CATALYSIS IN THE PRODUCTION OF FUTURE TRANSPORTATION FUELS

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CATALYSIS IN THE PRODUCTION OF FUTURE
TRANSPORTATION FUELS

• Paul Ratnasamy
• National Chemical Laboratory
• Pune, India

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How long will Fossil Hydrocarbon fuels last ?

• FUEL Reserve/Production
• Oil 40 years
• Natural Gas 65 years
• Coal / tar sands 200 years
• Note1. Increasing recent demand from India
  China are not taken into account.
• 2.New reserves since 2004 are not taken into
  account.
• British Petroleum Statistical review of World
  Energy, June 2004. (www.bp.com/statisticalreview20
  04)

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Role of Catalysis in a National Economy

• 24 of GDP from Products made using
  catalysts(Food,Fuels,Clothes,Polymers,Drug,Agro-ch
  emicals)
• gt 90 of petro refining petrochemicals
  processes use catalysts
• 90 of processes 60 of products in the
  chemical industry
• gt 95 of pollution control technologies
• Catalysis in the production/use of alternate
  fuels (NG,DME,H2,Fuel Cells,biofuels)

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OUTLINE OF TALK

• Catalysts for Natural Gas conversion to gasoline
  and diesel - Challenges
• Catalysts for conversion of Coal to
  Transportation Fuels-Challenges
• Catalysis in Hydrogen Production for Fuel Cells-
  Challenges
• Catalysts for Biodiesel Production
• Solar energy as future fuel-Catalysts for H2O and
  CO2 splitting .

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Natural gas to Transportation Fuels Options

• Natural Gas ? Syngas
• I. Syngas ?Methanol (DME) ? Gasoline
• II. Syngas ? Fischer-Tropsch Syndiesel
• Syndiesel Can use existing infrastructure
• III. Syngas ? H2 ? Fuel Cell driven
  carsStationary vs On-board supply options for
  Hydrogen.
• Natural Gas ?ElectricityMCFC and SOFC can
  generate electricity by direct internal reforming
  of NG at 650CNi/ Zr(La)Al2O4, loaded on anode
  problem is alkali poisoningfuel-to-electricity
  efficiency 60thermal eff 85 2 MW plants
  demonstrated

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Catalysts for conversion of NG to Transportation
Fuels

• I.Syngas Preparation
• Hydrodesulphurisation(Co/Ni-Mo-alumina)
• Syngas generation(H2/ CO 1) POX,steam,
  autothermal, dry reforming Ni(SR),Ru(POX)
  based catalysts Pt metals for POX for FT.
• 2.Fischer Tropsch Synthesis
• Co Wax and mid dist Fe - gasoline Cu K
  added. Cu increases mol wt of HC spray dried
  ,60 ?m size
• Supported Co preferred due to its lower WGS
  activity consequent lower loss of C as CO2.
• 3.Product Work up
• Wax Conversion to diesel and gasoline.
• Mild Hydro-cracking/ Isom catalysts(Pt
  metal- acidic oxide support )

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Petro- vs- Syn Diesel

• Property Petro-
  Syn-
• Boiling Range,oC 150-300 150-300
• Density at 15 C,kg/m3 820-845 780
• S, ppm vol 10 - 50
  lt1
• Aromatics, vol 30
  lt0.1
• Cetane No gt51
  gt70
• CFPP, oC -15
  -20
• Cloud point,oC -8(winter) -15
• Due to lower S, N and aromatics, GTL diesel
  generates less SOx and particulate matter.
• Oil Gas(Eur Mag)2/2007page 88

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Power and fuels from Coal / PetCoke
Gasification Texaco EECP Project Topics
Catalysis, 26 (2003)13

• FEED1235 TPD OF PetCoke
• PC ? SG ? (75)Power Plant
• ? 25FT fuel(tail gas ?Power)
• 55 MW Electricity Steam.
• 20 tpd diesel 4 tpd naptha
• 82 tpd Wax(?60 tpd diesel) 89 tpd S
• H2 CO 0.67Once-thru slurry(Fe) FT reactor RR
  15 at a refinery site.

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Coal To Syngas To Fuel Cells

• Catalysis in Coal / PetCoke gasification
• SR C H2O ?CO H2 (117 kJ/mol)
• Combust2C O2 ? 2CO (?H -243 kJ/mol)
• WGS CO H2O ? H2 CO2 ( -42 kJ/mol)
• Methan CO3 H2 ? CH4 H2O(- 205 kJ/mol)
• Methanation can supply the heat for steam
  gasification and lower oxygen plant cost. K Fe
  oxides lower temp of gasification
• H2/CO 0.6 in coal gasificationGood WGS is
  needed
• MCFC and SOFC can use H2,CO, CH4 as
• fuel to generate electricity.
• Low rank coals, Lignites gasify easier.

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Biomass Sources For Biofuels

• LignoCellulose ( cellulose, Hemicellulose,
  Lignin)
• Starch
• Sugars
• Lipid Glycerides ( Vegetable Oils Animal Fats)

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Structures in Lignocellulose
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Structures in Cellulose,Starch Lignin
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COMPOSITION OF VEGETABLE OILS
R, R, R C12 to C20 groups Fatty acid
triglyceride
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Pathways to Renewable Transportation Fuels

• Biomass

Methanol, Ethanol, FT( diesel,etc)
Gasifier
Syngas
Veg Oils Algae Oils
Biodiesel
Pyrolysis
Bio Oils
Refine to Liquid Fuels
Ferment to ethanol, butanol
Gasoline additives
Hydrolysis
Aqueous phase Reforming
Hydrogen
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Transportation Fuels from Cellulosic
Biomass(Pyrolysis Route)
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Sugar Cane Juice to H2

• AQUEOUS PHASE REFORMING
• C6H12O6 6H2O ? 12H2 6CO2(APR)
• Pt-alumina catalysts,200 C
• 1 kg of H2 (3-4)from 7.5 kg Sugar
• (2.25 at 300/ton)
• Fuel Efficiency of H2 gtgt diesel/gasoline
• Int.J.Hydrogen Energy,32(6)(2007)717

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H2 Production from GlycerineEnergy
Fuels,19(2005)1761

• Available from Veg oils(40-98 in H2O)
• C3H8O3 3H2O ?7H2 3CO2
• Ru Y2O3 catalysts 600 C
• 1 kg H2 from 7 kg glycerine
• H2 production from Biomass is less economically
  viable than production of ethanol and biodiesel
  from biomass.

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Transportation Fuels from BiomassBIODIESELS

• First generation biodiesel
• Fatty Acid methyl esters (FAME) methyl esters
  of C16 and C18 acids.
• Second generation Biodiesels
• Hydrocarbon Biodiesels C16 and C18
  saturated, branched Hydrocarbons similar to those
  in petrodiesel High cetane number (70 80).
• Third Generation Biofuels
• From (hemi)Cellulose and agricultural waste
  Enzyme technology for (hemi)Cellulose degradation
  and catalytic upgrading of products.

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First Generation Biodiesels Fatty Acid Methyl
EstersFirst Generation Technology

• Veg Oil methanol ? FAME glycerine
• Veg Oils Soya,rape seed,palm, jatropha,
  karanjia,cotton seed etc Algae oils.
• High melting point of some FAME ? CFPP Problems
  Me palmitate(30 C) Me stearate(39 C) Me
  oleate(-20 C) Linoleate(-35 C) Linolenate(-52
  C)
• CatalystsAlkali catalysts( Na/K methoxides)
  CSTRLarge water, acid usage in product
  separation

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Operational Problems in First Generation
Technology

• Non refined oils need pretreatment to remove
  water and Free Fatty Acids. Prior esterification
  needed. FFAs cause corrosion/ soap / emulsions.
• Need to use SS vessels (alkali / acid)
• Metal alcoholates sensitive to H2O. Presence of
  water consumes catalysts creates emulsions.
  Major problems in the biodiesel - glycerol
  separation step.

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Fuel Quality Problems in First Generation
Technology

• Lower glycerol purity Not suitable for
  production of chemicals( propanediol, acrolein
  etc)without major purificationSalts and H2O to
  be removed from Glycerol.
• Residual KOH in biodiesel creates excess ash
  content in the burned fuel/engine deposits/high
  abrasive wear on the pistons and cylinders.

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Catalysts for 1st generation Biodiesel.Second
Generation Technology for FAME

• Solid acid catalysts
• Feedstock flexibility
• Glycerine gt 98
• No use of water in product separation/
  purificationNo harmful effluents
• Fixed bed Reactor operation
• Reaction time longer than base catalysts

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Catalysts for 2nd Generation Biodiesel.
Hydrocarbon Biodiesel Technology

• Hydrocarbon Biodiesel consists of diesel-range
  hydrocarbons of high cetane number
• Deoxygenation and hydroisomerization of Veg Oil
  at high H2 pressures and temp.
• CatalystsNiMo(for deoxyg), Pt-SAPO-11(for isom)
  H2 at high pressure neededYield from VO is
  lowerC3 credit.
• Can be integrated with petro refinery
  operationsGreater Feedstock flexibility.
• Suitable for getting PP lt - 20 C (Jet Fuels).
• 40000 tpy plant in Finland 200K tpy in
  Singapore100K tpy plant using soya in SA.

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Convert Veg Oil to HC Diesel in Hydrotreaters in
Oil Refineries

• Hydrotreat /Crack mix of VO HVGO(5-10)
  S0.35N(ppm) 1614KUOP 12.1 density0.91
  g/cc)Conradson C 0.15 Sulfided NiMo/Si-Al
  Catalyst 350?C,50 bar LHSV 5 Diesel yield
  75wt.
• Advantages over the Trans Esterificat Route
• - Product identical to Petrodiesel(esp.PP )
• - Compatible with current refinery infrastruct
• - Engine compatibilityFeedstock flexibility
• (Appl.Cat.329(2007)120)

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Comparison Quality of Fuels
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Capital Costs EIA Annual Energy Outlook 2006
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Hydrogen Production Costs(The Economist / IEA)

• SOURCE USD /
  GJ
• Coal / gas/ oil/ biodiesel 1-5
• NG CO2 sequestration 8-10
• Coal CO2 sequestration 10-13
• Biomass(SynGas route) 12-18
• Nuclear (Electrolysis) 15-20
• Wind (Electrolysis) 15-30
• Solar (Electrolysis) 25-50
• Note Due to complications of H2 storage,
  distribution and dispensing compared to liquid
  hydrocarbon fuels, very little correlation
  between bulk hydrogen costs at a refinery and at
  the customers dispensing station.

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Catalysts for H2O and CO2 Photothermal
SplittingUsing Sunlight

• 1. H2O ? H2 0.5 O2
• 2. CO2 ? CO 0.5 O2
• FT SynthsisCO H2 ?(CH2)n ?petrol/Diesel
• Sandias Sunlight To Petrol Project Cobalt
  ferrite loses O atom at 1400o C When cooled to
  1100o C in presence of CO2 or H2O, it picks up O,
  catalyzing reactions 1 and 2 Solar absorber
  provides the energy.
• Challenge Find a solid which loses / absorbs O
  from H2O / CO2 reversibly at a lower temp.

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Splitting H2O- The Holy Grail
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Splitting H2O with visible light(Domain,18th
ICC, 2008)
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Future FuelsCatalysis Challenges

• Meeting Specifications of Future Fuels
• Remove S,N, aromatics, Particulate Matter
• Power Generation
• - Lower CO2 Production in Catalytic
  Gasification
• - Lower CO2 and H2/CO ratio in Syngas
  generation
• FT Synthesis Lower CH4 and CO2 Inhibit metal
  sintering Increase attrition strength Reactor
  design
• Biomass1.Cellulose to Ethanol ( enzymes)
• 2. Biomass gasification
  catalysts.
• Decentralized Production/ Use of H2 and
  Biofuels will avoid costs due to their storage
  and distribution.
• Holy Grail Challenges
• Direct Conversion of CH4 to methanol and C5.
• Catalytic Water and CO2 splitting using solar
  energy

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THANKS !