- Email: [email protected]
Applied catalysis
3JITOR I.R.H. Ross Department of Chemistry, Jniversity of Bradford, 3radford, Yorkshire 807 1DP. 2reat Britain ZOARESPONDENTS R.L. Age Depsrtamento Servicios T&nicos. Refineria de Petrdeos del Norte, S.A.. r(partado 1418, Bilbao 9, Spein t. Bweroft Leporte Industries Ltd., Moorfield Road, Widnes, Cheshire WA8 LNU, Greet Britain
H. Charcan lnstitut de Cetelvse, 2 Avenue Albert Einstein. 69628 Villeurbanne, France
Y.Muram Nikki Chemical Co. Ltd., New Ohtemschi Building, 2-1, Ohtemachi %Chome, Chivoda-ku, Tokyo, Japan
J.W. Geus Analvtisch Chemisch Labomtorium, Rijksuniveniteit Utrecht, Croesestreet 778.3522 AD Utrecht, The Netherlands
1
S. Nekmwa Central Research Laboratories, Kurarav Co. Ltd., 2645 Sakazu, Kureshiki, Oksyame, Japan
e. Gnnge 3roupe de PhvsicoChimie Mine’rale ?t de Cetelyse, Universite’ Cetholique k Louvein. Pfece Croix du Sud 1, 1348 Louvain-la-Neuve, Belgium
A. Norman h/son Refractories Sheffield S17 38J.
R.W. Jovnn Uew Technologv Division, British ‘etrdeum Research Centre, Zhartsev Road. Sunburyo”Thames, Vliddlesex lW16 7LN. Greet Britain
N. Pemicone Montedison S.p.A., G. Donegani Research Institute, Vie G. Fausrr 4. 28199 Novara, ltely
Moaburg, thd-Chemie AG, ostenrisdemtnm Moosburg,
A.G. Friedlandw Petroquimica General Mosconi, Maipu 464. PPiso, 1WS Buenos Aires, Argentina R.M. Friedman Process Sciences Department, Corporate Research, Monsanto Company, 800 North Lindbergh Blvd. 038, St. Lows, MO 63166, U.S.A. I. Furuoya Engineering Research Division, Takeda Chemicel Industries Ltd., 2-l 7-85 Juso.Ho”machi, Yodogewtku. Osaka. Japan
DeparVnent of Cbmisw. David Keir Building, Dueen’s University of Belfest. Belfast BTS 5AG, Northern Ireland
I
K. Kocfrloeff l+alyratcwenwcrk
8, i%
G.F.R.
WE. Dry Research Division, S8sol 1, P.O. Box 1 Seroiburg, South Africa
J.J. RoonY
::I,“: Assnciates Inc. 3266 Scott Boulevard. Building 7-E. 8.e”te Clara, CA 95051, U.S.A.
0-8652
Ltd., Owfer Bar, Great Britain
Lin Jimyi c/o School of Chemistry. Universitv of Bradford, Bradford, Yorkshire 8D7 1 DP, Greet Britain
’ 0. Martin0 lnrtitut Frewgair du Patrole, B.P. 311. 32566 Rueil-Melmeison, France
P.C.H. Mitchefl Department of Chemistry, The University of Reading, Whiteknights, Reading RG6 2AD. Great Britain
M.D. Mross BASF AG, M 310, D-6766 Ludwigshafe”, G.F.R.
~~~~dor
Tm&
AiS,
NvmYlevei 55,‘P.O. 80x 213, Lvngbv, Denmark I DK-2896 R.J. Sempson Research Technology Departme,,t, ICI Petrochemicals Division, P.O. Box 90, Wilton, Middlesborough, Clevefand 1~8 8~6, Great Britein
IJ.Schm Bereich Katalvse, Zentral lnetitut fBr Phvrischs Chamir, Rudowar Chausee 5. DDR-1199 BerlinAdlenhof, G.D.R.
1JJ.F. 8eboltm Depahent of Chemical Teehnofogv Delft University of Technology, Julianalaan 136.2628 8L Delft, /The Netherlands
330
A New Catalyst Laboratory
from a University
Results from university catalyst research programmes are rarely applicable to industry without a major development effort. The aim of the university research is by nature more fundamental and the long experimental programme which may eventually lead to improved catalyst performance is better suited to the goals of the industrial laboratory. An exception is provided by a new Indium catalyst for dehydrogenation of alcohols (US Pat. 4224190, Sept. 23, 1980) which was developed at the Instituttet for Kemiteknik. Danmarks Tekniske Hdjskole, and has-recently been sold to a major European chemical company. More than 10 years ago it was noted by Ogino and coworkers (J. Catal. 55 36 (1978) and earlier references contained therein) that metallic Indium has a remarkably high selectivity for the dehydrogenation of primary and secondary alcohols. No attempt was made, however, to disperse this expensive metal (which is molten at the reaction temperature 35Oo-45OoC), and the activity per g of In, when alcohol vapour was passed over the surface of a pool of molten In, was far too small to make the catalyst commercially attractive. The research group at Instituttet for Kemiteknik invented a method by which minute droplets (2 p diameter) of In were dispersed in a ceramic suppor (MgO with pore diameter 6-800 Fc1, thus creatinq an enormous free metallic surface which results in a 40000-fold increase in activity compared to the original papers. Mg(OH)2 (or MgO) and 0.4-l wt % In203 are mixed as powders, tabletted and calcined to form a firm porous MgO structure in which the In203 is Subsequent reduction encapsulated. ('in situ' with alcohol vapour or with H2) yields droplets of In metal hich are trapped in cages of the 700 x Since the metal does not MgO network. wet the ceramic support, no coalescense of drops or sweating-out of metal iS noted even after many weeks of continuous use. The vapour pressure of In is negligible at 35Oo-450°C, and no loss of activity is noticable after 4 weeks on stream. MgO has a small
but noticable dehydrogenation activity. It does not promote dehydration of the alcohol, the major side reaction in most other dehydrogenation catalysts. The activity of the new catalyst at 420°C is 5-20 times higher than for existing commercial catalysts. Its selectivity for dehydrogenation of several aliphatic and cvclic alcohols was shown to be better than 99.5%. The catalvst is used at a temperature which"is more than 120°C higher than e.g. that used for commercial copper oxide catalysts; this may be a major advantage as the equilibrium conversion at the maximum feasible operating temperature (% 28O'C) for the Cu catalysts is considerably less than one. Palladium
Hydrogenation
Catalysts
Johnson Matthey recently announced (see European Chemical News, Octs, 1981) a new type of selective hydrogenation catalysts for the preparation of halogenated aromatic amines used in the preparation of agrochemicals, pharmaceuticals and synthetic dyes. Catalysts previously used in these preparations, involvino the hvdroqenation of the corresponding n
Catalyst
Fluidised
for SNG Production Bed
in a
For the past five years, considerable attention has been paid to the development of fluidised'bed methanation catalysts. Besides the patent application of Sud-Chemie (W. Germany) (DE-OS 2816035: reference in ADDS. Catal. 1981, 1; 407) Ruhr Chemie (W. Germany),aE-OS 2952683, have recently revealed a new procedure for the production of such catalysts, based on the spray-drying technique. The
H. Charcan lnstitut de Cetelvse, 2 Avenue Albert Einstein. 69628 Villeurbanne, France
Y.Muram Nikki Chemical Co. Ltd., New Ohtemschi Building, 2-1, Ohtemachi %Chome, Chivoda-ku, Tokyo, Japan
J.W. Geus Analvtisch Chemisch Labomtorium, Rijksuniveniteit Utrecht, Croesestreet 778.3522 AD Utrecht, The Netherlands
1
S. Nekmwa Central Research Laboratories, Kurarav Co. Ltd., 2645 Sakazu, Kureshiki, Oksyame, Japan
e. Gnnge 3roupe de PhvsicoChimie Mine’rale ?t de Cetelyse, Universite’ Cetholique k Louvein. Pfece Croix du Sud 1, 1348 Louvain-la-Neuve, Belgium
A. Norman h/son Refractories Sheffield S17 38J.
R.W. Jovnn Uew Technologv Division, British ‘etrdeum Research Centre, Zhartsev Road. Sunburyo”Thames, Vliddlesex lW16 7LN. Greet Britain
N. Pemicone Montedison S.p.A., G. Donegani Research Institute, Vie G. Fausrr 4. 28199 Novara, ltely
Moaburg, thd-Chemie AG, ostenrisdemtnm Moosburg,
A.G. Friedlandw Petroquimica General Mosconi, Maipu 464. PPiso, 1WS Buenos Aires, Argentina R.M. Friedman Process Sciences Department, Corporate Research, Monsanto Company, 800 North Lindbergh Blvd. 038, St. Lows, MO 63166, U.S.A. I. Furuoya Engineering Research Division, Takeda Chemicel Industries Ltd., 2-l 7-85 Juso.Ho”machi, Yodogewtku. Osaka. Japan
DeparVnent of Cbmisw. David Keir Building, Dueen’s University of Belfest. Belfast BTS 5AG, Northern Ireland
I
K. Kocfrloeff l+alyratcwenwcrk
8, i%
G.F.R.
WE. Dry Research Division, S8sol 1, P.O. Box 1 Seroiburg, South Africa
J.J. RoonY
::I,“: Assnciates Inc. 3266 Scott Boulevard. Building 7-E. 8.e”te Clara, CA 95051, U.S.A.
0-8652
Ltd., Owfer Bar, Great Britain
Lin Jimyi c/o School of Chemistry. Universitv of Bradford, Bradford, Yorkshire 8D7 1 DP, Greet Britain
’ 0. Martin0 lnrtitut Frewgair du Patrole, B.P. 311. 32566 Rueil-Melmeison, France
P.C.H. Mitchefl Department of Chemistry, The University of Reading, Whiteknights, Reading RG6 2AD. Great Britain
M.D. Mross BASF AG, M 310, D-6766 Ludwigshafe”, G.F.R.
~~~~dor
Tm&
AiS,
NvmYlevei 55,‘P.O. 80x 213, Lvngbv, Denmark I DK-2896 R.J. Sempson Research Technology Departme,,t, ICI Petrochemicals Division, P.O. Box 90, Wilton, Middlesborough, Clevefand 1~8 8~6, Great Britein
IJ.Schm Bereich Katalvse, Zentral lnetitut fBr Phvrischs Chamir, Rudowar Chausee 5. DDR-1199 BerlinAdlenhof, G.D.R.
1JJ.F. 8eboltm Depahent of Chemical Teehnofogv Delft University of Technology, Julianalaan 136.2628 8L Delft, /The Netherlands
330
A New Catalyst Laboratory
from a University
Results from university catalyst research programmes are rarely applicable to industry without a major development effort. The aim of the university research is by nature more fundamental and the long experimental programme which may eventually lead to improved catalyst performance is better suited to the goals of the industrial laboratory. An exception is provided by a new Indium catalyst for dehydrogenation of alcohols (US Pat. 4224190, Sept. 23, 1980) which was developed at the Instituttet for Kemiteknik. Danmarks Tekniske Hdjskole, and has-recently been sold to a major European chemical company. More than 10 years ago it was noted by Ogino and coworkers (J. Catal. 55 36 (1978) and earlier references contained therein) that metallic Indium has a remarkably high selectivity for the dehydrogenation of primary and secondary alcohols. No attempt was made, however, to disperse this expensive metal (which is molten at the reaction temperature 35Oo-45OoC), and the activity per g of In, when alcohol vapour was passed over the surface of a pool of molten In, was far too small to make the catalyst commercially attractive. The research group at Instituttet for Kemiteknik invented a method by which minute droplets (2 p diameter) of In were dispersed in a ceramic suppor (MgO with pore diameter 6-800 Fc1, thus creatinq an enormous free metallic surface which results in a 40000-fold increase in activity compared to the original papers. Mg(OH)2 (or MgO) and 0.4-l wt % In203 are mixed as powders, tabletted and calcined to form a firm porous MgO structure in which the In203 is Subsequent reduction encapsulated. ('in situ' with alcohol vapour or with H2) yields droplets of In metal hich are trapped in cages of the 700 x Since the metal does not MgO network. wet the ceramic support, no coalescense of drops or sweating-out of metal iS noted even after many weeks of continuous use. The vapour pressure of In is negligible at 35Oo-450°C, and no loss of activity is noticable after 4 weeks on stream. MgO has a small
but noticable dehydrogenation activity. It does not promote dehydration of the alcohol, the major side reaction in most other dehydrogenation catalysts. The activity of the new catalyst at 420°C is 5-20 times higher than for existing commercial catalysts. Its selectivity for dehydrogenation of several aliphatic and cvclic alcohols was shown to be better than 99.5%. The catalvst is used at a temperature which"is more than 120°C higher than e.g. that used for commercial copper oxide catalysts; this may be a major advantage as the equilibrium conversion at the maximum feasible operating temperature (% 28O'C) for the Cu catalysts is considerably less than one. Palladium
Hydrogenation
Catalysts
Johnson Matthey recently announced (see European Chemical News, Octs, 1981) a new type of selective hydrogenation catalysts for the preparation of halogenated aromatic amines used in the preparation of agrochemicals, pharmaceuticals and synthetic dyes. Catalysts previously used in these preparations, involvino the hvdroqenation of the corresponding n
Catalyst
Fluidised
for SNG Production Bed
in a
For the past five years, considerable attention has been paid to the development of fluidised'bed methanation catalysts. Besides the patent application of Sud-Chemie (W. Germany) (DE-OS 2816035: reference in ADDS. Catal. 1981, 1; 407) Ruhr Chemie (W. Germany),aE-OS 2952683, have recently revealed a new procedure for the production of such catalysts, based on the spray-drying technique. The