Coal liquefaction

C
oal liquefaction is a process of converting coal into liquid hydrocarbons,
liquid fuels and petrochemicals. The conversion industry is commonly
referred to as "coal conversion" or "Coal To X". "Coal to Liquid Fuels" is
commonly called "CTL" or "coal liquefaction", although "liquefaction" is generally used
for a non-chemical process of becoming liquid.
1

Direct and indirect processes

Specific liquefaction technologies generally fall into two categories: direct (DCL) and
indirect liquefaction (ICL) processes. Indirect liquefaction processes generally involve
gasification of coal to a mixture of carbon monoxide and hydrogen (syngas) and then
using a process such as Fischer–Tropsch process to convert the syngas mixture into
liquid hydrocarbons By contrast, direct liquefaction processes convert coal into liquids
directly, without the intermediate step of gasification, by breaking down its organic
structure with application of solvents or catalysts in a high pressure and temperature
environment Since liquid hydrocarbons generally have a higher hydrogen-carbon molar
ratio than coals, either hydrogenation or carbon-rejection processes must be employed
in both ICL and DCL technologies.
As coal liquefaction generally is a high-temperature/high-pressure process, it requires a
significant energy consumption and, at industrial scales (thousands of barrels/day),
multibillion-dollar capital investments. Thus, coal liquefaction is only economically viable
at historically high oil prices, and therefore presents a high investment risk

Hydrogenation processes

One of the main methods of direct conversion of coal to liquids by hydrogenation process
is the Bergius process, developed by Friedrich Bergius in 1913. In this process, dry coal
is mixed with heavy oil recycled from the process. Catalyst is typically added to the
mixture. The reaction occurs at between 400 °C (752 °F) to 500 °C (932 °F) and 20 to
70 MPa hydrogen pressure. The reaction can be summarized as follows:
n C + (n + 1) H2 → CnH2 n + 2
After World War I several plants based on this technology were built in Germany; these
plants were extensively used during World War II to supply Germany with fuel and
lubricants. The Kohleoel Process, developed in Germany by Ruhrkohle and VEBA, was
used in the demonstration plant with the capacity of 200 ton of lignite per day, built
in Bottrop, Germany. This plant operated from 1981 to 1987. In this process, coal is mixed
with a recycle solvent and iron catalyst. After preheating and pressurizing, H 2 is added.
The process takes place in a tubular reactor at the pressure of 300 bar and at the
temperature of 470 °C (880 °F).[5] This process was also explored by SASOL in South
Africa.
In 1970-1980s, Japanese companies Nippon Kokan, Sumitomo Metal
Industries and Mitsubishi Heavy Industries developed the NEDOL process. In this
process, coal is mixed with a recycled solvent and a synthetic iron-based catalyst; after
preheating, H2 is added. The reaction takes place in a tubular reactor at a temperature
between 430 °C (810 °F) and 465 °C (870 °F) at the pressure 150-200 bar. The produced 2
oil has low quality and requires intensive upgrading. H-Coal process, developed by
Hydrocarbon Research, Inc., in 1963, mixes pulverized coal with recycled liquids,
hydrogen and catalyst in the ebulliated bed reactor. Advantages of this process are that
dissolution and oil upgrading are taking place in the single reactor, products have high
H/C ratio, and a fast reaction time, while the main disadvantages are high gas yield (this
is basically a thermal cracking process), high hydrogen consumption, and limitation of oil
usage only as a boiler oil because of impurities.
The SRC-I and SRC-II (Solvent Refined Coal) processes were developed by Gulf Oil and
implemented as pilot plants in the United States in the 1960s and 1970s The Nuclear
Utility Services Corporation developed hydrogenation process which was patented by
Wilburn C. Schroeder in 1976. The process involved dried, pulverized coal mixed with
roughly 1wt% molybdenum catalysts Hydrogenation occurred by use of high temperature
and pressure synthesis gas produced in a separate gasifier. The process ultimately
yielded a synthetic crude product, Naphtha, a limited amount of C3/C4 gas, light-medium
weight liquids (C5-C10) suitable for use as fuels, small amounts of NH3 and significant
amounts of CO2. Other single-stage hydrogenation processes are the Exxon Donor
Solvent Process, the Imhausen High-pressure Process, and the Conoco Zinc Chloride
Process
There are also a number of two-stage direct liquefaction processes; however, after the
1980s only the Catalytic Two-stage Liquefaction Process, modified from the H-Coal
Process; the Liquid Solvent Extraction Process by British Coal; and the Brown Coal
Liquefaction Process of Japan have been developed.
Shenhua, a Chinese coal mining company, decided in 2002 to build a direct liquefaction
plant in Erdos, Inner Mongolia (Erdos CTL), with barrel capacity of 20 thousand barrels
per day (3.2×103 m3/d) of liquid products including diesel oil, liquefied petroleum gas
(LPG) and naphtha (petroleum ether). First tests were implemented at the end of 2008.
A second and longer test campaign was started in October 2009. In 2011, Shenhua Group
reported that the direct liquefaction plant had been in continuous and stable operations
since November 2010, and that Shenhua had made 800 million yuan ($125.1 million) in
earnings before taxes in the first six months of 2011 on the project
Chevron Corporation developed a process invented by Joel W. Rosenthal called the
Chevron Coal Liquefaction Process (CCLP) It is unique due the close-coupling of the non-
catalytic dissolver and the catalytic hydro processing unit. The oil produced had
properties that were unique when compared to other coal oils; it was lighter and had far
fewer heteroatom impurities. The process was scaled-up to the 6 ton per day level, but
not proven commercially.

Pyrolysis and carbonization processes

Several carbonization processes exist. The carbonization conversion occurs

through pyrolysis or destructive distillation, and it produces condensable coal tar, oil and
water vapor, non-condensable synthetic gas, and a solid residue-char. The coal tar and
oil are then further processed by hydrotreating to remove sulfur and nitrogen species, 3
after which they are processed into fuels.
The typical example of carbonization is the Karrick process. In this low-
temperature carbonization process, coal is heated at 680 °F (360 °C) to 1,380 °F
(750 °C) in the absence of air. These temperatures optimize the production of coal tars
richer in lighter hydrocarbons than normal coal tar. However, the produced liquids are
mostly a by-product and the main product is semi-coke, a solid and smokeless fuel.
The COED Process, developed by FMC Corporation, uses a fluidized bed for
processing, in combination with increasing temperature, through four stages of
pyrolysis. Heat is transferred by hot gases produced by combustion of part of the
produced char. A modification of this process, the COGAS Process, involves the
addition of gasification of char. The TOSCOAL Process, an analogue to the TOSCO II
oil shale retorting process and Lurgi-Ruhrgas process, which is also used for the shale
oil extraction, uses hot recycled solids for the heat transfer.
Liquid yields of pyrolysis and Karrick processes are generally low for practical use for
synthetic liquid fuel production. Furthermore, the resulting liquids are of low quality and
require further treatment before they can be used as motor fuels. In summary, there is
little possibility that this process will yield economically viable volumes of liquid fuel.

Indirect conversion processes

Indirect coal liquefaction (ICL) processes operate in two stages. In the first stage, coal is
converted into syngas (a purified mixture of CO and H2 gas). In the second stage, the
syngas is converted into light hydrocarbons using one of three main processes: Fischer-
Tropsch synthesis, Methanol synthesis with subsequent conversion
to gasoline or petrochemicals, and methanation.
Fischer-Tropsch is the oldest of the ICL processes. It was first used on large technical
scale in Germany between 1934 and 1945 and is currently being used by Sasol in South
Africa.
In methanol synthesis processes syngas is converted to methanol, which is subsequently
polymerized into alkanes over a zeolite catalyst. This process, under the moniker MTG
(MTG for "Methanol To Gasoline"), was developed by Mobil in early 1970s, and is being
tested at a demonstration plant by Jincheng Anthracite Mining Group (JAMG) in Shanxi,
China.
based on this methanol synthesis, China has also developed a strong coal-to-
chemicals industry, with outputs such as olefins, MEG, DME and aromatics.
Methanation reaction converts syngas to substitute natural gas (SNG). The Great Plains
Gasification Plant in Beulah, North Dakota is a coal-to-SNG facility producing 160 million
cubic feet per day of SNG, and has been in operation since 1984. Several coal-to-
SNG plants are in operation or in project in China, South Korea and India.
The above instances of commercial plants based on indirect coal liquefaction processes,
4
as well as many others not listed here including those in planning stages and under
construction, are tabulated in the Gasification Technologies Council's World Gasification
Database

Environmental considerations

Most coal liquefaction processes are associated with significant CO2 emissions from the
gasification process or from heat and electricity inputs to the reactors thus contributing
to global warming especially if coal liquefaction is conducted without carbon capture and
storage technologies. High water consumption in water-gas shift or methane steam
reforming reactions is another adverse environmental effect. On the other hand,
synthetic fuels produced by indirect coal liquefaction processes tend to be 'cleaner' than
naturally occurring crudes, as heteroatom (e.g. sulfur) compounds are not synthesized
or are excluded from the final product.
Pyrolysis of coal produces polycyclic aromatic hydrocarbons, which are
known carcinogens.
CO2 emission control at Erdos CTL, an Inner Mongolian plant with a carbon capture and
storage demonstration project, involves injecting CO2 into the saline aquifer of Erdos
Basin, at a rate of 100,000 tonnes per year. As of late October 2013, an accumulated
amount of 154,000 tonnes of CO2 had been injected since 2010, which reached or
exceeded the design value.
Ultimately, coal liquefaction-derived fuels will be judged relative to targets established
for low-greenhouse gas emissions fuels. For example, in the United States,
the Renewable Fuel Standard and Low-carbon fuel standard such as enacted in the
State of California reflect an increasing demand for low carbon-footprint fuels. Also,
legislation in the United States has restricted the military's use of alternative liquid fuels
to only those demonstrated to have life-cycle GHG emissions less than or equal to
those of their conventional petroleum-based equivalent, as required by Section 526 of
the Energy Independence and Security Act (EISA) of 2007.
Research and development of coal

The United States military has an active program to promote alternative fuels use, and
utilizing vast domestic U.S. coal reserves to produce fuels through coal liquefaction
would have obvious economic and security advantages. But with their higher carbon
footprint, fuels from coal liquefaction face the significant challenge of reducing life-cycle
GHG emissions to competitive levels, which demands continued research and
development of liquefaction technology to increase efficiency and reduce emissions. A
number of avenues of research & development will need to be pursued, including: 5
 Carbon capture and storage including enhanced oil recovery and developmental
CCS methods to offset emissions from both synthesis and utilization of liquid fuels
from coal,
 Coal/biomass/natural gas feedstock blends for coal liquefaction: Utilizing carbon-
neutral biomass and hydrogen-rich natural gas as co-feeds in coal liquefaction
processes has significant potential for bringing fuel products' life-cycle GHG
emissions into competitive ranges,
 Hydrogen from renewables: the hydrogen demand of coal liquefaction processes
might be supplied through renewable energy sources including wind, solar, and
biomass, significantly reducing the emissions associated with traditional methods of
hydrogen synthesis (such as steam methane reforming or char gasification), and
 Process improvements such as intensification of the Fischer-Tropsch process,
hybrid liquefaction processes, and more efficient air separation technologies needed
for production of oxygen (e.g. ceramic membrane-based oxygen separation).
Since 2014, the U.S. Department of Energy and the Department of Defense have been
collaborating on supporting new research and development in the area of coal
liquefaction to produce military-specification liquid fuels, with an emphasis on jet fuel,
which would be both cost-effective and in accordance with EISA Section 526. Projects
underway in this area are described under the U.S. Department of Energy National
Energy Technology Laboratory's Advanced Fuels Synthesis R&D area in the Coal and
Coal-Biomass to Liquids Program.
Every year, a researcher or developer in coal conversion is rewarded by the industry in
receiving the World Coal to X Award. The 2016 Award recipient is Mr. Jona Pillay,
Executive director for Gasification & CTL, Jindal Steel & Power Ltd (India).
In terms of commercial development, coal conversion is experiencing a strong
acceleration. Geographically, most active projects and recently commissioned
operations are located in Asia, mainly in China, while U.S. projects have been delayed
or canceled due to the development of shale gas and shale oil.
COAL CARBONIZATION AND COKE OVEN PLANT

Coal carbonization is used for processing of coal to produce coke using metallurgical
grade coal. Coal carbonization involves heating of coal in the absence of air. Coke
making process is multistep complex process and variety of solid liquids and gaseous
products are produced which contain many valuable products. Various products from
coal carbonization in addition to coke are coke oven gases. coal tar, light oil, and
aqueous solution of ammonia and ammonia salt. Coke oven gases are about 310-340
cum per tone of dry coal which contains gaseous products, coal tar vapours, light oil 6
and water [Mukhulyonov et al., 1974]. With the development of steel industry there has
been continuous development in coke oven plant since latter half of nineteenth century.
to improve the process conditions, recovery of chemicals and environmental pollution
control strategies and energy consumption measures
Carbonization can be carried out at low temperature or high temperature. Low
temperature carbonization is used to produce liquid fuels while high temperature
carbonization is used to produce gaseous products [Trodakar & Belgaonnkar1991].
Low temperature carbonization (450-750oC): In low temperature carbonization
quantity of gaseous product is less while liquid products are large. High temperature
carbonization (above 900oC): In high temperature carbonization, the yield of gaseous
product is more than liquid products with production of tar relatively low. The potential
availability of chemicals from high temperature carbonization (above 900oC) and
low temperature carbonization (450-750oC) is given in Table M-II 2.1 and Table M-II 2.2
respectively.

COKE OVEN PLANT

Due to the development of iron and steel industry coke oven plant has become an
integral part of iron and steel industry. Due to increasing demand of iron and steel, there
has been a considerable increase in the coke oven capacity which resulted increase
output of coal chemicals.
Two types of coke manufacturing technologies use are:
 Coke making through by product recovery
 Coke making through non-recovery/ heat recovery
In India, building of coke oven batteries was initiated in the beginning of the ninth
century, now about 3000 ovens are in operation/ construction in the coke oven plant. By
the year 2011-12. The world coking coal requirement will be about 433 million metric
tons in which India’s requirement is estimated to about 54 million tones. By product from
coal gasification plant includes coke, coal tar, sulphur, ammonia. Coal tar distillation
produces tar, benzol, cresol, phenol, creosote.
Coking Coals: Blast furnace requires coke of uniform size, high mechanical strength,
and porosity with minimum volatile matter and minimum ash. Coking coal may be dived
I on the basis of their coking properties: prime coking coal, medium coking coal, semi
coking coal. The prime coking coal produce strong metallurgical coke while coals of
other groups yield hard coke only the concentration of moisture ash, Sulphur and
sometime phosphorous and ash fusion temperature are important in determining the
grade of coking coal since they influence the quality of coke produced. Low moisture,
ash, Sulphur and phosphorous content in the coal are desirable for production of good 7
quality coke. The desired analysis of typical coal charge to coke oven is.
Ash content: 16% ±0.5%
Moisture: 6-7%
Volatile matter: 22-25%
Fixed carbon: 58-60%%
Sulphur: 0.56%
Phosphorous: 0.09%
Some of the other factors affecting quality of coke are rank of coal, particle size, bulk
density, weathering of coal, coking temperature and coking rate, soaking time,
quenching practice.
Complexity in carbonization

A series of processes that involve carbonization.

Since carbonization is a pyrolytic reaction, it is considered a complex process in which

many reactions take place concurrently such as dehydrogenation, condensation,
hydrogen transfer and isomerization.
Carbonization differs from coalification in that it occurs much faster, due to its reaction
rate being faster by many orders of magnitude.
For the final pyrolysis temperature, the amount of heat applied controls the degree of
carbonization and the residual content of foreign elements. For example, at T ∼ 1200 K
the carbon content of the residue exceeds a mass fraction of 90 wt.%, whereas at T ∼
1600 K more than 99 wt.% carbon is found. Carbonization is often exothermic, which
means that it could in principle be made self-sustaining and be used as a source of
energy that does not produce carbon dioxide. In the case of glucose, the reaction
releases about 237 calories per gram.
When biomaterial is exposed to sudden searing heat (as in the case of an atomic
bomb explosion or pyroclastic flow from a volcano, for instance), it can be carbonized
extremely quickly, turning it into solid carbon. In the destruction of Herculaneum by a 9
volcano, many organic objects such as furniture were carbonized by the intense heat.

How wood is transformed into charcoal

The carbonization of wood in an industrial setting usually requires a temperature above

280°C, which liberates energy and hence this reaction is said to be exothermic. This
carbonization, which can also be seen as a spontaneous breakdown of the wood,
continues until only the carbonised residue called charcoal remains. Unless further
external heat is provided, the process stops and the temperature reaches a maximum of
about 400°C. This charcoal, however, will still contain appreciable amounts
of tarry residue, together with the ash of the original wood.

Industrial safety in carbonization

Carbonization produces substances which can prove harmful and simple precautions
should be taken to reduce risks.
The gas produced by carbonization has a high content of carbon monoxide which is
poisonous when breathed. Therefore, when working around the kiln or pit during
operation and when the kiln is opened for unloading, care must be taken that proper
ventilation is provided to allow the carbon monoxide, which is also produced during
unloading through spontaneous ignition of the hot fuel, to be dispersed.
The tars and smoke produced from carbonization, although not directly poisonous, may
have long-term damaging effects on the respiratory system. Housing areas should,
where possible, be located so that prevailing winds carry smoke from charcoal
operations away from them and batteries of kilns should not be located in close
proximity to housing areas.
Wood tars and pyro ligneous acid can be irritant to skin and care should be taken to
avoid prolonged skin contact by providing protective clothing and adopting working
procedures which minimize exposure.
The tars and pyro ligneous liquors can also seriously contaminate streams and affect
drinking water supplies for humans and animals. Fish may also be adversely affected.
Liquid effluents and waste water from medium and large scale charcoal operations
should be trapped in large settling ponds and allowed to evaporate so that this water
does not pass into the local drainage system and contaminate streams. Fortunately
kilns and pits, as distinct from retorts and other sophisticated systems, do not normally
produce liquid effluent - the by-products are mostly dispersed into the air as vapors.
Precautions against airborne contamination of the environment are of greater
importance in this case.

10
Carbonization and biodiesel fuels

In one study, carbonization was used to create a new catalyst for the generation
of biodiesel from ethanol and fatty acids. The catalyst was created by carbonization of
simple sugars such as glucose and sucrose. The sugars were processed for 15 hours at
400 °C under a nitrogen flow to a black carbon residue consisting of a complex mixture
of polycyclic aromatic carbon sheets. This material was then treated with sulfuric acid,
which functionalized the sheets with sulfonate, carboxyl, and hydroxyl catalytic sites.