CN111569888A - Preparation method of sulfur-resistant and high-temperature-resistant methanol catalyst with hollow core-shell structure - Google Patents

Preparation method of sulfur-resistant and high-temperature-resistant methanol catalyst with hollow core-shell structure Download PDF

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CN111569888A
CN111569888A CN202010489065.2A CN202010489065A CN111569888A CN 111569888 A CN111569888 A CN 111569888A CN 202010489065 A CN202010489065 A CN 202010489065A CN 111569888 A CN111569888 A CN 111569888A
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CN111569888B (en
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郭丹
林倩
史连军
李雯博
潘红艳
曹建新
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Guizhou University
Wengfu Group Co Ltd
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Wengfu Group Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • 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
    • B01J23/70—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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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
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Abstract

The invention discloses a preparation method of a sulfur-resistant and high-temperature-resistant hollow core-shell structure methanol catalyst, which comprises the steps of firstly preparing a copper-based catalyst with a core-shell structure, and then utilizing energy and H2Modifying the copper-based catalyst by using the modifier for the S reaction to obtain the sulfur-resistant and high-temperature-resistant methanol catalyst with the hollow core-shell structure. The copper-based catalyst prepared by the invention has the characteristics of good catalytic stability and long service life.

Description

Preparation method of sulfur-resistant and high-temperature-resistant methanol catalyst with hollow core-shell structure
Technical Field
The invention relates to a preparation method of a methanol catalyst, in particular to a preparation method of a sulfur-resistant and high-temperature-resistant methanol catalyst with a hollow core-shell structure
Background
For the catalyst for preparing methanol from synthesis gas, Cu/ZnO catalyst or Cu/ZnO/Al catalyst is adopted industrially2O3The catalysts all belong to copper-based catalysts.
However, the biggest problems of the currently industrially adopted copper-based catalyst are poor stability and short service life of the catalyst, and the shortening of the service life of the catalyst undoubtedly increases the production cost of enterprises and restricts the rapid development of the enterprises.
The reasons for poor stability and short service life are mainly two, namely, the sulfur-sensitive and sulfur-poisoning easily occur; secondly, the high temperature resistance is not high. For the first reason, mainly the catalyst is affected by a small amount of hydrogen sulfide in the synthesis gas during the working process, and the hydrogen sulfide is combined with the catalytic component Cu in the catalyst, so that the catalyst is failed; the second reason is that the catalytic activity of the copper-based catalyst is significantly reduced with the increase in the size of copper particles, while the copper nanoparticles are easily agglomerated during the corresponding high-temperature operation, resulting in deactivation and reduced stability.
Therefore, how to improve the catalytic stability of the copper-based catalyst and prolong the catalytic service life of the copper-based catalyst is an industry technical problem which needs to be solved urgently.
Disclosure of Invention
The invention aims to provide a preparation method of a sulfur-resistant and high-temperature-resistant methanol catalyst with a hollow core-shell structure. The copper-based catalyst prepared by the invention has the characteristics of good catalytic stability and long service life.
The technical scheme of the invention is as follows: a process for preparing the sulfur-resistant and high-temp-resistant methanol catalyst with hollow core-shell structure includes such steps as preparing the copper-base catalyst with core-shell structure, and mixing it with H2Modifying the copper-based catalyst by using the modifier of S reactionThus obtaining the sulfur-resistant and high-temperature-resistant methanol catalyst with the hollow core-shell structure.
In the preparation method of the sulfur-resistant and high-temperature-resistant methanol catalyst with the hollow core-shell structure, the core-shell structure is a hollow core-shell structure.
In the preparation method of the sulfur-resistant and high-temperature-resistant hollow core-shell structure methanol catalyst, the core of the copper-based catalyst is a Cu-Zn catalyst, and the shell is porous silicon dioxide.
In the preparation method of the sulfur-resistant and high-temperature-resistant methanol catalyst with the hollow core-shell structure, the specific preparation process of the catalyst is as follows:
(1) taking Cu (NO)3)2·3H2O and Zn (NO)3)2·6H2Dissolving O in deionized water to obtain product A;
(2) adding surfactant polyethylene glycol mono-hexadecane ether into solution containing cyclohexane and n-octanol, and dissolving in water bath at 30-40 deg.C under stirring to obtain product B;
(3) adding product A into product B, stirring, and adding NaBH4Adding ammonia water and fully stirring after the reaction is finished, adding TEOS (tetraethyl orthosilicate) and continuously stirring, adding 50mL of ethanol after the hydrolytic condensation reaction, finally centrifugally washing the ethanol, washing the product obtained by centrifugation by using ethanol to obtain CuZn @ SiO2(ii) a The core-shell structure obtained in the step is a solid core-shell structure similar to the structure of egg white and protein;
(4) the prepared CuZn @ SiO2Ultrasonically dispersing into deionized water, adding CTAB, and stirring at room temperature to form uniform dispersion to obtain product C;
(5) sequentially adding sodium metaaluminate and anhydrous sodium carbonate into the product C, continuously stirring for 2-4h at 90-100 ℃, naturally cooling to room temperature, and centrifugally washing with deionized water to obtain a product D; the product D obtained in the step is a hollow structure which is etched and stripped between the core shells and is similar to the structure of a peanut shell and a peanut kernel; the same applies to the preparation of the Cu-Zn-Al catalyst;
(6) drying product D in 75-85 deg.C oven overnight to obtain catalyst powder, mixing with modifier waterSoaking the solution for 20-30H, drying in a 75-85 deg.C oven, and calcining to obtain modified catalyst which is used in H2Reducing under the condition to obtain the modified Cu-Zn hollow core-shell structure catalyst.
In the preparation method of the sulfur-resistant and high-temperature-resistant methanol catalyst with the hollow core-shell structure, the ratio of Cu in the product A: the molar ratio of Zn is 7: 3; in the B product, each 40ml of cyclohexane contains 8-12ml of n-octanol and 8-9g of polyethylene glycol monocetyl ether; in the step (3), NaBH4The concentration of the solution was 10 wt%, NaBH was added4The post-reaction time of the solution is 5-15min, the concentration of ammonia water is 25-28 wt%, the post-reaction time after the ammonia water is added is 0.5-1.5h, and the post-reaction time after the TEOS is added is 4-8 h; CuZn @ SiO in step (4) and step (5)2The mass ratio of CTAB, sodium metaaluminate, anhydrous sodium carbonate and deionized water is 1: 0.25: 0.53: 0.41: 200 of a carrier; and (6) the roasting temperature is 400-500 ℃, and the modifier aqueous solution and the catalyst powder are impregnated in equal volume.
In the preparation method of the sulfur-resistant and high-temperature-resistant hollow core-shell structure methanol catalyst, the core of the copper-based catalyst is a Cu-Zn-Al catalyst, and the shell is porous silicon dioxide.
In the preparation method of the sulfur-resistant and high-temperature-resistant methanol catalyst with the hollow core-shell structure, the specific preparation process of the catalyst is as follows:
(1) taking Cu (NO)3)2·3H2O、Zn(NO3)2·6H2O and Al (NO)3)3·9H2Dissolving O in deionized water to obtain product A;
(2) adding surfactant polyethylene glycol mono-hexadecane ether into solution containing cyclohexane and n-octanol, and dissolving in water bath at 30-40 deg.C under stirring to obtain product B;
(3) adding product A into product B, stirring, and adding NaBH4Adding ammonia water into the solution after the reaction is finished, fully stirring the solution, adding TEOS (tetraethyl orthosilicate) into the solution, continuously stirring the solution, performing hydrolytic condensation reaction, adding 50mL of ethanol, finally performing centrifugal washing on the ethanol, and washing a product obtained by centrifugation by using ethanol to obtain CuZnAl @ SiO2；
(4) Will be provided withPrepared CuZnAl @ SiO2Ultrasonically dispersing into deionized water, adding CTAB, and stirring at room temperature to form uniform dispersion to obtain product C;
(5) sequentially adding sodium metaaluminate and anhydrous sodium carbonate into the product C, continuously stirring for 2-4h at 90-100 ℃, naturally cooling to room temperature, and centrifugally washing with deionized water to obtain a product D;
(6) drying product D in 75-85 deg.C oven overnight to obtain catalyst powder, soaking the catalyst powder and modifier aqueous solution for 20-30H, drying in 75-85 deg.C oven, calcining to obtain modified catalyst, and placing in H before use2Reducing under the condition to obtain the modified Cu-Zn-Al hollow core-shell structure catalyst.
In the preparation method of the sulfur-resistant and high-temperature-resistant methanol catalyst with the hollow core-shell structure, the ratio of Cu in the product A: zn: the molar ratio of Al is 6: 3: 1; in the B product, each 40ml of cyclohexane contains 8-12ml of n-octanol and 8-9g of polyethylene glycol monocetyl ether; in the step (3), NaBH4The concentration of the solution was 10 wt%, NaBH was added4The post-reaction time of the solution is 5-15min, the concentration of ammonia water is 25-28 wt%, the post-reaction time after the ammonia water is added is 0.5-1.5h, and the post-reaction time after the TEOS is added is 4-8 h; the CuZnAl @ SiO in the step (4) and the step (5)2The mass ratio of CTAB, sodium metaaluminate, anhydrous sodium carbonate and deionized water is 1: 0.25: 0.53: 0.41: 200 of a carrier; and (6) the roasting temperature is 400-500 ℃, and the modifier aqueous solution and the catalyst powder are impregnated in equal volume.
In the preparation method of the sulfur-resistant and high-temperature-resistant methanol catalyst with the hollow core-shell structure, the modifier is Ce (NO)3)3·6H2O、Mn(NO3)2、Fe(NO3)3·9H2O、(NH4)2MoO4And SnCl4·5H2O。
The invention has the advantages of
1. According to the invention, the copper-based catalyst is made into a hollow core-shell structure, the catalyst of the core part is protected by the porous silicon dioxide layer on the outer layer, synthesis gas enters the core through the shell layer and reacts under the catalytic action of the catalyst, and meanwhile, the protection of the catalyst is improved, the high temperature resistance is improved, the stability of the catalyst is enhanced, and the service life is prolonged by the confinement effect.
2. According to the invention, the shell of the copper-based catalyst with the hollow core-shell structure is modified, and the shell is modified and loaded with a substance which can react with hydrogen sulfide in the synthesis gas preferentially, so that a small amount of hydrogen sulfide gas in the synthesis gas can be filtered and eliminated before the synthesis gas enters the internal core catalyst, thereby greatly reducing the sulfur poisoning degree of the copper-based catalyst, improving the stability of the catalyst and prolonging the service life.
Examples of the experiments
The inventor respectively treats the high temperature resistance of the traditional Cu-Zn-Al catalyst and the Cu-Zn-Al catalyst with the core-shell structure prepared by the invention, and the traditional Cu-Zn-Al catalyst and the CeO prepared by the invention2The sulfur resistance of the modified core-shell Cu-Zn-Al catalyst was compared and the results are shown in table 1 and fig. 1, and table 2 and fig. 2, respectively.
TABLE 1 comparison of high temperature resistance
Figure BDA0002520224960000041
As shown in table 1 and fig. 1, the catalytic activity of the conventional Cu-Zn-Al catalyst and the Cu-Zn-Al catalyst with the core-shell structure prepared by the present invention gradually becomes stable with the lapse of catalytic time, but the catalytic activity of the conventional catalyst is lower than that of the catalyst with the core-shell structure of the present invention due to the lack of high temperature protection.
TABLE 2 Sulfur tolerance test
Catalyst and process for preparing same 3 4 5 6 7 8 9 10
Comparative example 3.78 3.96 4.53 4.47 4.65 4.58 4.63 4.61
Examples 8.43 9.67 9.72 9.75 9.69 9.82 9.88 9.78
As shown in table 2 and fig. 2, the catalytic activity of the conventional Cu-Zn-Al catalyst and the core-shell Cu-Zn-Al catalyst modified according to the present invention gradually became stable with the passage of catalytic time, but the catalytic activity of the conventional catalyst is lower than that of the core-shell Cu-Zn-Al catalyst modified according to the present invention due to poor sulfur tolerance.
Drawings
FIG. 1 is a flow chart of the present invention;
FIG. 2 is a comparison graph of high temperature resistance experimental data;
FIG. 3 is a graph comparing experimental data on sulfur tolerance.
Detailed Description
The present invention is further illustrated by the following examples, which are not to be construed as limiting the invention.
Examples of the invention
Example 1: a preparation method of a sulfur-resistant and high-temperature-resistant methanol Cu-Zn catalyst with a hollow core-shell structure comprises the following steps:
(1) taking Cu (NO)3)2·3H2O and Zn (NO)3)2·6H2Dissolving O in deionized water to obtain product A, wherein the molar ratio of Cu/Zn is 7: 3;
(2) adding 8.72g surfactant polyethylene glycol mono-hexadecane into solution containing 40ml cyclohexane and 10ml n-octanol, and dissolving in water bath at 35 deg.C under stirring to obtain product B;
(3) adding the product A into the product B, continuously stirring, and then adding NaBH with the concentration of 10 wt%4Reacting the solution with 300 mu L for 10min, adding ammonia water with the concentration of 26 wt%, fully stirring for 1h, adding TEOS, continuously stirring for 6h, performing hydrolytic condensation reaction, adding 50mL of ethanol, finally performing ethanol centrifugal washing, and washing the product obtained by centrifugation with ethanol to obtain CuZn @ SiO2；
(4) The prepared CuZn @ SiO2Ultrasonically dispersing into deionized water, adding CTAB, and stirring at room temperature to form uniform dispersion to obtain product C;
(5) adding sodium metaaluminate, anhydrous sodium carbonate and CuZn @ SiO into product C in sequence2The mass ratio of CTAB, sodium metaaluminate, anhydrous sodium carbonate and deionized water is 1: 0.25: 0.53: 0.41: 200, at 95 ℃ for a long timeStirring for 3h, naturally cooling to room temperature, and centrifugally washing with deionized water to obtain product D;
(6) drying product D in 80 deg.C oven overnight to obtain catalyst powder, and mixing with Ce (NO)3)3·6H2Soaking O aqueous solution in the same volume for 24H, drying in an oven at 80 ℃, roasting at 450 ℃ to obtain the modified CuO/ZnO @ HMAN catalyst, and placing in H before use2And reducing under the condition to obtain the modified CuZnO @ HMAN catalyst.
Example 2: a preparation method of a sulfur-resistant and high-temperature-resistant methanol Cu-Zn catalyst with a hollow core-shell structure comprises the following steps:
(1) taking Cu (NO)3)2·3H2O and Zn (NO)3)2·6H2Dissolving O in deionized water to obtain product A, wherein the molar ratio of Cu/Zn is 7: 3;
(2) adding 8g of surfactant polyethylene glycol mono-hexadecane ether into a solution containing 40ml of cyclohexane and 8ml of n-octanol, and stirring and dissolving in a water bath at 30 ℃ to obtain a product B;
(3) adding the product A into the product B, continuously stirring, and then adding NaBH with the concentration of 10 wt%4Reacting the solution for 5min, adding ammonia water with the concentration of 25 wt%, fully stirring for 0.5h, adding TEOS, continuously stirring for 4h, performing hydrolytic condensation reaction, adding 50mL of ethanol, finally performing ethanol centrifugal washing, and washing the product obtained by centrifugation with ethanol to obtain CuZn @ SiO2；
(4) The prepared CuZn @ SiO2Ultrasonically dispersing into deionized water, adding CTAB, and stirring at room temperature to form uniform dispersion to obtain product C;
(5) adding sodium metaaluminate, anhydrous sodium carbonate and CuZn @ SiO into product C in sequence2The mass ratio of CTAB, sodium metaaluminate, anhydrous sodium carbonate and deionized water is 1: 0.25: 0.53: 0.41: 200, continuously stirring for 2 hours at the temperature of 90 ℃, naturally cooling to room temperature, and centrifugally washing by deionized water to obtain a product D;
(6) drying product D in 75 deg.C oven overnight to obtain catalyst powder, and mixing with Mn (NO)3)2Soaking in water solution for 20 hr at equal volume, and oven drying at 75 deg.CAfter drying in a box, roasting at 400 ℃ to obtain the modified CuO/ZnO @ HMAN catalyst which is added with H before use2And reducing under the condition to obtain the modified CuZnO @ HMAN catalyst.
Example 3: a preparation method of a sulfur-resistant and high-temperature-resistant methanol Cu-Zn catalyst with a hollow core-shell structure comprises the following steps:
(1) taking Cu (NO)3)2·3H2O and Zn (NO)3)2·6H2Dissolving O in deionized water to obtain product A, wherein the molar ratio of Cu/Zn is 7: 3;
(2) adding 9g of surfactant polyethylene glycol mono-hexadecane ether into a solution containing 40ml of cyclohexane and 12ml of n-octanol, and stirring and dissolving in a water bath at 40 ℃ to obtain a product B;
(3) adding the product A into the product B, continuously stirring, and then adding NaBH with the concentration of 10 wt%4Reacting the solution for 15min, adding 28 wt% ammonia water, fully stirring for 1.5h, adding TEOS, continuously stirring for 8h, performing hydrolytic condensation reaction, adding 50mL ethanol, finally performing ethanol centrifugal washing, and washing the product obtained by centrifugation with ethanol to obtain CuZn @ SiO2；
(4) The prepared CuZn @ SiO2Ultrasonically dispersing into deionized water, adding CTAB, and stirring at room temperature to form uniform dispersion to obtain product C;
(5) adding sodium metaaluminate, anhydrous sodium carbonate and CuZn @ SiO into product C in sequence2The mass ratio of CTAB, sodium metaaluminate, anhydrous sodium carbonate and deionized water is 1: 0.25: 0.53: 0.41: 200, continuously stirring for 4 hours at the temperature of 100 ℃, naturally cooling to room temperature, and centrifugally washing by deionized water to obtain a product D;
(6) drying product D in 85 deg.C oven overnight to obtain catalyst powder, and mixing with Fe (NO)3)3·9H2Soaking O aqueous solution in the same volume for 30H, drying in an oven at 85 ℃, and then roasting at 500 ℃ to obtain the modified CuO/ZnO @ HMAN catalyst which is H before use2And reducing under the condition to obtain the modified CuZnO @ HMAN catalyst.
Example 4: a preparation method of a sulfur-resistant and high-temperature-resistant methanol Cu-Zn-Al catalyst with a hollow core-shell structure comprises the following steps:
(1) taking Cu (NO)3)2·3H2O、Zn(NO3)2·6H2O and Al (NO)3)3·9H2Dissolving O in deionized water to obtain product A, wherein the molar ratio of Cu/Zn/Al is 6: 3: 1;
(2) adding 8.72g surfactant polyethylene glycol mono-hexadecane into solution containing 40ml cyclohexane and 10ml n-octanol, and dissolving in water bath at 35 deg.C under stirring to obtain product B;
(3) adding the product A into the product B, continuously stirring, and then adding NaBH with the concentration of 10 wt%4Reacting the solution for 10min, adding ammonia water with the concentration of 26 wt%, fully stirring for 1h, adding TEOS, continuously stirring for 6h, performing hydrolytic condensation reaction, adding 50mL of ethanol, finally performing ethanol centrifugal washing, and washing the product obtained by centrifugation with ethanol to obtain CuZnAl @ SiO2；
(4) The prepared CuZnAl @ SiO2Ultrasonically dispersing into deionized water, adding CTAB, and stirring at room temperature to form uniform dispersion to obtain product C;
(5) sequentially adding sodium metaaluminate, anhydrous sodium carbonate and CuZnAl @ SiO into the product C2The mass ratio of CTAB, sodium metaaluminate, anhydrous sodium carbonate and deionized water is 1: 0.25: 0.53: 0.41: 200, continuously stirring for 3 hours at the temperature of 95 ℃, naturally cooling to room temperature, and centrifugally washing by deionized water to obtain a product D;
(6) drying product D in 80 deg.C oven overnight to obtain catalyst powder, and mixing with (NH)4)2MoO4Soaking the aqueous solution in the same volume for 24H, drying in an oven at 80 ℃, and then roasting at 450 ℃ to obtain the modified catalyst which is treated with H before use2Reducing under the condition.
Example 5: a preparation method of a sulfur-resistant and high-temperature-resistant methanol Cu-Zn-Al catalyst with a hollow core-shell structure comprises the following steps:
(1) taking Cu (NO)3)2·3H2O、Zn(NO3)2·6H2O and Al (NO)3)3·9H2Dissolving O in deionized water to obtain product A, whereinThe Cu/Zn/Al molar ratio is 6: 3: 1;
(2) adding 8g of surfactant polyethylene glycol mono-hexadecane ether into a solution containing 40ml of cyclohexane and 8ml of n-octanol, and stirring and dissolving in a water bath at 30 ℃ to obtain a product B;
(3) adding the product A into the product B, continuously stirring, and then adding NaBH with the concentration of 10 wt%4Reacting the solution for 5min, adding ammonia water with the concentration of 25 wt%, fully stirring for 0.5h, adding TEOS, continuously stirring for 4h, performing hydrolytic condensation reaction, adding 50mL of ethanol, finally performing ethanol centrifugal washing, and washing the product obtained by centrifugation with ethanol to obtain CuZnAl @ SiO2；
(4) The prepared CuZnAl @ SiO2Ultrasonically dispersing into deionized water, adding CTAB, and stirring at room temperature to form uniform dispersion to obtain product C;
(5) sequentially adding sodium metaaluminate, anhydrous sodium carbonate and CuZnAl @ SiO into the product C2The mass ratio of CTAB, sodium metaaluminate, anhydrous sodium carbonate and deionized water is 1: 0.25: 0.53: 0.41: 200, continuously stirring for 2 hours at the temperature of 90 ℃, naturally cooling to room temperature, and centrifugally washing by deionized water to obtain a product D;
(6) drying product D in 75 deg.C oven overnight to obtain catalyst powder, and mixing with SnCl4·5H2Soaking O water solution in the same volume for 20H, drying in a 75 ℃ oven, and then roasting at 400 ℃ to obtain the modified catalyst which is treated with H before use2Reducing under the condition.
Example 6: a preparation method of a sulfur-resistant and high-temperature-resistant methanol Cu-Zn-Al catalyst with a hollow core-shell structure comprises the following steps:
(1) taking Cu (NO)3)2·3H2O、Zn(NO3)2·6H2O and Al (NO)3)3·9H2Dissolving O in deionized water to obtain product A, wherein the molar ratio of Cu/Zn/Al is 6: 3: 1;
(2) adding 9g of surfactant polyethylene glycol mono-hexadecane ether into a solution containing 40ml of cyclohexane and 12ml of n-octanol, and stirring and dissolving in a water bath at 40 ℃ to obtain a product B;
(3) adding into BProduct A, continuously stirring, and then adding NaBH with the concentration of 10 wt%4Reacting the solution for 15min, adding 28 wt% ammonia water, fully stirring for 1.5h, adding TEOS, continuously stirring for 8h, performing hydrolytic condensation reaction, adding 50mL ethanol, finally performing ethanol centrifugal washing, and washing the product obtained by centrifugation with ethanol to obtain CuZnAl @ SiO2；
(4) The prepared CuZnAl @ SiO2Ultrasonically dispersing into deionized water, adding CTAB, and stirring at room temperature to form uniform dispersion to obtain product C;
(5) sequentially adding sodium metaaluminate, anhydrous sodium carbonate and CuZnAl @ SiO into the product C2The mass ratio of CTAB, sodium metaaluminate, anhydrous sodium carbonate and deionized water is 1: 0.25: 0.53: 0.41: 200, continuously stirring for 4 hours at the temperature of 100 ℃, naturally cooling to room temperature, and centrifugally washing by deionized water to obtain a product D;
(6) drying product D in 85 deg.C oven overnight to obtain catalyst powder, and mixing with Ce (NO)3)3·6H2Soaking O water solution in the same volume for 30H, drying in a 85 ℃ oven, and then roasting at 500 ℃ to obtain the modified catalyst which is treated with H before use2Reducing under the condition.
The above description is only for the purpose of illustrating the present invention and the appended claims, and the scope of the present invention is not limited thereto, and any person skilled in the art can substitute or change the technical solution and the inventive concept of the present invention within the technical scope of the present invention.

Claims (9)

1. A preparation method of a sulfur-resistant and high-temperature-resistant methanol catalyst with a hollow core-shell structure is characterized by comprising the following steps: firstly preparing a copper-based catalyst with a core-shell structure, and then utilizing energy and H2Modifying the copper-based catalyst by using the modifier for the S reaction to obtain the sulfur-resistant and high-temperature-resistant methanol catalyst with the hollow core-shell structure.
2. The preparation method of the sulfur-resistant and high-temperature-resistant hollow core-shell structure methanol catalyst according to claim 1, characterized by comprising the following steps: the core-shell structure is a hollow core-shell structure.
3. The preparation method of the sulfur-resistant and high-temperature-resistant hollow core-shell structure methanol catalyst according to claim 2, characterized by comprising the following steps: the core of the copper-based catalyst is a Cu-Zn catalyst, and the shell is porous silica.
4. The preparation method of the sulfur-resistant and high-temperature-resistant hollow core-shell structure methanol catalyst according to claim 3, characterized in that the specific preparation process of the catalyst is as follows:
(1) taking Cu (NO)3)2·3H2O and Zn (NO)3)2·6H2Dissolving O in deionized water to obtain product A;
(2) adding surfactant polyethylene glycol mono-hexadecane ether into solution containing cyclohexane and n-octanol, and dissolving in water bath at 30-40 deg.C under stirring to obtain product B;
(3) adding product A into product B, stirring, and adding NaBH4Adding ammonia water and fully stirring after the reaction is finished, adding TEOS (tetraethyl orthosilicate) and continuously stirring, adding 50mL of ethanol after the hydrolytic condensation reaction, finally centrifugally washing the ethanol, washing the product obtained by centrifugation by using ethanol to obtain CuZn @ SiO2；
(4) The prepared CuZn @ SiO2Ultrasonically dispersing into deionized water, adding CTAB, and stirring at room temperature to form uniform dispersion to obtain product C;
(5) sequentially adding sodium metaaluminate and anhydrous sodium carbonate into the product C, continuously stirring for 2-4h at 90-100 ℃, naturally cooling to room temperature, and centrifugally washing with deionized water to obtain a product D;
(6) drying product D in 75-85 deg.C oven overnight to obtain catalyst powder, soaking the catalyst powder and modifier aqueous solution for 20-30H, drying in 75-85 deg.C oven, calcining to obtain modified catalyst, and placing in H before use2Reducing under the condition to obtain the modified Cu-Zn hollow core-shell structure catalyst.
5. The preparation method of the sulfur-resistant and high-temperature-resistant hollow core-shell structure methanol catalyst according to claim 4, characterized by comprising the following steps: cu in the A product: the molar ratio of Zn is 7: 3; in the B product, each 40ml of cyclohexane contains 8-12ml of n-octanol and 8-9g of polyethylene glycol monocetyl ether; in the step (3), NaBH4The concentration of the solution was 10 wt%, NaBH was added4The post-reaction time of the solution is 5-15min, the concentration of ammonia water is 25-28 wt%, the post-reaction time after the ammonia water is added is 0.5-1.5h, and the post-reaction time after the TEOS is added is 4-8 h; CuZn @ SiO in step (4) and step (5)2The mass ratio of CTAB, sodium metaaluminate, anhydrous sodium carbonate and deionized water is 1: 0.25: 0.53: 0.41: 200 of a carrier; and (6) the roasting temperature is 400-500 ℃, and the modifier aqueous solution and the catalyst powder are impregnated in equal volume.
6. The preparation method of the sulfur-resistant and high-temperature-resistant hollow core-shell structure methanol catalyst according to claim 2, characterized by comprising the following steps: the core of the copper-based catalyst is a Cu-Zn-Al catalyst, and the shell is porous silicon dioxide.
7. The preparation method of the sulfur-resistant and high-temperature-resistant hollow core-shell structure methanol catalyst according to claim 6, characterized in that the specific preparation process of the catalyst is as follows:
(1) taking Cu (NO)3)2·3H2O、Zn(NO3)2·6H2O and Al (NO)3)3·9H2Dissolving O in deionized water to obtain product A;
(2) adding surfactant polyethylene glycol mono-hexadecane ether into solution containing cyclohexane and n-octanol, and dissolving in water bath at 30-40 deg.C under stirring to obtain product B;
(3) adding product A into product B, stirring, and adding NaBH4Adding ammonia water and fully stirring after the reaction is finished, adding TEOS (tetraethyl orthosilicate) and continuously stirring, adding 50mL of ethanol after the hydrolytic condensation reaction, finally centrifugally washing the ethanol, washing the product obtained by centrifugation by using ethanol to obtain CuZnAl@SiO2；
(4) The prepared CuZnAl @ SiO2Ultrasonically dispersing into deionized water, adding CTAB, and stirring at room temperature to form uniform dispersion to obtain product C;
(5) sequentially adding sodium metaaluminate and anhydrous sodium carbonate into the product C, continuously stirring for 2-4h at 90-100 ℃, naturally cooling to room temperature, and centrifugally washing with deionized water to obtain a product D;
(6) drying product D in 75-85 deg.C oven overnight to obtain catalyst powder, soaking the catalyst powder and modifier aqueous solution for 20-30H, drying in 75-85 deg.C oven, calcining to obtain modified catalyst, and placing in H before use2Reducing under the condition to obtain the modified Cu-Zn-Al hollow core-shell structure catalyst.
8. The preparation method of the sulfur-resistant and high-temperature-resistant hollow core-shell structure methanol catalyst according to claim 7, characterized by comprising the following steps: cu in the A product: zn: the molar ratio of Al is 6: 3: 1; in the B product, each 40ml of cyclohexane contains 8-12ml of n-octanol and 8-9g of polyethylene glycol monocetyl ether; in the step (3), NaBH4The concentration of the solution was 10 wt%, NaBH was added4The post-reaction time of the solution is 5-15min, the concentration of ammonia water is 25-28 wt%, the post-reaction time after the ammonia water is added is 0.5-1.5h, and the post-reaction time after the TEOS is added is 4-8 h; the CuZnAl @ SiO in the step (4) and the step (5)2The mass ratio of CTAB, sodium metaaluminate, anhydrous sodium carbonate and deionized water is 1: 0.25: 0.53: 0.41: 200 of a carrier; and (6) the roasting temperature is 400-500 ℃, and the modifier aqueous solution and the catalyst powder are impregnated in equal volume.
9. The preparation method of the sulfur-resistant and high-temperature-resistant hollow core-shell structure methanol catalyst according to claim 1, characterized by comprising the following steps: the modifier is Ce (NO)3)3·6H2O、Mn(NO3)2、Fe(NO3)3·9H2O、(NH4)2MoO4And SnCl4·5H2O。
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