A hydrogenated rosin catalyst and its preparation method and application
By dispersing palladium ions in the hydrotalcite support and combining the molar ratio of nickel and magnesium to 1:1, Pd/NiMg-HT catalyst was prepared, which solved the problem that traditional palladium carbon catalysts needed high temperature and high pressure conditions in the hydrogenation of rosin reaction, and achieved efficient catalytic hydrogenation of rosin under low conditions, reducing production costs and improving catalytic efficiency.
Patent Information
- Application Number
- CN202411992710.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-31
- Publication Date
- 2025-04-08
AI Technical Summary
Traditional palladium carbon catalysts require high temperature and high pressure conditions in hydrogenation rosin reaction, resulting in high production costs and complex production preparation, and expensive catalysts.
A new hydrogenated rosin catalyst was prepared by dispersing palladium ions in the form of nanoparticles in the hydrotalcite support, combining the molar ratio of nickel and magnesium to 1:1. The preparation method of the catalyst includes four steps: mixing, preparing, calcining and reducing, and the cost is reduced through a simple process.
It is achieved efficient catalyzing the hydrogenation of rosin under lower temperature and pressure conditions, reducing production costs, and the stability and catalytic efficiency of the catalyst are high, with a rosin conversion rate of 96.46% and a selectivity of hydrogenated rosin reaching 78.06%.
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Figure CN119771442A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the preparation and application of a natural product catalyst, and in particular to a hydrogenated rosin catalyst and a preparation method and application thereof. Background Art
[0002] Rosin comes from rosin, which is a resin secreted by pine trees and is known as "oil growing on trees". From the perspective of chemical composition, rosin is mainly a mixture of rosin resin acid and terpene components of turpentine oil. Rosin and turpentine oil can be obtained by steam distillation. Both are important chemical raw materials. The main component of rosin is abietic resin acid. The instability of rosin to oxygen and its corresponding yellowing tendency are mainly related to the conjugated double bond system of abietic resin acid. Its oxygen absorption can reach 10% of the weight of rosin, thereby deepening the color of rosin and reducing its quality. The use of catalytic hydrogenation can greatly improve its quality. Hydrogenated rosin mainly contains dihydroabietic acid and tetrahydroabietic acid. Hydrogenated rosin is widely used in adhesives, flux, coatings, inks, papermaking, electronics, food and other industrial sectors.
[0003] Due to the high viscosity of rosin, traditional palladium-carbon catalysts require harsh conditions of 260-280°C and 10-35MPa to react, which makes the hydrogenation cost high. In addition, palladium-carbon catalysts are complex to prepare and expensive, so improved catalysts have become a market consensus. Summary of the invention
[0004] In order to solve the above technical problems, the present invention provides a hydrogenated rosin catalyst and its preparation method and application, aiming to obtain a Pd / NiMg-HT catalyst which is simple to prepare, low in cost, good in stability and can be used for hydrogenated rosin reaction. The traditional palladium carbon (Pd / C) catalyst preparation technology is improved, the production cost of preparing hydrogenated rosin by catalytic rosin hydrogenation is reduced, and the reaction conditions are optimized.
[0005] To achieve the above purpose, the technical solution provided by the present invention is as follows:
[0006] A hydrogenated rosin catalyst has a molecular formula of Pd / NiMg-HT, wherein the active component palladium ions (Pd) are dispersed in a hydrotalcite carrier in the form of nanoparticles, wherein the mass loading of the palladium ions is 0.2-0.5wt.%, and the molar ratio of nickel ions to magnesium ions is 1:1.
[0007] Preferably, the palladium ion mass loading is 0.2 wt.%.
[0008] The preparation method of the hydrogenated rosin catalyst as described above comprises titrating a mixed nickel magnesium palladium nitrate solution and a sodium hydroxide solution into a constant temperature water bath, stirring for a period of time, aging and cooling, filtering to reduce the pH, drying, roasting and reducing to obtain a Pd / NiMg-HT catalyst, comprising the following steps:
[0009] (1) Mixing: dissolving nickel nitrate hexahydrate, palladium nitrate dihydrate and magnesium nitrate hexahydrate in deionized water to obtain a mixed nitrate solution, and preparing a sodium hydroxide aqueous solution and a sodium carbonate aqueous solution at the same time; (2) Preparation: heating the sodium carbonate aqueous solution obtained in step (1) to 70° C. in a water bath, titrating the mixed nitrate solution with the sodium hydroxide aqueous solution simultaneously, controlling the pH value in the process to be between 10 and 11, stirring vigorously during titration, reacting at 70° C. for 3 hours, then turning off the stirring and aging for 3 hours, cooling to room temperature, then filtering with suction and washing with deionized water until the filtrate is neutral, and drying in an oven at 80° C.;
[0010] (3) Calcination: The dried material obtained in step (2) is crushed and ground, passed through a 100-mesh sieve, and calcined at 400-450° C.
[0011] (4) Reduction: The material obtained after calcination in step (3) is reduced under a reducing atmosphere to obtain a Pd / NiMg-HT catalyst, which is a hydrogenated rosin catalyst.
[0012] Preferably, when the molar ratio of nickel ions to magnesium ions in step (1) is 1:1, the concentrations of nickel and magnesium are both 0.96 mol / L.
[0013] Preferably, in step (1), the amount of nickel nitrate hexahydrate added is 14.1058 g, the amount of palladium nitrate dihydrate added is 0.02 g, and the amount of magnesium nitrate hexahydrate added is 12.3590 g.
[0014] Preferably, in step (1), the sodium hydroxide aqueous solution and the sodium carbonate aqueous solution are prepared by weighing sodium hydroxide and dissolving it in water to obtain a 0.7596 mol / L sodium hydroxide aqueous solution; and weighing anhydrous sodium carbonate solution and dissolving it in water to obtain a 0.96 mol / L sodium carbonate aqueous solution.
[0015] Preferably, the calcination in step (3) is calcination at 450°C for 4 hours; the reducing atmosphere in step (4) is a mixed gas of hydrogen and nitrogen; specifically, a mixture of hydrogen and nitrogen in a volume ratio of 1:9; the reduction in step (4) is reduction at 450°C for 2.5 hours.
[0016] The hydrogenated rosin catalyst prepared as above is used in the preparation of hydrogenated rosin.
[0017] As described above, the operating method is to add the Pd / NiMg-HT catalyst to the rosin, carry out hydrogenation reaction at 170°C, maintain the hydrogen pressure at 3.5 MPa and the stirring speed at 600 r / min, react for 1 hour, and cool to room temperature after the reaction to obtain hydrogenated rosin.
[0018] Preferably, 0.05 g of Pd / NiMg-HT catalyst is added per 1 g of rosin.
[0019] Compared with the prior art, the present invention has the following beneficial effects:
[0020] (1) The method of the present invention uses nickel and magnesium hydrotalcite as a carrier, maintains a certain speed and continuously stirs to fully mix and impregnate the carrier and the active component solution. The process is simple, and nickel and magnesium are both cheap metals, which can greatly reduce the preparation cost of the catalyst in industrial applications;
[0021] (2) The method of the present invention can prepare a large amount of catalysts at the same time, greatly shortening the catalyst preparation time;
[0022] (3) The Pd / NiMg-HT catalyst prepared by the present invention is a powdered solid, which is suitable for heterogeneous catalytic rosin hydrogenation and has high catalytic efficiency. The rosin conversion rate reaches 96.46%, and the hydrogenated rosin selectivity reaches 78.06%. BRIEF DESCRIPTION OF THE DRAWINGS
[0023] Figure 1 This is the XRD diagram of the Pd / NiMg-HT catalyst prepared in Example 2 of the present invention.
[0024] Figure 2 This is a SEM image of the Pd / NiMg-HT catalyst prepared in Example 2 of the present invention. DETAILED DESCRIPTION
[0025] The specific implementation is described in detail below in conjunction with the accompanying drawings, but it should be understood that the protection scope of the present invention is not limited by the specific implementation. The raw materials and reagents used in the examples are all commercially available unless otherwise specified.
[0026] Example 1
[0027] A hydrogenated rosin catalyst and a preparation method thereof, the operating steps are as follows:
[0028] (1) Mixing: Weigh 14.02 g of nickel nitrate hexahydrate, 0.05 g of palladium nitrate dihydrate and 12.36 g of magnesium nitrate hexahydrate in a beaker, add 50 ml of deionized water to dissolve, control the molar ratio of nickel ions to magnesium ions to be 1, and at this time, the concentrations of nickel and magnesium are both 0.96 mol / L to obtain a mixed nitrate solution; weigh 7.47 g of sodium hydroxide and dissolve it in 250 ml of deionized water to obtain a 0.7596 mol / L sodium hydroxide aqueous solution, and then weigh 5.11 g of anhydrous sodium carbonate solution and dissolve it in 50 ml of deionized water to obtain a 0.96 mol / L sodium carbonate aqueous solution;
[0029] (2) Preparation: The sodium carbonate aqueous solution obtained in step (1) is heated in a water bath to 70° C., and the sodium hydroxide aqueous solution obtained in step (1) and the mixed nitrate solution obtained in step (1) are titrated simultaneously, and the pH value in the process is controlled to be 10-11. The mixture is stirred vigorously during the titration. After reacting at 70° C. for 3 hours, the mixture is aged for 3 hours with stirring turned off, and then cooled to room temperature. The substance obtained after aging is taken out and filtered, and washed with deionized water until the pH value is 7, and then placed in an oven at 80° C. for drying for 10 hours;
[0030] (3) Calcination: The dried material obtained in step (2) was crushed and ground to pass through a 100-mesh sieve. The sieved material was placed in a muffle furnace and calcined at 450° C. for 4 hours.
[0031] (4) Reduction: The material obtained after calcination in step (3) is reduced at 450° C. for 2.5 hours under a reducing atmosphere (the original atmosphere is a mixture of hydrogen and nitrogen in a volume ratio of 1:9) to obtain a Pd / NiMg-HT catalyst, namely a hydrogenated rosin catalyst.
[0032] The hydrogenated rosin catalyst prepared by the above method is used in the preparation of hydrogenated rosin, the method is to weigh 10g of rosin and dissolve it in 15g of No. 200 solvent oil, then put it into a 50mL micro-mechanical stirring reactor, then add 0.5g of the prepared Pd / NiMg-HT catalyst, pass hydrogen and perform three ventilation treatments, after completely replacing the original air in the reactor, at a temperature of 170°C, maintain a hydrogen pressure of 3.5Mpa and a stirring speed of 600r / min for hydrogenation reaction, react for 1 hour, cool to room temperature after the reaction, and obtain hydrogenated rosin. After filtering the sample through a filter membrane, take the filtrate for gas chromatography analysis, and calculate that the rosin conversion rate is 94.05% and the dihydroabietic acid selectivity is 83.32% (the palladium ion mass loading is 0.5wt.%).
[0033] Example 2
[0034] A hydrogenated rosin catalyst and a preparation method thereof, the operating steps are as follows:
[0035] (1) Mixing: Weigh 14.02 g of nickel nitrate hexahydrate, 0.02 g of palladium nitrate dihydrate and 12.36 g of magnesium nitrate hexahydrate in a beaker, add 50 ml of deionized water to dissolve, control the molar ratio of nickel ions to magnesium ions to be 1, and at this time, the concentrations of nickel and magnesium are both 0.96 mol / L to obtain a mixed nitrate solution; weigh 7.47 g of sodium hydroxide and dissolve it in 250 ml of deionized water to obtain a 0.7596 mol / L sodium hydroxide aqueous solution, and then weigh 5.11 g of anhydrous sodium carbonate solution and dissolve it in 50 ml of deionized water to obtain a 0.96 mol / L sodium carbonate aqueous solution;
[0036] (2) Preparation: The sodium carbonate aqueous solution obtained in step (1) is heated in a water bath to 70° C., and the sodium hydroxide aqueous solution obtained in step (1) and the mixed nitrate solution obtained in step (1) are titrated simultaneously, and the pH value in the process is controlled to be 10-11. The mixture is stirred vigorously during the titration. After reacting at 70° C. for 3 hours, the mixture is aged for 3 hours with stirring turned off, and then cooled to room temperature. The substance obtained after aging is taken out and filtered, and washed with deionized water until the pH value is 7, and then placed in an oven at 80° C. for drying for 10 hours;
[0037] (3) Calcination: The dried material obtained in step (2) was crushed and ground to pass through a 100-mesh sieve. The sieved material was placed in a muffle furnace and calcined at 450° C. for 4 hours.
[0038] (4) Reduction: The material obtained after calcination in step (3) was reduced at 450° C. for 2.5 hours under a reducing atmosphere (the original atmosphere was a mixture of hydrogen and nitrogen in a volume ratio of 1:9) to obtain a Pd / NiMg-HT catalyst, i.e., a hydrogenated rosin catalyst (the palladium ion mass loading was 0.2 wt.%).
[0039] The hydrogenated rosin catalyst prepared above is used in the preparation of hydrogenated rosin, the method is to weigh 10g of rosin and dissolve it in 15g of No. 200 solvent oil, then put it into a 50mL micro-mechanical stirring reactor, then add 0.5g of the prepared Pd / NiMg-HT catalyst, introduce hydrogen and perform three ventilation treatments, after completely replacing the original air in the reactor, at a temperature of 170°C, maintain a hydrogen pressure of 3.5Mpa and a stirring speed of 600r / min for hydrogenation reaction, react for 1 hour, cool to room temperature after the reaction, and obtain hydrogenated rosin. After filtering the sample through a filter membrane, take the filtrate for gas chromatography analysis, and calculate that the rosin conversion rate is 96.46% and the dihydroabietic acid selectivity is 78.06%.
[0040] Example 3
[0041] A hydrogenated rosin catalyst and a preparation method thereof, the operating steps are as follows:
[0042] (1) Mixing: Weigh 14.02 g of nickel nitrate hexahydrate, 0.03 g of palladium nitrate dihydrate and 12.36 g of magnesium nitrate hexahydrate in a beaker, add 50 ml of deionized water to dissolve, control the molar ratio of nickel ions to magnesium ions to be 1, and at this time, the concentrations of nickel and magnesium are both 0.96 mol / L to obtain a mixed nitrate solution; weigh 7.47 g of sodium hydroxide and dissolve it in 250 ml of deionized water to obtain a 0.7596 mol / L sodium hydroxide aqueous solution, and then weigh 5.11 g of anhydrous sodium carbonate solution and dissolve it in 50 ml of deionized water to obtain a 0.96 mol / L sodium carbonate aqueous solution;
[0043] The remaining operations and steps were the same as those in Example 2 to obtain a hydrogenated rosin catalyst (with a palladium ion mass loading of 0.3 wt.%).
[0044] The hydrogenated rosin catalyst prepared above is used in the preparation of hydrogenated rosin, the method is to weigh 10g of rosin and dissolve it in 15g of No. 200 solvent oil, then put it into a 50mL micro-mechanical stirring reactor, then add 0.5g of the prepared Pd / NiMg-HT catalyst, introduce hydrogen and perform three ventilation treatments, after completely replacing the original air in the reactor, at a temperature of 170°C, maintain a hydrogen pressure of 3.5Mpa and a stirring speed of 600r / min for hydrogenation reaction, react for 1 hour, cool to room temperature after the reaction, and obtain hydrogenated rosin. After filtering the sample through a filter membrane, take the filtrate for gas chromatography analysis, and calculate that the rosin conversion rate is 95.37% and the dihydroabietic acid selectivity is 74.79%.
[0045] Example 4
[0046] A hydrogenated rosin catalyst and a preparation method thereof, the operating steps are as follows:
[0047] (3) Calcination: The dried material obtained in step (2) is crushed and ground, and passed through a 100-mesh sieve. The sieved material is placed in a muffle furnace and calcined at 400° C. for 4 hours.
[0048] The remaining operations and steps were the same as those in Example 2 to obtain a hydrogenated rosin catalyst (with a palladium ion mass loading of 0.2 wt.%).
[0049] The hydrogenated rosin catalyst prepared above is used in the preparation of hydrogenated rosin, the method is to weigh 10g of rosin and dissolve it in 15g of No. 200 solvent oil, then put it into a 50mL micro-mechanical stirring reactor, then add 0.5g of the prepared Pd / NiMg-HT catalyst, introduce hydrogen and perform three ventilation treatments, after completely replacing the original air in the reactor, at a temperature of 170°C, maintain a hydrogen pressure of 3.5Mpa and a stirring speed of 600r / min for hydrogenation reaction, react for 1 hour, cool to room temperature after the reaction, and obtain hydrogenated rosin. After filtering the sample through a filter membrane, take the filtrate for gas chromatography analysis, and calculate that the rosin conversion rate is 95.23% and the dihydroabietic acid selectivity is 78.07%.
[0050] Comparative Example 1
[0051] A hydrogenated rosin catalyst and a preparation method thereof, the operating steps are as follows:
[0052] (1) Mixing: Weigh 16.43 g of nickel nitrate hexahydrate, 7.23 g of magnesium nitrate hexahydrate and 0.05 g of palladium nitrate dihydrate into a beaker, add 50 ml of deionized water to dissolve, and control the molar ratio of nickel ions to magnesium ions to be 2:1 to obtain a mixed nitrate solution; weigh 7.47 g of sodium hydroxide and dissolve it in 250 ml of deionized water to obtain a 0.7596 mol / L sodium hydroxide aqueous solution, and then weigh 5.11 g of anhydrous sodium carbonate solution and dissolve it in 50 ml of deionized water to obtain a 0.96 mol / L sodium carbonate aqueous solution;
[0053] The remaining operations and steps were the same as those in Example 2 to obtain a hydrogenated rosin catalyst (with a palladium ion mass loading of 0.5 wt.%).
[0054] The hydrogenated rosin catalyst prepared above is used in the preparation of hydrogenated rosin, the method is to weigh 10g of rosin and dissolve it in 15g of No. 200 solvent oil, then put it into a 50mL micro-mechanical stirring reactor, then add 0.5g of the prepared Pd / NiMg-HT catalyst, introduce hydrogen and perform three ventilation treatments, after completely replacing the original air in the reactor, at a temperature of 170°C, maintain a hydrogen pressure of 3.5Mpa and a stirring speed of 600r / min for hydrogenation reaction, react for 1 hour, cool to room temperature after the reaction, and obtain hydrogenated rosin. After filtering the sample through a filter membrane, take the filtrate for gas chromatography analysis, and calculate that the rosin conversion rate is 77.66% and the dihydroabietic acid selectivity is 77.06%.
[0055] Comparative Example 2
[0056] A hydrogenated rosin catalyst and a preparation method thereof, the operating steps are as follows:
[0057] (4) Reduction: The material obtained after calcination in step (3) was reduced at 400° C. for 2.5 hours in a reducing atmosphere (the original atmosphere was a mixture of hydrogen and nitrogen in a volume ratio of 1:9);
[0058] The remaining operations and steps were the same as those in Example 2 to obtain a hydrogenated rosin catalyst (with a palladium ion mass loading of 0.2 wt.%).
[0059] The hydrogenated rosin catalyst prepared above is used in the preparation of hydrogenated rosin, the method is to weigh 10g of rosin and dissolve it in 15g of No. 200 solvent oil, then put it into a 50mL micro-mechanical stirring reactor, then add 0.5g of the prepared Pd / NiMg-HT catalyst, introduce hydrogen and perform three ventilation treatments, after completely replacing the original air in the reactor, at a temperature of 170°C, maintain a hydrogen pressure of 3.5Mpa and a stirring speed of 600r / min for hydrogenation reaction, react for 1 hour, cool to room temperature after the reaction, and obtain hydrogenated rosin. After filtering the sample through a filter membrane, take the filtrate for gas chromatography analysis, and calculate that the rosin conversion rate is 79.07% and the dihydroabietic acid selectivity is 70.37%.
[0060] Figure 1 This is the XRD characterization analysis diagram of the 0.2wt% Pd / NiMg-HTC catalyst prepared in Example 2 of the present invention. Figure 1 It can be seen from the figure that the three peaks appearing at 2θ=37.01°, 43.07° and 62.57° are highly coincident with the characteristic diffraction peaks (009), (018) and (110) of hydrotalcite (HT). Therefore, the prepared catalyst is highly similar to hydrotalcite in structure.
[0061] Figure 2 This is the SEM characterization analysis of the 0.2wt% Pd / NiMg-HT catalyst prepared in Example 2 of the present invention at different magnifications. Figure 2 It can be seen that the catalyst is composed of a large number of microspherical particles with rough surfaces piled up to form a layered structure similar to hydrotalcite.
[0062] The foregoing description of specific exemplary embodiments of the present invention is for the purpose of illustration and demonstration. These descriptions are not intended to limit the present invention to the precise form disclosed, and it is clear that many changes and variations can be made based on the above teachings. The purpose of selecting and describing the exemplary embodiments is to explain the specific principles of the present invention and its practical application, so that those skilled in the art can realize and utilize various different exemplary embodiments of the present invention and various different selections and changes. The scope of the present invention is intended to be limited by the claims and their equivalents.
Claims
1. A hydrogenated rosin catalyst, characterized in that: The molecular formula is Pd / NiMg-HT, in which the active ingredient palladium ions (Pd) are dispersed in the hydrotalcite carrier in the form of nanoparticles, wherein the mass loading amount of palladium ions is 0.2-0.5wt.%, and the molar ratio of nickel ions to magnesium ions is 1:
1.
2. The hydrogenated rosin catalyst according to claim 1, characterized in that: The palladium ion mass loading is 0.2 wt.%.
3. The method for preparing a hydrogenated rosin catalyst as claimed in any one of claims 1 to 2, characterized in that: The following steps are included: (1) Mixing: dissolving nickel nitrate, palladium nitrate and magnesium nitrate in water to obtain a mixed nitrate solution, and simultaneously preparing a sodium hydroxide aqueous solution and a sodium carbonate aqueous solution; (2) Preparation: Heat the sodium carbonate aqueous solution obtained in step (1) in a water bath, titrate the mixed nitrate solution with sodium hydroxide aqueous solution simultaneously, control the pH value in the process to be between 10 and 11, stir vigorously during titration, react at 70° C. for 3 hours, turn off stirring and age for 3 hours, cool to room temperature, filter and wash with water until the filtrate is neutral, and dry in an oven at 80° C.; (3) Calcination: The dried material obtained in step (2) is crushed, ground, sieved, and calcined at 400-450°C; (4) Reduction: The material obtained after calcination in step (3) is reduced under a reducing atmosphere to obtain a Pd / NiMg-HT catalyst, which is a hydrogenated rosin catalyst.
4. The method for preparing the hydrogenated rosin catalyst according to claim 3, characterized in that: When the molar ratio of nickel ions to magnesium ions in step (1) is 1:1, the concentrations of nickel and magnesium are both 0.96 mol / L.
5. The method for preparing the hydrogenated rosin catalyst according to claim 3, characterized in that: In step (1), the amount of nickel nitrate hexahydrate added is 14.1058 g, the amount of palladium nitrate dihydrate added is 0.02 g, and the amount of magnesium nitrate hexahydrate added is 12.3590 g.
6. The method for preparing the hydrogenated rosin catalyst according to claim 3, characterized in that: The sodium hydroxide aqueous solution and the sodium carbonate aqueous solution are prepared in step (1) by weighing sodium hydroxide and dissolving it in water to obtain a 0.7596 mol / L sodium hydroxide aqueous solution; and weighing anhydrous sodium carbonate solution and dissolving it in water to obtain a 0.96 mol / L sodium carbonate aqueous solution.
7. The method for preparing the hydrogenated rosin catalyst according to claim 3, characterized in that: The calcination in step (3) is calcination at 450° C. for 4 hours; the reducing atmosphere in step (4) is a mixed gas of hydrogen and nitrogen; specifically, a mixture of hydrogen and nitrogen in a volume ratio of 1:9; the reduction in step (4) is reduction at 450° C. for 2.5 hours.
8. Use of the hydrogenated rosin catalyst prepared by the method according to any one of claims 4 to 7 in the preparation of hydrogenated rosin.
9. Use of the hydrogenated rosin catalyst as claimed in claim 8 in the preparation of hydrogenated rosin, characterized in that: The operation method is to add the Pd / NiMg-HT catalyst to the rosin, carry out hydrogenation reaction at 170°C, maintain the hydrogen pressure at 3.5Mpa, and stir at 600r / min for 1 hour, and cool to room temperature after the reaction to obtain hydrogenated rosin.
10. Use of the hydrogenated rosin catalyst according to claim 9 in the preparation of hydrogenated rosin, characterized in that: 0.05 g of Pd / NiMg-HT catalyst was added per 1 g of rosin.