CN113842914B - Catalyst for synthesizing methanol from carbon dioxide, and preparation method and application thereof - Google Patents
Catalyst for synthesizing methanol from carbon dioxide, and preparation method and application thereof Download PDFInfo
- Publication number
- CN113842914B CN113842914B CN202111273325.3A CN202111273325A CN113842914B CN 113842914 B CN113842914 B CN 113842914B CN 202111273325 A CN202111273325 A CN 202111273325A CN 113842914 B CN113842914 B CN 113842914B
- Authority
- CN
- China
- Prior art keywords
- salt
- reaction
- mixed solution
- crystallization
- controlling
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 132
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 35
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 35
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 156
- 238000001556 precipitation Methods 0.000 claims description 112
- 238000002425 crystallisation Methods 0.000 claims description 105
- 230000008025 crystallization Effects 0.000 claims description 105
- 239000011259 mixed solution Substances 0.000 claims description 90
- 150000003839 salts Chemical class 0.000 claims description 80
- 230000032683 aging Effects 0.000 claims description 56
- 239000002243 precursor Substances 0.000 claims description 37
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 36
- 239000004202 carbamide Substances 0.000 claims description 36
- 239000010949 copper Substances 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 26
- 238000005406 washing Methods 0.000 claims description 21
- 239000011701 zinc Substances 0.000 claims description 20
- 238000001914 filtration Methods 0.000 claims description 13
- 238000005984 hydrogenation reaction Methods 0.000 claims description 13
- 235000019441 ethanol Nutrition 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 239000010936 titanium Substances 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 10
- 239000012295 chemical reaction liquid Substances 0.000 claims description 9
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical group [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical group [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 3
- 238000011282 treatment Methods 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical group [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 description 64
- 230000001276 controlling effect Effects 0.000 description 44
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 14
- 235000011114 ammonium hydroxide Nutrition 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 238000011156 evaluation Methods 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 230000002431 foraging effect Effects 0.000 description 11
- 239000011521 glass Substances 0.000 description 11
- 230000001105 regulatory effect Effects 0.000 description 11
- 238000001035 drying Methods 0.000 description 10
- 238000000227 grinding Methods 0.000 description 10
- 238000012216 screening Methods 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910002535 CuZn Inorganic materials 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical group [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- -1 formaldehyde, olefin Chemical class 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000002572 peristaltic effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012360 testing method 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/60—Platinum group metals 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
- C07C29/156—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 iron group metals, platinum group metals 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
Landscapes
- 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
The invention relates to a catalyst for synthesizing methanol by carbon dioxide, a preparation method and application thereof, and the catalyst provided by the invention comprises the following components in percentage by mass: 45% -75% of CuO, 15% -40% of ZnO and Fe 2 O 3 4％‑30％、TiO 2 5% -30%. The catalyst provided by the invention can effectively improve the selectivity and heat resistance of methanol.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a catalyst for synthesizing methanol from carbon dioxide, a preparation method and application thereof.
Background
In recent years, along with the acceleration of industrialization progress, the excessive exploitation and utilization of fossil energy sources cause a large amount of carbon dioxide emission, environmental problems caused by global greenhouse effect are increasingly prominent, the capture and comprehensive utilization of carbon dioxide are also receiving more and more attention, and the utilization of carbon dioxide to convert the carbon dioxide into resources with high added value is an effective way for solving the environmental problems and the energy problems.
At present, most researches are carried out on the aspect of carbon dioxide utilization, namely, the carbon dioxide is converted into methanol through catalytic hydrogenation, renewable energy sources such as solar energy, wind energy and biomass are coupled through carbon dioxide hydrogenation reaction, and the renewable energy sources are a green and sustainable synthetic way of liquid fuels such as methanol and gasoline, and are an important ring of recycling economy including 'liquid sunlight' and 'methanol economy'. Methanol is a high-efficiency hydrogen storage material, and has the advantages of high energy density, low hydrogen storage cost and the like compared with other hydrogen storage materials under the condition of normal temperature and normal pressure. In addition, methanol is also an important chemical basic raw material, can be used for synthesizing chemical products with higher added values such as formic acid, formaldehyde, olefin, aromatic hydrocarbon and the like, particularly for preparing end products such as polypropylene, polyethylene and the like by using methanol, can be applied to daily production and life of people, relieves energy consumption in petrochemical industry, and is the most effective way for realizing carbon neutralization.
The catalyst for the hydrogenation conversion of carbon dioxide into methanol is mostly developed on the basis of the hydrogenation conversion of carbon monoxide into methanol, and mainly comprises a copper-based catalyst, a catalyst supported by taking noble metals as main active components, and the like. Optimization of catalyst performance through variations in catalyst composition, as well as variations in preparation methods, is a direction of effort by researchers.
The general copper-based catalyst has the advantages of uniform component dispersion, small particle size, large specific surface area and strong synergy between the active component and the auxiliary agent, but the preparation method is more complicated, the precipitation steps are more, and the industrial amplification is not easy. The copper-based catalyst is also a water gas shift reaction, so that a large amount of byproduct carbon monoxide is generated in the reaction of synthesizing the methanol from the carbon dioxide, and the selectivity of the methanol is reduced; and copper-based catalysts have poor heat resistance and cannot raise the catalytic reaction temperature.
Disclosure of Invention
The invention aims to solve the technical problems of poor heat resistance, low methanol selectivity and the like of the existing methanol synthesis catalyst by providing a catalyst for synthesizing methanol through carbon dioxide hydrogenation and a preparation method thereof.
The invention provides a catalyst for synthesizing methanol from carbon dioxide, which comprises the following components in percentage by mass: 45% -75% of CuO, 15% -40% of ZnO and Fe 2 O 3 4％-30％、TiO 2 5％-30％。
Preferably, the preparation method of the catalyst for synthesizing methanol by using carbon dioxide comprises the following steps:
1) Preparing a CuZnFeTi precursor;
2) And roasting the CuZnFeTi precursor to obtain the catalyst for synthesizing methanol by using carbon dioxide.
Preferably, the preparation of the CuZnFeTi precursor comprises the following steps:
step 1, mixing Cu salt, zn salt, fe salt, ti salt, urea and an organic alcohol solvent to obtain a mixed solution, and then carrying out crystallization precipitation reaction on the mixed solution;
and step 2, after the crystallization and precipitation reaction is finished, aging treatment, filtering and washing are carried out on the reaction mixed solution to obtain the CuZnFeTi precursor.
Preferably, in the step 1, the molar ratio of Cu salt, zn salt, fe salt, ti salt and urea is (0.15-0.85): (0.05-0.45): (0.02-0.2): (0.02-0.35): (0.1-1.4);
the concentration of Cu salt in the mixed solution in the step 1 is 0.15-0.85mol/L, the concentration of Zn salt is 0.05-0.45mol/L, the concentration of Fe salt is 0.02-0.2mol/L, the concentration of Ti salt is 0.02-0.35mol/L, and the concentration of urea is 0.1-1.4mol/L.
Preferably, the preparation of the CuZnFeTi precursor comprises the following steps:
s1, mixing urea, ti salt and an organic alcohol solvent to obtain a first mixed solution, and then carrying out a first crystallization precipitation reaction on the first mixed solution; s2, mixing Cu salt, zn salt, fe salt, urea and an organic alcohol solvent to obtain a second mixed solution, adding the second mixed solution into a reaction solution of the first crystallization precipitation reaction to perform a second crystallization precipitation reaction, and aging, filtering and washing the reaction mixed solution after the second crystallization precipitation reaction is finished to obtain the CuZnFeTi precursor.
Preferably, the molar ratio of urea to Ti salt in step S1 is (0.01-1.4): (0.02-0.35), wherein the concentration of urea in the first mixed solution is 0.01-1.4mol/L, and the concentration of Ti salt is 0.02-0.35mol/L;
in the step S2, the mol ratio of Cu salt, zn salt, fe salt and urea is (0.15-0.85): (0.05-0.45): (0.02-0.2): (0.1-1.4), the concentration of Cu salt in the second mixed solution is 0.15-0.85mol/L, the concentration of Zn salt is 0.05-0.45mol/L, the concentration of Fe salt is 0.02-0.2mol/L, and the concentration of urea is 0.1-1.4mol/L.
Preferably, the preparation of the CuZnFeTi precursor comprises the following steps:
a. mixing urea, ti salt and an organic alcohol solvent to obtain a third mixed solution, and then carrying out a first crystallization precipitation reaction on the third mixed solution;
b. mixing Cu salt, zn salt, fe salt, urea and an organic alcohol solvent to obtain a fourth mixed solution, and then carrying out a second crystallization precipitation reaction on the fourth mixed solution;
c. and mixing the reaction mixed solution of the first crystallization precipitation reaction and the reaction mixed solution of the second crystallization precipitation reaction to obtain a fifth mixed solution, aging the fifth mixed solution, filtering and washing to obtain the CuZnFeTi precursor.
Preferably, the molar ratio of urea to Ti salt in step a is (0.01-1.4): (0.02-0.35), wherein the concentration of urea in the third mixed solution is 0.01-1.4mol/L, and the concentration of Ti salt is 0.02-0.35mol/L;
in the step b, the molar ratio of Cu salt, zn salt, fe salt and urea is (0.15-0.85): (0.05-0.45): (0.02-0.2): (0.1-1.4), the concentration of Cu salt in the fourth mixed solution is 0.15-0.85mol/L, the concentration of Zn salt is 0.05-0.45mol/L, the concentration of Fe salt is 0.02-0.2mol/L, and the concentration of urea is 0.1-1.4mol/L.
Preferably, in the step 1, the pH value of the reaction solution is controlled to be 7-8.5 during the crystallization and precipitation reaction, the temperature of the crystallization and precipitation reaction is 100-120 ℃, the reaction pressure is 1.0-3.0MPa, the reaction time is 8-24h, the aging temperature in the step 2 is 60-150 ℃, and the aging time is 0.5-2.5h;
controlling the pH value of the reaction liquid to be 7-8.5 during the first crystallization and precipitation reaction in the step S1, controlling the temperature of the first crystallization and precipitation reaction to be 100-120 ℃, controlling the reaction pressure to be 1.0-3.0MPa, controlling the reaction time to be 8-24h, controlling the pH value of the reaction liquid to be 7-8.5 during the second crystallization and precipitation reaction in the step S2, controlling the temperature of the second crystallization and precipitation reaction to be 100-120 ℃, controlling the reaction pressure to be 1.0-3.0MPa, controlling the reaction time to be 8-24h, and controlling the aging temperature to be 60-150 ℃ and the aging time to be 0.5-2.5h;
controlling the pH value of the reaction liquid to 7-8.5 during the first crystallization and precipitation reaction in the step a, controlling the temperature of the first crystallization and precipitation reaction to 100-120 ℃, controlling the reaction pressure to 1.0-3.0MPa, controlling the reaction time to 8-24h, controlling the pH value of the reaction liquid to 7-8.5 during the second crystallization and precipitation reaction in the step b, controlling the temperature of the second crystallization and precipitation reaction to 100-120 ℃, controlling the reaction pressure to 1.0-3.0MPa, controlling the reaction time to 8-24h, and controlling the aging temperature to 60-150 ℃ and the aging time to 0.5-2.5h in the step c;
the washing is finished, and the washing product is dried at 80-150 ℃ for 12-24 hours;
the roasting temperature is 400-600 ℃, and the roasting time is 4-12h;
the organic alcohol solvent is absolute ethyl alcohol;
the Cu salt is selected from copper nitrate and/or copper acetate, the Zn salt is selected from zinc nitrate and/or zinc acetate, the Fe salt is selected from ferric nitrate and/or ferric acetate, and the Ti salt is selected from one or more of titanium tetrachloride, butyl titanate, titanium isopropoxide and titanyl sulfate.
The invention also provides an application of the catalyst or the catalyst prepared by the preparation method in the reaction of synthesizing methanol by hydrogenating carbon dioxide.
The beneficial effects are that:
1. the catalyst for synthesizing methanol from carbon dioxide provided by the invention comprises the following components in percentage by mass: 45% -75% of CuO, 15% -40% of ZnO and Fe 2 O 3 4％-30％、TiO 2 5% -30%. The invention utilizes TiO 2 The modified CuZn catalyst system can inhibit the generation of CO in the water gas shift reaction, regulate the surface acidity of the catalyst, inhibit carbon deposition of the catalyst and improve the selectivity of methanol; the catalyst system introduces Fe metal, not only can cooperate with the interaction of Cu and Zn between CuZn catalysts, but also can generate hydrotalcite structures, and the aged and roasted catalyst has more uniform dispersion of active components, higher activity and better heat resistance.
2. The invention provides the dioxideThe preparation method of the catalyst for synthesizing methanol by carbon provides a high-temperature and high-pressure environment for growth and aggregation of crystal grains in the precipitation reaction process, and forms stable CuFe, znFe hydrotalcite structure and CuZnFe hydrotalcite-like compound; and TiO generated under the process conditions 2 The carrier grains are finer and distributed more uniformly. By incorporating the amphoteric oxide TiO 2 TiO is used as a carrier 2 The modified CuZn catalyst system can inhibit the generation of CO in the water gas shift reaction, regulate the surface acidity of the catalyst, inhibit carbon deposition of the catalyst and improve the selectivity of methanol; the introduction of Fe metal improves the dispersity of the active components, not only can cooperate with the interaction of Cu and Zn between CuZn catalysts, but also can generate hydrotalcite structure, thereby being beneficial to cooperating with the chemical acting force between the active components and the carrier, improving the surface dispersity of the catalyst, improving the methanol selectivity of the catalyst, and being more beneficial to improving the heat resistance and the carbon deposition resistance of the catalyst.
Detailed Description
Example 1:
the embodiment provides a preparation method of a catalyst for synthesizing methanol by hydrogenation of carbon dioxide, which comprises the following steps:
20g of Cu (NO) 3 ) 2 ·3H 2 O, 18g of Zn (NO) 3 ) 2 ·6H 2 O, 4g of Fe (NO) 3 )3·9H 2 O, 4g TiCl 4 Mixing 11.95g of urea and 500ml of absolute ethyl alcohol to obtain a mixed solution, mechanically stirring the mixed solution at room temperature for 100min, and transferring the mixed solution into a high-temperature high-pressure stirring kettle for crystallization and precipitation reaction; regulating stirring rotation speed to 400r/min, controlling the center temperature of the high-temperature high-pressure stirring kettle to be 110 ℃, controlling the reaction pressure to be 2.0MPa, and carrying out crystallization precipitation reaction for 24h; during the crystallization and precipitation reaction, 0.10mol/L ammonia water is added to adjust the pH value of the crystallization and precipitation reaction to 8.5.
After the crystallization and precipitation reaction is finished, all the mixed solution is transferred into a glass flask and is placed into a microwave heating furnace for aging, wherein the aging temperature is 150 ℃, and the aging time is 0.5h. And filtering and washing to neutrality by using deionized water after the aging is finished, and obtaining the CuZnFeTi precursor.
And (3) placing the obtained CuZnFeTi precursor in an oven, drying at 120 ℃ for 12 hours, placing in a muffle furnace, roasting at 450 ℃ for 6 hours to obtain the CuZnFeTi catalyst, crushing, grinding and screening by 20-40 meshes for evaluating the reaction.
Example 2:
the embodiment provides a preparation method of a catalyst for synthesizing methanol by hydrogenation of carbon dioxide, which comprises the following steps:
40g of Cu (NO) 3 ) 2 3H 2 O, 20g of Zn (NO) 3 ) 2 ·6H 2 O, 6g of Fe (NO) 3 ) 3 ·9H 2 O, 5g TiOSO 4 Mixing 19.08g of urea and 500ml of absolute ethyl alcohol to obtain a mixed solution, mechanically stirring the mixed solution at room temperature for 60min, and transferring the mixed solution into a high-temperature high-pressure stirring kettle for crystallization and precipitation reaction; regulating the stirring rotation speed to 300r/min, controlling the center temperature of the high-temperature high-pressure stirring kettle to be 120 ℃, controlling the reaction pressure to be 1.5MPa, and carrying out crystallization precipitation reaction for 12h; during the crystallization and precipitation reaction, 0.10mol/L ammonia water is added to adjust the pH value of the crystallization and precipitation reaction to 7.5.
After the crystallization and precipitation reaction is finished, all the mixed solution is transferred into a glass flask and is placed into a microwave heating furnace for aging, wherein the aging temperature is 150 ℃, and the aging time is 1h. And filtering and washing to neutrality by using deionized water after the aging is finished, and obtaining the CuZnFeTi precursor.
And (3) placing the obtained CuZnFeTi precursor in an oven, drying at 120 ℃ for 24 hours, then placing in a muffle furnace, roasting at 600 ℃ for 6 hours to obtain the CuZnFeTi catalyst, crushing, grinding and screening by 20-40 meshes for evaluation.
Example 3:
the embodiment provides a preparation method of a catalyst for synthesizing methanol by hydrogenation of carbon dioxide, which comprises the following steps:
1.74g of CO (NH) 2 ) 2 5g TiCl 4 Mixing with 200ml absolute ethyl alcohol to obtain a first mixed solution, mechanically stirring the first mixed solution at room temperature for 100min, uniformly stirring, and then completely transferring into a high-temperature high-pressure stirring kettle for crystallization and precipitation reactionAdjusting the stirring rotation speed to 300r/min, controlling the central temperature of the high-temperature high-pressure stirring kettle to be 100 ℃, controlling the reaction pressure to be 1.0MPa, performing crystallization and precipitation reaction for 8h, and adding 0.10mol/L ammonia water to adjust the pH value of the precipitation reaction to 7.5.
50g of Cu (NO) 3 ) 2 ·3H 2 O, 18g of Zn (NO) 3 ) 2 ·6H 2 O, 6g of Fe (NO) 3 ) 3 ·9H 2 O and 19.31g of CO (NH) 2 ) 2 Mixing with 300ml of absolute ethyl alcohol to obtain a second mixed solution, mechanically stirring at room temperature for 100min, adding the second mixed solution into a high-temperature high-pressure stirring kettle for crystallization precipitation reaction through a peristaltic pump, performing secondary crystallization precipitation reaction, adjusting the stirring rotation speed to 400r/min, controlling the center temperature of the high-temperature high-pressure stirring kettle at 120 ℃, controlling the reaction pressure to be 1.0MPa, controlling the time of the secondary crystallization precipitation reaction to be 16h, and adding 0.10mol/L of ammonia water to adjust the pH value of the precipitation reaction to 8.5, thereby completing the secondary crystallization precipitation reaction.
After the second crystallization precipitation reaction is finished, all the mixed solution is transferred into a glass flask and is placed into a microwave heating furnace for aging, wherein the aging temperature is 150 ℃, and the aging time is 0.5h. And washing with deionized water to neutrality after the aging is finished, and obtaining the CuZnFeTi precursor.
And (3) placing the obtained CuZnFeTi precursor in an oven, drying at 110 ℃ for 12 hours, then placing in a muffle furnace, roasting at 450 ℃ for 12 hours to obtain the CuZnFeTi catalyst, crushing, grinding and screening for 20-40 meshes for evaluation.
Example 4:
the embodiment provides a preparation method of a catalyst for synthesizing methanol by hydrogenation of carbon dioxide, which comprises the following steps:
1.65g of CO (NH) 2 ) 2 TiOSO, 4g 4 Mixing with 200ml of absolute ethyl alcohol to obtain a third mixed solution, mechanically stirring the third mixed solution for 100min at room temperature, and completely transferring the mixed solution to a high-temperature high-pressure stirring kettle for a first crystallization precipitation reaction after uniform stirring; regulating stirring rotation speed to 400r/min, controlling the central temperature of the high-temperature high-pressure stirring kettle at 100deg.C and reaction pressure at 2.0MPa, and performing first crystallization precipitation reaction8 hours; during the first crystallization precipitation reaction, adding 0.10mol/L ammonia water to adjust the pH value of the first crystallization precipitation reaction to 7.5, and carrying out the first crystallization precipitation reaction.
60g of Cu (NO) 3 ) 2 ·3H 2 O, 15g of Zn (NO) 3 ) 2 ·6H 2 O and 5g of Fe (NO) 3 )3·9H 2 O and 21.1g of CO (NH) 2 ) 2 Mixing with 300ml of absolute ethyl alcohol to obtain a fourth mixed solution, mechanically stirring at room temperature for 60min, and completely transferring the fourth mixed solution into another high-temperature high-pressure stirring kettle to carry out a second crystallization precipitation reaction after uniform stirring; regulating the stirring rotation speed to 400r/min, controlling the central temperature of the high-temperature high-pressure stirring kettle to be 110 ℃, controlling the reaction pressure to be 2.0MPa, and carrying out secondary crystallization precipitation reaction for 8h; during the second crystallization precipitation reaction, adding 0.10mol/L ammonia water to adjust the pH value of the second crystallization precipitation reaction to 8.5, and carrying out the second crystallization precipitation reaction.
All the mixed solution after the reaction in the two high-temperature high-pressure stirring kettles is transferred into a glass flask and is placed into a microwave heating furnace for aging, wherein the aging temperature is 120 ℃, and the aging time is 1h; and filtering and washing to neutrality by using deionized water after the aging is finished, and obtaining the CuZnFeTi precursor.
And (3) placing the obtained CuZnFeTi precursor in an oven, drying at 100 ℃ for 12 hours, then placing in a muffle furnace, roasting at 460 ℃ for 8 hours to obtain the CuZnFeTi catalyst, crushing, grinding and screening for 20-40 meshes for evaluation.
Example 5:
the embodiment provides a preparation method of a catalyst for synthesizing methanol by hydrogenation of carbon dioxide, which comprises the following steps:
35g of Cu (CH) 3 COO) 2 ·H 2 O, 10g of Zn (CH) 3 COO) 2 15g of Fe (CH) 3 COO) 3 And 12g of TiCl 4 Mixing 23.62g of urea with 500ml of absolute ethyl alcohol to obtain a mixed solution, mechanically stirring the mixed solution at room temperature for 100min, and transferring the mixed solution into a high-temperature high-pressure stirring kettle for crystallization and precipitation reaction; regulating stirring rotation speed to 400r/min, and controlling the central temperature of the high-temperature high-pressure stirring kettleAt 100 ℃, the reaction pressure is 3.0MPa, and the crystallization precipitation method is carried out for 12 hours; during the crystallization and precipitation reaction, 0.10mol/L ammonia water is added to adjust the pH value of the crystallization and precipitation reaction to 8.5.
After the crystallization and precipitation reaction is finished, all the mixed solution is transferred into a glass flask and is placed into a microwave heating furnace for aging, wherein the aging temperature is 120 ℃, and the aging time is 2 hours. And filtering and washing to neutrality by using deionized water after the aging is finished, and obtaining the CuZnFeTi precursor.
And (3) placing the obtained CuZnFeTi precursor in an oven, drying at 100 ℃ for 24 hours, then placing in a muffle furnace, roasting at 500 ℃ for 12 hours to obtain the CuZnFeTi catalyst, crushing, grinding and screening by 20-40 meshes for evaluation.
Example 6:
the embodiment provides a preparation method of a catalyst for synthesizing methanol by hydrogenation of carbon dioxide, which comprises the following steps:
42g of Cu (CH) 3 COO) 2 ·H 2 O, 15g of Zn (CH) 3 COO) 2 12g of Fe (CH) 3 COO) 3 And 10g of TiOSO 4 Mixing 26.83g of urea and 500ml of absolute ethyl alcohol to obtain a mixed solution, mechanically stirring the mixed solution at room temperature for 100min, and transferring the mixed solution into a high-temperature high-pressure stirring kettle for crystallization and precipitation reaction; regulating the stirring rotation speed to 350r/min, controlling the center temperature of the high-temperature high-pressure stirring kettle to be 115 ℃ at 110 ℃ and the reaction pressure to be 2.5MPa, and carrying out crystallization precipitation reaction for 18h; during the crystallization precipitation reaction, 0.10mol/L ammonia water is added to adjust the pH value of the crystallization precipitation reaction to 8.5, thus completing the second crystallization precipitation reaction.
After the second crystallization precipitation reaction is finished, all the mixed solution is transferred into a glass flask and is placed into a microwave heating furnace for aging, wherein the aging temperature is 140 ℃, and the aging time is 1.5h. And washing with deionized water to neutrality after the aging is finished, and obtaining the CuZnFeTi precursor.
After the crystallization and precipitation reaction is finished, all the mixed solution is transferred into a glass flask and is placed into a microwave heating furnace for aging, wherein the aging temperature is 140 ℃, and the aging time is 1.5h. And washing with deionized water to neutrality after the aging is finished, and obtaining the CuZnFeTi precursor.
And (3) placing the obtained CuZnFeTi precursor in an oven, drying at 120 ℃ for 12 hours, then placing in a muffle furnace, roasting at 450 ℃ for 12 hours to obtain the CuZnFeTi catalyst, crushing, grinding and screening for 20-40 meshes for evaluation.
Example 7:
the embodiment provides a preparation method of a catalyst for synthesizing methanol by hydrogenation of carbon dioxide, which comprises the following steps:
1.74g of CO (NH) 2 ) 2 5g TiCl 4 Mixing with 200ml of absolute ethyl alcohol to obtain a first mixed solution, mechanically stirring the first mixed solution at room temperature for 100min, uniformly stirring, then completely transferring the first mixed solution into a high-temperature high-pressure stirring kettle to perform crystallization and precipitation reaction, regulating the stirring rotation speed to 400r/min, controlling the central temperature of the high-temperature high-pressure stirring kettle to be 110 ℃, performing crystallization and precipitation reaction for 12h, and adding 0.10mol/L ammonia water to regulate the pH value of the precipitation reaction to 8.0.
50g of Cu (CH) 3 COO) 2 ·H 2 O, 18g of Zn (CH) 3 COO) 2 6g of Fe (CH) 3 COO) 3 And 19.31g of CO (NH) 2 ) 2 Mixing with 300ml of absolute ethyl alcohol to obtain a second mixed solution, mechanically stirring for 30min at room temperature, adding the second mixed solution into a high-temperature high-pressure stirring kettle for crystallization precipitation reaction through a peristaltic pump, performing secondary crystallization precipitation reaction, adjusting the stirring rotation speed to 400r/min, controlling the center temperature of the high-temperature high-pressure stirring kettle at 120 ℃, controlling the reaction pressure to be 2.0MPa, controlling the time of the secondary crystallization precipitation reaction to be 12h, and adding 0.10mol/L ammonia water to adjust the pH value of the precipitation reaction to 8.5, thereby completing the secondary crystallization precipitation reaction.
After the second crystallization precipitation reaction is finished, all the mixed solution is transferred into a glass flask and is placed into a microwave heating furnace for aging, wherein the aging temperature is 150 ℃, and the aging time is 0.5h. And washing with deionized water to neutrality after the aging is finished, and obtaining the CuZnFeTi precursor.
And (3) placing the obtained CuZnFeTi precursor in an oven, drying at 110 ℃ for 12 hours, then placing in a muffle furnace, roasting at 500 ℃ for 8 hours to obtain the CuZnFeTi catalyst, crushing, grinding and screening by 20-40 meshes for evaluation.
Example 8:
the embodiment provides a preparation method of a catalyst for synthesizing methanol by hydrogenation of carbon dioxide, which comprises the following steps:
4.13g of CO (NH) 2 ) 2 TiOSO 10g 4 Mixing with 200ml of absolute ethyl alcohol to obtain a third mixed solution, mechanically stirring the third mixed solution for 100min at room temperature, and completely transferring the mixed solution to a high-temperature high-pressure stirring kettle for a first crystallization precipitation reaction after uniform stirring; regulating stirring rotation speed to 400r/min, controlling the center temperature of the high-temperature high-pressure stirring kettle to be 100 ℃, controlling the reaction pressure to be 2.0MPa, and carrying out primary crystallization precipitation reaction for 24h; during the first crystallization precipitation reaction, 0.10mol/L ammonia water is added to adjust the pH value of the precipitation reaction to 7.5, and the first crystallization precipitation reaction is carried out.
40g of Cu (CH) 3 COO) 2 ·H 2 O, 25g of Zn (CH) 3 COO) 2 And 8g of Fe (CH) 3 COO) 3 And 24.51g of CO (NH) 2 ) 2 Mixing with 300ml of absolute ethyl alcohol to obtain a fourth mixed solution, mechanically stirring for 40min at room temperature, and completely transferring the fourth mixed solution into another high-temperature high-pressure stirring kettle to carry out a second crystallization precipitation reaction after uniform stirring; regulating the stirring rotation speed to 400r/min, controlling the central temperature of the high-temperature high-pressure stirring kettle to be 110 ℃, controlling the reaction pressure to be 2.0MPa, and carrying out secondary crystallization precipitation reaction for 8h; and during the second crystallization precipitation reaction, adding 0.10mol/L ammonia water to adjust the pH value of the second crystallization precipitation reaction to 8.5, and carrying out second crystallization precipitation.
All the mixed solution after the reaction in the two high-temperature high-pressure stirring kettles is transferred into a glass flask and is placed into a microwave heating furnace for aging, wherein the aging temperature is 150 ℃, and the aging time is 0.5h; and filtering and washing to neutrality by using deionized water after the aging is finished, and obtaining the CuZnFeTi precursor.
And (3) placing the obtained CuZnFeTi precursor in an oven, drying at 100 ℃ for 12 hours, placing in a muffle furnace, and roasting at 600 ℃ for 12 hours to obtain the CuZnFeTi catalyst, crushing, grinding and screening for 20-40 meshes for evaluation.
Comparative example 1
20g of Cu (NO) 3 ) 2 ·3H 2 O, 18g of Zn (NO) 3 ) 2 ·6H 2 O, 4g of Fe (NO) 3 )3·9H 2 O, 4.5g of Al (NO) 3 ) 3 Mixing 12g of urea and 500ml of absolute ethyl alcohol to obtain a mixed solution, mechanically stirring the mixed solution at room temperature for 100min, and transferring the mixed solution into a high-temperature high-pressure stirring kettle for crystallization and precipitation reaction; regulating stirring rotation speed to 400r/min, controlling the center temperature of the high-temperature high-pressure stirring kettle to be 110 ℃, controlling the reaction pressure to be 2.0MPa, and carrying out crystallization precipitation reaction for 24h; during the crystallization and precipitation reaction, 0.10mol/L ammonia water is added to adjust the pH value of the crystallization and precipitation reaction to 8.5.
After the crystallization and precipitation reaction is finished, all the mixed solution is transferred into a glass flask and is placed into a microwave heating furnace for aging, wherein the aging temperature is 150 ℃, and the aging time is 0.5h. And filtering and washing to neutrality by using deionized water after the aging is finished, and obtaining the CuZnFeAl precursor.
And (3) placing the obtained CuZnFeAl precursor in an oven, drying at 120 ℃ for 12 hours, placing in a muffle furnace, roasting at 450 ℃ for 6 hours to obtain the CuZnFeAl catalyst, crushing, grinding and screening for 20-40 meshes, and evaluating the reaction.
Comparative example 2
20g of Cu (NO) 3 ) 2 ·3H 2 O, 18g of Zn (NO) 3 ) 2 ·6H 2 O, 4g TiCl 4 Mixing 12g of urea and 500ml of absolute ethyl alcohol to obtain a mixed solution, mechanically stirring the mixed solution at room temperature for 100min, and transferring the mixed solution into a high-temperature high-pressure stirring kettle for crystallization and precipitation reaction; regulating stirring rotation speed to 400r/min, controlling the center temperature of the high-temperature high-pressure stirring kettle to be 110 ℃, controlling the reaction pressure to be 2.0MPa, and carrying out crystallization precipitation reaction for 24h; during the crystallization and precipitation reaction, 0.10mol/L ammonia water is added to adjust the pH value of the crystallization and precipitation reaction to 8.5.
After the crystallization and precipitation reaction is finished, all the mixed solution is transferred into a glass flask and is placed into a microwave heating furnace for aging, wherein the aging temperature is 150 ℃, and the aging time is 0.5h. And filtering and washing to neutrality by using deionized water after the aging is finished, and obtaining the CuZnTi precursor.
And (3) placing the obtained CuZnTi precursor in an oven, drying at 120 ℃ for 12 hours, then placing in a muffle furnace, roasting at 450 ℃ for 6 hours to obtain the CuZnTi catalyst, crushing, grinding and screening for 20-40 meshes, and evaluating the reaction.
Results of evaluation of example activity:
the catalyst finished products prepared in the above examples and comparative examples were measured for their activity on an adiabatic fixed bed. 10g of catalyst finished product is filled into a stainless steel reaction tube, and the hydrothermal aging experiment is carried out on the catalyst: pressure = 5mpa, h 2 O/N 2 =10 (volume ratio), aging airspeed 30000h -1 Heating to 300 ℃ for accelerating aging for 20 hours; after the aging is finished, switching to N 2 /H 2 Mixed gas reduction of=9 (volume ratio), reduction airspeed 5000h -1 Reducing the temperature to 250 ℃ and reducing the temperature for 8 hours at constant temperature; cooling to 230 ℃ after reduction is finished, and switching to evaluate gas CO 2 :H 2 =3:1 (volume ratio), evaluation temperature 230 ℃, evaluation pressure 5MPa, evaluation airspeed 3000h -1 Stability evaluation was carried out for 100 hours, and the change in activity was measured, and the test results are shown in table 1:
TABLE 1
As can be seen from Table 1, the methanol synthesis catalyst in each example can maintain good methanol selectivity and carbon dioxide conversion rate in the evaluation experiment process after heat aging experiment treatment, which indicates that the catalyst has stable performance and good heat stability and anti-carbon deposition performance.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (5)
1. The catalyst for synthesizing methanol by using carbon dioxide is characterized by comprising the following components in percentage by mass: 45% -75% of CuO, 15% -40% of ZnO and Fe 2 O 3 4％-30％、TiO 2 5％-30％；
The preparation method of the catalyst for synthesizing methanol by using carbon dioxide comprises the following steps:
1) Preparing a CuZnFeTi precursor;
2) Roasting the CuZnFeTi precursor to obtain the catalyst for synthesizing methanol by using carbon dioxide;
the preparation of the CuZnFeTi precursor comprises the following steps:
step 1, mixing Cu salt, zn salt, fe salt, ti salt, urea and an organic alcohol solvent to obtain a mixed solution, and then carrying out crystallization precipitation reaction on the mixed solution;
step 2, after the crystallization precipitation reaction is finished, aging treatment is carried out on the reaction mixed solution, and filtering and washing are carried out to obtain the CuZnFeTi precursor;
or, the preparation of the CuZnFeTi precursor comprises the following steps:
s1, mixing urea, ti salt and an organic alcohol solvent to obtain a first mixed solution, and then carrying out a first crystallization precipitation reaction on the first mixed solution;
s2, mixing Cu salt, zn salt, fe salt, urea and an organic alcohol solvent to obtain a second mixed solution, adding the second mixed solution into a reaction solution of the first crystallization precipitation reaction to perform a second crystallization precipitation reaction, and aging, filtering and washing the reaction mixed solution after the second crystallization precipitation reaction is finished to obtain the CuZnFeTi precursor;
or, the preparation of the CuZnFeTi precursor comprises the following steps:
a. mixing urea, ti salt and an organic alcohol solvent to obtain a third mixed solution, and then carrying out a first crystallization precipitation reaction on the third mixed solution;
b. mixing Cu salt, zn salt, fe salt, urea and an organic alcohol solvent to obtain a fourth mixed solution, and then carrying out a second crystallization precipitation reaction on the fourth mixed solution;
c. mixing the reaction mixed solution of the first crystallization precipitation reaction and the reaction mixed solution of the second crystallization precipitation reaction to obtain a fifth mixed solution, aging the fifth mixed solution, filtering and washing to obtain the CuZnFeTi precursor;
wherein,,
in the step 1, the pH value of the reaction liquid is controlled to be 7-8.5 during the crystallization and precipitation reaction, the crystallization and precipitation reaction temperature is 100-120 ℃, the reaction pressure is 1.0-3.0MPa, the reaction time is 8-24h, the aging temperature in the step 2 is 60-150 ℃, and the aging time is 0.5-2.5h;
controlling the pH value of the reaction liquid to be 7-8.5 during the first crystallization and precipitation reaction in the step S1, controlling the temperature of the first crystallization and precipitation reaction to be 100-120 ℃, controlling the reaction pressure to be 1.0-3.0MPa, controlling the reaction time to be 8-24h, controlling the pH value of the reaction liquid to be 7-8.5 during the second crystallization and precipitation reaction in the step S2, controlling the temperature of the second crystallization and precipitation reaction to be 100-120 ℃, controlling the reaction pressure to be 1.0-3.0MPa, controlling the reaction time to be 8-24h, and controlling the aging temperature to be 60-150 ℃ and the aging time to be 0.5-2.5h;
controlling the pH value of the reaction liquid to 7-8.5 during the first crystallization and precipitation reaction in the step a, controlling the temperature of the first crystallization and precipitation reaction to 100-120 ℃, controlling the reaction pressure to 1.0-3.0MPa, controlling the reaction time to 8-24h, controlling the pH value of the reaction liquid to 7-8.5 during the second crystallization and precipitation reaction in the step b, controlling the temperature of the second crystallization and precipitation reaction to 100-120 ℃, controlling the reaction pressure to 1.0-3.0MPa, controlling the reaction time to 8-24h, and controlling the aging temperature to 60-150 ℃ and the aging time to 0.5-2.5h in the step c;
the washing is finished, and the washing product is dried at 80-150 ℃ for 12-24 hours;
the roasting temperature is 400-600 ℃, and the roasting time is 4-12h;
the organic alcohol solvent is absolute ethyl alcohol;
the Cu salt is selected from copper nitrate and/or copper acetate, the Zn salt is selected from zinc nitrate and/or zinc acetate, the Fe salt is selected from ferric nitrate and/or ferric acetate, and the Ti salt is selected from one or more of titanium tetrachloride, butyl titanate, titanium isopropoxide and titanyl sulfate.
2. The catalyst for synthesizing methanol from carbon dioxide according to claim 1, wherein,
in the step 1, the mol ratio of Cu salt, zn salt, fe salt, ti salt and urea is (0.15-0.85): (0.05-0.45): (0.02-0.2): (0.02-0.35): (0.1-1.4);
the concentration of Cu salt in the mixed solution in the step 1 is 0.15-0.85mol/L, the concentration of Zn salt is 0.05-0.45mol/L, the concentration of Fe salt is 0.02-0.2mol/L, the concentration of Ti salt is 0.02-0.35mol/L, and the concentration of urea is 0.1-1.4mol/L.
3. The catalyst for synthesizing methanol from carbon dioxide according to claim 1, wherein,
in the step S1, the molar ratio of urea to Ti salt is (0.01-1.4): (0.02-0.35), wherein the concentration of urea in the first mixed solution is 0.01-1.4mol/L, and the concentration of Ti salt is 0.02-0.35mol/L;
in the step S2, the mol ratio of Cu salt, zn salt, fe salt and urea is (0.15-0.85): (0.05-0.45): (0.02-0.2): (0.1-1.4), the concentration of Cu salt in the second mixed solution is 0.15-0.85mol/L, the concentration of Zn salt is 0.05-0.45mol/L, the concentration of Fe salt is 0.02-0.2mol/L, and the concentration of urea is 0.1-1.4mol/L.
4. The catalyst for synthesizing methanol from carbon dioxide according to claim 1, wherein,
in the step a, the molar ratio of urea to Ti salt is (0.01-1.4): (0.02-0.35), wherein the concentration of urea in the third mixed solution is 0.01-1.4mol/L, and the concentration of Ti salt is 0.02-0.35mol/L;
in the step b, the molar ratio of Cu salt, zn salt, fe salt and urea is (0.15-0.85): (0.05-0.45): (0.02-0.2): (0.1-1.4), the concentration of Cu salt in the fourth mixed solution is 0.15-0.85mol/L, the concentration of Zn salt is 0.05-0.45mol/L, the concentration of Fe salt is 0.02-0.2mol/L, and the concentration of urea is 0.1-1.4mol/L.
5. Use of the catalyst of claim 1 in a reaction for synthesizing methanol by hydrogenation of carbon dioxide.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111273325.3A CN113842914B (en) | 2021-10-29 | 2021-10-29 | Catalyst for synthesizing methanol from carbon dioxide, and preparation method and application thereof |
| PCT/CN2022/100990 WO2023071244A1 (en) | 2021-10-29 | 2022-06-24 | Catalyst for synthesizing carbon dioxide into methanol, preparation method therefor, and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111273325.3A CN113842914B (en) | 2021-10-29 | 2021-10-29 | Catalyst for synthesizing methanol from carbon dioxide, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113842914A CN113842914A (en) | 2021-12-28 |
| CN113842914B true CN113842914B (en) | 2023-06-23 |
Family
ID=78983563
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111273325.3A Active CN113842914B (en) | 2021-10-29 | 2021-10-29 | Catalyst for synthesizing methanol from carbon dioxide, and preparation method and application thereof |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN113842914B (en) |
| WO (1) | WO2023071244A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113842914B (en) * | 2021-10-29 | 2023-06-23 | 中国华能集团清洁能源技术研究院有限公司 | Catalyst for synthesizing methanol from carbon dioxide, and preparation method and application thereof |
| CN114602476B (en) * | 2022-03-04 | 2024-02-06 | 太原理工大学 | CO (carbon monoxide) 2 Hydrogenation for preparing C 2+ Preparation method and application of copper-iron-zinc-based catalyst of alcohol |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102500382B (en) * | 2011-11-03 | 2013-07-17 | 南京工业大学 | Catalyst for synthesizing methanol and preparation method thereof |
| CN102580750A (en) * | 2012-03-14 | 2012-07-18 | 上海华谊（集团）公司 | Catalyst for preparing methanol by hydrogenation of carbon dioxide and preparation method and application of catalyst |
| CN103933978B (en) * | 2014-04-10 | 2015-12-30 | 中国科学院福建物质结构研究所 | A kind of carrier nanometer catalyst for catalysis transform of carbon dioxide and its preparation method and application |
| CN107008332B (en) * | 2016-01-27 | 2019-07-26 | 中国科学院大连化学物理研究所 | A kind of catalyst of synthesizing methanol by hydrogenating carbon dioxide and its preparation and application |
| WO2018215943A1 (en) * | 2017-05-24 | 2018-11-29 | Sabic Global Technologies B.V. | Copper-zinc-zirconium-based catalyst for direct hydrogenation of co2 to methanol |
| CN109794276B (en) * | 2019-01-09 | 2021-11-30 | 沈阳化工大学 | Catalyst for preparing methanol by carbon dioxide hydrogenation and preparation method thereof |
| CN112755996A (en) * | 2020-12-11 | 2021-05-07 | 上海簇睿低碳能源技术有限公司 | Catalyst for synthesizing methanol by carbon dioxide hydrogenation, preparation method and application |
| CN113842914B (en) * | 2021-10-29 | 2023-06-23 | 中国华能集团清洁能源技术研究院有限公司 | Catalyst for synthesizing methanol from carbon dioxide, and preparation method and application thereof |
-
2021
- 2021-10-29 CN CN202111273325.3A patent/CN113842914B/en active Active
-
2022
- 2022-06-24 WO PCT/CN2022/100990 patent/WO2023071244A1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| WO2023071244A1 (en) | 2023-05-04 |
| CN113842914A (en) | 2021-12-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113842914B (en) | Catalyst for synthesizing methanol from carbon dioxide, and preparation method and application thereof | |
| CN115254100B (en) | For CO2Preparation and application of metal oxide doped type single-atom catalyst for preparing ethanol by hydrogenation | |
| CN103551153B (en) | A kind of copper-based catalysts for carbon dioxide methanation and preparation method thereof | |
| CN109569695B (en) | Preparation method and use method of core-shell structure catalyst for carbon dioxide hydrogenation | |
| CN100556538C (en) | A kind of slurried catalyst and preparation method thereof | |
| CN109126808A (en) | A kind of additive modification copper-based catalysts and preparation method and applications | |
| CN104028270A (en) | Methanation catalyst and preparation method thereof | |
| CN111111686B (en) | Ba-Mn perovskite type cobalt-based catalyst for autothermal reforming of acetic acid to produce hydrogen | |
| CN110327933A (en) | Hydrogenation of carbon dioxide prepares catalyst of methanol and its preparation method and application | |
| CN110215927A (en) | A kind of preparation method of the support type catalyst of phosphatizing nickel of high dispersive | |
| CN109499577A (en) | The preparation of Cu-Ni base catalyst for inverse water gas reaction and application method | |
| CN111389405B (en) | Method for preactivating methane vapor hydrogen production catalyst | |
| CN115837275A (en) | Perovskite type high-entropy oxide and preparation method and application thereof | |
| CN102500382B (en) | Catalyst for synthesizing methanol and preparation method thereof | |
| CN111437862A (en) | Catalyst for preparing methanol by carbon dioxide hydrogenation and preparation method thereof | |
| CN111282575A (en) | Catalyst for methanol steam reforming hydrogen production and preparation method and application thereof | |
| CN113663682A (en) | Non-supported mesoporous hydrodeoxygenation catalyst and preparation and application thereof | |
| CN100569366C (en) | The preparation method of full microwave radiation sulfur-tolerant type molybdenum base catalyst | |
| CN102794166B (en) | Dimethyl ether (DME) steam reforming hydrogen production catalyst and preparation and application thereof | |
| CN111744488B (en) | Catalyst for preparing dimethyl ether from slurry bed synthesis gas and preparation method thereof | |
| CN112517019A (en) | By TiO2Methanation catalyst with aerogel as carrier and preparation method and application thereof | |
| CN113731422A (en) | Preparation method of slurry bed methane synthesis catalyst | |
| CN109420485B (en) | CdO-TiO for preparing methanol by carbon dioxide hydrogenation2Catalyst, preparation and application | |
| CN112619654A (en) | Catalyst for preparing synthesis gas by reforming methane and carbon dioxide and preparation method thereof | |
| CN102626652B (en) | Molecular sieve catalyst for purifying methane in tail gas of natural gas vehicles, preparation and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |