ESE-800

Clean Coal Technologies

Part1:Coal to Liquid (CTL)

Lecture-11
Direct Coal Liquefaction

Presented By
Shahid Hussain Ansari
Assistant Professor
Centre for Energy Systems (CES)
National University of Sciences & Technology (NUST)
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 Direct Coal Liquefaction
 Direct liquefaction processes add hydrogen to the hydrogen
deficient organic structure of the coal, breaking it down only as
far as is necessary to produce distillable liquids
 Coal dissolution is accomplished under high temperature
(~400C) and pressure (~1500-3000 psi) with hydrogen and a
coal-derived solvent
 The coal fragments are further hydrocracked to produce a
synthetic crude oil
 This synthetic crude must then undergo refinery upgrading and
hydro-treating to produce acceptable transportation fuels

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Block Flow Diagram of Direct Coal Liquefaction

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 History of Direct Coal Liquefaction
 Direct coal liquefaction starts just prior to World War II by
Germany, and then continues the research by the U.S. Bureau of
Mines & others

 Since the early 1980s, interest has diminished due to the

decrease in crude oil prices, but the invasion of Kuwait by Iraq
in 1990 caused the world to reevaluate their position and think
about a national energy policy which will provide incentives to
develop U.S. natural resources

 This stimulates alternative fuel options to produce liquid

hydrocarbons from domestic energy resources such as coal

 Coal liquefaction would be an attractive option due to the vast

coal reserves
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 History of Direct Coal Liquefaction
 In 2008, Shenhua, China’s top coal producer, conducted trial
operations of a 1 million-ton/year (16,300 barrel/day) direct coal
to liquid (CTL) production facility producing quality diesel,
naphtha and oil
 This trial run made China the only country in the world to have
achieved key technologies for 1 million-ton-scale DCL facility
 The trial ended after 300 hours, but Shenhua made
improvements so it could conduct a 1,000-hour trial
 However, in 2009, China announced that the commercial plant
had been put on hold due to concerns of economics and
greenhouse gas emissions
 This DCL facility was reported to cost $1.46 billion

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 Second Generation Technology
 Second generation technology came along in the late 1970s and
early 1980s
 The U.S. pilot plants to develop these processes included:
1) SRC-II (solvent refined coal) in Tacoma, Washington and
Wilsonville, Alabama
2) EDS (Exxon Donor Solvent) in Baytown, Texas
3) H-Coal in Catlettsburg, Kentucky

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 Second Generation Technology
 Both the SRC-II and EDS process depended on a donor solvent
for hydrogen during the liquefaction and used the minerals in the
coal for a catalyst
 EDS did use a catalytic stage to hydro-treat part of the recycle
solvent in a second reactor but no catalyst was used in the coal
liquefaction unit
 The H-Coal process was developed by Hydrocarbon Research
Inc. (HRI) and was derived from their H-Oil process for
petroleum reside upgrading
 The basis of the process was a novel catalytic reactor in which
the catalyst was ebullated in the liquid phase, similar to the more
familiar gas-phase fluidized bed processes used in the petroleum
industry
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 Second Generation Technology
 The advantage of this type reactor is that the reactor contents are
well mixed helping to alleviate the excessive heat release
associated with coal liquefaction plus the ability to add and
withdraw catalyst from the reactor while it is operating so that
the catalyst activity is maintained at a relatively high and
constant level

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 Hydrogen/Carbon Mole Ratio

CTL

GTL

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 Hydrogen/Carbon Mole Ratio
 To make liquid fuels from coal -need to add hydrogen or reject
carbon
 To make liquid fuels from natural gas -need to reject hydrogen or
add carbon
 Adding hydrogen and rejecting carbon (or vice versa) may be
equivalent
 Water Gas Shift (WGS) Reaction (CO + H2O ↔CO2+ H2)

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 History of Direct Coal Liquefaction
 Direct conversion processes can be broadly broken up into two
different methods
1) Hydrogenation Processes (Bergius Process)
2) Pyrolysis or carbonization processes

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 Hydrogenation Process (Bergius Process)
 In this process, coal is liquefied by mixing it with hydrogen gas
and heating the system (hydrogenation)
 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 to 5,000 °C and 20 to 70 MPa hydrogen
pressure
 The reaction can be summarized as follows:
nC + (n+1)H2 = CnH2n+2

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Hydrogenation Process (Bergius Process)

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 Most Important Hydrogenation Processes
 Koheleol Process
 NEDOL Process
 H-Coal Process
 SRC-I Process (Solvent Refined Coal)
 SRC-II Process
 Exxon Donor Solvent (EDS) Process
 Imhausen High-pressure Process
 Conoco Zinc Chloride Process
 Lummus Integrated Two Stage Liquefaction (ITSL)
 Wilsonville Two Stage Liquefaction
 Catalytic Multi-stage Liquefaction (CMSL)
 Chevron Coal Liquefaction Process (CCLP)
 Advanced Liquefaction Concepts (ALC)
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 Most Important Carbonization Processes
 Karrick Process
 COED Process
 COGAS Process
 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

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 Single Stage & Two Stage Direct Liquefaction Processes
 A single-stage direct liquefaction process gives distillates via one
primary reactor. Such processes may include an integrated on-
line hydro-treating reactor, which is intended to upgrade the
primary distillates without directly increasing the overall
conversion
 A two-stage direct liquefaction process is designed to give
distillate products via two reactor stages in series. The primary
function of the first stage is coal dissolution and is operated
either without a catalyst or with only a low-activity disposable
catalyst. The heavy coal liquids produced in this way are hydro-
treated in the second stage in the presence of a high-activity
catalyst to produce additional distillate.

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 Pyrolysis or Carbonization Processes
 The carbonization conversion occurs through pyrolysis and it
produces condensable coal tar, oil & water vapor, non-
condensable synthetic gas, and a solid residue-char
 The condensed coal tar and oil are then further processed by
hydrogenation to remove sulfur and nitrogen species, after which
they are processed into fuels

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EDS Process

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 EDS Process
 Coal is slurried with a distillable recycled solvent that has been
re-hydrogenated to restore its hydrogen donation capacity
 The slurry is mixed with H2, preheated and fed to a simple up-
flow tubular reactor that operates at 425-450C and 2575 psig
 No catalyst is added to liquefaction reactor
 Naphtha, middle & heavy distillate products are recovered
 Re-hydrogenation in a fixed-bed catalytic reactor, using nickel-
molybdenum or cobalt-molybdenum on an alumina support
 The hydrogenation reactor is operated at 370 ºC &1600 psig,
although conditions are varied to control the degree of
hydrogenation of the solvent and thus maintain its quality
 Yields of up to 47% for lignite, 50% for sub-bituminous coals
and 60% for bituminous coals could be achieved
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H-Coal Process

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H-Coal Ebullated-Bed Reactor

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 H-Coal Process
 Coal is slurried with a recycle solvent that consists of a mixture
of a solids containing hydrocracker product with heavy and
middle distillates obtained by product fractionation
 H2 is added and the mixture is preheated and fed to an ebullated
bed hydrocracker, which is distinguishing feature of process
 This reactor operates at 425-455°C and a pressure of 2900 psig
 A conventional supported hydro-treating catalyst, either Ni-Mo or
Co-Mo alumina is used. The catalyst is fluidized by H2 and a
pumped internal recycle stream, for which the intake is
positioned above the upper limit of the expanded bed of catalyst
but still within the reactor liquid zone
 The ebullated-bed reactor system offers substantial advantages
over fixed-bed reactors, reactor contents are well mixed and
temperature monitoring and control are more easily effected
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 H-Coal Process
 Ebullated-bed reactors allow catalyst to be replaced while the
reactor remains in operation, enabling a constant catalyst
activity to be maintained
 The reactor products pass to a flash separator. Liquids in the
overheads are condensed and routed to an atmospheric
distillation column, producing naphtha and middle distillate
 The flash bottoms are fed to a bank of hydro-cyclones. The
overheads stream, which contains 1-2% solids, is recycled to the
slurrying stage. The underflow is routed to a vacuum distillation
column. Solids are removed with the vacuum column bottoms,
while the vacuum distillate forms part of the product for export
 As with other processes, yields are dependent on the coal

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Wilsonville Two Stage Liquefaction

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Catalytic Multi-stage Liquefaction

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 Catalytic Multi Stage Liquefaction
 In 1993, the two-stage liquefaction system evolved into the
catalytic multi-stage liquefaction (CMSL) system
 The sulfate-modified iron-based catalysts are more efficient as
compared to dispersed iron catalyst
 Addition of small amount of Mo (100 ppm) improved
conversion
 In CMSL system with iron-based catalyst in both reactors, coal
conversion is in the range of 93-96 wt %, reside conversion of
83-92 wt %
 The level of performance achieved was better than that obtained
with any other catalyst system

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 Catalytic Multi Stage Liquefaction
 The role of catalyst in the first stage of the CMSL process
 Promote hydrogenation of the solvent
 Stabilize the primary liquefaction products
 Hydrogenate the primary and recycle reside
 In the second stage
 Promote heteroatom removal & thus product quality improvement
 Convert reside to distillate
 Promote secondary conversion to lighter products, and aids in
avoiding dehydrogenation
 Types of catalyst
 Supported catalysts (Co/Mo, Co/Ni)
 Dispersed Catalyst (Fe, Mo)
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History of US Direct Coal Liquefaction

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History of Others Direct Coal Liquefaction

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Direct Coal Liquefaction Scale-up and Commercial
Development

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Shenhua Direct Coal Liquefaction Block Flow Diagram

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Axens H-Oil and Coal Liquefaction Reactors

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Shenhua Plant

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 Speculations About Shenhua DCL Plant
 Direct liquefaction–Conversion and hydrocracking to oils
 Two reactors in series
 Purpose: conversion and hydrocracking to oils
 Slurry catalyst
 Expanded bed reactors (probably slurry)
 Solvent Hydro-treating and upgrading
 Ebullated Bed (H-Oil)
 Hydro-treating
 Recycle solvent hydro-treating
 Manufactured petroleum catalyst (Co-Mo or Ni-Mo)
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 According to a test of direct coal liquefaction is performed using
a low rank bituminous coal as feedstock, and the operation
conditions and test results are as follows:

 Test operation conditions:

 Reactor temperature: 1st reactor 455°C, 2nd reactor 455°C
 Reactor pressure: 1st reactor 19.0MPa, 2nd reactor 19.0MPa
 Slurry coal concentration: 45/55(dry coal/solvent, mass ratio)
 Catalyst addition rate: 1.0 wt %(Fe/dry coal)
 Sulfur addition rate: S/Fe=2(molar ratio)
 Gas/liquid: 1000NL/Kg slurry
 Hydrogen in the recycle gas: 85vol %

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Direct Coal Liquefaction Scale-up and Commercial
Development

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Conceptual Flow of In-line Hydro-treating Section

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 Brown Coal Liquefaction Process
 The BCL process was developed by NEDO of Japan to a 50 tpd
pilot-plant scale, constructed at Morwell in Victoria, Australia
 The process is designed specifically to handle very low-rank
coals which may contain >60% moisture
 It was operated over the period 1985-1990, processing a total of
~60,000 ton of coal. Operations ceased in October 1990. The
plant was decommissioned in 1991 and demolished in 1992
 A crucial aspect is the efficient drying of the coal
 Following extensive pilot plant operation on a 0.1 tpd bench-
scale continuous liquefaction test facility & related equipment
was carried out until 1997 to improve reliability, economics &
environmental compatibility of coal liquefaction process

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 Brown Coal Liquefaction Process
 Based on the R&D results an improved BCL process was
proposed. This comprises slurry de-watering, liquefaction, in-
line hydr-otreating, and de-ashing, with the following features:
 Use of a high-active and inexpensive catalyst such as limonite ore
pulverized in oil
 Use of a heavy fraction solvent (bp 300-420ºC)
 Adoption of coal liquid bottom (CLB) bp>420ºC recycling
 It was estimated that the improved process could decrease the
crude oil equivalent nominal price by 24% compared with the
BCL process at the Australian pilot plant
 Yields are stated to be 65% distillate
 A new cooperation agreement was started between Japan (Sojitz)
and Indonesia in 2005 to build a 27,000 BPD plant
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Specification of BCL Products

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Hybrid DCL/ICL Plant Concept

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 Benefits of Direct Coal Liquefaction
 Direct liquefaction efficiency may be higher than indirect
technology. One ton of a high volatile bituminous coal can be
converted into approximately three barrels of high quality
distillate syncrude for refinery upgrading and blending
 Direct Liquefaction provides high octane, low sulfur gasoline
and a distillate that will require upgrading to make an acceptable
diesel blending stock
 Development of direct liquefaction technology could lead to
hybrid (direct/indirect) processes producing high quality gasoline
and diesel
 The NCC, others suggest that direct liquefaction may have a
better carbon footprint than indirect technology

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Potential Technology Vendors

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 Comparison of DCL & ICL
 In Direct Coal Liquefaction (DCL) pressure, heat and
catalyst are used to crack the coal to make liquids
 Theoretical efficiency can be high…roughly 70-75%
 Sledge hammer approach
 In Indirect Coal Liquefaction (ICL) coal is first gasified to
form syngas. Syngas is then converted to liquids by means of
a catalyst and Fischer Tropsch (FT) chemistry
 Synthesis Gas or Syngas (Mixture of CO, H2, CO2, H2O)
 Theoretical efficiency is lower…roughly 60-65%
 Engineered approach

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Comparison of DCL & ICL

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 Quality of Products from DCL
 Liquid Products are much more aromatic than indirect –DCL
Naphtha can be used to make very high octane gasoline
component; however aromatics content of Reformulated
Gasolines is now limited by EPA –DCL Distillate is poor diesel
blending component due to high aromatics which results in low
cetane versus U.S. average of about 46
 Raw DCL Liquids still contain contaminants: Sulfur, Nitrogen,
Oxygen, possibly metals and require extensive hydrotreatment
to meet Clean Fuels Specifications

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 Benefits of Direct Coal Liquefaction
 Direct liquefaction efficiency may be higher than indirect
technology. One ton of a high volatile bituminous coal can be
converted into approximately three barrels of high quality
distillate syncrude for refinery upgrading and blending
 Direct Liquefaction provides high octane, low sulfur gasoline
and a distillate that will require upgrading to make an acceptable
diesel blending stock
 Development of direct liquefaction technology could lead to
hybrid (direct/indirect) processes producing high quality gasoline
and diesel
 The NCC, others suggest that direct liquefaction may have a
better carbon footprint than indirect technology
 Current direct liquefaction distillate products can meet the
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 Potential Merits of Direct Coal Liquefaction
 DCL produces high octane gasoline
 DCL has higher thermal efficiency than indirect liquefaction
 Literature suggests that DCL with no CCS may have a lower
carbon footprint
 Opportunity for combined coal and renewable energy processes
with improved carbon footprint and carbon management
 Synergistic opportunities
 Hybrid direct/indirect technology integration
 Coprocessing with biomass (Hydrogen production)
 Coprocessing with heavy oil/refinery bottoms/wastes

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 Direct Liquefaction Technical Needs
 Advanced concepts
 Reduce carbon footprint
 Combination coal and renewable energy concepts
 Co-feeding concepts
 Less severe processing
 Lower capital and process cost
 Product integration with refinery or finished distillate products
 Component material and reliability studies

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 Challenges of Direct Coal Liquefaction
 Uncertainty in World Oil Prices, High Capital Costs, Investment
Risk, Technical Challenges
• First technology (since 2ndWorld War) is being commercialized in the PRC
(Shenhua) –need other first-of-kind large scale operation (with carbon
management) to verify baselines and economics
• R&D activity should focus on remaining process issues such as further
improvement in efficiency, product cost and quality, reliability of materials
and components
• The timelines for demonstration and development of direct liquefaction
technology and carbon capture and storage must be integrated.
• Hybrid technology needs development including integrated demonstration
 Environmental Challenges
• CO2and criteria pollutants
• Water use
 Concerns with increased coal use in U.S.
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Thank You

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