THE Next Generation Coal Conference

7/28/2019 THE Next Generation Coal Conference

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INSTITUTE OFCHEMICAL TECHNOLOGY

Production of Fuels and Chemicals

from Coal:

An Overview of Existing Technologies

and Future Challenges

PD Dr. Yvonne Traa

Newcastle, J uly 13, 2012


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2

Common Abbreviations for Reactants To Products

Y. Traa, Chem. Commun. 46 (2010) 2175.


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3

Influence of Feedstock

M. Sudiro, A. Bertucco, Int. J . Alternative Propulsion 2 (2008) 13.

Feedstock Fuel produced ona weight basis perunit of feedstock

CO2 emittedper kg ofliquid fuel

Natural gas 67 % 0.9 kg

Coal 33 % 4.8 kg

Wood 17 % 6.1 kg


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Production of Gasoline and Diesel from Coal



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Outline

Introduction

Coal conversion techniques

Fischer-Tropsch synthesis

Methanol-based techniques

Direct coal liquefaction

Conclusions and outlook


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6

Coal Conversion Processes

Coal, J .C. Crelling et al., in: Ullmanns Encyclopedia of IndustrialChemistry, Wiley-VCH, Weinheim, 2006.

Extraction Pyrolysisor Carbo-

nisation

Directlique-

faction

Gasifi-cation

Com-bustion

Mainproducts

montanwax

coke, coaltar,benzene,gas

gasoline synthesisgas

electricpower, heat

Furtherreactants

- - hydrogen air oroxygen,steam

air oroxygen

Tempera-ture / C

80-90 > 300-1300 400-480 370-1600 1000-1800

Pressure 0.1 MPa 0.1 MPa 15-70 MPa 0.1-3 MPa 0.1-3 MPaCatalyst no no yes usually no no

Increasing severity of process


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Outline

Introduction







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The Chemistry of Synthesis Gas



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9 Y. Traa, Chem. Commun. 46 (2010) 2175.

Scheme of Fischer-Tropsch Synthesis from Coal


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Reaction Mechanism of Fischer-Tropsch Synthesis

J .-D. Arndt et al., Chem. Ing. Tech. 79 (2007) 521;J . Gaube, H.-T. Klein, J . Molec. Catal. A: Chemical 283 (2008) 60.

Surface polymerisationwith

chain start (e.g., by adsorption of CO and formation of asurface species via reaction with H2),

chain growth (e.g., by insertion of CO and/or CH2units) and

chain termination (e.g., by hydrogenation yielding alkanes or

via the formation of alkenes).


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Mild Hydrocracking of Fischer-Tropsch Product

V.M.H. Van Wechem, M.M.G. Senden, Stud. Surf. Sci. Catal. 81 (1994) 43.

Mild hydrocracking ofthe Fischer-Tropschproduct maximisesthe yield of middledistillate.


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12 I.I. Rahmim, Oil Gas J . 106 (No. 12, 2008) 22.

I.I. Rahmim, Oil Gas J. 106 (No.12, 2008) 22.

Capital cost /106 US-$

Capital costpercentage

Coal and slurry preparation

Coal gasification

Air separation unit

Synthesis gas clean-up

425

1,150

425

850

67 %

Water gas shift and


51012 %

Product upgrading 210 5 %Power generation

Other cost (without CCS)

255

42516 %

Total 4,250 100 %

Typical Cost for 2.5 106 t/a Capacity


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13 M.E. Dry, A.P. Steynberg, Stud. Surf. Sci. Catal. 152 (2004) 406.

Carbon Efficiency and Stoichiometry


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14

Fischer-Tropsch Synthesis: Status 2008

A. de Klerk, Catal. Today 130 (2008) 439; I.I. Rahmim, Oil Gas J . 106 (No. 12,

2008) 22; M.E. Dry, in Handbook of Heterog. Catal., G. Ertl et al. (Hrsg.), 2.Aufl., Bd. 6, WILEY-VCH, Weinheim, 2008, S. 2965.

SMDS,Malaysia

Oryx GTL,Katar(Sasol,

Chevron)

PetroSA,South Africa

Sasol SynfuelsE & W,Secunda, South

Africa

Sasolburg,South Africa

Productionofsynthesisgas

Partialoxidation ofnatural gas

Natural gas Steamreforming ofnatural gas

CoalNatural gas

Reactor Multitubularreactor

Slurryreactor

Circulatingfluidised bed

Fixed fluidisedbed, i.e.

ebullating bed

Multitubularand slurry

reactor

Catalyst Co/SiO2 ? Co/SiO2/Al2O3 ?

Fe (fused) Fe(fused with K2Oand MgO orAl2O3) ?

Fe (co-precipitationwith Cu) ?

Reactionconditions

LTFT LTFT HTFT HTFT LTFT

Mainproduct

Waxes andparaffins

Diesel Gasoline Gasoline Waxes andparaffins

Capacity 0.7 106 t a-1 1.6 106 t a-1 1.1 106 t a-1 7 106 t a-1 0.3 106 t a-1


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Scheme of CTL with IGCC and CCS

I.I. Rahmim, Oil Gas J . 106 (No. 12, 2008) 22.


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Poly-Generation Plants

R.H. Williams et al., Energy Procedia 1 (2009) 4379.

Co-production of electricity and Fischer-Tropsch liquids

(FTL) leads to less costly FTL than via production thatmaximises the output of FTL.

In poly-generation plants, about of the feedstock

carbon can be recovered as CO2 in a concentrated

stream for which CCS costs are small relative to CCScosts for stand-alone power plants.

Co-processing biomass with coal is a cost-effective

way to reduce FTL greenhouse gas emissions,

requiring much less biomass input to realize ultralowemission rates for liquid fuels compared to

conventional non-food biofuels options such as

cellulosic ethanol.


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Handling H2-Deficient and CO2-Rich Syngas

O.O. J ames et al., Fuel Process. Technol. 91 (2010) 136.R.W. Dorner et al., A l. Catal. A: General 373 (2010) 112.

Fe-based catalysts needed: Water gas shift activity (on Co-basedcatalysts hydrogenation of CO2 yields CH4). Catalysts have to be adapted (e.g., large amounts of K promoter areknown to poison the Fe catalyst, but in CO2 hydrogenation largeramounts of K are beneficial).


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Greenhouse Gas Emissions

Xie et al., Environ. Sci. Technol. 45 (2011) 3047.


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Fischer-Tropsch Synthesis and Catalytic CH4 Decomposition

G.P. Huffman, Fuel 90 (2011) 2671.

H2/CO fromgasifier

H2/CO afterCDH

MWCNTproduced(t/d)

CO2emissionsavoided (t/d)

H2O saved(gal/day)

1 2.3 2153 13,575 1,330,836

0.8 2.1 1958 12,343 1,210,057

Calculations of products+environmental savings for a 50,000 bbl/d plant:


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UCG Combined with Fischer-Tropsch in Australia

h. www.lincenergy.com


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Brown Coal to Liquids in Australia

http://www.monashenergy.com.au.

The Monash Energy project utilises brown coal, which has a much highermoisture content than black coal. It is this higher moisture content which drivesthe lower efficiency ratings of brown coal fired power plants compared to blackcoal. The cost for lower efficiency is a higher output per unit of greenhouse gasemissions. For this reason, pre-drying of brown coal has long been identified asa potential means of improving the efficiency of combustion in brown coal firedpower plants.

The Monash

Energy Project isthe first to benominated fordevelopmentunder a CleanCoal EnergyAlliance formedbetween AngloAmerican andShell in May2006.
http://www.shell.com/home/content/media/news_and_library/press_releases/2006/clean_coal_alliance_25052006.htmlhttp://www.shell.com/home/content/media/news_and_library/press_releases/2006/clean_coal_alliance_25052006.htmlhttp://www.shell.com/home/content/media/news_and_library/press_releases/2006/clean_coal_alliance_25052006.htmlhttp://www.angloamerican.co.uk/http://www.angloamerican.co.uk/http://www.shell.com/http://www.shell.com/http://www.angloamerican.co.uk/http://www.angloamerican.co.uk/http://www.shell.com/home/content/media/news_and_library/press_releases/2006/clean_coal_alliance_25052006.htmlhttp://www.shell.com/home/content/media/news_and_library/press_releases/2006/clean_coal_alliance_25052006.htmlhttp://www.shell.com/home/content/media/news_and_library/press_releases/2006/clean_coal_alliance_25052006.html


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Outline

Introduction







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Basis: Lurgi MegaMethanol

http://www.lurgi.com/website/fileadmin/user_upload/1_PDF/1_Broshures_Flyer/englisch/0305e_Gas-to-Chemicals.pdf.


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Influence of the Residence Time on Product Yields

S. Kvisle et al., in Handbook of Heterog. Catal., G. Ertl et al. (eds.),2nd ed., Vol. 6, WILEY-VCH, Weinheim, 2008, p. 2950.


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Technologies for the Production of Olefins

E. Schwab et al. and H. Zimmermann, in: Preprints of the ConferenceProduction and Use of Light Olefins, DGMK Tagungsbericht 2009-2, S.

Ernst et al. (eds.), DGMK, Hamburg, 2009, p. 25 and p. 7; S. Kvisle et al., in:

Handbook of Heterogeneous Catalysis, 2nd

ed., Vol. 6, G. Ertl et al. (eds.),WILEY-VCH, Weinheim, 2008, p. 2950.

MTO(UOP/Hydro)

MTP(Lurgi)

FTTO(BASF)

Steam-cracking

Reactor fluidised bed fixed bed,DME pre-reactor

not disclosed crackingfurnace

Reactants methanol methanol synthesisgas

steam,naphtha

Temperature 350-600 C 450 C 340 C 820-850 C

Catalyst zeoliteH-SAPO-34

ZeoliteH-ZSM-5

probablyFe-based

none

Regenerationof catalyst

continuously,fluidised bed

fixed bed not disclosed not applicable

npropene/nethene 0.4 to 0.9 ca. 1.0 0.3


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Lurgis MTP Technology


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MTP from Coal in China (I)

http://www.dtpower.com/en/content/2011-01/20/content_89753.htm.


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MTP from Coal in China (II)

http://www.lurgi.com.

Engineering & Construction: A New Lurgi-MTP Unit for China

2011/08/26

Air Liquide is pleased to announce that its Engineering & Construction division has

signed a contract with the Shenhua Ningxia Coal Industry Group (SNCG) in China,

one of the worlds largest coal industrials, to build a 500,000 tpa Methanol-to-Propylene (MTP) plant, following the successful commissioning of the first industrial

scale unit built with the same client.

This will be the third large-scale MTP plant licensed by Lurgi. SNCG, in close

cooperation with the Lurgi team, played an important and constructive role in the

commissioning and startup phases of the MTP-1 first of a kind plant, thereby

contributing to proving at industrial scale the success of the Lurgi MTP technology

Air Liquide will remain the sole owner and licensor of the Lurgi MTP technology


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UOP/Hydro MTO

www.uop.com.

Total Petrochemicals/UOPs

olefin cracking process:cracking C4+olefins toethene and mainly propene


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P

http://www.exxonmobil.com/Apps/RefiningTechnologies/files/conference_2011.1204.MTG_World_CTL.pdf.


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ExxonMobil Research and Engineering: MTG

http://www.exxonmobil.com/Apps/RefiningTechnologies/files/conference_2011.1204.MTG_World_CTL.pdf.

Medicine Bow project, Wyoming

Mingo County project, West Virginia


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Methanol To Gasoline (MTG)

http://www.exxonmobil.com/Apps/RefiningTechnologies/files/sellsheet_09_mtg_brochure.pdf.


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Outline

Introduction







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Simplified Scheme of Direct Coal Liquefaction



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Shenhua: Direct Coal Liquefaction

www.worldcoal.org...coal_liquid_fuels_report...


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Shenhua: Direct Coal Liquefaction

Two ebullated bed reactors utilising a proprietary

dispersed superfine (nanosized) disposable Fe catalyst

(GelCat) prepared from iron sulfate.

Fixed-bed in-line hydrotreater with Ni-Mo/Al2O3 catalyst.

Feedstock: Bituminous coal.

Reaction conditions: 400 to 460 C, 17 MPa.

J uly 2011: 12 times of coal injection completed

10,670 operating hoursproducts: 550,000 t diesel

247,500 t naphtha

99,000 t LPG


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Integrated Coal-To-Liquids Process

WO Patent Application WO 2010/135381 A1, 25 November 2010,assigned to Accelergy Corp.

Algae production


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Possibilities for H2 Replacement during DCL

[1] K.Z. Yang et al., Fuel 76 (1997) 1105.[2] J . Cai et al., Fuel 87 (2008) 3388.[3] Z. Lei et al., Fuel Process. Technol. 91 (2010) 783.

[4] Z. Lei et al., Energy 36 (2011) 3058.[5] Y. Watanabe et al., Fuel 75 (1996) 46.

It has been reported that 40-50 % of the cost of DCL are due to

H2 generation [1]. In addition, H2 generation produces most of the

time large amounts of additional CO2.

CH4 or mixtures of CH4 and H2 can be used as hydrogenation

gas at higher temperatures or with certain catalysts [1,2].

Liquefaction of lignite withNaOH/MeOH at 300C + 13 MPa [3]

MeOH, CaO, FeS at 400C + 4 MPa [4].

Liquefaction in CO/H2

O: CO + H2

O CO2

+ H2

[5].


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Conclusions and Outlook

The reserves and resources of coal are distributed more evenly and

are significantly larger than those of oil and natural gas. Thus, coal-

based processes are gaining significance. The environmental problems related to coal mining and coal use are

large. Measures for environmental protection have to be taken.

The best option is to use a well balanced energy mix and to use all

energy sources efficiently avoiding unnecessary process steps. The coal conversion techniques discussed offer real alternatives tothe production of fuels and chemicals from crude oil.

Research and development in the area of renewable energy for the

production of electricity and heat should be fostered so that in the longterm the use of coal can be restricted to the production of chemicals

and liquid fuels for heavy-duty vehicles, ships and airplanes.

Because of the much smaller consumption for these purposes ascompared to the consumption for power production, the carbon dioxide

i i ill th b t bl

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