TopsoeCatalysisForum,August2728,2015

StructureandPerformance
ofSelective HydrogenationCatalysts
C.MartinLok
CatalokConsultancy

Main Message
Catalysts for Petrochemicals
Choice ofmainmetalextremelycritical
nmanyreactions(multple)promotersareessential
Mostexisting catalysts havebeenoptimized inthetraditionalway.
Fewpromoter combinations havebeenstudied inawide
concentration range,if atall.Fewternaryandquarternarymetal
systemshavebeenexplored.
Now
Betterunderstandingallowsamorejudciousselectionofpromoters
Highthroughputscreeningwillacceleratethedevelopmentofnewand
improvedcatalysts.Manycombinationofpromoterscanbestudied
Modelling becomes morepredictive

Citations
JacquesCoenen:
Catalystpreparationisliketightropewalking:onewrongstepand
thereisasteepdrop
MurrayRaney:
"Itisinthepreparationofcatalyststhatthechemistismostlikelyto
employalchemicalmethods.
Theworkshouldbeapproachedwithhumilityandsupplicationand
theproductionofagoodcatalystreceivedwithrejoicingand
thanksgiving.

Outline ofTalk

Reactions
Main metals
Promoters/additives
Examples
Modernresearchinselective hydrogenation

SelectiveHydrogenation
SomeReactionTypes
One or moreC=Cdoublebonds indienes andpolyenes
Acetylenestoolefins

C=CC=O,either C=Cor C=Ohydrogenation

Nitriles toprimary,secondary or tertiary amines
Benzene tocyclohexane,minimize byproducts
Syngas tomethanol,olefins

Choice ofMetal
Activity andSelectivity Ranking Depends on Application

Activity
Oftenpgms>Ni>Co>Cu

Selectivity
Oftenpgms<Ni<Co<Cu

Costs
Pt>Rh>Pd>Ru>Co>Ni>Cu

Ranking may change by addition

ofpromoters

Choice ofMetal
Activity andSelectivity Ranking Depends on Application

Activity

Worldproduction Price(US$/kg)
(tpa)
Oftenpgms>Ni>Co>Cu

Selectivity
Oftenpgms<Ni<Co<Cu

Cost
Pt>Rh>Pd>Ru>Co>Ni>Cu

nickel

1,600,000

10

cobalt

61,000

29

20,000,000

20

1,400

platinum

180

33,000

palladium

202

20,000

rhodium

30

27,000

copper
ruthenium

Choice ofMetal
Activity andSelectivity Ranking Depends on Application

Activity

Worldproduction Price(US$/kg)
(tpa)

Often pgm>Ni>Co>Cu

Selectivity
Oftenpgms<Ni<Co<Cu

Cost

nickel

1,600,000

10

cobalt

61,000

29

20,000,000

20

1,400

platinum

180

33,000

palladium

202

20,000

30

27,000

copper
ruthenium

Pt>Rh>Pd>Ru>Co>Ni>Cu rhodium

Loadingpgms(0.15wt%)typicallymuchlowerthanforbasemetals(590wt%)
Pgmscanberecycled

Choice ofMain Metal

Nickel
Polyolefins tomonoolefins,cistrans isomerization,doublebondmigration
Fullsaturation (whiteoil)
Nitriles toamines

Copper
Syngas tomethanol
Carboxylic acids/acids tosaturated alcohols (200bar,250C)
Aldehydes toalcohols

Cobalt
Nitriles toprimary amines

Iron
Syngas toolefins,alcohols,alkanes
Dinitriles todiamines (HMDA)

Palladium
Acetylenes toethylenes

Choice ofMain Metal

Nickel (Mg,S,K)
Polyolefins tomonoolefins,cistrans isomerization
Fullsaturation (whiteoil)
Nitriles toamines

Copper(Cr)
Syngas tomethanol
Carboxylic acids/acids tosaturated alcohols (200bar,250C)
Aldehydes toalcohols

Cobalt (Mn,Re,Pt,Ru)
Nitriles toprimary amines

Iron (Cu,K)
Syngas toolefins,alcohols,alkanes
Dinitriles todiamines (HMDA)

Palladium (Re,Pb)
Acetylenes toethylenes

Often thesecatalysts
contain promoters

Promoters
Apromoter isan additive which itself ismostly inactive but
which improves theactivity/selectivity and/or stability and/or
processability ofthemetalliccatalyst
Electronic:Sn/Pt(alloy)
Structural/textural:Mg/Ni(improves Nisurface area)
Process:Cu/Ni,Cu/Fe,Pt/Co,Ru/Co(reduction promoters)

Wikipedia:Theeffectofacatalyst may vary due to

thepresence ofother substances known asinhibitors
or poisons (which reduce thecatalytic activity)or
promoters (which increase theactivity)(I?)

Olefins Value Chain

acetylene
Steam
Cracking of
LPG,naphtha,
gasoil

ethylene

methylacetylene
propadiene

propylene

C4acetylenes

butadiene

pyrolysis gasoline

aromatics

butene

Overhydrogenation tosaturates should be prevented

Modified after JohnsonMatthey brochure

Acetylene Conversion

Acetylene poisons ethylene polymerization catalyst

Acetylene >ethylene 42kcal/mole

ethylene >ethane 33kcal/mole

Requirement:<1ppm acetylene inethylene

Avoid saturation toalkane,temperature runaway

Ethylene yield (%)

100

Activity ranking:Pd>Pt>Ni,Rh>Co>Fe>Cu>Ru

Pdmostselective

Catalysts:Ag/Pdor eggshell 0.0150.05%Pd/alumina

95

90

Other promoters:Pb,Cu,Rh,Zn,Cr,V,K,Ce,..

50

100

Surface area (m2/g)

Ternary systems:Cu2.75Ni0.25Fe

Lindlar:Pd/Pbon CaCO3:
Cishydrogenation

Winterbottom (1981)
Bailey,King(2001)
Sorbier etal. (2012)
Handbook ofCommercialCatalysts (2000)
Bailey etal. US2006217579toJohnsonMatthey
Bridier 2012

200 400m thick palladiumcrust andatotal

palladiumamount ofabout 0.3to0.5wt%

Selectivity by Poisoning
Inactivation ofsites
Promoter ischemisorbed onto sitesactive for unwanted reactions

Influences adsorption ofreactants

Ensemblecontrol
Promoter reduces ensemblesize

PromotionofNickel by Partial Sulphur Poisoning

Suppressesmonoenehydrogenation
butpromotescistransisomerization

Saturation concentration
0.4 0.5sulphuratompersurfacenickelatom

Fully Ssaturated Nicatalyst inactive

becomes gradually active under sulphurfree hydrogen
tomaintain selectivity feed should contain some sulphur

Lok,Catalysis,course manual,University ofLiverpool,1996

Pyrolysis Gasoline(Pygas)Hydrogenation
Hydrogenated pygas contains olefins andaromatics
Highoctane gasoline
Source ofaromatics

Hydrogenation
Removes polyenes
Improves colourandgumcontentingasoline
Reduces fouling indownstreamhydrotreating

Industrialcatalysts
Pdonalumina
Cleaner feeds

Sulphided Nionalumina
Orderofmagnitudehigher tolerance for heavymetals andsulphur than Pd
catalysts

Promotionby Sulphur:
Pyrolysis GasolineHydrogenation
120
100
80
Polyene
monoene

60

aromatic
40

saturated

20
0
feed

Ni
Lok,Catalysis,course manual,University of
Liverpool,1996

Nickel Catalysed Pyrolysis GasolineHydrogenation

120
Highly exothermic:temperature
runaway (750C):riskofexplosion
(pre)sulphiding required
(Goossensetal. 1997)

100
80

Polyene
monoene

60

aromatic
40

saturated

20
0
feed

Ni
Lok,Catalysis,course manual,University of
Liverpool,1996

Nickel Catalysed Pyrolysis GasolineHydrogenation

Promotionby Sulphur
120
100
80
Polyene
monoene

60

aromatic
40

saturated

20
0
feed

Ni

Adding Snhasasimilar effectUS2011166398 (A1)20110707toIFP

NiSpromoted
Lok,Catalysis,course manual,University of
Liverpool,1996

Phenylacetylene Hydrogenation
C8cut from steam cracking:mostly styrene andupto
1%phenylacetylene
Styrene spec:<300ppm phenylacetylene
Catalysts
Presulphided nickel,mostly for highsulphur andhighcontaminant
feeds
Palladium,higher selectivity incleaner feeds

EnsembleControl by Sulphur
Benzene toCyclohexane
Undesired byproducts:linear alkanes,methylcyclopentane

Ensemblesize
Hydrogenation:34Nisurface atoms
Hydrogenolysis tolinear alkanes:1522Nisurface atoms

Lowdosage ofS
Selectivity tocyclohexane increases to100%
Breaksupnickel surface insmallerensembles
Martin(1988)
Rekkeretal. US5856603(1994)toEngelhard

Sulphiding Procedures
1.

Reduction oftheoxidic catalyst followed by sulphiding

2.

Simultaneous reduction andsulphiding oftheoxidic catalyst

3.

Sulphiding oftheoxidic catalyst followed by reduction

Sulphiding agents:H2S,DMDS,polysulphides,etc.

B.W.Hoffer etal. Fuel 83(2004)18

B.W.Hoffer etal. J.Catalysis209(2002)245255

Sulphiding Procedures

TPRstudiesshowed that
presulphided oxidic catalysts
can be reduced atalower
temperature than theoriginal
nonsulphided catalyst

Nosignificant difference in
nickel surface area or
hydrogenation activity

B.W.Hoffer etal. Fuel 83(2004)18

B.W.Hoffer etal. J.Catalysis209(2002)245255

Nitrile Hydrogenation toPrimary Amines

Secondary andtertiary amines asbyproducts suppressed by NH3

Comuch moreselective than Ni;Sponge Nimoreselective than supported Ni

PromotionofNiandCowith bases

Ca,Mg,Na,K,improves selectivity

Adiponitrile tohexamethylenediamine (HMDA),highpressure

Co/Cu
fused iron catalyst with arangeofpromoters:Fe72,Mn 0.17,Al0.08,Ca0.03,Mg0.05,Si0.12,Ti0.01

Borninkhof etal. PatentUS5571943,toEngelhard

Ansmann etal.PatentDE 10151558,2003toBASF

Carbonyl Hydrogenation
aldehydes toalcohols

Primary gasphase hydrogenation mostly with copper catalysts (nickel too

unselective)

Tricklebed polishing with nickel toreduce carbonyl number

Sodium promotionincreases selectivity innickel catalysed hydrogenation

ofbutanal
Nickel catalyst

NoNa

1wt%Na

butanol

98.9

99.9

acetal

0.3

2ethylhexanol

0.1

dibutylether

0.1

Deckersetal.,USPatent5498587toHoechst

Unsaturated Carbonyl Hydrogenation

C=Cor C=O

Thechemoselective hydrogenation todesired unsatd.alcs.isdifficult toachieve asthe

hydrogenation oftheC=Cbondisthermodynamically preferred overC=Obond

Acrolein hydrogenation overPt:>99%C=Candonly <1%C=Ohydrogenation

OverPttheselectivity tounsaturated alcohols isgreatly improved by alloying with Sn,

Znor Fe

Theadsorption modesfavourable totheC=Chydrogenation areinhibited

PolarizationoftheC=Obond
Change inmetaldispersion
Sn+ speciespromotingattackofC=Obyhydrogen
Combinations thereof

Selectivity
crotonaldehyde >crotylalcohol
Pt/SiO2:0%
PtSn/SiO2:78%

Inaddition,selectivity isimproved by various promoters atthePtsurface like K

Further improvements:process conditions (highT),Ptcrystallite size anduse ofAuand

Ag
MakiArvela etal. (2005)
Gallezot etal. (1994,1998)
Chen etal. (2005)

UnsaturatedCarbonylHydrogenation
tounsaturatedalcohol

Importantreactions
Acrolein >allylalcohol

Crotonaldehyde >crotyl alcohol

Cinnamonaldehyde >cinnamylalcohol
Citral >geraniol

Selectivity can be tuned by additives

Mebi etal. 2007

Hydrogenation of5Ethoxyfurfural
ring(12)or C=O(13),parameterspace
Thefullfactorial combination of
theseparameterresults in576
combinations which were alltested
using highthroughput techniques

Rasetal. Top.Catal.53(2010)1202.

Hydrogenation of5Ethoxyfurfural
Ringvs. carbonyl hydrogenation

NiSnbased alloy catalysts

aldehydes toalcohols

Highselectivity to
exclusively unsaturated
alcohols.

BoththeNi3Sn2 andNi3Sn
alloy phases were found to
be responsible for the
enhancement ofthe
chemoselectivity.

Reusable withoutany
significantlossofselectivity.

Rodiansono (2012)

GlycerolHydrogenation
1,3 vs. 1,2propanediol

Nakagawa etal. (2014)

GlycerolHydrogenation
1,3 vs. 1,2propanediol

Main product

Nakagawa etal. (2014)

Glycerolto1,3propanediol
1,3 vs. 1,2propanediol

Key istoquickly hydrogenate 3

hydroxypropanolbefore interconversion
tomorestable acetol

Polyoxometalates,WOx clustersandRe
may stabilise cationic intermediates

Re/Ir:70%selectivity to1,3propanediol
declining athigher conversion
Nakagawa etal. (2010)

Methanolfrom CO2 using aNiGa Catalyst

ANiGa catalyst hasbeendiscovered
through adescriptorbased
computational analysis,andhasbeen
shown experimentally tobe
particularly active andselective.
Studt etal. compared thecopper
zincaluminum catalyst with
thousands ofother materials inthe
database.
Themostpromising candidate turned
outtobe anickelgallium.Athigh
temperatures,nickelgallium
produced moremethanolthan the
conventional copperzincaluminum
catalyst,andconsiderably less ofthe
carbonmonoxidebyproduct.
Studt etal. NatureChemistry 6(2014)320

Turnover frequency (TOF)isplotted asafunction ofEO,relative toCu(211).

Ni:dark
Ga:light
O:red

Catalytic Reaction Guide App

Alwaysuseful tocheck:
TheCatalytic Reaction Guide isafreemobileapplication designed to
providemobileaccess tocatalyst recommendations on over150
reactions inthearea ofhomogeneous,heterogeneous andasymmetric
catalysis.
DesignedforiPhoneandiPad(rated4.5basedon19ratings)
Some emphasis on finechemicals andpgm catalysts

Available viatheweb

Conclusions
Choice ofmainmetalextremelycritical
nmanyreactions(multple)promotersareessential
Mostexistingcatalystshavebeenoptimizedinthetraditionalway.
Fewpromotercombinationshavebeenstudiedinawide
concentrationrange,ifatall.Fewternaryandquarternarymetal
systemshavebeenexplored.
Now
Betterunderstandingallowsamorejudciousselectionofpromoters
Highthroughputscreeningwillacceleratethedevelopmentofnewand
improvedcatalysts.Manycombinationofpromoterscanbestudied
Modellingbecomesmorepredictive

Thank you for your attention