Department of Chemical Engineering

Institute of Technology, Nirma University

Chemists and Chemical Engineers Make the

World a Better Place through Modern

Developments in Heterogeneous Catalysis

Presented by

SANJAY PATEL

Chemistry & Chemical Engineering

History of Catalysis

Catalysis

Recent trends in Catalysis

Future trends in Catalysis

Summary

Content

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)

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-4

1960s

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-5

1970s

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

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-7

1990s

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

- Diffusion of Reactants (Bulk to Film to Surface)

- Adsorption

- Surface Reaction

- Desorption & Diffusion of Products

Steps of Catalytic Reaction

reactants

products

reactor

catalyst support

active

site

substrate

adsorption

reaction desorption

bed of

catalyst

particles

porous carrier

(catalyst

support)

product

Role of Chemists & Chemical Engineers

Team Work

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

Wet Impregnation Co-precipitation

Catalysts Preparation

WI CuO/ZnO/Al2O3 Catalyst

Calcined

WI CuO/ZnO/Al2O3 Catalyst

Calcined

Co-precipitation

Co/Al2O3

Calcined

Commercial Ni/Al2O3

Spent Commercial Ni/Al2O3

Commercial Fe2O3 catalyst

Spent Commercial Fe2O3 catalyst

Pt, Pd and Rh on the Metox metallic substrates

Pervoskite LATEST Research

Auto-catalysts

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

Surface area, Pore Volume, Pore Size & Pore size distribution

Major role of Chemical Engineer with Chemists for Hardware

0

20

40

60

80

100

120

140

160

180

200

0 100 200 300 400 500 600 700

Relative pressure, P/P 0

Volu

me a

dsorbed,

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

volu

me,

cm

3 g -1 A

0-1

CZCEA2

CZA2

Pore size distribution by BJH method N2 adsorption/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:30/20/50 m

0 k

2 V COSPlnP r RT

σ θσ θσ θσ θ−−−−====

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

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

Reactions involved in OSRM process

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

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

Operating Conditions for SRM & OSRM

Schematic diagram of Schematic diagram of Schematic diagram of Schematic diagram of OSRM processOSRM processOSRM processOSRM process

Schematic diagram of Schematic diagram of Schematic diagram of Schematic diagram of OSRM processOSRM processOSRM processOSRM process

L 770mm

Thermocouple

Reactants Inlet

ID 19mm

OD 25mm

Flange

Catalyst bed

Products

T=280 oC, W/F=11 kgcat s 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% 30/30/40 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

H2 rate, mmol s-1 kgcat-1

132 180 160 244 217

CO formation, ppm 9400 3400 1400 995 1240

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 TRENDSRECENT TRENDSRECENT TRENDSRECENT TRENDS

Big picture: Sustainable Development

Green Chemistry Is About...

Cost

Waste

Materials

Hazard

Risk

Energy

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

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 (1-6)

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

The 12 Principles of Green Chemistry (7-12)

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

Ac2 O

Al Cl3

C O C H3

HCl, A cO H , Al W aste

ClC H2 C O2E t

Na O Et

OEtO 2C

H Cl

H2O / H+

OH C

A c O H

NH2O H

O H NN

H2 O / H+

H O2C

N H3

Examples of Green Catalysis

Hoechst Route To Ibuprofen

O

HF

AcOH

Ac2O

H2 / Ni

OH

CO, Pd

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 (PHA’s)

Examples of Green Catalysis

‘TiO2’ A GREEN CATALYST:

CLEAN ENVIRONMENT

Examples of Green Catalysis

Photocatalysis

Photocatalyst

Starch + O2 Organic compound

Chlorophyll

CO2

H2O

CO2 + H2O

Organic

Compound

+ H2O + O2

Photocatalytic Applications

Self-Cleaning Effect

TiO2 - Photocatalysis

3.12 eV

(380 nm)

Photocatalytic Reactions

TiO2 + hν TiO2 (e- + h+)

h+ + H2O OH + H+

O2 + e- O2

-

O2 - + H+ HO2

HO2 + HO2 H2O2 + O2

O2 - HO2+

H2O2

O2 + HO2-

HO2- + Η+

H2O2 + hν OH2

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

Structured Beds

of Tomorrow

Random Packed

Today

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?

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

• 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

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

Biomass

Waste

Aqueous

Biomass

Stream

Extraction

Extraction

PEM

Fuel Cell

SOFC

ICE

Genset

Microturbine

Genset

Hydrogen

APR

Fuel Gas

APR

Energy

Crops

Process

Hydrogen

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

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

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

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.

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

Gasification based Technology Players

Company Location Technology Present Status

COSKATA USA Feed stock - Agri residue,

pet coke, MSW.

Gasification to syn-gas &

direct fermentation to

ethanol.

Completed pilot scale

optimization.

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 Technology Players

Biomass

Gasification based Cellulosic Ethanol Process

Gasifier

Bioreactor

Distillation/

dehydration

Microbe

Ethanol

99.7 wt%

Syn-gas

4 - 6% ethanol

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

107

Capital Costs : EIA Annual Energy Outlook 2006

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 from Reformed liquid HC

H2

Fuel

• Methanol

• Ethanol

• DME

H2 Combustion Engine

Similar to Gasoline Internal

Combustion Engine

Pure H2 Supply

• Compressed H2

• Liquid H2

• H2 Hydrid

H2 from Reformed liquid HC

H2

Fuel

• Methanol

• Ethanol

• DME

PEM Fuel Cell

Pure H2 Supply

• Compressed H2

• Liquid H2

• H2 Hydrid

H2 from Reformed liquid HC

H2

Fuel

• Methanol

• Ethanol

• DME

PEM Fuel Cell

H2 Production from

Fossil & Renewable

Sources

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

125

Splitting H2O with visible light

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