CN113828309A - Catalyst for synthesizing methanol by carbon dioxide hydrogenation, preparation and application thereof - Google Patents
Catalyst for synthesizing methanol by carbon dioxide hydrogenation, preparation and application thereof Download PDFInfo
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- CN113828309A CN113828309A CN202111151253.5A CN202111151253A CN113828309A CN 113828309 A CN113828309 A CN 113828309A CN 202111151253 A CN202111151253 A CN 202111151253A CN 113828309 A CN113828309 A CN 113828309A
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 141
- 239000003054 catalyst Substances 0.000 title claims abstract description 88
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 52
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 39
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 24
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000013208 UiO-67 Substances 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 239000002244 precipitate Substances 0.000 claims abstract description 33
- 239000012266 salt solution Substances 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 11
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 10
- 230000032683 aging Effects 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 239000000047 product Substances 0.000 claims abstract description 4
- 239000010949 copper Substances 0.000 claims description 69
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 35
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 24
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 12
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 9
- 235000019253 formic acid Nutrition 0.000 claims description 9
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 9
- HSSYVKMJJLDTKZ-UHFFFAOYSA-N 3-phenylphthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1C(O)=O HSSYVKMJJLDTKZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000006722 reduction reaction Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 19
- 239000002245 particle Substances 0.000 abstract description 8
- 239000011148 porous material Substances 0.000 abstract description 6
- 230000003993 interaction Effects 0.000 abstract description 5
- 239000000725 suspension Substances 0.000 description 24
- 239000007789 gas Substances 0.000 description 18
- 238000001556 precipitation Methods 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 239000002243 precursor Substances 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000012216 screening Methods 0.000 description 4
- 239000013207 UiO-66 Substances 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000006004 Quartz sand Substances 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000004177 carbon cycle Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- GWZCCUDJHOGOSO-UHFFFAOYSA-N diphenic acid Chemical compound OC(=O)C1=CC=CC=C1C1=CC=CC=C1C(O)=O GWZCCUDJHOGOSO-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention relates to a catalyst for synthesizing methanol by carbon dioxide hydrogenation, and preparation and application thereof, wherein UiO-67 in the catalyst is a carrier, and Cu is an active component, and the Cu accounts for 10-30% of the total mass of the catalyst; the method comprises the following steps: (1) dispersing UiO-67 in a Cu salt solution, and then adding a carbonate solution to obtain a first precipitate; (2) and aging the obtained first precipitate, and then filtering, drying and roasting to obtain a target product. The pore cage of the carrier UiO-67 in the catalyst has the functions of enriching and adsorbing CO2The Cu active center in the catalyst has higher hydrogenation activity due to the interaction of the Cu particles and the Zr nodes, so that the catalyst has higher hydrogenation activityCO of2Conversion and methanol selectivity. Compared with the prior art, the catalyst of the invention has the advantages of obviously improved activity, improved carbon dioxide conversion rate and methanol selectivity, and CO2The conversion rate of the methanol reaches more than 14 percent, and the selectivity of the methanol reaches more than 70 percent; UiO-67 is selected as a carrier, so that the stability is excellent.
Description
Technical Field
The invention belongs to the field of catalysts, and relates to a catalyst for synthesizing methanol by carbon dioxide hydrogenation, and preparation and application thereof.
Background
Excessive combustion of fossil fuels has led to a continuous rise in atmospheric carbon dioxide concentration, which has increased from 280ppm prior to the industrial revolution to 419ppm in 2021. The release of large amounts of carbon dioxide greatly disrupts the earth's natural carbon cycle, and the greenhouse effect caused by the increase in carbon dioxide concentration results in significant environmental effects such as global warming, ocean acidification, sea level elevation, and climate change. Indeed, slowing down carbon dioxide emissions has become an urgent issue. Therefore, green carbon science, which utilizes efficient carbon resources for processing, utilization and recovery, has great significance for reducing carbon dioxide emissions, alleviating greenhouse effects, and reducing dependence on fossil fuels. Among them, the hydrogenation of carbon dioxide to methanol is considered as one of the most popular processes.
Cu-based catalysts have been widely used for CO for the past decades2The methanol prepared by hydrogenation mainly comprises Cu/ZnO/Al2O3、Cu/ZnO/ZrO2、Cu/ZnO/SiO2And Cu/ZnO/CNT, wherein Cu is used as an active component and ZnO is used as an auxiliary agent. Active sites and surface charges of Cu are adjusted mainly by changing carriers, so that the dispersibility of active component Cu is improved, and the activity of Cu is further improved. Chinese patent application CN107987281A discloses that Cu is loaded on organically modified UiO-66, Cu-UiO-66 prepared by an impregnation method is used for preparing methanol from synthesis gas, and the catalyst shows higher catalytic activity and stability for the reaction of preparing methanol from synthesis gas under the condition of low temperature. However, the catalyst prepared by the existing method has low selectivity of methanol, which is not more than 50%, and the low selectivity not only causes the waste of raw materials, but also causes great trouble for the subsequent product separation.
Disclosure of Invention
The invention aims to provide a catalyst for synthesizing methanol by hydrogenating carbon dioxide and a preparation method thereof, which aim to solve the problems of low selectivity of methanol or low carbon dioxide conversion rate and the like in the prior art.
One of the technical schemes of the invention is to provide a catalyst for synthesizing methanol by carbon dioxide hydrogenation, wherein UiO-67 is a carrier, and Cu is an active component.
Further, the Cu accounts for 10-30% of the total mass of the catalyst, optionally 15-25%, and preferably 20%.
The second technical scheme of the invention is to provide a preparation method of the catalyst, which comprises the following steps:
(1) dispersing UiO-67 in a Cu salt solution, and then adding a carbonate solution to obtain a first precipitate;
(2) and aging the obtained first precipitate, and then filtering, drying and roasting to obtain a target product.
Further, in the step (1), the ratio of the addition amounts of the UiO-67, the Cu salt solution and the carbonate solution is (1-1.5) g: (8.7-19.2) mL: 50 mL.
Further, in the step (1), the preparation process of the UiO-67 is as follows:
and (3) dispersing zirconium tetrachloride and biphenyldicarboxylic acid in a mixed solution of N, N-dimethylformamide and formic acid, reacting to obtain a second precipitate, and finally washing and drying to obtain UiO-67.
Furthermore, the addition ratio of the zirconium tetrachloride, the diphenic acid, the N, N-dimethylformamide and the formic acid is as follows: (0.8-1.2) mol: 1 mol: (200-250) mL: (30-40) mL.
The further reaction temperature is 80-120 ℃ and the reaction time is 10-72 hours.
And further, washing the second precipitate by using N, N-dimethylformamide and acetone in sequence for 3-5 times respectively, drying at normal temperature, and drying the dried second precipitate in an oven for 12-16 hours to obtain the UiO-67.
Further, in the step (1), the Cu salt solution is an inorganic salt solution of copper.
Further, the inorganic salt of copper may be selected from copper nitrate, copper sulfate or copper chloride, preferably copper nitrate.
Further, in the step (1), the concentration of the Cu salt solution is 0.2-0.5 mol/L.
Further, in the step (1), the carbonate solution may be a sodium carbonate aqueous solution.
Further, in the step (1), the concentration of the carbonate solution is 0.5-1 mol/L.
Further, in the step (1), the precipitation is started after the carbonate solution is added, and the precipitation is finished when the pH of the mixed solution is 7-8.
Further, in the step (1), a carbonate solution is added to generate a precipitate, and the temperature of the process is 55-65 ℃.
Further, in the step (2), the aging time is 2-4 hours.
Further, in the step (2), the drying process specifically comprises:
keeping the temperature at 45 ℃ for 50 minutes, then heating to 75 ℃ for 60 minutes for the first time, and finally heating to 80-110 ℃ for the second time and keeping the temperature for 12 hours.
Furthermore, the rate of the first temperature rise is 1 ℃/min, and the rate of the second temperature rise is 0.5 ℃/min.
Further, in the step (2), the roasting process specifically comprises:
heating from normal temperature to 120 ℃ and keeping the temperature for 60 minutes in a muffle furnace, then heating to 240 ℃ and keeping the temperature for 120 minutes for the second time, and finally heating to 350-500 ℃ for the third time and roasting for 2-4 hours.
Furthermore, the rate of the first temperature rise is 2 ℃/min, the rate of the second temperature rise is 1 ℃/min, and the rate of the third temperature rise is 0.5 ℃/min.
Further, in the step (2), a suction filter is used for filtering, and the filtering times are 5-7 times.
The third technical scheme of the invention is to provide the application of the catalyst in the reaction of synthesizing methanol by hydrogenating carbon dioxide, which comprises the following specific steps:
(1) putting the obtained catalyst in a fixed bed reactor, and introducing reducing mixed gas for reduction reaction;
(2) and after the reduction is finished, introducing raw material mixed gas to perform a reaction of synthesizing the methanol by carbon dioxide hydrogenation.
Further, in the step (1), the composition of the reducing mixed gas is H2And N2。
Further, said H2The volume fraction of (A) is 5-15%.
Further, in the step (1), the temperature of the reduction reaction is 250-300 ℃, and the time of the reduction reaction is 1-3 hours.
Further, in the step (2), the gas composition of the raw material gas mixture is H2、CO2And N2。
Further, said H2、CO2And N2The volume fractions of (a) and (b) are respectively 64.5%, 23.5% and 12%.
Further, in the step (2), the reaction temperature is 200 ℃, the reaction pressure is 2-5MPa, and the reaction space velocity is 1000-cat·h)。
The catalyst prepared by the invention has a regular octahedral morphology, the pore structure in the octahedral catalyst particles comprises a regular octahedral cage and a tetrahedral cage, and Cu particles are uniformly dispersed in the pore cages and are connected with Zr nodes (Zr) in a UiO-67 carrier6(μ3-O)4(μ3-OH)4) A stronger interaction is formed. The pore cage of the carrier UiO-67 in the catalyst has the functions of enriching and adsorbing CO2The Cu active center in the catalyst has higher hydrogenation activity due to the interaction of the Cu particles and Zr nodes, so that the catalyst has higher CO2Conversion and methanol selectivity.
Compared with the prior art, the invention has the following advantages:
(1) when the catalyst prepared by the invention is used for preparing methanol by carbon dioxide hydrogenation, the activity of the catalyst is obviously improved, the conversion rate of carbon dioxide and the selectivity of methanol are improved, and CO is obtained2The conversion rate of the methanol reaches more than 14 percent, and the selectivity of the methanol reaches more than 70 percent；
(2) According to the invention, UiO-67 is selected as a carrier, so that the catalyst effect is obviously improved, and the stability is excellent.
Drawings
FIG. 1 is a TEM image of the catalyst prepared in example 2 after calcination;
FIG. 2 is a graph of the energy spectrum of the catalyst prepared in example 2 after calcination.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
Example 1:
0.42g of Cu (NO) was weighed3)2·3H2O, preparing a Cu salt solution with the concentration of 0.2mol/L, adding 1g of UiO-67 into the prepared Cu salt solution, and stirring to obtain a suspension. And (3) placing the suspension on a magnetic stirrer, stirring for 1 hour, and placing the suspension in a water bath kettle at 60 ℃ after stirring. Preparing 50ml of 0.5mol/L sodium carbonate aqueous solution, slowly adding the sodium carbonate aqueous solution into the suspension to obtain a first precipitate, and ending the precipitation until the pH value of the suspension is 7; after the precipitation is finished, the precipitate is aged (i.e. normally kept) for 2 hours, filtered for 5 times by a suction filter to obtain a catalyst oxide precursor, the obtained catalyst oxide precursor is kept at the constant temperature of 45 ℃ for 50 minutes, heated to 75 ℃ at the speed of 1 ℃/minute for 60 minutes, heated to 80 ℃ at the speed of 0.5 ℃/minute and kept at the constant temperature for 12 hours for drying. After drying, heating to 120 ℃ from normal temperature at the speed of 2 ℃/min in a muffle furnace, keeping the temperature for 60 minutes, then heating to 240 ℃ at the speed of 1 ℃/min, keeping the temperature for 120 minutes, then heating to 400 ℃ at the speed of 0.5 ℃/min, and roasting for 2 hours as a roasting temperature to prepare the Cu/UiO-67 catalyst with the Cu mass fraction of 10%.
The preparation method of UiO-67 comprises the following steps: adding 4.66g of zirconium tetrachloride and 4.844g of biphenyldicarboxylic acid into a mixed solution of 220mLN, N-dimethylformamide and 34mL of formic acid, and performing ultrasonic dissolution to obtain a mixed solution; and (3) placing the dissolved mixed solution at 100 ℃, preserving heat for 24 hours, cooling to room temperature to obtain a second precipitate, washing with N, N-dimethylformamide and acetone for 3 times respectively, carrying out suction filtration, drying at room temperature, and drying the dried second precipitate in an oven at 80 ℃ for 12 hours to obtain UiO-67.
Tabletting the prepared Cu/UiO-67 catalyst under the pressure of 2MPa, and crushing and screening the catalyst with 40-80 meshes for later use.
The catalyst activity evaluation is carried out on a fixed bed reactor, 0.15g of catalyst is weighed, 0.5g of quartz sand is mixed in, the mixture is placed in a 5mm stainless steel reaction tube, and before the reaction, the catalyst is put under normal pressure and H2Volume fraction of 10% of H2/N2Reducing for 2 hours at 300 ℃ in reducing gas atmosphere, the flow rate is 46.5mL/min, cooling to 260 ℃ after the reduction is finished, switching to raw material gas, and the volume ratio is 64.5% H2-23.5％CO2-12％N2) Simultaneously increasing the pressure to 3MPa, and keeping the reaction space velocity (GHSV) as 2400 mL/(g)catH), the activity of the catalyst is tested for 3-5 hours and is shown in Table 1.
Before the carbon dioxide hydrogenation reaction, the prepared catalyst is introduced into a fixed bed reactor (10% H by volume)2：90％N2) Reducing the mixed gas at 250 ℃ for 1 hour; then 64.5% H by volume is introduced2-23.5％CO2-12％N2At a reaction temperature of 200 ℃, a reaction pressure of 2MPa and a reaction space velocity (GHSV) of 1000 mL/(g)catH) carrying out the reaction of synthesizing methanol by hydrogenating carbon dioxide.
Example 2:
weigh 0.709g Cu (NO)3)2·3H2O, preparing a Cu salt solution with the concentration of 0.3mol/L, adding 1.2g of UiO-67 into the Cu salt solution, stirring to form a suspension, placing the suspension on a magnetic stirrer, stirring for 1 hour, placing the suspension in a 65 ℃ water bath kettle for precipitation after stirring is finished, preparing 50ml of 0.8mol/L sodium carbonate aqueous solution, slowly adding the sodium carbonate aqueous solution into the suspension to generate a first precipitate, and ending the precipitation until the pH value of the suspension is 7.8; after the precipitation is finished, aging the precipitate for 3.5 hours, filtering for 6 times by using a suction filter to obtain a catalyst oxide precursor, and obtaining the catalyst oxide precursorThe catalyst oxide precursor is dried for 12 hours at 90 ℃, then heated to 120 ℃ from normal temperature at the speed of 2 ℃/min for 60 minutes at constant temperature after being dried in a muffle furnace, then heated to 240 ℃ at the speed of 1 ℃/min for 120 minutes at constant temperature, and then heated to 500 ℃ at the speed of 0.5 ℃/min to be used as a roasting temperature for roasting for 3.5 hours, so as to prepare the Cu/UiO-67 catalyst with the Cu mass fraction of 15%, and the activity evaluation is shown in Table 1.
The preparation method of UiO-67 comprises the following steps: adding 4.66g of zirconium tetrachloride and 4.844g of biphenyldicarboxylic acid into 220mLN, N-dimethylformamide and 34mL of formic acid, and performing ultrasonic dissolution to obtain a mixed solution; and (3) placing the dissolved mixed solution at 110 ℃, preserving heat for 10 hours, cooling to room temperature to obtain a second precipitate, washing with N, N-dimethylformamide and acetone for 3 times respectively, placing the obtained second precipitate at room temperature for airing, and placing the aired second precipitate in a 90 ℃ oven for drying for 13 hours to obtain solid UiO-67 powder.
Tabletting the prepared Cu/UiO-67 catalyst under the pressure of 1.5MPa, and crushing and screening out the 40-80 mesh catalyst for later use.
Introducing H into the prepared catalyst in a fixed bed reactor before the carbon dioxide hydrogenation reaction is carried out2：N2Reducing the mixed gas at 275 ℃ for 1.5 hours, wherein the volume ratio is 1:9 (the same applies below); then 64.5% H by volume is introduced2+23.5％CO2+12％N2Mixed gas, the reaction temperature is 200 ℃, the reaction pressure is 3MPa, and the space velocity is 2000 mL/(g)catH) carrying out the reaction of synthesizing methanol by hydrogenating carbon dioxide.
Example 3:
weigh 0.945g Cu (NO)3)2·3H2O, preparing a Cu salt solution with the concentration of 0.3mol/L, adding 1.2g of UiO-67 into the Cu salt solution, stirring to form a suspension, placing the suspension on a magnetic stirrer, stirring for 1 hour, placing the suspension in a 65 ℃ water bath kettle for precipitation after stirring is finished, preparing 50ml of 0.6mol/L sodium carbonate aqueous solution, slowly adding the sodium carbonate aqueous solution into the suspension to generate a first precipitate, and ending the precipitation until the pH value of the suspension is 7.2; after the precipitation was completed, the precipitate was aged for 2.5 hours and filtered through a suction filterFiltering for 6 times to obtain a catalyst oxide precursor, keeping the temperature of the obtained catalyst oxide precursor at 45 ℃ for 50 minutes, heating to 75 ℃ at the speed of 1 ℃/minute, keeping the temperature for 60 minutes, heating to 90 ℃ at the speed of 0.5 ℃/minute, and keeping the temperature for 12 hours. After drying, the temperature is raised to 120 ℃ from the normal temperature at the speed of 2 ℃/minute in a muffle furnace and is kept for 60 minutes, then the temperature is raised to 240 ℃ at the speed of 1 ℃/minute and is kept for 120 minutes, then the temperature is raised to 350 ℃ at the speed of 0.5 ℃/minute and is used as the roasting temperature to roast for 2.5 hours, and the Cu/UiO-67 catalyst with the Cu mass fraction of 20% is prepared, and the activity evaluation is shown in Table 1.
The preparation method of UiO-67 comprises the following steps: adding 4.66g of zirconium tetrachloride and 4.844g of biphenyldicarboxylic acid into a mixed solution of 220mLN, N-dimethylformamide and 34mL of formic acid, and performing ultrasonic dissolution to obtain a mixed solution; and (3) placing the dissolved mixed solution at 80 ℃, preserving heat for 72 hours, cooling to room temperature to obtain a second precipitate, washing with N, N-dimethylformamide and acetone for 3 times respectively, placing the obtained second precipitate at room temperature for airing, and placing the aired second precipitate in a 90 ℃ oven for drying for 13 hours to obtain UiO-67.
Tabletting the prepared Cu/UiO-67 catalyst under the pressure of 2MPa, and crushing and screening the catalyst with 40-80 meshes for later use.
Introducing H into the prepared catalyst in a fixed bed reactor before the carbon dioxide hydrogenation reaction is carried out2：N2Reducing the mixed gas at 300 ℃ for 1.5 hours, wherein the ratio of the mixed gas to the mixed gas is 1: 9; then 64.5% H by volume is introduced2+23.5％CO2+12％N2Mixed gas, the reaction temperature is 200 ℃, the reaction pressure is 3MPa, and the space velocity is 2000 mL/(g)catH) carrying out the reaction of synthesizing methanol by hydrogenating carbon dioxide.
Example 4:
1.89g of Cu (NO) was weighed3)2·3H2And O, preparing a Cu salt solution with the concentration of 0.5mol/L, adding 1.5g of UiO-67 into the Cu salt solution, stirring to form a suspension, placing the suspension on a magnetic stirrer, stirring for 1.5 hours, and placing the suspension in a water bath kettle at 65 ℃. Preparing 50ml of 1mol/L sodium carbonate aqueous solution, and slowly adding the sodium carbonate aqueous solution into the suspension to producePrecipitating until the pH of the suspension is 8; after the precipitation is finished, the precipitate is aged for 4 hours, filtered for 6 times by a suction filter to obtain a catalyst oxide precursor, the obtained catalyst oxide precursor is kept at the constant temperature of 45 ℃ for 50 minutes, heated to 75 ℃ at the speed of 1 ℃/minute for 60 minutes, heated to 110 ℃ at the speed of 0.5 ℃/minute for 12 hours. After drying, the temperature is raised from the normal temperature to 120 ℃ at the speed of 2 ℃/minute and is kept for 60 minutes, then the temperature is raised to 240 ℃ at the speed of 1 ℃/minute and is kept for 120 minutes, then the temperature is raised to 450 ℃ at the speed of 0.5 ℃/minute and is used as a roasting temperature to roast for 4 hours, and the Cu/UiO-67 catalyst with the Cu mass fraction of 25% is prepared, and the activity evaluation is shown in table 1.
The preparation method of UiO-67 comprises the following steps: adding 4.66g of zirconium tetrachloride and 4.844g of biphenyldicarboxylic acid into a mixed solution of 220mLN, N-dimethylformamide and 34mL of formic acid, and performing ultrasonic dissolution to obtain a mixed solution; and (3) placing the dissolved mixed solution at 120 ℃, preserving heat for 36 hours, cooling to room temperature to obtain a second precipitate, washing with N, N-dimethylformamide and acetone for 3 times respectively, placing the obtained second precipitate at room temperature for airing, and placing the aired second precipitate in a 110 ℃ oven for drying for 16 hours to obtain UiO-67.
Introducing H into the prepared catalyst in a fixed bed reactor before the carbon dioxide hydrogenation reaction is carried out2Volume fraction of 5% of H2/N2Reducing the mixed gas at 300 ℃ for 3 hours; then 64.5% H by volume is introduced2-23.5％CO2-12％N2Reaction gas mixture, the reaction temperature is 200 ℃, the reaction pressure is 5MPa, and the space velocity is 10000 mL/(g)catH) carrying out the reaction of synthesizing methanol by hydrogenating carbon dioxide.
Example 5:
1.62g of Cu (NO) was weighed3)2·3H2O, preparing a Cu salt solution with the concentration of 0.35mol/L, and
adding 1.3g of UiO-67 into a Cu salt solution to form a suspension, placing the suspension on a magnetic stirrer, stirring for 1 hour, placing the suspension in a water bath kettle at 55 ℃ after stirring, precipitating, preparing 50ml of 0.7mol/L sodium carbonate aqueous solution, dropwise adding the sodium carbonate aqueous solution into the suspension to generate a first precipitate, and ending precipitation until the pH value of the liquid is 8.0; after the precipitation is finished, the precipitate is aged for 3 hours, filtered for 7 times by a suction filter to obtain a catalyst oxide precursor, the obtained catalyst oxide precursor is kept at a constant temperature of 45 ℃ for 50 minutes, heated to 75 ℃ at a speed of 1 ℃/minute for 60 minutes, heated to 110 ℃ at a speed of 0.5 ℃/minute for 12 hours, dried at a speed of 2 ℃/minute from the normal temperature to 120 ℃ for 60 minutes, heated to 240 ℃ at a speed of 1 ℃/minute for 120 minutes, and then heated to 500 ℃ at a speed of 0.5 ℃/minute to serve as a roasting temperature for roasting for 3 hours, so that the Cu/UiO-66 catalyst with the Cu mass fraction of 30% is prepared, and the activity evaluation is shown in Table 1.
The preparation method of UiO-67 comprises the following steps: adding 4.66g of zirconium tetrachloride and 4.844g of biphenyldicarboxylic acid into a mixed solution of 220mLN, N-dimethylformamide and 34mL of formic acid, and performing ultrasonic dissolution to obtain a mixed solution; and (3) placing the dissolved mixed solution at 90 ℃, preserving heat for 24 hours, cooling to room temperature to obtain a second precipitate, washing with N, N-dimethylformamide and acetone for 3 times respectively, placing the obtained second precipitate at room temperature for airing, and placing the aired second precipitate in a 100 ℃ oven for drying for 14 hours to obtain the UiO-67 material.
Tabletting the prepared Cu/UiO-67 catalyst under the pressure of 2MPa, and crushing and screening the catalyst with 40-80 meshes for later use.
Introducing H with the volume ratio of 15:85 into the fixed bed reactor before the carbon dioxide hydrogenation reaction2/N2Reducing the mixed gas at 270 ℃ for 2 hours; then 64.5% H was passed2-23.5％CO2-12％N2Reaction gas mixture, the reaction temperature is 200 ℃, the reaction pressure is 3.5MPa, and the space velocity is 3000 mL/(g)catH) carrying out the reaction of synthesizing methanol by hydrogenating carbon dioxide.
Comparative example 1:
0.945g of Cu (NO) was taken3)2·3H2O, preparing a Cu salt solution with a concentration of 0.3mol/L, and adding 1g of ZrO to the Cu salt solution2. Other preparation and evaluation were the same as in example 1, ZrO2The carrier is Zr (NO)3)4·5H2O was calcined in a muffle furnace at 500 ℃ for 4 hours to obtain a white powder. The catalyst is prepared from Cu/ZrO with the mass fraction of Cu of 20%2The catalyst activity evaluation is shown in Table 1.
Table 1 results of catalyst activity
As can be seen from the data in Table 1, the activity and selectivity of the catalyst obtained by the preparation method provided by the invention are greatly improved. In the range of 10-30% of Cu mass fraction, CO2The conversion rate of the methanol reaches more than 14 percent, and the selectivity of the methanol reaches more than 70 percent. At a Cu mass fraction of 20%, CO2The conversion was even close to 19% and the selectivity to methanol was 76.8%. The catalyst of comparative example 1, CO, prepared using the prior art2The conversion of (A) is less than 10%, and the selectivity of methanol is about 55%.
The catalyst prepared by the preparation method provided by the invention has the methanol yield of more than 10 percent, while the catalyst prepared by the prior art has the methanol yield of 5.53 percent, and even if the catalyst prepared by the invention has the lowest yield of 10.36 percent, the methanol yield is still improved by more than 87 percent compared with the prior art.
In order to analyze the catalyst prepared by the present invention, the catalyst prepared in example 3 was subjected to transmission electron microscopy and energy spectroscopy, and the results are shown in fig. 1 and 2, respectively. As can be seen from FIGS. 1 and 2, the catalyst prepared by the present invention has a relatively regular octahedral morphology, with the octahedral particle size being about 500 nm. The pore structure in the octahedral particles comprises octahedral cages with a diameter of 0.76nm and tetrahedral cages with a diameter of 0.62nm, and Cu particles with a diameter of about 0.1 to 0.3nm are uniformly dispersed in the above pore cages and form Zr nodes (Zr) with the UiO-67 carrier6(μ3-O)4(μ3-OH)4) A stronger interaction is formed.
The activity of the catalyst provided by the invention is analyzed, and the following reasons can be probably caused: vector UiO-67The hole cage has the functions of enriching and adsorbing CO2The interaction of Cu particles of 0.1-0.3nm and Zr nodes ensures that the Cu active center in the catalyst has higher hydrogenation activity, so the catalyst has higher CO2Conversion and methanol selectivity.
Example 6:
compared to example 1, most of them are the same except that in this example, 0.42g of Cu (NO) is used3)2·3H2O was changed to 0.278g copper sulfate.
Example 7:
compared to example 1, most of them are the same except that in this example, 0.42g of Cu (NO) is used3)2·3H2O was changed to 0.234g of cupric chloride.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. The catalyst for synthesizing the methanol by hydrogenating the carbon dioxide is characterized by taking UiO-67 as a carrier and Cu as an active component, wherein the active component Cu accounts for 10-30% of the total mass of the catalyst.
2. The method for preparing a catalyst for synthesizing methanol by hydrogenating carbon dioxide according to claim 1, comprising the steps of:
(1) dispersing UiO-67 in a Cu salt solution, and then adding a carbonate solution to obtain a first precipitate;
(2) and aging the obtained first precipitate, and then filtering, drying and roasting to obtain a target product.
3. The method for preparing the catalyst for synthesizing methanol by hydrogenating carbon dioxide according to claim 2, wherein in the step (1), the ratio of the addition amounts of the UiO-67, the Cu salt solution and the carbonate solution is (1-1.5) g: (8.7-19.2) mL: 50 mL.
4. The method for preparing a catalyst for synthesizing methanol by hydrogenating carbon dioxide according to claim 2, wherein in the step (1), the UiO-67 is prepared by:
dispersing zirconium tetrachloride and biphenyldicarboxylic acid in a mixed solution of N, N-dimethylformamide and formic acid, and then reacting to obtain UiO-67;
the addition ratio of the zirconium tetrachloride to the biphenyldicarboxylic acid to the N, N-dimethylformamide to the formic acid is as follows: (0.8-1.2) mol: 1 mol: (200-250) mL: (30-40) mL;
the reaction temperature is 80-120 ℃, and the reaction time is 10-72 hours.
5. The method for preparing a catalyst for synthesizing methanol by hydrogenating carbon dioxide according to claim 2, wherein in the step (1), the Cu salt solution is an inorganic salt solution of copper, and the concentration of the inorganic salt solution is 0.2 to 0.5 mol/L;
the solute of the Cu salt solution is copper nitrate, copper sulfate or copper chloride.
6. The method according to claim 2, wherein in the step (1), the carbonate solution is an aqueous solution of sodium carbonate with a concentration of 0.5-1 mol/L.
7. The method for preparing a catalyst for synthesizing methanol by hydrogenating carbon dioxide as claimed in claim 2, wherein the aging time in the step (2) is 2 to 4 hours.
8. The method for preparing a catalyst for synthesizing methanol by hydrogenating carbon dioxide according to claim 2, wherein in the step (2), the drying process comprises:
keeping the temperature at 45 ℃ for 50 minutes, then heating to 75 ℃ for 60 minutes for the first time, and finally heating to 80-110 ℃ for the second time and keeping the temperature for 12 hours.
9. The method for preparing the catalyst for synthesizing methanol by hydrogenating carbon dioxide according to claim 2, wherein in the step (2), the roasting process comprises:
heating from normal temperature to 120 ℃ and keeping the temperature for 60 minutes in a muffle furnace, then heating to 240 ℃ and keeping the temperature for 120 minutes for the second time, and finally heating to 350-500 ℃ for the third time and roasting for 2-4 hours.
10. The application of the catalyst for synthesizing methanol by hydrogenating carbon dioxide according to claim 1, wherein the catalyst is used in the reaction for synthesizing methanol by hydrogenating carbon dioxide, and the application comprises the following specific steps:
(1) the catalyst is placed in a fixed bed reactor and H is introduced2And N2Carrying out reduction reaction on the reduction mixed gas;
(2) after the reduction is completed, H is introduced2、CO2And N2The raw material gas mixture is subjected to a reaction of synthesizing methanol by hydrogenation of carbon dioxide.
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