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 Fe/K
NH3 NO NO2 HNO3 Pt
1920s: CO + 2H2 CH3OH (HP) (ZnCr)oxide
Fischer-Tropsch synthesis Co,Fe
SO2 SO3 H2SO4 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) Ti
C2H4 Polyethylene(Phillips) Cr-SiO2
Polyprop &Polybutadiene(Z-N) Ti
Steam reforming Ni-K- Al2O3
HDS, HDT of naphtha (Co-Mo)/Al2O3
C10H8 Phthalic anhydride (V,Mo)oxide
C6H6 C6H12 (Ni)
C6H11OH C6H10O (Cu)
C7H8+ H2 C6H6 +CH4 (Ni-SiAl)
 Industrial catalysis-4
1960s
Butene Maleic anhydride (V,P) oxides
C3H6 acrylonitrile(ammox) (BiMo)oxides
Bimetallic reforming PtRe/Al2O3
Metathesis(2C3 C2+C4) (W,Mo,Re)oxides
Catalytic cracking Zeolites
C2H4 vinyl acetate Pd/Cu
C2H4 vinyl chloride CuCl2
O-Xylene Phthalic anhydride V2O5/TiO2
Hydrocracking Ni-W/Al2O3
CO+H2O H2+CO2 (HTS) Fe2O3/Cr2O3/MgO
--do-- (LTS) 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 acidic ion exchange resin
C7H8+C9H12 C6H6 +C8H10 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 Pt/Zeolite
MTBE cat dist ion exchange resin
Oxdn of methacrolein Mo-V-P
N-C6 to benzene 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 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-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)

1. External diffusion, 2. Internal diffusion
- 3. Adsorption
- 4. Surface Reaction
- 5. Desorption & 6.7. 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 &
Catalysts Preparation
Alumina pellets
0.5M Na2CO3
Dropwise
addition
Wet Impregnation Co-precipitation
Nitrate Salts
Solution
Mixer cum shaker 70 oC, pH=7-8

Precipitates:
Ageing for 2 h Crushing

Round bottom flask with

Heating mental & Agitator Catalyst
Rotary Vacuum Evaporator

Sieving, 20/25 mesh

Filteration

Drying @ 125 oC for 12 h

Calcination,
Pelletizing
350 oC for 4 h Drying
@ 125 oC for 12 h

Catalyst

Calcination,
Crushing Sieving, Crushing 350 oC for 4 h
20/25 mesh
Calcined

WI CuO/ZnO/Al O Catalyst
Calcined

WI CuO/ZnO/Al O Catalyst
Co-precipitation Calcined
Co/Al2O3
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
Surface area, pore volume & size
Pore size distribution
Elemental composition of
catalysts
Phases present & Crystallinity
Morphology
Catalyst reducibility
Dispersion, SA and particle size
of active metal
Acidic/Basic site strength
Surface & Bulk Composition
Coke measurement
Methods
N2 Adsorption-Desorption Surface area
analyzer (BET and Langmuir)
BJH (Barret, Joyner and Halenda)
Metal Trace Analyzer / Atomic Absorption
Spectroscopy
X-ray Powder Diffraction
TG-DTA (for precursors)
Scanning Electron Microscopy
Temperature Programmed Reduction
CO Chemisorption, TEM
NH3-TPD, CO2 TPD
XPS
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
200
P2CZCeA CZCEA2
g (STP)

180 P2CZCeA 6.0E-3 CZA2

160

g -1 A0-1
-1
Volume adsorbed, cm

140 5.0E-3
3

120

3
4.0E-3

Pore volume, cm
100
80 3.0E-3
60
2.0E-3
40
20 P3CZA
1.0E-3
0
0 100 200 300 400 500 600 700 000.0E+0
10 100 1000
Relative pressure, P/P 0 Pore diameter, A 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 P 2 Vm COS

ln
P3CZA Cu/Zn/Al:30/20/50 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 FM-1 FM-2 FM-3
Catalytic Reactor

V-1 V-2 V-3

Chiller Condenser For Catalyst

FM-4
Reduction
Product Gases

G-L Separator O2 N2 H2

Methanol & Water

 Schematic diagram of
OSRM process
Reactants Inlet Vaporizer
cum Mixer
Thermocouple Methanol & Water Feed Pumps

Flange

OD 25mm

Gas Chromatograph with DAS

Packed Bed FM-1 FM-2 FM-3
Catalyst bed L 770mm Catalytic Reactor

V-1 V-2 V-3

ID 19mm

Chiller Condenser For Catalyst

FM-4
Reduction

Products Product Gases

G-L Separator O2 N2 H2

Methanol & Water

 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% 30/30/40 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, 108 80 101 52 69
X, % 60 77 69 100 90
H2 rate, mmol s-1 132 180 160 244 217
kgcat-1
CO formation, ppm 9400 3400 1400 995 1240

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 Lower
capital investment operating costs

Societal pressure Government legislation

Improved Less
public image hazardous materials

Safer
Green chemistry High fines for waste
and smaller plants

Producer
Pollution control
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 a ste HCl Ac O H

Ac 2 O H 2 O / H+
C lC H 2 C O 2 Et
AlC l 3
Na O Et

C O C H3

Et O 2 C
O O HC
Examples of Green Catalysis
N H2 O H

H 2 O / H+

N OHN
H O2C

N H3
Hoechst Route To Ibuprofen

AcOH

HF H2 / Ni CO, Pd
Ac2O

O HO HO2C

Examples of Green Catalysis

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 (PHAs)

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 + H2O + O2

Organic compound
Photocatalytic Applications
Self-Cleaning Effect
 TiO2 - Photocatalysis

3.12 eV
(380 nm)
 Photocatalytic Reactions
TiO2 + h TiO2 (e- + h+)

h+ + H2O OH + H+

O2 + e- O2 -

O2 - + H+ HO2

HO2 + HO2 H2O2 + O2

-
O2 + HO2 O2 + HO2-

HO2- + H2O2

H2O2 + h 2 OH
-
H2O2 + O2 HO + OH- + O2

H2O2 + e- HO + OH-
 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
Random Vs Structured Catalysts
Random Packed
Today

Structured Beds
of Tomorrow
 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?
 2D & 3D Tools, Fabrication &
Flowsheet CAD Solids Microscale Design Assembly Materials of
Synthesis Modeling Modules Construction
Microprocess
Components
Multiscale
Process Transport
Micro Systems
Engineering Component Engineering
Simulation & Integration
Control Flow Optimization Multi-scale
Systems Patterns Transport

Micro Process
Plant
Micro Analyzers (GC,
Raw Materials & Integrated LC, MS, TOF)
Feedstocks Sensors

Chemistry & Catalyst Sampling Micro Process

Characterization Sensors Analytical
Catalysis
Reaction Reaction Pathways & Data handling & Micro PAT Systems
Kinetics Mechanisms Chemometrics 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 Extraction Hydrogen
Crops
APR PEM
Fuel Cell

Biomass Extraction SOFC

Waste

ICE
Aqueous Fuel Gas
Genset
Biomass APR
Stream
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

Methanol,
Gasifier Syngas
Ethanol,
FT( diesel,etc)
Veg Oils
Biodiesel
Algae Oils
Refine to Liquid
Biomass Pyrolysis Bio Oils
Fuels

Ferment to Gasoline
ethanol, additives
butanol

Hydrolysis

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

Biomass Enzyme
Production

Pretreatment
Microbe

C5/C6 Sugars
Hydrolysis Distillation/
Bioreactor
dehydration
Lignin

Ethanol
Second Generation Bioethanol 99.7 wt%
 Gasification based Technology Players
Gasification based Technology Players
Company Location Technology Present Status

COSKATA USA Feed stock - Agri residue, Completed pilot scale

pet coke, MSW. optimization.
Gasification to syn-gas &
direct fermentation to
ethanol.

INEOS USA Feed stock - Agri residue, Process under study in

Bio MSW. Conventional pilot plant.
Gasification to syn-gas &
its fermentation to
ethanol.
 Gasification based Cellulosic Ethanol Process

Biomass Gasifier
Microbe

Syn-gas
Bioreactor

Distillation/
dehydration
4 - 6% ethanol

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; ~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 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 Petro- Syn-

Boiling 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 H2 Combustion Engine
Similar to Gasoline Internal
Fuel
Combustion Engine

H2 from Reformed liquid HC

Methanol
Ethanol
DME
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

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.
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