Direct Coal Liquefaction:

Lessons Learned

Ripudaman Malhotra
SRI International
Menlo Park, CA 94025

Presented at GCEP Advanced Coal Workshop, BYU, Provo, UT; Mar 16, 2005
Outline

ƒ Why Liquefaction? Changing needs

ƒ Overview of direct coal liquefaction process
♦ Types of processes
♦ Process evolution
♦ Current status
ƒ Chemical Lessons
♦ Reaction pathways
♦ Coal structure: what is needed to liquefy coal
ƒ Conclusions
♦ Opportunities for improvement
Why Coal Liquefaction?

ƒ Alternate source for liquid fuels: national energy security

♦ Germany, Japan, South Africa
ƒ Production of a clean and reactive solid fuel: SRC
♦ Liquids are a secondary product that may improve economics
ƒ Oil embargos in the 1970’s reinforced need for an
alternate source of transportation fuel
ƒ Low oil prices in the next two decades: declining interest
ƒ Now? Energy security, efficiency, climate…
Liquefaction

ƒ Increasing H/C ratio is a must; Two options

♦ Reject carbon
ƒ Most pyrolysis processes
♦ Add hydrogen
ƒ Dry pyrolysis with hydrogen not effective
ƒ Coal liquefaction; use a solvent to effect hydrogenation
ƒ Products often solid at room temperature
ƒ Liquefaction defined by solubility
Coal Liquefaction Approaches

ƒ Pyrolysis or mild gasification

ƒ Direct coal liquefaction
ƒ Indirect coal liquefaction
ƒ Co-processing
ƒ Bioliquefaction
ƒ Substantial overlap in the chemistry of mild gasification,
direct coal liquefaction, and co-processing
Direct Coal Liquefaction
Processes: 1970 to 1995

ƒ Single-Stage Process: SRC-II, H-Coal, EDS

ƒ Two-Stage Process: NTSL, ITSL, RITSL,
DITSL, CTSL, CMSL…
♦ Many variations depending on
ƒ Use of catalyst in the two stages (therm-cat, cat-cat)
ƒ Distillation between stages
ƒ Separation of solids between two stages or after second
stage
ƒ Recycle of ashy bottom
ƒ Operation in H-balance
Single-Stage Processes

ƒ Contact coal with a solvent (2:1) with hydrogen or with

hydrogenated solvent at ca. 450°C
ƒ Recycle light oil fraction
ƒ Yield about 3 bbl oil/ton of coal with bituminous coals
ƒ Not as effective for subbituminous coals
ƒ Product difficult to refine (high aromaticity, N)
ƒ High yield of light hydrocarbons; efficiency of hydrogen
utilization is low
ƒ Demonstrated the feasibility at ca. 200 tons/day
Lessons Learned

ƒ Dissolution itself is fast!

ƒ Coal liquefaction is better in heavier, more
aromatic solvents
ƒ Longer residence time is detrimental
ƒ Process economics require maximizing liquids
ƒ Higher temperatures lead to more gas
♦ poorer hydrogen efficiency
Two-Stage Liquefaction at
Wilsonville
ITSL Initial Run
Distillate Distillate

Coal Thermal Solvent Antisolvent L-C Fining HT Solvent

Slurry Liquefaction Recovery Deasher Recovery

Ash/Coke

• Short contact thermal liquefaction

• Inter-stage separation
• Catalytic hydrotreating of de-ashed liquid
• Recycle of heavy hydrotreated solvent
• Hydrogen balance from coke gasification
Two-Stage Liquefaction at
Wilsonville
ITSL Final Run
Distillate Distillate

Coal Catalytic L-C Fining HT Solvent Antisolvent

Slurry Liquefaction Recovery Deasher

Ash/Coke

• Low severity catalytic liquefaction

• No Inter-stage separation
• Moderate severity hydrotreating and hydrocracking
• Match rate of solvent hydrogenation with that of coal decomposition
• Ashy bottoms recycle
• Make hydrogen from steam reforming of methane
 Liquefaction Product Yields, Illinois #6

100
(5.4)
(5.4) (6.6) (x.x) H-consumption
(4.8)

80

60
C--C3 Gases
Liquids
Soluble reject
Char
40

20

0
EDS H-Coal ITSL-1983 ITSL-1989
Process
- Schindler, 1989
 Liquefaction Product Yields, Wyodak

100

(7.0) (x.x) H-consumption

(4.4)
(6.2)
80 (4.3)

60
C--C3 Gases
Liquids
Soluble reject
Char
40

20

0
EDS H-Coal ITSL-1983 ITSL-1989
Process
- Schindler, 1989
 Liquids Yield

4.5

3.5

2.5
Illinois #6
Wyodak
2

1.5

0.5

0
EDS H-Coal ITSL-1983 ITSL-1989
Process
- Schindler, 1989
Process Economics
1999 $/Barrel Equiv. Crude
Required Selling Price

80.00
O&M
60.00 Coal
Capital Related
40.00

20.00

0.00
H-Coal ITSL CMSL

Major Lesson: Liquefaction is extremely capital intensive

- Burke, Winschel, Gray, 2001

Summary

ƒ Coal liquefaction is technically feasible

ƒ Process demonstrated at large scale (~200 tpd) for a
variety of coals
♦ US: H-Coal, EDS
♦ Canada: Canmet Co-processing
♦ Japan: Victoria Brown Coal Liquefaction, NEDOL
♦ UK, Germany
♦ China: Shenhua project (2007)
ƒ Economics not competitive, but not prohibitive either
(~$20B for 50,000 bpd)
Traditional View of Bond Cleavage
During Liquefaction

WEAK BOND HOMOLYSIS

CH2 • + •CH2
CH2 CH2

Solvent

CH3 + CH3

Solvent merely stabilizes thermally generated

radicals; not involved in inducing bond cleavage.
Inadequacy of “Donor Solvent”

ƒ Liquefaction yields do not correlate with

weakness of C-H bond in the donor solvent
♦ Dihydroanthracene with a much weaker C-H bond
than dihydropyrene or dihydrophenanthrene
consistently yields lower conversion to THF-solubles
♦ Discrepancy even more glaring under “H-shuttling”
conditions
ƒ Bonds too strong to cleave by simple homolysis
are nonetheless broken under liquefaction
conditions
“Liquefaction” of a Bibenzyl Polymer
FI-Mass Spectrum
Hydrogenolysis of strong Caryl-Calkyl bond comparable to thermolysis of weak Calkyl-Calkyl bond

97 kcal/mol

54 kcal/mol
Emerging View of Bond Cleavage

SOLVENT MEDIATED HYDROGENOLYSIS OF STRONG BONDS

Solvent CH2
CH2 •
H
Solvent engenders bond scission

+
H •CH2

Solvent engenders bond scission

Implications of Solvent-Mediated
Hydrogenolysis

ƒ Draw attention to H-accepting and H-transfer

properties of solvent components
ƒ Rationalize otherwise inexplicable behavior
♦ Increased liquids yields from partial replacement of
donor hydroaromatic with nondonor aromatic
♦ Efficacy of pyrene and related PAH
♦ Role of C-supported catalysts
ƒ Design processes that maximize H-utilization
efficiency
Increased Coal Content Aids Conversion
of Coal and of Non-Distillables
HRI STIRRED-REACTOR COPROCESSING

80
CONVERSION (%)

% Coal in Feed

10
40
80

70

Coal 975°F +
Aromatics in coal mobilize the H in the resid for conversion
-Duddy, Panvelker, 1991
Coal Conversion with Dispersed
Catalysts
Recycled IOM is more effective than freshly activated catalyst

Yield (%maf coal)

Fresh Catalyst Recycled IOMs

THF-Solubles 86 95

Cyclohexane-Solubles 36 64

Conversion of Illinois No. 6, Burning Star coal in hydrotreated V-178 distillate

Programmed heating at 8°C/min to 425°C under H2 pressure

- Bockrath, 1992
Potential Role of H-Transfer in
Catalytic Systems

COAL

H H

H
H COAL
CATALYST
Coal Structure

ƒ Application of polymer theory

♦ Characterization of cluster size and mean molecular
weight between clusters
♦ Rank dependent trends
ƒ 13C-NMR: Relatively small clusters of 8 to 18
carbons only
ƒ Distribution of oxygen, sulfur, and nitrogen
functionalities
ƒ Role of non-covalent linkages
Emerging Opportunities

ƒ Thermal efficiency of coal to oil by DCL: ~65%

♦ About 7 times worse than crude oil refining (95%)
ƒ Facile dissolution of bituminous coals in certain solvents
(Iino)
♦ Possible application for hyper clean coal
ƒ Augmented Pyrolysis (Miura)
♦ Mild gasification of methanol soaked coals to co-produce liquids
and high reactivity chars
ƒ Direct carbon fuel cell: coal, biomass, petcoke…
Conclusions

ƒ Coal liquefaction: technically feasible, but the

process to synthetic crude is not economic
ƒ Converting coal to transportation fuel for IC
engines does not reduce CO2 emissions
ƒ If needed for energy security, milder processes
with high coal to oil yields must be
demonstrated at commercially relevant scales
Acknowledgments

ƒ M. Gorbaty, ExxonMobil
ƒ F. Burke, D. Winschel, Consol
ƒ D. Gray, Mitretek
ƒ D. F. McMillen