Pillared Clays and Related Catalysts PDF
Preview Pillared Clays and Related Catalysts
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 ©SpringerScience+BusinessMedia,LLC2010 All rights reserved. This work may not be translated or copied in whole or in part without the written permission of the publisher (Springer Science+Business Media, LLC, 233 Spring Street, New York, NY 10013, USA), except for brief excerpts in connection with reviews or scholarly analysis.Useinconnectionwithanyformofinformationstorageandretrieval,electronicadaptation, computer software, or by similar or dissimilar methodology now known or hereafter developed is forbidden. Theuseinthispublicationoftradenames,trademarks,servicemarks,andsimilarterms,eveniftheyare notidentifiedassuch,isnottobetakenasanexpressionofopinionastowhetherornottheyaresubject toproprietaryrights. Printedonacid-freepaper SpringerispartofSpringerScience+BusinessMedia(www.springer.com) 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
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