Scientific Bases for the Preparation of Heterogeneous Catalysts (eBook)
1150 Seiten
Elsevier Science (Verlag)
978-0-08-054074-0 (ISBN)
This volume containing the Proceedings of the 8th International Symposium on Scientific Bases for the Preparation of Heterogeneous Catalysts consists of papers summarizing most of the 139 oral communications and posters selected by the international scientific committee, composed of 27 experts in the field of catalyst preparation, holding an industrial or academia appointment.
The contributions focus on the aspects of catalyst preparation. The main topics are: new approaches in catalyst preparation, advanced preparations of nanoporous and mesoporous catalysts, catalysts preparation for special performances and purposes, catalysts for environmental purposes, and molecular catalysis. Emphasis is put on the role that catalysis can play as an essential element of sustainable development.
It has become a tradition that every four years, the Universite Catholique de Louvain and the Katholieke Universiteit Leuven jointly organize a symposium devoted to the scientific bases for the preparation of heterogeneous catalysts. These meetings bring together researchers from academia and industry and offer a forum for discussions on the chemistry involved in the preparation of industrial heterogeneous catalysts. This volume containing the Proceedings of the 8th International Symposium on Scientific Bases for the Preparation of Heterogeneous Catalysts consists of papers summarizing most of the 139 oral communications and posters selected by the international scientific committee, composed of 27 experts in the field of catalyst preparation, holding an industrial or academia appointment.The contributions focus on the aspects of catalyst preparation. The main topics are: new approaches in catalyst preparation; advanced preparations of nanoporous and mesoporous catalysts; catalysts preparation for special performances and purposes; catalysts for environmental purposes; and molecular catalysis. Emphasis is put on the role that catalysis can play as an essential element of sustainable development.
Front Cover 1
Scientific Bases for the Preparation of Heterogeneous Catalysts 4
Copyright Page 5
Contents 10
Foreword 6
Chapter 1. Aspects of scale-up of catalyst production 22
Chapter 2. Quantitative structure-activity relationships in zeolite-based catalysts: influence of framework structure 38
Chapter 3. Cogelation: an effective sol–gel method to produce sinter-proof finely dispersed metal catalysts supported on highly porous oxides 46
Chapter 4. Steam reforming of CH4 over Ni/Mg-Al catalyst prepared by spc-method from hydrotalcite 56
Chapter 5. Toward a molecular understanding of noble metal catalyst impregnation 66
Chapter 6. Support modification of cobalt based slurry phase Fischer-Tropsch catalysts 76
Chapter 7. The effects of nature and pretreatment of surface alumina support on the catalytic nickelsilicate membrane formation 88
Chapter 8. Supports and catalysts preparation by using metal alkoxides grafting technique 98
Chapter 9. Combinatorial approaches for speeding up heterogeneous catalyst discovery, optimisation and scaling-up 110
Chapter 10. High surface area metal oxides from matrix assisted preparation in activated carbons 114
Chapter 11. Effects of the impregnating and drying process factors on mechanical properties of a PCoMo/Al2O3 hydrotreating catalyst 122
Chapter 13. Influence of CeO2 content on Rh/TiO2 monolithic catalysts for N2O decomposition 132
Chapter 14. Pt combustion catalysts prepared from W/O microemulsions 142
Chapter 15. Preparation of stable catalysts for N2O decomposition under industrial conditions 152
Chapter 16. The Anderson-type heteropolyanions in the synthesis of alumina- and zeolite- supported HDS oxidic precursors 162
Chapter 17. Sol-gel preparation of pure and silica-dispersed vanadium and niobium catalysts active in oxidative dehydrogenation of propane 170
Chapter 18. Preparation of nickel-modified ceramic filters by the urea precipitation method for tar removal from biomass gasification gas 180
Chapter 19. Preparation of gold-titanosilicate catalysts for vapor-phase propylene epoxidation using H2 and O2 188
Chapter 20. Sol-gel synthesis of colloids and triflates containing hybrid type catalysts 198
Chapter 21. Preparation of zeogrids through interposed stapling and fusion of MFI zeolite type nanoslabs 206
Chapter 22. Large scale synthesis of carbon nanofibers by catalytic decomposition of hydrocarbon 214
Chapter 23. Synthesis and characterization of carbon nanofiber supported ruthenium catalysts 222
Chapter 24. Synthesis of high pore volume and specific surface area mesoporous alumina 230
Chapter 25. Investigation on acidity of zeolites bound with silica and alumina 238
Chapter 26. Preparation of BN catalyst supports from molecular precursors. Influence of the precursor on the properties of the B N ceramic 248
Chapter 27. Monitoring of the particle size of MoSx nanoparticles by a new microemulsion- based synthesis 260
Chapter 28. Transition metal phosphides. Novel hydrodenitrogenation catalysts 268
Chapter 29. The application of non-hydrothermally prepared stevensites as support for hydrodesulfurization catalysts 278
Chapter 30. NiMo/HNaY(x)-Al2O3 catalysts for the hydrodesulfurization of hindered dibenzothiophenes: effect of the preparation method 288
Chapter 31. Chiral dirhodium catalysts confined in porous hosts 298
Chapter 32. Synthesis and characterization of zeolite encaged enzyme-mimetic copper histidine complexes 308
Chapter 33. Strategies for the heterogenization of rhodium complexes on activated carbon 316
Chapter 34. Heterogeneous metathesis initiators 326
Chapter 35. Preparation of physically heterogeneous and chemically homogeneous catalysts on the base of metal complexes immobilized in polymer gels 334
Chapter 36. Hydrocracking catalyst to produce high quality diesel fraction 342
Chapter 37. Thermostable yttria-doped inorganic oxide catalyst supports for high temperature reactions 352
Chapter 38. Preparation and characterization of WOx-CeO2 catalysts 358
Chapter 39. Preparation of iridium catalysts by deposition precipitation: room temperature oxidation of CO 366
Chapter 40. New approach to preparation and investigation of active sites in sulfated zirconia catalysts for skeletal isomerization of alcanes 374
Chapter 41. Supported ruthenium carbido-cluster catalysts for the catalytic removal of nitrogen monoxide and sulfur dioxide: the preparation process monitored by sulfur K-edge X-ray absorption near-edge structure 382
Chapter 42. Catalytic transformation of dichloromethane over Y and X zeolites 390
Chapter 43. Preparation of new solid super-acid catalyst, titanium sulfate supported on zirconia and its acid catalytic properties 398
Chapter 44. Superacid WOx/ZrO2 catalysts for isomerization of n-hexane and for nitration of benzene 408
Chapter 45. Preparation of copper-oxide catalyst systems for hydrogenation 418
Chapter 46. Application of experimental design for NOx reduction by Pd–Cu catalysts 428
Chapter 47. Marked difference of catalytic behavior by preparation methods in CH4 reforming with CO2 over Mo2C and WC catalysts 436
Chapter 48. Synthesis and properties of new catalytic systems based on zirconium dioxide and pentasils for process of NOx selective catalytic reduction by hydrocarbons 446
Chapter 49. Preparation of chitosan based catalysts for several reactions of liquid phase hydrogenation 456
Chapter 50. Preparation of Mo/Al2O3 sulfide catalysts modified by Ir nanoparticles 464
Chapter 51. Peptization mechanisms of boehmite used as precursors for catalysts 474
Chapter 52. Influence of the treatment of Y zeolite by ammonium hexafluorosilicate on physicochemical and catalytic properties: application for chlororganics destruc- tion 484
Chapter 53. Preparation of SiO2 modified SnO2 and ZrO2 with novel thermal stability 492
Chapter 54. Control of the textural properties of cesium 12-molybdophosphate-based supports 502
Chapter 55. MnOx/CeO2–ZrO2 and MnOx/WO3–TiO2 catalysts for the total oxidation of methane and chlorinated hydrocarbons 510
Chapter 56. Catalytic behaviour of Rh-supported catalysts on lamellar and zeolitic structures by anchoring of organometallic compound 520
Chapter 57. The use of sol-gel technique to prepare the TiO2–A1203 binary system over a wide range of Ti–Al ratios 530
Chapter 58. Catalytic performance in the complete acetone oxidation of manganese and cobalt oxides supported on alumina and silica 538
Chapter 59. Unsupported and supported manganese oxides used in the catalytic combustion of methyl-ethyl-ketone 548
Chapter 60. Ni/Hß zeolite catalysts prepared by the deposition-precipitation method 558
Chapter 61. Sol-gel Al2O3 structure modification by Ti and Zr addition. A NMR study 568
Chapter 62. Promotion of Ru/ZrO2 catalysts by platinum 576
Chapter 63. Catalysts based on RhMo6 heteropolymetalates. Bulk and supported preparation and characterisation 586
Chapter 64. Metallosilicate mesoporous catalysts prepared by incorporation of transition metals in the MCM-41 molecular sieves and their catalytic activity in selective oxidation of aromatics (styrene and benzene) 596
Chapter 65. Controlled surface modification of alumina-supported Mo or Co–Mo sulfides by surface organometallic chemistry 606
Chapter 66. Novel one step synthesis of cobalt (II) phtalocyanine-hydrotalcite catalysts for mercaptan oxidation in light oil sweetening 614
Chapter 67. Structural and catalytic properties of Zr-Ce-Pr-O xerogels 622
Chapter 68. Influence of the precursor (nature and amount) on the morphology of MoO3 crystallites supported on silica 630
Chapter 69. Single step synthesis of metal catalysts supported on porous carbon with controlled texture 640
Chapter 70. Ag/SiO2 and Cu/SiO2 cogelled xerogel catalysts for benzene combustion and 2-butanol dehydrogenation 648
Chapter 71. Preparation of zeolite catalysts for dehydrogenation and isomerization of n-butane 658
Chapter 72. The application of well-dispersed nickel nanoparticles inside the mesopores of MCM-41 by use of a nickel citrate chelate as precursor 668
Chapter 73. Preparation of Ce–Zr–O composites by a polymerized complex method 680
Chapter 74. Sol–gel routes for the preparation of heterogeneous catalyst based on Ru, Rh, Pd supported metals 690
Chapter 75. Development of novel heterogeneous catalysts for oxidative reactions: prepa- ration and performance of Co–Nx catalysts in partial oxidation of toluene and n-butane 700
Chapter 76. Synthesis and modification of basic mesoporous materials for the selective etherification of glycerol 708
Chapter 77. Carbon nanotubes: a highly selective support for the C=C bond hydrogenation reaction 718
Chapter 78. Raman studies of the templated synthesis of zeolites 726
Chapter 79. Templateless synthesis of catalysts with narrow mesoporous distribution 736
Chapter 80. Control of pore structures of titanias and titania/aluminas using complexing agents 744
Chapter 81. Tungstophosphoric acid immobilized in polyvinyl alcohol hydrogel beads as heterogeneous catalyst 752
Chapter 82. Functionalized SiMCM-41 as support for heteropolyacid based catalysts 760
Chapter 83. Influence of the preparation method on the surface properties and activity of alumina-supported gallium oxide catalysts 768
Chapter 84. Preparation and properties of bimetallic Ru–Sn sol–gel catalysts: the influence of catalyst reduction 778
Chapter 85. A new insight into molybdate/boehmite interaction 788
Chapter 86. Controlled coating of high surface area silica with titania overlayers by atomic layer deposition 798
Chapter 87. Concept of the synthesis of novel platinum catalysts for selective hydrogenation of unsaturated carbonyl compounds 808
Chapter 88. Storage and supply of hydrogen mediated by iron oxide: modification of iron oxides 816
Chapter 89. Catalytic activity of bulk and supported sulfated zirconia 824
Chapter 90. New one-step synthesis of superacid sulfated zirconia 834
Chapter 91. Elaboration and characterization of a realistic Phillips model catalyst for ethylene polymerisation 844
Chapter 92. Preparation of new basic mesoporous silica catalysts by ammonia grafting 858
Chapter 93. Titania-silica catalysts prepared by sol-gel method for photoepoxidation of propene with molecular oxygen 866
Chapter 94. Preparation of large surface area MnOx–ZrO2 for sorptive NOx removal 876
Chapter 95. Preparation of CuOx–TiO2 nano-composite photocatalysts from intercalated layer structure 884
Chapter 96. Vanadia-doped titanium pillared clay: preparation, characterization and SCR activity of NO by ammonia 894
Chapter 97. Advanced preparation by sol–gel method of the encapsulated Pd/Al2O3 catalysts for methane combustion 902
Chapter 98. Non-ionic surfactant templated synthesis of mesoporous silica in the presence of platinum salts 912
Chapter 99. Synthesis and acid–base properties of catalysts based on magnesium and sodium-magnesium mixed phosphates 920
Chapter 100. Preparation of Pd–Ce/ZrO2 catalysts for methane oxidation 928
Chapter 101. The effect of cerium introduction on vanadium-USY catalysts 936
Chapter 102. Rh–Co mordenite catalysts for the selective reduction of NO by methane 946
Chapter 103. Surface characterization of WO3-TiO2/Al2O3 catalysts and reactivity on selective catalytic reaction of NO by NH3 954
Chapter 104. Catalytic materials for the synthesis of hydrofluorocarbons 962
Chapter 105. Preparation, characterization and reactivity in m-cresol methylation of new heterogeneous materials having basic properties 974
Chapter 106. The effect of glycols in the organic preparation of V/P mixed oxide catalyst for the oxidation of n-butane to maleic anhydride 984
Chapter 107. Synthesis and characterization of nanostructured MO2C on carbon material by carbothermal hydrogen reduction 996
Chapter 108. Carbon composite-based catalysts: new perspectives for the low-temperature H2S removal 1004
Chapter 109. Active carbon surface oxidation to optimize the support functionality and metallic dispersion of a Pd/C catalyst 1014
Chapter 110. n-Butane isomerization over Al-promoted sulfated zirconias. Influence of the sulfate content 1024
Chapter 111. Influence of preparation procedure on physical and catalytic properties of carbon-supported Pd-Au catalysts 1032
Chapter 112. Preparation of mesoporous highly dispersed Pd–Pt catalysts for deep hydrodesulfurization 1040
Chapter 113. Preparation of highly ordered CMI-1 and wormhole-like DWM mesoporous silica catalyst supports using C16(EO)10 as surfactant 1048
Chapter 114. Synthesis and characteriation of nanostructured mesoporous zirconia catalyst supports using non-ionic surfactants as templating agents 1056
Chapter 115. Effect of preparation parameters on the catalytic activities of sulfated ZrO2–SiO2 catalysts obtained by sol-gel process 1066
Chapter 116. Non-aggressive way for preparation of zirconium sulfate pillared clay using zirconium acetate developing high sulfur thermal stability over 830C 1074
Chapter 117. Influence of the preparation conditions on the structure of the active phase and catalytic properties of Ni-Co-molybdate propane oxydehydrogenation catalysts 1084
Chapter 118. Oxidized diamond as a new catalyst support 1094
Chapter 119. Preparation of catalytic membranes, micro-capsules and fabrics active in immobilized Fenton chemistry 1102
Chapter 120. Preparation of vanadium-based catalysts for selective catalytic reduction of nitrogen oxides using titania supports chemically modified with organosilanes 1110
Chapter 121. Design, preparation and testing of effective FeOx/SiO2 catalysts in methane to formaldehyde selective oxidation 1118
Chapter 122. New Fe–Mo–Ti mixed oxides prepared via the sol–gel method: comparison of the textural properties with solids obtained by impregnation 1128
Index 1136
Studies in Surface Science and Catalysis 1142
Aspects of scale-up of catalyst production
Keld Johansen kei@topsoe.dk Research & Development Division, Haldor Topsøe A/S Nymøllevej 55 DK-2800 Lyngby, Denmark
1 SCOPE OF CATALYST PRODUCTION
Catalyst production has a significant influence on the economy, since 80-90% of the chemicals used in a modern society are exposed to a catalyst. The value of the US catalyst market was 2.2 billion $ in 2000 [1]. A number of specialised catalyst companies in the world, many global, produce and supply a large number of products to the industry. It is said that products corresponding to 10% of the GNP of the industrialised countries are dependent on the availability of catalyst. Catalyst plants produce quantities of 0.1-100 t/day of each product dependant on the type. Thus, transfer of new products and implementation in catalyst plants are important technological disciplines for each catalyst company.
2 NATURE OF THE SCALE-UP PROBLEM
Before the decision is taken on transferring a new recipe from research and development departments to an existing catalyst plant or a new investment, considerable work has already been carried out – many test samples have been prepared and activity-tested. All candidates for a new product have one thing in common: in the starting phase they have been prepared and selected from the laboratory processes.
2.1 Description of laboratory prepared samples
Laboratory or bench scale prepared catalyst samples for screening are typically made in gram scale (10-50 g). The catalysts can be prepared in many ways depending on the type, but steps for three commonly used preparation routes are shown below in Fig. 1 and, for each step, examples of the typical laboratory equipment are given.
The laboratory equipment used is normally characterised by:
- Small dimensions with short mass and heat transport distances
- High energy intensity per volume for stirrer mixers and kneaders
- Pure chemicals
- Small layers in muffle furnaces with low temperature gradients, but long hea cycle
- H2 activation with low pH2O
- Drying with low but undefined pH2O
- Precipitation within small volume dimension
- Filtration without respect of agglomerate size
- Washing without respect of time or leakage of particles or ions
- Tabletting/forming of non-representative granules
- Generated heat during processes easily dissipated to cooling surface
A modern catalyst laboratory will analyse and describe in detail all intermediates final catalysts from the above three manufacturing routes by means of the methods follows: main chemical elements and trace elements, phases (if not amorphous), p distribution and BET or selective surface area. A more complete list of commonly v methods is given in Table 1 below:
Table 1
Physical and chemical characterisation methods
| Main chemical elements | ICP, AAS, XRF and electron micro probe analysis |
| Trace elements | AAS, ICP |
| Oxidation state | Electron micro probe analysis, EDS in SEM, EDS |
| Element distribution | in TEM |
| Physical |
| Surface area | BET (N2, Ar, K), or specific area, chemisorption of H2,CO, N2O |
| Pore volume - total | Water absorption –Hg intrusion |
| Pore size distribution | He, or Hg intrusion, N2 adsorption |
| Phases, crystallite size | XRD, TEM, Raman Spectroscopy |
| Surface composition | XPS, SIMS |
| Surface properties | IR, microcalorimetry, chemisorption/desorption (TPD,TPR) |
| Particle size distribution | LLD, SAXS, sieves, TEM, SEM |
| Structure and texture | TEM, SEM, optical microscopy |
| Thermogravimetry | TGA, DTA, dilatometer |
| Specially for finished product form |
| Abrasion resistance for granules |
| Attrition resistance for fluid cat and powders | Attrition loss |
| Crushing strength | Texture analyser |
However, all the above methods in Table 1 cannot give a scientifically exhaustive description of the intermediates nor of the final catalyst. Amorphous phases often obtained from precipitation cannot be characterised sufficiently (how many kinds of amorphous phases exist?) Furthermore, the final catalyst granule is formed from agglomerates of crystallites. Both crystallites (forming primary agglomerates) and the agglomerates have their own particle size distribution and binding properties. Particle size distribution of primary and secondary agglomerates controls the final pore size distribution. The pore size distribution and particle strength will have significant influence on the final performance of the product in the reactor. Even considering the methods listed in Table 1, there is no method or combined methods today that can give a full description of the crystallite-agglomerate multi-parameter system. To further illustrate the problem, it should be mentioned that even if the overall chemical composition is the same for two different manufacturing routes, the pore size distribution is most probably different. Thus, it is not possible to characterise an intermediate or final catalyst so you can be sure to have the same catalyst without preparing it in the same reproducible way.
2.2 Catalyst manufacturing – unit operations
The catalyst plant is operating in ton scale (typically 1-100 t/day) with processes and equipment completely different from bench scale as sketched in Fig. 1, even if the preparation steps are the same. In the open literature, description of catalyst manufacturing processes and equipment is sparse. The reference list contains important monographs and papers [2–24]. The patent literature gives some information, but catalyst manufacturing technologies are often not patented but kept secret. The single step in manufacturing is called a unit operation and can be performed by several types of equipment. Table 2 shows most of the unit operations used and examples of equipment for each. Most of the typical equipment will have more different time constants, heat transfer, flow patterns, temperature profiles etc. than bench scale equipment and, therefore, the final catalyst will achieve other properties.
Table 2
List of unit operations with typical equipment
| 1. Dissolution | Tanks with stirrer |
| 2. Precipitation | Pumps, specially designed reactors and stirrers |
| 3. Ageing and maturation, gel formation | Temperature-regulated tanks, autoclaves |
| 4. Filtration | Belt filter Drum filter Centrifuge Filter press |
| 5. Washing | Belt filter Drum filter Centrifuge |
| 6. Drying | Belt conveyor furnace Spray drying Fluid bed drying Rotary kiln Vacuum dryer |
| 7. Wet mixing (kneading) | Z-mixer Double screw mixer |
| 8. Dry mixing | Nauta mixer Double cone mixer Ribbon blender |
| 9. Grinding | Jet mill Roller mill Universal mill Pearl mill |
| 10. Sieving | Screen |
| 11. Forming | Tabletting Extrusion Granulation Spray drying Corrugation |
| 12. Calcination | Belt conveyor furnace Rotary kiln Shaft furnaces Chamber and muffle furnace Tunnel furnace Fluid bed |
| 13. Impregnation | Pore filling – incipient wetness Immersion in liquid Controlled chemisorption |
| 14. Decomposition | See under calcination |
| 15. Fusion | Electrical hearth |
| 16. Activation | Prereduction reactor |
| 17. Cooling and annealing | Fluid bed, chamber and muffle furnace |
| 18. Coating | Washcoater, dragee pan |
| 19. Leaching | Tanks with stirrer |
| 20. Reslurrying | Tanks with stirrer, kneader |
2.3 Optimal combinations
For every commercial catalyst an optimal combination of unit operation sequence exists for the manufacture of that...
| Erscheint lt. Verlag | 29.8.2002 |
|---|---|
| Sprache | englisch |
| Themenwelt | Naturwissenschaften ► Chemie ► Physikalische Chemie |
| Naturwissenschaften ► Chemie ► Technische Chemie | |
| Naturwissenschaften ► Geowissenschaften ► Mineralogie / Paläontologie | |
| Technik ► Bauwesen | |
| Technik ► Umwelttechnik / Biotechnologie | |
| ISBN-10 | 0-08-054074-0 / 0080540740 |
| ISBN-13 | 978-0-08-054074-0 / 9780080540740 |
| Haben Sie eine Frage zum Produkt? |
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