Applications of catalysis- Physical Chemistry

content-

Chemistry & Chemical Engineering

History of Catalysis

Catalysis

Recent trends in Catalysis

Future trends in Catalysis

Summary
role-
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, H2, Fuel Cells, biofuels…)

1. APPLICATION OF
CATALYSIS
BY-SANCHIT
DHANKHAR
1

2. Chemistry & Chemical Engineering
History of Catalysis
Catalysis
Recent trends in Catalysis
Future trends in Catalysis
Summary
Content

4. CHEMISTRY AND CHEMICAL ENGINEERING
MORE INTEGRATED TO THE SOCIETY
Society:
Cleaner and safer processes
Well accepted and integrated processes
Industry:
Speed-up processes
Energy and cost effective processes
New catalysts and catalytic processes
New technologies
Academia:
New innovations
Deeper knowledge and understanding of phenomena
Control of phenomena

5. 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…)

6. WHY R&D IN CATALYSIS IS IMPORTANT
For discovery/use of alternate sources of energy/fuels/raw material for
chemical industry
For Pollution control
For preparation of new materials
(organic & inorganic-eg: Carbon Nanotubes)

7. Three Scales of Knowledge Application

8. SOME DEVELOPMENTS IN INDUSTRIAL CATALYSIS-1
1900-1920S
Industrial Process Catalyst
1900s: CO + 3H
2CH
4+ H
2O Ni
Vegetable Oil + H
2butter/margarine Ni
1910s: Coal Liquefaction Ni
N
2+ 3H
22NH
3 Fe/K
NH
3NO NO
2HNO
3 Pt
1920s: CO + 2H
2CH
3OH (HP) (ZnCr)oxide
Fischer-Tropsch synthesis Co,Fe
SO
2SO
3H
2SO
4 V
2O
5

9. INDUSTRIAL CATALYSIS-2
1930S AND 1940S
1930s:Cat Cracking(fixed,Houdry) Mont.Clay
C
2H
4C
2H
4O Ag
C
6H
6Maleic anhydride V
2O
5
1940s:Cat Cracking(fluid) amorph. SiAl
alkylation (gasoline) HF/acid-clay
Platforming(gasoline) Pt/Al
2O
3
C
6H
6C
6H
12 Ni

10. INDUSTRIAL CATALYSIS-3
1950S
C
2H
4Polyethylene(Z-N) Ti
C
2H
4Polyethylene(Phillips) Cr-SiO
2
Polyprop &Polybutadiene(Z-N) Ti
Steam reforming Ni-K-Al
2O
3
HDS, HDT of naphtha (Co-Mo)/Al
2O
3
C
10H
8Phthalic anhydride (V,Mo)oxide
C
6H
6C
6H
12 (Ni)
C
6H
11OH C
6H
10O (Cu)
C
7H
8+ H
2C
6H
6+CH
4 (Ni-SiAl)

11. Butene Maleic anhydride (V,P) oxides
C
3H
6acrylonitrile(ammox) (BiMo)oxides
Bimetallic reforming PtRe/Al
2O
3
Metathesis(2C
3C
2+C
4) (W,Mo,Re)oxides
Catalytic cracking Zeolites
C
2H
4vinyl acetate Pd/Cu
C
2H
4vinyl chloride CuCl
2
O-Xylene Phthalic anhydride V
2O
5/TiO
2
Hydrocracking Ni-W/Al
2O
3
CO+H
2O H
2+CO
2(HTS) Fe
2O
3/Cr
2O
3/MgO
--do-- (LTS) CuO-ZnO-Al
2O
3
Industrial catalysis-4
1960s

12. Xylene Isom( for p-xylene) H-ZSM-5
Methanol (low press) Cu-Zn/Al
2O
3
Toluene to benzene and xylenes H-ZSM-5
Catalytic dewaxing H-ZSM-5
Autoexhaust catalyst Pt-Pd-Rh on oxide
Hydroisomerisation Pt-zeolite
SCR of NO(NH
3) V/ Ti
MTBE acidic ion exchange resin
C
7H
8+C
9H
12
C
6H
6+C
8H
10 Pt-Mordenite
Industrial catalysis-5
1970s

13. Ethyl benzene H-ZSM-5
Methanol to gasoline H-ZSM-5
Vinyl acetate Pd
Improved Coal liq NiCo sulfides
Syngas to diesel Co
HDW of kerosene/diesel.GO/VGO Pt/Zeolite
MTBE cat dist ion exchange resin
Oxdn of methacrolein Mo-V-P
N-C6 to benzene Pt-zeolite
Industrial catalysis-6
1980s

14. DMC from acetone Cu chloride
NH
3synthesis Ru/C
Phenol to HQ and catechol TS-1
Isom of butene-1(MTBE) H-Ferrierite
Ammoximation of cyclohexanone TS-1
Isom of oxime to caprolactam TS-1
Ultra deep HDS Co-Mo-Al
Olefin polym Supp. metallocene cats
Ethane to acetic acid Multi component oxide
Fuel cell catalysts Rh, Pt, ceria-zirconia
Cr-free HT WGS catalysts Fe,Cu-based
Industrial catalysis-7
1990
s

15. INDUSTRIAL CATALYSIS-8
2000+
Solid catalysts for biodiesel
-solid acids, Hydroisom catalysts
Catalysts for carbon nanotubes
-Fe (Ni)-Mo-SiO
2
For DevelopedCatalysts
MAINLY IMPROVEMENT IN
PERFORMANCE by New Synthesis Methods & use of PROMOTERS

16. GREEN CHEMISTRY IS CATALYSIS
Pollution control (air and waste streams; stationary and mobile)
Clean oxidation/halogenation processes using O
2,H
2O
2 (C
2H
4O, C
3H
6O)
Avoiding toxic chemicals in industry
(HF,COCl
2etc)
Fuel cells (H
2generation)
Latest Trends

17. CATALYSIS IN NANOTECHNOLOGY
Methods of Catalyst preparation are most suited for the preparation of
nanomaterials
Nano dimensions of catalysts
Common prep methods
Common Characterization tools
Catalysis in the preparation of carbon nanotubes
Latest Trends

18. CATALYSIS IN THE CHEMICAL INDUSTRY
Hydrogen Industry(coal,NH
3,methanol, FT,
hydrogenations/HDT,fuel cell)
Natural gas processing (SR,ATR,WGS,POX)
Petroleum refining (FCC, HDW,HDT,HCr,REF)
Petrochemicals (monomers,bulk chemicals)
Fine Chem. (pharma, agrochem, fragrance,
textile,coating,surfactants,laundry etc)
Environmental Catalysis (autoexhaust, deNOx, DOC)
Latest Trends

19. HETEROGENEOUS CATALYSIS
AN INRODUCTION

20. -Diffusion of Reactants (Bulk to Film to Surface)
-Adsorption
-Surface Reaction
-Desorption & Diffusion of Products
Steps of Catalytic Reaction

24. reactants
products
reactor
catalyst support
active
site
substrate
adsorption
reaction
desorption
bed of
catalyst
particles
porous carrier
(catalyst
support)
product

25. Role of Chemists & Chemical Engineers
Team Work

26. Wet impregnation:
•Preparation of precursors (Cu & Zn-nitrates) solution
•Impregnation of precursors on alumina support
•Rotary vacuum evaporation
•Drying
•Calcination
•Reduction
Rotary vacuum evaporator
Catalysts Preparation

27. Mixer cum shaker
Filteration
Drying @ 125
o
C for 12 h
Rotary Vacuum Evaporator
Crushing Sieving,
20/25 mesh
Round bottom flask with
Heating mental & Agitator
Drying
@ 125
o
C for 12 h
Crushing
Sieving, 20/25 mesh
Pelletizing
Crushing
Nitrate Salts solution &
Alumina pellets
Nitrate Salts
Solution
70
o
C, pH=7-8
Precipitates:
Ageing for 2 h
0.5M Na2CO3
Dropwise
addition
Calcination,
350
o
C for 4 h
Calcination,
350
o
C for 4 h
Catalyst
Catalyst Wet Impregnation Co-precipitation
Catalysts Preparation

28. WI CuO/ZnO/Al
2O
3Catalyst
Calcined

29. WI CuO/ZnO/Al
2O
3Catalyst
Calcined

30. Co-precipitation
Co/Al
2O
3
Calcined

31. Commercial Ni/Al
2O
3

32. Spent Commercial Ni/Al
2O
3

33. Commercial Fe
2O
3catalyst

34. Spent Commercial Fe
2O
3catalyst

35. Pt, Pd and Rh on the Metox metallic substrates
Pervoskite LATEST Research
Auto-catalysts

37. Honey Comb Catalysts

38. CATALYST CHARACTERIZATION
Bulk Physical Properties
Bulk Chemical Properties
Surface Chemical Properties
Surface Physical Properties
Catalytic Performance

39. BULK CHEMICAL PROPERTIES
Elemental composition (of the final catalyst)
XRD, electron microscopy (SEM,TEM)
Thermal Analysis(DTA/TGA)
NMR/IR/UV-Vis Spectrophotometer
TPR/TPO/TPD
EXAFS

40. SURFACE PROPERTIES
XPS,Auger, SIMS (bulk & surface structure)
Texture :Surface area-porosity
Counting “Active” Sites:
-Selective chemisorption (H
2,CO,O
2, NH
3,
Pyridine,CO
2);Surface reaction (N
2O)
Spectra of adsorbed species (IR/EPR/ NMR /
EXAFS etc)

41. PHYSICAL PROPERTIES OF CATALYSTS
Bulk density
Crushing strength & attrition loss
(comparative)
Particle size distribution
Porosimetry (micro(<2 nm), macro(>35 nm)
and meso pores

42. Catalysts Characterization
Characteristics Methods
Surface area, pore volume & sizeN
2
Adsorption-Desorption Surface area
analyzer (BET and Langmuir)
Pore size distribution BJH (Barret, Joyner and Halenda)
Elemental composition of
catalysts
Metal Trace Analyzer / Atomic Absorption
Spectroscopy
Phases present & Crystallinity X-ray Powder Diffraction
TG-DTA (for precursors)
Morphology Scanning Electron Microscopy
Catalyst reducibility Temperature Programmed Reduction
Dispersion, SA and particle size
of active metal
CO Chemisorption, TEM
Acidic/Basic site strength NH
3
-TPD, CO
2TPD
Surface & Bulk Composition XPS
Coke measurement Thermo Gravimetric Analysis, TPO

43. BET Surface Area Analyzer
Surface area, Pore Volume, Pore Size & Pore size distribution
Major role of Chemical Engineer with Chemists for Hardware

44. 0
20
40
60
80
100
120
140
160
180
200
0100200300400500600700
Relative pressure, P/P0
Volume adsorbed, cm
3
g
-
1
(STP)
000.0E+0
1.0E-3
2.0E-3
3.0E-3
4.0E-3
5.0E-3
6.0E-3
7.0E-3
10 100 1000
Pore diameter, A
0
Pore volume, cm
3
g
-
1
A
0
-
1
CZCEA2
CZA2
Pore size distribution by BJH methodN
2adsorption/desorption Isotherm
P2CZCeA
Surface Area and Pore size Distribution
Barret, Joyner, and Halenda (BJH)
P3CZA
P2CZCeA
P2CZCeA Cu/Zn/Ce/Al:30/20/10/40
P3CZA Cu/Zn/Al:30/20/50m
0k
2 V COSP
ln
P r RT



45. Chemisorption Analyzer
Dispersion, Metal Surface area and Metal Particle size; TPR, TPO, TPD

47. TGA/DTA Analyzers
Coke measurement
& TPO

48. Reactions involved in SRM process
CH
3OH + H
2O ↔ CO
2+ 3H
2
CO
2+ H
2↔ CO + H
2O
CH
3OH ↔ 2H
2+ CO
CH
3OH + (1-p)H
2O +0.5pO
2↔CO
2+ (3-p)H
2
∆H
0
= (49.5 -242*p) kJ mol
-1
CH
3OH + 0.75H
2O + 0.125O
2↔CO
2+ 2.75H
2 ∆H
0
= -10 kJ mol
-1
∆H
300 oC
= 0 kJ mol
-1
CH
3OH + 0.5H
2O + 0.25O
2↔CO
2+ 2.5H
2 ∆H
0
= -71.4 kJ mol
-1
CH
3OH + 0H
2O + 0.5O
2↔CO
2+ 2H
2 ∆H
0
= -192 kJ mol
-1
CH
3OH + 1.5O
2↔CO
2+ 2H
2O∆H
0
= -727 kJ mol
-1
Reactions involved in OSRM process

49. CATALYST ACTIVITY TESTING
Activity to be expressed as:
-Rate constants from kinetics
-Rates/weight
-Rates/volume
-Conversions at constant P,T and SV.
-Temp required for a given conversion at constant partial & total pressures
-Space velocity required for a given conversion at constant pressure and
temp

50. Parameters
Catalyst mass, g 1-3
Contact-time (W/F)
kg
cat
s mol
-1
3-15
Temperature,
o
C 200-300
S/M molar ratio 0-1.8 (SRM)
S/O/M molar ratio 1.5/0-0.5/1 (OSRM)
Pressure, atm 1
Operating Conditions for SRM & OSRM

51. Schematic diagram of
OSRM process
Packed Bed
Catalytic Reactor
Methanol & Water Feed Pumps
Vaporizer
cum Mixer

V-3

V-2

V-1
Condenser
G-L Separator
Methanol & Water
Product Gases
O2 N2 H2
FM-1 FM-2 FM-3
Gas Chromatograph with DAS
Chiller
FM-4
For Catalyst
Reduction

52. Schematic diagram of
OSRM process
Packed Bed
Catalytic Reactor
Methanol & Water Feed Pumps
Vaporizer
cum Mixer

V-3

V-2

V-1
Condenser
G-L Separator
Methanol & Water
Product Gases
O2 N2 H2
FM-1 FM-2 FM-3
Gas Chromatograph with DAS
Chiller
FM-4
For Catalyst
Reduction
L 770mm
Thermocouple
Reactants Inlet
ID 19mm
OD 25mm
Flange
Catalyst bed
Products

56. T=280
o
C, W/F=11 kg
cats mol
-1
, S/O/M=1.5/0.15/1 & P=1 atm
Characterization and Activities of ZnO & Ceria promoted Catalysts
Co-precipitation P4CZA P3CZA P1CZCeA P2CZCeA P3CZCeA
Cu/Zn/Al Cu/Zn/Al Cu/Zn/Ce/Al Cu/Zn/Ce/Al Cu/Zn/Ce/Al
Composition,wt% 30/30/4030/20/5030/25/5/40 30/20/10/40 30/10/20/40
BETSA,m
2
g
-1
92 106 96 108 101
Porevolume,cm
3
g
-1
0.26 0.32 0.28 0.34 0.29
Cudispersion,% 9.4 12.8 10.2 19.6 14.8
CuSA,m
2
g
-1
18.3 25.1 20.2 38.6 29.3
Cuparticlesize,Å 108 80 101 52 69
X,% 60 77 69 100 90
H
2
rate,mmols
-1
kg
cat
-1
132 180 160 244 217
COformation,ppm 9400 3400 1400 995 1240

57. At Lab Scale Activity at Kinetically
Controlled Conditions
Scale-up &
Commercialization
Major Role of Chemists & Chemical Engineers
Examples of Steam Reformer & Ammonia Reactor

58. Primary Reformer

59. Ammonia Converter

60. RECENT TRENDS

61. BIG PICTURE: SUSTAINABLE
DEVELOPMENT

62. GREEN CHEMISTRY IS ABOUT...
Cost
Waste
Materials
Hazard
Risk
Energy

63. The drivers of green chemistry
Green chemistry
Less
hazardous materials
High fines for waste
Producer
responsibility
Government legislation
Lower
capital investment
Lower
operating costs
Economic benefit
Pollution control
Safer
and smaller plants
Improved
public image
Societal pressure

64. THE 12 PRINCIPLES OF GREEN CHEMISTRY (1-6)
1. Prevention
It is better to prevent waste than to treat or clean up waste after it has been created.

2. Atom Economy
Synthetic methods should be designed to maximise the incorporation of all materials
used in the process into the final product.

3. Less Hazardous Chemical Synthesis
Wherever practicable, synthetic methods should be designed to use and generate
substances that possess little or no toxicity to people or the environment.

4. Designing Safer Chemicals
Chemical products should be designed to effect their desired function while minimising
their toxicity.

5. Safer Solvents and Auxiliaries
The use of auxiliary substances (e.g., solvents or separation agents) should be made
unnecessary whenever possible and innocuous when used.

6. Design for Energy Efficiency
Energy requirements of chemical processes should be recognised for their environmental
and economic impacts and should be minimised. If possible, synthetic methods should be
conducted at ambient temperature and pressure.

65. 7 Use of Renewable Feedstocks
A raw material or feedstock should be renewable rather than depleting
whenever technically and economically practicable.
8 Reduce Derivatives
Unnecessary derivatization(use of blocking groups, modification of
physical/chemical processes) should be minimised or avoided if possible,
because such steps require additional reagents and can generate waste.
9Catalysis
10 Design for Degradation
Chemical products should be designed so that at the end of their function they
break down into innocuous degradation products and do not persist in the
environment.
11 Real-time Analysis for Pollution Prevention
Analytical methodologies need to be further developed to allow for real-time,
in-process monitoring and control prior to the formation of hazardous
substances.
12 Inherently Safer Chemistry for Accident Prevention
THE 12 PRINCIPLES OF GREEN CHEMISTRY (7-12)

66. GREEN CATALYTIC PROCESSES
Alternative feedstocks, reagents, solvents, products
Enhanced process control
New catalysts
Greater integration of catalysis and reactor engineering:
membrane reactors, microreactors, monolith technology, phenomena
integration
Increased use of natural gas and biomass as feedstock
Photodecomposition of water into hydrogen and oxygen
Catalysts for depolymerizing polymers for recycle of the monomers
Improvements in fuel cell electrodes and their operation

67. CLEANER AND GREENER ENVIRONMENT: CATALYSIS
New directions for research driven by market, social & environmental needs:
Catalysis for energy-friendly technologies and processes (primary methods)
New advanced cleanup catalytic technologies (secondary methods)
Catalytic processes and technologies for reducing the environmental impact
of chemical and agro-industrial solid or liquid waste and improving the
quality and reuse of water (secondary methods)
Catalytic processes for a sustainable chemistry (green chemistry and
engineering approach)
Replacement of environmentally hazardous catalysts in existing processes

68. HOW TO DECREASE THE GREENHOUSE EFFECT?
New catalysts for high output fuel cells
•Electricity production via electrocatalytic oxidation of hydrocarbons
•Chemical energy of hydrocarbon is converted to electricity
Catalysts and processes for solar energy conversion and hydrogen
production
•CO
2or other greenhouse gases are not emitted into the atmosphere,
•First solar energy is converted into the chemical energy of synthesis gas
(CO + H
2) via the endothermic reaction of methane reforming
•Storage of the synthesis gas
•The stored energy can be released via the reverse exothermal
methanation reaction
CO + 3H
2→ CH
4+ H2O
•Efficiency from 43 to 70 %
Catalysts are needed for these reactions!!!

69. Classic Route to Ibuprofen
Ac
2
O
AlCl
3
COCH
3
HCl, AcOH, Al W aste
ClCH
2
CO
2
Et
NaOEt
O
EtO
2
C
HCl
H
2
O / H+
OHC
AcOH
NH
2
OH
OHN
N
H
2
O / H+
HO
2
C
NH
3 Examples of Green Catalysis

70. Hoechst Route To Ibuprofen
O
HF
AcOH
Ac
2
O
H
2
/ Ni
OH
CO, Pd
HO
2
C Examples of Green Catalysis

71. “THE USE OF AUXILIARY SUBSTANCES (E.G.
SOLVENTS,
SEPARATION AGENTS, ETC.) SHOULD BE
MINIMIZED”
Examples of Green Catalysis

72. POLY LACTIC ACID (PLA) FOR PLASTICS
PRODUCTION
Examples of Green Catalysis

73. POLYHYDROXYALKANOATES (PHA’S)
Examples of Green Catalysis

74. ‘TiO
2’AGREEN CATALYST:
CLEAN ENVIRONMENT
Examples of Green Catalysis

75. PHOTOCATALYSIS
Photocatalyst
Starch + O
2
Organic compound
Chlorophyll
CO
2
H
2O
CO
2+ H
2O
Organic
Compound
+ H
2O + O
2

76. PHOTOCATALYTICAPPLICATIONS

77. SELF-CLEANING EFFECT

78. TIO
2-PHOTOCATALYSIS
3.12 eV
(380 nm)

79. PHOTOCATALYTIC REACTIONSTiO
2 + h TiO
2 (e
-
+ h
+
)
h
+
+ H
2O OH + H
+
O
2 + e
-
O
2
-
O
2
-
+ H
+
HO
2
HO
2 +HO
2 H
2O
2 + O
2
O
2
-
HO
2
+
H
2O
2
O
2 + HO
2
-
HO
2
-
+ 

H
2O
2 + h OH2
H
2O
2 +O
2
-
HO + OH
-
+ O
2
H
2O
2 + e
-
HO + OH
-

80. MICROREACTORS –FUTURE
Catalytic processes
•Uniform channel structure, fractal catalyst supports
•Scale-up
•How microreactor is connected to the macroworld?
•Operating regimes
•Controlled periodic processing
•Programmable reactor
•Process control
•Miniaturized sensors and actuators
•Local feedback and programmable regimes
•Advanced structure, materials, process control
•Multiscale –finely defined; locally targeted –globally optimized

81. Random Vs Structured Catalysts
Structured Beds
of Tomorrow
Random Packed
Today

82. Monoliths (Structured) vs Pellets (Random)
Monolith catalyst
extruded from
commercial catalyst
support material
Conventional pellets
made from the same
material
Does the configuration alone improve performance?

83. Micro Process Plant
Chemistry &
Catalysis
Raw Materials &
Feedstocks
Catalyst
Characterization
Reaction Pathways &
Mechanisms
Reaction
Kinetics
Micro Systems
Engineering
Tools, Fabrication &
Assembly
Microprocess
Components
Materials of
Construction
Component
Integration
Multi-scale
Transport
Micro Process
Analytical
Integrated
Sensors
Sampling
Sensors
Data handling &
Chemometrics
Micro PAT Systems
Integration
Micro Analyzers (GC,
LC, MS, TOF)
Process
Engineering
Flowsheet
Synthesis
Control
Systems
2D & 3D
CAD Solids
Modeling
Microscale Design
Modules
Flow
Patterns
Simulation &
Optimization
Multiscale
Transport

84. High surface-to-volume area;
enhanced mass and heat transfer;
high volumetric productivity;
Laminar flow conditions; low
pressure drop
Some Advantages of Microreactors & Monoliths
•Residence time distribution and extent of back mixing controlled –
“precise reaction engineering”
•Low manufacturing, operating, and maintenance costs, and low
power consumption
•Minimal environmental hazards and increased safety due to small
volume
•“Scaling-out” or “numbering-up” instead of scaling-up

85. Some Potential Problems
•Short residence times require fast reactions
•Fast reactions require very active catalysts that are stable (The two
most often do not go together)
•Catalyst deactivation and frequent reactor repacking or
reactivation
•Fouling and clogging of channels
•Leaks between channels
•Malfunctioning of distributors
•Reliability for long time on-stream
•Structural issues
So far there are only two major commercial uses of micro-channel
systems (monoliths) –
•Automotive catalytic convectors (major success)
•Selective catalytic reduction (NH
3–SCR) of power plant NO
x

86. APPLICATIONS OF THE PROCESS UTILIZING
BIOMASS STREAMS
Biomass
Waste
Aqueous
Biomass
Stream
Extraction
Extraction
PEM
Fuel Cell
SOFC
ICE
Genset
Microturbine
Genset
Hydrogen
APR
Fuel Gas
APR
Energy
Crops
Process
Hydrogen

87. CATALYSIS IN THE PRODUCTION OF FUTURE
TRANSPORTATION FUELS

88. BIOFUELS LIFE CYCLE

89. TECHNOLOGY FOR GREEN & BIOFUELS

90. BIOMASS SOURCES FOR BIOFUELS
LignoCellulose (Cellulose, Hemicellulose, Lignin)
Starch
Sugars
Lipid Glycerides (Vegetable Oils & Animal Fats)

91. Structures in Lignocellulose

92. 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

93. BIOETHANOL OVERVIEW -GLOBAL
CurrentbioethanolproductioninUSis12billiongallons.
MostcarsontheroadinUStodaycanrunonblendsofupto10%ethanol.
USDOEhasestimatedthatthereisapotentialtoproduceover80Billiongallonsofbio-
ethanolfromcelluloseandhemi-cellulosepresentincornbiomassinthe9majorUS
cornproducingstates.
Thisequatestoover250Milliontonsofbio-ethanoland>$160Billionrevenue.
Iogen’sDemoplantproducingcellulosicethanolfromwheatstrawinCanadasince
2004.
DuPont-DaniscoJVhasstarteddemonstrationofcellulosicethanolfromcorncobssince
Jan.,2010inUSA.
Brazilcurrentlyblends25%ethanolingasolineandbioethanolisproduceddirectly
fromsugarcane.
Brazilianflexcarsarecapableofrunningonjusthydratedethanol(E100),orjustona
blendofgasolinewith20to25%anhydrousethanol,oronanyarbitrarycombinationof
bothfuels
Chinauses10%bioethanolingasoline.

95. 2
nd
Generation Bioethanol Technology Overview

96. Hydrolysis based Technology Players
Company Location Technology Present Status
DuPont-
Danisco
USA Feed stock -Agri residue.
Alkaline pretreatment ,
enzymatic hydrolysis +
C5/C6 Co-fermentation
Pilot Plant started
Iogen/
Shell
Canada Feed stock –Agri Biomass.
Pretreatment –steam
explosion. Enzymatic
hydrolysis & fermentation of
C5/C6 sugars
Demo. Plant operating,
since 2004. Commercial
Plant expected to be
commissioned in 2011.
Lignol Canada Feed stock -wood,
agribiomass. Organosolv
pretreatment & sepn. Of high
purity lignin. Enzymatic
hydrolysis and fermentation
of C5 & C6 sugars
separately
Technology proven at
Bench scale.
Pilot Scale under
Engineering design.

97. Enzymatic based Cellulosic Ethanol Process
Biomass
Lignin
Pretreatment
C5/C6 Sugars
Hydrolysis Distillation/
dehydration
Bioreactor
Ethanol
99.7 wt%
Enzyme
Production
Microbe
Second Generation Bioethanol

98. Gasification based Technology Players
CompanyLocationTechnology Present Status
COSKATAUSA Feed stock -Agri residue,
pet coke, MSW.
Gasification to syn-gas &
direct fermentation to
ethanol.
Completed pilot scale
optimization.
INEOS
Bio
USA Feed stock -Agriresidue,
MSW. Conventional
Gasification to syn-gas &
its fermentation to
ethanol.
Process under study in
pilot plant.
Gasification based Technology Players

99. Biomass
Gasification based Cellulosic Ethanol Process
Gasifier
Bioreactor
Distillation/
dehydration
Microbe
Ethanol
99.7 wt%
Syn-gas
4 -6% ethanol

101. Transportation Fuels from Cellulosic Biomass (Pyrolysis Route)

102. TRANSPORTATION FUELS FROM BIOMASS
BIODIESELS
First generation biodiesel
Fatty Acid methyl esters (FAME); methyl esters of C
16and C
18acids.
Second generation Biodiesels
“Hydrocarbon Biodiesels” ; C
16and C
18saturated, 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.

103. FIRST GENERATION BIODIESELS
FATTY ACID METHYL ESTERS
Veg Oil + methanol FAME + glycerine
Catalysts:Alkali catalysts( Na/K methoxides); CSTR;
Large water, acid usage in product separation

104. FUEL QUALITYPROBLEMS IN FIRST
GENERATION TECHNOLOGY
Lower glycerol purity; Not suitable for production of chemicals (propanediol,
acrolein etc) without major purification; Salts and H
2O 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.

105. 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
2at 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.

106. 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; ~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 infrastructure
-Engine compatibility; Feedstock flexibility

107. CAPITAL COSTS :EIA ANNUAL ENERGY OUTLOOK 2006
107

108. 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 SOFCcan generate electricity by direct
internal reforming of NG at 650C;Ni/ Zr(La)Al
2O
4, loaded on anode

109. CATALYSTS FOR CONVERSION OF NG TO
TRANSPORTATION FUELS
I.Syngas Preparation
-Hydrodesulphurisation(Co/Ni-Mo-alumina)
-Syngas generation(H
2/ CO); 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.
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 )

110. PETROLEUM -VS-SYNGAS :: 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.

111. POWER AND FUELS FROM COAL / PETCOKE
GASIFICATION TEXACO EECP PROJECT
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.

112. COAL TO SYNGAS TO FUEL CELLS
Catalysis 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 H
2+ CO
2( -42 kJ/mol)
Methan: CO+3 H
2CH
4+ H
2O(-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
4as
fuel to generate electricity.
Low rank coals, Lignites gasify easier.

113. HYDROGEN PRODUCTION COSTS
(THE ECONOMIST/ IEA)
SOURCE USD / GJ
Coal / gas/ oil/ biodiesel 1-5
NG + CO
2 sequestration 8-10
Coal + CO
2sequestration 10-13
Biomass(SynGas route) 12-18
Nuclear (Electrolysis) 15-20
Wind (Electrolysis) 15-30
Solar (Electrolysis) 25-50

115. SUGAR CANE JUICE TO H
2
AQUEOUS PHASE REFORMING
C
6H
12O
6+6H
2O 12H
2+6CO
2(APR)
Pt-alumina catalysts, 200
o
C
1 kg of H
2($3-4) from 7.5 kg Sugar
Fuel Efficiency of H
2>> diesel/gasoline

116. H
2PRODUCTION FROM GLYCERIN
Available from Veg oils(40-98% in H
2O)
C
3H
8O
3+3H
2O7H
2+ 3CO
2
Ru –Y
2O
3catalysts; 600
o
C
1 kg H
2from 7 kg glycerine
H
2production from Biomass is less economically viable than production of
ethanol and biodiesel from biomass.

117. Catalytic Direct Methane Decomposition
to H
2and Carbon Nanotubes

118. Catalytic Auto Thermal Reforming of
Methanol, Ethanol, DME to HYDROGEN
for FUEL CELL

119. Pure H
2Supply
•Compressed H
2
•Liquid H
2
•H
2Hydride
H
2from Reformed liquid HC
H
2
Fuel
•Methanol
•Ethanol
•DME
H
2Combustion Engine
Similar to Gasoline Internal
Combustion Engine

120. Pure H
2Supply
•Compressed H
2
•Liquid H
2
•H
2Hydrid
H
2from Reformed liquid HC
H
2
Fuel
•Methanol
•Ethanol
•DME
PEM Fuel Cell

121. Pure H
2Supply
•Compressed H
2
•Liquid H
2
•H
2Hydrid
H
2from Reformed liquid HC
H
2
Fuel
•Methanol
•Ethanol
•DME
PEM Fuel Cell
H
2Production from
Fossil & Renewable
Sources

122. CATALYSTS FOR H
2O AND CO
2PHOTOTHERMAL
SPLITTING
USING SUNLIGHT
1. H
2OH
2+ 0.5 O
2
2. CO
2CO +0.5 O
2
FT Synthsis: CO +H
2 (CH
2)
npetrol/Diesel
Sandia’s Sunlight To PetrolProject: Cobalt ferrite loses O
atom at 1400
o
C; When cooled to 1100
o
C in presence of CO
2
orH
2O, it picks up O, catalyzing reactions 1 and 2; Solar
absorber provides the energy.
Challenge: Find a solid which loses / absorbs O from H
2O /
CO
2reversiblyat a lower temp.

123. SPLITTING H
2O

124. 124

125. SPLITTING H
2O WITH VISIBLELIGHT
125

126. FUTURE FUELS: CATALYSIS CHALLENGES
Meeting Specifications of Future Fuels
Remove S,N, aromatics, Particulate Matter
Power Generation
-Lower CO
2Production in Catalytic Gasification
-Lower CO
2 and H
2/CO ratio in Syngas generation
FT Synthesis: Lower CH
4and 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
2and Biofuels will avoid costs due to
their storage and distribution.
“Holy Grail “ Challenges
Direct Conversion of CH
4to methanol and C
5
+
.
Catalytic Water and CO
2splitting using solar energy

127. 127