EPA-460/3-76-035
December 1976
IMPACT
OF COAL AND OIL
SHALE PRODUCTS
ON GASOLINE
COMPOSITION
1976-2000
TASK ONE
FINAL REPORT
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Air and Waste Management
Office of Mobile Source Air Pollution Control
Emission Control Technology Division
Ann Arbor, Michigan 48105
-------
EPA-460/3-76-035
IMPACT OF COAL
AND OIL SHALE PRODUCTS
ON GASOLINE COMPOSITION
1976-2000
TASK ONE - FINAL REPORT
bv
Frank M. Newman, John A. Russell,
John N. Bowden, and Alan A. Johnston
Mobile Energy Division
Southwest Research Institute
San Antonio, Texas
Contract No. 68-03-2377, Task No. 1
(Identification of Emissions From Gasolines
Derived from Coal and Oil Shale)
EPA Project Officer: Robert J. Garbe
Prepared for
ENVIRONMENTAL PROTECTION AGENCY
Office of Air and Waste Management
Office of Mobile Source Air Pollution Control
• Emission Control Technology Division
Ann Arbor, Michigan 48105
December 1976
-------
This report is issued by the Environmental Protection Agency to report
technical data of interest to a limited number of readers. Copies are
available free of charge to Federal employees, current contractors and
grantees, and nonprofit organizations - in limited quantities - from the
Library Services Office (MD-35) , Research Triangle Park, North Carolina
27711; or, for a fee, from the National Technical Information Service,
5285 Port Royal Road, Springfield, Virginia 22161.
This report was furnished to the Environmental Protection Agency by
Southwest Research Institute, San Antonio, Texas, in fulfillment of
Contract No. 68-03-2377, Task No. 1. The contents of this report are
reproduced herein as received from Southwest Research Institute. .
The opinions, findings, and conclusions expressed are those of the
author and not necessarily those of the Environmental Protection Agency.
Mention of company or product names is not to be considered as an
endorsement by the Environmental Protection Agency.
Publication No. EPA-460/3-76-035
11
-------
ABSTRACT
A consensus assessment is made of the impact of coal- and oil shale-derived crudes upon the
composition of gasoline. It is concluded that this impact will be negligible, since the most promising
area for utilization of such crudes will be as burner fuels and middle distillates. Such utilization of
coal and oil shale resources will in turn reduce the demand on petroleum resources which will
continue to be the principal source of gasoline for the remainder of the 20th century.
-------
TABLE OF CONTENTS
Page
SUMMARY . . 1
I. INTRODUCTION 3
II. RESOURCES 5
A. Oil Shale 5
B. Coal 6
C. Tar Sands 7
III. REVIEW OF PROCESSES 9
A. Oil Shale 9
1. Gas Combustion Process 9
2. TOSCO II Process 9
3. Paraho Process 10
4. In Situ Processes 10
B. Coal 10
1. COED Process 11
2. Hydrocarbonization Process 11
3. H-Coal Process 12
4. Solvent Refined Coal Process 13
5. Synthoil Process 13
6. Fischer-Tropsch Process 14
C. Tar Sands 14
IV. SYNTHETIC CRUDE PRODUCTS 15
A. Petroleum Crude 15
B. Oil Shale 15
1. Gas Combustion Process 15
2. TOSCO 11 Process 16
3. Paraho Process 17
4. Other Aboveground Processes 17
5. In Situ Processes 18
-------
TABLE OF CONTENTS (Cont'd)
Page
C. Coal 18
1. COED Process 18
2. Hydrocarbonization 19
3. H-Coal Process 19
4. Solvent-Refined Coal Process 19
5. Synthoil Process 20
6. Fischer-Tropsch Process 20
D. Tar Sands 22
V. TECHNOLOGY PROJECTIONS 23
A. Refining Industry 23
B. Automotive Industry 24
1. Spark Ignition Engine 25
2. Compression Ignition Engine 25
3. Gas Turbine Engine 26
4. Stirling Engine 26
VI. PROJECTED GASOLINE COMPOSITION 27
VII. ACKNOWLEDGEMENTS 29
BIBLIOGRAPHY 30
VI
-------
LIST OF TABLES
Table Page
1 Projected Gasoline Composition and Properties 2
2 Oil Reserves in Known Deposits in the Green River Formation 5
3 Rank of Identified U.S. Coal Resources 6
4 Coal Resources in U.S. Geological Survey Provinces 7
5 General Characteristics of Petroleum Crude from Bagley Field, New Mexico ... 15
6 Properties of Raw Oil Shale from USBM Gas Combustion Retort 15
7 Properties of Crude Shale Oil from TOSCO II Retort 16
8 Properties of Hydrotreated Shale Oil from TOSCO II Retort 16
9 Proposed Properties of Phase I Upgraded Shale Oil from Tract C-a Project .... 16
10 Proposed Properties of Phase II Upgraded Shale Oil from Tract C-a Project ... 16
11 Paraho Retort Crude Shale Oil 17
12 Properties of Shale Oil from Union Rock Pump Retort 18
13 Product Yield Distribution for COED Process 18
14 Properties of Hydrotreated Syncrude from COED Process 18
15 Syncrude Properties from COED Process 18
16 Product Properties from Hydrocarbonization Process 19
17 Properties of Products from H-Coal Process 19
18 Product Inspections of C4 + Liquid from H-Coal Process 19
19 Typical Properties of Solvent-Refined Coal 19
20 Properties of Product from Synthoil Process Using Kentucky Coal Feed 20
21 Properties of Product from Synthoil Process Using West Virginia Coal Feed ... 21
22 Properties of Liquid Products from SASOL Facility 21
23 Properties of Liquid Products from SASOL Facility 22
-------
LISTOFTABLES(Cont'd)
Table Page
24 Properties of Raw Bitumen from Athabasca Tar Sands 22
25 Properties of Synthetic Crude Produced from Athabasca Bitumen 22
26 Refiners Purchasing Quantities of Synthetic Crude Oil from GCOS 22
27 Estimated Daily Volumes of Hydrocarbon Type Crudes 24
28 Projected Distribution of U.S. Light-Duty Automotive Market 25
29 Composition of Synthetic Gasoline from the Paraho Process 27
30 Properties and Hydrocarbon Composition of Naphthas from Syncrudes .... 28
LIST OF FIGURES
Figure Page
1 Projected Volumes of Processed Crude from Various Sources 1
2 Projected Crude Sources for Gasoline Production 1
3 Distribution of U.S. Oil Shale Resources 5
4 Fixed Carbon Content of Major Coal Ranks 6
5 Heat Content of Major Coal Ranks 6
6 Distribution of United States Coal Resources 7
vui
-------
SUMMARY
This report covers Task 1 of a 5-task study intended to identify emissions from coal- and oil
shale-derived gasolines. The fundamental goal of Task 1 has been to define "best estimates" for
composition and properties of such gasolines for the time frame 1976-2000. The principal source of
relevant information for this projection was a comprehensive series of personal interviews with
industrial and governmental personnel directly involved in resource, process and automotive devel-
opmental efforts. This report is intended as a consensus resulting from these interviews.
It should be pointed out that the opinions summarized herein were neither (a) unanimous nor
(b) ill-considered. The individuals contacted were specifically chosen for their experience and cur-
rent involvement in marketing and/or technology forecasting for fuels and powerplants develop-
ment. An effort was made to cover the entire spectrum of each concerned industry. Consequently,
for virtually every statement or opinion reflected herein there is, somewhere, an opposing view
albeit a minority one.
The most significant generalization resulting from this study is that the impact of coal and oil
shale products on gasoline composition and properties during 1976-2000 will be negligible. There
are three principal reasons for this conclusion:
(1) The projected total quantity of crude production resulting from coal or oil shale pro-
cesses in 1976-2000 will be only a small fraction of conventional petroleum crude pro-
duction (see Figure 1)*.
(2) Anticipated use of coal and oil shale crudes is for burner fuels, middle distillates, etc.,
which will reduce the demand on petroleum resources, thus freeing more petroleum crude
for refining into automotive gasoline. Whereas gasoline may have some constituents theo-
retically traceable to coal or oil shale crude as a result of refinery blend-off, these
materials are not expected to constitute more than 3 to 4 percent of total production by
2000 AD (see Figure 2)* and will be indistinguishable from similar petroleum-derived
constituents.
30
Hi
Ui
u
o
ec >
S9
C ffl
O CO
I COAL LIQUIDS
| SHALE OIL
1 PETROLEUM
20
10
O
O
H
U
3
Q
O
-------
(3) Automotive engine technology development, more so than an emerging synfuels industry,
will be the overriding factor in tailoring gasoline composition/performance. The conven-
tional spark-ignition engine is expected to continue to dominate the private automobile
market for the balance of this century. Technological improvements in fuel economy and
emissions control may require changes to existing fuel specifications which can probably be
accommodated by the refinery industry.
Assuming that crudes derived from coal and oil shale will have no significant impact on gasoline
composition, the next logical question is: what will gasoline composition bel Table 1 presents princi-
pal properties and compositional ranges which
exist today and those projected for 1985 and TABLE i. PROJECTED GASOLINE COMPOSITION
2000. The summer/winter distillation and AND PROPERTIES
vapor pressure values shown for present gaso-
lines are the limits for fuels to be used in ex-
tremely hot or extremely cold environments,
the average summer fuels being somewhat more
volatile (10 to 11.5 Ib), and the average winter
fuels less volatile (11.5 to 13 Ib). These limits
have been established by the American Society
for Testing and Materials and by Federal speci-
fications. The compositional analysis data
represents a range of values obtained from
samplings of several nationwide gasoline sur-
veys (refinery and service station samples) re-
ported from 1969 to 1976. Based on regula-
tions promulgated by EPA in the Federal Regis-
ter, Vol.41, No. 164, Monday, Au-
gust 23, 1976, and on activities of the State of California Air Resources Board as reported on Decem-
ber 9, 1975 in the report entitled, "The Feasibility and Impact of Reducing Emissions by Reducing
Gasoline Volatility," it is logical to expect that volatility of gasolines will be reduced in order to meet
evaporative emission requirements for vehicles and service stations. This will be accomplished by the
reduction in concentration of the lighter hydrocarbons, butanes, and pentanes. These hydrocarbons
serve a far more valuable purpose as constituents in other petrochemical processes. Benzene, toluene,
and xylenes serve to increase octane number and either occur naturally as a result of specific gasoline-
producing processes or are added to the blend. Concentration of benzene and toluene will intentionally
be reduced in this time frame since they, too, can be put to better use in the petrochemical industry.
Octane levels will likely be maintained by increasing the concentration of isometric C6-C7 hydrocar-
bons. The heavier C9 + aromatic compounds, which also serve to increase octane number, will remain
relatively constant.
Lower volatility will cause harder starts and longer warmup in present day engines, although
vapor lock and hot start problems due to high volatility fuel will be virtually eliminated. It is antici-
pated, however, that engine manufacturers will modify carburetion or adopt fuel injection more exten-
sively so that performance problems associated with fuel volatility will be minimized. The traditional
mechanism of refining industry response to automotive industry specification is expected to continue.
The essential theme of this report is that gasoline will remain primarily a petroleum-derived
product through 2000 A.D. The material in the main body of the report is intended to provide
details of coal and oil shale crude composition, candidate conversion processes, and to discuss those
technological factors which will influence development of these energy resources.
Distillation,
»F
1 0% evap
50% evap
90% evap
End point
Reid Vapor
Pressure, max, Ib
C4-Cs,vol%
C6-C7,vol%
Benzene, vol %
Toluene, vol %
Xylenes, vol %
C9+ aromatics, vol%
Present
Summer
158 max
170-250
374 max
437 max
9
Winter
122 max
170-230
365 max
437 max
15
12-20
17-36
0.5-2.1
0.6-14.1
1.0-13.6
1.1-20.1
1985
140-165
180-250
374 max
450 max
6
5-8
20-40
<0.5
<10
10-20
10-20
2000
140-165
180-250
374 max
450 max
6
5-8
20-40
...
<10
15-20
13-18
-------
I. INTRODUCTION
Domestic production of petroleum oil and gas continues to decline while demand increases.
The lack of economic incentives inhibits exploration and recovery of more reserves. In this event,
the only alternative is the development of other types of energy sources. Most obviously there is
coal, a tremendously abundant hydrocarbon source material underlying vast areas of the nation.
Next there is oil shale, a rock containing a hydrocarbon material which can be thermally treated to
produce an oil very similar to conventional petroleum. On a far smaller scale there exists the
possibility of using oil extracted from tar sands.
While many improvements have yet to be made in efficiency, existing technology is capable of
converting all of these resources into liquid forms of energy. The reason this conversion is not
presently being done is that it is more difficult, and therefore more expensive, to make liquid fuel
from coal, oil shale, and the other resources than from petroleum crude oil which is available by
conventional drilling.
The factors which cause synthetic fuels from coal, oil shale, and tar sands to be more expensive
consist of more than just the degree of processing required. In particular, they relate to government
policies and incentives. From a purely technical point of view, dollar-for-dollar, liquid fuels could
probably be produced from coal and oil shale at about the same cost as the price we are now paying
for foreign crude. Because of the risks involved in building plants for this purpose, however,
investors are not willing to provide the necessary capital. The risk of plant failure is small; but there
is a remote possibility foreign prices could drop, thus making the synthetic fuels plant a white
elephant. The absence of government guarantees makes it likely that investment capital will not be
available for synthetic fuel plants in the near future.
In the event that a financial subsidy is provided at some future date for the manufacture of
gasoline exclusively from coal or oil shale resources, the cost of an initial batch of such synfuel
would be too high for public consumption. The obvious candidate for field evaluation of this new
fuel would be a government fleet—likely the military or a civilian federal fleet. A natural and
mandatory part of this fleet test evaluation would be measurement of exhaust emissions which, in a
well-designed experimental program, would result in direct comparison with control vehicles
operated on petroleum-derived gasoline. It is possible, therefore, that some fuel-emissions rela-
tionships would be defined in advance of general adoption of synfuel-based technology. Identifica-
tion of trace contaminants would likely not be a part of such an advance fleet test.
Technology is currently available to convert coal, oil shale and tar sands into synthetic crudes
which, in turn, can be refined into clean liquid fuels. Each of these sources of hydrocarbons must be
treated differently to produce useful products and should be discussed separately. The retorting of
oil shale results in a viscous, high molecular weight syncrude which could be refined into gasoline
and diesel and jet fuels similar in composition to products derived from petroleum crudes. Conver-
sion of coal to liquid fuels can be accomplished by many specific processes, which can be catego-
rized into four general types. Three of these process types yield viscous, high molecular weight
syncrudes, generally high in aromatics and sulfur content, which require considerable refining to yield
clean liquid fuels. The fourth type is an indirect liquefaction process whereby hydrocarbon gases
derived from coal are polymerized into liquid fuels. Other fuels that can be economically derived
from coal are methane and methanol; however, a discussion of these products is beyond the scope
of this work. Syncrudes extracted from tar sands are also viscous and high in sulfur, although in
-------
Canada the Athabasca tar sands syncrude is blended with petroleum crude for nearby refinery feed
stocks. Thus, most of the syncrudes derived from oil shale, coal and tar sands will be viscous, high
molecular weight materials containing sulfur, nitrogen and other nonhydrocarbon impurities, and
will require severe refinery processing to yield clean liquid fuels such as gasoline, kerosene and diesel
fuels. Economic considerations may dictate their use as boiler fuels, heating oils or petrochemical
feedstocks where less refining is required. By using them for this purpose, large quantities of
petroleum crude oil now being used in these applications could be refined into gasoline, kerosene
and diesel fuels. If cost is not a constraint to convert these syncrudes into gasoline, the physical and
chemical properties of the product could be made virtually identical to those of gasoline produced
from conventional petroleum crude.
Since this report deals specifically with the potential production of gasoline derived from coal
and oil shale, it should be noted that:
• Syncrude from shale will probably be used for manufacturing boiler fuels, as petro-
chemical feedstocks, or, at most, blending with conventional petroleum crude for refin-
ing into gasoline and other fuels.
• Syncrude from certain coal conversion processes will be utilized much the same as shale
oil syncrude.
• Indirect liquefaction utilizing the Fischer-Tropsch process produces low molecular weight
hydrocarbons identical to those occurring in petroleum derived gasoline. This process is in
commercial operation in South Africa.
• Syncrude production from tar sands will be minimal in this country; however, any pro-
duction will probably be blended with conventional crude for refining into fuels.
The above observations indicate that the production of gasoline in the U.S. from oil shale
syncrude is a remote possibility, while gasoline from coal is more probable. In any event, a know-
ledge of any adverse environmental effects from burning such fuels is important. The first step in
evaluation of emission compositions would be estimations of the compositional ranges of fuels
produced from specific source materials and processes felt to be representative of syncrude
technology.
-------
II. RESOURCES
The following is a brief discussion on each of the principal sources for raw materials from
which gasoline could be synthesized.
A. Oil Shale
Oil shale is a fine-grain sedimentary rock containing a solid organic material called kerogen,
which is released from shale when the rock is heated. Gaseous fractions as well as a heavy liquid can
be recovered, and the liquid can be upgraded to a syncrude, equivalent to a high-grade crude oil.
Deposits of oil shale are found in layers called zones, sandwiched between other layers of
sedimentary rock.
Oil shale is found over a wide area of the
U.S., but the richest deposits, which are at
least 10-ft thick and yield on the average
25 gallons or more of oil per ton of oil shale,
are located in the Green River Formation span-
ning Colorado, Utah, and Wyoming. In fact,
90 percent of the identified oil shale resources
of the U.S. are located in the Green River
Formation (Figure 3). The rich deposits in
this formation (Table 2) cover roughly 17,000
square miles and contain an estimated 4 trillion
TABLE 2. OIL RESERVES IN KNOWN DEPOSITS IN THE
GREEN RIVER FORMATION BILLION BARRELS
OF OIL EQUIVALENT
Shale Grade,
gal. oil/ton
25-65
10-25
5-10
Area totals
(Formation to
Piceance Creek
Basin, Colorado
450-500
800
200
1,500
tal = 4,050)
Uinta Basin
Utah
90
230
1,500
1,820
Green River
Basin, Wyoming
30
400
300
730
I Deposits on the
'Green River for-
mation .including
all identified high-
quality resources
1 Other deposits
FIGURE 3. DISTRIBUTION OF U.S. OIL SHALE RESOURCES
-------
barrels of oil equivalent. Distribution of reserves among the three basins which comprise the Green
River Formation is shown in Table 2.
B. Coal
The total remaining reserve of coal in the U.S. is estimated at 3.2 X 1012 tons, of which about
50 percent has not actually been identified but is surmised to exist on the basis of broad geological
knowledge and theory. Roughly 360 X 109 tons of known reserves
are surface mineable and 553 X 109 tons are recoverable by current
technology. The surface mineable characteristics of known western
subbituminous and lignite coal reserves make them attractive for
future liquefaction operations. Thus about 687 X 109 tons of known
coal resources await both technological advances in recovery tech-
niques and a receptive market.
TABLES. RANK OF IDEN-
TIFIED U.S. COAL
RESOURCES
Rank
Anthracite
Bituminous
Subbituminous
Lignite
Total
Identified
Resources
(billions of
tons)*
21
686
424
449
1580
Source: Averitt, 1973:137.
*In short tons (2000 Ib).
The classification of coals is based on compositional characteris-
tics such as fixed carbon content, heating value, and impurities.
Anthracite and bituminous coals contain more carbon than other
types and are ranked on this basis (Figure 4). Subbituminous and
lignite or brown coal are ranked on the basis of heating value as
shown in Figure 5. Anthracite and bituminous coals make up about
45 percent of the identified U.S. resources while subbituminous and
lignite make up the balance of 55 percent (Table 3).
100
80 -
60
"- 40
M
a.
20
RANK
14
12
10
2
§ 6
i
£
I
RANK
FIGURE 4. FIXED CARBON CONTENT OF
MAJOR COAL RANKS
FIGURES. HEAT CONTENT OF MAJOR
COAL RANKS
-------
Coals are also graded on the basis of moisture
and other impurities such as ash and sulfur.
Moisture content is related to rank inasmuch as the
higher the rank, the lower the moisture content.
Some anthracites contain 1 percent moisture while
some lignites have as much as 40 percent moisture.
Ash content can vary in samples from the same
seam, and investigators have found that, through-
out the U.S., ash content ranges from 2.5 to
33 percent. Sulfur compounds are present in coal,
and range in concentration from 0.2 to 7.0 percent
sulfur. The presence of sulfur compounds in the
coal resource is important from several aspects, not
the least of which are environmental considerations
in the conversion process and in the combustion of
the finished fuel. The low-sulfur coal (1 percent or
TABLE 4. COAL RESOURCES IN U.S. GEOLOGICAL
SURVEY PROVINCES*
Province
Eastern
Interior
Northern Great Plains
Rocky Mountains
Other
Total
Source: Averitt. 1973:
Identified
276
277
695
187
146
1581
Undiscovered
45
259
763
395
181
1643
Total
321
536
1458
582
327
3224
37.
* Because available estimates are by state and USGS
Provinces cross state boundaries the figures for these
provinces are only approximate.
"oast Province
sRocky Mountain Province
'Northern Great Plains Province
Interior Province
Anthracite
Bituminous coal
Subbituminous coal
Lignite
•Eastern Province
FIGURE 6. DISTRIBUTION OF UNITED STATES COAL RESOURCES
less) is predominantly found in the western area of the country, while the high-sulfur coals are more
common in the eastern fields. The western coals are lower in heating value than the eastern coals.
About 90 percent of the known deposits are located in four U.S. Geological Survey provinces:
Eastern, Interior, Northern Great Plains, and Rocky Mountains (Figure 6). Table 4 shows the dis-
tribution of coal resources among these provinces.
C. Tar Sands
, Tar sands (alias bituminous sands, oil impregnated sandstone, etc.) are present in significant
quantities in both the United States and Canada. Approximately one trillion barrels of oil in place
-------
are contained in an area of Alberta, Canada some 200 miles north of Edmonton. Since 1967 a
company known as Great Canadian Oil Sands, Limited, a subsidiary of Sun Oil Company, has been
producing approximately 50,000 barrels per day of high quality synthetic crude from the oil sands.
The reason for the relative success of the Canadian oil sands operations is the nature of the oil
sand deposits which exist there. Not only are the deposits gigantic, but they are easily accessible,
possess homogeneous properties, and therefore are fairly easy to treat. On the other hand, U.S.
deposits are almost miniscule by comparison, are largely inaccessible, and have properties which
make extraction very difficult.
The only U.S. deposits which can seriously be considered to have any commercial potential are
located in Utah. The in-place reserves of the five largest deposits total only 25 billion barrels and the
breakdown is as follows:
Asphalt Ridge 1.1 billion barrels
P.R. Spring 4.5
Suhnyside 4.0
Circle Cliffs 1.3
Tar Sand Triangle 12.5
Because these U.S. deposits are relatively small and are not amenable to recovery by any
currently known processes, it is unlikely that they will play any significant role in the future U.S.
energy supply picture.
8
-------
III. REVIEW OF PROCESSES
A. Oil Shale
Practically all processes designed to extract the hydrocarbon material (kerogen) from raw oil
shale involve the application of heat. This heat energy causes the kerogen to thermally degrade, or
pyrolyze, into a heavy hydrocarbon liquid syncrude. The conditions under which this pyrolysis
reaction takes place can significantly affect the properties of the resulting oil product. Specifically,
if the so-called "retorting" process requires the product oil to encounter excessively high tempera-
ture zones, some degree of thermal cracking may result, thus leading to the production of an
upgraded product and a higher gas yield. Similarly, if the pyrolysis reaction takes place at a very low
temperature, and therefore over a long period of time, noticeably greater concentrations of paraffi-
nic compounds are likely to be present in the final oil product.
In addition to the slightly different products generated by the various retorting processes, each
has associated with it a variety of environmental and operational advantages and disadvantages.
7. Gas Combustion Process
The Gas Combustion process has probably been the most thoroughly investigated retort-
ing process to date. In this process 3 to 4-inch shale feed is placed in a vertical retort and a firefront
is started in the bed. Combustion is maintained by the injection of air. As the firefront advances, it
heats up the shale immediately in front of it, driving off the products of pyrolysis. These products
are collected from the bottom of the retort.
This process can be modified to allow shale to be added and removed continuously. Raw
oil shale feed is continuously fed to the retort at the top and withdrawn from the bottom. As the
shale passes through the retort it encounters higher and higher temperatures until the majority of
the kerogen is pyrolyzed to oil. This product oil is collected at the top of the retort while the hot
shale passes downward into the combustion zone and the residual hydrocarbons and carbon are
burned off to provide heat for the pyrolysis reaction.
2. TOSCO II Process
The retorting process which has probably received the most attention during the past few
years is the TOSCO II process, developed by The Oil Shale Corporation (TOSCO). Unlike the Gas
Combustion process, in which the heat-generating combustion process takes place within the retort-
ing vessel, the TOSCO II technique employs indirect heating of the shale. The mechanism by which
the heat of retorting is supplied is through the use of ceramic heat carriers. These heat carriers are
1/2-inch diameter balls heated in an external heater and then mixed with the raw shale in a retorting
drum. The products of pyrolysis are collected from the drum and the spent shale and balls are sent
to a collection device where the balls are separated and returned to the heater.
Because the heat transfer mechanism employed by the process is primarily solid-solid
rather than gas-solid, the efficiency of the heating process is fairly low. In addition, due to the
required transfer of large quantities of ceramic balls as well as shale solids, the problems inherent in
solids material handling are increased. The primary offsetting advantages to these problems are the
process' proven operability and limited gas handling problems.
-------
3. Paraho Process
The Paraho process is capable of operating in essentially the same way as a Gas Combus-
tion retort. Unlike the Gas Combustion retort, however, the Paraho retort is capable of being
quickly modified to allow for the recycle of hot gas rather than internal combustion.
The hot gas recycle technique produces essentially the same type of high Btu gas and
shale oil as the TOSCO II retort, the tradeoff between systems lying primarily in the solids-versus-
gas handling problems. The TOSCO process requires the circulation of large quantities of solids
(shale and ceramic balls), and in addition the shale feed must be of under 1/2-inch size. The
Petrosix or Paraho (indirect heated mode) retort, on the other hand, involves the handling of large
quantities of gases but can process shale feed up to 3 to 4 inches in diameter, thus minimizing
crushing, handling, and disposal problems.
4. In Situ Processes
While many companies have investigated in situ production, both in bench scale and pilot
plant operations, the only firm currently conducting actual field tests is Occidental Petroleum.
Much of the theoretical work which led to the Occidental tests, however, was conducted at the
Laramie Energy Research Center in Wyoming. In these tests, oil shale rock was packed in above-
ground vessels and retorted in such a way as to simulate actual underground conditions.
Occidental Petroleum uses what is known as a modified in situ process, meaning that a
cavity is first mined conventionally and the overlying shale formation is explosively expanded to fill
the void. When done properly, the void space of the mine cavity is then distributed throughout the
rubblized rock. The "chimney" created by rubblized rock (120 X 120 X 310 ft for Oxy's commer-
cial operation) is then ignited at the top and a combustion front is allowed to move downward by
continued injection of air from the top. Oil is produced and collected in a sump at the bottom of
the retort and is subsequently pumped to the surface for further treatment.
B. Coal
The production of liquid products from coal requires the application of heat (up to 1500°F)
and pressure (up to 5,000 psig) to accomplish a combination of hydrogenation and pyrolysis of the
complex aromatic structures. Liquefaction processes by nature produce a range of products from
gases (high hydrocarbons, H2 CO, and CO2) to heavy synthetic crudes. Crudes derived from coal
generally have a lower hydrogen and higher nitrogen, sulfur, and aromatic content than conven-
tional petroleum crudes. For this reason, synthetic crudes from coal require a certain degree of
pretreatment before processing in a conventional petroleum refining facility. The aromatic content
of synthetic crudes may provide an economic advantage over natural crudes in terms of the net
value of the final products produced.
Coal liquefaction processes are of four general types: hydroliquefaction, solvent extraction,
pyrolysis, and indirect liquefaction (liquids synthesis from H2 and CO). Hydroliquefaction
includes processes involving direct hydrogenation of coal through catalytic action. Solvent
extraction implies processes which hydrogenate without catalysts through use of a hydrogen
donor solvent. Pyrolysis processes drive off the volatile hydrocarbon gases and liquids by
' thermal cracking and carbonization. Indirect liquefaction processes catalytically synthesize low
and middle distillate hydrocarbon compounds through polymerization of CO and H2 products
of coal gasification.
10
-------
Coal feedstocks are more variable than petroleum feedstocks, and coal product markets
are extremely susceptible to competition by easily transportable fluid fuels. Thus liquefaction
research is not characterized by monolithic development toward a single "ultimate" liquefaction
process, but rather, it is a continuing effort to broadly advance a series of processes specifically
suited to limited ranges of feedstocks and markets. It is worthwhile to view individual unit opera-
tions of processes under development as potential elements of novel processes. A demand for these
processes could arise in response to currently unforeseen supply/demand situations for which no
specific existing process was suitable. Regional considerations such as water supply, size of coal
sources, coal rank, composition, size of output capacity needs, and socio-economic factors may well
dictate development of a number of different processes. Current program emphasis is on near term
development of clean coal-based boiler fuel to supply existing oil-fired powerplants.
1. COED Process
The COED .process, developed by the FMC Corporation under ERDA sponsorship, is a
pyrolysis liquefaction process employing staged fluidized beds producing oil, char, and gas.
In the COED process, coal is crushed, dried and then heated to successively higher
temperatures in a series of fluidized-bed reactors. In each fluidized bed, a fraction of the volatile
matter of the coal is released. The temperature of each bed is selected to be just short of the
maximum temperature to which the coal can be heated without agglomerating and defluidizing the
bed. Typically, four stages operating at 600°F, 850°F, and 1500°F are involved. The number of
stages and the operating temperatures vary with the agglomerating properties of the coal. Heat for
the process is generated by burning char in the fourth stage and then using hot gases and the hot
char from the fourth stage to heat the other vessels.
The volatile matter released from the coal in the pyrolysis reactors is condensed in a
product recovery system. The pyrolysis oil product thus derived is filtered by a pressurized, rotary-
drum, precoat filter to remove solids representing char fines which are carried through the cyclones
of the fluidized-bed reactors.
Hydrotreating of the oil occurs in a fixed-bed catalytic reactor containing commercial
nickel-molybdenum catalyst. Hydrotreating reactions remove sulfur, nitrogen and oxygen from
the oil and can produce a 25-30° API synthetic crude oil product.
Yields based on Illinois No. 6 seam coal are: oil (19.3 percent), char (59.5 percent), gas
(15.1 percent), and liquor (6.1 percent).
2. Hydrocarbon ization Process
The conceptual design of a demonstration plant includes five processing areas:
• Coal preparation
• Hydrocarbonization
• Product cooling and liquids separation
• Gas processing
• Hydrogen generation.
Coal is sized and preheated prior to entering the reactor by entrainment in a stream of
hot hydrogen.
11
-------
Coal is injected directly into the fluid-bed reactor from the coal-feed vessel. The sole
fluidizing medium is hydrogen. Product gas and oil exit the reactor at the top, passing through two
cyclones to remove entrained ash and unreacted coal particles.
The hydrocarbonization process is essentially pyrolysis in a hydrogen atmosphere, pro-
ducing to a great extent hydrogenated products. The exothermic heat of reaction between the
hydrogen and coal maintains reactor temperature and is controlled as a reactor temperature
parameter.
The reaction products pass forward from the external cyclone for subsequent cooling and
separation. After removal of heavy and light oil products, hydrogen is removed cryogenically and is
returned to the coal hydrocarbonization area.
LPG and SNG (high-Btu pipeline quality gas) are subsequently recovered from the reactor
off-gas stream. Byproducts recovered are ammonia and sulfur.
Char from the hydrocarbonization area is gasified and the CO-rich gas shifted by steam
saturation and catalysis to a 3:1 H2 /CO, ratio to produce additional process hydrogen.
3. H-Coal Process
The H-Coal process has been developed as a further application of the catalytic,
ebullated-bed reactor technology employed to convert heavy oil residues into lighter fractions.
Design specifications call for a pilot plant to produce low-sulfur fuel oil, and synthetic
crude suitable for refinery processing into gasoline, kerosene, diesel fuel, fuel oil and petrochemical
feedstocks. Of the various categories of liquefaction processes, the H-Coal process would be termed
hydroliquefaction.
Prepared coal is slunied with process-derived oil to which is added compressed, make-up
hydrogen. The slurry and hydrogen are fed to preheaters at the base of the catalytic (Co/Mo)
ebullated-bed reactor, along with recycled high-pressure gas that is similarly preheated. The
catalyst in the reactor is suspended in the ebullated bed by the additional internal recycle-oil
flow.
Reaction products pass overhead for subsequent liquid/gas separation. The light ends are
removed as an overhead vapor product and sent to conventional recovery facilities such as absorp-
tion and low-temperature fractionation. Hydrogen gas is recycled to the reactor.
The liquid product, which is a slurry of oil, ash and unconverted coal, is flash-separated
with the overhead going to atmospheric distillation for separation into light and heavy distillates. A
portion of the bottoms liquid is partially clarified, in this case via a hydroclone, and the balance
goes to vacuum distillation along with the concentrated slurry from the hydroclone. A solids-free
heavy distillate is produced as the vacuum tower overhead/and a heavy residuum, containing
essentially all the solids from the reaction section, is produced as the bottoms. The recycle oil
for slurrying the coal can be a combination of partially clarified oil from the hydroclone with
heavy distillate from both the atmospheric and vacuum towers. Since the solids content of the
12
-------
slurry oil has an effect on the product distribution, it is beneficial to tailor its composition to
obtain the most desirable product spectrum.
4. Solvent Refined Coal Process
The SRC process is a solvent extraction process producing low ash, low sulfur coal extract
that is solid at ambient conditions. Further hydrogenation of the solvent refined coal yields a liquid
synthetic crude. Hydrotreatment studies of SRC have not been extensively conducted to date.
In the SRC process, the coal is first dissolved under moderate hydrogen pressure
(synthesis gas—CO and H2 —has been shown to effect solvation and may be a suitable substitute
for H2) in a heavy aromatic solvent derived from the process. The resulting coal solution is
filtered to remove ash and a small amount of insoluble organic material and fractionated to
recover the solvent. The main product from the process is a heavy organic material called Solvent
Refined Coal which has a melting point of about 350°F and contains less than 0.1 percent ash
and less than 0.8 percent sulfur. Its heating value is about 16,000 Btu per pound regardless of
the quality of the coal feedstock. Smaller quantities of hydrocarbon gases and light distillate
liquids are also produced. The solvent refining process removes all the inorganic sulfur and 60 to 70
percent of the organic sulfur in the coal. This organic sulfur is converted to H2 S by hydrogenation,
then recovered as elemental sulfur from the hydrogen recovery and gas desulfurization unit.
5. Synthoil Process
The Synthoil process is a catalytic coal hydroliquefaction process originally developed by
the Bureau of Mines.
The Synthoil process requires that ground dried coal be mixed with a recycled portion of
its own product oil. The resultant slurry, along with recycled hydrogen and makeup hydrogen is
preheated and conveyed through the fixed bed catalytic reactor. The flow of hydrogen through
both the preheater and the reactor is in the turbulent regime. The combined effect of hydrogen,
turbulence, and catalyst liquefies and desulfurizes the coal.
The reactor is packed with a commercially available catalyst (cobalt-molybdate on silica-
activated alumina) and operating conditions are 840°F and 2,000^,000 psig.
Effluent gases are separated from the extract in the high-pressure receiver and the hydro-
gen rich gas is recycled after the removal of H2S, NH3, H2O and gaseous hydrocarbon. Product
slurry oil pressure is reduced in passing to a low-pressure receiver and is then filtered (or centri-
fuged) to remove the unreacted solids consisting of mineral matter and refractory coal substance.
Part of the nonpolluting fuel oil is recycled as slurry oil. The product oil flows freely at room
temperature and has less than 0.3 percent sulfur content.
The solids from the solids separator go to a pyrolyzer, which yields an additional quantity
of product oil and a carbonaceous residue consisting mostly of mineral matter. This residue together
with the gaseous hydrocarbons from the gas purification system is fed to a gasifier to prepare
makeup hydrogen for the process.
Kentucky Coal, Pittsburgh Seam Coal, Indiana No. 5 Seam Coal, Middle Kentucky
Kittanning (Ohio) Coal and a Wyoming coal have been processed by this method, and in all cases a
product was obtained which contained less than 0.39 percent sulfur.
13
-------
6. Fischer-Tropsch Process
The Fischer-Tropsch process is a simple and proven process to produce synthetic hydro-
carbons and chemicals from hydrogen and carbon monoxide. The synthesis gas can be obtained by
gasification of coal and refining of natural gas. The process catalytically combines CO and H2
through polymerization reactions to produce straight long-chain hydrocarbons and alcohols. Pro-
ducts, after refining, include gasoline, fuel oil, SNG, and PG.
As only one commercial plant, SASOL in South Africa, is currently in operation to
produce liquid hydrocarbons from coal-derived synthesis gas via Fischer-Tropsch Synthesis, the
following description is for that plant.
Coal is gasified in a battery of 13 Lurgi gasifiers to produce a gas consisting essentially of
carbon monoxide and hydrogen. The gas stream from the gasifiers is quenched to remove tar and oil
and purified. The purified synthesis gas stream is partitioned and a part of the gas is passed through
a fixed-bed catalytic reactor (Arge synthesis). Synthesis occurs under conditions of 430°F and
360 psi. The products of the Arge synthesis are straight-chain, high-boiling hydrocarbons, with some
medium-boiling oils, diesel oil, LPG, and oxygenated compounds such as alcohols.
The portion of the synthesis gas which was not sent to the Arge unit goes to the Synthol
plant (Kellogg synthesis) which is a fluidized-bed catalytic (iron) reactor. Operating conditions are
600° to 625°F and 333 psi.
The raw products from the synthesis require certain treatment and then final purification
to make the specification products. From the gas phase, valuable hydrocarbon and chemical
products are scrubbed out and recovered. The oil phase is treated catalytically to remove dissolved
oxygenates and then distilled into gasoline and fuel oil fractions. The remaining liquor is distilled
and fractionated to produce chemical products. Heavy alcohols to pentanol are also recovered.
C. Tar Sands
There are no significant existing or anticipated processes for the recovery of United States' tar
sand hydrocarbon materials because of (a) the relatively small quantities of tar sands in the U.S.,
(b) the fundamentally different nature of U.S. tar sands agglomerate which requires dispropor-
tionate expenditure of energy to extract the material and (c) the fact that U.S. tar sand is some 10
to 20 feet below the surface in thin veins as opposed to the Canadian reserves which lie directly on
the surface.
14
-------
IV. SYNTHETIC CRUDE PRODUCTS
A. Petroleum Crude
Some of the more important properties of a petroleum crude oil are shown in Table 5 for
comparison with properties of the various syncrudes given subsequently in this section. It cannot be
said that this is a typical crude because properties of petroleum
crudes vary extensively. For example, gravities in API units can vary
from 13 to 60 deg and sulfur content from less than 0.10 weight
percent to 4 percent or more. Nitrogen contents of petroleum have
been found to range between <0.01 to around 0.7 percent.
TABLE 5. GENERAL CHARACTER-
ISTICS OF PETROLEUM CRUDE
FROM BAGLEY FIELD,
NEW MEXICO
B. Oil Shale
In general, raw shale oils derived from Green River oil shale
possess markedly different characteristics than conventional crude
petroleum. These differences include:
• High olefin content due to pyrolytic processing,
Gravity, "API
Carbon residue, %
Pour point, °F
Sulfur, wt %
Nitrogen, wt %
Distillation range, °F
IBP
Final BP
Residue, %
46.0
0.1
below 5
0.34
0.008
104
790
7.6
TABLE 6- PROPERTIES OF RAW OIL
SHALE FROM USBM GAS COM-
BUSTION RETORT
• High nitrogen and oxygen content derived from the shale organic material and
• High pour points and viscosities.
The specific values of each of the above properties vary somewhat, depending on the particular re-
torting process used, the temperature and pressure conditions existing during retorting, the grade of
the shale being processed, and the concentration of various mineral
constituents in the raw shale. In addition to the retorting variables,
one of the most important factors in determining the quality of the
final oil product is the efficiency and method of collecting the
hydrocarbon vapors and condensing them into oil. Because the oil
product is composed of hydrocarbon materials having a full range of
boiling points, the temperature and pressure of the collection appa-
ratus will determine how many of the materials end up in the liquid
product and how many are to be burned as process fuel gas. Differ-
ences in collection temperatures of 50°F could conceivably result in
liquid products having 3 to 5 deg API gravity differences.
Keeping the above comments in mind, and recognizing that
the properties of oil products from a pilot unit are not necessarily
the same as those to be expected from a commercial facility, one
may now examine the product properties of the major retorting
processes and make some fairly generalized observations.
7. Gas Combustion Process
The most comprehensive collection of data regarding
the Gas Combustion retorting process was that compiled by the
U.S. Bureau of Mines in Bulletin 635, published in 1966. A review
of the data shows that the average properties of the raw shale oil
produced were as shown in Table 6.
Oil collected, vol %
of Fischer Assay
Gravity, "API
Ramsbottom carbon, wt %
Pour point, °F
Sulfur content, wt %
Nitrogen content, wt %
Vacuum Distillation (ASTM
D-1160, corrected to
760 mm Hg)
IBP 369°F
2% 399
5 446
10 499
20 590
30 670
40 744
50 812
60 870
70 918
80 984
90 1065
Recovery, % 91
82
21
1.4
85
0.67
2.13
15
-------
Because the Gas Combustion process involves the combustion of material in the retort
vessel itself, it is likely that a substantial quantity of light hydrocarbons produced by the pyrolysis
reaction are also consumed. This is demonstrated by the fact the oil yield averaged only 82 volume
percent of Fischer Assay, whereas indirect heated type retorts generally yield in excess of
100 volume percent. A comparison of these product properties with those of some indirectly heated
retorts also shows the Gas Combustion oil to be slightly heavier, thus indicating that some quantity
of light ends is lacking in the oil.
2. TOSCO II Process
The source of most data regarding the TOSCO II process is from representatives of the Oil
Shale Corporation. According to their report, the crude shale oil produced by the TOSCO II process
would have the properties shown in Table 7. It was claimed that the process recovered substantially
100 percent of the recoverable hydrocarbon in the oil
TABLE 7. PROPERTIES OF CRUDE SHALE OIL shale as determined by the Fischer Assay technique.
FROM TOSCO II RETORT
The pour point of the oil product was initially
80° to 85°F, but TOSCO has a patented (U.S. Patent
No. 3,284,336) process by which this pour point may
be lowered to 30° F or less. This process reportedly in-
volves heating the heavy portion of the oil to 700° to
750°F for about 30 minutes and then recombining this
material with the cooler light ends. Evidently, the heat
treating step generates substances which can serve as
effective pour point depressants.
Component
CS-400°F
400-950° F
950° F +
Total
Vol%
17
60
23
100
°API
51
20
6.5
21
Sulfur
wt %
0.7
0.8
0.7
0.7
Nitrogen
wt%
0.4
2.0
2.9
1.9
TABLE 8. PROPERTIES OF HYDROTREATED
SHALE OIL FROM TOSCO II RETORT
Component
C5-400°F
400-650° F
650-EP
Total
Vol%
43
34
23
100
°API
50
35
30
40
Nitrogen
ppm
1
800
1200
TABLE 9. PROPOSED PROPERTIES OF
PHASE I UPGRADED SHALE OIL
FROM TRACT C-a PROJECT
Gravity, "API 28.6
Max true vapor pressure, psia 8.0
Max viscosity, SSU @ 30°F 800
Max pour point, °F 30
TABLE 10. PROPOSED PROPER-
TIES OF PHASE II UPGRADED
SHALE OIL FROM TRACT
C-a PROJECT
Gravity,0 API 45.2
Reid vapor pressure, psia 5
Sulfur, ppm 10
Nitrogen, ppm 510
Arsenic, ppm 8
The TOSCO report also describes an up-
grading scheme by which the crude shale oil can be
converted to a high quality synthetic crude. This process
would involve a delayed coking step followed by
naphtha and gas oil hydrotreaters. The upgraded pro-
duct would likely have the properties shown in Table 8.
The recently released Detailed Development
Plan for Tract C-a (DDP), published by Standard of
Indiana and Gulf Oil, describes a raw oil recovery sys-
tem and upgrading scheme by which the shale oil may
be converted into a pipelineable product having the
properties shown in Table 9.
Rather than using a series of hydrotreaters,
the Amoco-Gulf plan involves the initial fractionation of
the shale oil followed by a thermal cracking operation.
The DDP also describes a more comprehensive up-
grading scheme for the second phase of their operation.
This process involves an initial fractionation step
followed by delayed coking and two hydrotreating
trains. This process is similar to that described in the
TOSCO report. The properties of the product oil from
this process are shown in Table 10.
16
-------
3. Paraho Process
As described in the preceding section of this report, the
Paraho retort now in use at the Anvil Points facility is capable of
operating in both the direct and indirect heated mode. To date,
however, the only data available are in relation to the direct, or
internal combustion, mode of operation. Information provided in
the report entitled "The Production and Refining of Crude Shale
Oil into Military Fuels" by Applied Systems Corporation shows
that the raw shale oil produced by the Paraho retort had the
properties shown in Table 11.
It is highly unlikely that the trace metals shown in
Table 11 would be present in finished gasoline since they would be
removed by catalytic reactions used in conventional petroleum
refining processes. Virtually all the arsenic in the Paraho analysis
was contained in the residual sample (>843°F) and thus would
not be carried beyond the initial refining distillation phase.
The raw shale oil was subsequently refined in the Gary
Western refinery at Gilsonite, Colorado. The process involved the
use of a delayed coker and several trains of hydrotreaters and
desulfurizer units. Rather than a blended synthetic crude product,
an entire range of end products was included in the product slate,
and thus some catalytic cracking and reforming operations were
also involved. The products produced were:
Combat gasoline
JP-4
JP-5/Jet A
Diesel fuel marine/No. 2 diesel fuel
Heavy fuel oil.
TABLE 11. PARAHO RETORT
CRUDE SHALE OIL
Physical Properties
Gravity, °API 19.3
Spec gravity (60/60) 0.9383
Pour point, °F 85.0
Viscosity (cs(» 210°F) 6.38
Viscosity (csfe 140°F) 20.15
Tot acid no. mg KOH/gm 1.969
BS&W,vol% 0.4
Asphaltenes, wt % 0.819
Rams carbon, wt % 1.383
Ultimate Analysis, wt %
Carbon
Hydrogen
Oxygen
Nitrogen
Sulfur
84.90
11.50
1.40
2.19
0.61
Selected Metal Concentration, ppm
Arsenic
Nickel
Iron
Vanadium
19.6
2.5
71.2
0.37
D285 Hempel Distillation of Whole
Crude Shale Oil, vol%: (IBP-238°F)
270°F = 0.1
300°F = 0.3
340° F = 0.7
400° F = 2.0
450°F = 5.1
500°F = 11.8
500° + residue = 87.8
Distillation loss = 0.4
According to recently released reports on the refining operation, the products did
not meet all the specifications established by the military, but this was due to inadequate
processing rather than any major deficiencies in the oil shale feed itself.
4. Other Aboveground Processes
Because of the proprietary nature of the work being done by Superior Oil Company
on their circular grate retort, the detailed analysis of the product oil is not available.
Considering the conditions which would be expected in that type of retort, however, the
properties are likely to be very similar to those of oil produced in any other indirectly heated
retort such as the Petrosix or TOSCO II. Due to the fairly low heating rate which may be
expected, the paraffin pontent of the oil may be slightly greater than that from other
processes. It must also be taken into account that the oil shale feed for the Superior process
is from the northern outcrop area of the basin and this may significantly affect the final oil
properties.
17
-------
TABLE 12. PROPERTIES OF SHALE
OIL FROM UNION ROCK
PUMP RETORT
Gravity, °API 22.7
Carbon, wt 7, 84.8
Hydrogen, wt % 11.61
Nitrogen, wt % 1.74
Sulfur, wt % 0.81
Oxygen, wt % 0.90
Ash, ppm 50
Pour point, °F 60
Viscosity, sus @ 100°F 98.2
Distillation, Modified Engler
IBP 139°F
10% 400
50% 731
90% 960
EP 1077
Likewise, no information is immediately available regard-
ing the properties of oil from the Lurgi-Ruhrgas process. However,
one would naturally expect the values to be similar to those of oil
from the Petrosix or TOSCO 11 processes.
Recent publications by Union Oil Company give a very
brief description of the product oil expected from their "rock
pump" retort. These properties are shown in Table 12.
5. In Situ Processes
As discussed in Section III of this report, the most ad-
vanced in situ recovery technique is that of Occidental Petroleum.
Like the other proprietary processes for aboveground extraction,
very little detailed information is available on the properties of the
product from the Oxy process. From a totally theoretical point of
view, however, one would not expect the final product to be much
different than that produced by the Gas Combustion retort. The
retorting process is essentially the same with the only real difference being the vessel in which the
process takes place. For the aboveground processes the container is a steel drum whereas for the in
situ process the container is a solid wall of unbroken oil shale. Due to the dynamics of the
large-scale in situ operation, however, it would be reasonable to expect a significant change in
product properties from the beginning to the end of the retorting process.
TABLE 13. PRODUCT YIELD DISTRIBU-
TION FOR COED PROCESS
(PER TON)
Coal
Utah
Illinois
Colorado
W. Kentucky
Wyoming
N. Dakota (Lignite)
Syncrude
Bbl
1.3
1.1
1.0
0.9
0.7
0.4
Gas Scf
9,500
9,000
8,000
6,000
18,000
12,000
Char Ib
1,200
1,200
1,100
1,250
1,000
1,400
C. Coal
1. COED Process
The COED facility has operated on a variety
of coals, ranging from North Dakota lignite to West Vir-
ginia high-volatile A-bituminous. The final product
yields from some of these feeds are shown in Table 13.
The properties of the hydrotreated synthetic crude
from Illinois and Utah coal are shown in Table 14.
Additional data regarding the synthetic crude pro-
perties are shown in Table 15.
TABLE 14. PROPERTIES OF HYDROTREATED
SYNCRUDE FROM COED PROCESS
TABLE 15. SYNCRUDE PROPERTIES
FROM COED PROCESS
Property
Composition, vol %:
Paraffins
Naphthenes
Aroma tics
Distillation, °F:
Initial boiling point
50% distilled
End point
Fractionation, wt %:
IBP-180°F
180-390°
390-525°
525-650°
650-end point
Illinois
10.4
41.4
48.2
108
465
746 (98%)
2.5
30.2
26.7
24.3
16.3
Utah
23.7
42.2
34.1
260
562
868 (95%)
0.0
5.0
35.0
30.0
30.0
Test
Flash point, CC°F
Pour point, °F
Water and sediment, vol %
Ash, wt %
ASTM Distillation, °F
IBP
10%
50%
90%
95%
Viscosity, at 100°F
API Gravity
Result
46
<-36
Trace
<0.005
191
273
518
684
720
3.4
27.2
18
-------
2. Hydrocarbonization
Very little information is publically avail-
able regarding the properties of product from this
process as it has to date been developed privately.
Some data have been released, however. These data
are from a unit operated on low sulfur subbituminous
coal from the Lake De Smet region of Wyoming. The
product properties are shown in Table 16. Also
shown in the table are data for Pittsburgh No. 8 coal
to be expected using the De Smet data as a base.
3. H-Coal Process
The properties of product from the H-Coal
process are shown in Tables 17 and 18.
4. Sol vent-Re fined Coal Process
The typical properties of solvent-refined
coal are shown in Table 19. The refined coal has a
TABLE 16. PRODUCT PROPERTIES FROM
HYDROCARBONIZATION PROCESS
Product Properties
Lake De Smet
Pittsburgh
No. 8
Yields, lb/100 Ib MAP Coal
Liquids
Hydrocarbon gas
Water
CO,CO2,NH3,H2S
Char
Hydrogen uptake
21.25
13.20
11.41
13.28
43.02
-2.17
100.0
32.1
18.0
5.0
5.3
43.0
-3.4
100.0
Proximate Analysis (as received)
Moisture
Vola tiles
Fixed carbon
Ash
Total sulfur
Gross Heating Value,
Btu/lb
28.5
30.0
33.3
7.6
0.6
100.0
10,000
4.8
35.1
50.3
7.5
2.3
100.0
10,000
TABLE 17. PROPERTIES OF PRODUCTS FROM H-COAL PROCESS
Product Properties
Illinois Coal
Synthetic
Crude*
Low-Sulfur
Fuel Oil*
Wyodak Coal
Synthetic
Crude*
Normalized Product Distribution
C, -C3 hydrocarbons
C4 -400°F distillate
400-650°F distillate
65 0-9 75° F distillate
975° F + residual oil
Unreacted ash-free coal
H,0,NH3,H.!S,CO,C02
Total (100.0 + //2 Reacted)
Conversion, %
Hydrogen consumption, SCF/ton
10.7
17.2
28.2
18.6
10.0
5.2
15.0
104.9
94.8
18,600
5.4
12.1
19.3
17.3
29.5
6.8
12.8
103.2
93.2
12,200
10.2
26.1
19.8
6.5
11.1
9.8
22.7
106.2
90.2
23,600
*Desired Product.
TABLE 18. PRODUCT INSPECTIONS OF C4 + LIQUID
FROM H-COAL PROCESS
TABLE 19. TYPICAL PROPERTIES-OF
SOLVENT-REFINED COAL
Product
Properties
Gravity, "API
Hydrogen, wt %
Sulfur, wt %
Nitrogen, wt %
Illinois Coal
Synthetic
Crude*
15.0
9.48
0.19
0.68
-•
Low-Sulfur
Fuel Oil*
4,4
8.43
0.43
1.05
Wyodak Coal
Synthetic
Crude*
26.8
10.54
0.16
0.64
* Desired Product.
Properties
Carbon
Hydrogen
Nitrogen
Sulfur
Oxygen
Ash
Moisture
Feed
Coal*
70.7
4.7
1.1
3.4
10.0
7.1
3.0
100.0
Solvent
Refined Coal
88.5
5.1
1.8
0.8
3.7
0.1
0.0
100.0
*Western Kentucky Bituminous.
-------
heating value of about 16,000 Btu/lb and is fairly uniform in analysis regardless of the coal
feed used.
The raw refined coal is usually solid at ambient conditions but may be further hydro-
treated, hydrocracked, or coked to produce more valuable liquids.
5. Synthoil Process
The most recent data regarding the products of the Synthoil process were presented by
representatives of Pittsburgh Energy Research Center at the "Clean Fuels from Coal" Symposium in
1915. These data are shown in Tables 20 and 21.
6. Fischer-Tropsch Process
Table 22 shows the products obtained by the Fischer-Tropsch process with the Arge fixed
bed system as operated at the SASOL facility. This system is operated for production of light
TABLE 20. PROPERTIES OF PRODUCT FROM SYNTHOIL PROCESS
USING KENTUCKY COAL FEED
Products from Reactor
Preheater outlet temperature, °C
S in product oil, wt %
Ash in product oil, wt %
Viscosity of product oil, SSF
Specific gravity of product oil
60°F/60°F
Calorific value of product oil
Btu/lb
Yield of product oil, bbl/ton of
coal (as received)
Consumption of H2 , scf/bbl of
product oil
(1 at 77°F)
(2 at 180°F)
4,000
450
0.2
0.1-0.2
1 26440
1.020-1.082
17,400
3.3
4,375
psi
430
0.45
0.75
2 10-30
1.034-1.094
17,800
3.2
4,170
2,000 psi
430
0.5-0.7
1.3-2.9
2 14-98
1.060-1.148
16,640
3.0
3,450
Products Following Centrifugal ion
Pressure, psi
Preheater tempera ture,°C
Residues, wt % of whole product
S in residues, wt %
Solvent Analysis of Residues,
wt %
Ash
Organic benzene insolubles
Asphaltenes
Oil
Centiifuged liquids, wt % of
whole product
S in centrifuged liquids, wt %
Solvent Analysis of Centrifuged
Liquids, wt %
Ash
Organic benzene insolubles
Asphaltenes
Oil
4,000
450
11.7
4.6
52.8
14.9
3.1
29.2
88.3
0.2
0.1
0.8
10.8
88.3
psi
430
12.1
5.2
53.0
14.1
5.6
27.3
87.9
0.45
0.75
0.9
18.7
79.65
2,000 psi
430
12.1
4.9
55.3
17.5
6.5
20.7
87.9
0.6
2.1
4.4
27.6
65.9
20
-------
TABLE 21. PROPERTIES OF PRODUCT FROM SYNTHOIL
PROCESS USING WEST VIRGINIA COAL FEED
Products from Reactor
Preheater outlet temperature, °C
S in product oil, wt %
Ash in product oil, wt %
Viscosity of product oil, SSF1
Specific gravity of product oil,
60°F/60°F
Calorific value of product oil,
Btu/lb
Yield of product oil, bbl/ton of
coal (as received)
(1 at 180°F)
Products Following
Pressure, psi
Preheater temperature, °C
Residues, wt % of whole product
S in residues, wt %
Solvent Analysis of Residues,
wt %
Ash
Organic benzene insolubles
Asphaltenes
Oil
Centrifuged liquids, wt % of
whole product
S in centrifuged liquids, wt %
Solvent Analysis of Centrifuged
Liquids, wt %
Ash
Organic benzene insolubles
Asphaltenes
Oil
4,000 psi
450
0.4
0.5
18-40
1.056-1.093
17,000
3.4
Centrifugation
4,000 psi
450
8.2
4.9
41.7
22.9
6.4
29.0
91.8
0.4
0.4
2.4
21.3
75.9
2,000 psi
450
0.6
1.6
56-585
1.129-1.174
16,700
3.2
2,000 psi
450
9.1
5.8
34.6
26.0
11.2
28.2
90.9
0.6
1.6
13.0
30.1
55.3
TABLE 22. PROPERTIES OF LIQUID PRODUCTS
FROM SASOL FACILITY
Selectivities %
CH4
C2H4
C2H6
C3H6
C3H8
C«H8
C,H10
Petrol C5 -C, 3
Diesel C, 3 -C18
Heavy oilC19-Cj,
andC,,-C30
wax C31 +
NAC
Acids
Arge
5.0
0.2
2.4
2.0
2.8
3.0
2.2
22.5
15.0
6.0
17.0
18.0
3.5
0.4
100.0
Synthol
10.0
4.0
6.0
12.0
2.0
8.0
1.0
39.0
5.0
1.0
3.0
2.0
6.0
1.0
100.0
Pilot Plant
30
15
15
16
20
1.5
1.5
1
0.05
100.0
50
17
11
13
7
0.5
0.5
1
0.05
100.0
70
12
6
6
6
0.2
0.05
100.0
21
-------
TABLE 23. PROPERTIES OF LIQUID
PRODUCTS FROM SASOL
FACILITY
Liquid
Products
% Paraffins
% Olefins
% Aroma tics
% Alcohols
% Carbonyls
% n Paraffin
Arge
r -r
'-s^-i i
53
40
0
6
1
95
r -r
*- 1 3 ^- 1 8
65
28
0
6
1
93
Synthol
C5-C10
13
70
5
6
6
55
C -C
*~ 1 1 ^-1 4
15
60
15
5
5
60
TABLE 24. PROPERTIES OF
RAW BITUMEN FROM
ATHABASCA TAR
SANDS
Gravity,0 API
Viscosity, SUS @
Carbon, wt %
Hydrogen, wt %
Oxygen, wt %
Nitrogen, wt %
Sulfur, wt %
100°F
7.8
35,100
83.2
10.4
0.94
0.36
4.2
Distillation
IBP
5%
10%
30%
50%
EP
505° F
544
610
795
981
1030
hydrocarbons and motor fuels with some desira-
bility for light olefins such as ethylene and
propylene. By changing conditions, it is possible
that the fixed bed plant could be made to produce
the same slate as the Synthoil plant. Table 23 gives
a further breakdown of the properties.
D. Tar Sands
Although it has been stated earlier that the
production of oil from U.S. tar sands deposits will
TABLE 25. PROPERTIES OF SYN-
THETIC CRUDE PRODUCED
FROM ATHABASCA BITU-
MEN (DATA FROM
GCOS FACILITY)
Gravity, "API
Carbon, wt %
Hydrogen, wt %
Nitrogen, wt %
Sulfur, wt %
38.3
86.3
13.4
0.02
0.03
Distillation
IBP
5%
10%
30%
50%
90%
EP
162°F
221
254
408
507
615
715
TABLE 26. REFINERS PURCHASING
QUANTITIES OF SYNTHETIC
CRUDE OIL FROM GCOS
have little or no bearing on the future U.S. energy
supply picture, it should be emphasized that ex-
tremely high quality material can and is being pro-
duced from Canadian tar sands deposits. In its raw
state, bitumen from the tar sands is a much less
desirable material than raw shale oil from any avail-
able retorting process. The properties of raw Atha-
basca bitumen are shown in Table 24. However, with
proper treatment, this bitumen may be refined into
an exceptionally good refinery feedstock. The typical
properties of this synthetic crude oil are shown in Table 25. To demonstrate the value of this
material, Table 26 lists the refiners who consistently purchase quantities of synthetic crude from
the Great Canadian Oil Sands facility in Alberta.
Refiner
Northwestern Refining Co.
Shell Canada
Sun Oil, Ltd.
Location
St. Paul Park, Minnesota
St. Boniface, Manitoba
Corunna, Ontario
Sarnia, Ontario
Toledo, Ohio
22
-------
V. TECHNOLOGY PROJECTIONS
A. Refining Industry
The technology of today has been a continuously evolving process over the last 100 years in
which gradual steps have been taken. The need for new processes has been a continual but not
excessively demanding one, such that evolutionary progress and development was adequate. The
economic requirements have been such that compatibility with existing hardware and facilities
prevented radical growth or revision. The product specification demand has also been such that
growth and development have been gradual. The quality of crude has been premium in most cases,
and supply permitted selection of crude types to allow blending to meet process and product
requirements. This systematic growth has resulted in a refining and processing industry capable of
producing the required fuels for current automotive requirements.
In recent years, as the requirement has grown for specific products with more demanding
specifications and the supply of premium domestic crude has dwindled, new technology has been
developed to "reshape" the chemical nature of the crude regardless of its quality and source so that
the desired product type and quality are obtained. These processes of cracking, reforming and
hydrotreating when enhanced by long-practiced blending have served the fuels and chemicals
market well.
As a result, the petroleum industry has developed processes to meet product requirements.
Some of these processes are quite sophisticated and require very specific, carefully-controlled feed-
stocks. Deviation from the quality specifications of the feedstocks can result in serious degradation
of the process or the catalysts used, or, in some cases, destructive explosions. Therefore, pretreat-
ment of crudes and feedstocks is routinely performed to bring those materials into line before they
are introduced to the refining process. One such commonly used pretreatment is hydrotreating. This
process is applied at various points in the refining procedure, depending on the quality of the
feedstock, the required product quality, and the process involved. Some of the effects of hydro-
treating are the removal of elements such as oxygen, nitrogen and sulfur, the reduction of olefin
content, the saturation of some aromatics, and the improvement of long-term stability.
Hydrotreating, in general, is a very powerful technique to "clean-up" low quality, marginal
crudes and feedstocks. However, it does increase the cost of processing, with the more "con-
taminated" materials requiring more extensive and successive hydrotreating steps, thus further
increasing costs. With these points in mind, it is obvious why the petroleum industry seeks out and
processes high quality crudes in preference to those which would require heavy pretreatment and
cleanup.
It is reasonable to expect further advances in processing technology over the next 25 years
which will make new and improved methods available. However, the overall objectives of the
refining industry can be met now with today's technology, and future requirements are not ex-
pected to be drastically different from today. The major areas of improvement in technology will
probably be in higher efficiencies, better yields, better energy utilization and conservation, and
higher production.
Synthetic crudes are, in effect, among the worst case examples of marginal petroleum crudes.
These marginal crudes require, in many instances, extensive cleanup just to make them into reason-
ably stable and transportable materials. The shale oil produced from retorting contains olefins to
23
-------
such an extent that the oil is unstable. The high density, high viscosity,and high pour point clearly
demand significant supplemental processing such as hydrotreating to yield products of quality for
transport and further refining or consumption. Upon receipt of such feedstocks, a contemporary
refinery can preprocess the material to bring it within the acceptable specifications for that refinery.
However, this extensive hydrotreating and processing only further increases the cost of the final
products. As a result, syncrudes will have a severe handicap in competing with conventional crudes
as refinery feedstocks.
This conclusion can be drawn for all syncrudes, regardless of source. Not only are the produc-
tion processes new and expensive, but their future development will depend upon well-defined
governmental energy policies. Industry and investors are less than eager to sink large sums of capital
into programs which have uncertain, if not bleak, chances of financial success. As a direct conse-
quence, only limited quantities of unconven-
TABLE 27. ESTIMATED DAILY VOLUMES OF HYDRO- tional crudes are expected to be found on the
CARBON TYPE CRUDES MMBBLS/DAY crude market before 1990.
EAC"H SOURCE
By The Year
1985
1990
2000
Tai Sand
0.01
0.02
Oil Shale
0.15-0.25
0.3-0.75
1.0-2.0
Coal
0.05
0.2
0.3-0.5
Petroleum
21.9
23.3
25.5
During 1990-2000, increasing supplies of
syncrudes are anticipated but the total is still
not expected to be of major significance.
Table 27 gives an optimistic estimate of the
daily volumes of synthetic crudes produced.
Even though only a small percentage of the total may come from synthetic sources, a still
smaller percentage will be processed into gasoline. More likely, these syncrudes will be minimally
processed to provide heating fuels with easier-to-attain specifications (and less expensive) thus
relieving demands on petroleum crude supplies which can be processed more easily and at less cost.
In a minimum processing case for syncrudes, some desirable products are recoverable, such as
light gases and naphthas. These materials will readily find their way into appropriate markets.
Fortunately, these low-boilers are the least expensive to hydrotreat and process and are welcomed
by the refiner. The higher boiling materials will supply the furnace oil market where impurities can
be better tolerated and controlled.
Experts in the refining industry are currently in unanimous agreement that the influx of syn-
crudes will have no effect on the composition of future gasoline. The supply is not expected to be sig-
nificant; the use is not expected to be for refined products, and that which is refined into gasoline will
totally lose its identity in the refining process and in blending with streams refined from petroleum
crudes.
B. Automotive Industry
The consensus within the refining industry regarding gasoline compositions and performance
through the end of the 20th century is that (a) the industry can and will supply gasoline at any
performance level required by dominant gasoline-powered internal combustion engines, (b) the cost
of this gasoline will fluctuate (and rise) in response to recognized factors, and will be tolerated by
the public up to a level of two or three times today's prices, and (c) syncrude materials will have
little, if any, impact on gasoline quality or composition since the projected quantities from coal or
shale will be minute in comparison with petroleum crude throughout.
The principal criteria for customer satisfaction and consequent gasoline demand during the next
several decades will continue to be fuel performance and vehicle driveability. The projected quantities
and distributions for these several engine types are dependent upon the rate of development of
24
-------
Type
Spark Ignition
Diesel
Stirling
Gas Turbine
1975
99
1
0
0
1980
98
2
0
0
1985
90
10
0
0
1990
85
14
1
0
1995
75
20
5
0
2000
60
30
10
0
Assumptions:
(1) NOX Std 3=0.93 g/km; other stds. become increasingly
stringent.
(2) No dramatic economic advantages of light-duty diesel over
SI.
(3) Gas turbine remains uneconomical for light-duty vehicles.
(4) Stirling proves practicable, but requires long-term R&D.
less conventional automotive powerplants TABLE 28. PROJECTED DISTRIBUTION OF u.s.
such as gas turbine, (small) diesel, and Stirl- LIGHT-DUTY AUTOMOTIVE MARKET
ing. Each of these, in turn, will be highly
dependent upon the nature of vehicle emis-
sions regulations that may become effective
during the 1976-1980 time frame. Status of
such regulations may be described as being in
intermediate-to-advanced stages of finaliza-
tion within Congress at this time with pro-
mulgation possible by 1978. Of the several
components, by far the most pertinent and
critical to new engine development will be the
oxides of nitrogen (NOX) standards for light-
duty vehicles (currently 6000 Ib GVW or less,
which may be raised to 8500 GVW for light-
duty trucks). This is the largest single production category as regards personal and small commercial
vehicles. While there is some disagreement as to the exact value, promulgation of a NOX standard
above (roughly) 0.93 g/km will dramatically increase incentive to develop small diesel engines for
light-duty transport vehicles. This would result in a correspondingly increased demand upon the
middle distillate fraction of the refined hydrocarbon product. The conventional gasoline engine is
nevertheless expected to constitute the dominant percentage of this category through 2000 A.D.
Table 28 summarizes one such projection for the several engine types in the light-duty vehicle
category with the noted assumptions.
Each of these engine types will be discussed in the subsequent subsections.
/. Spark Ignition Engine
It has already been stated that this engine is expected to continue to dominate the
light-duty vehicle field for the balance of this century. This engine will probably require gasoline
representative of requirements for the most recent production engines.
The effect of the several approaches to emissions control for the spark ignition engine will
be dependent upon any "technological breakthroughs" (e.g., lean burn techniques, stratified charge)
which serve to displace the catalytic converter. Barring breakthroughs in either converter or anti-
knock technology, unleaded gasoline will become increasingly abundant as attrition reduces the
ranks of vehicle systems compatible with leaded gasoline.
Two other engine-related factors could conceivably affect gasoline front-end volatility.
These factors would be (a) promulgation of increasingly restrictive evaporative emissions standards,
and (b) more widespread use of fuel injection technology. The latter is highly dependent upon the
individual fuel injection design, some configurations being considerably more fuel-sensitive than
others.
2. Compression Ignition Engine
The diesel engine's potential for light-duty vehicle application will, as discussed pre-
viously, be strongly affected by the pending decision on NOX standards. Projections for the diesel's
expansion in this area would indicate a linear growth of almost 1 percent per year through
2000 A.D. As acceptance increases, and diesel fuel presumably becomes more widely available, this
25
-------
rate might conceivably double, especially if the small diesel proves to have economic advantages
over the spark ignition engine (e.g., maintenance, improved fuel economy).
3. Gas Turbine Engine
Few advocates of the gas turbine automotive powerplant forecast extensive automotive
use of this engine before 1985. Initial mass production-if manufacturing, maintenance and fuel
economy problems can be overcome—will undoubtedly be composed of heavy-duty trucking
engines with light-duty private vehicle marketing trailing by a few years. The gas turbine can—but
probably will not-operate on gasoline. Conventional middle distillates and methanol seem far more
likely at this point. Sulfur and metals content for gas turbine fuels, regardless of class, will be
critical due to inherent sensitivity to turbine blade erosion and other corrosion-sensitive characteris-
tics known for this powerplant.
The future for the automotive gas turbine remains clouded, with the several major
automotive manufacturers having widely divergent commitments and activity in research and devel-
opment. The most pessimistic viewpoints, of course, are that the above-mentioned costs of manu-
facture and sophistication of maintenance will negate potential for sales to the general public. (This
is reflected in Table 28). The most optimistic viewpoints project that the gas turbine will almost
totally supplant all other forms of automotive power by 2000 A.D. This will obviously be con-
tingent upon major technological breakthroughs which will permit operation at increased pressures
and temperatures, and with engine configurations less costly than existing turbine engines. Ceramic
turbine wheels offer hope for this kind of breakthrough, but their development has not progressed
enough to make a good estimate on their availability. It is noteworthy, too, that increasing pressures
and temperatures may increase the probability of increased NOX emissions. It remains to be seen, if
NOX is to be a serious problem with "automotive type" pressure ratio turbines of the future.
4. Stirling Engine
The Stirling external combustion engine is capable of operating on a broad range of fuels,
and is insensitive to octane or cetane numbers. Fuel metering and mixing for efficient combustion is
the only significant fuel tolerance problem to contend with. The Stirling will be in R&D and early
production stages during 1976-1990 and will be designed to utilize those fuels expected to be
generally available in 1985-2000. It is highly probable that (if diesel automotive engine technology
and production accelerates during 1980-1990) Stirling production configurations will be designed
around middle distillate fuels. Maximum projections for this engine indicate that it will take over no
more than 10 percent of the light-duty automotive market by 2000 A.D. (again reflected in
Table 28).
26
-------
VI. PROJECTED GASOLINE COMPOSITION
The majority opinion of knowledgeable parties in the fuel production and automotive manu-
facturing industries is that the spark ignition engine will continue its dominant role until the year
2000, and will continue to require gasoline as a fuel. If syncrudes become available and are refined
into gasoline, that gasoline's composition will be dictated by the engine technology of the time and
not by the crude source.
Fuel refining experts believe that gasoline will change gradually over the next 10 years with the
overall effect being small. The demand on the petrochemical market for propane and butanes will
cause a gradual disappearance of these components from gasoline. The same can be said for benzene
today and toluene will probably be reduced in the future for that reason also. Octane number is
expected to be maintained in the 90-92 RON range, and manganese will probably find popularity as
an octane improver even though not as capable as lead. Aromatics content of future gasolines will
probably be maintained in the 25- to 30-percent range as a maximum. The loss of butanes and
pentanes from the fuel will require increases in the C6-C7 range, thus altering the IBP and front-end
curve. The midpoint and FBP will see little or no change.
After 1985, significant improvements in engine fuel metering systems can be expected. With
computer-controlled "carburetion" and timing so that air-fuel ratios can be precisely maintained
and varied as driving conditions and emissions dictate, new and more demanding specifications for
gasoline will probably emerge. At that time, more narrow cuts of fuel will be required with more
precise control of chemical composition and carbon-hydrogen ratios. Increased application of fuel
injection systems would similarly place new requirements on gasoline composition. These require-
ments will not be met without additional costs, which must be borne by the consumer. High-volume
production will minimize the cost increases, but it must be kept in mind that the more specific and
stringent requirements become, the more expensive the product. If syncrudes are fed into the
system, the costs will climb even more because of the increased costs of processing. The refiner is
now under new pressure to provide finished fuels from the most efficient processes that result in the
best overall energy yields. From this viewpoint, the best energy yield is accomplished when the
finished fuel requires the least amount of refinery and crude energy. This, in turn, works against
sophisticated "rework" processes which are expensive in energy as well as in dollars.
Experimental batches of gasolines and
naphthas have been prepared from syncrudes
derived from coal and oil shale. The data in
Table 29 compare composition of gasoline
from shale oil to petroleum-derived gasoline,
and in Table 30 published data for syncrude
naphthas are shown. Although in actual
practice the snyfuels may have compositions
completely different from those shown, these
analyses do give an indication of what might
be expected. The data also indicate that the
composition of the naphtha is very dependent
on coal or oil shale source and the liquefac-
tion processes. The H-coal hydrogenation
produced more 21" ring aromatic compounds
than the COED pyrolysis, and the Wyoming
TABLE 29. COMPOSITION OF SYNTHETIC GASOLINE
FROM THE PARAHO PROCESS
Parafins. vol %
Olefins, vol %
Naphthenes, vol %
Aromatics, vol %
Aromatic distribution, vol %
Benzene
Toluene
Ethylbenzene
M&P Xylene
O-^Xylene
C,+ Aromatics
Oxygen, wt %
Nitrogen, wt %
Gasoline
from Shale
44
12
8
36
1.4
7.0
1.5
6.6
2.5
14.7
0.52
0.03
Commercial
Unleaded Gasoline
34
19
18
29
0.6
2.1
1.4
4.7
2.4
16.1
nil
nil
27
-------
TABLE 30. PROPERTIES AND HYDROCARBON COMPOSITION
OF NAPHTHAS FROM SYNCRUDES
Source
Liquefaction process
Treatment of crude oil
Boiling range. °F
Fraction of crude oil.
vol%
Gravity, "API
Hydrogen, wt %
Nitrogen, wt %
Sulfur, wt %
Octane number, Research
Hydrocarbon type, wt %:
Paraffins
Monocycloparaffins
Cycloparaffms, 2* rings
Alkyl benzenes
Aromatics, T rings
Nonhydrocarbons
Oil Shale, Wyoming
In Situ Combustion
Coked and
Hydrogenated
175° -350° F
22.4
52.6
—
0.0001
0.001
—
42.8
}43 4
«J.«
}13 8
i. J tO
<0.001
Oil Shale, Colorado
Combustion Retort
Coked and
Hydrogenated
180°-400°F
34.5
51.3
14.2
0.024
0.001
32.8
47.7
34.5
2.4
13.2
2.2
—
Bituminous Coal,
Illinois
COED, Pyrolysis
Hydrogenated
180° -390° F
33.1
43.8
—
0.013
0.009
70.1
7.1
58.9
12.5
19.8
1.7
—
Bituminous Coal,
Illinois
H-Coal,
Hydrogenation
—
C4-400°F
33
49.2
...
0.10
0.099
—
12.0
47.9
14.5
17.6
7.0
0.9
Subbituminous Coal,
Wyoming
H-Coal.
Hydrogenation
—
C«-400°F
57
50
_™
0.20
<0.07
—
18.9
44.5
15.0
14.2
5.9
1.7
subbituminous coal produced naphtha with higher concentration of nitrogen compounds than the
Illinois bituminous. It is anticipated that the last two naphthas would be refined further to
remove nitrogen and 21" ring aromatic compounds before using in gasoline blending.
28
-------
VII. ACKNOWLEDGEMENTS
As has been stated, all of the foregoing projections have been based upon the author's inter-
pretation of subject matter covered during personal interviews with technical personnel recognized
as currently active and highly competent in the oil shale, coal, refining, and automotive industries.
In all, about 75 individuals were contacted in face-to-face discussions. While each interviewer
cannot properly be identified individually, the authors wish to express their gratitude for the
uniform and consistent degrees of candor, clarity and objectivity exhibited by this most knowledge-
able group. The list of individual organizations from which these persons were selected is given
below. This listing is not intended to imply that any statements made in this report represent the
policies or opinions oj any given organization. Rather, the authors have made an effort to reflect
prevailing opinions in a technological area which changes so rapidly that specific statements may be
refuted tomorrow—and again accepted the day following.
Consultants
• Cameron Engineers, Incorporated
• University of Wisconsin, Department of Mechanical Engineering
• Stanford Research Institute
Automotive
• General Motors Research Center
• Ford Development Center
• Chrysler Engineering
Energy (Government)
• ERDA, Fossil Fuels, Washington, D.C.
• ERDA, Bartlesville Energy Research Center
Energy (Industry)
SOHIO Research & Development Division
Brown & Root Engineering
Shell Oil Company
EXXON Research & Development Center
Fluor Corporation
SASOL, South Africa
Charter Oil International
Pennzoil United
29
-------
BIBLIOGRAPHY
A. Oil Shale
Applied Systems Corporation, "The Production and Refining of Crude Shale Oil into Military
Fuels," Final Report, 1975.
Cameron Engineers, Synthetic Fuels,Quarterly Report, 1965-1976.
Gulf Oil Corporation and Standard Oil Company (Indiana), "Detailed Development Plan-
Tract C-a," Volume 3, 1976. '
Hendrickson, T. A., Synthetic Fuels Data Handbook, Cameron Engineers, Denver, Colorado,
1975.
Union Oil Company, "Oil Shale: Another Source of Oil for the United States." A report to
stockholders, 1974.
U.S. Bureau of Mines, "Development of the Bureau of Mines Gas Combustion Oil-Shale Re-
torting Process," Bulletin 635, U.S. Department of the Interior, 1966.
Whitcombe, J.A., and Vawter, R.G., "The TOSCO II Oil Shale Process," A presentation to the
79th National Meeting of the AICHE, 1975.
B. Oil Sands
Camp, F. W., The Tar Sands of Alberta, Canada, Cameron Engineers, Denver, Colorado, 1974.
Congressional Research Service—Library of Congress, "Energy from U.S. and Canadian Tar
Sands: Technical, Environmental, Economic, Legislative, and Policy Aspects," prepared for the
Subcommittee on Energy of the Committee on Science and Astronautics, U.S. House of
Representatives, 1974.
Hendrickson, T. A., Synthetic Fuels Data Handbook, Cameron Engineers, Denver, Colorado,
1975.
C. Coal
Hendrickson, T. A., Synthetic Fuels Data Handbook, Cameron Engineers, Denver, Colorado,
1975.
Howard-Smith, I., and Werner, G. J., "Coal Conversion Technology—A Review," Millmerran
Coal Pty. Ltd., Brisbane, Australia, 1975.
Institute of Gas Technology, "Clean Fuels from Coal," Proceedings of symposium held
September 10-14, 1973.
Institute of Gas Technology, "Clean Fuels from Coal," Proceedings of symposium held June
23-27, 1975.
30
-------
Schmid, B. K., "The Solvent Refined Coal Process," Presentation at the Symposium on Coal
Gasification and Liquefaction, University of Pittsburgh, August 6-8, 1974.
Tyler Industrial Products (subsidiary of Combustion Engineering), "Coal Technology," Pro-
ceedings of Conferences in Pittsburgh, St. Louis, and Denver, 1975.
U.S. Department of the Interior, "Shaping Coals' Future Through Technology," 1974-1975
Report by Office of Coal Research, 1975.
31
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-460/3-76-035
4. TITLE AND SUBTITLE
"Identification of Emissions from Gasolines Derived
from Coal and Oil Shale; Task I - Impact of Coal and
Oil Shale Products on Gasoline Composition: 1976-2000'
3. RECIPIENT'S ACCESSION»NO.
5. REPORT DATE
December 1976
6. PERFORMING ORGANIZATION CODE
11-4493
7. AUTHOR(S)
John A. Russell, John N. Bowden, Frank M.
Newman and Alan A. Johnston
8. PERFORMING ORGANIZATION REPORT NO
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Southwest Research Institute
8500 Culebra Road
San Antonio, Texas 78284
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
68-03-2377
12. SPONSORING AGENCY NAME AND ADDRESS
Environmental Protection Agency
Motor Vehicle Emission Laboratory
2565 Plymouth Rd
Ann Arbor. Mich 48105
13. TYPE OF REPORT AND PERIOD COVERED
Final Task I Feb 76 to Dec 76
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
16. ABSTRACT
A consensus assessment is made of the impact of coal- and oil shale-derived
crudes upon the composition of gasoline. It is concluded that this impact will
be negligible, since the most promising area for utilization of such crudes will
be as burner fuels and middle distillates. Such utilization of coal and oil shale
resources will in turn reduce the demand on petroleum resources which will continue
to be the principal source of gasoline for the remainder of the 20th century.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
c. COS AT I Field/Group
Exhaust Emissions
Motor Vehicles
Fossil Fuels
Coal gasoline
Shale-oil gasoline
8. DISTRIBUTION STATEMENT
Release Unlimited
19. SECURITY CLASS (This Report)
Unclassified
21. NO. OF PAGES
36
20. SECURITY CLASS (Thispage)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
------- |