Trujillano / Gil Pillared Clays and Related Catalysts

1. Auflage 2010
ISBN: 978-1-4419-6670-4
Verlag: Springer-Verlag
Format: PDF
Kopierschutz: Wasserzeichen (»Systemvoraussetzungen)

E-Book, Englisch, 522 Seiten

Since the first works introducing the aluminum intercalated clay family in the early 1970s, interest in the synthesis of pillared interlayered clays has increased tremendously, especially research into the properties and applications of new synthesis methods. The need for solids that could be used as cracking catalysts with larger pores than zeolitic materials has spurred the synthesis of new porous materials from clays. Pillared Clays and Related Catalysts reviews the properties and applications of pillared clays and other layered materials used as catalysts, focusing on: the acidity of pillared clays and the effect it has on catalytic performance the use of pillared clays as supports for catalytically active phases, and the use of the resulting solids in environmentally friendly reactions the applications of the selective reduction of NOx the comparison between the reactions of pillared clays and anionic clays.

Autoren/Hrsg.

Trujillano, Raquel

Gil, Antonio

Inhaltsverzeichnis

1;Foreword;4
2;Preface;6
3;Contents;9
4;Contributors;11
5;1 Microwave Effect on Clay Pillaring;15
5.1;1.1 Introduction;15
5.2;1.2 Experimental;17
5.3;1.3 Determinant Conditions;17
5.3.1;1.3.1 Irradiation Time;17
5.3.1.1;1.3.1.1 Alumina-Pillared Montmorillonite;17
5.3.1.2;1.3.1.2 Zirconia-Pillared Montmorillonite;19
5.3.1.3;1.3.1.3 Titania-Pillared Montmorillonite;20
5.3.1.4;1.3.1.4 Multimetallic-Pillared Montmorillonite;21
5.3.1.5;1.3.1.5 Remarks;22
5.3.2;1.3.2 Clay to Water Ratio;22
5.3.2.1;1.3.2.1 Alumina-Pillared Montmorillonite;22
5.3.2.2;1.3.2.2 Iron oxide-Pillared Montmorillonite;22
5.3.2.3;1.3.2.3 Remarks;23
5.3.3;1.3.3 Metal to Clay Ratio;23
5.3.3.1;1.3.3.1 Titanium-Pillared Clays;23
5.3.3.2;1.3.3.2 Zirconium-Pillared Montmorillonite;23
5.3.3.3;1.3.3.3 Remarks;24
5.3.4;1.3.4 Ultrasound Versus Microwave Irradiation;24
5.3.4.1;1.3.4.1 Remarks;26
5.4;1.4 Other Clays;27
5.4.1;1.4.1 Clay Synthesis;27
5.4.2;1.4.2 Aluminum-Intercalated Samples;27
5.4.3;1.4.3 Titania-Pillared Clays;27
5.4.4;1.4.4 Chromia and Tin Oxide-Pillared Montmorillonites and Laponites;28
5.4.5;1.4.5 Saponite Pillared with Fe-Organometallic by Microwave and Ultrasound Irradiation;29
5.4.6;1.4.6 Pillared Anionic Clays;29
5.4.6.1;1.4.6.1 Polyvanadate-Intercalated Hydrotalcites;29
5.4.6.2;1.4.6.2 PO430 and P2O740-Intercalated Hydrotalcites ;30
5.4.6.3;1.4.6.3 PET-Hydrotalcite Nanocomposites ;30
5.4.6.4;1.4.6.4 Remarks;30
5.5;1.5 Conclusion;31
6;References;31
7;2 Pillared Interlayered Clays as Adsorbents of Gases and Vapors;36
7.1;2.1 Introduction;36
7.2;2.2 Adsorption of Volatile Organic Compounds (VOCs);37
7.2.1;2.2.1 As Probe Molecules;37
7.2.2;2.2.2 For Separation/Purification;39
7.3;2.3 Adsorption of Water;41
7.4;2.4 Adsorption of Natural and Biogas Components;43
7.5;2.5 Conclusion;53
8;References;53
9;3 Characterization and Catalytic Performance of Montmorillonites with Mixed Aluminium/Lanthanide Pillars;56
9.1;3.1 Introduction;56
9.2;3.2 Experimental Section;57
9.2.1;3.2.1 Starting Material;57
9.2.2;3.2.2 Synthesis;57
9.2.2.1;3.2.2.1 Preparation of the Pillaring Agents;57
9.2.2.2;3.2.2.2 Pillaring Process;58
9.3;3.3 Results and Discussion;58
9.3.1;3.3.1 X-ray Diffraction (CuK radiation);59
9.3.2;3.3.2 MAS NMR Spectra;59
9.3.3;3.3.3 Textural Analysis;62
9.3.4;3.3.4 Acidity of Samples;67
9.3.5;3.3.5 Catalytic Activity;69
9.4;3.4 Conclusions;76
10;References;76
11;4 Synthetic Hectorite: Preparation, Pillaring and Applications in Catalysis;79
11.1;4.1 Introduction;79
11.2;4.2 Properties and Structure of Hectorite;81
11.3;4.3 Synthesis of Hectorite-Like Solids;83
11.3.1;4.3.1 A Brief History of Synthetic Hectorite;83
11.3.2;4.3.2 Synthesis Variables and Structure Characteristics;89
11.4;4.4 Pillaring and Further Modification;94
11.5;4.5 Catalysis;98
11.6;4.6 Summary and Prospects;102
12;References;103
13;5 Transition Metal Oxide-Pillared Clay Catalyst: Synthesis to Application;110
13.1;5.1 Introduction;110
13.2;5.2 Pillaring Process;111
13.2.1;5.2.1 Polynuclear Metal Oxo--hydroxo Cations;112
13.2.2;5.2.2 Cationic Metal Complex;112
13.2.3;5.2.3 Metal Cluster Complex;112
13.2.4;5.2.4 Positively Charged Colloidal Particles;113
13.3;5.3 Synthesis of Transition Metal Oxide-Pillared Clays;113
13.3.1;5.3.1 Titanium Oxide-Pillared Clays;116
13.3.2;5.3.2 Iron Oxide-Pillared Clays;117
13.3.3;5.3.3 Chromium Oxide-Pillared Clays;119
13.3.4;5.3.4 Manganese Oxide-Pillared Clay;121
13.3.5;5.3.5 Mixed Transition Metal Oxide-Pillared Clay;121
13.4;5.4 Acidity of Pillared Clay;123
13.4.1;5.4.1 Acid Activation of Clay Before Pillaring;124
13.4.2;5.4.2 Anion-Supported Pillared Clay;124
13.5;5.5 Catalytic Reaction;126
13.5.1;5.5.1 Acidic Reaction;126
13.5.2;5.5.2 Redox Reaction;127
13.5.3;5.5.3 Selective Catalytic Reduction (SCR) of NO x ;128
13.5.4;5.5.4 Photocatalytic Reaction;130
13.6;5.6 Conclusions;131
14;References;132
15;6 Use of Pillared Clay-Based Catalysts for Wastewater Treatment Through Fenton-Like Processes;140
15.1;6.1 Introduction;140
15.1.1;6.1.1 Water Treatment with Advanced Oxidation Processes;140
15.1.2;6.1.2 The Use of Pillared Clays in Heterogeneous Fenton-Based Processes;142
15.1.3;6.1.3 Pollutants Degraded or Wastewaters Treated with Pillared Clay-Based Catalysts;144
15.2;6.2 Fenton and Fenton-Like Process;145
15.2.1;6.2.1 Introduction;145
15.2.2;6.2.2 Effect of the Main Operating Conditions;147
15.2.2.1;6.2.2.1 Effect of the Initial pH;147
15.2.2.2;6.2.2.2 Effect of the Temperature;151
15.2.2.3;6.2.2.3 Effect of the Initial H 2 O 2 Concentration;152
15.2.2.4;6.2.2.4 Effect of the Catalyst Load;153
15.2.2.5;6.2.2.5 Effect of the Initial Parent Compound Concentration;157
15.2.2.6;6.2.2.6 Heterogeneous Versus Homogenous Process;157
15.2.3;6.2.3 Effect of the Type of Catalyst/Salt Precursor;159
15.2.4;6.2.4 Some Technological Issues;161
15.2.4.1;6.2.4.1 Catalyst Stability;161
15.2.4.2;6.2.4.2 Use of Continuous Flow Reactors;164
15.2.5;6.2.5 Mechanistic Studies;165
15.3;6.3 Modeling;165
15.3.1;6.3.1 Phenomenological Models;166
15.3.1.1;6.3.1.1 Langmuir--Hinshelwood Rate Equations;166
15.3.1.2;6.3.1.2 Apparent First-Order Rate Equations;170
15.3.2;6.3.2 Non-Phenomenological Models;170
15.4;6.4 Conclusions;172
16;References;173
17;7 Catalytic Wastewater Treatment Using Pillared Clays;177
17.1;7.1 Introduction;177
17.1.1;7.1.1 Issues in Using Solid Catalysts in Wastewater Treatment;179
17.1.2;7.1.2 PILCs and Catalytic AOP Methods;180
17.2;7.2 Wet Air Catalytic Oxidation ( WACO );182
17.2.1;7.2.1 PILC-Based Catalysts for Wet Oxidation;183
17.3;7.3 Wet Hydrogen Peroxide Catalytic Oxidation (WHPCO);186
17.3.1;7.3.1 Heterogeneous Versus Homogeneous Reactions;188
17.3.2;7.3.2 Mechanism of Organic Transformation;192
17.3.3;7.3.3 A Survey of Literature Data on the Use of PILC-Based Materials;193
17.4;7.4 Photocatalytic Behavior of Ti-PILC and Fe-PILC;197
17.4.1;7.4.1 Ti-PILC ;197
17.4.2;7.4.2 Fe-PILC for Photo-Fenton;201
17.5;7.5 Conclusions;202
18;References;203
19;8 FeAl-Pillared Clays: Catalysts for Wet Peroxide Oxidation of Phenol;211
19.1;8.1 Introduction;211
19.2;8.2 Experimental;212
19.2.1;8.2.1 Catalysts;212
19.2.2;8.2.2 Catalytic Phenol Oxidation;213
19.2.2.1;8.2.2.1 Reaction;213
19.2.2.2;8.2.2.2 Batch Reactor;214
19.2.2.3;8.2.2.3 Dynamic Fixed-Bed Reactor;214
19.2.2.4;8.2.2.4 Mössbauer Spectroscopy;215
19.2.2.5;8.2.2.5 ESR Spectroscopy;215
19.3;8.3 Results and Discussion;216
19.3.1;8.3.1 Phenol Oxidation;216
19.3.1.1;8.3.1.1 Batch Reactor;216
19.3.2;8.3.2 Catalyst Characterizations;226
19.3.2.1;8.3.2.1 Mössbauer;226
19.3.2.2;8.3.2.2 ESR;227
19.4;8.4 Conclusion;231
20;References;232
21;9 Pillared Clay-Supported Noble Metal and Metal Oxide Catalysts for Complete Oxidation of VOCs;235
21.1;9.1 Introduction;235
21.2;9.2 Pillared Clay-Supported Noble Metal Catalysts for Complete Oxidation of VOCs;236
21.3;9.3 Pillared Clay-Supported Metal Oxide Catalysts for Complete Oxidation of VOCs;249
21.4;9.4 Pillared Clays as Catalysts for Complete Oxidation of VOCs;259
21.5;9.5 Conclusions;261
22;References;261
23;10 Clay Materials for Selective Catalytic Reduction of NOx;265
23.1;10.1 Introduction;265
23.1.1;10.1.1 NOx Definition;265
23.1.2;10.1.2 NOx Origin;266
23.1.3;10.1.3 NOx Environmental Effects;267
23.1.4;10.1.4 Legislative Aspects;269
23.1.5;10.1.5 NOx Reduction Ways;269
23.1.6;10.1.6 NOx Removal by Catalytic Technologies;273
23.1.6.1;10.1.6.1 Selective Catalytic Reduction with Ammonia;273
23.1.6.2;10.1.6.2 Selective Catalytic Reduction with Hydrocarbons;275
23.1.6.3;10.1.6.3 Catalytic Reduction with CO;279
23.1.6.4;10.1.6.4 Catalytic Decomposition;280
23.2;10.2 Pillared Clays as DeNO x Catalysts;281
23.2.1;10.2.1 NOx Reduction with Ammonia;281
23.2.2;10.2.2 NOx Reduction with Hydrocarbons;289
23.2.3;10.2.3 NOx Catalytic Reduction with CO and NOx Catalytic Decomposition;293
23.3;10.3 HDL as DeNOx Catalysts;294
23.4;10.4 Porous clay Heterostructures (PCH) as DeNO x Catalysts;297
23.5;10.5 Concluding Remarks;299
24;References;300
25;11 Pillared Clay Catalysts in Green Oxidation Reactions;311
25.1;11.1 Introduction;311
25.2;11.2 Alkene Oxidation;312
25.2.1;11.2.1 Epoxidation;312
25.2.2;11.2.2 Oxidative Ketonization;315
25.2.3;11.2.3 Allylic Oxidation;316
25.3;11.3 Alkylaromatic Oxidation;317
25.3.1;11.3.1 Aromatic Ring Oxidation;317
25.4;11.4 Oxidation of Compounds Containing Oxygen;317
25.4.1;11.4.1 Alcohol Oxidation;317
25.4.2;11.4.2 Phenol Oxidation;318
25.4.3;11.4.3 Allylic Alcohol Epoxidation;320
25.5;11.5 Heteroatom Oxidation;321
25.5.1;11.5.1 Amine Oxidation;321
25.5.2;11.5.2 Sulfoxidation;322
25.6;11.6 Conclusions;322
26;References;323
27;12 Heterogeneous Catalysis by Polyoxometalate-Intercalated Layered Double Hydroxides;329
27.1;12.1 Introduction;329
27.2;12.2 Vanadium-Containing LDHs;337
27.3;12.3 Chromium-Containing LDHs;348
27.4;12.4 Molybdenum-Containing LDHs;354
27.5;12.5 Tungsten-Containing LDHs;367
27.6;12.6 Miscellaneous Systems;388
27.6.1;12.6.1 Boron-Containing LDHs;388
27.6.2;12.6.2 Manganese-Containing LDHs;389
27.6.3;12.6.3 Niobium-Containing LDHs;391
27.6.4;12.6.4 Osmium-Containing LDHs;392
27.7;12.7 Conclusions;395
28;References;395
29;13 Basicity, Catalytic and Adsorptive Properties of Hydrotalcites;408
29.1;13.1 Introduction;408
29.2;13.2 Activation of HDT;409
29.3;13.3 Recent Applications of HDT as Basic Catalyst;410
29.3.1;13.3.1 Isomerisation of Olefins;410
29.3.2;13.3.2 Aldolisation;411
29.3.3;13.3.3 Meerwein--Ponndorff--Verley Reductions of Carbonyls;413
29.3.4;13.3.4 Oxidations;414
29.4;13.4 Bifunctional Catalysis;416
29.5;13.5 Support Effects on Palladium;417
29.5.1;13.5.1 Electronic Effects;417
29.5.2;13.5.2 Catalytic Properties for Hydrogenations;418
29.5.3;13.5.3 Dechlorination of Trichlorobenzene;418
29.5.4;13.5.4 Catalysis of C--C Coupling Reactions;418
29.5.5;13.5.5 Merox Process;419
29.6;13.6 Solid Bases as Adsorbents and Anionic Exchangers;419
29.6.1;13.6.1 Trapping of Organic Compounds and Anions;419
29.6.2;13.6.2 SOx Additives for FCC;421
29.6.3;13.6.3 NOx Traps;422
29.7;13.7 Hydrotalcites as Reservoirs for Drugs;422
29.8;13.8 Conclusions;424
30;References;425
31;14 Mesoporous Phosphate Heterostructures: Synthesis and Application on Adsorption and Catalysis;432
31.1;14.1 Introduction;433
31.2;14.2 Synthesis of SiPPH;434
31.3;14.3 Doping the Silica Galleries;437
31.4;14.4 Functionalisation of Silica Galleries;439
31.5;14.5 PPH as Support of Other Chemical Species;442
31.6;14.6 Applications in Catalysis and Adsorption of SiPPH;445
32;References;452
33;15 Recent Advances in the Preparation and Application of Mesoporous Aluminophosphate-Based Materials;456
33.1;15.1 Introduction;456
33.2;15.2 Synthesis;457
33.3;15.3 Surfactant Removal;458
33.4;15.4 Block Copolymers as Surfactants;459
33.5;15.5 Aluminophosphate Modification;462
33.6;15.6 Applications of Mesoporous Aluminophosphates and Metal Aluminophosphates;465
33.7;15.7 Conclusions;468
34;References;469
35;16 Heterogeneous Complex Catalysts Having Ionically Macrocyclic Complex Bonded to Montmorillonite Clay for Industrial Reactions;473
35.1;16.1 Introduction;473
35.1.1;16.1.1 Montmorillonite as Catalyst;473
35.1.2;16.1.2 Complexes;474
35.1.3;16.1.3 Scope of the Present Work;490
35.2;16.2 Experimental;494
35.2.1;16.2.1 Preparation of the Macrocyclic Complex;494
35.2.1.1;16.2.1.1 Preparation of 2,6-Diformyl-4-methylphenol (Dialdehyde);494
35.2.1.2;16.2.1.2 Synthesis of Homonuclear CuCuL-1,2(CH 3 COO) [L-1 =(CH 3 C 6 H 2 (CH) 2 ON 2 C 6 H 4 ) 2 ] Macrocyclic Complex;496
35.2.1.3;16.2.1.3 Synthesis of Heterobinuclear FeCuL-2 (NO 3 ) 2 04H 2 O Macrocyclic Complex, L-2 = (CH 3 C 6 H 2 (CH) 2 O(CH 2 ) 3 N 2 ) 2 ;497
35.2.2;16.2.2 Synthesis of the Heterogeneous Complex Catalyst;499
35.3;16.3 Characterization of the Complexes and Their Catalysts;500
35.3.1;16.3.1 FTIR Analysis of Complex;500
35.3.2;16.3.2 C--H--N Analysis of the Complex;500
35.3.3;16.3.3 Scanning Electron Microscopy of the Complex and the Catalyst;503
35.3.4;16.3.4 Single--Crystal X-Ray Analysis of the Complex;503
35.3.5;16.3.5 Thermogravimetric Analysis (TGA) of the Complex and the Catalyst;505
35.3.6;16.3.6 Small-Angle X-Ray Diffraction Analysis of the Catalyst;505
35.4;16.4 Catalytic Oxidation of Cyclohexane Using Oxygen;506
35.4.1;16.4.1 Introduction;506
35.4.2;16.4.2 Reaction Procedure;509
35.4.3;16.4.3 Test for the Absence of Cyclohexyl Hydroperoxide in the Reaction Mass;510
35.4.4;16.4.4 Metal Leaching Test;511
35.4.5;16.4.5 Oxidation of Cyclohexane in the Presence of FeCuL-2/Montmorillonite and CuCuL-1/Montmorillonite Catalysts;511
35.4.6;16.4.6 Reaction Mechanism;512
35.4.7;16.4.7 Optimal Data Fitting;516
35.5;16.5 Conclusions;519
36;References;519
37;Index;525