PETROTECH – 2009

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P - 570

DEVELOPMENTS OF AN ALTERNATIVE ROUTE OF LIQUID

HYDROCARBON PRODUCTION FROM COAL, BIOMASS AND
NATURAL GAS DERIVED SYNGAS

Sudip Maity and Devendra Kumar Sakhre

Central Institute of Mining and Fuel Research, PO- FRI, Dhanbad – 828 108, India
Email: sudip_maity@yahoo.com

ABSTRACT

India ranks sixth in the world in total energy consumption and needs to accelerate the development of
this sector to meet its growth aspirations. The country is rich in coal, biomass and natural gas
reserves hence needs to take alternative route for production of liquid fuels derived from these
sources. Research and technological development have already been initiated by government, public
and private sector enterprises for production of liquid fuels by gasification of biomass as well as coal
and simultaneous liquid production via Fischer-Tropsch Synthesis (FTS). Natural gas reformation to
syngas (CO + H2) followed by FTS will also add hydrocarbon liquid to India’s oil pool. In the 10th V
Year Plan, Central Fuel Research Institute (CFRI), Dhanbad has worked for development of Gas-To-
Liquid (GTL) technology in collaboration with Indian Institute of Petroleum (IIP), Dehradun and
National Chemical Laboratory (NCL), Pune and achieved considerable success in this line. Syngas
generation, syngas conversion and hydroprocessing are commercially proven and individually
optimized, but their combined use for production of liquid hydrocarbon from these three sources
namely coal, biomass and natural gas is not yet to be widely used technology. India needs to speed
up the technological development to cut short some amount of crude oil import. The erstwhile CFRI,
Dhanbad is perusing coal to oil conversion for last several decades and laboratory scale research set-
up exists with modern analytical and catalyst testing facilities. In 1980’s the erstwhile CFRI also
established a multi-tubular fixed-bed Process Development Unit (PDU) with 3.2 L catalyst volume
capacity and tested activity of several iron-based catalyst for FTS. Experiments were also conducted
for development of suitable coal gasification technology for high ash Indian coals.

During completion of the last century, research was persuaded for conversion of synthesis gas to wax
in collaboration with Govt. of Russia under ILTP Project of DST, Govt. of India. Iron and cobalt based
catalysts were developed and patented also. Three cobalt-based catalysts are also developed for
GTL technology with potential of becoming a commercial catalyst and PDU scale testing is due for
these catalysts. Very recently, CIMFR is also in the verge of setting up a catalyst testing facility of
50.0 L/day liquid hydrocarbon production capacity for Biogas conversion in collaboration with a private
entrepreneur which is targeted for further scale up to commercialization. In the present paper, an
account has been produced for recent development in syngas production and conversion
technologies for liquid hydrocarbon synthesis in the national and international levels.

Introduction:
Ever increasing price of petroleum crude has driven the world for finding out an alternative route for
production of liquid hydrocarbons (LH). Coal, biomass and natural gas are taken as the starting
material for an alternative source. India is the third largest producer of coal and has huge biomass
reserve hence serious steps should be taken for commercial production of liquid hydrocarbon from
coal, biomass and natural gas. Few scientific research Institutes and universities started studies in
laboratory scale during early fifties of the last century but serious steps never been initiated for the
commercial development of Coal-to-Liquid (CTL), Gas-to-Liquid (GTL) or Biomass derived syngas-to-
Liquid (BTL) synthesis in India.

CTL/GTL/BTL technologies involve two fundamental steps which are production of syngas by
gasification of coal or biomass and reformation of natural gas, and further conversion of syngas for
liquid hydrocarbon by Fischer-Tropsch Synthesis (FTS). This is called indirect liquefaction of solid
hydrocarbon sources. FTS was invented by German scientists F. Fischer and H. Tropsch at Kaiser

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Wilhelm Institute for Coal Research. Initiation of experiments began for commercialization of the FTS
for LH production in 1925 leading up to an annual 600,000 tonnes industrial capacity in 1945. Though
the process was not commercially viable, but it was important for Germany during the World War II as
oil supply was stopped to this country. In 1950s, South African oil company SASOL started
commercial production of oil by FTS during apartheid. SASOL has expanded its production in 1980s
and currently producing ~ 40% of diesel requirement of South Africa. Several other oil companies like
Shell Oil, Chevron (Texaco), and ExxonMobil are conducting research and have built pilot plants or
smaller plants.
In collaboration with some private entrepreneurs, the National Energy Technology Laboratory (NETL),
under U. S. Department of Energy built and operated a pilot plant in LaPorte, Texas focusing on the
development of slurry-phase reactor technology. RIPI’S, Iran is setting up a GTL pilot plant for syngas
conversion directly to high octane number gasoline, there is no need for upgrading stage in the GTL
plant.

India is far behind the international level in the development of these technologies. Serious steps have
been initiated by government, public and private sector enterprises for commercial production of LH
from solid/gaseous hydrocarbon sources. Present article summarizes the recent development of
these technologies.

Syngas Production
The first step towards these technologies is the production of syngas from the sources like coal,
biomass and natural gases. The production and purification of syngas costs almost 60% of the total
cost for a commercial plant of CTL/BTL/GTL. It is a process that converts carbonaceous materials,
such as coal, natural gas and biomass into carbon monoxide and hydrogen by reacting the raw
material at high temperatures with a controlled amount of oxygen and/or steam. The resulting gas
mixture is called syngas and is itself a fuel. The syngas is more efficient than direct combustion of the
original fuel, more of the energy contained in the fuel is extracted. Syngas may be burned directly in
internal combustion engines, used to produce methanol and hydrogen or converted via the FTS into
synthetic fuel. Various sources and processes for syngas production yield different ratios of H2, to CO
and the availability of source material for syngas manufacture varies at different places in the world.
Matching the specific method of production of syngas with the use in a particular synthesis is an
important factor in determining the techno-economic value of the various processes.

Gasification is a very efficient method for extracting energy from many different types of organic
materials, and also has applications as a clean waste disposal technique. Gasification of coal
undergoes several different processes in the gasifier. Initially coal loses 70% of its weight to liberate
volatiles and to produce char which undergoes further gasification. The combustion process occurs as
the volatile products and some of the char reacts with oxygen to form CO2 and CO which further
provides heat for gasification. Considering coal as C, the reaction may be written as:
1
C + O2 ⇒ CO --------------------- (1)
2
Gasification process occurs as the char reacts with CO2 and steam to produce CO and H2 according
to the reaction:
C + H 2 O ⇒ H 2 + CO ------------- (2)
In addition, there is a very fast reversible gas phase reaction which balances the concentration of CO,
CO2, steam and H2 also called the water gas shift (WGS) reaction:
CO + H 2 O ⇒ CO2 + H 2 ------------------- (3)
A limited amount of oxygen or air is introduced into the gasifier to allow some of the coal to be
"burned" to produce CO and energy which drives the reaction that converts further coal to H2 and
additional CO2.

Types of Gasifier
Commonly four types of gasifier (1) are currently available for commercial use: i) counter-current fixed
bed, ii) co-current fixed bed, iii) fluidized bed and iv) entrained flow.
i) Counter-current fixed bed (up draft): It consists of a fixed bed of coal through which the
"gasification agent" (steam, oxygen and/or air) flows in counter-current configuration. The
ash is either removed dry or as a slag.

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ii) Co-current fixed bed (down draft): It is similar to the counter-current type, but the
gasification agent gas flows in co-current configuration with the coal (downwards). The
produced gas leaves the gasifier at a high temperature, and most of this heat is often
transferred to the gasification agent added in the top of the bed, resulting in energy
efficiency on level with the counter-current type.
iii) Fluidized bed: The coal is fluidized in oxygen and steam or air. The ash is removed dry or
as heavy agglomerates that defluidize. The temperatures are relatively low in dry ash
gasifiers, so the fuel must be highly reactive; low-grade coals are particularly suitable.
Fluidized bed gasifiers are most useful for fuels that form highly corrosive ash that would
damage the walls of slagging gasifiers.
iv) Entrained Bed: A dry pulverized coal, an atomized liquid fuel or a fuel slurry is gasified
with oxygen (much less frequent: air) in co-current flow. The gasification reactions take
place in a dense cloud of very fine particles. Most coals are suitable for this type of
gasifier because of the high operating temperatures and because the coal particles are
well separated from one another. All entrained flow gasifiers remove the major part of the
ash as a slag as the operating temperature is well above the ash fusion temperature of
coal.

Methane is produced by decomposition of the coals volatile matter or some coals may also have
methane surface absorbed within their pores. The survival of this methane in the final product gas
depends on the temperature and kinetics of the gasification process. At lower gasifier outlet
temperatures more of this methane survives. Since both fixed bed gasifiers (e.g. Lurgi, BGL) and
fluidized bed gasifiers (HT Winkler, KBR Transport, GTI U Gas) have lower outlet temperatures
(below the ash slagging temperatures) than the single stage entrained bed gasifiers (Texaco, Shell,
GSP/NOELL), the syngas from these gasifiers is of much higher methane content, representing
typically 10-15% of the coal’s carbon content at 28-35 Bar (400-500 psig). It may be noted that
because of their operating temperature, fluid bed gasifiers have lower carbon conversion and their
ash contains more carbon than the slag from other gasifiers.

Pressurized gasification is preferred for Integrated Gasification Combined Cycle (IGCC) to avoid large
auxiliary power losses for compression of the syngas up to gas turbine inlet pressure. Most
gasification processes currently in use are planned for IGCC applications which are oxygen blown.

Natural gas is the largest source of syngas at present and its use for this purpose is growing. Methane
is the chief constituent of natural gas. Syngas is produced by partial oxidation, CO2 or steam
reformation of methane in presence of commercially available coke resistant NiO/γ-alumina catalyst
(2). The CO concentration is reduced by the presence of H2 in the reaction product.

SASOL produces syngas by gasification of coal in LURGI dry ash gasifier where coal enters the
gasifier at around 600oC but gasification zone temperature is 1200oC at an operating pressure of 3
MPa. H2/CO ratio is ~ 1.8 which is suitable for wax synthesis by low temperature Fischer-Tropsch
(LTFT) process (3). Source of syngas in Mossgas Plant is the catalytic reformation of methane
(natural gas) whereas non-catalytic oxidation of methane is the source of syngas in Shell plant (4, 5).
Exxon proposed syngas generation via catalytic reforming of methane in fluidized bed reactors and
Syntroleum proposes syngas production by low pressure reformation of methane in air blown reactors
(6, 7).

Fischer-Tropsch Synthesis (FTS):

The FTS is a catalyzed chemical reaction in which synthesis gas in converted into liquid hydrocarbons
of different forms. Only the metals like Fe, Co, Ni and Ru have the required FT activity for commercial
application. Under practical operating conditions Ni produces too much CH4 and Ru is of very high
cost and insufficient availability leaving only Fe and Co as the viable catalysts. The principal purpose
of this process is to produce a synthetic petroleum substitute, from coal, biomass and natural gas.
The FTS catalysts are supported on a combination of high surface area refractory oxides called
supports like alumina (Al2O3), anatase/rutile (TiO2), silica (SiO2), zirconia (ZrO2) in combination with of
some alkaline oxides (K2O & Na2O) and other metal oxides (MgO & CuO). Iron-based catalysts are
generally prepared by precipitation techniques, promoted with Cu and K2O on silica support (3). The
iron content is high; typically the composition is 5.0 g K2O, 5.0 g Cu and 25.0 g SiO2 per 100 g of Fe.
The catalyst is pre-reduced with H2 at about 400oC. However, due to high cost, cobalt is dispersed on
high surface area stable support like alumina, titania and/or silica. Cobalt is generally loaded in the

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range of 10 – 30 g per 100 g of support material (8). These catalysts are generally promoted with
small amount of Ru, Re or Pt to enhance the reduction process. Cobalt catalysts are generally
prepared by incipient impregnation technique. The Co-based catalyst is pre-reduced with H2 or CO +
o
H2 at about 350 C.

The FT reaction in its simplest form may be written as:

(2n + 1) H 2 + nCO → C n H 2 n + 2 + nH 2 O -------- (4)
2nH 2 + nCO → C n H 2 n + nH 2 O --------- (5)

The H2/CO ratio in the syngas plays an important role for the selection of the catalyst. The syngas
generated from natural gas has the optimum composition of H2/CO with ratio of ~ 2.0. The main FT
reaction is described by the macro equation according to the stoichiometric chemistry.
2 H 2 + CO ⇒ (−CH 2 −) + H 2 O ------------------ (6)

The syngas from coal gasification has a H2/CO ratio in the range of 0.5 to 1.2. For the iron-based
catalysts, besides the main reaction (Equation - 6) and other side reactions producing oxygenates and
carbides, there also the WGS (Equation – 3). Thus this will rebalance the H2/CO to another optimum
macro stoichiometric value. It is also widely accepted that for iron based catalysts, the general FT
reaction may be described as:
H 2 + 2CO ⇒ (−CH 2 −) + CO2 ----------- (7)

The nature of polymerization and probability of the chain growth of (-CH2-) monomer in the equation 6
and 7 gives rise to different kind of hydrocarbon products.

FT Reactor Development
Since FTS is an exothermic process, it is important to remove heat quickly to avoid overheating of
catalyst which would otherwise increase rate of deactivation, sintering and fouling of the catalyst. Two
kinds of FT operations are used:
i) Low temperature (LTFT) where temperature is 200 – 240oC and both Co and Fe catalysts are
used mainly for high molecular linear waxes;
ii) High temperature (HTFT), where temperature is 300 – 350oC and only Fe based catalysts are
used for gasoline and low molecular hydrocarbon production.
Some of the HTFT commercial reactors are at Brownsville, TX plant, fixed fluidised bed (FFB) type
which operates at 300oC temperature and 2 MPa pressure and the Sasol plant at Sasolburg is the
Kellogg-designed circulating fluidised bed (CFB) reactors operated at about 2MPa and 340oC. Sasol’s
reactor technology was improved with efficient heat exchanger and catalyst fluidization named as
Synthol which was used at Sasol Plant at Secunda and Mossgas FT Complex.

Low temperature operations for FTS, wax trickles down from the catalyst bed for the top fed
multitubular reactors whereas wax needs to be continuously removed from the reactor for slurry bed
operations. Sasolburg plant currently operates with the ARGE type reactor with 2050 tubes at a
temperature of 230oC and 2.7 MPa pressure. Shell Bintulu plant also works with four large
multitubular reactors having 10,000 tubes per reactor. Exxon successfully operated first commercial
slurry reactor having a 1.2m i.d. for wax production using Kölbel’s pioneering work with cobalt-based
catalyst. It had commercial production of 8.5 X 103t per year (6). Khassin et. al (9) studied the
permeable composite monolith (PCM) membranes reactor for the Fischer–Tropsch synthesis for
achieving high productivity and selectivity at small temperature gradient and low pressure drop using
the PCM membranes with the diameter close to that of the industrial tubular fixed bed (ARGE type)
reactor. A comparison of the established or demonstrated systems for CTL/GTL is shown in Table 1.

Table 1: System comparison of CTL/GTL technology providers

Company Syngas generation Reactors used Catalyst
Sasol POX with O2 SMR Fixed Bed, Slurry Bed, Fluidized Iron
Bed, Fixed Fluidized Bed Cobalt
Shell POX with O2 Fixed Bed, Slurry Cobalt

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Exxon Catalytic POX with O2 Cobalt

Slurry
Rentech POX with O2 , SMR, Slurry Iron
ATR –with O2 / air
Syntroleum ATR–with air Fixed Bed, Novel Horizontal Bed & Cobalt
Others

A schematic flow sheet is produced for the CTL/GTL/BTL technology development in Fig-1.

Reformer
FBR
Coal Gasifier Product
Slurry Reactor
Biomass Gasifier

Fig: 1 A schematic Flow sheet for CTL/GTL/BTL

Worldwide GTL/CTL/BTL plants

GTL/CTL Plants:
Germany: First operated commercial CTL Plant in 1940

South Africa: Further developed and improved plant for commercial production of diesel and
gasoline from coal at Sasolburg. Since 1950’s, 40 MT of coal/year converted to 1,60,000 barrels/day
of crude oil equivalent. SASOL has invested millions of dollars to design innovative next generation F-
T Reactor at Sasolburg for GTL & ICTL technologies. GTL plant has been established at Mossel Bay,
South Africa with Statoil’s proprietary technology.

USA:
i) Ultra-low sulfur diesel fuel – ICTL Plant (Indirect) is at Wyoming, USA by Medicine Bowl Fuel &
Power LLC.
ii) Rentech Inc., Mingo County, FT ICTL Fuel Plant;
iii) Peabody Energy & Rentech Inc.: Illinois, ICTL Plant, Budget: $10 million, Capacity: 1,250 bpd;
Due Date: 2010.
iv) ConocoPhiliphs at Pona City, Okla: Budget: $75 million (Test Plant);
v) ExxonMobil, Baton Rouge La – GTL Plant (1990s).

China:
i) ShenHua Group: CTL Plant (Direct); Capacity: 60,000 bpd
ii) ICTL Plant in Collaboration with SASOL in North West China; Cost : $14 billion

Middle East:
i) Qatar Oryx jointly with SASOL & Chevron Texaco ~ world’s largest GTL Plant with 34,000 bpd
ii) Pearl GTL Project – Qatar – World’s largest GTL Complex to achieve zero liquid discharge

BTL Plants:
First commercial BTL plant: April 2008; Freiberg, Germany; Joint venture by Choren & Energy
Research Centre Shell Global, Netherland (Capacity: 18 million liter diesel/Annum)
Proposed Demonstration BTL Plants:
1. Repotec, Austria (30 MW power & 4,200 Ton Diesel Annual capacity)
2. Chrisgas Projects, Sweden
3. Namdalen, Norway
4. Bhavnagar, Gujrat (50 L/day capacity by CIMFR, India in collaboration with Gargca Steel,
Bhavnagar)

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National Status
The erstwhile CFRI, Dhanbad is perusing coal to oil conversion for last several decades and
laboratory scale research set-up exists with modern analytical and catalyst testing facilities. In 1980’s
the erstwhile CFRI also established a multi-tubular fixed-bed Process Development Unit (PDU) with
3.2 L catalyst volume capacity and tested activity of several iron-based catalyst for FTS. Experiments
were also conducted for development of suitable coal gasification technology for high ash Indian
coals. During completion of the last century, research was persuaded for conversion of synthesis gas
to wax in collaboration with Govt. of Russia under ILTP Project of DST, Govt. of India. Iron and cobalt
based catalysts were developed and patented also. Three cobalt-based catalysts are also developed
for GTL technology with potential of becoming a commercial catalyst and PDU scale testing is due for
these catalysts. In the 10th V Year Plan, Central Fuel Research Institute (CFRI), Dhanbad has worked
for development of Gas-To-Liquid (GTL) technology in collaboration with Indian Institute of Petroleum
(IIP), Dehradun and National Chemical Laboratory (NCL), Pune and achieved considerable success
in this line. CIMFR has several patents on catalysts (cobalt & iron based) and process development of
FTS. The patented catalysts are selective towards diesel and gasoline fractions. These catalysts have
been tested in a 100 mL catalyst volume fixed bed reactor (10). This institute is setting up a BTL Pilot
Plant of 50.0 L/day liquid hydrocarbon production capacity for Biomass derived syngas conversion in
collaboration with a private entrepreneur which is targeted for further scale up to commercialization.
Coal gasification studies are being persuaded with high priority and presently CIMFR is also working
on agglomeration formation in reducing condition in pressurized fluidized bed gasification with low
rank high ash Indian coals.

Conclusion
A summarized review with latest technology development for CTL/BTL/GTL is produced in this article.
Reliance and TATA are in the process of collaboration with foreign entrepreneurs for setting up
commercial plants for CTL in India. Several coal blocks have been earmarked for the development of
CTL technology. Figures for different type gasifiers and FT reactors could not be produced for the
space limitations of the articles. Anybody interested, may go through the references for the detail
description of gasifiers, catalysts and reactors (11 - 14). The Council of Scientific and Industrial
Research, India has taken serious steps for development of a Process Development Unit for
demonstration of CTL technology in the 11th V Year Plan of Govt. of India. Several sister laboratories
are working together for this purpose. Considering the high price of petroleum crude, it is the urgent
need of our country to have its own CTL/BTL commercial production in near future.

Acknowledgements
Authors are thankful to Director, CIMFR for permitting to publish this review article.

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