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Catalytic transformations for production of biofuels, specialty chemicals and

pharmaceuticals from woody biomass

Dmitry Yu. MurzinÅbo Akademi University

Turku/Åbo, Finland

1980-1986 МХТИ им. Д.И. Менделеева1986-1992 НИФХИ им. Л.Я. Карпова1992-1993 Universite de Strasbourg1994 Åbo Akademi1995-2000 BASF2000- Åbo Akademi

Murzin, D. Yu.; Konyukhov, V. Yu.; Kul'kova, N. V.; Temkin, M. I. Diffusion from the surface of suspended particles and specific power of mixing in vibrating reactors, Kinetika i Kataliz (1992), 33, 728

120 140 160 180 200 220 2400.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

1.8

y=2/3

y=1/2

y=1/3

Spe

cific

mix

ing

pow

er, W

/kg

Number of double movements

Turku/ÅboTurku/Åbo

Copyright E. Murzina, 2009

Chemical Engineering

• ≈ 760 undergraduate students• ≈ 140 graduate students

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Three main specialization areas• Process system engineering• Pulp and paper chemistry and

technology• Process chemistry

Education in Chemical EngineeringEducation in Chemical Engineering

From reaction mechanisms to reactor designFrom reaction mechanisms to reactor design

Reactor modellingCatalysis

Kinetics

Industrial Chemistry and ReactionEngineering

Industrial Chemistry and ReactionEngineering

Catalytic transformations for production of biofuels, specialty chemicals and

pharmaceuticals from woody biomass

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Chemical industryChemical industry

Approximately 90% of all our chemicals and materials have undergone catalysis at one point in the course of their production.

Catalysis

Catalyst sales in 2005 were estimated to be worth around US$11 billion.

Catalysis• A catalyst is a substance which increases the

reaction rate but is not consumed in the reaction.

• A catalyst provides an alternate reaction path with a lower activation energy.

Acids

Base

Sulphides

Oxides

MetalsDispersedPorousBulk

Pt/Al2O3, Ni/ Al2O3, Pd/ Al2O3Raney NickelPt, Pd, Ag gauze

Single Al2O3, Cr2O3, V2O5Dual, complex SiO2/Al2O3 , CuCr2O4Dispersed NiO/Al2O3 , MoO3/Al2O3

MoS2/Al2O3 , WS2/Al2O3

SiO2-Al2O3 ; zeolites; natural clays

CaO, MgO, K2O, Na2O

Cat

alyt

ic m

ater

ials

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Figure: a Volcano plot activity vs. adsorption energy

Adsorption energy (kJ/mol)

Act

ivit

y (a

rbit

ary

unit

s)

“Catalytic reaction has an optimum (maximum) rate as a function of the heat of adsorption”- Sabatier,1905:

If the adsorption is too weak,the catalyst has little effect;

If too strong, the adsorbates will be unable to desorb from the surface;

The interaction between reactants or products with surface should be neither too strong nor too weak.

Sabatier principle:

Sabatier principleSabatier principle

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Langmuir, Temkin, Frumkin

Asymmetric homogenous catalysis

L-DOPA

Length scales in Catalysis

catalyticsurface

catalytically active particles on a support

shaped catalyst particles

catalyst bedin a reactor

1 nm

10 mm

1 μm

1 m

microscopic mesoscopic macroscopic

Why does it look like that?What are the requirements?

One of the very fewcommercial Nano-materials

Trilobe extrudate

Reactors and catalyst

5 p.% Pt/Al5 p.% Pt/Al22OO33

11--2 m2 m

1010--20 m20 m

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Catalyst particle size distribution

11--5 mm5 mm

Catalyst powder

1010--1000 1000 µµmm

From mm (10-3)to micrometers (10-6)

Broad distributionBroad distribution

5.% Pt/Al5.% Pt/Al22OO33

22--4 nm4 nm

The active sites

TEM TEM imageimage

Metal particle size distribution

Active site = A site on the surface of a catalyst at which activity occurs.

22--4 nm4 nm

0.5 nm0.5 nm

Molecular or atomic level rearrangement of atoms that are responsible for catalytic properties

Images of Catalysis

Catalysis

Shaped catalysts

pellets

extrudates

fused catalyst

StrengthPressure dropMass transportHeat transport

Shapes

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Global catalyst market

Biomass is a plant matter of recent (nongeologic) origin or material derived there from and could be used to produce various useful chemicals and fuels

BiomassBiomass

BiomassBiomass

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Biomass as transportation fuelBiomass as transportation fuel

Other solutions?Other solutions?

WoodWoodFinland

16 m3 / person year

EU average 1.2

Globally 180 bil. ton /year

Forest resources: growthForest resources: growth

Part of lignin structure

WoodWood

• Gasification

•• PyrolysisPyrolysis

•• DepolymerizationDepolymerization to get low molecular mass components to get low molecular mass components (sugars, phenols, (sugars, phenols, furfurolfurfurol, etc. ), e.g. , etc. ), e.g. building blocksbuilding blocks

•• Delignification (cellulose, derivatives, paper)Delignification (cellulose, derivatives, paper)

•• Extraction of valuable chemicals (bioactive componentsExtraction of valuable chemicals (bioactive components))

Treatment of woodTreatment of wood

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GasificationGasification

Low temperature (200-240°C) and mid pressure (20-30 bar) to promote F-T over methanation reaction

Active catalyst based on IRON or COBALT

Production of high molecular weight linear waxes for further hydroprocessing step to optimize the overall liquid production, because it is impossible to produce directly a well defined range of products (i.e. middle distillates)

Fischer-Tropsch Reaction

nCO + 2nH2 n(-CH2-) + n H2O ΔH=-167 kJ/mole

CO + 3 H2 CH4 + H2O Methanation (ΔH=-206 kJ/mole)CO + H2O CO2 + H2 Water Gas Shift (ΔH=-41 kJ/mole)2CO C + CO2 Boudouard reaction (ΔH=-172 kJ/mole)H2 + CO C + H2O Coke formation (ΔH=-133 kJ/mole)

MainMain featuresfeatures of of modernmodern GTLGTL--FT:FT:

LiquidFuels

Product

upgradingNG

F-T

synthesis

Syngas

Production

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The Sasol Slurry Bed Reactor

The largest commercialThe largest commercial--sized FT reactor sized FT reactor -- SASOL SASOL Pictures Courtesy of Sasol

Technical challenges

CatalystsSummarySummary: FT : FT CatalystCatalystActive Phase: Active Phase: CobaltCobalt, , IronIron

PromoterPromoterStructural: Structural: increase metal dispersion (Re, Zr, Hf, Ce) Reduction: Reduction: increase extent of reduction (Ru, Pd, Pt, Cu)Activity: Activity: prevent coke deposition (Noble Metals)Selectivity: Selectivity: alter the product distribution (Na, K, Cs)

Carrier: SiOCarrier: SiO22, Al, Al22OO33, TiO, TiO22, mix, mixStructural promoter itselfInfluence selectivity due to secondary reaction (i.e. acid sites)

Co Co basedbased catalystcatalystExpensiveHigh selectivity to long chainparaffinsLow selectivity to olefins and oxygenatesresistant to deactivationlimited WGS activity

Fe Fe basedbased catalystcatalystEconomicLow selectivity to long chainparaffinsHigh selectivity to olefins and oxygenatesWGS catalystFast deactivation (coke)

Catalysis is Nano

High surface-area support

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Per exposed site!!!

Structure insensitive:

Structure sensitive reaction: Catalyst activity and/or selectivity depends on metal particle size and morphology

Every surface atom is catalytically active

Catalytically active site is composed of several atoms having specific coordination or geometry

Reactions on supported metal particles

NS/N

T

dc (Å)Crystal size ↓ then NS/NT ↑

Exposed atoms

Structure sensitive reactions

0

10

20

30

40

50

60

0 1 2 3 4 5Particle size (nm)

TOF

Rat

e pe

r mas

s

dc (Å)

Rate per unit of mass

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0 4 8 12 16 20 24 280

2

4

Act

ivity

(mol

/g s

)

Cobalt particle size

How to explain?

NS/N

T

dc (Å)

How to model selectivity?

Surf

ace

atom

s(%

)

Dispersion

Relative amounts of surface atoms

Edge

Corner

Face

Possible explanations

Differences in activities of different surface atoms

Metal Dispersion D

• Chemisorption: titration of surface sites

• number of moles

• in monolayer

Metal dispersion (D)

%100 N

ND ×=

total

surface

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Metal dispersion (Ntotal)

315N

1381263813N

N

ND surfacesurface

total

surface =+++

==

13

38

126

138

Metal dispersion (Nsurface)13-0=13

38-7=31

126-25 = 101

138-99= 39

99

25

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315-131=184

%58584.0315184

315N

D ==== surface

Dispersion D versus Diameter d

• Diameter d can be measured or calculated from several techniques

• – Electron Microscopy• – X-ray Diffraction, X-ray Photoelectron

Spectroscopy

Chemisorption - Experimental Techniques

• Gravimetry• Volumetry• Spectroscopy (Infrared, Raman)• Pulse techniques• Temperature Programmed Desorption

(TPD)

Pulse-Response Method

H2, CO

Pulse-Response Method

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Stoichiometry Stoichiometry

EM

• Electron microscopes often equipped with instrumentation for

• elemental analysis• – EDAX (Energy Dispersive Analysis of X-rays)• Two techniques:• – Transmission Electron Microscopy (TEM)• – Scanning Electron Microscopy (SEM)

TEM TEM: Rh/SiO2

10 nm

3 nm

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Transmission Electron MicroscopyCatalyst particle size distribution

Size (nm)

Transmission Electron MicroscopyCatalyst particle shape and morphology

SEM SEM