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Chinese advances in carbon monoxide hydrogenation catalysts
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tion; however, its high initial reactivity offers potential.
Chinese Advances in Carbon Monoxide Hydrogenation Catalysts
B. Zhong and his co-workers (Shanxi Institute of Coal Chemistry, China) have reported work on the selective synthesis of gasoline from syngas via a two-stage FT/ZSM-5 process (see Proc. of the 5th National Congress on Catalysis, Lanzhou, China, 20-23 August 1990, p. 5). The catalyst used in the first stage consisted of ultrafine particles of iron-manganese. It is claimed that the catalyst system (each stage with 5 ml of catalyst) gave a conversion of carbon monoxide of over 97% (in one pass), a yield of C1 ÷ hydrocarbons of 144-163 g/Nm 3 of CO and H2, the fraction of C5 ÷ being 103-122 g/Nm 3 of CO and H2; the following reaction conditions were used: stage 1,360°C, stage 2, 280-300°C; pressure 3.0 MPa; H j C O = 2; GHSV = 450-1330 h-~. STY's of C1 + and C5+ hydrocarbons as high as 0.169 and 0.122 g/gcatJh, respectively, were reported for a GHSV of 1330 h-~. The activity and selectivity remained practically unchanged at the end of a life test of 2300 h. Structural characterization indicated that the catalyst material was composed of mixed spinels of Fe-Mn with ultrafine particle sizes of 0.03-0.07~m, in which the iron was highly dispersed in the manganese component. A unique catalyst comprising a highly dispersed iron and manganese component supported on an activated carbon (AC) has been developed in the laboratory of Professor L. Lin, Dalian Institute of Chemical Physics, China (see Proc. of the 3rd China-Japan Symposium on Coal and C~ Chemistry, Kunming, China, 29 Oct.-1 Nov. 1990, p. 401). With this catalyst a high
yield of liquid fuels could be synthesized via the conventional single-stage F-T process. The catalytic results indicated that for these Fe/AC catalysts, the small average pore diameter of the AC supports favoured a higher yield of gasoline fraction due to the shape selective effects. With the addition of manganese oxides to the Fe/AC, the selectivity of liquid fuels and lower alkenes was enhanced. A typical catalyst with composition 8% Fe 4% Mn/AC gave a yield of C1+ hydrocarbons of 145 g/Nm 3 syngas, in which C5÷ liquid comprised 64-69 wt.-% (gasoline ca. 70% and diesel ca. 20%) and C2-C4 gaseous products 20-30 wt.-% (alkenes 80%); the reaction conditions were: reaction temperature 300°C; pressure 2.5 MPa; H2/CO = 1; GHSV = 1000 h-l; reaction time 36 h. A paper by W. Zhang and his co-workers, Lanzhou Institute of Chemical Physics, China (see Proc. of the 3rd China-Japan Symposium on Coal and C~ Chemistry, Kunming, China, 29 Oct.-1 Nov. 1990, p. 425) describes studies of carbon monoxide hydrogenation to ethene over M-Zr catalysts (metal or metal oxides containing zirconium). It is reported that the said catalyst showed a very high selectivity to ethene (more than 90%) for a short time at 360°C with the following conditions: 0.8 MPa, H~CO = 4.5 and SV = 345 h-1. Unstability of the catalysts caused a decrease of activity after 3 h. It was found that both ammonia and a small amount of O2-containing nitrogen can bring about a partial recovery of carbon monoxide conversion but not that of the selectivity to alkenes. The catalytic behaviours of M-Zr seem to be controlled by their acidity, basicity and the extent of the interaction between M and Zr; the formation of ethene possibly occurs via methanol as an intermediate.
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The catalytic properties of a K2CO3-promoted MoS2catalyst which is resistant to sulphur during the synthesis of lower alcohols from syngas have been reported by B. Leng and his co-workers from the Beijing Research Institute of Chemical Technology (see Proc. of the 5th National Congress on Catalysis, Lanzhou, China, 20-23 August 1990, p. 305). The synthesis reactions were carried out in a microreactor under the following conditions: temperature 280-320°C, pressure 5.0-9.5 MPa, H2/CO = 1.1 and SV = 3500-10,000 h-1, using a feed gas containing sulphur 100300 ng/ml. The results indicated that when the space velocity of the feed gas was 6000-10,000 h-~, the STY of the mixed alcohols reached 0.3 g/ml cat./h with a selectivity towards total alcohols of more than 80%, the proportion of C2+ alcohols was in the range 30-70%. This catalyst is claimed to possess improved stability and resistance to sulphur during a period of 200 h. The addition of a certain amount of cobalt to the catalyst appears to give a further increase in the alcohol selectivity. Partial Oxidation of Methane to Methanol This reaction has been studied by Z. Huang et al. in the presence of Cr3+-zr 4÷SO42-/silica gel catalyst (Cr203 2%) at about 250°C and 0.4 MPa. This catalyst gave a methane conversion of about 5% with a methanol yield of over 3%. The oxygenates formed were methanol, formaldehyde and the carbon oxides. The authors pointed out that the active sites of the catalyst were the super-strong B acid sites. They discuss a possible reaction pathway. (Source: Chinese Journal Natural Gas Chemical Industry, 5 (1989) 6)
Dehydrogenation of Methanol to Methyl Formate A plant with a scale of 2000 tons per year for the production of methyl formate from the dehydrogenation of methanol was built and put into operation in 1990 in the Wujin Chemical Fertilizer factory, China. This process, using a solid catalyst and operating at atmospheric pressure, was developed by the Southwest Research Institute of Chemical Technology, China. The products from this process have been claimed to cost 30-40% less than those from the conventional process. (Source: Comprehensive News, Qilu Petrochemical Corp., China, 8 December 199) Unicat signs Collaboration Agreement in the United States It has been announced that Unicat s.a., created at the end of 1989 in order to promote the research of several universities in the area of catalysis, has signed a collaboration agreement with Chemical Engineering Partners (CEP) located at Irvine (California). This company is part of the group Evergreen Oil Inc. (Irvine, California), which has a worldwide recognized expertise in catalytic processes, especially for petroleum refining. These catalytic processes require a multidisciplinary approach involving a collaboration between experts in organic chemistry, biochemistry, surface science, crystallography and chemical engineering. Unicat, which aims at being an interface on European level between industry and university for catalysis research, has already obtained the cooperation of several Belgian, Dutch and German laboratories. Negotiations are going on with other
tion; however, its high initial reactivity offers potential.
Chinese Advances in Carbon Monoxide Hydrogenation Catalysts
B. Zhong and his co-workers (Shanxi Institute of Coal Chemistry, China) have reported work on the selective synthesis of gasoline from syngas via a two-stage FT/ZSM-5 process (see Proc. of the 5th National Congress on Catalysis, Lanzhou, China, 20-23 August 1990, p. 5). The catalyst used in the first stage consisted of ultrafine particles of iron-manganese. It is claimed that the catalyst system (each stage with 5 ml of catalyst) gave a conversion of carbon monoxide of over 97% (in one pass), a yield of C1 ÷ hydrocarbons of 144-163 g/Nm 3 of CO and H2, the fraction of C5 ÷ being 103-122 g/Nm 3 of CO and H2; the following reaction conditions were used: stage 1,360°C, stage 2, 280-300°C; pressure 3.0 MPa; H j C O = 2; GHSV = 450-1330 h-~. STY's of C1 + and C5+ hydrocarbons as high as 0.169 and 0.122 g/gcatJh, respectively, were reported for a GHSV of 1330 h-~. The activity and selectivity remained practically unchanged at the end of a life test of 2300 h. Structural characterization indicated that the catalyst material was composed of mixed spinels of Fe-Mn with ultrafine particle sizes of 0.03-0.07~m, in which the iron was highly dispersed in the manganese component. A unique catalyst comprising a highly dispersed iron and manganese component supported on an activated carbon (AC) has been developed in the laboratory of Professor L. Lin, Dalian Institute of Chemical Physics, China (see Proc. of the 3rd China-Japan Symposium on Coal and C~ Chemistry, Kunming, China, 29 Oct.-1 Nov. 1990, p. 401). With this catalyst a high
yield of liquid fuels could be synthesized via the conventional single-stage F-T process. The catalytic results indicated that for these Fe/AC catalysts, the small average pore diameter of the AC supports favoured a higher yield of gasoline fraction due to the shape selective effects. With the addition of manganese oxides to the Fe/AC, the selectivity of liquid fuels and lower alkenes was enhanced. A typical catalyst with composition 8% Fe 4% Mn/AC gave a yield of C1+ hydrocarbons of 145 g/Nm 3 syngas, in which C5÷ liquid comprised 64-69 wt.-% (gasoline ca. 70% and diesel ca. 20%) and C2-C4 gaseous products 20-30 wt.-% (alkenes 80%); the reaction conditions were: reaction temperature 300°C; pressure 2.5 MPa; H2/CO = 1; GHSV = 1000 h-l; reaction time 36 h. A paper by W. Zhang and his co-workers, Lanzhou Institute of Chemical Physics, China (see Proc. of the 3rd China-Japan Symposium on Coal and C~ Chemistry, Kunming, China, 29 Oct.-1 Nov. 1990, p. 425) describes studies of carbon monoxide hydrogenation to ethene over M-Zr catalysts (metal or metal oxides containing zirconium). It is reported that the said catalyst showed a very high selectivity to ethene (more than 90%) for a short time at 360°C with the following conditions: 0.8 MPa, H~CO = 4.5 and SV = 345 h-1. Unstability of the catalysts caused a decrease of activity after 3 h. It was found that both ammonia and a small amount of O2-containing nitrogen can bring about a partial recovery of carbon monoxide conversion but not that of the selectivity to alkenes. The catalytic behaviours of M-Zr seem to be controlled by their acidity, basicity and the extent of the interaction between M and Zr; the formation of ethene possibly occurs via methanol as an intermediate.
N20
The catalytic properties of a K2CO3-promoted MoS2catalyst which is resistant to sulphur during the synthesis of lower alcohols from syngas have been reported by B. Leng and his co-workers from the Beijing Research Institute of Chemical Technology (see Proc. of the 5th National Congress on Catalysis, Lanzhou, China, 20-23 August 1990, p. 305). The synthesis reactions were carried out in a microreactor under the following conditions: temperature 280-320°C, pressure 5.0-9.5 MPa, H2/CO = 1.1 and SV = 3500-10,000 h-1, using a feed gas containing sulphur 100300 ng/ml. The results indicated that when the space velocity of the feed gas was 6000-10,000 h-~, the STY of the mixed alcohols reached 0.3 g/ml cat./h with a selectivity towards total alcohols of more than 80%, the proportion of C2+ alcohols was in the range 30-70%. This catalyst is claimed to possess improved stability and resistance to sulphur during a period of 200 h. The addition of a certain amount of cobalt to the catalyst appears to give a further increase in the alcohol selectivity. Partial Oxidation of Methane to Methanol This reaction has been studied by Z. Huang et al. in the presence of Cr3+-zr 4÷SO42-/silica gel catalyst (Cr203 2%) at about 250°C and 0.4 MPa. This catalyst gave a methane conversion of about 5% with a methanol yield of over 3%. The oxygenates formed were methanol, formaldehyde and the carbon oxides. The authors pointed out that the active sites of the catalyst were the super-strong B acid sites. They discuss a possible reaction pathway. (Source: Chinese Journal Natural Gas Chemical Industry, 5 (1989) 6)
Dehydrogenation of Methanol to Methyl Formate A plant with a scale of 2000 tons per year for the production of methyl formate from the dehydrogenation of methanol was built and put into operation in 1990 in the Wujin Chemical Fertilizer factory, China. This process, using a solid catalyst and operating at atmospheric pressure, was developed by the Southwest Research Institute of Chemical Technology, China. The products from this process have been claimed to cost 30-40% less than those from the conventional process. (Source: Comprehensive News, Qilu Petrochemical Corp., China, 8 December 199) Unicat signs Collaboration Agreement in the United States It has been announced that Unicat s.a., created at the end of 1989 in order to promote the research of several universities in the area of catalysis, has signed a collaboration agreement with Chemical Engineering Partners (CEP) located at Irvine (California). This company is part of the group Evergreen Oil Inc. (Irvine, California), which has a worldwide recognized expertise in catalytic processes, especially for petroleum refining. These catalytic processes require a multidisciplinary approach involving a collaboration between experts in organic chemistry, biochemistry, surface science, crystallography and chemical engineering. Unicat, which aims at being an interface on European level between industry and university for catalysis research, has already obtained the cooperation of several Belgian, Dutch and German laboratories. Negotiations are going on with other