Pillared Clays and Related Catalysts

531 Pages·2010·9.732 MB·English

by  Geolar Fetter, Pedro Bosch (auth.), Antonio Gil, Sophia A. Korili, Raquel Trujillano, Miguel Angel Vicente (eds.)

Pillared Clays and Related Catalysts
· · ·
Antonio Gil Sophia A. Korili Raquel Trujillano
Miguel Angel Vicente
Editors
Pillared Clays and Related
Catalysts
Foreword by Thomas J. Pinnavaia
123
Editors
Dr.AntonioGil Dr.SophiaA.Korili
DepartmentofAppliedChemistry DepartmentofAppliedChemistry
PublicUniversityofNavarra PublicUniversityofNavarra
Pamplona31080,Spain Pamplona31080,Spain
[email protected] sofi[email protected]
Dr.RaquelTrujillano Dr.MiguelAngelVicente
DepartmentofInorganicChemistry DepartmentofInorganicChemistry
UniversityofSalamanca UniversityofSalamanca
Salamanca37008,Spain Salamanca37008,Spain
[email protected] [email protected]
ISBN978-1-4419-6669-8 e-ISBN978-1-4419-6670-4
DOI10.1007/978-1-4419-6670-4
SpringerNewYorkDordrechtHeidelbergLondon
LibraryofCongressControlNumber:2010933724
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Foreword
The concept of using intercalation chemistry to transform a lamellar solid into a
porousanalogoriginatedmorethan55yearsagointheAberdeenUniversitylabo-
ratory of Professor Richard M. Barrer. In a seminal 1955 paper, co-authored with
graduatestudentD.M.MacLeodandpublishedintheTransactionsoftheFaraday
Society, Barrer described how the “replacement of inorganic cations in montmo-
rillonite by N(CH ) + and N(C H ) + cations opens up the lamellae and causes
3 4 2 5 4
profound changes in the sorption and intercalation of organic molecules.” The
paper also demonstrated sorptive selectivity based on the cross-sectional molecu-
lardiametersoftheadsorbates.Despitethepromisingmolecularsievingproperties
ofBarrer’salkylammoniumion-exchangedformsofsmectiteclays,hisinnovation
remained essentially undeveloped for two decades due primarily to the concomi-
tantdiscoveryofsyntheticzeolitesLindeTypeA(LTA)andTypeX(FAU).These
purelyinorganicmolecularsieveshadsurfaceareasandporevolumescomparable
toBarrer’sclayintercalates,buttheywerefarmorethermallystableincomparison
tothealkylammoniumion-exchangedformsofsmecticclays.
In1977,GeorgeW.BrindleyandR.E.Sempelsshowedthatthepartialreplace-
mentofNa+-exchangecationsbyhydroxyaluminumcationsinthegalleriesofthe
smecticclaybeidelliteaffordedintercalateswithnitrogenBETsurfaceareasupto
500 m2/g after calcination at 325 ◦C. This finding presaged the 1978 W.R. Grace
patentinventionofDavidE.W.Vaughan,RogerJ.Lussier,andJohnS.Magee,Jr.on
“PillaredInterlayeredClayMaterialsUsefulasCatalystsandSorbents.”Thisbreak-
through garnered the attention of the clay and zeolites research communities and
spawnedaflurryofresearchactivitythatpersiststothecurrentday.Todate,more
than 3,500 journal publications and 390 patents have been published on pillared
smectiteclaysandrelatedporousderivativesoflamellarcompounds.Moreover,the
advances in the applications of pillared materials continue to expand. The decade
following the pillared clay disclosure of Vaughan et al. witnessed the publication
of approximately 200 journal articles and 64 patents. In the decade of the 1990s,
the numbers grew to 1,300 journal articles and 170 patents. The decade following
theturnofthetwenty-firstcenturysawasustainedinterestinpillaredmaterials,as
evidencedbythepublicationofmorethan2,000additionaljournalarticlesand155
patents.
v
vi Foreword
Thedecadefollowing2010almostcertainlywillwitnesscontinuedresearchon
the applications of pillared layered materials. For this reason the present volume
on pillared intercalates is an exceptionally timely contribution that will serve as a
valuablereferencesource.Muchofthecontemporaryinterestinpillaredclaysand
related interaction compounds is stimulated by their properties as heterogeneous
catalystsfortheproductionoffinechemicalsandasselectiveadsorbentsformolec-
ular preparations, environmental remediation, and pollution control. The present
volumeprovidesathoroughandexpertaccountingoftherecentadvancesineachof
these application areas. Emphasis isunderstandably placed on pillaredversions of
smectiteclaysandlayereddoublehydroxides,alsoknownashydrotalcitesormixed
metal hydroxides, in part, because these are the most versatile and cost-effective
lamellarhoststructuresavailableincommercialquantitiesforpillaring.Inaddition,
detailed state-of-the art evaluations are also provided for layered phosphates and
porous aluminum phosphates. The 16 complementary chapters cover a very broad
rangeofcatalyticandsorptiveprocessesofenvironmentalandindustrialrelevance
with little or no redundancies. The level of coverage attests to the expertise of the
contributingauthorsinthefieldofpillaredlayeredmaterials.Thebooksurelywill
serveasanessentialreferencesourceoverthenextdecadeforworkersengagedin
the intercalation chemistry and materials applications of lamellar inorganic solids,
particularlylayeredoxidesandhydroxides.
UniversityDistinguishedProfessorofChemistry ThomasJ.Pinnavaia
MichiganStateUniversity
EastLansing,MI,USA
Preface
Theinterestinallaspectsrelatedtopillaredinterlayeredclays,suchasnewsynthesis
methodsorthestudyoftheirpropertiesandapplications,hasgreatlyincreasedover
thelastfewyears.Severalofthepapersdevotedtopillaredinterlayeredclays,both
as articles and as book chapters, have reviewed various aspects of the prepara-
tion, characterization, or applications of these solids. The approach that has been
commonly used in previous studies to organize such a large amount of informa-
tion is mainly based on the preparation of pillared clays, as well as some aspects
about the catalytic applications of these solids. As indicated earlier, the interest in
these solids is so large that, since our first comprehensive review on the synthesis
and catalytic applications published 9 years ago (Gil A, Gandia LM, Vicente MA
(2000)Recentadvancesinthesynthesisandcatalyticapplicationsofpillaredclays.
Catalysis Reviews, 42:145–212), more than 500 new references have appeared in
the literature and interest in this field is continuously increasing. A second review
dealswiththeporousstructuredevelopedbythesematerialsduringtheintercalation
process(GilA,KoriliSA,VicenteMA(2008)Recentadvancesinthecontroland
characterizationoftheporousstructureofpillaredclaycatalysts.CatalysisReviews,
50:153–221).Thisisaveryimportantaspectbecausethetexturalpropertiesofpil-
laredclaysplayakeyrolewhenthesematerialsareusedascatalysts,adsorbents,or
ingasseparation.
Since the first works introducing the aluminum intercalated clay family at the
beginning of the 1970s, the synthesis of pillared interlayered clays has expanded
enormously.Theneedforsolidsthatcouldbeusedascrackingcatalystswithlarger
poresthanthezeoliticmaterialsspurredthesynthesisofnewporousmaterialsfrom
clays. These solids are prepared by exchanging the charge-compensating cations
present in the interlamellar space of the swelling clays by hydroxyl-metal poly-
cations. On calcining, the inserted polycations yield rigid, thermally stable oxide
species, which prop the clay layers apart and prevent their collapse. The interca-
lation and pillaring processes produce the development of a porous structure with
thepresenceofparticularsurfacesites.Thesepropertiesdeterminethepotentialuse
of the solids in catalytic, purification, and sorption-based separation applications.
The properties of pillared clays synthesized in the presence of microwave irradia-
tionarecomparedtothosepreparedintheconventionalwaybyFetterandBoschin
vii
viii Preface
Chapter1. In Chapter 2, Pires and Pinto present the potential use of pillared clays
as selective adsorbents of natural and biogas components, such as carbon dioxide,
methane,ethane,andnitrogen.
Animportantcharacteristicofthepillaredclaysistheiracidity.Thetype,number,
andstrengthofsurfaceacidsitesdependonseveralfactors,suchastheexchangeof
cations,thepreparationmethod,andthenatureofthestartingclay.Theseareprop-
ertiesdirectlyrelatedtothecatalyticperformance.Therefore,thetypeofaciditycan
determine which type of reaction the clays can catalyze. Several types of reaction
havebeenstudied,suchasalkylation,dehydrogenation,hydrocracking,andisomer-
ization. Some examples of this type of applications are summarized in Chapters 3
and4.
Oneofthemoststudiedtopicsrelatedtopillaredclaysistheiruseassupportsfor
catalytically active phases, and the use of the resulting solids in several reactions,
particularlyinenvironment-friendlyones.Thenumberofarticlesinthisfieldisvery
extensive,includingcatalyststhatcontainCo,Cr,Cu,Fe,Mn,Ni,Pd,Pt,Rh,orV.
Mishrasummarizesthesynthesisandapplicationsoftransitionmetaloxide-pillared
claysinChapter5.Titanium,iron,chromium,manganese,andmixedoxideswere
considered,withemphasisontheirfuturepotentialascatalysts.Hydrocarboncrack-
ingandvariousexamplesrelatedtoenvironmentalprocessesasphotocatalysisand
pollution control in gas and liquid phases are presented by the author. The use of
pillared clays in catalytic waste water treatment is summarized in Chapters 6–8.
Herney-Ramirez and Madeira reviewed the use of pillared clays in heterogeneous
Fenton-likeadvancedoxidationprocesses.Theeffectofthemainoperatingcondi-
tions on oxidation efficiency is considered by the authors. Special attention to the
useofpillaredclaysinwetaircatalyticoxidation(WACO),wethydrogenperoxide
catalyticoxidation(WHPCO),andphoto-Fentonconversionofpollutantsisconsid-
eredbyPerathonerandCenti.Thecatalyticwetperoxideoxidationofphenolusing
pillaredclaysinacontinuousflowreactorispresentedbyGuélouetal.inChapter8.
The experimental results are very promising for developing a catalytic continuous
process for industrial wastewater purification. The chapter written by Zuo et al.
reviewstherecentdevelopmentsofferedfrompillaredclay-supportednoblemetals
andmetaloxidecatalystsforcompleteoxidationofrepresentative volatileorganic
compound (VOC) molecules such as benzene, toluene, chlorobenzene, phenol,
among others. Selective reduction of NOx has been the reaction to environmental
interestforwhichpillaredclayshavebeenmostwidelyused.Recenttrends,limits,
and opportunities offered from pillared clays and other related materials (layered
clays,layereddoublehydroxides(LDHs),andporousclayheterostructures(PCHs)
inthisfieldarediscussedbyBelverinChapter10.Specialattentionisfocusedon
the modification that led to materials with a higher or comparable activity to that
describedbycommercialsystems.InChapter11,Vicenteetal.presentstheuseof
pillaredclaysincatalyticoxidationreactionsrelatedtogreenchemistryconcepts.
The book also includes four Chapters (12–15) dealing with treatment of other
layered materials, mainly anionic clays, and mesoporous solids, comparing them
with the pillared clays. The state-of-the- art in the synthesis, characterization, and
Preface ix
catalytic performance of layered double hydroxides (LDH) with the hydrotalcite-
type structure containing several polyoxometalates (POM) in the interlayer is
presentedbytheRivesgroupinChapter12.Theimmobilizationofpolyoxometalate
species in the interlayers of layered double hydroxides with the hydrotalcite-type-
solids allows the preparation of homogeneous catalysts with tailored redox and
acidity properties. The authors indicate that the properties of these materials can
befinelytunedthroughthemodificationofthecationsinthebrucite-likelayersand
thepolyoxometalateintheinterlayer,inordertoapplythemtoseveralcatalyticpro-
cesses.Otherparameterssuchasthepolaritymodulationorthesolventscanmodify
thereactivityoftheLDH–POMcatalysts.InChapter13,Figueraspresentsthelatest
ideasonthemodificationofthebasicpropertiesofhydrotalcitesbyanionexchange
and on the properties of solid bases as catalysts. Several examples of applications
are given, with emphasis on industrial processes recently shown such as isomer-
izationofolefins,aldolization,oxidationofketones;supportsofmetalcatalysts;as
well as adsorbents and anionic exchangers. The synthetic pathways for obtaining
mesoporousphosphatestructuresandaluminophosphatesmakeupthesubjectspre-
sented in Chapters 14 and 15 by Moreno et al. and O’Malley et al., respectively.
Thepreparationofmetal-supportedcatalystsandtheirapplicationingasseparation,
adsorption,andcatalysisarealsoreviewed.
Inthefinalchapter,thesynthesisandapplicationtoindustrialcatalyticreactions
of macrocyclic complexes supported on clays with thermal and chemical stability
arepresentedbytheteamofKumaretal.
Theeditorsareverygratefultoalltheauthorsfortheirwillingnesstoparticipate
inthisproject,andfortheirenthusiasminwritingthecontributions,andforsharing
theirknowledgewiththereaders.
Navarra,Spain AntonioGil
Navarra,Spain SophiaA.Korili
Salamanca,Spain RaquelTrujillano
Salamanca,Spain MiguelAngelVicente
Contents
1 MicrowaveEffectonClayPillaring . . . . . . . . . . . . . . . . . . 1
GeolarFetterandPedroBosch
2 PillaredInterlayeredClaysasAdsorbentsofGasesandVapors . . 23
J.PiresandM.L.Pinto
3 Characterization and Catalytic Performance
ofMontmorilloniteswithMixedAluminium/LanthanidePillars . . 43
F.González,C.Pesquera,andC.Blanco
4 Synthetic Hectorite: Preparation, Pillaring
andApplicationsinCatalysis . . . . . . . . . . . . . . . . . . . . . 67
Chun-HuiZhou,DongshenTong,andXiaonianLi
5 TransitionMetalOxide-PillaredClayCatalyst:Synthesis
toApplication . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
TrilochanMishra
6 Use of Pillared Clay-Based Catalysts for Wastewater
TreatmentThroughFenton-LikeProcesses . . . . . . . . . . . . . 129
J.Herney-RamírezandLuisM.Madeira
7 CatalyticWastewaterTreatmentUsingPillaredClays . . . . . . . 167
SiglindaPerathonerandGabrieleCenti
8 Fe–Al-PillaredClays:CatalystsforWetPeroxideOxidation
ofPhenol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 201
ErwanGuélou,Jean-MichelTatibouët,andJoëlBarrault
9 PillaredClay-SupportedNobleMetalandMetalOxide
CatalystsforCompleteOxidationofVOCs. . . . . . . . . . . . . . 225
ShufengZuo,QinqinHuang,andRenxianZhou
10 ClayMaterialsforSelectiveCatalyticReductionofNO . . . . . . 255
x
CarolinaBelver
xi