CN112221509A - Preparation method of high-stability methanol synthesis catalyst - Google Patents
Preparation method of high-stability methanol synthesis catalyst Download PDFInfo
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- 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
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Abstract
The invention belongs to the technical field of catalysts, and particularly relates to a preparation method of a high-stability methanol synthesis catalyst. The method adopts an improved two-step precipitation method, and specifically comprises the steps of carrying out concurrent flow precipitation and aging reaction on a mixed salt solution of zinc nitrate and aluminum nitrate and an alkaline solution, filtering and washing aged slurry to obtain a filter cake, dispersing the obtained filter cake into the mixed salt solution of zinc nitrate, aluminum nitrate, copper nitrate and magnesium nitrate to obtain high-dispersion suspended slurry, carrying out concurrent flow precipitation and aging reaction on the high-dispersion suspended slurry and the alkaline solution, filtering, washing, drying, roasting, and tabletting for forming to obtain the high-dispersion suspended slurryObtaining the methanol synthesis catalyst. The invention has scientific design, simple method and convenient operation, and the methanol synthesis catalyst prepared by the invention can be widely used for CO-containing catalysts2CO and H2The synthesis gas can be used for producing methanol under the conditions of low temperature and low pressure, and the catalyst 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 preparation method of a high-stability methanol synthesis catalyst.
Background
Methanol is used as a basic organic raw material of C1 chemistry, is mainly used for producing Methyl Tertiary Butyl Ether (MTBE), dimethyl ether, formaldehyde, methyl formate, acetic acid and derivatives thereof, fumaric ester (DMF), gasoline and the like, and can also be used as potential alcohol ether fuel for vehicles, fuel for fuel cells and the like. With the popularization and application of methanol gasoline, the technical progress and the industrial breakthrough of methanol protein and methanol to olefin and the continuous development of downstream products such as dimethyl ether, acetic acid, methyl formate, dimethyl carbonate and the like have the advantages that the demand of methanol is continuously increased, and the methanol gasoline has bright application prospect. The production of methanol by a liquid-phase or gas-phase catalytic reaction process using synthesis gas as a raw material is a major method currently used in industry. Copper-based catalysts are generally used in this process, copper being considered the main active component. However, copper alone is very poor in activity and the introduction of other components can improve catalyst activity and stability to a large extent. The catalysts used in the world are basically mixed oxides of copper, zinc and aluminum.
The commonly used preparation methods of copper-based catalysts are precipitation methods and some methods improved on this basis, and there are great differences in the activity of the copper-based catalysts synthesized by these techniques. 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. At present, the domestic large-scale methanol device almost completely 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.
Disclosure of Invention
The present invention aims to solve the above technical problems and provide a method for preparing a high stability methanol synthesis catalyst. The methanol synthesis catalyst prepared by the method has the advantages of good low-temperature activity, good heat resistance, long service life, high selectivity and good stability.
In order to realize the purpose of the invention, the specific technical scheme of the invention is as follows:
a preparation method of a high-stability methanol synthesis catalyst comprises the following steps:
zn is added2+、Al3+The precipitate formed together is dispersed in the Cu-containing solution after washing and filtering2+、Zn2+、Al3+And Mg2+The mixed salt solution of (2) to form highly dispersed suspension slurry, then reacting the suspension slurry with alkali, filtering, washing, drying, roasting and molding to obtain the methanol synthesis catalyst.
Further, the preparation method of the high-stability methanol synthesis catalyst comprises the following specific steps:
step 1: dissolving zinc nitrate and aluminum nitrate in water to form a zinc-aluminum mixed salt solution A, dissolving zinc nitrate, aluminum nitrate, copper nitrate and magnesium nitrate in water to form a copper-zinc-magnesium-aluminum mixed salt solution B, and dissolving sodium carbonate in water to form an alkali solution C.
Step 2: and (3) carrying out a first-step precipitation reaction, namely, simultaneously dripping the saline solution A and the alkaline solution C into a reaction tank containing deionized water under the stirring action to react to generate a precipitate, stopping dripping the alkaline solution C after the dripping of the saline solution A is finished, and continuously aging for a certain time.
And step 3: and after the aging is finished, filtering and washing the precipitate, and dispersing a filter cake obtained by filtering into the mixed salt solution B to form high-dispersion suspension slurry D.
And 4, step 4: and (3) carrying out a second-step precipitation reaction, namely, simultaneously dropwise adding the suspension slurry D and the alkali solution C into a reaction tank containing deionized water under the stirring action to react to generate precipitates, stopping dropwise adding the alkali solution C after dropwise adding the suspension slurry D, and continuously aging for a certain time.
And 5: after the aging is finished, the precipitate is filtered and washed, and a filter cake obtained by filtering is dried.
Step 6: and decomposing the dried product at low temperature, adding graphite into the obtained decomposition product, uniformly mixing, and forming the mixture to obtain the methanol synthesis catalyst.
Further, in salt solution A and in salt solution B, Zn2+In a molar ratio of 1: 9-2: 3.
further, in the salt solution A and in the salt solution B, Al3+In a molar ratio of 7: 3-19: 1.
further, the reaction temperature is controlled to be 70-80 ℃, the pH value is controlled to be 6.0-8.0, and the aging temperature is the same as the reaction temperature in the two-step precipitation reaction (namely step 2 and step 4)).
Further, the aging time of the first precipitation reaction is 15-60 min, and the aging time of the second precipitation reaction is 60-120 min.
Further, the low-temperature decomposition temperature is 300-400 ℃, and the time is 2-6 hours; the amount of the graphite is 1-3 wt% of the mass of the mixture.
The methanol synthesis catalyst prepared by the preparation method comprises the following components in parts by mass based on the total mass of the catalyst: CuO: 55 to 75 parts of ZnO, 15 to 25 parts of Al2O3: 5-20 parts of MgO and 1-2 parts of MgO.
In the invention, in order to better control the reaction temperature, the raw materials are preheated in advance; and 3, dispersing the filter cake into the mixed salt solution B by using a circulating emulsification pump to form highly dispersed suspension slurry D.
Compared with the prior art, the invention has the following beneficial effects:
the methanol synthesis catalyst prepared by the method has the advantages of excellent low-temperature activity, good hydrothermal stability and high selectivity.
(II) in the present invention, Zn is added2+、Al3Precipitating together, filtering, and dispersing the precipitate containing Cu2+、Zn2+、Al3+And Mg2+Then precipitating in cocurrent with a base, which is conventionalCompared with the two-step precipitation method, the two-step precipitation method is more beneficial to uniformly mixing the second-step precipitate and the first-step precipitate, is beneficial to dispersing the second-step precipitate, and is beneficial to the second-step precipitate and the first-step precipitate entering microscopic pore canals of the two parties. Through the later stage roasting, because the precipitates in the two steps are uniformly mixed on the nano layer surface, and the active components in the second step enter the micro pore channels of the carrier to a certain extent, the metal specific surface area of the active components is favorably improved, and the low-temperature activity of the catalyst is favorably improved; the first-step precipitate plays a good role in dispersing the carrier, and the first-step precipitate is wrapped in microscopic pores by the second-step precipitate to a certain extent, so that the active components are further effectively isolated, the active components are uniformly dispersed and are not easy to gather, and the hydrothermal stability of the catalyst is favorably improved.
(III) in the present invention, Mg is introduced at the time of precipitation2+The method is not only beneficial to improving the hydrothermal stability of the catalyst, but also beneficial to increasing the alkalinity of the surface of the catalyst and improving the selectivity of the catalyst.
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 embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1:
the embodiment provides a preparation method of the methanol synthesis catalyst, which specifically comprises the following steps:
55.38g Zn (NO)3)2·6H2O and 140.48g Al (NO)3)3·9H2O is dissolved in 600ml of deionized water and stirred to dissolve it sufficiently to form a salt solution A. 253.12g of Cu (NO)3)2·3H2O，83.07g Zn(NO3)2·6H2O，60.2g Al(NO3)39H2O 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 NaCO3Dissolved in 2000ml of deionized waterStirring to dissolve fully, and forming alkali solution C needed by precipitation.
Preheating a salt solution A, a salt solution B and an alkali solution C, dropwise adding the salt solution A and the alkali solution C into a reaction tank containing a certain amount of deionized water simultaneously under strong stirring after the preheating temperature reaches 70 ℃, stopping dropwise adding the alkali C after dropwise adding the solution A, controlling the reaction temperature to be 70 ℃, and controlling the pH value to be 6.5-7.0. The constant temperature ageing at 70 ℃ is continued for 15min, followed by filtration and washing with deionized water until no Na is detected+. And (3) dispersing the filter cake of the precipitate in the first step into the mixed salt solution B by using a circulating emulsification pump to form highly dispersed suspension slurry D.
Under the condition of strong stirring, the suspension serous fluid D and the alkali solution C are simultaneously dripped into a reaction tank filled with a certain amount of deionized water; and stopping dropping the alkali C after the suspension slurry D is dropped, wherein the reaction temperature is 70 ℃, and the pH value is controlled to be 6.5-7.0. The temperature of 70 ℃ is kept constant and the aging is continued for 60min, then the filtration is carried out, and the washing is carried out by deionized water until no Na is detected+. Drying the obtained precipitate at 110 deg.C for 24 hr, and calcining the dried product at 300 deg.C for 6 hr. Adding graphite into the obtained roasted product, uniformly mixing to obtain a mixture, wherein the using amount of the graphite is 1% of the mass of the mixture, and forming to obtain a catalyst, wherein the catalyst is numbered as sample A (the mass percentages of the oxide components before forming are CuO: 55%, ZnO: 25%, MgO: 2%, and Al)2O3: 18 percent; in salt solution, Zn2+A：Zn2+B＝0.4:0.6，Al3+A：Al3+B＝0.7:0.3)。
Example 2:
the embodiment provides a preparation method of the methanol synthesis catalyst, which specifically comprises the following steps:
38.21g of Zn (NO)3)2·6H2O and 133.79g 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，89.16g Zn(NO3)2·6H2O，33.45g Al(NO3)39H2O 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 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, dropwise adding the salt solution A and the alkali solution C into a reaction tank containing a certain amount of deionized water simultaneously under strong stirring after the preheating temperature reaches 80 ℃, stopping dropwise adding the alkali C after dropwise adding the solution A, controlling the reaction temperature to be 80 ℃, and controlling the pH value to be 7.0-7.5. Aging at 80 deg.C for 30min, filtering, and washing with deionized water until no Na is detected+. And (3) dispersing the filter cake of the precipitate in the first step into the mixed salt solution B by using a circulating emulsification pump to form highly dispersed suspension slurry D.
Under the condition of strong stirring, the suspension serous fluid D and the alkali solution C are simultaneously dripped into a reaction tank filled with a certain amount of deionized water; stopping dropping the alkali C after the suspension slurry D is dropped, controlling the pH value at 80 ℃ and controlling the reaction temperature
The value is 7.0-7.5. The constant temperature ageing at 80 ℃ is continued for 60min, followed by filtration and washing with deionized water until no Na is detected+. Drying the obtained precipitate at 110 deg.C for 24 hr, and calcining the dried product at 350 deg.C for 4 hr. Adding graphite into the obtained roasted product, uniformly mixing to obtain a mixture, wherein the using amount of the graphite is 2% of the mass of the mixture, and forming to obtain a catalyst, wherein the number of the catalyst is sample B (the mass percentages of the oxide components before forming are CuO: 60%, ZnO: 23%, MgO: 2%, and Al: 60%)2O3:15 percent; in salt solution, Zn2+A：Zn2+B＝0.3:0.7，Al3+A：Al3+B＝0.8:0.2)。
Example 3:
the embodiment provides a preparation method of the methanol synthesis catalyst, which specifically comprises the following steps:
22.15g of Zn (NO)3)2·6H2O and 124.87g 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，88.61g Zn(NO3)2·6H2O，31.22g Al(NO3)39H2O and 9.71g 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, dropwise adding the salt solution A and the alkali solution C into a reaction tank containing a certain amount of deionized water simultaneously under strong stirring after the preheating temperature reaches 70 ℃, stopping dropwise adding the alkali C after dropwise adding the solution A, controlling the reaction temperature to be 70 ℃, and controlling the pH value to be 7.0-7.5. Aging at 70 deg.C for 30min, filtering, and washing with deionized water until no Na is detected+. And (3) dispersing the filter cake of the precipitate in the first step into the mixed salt solution B by using a circulating emulsification pump to form highly dispersed suspension slurry D.
Under the condition of strong stirring, the suspension serous fluid D and the alkali solution C are simultaneously dripped into a reaction tank filled with a certain amount of deionized water, after the suspension serous fluid D is dripped, the dripping of the alkali C is stopped, the reaction temperature is 70 ℃, and the pH value is controlled to be 7.0-7.5. The temperature of 70 ℃ is kept constant and the aging is continued for 120min, then the filtration is carried out, and the product is washed by deionized water until no Na is detected+. Drying the obtained precipitate at 110 deg.C for 24 hr, and calcining the dried product at 350 deg.C for 4 hr. Adding graphite into the obtained roasted product, uniformly mixing to obtain a mixture, wherein the using amount of the graphite is 2% of the mass of the mixture, and obtaining a catalyst after forming, wherein the number of the catalyst is sample C (the mass percentages of the oxide components before forming are CuO: 65%, ZnO: 20%, MgO: 1%, and Al: 65%)2O3: 14 percent; in salt solution, Zn2+A：Zn2+B＝0.2:0.8，Al3+A：Al3+B＝0.8:0.2)。
Example 4:
the embodiment provides a preparation method of the methanol synthesis catalyst, which specifically comprises the following steps:
9.41g of Zn (NO)3)2·6H2O and 110.38g 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，84.73g Zn(NO3)2·6H2O，12.26g Al(NO3)39H2O 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 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, dropwise adding the salt solution A and the alkali solution C into a reaction tank containing a certain amount of deionized water simultaneously under strong stirring after the preheating temperature reaches 80 ℃, stopping dropwise adding the alkali C after dropwise adding the solution A, controlling the reaction temperature to be 80 ℃, and controlling the pH value to be 7.0-7.5. The constant temperature ageing at 80 ℃ is continued for 60min, followed by filtration and washing with deionized water until no Na is detected+. And (3) dispersing the filter cake of the precipitate in the first step into the mixed salt solution B by using a circulating emulsification pump to form highly dispersed suspension slurry D.
Under the condition of strong stirring, the suspension serous fluid D and the alkali solution C are simultaneously dripped into a reaction tank filled with a certain amount of deionized water, after the suspension serous fluid D is dripped, the dripping of the alkali C is stopped, the reaction temperature is 80 ℃, and the pH value is controlled to be 7.0-7.5. Aging at 80 deg.C for 120min, filtering, and washing with deionized water until no Na is detected+. Drying the obtained precipitate at 110 deg.C for 24 hr, and calcining the dried product at 350 deg.C for 4 hr. Adding graphite into the obtained roasted product, uniformly mixing to obtain a mixture, wherein the using amount of the graphite is 2% of the mass of the mixture, and obtaining a catalyst after molding, wherein the catalyst is numbered as sample D (the mass percentages of the oxide components before molding are CuO: 70%, ZnO: 17%, MgO: 2%, and Al: 70%)2O3: 11 percent; in salt solution, Zn2+A：Zn2+B＝0.1:0.9，Al3+A：Al3+B＝0.9:0.1)。
Example 5:
the embodiment provides a preparation method of the methanol synthesis catalyst, which specifically comprises the following steps:
9.41g of Zn (NO)3)2·6H2O and 74.14g Al (NO)3)3·9H2O is dissolved in 400ml of deionized water and stirred to dissolve it sufficiently to form a salt solution A. 345.17g of Cu (NO)3)2·3H2O，84.73g Zn(NO3)2·6H2O，3.9g Al(NO3)39H2O and 9.71g 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, dropwise adding the salt solution A and the alkali solution C into a reaction tank containing a certain amount of deionized water simultaneously under strong stirring after the preheating temperature reaches 70 ℃, stopping dropwise adding the alkali C after dropwise adding the solution A, controlling the reaction temperature to be 70 ℃, and controlling the pH value to be 7.5-8.0. The temperature of 70 ℃ is kept constant and the aging is continued for 60min, then the filtration is carried out, and the washing is carried out by deionized water until no Na is detected+. And (3) dispersing the filter cake of the precipitate in the first step into the mixed salt solution B by using a circulating emulsification pump to form highly dispersed suspension slurry D.
Under the condition of strong stirring, the suspension serous fluid D and the alkali solution C are simultaneously dripped into a reaction tank filled with a certain amount of deionized water, after the suspension serous fluid D is dripped, the dripping of the alkali C is stopped, the reaction temperature is 70 ℃, and the pH value is controlled to be 7.5-8.0. The temperature of 70 ℃ is kept constant and the aging is continued for 120min, then the filtration is carried out, and the product is washed by deionized water until no Na is detected+. Drying the obtained precipitate at 110 deg.C for 24h, and calcining the dried product at 400 deg.C for 2 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 obtaining a catalyst after molding, wherein the catalyst is numbered as sample E (the mass percentages of the oxide components before molding are CuO: 75%, ZnO: 17%, MgO: 1%, and Al: 75%)2O3: 7 percent; in salt solution, Zn2+A：Zn2+B＝0.1:0.9，Al3+A：Al3+B＝0.95:0.05)。
Example 6:
this example is a comparative example, which provides a catalyst prepared by a conventional two-step precipitation method, as follows:
55.38g Zn (NO)3)2·6H2O and 140.48g Al (NO)3)3·9H2O is dissolved in 600ml of deionized water and stirred to dissolve it sufficiently to form a salt solution A. 253.12g of Cu (NO)3)2·3H2O，83.07g Zn(NO3)2·6H2O，60.2g 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 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, the pH values of the first reaction tank and the second reaction tank are 6.5-7.0, and the reaction temperatures of the first reaction tank and the second reaction tank are 70 ℃.
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 the mixture is aged for 60min at the constant temperature of 70 ℃ in the mixing tank.
After aging, the mixture is filtered and washed by deionized water until no Na is detected+Drying the obtained precipitate at 110 deg.C for 24 hr, and finally drying to obtain the product, and calcining at 300 deg.C for 6 hr. The obtained calcined product was mixed with graphite to obtain a mixture, the amount of graphite was 1% by mass of the mixture, and a comparative sample catalyst, sample F, was obtained after molding (the mass percentages of the components in the catalyst were the same as in the examples).
Example 7:
this example provides a method for evaluating the catalysts of examples 1-6, 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/N25/95 (volume ratio)) for 10-12 h, and the maximum reduction temperature is 220 ℃.
And (3) activity test: the raw material gas composition is as follows: 13.0-14.0% of CO, CO2＝4.0-5.0％，N210%, the remainder is H2The reaction pressure is 5.0MPa, and the space velocity is 10000h-1The reaction temperature is 235-245 ℃, and the CO conversion rate and CH before heat resistance are measured3OH 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 pressure is reduced to 0.1MPa, the reaction temperature is increased to 400 ℃, and the air speed is reduced to 3000h-1Post heat treatment for 10h, then returning to the activity test condition, and measuring CO conversion rate and CH after heat resistance3OH space-time yield.
The thermal stability of the catalyst is expressed as the ratio of the methanol space-time yield after the heat resistance test to the initial methanol space-time yield.
The catalysts of examples 1 to 6 were subjected to activity evaluation before and after heat resistance by the above-mentioned test methods, and the results are shown in Table 1. Since all catalysts tested had methanol selectivities above 99%, none of the catalysts are listed in the table.
TABLE 1 catalyst Heat resistant Pre-and post-catalyst activity data
As can be seen from the test results in Table 1, samples A, B, C, D and E exhibited CO conversion and CH conversion relative to comparative sample F3The OH space-time yield is clearly advantageous:
1. the catalyst prepared by the improved two-step precipitation method has the advantages that the CO conversion rate is up to 75 percent, and the space-time yield of methanol is higher than 1.38 g/(mL)catH); the CO conversion of the control sample is only 70.4%, and the space-time yield of methanol is only 1.29 g/(mL)cat·h)。
2. After the rapid aging test, the heat-resistant conversion rate of the catalyst prepared by the improved two-step precipitation method to CO is reduced, but the conversion rate is still more than 70 percent, and the space-time yield of the methanol is still 1.30 g/(mL)catH) above; the CO conversion of the control sample is reduced to 60.1%, and the space-time yield of methanol is reduced to 1.09 g/(mL)cat·h)。
3. Through rapid aging experiments, the catalyst prepared by the improved two-step precipitation method has the methanol space-time yield after heat resistance higher than that before heat resistance of 0.90, and the comparison sample has only 0.84, which shows that the catalyst prepared by the method has high thermal stability.
Overall, the catalyst prepared by the improved two-step precipitation process has excellent low temperature activity and good thermal 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 conform to the technical problems of the present invention, should be included in the scope of the present invention.
Claims (8)
1. A preparation method of a high-stability methanol synthesis catalyst is characterized by comprising the following steps:
zn is added2+、Al3+The precipitate formed together is dispersed in the Cu-containing solution after filtration and washing2+、Zn2+、Al3+And Mg2+The mixed salt solution of (2) to form highly dispersed suspension slurry, then the suspension slurry and alkali are reacted in a parallel flow manner, and then the methanol synthesis catalyst is prepared by filtering, washing, drying, roasting and tabletting forming.
2. The method for preparing a high-stability methanol synthesis catalyst according to claim 1, wherein: the method comprises the following steps:
step 1: dissolving zinc nitrate and aluminum nitrate in water to form a zinc-aluminum mixed salt solution A, dissolving zinc nitrate, aluminum nitrate, copper nitrate and magnesium nitrate in water to form a copper-zinc-magnesium-aluminum mixed salt solution B, and dissolving sodium carbonate in water to form an alkali solution C;
step 2: carrying out a first-step precipitation reaction, namely simultaneously dripping a salt solution A and an alkali solution C into a reaction tank containing deionized water under the stirring action to react to generate a precipitate I, stopping dripping the alkali solution C after the dripping of the salt solution A is finished, and continuously aging for a certain time;
and step 3: after the aging is finished, filtering and washing the precipitate, and dispersing a filter cake obtained by filtering into a mixed salt solution B to form high-dispersion suspension slurry D;
and 4, step 4: carrying out a second-step precipitation reaction, namely, simultaneously dropwise adding the suspension slurry D and the alkali solution C into a reaction tank containing deionized water under the stirring action to react to generate a precipitate II, stopping dropwise adding the alkali solution C after dropwise adding the suspension slurry D, and continuously aging for a certain time;
and 5: after the aging is finished, the precipitate is filtered and washed, and a filter cake obtained by filtering is dried.
Step 6: and (3) decomposing the dried product at low temperature, adding graphite into the obtained decomposition product, uniformly mixing, and forming the mixture to obtain the methanol synthesis catalyst.
3. The method for preparing a high-stability methanol synthesis catalyst according to claim 2, wherein: in salt solution A and salt solution B, Zn2+In a molar ratio of 1: 9-2: 3.
4. the method for preparing a high-stability methanol synthesis catalyst according to claim 2, wherein: in salt solution A and in salt solution B, Al3+In a molar ratio of 7: 3-19: 1.
5. the method for preparing a high-stability methanol synthesis catalyst according to claim 2, wherein: in the precipitation reaction in the step 2 and the step 4, the reaction temperature needs to be controlled to be 70-80 ℃, the pH value needs to be 6.0-8.0, and the aging temperature needs to be the same as the reaction temperature.
6. The method for preparing a high-stability methanol synthesis catalyst according to claim 2, wherein: the aging time of the step 2 is 15-60 min, and the aging time of the step 4 is 60-120 min.
7. The method for preparing a high-stability methanol synthesis catalyst according to claim 2, wherein: in the step 6, the low-temperature decomposition temperature is 300-400 ℃, and the time is 2-6 hours; the amount of the graphite is 1-3 wt% of the mass of the mixture.
8. The catalyst prepared by the method of any one of claims 1 to 7, characterized by comprising the following components in parts by mass: CuO: 55 to 75 parts of ZnO, 15 to 25 parts of Al2O3: 5-20 parts of MgO and 1-2 parts of MgO.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN114939412A (en) * | 2022-06-08 | 2022-08-26 | 西南化工研究设计院有限公司 | Preparation method of high-selectivity methanol synthesis catalyst |
| RU2781406C1 (en) * | 2021-10-29 | 2022-10-11 | Федеральное государственное автономное образовательное учреждение высшего образования «Национальный исследовательский Томский государственный университет» | Method for preparation of oxide catalysts |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4111847A (en) * | 1972-04-20 | 1978-09-05 | E. I. Du Pont De Nemours And Company | Methanol synthesis catalyst |
| CN1219445A (en) * | 1998-11-16 | 1999-06-16 | 天津大学 | New synthetic copper methoxide series catalysts and their preparation method |
| CN103272607A (en) * | 2013-06-08 | 2013-09-04 | 上海中科高等研究院 | Copper based catalyst used for hydrogenating carbon dioxide to synthesize methanol, and preparation method and application thereof |
| CN103721719A (en) * | 2014-01-03 | 2014-04-16 | 中国科学院山西煤炭化学研究所 | Catalyst for synthesizing methanol through CO2 hydrogenation as well as preparation method and application |
| CN106179360A (en) * | 2016-06-29 | 2016-12-07 | 西安向阳航天材料股份有限公司 | A kind of CuZnAl catalyst and preparation method thereof |
| CN107008332A (en) * | 2016-01-27 | 2017-08-04 | 中国科学院大连化学物理研究所 | A kind of catalyst of synthesizing methanol by hydrogenating carbon dioxide and its preparation and application |
| CN109126808A (en) * | 2018-10-24 | 2019-01-04 | 太原理工大学 | A kind of additive modification copper-based catalysts and preparation method and applications |
| CN109289854A (en) * | 2018-11-01 | 2019-02-01 | 四川天科技股份有限公司 | A kind of high stability high intensity catalst for synthesis of methanol and preparation method thereof |
| CN109289855A (en) * | 2018-11-01 | 2019-02-01 | 四川天科技股份有限公司 | A kind of synthesis gas catalyst for methanol and preparation method thereof |
| CN110314688A (en) * | 2018-03-28 | 2019-10-11 | 国家能源投资集团有限责任公司 | Methanol synthesis catalyst and preparation method thereof |
| CN110681383A (en) * | 2018-07-06 | 2020-01-14 | 中国石油化工股份有限公司 | Multi-component methanol synthesis catalyst and preparation method thereof |
| CN111215083A (en) * | 2018-11-23 | 2020-06-02 | 陈双云 | Preparation method of methanol catalyst |
| CN111686739A (en) * | 2019-03-12 | 2020-09-22 | 中国石油化工股份有限公司 | Preparation method of copper-containing catalyst |
-
2020
- 2020-10-16 CN CN202011110409.0A patent/CN112221509B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4111847A (en) * | 1972-04-20 | 1978-09-05 | E. I. Du Pont De Nemours And Company | Methanol synthesis catalyst |
| CN1219445A (en) * | 1998-11-16 | 1999-06-16 | 天津大学 | New synthetic copper methoxide series catalysts and their preparation method |
| CN103272607A (en) * | 2013-06-08 | 2013-09-04 | 上海中科高等研究院 | Copper based catalyst used for hydrogenating carbon dioxide to synthesize methanol, and preparation method and application thereof |
| CN103721719A (en) * | 2014-01-03 | 2014-04-16 | 中国科学院山西煤炭化学研究所 | Catalyst for synthesizing methanol through CO2 hydrogenation as well as preparation method and application |
| CN107008332A (en) * | 2016-01-27 | 2017-08-04 | 中国科学院大连化学物理研究所 | A kind of catalyst of synthesizing methanol by hydrogenating carbon dioxide and its preparation and application |
| CN106179360A (en) * | 2016-06-29 | 2016-12-07 | 西安向阳航天材料股份有限公司 | A kind of CuZnAl catalyst and preparation method thereof |
| CN110314688A (en) * | 2018-03-28 | 2019-10-11 | 国家能源投资集团有限责任公司 | Methanol synthesis catalyst and preparation method thereof |
| CN110681383A (en) * | 2018-07-06 | 2020-01-14 | 中国石油化工股份有限公司 | Multi-component methanol synthesis catalyst and preparation method thereof |
| CN109126808A (en) * | 2018-10-24 | 2019-01-04 | 太原理工大学 | A kind of additive modification copper-based catalysts and preparation method and applications |
| CN109289854A (en) * | 2018-11-01 | 2019-02-01 | 四川天科技股份有限公司 | A kind of high stability high intensity catalst for synthesis of methanol and preparation method thereof |
| CN109289855A (en) * | 2018-11-01 | 2019-02-01 | 四川天科技股份有限公司 | A kind of synthesis gas catalyst for methanol and preparation method thereof |
| CN111215083A (en) * | 2018-11-23 | 2020-06-02 | 陈双云 | Preparation method of methanol catalyst |
| CN111686739A (en) * | 2019-03-12 | 2020-09-22 | 中国石油化工股份有限公司 | Preparation method of copper-containing catalyst |
Non-Patent Citations (2)
| Title |
|---|
| 林胜达等: "沉淀方法对铜基甲醇合成催化剂前驱体及其性能的影响", 《催化学报》 * |
| 汤密: "基于铜基催化剂加氢合成甲醇技术的中国专利申请分析", 《山东化工》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2781406C1 (en) * | 2021-10-29 | 2022-10-11 | Федеральное государственное автономное образовательное учреждение высшего образования «Национальный исследовательский Томский государственный университет» | Method for preparation of oxide catalysts |
| RU2787818C1 (en) * | 2021-10-29 | 2023-01-12 | Федеральное государственное автономное образовательное учреждение высшего образования «Национальный исследовательский Томский государственный университет» | Method for producing an oxide catalyst for dehydrating organic substances |
| 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 |
| CN114939412A (en) * | 2022-06-08 | 2022-08-26 | 西南化工研究设计院有限公司 | Preparation method of high-selectivity methanol synthesis catalyst |
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