Polk 2004

COAL LIQUEFACTION
1. Introduction
Liquefaction is the generic term for converting coal to fuels and chemicals (see
also FUELS, SYNTHETIC—GASEOUS FUELS; FUELS, SYNTHETIC—LIQUID FUELS). Coal (qv)
has been described variously, depending on the context, as ‘‘nature’s dump’’
and ‘‘nature’s storehouse.’’ The reason is because, although the primary constitu-
ents of coal are carbon and hydrogen, one also finds oxygen, sulfur, and nitrogen
(generally classified as ‘‘heteroatoms’’). Lesser amounts of many other elements
can be detected (as inorganic oxides, or ‘‘mineral matter’’) as well. All methods for
converting coal to fuels, and most methods of converting coal to chemicals,
require both an increase in the hydrogen-to-carbon (H/C) ratio (from around
0.7 to around 2, order of magnitude, both molar) and removal of sulfur, nitrogen,
and the other elements.
Coal can be converted to liquid and gaseous fuels and chemicals by
two different processing routes, normally termed ‘‘direct’’ and ‘‘indirect.’’
Direct liquefaction processes result in primary products (liquids or solids) of
molecular weight greater than, or of the order of magnitude of, the fuels and
chemicals desired. Catalysts may be used. Secondary processing is usually
required to form fuels and chemicals. Some direct liquefaction schemes
also involve chemical pretreatment of the coal. Other schemes involve a second
feed source, generally heavy fractions of petroleum (coal-oil co-processing),
sometimes recyclable wastes (coal-waste co-processing). In indirect liquefaction
(IL) processes, however, the first step is always gasification of coal to
synthesis gas (‘‘syngas,’’ CO þ H2), and this is followed by additional steps in
which the syngas is catalytically recombined to form hydrocarbons and /or
oxygenates.
In the 1990s, the U.S. Department of Energy (USDOE) considered
catalytic two-stage liquefaction and coal/oil and coal/waste co-processing as
the two major elements of its direct coal liquefaction (DCL) program. The
major elements of the indirect coal liquefaction (ICL) program were advanced
Fischer–Tropsch technology for transportation fuels and processes for oxyge-
nated fuel additives and high-value chemicals. At the turn of the century,
the USDOE’s Vision 21 Concept had as a goal the development of a suite of
‘‘modules’’ that can be interconnected to design a plant that depends on local
resources and needs. The object was (and is) for the plant to be able to use
one or more fuel types (coal, natural gas, biomass, petroleum coke from oil refi-
neries, and waste from municipalities) and, coupled with carbon sequestration
techniques, to produce multiple products (one or more of electricity, heat, fuels,
chemicals, and hydrogen) at high efficiencies with no emission of greenhouse
gases (1).
Reviews of coal liquefaction may be found in References 2–5. In this
article, the processing schemes for DCL are first discussed, including
some of the research results on catalytic DCL, followed by co-processing
schemes. This is followed by a discussion of ICL, including some of the more-
recent bench-scale, pilot-scale, and demonstration-scale work worldwide.
Kirk-Othmer Encyclopedia of Chemical Technology. Copyright John Wiley & Sons, Inc. All rights reserved.
2 COAL LIQUEFACTION
2. Direct Coal Liquefaction
From the previous discussion, there are two chemical concerns and two physical/
engineering concerns in direct coal liquefaction (DCL). The two chemical con-
cerns are the introduction of hydrogen to the parent coal molecule and the
removal of heteroatoms (nitrogen, sulfur, and oxygen) and mineral matter. The
other concerns are the transport of solid and slurry-phase material, and separa-
tions, generally solid from liquid. The last two have ramifications in the econom-
ics of commercial-scale plant design.
Over the years, advances in the understanding of the use of catalysts and
improvements in catalyst formulations have allowed for significant advances in
DCL. One limitation of the thermal process was the production of large quanti-
ties of gaseous products; the introduction of improved catalytic processes has led
to a reduction in the amount of the light products and to an increase in the
desired liquid products, as illustrated in Figure 1 (6).
Hydrogenation (hydroprocessing, hydrorefining, solvent refining, or hydro-
liquefaction) and pyrolysis are the two means used for DCL. In hydrogenation,
the organic components of coal are dissolved under a moderate-to-high hydrogen
pressure using a solvent, generally a coal-derived heavy aromatic material (7).
Here the primary reactions are a combination of homogeneous thermal cracking
(ie, free-radical generation) and heterogeneous hydrogenation (involving hydro-
aromatics in the slurry vehicle and/or the coal itself as hydrogen-transfer
agents). Rapid and efficient capping of the primary free radicals generated by
heating is thought to be necessary to prevent retrogressive reactions leading to
formation of solid char (8). Other theories of coal liquefaction suggest that hydro-
gen can engender reactions involving scission of strong bonds in the coal macro-
molecule, and hence hydrogen can act as an active bond-cleaving agent rather
than simply as a passive radical quencher (9). Typically, the object of hydrogena-
tion is to maximize the yield of distillate fractions that can subsequently be
converted into fuels. [Distillate materials comprise the naphtha fraction, typi-
cally boiling between C5 and 420 F (215 C), plus the middle distillate fraction,
IG
Temperature, ºC
500
Saarberg
475
EDS Bottrop
450 Dow
H-Coal
Wilsonville
425
400
3 6 9 12 15 18 21
C1 – C4, Wt.%
Fig. 1. Role of catalysts during industrial coal liquefaction in reducing reaction tempera-
tures and light products (6).
COAL LIQUEFACTION 3
typically between 300 F and 700 F (150 C and 370 C), with the exact cuts
depending on product specifications].
Pyrolysis normally involves heating in an inert or reducing atmosphere and
produces char and oil, as well as often a low-BTU gas. The relative proportion of
char to the other products can be quite high; hence, the rationale for liquefaction
by pyrolysis is often not production of coal-derived distillate materials but rather
of the solid. Hydropyrolysis (heating in the presence of hydrogen) and/or pyroly-
sis under conditions of rapid heating can, however, generate yields of distillate
products significantly in excess of the volatile matter content of the starting coal.
2.1. Hydrogenation. Early Work. Bergius was awarded the Nobel
Prize for Chemistry in 1931 based on his pioneering work on DCL (10). The
work of I. G. Farben in Germany on the Bergius process led to the development
of a two-stage, direct-hydrogenation liquefaction process. Here, primary coal
solubilization was carried out in the first stage using added disposable catalysts
in bubble-column reactors. Distillate materials were then catalytically upgraded
to liquid transportation fuels using supported hydrotreating/hydrocracking cat-
alysts in fixed-bed reactors (11). The Bergius process was significant during
World War II but fell into disuse as a result of the decreasing price of crude.
In the 1930s, the U.S. Bureau of Mines experimented with direct liquefac-
tion using the Bergius process and a small-scale test unit that could process
100 lb/day (45 kg/day) of coal. This work led to modifications of the pyrolysis pro-
cesses then in use, and it made possible the Karrich process, where the coal is
heated to approximately 450–700 C to produce an oil and a carbonaceous resi-
due. Commercial-scale Karrich plants were built in the United States in the
1930s.
After World War II, the U.S. Bureau of Mines initiated a major efforts in
both direct and indirect coal liquefaction. For direct liquefaction, parts of a
plant were moved from Germany to an abandoned ammonia plant in Louisiana,
MO, and incorporated into a plant that produced 100 bbl/day of fuels. However,
the development and production of cheap crude oil in the Middle East caused the
plant to be shut down. In the 1970s, interest was rekindled when oil prices
increased and a better understanding of the fundamentals of hydrogen donation
made solvent refining more attractive as a DCL technique (7).
Solvent–Refined Coal Process. Work in the mid-1960s by the Spencer
Chemical Co. (12) and during the 1970s by its successor, the Gulf Chemical
Corp. (now Chevron) led to two solvent-refined coal (SRC) processing schemes:
SRC-I for production of low-ash solid boiler fuels and SRC-II for distillates, eg,
‘‘syncrude.’’
A schematic flow diagram for the SRC-I process is shown in Figure 2. Coal
is first slurried in a recycle solvent, then preheated, and finally reacted in a bub-
ble column-type reactor at 450 C in the presence of gaseous hydrogen. Because of
the high reactivities of the coals tested, primarily eastern U.S. high- and med-
ium-volatile bituminous coals, no catalysts were added and the reaction was car-
ried out at pressures as low as 6.9 MPa (1000 psig). The mean residence time in
the reactor was reported to be on the order of 30 min. Solids were removed by use
of either rotary pressure precoat filters or hydroclones. SRC yields (computed as
the mass of SRC-I per mass of moisture- and ash-free (maf) coal exclusive of light
hydrocarbon gas make) of approximately 60% were achieved. Ash removal was
4 COAL LIQUEFACTION
Vent gases
Recycle Fuel gas
Gas
hydrogen Sulfur
Fresh hydrogen treatment and
compressor
separation
Water
Slurry preparation Fired

preheater
Grinding Let-down
Reactor
and and flash
drying system
Feed coal
Supplemental
coal to
gasifier Slurry
feed
pump
Filter cake and carbon mineral matter Filtration
Steam Hydrogen
production
Oxygen Light
ends
Filtrate
Distillation
Solvent recycle
Mineral
matter
Solidification Solvent refined

and solvent coal (SRC)
recovery
Fig. 2. SRC-I process. The reactor operated at 450 C and 6.9 MPa (1000 psig).
high by this process and, depending on the forms of sulfur in the parent coal
(inorganic/organic), sulfur reduction was also substantial. Data for a Kentucky
No. 9 high-pyrite eastern U.S. coal showed SRC-I/parent-coal weight percent
ratios for total sulfur as 0.22 and for mineral matter as 0.0095. The heating-
value ratio was 1.2.
The SRC-I technology was tested at a large-scale (50 t/d) demonstration
plant in Fort Lewis, Wash., which was commissioned in 1974. This plant oper-
ated for several years, but severe problems were encountered, primarily with sol-
vent balance and with operation and reliability of the solids-separation portion of
the facility (12). The final design for this facility differs from Figure 1 in that an
expanded-bed hydrocracking unit was added as a second-stage reactor to
increase the yield of distillate material (13). Total solids [SRC plus two-stage
liquefaction (TSL)] were reduced to approximately 27% by this modification,
resulting in an increase in distillate materials. Bench-scale testing of the hydro-
cracking step indicated that the naphtha fraction, C5 to 420 F (215 C), would
be low in sulfur (0.01 wt %) but high in nitrogen (approximately 0.1%). Severe
hydrotreating of this material would be required before refining into gasoline
via catalytic reforming. An overall thermal efficiency (defined loosely as the
energy capable of being generated by combustion of product from a unit weight
of feed per energy generated by combustion of a unit weight of feed) of this pro-
posed facility was calculated to be 70%.
The SRC-II process, shown in Figure 3, was developed to minimize the pro-
duction of solids from the SRC-I coal-processing scheme. The principal variations
were incorporation of a recycle loop for the heavy ends of the primary liquefac-
tion process and imposition of more-severe conditions during hydrogenation (5).
It was quickly realized that minerals that were concentrated in this recycle
COAL LIQUEFACTION 5
Purified hydrogen
Vapor–liquid separators
Cryogenic
separation
Slurry Dissolver Pipeline
mixing tank gas
Dried
pulverized Slurry
coal preheater LPG
Acid gas removal
Product Light
Reciprocating slurry liquid
pump Sulfur
Light
Make-up distillate
hydrogen
Fuel oil
Shift conversion Gasifier
and purification
Fractionator Vacuum tower

Steam
Mineral residue slurry
Inert slag
Fig. 3. SRC-II process, where LPG is liquefied petroleum gas.
stream served as heterogeneous hydrogenation catalysts that aid in the produc-

tion of distillate. In particular, pyrrhotites, FexSy (where x and y are 1), non-
stoichiometric iron sulfides produced by reduction of iron pyrite (FeS2), were
identified as being especially important. Pyrite was subsequently added for
cases where the inherent pyrite content of the coal was low (15,16). Yields of
some of the primary liquefaction products formed when pyrite is added to a
slurry containing a moderately reactive but relatively low-pyrite coal are given
in Table 1.
A yield comparison between the products of the SRC-I and SRC-II processes
is given in Table 2.
Table 1. Yielda for Addition of Pyrite to Coalb

Pyrite addition, wt %
Product 0.0 3.0 7.5
c
light hydrocarbon gases 16.6 17.1 17.6
naphtha 7.3 9.4 11.4
total oil 37.5 40.9 44.7
SRC 29.8 27.5 23.5
insoluble organic matter 5.9 5.3 5.2
a
Based on wt % maf coal.
b
Pittsburgh seam bituminous coal from West Virginia containing 0.9 wt % pyrite.
c
Up to C4.
6 COAL LIQUEFACTION
Table 2. Comparison between Products of the SRC-I and SRC-II

Processesa
Process SRC-I SRC-II
Product yield, wt %
C1–C4 10.5 16.1
total oil 25.9 38.9
SRC solids 42.7 21.0
insoluble organic matter 4.1 5.1
H2 b 2.4 5.6
a
High-volatile Kentucky bituminous coal.
b
The negative sign indicates that hydrogen is being consumed.
Changing the process configuration to SRC-II was successful in producing

approximately 50% additional oil. However, a large increase in light hydrocarbon
gas make accompanied this increase, with an attendant reduction in hydrogen
utilization efficiency. Problems persisted using many coals, particularly subbitu-
minous coals (4).
Exxon Donor Solvent Process. A schematic flow diagram for the Exxon
Donor Solvent (EDS) process is shown in Figure 4. The principal modification in
this technology was the incorporation of a fixed-bed catalytic hydrogenating unit
Catalytic
solvent
hydrogenation
conditions,
260 – 475 °C
7–21 MPa H 2
Coal
H2 Gas
Catalytic
Liquefaction Distillation
reactor, solids Raw Product Liquid
H2 425 – 480 °C hydrogenation products
separation liquids
10–14 MPa
Heavy
bottoms H2
slurry
Raw
Fluid
coking liquids
Coke
H2O Hydrogen or
fuel gas H 2 or fuel gas
O2 or air production
Ash residue
Fig. 4. Exxon Donor Solvent process. To convert MPa to psi, multiply by 145.
COAL LIQUEFACTION 7
for the recycle solvent stream. This additional unit was required to keep the
hydrogen donating/shuttling capacity of the recycle solvent oil at an acceptably
high value (17). The use of bottoms slurry recycle to increase the solvent ‘‘make’’
fraction by taking advantage of the catalytic properties of minerals was also
investigated, and improved yields in the bottoms recycle mode were generally
reported. Recycle of this fraction was also reported to improve the operability
of the process dramatically, especially using low-rank coals where viscosity of
the bottoms stream was a significant problem (18). The primary liquefaction
part of the reaction system operated at temperatures of 425–480 C and pressures
of 10-–14 MPa (1450–2030 psi), using mean residence times in the range of
15 min to 2 h, depending on coal reactivity and process configuration. Operation
at these conditions required significant advances in hardware, such as the design
of a slurry let-down valve, required to reduce the pressure of the let-down slurry
(15% solids) from 14 MPa to 1 MPa at 450 C (19).
Operation of the EDS process was demonstrated in a 230 t/d unit in
Baytown, Tex., that started-up in 1980 and was dismantled in late 1982.
Exxon (now ExxonMobil) investigated the suitability of a wide range of different
U.S. coals for conversion. Data on the response of a variety of coals to once-
through and bottoms-recycle operations are shown in Figure 5. Figure 6 presents
typical liquefaction product distributions for the system operated both with and
without the Flexicoking (fluidized-bed coking) option.
ExxonMobil later developed a process known as Microcat in which a colloi-
dal catalyst is used for direct coal liquefaction. A group of former employees
formed Accelergy and acquired rights to these and other direct coal liquefaction
60
50
C3-538 °C Liquids, wt % MAF coal
40
30
20
10
0
Illinois Australian Wyoming Texas
Monterey Wandoan Wyodak Big Brown
Bituminous Subbituminous Lignitic
Fig. 5. Product yields for EDS process on (open) once-through basis and (shaded) bottoms-
recycle basis for various types of coal. MAF ¼ moisture- and ash-free; C3-538 C ¼ a boiling
fraction.
8 COAL LIQUEFACTION
b
50
C3-538 °C Liquids, wt %, MAF coal

40 a
30
20
10
0
Temp, °C 449 427 449
NRT, min 40 100 40
S/C/B, wt % 1.6/1/0 1.6/1/1 1.3/1/0.5 3/1/1
Fig. 6. Product yields for the EDS process in a 34-kg/d pilot plant (a) without, and
(b) with, the Flexicoking option. Gray bars represent gas, clear bars represent naphtha,
and dark bars represent oil. The pressure for the once-through process is 10.3 MPa and for
the recycle 13.8 MPa. NRT, nominal residence time; S/C/B solvent/coal/bottoms. To
convert MPa to psi, multiply by 145.
technologies of ExxonMobil. Accelergy now offers an improved process in which

the solvent hydrogenation in a separate unit is eliminated. This is claimed to
increase the thermal efficiency by 7%.
H-Coal. A significantly different scheme for DCL, developed by Hydrocar-
bon Research Inc. (HRI; now Headwaters Inc), was based on research and devel-
opment on the H-Oil ebullated-bed catalytic reactor for hydrotreating and
hydrocracking heavy oil. The heart of this process is the reactor, where coal, cat-
alyst, solvent, and hydrogen are all present in the same vessel (Figure 7). The
reactor is maintained in a ‘‘bubbling’’ or ebullated, ie, well-mixed, state by inter-
nal agitation using a slurry recirculation pump, coupled with the action of the
gas bubbling through the fluid. This process was piloted by the then-HRI and
Ashland Synthetic Fuels, Inc., in a 200–600 t/d pilot plant adjacent to Ashland’s
refinery in Catlettsburg, Ky. (13). The process (Figure 8) consists of slurry pre-
paration followed by catalytic hydrogenation/hydrocracking at 450 C and
15 MPa (2200 psi) in the ebullated-bed reactor.
A principal focus of this project was research and development for catalysts
that were tolerant of the coal-derived mineral matter in the reactor. Typical
early catalysts showed rapid deactivation because of coking and loss of
surface area, presumably from pore-mouth blockage by coke and metal laydown.
COAL LIQUEFACTION 9
Vapor
product
Catalyst
inlet
Expanded
catalyst
level
Liquid
Settled product
catalyst
level
Recycle tube
Distributor
Ebullating
pump
Feed Gas inlet

inlet
Catalyst
outlet
Fig. 7. H-Coal ebullating-bed reactor.
Plant fuel gas, 5.6 × 1013 J/day
Gas Fuel gas, 5.2 × 1013 J/day

clean-up Sulfur, 813 t/day
NH 3 , 138 t/day
Coal,
25,000 t/day Solids Naphtha, 240 m3/day
H-Coal separation Fuel oil, 7,650 m3/day
7,154 t/day
10.8 × 10 6 m 3 /day Hydrogen Oxygen, 4,792 t/day

manufacture
Fig. 8. Single-stage H-Coal process using Illinois No. 6 coal. To convert J to Btu, multiply
by 6.48 10-4. To convert m3 to bbl, multiply by 6.29. To convert m3 to standard cubic feet
(scf), multiply by 35.3.
10 COAL LIQUEFACTION
Coke buildups of 20–25 wt % and surface area reductions from 300 m2/g
for the fresh catalyst to 25 m2/g for the aged catalyst were reported after
only 5 days on stream (20). Although one of the primary advantages of the
H-Coal processing scheme was the ability to add and withdraw catalyst
continuously from the reactor in order to maintain a stable level of activity,
catalyst replacement, and consumption rates were unacceptably high under
these conditions. However, Ashland Oil completed a design for a 50,000-bpd
plant based on data generated by the H-Coal plant.
Wilsonville Coal-Liquefaction Facility. Beginning in 1973, a 6 t/d coal-
liquefaction pilot plant was built in Wilsonville, Ala., by the Edison Electric
Institute (EEI) and Southern Company Services. The Electric Power Research
Institute (EPRI) assumed project sponsorship in late 1973, and USDOE became
the primary sponsor in 1976. Amoco Oil Co. (now BP) joined the project in 1984.
The purpose of the Wilsonville Advanced Coal Liquefaction R&D facility was to
provide a flexible but reasonably large-scale pilot plant where effects of coal type
and processing, ie, reactor configuration, could be tested and evaluated. Research
on the Kerr–McGee critical solvent deashing (CSD) technology (also termed the
residual oil solvent extraction, or ROSE, process) was also carried out, resulting
in the development of alternative methods for solids removal from primary lique-
faction products. Because of the role of Wilsonville in demonstrating success or
failure on a consistent basis of a large number of concepts, many of whom were
initialized elsewhere, particular attention should be paid to the results from this
facility (21).
The plant began operation in 1974 in the SRC-I mode, but it evolved into a
two-stage operation using two ebullating-bed catalytic reactors (22). Initial
efforts in two-stage liquefaction focused on catalytic upgrading of the thermal
products or on nonintegrated two-stage liquefaction (NTSL). This configuration,
termed nonintegrated because the coal-derived resid hydrocracking step did not
interact with the primary thermal part of the plant, was excessively inefficient
because of the high hydrogen consumption associated with the thermal part of
the operation.
In the integrated two-stage approach (ITSL), a short contact-time
thermal reactor was close-coupled to an ebullating-bed catalytic reactor, and
process solvent was generated by distillation of the hydrocracked products.
The thermal resid produced in the ITSL at short contact times was more
reactive toward expanded-bed hydrocracking, thus permitting operation of
the ebullating-bed reactor at lower severity and minimizing gas make (23).
The results of liquefaction of an Illinois No. 6 high-volatile bituminous coal
using both the NTSL and ITSL modes at Wilsonville are shown in Table 3 (24).
Coal throughput, ie, space velocity per unit reactor volume, was substan-
tially improved in going to the ITSL mode. The higher reactivity of the coal-
derived resid permitted operation of the hydrocracker at lower temperature;
this would be expected to reduce the rate of coke laydown on catalyst, and to
improve hydrogen utilization efficiency by minimizing formation of light hydro-
carbon gases (higher distillate selectivity). A 35% increased yield of Cþ
4 distillate
was obtained.
Also explored were reconfigured integrated two-stage liquefaction (RITSL),
where solvent deashing was practiced after the hydrocracking step, and
Table 3. Operating Conditions and Yields at Wilsonville Planta
Mode of Operationb
parameter NTSL ITSL RITSL CC–ITSL CTSL
run number 241CD 7242BC; 243JK/244B 247D 250D 250G (a)
catalyst Armak Shell 324M Shell 324M Amocat IC Amocat
Thermal stage
average reactor temperature, C 429 460;432 432 440 443
coal space velocity at temp >371 C, kg/m3 320 690;450 430 320 320
pressure, MPac 15 17;10–17 17 17 17
Catalytic stage
average reactor temperature, C 416 382 377 399 399
space velocity catalystd, h1 1.7 1.0 0.9 2.08 2.23
catalyst age resid/cat 260–387 278–441; 380–850 446–671 697–786 346–439
Yieldse
11
C1–C3 gas 7 4;6 6 7 8
C4þ distillate 40 54;59 62 64 63
resid 23 8;6 3 2 5
hydrogen consumption 4.2 4.9;5.1 6.1 6.1 6.4
Other
hydrogen efficiency, C4þ distillate/H2 consumed 9.5 11;11.5 10.2 10.5 9.8
distillate selectivity, C2–C3/C4þ distillate 0.18 0.07;0.10 0.10 0.11 0.12
energy content of feed coal reject to ash concentrate, % 20 24;20–23 22 23 16
a
Illinois No. 6 coal.
b
See text for term definition.
c
To convert MPa to psi, multiply by 145.
d
On a wt of feed per wt of catalyst basis.
e
Wt % on a maf coal basis.
close-coupled integrated two-stage liquefaction (CC-ITSL), where the two reac-

tors (thermal/catalytic) were linked directly without any intervening processing
steps (25,26). Typical results for these processes are also shown in Table 3. Incre-
mental improvements in distillate yield and selectivity were realized by chan-
ging the process configuration but at the expense of increased hydrogen
consumption.
From 1985 to 1992, process studies at Wilsonville focused on development of
a catalytic/catalytic two-stage liquefaction (CTSL) scheme using ebullating-bed
catalytic reactors in both stages. Initial work (27) indicated that distillate yields
as high as 78% could be obtained by operating the first stage at low severity
(399 C) and by using a large-pore bimodal NiMo catalyst having a mean micro-
pore diameter in the 11.5–12.5-nm range. The deasher feed, now from the second
reactor, was sufficiently light that the deasher previously used could be replaced
by a simple pressure filter. The results from the CTSL mode for three different
coals are shown in Table 4. These data show the significant improvement in dis-
tillate production that can be achieved by use of catalyst in both stages, but
(again) at the cost of increasing levels of hydrogen consumption. Keep in mind,
though, that the hydrogen is used more efficiently.
Table 4. Operating Conditions and Yields at Wilsonville for Three Coals in CTSL Mode
Coal type
Parameter Illinois No. 6 Ohio 6a Wyodak

run number 253A 254G 251-IIIB
catalyst Shell 317 Shell 317 Shell 324
First stage
average reactor temperature, C 432 433 441
inlet hydrogen partial pressure, MPac 14.1 15.0 17.3
feed space velocity, h1 4.8 4.3 3.5
pressure, MPab 17.9 18.8 17.9
catalyst age, resid/catalyst 150–350 1003–1124 760–1040
Second stage
average reactor temperature, C 404 421 382
space velocity, feed/catalyst, h1 4.3 4.2 2.3
catalyst age, resid/catalyst 100–250 1166–1334 371–510
Yieldc
C1–C3 gas 6 8 11
C4þ distillate 70 78 60
resid 1 1 þ2
hydrogen consumption 6.8 6.9 7.7
Other
hydrogen efficiency, C4þ distillate/H2 10.3 11.3 7.8
consumed
distillate selectivity, C1–C3/C4þ distillate 0.08 0.11 0.18
energy content of feed coal rejected 20 10 15
to ash concentrate, %
a
Approximately 6% ash.
b
c
Wt % on a maf coal basis.
COAL LIQUEFACTION 13
Block diagrams of NTSL, ITSL, RITSL CC–ITSL, and CTSL operations at

Wilsonville are given in Figure 9. The Wilsonville Advanced Liquefaction R&D
facility was shut down in early 1992 and was decommissioned shortly thereafter.
NEDOL. The Japanese NEDOL process and the German Kohloel process
(as discussed in the subsequent section) are considered to be demonstrated and
suitable for commercialization by their companies. NEDOL is similar to the EDS
process. However, a catalyst is used (‘‘natural’’ pyrite of mean particle size 0.7m)
with the hydrogenated recycle solvents. A 150-t/d pilot plant was operated dur-
ing 1996–1998, with up to 80 days of continuous operation (28,29). A 2500-t/d
plant operating at mild reaction conditions, 16.8–18.8 MPa and 450 C has
been simulated (30). The pilot-plant schematic is shown in Figure 10.
Brown Coal Liquefaction Process. During the 1980s, a 50-t/d pilot plant
was built and operated by NEDOL in Australia, adjacent to the huge coal
reserves in the Latrobe Valley (31). These coals have a low ash content, but
the moisture content is very high, in the 55–65% range. A new dewatering pro-
cess was developed during the 1980s operation. During continuous runs of more
than 1000 h, yields of greater than 50% oils were achieved. The low price of crude
resulted in termination of runs in the 1990s, but process improvements contin-
ued to be developed in a 0.1-t/d bench-scale unit.
Pulverized coal
Slurry preparation
Thermal liquefaction Hydrogen

Process
solvent
Distillate solvent recovery Thermal distillate
Critical solvent deashing Ash concentrate
Hydrogen
Catalytic hydrogenation Hydrotreated resid (HR)
Hydrotreated
solvent
Hydrotreated solvent recovery Hydrotreated distillate
(a)
Fig. 9. Block diagrams for (a) NTSL, (b) ITSL, (c) RITSL, (d) CC-ITSL, and (e) CTSL
operations at Wilsonville (4).
Pulverized coal
Slurry preparation
Process
solvent
Catalytic hydrogenation Hydrogen
(b)
Pulverized coal
Slurry preparation
Process
solvent
(c)
Fig. 9. Continued
Pulverized coal
Slurry preparation
Hydro Thermal liquefaction Hydrogen

treated
solvent
hydro
treated
resid
(d)
Pulverized coal
Slurry preparation

Solvent/
resid/
solids

Hydrotreated
resid
Hydrotreated resid + ash
(e)
Fig. 9. Continued
Slurry preparation Liquefaction Distillation
Gas
Coal Fine iron
catalyst Recycle gas compressor
Hydrogen Atmospheric distillation tower Naphtha

fraction
Hydrogen Liquefaction
compressor reactor Separator
Slurry mixer
Preheating (three in
furnance series) Kerosine and
Coal bin High- light and fraction
temperature Vaccum distillation tower
Slurry heat separator
Heating
Slurry storage exchanger
furnance
tank Letdown
valve
16
Slurry charge pump
Fuel
Separator
Fuel
Solvent Preheating
Pulverizing and
Hydro furnace Residue
drying system Hydrogen
genation
reactor
Stripper
(Hydrogen donor solvent) (Heavy oil fraction)
Solvent feed
Solvent hydrogenation Fuel Pump
Fig. 10. Schematic of NEDOL Pilot Plant. Reprinted from Ref. 28 with permission from Elsevier Scientific.
Hydrogen Hydrogen recycle

Catalyst
Integrated
hydrogenation
Coal
Separation
Gases
Slurry
Flash
mixing
separator
LPG
Primary
reaction Light
oil
Vacuum
distillation Atmospheric
distillation
Recycle solvent Middle

oil
Vacuum
bottoms
Fig. 11. Schematic for Kohloel process (31).
Kohloel–Integrated Gross Oil Refining (IGORþ). Ruhrkohle and VEBA

Oel collaborated on this process. In the primary reactor, conditions were main-
tained at 30 MPa and 470 C, and an iron-oxide catalyst was used. Products
were separated hot, and the vapor products were hydrotreated at 30 MPa and
350–420 C. The liquid from the first separator was recycled as part of the sol-
vent. The liquid from the second separator was distilled at atmospheric pressure
to yield a light oil and a medium oil. The process schematic is shown in Figure 11
(31). Process yields are shown in Table 5. In 2001, key personnel of the Bottrop
plant founded h-tec and offered this process for licensing.
Table 5. Yields and Product Quality for the Kohloel Processa

Process yields Yield
hydrocarbon gases (C1–C4) 19.0
light oil (C5–200 C) 25.3
medium oil (200–325 C) 32.6
unreacted coal and pitch 22.1
Product quality Light oil Medium oil
hydrogen (%) 13.6 11.9
nitrogen (ppm) 39 174
oxygen (ppm) 153 84
sulfur (ppm) 12 <5
density (kg m3) 772 912
a
Prosper coal (German bituminous).
Fresh Hydrogen Recycle Hydrogen Gases
Coal Oils
Low-temp.
Separator
High-temp.
Catalyst
Separator
Vacuum
Preheater Distillation
Slurry
Hydrotreater
Mixing
1st Stage 2nd Stage
Ebullating Ebullating
Reactor Reactor
Atmospheric
Distillation
Residue
Recycle Solvent
Fig. 12. Schematic for Shenhua process.
Shenhua Process. This process has been developed since 2000 by the
Shenhua Group of China, with support from China Coal Research Institute.
The process was tested in a 0.1-t(coal)/d bench-scale unit and a 6-t(coal)/d process
development unit. It was then demonstrated in a 1-Mt(oil)/year production line
(Figure 12) in Inner Mongolia starting at the end of 2008. It was designed to pro-
duce approximately 800 kt/year of ultra-clean, low-sulfur diesel fuel, 200 kt/yr of
naphtha, and 100 kt/year of LPG (32). In the next 18 months, it operated five
times with a total production time of slightly less than 4200 h, and it produced
slightly less than 450 kt of fuels and chemicals. The process shown in Figure 12
uses two ebullating-bed reactors in series operated at 455 C and 18 MPa, with a
nanosize FeOOH catalyst for the liquefaction. A third ebullating-bed reactor is
used for the hydrogenation of recycle solvent, and residue separation occurs by
vacuum distillation (33). The plan was to build two additional lines, each with
the same capacity as this, in Phase I, and then two additional lines in Phase II.
Other Processes. Other variations of catalytic and noncatalytic coal
liquefaction schemes have also been developed. A 2.5-t/d pilot plant was operated
for 4 years by the National Coal Board in the United Kingdom at Point of Ayr in
Wales, but it has since been decommissioned (31,34). The catalytic coal liquids
(CCL) process (35) reacted a coal-oil slurry with hydrogen over baskets contain-
ing a proprietary catalyst developed by then-Gulf Oil (now Chevron), reportedly
unaffected by coal ash. The consolidation synthetic fuels (CSF) process used a
complicated multistage operation in place of the second-stage hydrogenation/
fractionation typically carried out in two-stage liquefaction processes (36).
Bench-Scale Research on Catalysts for DCL. Bench-scale test results
are generally looked at with skepticism because it is not clear how they relate
to processes going on in industrial-scale reactors. However, bench-scale research
is useful in formulating catalysts and in defining reaction mechanisms. Under
the right conditions, the results of bench-scale experiments are very relatable
to those in larger-scale reactors. Xu and co-workers (37) compared various
types of bench-scale reactors and found that results similar to those from a
large-scale, ebullating-bed reactor could be obtained from a microautoclave reac-

tor shaken at 400 cpm and containing a steel ball for efficient mixing.
As a result of the complexity of coal as a reactant and the vast variety of
products, understanding of the reaction mechanism of DCL is still in its infancy,
but it is developing. For example, researchers at the University of Kentucky
(38–40) used a variety of conditions to convert several coals, both bituminous
and nonbituminous, using bench-scale equipment, for both thermal and catalytic
conversions. For each run, a ‘‘severity index’’ was established, based on reaction
temperature and time. For a range of severity indices, they defined the produc-
tion of individual fractions (insolubles, preasphaltenes, asphaltenes, oils, and
gases) over a wide range of conversions. Using a ternary plot of three lumped
parameters and plots of individual fractions versus severity indices, they devel-
oped reaction pathways for the coals. They showed that the catalytic and thermal
pathways coincided for a given coal type, either bituminous or sub-bituminous.
However, the pathway for bituminous coals differed from that followed by the
subbituminous coals, as shown in Figure 13. Hence, the bench-scale reactions
make clear that the molecular-weight reductions are predominantly thermal
reactions: The role of the catalyst is to add hydrogen to transform stable bonding
into the hydrogenated counterpart that can be subjected to thermal degradation.
Because of the cost, large pilot plants usually are not used to produce data
over a wide range of conversions. However, considering data from a few of these
plants allows one to construct a plot (Figure 14) that shows that similar reaction
pathways are obtained for the larger plants as for the small laboratory reactors
used to generate the data in Figure 13. The limited data obtained at the large
Asphaltenes + Preasphaltenes
(wt.%, maf)
20 80
40 60
Observed
Thermal & Catalytic
Path
60 Bituminous Coals 40
80 20
Observed
Thermal & Catalytic
Path
Subbituminous Coals
Oils + Gases 20 40 60 80 IOM
(wt.%, maf) (wt.%, maf)
Fig. 13. Reaction pathways for thermal and catalytic liquefaction of bituminous and sub-
bituminous coals.
Asphaltenes + Preasphaltenes
(Wt. %, maf)
Wilsonville
Hoover ICRC
SRC2
H-Coal
Thermal
Oils + Gases IOM

(Wt. %, maf) (Wt. %, maf)
Fig. 14. Comparison of thermal (2-lb/h ICRC pilot plant; Thermal) and catalytic (SRC-2
plant at Ft. Lewis; Wilsonville Advanced Processes, and H-Coal Plant).
pilot plants appear to fall on a curve that would be predicted by the many results
obtained in the small laboratory reactors using a variety of coals.
Although materials like zinc chloride were tested as catalysts for DCL (41),
most catalytic research employed expensive materials such as molybdenum (42)
or cheap, disposable materials such as iron. The Dow Chemical Company devel-
oped a process using a molybdenum nanoscale catalyst. A hydroclone separation
allowed recovery of a solids-rich stream to be recycled; this stream returned at
least 75% of the molybdenum catalyst to the reactor. They scaled the process
to a plant that would convert approximately 200 lb/day (91 kg/day). The increase
in conversion using an emulsified molybdenum catalyst is shown in Table 6.
However, the costs and recovery of such material pose problems. Clearly, this
is not an expendable catalyst, in contrast to catalysts made using iron.
Table 6. Effect of Emulsified Mo Catalyst on Product Distributiona

Mo added, ppm 216 108 0
Product
gases and light oil, wt % 33.3 32.6 17.6
hexane-soluble oil, wt % 22.2 26.6 5.4
asphaltenesb 23.4 21.1 50.3
hydrogen consumedc 6.1 6.1 4.4
a
Pittsburgh No. 8 bituminous coal, 400 C, 13.7 MPa.
b
Defined as toluene-soluble, hexane-insoluble material.
c
kg H2/100 kg maf coal.
% Coal Conversion
% Yield of Oils
77
FeOOH/SO4
75
Fe7S8 38
71
Fe2O3/WO4 49
75
Fe2O3/MoO4 49
76
Fe2O3/SO4 45
71
Fe2O3 30
0 10 20 30 40 50 60 70 80 90 100
% Conversion/Yield
Fig. 15. Activities of iron (III) oxides, modified by small amounts of different anions.
DECS-17 coal, 400 C, 6.9 MPa (1000 psig) hydrogen pressure (cold), 300-mL stirred batch
autoclave, 1200 rpm, 60 min, tetralin/coal ¼ 3, Fe/coal ¼ 0.35 wt %. Reprinted from Re-
ference 44 with permission of the American Chemical Society.
In the 1990s, the USDOE started a consolidated program where various

iron-based catalysts were used in bench-scale tests in different laboratories.
Standard coals DECS-6 or DECS-17, chosen for their extremely low iron content,
were used for the bench-scale tests.
Researchers at the University of Pittsburgh used finely divided sulfated
iron oxides for the direct liquefaction of coal (43). Figure 15 shows results (44)
from liquefaction runs using DECS-17 with a series of anion-modified iron(III)
oxides and monoclinic pyrrhotite (Fe7S8) as catalysts (0.35 wt% Fe relative to
coal). The overall conversion of coal (defined as product soluble in methylene
chloride, MC, as a fraction of the initial coal) and the yield of oil (defined as an
MC-soluble, pentane-soluble product as a fraction of the initial coal) are both sig-
nificantly smaller for the unmodified iron oxide. Using the sulfated iron oxide
and the sulfated iron hydroxide results in conversions and yields comparable
with modifying the iron oxide with 5% tungstate or 5% molybdate anions, and
all are comparable with using pyrrhotite alone.
A series of catalysts were made at West Virginia University by preparing
and disproportionating ferric sulfide (Fe2S3) under various conditions. The dis-
proportionation is assumed to lead to an intimate mixture of pyrite, nonstoichio-
metric pyrrhotite, and elemental sulfur (45). The catalysts are extremely
sensitive to air or oxygen. The materials can be made as small particles by
preparing in situ on the coal surfaces (46) or in an aerosol reactor (47), or by
using surfactants (48). The in situ technique generally works best. Figure 16
shows the effect of various amounts of in situ impregnated catalyst on conversion
(THF-soluble) and oil þ gas yield (THF-soluble, hexane-soluble). The addition of
second metals as sulfides sometimes leads to alloys but with little improvement
in conversion or yield (49).
100
Conversion
Oil + gas yield
Total conversion (%), oil + gas yield (%)

80
60
40
20
0
0 1 2
Catalyst loading in IIS (wt %)
Fig. 16. Effect of loading of in situ impregnated ferric-sulfide-based catalyst. DECS-6

coal, 400 C, 6.9 MPa (1000 psig) hydrogen pressure (cold), 57-mL tubing-bomb reactor,
vertical agitation at 5 Hz, 30 min, 3-g coal, 5-mL hexadecane. Reprinted from Ref. 46
with permission from Elsevier Science.
Researchers at Pacific Northwest Laboratory developed techniques (50) for

generating iron-based catalysts in large quantities using flow-through techni-
ques termed rapid thermal decomposition of solutions (RTDS) and modified
reverse micelle (MRM) processes. In RTDS, precursors are exposed briefly to con-
ditions of high temperature and high pressure to initiate nucleation of iron oxide
and hydroxide. In MRM, high loadings of iron-bearing salts in water-in-oil micro-
emulsions are precipitated by changing the conditions of the microemulsions.
Various catalysts obtained using these methods were tested using the model
compound naphthyl bibenzylmethane:
CH2 CH2 CH2
Here the bonds marked by arrows are analogous to those that would be
cleaved in initial DCL reactions (‘‘primary’’ DCL), whereas cleavage of the
other bonds represent other, later, significant reactions in DCL. The results
for some of these tests are shown in Table 7.
A good snapshot of work on iron-based catalysts in laboratories supported
by USDOE as well as in other laboratories can be found in Reference 51.
However, Table 7 and Figures 15 and 16 demonstrate the difficulty in comparing
Table 7. Activity and Selectivity Using as Catalysts Iron Oxides and Hydroxide Made
via Flow-Through Techniquesa,b
Model compound
consumed (%) Selectivityc (%)
Catalyst sample no. Identified phase(s) ( 4%) ( 3%)
no catalyst <5 40–60
sulfur <20 50–70
RTDSd products
62–794 hematite 23 83
54–535 2-line ferrihydrite 20 84
54–503 hematite/6-line ferrihydrite 81 96
48–201 6-line ferrihydrite 90 96
48–197 6-line ferrihydrite <90 96
54–542 magnetite <90 98
54–561 ferric oxyhydroxysulfate <90 94
54–564 ferric oxyhydroxysulfate <90 96
MRMd products
MRM-7-2 2-line ferrihydrite 51 91
MRM-39-39 2-line ferrihydrite 41 90
MRM-7-2A magnetite/maghemite 77 89
MRM-39-39A maghemite 32 92
MRM-39-49 goethite/lepidocrocite 44 93
a
Reprinted with permission from Ref. 43. Copyright # 1994 American Chemical Society.
b
Naphthyl bibenzylmethane (NBBM), 9,10-dihydrophenanthrene (DHN), sulfur, 400 C; sealed tube,
25-mg NBBM, 10 mg S, 100 mg DHN, 10-mg catalyst precursor.
c
Cleavage of ‘‘primary’’ bonds (arrows in structure above) as a percentage of total bonds cleaved.
d
See text for acronyms.
catalyst performance by comparing results from different laboratories using not

only different reactors, but also different solvents, coals, conditions, and even
analytical techniques. To solve this problem, the USDOE commissioned Sandia
National Laboratories to test catalysts from different laboratories using an iden-
tical set of conditions and reagents and using a statistical design of experiments.
To the authors’ knowledge, the study was never completed. However, Table 8
shows the results from a partial report (52).
Table 8. Comparison of Three Iron-Based Catalysts with Pyrite as Catalyst and No Cat-
alyst (thermal)a,b
Catalyst THF Conv. (%)c DHP (%)d
1wt% WVU impregnated catalyst 93.0 13.4
thermal 51.7 1.73
1wt% PNL cat. precursor þ 1wt% sulfur 89.4 8.41
thermal þ 1wt% sulfur 63.6 2.35
1wt% U of Pitt cat. precursor þ 2wt% sulfur 82.3 5.35
thermal þ 2wt% sulfur 63.0 2.43
1wt% pyrite 73.4 3.88
thermal 54.9 1.08
a
From Ref. 45.
b
DECS-17 coal, 400 C, 800 psig hydrogen (cold) pressure; 43-mL microautoclave reactor, 60 min, 1.67
g coal, 3.34 g phenanthrene, 1 wt% catalyst.
c
THF soluble.
d
A measure of hydrogenating ability of the catalyst.
Researchers at the Institute of Coal Chemistry (ICC) of the Chinese Acad-

emy of Sciences (CAS) developed a ferrous sulfate catalyst impregnated on coal
on the bench scale. It was found that spraying FeSO4 actually yields well-
dispersed FeOOH on the coal surface. FeOOH needs sulfur to be active under
liquefaction conditions, in the form of a nonstoichiometric pyrrhotite (Fe1-xS).
The activity of the catalyst at 1 wt % in coal is higher than that of pyrite and
red mud at 3 wt % in coal (53–55).
2.2. Pyrolysis and Hydropyrolysis. The second category of DCL
aimed at producing distillate materials from coal is pyrolysis and hydropyrolysis.
Here a solvent is typically not used, and neither is a catalyst. Pyrolysis processes
are burdened with poor liquid yield, relative to hydrogenation, and the coal-
derived liquids are high in heteroatoms and in fine-particulate matter, both
organic and inorganic. Pyrolysis, sometimes called destructive distillation, essen-
tially involves heating the coal in an inert atmosphere, followed by recovery of
coal-derived tars and distillates in the off-gas stream (56). Pyrolysis carried
out in a hydrogen atmosphere is termed hydropyrolysis; pyrolysis at extremely
rapid heating rates is termed flash pyrolysis. These processes are not in use
for producing transportation fuels because of the yield and purity disadvantages
noted earlier.
Pyrolysis. Large-scale research and development on coal pyrolysis was
carried out on the char oil energy development (COED) process (57). This scheme
involved temperature-staged pyrolysis in a dryer-separator and three interacting
fluidized beds, as shown in Figure 17, and it was tested in a 36-t/d process
demonstration unit during the early 1970s. Pyrolysis temperatures ranged
To Synthesis gas
char Gas
cooler
Water Water
Vent
Scrubber Scrubber
Coal
dryer
Separator Separator
separ-
ator Stage Oil
Coal
Coa 1
191 °C l Water Stage 2 Water
258 °C
140 kPa Cha
r
454 °C
120 kPa
Stage 3
Stage
Preheated Preheated 538 °C 4
air air Cha
130 kPa r
871 °C Char to
140 kPa cooler
Steam
oxygen
synthesis gas
Fig. 17. COED process. To convert kPa to psi, multiply by 0.145.

Table 9. FMC/COED Process Product Distribution for Four U.S. Coals

Coal composition, wt% ND lignite Utah Illinois West Kentucky
Yields, dry coal basis
char 55.8 54.5 59.5 63.0
tar 5.3 21.5 19.3 17.3
gas 37.6 18.3 15.1 13.0
liquor (aq)a 1.3 5.7 6.1 6.7
a
Water containing water-soluble organics produced during pyrolysis.
from 191 to 871 C in the COED process, and the long residence times associated
with the fluid beds mandated low yields of liquid products. The typical product
yields for four different U.S. coals are shown in Table 9. The yield structure is
heavily weighted toward production of char and gas. Production of coal-derived
liquids ranged from 0.04 to 0.21 m3/t of coal as compared with 0.61–0.79 m3/t for
direct hydrogenation. Furthermore, the liquids produced were high in heteroa-
toms (especially nitrogen) and required extensive hydrotreating before use as a
synthetic crude oil.
Process development on fluidized-bed pyrolysis was also carried out by the
Consolidation Coal Co., culminating in operation of a 32-t/d pilot plant (58). The
resulting CONSOL pyrolysis process incorporated a novel stirred carbonizer as
the pyrolysis reactor, which made operation of the system feasible even when
using strongly agglomerating Eastern-U.S. bituminous coals. This allowed the
process to bypass the normal pre-oxidation step that is often used with caking
coals and resulted in a nearly 50% increase in tar yield. Use of a sweep gas to
remove volatiles rapidly from the pyrolysis reactor gave overall tar yields of
nearly 25% for a coal that had tar yields of only 15% as measured by the Fischer
assay, which is a standardized test to measure the amount of liquids produced by
pyrolysis.
Other large-scale coal pyrolysis process developments were carried out
by the Tosco Corp., with its TOSCOAL process (59). Essentially a direct copy
of Tosco’s rotating kiln technology that was developed for pyrolysis of oil
shale, this slow-heating scheme achieved tar yields at maximum temperatures
of 482–521 C that were essentially identical to those obtained by a Fischer assay.
Hydropyrolysis. Process development of the use of hydrogen as a radical
quenching agent for the primary pyrolysis was conducted (60). This process was
carried out in a fluidized-bed reactor at pressures of 3.7–6.9 MPa (540–1000 psi),
and at a temperature of 566 C. The reactor was designed to minimize vapor resi-
dence time in order to prevent cracking of coal volatiles, thus maximizing yield of
tars. Average residence times for gas and solids were quoted as 25 s and 5–10
min. A typical yield structure for hydropyrolysis of a sub-bituminous coal at
6.9 MPa (1000 psi) total pressure was char 38.4, oil 29.0, water 19.2, and gas
16.2, on a wt % MAF coal basis. Tar yields of approximately 0.32 m3/t were
quoted. Because the scheme used hydrogen, the liquids generally exhibited
lower heteroatom contents than conventional tars derived from coal pyrolysis
in an inert atmosphere. Process development proceeded through a 270-t/d semi-
works plant, which was operated successfully on noncaking coals. Operability for
caking coals was difficult, however.
Vent gases
6 Pyrolysis gas
Coal Middle oil

5 Water
3 Tar
1
4
Char
Air
Fig. 18. Lurgi–Ruhrgas flash-pyrolysis system, where 1 is a lift pipe; 2, primary pyrolysis
reactor; 3, screw feeder; 4, secondary pyrolysis reactor; 5 and 7, cyclones; and 6 and 8, pro-
duct recovery and tailgas cleaning.
Flash Pyrolysis. Development of a rapid, ie, flash, pyrolysis reaction

system was carried out by Lurgi–Ruhrgas (61). Between 1940 and 1960,
units processing 10 t/h were operated, and a small commercial plant was built
and has been operated in the former Yugoslavia since 1963. As shown
in Figure 18, coal is rapidly heated by mixing with hot recycled char in a
screw-conveyor-type reactor. Volatiles recovery is completed at 750 C in the sec-
ondary pyrolysis reactor. A typical product distribution for this system operating
on a high-volatile West Virginia bituminous coal gave a tar yield of 28 wt %, char
of 58 wt %, and gas þ liquor of 14 wt %, all on a basis of MAF coal.
Development of a flash-pyrolysis process was also carried out in the late
1960s and early 1970s (62). The process was designed to heat coal at rates in
excess of 5000 C/s. Process development proceeded through to a 2.7-t/d process
development unit using a variety of caking and noncaking coals. The reactor sec-
tion facilitated rapid heating by direct contact with hot char from the char bur-
ner. Gas residence times were brief (<2 s) and carefully controlled to minimize
secondary cracking reactions and to maximize the yield of coal-derived liquids.
Typical yield structures for pyrolysis at 580 C for two coals are shown in
Table 10. Rapid heating, and hence high tar yields, could be obtained with this
system. However, rapid quenching of reaction products proved to be a significant
problem, especially as the process was scaled up from the laboratory.
A novel high-pressure flash hydropyrolysis reaction system was designed
and operated by Rockwell Corp. during the mid-1970s (63). The process was
operated in a 1-t/h pilot plant, where the technology was successfully demon-
strated for a variety of different feed coals. The reactor was designed to mix
Table 10. Product Distribution for the Occidental Flash Pyrolysis

Process for Two U.S. Coals
Western Kentucky Wyoming
Coal bituminous bituminous
Yield, wt%
tar 35 27
char 56 52
gas 7 13
hot high-pressure hydrogen and coal in a highly turbulent zone such that extre-
mely rapid heating rates could be obtained, greater than 10,000 C/s. A schematic
of the reactor is shown in Figure 19a. In this system, the energy required to heat
coal to temperatures of 871–1038 C was generated by combustion of a portion of
the hydrogen feed to the reactor. Rapid heating then was facilitated by direct
contact with hot hydrogen and the combustion gases. The rapid heating, coupled
with extremely fast transition through the plastic regime of the coal, prevented
problems associated with operation using agglomerating coals. Furthermore, the
extremely short residence times for coal-derived volatiles and the activity of
hydrogen as a radical scavenger helped minimize secondary cracking reactions,
thus permitting yields of coal-derived tars to exceed greatly that predicted by the
Fischer assay. Whereas total coal conversion was relatively insensitive to reactor
residence time, the yield of liquid or oil was a maximum at 0.1 s for a U.S. bitu-
minous coal. Longer residence times favored formation of gases. The operating
pressure also had an effect on coal conversion and product distribution. Higher
pressures favored production of liquids.
Fluidized coal
70 Total liquids and gasses

Carbon conversion, wt %
Hot H 2 60
50
High velocity
hot H 2 40
Reactor
30
Low velocity
fluidized coal 20
10 Liquids
Quench
0
1000 2000 3000 4000
To separator Reactor residence time, ms
(a) (b)
Fig. 19. (a) Rockwell flash-hydropyrolysis reactor; (b) carbon conversion as a function of
reactor residence time. The reaction was run at 1038 C and 10.3 MPa (1500 psig).
2.3. Co-Processing. The main difference between co-processing and

hydroliquefaction is that the solvent is not simply a recycled stream from the
process but is a separate feed stream, either a resid fraction (or other fraction,
typically heavy) of petroleum or a waste (such as post-consumer plastic material,
tire rubber, or even municipal waste). The motivations for the additional feed are
to reduce the severity of the liquefaction conditions compared with coal-alone
hydroliquefaction, to recycle to extinction the heavy fraction, to take advantage
of synergies of operation, and to take advantage of the favorable economics and/
or politics in eliminating an unneeded stream.
Coal-Oil Co-Processing. Chevron, CANMET, and Ohio-Ontario Clean
Fuels are among the organizations that developed strategies and technologies
for coal-oil co-processing. The two-stage co-processing scheme of HRI (now Head-
waters) illustrated in Figure 20 (64,65) was used on coal ranks from lignite
through high-volatile bituminous, and with a variety of resids. As an example
of the synergistic benefits of co-processing, resid-based organometallic Ni and
V compounds (that would serve as poisons for downstream processing if present
in the liquid product) were found to be included in the solid (ash) phase contrib-
uted by the coal and, thereby, removable before downstream processing.
Furthermore, the conversion to the heaviest products (liquids boiling above
approximately 225 C) is greater in co-processing than the value expected for
individual processing of the feedstocks (60).
Coal-Waste Co-Processing. The use of catalysts, iron-based and
others, on coal-waste co-processing has been quantified in tests at the bench
scale and larger. Bench-scale tests have been carried out on a standard com-
mingled waste plastic developed by the American Plastics Council, as well as
on pure low density polyethylene, high density polyethylene, polypropylene
Gas to
Recycle hydrogen clean-up
Hydrogen IBP−350 °F
Atmospheric
First-stage 350−500 °F pressure
catalytic distillation
reactor 500−750 °F
Second-stage
catalytic 750−975 °F
Hydrogen reactor
Heater
Vacuum
distillation
Coal Slurry
mix
tank
Oil Vacuum
Slurry bottoms
heater
Recycle slurry oil
Fig. 20. Schematic of the HRI Two-Stage Co-Processing Scheme (64,65).

and poly(vinyl chloride); these were used alone, with coal, and with coal and
resid (66–68). Sawdust and farm manure have also been used in bench-scale
co-processing (69). A two-stage process was suggested for co-processing waste
rubber (from tires) with coal (70)—the tire would be liquefied noncatalytically
at relatively low severity conditions to obtain a tire oil and (marketable) carbon
black, and the tire oil would be combined with coal containing in situ ferric sul-
fide-based catalyst at higher temperatures and pressures.
HTI used a proof-of-concept bench-scale unit to study the effect of adding
waste plastics to either coal/resid feedstock or resid alone (71). The plastics
were obtained from curbside recycling in northern New Jersey, the coal was
sub-bituminous (Wyoming Black Thunder), and the resid was Hondo-VTB. A
proprietary iron catalyst was combined with Molyvan-A and used in a dispersed
slurry in a first-stage reactor. An interstage separator operated at high pres-
sure. After the second-stage reactor, the product was flashed and the light
ends hydrotreated to yield a naphtha-like fraction. The addition of the waste
plastics was found to increase the yield of distillate and to decrease the con-
sumption of hydrogen, regardless of whether coal/resid or resid alone was
used as the feedstock.
The Duales System Deutschland (DSD) has supported the recycling of
approximately 300,000 t/y of waste plastic, including mechanical recycling as
well as conversion to oil, chemical feedstocks, or synthesis gas in Germany. In
the United States, a feasibility study for a demonstration plant for co-processing
of waste plastics, tires, and coal was carried out (72). Base-case amounts were
200 t/d of plastic and 100 t/d of tires. Under these conditions, using typical tip-
ping fees and with oil priced at $20/barrel, the return on investment was found to
range between 9% and 20%.
Recent Analyses of DCL. The large DCL efforts in the western countries
ended by 2000. The USDOE effort was evaluated in 2001 (73). The general
conclusion was that the effort had not been based on sufficient research and
small-scale pilot plant work, and that there was a rush to build large plants
that were not used effectively. Internal reports to the USDOE (74,75) were in
general agreement regarding analyses and findings. They were somewhat
negative about direct-liquefaction efforts supported by the DOE because no com-
mercial plants were developed. In the case of the indirect-liquefaction efforts,
however, it was recognized that DOE support had led to commercial activities.
Winslow and Schmetz (75) further indicated that direct coal liquefaction had a
higher thermal efficiency than the indirect route. They noted that earlier
Bechtel designs for bituminous and sub-bituminous coals were thoroughly
done and authoritative. Robinson (76) also indicates that the energy efficiency
of the direct process is better than the indirect process. However, he notes that
the direct process is more difficult to operate than the indirect process. This is at
least partly a result of the erosion of pressure let-down valves because of the
abrasive nature of the coal slurry, the need to stay in donor solvent balance,
and the very difficult separation of solids from the liquid products. He notes
that the dominant product being in the gasoline range is a decided advantage.
Finally, Shui and co-workers (77) have reviewed some of the more recent multi-
staged processes, and Liu and co-workers (32) have discussed the corresponding
challenges in chemical reaction engineering.
3. Indirect Coal Liquefaction
The second category of coal liquefaction involves those processes that first gen-
erate synthesis gas (‘‘syngas’’), a mixture of CO and H2, by steam gasification of
coal:
CðsÞ þ H2 O ! CO þ H2 ð1Þ
followed by production of solid, liquid, and gaseous hydrocarbons and oxygenates

via catalytic reduction of CO in subsequent stages of the process (78). Whereas
coal is usually the preferred feedstock, other carbon-containing materials such as
coke, biomass, or natural gas can also be used (see FUELS FROM BIOMASS AND GAS,
NATURAL).
Processes whereby coal is gasified to syngas are not discussed here;
these involve commercial gasifiers such as those of GE, Kellogg, Koppers-
Totzek, Lurgi, or Shell. Processes to obtain fuels and/or chemicals from syngas
are discussed subsequently, regardless of the feedstock used for syngas.
Wender (79) illustrates the principal paths for fuels and chemicals as shown in
Figure 21.
In the general process, the raw syngas from the gasifier is first cleaned to
remove particulates and gasifier tars. The composition of the gas is then adjusted
using a sulfur-resistant catalyst to increase the H2/CO ratio via the water-gas-
shift reaction:
CO þ H2 O $ CO2 þ H2 ð2Þ
The shifted gas is cleaned for sulfur and CO2 before being converted to hydrocar-
bons and/or other products in a series of catalytic reactors. The synthesis reac-
tion is usually carried out using two or three reactors in series because of the
highly exothermic nature of the overall reaction. Generalized stoichiometric re-
lationships such as those below are often used to represent the fundamental as-
pects of the formation of hydrocarbons and oxygenates:
n CO þ 2n H2 ! ðCH2 Þn þ n H2 O ð3Þ
2n CO þ n H2 ! ðCH2 Þn þ n CO2 ð4Þ
n CO þ 2n H2 ! HðCH2 Þn OH þ ðn lÞ H2 O ð5Þ
However, the chemistry of the synthesis reactions is complex, and the formation
of hydrocarbons is fundamentally different in many respects from the formation
of oxygenates. Some of these issues are dealt with in a later section.
The first demonstration of catalytic conversion of synthesis gas to hydrocar-
bons was accomplished in 1902 using a nickel catalyst (80). In 1912, the Kaiser-
Wilhelm Institute for coal research was opened in M€ ulheim, Germany, and
Franz Fischer was appointed to head that laboratory the next year. The
announcement of direct coal liquefaction in 1913 by Frederich Bergius provided
Gasoline
(a) FISCHER-TROPSCH Diesel
FUEL CELLS Chemicals
Fe
CO
H O
H
2
2 CO + H2 METHANOL Isobulyene MTBE
wgs (DME)
ze
oli
te
(Z
SM
-5
)
CH4
(SNG) Gasoline
Medium BTU GAS
(b) DIMETHYL ACETIC

CARBONATE ANHYDRIDE
FORMIC ACID
ETHYLENE
GLYCOL
Rh CO
METHYL O2
CHEMICALS FORMATE
WAXES METHYL ACETATE
Na FORMALDEHYDE
F- OC
T H
3 CO CH3OH
Fe wgs Cu/ZnO Rh
AMMONIA H CO + H2 METHANOL ACETIC ACID
N2 2 Co
Co CHLORO METHYL O2
METHANES AMINES
Rh
Olefins Ethylene
(hydroformylation) ZSM-5
(Zeolites)
Acetaldehyde
Ethanol Rh Co
ALDEHYDES Olefins VINYL ACETATE

ALCOHOLS Aromatics
(2-ethylhexapol)
Commercial Near commercial, perhaps available for license Potential (next decade)
Fig. 21. Schematics for production from syngas of (a) fuels and (b) chemicals. Reprinted
from Ref. 79 with permission from Elsevier Science.
the incentive for the new institute to come up with a significant development.
The fundamental research and process development on the catalytic reduction
of carbon monoxide was carried out by Fischer, Tropsch, and Pichler (81). As
the German government recognized the need for a means for converting coal
to liquid fuels, the first Fischer–Tropsch commercial plant began operating in
1935. Sixteen additional plants were constructed by the Germans, and three
plants were constructed in Japan that were based on the German technology.
By the early 1940s, nine industrial plants that were operating within the
German borders produced 600,000 t/y of liquid hydrocarbons. However, the con-
struction of additional Fischer–Tropsch plants had been terminated by 1940. By
default, the direct coal liquefaction process became the dominant coal conversion
pathway and accounted for approximately 90% of the production during the war
years. It seems that at least a part of the abandonment of the continued growth
of the Fischer–Tropsch commercial plant construction was a result of politics and
the influence of I.G. officials who favored the direct liquefaction process (82). The
Fischer–Tropsch output was primarily for the production of chemicals and lubri-
cating oils. The olefins were used in the oxo process for the production of alcohols
that in turn were used for the manufacture of soaps, and it was planned to
expand this to make edible fat. After the end of World War II, the commercial
plant operations were downplayed and the only plant that continued to operate
was one that was transported to Russia. Operation continued at the pilot plant
scale, but this effort was reduced to the laboratory scale by 1960.
The U.S. government foresaw the lack of crude after World War II and
initiated a major effort to continue work on the conversion of coal to fuels that
could use the German work as a starting point. Accordingly, a 100-b/d plant
for Fischer–Tropsch synthesis was constructed in Louisiana, MO, along with
the direct-liquefaction facility mentioned earlier. However, by the time the
Fischer–Tropsch plant had been made operational, the Middle East petroleum
resources had been discovered, and the development of these caused the U.S.
government to abandon the liquefaction programs in the early 1950s. Conversion
of syngas to fuels and chemicals proceeded only on the laboratory scale for many
years thereafter. In the United States, interest in indirect liquefaction resumed
in the 1990s.
In South Africa, the government recognized the need to develop an industry
to produce oil from coal and established the South African Coal Oil and Gas Cor-
poration Ltd. (SASOL). During the 1940s, SASOL considered both direct and
indirect coal liquefaction, and decided in favor of indirect coal liquefaction.
Despite the discovery of Middle East petroleum, South Africa continued to sup-
port the development of synthetic fuels production from its coal. This was accom-
plished by the government guaranteeing a floor price for the oil that was
produced. Although the government had to subsidize SASOL production for
years, the company improved the process so that eventually it was making pay-
ments to the government. SASOL became an international company that oper-
ated without government subsidy, and it is now a large tax-paying company.
SASOL has expanded outside the country, with the production of 35,000 b/d in
Qatar based on natural gas as a feedstock.
Current interest in indirect liquefaction is worldwide. By proper selection of
catalyst and reaction conditions, including the H2/CO ratio, hydrocarbons and
oxygenates ranging from methane and methanol through paraffin waxes of
high molecular weight (>10,000) can be synthesized, as indicated in Figure 22
(83).
3.1. Production of Hydrocarbon Fuels. By convention, only the pro-
duction of hydrocarbons is termed Fischer–Tropsch (FT) synthesis. Hydrocar-
bons are typically used as fuels or fuel enhancers, generally diesel fuel.
Processes that operated at relatively low pressures, in the range of 100–200
kPa (1–2 atm) dominated commercial applications of FT synthesis in Germany
prior to 1939 (84). Catalysts were primarily based on cobalt. However, catalyst
lifetimes were short and deactivation was difficult to reverse. At the other
extreme, high pressure synthesis has been carried out at pressures in the
range 5–100 M Pa (50–1000 atm) and temperatures of 100–400 C. Supported
ruthenium catalysts are used, and the products are typically straight-chain
paraffin waxes (85).
500
Aromatics
alicyclics
branched-chain
paraffins
450 (Th02 –CCH3OCH3)
(ZnO + Al20 3 )
Branched-chain
olefins and alcohols
400
Temperature, °C
(Zn0 + alkali)
350 Methanol and
higher alcohols
Fluid-bed
300 (Zn0)
Methanol
(Fe)
Olefins
250 paraffins
chemicals
CH4 (g)
Fixed-bed
200 (Co–Carbonyls) (Ru–Carbonyls)
(Ni–Carbonyls)
Paraffins Paraffins High melting
olefins olefins paraffins
150
0 0.1 1 10 100 1000
Pressure, MPa
Fig. 22. Optimum pressure–temperature ranges for indirect synthesis processes showing
the various catalysts in parentheses. To convert MPa to psi, multiply by 145.
In contrast to the German work, the greatest successes of the processes

used by SASOL (and others) have occurred at medium pressures, typically in
the range 0.5–5 M Pa (5–50 atm). Cobalt catalysts, similar to those used for
the low pressure synthesis, were typically used at temperatures of 170–200 C.
Iron catalysts, usually promoted, have also been used in the SASOL process,
but at temperatures of 220–340 C. The primary differences between low and
medium pressure synthesis are increased catalyst life for the medium pressure
process, more diesel fuel, and a higher hydrocarbon yield.
SASOL. The SASOL plants are worthy of mention as the most successful
coal-based commercial facilities currently operating, as mentioned above. They
have supplied between one third and one half of South Africa’s fuel require-
ments.
SASOL-I. This was the first plant, put into operation at Sasolburg, South
Africa, in 1955 (86). An overall flow schematic for the original setup of SASOL-I
is shown in Figure 23. The product slate from this facility comprised materials
ranging from FT products (hydrocarbons) to oxygenates, including alcohols and
acids.
The plant uses iron catalysts. The catalyst is manufactured by precipitation
from an iron nitrate solution using sodium carbonate. Copper and potassium are
added as promoters, and the final material is pelletized and reduced with hydro-
gen prior to use. Catalyst life is variously reported to be 100 days to 6 months.
The overall processing scheme at SASOL-I involved steam-oxygen gasifica-
tion of coal using high pressure (3 MPa, 30 atm) Lurgi gasifiers producing
22,500 m3 each of raw gas having a H2/CO ratio of 1.7. The feed to the plant
was coal of high ash (35 wt %) and low energy content (23 MJ/kg) from mines
near Sasolburg. SASOL-I consumed approximately 5.5 million tons per year of
coal, with 60% going for gasification and synthesis and 40% for generation of
Nitrogen
Air Oxygen plant Oxygen
Liquor Crude phenols

Phenosolvan
Process Ammonium sulfate
oxygen By-products
separation
Tar Road prime
Tar distillation Creosote
Gasification Pitch
Raw gas Raw naphtha

Rectisol–gas Raw naphtha
Extrainer benzene
purification Motor benzole
Pure gas, Pure gas, Naphtha Batch distillation Toluol
high ratio low ratio hydrogenation of naphtha Xylol
Light naphtha
2.24 MPa
Heavy naphtha
Fixed–bed
Reactor wax
synthesis
Reactor
Wax deoiling
wax
Soft waxes
Vacuum Wax Medium waxes
distillation hydrogenation Hard waxes
Superhard wax
Paraforming
Coal
Fuel oil, cracking
Bottoms
C3 + C4 stock, etc
Hot condensate Gasoline

Distillation
Paraffin
and refining
Diesel oil
Cold condensate
Tail gas Petroleum
fraction
Tail gas
Gas reforming Rectisol wash
External recycle Olefins
1.90 MPa
Olefins
Catalytic Liquid petroleum gases
Gas absorption
polymerization
Tail gas Light oil Light oil
Fluid-bed
synthesis Liquid hydrocarbon recovery
Alcohols
Heavy oil Acetone
Methyl ethyl ketone
Primary chemicals Secondary recovery Higher ketones
Water-soluble recovery and batch distillation Methanol
chemicals Motor alcohol
Solvents
Ethanol
Process water, steam,
C3 and higher alcohols
and electricity
Neutralization
Salts of lower fatty acids
evaporation
Power station Fly ash

Water
Fig. 23. Flow scheme for the SASOL-I Fischer–Tropsch process. To convert MPa to psi,
multiply by 145.
onsite power. The raw gas was purified using Rectisol (chilled methanol) technol-
ogy for removal of gasification tars, H2S, CO2, and some methane. The purified
gas was then sent to the reactors.
By 2010, the SASOL-I plant had been modified to use imported natural gas
as the feedstock. The Haldor-Tøpsoe autothermal reforming process is currently
used to generate the syngas feed for SASOL-I.
Originally, both fixed-bed reactors (ARGE) and fluidized-bed reactors
(Synthol) were used.
The fixed-bed reactors, designed by Lurgi, contain approximately 40 m3 of
catalyst in more than 2000 vertical tubes having diameters of 4.5 cm OD.
There are six fixed-bed reactor trains in parallel, with each reactor processing
30,000 m3/d of feed at relatively low temperature (220–255 C) and medium pres-
sure (2.5 MPa, 25 atm), and producing 87.4 m3 (550 barrels) of product per day
(87). A flowsheet showing one fixed-bed reactor train is given in Figure 24.
In 1992, three fluidized-bed reactors of SASOL-I were shut down and
replaced by a single low temperature slurry-bed reactor. The SASOL Slurry-
Bed Reactor (SSBR) is 5 m in diameter and 22 m high and has a capacity of
2,500 bbl/d (88). It contains the catalyst suspended as a slurry in a FT wax or
other liquid. The SSBR is cheaper to build, can be scaled up, permits near-iso-
thermal behavior, and results in improved catalyst economy. A sketch of the
SSBR is given as Figure 25.
The primary products of SASOL-I are waxes and waxy products. The idea
was to crack the waxes to obtain diesel fuel, but economics dictates that their use
as waxes produces a higher return than what could be obtained from transporta-
tion fuels. Oxygenates and other products are also formed.
Total feed
Steam
Water
Lye circulation
Pressure
gasification Tail gas
Fuel gas
Heat Condenser Rectisol
Reactor C3 + C4
exchanger wash
C5+ fraction
Rectisol
purification
Water Light oil
Separator Recycle
gas Lye
Booster Cold condensate
Aqueous chemicals
Separators
Fresh feed Hot condensate
Reactor wax
Fig. 24. Flowsheet of medium-pressure synthesis, fixed-bed reactor (Lurgi–Ruhrchemie–

Sasol) having process conditions for SASOL-I of an alkaline, precipitated-iron catalyst,
reduction degree 20–25%; having a catalyst charge of 32–36 t, at 220–255 C and 2.48
MPa (360 psig) at a fresh feed rate of 20,000–22,000 m3/h in the reactor.
Light
Products
Fresh
Catalyst
Spent
Catalyst
Steam
To
wax/solid
separation
Synthesis
Gas
Fig. 25. Sketch of SSBR operating at low temperatures (220–270 C) and medium pres-
sure (2–3 MPa, 20–30 atm) for conversion of syngas to Fischer–Tropsch waxes (79).
SASOL has announced that it plans to expand the SASOL-I plant to double
production by 2013.
SASOL-II and -III. Two additional plants were built near Secunda,
South Africa: SASOL-II in 1980, and SASOL-III, essentially identical to
SASOL-II, in 1983. A block flow diagram for the original SASOL-II and -III pro-
cesses is shown in Figure 26.
The catalysts are made from millscale from a steelworks, ground, combined
with alkali and other promoters, and fused in an open-arc furnace. The consump-
tion of coal for these two plants combined is approximately 35 million t/year, and
these plants together produce approximately 1.6 104m3 (100,000 bbl) per day of
transportation fuels. As shown in Figure 26, the original design of the SASOL-II
and SASOL-III plants used only the fluid-bed Synthol reactor, and extensive sec-
ondary catalytic processing of intermediates (alkylation, polymerization, etc)
maximized the production of transportation fuels. Product selectivities of the
fixed-bed reactor and the Synthol reactor are given in Table 11 (89). As shown,
the fixed-bed system is more selective for middle distillates as well as for heavy
oils and waxes, whereas the fluidized-bed system is considerably more selective
for formation of C2–C4 olefins as well as for products in the gasoline (C5–C11) boil-
ing range.
In 1989, a fixed fluidized-bed reactor was coupled to the existing production
facility. The SASOL Advanced Synthol (SAS) reactor is less than half the size
and half the cost of the Synthol reactor, and it eliminates the recirculation of
the catalyst. The SAS reactor results in a higher conversion and higher selectiv-
ity to oil; scale-up is also easier than for the original Synthol reactor (89). The
Synthol reactor and the SAS reactor are shown in Figure 27. In 1989, the 16
Synthol reactors were replaced by 8 SAS reactors. Between 1989 and 2005, an
additional 8 SAS reactors of larger diameters have been placed in SASOL-II
Air
separation
12,000 t/day Steam
6 units
Ethylene
C1 C1 C2 C2 560 t/day
Oxygen
Bosjessprint partial cracking
subbituminous oxidation
coal 37,000 t/day 3.402 t/day 8 units Water to
as received Water cooling
Sized Syngas
phase tower
coal
Acid gas Alcohols
Lurgi F-T 250 t/day
Condensate Product Alcohols
Coal mark IV synthol
removal separation purification
handling 36 units 7 units
preparation 4 units
LPG
H2 S Recycle syngas Oil 640 m 3 /day
Fines CO2 phase
Ash
12,000 t/day Gasoline
Alkylation 3800 m 3 /day
Utilities Plant Sulfur H2 Hydrotreating
Steam Hydrogen Blending
6 units use recovery Isomerization Jet and diesel
plant storage
stretford platforming 2080 m 3 /day
polmerization
Electric
Ash BTX
Waste- Tar Sulfur 270 t/day

500 MW Dusty tar Tar oil
from local hydro water fractionation
to gasifiers
treating purification Tar products 540 t/day
Water to
cooling tower Ammonia 360 t/day
Fig. 26. Block flow diagram, SASOL-II and -III, where F-T corresponds to Fischer–
Tropsch, and BTX is benzene–toluene–xylene. To convert m3 to barrels, multiply by
6.29.
and SASOL-III (90). Both the Synthol and SAS reactors are operated at rela-
tively high temperatures, around 340 C.
Indirect Liquefaction in China. During the 1950s and early 1960s, China
had 74 FT synthesis units. These were based on BASF’s cobalt-based catalyst
and used fixed-bed reactors. Total production was relatively small, slightly less
than 500 kt. Staring from the late 1970s, China resumed FT synthesis research
at ICC, initially with emphases on fused iron catalysts and fixed-bed reactors. In
Table 11. Product Selectivities of SASOL Commercial Reactorsa

Product Fixed bed Synthol (Fluidized bed)
CH4 4 7
C2–C4 olefins 4 24
C2–C4 paraffins 4 6
gasoline 18 36
middle distillate 19 12
heavy oils and waxes 48 9
water soluble oxygenates 3 6
a
Reprinted with permission from Ref. 89.
Products
Cooling Products
oil
Cyclones
Catalyst
selling
hopper Boiler
Steam
feed
Aeration water
gas
Synthesis
gas
Synthesis
gas
(a) (b)
Fig. 27. (a) Synthol reactor and (b) SAS reactor used in SASOL-II and -III (79).
the late 1980s, precipitated iron catalysts started to be used. Research was
shifted to slurry-phase reactor technology in 1995, and ICC has operated a
750-t/year (approximately 20 bbl/d) slurry-phase pilot plant using iron catalysts
since 2001 (32,91).
Since 2006, Synfuels China, Ltd., a company evolved from ICC, has carried
out work on proprietary catalysts, reactor scale-up, and process integration
under the framework of the China Coal Utilization Program. Since 2008, three
commercial-scale demonstration plants based on high temperature slurry
Fischer–Tropsch process (HTSFTP) technology have been commissioned in dif-
ferent parts of the country, each with a capacity of 160 kt/year (approximately
3500 bbl/d) and an iron catalyst. These plants use different gasification technol-
ogies: coal-water slurry gasification is used in Yitai (Inner Mongolia), pressur-
ized fixed-bed gasification is used in Luan (Shanxi), and Shell gasification is
used in Shenhua (Inner Mongolia).
Indirect Liquefaction from Natural Gas. These are mentioned here for
completeness. The idea here is to convert natural gas (rather than coal) to syngas
and then to naphtha and diesel fuel.
The methanol-to-gasoline (MTG) process developed by Mobil (now Exxon-
Mobil) was used in New Zealand to convert natural gas to methanol and then
to gasoline, using a ZSM-5 zeolite catalyst. Currently, however, the process
stops at methanol production.
As mentioned, the SASOL slurry-phase distillate (SSPD) process went
online in 1991. Originally, a syngas derived from coal was used as the feedstock.
However, by 2010, SASOL had switched the SASOL-I plant from coal to
imported natural gas as the feedstock. Even though the syngas is derived from
natural gas, the slurry reactor uses an iron catalyst. The plant currently oper-
ates at the 2500-bbl/d range. SASOL has expanded its operation to Qatar
where it constructed, together with Qatar Petroleum, a 35,000-bbl/d FT plant
based on a natural-gas feedstock. In the first quarter of 2011, the plant was oper-
ating at 87% of the name-plate capacity.
PetroSA (formerly Mossgas) uses natural gas as a feedstock, and the
SASOL technology for the circulating-fluid-bed reactor, to produce approxi-
mately 40,000-bbl/d fuels. PetroSA, in a joint effort with Statoil, operated a
1000-bbl/d slurry reactor that used a cobalt-alumina catalyst. These two compa-
nies joined with Lurgi to offer gas-to-liquid (GTL) FT technology. Very recently,
Statoil has left the group.
The Shell middle-distillate synthesis (SMDS) process produces fuel from
natural gas. Proprietary catalysts are used to convert the syngas to long-chain
paraffins, which are then hydrocracked to give the required middle distillates.
Conditions can be altered to maximize diesel fuel or kerosene. Shell has operated
a 12,500-bbl/d plant in Malaysia. It has recently been expanded to 14,700 bbl/d.
The plant uses a cobalt-silica catalyst in fixed-bed reactors. Shell is scheduled to
operate a much larger plant in Qatar beginning in 2011.
3.2. Production of Alcohols and Other Oxygenates. Methanol is
used as a fuel in its own right, as an octane extender for gasoline, and as a feed-
stock for the production of polymers and other chemicals. Methanol has been
obtained from syngas since the Bayer patent in 1923. The original process
operated at high temperatures and pressures (350–450 C, 25–35 MPa) using a
zinc-oxide/chromium catalyst. Since 1966, ICI plants operate at low tempera-
tures and pressures (220–280 C, 5–10 MPa) using a Cu/ZnO/Al2O3 catalyst in
a multiquench reactor. Lurgi plants operate under similar conditions but in a
multitubular reactor. In both cases, naphtha or natural gas is preferred to coal
as a feed material for the syngas. Space-time yields of 1-kg methanol per liter of
catalyst per hour are typical.
Higher molecular-weight alcohols (‘‘higher alcohols,’’ HAs) are preferred as
fuel additives because of their lower vapor pressure. The compositions of various
mixed alcohols from syngas using various processes are provided in Table 12
(92).
3.3. Bench-scale Research on Catalysts for ICL. Kinetic expres-
sions obtained from reasonably well-characterized flow systems and reactors
using Fe-based catalysts are gathered in Table 13 (93–98). These are typically
Table 12. Composition of Some Fuel Alcohols from Syngasa

Alcohol (%) C1 C2 C3 C4 C5 Catalyst
MAS (SEHT) 69 3 4 13 9 K/Zn/Cr
Substifuel (IFP) 64 25 6 2 2.5 K/Cu/Co/Al
Octamix (Lurgi)b 62 7 4 8 19 alkali/Cu/Zn/Cr
HAS (Dow)c 26d 48 14 3.5 0.5 CoS/MoS2/K
a
See Ref. 72.
b
Isobutanol is 70% of C4 alcohols.
c
Straight-chain alcohols.
d
Methanol can be recycled to extinction, increasing the amount of ethanol.
Table 13. Iron-based Kinetic Rate Models
Rate model, rFT ¼ Catalyst T ( C) k (mol/gcat/h/MPa) P (MPa)a a H2/CO Ref.
k PCO PH2
fused iron (CCI) 250–315 0.0017–0.013 NA 0.028 NA 93
PCO þ a PH2 O
k PCO PH2
precipitated Fe 270 0.018 NA 4.51 NA 94
PCO þ a PH2 O
k PCO P2H2
fused iron (UCI C-73) 232–263 0.013–0.042 NA 2.56–0.67 NA 95
PCO PH2 þ a PH2 O
40
k PCO PH2
fused iron (BASF S6-10) 240 0.010 NA 0.19 NA 94
PCO þ a PCO2
k PCO PH2
100 precipitated Fe/1.3 K 220–260 NA NA 0.255–0.237 NA 96
PCO þ a PCO2
k PH 2 fused Fe/K 225–265 NA 1.01–1.83 NA 1.2–7.2 97
k PCO PH2
precipitated Fe/K/Cu 250 NA 220–441 NA 0.6–1.0 98
PCO þ K PH2 O
a
of the Langmuir–Hinshelwood type, indicating the importance of chemisorption

in the reaction. Most of these expressions have been obtained using simplified
models. More complex models incorporate the polymerization characteristic of
these reactions, incorporating initiation (adsorption), propagation (chain
growth), and termination (desorption). Of these complex models, the alkyl
mechanism was originally proposed by Fischer and Tropsch (99). Here initiation
takes place by dissociative chemisorption of CO. The surface carbon further
hydrogenates sequentially to surface species CH, CH2, and CH3. The last of
these, M-CH3, is the initiator, where M is a surface atom. Chain growth takes
place by multiple additions of the monomer species M CH2:
þH
MCH2 R þ M ¼ CH2 ! MCH2 CH2 R þ M ð3Þ
where R represents a growing alkyl group, -(CH2)nH, with n ¼ 0, 1, etc. The

chain can desorb, terminating the polymerization, in one of three ways: with
a loss of H, forming an olefin, CH2¼CH-R; with an addition of H, forming a par-
affin, CH3-CH2-R; or by abstracting OH, forming an alcohol, CH2OH-CH2-R.
However, this mechanism does not explain the formation of branched hydrocar-
bons or other oxygenates.
CO insertion, attributed to Sternberg and Wender (100), is considered the
main mechanism for the formation of oxygenates. Here M CO is the monomer,
while the chain initiator, M-CH3, is formed by the addition of hydrogen and
removal of water. Propagation steps may be written as:
2H þ2H;H2 O
MR þ M ¼ CO ! MCðRÞ ¼ O ! MCHðRÞOH ! MCH2 R
ð4Þ
Any of the last two species can terminate: M-CH2-R hydrogenating to form a par-
affin or dehydrogenating to form an olefin; and M-CH(R)-OH hydrogenating to
form an alcohol or dehydrogenating to form an aldehyde.
Storch et al. (101) proposed surface species that contain O, enols. Two pos-
sible monomers were postulated: M-CH2-OH and M-CH3. Then M-CH3 is added
to M CO to form M C(CH3)-OH, while a second surface enol, M-C(H)-OH, is
formed by multiple surface hydrogen additions to M CO. Chain growth occurs
with the two enols via:
2H;H2 O
M ¼ CðRÞOH þ HO ðHÞC ¼ M ! M ¼ CðCH2 RÞOH ð5Þ
The termination step yields oxygenates RCH2CHO and RCH2CH2OH and olefins
R¼CH2 as primary products; paraffins R-CH3 are formed as secondary products
from olefins. Several other mechanisms have been proposed to explain other
details of the product distribution observed.
For the associated water-gas shift (WGS) reaction, the literature (102) indi-
cates four possible mechanisms: redox, formate, associative, and carbonate. In
the redox mechanism, the surface is first oxidized by adsorbed O from H2O,
with release of H2; then reduction occurs by adsorbed CO, which is oxidized to
CO2. In the formate mechanism, adsorbed water dissociates into hydrogen and a
hydroxyl group; the latter reacts with adsorbed CO to form an adsorbed formate,
which decomposes into H2 and CO. In the associative mechanism, the adsorbed
hydroxyl interacts with an adsorbed CO to form CO2 and atomic hydrogen. In the
carbonate mechanism, hydroxyl groups from adsorbed water form adsorbed oxy-
gen that reacts with adsorbed CO to form a surface carbonate; this decomposes
into CO2.
Products formed using Fe-based and Co-based catalysts can be distin-
guished as follows:
Methanation: Fe forms little methane, even at high temperatures and low

CO partial pressures (103,104); methane formation over Co increases with
temperature. Hence, Co is best used at low temperatures, 180–220 C
(105).
Chain growth: With increasing CO partial pressure, chain growth in-
creases over Co but decreases over Fe (106). Over Fe, the chain length is
reduced with increasing temperatures (103), whereas increasing tempera-
tures over Co reduce the average molecular weight (105).
Chain branching: For Co, branching is more at short times, but it decreases
with time on stream (107), whereas branching increases with time for Fe
(108).
Secondary reactions: Olefin hydrogenation and isomerization are enhanced
with increasing temperature over Co. Iron produces more olefins and oxy-
genated products (108).
Nickel is generally not used as it forms carbonyls at high pressures. At high

temperatures, the main product is methane (109).
Supports/structural promoters such as silica, alumina, and magnesia pre-
vent sintering but decrease the activity resulting from metal-support interac-
tions (110–114). Some evidence indicates that the product chain length is
restricted to below C35 for activated-carbon (AC) supports (115,116). AC used
as a support also allows more complete reduction of the Fe and provides higher
olefin/paraffin ratios (115,116). The effects of properties of different AC supports
on FT products have been demonstrated (117).
To counteract the effect of metal-support interactions, chemical
promoters are added to the catalyst, eg, K, Cu, and Mo for Fe. Cu and K improve
the adsorption and dissociation of CO (118). The addition of K has been shown to
result in an increase in WGS (112,119–121) and in an increase in olefin selectiv-
ity resulting from enhanced surface basicity (122). The addition of Cu improves
the rate of activation of Fe and reduces the reduction temperature
(120,122,123). The addition of Mo can be shown to decrease activity but improve
stability (124). Mo is thought to facilitate the secondary reactions of olefins
(125). The addition of zeolites can result in the cracking of long-chain molecules
to increase the gasoline- and diesel-range cuts (126). The shape-selective proper-
ties of ZSM-5 and similar zeolites also influence the product distribution.
Secondary oligomerization, aromatization, and isomerization are also increased
(127).
60
C1
C2-4
50 C5-11
C12+
40
wi
(wt%) 30
20
10
0
H2 H2 CO H2/CO=0.7 H2/CO=2.0
250ºC 280ºC 280ºC 280ºC 310ºC
Pretreatment conditions
Fig. 28. Effect of pretreatment conditions on hydrocarbon selectivity over a Fe/Cu/K/SiO2

catalyst. Reaction conditions: 250 C, 1.45 MPa, H2/CO ¼ 0.67, 2 Nl/g-cat/h. To convert MPa
to psi, multiply by 145. Based on Ref. 128.
Pretreatment of catalysts has been extensively studied in bench-scale reac-

tors. Pretreatment essentially consists of reduction, whether by H2, CO, or syn-
gas. Figure 28 (128) shows that the performance of an iron-based catalyst can be
altered to increase products in the C5-11 range or the C12þ range depending on
prereduction gases and temperatures.
The influence of process conditions on product selectivity can be summar-
ized as follows (129,130). Increasing the reaction temperature increases the
desorption rate and favors the selectivity of lower molecular-weight hydrocar-
bons. Increasing the pressure increases the extent of reaction and product
chain length. Increasing the H2/CO ratio increases the probability of
chain termination by hydrogenation, decreases the mobility of the monomeric
species on the catalyst surface, and increases the desorption probability.
Hence, the paraffin yield increases, and the olefin selectivity and alcohol selec-
tivity decrease.
3.4. Production of Other Chemicals. Many chemicals attributed to
the indirect liquefaction of coal are formed from methanol; see Figure 21b. How-
ever, it is worth noting the hydroformylation (oxo) reaction. Here aldehydes are
produced by reacting olefins with CO using complexes of Group VIII metals such
as Co or Rh as a homogeneous catalyst. Hydroformylation is the fourth largest
use of synthesis gas, after the production of hydrogen, methanol synthesis, and
FT synthesis (131). As an example of hydroformylation, propylene can be
converted to n-butyraldehyde:
CH3 CH ¼ CH2 þ CO þ H2 ! CH3 CH2 CH2 CHO þ CH3 CHðCH3 ÞCHO ð6Þ
used in the synthesis of 2-ethyl-hexanol, a plasticizer. This is a multimillion-

ton/year operation. More details on the hydroformylation reaction can be found
in, eg, References 131 and 132.
3.5. Developments in Indirect Liquefaction. Much of the research
and process development on indirect liquefaction after the 1990s is aimed at
matching the synthesis conditions with modern, efficient coal gasifiers such
as those developed by Texaco, Dow, and Shell (see COAL CONVERSION PROCESSES,
GASIFICATION). Whereas the newer gasifiers are considerably more efficient, the
gas produced has a much lower H2/CO ratio than the SASOL-Lurgi gasifier.
The slurry reactor has been shown to be capable of using this type of feedstock,
under the right conditions. Optimization of the performance of the slurry-bed
reactor requires work on improved catalysts and on the separation of catalyst
and wax in the product stream (133).
In the production of oxygenates and chemicals from syngas, the Alternate
Fuels Development Unit in LaPorte, Tex., has been used by Air Products and
Chemicals Inc. to test several strategies for the USDOE. This includes develop-
ment of the slurry-phase methanol reactor and the formation of dimethyl ether.
A slurry bubble-column reactor is also used. In bench-scale tests, molybdenum-
or nickel-based catalysts have been used for the production of high molecular
weight alcohols. A promising development is the introduction of a high boiling
inert solvent, such as tetraglyme, in concurrent flow with the syngas in a
fixed-bed reactor (134). The solvent absorbs methanol as it is produced, and it
shifts the chemical equilibrium to the ‘‘right’’ so that more methanol is produced.
4. Recent Comparisons of DCL and ICL
Several reports have made comparisons of the direct and indirect coal-to-liquids
processes (135,136). Miller (137) indicates that an estimated $3.5–4.5 billion
investment would be required for the initial 50,000-b/d plant, on the basis of a
capital cost requirement of $70,000–90,000 per b/d. On this basis, plants may
be profitable with crude oil prices between $45 and 60/bbl. Carbon storage was
estimated to account for $4/bbl of the required selling price. Miller also indicates
that the integrated operation of advanced CTL technologies has never been
demonstrated. USDOE reports (138) indicate that ‘‘the scale of United States
oil consumption is enormous . . . [M]aking massive changes quickly will require
a gigantic, expensive crash program effort and at least two decades . . . [But]
such a transition also leverages U.S. natural resources and will substantially
improve the U.S. balance of payments.’’
Notes of caution also abound. Couch (139) concludes that ‘‘only when opera-
tional results have been obtained and lessons have been learned from the first
group of demonstration plants will it be possible to assess the contribution
which the technologies are likely to make in the longer term.’’ Williams and
Larson (140) note that ICL using FT can outperform fuels derived from crude
oil with regard to both air pollution and greenhouse-gas emissions, but fuels
derived from DCL cannot. They conclude that the supporting technological infra-
structures are much stronger for ICL than for DCL technologies. However, today
most would agree with Boroujeni (141) who points out that, ‘‘in a comparative
way for both ICL and DCL processes, the final selection is not usually so easy. It
is a matter of specific study for each case, and several factors including the geo-
graphical location of plant, product market and specifications, CO2 regulation,
price and availability of feedstock including feedstock to make hydrogen, etc.
should be considered.’’
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DADY B. DADYBURJOR
West Virginia University
ZHENYU LIU
Beijing University of Chemical Technology
BURTRON H. DAVIS
University of Kentucky

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COAL LIQUEFACTION

2. Direct Coal Liquefaction

Slurry preparation Fired

Solidification Solvent refined

Acid gas removal

Fractionator Vacuum tower

Fig. 3. SRC-II process, where LPG is liquefied petroleum gas.

stream served as heterogeneous hydrogenation catalysts that aid in the produc-

Table 1. Yielda for Addition of Pyrite to Coalb

Table 2. Comparison between Products of the SRC-I and SRC-II

Changing the process configuration to SRC-II was successful in producing

C3-538 °C Liquids, wt %, MAF coal

technologies of ExxonMobil. Accelergy now offers an improved process in which

Feed Gas inlet

Fig. 7. H-Coal ebullating-bed reactor.

Plant fuel gas, 5.6 × 1013 J/day

Gas Fuel gas, 5.2 × 1013 J/day

10.8 × 10 6 m 3 /day Hydrogen Oxygen, 4,792 t/day

close-coupled integrated two-stage liquefaction (CC-ITSL), where the two reac-

Parameter Illinois No. 6 Ohio 6a Wyodak

Block diagrams of NTSL, ITSL, RITSL CC–ITSL, and CTSL operations at

Thermal liquefaction Hydrogen

Distillate solvent recovery Thermal distillate

Critical solvent deashing Ash concentrate

Hydrotreated solvent recovery Hydrotreated distillate

Thermal liquefaction Hydrogen

Distillate solvent recovery Thermal distillate

Catalytic hydrogenation Hydrogen

Hydrotreated solvent recovery Hydrotreated distillate

Thermal liquefaction Hydrogen

Distillate solvent recovery Thermal distillate

Catalytic hydrogenation Hydrogen

Hydrotreated solvent recovery Hydrotreated distillate

Critical solvent deashing Ash concentrate

Hydro Thermal liquefaction Hydrogen

Catalytic hydrogenation Hydrogen

Hydrotreated solvent recovery Hydrotreated distillate

Critical solvent deashing Ash concentrate

Thermal liquefaction Hydrogen

Catalytic hydrogenation Hydrogen

Hydrotreated solvent recovery Hydrotreated distillate

Hydrotreated resid + ash

Critical solvent deashing Ash concentrate

Hydrogen Atmospheric distillation tower Naphtha

Hydrogen Hydrogen recycle

Recycle solvent Middle

Fig. 11. Schematic for Kohloel process (31).

Kohloel–Integrated Gross Oil Refining (IGORþ). Ruhrkohle and VEBA

Table 5. Yields and Product Quality for the Kohloel Processa

Fresh Hydrogen Recycle Hydrogen Gases

Fig. 12. Schematic for Shenhua process.

large-scale, ebullating-bed reactor could be obtained from a microautoclave reac-

Oils + Gases IOM

Table 6. Effect of Emulsified Mo Catalyst on Product Distributiona

In the 1990s, the USDOE started a consolidated program where various

Total conversion (%), oil + gas yield (%)

Fig. 16. Effect of loading of in situ impregnated ferric-sulfide-based catalyst. DECS-6

Researchers at Pacific Northwest Laboratory developed techniques (50) for

CH2 CH2 CH2

catalyst performance by comparing results from different laboratories using not

Researchers at the Institute of Coal Chemistry (ICC) of the Chinese Acad-

Fig. 17. COED process. To convert kPa to psi, multiply by 0.145.

Table 9. FMC/COED Process Product Distribution for Four U.S. Coals

Coal Middle oil

Methanation: Fe forms little methane, even at high temperatures and low