Supported Metals In Catalysis

by James Arthur Anderson, Marcos Fernandez Garcia

Overview

With contributions from experts in supported metal catalysis, from both the industry and academia, this book presents the recent developments in characterization and application of supported metals in heterogeneous catalysis. In addition to a thorough and updated coverage of the traditional aspects of heterogeneous catalysis such as preparation, characterization and use in well-established technologies such as Naphtha reforming, the book also includes emerging areas where supported metal catalysis will make significant contributions in future developments, such as hydrogen production and fine chemicals synthesis.

Product Details

ISBN-13:	9781860944901
Publisher:	Imperial College Press
Publication date:	05/09/2005
Series:	Catalytic Science Series , #5
Pages:	380
Product dimensions:	5.90(w) x 9.00(h) x 1.00(d)

Table of Contents

	Preface	xi
1	Preparation of Supported Metal Catalysts	1
1.1	Introduction	1
1.2	General Description of Preparation Methods	3
1.2.1	Impregnation	3
1.3	Case Studies	14
1.3.1	Impregnation: Preparation of Pt catalysts, the effect of the pre-treatment conditions	15
1.3.2	Precipitation vs. Impregnation by Ion-exchange: Au precursors, and the effect of the method of preparation and selected support on performance in selective epoxidation of propene over Au/TiO[subscript 2] catalysts	19
1.3.3	Co-precipitation: Preparation of advanced CaCO[subscript 3] supported Ag catalysts for propylene epoxidation by a novel co-precipitation route	23
1.4	General Conclusions on the Preparation of Metal Catalysts	29
2	Theoretical Description of the Metal-oxide Interface by First Principle Methods	33
2.1	Introduction	33
2.2	Experimental Models and Techniques on Oxide Surfaces and Metal-oxide Interfaces	34
2.3	Theoretical Methods	39
2.3.1	Physical approaches to the metal-oxide interface	39
2.3.2	Methods of electronic structure calculation	42
2.3.3	Basis sets and related concepts	45
2.3.4	Approaches on the dynamics of the systems	47
2.4	Interaction of Metals with MgO(001)	48
2.4.1	Isolated atoms on MgO(001)	48
2.4.2	Metallic films on the MgO(001) surface	52
2.4.3	Interaction of metal atoms with point defects of the MgO(001) surface	53
2.4.4	Interaction of metal clusters with perfect and defective MgO(001)	56
2.4.5	Reactivity of metals on MgO	58
2.4.6	Other properties: Mobility of metals on oxides	60
2.5	Interaction of Metals with Other Faces of MgO and Other Alkaline-earth Oxides	60
2.6	Metal-support Interaction Involving Ionic Oxides with Complex Structures: The Case of the [alpha]-Al[subscript 2]O[subscript 3] (0001) Surface	61
2.7	Interaction of Metal Atoms and Cluster with Covalent and Semicovalent Oxide Surfaces	66
2.8	Conclusions	73
3	Characterisation of Supported Metal Catalysts by Spectroscopic Techniques	83
3.1	Introduction	83
3.2	Main Properties of Monometallic Systems	84
3.3	Main Properties of Bimetallic Systems	86
3.4	In-situ Characterisation	90
3.4.1	XAFS spectroscopies	90
3.4.2	Vibrational spectroscopy	103
3.4.3	Valence and core photoelectron spectroscopies	112
3.4.4	Other techniques	115
4	Determination of Dispersion and Supported Metal Crystallite Size	123
4.1	Introduction	123
4.2	General Considerations	124
4.2.1	Physical methods	124
4.2.2	Chemical methods	130
5	Recent Progress in Supported Metal Catalysed C1 Chemistry	155
5.1	Introduction	155
5.2	Fischer-Tropsch Synthesis	158
5.3	Methanol Production and Higher Alcohols from Syngas	164
5.4	Hydrogenation Reactions and Other Possibilities Aimed to Reuse CO[subscript 2]	171
5.5	Hydroformylation of Olefins with Synthesis Gas	174
5.6	Catalysed Reactions Involving CH[subscript 4]	175
5.7	CH[subscript 3]OH to Hydrocarbons and to Other Intermediate Compounds	176
6	Supported Metal Catalysts in Reforming	187
6.1	Introduction	187
6.1.1	Hydrogen pressure	191
6.2	Structural Requirements of Reforming Reactions	192
6.3	The Reforming Cycle	196
6.4	Deactivation	196
6.4.1	Observed effect of parameters	198
6.5	Regeneration	206
6.6	Improvements to Yields and Life	207
6.6.1	The use of multimetallic catalysts in S/R	208
6.6.2	Alloys and clusters	209
6.6.3	Pt-Re structures	209
6.6.4	Pt-ReS	211
6.6.5	Pt-Ir, the "rational scientific design"	213
6.6.6	Parallel developments in quality/purity of alumina	214
6.6.7	Continuous catalyst regeneration	214
6.6.8	Pt-Sn	215
6.7	Monofunctional Zeolite-based Reforming	217
6.7.1	PtKL	217
6.7.2	The technological process	219
6.8	Conclusions	221
7	Supported Metals in the Production of Hydrogen	229
7.1	Introduction	229
7.2	Methane Conversion	230
7.2.1	Steam methane reforming	231
7.2.1.1	Carbon formation	233
7.2.1.2	Promoter effects	235
7.2.2	Methane decomposition	236
7.2.2.1	Nickel catalysts	237
7.2.2.2	Diamond-supported transition metals	238
7.2.2.3	Cobalt catalysts	238
7.2.2.4	Nature of the carbon by-product	239
7.2.2.5	Theoretical investigation	243
7.2.3	Partial oxidation and dry reforming of methane	245
7.2.3.1	Catalytic mechanism and heat exchange	246
7.2.3.2	Catalysts supports	251
7.2.3.3	Reaction intermediates	253
7.2.3.4	Promoting effects	254
7.2.3.5	Perovskite and hydrotalcite precursors	255
7.3	Alcohol Conversion	258
7.3.1	Methanol	258
7.3.1.1	Methanol decomposition	258
7.3.1.2	Methanol steam reforming	259
7.3.1.3	Partial oxidation of methanol	260
7.3.1.4	Autothermal reforming of methanol	266
7.3.2	Ethanol oxidation	267
7.3.2.1	Cobalt catalysts	270
7.4	Conversion of other Hydrocarbon Feeds	273
8	Supported Metals in Vehicle Emission Control	283
8.1	Introduction	283
8.2	Emissions Produced at Stoichiometric Conditions	285
8.2.1	Classical TWC	285
8.2.2	Modern TWC	289
8.2.2.1	New oxygen buffering oxides	289
8.2.2.2	The shift towards the use of palladium	292
8.2.2.3	Promotion of Pd by base metals	296
8.3	Lean-burn Emissions	297
8.3.1	Oxidation catalysts	298
8.3.2	Treatment of soot	299
8.3.3	Catalysts for selective reduction of NO[subscript x] with hydrocarbons	301
8.3.3.1	Platinum group metal systems	303
8.3.3.2	Base metal systems	307
8.3.3.3	Practical approaches	313
8.4	Mixed Oscillating Emissions	314
8.4.1	NO[subscript x] Storage and reduction catalysts	314
9	Catalysis for Fine Chemicals Manufacture	327
9.1	Introduction	327
9.2	Selective Hydrogenation over Supported Metal Catalysts	328
9.2.1	The hydrogenation of buta-1,3-diene over non-modified metal catalysts	328
9.2.2	The hydrogenation of buta-1,3-diene over modified metal catalysts	332
9.2.3	The hydrogenation of [alpha], [beta]-unsaturated aldehydes over non-modified metal catalysts	333
9.2.4	The hydrogenation of [alpha], [beta]-unsaturated aldehydes over modified metal catalysts	334
9.3	Selective Oxidation	337
9.3.1	Supported platinum-group metals	337
9.3.2	Supported gold and silver	339
9.3.3	Catalyst deactivation	341
9.4	Enantioselective Reactions	342
9.4.1	Enantioselective hydrogenation of activated ketones over supported Platinum	343
9.4.2	Enantioselective hydrogenation over other supported metals	351
9.5	Conclusions	353
	Index	359