Molecular Sieve Catalysts

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1 Molecular Sieve Catalysts P. MICHIELS and O. C. E. DE HERDT European Patent Office, The Hague, The Netherlands Pergamon Infoline Inc. a member of the Pergamon Group PERGAMON PRESS OXFORD NEW YORK BEIJING FRANKFURT SÄO PAULO SYDNEY TOKYO TORONTO

CONTENTS Page PREFACE NOTE ON CITED PATENT DOCUMENTS vn PART ONE : GENERAL PROCESSES INTRODUCTION CHAPTER I 1 MOLECULAR SIEVE CATALYSTS IN GENERAL SYNTHESIS OF CRYSTALLINE ZEOLITIC ALUMINOSILICATES

2 CONTENTS Page PREFACE NOTE ON CITED PATENT DOCUMENTS vn PART ONE : GENERAL PROCESSES INTRODUCTION CHAPTER I 1 MOLECULAR SIEVE CATALYSTS IN GENERAL SYNTHESIS OF CRYSTALLINE ZEOLITIC ALUMINOSILICATES Synthesis of the zeolite Direct synthesis of a compositlon containig zeolite in a matrix Conversion of one type of crystalline alumlnosi1icate zeolite into another type INCREASING THE SILICA/ALUMINA RATIO; DEALUMINATION 11 TREATMENT OF CRYSTALLINE ALUMINOSILICATE ZEOLITES 13 Elimination of transition metal elements 13 Reduction of crystal1inity 13 Selective deactivation 13 Activation by oxygen and/or hydrogen treatment 14 Treatment with halogens 15 ix

x CONTENTS 4 : SILICA-MODIFIED ZEOLITES 15 5 : ALUMINA-COATED ZEOLITES 16 6 : TECHNIQUES FOR ION-EXCHANGE AND/OR FOR 17 INTRODUCTION OF METALLIC ELEMENTS IN OR ON THE SIEVE 7 : ION-EXCHANGE METHODS

3 x CONTENTS 4 : SILICA-MODIFIED ZEOLITES 15 5 : ALUMINA-COATED ZEOLITES 16 6 : TECHNIQUES FOR ION-EXCHANGE AND/OR FOR 17 INTRODUCTION OF METALLIC ELEMENTS IN OR ON THE SIEVE 7 : ION-EXCHANGE METHODS TO REDUCE THE SODIUM CONTENT 19 8 : INTRODUCTION OF SPECIFIED METALS BY ION-EXCHANGE 21 9 : COMPOSITIONS OF METALS WITH MOLECULAR SIEVES : COMPOSITIONS OF CRYSTALLINE ALUMINOSILICATE 25 ZEOLITES WITH CATALYTIC ELEMENTS AND WITH AMORPHOUS OXIDES 11 : MATRIX AND BINDING AGENT 28 Chemical composition of the matrix or 28 binding agent Preparatlon and treatment of the matrix 30 Matrix or catalyst ingredients characterized 31 by their surface and porosity parameters Catalyst Supports containing the zeolite 32 material in their pores 12 : PREPARATION OF THE PARTICLES 32 By spray drying 32 By other particle forming techniques; 34 extrusion; granulating Adding materials during particle formation 35 Extruded products of partlcular form 36 After-treatment of the matrix-zeolite composites 36 Reduction of the particle size 37 CHAPTER II : FAUJASITE INTRODUCTION : 2 : Zeolite X D value of reflection in Ä Zeolite Y SYNTHESIS OF FAUJASITE TYPE ALUMINOSILICATE ZEOLITES New synthetic forms of faujasite DEALUMINATION

CONTENTS xi 3 : PREPARATION OF DEFECT-ZEOLITES 50 4 : ULTRA-STABLE Y-TYPE ZEOLITES 50 Other processes for lon-exchange of faujasites 53 5 : FLUORIZATION 55 6 : CALCINATION 56 7 : FAUJASITE-TYPE

4 CONTENTS xi 3 : PREPARATION OF DEFECT-ZEOLITES 50 4 : ULTRA-STABLE Y-TYPE ZEOLITES 50 Other processes for lon-exchange of faujasites 53 5 : FLUORIZATION 55 6 : CALCINATION 56 7 : FAUJASITE-TYPE COMPOSITIONS CONTAINING 56 ACTIVE METALS 8 : COMPOSITIONS INCLUDING CATALYTICALLY ACTIVE 60 METALS AND NON-ZEOLITIC INORGANIC OXIDES 9 : CATALYST COMPOSITIONS COMPRISING OTHER OXIDES : PREPARATION OF THE CATALYST PARTICLES : CATALYST CONTAINING ZEOLITE X : CATALYST CONTAINING ZSM CHAPTER III : MORDENITE 69 INTRODUCTION 69 1 : SYNTHESIS 70 Dyrect synthesis 70 Other synthesis methods 71 2 : DEALUMINATION 71 3 : ION EXCHANGE 73 4 : ACTIVATION 74 5 : SELECTIVE DEACTIVATION 75 6 : CATALYSTS COMPRISING COMBINATIONS OF METALLIC 75 ACTIVE COMPONENTS AND MORDENITE 7 : COMPOSITIONS OF MORDENITE WITH OTHER CATALYSTS 78 OR WITH OXIDES CHAPTER IV 1 2 ZEOLITES OF THE CHABAZITE TYPE ERIONITE OFFRETITE

xi i CONTENTS Synthesis lon-exchange Composltions 3 : 4 : GMELINITE ZEOLITE L Patents concerning the group In general CHAPTER V FERRIERITE INTRODUCTION 1 2 3 SYNTHESIS TREATMENT OF NATURAL FERRIERITE

5 xi i CONTENTS Synthesis lon-exchange Composltions 3 : 4 : GMELINITE ZEOLITE L Patents concerning the group In general CHAPTER V FERRIERITE INTRODUCTION SYNTHESIS TREATMENT OF NATURAL FERRIERITE CATALYTIC COMPOSITIONS INCLUDING FERRIERITE CHAPTER VI : OTHER NATURAL ZEOLITIC CRYSTALLINE ALUMINOSILICATES 1 : 2 : CLINOPTILONITE NATURAL TUFS FROM JAPAN CHAPTER VII : ZEOLITE A CHAPTER VIII : ZEOLITES OF THE ZSM-5 FAMILY INTRODUCTION 1 : THE ZSM-5 FAMILY Contraint index ZSM-5 ZSM-11 ZSM-12 ZSM-23 ZSM-35 and ZSM-38 ZSM-48 2 : SYNTHESIS OF ZSM-5 GROUP ZEOLITES New synthesis methods for ZSM-5 New synthesis methods for ZSM-11 ZSM-5/ZSM-11 Intermediates New synthesis of ZSM-12 Synthesis of ZSM-35

CONTENTS xiii Synthesis of ZSM-5 type catalysts 117 ZSM-5 type catalysts havlng core and shell 119 of different compositlons 3 : DEALUMINATION 120 4 : REMOVING ORGANIC CATIONS FROM THE ZEOLITE 120 5

6 CONTENTS xiii Synthesis of ZSM-5 type catalysts 117 ZSM-5 type catalysts havlng core and shell 119 of different compositlons 3 : DEALUMINATION : REMOVING ORGANIC CATIONS FROM THE ZEOLITE : MODIFICATION BY TREATMENT WITH ORGANIC COMPOUNDS : STABILISATION/MODIFICATION : ACTIVATION 122 Activation of zeolites havlng a high 123 silica/alumina ratio 8 : REDUCING ACTIVITY : INCORPORATION OF ELEMENTS 127 Introductlon of slllca 127 Introduction of alumina 127 Introductlon of elements to enhance 128 the para-selectivlty StabiUsatlon of zinc containing ZSM-5 catalysts 132 Modificatlon with gallium : COMBINATION WITH CATALYTICALLY ACTIVE METALS : ZSM-5 FAMILY ZEOLITES ADMIXED WITH MATRIX 136 FORMING MATERIALS AND/OR OTHER CATALYSTS Hydroconversion catalysts 136 Catalysts for the conversion of synthesis 137 gas into liquid hydrocarbons Cracking catalyst compositlons 139 Matrixes of specific compositlon : PREPARING CATALYST PARTICLES 140 CHAPTER IX : OTHER SYNTHETIC CRYSTALLINE ALUMINOSILICATES : CRYSTALLINE ALUMINOSILICATES RELATED 141 TO THE ZSM-5 FAMILY 2 : CATALYSTS OF (J-ZEOLITE FAMILY : ERIONITE RELATED ZEOLITES : CATALYSTS OF THE LEVYNITE TYPE : CATALYSTS OF THE HERSCHELITE TYPE 163

xiv CONTENTS 6 FU-1 CATALYSTS 164 7 ZEOLITE ZK-5 165 8 ZSM-4 166 9 OTHER SYNTHETIC ALUMINOSILICATE ZEOLITES 167 ZSM-22 / Nu-10 Catalysts containing zeolites I or J 171 185 CHAPTER X : MOLECULAR

7 xiv CONTENTS 6 FU-1 CATALYSTS ZEOLITE ZK ZSM OTHER SYNTHETIC ALUMINOSILICATE ZEOLITES 167 ZSM-22 / Nu-10 Catalysts containing zeolites I or J CHAPTER X : MOLECULAR SIEVES OTHER THAN ALUMINOSILICATES 187 OR CONSISTING OF ALUMINOSILICATES CONTAINING OTHER ELEMENTS IN THEIR FRAMEWORK 1 : METAL (ALUMINO)SILICATES IN GENERAL : BORO(ALUMINO)SILICATES 190 Synthesis 190 Treatment 193 Compositlons 194 Shaping 194 Reactivation 194 Tltanoborosilicate : GALLO- OR INDIO(ALUMINO)SILICATES : ARSENIUM SILICATES : VANADIUM SILICATES : IRON (ALUMINO)SILICATES : COBALT (ALUMINOSILICATES : CHROMIA (ALUMINO)SILICATES : (ALUMINOSILICATES OF RARE EARTHS : NIOBIUM SILICATES : (ALUMINO)SILICATES OF ZIRCONIUM, HAFNIUM 207 OR TELLURIUM 12 : SILICATES OF ZINC, TIN OR TITANIUM : BERYLLO-(ALUMINOSILICATES : PHOSPHO-(ALUMINO)SILICATES : METALLOPHOSPHATE ZEOLITES 212

CONTENTS xv 16 : SILICA-POLYMORPH(SILICALITE) 212 Catalyst compositions 215 17 : CRISTALS WITH A CORE DIFFERENT FROM THE SHELL 217 18 : CARBONACEOUS MOLECULAR SIEVES 217 CHAPTER XI : MIXTURES OF

8 CONTENTS xv 16 : SILICA-POLYMORPH(SILICALITE) 212 Catalyst compositions : CRISTALS WITH A CORE DIFFERENT FROM THE SHELL : CARBONACEOUS MOLECULAR SIEVES 217 CHAPTER XI : MIXTURES OF DIFFERENT KINDS OF MOLECULAR SIEVE CATALYSTS 219 CHAPTER XII : REGENERATION, REACTIVATION REDISPERSION OF NOBLE METALS REMOVING METALLIC CONTAMINANTS OTHER REACTIVATION PROCESSES PART TWO HYDROCARBON PROCESSES IN WHICH MOLECULAR SIEVE CATALYSTS ARE USED 229 INTRODUCTION 231 CHAPTER I : CATALYTIC CRACKING 1 : CRACKING Cracking wlth faujasites Cracking with zeolite-y catalysts Cracking with mordenite Cracking with ZSM-5 type catalysts Cracking with other types of catalysts Cracking with special matrices containing catalysts : GENERAL CATALYSTS General Regeneration of cracking catalyst Passivation Co-combustors containing catalysts Addition of sulphur oxide acceptors CHAPTER II : HYDROCRACKING : HYDROCRACKING WITH MOLECULAR SIEVES IN GENERAL 275

9 xvi CONTENTS. 2 : HYDROCRACKING WITH MOLECULAR SIEVES COMPRISING 281 PT-GROUP METALS 3 : HYDROCRACKING WITH ZSM-TYPE CATALYSTS : HYDROCRACKING WITH OTHER TYPES OF ZEOLITES : PREPARATION OF HYDROCRACKING ZEOLITIC CATALYSTS : REGENERATION AND REJUVENATION OF ZEOLITIC 287 HYDROCRACKING CATALYSTS CHAPTER III : HYDROTREATING REACTIONS : REMOVAL OF HETEROATOMS 2 : HYDROGENATION OF UNSATURATED COMPOUNDS CHAPTER IV : HYDROCRACKING/HYDROREFINING 293 CHAPTER V REFORMING OR AROMATIZATION OF HYDROCARBONS BOILING IN THE NAPHTHA BOILING RANGE : GENERAL 2 : SPECIAL TYPES OF CATALYSTS : ZSM-TYPE CATALYSTS ~~ 300 CHAPTER VI : CARBON SKELETON CHANGES AND OTHER HYDROGENE TREATMENTS : ALKYLATION General Aikylation processes using ZSM-type catalysts Aikylation processes using special catalysts 2 : DEALKYLATION, HYDRODEALKYLATION 3 : ISOMERISATION 4 : SELECTIVE CRACKING, DEWAXING ZSM-type catalysts Other catalysts

CONTENTS xvii CHAPTER VII : CONVERSION OF OXYGEN CONTAINING COMPOUNDS INTO HYDROCARBONS 325 1 : CONVERSION OF SYNTHESIS GAS INTO HYDROCARBONS 2 : CONVERSION OF OXYGEN

10 CONTENTS xvii CHAPTER VII : CONVERSION OF OXYGEN CONTAINING COMPOUNDS INTO HYDROCARBONS : CONVERSION OF SYNTHESIS GAS INTO HYDROCARBONS 2 : CONVERSION OF OXYGEN COMPOUNDS INTO GAS Uslng ZSM type of catalysts Using other types of catalysts LIST OF CITED PATENT DOCUMENTS 335 LIST OF PATENTEES 351 SUBJECT INDEX 383

Catalytic Chemistry. Bruce C. Gates. John Wiley & Sons, Inc. New York Chichester Brisbane Toronto Singapore. University of Delaware ^.'-'.

Catalytic Chemistry. Bruce C. Gates. John Wiley & Sons, Inc. New York Chichester Brisbane Toronto Singapore. University of Delaware ^.'-'. : s / ; '.... ;. : : ^.'-'. Catalytic Chemistry Bruce C. Gates University of Delaware John Wiley & Sons, Inc. New York Chichester Brisbane Toronto Singapore Contents List of Notation xix 1 INTRODUCTION