Preparation method of 1, 4-butanediol
By using a double hydrolysis method to prepare a large-pore copper-based catalyst, the problems of low catalyst selectivity and numerous by-products in the existing technology have been solved, achieving efficient 1,4-butanediol production and reducing costs and energy consumption.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- CHINA PETROLEUM & CHEMICAL CORP
- Filing Date
- 2024-11-18
- Publication Date
- 2026-05-19
AI Technical Summary
In existing technologies, catalysts have low selectivity and easily generate tetrahydrofuran as a byproduct during the hydrogenation of γ-butyrolactone. In particular, the use of precious metal palladium catalysts results in high costs and easy loss, while copper catalysts have higher selectivity for the byproduct 1-butanol.
A copper-based catalyst was prepared via a double hydrolysis co-precipitation method. Alumina and a high-molecular polymer containing nitrogen-containing heterocyclic side groups were used as dispersants to avoid copper hydroxide impurities and form a large-pore layered structure, thereby improving the uniformity and selectivity of the catalyst.
It significantly reduced the formation of tetrahydrofuran during the hydrogenation of γ-butyrolactone, improved the selectivity and conversion rate of 1,4-butanediol, reduced the formation of by-products, and decreased separation energy consumption and equipment investment.
Smart Images
Figure CN122059802A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of catalytic hydrogenation technology, specifically, it relates to a method for preparing 1,4-butanediol. Background Technology
[0002] 1,4-Butanediol (BDO) is an important industrial chemical used to produce many basic chemicals, such as tetrahydrofuran (THF), polybutylene terephthalate (PBT), polybutylene succinate (PBS), polyurethane, and polyester polyols. There are three main commercial production routes for BDO: (1) hydrogenation of butynediol produced by carbonylation of acetylene and formaldehyde (Reppe method); (2) hydrogenation of maleic anhydride (MA); and (3) acetoxylation of butadiene. Due to its safe operation and low-cost n-butane feedstock, the process of preparing MA by oxidation of n-butane and then hydrogenating it to produce 1,4-butanediol has attracted increasing interest. The preparation of 1,4-butanediol from MA generally involves two reaction steps: first, hydrogenation of MA to butyrolactone, and second, hydrogenation of butyrolactone to 1,4-butanediol. Currently, butyrolactone hydrogenation generally uses noble metal or copper catalysts.
[0003] JP07082189A discloses a method for preparing 1,4-butanediol by hydrogenation of γ-butyrolactone. The method uses Pd / C as a catalyst and GBL under intermittent conditions at 180°C and 10 MPa hydrogen pressure. The selectivity of BDO is 88.6% and the conversion rate is 98%.
[0004] The catalytic selectivity in biomass-derived succiCuc acid hydrogenation on FeOx-modified Pd catalysts was reported. In the hydrogenation reaction of γ-butyrolactone, Pd / C modified with Fe exhibited a BDO selectivity of 70.8% and a conversion rate of 76.4% at 200 °C and 5 MPa hydrogen pressure. However, palladium, as a precious metal, is expensive to use and prone to loss during the reaction process.
[0005] JP03178943 uses a copper-chromite catalyst (Cu / CrBaMnO, where the mass percentages of Cu, Cr, Ba, and Mn are 27.6%, 31.2%, 0.6%, and 2.5%, respectively). Under conditions of 210℃ and 6MPa hydrogen pressure, the conversion rate of γ-butyrolactone is 73%, the selectivity of 1,4-butanediol is 83.5%, and the selectivity of the byproduct 1-butanol is approximately 5%.
[0006] US4797382 discloses a SiO2-supported multi-component Cu-Pd-KOH catalyst that achieves a GBL conversion of 96.5% and a BDO selectivity of 99.0% under hydrogen conditions of 160 °C and 6.2 MPa.
[0007] US4652685 discloses a method for producing 1,4-butanediol by gas-phase GBL hydrogenation, in which gas-phase GBL is hydrogenated on CuCrOx at 210 °C, selectively producing BDO (87-97%) with a conversion of 60-70%, and 1-butanol (1-Bol) and THF with selectivities as high as 1.1% and 5.5%, respectively.
[0008] CN11544881A discloses a silica-supported Cu-Co hydrogenation catalyst. Under conditions of 160℃ and 5MPa hydrogen pressure for 4 hours, the conversion rate of γ-butyrolactone reached 80.5%, and the selectivity for 1,4-butanediol was 97%. This demonstrates that improving catalyst selectivity and reducing byproducts during the reaction are key research areas when using copper catalysts. Summary of the Invention
[0009] The purpose of this invention is to overcome the problems of low catalyst selectivity and byproduct generation in the preparation process of existing technologies, and to provide a method for preparing 1,4-butanediol. The copper-based catalyst used in this method has high catalytic hydrogenation selectivity and can significantly reduce the generation of tetrahydrofuran, a byproduct, during the hydrogenation of γ-butyrolactone.
[0010] To achieve the above objectives, the present invention provides a method for preparing 1,4-butanediol, the method comprising: reacting a catalyst, γ-butyrolactone, and an organic solvent in the presence of hydrogen to obtain a product containing 1,4-butanediol; wherein the catalyst is a copper-based catalyst, the copper-based catalyst contains an active component copper and a dispersant alumina, and the most probable pore size of the copper-based catalyst is 18-40 nm.
[0011] Through the above technical solution, the large-pore copper-based catalyst used in this invention can avoid copper hydroxide impurities during the precipitation process, resulting in a catalyst with a more uniform structure, which can significantly reduce the formation of tetrahydrofuran, a byproduct, during the hydrogenation of γ-butyrolactone. Attached Figure Description
[0012] Figure 1 The images show the XRD patterns of the copper-based catalysts prepared in Preparation Examples 1-4 and Comparative Preparation Examples 1-3.
[0013] Figure 2 The diagram shows the most probable pore size distribution of the copper-based catalysts prepared in Preparation Examples 1-4 and Comparative Preparation Examples 1-3. Detailed Implementation
[0014] The endpoints and any values of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, the endpoint values of the various ranges, the endpoint values of the various ranges and individual point values, and individual point values can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.
[0015] As previously stated, the present invention provides a method for preparing 1,4-butanediol, the method comprising: reacting a catalyst, γ-butyrolactone and an organic solvent in the presence of hydrogen to obtain a product containing 1,4-butanediol; wherein the catalyst is a copper-based catalyst, the copper-based catalyst contains an active component copper and a dispersant alumina, and copper hydroxide without impurities, and the most probable pore size of the copper-based catalyst is 18-40 nm.
[0016] The inventors of this invention discovered that in the method for preparing 1,4-butanediol, the copper-based catalyst used is prepared by a double hydrolysis co-precipitation method. The use of a mixed alkaline solution effectively suppresses the formation of copper hydroxide impurities. Because copper hydroxide impurities are absent, the catalytic sites of the catalyst are more uniform, thus significantly improving the selectivity of 1,4-butanediol in the catalytic hydrogenation of γ-butyrolactone. Furthermore, in the preparation of the copper-based catalyst, a polymer with nitrogen-containing heterocyclic side groups is used as a template agent. Due to the coordination and supporting effect of the template agent with metal ions, a pore-expanding effect is achieved, resulting in high catalytic hydrogenation selectivity and significantly reducing the formation of tetrahydrofuran, a byproduct, during the hydrogenation of γ-butyrolactone.
[0017] According to the present invention, the most probable pore size of the copper-based catalyst is 25-35 nm.
[0018] According to the present invention, the copper-based catalyst is a layered copper-based catalyst.
[0019] According to the present invention, the copper content is 60-80 wt%, preferably 63-80 wt%, based on the total weight of the copper-based catalyst.
[0020] According to the present invention, the method for preparing the copper-based catalyst includes:
[0021] (1) A double hydrolysis reaction is carried out by contacting a copper salt solution and a mixed alkaline solution; wherein the mixed alkaline solution contains aluminate, alkali and a high molecular polymer containing nitrogen heterocyclic side groups;
[0022] (2) The product obtained from step (1) is filtered, washed and dried to obtain a copper-based catalyst.
[0023] According to the present invention, the copper salt in the copper-containing solution is selected from copper nitrate and / or copper sulfate.
[0024] According to the present invention, the concentration of the copper salt solution is 0.05-4 mol / L, preferably 0.15-3 mol / L.
[0025] According to the present invention, the aluminate is sodium aluminate and / or potassium aluminate; preferably, in the mixed alkaline solution, the concentration of the aluminate is 0.01-2 mol / L, more preferably 0.05-1 mol / L.
[0026] According to the present invention, the alkali is selected from at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, and potassium bicarbonate; preferably, in the mixed alkali solution, the concentration of the alkali is 0.01-4 mol / L, more preferably 0.1-2 mol / L.
[0027] According to the present invention, the polymer containing nitrogen-containing heterocyclic side groups is polyvinylimidazole; preferably, in the mixed alkaline solution, the concentration of the polymer containing nitrogen-containing heterocyclic side groups is 0.01-0.5 mol / L, more preferably 0.01-0.1 mol / L.
[0028] According to the present invention, in step (1), the copper salt solution and the mixed alkaline solution are first mixed by contact, wherein the mixing conditions may include mixing at a temperature of 20-50°C, preferably mixing under stirring conditions, wherein there is no particular limitation on the stirring rate, as long as it promotes uniform mixing.
[0029] According to the present invention, the conditions for the double hydrolysis reaction include a temperature of 20-50°C and a time of 10-360 min. Limiting the conditions of the double hydrolysis reaction to the aforementioned range in this invention has the advantage of being suitable for actual industrial production. If the temperature is too low, an additional cooling process is required; if the temperature is too high, the generated precipitate will decompose, resulting in black copper oxide.
[0030] According to the present invention, the conditions for the double hydrolysis reaction include: pH 8-12, preferably 9-11; in the present invention, the pH condition is limited to the aforementioned range, and the copper and aluminum ions are completely precipitated. If the pH is too low, some metal ions will not be able to precipitate, and if the pH is too high, aluminum ions will redissolve.
[0031] According to the present invention, in step (2), the product obtained by the reaction in step (1) is filtered, washed and dried to obtain a copper-based catalyst; wherein, the filtration can be carried out by a method well known in the art; the washing can be done with deionized water, and the number of washings is not particularly limited, preferably 3-5 times; the drying conditions include: a temperature of 40-100℃ and drying for 4-24h; preferably, drying at a temperature of 40-50℃ for 4-12h.
[0032] According to a particularly preferred embodiment of the present invention, a method for preparing a large-pore copper-based catalyst includes the following steps:
[0033] (1) A copper salt solution and a mixed alkaline solution are obtained respectively; wherein the mixed alkaline solution contains aluminate, alkali and a polymer containing nitrogen heterocyclic side groups;
[0034] (2) The copper salt aqueous solution and the mixed alkaline solution from step (1) are stirred and mixed to obtain a suspension for reaction, thereby obtaining the thin-film copper catalyst.
[0035] According to the present invention, the organic solvent includes one or more of dioxane, tetrahydrofuran and N,N-dimethylformamide, preferably dioxane.
[0036] According to the present invention, the weight ratio of the copper-based catalyst, γ-butyrolactone and organic solvent is (1-2):1:(19-99); preferably 2:1:19.
[0037] According to the present invention, the reaction conditions for the catalyst, γ-butyrolactone and organic solvent to react include: a reaction temperature of 100-250°C and a reaction pressure of 3-7 MPa; preferably, the reaction temperature is 150-200°C and the reaction pressure is 4-5 MPa.
[0038] The present invention will be described in detail below through embodiments.
[0039] In the following preparation examples, comparative preparation examples, examples, and comparative examples:
[0040] The pore size distribution was measured by N2 adsorption-desorption method.
[0041] The content of copper component was determined by X-ray fluorescence spectrometry.
[0042] XRD characterization was performed using an X-ray powder diffractometer.
[0043] All reagents used were commercially available and of analytical grade.
[0044] Preparation Example 1
[0045] This preparation example illustrates a copper-based catalyst prepared by co-precipitation using a dual hydrolysis method.
[0046] (1) Prepare a copper nitrate aqueous solution with a concentration of 0.75 mol / L, and prepare mixed solutions of sodium aluminate, sodium carbonate and polyvinyl imidazole with concentrations of 0.25 mol / L, 0.5 mol / L and 0.05 mol / L respectively. Mix the two solutions at 30°C with stirring, and keep the pH of the system at 11 during the mixing process.
[0047] (2) When the volume of the mixed solution reaches 200 ml, stop mixing and transfer it to a hydrothermal reactor and keep it at 40 °C for 60 min; filter the obtained product, wash it with deionized water, and dry it at 50 °C for 4 h to obtain the copper-based catalyst, labeled as S1.
[0048] X-ray fluorescence spectroscopy (XRF) analysis showed that the Cu content in this copper-based catalyst was 79.7 wt%.
[0049] Figure 1 These are the XRD patterns of the copper-based catalysts prepared in Preparation Examples 1-4 and Comparative Preparation Examples 1-3, where the horizontal axis represents the diffraction angle 2θ (°). XRD characterization is shown in [reference needed]. Figure 1 The characteristic peaks of copper hydroxide at diffraction angles of 16.7° and 63.1° indicate that no impurity copper hydroxide is formed in the S1 structure.
[0050] Determined by N2 adsorption-desorption method, see [reference]. Figure 2 The most probable pore size distribution of the copper-based catalyst, with the most probable pore size of S1 being 35 nm.
[0051] Preparation Example 2
[0052] This preparation example illustrates a copper-based catalyst prepared by co-precipitation using a dual hydrolysis method.
[0053] (1) Prepare a copper nitrate aqueous solution with a concentration of 0.75 mol / L, and prepare mixed solutions of sodium aluminate, sodium carbonate and polyvinyl imidazole with concentrations of 0.25 mol / L, 0.5 mol / L and 0.05 mol / L respectively. Mix the two solutions at 30°C with stirring, and keep the pH of the system at 10 during the mixing process.
[0054] (2) When the volume of the mixed solution reaches 200 ml, stop mixing and transfer it to a hydrothermal reactor and keep it at 40 °C for 120 min; filter the obtained product, wash it with deionized water, and dry it at 40 °C for 10 h to obtain the copper-based catalyst, labeled as S2.
[0055] XRF characterization showed that the Cu content in this copper-based catalyst was 77.6 wt%.
[0056] XRD characterization, see [link / reference] Figure 1The characteristic peaks of copper hydroxide at diffraction angles of 16.7° and 63.1° indicate that no impurity copper hydroxide is formed in the S2 structure.
[0057] Determined by N2 adsorption-desorption method, see [reference]. Figure 2 The most probable pore size distribution of the copper-based catalyst, with the most probable pore size of S2 being 31 nm.
[0058] Preparation Example 3
[0059] This preparation example illustrates a copper-based catalyst prepared by co-precipitation using a dual hydrolysis method.
[0060] (1) Prepare a copper nitrate aqueous solution with a concentration of 1.5 mol / L, and prepare mixed solutions of sodium aluminate, sodium carbonate and polyvinyl imidazole with concentrations of 0.5 mol / L, 1 mol / L and 0.1 mol / L respectively. Mix the two solutions at 30°C with stirring, and keep the pH of the system at 9 during the mixing process.
[0061] (2) When the volume of the mixed solution reaches 200 ml, stop mixing and transfer it to a hydrothermal reactor and keep it at 40 °C for 360 min; filter the obtained product, wash it with deionized water, and dry it at 40 °C for 12 h to obtain the copper-based catalyst, labeled as S3.
[0062] XRF characterization showed that the Cu content in this copper-based catalyst was 67.3 wt%.
[0063] XRD characterization, see [link / reference] Figure 1 The characteristic peaks of copper hydroxide at diffraction angles of 16.7° and 63.1° indicate that no impurity copper hydroxide is formed in the S3 structure.
[0064] Determined by N2 adsorption-desorption method, see [reference]. Figure 2 The most probable pore size distribution of the copper-based catalyst, with the most probable pore size of S3 being 26 nm.
[0065] Preparation Example 4
[0066] This preparation example illustrates a copper-based catalyst prepared by co-precipitation using a dual hydrolysis method.
[0067] (1) Prepare a copper nitrate aqueous solution with a concentration of 0.1 mol / L, and prepare mixed solutions of sodium aluminate, sodium carbonate and polyvinyl imidazole with concentrations of 0.25 mol / L, 0.5 mol / L and 0.05 mol / L respectively. Mix the two solutions at 30°C with stirring, and keep the pH of the system at 8 during the mixing process.
[0068] (2) When the volume of the mixed solution reaches 200 ml, stop mixing and transfer it to a hydrothermal reactor and keep it at 40 °C for 120 min; filter the obtained product, wash it with deionized water, and dry it at 40 °C for 12 h to obtain the copper-based catalyst, labeled as S4.
[0069] XRF characterization revealed that the Cu content in this copper-based catalyst was 63.9 wt%.
[0070] XRD characterization, see [link / reference] Figure 1 The characteristic peaks of copper hydroxide at diffraction angles of 16.7° and 63.1° indicate that no impurity copper hydroxide is formed in the S4 structure.
[0071] Determined by N2 adsorption-desorption method, see [reference]. Figure 2 The most probable pore size distribution of the copper-based catalyst, with the most probable pore size of S4 being 25 nm.
[0072] Comparative Preparation Example 1
[0073] Copper catalysts were prepared using a conventional coprecipitation method.
[0074] Prepare a mixed aqueous solution of copper nitrate (0.75 mol / L) and aluminum nitrate (0.25 mol / L), and mixed solutions of sodium hydroxide (1.2 mol / L) and sodium carbonate (0.8 mol / L). Mix the two solutions at 30°C with stirring, maintaining the pH of the system at 10 during the mixing process. When the volume of the mixed solution reaches 200 ml, stop mixing and transfer the solution to a hydrothermal reactor and maintain it at 40°C for 120 min. Filter the obtained product, wash it with deionized water, and dry it at 60°C for 12 h to obtain product D1.
[0075] XRF characterization showed that the catalyst contained 74.3 wt% Cu.
[0076] XRD characterization, see [link / reference] Figure 1 The characteristic peaks of copper hydroxide at diffraction angles of 16.7° and 63.1° indicate the presence of copper hydroxide impurities in the D1 structure.
[0077] Determined by N2 adsorption-desorption method, see [reference]. Figure 2 The most probable pore size distribution of the copper-based catalyst, with the most probable pore size of D1 being 8 nm.
[0078] Comparative Preparation Example 2
[0079] The copper-based catalyst was prepared using the same method as in Preparation Example 1, except that the three mixed bases used in Preparation Example 1 were not employed; that is, the "sodium aluminate solution" in Preparation Example 1 was removed.
[0080] The resulting copper-based catalyst was labeled D2.
[0081] XRF characterization showed that the Cu content in this copper-based catalyst was 81.2 wt%.
[0082] XRD characterization, see [link / reference] Figure 1 The characteristic peaks at diffraction angles of 24.1° and 34.2° indicate that D2 has a basic copper carbonate structure.
[0083] Determined by N2 adsorption-desorption method, see [reference]. Figure 2 The most probable pore size distribution of the copper-based catalyst, with the most probable pore size of D2 being 4 nm.
[0084] Comparative preparation example 3
[0085] The copper-based catalyst was prepared using the same method as in Preparation Example 1, except that the three mixed bases used in Preparation Example 1 were not employed; that is, the "polyvinylimidazole solution" in Preparation Example 1 was removed.
[0086] The resulting copper-based catalyst was labeled D3.
[0087] XRD characterization, see [link / reference] Figure 1 The characteristic peaks of copper hydroxide at diffraction angles of 16.7° and 63.1° indicate that there is no impurity copper hydroxide in the D3 structure.
[0088] XRF characterization revealed that the Cu content in this copper-based catalyst was 78.4 wt%.
[0089] Determined by N2 adsorption-desorption method, see [reference]. Figure 2 The most probable pore size distribution of the copper-based catalyst, with the most probable pore size of D3 being 13 nm.
[0090] Example 1
[0091] This embodiment illustrates the preparation of 1,4-butanediol using the copper-based catalyst S1 prepared in Preparation Example 1.
[0092] The copper-based catalyst S1 prepared in Example 1 was reduced at 300°C under a hydrogen atmosphere for 4 h. Then, 2 g of the reduced copper-based catalyst, 1 g of γ-butyrolactone, and 19 g of dioxane were added to a stainless steel reactor, which was completely sealed. The air inside the reactor was replaced three times with high-purity hydrogen. The reaction was carried out for 4 h at the appropriate reaction temperature and hydrogen pressure, with a stirring rate of 200 rpm, to obtain a product containing 1,4-butanediol. The experimental conditions and results are shown in Table 1. The composition of the liquid after the reaction was analyzed by gas chromatography.
[0093] Example 2
[0094] 1,4-Butanediol was prepared using the same method as in Example 1, except that “copper-based catalyst S1 prepared in Example 1” was replaced with “copper-based catalyst S2 prepared in Example 2”; in addition, the reaction pressure and reaction temperature are listed in Table 1.
[0095] Example 3
[0096] 1,4-Butanediol was prepared using the same method as in Example 1, except that “copper-based catalyst S1 prepared in Example 1” was replaced with “copper-based catalyst S3 prepared in Example 3”; in addition, the reaction pressure and reaction temperature are listed in Table 1.
[0097] Example 4
[0098] 1,4-Butanediol was prepared using the same method as in Example 1, except that “copper-based catalyst S1 prepared in Example 1” was replaced with “copper-based catalyst S4 prepared in Example 4”; in addition, the reaction pressure and reaction temperature are listed in Table 1.
[0099] Comparative Example 1
[0100] 1,4-Butanediol was prepared using the same method as in Example 1, except that “copper-based catalyst S1 prepared in Example 1” was replaced with “copper-based catalyst D1 prepared in Comparative Example 1”; in addition, the reaction pressure and reaction temperature are listed in Table 1.
[0101] Comparative Example 2
[0102] 1,4-Butanediol was prepared using the same method as in Example 1, except that “copper-based catalyst S1 prepared in Example 1” was replaced with “copper-based catalyst D2 prepared in Comparative Example 2”; in addition, the reaction pressure and reaction temperature are listed in Table 1.
[0103] Comparative Example 3
[0104] 1,4-Butanediol was prepared using the same method as in Example 1, except that “copper-based catalyst S1 prepared in Example 1” was replaced with “copper-based catalyst D3 prepared in Comparative Example 3”; in addition, the reaction pressure and reaction temperature are listed in Table 1.
[0105] Table 1
[0106]
[0107] As shown in Table 1, compared with copper catalysts prepared by the traditional co-precipitation method, the plate-like copper-based catalyst of this invention exhibits higher γ-butyrolactone hydrogenation activity and 1,4-butanediol selectivity under the same reaction conditions. This is because the double hydrolysis method can avoid the copper hydroxide impurities generated during catalyst preparation.
[0108] I94624BHY
[0109] The resulting catalyst exhibits more uniform active sites. According to experimental results, the sheet-like copper-based catalyst prepared by the dual hydrolysis method can completely avoid the formation of the byproduct tetrahydrofuran at a reaction temperature of 150℃. In industrial production, this can reduce the need for a tetrahydrofuran distillation tower, lower energy consumption for tetrahydrofuran separation, save on equipment investment and energy consumption, thereby increasing profitability.
[0110] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.
Claims
1. A method for preparing 1,4-butanediol, the method comprising: In the presence of hydrogen, a catalyst, γ-butyrolactone, and an organic solvent are brought into contact to react and a product containing 1,4-butanediol is obtained; characterized in that the catalyst is a copper-based catalyst, the copper-based catalyst contains the active component copper and the dispersant alumina, and the most probable pore size of the copper-based catalyst is 18-40 nm.
2. According to the preparation method of claim 1, the most probable pore size of the copper-based catalyst is 25-35 nm; And / or, based on the total weight of the copper-based catalyst, the copper content is 60-80 wt%, preferably 63-80 wt%.
3. The preparation method according to claim 1 or 2, wherein, The preparation method of the copper-based catalyst includes: (1) A double hydrolysis reaction is carried out by contacting a copper salt solution and a mixed alkaline solution; wherein the mixed alkaline solution contains aluminate, alkali and a high molecular polymer containing nitrogen heterocyclic side groups; (2) The product obtained from step (1) is filtered, washed and dried to obtain a copper-based catalyst.
4. The preparation method according to claim 3, wherein, The copper salt in the copper-containing solution is selected from copper nitrate and / or copper sulfate; And / or, the concentration of the copper salt solution is 0.05-4 mol / L, preferably 0.15-3 mol / L.
5. The preparation method according to claim 3, wherein, The aluminate is sodium aluminate and / or potassium aluminate; And / or, the base is selected from at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, and potassium bicarbonate; And / or, the polymer containing nitrogen-containing heterocyclic side groups is polyvinylimidazole.
6. The preparation method according to claim 5, wherein, In the mixed alkaline solution, the concentration of the aluminate is 0.01-2 mol / L, preferably 0.05-1 mol / L; And / or, the concentration of the alkali is 0.01-4 mol / L, preferably 0.1-2 mol / L; And / or, the concentration of the polymer containing nitrogen-containing heterocyclic side groups is 0.01-0.5 mol / L, preferably 0.01-0.1 mol / L.
7. The preparation method according to claim 3, wherein, In step (1), the reaction conditions include: a reaction temperature of 20-50℃ and a reaction time of 10-360 min; Preferably, in step (1), the reaction conditions include: pH 8-12, preferably 9-11.
8. The preparation method according to claim 1, wherein, The organic solvent includes one or more of dioxane, tetrahydrofuran, and N,N-dimethylformamide, preferably dioxane.
9. The preparation method according to claim 1, wherein, The weight ratio of the copper-based catalyst, γ-butyrolactone, and organic solvent is (1-2):1:(19-99).
10. The preparation method according to claim 1, wherein, The conditions for the reaction of catalyst, γ-butyrolactone and organic solvent include: reaction temperature 100-250℃ and reaction pressure 3-7 MPa. Preferably, the reaction temperature is 150-200℃ and the reaction pressure is 4-5 MPa.