CN110327933B - Catalyst for preparing methanol by carbon dioxide hydrogenation, preparation method and application thereof - Google Patents
Catalyst for preparing methanol by carbon dioxide hydrogenation, preparation method and application thereof Download PDFInfo
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 154
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 239000003054 catalyst Substances 0.000 title claims abstract description 97
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 77
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 77
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title abstract description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 58
- 239000012065 filter cake Substances 0.000 claims abstract description 34
- 229910052751 metal Inorganic materials 0.000 claims abstract description 30
- 239000002184 metal Substances 0.000 claims abstract description 30
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 29
- 238000003756 stirring Methods 0.000 claims abstract description 28
- 239000000243 solution Substances 0.000 claims abstract description 27
- 238000001556 precipitation Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 19
- 239000012266 salt solution Substances 0.000 claims abstract description 18
- 238000001816 cooling Methods 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 15
- 238000011049 filling Methods 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 14
- 230000032683 aging Effects 0.000 claims abstract description 7
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 7
- 150000001879 copper Chemical class 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 150000003751 zinc Chemical class 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims description 21
- 239000010949 copper Substances 0.000 claims description 17
- 230000002431 foraging effect Effects 0.000 claims description 13
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 5
- 238000011065 in-situ storage Methods 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000013078 crystal Substances 0.000 abstract description 4
- 239000008367 deionised water Substances 0.000 description 18
- 229910021641 deionized water Inorganic materials 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 230000001276 controlling effect Effects 0.000 description 17
- 239000000047 product Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 150000002739 metals Chemical class 0.000 description 10
- 238000000465 moulding Methods 0.000 description 10
- 239000002243 precursor Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 8
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 8
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 8
- 239000008188 pellet Substances 0.000 description 8
- 230000001105 regulatory effect Effects 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 238000000975 co-precipitation Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000001651 catalytic steam reforming of methanol Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- -1 nitrate ions Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005303 weighing Methods 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a catalyst for preparing methanol, in particular to a catalyst for preparing methanol by carbon dioxide hydrogenation and a preparation method and application thereof. Mixing and stirring mixed metal salt solution of copper salt, zinc salt and aluminum salt and sodium carbonate solution for precipitation, aging, filtering, drying a filter cake, then placing the filter cake into a container, filling carbon dioxide gas for roasting, keeping the pressure at 2-4MPa in the roasting process, cooling and depressurizing after the roasting is finished to obtain a catalyst precursor, and forming to obtain the catalyst. The catalyst has high activity and high methanol selectivity, and under the condition of lower reaction temperature (200 ℃), the conversion rate of carbon dioxide reaches more than 25 percent, and the selectivity of methanol reaches more than 85 percent. The preparation method provided by the invention enables the crystal form of the catalyst to be converted into a crystal form which is easier to adsorb and activate carbon dioxide, thereby greatly improving the catalytic performance of the catalyst.
Description
Technical Field
The invention relates to a catalyst for preparing methanol, in particular to a catalyst for preparing methanol by carbon dioxide hydrogenation and a preparation method and application thereof.
Background
The large use of fossil fuels since the industrial revolution brought about a rapid development of the human economy, while at the same time too much CO 2 The emission also brings a series of global environmental problems of greenhouse effect, climate warming, glacier melting, climate abnormity and the like, and CO is reasonably utilized 2 As a carbon source, the carbon source can be regenerated by chemical and chemical means to form the cyclic utilization of carbon resources, which not only can reduce the dependence on the traditional fossil energy, but also has important practical significance for improving the environment and ensuring the sustainable development of human beings, wherein CO 2 The application of hydrogenation to synthesize methanol is to CO in modern society 2 One of the important ways of recycling, but with respect to CO 2 An important problem in the industrial production of methanol is the selectivity of the catalystLower ratio and poorer conversion rate.
CO 2 Most of catalysts for preparing methanol by hydrogenation are developed on the basis of catalysts for preparing methanol by CO hydrogenation, and the current reaction catalysts for preparing methanol by carbon dioxide can be roughly divided into three main groups, the first group is copper-based catalysts, and the main catalysts are Cu/ZnO/Al for example 2 O 3 、Cu/ZnO/ZrO 2 、Cu/ZnO/SiO 2 、Cu/NiO 2 /TiO 2 Etc., wherein Cu is the main active component, ZnO, NiO 2 Etc. as assistant to promote reaction, Al 2 O 3 、SiO 2 、 TiO 2 The catalyst can be used as a carrier to play a role of a framework, and can also disperse the active components of the catalyst to improve CO 2 Adsorption and conversion. The copper-based catalyst is always the focus of domestic and foreign research, and especially the addition and doping of other metals into the copper-based catalyst is always CO 2 The mainstream direction of the development and research of the catalyst for synthesizing methanol by hydrogenation is in CuO/ZnO/Al 2 O 3 The catalyst is modified by adding Ni and Fe auxiliaries, so that the activity of the catalyst can be improved, and the catalyst has better activity when the Ni content is lower and the Fe content is higher. In Cu/ZnO/Al 2 O 3 Adding B to the catalyst 2 O 3 In addition, factors such as the proportion of each component in the catalyst, the dispersity of copper, the preparation method of the catalyst, the surface appearance of the catalyst and the like also have important influence on the performance of the copper-based catalyst, the special coprecipitation method is adopted to prepare the nano Cu/Zn/Al/Zr fiber catalyst, and the nano Cu/Zn/Al/Zr fiber catalyst has the characteristics of large specific surface area, small particle size and excellent thermal stability, and after the Zr auxiliary agent is added into the catalyst, the activity of the catalyst is improved, but the activity and the selectivity of the catalyst can not meet the requirements.
The second catalyst for methanolizing carbon dioxide is a supported catalyst containing a transition metal or a noble metal (Pt, Pd, Au, Rh, etc.) as a main active component, in addition to a copper-based catalyst, because the noble metal has a strong surface H 2 Dissociation and activation capability, such goldCan be used as a catalyst for preparing methanol by carbon dioxide hydrogenation, such as Pd/SiO 2 、Pd/Al 2 O 3 、Pd/ThO 2 Etc., Solymosi et al supported Pd on SiO 2 、MgO、Al 2 O 3 The supported catalyst prepared on the oxide is applied to the carbon dioxide hydrogenation reaction, wherein the dispersion degree of Pd has a particularly obvious effect on the selectivity of the product, the main product of the reaction is methane when the dispersion degree is higher, and methanol is generated when the dispersion degree is lower, for the catalyst systems of a large amount of metals/oxides, a generalized classification is carried out on the catalyst systems by Chenjing of the national laboratory of Bruk Highui, a systematic summary is carried out on the selectivity and the yield of the catalyst systems, Liu Chi university provides a method for modifying the nano ZnS/polyaniline composite photocatalyst by introducing noble metal in the published patent of Liu Chi university, and other types of catalysts can also be used for the reaction for preparing methanol from carbon dioxide, like metal carbide is often used as a catalyst carrier due to the stable chemical property of the metal carbide. Vidal et al supported Au and Cu particles on Mo 2 C、Fe 3 C. On TaC and TiC, preparing a series of catalysts. ZnO-CrO developed by BASF and mainly containing chromium and zinc 3 Or ZnO-Cr 2 O 3 A catalyst. However, the conversion of carbon dioxide in these catalysts is still not commercially desirable.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a catalyst for preparing methanol by hydrogenating carbon dioxide, which has high activity and high methanol selectivity and has good catalytic activity at lower reaction temperature and low temperature; the invention also provides a preparation method and application thereof.
The catalyst for preparing methanol by carbon dioxide hydrogenation is prepared by mixing and stirring mixed metal salt solution of copper salt, zinc salt and aluminum salt and sodium carbonate solution for precipitation, aging, filtering, drying a filter cake, placing the filter cake in a container, filling carbon dioxide gas for roasting, keeping the pressure at 2-4MPa in the roasting process, cooling and depressurizing after roasting is finished to obtain a catalyst precursor, and forming to obtain the catalyst.
Controlling the dropping speed of the sodium carbonate solution to ensure that the pH value of a precipitation system is 8-9; the temperature for precipitation is controlled at 70-80 ℃.
The molar ratio of Cu, Zn and Al in the mixed metal salt solution is 1:0.5-1: 2.5-3.
Then carrying out aging: stirring for 2-2.5 hours for aging.
The conditions for drying the filter cake were: drying in an oven at 100-105 ℃ for 0.8-1 hour.
The roasting time is 10-12 hours, and the roasting temperature is 600-700 ℃.
The preparation method of the catalyst for preparing methanol by carbon dioxide hydrogenation comprises the following steps: preparation of CuO-ZnO-Al by coprecipitation method 2 O 3 The composite metal oxide is prepared by mixing mixed metal salt solution of copper salt, zinc salt and aluminum salt with sodium carbonate solution, stirring for precipitation, aging, filtering, drying filter cake, placing in a container, introducing carbon dioxide gas for roasting, keeping the pressure at 2-4MPa in the roasting process, cooling and depressurizing after roasting to obtain a catalyst precursor, and molding to obtain the catalyst.
As a preferred technical scheme, the preparation method of the catalyst for preparing methanol by hydrogenating carbon dioxide, provided by the invention, comprises the following steps: preparation of CuO-ZnO-Al by coprecipitation method 2 O 3 Weighing copper nitrate, zinc nitrate and aluminum nitrate with different masses, dissolving the copper nitrate, the zinc nitrate and the aluminum nitrate in deionized water, uniformly stirring, preparing a sodium carbonate solution with a certain concentration, and slightly excessive to ensure that metal ions can be completely precipitated. Mixing and stirring mixed metal salt solution of copper salt, zinc salt and aluminum salt and sodium carbonate solution for precipitation, controlling the dropping speed of sodium carbonate to ensure that the pH value of a precipitation system is 8-9, controlling the temperature of the precipitation system to be 70-80 ℃, then stirring for 2-2.5 hours for aging, filtering, drying a filter cake, then placing the filter cake into a container, filling carbon dioxide gas for roasting, roasting at the temperature of 600-700 ℃, keeping the pressure at 2-4MPa in the roasting process, roasting for 10-12 hours, cooling and depressurizing after the roasting is finished to obtain a catalyst precursor, and forming to obtain the catalyst.
Preferably, the mixed metal salt solution and the sodium carbonate solution are simultaneously dripped into a round-bottom flask, the mixture is fully stirred, the temperature of the system is controlled to be 70-80 ℃, the pH value is 8-9, the mixture is continuously stirred for 2-2.5 hours after complete precipitation for aging, then the mixture is filtered, the filter cake is fully and repeatedly washed by deionized water, nitrate ions and sodium ions remained in the filter cake are removed as far as possible, the filter cake is dried in an oven at 105 ℃ for 0.8-1 hour, the obtained product is placed in a pressure-bearing container, carbon dioxide gas is filled in the pressure-bearing container, roasting is carried out at 600-700 ℃, in the roasting process, the pressure in the pressure-bearing container is adjusted by a pressure adjusting valve, the pressure is kept at 2-4MPa, the roasting is carried out for 10-12 hours, the temperature and the pressure are reduced to obtain a precursor of the catalyst for preparing the methanol by carbon dioxide hydrogenation, and the catalyst is obtained after molding.
The main problem of the carbon dioxide hydrogenation reaction is the adsorption and activation of carbon dioxide, which is different from carbon monoxide, and carbon dioxide has a stable structure and is not easy to chemically adsorb with a carrier and be activated, so that to improve the catalytic activity of the catalyst, the microstructure of the catalyst is required to be more easy to chemically adsorb with carbon dioxide and be activated into an intermediate adsorption state in which the hydrogenation reaction is easy to occur. Depending on how the microstructure of the support, the auxiliary agent and the active centre is constructed with a high capacity for adsorbing carbon dioxide. The invention adopts a coprecipitation method to prepare CuO-ZnO-Al 2 O 3 The composite metal oxide is prepared by introducing high-pressure carbon dioxide atmosphere in the process of roasting the precursor, so that the prepared metal oxide has a carbon dioxide-philic crystal form, the chemical adsorption capacity of the composite metal oxide on carbon dioxide is improved, and the conversion rate of carbon dioxide is improved.
The application of the catalyst for preparing methanol by carbon dioxide hydrogenation comprises the following steps: before the carbon dioxide hydrogenation reaction is carried out, introducing normal-pressure hydrogen into the catalyst in a reactor, carrying out in-situ reduction at 280-320 ℃, then introducing 3-3.5:1 of mixed gas of carbon dioxide and hydrogen, and carrying out the carbon dioxide hydrogenation reaction at 180-200 ℃ and 1.8-2.2 MPa.
Preferably, before the carbon dioxide hydrogenation reaction is carried out, normal pressure hydrogen is introduced into the catalyst in a reactor, the catalyst is reduced in situ for 3 hours at 300 ℃, then a mixed gas of carbon dioxide and hydrogen with the ratio of 3:1 is introduced, and the carbon dioxide hydrogenation reaction is carried out at 200 ℃ and 2.0 MPa.
Compared with the prior art, the invention has the following advantages:
(1) the catalyst for preparing methanol by carbon dioxide hydrogenation has high activity and high methanol selectivity, and the volume space velocity is 2000-3000h -1 The catalyst has good catalytic activity at a low reaction temperature and a low temperature, the carbon dioxide conversion rate reaches over 25 percent and the selectivity of methanol reaches over 85 percent at the low reaction temperature (200 ℃).
(2) The preparation method provided by the invention uses the high-pressure carbon dioxide to modify the catalyst in the roasting process, so that the crystal form of the catalyst is converted to the form which is easier to adsorb and activate the carbon dioxide, thereby greatly improving the catalytic performance of the catalyst.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
241.6 g of copper nitrate trihydrate, 148.7 g of zinc nitrate hexahydrate and 1775.5 g of aluminum nitrate nonahydrate are weighed and dissolved in 10000 g of deionized water, the molar ratio of the three metals is 1:0.5:2.5, the mixture is uniformly stirred, and 5% of sodium carbonate solution is prepared to be completely precipitated. Simultaneously dripping a mixed metal salt solution and a sodium carbonate solution into a round-bottom flask, fully stirring, controlling the temperature of a system to be 70 ℃, controlling the pH value to be 8, continuously stirring for 2 hours for aging after complete precipitation, then filtering, washing a filter cake with deionized water until the pH value of effluent is 7, drying the filter cake in an oven at 105 ℃ for 1 hour, placing an obtained product into a pressure-bearing container, filling carbon dioxide gas into the pressure-bearing container, roasting at 600 ℃, regulating the pressure in the pressure-bearing container through a pressure regulating valve in the roasting process, keeping the pressure at 2MPa, roasting for 10 hours, cooling and reducing the pressure to obtain a precursor of the catalyst for preparing methanol by carbon dioxide hydrogenation. The catalyst was obtained by molding into columnar pellets having a diameter of 2.5mm and a length of 3 mm.
Example 2
241.6 g of copper nitrate trihydrate, 148.7 g of zinc nitrate hexahydrate and 1775.5 g of aluminum nitrate nonahydrate are weighed and dissolved in 10000 g of deionized water, the molar ratio of the three metals is 1:0.5:2.5, the mixture is uniformly stirred, and 5% of sodium carbonate solution is prepared to be completely precipitated. Simultaneously dripping mixed metal salt solution and sodium carbonate solution into a round-bottom flask, fully stirring, controlling the temperature of a system to be 80 ℃, controlling the pH to be 9, continuously stirring for 2 hours for aging after complete precipitation, then filtering, washing a filter cake with deionized water until the pH of effluent is 7, drying the filter cake in an oven at 105 ℃ for 1 hour, placing an obtained product into a pressure-bearing container, filling carbon dioxide gas into the pressure-bearing container, roasting at 700 ℃, regulating the pressure in the pressure-bearing container through a pressure regulating valve in the roasting process, keeping the pressure at 4MPa, roasting for 12 hours, cooling and reducing the pressure to obtain a precursor of the catalyst for preparing methanol by carbon dioxide hydrogenation. The catalyst was obtained by molding into columnar pellets having a diameter of 2.5mm and a length of 3 mm.
Example 3
241.6 g of copper nitrate trihydrate, 297.4 g of zinc nitrate hexahydrate and 2130.6 g of aluminum nitrate nonahydrate are weighed and dissolved in 10000 g of deionized water, the molar ratio of the three metals is 1:1:3, the mixture is stirred uniformly, and 5% of sodium carbonate solution is prepared to be completely precipitated. Simultaneously dripping mixed metal salt solution and sodium carbonate solution into a round-bottom flask, fully stirring, controlling the temperature of a system at 80 ℃, controlling the pH value at 8, continuously stirring for 2 hours for aging after complete precipitation, then filtering, washing a filter cake with deionized water until the pH value of effluent is 7, drying the filter cake in an oven at 105 ℃ for 1 hour, placing an obtained product into a pressure-bearing container, filling carbon dioxide gas into the pressure-bearing container, roasting at 600 ℃, regulating the pressure in the pressure-bearing container through a pressure regulating valve in the roasting process, keeping the pressure at 2MPa, roasting for 12 hours, cooling and reducing the pressure to obtain a precursor of the catalyst for preparing methanol by carbon dioxide hydrogenation. The catalyst was obtained by molding into columnar pellets having a diameter of 2.5mm and a length of 3 mm.
Example 4
241.6 g of copper nitrate trihydrate, 297.4 g of zinc nitrate hexahydrate and 2130.6 g of aluminum nitrate nonahydrate are weighed and dissolved in 10000 g of deionized water, the molar ratio of the three metals is 1:1:3, the mixture is uniformly stirred, and 5% of sodium carbonate solution is prepared to be completely precipitated. Simultaneously dripping mixed metal salt solution and sodium carbonate solution into a round-bottom flask, fully stirring, controlling the temperature of a system to be 80 ℃, controlling the pH to be 9, continuously stirring for 2 hours for aging after complete precipitation, then filtering, washing a filter cake with deionized water until the pH of effluent is 7, drying the filter cake in an oven at 105 ℃ for 1 hour, placing an obtained product into a pressure-bearing container, filling carbon dioxide gas into the pressure-bearing container, roasting at 700 ℃, regulating the pressure in the pressure-bearing container through a pressure regulating valve in the roasting process, keeping the pressure at 4MPa, roasting for 10 hours, cooling and reducing the pressure to obtain a precursor of the catalyst for preparing methanol by carbon dioxide hydrogenation. The catalyst was obtained by molding into columnar pellets having a diameter of 2.5mm and a length of 3 mm.
Comparative example 1
241.6 g of copper nitrate trihydrate, 148.7 g of zinc nitrate hexahydrate and 1775.5 g of aluminum nitrate nonahydrate are weighed and dissolved in 10000 g of deionized water, the molar ratio of the three metals is 1:0.5:2.5, the mixture is uniformly stirred, and 5% of sodium carbonate solution is prepared to be completely precipitated. Simultaneously dripping mixed metal salt solution and sodium carbonate solution into a round-bottom flask, fully stirring, controlling the temperature of the system at 70 ℃ and the pH value at 8, continuously stirring for 2 hours for aging after complete precipitation, then filtering, washing a filter cake with deionized water until the pH value of effluent is 7, drying the filter cake in an oven at 105 ℃ for 1 hour, placing the obtained product into a pressure-bearing container, filling carbon dioxide gas into the pressure-bearing container, roasting at 600 ℃, roasting in the atmosphere of atmospheric air, roasting for 10 hours, and cooling to obtain a precursor of the catalyst for preparing methanol by carbon dioxide hydrogenation. The catalyst was obtained by molding into columnar pellets having a diameter of 2.5mm and a length of 3 mm.
Comparative example 2
241.6 g of copper nitrate trihydrate, 148.7 g of zinc nitrate hexahydrate and 1775.5 g of aluminum nitrate nonahydrate are weighed and dissolved in 10000 g of deionized water, the molar ratio of the three metals is 1:0.5:2.5, the mixture is uniformly stirred, and 5% of sodium carbonate solution is prepared to be completely precipitated. Simultaneously dripping a mixed metal salt solution and a sodium carbonate solution into a round-bottom flask, fully stirring, controlling the temperature of the system to be 80 ℃, controlling the pH value to be 9, continuously stirring for 2 hours after complete precipitation for aging, then filtering, washing a filter cake with deionized water until the pH value of effluent is 7, drying the filter cake in an oven at 105 ℃ for 1 hour, placing an obtained product into a pressure-bearing container, filling carbon dioxide gas into the container, roasting at 700 ℃, roasting in an atmospheric air atmosphere, roasting for 12 hours, and cooling to obtain a precursor of the catalyst for preparing methanol by carbon dioxide hydrogenation. The catalyst was obtained by molding into columnar pellets having a diameter of 2.5mm and a length of 3 mm.
Comparative example 3
241.6 g of copper nitrate trihydrate, 297.4 g of zinc nitrate hexahydrate and 2130.6 g of aluminum nitrate nonahydrate are weighed and dissolved in 10000 g of deionized water, the molar ratio of the three metals is 1:1:3, the mixture is uniformly stirred, and 5% of sodium carbonate solution is prepared to be completely precipitated. Simultaneously dripping a mixed metal salt solution and a sodium carbonate solution into a round-bottom flask, fully stirring, controlling the temperature of a system at 80 ℃, controlling the pH value at 8, continuously stirring for 2 hours for aging after complete precipitation, then filtering, washing a filter cake with deionized water until the pH value of effluent is 7, drying the filter cake in an oven at 105 ℃ for 1 hour, placing an obtained product into a pressure-bearing container, filling carbon dioxide gas into the pressure-bearing container, roasting at 600 ℃, roasting in an atmosphere of atmospheric air, roasting for 12 hours, and cooling to obtain a precursor of the catalyst for preparing methanol by carbon dioxide hydrogenation. The catalyst was obtained by molding into columnar pellets having a diameter of 2.5mm and a length of 3 mm.
Comparative example 4
241.6 g of copper nitrate trihydrate, 297.4 g of zinc nitrate hexahydrate and 2130.6 g of aluminum nitrate nonahydrate are weighed and dissolved in 10000 g of deionized water, the molar ratio of the three metals is 1:1:3, the mixture is uniformly stirred, and 5% of sodium carbonate solution is prepared to be completely precipitated. Simultaneously dripping a mixed metal salt solution and a sodium carbonate solution into a round-bottom flask, fully stirring, controlling the temperature of a system to be 80 ℃ and the pH value to be 9, continuously stirring for 2 hours for aging after complete precipitation, then filtering, washing a filter cake with deionized water until the pH value of effluent is 7, drying the filter cake in an oven at 105 ℃ for 1 hour, placing an obtained product into a pressure-bearing container, filling carbon dioxide gas into the pressure-bearing container, roasting at 700 ℃, roasting in an atmosphere of atmospheric air, roasting for 10 hours, and cooling to obtain a precursor of the catalyst for preparing methanol by carbon dioxide hydrogenation. The catalyst was obtained by molding into columnar pellets having a diameter of 2.5mm and a length of 3 mm.
Comparative example 5
Comparative example 5 was prepared in the same manner as example 1, with the only difference that: the pressure of carbon dioxide gas during calcination was 10 MPa.
Comparative example 6
Comparative example 6 was prepared in the same manner as example 1, with the only difference that: the pressure of carbon dioxide gas during calcination was 0.5 MPa.
And (3) performance testing:
respectively loading the catalysts prepared in examples 1-4 and comparative examples 1-6 into a fixed bed reactor, introducing normal pressure hydrogen into the reactor, reducing in situ for 3 hours at 300 ℃, then introducing a mixed gas of carbon dioxide and hydrogen with the volume of 3:1, wherein the volume space velocity is 3000h -1 The carbon dioxide hydrogenation reaction is carried out at 200 ℃ and 2.0 MPa. The product was collected and decomposed, and the results are shown in Table 1.
TABLE 1 evaluation results of methanol steam reforming experiment
As can be seen from the data in the table, the catalyst obtained by roasting in the carbon dioxide atmosphere has obviously higher catalytic activity and selectivity than the catalyst obtained by roasting in the common method. Too high and too low a pressure of the atmosphere of the calcined carbon dioxide are also detrimental to the catalyst performance.
Claims (8)
1. A catalyst for preparing methanol by carbon dioxide hydrogenation is characterized in that: mixing and stirring mixed metal salt solutions of copper salt, zinc salt and aluminum salt and a sodium carbonate solution for precipitation, then aging, filtering, drying a filter cake, then placing the filter cake into a container, filling carbon dioxide gas for roasting, keeping the pressure at 2-4MPa in the roasting process, cooling and depressurizing after the roasting is finished to obtain a catalyst precursor, and forming to obtain a catalyst;
the molar ratio of Cu, Zn and Al in the mixed metal salt solution is 1:0.5-1: 2.5-3;
the roasting time is 10-12 hours;
controlling the dropping speed of the sodium carbonate solution to ensure that the pH value of the precipitation system is 8-9.
2. The catalyst for preparing methanol by hydrogenating carbon dioxide according to claim 1, wherein: the temperature for precipitation is controlled at 70-80 ℃.
3. The catalyst for preparing methanol by hydrogenating carbon dioxide according to claim 1, wherein: then carrying out aging: stirring for 2-2.5 hours for aging.
4. The catalyst for preparing methanol by hydrogenating carbon dioxide according to claim 1, wherein: the conditions for drying the filter cake were: drying in an oven at 100-105 ℃ for 0.8-1 h.
5. The catalyst for preparing methanol by hydrogenating carbon dioxide according to claim 1, wherein: the roasting temperature is 600-700 ℃.
6. A method for preparing a catalyst for preparing methanol by hydrogenating carbon dioxide according to any one of claims 1 to 5, wherein: mixing and stirring mixed metal salt solution of copper salt, zinc salt and aluminum salt and sodium carbonate solution for precipitation, aging, filtering, drying a filter cake, then placing the filter cake into a container, filling carbon dioxide gas for roasting, keeping the pressure at 2-4MPa in the roasting process, cooling and depressurizing after the roasting is finished to obtain a catalyst precursor, and forming to obtain the catalyst.
7. The method for preparing a catalyst for preparing methanol by hydrogenating carbon dioxide according to claim 6, wherein: mixing and stirring mixed metal salt solutions of copper salt, zinc salt and aluminum salt and a sodium carbonate solution for precipitation, controlling the dropping speed of sodium carbonate to ensure that the pH value of a precipitation system is 8-9, controlling the temperature of the precipitation system to be 70-80 ℃, then stirring for 2-2.5 hours for aging, filtering, drying a filter cake, then placing the filter cake into a container, filling carbon dioxide gas for roasting, roasting at 600-700 ℃, keeping the pressure at 2-4MPa in the roasting process, roasting for 10-12 hours, cooling and depressurizing after the roasting is finished to obtain a catalyst precursor, and forming to obtain the catalyst.
8. Use of a catalyst for the hydrogenation of carbon dioxide to methanol according to any one of claims 1 to 5, wherein: before the carbon dioxide hydrogenation reaction is carried out, normal pressure hydrogen is introduced into the catalyst in a reactor, in-situ reduction is carried out at the temperature of 280-320 ℃, then mixed gas of carbon dioxide and hydrogen with the ratio of 3-3.5:1 is introduced, and the carbon dioxide hydrogenation reaction is carried out at the temperature of 180-200 ℃ and the pressure of 1.8-2.2 MPa.
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| CN111389401B (en) * | 2020-03-27 | 2021-07-23 | 北京化工大学 | For the efficient catalytic conversion of CO2Preparation method of microorganism coupling catalytic system |
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| CN113856688B (en) * | 2021-11-16 | 2023-11-10 | 扬州大学 | For CO 2 Preparation method of Cu-based catalyst for preparing methanol by hydrogenation |
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| CN114849718A (en) * | 2022-05-17 | 2022-08-05 | 山东亮剑环保新材料有限公司 | Rare earth doped CO 2 Preparation method of hydrogenation composite catalyst |
| CN116173959A (en) * | 2022-12-12 | 2023-05-30 | 陕西科技大学 | Reverse ZrO 2 -Co catalyst and catalytic Co thereof 2 Hydrogenation synthesis C 5+ Use of alkanes |
| CN117282432B (en) * | 2023-08-28 | 2024-06-18 | 中国科学院大连化学物理研究所 | Catalyst for synthesizing green methanol by biomass gasification coupling renewable energy source hydrogen production and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1036711A (en) * | 1988-03-04 | 1989-11-01 | 纳幕尔杜邦公司 | The carbon dioxide roasting of preparing copper bearing methanol dissociation catalysts |
| US5106810A (en) * | 1989-06-29 | 1992-04-21 | E. I. Du Pont De Nemours And Company | Methanol dissociation catalysts |
| CN101530803A (en) * | 2009-04-08 | 2009-09-16 | 太原理工大学 | Method for preparing catalyst for methanol synthesis in slurry reactor and application thereof |
| WO2012040977A1 (en) * | 2010-09-29 | 2012-04-05 | 大连理工大学 | Catalyst for catalytically hydrogenating co2 to methanol and preparation thereof |
| CN104096566A (en) * | 2013-04-12 | 2014-10-15 | 中国石油化工股份有限公司 | Method for preparing copper series methanol synthesis catalyst through precipitation-impregnation process |
-
2019
- 2019-07-25 CN CN201910675995.4A patent/CN110327933B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1036711A (en) * | 1988-03-04 | 1989-11-01 | 纳幕尔杜邦公司 | The carbon dioxide roasting of preparing copper bearing methanol dissociation catalysts |
| US5106810A (en) * | 1989-06-29 | 1992-04-21 | E. I. Du Pont De Nemours And Company | Methanol dissociation catalysts |
| CN101530803A (en) * | 2009-04-08 | 2009-09-16 | 太原理工大学 | Method for preparing catalyst for methanol synthesis in slurry reactor and application thereof |
| WO2012040977A1 (en) * | 2010-09-29 | 2012-04-05 | 大连理工大学 | Catalyst for catalytically hydrogenating co2 to methanol and preparation thereof |
| CN104096566A (en) * | 2013-04-12 | 2014-10-15 | 中国石油化工股份有限公司 | Method for preparing copper series methanol synthesis catalyst through precipitation-impregnation process |
Non-Patent Citations (1)
| Title |
|---|
| CO2制备甲醇催化剂研究进展;韩睿 等;《工业催化》;20150930;第23卷(第9期);第678页左栏第2-6段 * |
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