Dr. Ankit A. Jain & Dr. Ajay Gupta

Refining R&D Jamnagar

Direct Coal Liquefaction: Comprehensive Review Of Current

State Of The Art

Presented at 6th World Petrocoal Congress, 15-17th Feb, 2016, New Delhi

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© Reliance Industries Ltd., 2015

Dhirubhai H. Ambani Founder Chairman Reliance Group

• 1966- Establishes Textile mill in Naroda

• 1977- Public share offering Raised money from public

offerings oversubscribed 7X

• 1982- Builds fiber/filament plant in Patalganga

• 1995- Builds Polyolefin plants at Hazira

• 1997- Builds multi-feed cracker at Hazira

• 1999- Builds Jamnagar refinery

• 2002- Acquired IPCL a state run company

• 2008- Builds JERP refinery at Jamnagar

• 2009- Begins KG D6 gas production

• 2013- Builds PBR/SBR plants at Hazira

• 2014- Builds PTA plant at Dahej

• 2014- Builds PET plant at Dahej

RIL - BRIEF INTRODUCTION

© Reliance Industries Ltd., 2015

An

nu

al

oil

pro

du

ctio

n

Calendar Year

Peak Oil

Which year ?

Already reached ?Phase 1

- Easy to extract oil

- Oil > Demand Phase 2

- Tougher to extract oil

- Oil < Demand

Drivers for Coal Liquefaction (CTL)

Coal Resource

CTL Technology

Energy Market

Ideal Scenario for a CTL project

Available

High

demand/prices

Suitable for

high ash coal

Hubbert’s Curve (adapted [1])

World coal reserves [2]

Coal liquefaction [3]

[1] Ivanhoe, L.F., 1996. Updated Hubbert curves analyze world oil supply. World Oil, 217(11).

[2] WEB: http://chartsbin.com/view/n1n

[3] Shui, H., Cai, Z. & Xu, C., 2010. Recent advances in direct coal liquefaction. Energies, 3(2), pp.155–170.

Routes of coal liquefaction

• Indirect coal to liquid (ICL): Reaction of coal with steam/oxygen

(primarily CO + H2) which is then converted into liquids via Fischer-

Tropsch (F-T) reaction.

• Direct coal to liquid (DCL): Hydrogenation at relatively high

temperature and pressure.

nCH0.8 + xH2 → −CH2 − n

CH0.8 + H2O O2 → CO + H2 → −CH2 − + H2O

https://en.wikipedia.org/wiki/Friedrich_Bergius

Studies comparing the two routes of CTL

• Comparison of DCL and ICL [4-7]

• Relative analysis ([8])

[4] J. P. Longwell, E. S. Rubin and J. Wilson, Prog. Energy Combust. Sci., 1995, 21, 269–360.

[5] T. B. Simpson, Energy Fuels, 2002, 16, 1599–1600.

[6] Z. Zhang and Z. Men, Petroleum Refinery Engineering, Lianyou Sheji Bianjibu, 2003, vol. 33, pp. 58–61.

[7] R. H. Williams and E. D. Larson, Energy Sustainable Dev., 2003, 7,103–129.

[8] Coal liquefaction technologies- direct and indirect routes. Theo LK Lee, Headwater technology innovation group (USA) (online ppt)

[9] http://www.processonline.com.au/content/software-it/article/cutting-time-to-market-of-coal-to-liquid-energy-projects-1369718154 (last accessed, 12th Feb. 2016)

• Advantage DCL o 5-10 % more thermally efficient

o Lesser water consumption

o Lesser production of CO2

o Lower capital cost (~ 30 %)

o Higher liquid yields

o Can process wide stock of coal

Relative economic data Hybrid Direct Indirect

Total capital 1.031 1 1.135

Coal cost 1 1.018 1.160

Total operating cost 1 1.057 1.137

Required selling price 1 1.008 1.093

Hybrid DCL/ICL diagram [9]

DCL Technologies

1900 1920 1940 1960 1980 2000 2020

Tech

nic

al L

evel

Year

Two stage

Single stage

Single stage, very high pressure

Bergius Process, IG Fabren Process

ERC, EDS, SRC I, SRC II, H-Coal,IGOR+, IHP, CZC, NEDOL

BCL, LSE, CSTL, CCLP, ITSL, etc.- Better catalyst- Milder reaction conditions- Hydrogenated solvent

• DCL processes aim to add

hydrogen to the organic structure

of coal

• DCL technologies

Single stage processes

Two stage processes

• Co-processing (petroleum derived

oil/ coal) technologies

CTL

GTL

Brief history of DCL technologies [10]

[10] Dong, Xiucheng, et al. "EROI Analysis for Direct Coal Liquefaction without and with CCS: The Case of the Shenhua DCL Project in China." Energies 8.2 (2015): 786-807.

Hydrogen/carbon ratio [4]

Single/Two stage processes

• Two stage DCL process give distillate products via

two reactors or reactor train in series

o Primary reactor: Solubilize coal

(with/without low activity disposable

catalyst)

o Second reactor: Heavy coal liquids are hydro

treated in presence of a high activity catalyst

to produce additional distillates

• Single stage DCL process give distillates products via

one primary reactors or train of reactor in series

Schematic diagram: H-Coal process [11] Schematic diagram: Catalytic two stage liquefaction process [11]

[10] Department of trade and industry, 1999. Technology status: coal liquefaction, London.

Single Stage Processes

No. Technology Company

1 IGOR (VCC)

Process

Ruhrkohle, Germany

Veba Oil, Germany

(Now: BP/KBR)

2 NEDOL Process NEDO, Japan

3 H-Coal Process HRI, USA

4 Exxon Donor

Solvent (EDS)

Exxon, USA

5 Solvent Refined

Coal (SRC-I and

SRC-II)

Gulf Oil, USA

6 Imhausen High-

Pressure Process

Germany

7 Conoco Zinc

Chloride Process

Conoco, USA

No. Technology Company

1 Catalytic Two-stage Liquefaction (DOE, HTI, USA)

2 Liquid Solvent Extraction (British Coal Corporation,

UK)

3 Brown Coal Liquefaction (NEDO, Japan)

4 Consol Synthetic Fuel (CSF) (Consolidation Coal Co,

USA)

5 Chevron Coal Liquefaction

(CCLP)

(Chevron, USA)

6 Kerr-McGee ITSL (Kerr-McGee, USA)

7 Mitsubishi Solvolysis (Mitsubishi Heavy

Industries, Japan)

8 Pyrosol (Saarbergwerke, Germany)

9 Amoco CC-TSL (Amoco, USA)

10 Supercritical Gas Extraction

(SGE)

(British Coal Corporation,

UK)

11 Integrated Two-stage liquefaction (Lummus, USA)

Technologies differ on the reaction scheme/ catalyst / hydrogenation solvent

NEDOL, IGOR+,CTSL, LSE are considered ready for commercialization by developers

Three phase (slurry/ebullated) bed reactors used in most process

DCL Technologies

Process Organization Capacity Year Operating parameters Remarks

NEDOL Process

New Energy

Development

Organization

(NEDO), Japan

150 TPD

(Kashima, Japan)

1996-

2000

(1) 435-446 deg. C, 150-200

bar

- Fe based catalyst

- Solvent hydrogenation

step at 320 deg. C

-

IGOR+ Ruhrkohle, Germany

Veba Oil, Germany

200 TPD

(Bottrop,

Germany)

1981-

1987 470 deg. C, 300 bar

- Fe based catalyst

- Feasibility studies for

CCRI (China) done for

5000 TPD

Catalytic two stage

liquefaction process

(CTSL)

Headwaters Inc.,

USA

200 TPD

(Cattlesburg,

Kentucky, USA)

1980-

1992

(1) 400 deg. C, 170 bar

(2) 440 deg. C, 170 bar

- Fe based catalyst in

first reactor

Liquid solvent

extraction process

(LSE)

British Coal

Corporation, UK

2.5 TPD

(Point of Ayr,

North Wales)

1973-

1995

(1) 410-440 deg. C, 10-20 bar

(2) 400-440 deg. C, 200 bar

- Detailed design of 65

TPD demo plant done

- Non catalytic process

Shenhua DCL Plant

Organization Shenhua Group Corporation

(Largest coal supplier in world)

Design basis 12000 MT/day (4.38 MMTPA)

~ 50000 barrels of oil per day

Project period 2004 (construction)- 2008 (Phase 1 commission)

Cost of project US $.1.52 billion (1997 projection) [11]

Revenues $ 125.1 million (six months operation in earnings

before taxes) (~ 22000 barrels of oil per day) [12]

Remarks - Based on catalytic two stage liquefaction (CTSL)

process (Headwaters Inc.) [13]

- Bench scale, pilot scale and demo scale plant

facilities developed

- In-house catalyst (Fe based) development

- Project management (ABB Lummus Global) [14]

Shenhua DCL Plant, Inner Mongolia [13]

[11] Comolli, Alfred G., et al. "The Shenhua coal direct liquefaction plant." Fuel Processing Technology 59.2 (1999): 207-215.

[12] http://www.reuters.com/article/2011/09/08/shenhua-oil-coal-idUSL3E7K732020110908

[13] https://www.netl.doe.gov/File%20Library/events/2012/co2%20capture%20meeting/Z-Ye-Shenhua-Group-Demonstration-Project.pdf (last accesed, 12th June, 2015)

[14] http://www.abb.com/cawp/seitp202/03ea4f3dc6ed15df85256c94006ae156.aspx (last accessed, 12th June, 2015)

Expected payback period: 3-4 years

YPC (Yulin) Co-processing Unit

Organization Yanchang petroleum company (Yulin, China)

Technologist Kellogg Brown & Root (KBR, USA) (VCC)

Design basis 450 KTA ( AR/FCC Slurry + Coal 60:40 ratio) [15]

Project period 2011 – 2015 (Commissioned Jan 2015)

Cost of project NA

Revenues NA

Remarks - Based on single stage liquefaction process (IGOR)

- China V specifications attained

Feed stock

Residue + Coal wt (%) 100

Conversion

Residue wt (%) 95

Coal wt (%) XX

Products

Naptha wt (%) XX

Diesel wt (%) XX

3500 bpd VCC reactor [15]

[15] https://www.usea.org/sites/default/files/event-/Wang%20Mingfeng-EN.pdf

DCL Economics

S. No. Source Equivalent crude required selling price Basis

1 Sun et al. (2005) $31.73 CTSL

2 NETL report (2007) $54-$60

3 Bloomberg (2007) $30 Shenhua Plant

4 Bartis et al. (2008) $62-$75

5 Winslow and Schemtz (2009) $38.06 CTSL

6 Hydrocarbons-technology (2010) $67-$82 Shenhua Plant

7 Reuters (2011) $60 Shenhua Plant

1. Sun, Qingyun, et al. "Comparative analysis of costs of alternative coal liquefaction processes." Energy & fuels 19.3 (2005): 1160-1164.

2. https://www.netl.doe.gov/File%20Library/newsroom/accomp_fy07.pdf , (Last accessed, 12th June 2015)

3. http://www.bloomberg.com/apps/news?pid=conewsstory&refer=conews&tkr=YZC:US&sid=a6VwxDlvG4nM (Last accessed: 8th June 2015)

4. Bartis, T.J., Camm, F., Ortiz, D.S., “Producing Liquid Fuels from Coal: Prospects and Policy Issues”, Rand Corporation, CA (2008).

5. Winslow, J, Schemtz, E, Direct Coal Liquefaction Overview (2009). http://bellona.org/filearchive/fil_Direct_Coal_Liquefaction_Overview.pdf (Last retrieved, 20 May, 2015)

6. http://www.hydrocarbons-technology.com/projects/shenhua/ (Last acceses, 24th May, 2015)

7. http://www.reuters.com/article/2011/09/08/shenhua-oil-coal-idUSL3E7K732020110908 (Last accessed: 19th May 2015).

Detailed feasibility studies of DCL (Indian application) is essential to understand its potential (economic

competitiveness) for production of chemical and fuels

Factors affecting the DCL yield

• Pretreatment of coal

• Preheat treatment

• Hydrothermal treatment

• Drying and oxidation

• Coal swelling in solvents

• Coal rank

• Solvents

• Hydrogen transfer mechanisms

• Catalyst mediated hydrogen transfer

• Catalysts in direct coal liquefaction

• Dissolution catalysts • (Fe-based catalysts, non Fe-based catalysts, Acid Catalyts)

• Catalyst for coal liquids upgrading

• Catalyst deactivation

Summary and Conclusion

• Various single and two stage processes have been developed for DCL. IGOR/VCC, NEDOL in

single stage and LSE, CTSL in two stage processes are available for licensing.

• Equivalent crude selling price for DCL to be profitable range between $30-$82. Detailed feasibility

studies of DCL is essential to understand its potential for production of chemical and fuels.

• Hybrid DCL/ICL plant are more cost competitive, feasibility studies of such plants need to be

looked into.

• Shenhua commercial DCL plant in China has shown acceptable liquid yields as per figures in open

literature. Plant at YPC, China based on VCC technology has shown excellent conversion for co-

processing residue and coal.

• Shenhua corporations have developed their commercial plants (scaling from lab, bench, pilot to

demo scale facilities) and in the process filed ~104 patents (37 granted) between 2004-2010.

• R&D facilities for DCL in India need to be developed for understanding the kinetics and

hydrodynamics of DCL technologies specific to coal of our interest.

• Consortium of Public-Private companies, CSIR, Academia labs need to formulated to develop

CTX technologies.

Path Forward Thank You &

Jai Hind !

The man who moves a mountain begins by carrying away small stones – Confucius