- Email: [email protected]
Recent patents and publications
N13
New Engelhard
Catalyst
Plant In Ter-
neuzen September saw the opening in Terneuzen (The Netherlands) by Engelhard of a new plant and laboratory for the production of FCC catalysts for the cracking of crude oil. Claimed to be the most advanced plant of its kind in the world, this is the first FCC plant of Engelhard outside the U.S.; it will supply catalysts to refineries in Europe, Africa and the Middle East. It will produce the newest Engelhard catalysts, Precision and Octidyne Extra, introduced at the beginning of 1989. Catalyst Consuttants This organisation, based in Spring House, Pennsylvania, U.S.A., have reorganised to market their services under The Catalyst Group which will consist of four companies: Catalyst Consultants, Inc., Catalyst Consultants Europe Ltd., Environmental Catalyst Consultants, and Catalyst Consultants Publishing Company (which will take over publishing of The Catalyst Review). Recent Patents and Publications
Shape selective synthesis Styrene from n-Octane
of
In a recently issued U.S. Patent assigned to the Mobil Oil Corporation, R.M. Dessau and E.W. Valyocsik (U.S. Patent 4 922 942) described the use of an indium (0.01 to 20 wt.-%)-containing ZSM-5 catalyst for the shape-selective synthesis of styrenefrom n-octane. Withinthe specifications of the patent they provide and interesting table Fable A) which describes hydrocarbon conversion and benzene/toluene seleotiviiies for platinum-coated boron- or
applied catalysis -
indium-containing ZSM-5 catalysts. With n-heptane, both boron-treated or SilZSM-5 gave mixtures of benzene and toluene on dehydrogenation. However, the indium ZSM-5 gives 97% selectivll to toluene at 99% conversion. Example 1 within the patent (containing 1.85% platinum on In/ZSM5) reports a 99.4% conversion at 550°C of n-octane to yield 94.3% styrene.
Carbon Dioxide and Methane as Feedstocks H. Arakawa, in Technology Japan, (21(19&3)31), provides a review entitled “Development Trends of Direct Utilization of Methane and Carbon Dioxide as Feedstocks for Chemicals” which focuses on selective methane oxidation as well as selective CO:! reduction. The review is targeted at utilizing C, chemistry in anticipation of any future worldwide oil crisis. He reports that the consensus is “that C, chemical industry will eventually replace the petrochemical industry in the future”. The paper reviews the solid acid catalyst processes which might eventually lead to improved catalysts to fix methane and COB. NOx Abatement M. Grove and W. Sturm (Ceramic Engineering Science Proceedings, 10(1999)325) have described the CER-NO,” processfor the selective catalytic reduction of NO, as applied particularly to glass metting furnaces which generate NO,. The CERNOx” process is a turnkey NO, (SCR) abatement process which uses a ceramic, molecular sieve catalyst honeycomb module. The article claims that unlike metal type SCR catalysts, the molecular sieve catalysts are virtually immune to poisoning, plugging and masking. They suggest that high electrostatic forces within the pores reduces the reaction potential of NO, and
Volume 55 No. 2 -15 November 1989
N14
ammoniawhich allows a lowertemperature of reaction (300°C). The exothermic reaction in the small pore space generates nitrogen gas and water vapour which is expelled from the pore structure and thus self-cleans the catalyst surface. The authors from Steuler International (and Industriewerke) report that this abatement system has a successful track record over the lastfiieyears in Europe, and it is technically viable in combination with the removal of SOdSOs, HF, HCI and dust.
Fixation of Molecular Nitrogen V. Vishwanathan has shown (J. Chem. Sot., Chem. Commun., (1989)848) thatfixation of molecular nitrogen can occur on a rhodium/riOn catalyst. Prereduced in hydrogen, the 1% Rhodium/titania catalyst reduced at various temperatures gives rise to two ESR signals. Adsorption of carbon monoxide and nitrogen increase with reduction temperature; while titania alone shows some adsorption of nitrogen, the rhodium on titania system shows a much larger increase above 573 K. Vishwanathan suggeststhe possibility of direct interaction between Ti3+ and the nitrogen molecule and speculates on the use of this catalyst for the synthesis of ammonia.
Linde X. Instead, the pure cerium source was mislabelled and consisted of a mixture of rare earth elements! This lead to rare earth Y and USY. A historical account of the development of ZSM-5 is also provided. Kerr concludes that what is needed for the future ‘is insight that will enable chemists to predict structures and other properties that will emerge when various starting ingredients are mixed together in specific ratios at particular temperatures and pressures. Until then, trial and error will prevail. Fottunately, that approach has served industry rather well so far.”
Selective tylene
hydrogenation
of ace-
A recent Japanese patent (JO1022-826A) describes the selective hydrogenation of acetylenic compounds to prepare ethylenic compounds. Specifically, a thin ruthenium film of 5-800 A is formed via glow discharge onto a suitable solid support. A dilute acetylene mixture was fed to the catalyst (inside the degassed reactor) and the reaction carried out at 300°C under 140 Torr of hydrogen for 90 min to yield a conversion of 99% with a selectivity of 99.7% to ethylene.
Catalysis to produce a lubricant History of Zeolite Science George T. Kerr has provided a useful review of the history of zeolite synthesis in Scientific American (July 1989, pp. IOO105). This is an interesting personal perspective of the pioneering work of McBain, Barrer, Milton, Breck, Kerr, N.Y. Chen, Haag and many others. The discovery of Linde A, X and Y zeolites is described. The chance discovery of Durabead 5, the first zeolite-based gas-oil cracking catalyst, arose because of a misunderstanding. The intent was to substitute Ce(lll) for AI(III) in
applied catalysis -Volume
55 No. 2 -15
An interesting article by J.L. Lauer and B.G. Bunting in Tribol. Trans. (31(1988) 339) describes the generation of a lubricant carbon film produced by the catalytic decomposition of ethylene on nickel-containing surfaces and alloys. The resulting carbon films reduce the friction at a sliding interface at temperatures up to 650°C.
VPI Synthesis Plant A description of the synthesis of VPI-5 has now appeared in an international patent citation (VU0 8961-912-A, to Dow Chemical Corporation). One example de-
November 1989
N15
scribes the preparation as follows: “A slurry of 55 g of A1203dihydrate in 150 g of water was added to a solution of 90 g of 85% phosphoric acid in 100 g of water. The mixture was aged for 2 h and 189 g of 55% TBA was added and the resulting mixture stirred for 2 l/2 h at room temperature followed by heating in an autoclave for 24 h at 145°C. The crystals which were formed were filtered and washed with water and dried at room temperature.” Some Recent Articles The following is a listing of some of the items which have recently been listed in the API Abstracts Series, Catalysts and Catatysis. Vol. 36, No. 29 D.K. Patel, Oxidative dehydrogenation of alkanes over mixed V Mg oxides, magnesium vanadates, and various metal orthovanadates, Diss. Abstr. Int., B 49(1989) 4930-B. J.A.S.P. Carreiro and M. Baerns, Oxidative coupling of methane. 1. Alkaline earth compound catalysts, J, Catal., 117(1989) 258. D.J.C. Yates et al., Supported lithium tetraborate as a catalyst for the continuous oxidative dehydrogenation of methane, J. Catal., 117(1989)299. A.A. Tsyganenko et al., lnrfared study of low-temperature CO adsorption on La203, J. Phys. Chem., 93(1989)4189. H. Kodama et al., Catalytic activity of H mordenite treated with chlorofluoromethanes for alkylation of chlorobenzene with Nippon Kagaku Kaishi, methanol, 3(1989)498. A. Miyake et al., Roles of pore structure and acidity of RNHZSM-5 and Pt/HZSM-5
applied catalysis -
in the conversion of hexanes, Nippon Kagaku Kaishi, 3(1989)509. H. Nishijima et al., Conversion of the light naphtha to aromatic hydrocarbons on MFI type zeolites, Nippon Kagaku Kaishi, 3(1989)591. Vol. 36, No. 30 P.L. Layman and D.A. O’Sullivan, BP Chemicals boosts global acetic acid capacity, Chem. Eng. News, 67(27)(1989) 1880. P.S. Kuo and B.L. Yang, AIP04 as a support material for VP0 catalysts, J. Catal., 117(1989)301. S.S. Shepelev and KG. lone, Oxidative synthesis of higher hydrocarbons from methane on zeolites, J. Catal., 117(1989)362. E. lwamatsu and K. Aika, Kinetic anaiysis of oxidative coupling of methane over Na+-doped MgO, J. Catal., 117(1989)416. J.A.S.P. Carreiro and M. Baerns, Oxidative coupling of methane. 2. Composite catalysts of basic materials, J. Catal., 117 (1989)396. Catalysts in automobiles: A history, Automot. Eng. (Pittsb.), 97(6)(June 1989) 69. Catalytic reactor retrofit (for air pollution control equipment), J. Air Waste Manage. Assoc., 39(5)(May 1989)759. J.F. Tanguay et al., Dichloromethane photodegradation using titanium catalysts, J. Catal., 117(1989)335. Vol. 36, No. 37 R. Westerholm et al., Exhaust emission reduction from a heavy-duty diesel truck, using a catalyst and a particulate trap, Fuel, 88(1989)858. H. Weltens et al., Design of exhaust catalyst systems for European applica-
Volume 55 No. 2 -15 November 1989
New Engelhard
Catalyst
Plant In Ter-
neuzen September saw the opening in Terneuzen (The Netherlands) by Engelhard of a new plant and laboratory for the production of FCC catalysts for the cracking of crude oil. Claimed to be the most advanced plant of its kind in the world, this is the first FCC plant of Engelhard outside the U.S.; it will supply catalysts to refineries in Europe, Africa and the Middle East. It will produce the newest Engelhard catalysts, Precision and Octidyne Extra, introduced at the beginning of 1989. Catalyst Consuttants This organisation, based in Spring House, Pennsylvania, U.S.A., have reorganised to market their services under The Catalyst Group which will consist of four companies: Catalyst Consultants, Inc., Catalyst Consultants Europe Ltd., Environmental Catalyst Consultants, and Catalyst Consultants Publishing Company (which will take over publishing of The Catalyst Review). Recent Patents and Publications
Shape selective synthesis Styrene from n-Octane
of
In a recently issued U.S. Patent assigned to the Mobil Oil Corporation, R.M. Dessau and E.W. Valyocsik (U.S. Patent 4 922 942) described the use of an indium (0.01 to 20 wt.-%)-containing ZSM-5 catalyst for the shape-selective synthesis of styrenefrom n-octane. Withinthe specifications of the patent they provide and interesting table Fable A) which describes hydrocarbon conversion and benzene/toluene seleotiviiies for platinum-coated boron- or
applied catalysis -
indium-containing ZSM-5 catalysts. With n-heptane, both boron-treated or SilZSM-5 gave mixtures of benzene and toluene on dehydrogenation. However, the indium ZSM-5 gives 97% selectivll to toluene at 99% conversion. Example 1 within the patent (containing 1.85% platinum on In/ZSM5) reports a 99.4% conversion at 550°C of n-octane to yield 94.3% styrene.
Carbon Dioxide and Methane as Feedstocks H. Arakawa, in Technology Japan, (21(19&3)31), provides a review entitled “Development Trends of Direct Utilization of Methane and Carbon Dioxide as Feedstocks for Chemicals” which focuses on selective methane oxidation as well as selective CO:! reduction. The review is targeted at utilizing C, chemistry in anticipation of any future worldwide oil crisis. He reports that the consensus is “that C, chemical industry will eventually replace the petrochemical industry in the future”. The paper reviews the solid acid catalyst processes which might eventually lead to improved catalysts to fix methane and COB. NOx Abatement M. Grove and W. Sturm (Ceramic Engineering Science Proceedings, 10(1999)325) have described the CER-NO,” processfor the selective catalytic reduction of NO, as applied particularly to glass metting furnaces which generate NO,. The CERNOx” process is a turnkey NO, (SCR) abatement process which uses a ceramic, molecular sieve catalyst honeycomb module. The article claims that unlike metal type SCR catalysts, the molecular sieve catalysts are virtually immune to poisoning, plugging and masking. They suggest that high electrostatic forces within the pores reduces the reaction potential of NO, and
Volume 55 No. 2 -15 November 1989
N14
ammoniawhich allows a lowertemperature of reaction (300°C). The exothermic reaction in the small pore space generates nitrogen gas and water vapour which is expelled from the pore structure and thus self-cleans the catalyst surface. The authors from Steuler International (and Industriewerke) report that this abatement system has a successful track record over the lastfiieyears in Europe, and it is technically viable in combination with the removal of SOdSOs, HF, HCI and dust.
Fixation of Molecular Nitrogen V. Vishwanathan has shown (J. Chem. Sot., Chem. Commun., (1989)848) thatfixation of molecular nitrogen can occur on a rhodium/riOn catalyst. Prereduced in hydrogen, the 1% Rhodium/titania catalyst reduced at various temperatures gives rise to two ESR signals. Adsorption of carbon monoxide and nitrogen increase with reduction temperature; while titania alone shows some adsorption of nitrogen, the rhodium on titania system shows a much larger increase above 573 K. Vishwanathan suggeststhe possibility of direct interaction between Ti3+ and the nitrogen molecule and speculates on the use of this catalyst for the synthesis of ammonia.
Linde X. Instead, the pure cerium source was mislabelled and consisted of a mixture of rare earth elements! This lead to rare earth Y and USY. A historical account of the development of ZSM-5 is also provided. Kerr concludes that what is needed for the future ‘is insight that will enable chemists to predict structures and other properties that will emerge when various starting ingredients are mixed together in specific ratios at particular temperatures and pressures. Until then, trial and error will prevail. Fottunately, that approach has served industry rather well so far.”
Selective tylene
hydrogenation
of ace-
A recent Japanese patent (JO1022-826A) describes the selective hydrogenation of acetylenic compounds to prepare ethylenic compounds. Specifically, a thin ruthenium film of 5-800 A is formed via glow discharge onto a suitable solid support. A dilute acetylene mixture was fed to the catalyst (inside the degassed reactor) and the reaction carried out at 300°C under 140 Torr of hydrogen for 90 min to yield a conversion of 99% with a selectivity of 99.7% to ethylene.
Catalysis to produce a lubricant History of Zeolite Science George T. Kerr has provided a useful review of the history of zeolite synthesis in Scientific American (July 1989, pp. IOO105). This is an interesting personal perspective of the pioneering work of McBain, Barrer, Milton, Breck, Kerr, N.Y. Chen, Haag and many others. The discovery of Linde A, X and Y zeolites is described. The chance discovery of Durabead 5, the first zeolite-based gas-oil cracking catalyst, arose because of a misunderstanding. The intent was to substitute Ce(lll) for AI(III) in
applied catalysis -Volume
55 No. 2 -15
An interesting article by J.L. Lauer and B.G. Bunting in Tribol. Trans. (31(1988) 339) describes the generation of a lubricant carbon film produced by the catalytic decomposition of ethylene on nickel-containing surfaces and alloys. The resulting carbon films reduce the friction at a sliding interface at temperatures up to 650°C.
VPI Synthesis Plant A description of the synthesis of VPI-5 has now appeared in an international patent citation (VU0 8961-912-A, to Dow Chemical Corporation). One example de-
November 1989
N15
scribes the preparation as follows: “A slurry of 55 g of A1203dihydrate in 150 g of water was added to a solution of 90 g of 85% phosphoric acid in 100 g of water. The mixture was aged for 2 h and 189 g of 55% TBA was added and the resulting mixture stirred for 2 l/2 h at room temperature followed by heating in an autoclave for 24 h at 145°C. The crystals which were formed were filtered and washed with water and dried at room temperature.” Some Recent Articles The following is a listing of some of the items which have recently been listed in the API Abstracts Series, Catalysts and Catatysis. Vol. 36, No. 29 D.K. Patel, Oxidative dehydrogenation of alkanes over mixed V Mg oxides, magnesium vanadates, and various metal orthovanadates, Diss. Abstr. Int., B 49(1989) 4930-B. J.A.S.P. Carreiro and M. Baerns, Oxidative coupling of methane. 1. Alkaline earth compound catalysts, J, Catal., 117(1989) 258. D.J.C. Yates et al., Supported lithium tetraborate as a catalyst for the continuous oxidative dehydrogenation of methane, J. Catal., 117(1989)299. A.A. Tsyganenko et al., lnrfared study of low-temperature CO adsorption on La203, J. Phys. Chem., 93(1989)4189. H. Kodama et al., Catalytic activity of H mordenite treated with chlorofluoromethanes for alkylation of chlorobenzene with Nippon Kagaku Kaishi, methanol, 3(1989)498. A. Miyake et al., Roles of pore structure and acidity of RNHZSM-5 and Pt/HZSM-5
applied catalysis -
in the conversion of hexanes, Nippon Kagaku Kaishi, 3(1989)509. H. Nishijima et al., Conversion of the light naphtha to aromatic hydrocarbons on MFI type zeolites, Nippon Kagaku Kaishi, 3(1989)591. Vol. 36, No. 30 P.L. Layman and D.A. O’Sullivan, BP Chemicals boosts global acetic acid capacity, Chem. Eng. News, 67(27)(1989) 1880. P.S. Kuo and B.L. Yang, AIP04 as a support material for VP0 catalysts, J. Catal., 117(1989)301. S.S. Shepelev and KG. lone, Oxidative synthesis of higher hydrocarbons from methane on zeolites, J. Catal., 117(1989)362. E. lwamatsu and K. Aika, Kinetic anaiysis of oxidative coupling of methane over Na+-doped MgO, J. Catal., 117(1989)416. J.A.S.P. Carreiro and M. Baerns, Oxidative coupling of methane. 2. Composite catalysts of basic materials, J. Catal., 117 (1989)396. Catalysts in automobiles: A history, Automot. Eng. (Pittsb.), 97(6)(June 1989) 69. Catalytic reactor retrofit (for air pollution control equipment), J. Air Waste Manage. Assoc., 39(5)(May 1989)759. J.F. Tanguay et al., Dichloromethane photodegradation using titanium catalysts, J. Catal., 117(1989)335. Vol. 36, No. 37 R. Westerholm et al., Exhaust emission reduction from a heavy-duty diesel truck, using a catalyst and a particulate trap, Fuel, 88(1989)858. H. Weltens et al., Design of exhaust catalyst systems for European applica-
Volume 55 No. 2 -15 November 1989