Coal To Liquid Fuels

under the guidance of

Prof. K.K. Pant
Department of Chemical Engineering
Indian Institute of Technology-Delhi
Mirza Minhaz Baig (2012CHE2965) Sukhdeep Singh (2012CHE2768)
Noor Mohammed (2012CHE2774) Vaibhav Varshney (2012CHE2010)
1
Outline
Coal classification
Need for liquefaction
Products obtainable
Liquefaction processes
Comparison of DCL & ICL
ASPEN-HYSYS simulation of CTL, GTL & BTL
Techno-Economic evaluation of CTL
Conclusion
References
2
Coal classification
Coal Type Heat content
(MJ/Kg)
Fixed carbon
(% by wt)
Moisture
(% by wt)
Ash
(% by wt)
Anthracite 30-35 85 -98 < 15 10-20
Bituminous 25-35 45-85 2-15 3-12
Sub-Bituminous 20-30 35-45 10-45 < 10
Lignite 10-20 25-35 30-60 10-50
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Need for liquefaction
Efficient usage of low quality solid coal
Easy transportation
Easy storage
Conversion to liquid fuels offer more usage diversity
Better combustion efficiencies
Less environmental concerns
Variety of by products
4
Products obtainable
5
Liquefaction processes
Liquefaction
Direct Indirect
6
Direct Liquefaction
Coal is reacted with hydrogen under stringent catalytic conditions to produce a
crude, which is distilled further.
7
Flow sheet @ Direct process
8
Indirect Liquefaction
Coal is gasified first, then converted to liquid fuels via Fisher-Tropsh synthesis.
9
Flow sheet @ Indirect process
Source: Biofuels Academy & United state Department of Energy.
10
Comparison b/w DCL & ICL
11
Fixed Slurry bed reactors
Concept
Collection of solid catalyst
particles dispersed in a liquid
phase(slurry).
The slurry is circulating at a high
velocity impelled by an axial
pump.
The mixing pattern is well
defined.
12
13
Concept
Collection of fixed solid
particles.
The particles may serve as
a catalyst or an adsorbent.
Continuous gas flow
Applications
Synthesis gas production
Methanol synthesis
Ammonia synthesis
Fischer-Tropsch synthesis
Gas cleaning (adsorption)
Multi tubular Fixed Bed Reactors
Circulating Fluidized Bed Reactors
Advantages/Disadvantages
Conversion may be poor if gas is
bypassing.
Erosion of vessel and pipe lines.
Uniform temperature
Efficient heat-exchange
Can handle rapid deactivating
processes.
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Fixed Fluidized Bed Reactor
Advantages
Uniform Particle Mixing
Uniform Temperature Gradients.
Ability to Operate Reactor in Continuous State.
Disadvantages
Increased Reactor Vessel Size
Pumping Requirements and
Pressure Drop
Particle Entrainment
Erosion of Internal Components
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Direct Coal to Liquid Process
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.
Direct processes are :
1. Carbonization
2. Hydrogenation
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Direct Coal Liquefaction Process
17
Make-Up H
2
Recycle H
2
Coal + Catalyst
Slurry
H-Donor
Slurry
DAO
H
2
S, NH
3
, CO
x
C
1
C
2
LPG
Gasoline
Diesel Fuel
HVGO
Ash Reject
Coal
Liquefaction
HTU
Gas Recovery
Treatment
Refining
Fractionation
Solvent
De-ashing
Pyrolysis and Carbonisation Process
Carbonization occurs through pyrolysis or destructive distillation.
It produces coal tar, oil and water vapor, synthetic gas, and a solid
residue-char.
The coal tar and oil are then further processed by hydro treating to
remove sulfur and nitrogen.
Karrick(low T) Process: Coal is heated at 680 F (360 C) to 1,380
F (750 C) in the absence of air.
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Hydrogenation Process
Bergius process developed by Friedrich Bergius in 1913
Reaction: nC + (n -x+ 1)H
2
C
n
H
2 n-2x + 2
x=Degree of unsaturation
Reaction occurs at betwen 400 C to 500 C and 20 to
70 MPa H
2
pressure
Catalyst: tungsten or molybdenum sulfides, tin or nickel
oleate
produces heavy oils, middle oils, gasoline, and gases.
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Coal-To-Liquids: Current Status
Costs many systems analyses ongoing; for 50,000 bpd plant:
Capital costs estimated at $3.54.5 billion
Product cost at $40/bbl
Technology considered commercial
DOE/industry completed program for development of direct liquefaction technology
Sasol producing 150,000 bpd of F-T products
Shenhua China Coal Liquefaction Corp. constructing 20,000 bpd plant; additional
180,000 bpd planned
Shenhua supports feasibility studies for two 80,000 bpd coal-to-liquid plants
Improved processes, catalysts, and slurry reactors available
Bench and pilot facilities at Rentech, Headwaters, Syntroleum, and ConocoPhillips
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Coal Liquefaction: Material Balance
Coal Gasifier Air Separation
Unit
Gas
Cleaning
Water Gas Shift
Reactor
H
2
/CO = 2
CO
2
vented or
to storage
535 TPH
Fischer Tropsch
Synthesis
C
1
-C
4
18 TPH
C
5
-C
10
35 TPH
C
10
-C
20
56 TPH
>C
20
31 TPH
Air
1482 TPH
Coal
450 TPH
N
2
1118 TPH
Syngas
906 TPH
Slag
58 TPH
Residual Gases
215 TPH
890 TPH
Water
150 TPH
Oxidant
364 TPH
O H CH H CO
2 2 2
2
Basic FT reaction
Water Gas Shift reaction
CO + H
2
O = CO
2
+ H
2
Coal gasification
Coal + Air/Oxygen = CO + H
2
O + CO
2
+ H
2
O
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ASPEN-HYSYS Simulation @ CTL
22
Results for various Coals
23
(Wt. %) Anthracite Bituminous Sub-Bituminous Lignite
C 0.85 0.789 0.7433 0.7049
H 0.025 0.055 0.054 0.0475
N 0.009 0.0138 0.01 0.0122
S 0.005 0.04 0.0051 0.0214
O 0.111 0.1022 0.1876 0.214
GAS(mol%) Anthracite Butuminous Sub-Bituminous Lignite
CO 0.6125 0.5493 0.5649 0.5687
H2 0.0299 0.0421 0.0505 0.0505
CO2 0.2479 0.266 0.2793 0.2697
H2S 0.0024 0.0193 0.0025 0.0101

Composition @ Ultimate Analysis
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Syngas composition @ various Coals
25
Andersen Schultz Flory Distribution
26
where W
n
is the weight fraction of hydrocarbon molecules containing n carbon atoms. is the
chain growth probability or the probability that a molecule will continue reacting to form a
longer chain. In general, is largely determined by the catalyst and the specific process
conditions
FT Process Product Distribution
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FT Process Outputs
28
Coal Consumption 2.7 million tons
(same as 1000 MW power plant)
Products
Light Hydrocarbons(C
1
C
4
) 0.11 million tons
Naphtha (C
5
C
10
) 0.21 million tons
Diesel (C
11
C
20
) 0.34 million tons
Wax (>C
20
) 0.19 million tons
CO
2
emissions 3.20 million tons (Problem)
FT Diesel Exhaust Emissions
29
-42
-33
-9
-28
-45
-40
-35
-30
-25
-20
-15
-10
-5
0
Hydrocarbon CO N0x Particulates
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F
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)
Comparison of Petroleum & Coal derived Diesel
Properties Diesel FT Diesel
Density, g/cm
3
(20
o
C)
Viscosity, mm
2
/s (20
o
C)
Potential Aromatic, w%
S, ppm
N, ppm
Cetane No.
Flash Point,
o
C
Solidification Point,
o
C
Cold Filter Plugging Point,
o
C
0.832
2 - 6
68.8
<6
<0.5
51
65
-15
-55
0.8648
3.69
81.9
<5
<1
46.7
76
-26
-90
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ASPEN-HYSYS Coal To Liquid process
31
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Assumptions:
100 % conversion.
All reactors are completely insulated.
Energy balance equation:
Heat in+Heat Given=Heat out+Heat of reaction
Cp/R=A+BT+CT
2
Where A,B and C are constant.
CTL Process Energy balance
Contd
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Sensible heat for water @ 1.013 bar(25C to
800C)
Q= 32402.75KJ
Heat of reaction =-401.9KJ/mol
For stream @ 2.026 bar, Specific enthalpy(total heat)
Q= 27062.9 KJ
Contd
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Qtotal at mixer
inlet=(32402.75+27062.9+0.033)KJ
=59465.68KJ
Heat recovery from cooler is 20%
So; Energy released from the cooler to the
atmosphere=
59465.68KJ *20/100=11893.13KJ
Contd
35
Energy from cooler out=47572.5433KJ
Latent heat for Syn gas=517.5KJ/Kg@NTP
Q=55Kg*517.5KJ/Kg=28462.5KJ
Heat of reaction for water gas shift reaction
=-42.3KJ/kmol
(Energy out from cooler+ heat of reaction of water gas
shift reaction)=47572.5433KJ
So;Heat out from 2
nd
cooler=(47572.5433-
28462.5)KJ=19110.0433KJ
GTL Gas Composition
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GTL Mass Fraction
CH4 0.9863
N 0.0135
O 0.002
GTL-Syngas
Comp.
Mole
Frac. kg/h
CO 0.1306 3.765
H2 0.637 17.175
CO2 0.3223 8.0575
H2S 0 0
Source: http://www.uniongas.com/aboutus/aboutng/composition.asp
BTL-Biomass Composition
37
BTL Mass Fraction
C 0.5
H 0.063
N 0.008
O 0.43
S 0.0003
Biomass: Agricultural waste.
BTL-Syngas
Comp. Mole Frac. kg/h
CO 0.1506 3.765
H2 0.647 17.175
CO2 0.3923 8.0575
H2S 0.00002 1.054
Source: Jared P. Ciferno, John J. Marano, Benchmarking Biomass Gasification Technologies for Fuels, Chemicals and Hydrogen
Production, U.S. Department of Energy National Energy Technology Laboratory, pp-6, June 2002
CO2 @ CTL,GTL & BTL Process
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Techno-Economic Analysis of CTL
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CTL Life Cycle Emissions, $0/ton CO2
Source: Paulina Jaramillo, A Life Cycle Comparison of Coal and Natural Gas for Electricity Generation and the Production
of Transportation Fuels, PhD Thesis, Carnegie Mellon University Pittsburgh, Pennsylvania, pp-82-97, 2007.
Contd..
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CTL Life Cycle Emissions, $100/ton CO2
Source: Paulina Jaramillo, A Life Cycle Comparison of Coal and Natural Gas for Electricity Generation and the Production
of Transportation Fuels, PhD Thesis, Carnegie Mellon University Pittsburgh, Pennsylvania, pp-82-97, 2007.
Conclusion
Out of GLT,CTL & BTL: CTL produces less CO2 in comparison with other processes.
CO2 generation is the main concern with all the processes. So Carbon capturing need to be
employed.
Feasibility of CTL is quite sensitive to the price of crude oil & Coal. If the carbon tax increases for a
given crude oil price, coal price has to decrease to make CTL economically favorable.
A wide range of reactor configurations are available for gasification of Coal with different heat &
mass transfer characteristics.
Indirect FT-synthesis happens to be the work-horse of Coal gasification.
CTL fuels seems to offer less harm to environment as compared to conventional petroleum fuels.
Not very significant change is observed in syngas composition as coal type is changed.
IN NUTSHELL, THERE EXIST A GREAT POTENTIAL TO SWITCH CTL, PROVIDED CO2 IS HANDLED
PROPERLY.
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References
1. http://www.worldcoal.org/coal/what-is-coal/
2. http://www.netl.doe.gov/technologies/hydrogen_clean_fuels/refshelf/presentations/20090409_LTI_
DC %20Presentation%20-%20Comprehensive%20Overview.pdf
3. http://www.antiessays.com/free-essays/359709.html
4. http://www.engineeringtoolbox.com/coal-heating-values-d_1675.html
5. http://www.biofuelsacademy.org
6. http://en.wikipedia.org/wiki/Heat_of_combustion
7. http://gcep.stanford.edu/pdfs/RxsY3908kaqwVPacX9DLcQ/bajura_coal_mar05.pdf
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Contd
7. http://www.fischertropsch.org/primary_documents/patents/US/us1746464.pdf
8. http://www.sasol.com/sasol_internet/frontend/navigation.jsp?navid=1600033&rootid=2"t
echnologies & processes" Sasol
9. http://www.fischer-tropsch.org/DOE/DOE_reports/510/510-34929/510-34929.pdf P.L.
Spath and D.C. Dayton. "Preliminary Screening Technical and Economic Assessment
of Synthesis Gas to Fuels and Chemicals with Emphasis on the Potential for Biomass-
Derived Syngas", NREL/TP510-34929,December, 2003, pp. 95
10. http://www.netl.doe.gov/technologies/coalpower/gasification/gasifipedia/5-support/5-
11_ftsynthesis.html.
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