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BASF NanoSelect™ Technology

Innovative Lead-Free Replacements forLindlar Catalysts

BASF NanoSelect™ Technology

Innovative Lead-Free Replacements forLindlar Catalysts

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World chemicals sales2006World chemicals sales2006

765

672

569

130

42

Europe Asia NAFTA Latin America Others

[billion €]

Total €2178 billion

Source: Cefic Chemdata International

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Chemicals Industry Sales 2006Chemicals Industry Sales 2006

Perfumes & cosmetics

Pharmaceuticals

Petrochemicals

Plastics &synthetic rubber

Man-made fibresOther basic inorganics

Industrial gasesFertilisers

Other specialty chemicalsPaints & inksCrop protection

Sectoral breakdown (Europe)

Soap & detergents

Base chemicals 42.7%Pharmaceuticals 27.9%Specialty chemicals 19.2%Consumer chemicals 10.2%

Source: Cefic, Facts and Figures, 2007 (www.cefic.be)

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Global catalyst market2007Global catalyst market2007

Automotive

Stationary

Heterogeneous catalysts[billion US $]

Chemicals

5.2

1.0 3.9

1.4Total

approx.US $14 bn

2.7

Polymers

Refinery

Environment US $6.2 bn 44.0%Chemical industry US $4.1 bn 29.0%Refinery US $3.9 bn 27.0%

Source: The Catalyst Group Resources, “Intelligence Report”, 2008 BASF estimates

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Some things which would be different without catalysisSome things which would be different without catalysis

Much less people since food for 6 billion people can not be produced without fertilizers

Much higher pollution levels due to lack of catalytic flue gas treatment

Much higher gasoline prices and lower remaining reserves due to lack of catalytic cracking

Completely different slates of materials for most purposes at much higher prices

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Economic Impact of CatalysisEconomic Impact of Catalysis

At BASF, we employ catalysts in more than 80% of our own production facilitiesSource: BASF

>80% of all chemical and pharmaceutical production processes, worth ~ €1500 billion, depend on catalytic technologiesSource: SusChem 2005

Catalysis contributes directly 2 – 3% of the EU’s GDP and 10 times this amount taking into account industries depending on chemical raw materialsSource: SusChem 2005

Catalysis is a decisive technology in tapping new feedstock, producing high performance materials and creating environment-friendly processesSource: SusChem, Vision 2025

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Importance of heterogeneous catalysts to the chemical industryImportance of heterogeneous catalysts to the chemical industry

EconomyCapital expenditure Manufacturing costs

Broad range of applications(Feedstock purification, synthesis, product separation)

Ecology

Technical advances

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Homogeneous vs. Heterogeneous Catalysis Properties determine fields of applicationHomogeneous vs. Heterogeneous Catalysis Properties determine fields of application

Sweetenedwater

+ = + =Sugar Water Sand Water Beach

“Homogeneous (catalysis)” “Heterogeneous (catalysis)”

Only surface sites are active, activity differs for each site (“hot spots”)

Easy separation, very lean process designspossible

Each catalyst molecule (beyond nano!) easily accessible and highly active

Homogeneous catalysts are not easily separated from the products

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Homogeneous vs. Heterogeneous Catalysis Modes of actionHomogeneous vs. Heterogeneous Catalysis Modes of action

Heterogeneous catalyst Homogeneous catalyst

Reactivity controlled by:Particle and pore size, character of catalytic site, element composition, type of support material, external (process) parameters, ...

Reactivity controlled by:Choice of metalType of ancillary ligands

Improvements through geometric and electronic tuning of reactive coordination sites possibleVery high complexity

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Challenges for catalysisChallenges for catalysis

Novel Feedstocks

Novel Materials

Novel Methods

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BASF’s research sites for heterogeneous catalysisBASF’s research sites for heterogeneous catalysis

Huntsville, AL

Pasadena, TX

Beachwood, OH

Union, NJ

Iselin, NJ Shanghai

Ludwigshafen

Guilin

De Meern, NL

Nienburg

Hannover

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Heterogeneous catalyst preparation techniquesHeterogeneous catalyst preparation techniques

Traditional techniques:ImpregnationPrecipitation-depositionCo-precipitation

Important catalyst parameterMetal crystallite size / dispersion / metal surface area

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Heterogeneous catalyst preparation techniquesHeterogeneous catalyst preparation techniques

First step yields supported unreduced metal crystallites

Extra processing step used to prepare final catalyst

Initial metal crystallite size alters after extra processing steps

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Heterogeneous catalyst prepared by traditional methodsHeterogeneous catalyst prepared by traditional methods

Variable metal crystallites sizes

Some very large metal crystallites also present

HOW TO CONTROL ??!!

TEM photograph of commercial 5%Pd/CP

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Alternative method:Reduction-Deposition technologyAlternative method:Reduction-Deposition technology

Metal crystallite size independent of support

Metal crystallite size does not change after first formation

Citrate as reducing and stabilizing reagent: Turkevich et. Al. Science, 1970, 169, 873

Alcohol as reducing agent and PVP as stabilizer: Hirai et. Al. Reactive Polymers, 1985, 3, 127

Ammonium Borohydride as reducing and stabilizing reagent: Bönnemann et. Al. Appl. Organometall. Chem., 1994, 8, 361

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BASF NanoSelectTM technologyBASF NanoSelectTM technology

metal salt + HHDMA metal colloid

Reducing and stabilizing function combined in one reagent

Hexadecyl(2-hydroxyethyl)-dimethylammonium

dihydrogenphosphate

Water-soluble, air-stable, BASF compound

EP08150726.1-2104

N

HO

H2PO4

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NanoSelect Technology NanoSelect Technology

Free colloids Heterogenized colloids

EP08150726.1-21041717171717

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NanoSelect Technology Pd-Pt bimetallic catalystNanoSelect Technology Pd-Pt bimetallic catalyst

0

100

200

300

400

500

0 1 2 3 4 5 7 8 9 10

Location

Inte

nsity

(Arb

itrar

y un

its)

Pt MPd L

0

100

200

300

400

500

600

700

800

900

0 11 22 33 44 55 66 77 87 98

Location

Inte

nsity

(Arb

itrar

y un

its)

Pt MPd L

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NanoSelectTM TechnologyNanoSelectTM Technology

Heterogeneous catalysts prepared by reduction-deposition

Better control over metal crystallite sizeReaction temperature, ratio metal/stabilizer, stabilizer, pH, metal concentrationNo effect of extra conditioning steps or of the support

Commercial manufacturing method:No organic solvents, no protective atmosphere, high metal concentration possible

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NanoSelect Pd-catalysts (partial hydrogenation of alkynes)NanoSelect Pd-catalysts (partial hydrogenation of alkynes)

NanoSelect LF 1000.6% Pd-colloid on C

NanoSelect LF 2000.5% Pd-colloid on TiS

For comparisonCommercial 5%Pd/CLindlar catalyst 5%Pd-2.7%Pb/CaCO3

2020

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Hydrogenation of 3-hexyn-1-olHydrogenation of 3-hexyn-1-ol

Catalyst, 100 mL 95% EtOH, 5 mL 3-hexyn-1-ol

30oC

3 bar H2

H2 consumption recorded

2 L H2 is 100% hexanol formation

OH OH OH

2121212121

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0

1

2

3

0 20 40 60 80 100 120

time (min)

hydr

ogen

upt

ake

(L)

NanoSelect LF 200 vs. LindlarNanoSelect LF 200 vs. Lindlar

cis/trans = 97/3

cis/trans = 86/14

OH OH

cis/trans = 97/3

cis/trans = >99/1

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Heterogeneous or homogeneous?Heterogeneous or homogeneous?

Filtration experiments indicate that no metal leaching takes place at low Pd-loadings

0.6%Pd/C or 0.5%Pd/TiS

At higher Pd-loading leaching occurs

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NanoSelect LF 200 vs. Lindlar catalyst(50 mg catalyst)NanoSelect LF 200 vs. Lindlar catalyst(50 mg catalyst)

0

1

2

3

0 20 40 60 80 100 120

time (min)

hydr

ogen

upt

ake

(L)

OH OH

conversion olefin cis/trans

97% 99% 96/4

5%Pd/CP

NanoSelect LF 200

Lindlar catalyst

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Substrates scope NanoSelect LF 100, LF 200 vs. LindlarSubstrates scope NanoSelect LF 100, LF 200 vs. Lindlar

catalyst conversion (%)

olefin (%)

cis product (%)

LF-100 96 >99 98LF-200 97 99 97Lindlar 95 >99 >99LF-100 98 95 n.a.LF-200 97 95 n.a.Lindlar >99 96 n.a.LF-100 96 95 n.a.LF-200 93 94 n.a.

Lindlar * 95 97 n.a.LF-100 * 85 92 97LF-200 * 90 89 97Lindlar * 48 ** 96 98

n.a. = not applicable* = 5 times more catalyst is used** = reaction stops before full conversion is reached

substrate

OH

OH

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Conclusions

CONTROLLED FLEXIBILITY

Conclusions

CONTROLLED FLEXIBILITY

NanoSelect technology for commercial manufacturing of heterogeneous catalysts:

Better control over metal crystallite size and size distribution

Various mono- and bimetallic catalysts possible

Different supports possible

NanoSelect LF 100 and LF 200: are new lead-free Pd-catalysts that can be used as alternatives for Lindlar catalysts:

Lead-free replacements for Lindlar catalysts

Same activity and selectivity as Lindlar catalysts

Tenfold decrease in Pd amount

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NanoSelect LF 100 and LF 200Lead-free Lindlar catalyst replacementNanoSelect LF 100 and LF 200Lead-free Lindlar catalyst replacement

Innovative nano-colloid technology

Unimodal Pd colloids formed

Highly active for alkyne-to-alkene hydrogenation

High selectivity towards cis-product

10-fold lower palladium content BASFCome and visit usHall 1, Booth D 5