CN114345339B - Supported binary metal catalyst, preparation method and application thereof - Google Patents
Supported binary metal catalyst, preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a supported binary metal catalyst, which comprises a main metal Cu, a promoter metal M and SiO 2 A carrier; the precursor of the catalyst obtained by the reaction of the alkoxy metal compound and the alkyl silanol is silicon alkoxy copper, and after roasting, partial hydroxyl on the surface of silicon dioxide is replaced by metal oxygen bonds, so that the catalyst has a certain inhibiting effect on beta-hydroxyl dehydration. The catalyst can be used for the reaction of preparing 1, 3-propylene glycol by hydrogenating methyl 3-hydroxypropionate, the conversion rate can reach 90-100 percent, and the selectivity of the 1, 3-propylene glycol can reach 70-85 percent.
Description
Technical Field
The invention relates to a supported binary metal catalyst, which is used for preparing 1, 3-propylene glycol by hydrogenation of malonate and 3-hydroxypropionate compounds and is also suitable for preparing other dihydric alcohol and monohydric alcohol by catalytic hydrogenation reaction of other diesters and monoesters.
Background
1, 3-propylene glycol is an important chemical raw material and is used in the fields of food, medicine, cosmetics and the like. It is also an important chemical monomer for preparing various polymers, for example, the condensation reaction of 1, 3-propanediol and terephthalic acid to prepare polytrimethylene terephthalate, which is a high-elasticity polyester fiber and has wide industrial application prospect.
The ethylene oxide hydrogen esterification method can prepare 3-hydroxy propionate (3-HP), and the hydrogenation of 3-hydroxy propionate is an important route for synthesizing 1, 3-propylene glycol (1, 3-PDO) which needs to be developed in industry. However, 3-HP is susceptible to side reactions such as dehydration and deacidification, and thus has low reactivity and selectivity (Surface Review and Letters,2009,16, 343-349). At present, the catalytic technology of hydrogenation does not meet the industrial requirement yet. In 2001, shell reported Cu-ZnO catalysts and Cu-ZnO catalysts doped with Zr and Ba (US 6191321B1 and WO 00/18712). The patent application for copper chromate or Pd/C catalysts was filed by Samsung corporation in 2002 (US 6348632B1 and US6521801B 2). The 2005 U.S. Jiaji Co Ltd discloses a Ru/C catalyst doped with Mo, W, ti, zr, nb, V and Cr components (CN 1711228A). In contrast, metal catalysts supported on silica gel supports are of interest. As reported by Samsung corporation subsequently, cu/SiO 2 Catalysts, other metals such as Re, ru, pd, pt, rh, ag, se, te, mo and Mn can be used as promoters to increase the catalytic activity. These catalysts are obtained by adding an alkaline precipitant, which is an alkali metal carbonate and sodium hydroxide (CN 1355160A), to an aqueous solution containing a metal salt to form particles, and then adding colloidal silica to age. The catalyst CuO (77 wt%) -MnO (3 wt%)/SiO (20 wt%) is subjected to hydrophobic treatment on the surface of the silica carrier by using tetraglyme as a high boiling point solvent, so that the conversion rate of 3-HP is 10.25-90.92% and the selectivity of 1,3-PDO is 21.60-100% (U.S. 2003/0069456A 1). However, this technique still has drawbacks such as large reaction pressure, long cycle, unstable activity, short life, and the like.
Cu/TiO as disclosed in the Lanzhou chemical and physical research institute of 2007 2 -SiO 2 The catalyst is prepared by the following specific steps: preparing the compound containing each component of the catalyst into solution according to the required components and proportion, coprecipitating with sodium hydroxide, or mixing the coprecipitate of the compound containing the active component and the cocatalyst CuCl with the common precipitate of the compound containing titanium and silicon, filteringWashing, drying and roasting, or soaking the CuCl auxiliary agent on the surface of the catalyst, roasting, and then crushing and molding to obtain the catalyst (CN 101020635A and US20070191629A 1). Cu/SiO published in CN101195558A 2 The catalyst is prepared by an alcohol heating method, namely, alcohol solution of copper sulfate, copper acetate, copper chloride or copper nitrate reacts with ethyl orthosilicate alcohol and is aged. The university of Compound Dan and Shanghai coking Co Ltd disclose a Cu/Al 2 O 3 -SiO 2 The catalyst is prepared by the following specific steps: under the condition of existence of alcohol solvent, copper salt and organic amine of a certain component are reacted to generate complex, then a certain amount of orthosilicic acid alcohol ester, fatty alcohol aluminum and gelling agent are added to form sol and gel, and the obtained gel is dried, roasted and reduced to be used as a catalyst (CN 1911507A). The technical proposal is characterized by larger liquid hourly space velocity, and further discloses CuO-MnO 2 /SiO 2 Catalyst (CN 101385980A). Qingdao university of science and technology claims CuO-ZnO-P/SiO 2 The catalyst is prepared by the following specific steps: complexing copper salt and ammonium salt, mixing with a salt solution containing a certain amount of Cu and Zn, sequentially adding ammonium hypophosphite and silica sol, aging, filtering, drying, molding, and high-temperature roasting to obtain the catalyst (CN 101176848A). In 2011, guangdong institute of petrochemical engineering disclosed Cu-Mn/ZrO 2 The catalyst is prepared by the following specific steps: preparing copper, manganese and zirconium salts into a solution with the total mass concentration by using water, and preparing the catalyst by coprecipitating the solution and an alkaline precipitator, aging, washing, drying and roasting (CN 102059125A). They also prepared an oxide catalyst (CN 101993352A) with a molar ratio of Cu: mn: cr of 1. Catalyst CuO-MnO 2 -MoO 3 /P 2 O 5 -SiO 2 (CN 103721734A) and CuO-NiO-MoO 3 -ZnO/SiO 2 (CN 103801315A) is also reported, the preparation process of the latter is: dissolving a precursor obtained by Cu, zn, ni and Si elements in deionized water, uniformly mixing, then dropwise adding a precipitator for precipitation, then adding ammonium molybdate and potassium salt to obtain a mixed aqueous solution, then aging, filtering, washing, drying, then roasting, tabletting, forming and crushing to obtain the catalyst. 2016 report on Cu-M/SiO in King's gold book 2 The catalyst and the assistant M are Zn and Zr, mn, la, P, mo and Ni, and the specific preparation process comprises the following steps: and (2) dissolving a measured precursor of Cu and the auxiliary agent in deionized water to form a solution, carrying out coprecipitation on the solution and an alkaline solution obtained by adding an alkaline precipitator at a certain speed, adding silica sol into the precipitate, further aging, drying and roasting to obtain the catalyst (CN 106111155A). CN106179361A discloses CuO-ZrO 2 -ZnO/SiO 2 A catalyst.
Disclosure of Invention
The research of the invention finds that the single metal components Cu and SiO 2 Catalyst composed of carrier (Cu/SiO) 2 ) The catalytic performance is not ideal. Under the hydrogen condition, cu (0) (zero-valent copper) and Cu (I) (monovalent copper) need to act synergistically, wherein the Cu (I) plays the role of Lewis acid, adsorbs 3-hydroxypropionate and activates the same; cu (0) is responsible for H 2 The activation of (a) produces H-for the hydrogenation of the ester group in the 3-hydroxypropionate, which together allow the catalytic conversion of the 3-hydroxypropionate to 1, 3-propanediol. Aiming at a reaction system for synthesizing 1, 3-propylene glycol by hydrogenating 3-hydroxy propionate, other metals are required to be introduced when stable Cu (0) and Cu (I) are generated for catalysis. Further studies by the inventors suggest that the incorporation of one of the other metals may achieve the desired reaction results. Further research by the inventors shows that the SiO-based alloy contains Cu and other metals 2 When a binary metal supported catalyst is formed on a carrier, the selection and preparation method of a metal precursor in the catalyst have important influence on the performance of ester hydrogenation reaction.
The application provides a supported binary metal catalyst, which comprises two metals and a carrier, wherein one metal is limited to copper, and the other metal is selected from one of cerium, manganese, chromium, iron, cobalt, nickel, molybdenum, ruthenium, rhodium and palladium; the carrier being SiO 2 。
In the embodiment of the present invention, the molar ratio of Cu to another metal is controlled to 1 to 40.
In the embodiments of the present invention, siO is mentioned 2 When the supported binary metal catalyst is used as a carrier component, the structural general formula of the supported binary metal catalyst can be expressed as Cu m M n Si x O y 。
In Cu m M n Si x O y In, O y The calculation result of (2) holds Cu m M n Si x O y The molecule is neutral, m: x =0.01 to 0.74, preferably 0.1 to 0.3, n: x =0.001 to 0.1, preferably 0.003 to 0.05; high silicon ratio catalyst: m: x =0.01 to 0.1, preferably 0.01 to 0.05; n: x =0.0001 to 0.002, preferably 0.0006 to 0.001; m: n =1 to 40, preferably 2 to 21.
For controlling the generation of a compound with the general formula of Cu m M n Si x O y The invention selects the organosilicone copper as a precursor species of Cu, and the organosilicone copper is selected from CuOSiR 3 、Cu 2 (O 2 SiR 2 )、Cu 3 (O 3 SiR)、Cu(OSiR 3 ) 2 、Cu[(R 2 SiO) 2 O]、Cu 3 [R 7 Si 7 O 12 ] 2 、Cu(RSiO 2 )、Cu 3 [(RSiO 2 ) 3 ] 2 、Cu 2 [(RSiO 2 ) 4 ]R is an organic group selected from one of alkyl, aryl, alkoxy, phenolic group and amido.
According to an embodiment of the present invention, the method of preparing organosilicooxy copper is as follows: the copper compound and the organic silanol with the set molar ratio are dissolved in an organic solvent and stirred at room temperature to form a uniform solution. Heating to reflux state, maintaining the state for a certain time, removing organic solvent by heating evaporation, and drying the residue.
In an embodiment of the invention, the copper compound is selected from the group consisting of alkyl copper, aromatic copper, amine copper, alkoxy copper, phenol copper, copper phyllosilicate, basic copper carbonate. The alkyl group is preferably a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclopentyl group, a cyclohexyl group, an aromatic group is preferably a phenyl group and a substituted phenyl group, the alkoxy group is preferably an oxymethyl group, an oxyethyl group, an oxypropyl group, an oxybutyl group, an oxypentyl group, an oxyhexyl group, an oxocyclopentyl group, an oxocyclohexyl group, the phenol group is preferably a phenol group and a substituted phenol group, the amine group is preferably a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, a dipentylamin group, a dihexylamino group, a methylphenylamino group, an ethylphenylamino group, a propylphenylamino group, a butylphenyl amino group, a pentylphenylamino group, a hexylphenylamino group, a silylphenylamino group, a silyl-substituted phenylamino group.
In an embodiment of the present invention, the organosilols are of the general molecular structural formula SiR n (OH) 4-n (n＝1,2,3)、(R 2 SiOH) 2 O]、H 2 [R 7 Si 7 O 12 ]The compound of (1), wherein R is one of alkyl, aryl, alkoxy, phenol group and amino, the alkyl is preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl and cyclohexyl, the aryl is preferably phenyl and substituted phenyl, the alkoxy is preferably oxymethyl, oxyethyl, oxypropyl, oxybutyl, oxypentyl, oxyhexyl, oxycyclopentyl and oxycyclohexyl, the phenol is preferably phenol group and substituted phenol group, and the amino is preferably dimethylamino, diethylamino, dipropylamino, dibutylamino, dipentylamin, dihexylamino, methylphenylamino, ethylphenylamino, propylphenylamino, butylphenylamino, pentylphenylamino, hexylphenylamino, silylphenylamino and silyl-substituted phenylamino.
In an embodiment of the invention, the organic solvent is selected from methanol, ethanol, isopropanol, hexane, heptane, benzene, toluene, diethyl ether, tetrahydrofuran, 1, 4-dioxane, preferably isopropanol, tetrahydrofuran, 1, 4-dioxane.
For controlling the generation of a compound with the structural formula of Cu m M n Si x O y The invention selects the precursor species of organic silicon oxygen-based metal M, M and [ R ] in different oxidation states 3 SiO]ˉ、[R 2 SiO 2 ] 2 ˉ、[(R 2 SiO) 2 O] 2 ˉ、[RSiO 3 ] 3 ˉ、[R 7 Si 7 O 12 ] 3 ˉ、[(RSiO 2 ) n ] n The corresponding compounds. R is organic radical, and refers to one of alkyl, aryl, alkoxy, phenol radical, and amino, wherein the alkyl is preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, and cyclohexyl, and the aryl is preferably aromaticPhenyl and substituted phenyl, alkoxy is preferably oxymethyl, oxyethyl, oxypropyl, oxybutyl, oxypentyl, oxyhexyl, oxocyclopentyl, oxocyclohexyl, phenolic group is preferably phenolic group and substituted phenolic group, amino is preferably dimethylamino, diethylamino, dipropylamino, dibutylamino, dipentylamino, dihexylamino, methylphenylamino, ethylphenylamino, propylphenylamino, butylphenyl amino, pentylphenylamino, hexylphenylamino, silylphenylamino, silylsubstituted phenylamino.
In an embodiment of the present invention, the preparation method of the metal organosiloxane M is as follows: the metal M compound and the organic silanol with the set molar ratio are dissolved in an organic solvent and stirred at room temperature to form a uniform solution. Heating to reflux state, maintaining the state for a certain time, removing organic solvent by heating evaporation, and suction filtering and drying the residue.
In an embodiment of the invention, the M metal compound is selected from the group consisting of metal alkyls, metal aromatics, metal amides, metal alkoxides, metal phenolates, phyllosilicates, and hydroxycarbonates. The alkyl group is preferably a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclopentyl group, a cyclohexyl group, an aromatic group is preferably a phenyl group and a substituted phenyl group, the alkoxy group is preferably an oxymethyl group, an oxyethyl group, an oxypropyl group, an oxybutyl group, an oxypentyl group, an oxyhexyl group, an oxocyclopentyl group, an oxocyclohexyl group, the phenol group is preferably a phenol group and a substituted phenol group, the amine group is preferably a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, a dipentylamin group, a dihexylamino group, a methylphenylamino group, an ethylphenylamino group, a propylphenylamino group, a butylphenyl amino group, a pentylphenylamino group, a hexylphenylamino group, a silylphenylamino group, a silyl-substituted phenylamino group.
According to an embodiment of the present invention, cu m M n Si x O y The preparation method comprises the following steps: the preparation method comprises the steps of selecting organic silica-based copper, organic silica-based metal and organic silanol with a certain molar ratio, dissolving the organic solvents in the organic solvents, and stirring the organic solvents at room temperature to form a uniform solution. The organic solvent is removed by volatilization. The residue was calcined in a muffle furnace until no volatile material was produced. The obtained solidPulverizing, tabletting, grinding, and sieving to obtain granules with certain mesh.
In a preferred embodiment of the present invention, cu with a high Si ratio is prepared m M n Si x O y The molar ratio of the organosilicooxy copper to the organosilicooxy metal M can be increased by the corresponding [ R ] 3 SiO]H、[R 2 SiO 2 ]H 2 、[(R 2 SiO) 2 O]H 2 、[RSiO 3 ]H 3 、[R 7 Si 7 O 12 ]H 3 The amount of (c).
According to an embodiment of the present invention, cu of high Si ratio m M n Si x O y The preparation method comprises the following steps: the preparation method comprises the steps of selecting organic silica-based copper, organic silica-based metal and organic silanol with a certain molar ratio, dissolving the organic solvents in the organic solvents, and stirring the organic solvents at room temperature to form a uniform solution. The organic solvent is removed by volatilization. The residue was calcined in a muffle furnace until no volatile material was produced. The obtained solid is crushed, pressed into tablets, ground and sieved to form particles with a certain mesh number for standby.
According to embodiments of the present invention, the catalysts produced are generally divided into two categories, namely Cu m M n Si x O y And Cu of high Si ratio m M n Si x O y 。
According to an embodiment of the present invention, cu m M n Si x O y According to the set molar ratio of the organosilicooxy copper to the organosilicooxy metal M, the reaction is carried out in an organic solvent.
According to an embodiment of the present invention, the firing atmosphere is selected from one of air, oxygen, and nitrogen.
According to an embodiment of the invention, the calcination temperature is set to 150 to 800 ℃, preferably 350 to 650 ℃; the roasting time is 1 to 72 hours, preferably 3 to 48 hours; the roasting temperature rise rate is 1-50 ℃/min, preferably 4-20 ℃/min.
According to the embodiment of the invention, the calcined catalyst is crushed, ground and tabletted to form a sieve with 40-60 meshes, and 1g of the catalyst is taken and filled in a reaction tube of a fixed bed reactor.
According to the embodiment of the invention, the loaded catalyst is pre-reduced by using hydrogen-argon mixed gas, and the reduction steps are as follows:
3) Heating to 150 deg.C at a rate of 1 deg.C/min from room temperature, and maintaining for 1min;
4) Then the temperature is increased to 300 ℃ at the speed of 10 ℃/min, and the temperature is kept for 10 to 12 hours.
According to an embodiment of the invention, the evaluation is started after the catalyst has been pre-reduced, the evaluation steps being as follows:
1) Firstly, cooling a bed layer to a reaction temperature, replacing hydrogen and argon mixed gas with hydrogen, and increasing the pressure in a reaction tube to the reaction pressure;
2) Waiting for the bed layer temperature to be stable and the pressure in the pipe to be stable;
3) Pumping reaction liquid with certain flow rate by a double-plunger micro pump, simultaneously introducing hydrogen with certain flow rate all the time to start reaction, determining the flow rate of the reaction liquid and the hydrogen by liquid hourly space velocity and hydrogen-ester ratio, obtaining reaction products after passing through a catalyst bed layer, cooling and collecting the products for later use, and recording and analyzing the products.
According to an embodiment of the present invention, the reaction temperature is set to 130 to 270 ℃, preferably 140 to 190 ℃, and the reaction pressure of hydrogen is set to 10 to 100Bar, preferably 40 to 80Bar.
According to an embodiment of the invention, the solvent in the reactant solution is selected from C 1 ～C 20 Or selected from the group consisting of alcohols, water, ethers, saturated alkanes, saturated aromatics, or from the group consisting of no solvents, preferably from the group consisting of methanol, ethanol, propanol, butanol, pentanol, dimethyl ether, diethyl ether, methyl tert-butyl ether, tetrahydrofuran, 2, 6-oxolane, pentane, hexane, heptane, octane, or from the group consisting of no solvents.
According to an embodiment of the present 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, pentyl 3-hydroxypropionate.
According to an embodiment of the invention, the volume fraction of reactants in the reactant solution is selected from 10 to 100%, preferably 12 to 50%, or preferably 100% (i.e. solvent-free state).
According to an embodiment of the invention, the molar ratio of hydrogen to reactants is selected from 20 to 1000, preferably from 100 to 400.
According to an embodiment of the present invention, the liquid hourly space velocity is selected from 0.01 to 1h –1 Preferably 0.1 to 0.5h –1
Detailed Description
The catalyst provided by the invention can be realized by the following implementation:
example 1：
Selecting a reaction vessel, weighing 3.93g of methoxy copper, adding 533mL of hexane, adding 161.23g of triphenyl silanol while stirring, stirring for 3 hours, heating to 70 ℃, refluxing for 10 hours, then draining the mixed solution under vacuum, and stopping stirring. Drying the mixture at 100 ℃ for 12h, and then roasting, wherein the roasting procedure is as follows: raising the room temperature to 450 ℃ at a heating rate of 10 ℃/min, roasting for 4h, then raising the room temperature to 650 ℃ at 1 ℃/min, roasting for 5h, completing roasting, forming and screening the obtained solid, selecting a granular solid of 40-60 meshes, placing the granular solid in a fixed bed type reactor, and reducing for 12h at 300 ℃ in a hydrogen/argon mixed gas atmosphere with the hydrogen volume fraction of 5%, thus obtaining the catalyst, wherein the mass fraction of the roasted copper in the catalyst is 10%, and the following structural formula can be obtained by converting the mass ratio of the materials: cu 0.0625 Si 0.583 O 1.229 。
Then the temperature is 160 ℃, the pressure is 60bar, and the liquid hourly space velocity is 0.1h –1 And the hydrogenation reaction of methyl 3-hydroxypropionate was carried out under the condition that the molar ratio of hydrogen to methyl 3-hydroxypropionate was 200, and the obtained product was collected and analyzed by gas chromatography, and the evaluation data are shown in table 1.
Comparative example:
selecting a reaction vessel, weighing the triphenyl siloxy copper, adding 533ml of hexane, stirring for 3 hours, draining the mixed solution under vacuum, and stopping stirring. The subsequent preparation and evaluation processes are consistent with those of example 1, and the mass fraction of copper in the catalyst after roasting is 10 percentBy converting the amount ratio into the substance, the following structural formula can be obtained: cu 0.0625 Si 0.583 O 1.229 . The evaluation results are shown in Table 1.
Example 2：
Selecting a reaction vessel, weighing 3.93g of methoxy copper and 0.56g of methoxy cerium respectively, adding 533mL of hexane, adding 158.96g of triphenyl silanol while stirring, stirring for 3h, heating to 70 ℃, refluxing for 10h, then draining the mixed solution under vacuum, and stopping stirring. The subsequent preparation and evaluation procedures are consistent with those of example 1, the mass fractions of copper and cerium in the catalyst after calcination are respectively 10% and 1%, and the following structural formula can be obtained by converting the mass fractions into mass ratios of the substances: cu (copper) 0.0625 Ce 0.003 Si 0.575 O 1.218 . The evaluation results are shown in Table 1.
Example 3：
Selecting a reaction vessel, weighing 3.93g of methoxy copper and 1.69g of methoxy cerium respectively, adding 533mL of hexane, adding 154.44g of triphenyl silanol while stirring, stirring for 3h, heating to 70 ℃, refluxing for 10h, then draining the mixed solution under vacuum, and stopping stirring. The subsequent preparation and evaluation procedures are consistent with those of example 1, the mass fractions of copper and cerium in the catalyst after calcination are respectively 10% and 3%, and the following structural formula can be obtained by converting the mass fractions into mass ratios: cu 0.0625 Ce 0.009 Si 0.559 O 1.197 . The evaluation results are shown in Table 1.
Example 4：
Selecting a reaction vessel, weighing 3.93g of methoxy copper and 2.82g of methoxy cerium respectively, adding 533mL of hexane, adding 149.91g of triphenyl silanol while stirring, stirring for 3h, heating to 70 ℃, refluxing for 10h, then draining the mixed solution under vacuum, and stopping stirring. The subsequent preparation and evaluation procedures are consistent with those of example 1, the mass fractions of copper and cerium in the catalyst after calcination are respectively 10% and 5%, and the following structural formula can be obtained by converting the mass fractions into mass ratios: cu (copper) 0.0625 Ce 0.014 Si 0.542 O 1.176 . The evaluation results are shown in Table 1.
Example 5：
Selecting a reaction vessel, weighing 3.93g of methoxy copper and 3.95g of methoxy cerium respectively, adding 533mL of hexane, adding 145.38g of triphenyl silanol while stirring, stirring for 3h, heating to 70 ℃, refluxing for 10h, then draining the mixed solution under vacuum, and stopping stirring. The subsequent preparation and evaluation processes are consistent with those of example 1, the mass fractions of copper and cerium in the catalyst after calcination are respectively 10% and 7%, and the following structural formula can be obtained by converting the mass ratios of the substances: cu (copper) 0.0625 Ce 0.020 Si 0.526 O 1.154 . The evaluation results are shown in Table 1.
Example 6：
Selecting a reaction vessel, weighing 3.93g of methoxy copper and 5.08g of methoxy cerium respectively, adding 533mL of hexane, adding 140.86g of triphenyl silanol while stirring, stirring for 3h, heating to 70 ℃, refluxing for 10h, then draining the mixed solution under vacuum, and stopping stirring. The subsequent preparation and evaluation procedures are consistent with those of example 1, the mass fractions of copper and cerium in the catalyst after calcination are respectively 10% and 9%, and the following structural formula can be obtained by converting the mass fractions into mass ratios: cu 0.0625 Ce 0.026 Si 0.510 O 1.133 . The evaluation results are shown in Table 1.
TABLE 1 summary of the reaction results
Note: the raw material is a methanol solution of 20 mass percent of methyl 3-hydroxypropionate; the reaction temperature =160 ℃, the reaction pressure =60bar, and the liquid hourly space velocity =0.1h –1 Hydrogen to ester ratio =200
As can be seen from the reaction results in Table 1, the performance of the catalyst prepared by the in-situ preparation in the laboratory and the commercial use of the copper triphenyl siloxide is almost the same, and the conversion rate and the selectivity of the catalyst are improved after the second metal Ce is added, but the content of the metal Ce is too high, which is not beneficial to the performance of the catalyst.
Examples 7 to 10: changing the type of M, changing n and y, and keeping M and x unchanged.
Example 7:
selecting a reaction vessel, weighing 3.93g of methoxy copper and 0.61g of methoxy nickel respectively, adding 533mL of hexane, adding 158.88g of triphenyl silanol while stirring, stirring for 3 hours, heating to 70 ℃, refluxing for 10 hours, then draining the mixed solution under vacuum, and stopping stirring. The subsequent preparation and evaluation procedures are consistent with those of example 1, the mass fractions of copper and nickel in the catalyst after calcination are respectively 10% and 1%, and the following structural formula can be obtained by converting the mass fractions into mass ratios of the materials: cu (copper) 0.0625 Ni 0.007 Si 0.575 O 1.226 . The results are shown in Table 2.
Example 8:
selecting a reaction vessel, weighing 3.93g of methoxy copper and 0.87g of methoxy chromium respectively, adding 533mL of hexane, adding 159.01g of triphenyl silanol while stirring, stirring for 3h, heating to 70 ℃, refluxing for 10h, then draining the mixed solution under vacuum, and stopping stirring. The subsequent preparation and evaluation procedures are consistent with those of example 1, the mass fractions of copper and chromium after the catalyst calcination are respectively 10% and 1%, and the following structural formula can be obtained by converting the mass fractions into mass ratios of the materials: cu 0.0625 Cr 0.008 Si 0.575 O 1.218 . The results are shown in Table 2.
Example 9:
selecting a reaction vessel, weighing 3.93g of methoxy copper and 0.58g of methoxy lanthanum respectively, adding 533mL of hexane, adding 159.24g of triphenyl silanol while stirring, stirring for 3h, heating to 70 ℃, refluxing for 10h, then draining the mixed solution under vacuum, and stopping stirring. The subsequent preparation and evaluation processes are consistent with those of example 1, the mass fractions of copper and lanthanum in the catalyst after calcination are respectively 10% and 1%, and the following structural formula can be obtained by converting the mass fractions into mass ratios of the substances: cu 0.0625 La 0.003 Si 0.576 O 1.217 . The results are shown in Table 2.
Example 10:
selecting a reaction vessel, weighing 3.93g of methoxy copper and 0.82g of methoxy cobalt respectively, adding 533mL of hexane, 159.05g of triphenylsilanol was added under stirring, the mixture was stirred for 3 hours, heated to 70 ℃ under reflux for 10 hours, and then the mixed solution was dried under vacuum and the stirring was stopped. The subsequent preparation and evaluation processes are consistent with those of example 1, the mass fractions of copper and cobalt in the catalyst after calcination are respectively 10% and 1%, and the following structural formula can be obtained by converting the mass ratios of the materials: cu 0.0625 Co 0.007 Si 0.575 O 1.218 . The results are shown in Table 2.
TABLE 2 summary of the reaction results
Note: the raw material is a methanol solution of 20 mass percent of methyl 3-hydroxypropionate; reaction temperature =160 ℃, reaction pressure =60bar, liquid hourly space velocity =0.1h –1 Hydrogen to ester ratio =200
It can be seen from the summary of the reaction results in Table 2 and Table 1 that the added promoter metal has little influence on the precipitation form of copper but has a large influence on the reaction performance, wherein La and Co are favorable for the selectivity of 1, 3-propanediol, and Cr and Ni are favorable for improving the hydrogenation performance of methyl 3-hydroxypropionate.
Examples 11 to 19:
this section examines the Cu prepared from organosilanols of different R groups 0.0625 Ce 0.003 Si 0.575 O 1.218 The catalytic hydrogenation performance of (1) was as shown in examples 11 to 21, wherein R groups were methyl, propyl, butyl, hexyl, cyclohexyl, phenyl, methoxy, oxypropyl, oxybutyl, oxyhexyl, and oxocyclohexyl, and the catalyst evaluation methods were as in example 1, and the results are shown in Table 3.
TABLE 3 summary of reaction results
Note: the raw material is a methanol solution of 20 mass percent of methyl 3-hydroxypropionate; reaction temperature =160 ℃, reaction pressure =60bar, liquid hourly space velocity =0.1h –1 Hydrogen to ester ratio =200
Examples 22 to 27:
this section examines Cu at different firing temperatures 0.0625 Ce 0.003 Si 0.575 O 1.218 The catalytic hydrogenation performance of (2) was evaluated in examples 22 to 27 at calcination temperatures of 300 ℃, 400 ℃, 500 ℃, 600 ℃, 700 ℃ and 800 ℃ in the same manner as in example 1, and the results are shown in Table 4.
TABLE 4 summary of the reaction results
Note: the raw material is a methanol solution of 20 mass percent of methyl 3-hydroxypropionate; reaction temperature =160 ℃, reaction pressure =60bar, liquid hourly space velocity =0.1h –1 Hydrogen to ester ratio =200
Examples 28 to 33:
examination of Cu in this section 0.0625 Ce 0.003 Si 0.575 O 1.218 The catalytic hydrogenation performance of different feed molecules, from examples 28 to 33, were dimethyl malonate, diethyl malonate, ethyl 3-hydroxypropionate, n-propyl 3-hydroxypropionate, n-butyl 3-hydroxypropionate and t-butyl 3-hydroxypropionate, respectively, and the catalyst evaluation methods were as in example 1, and the results are shown in Table 5.
TABLE 5 summary of the reaction results
Note: the raw material is a methanol solution with the mass number of 20%; the reaction temperature =160 ℃, the reaction pressure =60bar, and the liquid hourly space velocity =0.1h –1 Hydrogen to ester ratio =200
Examples 34 to 36: keeping others unchanged, changing x
Example 34:
selecting a reaction vessel, weighing 3.93g of methoxy copper and 0.56g of methoxy cerium respectively, adding 533mL of hexane, adding 414.60g of triphenyl silanol while stirring, stirring for 3h, heating to 70 ℃, refluxing for 10h, then draining the mixed solution under vacuum, and stopping stirring. The subsequent preparation and evaluation processes are the same as those in example 1, and the catalyst is calcined Cu or SiO 2 The mass fractions of (a) and (b) were 4.2% and 94.2%, respectively, and the following structural formula was obtained by converting the mass fractions into mass ratios of the substances: cu 0.0625 Ce 0.003 Si 1.5 O 3.069 . The evaluation results are shown in Table 6.Example 35:
selecting a reaction vessel, weighing 3.93g of methoxy copper and 0.56g of methoxy cerium respectively, adding 533mL of hexane, adding 691.00g of triphenyl silanol while stirring, stirring for 3h, heating to 70 ℃, refluxing for 10h, then draining the mixed solution under vacuum, and stopping stirring. The subsequent preparation and evaluation processes are the same as those in example 1, and the catalyst is calcined Cu or SiO 2 The mass fractions of (a) and (b) are 2.6% and 96.4%, respectively, and the following structural formula can be obtained by converting the mass fractions into mass ratios of the substances: cu (copper) 0.0625 Ce 0.003 Si 2.5 O 5.069 . The evaluation results are shown in Table 6.
Example 36:
selecting a reaction vessel, weighing 3.93g of methoxy copper and 0.25g of methoxy cerium respectively, adding 533mL of hexane, adding 967.4g of triphenyl silanol while stirring, stirring for 3 hours, heating to 70 ℃, refluxing for 10 hours, then draining the mixed solution under vacuum, and stopping stirring. The subsequent preparation and evaluation procedures were the same as in example 1, and the catalyst was calcined to obtain Cu and SiO 2 The mass fractions of (a) and (b) are 1.8% and 97.44%, respectively, and the following structural formula can be obtained by converting the mass fractions into mass ratios of the substances: cu 0.0625 Ce 0.003 Si 3.5 O 7.069 . The evaluation results are shown in Table 6.
Example 37:
selecting a reaction vessel, weighing 3.93g of methoxy copper and 0.25g of methoxy cerium respectively, adding 533mL of hexane, adding 1243.8g of triphenyl silanol while stirring, stirring for 3h, heating to 70 ℃, and refluxingAfter 10h, the mixture was drained under vacuum and the stirring was stopped. The subsequent preparation and evaluation processes are the same as those in example 1, and the catalyst is calcined Cu or SiO 2 The mass fractions of (a) and (b) are 1.5% and 98%, respectively, and the following structural formula can be obtained by converting the mass fractions into mass ratios of the substances: cu (copper) 0.0625 Ce 0.003 Si 4.5 O 9.069 . The evaluation results are shown in Table 6.
Example 38:
selecting a reaction vessel, weighing 3.93g of methoxy copper and 0.25g of methoxy cerium respectively, adding 533mL of hexane, adding 1796.6g of triphenyl silanol while stirring, stirring for 3h, heating to 70 ℃, refluxing for 10h, then draining the mixed solution under vacuum, and stopping stirring. The subsequent preparation and evaluation processes are the same as those in example 1, and the catalyst is calcined Cu or SiO 2 The mass fractions of (a) and (b) are 1% and 98.61%, respectively, and the following structural formula can be obtained by converting the mass fractions into mass ratios of the substances: cu 0.0625 Ce 0.003 Si 6.5 O 13.069 . The evaluation results are shown in Table 6.
TABLE 6 summary of the reaction results
Note: the raw material is a methanol solution with the mass number of 20%; reaction temperature =160 ℃, reaction pressure =60bar, liquid hourly space velocity =0.1h –1 Hydrogen to ester ratio =200
The present invention has been described in the above examples, but 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 the compound formed by organic copper and other metal ions or the doped mixed valence copper catalyst directly commercialized without departing from the spirit of the present invention, and these modifications are all within the protection of the present invention.
Claims (9)
1. Load type binaryA metal catalyst comprising a main metal Cu, a promoter metal M, and SiO 2 The structural general formula of the binary metal catalyst of the carrier can be expressed as Cu m M n Si x O y The auxiliary metal element component M is one of cerium, manganese, chromium, iron, cobalt, nickel, zinc, molybdenum, ruthenium, rhodium and palladium; in Cu m M n Si x O y In, O y The calculation result of (2) holds Cu m M n Si x O y The molecule is neutral, cu comprises Cu (0) and Cu (I), m: x =0.01 to 0.74, n: x =0.001 to 0.1;
the copper is selected from the group consisting of copper organo-siloxy as a precursor species of Cu, and copper organo-siloxy is selected from the group consisting of CuOSiR 3 、Cu 2 (O 2 SiR 2 )、Cu 3 (O 3 SiR)、Cu(OSiR 3 ) 2 、Cu[(R 2 SiO) 2 O]、Cu 3 [R 7 Si 7 O 1 2 ] 2 、Cu(RSiO 2 )、Cu 3 [(RSiO 2 ) 3 ] 2 、Cu 2 [(RSiO 2 ) 4 ]R is an organic group selected from one of alkyl, aryl, alkoxy, phenolic group and amino;
the assistant metal M is selected from the precursor species of organic silicon oxygen metal M, M and [ R ] in different oxidation states 3 SiO] - 、[R 2 SiO 2 ] 2- 、[(R 2 SiO) 2 O] 2- 、[RSiO 3 ] 3- 、[R 7 Si 7 O12] 3- 、[(RSiO 2 ) n ] n- To form the corresponding compound; r is an organic group and refers to one of alkyl, aryl, alkoxy, phenolic group and amido;
the alkyl is selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl; the aryl is selected from phenyl and substituted phenyl; the alkoxy is selected from oxymethyl, oxyethyl, oxypropyl, oxybutyl, oxypentyl, oxyhexyl, oxocyclopentyl, oxocyclohexyl; the phenol group is selected from phenol group and substituted phenol group; the amino group is selected from dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, dipentylamino group, dihexylamino group, methylphenylamino group, ethylphenylamino group, propylphenylamino group, butylphenyl amino group, pentylphenylamino group, hexylphenylamino group, silylphenylamino group, and silyl-substituted phenylamino group.
2. A process for the preparation of a supported bimetallic catalyst according to claim 1, characterized in that said organosilicone copper is prepared as follows: selecting a copper compound and organic silanol with a set molar ratio, and dissolving the copper compound and the organic silanol in an organic solvent; heating to reflux state, maintaining the state for a certain time, heating to evaporate to remove organic solvent, and drying the residue; the preparation method of the organosilicone-based metal M comprises the following steps: and (2) dissolving a metal M compound and organic silanol with a set molar ratio in an organic solvent, heating to a reflux state, keeping the reflux state for a certain time, heating for evaporation, removing the organic solvent, and performing suction filtration and drying on the remainder to obtain the metal M compound.
3. The process for preparing a supported bimetallic catalyst of claim 2, characterized in that said copper compound is selected from the group consisting of alkyl copper, aromatic copper, amine copper, alkoxy copper, phenol copper, copper phyllosilicate, basic copper carbonate; the alkyl is selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl and cyclohexyl; the aryl is selected from phenyl and substituted phenyl; the alkoxy is selected from oxymethyl, oxyethyl, oxypropyl, oxybutyl, oxypentyl, oxyhexyl, oxocyclopentyl, oxocyclohexyl; the phenol group is selected from phenol group and substituted phenol group, the amino group is selected from dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, dipentylamino group, dihexylamino group, methylphenylamino group, ethylphenylamino group, propylphenylamino group, butylphenylamino group, pentylphenylamino group, hexylphenylamino group, silylphenylamino group, and silylsubstituted phenylamino group.
4. The method for preparing a supported binary metal catalyst according to claim 2, wherein the organosilicone alcohol refers to a compound having a molecular structure of the general formula SiR n (OH) 4- n (n＝1,2,3)、(R 2 SiOH) 2 O]、H 2 [R 7 Si 7 O 12 ]Wherein R is one of alkyl, aryl, alkoxy, phenolic group and amino; the alkyl is selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl and cyclohexyl; the aryl is selected from phenyl and substituted phenyl; the alkoxy is selected from oxymethyl, oxyethyl, oxypropyl, oxybutyl, oxypentyl, oxyhexyl, oxocyclopentyl, oxocyclohexyl; the phenol group is selected from phenol group and substituted phenol group; the amino group is selected from dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, dipentylamino group, dihexylamino group, methylphenylamino group, ethylphenylamino group, propylphenylamino group, butylphenyl amino group, pentylphenylamino group, hexylphenylamino group, silylphenylamino group and silyl-substituted phenylamino group.
5. A process for preparing a supported bimetallic catalyst according to claim 2, characterized in that the M metal compound is selected from the group consisting of alkyl metals, aromatic metals, amino metals, alkoxy metals, phenolic metals, phyllosilicates, hydroxycarbonates; the alkyl is selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl and cyclohexyl; the aryl is selected from phenyl and substituted phenyl; the alkoxy is selected from oxymethyl, oxyethyl, oxypropyl, oxybutyl, oxypentyl, oxyhexyl, oxocyclopentyl, oxocyclohexyl; the phenol group is selected from phenol group and substituted phenol group; the amino group is selected from dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, dipentylamino group, dihexylamino group, methylphenylamino group, ethylphenylamino group, propylphenylamino group, butylphenyl amino group, pentylphenylamino group, hexylphenylamino group, silylphenylamino group, and silyl-substituted phenylamino group.
6. A process for preparing a supported binary metal catalyst according to claim 1 or 2, characterized by comprising the steps of: step 1): mixing an organic compound comprising copper, a metal M, and a silicone alcohol, wherein the copper is mixed with M metal M: n is 1 to 40:1, dissolved in an organic solvent; step 2): heating reflux and reaction: 3-24h; step 3): vacuum pumping organic solvent, drying, roasting and pre-reducing; the roasting temperature is set to be 350-650 ℃; the roasting time is 3-48 h; the roasting temperature rise rate is 4-20 ℃/min.
7. The process for preparing a supported binary metal catalyst according to claim 6, wherein the pre-reduction is carried out using a hydrogen-argon mixture, and the reduction step is as follows: 1) Raising the temperature from room temperature to 150 ℃ at the speed of 1 ℃/min, and keeping the temperature for 1min; 2) Then the temperature is increased to 300 ℃ at the speed of 10 ℃/min and is kept for 10-12h.
8. The method for preparing a supported binary metal catalyst according to claim 7, characterized in that the evaluation is carried out using a fixed bed reactor, and the evaluation steps are as follows: 1) Firstly, cooling a bed layer to a reaction temperature, replacing hydrogen and argon mixed gas with hydrogen, and increasing the pressure in a reaction tube to the reaction pressure; 2) Until the bed temperature is stable and the pressure in the pipe is stable; 3) Pumping reaction liquid with certain flow rate by a double-plunger micro pump, introducing hydrogen with certain flow rate to start reaction, determining the flow rate of the reaction liquid and the hydrogen by liquid hourly space velocity and hydrogen-ester ratio, obtaining reaction products after passing through a catalyst bed layer, cooling and collecting the products for later use, and recording and analyzing the products.
9. A method for preparing a supported binary metal catalyst according to claim 8, characterized in that: the reaction temperature is 130-270 ℃, and the reaction pressure of hydrogen is 10-100 Bar.
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