CN113145113A - Carbon dioxide hydrogenation catalyst, preparation method and application thereof - Google Patents
Carbon dioxide hydrogenation catalyst, preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 66
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 21
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 102
- 238000006243 chemical reaction Methods 0.000 claims abstract description 86
- 239000006104 solid solution Substances 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 42
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 6
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 6
- 230000009467 reduction Effects 0.000 claims description 65
- 239000000243 solution Substances 0.000 claims description 57
- 239000002244 precipitate Substances 0.000 claims description 45
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 43
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical group [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 26
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical group [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 26
- 238000000975 co-precipitation Methods 0.000 claims description 18
- 239000003513 alkali Substances 0.000 claims description 15
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 14
- 239000001099 ammonium carbonate Substances 0.000 claims description 14
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 14
- 229910052763 palladium Inorganic materials 0.000 claims description 13
- 239000012495 reaction gas Substances 0.000 claims description 13
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical group [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 12
- 239000011701 zinc Substances 0.000 claims description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 19
- 230000008569 process Effects 0.000 abstract description 12
- 230000008878 coupling Effects 0.000 abstract 1
- 238000010168 coupling process Methods 0.000 abstract 1
- 238000005859 coupling reaction Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 38
- 239000008367 deionised water Substances 0.000 description 33
- 229910021641 deionized water Inorganic materials 0.000 description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- 239000012266 salt solution Substances 0.000 description 21
- 238000003756 stirring Methods 0.000 description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 238000001816 cooling Methods 0.000 description 11
- 238000000703 high-speed centrifugation Methods 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 230000002572 peristaltic effect Effects 0.000 description 11
- 238000010926 purge Methods 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- 150000002823 nitrates Chemical class 0.000 description 10
- 238000011946 reduction process Methods 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000000446 fuel Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910017518 Cu Zn Inorganic materials 0.000 description 1
- 229910017752 Cu-Zn Inorganic materials 0.000 description 1
- 229910017943 Cu—Zn Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 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
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004177 carbon cycle Methods 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical group 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
- B01J23/38—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
-
- 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
-
- 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
- C07C29/157—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 containing platinum group metals or compounds thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention provides a carbon dioxide hydrogenation catalyst, a preparation method and application thereof, wherein the catalyst is a Pd-doped metal oxide solid solution, and the general formula of the metal oxide solid solution is ZnxZr1‑xO and x are 0.13 to 0.5. The catalyst has the characteristics of high activity, high methanol selectivity and long-time stable operation at higher temperature and pressure, and provides wide prospects for subsequent industrial application and coupling of a subsequent methanol conversion process.
Description
Technical Field
The invention relates to the technical field of catalytic conversion of carbon dioxide hydrogenation, in particular to a catalyst for preparing methanol by carbon dioxide hydrogenation and a preparation method and application thereof.
Background
Methanol is an important chemical intermediate raw material, can be used as a fuel of an internal combustion engine and a fuel cell, and can be gradually used as non-renewable energyThe methanol is gradually reduced and can be used as a replaceable chemical raw material to synthesize various chemicals, gasoline and other fuels. In recent years, with the development of technologies such as a molecular sieve catalyst, Methanol To Olefin (MTO), Methanol to aromatic (MTG), and the like, the Demand of a fuel obtained from Methanol in the international market has been rapidly increasing (Johnson, d.global Methanol Demand Growth; IHS inc., 2016). The traditional industrial preparation of methanol adopts a synthesis gas conversion method, but mainly faces to a catalyst (Cu/ZnO/Al)2O3) The active sites are easy to sinter under the reaction conditions, which causes poor stability, and moreover, the raw material synthesis gas output of the process is often accompanied with the consumption of fossil resources such as coal, natural gas and the like and CO caused by the conversion process2Discharge and environmental pollution.
CO2Are the main components of greenhouse gases in the atmosphere, which result from the combustion of large quantities of fossil fuels and lead to increasingly deeper global climate change over the past decades. Human activity emits CO to the atmosphere every year2Nearly 400 hundred million tons of atmospheric CO in 20192The content is as high as 407ppm, and the growth is 20 percent in the last 40 years. Reduction of CO2The amount of discharge is certainly a pressing issue. If mixing CO with2By converting renewable energy into chemical raw materials, not only can CO be solved2Excess emission problem, and CO generation2Becomes a novel carbon source for replacing the traditional fossil fuel. CO 22The molecules being chemically inert but incorporating H having a high free energy2The molecule as a reactant makes the reaction thermodynamically easy, while H2If the water is obtained by a renewable mode such as electrolytic water or photolytic water, the whole process has wide prospects in environment and economy. Thus, using CO2Catalytic hydrogenation to methanol is an attractive means of reducing CO2Discharge and create a new carbon cycle process scenario.
At present, CO2The hydrogenation for preparing methanol mainly adopts a supported metal or metal oxide catalyst, such as traditional Cu/ZnO/Al2O3(Science 352 2016 969–974),Cu/ZrO2(J.Am.Chem.Soc.138 2016 12440–12450)，Pd/ZnO(J.Catal.343 2016 133-146), and the like. GmbH&Lurgi GmbH adopted catalyst Cu/ZnO/Al in 20102O3A methanol yield of 0.6kg at 40% conversion per pass was achieved in a commercial pilot plantCH3OH/LcatH, this type of catalytic performance is often affected by changes in the surface chemistry of Cu and is easily deactivated by agglomeration under conditions where the reaction generates large amounts of water. At slightly higher temperatures, the selectivity of methanol in the product decreases, which in turn produces CO as a by-product. In recent years, Cu-Zn materials modified with transition metals have also been studied extensively, e.g., CuZnGa-hydrotalcite in CO2The yield of the methanol is 0.59kg under the condition that the conversion rate is 20 percentCH3OH/LcatH, but the methanol selectivity was only around 50% (ACS Catal.2018,8, 4390-one 4401). And adopts noble metal loaded Pd/CeO2The methanol selectivity of the catalyst reaches 92 percent, but CO2Conversion is not ideal (J.Catal.,1994,150, 217-220). Therefore, the method designs the catalyst which can stably operate under the reaction condition and has higher CO2The catalyst for conversion rate and methanol selectivity is to realize CO2The industrial application of hydrogenation to prepare methanol is an urgent problem.
Disclosure of Invention
In view of the above-mentioned disadvantages of the prior art, it is an object of the present invention to provide a catalyst for preparing methanol by hydrogenating carbon dioxide, a preparation method and a use thereof, which are used to solve the problems of the prior art.
To achieve the above objects and other related objects, the present invention is achieved by the following technical solutions.
The invention provides a catalyst which is Pd-doped metal oxide solid solution, and the general formula of the metal oxide solid solution is ZnxZr1-xO and x are 0.13 to 0.5.
According to the catalyst, the doping amount of the Pd element is 0.1-1 wt% based on the mass of the catalyst.
The invention also provides a preparation method of the catalyst, which adopts a coprecipitation method to prepare the zinc source, the zirconium source and the palladium source, and then roasting.
According to the preparation method, the roasting temperature is 450-550 ℃.
According to the preparation method, the zinc source is zinc nitrate.
According to the preparation method, the zirconium source is zirconium nitrate.
According to the preparation method, the palladium source is palladium nitrate.
According to the preparation method, the coprecipitation method is to add an aqueous solution containing a zinc source, a zirconium source and a palladium source into an alkali solution to obtain a precipitate.
According to the above production method, the aqueous solution of ammonium carbonate is an alkali solution.
According to the preparation method, the reaction temperature of the coprecipitation method is 60-80 ℃. For example, it may be 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃.
The invention also discloses application of the catalyst in preparation of methanol by hydrogenation of carbon dioxide.
According to the application, before the catalyst is used for preparing methanol by carbon dioxide hydrogenation, hydrogenation reduction is carried out.
According to the application, the temperature is 300-400 ℃ during hydrogenation reduction. For example, the temperature may be 300 ℃, 350 ℃ or 400 ℃.
According to the above-mentioned use, the time for the hydrogenation reduction is at least 6 hours. Such as 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h or 16 h.
According to the application, the reduction pressure is 0.01-0.5 MPa during hydrogenation reduction. For example, it may be 0.05MPa, 0.1MPa, 0.15MPa, 0.2MPa, 0.25MPa, 0.3MPa, 0.35MPa, 0.4MPa, 0.45MPa or 0.5 MPa.
According to the application, during hydrogenation and reduction, the space velocity of hydrogen can be determined according to actual conditions, such as 2500-3500 ml/g/h.
The invention also discloses a method for preparing methanol by carbon dioxide hydrogenation, which adopts the catalyst, and the reaction raw material gas is CO2And H2And (4) forming. Preferably, one or more of the following features are included: CO 22And H2Body ofThe volume ratio is 1 (2-7), the reaction temperature is 300-400 ℃, and the reaction pressure is 2-7 MPa. More preferably, CO2And H2Is 1: 3. More preferably, the reaction temperature is 320 ℃. More preferably, the reaction pressure is 5 MPa.
According to the method, the reaction space velocity is 5000-24000 ml/g/h.
Compared with the prior art, the method for preparing CO provided by the invention2The technical scheme of the catalyst for preparing methanol by hydrogenation has the following beneficial effects:
1) the invention dopes noble metal Pd into the traditional ZnZrO oxide solid solution and utilizes noble metal H2The catalyst has the characteristics of strong adsorption performance, improves the reaction activity of the catalyst, utilizes a small amount of Pd atoms for doping, ensures that the crystal lattice of the original ZnZrO oxide solid solution generates expansion strain, and effectively changes the catalytic performance of the traditional ZnZrO oxide solid solution.
2) The catalyst of the invention has excellent catalytic performance, CO2The conversion rate and the methanol selectivity are excellent.
3) The catalyst causes the position of Pd in ZnZrO solid solution to change by regulating and controlling the doping amount of Pd, thereby changing the selectivity of methanol. The doping of trace Pd is proved to have the best methanol yield in the reaction, and the reduction of the consumption of noble metal is beneficial to reducing the cost and utilizing large-scale industrial application.
4) The preparation process of the catalyst is simple and easy to repeat, and the catalyst can be prepared in a large scale.
In conclusion, the invention provides a new Pd precious metal doped ZnZrO solid solution catalyst and a preparation method thereof, and the catalyst is used for evaluating the reaction performance in a fixed bed reactor, has the characteristics of high activity, high methanol selectivity and long-time stable operation at higher temperature and pressure, and provides wide prospects for subsequent industrial application and coupled methanol subsequent conversion processes (MTO, MTG).
Drawings
FIG. 1 is a graph showing the effect of catalytic stability of the catalyst described in example 1 over a long period of operation.
FIG. 2 shows XRD spectra of catalysts of examples 4-6 of the present invention.
Detailed Description
The following description of the embodiments of the present invention is provided for illustrative purposes, and other advantages and effects of the present invention will become apparent to those skilled in the art from the present disclosure.
Before the present embodiments are further described, it is to be understood that the scope of the invention is not limited to the particular embodiments described below; it is also to be understood that the terminology used in the examples is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the present invention. Test methods in which specific conditions are not specified in the following examples are generally carried out under conventional conditions or under conditions recommended by the respective manufacturers.
When numerical ranges are given in the examples, it is understood that both endpoints of each of the numerical ranges and any value therebetween can be selected unless the invention otherwise indicated. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In addition to the specific methods, devices, and materials used in the examples, any methods, devices, and materials similar or equivalent to those described in the examples may be used in the practice of the invention in addition to the specific methods, devices, and materials used in the examples, in keeping with the knowledge of one skilled in the art and with the description of the invention.
Example 1
Preparation of Pd-doped ZnZr oxide solid solution (Pd-Zn) by coprecipitation methodxZr1-xO): zinc nitrate and zirconium nitrate are dissolved in 240mL of deionized water according to the molar ratio of 0.13:0.87 to form a salt solution A (the mass of the added two nitrates is 1.313g and 12.685g respectively), the solution A is stirred at 30 ℃ for 1h, and then palladium nitrate with the corresponding mass of 0.004g Pd is added and dissolved in the salt solution A with stirring. 6.660g of ammonium carbonate was dissolved in 220mL of deionized water and thoroughly stirred to form an alkali solution B. The A solution was transferred to a round bottom flask and preheated in a 70 ℃ oil bath, then the B solution was added to the round bottom flask with a peristaltic pump at 3ml/min under nitrogen purge, after which it was added at 7Stirring was continued for 3h at 0 ℃. Cooling the obtained precipitate to room temperature, separating the precipitate from the solution under high-speed centrifugation, washing the precipitate with deionized water, centrifuging again, repeating the process for three times, and drying the precipitate at 60 ℃ for 12 hours. Roasting: then roasting the mixture for 3 hours at 500 ℃ in the air to obtain ZnZr oxide solid solution (Pd-Zn) with 0.1wt percent of Pd contentxZr1-xO) catalyst (x ═ 0.13).
Reduction: the obtained Pd-doped ZnZr oxide solid solution (Pd-Zn)xZr1-xO) catalyst is placed in a fixed bed high-pressure micro reactor, and hydrogen is introduced to carry out reduction under normal pressure, wherein the reduction space velocity is 3000ml/g/h, the reduction temperature is 400 ℃, and the reduction time is 12 h.
Catalyzing: after the reduction process is finished, the reaction furnace is cooled to room temperature, and H is introduced2/CO2The reaction is carried out by the reaction gas with the ratio of 3, the reaction pressure is 5MPa, and the reaction space velocity is 5000ml g-1·h-1The reaction temperature was 320 ℃ and the results of activity evaluation are shown in Table 1.
FIG. 1 shows the catalyst of this example in CO2The effect diagram of the stability test in the reaction of preparing methanol by hydrogenation is shown in fig. 1, and the catalyst has better catalytic stability.
Example 2
Preparation of Pd-doped ZnZr oxide solid solution (Pd-Zn) by coprecipitation methodxZr1-xO): zinc nitrate and zirconium nitrate are dissolved in 240mL of deionized water according to the molar ratio of 0.13:0.87 to form a salt solution A (the mass of the added two nitrates is 1.313g and 12.685g respectively), the solution A is stirred at 30 ℃ for 1h, and then palladium nitrate with the corresponding mass of 0.008g Pd is added and dissolved in the salt solution A with stirring. 6.660g of ammonium carbonate was dissolved in 220mL of deionized water and thoroughly stirred to form an alkali solution B. The A solution was transferred to a round bottom flask and preheated in a 70 ℃ oil bath, then the B solution was added to the round bottom flask with a peristaltic pump at 3ml/min under nitrogen purge, after which stirring was continued at 70 ℃ for 3 h. Cooling the obtained precipitate to room temperature, separating the precipitate from the solution under high-speed centrifugation, washing the precipitate with deionized water, centrifuging again, repeating the process for three times, and drying the precipitate at 60 ℃ for 12 hours. Baking at 500 ℃ in airFiring for 3 hours to obtain ZnZr oxide solid solution (Pd-Zn) with 0.2wt percent of Pd contentxZr1-xO) catalyst (x ═ 0.13).
Reduction: the obtained Pd-doped ZnZr oxide solid solution (Pd-Zn)xZr1-xO) catalyst is placed in a fixed bed high-pressure micro reactor, and hydrogen is introduced to carry out reduction under normal pressure, wherein the reduction space velocity is 3000ml/g/h, the reduction temperature is 400 ℃, and the reduction time is 12 h.
Catalyzing: after the reduction process is finished, the reaction furnace is cooled to room temperature, and H is introduced2/CO2The reaction is carried out by the reaction gas with the ratio of 3, the reaction pressure is 5MPa, and the reaction space velocity is 5000ml g-1·h-1The reaction temperature was 320 ℃ and the results of activity evaluation are shown in Table 1.
Example 3
Preparation of Pd-doped ZnZr oxide solid solution (Pd-Zn) by coprecipitation methodxZr1-xO): zinc nitrate and zirconium nitrate are dissolved in 240mL of deionized water according to the molar ratio of 0.13:0.87 to form a salt solution A (the mass of the two nitrates is 1.313g and 12.685g respectively), the solution A is stirred at 30 ℃ for 1h, and then palladium nitrate with the corresponding mass of 0.020g Pd is added and dissolved in the salt solution A with stirring. 6.660g of ammonium carbonate was dissolved in 220mL of deionized water and thoroughly stirred to form an alkali solution B. The A solution was transferred to a round bottom flask and preheated in a 70 ℃ oil bath, then the B solution was added to the round bottom flask with a peristaltic pump at 3ml/min under nitrogen purge, after which stirring was continued at 70 ℃ for 3 h. Cooling the obtained precipitate to room temperature, separating the precipitate from the solution under high-speed centrifugation, washing the precipitate with deionized water, centrifuging again, repeating the process for three times, and drying the precipitate at 60 ℃ for 12 hours. Then roasting the mixture for 3 hours at 500 ℃ in the air to obtain ZnZr oxide solid solution (Pd-Zn) with 0.5wt percent of Pd contentxZr1-xO) catalyst (x ═ 0.13).
Reduction: the obtained Pd-doped ZnZr oxide solid solution (Pd-Zn)xZr1-xO) catalyst is placed in a fixed bed high-pressure micro reactor, and hydrogen is introduced to carry out reduction under normal pressure, wherein the reduction space velocity is 3000ml/g/h, the reduction temperature is 400 ℃, and the reduction time is 12 h.
Catalyzing: after the reduction process is finished, the reaction furnace is cooled to room temperature, and H is introduced2/CO2The reaction is carried out by the reaction gas with the ratio of 3, the reaction pressure is 5MPa, and the reaction space velocity is 5000ml g-1·h-1The reaction temperature was 320 ℃ and the results of activity evaluation are shown in Table 1.
Example 4
Preparation of Pd-doped ZnZr oxide solid solution (Pd-Zn) by coprecipitation methodxZr1-xO): zinc nitrate and zirconium nitrate are dissolved in 240mL of deionized water according to the molar ratio of 0.33:0.67 to form a salt solution A (the mass of the added two nitrates is 1.313g and 12.685g respectively), the solution A is stirred at 30 ℃ for 1h, and then palladium nitrate with the corresponding mass of 0.040g Pd is added and dissolved in the salt solution A. 6.660g of ammonium carbonate was dissolved in 220mL of deionized water and thoroughly stirred to form an alkali solution B. The A solution was transferred to a round bottom flask and preheated in a 70 ℃ oil bath, then the B solution was added to the round bottom flask with a peristaltic pump at 3ml/min under nitrogen purge, after which stirring was continued at 70 ℃ for 3 h. Cooling the obtained precipitate to room temperature, separating the precipitate from the solution under high-speed centrifugation, washing the precipitate with deionized water, centrifuging again, repeating the process for three times, and drying the precipitate at 60 ℃ for 12 hours. Roasting in air at 500 ℃ for 3 hours to obtain ZnZr oxide solid solution (Pd-Zn) with 1wt percent of Pd contentxZr1- xO) catalyst (x ═ 0.13).
Reduction: pd-doped ZnZr oxide solid solution (Pd-Zn)xZr1-xO) catalyst is placed in a fixed bed high-pressure micro reactor, and hydrogen is introduced to carry out reduction under normal pressure, wherein the reduction space velocity is 3000ml/g/h, the reduction temperature is 400 ℃, and the reduction time is 12 h.
Catalyzing: after the reaction is finished, the temperature of the reaction furnace is reduced to room temperature, and H is introduced2/CO2The reaction is carried out by the reaction gas with the ratio of 3, the reaction pressure is 5MPa, and the reaction space velocity is 5000ml g-1·h-1The reaction temperature was 320 ℃ and the results of activity evaluation are shown in Table 1.
Example 5
Preparation of Pd-doped ZnZr oxide solid solution (Pd-Zn) by coprecipitation methodxZr1-xO): zinc nitrate and zirconium nitrate according to the molar ratio of0.33:0.67 was dissolved in 240mL of deionized water to form a salt solution A (1.313 g and 3.795g for each mass of nitrate added), stirred at 30 ℃ for 1h, and then added with a corresponding mass of palladium nitrate containing 0.0145g Pd and dissolved in the salt solution A with stirring. 6.660g of ammonium carbonate was dissolved in 220mL of deionized water and thoroughly stirred to form an alkali solution B. The A solution was transferred to a round bottom flask and preheated in a 70 ℃ oil bath, then the B solution was added to the round bottom flask with a peristaltic pump at 3ml/min under nitrogen purge, after which stirring was continued at 70 ℃ for 3 h. Cooling the obtained precipitate to room temperature, separating the precipitate from the solution under high-speed centrifugation, washing the precipitate with deionized water, centrifuging again, repeating the process for three times, and drying the precipitate at 60 ℃ for 12 hours. Roasting in air at 500 ℃ for 3 hours to obtain ZnZr oxide solid solution (Pd-Zn) with 1wt percent of Pd contentxZr1- xO) catalyst (x ═ 0.33).
Reduction: the obtained Pd-doped ZnZr oxide solid solution (Pd-Zn)xZr1-xO) catalyst is placed in a fixed bed high-pressure micro reactor, and hydrogen is introduced to carry out reduction under normal pressure, wherein the reduction space velocity is 3000ml/g/h, the reduction temperature is 400 ℃, and the reduction time is 12 h.
Catalyzing: after the reduction process is finished, the reaction furnace is cooled to room temperature, and H is introduced2/CO2The reaction is carried out by the reaction gas with the ratio of 3, the reaction pressure is 5MPa, and the reaction space velocity is 5000ml g-1·h-1The reaction temperature was 320 ℃ and the results of activity evaluation are shown in Table 1.
Example 6
Preparation of Pd-doped ZnZr oxide solid solution (Pd-Zn) by coprecipitation methodxZr1-xO): zinc nitrate and zirconium nitrate are dissolved in 240mL of deionized water according to the molar ratio of 1:1 to form a salt solution A (the mass of the two nitrates is 1.313g and 1.898g respectively), the solution A is stirred at 30 ℃ for 1h, and then palladium nitrate with the corresponding mass of 0.009g Pd is added and dissolved in the salt solution A under stirring. 6.660g of ammonium carbonate was dissolved in 220mL of deionized water and thoroughly stirred to form an alkali solution B. The solution A was transferred to a round bottom flask and preheated in a 70 ℃ oil bath, then the solution B was added to the round bottom flask with a peristaltic pump at a rate of 3ml/min under a nitrogen purge,stirring was then continued at 70 ℃ for 3 h. Cooling the obtained precipitate to room temperature, separating the precipitate from the solution under high-speed centrifugation, washing the precipitate with deionized water, centrifuging again, repeating the process for three times, and drying the precipitate at 60 ℃ for 12 hours. Then roasting the mixture for 3 hours at 500 ℃ in the air to obtain ZnZr oxide solid solution (Pd-Zn) with 1wt percent of Pd contentxZr1-xO) catalyst (x ═ 0.5).
Reduction: the obtained Pd-doped ZnZr oxide solid solution (Pd-Zn)xZr1-xO) catalyst is placed in a fixed bed high-pressure micro reactor, and hydrogen is introduced to carry out reduction under normal pressure, wherein the reduction space velocity is 3000ml/g/h, the reduction temperature is 400 ℃, and the reduction time is 12 h.
Catalyzing: after the reduction process is finished, the reaction furnace is cooled to room temperature, and H is introduced2/CO2The reaction is carried out by the reaction gas with the ratio of 3, the reaction pressure is 5MPa, and the reaction space velocity is 5000ml g-1·h-1The reaction temperature was 320 ℃ and the results of activity evaluation are shown in Table 1.
Example 7
Preparation of Pd-doped ZnZr oxide solid solution (Pd-Zn) by coprecipitation methodxZr1-xO): zinc nitrate and zirconium nitrate are dissolved in 240mL of deionized water according to the molar ratio of 0.13:0.87 to form a salt solution A (the mass of the added two nitrates is 1.313g and 12.685g respectively), the solution A is stirred at 30 ℃ for 1h, and then palladium nitrate with the corresponding mass of 0.004g Pd is added and dissolved in the salt solution A with stirring. 6.660g of ammonium carbonate was dissolved in 220mL of deionized water and thoroughly stirred to form an alkali solution B. The A solution was transferred to a round bottom flask and preheated in a 70 ℃ oil bath, then the B solution was added to the round bottom flask with a peristaltic pump at 3ml/min under nitrogen purge, after which stirring was continued at 70 ℃ for 3 h. Cooling the obtained precipitate to room temperature, separating the precipitate from the solution under high-speed centrifugation, washing the precipitate with deionized water, centrifuging again, repeating the process for three times, and drying the precipitate at 60 ℃ for 12 hours. Then roasting the mixture for 3 hours at 500 ℃ in the air to obtain ZnZr oxide solid solution (Pd-Zn) with 0.1wt percent of Pd contentxZr1-xO) catalyst (x ═ 0.13).
Reduction: the obtained Pd-doped ZnZr oxide solid solution (Pd)-ZnxZr1-xO) catalyst is placed in a fixed bed high-pressure micro reactor, and hydrogen is introduced to carry out reduction under normal pressure, wherein the reduction space velocity is 3000ml/g/h, the reduction temperature is 300 ℃, and the reduction time is 12 h.
Catalyzing: after the reduction process is finished, the reaction furnace is cooled to room temperature, and H is introduced2/CO2The reaction is carried out by the reaction gas with the ratio of 3, the reaction pressure is 5MPa, and the reaction space velocity is 5000ml g-1·h-1The reaction temperature was 320 ℃ and the results of activity evaluation are shown in Table 1.
Example 8
Preparation of Pd-doped ZnZr oxide solid solution (Pd-Zn) by coprecipitation methodxZr1-xO): zinc nitrate and zirconium nitrate are dissolved in 240mL of deionized water according to the molar ratio of 0.13:0.87 to form a salt solution A (the mass of the added two nitrates is 1.313g and 12.685g respectively), the solution A is stirred at 30 ℃ for 1h, and then palladium nitrate with the corresponding mass of 0.004g Pd is added and dissolved in the salt solution A with stirring. 6.660g of ammonium carbonate was dissolved in 220mL of deionized water and thoroughly stirred to form an alkali solution B. The A solution was transferred to a round bottom flask and preheated in a 70 ℃ oil bath, then the B solution was added to the round bottom flask with a peristaltic pump at 3ml/min under nitrogen purge, after which stirring was continued at 70 ℃ for 3 h. Cooling the obtained precipitate to room temperature, separating the precipitate from the solution under high-speed centrifugation, washing the precipitate with deionized water, centrifuging again, repeating the steps for three times, drying the precipitate at 60 ℃ for 12 hours, and roasting at 500 ℃ in the air for 3 hours to obtain the ZnZr oxide solid solution (Pd-Zn) with the Pd content of 0.1wt percentxZr1-xO) catalyst (x ═ 0.13).
Reduction: the obtained Pd-doped ZnZr oxide solid solution (Pd-Zn)xZr1-xO) catalyst is placed in a fixed bed high-pressure micro reactor, and hydrogen is introduced to carry out reduction under normal pressure, wherein the reduction space velocity is 3000ml/g/h, the reduction temperature is 320 ℃, and the reduction time is 12 h.
Catalyzing: after the reduction process is finished, the reaction furnace is cooled to room temperature, and H is introduced2/CO2The reaction is carried out by the reaction gas with the ratio of 3, the reaction pressure is 5MPa, and the reaction space velocity is 5000ml g-1·h-1At a reaction temperature ofThe results of the activity evaluation at 320 ℃ are shown in Table 1.
Example 9
Preparation of Pd-doped ZnZr oxide solid solution (Pd-Zn) by coprecipitation methodxZr1-xO): zinc nitrate and zirconium nitrate are dissolved in 240mL of deionized water according to the molar ratio of 0.13:0.87 to form a salt solution A (the mass of the added two nitrates is 1.313g and 12.685g respectively), the solution A is stirred at 30 ℃ for 1h, and then palladium nitrate with the corresponding mass of 0.004g Pd is added and dissolved in the salt solution A with stirring. 6.660g of ammonium carbonate was dissolved in 220mL of deionized water and thoroughly stirred to form an alkali solution B. The A solution was transferred to a round bottom flask and preheated in a 70 ℃ oil bath, then the B solution was added to the round bottom flask with a peristaltic pump at 3ml/min under nitrogen purge, after which stirring was continued at 70 ℃ for 3 h. Cooling the obtained precipitate to room temperature, separating the precipitate from the solution under high-speed centrifugation, washing the precipitate with deionized water, centrifuging again, repeating the steps for three times, drying the precipitate at 60 ℃ for 12 hours, and roasting at 500 ℃ in the air for 3 hours to obtain the ZnZr oxide solid solution (Pd-Zn) with the Pd content of 0.1wt percentxZr1-xO) catalyst (x ═ 0.13).
Reduction: the obtained Pd-doped ZnZr oxide solid solution (Pd-Zn)xZr1-xO) catalyst is placed in a fixed bed high-pressure micro reactor, and hydrogen is introduced to carry out reduction under normal pressure, wherein the reduction space velocity is 3000ml/g/h, the reduction temperature is 360 ℃, and the reduction time is 12 h.
Catalyzing: after the reduction process is finished, the reaction furnace is cooled to room temperature, and H is introduced2/CO2The reaction is carried out by the reaction gas with the ratio of 3, the reaction pressure is 5MPa, and the reaction space velocity is 5000ml g-1·h-1The reaction temperature was 320 ℃ and the results of activity evaluation are shown in Table 1.
Example 10
Preparation of Pd-doped ZnZr oxide solid solution (Pd-Zn) by coprecipitation methodxZr1-xO): dissolving zinc nitrate and zirconium nitrate in deionized water at a molar ratio of 0.13:0.87 to form a salt solution A (the mass of the two nitrates is 1.313g and 12.685g respectively), stirring at 30 deg.C for 1h, and adding palladium nitrate containing 0.004g Pd and corresponding mass to the salt solution AThe solution A is stirred and dissolved. 6.660g of ammonium carbonate was dissolved in 220mL of deionized water and thoroughly stirred to form an alkali solution B. The A solution was transferred to a round bottom flask and preheated in a 70 ℃ oil bath, then the B solution was added to the round bottom flask with a peristaltic pump at 3ml/min under nitrogen purge, after which stirring was continued at 70 ℃ for 3 h. Cooling the obtained precipitate to room temperature, separating the precipitate from the solution under high-speed centrifugation, washing the precipitate with deionized water, centrifuging again, repeating the steps for three times, drying the precipitate at 60 ℃ for 12 hours, and roasting at 500 ℃ in the air for 3 hours to obtain the ZnZr oxide solid solution (Pd-Zn) with the Pd content of 0.1wt percentxZr1-xO) catalyst (x ═ 0.13).
Reduction: the obtained Pd-doped ZnZr oxide solid solution (Pd-Zn)xZr1-xO) catalyst is placed in a fixed bed high-pressure micro reactor, and hydrogen is introduced to carry out reduction under normal pressure, wherein the reduction space velocity is 3000ml/g/h, the reduction temperature is 400 ℃, and the reduction time is 12 h.
Catalyzing: after the reduction process is finished, the reaction furnace is cooled to room temperature, and H is introduced2/CO2Reacting with 3 of reaction gas, the reaction pressure is 5MPa, and the reaction space velocity is 24000ml/g-1·h-1The reaction temperature was 320 ℃ and the results of activity evaluation are shown in Table 1.
TABLE 1
Comparative example 1
Preparation of ZnZr oxide solid solution (Zn) by coprecipitation methodxZr1-xO): dissolving zinc nitrate and zirconium nitrate in deionized water at a molar ratio of 0.13:0.87 to form a salt solution A (the mass of the two nitrates is 1.313g and 12.685g respectively), stirring at 30 ℃ for 1h, and dissolving 6.660g of ammonium carbonate in 220mL of deionized water to form an alkali solution B. The A solution was transferred to a round bottom flask and preheated in a 70 ℃ oil bath, then the B solution was added to the round bottom flask with a peristaltic pump at 3ml/min under nitrogen purge, after which stirring was continued at 70 ℃ for 3 h. Cooling the obtained precipitateCooling to room temperature, separating precipitate and solution under high-speed centrifugation, washing the precipitate with deionized water, centrifuging again, repeating for three times, drying the precipitate at 60 ℃ for 12h, and roasting at 500 ℃ in air for 3h to obtain ZnZr oxide solid solution (Zn)xZr1-xO) catalyst (x ═ 0.13).
Reduction: the obtained ZnZr oxide solid solution (Zn)xZr1-xO) catalyst is placed in a fixed bed high-pressure micro reactor, and hydrogen is introduced to carry out reduction under normal pressure, wherein the reduction space velocity is 3000ml/g/h, the reduction temperature is 400 ℃, and the reduction time is 12 h.
Catalyzing: after the reduction process is finished, the reaction furnace is cooled to room temperature, and H is introduced2/CO2The reaction is carried out by the reaction gas with the ratio of 3, the reaction pressure is 5MPa, the reaction space velocity is 5000ml g-1 h-1, the reaction temperature is 320 ℃, and the activity evaluation result is shown in the table 1.
Comparative example 2
Preparation of 0.58 wt% Pt-doped Pt/In by coprecipitation2O3Oxide catalyst: ammonium carbonate (15.6g) was dissolved in 200ml of water, followed by addition of an aqueous solution (300ml) of ammonium chloroplatinate (0.7g) and indium nitrate (28.6 g). Stirring at 70 deg.C for 2 h. Drying at 70 deg.C, and calcining in air at 450 deg.C for 3 hr. Pt/In is obtained2O3Catalyst (ref J.Catal.,2021,39, 4236-4244).
Catalyzing: without reduction, H is passed in2/CO2Reacting with 3 of reaction gas, the reaction pressure is 5MPa, and the reaction space velocity is 24000ml/g-1·h-1The reaction temperature was 300 ℃ and the results of activity evaluation are shown in Table 1. As is clear from comparison with example 10, the catalyst of the present invention has a higher methanol selectivity.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (10)
1. A catalyst, characterized in that the catalyst is a Pd-doped metal oxide solid solution having the general formula ZnxZr1-xO and x are 0.13 to 0.5.
2. The catalyst according to claim 1, wherein the Pd element is doped in an amount of 0.1-1 wt% based on the mass of the catalyst.
3. A method for preparing a catalyst according to any one of claims 1 to 2, characterized in that a zinc source, a zirconium source and a palladium source are used for preparation by a coprecipitation method and then calcined.
4. The preparation method of claim 3, wherein the roasting temperature is 450-550 ℃; and/or the reaction temperature of the coprecipitation method is 60-80 ℃.
5. The production method according to claim 3, wherein the zinc source is zinc nitrate; and/or the zirconium source is zirconium nitrate; and/or the palladium source is palladium nitrate; and/or the coprecipitation method is to add an aqueous solution containing a zinc source, a zirconium source and a palladium source into an alkali solution to obtain a precipitate.
6. The method according to claim 5, wherein the aqueous solution of ammonium carbonate is an aqueous solution of alkali.
7. Use of a catalyst according to any one of claims 1 to 2 in the preparation of methanol by hydrogenation of carbon dioxide.
8. Use according to claim 7, characterized in that prior to use in the hydrogenation of carbon dioxide for the preparation of methanol, a hydrogenation reduction is carried out.
9. A method for preparing methanol by hydrogenation of carbon dioxide is characterized in that the catalyst according to any one of claims 1-2 is adopted, and raw reaction gas is CO2And H2And (4) forming.
10. The method of claim 9, wherein the CO is2And H2The volume ratio of (1) to (2-7); and/or the reaction temperature is 300-400 ℃; and/or the reaction pressure is 2-7 MPa.
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