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Some new catalysts containing rhodium
117 Mr. Robin Paul (Deputy Chairman of Mond Division) will be responsible for the programnes and performance of the Separate units at Wilton, Grouo. Welwyn and'in Mond Division will carry out research in direct support of the Divisions' existing business. Catalysis will continue to feature strongly in the programmes of these units. There will continue to be strong links with Agricultural Division, which will maintain its current catalyst activities. research. The Synthesis
of Hydrogen
Peroxide
Air Products Limited has recently developed a new catalytic route for the synthesis of hydrogen peroxide (British Patent Applications 2074040 and 2074145). The work'was described at the American . Chemical Society's 1981 meetino in New York in August in a paper by one of the inventors, Dr. P. N. Dyer. High pressure, oxygen-lean, hydrogen-oxygen mixtures outside the flamnable limits are sparged through a two phase immiscible liquid mixture of de-ionized water and, for example I,1 2- trichlorotrifluoroethane. at from I* to IOoC. Initially, the organic layer contains the palladium complex PdCl2(P(C5F5)3)2, but under reaction conditions this rapidly forms a very active catalyst film at the water-halofluorocarbon interface, probably by hydrolysis and reduction. Agitation, for instance by sparging, leads to the dispersion of water in the halofluorocarbon with each water droplet surrounded by a film. Hydrogen peroxide is formed at the film and extracted rapidly into the water droplets away from the catalyst. Phase separation is almost instantaneous when sparging ceases; the catalyst remains at the interface and a palladium free peroxide containing water layer can be taken off. Resparging at the correct rate for good mixing restores the synthesis, No phosphine oxidation can be detected. The rate of peroxide production is proportional to oxygen pressure and independent of hydrogen pressure and catalyst concentration down to the low level of about 1.5 x IO-4 M of initial comolex in solution. There is evidence that this initial concentration of catalyst is the minimum required which in due course just "covers" the liquid interface under the experimental dispersion conditions. Greater amounts of catalyst do not then
In 90 ml of water enhance the rate. with twi ce as much halofluorocarbon, maximum catalyst turnover rates are around 1,000 wt % peroxide/hr/psi oxygen gm. mole of catalyst complex. The rate does not decrease greatly as the peroxide concentration approaches 5 wt % and the selectivity to peroxide is generally above 70% of-the oxygen consumed, no doubt because of rapid extraction of the product into the aqueous layer away from the film. The advantages of a liquid/liquid-interfacesupported catalyst are: (a) effective utilisation of metal content leading to high activity; (b) negligible catalyst loss from reactor; (c) easy product separation and removal; and (b) high selectivity due to reaction followed by extraction. F. Moseley Aromatics
from Synthesis
Gas
Shell International Research have produced a new iron silicate catalyst fEuropean Patent 30.751) for the manufacture of aromatic'hydrocarbons from carbon monoxide and hydrogen mixtures by reacting silica and iron oxides together in the presence of an amine (e.g. butylamine). Some New Catalysts
Containing
Rhodium
Two new rhodium-containing catalysts for the production, inter alia, of simple alcohols from COd Hp, have recently been patented. The first, claimed by the British Petroleum Co. Ltd (European Patent 33,212) produces alcohols and aldehydes in liquid media and comprises a silica carrier supporting rhodium and one or more of a number of other elements (Mg, Fe, Zr, Mn, MO, W etc). The second, claimed by the Ethyl Corporation (US Patent 4,272,410) produces (also from CO and H2) mixtures of lower aliphatic alcohols, acetic acid and acetate esters; it is composed of 0.5 - 15% of rhodium, 1.0 - 25% of tungsten, 0.5 - 10% of sodium, all supported on alumina. A third patent, to Imperial Chemical Industries Ltd. (European Patent 33,425) describes a catalyst used to produce ethylene glycol from CO and H2 in a liquid medium; it comprises of ruthenium, another group VIII metal (preferably rhodium) and, optionally, a Group IA, IIA or IIB metal oxide, hydroxide or
118 salt or a nitrogen base. The French Institute of Petroleum have recently disclosed (German Patent 3,042,297) a new catalyst for the production of benzene by the steam dealkylation of xylene and/or toluene. This contains rhodium (0.1 - 2%), cooper, silver or qold (0.05 - 2%). rhenium (0.05 - 2%j and; optionally, one or more other platinum group metal (0.1 - 1%)) all supported on an alumina carrier. The Norton Company have patented (British Patent 1,589,661) a hydrogenmordenite based catalyst, with a specified Si02:A1203 ratio, loaded with at least 0.2% of elemental rhodium, and optionally containing palladium in combination with the rhodium. This may be used for the hydrocracking of hydrocarbons to gasoline-range products. Monsanto's
New Maleic Anhydride
Plant
Monsanto Company has broken ground for the world's largest maleic anhydride plant. Located in Pensacola, Florida, it will have a 130 million-pound-peryear capacity and is scheduied to‘be on stream earlv in 1983. The new facilitv will use Monsanto's butane feedstock technology. At present, benzene is the primary feedstock for the manufacture of maleic anhydride. Butane has several advantages over benzene: it is environmentally less controversial; it is less expensive raw material; and it will more readily be available in the future. Monsanto is also converting to butane technology its 115 billion-pound-peryear maleic anhydride unit, located at its John F. Queeny Plant in St. Louis. Advances
in Catalytic
Chemistry
II
This meeting, honouring Dr. Heinz Heinemann, is to be held under the auspices of the Department of Fuel Engineering, University of Utah, at Hotel Utah, Salt Lake City, from 18 to The symposium will comp21 May 1982. rise of eight sessions on zeolite catalysis, catalytic processing of heavy oils and residuals, supported metal catalysis, modern spectroscopic techniques applied to catalysis, hydrogenation of carbon monoxide, catalysis over supported metal oxides and sulphides, homogeneous catalysis The and chemical process industries. honorary symposium chairman is Professor Alex 6. Oblad.
Fluidised
Cracking
Catalysts
The increase in the number of fluidised catalytic cracking (FCC) units in Europe of approximately 50% over the last few years has led to an equivalent increase in demand for FCC catalysts (see Applied Catalysis, 1981, 1, 99). A recent article in Oil and Gas Journal (June 29th, 1981) describes some results obtained with the Katalistics EKZ series of FCC catalysts; some of these results were obtained in their own laboratories and some in tests in Elf France's Amb& Refinery (near Bordeaux) and Deutshe BP's Refinery at Vohburg. A number of advantageous features of the EKZ series of catalysts are highlighted. The catalyst consist of a zeolite component in a matrix; the latter have low surface areas and this gives rise to improved selectivity towards gasoline. They have a hydrothermal stability equal to or better than cracking catalysts commercially available. The reqeneration of the catalysts required-a lower quantity of coke formation than the competitive samples previously used because of a greater activity for CO combustion to C02; almost complete removal of CO was achieved. The hydrogen to methane ratio of the products was also reduced,despite an increase in the metals content of the feedstock used,compared with previous operation.
Lead Tolerant
Catalysts
for Car Exhausts
Catalysts developed for car exhaust systems to meet the emission regulations in the US, where unleaded fuels are not used, are not resistant to poisoning by the lead compounds and other additives present in typical European fuels. A recent article in Platinum Metals Review (1981, 2, 142) b.v A. F. Diwell and 8. Harrison describes experiments in which a typical ceramic monolith supported catalyst was tested using different fuel compositions and exhaust system designs (eg. catalyst inlet temperature). A new series of lead tolerant catalysts, using pure platinum on a "Fecralloy" metal substrate, was tested and it was found that they were much more resistant to poisoning than the ceramic-based materials. It is currently being evaluated by the leading Europen motor companies.
of Hydrogen
Peroxide
Air Products Limited has recently developed a new catalytic route for the synthesis of hydrogen peroxide (British Patent Applications 2074040 and 2074145). The work'was described at the American . Chemical Society's 1981 meetino in New York in August in a paper by one of the inventors, Dr. P. N. Dyer. High pressure, oxygen-lean, hydrogen-oxygen mixtures outside the flamnable limits are sparged through a two phase immiscible liquid mixture of de-ionized water and, for example I,1 2- trichlorotrifluoroethane. at from I* to IOoC. Initially, the organic layer contains the palladium complex PdCl2(P(C5F5)3)2, but under reaction conditions this rapidly forms a very active catalyst film at the water-halofluorocarbon interface, probably by hydrolysis and reduction. Agitation, for instance by sparging, leads to the dispersion of water in the halofluorocarbon with each water droplet surrounded by a film. Hydrogen peroxide is formed at the film and extracted rapidly into the water droplets away from the catalyst. Phase separation is almost instantaneous when sparging ceases; the catalyst remains at the interface and a palladium free peroxide containing water layer can be taken off. Resparging at the correct rate for good mixing restores the synthesis, No phosphine oxidation can be detected. The rate of peroxide production is proportional to oxygen pressure and independent of hydrogen pressure and catalyst concentration down to the low level of about 1.5 x IO-4 M of initial comolex in solution. There is evidence that this initial concentration of catalyst is the minimum required which in due course just "covers" the liquid interface under the experimental dispersion conditions. Greater amounts of catalyst do not then
In 90 ml of water enhance the rate. with twi ce as much halofluorocarbon, maximum catalyst turnover rates are around 1,000 wt % peroxide/hr/psi oxygen gm. mole of catalyst complex. The rate does not decrease greatly as the peroxide concentration approaches 5 wt % and the selectivity to peroxide is generally above 70% of-the oxygen consumed, no doubt because of rapid extraction of the product into the aqueous layer away from the film. The advantages of a liquid/liquid-interfacesupported catalyst are: (a) effective utilisation of metal content leading to high activity; (b) negligible catalyst loss from reactor; (c) easy product separation and removal; and (b) high selectivity due to reaction followed by extraction. F. Moseley Aromatics
from Synthesis
Gas
Shell International Research have produced a new iron silicate catalyst fEuropean Patent 30.751) for the manufacture of aromatic'hydrocarbons from carbon monoxide and hydrogen mixtures by reacting silica and iron oxides together in the presence of an amine (e.g. butylamine). Some New Catalysts
Containing
Rhodium
Two new rhodium-containing catalysts for the production, inter alia, of simple alcohols from COd Hp, have recently been patented. The first, claimed by the British Petroleum Co. Ltd (European Patent 33,212) produces alcohols and aldehydes in liquid media and comprises a silica carrier supporting rhodium and one or more of a number of other elements (Mg, Fe, Zr, Mn, MO, W etc). The second, claimed by the Ethyl Corporation (US Patent 4,272,410) produces (also from CO and H2) mixtures of lower aliphatic alcohols, acetic acid and acetate esters; it is composed of 0.5 - 15% of rhodium, 1.0 - 25% of tungsten, 0.5 - 10% of sodium, all supported on alumina. A third patent, to Imperial Chemical Industries Ltd. (European Patent 33,425) describes a catalyst used to produce ethylene glycol from CO and H2 in a liquid medium; it comprises of ruthenium, another group VIII metal (preferably rhodium) and, optionally, a Group IA, IIA or IIB metal oxide, hydroxide or
118 salt or a nitrogen base. The French Institute of Petroleum have recently disclosed (German Patent 3,042,297) a new catalyst for the production of benzene by the steam dealkylation of xylene and/or toluene. This contains rhodium (0.1 - 2%), cooper, silver or qold (0.05 - 2%). rhenium (0.05 - 2%j and; optionally, one or more other platinum group metal (0.1 - 1%)) all supported on an alumina carrier. The Norton Company have patented (British Patent 1,589,661) a hydrogenmordenite based catalyst, with a specified Si02:A1203 ratio, loaded with at least 0.2% of elemental rhodium, and optionally containing palladium in combination with the rhodium. This may be used for the hydrocracking of hydrocarbons to gasoline-range products. Monsanto's
New Maleic Anhydride
Plant
Monsanto Company has broken ground for the world's largest maleic anhydride plant. Located in Pensacola, Florida, it will have a 130 million-pound-peryear capacity and is scheduied to‘be on stream earlv in 1983. The new facilitv will use Monsanto's butane feedstock technology. At present, benzene is the primary feedstock for the manufacture of maleic anhydride. Butane has several advantages over benzene: it is environmentally less controversial; it is less expensive raw material; and it will more readily be available in the future. Monsanto is also converting to butane technology its 115 billion-pound-peryear maleic anhydride unit, located at its John F. Queeny Plant in St. Louis. Advances
in Catalytic
Chemistry
II
This meeting, honouring Dr. Heinz Heinemann, is to be held under the auspices of the Department of Fuel Engineering, University of Utah, at Hotel Utah, Salt Lake City, from 18 to The symposium will comp21 May 1982. rise of eight sessions on zeolite catalysis, catalytic processing of heavy oils and residuals, supported metal catalysis, modern spectroscopic techniques applied to catalysis, hydrogenation of carbon monoxide, catalysis over supported metal oxides and sulphides, homogeneous catalysis The and chemical process industries. honorary symposium chairman is Professor Alex 6. Oblad.
Fluidised
Cracking
Catalysts
The increase in the number of fluidised catalytic cracking (FCC) units in Europe of approximately 50% over the last few years has led to an equivalent increase in demand for FCC catalysts (see Applied Catalysis, 1981, 1, 99). A recent article in Oil and Gas Journal (June 29th, 1981) describes some results obtained with the Katalistics EKZ series of FCC catalysts; some of these results were obtained in their own laboratories and some in tests in Elf France's Amb& Refinery (near Bordeaux) and Deutshe BP's Refinery at Vohburg. A number of advantageous features of the EKZ series of catalysts are highlighted. The catalyst consist of a zeolite component in a matrix; the latter have low surface areas and this gives rise to improved selectivity towards gasoline. They have a hydrothermal stability equal to or better than cracking catalysts commercially available. The reqeneration of the catalysts required-a lower quantity of coke formation than the competitive samples previously used because of a greater activity for CO combustion to C02; almost complete removal of CO was achieved. The hydrogen to methane ratio of the products was also reduced,despite an increase in the metals content of the feedstock used,compared with previous operation.
Lead Tolerant
Catalysts
for Car Exhausts
Catalysts developed for car exhaust systems to meet the emission regulations in the US, where unleaded fuels are not used, are not resistant to poisoning by the lead compounds and other additives present in typical European fuels. A recent article in Platinum Metals Review (1981, 2, 142) b.v A. F. Diwell and 8. Harrison describes experiments in which a typical ceramic monolith supported catalyst was tested using different fuel compositions and exhaust system designs (eg. catalyst inlet temperature). A new series of lead tolerant catalysts, using pure platinum on a "Fecralloy" metal substrate, was tested and it was found that they were much more resistant to poisoning than the ceramic-based materials. It is currently being evaluated by the leading Europen motor companies.