CN111569888B - 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 PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 124
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 239000011258 core-shell material Substances 0.000 title claims abstract description 51
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 36
- 239000011593 sulfur Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000010949 copper Substances 0.000 claims abstract description 41
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052802 copper Inorganic materials 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
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- 238000003756 stirring Methods 0.000 claims description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 54
- 239000008367 deionised water Substances 0.000 claims description 40
- 229910021641 deionized water Inorganic materials 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 29
- 238000005406 washing Methods 0.000 claims description 29
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 28
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 24
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 20
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 20
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 20
- 239000011734 sodium Substances 0.000 claims description 20
- 229910052708 sodium Inorganic materials 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 19
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 18
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 18
- 229910017773 Cu-Zn-Al Inorganic materials 0.000 claims description 17
- 229910002535 CuZn Inorganic materials 0.000 claims description 15
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 14
- 239000002202 Polyethylene glycol Substances 0.000 claims description 14
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 14
- 229920001223 polyethylene glycol Polymers 0.000 claims description 14
- 238000002791 soaking Methods 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000006482 condensation reaction Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 10
- 239000004094 surface-active agent Substances 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 7
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical group [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 claims description 7
- 229910017518 Cu Zn Inorganic materials 0.000 claims description 5
- 229910017752 Cu-Zn Inorganic materials 0.000 claims description 5
- 229910017943 Cu—Zn Inorganic materials 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 5
- 230000003301 hydrolyzing effect Effects 0.000 claims description 5
- 229910021426 porous silicon Inorganic materials 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- FDCJDKXCCYFOCV-UHFFFAOYSA-N 1-hexadecoxyhexadecane Chemical compound CCCCCCCCCCCCCCCCOCCCCCCCCCCCCCCCC FDCJDKXCCYFOCV-UHFFFAOYSA-N 0.000 claims description 4
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 239000007789 gas Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
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- 238000006460 hydrolysis reaction Methods 0.000 description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 4
- 235000017060 Arachis glabrata Nutrition 0.000 description 2
- 241001553178 Arachis glabrata Species 0.000 description 2
- 235000010777 Arachis hypogaea Nutrition 0.000 description 2
- 235000018262 Arachis monticola Nutrition 0.000 description 2
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- 235000020232 peanut Nutrition 0.000 description 2
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- QCVGEOXPDFCNHA-UHFFFAOYSA-N 5,5-dimethyl-2,4-dioxo-1,3-oxazolidine-3-carboxamide Chemical compound CC1(C)OC(=O)N(C(N)=O)C1=O QCVGEOXPDFCNHA-UHFFFAOYSA-N 0.000 description 1
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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
-
- B01J35/397—
-
- 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
- B01J37/02—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
- 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
- B01J37/34—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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a 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 H 2 Modifying the copper-based catalyst by using the modifier of 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
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 industrially 2 O 3 The catalysts all belong to copper-based catalysts.
However, the biggest problems of the copper-based catalyst adopted in the industry at present are that the stability of the catalyst is poor, the service life of the catalyst is short, 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 coating does not resist high temperature. 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 H 2 Modifying 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.
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 hollow core-shell structure methanol catalyst, the specific preparation process of the catalyst is as follows:
(1) Taking Cu (NO) 3 ) 2 ·3H 2 O and Zn (NO) 3 ) 2 ·6H 2 Dissolving 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 NaBH 4 Adding 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 @ SiO 2 (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) Prepared CuZn @ SiO 2 Ultrasonically 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 following Cu-Zn-Al catalyst;
(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 use 2 Reducing 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 hollow core-shell structure methanol catalyst, the ratio of Cu: 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), naBH 4 The concentration of the solution was 10wt%, naBH was added 4 The post-reaction time of the solution is 5-15min, the concentration of ammonia water is 25-28wt%, the post-reaction time after adding the ammonia water is 0.5-1.5h, and the post-reaction time after adding TEOS is 4-8h; step (4) and step (5) the CuZn @SiO 2 And the mass ratio of CTAB, sodium metaaluminate, anhydrous sodium carbonate and deionized water is 1:0.25:0.53:0.41:200 of a carrier; in the step (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 ·3H 2 O、Zn(NO 3 ) 2 ·6H 2 O and Al (NO) 3 ) 3 ·9H 2 Dissolving 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 NaBH 4 Adding 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 @ SiO 2 ；
(4) Preparing CuZnAl @ SiO 2 Ultrasonically 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 water solution for 20-30h, drying in 75-85 deg.C oven, calcining to obtain modified catalyst, and placing in H before use 2 Reducing 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; the above-mentionedIn step (3), naBH 4 The concentration of the solution was 10wt%, naBH was added 4 The post-reaction time of the solution is 5-15min, the concentration of ammonia water is 25-28wt%, 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 4-8h; step (4) and step (5) the CuZnAl @ SiO 2 The mass ratio of CTAB, sodium metaaluminate, anhydrous sodium carbonate and deionized water is 1:0.25:0.53:0.41:200; and (6) roasting at 400-500 ℃, and soaking the modifier aqueous solution and the catalyst powder 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 ·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 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 the substances 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, thus the sulfur poisoning degree of the copper-based catalyst is greatly reduced, the stability of the catalyst is improved, and the service life is prolonged.
Examples of the experiments
The inventor respectively tests 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 invention 2 Modified Cu-Zn-Al catalyst with core-shell structureThe results of comparative experiments on the sulfur resistance of (A) are shown in Table 1 and FIG. 1, and Table 2 and FIG. 2, respectively.
TABLE 1 comparison of high temperature resistance
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 producing the 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 ·3H 2 O and Zn (NO) 3 ) 2 ·6H 2 Dissolving O in deionized water to obtain product A, wherein the Cu/Zn molar ratio =7:3;
(2) Adding 8.72g surfactant polyethylene glycol mono-hexadecane ether into solution containing 40ml cyclohexane and 10ml n-octanol, and stirring and dissolving in water bath at 35 deg.C to obtain product B;
(3) Adding product A to product B, stirring, and adding NaBH to a concentration of 10wt% 4 Reacting the solution 300 mu L for 10min, adding 26wt% ammonia water, stirring for 1h, adding TEOS, stirring for 6h, performing hydrolysis condensation reaction, adding 50mL ethanol, centrifuging, washing the product with ethanol, and washing the product with ethanol to obtain CuZn @ SiO 2 ；
(4) Preparing CuZn @ SiO 2 Ultrasonically 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 @SiOinto product C in sequence 2 The 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 Ce (NO) 3 ) 3 ·6H 2 Soaking O aqueous solution in equal volume for 24h, drying in 80 deg.C oven, calcining at 450 deg.C to obtain modified CuO/ZnO @ HMAN catalyst, and adding H before use 2 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 ·3H 2 O and Zn (NO) 3 ) 2 ·6H 2 Dissolving O in deionized water to obtain product A, wherein the Cu/Zn molar ratio =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 product A to product B, stirring, and adding into 10wt% of NaBH 4 Reacting the solution for 5min, adding 25wt% ammonia water, stirring for 0.5h, adding TEOS, stirring for 4h, performing hydrolysis condensation reaction, adding 50mL ethanol, centrifuging, washing with ethanol, and washing with ethanol to obtain CuZn @ SiO 2 ；
(4) Prepared CuZn @ SiO 2 Ultrasonically 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 @SiOinto product C in sequence 2 The 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 ) 2 Soaking the aqueous solution in an equal volume for 20h, drying in a 75 ℃ oven, and then roasting at 400 ℃ to obtain a modified CuO/ZnO @ HMAN catalyst which is added with H before use 2 And 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 ·3H 2 O and Zn (NO) 3 ) 2 ·6H 2 Dissolving O in deionized water to obtain product A, wherein the Cu/Zn molar ratio =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 product A to product B, stirring, and adding NaBH to a concentration of 10wt% 4 Reacting the solution for 15min, adding 28wt% ammonia water, stirring for 1.5h, and stirringAdding TEOS, stirring for 8 hr, performing hydrolysis condensation reaction, adding 50mL ethanol, centrifuging with ethanol, washing the product with ethanol to obtain CuZn @ SiO 2 ；
(4) Prepared CuZn @ SiO 2 Ultrasonically 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 sequence 2 The 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 the catalyst powder with Fe (NO) 3 ) 3 ·9H 2 Soaking in O water solution for 30h in equal volume, drying in oven at 85 deg.C, and calcining at 500 deg.C to obtain modified CuO/ZnO @ HMAN catalyst 2 And 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 ·3H 2 O、Zn(NO 3 ) 2 ·6H 2 O and Al (NO) 3 ) 3 ·9H 2 Dissolving 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 product A to product B, stirring, and adding NaBH to a concentration of 10wt% 4 Reacting the solution with 300 mu L for 10min, adding ammonia water with the concentration of 26wt%, 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 @ SiO 2 ；
(4) Preparing CuZnAl @ SiO 2 Ultrasonically 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 CuZnAl @ SiO into product C in sequence 2 And the 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 ) 2 MoO 4 Soaking the aqueous solution in equal volume for 24h, drying in an oven at 80 ℃, and then roasting at 450 ℃ to obtain the modified catalyst which is subjected to H before use 2 Reducing 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 ·3H 2 O、Zn(NO 3 ) 2 ·6H 2 O and Al (NO) 3 ) 3 ·9H 2 Dissolving O in deionized water to obtain a product A, wherein the Cu/Zn/Al molar ratio =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 product A to product B, stirring, and adding NaBH to a concentration of 10wt% 4 Reacting the solution for 5min, adding 25wt% ammonia water, stirring for 0.5h, adding TEOS, stirring for 4h, performing hydrolysis condensation reaction, adding 50mL ethanol, centrifuging, washing with ethanol, and washing with ethanol to obtain CuZnAl @ SiO 2 ；
(4) Preparing CuZnAl @ SiO 2 Ultrasonically 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 CuZnAl @ SiO into product C in sequence 2 And the 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 SnCl 4 ·5H 2 Soaking O water solution in the same volume for 20h, drying in a 75 ℃ oven, roasting at 400 ℃ to obtain a modified catalyst, and before use, adding H 2 And (3) reducing 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 ·3H 2 O、Zn(NO 3 ) 2 ·6H 2 O and Al (NO) 3 ) 3 ·9H 2 Dissolving O in deionized water to obtain product A, wherein the molar ratio of Cu/Zn/Al is =6:3:1;
(2) Adding 9g surfactant polyethylene glycol mono-hexadecane ether into solution containing 40ml cyclohexane and 12ml n-octanol, and stirring and dissolving in water bath at 40 deg.C to obtain product B;
(3) Adding product A to product B, stirring, and adding into 10wt% of NaBH 4 Reacting the solution for 15min, adding 28wt% ammonia water, stirring for 1.5h, adding TEOS, stirring for 8h, performing hydrolysis condensation reaction, adding 50mL ethanol, centrifuging, washing with ethanol, and washing the product with ethanol to obtain CuZnAl @ SiO 2 ；
(4) Preparing CuZnAl @ SiO 2 Ultrasonically 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 CuZnAl @ SiO into product C in sequence 2 And the 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) Baking D at 85 deg.COven dried overnight to obtain a catalyst powder, and then the catalyst powder was mixed with Ce (NO) 3 ) 3 ·6H 2 Soaking in O water solution at equal volume for 30h, drying in oven at 85 deg.C, and calcining at 500 deg.C to obtain modified catalyst, which is used in H before use 2 And (3) reducing 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 (5)
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 H 2 Modifying the copper-based catalyst by using a modifier of the S reaction to obtain a sulfur-resistant and high-temperature-resistant methanol catalyst with a hollow core-shell structure; the core-shell structure is a hollow core-shell structure; the core of the copper-based catalyst is a Cu-Zn-Al catalyst, and the shell is porous silicon dioxide; the specific preparation process of the sulfur-resistant and high-temperature-resistant methanol catalyst with the hollow core-shell structure comprises the following steps:
(1) Taking Cu (NO) 3 ) 2 ·3H 2 O、Zn(NO 3 ) 2 ·6H 2 O and Al (NO) 3 ) 3 ·9H 2 Dissolving O in deionized water to obtain product A;
(2) Adding surfactant polyethylene glycol mono-hexadecane ether into solution containing cyclohexane and n-octanol, and stirring in water bath at 30-40 deg.C to dissolve to obtain product B;
(3) Adding product A into product B, stirring, and adding NaBH 4 Adding 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 @ SiO 2 ；
(4) Prepared CuZnAl@SiO 2 Ultrasonically 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 use 2 Reducing under the condition to obtain the modified Cu-Zn-Al hollow core-shell structure catalyst.
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 of the copper-based catalyst is a Cu-Zn catalyst, and the shell is porous silicon dioxide; the specific preparation process of the sulfur-resistant and high-temperature-resistant methanol catalyst with the hollow core-shell structure comprises the following steps:
(1) Taking Cu (NO) 3 ) 2 ·3H 2 O and Zn (NO) 3 ) 2 ·6H 2 Dissolving O in deionized water to obtain product A;
(2) Adding surfactant polyethylene glycol mono-hexadecane ether into solution containing cyclohexane and n-octanol, and stirring in water bath at 30-40 deg.C to dissolve to obtain product B;
(3) Adding product A into product B, stirring, and adding NaBH 4 Adding 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 @ SiO 2 ；
(4) Prepared CuZn @ SiO 2 Ultrasonically 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 use 2 Reducing under the condition to obtain the modified Cu-Zn hollow core-shell structure catalyst.
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: 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), naBH 4 The concentration of the solution was 10wt%, naBH was added 4 The post-reaction time of the solution is 5-15min, the concentration of ammonia water is 25-28wt%, 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 4-8h; step (4) and step (5) the CuZn @ SiO 2 The mass ratio of CTAB, sodium metaaluminate, anhydrous sodium carbonate and deionized water is 1:0.25:0.53:0.41:200 of a carrier; in the step (6), the roasting temperature is 400-500 ℃, and the modifier aqueous solution and the catalyst powder are impregnated in equal volume.
4. 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: 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), naBH 4 The concentration of the solution was 10wt%, naBH was added 4 The post-reaction time of the solution is 5-15min, the concentration of ammonia water is 25-28wt%, 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 4-8h; step (4) and step (5) the CuZnAl @ SiO 2 The mass ratio of CTAB, sodium metaaluminate, anhydrous sodium carbonate and deionized water is 1:0.25:0.53:0.41:200 of a carrier; in the step (6), the roasting temperature is 400-500 ℃, and the modifier aqueous solution and the catalyst powder areAnd (5) soaking in equal volume.
5. The preparation method of the sulfur-resistant and high-temperature-resistant hollow core-shell structure methanol catalyst according to claim 1 or 2, characterized by comprising the following steps: the modifier is 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。
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