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Review Synthesis of Methanol Part 1. Catalysts and Kinetics

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Applied Catalysis, 36 (1988) 1-65

Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

Review

Synthesis of Methanol

Part 1. Catalysts and Kinetics

G.C. CHINCHEN, P.J. DENNY, J.R. JENNINGS**, MS. SPENCER and K.C. WAUGH
ICI Chemicals & Polymers Group, Research & Technology Department, Billingham Catalysis
Centre, P.O. Box 1, Billingham, Cleveland TS23 ILB (U.K.)
(Received 20 March 1987, accepted 9 July 1987)

CONTENTS

1. Introduction.. ............................................................................................................................... 2
2. Catalysts and catalyst development.. ......................................................................................... 4
2.1. Introduction .................................................................................................................... 4
2.2. Precipitated copper/zinc oxide/alumina catalysts.. .................................................... 5
2.2.1. Effects of additives.. ....................................................................................................... 6
2.3. Raney copper catalysts.. ................................................................................................ 9
2.4. Intermetallic compounds ............................................................................................... 11
2.5. Precious metal catalysts ............................................................................................... .15
2.5.1. Palladium catalysts ....................................................................................................... .15
2.5.2. Other precious metals ................................................................................................... .20
3. Selectivity of copper-based catalysts ........................................................................................ .23
3.1. General background.. .................................................................................................... .23
3.2. Higher alcohols ............................................................................................................... 27
3.3. Hydrocarbons ................................................................................................................. 29
3.4. Esters.. ............................................................................................................................. 31
3.5. Ethers.. ............................................................................................................................ 32
3.6. Ketones ........................................................................................................................... 33
4. Equilibrium and kinetics.. .......................................................................................................... .34
4.1. Introduction.. ................................................................................................................. .34
4.2. Equilibrium of methanol synthesis ............................................................................. .34
4.3. Equilibria of reactions related to methanol synthesis ............................................... .37
4.4. Kinetic expressions.. ..................................................................................................... .38
4.5. Kinetics of synthesis from hydrogen-carbon monoxide mixtures over supported
copper catalysts.. ........................................................................................................... .39
4.6. Kinetics of synthesis from hydrogen-carbon monoxide-carbon dioxide mixtures
over supported copper catalysts.. ................................................................................. .41
4.6.1. Copper/zinc oxide catalysts ......................................................................................... .41
4.6.2. Commercial copper/zinc oxide/alumina catalysts ..................................................... .43
4.6.3. Other supported copper catalysts ................................................................................ .47

*ICI Chemicals and Polymers Group, Research and Technology Department, P.O. Box 90,
Wilton, Middlesbrough, Cleveland TS6 8JE, lJ.K.

0166-9834/88/$03.50 0 1988 Elsevier Science Publishers B.V.

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