Hydrogenation catalyst for aldehyde-terminated polyvinyl ether
By adjusting the types of organosilanes and organic acids in the support treatment, a semi-porous structure hydrogenation catalyst was prepared, which solved the problems of short duration and slow volume of existing catalysts, and achieved higher liquid-time space-speed and yield.
Patent Information
- Application Number
- CN202510341995.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-21
- Publication Date
- 2025-06-13
AI Technical Summary
The existing catalysts have a short duration and a slow volume space rate during the hydrogenation catalysis process, resulting in unsatisfactory yield and selectivity of terminal acetal-based polyvinyl ethers.
By adjusting the type of organosilane in the support silanization treatment and the type of organic acid during the support impregnation process, a hydrogenation catalyst with a mutually supported semi-porous structure was prepared. The use of this catalyst in a fixed bed reactor can increase liquid time-time space velocity while maintaining high conversion and selectivity.
The hydrogenation catalyst has been achieved for a longer duration, an increased volume space speed, and high conversion and selectivity are maintained in the fixed bed reactor, which improves the yield of terminal acetal-based polyethylene ether.
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Figure CN120132919A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of catalytic hydrogenation, and particularly relates to a hydrogenation catalyst for terminal acetal group polyethylene ether. Background Art
[0002] Terminal ether group polyethylene ether is usually prepared by catalytic hydrogenation of terminal acetal group polyethylene ether. Common hydrogenation catalysts are metal oxides such as silica, titanium oxide, alumina, and magnesia loaded with metals such as nickel and platinum. The yield of terminal ether group polyethylene ether calculated by conventional conversion rate and selectivity is about 80%. However, the current catalysts have problems of short duration and too slow volume space velocity in the actual production process.
[0003] Therefore, a hydrogenation catalyst for terminal acetal group polyethylene ether is proposed, so that the hydrogenation catalyst has a longer duration and can further increase the liquid hourly space velocity during the hydrogenation catalysis process. Summary of the Invention
[0004] The present invention aims to solve at least one of the technical problems existing in the above prior art. For this purpose, the present invention provides a hydrogenation catalyst for terminal acetal group polyethylene ether, so that the hydrogenation catalyst has a longer duration during the hydrogenation catalysis process and can further increase the liquid hourly space velocity (LHSV) of the fixed reaction bed.
[0005] The inventive concept of the present invention is: by adjusting the type of organosilane in the carrier silanization treatment and the type of organic acid in the carrier impregnation process, the calcined hydrogenation catalyst presents a mutually supported semi-porous structure, so that high conversion rate and selectivity can be maintained on the premise of increasing the liquid hourly space velocity during the catalytic hydrogenation stage in the fixed bed reactor.
[0006] The first aspect of the present invention provides a hydrogenation catalyst for terminal acetal group polyethylene ether.
[0007] Specifically, a hydrogenation catalyst for terminal acetal group polyethylene ether, the preparation steps of the hydrogenation catalyst include: (1) Phenolic resin is treated with an aqueous solution of organosilane, and then diluted, stirred, and subjected to hydrothermal reaction to obtain a carrier; (2) The carrier is impregnated with an aqueous solution of nickel organic acid, dried, and then calcined in a nitrogen atmosphere to obtain the hydrogenation catalyst.
[0008] Compared with the prior art, the beneficial effects of the hydrogenation catalyst for terminal acetal group polyethylene ether provided by this first aspect are as follows: the hydrogenation catalyst presents a mutually supported semi-porous structure, so that high conversion rate and selectivity can be maintained on the premise of increasing the liquid hourly space velocity during the catalytic hydrogenation stage in the fixed bed reactor.
[0009] Preferably, the preparation steps of the phenolic resin include reacting sodium phenoxide with formaldehyde at 70 - 90 °C for 25 - 35 min.
[0010] Preferably, the preparation steps of the phenolic resin include adding 1.5 - 2 g of phenol to 40 - 50 mL of 0.1 mL sodium hydroxide solution at 50 - 60 °C and stirring for 10 - 15 min to obtain the sodium phenoxide, then adding 5 - 7 mL of 35 - 40 wt% formaldehyde solution and reacting at 75 - 85 °C for 25 - 35 min to obtain the phenolic resin.
[0011] Preferably, the aqueous solution of organosilane includes an aqueous solution of trimethylsilane.
[0012] Preferably, the steps of treating with the aqueous solution of organosilane include adding 125 - 175 mL of the aqueous solution of organosilane to the phenolic resin and stirring at 55 - 65 °C for 10 - 14 h.
[0013] Preferably, in the step (1), the dilution step includes diluting with water at a ratio of 1:3.5 - 4.5.
[0014] Preferably, in the step (1), the conditions of the hydrothermal reaction include reacting at 120 - 140 °C for 10 - 14 h.
[0015] Preferably, in the step (1), the support further includes a post - treatment step, and the post - treatment step includes centrifugation, suction filtration, washing, and drying.
[0016] Preferably, in the step (2), the calcination temperature is 425 - 475 °C and the calcination time is 2.5 - 3.5 h.
[0017] Preferably, in the step (2), the nickel organic acid includes nickel acetate.
[0018] Preferably, in the step (2), the concentration of the nickel organic acid is 0.10 - 0.20 g / mL.
[0019] Compared with the prior art, the beneficial effects of the present invention are as follows: The hydrogenation catalyst presents a mutually supported semi - porous structure, enabling high conversion and selectivity to be maintained under the premise of increasing the liquid hourly space velocity during the catalytic hydrogenation stage in a fixed - bed reactor. BRIEF DESCRIPTION OF THE DRAWINGS
[0020] Figure 1 It is a scanning electron micrograph of the hydrogenation catalyst of the terminal - acetal - group - containing polyvinyl ether prepared in Example 1. DETAILED DESCRIPTION OF THE EMBODIMENTS
[0021] To make the technical solutions of the present invention clearer and more understandable to those skilled in the art, the following embodiments are listed for illustration. It should be noted that the following embodiments do not limit the scope of protection required by the present invention.
[0022] Unless otherwise specified, the raw materials, reagents or devices used in the following embodiments can be obtained from conventional commercial channels or can be obtained by existing known methods.
[0023] The catalysts of the embodiments of the present invention and the solvents equipped with the present invention can be prepared in multiple batches to reach the usage amount required for subsequent use.
[0024] Preparation steps of trimethylsilane aqueous solution: 1.4 g of trimethylsilane is dissolved in 1 L of deionized water at 30°C.
[0025] Preparation steps of nickel acetate aqueous solution: 1.5 g of nickel acetate is dissolved in 10 mL of deionized water at 30°C.
[0026] Preparation steps of terminal acetal group polyvinyl ether: Add 250 mL of n-hexane, 40 mL of ethanol, 40 mL of boron trifluoride diethyl ether to a reaction kettle equipped with a dropping funnel, an ice bath, and a magnetic stirrer. While maintaining the reaction system at 25 ± 1°C in the ice bath, dropwise add 500 mL of vinyl ether to start the polymerization reaction. After the addition is completed, continue to maintain the reaction system at 25 ± 1°C and continue the reaction for 30 min. After the reaction is completed, it is obtained by alkali washing, water washing, and vacuum distillation to obtain terminal acetal group polyvinyl ether.
[0027] Hydrogenation catalysis of terminal acetal group polyvinyl ether to terminal ether group polyvinyl ether to detect the performance of the hydrogenation catalyst of the prepared terminal acetal group polyvinyl ether: Load an equal volume (100 mL) of hydrogenation catalyst into a fixed-bed reactor. Introduce a mixed solution of terminal acetal group polyvinyl ether and n-hexane with a dilution ratio of 1:4 and hydrogen (hydrogen-oil ratio of 1:500) into the fixed-bed reactor. Set the liquid hourly space velocity LHSV, reaction temperature, record the hydrogen partial pressure, and test and record the conversion rate and selectivity. Example 1
[0028] The preparation steps of the hydrogenation catalyst of terminal acetal group polyvinyl ether are as follows: (1) Add 1.8 g of phenol to 45 ml of 0.1 mol / L sodium hydroxide solution at 50°C, stir for 10 - 15 minutes, add 6.2 ml of 37% formaldehyde solution, and react at 80°C for 30 minutes to obtain sodium phenoxide; cool down to 60°C, stir for three hours, add 150 ml of trimethylsilane aqueous solution, stir for 12 hours, terminate the reaction, and naturally cool to room temperature to obtain a reaction solution; dilute every 35 ml of the reaction solution with 105 ml of deionized water, add it to a hydrothermal kettle, hydrothermal at 130°C for 36 h, naturally cool to room temperature, centrifuge, filter, wash, and dry at 100°C for 12 hours to obtain a support; (2) The carrier was impregnated with an equal volume of an aqueous nickel acetate solution until all the liquid had evaporated completely, and then dried in a vacuum oven at 100 °C for 4 hours; it was calcined in a tubular furnace at 450 °C for 3 h under a nitrogen atmosphere to obtain a hydrogenation catalyst for terminal acetal polyethylene ether.
[0029] Figure 1 It is the scanning electron micrograph of the hydrogenation catalyst for terminal acetal polyethylene ether prepared in Example 1; it can be seen that the surface of the prepared hydrogenation catalyst has an obvious semi-porous structure. The hydrogenation catalyst presents a semi-porous structure with mutual support, enabling high conversion and selectivity to be maintained under the premise of increasing the liquid hourly space velocity during the catalytic hydrogenation stage in a fixed-bed reactor.
[0030] The performance of the prepared hydrogenation catalyst (hydrogenation catalysis of terminal acetal polyethylene ether to terminal ether polyethylene ether) was tested, and the liquid hourly space velocity, reaction temperature, hydrogen partial pressure, conversion rate and selectivity were recorded in Table 1.
[0031] Examples 2 and 3 The hydrogenation catalysts for terminal acetal polyethylene ether in Examples 2 and 3 were the same as that in Example 1, except that the liquid hourly space velocity and reaction temperature were different when testing the performance of the hydrogenation catalyst. The detailed parameters and results were recorded in Table 1.
[0032] Comparative Example 1 The difference between Comparative Example 1 and Example 1 was that nickel acetate in the preparation step (2) was replaced with nickel nitrate of the same molar concentration, and the rest of the preparation methods were the same.
[0033] The performance of the prepared hydrogenation catalyst (hydrogenation catalysis of terminal acetal polyethylene ether to terminal ether polyethylene ether) was tested, and the liquid hourly space velocity, reaction temperature, hydrogen partial pressure, conversion rate and selectivity were recorded in Table 1.
[0034] Comparative Examples 2 and 3 The hydrogenation catalysts for terminal acetal polyethylene ether in Comparative Examples 2 and 3 were the same as that in Comparative Example 1, except that the liquid hourly space velocity and reaction temperature were different when testing the performance of the hydrogenation catalyst. The detailed parameters and results were recorded in Table 1.
[0035] Comparative Example 4 The preparation steps of the hydrogenation catalyst for terminal acetal polyethylene ether are as follows: (1) 2.22 g of high-purity nano-alumina powder (γ phase, particle size 10 - 20 nm) was added to 150 ml of an aqueous trimethylsilane solution, and stirred at 60 °C for 12 hours, and then naturally cooled to room temperature to obtain a reaction solution; every 35 ml of the reaction solution was diluted with 105 ml of deionized water, added to a hydrothermal autoclave, and hydrothermally treated at 130 °C for 36 h, and then naturally cooled to room temperature, centrifuged, filtered, washed, and dried at 100 °C for 12 hours to obtain a carrier; (2) The carrier was impregnated with an equal volume of nickel acetate aqueous solution until all the liquid evaporated completely, and then dried in a vacuum oven at 100 °C for 4 hours; it was calcined in a tubular furnace at 450 °C for 3 h under a nitrogen atmosphere to obtain a hydrogenation catalyst for the hydrogenation of terminal acetal group polyethylene ether.
[0036] The performance of the prepared hydrogenation catalyst (hydrogenation of terminal acetal group polyethylene ether to prepare terminal ether group polyethylene ether) was tested, and the liquid hourly space velocity, reaction temperature, hydrogen partial pressure, conversion rate and selectivity were recorded in Table 1.
[0037] Comparative Examples 5 and 6 The hydrogenation catalysts for terminal acetal group polyethylene ether in Comparative Examples 5 and 6 were the same as those in Comparative Example 4, except that the liquid hourly space velocity and reaction temperature were different when testing the performance of the hydrogenation catalyst. The detailed parameters and results were recorded in Table 1.
[0038] Table 1 Liquid hourly space velocity, reaction temperature, hydrogen partial pressure, conversion rate and selectivity of Examples 1-3 and Comparative Examples 1-6 <![CDATA[Liquid hourly space velocity (h -1 ).]]> Reaction temperature (°C) Hydrogen partial pressure (MPa) Conversion rate (%) Selectivity (%) Example 1 1 120 3.8 93 94 Example 2 0.8 120 3.8 96 95 Example 3 1 160 3.8 95 92 Comparative Example 1 1 120 3.8 78 90 Comparative Example 2 0.8 120 3.8 84 91 Comparative Example 3 1 160 3.8 94 93 Comparative Example 4 1 120 3.8 69 83 Comparative Example 5 0.8 120 3.8 76 84 Comparative Example 6 1 160 3.8 85 79 The yield of Example 1 was conversion rate × selectivity = 93% × 94% = 87.42%.
Claims
1. A hydrogenation catalyst for terminal acetal polyethylene ether, characterized in that The preparation steps of the hydrogenation catalyst include: (1) The phenolic resin is treated with an organic silane aqueous solution, and then diluted, stirred, and subjected to a hydrothermal reaction to obtain a carrier; (2) The carrier is impregnated with an aqueous solution of organic acid nickel, dried, and then calcined under a nitrogen atmosphere to obtain the hydrogenation catalyst.
2. The preparation method according to claim 1, characterized in that: The preparation step of the phenolic resin comprises reacting sodium phenolate with formaldehyde at 70-90° C. for 25-35 minutes.
3. The preparation method according to claim 2, characterized in that: The preparation steps of the phenolic resin include adding 1.5-2g of phenol to 40-50mL of 0.1mL sodium hydroxide solution at a temperature of 50-60°C and stirring for 10-15min to obtain the sodium phenolate, then adding 5-7mL of 35-40wt% formaldehyde solution, and reacting at 75-85°C for 25-35min to obtain the phenolic resin.
4. The preparation method according to claim 1, characterized in that: The organic silane aqueous solution includes a trimethylsilane aqueous solution.
5. The preparation method according to claim 1, characterized in that: The step of treating the organosilane aqueous solution comprises adding 125-175 mL of the organosilane aqueous solution to the phenolic resin and stirring at 55-65° C. for 10-14 hours.
6. The preparation method according to claim 1, characterized in that: In the step (1), the hydrothermal reaction conditions include 120-140° C. for 10-14 hours.
7. The preparation method according to claim 1, characterized in that: In the step (1), the carrier further comprises a post-processing step, and the post-processing step comprises centrifugation, filtration, washing, and drying.
8. The preparation method according to claim 1, characterized in that: In the step (2), the calcination temperature is 425-475° C. and the calcination time is 2.5-3.5 hours.
9. The preparation method according to claim 1, characterized in that: In the step (2), the organic acid nickel includes nickel acetate.
10. The preparation method according to claim 1, characterized in that: In the step (2), the organic acid nickel concentration of the organic acid nickel aqueous solution is 0.10-0.20 g / mL.