CN111790390A - Preparation method and application of copper-based catalyst with interface synergistic effect - Google Patents
Preparation method and application of copper-based catalyst with interface synergistic effect Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- 239000010949 copper Substances 0.000 title claims abstract description 56
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 47
- 230000002195 synergetic effect Effects 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical group [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 16
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 14
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 14
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 238000002425 crystallisation Methods 0.000 claims abstract description 6
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- 239000000243 solution Substances 0.000 claims description 12
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- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 9
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000084 colloidal system Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 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 4
- 239000007789 gas Substances 0.000 claims description 4
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 3
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- 238000005406 washing Methods 0.000 claims description 3
- 239000006004 Quartz sand Substances 0.000 claims description 2
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical class [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims description 2
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
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- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 8
- 239000011943 nanocatalyst Substances 0.000 abstract description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 abstract description 3
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- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
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- XTYUEDCPRIMJNG-UHFFFAOYSA-N copper zirconium Chemical compound [Cu].[Zr] XTYUEDCPRIMJNG-UHFFFAOYSA-N 0.000 description 8
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- 238000000864 Auger spectrum Methods 0.000 description 1
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- 229910001051 Magnalium Inorganic materials 0.000 description 1
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- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
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- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Inorganic materials [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 1
- LBVWQMVSUSYKGQ-UHFFFAOYSA-J zirconium(4+) tetranitrite Chemical compound [Zr+4].[O-]N=O.[O-]N=O.[O-]N=O.[O-]N=O LBVWQMVSUSYKGQ-UHFFFAOYSA-J 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
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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
- B01J23/007—Mixed salts
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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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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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
- C07C29/132—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 an oxygen containing functional group
- C07C29/136—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 an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—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 an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—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 an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
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Abstract
The invention discloses a preparation method and application of a copper-based catalyst with an interface synergistic effect. The preparation method comprises the following steps: firstly, a CuXMgAl multi-hydrotalcite precursor is synthesized by a nucleation crystallization isolation method, wherein X is one or more of Zr, Ti, Zn and Mn, and then the copper-based catalyst with the interface synergistic effect is prepared by in-situ hydrotalcite structure topology transformation reaction. The copper-based nano catalyst with rich interface structure (copper-oxygen-X-oxygen vacancy) prepared by the invention has the outstanding active structure characteristics of enhanced active metal and carrier interface concerted catalysis, controllable surface defect structure and the like; the structural characteristics promote the effective activation of the carbonyl of dimethyl oxalate molecules and the dissociation of hydrogen, and meanwhile, the catalyst also has the structural and performance advantages of larger active specific surface area, layered nano structure, long service life of the catalyst and the like. Has wide application prospect in the fields of energy catalysis, traditional industrial catalysis, petrochemical industry and the like.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a preparation method of a copper-based catalyst with an interface synergistic effect and application of the copper-based catalyst in catalyzing dimethyl oxalate hydrogenation reaction.
Background
Ethylene glycol is an important bulk organic chemical raw material and is widely used for producing fine chemical products such as polyester fibers, films, antifreeze, plastics, unsaturated polyester resins, lubricants and the like. With the development of economy and the release of downstream requirements, the consumption of ethylene glycol is continuously increased in recent years, the ethylene glycol has wide application prospect and strong market demand, and the dependence of the ethylene glycol industry in China on external import reaches more than 40%. At present, the production process route for industrially synthesizing ethylene glycol mainly comprises the steps of oxidizing ethylene to generate ethylene oxide, and hydrating the ethylene oxide to obtain the ethylene glycol. However, the production method not only exposes the defects of high cost, long production route, large energy consumption, relatively low ethylene glycol selectivity and the like; and the preparation process and the core technology of catalyst synthesis are mastered by foreign companies.
In recent years, according to the characteristics of rich coal in China, the technology for preparing ethylene glycol from coal (preparing synthetic gas from coal, and hydrogenating ethylene glycol by dimethyl oxalate catalysis) has become one of the most competitive emerging ethylene glycol synthesis routes in China due to the advantages of mild conditions, high product purity, good atom economy and the like. The hydrogenation of dimethyl oxalate is an important reaction process, and the design and development of a hydrogenation catalyst with high activity, high selectivity and high stability become core and difficult problems to be faced by domestic and foreign research institutions in the research process of a process route for preparing ethylene glycol by hydrogenating dimethyl oxalate. In the dimethyl oxalate hydrogenation reaction, the supported Cu-based catalyst shows excellent hydrogenation catalytic performance due to the advantages of high carbonyl hydrogenation selectivity, relatively low price and the like, and becomes a metal-based hydrogenation catalyst which is most widely researched and applied at present. The simple copper-based catalyst has harsh reaction conditions, and a single active site is easy to inactivate, so that a structure of the synergistic action of the metal Cu and the carrier interface is constructed, and a promising approach is provided for solving the problems.
Hydrotalcite is a class of classical two-dimensional anionic layered clay materials formed by non-covalent interactions of interlayer anions and host laminae of positively charged metals. Due to the structural advantages of adjustable layer plate element types, adjustable particle size and distribution of assemblies and the like of the hydrotalcite, the supported copper-based nano catalyst with high dispersity and uniform and stable interface structure can be prepared by utilizing the structural characteristics of topological transformation, and the increase or agglomeration of copper particles under the reaction condition can be effectively inhibited, so that the activity and stability of catalytic reaction are improved.
Disclosure of Invention
The invention aims to provide a preparation method of a copper-based catalyst with an interface synergistic effect and application of the copper-based catalyst in catalyzing dimethyl oxalate hydrogenation reaction. The preparation method is rapid and simple, is green and economical, obtains the nano-level interface structured copper-based catalyst, and has wide application prospects in the fields of energy catalysis, traditional industrial catalysis, petrochemical industry and the like.
The structure of the copper-based catalyst with the interface synergistic effect is as follows: copper nanoparticles anchored in a highly dispersed manner on a layered structure of a magnesium-aluminum composite metal oxide support, a reducible metal oxide XO2Coating and dispersing on the surface interface around the copper nano-particles to form a copper-based interface structure of a copper-oxygen-X-oxygen vacancy, wherein X is one or more of Zr, Ti, Zn and Mn; the copper-based catalyst contains 10-40% of Cu by mass, 10-35% of X by mass, 3-10nm of copper nanoparticles by average particle size, and 90-150m of specific surface area2/g。
The preparation method of the copper-based catalyst with the interface synergistic effect comprises the following steps: firstly, a CuXMgAl multi-hydrotalcite precursor is synthesized by a nucleation crystallization isolation method, wherein X is one or more of Zr, Ti, Zn and Mn, and then the copper-based catalyst with the interface synergistic effect is prepared by in-situ hydrotalcite structure topology transformation reaction.
The method for synthesizing the CuXMgAl multi-element hydrotalcite precursor by the nucleation crystallization isolation method comprises the following specific steps: preparing a mixed salt solution of copper nitrate, magnesium nitrate, aluminum nitrate and nitrate of X by using deionized water, wherein the sum of the concentrations of the copper nitrate, the magnesium nitrate and the nitrate of X is 0.5-2.0mol/L, and the concentration of the aluminum nitrate is 0.1-1.2 mol/L; then preparing a mixed alkali solution of sodium hydroxide and sodium carbonate, wherein the concentration of the sodium hydroxide is 0.1-2mol/L, and the concentration of the sodium carbonate is 0.1-1.5 mol/L; adding the prepared mixed salt solution and the mixed alkali solution into a colloid mill reactor at the same speed, wherein the rotation speed of a colloid mill is 3000-; crystallizing the slurry at 60-100 deg.C for 6-48 hr, cooling to room temperature, washing the obtained precipitate with deionized water and ethanol to neutrality, and oven drying at 50-80 deg.C for 8-24 hr.
The specific conditions of the in-situ hydrotalcite structure topology transformation reaction are as follows: placing the dried and ground CuXMgAl multi-element hydrotalcite precursor into a quartz reaction tube, placing the quartz reaction tube into a stainless steel tube of a miniature fixed bed, raising the temperature to 400-800 ℃ at an initial heating rate of 1-10 ℃/min in 20-60mL/min nitrogen gas flow, keeping the temperature for 3-8 hours, then lowering the temperature to room temperature, then raising the temperature to 200-600 ℃ at an initial heating rate of 1-10 ℃/min in 30-100mL/min hydrogen gas flow, keeping the temperature for 3-8 hours, and then lowering the temperature to room temperature to obtain the copper-based catalyst with the interface synergistic effect.
The prepared copper-based catalyst with the interface synergistic effect is applied to catalyzing dimethyl oxalate hydrogenation reaction. The conditions for catalyzing the dimethyl oxalate hydrogenation reaction are as follows: 0.1-3.0g of copper-based catalyst with the interface synergistic effect and 0.5-2 times of quartz sand or SiC are fully and uniformly mixed and placed in a catalytic reaction quartz tube, a methanol solution of dimethyl oxalate is injected into the quartz tube for vaporization by adopting an injection pump at the speed of 0.1-3mL/min under the conditions of 150-300 ℃ and 1.5-4.0MPa, the volume ratio of the dimethyl oxalate to the methanol is 1:9-1:5, hydrogen is introduced at the flow speed of 10-100mL/min for gas phase hydrogenation reaction, and the reaction time is 2-10 h.
The invention has the main advantages that: based on the anchoring of the net trap effect of the magnalium composite metal oxide on the hydro-ski layer plate to the active metal copper sites, the loaded copper-based nano with high dispersion degree of the active metal copper and uniform nano particle size is obtainedA rice catalyst; by reducible metal oxides XO2And (X ═ Zr, Ti, Ce and Mn) coating and regulating, and preparing the high-dispersion supported copper-based interface structure catalyst which has a geometric structure and an electronic structure different from those of single copper metal. The copper-based nano catalyst with rich interface structure (copper-oxygen-X-oxygen vacancy) prepared by the invention has the outstanding active structure characteristics of enhanced active metal and carrier interface concerted catalysis, controllable surface defect structure and the like; the structural characteristics promote the effective activation of the carbonyl of dimethyl oxalate molecules and the dissociation of hydrogen, and meanwhile, the catalyst also has the structural and performance advantages of larger active specific surface area, layered nano structure, long service life of the catalyst and the like. Based on the method, the catalyst has good catalytic performance in the gas-phase hydrogenation reaction of dimethyl oxalate, the conversion rate of the dimethyl oxalate reaches 60-99% and the selectivity of ethylene glycol reaches 45-99% at the mild reaction temperature of 180-200 ℃. And the catalyst stability in the reaction is good, and the activity and the selectivity are only reduced by less than 5 percent after the reaction is continuously carried out for 120 hours.
Drawings
Fig. 1 is an SEM image of CuZrMgAl quaternary hydrotalcite prepared in example 1.
FIG. 2A is an XRD pattern of a CuZrMgAl quaternary hydrotalcite prepared in example 1 and a CuMgAl hydrotalcite prepared in comparative example 1; fig. 2B is an XRD pattern of the copper zirconium interfacial catalyst prepared in example 1, and an XRD pattern of the general copper-based catalyst prepared in comparative example 1.
Figure 3 is an HRTEM of the copper zirconium interfacial catalyst prepared in example 1.
Fig. 4 is a TEM image of a general copper-based catalyst prepared in comparative example 1.
Fig. 5 is an XPS auger spectra comparison of Cu in the copper zirconium interfacial catalyst of example 1 and the common copper-based catalyst of comparative example 1.
FIG. 6 shows the copper zirconium interface catalyst of example 1 and a standard sample ZrO2XPS spectra of Zr in (1) are compared.
Figure 7 is an XPS spectra of O in the copper zirconium interfacial catalyst of example 1 compared to the conventional copper based catalyst of comparative example 1.
Detailed Description
Example 1
Separately weighing Cu (NO)3)2·3H2O，Mg(NO3)2·6H2O，Zr(NO3)4·5H2O and Al (NO)3)3·9H2O mixed and dissolved in 100ml of deionized water, wherein [ Cu ]2+]＝0.2mol/L，[Mg2+]＝0.6mol/L，[Zr4+]＝0.01mol/L，[Al3+]0.2mol/L of solution A, and fully stirring until the solution A is completely dissolved; weighing NaOH and Na2CO3Dissolved in 100ml of deionized water, wherein [ NaOH ]]1.6mol/L, [ CO ]3 2-]＝2[Al3+]Designated as solution B, was stirred well until completely dissolved. And (3) simultaneously introducing the solution A and the solution B into a colloid mill instrument, regulating the rotating speed of the colloid mill to 4500rpm, and reacting for 3min to obtain the slurry-like mixed solution with uniform nucleation. And (3) placing the mixed solution into a hydrothermal kettle for crystallization reaction at 90 ℃ for 48 hours, taking out and cooling to room temperature. The resulting precipitate was washed with deionized water and ethanol to neutrality (PH 7) and dried in an oven at 60 ℃ for 12 h. The CuZrMgAl quaternary hydrotalcite layered structure precursor with the sheet shape is proved to be prepared through the characterization of a scanning electron microscope picture and an X-ray diffraction picture.
Fully grinding a CuZrMgAl quaternary hydrotalcite precursor by using a quartz mortar, putting the ground CuZrMgAl quaternary hydrotalcite precursor into a quartz reaction tube, putting the quartz reaction tube into a stainless steel tube of a miniature fixed bed, heating to 550 ℃ at an initial heating rate of 5 ℃/min in 50mL/min nitrogen gas flow, keeping the temperature for 4 hours, then cooling to room temperature, heating to 250 ℃ at an initial heating rate of 5 ℃/min in 50mL/min hydrogen gas flow, keeping the temperature for 5 hours, and then cooling to room temperature. Through the combined technical analysis of high-resolution electron microscope observation, X-ray diffraction pattern, XPS photoelectron spectrogram, Auger spectrogram and the like, the copper-based nano catalyst with the copper-zirconium interface structure (copper-oxygen-X-oxygen vacancy) is found to be obtained.
Comparative example 1
Different from example 1 is [ Zr ]4+]The addition amount of (A) is 0, and the other preparation conditions are the same, and the catalyst is marked as a Cu/MMO common copper-based catalyst. Observed by a high-resolution electron microscope and subjected to X-ray diffraction patternAnd XPS photoelectron spectrum and Auger spectrum to obtain common nanometer copper particle supported on the composite metal oxide carrier.
Application example 1
1.5g of the catalysts prepared in example 1 and comparative example 1 were uniformly mixed with 2ml of SiC (40 to 60 mesh), respectively, and then filled into a reactor. A methanol solution of dimethyl oxalate (the volume ratio of dimethyl oxalate to methanol is 1:9) as a raw material is injected at the speed of 0.3ml/min by a syringe pump and enters a reaction bed layer after being vaporized. Introducing H at 180 ℃ and 2.0MPa at a flow rate of 50mL/min2The gas flow makes the reactant dimethyl oxalate and the catalyst carry out gas-phase hydrogenation reaction for 4 hours. And separating the reacted catalyst from the reaction liquid, washing and drying the separated catalyst for recycling, and using the reaction liquid for gas chromatography analysis. Experimental results for the copper zirconium interface catalyst of example 1: the conversion rate of dimethyl oxalate reaches 98%, the selectivity of ethylene glycol reaches 96%, and good activity is shown. While the common copper-based catalyst Cu/MMO only shows 85 percent of conversion rate and 80 percent of glycol selectivity. This fully embodies the excellent catalytic performance of the copper zirconium interface catalyst.
Claims (6)
1. A copper-based catalyst with interfacial synergism, characterized in that the structure of the copper-based catalyst with interfacial synergism is as follows: copper nanoparticles anchored in a highly dispersed manner on a layered structure of a magnesium-aluminum composite metal oxide support, a reducible metal oxide XO2Coating and dispersing on the surface interface around the copper nano-particles to form a copper-based interface structure of a copper-oxygen-X-oxygen vacancy, wherein X is one or more of Zr, Ti, Zn and Mn; the copper-based catalyst contains 10-40% of Cu by mass, 10-35% of X by mass, 3-10nm of copper nanoparticles by average particle size, and 90-150m of specific surface area2/g。
2. A preparation method of a copper-based catalyst with an interface synergistic effect is characterized by comprising the following steps: firstly, a CuXMgAl multi-hydrotalcite precursor is synthesized by a nucleation crystallization isolation method, wherein X is one or more of Zr, Ti, Zn and Mn, and then the copper-based catalyst with the interface synergistic effect is prepared by in-situ hydrotalcite structure topology transformation reaction.
3. The preparation method according to claim 2, wherein the nucleation crystallization isolation method comprises the following specific steps: preparing a mixed salt solution of copper nitrate, magnesium nitrate, aluminum nitrate and nitrate of X by using deionized water, wherein the sum of the concentrations of the copper nitrate, the magnesium nitrate and the nitrate of X is 0.5-2.0mol/L, and the concentration of the aluminum nitrate is 0.1-1.2 mol/L; then preparing a mixed alkali solution of sodium hydroxide and sodium carbonate, wherein the concentration of the sodium hydroxide is 0.1-2mol/L, and the concentration of the sodium carbonate is 0.1-1.5 mol/L; adding the prepared mixed salt solution and the mixed alkali solution into a colloid mill reactor at the same speed, wherein the rotation speed of a colloid mill is 3000-; crystallizing the slurry at 60-100 deg.C for 6-48 hr, cooling to room temperature, washing the obtained precipitate with deionized water and ethanol to neutrality, and oven drying at 50-80 deg.C for 8-24 hr.
4. The preparation method according to claim 2, wherein the specific conditions of the in-situ hydrotalcite structure topology transformation reaction are as follows: placing the dried and ground CuXMgAl multi-element hydrotalcite precursor into a quartz reaction tube, placing the quartz reaction tube into a stainless steel tube of a miniature fixed bed, raising the temperature to 400-800 ℃ at an initial heating rate of 1-10 ℃/min in 20-60mL/min nitrogen gas flow, keeping the temperature for 3-8 hours, then lowering the temperature to room temperature, then raising the temperature to 200-600 ℃ at an initial heating rate of 1-10 ℃/min in 30-100mL/min hydrogen gas flow, keeping the temperature for 3-8 hours, and then lowering the temperature to room temperature to obtain the copper-based catalyst with the interface synergistic effect.
5. Use of a copper-based catalyst with interfacial synergism prepared according to any of claims 2-4 for catalyzing the hydrogenation of dimethyl oxalate.
6. The use of claim 5, wherein the conditions for catalyzing the hydrogenation reaction of dimethyl oxalate are as follows: 0.1-3.0g of copper-based catalyst with the interface synergistic effect and 0.5-2 times of quartz sand or SiC are fully and uniformly mixed and placed in a catalytic reaction quartz tube, a methanol solution of dimethyl oxalate is injected into the quartz tube for vaporization by adopting an injection pump at the speed of 0.1-3mL/min under the conditions of 150-300 ℃ and 1.5-4.0MPa, the volume ratio of the dimethyl oxalate to the methanol is 1:9-1:5, hydrogen is introduced at the flow speed of 10-100mL/min for gas phase hydrogenation reaction, and the reaction time is 2-10 h.
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