Christian College Talk

8/12/2019 Christian College Talk

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CATALYSIS IN THE PRODUCTION OFFUTURE TRANSPORTATION FUELS

Paul RatnasamyNational Chemical Laboratory

Pune, India


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How long will FossilHydrocarbon fuels last ?

FUEL Reserve/Production

Oil 40 yearsNatural Gas 65 yearsCoal / tar sands 200 years

Note :1. Increasing recent demand from India & Chinaare 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/statisticalreview2004)


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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 forFuel Cells- Challenges Catalysts for Biodiesel Production Solar energy as future fuel-Catalysts

for H 2O and CO 2 splitting .


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Natural gas to TransportationFuels : 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

cars:Stationary vs On-board supply optionsfor Hydrogen.

Natural Gas Electricity;MCFC and SOFC can generate electricity by direct internalreforming of NG at 650C;Ni/ Zr(La)Al 2O4,loaded on anode; problem is alkalipoisoning;fuel-to-electricity efficiency ~60%;thermal eff ~85%; 2 MW plants


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Catalysts for conversion of NG toTransportation Fuels

I.Syngas Preparation- Hydrodesulphurisation(Co/Ni-Mo-alumina)- Syngas generation(H 2 / 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 CO 2.

3.Product Work up :Wax Conversion to diesel and gasoline.Mild Hydro-cracking/ Isom catalysts(Pt metal- acidicoxide support )


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Petro- vs- Syn DieselProperty Petro- Syn-

Boiling Range,oC 150-300 150-300

Density at 15 C,kg/m 3 820-845 780S, ppm vol 10 - 50 70CFPP, oC -15 -20Cloud point, oC -8(winter) -15

Due to lower S, N and aromatics, GTL dieselgenerates less SOx and particulate matter.

Oil & Gas(Eur Mag);2/2007;page 88


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Power and fuels from Coal / PetCokeGasification Texaco EECP Project: Topics

Catalysis, 26 (2003)13

FEED:1235 TPD OF PetCokePC SG (75%)Power Plant

25%FT 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 = 0.67;Once-thru slurry(Fe) FT

reactor; RR = 15 % at a refinery site.


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Coal To Syngas To Fuel CellsCatalysis in Coal / PetCoke gasification SR: C + H 2O CO + H 2 (+117 kJ/mol)

Combust :2C+ O 2 2CO ( H = -243 kJ/mol)WGS :CO + H 2O H2 + CO 2 ( -42 kJ/mol)Methan : CO+3 H 2 CH 4 + H2O(- 205 kJ/mol)

Methanation can supply the heat for steamgasification and lower oxygen plant cost. K &Fe oxides lower temp of gasification

H2 /CO ~0.6 in coal gasification;Good WGS isneeded;

MCFC and SOFC can use H 2,CO, & CH 4 asfuel 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 = C 12 to C 20 groups

Fatty acid triglyceride HC-O-C-R''

O

H2C-O-C-R'

O

H2C-O-C-R'"

O

FA Comp. Sun Rape/Canola

Cottonseed

Soyabean

Palm

Palmitic C16.0 6.8 3.49 11.67 11.75 45

Stearic C18.0 3.26 0.85 0.89 3.15 5Oleic C18.1 16.93 64.4 13.27 23.26 39Linoleic C18.2 73.73 22.3 57.51 55.53 10Linolenic C18.3 0 8.23 0 6.31 0

Jatropha

12-17

5 - 637-6319-40-


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Pathways to RenewableTransportation Fuels

Biomass

Gasifier

Pyrolysis

Hydrolysis

Syngas

Bio Oils

Methanol,Ethanol,

FT( diesel,etc)

Refine to LiquidFuels

Ferment toethanol,

butanol

Aqueous phaseReforming Hydrogen

Gasolineadditives

Veg OilsAlgae Oils Biodiesel


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Transportation Fuels from Cellulosic Biomass(Pyrolysis Route)


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Sugar Cane Juice to H 2

AQUEOUS PHASE REFORMING

C6H12O6 +6H 2O 12H 2 +6CO 2(APR) Pt-alumina catalysts,200 C 1 kg of H 2 ($3-4)from 7.5 kg Sugar

($2.25 at $300/ton) Fuel Efficiency of H 2 >> diesel/gasolineInt.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 H 2O) C3H8O3 +3H 2O 7H2 + 3CO 2

Ru Y2O3 catalysts; 600 C; 1 kg H 2 from 7 kg glycerine

H2 production from Biomass is less

economically viable than production ofethanol and biodiesel from biomass.


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Transportation Fuels from BiomassBIODIESELS

First generation biodieselFatty Acid methyl esters (FAME); methyl esters of C 16 and C 18 acids.

Second generation BiodieselsHydrocarbon Biodiesels ; C 16 and C 18 saturated,branched Hydrocarbons similar to those inpetrodiesel; High cetane number (70 80).

Third Generation BiofuelsFrom (hemi)Cellulose and agricultural waste;Enzyme technology for (hemi)Cellulose degradationand catalytic upgrading of products.

Fi t G ti Bi di l


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First Generation BiodieselsFatty Acid Methyl Esters

First 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); Mestearate(39 C); Me oleate(-20 C); Linoleate(-35 C); Linolenate(-52 C);

Catalysts: Alkali catalysts( Na/K methoxides);CSTR;Large water, acid usage in productseparation


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Operational Problems in FirstGeneration Technology

Non refined oils need pretreatment toremove water and Free Fatty Acids.Prior esterification needed. FFAscause corrosion/ soap / emulsions.

Need to use SS vessels (alkali / acid) Metal alcoholates sensitive to H 2O.

Presence of water consumescatalysts & creates emulsions. Majorproblems in the biodiesel - glycerolseparation step.


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Fuel Quality Problems in FirstGeneration Technology

Lower glycerol purity; Not suitable forproduction of chemicals ( propanediol,acrolein etc)without major

purification;Salts and H 2O to beremoved from Glycerol. Residual KOH in biodiesel creates

excess ash content in the burnedfuel/engine deposits/high abrasive wearon the pistons and cylinders.


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

Solid acid catalysts Feedstock flexibility

Glycerine > 98% No use of water in product separation/

purification;No harmful effluents;

Fixed bed Reactor operation Reaction time longer than base

catalysts


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Catalysts for 2 nd Generation Biodiesel.Hydrocarbon Biodiesel Technology

Hydrocarbon Biodiesel consists of diesel -range hydrocarbons of high cetane number

Deoxygenation and hydroisomerization ofVeg Oil at high H 2 pressures and temp.

Catalysts :NiMo(for deoxyg), Pt-SAPO-11(forisom); H 2 at high pressure needed;Yield fromVO is lower;C3 credit.

Can be integrated with petro refinery

operations;Greater Feedstock flexibility.

Suitable for getting PP < - 20 C (Jet Fuels). 40000 tpy plant in Finland; 200K tpy in

Singapore;100K tpy plant using soya in SA.


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Convert Veg Oil to HC Diesel inHydrotreaters in Oil Refineries

Hydrotreat /Crack mix of VO + HVGO(5-10%);S=0.35%;N(ppm)= 1614;K UOP = 12.1;density=0.91 g/cc);Conradson C = 0.15%;Sulfided NiMo/Si-Al Catalyst; ~350 C,50 bar;LHSV = 5; Diesel yield ~ 75%wt.

Advantages over the Trans Esterificat Route - Product identical to Petrodiesel(esp.PP )

- Compatible with current refinery infrastruct- Engine compatibility;Feedstock flexibility

(Appl.Cat.329(2007)120)


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Comparison: Quality of Fuels BD- 2 GenNeste BioDiesel

GTL Diesel BD-1GenFAME

PetroDiesel

winterMK1

Density @ +15C (kg/m 3) 775 - 785 770 785 885 800 - 820

Viscosity @ + 40C (mm 2/s) 2.9 3.5 3.2 4.5 4.5 1.5 - 4

Cetane number 84 99 73 81 51 51

10% distillation (C) 260 270 260 340 21090% distillation (C) 295 300 325 330 355 275

Cloud point (C) -5 to -30 0 to -25 -5 -22 to 36

Heating value (lower) (MJ/kg) 44 43 38 44

Heating value (MJ/l) 34 34 34 35Polyaromatic content (wt%) 0 0 0 0

Oxygen content (wt%) 0 0 11 0

Sulfur content (mg/kg) 0 < 10 < 10 < 10

EN590/05Diesel fuel

Summer

835

3.5

53

200 350

-5

43

36

4

0

< 10


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Capital Costs : EIA Annual Energy Outlook 2006


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Hydrogen Production Costs(T h e E c o n o m i s t / IEA)

SOURCE USD / GJCoal / gas/ oil/ biodiesel 1-5NG + CO 2 sequestration 8-10

Coal + CO 2 sequestration 10-13Biomass(SynGas route) 12-18Nuclear (Electrolysis) 15-20Wind (Electrolysis) 15-30Solar (Electrolysis) 25-50Note: Due to complications of H 2 storage, distribution

and dispensing compared to liquid hydrocarbonfuels, very little correlation between bulk hydrogencosts at a refinery and at the customers dispensingstation.


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Catalysts for H 2O and CO 2 Photothermal SplittingUsing Sunlight

1. H2O H2 + 0.5 O 22. CO 2 CO +0.5 O 2 FT Synthsis:CO + H2 (CH2)n petrol/Diesel

Sandias Sunlight To Petrol Project: Cobaltferrite loses O atom at 1400 o C; When cooledto 1100 o C in presence of CO 2 or H2O, it picksup O, catalyzing reactions 1 and 2; Solar

absorber provides the energy. Challenge: Find a solid which loses / absorbsO from H2O / CO 2 reversibly at a lower temp.


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Splitting H 2O- The Holy Grail


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Splitting H 2O with visible light(Domain,18 th ICC, 2008)


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Future Fuels:Catalysis Challenges Meeting Specifications of Future Fuels

Remove S,N, aromatics, Particulate Matter Power Generation

- Lower CO 2 Production in Catalytic Gasification- Lower CO 2 and H 2 /CO ratio in Syngas generation

FT Synthesis : Lower CH4 and CO

2 ;Inhibit metal

sintering; Increase attrition strength; Reactor design Biomass :1.Cellulose to Ethanol ( enzymes)

2. Biomass gasification catalysts.Decentralized Production/ Use of H 2 and Biofuels will

avoid costs due to their s torage and distribution.Holy Grail Challenges Direct Conversion of CH 4 to methanol and C 5+. Catalytic Water and CO 2 splitting using solar energy


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THANKS !

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