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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

Note:1. 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/statisticalreview2004)
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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-chemicals)
> 90 % of petro refining & petrochemicals
processes use catalysts
90 % of processes & 60 % of products in the
chemical industry
> 95% of pollution control technologies
Catalysis in the production/use of alternate
fuels (NG,DME,H
2
,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 H
2
O and CO
2
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 H
2
Fuel Cell driven
cars:Stationary vs On-board supply options
for Hydrogen.
Natural Gas Electricity;MCFC and SOFC
can generate electricity by direct internal
reforming of NG at 650C;Ni/ Zr(La)Al
2
O
4
,
loaded on anode; problem is alkali
poisoning;fuel-to-electricity efficiency ~
60%;thermal 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(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- acidic
oxide support )

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Petro- vs- Syn Diesel
Property Petro- Syn-
Boiling Range,
o
C 150-300 150-300
Density at 15 C,kg/m
3
820-845 780
S, ppm vol 10 - 50 <1
Aromatics,% vol 30 <0.1
Cetane No >51 >70
CFPP,
o
C -15 -20
Cloud point,
o
C -8(winter) -15
Due to lower S, N and aromatics, GTL diesel
generates less SOx and particulate matter.

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

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



FEED:1235 TPD OF PetCoke
PC 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;
H
2
: CO = 0.67;Once-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 + H
2
O CO + H
2
(+117 kJ/mol)
Combust:2C+ O
2
2CO (H = -243 kJ/mol)
WGS :CO + H
2
O H
2
+ CO
2
( -42 kJ/mol)
Methan: CO+3 H
2
CH
4
+ H
2
O(- 205 kJ/mol)
Methanation can supply the heat for steam
gasification and lower oxygen plant cost. K &
Fe oxides lower temp of gasification
H
2
/CO ~0.6 in coal gasification;Good WGS is
needed;
MCFC and SOFC can use H
2
,CO, & CH
4
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
12
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
H
2
C-O-C-R'
O
H
2
C-O-C-R'"
O
FA Comp. Sun Rape/
Canola
Cotton
seed
Soya
bean
Palm
Palmitic C
16.0
6.8 3.49 11.67 11.75 45
Stearic C
18.0
3.26 0.85 0.89 3.15 5
Oleic C
18.1
16.93 64.4 13.27 23.26 39
Linoleic C
18.2
73.73 22.3 57.51 55.53 10
Linolenic C
18.3
0 8.23 0 6.31 0
Jatro
pha
12-17
5 - 6
37-63
19-40
-
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Pathways to Renewable
Transportation Fuels



Biomass
Gasifier
Pyrolysis
Hydrolysis
Syngas
Bio Oils
Methanol,
Ethanol,
FT( diesel,etc)
Refine to Liquid
Fuels
Ferment to
ethanol,
butanol
Aqueous phase
Reforming
Hydrogen
Gasoline
additives
Veg Oils
Algae Oils
Biodiesel
15

Transportation Fuels from Cellulosic Biomass(Pyrolysis Route)
16
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Sugar Cane Juice to H
2

AQUEOUS PHASE REFORMING

C
6
H
12
O
6
+6H
2
O 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/gasoline

Int.J.Hydrogen Energy,32(6)(2007)717
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H
2
Production from Glycerine
Energy & Fuels,19(2005)1761
Available from Veg oils(40-98% in H
2
O)
C
3
H
8
O
3
+3H
2
O 7H
2
+ 3CO
2
Ru Y
2
O
3
catalysts; 600 C;
1 kg H
2
from 7 kg glycerine
H
2
production from Biomass is less
economically viable than production of
ethanol and biodiesel from biomass.
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Transportation Fuels from Biomass
BIODIESELS
First generation biodiesel
Fatty Acid methyl esters (FAME); methyl esters of C
16

and C
18
acids.
Second generation Biodiesels
Hydrocarbon Biodiesels ; C
16
and C
18
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 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); Me
stearate(39 C); Me oleate(-20 C); Linoleate(-
35 C); Linolenate(-52 C);
Catalysts:Alkali catalysts( Na/K methoxides);
CSTR;Large 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 H
2
O.
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
purification;Salts and H
2
O 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 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 of
Veg Oil at high H
2
pressures and temp.
Catalysts:NiMo(for deoxyg), Pt-SAPO-11(for
isom); H
2
at high pressure needed;Yield from
VO 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 in
Hydrotreaters 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; ~350C,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 Gen
Neste Bio
Diesel
GTL Diesel BD-1
Gen
FAME
Petro
Diesel
winter
MK1
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) 260 270 260 340 210
90% 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 35
Polyaromatic content (wt%) 0 0 0 0
Oxygen content (wt%) 0 0 11 0
Sulfur content (mg/kg) 0 < 10 < 10 < 10
EN590/05
Diesel 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
(The Economist / IEA)


SOURCE USD / GJ
Coal / gas/ oil/ biodiesel 1-5
NG + CO
2
sequestration 8-10
Coal + CO
2
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 H
2
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 H
2
O and CO
2
Photothermal Splitting
Using Sunlight
1. H
2
O H
2
+ 0.5 O
2
2. CO
2
CO +0.5 O
2
FT Synthsis:CO +

H
2
(CH
2
)
n
petrol/Diesel
Sandias Sunlight To Petrol Project: Cobalt
ferrite loses O atom at 1400
o
C; When cooled
to 1100
o
C in presence of CO
2
or H
2
O, it picks
up O, catalyzing reactions 1 and 2; Solar
absorber provides the energy.


Challenge: Find a solid which loses / absorbs
O from H
2
O / CO
2
reversibly at a lower temp.

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Splitting H
2
O- The Holy Grail
31
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Splitting H
2
O 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 CH
4
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 storage 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 !