EPA-600/7-78-077
J.S. Environmental Protection Agency Industrial Environmental Research EPA-600/
Office of Research and Development Laboratory
Research Triangle Park. Nortfi Carolina 27711 May 1978
ADVANCED OIL
PROCESSING/UTILIZATION
ENVIRONMENTAL ENGINEERING;
EPA Program Status Report
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 nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7. Interagency Energy-Environment Research and Development
8. "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the INTERAGENCY ENERGY-ENVIRONMENT
RESEARCH AND DEVELOPMENT series. Reports in this series result from the
effort funded under the 17-agency 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 sys-
tems. The goal of the Program is to assure the rapid development of domestic
energy supplies in an environmentally-compatible manner by providing the nec-
essary environmental data and control technology. Investigations include analy-
ses 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 environ-
mental issues.
EPA 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 recommendation for use.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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EPA-600/7-78-077
May 1978
ADVANCED OIL
PROCESSING/UTILIZATION
ENVIRONMENTAL ENGINEERING:
EPA Program Status Report
by
P.P. Turner, S.L. Rakes, and T.W. Petrie
Environmental Protection Agency
Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, North Carolina 27711
Program Element No. EHE623A
Prepared for
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, D.C. 20460
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Abstract
This report is an annual status report of the IERL-RTP Advanced
Oil Processing Program. The amounts and the normal practice and
patterns of the usage of residual oil and contaminants in residual
oil are projected, with the emission standards serving as a yardstick
to indicate where potential problems exist. The development of both
Environmental Assessment and Control Technology is given, and the
alternatives, or choices of methods to use residual oil, are discussed.
Methods available or considered for the use of residual oil include
direct combustion, fluid bed combustion, partial oxidation, chemically
active flutd bed (CAFB), direct hydrodesulfurization (HDS), and com-
binations of these technologies.
The history of the IERL-RTP program and the relationship of the
CAFB to other alternatives are presented. The Environmental Assess-
ment of residual oil usage and the control technology development
efforts are outlined. The subobjectives, work tasks, and accomplishment
plans, with funding levels, are presented. The participating contractors
and grantees, with their scope of work outlines, and project descriptions
are discussed. A section deals with the effort toward advanced HDS,
hydrodenitrogenation (HDN), and demetallization techniques for residual
oils and like-derived fuels. References and EPA reports and staff
papers are listed in the appendices.
ii
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CONTENTS
Section Page
Abstract ii
List of Figures v
List of Tables vi
1. SUMMARY 1
1.1 Executive Summary 1
1.1.1 Mission of Standards Development/ 2
Implementation
1.1.2 Program Areas (Subobjective/Work Plan 2
Titles)
1.1.3 Funding Levels 3
1.2 Summary of Accomplishments 3
1.3 List of Contractors/Grantees 6
2. BACKGROUND 8
2.1 The Residual Oil Environmental Problem 8
2.1.1 Amounts and Ways Residual Oil Is Used in 9
the U. S.
2.1.2 Contaminants in Residual Oils 15
2.1.3 Emission Standards 23
2.2 Definition of Environmental Assessment and Control 26
Technology Development
2.3 Alternatives for Residual Oil Combustion/ 29
Utilization/Control
2.3.1 Direct Combustion With or Without 29
Particulate Control
2.3.2 Direct Combustion With Flue Gas 30
Desulfurization
2.3.3 Direct Combustion in Fluid Bed'Of 33
Limestone (AFBC)
2.3.4 Partial Combustion at Atmospheric 33
Pressure—Partial Oxidation (POX)
Followed by Cleanup and Conventional
Combustion
2.3.5 Partial Combustion in a Chemically 36
Active Fluid Bed (CAFB) Followed by
Conventional Combustion
2.3.6 Direct Hydrodesulfurization (HDS) of 38
Residual Oil for Combustion
2.3.7 Upgrading of Residual Oil Followed by 42
HDS and Conventional Combustion
iii
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CONTENTS (continued)
Section
2.4 History of the IERL-RTP Program Relating to 43
Residual Oil
2.4.1 The CAFB Process and Its Relationship 43
to Alternatives
2.4.2 Environmental Assessment of Residual 46
Oil Usage
2.4.3 Control Technology Development for 48
Residual Oil Treatment
3. ACCOMPLISHMENT PLANS/SUBOBJECTIVES/WORK TASKS 50
4. MEANS OF ACCOMPLISHMENT 51
4.1 Participating Contractors, Grantees 51
4.2 Scope of Work Outlines and Descriptions of 52
Active Projects
5. CURRENT STATUS: ENVIRONMENTAL ASSESSMENT 66
5.1 Progress 66
5.1.1 General 66
5.1.2 Project by Project 66
5.2 Plans 72
6. CURRENT STATUS: CAFB 75
6.1 Progress 75
6.1.1 General 75
6.1.2 Project by Project 77
6.2 Plans 80
6.2.1 CAFB Demonstration (Foster Wheeler) 80
6.2.2 CAFB Development and Technical Support 82
(Esso Petroleum)
6.2.3 Engineering Analyses and Support 82
(Westinghouse Research)
7. CURRENT STATUS: HDS/HDN/DEMETALLIZATION 88
7.1 Progress 88
7.2 Future Plans 89
8. APPENDICES 93
8.1 References 93
8.2 EPA Reports and Papers 95
iv
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FIGURES
No. Page
1 Environmental assessment/control technology 27
development diagram
2 Control technology development diagram 28
3 CAFB continuous pilot plant flow plan 39
4 The Esso England continuous CAFB pilot plant 40
5 Catalytic contract 42720, schedule/milestones 74
6 Model of CAFB demonstration unit under construction 76
by CPL at San Bern* to
7 Foster Wheeler CAFB program, schedule/milestones 81
8 Esso Petroleum contract 68-02-2159, schedule 83
9 Westinghouse Research contract 68-03-2142, 87
schedule/mi1estones
10 MIT catalytic HDN/HDS facility—continuous microreactor 90
featuring temperature control by a fluidized sand bath
11 MIT catalytic HDN/HDS facility—continuous microreactor 91
instrumentation for high-pressure, low-flow operation
12 Hydrocarbon Research bench-scale demetallization unit 92
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TABLES
No. Page
1 Domestic Production and Import of Residual Fuel
Oil by Sulfur Content for 1972 11
2 Imports of Residual Fuel Oils by Sulfur Content
for 1972 12
3 Domestic Demand for Residual Fuel 011 by Uses
for 1971 and 1972 14
4 General Crude Oil Characteristics by Region 16
5 Total Sulfur Content of Residual Fuel Oil for 1972 18
6 Typical Sulfur, Nitrogen, and Trace Metal Analyses
of Residual Fuel Oil 20
7 Typical Sulfur and Trace Metal Analyses of Residual
Fuel Oil 21
8 Nitrogen, Nickel, and Vanadium Content of Residual
Fuel Oil 22
9 Estimated Trace Metal Analyses of Residual Fuel
Oil 24
10 Operating Data and Results, Combustion of Residual
Fuel Oil in Excess Air 34
11 Esso Petroleum Contract 68-02-2159 Program
Milestones 84
vi
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1. SUMMARY
1.1 Executive Summary
The Industrial Environmental Research Laboratory, Research Triangle
Park (IERL-RTP), North Carolina, is a part of the Office of Research and
Development (ORD) within the Environmental Protection Agency (EPA). The
IERL-RTP is responsible for managing programs to develop and demonstrate
cost effective technologies to prevent, control, or abate pollution from
operations with multimedia environmental impacts associated with the
extraction, processing, conversion, and utilization of energy and mineral
resources, as well as with industrial processing and manufacturing. The
Laboratory also supports the identification and evaluation of environmental
control alternatives of the program, consisting of in-house activities,
contracts, grants, and interagency agreements, and contributes signifi-
cantly to the protection of National health and welfare through the
research and development of timely and cost-effective pollution control
technologies.
Although EPA is primarily a regulatory agency, the vital supportive
role of research and development activities within the overall EPA mission
must not be overlooked. Adequate pollution control technology, for example,
must be available before effective standards for the protection of public
health and welfare can be set and successfully enforced; the development
of ever more efficient and economical environmental control technology
benefits not only the affected industry, but ultimately everyone. This is
particularly true considering the present situation; in the long run,
the protection of our environment and the conservation of our natural
1
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resources are integral parts of meeting energy requirements in a viable
manner. Advanced Oil Processing programs are concerned primarily with
the area of energy resources utilization, especially the combustion and
processing of residual oils, with secondary emphasis on applying new
technologies to other fuels.
1.1.1 Mission of Standards Development/Implementation
It is one of the IERL-RTP stated objectives to establish a
technical and economic research data base to support development of
New Source Performance Standards (NSPS). Indeed, much of its research
and development effort in fuel cleaning programs has been with the
control of sulfur oxides as the basis for development/implementation
of standards.
1.1.2 Program Areas (Subobjective/Work Plan Titles)
The Advanced Oil Processing program has three subobjectives, each
with a number of project work areas:
A. Environmental Assessment-
Environmental Assessment of Residual Oil Usages
Analytical Support for Residual Oil Usage/Determination of
Hazardous Substances
B. Chemically Active Fluid Bed Residual Oil Cleanup--
Chemically Active Fluid Bed Development and Support/Esso England
Chemically Active Fluid Bed Demonstration on Small Commercial Scale
Engineering Support of Chemically Active Fluid Bed Demonstration
Multiple Optional Service Contract Tasks in Support of the
Fluid Bed Demonstration
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C. Control Technology Development--
Hydrodesulfurization/Hydrodenitrification (HDS/HDN) Interactions
in Liquid Fuels
Control Technology for HDS/HDN of Liquid Fuels
1.1.3 Funding Levels
Subobjective A (from Section 1.1.2) is funded at a level
of $356,000.
Subobjective B (from Section 1.1.2) is funded at a level
of $978,000.
Subobjective C (from Section 1.1.2) is funded at a level
of $203,000.
1.2 Summary of Accomplishments
Accomplishments under the three subobjectives are:
0 Advanced Oil Processing (Environmental Assessment)—Character!za-
tion of waste streams from oil processing methods and evaluation of the
applicability of alternate advanced oil processing methods for utiliza-
tion of petroleum residuals; evaluation of the application of available
control technology; and publication of a manual of best available tech-
nology in coordination with the standards setting timetables. Signifi-
cant accomplishments include:
00 Identification made of residual oil conversion/utilization as a
national multimedia environmental problem with diverse potential
consequences ranging from atmospheric sulfates to hazardous oil
spills.
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00
Inventory completed of potential pollutants in crude oils
from specific locations (domestic and foreign).
Background report developed entitled "Residuum and Residual
Fuel Oil Supply and Demand in the United States...1973-1985."*
Major environmental assessment contractor brought on board to
identify environmental tradeoffs on all existing and projected
processing/utilization options for residual oil.
Contract negotiations initiated for comprehensive categoriza-
tion and characterization of residual oils.
Report issued by Radian entitled "Environmental Problem Definition
for Petroleum Refineries, Synthetic Natural Gas Plants, and Lique-
fied Natural Gas Plants."
0 Advanced Oil Processing (CAFB Development)—Demonstration at
small to moderate commercial-scale of the chemically active fluid bed
(CAFB) process for converting heavy high-sulfur, high-metals content
residual oils to clean, high-temperature gaseous fuel. Significant
accomplishments include:
30 Success achieved in the pilot plant program with design work
begun on demonstration of CAFB process on utility boiler as an
environmentally sound fuel switching technique.
"'* Progress report issued entitled "Development of the Chemically
Active Fluid Bed Process, A Status Report and Discussion."
(See S. L. Rakes in Section 8.2.)
00 Continuous operation of the CAFB pilot plant at Esso Petroleum,
Ltd., for periods as long as 412 hours, with 212 hours between
decaklng or cleaning of the gas duct. Sulfur removal of 85
(*) All EPA reports cited 1n this document are more completely
Identified on Section 8.2
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00
percent and vanadium retention of TOO percent on the bed material
were based on the residual oil inputs.
Pilot testing of coal feedstocks in the continuous CAFB pilot
plant begun in support of the planned demonstration.
Design/construction of a 10 MW demonstration plant at Central
Power and Light (CPL), San Bern*to, Texas, underway with Foster
Wheeler Corporation as prime contractor.
Westinghouse control technology studies show that the trace
metals sequestered by the bed material are bound tightly and
will not leach out into the environment. The spent sorbent
shows promise as a component of concrete. The spent bed
material was found to contain very little, if any, organic
compounds.
0 Advanced Oil Processing (Control Technology Development)--
Development and demonstration, where needed, of technologies for the
removal of sulfur, nitrogen, and potentially hazardous trace materials
from petroleum, petroleum derivatives, and other liquid fuels. Develop-
ment and evaluation of the best practical control technologies for
commercial or near-commercial processes.
00 Determination of the fundamental characteristics of the
reactions involved in simultaneous hydrodesulfurization and
hydrodenitrogenation. Report issued entitled "Catalytic Desul-
furization and Denitrogenation."
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oo
00
Identification of specific catalysts that tend to optimize
demetallization of oils, and preliminary estimates of
catalytic demetallization and desulfurization of specific
Venezuelan, Soviet, and Iranian Oils. Phase III report
issued entitled "Demetallization of Heavy Residual Oils."
Work initiated to optimize denitrogenation of residual oils.
1.3 List of Contractors/Grantees
The following organizations are carrying out work in the areas
indicated:
0 Environmental Assessment of the Uses of Residual Oils
Contractor: Catalytic, Inc.
Contract No.: 68-02-2155
0 Chemically Active Fluid Bed Development and Support
Contractor: Esso Petroleum Company, England
Contract No.: 68-02-2159
0 Preliminary Environmental Assessment of the CAFB
Process; Coal and Lignite
Contractor: GCA Corporation
Contract No.: 68-02-2632
0 Engineering Support for the Demonstration of Chemically
Active Fluid Bed Process
Contractor: Westinghouse
Contract No.: 68-02-2142
0 Demonstration of the Chemically Active Fluid Bed Process
Contractor: Foster Wheeler
Contract No.: 68-02-2106
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0 Analytical Support to Include Comprehensive Analysis of
Hazardous Substances in Residual Oils
Contractor: Westinghouse
Contract No.: 68-02-2638
0 HDS/HDN Interactions in Liquid Fuels
Grantee: MIT
Grant No.: R804123
0 Control Technology for HDS/HDN of Liquid Fuels
Contractor: Hydrocarbon Research, Inc.
Contract No.: 68-02-0293
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2. BACKGROUND
2.1 The Residual 011 Environmental Problem
The two primary environmental problems associated with residual
oil are air pollution from its processing and combustion as a fuel, and
water pollution from leakage and spills during its transport and handling.
Combustion of residual fuel oil produces gaseous and particulate
emissions. Gaseous pollutants include oxides of sulfur and nitrogen and
relatively smaller amounts of carbon monoxide, hydrocarbons, and aldehydes.
Particulate emissions contain the trace elements originally present in
the residual oil, such as vanadium, as well as unburned carbon and sulfates
Recent data indicate that residual oil containing vanadium may produce
higher primary sulfate emissions than coal. * ' More data are needed
to confirm this. Moreover, little is known about the toxicity of partic-
ulate emissions from residual oil compared to those from coal. The
possibility exists that they are much more toxic than those from coal.
Leakage and spills of residual oil from oil transfer operations,
tank cleaning, ballast disposal, tanker accidents, and other operations
result in discharge of residual oils to the water and wet land environ-
ments. Residual oil contains relatively concentrated fractions of toxic
substances which, besides being health and ecological hazards, are
extremely slow to degrade. In addition, substances used as dispersants
in cleaning up oil spills can also have undesirable effects.
8
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Fuel oils are classified by the American Society for Testing and
Materials (ASTM) into five grades, Nos. 1, 2, 4, 5, and 6. Nos. 1 and 2
are distillate oils for use in burners requiring a volatile or moderately
volatile fuel, respectively. Nos. 4, 5 and 6 oils are marketed in the
(2)
United States as residual fuel oils. ' Nos. 4 and 5 are produced either
as straight-run fractions or by blending No. 6 and No. 2. Their primary
use is in space heating for large apartments and commercial buildings.
No. 6 is the heaviest oil and is used in large industrial and electric
utility boilers for process steam and power generation. It also is a
fuel for marine engines and is then referred to as bunker fuel oil or
Bunker C.
2.1.1 Amounts and Ways Residual Oil is Used in the U. S.
The U. S., with the exception of the East Coast, has historically
relied on low-cost domestic supplies of natural gas and coal to meet
its need for industrial and public utility energy resources. The East
Coast, being physically separated from Western reserves of coal and
Southern reserves of natural gas, developed a dependence on residual
fuel oil from Caribbean refineries for use in public utility and industrial
boi1ers.
In the sixties and early seventies, shortages of natural gas
shifted domestic energy demand toward residual fuel oil and coal,
causing more areas in the U. S. to join the East Coast's dependence
on fuel oil imports. Over the period 1969-1972 annual domestic demand
for fuel oil increased 203 x 106 bbl (32.3 x 106 m3) from the 1969 demand
of 722 x 106 bbl (115 x 106 m3) to 925 x 106 bbl (147 x 106 m3) in 1972.
In response, fuel oil imports jumped 176 x 106 bbl (28 x 106 m3) (38 percent)
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to 637 x 106 bbl (101 x 106 m3), while domestic production of fuel oil
rose only from 28 x 106 bbl (4.5 x 106 m3) (10 percent) to 293 x 106 bbl
c 3
(46.6 x 10 m ) per year. To counteract this trend, the U. S. Government
initiated the Old Oil Entitlements and Oil Import Fee Program after 1972.
The relative growth rates of fuel oil imports and domestic production
were reversed in 1974. Under these programs domestic crude prices were
pegged at a level well below the world crude market price, and a fee
was levied on all crude oil and product imports. Caribbean refiners
faced world prices for crude and potentially lower U. S. market prices
for residual fuel oil. Due to the availability of low-cost domestic
crude, U. S. refiners had the advantage of a composite crude oil cost
that fell below world levels, and a residual fuel oil product price
that was set by relatively high-priced Caribbean substitutes. Thus,
there was an obvious economic incentive for domestic refiners to increase
their fuel oil yield. From 1972 to 1974, U. S. demand for residual fuel
oil rose 32 x 106 bbl (5 x 106 m3) (48 percent) to a total of 390 x 106 bbl
(62 x 106 m3), while imports actually dropped 64 x 106 bbl (10 x 106 m3)
(10 percent) to a total of 574 x 106 bbl (91 x 106 m3) per year.
The total supply of residual fuel oil was over 927 x 10 bbl
(148 x 106 m3) in 1972.^ The supply of residual fuel oil by grades
(No. 5 and No. 6 combined and No. 4), point of origin (domestic production
and import), and sulfur levels is shown in Table 1. About two-thirds of
the total U. S. supply was Imported. Statistics on imports of residual
fuel oil are shown in Table 2. The great majority of imports came from
10
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TABLE 1. DOMESTIC PRODUCTION AND IMPORT.QF RESIDUAL FUEL
OIL BY SULFUR CONTENT FOR 1972^3)
Sulfur Content,
Percent
Zero-0.
0.51-1.
1.01-2.
Over 2.
50
00
00
00
No. 5
Domestic
Production
64,855
70,824
92,652
64,188
292,519
(10.3)
(11.3)
(14.8)
(10.2)
(46.6)
and No.
6 Fuel
Import
203,137
163,764
79,316
145,447
591 ,664
(32.3)
(26.1)
(12.6)
(23.0)
(94.0)
Quantity, 1000
Oil
Subtotal
267,992 (42.7)
234,588 (37.3)
171,968 (27.4)
209,635 (33.4)
884,183(140.8)
barrels
(m3 X
Domestic
Production
6,621
3,117
1,683
609
12,030
(1.1)
(0.5)
(0.3)
(0.1)
(1.9)
106)3
No. 4 Fuel Oil
Import
22,223 (3.5)
5,967 (0.9)
2,925 (0.5)
133
31,248 (4.9)
Subtotal
28,844 (4.6)
9,084 (1.5)
4,608 (0.7)
742 (0.1)
43,278 (6.9)
Total
296,836 (47.2)
243,672 (38.7)
176,576 (28.1)
210,377 (33.5)
927,461(147.5)
Metric units may not add to totals because of rounding in conversion from barrels.
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TABLE 2. IMPORTS OF RESIDUAL FUEL OILS BY SULFUR CONTENT FOR 1972
(3)
Quantity, 1000 barrels (m3
x io6)a
Sulfur Content, percent
Country
Venezuel a
N.U.I.
Virgin Is.
Trinidad
Bahamas
Canada
Italy
Others
TOTAL
0-0.5
40,059
21 ,878
56,785
13,243
33,491
8,864
17,198
33,842
225,360
( 6.4)
( 3.5)
( 9.0)
( 2.1)
( 5.3)
( 1.4)
( 2.7)
( 5.4)
(35.8)
0.51-1.00
39,185
34,868
29,669
24,193
9,339
9,936
11,143
11,398
169,731
( 6.2)
( 5.5)
( 4.7)
( 3.8)
( 1.5)
( 1.6)
( 1.8)
( 1.8)
(27.0)
1.01-2,
45,250
7,734
660
14,033
8,960
1,593
87
3,924
82,241
(
(
(
(
(
(
1
.00
7.2)
1.2)
0.1)
2.2)
1.4)
0.3)
0.6)
(13.1)
Over
69,600
47,988
9,134
5,105
1,825
8,265
3,663
145,580
2.00
(11.1)
( 7.6)
( 1.5)
( 0.8)
( 0.3)
( 1-3)
( 0.6)
(23.1)
Total
194,094
112,468
96,248
56,574
53,615
28,658
28,428
52,827
622,912
(30.9)
(17.9)
(15.3)
( 9.0)
( 8.5)
( 4.6)
( 4.5)
( 8.4)
(99.0)
aMetric units may not add to totals because of rounding in conversion from barrels.
12
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Venezuela and the Caribbean area. The available data indicate that
only 4.7 percent of the total supply is No. 4 fuel oil. The break-
down of the remaining 95.3 percent between No. 5 and No. 6 is not
available. Most of it probably is No. 6 fuel oil.
Domestic demand for residual fuel oil by consumption categories is
shown in Table 3 for 1971 and 1972. The 1971 statistics were taken
(4\
directly from published data. x The 1972 data were derived from the
1971 data assuming that: (1) the total demand is equal to the total
supply in 1972, and (2) the percentage breakdown by consumption cate-
tories is the same in 1971 and 1972. The difference between the
supply and the demand is probably insignificant when small adjustments
are made for export change in stocks. The major consumption categories
are electric utilities, space heating for apartments and commercial
buildings, industrial uses, and vessel bunkering. All of the No. 4
fuel oil probably is used for space heating of apartments and commercial
buildings. Almost all of the residual oil is burned in boilers for
the production of steam for various uses, such as heating, electric
power generation, and vessel propulsion.
Since most of the residual fuel oil is used in boilers to generate
steam for space heating, power generation, industrial process applica-
tions, and vessel propulsion, the primary source of pollution is steam
boilers. No useful data could be found to break down the residual fuel
oil demand in each consumption category by the type and size of boilers
or other combustion process.
13
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TABLE 3. DOMESTIC DEMAND FOR RESIDUAL FUEL OIL BY USES FOR 1971(4) AND 1972
Uses
Heating Oils (apartments and commercial)
Industrial Uses (excluding refinery fuel)
Refinery Fuel (excluding heating oils)
Electric Utilities
Railroads
Military
Vessel Bunkering (excluding military)
Miscellaneous
TOTAL
1971
Quantity, 1000 bbl
(m3 X 106)
182,639 ( 29.0)
135,469 ( 21.5)
32,626 ( 5.2)
371,820 ( 59.1)
1,262 ( 0.2)
29,217 ( 4.6)
78,727 ( 12.5)
6,285 ( 1.0)
838,045 (133.2)
Percent
21.79
16.17
3.89
44.37
0.15
3.49
9.39
0.75
100.00
1972a,b
Quantity, 1000 bbl
(m3 X 100)
202,100 ( 32.1)
150,000 ( 23.8)
36,100 ( 5.7)
411,400 ( 65.4)
1,400 ( 0.2)
32.400 ( 5.2)
87,100 ( 13.8)
7,000 ( 1.1)
927,500 (147.5)
1972 figures were estimated based on 1971 figures.
Metric units may not add to totals because of rounding in the conversion from barrels.
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Industries use residual fuel oil primarily to raise steam which
then is used for process and space heating, for power generation, and
to drive equipment. A small fraction is used in direct-fired heaters
and furnaces. In most cases, it is doubtful that an industry or a
company has accurate knowledge of the ultimate fuel use. It is esti-
mated that about 90 percent of the industrial residual fuel oils is
used to raise steam for process and space heating, 5 percent for power
generation, and 5 percent in direct-fired process heaters. In petroleum
refineries, about 60 percent of residual fuel oil is probably consumed
in fired process heaters and 40 percent to raise process steam.
Refineries normally generate very little power but rely on purchased
power.
Uses of residual fuel oil by railroads probably include space heat-
ing and possibly operation of tugboats owned by railroads. A major
fraction of the military uses is probably as bunkering fuel by the
Navy.
2.1.2 Contaminants in Residual Oils
The composition of residual fuel oils—with respect to the poten-
tially polluting constituents, such as sulfur, nitrogen, trace elements and
organics—depends largely on the crude oil from which the residual fuel oil
comes. Characteristics of crude oils from major oil-producing regions
are described in Table 4. It should be noted that the characteristics
vary widely among the crude oils of a given region, or even a given country
or an area. Generalization of crude oil characteristics nontheless serves
to obtain a rough estimate of the polluting constituents in residual fuel oil
15
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TABLE 4. GENERAL CRUDE OIL CHARACTERISTICS BY REGION
(5)
Region
North America
South America
Country
U.S.
U.S.
Canada
Venezuela
Area
California
Midcontlnent
Alberta/ B.C.
Lake Maracaibo
Characteristics
Medium to high
elements
Low S, N, and
Similar to U.S
Medium to high
S, N, and trace
trace elements
. Mldcontinent
S; high trace elements
Africa
Middle East
Asia
Algeria, Libya
Nigeria and other
West African
Saudi Arabia,
Iran, etc.
Indonesia
Low S and trace elements but medium
nitrogen in relation to S
High S and moderate trace elements
Low S, N, and trace elements
-------
Sulfur
The sulfur content of residual fuel oil is reported in Mineral
Industry Surveys published monthly by the Bureau of Mines. The latest
annual statistics available for 1972 are shown in Table 1. Sulfur content
is given by ranges. To estimate the total quantity of sulfur, a
weighted average was estimated for each range based upon state and
local regulations pertaining to fuel oil sulfur levels as follows:
(1) For the zero to 0.50 percent range, the weighted average
was taken at 0.4 percent as an average of the
established 0.3 and 0.5 percent limits.
(2) For 0.51 to 1.00 percent range, the weighted average
was taken at the established 1.0 percent limit.
(3) For sulfur content above 1.0 percent, no fuel oil
sulfur regulations exist. Therefore, weighted averages
were assumed at 1.5 percent for the 1.01 to 2.00 percent
range and at 2.4 percent for the over 2.00 percent range.
The total sulfur contents of residual fuel oil derived from the
weighted averages of sulfur levels are shown in Table 5.
17
-------
TABLE 5. TOTAL SULFUR CONTENT OF RESIDUAL FUEL OIL FOR 1972
00
Sulfur Content, Percent
Range
Zero-0.50
0.51-1.00
1.01-2.00
Over 2.00
TOTAL
Weighted
Average b
0.4
1.0
1.5
2.4
No. 5 and No.
Domestic
42,900 (38.9)
117,200 (106.3)
230,000 (208.7)
255,000 (231.3)
645,100 (585.2)
9 r
Quantity of Sulfur, ton3 (10 g)
6 Fuel 011
Import
134,500 (122)
271,000 (245.8)
196,900 (178.6)
577,700 (524)
1,180,100 (1,070.5)
No.
Domestic
4,400 (4)
5,200 (4.7)
4,200 (3.8)
2,400 (2.2)
16,200 (14.7)
4 Fuel 011
Import
14,700 (13.3)
9,900 (9)
7,300 (6.6)
500 (0.5)
32,400 (29.4)
Total
196,500 (178.3)
403,300 (365.9)
438,400 (397.7)
835,600 (758)
1,873,800 (1699.9)
aBased upon a density of residual fuel oil at 331 Ib/bbl (944 kg/m3).
Estimated by Battelle.
GMetric units may not add to totals because of rounding.
in conversion from tons.
(4)
-------
Nitrogen and Trace Elements
Data on nitrogen, trace elements, and fine particulates are not as
readily available or complete as those on sulfur. Analyses of nitrogen,
nickel, and vanadium for residual fuel oils produced from several crude
oil sources are shown in Table 6. More extensive data on trace metals
by grades of residual fuel oil are shown in Table 7. The data in Table
7 indicate no apparent correlations among the fuel oil grades, sulfur
levels, and trace metal analyses. The following methodology was used
for estimating the nitrogen and trace metal content of residual fuel oil:
(1) Nitrogen, nickel, and vanadium were estimated by breaking
down the total residual fuel oil supply by crude oil sources
and applying the analysis data for each source (Table 6).
(2) Other trace metals were estimated by taking the ratios relative
to the sum of nickel and vanadium content for the entire residual
fuel oil supply.
The breakdown of the residual oil supply by crude oil sources, and
the quantities of nitrogen, nickel, and vanadium are shown in Table 8. The
compositions of residual fuel oil were taken from Table 6. For the U. S.,
Venezuelan, and Middle East crude oils, average values of the composition
data given in Table 6 were used. The compositions of the residual fuel
oils from African and Indonesian crudes were estimated by Battelle. The
concentrations of nitrogen, nickel, and vanadium averaged over the total
residual fuel oil supply were estimated at 0.45 percent, 46 ppm, and 140
ppm, respectively.
19
-------
TABLE 6. TYPICAL SULFUR, NITROGEN, AND TRACE METAL ANALYSES OF RESIDUAL FUEL OIL
Crude Source
Domestic
Venezuelan
Venezuelan (Tijuana)
Middle East
Middle East (Kuwait)
Middle East
Middle East
Middle East
Middle East (Kuwait)
Sulfur,
percent
4.0
2.6
2.2
5.2
4.4
4.3
2.6
4.1
4.1
Nitrogen,
percent
0.53
0.61
—
0.41
0.26
0.16
0.37
0.29
0.23
Nickel,
ppm
45.
94
39
58
14
9
57
48
19
Vanadium,
ppm
138
218
200
167
50
32
88
127
53
Reference
(5)
(5)
(6)
(5)
(5)
(5)
(5)
(5)
(6)
-------
TABLE 7. TYPICAL SULFUR AND TRACE METAL ANALYSES OF RESIDUAL FUEL
ro
Fuel 011 Grade
Sulfur
Trace
Type
, percent
Metals, ppm
Al
Ca
Cu
Fe
Pb
Mg
Mn
Ni
K
Si
Na
Sn
V
Zn
No. 4
ABC
0.58 0.57 1.90
0.6 4 4
0.3 3 2.8
0.05 0.04
4 1 1.2
1 0.9
0.6 1 19
0.08 0.1
0.2 -- 8
0.09 « 0.4
1 2 2.4
0.4 4 10
0.3 0.3
0.7 4 167
4
A
0.59
4
2.5
0.3
15
10
5
0.5
10
0.4
4.0
6.5
1.5
3.5
— —
No. 5
B
0.69
20
1
0.3
10
3
1
0.3
10
5
30
5
0.4
11
— —
E
1.90
5
4
0.1
8
2
9
0.5
20
0.1
4
14
--
71
_ _
F
0.69
4
5
0.3
20
3
5
0.7
10
1
3
17
--
8
_ _
B
0.78
40
3
0.5
40
9
4
1
20
1
40
11
--
14
__
No. 6
C
2.36
10
7
--
3
--
47
--
20
1
6
26
--
417
. _
H
3.07
30
4
0.4
5
8
10
0.7
20
1
20
14
0.3
110
—
G
3.95
1.5
1
0.04
0.6
0.4
1
--
12
0.2
5.7
4.0
—
40
__
-------
TABLE 8. NITROGEN, NICKEL, AND VANADIUM CONTENT OF RESIDUAL FUEL OIL
Source of
Crude Oil
, Residual fuel Oil. Produced ,0
10Jbarrels (10° nr) 10J tons (10'^g)
Polluting Constituents in Residual Fuel Oil
Nitrogen^* « Nickel c „ Vanadium1-
percent tons (10 g) ppm tons (10 g) ppm tons
o
(10Jg)
U. S. and Canada3 243,979 (38.8) 40,379 (36.6) 0.53 214,000 (194.1) 45 1,820 (1.65) 138 5,570 (5.05)
Venezuela3 392,235 (62.4) 64,915 (58.9) 0.61 396,000 (359.2) 67 4,350 (3.95) 209 13,570 (12.31)
Middle East3 120,048(19.1) 19,868(18) 0.29 58,000(52.6) 34 680(0.62) 86 1,710(1.55)
1X5 Africa6 120,048 (19.1) 19,868 (18) 0.10 20,000 (18.1) 10 200 (0.18) 20 400 (0.36)
Indonesia6 51,151 ( 8.1) 8,465 ( 7.6) 0.10 8,000 (7.25) 10 80 (0.07) 20 170 (0.15)
TOTAL 927,461 (147.5) 153,495 (139.2) 696,000 (631.4) 7,130 (6.47) 21,420 (19.43)
3Contaminant analyses based on data given in Table 7.
Contaminant analyses estimated by Battelle.
°Average concentrations were estimated at: N = 0.45 percent (750 tons/106barrels) (4.28~kg/m3)
Ni = 46 ppm (7.7 tons/10° barrels) (43.97 g/mjl
V - I/Iff nnm t Ot 4-«»,r. / 1 fW k-*t*w*A1»\ /1O1 O"7 „ /m^ 1
V = 140 ppm (23 tons/10 barrels) (131.27 g/nT)
rounding in conversion from reported units.
Metric units may not add to totals because of
-------
Concentrations of other trace elements were estimated by taking
the ratios relative to the sum of nickel and vanadium content (i.e.,
weight of trace element per weight of Ni + V). Data were compiled from
direct analysis of residual fuel oil (data for No. 6 fuel oil in Table 7),
(5)
crude oil analysis, v ; analysis of particulate emissions from combustion
of a No. 6 fuel oil, and other sources. (8,9,10) Results for trace
metal content of residual fuel oil are summarized in Table 9.
Organ ics
The nature of the organic fractions found in burning residual oil
is primarily polycyclic organic matter (POM) and CO; these potentially
hazardous pollutants result from incomplete combustion. ' The POM
class includes polynuclear aromatic hydrocarbons commonly identified
as PNA or PAH, and nitrogen-containing heterocyclic compounds. Although
the physical states of POM and soot are different, they probably have
common origins and similar chemical reactivity. The materials labeled
POM are emitted in small or trace quantities during the combustion of
residual oil. Studies of the mode of formation and destruction of POM
in the combustion process are difficult to carry out because of the very
low concentrations, the lack of simple analytical procedures for identifying
them, and the large number of individual compounds making up this class
of material. Typical POM that have been observed are anthracene, pyrene,
methyl anthracene, fluoranthene, methyl fluoranthenes/pyrenes, chrysene,
perylene, benzo(ghi)perylene, and coronene.
2.1.3 Emission Standards
Current emission standards for S09, NO , and particulates from oil-fired
£ A
boilers are 1.2 (0.516), 0.70 (0.3), and 0.10 (0.04 kg) Ib per 106 Btu (GJ),
respectively.
23
-------
TABLE 9. ESTIMATED TRACE METAL ANALYSES OF RESIDUAL FUEL OIL
El ement
Fe
B
Si
Mg
Mn
Pb
Al
Mo
Cu
Ca
Cr
Ba
Co
K
Sn
Ag
Na
Zn
T1
As
Sb
Hg
Concentration -
ppm ton/10 barrels (g/m )
19
0.9
21
19
2.5
16
24
0.13
1.0
5.4
1.5
2.5
7.7
1.2
0.4
0.4
20
0.9
1.5
0.22
0.54
0.05
3.1
0.15
3.5
3.1
0.41
2.6
4.0
0.022
0.17
0.89
0.25
0.41
1.3
0.20
0.066
0.066
3.3
0.15
0.25
0.036
0.089
0.0083
(17.69)
( O.S56)
(19.97)
(17.69)
( 2.34)
(14.84)
(22.82)
( 0.136)
( 0.970)
( 5.08)
( 1-43)
( 2.34)
( 7.42)
( 1.14)
( 0.377)
( 0.377)
(18.83)
( 0.856)
( 1.43)
( 0,205)
( 0.508)
( 0.0047)
Percent of
Total Metal Content
5.6
0.27
6.4
5.6
0.75
4.7
7.3
0.040
0.31
1.6
0.45
0.75
2.4
0.36
0.12
0.12
6.0
0.27
0.45
0.065
0.16
0.015
Reference
(8)
(9)
(8)
(8)
(8)
(8)
(8)
(9)
(8)
(8)
(9)
(9)
(9)
(8)
(8)
(9)
(8)
(9)
(9)
(5)
(5)
(10)
24
-------
TABLE 9. ESTIMATED TRACE METAL ANALYSES OF RESIDUAL FUEL OIL (continued)
Concentration 3 Percent of
Element ppmton/10 barrels (g/m ) Total Metal Content Reference
Se 2.4 0.40 ( 2.28) 0.73 (11,12)
Ni 46 7.6 (43.37) 13.8 (Table 8)
V 140 23 (131.24) 41.8 (Table 8)
TOTAL 334 55 (313.83) 100.1
25
-------
2.2 Definition of Environmental Assessment and Control Technology
Development
An environmental assessment, as defined for IERL-RTP studies of fossil
energy processes, is a continuing iterative study aimed at:
(1) determining the comprehensive multimedia environmental
loadings and environmental control costs, from the
application of the existing and best future definable
sets of control/disposal options, to a particular set
of sources, processes, or industries; and
(2) comparing the nature of these loadings with existing
standards, estimated multimedia environmental goals,
and bioassay specifications as a basis for prioritization
of problems/control needs and for judgment of environ-
mental effectiveness.
Figure 1 includes a more comprehensive delineation of environmental
assessment in the form of a flow schematic.
The overall nature of control technology development is depicted
in Figure 2.
26
-------
CONTROLTECHNOLOGY
DEVELOPMENT
• ENGINEERING ANALYSIS
• IASK MO APPLIED PROCEMS
DEVELOPMENT
• SPECIFIC PROCESS DEVELOP
HINT AND EVALUATION
MAYK
s*\
/IETTER\
mf rnitTani N
CURRENT PROCESS TECH
NOLOGY IACKGROUNO
• PROCESS INFORMATION
• SCHEDULES
• STATUS
• PRIORITIES FOR FUR
THEM STUD*
ENVIRONMENTAL DATA ACQUISITION
• EXISTING DATA FOR EACH PROCESS
• IDENTIFY SAMPHUG AID ANALYTI
CAl TECHNIQUES INCLUDING
IIDAtUYS
• TEST MOGNAM DEVEIOWEIIT
• COHfREMEIISIVt WASTE STREAM
CHARACTERIIATIOIIIEVEISI II.
Illl
• IWUT OUT*UT HATERIAIS
CHARACTERIZATIOI
•CONTROL ASSAYS
to
CURREIT l«VIRO*ME«TAl
IACKG*OU«0
• rOTtHTIAirOLLUTMTS
AID U» ACTS (HAIL
MEDIA
• DOSE REVOUSE DATA
• fEDSTATESTOS CRITERIA
• TRAkSfORT MODELS
• SUMMARIIEIIDUSTRY
RELATED OCCUPATIONAL
HEALTH E'IOEMIOIOGIC«L
LITERATURE
CACTS
• PROCESS ENGINEERING POLLUT
ANT/COST SENSITIVITY STUDIES
• ACCIDENTAL RELEASE. MAIFUNC
TION TRANSIENT OPERATION
STUDIES
• FIELD TESTING IN RELATED
APPLICATIONS
• DEFINE IEST CONTROL TECH
NIOUE FOR EACH GOAL
• POLLUTANT CONTROL SYSTEMS
STUDIES
• CONTROL TECHNOLOGY H40
PLANS AND GOALS
CONTROL
VNEEDEDV
ENVIRONMENTAL ALTERNATIVES ANALYSES
SELECT AND APPIV
ASSESSMENT ALTERNATIVES-
ALTERNATIVE SETS OF MUITI
MEDIA ENVIRONMENTAL GOALS
(MEG-SI
• IEST TECHNOLOGY
• EIISTINC AMIIENT STOS
• ESTIMATED PERMISSIILE
CONC
• NATURAL IACKGROUND
IELIMINATION OF DISCHARGE!
•SIGNIFICANT DETERIORATION
• MINMUM ACUTE TOIICITY
EFFLUENT
• QUANTIFIED CONTROL RlOkEEOS
• QUANTIFIED CONTROL ALTERNATIVES
• QUANTIFIED MEDIA DEGRADATION
ALTERNATIVES
• QUANTIFIED NONPOLLUTANT EFFECTS
AND SITING CRITERIA ALTERNATIVES
• DEFINED RESEARCH DATA IASE FOR
STANDARDS
ENVIRONMENTAL SCIENCES RID
• HEALTH'ECOLOGICAl EFFECTS
RESEARCH
• TRANSPORTTRANSFORMATION
RESEARCH
MEDIA DEGRADATION AND
HEALTHrECOLOGICAl
IMPACTS ANALYSIS
0 AIR MATER AND LAND
QUALI1V
• INCREASED SICKNESS
ANDDEA1HS
• ICOIOCY RdATEO
IMtCTS
0 MAIIHIAl KIlAIIO
II'UIS
Figure 1. Environmental assessment/control technology development diagram.
-------
CONTROL APPROACHES:
ENVIRONMENTAL
ASSESSMENT
A Specific
Control
Needs
Defined ,
to
00
PRELIMINARY
CONTROL
APPROACH
SELECTION
1 0« 1
J Treatment •>
r fv
r ItX
Liquids
Treatment
Solids
Treatment
Final
Disposal
Process
Modifications
Combustion
Modifications
Fuel
Cleaning
Fugitive
Emissions
Control
Accidental
Release
Technology
\\
. *
11
1
1 \
n
1
1
1
\
BASIC AND APPLIED R&D
• Bench and Pilot Experimental
Studies to Assess Generic Types
for Effectiveness & Secondary
Environmental Problems
• Fundamental Studies
1 1
1 ENGINEERING ANALYSIS
• Review Control Tech. Alternatives
Based on Phys/Chem. Conditions,
Pollutant Cone., etc.
• Assess Potential for Application
(New, Retrofit, Size, etc.)
• Preliminary Design & Con Studies
• Systems Comparisons
SPECIFIC CONTROL PROCESS
DEVELOPMENT, EVALUATION
• Conceptual Design & Con Studies
• Optimized Integration in
Systems To Be Controlled
«> Pilot & Demonstration Studies
• Field Testing of State of the Art
and Related Systems
I Quantified
Effectiveness,
Economics, &
Energy Costs
TECHNOLOGY
TRANSFER
MULTIMEDIA
ENVIRONMENTAL
CONTROL
ENGINEERING
MANUAL
• Additions
• Revisions
Figure 2. Control technology development diagram.
-------
2.3 Alternatives for Residual Oil Combustion/Utilization/Control
Pollution control alternatives for stationary sources using residual
oil can be grouped into the following categories:
0 Direct Combustion With or Without Particulate Control
0 Direct Combustion With Flue Gas Desulfurization
0 Direct Combustion in Fluid Bed of Limestone at Atmospheric
Pressure (AFBC)
0 Partial Combustion at Atmospheric Pressure—Partial
Oxidation (POX) Followed by Cleanup and Conventional
Combustion
0 Partial Combustion in a Chemically Active Fluid Bed
(CAFB) Followed by Conventional Combustion
0 Direct Hydrodesulfurization (HDS) of Residual Oil
for Combustion
0 Upgrading of Residual Oil Followed by HDS and
Conventional Combustion
2.3.1 Direct Combustion With or Without Particulate Control
This category depends on crude oil low enough in sulfur so that the
residual oil remaining after refining is low in sulfur and will meet
standards when burned with no controls. Where particulate control is
necessary, both baghouse filters (fiberglass) and electrostatic precipit-
ators (ESPs) have been used; however, these collectors do not exhibit
high collection efficiencies in the submicron range. Though the weight
of these fines is not appreciable they do contribute significantly to
visible emissions. ^14^ While the theoretical efficiency of the ESP
29
-------
is quite high, the average operating efficiency is found to be much lower.
The shorting out of one electrode can cause an entire section of electrodes
to go out of service. Component failure of this kind cannot be corrected
until the unit is removed from service. Day-to-day fluctutations of the
dust resistivity can result in lowering the efficiency. This can be
caused by variations in the S03 concentration which acts as a catalyst in
i
gas.
(16)
the collection mechanism or the moisture content of the flue gas. For
these reasons, baghouse filters would be preferred over ESPs.
2.3.2 Direct Combustion with Flue Gas Desulfurization
Flue gas desulfurization (FGD) processes are generally of the
throwaway type, which produce an unusable mixture of sulfur compounds,
or regenerable processes which can ultimately produce either elemental
sulfur or sulfuric acid as a by-product. Elemental sulfur is normally
preferred because it is a non-corrosive solid which is easily handled,
stored, and shipped.
Non-Slurry Processes
0 Sodium Solution Scrubbing — SOg Regeneration and Reduction to Sulfur
Stack gas is washed with water in a venturi scrubber for removal of
particulates and then washed 1n a spray scrubber with a recirculating
solution of sodium salts 1n water for S0« removal. Makeup sodium car-
bonate is added to cover handling and oxidation losses of sodium sulfite
and sulfate. Sodium sulfate crystals are purged from the system, dried,
and sold. Water is evaporated from the scrubbing solution using a
30
-------
single-effect evaporator to crystallize and thermally decompose sodium
bisulfite, driving off concentrated S0«. The resulting sodium sulfite is
recycled to the scrubber and the SOp is reacted with methane for reduction
to elemental sulfur. The regeneration and reduction areas are designed
as a cyclic absorption/desorption process for removing SCL from waste
gases and producing a concentrated SCL gas for feed to a contact sulfuric
acid plant or to a Claus sulfur plant.
0 Ammonia Process
Flue gas is passed through a scrubbing tower and S0? is absorbed by
an aqueous stream of ammonium hydroxide, bisulfite, and sulfite. Makeup
ammonia is injected into the flue gas ahead of the scrubber. The scrubber
effluent is filtered to remove sludge and then aerated to oxidize the
ammonium sulfite to ammonium sulfate. The ammonium sulfate is crystallized
in an evaporator and then centrifuged and dried.
0 Aluminum Sulfate Process
Flue gas, after the acid mist has been removed, is sent to an absorp-
tion tower where SQ* ""s absorbed by a basic aluminum sulfate solution.
The enriched solution goes to a regenerator and S02 is stripped off by
steam heating. The S02 stream is dried and returned to the sulfuric
acid plant. A side stream of enriched solution is reacted with calcium
carbonate to prevent buildup of S03 in the absorbent. The calcium
sulfate is removed by filtration.
31
-------
Slurry Processes
0 Limestone Slurry Scrubbing
Stack gas is washed with a recirculating slurry (pH of 5.8-6.4) of
limestone and reacted calcium salts in water, using a two-stage (venturi
and mobile bed) scrubber system for particulate and SOg removal. Lime-
stone feed is ground wet prior to addition to the scrubber effluent hold
tank. Calcium sulfite and sulfate salts are withdrawn to a disposal
area for discard. Reheat of stack gas to 175°F (80°c) is provided.
0 Lime Slurry Scrubbing
Stack gas is washed with a recirculating slurry (pH of 6.0-8.0) of
calcined limestone (lime) and reacted calcium salts in water using two
stages of venturi scrubbing. Lime is purchased from a nearby calcination
operation, slaked, and added to both circulation streams. Calcium sulfite
and sulfate are withdrawn to a disposal area for discard. Reheat of stack
O 0
gas to 175 F (80 C) is provided.
0 Magnesia Slurry Scrubbing — Regeneration to HoSO,
Stack gas is washed using two separate stages of venturi scrubbing--
the first utilizing water for removal of particulates, and the second
utilizing a recirculating slurry (pH of 7.5-8.5) of magnesia (MgO) and
reacted magnesium-sulfur salts in water for removal of S02- Makeup
magnesia is slaked and added to cover only handling losses, since the
sulfates formed are reduced during regeneration. Slurry from the S09
32
-------
scrubber is dewatered, dried, calcined, and recycled during which con-
centrated SOg is evolved to a contact sulfuric acid plant producing 98
percent acid.
2.3.3 Direct Combustion in Fluid Bed of Limestone (AFBC)
To assess the removal of SOg from combustion gases when residual
fuel oil is burned in a fluidized bed of sulfated lime with continuous
feeding of limestone additive, experiments were performed in a 6-in. (15.2 cm)
diameter fluidized-bed combustor at a variety of operating conditions.
Residual fuel oil (containing 1.9% S) was burned in an excess of oxygen at
o o
bed temperatures ranging from 1450 to 1650 F (790 to 900 C), Ca/S mole
ratios up to 11.9, a gas velocity of <3 ft/sec (0.91 m/sec) (except for
one experiment at 5.5 ft/sec [1.68 m/sec]), and with 3 vol % oxygen in
the flue gas (except in one experiment with 1 vol % oxygen in the flue gas).
Table 10 lists operating data, concentrations of some components
of the flue gas, and calculated sulfur retention and combustion efficiency
data for the experiments in which limestone was fed to the combustor.
2.3.4 Partial Combustion at Atmospheric Pressure—Partial Oxidation
(POX) Followed by Cleanup and Conventional Combustion
Over 100 commerical Partial Oxidation Units are now in successful
operation around the world. Over half of these are charging residual
fuel oil, with many others on crude oil. Others operate on light oil,
naphtha, and natural gas. There is only one commercial unit in the
33
-------
TABLE 10
OPERATING DATA AND RESULTS. COMBUSTION OF RESIDUAL FUEL OIL IN EXCESS AIR
Equipment: ANL 6-in. (150 mm) dia fluidized-bed combustor
011: Esso residual fuel oil, 1.97 wt % sulfur
Additive: Limestone No. 1359, as received (94.8 wt % CaCO,, 0.9 wt % MgCOv
609 urn average particle size)
Starting Fluidized Bed: 17.3 Ib (7,850 g) partially sulfated and calcined limestone No.
1359 (-\-24-1n. (600 mm) fluidized-bed depth) Note: The final
bed from a run was used as the starting bed for the following run.
02 Concentration in Flue Gas: ^3% (except 4A-1, 1%)
Fluidi zed-
Experiment Bed
011 Temp
2
3A
3B
3C
4A
4B
4A-1
1650
1550
1550
1550
1450
1650
1450
(900)
(840)
(840)
(840)
(790)
(900)
(790)
011 Limestone
Feed Rate Feed Rate
(Ib/hr) (g/s) (Ib/hr) (g/s)
5.8
3.3
3.0
3.3
3.2
3.2
4.8
(0.73)
(0.42)
(0.38)
(0.42)
(0.40)
(0.40)
(0.60)
0.6
0.8
2.2
1.1
1.2
1.2
1.2
(0.08)
(0.1)
(0.28)
(0.14)
(0.15)
(0.15)
(0.15)
Gas
Ca/S Velocity
Mole Ratio (ft/sec ) fm/s)
1.6
4.1
11.9
5.4
6.0
6.0
4.0
5.5 (1.68)
3.2 (0.98)
3.2 (0.98)
3.0 (0.91)
3.1 (0.94)
3.1 (0.94)
3.3 (1.0)
Flue Gas Composition
so2
(ppm)
1350
630
170
200
350
550
520
NO CO
(ppm) (ppm)
135
110
140
150
140
130
190
8500
6000
6000
5000
5000
5000
>1 2000
(ppm)
>3400
1500
800
1200
1100
1000
>3400
(°?
D^a
14.4
15.0
14.2
15.0
14.0
No
Sulfur Combustion
Retention Efficiency
(*) (%)
16
60
90
88
78
66
68
<92
95
94
No Data
95
96
No Data
Data
-------
Continental United States. This unit charges residual fuel oil and produces
hydrogen. Another unit is operating on mixed feeds in Puerto Rico. Two
additional units are planned for completion in the near future.
Essentially, any residual fuel oil or lighter hydrocarbon can be
charged. The residual fuel oil is partially oxidized to form a gaseous
mixture of carbon monoxide (CO) and hydrogen (H2) with a small amount of
methane (CH4). Either oxygen (02) or air (02 + N2) can be used for the
partial oxidation. Some carbon dioxide (C02) and carbon soot (C) are
formed as by-products. When air is used, the nitrogen remains in the
gas product. When oxygen is used, the peak temperatures are usually
controlled by a diluent such as steam or carbon dioxide. Carbon soot
is produced as a result of incomplete combustion.
Residual fuel oil contains hydrocarbons and certain contaminants
such as sulfur (S), nitrogen (N), ash, and various metals, which are
mainly sodium (Na), vanadium (V) and nickel (Ni). The sodium is usually
reduced to a sufficiently low level by crude oil desalting before the
residue is fed to the reactor. Excessive sodium could damage the
reactor lining. Some of the ash components, including vanadium and
nickel compounds, along with some hydrogen cyanide (HCN), ammonia (NH.J,
and any formic acid (HC02H) formed, are removed from the product gas in
a water scrubber, since they are either soluble or suspended in water.
The carbon soot remains in suspension in the water and can be removed
by naphtha extraction or other recovery methods. The soot may then be
recycled to the reactor for further reaction. Some ash is removed from
the reactor as friable slag during shutdown for inspection. The sulfur
products are only slightly soluble in water and therefore remain in
35
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the product gas stream as hydrogen sulfide (H2S), with some carbonyl
sulfide (COS) and a trace of carbon disulfide (CS2).
Several commercial processes are reported to be available for removal
of up to 99+ percent of the H2S from the product gas. Some processes
selectively remove the H2S, leaving much of the C02 in the gas. The C02
is desirable when using the gas as fuel to a gas turbine. By removal
of much of the C02, using other absorbents, the product gas will have a
higher Btu content.
The desulfurized product gas with essentially all the C02 removed will
have a higher heating value (320 to 325 Btu/scf [9.56 to 9.71 kJ/M3]) when 02
is used for the oxidation. By comparison, the product from air oxidation
will have a heating value of 120 to 125 Btu/scf (3.58 to 3,73 kJ/m3) because of
the nitrogen remaining in the gas. Because 02 is more costly than air,
6 Q
the product gas from 02 partial oxidation is more costly per 10 Btu (10 .1)
produced.
2.3.5 Partial Combustion in a Chemically Active Fluid Bed (CAFB)
Followed by Conventional Combustion
The Chemically Active Fluid Bed (CAFB) process uses a shallow
fluidized bed of lime or like material to produce a clean, hot gaseous
fuel from heavy high-sulfur feedstocks, such as residual oils or refinery
bottoms. Fuels which are normally solid, such as coal, have also been
tested. The CAFB performs three operations simultaneously: (1) gasification
and/or cracking of the feedstock; (2) removal of sulfur; (3) removal of
36
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vanadium and other metals. The sulfur, vanadium, and other metals are
captured by the CAFB. The CAFB has operated at temperatures in the range
of 1600 to 1700°F (870 to 930°C) for that portion of the bed receiving the
feedstock, commonly called the gasifier. The necessary heat release to
maintain this temperature in the gasifier is accomplished by partial
combustion of the feedstock. Flue gas recycle has been used to control
the bed temperature. The amount of air to the CAFB is about 20 percent
of that required for complete combustion of the feedstock, and is varied
from this percentage to match the attributes of the feedstock to the
capabilities of the process.
As the feedstock is gasified, the sulfur is captured by the CAFB as
calcium sulfide, because the reaction occurs in an oxygen deficient or
reducing atmosphere. The bed material is then moved, via fluidization,
to the regenerator section of the reaction vessel. In current practice,
this regenerator section is separated from the gasifier portion by a
refractory divider and has a separate plenum or air passage to supply
air for the regeneration reaction. The regeneration reaction is
accomplished by passing air through the fluid bed. The calcium sulfide
in the bed is oxidized to sulfur dioxide and calcium oxide. A minor
amount of calcium sulfate is also produced during the regeneration step.
The heat required to sustain the regeneration reaction at about 1500°F
(815°C) is produced by the oxidation of the calcium sulfide with a
contribution from the oxidation of carbon deposited on the surface of the
bed material. The gaseous stream from the regenerator contains 6 to 10
percent, by volume, of S02 with 1 to 4 percent C02 and virtually no
oxygen. This gas stream can be converted to either elemental sulfur or
other products using existing technology. The regenerated bed material
37
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is returned, via fluidization, to the gasifier portion of the vessel and
the cycle is repeated.
The clean, hot product gas for the gasifier is ducted, through
cyclones, to a boiler and burned in the normal manner, using burners
designed specifically for the hot low-heating-value product gas.
From the above description, the basic areas of the CAFB process
can be described as: (1) a fluid lime-bed particle combustor or gasifier;
(2) an air blown regenerator; (3) solids transfer, makeup, and with-
drawal; (4) fuel (feedstock) supply; (5) air supply; and (6) product
gas ducting.
The process, as developed under U. S. Environmental Protection
Agency (EPA) sponsorship, operates at atmospheric pressure. Pressure
differentials throughout the system are required to induce fuel and
materials flow and are on the order of those found in conventional
boiler systems; that is on the order of 10 kPa. Figure 3 is a line
diagram of the CAFB flow plan, and Figure 4 is a photograph of the
Esso England Continuous CAFB Pilot Plant.
2.3.6 Direct Hydrodesulfurization (HDS) of Residual Oil for Combustion
The rapid growth of energy consumption in heavily industrialized
countries, such as Japan and the United States, has created a large
demand for heavy fuel oils. The increase in consumption created a rise
in ambient S02 concentrations. To reduce the environmental impact of the
38
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CO
CO
-i
HEAT EXCHANGER
COMBUSTION AIR BLOWER
REGENERATOR AIR BLOWERS
FUEL INJECTION
AIR
(3)
N2 FOR SOLIDS A
TRANSFER
GASIFIER AIR BLOWERS
PROPANE FOR
STARTUP
Figure 3. CAFB continuous pilot plant flow plan
-------
Figure 4. The Esso England continuous CAFB pilot plant.
40
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environmental impact of the combustion of these fuels, sulfur-in-fuel
regulations were adopted. In Japan, for instance, utilities are required
to burn fuels with as low as 0.1 percent sulfur by weight to no greater
than about 1.0 percent sulfur. One method of producing these low sulfur
fuel oils (LSFO) is direct HDS of reduced atmospheric crudes.
Since 1968, reduced crude direct HDS technology has been applied to
product LSFO from Middle East atmospheric residues. There are at this
time 11 commercial direct HDS units operating with a combined production
capacity of 459,000 barrels (73 x 103 m3) per day of LSFO. Ten of the
11 units are in Japan.
The direct HDS process consists of seven interconnected unit
operations:
1. Storage and Pretreatment.
2. Reaction.
3. Separation.
4. Recycle Gas Purification.
5. Sulfur Recovery.
6. Tail Gas Treatment.
7. Fractionation.
Atmospheric reduced crude from the storage and pretreatment section
passes into the reactor after being combined with makeup hydrogen and
recycle gas. In the reactor, the sulfur in the reduced crude combines
with the hydrogen to form hydrogen sulfide (H2S). The reactor effluent
41
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enters a series of flash vessels which separate the stream into liquid,
recycle-gas, and sour fuel gas fractions. The liquid streams pass to a
distillation column for fractionation into LSFO, middle distillate, naphtha,
and sour fuel gas. The recycle gas goes to an amine scrubber where the
li^S is removed. (It is necessary to remove the f^S, since its presence
in the hydrogen-rich recycle gas would reduce the desulfurization rate.)
This purified recycle gas is either used as quench gas to moderate the
reactor's temperature or mixed with the feed and makeup hydrogen. The
rich amine passes to an amine regenerator for separation of the recycle
amine and hLS.
The H£$ rich off-gas stream from the amine regenerator passes to a
Claus unit for recovery of the sulfur. The Claus feed stream may contain
95-99 percent H«S, of which about 97 percent is converted into molten
sulfur. The unconverted HgS exits the unit in the form of SOo- Since
the SOg concentrations in the Claus tail-gas are generally significantly
higher than national or local standards, additional control, in the form
of a tail-gas treater (TGT), is required.
2.3.7 Upgrading of Residual Oil Followed by HDS and Conventional
Combustion
This category of residual oil usage involves the upgrading of residual
oil and then using HDS followed by conventional combustion. The up-
grading can be a simple demetalUzatlon which uses techniques and catalysts
like those used for HDS. Another upgrading technique involves Flexi coking^
42
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which is de-asphalting or coking followed by HDS. In some cases only a
vacuum still is used to prepare the feed for the HDS unit. Once the
pretreatment has been accomplished, the HDS follows the path outlined
in the HDS section above.
2.4 History of the IERL-RTP Program Relating to Residual Oil
The IERL-RTP program for residual oil may be considered in several
parts: one part concerned mainly with the CAFB process and its relation-
ship to alternate processes, a second part concerned with the environ-
mental assessment of residual oil usage in general, and a third part
dealing with control technology development for the treatment of
residual oil.
2.4.1 The CAFB Process and Its Relationship to Alternatives
The CAFB portion of the IERL-RTP program began in June 1970, when
a predecessor agency of EPA entered into a joint development program
with Esso Petroleum Company, Ltd. Development of the process had
begun in 1966, with Dr. Gerald Moss of Esso Research Centre, Abingdon,
U.K., and others undertaking experimental work. A patent was issued based
on this early work, which was done under the sole sponsorship of Esso
Petroleum, Ltd.
The EPA involvement resulted in six separate contracts with Esso
Research Centre, Abingdon (ERCA). The work through 1973 is described in
a series of reports to the EPA. During this period, a continuous unit
(as opposed to the previous batch type units) was commissioned. Runs in
43
-------
excess of 300 hours were made in this unit using a feedstock of atmospheric
distillation bottoms from the Amuay refinery. Ten runs have been completed
on the continuous unit and over 3000 hours of operation have been logged.
Subsequent to the findings of the development effort, EPA obtained a
technical and predicted cost review which confirmed that the CAFB was
viable when compared to the alternatives such as flue gas scrubbing or HDS
of heavy residual oil. The review is updated periodically and a current
EPA contract, 68-02-2142, with Westinghouse Research Laboratories has,
as a part of the effort, current review and update of the CAFB process.
In 1972, a search for a utility partner for a possible demonstration
was launched, and in early 1973, a utility agreed to participate in
further studies and in the design effort for a demonstration of the
atmospheric-pressure CAFB process. A preliminary design and cost estimate
for a 50 MWe unit was carried out through cooperation of the EPA contractor,
the utility partner, an engineering firm under subcontract, and a sulfur
recovery process developer. At the time a decision point was reached, in
April 1975, strong pressure was exerted by the U. S. Government to turn
all boilers capable of firing coal to this fuel. Since the specific boiler
under consideration was capable of firing coal, the conversion from the
low sulfur oil then being fired in the boiler to a high sulfur residual
oil via the CAFB process was dropped.
In April 1975, a utility and an engineering firm who had been considering
the CAFB process on private basis were located. Discussions indicated that
agreement could be reached in which EPA would underwrite the design costs
44
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and the utility would underwrite the equipment and fabrication effort.
This avoided both the complexity of a three-party contract and the need
for the Government to acquire an interest in capital equipment, which would
require a complex "buy back" negotiation to protect the interests of the
Government.
In June 1975, a letter contract (68-02-2106) was signed by EPA with
the engineering firm Foster Wheeler Energy Corporation (FWEC), and the
details of a contract between FWEC and the utility (Central Power and
Light (CPL) of Corpus Christi, Texas) were negotiated. Design work
under the EPA contract began immediately, but the CPL-FWEC contract could
not become operative until the arrangements between CPL and other utilities
sharing in the effort received the approval of the Securities and
Exchange Commission. The final approval was received and the contract
made operative in March 1976. Shortly afterwards, the EPA-FWEC contract
for the design effort was converted from a letter contract to a standard
contract with all clauses and provisions, costs, and other items defined
exactly.
Reference was made to supporting contracts for the CAFB demonstration.
In mid-April of 1977, a count showed 10 contracts active in direct support
of the CAFB demonstration effort. Some of these were relatively limited
in both scope and period of performance, such as the contract with GCA of
Bedford, Mass., for sampling of the continuous unit and for preliminary
environmental assessment of the CAFB process based on the sampling effort
and contract reports. Others, such as the contract for the basic effort
with FWEC, were much broader in scope, giving rise to subcontracts, and
extended for 3 to 4 years.
45
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The EPA program does not aim solely for demonstration of a process,
but rather seeks to develop an economically viable process with consider-
ation for the multimedia effects on the environment from the beginning of
development. This concern is exemplified by the infrastructure of supporting
contracts which are included in the EPA supported CAFB program. All of
the contracts contain tasks related to assessing the environmental impacts
and to solving any potential adverse environmental impacts which may
result from operation of the CAFB process. The availability and handling
of heavy residual fuels, the possible means of disposal or sale of spent
bed material, the properties of spent bed material after various treatments,
the possibility of rejecting all sulfur as calcium sulfate, the applica-
bility of the CAFB as a retrofit, the size of the market, the composition
of the market, the locality of probable CAFB usage related to the raw
material supply of bed material, the limits of fuel parameters acceptable
for CAFB feedstock, the removal and retention of trace and hazardous
materials by the CAFB process, and the sulfur removal efficiency are
but a few of the areas of the CAFB process considered in the program
administered by the Industrial Environmental Research Laboratory at
Research Triangle Park, N. C., under EPA's Office of Research and
Development.
2.4.2 Environmental Assessment of Residual Oil Usage
The second part of the IERL-RTP residual oil program can be traced
from May 1976, when Catalytic, Inc., began environmental and economic
assessments of methods utilizing (or capable of utilizing) residual
oil to produce electricity. The methods were classified by state of
development into one of three categories or phases of work:
46
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Phase I:
Processes, such as hydrodesulfurization (HDS),
flue gas desulfurization (FGD), and partial
oxidation (POX), which are operating or in
commercial design.
Phase II: Processes, such as Chemically Active Fluidized
Bed (CAFB), which are in the demonstration
plant design but have a good chance of becoming
commercially feasible during the 3 years of the
contract.
Phase III: Processes, such as residual oil solvent extraction
(ROSE), which are in the pilot plant phase of
development.
The effort during the first year (May 1976-May 1977) was the asses-
ment of the Phase I processes. A Catalytic, Inc. report (see Section 8.2) pre-
sents the information obtained, status, conclusions, and recommendations for the
three Phase I processes: HDS, FGO, and POX. Preparation of the work plan
for the Phase II assessment of CAFB is underway.
Descriptions of the POX, HDS, and FGD processes appear in the report.
Since HDS and FGD are commercial and operating, the emphasis for each of
these is on the presentation and discussion of information obtained on the
units visited.
Catalytic prepared a work plan describing six major task areas. The
Catalytic report descusses the work performed and the status of each task.
47
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Based on the information obtained and the progress made, Catalytic drew
conclusions as to the environmental information necessary for each process.
2.4.3 Control Technology Development for Residual Oil Treatment
The third part of the program began in the early 1970's and involves
two types of investigations. One is a research grant project with
Dr. Satterfield at MIT to develop basic data on the interactions between
HDS and hydrodenitrogenation (HDN); the other is a development program
to obtain better catalysts to promote HDS and HDN.
The research program began with simple model compounds, and looked
at the gas phase reactions for the compounds alone and in the presence
of each other. As a start, work was conducted at low pressures (less than
12 atmospheres), and temperatures of 200 to 400°C with various commercial
catalysts in a flow microreactor. The model compounds were pyridine and
thiophene. Results indicated that interactions are affected by changes in
temperature caused primarily by a shift in the rate-controlling step.
Work continues at high pressures with more complex compounds such as
quinoline.
A catalyst/sorbent development program was initiated in 1972, with
Hydrocarbon Research, Inc., at Trenton, New Jersey. The initial objectives
were to investigate low cost demetallization catalysts at the laboratory
level, select and test the most promising, and estimate the cost and
viability of using the demetallization step before conventional HDS.
These objectives were met with a 1973 publication which indicated the
potential for the technique. The low cost demetallization catalyst was
48
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a 20 x 50 mesh activated bauxite, impregnated with small amounts of
molybdenum.
The next phase of the work investigated optimizing the amount of
molybdenum, exploring commercial technology for producing the catalyst,
and testing of the catalyst which was produced using commercial techni-
ques. A 1975 report on this work indicated that the 1 percent molybdenum
loading had the best potential, and small-scale pilot plant testing with
different difficult-to-desulfurize vacuum residual oils was conducted.
These tests indicated that the technique was still viable, but additional
tests would be required to determine the tradeoff of metals and sulfur
removal in the first step, demetallization, versus their removal in the
second step, HDS.
Tests were conducted at various demetallization operating conditions
to optimize the overall desulfurization. These were reported in a 1976
publication, and they indicated that the new first stage catalyst, when
used in an overall two-stage demetallization/desulfurization process,
offers a substantial operating cost advantage over a direct desulfuriza-
tion process for producing low sulfur fuel oils from high metals petroleum
vacuum residua. Work since then has concentrated on the effect of pore
size distribution on catalyst activity for HDN.
49
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3. ACCOMPLISHMENT PLANS/SUBOBJECTIVES/WORK TASKS
All work underway on Residual Oil Processing Is being done under
the Accomplishment Plan for "Energy Control Technology - Fuel Processing."
The following Subobjectives and Work Tasks are being pursued:
Subobjective: Environmental Assessment
Work Tasks: Environmental Assessment of Residual Oil
Usages
Analytical Support for Residual Oil Usage/
Determination of Hazardous Substances
Subobjective: Chemically Active Fluid Bed Residual Oil
Cleanup
Work Tasks: Chemically Active Fluid Bed on
Small Commercial Scale
Demonstrate Chemically Active Fluid Bed
on Small Commercial Scale
Engineering Support of Chemically Active
Fluid Bed Demonstration
Multiple Option Service Contract Tasks in
Support of the Fluid Bed Demonstration
Subobjective: Control Technology Development
Work Tasks: HDS/HDN Interactions in Liquid Fuels
Control Technology for HDS/HDN of Liquid
Fuels
50
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4. MEANS OF ACCOMPLISHMENT
4.1 Participating Contractors/Grantees
The following listing of all participating contractors and grantees
by Work Task includes Project Officer, Contract Number, start date, and
contract period:
0 "Environmental Assessment of Residual Oil Usages," Catalytic,
Inc., S. L. Rakes, Contract No. 68-02-2155, started 5-11-76,
to run for 36 months.
0 "Analytical Support for Residual Oil Usage/Determination of
Hazardous Substances," Westinghouse R&D Center, S. L. Rakes,
Contract No. 68-02-2638, started 5-12-77, to run for 24 months.
0 "Chemically Active Fluid Bed Development and Support," Esso
England, S. L. Rakes, Contract No. 68-02-2159, started 5-6-76,
to run for 36 months.
0 "Residual Oil Disposition Status Report," A. D. Little, S. L.
Rakes, Contract No. 68-02-1332, Task 19. Started 8-21-75,
ended 4/76.
0 "Demonstrate Chemically Active Fluid Bed on Small Commercial
Scale," Foster Wheeler, S. L. Rakes, Contract No. 68-02-2106,
started 6-17-75, to run for 55 months.
0 "Engineering Support of Chemically Active Fluid Bed Demonstra-
tion," Westinghouse R&D Center, S. L. Rakes, Contract No.
68-02-2142, started 2-16-76, to run for 30 months.
51
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0 "Multiple Option Service Contract Tasks in Support of Fluid Bed
Demonstration," GCA Corporation, S. L. Rakes, Contract No.
68-02-2632, started 1-21-77, to run for 12 months.
0 "HDS/HDN Interactions in Liquid Fuels," MIT, T. W. Petrie, Grant
No. R804123, started 8-1-75, to run for 36 months.
0 "Control Technology for HDS/HDN of Liquid Fuels," Hydrocarbon
Research, Inc., T. W. Petrie, Contract No. 68-02-0293, started
12-13-72, to run for 55 months.
0 "Environmental Assessment of Residues from the FBC of Coal and
the Gasification of High-Sulfur Fuel Oils," Ralph M. Stone and Co.,
S. L. Rakes, Contract No. 68-03-2347, started 12-5-75, to run for
48 months.
4.2 Scope of Work Outlines and Descriptions of Active Projects
0 Environmental Assessment with Systems Analysis and Program Support
for Residual Oil Usage. Catalytic, Charlotte, N. C., Contract
No. 68-02-2155.
A. This will be a continuing, broad, and comprehensive environ-
mental and engineering analysis, with source sampling and
ambient monitoring.
B. Contractor Tasks.
1. Review of existing environmental, engineering and
cost data.
52
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2. Identification of important pollutants and pro-
jection of attainable emission levels.
3. Identification of missing information and design of
program to develop this information.
4. Design and execution of source sampling, fugitive
emission, and ambient measurement program.
5. Provide general program support.
a. Literature searches.
b. Information storage and retrieval.
c. Assessment of related R&D
d. Technical review and evaluation.
e. Others as required.
Analytical Support, Hazardous Substances. Westinghouse Research
Laboratories, Contract No. 68-02-2638.
A. An analytical support effort to determine what substances
are present in residual oil which could become environ-
mental pollutants. This work is coordinated with the work
being done by the Process Measurements Branch (PMB) of IERL-
RTP. The Health Effects Research Lab (HERL) also has input
to this effort.
B. Contractor Tasks.
1. Survey of currently available data.
2. Survey and classification of residua.
3. Selection of samples and test plan.
4. Sample acquisition.
5. Analysis of samples (including bioassay).
6. Recommendations for use of the various residua.
53
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Preliminary Environmental Assessment of the CAFB Process.
GCA, MOSC Task 14, Contract No. 68-02-1316.
A. A MOSC Task (3000 hours) to sample the CAFB pilot unit and
to lay the groundwork for Environmental Assessment of the
process.
B. Contractor Tasks.
1. Analyze, in depth, the potential multimedia environ-
mental impact of the CAFB process.
2. Determine the tests which should be run on the Esso
Petroleum Pilot Plant to comprehensively evaluate
the existence of various pollutants.
3. Evaluate the tests made.
4. Analyze the gas absorption, particulate, and generator
bed material samples.
5. Compare the CAFB process with other gasification schemes.
6. Perform ESCA (Electron Spectroscopy for Chemical
Analysis) on selected samples.
7. Make recommendations for the sampling plan to be
followed for the CAFB demonstration.
8. Prepare a report with recommendations on followup for:
(1) the Esso Petroleum project; (2) CAFB Demo test pro-
gram; (3) the full Environmental Assessment project.
Residual Oil Disposition Status Report. A. D. Little, MOSC Task 19,
Contract No. 68-02-1332.
A. A MOSC Task (1000 hours) to provide input for the planning of
the residual oil program and to assess the probable extent
and trends of the use of residual oil.
54
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B. Contractor Tasks.
1. Determine the approximate supply of residual oil in the
U. S. available for fuel use, now and in the future.
2. Determine the distribution of this residual oil supply.
3. Determine the present usage of residual oil.
4. Project how the supply and demand might be modified if
an environmentally sound use of residual oil as a fuel
were available.
Study of Chemically Active Fluid Bed Process (CAFB) for Sulfur
Removal During Gasification of Heavy Fuel Oil. Esso Petroleum
Company, Esso Research Centre, Abingdon (ERCA), Contract No.
68-02-1359.
A. This contract covers phase III of a six-phase program con-
ceived for the development of the CAFB process. The purpose
is to provide design information to permit a conceptual
design for a conversion of a utility boiler to the CAFB
process.
B. Contractor Tasks.
1. Test three sorbent stones (U.S. limestones) and two fuel
oils in the batch units to measure reactivity and dust
formation.
2. Derive a useful engineering design guide to the process
from data gathered in phases I and II.
3. Modify the continuous unit and test a U.S. stone and
oil (Run 8).
4. Run the continuous unit to provide design data and/or
55
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test alternative limestone (Run 9).
5. Provide advice and consultation to other EPA con-
tractors working on the CAFB effort.
6. Test materials of construction.
7. Determine trace metals retention by the sorbent bed
material.
8. Determine the feasibility of burner design modifica-
tion to permit on-stream decoking of the gas duct.
9. Evaluate alternate low cost methods for purge stone
and regenerator off-gas disposal.
Studies of the CAFB Gasification Process for Reduction of Sulfur
Oxide Emissions. ERCA, Contract No. 68-02-1479.
A. This is a follow-on contract to -1359 to allow uninterrupted
development of the CAFB process with emphasis on acquiring
design information and providing support for the design of a
U. S. demonstration. This contract begins phase IV of the
six-phase effort outlined for the CAFB process development.
B. Contractor Tasks.
1. Test a new fuel and three new limestones in the
batch units.
2. Analyze data from previous tests, predict performance
of continuous unit.
3. Test proposed design features of demonstration unit in
the continuous unit (Run 10).
4. Evaluate, in a continuous unit run, up to six items
related to the planned demonstration (Run 11).
56
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5. Provide advice, consultation, and technical expertise
to support the design of the demonstration unit.
6. Determine effect of CAFB process on potentially
harmful elements, including sulfates and free acids,
other than S0? and NO .
» ^
Environmental Assessment and Development of CAFB Process for
Evaluation of a Clean Fuel Gas in an Existing (or New) Combustor.
ERCA, Contract No. 68-02-2115.
A. This contract is to make available, to the CAFB demonstration
design effort, Esso-generated data on the potential for
employing the CAFB process on solid fuels.
B. Contractor Tasks.
1. Abstract data and conclusions from Esso proprietary
reports on laboratory studies made for gasification of
a number of coals and lignites; prepare a formal
report to EPA.
2. Evaluate the Esso continuous unit for use in test
of various gas cleanup schemes.
3. Make maximum use of proprietary studies, produce a
conceptual design for a pressurized CAFB process, and
compare to alternative clean power generation systems.
Technical Support for the CAFB Demonstration. ERCA, Contract No.
68-02-2159.
A. This contract will cover phases V and VI of the planned
six-phase CAFB development program, and provide the
57
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necessary support by ERCA to the CAFB demonstration.
B. Contractor Tasks.
1. Provide coal feed and steam supply to the continuous
unit. Add data logging equipment, and test design
and operating parameters concurrent with Run 11.
2. Modify continuous unit to include design features of
the demonstration unit and test in continuous Run 12
under long-day operating conditions.
3. Modify continuous unit and operate (Run 13) to provide
problem solution for verification of the demonstration
shakedown and commissioning activities.
4. Provide input for and attend design review meetings
conducted during the demonstration project.
5. Conduct batch unit tests on three solid fuels and two bed
materials selected for the demonstration unit.
6. Investigate and recommend a solution for dealing with
the coal ash in the CAFB unit.
7. Refine previous data analyses and develop a predictive
mathematical model for the CAFB process.
8. Provide information needed, and help prepare, an operations
manual for the demonstration unit.
9. Assist in the commissioning of the demonstration plant
and provide assistance at key points in the experimental
program.
Demonstration of the Chemically Active Fluid Bed (CAFB) Process on
a Small Commercial Scale. Foster Wheeler Energy Corporation (FWEC),
58
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Contract No. 68-02-2106.
A. This contract is to develop a definitive process design for
a CAFB process to feed two burners of the No. 4 unit at La Palma
Station of the Central Power and Light Company (CPL) at
San Bern'to, TX. The overall objective of the program is to
demonstrate the effectiveness and practicality of the CAFB
process to provide fuel from feedstock not environmentally
acceptable if fired directly. Fabrication of vessels, con-
struction of the units, etc. are covered under a private con-
tract between CPL and FWEC.
B. Contractor Tasks.
1. Design preparation and review.
a. Design development.
b. Fuel selection.
c. Definitive design.
d. Process design manual.
2. Construction planning.
a. Site planning and approval.
b. Construction and fabrication drawings.
c. Monitor construction progress.
3. Experimental test program.
a. Operating variables (primary liquid fuel).
b. Daily inspections.
c. Emission measurements.
d. Emission correlations.
e. Spent materials studies.
59
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4. Performance and emission testing.
a. Records of power, maintenance supplies, etc.
b. Daily inspections.
c. Emission measurements.
d. Emission correlations.
e. Spent materials studies.
5. System evaluation.
a. Process design manual update.
b. Conceptual design of commercial system.
0 Evaluation of the Fluidized Bed Combustion Process, Fluidized Bed
Residual Oil Gasification/Desulfurization Demonstration.
Westinghouse Research Laboratories, Contract No. 68-02-0605.
A. A contract designed to provide engineering and program
support for the CAFB program. Only modification 6, to
the basic contract, is concerned with CAFB and active at
this time.
B. Contractor Tasks.
1. Sulfur removal system.
a. Sorbent selection.
b. Spent sorbent processing.
c. Spent sorbent utilization.
d. Environmental impact of spent sorbent disposal.
e. Sulfur recovery.
2. Solids transport testing.
3. Boiler gasifier interfaces.
4. Pilot plant test program support.
60
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5. Process design cost and evaluation.
6. Market studies.
a. Fuel.
b. Limestone.
c. Applications.
d. Competitive technology.
Engineering Support of the CAFB Demonstration. Westinghouse
Research Laboratories, Contract No. 68-02-2142.
A. This contract is a follow-on to -0605 and is designed to
provide engineering and program support for the CAFB
demonstration.
The engineering and laboratory scale regenerative work
under this contract is meshed with the CAFB demonstration
in Texas, while the work under -0605 was general, or was
meshed with a once-through CAFB demonstration that was
contemplated in New England.
B. Contractor Tasks.
1. Sulfur removal system.
a. Sorbent screening and selection.
b. Sorbent disposal.
c. Environmental impact.
d. Sulfur recovery.
61
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2. Alternative concepts.
a. Sorbents.
b. Fuels.
c. Applications,
d. Catalysts in regenerator.
e. Process.
f. Design and operating concepts.
3. Environmental control technology.
a. Waste gas cleaning.
b. Waste water control.
c. Waste solids treatment.
4. Environmental impact for off-design conditions
a. Startup.
b. Shutdown.
c. Burnout.
d. Equipment malfunction.
e. Emergency conditions.
5. System evaluation.
a. Plant emission control.
b. Capital and operating costs.
c. Reliability.
6. Program assistance.
a. Data evaluation.
b. Critical design features and experiments.
c. Market potential.
d. Related technology.
62
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Development of Sampling and Analytical Techniques.
A. Studies are being done in-house by the Process Measurements
Branch (PMB) to include close liaison with contractors who
are performing sampling and analytical work.
0 Environmental Assessment of Residues from the Fluidized Bed Com-
bustion of Coal and the Gasification of High-Sulfur Fuel Oils.
Ralph M. Stone and Co., Contract No. 68-03-2347.
A. This contract is administered by the EPA's Environmental
Research Laboratory (Cincinnati) with funding from both the
FBC and CAFB sector of the Industrial Environmental Research
Laboratory (Research Triangle Park). The objective is to
determine the environmental impact of solid waste from
the CAFB process.
B. Contractor Tasks.
1. Residue and preliminary leachate characterization.
2. Literature review of environmental impact of like
substances.
3. Environmental impact — laboratory studies using
columns to simulate terrestrial disposal.
4. Market study -- possible sale for manufacturing use.
5. Residue treatment and disposal study.
0 Catalytic Desulfurization and Denitrogenation Interactions.
MIT, Grant R804123.
A. This is a continuing research effort to determine the charac-
teristics and kinetics of simultaneous HDS/HDN reactions in
63
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order to develop improved methods of converting organo-
nltrogen compounds to Innocuous products.
B. Grantee Tasks.
1. Conduct experimental studies of HDN and HDS at pressures
representative of industrial practice.
2. Use model compounds typical of more complex sulfur and
nitrogen compounds (multi-ring compounds).
3. Determine thermodynamic limits on steps in denitrogenation
pathways.
4. Formulate interactive kinetics of HDS/HDN, including
effects of H2S and NH3.
5. Determine the effects of catalyst variations (e.g.,
activity) on the reactions.
Demetallization of Heavy Residual Oils and Denitrogenation
Catalyst Evaluation. Hydrocarbon Research, Inc., Contract No. 68-02-0293,
A. This effort has two main thrusts. The first is to
develop and evaluate scavenger pretreatment systems
for high-metals, high-sulfur residual oils, and the
second is to evaluate catalyst characteristics for
removal of nitrogen from liquid fuels.
B. Contractor Tasks.
1. Survey to determine types of compounds and supports
that might be suitable for demetallization.
2. Evaluate selected combinations via screening runs.
3. Optimize the promoter/scavenger catalyst and
64
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evaluate a commercial production of the catalyst.
4. Optimize the run conditions for the pretreatment
using the developed catalyst and different residual
oils.
5. Evaluate similar technology in the USSR for
pretreatment.
6. Evaluate catalyst characteristics for denitrogena-
tlon of liquid fuels.
65
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5. CURRENT STATUS: ENVIRONMENTAL ASSESSMENT
5.1 Progress
5.1.1 General
The environmental assessment tasks included in the Control Tech-
nology contracts have progressed well. Esso Petroleum has studied trace
metal retentions by the bed material and disposal and weathering of treated
bed material. Experimental effort by Esso in the dry sulfation technique
was not promising. Westinghouse achieved some very promising results on
snail scale Thermal Gravimetric Analysis (TGA) and theoretical studies of this
dry sulfation technique. The GCA effort in performing sampling and in
preliminary Environmental Assessment of the CAFB process, including
projection of results at the Texas demonstration site, was well received;
and indicates favorable results for the CAFB process. The Catalytic
effort has classified residual oil usage techniques into five categories
and has begun detailed assessment of each process category. Many data
have been gathered which will be anlayzed, and then plans will be made
to fill the data gaps.
5.1.2 Project by Project
Much Environmental Assessment work is included in the Control Tech-
nology Development contracts for the Chemically Active Fluid Bed Process.
The Esso Petroleum Ltd. effort includes determination of the retention
by the bed of trace and potentially hazardous materials. Significant
retention by the bed material of vanadium, nickel, sodium and other trace
minerals was shown by spark source mass spectrometry. Neutron Activation
analysis was used on some samples for a comparison analysis. Mass balances
66
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were computed for beryllium, cadmium, antimony, molybdenum, nickel, vanadium,
tellurium, arsenic, selenium, chromium, manganese, cobalt, boron, lead,
sodium, and potassium. Significant retention of many of the elements was
indicated.
Another environmental assessment effort by Esso Petroleum investigated
the disposal of spent bed material via two routes: first, deadburning;
second, the "dry sulfation" technique. Material which had been deadburned
under several conditions and untreated bed material were exposed to out-
side weathering for 1 year. Temperature rises were monitored and tests
of leachate water and of the bed material were conducted periodically.
The results were compared to World Health Organization standards for
potable water. Various trials and tests were conducted of the dry sulfation
technique, in which spent bed material is converted to calcium sulfate
(CaSO.), and SOg from the regeneration step is captured.
The results of the Esso Petroleum effort are given in report
EPA-600/2-76-248, September 1976. In summary, the dry sulfation approach
does not appear commercially attractive, while deadburning produces a
product that seems easily disposable.
The Westinghouse Research Laboratories engineering analysis/support
contract includes detailed sorbent disposal and usage studies. Westing-
house has performed small scale tests and paper studies on the dry sulfation
step for disposal. They believe that it may be made into a viable process,
especially since this option eliminates a sulfur recovery plant when setting
up a CAFB process unit. The use of spent bed material by the building
industry as aggregate, and perhaps as a constituent of mortar and
cement, is possible. Two markets identified for bed materials which
67
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are under exploration by other groups are agricultural use and use in
sewage treatment. Various concrete mixtures have been tested by Westing-
house using spent bed material and fly ash. The Belgian Trief process
Is being closely Investigated by Westlnghouse: this process uses spent
bed material as a substitute for Portland cement in concrete.
The environmental Impact of land disposal 1s a task that Westlnghouse
has Investigated using leaching tests, photomicrographs, scanning electron
microscopy, and other techniques. Methods, parameters, and leachate char-
acteristics have been Identified. The summary trace element results
are compared to drinking water standards. In all cases the trace elements
in the leachate were within drinking water standards. The permissible
calcium level was exceeded, but it was noted that calcium in leachate
from natural gypsum deposits also exceeds drinking water standards.
Ocean dumping Is not considered a likely solution to spent sorbent
disposal; however, use of the material to build artificial reefs for Im-
proved fish habitat 1s being considered.
The Foster Wheeler contract for demonstration of the CAFB process
Includes effort on the determination of the disposal characteristics of
the spent bed material. This 1s largely covered in a subcontract from
Foster Wheeler to Battelle Columbus Laboratories. Other EA effort planned
for FWEC calls for trace element analysis on bed material and effluents
and emissions tests per NSPS requirements. This work 1s not now active.
The baseline testing of the boiler, as found before the CAFB retrofit,
Is complete.
68
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One preliminary environmental assessment task was completed under
a multioption services contract (MOSC) by the GCA Corporation. This task
included sampling the Esso Petroleum continuous pilot unit while using
residual oil and bitumen as a feedstock, and making a preliminary environ-
mental assessment of the process with projections of emissions from those
of the Esso pilot to those of the demonstration unit in Texas. The analy-
tical techniques used included ESCA (electron spectroscopy for chemical
analysis), mass spectrometry, and chromatographic techniques. The prob-
able environmental impact of the unit in Texas was judged acceptable.
The one possible area of concern was in particulate emissions. This effort
is reported in detail, with the necessary background information, in
report EPA-600/7-76-017, "Preliminary Environmental Assessment of the
CAFB."
Another MOSC task in the EA area was that on Residual Oil Supply and
Usage in the U.S., with consideration of environmental consequences,
which Arthur D. Little performed. This effort projected the residual fuel
supply and demand to 1985 and indicated areas of concern. This work is
reported in EPA-600/2-76-166, "Residum and Residual Fuel Oil Supply and
Demand in the U.S. 1973-1985."
The major environmental assessment contract for residual oil usage
is held by Catalytic, Charlotte, North Carolina. This contract was effect-
ive in May 1976.
The objective of this work is to execute an environmental assessment
from a system analysis of the present commercially operating processes
69
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capable of using residual fuel oil to generate electricity. The processes
under study include:
1. Pretreatment - Hydrodesulfurization (HDS) processing
removes sulfur and other pollutants from fuel oil
prior to combustion.
2. Conversion - Partial oxidation (POX) and chemically
active fluidized bed (CAFB) processing convert resi-
dual fuel to an environmentally acceptable gas, which
can be used directly or in a combined cycle system.
3. Post-treatment - flue gas desulfurization (FGD) tech-
niques remove pollutants by cleaning the tail-gas
from conventional boiler combustion.
To date, all existing data have been compiled on residual fuel oil
processes. An intensive study of three major processes was required
for the assessment of present commercial technology. The information
obtained on the processes was reviewed for a detailed engineering and
cost analysis. At the present time, several economic studies are being
conducted for commercial POX schemes. Five FGD systems and four HDS
processes have been reviewed. A study of combined cycle units is under-
way. The commercial status of the processes under study shows that
there are numerous units now in operation having significant capacities
and operating experience.
Residual fuel oil contains hydrocarbons and certain contaminants
such as sulfur, ash, and metal. These contaminants can be potential
pollution problems as they are transferred to various forms in the
different processes. Sulfur data are well defined on all H2S and SOp
70
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removal processes.
Very little data are available on other potential pollutants
including vanadium, nickel, NOX, ash, particulates, and carcinogenic
compounds. All important emission levels from the process units
have been calculated; however, it will be necessary to analyze samples
from various cleanup processes in order to determine present and future
emission levels. No problems are anticipated with excess pollution
from sulfur in the effluent gas from these processes.
Investment costs and operating requirements have been used to
estimate the control costs and efficiencies. Data collected on a trip
to Japan were helpful in making these estimates and in obtaining missing
information on commercial HDS, POX, and FGD processes. Some missing
information still exists in the area of treatment and final disposal
of some effluent streams, which contain important pollutants such as
metals, carbon, and ash compounds. Further plant visits will be required
to obtain samples of these streams. Samples from plants will be analyzed
to determine the potential pollution products. The necessity of a
sampling program for each process will be considered. Calculations
within an order of magnitude would perhaps suffice in some cases; however,
emission data are required through sampling to complete the environmental
assessment.
It is concluded that each process under study is established as an
acceptable unit by operating experience on a commercial scale. The flex-
ibility of each process has been demonstrated by a proven acceptance of
variable feedstocks within certain design limits. Contaminants such as
71
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sulfur, nickel, and vanadium are successfully removed from the fuel.
In some cases, they may be used for the production of salable by-products.
Additional process equipment is required in most cases to upgrade by-
products to a final form. At least 80 to 90 percent removal
efficiencies have been demonstrated for most contaminants. Sulfur
removal efficiencies of 96 to 99 percent are common in FGD processes.
The capital and operating cost estimates indicate that the price
for these processes is high for the U.S.A. The process cost is very
sensitive to feed composition. It should become more economical in
the future to charge heavier lower-priced feeds into the POX process,
middle-range feeds into the HDS process, and low sulfur fuel oils into
FGD units.
5.2 Plans
One environmental assessment contract for Analytical Support/
Hazardous Substances in Residual Oil has just been awarded to Westinghouse
Research Laboratories. This effort will analyze, in great detail, 100
samples of residual oil. This analysis will include bioassy and radio-
nuclide assay as well as detailed organic and trace element analysis.
The GCA Corporation has been awarded a contract to sample the Esso
CAFB unit using coal and lignite as a feed, and to compare these results
to those found in the earlier effort where oil and bitumen were the
feedstocks. The results will be projected to the demonstration unit,
and the Preliminary Assessment will be updated.
72
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Milestone charts for each of the two existing EA contracts follow.
The work plan for a Westinghouse contract, is currently under development
1. GCA -- Preliminary EA of CAFB — Coal and Lignite
Complete Field Testing October 1977
Complete Engineering Analysis January 1978
Submit Draft Final Report March 1978
2. Catalytic, Charlotte — EA of Residual Oil Usage
(See Figure 5.)
73
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A Submission of Monthly
PROJECT SCHEDULE AND MILESTONES
ENVIRONMENTAL ASSESSMENT/SYSTEMS ANALYSIS
Date:
3 Junt1976
Cittlytk Contract No. 4272°
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Phased! V Milestones 1976 | 1977
DESCRIPTION
Projtct Management •
Review & Analysis of Environmental. Engintering, Cost Date
Review & Analysis of Existing Environmental Data
Rtvitw A Analysis of Existing Ruidual Oil Gasification Procass,
Enginaaring & Cost Data
Idtntification of Important Pollutants & Projaction of
Attainabla Emission Lavals
Otfinition of Pollutants ft Environmantal Impacts
IdantiTication of Important Pollutants
Enginatring Rtvitw of Emission Sources within Procass
Analysis of Control Efficiency
Analysis of Control Cost as a Function of Control Efficiency
Analysis of Environmantal Standards
Determination of Emission Goals for the Environmentally
Sound use of Residual Oil
Identification of Missing Information & Design of Program to
Develop Such Information
Idtntification of Problem Areas & Additional Data Requirements
Design of Test Program to Obtain Required Data
Development of Required Data
)esign & Execution of Source Sampling Fugitive Emission &
Ambient Measurement Program
Design & Conduct Source Sampling Program
)esign & Conduct Fugitive Emission of Ambient
Aeesurement Program
General Program Support
Maintenance of a System for Storage & Retrieval of Information
Work Plan and Final Report
1978
1979
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6. CURRENT STATUS: CAFB
6.1 Progress
6.1.1 General
The Chemically Active Fluid Bed (CAFB) program of IERL-RTP has defined
the operation of the CAFB using residual oils as a feedstock. The CAFB
process has been found to effectively desulfurize the residual oil
feedstocks and to give stable process operating conditions. Moderate stone
make-up rates of 1.0 to 1.5 moles of calcium to 1 mole of sulfur in the
feedstock were found to give sulfur removal effeciencies of 80 percent
or more. The ease of control and the efficiency of the process indicated
that commercial application was likely. Trials of various solid fuels
in batch units, conducted under private sponsorship, indicated that these
feedstocks were also feasible for the CAFB process.
The design of the small semi-commercial demonstration unit has been
completed, except for minor design changes and field retrofit adjustments
found necessary during the construction which began in May 1977. The
equipment fabrication and construction of the unit is being done under
a contract between Central Power & Light (CPL) and Foster Wheeler (FWEC).
CPL is funding the equipment fabrication and the construction of the unit.
Figure 6 is a photograph of the CAFB demonstration model.
A contract, for further development of the CAFB process and for
technical support of the demonstration effort, was definitized with Esso
Petroleum, Ltd. Other contracts for support of the CAFB demonstration
were arranged. Ancillary arrangements and subcontracts for fuel, stone,
materials handling, etc. are either awarded or are in the advanced
review stage. 75
-------
Figure 6. Model of CAFB demonstration unit under construction by CPL at San Benito,
76
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6.1.2 Project by Project
CAFB Demonstration Unit—Foster Wheeler Energy Corp. (FWEC)
Task 1, design preparation and review, is complete except for review
meetings, which will be held periodically throughout the period of
performance of the contract. FWEC has nearly completed the construction
and fabrication drawings. A model, on a scale of 1 to 32, was constructed
of the CAFB demonstration unit. Photographs of this model serve the
same purpose as isometric drawings of the unit. The model is now being
used in construction planning and will be used in operator training.
FWEC is monitoring the construction effort and providing periodic
briefings to EPA on the progress.
The performance and emission testing planning is nearing completion.
The boiler unit has been tested in its original condition. Analysis
of the power produced, fuel consumed, and operating conditions is
underway.
The theoretical failure analysis portion of Task 5 system evaluation
was completed in 1977, and will be updated in 1978 as design changes
are made. The remainder of Task 5 deals with the process design manual
update and the conceptual design of a larger commercial system. Work
will be started after the experimental test program is completed and the
information generated by the tests is analyzed.
The remaining two areas of the FWEC contract, Task 6 (reports of
work) and Task 7 (management), are on schedule and no significant problems
have been found.
77
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CAFB Development and Technical Support of Demonstrat1on--Esso Petroleum
Esso has operated the continuous unit pilot plant to perform preliminary
testing of coals, stones, and equipment features to be used in the demonstra-
tion plant. "Long-day" operation, that is, startup in the morning, shutdown
at night, and startup the next morning, has been demonstrated. Checkout
of the data logging equipment is near completion. The scanning and display
programs are operational. The pressures, temperatures, and gas analyses
are displayed. Several short runs on the continuous unit used a minus
12 mm lignite sizing. Esso demonstrated that, by increasing the pressure
drop across the cyclones from the range of 0.25 - 0.5 kPa to the range of
1 - 2 kPa, the efficiency is improved markedly and particulate carryover
to the burner is decreased.
Esso completed compilation of a CAFB operating manual, except for sections
on data logging and coal feeding. These sections will be completed after
Esso has operated the two systems and acquired the experience necessary
to write the sections.
Adequate lignite to test the primary solid feedstock for the Texas
demonstration in the Esso pilot unit is on hand in England. Some Texas
limestone may need to be procured and sent to England at a future date.
Esso has also conducted trace metal determinations on both the in-
coming feed and the sorbent bed to determine the retention of various
elements by the bed material. The retention of these trace metals prevents
them from entering the environment where they may inflict ecological
damage. Retention also prevents them from causing damage to the boiler
via corrosion and fouling.
78
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A conceptual study of the CAFB process, operated at a pressure of
about 1.8 MPa, has been completed by Esso Research Center Abingdon and
Exxon R&E, Florham Park. This form of the CAFB process is very attractive
for use in conjuction with turbines and combined cycle applications.
Based on experience of 10 runs totaling 3,000 hours on the continuous
unit, Esso is developing a mathematical model of the CAFB process to be
used as a predictive tool in the design and operation of larger CAFB
units.
Engineering Analyses and Support of the CAFB Demonstration --
Westinghouse Research
Westinghouse tested several stones for use at the CAFB demonstration
site; stones were tested for sulfur removal and attrition. Morphological
studies were made in an effort to relate grain size and type of grain
structure to stone properties. Both optical and electron microscopes
were used in the studies. Stone attrition appears greatest in nearly
pure stones with large calcite type grain structure. Various types of
stone attrition are being studied; e.g., during initial heating and
calcination, fluidization, transport between areas of the CAFB unit,
and regeneration.
Westinghouse has investigated spent sorbent processing, spent sorbent
utilization, and spent sorbent disposal/environment impact. Their purposes
were to determine the properties of spent sorbent, to identify process
alternatives, and to identify and solve problems likely to be encountered
when dealing with the spent sorbent. Alternate concepts for the CAFB
79
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process — including alternates to the limestone sorbents, other fuels,
applications other than utility usage, and alternate subsystems for
regeneration, sulfur recovery, and solids transport — have been explored
under this contract.
Other control technology evaluation for subsets of the unit operations
making up the CAFB process — such as waste gas cleaning, trace element
retention, and waste water control — is being explored as part of the
engineering support for the CAFB demonstration.
6.2 Plans
6.2.1 CAFB Demonstration (Foster Wheeler)
The largest remaining effort under the EPA contract is the procurement
and delivery of fuels and feedstocks to the demonstration site and testing
of the unit for performance and criteria pollutant emissions. Other than
the EPA work, the major remaining effort is the construction, check out,
and operation of the unit. This is the subject of a contract between
FWEC and CPL.
The schedules for both the EPA funded effort and the CPL/FWEC effort
are reflected in the Figure 7 milestone chart. The final report will also
include a conceptual design for a much larger CAFB unit. This will draw
on the data generated by, and the lessons learned during, operation of
the La Palma unit and further operation of the Esso pilot plant in
England.
80
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KIT
i woMit PLAN
2 OIPINITIVI Of (ION
3 PMILIMINARV OISION MANUAL
4 CONSTRUCTION START
9 START4JP
• TIST PROGRAM START
T ORAPT OP FINAL RI PORT
I FINAL RIPORT
OUf DATC OF RIPOHT
M(tTINGSCMIOULlD
MILfSrONI
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• IVISCOISTIMATE AT
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RJVlStQS I 10 U 75
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MTINSIVE fttVlilONt RtFlf CTlS
ADDtTlO«rt TO SCOPE OF AOFJ*
CHANG IS IS SCHEDULE 1 'ROGRAI
SLIPPAGE
Figure 7. Foster Wheeler CAFB program, schedule/milestones.
-------
6.2.2 CAFB Development and Technical Support (Esso Petroleum)
Esso will complete run 11 with an around-the-clock run of 200-plus
hours and conduct two additional runs (12 and 13) to support the demon-
stration effort. These last two runs will either be problem solving or
confirmation runs, as required. The runs will use the "long-day"
technique to derive the maximum benefit from the test. Some exploratory
effort may be conducted during runs 12 and 13 if the situation permits.
Each run will include an around-the-clock 200-plus hours of operation.
Esso personnel will be on site and assist in the startup of the La
Raima demonstration. Further training on the Esso England unit is
planned for Foster Wheeler startup engineers and possibly some CPL
operations personnel.
The Esso schedule (Figure 8) and milestone chart (Table 11) give
an overview of the effort planned under this contract (68-02-2159).
6.2.3 Engineering Analyses and Support (Westinghouse Research)
The Westinghouse support effort will place heavy emphasis upon
operation of the solids transport facility. The spent sorbent disposal/
evaluation effort will continue to provide timely information to guide
the CAFB program and to provide information for the EA portion of the
program. The sorbent selection effort will focus on the development
of generalized criteria for sorbent stone selection. The spent sorbent
processing and utilization effort will focus on the exact stone/fly-ash/
spent-bed combination expected from the La Palma site as applied to
potential uses or disposal 1n the Immediate area of the demonstration plant.
82
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00
CO
TASK
1
2
3
4
5
6
7
8
9
10
1976
M J Jy A S 0 N D
M1»V M2*
("MILESTONES ARE DEF
1977
JFMAMJJyASOND
^~""~™ \ "j
RUN 11
MV
.yM9
J7M12
NED IN TABLE 11.)
1978
JFMAMJ JyASOND
_^M3
__ „_ J^M4
i i Mr.
RUN 12 V
l_ i
RUN 13
S7M7
S7M10
?M13
M16
_J7M14 _J7M15 _?
1979
J F M A M J Jy
M11 v
M17
Figure 8. Esso Petroleum contract 68-02-2159, schedule.
-------
TABLE 11. ESSO PETROLEUM CONTRACT
68-02-2159 PROGRAM MILESTONES
Mla Complete mini-run on coal.
M2 Topical report on mini-run.
M3 Topical report on Run 11.
M4 Topical report on Run 12.
M5 Topical report on Run 13.
M6 Topical report on batch tests.
M7 Topical report on coal ash separation.
M8-M11 Incorporate data from mini-run, and Runs 11, 12,
and 13 into mathematical model of process.
Ml2 Complete assistance to Foster Wheeler on operating
procedure for oil and oil test program (Contract
68-02-2106).
Ml3 Complete assistance to Foster Wheeler on operating
procedures for coal and coal test program (Contract
68-02-2106).
M14-M16 Complete visits to demonstration site to advise on
startup, oil and coal test programs.
Ml7 Complete first draft of final report.
a Schedule complementing these milestones is shown
in Figure 8.
84
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Under the alternate concepts work area, Westinghouse will closely
analyze the data developed at the demonstration unit to verify previous
projections.
A number of alternative concepts for the CAFB process exist which
have not been assessed in sufficient detail to draw conclusions as to
their feasibility or performance. Experimentation, design, and cost
and performance evaluations are required in the following suggested
alternate areas in order to determine the proper direction for the
demonstration plant program and CAFB commercial development:
0 Sorbents.
0 Fuels.
0 CAFB applications.
0 Processes (regenerative and once-through).
0 Process arrangements.
0 Plant component designs (solids transport systems).
0 Plant layouts.
0 Gasifier/boiler interface arrangements.
0 Operating conditions.
0 Operating procedures (turndown, startup, emergency).
0 Control techniques.
Numerous alternatives to the base design exist which may improve
the process economics and performance or may broaden its commercial
applicability. Preliminary and conceptual assessments of these alterna-
tives will be carried out with respect to the base design. Evaluations
85
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will consider economic and environmental feasibility, problem areas,
and development requirements.
Alternative concepts considered will include sorbents, fuels,
applications, processes, designs, and operating concepts. Westinghouse
will orient their activity to support more closely the demonstration
effort. The Environmental Control Technology area will continue as
before. As shown in the Figure 9 milestone chart, the multimedia
emission and system evaluation will continue.
86
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TASK
21
1 . Sulfur Removal System
1.1 Sorbent Selection
Stone Analysis
Sulfur Removal Properties
Attrition Characteristics
Regeneration Characteristics
Recommend Candidate Stones
Generalized Criteria
1.2 Spent Sorbent Processing
Characterize Spent Sorbents
Process Design and Economics
Experimental Test Program
Process Evaluation
1.3 Spent Sorbent Utilization
1.4 Spent Sorbent Disposal/Environ-
mental Impact
Land Disposal
Leaching Properties
- Heat Release Properties
Landfill Properties
Commercial Projections
Ocean Dumping
Evaluation
2. Alternate Concepts
Fuels
Applications
Sub-systems
Solids Transport Model
Design end Operation
3. Environmental Control Technology
Evaluation and Development
Waste Gas Cleaning
- Trace Elements
Waste Water Control
Waste Solids Treatment
- Develop Treatment Alternatives
4. Environmental Impact of Off-Design
Conditions
5. Multi-Media Emissions and System
Evaluation
6. Progum Assistance
Documentation
Work Plan
Technical Progress Narratives
Annual Report
76 8/
1 1 F IT
-- - ^
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A •
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.&
A-=i
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ft t
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Figure 9. Westinghouse Research contract 68-02-2142, schedule/milestones.
87
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7. CURRENT STATUS: HDS/HDN/DEMETALLIZATION
7.1 Progress
The work by Hydrocarbon Research (HRI) initially dealt with demetallization
of residual oils. In a cooperative program between the U.S. and the
Soviet Union, each side tested the other's demetallization catalyst
on various residua to determine the relative merits of each. The results
of this program are being evaluated.
As an offshoot of the demetallization project, an investigation was
begun to evaluate the characteristics of available HDN catalysts using
techniques that were similar to those used in the demetallization work.
These evaluations are underway. The results of this phase are expected
to provide data on the types of characteristics, such as active metal
pairs and pore size distribution that would be most desirable in a
catalyst for removal of nitrogen from high nitrogen liquid fuels.
The MIT work began with low pressure HDS/HDN of pyridene and
thiophene. As mechanisms and theories were postulated, the work was
expanded to include other model compounds (e.g., multi-ring sulfur and
nitrogen compounds), higher pressure operation in order to be more represent-
ative of commercial operation, and better instrumentation. This work
is providing information which will contribute to our understanding of
the complex interactions; it will also help define better methods of
removal of sulfur and nitrogen compounds from liquid fuels. These methods
may involve different operating regimes, process sequence changes, or
changes in catalysts.
88
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Figures 10-12 show equipment being used for the HDS/HDN/Demetallization
work.
i
7.2 Future Plans
The HRI program terminated in February 1978, and the MIT work will
end in July 1978.
89
-------
Figure 10. MIT Catalytic HDN/HDS facility—continuous microreactor
featuring temperature control by a fluidized sand bath.
90
-------
Figure 11. MIT Catalytic HDN/HDS facility—continuous microreactor
instrumentation for high-pressure, low-flow operation.
91
-------
Figure 12. Hydrocarbon Research bench-scale demetallization unit
92
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8. APPENDICES
8.1 References
1. Homolya, J. B., Barnes, H. M., and Fortune, C. R. "A Character-
ization of the Gaseous Sulfur Emissions from Coal and Oil-fired
Boilers," Proceedings of the Fourth National Conference on Energy
and the Environment, October 3-7, 1976, Stouffer's Inn, Cincinnati,
Ohio, published and distributed by the Dayton, Ohio, Section of
AIChE, pp. 490-494.
2. "Control Techniques for Sulfur Oxide Air Pollutants," U.S. Dept. of
Health, Education, and Welfare, Public Health Service, National Air
Pollution Control Administration, Washington, D. C., NAPCA Publication
AP-52 (NTIS No. PB190254), (1969).
3. "Availability of Heavy Fuel Oils by Sulfur Levels," in Fuel Oils by
Sulfur Content, Monthly, Mineral Industry Surveys, U.S. Dept. of
the Interior, Bureau of Mines, Washington, D. C., December (1972).
4. Annual Statistical Review, U.S. Petroleum Industries Statistics
1956-1972, Division of Statistics and Economics, American Petroleum
Institute, Washington, D. C. (1973).
5. Magee, E. M., Hall, E. J., and Varga, E. M., Jr. "Potential
Pollutants in Fossil Fuels," Esso Research and Engineering,
EPA-R2-73-249 (NTIS No. PB225039), June (1973).
6. Guthrie, V. B., ed. "Petroleum Products Handbook," McGraw-Hill,
pp. 8-25 (1960).
7. Levy, A., et al. "A Field Investigation of Emissions from Fuel Oil
Combustion for Space Heating," Research Report by Battelle - Columbus
Laboratories to American Petroleum Institute, November (1971).
93
-------
8. Chen, M. Private Communication to G. F. Sachsel, Battelle-
Columbus Laboratories, State Department of Environmental Conservation,
Albany, N. Y., August 9 (1971).
9. Hashimoto, Y., et al. "Possible Source of Atmospheric Pollution of
Selenium," Environmental Science & Technology, 4_ (2), 157-158 (1970).
10. Pillay, K.K.S., et al. "Neutron Activation Analysis of the
Selenium Content of Fossil Fuels," Nuclear Applications and
Technology, 1 (11), 478-482 (1969).
11. "Compilation of Air Pollutant Emission Factors," Second Edition,
Environmental Protection Agency, Office of Air and Water Programs,
AP-42 (NTIS No. PB223996), April (1973).
12. Barrett, R. E., et al. "Field Investigation of Emissions from
Combustion Equipment for Space Heating," Battelle, EPA-R2-73-084a
(API Publication 4180) (NTIS No. PB223148), June (1973).
13. Bennett, R. L., and Knapp, K. T. "Chemical Characterization of
Particulate Emissions from Oil-Fired Power Plants," Proceedings
of the Fourth National Conference on Energy and the Environment,
October 3-7, 1976, Stouffer's Inn, Cincinnati, Ohio, published and
distributed by the Dayton, Ohio, Section of AIChE, pp. 501-506.
14. Gosslin, A. E., Jr. "Pilot Plant Investigation of the Bag Filter-
house for Control of Visible Stack Emissions from Oil-Fired Steam-
Electric Generating Stations," Vol. XXVI, Proceedings of the
American Power Conference, pp. 128-137 (1964).
15. Engelbrecht, H. L. "Electrostatic Precipitators in Thermal Power
Stations Using Low-Grade Coal," Presented at the American Power
Conference, April 28 (1966).
16. Personal Communication, Dale L. Harmon, EPA/IERL-RTP, June 3 (1977).
94
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8.2 EPA Reports and Papers
Amoco
(68-02-1314)
Battelle
(68-02-1323)
Bechtel
(Ph 86-64-38)
Catalytic
(68-02-2155)
Esso, England
(CPA 70-46)
Esso, England
(68-02-0300)
Esso, England
(68-02-1359)
Esso, England
(68-02-2159)
GCA
(68-02-1316)
General Electric
(PH 86-65-01)
Hydrocarbon Rsrch
(68-02-0293)
PB 243-363/AS
EPA-650/2-75-042
PB 242-535/AS
EPA-650/2-75-034
PB 166-443
(APTD 1246)
PB 271-962/AS
EPA-600/7-77-081
PB 211-438
EPA-R2-72-020
PB 240-632
EPA-650/2-74-109
PB 268-492/AS
EPA-600/2-76-248
PB 274-947/AS
EPA-600/7-77-027
PB 262-001/AS
EPA-600/7-76-017
PB 185-466
(APTD 1253)
PB 227-568
EPA-650/2-73-041
PB 241-901/AS
EPA-650/2-73-041a
PB 255-983/AS
EPA-600/2-76-165
Demonstration of reduced hydrocarbon
emissions from gasoline loading
terminals—6/75
Fuels technology: a state of the
art review (task 14)—4/75
The economics of residual fuel oil
desulfurization (final report)—6/64
Process technology background for
envi ronmental assessment/systems
analysis utilizing fuel oil--8/77
Study of CAFB gasifier for reduction
of sulfur oxide emissions (final
report)—6/72
CAFB process for sulphur removal
during gasification of heavy fuel
oil—11/74
Chemically active fluid-bed process
for sulphur removal during gasification
of heavy fuel oil (third phase)—9/76
First trials of CAFB pilot plant on
coal—3/77
Preliminary environmental assessment
of the CAFB (task 14)-10/76
Feasibility study—hydrodesulfurization
of fuels under corona discharge catalysis
(final report)—3/65
Demetallization of heavy residual oils--
12/73
Same. Phase II—2/75
Same. Phase III—6/76
95
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Inst. of Gas Tech
(PH 22-68-58)
Int. Materials
Corp
(68-02-0296)
A. D. Little
(68-03-1332)
M. W. Kellogg
(CPA 70-68)
M. W. Kellogg
(86-02-1308)
MIT
(Grant R-800897)
Monsanto
(68-02-1320)
PEDCO
(68-02-1321)
Processes Rsrch
(CPA 70-1)
PB 184-353
(APTD 1263)
PB 223-653/AS
EPA-R2-73-272
PB 255-625/AS
EPA-600/2-76-166
PB 198-817
(APTD 0668)
PB 241-261/AS
EPA-650/2-75-030
PB 251-136/AS
EPA-600/2-76-044a
PB 243-977
EPA-600/2-76-044b
PB 248-101/AS
EPA-600/2-75-063
PB 237-756/AS
EPA-650/2-74-082
PB 239-343
EPA-650/2-74-082a
PB 250-585/AS
EPA-600/2-76-013a
PB 208-236
(APTD 1066)
LNG: a sulfur-free fuel for power
generation (final report)--5/69
f
Limited oil gasification experiment-
6/73
Residuum and residual fuel oil supply
and demand in the United States—1973-
1985 (task 19)—6/76
Availability of residual fuel oil
(final report, task 2)—12/70
Sulfur compound emissions of the
petroleum production industry
(task 26)—12/74
Energy supply, demand/need, and the
gaps between; vol I—an overview
(task 27)-3/76
Same; vol II— monographs and working
papers (task 27)—3/76
Catalytic desulfurization and
denitrogenation—10/75
Refinery catalytic cracker regenerator
SOV control process survey (task 1)~
9/74
Refinery catalytic cracker regenerator
SO control-steam stripper laboratory
te§t (task 1)—11/74
S02 abatement for stationary sources
in Japan (task 6)—1/76
Recent developments in desulfurization
of oil and waste gas in Japan, 1972
(task 16)--l/72
96
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Processes Rsrch
(68-02-0242)
Radian
(68-02-1319)
Rakes, S. L.
EPA/IERL-RTP
Research Triangle
Institute
(68-02-1325)
U.S. Bureau of
Mines
Westinghouse
(68-02-0217)
Westinghouse
(68-02-0605)
PB 221-439
EPA-R2-73-229
PB 252-245/AS
EPA-600/2-75-068
PB 237-343/AS
EPA-650/2-74-
097
1C 8156
(APT1C 00363)
PB 233-101/AS
EPA-650/2-73-
048d
PB 241-834/AS
EPA-650/2-75-
027a
Recent developments in desulfurization
of fuel oil and waste gas in Japan
(task 11)—5/73
Environmental problem definition for
petroleum refineries, synthetic
natural gas plants, and liquefied
natural gas plants (task 18)--ll/75
"Development of the chemically active
fluid bed process, a status report and
discussion," 76-JPGC-Fu-4. ASME,
United Engineering Center, 345 East
47th Street, NY, NY 10017—9/76
Vinyl chloride—an assessment of
emissions control techniques and costs
(task 17)-9/74
A survey of methods for desulfurizing
residual fuel oil—1963
Evaluation of the fluidized-bed
combustion process, Vol IV. Fluidized-
bed oil gasification/desulfurization--
12/73
Fluidized bed combustion process
evaluation (phase I—residual oil
gasification/desulfurization demon-
stration at atmospheric pressure),
Vol. I, summary—3/75
97
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TECHNICAL REPORT DATA
(Please read I attract ions on the reverse before completing)
1 REPORT NO.
EPA-600/7-78-077
3. RECIPIENT'S ACCESSION NO.
«-TITLE ANDsuBT,TLEAdvanced on Processing/Utilization
Environmental Engineering: EPA Program Status
Report
5. REPORT DATE
May 1978
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
P. P. Turner, S. L. Rakes, and T. W. Petrie
8. PERFORMING ORGANIZATION REPORT NO.
9 PERF JRMING ORGANIZATION NAME AND ADDRESS
10. PROGRAM ELEMENT NO.
E HE 62 3 A
See block 12.
11. CONTRACT/GRANT NO.
NA (Inhouse Report)
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 PERIOD COVERED
Inhouse: 6/70 - 12/77
14. SPONSORING AGENCY CODE
EPA/600/13
is. SUPPLEMENTARY NOTES Coauthor Turner can be Cached at Mail Drop 61, 919/541-2825.
16. ABSTRACT The rep()rt gives the status of E PA/IERL-RTP's Advanced Oil Processing
Program. It projects the amounts and normal practice and patterns of the use of
residual oil and the contaminants in residual oil, using emission standards as a yard
stick to indicate where potential problems exist. It describes the development of
environmental assessment and control technology, and discusses alternatives or
choices of methods for the use of residual oil. Methods available or considered for
the use of residual oil include: direct combustion, fluid-bed combustion, partial
oxidation, chemically active fluid-bed (CAFB) combustion, direct hydrodesulfuriza-
tion (HDS), and combinations of these technologies. It gives the history of EERL-
RTP's program and the relationship of CAFB to other alternatives. It outlines the
environmental assessment of residual oil use and control technology development.
It gives program subobjectives, work tasks, and accomplishment plans, with fun-
ding levels. It discusses participating contractors and grantees, with their scope
of work outlines and project descriptions. A section deals with the effort toward
HDS, hydrodenitrogenatton(HDN), and demetallization techniques for residual oils
and like-derived fuels. It lists references and related EPA reports and staff papers.
7.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
Pollution
Fuel Oil
Processing
Residual Oils
Combustion
Fluidized Bed Processing
Oxidation
Desulfurization
Metals
18. DISTRIBUTION STATEMENT
Unlimited
b.lDENTIFIERS/OPEN ENDED TERMS
Pollution Control
Stationary Sources
Advanced Oil Processes
Hydrodenitrogenation
CAFB
Hydrodesulfurlzation
tallization
19. SECURITY CLASS (This Report)
Unclassified
20. SECURITY CLASS (This page)
Unclassified
EPA Form 2220-1 (9-73)
c. COS AT I I icId/C.roup
13B 07A,07D
21D,11H 11F
13H
21B
07B.07C
21. NO. OF PAGES
104
22. PRICE
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