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Today, the conditions for the use of dimethyl ether as a civilian fuel for alcohol ether fuels and alternative fuels for diesel vehicles are maturing. In addition, DME will also replace HCFCs for aerosols, refrigerants and blowing agents in order to meet the environmental protection situation. Needless to say, the prospects for the production and application of dimethyl ether are very bright. However, the current dimethyl ether production technology is still not perfect, affecting the project scale, investment and energy consumption and other indicators to a certain extent, and it is urgent to make a breakthrough.
Recently, the latest research results of the Dalian Institute of Chemical Physics of the Chinese Academy of Sciences showed a major highlight to the industry. They successfully developed a two-step methanol dehydration method to prepare dimethyl ether upgrading technology - catalytic distillation of dimethyl ether technology. The reporter interviewed one of the main researchers of the technology, Sun Xinde, a research associate at the Dalian Institute of Chemicals.
Reporter: Dalian Institute of Chemical Physics, Chinese Academy of Sciences, has developed a gas-phase dehydration process of methanol to make dimethyl ether. Why should we continue to develop catalytic distillation to make dimethyl ether technology?
Sun Xinde: Although the existing dimethyl ether technology has achieved success, it is still not perfect.
At present, the production method of dimethyl ether has one-step method and two-step method. In theory, the one-step process has the advantages of short process and high syngas conversion ratio compared with methanol dehydration two-step process. However, the catalyst life is short, the equipment is complicated, the reaction product separation is difficult, the energy consumption is high, and it is not mature enough. There are no large-scale production facilities outside.
At present, most of the large-scale dimethyl ether construction projects announced at home and abroad adopt two-step process technology, indicating that the law has a strong comprehensive competitiveness. The two-step method can be further divided into liquid-phase dehydration method and gas-phase dehydration method. Domestically, it is represented by the compound acid liquid-phase method of Shandong Jiutai Chemical Co., Ltd., the Southwest Research and Design Institute of Chemical Industry, and the gas phase dehydration method of the Dalian Institute of Chemical Physics of the Chinese Academy of Sciences. Both have built larger production facilities. These technologies still have some areas for improvement, such as longer processes, greater investment, higher energy consumption, and slightly more side effects. The gas-phase methanol conversion rate is low (70% to 80%), the temperature rise of the reactor bed is large, and the device is not easy to increase in size. In response to the above problems, Dalian Institute of Technology proposed to apply catalytic distillation technology to the process of methanol dehydration to dimethyl ether to achieve technology upgrading.
Reporter: Why did you choose to develop catalytic distillation technology as an upgrade technology for DME?
Sun Xinde: Catalytic distillation technology is a chemical engineering method that allows the catalytic reaction process and the distillation separation process to be carried out simultaneously in a catalyst-containing catalytic distillation column. It has been successful in the production of methyl tert-butyl ether and many other chemical processes. use.
In the reaction system of methanol dehydration to dimethyl ether, the volatility of methanol is between the reaction product dimethyl ether and water, and the reaction is an exothermic reaction, and is particularly suitable for catalytic distillation technology. The reaction zone in the central part of the catalytic distillation column is filled with a catalyst. Dimethyl ether and water are respectively discharged from the top of the catalytic distillation column and the column reactor, and methanol is enriched in the reaction zone in the middle of the catalytic distillation column. Highly efficient conversion.
Based on the solid-acid catalytic catalysis of methanol dehydration to produce dimethyl ether fixed bed technology, Dalian Chemical Industry Co., Ltd. has developed a new catalyst for the catalytic distillation of dimethyl ether and catalytic distillation technology based on the characteristics of methanol dehydration. At present, the technology has applied for 6 patents.
Reporter: What are the advantages of catalytic distillation technology over existing dimethyl ether production technologies?
Sun Xinde: Dalian Chemicals has conducted a lot of research work on the activity, selectivity, and especially the stability and catalytic distillation process of catalytic distillation catalysts, and has made major breakthroughs. The technical indexes of catalytic distillation technology developed by Dalian Institute of Chemical Industry are: methanol single conversion rate ≥ 95%, dimethyl ether selectivity ≥ 99.98%, raw material consumption ≤ 1.405 tons/ton, steam consumption 0.5 tons/ton, dimethyl ether product purity It is 99.9%. Catalytic distillation catalyst has a good stability, can run long below 180 °C, the selectivity of dimethyl ether up to 99.99%. Compared with the traditional methanol dehydration technology, the new technology has the following advantages:
First, the technical reaction temperature is easy to control, which eliminates the defects of the easy-to-overtemperature existing in the traditional gas phase method.
The second is the high selectivity of conversion. This technology breaks the chemical equilibrium limitation of the methanol dehydration reaction, the methanol is almost completely converted, the occurrence of side reactions is suppressed, the selectivity of the target product is improved, and the distillation loss of dimethyl ether is reduced. Low methanol consumption.
The third is to save investment and production costs. The technical process is simple, the number of equipments is reduced, and the investment is saved; the heat utilization is sufficient, and the reaction heat is directly used as the heat required for evaporation. The investment in catalytic distillation technology is about 60% to 70% of gas phase technology, and the energy consumption is only 40% of gas phase technology. The production cost of dimethyl ether is greatly reduced.
Fourth, the catalyst life is longer. In the catalytic distillation process, the dimethyl ether produced by the reaction and the possible trace olefin by-products generated rapidly leave the reaction zone and accumulate to the top of the tower. Their concentration in the liquid phase of the reaction zone is very low, and both the reaction rate of dimethyl ether to produce olefins and the reaction rate of olefins to generate carbon deposits are greatly suppressed. In addition, under the reaction conditions of the catalytic distillation process, the saturated liquid phase material mainly containing alcohol diffuses into the catalyst particles to perform the reaction, and the change of the material components after the reaction lowers the saturated vapor pressure. This will vaporize some of the material, and the heat absorbed by the vaporization is much greater than the heat released by the reaction, so that the internal temperature of the particles is lower than the surface temperature. These factors are all conducive to extending the life of the catalyst. In the catalytic distillation process, the catalyst life can reach 2 years.
This technology overcomes the problems of long process flow, high energy consumption, and large investment in the existing technology. It is a major advancement in the production technology of dimethyl ether. At present, it has completed the pilot test and has the conditions for industrialization. The Dalian Institute of Chemical Industry hopes to cooperate with relevant companies and jointly promote the technology to industrialization.
Recently, the latest research results of the Dalian Institute of Chemical Physics of the Chinese Academy of Sciences showed a major highlight to the industry. They successfully developed a two-step methanol dehydration method to prepare dimethyl ether upgrading technology - catalytic distillation of dimethyl ether technology. The reporter interviewed one of the main researchers of the technology, Sun Xinde, a research associate at the Dalian Institute of Chemicals.
Reporter: Dalian Institute of Chemical Physics, Chinese Academy of Sciences, has developed a gas-phase dehydration process of methanol to make dimethyl ether. Why should we continue to develop catalytic distillation to make dimethyl ether technology?
Sun Xinde: Although the existing dimethyl ether technology has achieved success, it is still not perfect.
At present, the production method of dimethyl ether has one-step method and two-step method. In theory, the one-step process has the advantages of short process and high syngas conversion ratio compared with methanol dehydration two-step process. However, the catalyst life is short, the equipment is complicated, the reaction product separation is difficult, the energy consumption is high, and it is not mature enough. There are no large-scale production facilities outside.
At present, most of the large-scale dimethyl ether construction projects announced at home and abroad adopt two-step process technology, indicating that the law has a strong comprehensive competitiveness. The two-step method can be further divided into liquid-phase dehydration method and gas-phase dehydration method. Domestically, it is represented by the compound acid liquid-phase method of Shandong Jiutai Chemical Co., Ltd., the Southwest Research and Design Institute of Chemical Industry, and the gas phase dehydration method of the Dalian Institute of Chemical Physics of the Chinese Academy of Sciences. Both have built larger production facilities. These technologies still have some areas for improvement, such as longer processes, greater investment, higher energy consumption, and slightly more side effects. The gas-phase methanol conversion rate is low (70% to 80%), the temperature rise of the reactor bed is large, and the device is not easy to increase in size. In response to the above problems, Dalian Institute of Technology proposed to apply catalytic distillation technology to the process of methanol dehydration to dimethyl ether to achieve technology upgrading.
Reporter: Why did you choose to develop catalytic distillation technology as an upgrade technology for DME?
Sun Xinde: Catalytic distillation technology is a chemical engineering method that allows the catalytic reaction process and the distillation separation process to be carried out simultaneously in a catalyst-containing catalytic distillation column. It has been successful in the production of methyl tert-butyl ether and many other chemical processes. use.
In the reaction system of methanol dehydration to dimethyl ether, the volatility of methanol is between the reaction product dimethyl ether and water, and the reaction is an exothermic reaction, and is particularly suitable for catalytic distillation technology. The reaction zone in the central part of the catalytic distillation column is filled with a catalyst. Dimethyl ether and water are respectively discharged from the top of the catalytic distillation column and the column reactor, and methanol is enriched in the reaction zone in the middle of the catalytic distillation column. Highly efficient conversion.
Based on the solid-acid catalytic catalysis of methanol dehydration to produce dimethyl ether fixed bed technology, Dalian Chemical Industry Co., Ltd. has developed a new catalyst for the catalytic distillation of dimethyl ether and catalytic distillation technology based on the characteristics of methanol dehydration. At present, the technology has applied for 6 patents.
Reporter: What are the advantages of catalytic distillation technology over existing dimethyl ether production technologies?
Sun Xinde: Dalian Chemicals has conducted a lot of research work on the activity, selectivity, and especially the stability and catalytic distillation process of catalytic distillation catalysts, and has made major breakthroughs. The technical indexes of catalytic distillation technology developed by Dalian Institute of Chemical Industry are: methanol single conversion rate ≥ 95%, dimethyl ether selectivity ≥ 99.98%, raw material consumption ≤ 1.405 tons/ton, steam consumption 0.5 tons/ton, dimethyl ether product purity It is 99.9%. Catalytic distillation catalyst has a good stability, can run long below 180 °C, the selectivity of dimethyl ether up to 99.99%. Compared with the traditional methanol dehydration technology, the new technology has the following advantages:
First, the technical reaction temperature is easy to control, which eliminates the defects of the easy-to-overtemperature existing in the traditional gas phase method.
The second is the high selectivity of conversion. This technology breaks the chemical equilibrium limitation of the methanol dehydration reaction, the methanol is almost completely converted, the occurrence of side reactions is suppressed, the selectivity of the target product is improved, and the distillation loss of dimethyl ether is reduced. Low methanol consumption.
The third is to save investment and production costs. The technical process is simple, the number of equipments is reduced, and the investment is saved; the heat utilization is sufficient, and the reaction heat is directly used as the heat required for evaporation. The investment in catalytic distillation technology is about 60% to 70% of gas phase technology, and the energy consumption is only 40% of gas phase technology. The production cost of dimethyl ether is greatly reduced.
Fourth, the catalyst life is longer. In the catalytic distillation process, the dimethyl ether produced by the reaction and the possible trace olefin by-products generated rapidly leave the reaction zone and accumulate to the top of the tower. Their concentration in the liquid phase of the reaction zone is very low, and both the reaction rate of dimethyl ether to produce olefins and the reaction rate of olefins to generate carbon deposits are greatly suppressed. In addition, under the reaction conditions of the catalytic distillation process, the saturated liquid phase material mainly containing alcohol diffuses into the catalyst particles to perform the reaction, and the change of the material components after the reaction lowers the saturated vapor pressure. This will vaporize some of the material, and the heat absorbed by the vaporization is much greater than the heat released by the reaction, so that the internal temperature of the particles is lower than the surface temperature. These factors are all conducive to extending the life of the catalyst. In the catalytic distillation process, the catalyst life can reach 2 years.
This technology overcomes the problems of long process flow, high energy consumption, and large investment in the existing technology. It is a major advancement in the production technology of dimethyl ether. At present, it has completed the pilot test and has the conditions for industrialization. The Dalian Institute of Chemical Industry hopes to cooperate with relevant companies and jointly promote the technology to industrialization.
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