Chemists and Chemical Engineers Make the
World a Better Place through Modern
Developments in Heterogeneous Catalysis
Presented by
SANJAY PATEL
Department of Chemical Engineering
Institute of Technology, Nirma University
Content
Chemistry & Chemical Engineering
History of Catalysis
Catalysis
Recent trends in Catalysis
Future trends in Catalysis
Summary
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
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, H2, Fuel Cells, biofuels…)
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)
Three Scales of Knowledge Application
Some Developments in Industrial catalysis-1
1900- 1920s
Industrial Process
Catalyst
1900s: CO + 3H2  CH4 + H2O
Ni
Vegetable Oil + H2  butter/margarine
Ni
1910s: Coal Liquefaction
Ni
N2 + 3H2  2NH3
NH3 NO NO2 HNO3
1920s: CO + 2H2  CH3OH (HP)
Fischer-Tropsch synthesis
SO2  SO3 H2SO4
Fe/K
Pt
(ZnCr)oxide
Co,Fe
V2O5
Industrial catalysis-2
1930s and 1940s
1930s:Cat Cracking(fixed,Houdry)
Mont.Clay
C2H4 C2H4O
Ag
C6H6  Maleic anhydride
V2O5
1940s:Cat Cracking(fluid)
amorph. SiAl
alkylation (gasoline)
HF/acid- clay
Platforming(gasoline)
Pt/Al2O3
C6H6 C6H12
Ni
Industrial catalysis-3
1950s
C2H4 Polyethylene(Z-N)
C2H4 Polyethylene(Phillips)
Polyprop &Polybutadiene(Z-N)
Steam reforming
HDS, HDT of naphtha
C10H8  Phthalic anhydride
C6H6  C6H12
C6H11OH C6H10O
C7H8+ H2 C6H6 +CH4
Ti
Cr-SiO2
Ti
Ni-K- Al2O3
(Co-Mo)/Al2O3
(V,Mo)oxide
(Ni)
(Cu)
(Ni-SiAl)
Industrial catalysis-4
1960s
Butene Maleic anhydride
(V,P) oxides
C3H6  acrylonitrile(ammox)
Bimetallic reforming
(BiMo)oxides
PtRe/Al2O3
Metathesis(2C3 C2+C4)
Catalytic cracking
(W,Mo,Re)oxides
Zeolites
C2H4 vinyl acetate
Pd/Cu
C2H4  vinyl chloride
CuCl2
O-Xylene Phthalic anhydride
Hydrocracking
V2O5/TiO2
Ni-W/Al2O3
CO+H2O H2+CO2 (HTS)
--do-(LTS)
Fe2O3/Cr2O3/MgO
CuO-ZnO- Al2O3
Industrial catalysis-5
1970s
Xylene Isom( for p-xylene)
H-ZSM-5
Methanol (low press)
Cu-Zn/Al2O3
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(NH3)
V/ Ti
MTBE
C7H8+C9H12 C6H6 +C8H10
acidic ion exchange resin
Pt-Mordenite
Industrial catalysis-6
1980s
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
MTBE cat dist
Oxdn of methacrolein
N-C6 to benzene
Pt/Zeolite
ion exchange resin
Mo-V-P
Pt-zeolite
Industrial catalysis-7
1990s
DMC from acetone
Cu chloride
NH3 synthesis
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
Olefin polym
Co-Mo-Al
Supp. metallocene cats
Ethane to acetic acid
Fuel cell catalysts
Cr-free HT WGS catalysts
Multi component oxide
Rh, Pt, ceria-zirconia
Fe,Cu- based
Industrial catalysis-8
2000+
• Solid catalysts for biodiesel
- solid acids, Hydroisom catalysts
• Catalysts for carbon nanotubes
- Fe (Ni)-Mo-SiO2
For Developed Catalysts MAINLY IMPROVEMENT IN
PERFORMANCE by New Synthesis Methods & use of PROMOTERS
Green Chemistry is Catalysis
• Pollution control (air and waste streams;
stationary and mobile)
• Clean oxidation/halogenation processes using
O2,H2O2 (C2H4O, C3H6O)
• Avoiding toxic chemicals in industry
(HF,COCl2 etc)
• Fuel cells (H2 generation)
Latest Trends
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
Catalysis in the Chemical Industry
• Hydrogen Industry(coal,NH3,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
HETEROGENEOUS CATALYSIS
AN INRODUCTION
Steps of Catalytic Reaction
- Diffusion of Reactants (Bulk to Film to Surface)
- Adsorption
- Surface Reaction
- Desorption & Diffusion of Products
porous carrier
(catalyst
support)
bed of
catalyst
particles
reactants
substrate
product
reactor
reaction desorption
adsorption
products
catalyst support
active
site
Role of Chemists & Chemical Engineers
Team Work
Catalysts Preparation
Wet impregnation:
• Preparation of precursors (Cu & Zn-nitrates) solution
• Impregnation of precursors on alumina support
• Rotary vacuum evaporation
• Drying
• Calcination
• Reduction
Rotary vacuum evaporator
Nitrate Salts solution &
Alumina pellets
Catalysts Preparation
0.5M Na2CO3
Dropwise
addition
Wet Impregnation
Co-precipitation
Nitrate Salts
Solution
70 oC, pH=7-8
Mixer cum shaker
Precipitates:
Ageing for 2 h
Round bottom flask with
Heating mental & Agitator
Crushing
Catalyst
Rotary Vacuum Evaporator
Sieving, 20/25 mesh
Filteration
Drying @ 125 oC for 12 h
Calcination,
350 oC for 4 h
Drying
@ 125 oC for 12 h
Pelletizing
Catalyst
Crushing
Sieving,
20/25 mesh
Crushing
Calcination,
350 oC for 4 h
Calcined
WI CuO/ZnO/Al O Catalyst
Calcined
WI CuO/ZnO/Al O Catalyst
Co-precipitation
Co/Al2O3
Calcined
Commercial Ni/Al2O3
Spent Commercial Ni/Al2O3
Commercial Fe2O3 catalyst
Spent Commercial Fe2O3 catalyst
Auto-catalysts
Pt, Pd and Rh on the Metox metallic substrates
Pervoskite LATEST Research
Honey Comb Catalysts
CATALYST CHARACTERIZATION
• Bulk Physical Properties
• Bulk Chemical Properties
• Surface Chemical Properties
• Surface Physical Properties
• Catalytic Performance
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
Surface Properties
• XPS,Auger, SIMS (bulk & surface structure)
• Texture :Surface area- porosity
• Counting “Active” Sites:
-Selective chemisorption (H2,CO,O2, NH3,
Pyridine,CO2);Surface reaction (N2O)
• Spectra of adsorbed species (IR/EPR/ NMR /
EXAFS etc)
Physical properties of catalysts
• Bulk density
• Crushing strength & attrition loss
(comparative)
• Particle size distribution
• Porosimetry (micro(<2 nm), macro(>35
nm) and meso pores
Catalysts Characterization
Characteristics
Methods
Surface area, pore volume & size
N2 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
NH3-TPD, CO2 TPD
Surface & Bulk Composition
XPS
Coke measurement
Thermo Gravimetric Analysis, TPO
BET Surface Area Analyzer
Major role of Chemical Engineer with Chemists for Hardware
Surface area, Pore Volume, Pore Size & Pore size distribution
Surface Area and Pore size Distribution
7.0E-3
CZCEA2
P2CZCeA
P2CZCeA
180
6.0E-3
g -1 A0-1
160
140
CZA2
5.0E-3
3
120
100
Pore volume, cm
3
-1
Volume adsorbed, cm
g (STP)
200
80
60
40
20
4.0E-3
3.0E-3
2.0E-3
P3CZA
1.0E-3
0
0
100
200
300
400
500
600
700
000.0E+0
10
Relative pressure, P/P
0
100
Pore diameter, A
1000
0
N2 adsorption/desorption Isotherm Pore size distribution by BJH method
Barret, Joyner, and Halenda (BJH)
P2CZCeA Cu/Zn/Ce/Al:30/20/10/40
P3CZA
Cu/Zn/Al:30/20/50
P 2 Vm COS
ln

P0
rk RT
Chemisorption Analyzer
Dispersion, Metal Surface area and Metal Particle size; TPR, TPO, TPD
TGA/DTA Analyzers
Coke measurement
& TPO
Reactions involved in SRM process
CH3OH + H2O ↔ CO2 + 3H2
CO2 + H2 ↔ CO + H2O
CH3OH ↔ 2H2 + CO
Reactions involved in OSRM process
CH3OH + (1-p)H2O +0.5pO2 ↔ CO2 + (3-p)H2
∆H0 = (49.5 - 242*p) kJ mol-1
CH3OH + 0.75H2O + 0.125O2 ↔ CO2 + 2.75H2 ∆H0 = -10 kJ mol-1
∆H300 oC = 0 kJ mol-1
CH3OH + 0.5H2O + 0.25O2 ↔ CO2 + 2.5H2 ∆H0 = -71.4 kJ mol-1
CH3OH + 0H2O + 0.5O2 ↔ CO2 + 2H2
∆H0 = -192 kJ mol-1
CH3OH + 1.5O2 ↔ CO2 + 2H2O
∆H0 = -727 kJ mol-1
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
Operating Conditions for SRM & OSRM
Parameters
Catalyst mass, g
1-3
Contact-time (W/F)
kgcat s mol-1
3-15
Temperature, oC
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
Schematic diagram of
OSRM process
Vaporizer
cum Mixer
Methanol & Water Feed Pumps
Gas Chromatograph with DAS
Packed Bed
Catalytic Reactor
Chiller
FM-1
FM-2
V-1
V-2
FM-3
V-3
Condenser
For Catalyst
Reduction
FM-4
Product Gases
G-L Separator
Methanol & Water
O2
N2
H2
Schematic diagram of
OSRM process
Vaporizer
cum Mixer
Methanol & Water Feed Pumps
Reactants Inlet
Thermocouple
Flange
OD 25mm
Gas Chromatograph with DAS
Catalyst bed
Packed Bed
Catalytic Reactor
L 770mm
FM-1
FM-2
V-1
V-2
FM-3
V-3
ID 19mm
Condenser
Chiller
For Catalyst
Reduction
FM-4
Products
Product Gases
G-L Separator
Methanol & Water
O2
N2
H2
Characterization and Activities of ZnO & Ceria promoted Catalysts
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%
30/30/40
30/20/50
30/25/5/40
30/20/10/40
30/10/20/40
BET SA, m2 g-1
92
106
96
108
101
Pore volume, cm3 g-1
0.26
0.32
0.28
0.34
0.29
Cu dispersion, %
9.4
12.8
10.2
19.6
14.8
Cu SA, m2 g-1
18.3
25.1
20.2
38.6
29.3
Cu particle size, Å
108
80
101
52
69
X, %
60
77
69
100
90
180
160
244
217
3400
1400
995
1240
Co-precipitation
H2 rate,
kgcat-1
mmol
CO formation, ppm
s-1 132
9400
T=280 oC, W/F=11 kgcat s mol-1, S/O/M=1.5/0.15/1 & P=1 atm
At Lab Scale Activity at Kinetically
Controlled Conditions
Scale-up &
Commercialization
Major Role of Chemists & Chemical Engineers
Examples of Steam Reformer & Ammonia Reactor
Primary Reformer
Ammonia Converter
RECENT TRENDS
Big picture: Sustainable Development
Green Chemistry Is About...
Waste
Materials
Hazard
Risk
Energy
Cost
The drivers of green chemistry
Economic benefit
Lower
capital investment
Lower
operating costs
Societal pressure
Government legislation
Improved
public image
Safer
and smaller plants
Pollution control
Less
hazardous materials
Green chemistry
High fines for waste
Producer
responsibility
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.
The 12 Principles of Green Chemistry (7-12)
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.
9 Catalysis
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
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
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
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
•CO2 or other greenhouse gases are not emitted into the atmosphere,
• First solar energy is converted into the chemical energy of synthesis gas
(CO + H2) 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 + 3H2 → CH4 + H2O
•Efficiency from 43 to 70 %
Catalysts are needed for these reactions!!!
Classic Route to Ibuprofen
H C l, A cO H , A l W aste
Ac 2 O
Ac O H
HCl
H 2 O / H+
Cl C H 2 C O 2 Et
A l Cl 3
Na O Et
C O C H3
Et O 2 C
Examples of Green Catalysis
OHC
O
N H2 O H
H 2 O / H+
N
H O2 C
N H3
OHN
Hoechst Route To Ibuprofen
AcOH
HF
H2 / Ni
CO, Pd
Ac2O
O
HO
Examples of Green Catalysis
HO2C
“The use of auxiliary substances (e.g. solvents,
separation agents, etc.) should be minimized”
Examples of Green Catalysis
Poly lactic acid (PLA) for plastics production
Examples of Green Catalysis
Polyhydroxyalkanoates (PHA’s)
Examples of Green Catalysis
‘TiO2’ A GREEN CATALYST:
CLEAN ENVIRONMENT
Examples of Green Catalysis
Photocatalysis
CO2 + H2O
CO2
Chlorophyll
Photocatalyst
Organic
Compound
H2O
Starch + O2
Organic compound
+ H2O + O2
Photocatalytic Applications
Self-Cleaning Effect
TiO2 - Photocatalysis
3.12 eV
(380 nm)
Photocatalytic Reactions
TiO2 + h
h+ + H2O
O2 + eO2 - + H+
HO2 + HO2
O2
-
+ HO2
TiO2 (e- + h+)
OH + H+
O2
-
HO2
H2O2 + O2
O2 + HO2-
HO2- + 
H2O2
H2O2 + h
2 OH
H2O2 + O2
-
H2O2 + e-
HO + OH- + O2
HO + OH-
Catalytic processes
Microreactors – Future
• 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
Random Vs Structured Catalysts
Random Packed
Today
Structured Beds
of Tomorrow
Monoliths (Structured) vs Pellets (Random)
Monolith catalyst
extruded from
commercial catalyst
support material
Does the configuration alone improve performance?
Conventional pellets
made from the same
material
Flowsheet
Synthesis
2D & 3D
CAD Solids
Modeling
Multiscale
Transport
Process
Engineering
Control
Systems
Microscale Design
Modules
Flow
Patterns
Simulation &
Optimization
Tools, Fabrication &
Assembly
Materials of
Construction
Microprocess
Components
Component
Integration
Micro Systems
Engineering
Multi-scale
Transport
Micro Process
Plant
Raw Materials &
Feedstocks
Chemistry &
Catalysis
Reaction
Kinetics
Integrated
Sensors
Catalyst
Characterization
Reaction Pathways &
Mechanisms
Sampling
Sensors
Data handling &
Chemometrics
Micro Analyzers (GC,
LC, MS, TOF)
Micro Process
Analytical
Micro PAT Systems
Integration
Some Advantages of Microreactors & Monoliths
• High surface-to-volume area;
enhanced mass and heat
transfer;
• high volumetric productivity;
• Laminar flow conditions; low
pressure drop
• 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
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 (NH3 – SCR) of power plant NOx
Applications of the Process Utilizing Biomass Streams
Process
Hydrogen
Energy
Crops
Biomass
Waste
Aqueous
Biomass
Stream
Extraction
Hydrogen
APR
Extraction
PEM
Fuel Cell
SOFC
Fuel Gas
APR
ICE
Genset
Microturbine
Genset
CATALYSIS IN THE PRODUCTION OF FUTURE
TRANSPORTATION FUELS
Biofuels Life Cycle
Technology for Green & Biofuels
Biomass Sources For Biofuels
•
•
•
•
LignoCellulose (Cellulose, Hemicellulose, Lignin)
Starch
Sugars
Lipid Glycerides (Vegetable Oils & Animal Fats)
Structures in Lignocellulose
Pathways to Renewable
Transportation Fuels
Gasifier
Veg Oils
Algae Oils
Biomass
Pyrolysis
Syngas
Methanol,
Ethanol,
FT( diesel,etc)
Biodiesel
Bio Oils
Ferment to
ethanol,
butanol
Refine to Liquid
Fuels
Gasoline
additives
Hydrolysis
Aqueous phase
Reforming
Hydrogen
Bioethanol Overview - Global
• Current bioethanol production in US is 12 billion gallons.
• Most cars on the road in US today can run on blends of up to 10% ethanol.
• US DOE has estimated that there is a potential to produce over 80 Billion
gallons of bio-ethanol from cellulose and hemi-cellulose present in corn
biomass in the 9 major US corn producing states.
• This equates to over 250 Million tons of bio-ethanol and >$160 Billion revenue.
• Iogen’s Demo plant producing cellulosic ethanol from wheat straw in Canada
since 2004.
• DuPont-Danisco JV has started demonstration of cellulosic ethanol from
corncobs since Jan., 2010 in USA.
• Brazil currently blends 25% ethanol in gasoline and bioethanol is produced
directly from sugarcane.
• Brazilian flex cars are capable of running on just hydrated ethanol (E100), or
just on a blend of gasoline with 20 to 25% anhydrous ethanol, or on any
arbitrary combination of both fuels
• China uses 10% bioethanol in gasoline .
2nd Generation Bioethanol
Technology Overview
Company
Location
Technology
Present Status
Hydrolysis
based
Technology
Players
DuPontUSA
Feed stock - Agri residue.
Pilot Plant started
Danisco
Iogen/
Alkaline pretreatment ,
enzymatic hydrolysis +
C5/C6 Co-fermentation
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.
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.
Shell
Lignol
Pilot Scale under
Engineering design.
Enzymatic based Cellulosic Ethanol Process
Biomass
Enzyme
Production
Pretreatment
Microbe
Hydrolysis
C5/C6 Sugars
Bioreactor
Distillation/
dehydration
Lignin
Second Generation Bioethanol
Ethanol
99.7 wt%
Gasification based Technology Players
Gasification based Technology Players
Company Location Technology
Present Status
COSKATA USA
Completed pilot scale
optimization.
Feed stock - Agri residue,
pet coke, MSW.
Gasification to syn-gas &
direct fermentation to
ethanol.
INEOS
Bio
USA
Feed stock - Agri residue,
MSW. Conventional
Gasification to syn-gas &
its fermentation to
ethanol.
Process under study in
pilot plant.
Gasification based Cellulosic Ethanol Process
Biomass
Gasifier
Microbe
Syn-gas
Bioreactor
Distillation/
4 - 6% ethanol
dehydration
Ethanol
99.7 wt%
Transportation Fuels from Cellulosic Biomass (Pyrolysis Route)
Transportation Fuels from Biomass
BIODIESELS
• 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.
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
Fuel Quality Problems in First Generation
Technology
• Lower glycerol purity; Not suitable for production
of chemicals (propanediol, acrolein etc) without
major purification; Salts 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.
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.
• Catalysts:NiMo(for deoxyg), Pt-SAPO-11(for isom); H2 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.
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;KUOP = 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
Capital Costs : EIA Annual Energy Outlook 2006
107
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 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)Al2O4, loaded
on anode
Catalysts for conversion of NG to Transportation Fuels
I.Syngas Preparation
- Hydrodesulphurisation(Co/Ni-Mo-alumina)
- Syngas generation(H2/ 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 CO2.
3.Product Work up:
Wax Conversion to diesel and gasoline.
Mild Hydro-cracking/Isom catalysts
(Pt metal- acidic oxide support )
Petroleum - vs- Syngas :: Diesel
Property
PetroSynBoiling Range,oC
150-300 150-300
Density at 15 C,kg/m3 820-845 780
S, ppm vol
10 - 50
<1
Aromatics,% vol
30
<0.1
Cetane No
>51
>70
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.
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;
• H2: CO = 0.67;Once-thru slurry(Fe) FT reactor; RR = 15 % at a
refinery site.
Coal To Syngas To Fuel Cells
Catalysis in Coal / PetCoke gasification
• SR: C + H2O CO + H2 (+117 kJ/mol)
Combust:2C+ O2  2CO (H = -243 kJ/mol)
WGS :CO + H2O  H2 + CO2 ( -42 kJ/mol)
Methan: CO+3 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 gasification;Good WGS is needed;
• MCFC and SOFC can use H2,CO, & CH4 as
fuel to generate electricity.
• Low rank coals, Lignites gasify easier.
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
Sugar Cane Juice to H2
AQUEOUS PHASE REFORMING
• C6H12O6 +6H2O  12H2 +6CO2(APR)
• Pt-alumina catalysts, 200 oC
• 1 kg of H2 ($3-4) from 7.5 kg Sugar
Fuel Efficiency of H2 >> diesel/gasoline
H2 Production from Glycerin
• Available from Veg oils(40-98% in H2O)
• C3H8O3 +3H2O 7H2 + 3CO2
• Ru – Y2O3 catalysts; 600 oC
• 1 kg H2 from 7 kg glycerine
H2 production from Biomass is less economically
viable than production of ethanol and biodiesel
from biomass.
Catalytic Direct Methane Decomposition
to H2 and Carbon Nanotubes
Catalytic Auto Thermal Reforming of
Methanol, Ethanol, DME to HYDROGEN
for FUEL CELL
Pure H2 Supply
• Compressed H2
• Liquid H2
• H2 Hydride
H2
Fuel
H2 from Reformed liquid HC
• Methanol
• Ethanol
• DME
H2 Combustion Engine
Similar to Gasoline Internal
Combustion Engine
Pure H2 Supply
• Compressed H2
• Liquid H2
• H2 Hydrid
PEM Fuel Cell
H2
Fuel
H2 from Reformed liquid HC
• Methanol
• Ethanol
• DME
Pure H2 Supply
• Compressed H2
• Liquid H2
• H2 Hydrid
PEM Fuel Cell
H2 Production
H2 from
Fossil & Renewable
Fuel
Sources
H2 from Reformed liquid HC
• Methanol
• Ethanol
• DME
Catalysts for H2O and CO2 Photothermal Splitting
Using Sunlight
1. H2O  H2 + 0.5 O2
2. CO2  CO +0.5 O2
• FT Synthsis: CO + H2 (CH2)n petrol/Diesel
Sandia’s 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.
Splitting H2O
124
Splitting H2O with visible light
125
Future Fuels: Catalysis 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
• Biomass:1.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
Thanks
Discussion