CN107285995B - Method for preparing methanol by using carbon dioxide and hydrogen - Google Patents
Method for preparing methanol by using carbon dioxide and hydrogen Download PDFInfo
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Abstract
The method comprises the following steps: (a) reacting carbon dioxide and hydrogen in an adiabatic fixed bed reactor under the action of a reverse water-gas shift catalyst to obtain a material I; the adiabatic fixed bed reactor comprises a plurality of sections of adiabatic reaction zones, reaction products in the previous section of adiabatic reaction zone are dehydrated or not dehydrated and enter the next section of adiabatic reaction zone, and carbon dioxide feeding materials enter each adiabatic reaction zone in a plurality of strands respectively; (b) cooling the material I, and carrying out gas-liquid separation to remove liquid water to obtain a material II containing carbon monoxide, carbon dioxide and hydrogen; (c) reacting the material II in a methanol synthesis reactor under the action of a methanol synthesis catalyst to generate methanol and water, cooling the discharged material of the methanol synthesis reaction, separating gas from liquid, obtaining a crude methanol product in a liquid phase, compressing a mixed gas containing carbon monoxide, carbon dioxide and hydrogen in a gas phase, and returning the mixed gas to the methanol synthesis reactor; the molar ratio of hydrogen to carbon dioxide in the feed of each adiabatic reaction zone is 3-15.
Description
Technical Field
The present invention relates to a process for the preparation of methanol using carbon dioxide and hydrogen.
Background
With the rapid development of society, the greenhouse gas emitted by human life and production activities is increased continuously, the global greenhouse effect is increased continuously, and the survival of human beings is threatened. Greenhouse gases are various, carbon dioxide is particularly prominent, and the increase of the carbon dioxide content in the atmosphere is one of the main causes of global warming. According to Global Carbon Program (GCP) data, the global carbon dioxide emission in 2013 reaches 360 hundred million tons, and the resource utilization is less than 1 percent; it is expected that emissions will reach 400 hundred million tons by 2020. Carbon dioxide emission reduction is one of the major problems which are urgently needed to be faced and solved in all countries in the world at present.
The global attention on carbon dioxide emission reduction, capture and utilization reaches unprecedented height at present. Chemical conversion and utilization of carbon dioxide have attracted extensive attention in the industry, and many chemical enterprises are developing new technologies to promote resource utilization of carbon dioxide. For example, carbon dioxide is used as a raw material to produce products such as high polymer materials such as urea, salicylic acid, methanol, polycarbonate and the like, clean fuels and the like. Of these, the hydroconversion of carbon dioxide once initiated a global discussion of the "methanol economy". The Nobel chemical prize-winning and famous organic chemist George.A. OLa proposes that the recycling mode of producing hydrogen by renewable energy and synthesizing methanol by hydrogenation of carbon dioxide can be used as a solution to the problem of energy shortage after the oil and gas era. The Nobel prize winner Carlo Lubia also discloses and suggests a way of preparing methanol by carbon dioxide to replace the carbon capture and sequestration in the current vogue, so that the raw materials are provided for the industry while the emission reduction is realized.
At present, the preparation of methanol by hydrogenation of carbon dioxide has become a research hotspot, and the production method mainly comprises two routes of a direct method and an indirect method. The direct method is to directly hydrogenate carbon dioxide to prepare methanol, the adopted catalyst is mainly a Cu-ZnO-based catalyst, and the method is limited by thermodynamic equilibrium, so that the equilibrium conversion rate of carbon dioxide is 20-30%, and the equilibrium yield of methanol is less than 21%; the indirect method is to convert carbon dioxide into carbon monoxide through reverse water gas, and then synthesize the carbon monoxide, the carbon dioxide and hydrogen into methanol, the route can break through thermodynamic equilibrium limitation, the equilibrium conversion rate of the carbon dioxide is more than or equal to 45%, the equilibrium yield of the methanol is more than or equal to 40%, and the key of the route is to efficiently convert the carbon dioxide into the carbon monoxide. For many years, companies, colleges and universities, scientific research institutions and the like at home and abroad continuously enhance the research and development of preparing methanol by hydrogenation of carbon dioxide. The Japan three-well chemical engineering is built into a first 100 ton/year carbon dioxide direct methanol preparation pilot plant in the world, and the pilot plant is completed in 2011 and 5 months (no subsequent report). The iceland CRI company takes geothermal power generation hydrolysis hydrogen production as a hydrogen source for the first time, and adopts a 4000 ton/year demonstration device for preparing methanol by an indirect method to put into production in 2013. Meanwhile, Danish Topusol, Japan Guanxi electric power company and Mitsubishi heavy industry, Germany Lurgi company, Korea institute of science and technology, etc. are also conducting the research on the attack of the carbon dioxide hydroconversion catalyst. But at present, the industrialization is not realized. The national institutes of coal chemical institute in Shanxi province, chemical research and design institute in southwest, Wuhan university, etc. are actively researching and developing the related technology for preparing methanol by carbon dioxide hydrogenation and have made certain progress.
CN101386564B introduces a process method for synthesizing methanol from hydrogen and carbon dioxide, which adopts two reactors, hydrogen and carbon dioxide are directly synthesized into methanol by a copper-based catalyst, in the first reactor, the hydrogen and the carbon dioxide react under the action of the copper-based catalyst to obtain products such as methanol, water, carbon monoxide and the like, the first reaction product is condensed and separated into gas and liquid, a liquid phase material flow containing methanol and water is separated out as a product, a gas phase material flow containing carbon monoxide, hydrogen and carbon dioxide enters the second reactor, the reaction is continued under the action of the copper-based catalyst to obtain products such as methanol, water and the like, the second reaction product is condensed and separated into gas and liquid, the liquid phase material flow containing methanol and water is separated out as a product, and the gas phase material flow containing carbon monoxide, hydrogen and carbon dioxide returns to the first reactor for recycling. WO2013/144041a1 describes a method for preparing methanol by carbon dioxide hydrogenation, which is characterized in that a stripping tower is added in comparison with other direct methods for producing methanol, raw material hydrogen is not directly mixed with carbon dioxide, but is firstly fed into the stripping tower to strip carbon dioxide and carbon monoxide dissolved in a crude methanol material flow, the gas is compressed and pressurized and then mixed with a fresh carbon dioxide raw material and then fed into a methanol synthesis reactor, a reaction product is condensed and subjected to gas-liquid separation, a liquid phase material flow containing methanol and water is fed into the stripping tower, a gas phase material flow containing carbon monoxide, hydrogen and carbon dioxide is compressed and pressurized and then fed back to the methanol synthesis reactor for recycling, and the method improves the utilization efficiency of resources by recovering the carbon dioxide and the carbon monoxide dissolved in a crude methanol product. A method for preparing Methanol by hydrogenating Carbon Dioxide is disclosed in the document Carbon Dioxide Hydrogenation To Form methane via-Water-Gas-Shift Reaction (Ind. Eng. chem. Res.1999,38, 1808-containing material 1802), wherein the method adopts an indirect method To produce Methanol, mainly comprises two isothermal reactors, Carbon Dioxide carries out a Reverse Water-Gas Shift Reaction in the first isothermal reactor To generate Carbon monoxide, a part of Reaction products is recycled To the first reactor after Water is removed by a separator, and the other part of Reaction products is removed from the second isothermal reactor To synthesize Methanol; and after the second reaction product is subjected to gas-liquid separation, the liquid-phase crude methanol product is sent to a subsequent rectifying tower for further refining, and unreacted gas returns to the second reactor for recycling.
Disclosure of Invention
The present invention relates to a process for the preparation of methanol using carbon dioxide and hydrogen. The invention aims to solve the technical problems of low carbon dioxide conversion rate and low methanol yield in the prior art. A novel process for the production of methanol from carbon dioxide is provided. When the method is used for preparing the methanol by utilizing the carbon dioxide, the method has the characteristics of high carbon dioxide conversion rate, high methanol yield, small reaction gas circulation amount and easy realization of industrialization.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a process for the production of methanol from carbon dioxide and hydrogen comprising the steps of:
(a) reacting carbon dioxide and hydrogen in an adiabatic fixed bed reactor under the action of a reverse water-gas shift catalyst to obtain a material I; the adiabatic fixed bed reactor comprises a plurality of sections of adiabatic reaction zones, reaction products in the previous section of adiabatic reaction zone are dehydrated or not dehydrated and enter the next section of adiabatic reaction zone, and feeding materials of the carbon dioxide reactor enter each adiabatic reaction zone in a plurality of strands respectively;
(b) cooling the material I, and carrying out gas-liquid separation to remove liquid water to obtain a material II containing carbon monoxide, carbon dioxide and hydrogen;
(c) reacting the material II in a methanol synthesis reactor under the action of a methanol synthesis catalyst to generate methanol and water, cooling the discharged material of the methanol synthesis reaction, separating gas from liquid, obtaining a crude methanol product in a liquid phase, compressing a mixed gas containing carbon monoxide, carbon dioxide and hydrogen in a gas phase, and returning the mixed gas to the methanol synthesis reactor;
the molar ratio of hydrogen to carbon dioxide in the feed of each adiabatic reaction zone is preferably 3-15, and more preferably 3-10.
In the above technical scheme, the adiabatic fixed bed reactor is not particularly limited in the number of specific stages as long as it includes 2 stages of adiabatic reaction zones or more. For example, but not limited to, the number of stages of an adiabatic fixed bed reactor having an adiabatic reaction zone is 2 to 5 stages, such as 2, 3, 4, or 5 stages.
In the above technical solutions, any reverse water gas shift catalyst may be used in the present invention, for example, but not limited to, a manganese-based spinel catalyst containing copper and manganese. The active components in the manganese-based spinel catalyst containing copper and manganese are not limited, for example, but not limited to, by weight, the manganese content in the catalyst is 1-40%, the copper content is 0.1-10%, the carrier is alumina and/or zinc oxide, in a specific embodiment, the manganese content in the catalyst is 20%, and the copper content is 3%.
In the technical scheme, the reaction temperature of the adiabatic reaction zone is preferably 550-700 ℃, and more preferably 580-680 ℃.
In the technical scheme, the reaction pressure of the adiabatic reaction zone is preferably 0-1.5 MPaG, and more preferably 0-1 MPaG.
In the technical scheme, the adiabatic reaction zones are combined by hydrogen and carbon dioxide, and the volume airspeed is preferably 6000-20000 h-1More preferably 8000 to 16000h-1。
In the above technical scheme, the methanol synthesis catalyst including hydrogen and carbon monoxide as reaction raw materials can be used in the present invention, for example, but not limited to, copper-based catalyst containing copper, zinc and aluminum. The active components in the copper-zinc-aluminum-containing copper-based catalyst are not limited, for example, but not limited to, by weight, the content of copper in the catalyst is 15-70%, the content of zinc in the catalyst is 15-60%, the carrier is alumina, and the content of copper in the catalyst is 50% and the content of zinc in the catalyst is 30%.
In the technical scheme, the reaction temperature of the methanol synthesis reaction is preferably 200-280 ℃, the reaction pressure is preferably 4.5-6.5 MPaG, and the volume space velocity is preferably 3000-10000 h-1。
According to the invention, methanol is prepared by adopting an indirect method of reverse water gas shift reaction and methanol synthesis reaction, a multi-section heat-insulating fixed bed reactor is adopted in the reverse water gas shift reaction unit, carbon dioxide is converted into carbon monoxide at high temperature, the difficulty that high temperature and isothermy are difficult to realize in the reverse water gas shift reaction by adopting an isothermal bed technology is avoided, and industrialization is easy to realize; meanwhile, the content of carbon monoxide entering the methanol synthesis unit is improved, the conversion rate of carbon dioxide and the yield of methanol are improved, the circulation amount of reaction gas of the methanol synthesis unit is reduced, and a better technical effect is achieved.
Drawings
FIG. 1 is a schematic process flow diagram of a method for preparing methanol by using carbon dioxide and hydrogen according to the present invention.
In fig. 1, 1 is a carbon dioxide raw material, 2 is a hydrogen raw material, 3 is a first adiabatic reaction discharge material, 4 is a second adiabatic reaction discharge material, 5 is liquid water, 6 is a methanol synthesis reaction discharge material, 7 is a methanol synthesis reaction circulation gas, 8 is a crude methanol product, R1 is a first adiabatic reactor, R2 is a second adiabatic reactor, R3 is a methanol synthesis reactor, E1 is a feed-in and feed-out heat exchanger, E2 is a first feed heater, E3 is a second feed heater, E4 is a first discharge cooler, E5 is a third feed heater, E6 is a second discharge cooler, D1 is a dryer, V1 is a first gas-liquid separation tank, V2 is a second gas-liquid separation tank, K1 is a first compressor, K2 is a second compressor,
according to the flow shown in fig. 1, a part of carbon dioxide raw material 1 and hydrogen raw material 2 are mixed and then enter a feeding and discharging heat exchanger E1, and the reaction gas after heat exchange enters a first adiabatic reactor R1 to carry out reverse water gas shift reaction after being heated to a specified temperature by a first feeding heater E2. The first adiabatic reaction discharge 3 is dewatered by a drier D1 and then mixed with the rest part of the carbon dioxide raw material 1, and the mixed gas is heated to a specified temperature by a second feeding heater E3 and then enters a second adiabatic reactor R2 to continue the reverse water gas shift reaction. The second adiabatic reaction discharge 4 passes through a feed-discharge heat exchanger E1 and a first discharge cooler E4, then enters a first gas-liquid separation tank V1, liquid water 5 is discharged from the bottom, and the gas mixture at the top enters a first compressor K1. The pressurized gas mixture is heated to a specified temperature by a third heater E5 and then enters a methanol synthesis reactor R3 for methanol synthesis reaction, a methanol synthesis reaction discharge 6 passes through a second discharge cooler E6 and then enters a second gas-liquid separation tank V2, the top methanol synthesis reaction circulating gas 7 is pressurized by a second compressor K2 and then returns to the methanol synthesis reactor R3, and a bottom crude methanol product 8 is fed to a subsequent rectification unit for rectification.
The present invention will be further described with reference to specific examples, but the scope of the present invention is not limited to the scope covered by the examples.
Detailed Description
[ example 1 ]
As shown in figure 1, the reverse water gas shift reaction unit adopts two sections of heat-insulating fixed bed reactors, the inlet temperature of the first section of heat-insulating fixed bed reactor is 680 ℃, the inlet pressure is 1MPaG, the molar ratio of hydrogen to carbon dioxide at the inlet is 3, and the volume space velocity is 16000h-1(ii) a The inlet temperature of the second section of the adiabatic fixed bed reactor is 680 ℃, the inlet pressure is 0.97MPaG, the molar ratio of hydrogen to carbon dioxide at the inlet is 4.3, and the volume space velocity is 14000h-1(ii) a Manganese-based catalysts are adopted in the two sections of adiabatic reactors, and 60.9 percent of carbon dioxide is converted into carbon monoxide in a reverse water-gas shift reaction unit. The methanol synthesis unit adopts an isothermal fixed bed reactor, the reaction temperature is 250 ℃, the reaction pressure is 5MPaG, and the volume space velocity is 8000h-1The yield of methanol was 94.8% (relative to the carbon dioxide raw material, the same applies hereinafter) using a copper-based catalyst, and the mass ratio of the methanol synthesis reaction recycle gas to the raw material (the total amount of carbon dioxide and hydrogen, the same applies hereinafter) was 1.7.
[ example 2 ]
As shown in figure 1, the reverse water gas shift reaction unit adopts two sections of heat-insulating fixed bed reactors, the inlet temperature of the first section of heat-insulating fixed bed reactor is 670 ℃, the inlet pressure is 0.70MPaG, the molar ratio of hydrogen to carbon dioxide at the inlet is 4, and the volume space velocity is 12000h-1(ii) a The inlet temperature of the second-stage adiabatic fixed bed reactor is 670 ℃, the inlet pressure is 0.67MPaG, the molar ratio of hydrogen to carbon dioxide at the inlet is 3.9, and the volume space velocity is 12000h-1(ii) a Manganese-based catalysts are adopted in the two sections of adiabatic reactors, and 56.1 percent of carbon dioxide is converted into carbon monoxide in a reverse water-gas shift reaction unit. The methanol synthesis unit adopts an isothermal fixed bed reactor, the reaction temperature is 240 ℃, the reaction pressure is 5MPaG, and the volume space velocity is 6000h-1The copper-based catalyst is adopted, the yield of the methanol is 94.5 percent, and the mass ratio of the methanol synthesis reaction circulating gas to the raw material is 1.9.
[ example 3 ]
As shown in figure 1, the reverse water gas shift reaction unit adopts three sections of adiabatic fixed bed reactors, wherein the inlet temperature of the first section of adiabatic fixed bed reactor is 660 ℃, the inlet pressure is 0.30MPaG, and the molar ratio of hydrogen to carbon dioxide at the inlet isIs 6, the volume space velocity is 10000h-1(ii) a The inlet temperature of the second section of the adiabatic fixed bed reactor is 660 ℃, the inlet pressure is 0.28MPaG, the molar ratio of hydrogen to carbon dioxide at the inlet is 4.7, and the volume space velocity is 10000h-1(ii) a The inlet temperature of the third-stage adiabatic fixed bed reactor is 660 ℃, the inlet pressure is 0.26MPaG, the molar ratio of hydrogen to carbon dioxide at the inlet is 4.8, and the volume space velocity is 10000h-1(ii) a A manganese-based catalyst is adopted in the three-section adiabatic reactor, and 65.5 percent of carbon dioxide is converted into carbon monoxide in a reverse water-gas shift reaction unit. The methanol synthesis unit adopts an isothermal fixed bed reactor, the reaction temperature is 240 ℃, the reaction pressure is 5.5MPaG, and the volume space velocity is 5000h-1The copper-based catalyst is adopted, the yield of the methanol is 94.6 percent, and the mass ratio of the methanol synthesis reaction circulating gas to the raw material is 1.8.
[ example 4 ]
As shown in figure 1, the reverse water gas shift reaction unit adopts three sections of adiabatic fixed bed reactors, the inlet temperature of the first section of adiabatic fixed bed reactor is 650 ℃, the inlet pressure is 0.15MPaG, the molar ratio of hydrogen to carbon dioxide at the inlet is 9, and the volume space velocity is 8000h-1(ii) a The inlet temperature of the second-stage adiabatic fixed bed reactor is 650 ℃, the inlet pressure is 0.13MPaG, the molar ratio of hydrogen to carbon dioxide at the inlet is 6.1, and the volume space velocity is 8000h-1(ii) a The inlet temperature of the third-stage adiabatic fixed bed reactor is 650 ℃, the inlet pressure is 0.11MPaG, the molar ratio of hydrogen to carbon dioxide at the inlet is 4.3, and the volume space velocity is 8000h-1(ii) a A manganese-based catalyst is adopted in the three-section adiabatic reactor, and 60.2 percent of carbon dioxide is converted into carbon monoxide in a reverse water-gas shift reaction unit. The methanol synthesis unit adopts an isothermal fixed bed reactor, the reaction temperature is 240 ℃, the reaction pressure is 6MPaG, and the volume space velocity is 4000h-1The copper-based catalyst is adopted, the yield of the methanol is 94.4 percent, and the mass ratio of the methanol synthesis reaction circulating gas to the raw material is 1.9.
[ COMPARATIVE EXAMPLE 1 ]
The method is the same proportion as that of the embodiment 1, and specifically comprises the following steps:
as shown in figure 1, the reverse water gas shift reaction unit adopts a single-stage adiabatic fixed bed reactor for reactionThe inlet temperature of the reactor is 680 ℃, the inlet pressure is 1MPaG, the molar ratio of hydrogen to carbon dioxide at the inlet is 3, and the volume space velocity is 16000h-1(ii) a A manganese-based catalyst is adopted in the adiabatic reactor, and 39.3 percent of carbon dioxide is converted into carbon monoxide in a reverse water-gas shift reaction unit. The methanol synthesis unit adopts an isothermal fixed bed reactor, the reaction temperature is 250 ℃, the reaction pressure is 5MPaG, and the volume space velocity is 8000h-1The copper-based catalyst is adopted, the yield of the methanol is 94.0 percent, and the mass ratio of the methanol synthesis reaction circulating gas to the raw material is 2.3.
Claims (7)
1. A process for the production of methanol from carbon dioxide and hydrogen comprising the steps of:
(a) reacting carbon dioxide and hydrogen in an adiabatic fixed bed reactor under the action of a reverse water-gas shift catalyst to obtain a material I; the adiabatic fixed bed reactor comprises a plurality of sections of adiabatic reaction zones, reaction products in the previous section of adiabatic reaction zone are dehydrated or not dehydrated and enter the next section of adiabatic reaction zone, and carbon dioxide feeding materials enter each adiabatic reaction zone in a plurality of strands respectively;
(b) cooling the material I, and carrying out gas-liquid separation to remove liquid water to obtain a material II containing carbon monoxide, carbon dioxide and hydrogen;
(c) reacting the material II in a methanol synthesis reactor under the action of a methanol synthesis catalyst to generate methanol and water, cooling the discharged material of the methanol synthesis reaction, separating gas from liquid, obtaining a crude methanol product in a liquid phase, compressing a mixed gas containing carbon monoxide, carbon dioxide and hydrogen in a gas phase, and returning the mixed gas to the methanol synthesis reactor;
the molar ratio of hydrogen to carbon dioxide in the feed of each adiabatic reaction zone is 3-15;
the reverse water gas shift catalyst is a manganese-based spinel catalyst containing copper and manganese, wherein the content of manganese in the catalyst is 20-40% and the content of copper in the catalyst is 3-10% by weight.
2. The method as set forth in claim 1, characterized in that the adiabatic fixed-bed reactor has 2 to 5 stages of adiabatic reaction zones.
3. The method as set forth in claim 1, wherein the reaction temperature of the adiabatic reaction zone is 550 to 700 ℃.
4. The process of claim 1, wherein the adiabatic reaction zone has a reaction pressure of 0 to 1.5 MPaG.
5. The method as set forth in claim 1, wherein the volume space velocity of each adiabatic reaction zone is 6000-20000 h by adding hydrogen and carbon dioxide together-1。
6. The process as set forth in claim 1, characterized in that said methanol synthesis catalyst is a copper-based catalyst containing copper, zinc and aluminum.
7. The method according to claim 1, wherein the reaction temperature of the methanol synthesis reaction is 200 to 280 ℃, the reaction pressure is 4.5 to 6.5MPaG, and the volume space velocity is 3000 to 10000h-1。
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| GB201808019D0 (en) * | 2018-05-17 | 2018-07-04 | Johnson Matthey Davy Technologies Ltd | Process for synthesising methanol |
| CN109772342A (en) * | 2019-03-06 | 2019-05-21 | 南京工业大学 | A kind of preparation method of hydrogenation of carbon dioxide methanol catalyst |
| CN112194566A (en) * | 2020-09-29 | 2021-01-08 | 浙江工业大学 | Device and process for synthesizing methanol based on carbon dioxide hydrogenation |
| CN113663678B (en) * | 2021-08-11 | 2022-11-25 | 清华大学 | Cu-based spinel catalyst for preparing methanol by carbon dioxide hydrogenation and preparation method and application thereof |
| CN114907187B (en) * | 2022-04-24 | 2023-12-22 | 中国成达工程有限公司 | Method for directly preparing methanol by pure/rich carbon dioxide and hydrogen |
| CN114907186A (en) * | 2022-04-24 | 2022-08-16 | 中国成达工程有限公司 | Method for directly preparing methanol from carbon dioxide and hydrogen |
| CN115504861B (en) * | 2022-09-22 | 2023-06-23 | 中国五环工程有限公司 | Coupling CO 2 Process method for preparing methanol by hydrogenation |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005026093A1 (en) * | 2003-09-17 | 2005-03-24 | Korea Institute Of Science And Technology | Method for the production of dimethyl ether |
| CN1880414A (en) * | 2006-05-17 | 2006-12-20 | 成都恒新威石化科技有限公司 | Method for optimization of synthetic gas components by reversed water-gas shift reaction technology and flow therefor |
| CN101386564A (en) * | 2008-10-29 | 2009-03-18 | 西南化工研究设计院 | Technique for synthesizing methanol by hydrogen and carbon dioxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005026093A1 (en) * | 2003-09-17 | 2005-03-24 | Korea Institute Of Science And Technology | Method for the production of dimethyl ether |
| CN1880414A (en) * | 2006-05-17 | 2006-12-20 | 成都恒新威石化科技有限公司 | Method for optimization of synthetic gas components by reversed water-gas shift reaction technology and flow therefor |
| CN101386564A (en) * | 2008-10-29 | 2009-03-18 | 西南化工研究设计院 | Technique for synthesizing methanol by hydrogen and carbon dioxide |
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