- Email: [email protected]
Oxidative dehydrogenation of butanes to butadiene in China
N6
a catalyst with a composition of 50% BiVo.,Moo.sO, on 25% silica/alumina was mixed with a catalyst with a composition 50 wt.-% Bi4Ce4Mo10W20Xon silica at 470°C (molar feed ratio of 5 parts of propane:1 part of ammonia:20 parts of 02:1 part of water and a contact time of 1.4 s). The propane conversion was 1%. The yield and selectivity of propane to acrylonitrile were 6.3 and 5% respectively.
One-step Synthesis of Amides In a recent patentfromTexaco, Inc., J.J. Lin (U.S. Patent 4866177) reports a preparation of amides via alkenes, carbon monoxide and amines over a rhodium catalyst. In one example, they report using an autoclave reactor containing Rh203.5H20 (0.73 mm), diethylamide (205 mm), water 277 mm) in p-dioxane. The reactor was charged with 10 g of ethene, pressured with carbon monoxide at 2000 psi, and heated to 150°C in the presence of styrene. After 4 h the homogeneous solution was recovered with 95% yield to N,N-diethylpropionamide. They report lower yields with NH.,OH/ethene/CO.
Sonochemistry There has been a recent outpouring on articles dealing with sonochemistry, including its application to catalysis. Review articles include: KS. Suslick in Science, 247 (1990) 1439 and T.J. Mason and J.P. Lorimer in Endeavour, 13 (1989) 123. Two articles appropriate to catalysis include that by K.S. Suslick, D.J. Casadonte and S.J. Doktycz in Solid State lonics, 32 (1989) 444, in which the authors discuss the ultrasonic irradiation of nickel and copper powders, leading to dramatic changes in morphology. This results in an enhancement in the catalyst activity by a factor of 105. These effects are believed to be due applied catalysis -
Volume 65 No. 1 -3
to interparticle collisions removing a passivating layer of surface oxide. In the second article by S.J. Doktycz and K.S. Suslick, in Science, 247 (1990) 1067, the authors describe the irradiation of metal panicles in hydrocarbon liquids by ultrasound in order to estimate the maximum temperatures and speed reached during interpanicle collisions. Localized effective temperatures are estimated to reach 2600 to 3400°C at the point of impact for particles with an average diameter of approximately lOpurn. Pairs of panicles are observed with neck formation from localised melting. Selective
Oxidation of Hydrocar-
bons to Alcohols In additional work from the Sun Refining and Marketing Co., P.E. Ellis Jr., J.E. Lyons and H.M. Kyers, Jr. repot-l (U.S. Patent 4900871) relatively high yields for the selective oxidation of hydrocarbons to alcohol over a number of different catalysts. In particular, they find that when they halogenate the tetraphenylporphyrin ligand, they see a marked jump in the oxidation product. For example, using 0.023 mm of tetrakispentafluorophenylporphyrinato iron(lll) chloride for a period of 6 h at 125°C they convert propane (1.36 mm) in benzene to a mixture of isopropyl alcohol and acetone. During this time, in 10,000 psig of air, catalyst turnovers reach values of 675. Oxidative Dehydrogenation of Butenes to Butadiene In China A project on the oxidative dehydrogenation of butenes to butadiene has been conducted in China since the early 1960’s. In 1966, the Lanzhou Institute of Chemical Physics, Academia Sinica, developed a MO-containing three-component catalyst for the reaction, Later, both the Lanzhou October 1990
N7
Research Institute of Chemical Industry and Jinzhou Refinery performed pilot tests with this catalyst using both an adiabatic fixed-bed reactor and a multi-tube reactor. However, the tests had to be stopped due to difficulty in the control of the reaction temperature and severe coking. Later, the Jinzhou Refinery and the Institute of Coal Chemistry jointly finished a pilot test using a baffled fluidized-bed reactor and put this into commercial use. Several systems with butadiene capacities of 6000-15,000 tons per year have been built up, with a total capacity of up to 60,000 tons per year; however, only one of the plants reached the designed capacity due to a shortage of feedstock. This system operated at 496”C, 0.085 MPa, a space velocity of 82.6 h-l, a Odalkene molar ratio of 1.02 and a HaO/alkenes molar ratio of 4.6, giving a butene conversion of 63.4% and a butadiene yield of 52.7%. The main problems emerging were a MO loss from the catalyst, a lower selectivity, more oxygenated compounds in the products and blockages of the system due to condensation. In 1973, the Lanzhou Research Institute of Chemical Industry started to study a MO-containing six-component catalyst. Based on this, an industrial test was put into operation in the Synthetic Rubber Works of the Qilu Petrochemical Co. in February 1979. By the end of May 1982, thetotal accumulativetime on stream was over 15700 h. The new catalyst was thus superior to the three-component material. The active components of the catalyst are MO, Bi, Ni, Fe, P and K. The support is a spherical silica with large pores and a particle size of 30-60 mesh. The ratio of active components to support is 30:70. The catalysts are prepared by means of impregnation in a fluidized bed. Compared with the three-component material, the catalyst exhibits higher a buta-
applied catalysis -
diene yield (55%) and selectivity, but the yield of oxygenated compounds, especially of organic acids, is higher than with the older formulation. In 1981, the Lanzhou Research Institute of Chemical Physics successfully developed a ferrite catalyst with a spine1 structure which was designated H-198. The Jinzhou Refinery and the Synthetic Rubber Works of Yueyang Petrochemical Complex Works have now produced butadiene with a director-fluidized bed reactor, using H-198 instead of a MO-containing catalyst. The technology used is advanced; environmental pollution has been overcome and the production cost has been reduced remarkably. The operating conditions and technological specifications are much superior to those of the MO-containing catalyst and the new catalyst is a match for the commercial material of Petro-Tex, U.S.A. Typical data are as follows: reactor diameter, 2600 mm; temperature, 360°C; space velocity, 410.5 h-‘; Odalkenes molar ratio, 0.79; HgO/alkenes ratio, 10.2; butene conversion, 75%; selectivity, 90.4%; and butadiene yield, 66%. The Synthetic Rubber Works of Yanshan Petrochemical Co. has in the meantime developed a novel chromium-freeferrite catalyst designated B-02. The East China Institute of Chemical Technology has developed a technological process using two axial adiabatic bed reactors in series, making use of the B-02 catalyst. In the spring of 1986, the Synthetic Rubber Works of Qilu Petrochemical Co. built a system with a capacity of 16,000 tons of butadiene per year and ran this successfully, based on pilot test results. This makes the butadiene production in China by means of the oxidative dehydrogenation of butenes approach advanced world levels, The system uses two axial adiabatic
Volume 65 No. 1 - 3 October 1990
N8
NEW BOOK INFORMATION
Chemical Applications Therapy
of Group
Third Edition
A New Book Wiley have announced the publication of the third edition of “Chemical Applications of Group Therapy”, by F. Albert Cotton. Perhaps this is likely to become an important subject in the future, as I have recently heard complaints of over-stress in their work from many colleagues. However, further perusal of the leaflet shows that even chemical publishers can make mistakes in their proof-reading: Therapy should read Theory! JULIAN ROSS
fixed-bed reactors with a diameter of 3000 mm in a two-stage process. Typical data are: in the first stage, temperature of the inlet, 330-360X and of the outlet, 510550°C; space velocity, 180-190 h-‘; Odalkenes ratio, 0.47-0.50; H*O/alkenes ratio, 20-22; and in the and-stage, temperature of the inlet, 335-37O”C and of the outlet, 550-570°C; space velocity, 210-250 h-‘; Odalkenes ratio, 0.55-0.60; H20/alkenes ratio, 16-19; apparent conversion, 6670.8%; apparent selectivity, 89.0-91.6%, accumulative time on stream over 5137 h. This kind of reactor is characterized by a simple structure, easy operation and maintenance, lack of blocking from catalyst powder and effective heat recovery. (Source: Chinese J. Petrochem. Tech., 19 (1990) 183).
Catalytica 7th Annual Science and Technology Seminar
The Catalytica Studies Division has announced that its 7th annual Advances in applied catalysis -
Volume 65 No. 1 -3
Catalytic Technologies (ACT) seminar will be held from 14th to 16th October 1990, at the Santa Clara Convention Center in Santa Clara, California. This seminar is designed to provide a wide view of opportunities in the field of catalysis for seniorlevel chemical industry representatives. International academic and industrial experts will present new catalytic theory and practical commercial perspective. A session on worldwide trends in catalysis research and applications will include Kirill Zamaraev on catalysis research in the Soviet Union, Danielie Olivier on research in France and Makoto Misono on catalysis in Japan. A look at the frontiers of catalysis features Julius Rebek of MIT on new molecular shapes and Gaien Stucky of the University of California, Santa Barbara, on zeolites. New applications of NMR techniques to catalysis will be presented by Alexander Pines of the University of California, Berkeley, and Hugh Fleming of GFT will examine inorganic membranes. In the area of applications, Bruno Notari will talk
October 1990
a catalyst with a composition of 50% BiVo.,Moo.sO, on 25% silica/alumina was mixed with a catalyst with a composition 50 wt.-% Bi4Ce4Mo10W20Xon silica at 470°C (molar feed ratio of 5 parts of propane:1 part of ammonia:20 parts of 02:1 part of water and a contact time of 1.4 s). The propane conversion was 1%. The yield and selectivity of propane to acrylonitrile were 6.3 and 5% respectively.
One-step Synthesis of Amides In a recent patentfromTexaco, Inc., J.J. Lin (U.S. Patent 4866177) reports a preparation of amides via alkenes, carbon monoxide and amines over a rhodium catalyst. In one example, they report using an autoclave reactor containing Rh203.5H20 (0.73 mm), diethylamide (205 mm), water 277 mm) in p-dioxane. The reactor was charged with 10 g of ethene, pressured with carbon monoxide at 2000 psi, and heated to 150°C in the presence of styrene. After 4 h the homogeneous solution was recovered with 95% yield to N,N-diethylpropionamide. They report lower yields with NH.,OH/ethene/CO.
Sonochemistry There has been a recent outpouring on articles dealing with sonochemistry, including its application to catalysis. Review articles include: KS. Suslick in Science, 247 (1990) 1439 and T.J. Mason and J.P. Lorimer in Endeavour, 13 (1989) 123. Two articles appropriate to catalysis include that by K.S. Suslick, D.J. Casadonte and S.J. Doktycz in Solid State lonics, 32 (1989) 444, in which the authors discuss the ultrasonic irradiation of nickel and copper powders, leading to dramatic changes in morphology. This results in an enhancement in the catalyst activity by a factor of 105. These effects are believed to be due applied catalysis -
Volume 65 No. 1 -3
to interparticle collisions removing a passivating layer of surface oxide. In the second article by S.J. Doktycz and K.S. Suslick, in Science, 247 (1990) 1067, the authors describe the irradiation of metal panicles in hydrocarbon liquids by ultrasound in order to estimate the maximum temperatures and speed reached during interpanicle collisions. Localized effective temperatures are estimated to reach 2600 to 3400°C at the point of impact for particles with an average diameter of approximately lOpurn. Pairs of panicles are observed with neck formation from localised melting. Selective
Oxidation of Hydrocar-
bons to Alcohols In additional work from the Sun Refining and Marketing Co., P.E. Ellis Jr., J.E. Lyons and H.M. Kyers, Jr. repot-l (U.S. Patent 4900871) relatively high yields for the selective oxidation of hydrocarbons to alcohol over a number of different catalysts. In particular, they find that when they halogenate the tetraphenylporphyrin ligand, they see a marked jump in the oxidation product. For example, using 0.023 mm of tetrakispentafluorophenylporphyrinato iron(lll) chloride for a period of 6 h at 125°C they convert propane (1.36 mm) in benzene to a mixture of isopropyl alcohol and acetone. During this time, in 10,000 psig of air, catalyst turnovers reach values of 675. Oxidative Dehydrogenation of Butenes to Butadiene In China A project on the oxidative dehydrogenation of butenes to butadiene has been conducted in China since the early 1960’s. In 1966, the Lanzhou Institute of Chemical Physics, Academia Sinica, developed a MO-containing three-component catalyst for the reaction, Later, both the Lanzhou October 1990
N7
Research Institute of Chemical Industry and Jinzhou Refinery performed pilot tests with this catalyst using both an adiabatic fixed-bed reactor and a multi-tube reactor. However, the tests had to be stopped due to difficulty in the control of the reaction temperature and severe coking. Later, the Jinzhou Refinery and the Institute of Coal Chemistry jointly finished a pilot test using a baffled fluidized-bed reactor and put this into commercial use. Several systems with butadiene capacities of 6000-15,000 tons per year have been built up, with a total capacity of up to 60,000 tons per year; however, only one of the plants reached the designed capacity due to a shortage of feedstock. This system operated at 496”C, 0.085 MPa, a space velocity of 82.6 h-l, a Odalkene molar ratio of 1.02 and a HaO/alkenes molar ratio of 4.6, giving a butene conversion of 63.4% and a butadiene yield of 52.7%. The main problems emerging were a MO loss from the catalyst, a lower selectivity, more oxygenated compounds in the products and blockages of the system due to condensation. In 1973, the Lanzhou Research Institute of Chemical Industry started to study a MO-containing six-component catalyst. Based on this, an industrial test was put into operation in the Synthetic Rubber Works of the Qilu Petrochemical Co. in February 1979. By the end of May 1982, thetotal accumulativetime on stream was over 15700 h. The new catalyst was thus superior to the three-component material. The active components of the catalyst are MO, Bi, Ni, Fe, P and K. The support is a spherical silica with large pores and a particle size of 30-60 mesh. The ratio of active components to support is 30:70. The catalysts are prepared by means of impregnation in a fluidized bed. Compared with the three-component material, the catalyst exhibits higher a buta-
applied catalysis -
diene yield (55%) and selectivity, but the yield of oxygenated compounds, especially of organic acids, is higher than with the older formulation. In 1981, the Lanzhou Research Institute of Chemical Physics successfully developed a ferrite catalyst with a spine1 structure which was designated H-198. The Jinzhou Refinery and the Synthetic Rubber Works of Yueyang Petrochemical Complex Works have now produced butadiene with a director-fluidized bed reactor, using H-198 instead of a MO-containing catalyst. The technology used is advanced; environmental pollution has been overcome and the production cost has been reduced remarkably. The operating conditions and technological specifications are much superior to those of the MO-containing catalyst and the new catalyst is a match for the commercial material of Petro-Tex, U.S.A. Typical data are as follows: reactor diameter, 2600 mm; temperature, 360°C; space velocity, 410.5 h-‘; Odalkenes molar ratio, 0.79; HgO/alkenes ratio, 10.2; butene conversion, 75%; selectivity, 90.4%; and butadiene yield, 66%. The Synthetic Rubber Works of Yanshan Petrochemical Co. has in the meantime developed a novel chromium-freeferrite catalyst designated B-02. The East China Institute of Chemical Technology has developed a technological process using two axial adiabatic bed reactors in series, making use of the B-02 catalyst. In the spring of 1986, the Synthetic Rubber Works of Qilu Petrochemical Co. built a system with a capacity of 16,000 tons of butadiene per year and ran this successfully, based on pilot test results. This makes the butadiene production in China by means of the oxidative dehydrogenation of butenes approach advanced world levels, The system uses two axial adiabatic
Volume 65 No. 1 - 3 October 1990
N8
NEW BOOK INFORMATION
Chemical Applications Therapy
of Group
Third Edition
A New Book Wiley have announced the publication of the third edition of “Chemical Applications of Group Therapy”, by F. Albert Cotton. Perhaps this is likely to become an important subject in the future, as I have recently heard complaints of over-stress in their work from many colleagues. However, further perusal of the leaflet shows that even chemical publishers can make mistakes in their proof-reading: Therapy should read Theory! JULIAN ROSS
fixed-bed reactors with a diameter of 3000 mm in a two-stage process. Typical data are: in the first stage, temperature of the inlet, 330-360X and of the outlet, 510550°C; space velocity, 180-190 h-‘; Odalkenes ratio, 0.47-0.50; H*O/alkenes ratio, 20-22; and in the and-stage, temperature of the inlet, 335-37O”C and of the outlet, 550-570°C; space velocity, 210-250 h-‘; Odalkenes ratio, 0.55-0.60; H20/alkenes ratio, 16-19; apparent conversion, 6670.8%; apparent selectivity, 89.0-91.6%, accumulative time on stream over 5137 h. This kind of reactor is characterized by a simple structure, easy operation and maintenance, lack of blocking from catalyst powder and effective heat recovery. (Source: Chinese J. Petrochem. Tech., 19 (1990) 183).
Catalytica 7th Annual Science and Technology Seminar
The Catalytica Studies Division has announced that its 7th annual Advances in applied catalysis -
Volume 65 No. 1 -3
Catalytic Technologies (ACT) seminar will be held from 14th to 16th October 1990, at the Santa Clara Convention Center in Santa Clara, California. This seminar is designed to provide a wide view of opportunities in the field of catalysis for seniorlevel chemical industry representatives. International academic and industrial experts will present new catalytic theory and practical commercial perspective. A session on worldwide trends in catalysis research and applications will include Kirill Zamaraev on catalysis research in the Soviet Union, Danielie Olivier on research in France and Makoto Misono on catalysis in Japan. A look at the frontiers of catalysis features Julius Rebek of MIT on new molecular shapes and Gaien Stucky of the University of California, Santa Barbara, on zeolites. New applications of NMR techniques to catalysis will be presented by Alexander Pines of the University of California, Berkeley, and Hugh Fleming of GFT will examine inorganic membranes. In the area of applications, Bruno Notari will talk
October 1990