Ref 5 new solid acids and bases

Studies in Surface Science and Catalysis 51 NEW SOLID ACIDS AND BASES their catalytic properties This Page Intentionally Left Blank Studies in Surface Science and Catalysis Advisory Editors: B Delmon and J T Yates Vol 51 NEW SOLID ACIDS AND BASES - THEIR CATALYTIC PROPERTIES by Kozo TANABE Professor, Department of C h i s t r y , Faculty of Science, Hokkaido University, Sapporo, Japan Makoto MISONO Professor, Department of Synthetic Chemistry, Faculty of Engineering, Tht University of Tokyo, Tokyo, Japan Yoshio O N Professor, Department of Chcmical Engineering, Faculty Enginemng, Tokyo Institute of Technoloo, Tokyo, Japan of Hideshi HATTORI Associate Professor, Department of Chemistry, Faculty Science, HokAaido University, Sapporo, Japan of KODANSHA Tokyo 1989 ELSEVIER Amsterdam -Oxford - New York - Tokyo Copublistud by KODANSHA LTD., Tokyo and ELSEVIER SCIENCE PUBLISHERS B.V., Amsterdam exclusive sales rights in Japan KODANSHA LTD 12-21, Otowa 2-chome, Bunkyo-ku, Tokyo 112, Japan for the U.S.A and C a d ELSEVIER SCIENCE PUBLISHING COMPANY, INC 655 Avenue of the Americas, New York, N.Y 10010, U.S.A for the rest of flu world ELSEVIER SCIENCE PUBLISHERS B.V 25 Sara Burgerhartstraat, P.O Box 211, 1000 AE Amsterdam, The Netherlands Library of Congress Cataloging-in-Publication Data : t h e i r catalyttc p r o p e r t l e s I b y Kozo Tanabe [et a l cn ( S t u d l e s i n surface science a n d catalysis ; 51) p Includes b i b l i O g r a p h l C a references New s o l i d acids a n d bases ISBN 0-444-98800-9 A c i d s Bases (Chemistry) 11 S e r i e s OD477.N49 1989 646'.24 dc20 Catalysts I Tanabe K o z i 89-23475 CIP ISBN 0-444-98800-9 (V01.51) ISBN 0-444-41801-6 (Series) ISBN 4-06-204394-7 (Japan) Copyright 01989 by Kodansha Ltd All rights reserved No part of this book may be reproduced in any form, by photostat, microfilm, retrieval system, or any other means, without the written permission of Kodansha Ltd (except in the case of brief quotation for criticism or review) PRINTED INJAPAN Preface Nineteen years have passed since the monograph "Solid Acids and Bases" was published in 1970 During this period many new kinds of solid acids and bases have been found and synthesized The surface properties (in particular, acidic and basic properties) and the structures of the new solids have been clarified by newly developed measurement methods using modern instruments and techniques The characterized solid acids and bases have been applied as catalysts for diversified reactions, many good correlations being obtained between the acid-base properties and the catalytic activities or selectivities Recently, acid-base bifunctional catalysis on solid surfaces is becoming an ever more important and intriguing field of study It has been recognized that the acidic and basic properties of catalysts and catalyst supports play an important role even in oxidation, reduction, hydrogenation, hydrocracking, etc The effect of the preparation method and the pretreatment condition of solid acids and bases on the acidic and basic properties, the nature of acidic and basic sites and the mechanism regarding the generation of acidity and basicity have been elucidated experimentally and theoretically On the basis of the accumulated knowledge of solid acids and bases, it is now possible to design and develop highly active and selective solid acid and base catalysts for particular reations Moreover, the chemistry of solid acids and bases is being related to and utilized in numerous areas including adsorbents, sensors, cosmetics, fuel cells, sensitized pressed papers, and others In the present volume, the great progress in solid acids and bases made over the past two decades is summarized and reviewed with emphasis on fundamental aspects and chemical principles We wish to express our gratitude to Ms Cecilia M Hamagami and Mr I Ohta of Kodansha Scientific Ltd for their invaluable assistance of the preparation of the English manuscripts which comprise this book Summer 1989 KOZOTANABE Makoto MISONO Yoshio O N Hideshi HATTORI This Page Intentionally Left Blank Contents Preface v Definition and Classification of Solid Acids and Bases Determination of Acidic and Basic Properties on Solid Surfaces 2.1 Acidic Property Strength and Amount of Solid Acid Bnansted and Lewis Acid Sites 11 2.1.1 2.1.2 2.2 Basic Property 2.3 2.3.1 2.3.2 5 14 2.2.1 Benzoic Acid Titration Method Using Indicators 16 2.2.2 Gaseous Acid Adsorption Method 17 2.2.3 Other Methods 14 Acid-Base Property 18 Representative Parameter, H0,- of Acid-Base Property Acid-Base Pair Sites 22 18 Acid and Base Centers : Structure and Acid-Base Property 27 3.1 Metal Oxides 27 3.1.1 Li20, NazO, K20, R h o , CNO 27 3.1.2 BeO, MgO, CaO, SrO, BaO, RaO, Ba (0H)z 29 3.1.3 Oxides of Rare Earth Elements (Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, cd,Tb, Dy, Ho, Er, Tm, Yb, Lu), Actinide Oxides(ThO2, UOz) 41 3.1.4 TiOz, ZrO2 47 60 3.1.5 VzO5, Nb205, Ta205 3.1.6 Oxides of Cr, Mo, W 64 3.1.7 Oxides of Mn, Re 69 70 3.1.8 Oxides of Fe, Co, Ni 72 3.1.9 Oxides of Cu, Ag, Ay 3.1.10 ZnO, CdO 73 78 3.1.11 Oxides of B, Al, Ga 91 3.1.12 SO*, GeO2, SnOz, PbO, PbOz 105 3.1.13 Oxides of P, As, Sb, Bi 108 3.1.14 Oxides of Se, Te 3.2 3.2.1 3.2.2 Mixed Metal Oxides 108 Mechanism of Acidity Generation 108 Acid and Base Data on Binary Oxides 114 vii viii CONTENTS 3.3 3.3.1 3.3.2 3.3.3 3.3.4 3.3.5 Clay Minerals 128 Sheet Silicates 128 Acidity of Sheet Silica and Pillared Clays 129 Organic Reactions Catalyzed by Sheet Silicates Catalysis by Pillared Clays 138 Catalysis by Other Clays 139 3.4 Zeolites 3.4.1 3.4.2 3.4.3 3.4.4 3.4.5 3.4.6 3.4.7 3.4.8 3.4.9 3.5 3.5.1 3.5.2 3.5.3 3.5.4 132 142 Structure of Zeolites 142 Acidity of Zeolites 143 148 Acidity Measurement of Faujasites by Means of Hammett Indicator 159 Acidity of Different Ziolites - Effect of (Si02/Al20)3 Ratio Effect of Dealumination on Acidic Properties 151 Acidity of Metallosilicate 154 AlP04-n, SAPO-n and Related Materials 156 Zeolites as Base Catalysts 158 Shape Selective Reactions over Zeolites 159 Heteropoly Compounds 163 General Remarks 163 Preparation and Physical Properties Acidic Properties in the Solid State Acid Catalysis 168 165 166 3.6 Ion-Exchange Resins 173 Structure of Ion-exchange Resins 173 Characteristics of Styrene-Divinylbenzene Ion Exchange Resins aa Catalyst 175 3.6.3 Catalysis by Anion Exchange Resins 178 180 3.6.4 Nafion-H aa a Catalyst for Organic Reactions 3.6.1 3.6.2 3.7 Metal Sulfides 3.8 Metal Sulfates and Phosphates 185 Metal Sulfates 185 Metal Phosphate (Phosphorous Metal Oxide) 3.8.1 3.8.2 3.9 3.9.1 3.9.2 3.10 183 Superacids 199 Ti0~ S04~-,ZrO2- S042-, Fe203- SO4*199 Complex Metal Halides and Mounted Superacids 206 Superbases 211 Catalytic Activity and Selectivity 4.1 4.1.1 4.1.2 4.1.3 4.1.4 4.1.5 4.2 4.2.1 4.2.2 4.2.3 188 Isomerization 215 General Remarks 15 Double-Bond Isomerization 215 Isomerization of Paraffins 220 Isomerization of Alkylbenzenes 223 Isomerization Including Heteroatoms 215 223 Alkylation 225 Alkylation of Aromatics with Alcohols 225 Alkylation of Aromatics with Olefms 227 Alkylation of Aromatics with Alkyl Halides 230 Contents ix Alkylation of Aromatics with Alkyl Chloroformates and Oxalates Alkylation of Phenols with Alcohols and Olefins 231 Side-chain Alkylation of Aromatics 233 N-Alkylation of Aniline with Methanol or Dimethyl Ether 235 Alkylation of Isobutane with Olefins 236 4.2.4 4.2.5 4.2.6 4.2.7 4.2.8 4.3 Acylation 4.4 Transalkylation of Alkylaromatics 241 General Mechanism 241 Disproportionation of Toluene 242 Transalkylation of Alkylaromatics Other Than Toluene 4.4.1 4.4.2 4.4.3 4.5 239 Hydration of Olefins 247 Acidic Property us Catalytic Activity and Selectivity Mechanism of Hydration 250 Design of Hydration Catalyst 252 4.5.1 4.5.2 4.5.3 Conversion of Methanol into Hydrocarbons Methanol to Gasoline Process 254 Reaction Mechanism 255 Modification of Product Distribution 258 4.6 4.6.1 4.6.2 4.6.3 4.7 4.7.1 4.7.2 4.7.3 4.7.4 4.7.5 4.7.6 4.7.7 4.7.8 4.7.9 4.7.10 244 248 254 Dehydration 260 Dehydration of Alcohols 260 Mechanisms and Selectivities of Alcohol Dehydration 261 Dehydration of Alcohol with Ring Transformation 267 Dehydration of Heterocyclic Alcohols 267 Dehydration of Diols 268 Dehydration of Carbohydrates 268 Dehydration of Cyclic Ethers and Epoxides 269 Dehydration of Aldehydes 269 Dehydration of Carboxylic Acids 269 Dehydration of Amides 270 4.8 Dehydrohalogenation 4.9 Oligomerization and Polymerization 275 Oligomerization of Lower Olefins with Solid Acid Catalysts Dimerization of Olefins with Alkali Metals 279 Polymerization of Alkene Oxides 280 Miscellaneous Polymerization over Solid Acids and Bases 4.9.1 4.9.2 4.9.3 4.9.4 4.10 4.10.1 4.10.2 4.10.3 4.10.4 4.11 4.11.1 4.11.2 4.1 1.3 4.11.4 4.11.5 4.11.6 272 Esterification 283 General Remarks 283 Reaction Mechanism 283 Effects of Chemical Porperties of Catalyst Typical Solid Acid Catalysts 285 275 280 284 Hydrolysis 286 Hydrolysis of Esters 286 Hydrolysis of Ethers 286 Hydrolysis of Carbohydrates 287 Hydrolysis of Nucleosides 289 Hydrolysis of Acetals 289 Hydrolysis of Methylhalides and Methylene Chloride 290 230 356 SUBJECT INDEX bentonite 35 benzaldehyde 32 benzaldehyde esterification 37 1,2-benzenediol with methanol 192 benzene hydrogenation 29 benzoic acid titration method 14 benzophenone 239 benzyl chloride 239 benzyl-benzilic acid rearrangement 40 bicarbonate 81 bidentate 33 bifunctional catalyst 220 bimetallic catalyst 341 binary oxide 108 7, 50, 62, 119, 126, 186, 217, Brgnsted acid 248, 341 BrCnsted acidity 13, 121 BrC,nsted base 32 Brfinsted definition Br+nsted rule 89 bulk acidity 166 bulk-type catalysis 168 1,3-butadiene 12 , F b u t a d i e n e hydrogenation 43, 44, 310 butanamine 56 butane 205 n-butane 324 a-butanol 283 sec-butanol 56 2-butanol 319 1-butanol dehydration 190 2-butanol dehydration 121, 196 butene 216, 318 1-butene 56 butene isomerization 27, 35, 119-121, 190, 194 1-butene isomerization 43, 44, 66 set-butyl alcohol 318 n-butylamine t-hutylation of phenol 94 china clay 351 chlorination 137 0-chlorobenzoyl chloride 239 chloroform 32 Ciaisen-Schmidt reaction 40 Claus reaction 159 C N D O / - +molecular orbital calculation CO 56, 70, 74 CO2 56, 70, 72, 74 CO adsorption 81 C adsorption 52 coal liquid 343 coisomerization of ck-2-butene-do/d, 11 coke 339 concerted mechanism +EL! S-&-conformer 310 S-trans-conformer 310 constraint index 298 conversion of amide to nitrile 192 of methanol to hydrorarbon 169, 254 of propane 207 coordinately bonded pyridine 12 coordinative unsaturation 71, 184 cosmetic pigment 352 C P (cross polar) ii cracking 132, 138 of hydrocarbon 120 by ZSM-5 152 cracking rate 297 cross aldol condensation of formaldehyde 328 cross aldol reaction of silyl butene acetal 329 cyanoethylation of alcohol 178 cyclohexadiene 12 cyclohexane 207, 222, 317 cyclohexene skeletal isomerization 190 cyclopropane ring opening 194 cymene 121 p-cymene 353 camphene 51 carbenium ion 66 carbenium (C + ) i o n mechanism-El carbonarcous material 339 carbonate 33, 81 carbon dioxide 17 carbonless paper 350 carbon monoxide hydrogenation carene isomerization 121 catalyst support 51, 58 catalytic cracking 292, 345 catalytic reforming 302 c-harzr difference 109 deactivation 339, 342 dealumination of zeolite 151, 154 1-decane oligomerization 192 decomposition of diacetone alcohol 123 of hydrogen peroxide 121, 133, 168, 170 dehydration 86, 87, 133, 168, 170 of alcohol 43, 120, 192, 194, 205, 260 of aldehyde 269 ofamide 270 of 2-butanol 62 of butyl alcohol 159 of carbohydrate 268 13 ~ Subject Index of of of of of carboxylic acid 269 diol 268 forinainide 270 heterocyclic alcohol 267 isobutyl alcohol 159 of isopropyl alcohol , 22, 335 of 4-methyl-2-pentanol 123 dehydrobroinination 272 of 2-hrornobutane 100 of2,3-dibromobutane 100 dehydrochloririation 272 dehydrogenation 67, 316 of ethylbenzene 123 of isopropyl alcohol 18, 349 of isopropylbenzene 212 of d-Iirnonenr 353 dehydrohalogenation 88 dehydroxylation 84 depolymerization 120 of paraldehyde 8, 185 design of hydration catalyst 252 deuteration 310 deuterium exchange 250 dewaxing 161, 349 diacetone alrohol decomposition 37 Diels-Alder reaction 181 diethyl ether 248 differential thermal analysis *DTA diffusion 284, 342 dihydrogen 74 dimerization 323 of propene 279 dirnethyI-2-but~nylalnine 330 dimethyl pyridine 82 diphenylarnine 17, 52 diphenylmethane hydrocracking 301 diphenylnitroxide radical 17, 52 disproportionation 139 of ethylbenzene 244, 245 of m-xylem 245 of toluene 242, 245 dissociation 86 I320 55 double bond isomerization 85, 213 D?’A 9, 48 EABP(equi acid-base point) 69 ElcB mechanism 46, 273 electron donating property 30 electronegativity 187, 219, 316 of metal ions 113 electrostatic valence rule 85 /3-eliinination 272 E l mechanism 273 357 E2 mechanism 273 electron pair transfer enol-type 318 El process 190 E2 process 190 equilibrium constant 251 ESR (electron spin resonance) 186, 201 esterification 36, 63, 171, 283, 285 of terephthalic acid 265 ethanol 248, 250, 251 ethanol synthesis 247 etheration 168, 171 ethylamine 330 ethylbenzene 316 ethyl carbenium ion 252 ethylene 247, 251 ethylene glycol 204 ethylene hydration 124 ethylene oxide 224 ethylene polymer 248 l3-ethylpyridine 22 exchange 36 fluid catalytic cracking 294 formaldehyde 57, 319 formic acid 57, 74, 169, 317 fuller’s earth 351 gamma irradiation 187 gaseous acid 16 gas sensor 347 generation of acid site 122 o-/P-H, conversion 86 haloniurn intermediate 274 Hammett acidity function Harnmett indicator 8, 18, 120 H-D exchange 55 HDS 121, 183, 342 heat of N H J adsorption 10, 83 heterogeneous precipitation 117 heterolytic dissociation of hydrogen 33 heteropoly acid 163 heteropolyanions 163 hexane cracking 160, 292 hexene 207 Hofmann orientation 262 HOMO 125 homogeneous precipitation 117 Hougen-Watson’s rate equation 250 HSAB(hard and soft acids and bases) 13 humidity sensor 348 hydration 63, 77, 168 of ethylene 248 358 SUBJECTINDEX of nitrile 69 of olefin 247 of propylene 249 hydride shift 222 hydrocracking 68, 69, 300 hydrodemetallation 342 hydrodesulfurization HDS hydrogenation 28, 36, 308, 343 of alkene 212 of carbon monoxide 313 hydrogenation of butadiene 56 hydrogenolysis 70, 300 hydrogen shift 216 hydrogen transfer of cyclohexane 192 hydrolysis 63 of acetal 289 287 of carbohydrate of ester 286 of lactose 287 of methyl chloride 291 of methylene chloride 186 of methylhalide 290 of nucleoside 289 hydrodelnitrogenation 121 hydrophilic surface of zeolite 348 hydrophobicity 284 hydrophobic surface of zeolite 348 hydrotreatment 341 hydroxyl group 11 hypothesis 108, 112 inductive effect 84 infrared(1R) 12, 33, 186, 202 infrared diffuse reflectance spectroscopy 11 19 intramolecular hydrogen shift inverse volcano pattern 273 inversion of sucrose 287 ion-exchange of silica gel 99 isobutene 56, 249 isobutyric acid 319 isoelectric point 80 isomerization 90 of alkylbenzene 223 ofbutane 168 of 1-butene 50, 62, 205 of cyclopropane 205 of double bond 36 of epoxide 223 of n-butene 187 of paraffin 220 of u-pinene 186 of 2-pinene 353 12 of 5-vinylbicycloC2,2,1 lheptene isopentane 207 249 isopropyl alcohol 32, 74 isopropyl alcohol-d8 55 isotopic exchange 86, 87 kaoline 351 Keggin structure 163 keto-type 318 Knoevenagel condensation 140, 178 Langmuir type equation Lewis acid 7, 11,62, 118, 186, 239, 248, 341 Lewis acidity 13, 112 Lewis acid site 82, 217 Lewis base 32 Lewis definition limonene 51 d-limonene oxide 353 linalool 353 luminescence 38 LUMO 125 maleic anhydride 322 MAS-NMR 11, 168 mechanism of acidity generation 108 of alcohol dehydration 261 of coke formation 340 of cracking 295 of hydration 250 medicament 353 menthadiene 51, 121 methacrilonitrile 334 metathesis 68 methacrolein 323 methacrylic acid 319 methane-D2 exchange 44 methanol 56, 74, 319 with nitrile 334 methylation 77 of toluene 13 -methyl - 1,3-bu tadiene (isoprene) hydrogenation 310 2-methylbutane 207 methylcyclohexene oxide 123 methylcyclopentane 207 methylethylketone 18 methylformate 57 methylformate decomposition 21 methyl vinyl ketone 334 Michael addition 40 140 Michael reaction microcapsule 351 Mobil/Badger ethvlbenzene Drocess 227 modification of silica gel $9 Subject Index molecular orbital calculation 125 monoclinic phase 56, 201 montmorillonite 351 Mossbauer effect 186 MTG process (methanol to gasoline process) 161, 254 NH.j 8, 65, 68, 70, 74, 81, 184, 336 niobic acid 61 nitration of benzene 102 0-nitroaniline 82 nitrobenzene 50, 53 nitrobenzene anion radical 50 NMR(nuclear magnetic resonance) 11, 186 NO 325 293 octane number 303 tr-olefin 55 olefin from methanol 258 oligomerization 275 of isobutene 278 ofolefins 275 ofpropene 275, 276 of styrene 280 oxidative coupling 19 oxidative dehydrogenation 319 of ethylbenzene 190 oxidation 320 of propane 59 oxidizing property 201 paraldehyde decomposition 121 pentane conversion 207 perfume 353 phenol 23 phenylnitroxide radical 52 pH swing method 80 pigment 353 pillared montmorillonite 132 tr-pinene 51 piperidinc 330 "P-MAS-NMK 194 polycondensation of benzyl chloride polymerization 275 of acetaldehyde 281 of alkene oxide 280 of benzyl alcohol 281 of ether 205 of ethylene oxide 280 of ethylenimine 281 of P-propiolactone 281 of propene 62 of propylene oxide 280 pore size distribution 80 porous glass 318 potentiometric acid- base titration method 11 pressure sensitive recording paper 350 primary structure 164 propene 249, 322, 343, 353 propene-oligomer gasoline 276 propene oligomerization 277, 278 propionitrile 333 propylene chemisorption 76 propylene oxide 223 propylene oxide isomerization 194 proton transfer pseudo-liquid phase 166 P-xylene 13 pyridine 8, 12, 52, 62, 65, 68, 70, 82, 184 pyridinium ion 12 quantum chemical studies 38, 124 rate-determining step 250, 252 reaction intermediate 216 reaction of d-limonene oxide 353 racemization 274 reducing property 50, 53 of N O 58 335 of N 51 reforming 222, 341, 345 reforming process 306 regeneration 345 regional analysis 89 retention of molecular indentity 31 230 359 Saytzeff orientation 262 selectforming 160 self-poisoning 343 shape selectivity 225, 244, 342 shape-selective adsorption 348 shape-selective catalysis 159 shape-selective conversion 278 shape-selective cracking 297 shape-selective hydrocracking 297 sheet silicate 132 side-chain alkylation 29 of aromatics 233 of toluene 159, 233, 234 silanol groups 91 skeletal isomerization 86, 220 of butane 11, 205 of paraffin 205 of pentane 205 softness 164 solid superacid 2, 199 360 SUBJECT INDEX solid superbase 349 steaming 152 stereochemistry 217, 273 styrene 316 sulfate ion 347 superacid 206 superbase 11 supported heteropoly compounds 170 surface acidity 166 surface area 201 84 surface model of alumina surfare OH-density 81 surface-type catalysis 168 synthesis of isopropylbenzene 229 so, temperature-programmed oxidation 345 terpinene 354 tetragonal phase 56, 201 ‘TG (thermogravimetry) Tishchenks reaction of benzaldehyde 16 TPD(temperature programmed desorption) 8, 23, 33, 34, 55, 70 167 of NH,, of pyridine 166 transalkylation 160 of alkylaromatics 241 transfer hydrogenation 312 1,1,2-trichIoroethane 88 tricyclene 51 trimethylamine 330 ru,,3-unsaturated compound urea 116 UV absorption 38 333 Wagner-Meewein rearrangemerlt Wiliamson’ s ether synthesis 40 Wittig-Horner reaction 40 267 XPS (x-ray photoelectron spectroscopy) 18, 202, 203 x-ray 56, 186 xylene 223, 349 0-xylene 13 zeolite as base catalyst Z n O (single crystal) 158 75 Index to Catalysts acidic cation-exchange resin 289 actinide oxides 41, 44 activated A120.1 21 Ag , 224 AICI:! 206, 239, 241 alkali metal 279 alkali metal oxide 234 alkaline earth oxide 262 A120.j 7, 17, 18, 78, 216, 235, 261, 264-269, 281, 286, 304 tr-A120,i 78 21, 79, 290 7-AlZOj c-AltOj 79 AI2Og-BirOp 11 AIIO,j-B20,+ 111 A120:l-C:a0 114 AI,03-Ms0 18, 111, 113, 121, 334 A1,Oj-MoO.I AI?O3-Sb,O, 111 AI,0.i-Ti02 121 A120:+-V205 AI,Oj-WO:{ AI2O3-Zn0 113-115, 121 A1201-Zr02 111 Alp04 21, 188, 216, 266 AIP04-n 156, 157 Al,(SOI),j 21, 187, 248 189 aluminum phosphorous oxide AP ion-exchanged montmorillonite 137 Amberlyst 15 229, 268 anion exchange resin 178 106 As Au 73 A zeolite 142, 249, 287 Bi2-Si02 269 black iron oxide 353 B203 21, 78 boron phosphorous oxide borophosphate 269 B203/Si02 78, 224 BPO, 188, 264, 265 [BI-ZSM-5 259 192 Ca-A zeolite 159, 160, 297 CaC03 16, 21, 353 CaHP04 266 calcium phosphate 195 calcium phosphorous oxide 195 Ca-Ni phosphate 316 CaO 15, 17, 29, 216, 219, 220, 232, 261, 265, 330 Ca(OH), 16 CaPO, 188 188 Ca3(POJ2 Calo(P04)6(0H)2 188, 195, 232, 265, 266, 350 carbonate of alkaline earth metal 279 CaSO, 249 21 CaSO, 0.5H,O cation-exchange resin 261, 289 CaWO, 21 CaX zeolite 159, 160 CdO 77, 216 CdSO,.8H20 187 CeO, 18, 42, 216, 308 187 C e ( S ) H CFjSO3H 239 chabasite 258 clay 128, 292, 352 CoAlPO-5 157, 158 cobalt blue 352 CoMo-A1203 67, 299, 301 COO 71 C02O3 281 c0304 71, 73, 216 CO304-K20 17 copper-chromia oxide 267 + BaO 17, 21, 29 Ba(OH), 21, 29, 40 Ba.i(P04) 266 BaSO, 187, 353 Be0 29 Be(OH)2 280 269 Bi20.,- S i Bi 106 21 Bi20.i 36 362 INDEX To CATALYSTS copper oxide 72 Cr20,-Mg0 334 Cr203 270, 317 crZ(so4)3 249 crysotile 139 CSZsHo spw~zo+o 169 Cs,O 27 C~jPWl20w 167 Csx-zeolite 233, 234 CuC12 206 CuO 72, 317 C U O ~ 72 CuO-MgO 334 C ~ ~ / z P W ~ z o167 C U S O ~ 21, 187, 249 DYD? erionite heteropoly acid 261 ' heteropoly compounds 163 12-heteropolymolybdate 323 HF-AIfOj 84 H mordenite 222 H ~ P M o ~ ~ O M167 HiPMolIVO4o 324 H3PW120+o 164, 216, 285 H2SO4 216 HY 295 hydrated chromium oxide 353 hydrotalcite 280, 327 hydroxide of alkaline earth metal 280 hydroxyapatite 195, 349 H-ZSM-5 227, 232, 244, 283, 297 H-ZSM-11 244 18 ion-exchanged zeolite 216 ion-exchange resin 173, 233, 283, 287 iron oxide 347, 352 sulfate 230 iron ( or 258 m) F-AIZO, 22 Fe/A1203 71 FeC13 239, 241 Fe/MgO 71, 334 FeZ03 18, 70, 301, 317 cr-FeZ03 73 r-Fe203 70 Fe2O3-AI2O3 301 Fe(0H)j 204 Fe203-HZS 200 Fe2Os-MgO 301 Fe203-Nb205 301 Fe203-Si02 300, 301 Fe2O3-SnOZ 301 FezO3-SO2 200 Fe203-S042199, 203, 205 Fe203-Ti02 319 Fe oxide 316 F e203-Zn0 301, 319 Fe,03-Zr02 301, 319 FeS04 187, 239, 241 Fe2(S04)s 249 187 Fe2(SO+)3 xHZO Fe/TiO:, 71 FSOjH 208, 239 FSO:j-SbFj 208 gallosilicate 154 Ga20:j 90 GeO, 18 germanium oxide 104 graphite inclusion compound HDS catalyst 345 kaolinite 353 KCa 28 KHSO4 187 K20 27 KOH-SiOz 88 KO-t-Bu 216 K3PO4 188 K?SO+ 187 K-X zeolite 233 18, 42, 216, 220, 262, 265, 311, 329 La2 LaPO4 188 Lao.8sro.*coo3 59 La-Y zeolite 342 lead oxide 104 Li-doped MgO 319 Li/MgO 341 Li20 27 Li3P04 188, 223 L zeolite 278 233 MeAPO-?t 157 MeSAPO-?t 157 metal-ion exchanged silica gel 274 metallosilicate 154 metal oxide 260 metal phosphate 223, 260 metal sulfate 185, 219, 247 metal sulfates/Si02 216 MgCrzO4 348 17, 23, 29, 114, 216, 219, 220, 308, MgO 311, 313, 317, 330, 334 Index to Catalysts doped with transition metal ion 333 281 MgO-Al203 MgO-Cs 212 Mg(OHl2 21 MgO-K 212 MgO-Na 212 MgO-SiO? 319 MgO-Ti02 116 MgS04 20, 21, 187 MgS04-Si02 218 MgWO4 21 Mg-Y 240 mica 352 mixed oxide 231, 270 Mn02 69 MnSOL 21 187 249 montmorillonite 129, 132, 292, 329 M003 11, 18, 20, 21, 58, 67, 263, 271, 281 MoOj/active carbon 51, 59 Mo03/A1203 51, 59, 67, 300, 341 MoO,/MgO 51, 59 MoO:,/Si02 51, 59, 67 Moo,-SnO? 59 Mo03/Ti02(n) 51, 59 Mo03/Ti02(j) 51, 59 Mo0:3-TiO2-SiO2 59 Mo0,-Ti02 216, 336 M003-Zr02 59 Mo03-Zr02-Ti02 59 Mo-P oxide 321 mordenite 143, 242, 284 M o S ~ 184, 216 Na/AI2O3 22, 216, 308 Nafion' 174, 180, 229-231, 241, 246, 281, 283, 284 Na-Na(OH)2-A1203 211, 212 Na2O 27 Na3PW,2040 167 N a W H 21 Na-Y zeolite 269 Nb205 60 Nb205.HH2O 61, 253 Nd203 44 ( N H J ~ S O ~ 48 nickel sulfate 13, 249, 291 Ni-MgO 334 Ni.Mo/A12O3 299, 301, 343 NiO 71, 249 niobic acid 61, 285 NiO, gold supported on 73 NiO-SO2 72 Ni0-SiO2-AI2O3 71 NiSO+ 21, 249, 250, 253 NiS04.xH20 363 186 oxide of alkaline earth metal of antimony 106 of arsenic 106 of Be 280 ofBi 106 ofCa 280 ofMg 280 of rare earth element 279, 280 41 P 105 PbSOt 187 perfluoresinsulfonic acid 241 phosphoric acid(P205) 105, 231, 247, 269 pillared beidellite 131, 138 pillared clay 128, 137 pillared montmorillonite 131 P205 18, 229 porous glass 317 Pr6OI1 42, 308 Pt/AI2O3 269, 345 Pt-Re 222 Pt-Y zeolite 220 PW,2/Carbon 169 RaO 29 RbzO 27 red iron oxide 353 Re207 69 Re oxide 69 REY (rare earth-exchanged Y zeolite) Rh/A1203 58 Rh/MgO 58 Rh/Nb205 58 Rh/ZrOp 58 295 SAPO-n 156, 157, 278, 279 Sb 106 SbCIS 208 SbFS 206 SbF5- SiO2-AI2O3 10 Se 108 sepiolite 139 sheet silicate 128 silica-alumina 217, 231, 267,268, 281, 284, 292, 292, 342 silica gel 91 having sulfobenzyl groups having sulfo groups 100 silicate 93 silicophosphoric acid 247 silicotungstic acid 247 279 364 INDEX T O CATALYSTS 73 silver oxide Si02 10, 12, 17,18,91 9,10, 18,23,63,88,111, 118, Si02-A1203 119,126,216,220,232,239,240,242, 249,262,263,268,275 effect of 150 SiO2-AI203-NH,F 240 Si02-Ba0 111 Si02-Be0 111 Si02-Ca0 111 Si02-Fe203 111 Si02-Ga203 11 Si02-La203 11 18,111, 120,126,249 Si02-M@ 8,11, 114,115, 120 SiOZ-MoOj 111 Si02-Sr0 Si02-supported N a O H 327 Si02-Ti02 119 Si02-V205 Si02-W03 Si02-Y203 11 Si02-Zn0 114,120 SiO2-ZrO2 111 smectite 138 Sm201 18,44,265 SnCI, 239 Sn02 319,323 Sn02-Mo03 318,323 solid phosphoric acid 247,251, 275,276, 285 216 S02/Si02 SrO 17,21,29,220,330 sulfonated polyorganosiloxane 102 synthesized pigment G 353 talc 353 Ta205 21, 60,64 Ta05.nH20 65 Tb4Oi 42,308 Te 108 Tho2 44,216,261,263,265,267,309, 311, 329 TiCI4 239 Ti(HP0,)2 188 tin oxide 102 Ti02 20,21,47,48,216,232 TiO2-AI2O3 111 Ti02-Bi203 11 TiO2-CdO 111 Ti02-Cu0 111 Ti02-Fe203 11 TiO2-MgO 111, 113-115, 122 Ti02-Pb0 111 Ti02-Si02 109,111, 117 Ti02-Sn02 124 Ti02-S042204,205,240,285 Ti02-Zn0 1 , 114,116,117, 124,253 222,317 Ti02-Zr02-V205 titanium dioxide 353 titanium oxide 352 Ti-V-P 321 TOp-Zr02 113 ultramarine blue 353 ultrastable Y zeolite 293 UO2 44,46 V205 20,21,60,325 V2OS-K2SO+-H2SO+ 18 (V0)2P207 325 11, 21,67,269 W03-A1203 68 W03/Zr02 124 W sulfide 183 wo3 xonotlite X zeolite 140 142,225,287 Y203 18,308 Y zeolite 142,221,225, 232,284,287 zeolite 142,225,292,348 acidity of 150 zinc oxide 353 zinc sulfide 291 zirconium phosphorous oxide 193 Zn 232 ZnO 7,12,21, 216,220,317,319 7,111 Zn0-A1203 ZnO/AI(OH) s/u-alumina 291 ZnO-Bi203 11 ZnO-Fe203 232 ZnO-MgO 111 ZnO-PbO 111 ZnO-Sb,03 77 ZnO- S i 12,77, 1 ZnO-Ti02 77 ZnO-ZrO, 110-112 187 Z n ~ ( P , ) ~ H ~ 21 ZnS 184,249 ZnS04 187 ZnSO, H20 21 Zr(HP04)2 188 17, 21, 23, 47,51,56-59, 216, 220, ZrOz 240,261,309,311,312 111 ZrOZ-CdO Index to Catalysts Z r ( O H ) + 55 ZrO>-NH+F 240 ZrO1-SnO1 124 %r01-Sn01-S04LZrO1-SO, 284 240 365 Zr02-SOt2199, 201, 205, 239, 240 ZSM-5 9, 143, 225, 228, 235, 237, 239, 240, 245, 254, 259, 270, 277, 279, 285, 286, 297 ZSM-11 297 This Page Intentionally Left Blank Studles In Surface Sclence and Catalysls Mvlsory Edltors: B Delmonl.UnlversltB Cathollque de Louvaln, Louvaln-la-Neuve, Belglum J.T Yates, U n l v e r s l t y o f Plttsburgh, Plttsburgh, PA, U.S.A Volume Preparatlon of Catalysts S c l e n t l f l c Bases for t h e P r e p a r a t l o n o f Heterogeneous Catalysts Proceedlngs o f t h e Flrst l n t e r n a t l o n a l Symposlum held a t t h e Solvay Research Centre, Brussels, October 14-17, 1975 e d l t e d by B Delmn, P.A Jacobs and Poncelet Volume The Control of the Reactlvlty o f Sollds A C r l t l c a l Survey o f t h e Factors t h a t Influence t h e R e a c t l v l t y o f Sollds, w l t h Speclal Emphasls on t h e Control o f t h e Chemlcal Processes I n R e l a t l o n t o Practlcal Appllcatlons by V.V Boldyrev, M Bulens and B Delmn Volume Preparatlon of Catalysts I I S c l e n t l f l c Bases f o r t h e P r e p a r s t l o n o f Heterogeneous Catalysts Proceedlngs o f t h e Second l n t e r n a t l o n a l Symposlum, Louvaln-la-Neuve, September 4-7, 1978 e d l t e d by B Delnon, P Grange P Jacobs and Poncelet Volume Growth and Propertles o f Metal Clusters A p p l l c a t l o n s t o C a t a l y s l s and t h e Photographlc Process Proceedlngs of t h e 32nd l n t e r n a t l o n a l Meetlng o f t h e Soclbt6 de Chlmle Physique, Vllleurbanne, September 24-28 1979 ed l t e d by J Bourdon Volume Catalysls by Zeolites Proceedlngs o f an l n t e r n a t l o n a l Symposlum CNRS organlzed by t h e l n s t l t u t de Recherche sur l a Catalyse Vllleurbanne, and sponsored by t h e Centre Natlonal de Recherche S c l e n t l f l q u e , Ecul l y (Lyon), September 9-11, 1980 Vedrlne e d l t e d by B lmellk C Naccache, Y Ben Taarlt, J.C Coudurler and H Prallaud Volume Catalyst Deactlvatlon Proceedlngs of t h e l n t e r n a t l o n a l Symposlum, Antwerp, October 13-15 1980 e d i t e d by B Dellon and 6.F Fronent Volume New Horlzons I n Catalysls Proceedlngs o f t h e t h l n t e r n a t l o n a l Congress on Catalysls Tokyo, June 30 J u l y 4, 1980 e d i t e d by T Selyma and K Tanabe Volume Catalysls by Supported colplexes - - by Yu.1 Volume Volume 10 - Yerndtov B.N Kuznetsov and V.A Zdthamv Physlcs of Solid Surfaces Proceedlngs o f t h e Symposlum held I n Bechyne, Czechoslovakla, September 29 October 3, 1980 e d l t e d by M Lbznlcka - Adsorptlon a t the Gas-Sol Id and Llquld-Sol Id Interface Proceed lngs o f an l n t e r n a t l o n a l Symposlum held I n Alx-en-Provence, September 21-23 1981 e d l t e d by J Rouquerol and K.S.W Slng Volume 11 Metal-Support and Metal-Mdltlve Effects I n Catalysls Proceed lngs of an l n t e r n a t l o n a l Symposlum organlzed by t h e l n s t l t u t de Recherches CNRS Vllleurbanne, and sponsored by t h e Centre sur l a Catalyse Natlonal de l a Recherche S c l e n t l f l q u e , E c u l l y (Lyon), September 14-16, 1982 e d l t e d by lllellk C Naccache G Courdurler H Prallaud P krlaudeau P Gallezot G.A Martin and J.C Vedrlne - - - - Volume 12 ProDertles Metal Wlcrostructures In Zeolltes PreDaration Appl l c a t l o n s Proceed lngs of a Workshop, Bremen, Sepiember 22-24, 1982 e d i t e d by P.A Jacobs N.I Jaeger P J l r u and Schulz-Ekloff Volume 13 Msorptlon on Metal Surfaces An I n t e g r a t e d Approach e d l t e d by J BBnard Volume 14 Vlbratlon at Surfaces Proceedings of t h e T h l r d l n t e r n a t l o n a l Conference, Asllcinar, C a l l f o r n l a U.S.A., September 1-4, 1982 e d l t e d by C.R Brundle and H l b r a l t z Volume 15 Heterogeneous Catalytlc Reactlons lnvolvlng Molecular Oxygen by 6.1 Golcdets Volume 16 Preparatlon of Catalysts 1 S c l e n t l f l c Bases f o r t h e P r e p a r a t i o n o f Heterogeneous Catalysts Proceedlngs o f t h e T h i r d l n t e r n a t l o n a l Symposium, Louvaln-la-Neuve, September 6-9 1982 e d l t e d by PonceIet P Grange and P.A Jacobs Volume 17 Spillover of Adsorbed Specles Proceedlngs o f t h e l n t e r n a t l o n a l Symposlum, Lyon-Vllleurbanne, September 12-16, 1983 e d l t e d by G.W PaJonk S.J Telchner and J.E GemaIn Volume 18 Structure and Reactlvlty o f Wodlfled Zeolltes Proceedlngs o f an I n t e r n a t l o n a l Conference, Prague, J u l y 9-13, 1984 e d i t e d by P.A Jacobs N.I Jaeger P Jlru V.B Kazansky and SchuIz-Ekloff Volume 19 Catalysls on the Energy Scene Proceedlngs of t h e t h Canadlan Symposlum Quebec, P.Q., September 30 e d l t e d by S Kal lagulne and A Mahay Vol ume 20 - October 3, 1984 Catalysls by k l d s and Bases Proceedlngs of an l n t e r n a t l o n a l Symposium organized by t h e l n s t l t u t de Recherches sur l a Catalyse CNRS Vllleurbanne and sponsored by t h e Centre National de la Recherche S c l e n t l f l q u e Vllleurbanne (Lyon), September 25-27, 1984 e d l t e d by B lnellk C Naccache G.Coudurler Y Ben TaarIt and J.C Vedrlne - Volume 21 Adsorptlon and Catalysls on Oxlde Surfaces Proceedlngs o f a Symposlurn, Brunel U n l v e r s l t y , Uxbridge, June 28-29, 1984 edlted by W Che and G.C Bond Vo I ume 22 Unsteady Processes In Catalytic Reactors by Yu.Sh Matros Vol ume 23 Physlcs of SolId Surfaces 1984 e d l t e d by J KwkaI - Vol ume 24 Zeolltes Synthesis Structure Technology and Appllcatlon Proceedlngs of t h e l n t e r n a t l o n a l Symposlum, Portoror-Portorose, September 3-8, 1984 e d l t e d by DrzaJ, S Hocevar and S PeJovnIk Vol ume 25 Catalytlc Polyaerlzatlon of Oleflns Proceedlngs o f the l n t e r n a t l o n a l Symposium on Future Aspects o f O l e f l n PolymerIration, Tokyo, Japan J u l y 4-68 1985 edited by T K e l l and K !bga Volume 26 Vlbratlons a t Surfaces 1985 Proceedlngs o f t h e Fourfh l n t e r n a t l o n a l Conference, Bowness-on-Wlndermeret U.K., September 15-19, 1985 ed l t e d by D.A King N.V Richardson and S Hol l a a y Volume 27 Catalytlc Hydrogenatlon by L Cerveny Vol urne 28 New Developments In Zeollte Sclence and Technology Proceedlngs o f t h e t h I n t e r n a t i o n a l Z e o l i t e Conference, e d l t e d by Y Murdcanl, A I I J I M and J.W Tokyo August 17-22, Ward 1986 Volume 29 Uetal Clusters I n Catalysls edlted by B.C Gates L Guczl and H KMzInger Yo1 ume 30 Catalysls and Autoratlve Pollution Control Proceedlngs o f t h e F l r s t l n t e r n a t l o n a l Symposium (CAPOC I), Brussels, September 8-11, 1986 e d i t e d by A Crucq and A Frennet Volume 31 Preparatlon o f Catalysts IV S c l e n t l f l c Bases f o r t h e P r e p a r a t l o n o f Heterogeneous Catalysts Proceedlngs o f t h e Fourth l n t e r n a t l o n a l Symposium, Louvaln-la-Neuve, September 1-4, 1986 e d l t e d by B D e l m P Grange P.A Jacobs and Poncelet Vol ume 32 Volume 33 Thln Metal Fllms and Gas Chaisorptlon e d i t e d by P Wlsslann Synthesls of Hlgh-Slllca Alumlnosollcate Zeolltes Jacobs and J.A Martens by P.A Vol ume 34 Catalyst Deactlvatlon 1987 Proceedlngs o f t h e t h I n t e r n a t i o n a l October 1, 1987 Symposlum Antwerp, September 29 edlted by B Delmn and G.F Froaent Volume 35 Keynutes i n Energy-Related Catalysls edlted by S Kallagulne Vol ume 36 - Uethane h v e r s l o n Proceedlngs of a Symposlum on t h e P r d u c t l o n s o f Fuels and Chemlcals from Natural Gas, Auckland, A p r l I 27-30, edlted by D.M Blbby C.D Chang R.F Hae and S Yurchdc Volume 37 1987 Innovation I n Zeolite Uaterlals Sclence Proceedlngs of an I n t e r n a t i o n a l Symposlum, Nleuwpoort (Eelglum), September 13-17, e d l t e d by P.J Grobetr W.J Wortler E.F Vansant and 1987 SchuIz-Ekloff Vol ume 38 Catalysls 1987 Proceedlngs of t h e 10th North American Meeting o f t h e C a t a l y s l s Society, San Dlego, CA, May 7-22, 1987 edlted by J.W Ward Vol ume 39 Characterlzatlon of Porous Sollds Proceedlngs o f t h e IUPAC Symposlum (COPS I ) , Bad Soden a.Ts.1 F.R.G., A p r l l 26-29, 1987 edlted by K.K Unger J Rouquerol, K.S.W Slng and H K r a l Vol ume 40 Physlcs of Solid Surfaces 1987 edlted by J KoukaI Volume 41 Heterogeneous Catalysls o f Flne C h a l c a l s edlted by W Gulsnet J Barrault C Bouchoule D Duprez C l b n t a s s l e r and PBrot Vol ume 42 Laboratory Studles o f Heterogeneous C a t a l y t i c Processes by E.G C h r l s t o f f e l and Psbl Vol ume 43 C a t a l y t l c Processes under Unsteady-State Condltlons by Yu.Sh Matros Vol ume 44 Successful Design of Catalysts edlted by T l n u l Vol ume 45 T r a n s l t l o n Metal Oxldes Surface C h l s t r y and Catalysls by H.H Kung Vol ume 46 Zeolltes as Catalysts, Sorbents and Detergent Bullders Appllcatlons and Innovatlons Proceedlngs o f an lnternatlonal Symposlum WDrzburg, F.R.G., September 4-8, 1988 edlted by H.G Karge and J Weltkap Vol ume 47 Photochemlstry on Sol I d Surfaces edlted by W Anpo and T Matsuura Vo I ume 48 Structure and R e a c t l v l t y of Surfaces Proceedlngs o f a European Conference, Trleste, I t a l y , September 13-16, 1988 ed lted by C Ibrterra A Zecch Ina and Costa Vol ume 49 Zeolltes: Facts, Flgures, Future Proceedlngs of t h e 8th lnternatlonal Zeol I t e Conference Amsterdam, The Netherlands, July 10-14, 1989 edlted by P.A Jacobs and R.A van Santen Vol ume 50 Hydrotreatlng Catalysts Preparatlon, Characterlzatlon and Performance Prcceedlngs o f the Annual lnternatlonal AlChE Meetlng, Washlngton DC November 27 December 2, 1988 ed lted by W.L Occel II and R.G Anthony - Future Requlremnts and Developlent - Volume 51 - Ner SolId k l d s and Bases t h e l r c a t a l y t l c propertfes by K T a n d m W Wlsonor Y On0 and H Hattorl ... Definition and Classification of Solid Acids and Bases In accordance with the above definitions, a summarized list of solid acids and bases is given in Tables 1.1 and 1.2, The first group of solid acids. .. Definition and Classification of Solid Acids and Bases Determination of Acidic and Basic Properties on Solid Surfaces 2.1 Acidic Property Strength and Amount of Solid Acid Bnansted and Lewis Acid... monograph "Solid Acids and Bases" was published in 1970 During this period many new kinds of solid acids and bases have been found and synthesized The surface properties (in particular, acidic and basic