CN111569888A - A kind of preparation method of sulfur-resistant, high-temperature-resistant hollow core-shell methanol catalyst - Google Patents

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

A kind of preparation method of sulfur-resistant, high-temperature-resistant hollow core-shell methanol catalyst

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 hollow core-shell structure methanol catalyst

Background technique

For the catalysts for producing methanol from syngas, Cu/ZnO catalysts or Cu/ZnO/Al ₂ O ₃ catalysts are industrially used, both of which belong to copper-based catalysts.

However, the biggest problem of the copper-based catalysts currently used in industry is the poor stability and short service life of the catalyst. The shortening of the service life of the catalyst will undoubtedly increase the production cost of the enterprise and restrict the rapid development of the enterprise.

There are two main reasons for poor stability and short service life, one is sensitive to sulfur and easy to be poisoned by sulfur; the other is not resistant to high temperature. For the first reason, the main reason is that the catalyst will be affected by a small amount of hydrogen sulfide in the synthesis gas during the working process, and the hydrogen sulfide will combine with the catalytic component Cu in the catalyst, resulting in the failure of the catalyst; while the second reason is that Because the catalytic activity of copper-based catalysts decreases significantly with the increase of copper particle size, however, copper nanoparticles tend to agglomerate during the corresponding high-temperature working process, resulting in deactivation and reduced stability.

Therefore, how to improve the catalytic stability of copper-based catalysts and prolong their catalytic service life is an urgent technical problem in the industry that needs to be solved.

SUMMARY OF THE INVENTION

The purpose of the present invention is to provide a preparation method of a sulfur-resistant and high-temperature-resistant hollow core-shell methanol catalyst. The copper-based catalyst prepared by the invention has the characteristics of good catalytic stability and long service life.

The technical scheme of the present invention is as follows: a preparation method of a sulfur-resistant and high-temperature-resistant hollow core-shell structure methanol catalyst is to first prepare a copper-based catalyst with a core-shell structure, and then use a modifier capable of reacting with H ₂ S to treat the copper By modifying the base catalyst, a sulfur-resistant and high-temperature-resistant hollow core-shell methanol catalyst can be obtained.

For the preparation method of the aforementioned sulfur-resistant and high-temperature-resistant hollow core-shell structure methanol catalyst, the core-shell structure is a hollow core-shell structure.

In the preparation method of the aforementioned sulfur-resistant and high-temperature-resistant hollow core-shell methanol catalyst, the core of the copper-based catalyst is a Cu-Zn catalyst, and the shell is porous silica.

The preparation method of the aforementioned sulfur-resistant and high-temperature-resistant hollow core-shell methanol catalyst, the specific preparation process of the catalyst is as follows:

(1) Dissolve Cu(NO ₃ ) ₂ ·3H ₂ O and Zn(NO ₃ ) ₂ ·6H ₂ O in deionized water to obtain product A;

(2) Take the surfactant polyethylene glycol monohexadecyl ether, add it to the solution containing cyclohexane and n-octanol, stir and dissolve in a water bath at 30-40° C. to obtain product B;

( ₃ ) Add product A to product B, continue stirring, then add NaBH solution, after the reaction is completed, add ammonia water and stir well, then add TEOS to continue stirring, add 50 mL of ethanol after hydrolysis condensation reaction, and finally wash by ethanol centrifugation , the product obtained by centrifugation was washed with ethanol to obtain CuZn@SiO ₂ ; the core-shell structure obtained in this step was a solid core-shell structure, similar to the structure of egg white and protein;

( ₄ ) ultrasonically dispersing the prepared CuZn@SiO into deionized water, then adding CTAB, stirring at room temperature to form a uniform dispersion, and obtaining C product;

(5) Add sodium metaaluminate and anhydrous sodium carbonate to product C in turn, continue stirring for 2-4h under the condition of 90-100°C, then naturally cool to room temperature and wash by centrifugation with deionized water to obtain product D; this The D product obtained in the step is a hollow structure that is etched and peeled off between the core and shell, which is similar to the structure of peanut shells and peanut kernels; the same is true for the preparation of the following Cu-Zn-Al catalysts;

(6) put product D in a 75-85 ℃ oven to dry overnight to obtain catalyst powder, then immerse the catalyst powder and modifier aqueous solution for 20-30 hours, dry in an oven at 75-85 ℃ and bake to obtain a modified catalyst, The modified Cu-Zn hollow core-shell structure catalyst was obtained by reduction under _H2 condition before use.

For the preparation method of the aforementioned sulfur-resistant and high-temperature-resistant hollow core-shell methanol catalyst, the molar ratio of Cu:Zn in the A product is 7:3; in the B product, every 40 ml of cyclohexane contains 8-12 ml of cyclohexane. n-octanol and 8-9g polyethylene glycol monohexadecyl ether; in the step (3), the concentration of NaBH ₄ solution is 10wt%, the reaction time after adding NaBH ₄ solution is 5-15min, and the concentration of ammonia water is 25- 28wt%, the reaction time is 0.5-1.5h after adding ammonia water, and the reaction time is 4-8h after adding TEOS; CuZn@SiO ₂ , CTAB, sodium metaaluminate, anhydrous carbonic acid described in step (4) and step (5) The mass ratio of sodium and deionized water is 1:0.25:0.53:0.41:200; the roasting temperature in step (6) is 400-500°C, and the modifier aqueous solution and the catalyst powder are impregnated in equal volumes.

In the preparation method of the aforementioned sulfur-resistant and high-temperature-resistant hollow core-shell methanol catalyst, the core of the copper-based catalyst is a Cu-Zn-Al catalyst, and the shell is porous silica.

The preparation method of the aforementioned sulfur-resistant and high-temperature-resistant hollow core-shell methanol catalyst, the specific preparation process of the catalyst is as follows:

(1) Dissolve Cu(NO ₃ ) ₂ .3H ₂ O, Zn(NO ₃ ) ₂ .6H ₂ O and Al(NO ₃ ) ₃ .9H ₂ O in deionized water to obtain product A;

(2) Take the surfactant polyethylene glycol monohexadecyl ether, add it to the solution containing cyclohexane and n-octanol, stir and dissolve in a water bath at 30-40° C. to obtain product B;

( ₃ ) Add product A to product B, continue stirring, then add NaBH solution, after the reaction is completed, add ammonia water and stir well, then add TEOS to continue stirring, add 50 mL of ethanol after hydrolysis condensation reaction, and finally wash by ethanol centrifugation , the product obtained by centrifugation was washed with ethanol to obtain CuZnAl@SiO ₂ ;

( ₄ ) ultrasonically dispersing the prepared CuZnAl@SiO into deionized water, then adding CTAB, stirring at room temperature to form a uniform dispersion, and obtaining C product;

(5) Add sodium metaaluminate and anhydrous sodium carbonate to product C in turn, continue stirring at 90-100 ° C for 2-4h, then naturally cool to room temperature and then centrifugally wash with deionized water to obtain product D;

(6) put product D in a 75-85 ℃ oven to dry overnight to obtain catalyst powder, then immerse the catalyst powder and modifier aqueous solution for 20-30 hours, dry in an oven at 75-85 ℃ and bake to obtain a modified catalyst, The modified Cu-Zn-Al hollow core-shell structure catalyst was obtained by reduction under _H2 condition before use.

In the preparation method of the aforementioned sulfur-resistant and high-temperature-resistant hollow core-shell methanol catalyst, the molar ratio of Cu:Zn:Al in the A product is 6:3:1; in the B product, every 40 ml of cyclohexane Contains 8-12ml n-octanol and 8-9g polyethylene glycol monohexadecyl ether; in the step ( ₃ ), the concentration of the NaBH solution is 10wt%, and the reaction time after adding the NaBH solution is _5-15min , and the ammoniacal The concentration is 25-28wt%, the reaction time after adding ammonia water is 0.5-1.5h, and the reaction time after adding TEOS is 4-8h; CuZnAl@SiO ₂ , CTAB, sodium metaaluminate described in step (4) and step (5) , the mass ratio of anhydrous sodium carbonate and deionized water is 1: 0.25: 0.53: 0.41: 200; the temperature of the roasting in step (6) is 400-500 ° C, and the modifier aqueous solution and the catalyst powder are equal volumes dipping.

The preparation method of the aforementioned sulfur-resistant and high-temperature-resistant hollow core-shell methanol catalyst, wherein the modifiers are Ce(NO ₃ ) ₃ ·6H ₂ O, Mn(NO ₃ ) ₂ , Fe(NO ₃ ) ₃ ·9H ₂ O, (NH ₄ ) ₂ MoO ₄ and SnCl ₄ .5H ₂ O.

The beneficial effects of the present invention

1. In the present invention, the copper-based catalyst is made into a hollow core-shell structure, and the catalyst in the inner core part is protected by the porous silica layer of the outer layer, which does not affect the catalysis of the synthesis gas entering the inner core through the shell layer and in the catalyst. At the same time, through the confinement effect, the protection of the catalyst is improved, the high temperature resistance performance is improved, the stability of the catalyst is strengthened, and the service life is prolonged.

2. In the present invention, by modifying the shell layer of the copper-based catalyst with the hollow core-shell structure, the modified shell layer loads substances that can react preferentially with hydrogen sulfide in the synthesis gas, which can be removed before the synthesis gas enters the inner core catalyst. A small amount of hydrogen sulfide gas in the synthesis gas is filtered and eliminated, which greatly reduces the sulfur poisoning degree of the copper-based catalyst, improves the stability of the catalyst, and prolongs the service life.

Experimental example

The inventors respectively compared the high temperature resistance performance of the traditional Cu-Zn-Al catalyst and the core-shell structure Cu-Zn-Al catalyst prepared by the present invention, as well as the traditional Cu-Zn _- Al catalyst and the CeO2 prepared by the present invention. The sulfur resistance performance of the modified core-shell structure Cu-Zn-Al catalyst was compared, and the results are shown in Table 1, Figure 1, Table 2, and Figure 2, respectively.

Table 1 Comparison of high temperature resistance performance

As shown in Table 1 and Figure 1, the catalytic activity of the traditional Cu-Zn-Al catalyst and the core-shell structure Cu-Zn-Al catalyst prepared by the present invention gradually tends to be stable with the passage of catalytic time. However, Due to the lack of high temperature protection of traditional catalysts, the catalytic activity is lower than that of the catalyst with the core-shell structure of the present invention.

Table 2 Sulfur resistance test

catalyst 3 4 5 6 7 8 9 10 Comparative ratio 3.78 3.96 4.53 4.47 4.65 4.58 4.63 4.61 Example 8.43 9.67 9.72 9.75 9.69 9.82 9.88 9.78

As shown in Table 2 and Figure 2, the catalytic activity of the traditional Cu-Zn-Al catalyst and the core-shell structure Cu-Zn-Al catalyst modified by the present invention gradually tends to be stable with the passage of catalytic time. However, the catalytic activity of the traditional catalyst is lower than that of the modified core-shell structure catalyst of the present invention due to its poor sulfur resistance.

Description of drawings

Accompanying drawing 1 is the preparation flow chart of the present invention;

Accompanying drawing 2 is the comparison chart of high temperature resistance experimental data;

Accompanying drawing 3 is the comparison chart of sulfur tolerance experiment data.

Detailed ways

The present invention will be further described below in conjunction with the examples, but not as a basis for limiting the present invention.

Embodiments of the present invention

Embodiment 1: a kind of preparation method of sulfur-resistant, high-temperature-resistant hollow core-shell methanol Cu-Zn catalyst, the process is as follows:

(1) Dissolve Cu(NO ₃ ) ₂ ·3H ₂ O and Zn(NO ₃ ) ₂ ·6H ₂ O in deionized water to obtain product A, where Cu/Zn molar ratio=7:3;

(2) Get 8.72g of surfactant polyethylene glycol monohexadecyl ether, add it to a solution containing 40ml of cyclohexane and 10ml of n-octanol, stir and dissolve in a water bath at 35°C to obtain product B;

( ₃ ) Add product A to product B, keep stirring, then add 300 μL of NaBH solution with a concentration of 10wt%, react for 10min, add ammonia water with a concentration of 26wt% and fully stir for 1h, then add TEOS and continue stirring for 6h to carry out the hydrolysis condensation reaction After adding 50 mL of ethanol, and finally washing by ethanol centrifugation, the product obtained by centrifugation was washed with ethanol to obtain CuZn@SiO ₂ ;

( ₄ ) ultrasonically dispersing the prepared CuZn@SiO into deionized water, then adding CTAB, stirring at room temperature to form a uniform dispersion, and obtaining C product;

(5) Add sodium metaaluminate and anhydrous sodium carbonate to C product in turn, the mass ratio of CuZn@SiO ₂ , CTAB, sodium metaaluminate, anhydrous sodium carbonate and deionized water is 1:0.25:0.53:0.41 : 200, continue stirring at 95°C for 3h, then naturally cooled to room temperature, and washed with deionized water by centrifugation to obtain product D;

(6) Product D was dried in an oven at 80°C overnight to obtain catalyst powder, and then the catalyst powder was immersed in an equal volume of Ce(NO ₃ ) ₃ ·6H ₂ O aqueous solution for 24 hours, dried in an oven at 80° C. and calcined at 450° C. to obtain The modified _CuO /ZnO@HMAN catalyst was reduced under H before use to obtain the modified CuZnO@HMAN catalyst.

Embodiment 2: a kind of preparation method of sulfur-resistant, high-temperature-resistant hollow core-shell methanol Cu-Zn catalyst, the process is as follows:

(1) Dissolve Cu(NO ₃ ) ₂ ·3H ₂ O and Zn(NO ₃ ) ₂ ·6H ₂ O in deionized water to obtain product A, where Cu/Zn molar ratio=7:3;

(2) Get 8g of surfactant polyethylene glycol monohexadecyl ether, add it to a solution containing 40ml of cyclohexane and 8ml of n-octanol, stir and dissolve in a water bath at 30°C to obtain product B;

(3) Add product A to product B, keep stirring, then add 10wt% NaBH ₄ solution, react for 5min, add 25wt% ammonia water and fully stir for 0.5h, then add TEOS and continue stirring for 4h to carry out hydrolysis condensation reaction After adding 50 mL of ethanol, and finally washing by ethanol centrifugation, the product obtained by centrifugation was washed with ethanol to obtain CuZn@SiO ₂ ;

( ₄ ) ultrasonically dispersing the prepared CuZn@SiO into deionized water, then adding CTAB, stirring at room temperature to form a uniform dispersion, and obtaining C product;

(5) Add sodium metaaluminate and anhydrous sodium carbonate to C product in turn, the mass ratio of CuZn@SiO ₂ , CTAB, sodium metaaluminate, anhydrous sodium carbonate and deionized water is 1:0.25:0.53:0.41 : 200, stirring continuously for 2 hours at 90°C, then cooling to room temperature naturally, and washing with deionized water by centrifugation to obtain product D;

(6) Dry product D in a 75°C oven overnight to obtain catalyst powder, then immerse the catalyst powder in an equal volume of Mn(NO ₃ ) ₂ aqueous solution for 20h, dry in an oven at 75°C and bake at 400°C to obtain modified CuO /ZnO@HMAN catalyst, the modified CuZnO@ _HMAN catalyst was obtained by reduction under H before use.

Embodiment 3: a kind of preparation method of sulfur-resistant, high-temperature-resistant hollow core-shell methanol Cu-Zn catalyst, the process is as follows:

(1) Dissolve Cu(NO ₃ ) ₂ ·3H ₂ O and Zn(NO ₃ ) ₂ ·6H ₂ O in deionized water to obtain product A, where Cu/Zn molar ratio=7:3;

(2) Get 9g of surfactant polyethylene glycol monohexadecyl ether, add it to a solution containing 40ml of cyclohexane and 12ml of n-octanol, stir and dissolve in a water bath at 40°C to obtain product B;

( ₃ ) Add product A to product B, keep stirring, then add NaBH solution with a concentration of 10wt%, react for 15min, add ammonia water with a concentration of 28wt% and fully stir for 1.5h, then add TEOS and continue stirring for 8h to carry out the hydrolysis condensation reaction After adding 50 mL of ethanol, and finally washing by ethanol centrifugation, the product obtained by centrifugation was washed with ethanol to obtain CuZn@SiO ₂ ;

( ₄ ) ultrasonically dispersing the prepared CuZn@SiO into deionized water, then adding CTAB, stirring at room temperature to form a uniform dispersion, and obtaining C product;

(5) Add sodium metaaluminate and anhydrous sodium carbonate to C product in turn, the mass ratio of CuZn@SiO ₂ , CTAB, sodium metaaluminate, anhydrous sodium carbonate and deionized water is 1:0.25:0.53:0.41 : 200, continue to stir at 100 °C for 4 hours, then naturally cool to room temperature and wash by centrifugation with deionized water to obtain D product;

(6) Put product D in an oven at 85°C to dry overnight to obtain catalyst powder, then immerse the catalyst powder in an equal volume of Fe(NO ₃ ) ₃ ·9H ₂ O aqueous solution for 30 hours, dry in an oven at 85° C. and bake at 500° C. to obtain The modified _CuO /ZnO@HMAN catalyst was reduced under H before use to obtain the modified CuZnO@HMAN catalyst.

Embodiment 4: a kind of preparation method of sulfur-resistant, high-temperature-resistant hollow core-shell methanol Cu-Zn-Al catalyst, the process is as follows:

(1) Dissolve Cu(NO ₃ ) ₂ .3H ₂ O, Zn(NO ₃ ) ₂ .6H ₂ O and Al(NO ₃ ) ₃ .9H ₂ O in deionized water to obtain product A, in which Cu/Zn /Al molar ratio=6:3:1;

(2) Get 8.72g of surfactant polyethylene glycol monohexadecyl ether, add it to a solution containing 40ml of cyclohexane and 10ml of n-octanol, stir and dissolve in a water bath at 35°C to obtain product B;

( ₃ ) Add product A to product B, keep stirring, then add 300 μL of NaBH solution with a concentration of 10wt%, react for 10min, add ammonia water with a concentration of 26wt% and fully stir for 1h, then add TEOS and continue stirring for 6h to carry out the hydrolysis condensation reaction 50 mL of ethanol was then added, and finally washed with ethanol by centrifugation, and the product obtained by centrifugation was washed with ethanol to obtain CuZnAl@SiO ₂ ;

( ₄ ) ultrasonically dispersing the prepared CuZnAl@SiO into deionized water, then adding CTAB, stirring at room temperature to form a uniform dispersion, and obtaining C product;

(5) Add sodium metaaluminate and anhydrous sodium carbonate to C product in turn, the mass ratio of CuZnAl@SiO ₂ , CTAB, sodium metaaluminate, anhydrous sodium carbonate and deionized water is 1:0.25:0.53:0.41 : 200, continue stirring at 95°C for 3h, then naturally cooled to room temperature, and washed with deionized water by centrifugation to obtain product D;

(6) Put D product in an oven at 80°C to dry overnight to obtain catalyst powder, then immerse the catalyst powder in an equal volume of (NH ₄ ) ₂ MoO ₄ aqueous solution for 24 hours, dry in an oven at 80° C. and bake at 450° C. to obtain the modified catalyst _Catalyst , reduced under H before use.

Embodiment 5: a kind of preparation method of sulfur-resistant, high-temperature-resistant hollow core-shell methanol Cu-Zn-Al catalyst, the process is as follows:

(1) Dissolve Cu(NO ₃ ) ₂ .3H ₂ O, Zn(NO ₃ ) ₂ .6H ₂ O and Al(NO ₃ ) ₃ .9H ₂ O in deionized water to obtain product A, in which Cu/Zn /Al molar ratio=6:3:1;

(2) Get 8g of surfactant polyethylene glycol monohexadecyl ether, add it to a solution containing 40ml of cyclohexane and 8ml of n-octanol, stir and dissolve in a water bath at 30°C to obtain product B;

(3) Add product A to product B, keep stirring, then add 10wt% NaBH ₄ solution, react for 5min, add 25wt% ammonia water and fully stir for 0.5h, then add TEOS and continue stirring for 4h to carry out hydrolysis condensation reaction 50 mL of ethanol was then added, and finally washed with ethanol by centrifugation, and the product obtained by centrifugation was washed with ethanol to obtain CuZnAl@SiO ₂ ;

( ₄ ) ultrasonically dispersing the prepared CuZnAl@SiO into deionized water, then adding CTAB, stirring at room temperature to form a uniform dispersion, and obtaining C product;

(5) Add sodium metaaluminate and anhydrous sodium carbonate to C product in turn, the mass ratio of CuZnAl@SiO ₂ , CTAB, sodium metaaluminate, anhydrous sodium carbonate and deionized water is 1:0.25:0.53:0.41 : 200, stirring continuously for 2 hours at 90°C, then cooling to room temperature naturally, and washing with deionized water by centrifugation to obtain product D;

(6) Dry product D in a 75°C oven overnight to obtain catalyst powder, then immerse the catalyst powder in an equal volume of SnCl ₄ ·5H ₂ O aqueous solution for 20 hours, dry in an oven at 75° C, and bake at 400° C to obtain a modified catalyst , reduced under _H2 conditions before use.

Embodiment 6: a kind of preparation method of sulfur-resistant, high-temperature-resistant hollow core-shell methanol Cu-Zn-Al catalyst, the process is as follows:

(1) Dissolve Cu(NO ₃ ) ₂ .3H ₂ O, Zn(NO ₃ ) ₂ .6H ₂ O and Al(NO ₃ ) ₃ .9H ₂ O in deionized water to obtain product A, in which Cu/Zn /Al molar ratio=6:3:1;

(2) Get 9g of surfactant polyethylene glycol monohexadecyl ether, add it to a solution containing 40ml of cyclohexane and 12ml of n-octanol, stir and dissolve in a water bath at 40°C to obtain product B;

( ₃ ) Add product A to product B, keep stirring, then add NaBH solution with a concentration of 10wt%, react for 15min, add ammonia water with a concentration of 28wt% and fully stir for 1.5h, then add TEOS and continue stirring for 8h to carry out the hydrolysis condensation reaction 50 mL of ethanol was then added, and finally washed with ethanol by centrifugation, and the product obtained by centrifugation was washed with ethanol to obtain CuZnAl@SiO ₂ ;

( ₄ ) ultrasonically dispersing the prepared CuZnAl@SiO into deionized water, then adding CTAB, stirring at room temperature to form a uniform dispersion, and obtaining C product;

(5) Add sodium metaaluminate and anhydrous sodium carbonate to C product in turn, the mass ratio of CuZnAl@SiO ₂ , CTAB, sodium metaaluminate, anhydrous sodium carbonate and deionized water is 1:0.25:0.53:0.41 : 200, continue to stir at 100 °C for 4 hours, then naturally cool to room temperature and wash by centrifugation with deionized water to obtain D product;

(6) Put D product in an oven at 85°C to dry overnight to obtain catalyst powder, then immerse the catalyst powder in an equal volume of Ce(NO ₃ ) ₃ ·6H ₂ O aqueous solution for 30 hours, dry in an oven at 85° C. and bake at 500° C. to obtain The modified catalyst was reduced under _H2 conditions before use.

The above description is only a preferred embodiment of the present invention, but the protection scope of the present invention is not limited to this. The equivalent replacement or modification of the created technical solution and its inventive concept shall be included within the protection scope of the present invention.

Claims (9)

1. a preparation method of a sulfur-resistant, high-temperature-resistant hollow core-shell structure methanol catalyst, is characterized in that: be to first prepare the copper-based catalyst with core-shell structure, then utilize the modifier that can react with H ₂ S to copper By modifying the base catalyst, a sulfur-resistant and high-temperature-resistant hollow core-shell methanol catalyst can be obtained. 2 . The method for preparing a sulfur-resistant and high-temperature-resistant methanol catalyst with a hollow core-shell structure according to claim 1 , wherein the core-shell structure is a hollow core-shell structure. 3 . 3 . The method for preparing a sulfur- and high-temperature-resistant hollow core-shell methanol catalyst according to claim 2 , wherein the core of the copper-based catalyst is a Cu-Zn catalyst, and the shell is porous silica. 4 . 4. the preparation method of sulfur-resistant, high temperature-resistant hollow core-shell structure methanol catalyst according to claim 3, is characterized in that, the concrete preparation process of described catalyst is as follows: (1) Dissolve Cu(NO ₃ ) ₂ ·3H ₂ O and Zn(NO ₃ ) ₂ ·6H ₂ O in deionized water to obtain product A; (2) Take the surfactant polyethylene glycol monohexadecyl ether, add it to the solution containing cyclohexane and n-octanol, stir and dissolve in a water bath at 30-40° C. to obtain product B; ( ₃ ) Add product A to product B, continue stirring, then add NaBH solution, after the reaction is completed, add ammonia water and stir well, then add TEOS to continue stirring, add 50 mL of ethanol after hydrolysis condensation reaction, and finally wash by ethanol centrifugation , the product obtained by centrifugation was washed with ethanol to obtain CuZn@SiO ₂ ; ( ₄ ) ultrasonically dispersing the prepared CuZn@SiO into deionized water, then adding CTAB, stirring at room temperature to form a uniform dispersion, and obtaining C product; (5) Add sodium metaaluminate and anhydrous sodium carbonate to product C in turn, continue stirring at 90-100 ° C for 2-4h, then naturally cool to room temperature and then centrifugally wash with deionized water to obtain product D; (6) put product D in a 75-85 ℃ oven to dry overnight to obtain catalyst powder, then immerse the catalyst powder and modifier aqueous solution for 20-30 hours, dry in an oven at 75-85 ℃ and bake to obtain a modified catalyst, The modified Cu-Zn hollow core-shell structure catalyst was obtained by reduction under _H2 condition before use. 5. The preparation method of sulfur-resistant and high-temperature-resistant hollow core-shell methanol catalyst according to claim 4, characterized in that: in the described product A, the molar ratio of Cu:Zn is 7:3; in the described product B , every 40ml of cyclohexane contains 8-12ml of n-octanol and 8-9g of polyethylene glycol monohexadecyl ether; in the step (3), the concentration of NaBH ₄ solution is 10wt%, and the reaction time after adding NaBH ₄ solution It is 5-15min, the concentration of ammonia water is 25-28wt%, the reaction time after adding ammonia water is 0.5-1.5h, and the reaction time after adding TEOS is 4-8h; CuZn@SiO ₂ described in step (4) and step (5) The mass ratio of , CTAB, sodium metaaluminate, anhydrous sodium carbonate and deionized water is 1: 0.25: 0.53: 0.41: 200; the temperature of the roasting in step (6) is 400-500 ° C, the modifier The aqueous solution and the catalyst powder are impregnated in equal volumes. 6. The preparation method of the sulfur-resistant and high-temperature-resistant hollow core-shell methanol catalyst according to claim 2, wherein the core of the copper-based catalyst is a Cu-Zn-Al catalyst, and the shell is a porous silica . 7. the preparation method of sulfur-resistant, high-temperature-resistant hollow core-shell methanol catalyst according to claim 6, is characterized in that, the concrete preparation process of described catalyst is as follows: (1) Dissolve Cu(NO ₃ ) ₂ .3H ₂ O, Zn(NO ₃ ) ₂ .6H ₂ O and Al(NO ₃ ) ₃ .9H ₂ O in deionized water to obtain product A; (2) Take the surfactant polyethylene glycol monohexadecyl ether, add it to the solution containing cyclohexane and n-octanol, stir and dissolve in a water bath at 30-40° C. to obtain product B; ( ₃ ) Add product A to product B, continue stirring, then add NaBH solution, after the reaction is completed, add ammonia water and stir well, then add TEOS to continue stirring, add 50 mL of ethanol after hydrolysis condensation reaction, and finally wash by ethanol centrifugation , the product obtained by centrifugation was washed with ethanol to obtain CuZnAl@SiO ₂ ; ( ₄ ) ultrasonically dispersing the prepared CuZnAl@SiO into deionized water, then adding CTAB, stirring at room temperature to form a uniform dispersion, and obtaining C product; (5) Add sodium metaaluminate and anhydrous sodium carbonate to product C in turn, continue stirring at 90-100 ° C for 2-4h, then naturally cool to room temperature and then centrifugally wash with deionized water to obtain product D; (6) put product D in a 75-85 ℃ oven to dry overnight to obtain catalyst powder, then immerse the catalyst powder and modifier aqueous solution for 20-30 hours, dry in an oven at 75-85 ℃ and bake to obtain a modified catalyst, The modified Cu-Zn-Al hollow core-shell structure catalyst was obtained by reduction under _H2 condition before use. 8 . The method for preparing a sulfur-resistant and high-temperature-resistant hollow core-shell methanol catalyst according to claim 7 , wherein the molar ratio of Cu:Zn:Al in the A product is 6:3:1; In the above-mentioned product B, every 40ml of cyclohexane contains 8-12ml of n-octanol and 8-9g of polyethylene glycol monohexadecyl ether; in the step ( ₃ ), the concentration of the NaBH solution is 10wt%, adding NaBH ₄ The reaction time after the solution is 5-15min, the concentration of ammonia water is 25-28wt%, the reaction time after adding ammonia water is 0.5-1.5h, and the reaction time after adding TEOS is 4-8h; step (4) and step (5) described The mass ratio of CuZnAl@SiO ₂ , CTAB, sodium metaaluminate, anhydrous sodium carbonate and deionized water is 1:0.25:0.53:0.41:200; the roasting temperature in step (6) is 400-500°C, so The aqueous solution of the modifier and the catalyst powder are impregnated in equal volumes. 9 . The method for preparing a sulfur-resistant and high-temperature-resistant hollow core-shell methanol catalyst according to claim 1 , wherein the modifier is Ce(NO ₃ ) ₃ .6H ₂ O, Mn(NO ₃ . 10 . ) ₂ , Fe(NO ₃ ) ₃ .9H ₂ O, (NH ₄ ) ₂ MoO ₄ and SnCl ₄ .5H ₂ O.

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