hard, slightly sticky,
and slightly plastic.
76
-------
' "Source:"
PA CI^IC O CEA N
i i
LFGEND
1 J Clay loam
Sandy loam
Silly loam
0.5 1.0km
Scale* 7.7 cm = 1.0 km
1 cm = 0.13 km
Figure 23. Original location of representative soil samples.
77
-------
TABLE 38, ESTIMATED RESIDENTIAL AND COMMERCIAL SOLID WASTE GENERATION
— UJ IXIINL-/ v^r iv\f* I CM/-VI — MIMIJ rnv juii\.. i .-tunny. r v.^irvnv
Product Source Categories ,
"As Generated" Basis (kkg x 10 )
Materials C _ «
O JJ
Z •<
Paper 9.3
Glass
Metals
Ferrous —
Aluminum
Other non-ferrous
Plastics tr
Rubber and leather
Textiles tr
Wood
Non-.food product 9.3
52 ?
a> .£
C CD
'•§"8 1
§° 1
u °-
18.5
10.1
5.5
4.9
0.5
0.1
2.3
tr
tr
1.6
38.0
V) 4A f-
~O
-------
Product Source Categories ,
"As Generated" Basis (kkg x 10 )
Materials
Food waste
Product totals
Yard waste
Miscellaneous
inorganics
Total waste
i.il s 1 ,
§• o ,E .c o> o
D_ u) t! D"" 3 *Z3
i/i v O •*- C -* ^
£ 0 S> CD U ^
u
c
a
"oL
Q.
Furniture
and
Furnishings
Clothing and
Footwear
As
-------
TABLE 39. SANITARY LANDFILL TEST COLUMN-AS,MLXED_
Materials
Percent
Description
Paper
Glass
Metals
Plastics
8.39
2.27
2.15
0.86
Rubber and Leather
Textiles
0.59
0.23
Wood 0.77
Non-Food Product Total 15.26
Food Waste 3.18
Product Total 18.44
Yard Waste 3.40
Miscellaneous Inorganics 0.39
Total 22.23
37.7 Shredded newspaper and shredded
paper.
10.2 Broken bottles, colored and clear.
9.7 Cut-up tin cans,
cans and cut wire.
3.9 Shredded plastic trash bags and
miscellaneous plastics from trash.
2.7 Cut-up shoes.
1.0 Shredded drapes and rags.
3.5 Cut-up wood crates.
68.7
14.3 Miscellaneous household food
15.3 Miscellaneous yard waste.
1.7 River gravel and silica sand.
100.0
80
-------
TABLE 40. MATERIALS IN TEST COLUMN LAYERS BY WEIGHT
00
Column Layers in . .
Oj r AJ-I'J.' Limestone
rder of Addition _
Quarry
Pea gravel (.95 cm)
Pea gravel (.64cm) 12.2°
Silica sand #1 6 5.4
Silica sand #60 27.2
Clay: #60 sand 1:4 22.2
Limestone 50.3
Dolomite
Granite p-gravel: decomposed
granite 3:1
Silica sand #16
Silica sand #60 4.1
Clay: #60 sand 1 :4
Solid waste
Bituminous coal
Soil horizon B
Soil horizon A
Silica sand #16
Average Weight
Dolomite Ocean
Quarry Disposal
12.2° 12.2°
5.4 5.4
27.2 97.7
22.2
43.1
4.1
per Layer
Sanitary
Landfill
12.2°
5.4
34.9
6.4
16.8
14.1
12.2
8.2
by Column Type (kg)
Coal Sandy Clay Loam: Silty Loam
Mine Loam sand 1:4 sand 1:3
11.3 11.3 11.3
12.2° 6.4 6.4 6.8
5.4
13.2
25.9
4.1
23.6
17.2
80.5 88.9 76.9
17.9 15.0 12.5
5.4
Columns 21-30 contain 6.8 kg of 0.95 cm gravel covered by 5.4 kg of 0.64 cm gravel.
-------
Lysimeter
Tube
Leachate
Bottom
Drain Collection
Bucket
Collection Flask
1/4" Polyethelene Tubing
Y Connector
To Vacuum Pump
Moisture Trap
Figure 24, . Typical test column leachate collection system schematic.
82
-------
For the soils tett columns, the leachate lysimeters were left attached to the string
for several days while the columns were washed with tap water and the simulated strata
compacted. A detailed diagram of the lysimeter construction and placement is given in
Figure 24. After filling the test columns, the external leachafe collection tubing and
flasks, connectors and manifold were added, as shown in Figure.25.
Sample Bottle Labeling
Each lysimeter had its own sample collection flask, labeled with the appropriate
identifying column number and lysimeter letter. All lysimeters, drains, and columns were
identified sequentially from the bottom of the column up, starting with A as the bottom
drain for all the columns. Leachate sample collection bottles were placed and labeled
as follows in the typical example:
Column number, column abbreviation, lysimeter letter, and lysimeter location =
2 LQ-C-top lysimeter
Column Washing
Before adding the residues, the strata materials in each column were leached with
tap water to ensure washed compacted strata and to establish the base-line column leachafe
quality and flow quantity. Tap water was added daily for at least two weeks, or until the
chemical analysis revealed a nearly constant or zero level of leached constituents. Results
of the baseline analyses are given in Figures 32 - 196. To determine the flow rate
characteristics of each column, the drains were kept open for two days until there was no
further leachate flow into the drain. 7.6 liters of tap water were added at the top, and the
rate of water leached for each time period was measured over a period of 27 to 30 hours.
In column 14, the residue solidified, in situ, and the water was perched over the top layers.
This column was repacked with a sand mixture to eliminate the percolation obstruction.
All the columns were successful in percolating water. The column percolation data are
shown in Figures 26-30 . Analyses of fresh and sea water used for column washing are
shown in Tables41 and42 . Reduction in percolation rates occurred over the 15 months of
leaching.
Residue Preparation and Addition
In laboratory studies, it was found that when some residues reacted with water, a large
amount of heat was released. To avoid heat damage to the columns, weighed amounts of
residues were first placed in an inert container to which water had been added so as to
slake and dissipate the heat of reaction. Filter paper (20.3 cm diameter, *1 qualitative)
was placed in the columns above the stratum materials before residue addition. The amounts
of fluidized-bed combustion residues added to each column are shown on Table 43 ,
83
-------
"ۥ
i
Figure 25 . Outdoor columns (eachate sampling apparatus.
84
-------
7500 -
7000 -
6500 -
6000 -
5500 -
5000 -
5 4500 -
V.
0>
| 4000 -
Cfc.
O
I* 3500 -
o
° 3000 -
2500 -
2000 -
1500 -
1000 -
500
3 after
residue added
I I I I I I I I I I
200 400 600 800 1000 1200 1400 1600 1800 2000
Time (minutes)
Figure 26 . Drainage through limestone quarry columns.
85
-------
7500 -
7000 -
6500 -
6000
5500
5000
5 4500
i_
o
S 4000 -J
•I" 3500
3000 ~
2500 -
2000 -
1500 -
1000 -
500
' ' //
\ I /
\ \ :
' / J
•' / //
1 / ••
f '• /
• it /
/ f /
i /
1 1/
>f
nt
'dJ
Legend
Column
A
^«- ~» ««• «M* •«• «•• — — y
0
9
Number
fter residue
added
ITII I I i 1 T7I
200 400 600 800 1000 1200 1400 1600 1800 2000
Time (minutes)
Figure 27 . Drainage through dolomite quarry columns.
86
-------
7500 -
7000 -
6500 -
6000 -
5500 -
5000 -
5f 4500 -
i_
-------
Legend
0>
"6
7500
7000
6500
6000
5500
5000
4500
4000
Column Number
£ 3500
o
° 3000
2500
2000
1500
1000
500
I I I I i I i I 1 I
200 400 600 800 1000 1200 1400 1600 1800 2000
Time (minutes)
Figure 29 • Drainage through coal mine columns.
-------
7500 -•
7000 -
6500 -
.»•
• •
x
X"
^
1
«*-
O
X
•4—
o
3
6000 -
5500 -
5000 -
4500 -
4000 -
3500 -
3000 -
2500 -
•
2000 -
1500 -
•
1000 -
1
XX ' -^
' / ' /'
• / / /
/ ///
i ///
! /// ^-^
•'/// /x
// / X
// / /
. / /
1 / '
' /
I/ /
1 / / Legend
I-* m Column Number
t/ / 1
'/ / 18
I/ .!
/
• ««
/ 20
f
/ . i r, • i
y 1 .. . . . i atf.er residue
•If added
/
t i./
500" f fir
LJf
o
200 400 600 800 1000 1200 1400 1600 1800 2000
Time (minutes)
Figure 30 . Drainage through ocean disposal columns.
89
-------
TABLE 41 . COMPLETE
ANALYSIS OF LOS ANGELES OWENS RIVER AQUEDUCT
(FRESH WATER) COLUMNS TEST
Analysis 1975-1976 Averages
Spec. El ec. Cond.
(Kxl06)
TDR (Calc.)
Total Hardness (CaCOg)
Color (apparent)
Turbidity (units)
Temperature (°C )
pH
Saturation index
Stability index
Calcium
Magnesium
Sodium
Potassium
Alkalinity (CaCO3)
Sulfate
Chloride
Nitrate (NO3)
Boron
Carbon dioxide
Fluoride
Iron
Oxygen (dissolved)
Silica
BOD5
COD
Nitrogen, TKN (as N)
Nitrogen (ammonia)
Nitrogen (nitrite)
Nitrogen (nitrate)
299
184
79
8
3.2
14.5
7.95
-0.30
8.55
24
5.0
30
32
109
20
13
0.8
0.34
3
0.52
0.09
8.9
22
1.7
4
0.10
<0.01
<0.001
0.18
Analysis
Aluminum
Antimony
Arsenic
Barium
Bismuth
Bromide
Cadmium
Chromium
Copper
Cyanide
Detergents (MBAS)
Gallium
Iodide
Lead
Manganese
Mercury
Molybdenum
Nickel
Phenol
Phosphate (PO4)
Selenium
Silver
Tin
Titanium
Tungsten
Vanadium
Zinc
Zirconium
1975- 1976 Averages0
0.07
<0.01
0.02
0.1
0.003
<0.1
<0.002
0.01
0.06
<0.01
<0.05
<0.0002.
0.01
0.01
<0.01
<0.0001
0.005
<0.0009
<0.001
0.16
<0.002
<0.02
0.0005
0.002
<0.07
0.002
0.01
<0.0003
Chemical results m mg/l, except as noted.
bTotal dissolved residue = Anions + Cations + COg + HCOl/2 + SiO .
Source: 185.
90
-------
TABLE 42. SEA WATER ANALYSIS
A. GENERAL: DITMAR'S VALVES FOR THE MAJOR CONSTITUENTS, 1940
(Values in. Grams Per Kilogram. /100)
Constituent
1940 Valves
Cl = 19
Chlorine
Bromine
Sulfate
Carbonate
Bicarbonate
Fluorine
Boric Acid
Magnesium
Calcium
Strontium
Potassium
Sodium
Total
18.980
0.065
2.649
0.071
0.14
0.001
0.026
1.272
0.400
0.013
0.380
10.556
34.553
55.04
0.19
7.68
0.21
0.41
0.00
0.07
3.69
1.16
0.04
1.10
30.61
B. PARTIAL ANALYSES OF COLUMNS TEST SEA WATFR
1975-1976 Averages
Constituent
Sulfate
Iron
Zinc
Nickel
Mercury
Lead
Cl = 19°/00
.0032
.00052
.00003
.001
.0000105
.00044
%
.00931
.0015
.0001
.003
.00003
.0013
1
Source 190.
91
-------
TABLE 43. RESIDUES ADDED TO COLUMNS
Residue Type
Quantify Added
(kg)
Remarks
Pope, Evans, & Robbins
Virginia Fly Ash
Pope, Evans, & Robbins
Virginia Spent Bed Material
9.07
13.61
slaked with 3.81 water over
two days.
unslaked weight.
Exxon Miniplant
New Jersey Fly Ash
13.61
Exxon Miniplant
New Jersey Spent Bed Material 9.98
Esso Gasifier Plant
England Fly Ash 11.34
Esso Gasifier Plant
England Spent Bed Material 6.35
unslaked weight.
slaked with 7.6 I water over
two days, slaked (dry) weight,
Equivalent unslaked weight,
8.7 kg.
slaked with 3.8 I water over
one day, unslaked weight.
slaked with 3.8 I over one
day, unslaked weight.
92
-------
Water Addition
Tri-weekly (every Monday, Wednesday, and Friday afternoons), potable water was
added to all columns, except for the ocean disposal columns which received sea water.
All clamps on drains were closed before the fresh or sea water was added, and the water
was retained in the columns through the next sampling day. Ideally, 7.6 liters of water
were added each time. However, some columns gradually reduced their drainage after
several months so that they received less than 7.6 liters at the top of the column. Pro-
cedures for the sea water columns were changed after six months to investigate leaching
in a flooded environment; i.e., the sea water columns were kept saturated except for
partial surface drainage which allowed the addition of fresh sea water. The purpose of
the flooding test was to simulate the addition of a residual landfill into an ocean environ-
ment rather than in the former tidal prism environment.
Leachate Sampling
Leachate samples from the column drains and lysimeters were collected to measure
the results of the previous day's water addition. See Table 44 for discussion of ocean
water test column procedures. Every Monday morning, sampling was started after emptying
the lysimeter collection flasks containing weekend drainage. With a vacuum pump set at
a vacuum of about 1,760 cm of water, 5 to 6 hours of collecting time normally provided
sufficient sample for analysis. All column lysimeters were sampled simultaneously using
the interconnected tubing and flask systems linked to the vacuum pump (See Figure 24 above).
After the vacuum pump was started, a collection container was placed beneath each
drain tube and the drain valve was opened. At the end of the day, the amount collected
in the container was noted and the sample was taken. Equal amounts of daily samples were
composited to make up one weekly sample of 250 ml. If there was insufficient sample at the
end of the day, pumping was maintained until the amount needed for analysis was obtained.
After sampling all outlet valves for the leachate, drains were closed to prepare for the next
water addition.
Next, the leachate containers were rinsed clean with tap water to avoid contamination
of the next sample. Notes were made in a daily log regarding routine activities or varia-
tions in the usual procedures and noted observations.
Leachate Analysis
The composite samples were analyzed for pH, sulfate, chloride, iron,zinc,
nickel, lead, specific conductivity, and total dissolved solids. During the first 25 weeks
of column operation, weekly composites were analyzed; thereafter, the frequency of labora-
tory analysis was reduced to once for each two-week period, and after 32 weeks, to once
for each four-week period. See Tables 45 through 51 for results of these analyses and
drinking water standards. Figures 31 through 159 give results of studies of leachate versus
total volume of water applied. Figures 31 through 143 also show the total grams of consti-
tuents in the columns before the leachate sampling was initiated. Figures 160 - 176
illustrate the change in pH with the total volume of water applied.
93
-------
TABLE 44. PROCEDURE FOR SAMPLING AND FILLING THE FLOODED
OCEAN WATER TEST COLUMNS
1. Filled columns initially with ocean water.
2. Collected leachate samples from opened lysimeters per original procedure (at 8:00 A.M.
on Monday, Wednesday, and Friday).
3. Closed leachate lysimeter valves at 9:00 A.M.
4. Shut off the leachate valves which provided sufficient sampling amounts.
5. In the afternoon, refilled the column with the same amount of ocean water as was
gravity or vacuum leached.
6. All other routine compositing and analytical procedures were maintained. '
94
-------
TABLE 45 . CONSTITUENT REMOVAL BY OCEAN DISPOSAL COLUMN STRATA
Column Layer
Column 1
Water
Residue
Sandstone
(Upper)
Sandstone
(Lower)
Drain
Column 18
Water
Residue
Sandstone
(Upper)
Sandstone
(Lower)
Drain
Column 19
Water
Residue
Sandstone
(Upper)
Sandstone
(Lower)
Drain
Column 20
Water
Residue
Sandstone
(Upper)
Sandstone
(Lower)
Drain
Sulfate
ga %b
1100
360
360
360
100
1100
1000
1000
1000
100
1100
370
370
370
100
1100
850
850
850
100
Iron
g %
0.540
0.950
0.950
0.500 47
53
0.540
0.740
0.740
0.180 76
24
0.540
0.270
0.270
0.240 11
89
0.540
0.220
0.220
0.220 47
53
Zinc
g %
0.052
0.052
0.032 38
0.032
62
0.052
0.052
0.052
0.052
100
0.052
0.052
0.052
0.052 28
72
0.052
0.047
0.047
0.034 28
62
Nickel
g %
0.700
0.700
0.350 50
0.350
50
0.700
0.700
0.700
0.700
100
0.700
0.700
0.550 21
0.550
79
0.700
0.700
0.550 50
0.550
50
Mercury
g %
1.500
1.500
1.500
1.500
100
1.500
1.500
1.500
1.500
100
1.500
1.500
1.500
--
1.500
100
1.500
1.500
1.500
1.500
100
Lead
g %
0.750
0.440
0.440
0.440
0.750
0.220
0.220
0.220
0.750
0.150
0.150
0.150
0.750
0.150
0.150
0.150
100
100
100
100
ag = Grams of constituent in leachate leaving column layer (or applied in tap water).
k%= Percent removal of constituent in leachate from residue layer.
95
-------
TABLE 46. . CONSTITUENT REMOVAL BY LIMESTONE QUARRY COLUMN STRATA
Sulfate
Column Layer"
ga %b
Column 2
Water
Residue
Limestone
Claystone
Sandstone
Drain
Lysimeter loss
Column 3
Water
Residue
Limestone
Claystone
Sandstone
Drain
Column 4
Water
Residue
Limestone
Claystone
Sandstone
Drain
Column 5
Water
Residue
Limestone
Claystone
Sandstone
Drain
10
450
130 71
100 7
100
22
10
375
220 41
170 13
170
46
10
330
280 15
280
280
85
10
310
220 29
170 16
170
55
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
—
Iron
g %
.055
.055
.028 49
.028
.028
51
.055
.055
.045 18
.045
.045
82
.055
.055
.027 51
.027
.027
49
.055
.055
.025 55
.025
.025
45
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Zinc
g %
.002
.027
.018 33
.018
.018
67
.002
.013
.007 46
.007
.007
54
.002
.019
.009 53
.009
.009
47
.002
.013
.007 46
.007
.007
54
Nickel
g %
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
000
070
045 36
025 -c
025
9
55
000
084
040 52
040
040
48
000
104
05448
054
054
52
000
104
050 52
050
050
48
Msrcury
g %
0.000
0.130
0.130
0.130
OclSO
0.000
0.225
0.225
0.225
0.225
0.000
0.370
0.370
0.270
0.270
0.000
0.190
0.190
0.190
0.190
0
0
0
0
0
100
0
0
0
0
0
100
0
0
0
37 o
0
63
0
0
0
0
0
100
Lead
g %
.000
.042
.042
.028
.028
.000
.035
.035
.035
.035
.000
.026
.026
.026
.026
.000
.032
.032
.032
.032
33
67
100
100
100
°g = Grams of constituent in leachate leaving column layer (or applied in tap water).
"%= Percent removal of constituent in leachate from residue layer.
c = Difference in quantities is due to removal of constituent in lysimeter leachate,
not in column material.
96
-------
TABLE 47. CONSTITUENT REMOVAL BY DOLOMITE QUARRY COLUMN STRATA
Column Layer
Column 6
Water
Residue
Dolomite
Claystone
Sandstone
Drain
Lysimeter loss
Column 7
Water
Residue
Dolomite
Claystone
Sandstone
Drain
Column 8
Water
Residue
Dolomite
Claystone
Sandstone
Drain
Column 9
Water
Residue
Dolomite
Claystone
Sandstone
Drain
Sulfate
ga %b
10
380
200
200
200
10
420
320
180
180
10
360
300
250
250
10
300
150
150
150
47
53
24
33
43
17
14
69
50
50
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Iron
g %
.055
.055
.045 18
.045
.045
82
.055
.055
.038 31
.038
.038
69
.055
.055
.044 20
.044
.044
80
.055
.055
.044 20
.044
.044
80
Zinc
g %
0.003
0.038
0.029
0.017
0.012
0.003
0.023
0.013
0.007
0.007
0.003
0.018
0.007
0.005
0.005
0.003
0.019
0.008
0.008
0.008
24
21
32
23
43
26
31
61
11
28
58
42
g
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
Nickel
%
000
103
03368
033
033
32
000
070
036 49
036
036
51
000
104
Q. 042 40
0.
0.
0.
0.
042
042
60
000
104
0.047 55
0.
0.
047
047
45
Mercury
g %
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
000
145
145
145
145
100
000
500
500
190 62
190
38
000
270
0.270
0,
0.
0.
0.
0.
0.
0.
,240 11
240
89
000
180
180
140 22
140
78
Lead
g %
0.000
0.056
0.056
0.056
0.056
100
.
0.000
0.050
0.050
0.050
0.050
100
0.000
0.036
0.036
0.025 31
0.025
69
0.000
0.018
0.018
O.Ofl 39
0.011
61
Grams of constituent in leachate leaving column layer (or applied in tap water),
= Percent removal of constituent in leachate from residue layer.
Difference in quantities is due to removal of constituent in lysimeter leachate,
not in column material.
97
-------
CONSTITUENT REM(
COLUMN STRATA
Column Layer
Column 10
Water
Residue
Landfill
Claystone
Granite
Drain
Column 1 1
Water
Residue
Landfill
Claystone
Granite
Drain
Lysimeter loss
Column 12
Water
Residue
Landfill
Claystone
Granite
Drain
Lysimeter loss
Column 13
Water
Residue
Landfill
Claystone
Granite
Drain
Sulfate Iron Zinc
ga °/J> g % g %
10
330
50
50
50
10
370
160
135
135
10
440
120
75
75
10
470
50
50
50
85
15
57
36
7
73
6
17
4
89
11
0.0025
0.0045
0.0045
0.0045
0.0045
100
0.0025
0.022
0.022
0.018 18
0.018
82
0.0025
0.007
0.007
0.006 14
0.006
86
0.0025
0.008
0.008 38
0.005
0.005 25
37
Nickel
g %
0.000
0.105
0.032 70
0.024 8
0.024
22
0.000
0.105
0.050 52
0.040 10
0.040
38
0.00
0.10
0.06 40
0.040C
0.040
27
33
0.0025
0.065
0.042 20
0.035 11
0.035
69
Mercury
g %
0.000
0.125
0.125
0.095 24
0.095
76
0.000
0200
0.200
0.150 25
0.150
75
0.00
0.275
0.275
0275
0.275
100
0.000
0.165
0.165
0.125 24
0.125
76
Lead
g %
0.000
0.018
0.018
0.013 28
0.013
72
0.000
0.070
0.070
0.054 23
0.054
77
0.000
0290
0.290
0.190 34
0.190
66
0.000
0.019
0.0195
0.0105 41
0.0105
59
ag = Grams of constituent in leachate leaving column layer (or applied in tap water).
°% = Percent removal of constituent in leachate from residue layer.
c = Difference in quantities is due to removal of constituent in lysimeter leachate, not
in column material.
98
-------
Column Layer
Column 14
Water
Residue
Bitum. coal
Claystone
Limestone
Sandstone
Drain
Lysimeter loss
Column 15
Water
Residue
Bitum. coal
Claystone
Limestone
Sandstone
Drain
Lysimeter loss
Column 16
Water
Residue
Bitum. coal
Claystone
Limestone
Sandstone
Drain
Column 17
Water
Residue
Bitum. coal
Claystone
Limestone
Sandstone
JDrain
Sulfate
a b
g %
5
370
180
115
115
115
5
450
225
180
125
125
5
350
250
250
250
250
5
300
200
200
200
200
51
18
31
50
10
12
28
29
Iron
g %
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.055
.055
.035 36
.035
.035
.035
64
.055
.055
.023 58
.023
.023
.023
42
.055
.055
.030 45
.030 '
0,030
71
33
67
0
0
0
0
0
0
0
.030
55
.055
.055
.022 60
.022
.022
.022
40
Zinc
g %
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
003
020
020
020
012 40
012
60
003
023
023
Oil 52
004 30
004
18
003
026
026
026
007 73
007
27
003
018
018
018
005 72
005
2$
WW/^U-tiQlLXi.
Nickel
g %
0.000
0.104
0.038
0.038
0.026
0.026
0.000
0.070
0.042
0.042
0.028
0.028
0.000
0.103
0.048
0.048
0.038
0.038
0.000
0.102
0.080
0.080
0.040
0.040
63
12
25
40
20
40
53
10
37
22
39
39
-\*vuuixu3-3,
Mercury
g %
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.000
.190
.190
.080 58
.080
.080
42
.000
.125
J25
.090 28
.090
,090
72
.000
.135
.135
.110 19
.110
.110
81
.000
.180
.180
.150 17
.150
.150
83
JKMIM
Lead
g %
0.000
0.075
0.075
0.048 36
0.034 8
0.028 — c
35
21
0.000
0.033
0.033
0.033
0.022 33
0.011 **
33
33
0.000
Oj024
0.024
0.024
0.013 46
0.013
54
0.000
0.023
0.023
0.023
0.020 13
0.020
87
ag = Grams of constituent in leachate leaving column layer (or applied in tap water).
b % = Percent removal of constituent in leachate from residue layer.
c = Difference in quantities is due to removal of constituent in lysimeter leachate,not in
column material.
-------
TABLE 50 . EPA PROPOSED REGULATIONS ON INTERIM
PRIMARY DRINKING WATER STANDARDS, 1975
Constituent or characteristic
Value
Reason for standard
Physical
Turbidity, units
Chemical, mg/l
Arsenic
Barium
Cadmium
Carbon chloroform extract
Chromium,hexavalent
Cyanide
Fluoride
Lead
Mercury
Nitrates as N
Selenium
Silver
Bacteriological
Total coliform, per 100 ml
0.05
1.0
0.01
0.7
0.05
0.2 ,
1.4-2 A
0.05
0.002
10
0.01
0.05
Aestheti c
Toxic
Toxic
Toxic
Toxic
Toxic
Toxic
Toxic
Toxic
Toxic
Toxic
Toxic
Cosmetic
Disease
Pesticides, mg/I
Chlordane
Endrin
Heptachlor
Heptachlor epoxide
Lindane
Methoxychlor
Toxaphene
2,4-D
2,4,5-TP
0.003
0.0002
0.0001
0.0001
0.004
0.1
0.005
0.1
0.01
Toxic
Toxic
Toxic
Toxic
Toxic
Toxic
Toxic
Toxic
Five mg/l may be substituted if it can be demonstrated that it does not interfere with
.disinfection.
Dspendent upon temperature: higher limits for lower temperatures.
Source: 162.
100
-------
TABLE 51 . SURFACE WATER CRITERIA FOR PUBLIC WATER SUPPLIES
Constituent or characteristic
Microbiological:
Total col i form
Fecal colifonn
Inorganic chemicals: (mg/l)
Ammonia
Arsenic
Barium
Boron
Cadmium
Chloride
Chromium, hexavalent
Copper
Dissolved oxygen
Iron (filterable)
Lead
Manganese (filterable)
Nitrates plus nitrite
pH (range)
Selenium
Silver
Sulfate
Total dissolved solids
(filterable residue)
Uranyl ion
Zinc
Organic chemicals: (mg/l)
Carbon chloroform extract (CCE)
Cyanide
Methyl ene blue active substances
Oil and grease
Pesticides:
Aldrin
Chlordane
DDT
Dieldrin
Endrin
Heprachlor
Heptachlor epoxide
Lindane
Methoxychlor
Permissible criteria
1
10, 000/1 00 ml
2, 000/1 00 ml1
0.5 (as N)
0.05
1.0
1.0
0.01
250
0.05
1.0
4 (monthly mean)
3 (individual sample)
0.3
0.05
0.05
10 (as N)
5.0-8.5
0.01
0.05
250
500
5
5
0.15
0.20
0.5
Virtually absent
0.017
0.003
0.042
0.017
0.001
0.018
0.018
0.056
0.035
(continued)
101
Desirable criteria
i
100/1 00 ml
20/1 00 ml'
0.01
Absent
do
do
do
25
Absent
Virtually absent
Near saturation
Virtually absent
Absent
do
Virtually absent
Narrative
Absent
do
50
200
Absent
Virtually absent
0.04
Absent
Virtually absent
Absent
do
do
do
do
do
do
do
do
do
-------
TABLE 51 (continued)
Constituent or characteristic Permissible criteria Desirable criteria
f-
Organic chemicals:
Pesticides: (Cont.)
Organic phosphates plus carbamates
Toxaphene
Herbicides:
2,4-D plus 2,4,5-T,plus 2,4,5-TP
Phenols
Radioactivity:
Gross beta
Radium-226
Strontium-90
2
o.r
0.005
0.1
0.001
1,000
3
10
do
do
do
do
100
1
2
Microbiological limits are monthly aruithmetic averages based upon an adequate number
of samples. Total coliform limit may be relaxed if fecal coliform concentration does not
exceed the specified limit.
2
As parathion in cholinesterase inhibition, it may be necessary to resort to even lower
concentrations for some compounds or mixtures.
Source: 72.
102
-------
-10
11
20
21
[30
,50
Influent (Water or Sea Water)
Residue
Lysfmeter Leachate
-^(Columns 10-13)
Lysimeter Leachate
(Columns 2-17)
Lysimeter Leachate
(Columns 1-20)
j 51 Drain Leachate
00 - Baseline leachate = column drainage without residue
Figure 3]. Legend of typical columns for Figures 32 through 176.
103
-------
30
i
u
1 20
"o
10
Total Cf
Figure 32 so
Column 2
Limestone •_
NJSBM i 20
/ 10,11,20,21, 30,31,40,41 j?
O
10
00
200 400 600 800 1,000 1,200 1,400
-Total Cl _„ 00
Figure °y
Column 3
Limestone
VSBM
.10,20,21,30,31,40,41
- /
S r , , nA lit.
200 400 600 800 1,000 1,200 1,400
Total omount of water applied and leached (1) ,..,,,,„,
Total amount of water applied and leached (1)
30
O .
•*"• u
i/i
| 20
D)
i.
10
Figure 34
-To'Qlcf Column 4
... 30
Limestone
NJFA
u
I 20
10,11,20,21,30,31,40,41 ~
jS 10
/ 00
Figure 35
-Tofal cf Column 5.
Limestone
VFA
.
10,11,20,21,30,31,40,41
- /
/, ^^
200 400 600 300 1,000 1,200 1,400
Totol amount of woter cppliod gnd leached (I)
Note; See Figure 3] for further legend explanation.
200 400 600 803 1,000 1,200 1,400
Totol amount of wafer applied and Uached (I)
Figures 32 ~ 35 , Test column leachate cumulative balances: Chloride.
-------
o
Oi
u
i
I
Figure 36
Column 6
Dolomite
VSBM
10,20,21,30,31,40,4V
200
Total CI
400 600 800 1,000 1,200 1,400
Total amount1 of water applied and leached (1)
,10,20,21,30,31,40,41
Figure 38
ColumnS
Dolomite
VSBM
oo
200 400 600 600 1,000 1,200 1,400
Total amount of water cpplted and loathed (I)
15
u
I10
0)
Jotal Cf
15 -
10 -
200
Total C!
Figure 37
Column 7
Dolomite
NJSBM
.10,20,21,30,31,40,41
00
400 600 BOO 1,000 1,200 1,400
Total amount' of water applied and leached (I)
Figure 39
Column 9
Dolomite
VFA
710,20,21,30,31,40,41
00
-1.
JL
J_
_L
200 400 600 800 1,000 1,200 1,400
Total amount of water applied and leachcJ (I)
Note; See Figure 31 for further legend explanation.
Figures 36 - 39 , Test column leachate cumulative balances; Chloride.
-------
O
O
i
6
o
vt
O
"5
"o
10,20,21,30,31,4(0,41
Figure 40
Column 10
Landfill
VFA
oo
200 400 600 800 1,000 1,200 1,400
Total amount of wator applied and leached (I)
10,20,21,30,31,40,41
Figure 42
Column 12
Landfill.
NJFA
200 400 600 800 1,000 1,200 1,400
Total amount of water applied and leached 0)
10
o
I
15
n 10
o
10,20,21,30,31,40,41
Figure 41
Column 11
Landfill
VSBM
oo
200 400 600 800 1,000 1,200 1,400
Total amount of water applied and leached (I)
10,20,21,30,31,40,41
Figure 43
Column 13
Landfill
NJSBM
200 400 600 800 1,000 1,200 1,400
Total cmouc.t of watec applied end leaehed (!)
Note; See Figure 31 for further legend explanation.
Figures 40-43, Test column leachate cumulative balances: Chloride.
-------
30
U
E
I20
z
o
10
Total Cl
30
U
S 20
u>
"5
•5
10
Total C!
200
30
Figure 44
Column 14 <_
Coal mine g 20
VSBM |
o
10,20,21,30,31,40,41,50,51
10
00
•^4 I-TT- 1 1 1 I.I
400 600 800 1,000 1,200 1,400
_ Total Cl"
Figure 45
Column 15
Coal mine
NJSBM
10,20,21,30,31,40,41,50,51
/
^
^_ -M ,
200 400 £00 800 1,C€3 1,200 1,400
Total amount of woter epplied and leached (1) Toha! amounf of wafer ^P1^ ond leac*led (1)
Figure 46 3Q
Column 16
Coal mine •_.
NJFA »
S20
10,20,21,30,31,40,41,50,51 |
v' »S
10
I ',.,1,00 , iiij
400 600 800 1,000 1,200 1,400
jotai ci" Figure 47
Column 17
Coal mine
VFA
10,20,21,30,31,40,41,50,51
200 400 600 BOO 1,000 1,200 1,400 "
Total amount of water applied end leached (I)
Total amount of water applied and leacVied (I)
Note: See Figure 31 for further legend explanation.
Figures 44-47 . Test column leachate cumulative balances: Chloride.
-------
o
00
0.15
2 0.10
0.05
Total F« I99g
0.15
0.10
0.05
Total Fe 950g
Figure 48
Column 2
Limestone
10,20 NJSBM
21,30,31,40,41
00
_L
200 400 600 800 1,000 1,200 1,400
Total amount of water applied and leached (I)
10,20
21,30,31,40,41
Figure 50
Column 4
Limestone
NJFA
200 400 600 800 1,000 1,200 1,400
Total amount of water applied and leached (I)
Note; See Figure 31 for further legend explanation.
0.15
S 0.10
G>
0.05
Total Fe 128g
0.15
I °-10
,2
0.05
_Total Fe 996g
Figure 49
Column 3
Limestone
10'20 VSBM
21,30,31,40,41,50,51
JL
200 400
600 800 1,000 1,200 1,400
Total amount of water applied and leached (I)
Figure 51
Column 5
Limestone
10,20
21,30,31,40,41
200 400 600 800 1,000 1,200 1,400
Total amount of water applied and leached 0}
Figures 48 -51 . Test column Ieachate cumulative balances: Iron.
-------
0.3
£.
I
I 0.2
"s
a
H-
0.1
Total Fe 128g
Figure 52
Column 6
Dolomite
VSBM
10,20
.^^' 21,30,31,40,41
200 400 600 800 1
Total amount of water
0.15
V
U-
fe 0.10
~Q
3
0.05
.Total Fe 950g
10,20
/ .21,30,31,40,41
// Figure 54
// Column 8
// Dolomite
// NJFA
f i ,1 - °° -
200 400 600 800 1
,000 1,200 1,400
applied and leached (!)
,000 1,200 1,400
0.15
6
s o.io
0.05
Jotal Fe 199g
0.151 Total Fe 96g
0.10
O.C5
Figure 53
0,20 Column 7
Dolomite
NJSBM
21,30,31,40,41
., 00
200 400
600 800 1,000 1,200 1,400
Total amount of wafer applied and leached (I)
10,20
21,30,31,40,41
Figure 55
Column 9
Dolomite
VFA
oo
Total amount of water applied and leached (I)
200 400 600 800 1,000 1,200 1,400
Total amount of water applied and leached (I)
.Note: See Figure 31 for further legend explanation.
Figures 52 - 55 . Test column leachate cumulative balances; Iron.
-------
0.3
£ 0.2
0.1
Total Fa 128g
Figure 56
Column 14
Coal mine
VSBM
10,20
21,30,31,40,41,50,51
00
0.15
0.10
0.05
200
_Total Fa 950g
400 600 800 1,000 1,200 1,400
Total amount of water applied and leached (I)
Figure 58
Column 16
Coal mine
10.20 NJFA
200 400 600 800 1,000 1,200 , 1,400
Total amount of water applied anel leached (I)
0.15
0.1
2
o
0.05
Total Fa 1998
£
o
0.15
0.10
0.05
200
Total Fa 96g
Figure 57
Column 15
10,20 Coal mine
NJSBM
20,21,30,31,40,41,50,51
00
400 600 800 1,000 1,200 1,400
Total amount of water applied and leached (1)
Figure 59
Column 17
Coal mine
10,20
VFA
200 400 600 800 1,000 1,200 1,400
Total cunovnt of water applied and lecwhad (t)
Note: See Figure 31 for further legend explanation.
Figures 56 - 59 , Test column leachate cumulative balances: Iron,
-------
3.0
2.0
O
£
1.0
Total Fa 123 g
1.5
O
1
i.o
0.5
20,21,30
Figure 60
Column 1
Ocean
VSBM
200 400
Total Fs 199 g
600 SCO V,000 1,200 1,400
Total orr.ounr of water applied and leached (!)
Figure 62
Column 19
Ocean
NJSBM
20,21,30
200 400 600 800 1,000 1,200 1,400
Total amount of water applied and leached (I)
1.5
1.0
O
0.5
Total Fe 950 g
1.5
1.0
I
0.5
20,21,30
200 400
Total Fe 926 g
Figure 61
Column 18
Ocean
NJFA
600 800 1,000 1,200 1,400
Tetal amount of vrtrter applied end leached (1)
Figure 63
Column 20
Ocean
VFA
200 400 600 800 1,000 1,200 1,400
Total cmounr of water applied and leach&d (I)
Note: See Figure 31 for further legend explanation.
Figures 60 - 63 . Test column leachate cumulative balances: Iron.
-------
0.06
i
0 0.04
1
0.02
Total Pb 0.4 g
x 20, 21, 30
/ Figure 64 °-w
/ Column 2 ^
/ Limestone » o 04
/ NJSBM |
//31, 40,41
// °-02
f 00,10
Total Pb<0.453g
20,21,30,40,41 . ,_
/Figure 65
Column 5
Limestone
VFA
i mJ10 i r t t
""20"' 400 600 800 lW 1,'aOO •!% »JO 400 600 SOO 1,000 1,200 1,400
Total amount of water typllcd and leached (!) Tota! amount of water °PfUe
-------
20,21,30,31,40,41
Figure 68
Column 6
Dolomite
VSBM
0.06
£
E
0.04
0.02
Total Pb 0.544g
20,21,30
31,40,41
Figure 70
Column 8
Dolomite
NJFA
200 400 600 800 1,000 1,200 1,400
Total amount of water applied and leached (I)
0.15
£
*A
1 0.10
"5
0.05
600 600 1,000 1,200 1,400
Total amount of watar applied ond leached (I)
-Total Pb 0.4 9
0.06
£
°> 0.04
I
0.02
200
Total Pb 0.453g
20,21,30,31,40,41
Figure 69
Column 7
Dolomite
NJSBM
00,10
600 800 1,000 1,200 1,400
Tofol amount of water applied and leachea* (!)
Figure 71
Column 9
Dolomite
20,21,30 VFA
200 400 600 SOO 1,000 1,200 1,400
Total amount of wat«r applied and leached (I)
Note; See Figure 31 for further legend explanation.
Figures 68 - 71 . Test column leachate cumulative balances: Lead,
-------
0.03
0.02
0.01
Total Pb 0.453g
Figure 72
Column 10
Landfill
VFA
50.10
_L
0.3
£
I
*P
•5
0.2
0.1
200 400
Total Pb 0.544
20,21,30
1,40,41
_L
_L
600 800 1,000 1,200 1,400
Total amount of water applied end Uoched (I)
Figure 74
Column 12
Landfill
NJFA
. 00.10
600 800 1,000 1,200 1,400
Tofal omovnt of water applied jond.leached (I)
0.10 -
0.05
Total Pb 0.68g
Figure 73
Column 11
Landfill
VSBM
200 400 600 800 1,000 1,200 1,400
Total amount of water applied and leached (I)
O
0.03
0.02
0.01
Total Pb 0.4 g
20,21,30
11,40,41
Figure 75
Column 13
Landfill
NJSBM
j_
2CO 400 600 SCO 1,000 1,200 1,4CO
Total amount of water applied and leached (1)
Note: See Figure 31 for further legend explanation,
Figures 72 - 75 . Test column leachate cumulative balances: Lead.
-------
0.15
£ 0.10
i
o
"5
*~ 0.05
Total Pb 0.68 g _. —,
Figure 76
Column 14
Coalmine °-°°
VSBM \
§
-20,21,30 <5 0.04
f 1
" -//t^ °'°2
^^X><50,51
KS 00,10
Totol Pb 0.4 g
Figure 77
Column 15
Coal mine
20,21,30,31,40 NJSBM
/
/
/'/41, 50,51
//
/S 00,10
200 400 600 800 1,000 1,200 1,400 200 400 600 300 1,000 1,200 1,400
Total amount of wafer applied and leeched (1) Total amount of water applied and leached (1)
0.03
£
J0.02
"75
&
0.01
Total Pb0.5449 F19Ur6 78
Column 16
Coal mine
10 ir A °'°0
NJFA
X20,21, 30,31,40 £
- f | °'04
/ 1
/ --41,50,51 (2
~ If 0.02
{^_ , J10'10 ,
Total Pb 0.45 g Figure 79
Column 17
Coal mine
VFA
^^20,21,30,31,40
/^-~" 41 ,50, 51
f 00,10
200 400 600 800 1,000 1,200 1,400
Total amount of water applied and leached (I)
200 400 600 £00 1,000 1,200 1,<00
Total amount of water applied and leached (I)
Note: See Figure 31 for further legend explanation.
Figures 76 - 79 . Test column leachate cumulative balances« Lead.
-------
CS
1.5
Q_
in
£
O 1 *0
O)
"a
"o
t—
0.5
0.6
£
g
o
01 0.4
1
0.2
- Total Pb 0.68 g r. __ 1.5
Figure 80
Column 1
Ocean t
VSflM g,1'0
20,21,30,31 -
jr t-
er °PPlied and Ie0ched (l)
Total Pfa0.4g
Figure 82
Column 19
Ocean °-6
NJSBM i
i
o 0.4
20,21,30,31 5
/^TO °'2
Total Pb0.4533
Figure 83
Column 20
Ocean
VFA
_
20,21,30,31
^"*f^ i OCl i i i i
200 400 600 800 1,000 1,200 1,400
Total omount of wafer applied and leached (I)
200 400 600 800 1,000 1,200 1,400
Total amount of water applied and ieacfied fl)
Note: See Figure 31 for further legend explanation,
Figures 80- 83 , Test column leachate cumulative balances; Lead,
-------
0.3
I 0.2
I
0.1
Total Is unknown
Figure 84
Column 2
Limestone
NJSBM
21,3031,40,41
,-00-lQ I L
J_
JL
0.3
Z
,0.2
0.1
Total is unknown
200 400 600 800 1,000 1,200 1,400
Total amount of .water applied and leached (1)
Figure 86
Column 4
Limestone
NJFA
1,30,31,40,41
, 00,10 ,
200 400 600 800 1,000 1,200 1.4CC
Total amount oF water applied and leached (I)
Note: See Figure 31. for Further legend explanation.
0.3
k> 0.2
0.1
Total It unknown
Figure 85
Column 3
Limestone
VSBM
21,30,31,40,41
00,10
0.3 -
Z
a
I °'2
0.1
200 400
Total is unknown
600 800 1,000 1,200 1,400
Total amount of water applied and leeched (I)
Figure 87
Column 5
Limestone
VFA
21,30,31,40,41
200 400 600 800 1,000 !,200 1,4CC
Total amount of water applied ant/ leached (I)
Figures 84 - 87, jest column ieachate cumulative balances: Nickel.
-------
0.15
0
~o
'5
0.10
0.05
Total Is unknown
20
Figure 88
Column 6
Dolomite
VSBM
21,30,31,40,41
00,10
200 400 600 800 1,000 1,200 1,400
Total amount of water applied and (cached (I)
0.15
w
I 0.10
o
o
0.05
Total Ni
20
Figure 89
Column 7
Dolomite
NJSBM
21,30,31,40,41
_L
i
100 400 600 800 1,000 1,200 1,400
Total amount of water applied and leodud (I)
00
0.15
0.10
0.05
Total Is unknown
Figure 90
Column 8
Dolomite
NJFA
21,30,31,40,41
00,10
200 400 600 ""800" 1,000 1,200 1,400
Total amount of water applied and leached (I)
0.15
0.10
0.05
Total it unknown
Figure 91
Column 9
Dolomite
VFA
21,30,31,40,41
00,10,
200 400 600 800 1,000 1,200 1,400
Total amount of water applied and leached (I)
Note: See Figure 31 For further legend explanation,
Figures 88 - 91. Test column leachate cumulative balances: Nickel.
-------
•o
Figure 92
Column 10
Landfill
VFA
, 40, 41 ,50,51
00,10
°-3 -
0.1
200
Total is unknown
-l_
600 800 1,000 1,200 1,400
Total amount of water applied and leeched (I)
Figure 94
Column 12
Landfill
NJFA
21, 30,31 ,40,41
00, 10
200 400 600 800 1,000 1,200 1,400
Total amount of water applied and Uached (I)
0.3
\
I
0'2
0.!
Total Ii unknown
0.10-
Figure 93.
Column 1 1
Landfill
VSBM
200 400
Total Nt
600 800 1,000 1,200 1,400
Total amount of water applied and leached (I)
20
31, 40,41
Figure ?5
Column 13
Landfill
NJSBM
00,10
200 400 600 800 1,000 1,200 1,400
Total amount of water applied and leached (I)
Note : See Figure 31 for further legend explanation.
Figures 92-95. Test column leachate cumulative balances: Nickel,
-------
0.15
o> 0.10
0.05
Total Is unknown
20
Total Is unknown
Figure 96
Column 14
Coal mine
VSBM
JXi.i 10
JL.
_L
200 400
600 800 1,000 1,200 1,400
Total amount of water applied and leached (I)
0.15
0.10
0.02
- Total Nt
20
Figure 98
Column 16
Coal mine
NJFA
200 400 600 800 1,000 1,200 1,400
Totql amount of water applied and leached (I)
0.15
0.15
Figure 97
Column 15
Coal mine
NJSBM
21,30,31,40
5W.\ 10 i
200 400 600 800 1,000 1,200 1,400
Total amount of water applied and leached (I)
21,30,31,40
Figure 99
Column 17
Coal mine
OC,10
200
600 800 1,000 1,200 1,406
Total amount of water applied and leached (I)
Note: See Figure 31 for further legend explanation.
Figures 96 - 99. Test column leachate cumulative balances: Nickel,
-------
3 ~
1 -
0
Total Ni 3
Figure 100
Column 1
Ocean z
VSBM I
o
I
*~ i
^^^^--—'20,21,30,31
200 400 600 300 1,000 1,200 1,400
Total amount of voter applied and leached (1)
Total It unknown
Figure 102 3
Column 19
Ocean ~
NJSBM | 2
0
"o
f.
.,, 20,21,30,31 1
^^^^ . 00. ,
200 400 600 800 1,OCO 1,200 1,400
Total is unknown
Figure 101
Column 18
Ocean
S 20,21,30,31
;S
S/
^-^^l
200 400 600 800 1,000 1,200 1,400
Total amount of water applied and leached (1)
Total Is unknown _. • no
Figure lOo
Column 20
Ocean
VFA
^- 20,21,30,31
^^•^^^^
1 -
Total amount of water applied and leeched (!)
230 400 600 800 1,COO 1,20C 1,400
Total amount of wa»er applied end leached (I)
Note: See Figure 31 for further legend explanation,
Figures 100-103, Test column leachate cumulative balances: Nickel.
-------
to
NJ
600
8
CA
J400
o
o
200
Tt>tolSO4't200g
20 Figure 104
Column 2
Limestone
NJSBM
200 400 600 800 1,000 1,200 1,400
Totol amount of water applied and leached (!)
Total SO4 953 g
Figure 106
Column 4
Limestone
NJFA
200 400 600 SOO 1,000 1,200 1,400
Total amount of water applied and leached (I)
300
200
100
600
o*
IS)
| 400
200
Total SO4 3344 g
20 Figure 105
Column 3
Limestone
VSBM
400
21,30
600 800 1,000 1,200 1,400
Total amount of water applied and leached (1)
Total SO4 499g
Figure 107
20 Column 5
Limestone
VFA
'31,40,41
10
00,
200 400 600 800 1,000 1,200 1,400
Total amount of wars' applied ant) leached (I)
Note: See Figure 31 for further legend explanation.
Figures 104-107. Test column leachate cumulative balances: Sulfate.
-------
CO
1500
"
•a
t2 500
1,500
•»
X
I i.oco
^*
p
6
500-
Total SO° 3,3448
Figure 108
Column 6
Dolomite
VSBM
s 20
/
/ ^> 21,30,31,40,41
^•^_._, _ 1_— i i i i i
200 400 600 800 1,000 1,200 1,400
Total amount of water applied and leached (1)
Total SO° 953g
4 Figure 110
Column 8
Dolomite
NJFA
20
J/
XX1' 30
X^VW. 41
Xfl .. , _»00'«> ,
1,500
"sT
1 i,coo
1
1
500
600
8
E
e 400
en
^
l2
200
Jofo! SO^ 1,200g
Figure ]Q9
Column 7
Dolomite
20 NJSBM
200 400 600 300 1,000 1,200 1,400
Total amount of water applied and leached (I)
Note: See Figure 31 for further legend explanation.
00,10
200 400 600 800 1,000 1,200 1,400
Total amount of vrater applied and leeched (I)
Total S0° 493g
Figure Ill-
Column 9
,JO Dolomite
VFA
200 400 600 600 1,000 1,200 1,400
Total amount of woter applied and leached (\)
Figures 108-111,. Test column leachate cumulative balances: Sulfate.
-------
K)
600
2 400
200 -
Totol SO* 499g
Figure 112
Column 10
Landfill
VFA
—21,30,31,40,41,50,51 10
1 ' i- i i, , -,r
200 400 600 800 1,000 1,200 1,400
Total amount of water applied end leached (I)
Total SO^ 953g
Figure 114
Column 12
Landfill
NJFA
io00
i J=r ss =& uu
200 400 600 800 1,000 1,200 1,400
Total amount of water applied and leachad (I)
Note: See Figure 31 for further legend explanation.
Total SO 3,344g
Figure 113
Column 11
Landfill
VSBM
.200 -
i i
200 400 600 800 1,000 1,200 1,4
Total amount of water applied and leached (I)
600 -
s
§> 400
200
Total SOj l,200g
Figure 115
Column 13
Landfill
NJSBM
21,30,31,40,41
-L_u^_—=1™-- = = == ^e 00
200 400 600 SCO 1,000 1,200 1,400
Total amount of water applied and leached (I)
Figures 112-115, Test column leachate cumulative balances: Sulfate,
-------
NJ
Ol
Total SO~ 3,344g
300
"o*
8 200
O
I
100
Figure. 116
Column 14
Coal mine
VSBM
200 400 600 800 1,000 1,200 1,400
Totol omount of water applied and leeched (I)
20
n 16
Coal mine
NJFA
21,30,31,40,41,50,51
00,10
200
4CO 600
800
1,000 1,200 1,400
Total amounrof water cppllod and leoehcd (I)
Note: See Figure 31 for further legend explanation.
300
'sT
200
100
300
20°
100
Total SO4 l,200g
20
Figure H7
Column 15
Coal mine
NJSBM
00,10
400
600 800 1,000 1,200 1,400
Total cmounf of water applied and leached (I)
20
Total SOT 499 g
4 Figure 119
Column 17
Coal mine
VFA
21,30,31,40,41,50
400
600 300 1,000 1,200 1,400
Total amount of water opplled and leeched (!)
Figures 116 - 119. Test column leachate cumulative balances: Sulfate.
-------
1500 -
Total SO4 3,344g
10
20,21,30,31
Figure 120
Column 1
Ocean
VSBM
00
200 400 600 800 1,000 " 1,200 1,400
Total amount ef water applied and leached (I)
P
o
1500
1000
500
Total S04l,200g
•10
Figure 122
Column 19
Ocean
NJSBM
20,21,30,31
00 .
200 400 600 800 1,000 1,200 1,400
Total amount of water applied and leached (I)
1500 -
Total SO4- 953 g
20,21,30,31
Figure 121
Column 18
Ocean
NJFA
200 400 6CO 800 1,000 1,200 1,400
Total amount of water applied end leoched (I)
1500 • -
•6*
1000
a
1
500
20,21>30,31
Figure 123
Column 20
Ocean
VFA
400
600 800 I.,000 1,200 1,400
Total amount of water oppltod and leached fl}
Note: See Figure 31 for further legend explanation.
Figures 120 - 123, Test column leachate cumulative balances: Sulfate.
-------
o
•
0.06
0.04
0.62
Total Zn 0.53 g
20
Figure 124
"21 Column 6
Dolomite
VSBM
200 400
0.06
0.02
Total Zn 0.82 g
600 800 1,000 1,200 1,400
Total amount of water applied and leached (I)
Figure 126
Column 8
Dolomite
NJFA
200 400
1,400
600 800 T7000 1,200
Toto) amount of water applied and leached (I)
0.06
S 0.04
O
0.02
Total Zn 4.7 g
0.06
5 0.04
0.02
200
Total Zn 0.735 g
Figure 125
Column 7
Dolomite
NJSBM
400 600 800 1,000 1,200 1,400
Total amount of water applied and leocheo' (i)
Figure 127
Column 9
Dolomite
VFA
21,30,31,40,41
0
200
800 1,000 1,200 1,400
Total amount of water applied end leached (I)
Note: See Figure 31 for further legend explanation.
Figures 124 - 127. Test column leachate cumulative balances: Zinc.
-------
to
00
0.03
c
N
g
ro 0.02
o
i—
0.01
0.06
c
N
a
J> O.C4
"3
i2
0.02
Total Zn 0.735 g - _- . ..
Figure 1*0 "•'J
Column 10
Landfill N
VFA | o.io
"5
~ j°
0.05
-
20,21,30,31,40,41,50,51
2
0.01
20,21,30
^*~Z*~~~ 11 i^ft i fC\ — C0,10
^•s;^ i i i \ i
Total Zn 0.53g
Figure 129
Column 1 1
Landfill
vsm
«
20,21,30
• ' ij i in 11
^ZZ^^W M/10
s^~-—l 1 i 111!
200 400 600 800 1,000 1,200 1,400
Total amount of water applied and leached (1)
Total Zn 4.7g
Figure 131
Column 13
Landfill
NJSBM
-
^20,21,30
-X^«- 31 -j°^_^io
/^^^^^^==^~"^
J»i^s!ga^T i 1 ' T i . — 1 — ^ 1 !_
200 400 600 600 1,000 1,200 1,400
Total amount of water applied and leached (I)
200 400 600 800
Total amount of water applied and leached (1)
Note; See Figure 3V for further legend explanation.
Figures 128 - 131. Test column I each ate cumulative balances: Zinc,
-------
s>
S3
0.06
"5
i
O 0.04
2
,2
0.02
Total Zn 4.7 g
Figure 1 32
Column 2
Limestone °-°6
NJSBM £
,20 1
/ 0 °.°4
// x-21, 30,31,40,41 |
/ S 0.02
x ^^*
XX 10
r. rrt-— — ~~lT~00 1 tit!
200 400 600 800 1,000 1,200 1,400
Total Zn 0.58 g
Figure 133
Column 3
Limestone
VSBM
-. 20
^^^\_^— - 21 ,30,31 ,40,41
^^-'^~^-— ?JT10
200 400 600 800 1,000 1,200 l,4uO
Total amount of water applied and leached (1) ^ ^^ ftf ^^ ^.^ and |Mehcd fl)
0.06
iQ
I 0.04
o
1
0.02
Total Zn 0.82 g
Figure 134
Column 4 o.o6
Limestone ,5
NJFA 1
& 0.04
"o
°
jr 0,02
x/ ^x'2'.3°.3'i'«5,41
./^^^^ 10
Total Zn 0.735g
Figure 135
Column 5
Limestone
VFA
-
J»
^^^21,30,31,40,41
^ -10
<^~*~r^i r M l 1 (10 i i i i i
^ *fif-.. '.T1 r?r ^ Ar.-~ -T ' „ T^SR. 200 400 6co aoo 1,000 1,200 1,00
200 400 600 800 1,000 1,200 1,400
Total amount of water applied and leached (I)
Note; See Figure 31 for further legend explanation.
Total amount of water applied and leached (I)
Figures 132 - 135, jest column leachate cumulative balances: Zinc,
-------
0.06
i5
$ 0.04
~
£
0.02
c 0.06
N
!£ 0.04
o
3
0.02
Total Zn 0.58g
Figure 136
Column 14 0 04
Coal mine
VSBM I
J 0.04
1
^•20,21,30,31,40 Q>02
/\^>~ 41 ,50,51
200 400 600 800 1,000 1,200 1,400
Total amount of water applied and leached (1)
Total Zn 4.7 9
Figure 137
Column 15
Coal mine
NJSBM
-
f 20,21,30
- /
X^^Sl^-p--10 .
'HjorTi39 , Test column leachate cumulative balances:Zinc.
-------
0.3
(5 0.2
i
o
"o
"o
" 0.1
Total Zn 0.58 g
0.4
Figure 140
Column 1
Ccean fi 0.3
VSBM §
^ 20,21 2
X^ 1 0.2
^X"^ ,2
s^^ 30,31
x<^-^^^^ o.i
^^\ , 00 , i i 1
200 400 6CO 300 1,000 1,200 1,400
T«*«i nmntmf t\f \wnfc1" acolied ond leached (1)
Total Zn 0.82 g r. « j»
H Figure 141
Column 18
Ocean
N1FA
^^ 20,21,30,31
^^^-^"^
^^^^
^^^ 10
' .11 .••riWri i -!„ 1 00 , . .'
lOTQl QTuOUnr Oi wcic* 4^»j*nvw wn« t*.™^ — \ i — — • -^ ^~*m^m^^^^^^
200 400 600 300 1,000 1,200 1,400
0.3
*o.i
O
"5
.2
0.1
_ Total Zn 4.7 g
Figure 142
Column 19
Ocean ,g Q ,
NJSBM 1
o
M.
^X 20,21,30,31 1
^X^^
^X^"^ 0-05
^'^———2 oo
r^Tr -TTV^n...-^ ._sa=i 1 1 I t
200 400 600 800 1,000 1,200 1,400
T**-t — *....* _(.,._.. » !! i i i i i m
Total amount of water applied and leached 0)
Total Zn 0.735 g
Figure 143
Column 20
Ocean
VFA
/20,21
/
// 30,31
.^^ — 10
•" -'• ' , rri *" l i j ,
200 4°0 600 800 1,000 1,200 1,400
Total amount of water implied and leached (I)
Total amount of water applied and leeched (I)
Note:, See Figure 31 for further legend explanation.
Figures 140-143. Test column leachate cumulative balances: Zinc.
-------
4000
3000
o
_3
u 2000
•
00
1000
O 21 (S.C. = 8,500) Figure 144
O 31 /41 Column 2
Limestone
1
f
I
i
a
cu
fr
200 400 600 800
Volume of Wafer Applied (lifers)
1000
- 3
- 2
4000
^ 3000
o
_Q
E
^ 2000
u
i/»
1000
Figure 145
Column 3
Limestone __
-
— —
— «.
— —
1 ! 1 ! I f ! f I r I
8.
ft-
- 1
200
400
600
800
1000
Volume of Wafer Applied (liters)
NOTE: See Figure 31 for further legend explanation.
Figures 144 and 145, Specific conductivity and total dissolved solids of leachate from
Columns 2 and 3 - Limestone quarry.
ir?
-------
4000
-£ 3000
o
"i
^ 2000
u
u-.
1000
_ Figure 146 —
Column 4
__ Limestone •__
_
,21
-
j *\.
A -
i/ \ '
J \^41
-^
•* * ^**
_ . —
200 400 600 800 1000
3
o1
o_
VI
t/t
O
<
2 1
El
to
^
1
Volume of Water Applied (liters)
4000
>« 3000
o
~i
3.
~ 2000
u
in
1000
Figure 147
Column 5
,_ Limestone _
,21
'
" /31
- / _
/ /\
- LS \
\41
I 1 1 1 I ! ! 1 ! 1 1
200 400 600 800 1000
3
o1
si
a
4
§L
tf
HI
^
I ~
Volume of Water Applied
NOTE: See Figure 31 for further legend explanation.
Figures 146 and 147. Specific conductivity and total dissolved solids of leachate from
Columns 4 and 5 - Limestone quarry.
133
-------
4000
,_^
"> 3000
J§
H
^i
U 2000
to
1000
Figure 148 ~
' Column 6
- Dolomite' —
- —
A/41
IV
1
' 031
— —
—
1 I 1 1 1 ! 1 ! ! 1 1
3
•H
O
cf
H
<"
2 8.
£.
al
t/>
S
1
200 400 600 800 1000
Volume of Wafer Applied (liters)
9000
8000
7000
^6000
£
"> 5000
Jg
E
a 4000
u
to* 300°
2000
1000
\/21 Figure 149
"~ Column 7
y Dolomite ~
/
/
_
«•
—
XV41
X
^
«•
o 31
l*J v 1
I 1 1 I 1 ! 1 I 1 I 1
5
g
«L
4|
a.
3 ^
51
in
{Q*
2 o
1
200 400 600 800 1000
Volume of Water Applied (liters)
NOTE: See Figure 31 for further legend explanation.
Figures 148and 149. Specific conductivity and total dissolved solids of leachate from
Columns 6 and 7 - Dolomite quarry.
134
-------
4000
^
< 3000
(/>
JB
3:
"7 2000
u
t/1
1000
4000
,| 3000
1
^ 2000
U
1000
Figure 150 —
Column 8
- Dolomite: —
fl\
\/TV.4I
-•• —
i i i i i i i i I r !
200 400 600 800 1000
Volume of Water Applied (liters)
- Figure 151 "~
Column 9
- Dolomite —
- ' —
MM ^"
- -
_. _
/21
- n /
J^\
i f '"n 1^1 i i i i r i
200 400 600 800 1000
3
o
ff
0
in
O
2 i
51
>
1
3
£
D
VI
2 1
51
^
, ^
Volume of Water Applied (liters)
NOTE: See Figure 31 for further legend explanation.
Figures 150 and!51 . Specific conductivity and total dissolved solids of leachafe from
Columns 8 and 9 - Dolomite quarry.
135
-------
4000
"i"
o
E 3000
=3.
(J
v>" 2000
1000
4000
-f 3000
51
e
u
w 2000
1000
Figure 152
Column 10
~" Sanitary landfill
_ —
~ ""
^™ • ^"«
-31 — 21
1 1 1-1 1 1 1 I ! | 1
200 400 600 800 1000
Volume of Water Applied (liters)
Figure 153
Column 1 1
"~ Sanitary landfill "~
_ —
-.
51
1 i i i i i i i i f i
200 400 600 800 1000
3
o
£L,
Dissolved
CN
to
~
I
3
0*
•M*
2 j?
i
o_
?
1 ^17
Volume of Water Applied (liters)
NOTE: See Figure 31 for further legend explanation.
Figures 152 and 153 . Specific conductivity and total dissolved solids of leachate from
Columns 10 and 11 - Sanitary landfill.
136
-------
4000
1=
"| 3000
E
4 2000
00
1000
*~ Figure 154
Column 12
~~ Sanitary landfill ~
— ••
31
1
- I
V
_\51 2"
i i i i i i i I 1 ' f
3
sL
o
i.
?
i ~
4,000
J3,000
CO
^
E
2,000
VJ
1,000
200 400 600 800
Volume of Water Applied (liters)
Figure 155
Column 13
Sanitary landfill
1000
8.
o
2 r
a.
CO
200 400 600 800 1,000
Volume of Water Applied (liters)
NOTE: See Figure 31 for further legend explanation.
Figures 154 and 155. Specific conductivity and total dissolved solids of leachate from
Columns 12 and 13- Sanitary landfill.
137
-------
4000
§ 3000
^V^
trt
"i
a.
~ 2000
u
in
1000
~ Figure 156 ""
Column 14
Coal mine ""
„_
-
O31
21 ©
A51'41
I 1 1 I 1 1 1 ! 1 ! !
3
— i
cT
i.
in*
2 1
ft
Q_
£
El
t»
_
1 *"""*
4000
,0 3000
I
3.
T 2000
1000
200 400 600 800
Volume of Water Applied (liters)
Figure 157
Column 15
Coal mine
1000
J I
I
I
I
o
3-
2
' (A
8
CD
a.
200 400 600 800
Volume of Water Applied (liters)
NOTE: See Figure 31 for further legend explanation.
Figures 156 and 157. Specific conductivity and total dissolved solids of leachate from
Columns 14 and 15 - Coal mine.
138
-------
4000
IT
< 3000
J?
•-U
£
a.
~ 2000
u
t
tn
1000
Figure 158
Column 1 6
- Coal mine -1
—
031
MB M^
^™ •»
A
- \ /JU41 H
\^\
^51
—
! 1 1 ! 1 ! ! 1 1 i !
3
c^
S1
LJ
O
»•
VI
8
9 <
*• n>
a.
^
ol
to
to"
1 "
200 400 600 800
8000
7000
--6000
J 5000
34000
u
oo* 3000
2000
1000
0.0
Volume of Water Applied (liters)
Figure 159
Column 17 —
- Coal mine
A ; 31
/
' M
-
-
I
\ V 21
.^^
» i 1 I 51 I i i I I r 1
5.0 5,
ET
40 M*
8
^~
8.
3.0 £
El
u«
20^-
*. 9 W -^
1.0
200 400 600 800 1000
Volume of Water Applied (lifers)
NOTE: See Figure 31 for further legend explanation.
Figures 158 and 159. Specific conductivity and total dissolved solids of leachate from
Columns 16 and 17 - Coal mine.
139
-------
5 L
Figure 160
Column 1
Ocean
200
400
600 800 1,000 1,200
Volume of Water Applied (liters)
Note: See Figure 31 for further legend explanation.
1,400 1,600
Figure 160 o pH of leachate from Column 1 -Ocean.
-------
Figure 161
Column 2
Limestone
51
200 400 600
Volume of Water Applied (liters)
NOTE: See Figure 31 for further legend explanation.
80U
Figure 162
Column 3
Limestone
6
5
A
-
_.
I t t 1 1 t 1 1
Volume of Water Applied (liters)
Figures 161 and 162. pH of leachate from Columns 2 and 3 - Limestone quarry,
-------
S3
Figure 163
Column 4
Limestone
00,10
200 400 600 800
Volume of Water Applied (liters)
NOTE: See Figure 31 for further legend explanation.
13
12
11
10
5. 8
7
6
5
4
Figure 164
Column 5
Limestone
41
00,10
200 400 600 800
Volume of Water Applied (liters)
Figures 163, and 1.64 . pH of leachate from Columns 4 and 5 - Limestone quarry,
-------
CO
Figure 165
Column 6
Dolomite
200 400 600 800
Volume of Water Applied (liters)
NOTE: See Figure 31 for further legend explanation
Figure 166
Column 7
Dolomite
200 400 600
Volume of Water Applied (liters)
800
Figures 165 and 166. pH of leachate from Columns 6 and 7 - Dolomite qua-ry.
-------
13
12
11
10
Figure 167
Column 8
Dolomite
11
00710
200 400 600
Volume of Water Applied (liters)
NOTE: See Figure 31 for further legend explanation.
800
Figure 168
Column 9
Dolomite
13
12
11
10
9
o. 8
7
6
5
A
-, 11
- A
• /w"
MA
fN Jf V,,
^^^~"_J 00,10
-
-
1 ! I t 1 1 1 1
Volume of Water Applied (liters)
Figures 167 and 168, pH of leachate from Columns 8 and 9 - Dolomite quarry.
-------
.Figure 169
Column 10
Figure 170
Column 11
13
12
11
10
9
8
7
6
5
4
banitary landfill
13
12
11
10
9
^ 41 8
/-x^X^-31 a
—£ 5|
/ 00,10
-^ 6
5
i i i i i i r 1 4 . • •
Sanitary lanarm
-
-
-
«.
nn 1 r»
-—• UU, I U
*~ ^^-" — 51,41,31
^21
i i i I t i i i
200 400 600 800 " 200 400 600 800
Volume of Water Applied (lifers)
NOTE: See Figure31 further legend explanation.
Volume of Water Applied (liters)
Figures 169 and 170. pH of leachate from Columns 10 and 11 - Sanitary landfill.
-------
13 r-
12
11
10
9
8
6
5 r-
31,21
Figure 171
Column 12
Sanitary landfill
00,10
•51,41
200 400 600 800
Volume of Water Applied (liters)
NOTE: See Figure 31 for further legend explanation,
14
13
12
11
10
9
8
R0ure 172
Column 13
Sanitary landfill
• 11
•00,10
51
/ /
200 400 600 800
Volume of Water Applied (liters)
Figures 171 and 172. pH of leachate from Columns 12 and 13 - Sanitary landfill.
-------
Figure 173
Column 14
Coal mine
200 400 600
Volume of Water Applied (liters)
NOTE: See Figure 31 for further legend explanation.
800
Figure 174
Column 15
Coal mine
200 400 600
Volume of Water Applied (liters)
Figures 173and 174. pH of leachate from Columns Hand 15 - Coal mine.
-------
00
Figure 175
Column 16
Coal mine
13
12
11
10
9
a 8
7
6
5
4
-
• .11
A
-
^
_
/)
//
nl
Ml//
w
n
\
j^fj ^ 21 --31
-
—
i i i \ fiti
200 400 600
Volume of Water Applied (liters)
NOTE: See Figure 31 for further legend explanation.
800
Figure 176
Column 17
Coal mine
11
21
200 400 600
Volume of Water Applied (liters)
Figures 175and 176. pH of leachate from Columns 16 and 17 - Coal mine.
-------
CHAPTER 7
REUSE POTENTIAL FOR FLUIDIZED-BED RESIDUES
Introduction
Coal and oil combustion generate large quantities of residues. In 1972, for example,
approximately 30 million kkg of coal residues were produced. Residue quantities are
projected to increase substantially during the period 1970-90, primarily as a result of
increased power demand. During that period, the electric utility industry is predicted to
increase its consumption of coal by 100 percent and of oil by 150 percent. Residue
quantities are likely to increase more than proportionately for several reasons. First, as
supplies of low-ash fuel are depleted, greater use will be made of higher-ash fuels. Second,
more stringent pollution control regulations will result in fewer emissions to the environment
and therefore greater solid waste process residue quantities. Third, fluidized-bed coal
combustion and oil gasification methods may be adopted by a significant portion of the
industry. Both once-through and regenerative limestone/dolomite fluidized-bed systems
generate substantially more residues than conventional systems, although the increase is
greatest with once-through systems. Preliminary work suggests that once-through systems
are favored by current economics: the projected expense of regeneration (less the value of
recovered sulfur products) appears to be greater than the saving from reduced limestone con-
sumption. For coal boilers, once-through fluidized-bed systems should generate a minimum
of 50 percent more residues than do conventional coal-fired power plants.
This chapter evaluates possible residue application areas and the market prospects for
fluidized-bed residues. The following topics are considered:
• Overall reuse prospects for fluidized-bed residues.
• Review of applications for conventional coal ash and lime/limestone wet scrubber
residues.
• Evaluation of specific, feasible reclamation applications of residues in concrete,
asphalt, agriculture (soil amendment), soil cover (strip mines and landfills), soil
cement, pozzolan cements (LFA and LCFA), acid mine drainage treatment, and
road ice control.
• Preliminary assessment of market potential for residue applications.
Overall Reuse Prospects
The history of reuse for conventional coal ash provides an insight into what the utiliza-
tion prospects for fluidized-bed residues might be. Relatively little of the conventional
ash generated has found its way into productive use—about 16 percent in 1972. Until about
1968, the ash utilization rate had been increasing rapidly, moving from 2 percent in 1955
to 17.5 percent in 1968. Since then, however, the rate has remained relatively constant,
149
-------
although in total quantities reuse has continued to increase. The utilization rate has re-
mained low even though many technically sound applications have been developed which
potentially could absorb more than the annual quantities generated." Table52 presents
estimated maximunvtechnically feasible,utilization potentials. Although many reuse applica-
tions exist, it is not likely that the utilization rate will consume the available supply in the
near future.
Factors other than technical feasibility also influence actual utilization. These factors
include:
• Technical complexity of the application. Potential users are less likely to adopt a
new residue material if it is significantly more complicated, or if it requires major
changes in production methods.
• Reliability of the new raw residue process or product.
* Sufficient information about the potential application.
• Existence of a reliable source of supply for residues or residue-based products.
• Uniformity and quality of the residue or residue-based product.
Given favorable conditions in the above areas, a potential user's decision will be
based on the relative prices of conventional and residue materials, transport, and any
necessary preprocessing of the residues over that required for the competing conventional
material. A potential user will adopt that application which reduces his production costs
and maintains desired product quality.
,v In comparing the magnitude of the technically feasible applications of conventional ash
wfth actual utilization, there are indications of substantial economic and other impediments
to greater increased use. Many of these barriers may be overcome in time, but unless
further reuse incentives are provided, most of the increased residues generated for 1970-90
will not be reused, but instead,will require disposal. This conclusion must be modified for
fluidized-bed residues, however, since their composition and characteristics are substan-
tially different from those of conventional combustion ash residues. This is illustrated in
Tables 53 and 54, which compare the composition of conventional coal ash, modified ash
(MFA), and fluid!zed-bed ash. Lime or dolomite modified fly ash is generated by flue gas
desulfurization (FGD) systems (e.g., wet limestone scrubbers) and fluidized-bed com bus tors.
Since differences affect the suitability of a residue for a given application, it is difficult to
predict the successes or failures of FBC residue applications. The FGD residues (particularly
those from dry systems) are quite similar to fluidized-bed residues. Hence, the reuse poten-
tial of FGD and fluidized-bed residues may be compared with some reliability.
There is considerable literature on applications for residues from conventional caa I
combustion, from municipal waste incineration, and from lime-limestone scrubbing (fre-
quently used for air pollution control on coal-fired generating units). In addition, there is
150
-------
TABLE 52. ESTIMATED ASH UTILIZATION POTENTIAL (10 kkg/yr)
Maximum
Utilization
Use Technically
Feasible
1970
Utilization
Estimated
Utilization
1971
Conditions
Potential
Improved
Utilization
Fly ash concrete (structural,
mass and concrete products) 9-14
Lightweight aggregate 12
Raw material for cement clinker 12
Bricks 9
Filler in bituminous products 1-2
Base stabilizer for roads(^Pa)
Agriculture and land recovery
(AP) —
Control of mine subsidence and > 1
fires
Structural fill for roads
construction sites, land,
0.49
0.19
0.15
0.12
0.10
0.01
AP - annual production.
Source: 130.
3.2
0.5
0.23
0.68
0.3
0.68
5.4
2.7
>0.9
reclamation, etc. (AP)
Others
Total
0.29
0.15
1 .50
0.5
0.23
6.3
151
-------
TABLE 53. COMPARISON OF ASH COMPOSITION (%)
Constituent
Coal
Ash
SiO2 49.10
ALO 16.25
Fe0O_ 22.31
2 3
Ti02
CaO
MgO
Na20
K2O
S03
c
H2O soluble
1.09
4.48
1.00
0.05
1.42
0.73
2.21
2.51
TABLE 54.
Constituent
Fe2°3
CaO
MgO
S03
H2O soluble
Exxon
9
13
0
5
0
Lime Modified Dolomite Modified Lignite Ash
Ash Ash
30.85
13.70
11.59
0.68
33.58
1.49
1.12
0.71
2.20
1.12
22.11
30.81
12.54
10.72
0.42
17.90
14.77
0.72
0*99
8.09
1.76
—
32.60
10.70
10.0
0.56
18.00
7.31
0.87
0.68
2.60
0.11
8.55
COMPARISON OF FBC RESIDUE COMPOSITIONS
Ash Composition (%
Miniplant Pope,Evans and
.99 15.71
.44 4.9
.61 0.32
.81 4.56
.21 0.42
)Q
Robbins Plant
Esso, England
Gasifier
0.02
10.5
0.07
6.22
These values do not sum to 100 percent. The remainder is primarily silicon dioxide with
traces of unburned carbon and metal oxides.
Source: 42.
152
-------
literature for proposed or experimental uses.
Types of Coal Ash
There are three types of residues collected from coal combustion: fly ash, bottom ash,
and slag. Fly ash is the ash collected from the stack effluent; bottom ash and slag are the
residues collected from the bottom of the boiler. Whether these bottom residues are an ash
or a slag depends on the design of the particular boiler. For any specific boiler unit the fly
ash and bottom ash will have a .(similar chemical composition, except that the bottom ash
will be lower in carbon content.
Physically, fly ash consists of finely divided spheroids of siliceous glass ranging from
1 to 50 microns in diameter. Some of these spheroids are considerably finer than portland
cement, and a minor fraction consists of larger, irregularly shaped particles, some opaque
and some transparent or translucent. Carbon is present chiefly in the form of irregularly
shaped particles of coke. Depending upon the type of coal and combustion conditions,
the carbon content of fly josh in the United States ranges from less than 1 to more than 20
percent. The physical and chemical characteristics of fly ash emitted from any combustion
chamber depends on the type of combustion equipment and its design; the combustion or
firing rate; the oxygen ratio, burning characteristics, and particle size of the coal; varia-
tions in steam load, draft, and combustion controls; and operator skill. About 70 percent
of the coal ash residue is collected as fly ash.
The bottom ash is collected either as an ash or slag depending on the particular boiler
design. The ash is grey to black in color, quite angular, and has a porous surface. The
slag particles are normally black, angular particles having a glass appearance. The bottom
ash particles have an average particle diameter size of 2-1/2 millimeters and an average
specific gravity of about 2.5. When there are reuse markets for fly ash, it is handled dry by
a pneumatic system, stored in silos or bins on the plant site, and then transported in closed
tank trucks or rail cars. Slags to be sold are pumped from quench tanks below the boiler
to draining bins and then are generally stored in piles until marketed. Bottom ash and slag
are granular materials and lend themselves to mechanical handling schemes.
Pulverized coal-fired units are "wet" or "dry" bottom, with the amount of fly ash and
bottom residue in each related to furnace design and the pulverization level, volatile
matter, and ash content of the coal. In the wet bottom design, up to half of the total
ash can be trapped within the furnace as ash or slag; however, bottom ash in "dry" bottom
units amounts to only 20-25 percent of the total ash.
Coal Ash Utilization
United States.
Table 55 compares ash generation and use; in 1972 only about 16 percent of the ash
153
-------
en
TABLE 55. COMPARATIVE ASH PRODUCTION AND UTILIZATION, 1966-1972
*°kdkUgC)ti0n 1966 1967 1968 1969 197° 1971 1972
Fly ash 15,533,855 16,701,139 17,974,729 20,234,314 24,074,886 25,175,333 28,855,791
Bottom ash 7,317,065 8,283,915 6,585,446 7,295,595 8,972,920 9,125,341 9,682,256
Boiler slag — — 2,317,466 2,739,954 2,541,455 4,509,421 3,430,664
Total 22,850,920 24,985,053 26,877,641 30,269,863 35,589,261 38,810,095 41,968,711
Utilization
Total (kkg)
Fly ash (%)
Bottom ash (%)
Boiler slag (%)
Total (%)
1966
2,767,520
7.9
21.0
—
12.11
1967
3,442,507
8.2
25.0
—
13.78
1968
4,711,932
9.6
25.0
57.8
17.53
1969
4,814,215
8.13
25.0
57.8
15.90
1970
4,622,704
8.13
18.63
39.06
13
1971
7,805,163
11.7
16.03
75.21
20
1972
6,872,381
11.4
24.3
35.3
16.3
Source:
-------
and slag produced found application (11.4 percent of the fly ash, 24.3 percent of the bottom
ash, and 35.3 percent of the boiler slag). Ash collection and utilization for a typical year
(1971) are shown in Table 56; estimated 1976 ash generation is included for comparison. The
main applications were as an additive to cement, a fill material for road and other construc-
tion, and a filler in asphalt mix. The "miscellaneous" use category was also quite large;
Table 57 lists some of the applications aggregated under that heading. It can be inferred
that a large quantity of residues was removed at no cost to utilities and found its way into
useful applications. Some of these applications (and known quantities) are listed in Table 58.
Yearly fluctuations in coal ash used suggest that the trends are influenced by market
factors; thus, valid projections for future consumption are difficult to make. Boiler slag
has been found useful in increasing the skid resistance of asphalt pavement. The use of coal
ash as a raw material in the manufacture of portland cement is another application where
usage has increased in the past several years. Recent research results indicate that
large quantities of coal ash could also be effectively used for agriculture and land reclama-
tion products. The use of coal ash as a raw material in the manufacture of portland cement
is another application where usage has increased in the past several years. Recent research
results also indicate that large quantities of coal ash could also be effectively used for
agriculture and land reclamation products. The use of coal ash for lightweight aggregate
initially looked promising, but in the last few years its use has;declined.
Effective utilization of coal ash requires that the ash satisfy the technical specifications
for the application and be economically competitive. Ideally, any production or utilization
process should be located close to the source of raw material; that is, at the power plant.
However, this is not always possible. Thus, transporting coal ash to where it is to be used
is a major economic factor. Using trucks, fly ash can be transported from a source at an
average 1976 cost of $0.04 per kkg/km (18 to 27 kkg per truck). The cost of loading and
unloading is about $2.00 per truck load. Furthermore, trucks can be expected to operate
with maximum economy only to a range of about 150 to 175 miles, depending on road con-
ditions. This enables the trucker to get to his destination, unload, and return in the same
day, avoiding any overtime or stayover.
Fly ash used in cement and concrete applications competes with natural raw materials
and cement industry products. Its use is hampered by the fact that 1976 freight rates for
shipping fly ash are about 20 percent higher than for the natural products. This is because
of tariffs that give an advantage to natural or virgin materials over secondary materials.
Europe.
In 1971, the Federal Republic of Germany was using 79 percent of its total ash produc-
tion of 6,500,000 kkg, France was using 65 percent of its production of 4,185.000 kkg, and
the United Kingdom was using 54 percent of its production of 10,370,000 kkg. ^ The prin-
cipal uses of the coal ash were in road construction, compacted concrete, and construction site
fills.
155
-------
Ash utilized:
Mixed with raw material before forming
cement clinker
Mixed with cement clinker or mixed with
cement (pozzolan cement)
Partial replacement of cement
Concrete pjtoducts
Structural concrete
Dams and other massive concrete
Lightweight aggregate
Fill material for roads, construction
sites, etc.
Stabilizer for road bases, parking areas,
etc.
Filler in asphalt mix
Miscellaneous
Total
Ash removed at plant site at no cost to utility
but not covered in categories
listed under "ash utilized"
Total ash utilized
Ash removed to disposal areas at company
Fly Ash (kkg)
94,550
15,001
160,725
1 68,256
64,784
162,294
329,663
33,511
133,953
89,633
1 ,252,370
1 ,698,938
2,951,308
22,224,448
Bottom
Ash (kkg)
NAa
NA
32,094
NA
NA
12,648
484,156
7,149
2,570
431 ,299
969,916
492,514
1,462,430
7,663,065
Boiler
Slag (kkg)
83,440
NA
68,551
NA
NA
NA
2,384,924
44,964
74,118
388,305
3,044,302
346,346
3,390,648
1,117,941
expense
Total ash collected 25,175,756 9,125,495 4,508,589
Estimated 1976 ash production 33,561,352 10,651,580 2,284,060
Not applicable.
Source: 31.
156
-------
TABLE 57. KNOWN MISCELLANEOUS USES FOR ASH AND SLAG
Oil well cementing Oil well drilling
Mine fire control Industrial testing
Mine subsidence control Vanadium recovery
Neutralization of acid mine drainage Ice control
Cleaning abrasive Outdoor school tracks
Spontaneous combustion control Asphalt shingles
Highway bridges Sandblastingg.it
Test caps Filler for glass
Refrectory add mix Filler for fertilizer
Insulating cement Filler for paint
Grouting Filler for plastics
Snow sanding Dike repair and buildings
Pipe coating Drainage filter
Foundries Aggregate
sand Landfill
manufacturer products Agriculture
Chemical products Dust control
Poz-O-Paca Seal coating
Sewage treatment plants (filtration) Roofing granules
Substrate course (heavy construction) Railroad base
Ready mix Mineral wool production
A pozzolan.
Sources: 1,2,4,23,26,29,31,33,34,37,40-42,46,50,53,54,59,68-70,80-82,
96, 101-103,110,111,114,116-118, 126,128-131,139,140,143-154,
167,189.
157
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TABLE 58. KNOWN USES FOR ASH REMOVED FROM PLANT
rvi i>iv^ <-^-J i i^-» .
Application
Manufacturing cement
Mine fire control
Antiskid winter roads
Building blocks and fill material
Experimental soil condition
Miscellaneous fill material
Airport pavement
Soil stabilization
Fertilizer filler
Rubber filler
Vanadium recovery
Dust control
Asphaltic wear course aggregate
Total
J, 1 1 U 1 1 1 f \ II 1
Fly Ash (kkg)
46,900
75,250
NAb
23
433,567
14,697
4,568
1,198
269
181
NAp
NAP
693,916
Bottom Ash
(kkg)
NApa
35,325
161,775
13,373
NAp
31 ,534
NAp
NAp
NAp
NAp
181
10,237
NAp
252,425
Boiler Slag
(kkg)
NAp
NAp
150,714
NAp
NAp
208,105
NAp
NAp
NAp
NAp
NAp
NAp
1,932
360,751
Not applicable.
Not available.
Source; 31.
158
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About 22 percent of the total amount of ash used was employed in road construction,
mainly in France and the United Kingdom. Eighteen percent of the total was used in con-
crete. Construction filler accounted for about 28 percent of the total used. Miscellaneous
uses included coal mine fire control, addition of fly ash to foundry sand, use as a compo-
nent of blasting compounds for cleaning metal surfaces, manufacture of acoustical block,
pesticides, soap, etc. Table 59 gives the figures for hard coal and lignite ash production.
and utilization in Europe and the United States in 1967, 1969, and 1971. Annual fly ash
production in the United Kingdom is approximately 10 million kkg. The low density ash is
useful for road fill, especially when embankments have to be constructed over poor ground
support such as compressible alluvial clay or silt. In such situations, excessive road founda-
tion weight could produce settlement beyond allowable limits and may even produce a com-
plete failure of the subsoil foundations.
In England the wet weight of fly ash per compacted cubic meter is between 1.17 and
1.44 kkg/m depending on the source and moisture content of the material. This compares
"avorably with the weight of traditional (British) fill material. Table 60 gives a comparison
of fly ash densities with other traditional fill materials.
The stability of fly ash is such that it is now being used in Great Britain behind bridge
abutments, etc. Fly ash, being pozzolanic, has both a high angle of shearing resistance
and high cohesion. The relatively high shear strength of fly ash together with its low density
suggests its use as a support .edge for selected filling behind earth retaining structures.
Being both granular and porous, it is also an excellent drainage medium. Because of its
self-hardening properties, there is little settling in the compacted fly ash. Being light and
fine, fly ash can be readily transported without special equipment, even in confined areas.
Fly ash is being used throughout the United Kingdom and other European countries for
load-bearing structural fills at industrial, schools, and other sites since it has excellent load-
bearing and foundation strength. Furthermore, because of its low density and self-harden ing
capacity, fly ash makes an ideal stabilized sub-foundation support for buildings built on un-
stable ground. Because it is self-hardening, fly ash is ideal for trenching, as deep neat
trenches can be excavated using minimal trench supports. An ash fill, after hardening, is
excellent material for trimming and so it is ideal for excavating pad foundations, manholes',
utilities, etc. Small to medium-sized rollers of the vibrating type can compact fly ash
adequately. Ash is inert and alkaline. Although tests have demonstrated few adverse effects
on cast iron, lead,copper, PVC, or glazed stoneware pipes embedded in ash fills, it is im-
portant to remove soluble salts from new ash to prevent electrolytic metal corrosion or water
pollution.
Specific Applications for Coal Ash
This section considers the following specific application areas for coal ash:
• Concrete
• Stabilized bed construction
159
-------
TABLE 59 .DEVELOPMENT OF ASH PRODUCTION AND USE IN THE
Os
o
Ash Source
i
Hard coal
Europe
U. S. A.
Total
Lignite
Europe
U. S. A.
Total
Production
(103 kkg)
27,250
27,500
54,750
21,370
400
21,770
1967
Amount
(103kkg)
12,477
3,744
16,221
1,380
6
1,386
Use
%of
Production
45.3
13.6
29.6
6.4
1.5
6.4
Production
(103 kkg)
35,710
31,661
67,371
23,017
NAb
23,017
1969
Use
Amount % of
(103 kkg) Production
13,630
4,862
18,482
1,278
N A
1,278
34.8
15.3
27.5
5.5
N A
5.5
Production
(103 kkg)
59,922
42,781
102,703
36,353
449
36,802
1971
Use
Amount % of
(103 kkg) Production
15,983
8,604
24,587
1,658
18
1,676
26.7
20.1
23.9
4.6
4.1
4.6
0 The UN Economic Commission for Europe (ECE) is composed of 32 countries in the European geographical region and
the U.S.A. Its purpose is to present economic collaboration among all those countries.
b NA - Not available.
Source: 132.
-------
TABLE 60. DENSITY OF FLY ASH COMPARED WITH TRADITIONAL FILLS
Material Compacted Density
(kkg/cu m)
PFA 1.1 - 1.3
Limestone 1.6-2.0
Burnt colliery shale 1.7 - 2-0
Sand <2.10
Clay <1.77
Hoggin (sand/clay) < 2.14
Chalk <1.75
Source: 137.
161
-------
• Fill material
• Agriculture and reclamation
• Brick manufacture
• Water quality improvement
• Miscellaneous
Current and experimental applications are considered.
Concrete.
The addition of fly ash to concrete can improve its strength, resistance to sulfate
attack, workability, and permeability; it may also help control shrinkage and evolution
of Kent during setting. Fly ash concrete reportedly clings less tenaciously to form and
retains sharper comers and details, thus enhancing the concrete's architectural value.
Fly ash is valuable in cement and concrete primarily because it is a pozzolan.
Pozzolans are siliceous-aluminous materials that have little or no cementitious value
theB»seJves,lxit, in finely divided form and in the presence of moisture, are able to react
chemically with calcium hydroxide and other alkaline earth hydroxides to form compounds
that harden. Fly ash in concrete also acts as a mechanical filler supplementing or re-
placing fine |s@Rd) aggregate. Its spherical shaog impaaves the workability of the plastic
concrete and the ease with which it is finished. In domestic sewers, concrete is frequently
exposed to attack by sulfuric acid formed through the contact of hydrogen sulfide with wet
surfaces. Addition of fly ash to concrete mixes can materially increase a concrete's resis-
tance to sulfurJc acid attacfe.
Mast fly ash concretes require more air-entraining agent to achieve a similar air con-
tent to that required for regular concrete. Entraining agent requirements for a constant air
content increases with the percentage of fly ash and its carbon content present as a replace-
ment for portland cement.
Specifications fvr fly ash in concrete, bituminous pavement, and light-weight aggregate
should be a performance type, expressed in terms of desired characteristics for the final
product. Specifications are primarily based on experience with particular fly ashes since
some fly ash may not comply with a given specification for producing an acceptable product.
The economy of using fly ash depends almost entirely on its quality, generation, location,
and cost relative to cement, although there may be economic advantages from reduced pouring
and finishing time compared to standard concrete. Significant savings in using fly ash can
result when large quantities of concrete are involved.
162
-------
There are some materials handling problems associated with the use of fly ash in concrete.
Low viscosity, for instance, may cause problems in feeding and weighing, and the extreme
fineness of fly ash can lead to air pollution and other problems, such as poor insulating
properties of concrete used in electrical boxes and switches. Proper design of feeders and
scales and the installation of dust-collecting systems can eliminate these problems.
Stabilized Bed Construction.
The use of granular material in base and sub-base construction for road and airfield
pavements runs into billions of kkg per year. Because of the vast quantities of materials
used for this type of construction, an attractive and promising method for utilizing fly ash
is provided. There has also been a substantial increase in the use of lime fly-ash aggregate
(LFA) and lime-cement fly-ash aggregate (LCFA) mixtures in pavement construction during
recent years. Many state and federal agencies have expanded their specifications to in-
clude LFA and LCFA as acceptable paving materials. Based on their properties, great po-
tential markets can be developed for the use of LFA and LCFA materials in paving construc-
tion.
LFA mixtures are blends of aggregate, lime, fly ash, and water which, when compacted
to a relatively high density, produce hard surface paving materials; LCFA contains concrete
in addition to the materials in LFA. Aggregates which can be successfully used in LFA and
LCFA mixtures cover the entire spectrum, including sands, gravels, crushed stones, and
several types of slag. Typical proportions are 2-1/2 to 3-1/2 percent lime and 10 to 25
percent fly ash, depending on the gradations of the aggregates. When cement is used
in the LCFA mixtures, the ratio of lime to cement is usually 3:1 or 4:1. The optimum fly
ash content for a particular mix is the quantity needed to achieve maximum density in the
compacted mixture, that is, fill the voids in the aggregate lime content. The optimum
content can be established by trial batch procedures for desired strength and durability
characteristics.
Important properties of paving materials are durability, dimensional stability, strength,
and stiffness. The standard test for durability of LFA and LCFA mixtures is the cyclic
freeze-thaw ASTM C593 designated test. Figure 177 shows the pattern of strength loss and
gain of a typical LCFA material during alternate periods of freezing and thawing. As the
curing period for the materials increased, the loss in strength decreased until ultimately the
material showed a gain in strength, even during the cycle freezing and thawing period.
When the latter condition exists, durability of the material is improved. All paving materials
in which the aggregate particles are bound together with binders such as cement, asphalt,
or lime fly-ash change dimensions with temperature and moisture conditions. Good pave-
ment performance requires that the coefficients of linear thermal expansion of the layers be
limited to less than 10 . If large dimensional changes occur, the pavement will crack
excessively, permitting the infiltration of water and foreign material into the pavement with
a concomitant failure in pavement performance. Dimensional changes of a typical LFA
material under varying moisture and temperature conditions are shown in Figure 178- As a
general rule, the coefficients of linear thermal expansion for hardened LFA and LCFA
materials can be taken as 5 x 10 , or about the same as portland cement concrete.
163
-------
26 28
Legend
Period of constant 49*t temperature
Period of ten freeze-thaw cycles
Source; 23
Figure 177. Effect of freeze-thaw cycles on LCFA compress!ve strength.
164
-------
60
40
0)
H
S.20
D)
-------
The higher the compressive strength,the better the quality of the LFA mixture. The
strength of LFA and LCFA are time and temperature dependent. Some time and temperature
versus strength relationships for typical LFA and LCFA mixtures are shown in Figures 179
and ISO,/ respectively. Data in Table 61 shows how the strength and durability of the well-
gcnded aggregate vary with the fly ash content.
Figure 181 shows the effect of lime content on compressive strength of LFA mixtures;
Figure 182shows the effect on density of LFA mixtures. LCF and LCFA mixtures have an
excellent performance record as paving materials. One of the best examples of the use of
LFA and LCFA materials for pavement construction is at the Newark, New Jersey airport.
A recent survey of the Newark airport facilities found the primary runway and taxiway system
to be in excellent condition. LFA and LCFA materials are also being used extensively by
the Port Authorities of New York and New Jersey in the rehabilitation and upgrading of the
pavements at Kennedy International Airport. Still, the application and marketing of fly ash
as paving materials has not been fully exploited. The paving material market is tremendously
large, and with additional effort on a national level it appears that this market could absorb
a substantial portion of all fly ash produced.
Fill Material
Most fly ash applications require substantial capital investment in processing equipment,
and time to develop markets. Using ash as a fill material, however, offers the advantage
of minimum processing costs and a large existing market. The important material properties
when considering fly ash as a fill material are its grain size, density, compaction charac-
teristics, shear strength, and permeability.
The compacted dry density of fly ash is usually in the range of 1 to 1.5 g/cu cm, which
is a high weight when compared with most conventional fill materials; the optimum moisture
content is normally in the range of 18 to 30 percent by weight. The permeability of compacted
fly ash is low, typically in the range of 10~3 to 10"^ cm per minute. This is quite adequate
for a homogenous, compacted fill material. Apart from slight solubility in water, fly ash is
chemically very stable, and there is little deterioration on exposure to the atmosphere. Also,
since the small soluble content is partially fixed after participation in the pozzolanic action,
leachate water passing over or through fly ashfill will pick up somewhat lower quantities of
soluble chemicals. Strength characteristics are enhanced by the pozzolanic action, and there
is a gradual increase of strength with time, as with portland cement.
Fly ash's low unit weight and low compressibility help to reduce differential settlement
between the approach embankment and the structure itself. Fly ash has also been used as
structural fill to retain slurry at Grossblidergtroff Station of the Houilleres du Bassin Lorraine
(HBL) in eastern France. Fly ash fill dams were constructed in the valley and the area be-
hind them was then filled with water from a small tributary stream of the Soar river. Waste
ash from the generating station was later filled to reclaim land.
166
-------
120
E
o
_C
"a>
90 -
60
I
o
u
30
40 60
Curing Time (days)
LFA Components (%)
Lime—2.5
Fly Ash—10
Aggregate—87.5
Source: 23.
Figure 179. Effect of curing time and temperature on LFA compressive strength.
167
-------
120
E
u
0>
90 -
I 60
£
Q.
O
(J
30
0
10
20 30 40
Curing Time (days)
60
Source: 23.
Figure 180. Effect of curing time and temperature on LCFA compressive strength.
168
-------
TABLE 61. EFFECT OF FLY ASH CONTENT ON LFA STRENGTH AND DURABILITY
Fly Ash
Aggregate Content (%)
Type
Crushed stone
(well graded)
Slag
(uniformly sized)
10
12
15
20
24
28
Compressive
Strength
(kgf/sq cm)
33
56
79
46
54
61
Durability
Weight Compressive
Loss (%) Strength
(kgf/sq cm)
100
23
45
100
58
10
0
49
69
0
3
58
All samples contain 3 percent lime.
Source: 23.
169
-------
E
u
,g" 70
f
to
35
U
36 Days at 21°C
8
Lime Content (%)
12
Source: 23.
Figure 181 , Effect of lime content and curing conditions on LFA strength.
170
-------
100
IS1
C
-------
The major risks with compacted fly-ash fills are ash erosion (both internally and ex-
ternally) and liquefaction. Internal erosion can be controlled by a properly designed
drainage and filter system to ensure that fine material is not carried out of the dam as a
suspension in seepage water. External erosion due to wind, rain, and wave action can
be controlled by suitable cover vegetation on the downstream slope and slope protection
on the upstream slope.
Liquefaction is the sudden decrease in the shear resistance to almost zero caused by
collapse of the structure of the material associated with a sudden but temporary increase
in the pore pressure. Liquefaction can be prevented by avoiding the following conditions:
• Material gradation typically in the fine sand/coarse silt range
• Shock loadings
• Loose material with large percentage of voids
• High water table or excess pore water pressure
Soil Stabilization
The degree of stability in a soil (wet or dry) refers to its ability to resist deformation
under repeated or continuing loads. Treating the soil to improve deformation resistance
and strength is called stabilization. 34 A variety of stabilization methods are available;
however, no one method is best for all soil types because each soil differs markedly in its
properties and reactions to different stabilization methods. LFA and LCFA mixtures are two
materials which have been successfully used for soil stabilization in many applications, and
there is a developed technology concerning their use.
When compacted to high densities, the proper combination of lime, fly ash, aggregate
and water dries into a stable, hard, continuous slab which can be used as the subbase or base
for bituminous or concrete paving. The amorphous glassy materials in fly ash react to form
complex silicates and aluminate which in turn react with the calcium hydroxide and magne-
sium oxide in lime to form a cementitious matrix. The difference between LCFA and LFA
mixtures is in the addition of cement, which gives the LCFA material more strength.
Aggregate. The type of material to be stabilized is an important parameter in LFA/LCFA
design. For this purpose, five categories can be identified: clays, silty soils, sandy soils,
coarse granular soils, and other fill (pozzolanic materials). Treatment of clays depends
greatly on the chemical composition and particle size of the material. The sodium-calcium
ion balance is an important factor affecting pozzolanic strength. In practice, ratios of 5-9
percent lime and 10-25 percent fly ash are used in clay soils.
Silty soils composed of less than 10-12 percent clay can be stabilized with lime alone,
or with a lime/fly ash ratio of about 1:2. Silty soils containing greater amounts of clay
require larger percentages of fly ash.
172
-------
Sandy soils almost always need the addition of fly ash to promote stabilization because
of their coarseness. Sandy soils containing silt and clay (10-30 percent) may be stabilized
by lime alone if the clay is sufficiently pozzolan. However, addition of fly ash will pro-
duce better results. Lime-fly ash ratio of 1:5 are common for sandy soils alone, but grada-
tion will improve strength and durability.
Coarse soils generally need little (2-4 percent) or no lime to meet stability requirements
for base courses. The strength of mixes containing clay or caliche can be further enhanced
by the addition of fly ash (lime/fly ash ratios of 1:5 are appropriate). Materials such as
scoria, cinders, chert, or water-cooled slag have been used in LFA/LCFA compositions with
strengths approaching that of portland cement being reported. Fly ash iot only contributes
to the natural pozzolanic qualities of the above mixtures, but also improves the gradation
which results in greater strength.
Lime. Dolomite limes (quicklime and monohydrate) result in 30 percent stronger products
than calcitic limes, except in kaolinitic material where the strengths are about the same.
Currently, it is believed that the MgO in dolomitic limes acts as a catalyst in the soil-lime
reaction. Calcium to mg ratios of 1:1 and 2:lare optimal (magnesium must be in the oxidized
state), and most commercial dolomitic monohydrate limes are within these limits. No opti-
mum ratio of lime to fly ash has been found which satisfactorily stabilizes all soils. As the
lime to fly ash ratio is not very critical, and lime is 5 to 10 times more costly than fly ash,
it is desirable to use mixtures which maximize the percentage of fly ash.
Moisture. To obtain maximum strength in the hardened product the moisture content of
the LFA/LCFA mixture must be near optimum. Optimum moisture content varies depending
on the lime/fly ash ratio. In general, the moisture content which results in the maximum
bulk density of the lime-fly ash mixture is slightly higher than that needed for the maximum
hardened strength. The carbon content and fineness of the fly ash, as well as the floccula-
ting effects of the lime, all affect moisture content. Determining the optimum moisture
content for a particular mix of lime, fly ash, and aggregate can be facilitated by preparing
a figure similar to Figure 183. In this case, limits of 50:50 soil-lime,50:50 soil-fly ash,
and 100 percent aggregate were selected. Laboratory analysis determined the optimum
moisture concentrations for these limits to be 29.2, 17.9/and 16.7, respectively. Inter-
mediate moisture concentrations are scaled off as shown from 18 to 28 percent. The approxi-
mate optimum moisture content can then be read for any soil mix within the original limits.
There are two questions which remain to be answered with respect to fluidized-bed
residues in LFA and LCFA soil stabilization mixtures. First, do they work as well as con-
ventional fly ash? Second, because of the limestone content and the pozzolanic action
of the residues, can some of the lime and/or cement be replaced by the fluidized-bed
residues? Work is in progress to answer these questions.
Neutralization of Acid Mine Drainage
Acid mine drainage (AMD) annually causes millions of dollars of environmental damage.
Polluted water taken by downstream users for industrial, agricultural, or potable
173
-------
29.2
Soil (%)
Figure 183. LFA moisture correlation chart.
174
-------
applications may require additional pretreatment; fish and vegetation may be killed,
agricultural land damaged, and an area's recreational value reduced. The problem arises
when mining activities expose pyrites and marcasites to the oxygen in the air. In the
presence of moist air, sulfuric acid is formed. Every kg of iron sulfide exposed has the
potential to produce as much as 1.6 kg of sulfuric acid. The extent of the pollution
damage depends on how much sulfide oxidation has occurred and how much acid has been
released into the environment.
There are two basic approaches to dealing with AMD: prevent its formation or prevent
it from contaminating ground or surface waters. One approach which has been tried ex-
perimentally is to collect the acid as it forms and pump it to storage and treatment facilities,
where it is neutralized with lime or other chemicals before discharge. This is an expensive
alternative, especially if taken to its ultimate end of a treatment plant for every coal mine,
operating or abandoned. Since the formation of acid is initiated by oxygen, attempts have
been made to prevent contact between the sulfides and air or water. Mines have been
sealed to prevent water infiltration or exclude air, but results have not been promising.
Work has been done with using conventional coal fly ash residues for reclamation of
surface-mine spoils. The residues provided nutrients needed by the soil, served as a
conditioner, and their alkakinity has reduced the AMD. Our preliminary analysis suggests
that fluidized-bed residues could be used to neutralize AMD, both from strip and subsurface
mines. Neutralization capacity varies widely with the type of residue (see Figure 184).
Potential use for AMD control will therefore depend partially on the characteristics of the
specific residues available.
The marketing potential of fluidized-bed residues for AMD is difficult to determine.
Residues used in this way are not directly part of the mining production process. If this
application proves feasible, the demand for residues would depend primarily on environ-
mental regulations—the more restrictions placed on AMD and the more stringent the re-
quirements on strip-mine reclamation, the higher the demand. Power producers must, as
part of their normal production process, dispose of the residues generated. They will dis-
pose of them by the least expensive means. The assumption of a zero f.o.b. price at the
power plant for the residues would not be likely to hold for AMD application. The large
quantities of residues required plus their low return to the mine owner suggest that the
power plant would need to contribute some or all of the freight charges.
In general, residues would most likely be used for AMD control where the mine
site is as close or closer than the landfill site. The mine could be expected to pay the cost
of spreading the residues and perhaps some of the transport costs, and special environmental
protection measures and other costs would likely be incurred by a landfill operator, but not
by the mine operator. Thus, it is likely that fluidized-bed residues could be economically
shipped somewhat farther for AMD neutralization than for landfilling.
The market potential for fluidized-bed residues will thus be primarily determined,
assuming the application is technically feasible and there are significant regulations con-
cerning AMD, by i'..3 location of mine sites relative to power plants. Residues from
175
-------
X
Q.
14
13
12
n
10
9
8
7
6
5
4
3
2
1
Legend
• Control
0 VFA
0 VSBM
D NJFA
D NJSBM
A CFA
A FSFA
I I I I I I | I I !
I I I I I I I I I 1 I
I I I I
0 1020304050
100
150
200
250
300
350
ml H2O
Figure 184. pH of leachate for acid mine drainage control.
-------
coal-burning plants will,at present,tend to be available only for eastern United States mines,
as most coal-fired power plants are now located in the East. There are several areas in the
East where power plants and mining areas are in particularly close proximity. If fluidized-
bed oil gasification becomes widely adopted, many more mining areas will have a nearby
source of residues.
Soil Cement
Soil cement is a mixture of soil, portland cement, and water. Compacted at optimum
moisture content and cured to hydrate the cement, soil cement forms a strong stable base
that is resistant to variations in moisture and temperature. Soil cementi typically have
modules of elasticities which range from 100,000 (for clayey soils with little cement) up
to 10° (for stronger mixtures), and are far more elastic than concrete. Soil cement mix-
tures are used for base courses under pavement, roadway shoulders, patching, ditch and
channel linings, dam facings, and miscellaneous uses.
In general, there are three types of soil cement: compacted soil cement, cement modi-
fied soil, and plastic soil cement. Compacted soil cement contains the stoichiometric
amount of cement to harden the soil and the stoichiometric amount of water to hydrate
the cement. Cement-modified soil is an unhardened or partially hardened mixture of soil
and cement. Just enough cement and water are added to the soil to change.its chemical
and physical properties. Addition of cement to soil reduces the soil's plasticity and water
holding capacity, and increases its bearing value. Plastic soil cement contains sufficient
water, at the time of placing, to give the mix a consistency similar to that of plastering
mortar.
The surface of a cured soil cement mixture is friable, hence it cannot be used as a
running surface for motor vehicles without experiencing scuffing and pitting. It is usually
overlaid with a layer of bituminous or concrete paving, the type of covering determining
to some extent the type and thickness of the soil cement sub-base.
Soil cement is an inexpensive paving material because of the three basic materials
needed. Soil and water are either found at the site or transported only short distances.
The work "soil" as used in "soil cement" means any combination of gravel, sand, silt,clay,
or filler (such as cinders, shale, chat, etc.). The water used in soil cement preparation
serves two purposes: it aids in compaction by lubricating soil grains, and it is necessary
for cement hydration.
Soil gradation is an important factor in proper soil cement design. Sandy and gravelly
soils with about 10-35 percent silt and clay combined are the most desirable soil cement
aggregates and generally require the least amount of cement for satisfactory curing. Coarse
soils containing 55 percent or more material passing the number four sieve also make good
soil cement aggregates. Sandy soils deficient in fines can make adequate soil cement,
although the amount of cement needed increases as the percentage of fines decreases. Silty
and clayey soils also can be used to make satisfactory soil cement; however, the higher the
clay content, the greater the amount of cement needed to provide adequate hardening.
177
-------
Silty and clayey soils are sensitive to weather conditions (much more so than coarse or
well graded soils.
The amount of portland cement needed to construct a suitable soil cement pavement
depends on soil type and design load. Any type of portland cement which complies with
ASTM or AASHTO specifications is satisfactory. Types 1 and 1A, normal and air-entrain-
ing portland cements are most commonly used. Tables 62 and 63 show representative cement
concentrations for various soil types.
When possible, the optimum amount of moisture to add to a soil cement mixture should
be determined by a laboratory test, such as AASHTO T134 "Standard Method of Test for
Moisture-Density Relations of Soil-Cement Mixtures." In general, sandy mixtures will
require approximately 22 I of water per sq m for a 15-cm compacted thickness. Silty and
clayey mixtures will require about 32 I of water per sq m. Experienced users can, within
practical limits, determine the optimum moisture content by test. Soil cement at optimum
moisture contains sufficient water to form a firm cast; when squeezed in the hand, water
cannot be squeezed out.
In practice, soil cement is generally mixed ?n-s?tu or less commonly away from the
construction site and then trucked in. In-place mixing is more economical; off-site mixing
is used only when the quantity or quality of the aggregate at the site is not adequate
enough to meet the design standards. Mixing of the aggregate and cement can be either
on the ground (continuous mixing) or in a mixer (either traveling or stationary). Mixers
provide a better control over the amount and blending of the components. Groundmixing
is cheaper and usually faster; it can be done using a dump truck or even by hand. Compac-
tion is usually done by rollers; however, in sandy soils or coarse soils lacking in fines,
compaction must be done by vibration.
Curing soil cement mixtures have to be protected from the weather in order to prevent
moisture imbalance. Bituminous coatings; are generally used, but dirt, straw, and paper
have all been successfully applied.
Agriculture and Reclamation
Residues can be used to eliminate acid type agricultural soils. Soil pH is also an
important factor in c'etermining the solubility of many compounds such as the concentration of
heavy metals present in crops . It had been observed that in a strongly acid soi I, large
amounts of metals such as iron, aluminum, and manganese may come into solution and may be
adsorbed on the surface of the soil particle. Plants can easily take up metals in this form. '
Soil with a safe toxic metal content atpH 7 can easily be lethal to most crops at pH 5.5.
However, it has also been found that an increase in pH will decrease the plant uptake of heavy
metals. Application of sewage sludge or effluent irrigation may generally tend to lower the
soil pH, and the addition of calcerous or magnesium compounds to soil can correct or eliminate
acidic soil conditions.
178
-------
Material _ Percent by Volume Percent by Weight
Caliche
Chat
Chert
Cinders
Limestone screenings
Marl
Red dog
Scoria containing plus No. 4
material
Scoria (minus No . 4 material only)
Shale or disintegrated shale
Shell soils
Slag (air-cooled)
Slag (water-cooled)
8
8
9
8
7
11
9
12
8
11
8
9
10
7
7
8
8
5
11
8
11
7
10
7
7
12
Source: 189.
TABLE 63. NORMAL RANGE OF CEMENT REQUIREMENTS
FOR B AND C HORIZON SOILS0
AASHO Soil Group
A-l-a
A-l-b
A-2-4, A-2-5, A-2-6, A-2-7
A-3
A-4
A-5
A-6
A-7
Percent by Volume
5-7
7-9
7-10
8-12
8-12
8-12
10-14
10-14
Percent by Weight
3-5
5-8
5-9
7-11
7-12
8-13
9-15
10-16
"A" horizon soils may contain organic or other material detrimental to cement reaction
and may require higher cement factors. For dark grey to gret A horizon soils, increase
the above cement contents four percentage points; for black A horizon soils, six percentage
points.
Source: 189.
179
-------
Related information on the effects of zinc level and soil pH on chard plants are shown
in Table 64. Inorganic zinc (and cadmium at one percent of the added zinc) was added
to a sassafras sandy loam soil and the pH was adjusted to 5.3, 6.4, or 7.2 in the metal
amended soil. The concentration of zinc uptake in plants may be significantly reduced
when the soil pH is increased by the addition of lime or other pertinent alkaline materials.
(A brief literature search identified previously published data and conclusions showing the
same trace metal uptake improvement).
Addition of sulfur will reduce the soil pH. The reduction of soil pH is directly pro-
portional to the quantity of sulfur added. Lowering the soil pH increased the concentra-
tion of metals as shown in Table 65 and certain other elements such as silicon, phos-
phorus and potassium.
At the Virginia Polytechnical Institute, other field research on using fly. ash as* a
fertilizer is seeking to determine (1) the plant nutrients available in fly ash and (2) the
effects of different fly ash application rates. Research on revegetating several barren
experimental sites has proven that fly ash could act as a neutralizing agent, diluent,
and soil conditioner to provide needed nutrients which enhance vegetation growth.84
The U.S. Park Service, Washington,D.C., is testing sintered fly ash for use as an
additive to soils subjected to continuous use (bicycle paths, camping areas, hiking trails,
picnic areas), fa this application, sintered fly ash would be added for its porosity and
resistance to degradation.
Brick Manufacture.
Using fly ash as an additive can extend the life of a clay or shale deposit; this is of
particular value to brick plants with limited raw materials supplies. Extensive research
on fly ash in brick has been done at the Coal Research Bureau of West Virginia University.
This research has yielded tolerance levels for many fly ash constituents which, when ex-
ceeded, contribute to a poor quality brick. These constituents include: water soluble
minerals, water soluble sulfur, carbon, iron, and alkaline earths. The first commercial
fly ash brick plant using the process developed at the Coal Research Bureau is operating
at Edmonton,Alberta. The plant has a design capacity of 35 million bricks per year.
Economic studies currently underway indicate that the cost of the Coal Research Bureau
process is less than that of the conventional clay-brick manufacturing process. Several
firms are currently examining the process for commercial exploitation. Research is under-
way on coloring and texturing the brick, and on producing large size bricks.
Water Quality Improvement.
Fly ash as a treatment miaterial for reclaiming small eutrophic or algae-overgrown
lakes is under study at Notre Dame University. Fly ash can remove phosphates in the
water and seal the bottom mud so that the release of pollutants is controlled. A process
for the removal of phosphates from water using fly ash has been developed at the Poly-
technic Institute, Brooklyn, N.Y. When used for water treatment, fly ash will (1) increase
180
-------
TABLE 64. EFFECTS OF ADDING Zn AND VARYING THE pH
IN THE SOIL ON Zn CONTENT AND YIELD REDUCTION
OF CHARD LEAVES
Added Zn
ppm
1.31
32.7
65.4
131.0
262.0
5.3
210
754
1058(7)°
2763(41)
2692(95)
Soil pHb
6.4
116
237
337(5)
765(9)
1678(22)
7.2
12
74
100
177
406(27)
• Yield reduction in parentheses (%).
g. Zn/g dry weight.
Source: 191.
TABLE 65. EFFECTS OF SOIL pH ON SOYBEAN PLANT'S MINERAL UPTAKE
Elements
in ppm
Fe
Mn
Zn
Co
Mo
Al
B
Ni
Si
P
K
Soil
7.4a
31
47
40
6.6
9.5
9.6
72
4.4
2000
4300
17,300
pH
6.1b
81
209
68
12.3
12.6
16.4
123.0
7.7
3800
6500
25,900
% Elements yield g 1 plant
Increase 7^a ^^
261.2 5.6 18.5
444.6 8.5 47.7
170.0 1.72 2.87
186.3
132.6
170.8
170.8
175.0
190.0
151.1
149.7
° No sulfur added.
b 10% sulfur added.
P154619-5-1 soybean variety.
Source: 192.
181
-------
the growth of floes, thus enhance settling, (2) condition the waste sludge as a physical
aid to filtration, (3) remove phosphates, and (4) absorb organic molecules in solution.
Miscellaneous.
Industrial applications for the hollow, spherical, and extremely light-weight fly ash
particles known as cenospheres are being developed at Washington State University. One
application, known as "syntactic foam," is used to achieve buoyancy in deep ocean en-
vironments. Syntactic foam is formed by vacuum impregnating cenospheres with an appro-
priate resin. Research on aerospace applications of cenospheres is underway at the
Grumman Aerospace Corporation. From this research, a closed pore insulation material
for use on the space shuttle has been developed. A unique application using cenospheres
in the production of a tape for fire proofing and insulating high-voltage electrical cable,
has been developed by the Quelcor Corporation.
Specific Applications of Lime/Limestone Wet Scrubber Residues
"Modified fly ash," the solid by-product from lime/limestone wet-scrubbing, is a new
solid waste material which has different chemical and physical properties from regular fly
ash. Modified fly ash has little potential for mineral separation and benefication, and
therefore, must be used in its homogeneous state. The Coal Research Bureau has developed
several promising uses for modified fly ash. Several potential applications are considered
below:
* Soil amendment
• Highway construction
• Aerated concrete
• Poured concrete
Soil Amendments.
Dried modified fly ash can be used as a soil amendment to increase the calcareous
component, and \ •> neutralize acid soil. Modified fly ash may also increase the concen-
trations of boron and other trace elements, and also increase the texture and drainage
characteristics of soils.m Further research is needed to determine if pollution would be
created by water leacning.
Highway Construction.
Combustion Engineering participated in a project with the Research and Development
Division of the Federal Highway Department to study the use of residues as a highway con-
struction material. The program was part of the International Transportation Exposition
(Transpo '72} that was held from May 24 to June 4, 1972 at the Dulles Airport in Washing-
ton, D.C. To accommodate the 50,000 automobiles and 600 buses' arriving daily at the
182
-------
exposition, a 49 hectare parking lot was constructed. The Research and Development
Division of the Federal Highway Administration used this opportunity to demonstrate the
recycling of waste products as highway construction materials. The major portion of the
parking lot was paved with a mixture of modified fly ash and sulfate sludge from an acid
plant.
Aerated Concrete.
Aerated concrete has been widely developed in Europe. Almost all new factory build-
ings in Sweden and West Germany are constructed, in part, using this material. Aerated
concrete is a light-weight structural material consisting of small non-communicating gas
cells entrained in a calcium silicate matrix. A process flow sheet for the production of
aerated or foamed cellular concrete from modified ash is shown in Figure .185 . It is
necessary to add cement and a gas-producing agent to modified fly ash in making this
product. Commercial aerated concrete varies from 0.3-0.8 g/cu cm in density, and has
a compressive strength of about 30-60 kgf/sq cm.
Aerated concrete material can be sawed, nailed, drilled, screwed, or glued as wood,
but has the thermal and fire resistant properties of concrete. Potential uses include non-
load-bearing walls, sandwich construction with brick or concrete for insulating purposes,
and.interior surfacing for exterior walls. It can be formed in any desired shape or cut
from panels and is suitable for modular construction,
Poured Concrete.
Figure 186 is a process flow sheet for the manufacture of poured concrete materials.
The material is poured into molds for curing instead of being pressed as in the manufacture
of CS brick. The resulting poured concrete block has a density of 1 J5 g/cu cm and com-
pressive strength of about 60 kgf/cu cm. Modified ash does not require grinding or curing
prior to use in poured concrete.
The advantages of producing autoclaved calcium-silicate products from limestone fly
ash include:
• No SO~ capture or marketing problems would result as processing occurs below
the temperature for sulfur dioxide regeneration.
• Little or no storage or curing time is required before use since structural materials
produced are durable, pre-shrunk, and pre-strengthened.
• No exotic equipment is required for production.
• Minimum pollution occurs at the plant since all rejects and process waters may be
recycled.
• A potentially large market exists in low-cost housing or other construction.
183
-------
Mech Precip - Dry Collected
Limestone Modified Fly Ash (92%)
8% Portland Cement
Type I, Normal
0.16% Aluminum Powder
Paddle Mixer (10 Minutes)
Pour into Molds
8 hours
Air Set
Autoclave, 16 hours
!» 16kgf/sq cm, 185C
Air Drying
(72 hours)
51% H20
@60C
Source; 46.
Figure 185. Aerated or foamed cellular concrete production flow diagram,
184
-------
Silica Sand
Wet Collected Limestone
Modified Fly Ash
(10% Slurry)
Dewater Ash to 58% H2O
Lime (CaO) 96% Pure
50% Ash+ 11% CaO
+ 39% Sand
Paddle Mixer
(10 Minutes)
Pouring into Molds
24 hours Them
al Set (HOC)
Autoclave, 16 hours
@ 16kgf/sq cm, 185 C
Air Drying
(72 hours)
Source: 46.
Figure 186. Formed concrete production flow sheet.
185
-------
Autocloved Products.
Because absorbed sulfur dioxide is liberated when modified fly ash is heated, it is
necessary to find a technique for totally using the ash which would either lock the sulfur
into the product or not require heating. Autoclaving has the advantage of locking sulfur
into the final product. The products with the greatest potential for using modified fly ash
are:
• Bricks and blocks
• Aerated or fo,amed concrete
• Concrete materials
Calcium silicate (CS) brick production has been examined as a potential large tonnage
application of limestone modified fly ash. Bricks produced by this method have the ad-
vantage of binding the sulfur components within a calcium-silicate matrix. These bricks
surpass the standards for conventional sand-lime brick. Figure 187'is a process flow sheet
for the production of CS brick. Mixing and humidity curing are two important process
parameters in producing CS brick. Promising areas for using calcium silicate brick include
low-cost construction materials, interior walls, decorative walls, patios, and thermal or
acoustic insulation.
Potential Structural Materials Applications: Test Results
Several beneficial materials applications for conventional coal-combustion residues
were discussed earlier in this chapter. Because of limited material, it was not possible to
undertake a comprehensive structural testing program investigating all the possible uses of
fluidized-bed coal combustion residues; several preliminary screening tests were run on
applications for the residues in concrete and asphalt. These tests are listed in Table 66.
Concrete and asphalt are discussed separately below. Tests are currently being done on
residue application in pozzolan cements, soil cement, acid mine drainage, and load
bearing fill, which will be discussed in the final report.
Concrete.
Procedure. The residue addition to concrete was tested for compressive strength.
Twenty batches of concrete were mixed, differing in the amount and type of residue added.
Two of the twenty were control samples in which no residues were added. Four sample
specimen cylinders were made from each batch. The procedure followed for making the
cylinders was ASTM CI92-69 ("standard method of making and curing concrete test speci-
mens in the laboratory"); the cylinders were approximately 5 cm in diameter by 10 cm in
length. Table 67 gives the composition of each batch. The mixtures are considered
"rich mixes" because of the high cement content (approximately 15 percent).
186
-------
Wet Collected Limestone
Modified Fly Ash (1% Slurry)
Silica Sand
30 x 100 Mesh
Dewater Ash to
34% H2O
50% Fly Ash+ 11% CaO
+ 39% Silica Sand
Paddle Mixer (10 min)
@20.4% H2O
Lime (CaO)
96% Pure
Slaking Reactor
(1 hour)
Forming Pressure
200 kgf/sq cm,
17.7% H2O
24-Hour Humidity
Storage: 95% Humidity
atSTP
Autoclave
8hr, 16kgf/sq cm, 185C
Air Drying
(72 hours)
Figure 187« CS brick production flow diagram;
187
-------
TABLE 66 . POTENTIAL STRUCTURAL MATERIALS APPLICATIONS:
TESTS PERFORMED
Application Test Description Method
Concrete Compressive strength of cylindrical ASTM C39
concrete specimens
Asphalt Compressive strength of bituminous ASTM D1074
mixtures
Effect of water on cohesion of compacted ASTM D1075
mixtures
Pozzolan cements
LFA mixtures Compressive strength of cylindrical con- ASTM C-593
crete specimens
Soil cement Compressive strength of molded soil- ASTM D1633
cement
Load-bearing fill Classification for engineering purposes
Direct shear: soil under consolidated ASTM D3080
condition
Reference numbers as found in 1974 Annual Book of ASTM Standards. Philadelphia:
American Society for Testing and Materials (ASTM), 1974.
188
-------
TABLE 67. COMPOSITION OF CONCRETE TEST CYLINDERS
Batch Type of,
No.a Residue
1 Control
2 VSBM
3
4
5 NJFA
6
7
8 VFA
9
10
1 1 Control
12 NJSBM
13
14
15 EFA
16
17
18 ESBM
19
20
Concrete Composition (% by weight)
Residue Fine Aggregate Portland Cement
0
5.2
15.8
25.0
5.3
15.7
25.0
5.2
15.0
24.7
0
5.3
15.2
25.7
5.2
15.2
25.1
5.3
15.2
25.1
71.5
64.8
53.6
41.0
64.7
53.4
41.0
63.7
51.0
40.5
71.5
64.7
53.7
43.2
64.8
53.7
41.0
64.7
53.7
41.0
15.2
14.9
14.7
14.0
14.9
14.7
14.0
14.6
14.0
13.8
15.2
14.9
14.7
14.7
14.9
14.7
14.0
14.9
14.7
14.0
Water
13.3
15.1
15.9
20.0
15.1
16.2
20.0
16.5
20.0
20.9
13.3
15.1
16.4
16.4
15.1
16.4
20.0
15.1
16.4
20.0
, Two samples for each batch.
Residue source code presented in Table 6.
189
-------
One sample from each batch was tested after curing for seven days; another , after
twenty-eight days. After curing, the cylindrical molds were removed and the diameter
of the cylinders measured to obtain average cross-sectional area; the results are shown in
Tables 68 and 69. Each cylinder was then capped to prepare them for the actual com-
pressive strength tests. The results of the tests are presented in Table 70 for the seven
day curing and in Table 71 for the twenty-eight day curing.
Results. The results are shown graphically in Figures 188to 191, which plot compressive
strength versus residue strength. In general, the strength increased with curing time for
all the fluidized bed residues. The only exception was the concrete containing more than
about 18 percent by weight of EFA. This was due to the unique property of the 7 day
cured EFA. Like the other residues, the strength of the concrete decreased from 5 to 15
percent residue; however, at 25 percent residue content, the compressive strength had
increased to a value higher than the concrete containing 5 percent residue.
Optimum residue percentages varied widely. Strengths increased with increasing
residue concentration for fly (7 day cure) and spent bed materials from the Exxon, New
Jersey, pressurized msnipiant. On the contrary, with the exception of VFA (28 day cure)
and the EFA (7 day cure)F strengths decreased with Increasing content of residues from the
PER, Virginia atmospheric pressure unit and from the Esso gasifier. The following concrete
test specimens showed unconfined couipresslve strengths greater than the contra' specimens:
5 percent VSBM/^ day cure; 5,! 5, and 25 percent VSBM/28 day cure; 5, 15, .and 25
zmcetit NJFA/28 Jay cure; and 5 percent VFA/28 day cure. The 25 day NJFA/7 day cure
material was nearly equal to the control.
Asphait
Procedure. Residues were tested as replacements for aggregate filler in asphalt. Samples
were made and tested for compressive strength following the procedures outlined in ASTM-
D-1074; test cylinders were approximately 10 cm in diameter and length. Residue contents
tested were 0, 20, 45, 82, and 92 percent of aggregate volume (measured by weight from
specific gravities). The aggregate conformed to State of California Department of Trans-
portation 3/8-inch maximum gradation specifications. To simplify handling and to lower
test cost, emulsified asphalt (SS-1 H) was used in concentrations of 8 to 13 percent by weight..
Compression tests were also performed for samples containing portland cement, lime or
hydrochloric acid additives. Table 72 summarizes the sample compositions.
All residues were slaked before being added to the asphalt mixtures. Unslaked residues
produced poor results, particularly the Exxon spent bed material. Reactions between the
residue and the emulsified asphalt resulted in a significant decrease in density. In some
cases, expansion of the residue was enough to completely disintegrate the test specimen
which resulted in a crumbly pile of aggregate and partially coated residue (See Figure 192).
Samples were subjected to a compacting load of 17,199 kg for two minutes. Samples
were then measured and coded, and those that were within 10.16 + 0.64 cm in length were
cured in an oven at 60 ± 3°C. One sample of each composition was cured for 29 hours and
one for 7 days.
190
-------
TABLE 68 . DIAMETER AND AREA OF CONCRETE TEST CYLINDERS:
SEVEN-DAY CURE
Batch
No.°
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
b
5.37
5.45
5.61
5.77
5.45
5.37
5.53
5.77
5.77
5.61
5.40
5.24
5.40
5.40
5.40
5.40
5.40
5.32
5.40
5.40
Diameter
b
5.77
5.77
5.77
5.77
5.77
5.85
5.69
5.45
5.45
5.53
5.32
5.24
5.40
5.40
5.40
5.40
5.40
5.32
5.40
5.40
(cm)
c
5.69
5.85
5.69
5.37
5.77
5.85
5.69
5.45
5.45
5.53
5.40
5.40
5.24
5.24
5.24
5.32
5.16
5.24
5.32
5.32
c
5.45
5.45
5.69
5.77
5.61
5.37
5.61
5.69
5.77
5.61
5.32
5.40
5.24
5.24
5.24
5.24
5.24
5.24
5.32
5.32
Average
Diameter
(cm)
5.57
5.63
5.69
5.67
5.65
5.61
5.63
5.59
5.61
5.57
5.36
5.32
5.32
5.32
5.32
5.34
5.30
5.28
5.36
5.36
Average Cross-
sectional Area
(sq cm)
24.37
24.89
25.43
25.25
25.07
24.72
24.89
24.54
24.72
24.37
22.56
22.23
22.23
22.23
22.23
22.40
22.06
21.90
22.56
22.56
, Two samples for each batch.
First sample of the batch; two diameter measurements taken to minimize effect of
random irregularities.
° Second sample of the batch; two diameter measurements taken to minimize effect of
random irregularities.
191
-------
TABLE 69. DIAMETER AND AREA OF CONCRETE TEST CYLINDERS:
TWENTY-EIGHT DAY CURE
Batch
No.a
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
b
5.29
5.45
5.37
5.37
5.29
5.45
5.29
5.29
5.45
5.45
5.32
5.40
5.32
5.40
5.40
5.40
5.40
5.40
5.40
5.40
Diameter
b
5.29
5.45
5.37
5.37
5.29
5.45
5.29
5.29
5.45
5.37
5.32
5.40
5.32
5.40
5.40
5.40
5.40
5.40
5.40
5.40
(cm)
c
5.45
5.21
5.45
5.37
5.45
5.29
5.45
5.45
5.29
5.37
5.40
5.24
5.32
5.24
5.24
5.24
5.24
5.16
5.24
5.24
c
5.45
5.21
5.37
5.37
5.45
5.37
5.45
5.37
5.29
5.37
5.40
5.24
5.32
5.24
5.24
5.16
5.32
5.24
5.24
5.24
Average
Diameter
(cm)
5.37
5.33
5.39
5.37
5.37
. 5.39
5.37
5.35
5.37
5.39
5.36
5.32
5.32
5,32
5.32
5.30
5.34
5.30
5.32
5.32
Average Cross-
sectional Area
(sq cm)
22.65
22.31
22.82
22.65
22.65
22.82
22.65
22.48
22.65
22.82
22.56
22.23
22.23
22.23
22.23
22.06
22.40
22.06
22.23
22.23
, Two samples for each batch.
First sample of the batch; two diameter measurements taken to minimize effect of
random irregularities.
Second sample of the batch; two diameter measurements taken to minimize effect of
random irregularities.
192
-------
TABLE 70. RESULTS OF COMPRESSIVE CONCRETE STRENGTH TEST
AFTER SEVEN DAYS
CO
Batch No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
Type of
Residue0
Control
VSBM
NJFA
VFA
Control
NJSBM
EFA
ESBM
Residue
Content
(%)
0
5.2
15.8
25.0
5.3
15.7
25.0
5.2
15.0
24.7
0
5.3
15.2
25.7
5.2
15.2
25.1
5.3
15.2
25.1
Cross-Sec-
tional Area
(sq cm)
24.37
24.89
25.43
25.25
25.07
24.72
24.89
24.54
24.72
24.37
22.56
22.23
22.23
22.23
22.23
22.40
22.06
21.90
22.56
22.56
Max Load
Before Fail-
ure (kg)
3,856
4,763
3,175
2,948
3,402
3,629
3,856
2,948
2,495
2,268
3,855
2,041
2,494
2,721
3,175
1,814
3,401
1,587
1,361
1,134
Time Load
Applied
(sec)
2.0
1.8
1.6
1.8
1.8
1.5
1.5
1.6
1.5
1.4
20
20
10
10
10
10
17
7
10
10
Strength
(kg/sq cm)
158.2
191.4
124.9
116.8
135.7
146.8
154.9
120.1
100.9
93.1
170.88
91.81
112.40
122.40
142.83
80.98
154.17
72.47
60.33
50.27
Fracture
Description
Conical , diagonal
Vertical and less
diagonal
Conical, diagonal
Diagonal
Conical , diagonal
Vertical, diagonal
Diagonal
Conical with small
vertical
Diagonal
Diagonal
Conical , diagonal
Diagonal , vertical
conical
Diagonal, vertical
Diagonal, vertical,
shearing
Diagonal, vertical
Diagonal, vertical
Diagonal, vertical
Diagonal, vertical
Diagonal
Diagonal, vertical
Residue source code presented in Table 6.
-------
TABLE 71. RESULTS OF COMPRESSIVE CONCRETE STRENGTH TEST AFTER TWENTY-EIGHT DAYS
Batch No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
Type of
Residue0
Control
VSBM
NJFA
VFA
Control
NJSBM
EFA
ESBM
Residue
Content
(%)
0
5.2
15.8
25.0
5.3
15.7
25.0
5.2
15.0
24.7
0
5.3
15.2
25.V
5.2
15.2
25.1
5.3
15.2
25.1
Cross-Sec-
tional Area
(sq cm)
22.65
22.31
22.82
22.65
22.65
22.82
22.65
22.48
22.65
22.82
22.56
22.23
22.23
22.23
22.23
22.06
22.40
22.06
22.23
22.23
Max Load
(kg)
3,629
4,763
4,536
3,856
5,443
5,670
5,897
4,536
2,948
2,722
5,443
2,722
3,175
3,856
3,629
2,495
1,361
3,629
1,814
1,134
Time Load
Applied
(sec)
3.0
2.5
2.5
2.5
3.5
3.0
3.0
4.0
2.0
3.0
8.0
10.0
6.0
8.0
7.0
5.0
3.0
6.0
5.0
5.0
Strength
(kg/sq cm)
160.2
213.5
198.8
170.2
240.3
248.5
260.4
201.8
130.2
119.3
241.0
122.4
142.8
173.5
163.2
113.1
60.8
164.5
81.6
51.0
Fracture Description
Conical and diagonal
Conical and diagonal
Conical and diagonal
Conical and diagonal
Conical and diagonal
Conical and diagonal
Conical and diagonal
Conical and diagonal
Conical and diagonal
Conical and diagonal
Conical and diagonal
Conical and diagonal
Conical and diagonal
Conical and diagonal
Conical and diagonal
Conical and diagonal
Conical and diagonal
Conical and diagonal
Conical and diagonal
Conical and diagonal
Residue source code presented in Table 6.
-------
300>-
250h
y
o- 200
D)
g> 150h
NO tO
2
E lOOh
50H
0
Legend
^ Control
A NJFA
O VFA
D VSBM
5
10 15 20
Residue Content (% by weight)
25
30
Figure 188. Concrete, compressive strength tests: NJFA, VFA, VSBM after seven day cure,
-------
300
250
£-
O)
200
150
0)
(D
cL
o
U
100
50
0
Legend
• Control
A NJFA
O VFA
D VSBM
I
I
10
25
Figure 1-89
15 20
Residue Content (% by weight)
Concrete compresslve strength tests: -NJFA, VFA, VSBM after 28-day cure,
30
-------
Legend
• Control
<3> NJSBM
* ESBM
® EFA
50
I
1
1
10
25
30
15 20
Residue Content (% by weight)
Figure 190. Concrete compresstve srrength tests: NJSBM/ESBM^EB^after seven day cure.
-------
300
250
£ 200
I
CD
£ 150
O 0)
00 >
100
U
50
Legend
• Control
A NJSBM
Q EFA
D ESBM
I
I
I
10 15 20
Residue Content (% by weight)
25
30
Figure 191 . Concrete compressive strength tests: NJSBM, EFA, ESBM after
28 day cure.
-------
TABLE 72. ASPHALT SAMPLE COMPOSITIONS
Number
of
Samples
12
24
24
24
4
24
4
24
4
24
68
Asphalt
8
8
8
8
8
8
8
8
8
8
Sample Composition ,
i
Aggregate
92
72
47
..
82
MM
82
*mmm
92
—
Percent by Weight
Fly Ash or
Bed Material
—
20
45
92
•MM
82
—
82
Other
Components
— .
—
«.
—
10 cement
10 cement
10 lime
10 lime
0;24V7*HCL
91.76-85 0
.24-7* HCL
Depending on type of residue
199
-------
Figure 192 . Result of reaction between residues and emulsified asphalt,
200
-------
Results. In most cases, substitution of fluidized-bed combustion residues for aggregate
did not have a significant beneficial or adverse effect on asphalt compressive strength
(see Figures 193 through 196). In several cases, test specimens containing New Jersey spent
bed material showed significantly increased strength (e.g., specimens 7 day cure/90 per-
cent residue, 29 hour cure/45 percent residue). In some instances a major reduction in
strength occurred (e.g., 7 day cure/82 percent NJFA),.
Samples showed large increases in strength when other treatment additives (portland
cement, lime or hydrochloric acid) were also included. Replacement of 10 percent by
volume of residues with portland cement increased strength from 200 to 300 percent.
Replacement with lime similarly increased compressive strength. The strength increase
was more than with comparable cement samples when short curing times were used, but
less than for comparable cement samples following longer curing times. Neutralization
of residue pH with hydrochloric acid also resulted in some increased sample compressive
strength.
Potential Agricultural Application of FBC Residues
Plants, to complete their life cycle successfully, require some trace zinc, copper,
iron, manganese, boron, chlorine, and aluminum, as well as large quantities of oxygen,
carbon, hydrogen, nitrogen, phosphorus, potassium, magnesium, and calcium. The former
group of elements is called the micronutrients and the latter, the macronutrients. Any
material which contains these nutrients in plant-available form has potential value as a
soil conditioner. Fly ash and spent bed material contain most of the micronutrients and
some of the macronutrients in plant-available form, as shown in Tables 17 to 20, which
present the results of residue chemical characterizations. Residues, because of composi-
tion and particle size, may be a good soil conditioner with considerable nutritive value.
Residues could also be used as liming material to reduce soil acidity. Soil acidity
develops in humid regions (such as the eastern United States) where the calcium and
magnesium may be gradually leached; it is accelerated by crop removal and cultivation.
Soil pH is a major determinant of plant growth. Most plants grow best between the range
of 7.0 to 7.5, hence both high and low pH's may be detrimental.
In acid soils, large amounts of iron, aluminum, manganese, copper, zinc, and boron
may enter into solution and be adsorbed on the surface of the soil particles in a form that
plants can readily assimilate. High levels of soluble manganese, iron, aluminum, and
boron may be toxic to crops, but liming can correct this condition. In contrast, molybde-
num is more soluble in alkaline soils than in acid soils, and thus uptake of this micronu-
trient may be increased with liming. However, if soil has a pH greater than 8.0, most of
the trace elements are fixed in the soil matrix and are unavailable to plants.
The potential for residue agricultural applications was evaluated in a series of small-
scale plant growth tests. Table 73 presents the test schedule.
201
-------
ro
Legend
• Control
A VSBM
O NJSBM
D ESBM
20
30
40 50 60 70
Residue Content (% by weight)
80
90
100
Figure 193. Asphalt compressive strength tests: VSBM, NJSBM, ESBM after 29 hour cure,
-------
lOOr-
80
E
o
60
8
O)
.1 40
I
u
20
Legend
• Control
A VSBM
O NJSBM
D ESBM
I
I
J
10
20
30
40 50 60 70
Residue Content {% by weight)
80
90
100
Figure :194^ Asphalt compressive strength tests: VSBM, NJSBM, ESBM after seven day cure.
-------
100
Legend
• Control
O NJFA
O EFA
80
cr
tsi
O)
60
8
O)
(U
I
I
I
10
20
30
40 50 60 70
Residue Content (% by weight)
80
90
100
Figure 195 . Asphalt compressive strength tests: NJFA/ EFA after 29 hour cure.
-------
100,-
Legend
80 -
• Control
O NJFA
O EFA
E
u
60
s
U)
> 40
U)
0)
_
E
c
U
20
1
_L
10
20
30
40 50 60 70
Residue Content (% by weight)
80
90
100
Figure 196-. Asphalt compressive strength tests: NJFA, EFA after seven day cure.
-------
TABLE 73 PI ANTING SCHEDULE FOR AGRICULTURAL TESTS
No.a'b
1
2
Date
Planting
3 March 1976
12 June
of
Harvesting
7 May
29 July
Tomato
c
Tomato
Residue Weight
(g/400 g of soil, dry wt.)
75,150,225,300
2.5,12.5,25.0,37.5
Remarks
Completed
Completed
Numerals refer to a given set of pots in which crops are being planted sequentially; letters refer to specific rotation
, in any given set of pots.
Six residues were tested (CFA, FSFA, VFA, VSBM,NJFA, and NJSBM), with one set of pots for each residue type,
and one set as a control. 1,000 cu cm pots were used.
Cherry tomato.
-------
Experiment 1.
Procedure. Small plastic pots (10.26 by 10.26 by 10.26 cm with about 1.061 cu cm
volume were filled with a commercial poiting mixture (SupersoiS). The average weight of
potting mixture used was about 400 grams. The pots were too small to permit the test
plants to complete their entire life cycle. Residues were mixed into the potting mixture
at application rates of 75, 150, 225, and 300 grams per pot, which corresponds to field
application rates of 67.2,134.4, 201.7, and 268.9 kkg per hectare. Six residues were
tested: CFA, FSFA, VFA, VSBM, NJFA, and NJSBM (these are identified in Chapter 1,
Table 6). There were two control pots, and a total of 50 pots used. Fertilizer was surface-
applied to each of the soil/residue (and control) mixtures: one gram of ammonium sulfate
as* a source of nitrogen and one gram of monobasic potassium phosphate as a source of
phosphate and potassium. These fertilizers were applied in two equal doses of 0.5 grams
each. The first application was made two weeks after planting, and the second four weeks
after planting.
Germinated cherry tomato seeds were planted (3 March 1976); each pot was subsequently
thinned to one plant per pot. There were two replications for each residue application rate;
this was donee to reduce the impact of genetic and environmental variability on the test
results. The tomato plants were irrigated once a week. The plants were harvested on
May 7, 1976.
Results. The results are shown In Figure 197 and 198, (T. represents the lowest applica-
tion rate and T, the highest). No pictures are shown of CFA or FSFA because the tomato
plants did not grow at all in those fluid!zed-bed oil gasification residues. The very high
soil pH produced by the residues significantly suppressed root development for all residues
at all application rates. Also, plant growth was significantly less for the test plants than
for the controls, and higher application rates were associated with reduced growth. From
this experiment it was concluded that (1) there are differences among the six residues in
their effects on plant growth, and (2) at these high application rates there is a significant
negative impact on plant growth and root development. Based on these conclusions, a
second experiment was devised to test the impact of lower application rates (below 35 kkg
per hectare).
Experiment 2.
Procedure. This experiment was identical to the previous one, except as noted.
Application rates were 2.5, 12.5, 25.0, and 37.5 grams per pot, corresponding to field
application rates of 2.2, 11.2, 22.4, and 33.6 kkg per hectare. Three replications were
performed for each application rate, and two controls. There were seventy-four pots used
in total. Fertilizer was applied as above and the plants were irrigated once per week, with
the exception that of the first three weeks when exceptionally warm weather required
irrigation twice per week. Planting occurred on 12 June 1976, and harvesting on 29 July
1976. Above-ground plant tissues were digested and analyzed using the procedures out-
lined in Appendix A.
207
-------
Exxon, New Jersey fly ash
Exxon, New Jersey spent bed material
Figure 197. Experiment 1, tomato plant growth
208
-------
PER, Virginia fly ash
PER, Virginia, and Exxon, New Jersey fly ash
Figure 198. Experiment l^omaro plant growth .
209
-------
Results. Photographs taken of the plants just before harvesting are shown in Figure 199.
The impact of residue application on plant growth is given quantitatively in Table 74 and
graphically in Figures 200 and 201 . Table 74 presents the wet and dry weight and the
ratio of wet to dry weight.
The results show a significant improved growth response at application rates of 2.2 and
11.2 kkg per hectare for CFA, FSFA, VFA, and NJFA residues. For these same residue
types, growth was repressed at 22.4 and 33.6 kkg per hectare application rates. There
was a significant positive growth response at all application rates for the VSBM, and
NJSBM residues. Percent dry weight increased from 5 to 80 percent for all residue types
for application rates of 2.2 and 11.2 kkg per hectare. For CFA, percent dry weight
decreased significantly at a 22.4 kkg per hectare application rate.
The potting mixture used in the experiments had a high ievel of humic acid and, con-
sequently, a low pH (about 5.5). Since the fly ash and spent bed residues are quite alka-
line, adding them to the potting mixture raised soil pH (as shown in Tables 75 and 76).
The effect on plant growth plotted against soil pH is presented in Figure 202. The figure
shows growth improvements (in comparison to the control) when pH was in a range from
6.2-7.8. This improvement is almost certainly at least partially the result of the residues
having increased the pH to more optimal values.
The biodegradatlon of the residue materials by soil microorganisms may also have re-
leased micronutrienfs for plant uptake. If the pH adjustment mechanism were beneficial,
one would expect it would make little difference what type and source of fluidized-bed
residue were used. But, as Figure 2Q2 shows, there is considerable variability in results
for a given pH. Since the various residues differ substantially in chemical composition,
it may be tentatively assumed that this dispersion reflects differences in the availability
and quantity of nutrients that were provided to the plants in the residues.
Results for chemical analyses of plant tissues are given in Table 77, and graphically
in Figures 203 fe 208» Tomato plants grown on residue-treated soil showed significantly
lower concentrations of analyzed heavy metals than the control plants. This effect is
undoubtedly pH-related,, For the most part, sulfate concentrations were not significantly
different for treated and control plants. Exceptions were FSFA/lL, VFA/T., NJFA/T9/
and NJSBA/VX, Lj, and T^. There was no significant difference in the concentration
of magnesium between the control and residue-treated vegetation except for NJFA/X-.
All residue-treated vegetation (except VFA/TJ showed significantly higher concentrations
of calcium, which is associated with Improve*!cell turgidity. Although the calcium con-
centration was higher in the treated plants, they did not show signs of a toxic calcium
level.
From this experiment, it appears that residues applied at reasonably low concentrations
increased the soil pH and therefore restricted the uptake of heavy metals by plants, and
even reduced their concentration En plant tissues. Excessive concentrations of heavy metals
in plants utilized for direct or indirect human consumption are undesirable; specifically
any food with an increased cadmium metal content is considered dangerous for human
210
-------
Control
'1 '3
PER, Virginia fly ash
Control T T. 1 T
2. o 4
PER, Virginia spent bed material
Control T
Exxon, New Jersey fly ash
Conh-ol T, T2 T3
Exxon, New Jersey spent bed material
Control T
,
Esso, England cyclone fly ash
Figure 199.
Control T
Esso, England fines, stack fly ash
Experiment 2-A, tomato plant growth.
211
-------
TABLE 74. EXPERIMENT 2-A: TOMATO PLANT
GROWTH RESULTS
Application
Treatment Rate
Code0 (kkg/ha)
Control 0
CFA 2.2
11.2
22.4
33,6
^ FSFA 2.2
to
11.2
22.4
33.6
VFA 2.2
11.2
22.4
33.6
VSBM 2.2
11.2
22.4
33.6
*,"
31
30
34
15
5
33
27
19
14
36
37
36
43
43
39
35
35
Plant Height
«2B
28
30
33
20
16
35
35
22
9
43
43
43
37
45
40
35
43
(cm)
|3
*»-O
17
29
35
11
13
41
36
19
8
45
45
47
43
40
41
36
37
(continued)
Mean
Height
(cm)
25.3
29.6
34.0
15.3
11.3
39.6
32.6
20.0
10.3
41.3
41.3
42.6
42.3
42.6
40.6
35.3
' 38.7
Green
Weight
of Shoots
(9)
40.0
31.1
57.5
11.4
5.3
62.0
55.0
15.0
13.0
48.8
60.2
64.3
64.4
61.6
28.3
40.0
Dry
Weight
of Shoots
(g)
3.5
4.9
5.2
0.7
0.5
5.5
4.7
1.4
0.9
5.6
6.3
4.2
6.4
5.7
1.9
3.7
Ratio of
Dry to Wet
Weight
8.75
16.55
15.29
4.57
9.43
13.88
14.41
7.01
8.73
13.55
10.46
6.53
9.93
9.25
6.71
9.25
-------
TABLE 74 (Cont.)
CO
Treatment
Code
NJFA
NJSBM
Application
Rate
(kkg/ha)
2.2
11.2
22.4
33.6
2.2
11.2
22.4
33.6
Rb
Rl
43
33
10
5
37
45
43
37
Plant Height (cm)
R2b
36
40
8
8
39
43
45
32
R3b
39
34
3
42
44
37
30
Mean
Height
(cm)
39.3
37.0
7.0
6.5
39.3
44.0
41.6
33.3
Green
Weight
of Shoots
(g)
55.1
38.7
3.9
4.8
35.6
35.2
75.9
33.6
Dry
Weight
of Shoots
(g)
5.4
3.4
0.3
0.4
3.0
3.0
6.0
3.2
Ratio of
Dry to Wet
Weight
9.80
8.78
7.69
8.33
7.63
8.52
7.90
9.52
i Residue source code presented in Table 6.
Replicate
-------
D)
"5
8 20
15
10
e
D VFA
A FSFA
O CFA
I
10 20 30
Residue Concentration (kkg/ha)
Q-See Table 6 for explanation of letter code.
Figure, 200. Mean tomato plant height, Experiment 2: VFA, FSFA, CFA
40
-------
to
Cn
45 r-
40 -
35 -
30
25
§ 20
15
10
5
0
O NJSBM
D VSBM
O NJFA
10
I
I
20 30
Residue Concentration (kkg/ha)
40
See Table 6 for explanation of letter code.
Figure 201 . Mean tomato plant height: Experiment 2: NJSBM, VSBM, NJFA.
-------
Application
Treatment Code Rate
(kkg/ha)
Control
CFA
FSFA
VFA
VSBM
NJFA
NJSBM
0
2.2
11.2
22.4
33.6
2.2
11.2
22.4
33.6
2.2
11.2
22.4
33.6
2.2
11.2 _
22.4
33.6
2.2
11.2
22.4
33.6
2.2
11.2
22.4
33.6
R C
Rl
5.52
7.01
7.43
6.91
7.71
7.07
7.72
7.53
8.22
7.52
7.18
7.59
7.11
6.33
8.21
8.73
7.91
6.83
7.80
8.29
7.42
8.72
7.32
6.61
6.63
Soil
R/
5.62
7.23
7.22
7.72
7.62
7.01
7.51
7.72
10.32
8.49
6.82
7.81
7.83
6.91
7.26
7.51
7.75
6.50
7.69
8.51
8.50
7.62
8.01
8.11
6.42
PHb
*3C
5.55
7.20
7.32
7.70
7.81
7.20
7.73
8.20
9.73
7.62
7.64
6.48
6.31
6.81
7.56
7.92
7.72
6.42
7.25
8.21
6.81
6.91
7.68
8.39
7.42
Mean
5.56
7.14
7.32
7.44
7.71
7.09
7.65
7.81
9.42
7.87
7.21
7.29
7.08
6.68
7.67
8.05
7.79
6.58
7.58
8.33
7.57
7.75
7.67
7.70
6.82
, Residue source code presented in Table 6.
Soil and water mixed in 1:1 ratio.
Replicate
216
-------
TABLE 76. pH OF SOIL RESIDUE MIXTURE AFTER CROP 2 HARVEST
Applicatioi
Treatment Code Rate
(kkg/ha)
Control
CFA
FSFA
VFA
VSBM
NJFA
NJSBM
2.2
' 11.2
22.4
33.6
2.2
11.2
22.4
33.6
2.2
11.2
22,4
33.6
2.2
11.2
22.4
33.6
2.2
11.2
22.4
33.6
2.2
11.2
22.4
33.6
n
R,°
6.7
6.73
7.54
7.17
7.13
7.21
7.80
8.04
8.33
7.14
6.34
7.15
6.76
5.90
7.36
7.82
7.31
7.27
7.75
8.30
6.20
6.24
6.81
7.66
7.35
Soil
R2°
7.1
6.70
6.90
7.60
7.80
7.20
7.60
8.00
7.50
7.60
7.10
6.80
6.30
6.60
6.64
6.71
7.33
6.70
7.0
8.0
6.50
6.12
7.13
7.10
7.60
PHb
R3°
6.9
7.30
7.10
7.40
8.20
6.80
7.40
7.00
8.50
7.40
6.90
7.20
6.20
6.40
7.33
7.43
7.42
7.30
7.0
7.70
6.50
6.21
6.82
6.90
7.50
Mean
6.90
6.91
7.18
7.39
7.90
7.07
7.60
7.68
8.11
7.38
6.78
7.05
6.42
6.30
7.11
7.32
7.35
7.09
7.25
8.00
6.40
6.19
6.92
7.22
7.45
.Residue source code presented in Table 6,
Soil and water mixed in 1:1 ratio.
Replicate
217
-------
CO
45
40
35
30
o
r 25
CO
20
15
10
I
I
Legend
• VFA
A VSBM
O NJFA
O FSFA
D NJSBM
• CFA
I
6789
Soil pH
Figure 202.. Tomato plant growth vs. so?l pH, Experiment 2.
10
-------
TABLE 77. TOMATO PLANT DIGESTION ANALYSIS RESULTS FROM EXPERIMENT 2
Treatment
Control
CFAA,
CFAA2
FSFAA1
FSFAA2
VFAAT
VFAA3
VFAA4
VSBMA1
VSBMA2
VSBMA4
NJFAA1
NJFAA2
NJSBMA1
NJSBMA2
NJSBMAo
o
NJSBMA4
Ca
0.08
0.19
0.19
0.22
1.22
0.12
0.05
0.37
0.17
0.16
0.56
0.12
0.15
0.38
0.30
0.86
0.66
Mg
0.158
0.197
0.145
0.155
0.202
0.153
0.151
0.148
0.211
0.102
0.140
0.135
0.523
0.182
0.130
0.178
0.170
s%°<
1.65
1.50
1.00
0.60
4.30
1.40
0.80
2.30
1.60
0.50
1.90
0.90
3.75
2.60
1.60
3.70
3.40
Mn
ppm
68
93
14
3
14
18 .
17
6
N.D.
N.D.
N.D.
22
N.D.
16
10
12
N.D.
Zn
ppm
51
20
2
20
2
10
5
4
2
7
3
6
0.1
1
1
N.D.
4
Fe
ppm
130
90
N.D.a
N.D.
N.D.
90
30
30
N.D.
40
60
70
N.D.
20
20
N.D.
40
N.D. = None detected.
219
-------
to
S3
O
Legend
O CFA
A FSFA
O NJFA
O NJSBM
D VFA
D VSBM
]Q 2Q 30
Residue Concentration (kkg/ha)
Figure 203. Calcium content in digested tomato plant tissue; Experiment 2.
-------
K>
10
Legend
O CFA
A FSFA
° NJFA
0 NJSBM
D VFA
D VSBM
20
30
40
Residue Concentration (kkg/ha)
Figure 204 Magnesium content in digested tomato plant tissue : Experiment 2,
-------
K>
ro
160
140
I
,? • 80H
Legend
O CFA
0 NJFA
2 NJSBM
D VFA
D VSBM
A FSFA (T , T2/=Oppm)
20 ~ 30
Residue Concentration (kkg/ha)
Figure 205 . Iron content in digested tomato plant tissue: Experiment 2.
-------
90 _
ro
10
CO
10
Legend
D VFA
O CFA
A FSFA
O NJSBM
O NJFA
D VSBM(Tr
T4=0ppm)
20 30
Residue Concentration (kkg/ha)
40
Figure 206 . Manganese content in digested tomato plant tissue: Experiment 2.
-------
'10
Legend
O CFA
A FSFA
- VFA
D VSBM
Q NJFA
O NJSBM
20 30
Residue Concentration (kkg/ha)
Figure 207. Sulfate content in digested tomato plant tissue: Experiment 2,
-------
ro
K>
Oi
Legend
D VFA
° VSBM
Q NJFA
0 NJSBM
A FSFA
O CFA
10
20' 30
Residue Concentration (kkg/ha)
40
Figure 208 . Zinc content in digested tomato plant tissue: Experiment 2,
-------
consumption. Soils containing low pH, high heavy metal levels, or deficiencies in trace
metals appear to benefit most from residue application.
Marketing Analysis Methodology
The method of estimating the potential market for fluidized-bed residues in specific
applications involved converting data on prices of transport, residues, and conventional
materials into the cost-equivalent distance that residues could be economically hauled,
and then using data on power plant locations to determine the geographical extent of the
potential market. Figure 209 shows the location of large coal-fired power plants in the
United States and adjacent areas within a 240 and 480 km range of the plant. The 240
km distance is shown because after approximately that location it may be more economical
to ship by rail. 54 The 480 km distance is shown only for comparative purposes in order
to illustrate that increase in market area coverage may not be proportional to the increase
in travel distance from power plants. Established market patterns that are not easily disrupted,
price rfatio. changes as market penetration increases, and other factors could limit pene-
tration .
The value attributed to residues for any given use should not be considered as the es-
timate of its market price. First, the residues have more than one possible use. For each
use there will be a certain relationship between the demand for the residues and their
delivered price. The aggregate demand relationship for the residues will be the sum of
the demand functions for the different uses. Second, the willingness of sources to supply
residues at various prices would also influence their market price. In other words, market
price is determined by the interaction of both demand and supply conditions, not just by
use value.
The most direct method of estimating the value of a substitute input to a production
process is to raipute its value from the cost of the inputs replaced by the new input, hold-
ing the output constant. Suppose, for example, that 1,000 kg of peanuts could be grown
on a given plot using either 100 kg of ordinary lime (the conventional input) or by using
200 kg of spent bed material from a fluid!zed-bed power plant (the new input). Suppose
further that the delivered price for ordinary lime is $2 per kg and that there is no established
market (and thus no price) for the residues. In this situation, the imputed value of the
residues would be $] oer kg (delivered), based on 200 kg ($200) residue equalling TOO kg
($200) of lime as a so! conditioner. This means that if a market for residues were es-
tablished, a rational producer would switch from lime to residues if their delivered price
was less than $1 per kg.
Sometimes it may not be possible to impute the value of the residues in a given applica-
tion from the cost of the displaced inputs. This would be the case if it cannot be readily
determined how much of which inputs can be replaced by a unit of the new input at the
given output level. In such as case, it may be possible to impute the value of the residues
from their impact on output. Several examples are given below to illustrate the method
and its pitfalls.
226
-------
K)
*-J
Legend
• Power plant site
0-240 km from power plant
km from power plant
Source: 54.
Figure 209 . Distance to large U.S. coal-fired power plants.
-------
If the experimental data available indicated that 200 kg of residues yielded 1,000 kg
of peanuts and that the price of peanuts is $0.50 per kg, we could not conclude that the
value of the residues is $2.50 per kg (1,000 x 0.50/200). It is likely that, even without
any residues, some peanuts would have been produced. Suppose, then, that without any
inputs 500 kg of peanuts would have been produced. Again, this does not imply that the
value of the residues is $1.25 per kg (500 x 0.50/200) since other inputs might be able
to achieve the same result (in this case 100 kg of lime). Taking the example a bit further,
suppose that 300 kg of residues would yield 1,400 kg of peanuts. The value of the extra
output would be $200 and the residues would still be replacing $200 worth of lime. Could
we conclude from this that the proper input value for the residues is $1.33 per kg? Perhaps,
but only if several restrictive conditions were shown (or assumed) to hold. The imputed
value would be wrong, for instance, if a higher lime application rate could achieve the
same yield. It would also be wrong if a third input (a source of sulfur,for example) could
be used in conjunction with lime to achieve the same yield. This would be the case where
the residues serve a function not served by the input being replaced. The problem with
imputations based on output changes is that they may misrepresent the situation. The
appropriate question with respect to any imputed value for an input is, whether or not a
rational producer would adopt that input if its price were less than the imputed value. If
not, then the imputed value is invalid.
The delivered cost of standard quality residues is a prime consideration to the potential
user. Most of the ash currently being reused is removed by a broker (or the ultimate user)
at no cost to the utility. In that situation, the price (or cost) to the user will represent
charges for (1) pick-up, (2) transport, (3) quality standardization, and (4) profit to the
broker. For purposes of analysis, the broker profit will be neglected, although a fixed
percentage could be included in the calculation. For many reuse applications it is im-
portant that the chemical and physical characteristics of the residues are standardized
within reasonable limits. Variations in residue parameters may limit its usability. Ob-
viously, for some applications, physical and chemical variations would be significant; for
others they may make little difference. For certain uses it has been estimated that the
delivered price of fly ash assuming uniform quality could be as high as $10 to $14 per kkg.
Shipping costs will affect the delivered prices for residues and virgin raw materials.
With widespread adoption of fluidized-bed processes, most areas of the nation (with the
possible exception of the West) will have ready, close-by access to residues, in many
cases, access to residues may even be better than for alternative conventional raw materials.
Approximate truck transport costs are $0.04 per kkg/km (with 18 to 27 kkg per truck).
For short hauls, an extra charge of $1.00 for loading and the same charge for unloading
has been assumed. As stated previously, the maximum efficient range for truck transport
is estimated to be about 240 km (depending on road conditions), since at that distance
the driver can get to his destination, unload, and return on the same day, while avoiding
overtime and other costs for a layover. 4 For rail transport, a car-lot is about 50-54 kkg
and transport cost about $0.02 per kkg/km, plus an additional fee for shaking the car to
complete unloading. It should be noted that rail freight rates discriminate about 20 percent
against secondary materials (such as fly ash) in comparison to primary materials.
228
-------
Although current practice provides zero-cost pickup of residues from some power plants,
it may be reasonable to assume that utilities must generally pay to have them removed.
The value of the fly ash to them is not zeio, but rather is less than zero by the unit they
have to pay to dispose of the residues. The cost of land disposal has been, and is projected
to continue increasing in response to: (1) the impact of general inflation on transport and
handling costs, (2) increasing scarcity of acceptable, close-by landfill sites, and (3) in-
creasing strict environmental regulations on waste disposal. Disposal cost will vary from
place to place, but can generally range from $3-6 per kkg. Costs may be even higher if
special treatment is necessary prior to disposal. For example, chemical fixation followed
by landfilling is one method of treatment for the residues from limestone flue-gas desulfurf-
zation systems. The experience of several firms with that process is shewn in Table 78.
Thus, certain applications not judged economically feasible if the residue cost was
zero at the power plant site may be acceptable if the power plant paid for removal of the
residues. Because of the difficulties in estimating (1) what the utility would be willing to
pay for residue removal, and (2) the cost of insuring adequate residue quality, in the re-
mainder of the analysis, it will be assumed that these two factors balance one another and
that the residues are available at a zero cost.
Economic Analysis of Specific Applications
Concrete.
Substantial research (discussed above) exists showing that adding fly ash to concrete
can improve the characteristics of the concrete. The fly ash can be used to replace aggre-
gate and, because it is also a pozzolan, a portion of the portland cement. Based on pre-
liminary research results, concrete mixtures with approximately 5 percent residue content
dispiay improved strength characteristics. Table 79 compares the composition of the op-
timal concrete mix (as determined in the testing program) containing residues to that of a
standard concrete mix (used as a control for the tests). The table also estimates the cost
savings from using residues as a partial substitute for aggregate and portland cement which
would result if residues were available at a free delivered price. This saving would be
$0.50 per kkg of concrete. Since 53 kg of residues would be used in one kkg of concrete,
the imputed value of the residues would be $0.50/53 kg or about $0.01 per kg of residue.
This implies that a concrete producer would (all other things equal) use the residues if their
delivered price were about $0.01 per kg or less. To the extent that the improved character-
istics imparted by the residues to the concrete results in a higher matket price for the
concrete, the producer may be willing to pay in excess of $0.01 per kg delivered for the
residues. Assuming an imputed value of $0.01 per kg, a rail freight rate of $0.02 per
kkg-km, and a zero f .o.b. price for the residues at the power plant site, residues could
be rail-hauled a distance up to 472 km and remain competitive. By truck they could be
economically transported about one-half that distance.
Asphalt.
Coal ash has been used successfully as a replacement for aggregate in asphalt for some
229
-------
TABLE 78 . SLUDGE FIXATION COSTING ESTIMATES
All values are condition and site dependent
Source
Commonwealth Edison
Company, Will County
Station
Duquesne Light Company,
Phillips Station
International Utilities
Conversion Systems, Inc.
Chemfix
Dravo Corporation
Cost
($Akg,50% solids)
6.50
9.41
5.78
11.00
5.50
7.98
1.65-2.75
5.50
1.65-3.30
Remarks
On-site disposal — vendor quote
Current estimate
Best experience
Worst experience
Target
Total disposal
On-site disposal
On-site disposal
Total cost to customer; includes pump-
ing to 10 mi
Company Operation - on-site disposal; excludes capital costs.
TABLE 79, RESIDUE VALUE FOR USE IN CONCRETE
Composition (%) Value ($Akq)a
Control Residue Added Control Residue Added
Item
Cost Reduction
($Akg)
Concrete compo-
nent
Fly ash
Aggregate
Portland cement
Water
Total
0
71.5
15.2
13.3
100
5.3
64.7
14.9
15.1
100
0
3.55
8.02
0
11.57
b
3.21
7.86
0
11.07
0
0.34
0.16
0
0.50
Based on a delivered cost (in Los Angeles) for portland cement of $52.78/kkg and for
, aggregate of $4.96/kkg.
Value of residue to be imputed from savings from its use ($11.57 - $11.07 = $0.50/kkg).
230
-------
time. For example, the West Virginia Department of Highways has found that an asphalt
surface coating with a thickness of 5 to 7.5 cm made from dry bottom-ash and emulsified
asphalt works satisfactorily and its cost is about half that of conventional asphalt. The
low cost results, from two factors. First, there is a large, readily available supply of coal
ash located conveniently throughout the state. Second, the technology required is simple
and the same as needed with conventional asphalt. Ash is loaded into a portable con-
tinuous pugmili, frequently located at the power plant site, and mixed with a metered
amount of emulsified asphalt. Then it is either loaded directly on trucks or stockpiled for
future use. The well-graded ash usually requires no additional blending. Using emulsified
asphalt makes heating and drying unnecessary, thus eliminating the need for relatively
costly hot bins or dryers.
Other examples of successful use of coal-ash residues in asphalt could be cited. But
even though the technology appears simple and sound, use in this application has remained
quite limited (approximately 180,000 kkg of residues in 1972)J3l There does appear to
be a substantial potential market, however. In comparison to a delivered (Los Angeles)
price of aggregate of $4.96 per kkg, conventional coal-combustion residues could be
transported approximately 250 km by rail (at $0.02/kkg-km) or 125 km by truck (at $0.04/
kkg-km) and be competitive.
Little work has been done on limestone or dolomite modified residues. Wet-collected
residues from flue gas desulfurization systems appear to have some promise in asphalt
applications. However, if substantial dewatering or drying is required prior to use, their
cost may be prohibitive. Fluidized-bed residues are collected dry, and appear to have a
higher potential. Preliminary tests were conducted to determine the technical feasibility
of using fluidized-bed residues in a mixture with emulsified asphalt. The results indicated
that up to 92 percent of the aggregate could be replaced. Table 80 shows the approximate
savings which could be realized assuming a free delivered price for the residues, and 92
percent replacement. For any given transport distance (or delivered price for residues)
the net savings or costs per unit of asphalt can be easily calculated.
TABLE 80. IMPUTED VALUE OF RESIDUES IN ASPHALT APPLICATIONS
Item
Asphalt Component
Emulsified asphalt
Aggregate
Fly ash
Total
Composition (%r
_ t , Residue
Confrcl Added
8
92
0
Too
8
0
92
Too
Control
94.53
4.96
0
99749
($/kkg)a
Residue
Added
94.53
0
b
•HBWMW-v
94.53
Cost
Reduction
( $Akg)
0
4.96
0
4~96~
QBased on a delivered cost (an Los Angeles) for asphalt of $93.53/kkg and for aggregate of $4.96,
Value of residue to be imputed from savings from its use.
231
-------
Agriculture
Fluidized-bed residues can improve crop growth and yield by (1) altering pH (the residues
are quite alkaline), (2) improving soi! structure, (3) providing essential micronutrients
(Zn,Cu/Fe,Mn/B/Cl/AI)/ (4) providing sulfur, and (5) serving as a source for macro-
nutrients (O,C,H,N,P,K,Mg,Ca). Thus, the residues can serve many functions as an
agricultural input. The purpose of this analysis is to estimate the value of the residues
for agricultural applications. Because both the residues and many conventional agricul-
tural inputs serve multiple functions, it is sometimes difficult to identify the inputs which,
in a given application, could be replaced by fluidized-bed residues. Therefore, some of
the analysis below will be based on the value of yield changes.
Research currently being conducted at the Virginia Polytechnic Institute and State Univer-
sity has indicated that fluidized-bed residues can be used as a source of calcium for
large-seeded peanuts, at least partially replacing application of calcium carbonate. The
impact of providing a calcium source and a comparison between equal applications (980
kg/ha) of residue and calcium carbonate on yield were beneficial. On the average, both
had a positive impact on yield,with the calcium carbonate increasing yield by 17 percent
and the residue increasing it by 11 percent. However, at the given application rate, it is
implied that the delivered price of residues would have to be significantly less than that
for calcium carbonate to make up for the lower yield obtained. For example, the de-
livered price of calcium carbonate in Los Angeles,California, is about $13.60 per kkg.
Applying. 980 kg to one hectare would cost $13.33 for the material and result in (on the
average) an extra $84 of peanut production. Because the residues, as a source of calcium,
are not as good ess calcium carbonate on an equal weight basis, the farmer would have to
be paid $72.11/kkg to accept residues to make it economical for him to do so. Since this
payment is unrealistic, use of residues in this application cannot be predicted on the basis
of the field test results.
However, one factor, transporting costs, suggests that such application could be economically
feasible. Although the calcium content of available calcium carbonate is about 40 percent,
in comparison to the residues' approximate 10 percent, a higher residue application, rate
may result in matching yields achieved with calcium carbonate. For example, suppose
3,860 kg of residues per hectare could achieve the same yield as 980 kg of calcium car-
bonate per hectare (this would equalize calcium content). In this situation,the imputed
value would be $3.40 per kkg and, assuming the residues had a zero f.o.b.price at the
power plant, the economically feasible transport distance would be 170 km by rail and 85
km by truck. This is, of course, a hypothetical result and more experimental work needs
to be completed before the economic feasibility of this application can be determined.
Test pi lot Din Table 81 shows an improvement in yield for the spent bed material versus
the calcium carbonate. As discussed above, the residues may fulfill several functions in
plant growth. Apparently in Plot D, a growth requirement is being met by the residues
232
-------
which calcium carbonate does not meet. The value (relative to calcium carbonate) in
this application is $250 for increased yield and $13 saved by replacing calcium carbonate,
for a total value of $263 per 980 kg. This represents an imputed value for the spent-bed
material of $268 per kkg. However, there would likely be other inputs capable of filling
the same need, and the proper comparison would be without that input. There is some
evidence that in certain types of soil the fluidized-bed residues will achieve higher yields
than will ordinary limestone, even at equal application rates. The VPI study identified
"Woodstock loamy fine sand" as possibly being such a soil type.
TABLE 81. FLUIDIZED- BED RESIDUES AS A SUBSTITUTE
FOR CALCIUM CARBONATE IN PEANUT GROWING
Material Applied
Application Rate Yield ($Aa)
(kg/ha)
B C D E Avg
Control 0 1190 1097 1907 1225 1862 1457
Calcium carbonate 980 1420 1337 2109 1489 1894 1699
Spent bed material 980 1317 1151 2040 1739 1830 1615
Source: 84.
Fluidized-bed ash and spent bed material are both quite alkaline and hence can be used
to raise soil pH. In that function, it is a substitute for slaked iime (Ca(OH)2). The
delivered price of slaked lime in Los Angeles is approximately $65 per kkg. The amount of
NJFA necessary to cause the same pH adjustment as the slaked lime has been estimated to be
13.5 kg; for NJSBM the equivalent is 5.5 kg. This corresponds to an imputed value for NJFA
of $4.80 per kkg and for NJSBM of $11.80 per kkg. Again, assuming a zero f.o.b. price at
the power plant, the NJFA residues could be economically transported 240 km, and the NJSBM
residues 590 km by rail. It should be stressed, however, that these calculations assume that the
only function provided by either the residues or the slaked lime is pH adjustment. Since
this is not the case, it would be necessary to know the yield response for different types of
soils and plants to draw firm conclusions on the economic feasibility of this application. Each
conclusion would be specific for a given type of crop and soil condition.
The market for pH adjustment materials is quite large. On an average, 675-900 kg/ha/year
of limestone is needed to maintain optimal soil pH in areas where large quantities of nitrogen
233
-------
fertilizers are used. For several reasons, one of which is the expense of limestone, less
limestone is used than is necessary for optimal yields. It has been estimated that in the .-
United States, about 80-90 million kkg of limestone could be used annually to advantage.
In those areas where the delivered price of residues is significantly less than for limestone,
on an equivalent basis it can be expected that farmers would more nearly approach the
optimal level of application. The potential market for the residues is therefore substantially
greater than our projected generation rate of 2 to 12 million kkg per year for 1995. As
discussed previously, however, there are also substantial impediments to large-scale
utilization for this purpose, such as transportation costs and the need for farmer education.
234
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Floidized-Bed Combustion Pmgmm. 76~9E3-FBCQM-R4l''^. K-,ty~K,'gress Report,
February 1976. Prepared for the United States Environmental <*Yofectk*n. Agency.
173. Westinghouse Research Laboratories. Experimental and Enginepnng Support of the
Fluidized Bed Combustion Program. 76-9E3-FBCOM-R5. Monthly Progress Report,
March 1976. Prepared for the United States Environmental Protection Agency.
174. Westinghouse Research Laboratories .Experimental and Engineering Support of the
Fluidized Bed Combustion Program. 76-9E3-FBCOM-R6. Monthly Progress Report,
April 1976. Prepared for the United States Environmental Protection Agency.
175. Westinghouse Research Laboratories. Experimental and Engineering Support of the
Fluidized-Bed Combustion Program. 68-02-2132. Monthly Progress Report, May
1976, Prepared for U.S. Environmental Protection Agency.
176. Westinghouse Research Laboratories. Experimental and Engineering Support of the
Fluidized-Bed Combustion Program. 7th Monthly Progress Report, June 1976.
Prepared for the U.S. Environmental Protection Agency.
177. Westinghouse Research Laboratories. Experimental and Engineering Support of the
Fluidized-Bed Combustion Program. Monthly Progress Report, July 1976. Prepared
for the United States Environmental Protection Agency.
249
-------
1/8. Westinghouse Research Laboratories. Experimental and Engineering Support of the
Fluidized-Bed Combustion Program. Ninth Monthly Progress Report,, August 1976.
Prepared for the United States Environmental Protection Agency.
179. Westinghouse Research Laboratories. Experimental and Engineering Support of the
Fluidized-Bed Combustion Program. Tenth Monthly Progress Report, September 1976.
Prepared for the United States Environmental Protection Agency.
180. Westinghouse Research Laboratories. Experimental and Engineering Support of the
Fluidized Bed Combustion Program. Eleventh Monthly Progress Report, October
1976. Prepared for the U.S. Environmental Protection Agency.
181. Westinghouse Research Laboratories. Experimental and Engineering Support of the
Fluidized Bed Combustion Program. Twelfth Monthly Progress Report, November 1976.
Prepared for the U.S. Environmental Protection Agency.
182. Westinghouse Research Laboratories. Experimental and Engineering Support of the
Fluidized Bed Combustion Program. Thirteenth Monthly Progress Report, December
1976. Prepared for the U.S. Environmental Protection Agency.
183. Wong^G.S* and A.D. Buck. Detection of Calcium Sulfates and Magnesium Oxide
in Fly Ash by X-Ray Diffraction (Final Report).U.S. Army Engineer Waterways
Experiment Station Miscellaneous Paper C-76-5. Prepared for the Assistant Secretary
of the Army (R & D)f Department of the Army* June 1976.
184. Yeager,K.E. "The Effect of Desulfurization Methods on Ambien; Air Quality." In
Gould, R.F, Pollution Control and Energy Needs, Washington,D.C.: Arnorican
Chemical Society, 1973, p. 48-68.
185. City of Los Angeles, Department of Water and Power, Sanitary Engineering Division.
"Complete Analyses of Major Los Angeles Water Sources, 1975-1976 Averages."
186. Personal communication. Robert R. Reed, Pope, Evans and Robbins, Inc., to Ralph
Stone, Ralph Stone and Company, Inc., March 23, 1976.
187. Personal communication. R. C. Hoke, Exxon Research and Engineering Co., to
Ralph Stone, Ralph Stone and Company, Inc., March 19, 1976.
188. Personal communication. M. Alphandary, Esso Research Centre, to Ralph Stone,
Ralph Stone and Company, Inc., October 13, 1976.
189. Portland Cement Association. Soil-Cement Laboratory Handbook. Skokie, III.: 1971.
250
-------
190. Sverdrup, H. V., Martin W. Johnson, and Richard Fleming. The Oceans— Their
Physic, Chemistry, and General Biology, (p. 166) Prentice Hall, Inc., 1942.
191. Chaney, R. L. Crop and Food Chain Effects of Toxic Elements in Sludges and
Effluents. Proc. of the Joint Conference on Recycling Municipal Sludges and
Effluents on Land. Published: National Association of State Universities and Land-
Grant Colleges, Washington, D. C. pp. 129-143, 1973.
192. Procopiou, J., A. Wallace, and G. V. Alexander. Microelement Composition
of Plants Grown with Low to High Levels of Sulfur Applied to Calcaneous Soil in
a Glass House. Plant and Soil, pp.. 44,359-365 (1976).
251
-------
APPENDIX A
LABORATORY ANALYTICAL METHODS
Chemical analyses were performed on leachate from the laboratory-scale columns,
the pilot scale columns, and test cells. Environmental Protection Agency methods
(Manual of Methods for Chemical Analysis of Water and Wastes, EPA 625/6-74-003) were
used for all analyses. The analyses performed, the methods used, and references for the
methods are shown in Tables A-l and A-2.
To insure the validity of the test results, EPA-approved quality control procedures
were instituted. The program involved co-analysis of a series of standards, duplicate
unknowns, and spiked unknowns. One duplicate was run for every four samples; where
there were fewer than four samples, all were duplicated. Spikes were run on one of every
eight samples; for fewer than eight samples, at least one spike was run. Standards were
scattered throughout the runs to maintain instrument calibration. All reagents were checked
for stability on a rotating basis which covered each reagent at least twice yearly.
252
-------
TABLE A-l. SOIL PREPARATORY METHODS
n * A I.L j Reference0
Purpose Method (page number)
Total Residue Characterization Hydrofluoric and perchloric
acid digestion 1019
Soluble Fraction Analyses Water extraction 935
Acid extraction (1.0 N_
nitric acid) 935
Base extraction (1.0 N_
sodium hydroxide) 935
Cation Exchange Capacity Sodium saturation 899
Tomato Plant Analyses Wet digestion 11
American Society of Agronomy. Methods of Soil Analysis, Part 2, Madison, Wisconsin^
, 1965; except as noted.
Same as water extraction, except nitric acid solution was substituted for dist'Hed water.
Same as water extraction, except sodium hyc. ,,:
-------
TABLE A-2. ANALYTICAL METHODS
Parameter
Metals
Aluminum
Arsenic
Beryllium
Cadmium
Calcium
Chromium
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Pofastum
Silver
Sodium
Zinc
Physical
Total Dissolved
Solids
Specific
Conductance
Inorganic
Boron
Chloride
Nitrate
PH
Phosphate
Sulfate
Organic
BOD
COD
RC°
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Performed on Reference6
LCL^ PCL° P D^ Method (page number)
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Colorimetric
(Eriochrome cyanide R)
Colorimetric (Silver
diethyldithiocarbamate
Atomic Absorption
Atomic Absorption
Flame Emission
Atomic Absorption
Atomic Absorption
X Atomic Absorption
Atomic Absorption
X Atomic Absorption
X Atomic Absorption
Flameless Atomic Absorption
Atomic Absorption
Flame Emission
Atomic Absorption
Flame Emission
X Atomic Absorption
Gravimetric
Electrometric (platinum
electrode)
Colorimetric (Curcumin)
Titrimetric (Mercuric nitrate)
r Colorimetric (Brucine)
X Electrometric
Colorimetric (Ascorbic Acid)
X Turbidimetric
92
9
99
101
103
105
108
110
112
114
116
118
141
143
146
147
155
267
275
13
29
197
239
481 g
277
*
Manometric 1558h
X
X
Dichromate reflux
Low Levels
High Levels for Saline Samples
21
25
(continued)
254
-------
TABLE A-2 (continued)
RC - Residue characterization.
LCL - Lab column leachate.
^ PCL - Pilot column leachate.
PD - Plant digested sample.
U.S. Environmental Protection Agency. Manual of Methods for Chemical Analysis of
of Water and Wastes. EPA-625/6-74-003 . Washington, D. C. Office of Technology
Transfer, US EPA, 1974.
Analyzed on 1:1 plant/distilled water mixture.
^ American Public Health Association, Standard Methods , Nth ed., Washington, D. C.,
h
American Society of Agronomy. Methods of Soil Analysis, Part 2. Madison, Wisconsin,
1965.
255
-------
APPENDIX B
SAMPLE DATA SHEET
SURVEY OF Pi LOT PLANTS USING FLUiDIZED BEDS FOR THE COMBUSTION OF
COAL AND THE GASIFICATION OF HIGH-SULFUR FUEL OILS
We are conducting special studies for the U.S. EPA (Contract No. 68-03-2347; Project Officer,
Richard Chapman: 1346 Willow Road, Menlo Park, California 94025) on the residues from the
fiuldized bed combustion of coal and the gasification of high-sulfur fuel oils. The purpose of
this questionnaire is to provide us with basic design Information on the pilot plants covered by
the study to aid in our assessment of residue disposal Impacts. Please complete and return to:
Ralph Stone and Company, Inc.
10954 Santa Monica Boulevard
Los Angeles, California 90025 USA
Phone: (213) 478-1501 and 879-1115
1 . General Pilot Plant Characteristics
a. Name of plant:
b. Address:
c. Designer:
Address:
d. Operating organization:
2. Construction Information
a. General contractor:
b. Construction commencement date:
c. Construction completion date:
d. Start-up date:
e. Total capital cost:
3. General Information
a. Number of employees required to operate pilot plant:
b. Number of operating days in 1975:
c. Number of days shut down for maintenance, process modification, etc.
d. Estimated annual operating cost: ^^
256
-------
4. Operating Information. Please give design estimates rather than actual operating values.
Answer in listed units of measure, if possible; if other units are used, please specify them.
a. Bed volume (cu m):
b. Quantity of bed material (kg):
c. Average bed material feed rate (kg/m?n):
d. Average particle size of bed material (cm):
e. Mode of operation
(1) Number of stages:
(2) ( ) Baich; ( ) continuous (check one)
(3) ( ) Once through; ( ) regenerated (check one)
f. Coal or oil feed rate (kg/hr):
g. Air requirements (scfm):
Fuel hydrogen requirements (scfm):
Combustion efficiency:
Power output (kwhr):
k. Heat released (Btu/hr):
I. Please describe number and types of flue gas control equipment (cyclones, scrubbers,
etc.).
m. Quantities and types of wastes produced.
solid:
fly ash:
spent bed material: ____________
liquid:
type: ; quantity:
type: - ; quantity:
257
-------
4. Operating Information (cont.)
n. Describe handling and storage facilities used for the different kinds of wastes.
5. Please provide a copy of the results of any analyses which have been conducted on the
spent bed material and fly ash and copies of recent progress or other reports.
Use the space below or an additional page for additional comments.
Thank you for your generous cooperation.
258
-------
APPENDIX C
COLUMN LEACHATE CONCENTRATIONS
Figures C-1 through C-130 present the amounts of chloride, iron, lead,
nickel, sulfate, zinc, and pH of leachate from the pilot test columns over a period of
eight months. Tables C-1 through C-5 show the variation in leachate constituents from
residues in the coal mine, sanitary landfill, dolomite and limestone quarry, and sea
water columns.
259
-------
!'20
T
IH
o
5 80
40
^120
1
fl>
5*
r5 so
40
Figure C-l
Column 2
Limestone
NJSBM
|120
a>
22
t
2 80
Xi 40
\ iV O /
\\J>£X/
1 I 1 \^ } !_...!_ 1 I J 1 J 1 J 1 1 J
Months 12
Figure C-3
Column 4
Limestone
% 120
4)
ft
-/•x 6 G0
I \
, \
"A"M /"' 40
il V' V
LJS. • \
iiit i"~Pi — r i i i i i i i i i i
Figure C-2
Column 3
Limestone
VSBM
-
^~,
, i i iV7"'r 1 i i i I I I 1 t I r -
Months 12
Figure C-4
Column 5
Limestone
VFA
^\
\
\
l
•Kl ^
! \
^i \
A \ \
/ ' \iir^a—
' I 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1
Months 12 Months 12
Legend
Top lysimeter
Bottom lysimeter — — » •
Top and bottom lysimeters ± A——
Drain —
Figures C-l - C-4. Chloride leachate from Columns 2 to 5. Limestone quarry.
260
-------
Figure C-5
Column 6
Dolomite
VSBM
120
-g
'i
i5 80
40
?i i i i i i i i i i
I 1 1 1 i t
Months 12
Figure C-7
Column 8
Dolomite
NJFA
-J20
I
80
-------
1J120
J.
T>
J
u 80
40
Figure C-9
Column 10
Landfill
VFA
?120
T>
O
80
40
'"V\
i M
V'' x>\
x. * v*.^
Figure C-10
Column 11
Landfill
VSBM
Months
Months
i i i i i i t i i
120
•o
1 00
U
40
Figure C-l 1
Column 12
Landfill
NJFA
80
Figurs C-l 2
Column 13
Landfill
NJSBM
1 1 1 1 1 1 1 1 f ! 1 I 1 1 1 1 1 1 1
Months 12
12
Top lysimeter — —
Middle lysimeler
Bottom lysimeter —• — > —
Drain • ——-
Legend
Top, middle, and bottom lysimeters —»—T—
Drain and top and middle lysimeters —O—0—
Drain and middle lysimeters —7—v —
Figures C-9 - C-12. Chloride leached from Columns 10 to 13. Sanitary landfill,
262
-------
Pi 20
40 '-
FigureC-13
Column 14
Coal Mine
VSBM
J_l
CO
Figure C-14
Column 15
Coal Mine
NJSBM
Months
I I ) I I I I ii 1 I LI ! i I I I I
Months 12
*
6 80
40
Figure C-15
Column 16
Coal Mine
NJFA
i i i i i "
i i i
i i i
Figure C-16
Column 17
Coal Mine
VFA
Months 12
Months
Top lysimeter
Middle lysimeter —
Bottom lysimeter —. — » —
Drain
Legend
Drain ancl middle lysimeter
Top and middle lysimeters
Top and bottom lysimeters
— v—v— Drain and bottom lysimeter
—*—*— Drain & top, middle & bottom
-~»—*— lysimeters
Figures C-13 - C-16. Chloride leached from Columns 14 - 17: Coal mine,
263
-------
I 4.0
2.0
Figure C-17
Column 1
Ocean
VSBM
-o —o —
I I I I I I I I 1 I I I l_.i,.l_...l.. I
Months 12
I
2.0
1.0
FigureC-19
Columns 3 and 4
Limestone
VSBM and NJFA
I I I I I I I I I I !--.
Months 12
2.0
1.0
Figure C-18
Column 2
Limestone
NJSBM
Jl
Hi
M
IT°r~?~i°"t I i..i__ i i I i I i i i i
2.0
Months 12
Figure C-20
Column 5
Limestone
VFA
-0 o~~o —O—o— O O -*- 0 ——
II I I I I I 1 I I I I I 1 I I I I
Months 12
Legend
BoHom lysimeter
Drain and top lysimcters
Top and bottom lysi meters
Drain and top and bottom lysimcters
—a—o-
A A-
O O-
Figures C-17 - C-20. Iron leached from Columns 1 to 5: Ocean and Limestone
quarry.
264
-------
1.0
1.0
Figure C-21
Column 6
Dolomite
VSBM
Months 12
Figure C-23
Column 8
Dolomite
NSFA
Months
12
I
e 2.0
i.o
S. i.o
0.5
Figure C-22
Column 7
Dolomite
NJSBM
I I I I I I I I I I I I
Months 12
Figure C-24
Column 9
Dolomite
VFA
Months 12
Legend
Top and bottom lysimeters
Drain
Drain & top & bottom lysimeters
Figures C-21 - C-24. Iron leached from Columns 6 to 9. Dolomite quarry.
265
-------
0.5-
| 2.0 -
1.0 -
Figure C-25
Column 14
Coal Mine
VSBM
i
| 2.0
1.0
' 1 1 1 1 mr-U-lm-L.r±-l 111 1 J J | _] I
Figure C-26
Column 15
Coal Mine
NJSBM
_
-
Months 12 Months 12
Figure C-27
Column 16
Coal Mine
NJFA
J.1.0
0.5
'•*TATi?r~f~^-»- 1 i i i i i i i i i t ]_
Figure C-28
Column 17
Coal Mine
VFA
f O— O— b«v.
' 1 1 1 1 V-P— t 1 I 1 1 1 1 1 1 1 1 1 1
Months 12 Months 12
Legend
Middle lysimeter
Drain & top & bottom lysimefers — o—-o —
Drain and middle lysimeter — v—v —
Top and bottom lysimeter — *— A —
Drain, lop, middle & bottom —B—• —
lysimeters
Figures C-25 - C-28. Iron leached from Columns 14 to 17: Coal mine,
266
-------
I
- 8.0
4.0
Figure C-29
Column 18
Ocean
NJFA
nn
2.0
Months 12
Figure C-31
Column 20
Ocean
VFA
D — — D— -a —
tiii
Figure C-30
Column 19
Ocean
NJSBM
J4.oh
2.0
•o
34
i i.i i i i i i i i..i ii t. 1.1. i i i
Months 12
Figure C-32
Column 1
Ocean
VSBM
Months . 12
Months 12
Legend
Drain
Bottom lysimetcr —• — • —
Top lysimetcr — — »— —
Drain and top lysirneter —o—o~
Incoming water 0
Figures C-29 - C-32. Iron and lead leached from Columns 18 to 20 & 1: Ocean.
267
-------
1?
T)
8
0.2
0.1
1 0.2
0.1
Figure C-33
Column 2
Limestone
NJSBM
i
3 0.4
1 1 1 | 1 T'F^H 1 1 1 1 1 | 1 ! 1 I
Months 12
Figure C-35
Column 4
Limestone
NJFA
_>•>
•**
1
TJ
8 0.2
' 1 | 1 l 1 T=K-"-| i i 1 1 1 1 i | I | |
Figure C-34
Column 3
Limeston e
VSBM
-
- r.
J/| ^
' | i T-Ti^r^P1*!" i i I 1 1 | i l i i I
Months 12
Figure C-36
Column 5
Limestone
VFA
- ,^.-ON
f \ L III IT^i 1 1 1 1 1 1 r 1 l l 1
Months 12 Months 12
Legend
Top lysimeter _____
Bottom lysimeter — « — • —
Drain «_-_-«—_
Figures C-33 - C-36. Lead leached from Columns 2 to 5: Limestone quarry.
268
-------
»w
•o
5
0.8
0.4
1
-i
0.4
Figure C-37
Column 6
Dolomite
VSBM
r Ǥ- 0-8
t>
o
0.4
V i \ 1 1 1 FT— 1_ 1 . i 1 1 II i 1 1 II
Months 12
Figure C-39
Column 8
Dolomite
NJFA
1
0.2
/yv
W \ iV^f^^! 1 I 1 ! 1 ' ' 1 ' 1—
Figure C-38
Column 7
Dolomite
NJSBM
-
_ ^
-1 \
tt\ i i r^t=fei i i_.i t i i i i i i i
Months 12 '
Figure C-4Q
Column 9
Dolomite
VFA
-
-^
/t.-H-'-t— t~4"-t-=t 1 1 1 .1 1 1 1 1 l_l 1 1
AAonths 12
Legend
Top lysimefer — —
Bottom lysimefer • • —
Drain
Figures C-37 - C-40. Lead leached from Columns 6 to 9: Dolomite quarry,
269
-------
* »
I
TO
J5
0.2
0.2
Figure C-41
Column 10
Landfill
VFA
i
Months 12
Figure C-43
Column 12
Landfill
NJFA
Monti*
Legend
Top lysimeter
Middle lysimeter
Bottom lysimeter
Figure C-42
Column 11
Landfill
VSBM
0.2
Months 12
Figure C-44
Column 13
Landfill
NJSBM
' i '
Months 12
i .1.
Figures C-41 - C-44. Lead leached from Columns 10 to 13. Sanitary landfill,
270
-------
I
TJ
-§0.8
0.4
Figure C-45
Column 14
Coal Mine
VSBM
-
" f\
1 i
/M \
i'lfi \
iil \
I i \V s^
•VI V^---_- X.
/, , r«£E5=t=s ,11111
Months 12
s
]
0.2
Figure C-47
Column 16
Coal Mine
NJFA
>-
-
i^C'TrfV
m \\ i\
riv'H V
/^ '•LvArirar^ i i. .]_l_l_J_
Months 12
f
, E
•o
J
J0.4
0.2
1 , i i 1
Figure C-46
Column 15
Coal Mine
NJSBM
-
i\
l\
II
' W\
f^.f- — vf~\r~-. ^
L^v-^( , iTr", i i i I i I r t i i i
Months 12
|
1 0.4
0.2
1 1 i ? 1
Figure C-48
Column 17
Coal Mine
VFA
-
-
Mv\
\\
\ \ ,
„„;., 1^ ,11111,111
Months 12
Legend
Top lysimeter
Middle
Bottom
lysimeter
lysimeter "~
Figures C-45 - C-48. Lead leached from Columns 14 to 17: Coal Mine,
271
-------
Figure C-49
Column 18
Ocean
NJFA
i i i i i i I i_ i i i._.]..i I i i i i ;
Months 12
Figure C-51
Column 20
Ocean
VFA
1.2
.§0.
0.4
\ 1 1 1 1 ) 1 1 1 1 1 1 1 1 I ! 1 1
°-8
•o
Months 12
Figure C-50
Column 19
Ocean
NJSBM
i i i i j i i i i i i i i i i
Months 12
Figure C-52
Column 1
Ocean
VSBM
Legend
Top lysi meter
Bottom lysimeter
Drain
« - « —
Figures C-49 - C-52. Lead leached from Columns 18 to 20 and 1: Ocean,
272
-------
i
1
0.8
0.4
|
3
V
2
0.8
0.4
Figure C-53
Column 2
Limestone
NJSBM
1
"o
u
2
0.8
~<~N A °'4
!U- X f i i t i i t i i i i i ii i i
Months 12
Figure C-55
Column 4
Limestone
NJFA
1
1
o
0.8
vfL
7 i Vf 1 1 1 1 i i 1 1 ! 1 L.J 1 1_!_L
Figure C-54
Column 3
Limestone
VSBM
-
j*A
!xi 1 1 1" 1 I 1 i 1 1 1 ! 1 1 i 1 1 1 1
Figure C-56
Column 5
Limestone
VFA
"A ^
T~f="'f' 'I ! 1 1 J 1 I I 1 1 1 | 1 1 1
Months '2
12
Legend
Top lysimeter — — ~~
Bottom lysimeter ~~ "~"
Drain •
Figures C-53 - C-56. Nickel leached from Columns 2 to 5: Limestone quarry,
273
-------
1
O
-B
2
0.8
0.4
«— >
"«
•8
Z
0.0
0.4
Figure C-57
Column 6
Dolomite
VSBM
!
.s
u
2
0.8
-fr
IK'."-
** 1 1 1 ! 1 till 1 1 ! 1 1 1 | | | 1 |:
Months 12
Figars C-59
Column 8
Dolomite
NJFA
^**
^
J-
"«J
•8
2
0.8
0.4
A^v-A-fl—
KV/^nr iC/t Vi i. i i i i i i i i i_i
Figure C-58
Column 7
Dolomite
NJSBM
-
-
-
/*!>.
£&£\ i i rT~i i i i i i i i i i i i
Months 12
Figure C-60
Column 9
Dolomite
VFA
/•"x
/ /s \ ^-,
-•'f' 1 1 T 1 l 1 ii i 111 1 ti r i 1
Months 12
Months 12
Legend
Top lysimeter
Bottom lysimeter
Drain ~
Figures C-57 - C-60. Nickel leached from columns 6 to 9. Dolomite quarry,
274
-------
t~*
1
"
W ^LTT \ ^^^^J""*"
ri j rx^t'-F^Tr^ i i i I ] |_ i j | j |
Months 12
Figure C-63
Column 12
Landfill
NJFA
f
^.
— "5
•iS
z
0.8
0.4
A
j/', ,^p^^>-H i t 1 1 -LJ 1 1 1 1 1
Figure C-62
Column 11
Landfill
VSBM
-
-
f •*
l/^^^
v \ i^r i i i T^I i j i i i i i i i i i
Months 12
Figure C-64
Column 13
Landfill
NJSBM
-
-
/x .. .._.
W T_-'-:^----
»T;\.I i^f-Trr-! i i i i i i i i i .i . i
Ki-_»L, 19
Months 12
Legend
Top lysimeter
Middle lysimeter
Bottom lysimeter • •
Drain —
Figure C-61 - C-64. Nickel leached from Columns 10 to 13: Sanitary landfill,
275
-------
0.8
0.4
1
•^
Z
0.8
0.4
Figure C-65
Column 14
Coal Mine
VSBM
-8
z
0.£
"•^^
V\ ir'VT^4-"t— 1 i I 1 1 | 1 ' ' ' ' '
Months '2
Figure C-67
Column 16
Coal Mine
NJFA
1
"el
2
0.8
0.4
/•Cx^
^f^i^^/\^rfT/\ i • ' ' > j ' * * r
Months 1 2
Legend
Top lysimeter — —
Middle lysimeter
Bottom lysimeter •
Figure C-66
Column 15
Coal Mine
NJSBM
- .
-
vx
^r^r^^,., ..it.,..,,
Months 12
Figure C-68
Column 17
Coal Mine
VFA
i/^^Q?
£1 i i i i iTS , i i i i i i . . i i
Months 12
.
Figures C-65 - C-68. Nickel leached from Columns 14 to 17: Coal mine.
276
-------
z
D.O -
4.0 -
/w
/ 1 l^l 1 1 1
Figure C-69
Column 18
Ocean
NJFA
\
I ! 1 1 1 I 1 1 1 1 1 1 1
c.o
4.0
Figure C-70
Column 19
Ocean
NJSBM
_ ~..p._
1 i i i i r i1 i i i i i
8.0
4.0
Months 12
Figure C-71
Column 20
Ocean
VPA
2.0
1.0
i i i I i I i i i I I I I i I i t I
Months 12
Months 12
Figure C-72
Column 1
Ocean
VSBM
i i
12
Top lysimeter
Bottom lysimeter -—
Drain
Incoming water ©
Figures C-69 - C-72. Nickel leached from Column 18 to 20 and 1. Ocean,
277
-------
^3000
2000
1000
Figure C-73
Column 2
Limestone
NJSBM
c
t
2000
TOOO
Figure C-75
Column 4
Limestone
NJFA
fc_i
2000
.1000
Figure C-74
Column 3
Limestone
VSBM
•/
f\ i i i i i i i t i i i i i i i t i i
12
3000
2000
1000
1 1 1 1 1 1 1 1 1 1 1 1 1 I 1
Months
12
C-76
Column 5
Limestone
VFA
/-"TxT^:
/> "-
I I ' I ' I I I I .1 I, I I I. I !
Months 12
legend
Top lysimeter
Bottom lysimeter
Figures C-73 - C-76. Sulfate leached from Columns 2 to 5: Limestone quarry.
278
-------
1
^ 3000
H
2000
1000
Figure C-77
_ Column 6
Dolomite
VSBM
/ \
-jT-^y
' I 1 1 1 1 i 1 >1 1 1 ! 1 \ 1 I 1 I t |
3000
2000
1000
Figure C-78
Column 7
Dolomite
NJSBM
\ I 1 1 1 1 1 1 1 I ! 1 1 I 1 I 1
2000
1000
Months 12
Figure C-79
Column 8
Dolomite
NJFA
2000
1 1 ! 1 1 I 1 1 1 1 1 1 1 1 1 1 1
12
Figure C-80
Column 9
Dolomite
VFA
Montltt 12
Months 12
legend
Top lysimeter
Bottom lysimefer
Drain
Drain and bottom
lysimeter
Figures C-77 - C80. Sulfate leached from Columns 6 to 9: Dolomite quarry.
279
-------
400
200 -
Figure C-81
Column 10
Landfill
VFA
V
2000
t^
vxA
i^J^TLl-^t^*^^ 1 1 1 I 1 1 T 1 1 T 1
Months 12
Figure C-83
Column 12
Landfill
NJFA
1
V
£
"3
*/»
2000
VTK
' -/_ . 1 *-V* — — TTJm» 1
f./w"^\
^< \ 1 ^f^""^1,,^,^} I 1 1 T 1 1 1 1 f | |
Months 12
Legend
T !•-•
Middle lysimeter — —
Bottom lysimeter —_.__..
Drain
Bottom and middle
lysimeter X X-
I Figure C-82
Column 11
Landfill
VSBM
-
-
ft
1' te£>o^"'
Y j | ^sfZ^»-^t^Ci"*^t -J t 1 I 1 I I I 1 t 1
Months '2
Figure C-84
Column 13
Landfill
NJSBM
-ri'-Vyy^vV-yriw y -jx*_j. i i \ \ \ \ \ \ \ \ \
Months 12
3000 -
2000 -
1000 - _
Figures C-81 to C-84. Sulfate leached from Columns 10 to 13: Sanitary landfill,
280
-------
2000
1000
2000
1000
Figure C-85
Column 14
Coal mine
VSBM
|
3000
2000
1000
i ?
i i i i i
Figure C-86
Column 15
Coal mine
NJSBM
1 1 1 I 1 1 I 1 1 1
Figure C-87
Column 16
Coal mine
NJFA
„ 3000
2000
1000
i i i i |
i
i i i i i i
i i i _L
Months 12
Figure C-81
Column 17
Coal mine
VFA
Months 12
Months 12
Legend
Top lysimefer Top, middle, and bottom
Middle lysimefer
Bottom lysimefer • •
Drain ————
lysimeters
Bottom and top lysimeters
Figures C-85 - C88. Sulfate leached from Columns 14-17: Coal mine,
281
-------
J.
» 12000
8000
4000
Figure C-89
Column 18
Ocean
NJFA
1 1 ! 1 1 1 t t 1 1 ! ! t I 1 1 ! !
12,000
8000
4000
Months 12
Figure C-91
Column 20
Ocean
VFA
3000
2000
1000
Figure C-90
Column 19
Ocean
NJSBM
i i i i i i i i i i i t i i t i i i i
i ii i i i i i 11 i i t i i i i
Months 12
Months 12
Figure C-92
Column 1
Ocean
VSBM
3000- -.
2000 -
1000
I i I l l 1 I l__l 1 t l i i
Months 12
Legend
Top lysimeter — — —
Bottom lysimeter ^—• •
Drain .——
Figures C-89 - C-92. Sulfate leached from Columns 18 to 20 and 1: Ocean.
282
-------
io.s
5?
H
0.2
0.1
*«•
1
•* 0.3
2
N
0.2
0.1
Figure C-93
Column 2
Limestone
NJSBM
} 0.3
u
c
R
0.2
"^\ x- °J
/ / • \ X x
// \^ \
v' l \
^i Ir^^rl'^-t— ^=~i ! 1 1 1 ) 1 i 1 I I 1
Figure C-94
Column 3
Limestone
VSBM
o
- i
.' 1
>fcW^>4^>V^I I I 1 1 1 1 r
Months 12 ™"»» «
Figure C-95
Column 5
Limestone
VFA
!
o °-3
c
R
0.2
0.1
£*fxv3=ttr=v=fcz\ i i i I i i ' i ' i i
1 1 1 1
Figure C-96
Column 4
Limestone
NJFA
-
-
/T-r"t--i~l--t— • >~\ ill. !,., 1 !. .!,..
k^^lU, 19
till
Months 12
Legend
Top lysimcter
Bottom lysimeter
Drain
Top and bottom
lysimeters
Figures C-93 - C-96. Zinc leached from Columns 2 to5 : Limestone quarry,
283
-------
1
o 0.3
c
tCi
N
0.2
0.1
Figure C-97
Column 6
Dolomite
VSBM
-
/\
/ i
i \
i \
n / A
I / A 1
\* / \i -
f , •'S^— **• f f£ *V"^"^
£,?vrK/ FTT P-i i i i
^0.3
°°~^
a
c
R
0.2
0.1
1 1 ! I t 1 1 1
Figure C-98
Column 7
Dolomite
NJSBM
-
~t^"^
\
/ N
/-A~l. J-Af— Uj.OlA-1 1 1 1 t 1 1 1 1 1 1 1
Wo-*1* 12 Months 12
J 0.3
C
R
0.2
0.1
Figure C-99
Column 8
Dolomite
NJFA
/"V"'"x
/ •' *v
/ / \ N-
/ / \ V'v.
fr-^ — (— p-j-a^n-rofm | j |
^
f o-3
c
R
0.2
0.1
1 1 1 1 ( | f !
Figure C-100
Column 9
Dolomite
VFA
-
x-x\
"~/ \
' /ii
/V'T'T1'
'' i V i r^«»-.^=i i i i i i i i i i i i
Months 12
Months 12
Top lysimeter
Bottom lysimeter ——
Drain
Drain and top lysimeter — — ——
Drain and bottom lysimefer — ——
Figures C-97 - C-100. Zinc leached from Columns 6 to 9: Dolomite
quarry,
284
-------
•£ 0.3
o
H
0.2
0,1
0.3 -
0.2 ~
0.1 -
Figure C-l 01
Column 10
Landfill
VFA
V 0.3
0.2
0.1
] 1 1 1 1 1 1 1 1 |
Figure C-l02
Column 11
Landfill
VSBM
Months 12
Figure C-l 03
Column 12
Landfill
NJFA
•£ 0.3
u
c
R
0.2
0.1
Figure C-l 04
Column 13
Landfill
NJSBM
-
/Jf^r=r^^=f^y . II I 1 1 1 i I l 1 1
Months 12
Months 12
Top lysimeter
Middle lysimeter
Drain
Legend
Bottom lysimeter
Top, middle, and bottom
lysimeters
Figures C-101 - C-104. Zinc leached from Columns 10 to 13: Sanitary landfil
285
-------
J.
o 0.3
c
R
0.2
0.1
Figure
Column
C-105
14
Coal mine
VSBM
/ ^CV£\
Months
5 0.3
1
0.2
0.1
J 0.3
R
0.2
' 0.1
1 1 1 1 [ | 1 1 !
Figure C-106
Column 15
Coal mine
NJSBM
-
/ -jrTY_^
^^fr-,5^17 . . t i t i , i
12 Months 12
Figure C-107
Column
16
Coal mine
NJFA
"*
-
A
I'/vl
//--•YhrV-.
1/7 \VA \_ "^
V, , , V-£
-------
N
2.0
1.5
1.0
0.5
Figure C-109
Column 18
Ocean
NJFA
"
1.5
j.
0
— c
."•\ N '•"
.' \
\
- \ 0.5
/ \
/ X" "^v
// ^ss^
/i i i i i'5r=T=!rj i i i i i i i i i i i
Figure C-110
Column 19
Ocean
NJSBM
—
-
* \
/ \
- . \
1 \
I \
/s~^*. »»-.——
^i i r-r-T-r 1 "i i i i i i i i i i i i
Months 12 Months 12
0.6
0.4
0.2
Figure C-lll
Column 20
Ocean
VFA
|
*tT
c:
R2.0
/ \
1 1
i i
1 *
1 \ 1.0
"~ /
/ ^-_
/^/ ^v,^
^/ i. i i.i iT~i i J i i i i i i i i .i
Figure C-l 12
Column 1
Ocean
VSBM
-
' J
1 |
' I
/ \
/ \
/ ^ \
/./*\ 's.V
j£*£/ i V+^'l i ' J_ 1 J l i i i i L
Months 12
Months 12
Legend
Top lysimeter
Drain
Figures C-109 - C112. Zinc leached from Columns 18 to 20 and 1: Ocean.
287
-------
16
12
x
O.
Figure C-113
Column 2
Limestone
HJSBM
v 2.
V
,1_L.1._1_. .!_.! .1 1 I -I—1 ..I--I—t—1-1
12
I
a.
Montis 1 2
Figure C-115
Column 4
Limestone
NJFA
7°
I /•'
llilltjiilllliJiiJ
Months 12
12
Q.
Figure C-114
Column 3
Limestone
VSBM
i i i i i i i....i .I..-I...1 i i.
Months 12
.I—I..
12
Figure C-116
Column 5
Limestone
VFA
! 1 1 1 ! 1 L 1 1 1 .1 1 1 1 1 1 1 1
Months I2
legond
Top lysimeter
Bottom lysimeter —~
Drain
Figures C-113 - C-116. pH of leachate from Columns 2 to 5: Limestone quarry.
288
-------
X
a.
-
Y**—
A
: \
\
^
iitii
Figure C-117
Column 6
Dolomite
VSBM
i i i i i i i i i i i i i
12
Months 12
Figure C-119
CoJumn 8
Dolomite
NJFA
| I I l_ l._l I I I I I ...I-J-1—l—t
Month* 12
12
Figure C-11 8
CoJumn 7
Dolomite
NJSBM
il | I III 11 ; I I I I i I i _i_j
Months 12
12
r
D.
Figure C-120
CoJumn 9
Dolomite
VFA
i i i t i i i i i t i i i i i i i i i
Months U
Legend
Top lysimeter
Bottom lysimeter
Drain
Drain and bottom
lysimcter
Figures C-117 - C-120. pH of leachare from Columns 6 to 9: Dolomite quarry.
289
-------
12
12 -
Figure C-121
Column 10
Landfill
VFA
12
X
a.
I I i I i I i i I I I I I i I i i
Months 12
FigureC-123
Column 14
Coal mine
VSBM
Figure C-122
Column 11
Landfill
VSBM,NJFA,NJSBM
j_J..J-L-L.'.J-J-Ti-J I I I I i I I
Months 12
X
CL
12
1_LJL
Months 12
Figure C-124
Column 15
Coal mine
NJSBM
Months 12
,1 I,...I. .1 J
Legend
Top lysimeter
Middle lysimeter
Bottom lysimeter —. --
Drain
Figures C-121
Top and middle lysimeters * *—
Top, middle, and bottom
lyiimeter -^—*—— i —
Drain and top, middle, and
bottom lysimr.ters » •—
- C-124. pH of leachate from Columns 10 - 15: Sanitary landfill
and ocean.
290
-------
12
a
Figure C-125
Column 16
Coal mine
NJFA
i i i i i
X
a.
12
Months 12
Figure C-l 27
Column 18
Ocean
NJFA
3— n— 0-°-
J__l_L_JLJ_
_ULJ__UU
Months
12
x
a.
12
Figure C-l 29
Column 20
Ocean
VFA
_u
_L_I_JL_L
Months ] 2
X
Q.
12
r
-n>o*"~c
Figure C-l26
Column 17
Coal mine
VFA
t I I I I I I. I.. I.. l_l-i-J_(-J_L-L
Months 12
X
a.
12
Figure C-l 28
Column 19
Ocean
NJSBM
|._.,l-.l-. lr I I I I.I I I I 1 I i I i i
Months 12
12
X
CL
..!.. I. .1-1—i
Legend
Figure C-l30
Column 1
Ocean
VSBM
i ,i i i i i i i i i i i i i i i i
Months 12
Top lysirneter Drain and top lysimeter -
Middle lysimeter Drain and top and bottom
Bottom lysimefer »—-• lysimeters
Drain —
Figures C-125 to C-130. pH of leachate from Columns 16 to 20 and 1;
Coal mine and ocean.
291
-------
TABLE C-l . VARIATION IN COAL MINE COLUMN LEACHATE CONSTITUENTS
to
rS
Residue
Type
NJFA
Top lysimeter
Middle lysimeter
Bottom lysimeter
Drain
NJSBM
Top lysimeter
Middle lysimeter
Bottom lysimeter
Drain
VFA
Top lysimeter
Middle lysimeter
Bottom lysimeter
Drain
VSBM
Top lysimeter
Middle lysimeter
Bottom lysimeter
Drain
S
min
700
375
700
—
870
140
90
240
30
280
40
30
80
160
40
30
=
max
1000
990
1000
1000
1250
1280
840
875
1000
1480
1125
1010
1000
1550
1250
1300
Cl
min
12
8
21
12
18
15
18
23
13
20
17
25
19
12
15
24
Range of Concentration
Fe Zn
max
103
60
47
57
63
70
80
60
80
80
39
76
110
96
83
90
min
0.10
0.10
0.10
0.10
0.05
0.05
0.05
0.05
0.03
0.03
0.03
0.03
0.05
0.05
0.05
0.05
max min
0.23 < 0.01 '
0.40 0.01
0.23 0.03
0.40 <0. 01
0.23 <0.01
0.30<0.01
0.25<0.01
0.23<0.01
0 10 0.01
0.25<0.01
O.KK0.01
0.10 <0.01
0.25 0.01
0.40 0.01
0.25 0.01
0.40 0.01
max
0.10
0.20
0.05
0.08
0.05
0.09
0.02
0.05
0.07
0.32
0.06
0.09
0.07
0.07
0.10
0.05
(mg/l)
Ni
min
0.02
0.07
0.04
0.12
0.01
0.01
0.02
0.16
0.06
0.10
0.07
0.03
0.02
0.15
0.04
0.08
max
0.20
0.34
0.17
0.14
0.17
0.12
0.39
0.20
0.09
0.35
0.30
0.20
0.22
0.32
0.20
0.12
Pb
min
0.02,
O.OT
0.02
0.02
0.06
0.02
0.04
0.02.
0.01
0.02
0.02
0.01
0.06
0.02
0.04
0.02
max
0.20
0.20
0.20
0.20
3.20
0.38
0.11
0.22
0.20
0.22
0.19
0.22
0.80
0.63
0.65
0.62
See Table 6 for residue identification.
-------
TABLE C-2. VARIATION IN SANITARY LANDFILL COLUMN LEACHATE CONSTITUENTS
Isi
tS
Residue0
Type
NJFA
Top lysi meter
Middle lysi meter
Bottom lysi meter
Drain
NJSBM
Top lysi meter
Middle lysimeter
Bottom lysimeter
Drain
VFA
Top lysimeter
Middle lysimeter
Bottom lysimeter
Drain
VSBM
Top lysimeter
Middle lysimeter
Bottom lysimeter
Drain
min
35
15
—
63
5
10
10
10
9
12
15
4
140
75
124
170
S04
max
1000
620
675
960
255
500
500
370
207
165
160
25
1365
1370
1250
1260
Range of Concentration
CI" Fe Zn
min
21
22
15
15
10
17
10
15
10
9
12
17
30
32
30
26
max min
ND
64
65
90
40
ND
120
58
87
80
ND
105
56
75
73
ND
120
117
110
115
max
ND
<0
<0
<0
<0
ND
<0
<0
<0
<0
ND
-------
TABLE 03. VARIATION IN DOLOMITE QUARRY COLUMN LEACHATE CONSTITUENTS
S3
Residue0
Type
NJFA
Top lysi meter
Bottom lysi meter
Drain
NJSBM
Top lysimeter
Bottom lysimeter
Drain
VFA
Top lysimeter
Bottom lysimeter
Drain
VSBM
Top lysimeter
Bottom lysimeter
Drain
so.
min
1000
ND
1000
165
420
240
35
490
130
300
400
130
max
1360
ND
1500
950
630
510
1100
1120
1280
1500
1100
1100
cf
min
—
ND
14
13
16
17
21
35
15
15
12
15
max
30
ND
60
107
100
95
80
80
80
120
106
96
Range of Concentration (mg/l)
Fe Zn Ni
min
0 ,01
0.01
O.Oi
0,01
0,01
0,01
0.01
0.01
0.01
0.01
0.01
0.01
max min
0,5 0.01
0,5 0.01
Q.5<0.01
0.3 0»02
0.3<0;0'1
0,3<0.01
O.K0.01
0.1 <0.01
0.1<0.01 .
0.5 0.02
0.5<0.01
0.5 0.01
max
0.09
0.09
0.01
0,1
0.02
0.02
0.05
0.12
0.09
0.18
0.02
0.07
min
0.22
0.06
0.02
0.08
0.05
0.13
0.12
0.08
0.13
0.12
0.13
<0.01
max
0.25
0.14
0.30
0.27
0.25
0.30
0.38
0.25
0.20
0.40
0.25
' 0.38
Pb
min
0.04
0.05
0.03
0.05
0.02
0.03
0.02
0.01
0.02
0.05
0.07
0.02
max
0.38
0.17
0.16
0.80
0.20
0.40
0.18
0.19
0.02
0.61
0.57
0.55
See Table 6 for residue identification.
-------
TABLE C-4. VARIATION IN LIMESTONE QUARRY COLUMN LEACHATE CONSTITUENTS
NJ
NO
Ol
Residue
Type
NJFA
Top lysimeter
Bottom lysimeter
Drain
NJSBM
Top lysimeter
Bottom lysimeter
Drain
VFA
Top lysimeter
Bottom lysimeter
Drain
VSBM
Top lysimeter
Bottom lysimeter
Drain
S*
min
1030
1030
1190
—
200
800
500
700
875
980
750
750
4
max
1130
1100
1450
1000
500
450
1125
1250
1000
1680
1125
1000
a"
min
5
13
14
19
--
10
15
14
12
—
—
"
max
78
41
40
70
—
40
105
67
38
no
105
110
Range of Concentration (mg/l)
Fe Zn Ni
min
0.15
0.15
0.15
0.10
0.10
0.10
0.15
0.15
0.15
0.15
0.15
0.15
max min
0.25<0.01
0.25 0.01
0.25 0.01
0.10 0.02
1.50 0.01
0.10<0.01
0.25<0.01
0.25<0.01
0.25<0.01
0.25 0.01
0.25 0.01
0.25 0.05
max
0.01
0.1
0.08
0.10
0.10
0.025
0.012
0.012
0.01
0.05
0.17'
0.02
min
0.13
0.15
0.15
0.10
0.06
0.07
0.10
0.06
0.05
0.02
0.07
0.06
max
0.35
0.43
0.44
0.4
0.32
0.39
0.4
0.38
0.2
0.36
0.38
0.40
Pb
.min
0.025
0.025
0.025
0.025
0.037
0.60
0.02
0.025
0.025
0.05
0.10
0.04
max
0.37
0.16
0.37
0.14
0.2
1.8
0.2
0.19
0.18
0.6
0.78
0.25
See Table 6 for residue identification.
-------
TABLE C-5. VARIATION IN SEA WATER COLUMN LEACHATE CONSTITUENTS
ro
Range of Concentration
Residue
NJFA
Top lysi meter
Drain
NJSBM
Top lysi meter
Drain
VFA
Top lysi meter
Drain
VSBM
Top lysi meter
Bottom lysi meter
Drain
50= Cf
min
3800
2500
1250
2450
1900
3400
1750
1500
1500
max min
ND
7000
8500
ND
2000
2550
ND
6300
6000
ND
3000
2300
2300
Fe
max min
ND
1
ND
0
0
ND
0
0
ND
0
0
0
.0
—
.5
.5
.5
.5
.5
.5
.5
max
5.5
0.5
1.4
1.4
1.5
1.5
3.4
3.4
2.8
Zn
min
0.05
0.06
0.15
0.05
0.12
0.02
0.15
0.1
0.05
max
0.90
0.60
0.90
0.17
0.42
0.12
1.80
0.40
0.40
(mg/l)
Ni
min
0.26
0.06
0.06
0.06
0.22
0.23
0.62
0.80
0.35
max
0.38
0.33
0.24
0.24
0.30
0.27
1.37
1.40
2.0
Pb
min
0.40
0.70
0.15
0.16
0.2
0.63
0.55
0.30
0.30
max
1.60
0.78
1.03
0.85
0.87
0.90
2.25
2.75
3.00
See Table 6 for residue identification.
-------
APPENDIX D
CHARACTERIZATION OF SIMILAR RESIDUES
Coal Ash
Cpal ash Is primarily an iron-aluminum-silicate material which contains lime,
magnesia, sulfur trioxide, sodium and potassium oxides, and carbon, as well as traces
of heavy metals. Although the specific composition of a coal ash is mainly dictated
by the geology of the coal deposit and the operating parameters of the boiler unit, many
common minerals are present in U.S. coal. A breakdown of these minerals is given in
Table D-l . Table D-2 tabulates a more detailed compilation of typical coal ash chemical
constituents. The soluble constituents of coal ash from distilled water are summarized
in Table D-3.
During combustion, the inorganic minerals in the coal are subjected to furnace
temperatures between 1400°C and 1700°C. At these temperatures the minerals will
react to form muJIite, quartz, hemmatite, and calcium-sulfate. The distribution range for
these mineral phcses is compiled in Table D-4.
Fly ash generally occurs as fine spherical particulates ranging in diameter frorr 0.5/u
to lOOju, and having an average diameter of 7/u. The color of fly ash will range from
light tan to gray to black, depending on the iron and carbon content. The pH of fly
ash will vary from 6.5 to 11 .5 and will average about 11. A summary of the typical
physical properties of fly ash is presented in Table D-5. Figure D-l diagrams the con-
centration range of the major constituents in U.S. fly ash.
The residue recovered from the bottom of a coal-fired boiler unit occurs as either
bottom ash or slag. These residues are typically composed of gray to black porous,
angular particles. Depending on the type of boiler process used, some particles will
have a glassy appearance.
The fly ash modified by limestone or dolomite injection into boilers will have signifi-
cantly different composition from normal fly ash. The ash compositions generated by the
combustion of bituminous coal and lignite coal are compared with the ashes obtained in the
limestone and dolomite injection processes in Table 53.
Municipal Incinerator Residue
During incineration, furnace temperatures are between 980 C and 1100 C, with
flame temperatures at approximately 1400 C. This process results in the reduction of the
incinerated refuse to 25 to 35 percent of its original weight and to less than 10 percent of
its volume. The resultant residue after quenching is a wet, complex mixture of metal, glass,
slag, charred and burned paper, and ash. It is the ash that is important here because its
chemical composition is very similar to that of fly ash from coal-burning boilers.
297
-------
ABLED=T_.__£QMMQbLMINERALS
Pyrite, marcasite - FeS2
Chalcopyrite - CuFeS«
Arsenopyrite - (FeS2 • FeAs«)
Stibnite - Sb2S3
Gypsum - CaSO4 •
Calcite - CaCO«
Quartz - SiO2
Siderite - FeCO,
(7)
Kaolinite - AI^O
Dolomite -CaMg(CO3)2
Apatite - Ca5(F, Cl, OH)
Mica-KAI2(Si, AI)301Q(OH)2
TABLE D-2 .
Constituents
Silica (SiO2)
Alumina (ALO_)
Ferric oxide (Fe«O_)
Calcium oxide (CaO)
Magnesium oxide (MgO)
Titanium dioxide (TiO«)
Potassium oxide (K«O)
Sodium oxide (Na«O)
Sulfur trioxide (SO )
Carbon (C)
Boron (B)
Phosphorus (P)
Manganese (Mn)
Molybdenum (Mo)
Zinc (Zn)
Copper (Cu)
Mercury (Hg)
Uranium (U)
CHEMICAL CONSTITUENTS OF COAL
Range
20-60
10-35
5-35
1 -20
0.25 - 4
0.5-2.5
1.0-4.0
0.4-1.5
0.1 -12
0.1 -20
0.01 -0.6
0.01 - 0.3
0.01 - 0.3
0.01 -0.1
0.01 -0.2
0.01 -0.1
0.0-002
0.0-0.1
ASH
Average
48
26
15
5
2
1
2
1
2
4
Trace
Trace
Trace
Trace
Trace
Trace
Trace
Trace
"Alkalies
Source:
298
-------
TABLE D-3. CHEMICAL CONSTITUENTS OF COAL ASH _
Soluble Ions Range (for 1 -1.7% dry solids)
Co4"4" 200 - 850 ppm
r-t,,.y
Mg 185 - 400 ppm
SO4~ 200 - 250 ppm
K+ Trace
Na Trace
PO4~ 0-5 ppm
BG>3~ 0-10 ppm
Source: 128.
TABLE D-4. MINERAL PHASES FOUND IN COAL ASH
Phase
Quartz
Mullite
Magnetite
Hematite
Glass
Percent
0-4
0-16
0-30
1-8
50-90
Source: 126.
299
-------
TABLE D-5. PHYSICAL PROPERTIES OF FLY ASH FROM PULVERIZED
COAL FIRED PLANTS
Constituents
Unit
Range
Range of particle size
Average percent passing No. 325 sieve (44/n)
Bulk density (compacted)
Specific gravity
Specific area/gram
microns
percent
kg/cu m
cu cm,
I/O
0.5-100
60-90
1,TOO-1,300
2.1-2.6
3,300-6,400
Source: 69.
300
-------
ou
50
40
g
§
'•J5 30
4-
c
§8
U 20
10
II II
1
1
1
1
1 r
1
1 Range ~
1
1
! ' L
- i !
•
I
! r
i
1
1 1
• !
i i
1 i
* :
i i i i *
SiOo AI2Os FeoOo CaO MgO
fc ij
Constituent
1 1 1
_
1 |
1 / Average
t^
1
-
—
^
t
i
• ^ 4"
SOg Na2O Other Loss on
Ignitioi
Source: 34.
Figure D-l . Concentration range and average of U. S. fly ash consfituents.
-------
In comparison, the fly ash is predominately 200 microns in size, and consists of wood and
paper ash, aluminum foil, carbon particles, metal pins and wire, glass, sand, and iron
scale. A general analysis of the inorganic components found in fly ash is presented in
Table D-6. A comprehensive elemental analysis for four different municipal incinerator
fly ashes is presented in Table D-7. It has also been reported that small amounts of cad-
mium, lead, and mercury have been found in fly ash samples.
Sludge From Li me-Limestone Scrubbing Processes
In Table D-8, chemical analyses of nine sludges collected from nine different lime-lime-
stone scrubbing processes are presented. The nine different sources or conditions under
which these sludges were produced are listed in Table D-9. The results of an X-ray analysis
performed on these sludges are listed in Table D-10.
TABLE D-6. OXIDE ANALYSES OF INCINERATOR FLY ASH FROM TYPICAL REFUSE
Component Total Oxide Content (%)
sio2
AI2°3
Fe2°3
CaO
MgO
Na2O
K20
TiCL
2
S0_
3
P2°5
ZnO
BaO
53.0
8.2
2.6
14.8
9.3
4.3
3.5
4.2
0.1
1.5
0.4
0.1
102.0
Source: 41.
302
-------
TABLE D-7. ELEMENTAL HEAD SAMPLE ANALYSES OF MUNICIPAL
INCINERATOR FLY ASHES (% by weight)
Sample
F-l
F-2
F-3
co F-4
CO
Sample
F-l
F-2
F-3
F-4
Ag
0.02
0.01
0.07
0.01
Ni
0.04
0.03
0.03
0.02
Al
11.63
11.03
13.31
11.51
P
0.76
0.63
0.60
0.63
Ba
0.11
0.09
0.23
0.11
Pb
0.50
0.40
0.26
0.38
C
5.16
0.68
0.42
11.18
S
0.47
0.40
0.51
0.32
Ca
5.23
6.09
4.25
4.16
SI
17.98
22.88
20.57
18.03
Cu
0.08
0.13
0.06
0.05
Sn
0.18
0.14
0.13
0.18
Cr
0.11
0.06
0.05
0.06
Ti
1.54
1.13
1.88
1.41
Fe
3.22
3.21
2.05
2.11
Zn
0.74
0.60
1.50
0.63
1
0
1
1
0
0
0
0
K Mg Mn
.66 0.99 0.40
.76 0.94 0.11
.12 0.99 0.07
.92 0.92 0.15
Au
.01
.01
.01
.01
Na
1.93
2.28
1.55
1.09
Source: 33.
-------
TABLE D-8. WET CHEMICAL ANALYSIS OF SLUDGE STANDARDS0
STD 1
SiO2
AI203
Fe203
CaO
MgO
Na2O
CO
2 K20
TiO2
?205
CO2
SO2
S03
CaCO3
46
23
13
4
0
0
2
1
0
2
0
5
.7
.2
.7
.7
.9
.3
.6
.5
.3
.6
-
.8
.9
STD II
1.5
0.32
0.27
49.6
0.54
0.04
0.17
<0.02
0.05
29.2
11.7
3.5
65.7
STD III
30.7
6.6
8.6
22 .7
1.5
0.50
1.1
0.26
0.11
5.3
5.8
6.5
12.0
STD IV
0.79
0.05
0.18
42.5
0.10
0.03
0.05
<0.02
0.06
3.7
38.8
3.3
8.4
STD V
19.4
6.8
5.4
27.6
3.2
0.08
0.24
0.32
0.08
7.2
2.2
12.3
16.3
STD VI
1.1
0.01
0.09
52.5
0.52
0.02
0.14
< 0.02
0.13
36.6
6.3
0.5
80.6
STD VIA
27 .7
14.7
8.3
24.2
0.70
0.16
1.2
0.79
0.19
15.3
3.4
<0.1
34.7
STD VII
4.6
2.3
1.6
40.1
0.20
0.05
0.29
0.11
0.08
13.6
5.4
24.9
30.9
STD VIII
1.2
0.48
0.72
42.5
0.90
0.05
0.07
<0.02
0.06
11.5
24.1
8.4
26.1
STD IX
2.0
0.45
0.72
46.2
0.40
0.04
0.21
<0.02
0.07
24.4
13.7
4.4
55.4
a Standards are identified in Table D-9.
Source: 144.
-------
TABLE D-9. IDENTIFICATION OF ARCS SLUDGE STANDARDS
Standard Description
I Fly ash from Connecticut Light and Power Company's Devon Station.
11 C-E sludge0—CaCOa • 150% of stoichiometric. 2,000 ppm SO2.
Ill Kansas Power and Light sludge.
IV C-E sludge—-Co (OH)2. 38% to 50% of stoic hiometric. 50 to 60%
SC>2 removal. Slurry feed 830 liters/min. Recycle 625 liters/min
with 210 liters/min blowdown.
V Union Electric sludge.
VI C-E sludge—CaCOg. 150% of stoic hiometric. 45 to 55% removal.
No recycle.
VIA Standard VI plus 50% Standard I (fly ash).
VII C-E sludge—300 to 325% of stoichiometric. 64% SO2 removal.
135 kg/hr fly ash. 250 kg CaCO3.
VI11 C-E sludge—120 to 130% of stoichiometric Ca(OH)2. 90.8% re-
moval. 450 liters/min Ca(OH)2 slurry underbed. Inlet SO2 860 to
840 ppm. Outlet SC^ 80 ppm. 65 kg/hr Ca(OH)2. No fly ash
addition.
IX C-E sludge—830 liters/min H2O spray. 125 kgAr lime feed. 150 C
reaction temperature.
a Sludge from the Combustion Engineering pilot plant.
Source: 144.
305
-------
TABLE D-10. X-RAY ANALYSIS OF APCS SLUDGES
Standard Major Minor Trace
I SiO2 Fe0O0 CaCO^
Source: 144.
III Si00 Fe304 3AI2O3-SiO,
2 CaCOs Ca(OH)2
2CaSO3-H2O CaSO4
MgO
IV 2CsSO3-H2O
V SiO2
CaC03
VI CaCOs
VIA CaCO3
VII 2CaSO3-H2O
VIII 2CaSO3-H2O
IX CaCOs
—
CaSO4-2H2O
2CaSOs-H2O
SiO2
2AI2O3^2SiO2
CaCO3
CaCOs
Si O2
Ca(OH)2
2CaSOs-H2O
Fe304
3Al2O3-2SiO2
CaSO4
SiO2
2CaSOs*H2O
CaSO4
Fe203
2CaSOs*H2O
CaSO4-2H2O
SiO2
Ca(OH)2
Si 62
SiO2
CaSO4-2H2O
Fe203
Ca(OH)2
306
-------
APPENDIX E
DESCRIPTION OF FBC UNITS
PROVIDING RESIDUES
Pope, Evans, and Robblns Process (Alexandria, Virginia)
The U.S. Energy Research and Development Administration supports one pilot-scale
and one full-scale fluidized bed coal combustion unit operated by Pope, Evans, and Robbins
(PER). In an earlier project on the PER unit (spnsored by the National Air Pollution Con-
trol Administration), they monitored air pollution emissions from the fluidized-bed combus-
tion of coal under different conditions to determine those most favorable for reducing SO2
emissions. Major test variables and ranges were:
Coal type Medium and high sulfur
Bed temperature 815-1,038 C
Bed depth 15-51 cm
Bed material Sintered ash and limestone
Flue gas oxygen content 0.5-5.0%
Superficial gas velocity 1 .8-4.3 m/sec
Sorbent type Dolomite 1337
Limestone 1359
Sorbent state Raw, hydrated, and precalcined
Sorbent particle size 7-325 mesh
Fly-ash recirculation Full range (0-80%)
Method of sorbent feed Pneumatic feed with the coal,
pneumatic feed remote from
the coal feed and premixed
with the coal
Tests were conducted on both pilot-scale and full-scale test units. This study tested
residues from the full-scale unit located at Rivesville, West Virginia, only.
Fluidized-Bed Combustor (FBC)
The FBC tests explored SO9 capture on a bench scale prior to a major expenditure of
resources in testing the full-scale unit. Flue gas analyses, sulfur balances, and bed particle
size versus time analyses were compiled for these tests. Portions of the operation also tested
used salt addition for sorbent SO2 activity enhancement, and for combustion catalysis in a
once-through operation. The bench scale fluidized-bed combustor (FBC) contained a rec-
tangular bed with dimensions 30.5 by 40.6 cm. The combustor was enclosed by an air
distribution grid at the bottom, and water walls around the periphery. Side and front views
307
-------
are shown in Figures E-l and E-2.
Air passed into a plenum below the grid, through the grid buttons, and into the com-
bustion chamber to fluidize the bed material and provide combustion oxygen. The bed
material generally consisted of sintered coal ash crushed and double -screened to a mesh size of
<8 to >14(or of limestone 1359 of mesh size
-------
Combusted Gases
Water Wai led
Column
Fly Ash (fuel)
Feed Scre
Start-up Coal
Feed Screw
Injection
Air
Fuel Injection
Port
Source: 124.
Welded Seam Duct
Sight Port
Water Cooled Hood
Light-off Burner Port
Thermocouple Ports
Wall
Auxiliary Feed
Ports (2)
Plenum Chamber
Figure E^-l. FBC construction detail (side view),
309
-------
. Co
-------
CO
FBM Gas
Breeching
Steam
Drum
Front Panel
Ughtoff
Burner
FBM Exhaust
A
Vertical Coal-
Feeder Inlet
Additive or
Ash Feed
Port (auxiliary)
Air Plenum
.Fluidized Bed
Header
Down comers
Source:124.
Figure E-3, Fluidized bed module: internal construction.
-------
To FBM
Dust
Collector
and Stack
GO
CBC Flue, Gas to CBC
Dust Collector and Stack
Air
Heater
Air
Source: 121 .
BC (behind FBM)
Gas to Sample System
FBM
o o
«—Greatly Exaggerated Separation-*-]
Connecting Slot
Gravity Bed Feed
Inclined Screw
Drop Leg
Gas Outlet
Gas Cooler
X
X
LU
_«)
O.
t/1
p
E
2 .
V 1'
Bed Sample
£t
*~
i_
<
£
E
^.
C CN
6 ^
\J •
x
-------
An experimental carbon burn-up cell (CBC) was added to the FBM to raise the system
carbon burn-up from 90 percent into the 98-100 percent range, and to determine the
problems of operating with two distinct temperature zones (815° C in the FBM and 1,038° C
in the CBC). The CBC consisted of a chamber with a rectangular cross section (27 by 40
cm). The uncooled insulated walls of the CBC were fabricated of 27 percent chromium steel.
The CBC was an integral part of the FBM and was located at the back of the combustor under
the steam drum. Figure E-5 is the section view of the integrated FBM/CBC unit. The CBC
operated continuously and burned the carbon-con tain ing fly ash from the FBM. Coal was
fed with the fly ash when ash alone could not maintain the desired 1,038-1,149° C bed
temperature. Fly ash from the CBC's own collector was also recycled during most tests.
CBC emissions of hydrocarbons and< carbon monoxide were essentially zero. Figure E-6
shows the flow path of bed material for the FBM, CBC, and regenerator.
Exxon Research and Engineering's Process (Linden, New Jersey)
The U.S. EPA (Office of Research and Development) sponsored a two-phase program
to investigate the feasibility of producing large amounts of heat at low SO emission levels
by burning coal under high pressure in a fluidized bed of limestone. The first phase of the
program involved the design and construction of a continuous f luidized-bed combustion/time
regeneration pilot unit—the FBCR miniplant (shewn In figure E-7). Design parameters of
the process (mainly combustor and regenerator) are shown In Table E-l. The unit has been
designed to operate at pressures up to 10 atmospheres with a heat release rate of about 1.5
million kcal per hour, equivalent to a power plant capacity of approximately 635 kilowatts.
The combustor was constructed from a 61-cm., refrectory-lined pipe with a final 'nside
diameter of 30 cm. It was designed with 5 flanged sections (each 0.9 m long), a bottom
plenum for air intake below the removable distributor plate, and an upper bed expansion
section containing the gas discharge outlet to the cyclones. The regenerator was constructed
from a 46-cm pipe, refractory lined to 13 cm internal diameter.
Fluidizing air to the combustor and regenerator was supplied by a stationary compressor
with a capacity of 36.8 std cu m/min. Control valves and differential pressure transmitter
controlled the superficial bed velocities. In the combustor, the air passed through the
distributing grid and then the fluidized bed, to a heat exchanger for cooling, and out
through two refractory-lined cyclones for participate removal. Air for the reducing-gas
regenerator was electrically preheated. The reducing gas from the regenerator passed
through a ceramic distributor plate supporting the regeneration bed, a refractory-lined
cyclone, and a heat exchanger before being discharged through a butterfly valve. Pressure
on the combustor and regenerator was kept the same by a differential pressure controlled by
positioning the butterfly valve in the regenerator discharge line.
Heat extraction and temperature control in the fluidized bed was accomplished by
boiling water in the vertical zones of the reactor. Solids transfer between reactors and
discharge from the regenerator was accomplished using a pulsed air transport technique
controlled by pressure differentials across and between the fluidized beds.
313
-------
FBM Exhaust
,_ A A A _.
*^v^ -»•• — — •»_ -> /• -,/ ^s^,'1? nr -^,-v- •• * - fT* - r*** • •* ^ f. •
•• •" y — / ,y f ^ •* ***. .f • *• ^ •( v •• r
CO
CBC
Exhaust
P',., f-l . P,, P NR P . }>. >T; . A« - P,
^i .^.'r^ i^1. u'\» ^' •:>>.; :-u..;ft-. :
I 0.2m -t^
~T\. Insulation
Additive Ash
Port #1 (typical)
Coal Feeder
(partial view)
2.5 x 5.1 cm
Intercommunication Slots
Access Door
i
Mushroom Feeder (fly ash)
Air Distribution Grid
Source: 124.
Figure E-5. Section view of the integrated FBM/CBC unit.
-------
Uncontrolled Flow
Paths
FBM
Controlled Flow Path
Key
Source: 12.4.
Bed material may flow in both
directions - via gravity, pressure
difference, or diffusion. Rates
uncontrolled.
Bed material can flow only in
direction of arrow with rate
control.
Figure E-6. Bed material flow paths: FBM,CBC and regenerator.
315
-------
City Water Cooling Water
CO
To Scrubber
in uur
t A i
[ Heat Exchgngerk»*T*> To
Scrubber
Heat Exchanger]
Water FeedPump
Water Out
Water In
76 liters/min
4.2 kg/sq cm
*- Water Oul
— Water In
Discard \
Limestone
& Coal
Fuel
Storage
Injection
Air
-a
o
Air Compressor
5.6 cu m*/mln @ 12.3 kg/sq cm
-a
•o
Air Compressor
39.2 cu m*/min
8.8 kg/sq cm (gauge)
* At STP
Source: 43.
Legend
CS - Cyclone Separator PF - Pulse Feeder
CV - Collector Vessel RV - Refill Vessel
Figure E-7* Pressurised F&Cpilot plant, Linden, New Jersey.
-------
TABLL E-l DESIGN PARAMETERS: EXXON MINI PLANT
Parameter
Unit
Component
Combustor Regenerator
Unit dimensions
Height
Internal diameter
Maximum operating conditions
Temperature
Pressure
Superficial bed velocity
Heat released by combustion
Cooling load
Maximum material rates
Air
Coal
Limestone
Natural gas
U output
cm
cm
°C
atm
m/sec
103 kcal/hr
103 kcal/hr
std cu m/min
kg/hr
kg/hr
std cu m/min
kg/hr
71.10
31.75
927
10
3.05
1,588
907
33.98
218
30.84
48.30
12.70
1,093
10
1.52
2.55
0.28
18.14
Source? 43.
317
-------
The second phase of the program involved a study of the factors influencing the forma-
tion and the control of nitrogen oxides (NO ) in fluidized bed combustion. For these
studies, a 7.6 cm ID fluidized bed combustor and two smaller electrically heated fixed
bed reactors were used. An automatic instrument continuously measured NO,SO,,, and
O_ emissions. The operating factors that were studied included excess air level, rempera-
ture, and bed composition.
The 7.6-cm unit was modified to operate as a two-stage combustor, in order to test a
reactor configuration that would yield low NO emissions by promoting the reduction of
NO by CO and then the reaction of NO with £t)_and lime. Operating at substoichio-
metric conditions, the NO-CO reaction was permitted and secondary air was added at a
higher point in the bed to complete the combustion and provide SO- for reaction with the
remaining NO. A schematic diagram of the Exxon fluid bed combustion unit is shown in
Figure E-8.
318
-------
CO
Vent
WTM
Instrument Calibration By-Pass
Feeder
Scale
Coal
Hopper
and Feeder
Cyclone and
Filter
Air
Condenser
Reactor
Water
Condenser
N2 CO SO2
O2 NO Air
Gas Rotameters
Refrigerator
T
Condensate
Figure E-'8.. Exxon FBC unit.
IR SO2
Analyzer
IRCO
Analyzer
I
WTM
NO Analyzer
WTM
Polarographic
O2 Analyzer
J
Intermittent
Gas Sampler
Source: 43
-------
APPENDIX F
FLUIDIZEDH8ED OIL GASIFICATION
Introduction
Fluidlzed-bed oil gasification provides the technology for utilizing high-sulfur residual
oils and asphalts for clean power generation. Oil can be gasified at either atmospheric or
elevated pressure. At atmospheric pressure, a fluidized-bed gasifier provides clean fuel to
a boiler. At elevated pressure, the fuel goes to a combined-cycle gas and steam turbine
power plant. Power-cycle schematics for low and high pressure alternatives are shown in
Figures F-l and F-2.
Low and high pressure systems may use either once-through operation, or regeneration
of the limestone or dolomite sorbent. The quality of waste material is minimized by keeping
the spent sorbent dry, which makes it potentially suitable for other uses.
The atmospheric (low) pressure process can be used to retrofit an existing boiler or as
a design feature on a new boiler., Capital costs of a retrofit, once-through oil gasification
system may be 50 to 70 percent less than a retrofit stack gas cleaning system.
v
Process Descriptions
Low-Pressure Gasification
The gasiflcation/desulfurization operation can be accomplished by either the regenera-
tive or the once-through mode. Figure F-3 illustrates the major process streams and elements
of the two operational modes. The specifications assumed for design of a commercial plant
are shown in Table F-l .
Regenerative Operation
The major components of the regenerative operation are the gasifier and regenerator
vessels. The gasifier Is an air-fluidlzed bed of lime operated at 870°C with subtaichiometric
air fc20 percent of stoichiometric). Heavy residual oil is injected into the gasifier vessel
where it cracks and is partially cpmbusted to form a hot, low-sulfur gas. Hydrogen sulfide
produced during gasification reacts with the lime to produce calcium sulfide and water:
H2S + CaO —CaS + H2O
The hot fuel gas is transported to the boiler burners where combustion is completed, and the
calcium sulfide is sent to the regenerator. The regenerator is an air-fluidlzed vessel operated
with a slight excess of air at about 1,000 C. Regeneration takes place by reaction of
oxygen with the calcium sulfide (spent lime) to give an SO~ rich stream (of about 10 mole
percent $02) and a regenerated Hme having a slightJy decreased activity compared to that
of fresh lime:
CaS + 3/2 O2 »-CaO + SO2
320
-------
Cyclone
Stack Gas
Hot Fuel Gas
CO
1-0
Oil
Limestone
(CaCO3)
Regenerated
Limestone
or --_
CaSGv
1800-3600 kca I/cum*
Particulates
Fluidized Bed
Gasifier/
Desulfurizer
1 Atm, 870 C
Spent
Limestone
Limestone
Processing
for Reuse or
Disposal
7
Booster
Fan
Conventional
Boiler
Turbines
Generator
* AtSTP.
Source: 104.
Figure FrK Low pressure fluidized bed oil gasification for power generation,
-------
one
CO
ro
Stack Gas
Hot Fuel Gas
Oil •
Steam *
Lime- •
stone
(CaCOg)
Regenerated
Limesjone
or __
CaSC
aAt STP.
Source. 104.
1800-3600 kca!/cu
Fluidised Bed
Gasifier/
Desulfurizer
10-15atm, 870 C
Spent
Limestone
Limestone
Processing
for Reuse or
Disposal
High Temp.
Gas
Combustor
rteat
Recovery
Boiler
Turbine
Generator
Generator
Figure F-2. High pressure (I jidfzed bed oil gasification for power generation.
-------
Once-through Mode
Stack Gas
Combustion Air
Combustion Air
Regenerative Mode
Stack Gas
I
CO
to
CO
-*. 1. - J ' 1 L--
Clean Fuel Gas Bo|ler
Final OH 1 ; ^
! T
1
Clean Fuel C
r
i
1
^^
-* Limestone Feed Lmieslone ^ Gasifier
~ .c. ' Make-up
Gasifier r -«•
~* Temperature
A Control Stream
1 f Spent
L | ,S.penf Lime
i «S) (CaS) 1
j_ Sulfate AIr *" Reaen
Legend
Gas
CaSO4 Liquid Ca
n. , Solid Feed D's
Disposal
— •• Solid Circulation
1 Regener
so2-
eratOT ~~Str«
S°4
3OSOI
Boiler
JOS
c.10| r\t\
Temperature
Control Stream
ated Lime
Rich ^ Sulfur
am Recovery
Source: 104.
Figure F-3 . Modes of operation, fluJdized bed oil gasification plant.
-------
TABLE F-U ATMOSPHERIC PRESSURE OIL GASIFICATION SPECIFICATIONS
Process Specifications
Design Variables
Sulfur Removal: 90-95% Boiler Size: 600 Mw
Fuel Oil: 3% sulfur by wt.;LHV = 9.81 x 10 kcal/kg Load Factor: 40%, 80%
Limestone: 98.6% CaO yield Turndown: 4/1
Parameter
Operating Variables
Regenerative System Once-Through System
Gasifier temperature (C) 870
Regenerator (sulfate 1,000
generator) temperature (C)
Limestone make-up rate 1 mole CaO/mole sulfur
Air/fuel naiio 20%of sta'chiometric
Limestone utilization 5% sulfur by wt. In bed
Fluidization velocity (m/sec) 2.4
Minimum fluidizafion 0.9
velocity (m/sec)
Particle sizes, avg. ( n ) 2,000
Gasifier bed depth, static (m) 0.8 - 1.1
870
820
3 moles CaO/mole sulfur
20% of stoSchiometric
19% sulfur by wt. in bed
2.4
0,3
1,000
1.1 - 1.2
Source: 104.
324
-------
The SO- stream is transported to a sulfur recovery system, and the regenerated lime is re-
turned ro the gasifier along with an approximately stoichiometric amount of fresh make-up
limestone.
Once-Through Operation. The elements of the once-through operation are a gasifier vessel
and a sulfate generator,or a predisposal vessel.The operation of the gasifier is the same as
for the regenerative operation. The sulfate generator operates similarly to the regenerator but at
a lower temperature ( ~ 800 C), so that the calcium sulfide from the gasifier is converted
to calcium sulfate rather than calcium oxide. The dry calcium sulfate may be disposed of,
and the gas stream from the sulfate generator is sent to the gasifier. A limestone addition
rate of up to three times that used in rhe regenerative operation may be necessary to achieve
sulfur removal of 90 to 95 percent.
High-Pressure Combined-Cycle Gasification
The high pressure combined-cycle gasification process can be accomplished by either
once-through or regenerative operation. Table F-2 lists the factors specified for the con-
ceptual design of the high pressure fluid-bed oil gasification process. Figure F-4 shows a
flow diagram of the energy balances for the high pressure fluid-bed oil gasification process.
Regenerative Operation. The high pressure regenerative process shown in Figure F-5 consists
of a Ffuidized-bed gasifier/desulfurizer vessel, a limestone/dolomite regenerator, and a
sulfur recovery section. Residual oil is injected into the gasifier vessel and fluids zed-bed
of lime operated at 870° C with substoichiometric air (]4 to 25 percent of stoichiometric).
This yields (by cracking, partial combustion, and hLS absorption by the limestone or dolomite)
a hot fuel gas of low energy value and sulfided lime or dolomite. The gas is transported to
the combined-cycle plant where combustion is completed, and the suffided lime or dolomite
is sent to the regenerator. The regenerator may be designed to produce gas rich in FLS or
SO9 and regenerated sorbent with a decreased activity. The SO« or \ij> stream is trans-
ported to a sulfur recovery system, and the regenerated sorbent is returned to the gasifier
along with a nearly stoichiometric amount of fresh make-up sorbent.
The regeneration of calcium sulfide and the production of a high-sulfur gas for recovery
can be achieved by either of two processes, as follows:
1) Regeneration with CO^ and H2O to produce H2S:
CaS + H20 + CO2 —* CaC03 +
2) Regeneration with air to produce
CaS + 3/2 O2 —> CaO + SO2
Table F«3 lists the gasification product compositions and fuel heat values for a high-pressure
fluidized-bed gasification system with limestone regeneration.
325
-------
TABLE F-2. SPECIFICATIONS FOR HIGH PRESSURE
FLUIDIZED BED OPERATION
Item
Specification
Plant electrical capacity
Capacity factor
Turndown ratio
Number of gasifier modules
Modes of operation
Gasifier pressure
Pressure of gas turbine
Sulfur removal
Residual oil
Gasifier temperature
Regenerator temperature
Sulfate generator temperature
Air/fuel ratios
Lime particle diameters
Regenerative lime utilization
Once-through lime utilization
Limestone make-up rate
Gasifier temperature control
Regenerator temperature control
Sulfate generator temperature
control
Plant heat rate
250 Mw (PACE Plant)
70%
4/1
2
Regenerative or once-through
~ 15 atm
11 atm (11.6 kgf/sq cm to turbine)
90-95%
3 wt % sulfur
870 C
600 Ca
930 C with once-through option
14 (minimum) & 25% stoichiometric
500-2000^1 average diameter
10%
35%
1 mole CaO/mole sulfur fed
Stack gas recycle, steam or water injection
Lime circulation rate; water injection
Excess air circulation (~200% excess)
2300 kcal/kwh (assumed for purposes of
material balances)
a With CO2/H2O regeneration; 1150 C with air regeneration*
Source: 104.
326
-------
Limestone/Dolomite 30 C
Steam
Water
GO
10
Hot (870 C) Fuel Gas to
combined cycle plant
Residual
Fuel Oil
Fluidized Bed
Oil Gasification
System
Booster Com- |
pressor Power |
Energy Losses (heat losses, carbon deposition,
sensible heat of the flue gas, cooling water)
Limestone/bolomite (1000C)
Sulfur
' Auxiliary Power (cooling water pumping, oil pumping,
j solid circulation, compression for regeneration)
Booster Compressor
Air from GT Compressor (air/fuel ratio = 14-25% of
stoichiometric)
Source; 104.
Figure F-4 . Energy balances flow diagram,
-------
Clean Fuel Gas to Combined
Cycle Plant
Cyclone
Fines
Fines
Disposal Disposal
H2S or SC»2 to
"Sulfur Recovery
Cyclont
CO
10
00
Make-up Sorbent
Temperature Control
Residual Oil
Pressurized Air from
Gas Turbine Compressor
Source: 104.
Oil
Gasifier
Utilized Sorbent
Regenerated Sorbent
Sorbent
Disposal
Booster
Compressor
Sorbent
Regenerator
KLO and CO2 or Air
Figure F-5 . Regenerative high-pressure oil gasification process.
-------
TABLE .F-3. GASIFICATION PRODUCT COMPOS HiQMS
Composition (% by volume)
Gas
_______ 14%A/F° 25% A/F
N2 50.74 47.74
H2 0.82 2.64
CO 13.40 7.97
C02 6.70 7.97
H2O 0.00 20.56
CH4 9.43 6.55
C2H4 18.86 6.55
0.05 0.02
Low heating value (hot) (10^ kcal/cu m) ~ 70 ~ 40
QAir/fuel ratio.
Source: 104.
329
-------
Once-Through Operation . If a high sorbent make-up rate is required for the regenerative
processes and if high sorbent utilization can be achieved in the gasifier, a once-through
system may be attractive. A flow diagram of the once-through system was presented in
Figure E-4. Once-through operation would require conversion of calcium sulfide to calcium
sulfate before disposal of the sorbent. The reaction is:
CaS+2CL — *• CaSO,.
£. 4
Process Environmental Comparison
Table F-4 compares environmental factors for power generation by oil gasification (with
a conventional plant or with a combined-cycle steam and gas turbine plant) with the en-
vironmental effects of a conventional oil-fired power plant using limestone scrubbing.
The spent sorbent from the fluidized bed oil gasification/desu If urieation process is dry
and granular ( ~ 6 mm). The composition is primarily calcium oxide and calcium sulfide
with small amounts of calcium sulfate— the spent stone from regenerative operation contain-
ing approximately 1 to 2 percent CaS and, from once-through operation, a projection of 30
to 80 percent CaS. Table F-5 lists some advantages of low-pressure oil gasification over
stack gas wet scrubbers.
Preliminary indications suggest that the once-through operation may be somewhat more
attractive to a utility than the regenerative operation.
Esso Research Center's Process (Abingdon, England)
CAFB Pilot Plant
The Chemically Active Fluid-Bed (CAFB) developed by Esso reduces sulfur oxide pollu-
tion while using high sulfur oil to produce power. The process uses a fluidized-bed of lime
particles to convert the oil into a hot, low sulfur gas ready for combustion in an adjacent
boiler. The process has the additional benefit of removing vanadium before the final com-
bustion states and thus eliminating a source of internal boiler corrosion.
When oil is combusted under sub-stoichiometric conditions, the sulfur is trapped by
lime as calcium sulfide:
H2S
+ CaO — * CaS +
CaS formed by the reaction of H_S and CaO in the gasifier fluid-bed is converted back to
CaO in a fluid-bed regenerator By contact with air:
CaS + 3/2 O2 — * CaO + SO2.
The amount of regenerated lime removed is made up by the addition of fresh limestone tovthe
combustor; sulfur is recovered during the regeneration process in several ways, such as con-
version to hLSO . or elemental sulfur.
2 4 330
-------
TABLE F-4. ENVIRONMENTAL IMPACT COMPARISON
CO
CO
Environmental Factors
Conventional Oil- Conventional Oil-Fired
Fired Power Plant Plant with Atm-Pressure
with Limestone Oil Gasification
Wet Scrubbing
Regenerative Once-through Regenerative Once-through
Combined Cycle Power Plant
with
Pressurized Oil Gasification
Plant capital investment ($/kw)
Plant energy cost (mills/kwhr)
Limestone waste (kkg/day)
Water usage (kkg/day)
SO^ emission (kg/10 kcal)
NO emission (kg/106 kcal)
Particulate emission (kg/10 kcal)
325
13.1
440 (sludge)
450 (sludge)
0.63
1.44
0.04
Thermal emission (% of conventional plant) 100
Auxiliary power & fuel (% of plant
Plant heat rate (kcal/kwhr)
Land requirement
input) 4.0
2,400
large area for
disposal pond
310
12.7
80-160
0.63
0.29
0.04
~ 100
2.5
2,400
large area
300
12.5
450-730
0.63
0.29
0.04
-100
2.5
2,400
large area
180
9.7
80-160
0.63
0.29
0.04
— 50
7.5
2,400
more compact
plant
160
9.2
450-700
0.63
0.29
0.04
-50
5.0
2,300
power
Basis: 635 Mw power plant @ 1973 costs; capitalization at 15%; residual oil at $1.79/10° kcal; gasification at air/fuel
ratio of 20% of sroichiometric; limestone make-up rate of 0.5 to 1.0 times stoichiometric for regeneration and 1.5
to 3.0 times stoichiometric for once-through; for wet scrubbing a make-up rate of 1.2 times stoichiometric; NO
emission for gasifier based on pilot plant measurements; combined cycle plant based on conventional gas-turbine*
technology, advanced gas turbine conditions can reduce plant costs and total emissions; gasification process con-
sists of two independent gasifier modules.
Source: 104.
-------
TABLE F-5. ADVANTAGES OF ATMOSPHERIC PRESSURE OIL GASIFICATION
OVER STACK GAS WET SCRUBBERS
1 . Corrosion and fouling problems minimized in SO2 removal process and in boiler
(minimum SO and V)
A
2. No flue gas reheat required.
30 Uses crushed limestone - no limestone pulverizing system needed.
4. Simplified disposal - dry solids and no disposal pond.
5. More compact system.
6, Reduced structural costs.
7. Lower auxilary power requirement.
8. Reduced energy cost.
9. Improved NO control.
/x
10. Potential market for spent CaO
Source: 104.
332
-------
The main unit of the CAFB process is the combustor and regenerator system, which is
made of an insulated steel shell contained in a refractory concrete cast. The gasifier and
regenerator are cavities in a single refractory concrete block. The block contains other
cavities which make up the gasifier outlet "cyclones, the gas transfer ducfs, and transfer
lines through which solids circulate. The gasifier product gas fires a 2,930 kw pressurized
water boiler. The hot water is heat-exchanged through a forced convection cooling tower.
The rest of the system consists of the necessary blowers, pumps, and instruments to operate
the gasifier, regenerator, burner, and solid circulation system.
Batch Reactor and CAFB Experiments
Under contract to EPA's Office of Research and Development, Esso (England) investiga-
ted sulfur absorption and lime regeneration operating variables. The experimental equipment
used in the study consisted of two batch reactor units and the continuous CAFB pilot plant.
Changes were made to various sections between test runs as a result of experience, and to
achieve specific objectives. The oils used were heavy fuel oils from Venezuela crudes ob-
tained from the Amuary Refinery of the Crude Petroleum Co. Pilot plant runs had employed
U.S. Stone BCR 1691 and a U.K. limestone from Denbighshire. Batch units had employed
the latter two stones, as well as U.S. Stone BCR 1359. A summary of the experimental
results appears in Table F-6.
Each batch unit contained a reactor, air and fuel systems, a flare for product gas
disposal, and a gas sampling and analysis system, as shown in Figure F-6. The reactors were
made of stainless steel with a refractory lining. The lower section, which contained the
fluid bed, was 17.8 cm (ID) by 84 cm high. The reactors used in the original tests were
not fitted with cyclones and, therefore, were used only in low gas velocity experiments.
The unit has no provision for temperature control other than by adjusting the quantity of
insulation around the reactor. The insulation was arranged to permit the unit to operate
in the range of 800 to 900 C with air velocity of 1.2 m/sec and an excess air of over
30 percent to that required for combustion.
When operating under combustion conditions and also during regeneration of bed
material, the gas from the bed was monitored directly for CCL,CO, (X and for appropriate
information on combustion efficiency, sulfur removal efficiency, or sulfur release deduced.
During gasification, a portion of the product gas was burned in a sample flame located just
above the reactor, and the combustion products were analyzed for SCU, O_, CO, and COj.
The desulfurizing efficiency of the gasifier was calculated from the analysis of the fully
combusted gas. The first reactors were used in the initial fuel oil screening work; the two
later batch reactors were designed and constructed for studies of various operating modes.
The upper section of the reactor was redesigned to permit installation of two internal
cyclones and to allow drainage of the cyclone for external sample collection. Internal
cooling coils contained in the reactor allowed the temperature to be controlled indepen-
dently of fuel and air rates. The type of reactor used for these studies is shown in Figure F—7*
333
-------
TABLE F-6, SUMMARY OF EXPERIMENTAL RESULTS
Batch Tests
I. Nearly 100% sulfur removal at 870 C, 20% air/fuel ratio, with limestone
make-up rate of 1 mole CaO/mole of sulfur bed.
2. Nearly 100% of fuel vanadium removed.
3. About 20% of fuel sodium removed.
4. Clean product fuel is easily combustible with a luminous smoke-free flame,
5. Regeneration at 1000 C gives a 10% SC^-gas product and a regenerated
lime having reduced activity.
Continuous Unit
1 . Results indicate superior behavior during continuous operation due to the
improved temperature control.
- Lower air/fuel ratios, down to 17% of stoichiometric, have been
demonstrated.
- 90% sulfur removal has been demonstrated.
Source: 104.
334
-------
CO
CO
Oi
Air
Propane (for
start-up)
Oil
CAFB Batch Reactor
Fuel
Metering
Pump
Sample Flame
Fuel Injector
Air
Source; 53.
Figure F-6. Esso,England batch reactor oil gasification system,
-------
Outgoing Gas Will
Be Burned Here
External
Cyclone
Fuel Injection
Source: 53.
Distributor
Gas Preheater
Air Supply
Figure F-7 -Batch reactor.
14cm Bed
•*— Datum
336
-------
TECHNICAL REPORT DATA
(Please read htuntctions on the reverse before completing)
REPORT NO.
EPA-
-77-139
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
Environmental Assessment of Solid Residues from
Fluidized-Bed Fuel Processing
5. REPORT DATE
December 1977
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
Ralph Stone and Richard Kahle
8. PERFORMING ORGANIZATION REPORT NO,
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Ralph Stone and Co. , Inc.
10954 Santa Monica Boulevard
Los Angeles, California 90025
10. PROGRAM ELEMENT NO.
EHB536
11. CONTRACT/GRANT NO.
68-03-2347
12. 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 PE
Initial; 11/75-12/76
PERIOD COVERED
14. SPONSORING AGENCY CODE
EPA/600/13
15.SUPPLEMENTARY NOTES TERL-RTP project officer for this report is Walter B; Steen, Mail
Drop 31, £19/541-2825.
16. ABSTRACT
The report gives results of the first 15 months of an environmental assess-
ment of solid residues generated by fluidized-bed combustion (FBC) of coal and gasi-
fication of oil. Included are a literature search, c'lemical and physical residue char-
acterization, laboratory leaching studies, and testing of residues in various materi-
als and agricultural applications. The literature search reviewed current FBC tech-
nology, identified products in which residues might be used, and gave data on typical
soil and geologic conditions at the evaluated disposal sites. Laboratory tests included
total chemical characterization, composition of acid-, base-, and water-soluble fi-ac-
tions, cation exchange capacity, BOD, temperature change from water addition, par-
ticle size distribution, dry density, specific gravity, permeability, water-holding
capacity, moisture content, and small-scale column leaching studies. Pilot-scale
columns simulated abandoned coal mines, dolomite and limestone quarries, sanitary
landfills, soils, and the ocean. Water was added to columns on a prescribed schedule
and the resulting leachate was collected and analyzed for chemical constituents. The
data were used to assess the potential for impact on water quality, and the capacity
of the disposal environment to attenuate degradation. Residue use was considered for
concrete, asphalt, soil cement, and lime/flyash aggregate.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
COS AT I Field/Group
Pollution
Assessments
Solids
Residues
Coal
Fluidized-Bed
Processing
Combustion
Fuel OH
Gasification
Water Quality
Leaching
Soils
Geology
Pollution Control
Stationary Sources
Environmental Assess-
ment
Fluidized-Bed Combus-
tion
Acid Mine Drainage
13B
14B
07D
21D
13H.07A
21B
08G,08W
18. DISTRIBUTION STATEMENT
19. SECURITY CLASS (TinsReport)
Unclassified
21. NO. OF PAGES
350
Unlimited
20. SECURITY CLASS (Thispage)
Unclassified
22. PRKfr
EPA Form 2220-1 (9-73)
337
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