Heterogeneous Catalytic Materials. Solid State Chemistry, Surface Chemistry and Catalytic Behaviour

458 Pages·2014·16.887 MB·English

by  Guido Busca (Auth.)

Heterogeneous
Catalytic Materials
Solid State Chemistry,
Surface Chemistry and
Catalytic Behaviour
Guido Busca
AMSTERDAM(cid:129)BOSTON(cid:129)HEIDELBERG(cid:129)LONDON(cid:129)NEWYORK(cid:129)OXFORD
PARIS(cid:129)SANDIEGO(cid:129)SANFRANCISCO(cid:129)SINGAPORE(cid:129)SYDNEY(cid:129)TOKYO
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CHAPTER
1
Heterogeneous Catalysts
CHAPTER OUTLINE
1.1 Introduction.........................................................................................................1
1.1.1 Onthemeritsofindustrialchemistryasaproductionactivity.................1
1.1.2 Catalysisanditsroleinindustrialchemistry.........................................2
1.1.3 Whysolidcatalysts?............................................................................3
1.1.4 Industrialcatalyticmaterials...............................................................5
References.................................................................................................................7
1.1 Introduction
1.1.1 On the merits of industrial chemistry as a production activity
Atthebeginningofthethirdmillennium,fewdisciplinessuchasindustrialchemis-
tryareinadifficultsituationand,together,transformationwithexcitingprospects.
Publicopinionattributestochemistry,andnotwithoutafewgoodreasons,theenvi-
ronmental degradation,with itsharmfulconsequences.
However,themeritsofchemistryasanindustrialactivityareactuallylargelyun-
knowntopeopleandneglectedbyexpertsthatwouldknowthem.Infact,industrial
chemistryisaserviceactivity,allowinginparticulartheproductionofmaterialsand
molecules that are strictly neededby otheractivitiestoobtaintheirgoals.
It is well evident, for example, that the exponential growth and improving of
information and telecommunication technologies are largely dependent from the
developmentofsuitablematerialsmadeavailablebytheproductandprocessdevel-
opmentsofindustrialchemistry.Itissufficienttothinkaboutthenumberofchem-
ical components (constituting conducting electrodes, insulating components, dyes,
polymers)involvedinthei-phonetouchscreens,andtounderstandhowchemistry
andindustrialchemistrycontributedtothedevelopmentofelectronictechnologies.
Byanalogy,wecansaythat,withoutthepastdevelopmentofindustrialchemis-
tryandprocesses,thecars,aircraft,householdelectricalappliancesandequipments,
etc., of today would notbe available.
Similarly,partofthedevelopmentofmedicineisduetothedevelopment,atthe
researchlevel,ofnewactivedrugmoleculesaswellas,attheindustriallevel,ofeffi-
cientsynthesisprocesses,allowingthemtobeobtainedatmoderatecosts.Medicine
1
HeterogeneousCatalyticMaterials.http://dx.doi.org/10.1016/B978-0-444-59524-9.00001-8
Copyright©2014ElsevierB.V.Allrightsreserved.
2 CHAPTER 1 Heterogeneous Catalysts
alsotakesadvantageofinstrumentationsinpart,basedonchemicalanalyticaltech-
niques, as well as of materials and chemicals that become unique. An example is
polyvinyl chloride, which is the main component of hospital wastes, proving its
verylargeapplicationinthemedicalequipment.Anotherexampleisthatofsodium
hypochlorite,whichisuniversallyconsidered todayasauniquedisinfectingagent.
Boththesechemicalspecieshavebeentheobjectofcriticismduetosafetyandenvi-
ronmental concerns in their preparation and end-of-life destiny. However, both of
them proved to have unique and irreplaceable behavior, while safety and environ-
mental concerns have been addressed and largely (if not completely) resolved
technologically.
Another important and disputed example is that of crop protection technology,
which includes the developments of processes allowing the large scale production
of pesticides, herbicides, insecticides, fungicides, etc. These chemical products
helpcontrolthethousandsofweedspecies,harmfulinsectsandnumerousplantdis-
easesthatafflictcrops.Thedevelopmentofthesemoleculesandoftheprocessesfor
theirproductionallowedmillionsofpeopletobefedandanumberoflethalillnesses
tobe reset.
Chemical activities are usually considered to be responsible for environmental
degradation. This is largely true, but it is quite evident that this is right as a result
oftheinitialdevelopmentofchemicaltechnologiesattheirchildhoodlevel,mixed
with (at times) a still poor knowledge of several natural phenomena and of some
chemical phenomena too. A better knowledge of environmental chemistry and
biochemistryreachedinmorerecentyearsallowedtoactuallyresolvemostofenvi-
ronmental issues of chemical production technologies. Today, and sometimes also
earlier, environmental problems arise from the lack of application of technologies
thathavebeendevelopedjusttoreduceandsometimesneutralizeanyenvironmental
concern.Ontheotherhand,itisevidentthatchemistryandindustrialchemistryare
leading actorsinthe environment remediationtoo.
Inspiteoftheevidentconcernsassociatedwiththeenvironmentdegradation,itis
without any doubt that industrial chemistry has been a major leading actor in the
exponentialtechnologicaldevelopmentthatoccurredinthelast150years,allowing
averyhigh levelof wealth reached today by mostof the populations of the devel-
oped countries. It is certainly a pity, and a dishonor for our civilization, that this
highlevelofwealthdidnotcatchupwithmostofthepopulationsoflessdeveloped
countriesandalsowithalargepartoftheinhabitantsofourindustrializedcountries.
Butthis isa matter ofpolitics morethan ofthat ofscience andtechnology.
1.1.2 Catalysis and its role in industrial chemistry
AsfirstrecognizedbytheSwedishchemistJ.J.Berzeliusin1835,catalysisisaphe-
nomenonallowingachemicalreactionoccurringfasterwhenanonreactantspecies
ispresent.Inspiteoftheapparentlimitedinterestofdoingareactionfaster,catalysis
gives rise to very relevant practical effects. In fact, the increase of the rate of a
reaction can in practice result in many cases in its practical feasibility. The
1.1 Introduction 3
acceleration of a desirable chemical conversion, in fact, frequently allows it to be
realized instead of other competitive reactions, less desirable, being definitely
slower. Thus, finding an appropriate catalyst to make the desired reaction faster
than the competitive ones, as well as allowing it to perform with high efficiency,
iscrucialindevelopingindustrialprocesses.Thus,sincemaybe180years(thecon-
tact process for sulfuric acid production was developed in 1831), heterogeneous
catalysis is a keystone in industrial chemistry.1 For this reason, catalysts are also
important products of the chemical industry itself and their industrial production
represents a bigbusiness,like 13billion dollars per year.
1.1.3 Why solid catalysts?
Inpractice,alargemajorityofindustrialchemicalprocesses(likely85%2)arecata-
lyzedandmostofthemarecatalyzedbysolids.Themainreasonstousecatalystsare
synthetically the following:
1. The catalyst allows the desired reaction to become faster than competitive
reactionsthus allowing the desired reactionto beactuallyrealized.
2. For exothermic equilibrium reactions: the catalyst allows the reaction to be
performedalsoat lower temperature, whereit would bekinetically hindered
withoutit. Thus, it allows the reaction to berealized inconditions where
thermodynamicsis morefavorable.
3. For endothermic equilibrium reactions: the catalyst allows the reaction to be
performedalsoatmoderatelyhightemperatures,whereitwouldbekinetically
hindered withoutit. Thus, itallows the reaction tobe realized inconditions
wherethermodynamicsisalreadyquitefavorablewithlowerenergywasteand
allowingcheapermaterials to beused for the reactor.
4. For exothermic nonequilibrium reactions: the catalyst allows reactions less
favored bythermodynamicsand kinetics (without it)tobe realized insteadof
morefavored and otherwise faster reactions.
5. Abettercatalystallowsreactionstobeperformedinsmallerflowreactorswith
the sameperformances, orwithbetter performances andlower recycles of
unconvertedreactants in the same reactor,orevenwith shorter times inbatch
reactors.
Solid catalysts are usually preferred in the industry with respect to liquid catalysts
because of their easier separation from the reaction fluid. On the other hand, solid
catalystsarefrequentlymoreenvironmentallyfriendlythanliquidcatalystsandtheir
manipulation far safer. A typical example is that of acid catalysts for refinery and
petrochemistry. Protonic zeolites substituted for liquid acids catalysts in some
importantprocesses.Inpractice,dangerouscorrosiveliquidscharacterizedbyunsafe
manipulation procedures, difficult regeneration and unappropriate disposal, like
sulfuricacid,andAlCl -basedFriedelCraftstypeliquidacid,andverytoxicandvol-
3
atileacidslikehydrofluoricacidhavebeensubstitutedbyenvironmentallyfriendly
silicoaluminates. Additionally,catalyst performances havealsobeen improved.
4 CHAPTER 1 Heterogeneous Catalysts
Table1.1 SummaryofSomeMostRelevantFamiliesofIndustrialCatalysts
OxideCatalysts ExampleReaction
Bulksingleoxide Alcoholdehydration g-Al O Lewisacidiccatalyst
2 3
toolefins
Bulkmixedoxide Aldolcondensation MgO–Al O Basiccatalyst
2 3
calcined
hydrotalcite
Propane V/MoNb/Sboxides (Amm)oxidation
toacrylonitrile
Oxidesupported o-Xylenetophthalic V O –TiO Selectiveoxidation
2 5 2
onoxide anhydride
Isobutane K O–Cr O /Al O Dehydrogenation
2 2 3 2 3
toisobutene
Impregnatedmelt SO toSO K SO –V O /SiO Oxidation
2 3 2 4 2 5 2
orliquid
Olefin H PO /SiO (“solid Protonicacid
3 4 2
oligomerization phosphoricacid”) catalyst
ZeoliteCatalysts ExampleReaction
Protoniczeolite Benzeneþethylene H-BEA Protonicacid
toethylbenzene catalyst
Metalexchanged N Odecomposition/ Fe–MFI Redoxcatalyst
2
zeolite reduction
MetalCatalysts ExampleReaction
Bulkmetals Ammoniasynthesis Fe(CaO,K O, Hydrogenation
2
Al O ,SiO
2 3 2
promoters)
Metalgauzes Ammoniaoxidation Pt(Rhstabilizer) Selectiveoxidation
toNO
Supportedmetal Acetylene Pd/Al O (Ag Preferential
2 3
hydrogenation promoter) hydrogenation
inethylene
Carcatalytic Pt–Rh/Al O – CombustionþNO
2 3
mufflers CeO –ZrO red
2 2
Alcohols Pt/Carbon Liquidphase
toaldehydes oxidation
Aromatization Pt/K-Lzeolite Dehydrogenation
ofparaffins
SulfideCatalysts ExampleReaction
Bulksulfide Bituminoussands MoS Hydrocracking
2
tooilfractions
Supportedsulfides Gasolinetreatment NiS–MoS /g-Al O Hydrodesulfurization
2 2 3
1.1 Introduction 5
1.1.4 Industrial catalytic materials
InTable1.1,someexamplesofdifferentkindsofcatalystsactuallyusedinthechem-
ical industry are summarized.
The research in the field of heterogeneous catalysis is very active, as demon-
stratedbytherelevantnumberofspecializedinternationaljournalsandbookseries
covering the catalysis subject (Table 1.2). Catalysisjournals are also characterized
bysignificantlyhighimpactfactors,showingagainthehighactivitycharacterizing
this research field. As obvious,excellentcatalysis research isalso published inthe
mostdistinguishedgeneralchemistryjournals,suchasNature,Science,Angwandte
Table1.2 ScientificPublicationsofHeterogeneousCatalysisResearch
SeriesofBooksReportingHigh-levelReviewsinCatalysis
1 CatalysisReviewsdScienceand Taylorand
Engineering Francis
2 AdvancesinCatalysis Elsevier
3 CatalysisdSpecialistPeriodicalReports RSC
SeriesofBooksReportingFullPapersComingfromConferencePapers
StudiesinSurfaceScienceandCatalysis Elsevier
SpecialisticJournals(ImpactFactor2012)
1 AppliedCatalysisB:Environmental Elsevier 5.825
2 JournalofCatalysis Elsevier 5.787
3 ACSCatalysis ACS 5.265
4 ChemCatChem Wiley 5.181
5 Catalysis:ScienceandTechnology RSC 3.753
6 AppliedCatalysisA:General Elsevier 3.410
7 JournalofMolecularCatalysisA: Elsevier 3.187
Chemical
8 CatalysisToday Elsevier 2.980
9 CatalysisCommunications Elsevier 2.915
10 TopicsinCatalysis Springer 2.608
11 CatalysisLetters Springer 2.244
12 CatalysisSurveysfromAsia Springer 1.897
13 ChineseJournalofCatalysis Science 1.304
Press
14 ReactionKinetics,Mechanismsand Springer 1.104
Catalysis
15 KineticsandCatalysis Maik 0.543
16 OpenCatalysisJournal Bentham
17 CatalysisinIndustry Maik
Continued
6 CHAPTER 1 Heterogeneous Catalysts
Table1.2 ScientificPublicationsofHeterogeneousCatalysis
Researchdcont’d
OtherJournalsPublishingPapersintheCatalysisandintheCatalysts
Fields(ImpactFactor2012)
1 ChemSusChem Wiley 7.475
2 GreenChemistry RSC 6.828
3 JournalofPhysicalChemistryC ACS 4.814
4 AppliedEnergy Elsevier 4.781
5 JournalofPowerSources Elsevier 4.675
6 Langmuir ACS 4.187
7 InternationalJournalofHydrogenEnergy Elsevier 3.548
8 ChemicalEngineeringJournal Elsevier 3.473
9 MicroporousandMesoporousMaterials Elsevier 3.365
10 Fuel Elsevier 3.357
11 FuelProcessingTechnology Elsevier 2.816
12 EnergyandFuels ACS 2.853
13 ChemicalEngineeringScience Elsevier 2.386
14 IndustrialandEngineeringChemistry ACS 2.206
Research
Chemie,whileanumberofhigh-levelreviewscanalsobefoundintypicalgeneral
chemistry-reviewpublicationjournalssuchasChemicalReviews(ACS)andChem-
ical SocietyReviews (RSC).
Duetothisenormousexperimentalwork,averybignumberofnewcatalystsor
catalytic materials are prepared, characterized and tested in a number of different
reactions. It is obvious that the large majority of them lack activity, selectivity,
Table1.3 SomeLeadingCatalystProducers
1 HaldorTopsoe Refining,petrochemicals Denmark
2 UOP Refining,petrochemicals USA
3 Axens Refining,petrochemicals France
4 JohnsonMatthey Refining,petrochemicals UK
5 Criterion Refining USA
6 Clariant(Su¨dChemie) Refining,petrochemicals Switzerland/Germany
7 Albemarle Refining,petrochemicals USA
8 GraceDavison Refining USA
9 BASF Refining,petrochemicals Germany
10 ExxonMobil Refining,petrochemicals USA
References 7
stability to arrive to optimization and industrial exploitation. In this book, really
industrially applied catalysts will be considered with some detail. This is because
inthis case thegoodpractical behaviorisactuallyproven.
Besides the many papers published in open journals, information can also be
foundinpatentliteratureandfromdatareportedbythecatalystproducerindustries,
some of them being reported in Table 1.3. Indeed most of these companies reveal
someinformationontheircommercialcatalystsinsomeexcellentbrochuresavail-
able at their Websites.
References
1. ArmorJN.CatalToday2011;163:3e9.
2. de Jong KP. In: de Jong KP, editor. Synthesis of solid catalysts. Wiley-VCH; 2009.
pp.3e11.
CHAPTER
2
Preparation of Solid
Catalysts: A Short
Summary
CHAPTER OUTLINE
2.1 Preparationofcatalystprecursors.......................................................................11
2.1.1 Choiceofthestartingcompounds......................................................11
2.1.2 Drypreparationprocedures................................................................11
2.1.2.1 Thermaldecompositionofprecursors.......................................11
2.1.2.2 Solid-statereaction...................................................................11
2.1.2.3 Flamehydrolysisofmetalchlorides...........................................11
2.1.2.4 Solid-statewetting....................................................................12
2.1.2.5 Solid-stateionexchange...........................................................12
2.1.2.6 Combustionsynthesismethods.................................................12
2.1.2.7 Preparationoffusedcatalysts...................................................13
2.1.3 Wetcatalystpreparationsandotherslurry-phasepreparationmethods..13
2.1.3.1 Precipitationandcoprecipitation...............................................13
2.1.3.2 Solegelpreparations................................................................14
2.1.3.3 Aerogelpreparations(solegelchemistryfollowed
bysupercriticaldrying).............................................................14
2.1.3.4 Directsolegelpreparationinsupercriticalliquids......................15
2.1.3.5 Microemulsionandreversemicellemethods.............................15
2.1.3.6 Hydrothermalandothersolvothermalmethods.........................16
2.1.3.7 The“polyol”technique.............................................................16
2.1.3.8 Template-drivenhydrothermalpreparationprocedures
ofporousmaterials...................................................................17
2.1.3.9 Solutioncombustionsynthesis..................................................17
2.1.3.10 Thecitrateautocombustionmethod..........................................17
2.1.3.11 Impregnationmethods..............................................................18
2.1.3.12 Deposition/precipitation............................................................18
2.1.3.13 Ionexchangeandadsorption....................................................18
2.1.3.14 Grafting....................................................................................18
2.1.3.15 Plasmaechemicalsyntheses....................................................19
2.1.4 Intermediateandfinaltreatmentsinpreparationchemistry..................19
References...............................................................................................................20
9
HeterogeneousCatalyticMaterials.http://dx.doi.org/10.1016/B978-0-444-59524-9.00002-X
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