CN110694672B - Preparation method of supported copper-based catalyst and application of supported copper-based catalyst in synthesis of ethylene glycol - Google Patents

Preparation method of supported copper-based catalyst and application of supported copper-based catalyst in synthesis of ethylene glycol Download PDF

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CN110694672B
CN110694672B CN201911072747.7A CN201911072747A CN110694672B CN 110694672 B CN110694672 B CN 110694672B CN 201911072747 A CN201911072747 A CN 201911072747A CN 110694672 B CN110694672 B CN 110694672B
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CN110694672A (en
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王志光
李进
王贤彬
王炳春
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China Catalyst Holding Co ltd
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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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
    • B01J29/0333—Iron group metals or copper
    • 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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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention discloses a preparation method of a supported copper-based catalyst and application thereof in synthesizing ethylene glycol, wherein a silicon mesoporous molecular sieve is taken to react with sulfonic acid, then the silicon mesoporous molecular sieve and a silane coupling agent are subjected to hydroxyl condensation reaction, the obtained modified silicon mesoporous molecular sieve is further subjected to graft copolymerization reaction with an initiator and an acrylic acid compound, the obtained solid sample is added into an ethanol/water solution mixed solvent of soluble copper salt, heating reflux reaction is carried out, the obtained product is filtered again, deionized water is repeatedly washed, and the modified silicon mesoporous molecular sieve supported copper-based catalyst is obtained after drying and roasting. The preparation method can regulate and control the dispersion degree of copper species in the final catalyst, improve the synergistic effect of monovalent copper and zero-valent copper and obtain the high-dispersion supported nano-copper catalyst; the catalyst is used for the reaction of synthesizing the ethylene glycol by hydrogenating the dimethyl oxalate, wherein the conversion rate of the dimethyl oxalate is more than 99.4 percent, the selectivity of the ethylene glycol is more than 96 percent, the preparation process of the catalyst is simple, the cost is low, and the catalyst is beneficial to realizing industrial application.

Description

Preparation method of supported copper-based catalyst and application of supported copper-based catalyst in synthesis of ethylene glycol
Technical Field
The invention relates to a preparation method of a supported copper-based catalyst and application of the supported copper-based catalyst in synthesis of ethylene glycol, and belongs to the technical field of catalytic chemical engineering.
Background
Dimethyl oxalate (DMO) hydrogenation is the most critical step in the process of synthesizing ethylene glycol by CO coupling method. Meanwhile, dimethyl oxalate hydrogenation can be used for producing ethylene glycol, Methyl Glycolate (MG) and ethanol, which are important components of the coal chemical industry chain. After the UCC company in the United states and the Xingyu company in the 70 th century of the 20 th century established the process for synthesizing the oxalate by the normal-pressure gas-phase catalysis of the synthesis gas, the research on the preparation of the ethylene glycol by the Cu-based catalyst through the gas-phase hydrogenation of the oxalate is developed. U.S. UCC applied two patents on dimethyl oxalate hydrogenation in 1985, and U.S. Pat. No. 4,467,7234 discloses a Cu-Si catalyst prepared by using copper carbonate and ammonium carbonate as raw materials; US4628128 discloses a Cu-Si catalyst prepared by an impregnation process. In Japanese patent application JPS57122946, JPS57123127, JPS57180432, JPS57122941 and the like filed by the Kyoho company of Japan, 1982, the effects of a carrier supporting a Cu-based catalyst (Al2O3, SiO2, La2O3 and the like), an auxiliary agent (K, Zn, Ag and the like), a preparation method and the like on the catalytic activity and selectivity of the catalyst are disclosed, and the results show that the selectivity of ethylene glycol can be improved by adding Zn and the selectivity of methyl glycolate can be improved by adding Ag. The preparation method of the catalyst disclosed in the patent US4112245 mainly adopts a coprecipitation method to prepare Cu-Zn-Cr and Cu-Cr system catalysts, and introduces auxiliaries such as Ca, Cr and the like. The dimethyl oxalate hydrogenation catalyst mainly comprises a Cu-Si system and a Cu-Cr system, and although the Cu-Cr catalyst has better activity, Cr is extremely toxic and has large pollution, so that the catalyst is basically eliminated at present. Therefore, the Cu-Si system catalyst has good development prospect. However, various auxiliaries are introduced into the Cu-Si system, and the action mechanism and the action effect of the auxiliaries are unclear.
In a diethyl oxalate hydrogenation reaction, when the conversion rate of oxalic ester is 100%, the highest selectivity of glycol reaches 99.5%; as copper metal has the defects of low activity, easy sintering at high temperature, poor strength and the like, the stability of the pure Cu/SiO2 catalyst is poor, and the service life of the catalyst cannot meet the requirement of industrial application. Patent CN101455976A discloses an oxalate hydrogenation catalyst loaded with copper and other auxiliary metals, wherein a Cu-Mn/SiO2 catalyst with manganese as an auxiliary is used as a carrier to prepare an oxalate hydrogenation catalyst loaded with copper and other auxiliary metals, wherein in a dimethyl oxalate hydrogenation reaction, the reaction pressure is 3.0MPa, the reaction temperature is 200 ℃, and when H2/DMO is 50(mo1/mo1), the conversion rate of oxalate can reach 100%, the ethylene glycol selectivity is 91%, and when other conditions are not changed, when H2/DMO is increased to 180(mol/mol), the ethylene glycol selectivity is 95%. However, too high a hydrogen ester ratio also places high performance demands on the recycle compressor, which can add significantly to the production costs. Patents CN101138730A and CN102463122A also disclose a Cu-Ag/SiO2 catalyst for hydrogenation of oxalate, which is prepared by an impregnation method and a sol-gel method, respectively, and the catalyst has the disadvantages of complex preparation process, poor repeatability, large metal crystal grain, and poor dispersibility, and is difficult to achieve ideal effects in actual production.
The catalyst has high reaction temperature and pressure and low ethylene glycol selectivity, so that the heat and power consumption is high, the byproducts are increased, and in addition, the copper catalyst is easy to generate grain agglomeration and inactivation, so that the service life of the catalyst is difficult to meet the industrial requirement. Therefore, the oxalate hydrogenation catalyst suitable for industrial application firstly needs to have the stability capable of meeting the requirements of industrial application, and secondly has high oxalate conversion rate and high glycol selectivity on the basis of high stability.
Disclosure of Invention
The invention aims to solve the technical problem of the prior art and provides a preparation method of a supported copper-based catalyst and application of the supported copper-based catalyst in the catalytic synthesis of ethylene glycol by dimethyl oxalate hydrogenation.
The preparation method of the catalyst adopts hydroxylation on the surface of a silicon mesoporous molecular sieve, then carries out graft copolymerization to form-NH 2, -COOH and-OH groups, carries out copper ion loading through ion exchange and coordination, so that copper ions are uniformly distributed on the surface of the silicon mesoporous molecular sieve, dries, roasts and reduces to obtain sub-nanometer metal species with high thermal stability, regulates and controls the size and dispersion degree of the copper species in the final catalyst, improves the synergistic action of monovalent copper and zero-valent copper, improves the catalytic performance, stability and carbon deposition resistance and inactivation capacity, is favorable for the diffusion of substances and the arrangement of active sites, can be particularly applied to metal loading type catalyst carriers, improves the dispersion degree and reaction center activity of metal active components, increases the stability of industrial application and prolongs the service life.
The invention provides a preparation method of a supported copper-based catalyst, which is characterized by comprising the following preparation steps: taking a silicon mesoporous molecular sieve to react with sulfonic acid to increase the number of surface hydroxyl groups, and then carrying out hydroxyl condensation reaction with a silane coupling agent to form a modified silicon mesoporous molecular sieve product with double bonds bonded on the surface; and carrying out graft copolymerization reaction on the modified silicon mesoporous molecular sieve, an initiator and an acrylic compound, adding the obtained solid sample into an ethanol/water solution mixed solvent of soluble copper salt, heating and refluxing for reaction, filtering the obtained product again, repeatedly washing the product with deionized water, and drying and roasting the product to obtain the modified silicon mesoporous molecular sieve supported copper-based catalyst. The copper content in the catalyst is 10-45% of the total weight of the catalyst; the content of the monovalent copper after the reduction and activation of the catalyst is 20-60 mol% of the total mole of the active copper.
Further, in the above technical scheme, the specific preparation method of the silicon mesoporous molecular sieve supported copper-based catalyst of the present invention is characterized in that:
1) the silicon mesoporous molecular Sieve (SiO)2Meter) with sulfonic acid (R-SO)3H) According to molar ratio nSiO2：nR-SO3H1: (0.5-1.5) fully stirring and mixing for 0.5-4 hours at 50-80 ℃, wherein the concentration of sulfonic acid is 0.5-1.5 mol/L, then recovering solids by suction filtration or centrifugation, washing the solids to be nearly neutral by deionized water, and carrying out vacuum drying for 12-48 hours at 60-80 ℃ to obtain a surface modified mesoporous silicon molecular sieve sample.
2) The silicon mesoporous molecular Sieve (SiO) after surface modification2Metering) with silane coupling agent (Y-R-Si (OR)3) According to molar ratio nSiO2：nY-R-Si(OR)3Adding the mixture into an ethanol/water mixed solvent at 40-80 ℃ for reaction for 2-12 h, wherein the solvent accounts for 60-90% of the total mass, the ethanol content in the mixed solvent is 40-80%, and filtering or centrifuging after the reaction is finished to obtain a solid sample;
3) mixing the solid product obtained in the step 2) with an initiator and an acrylic compound in ethanol for graft copolymerization for 0.5-6 hours, wherein the concentration of the initiator is 0.5-0.8 mmol/L, the acrylic compound is 0.5-5 times of the mole number of a silane coupling agent added in the step 2), and the ethanol accounts for 60-90% of the total mass of the mixture; and (3) filtering or centrifugally recovering a product after reaction, fully washing the product with deionized water until the pH value is neutral, and performing vacuum drying at the temperature of 60-80 ℃ for 4-24 hours to obtain a solid sample.
4) According to the solid-liquid mass ratio of 1: (10-20) adding the solid sample obtained in the step 3) into a soluble copper salt ethanol/water solution mixed solvent with the concentration of 0.05-2.5 mol/L, wherein the ethanol content in the mixed solvent is 20-80%, refluxing for 2-24 hours at 80-100 ℃, vacuum filtering, fully washing with deionized water, vacuum drying for 12-48 hours at 60-80 ℃, and roasting for 2-8 hours at 400-600 ℃ to obtain the supported copper-based catalyst.
Further, in the technical scheme, the silicon mesoporous molecular sieve in the step 2) is one or a combination of SBA-15, MCM-41, MSU-G, MSU-1, FDU-7, FDU-12, KIT-6, HMS and MCF;
further, in the above technical solution, the soluble copper salt in step 3) is any one of copper nitrate, copper chloride, copper sulfate and copper acetate, and the content of copper element in the obtained catalyst is 15% to 40% of the total weight.
Further, in the technical scheme, the silicon mesoporous molecular sieve in the step 2) is one or a combination of SBA-15, MCM-41, MSU-G, MSU-1, FDU-7, FDU-12, KIT-6, HMS and MCF; the soluble copper salt in the step 3) is any one of copper nitrate, copper chloride, copper sulfate and copper acetate, and the content of copper element in the obtained catalyst is 15-40% of the total weight.
Further, in the above technical solution, the aminosilane coupling agent in the preparation process of the present invention includes gamma-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (beta-methoxyethoxy) silane, methylvinyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, methylvinyldimethoxysilane, vinyltriisopropoxysilane, methacryloxypropyltriethoxysilane, methacryloxypropylmethyldiethoxysilane, 5-hexenyltrimethoxysilane, N- (3-acryloyloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, allyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, and the like, Styrene ethyl trimethoxy silane, 7-octenyltrimethoxy silane, gamma-methacryloxypropyl methyl dimethoxy silane, 3- (acryloxy) propyl trimethoxy silane, 3- (N-allylamino) propyl trimethoxy silane, methacryloxymethyl triethoxy silane, acryloxymethyl trimethoxy silane, preferably gamma-methacryloxypropyl trimethoxy silane, vinyl triethoxy silane, vinyl trimethoxy silane, vinyl triisopropoxy silane, methacryloxypropyl triethoxy silane, 5-hexenyltrimethoxy silane, allyl triethoxy silane, allyl trimethoxy silane, 7-octenyltrimethoxy silane, methacryloxymethyl triethoxy silane, poly (vinyl ether, One or more of acryloyloxymethyl trimethoxysilane, 3- (acryloyloxy) propyl trimethoxysilane and 3- (N-allylamino) propyl trimethoxysilane.
Further, in the above technical scheme, in the preparation process of the present invention, the initiator includes any one or more of ammonium persulfate, potassium persulfate, sodium persulfate, azobisisobutyronitrile, cerium ammonium nitrate, azobisisobutyronitrile formamide, dimethyl azobisisobutyrate, azobisisobutyramidine hydrochloride, and azobisisobutyrimidazoline hydrochloride, and preferably any one or more of ammonium persulfate, potassium persulfate, azobisisobutyronitrile, cerium ammonium nitrate, and azobisisobutyronitrile formamide.
Further, in the above technical scheme, in the preparation process of the present invention, the acrylic acid compound includes any one or more of acrylic acid, methacrylic acid, phenylacrylic acid, 2- (trifluoromethyl) acrylic acid, 2-furan acrylic acid, 3-dimethylacrylic acid, 2-chloropropenoic acid, and 3- (3-pyridine) acrylic acid; any one or more of acrylic acid, methacrylic acid and phenylacrylic acid is preferred.
The catalyst prepared by the invention can be used for the reaction of synthesizing ethylene glycol by hydrogenating dimethyl oxalate, and is characterized in that the catalyst is placed in a constant temperature section of a fixed bed reactor, then dimethyl oxalate methanol solution is introduced into a gasification chamber and mixed with hydrogen, the mass ratio of hydrogen/ester substances is 20-100, the space velocity of hydrogen is 1500-5000 h < -1 >, the hydrogen partial pressure is 1-3 MPa, and the reaction temperature is 180-200 ℃.
In the process of dimethyl oxalate hydrogenation reaction, Cu0The active site mainly acts to activate H2Action of molecules, and Cu+The active site plays a role in polarizing and activating ester groups in the dimethyl oxalate, and the high conversion rate of the dimethyl oxalate hydrogenation reaction and the high selectivity of a target product are realized by the synergistic effect of the active site and the ester groups. During the reaction process, Cu is influenced by factors such as the increase of the agglomeration of copper particles and the change of metal-carrier interaction0/Cu+The ratio of (A) to (B) also varies greatly, and once the synergy is destroyed, the catalytic activity of the catalyst is reduced sharply, and the catalyst is apparently deactivated.
The preparation method of the catalyst provided by the invention can improve the loading capacity of the copper active component and the dispersity of the copper active component, reduce the diffusion resistance of reactant molecules and products on the catalyst, undoubtedly improve the conversion rate of dimethyl oxalate reaction and the selectivity of ethylene glycol products, reduce the inactivation rate and prolong the service life of the catalyst.
The invention aims to provide the catalyst for synthesizing the ethylene glycol by hydrogenating the dimethyl oxalate, which has the advantages of high activity, simple preparation process, low cost and environmental friendliness, wherein the conversion rate of the dimethyl oxalate can reach more than 99 percent, the selectivity of the ethylene glycol reaches 96 percent, the reaction is stable, and the control is easy.
Drawings
FIG. 1: example 1, a transmission electron microscope image of Cu/gcoSi-1 loaded copper-based catalyst is obtained;
FIG. 2 is a schematic diagram: example 2 transmission electron micrographs of Cu/gcoSi-2 loaded copper-based catalyst were obtained;
FIG. 3: the transmission electron micrograph of the Cu/gcoSi-3 loaded copper-based catalyst is obtained in example 3;
Detailed Description
The embodiments and the effects of the present invention are further illustrated by examples and comparative examples, but the scope of the present invention is not limited to the contents listed in the examples.
Example 1
A preparation method of a supported copper-based catalyst comprises the following steps:
1) will be provided with20.0g of silicon mesoporous molecular sieve SBA-15 and 181.56ml of methanesulfonic acid (CH) with the concentration of 1.1mol/L3SO3H) The solution is fully stirred and mixed for 2 hours at the temperature of 60 ℃, then the solid is recovered by suction filtration, the solution is washed by deionized water to be nearly neutral, and the solution is dried for 12 hours in vacuum at the temperature of 80 ℃ to obtain a surface modified silicon mesoporous molecular sieve sample.
2) Adding the surface-modified silicon mesoporous molecular sieve obtained in the step 1) and 413.34g of gamma-methacryloxypropyltrimethoxysilane into 2375.78g of an ethanol/water mixed solvent (the ethanol content is 80%) to react for 6 hours at 60 ℃, and filtering to obtain a solid sample after the reaction is finished;
3) mixing the solid sample in the step 2) with 0.05954g of ammonium persulfate and 179.90g of acrylic acid in 326.15g of ethanol for graft copolymerization reaction for 4 hours, filtering and recovering a product after the reaction, fully washing the pH value to be neutral by deionized water, and performing vacuum drying at 80 ℃ for 12 hours to obtain the solid sample.
4) Adding the solid sample obtained in the step 3) into a copper chloride ethanol/water mixed solution with the concentration of 0.5mol/L, wherein the mixed solution amount is 885.19ml, the mass content of ethanol is 40%, refluxing at 85 ℃ for 8h, carrying out vacuum filtration on a product, fully washing with deionized water, carrying out vacuum drying at 80 ℃ for 12h, roasting at 500 ℃ for 4h to obtain a supported copper-based catalyst, and recording the product of the catalyst as Cu/gcoSi-1, wherein the Cu content is 36.2% as measured by XRF.
Example 2
A preparation method of a supported copper-based catalyst comprises the following steps:
1) 20.0g of silicon mesoporous molecular sieve MCM-41 and 443.82ml of beta-naphthalenesulfonic acid (C10H8O3S) solution with the concentration of 0.90mol/L are fully stirred and mixed for 4 hours at the temperature of 55 ℃, then solid is recovered by suction filtration, the mixture is washed by deionized water to be nearly neutral, and the mixture is dried in vacuum for 16 hours at the temperature of 80 ℃ to obtain a surface modified silicon mesoporous molecular sieve sample.
2) Adding the surface-modified silicon mesoporous molecular sieve obtained in the step 1) and 394.73g of vinyl trimethoxy silane into 1289.64g of ethanol/water mixed solvent (ethanol content is 71%) to react for 6 hours at 60 ℃, and filtering to obtain a solid sample after the reaction is finished;
3) mixing the solid sample in the step 2) with 0.4774g of potassium persulfate and 733.60g of methacrylic acid in 2522.93g of ethanol for graft copolymerization reaction for 6 hours, filtering and recovering a product after the reaction, fully washing the pH value to be neutral by deionized water, and performing vacuum drying at 80 ℃ for 12 hours to obtain the solid sample.
4) Adding the solid sample obtained in the step 3) into a copper sulfate ethanol/water mixed solution with the concentration of 1.2mol/L, wherein the mixed solution amount is 195.75ml, the mass content of ethanol is 60%, refluxing for 12h at 80 ℃, performing vacuum filtration on a product, fully washing with deionized water, performing vacuum drying for 24h at 70 ℃, roasting for 4h at 500 ℃ to obtain a supported copper-based catalyst, and recording the product of the catalyst as Cu/gcoSi-2, wherein the Cu% content is 18.2% as measured by XRF.
Example 3
A preparation method of a supported copper-based catalyst comprises the following steps:
1) 20.0g of silicon mesoporous molecular sieve MSU-1 and 457.69ml of benzene sulfonic acid (C6H6O3S) solution with the concentration of 0.8mol/L are fully stirred and mixed for 2 hours at the temperature of 60 ℃, then solid is recovered by suction filtration, the mixture is washed by deionized water to be approximately neutral, and the mixture is dried for 12 hours in vacuum at the temperature of 80 ℃ to obtain a surface modified silicon mesoporous molecular sieve sample.
2) Adding the surface-modified silicon mesoporous molecular sieve obtained in the step 1) and 870.06g of methacryloxypropyltriethoxysilane into 1878.54g of ethanol/water mixed solvent (ethanol content is 67%) to react for 6 hours at 60 ℃, and filtering to obtain a solid sample after the reaction is finished;
3) mixing the solid sample obtained in the step 2) with 0.1286g of azodiisobutyronitrile and 399.47g of phenylacrylic acid in 978.77g of ethanol for graft copolymerization for 4 hours, filtering and recovering a product after the reaction, fully washing the pH value to be neutral by deionized water, and performing vacuum drying at 80 ℃ for 12 hours to obtain the solid sample.
4) Adding the solid sample obtained in the step 3) into a copper nitrate ethanol/water mixed solution with the concentration of 0.75mol/L, wherein the mixed solution amount is 574.28ml, the mass content of ethanol is 80%, refluxing for 6h at 80 ℃, performing vacuum filtration on a product, fully washing with deionized water, performing vacuum drying for 24h at 60 ℃, roasting for 8h at 450 ℃ to obtain a supported copper-based catalyst, and recording the product of the catalyst as Cu/gcoSi-3, wherein the Cu% content is 26.9% as measured by XRF.
Example 4
A preparation method of a supported copper-based catalyst comprises the following steps:
1) 20.0g of silicon mesoporous molecular sieve KIT-6 and 499.30ml of methanesulfonic acid (CH3SO3H) solution with the concentration of 0.6mol/L are fully stirred and mixed for 2 hours at the temperature of 60 ℃, then solid is recovered by suction filtration, the mixture is washed to be nearly neutral by deionized water, and the mixture is dried for 12 hours in vacuum at the temperature of 80 ℃ to obtain a surface modified silicon mesoporous molecular sieve sample.
2) Adding the surface-modified silicon mesoporous molecular sieve obtained in the step 1) and 540.11g of allyl trimethoxy silane into 921.10g of ethanol/water mixed solvent (ethanol content is 56%) to react for 6 hours at 90 ℃, and filtering to obtain a solid sample after the reaction is finished;
3) mixing the solid sample obtained in the step 2) with 1.3284g of ammonium ceric nitrate and 1191.53g of 3- (3-pyridine) acrylic acid in 4846.10g of ethanol for graft copolymerization for 4 hours, filtering and recovering a product after the reaction, fully washing the pH value to be neutral by deionized water, and performing vacuum drying at 80 ℃ for 12 hours to obtain the solid sample.
4) Adding the solid sample obtained in the step 3) into a copper acetate ethanol/water mixed solution with the concentration of 0.5mol/L, wherein the mixed solution amount is 707.01ml, the mass content of ethanol is 70%, refluxing at 90 ℃ for 8h, carrying out vacuum filtration on a product, fully washing with deionized water, carrying out vacuum drying at 80 ℃ for 8h, roasting at 500 ℃ for 6h to obtain a supported copper-based catalyst, and recording the product of the catalyst as Cu/gcoSi-4, wherein the Cu content is 30.8% as measured by XRF.
Example 5
A preparation method of a supported copper-based catalyst comprises the following steps:
1) 20.0g of silicon mesoporous molecular sieve FDU-7 and 204.84ml of benzenesulfonic acid (C6H6O3S) solution with the concentration of 1.3mol/L are fully stirred and mixed for 2 hours at the temperature of 60 ℃, then solid is recovered by suction filtration, the mixture is washed to be nearly neutral by deionized water, and the mixture is dried for 12 hours in vacuum at the temperature of 80 ℃ to obtain a surface modified silicon mesoporous molecular sieve sample.
2) Adding the surface-modified silicon mesoporous molecular sieve obtained in the step 1) and 524.01g of methacryloxymethyltriethoxysilane into 3499.00g of ethanol/water mixed solvent (ethanol content is 50%) to react for 8 hours at 80 ℃, and filtering to obtain a solid sample after the reaction is finished;
3) mixing the solid sample in the step 2) with 0.6617g of azo isobutyryl cyano formamide and 899.82g of 3, 3-dimethyl acrylic acid in 6745.32g of ethanol for graft copolymerization for 5 hours, filtering and recovering a product after the reaction, fully washing the pH value to be neutral by deionized water, and performing vacuum drying at 80 ℃ for 12 hours to obtain the solid sample.
4) Adding the solid sample obtained in the step 3) into a copper chloride ethanol/water mixed solution with the concentration of 0.6mol/L, wherein the mixed solution amount is 390.43ml, the mass content of ethanol is 40%, refluxing at 85 ℃ for 8h, carrying out vacuum filtration on a product, fully washing with deionized water, carrying out vacuum drying at 80 ℃ for 12h, roasting at 500 ℃ for 4h to obtain a supported copper-based catalyst, and recording the product of the catalyst as Cu/gcoSi-5, wherein the Cu% content is 21.4% as measured by XRF.
Example 6
A preparation method of a supported copper-based catalyst comprises the following steps:
1) 20.0g of silicon mesoporous molecular sieve FDU-12 and 310.67ml of beta-naphthalenesulfonic acid (C10H8O3S) solution with the concentration of 1.5mol/L are fully stirred and mixed for 2 hours at the temperature of 60 ℃, then solid is recovered by suction filtration, the mixture is washed by deionized water to be nearly neutral, and the mixture is dried in vacuum at the temperature of 80 ℃ for 12 hours to obtain a surface modified silicon mesoporous molecular sieve sample.
2) Adding the surface-modified silicon mesoporous molecular sieve obtained in the step 1) and 513.30g of acryloyloxy methyl trimethoxy silane into 2312.34g of ethanol/water mixed solvent (ethanol content is 42%) to react for 4 hours at 90 ℃, and filtering to obtain a solid sample after the reaction is finished;
3) mixing the solid sample obtained in the step 2) with 0.1823g of azodiisobutyronitrile and 386.19g of 2-furan acrylic acid in 1850.44g of ethanol for graft copolymerization reaction for 6 hours, filtering and recovering a product after the reaction, fully washing the pH value to be neutral by deionized water, and performing vacuum drying at 60 ℃ for 24 hours to obtain the solid sample.
4) Adding the solid sample obtained in the step 3) into a copper nitrate ethanol/water mixed solution with the concentration of 1.1mol/L, wherein the mixed solution amount is 295.66ml, the mass content of ethanol is 75%, refluxing at 80 ℃ for 8h, carrying out vacuum filtration on a product, fully washing with deionized water, carrying out vacuum drying at 80 ℃ for 12h, roasting at 500 ℃ for 4h to obtain a supported copper-based catalyst, and recording the product of the catalyst as Cu/gcoSi-6, wherein the Cu content is 24.7% as measured by XRF.
Comparative example 1: the catalyst was prepared according to the method described in the example of patent CN 103816915A:
7.6g of Cu (NO)3)2·3H2Dissolving O in 500ml of deionized water to form a solution, adjusting the pH value of the solution to 2-3 by using nitric acid, adding 10g of urea, and then adding 7.89g of mesoporous SiO2Support (HMS), stirred vigorously for 4 hours to form a mixed solution.
The three-necked flask containing the mixed solution was put in a 90 ℃ oil bath and stirred, and heated to reflux the vapor. The pH value of the solution gradually rises along with the decomposition of the urea, stirring is stopped when the pH value of the solution rises to 7.0, the solution is filtered while the solution is hot, the obtained filter cake (precipitate) is washed by deionized water, the precipitate is dried at 120 ℃ for 12 hours, then the dried precipitate is moved to a muffle furnace, the temperature is raised to 450 ℃ at the speed of 1 ℃/min under the air atmosphere, and then the temperature is maintained for 4 hours, so that the Cu/HMS catalyst with the copper mass percentage content of 20.3 percent is obtained, and the catalyst product is marked as CuSiVS-1.
Comparative example 2: the catalyst was prepared according to the method described in the patent CN106563449A example:
dissolving 10.6g of copper nitrate and 0.5g of mannitol in 100g of distilled water, fully dissolving, and then placing in an ultrasonic instrument for ultrasonic oscillation for 20min, wherein the ultrasonic frequency is 25 kHz. 5.0g of urea was added to the above solution and dissolved by stirring, and then 20m of 1m of ammonia water was added thereto and stirred sufficiently for 30 min. Finally, 21g of an alkaline silica sol containing 40% SiO2 was added dropwise, the mixture was mechanically stirred and placed in a water bath at 80 ℃ for 5 hours, and heating was stopped until the pH of the solution reached approximately 7. And filtering to obtain a filter cake, washing the filter cake with distilled water for multiple times, drying the obtained filter cake in air at 120 ℃ for 24 hours, and roasting at 450 ℃ for 4 hours in an air atmosphere to obtain the Cu/SiO2 catalyst, wherein the mass fraction of Cu is 24.9 wt%, and the catalyst product is marked as CuSiVS-2.
Examples 7 to 14
The application example is as follows:
application investigation was performed on the catalysts obtained in examples 1 to 6 and comparative examples 1 to 2:
respectively taking 10ml of the catalysts obtained in the examples 1-6 and the comparative examples 1-2 and filling the catalysts into a tubular reactor; the reaction tube is heated to 250 ℃ from room temperature at the speed of 2 ℃/min, the hydrogen content is gradually increased to 100 percent from 10 percent, after the temperature of the reaction tube is heated to 250 ℃, the reaction tube is reduced for 5 hours by hydrogen with the flow rate of 50m1/(min ml cat.)99.99 percent, and the reduction pressure is 1.2 MPa; then the prepared 0.2g/ml dimethyl oxalate methanol solution is introduced into a gasification chamber and mixed with hydrogen. Dimethyl oxalate is taken as a raw material, and the hydrogen/ester molar ratio is 50: 1, the space velocity of hydrogen is 2000h < -1 >, the reaction temperature is controlled to be 180-200 ℃, the reaction pressure is about 2.0MPa, the operation is carried out for 48 hours, various data of the catalyst are measured, and the result is shown in a table 2, wherein DMO represents dimethyl oxalate, EG represents ethylene glycol, and MG represents methyl glycolate.
Table 1: catalytic performance of different catalysts
Figure BDA0002261462090000141
*: the percentage of monovalent copper Cu + in the reduced copper-based catalyst was determined by XPS.
As can be seen from the analysis of Table 1, the catalyst prepared by the embodiment of the invention has the conversion rate of 99.4 percent, the selectivity of the product ethylene glycol of 96 percent and the byproduct methyl glycolate of 4 percent in the hydrogenation reaction of dimethyl oxalate; in the reaction of the catalyst obtained in the comparative example under the same conditions, the conversion rate of dimethyl oxalate is less than 99%, the selectivity of ethylene glycol is less than 87%, and the by-product methyl glycolate is more than 13%; the conversion rate and the product conversion rate of the catalyst prepared by the invention are higher, the selectivity of byproducts is lower, and the overall catalytic activity has obvious advantages.
The above examples are only for illustrating the technical concept and features of the present invention, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.

Claims (10)

1. A preparation method of a supported copper-based catalyst is characterized by comprising the following steps: taking a silicon mesoporous molecular sieve to react with sulfonic acid to increase the number of surface hydroxyl groups, and then carrying out hydroxyl condensation reaction with a silane coupling agent to form a modified silicon mesoporous molecular sieve product with double bonds bonded on the surface; carrying out graft copolymerization reaction on the modified silicon mesoporous molecular sieve, an initiator and an acrylic compound, adding an obtained solid sample into an ethanol/water solution mixed solvent of a soluble copper salt, heating and refluxing for reaction, filtering an obtained product again, washing the product with deionized water, drying and roasting to obtain the modified silicon mesoporous molecular sieve supported copper-based catalyst, wherein the copper content in the catalyst is 10-45% of the total weight of the catalyst; the content of the monovalent copper after the reduction and activation of the catalyst is 20-60 mol% of the total mole of the active copper;
the silane coupling agent comprises gamma-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (beta-methoxyethoxy) silane, methylvinyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, methylvinyldimethoxysilane, vinyltriisopropoxysilane, methacryloxypropyltriethoxysilane, methacryloxypropylmethyldiethoxysilane, 5-hexenyltrimethoxysilane, N- (3-acryloyloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, allyltriethoxysilane, allyltrimethoxysilane, styrethyltrimethoxysilane, 7-octenyltrimethoxysilane, vinylethoxysilane, vinyltrimethoxysilane, or a mixture of a compound of a formula (I, a compound of a compound, Gamma-methacryloxypropylmethyldimethoxysilane, 3- (acryloyloxy) propyltrimethoxysilane, 3- (N-allylamino) propyltrimethoxysilane, methacryloxymethyltriethoxysilane, and acryloyloxymethyltrimethoxysilane.
2. The method of claim 1, wherein: the specific preparation method of the silicon mesoporous molecular sieve supported copper-based catalyst is characterized in that:
1) the silicon mesoporous molecular sieve is made of SiO2Counting with sulfonic acid R-SO3H is expressed by molar ratio nSiO2：nR-SO3H =1: (0.5-1.5) fully stirring and mixing for 0.5-4 hours at 50-80 ℃, wherein the concentration of sulfonic acid is 0.5-1.5 mol/L, then recovering solids by suction filtration or centrifugation,washing the silicon mesoporous molecular sieve with deionized water to be approximately neutral, and carrying out vacuum drying at the temperature of 60-80 ℃ for 12-48 hours to obtain a surface modified silicon mesoporous molecular sieve sample;
2) the surface modified silicon mesoporous molecular sieve is treated with SiO2Metering with silane coupling agent Y-R-Si (OR)3According to molar ratio nSiO2：nY-R-Si(OR)3(5-10), adding the mixture into an ethanol/water mixed solvent, reacting for 2-12 hours at 40-80 ℃, wherein the solvent accounts for 60-90% of the total mass, the ethanol content in the mixed solvent is 40-80%, and filtering or centrifuging the mixture after the reaction is finished to obtain a solid sample;
3) mixing the solid sample obtained in the step 2) with an initiator and an acrylic compound in ethanol to perform a graft copolymerization reaction for 0.5-6 hours, wherein the concentration of the initiator is 0.5-0.8 mmol/L, the acrylic compound is 0.5-5 times of the mole number of a silane coupling agent added into the solid sample obtained in the step 2), and the ethanol accounts for 60-90% of the total mass of the mixture; filtering or centrifugally recovering a product after reaction, fully washing the product with deionized water until the pH value is neutral, and performing vacuum drying at the temperature of 60-80 ℃ for 4-24 hours to obtain a solid sample;
4) according to the solid-liquid mass ratio of 1: (10-20) adding the solid sample obtained in the step 3) into a soluble copper salt ethanol/water solution mixed solvent with the concentration of 0.05-2.5 mol/L, wherein the ethanol content in the mixed solvent is 20-80%, refluxing at 80-100 ℃ for 2-24 h, carrying out vacuum filtration, fully washing with deionized water, carrying out vacuum drying at 60-80 ℃ for 12-48 h, and roasting at 400-600 ℃ for 2-8 h to obtain the supported copper-based catalyst.
3. The method of claim 2, wherein: the silicon mesoporous molecular sieve in the step 2) is one or the combination of SBA-15, MCM-41, MSU-G, MSU-1, FDU-7, FDU-12, KIT-6, HMS and MCF.
4. The method of claim 2, wherein: the soluble copper salt in the step 3) is any one of copper nitrate, copper chloride, copper sulfate and copper acetate, and the content of copper element in the obtained catalyst is 15-40% of the total weight.
5. The production method according to claim 1 or 2, characterized in that: the silane coupling agent comprises any one or more of gamma-methacryloxypropyltrimethoxysilane, vinyl triethoxysilane, vinyl trimethoxysilane, vinyl triisopropoxysilane, methacryloxypropyltriethoxysilane, 5-hexenyltrimethoxysilane, allyl triethoxysilane, allyl trimethoxysilane, 7-octenyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, 3- (acryloyloxy) propyltrimethoxysilane and 3- (N-allylamino) propyltrimethoxysilane.
6. The production method according to claim 1 or 2, characterized in that: the initiator comprises any one or more of ammonium persulfate, potassium persulfate, sodium persulfate, azobisisobutyronitrile, ammonium ceric nitrate, azoisobutyronitrile formamide, azodiisobutyronidine dimethyl isobutyrate, azodiisobutymidine hydrochloride and azodiisobutylimidazoline hydrochloride.
7. The production method according to claim 1 or 2, characterized in that: the initiator comprises any one or more of ammonium persulfate, potassium persulfate, azodiisobutyronitrile, ammonium ceric nitrate and azoisobutyryl cyano formamide.
8. The production method according to claim 1 or 2, characterized in that: the acrylic acid compound comprises any one or more of acrylic acid, methacrylic acid, phenyl acrylic acid, 2- (trifluoromethyl) acrylic acid, 2-furan acrylic acid, 3-dimethylacrylic acid, 2-chloropropenoic acid and 3- (3-pyridine) acrylic acid.
9. The production method according to claim 1 or 2, characterized in that: the acrylic acid compound comprises any one or more of acrylic acid, methacrylic acid and phenyl acrylic acid.
10. A process for the synthesis of ethylene glycol, characterized in that the process of any of claims 1 to 9The catalyst obtained by the preparation method is placed in a constant temperature section of a fixed bed reactor, then dimethyl oxalate methanol solution is introduced into a gasification chamber and mixed with hydrogen, the mass ratio of hydrogen to ester substances is 20-100, and the air speed of the hydrogen is 1500-5000 h-1The hydrogen partial pressure is 1-3 MPa, and the reaction temperature is 180-200 ℃.
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