CN116637624A - High-selectivity high-stability catalyst for preparing methanol from carbon dioxide and preparation method thereof - Google Patents
High-selectivity high-stability catalyst for preparing methanol from carbon dioxide and preparation method thereof Download PDFInfo
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- CN116637624A CN116637624A CN202210139341.1A CN202210139341A CN116637624A CN 116637624 A CN116637624 A CN 116637624A CN 202210139341 A CN202210139341 A CN 202210139341A CN 116637624 A CN116637624 A CN 116637624A
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 120
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 239000003054 catalyst Substances 0.000 title claims abstract description 108
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 57
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 52
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 52
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 239000010949 copper Substances 0.000 claims abstract description 41
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052802 copper Inorganic materials 0.000 claims abstract description 36
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 31
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 23
- 229910021331 inorganic silicon compound Inorganic materials 0.000 claims abstract description 20
- 239000011247 coating layer Substances 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 15
- 150000001282 organosilanes Chemical class 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims description 66
- 238000001035 drying Methods 0.000 claims description 42
- 239000007787 solid Substances 0.000 claims description 38
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 36
- 239000012265 solid product Substances 0.000 claims description 33
- 238000001816 cooling Methods 0.000 claims description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims description 23
- 239000012065 filter cake Substances 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 21
- 238000009210 therapy by ultrasound Methods 0.000 claims description 17
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 15
- 239000000725 suspension Substances 0.000 claims description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 14
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 14
- 229910052710 silicon Inorganic materials 0.000 claims description 14
- 239000010703 silicon Substances 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 239000012495 reaction gas Substances 0.000 claims description 10
- CDZGJSREWGPJMG-UHFFFAOYSA-N copper gallium Chemical compound [Cu].[Ga] CDZGJSREWGPJMG-UHFFFAOYSA-N 0.000 claims description 9
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 8
- KQIADDMXRMTWHZ-UHFFFAOYSA-N chloro-tri(propan-2-yl)silane Chemical compound CC(C)[Si](Cl)(C(C)C)C(C)C KQIADDMXRMTWHZ-UHFFFAOYSA-N 0.000 claims description 7
- -1 copper zinc aluminum Chemical compound 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000005051 trimethylchlorosilane Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 5
- PDYPRPVKBUOHDH-UHFFFAOYSA-N ditert-butyl(dichloro)silane Chemical compound CC(C)(C)[Si](Cl)(Cl)C(C)(C)C PDYPRPVKBUOHDH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- GZSJSGZGZXGFOW-UHFFFAOYSA-N [Zn].[Ce].[Cu] Chemical compound [Zn].[Ce].[Cu] GZSJSGZGZXGFOW-UHFFFAOYSA-N 0.000 claims description 3
- HLZWDTGLZQJWNL-UHFFFAOYSA-N [Zn].[Cu].[Y] Chemical compound [Zn].[Cu].[Y] HLZWDTGLZQJWNL-UHFFFAOYSA-N 0.000 claims description 3
- CTHCNINEXYPGQP-UHFFFAOYSA-N [Zn].[Cu].[Zr] Chemical compound [Zn].[Cu].[Zr] CTHCNINEXYPGQP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000000975 co-precipitation Methods 0.000 claims description 3
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 claims description 3
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 238000003980 solgel method Methods 0.000 claims description 3
- BCNZYOJHNLTNEZ-UHFFFAOYSA-N tert-butyldimethylsilyl chloride Chemical compound CC(C)(C)[Si](C)(C)Cl BCNZYOJHNLTNEZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 description 64
- 238000007873 sieving Methods 0.000 description 28
- 239000011259 mixed solution Substances 0.000 description 23
- 239000012018 catalyst precursor Substances 0.000 description 20
- 238000000227 grinding Methods 0.000 description 19
- 239000004570 mortar (masonry) Substances 0.000 description 17
- 238000011156 evaluation Methods 0.000 description 12
- 238000011068 loading method Methods 0.000 description 10
- 230000001105 regulatory effect Effects 0.000 description 9
- 238000005303 weighing Methods 0.000 description 8
- 229910017773 Cu-Zn-Al Inorganic materials 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- MXOSTENCGSDMRE-UHFFFAOYSA-N butyl-chloro-dimethylsilane Chemical group CCCC[Si](C)(C)Cl MXOSTENCGSDMRE-UHFFFAOYSA-N 0.000 description 1
- 230000035425 carbon utilization Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/154—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing copper, silver, gold, or compounds thereof
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A high-selectivity high-stability catalyst for preparing methanol from carbon dioxide and a preparation method thereof comprise a copper-based metal oxide and a silicon dioxide coating layer, wherein the silicon dioxide coating layer comprises an inorganic silicon compound and an organosilane hydrophobizing agent; the mass fraction of the copper-based metal oxide is 50-70% based on the total mass of the catalyst, and the balance is a silicon dioxide coating layer; in the silicon dioxide coating layer, the mass fraction of the inorganic silicon compound is 40% -70%, and the mass fraction of the organosilane hydrophobizing agent is 30% -60%. The catalyst is suitable for hydrogenation reaction of carbon dioxide, the conversion rate of the carbon dioxide is over 18%, the selectivity of methanol is higher than 87%, and the stability is good. The catalyst has the advantages of simple preparation method, low price, excellent performance and wide industrial application prospect.
Description
Technical Field
The invention relates to the field of hydrogenation catalysts, in particular to a catalyst for preparing methanol from carbon dioxide with high selectivity and high stability and a preparation method thereof.
Background
Under the background of the strong development of renewable energy sources such as solar energy and wind energy, renewable energy sources are utilized to generate electricity and electrolyze water to prepare hydrogen, namely green hydrogen, so as to hydrogenate and convert carbon dioxide into basic chemical methanol. Methanol is an important basic chemical raw material, can be used as a substitute fuel, and can be used for synthesizing various chemicals such as dimethyl ether, olefin, aromatic hydrocarbon, acetic acid, esters and the like. Currently, the methanol production in China mainly adopts a coal chemical industry route, namely, coal-based synthesis gas is used as a raw material to directly synthesize the methanol. The main catalyst systems for preparing methanol by catalytic hydrogenation of carbon dioxide reported at present are of three main types: cu-based catalysts, in-based catalysts, and metal oxide catalysts.
Cu-based catalysts, e.g. Cu/ZnO, cu/ZrO 2 、Cu/ZnO/Al 2 O 3 And the like, has better catalytic conversion activity of carbon dioxide, and is considered as a catalyst with the most industrial application prospect. However, cu-based catalysts have problems of easy sintering and oxidation in the reaction atmosphere, and thus the catalyst is deactivated, and in addition, the selectivity of CO, alkane and other byproducts is relatively high. In-based catalysts are largely divided into two classes, supported and bulk, such as In 2 O 3 -Pd、In 2 O 3 -ZrO 2 Etc., wherein In 2 O 3 The oxygen vacancies In the catalyst can effectively activate carbon dioxide, inhibit the formation of carbon monoxide while generating methanol, but the active components of the catalyst are easy to lose and deactivate at high temperature, and In is expensive, so that the catalyst is not suitable for large-scale application. Metal oxide catalysts, e.g. ZnZrO X 、GaZrO X Etc., wherein the strong synergistic effect of the two metal components enhances H 2 The heterogeneous dissociation of the catalyst leads to high activity and high methanol selectivity, the conversion rate of the catalyst is lower at low temperature, and the catalyst needs to have certain activity at higher temperature, but CO byproducts are easy to generate at high temperature, so that the carbon utilization efficiency is influenced.
In summary, the existing methanol catalyst mainly comprises a Cu-based catalyst, but under long-time reaction conditions, the Cu-based catalyst is easy to sinter and deactivate, so that the catalytic performance, particularly the carbon dioxide conversion rate and the methanol selectivity, are difficult to improve at the same time, which limits the industrial application of the catalyst. Therefore, the development of the carbon dioxide hydrogenation catalyst with low reverse steam conversion activity and high stability has important significance.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provide a catalyst with low reverse steam conversion activity and high stability for preparing methanol by hydrogenating carbon dioxide and a preparation method thereof.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a high-selectivity high-stability catalyst for preparing methanol from carbon dioxide comprises copper-based metal oxide and a silicon dioxide coating layer, wherein the silicon dioxide coating layer comprises an inorganic silicon compound and an organosilane hydrophobizing agent; the mass fraction of the copper-based metal oxide is 50-70% based on the total mass of the catalyst, and the balance is a silicon dioxide coating layer; in the silicon dioxide coating layer, the mass fraction of the inorganic silicon compound is 40% -70%, and the mass fraction of the organosilane hydrophobizing agent is 30% -60%.
The inorganic silicon compound comprises at least one of white carbon black, silica sol and silicate, and the organosilane hydrophobizing agent comprises at least one of trimethylchlorosilane, tert-butyldimethylchlorosilane, triisopropylchlorosilane and di-tert-butyldichlorosilane.
The copper-based metal oxide comprises at least one of copper zinc, copper zinc aluminum, copper zinc zirconium, copper zinc aluminum zirconium, copper zinc yttrium, copper zinc cerium, copper gallium zirconium, copper gallium aluminum and copper gallium cerium.
The preparation method of the catalyst for preparing methanol from carbon dioxide with high selectivity and high stability comprises the following steps:
1) Adding copper-based metal oxide into absolute ethyl alcohol for dispersion, then adding inorganic silicon compound, stirring, adding ammonia water, continuously stirring, and finally centrifugally washing to obtain a filter cake;
2) Drying and roasting the filter cake obtained in the step 1) to obtain an inorganic silicon coated copper-based metal oxide solid sample;
3) Adding the inorganic silicon coated copper-based metal oxide solid sample obtained in the step 2) into n-hexane, stirring, adding an organosilane hydrophobizing agent, continuously stirring, and performing ultrasonic treatment to obtain a suspension;
4) And (3) centrifugally washing the suspension obtained in the step (3), drying, and reducing to obtain the catalyst for preparing the methanol by hydrogenating the carbon dioxide.
In the step 1), the copper-based metal oxide is prepared by adopting a coprecipitation method, a sol-gel method or a hydrothermal method.
In the step 1), the mass ratio of the absolute ethyl alcohol to the copper-based metal oxide is (100-200): 1; the mass ratio of the ammonia water to the inorganic silicon compound is (10-20): 1, and the concentration of the ammonia water is 25% -28%; in the step 2), the mass ratio of the n-hexane to the inorganic silicon compound is (50 to 100): 1.
In the step 1), the stirring speed is 200-1000r/min, the stirring temperature is 20-60 ℃, and the stirring time is 2-8 h; in the step 3), the stirring speed is 200-1000r/min, the stirring temperature is 20-60 ℃, the stirring time is 0.5-1.5 h, and the ultrasonic time is 1-4 h.
In the step 2), the step of drying is as follows: drying in a drying oven at 100-120 ℃ for 2-10 h, taking out the dried solid product, cooling, and then transferring to a vacuum drying oven at 130-160 ℃ for drying for 5-12 h; the roasting step is as follows: roasting at 300-600 deg.c in air atmosphere for 2-12 hr.
In step 4), the reduction conditions are: at H 2 H with concentration of 5% -50% 2 /N 2 Or H 2 Ar or pure H 2 Reducing for 0.5-10 h at 200-500 deg.C under atmosphere.
The catalyst for preparing methanol from carbon dioxide with high selectivity and high stability is applied to the reaction for preparing methanol by carbon dioxide hydrogenation, and the reaction conditions are as follows: the hydrogenation reaction pressure of carbon dioxide is 5-150 bar, the reaction temperature is 180-320 ℃, H 2 With CO 2 The volume ratio of (1:9) - (9:1), the space velocity of the reaction gas is 1000-50000mL h -1 g -1 。
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
1. the catalyst of the invention has excellent low reverse steam conversion activity and stability for preparing methanol by hydrogenation and selective hydrogenation of carbon dioxide, the carbon dioxide conversion rate is more than 18%, and the methanol selectivity can reach more than 87%;
2. the silicon dioxide surface coating added in the preparation process of the catalyst can inhibit generated water from entering the surface of the catalyst to contact the copper-based catalyst, so that the copper-based catalyst is protected from being oxidized by water generated in the methanol synthesis process, and meanwhile, the migration of ZnO can be inhibited, further, the reverse steam shift reaction is inhibited from generating CO, and the catalyst is obviously inhibited from being deactivated;
3. the catalyst has the advantages of simple preparation process, good repeatability and easy mass production;
4. the catalyst is non-noble metal, has low price, low industrial production cost and good application prospect.
Drawings
FIG. 1 is a graph showing the results of evaluation of the stability of the catalyst prepared in example 1;
FIG. 2 is a graph showing the results of evaluating the stability of the catalyst prepared in comparative example 2.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clear and obvious, the invention is further described in detail below with reference to the accompanying drawings and embodiments.
The invention relates to a high-selectivity high-stability catalyst for preparing methanol from carbon dioxide, which comprises copper-based metal oxide and a silicon dioxide coating layer, wherein the silicon dioxide coating layer comprises an inorganic silicon compound and an organosilane hydrophobizing agent; the mass fraction of the copper-based metal oxide is 50-70% based on the total mass of the catalyst, and the balance is a silicon dioxide coating layer; in the silicon dioxide coating layer, the mass fraction of the inorganic silicon compound is 40% -70%, and the mass fraction of the organosilane hydrophobizing agent is 30% -60%.
Specifically, the inorganic silicon compound comprises at least one of white carbon black, silica sol and silicate, and the organosilane hydrophobizing agent comprises at least one of trimethylchlorosilane, tert-butyldimethylchlorosilane, triisopropylchlorosilane and di-tert-butyldichlorosilane.
Specifically, the copper-based metal oxide comprises at least one of copper zinc, copper zinc aluminum, copper zinc zirconium, copper zinc aluminum zirconium, copper zinc yttrium, copper zinc cerium, copper gallium zirconium, copper gallium aluminum and copper gallium cerium, and is prepared by adopting a coprecipitation method, a sol-gel method or a hydrothermal method.
The invention relates to a high-selectivity high-stability catalyst for preparing methanol from carbon dioxide, which comprises the following specific preparation steps:
(1) Taking a metered amount of copper-based metal oxide, placing the copper-based metal oxide into a mortar for grinding to powder, and sieving the powder by 100 to 200 meshes to obtain uniform powder;
(2) Weighing the powder obtained in the steps, adding the powder into metered absolute ethyl alcohol, and carrying out ultrasonic treatment at 20-60 ℃ for 0.5-2.0 h to uniformly disperse a powder sample;
(3) Adding a metered inorganic silicon compound into the mixed solution obtained in the step (2), and stirring for 2-8 h at 20-60 ℃ at the rotating speed of 200-1000 r/min; adding metered ammonia water (25-28%), maintaining the same rotation speed and reaction temperature, continuously stirring for 2-8 h, centrifuging the mixed solution, and washing with absolute ethyl alcohol to obtain a filter cake;
(4) Transferring the obtained filter cake into a drying oven at 100-120 ℃ for drying for 2-10 h, taking out the dried solid product, cooling to 30 ℃, transferring into a vacuum drying oven at 130-160 ℃ for drying for 5-12 h, and cooling to 30 ℃ to obtain a solid sample;
(5) Placing the solid sample into a muffle furnace for roasting, and roasting at 300-600 ℃ in an air atmosphere for 2-12 h to obtain an inorganic silicon coated copper-based metal oxide solid sample;
(6) Adding the inorganic silicon coated copper-based metal oxide solid sample into metered n-hexane, and stirring for 0.5-1.5 h at 20-60 ℃ at the rotating speed of 200-1000 r/min; adding a metered organosilane hydrophobizing agent, maintaining the same rotation speed and reaction temperature, continuously stirring for 0.5-1.5 h, and carrying out ultrasonic treatment for 1-4 h to obtain a suspension;
(7) Centrifuging the obtained suspension, washing with n-hexane, transferring to a vacuum oven at 70-100 ℃ for drying for 5-12 h, taking out the dried solid product, cooling to 30 ℃, placing the solid product in a mortar for grinding to powder, sieving with 100-200 meshes to obtain uniform powder, tabletting with 30-60 KN pressure, and sieving with 30-60 meshes of catalyst precursors;
(8) Loading a catalyst precursor into a reactor, at H 2 H with concentration of 5-50% 2 /N 2 Or H 2 Ar or pure H 2 Under the atmosphere, the temperature is raised to 200-500 ℃ at 1 ℃/min, and the catalyst is reduced for 0.5-10 h, so as to obtain the catalyst for preparing the methanol by the hydrogenation of the carbon dioxide.
The solid-to-liquid ratio of the absolute ethyl alcohol to the copper-based metal oxide is (100-200): 1; the solid-to-liquid ratio of the ammonia water (25-28%) to the inorganic silicon compound is (10-20): 1; the solid-to-liquid ratio of the n-hexane to the inorganic silicon compound is (50-100): 1.
The invention relates to a high-selectivity high-stability catalyst for preparing methanol by carbon dioxide, which is used for the reaction of preparing methanol by carbon dioxide hydrogenation, and the specific reaction conditions are as follows: the hydrogenation reaction pressure of carbon dioxide is 5-150 bar, the reaction temperature is 180-320 ℃, H 2 With CO 2 The volume ratio of (1:9) - (9:1), the space velocity of the reaction gas is 1000-50000mL h -1 g -1 。
Example 1
Taking 10 small cylindrical Cu-Zn-Zr metal oxides, putting the metal oxides into a mortar for crushing and grinding to powder, and sieving the powder by 120 meshes to obtain uniform powder. Weighing 2.0g of powder, adding 300mL of absolute ethyl alcohol into a beaker, carrying out ultrasonic treatment at 40 ℃ for 1h, adding 1.0mL of silica sol into the mixed solution, placing the mixed solution on a stirring table, stirring at 40 ℃ for 4h, adding 25mL of ammonia water (25% -28%) at the same rotating speed and reaction temperature, continuously stirring for 4h, centrifugally washing the mixed solution by the absolute ethyl alcohol to obtain a filter cake, transferring the filter cake into a 100-120 ℃ oven for drying for 10h, taking out the dried solid product, cooling to 30 ℃, transferring the filter cake into a 150 ℃ vacuum oven for drying for 11h, cooling to 30 ℃ to obtain a solid sample, roasting at 400 ℃ for 4h to obtain an inorganic silicon coated copper-based metal oxide solid sample, adding the solid sample into 150mL of normal hexane, placing the solid sample on the stirring table, and transferring the solid sample to the stirring table at 450r/minStirring at 40 ℃ for 0.5h, adding 0.8mL of trimethylchlorosilane, continuously stirring at the same rotating speed and reaction temperature for 0.5h, carrying out ultrasonic treatment for 3h to obtain suspension, centrifuging and washing by normal hexane, transferring to a vacuum oven at 80 ℃ for drying for 11h, taking out the dried solid product, cooling to 30 ℃, placing the solid product in a mortar for grinding to powder, sieving with 120 meshes to obtain uniform powder, tabletting by using 30KN pressure, and sieving with 30-60 meshes of particles to obtain the catalyst precursor. The catalyst precursor is filled into a reactor and is subjected to 10% H at normal pressure 2 /N 2 And (3) under the atmosphere, heating to 300 ℃ at 1 ℃/min, and reducing for 2 hours to obtain the Cu-Zn-Zr/silica sol-TMSCl catalyst.
The catalyst is used for evaluating the hydrogenation reaction of carbon dioxide. The specific operation is as follows: adopting a fixed bed reactor, wherein the catalyst loading amount is 0.5g, the carbon dioxide hydrogenation reaction pressure is regulated to be 60bar, the reaction temperature is 230 ℃, and H 2 With CO 2 The volume ratio of (2) is 3:1, and the space velocity of the reaction gas is 9000mL h -1 g -1 . The results of the performance evaluation of the catalyst are shown in Table 1. FIG. 1 shows the results of catalyst stability evaluation. From the graph, the carbon dioxide conversion rate and the methanol selectivity of the Cu-Zn-Zr/silica sol-TMSCl catalyst are not changed remarkably in the estimated 100h reaction time, and the catalyst shows good stability.
Example 2
Taking 10 small cylindrical Cu-Zn-Zr metal oxides, putting the metal oxides into a mortar for crushing and grinding to powder, and sieving the powder by 120 meshes to obtain uniform powder. Weighing 2.0g of powder, adding 300mL of absolute ethyl alcohol into a beaker, carrying out ultrasonic treatment at 40 ℃ for 1h, adding 1.0mL of silica sol into the mixed solution, placing the mixed solution on a stirring table, stirring at 40 ℃ for 4h, adding 25mL of ammonia water (25% -28%) at the same rotating speed and reaction temperature, continuously stirring for 4h, centrifugally washing the mixed solution by the absolute ethyl alcohol to obtain a filter cake, transferring the filter cake into a 100-120 ℃ oven for drying for 10h, taking out the dried solid product, cooling to 30 ℃, transferring the filter cake into a 150 ℃ vacuum oven for drying for 11h, cooling to 30 ℃ to obtain a solid sample, roasting for 4h at 400 ℃ under the air condition to obtain an inorganic silicon coated copper-based metal oxide solid sample, adding the solid sample into 150mL of n-hexane, and placingStirring for 0.5h at a speed of 450r/min on a stirring table at a temperature of 40 ℃, adding 0.8mL of tertiary butyl dimethyl chlorosilane, continuously stirring for 0.5h at the same speed and reaction temperature, performing ultrasonic treatment for 3h to obtain suspension, centrifuging and washing by normal hexane, transferring into a vacuum oven at 80 ℃ for drying for 11h, taking out the dried solid product, cooling to 30 ℃, placing into a mortar for grinding to powder, sieving to obtain uniform powder, tabletting by using 30KN pressure, and sieving to obtain catalyst precursor by using 30-60 meshes of particles. The catalyst precursor is filled into a reactor and is subjected to 10% H at normal pressure 2 /N 2 And (3) under the atmosphere, heating to 300 ℃ at 1 ℃/min, and reducing for 2 hours to obtain the Cu-Zn-Zr/silica sol-TBSCl catalyst.
The catalyst is used for evaluating the hydrogenation reaction of carbon dioxide. The specific operation is as follows: adopting a fixed bed reactor, wherein the catalyst loading amount is 0.5g, the carbon dioxide hydrogenation reaction pressure is regulated to be 60bar, the reaction temperature is 230 ℃, and H 2 With CO 2 The volume ratio of (2) is 3:1, and the space velocity of the reaction gas is 9000mL h -1 g -1 . The results of the performance evaluation of the catalyst are shown in Table 1.
Example 3
Taking 10 small cylindrical Cu-Zn-Zr metal oxides, putting the metal oxides into a mortar for crushing and grinding to powder, and sieving the powder by 120 meshes to obtain uniform powder. Weighing 2.0g of powder, adding 300mL of absolute ethyl alcohol into a beaker, carrying out ultrasonic treatment at 40 ℃ for 1h, adding 1.0mL of silica sol into the mixed solution, placing the mixed solution on a stirring table, stirring at 40 ℃ for 4h, adding 25mL of ammonia water (25% -28%) at the same rotating speed and reaction temperature, continuously stirring for 4h, centrifugally washing the mixed solution by the absolute ethyl alcohol to obtain a filter cake, transferring the filter cake into a baking oven at 100-120 ℃ for drying for 10h, taking out the dried solid product, cooling to 30 ℃, transferring the dried solid product into a vacuum baking oven at 150 ℃ for drying for 11h, cooling to 30 ℃ to obtain a solid sample, roasting at 400 ℃ for 4h to obtain an inorganic silicon coated copper-based metal oxide solid sample, adding the solid sample into 150mL of n-hexane, placing the solid sample into the stirring table, stirring at 450r/min for 0.5h at 40 ℃, continuously stirring at the same rotating speed and reaction temperature for 0.5h, and continuously stirring for 0.5h, carrying out ultrasonic treatment for 3h to obtain the inorganic silicon coated copper-based metal oxide solid sampleAnd (3) centrifuging and washing the suspension by normal hexane, transferring to a vacuum oven at 80 ℃ for drying for 11 hours, taking out the dried solid product, cooling to 30 ℃, placing the solid product in a mortar for grinding to powder, sieving the powder to 120 meshes to obtain uniform powder, tabletting by using 30KN pressure, and sieving the granules of 30 to 60 meshes to obtain the catalyst precursor. The catalyst precursor is filled into a reactor and is subjected to 10% H at normal pressure 2 /N 2 And (3) under the atmosphere, heating to 300 ℃ at 1 ℃/min, and reducing for 2 hours to obtain the Cu-Zn-Zr/silica sol-TIPSCl catalyst.
The catalyst is used for evaluating the hydrogenation reaction of carbon dioxide. The specific operation is as follows: adopting a fixed bed reactor, wherein the catalyst loading amount is 0.5g, the carbon dioxide hydrogenation reaction pressure is regulated to be 60bar, the reaction temperature is 230 ℃, and H 2 With CO 2 The volume ratio of (2) is 3:1, and the space velocity of the reaction gas is 9000mL h -1 g -1 . The results of the performance evaluation of the catalyst are shown in Table 1.
Example 4
Taking 10 small cylindrical Cu-Zn-Zr metal oxides, putting the metal oxides into a mortar for crushing and grinding to powder, and sieving the powder by 120 meshes to obtain uniform powder. Weighing 2.0g of powder, adding 300mL of absolute ethyl alcohol into the powder in a beaker, carrying out ultrasonic treatment at 40 ℃ for 1h, adding 1.0mL of silica sol into the mixed solution, placing the mixed solution on a stirring table, stirring at 40 ℃ for 4h, adding 25mL of ammonia water (25% -28%) at the same rotating speed and reaction temperature, continuing stirring for 4h, carrying out centrifugal washing on the mixed solution by the absolute ethyl alcohol to obtain a filter cake, transferring the filter cake into a 100-120 ℃ oven for drying for 10h, taking out the dried solid product, cooling to 30 ℃ and then transferring the solid product into a 150 ℃ vacuum oven for drying for 11h, cooling to 30 ℃ to obtain a solid sample, roasting at 400 ℃ for 4h to obtain an inorganic silicon coated copper-based metal oxide solid sample, adding the solid sample into 150mL of n-hexane, placing the solid sample into the stirring table, stirring at 450r/min for 0.5h at 40 ℃, adding 0.8mL of di-tert-butyldichlorosilane at the same rotating speed and reaction temperature, continuing stirring for 0.5h, carrying out ultrasonic washing at the same rotating speed and reaction temperature, transferring the dried solid product into the vacuum oven for 3 ℃ for drying for 11h, carrying out centrifugal washing to obtain a solid product, and carrying out centrifugal drying for 12h, grinding, drying to obtain a solid product, and carrying out grinding, and drying to obtain a solid product, and sieving in a vacuum oven for 12h, after cooling to obtain a dry product, and drying to obtain a solid product, and drying to be dried into a dry product0 mesh to obtain uniform powder, tabletting with 30KN pressure, and sieving with 30-60 mesh sieve to obtain catalyst precursor. The catalyst precursor is filled into a reactor and is subjected to 10% H at normal pressure 2 /N 2 Reducing for 2h at the temperature of 1 ℃/min to 300 ℃ under the atmosphere to prepare the Cu-Zn-Zr/silica sol-DTBSCl 2 A catalyst.
The catalyst is used for evaluating the hydrogenation reaction of carbon dioxide. The specific operation is as follows: adopting a fixed bed reactor, wherein the catalyst loading amount is 0.5g, the carbon dioxide hydrogenation reaction pressure is regulated to be 60bar, the reaction temperature is 230 ℃, and H 2 With CO 2 The volume ratio of (2) is 3:1, and the space velocity of the reaction gas is 9000mL h -1 g -1 . The results of the performance evaluation of the catalyst are shown in Table 1.
Example 5
Taking 10 small cylindrical Cu-Zn-Al metal oxides, putting the metal oxides into a mortar, crushing and grinding the metal oxides into powder, and sieving the powder with 120 meshes to obtain uniform powder. Weighing 2.0g of powder, adding 300mL of absolute ethyl alcohol into the powder in a beaker, carrying out ultrasonic treatment at 40 ℃ for 1h, adding 1.0mL of silica sol into the mixed solution, placing the mixed solution on a stirring table, stirring at 40 ℃ for 4h, adding 25mL of ammonia water (25% -28%), continuing stirring at the same rotating speed and reaction temperature for 4h, centrifugally washing the mixed solution by the absolute ethyl alcohol to obtain a filter cake, transferring the filter cake into a baking oven at 100-120 ℃ for drying for 10h, taking out the dried solid product, cooling to 30 ℃, transferring the solid product into a vacuum baking oven at 150 ℃ for drying for 11h, cooling to 30 ℃ to obtain a solid sample, baking the solid sample for 4h under the air condition of 400 ℃, obtaining an inorganic silicon coated copper-based metal oxide solid sample, adding the solid sample into 150mL of n-hexane, placing the solid sample on a stirring table, stirring at the rotation speed of 450r/min for 0.5h at the temperature of 40 ℃, adding 0.8mL of trimethylchlorosilane, continuing stirring at the same rotation speed and reaction temperature for 0.5h, carrying out ultrasonic treatment for 3h to obtain a suspension, centrifuging and washing by n-hexane, transferring the suspension into a vacuum oven at 80 ℃ for drying for 11h, taking out the dried solid product, cooling to 30 ℃, placing the dried solid product into a mortar, grinding to powder, sieving for 120 meshes to obtain uniform powder, tabletting by using the pressure of 30KN, and sieving particles of 30 to 60 meshes to obtain a catalyst precursor. The catalyst precursor is filled into a reactor and is subjected to 10% H at normal pressure 2 /N 2 And (3) under the atmosphere, heating to 300 ℃ at 1 ℃/min, and reducing for 2 hours to obtain the Cu-Zn-Al/silica sol-TMSCl catalyst.
The catalyst is used for evaluating the hydrogenation reaction of carbon dioxide. The specific operation is as follows: adopting a fixed bed reactor, wherein the catalyst loading amount is 0.5g, the carbon dioxide hydrogenation reaction pressure is regulated to be 60bar, the reaction temperature is 230 ℃, and H 2 With CO 2 The volume ratio of (2) is 3:1, and the space velocity of the reaction gas is 9000mL h -1 g -1 . The results of the performance evaluation of the catalyst are shown in Table 1.
Example 6
Taking 10 small cylindrical Cu-Zn-Zr metal oxides, putting the metal oxides into a mortar for crushing and grinding to powder, and sieving the powder by 120 meshes to obtain uniform powder. Weighing 2.0g of powder, adding 300mL of absolute ethyl alcohol into the powder in a beaker, carrying out ultrasonic treatment at 40 ℃ for 1h, adding 0.5mL of sodium silicate into the mixed solution, placing the mixed solution on a stirring table, stirring at 40 ℃ for 4h, adding 25mL of ammonia water (25% -28%) at the same rotating speed and reaction temperature, continuously stirring for 4h, centrifugally washing the mixed solution by the absolute ethyl alcohol to obtain a filter cake, transferring the filter cake into a baking oven at 100-120 ℃ for drying for 10h, taking out the dried solid product, cooling to 30 ℃, transferring the solid product into a vacuum baking oven at 150 ℃ for drying for 11h, cooling to 30 ℃ to obtain a solid sample, roasting at 400 ℃ for 4h, obtaining an inorganic silicon coated copper-based metal oxide solid sample, adding the solid sample into 150mL of n-hexane, placing the solid sample on a stirring table, stirring at the rotation speed of 450r/min for 0.5h at the temperature of 40 ℃, adding 0.8mL of trimethylchlorosilane, continuing stirring at the same rotation speed and reaction temperature for 0.5h, carrying out ultrasonic treatment for 3h to obtain a suspension, centrifuging and washing by n-hexane, transferring the suspension into a vacuum oven at 80 ℃ for drying for 11h, taking out the dried solid product, cooling to 30 ℃, placing the dried solid product into a mortar, grinding to powder, sieving for 120 meshes to obtain uniform powder, tabletting by using the pressure of 30KN, and sieving particles of 30 to 60 meshes to obtain a catalyst precursor. The catalyst precursor is filled into a reactor and is subjected to 10% H at normal pressure 2 /N 2 And (3) under the atmosphere, heating to 300 ℃ at 1 ℃/min, and reducing for 2 hours to obtain the Cu-Zn-Zr/sodium silicate-TMSCl catalyst.
The catalyst is used for carbon dioxide hydrogenation reactionShould be evaluated. The specific operation is as follows: adopting a fixed bed reactor, wherein the catalyst loading amount is 0.5g, the carbon dioxide hydrogenation reaction pressure is regulated to be 60bar, the reaction temperature is 230 ℃, and H 2 With CO 2 The volume ratio of (2) is 3:1, and the space velocity of the reaction gas is 9000mL h -1 g -1 . The results of the performance evaluation of the catalyst are shown in Table 1.
Example 7
Taking 10 small cylindrical Cu-Zn-Al metal oxides, putting the metal oxides into a mortar, crushing and grinding the metal oxides into powder, and sieving the powder with 120 meshes to obtain uniform powder. Weighing 2.0g of powder, adding 300mL of absolute ethyl alcohol into the powder in a beaker, carrying out ultrasonic treatment at 40 ℃ for 1h, adding 0.5mL of sodium silicate into the mixed solution, placing the mixed solution on a stirring table, stirring at 40 ℃ for 4h, adding 25mL of ammonia water (25% -28%) at the same rotating speed and reaction temperature, continuously stirring for 4h, centrifugally washing the mixed solution by the absolute ethyl alcohol to obtain a filter cake, transferring the filter cake into a baking oven at 100-120 ℃ for drying for 10h, taking out the dried solid product, cooling to 30 ℃, transferring the solid product into a vacuum baking oven at 150 ℃ for drying for 11h, cooling to 30 ℃ to obtain a solid sample, roasting at 400 ℃ for 4h, obtaining an inorganic silicon coated copper-based metal oxide solid sample, adding the solid sample into 150mL of n-hexane, placing the solid sample on a stirring table, stirring at the rotation speed of 450r/min for 0.5h at the temperature of 40 ℃, adding 0.8mL of trimethylchlorosilane, continuing stirring at the same rotation speed and reaction temperature for 0.5h, carrying out ultrasonic treatment for 3h to obtain a suspension, centrifuging and washing by n-hexane, transferring the suspension into a vacuum oven at 80 ℃ for drying for 11h, taking out the dried solid product, cooling to 30 ℃, placing the dried solid product into a mortar, grinding to powder, sieving for 120 meshes to obtain uniform powder, tabletting by using the pressure of 30KN, and sieving particles of 30 to 60 meshes to obtain a catalyst precursor. The catalyst precursor is filled into a reactor and is subjected to 10% H at normal pressure 2 /N 2 And (3) under the atmosphere, heating to 300 ℃ at 1 ℃/min, and reducing for 2 hours to obtain the Cu-Zn-Al/sodium silicate-TMSCl catalyst.
The catalyst is used for evaluating the hydrogenation reaction of carbon dioxide. The specific operation is as follows: adopting a fixed bed reactor, wherein the catalyst loading amount is 0.5g, the carbon dioxide hydrogenation reaction pressure is regulated to be 60bar, the reaction temperature is 230 ℃, and H 2 With CO 2 The volume ratio of (2) is 3:1, and the space velocity of the reaction gas is 9000mL h -1 g -1 . The results of the performance evaluation of the catalyst are shown in Table 1.
Comparative example 1
Taking 10 small cylindrical Cu-Zn-Al industrial methanol catalysts, putting the catalysts into a mortar, crushing and grinding the catalysts into powder, sieving the powder with 120 meshes to obtain uniform powder, tabletting the uniform powder by using 30KN pressure, and sieving the powder with 30 to 60 meshes to obtain a catalyst precursor. The catalyst precursor is filled into a reactor and is subjected to 10% H at normal pressure 2 /N 2 And (3) under the atmosphere, heating to 300 ℃ at 1 ℃/min, and reducing for 2 hours to obtain the Cu-Zn-Al catalyst, which is named as Cu-Zn-Al.
The catalyst is used for evaluating the hydrogenation reaction of carbon dioxide. The specific operation is as follows: adopting a fixed bed reactor, wherein the catalyst loading amount is 0.5g, the carbon dioxide hydrogenation reaction pressure is regulated to be 60bar, the reaction temperature is 230 ℃, and H 2 With CO 2 The volume ratio of (3) to (1) is 12000mL h -1 g -1 . The results of the performance evaluation of the catalyst are shown in Table 1.
Comparative example 2
Taking 10 small cylindrical Cu-Zn-Zr industrial methanol catalysts, putting the catalysts into a mortar, crushing and grinding the catalysts into powder, sieving the powder with 120 meshes to obtain uniform powder, tabletting the uniform powder by using 30KN pressure, and sieving the powder with 30 to 60 meshes to obtain a catalyst precursor. The catalyst precursor is filled into a reactor and is subjected to 10% H at normal pressure 2 /N 2 Under the atmosphere, the temperature is increased to 300 ℃ at 1 ℃/min for reduction for 2 hours, and the Cu-Zn-Zr catalyst is prepared and is marked as Cu-Zn-Zr.
The catalyst is used for evaluating the hydrogenation reaction of carbon dioxide. The specific operation is as follows: adopting a fixed bed reactor, wherein the catalyst loading amount is 0.5g, the carbon dioxide hydrogenation reaction pressure is regulated to be 60bar, the reaction temperature is 230 ℃, and H 2 With CO 2 The volume ratio of (3) to (1) is 12000mL h -1 g -1 . The results of the performance evaluation of the catalyst are shown in Table 1. Fig. 2 shows the results of catalyst stability evaluation. As can be seen from the figure, the conversion of carbon dioxide on the Cu-Zn-Zr catalyst is reduced, the selectivity of methanol is obviously reduced, and the selectivity of by-product carbon monoxide is sharply increased along with the extension of the reaction time, namely the catalystThe agent is deactivated.
TABLE 1
The catalyst is suitable for hydrogenation reaction of carbon dioxide, the conversion rate of the carbon dioxide is over 18%, the selectivity of methanol is higher than 87%, and the stability is good. The catalyst has the advantages of simple preparation method, low price, excellent performance and wide industrial application prospect.
Claims (10)
1. A catalyst for preparing methanol from carbon dioxide with high selectivity and high stability is characterized in that: comprising a copper-based metal oxide and a silica coating layer, wherein the silica coating layer comprises an inorganic silicon compound and an organosilane hydrophobizing agent; the mass fraction of the copper-based metal oxide is 50-70% based on the total mass of the catalyst, and the balance is a silicon dioxide coating layer; in the silicon dioxide coating layer, the mass fraction of the inorganic silicon compound is 40% -70%, and the mass fraction of the organosilane hydrophobizing agent is 30% -60%.
2. A high selectivity high stability catalyst for producing methanol from carbon dioxide as defined in claim 1, wherein: the inorganic silicon compound comprises at least one of white carbon black, silica sol and silicate, and the organosilane hydrophobizing agent comprises at least one of trimethylchlorosilane, tert-butyldimethylchlorosilane, triisopropylchlorosilane and di-tert-butyldichlorosilane.
3. A high selectivity high stability catalyst for producing methanol from carbon dioxide as defined in claim 1, wherein: the copper-based metal oxide comprises at least one of copper zinc, copper zinc aluminum, copper zinc zirconium, copper zinc aluminum zirconium, copper zinc yttrium, copper zinc cerium, copper gallium zirconium, copper gallium aluminum and copper gallium cerium.
4. A method for preparing a catalyst for preparing methanol from carbon dioxide with high selectivity and high stability as claimed in any one of claims 1 to 3, comprising the steps of:
1) Adding copper-based metal oxide into absolute ethyl alcohol for dispersion, then adding inorganic silicon compound, stirring, adding ammonia water, continuously stirring, and finally centrifugally washing to obtain a filter cake;
2) Drying and roasting the filter cake obtained in the step 1) to obtain an inorganic silicon coated copper-based metal oxide solid sample;
3) Adding the inorganic silicon coated copper-based metal oxide solid sample obtained in the step 2) into n-hexane, stirring, adding an organosilane hydrophobizing agent, continuously stirring, and performing ultrasonic treatment to obtain a suspension;
4) And (3) centrifugally washing the suspension obtained in the step (3), drying, and reducing to obtain the catalyst for preparing the methanol by hydrogenating the carbon dioxide.
5. The method of manufacturing according to claim 4, wherein: in the step 1), the copper-based metal oxide is prepared by adopting a coprecipitation method, a sol-gel method or a hydrothermal method.
6. The method of manufacturing according to claim 4, wherein: in the step 1), the mass ratio of the absolute ethyl alcohol to the copper-based metal oxide is (100-200): 1; the mass ratio of the ammonia water to the inorganic silicon compound is (10-20): 1, and the concentration of the ammonia water is 25% -28%; in the step 3), the mass ratio of the n-hexane to the inorganic silicon compound is (50 to 100): 1.
7. The method of manufacturing according to claim 4, wherein: in the step 1), the stirring speed is 200-1000r/min, the stirring temperature is 20-60 ℃, and the stirring time is 2-8 h; in the step 3), the stirring speed is 200-1000r/min, the stirring temperature is 20-60 ℃, the stirring time is 0.5-1.5 h, and the ultrasonic time is 1-4 h.
8. The method of manufacturing according to claim 4, wherein: in the step 2), the step of drying is as follows: drying in a drying oven at 100-120 ℃ for 2-10 h, taking out the dried solid product, cooling, and then transferring to a vacuum drying oven at 130-160 ℃ for drying for 5-12 h; the roasting step is as follows: roasting at 300-600 deg.c in air atmosphere for 2-12 hr.
9. The method of manufacturing according to claim 4, wherein: in step 4), the reduction conditions are: at H 2 H with concentration of 5% -50% 2 /N 2 Or H 2 Ar or pure H 2 Reducing for 0.5-10 h at 200-500 deg.C under atmosphere.
10. The catalyst for preparing methanol from carbon dioxide with high selectivity and high stability as claimed in any one of claims 1 to 3 and the catalyst prepared by the preparation method as claimed in any one of claims 5 to 9, which are applied to the reaction for preparing methanol by hydrogenation of carbon dioxide, wherein the reaction conditions are as follows: the hydrogenation reaction pressure of carbon dioxide is 5-150 bar, the reaction temperature is 180-320 ℃, H 2 With CO 2 The volume ratio of (1:9) - (9:1), the space velocity of the reaction gas is 1000-50000mL h -1 g -1 。
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04124152A (en) * | 1990-09-13 | 1992-04-24 | Agency Of Ind Science & Technol | Production of methanol by catalytic hydrogenation of carbon dioxide gas |
| CN101983765A (en) * | 2010-11-15 | 2011-03-09 | 大连理工大学 | Catalyst for preparing methyl alcohol by catalytic hydrogenation on assistant modified carbon dioxide and preparation method thereof |
| WO2012151776A1 (en) * | 2011-05-12 | 2012-11-15 | 大连理工大学 | Modified catalyst for producing methanol by catalytic hydrogenation of carbon dioxide and method for preparing same |
| CN105170151A (en) * | 2015-10-23 | 2015-12-23 | 中国科学院上海高等研究院 | Core-shell structure type copper-based catalyst as well as preparation method and application thereof |
| CN112588320A (en) * | 2020-12-28 | 2021-04-02 | 浙江工业大学 | Catalyst for synthesizing methanol by hydrogenation of hydrophobic carbon dioxide and preparation method and application thereof |
-
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- 2022-02-15 CN CN202210139341.1A patent/CN116637624A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04124152A (en) * | 1990-09-13 | 1992-04-24 | Agency Of Ind Science & Technol | Production of methanol by catalytic hydrogenation of carbon dioxide gas |
| CN101983765A (en) * | 2010-11-15 | 2011-03-09 | 大连理工大学 | Catalyst for preparing methyl alcohol by catalytic hydrogenation on assistant modified carbon dioxide and preparation method thereof |
| WO2012151776A1 (en) * | 2011-05-12 | 2012-11-15 | 大连理工大学 | Modified catalyst for producing methanol by catalytic hydrogenation of carbon dioxide and method for preparing same |
| CN105170151A (en) * | 2015-10-23 | 2015-12-23 | 中国科学院上海高等研究院 | Core-shell structure type copper-based catalyst as well as preparation method and application thereof |
| CN112588320A (en) * | 2020-12-28 | 2021-04-02 | 浙江工业大学 | Catalyst for synthesizing methanol by hydrogenation of hydrophobic carbon dioxide and preparation method and application thereof |
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