CN109289855B - Methanol catalyst for synthesis gas and preparation method thereof - Google Patents
Methanol catalyst for synthesis gas and preparation method thereof Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/154—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing copper, silver, gold, or compounds thereof
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a synthesis gas methanol catalyst and a preparation method thereof. The synthesis gas methanol catalyst comprises the following components in parts by mass: CuO: 55 to 75 parts of ZnO, 15 to 25 parts of Al2O3: 10-15 parts of MgO and 1-3 parts of MgO. The preparation method of the synthesis gas methanol catalyst adopts a two-step simultaneous precipitation method and simultaneously mixes Zn2+、Al3+Precipitate 1 and Cu formed together2+、Zn2+、Al3+And Mg2+And precipitating the precipitate 2 formed together, and then filtering, washing, drying and roasting to obtain the synthesis gas methanol catalyst. The synthesis gas methanol catalyst prepared by the method has the advantages of scientific design, simple method and convenient operation, and has excellent low-temperature activity, good hydrothermal stability and high selectivity.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a synthesis gas methanol catalyst and a preparation method thereof.
Background
Methanol is a chemical product and an important organic chemical raw material which are second only to ammonia synthesis, is a chemical basic substance and is a clean fuel. At present, methanol is synthesized by adopting a medium-pressure and low-pressure gas phase method in the world, and the used catalyst is basically mixed oxide of copper, zinc and aluminum. CuO, ZnO and Al in synthetic methanol catalyst2O3The three components have different functions, CuO is used as a main active component, ZnO and Al2O3Is an auxiliary agent. The addition of ZnO can make the catalyst form Cu/Zn synergetics, greatly raise activity and selectivity of catalyst, Al2O3Not only plays a role of a framework in the catalyst, but also can disperse active components in the catalyst.
In the prior art, the activity of copper-based catalysts for synthesis gas methanol is very different. The preparation method of the copper-based catalyst can obviously affect the structure of precursor species and the phase composition of a product catalyst, and finally the activity of the catalyst. The domestic large-scale methanol plant almost totally uses foreign technologies. The development of the methanol catalyst with more excellent performance has practical significance for breaking monopoly in the technical field of the catalyst. Therefore, it is an urgent problem to be solved by those skilled in the art to provide a syngas methanol catalyst with excellent activity.
Disclosure of Invention
It is an object of the present invention to provide a syngas methanol catalyst having excellent low temperature activity, good hydrothermal stability, and high selectivity.
The invention also aims to provide a preparation method of the synthesis gas methanol catalyst, which is simple and convenient to operate.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention relates to a methanol catalyst for synthesis gasThe oxidant comprises the following components in parts by mass: CuO: 55 to 75 parts of ZnO, 15 to 25 parts of Al2O3: 10-15 parts of MgO and 1-3 parts of MgO.
The preparation method of the synthesis gas methanol catalyst adopts a two-step simultaneous precipitation method and simultaneously mixes Zn2+、Al3+Precipitate 1 and Cu formed together2+、Zn2+、Al3+And Mg2+And precipitating the precipitate 2 formed together, and then filtering, washing, drying and roasting to obtain the synthesis gas methanol catalyst.
Further, the method comprises the following steps:
step 1, Zn is added2+、Al3+Dissolving the salt solution in water, stirring, dissolving and uniformly mixing to form a salt solution A;
step 6, stopping dripping the alkali solution C after the salt solution A and the salt solution B are dripped;
step 7, after the precipitate 1 and the precipitate 2 are completely in parallel flow and are dripped into the mixing tank, continuing to age in the mixing tank for a certain time;
step 8, after the aging is finished, centrifugally filtering the precipitate to obtain a catalyst precursor, washing and drying;
and 9, decomposing the dried product at low temperature, adding graphite into the obtained decomposition product, uniformly mixing, and forming the mixture to obtain the synthesis gas methanol catalyst.
Furthermore, the molar ratio of Zn to Al in the precipitate 1 is 1: 1-1: 3.
Further, the molar ratio of the Al in the precipitate 1 to the precipitate 2 is 1: 1.
Further, the temperature of the first reaction tank, the temperature of the second reaction tank and the temperature of the mixing tank are controlled to be 70-90 ℃, and the pH value of the first reaction tank and the pH value of the second reaction tank in the titration and precipitation process are 6-8.
Further, in the step 5, after the precipitate 1 and the precipitate 2 are formed for 5-15 min, the precipitate 1 and the precipitate 2 are dripped into a mixing tank containing deionized water in a parallel flow manner, and the stirring reaction is continued.
Further, in the step 7, the aging time is 2-4 hours.
Further, in the step 9, the low-temperature decomposition temperature is 300-400 ℃, and the time is 2-6 hours; the amount of the graphite is 1-3wt% of the mass of the mixture.
Further, in the step 4, the salt solution a, the salt solution B and the alkali solution C are preheated to the reaction temperature, and then are respectively added dropwise and reacted.
In the step 5, the precipitate 1 and the precipitate 2 are dripped into a mixing tank containing deionized water in a parallel flow manner, and are emulsified circularly under the action of the circulating emulsifying pump so as to achieve the purpose of stirring reaction; and 7, after the precipitate 1 and the precipitate 2 are completely in parallel flow and dropwise added into the mixing tank, continuously performing circulating emulsification under the action of a circulating emulsification pump so as to age for a certain time.
Compared with the prior art, the invention has the following beneficial effects:
the synthesis gas methanol catalyst prepared by the method has the advantages of scientific design, simple method and convenient operation, and has excellent low-temperature activity, good hydrothermal stability and high selectivity.
In the present invention, Zn is added2+、Al3+Simultaneously precipitating to form a hydrotalcite structure, and further roasting in the subsequent stepThe process is more favorable for forming a stable Zn-Al spinel structure, thereby effectively isolating active components and improving the high-temperature hydrothermal stability of the catalyst.
In the present invention, Cu is added2+、Zn2+、Al3+And Mg2+The precipitate is beneficial to increasing the relative content of the active components; and introducing Mg at the time of precipitation2+The method is not only beneficial to improving the thermal stability of the catalyst, but also beneficial to increasing the alkalinity of the surface of the catalyst and improving the selectivity of the catalyst.
In the present invention, Zn is added2+、Al3+Precipitate 1, Cu formed together2+、Zn2+、Al3+And Mg2+The precipitate 2 formed by precipitation is circularly emulsified and mixed in the reaction process, which belongs to the nano-scale mixing reaction, is more beneficial to the stability of the structure and the dispersion of active components, and is finally beneficial to the low-temperature activity and the high-temperature hydrothermal stability of the catalyst.
Drawings
FIG. 1 is a schematic diagram of the titration process of the catalyst precursor of the present invention.
Wherein, the names corresponding to the reference numbers are: 1-a first reaction tank, 2-a mixing tank, 3-a second reaction tank, 4-a stirrer and 5-a circulating emulsification pump.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
As shown in fig. 1, the device used in the titration process of the catalyst precursor of the present invention comprises a first reaction tank 1, a second reaction tank 3 and a mixing tank 2, wherein stirrers 4 for stirring reaction are arranged in the first reaction tank 1 and the second reaction tank 3, the mixing tank 2 is provided with a circulating emulsification pump 5 for stirring and mixing, the first reaction tank 1 is provided with a pipeline for dripping the precipitate 1 into the mixing tank 2 in a cocurrent manner, and the second reaction tank 3 is provided with a pipeline for dripping the precipitate 1 into the mixing tank 2 in a cocurrent manner.
Example 1
The embodiment provides a preparation method of a synthesis gas methanol catalyst, which specifically comprises the following steps:
26.52g of Zn (NO)3)2·6H2O and 66.89g Al (NO)3)3·9H2O is dissolved in 600ml of deionized water and stirred to dissolve it sufficiently to form a salt solution A.
276.13g of Cu (NO)3)2·3H2O，111.93g Zn(NO3)2·6H2O,66.89g Al(NO3)39H2O and 29.14g Mg (NO)3)2.6H2O was dissolved in 1300ml of deionized water and stirred to dissolve it sufficiently to form a salt solution B.
256.95g NaCO3Dissolved in 2000ml deionized water and stirred to dissolve completely to form alkali solution C for precipitation.
Preheating a salt solution A, a salt solution B and an alkali solution C, and after the preheating temperature reaches 90 ℃, dropwise adding the salt solution A and the alkali solution C into a first reaction tank containing a certain amount of deionized water simultaneously under strong stirring; simultaneously, the salt solution B and the alkali solution C are simultaneously added dropwise into a second reaction tank containing a certain amount of deionized water under strong stirring.
And after the precipitates of the first reaction tank and the second reaction tank are formed for 15min, the precipitates of the first reaction tank and the second reaction tank are dripped into the mixing tank in a parallel flow manner, and the circulating emulsification is carried out in the mixing tank.
And stopping dropping the alkali C after the solution A and the solution B are dropped. The pH value of the first reaction tank and the second reaction tank is controlled to be 6.0-6.5 in the whole process, and the reaction temperature of the first reaction tank, the second reaction tank and the mixing tank is controlled to be 90 ℃ by using a water bath.
And after the precipitates in the first reaction tank and the second reaction tank completely enter the mixing tank, continuously circulating and emulsifying the precipitates in the mixing tank, and aging for 6 hours at constant temperature.
After aging was complete, filtration was performed and the precipitate was washed with deionized water until free of Na+. The obtained precipitate was dried at 90 deg.CAnd drying for 24 hours.
The dried product is heated to 300 ℃ at the speed of 5 ℃/min and roasted for 6 h. Adding graphite into the obtained roasted product, uniformly mixing to obtain a mixture, wherein the using amount of the graphite is 3% of the mass of the mixture, and forming to obtain a catalyst, wherein the number of the catalyst is sample A
Example 2
The embodiment provides a preparation method of a synthesis gas methanol catalyst, which specifically comprises the following steps:
57.47g of Zn (NO)3)2·6H2O and 72.47g Al (NO)3)3·9H2O is dissolved in 600ml of deionized water and stirred to dissolve it sufficiently to form a salt solution A.
299.14g of Cu (NO)3)2·3H2O，53.29g Zn(NO3)2·6H2O,72.47g Al(NO3)3·9H2O and 19.43g Mg (NO)3)2.6H2O was dissolved in 1300ml of deionized water and stirred to dissolve it sufficiently to form a salt solution B.
256.95g of NaCO3 was dissolved in 2000ml of deionized water and stirred to dissolve it sufficiently to form the alkali solution C required for precipitation.
Preheating a salt solution A, a salt solution B and an alkali solution C, and after the preheating temperature reaches 80 ℃, dropwise adding the salt solution A and the alkali solution C into a first reaction tank containing a certain amount of deionized water simultaneously under strong stirring; meanwhile, under the condition of strong stirring, the salt solution B and the alkali solution C are simultaneously dripped into a second reaction tank filled with a certain amount of deionized water, and after the precipitates of the first reaction tank and the second reaction tank are formed for 10min, the precipitates of the first reaction tank and the second reaction tank are dripped into a mixing tank in a parallel flow manner, and are circularly emulsified in the mixing tank.
And stopping dropping the alkali C after the solution A and the solution B are dropped. The pH values of the first reaction tank and the second reaction tank are controlled to be 6.5-7.0 in the whole process, and the reaction temperatures of the first reaction tank, the second reaction tank and the mixing tank are controlled to be 80 ℃ by using a water bath.
And after the precipitates in the first reaction tank and the second reaction tank completely enter the mixing tank, continuously circulating and emulsifying the precipitates in the mixing tank, and aging for 4 hours at constant temperature.
After aging was complete, filtration was performed and the precipitate was washed with deionized water until free of Na+. Drying the obtained precipitate at 110 deg.C for 24h, and roasting the dried product at 350 deg.C/min for 4 h. And adding graphite into the obtained roasted product, uniformly mixing to obtain a mixture, wherein the using amount of the graphite is 3% of the mass of the mixture, and forming to obtain the catalyst, wherein the number of the catalyst is sample B.
Example 3
The embodiment provides a preparation method of a synthesis gas methanol catalyst, which specifically comprises the following steps:
20.63g of Zn (NO)3)26H2O and 78.04g Al (NO)3)3·9H2O is dissolved in 600ml of deionized water and stirred to dissolve it sufficiently to form a salt solution A.
322.16g of Cu (NO)3)2·3H2O，62.44g Zn(NO3)2·6H2O,78.04g Al(NO3)3·9H2O and 9.71g Mg (NO)3)2.6H2O is dissolved in 1300ml of deionized water and stirred to dissolve it sufficiently to form a second salt solution B.
256.95g NaCO3Dissolved in 2000ml deionized water and stirred to dissolve completely to form alkali solution C for precipitation.
Preheating a salt solution A, a salt solution B and an alkali solution C, and after the preheating temperature reaches 70 ℃, dropwise adding the salt solution A and the alkali solution C into a first reaction tank containing a certain amount of deionized water simultaneously under strong stirring; meanwhile, under the condition of strong stirring, the salt solution B and the alkali solution C are simultaneously dripped into a second reaction tank filled with a certain amount of deionized water, and after the precipitates of the first reaction tank and the second reaction tank are formed for 5min, the precipitates of the first reaction tank and the second reaction tank are dripped into a mixing tank in a parallel flow manner, and are circularly emulsified in the mixing tank.
And stopping dropping the alkali C after the solution A and the solution B are dropped. The pH values of the first reaction tank and the second reaction tank are controlled to be 7.0-7.5 in the whole process, and the reaction temperature of the first reaction tank, the second reaction tank and the mixing tank is controlled to be 70 ℃ by using a water bath.
And after the precipitates in the first reaction tank and the second reaction tank completely enter the mixing tank, the precipitates continue to be circularly emulsified in the mixing tank, and are aged for 2 hours at constant temperature.
After aging was complete, filtration was performed and the precipitate was washed with deionized water until free of Na+. Drying the obtained precipitate at 120 deg.C for 24h, and roasting the dried product at 400 deg.C at 5 deg.C/min for 2 h. And adding graphite into the obtained roasted product, uniformly mixing to obtain a mixture, wherein the using amount of the graphite is 3% of the mass of the mixture, and forming to obtain the catalyst, wherein the number of the catalyst is sample C.
Example 4
This example is a comparative example, which provides a catalyst prepared by a conventional two-step precipitation method, as follows:
26.52g of Zn (NO)3)2·6H2O and 66.89g Al (NO)3)3·9H2O is dissolved in 600ml of deionized water and stirred to dissolve it sufficiently to form a salt solution A.
276.13g of Cu (NO)3)2·3H2O，111.93g Zn(NO3)2·6H2O,66.89g Al(NO3)3·9H2O and 29.14g Mg (NO)3)2.6H2O was dissolved in 1300ml of deionized water and stirred to dissolve it sufficiently to form a salt solution B.
256.95g NaCO3Dissolved in 2000ml deionized water and stirred to dissolve completely to form alkali solution C for precipitation.
Preheating a salt solution A, a salt solution B and an alkali solution C, and after the preheating temperature reaches 90 ℃, dropwise adding the salt solution A and the alkali solution C into a first reaction tank containing a certain amount of deionized water simultaneously under strong stirring; simultaneously, the salt solution B and the alkali solution C are simultaneously added dropwise into a second reaction tank containing a certain amount of deionized water under strong stirring.
And stopping dropping the alkali C after the solution A and the solution B are dropped. Then the precipitates of the first reaction tank and the second reaction tank are quickly mixed in a mixing tank for pulping, and are aged for 6 hours at constant temperature in the mixing tank. The pH value of the first reaction tank and the second reaction tank is controlled to be 6.0-6.5 in the whole process, and the reaction temperature of the first reaction tank, the second reaction tank and the mixing tank is controlled to be 90 ℃ by using a water bath.
After aging, filtering, and washing the precipitate with deionized water until no Na exists+Drying the obtained precipitate at 90 deg.C for 24h, and roasting the dried product at 300 deg.C at 5 deg.C/min for 6 h. And adding graphite into the obtained roasted product, uniformly mixing to obtain a mixture, wherein the using amount of the graphite is 3% of the mass of the mixture, and forming to obtain a reference sample catalyst, wherein the number of the reference sample catalyst is sample D.
Example 5
This example provides a method for evaluating the catalysts of examples 1-4, as follows:
sample particle size: 16-40 meshes. Loading amount: 4mL (2mL catalyst +2mL inert support).
Activating a sample: samples were run with low concentrations of hydrogen (H) before being active and heat resistant2/N 23/97 (volume ratio)) of the mixed gas of hydrogen and nitrogen is reduced for 16-20 h, and the maximum reduction temperature is 235 ℃.
And (3) activity test: the raw material gas composition is CO/H2/CO2/N212/70/5/13 (volume ratio), reaction pressure of 5.0MPa and space velocity of 10000h-1The reaction temperature is 230-240 ℃, and the CO conversion rate and CH before heat resistance are measured3OH selectivity and CH3OH space time yield (amount of methanol produced per mL of catalyst per hour).
Activity test after heat resistance: after the initial activity of the sample is measured, the reaction temperature is increased to 400 ℃ for heat treatment for 10h, then the test conditions are restored, and the CO conversion rate and CH after heat resistance are measured3OH selectivity and CH3OH space-time yield.
The catalysts of examples 1-4 were evaluated for initial activity and heat resistance using the test methods described above. The results are shown in Table 1.
TABLE 1 CO conversion, CH, before and after heat resistance of the catalyst3OH selectivity and CH3OH space-time yield
As can be seen from the test results in Table 1, sample A, B, C has both CO conversion and CH conversion relative to comparative sample D3The OH space-time yield is clearly advantageous:
1. the catalyst prepared by the two-step simultaneous precipitation method of the invention has CO conversion rate and CH3The initial activity of OH selectivity is good, the CO conversion rate is up to 75 percent, and CH3The OH selectivity is as high as 99 percent; the CO conversion of the control was less than 60%, and the methanol space-time yield was only 1.36 g/mLcat/h.
2. After a rapid aging experiment, the heat-resistant conversion rate of the catalyst prepared by the two-step simultaneous precipitation method to CO is reduced, but the conversion rate is still over 60 percent, and CH3The heat-resistant selectivity of OH is still more than 99 percent; the CO conversion of the control sample was reduced to 60% and the space-time yield of methanol was reduced to 0.76 g/mLcat/h.
Overall, the catalyst prepared by the two-step simultaneous precipitation method has excellent low-temperature activity, high selectivity, and good hydrothermal stability.
The above-mentioned embodiment is only one of the preferred embodiments of the present invention, and should not be used to limit the scope of the present invention, but all the insubstantial modifications or changes made within the spirit and scope of the main design of the present invention, which still solve the technical problems consistent with the present invention, should be included in the scope of the present invention.
Claims (8)
1. The preparation method of the catalyst for preparing methanol from synthesis gas is characterized in that the catalyst for preparing methanol from synthesis gas comprises the following components in parts by mass: CuO: 55 to 75 parts of ZnO, 15 to 25 parts of Al2O3: 10-15 parts of MgO, 1-3 parts of MgO;
the preparation method adopts a two-step simultaneous precipitation method and simultaneously mixes Zn2+、Al3+Precipitate 1 and Cu formed together2+、Zn2+、Al3+And Mg2+Precipitating the formed precipitate 2 together, and thenFiltering, washing, drying and roasting to prepare the synthesis gas methanol catalyst; the simultaneous mixing means that the precipitate 1 and the precipitate 2 are dripped into a mixing tank containing deionized water in a parallel flow manner to continue stirring and reacting;
the preparation method comprises the following steps:
step 1, Zn is added2+、Al3+Dissolving salt in water, stirring, dissolving and uniformly mixing to form a salt solution A;
step 2, adding Cu2+、Zn2+、Al3+And Mg2+Dissolving salt in water, stirring, dissolving and uniformly mixing to form a salt solution B;
step 3, adding Na2CO3Dissolving in water, stirring, dissolving and uniformly mixing to form an alkali solution C;
step 4, under the stirring action, simultaneously dripping a salt solution A and an alkali solution C into a first reaction tank containing deionized water, and reacting to generate a precipitate 1; simultaneously, under the stirring action, dropwise adding a salt solution B and an alkali solution C into a second reaction tank containing deionized water at the same time, and reacting to generate a precipitate 2;
step 5, after the precipitate 1 and the precipitate 2 are formed for a certain time, dropwise adding the precipitate 1 and the precipitate 2 in a parallel flow manner into a mixing tank containing deionized water, and continuously stirring for reaction;
step 6, stopping dripping the alkali solution C after the salt solution A and the salt solution B are dripped;
step 7, after the precipitate 1 and the precipitate 2 are completely in parallel flow and are dripped into the mixing tank, continuing to age in the mixing tank for a certain time;
step 8, after the aging is finished, centrifugally filtering the precipitate to obtain a catalyst precursor, washing and drying;
and 9, decomposing the dried product at low temperature, adding graphite into the obtained decomposition product, uniformly mixing, and forming the mixture to obtain the synthesis gas methanol catalyst, wherein the low-temperature decomposition temperature is 300-400 ℃.
2. The method for preparing the methanol catalyst from the synthesis gas as claimed in claim 1, wherein the molar ratio of Zn to Al in the precipitate 1 is 1: 1-1: 3.
3. The method according to claim 1, wherein the molar ratio of Al in precipitate 1 to Al in precipitate 2 is 1: 1.
4. The method for preparing the catalyst for preparing the methanol from the synthesis gas according to claim 1, wherein the temperatures of the first reaction tank, the second reaction tank and the mixing tank are controlled to be 70-90 ℃, and the pH value of the first reaction tank and the second reaction tank in the process of titration and precipitation is 6-8.
5. The method for preparing the catalyst for preparing methanol from synthesis gas according to claim 1, wherein in the step 5, after the precipitate 1 and the precipitate 2 are formed for 5-15 min, the precipitate 1 and the precipitate 2 are dripped into a mixing tank containing deionized water in a parallel flow manner, and the stirring reaction is continued.
6. The method for preparing the catalyst for preparing the methanol from the synthesis gas according to claim 1, wherein in the step 7, the aging time is 2 to 4 hours.
7. The method for preparing the catalyst for preparing methanol from synthesis gas according to claim 1, wherein in the step 9, the time of low-temperature decomposition is 2-6 hours; the amount of the graphite is 1-3wt% of the mass of the mixture.
8. The method of claim 1, wherein in step 4, the salt solution A, the salt solution B and the alkali solution C are pre-heated to the reaction temperature, and then are respectively added dropwise and reacted.
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| CN112023933A (en) * | 2020-08-11 | 2020-12-04 | 河北瑞克新能源科技有限公司 | Preparation method of catalyst for preparing methanol from synthesis gas |
| CN112221509B (en) * | 2020-10-16 | 2021-10-15 | 西南化工研究设计院有限公司 | Preparation method of high-stability methanol synthesis catalyst |
| CN112237916B (en) * | 2020-10-16 | 2021-10-15 | 西南化工研究设计院有限公司 | Preparation method of high-activity methanol synthesis catalyst |
| CN112264026B (en) * | 2020-11-18 | 2021-10-15 | 西南化工研究设计院有限公司 | Preparation method of high-activity high-selectivity methanol synthesis catalyst |
| CN112264025B (en) * | 2020-11-18 | 2021-10-15 | 西南化工研究设计院有限公司 | Simple, energy-saving and environment-friendly preparation method of methanol synthesis catalyst |
| CN114192149A (en) * | 2021-12-29 | 2022-03-18 | 上海方民科技有限公司 | Catalyst for preparing methanol by carbon dioxide hydrogenation and preparation method thereof |
| CN114939412B (en) * | 2022-06-08 | 2023-05-23 | 西南化工研究设计院有限公司 | Preparation method of high-selectivity methanol synthesis catalyst |
| CN114939411A (en) * | 2022-06-08 | 2022-08-26 | 西南化工研究设计院有限公司 | Preparation method of methanol synthesis catalyst with three-stage emulsifier |
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