Alloy catalyst Raney Ni and preparation method and application thereof
By using a screen to separate aluminum hydroxide during the activation process of the Raney Nickel catalyst, the alloy catalyst Raney Ni is prepared, which solves the problem of the active sites of the catalyst being blocked and achieves efficient catalytic performance and low-cost production.
Patent Information
- Application Number
- CN202411437446.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-15
- Publication Date
- 2025-01-21
AI Technical Summary
During the activation process, the active site is blocked due to the production of aluminum hydroxide, and the catalytic performance is reduced.
By using a screen to separate the aluminum hydroxide produced during the activation process, the alloy catalyst Raney Ni is prepared, ensuring that more nickel active centers are exposed and improving catalytic activity.
The activity and selectivity of the catalyst are significantly improved, and the hydrogenation reaction of 1,4-butynediol and 1,4-butenediol can be efficiently catalyzed under low pressure conditions, thereby reducing the cost of the production process.
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Abstract
Description
Technical Field
[0001] The invention relates to the technical field of catalytic hydrogenation and is an alloy catalyst Raney Ni and a preparation method and application thereof. Background Art
[0002] 1,4-Butenediol (BED), a colorless, transparent or light yellow liquid, is an important organic chemical raw material with a wide range of uses in the fields of chemical industry, medicine, pesticides, papermaking and engineering plastics. In medicine, BED can be used to synthesize n-propyldioxo seven-membered ring to prepare vitamin B6. At present, my country's vitamin B6 production capacity exceeds 5,000 tons, accounting for more than 50% of the global market, most of which are exported; in pesticides, BED can be used to synthesize the intermediate thiosulfan alcohol of the organochlorine insecticide thiosulfan; in the chemical industry, BED can be used as an electroplating additive to prepare nickel layers with good ductility. Because it has a dicarbonyl structure and unsaturated double bonds, it is also an organic chemical intermediate raw material with great application prospects. It can be used to produce vitamin A, vitamin B6, resins, and is widely used in the textile and paper industries.
[0003] 1,4-Butanediol (BDO), as an important organic chemical and fine chemical raw material, can be used to produce major chemical products such as tetrahydrofuran (THF), γ-butyrolactone (GBL), and N-methylpyrrolidone (NMP). It is widely used in many industries such as medicine, automobiles, building materials, textiles, and chemicals.
[0004] The Reppe process is an important method for the industrial production of 1,4-butenediol (BED) and 1,4-butanediol (BDO). In recent years, due to the growing demand for downstream derivatives of BED and BDO, the Reppe hydrogenation process has attracted widespread attention. Considering the current national conditions of my country, which is "rich in coal and poor in oil", and the vigorous development of the coal chemical industry in the northwest region in recent years, the Reppe process, which uses acetylene and methanol, downstream products of the coal chemical industry, as raw materials, has unique advantages. The method consists of two stages: the acetylation stage and the hydrogenation stage: in the acetylation stage, acetylene and formaldehyde are used as raw materials to generate BYD under the action of a copper catalyst; in the hydrogenation stage, BYD is hydrogenated to generate the intermediate product BED, and BED is further hydrogenated to finally generate the product BDO.
[0005] The core technology of the production process of BYD hydrogenation to BED and BDO is the hydrogenation catalyst. Most of the catalysts used are precious metal catalysts, and the industrial production cost is high, which restricts the development of the downstream industrial chain. In the acetylene aldehyde production process, the Raney-Ni catalyst (Raney nickel catalyst) used to synthesize 1,4-butanediol (including 1,4-butenediol) from 1,4-butynediol at high temperature (130°C to 150°C) and high pressure (20MPa to 30 MPa) has the advantages of high activity, high selectivity, and low cost, and is widely used in hydrogenation-dehydrogenation, rearrangement and isomerization reactions. The Raney-Ni catalyst used has been monopolized by the United States, Germany and other countries. At present, the hydrogenation catalyst is only reported in the form of a small number of patents.
[0006] Raney nickel catalyst is an important heterogeneous catalyst that has shown excellent performance in many hydrogenation reactions. It consists of a porous nickel skeleton and was originally developed by American engineer Murray Raney in 1962 for oil hydrogenation in industrial production. Today, Raney nickel is favored for its high catalytic activity, low cost and good selectivity, and is widely used in various organic synthesis and hydrogenation reactions. Its catalytic activity stems from its unique porous structure, which provides a large number of active sites, thereby improving the catalytic efficiency. In addition, due to the presence of aluminum, Raney nickel catalyst has good stability and can withstand multiple cycles without significantly reducing its activity. However, during the activation process, due to the production of aluminum hydroxide, it adheres to the catalyst surface, which causes some active sites to be blocked, ultimately affecting the catalytic performance of the catalyst. Summary of the invention
[0007] The present invention provides an alloy catalyst Raney Ni and a preparation method and application thereof, which overcome the deficiencies of the above-mentioned prior art and can effectively solve the problem that the active sites on the catalyst surface of the existing Raney nickel catalyst are blocked and the catalytic performance is reduced.
[0008] One of the technical solutions of the present invention is achieved by the following measures: A method for preparing an alloy catalyst Raney Ni, characterized in that it is carried out according to the following method: The first step is to crush the required amount of nickel-aluminum alloy and sieve to obtain nickel-aluminum alloy powder; The second step is to prepare a sodium hydroxide aqueous solution and heat it to obtain an etching solution; The third step is to immerse the screen in the etching solution and place the nickel-aluminum alloy powder on the screen to perform an activation reaction to obtain an alloy catalyst; The fourth step is to wash the alloy catalyst to obtain the alloy catalyst Raney Ni.
[0009] The following is a further optimization and / or improvement of one of the above-mentioned technical solutions: In the first step above, the nickel-aluminum alloy is composed of 45% to 80% nickel and 20% to 55% aluminum, and the crushed nickel-aluminum alloy is sieved with one of the mesh sizes of 8 to 14, 14 to 20, 20 to 40, and 40 to 60.
[0010] In the above second step, the mass fraction of sodium hydroxide in the sodium hydroxide aqueous solution is 0.1% to 3.5%, and the heating temperature is 50° C. to 70° C.
[0011] In the above-mentioned third step, the screen is a metal screen, the mesh size of the metal screen is 60 to 180 mesh, the activation reaction temperature is 50°C to 70°C, and the activation reaction time is 60 minutes to 440 minutes; or / and, in the fourth step, the detergent used during washing is deionized water, and the washing is performed until the pH value of the washing liquid is 6 to 9.
[0012] The second technical solution of the present invention is achieved by the following measures: an alloy catalyst Raney Ni is prepared according to the following method: The first step is to crush the required amount of nickel-aluminum alloy and sieve to obtain nickel-aluminum alloy powder; The second step is to prepare a sodium hydroxide aqueous solution and heat it to obtain an etching solution; The third step is to immerse the screen in the etching solution and place the nickel-aluminum alloy powder on the screen to perform an activation reaction to obtain an alloy catalyst; The fourth step is to wash the alloy catalyst to obtain the alloy catalyst Raney Ni.
[0013] The following is a further optimization and / or improvement of the second technical solution of the above invention: In the first step, the nickel-aluminum alloy is composed of 45% to 80% nickel and 20% to 55% aluminum, and the mesh size of the crushed nickel-aluminum alloy is 8 to 14 mesh, 14 to 20 mesh, 20 to 40 mesh, and 40 to 60 mesh; or / and, in the second step, the mass fraction of sodium hydroxide in the sodium hydroxide aqueous solution is 0.1% to 3.5%, and the heating temperature is 50°C to 70°C; or / and, in the third step, the screen is a metal screen, the mesh size of the metal screen is 60 to 180 mesh, the activation reaction temperature is 50°C to 70°C, and the activation reaction time is 60 minutes to 440 minutes; or / and, in the fourth step, the detergent used for washing is deionized water, and the washing liquid is washed until the pH value is 6 to 9.
[0014] The third technical solution of the present invention is achieved by the following measures: an alloy catalyst Raney Ni is used in the catalytic hydrogenation of 1,4-butynediol in a heterogeneous system, comprising the following steps: S1, adding a required amount of a reaction substrate 1,4-butynediol into a solvent, dissolving it, and obtaining a reaction solution; S2, adding a required amount of alloy catalyst Raney Ni to the reaction solution to carry out a reaction to obtain a crude reaction product; S3, separating the crude reaction product to obtain 1,4-butenediol and 1,4-butanediol respectively.
[0015] The following is a further optimization and / or improvement of the third technical solution of the above invention: In the above step S1, the solvent is ultrapure water, and the mass concentration of the reaction liquid is 6% to 60%; or / and, in step S2, the reaction equipment is a reactor with an agitator, the agitator speed is 300 rpm to 800 rpm, the reaction pressure is 5 MPa to 10 MPa, the reaction temperature is 120°C to 130°C, and the reaction time is 4 hours to 8 hours.
[0016] The fourth technical solution of the present invention is achieved by the following measures: an alloy catalyst Raney Ni is used in catalyzing the hydrogenation of 1,4-butenediol in a heterogeneous system, comprising the following steps: S11, adding a reaction substrate 1,4-butenediol into a solvent to dissolve it and obtain a reaction solution; S12, adding a required amount of alloy catalyst Raney Ni to the reaction solution to carry out a reaction to obtain a crude reaction product; S13, separating the crude reaction product to obtain 1,4-butanediol.
[0017] The following is a further optimization and / or improvement of the fourth technical solution of the above invention: In the above step S11, the solvent is ultrapure water, and the mass concentration of the reaction liquid is 6% to 60%; or / and, in step S12, the reaction equipment is a reactor with an agitator, the agitator speed is 300 rpm to 800 rpm, the reaction pressure is 5 MPa to 10 MPa, the reaction temperature is 120°C to 130°C, and the reaction time is 1 hour to 4 hours.
[0018] The alloy catalyst Raney Ni in the present invention is a porous Raney nickel-based alloy catalyst. During the preparation process, a screen is used to effectively separate the aluminum hydroxide produced during the activation process. The prepared alloy catalyst Raney Ni has high selectivity for the target product and is used in catalyzing the hydrogenation reaction of 1,4-butynediol and 1,4-butenediol in a heterogeneous system. It can efficiently exert a catalytic effect under low pressure conditions of 5MPa to 10MPa. BRIEF DESCRIPTION OF THE DRAWINGS
[0019] Attached Figure 1 This is the activated catalyst mapping diagram of the alloy catalyst Raney Ni prepared in Example 21 of the present invention.
[0020] Attached Figure 2 This is the activated catalyst mapping diagram of the alloy catalyst Raney Ni prepared in Comparative Example 1 of the present invention.
[0021] Attached Figure 3 This is a scanning electron microscope image of the alloy catalyst Raney Ni prepared in Example 16 of the present invention.
[0022] Attached Figure 4 This is a graph showing the performance evaluation of 1,4-butynediol hydrogenation catalyzed by Raney Ni alloy catalysts prepared by different methods.
[0023] Attached Figure 5 This is the evaluation diagram of the hydrogenation of 1,4-butynediol catalyzed by Raney Ni alloy catalysts prepared by different methods over time.
[0024] Attached Figure 6 This is a graph showing the performance evaluation of 1,4-butenediol hydrogenation catalyzed by Raney Ni alloy catalysts prepared by different methods. DETAILED DESCRIPTION
[0025] The present invention is not limited by the following embodiments, and the specific implementation method can be determined according to the technical scheme of the present invention and the actual situation. Unless otherwise specified, the various chemical reagents and chemicals mentioned in the present invention are all known and commonly used chemical reagents and chemicals in the prior art; unless otherwise specified, the percentages in the present invention are all mass percentages; unless otherwise specified, the solutions in the present invention are all aqueous solutions with water as the solvent, for example, hydrochloric acid solution is a hydrochloric acid aqueous solution; the normal temperature and room temperature in the present invention generally refer to a temperature of 15°C to 25°C, and are generally defined as 25°C.
[0026] The present invention will be further described below in conjunction with embodiments: Example 1: A method for preparing the alloy catalyst Raney Ni, characterized in that the method is carried out as follows: The first step is to crush the required amount of nickel-aluminum alloy and sieve to obtain nickel-aluminum alloy powder; The second step is to prepare a sodium hydroxide aqueous solution and heat it to obtain an etching solution; The third step is to immerse the screen in the etching solution and place the nickel-aluminum alloy powder on the screen to perform an activation reaction to obtain an alloy catalyst; The fourth step is to wash the alloy catalyst to obtain the alloy catalyst Raney Ni.
[0027] As needed, a screen is placed in the etching solution. During the activation process of the nickel-aluminum alloy powder, the alloy catalyst is located above the screen, and the aluminum hydroxide flocs produced by the reaction are separated and located below the screen.
[0028] Example 2: As an optimization of the above example, in the first step, the nickel-aluminum alloy is composed of 45% to 80% nickel and 20% to 55% aluminum, and the mesh size of the crushed nickel-aluminum alloy is sieved to be one of 8 to 14 mesh, 14 to 20 mesh, 20 to 40 mesh, and 40 to 60 mesh.
[0029] Embodiment 3: As the optimization of the above embodiment, in the second step, the mass fraction of sodium hydroxide in the sodium hydroxide aqueous solution is 0.1% to 3.5%, and the heating temperature is 50°C to 70°C.
[0030] Embodiment 4: As an optimization of the above embodiment, in the third step, the screen is a metal screen, the mesh size of the metal screen is 60 to 180 meshes, the activation reaction temperature is 50°C to 70°C, and the activation reaction time is 60 minutes to 440 minutes.
[0031] Example 5: As an optimization of the above example, in the fourth step, the detergent used for washing is deionized water, and the washing is performed until the pH value of the washing liquid is 6 to 9.
[0032] Example 6: The alloy catalyst Raney Ni was prepared according to the following method: The first step is to crush the required amount of nickel-aluminum alloy and sieve to obtain nickel-aluminum alloy powder; The second step is to prepare a sodium hydroxide aqueous solution and heat it to obtain an etching solution; The third step is to immerse the screen in the etching solution and place the nickel-aluminum alloy powder on the screen to perform an activation reaction to obtain an alloy catalyst; The fourth step is to wash the alloy catalyst to obtain the alloy catalyst Raney Ni.
[0033] Example 7: Application of the alloy catalyst Raney Ni in catalyzing the hydrogenation of 1,4-butynediol in a heterogeneous system comprises the following steps: S1, adding a required amount of a reaction substrate 1,4-butynediol into a solvent, dissolving it, and obtaining a reaction solution; S2, adding a required amount of alloy catalyst Raney Ni to the reaction solution to carry out a reaction to obtain a crude reaction product; S3, separating the crude reaction product to obtain 1,4-butenediol and 1,4-butanediol respectively.
[0034] Example 8: As an optimization of the above example, in step S1, the solvent is ultrapure water, and the mass concentration of the reaction liquid is 6% to 60%.
[0035] Example 9: As an optimization of the above example, in step S2, the reaction equipment is a reactor with an agitator, the agitator speed is 300 rpm to 800 rpm, the reaction pressure is 5 MPa to 10 MPa, the reaction temperature is 120°C to 130°C, and the reaction time is 4 hours to 8 hours.
[0036] Example 10: Application of the alloy catalyst Raney Ni in catalyzing the hydrogenation of 1,4-butenediol in a heterogeneous system, characterized in that it comprises the following steps: S11, adding a reaction substrate 1,4-butenediol into a solvent to dissolve it and obtain a reaction solution; S12, adding a required amount of alloy catalyst Raney Ni to the reaction solution to carry out a reaction to obtain a crude reaction product; S13, separating the crude reaction product to obtain 1,4-butanediol.
[0037] Example 11: As an optimization of the above example, in step S11, the solvent is ultrapure water, and the mass concentration of the reaction liquid is 6% to 60%.
[0038] Example 12: As an optimization of the above example, in step S12, the reaction equipment is a reactor with an agitator, the agitator speed is 300 rpm to 800 rpm, the reaction pressure is 5 MPa to 10 MPa, the reaction temperature is 120°C to 130°C, and the reaction time is 1 hour to 4 hours.
[0039] According to the needs, in the application of alloy catalyst Raney Ni in catalytic hydrogenation of 1,4-butynediol in a heterogeneous system, after filtering the reaction product, take 5mL and place it in a 25mL volumetric flask, dilute it with anhydrous ethanol to make up the volume, and then use a pipette to take 1µL for chromatographic sampling. Use a micro-injection needle to draw 1uL of sample and inject it into the gas chromatograph to detect the substance content. The equipment used for chromatographic sampling is: SH-Rtx-Wax chromatographic column (30 m×0.25mm×0.25µm), hydrogen flame ionization (FID) detector, among which the gas chromatograph vaporization chamber temperature is 240℃ and the detector temperature is 260℃.
[0040] BYD conversion rate: X = [1-C1 / (C1+C2+C3+C4+C5)] × 100%; BDO selectivity: S = [C2 / (C2+C3+C4+C5)] × 100%; BDO yield: W = X * S.
[0041] In the above formula, C i Represents the mass fraction of component i. Where i=1, 2, 3, 4, 5 represent components BYD, BED, BDO, HTHF, BOL respectively.
[0042] In the application of alloy catalyst Raney Ni in catalytic hydrogenation of 1,4-butenediol in heterogeneous system, after filtering the reaction product, take 5mL and place it in a 25mL volumetric flask, dilute it with anhydrous ethanol to make up the volume, and then use a pipette to take 1µL for chromatographic sampling. Use a micro-injection needle to draw 1uL and inject it into the gas chromatograph to measure the substance content. Use SH-Rtx-Wax chromatographic column (30 m×0.25mm×0.25µm) and hydrogen flame ionization (FID) detector, where the gas chromatograph vaporization chamber temperature is 240℃ and the detector temperature is 260℃.
[0043] BED conversion rate: X = [1-C1 / (C1+C2+C3+C4)] × 100%; BDO yield: S = [C2 / (C2+C3+C4)] × 100%; In the above formula, C i Represents the mass fraction of component i. Where i=1, 2, 3, 4 represent components BED, BDO, HTHF, BOL respectively.
[0044] Example 13: According to the present invention, the alloy catalyst Raney Ni is prepared by the following method: The first step is to weigh 0.6g of 8-14 mesh nickel-aluminum alloy, in which the mass proportions of nickel and aluminum are 45% and 55% respectively; The second step is to weigh 0.1 g of sodium hydroxide and prepare 100 mL of 0.1% NaOH solution, heat it to 50° C., and stir it evenly to obtain an etching solution; The third step is to put a 160-mesh screen into the etching solution and fix it on the reactor; The fourth step is to place the nickel-aluminum alloy powder on a sieve and activate it at a temperature of 50° C. for 440 minutes to obtain an alloy catalyst; The fifth step is to wash with deionized water until the pH value of the washing solution is 7.5, thereby obtaining the alloy catalyst Raney Ni, which is recorded as sample 1.
[0045] Example 14: 0.6 g of 20-40 mesh nickel-aluminum alloy was prepared according to the preparation method of Example 13 to obtain sample 2.
[0046] Example 15: 0.6 g of 40-60 mesh nickel-aluminum alloy was prepared according to the preparation method of Example 13 to obtain sample 3.
[0047] Example 16: The difference from Example 13 is that the mesh size of the nickel-aluminum alloy particles is 40 to 60 mesh, the concentration of the NaOH solution is 3.5%, the activation time is 60 minutes, and sample 4 is obtained according to the preparation method of Example 13.
[0048] Example 17: The difference from Example 13 is that the mesh size of the nickel-aluminum alloy particles is 40 to 60 mesh, the concentration of the NaOH solution is 3.5%, the activation time is 60 minutes, and sample 5 is obtained according to the preparation method of Example 13.
[0049] Example 18: The difference from Example 13 is that no screen is added to the etching solution. Sample 7 is obtained according to the preparation method of Example 13.
[0050] Example 19: The difference from Example 14 is that no screen is added to the etching solution. Sample 7 is obtained according to the preparation method of Example 14.
[0051] Example 20: The difference from Example 15 is that no screen is added to the etching solution. Sample 8 is obtained according to the preparation method of Example 15.
[0052] Example 21: 0.6 g of 14-20 mesh nickel-aluminum alloy was prepared according to the preparation method of Example 13 to obtain sample 9.
[0053] Comparative Example 1: The difference from Example 21 is that no screen is added to the etching solution. Sample 10 is obtained according to the preparation method of Example 21.
[0054] The mapping element analysis test and sample component ICP analysis were performed on samples 9 and 10 respectively, and the activation catalyst mapping diagram of the alloy catalyst Raney Ni was obtained, as shown in FIG. Figure 1 , Figure 2 The ICP test results are shown in Table 2. Figure 1 It can be seen that the Ni element distribution in the RaneyNi catalyst after screen etching accounts for a larger proportion, while the Al element distribution is relatively sparse. Figure 2 It can be seen that the distribution of Ni and Al elements in the RaneyNi catalyst without mesh etching is relatively uniform, which is consistent with the ICP characterization results. This is because the mesh effectively filters out aluminum hydroxide during the etching process, exposing more nickel active centers and significantly improving its catalytic activity; Al reacts with NaOH in the etching solution and dissolves, exposing Ni, thereby improving its catalytic activity.
[0055] Example 22: Application of the alloy catalyst Raney Ni in catalyzing the hydrogenation of 1,4-butynediol in a heterogeneous system is carried out according to the following steps: Step S1, weigh 21 g of 1,4-butynediol, dissolve it in ultrapure water, and disperse it evenly using ultrasound to prepare a 10% reaction solution; Step S2, placing the reaction liquid in a 200mL stainless steel reactor, adding 0.6g of alloy catalyst Raney Ni sample 9 to the reaction liquid; after sealing the reactor, at room temperature, increasing the hydrogen pressure to 1.5MPa, replacing the gas with hydrogen 3 times, and checking the air tightness; after checking the air tightness, adjusting the agitator speed to 300rpm, raising the reactor temperature to 120°C, and introducing hydrogen until the pressure reaches 5MPa; reacting for 4 hours, after the reactor is cooled to room temperature, opening the reactor gas valve, discharging hydrogen until the pressure is 0MPa, and obtaining a mixture of reaction product and catalyst; Step S3, separating the mixture to obtain 1,4-butenediol and 1,4-butanediol respectively, and performing chromatographic sampling. The conversion rate of 1,4-butynediol obtained is 96.25%, the yield of 1,4-butenediol is 75.48%, and the yield of 1,4-butanediol is 7.95%.
[0056] Example 23: The difference from Example 22 is that the concentration of the 1,4-butynediol aqueous solution is 6%, the hydrogen pressure is 7 MPa, the reaction temperature is 130°C, the agitator speed is 800 r / min, the conversion rate of 1,4-butynediol obtained is 100.0%, the yield of 1,4-butenediol is 13.29%, and the yield of 1,4-butanediol is 67.94%.
[0057] Example 24: The difference from Example 22 is that the reaction temperature is 130°C, the agitator speed is 800r / min, the conversion rate of 1,4-butynediol obtained is 100.0%, the yield of 1,4-butenediol is 66.66%, and the yield of 1,4-butanediol is 18.90%.
[0058] Example 25: The difference from Example 22 is that the catalyst used is sample 4, the reaction temperature is 130°C, the agitator speed is 800r / min, the conversion rate of 1,4-butynediol obtained is 100.0%, the yield of 1,4-butenediol is 20.03%, and the yield of 1,4-butanediol is 51.10%.
[0059] Example 26: The difference from Example 22 is that the concentration of the 1,4-butynediol aqueous solution is 60%, the conversion rate of 1,4-butynediol obtained is 14.07%, the yield of 1,4-butenediol is 12.90%, and the yield of 1,4-butanediol is 0.35%.
[0060] Example 27: The difference from Example 22 is that the catalyst used is sample 3, the hydrogen pressure is 10 MPa, the reaction temperature is 130°C, the agitator speed is 800 r / min, the conversion rate of 1,4-butynediol obtained is 100%, the yield of 1,4-butenediol is 1.4%, and the yield of 1,4-butanediol is 87.31%.
[0061] Example 28: Application of the alloy catalyst Raney Ni in catalyzing the hydrogenation of 1,4-butenediol in a heterogeneous system is carried out according to the following steps: Step S11, weighing 21 g of 1,4-butenediol, dissolving it in ultrapure water to prepare a 35% aqueous solution, and uniformly dispersing it by ultrasonication to obtain a reaction solution; Step S12, placing the reaction liquid in a 200 mL stainless steel reactor, adding 0.6 g of alloy catalyst Raney Ni sample 4 to the reaction liquid; adjusting the speed of the stirrer to 800 rpm, raising the temperature of the reactor to 130° C., and introducing hydrogen until the pressure reaches 5 MPa; after reacting for 4 hours, the reactor is cooled to room temperature, opening the gas valve of the reactor, releasing hydrogen until the pressure is 0 MPa, and obtaining a mixed phase of the reaction product and the catalyst; Step S13, separating the mixed phase to obtain 1,4-butanediol, and performing chromatographic sampling. The obtained 1,4-butenediol conversion rate is 99.86%, and the 1,4-butanediol yield is 94.64%.
[0062] Example 29: The difference from Example 28 is that the catalyst used is sample 9, the concentration of the reaction substrate 1,4-butenediol is 10%, the agitator speed is 800 rpm, the reaction temperature is 120°C, the conversion rate of 1,4-butenediol obtained is 97.60%, and the yield of 1,4-butanediol is 89.30%.
[0063] Example 30: The difference from Example 28 is that the catalyst used is sample 9, the concentration of the reaction substrate 1,4-butenediol is 60%, the conversion rate of 1,4-butenediol obtained is 86.20%, and the yield of 1,4-butanediol is 76.70%.
[0064] Example 31: The difference from Example 28 is that the hydrogen pressure is 7 MPa, the conversion rate of 1,4-butene diol obtained is 100.0%, and the yield of 1,4-butanediol is 94.90%.
[0065] Example 32: The difference from Example 28 is that the reaction time is 1 hour, the conversion rate of 1,4-butenediol obtained is 51.70%, and the yield of 1,4-butanediol is 43.00%.
[0066] Example 33: The difference from Example 28 is that the catalyst used is sample 5, the hydrogen pressure is 10 MPa, the conversion rate of 1,4-butene diol obtained is 100%, and the yield of 1,4-butanediol is 99.88%.
[0067] Example 34: 0.6 g of sample 9 was placed in a reactor, and the concentration of the reaction substrate 1,4-butynediol was prepared to be 35%. The reaction was carried out according to the steps of Example 22. The conversion rate of 1,4-butynediol was 28.83%, the yield of 1,4-butenediol was 26.11%, and the yield of 1,4-butanediol was 0.49%.
[0068] Comparative Example 2: The difference from Example 34 is that the catalytic reaction time of 1,4-butynediol is 5 hours, the conversion rate of 1,4-butynediol obtained is 29.39%, the yield of 1,4-butenediol is 26.91%, and the yield of 1,4-butanediol is 0.48%.
[0069] Comparative Example 3: The difference from Example 34 is that the catalytic reaction time of 1,4-butynediol is 6 hours, the conversion rate of 1,4-butynediol obtained is 37.09%, the yield of 1,4-butenediol is 33.66%, and the yield of 1,4-butanediol is 0.52%.
[0070] Comparative Example 4: The difference from Example 34 is that the catalytic reaction time of 1,4-butynediol is 7 hours, the conversion rate of 1,4-butynediol obtained is 42.47%, the yield of 1,4-butenediol is 38.38%, and the yield of 1,4-butanediol is 0.53%.
[0071] Comparative Example 5: The difference from Example 34 is that the catalytic reaction time of 1,4-butynediol is 8 hours, the conversion rate of 1,4-butynediol obtained is 46.19%, the yield of 1,4-butenediol is 41.90%, and the yield of 1,4-butanediol is 0.59%.
[0072] Comparative Example 6: The difference from Example 34 is that the catalyst used is Sample 1, the conversion rate of 1,4-butynediol obtained is 32.58%, the yield of 1,4-butenediol is 28.95%, and the yield of 1,4-butanediol is 1.05%.
[0073] Comparative Example 7: The difference from Example 34 is that the catalyst used is Sample 2, the conversion rate of 1,4-butynediol obtained is 24.60%, the yield of 1,4-butenediol is 22.35%, and the yield of 1,4-butanediol is 0.50%.
[0074] Comparative Example 8: The difference from Example 34 is that the catalyst used is Sample 3, the conversion rate of 1,4-butynediol obtained is 20.69%, the yield of 1,4-butenediol is 19.2%, and the yield of 1,4-butanediol is 0.13%.
[0075] Comparative Example 9: The difference from Example 34 is that the catalyst used is Sample 6, the conversion rate of 1,4-butynediol obtained is 29.02%, the yield of 1,4-butenediol is 26.15%, and the yield of 1,4-butanediol is 0.55%.
[0076] Comparative Example 10: The difference from Example 34 is that the catalyst used is sample 10, the conversion rate of 1,4-butynediol obtained is 27.33%, the yield of 1,4-butenediol is 24.78%, and the yield of 1,4-butanediol is 0.49%.
[0077] Comparative Example 11: The difference from Example 34 is that the catalyst used is Sample 7, the conversion rate of 1,4-butynediol obtained is 22.55%, the yield of 1,4-butenediol is 20.39%, and the yield of 1,4-butanediol is 0.48%.
[0078] Comparative Example 12: The difference from Example 34 is that the catalyst used is Sample 8, the conversion rate of 1,4-butynediol obtained is 19.83%, the yield of 1,4-butenediol is 18%, and the yield of 1,4-butanediol is 0.44%.
[0079] Example 34 and Comparative Examples 2 to 5 are the effects of different reaction times on the hydrogenation performance of BYD. The performance and parameters of the products were obtained by testing. The test results are shown in Table 2. The performance evaluation of the alloy catalyst Raney Ni prepared by different methods for catalyzing the hydrogenation of 1,4-butynediol is shown in Table 2. Figure 4 As shown in Table 2 and Figure 4 It can be seen that the reaction time has a great influence on the hydrogenation performance of BYD, and BED has a high selectivity. Increasing the reaction time can significantly improve the conversion rate of BYD.
[0080] Example 34 and Comparative Examples 6 to 12 are, in the hydrogenation reaction of 1,4-butynediol, under the same reaction conditions (hydrogen pressure 5MPa, reaction temperature 120°C, reaction time 4 hours, stirrer speed 300r / min, catalyst 0.6g (0.1wt.% sodium hydroxide), 1,4-butynediol aqueous solution concentration 35%), when the alloy catalyst Raney Ni is prepared, whether the mesh is added for activation, the effect on the hydrogenation reaction of 1,4-butynediol, the performance and parameters of the product are detected, and the test results are shown in Table 3. The evaluation graph of the hydrogenation of 1,4-butynediol catalyzed by the alloy catalyst Raney Ni with different preparation methods over time is as shown in Figure 5 As shown in Table 3 and Figure 5 It can be seen that whether to add a screen has a great influence on the activity of the alloy catalyst. Adding a screen can significantly improve the activity of the catalyst and the conversion rate of BYD.
[0081] Example 35: 0.6 g of sample 9 was placed in a reactor, and the concentration of the reaction substrate 1,4-butenediol was prepared to be 35%. The reaction was carried out according to the steps of Example 29. The conversion rate of 1,4-butenediol was 31.27%, and the yield of 1,4-butanediol was 23.89%.
[0082] Comparative Example 13: The difference from Example 35 is that the catalyst used is Sample 1, the conversion rate of 1,4-butene diol obtained is 34.46%, and the yield of 1,4-butanediol is 25.37%.
[0083] Comparative Example 14: The difference from Example 35 is that the catalyst used is Sample 2, the conversion rate of 1,4-butene diol obtained is 29.36%, and the yield of 1,4-butanediol is 22.60%.
[0084] Comparative Example 15: The difference from Example 35 is that the catalyst used is Sample 3, the conversion rate of 1,4-butene diol obtained is 28.93%, and the yield of 1,4-butanediol is 19.73%.
[0085] Comparative Example 16: The difference from Example 35 is that the catalyst used is Sample 6, the conversion rate of 1,4-butene diol obtained is 24.40%, and the yield of 1,4-butanediol is 19.69%.
[0086] Comparative Example 17: The difference from Example 35 is that the catalyst used is sample 10, the conversion rate of 1,4-butene diol obtained is 26.62%, and the yield of 1,4-butanediol is 20.92%.
[0087] Comparative Example 18: The difference from Example 35 is that the catalyst used is Sample 7, the conversion rate of 1,4-butene diol obtained is 23.05%, and the yield of 1,4-butanediol is 18.69%.
[0088] Comparative Example 19: The difference from Example 35 is that the catalyst used is Sample 8, the conversion rate of 1,4-butenediol obtained is 20.60%, and the yield of 1,4-butenediol is 15.34%.
[0089] Example 35 and Comparative Examples 13 to 19 are, in the hydrogenation reaction of 1,4-butenediol, under the same reaction conditions (hydrogen pressure 5MPa, reaction temperature 120°C, reaction time 4 hours, stirrer speed 300r / min, catalyst 0.6g (0.1wt.% sodium hydroxide), 1,4-butynediol aqueous solution concentration 35%), whether the alloy catalyst Raney Ni is activated with a screen during preparation, the effect on the hydrogenation reaction of 1,4-butenediol, the performance and parameters of the products obtained are tested, and the test results are shown in Table 4. The performance evaluation diagram of 1,4-butenediol hydrogenation catalyzed by the alloy catalyst Raney Ni prepared by different methods is shown in Table 4. Figure 6 As shown in Table 4 and Figure 6 It can be seen that whether to add a screen has a great influence on the activity of the alloy catalyst. Adding a screen can significantly improve the activity of the catalyst and the conversion rate of BED.
[0090] In summary, based on the original method for activating the Raney nickel catalyst, the present invention creatively uses a screen to effectively separate the aluminum hydroxide produced during the activation process. The preparation method is simple, the raw materials are easily available, the cost is low, the target product has high selectivity, is easy to separate, has excellent catalytic performance, and can effectively improve the conversion rate of the raw materials and the yield of the product under low pressure conditions of 5MPa to 10MPa, thereby reducing the production process cost and having broad industrial prospects.
[0091] The above technical features respectively constitute various embodiments of the present invention, which have strong adaptability and implementation effect. Non-essential technical features can be added or reduced according to actual needs to meet the requirements of different situations.
Claims
1. A method for preparing an alloy catalyst Raney Ni, characterized in that Proceed as follows: The first step is to crush the required amount of nickel-aluminum alloy and sieve to obtain nickel-aluminum alloy powder; The second step is to prepare a sodium hydroxide aqueous solution and heat it to obtain an etching solution; The third step is to immerse the screen in the etching solution and place the nickel-aluminum alloy powder on the screen to perform an activation reaction to obtain an alloy catalyst; The fourth step is to wash the alloy catalyst to obtain the alloy catalyst Raney Ni.
2. The method for preparing the alloy catalyst Raney Ni according to claim 1, characterized in that In the first step, the nickel-aluminum alloy is composed of 45% to 80% nickel and 20% to 55% aluminum, and the crushed nickel-aluminum alloy is sieved with one of the mesh sizes of 8 to 14, 14 to 20, 20 to 40, and 40 to 60.
3. The method for preparing the alloy catalyst Raney Ni according to claim 1 or 2, characterized in that In the second step, the mass fraction of sodium hydroxide in the sodium hydroxide aqueous solution is 0.1% to 3.5%, and the heating temperature is 50° C. to 70° C.
4. The method for preparing the alloy catalyst Raney Ni according to claim 1, 2 or 3, characterized in that In the third step, the screen is a metal screen with a mesh size of 60 to 180, the activation reaction temperature is 50°C to 70°C, and the activation reaction time is 60 minutes to 440 minutes; or / and, in the fourth step, the detergent used for washing is deionized water, and the washing is performed until the pH value of the washing liquid is 6 to 9.
5. An alloy catalyst Raney Ni obtained by the preparation method of the alloy catalyst Raney Ni according to any one of claims 1 to 4, characterized in that Prepared according to the following method: The first step is to crush the required amount of nickel-aluminum alloy and sieve to obtain nickel-aluminum alloy powder; The second step is to prepare a sodium hydroxide aqueous solution and heat it to obtain an etching solution; The third step is to immerse the screen in the etching solution and place the nickel-aluminum alloy powder on the screen to perform an activation reaction to obtain an alloy catalyst; The fourth step is to wash the alloy catalyst to obtain the alloy catalyst Raney Ni.
6. The alloy catalyst RaneyNi obtained by the preparation method of the alloy catalyst RaneyNi according to claim 5, characterized in that In the first step, the nickel-aluminum alloy is composed of 45% to 80% nickel and 20% to 55% aluminum, and the mesh number of the crushed nickel-aluminum alloy is 8 to 14 mesh, 14 to 20 mesh, 20 to 40 mesh, and 40 to 60 mesh; or / and, in the second step, the mass fraction of sodium hydroxide in the sodium hydroxide aqueous solution is 0.1% to 3.5%, and the heating temperature is 50°C to 70°C; or / and, in the third step, the screen is a metal screen, the mesh number of the metal screen is 60 to 180 mesh, the activation reaction temperature is 50°C to 70°C, and the activation reaction time is 60 minutes to 440 minutes; or / and, in the fourth step, the detergent used in washing is deionized water, and the washing is performed until the pH value of the washing liquid is 6 to 9.
7. A use of the alloy catalyst Raney Ni according to claim 6 in catalyzing the hydrogenation of 1,4-butynediol in a heterogeneous system, characterized in that The steps include: S1, adding a required amount of a reaction substrate 1,4-butynediol into a solvent, dissolving it, and obtaining a reaction solution; S2, adding a required amount of alloy catalyst Raney Ni to the reaction solution to carry out a reaction to obtain a crude reaction product; S3, separating the crude reaction product to obtain 1,4-butenediol and 1,4-butanediol respectively.
8. Use of the alloy catalyst Raney Ni according to claim 7 in catalyzing the hydrogenation of 1,4-butynediol in a heterogeneous system, characterized in that In step S1, the solvent is ultrapure water, and the mass concentration of the reaction liquid is 6% to 60%; or / and, in step S2, the reaction equipment is a reactor with an agitator, the agitator speed is 300 rpm to 800 rpm, the reaction pressure is 5 MPa to 10 MPa, the reaction temperature is 120°C to 130°C, and the reaction time is 4 hours to 8 hours.
9. An application of the alloy catalyst Raney Ni according to claim 6 in catalyzing the hydrogenation of 1,4-butenediol in a heterogeneous system, characterized in that The steps include: S11, adding a reaction substrate 1,4-butenediol into a solvent to dissolve it and obtain a reaction solution; S12, adding a required amount of alloy catalyst Raney Ni to the reaction solution to carry out a reaction to obtain a crude reaction product; S13, separating the crude reaction product to obtain 1,4-butanediol.
10. Use of the alloy catalyst Raney Ni according to claim 9 in catalyzing the hydrogenation of 1,4-butenediol in a heterogeneous system, characterized in that In step S11, the solvent is ultrapure water, and the mass concentration of the reaction liquid is 6% to 60%; or / and, in step S12, the reaction equipment is a reactor with an agitator, the agitator speed is 300 rpm to 800 rpm, the reaction pressure is 5 MPa to 10 MPa, the reaction temperature is 120°C to 130°C, and the reaction time is 1 hour to 4 hours.