CN113101937A - Doped mixed-valence copper catalyst and preparation method and application thereof - Google Patents

Doped mixed-valence copper catalyst and preparation method and application thereof Download PDF

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CN113101937A
CN113101937A CN202110439320.7A CN202110439320A CN113101937A CN 113101937 A CN113101937 A CN 113101937A CN 202110439320 A CN202110439320 A CN 202110439320A CN 113101937 A CN113101937 A CN 113101937A
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nitrate
chloride
acetate
sulfate
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朱红平
赖恩义
陈艺林
赵金波
江云宝
李军
江巧珠
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Xiamen University
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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    • 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
    • B01J23/83—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 rare earths or actinides
    • 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
    • B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • 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
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8953—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—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 relates to a doped mixed-valence copper catalyst and a preparation method and application thereof. The doped mixed-valence copper catalyst comprises a carrier and a metal element component, wherein the metal element component comprises Cu (0), Cu (I), other metal elements M 'with valence of 0 and other metal elements M' with valence of other. The catalyst can be applied to hydrogenation of malonate or 3-hydracrylic acid ester compounds to prepare 1, 3-propylene glycol.

Description

Doped mixed-valence copper catalyst and preparation method and application thereof
Technical Field
The invention relates to a doped mixed-valence copper catalyst and a preparation method thereof, and the catalyst can be used for preparing 1, 3-propylene glycol by hydrogenation of malonate and 3-hydroxypropionate compounds.
Background
1, 3-propanediol is an important organic intermediate of glycols, and is widely used as an additive or a basic synthetic material for foods, medicines, cosmetics, paints, and the like. 1, 3-propanediol is also an important monomer, and can be subjected to polymerization reaction with multistage organic acids, multistage isonitrile acid esters, multistage acyl chlorides and the like to produce polymeric materials such as polyesters, polyamides and the like. The prominent one is that 1, 3-propanediol reacts with terephthalic acid to synthesize polytrimethylene terephthalate, and the polyester is a high-end polyester elastic fiber and has wide market application.
The ethylene oxide hydrogen esterification method can prepare 3-hydroxy propionate, and the hydrogenation reaction of 3-hydroxy propionate can synthesize 1, 3-propanediol, but the latter is easy to generate side reactions such as dehydration and deacidification, so the reaction selectivity is not high (Surface Review and Letters, 2009, 16, 343-349). 2001 U.S. Pat. No. 4, 6191321, 1 and WO00/18712 of Shell company claims Cu-ZnO catalysts and Zr-and Ba-doped Cu-ZnO catalysts, the examples showing a liquid hourly space velocity of 1h-1The conversion of 3-hydroxypropionate varied from 50.19 to 99.60% at 1500psig and 165-190 ℃ with corresponding 1, 3-propanediol selectivities of 40.31 to 60.73%. Patent application of copper chromate or Pd/C catalyst was made by Samsung corporation 2002, and performance tests in a tank reactor are mentioned in the examples, which showed that copper chromate catalyzed only 5% conversion of 3-hydroxypropionate at 1500psig pressure, 180 ℃ and 15h reaction time, and that the selectivity to the product 1, 3-propanediol was only 3% (US6348632B1 and US6521801B 2). The Lanzhou chemical and physical research institute patents CN101020635A and US20070191629A1 disclose Cu/TiO in 20072-SiO2The catalyst and the fixed bed reactor obtain the 3-methyl hydroxypropionate with the conversion rate of 80.3-93.9% and the selectivity of 1, 3-propanediol of 79.6-88.2% at the temperature of 140 ℃ and the pressure of 7 MPa.
Disclosure of Invention
The research of the inventor finds that Cu/SiO2Catalyst for converting 3-hydroxy propionate into 1, 3-propylene glycol and its catalytic machineIt is based on the synergistic effect of Cu (0) and Cu (I) in the presence of hydrogen, wherein Cu (0) is responsible for H2Activation of (2) to produce H-Cu (I) acts as a Lewis acid to adsorb and activate the 3-hydroxypropionate, and the two act together to catalyze the conversion of the 3-hydroxypropionate to 1, 3-propanediol. Therefore, in this type of catalyst, the key point is to control the production of Cu (0) and Cu (I) in the presence of hydrogen. The inventors further studied and found that the ratio of Cu (0) to Cu (I) is controlled to be important, which also determines the reaction stability of the catalyst. The present inventors have further studied and found that the control of the Cu (0) component requires the addition of other suitable metals, while the control of the Cu (i) component also requires the addition of other suitable metals. Based on this, the present application is proposed.
In a first aspect, the present application provides a doped mixed-valence copper catalyst, which comprises a carrier and a metal element component, wherein the metal element component comprises Cu (0), Cu (I), other metal element M' with valence of 0 and other metal element M ″ with valence of other elements.
According to some embodiments of the invention, the molar ratio of Cu (0) to Cu (i) is 0.25 to 4.0, such as 0.5, 1.0, 1.3, 1.5, 1.8, 2.1, 2.5, 2.9, 3.0, 3.5, 3.8, and the like. In some embodiments, the molar ratio of Cu (0) to Cu (i) is 1-4. In some embodiments, the molar ratio of Cu (0) to Cu (i) is 2 to 4.
According to some embodiments of the invention, the molar ratio of the 0-valent further metal element M' to Cu (0) is in the range of 0.01 to 0.30, e.g. 0.01, 0.03, 0.05, 0.08, 0.1, 0.12, 0.15, 0.18, 0.2, 0.22, 0.25, 0.3. In some embodiments, the molar ratio of the 0-valent other metal element M' to Cu (0) is 0.1 to 0.15.
According to some embodiments of the invention, the molar ratio of the other metal element M "in other valence states to cu (i) is 0.01-0.30, e.g. 0.01, 0.03, 0.05, 0.08, 0.1, 0.12, 0.15, 0.18, 0.2, 0.22, 0.25, 0.3. In some embodiments, the molar ratio of the other metal element M' in other valence states to Cu (I) is 0.1-0.15.
According to some embodiments of the invention, the carrier is silica gel. According to some embodiments of the inventionFormula (II) [ Cu (0) + Cu (I)]With silica gel (in SiO)2In terms of moles) of 0.11 to 1.50, preferably 0.23 to 1.2.
According to some embodiments of the invention, M' is selected from one or several of transition metals, preferably one or more of ruthenium, nickel, cobalt, iron, silver, osmium, rhodium, gold.
According to some embodiments of the invention, M "is selected from one or more of transition metals, preferably zinc, manganese, chromium, cadmium, zirconium, titanium, hafnium, lanthanides, or alkali metals; the lanthanide metal is preferably lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium; the alkali metal is preferably magnesium, calcium, strontium, barium.
According to some embodiments of the invention, the catalyst is represented by the general formula:
[Cu(0)mM′(0)n][Cu(I)xM″yOz](SiO2)f
wherein Cu (0) means 0-valent copper, and M' (0) means other metal of 0-valent; cu (I) means positive 1-valent copper, M "means other metals of other valences, SiO2Refers to a silica gel carrier; m: x is 0.25-4.0, n: m is 0.01 to 0.30, y: x is 0.01-0.30, and z is [ Cu (0) ]mM′(0)n][Cu(I)xM″yOz](SiO2)fIs in a neutral molecular state, and f is selected to be [ Cu (0) + Cu (I)]With SiO2In a molar ratio of 0.11 to 1.50.
According to an embodiment of the present invention, the above formula is obtained by subjecting the catalyst to photoelectron spectroscopy.
In a second aspect, the present application provides a method for preparing a doped mixed-valence copper catalyst, comprising the steps of:
s1: mixing a copper salt, an M' salt and a carrier solution;
s2: mixing the mixture obtained in the step S1 with an alkaline precipitant solution to generate a solid precipitate;
s3: roasting the solid precipitate;
s4: and reducing the roasted product.
According to some embodiments of the invention, in S1, the copper salt is selected from one or more of a divalent copper salt and a monovalent copper salt. Specifically, the copper salt may be one or more of copper sulfate, copper nitrate, copper halide, copper perchlorate, copper organic acid, copper amine solution, cuprous sulfate, cuprous nitrate, cuprous halide, copper perchlorate, and cuprous organic acid, and preferably one or both of copper nitrate and copper acetate.
According to some embodiments of the invention, in step S1, the M' salt is selected from at least one of ruthenium trichloride, ruthenium acetate, potassium chlororuthenate, nickel sulfate, nickel nitrate, nickel chloride, nickel acetate, cobalt sulfate, cobalt nitrate, cobalt chloride, cobalt acetate, osmium chloride, iron sulfate, iron nitrate, iron chloride, iron acetate, silver sulfate, silver nitrate, silver acetate, rhodium nitrate, rhodium chloride, chloroauric acid, preferably one or more of rhodium chloride, nickel nitrate, cobalt nitrate, and silver nitrate.
According to some embodiments of the invention, in step S1, zinc sulfate, zinc nitrate, zinc chloride, zinc acetate, manganese sulfate, manganese nitrate, manganese chloride, manganese acetate, chromium sulfate, chromium nitrate, chromium chloride, chromium acetate, lanthanum nitrate, lanthanum acetate, ceric ammonium sulfate, cerium nitrate, ceric ammonium nitrate, cerium acetate, praseodymium sulfate, praseodymium chloride, praseodymium nitrate, praseodymium acetate, neodymium sulfate, neodymium nitrate, neodymium chloride, neodymium acetate, samarium sulfate, samarium nitrate, samarium chloride, samarium acetate, europium sulfate, europium nitrate, europium chloride, europium acetate, gadolinium sulfate, gadolinium nitrate, gadolinium chloride, gadolinium acetate, terbium sulfate, terbium nitrate, terbium chloride, terbium acetate, dysprosium sulfate, dysprosium chloride, dysprosium acetate, dysprosium sulfate, holmium nitrate, holmium chloride, erbium sulfate, erbium nitrate, erbium chloride, erbium acetate, thulium sulfate, thulium nitrate, thulium chloride, thulium acetate, ytterbium chloride, ytterbium acetate, Cadmium chloride, cadmium acetate, cadmium sulfate, cadmium nitrate, magnesium sulfate, magnesium nitrate, magnesium chloride, magnesium acetate, calcium nitrate, calcium chloride, calcium acetate, strontium chloride, strontium acetate, barium chloride, barium nitrate, barium acetate, zirconium sulfate, zirconium nitrate, zirconium chloride, zirconium acetate, titanium chloride, hafnium sulfate, hafnium chloride, magnesium sulfate, magnesium nitrate, magnesium chloride, magnesium acetate, calcium chloride, strontium sulfate, calcium nitrate, strontium chloride, strontium acetate, barium chloride, barium nitrate, barium acetate, preferably one or more selected from zinc nitrate, zirconium nitrate, manganese nitrate and cerium nitrate.
According to some embodiments of the present invention, in step S1, the alkaline precipitant is selected from sodium hydroxide, lithium hydroxide, potassium hydroxide, ammonia water, sodium carbonate, lithium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, urea, ammonia water, ammonium carbonate, ammonium bicarbonate, sodium methoxide, sodium ethoxide, sodium n-propoxide, sodium isopropoxide, sodium n-butoxide, sodium t-butoxide, lithium methoxide, lithium ethoxide, lithium n-propoxide, lithium n-butoxide, lithium isobutoxide, lithium t-butoxide, potassium methoxide, potassium ethoxide, potassium n-propoxide, potassium isopropoxide, potassium n-butoxide, potassium isobutoxide, potassium t-butoxide, sodium amide, lithium amide, potassium amide, sodium alkylamino, lithium alkylamino, potassium alkylamino, preferably one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonium bicarbonate, ammonia, urea, sodium methoxide, sodium carbonate, potassium hydroxide, ammonium bicarbonate, ammonia water, urea, potassium carbonate, sodium isopropoxide, one or more of sodium ethoxide.
According to some embodiments of the invention, the carrier solution is a silica sol solution, preferably having a silica sol solution mass fraction concentration of 5-50%, more preferably 10-35%.
According to some embodiments of the present invention, heating is performed before adding the alkaline precipitant in step S2, and the heating temperature may be 40 to 99 ℃, preferably 50 to 90 ℃.
According to some embodiments of the present invention, in step S2, aging is performed after adding an alkaline precipitant to precipitate a solid, and the aging time may be 1 to 120 hours, preferably 5 to 72 hours.
According to some embodiments of the present invention, in step S2, the solid precipitate is filtered, and the filtering method may be selected from one of vacuum filtration, centrifugal filtration, rotary vacuum filtration and pressure filtration.
According to some embodiments of the present invention, in step S2, the obtained filter cake is washed, and the washing solvent is selected from one or more of methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, and deionized water.
According to some embodiments of the present invention, in step S2, the washing with the solvent is performed sufficiently until the concentration of the metal ions in the washing solution does not decrease any more, wherein the requirement for the conductivity measurement is that the conductivity measurement value does not decrease any more.
According to some embodiments of the present invention, in step S2, the solid precipitate is dried, and the drying temperature may be 50 to 250 ℃, preferably 70 to 200 ℃; the drying time at this temperature may be set to 1 to 120 hours, preferably 5 to 72 hours.
According to some embodiments of the present invention, in step S3, the calcination temperature is 350-700 deg.C, the calcination time is 1-48 hours, and the calcination time is preferably 1-24 hours.
According to some embodiments of the present invention, the solid precipitate is pulverized, shaped, and sieved, preferably with a mesh size of 5-80 mesh, before the reduction treatment in step S4.
According to some embodiments of the present invention, in step S4, the reduction treatment is performed in a reducing atmosphere. According to some embodiments of the invention, the reducing gas uses hydrogen, a hydrogen/nitrogen mixture or carbon monoxide, preferably hydrogen and a hydrogen/nitrogen mixture. When a hydrogen/nitrogen mixture is used, the volume fraction of hydrogen is selected from 1 to 50%, preferably from 5 to 20%.
According to some embodiments of the present invention, in step S4, the temperature of the reduction treatment is 100 ℃ and 500 ℃, and the reduction time can be 1-48 hours, preferably 1-20 hours.
The catalyst prepared by the preparation method can accurately control the composition of various elements, and can keep relatively uniform structure and composition of the catalyst prepared in batches. The catalyst prepared by the method can effectively obtain the expected catalytic reaction activity and the selectivity of the target product.
In a third aspect, the present application provides the use of a catalyst as described in the first aspect of the present application or a catalyst prepared by the preparation process as described in the second aspect of the present application in a hydrogenation reaction.
According to an embodiment of the invention, in this application, the feedstock for the hydrogenation reaction is a carboxylic acid ester.
According to some embodiments of the invention, in this application, the hydrogenation feedstock is selected from one or more of methyl malonate, ethyl malonate, propyl malonate, butyl malonate, pentyl malonate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, and pentyl 3-hydroxypropionate.
According to an embodiment of the invention, in this application, the product of the hydrogenation reaction comprises 1, 3-propanediol.
In a fourth aspect, the present application provides a hydrogenation process or a process for the production of 1, 3-propanediol comprising subjecting a hydrogenation feedstock to a hydrogenation reaction in the presence of a catalyst as described in the first aspect of the present application or a catalyst produced by a production process as described in the second aspect of the present application.
According to some embodiments of the invention, the hydrogenation feedstock is a carboxylic acid ester, preferably at least one of malonate or 3-hydroxypropionate based compounds.
According to some embodiments of the present invention, the malonate type compound has a structure represented by formula I, the 3-hydroxypropionate type compound has a structure represented by formula II,
Figure BSA0000240366530000051
wherein R is selected from C1-C8 alkyl, such as methyl, ethyl, propyl, butyl, pentyl or hexyl.
According to some embodiments of the invention, the hydrogenation feedstock is selected from one or more of methyl malonate, ethyl malonate, propyl malonate, butyl malonate, pentyl malonate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, pentyl 3-hydroxypropionate.
According to some embodiments of the invention, the reaction scheme of the hydrogenation reaction is as follows:
Figure BSA0000240366530000061
in some embodiments of the invention, the temperature of the hydrogenation reaction is 130-.
In some embodiments of the invention, the pressure of the hydrogenation reaction is between 10 and 100bar, preferably between 40 and 80 bar.
In some embodiments of the invention, the hydrogenation feedstock is hydrogenated in a solvent-free or solution form. In solution form, the solvent used may be chosen from C1-C20The solvent is preferably one or more selected from methanol, ethanol, propanol, butanol, pentanol, dimethyl ether, diethyl ether, methyl tert-butyl ether, tetrahydrofuran, 2, 6-oxolane, pentane, hexane, heptane and octane.
In some embodiments of the invention, the mass fraction of the hydrogenated feedstock solution is selected from 10 to 100%, preferably 12 to 50%, or preferably 100% (i.e., in the solvent-free state).
In some embodiments of the invention, the molar ratio of hydrogen to hydrogenation feedstock is selected from the range of 20 to 1000, preferably 100-400.
In some embodiments of the invention, the liquid hourly space velocity is in the range of from 0.01 to 1 hour-1Preferably 0.1 to 0.5h-1。
The catalyst is adopted to carry out the hydrogenation of malonate or 3-hydracrylic acid ester compounds to prepare the 1, 3-propylene glycol, the reaction temperature is 130-270 ℃, the reaction pressure of hydrogen is 10-100bar, the hydrogen-ester ratio is 20-1000, and the liquid hourly space velocity is 0.01-1h-1In the case, the conversion rate of malonate and 3-hydracrylic acid ester compounds can reach 94%, and the selectivity of 1, 3-propylene glycol can reach 90%.
Drawings
FIG. 1 is a photoelectron spectroscopy analysis chart of the catalyst prepared in example.
Detailed Description
The present invention is described in detail below with reference to specific examples, and those skilled in the art will recognize that the present invention is not limited to the following.
Example 1
Selecting a reaction vessel, injecting 1000mL of deionized water, starting stirring, and respectively weighing 114.76 g of Cu (NO)3)2·3H2O, 3.63 g Ni (NO)3)2·6H2O, 2.97 g Zn (NO)3)2·6H2O, adding weighed Cu (NO) one by one under stirring3)2·3H2O、Ni(NO3)2·6H2O、Zn(NO3)2·6H2And O, then adding the obtained metal ion mixed solution into 110.15 g of silica sol solution with the mass fraction of 30%, and stirring to reach a uniform degree. The mixture was heated to 75 ℃, and an aqueous solution containing 79.6 grams of sodium hydroxide was added thereto to maximize the formation of precipitates of metal ions with the silica sol. After the addition, the mixture was kept at 75 ℃ and stirred for 12 hours. And filtering the mixture by adopting a reduced pressure suction filtration mode to obtain a filter cake, and fully washing the filter cake by using deionized water until the conductivity of the washing liquid is constant. The obtained filter cake was placed in a drying oven and dried at 100 ℃ for 20 hours to obtain a granular solid. The obtained granular solid is placed in a heating furnace and roasted for 6 hours at 450 ℃ to obtain the roasted granular solid. And (3) crushing, forming and screening the roasted granular solid, selecting 20-40 meshes of granular solid, loading the granular solid on a fixed bed type reactor, and reducing for 12 hours at 300 ℃ in the atmosphere of hydrogen/nitrogen mixed gas with the hydrogen volume fraction of 5% to obtain the doped mixed-valence copper catalyst.
Then the reducing gas was replaced by hydrogen atmosphere, cooled to 155 ℃ and the system was gradually raised to 70 bar. Pumping 20 percent of 3-methyl hydroxypropionate solution and hydrogen into a reactor loaded with a certain mesh number of doped mixed valence copper catalysts, controlling the molar ratio of the hydrogen to the 3-methyl hydroxypropionate to be 200: 1 and controlling the liquid hourly space velocity to be 0.1h-1The reaction was started, the product solution was obtained after passing through the catalyst bed and cooled, the sample was analyzed, the product was collected for future use, and the catalyst evaluation data are listed in table 1. The doped mixed valence copper catalyst is analyzed by photoelectron spectroscopyAnd then has the following structural formula: [ Cu (0)0.65Ni(0)0.025][Cu(I)0.3Zn0.02O0.17](SiO2)1 1。
Figure BSA0000240366530000071
Comparative example 1:
selecting a reaction vessel, injecting 1000mL of deionized water, starting stirring, and respectively weighing 114.76 g of Cu (NO)3)2·3H2O, adding weighed Cu (NO) one by one under stirring3)2·3H2And O, then adding the obtained metal ion mixed solution into 110.15 g of silica sol solution with the mass fraction of 30%, and stirring to reach a uniform degree. The mixture was heated to 75 ℃ and an aqueous solution containing 76 g of sodium hydroxide was added thereto to maximize the formation of precipitates of metal ions with the silica sol. The subsequent preparation and evaluation of the catalyst were carried out as in example 1, and the catalyst evaluation data are given in Table 1. The doped mixed valence copper catalyst has the following structural formula after being analyzed by photoelectron spectroscopy: [ Cu (0)0.80][Cu(I)0.15O0 15](SiO2)1 1。
Comparative example 2
Selecting a reaction vessel, injecting 1000mL of deionized water, starting stirring, and respectively weighing 114.76 g of Cu (NO)3)2·3H2O, 3.63 g Ni (NO)3)2·6H2O, adding weighed Cu (NO) one by one under stirring3)2·3H2O、Ni(NO3)2·6H2And O, then adding the obtained metal ion mixed solution into 110.15 g of silica sol solution with the mass fraction of 30%, and stirring to reach a uniform degree. The mixture was heated to 75 ℃ and an aqueous solution containing 78 g of sodium hydroxide was added to maximize the formation of precipitates of metal ions with the silica sol. The subsequent preparation and evaluation of the catalyst were carried out as in example 1, and the catalyst evaluation data are given in Table 1. Doping typeThe mixed valence copper catalyst has the following structural formula after being analyzed by photoelectron spectroscopy: [ Cu (0)0.90Ni(0)0 025][Cu(I)0 05O0.025](SiO2)1.1。
Comparative example 3
Selecting a reaction vessel, injecting 1000mL of deionized water, starting stirring, and respectively weighing 114.76 g of Cu (NO)3)2·3H2O, 2.97 g Zn (NO)3)2·6H2O, adding weighed Cu (NO) one by one under stirring3)2·3H2O、Zn(NO3)2·6H2And O, then adding the obtained metal ion mixed solution into 110.15 g of silica sol solution with the mass fraction of 30%, and stirring to reach a uniform degree. The mixture was heated to 75 ℃, and an aqueous solution containing 77.6 grams of sodium hydroxide was added to maximize the formation of precipitates of metal ions with the silica sol. The subsequent preparation and evaluation of the catalyst were carried out as in example 1, and the catalyst evaluation data are given in Table 1. The doped mixed valence copper catalyst has the following structural formula after being analyzed by photoelectron spectroscopy: [ Cu (0)0.15][Cu(I)0 80Zn0.02O0.41](SiO2)1 1。
TABLE 1 summary of the reaction results
Figure BSA0000240366530000081
Note: the raw material is a methanol solution of 20 mass percent of methyl 3-hydroxypropionate; the reaction temperature is 155 ℃, the reaction pressure is 70bar, and the liquid hourly space velocity is 0.1h-1Hydrogen to ester ratio of 200
It is apparent from the results of example 1 and comparative examples 1 to 3 that without the regulation of M' (0) and M ", the ratio of Cu (0)/Cu (I) is unbalanced, thereby reducing the conversion of methyl 3-hydroxypropionate and the selectivity of 1, 3-propanediol.
Examples 2 to 6, while keeping the values of y and f constant, the values of n are changed and x, m and z are changed accordingly
Example 2
Selecting a reaction vessel, injecting 1000mL of deionized water, starting stirring, and respectively weighing 114.76 g of Cu (NO)3)2·3H2O, 5.09 g Ni (NO)3)2·6H2O, 2.97 g Zn (NO)3)2·6H2O, the mass of NaOH in the alkaline precipitant solution was 80.4 grams. The subsequent preparation and evaluation of the catalyst were carried out as in example 1, and the catalyst evaluation data are given in Table 1. The doped mixed valence copper catalyst has the following structural formula after being analyzed by photoelectron spectroscopy: [ Cu (0)0.68Ni(0)0 035][Cu(I)0.27Zn0.02O0 155](SiO2)1.1。
Example 3
Selecting a reaction vessel, injecting 1000mL of deionized water, starting stirring, and respectively weighing 114.76 g of Cu (NO)3)2·3H2O, 6.54 g Ni (NO)3)2·6H2O, 2.97 g Zn (NO)3)2·6H2O, the mass of NaOH in the alkaline precipitant solution was 81.2 grams. The subsequent preparation and evaluation of the catalyst were carried out as in example 1, and the catalyst evaluation data are given in Table 2. The doped mixed valence copper catalyst has the following structural formula after being analyzed by photoelectron spectroscopy: [ Cu (0)0.7Ni(0)0.045][Cu(I)0 25Zn0.02O0.145](SiO2)1.1。
Example 4
Selecting a reaction vessel, injecting 1000mL of deionized water, starting stirring, and respectively weighing 114.76 g of Cu (NO)3)2·3H2O, 8.00 g Ni (NO)3)2·6H2O, 2.97 g Zn (NO)3)2·6H2O, the mass of NaOH in the alkaline precipitant solution was 82.0 grams. The subsequent preparation and evaluation of the catalyst were carried out as in example 1, and the catalyst evaluation data are given in Table 2. The doped mixed valence copper catalyst has the following structural formula after being analyzed by photoelectron spectroscopy: [ Cu (0)0 72Ni(0)0.055][Cu(I)0.23Zn0.02O0.135](SiO2)1 1。
Example 5
Selecting a reaction vessel, injecting 1000mL of deionized water, starting stirring, and respectively weighing 114.76 g of Cu (NO)3)2·3H2O, 9.45 g Ni (NO)3)2·6H2O, 2.97 g Zn (NO)3)2·6H2O, the mass of NaOH in the alkaline precipitant solution was 82.8 grams. The subsequent preparation and evaluation of the catalyst were carried out as in example 1, and the catalyst evaluation data are given in Table 2. The doped mixed valence copper catalyst has the following structural formula after being analyzed by photoelectron spectroscopy: [ Cu (0)0 73Ni(0)0 065][Cu(I)0 22Zn0 02O0.13](SiO2)1 1。
Example 6
Selecting a reaction vessel, injecting 1000mL of deionized water, starting stirring, and respectively weighing 114.76 g of Cu (NO)3)2·3H2O, 10.90 g Ni (NO)3)2·6H2O, 2.97 g Zn (NO)3)2·6H2O, the mass of NaOH in the alkaline precipitant solution was 83.6 grams. The subsequent preparation and evaluation of the catalyst were carried out as in example 1, and the catalyst evaluation data are given in Table 2. The doped mixed valence copper catalyst has the following structural formula after being analyzed by photoelectron spectroscopy: [ Cu (0)0.74Ni(0)0 075][Cu(I)0 21Zn0 02O0 125](SiO2)1 1。
Examples 7-12 with the values of n and f unchanged, the values of y are transformed, and the values of x, m and z are changed
Example 7
Selecting a reaction vessel, injecting 1000mL of deionized water, starting stirring, and respectively weighing 114.76 g of Cu (NO)3)2·3H2O, 8.00 g Ni (NO)3)2·6H2O, 4.46 g Zn (NO)3)2·6H2O, the mass of NaOH in the alkaline precipitant solution was 82.8 grams. Catalyst and process for preparing sameThe subsequent preparation and evaluation were carried out as in example 1, and the catalyst evaluation data are shown in Table 1. The doped mixed valence copper catalyst has the following structural formula after being analyzed by photoelectron spectroscopy: [ Cu (0)0 69Ni(0)0 055][Cu(I)0.26Zn0.03O0.16](SiO2)1.1。
Example 8
Selecting a reaction vessel, injecting 1000mL of deionized water, starting stirring, and respectively weighing 114.76 g of Cu (NO)3)2·3H2O, 8.00 g Ni (NO)3)2·6H2O, 5.95 g Zn (NO)3)2·6H2O, the mass of NaOH in the alkaline precipitant solution was 83.6 grams. The subsequent preparation and evaluation of the catalyst were carried out as in example 1, and the catalyst evaluation data are given in Table 2. The doped mixed valence copper catalyst has the following structural formula after being analyzed by photoelectron spectroscopy: [ Cu (0)0.65Ni(0)0.055][Cu(I)0.3Zn0.04O0.19](SiO2)1.1。
Example 9
Selecting a reaction vessel, injecting 1000mL of deionized water, starting stirring, and respectively weighing 114.76 g of Cu (NO)3)2·3H2O, 8.00 g Ni (NO)3)2·6H2O, 7.44 g Zn (NO)3)2·6H2O, the mass of NaOH in the alkaline precipitant solution was 84.4 grams. The subsequent preparation and evaluation of the catalyst were carried out as in example 1, and the catalyst evaluation data are given in Table 1. The doped mixed valence copper catalyst has the following structural formula after being analyzed by photoelectron spectroscopy: [ Cu (0)0.63Ni(0)0.055][Cu(I)0 32Zn0 05O0.21](SiO2)1 1。
Example 10
Selecting a reaction vessel, injecting 1000mL of deionized water, starting stirring, and respectively weighing 114.76 g of Cu (NO)3)2·3H2O, 8.00 g Ni (NO)3)2·6H2O、8.92Gram of Zn (NO)3)2·6H2O, the mass of NaOH in the alkaline precipitant solution was 85.2 grams. The subsequent preparation and evaluation of the catalyst were carried out as in example 1, and the catalyst evaluation data are given in Table 2. The doped mixed valence copper catalyst has the following structural formula after being analyzed by photoelectron spectroscopy: [ Cu (0)0.61Ni(0)0 055][Cu(I)0 34Zn0 06O0 23](SiO2)1.1。
Example 11
Selecting a reaction vessel, injecting 1000mL of deionized water, starting stirring, and respectively weighing 114.76 g of Cu (NO)3)2·3H2O, 8.00 g Ni (NO)3)2·6H2O, 10.41 g Zn (NO)3)2·6H2O, the mass of NaOH in the alkaline precipitant solution was 86.0 grams. The subsequent preparation and evaluation of the catalyst were carried out as in example 1, and the catalyst evaluation data are given in Table 2. The doped mixed valence copper catalyst has the following structural formula after being analyzed by photoelectron spectroscopy: [ Cu (0)0 59Ni(0)0 055][Cu(I)0.36Zn0 07O0.25](SiO2)1.1。
Example 12
Selecting a reaction vessel, injecting 1000mL of deionized water, starting stirring, and respectively weighing 114.76 g of Cu (NO)3)2·3H2O, 8.00 g Ni (NO)3)2·6H2O, 11.90 g Zn (NO)3)2·6H2O, the mass of NaOH in the alkaline precipitant solution was 86.8 grams. The subsequent preparation and evaluation of the catalyst were carried out as in example 1, and the catalyst evaluation data are given in Table 2. The doped mixed valence copper catalyst has the following structural formula after being analyzed by photoelectron spectroscopy: [ Cu (0)0.55Ni(0)0 055][Cu(I)0.4Zn0.08O0.28](SiO2)1.1。
Examples 13 to 18, the values of n and y were kept constant, the value of f was changed, and the values of x, m and z were changed
Example 13
Selecting a reaction vessel, injecting 1000mL of deionized water, starting stirring, and respectively weighing 114.76 g of Cu (NO)3)2·3H2O, 8.00 g Ni (NO)3)2·6H2O, 2.97 g Zn (NO)3)2·6H2And O. Adding weighed Cu (NO) one by one under stirring3)2·3H2O、Ni(NO3)2·6H2O、Zn(NO3)2·6H2And O, then adding the obtained metal ion mixed solution into 80.11 g of silica sol solution with the mass fraction of 30%, and stirring to reach a uniform degree. The mixture was heated to 75 deg.c and an aqueous solution containing 82.0 grams of sodium hydroxide was added to maximize the formation of precipitates of metal ions with the silica sol. The subsequent preparation and evaluation of the catalyst were carried out as in example 1, and the catalyst evaluation data are given in Table 1. The doped mixed valence copper catalyst has the following structural formula after being analyzed by photoelectron spectroscopy: [ Cu (0)0.74Ni(0)0 055][Cu(I)0.21Zn0.02O0.125](SiO2)0.8。
Example 14
Selecting a reaction vessel, injecting 1000mL of deionized water, starting stirring, and respectively weighing 114.76 g of Cu (NO)3)2·3H2O, 8.00 g Ni (NO)3)2·6H2O, 2.97 g Zn (NO)3)2·6H2And O. Adding weighed Cu (NO) one by one under stirring3)2·3H2O、Ni(NO3)2·6H2O、Zn(NO3)2·6H2And O, then adding the obtained metal ion mixed solution into 90.12 g of silica sol solution with the mass fraction of 30%, and stirring to reach a uniform degree. The subsequent preparation and evaluation of the catalyst were carried out as in example 13, and the catalyst evaluation data are given in Table 2. The doped mixed valence copper catalyst has the following structural formula after being analyzed by photoelectron spectroscopy: [ Cu (0)0 73Ni(0)0 055][Cu(I)0 22Zn0 02O0.13](SiO2)0 9。
Example 15
Selecting a reaction vessel, injecting 1000mL of deionized water, starting stirring, and respectively weighing 114.76 g of Cu (NO)3)2·3H2O, 8.00 g Ni (NO)3)2·6H2O, 2.97 g Zn (NO)3)2·6H2And O. Adding weighed Cu (NO) one by one under stirring3)2·3H2O、Ni(NO3)2·6H2O、Zn(NO3)2·6H2And O, then adding the obtained metal ion mixed solution into 100.13 g of 30 mass percent silica sol solution, and stirring to achieve a uniform degree. The subsequent preparation and evaluation of the catalyst were carried out as in example 13, and the catalyst evaluation data are given in Table 2. The doped mixed valence copper catalyst has the following structural formula after being analyzed by photoelectron spectroscopy: [ Cu (0)0.71Ni(0)0.055][Cu(I)0.24Zn0.02O0.14](SiO2)1.0。
Example 16
Selecting a reaction vessel, injecting 1000mL of deionized water, starting stirring, and respectively weighing 114.76 g of Cu (NO)3)2·3H2O, 8.00 g Ni (NO)3)2·6H2O, 2.97 g Zn (NO)3)2·6H2And O. Adding weighed Cu (NO) one by one under stirring3)2·3H2O、Ni(NO3)2·6H2O、Zn(NO3)2·6H2And O, then adding the obtained metal ion mixed solution into 120.16 g of 30 mass percent silica sol solution, and stirring to achieve a uniform degree. The subsequent preparation and evaluation of the catalyst were carried out as in example 13, and the catalyst evaluation data are given in Table 2. The doped mixed valence copper catalyst has the following structural formula after being analyzed by photoelectron spectroscopy: [ Cu (0)0.70Ni(0)0.055][Cu(I)0.25Zn0.02O0.145](SiO2)1.2。
Example 17
Selecting a reaction vessel, injecting 1000mL of deionized water, starting stirring, and respectively weighing 114.76 g of Cu (NO)3)2·3H2O, 8.00 g Ni (NO)3)2·6H2O, 2.97 g Zn (NO)3)2·6H2And O. Adding weighed Cu (NO) one by one under stirring3)2·3H2O、Ni(NO3)2·6H2O、Zn(NO3)2·6H2And O, then adding the obtained metal ion mixed solution into 130.17 g of 30 mass percent silica sol solution, and stirring to achieve a uniform degree. The subsequent preparation and evaluation of the catalyst were carried out as in example 13, and the catalyst evaluation data are given in Table 2. The doped mixed valence copper catalyst has the following structural formula after being analyzed by photoelectron spectroscopy: [ Cu (0)0.68Ni(0)0 055][Cu(I)0 27Zn0 02O0.155](SiO2)1.3。
Example 18
Selecting a reaction vessel, injecting 1000mL of deionized water, starting stirring, and respectively weighing 114.76 g of Cu (NO)3)2·3H2O, 8.00 g Ni (NO)3)2·6H2O, 2.97 g Zn (NO)3)2·6H2And O. Adding weighed Cu (NO) one by one under stirring3)2·3H2O、Ni(NO3)2·6H2O、Zn(NO3)2·6H2And O, then adding the obtained metal ion mixed solution into 140.19 g of 30 mass percent silica sol solution, and stirring to achieve a uniform degree. The subsequent preparation and evaluation of the catalyst were carried out as in example 13, and the catalyst evaluation data are given in Table 2. The doped mixed valence copper catalyst has the following structural formula after being analyzed by photoelectron spectroscopy: [ Cu (0)0.65Ni(0)0 055][Cu(I)0.3Zn0 02O0 17](SiO2)1 4。
TABLE 2 summary of the reaction results
Figure BSA0000240366530000131
Note: the raw material is a methanol solution of 20 mass percent of methyl 3-hydroxypropionate; the reaction temperature is 155 ℃, the reaction pressure is 70bar, and the liquid hourly space velocity is 0.1h-1Hydrogen to ester ratio of 200
Example 19
Selecting a reaction vessel, injecting 1000mL of deionized water, starting stirring, and respectively weighing 114.76 g of Cu (NO)3)2·3H2O, 4.67 g of anhydrous AgNO32.97 g Zn (NO)3)2·6H2O, mass of NaOH in alkaline precipitant solution was 79.8 g. The subsequent preparation and evaluation of the catalyst were carried out as in example 1, and the catalyst evaluation data are given in Table 3. The doped mixed valence copper catalyst has the following structural formula after being analyzed by photoelectron spectroscopy: [ Cu (0)0 75Ag(0)0.055][Cu(I)0 20Zn0.02O0.12](SiO2)1.1。
Example 20
Selecting a reaction vessel, injecting 1000mL of deionized water, starting stirring, and respectively weighing 114.76 g of Cu (NO)3)2·3H2O, 8.00 g Co (NO)3)2·6H2O, 2.97 g Zn (NO)3)2·6H2O, the mass of NaOH in the alkaline precipitant solution was 82.0 grams. The subsequent preparation and evaluation of the catalyst were carried out as in example 1, and the catalyst evaluation data are given in Table 3. The doped mixed valence copper catalyst has the following structural formula after being analyzed by photoelectron spectroscopy: [ Cu (0)0 69Co(0)0 055][Cu(I)0.26Zn0.02O0.15](SiO2)1.1。
Example 21
Selecting a reaction vessel, injecting 1000mL of deionized water, starting stirring, and respectively weighing 114.76 g of Cu (NO)3)2·3H2O, 7.02 g RuCl3·3H2O, 2.97 g Zn (NO)3)2·6H2O, the mass of NaOH in the alkaline precipitant solution was 84.2 grams. The subsequent preparation and evaluation of the catalyst were carried out as in example 1, and the catalyst evaluation data are given in Table 3. The doped mixed valence copper catalyst has the following structural formula after being analyzed by photoelectron spectroscopy: [ Cu (0)0.76Ru(0)0.055][Cu(I)0.19Zn0 02O0.115](SiO2)1 1。
Example 22
Selecting a reaction vessel, injecting 1000mL of deionized water, starting stirring, and respectively weighing 114.76 g of Cu (NO)3)2·3H2O, 8.00 g Ni (NO)3)2·6H2O, 1.79 g Mn (OAc)2·4H2O, the mass of NaOH in the alkaline precipitant solution was 84.2 grams. The subsequent preparation and evaluation of the catalyst were carried out as in example 1, and the catalyst evaluation data are given in Table 3. The doped mixed valence copper catalyst has the following structural formula after being analyzed by photoelectron spectroscopy: [ Cu (0)0 66Ni(0)0 055][Cu(I)0 29Mn0.02O0 165](SiO2)1.1。
Example 23
Selecting a reaction vessel, injecting 1000mL of deionized water, starting stirring, and respectively weighing 114.76 g of Cu (NO)3)2·3H2O, 8.00 g Ni (NO)3)2·6H2O, 4.33 g La (NO)3)3·6H2O, the mass of NaOH in the alkaline precipitant solution was 82.8 grams. The subsequent preparation and evaluation of the catalyst were carried out as in example 1, and the catalyst evaluation data are given in Table 3. The doped mixed valence copper catalyst has the following structural formula after being analyzed by photoelectron spectroscopy: [ Cu (0)0.61Ni(0)0 055][Cu(I)0 34La0.02O0.2](SiO2)1 1。
Example 24
Selecting a reaction vessel, injecting 1000mL of deionized water, starting stirring, and respectively weighing 114.76 g of Cu (N)O3)2·3H2O, 8.00 g Ni (NO)3)2·6H2O, 4.34 g Ce (NO)3)3·6H2O, the mass of NaOH in the alkaline precipitant solution was 82.8 grams. The subsequent preparation and evaluation of the catalyst were carried out as in example 1, and the catalyst evaluation data are given in Table 3. The doped mixed valence copper catalyst has the following structural formula after being analyzed by photoelectron spectroscopy: [ Cu (0)0 62Ni(0)0.055][Cu(I)0 33Ce0.02O0.195](SiO2)1.1。
TABLE 3 summary of the reaction results
Figure BSA0000240366530000141
Figure BSA0000240366530000151
Note: the raw material is a methanol solution of 20 mass percent of methyl 3-hydroxypropionate; the reaction temperature is 155 ℃, the reaction pressure is 70bar, and the liquid hourly space velocity is 0.1h-1Hydrogen to ester ratio of 200
Examples 25 to 30
Examination of this section [ Cu (0)0.69Co(0)0 055][Cu(I)0.26Zn0.02O0.15](SiO2)1 1The catalytic hydrogenation performance of different feed molecules, from examples 25-30, were dimethyl malonate, diethyl malonate, ethyl 3-hydroxypropionate, n-propyl 3-hydroxypropionate, n-butyl 3-hydroxypropionate, and tert-butyl 3-hydroxypropionate, respectively, and the catalyst evaluation methods were as in example 1, and the results are shown in Table 4.
TABLE 4 summary of the reaction results
Figure BSA0000240366530000152
Note: the raw material is methanol solution with the mass number of 20%Liquid; the reaction temperature is 155 ℃, the reaction pressure is 70bar, and the liquid hourly space velocity is 0.1h-1Hydrogen to ester ratio of 200
Although the present invention has been described in the above examples, the present invention is not limited to the above embodiments, which are only illustrative and not restrictive, and those skilled in the art can make many modifications of various compounds formed by copper and other metal ions or directly commercialized doped mixed-valence copper catalysts without departing from the spirit of the present invention, which falls within the protection of the present invention.

Claims (10)

1. A doped mixed-valence copper catalyst comprises a carrier and a metal element component, wherein the metal element component comprises Cu (0), Cu (T), other metal elements M 'with valence of 0 and other metal elements M' with valence of other.
2. The catalyst according to claim 1,
the molar ratio of Cu (0) to Cu (I) is 0.25-4.0 or 1-4 or 1.5-4;
the molar ratio of the other 0-valent metal element M' to Cu (0) is 0.01-0.30;
the molar ratio of other metal elements M' in other valence states to Cu (I) is 0.01-0.30 or 0.1-0.15;
[Cu(0)+Cu(I)]with silica gel (in SiO)2Calculated by weight) of 0.11 to 1.50 or 0.23 to 1.2.
3. The catalyst according to claim 1,
the carrier is silica gel;
m' is selected from one or more transition metals, preferably one or more of ruthenium, nickel, cobalt, iron, silver, osmium, rhodium and gold;
m' is selected from one or more of transition metal, lanthanide series metal or alkali metal, the transition metal is preferably zinc, manganese, chromium, cadmium, zirconium, titanium and hafnium; the lanthanide metal is preferably lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium and ytterbium, and the alkali metal is preferably magnesium, calcium, strontium and barium.
4. The catalyst of claim 1, wherein the catalyst is represented by the general formula:
[Cu(0)mM′(0)n][Cu(I)xM″yOz](SiO2)f
wherein Cu (0) means 0-valent copper, and M' (0) means other metal of 0-valent; cu (I) means positive 1 valent copper, M "means other metals in other valence states; SiO 22Silica gel carrier, m: x is 0.25-4.0, n: m is 0.01 to 0.30, y: x is 0.01-0.30, and z is [ Cu (0) ]mM′(0)n][Cu(I)xM″yOz](SiO2)fIs in a neutral molecular state, and f is selected to be [ Cu (0) + Cu (I)]With SiO2In a molar ratio of 0.11 to 1.50.
5. A preparation method of a doped mixed-valence copper catalyst comprises the following steps:
s1: mixing a copper salt, an M' salt and a carrier solution;
s2: mixing the mixture obtained in the step S1 with an alkaline precipitant solution to generate a solid precipitate;
s3: roasting the solid precipitate;
s4: and reducing the roasted product.
6. The method according to claim 5, wherein the copper salt is selected from one or more of a divalent copper salt and a monovalent copper salt, specifically, the copper salt may be one or more of copper sulfate, copper nitrate, copper halide, copper perchlorate, copper amine solution, cuprous sulfate, cuprous nitrate, cuprous halide, copper perchlorate, cuprous organic acid, preferably one or two of cupric nitrate and cupric acetate;
m' salt is selected from at least one of ruthenium trichloride, ruthenium acetate, potassium chlororuthenate, nickel sulfate, nickel nitrate, nickel chloride, nickel acetate, cobalt sulfate, cobalt nitrate, cobalt chloride, cobalt acetate, osmium chloride, ferric sulfate, ferric nitrate, ferric chloride, ferric acetate, silver sulfate, silver nitrate, silver acetate, rhodium nitrate, rhodium chloride and chloroauric acid, and is preferably selected from one or more of rhodium chloride, nickel nitrate, cobalt nitrate and silver nitrate;
m' salt is selected from zinc sulfate, zinc nitrate, zinc chloride, zinc acetate, manganese sulfate, manganese nitrate, manganese chloride, manganese acetate, chromium sulfate, chromium nitrate, chromium chloride, chromium acetate, lanthanum nitrate, lanthanum acetate, cerium ammonium sulfate, cerium nitrate, cerium ammonium nitrate, cerium acetate, praseodymium sulfate, praseodymium chloride, praseodymium nitrate, praseodymium acetate, neodymium sulfate, neodymium nitrate, neodymium chloride, neodymium acetate, samarium sulfate, samarium nitrate, samarium chloride, samarium acetate, europium sulfate, europium nitrate, europium chloride, europium acetate, gadolinium sulfate, gadolinium nitrate, gadolinium chloride, gadolinium acetate, terbium sulfate, terbium nitrate, terbium chloride, terbium acetate, dysprosium sulfate, nitric acid, dysprosium chloride, dysprosium acetate, holmium sulfate, holmium nitrate, holmium chloride, erbium acetate, erbium nitrate, erbium chloride, erbium acetate, thulium sulfate, thulium nitrate, thulium chloride, thulium acetate, ytterbium chloride, cadmium acetate, cadmium sulfate, cadmium nitrate, zinc nitrate, cerium ammonium nitrate, cerium chloride, cerium nitrate, neodymium, Cadmium nitrate, magnesium sulfate, magnesium nitrate, magnesium chloride, magnesium acetate, calcium nitrate, calcium chloride, calcium acetate, strontium chloride, strontium acetate, barium chloride, barium nitrate, barium acetate, zirconium sulfate, zirconium nitrate, zirconium chloride, zirconium acetate, titanium chloride, hafnium sulfate, hafnium chloride, magnesium sulfate, magnesium nitrate, magnesium chloride, magnesium acetate, calcium chloride, strontium sulfate, calcium nitrate, strontium chloride, strontium acetate, barium chloride, barium nitrate, barium acetate, at least one of barium nitrate, preferably one or more of zinc nitrate, zirconium nitrate, manganese nitrate and cerium nitrate;
the alkaline precipitant is selected from one or more of sodium hydroxide, lithium hydroxide, potassium hydroxide, sodium carbonate, lithium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, urea, ammonia water, ammonium carbonate, ammonium bicarbonate, sodium methoxide, sodium ethoxide, sodium n-propoxide, sodium isopropoxide, sodium n-propoxide, sodium n-butoxide, sodium t-butoxide, lithium methoxide, lithium ethoxide, lithium n-propoxide, lithium n-butoxide, lithium isobutyl alkoxide, lithium t-butoxide, potassium methoxide, potassium ethoxide, potassium n-propoxide, potassium isopropoxide, potassium n-butoxide, potassium isobutyl alkoxide, potassium t-butoxide, sodium amide, lithium amide, potassium amide, sodium alkylamino, lithium alkylamino and potassium alkylamino, preferably one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonium bicarbonate, ammonia water, urea, sodium methoxide and sodium ethoxide;
the carrier solution is a silica sol solution, preferably the silica sol solution has a mass fraction concentration of 5-50%, more preferably 10-35%.
7. The method of claim 5, wherein in step S2, heating is performed before adding the alkaline precipitant, and the heating temperature can be 40-99 ℃, preferably 50-90 ℃;
in step S3, the roasting temperature is 350-700 ℃, the roasting time is 1-48 hours, and the preferred roasting time is 1-24 hours;
in step S4, the reduction treatment is performed in a reducing atmosphere using hydrogen, a hydrogen/nitrogen mixed gas, or carbon monoxide, preferably hydrogen and a hydrogen/nitrogen mixed gas; the temperature of the reduction treatment is 100 ℃ and 500 ℃, and the reduction time is 1-48 hours, preferably 1-20 hours.
8. Use of a catalyst according to any one of claims 1 to 4 or a catalyst prepared by a preparation process according to any one of claims 5 to 7 in a hydrogenation reaction.
9. A hydrogenation process or a process for the production of 1, 3-propanediol comprising subjecting a hydrogenation feedstock to a hydrogenation reaction in the presence of a catalyst as claimed in any one of claims 1 to 4 or a catalyst produced by a process according to any one of claims 5 to 7.
10. The hydrogenation method or the preparation method of 1, 3-propanediol according to claim 9, wherein the hydrogenation raw material is selected from one or more of malonic acid esters and 3-hydroxypropionic acid ester compounds, preferably the hydrogenation raw material is selected from one or more of methyl malonate, ethyl malonate, propyl malonate, butyl malonate, pentyl malonate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate and pentyl 3-hydroxypropionate.
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