8

Coal Liquefaction
There are several avenues which can be employed to produce liquids from
coal. Figure 8-1 summarizes the various paths of converting coal to liquid fuels,
which generally are classified as either indirect or direct liquefaction. Indirect
liquefaction, which is already commercialized, involves gasification of the coal
followed by chemical processing at high pressure to yield a variety of liquid hy-
drocarbons. One advantage of indirect liquefaction is that it yields a product mix
with a high percentage of liquid transportation fuel (e.g., gasoline), thus satisfy-
ing one of America's primary energy needs.
The second approach is direct liquefaction, where the coal is hydrogenated un-
der high pressures to form a liquid plus a solid residue. While this latter approach
has the attractive features of higher thermal efficiency and potentially lower pro-
cessing costs than for indirect liquefaction, significant research and development
problems remain to be solved. Commercialization of these processes will proba-
bly not occur until after 1990.! Direct liquefaction also does not yield a high
percentage of gasoline but rather produces heavier components which do not
match up well with current fuel demands.!
Given the choice between liquid and gaseous synfuel products from coal, coal
liquids have several distinct advantages over synthetic natural gas:
I. Liquefaction requires less chemical transformation and hydrogenation than
high Btu gasification. Since the HIC ratio of coal is 0.8, less hydrogen is
required to form a liquid (H/C =2) than methane (H/C =4). This should
also make liquefaction more thermally efficient and less expensive.
2. Process conditions (especially temperature) are less severe for direct lique-
faction, which could reduce equipment costs.
193
194 Coal Processing and Pollution Control
LIQUID HYDROCARBCNS
LIQUID HYDROCARBONS
GASOLINE
METHANOL
LIQUID
HYDROCARBONS
SOLID AND LIQUID
HYDROCARBONS
METHANOL
SYNTHESIS
METHANOL
CONVERSION
FISHER-TROPSCH
SYNTHESI S
Figure 8-1. Schematic diagram of the coal liquefaction processes.
3. Synthetic oil is a more concentrated form of energy and is more economi-
cal to transport for long distances than gas.
4. Synthetic oil is more easily stored than gas.
5. Compared to gasification, liquefaction plants have smaller water require-
ments; air and water pollutant streams are smaller in magnitude.
In this chapter the indirect liquefaction methods (production of methanol and
gasoline) are covered first, followed by a discussion of the chemistry and process
flowsheets for direct liquefaction. Upgrading of coal liquids and commercializa-
tion potential of liquefaction processes are covered next, concluded by an eco-
nomic comparison of direct and indirect liquefaction processes.
Indirect Liquefaction of Coal
Once coal is gasified to CO, H2, and CH4, these components can be further
processed to yield a variety of liquid products, such as gasoline, methanol, diesel
fuel, heavy oils, waxes, middle distillates, and various petrochemicals. The dis-
tribution of the products is largely influenced by the H2/CO ratio in the feed gas.
While the H2/CO ratio from the gasifier may vary from 0.5 to nearly 2.0 depend-
ing upon the specific gasification process used, the medium Btu gas can subse-
quently be treated to yield the desired gas composition. Using a CO shift cata-
lytic reactor (see Figure 7-1), the ratio of H2/CO is adjusted via the reaction
(7-6)
Coal Liquefaction 195
Indirect liquefaction of coal generally follows one of three process schemes:
1. Fischer- Tropsch
2. Methanol synthesis
3. Catalytic conversion of methanol to gasoline
Normally Schemes 2 and 3 are integrated in the same plant in order to maximize
production of gasoline. Using Fischer- Tropsch synthesis, it is possible to obtain
high yields of both low and high molecular weight products, but the selectivity
towards intermediate weight products such as gasoline or diesel fuel is not good.
In order to maximize gasoline product and minimize heavy ends production,
methanol is first produced, followed by Scheme 3 using the Mobil "M" process.
Fischer- Tropsch Processing
In 1925, the German chemist team of Franz Fischer and Hans Tropsch devel-
oped a catalytic process to produce a variety of fuels from reacting carbon mon-
oxide with hydrogen. This technology was used in several German plants during
World War II for the manufacture of gasoline and other products. After World
War II, a pilot plant was operated by the U.S. Bureau of Mines in Missouri, and
a commercial plant (7,000 bbllday) was operated during the 1950s in Browns-
ville, Texas. This latter plant suffered a number of operational difficulties and
was shut down when cheap sources of natural gas and oil became available.
In 1980 the only major coal liquefaction plant operating on a commercial scale
in the world was the Sasol (Afrikaans acronym for South African Coal, Oil, and
Gas Corporation) I plant in Sasolburg, South Africa, which uses Fischer-Tropsch
processing to produce coal liquids. 2 At Sasol I a high ash subbituminous coal is
gasified in Lurgi gasifiers. The raw synthesis gas produced in this manner is
purified and then converted to gasoline, other hydrocarbon products, oxygenated
chemicals, and medium Btu gas (650Btu/scf). The Sasolliquefaction plant uses
both the high-velocity fluid-bed Synthol and the fixed-bed German Arge pro-
cesses. Sasol I has been operating since 1955 and produces gasoline, jet fuel,
diesel oil, middle distillates, and heavy oil. Two other plants, Sasol II and Sasol
III, both five times larger than Sasol I in terms of coal consumption, have been
constructed in South Africa. As of 1982, Sasol II, located at Secunda, 100 miles
from Sasolburg, was operational. In this plant only the high velocity, fluid-bed
Synthol process is used for liquefaction. The major liquid product is gasoline,
providing more than 50% of South Africa's motor fuel requirements. The liquid
output of Sasol II is ten times that of Sasol I.
The main products from Fischer-Tropsch processing are paraffins and olefins,
with smaller amounts of ketones, acids, and alcohols. For example, reactions
such as
(2n + I)H2 +nCO
(8-1)
196 Coal Processing and Pollution Control
(8-2)
(8-3)
can occur. 3,4 In addition the above products can undergo secondary isomerization
and/or cyclization to form branched-chain and aromatic compounds. The selec-
tivity and product mix of a given process is determined by the reactor configura-
tion, catalyst composition, H2/CO feed ratio, and operating conditions (tempera-
ture and pressure). The types of catalysts employed commercially include iron,
cobalt, nickel, ruthenium, and zinc, and often contain promoters (such as potas- ~-/
sium oxide) in small percentages.
For instance, if the fixed-bed (Arge) process is operated with an alkali-rich
iron-based catalyst, a low H2/CO feed gas, and a low temperature, the wax selec-
tivity can be increased from the normal 50% to above 75%. On the other hand,
operating the fluidized bed (Kellogg Synthol) with an iron catalyst of low alkali-
content and hydrogen-rich feed gas increases the methane selectivity from 10%
to about 80%. Table 8-1 gives the typical product distribution for fixed- and
fluid-bed reactors. A wide product distribution is an inherent feature of the Fis-
cher-Tropsch process. The maximum yields of gasoline and diesel fuel which
can be obtained in normal Fischer-Tropsch operation are about 40% and 18%,
respectively. The normal H2/CO ratio is about 2: 1, with a temperature range of
450F to 700F and pressures from 5 to 40 atm.
In South Africa the liquefaction process is usually operated to give maximum
gasoline selectivity. To meet octane specifications the required amount of gaso-
line is hydrorefined to saturate olefins and remove all traces of oxygen-contain-
ing compounds, followed by catalytic reforming. Hydrogenation is carried out
because straight-chain hydrocarbons produced by primary synthesis make a poor
quality gasoline. In contrast, a good quality diesel fuel requires mainly straight-
chain paraffins. Sasol II is designed to produce a mix of products: methane, light
petroleum gases, gasoline, and diesel fuel. 2
Improvements of yields from Fischer-Tropsch processing continues to be an
active research area. Mobil Oil Corporation has recently announced a two-stage
Fischer-Tropsch process, where the F-T product from a conventional reactor is
passed to a second reactor containing a zeolite catalyst (ZSM-5). The zeolite cat-
alyst is also used to produce gasoline from methanol and has the following reac-
tion characteristics:
1. The high boiling distillate and wax fractions are cracked to naphtha.
2. A large fraction of aromatics (yielding high octane) are produced.
3. Oxygenated compounds are converted to water and hydrocarbons.
Mobil has reported yields of 8% fuel gas, 6% LPG, and 86% gasoline (including
alkyl ate) in pilot plant testing of this process.
Coal Liquefaction 197
Table 8-1
Product Distribution in Sasol 13,4
Product
Methane (CI)
Light gas (C,-C.)
Gasoline (Cs-C12)
Light distillate (CIJ-CI9)
Soft wax (C,o-C30)
Hard wax (C30 +)
Oxygenates
Methanol Synthesis
Fixed Bed
ARGE
5
13
22
15
23
18
4
Fluid Bed
SYNTHOL
10
33
39
5
4
2
7
Methanol has the potential to be used directly as a transportation fuel, I but it
can also be converted to gasoline. The selective synthesis of methanol from CO
and H2 involves the following reaction:
(8-4)
Carbon monoxide and hydrogen may react in many other ways, but elimination
of the side reactions is accomplished by using very selective catalysts and appro-
priate operating conditions. By minimizing the undesirable reactions, the synthe-
sis reaction will proceed until equilibrium is reached. The equilibrium methanol
content in the effluent mixture decreases with increasing temperature and in-
creases with the square of the pressure. Two generic methanol synthesis pro-
cesses, called low and high pressure, are used commercially. 5.6 The low pressure
process operates at a lower temperature than the high pressure process, using a
different catalyst. Its advantage is that lower compressor costs are achieved.
The synthesis gas prepared for methanol production from coal gasification can
contain carbon dioxide as well as carbon monoxide. If the CO2 concentration is
not too high relative to the CO and H2 concentrations, no adjustments need be
made in synthesis gas preparation.5,6 The CO2 will be reacted later in the con-
verter according to:
(8-5)
or:
(8-6)
followed by:
(8-4)
198 Coal Processing and Pollution Control
The use of carbon dioxide in the synthesis requires 50% more hydrogen than car-
bon monoxide, thereby increasing the cost of gas compression. This disadvan-
tage is compensated somewhat by elimination of the need to remove carbon diox-
ide from the synthesis gas.
Preparation of the makeup gas (synthesis gas) is the same for both the high and
low pressure processes, except sulfur removal is more rigorous in the low pres-
sure case.7 The synthesis makeup gas might have the following composition:
Component
Hydrogen
Carbon Monoxide
Carbon Dioxide
Methane
Argon
Volume % (dry)
63.0
26.0
7.0
3.8
0.2
The hydrogen to carbon monoxide ratio from the gasifier is adjusted in a shift
reactor to achieve the above composition. Note that the ratio of 2: I for H2/CO is
not strictly required; generally a ratio between 2.3 to 2.5 is employed.
The high pressure process operates at about 5,000 psig. In large plants it is
economical to do all compression with centrifugal compressors. The minimum
capacity for such a plant is about 700 tons per day.6.7 The makeup gas is mixed
with the recycle stream in the last stage of the compressor and then proceeds to
the converter. Large plants typically use gas-quenched catalyst beds in the con-
verter for temperature control. The converter outlet stream contains about 5%
methanol by volume; the yield, based on CO +CO2 conversion, is approximately
95%-96%.
In the low pressure process developed by ICI (see Figure 8-2), the makeup gas
is compressed to about 765 psig. It is then mixed with the recycle gas from the
synthesis loop and fed to the converter. The converter is similar to that used in
the high pressure process. As mentioned earlier, the use of a lower temperature
and highly selective catalyst partially compensates for the equilibrium penalty of
low pressure operation. The converter effluent, however, has a lower concentra-
tion of methanol. This results in a higher recirculation rate but the lower rate of
production also eliminates the need for cooling coils and hydrogen quench in the
converter. This version of methanol synthesis appears to be more economically
attractive than the high pressure process.
In both high and low pressure processes, the converter effluent passes through
a condenser and a gas-liquid separator. The crude liquid product is 75% to 90%
methanol. The gas stream is water-scrubbed to remove methanol vapor. The
crude product is then purified in extractive distillation and refining columns.
Sidestreams of about 0.5% of the product streams remove impurities. The over-
head product stream from the refining column is 99.85%-99.95% methanol, and
the bottom stream is essentially pure water which is recycled to the top of the
Coal Liquefaction 199
NAPHTHA, SYNTHESIS GAS, ETC.
F'EEOSTOCIC
(NAPHTHA OR
HYQROCARBON
GAS-C02)
CRUOE
"ETHANOL
TAN'"
IMP\mITJ[S
HIGH-SOILING IMPURITIES
Figure 8-2. The ICI low-pressure methanol synthesis process.
extraction column. Thermal efficiencies for either methanol process are in the
50% to 55% range.
Gasoline Synthesis
Currently, there is only one commercially available process for the synthesis
of gasoline from methano1.4,s This is Mobil's MTG process. Methanol is con-
verted via a reversible dehydration to form dimethyl ether and then olefins:
2CH30H = CH30CH3 +H20 ~ olefins +H20
(C2H2n)
(8-7)
With a unique zeolite catalyst of high selectivity (ZSM-5) developed by Mobil, a
100 bbllday pilot plant is now in use in a cooperative project in West Germany
and a 12,000-14,000 bbl/day gasoline plant is scheduled to be completed in New
Zealand in 1985, using offshore natural gas as the primary feedstock.
In the MTG process (Figure 8-3), methanol is first dehydrated to an equilib-
rium mixture of methanol, dimethylether, and water in the dehydration reactor.
This mixture is then diluted with recycle gas and converted to hydrocarbons and
water over the ZSM-5 zeolite catalyst in the conversion reactor, which can be
either a fixed or fluid bed. The recycle gas is primarily light hydrocarbon prod-
ucts and provides some thermal mass to absorb the heat of reaction and reduce
200 Coal Processing and Pollution Control
the temperature rise in the converter to a manageable level. About 80% of the
total heat of reaction is released in the conversion reactor. The reactor effluent is
condensed and the aqueous, liquid hydrocarbon, and gaseous phases are sepa-
rated. Most of the gas is recycled. The converter may typically operate for 20
days before coking of the catalyst necessitates regeneration.
Table 8-2 gives material balance data for the Mobil M (fixed-bed) process.
Pilot plant tests at the 4 barrel per day level have shown methanol conversion to
be very nearly stoichiometric, with 56% water and 43.5% hydrocarbons being
formed. About 75% of the hydrocarbons are in the gasoline fraction. In formulat-
ing a gasoline of proper volatility, some of the n-butane formed is made part of ::-~
the gasoline. In addition, the remaining C3 and C4 gases, olefins, and isobutane
are alkylated to high-octane gasoline.8 Including the alkylation step raises the
yield of gasoline to nearly 90%. The following are typical properties of the syn-
thetic gasoline:
Molecular Weight
Specific Gravity
Research Octane Number
Direct Liquefaction
93
0.720
96.8
Direct liquefaction requires addition of hydrogen to coal so that the H/C ratio
is increased to the range where the product is a liquid. Liquids produced are of
two principal types:
I. A synthetic, largely aromatic, crude suitable for further processing to gaso-
line and other products.
2. A heavy fuel oil for use in boilers.
Only high volatile bituminous, subbituminous, and lignite coals are suitable for
direct liquefaction.
Like indirect liquefaction, direct liquefaction processes have their roots in
Germany,9 where about 100,000 barrels per day of synthetic liquids were pro-
duced towards the end of World War II. Reportedly, 90% of the German aviation
fuel was manufactured from coal. At about the same time liquefaction plants
were also operating in England, France, and Russia. At the conclusion of World
WarlI, the U.S. Bureau of Mines acquired documents and some equipment from
Germany and constructed a 300-barrel-per-day coal liquefaction plant. This
plant was operated between 1949 and 1954. After 1954, there was essentially no
activity until the late 1960s. Most of the recent research and development to de-
velop second-generation liquefaction processes have concentrated on operating
at less severe conditions, especially pressure. This is done by obtaining greater
rates of hydrogen transfer from the solvent to coal and by recycling liquids to
Coal Liquefaction 201
Table 8-2
Product Distribution for Mobil MTG Process
Operating Conditions:
Converter Outlet Temp.
Pressure
Recycle Ratio
Space Velocity
Product Distribution:
Yields: wt % of Methanol Charged
Methanol +Ether
Hydrocarbons
Water
CO, CO2
Coke +Others
Total
Hydrocarbon Distribution
Light Gas
Propane
Propylene
I-Butane
N-Butane
Butenes
Cs +Gasoline
Total
Gasoline
(Including Alkylate)
LPG
Fuel Gas
Total
Source: Mobil Oil Corporation
780F
315 psig
9:1
2.0
0.0
43.4
56.0
0.4
0.2
100.0
%
1.4
5.5
0.2
8.6
3.3
l.l
79.9
100.0
85.0
13.6
1.4
100.0
increase conversion. These engineering improvements ultimately translate to
lower costs. 10
Chemistry of Coal Liquefaction
The chemistry of coal liquefaction is significantly more complicated than that
of coal gasification, where primary consideration can be given to five to ten gas-
eous compounds of relatively simple structure. In coal gasification the operating
conditions are so severe that almost all chemical bonds in coal are broken, fol-
lowed by rapid reaction of the constituents with oxygen and steam. Under less
severe conditions (e.g., 750F), such as are used in coal liquefaction, chemical
bond breakage is not severe and only the weak connecting bonds will cleave,
which leads to release of a variety of chemical species appearing as liquid prod-
ucts.
202 Coal Processing and Pollution Control
Figure 8-3. Methanol-to-gasoline route.
The design of a coal liquefaction process has the objective of generating a
product which has a composition as close as possible to existing liquid fuels.
This implies that the hydrogen to carbon ratio must be increased (by adding hy-
drogen); other design objectives include removal of sulfur and nitrogen com-
pounds and mineral matter. Liquefaction is accompanied by evolution of gaseous
hydrocarbons, water vapor, ammonia, and hydrogen sulfide (not all nitrogen and
sulfur is released from the coal, however).
The liquefaction process is intimately related to low temperature pyrolysis4 in
the range between 350C and 550C. In fact, for most liquefaction processes,
pyrolysis is the rate-determining step. Pyrolysis reactions include loss of hy-
droxyl groups, dehydrogenation of some aromatics, cleavage of methylene
bridges, and rupture of alicyclic rings, all leading to generation of free radical
species which participate in rapid secondary reactions. The products of these re-
actions are very dependent upon the availability of free hydrogen and the pres-
ence of catalysts. The compactness of the coal molecular structure also affects
the type of free radicals. The possibility of escape of large molecules from the
solid coal matrix can be maximized by contacting (diluting) the coal with organic
solvents, sometimes formed from pyrolysis products of the same coal. This low-
ers the chance of recombination of the desired products.
The intrinsic nature of a given coal (i.e., its chemical structure) has a profound
influence on the liquefaction yields. 11-15 The majority of the bonds which can be
broken are identified in Figure 2-3, which is the Wiser molecular model for
coal. 16 This is but one of several models proposed by researchers. Given the wide
range of coals to be considered, no one molecular structure is generally accepted.
Table 8-3 shows a list of the major compounds produced from coal liquefac-
tion. Table 8-4 illustrates how the choice of liquefaction approach (low tempera-
Coal Liquefaction 203
ture carbonization, pyrolysis, solvent extraction, hydrogenation) affects the
product yields for the same coal. 15 The large variation in light and residual oil
yields is noteworthy.
Most coals when contacted with organic solvents imbibe fluid, swell, and dis-
solve to some extent in the solvent. A solvent such as pyridine can dissolve a
large percentage of coal at low temperature, and its behavior is non-selective,
i.e., the residue resembles the dissolved material. The dissolved coal may be a
true solution or a colloidal suspension.
At temperatures above 350C, a solvent such as anthracene oil can be em-
ployed to dissolve the coal. This solvent promotes thermal depolymerization re-
actions and increases liquid yields. A hydrogen atmosphere (high pressure) can
further increase th~ yields and quality of the extract by stabilizing the free radi-
cal reactions, thus reducing the molecular weight of the product. These hydro-
genation reactions are catalyzed by the mineral matter of the coal as well as by
Table 8-3
Composition of Coal Liquids
Hydrocarbons
N-paraffins
Isoparaffins
Cycloparaffins
Benzene
Naphthalene
Tetralin
Anthracene
Phenanthrene
Acenaphthylene
Pyrene
Chrysene
Fluorene
Oxygen Compounds
Phenol
Indanol
Dibenzofuran
Benzonaphthofuran
Sulfur Compounds
Thiophene
Benzothiophene
Dibenzothiophene
Nitrogen Compounds
Indole
Quinoline
Carbazole
Acridine
Benzacridine
Dibenzacridine
Table 8-4
Coal Liquids Obtained from Processing a
Utah Coal by Different Process Techniques15
Low-Temperature
Solvent
Liquids
Carbon ization
Pyrolysis
Extraction
Hydrogenation
Sulfur (Wt %)
0.82 0.98 I. 15 0.64
Nitrogen (Wt %)
0.91 0.86 1.04 0.76
Oxygen (Wt %)
3.8 4.5 8.02.8
Light Oil, up 10 200C (Vol %)
5.0 7.0 3.018.0
Residual Oil, +370C
(Vol %)
27.0 30.0 50.025.0
204 Coal Processing and Pollution Control
added external catalysts. Hydrogenation of the free radicals can also be enhanced
by using a hydrogen donor solvent such as tetralin. A hydrogen donor solvent
reacts with molecular gas-phase hydrogen and then transfers the hydrogen to
coal. The lower molecular weight liquefaction products then are more easily dis-
solved in the solvent. Tetralin as well as some other solvents provide hydrogen
molecules which are more mobile than hydrogen gas alone, thus allowing lower
operating pressures. In these solvents the extraction efficiency can approach
100% under laboratory conditions.
The products from liquefaction are difficult to characterize chemically. Other
means of characterizing these liquids must therefore be employed, inCiudingl3.14 '._J
1. Elemental analysis
2. Density, API gravity, viscosity
3. Distillation properties
4. Distribution of acidic, basic, and neutral compounds
5. Aromatic, paraffinic, olefinic carbons
6. Solubility in various solvents (pentane, benzene, pyridine)
Direct Liquefaction Processes
Liquefaction process research and development has been particularly active in
the United States during the past decade; 17-19there are presently no commercial
processes of this type. Table 8-5 lists the current development programs which
are being tested on a pilot scale (5 to 1,000 tons per day).IO These processes have
all shown enough promise to pass beyond the small bench scale to the pilot stage.
They may be grouped under the following headings:
1. Solvent extraction (SRC, Consol, Exxon Donor Solvent)
2. Catalytic hydrogenation (H-Coal)
The forerunner of the solvent extraction processes was the Pott-Broche process
developed in Germany, while the Bergius process is the original prototype for
catalytic hydrogenation in the presence of a solvent. Both processes were oper-
ated at pressures exceeding 2,000 psia.9,17
The term liquefaction can be misleading in some cases because the products
may be in liquid form only at high temperature (they solidify at room tempera-
ture). No liquefaction process is capable of complete conversion of the maf coal,
with about 75% being the maximum conversion expected. The flowsheets
for the various liquefaction processes are structurally similar, as discussed later.
Table 8-6 presents a comparison of the major liquefaction processes currently
being developed. 10
Coal Liquefaction
205
Table 8-5
Status of Direct Coal Liquefaction Projects
Process Type
Process
Developer
Location Size
Solvent
SRC-I
Southern Company
Wilsonville,
6 tons/day
Refining
Services AL
SRC-I1
Pittsburg &
Ft. Lewis
50 tons/day
Midway Coal
(Tacoma), WA
Company (Gulf Oil)
Slurry
H-Coal
Hydrocarbon Catlettsburg,
250-600
Hydrogenation
Research, Inc.
KY
tons/day
Synthoil
U.S. Bureau of
Bruceton, PA
0.25 to 10
-OJ
Mines
tons/day
Hydrogen
CSF Consolidation
Cresap, W VA 20 tons/day
Donor
Coal Company(now moth-
Solvent
balled)
Exxon EDS
Baytown, TX 250 tons/day
(mothballed)
Note: See Chapter 6 for a discussion of pilot plants based on hydropyrolysis processes (Toscoal,
Coalcon, CS/R).
Table 8-6
Comparison of Major Coal Liquefaction Processes10
SRC-I SRC-II EDS H-Coal
Operating conditions:
Pressure, psia
1,500 1,950 2,000 2,200
Temperature, of
850 850 850 850
Residence time, min
40 6040 30-70
Liquid yield, wt% maf coal
76 70 50* 74
Coal conversion, wt% maf coal
95 9570 94
H2 Consumption, wt% maf coal
2.4 4.74.3 3.8-5.3
Recycle system
Recycle of Recycle of Recycle of Recycle of
process
reactor
hydrogen- heavy
solvent
slurry
ated solvent distillate
Reactor
Upflow Upflow Upflow, plug-
Ebullated-
column
column flow tubular
bed cataly-
reactor
reactor reactor tic reactor
Catalyst
Mineral Ni-Mo for Co-Mo or
matter
solvent Ni-Mo
hydrogena-
tion
* C.-975F distillate.
206 Coal Processing and Pollution Control
Solvent Refined Coal Process (SRC). This process has been tested success-
fully at the 50-ton-per-day level at Ft. Lewis, Washington and at Wilsonville,
Alabama, but plans to build two 8,000-ton-per-day plants were cancelled in the
early 1980s. In the SRC process, the raw coal is first dried, pulverized, and
mixed with a coal-derived (anthracene-type) solvent boiling in the range of 500F
to 800F. The slurry is pumped with hydrogen (about 30 to 40 lb hydrogen per
ton of coal) to between 1,500 and 2,100 psig and heated to about 850F. The
structure of the coal is broken down, about 95% of the maf-coal hydrocarbons
dissolve, and a small amount of the carbon reacts with the hydrogen, producing
light hydrocarbons.lol? "'.-~
As shown in Figure 8-4, the effluent from the dissolver section goes to a sepa-
rator where the overhead gas is condensed to liquid hydrocarbons. The noncon-
densable hydrocarbon gases and hydrogen are recycled to the process. The
slurry-bottoms from the separator consists of the coal solution and unconverted
coal and is fed to a filter feed tank. The slurry from the bottom of the filter tank
is filtered and the undissolved coal is separated as a filter cake. The filtrate is
preheated and vacuum-flashed to remove recycle solvent. The liquid vacuum
bottoms is the product SRC (which solidifies at 300F-400F), suitable for use
as a power plant fuel. This product typically has low ash (0.1 %) and low sulfur
1%), with heating value of 16,000 Btu/lb.
The SRC-I filter cake is washed and dried to remove wash solvent. The dried
residue is composed of about 40% organic (mostly coal) material and 60% ash.
The residue contains all of the inorganic sulfur and sometimes up to 50% of the
COAL HYDROGEN
SLURRYING
1200 psi
23 D'C
DiSSOLUTION
1000 psi
440'C
FilTRATION
VENT GAS
SOLVENT
RECOVERY
CHEM.
PRODUCTS
DEASHED
FUEL
LlQU I D
PRODUCTS
ASH WITH
INORGANIC SULFUR
ASH
SOLVENT RECYCLE
SULFUR
Figure 8-4. The solvent refined coal process.
Coal Liquefaction 207
organic sulfur. In most cases the residue will not satisfy a 70% sulfur removal
requirement. The overhead from the vacuum flash, the wash solvent, and light
liquids removed in other parts of the process are separated into (I) a light C5 to
400F liquid by-product, (2) a 400F to 500F boiling liquid, used as filter wash
solvent, and (3) a 500F to 800F boiling process solvent, which is recycled. Ta-
ble 8-7 presents the typical product distribution for the SRC-I process. SRC-I
tests at Ft. Lewis and Wilsonville have indicated that the process is operationally
reliable except for mechanical problems with valves and solid/liquid filtration.
Some valves do not survive beyond one month of operation. Promising ap-
Table 87
Product Distribution for Solvent Refined Coal (SRC-1)10
Typical SRC Composition:
C
H
N
o
S
Ash
HHV
Operating Conditions:
Temperature
Pressure
Coal Feed Rate
Solvent/Coal Ratio
Gas Feed Rate
Hz Cone. in Feed Gas
Typical Yields:
CI
C2
C3
C4
CO
COz
HzS
Light Oil
Wash Solvent
Process Solvent
SRC
Ash
Unreacted Coal
HzO
Total
Hz Consumption
87.7
5.3
1.2
5.0
<0.5
0.2
16,000 Btullb
800-900F
1,000-2,500 psig
25-100 Ibthrtft3
1.5-3.0 (weight basis)
15,000-30,000 scf/ton-coal
60-95 mol %
Yield (wt% dry coal)
2.2
1.3
1.1
0.8
0.1
1.2
2.1
6.6
8.0
0.1
58.3
9.3
6.6
4.7
102.4
2.4 by weight of dry coal
208 Coal Processing and Pollution Control
proaches to replace leaf filters include continuous centrifugation and the Kerr-
McGee critical solvent deashing process. 20
Another version of this process, called SRC-II, produces an all-distillate liquid
product at the expense of higher hydrogen consumption. This is done by increas-
ing the residence time and using a recycle slurry of catalytically active minerals,
such as iron sulfide (pyrite), yielding 15%-20% gas (CI-C4), 45%-50% distil-
late syncrude (including 15% naphtha), and 35%-40% residue (5%-10% undis-
solved coal, the rest SRC). The distillate yield is about 2.5 bbllton coal with a
hydrogen requirement of 5% of the coal weight. 20.21 The sulfur level of the SRC
usually satisfies the 70% removal standard. The SRC-II process eliminates the ,-
solid/liquid separation step. Not all coals are suitable for SRC production, with
coal mineral matter believed to be one reason for high variability in process per-
formance.
Consol Synthetic Fuels (CSF). This process is an early example of the first
class of liquefaction processes, involving a combination of pyrolysis and hydro-
genation. Hydrogen is usually supplied through a hydrogen donor solvent such as
tetralin, although sometimes a small amount of molecular hydrogen is added.
Ash is filtered or otherwise separated and the partially hydrogenated coal further
hydrogenated. The CSF process, shown in Figure 8-5, used a ZnCh catalyst at
4,200 psi and 465C for this stage. The hydrogenated solvent was recovered for
recycle. The CSF process was operated previously at the 20-ton-per-day level,
HYDROCARBONS
COAL
HYDROCARBON
GASES TO REFINERY
SYNTHETIC CRUDE
OIL TO REFINERY
ASH
HYDROGEN RECYCLE
Figure 8-5. Simplified flowsheet for H-coal process.
Coal Liquefaction 209
HYDROGEN GAS
COAL
HEAVY SYN.CRUDE
,SYN. CRUDE
SLURRYING
95'C
EXTRACTION
380'C
SLURRY
SOLVENT
RECOVERY
LI G HT
Oil Ii
SOLVENT
EXTRACT
HYDROGENATION
4200 psj
465'C
HYDROGEN
DISTillATION
GAS
RECYCLE SOLVENT
lOW
TEMPERATURE
CARBONIZATION
CHAR
HYDROGEN - DONOR SOLVENT
Figure 8-6. CSF process-synthetic crude from coal.
but has now been abandoned as a commercial candidate due to operational prob-
lems, mainly in solid-liquid separation at high temperature and pressure. I?
Exxon Donor Solvent (EDS). This process is similar to the CSF process and
is now the leading commercial donor solvent candidate. The EDS process is de-
signed to maximize liquid products. It has been operated at a pilot scale (1.0 ton
per day), and demonstration scale (250 tons per day) in Baytown, Texas. The
feed coal is crushed, dried, and slurried with hydrogenated recycle solvent (see
Figure 8-6, References 10 and 22). This slurry is fed to the non-catalytic lique-
faction reactor with gaseous hydrogen. The reactor is an upward plug flow de-
sign which liquefies the coal at 800F to 880F and 1,500 to 2,000 psig. The
hydrogen donor-solvent is a 400o/850F boiling range material and is fractionated
from the middle boiling range of the liquid product. Table 8-8 gives the yield
distribution of the process for three coals tested.
The reactor effluent is separated by a series of conventional distillations into
the recycle solvent depleted in donor hydrogen, light hydrocarbon gases, C4-
1000F distillate and a heavy vacuum bottoms stream. Therefore no filtration is
required. The vacuum bottoms slurry contains 1000F + liquids, unconverted
coal, and coal mineral matter. The recycle stream, which is relatively free of
catalyst poisons, is hydrogenated in a conventional fixed-bed catalytic reactor,
using cobalt or nickel molybdate catalyst.
In the original flow sheet, the vacuum bottoms stream was sent to a Flexicok-
ing unit with air and steam to produce additional liquid products and low Btu fuel
gas for process heating. Flexicoking uses low pressure fluidized beds to convert
210 Coal Processing and Pollution Control
Table 8-8
Product Yields of EDS Process for Different Coals 10
Residence time, min
Yields, wt% maf coal:
H2
H20 +CO,
H2S +NH3
C,-C3 gas
C.-IOOOF liquid
IOOOF+bottoms
Illinois
bituminous
40
-4.3*
12.2
4.2
7.3
38.8
41.8
Wyoming
subbituminous
60
-4.6
22.3
0.9
9.3
33.3
38.8
Texas
lignite
25-40
-3.9
21.7
1.7
9.1
33.3
38.1
* Negative values denote consumption
essentially all of the organic matter in the bottoms to liquid products and fuel
gas. Hydrogen for the process is produced by steam reforming of the light hydro-
carbon gases. Alternatively, partial oxidation gasification or direct combustion
of the vacuum bottoms may be employed. In the current version of EDS, the
latter approaches are preferred over Flexicoking.
The total liquid product is a mixture of the liquefaction and Flexicoking prod-
uct streams. That portion of the liquids which boils below 350F is suitable for
gasoline and petrochemical manufacturing, while the higher boiling components
may be used in fuel oil applications. The higher boiling fraction contains about
0.6% (wt) sulfur and 0.8% (wt) nitrogen. These levels maybe reduced by further
hydrotreating.
The testing of the EDS process has been sponsored by Exxon plus other pri-
vate and public organizations. The coals tested up to 1982 included Illinois No.6
bituminous (Monterey No.1 mine), Wyoming subbituminous (Wyodak mine),
and Texas lignite (Big Brown mine). For the three coals, the optimum reactor
residence time was 25 to 40 minutes. Longer residence times causes cracking of
liquids to gases. While the lower rank coals gave higher conversions and demon-
strated enhanced reactivity, the liquid yield for the bituminous coal was superior
to the low rank coals, when the yield from Flexicoking is included. Another
problem with low rank coals is calcium contained in the ash, which causes de-
posits on the reactor walls. 23,24
H-Coal. This process developed by Hydrocarbon Research, Inc. has been suc-
cessfully piloted at the 3-ton-per-day and 600-ton-per-day levels. In this process
coal is dried, pulverized to 40 mesh, and slurried with recycle oil produced in the
process (see Figure 8_7).25,26The slurry is pumped to the 2,260 psig reactor oper-
ating pressure, mixed with hydrogen, preheated to about 845F and fed to the
reactor. The reactor feed and recycle stream enter the reactor at the bottom of the
Coal Liquefaction 211
HYDROGEN RECYCLE
H20
FUEL GAS
Figure 8-7. Exxon donor solvent (EDS) process.
bed of ebullated catalyst. The cobalt-molybdate catalyst is fluidized by the liquid
feed. Depending on the operating conditions, the product yield can be all distil-
late material or distillate plus a liquefied residual.
The gaseous output from the reactor is scrubbed with a medium volatility oil to
remove light hydrocarbons, and the resulting stream of hydrogen is recycled.
The liquid slurry leaves the top of the reactor and is flashed to atmospheric pres-
sure. The vapor phase from the flash is a high-Btu gas after purification to re-
move H2S and CO2 The liquid phase consists of syncrude, ash, and unreacted
coal, which is flashed in a vacuum drum to obtain a vacuum-overhead distillate
and a vacuum-bottoms slurry. Some of the overhead fraction is recycled to form
the coal slurry feed. If the process is operated to produce fuel oil rather than
distillate, solid/liquid separation is problematic.
This process can produce a syncrude which may be processed to yield 100 +
octane gasoline. At milder operating conditions using less hydrogen, a low sulfur
fuel oil results. Hydrogen (14,000 to 20,000 scflton coal liquefied) is produced
by gasification of coal, steam reforming the hydrocarbon gases, or gasification
of the vacuum bottoms. Table 8-9 gives the H-Coal product distribution.
The 600-ton-per-day H-Coal pilot plant at Catlettsburg, Kentucky is the larg-
est direct liquefaction plant ever constructed in the United States. Sponsored by
both private and public entities, the plant was operated between 1980 and 1982
using Kentucky, Illinois, and Wyodak coal. The longest sustained operation was
45 days. The operating conditions were adjusted to produce either syncrude or
212 Coal Processing and Pollution Control
Table 8-9
Product Yields of H-Coal Process10
Recycle oil/coal ratio
Reactor temperature, of
Hydrogen partial pressure, psia
Yields, wt% of dry coal:
C,-C3
C4-400F
400-975F
975F +
Unconverted coal
Ash
H20
NH3
H2S
CO +COz
Total
Hz consumption, wt% of dry coal
Sulfur in 400F +oil, wt%
Fuel-oil mode
2.1
850
1,760
7.71
16.90
18.28
32.45
6.75
10.95
6.67
0.53
2.55
l.01
103.80
3.80
0.49
Syncrude mode
2.1
850
1,830
9.97
23.66
23.21
19.25
5.68
11.67
7.37
0.84
2.65
0.95
105.25
5.25
0.26
boiler fuel. The major problems experienced in these tests were largely mechani-
cal (e.g., valve and pump failures);25,26 in addition, various components in coal
can contribute to catalyst poisoning.
A similar process (Synthoil) was tested by the Bureau of Mines in the
1970s.4,I0,17Coal (high sulfur bituminous) forms a 30% slurry in coal-derived oil
and passes through a fixed bed of pelletized cobalt-molybdate catalysts under
conditions of turbulent flow. Pressures and temperatures are the same as for H-
Coal. Turbulence promotes contacting and prevents obstruction, resulting in a
low sulfur and ash product. This process is no longer a candidate for commercial-
ization because of catalyst poisoning problems.
Third generation liquefaction processes. A number of so-called advanced
liquefaction processes are under development, including two-stage solvent refin-
ing and supercritical extraction. 4,27The latter process exploits the characteristic
of supercritical solvents that the low volatility compounds in coal are highly solu-
ble in a compressed gas above its critical temperature, thus increasing liquid
yields. The extraction gas should have a critical temperature near the pyrolysis
temperature of coal; according to tests by the National Coal Board in England,
toluene is an attractive extraction gas with a critical temperature of 606F. To-
luene is capable of processing caking coals. The coal liquids are separated from
the extract by pressure letdown. A typical yield by supercritical extraction is 21%
extract, 67% char, and 6% gas. The product is a low-melting, glassy solid, with
a softening temperature of 120F to 150F, and molecular weight ranging from
Coal Liquefaction 213
300 to 500. The solid residue is similar to char, although with a higher volatile
content than with most chars obtained from pyrolysis.4
Properties of coal liquids. Coal liquids produced from direct liquefaction are
not suitable for use as a high grade fuel without further processing. Coal liquids
generally resemble petroleum residual oils (black oils) more than other petroleum
products, although their physical and chemical characteristics are sufficiently
different to place them in a separate classification.28 The distillation curves of
several coal liquids and of a typical domestic crude oil are compared in Figure 8-
8. In general terms coal liquids contain more nitrogen and oxygen than petro-
leum crudes. 29 Coal liquids are more aromatic and correspondingly more hydro:
gen-deficient than equivalent cuts from crude oils, thus the carbonlhydrogen
ratios of most coal liquids are considerably higher than those for petroleum
100
COED SYNCRUDE
~
60

~
w
::1: ;:)
...J
0> 40 I
I I~;
J
I
UPGRADED
f!t
SRC (0)
80
o
o
TEXAS CRUDE
200 400
TEMPERATURE (oC)
600
Figure 8-8. Distillation curves for coal liquids.
214 Coal Processing and Pollution Control
crudes (see Table 8-10). Some coal liquids contain substantial quantities of as-
phaltenes, a potential problem for subsequent upgrading. Coal liquids contain a
far higher proportion of higher boiling materials.
The upgrading of coal-derived liquids should achieve the following goals:
1. Reduction or removal of sulfur, nitrogen, oxygen, trace metals, ash.
2. Hydrogenation and increase of the hydrogen/carbon ratio.
3. Reduction in viscosity and boiling range.
4. Improvement of storage stability.
5. Reduction in toxicity and carcinogenicity.
(For data on upgrading of synthetic crudes, see References 28, 30, and 31.)
Commercialization and Economics of Synfuel Production
During the 1970s a great deal of interest in synthetic fuels arose in the United
States as well as the world because of the rapidly escalating price of oil and
shortfalls in oil supply. However, it appears that responses to the supply-demand
situation, such as increased conservation, production of more fuel-efficient auto-
mobiles, additional oil production, and a flattening of oil prices, have considera-
bly eased market pressures. It is doubtful that there will be much incentive (other
than for strategic purposes) during the 1980s to develop synthetic fuels, simply
because the cost of coal liquids is higher than that for crude oil. If oil prices
remain stable during this decade, the economic justification of a liquid synfuels
venture is very unlikely and may actually grow less attractive.
Even when the projected costs of synfuels appeared to be comparable to those
of conventional fuels in the late 1970s, there was still too much uncertainty in
market conditions to undertake a large-scale commercial venture with capital
costs of $2 billion to $4 billion. As discussed in Chapter 7, there was also a tendency
to underestimate the cost of synfuels, mainly due to a lack of experience in syn-
fuels production. The formation of a U.S. synfuels industry mainly is limited by
Table 8-10
Comparison of Typical Coal Syncrudes with Petroleum Crude OilS29
Hydrogen (% by mass)
Nitrogen (% by mass)
Basic nitrogen (% of nitrogen mass)
Oxygen (% of mass)
Sulfur (% of mass)
Aromaticity (Atom % aromatic carbon)
Petroleum Crudes
11
0.41
25-30
0.30
1.96
20-35
Coal Syncrudes
6-8
1.40
40-70
3.60
0.95
60-75
Coal Liquefaction 215
1. The difficulty in raising large amounts of risk capital by developers.
2. The lack of financial incentives, including faster depreciation, higher debt
financing, and tax credits. 32
3. The uncertainty about future world oil prices as well as future monetary
inflation.
In the absence of a concerted government program to stimulate synfuels, the pri-
vate sector is and will be very reluctant to undertake a major program in coal
liquefaction.! _
Based on a variety of studies on costs of synthetic fuels from coal and oil
shale,33,34 it appears that oil from oil shale and medium Btu gas are the most
economically attractive options for the near future. Table 8-11 summarizes the
approximate capital and operating costs (1980 dollars) for a variety of synfuel
options for equivalent 50,000-barrel-per-day plants, while Table 8-12 gives the
cost of fuels using 100% equity financing and a 10% rate of return (no inflation
effects).!,33 The strategy which is most attractive appears to be combined produc-
tion of liquid fuels with SNG, rather than production of methanol or gasoline
only. The costs stated here probably have 30% reliability, which makes syn-
fuel production potentially much more expensive than gasoline from crude oil.
Table 8-13 gives the distribution of various products and energy efficiencies ex-
pected from various synthetic fuel options.! The fraction of transportation fuel
includes methanol, gasoline, and LPG. In general fuels produced from indirect
Table 8-11
Best Available Capital and Operating Cost Estimates for Synfuel Plants
Producing 50,000 BID Oil Equivalent of Fuel to End Users1
Annual Operating Costs
(Exclusive of Coal Costs)
(Million 1980 $)
250
150
200
Process
Oil Shale
MethanollSNG
Methanol
Mobil Methanol
to Gasoline/SNG
Mobil Methanol
to Gasoline
Fischer TropschlSNG
Direct Coal Liquefaction
SNG
Methanol from
Wood
Ethanol from Grain
Capital Investment
(Billion 1980 $)
2.2
2.1
2.8
2.4
3.3
2.5
3.0
2.2
2.9
1.8
170
230
190
250
150
610
860
216 Coal Processing and Pollution Control
Table 8-12
Consumer Cost of Various Synthetic Transportation Fuels
With 100% Equity Financing and 10% Real Return on
Investment Plant or Refining Gate'
Plant or Refinery Gate
Delivered Consumer Cost of Fuel
Product Cost
$/Gallon Gasoline
Process
$/bbl 011 Equivalent Equivalent $/106 Btu
Reference Cost of
Gasoline from $32/bbl Crude Oil
47 1.20 9.50
Oil Shale
52 1.30 10.40
MethanoUSNG
43 1.30 10.60
Methanol
58 1.60 13.00
Mobil Methanol to Gasoline/SNG
49 1.25 10.00
Mobil Methanol to Gasoline
67 1.60 12.90
Fischer TropschlSNG
52 1.30 10.40
Direct Coal Liquefaction
77 1.85 14.60
SNG
45 1.15 9.10
Methanol from Wood
68 1.85 14.70
Ethanol from Grain
71 1.80 14.50
liquefaction tend to match up better with U.S. transportation fuel requirements
than those from direct liquefaction. While there are some practical problems in
using methanol or methanol! gasoline in current automobiles, 35 there is long-
range potential for the transportation market, possibly in fleets which are exclu-
sively based on methanol use. Methanol can also be employed to manufacture
octane extenders such as methyl tertiary butylether (MTBE).
A number of cost studies on indirect liquefaction of coal to produce methanol
and gasoline have been performed recently.36-47 These references provide more
details on the costs of various pieces of equipment and financial assumptions em-
ployed in cost estimating, and are a valuable source of data on gasification costs.
There has also been some disagreement on the relative costs of indirect versus
direct liquefaction. The adherents of direct liquefaction have argued that in the
long term, these processes should be less expensive than indirect liquefaction,
while acknowledging that in the short term established technologies such as Fis-
cher-Tropsch or methanol are probably more attractive. However, other re-
searchers have argued that indirect liquefaction will always be preferred over di-
rect liquefaction, mainly because of the relatively high cost of hydrogen required
(versus steam for gasification).47
Coal Liquefaction 217
It is clear that research and development funding required to bring a single
direct liquefaction process to commercialization is significant, on the order of
several billion dollars. Hence when only a few plants are to be constructed, it
will be difficult for the private sector to absorb this front-end capital require-
ment. Another impediment facing direct liquefaction plants is the wide variety of
compounds, some of which are carcinogenic, that are produced during process-
ing.48 On the other hand, indirect liquefaction plants also pose a range of occupa-
tional hazards;1 processes based on the Lurgi gasifier will generate a large quan-
tity of pyrolysis products. For this reason entrained-bed gasification (such as
Texaco) may be preferred over the fixed-bed systems.
Table 8-13
Selected Synfuel Processes and Products and their Efficiencies'
Energy Efficiency (%)
Fuel Transportation Fuel
Product Product
(Coal Input) (Coal Input)
NA NA
Process
Oil Shale
MethanoliSynthetic
Natural Gas (SNG)
Methanol
Mobil Methanol to
Gasoline/SNG
Mobil Methanol to
Gasoline
Fischer Tropsch/
SNG
Direct Coal
Liquefaction
Synthetic Natural Gas
Methanol from
Wood
Ethanol from
Grain
NA = not applicable
Fuel
Product
(% of output)
Gasoline (19)
Jet Fuel (22)
Diesel Fuel (59)
Methanol (48)
SNG (49)
Other (3)
Methanol (100)
Gasoline (40)
SNG (52)
Other (8)
Gasoline (87)
Other (13)
Gasoline (33)
SNG (65)
Other (2)
Gasoline (33)
Jet Fuel (49)
Other (18)
SNG (100)
Methanol (100)
Ethanol (100)
65
55
63
47
56
57
59
47
NA
33
55
27
41
17
47
o
47
NA
218 Coal Processing and Pollution Control
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