A nickel-based catalyst for hydrogenation of c9 petroleum resin and preparation and application thereof
By adding polyvinylpyrrolidone (PVP) as an additive to a Ni-based catalyst, a supported Ni-based catalyst with small particle size was prepared, which solved the problem of insufficient activity and stability of Ni-based catalysts in the hydrogenation reaction of C9 petroleum resin and achieved a highly efficient hydrogenation effect.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- ZHEJIANG UNIV OF TECH
- Filing Date
- 2026-03-18
- Publication Date
- 2026-06-19
AI Technical Summary
Existing Ni-based catalysts exhibit weak hydrogenation activity and poor catalyst stability in the hydrogenation reaction of C9 petroleum resins, which hinders the widespread application of petroleum resins.
Using polyvinylpyrrolidone (PVP) as an additive, a method for preparing supported Ni-based catalysts was employed, including SiO2 support treatment, nickel salt solution mixing, calcination, and reduction treatment, to prepare Ni particles with small particle size, thereby improving catalytic activity and enhancing stability.
The prepared Ni-based catalyst exhibits excellent catalytic activity and stability in the hydrogenation reaction of C9 petroleum resin, and the preparation process is environmentally friendly and non-toxic, avoiding the influence of high temperature and high pressure conditions.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of catalysts, and more specifically, to a nickel-based catalyst for the hydrogenation of C9 petroleum resins, its preparation method, and its application. Background Technology
[0002] Ni-based catalysts possess advantages such as abundant resources, low cost, and excellent resistance to poisoning, making them promising candidates for the hydrogenation of C9 petroleum resins. However, the hydrogenation activity of Ni-based catalysts is relatively weak, typically requiring high temperatures and pressures for the reaction, which can affect the performance of petroleum resins and consequently limit their widespread application. Early C9 petroleum resin hydrogenation catalysts were primarily Raney nickel-based, but these were difficult to store. Later, researchers increasingly employed supported Ni-based catalysts for C9 petroleum resin hydrogenation. However, these catalysts generally suffer from low hydrogenation efficiency, poor catalyst stability, and high product unsaturation. Adding chelating agents, dispersants, or additives during catalyst preparation can typically improve the dispersion of the active components and enhance the catalyst's hydrogenation performance.
[0003] Based on the characteristics and existing problems of Ni-based catalysts, this invention reports a technique for preparing Ni-based catalysts and their application in the hydrogenation reaction of petroleum resins. This technique enables large-scale production of the catalyst and improves its hydrogenation activity and stability. Solving the aforementioned problems is of great significance for the application of petroleum resin hydrogenation. Summary of the Invention
[0004] To address the issue that the catalytic activity of existing Ni-based catalysts for the hydrogenation of C9 petroleum resin needs to be improved, this invention provides a method for preparing a Ni-based catalyst for the hydrogenation of C9 petroleum resin. This catalyst preparation method is simple and exhibits good catalytic performance in the catalytic hydrogenation reaction of C9 petroleum resin.
[0005] The technical solutions adopted to solve the above problems are described below.
[0006] In a first aspect, the present invention provides a method for preparing a nickel-based catalyst for the hydrogenation of C9 petroleum resin, the method comprising the following steps: (a) A surface area of not less than 300 m² 2 / g of SiO2 powder was added to a nitric acid solution and stirred. Then, the SiO2 support was obtained by filtration, washing, drying and high-temperature calcination. (b) Dissolve the nickel salt and the auxiliary agent in deionized water to obtain a mixed aqueous solution; wherein the nickel salt is one of nickel nitrate hexahydrate, anhydrous nickel sulfate, nickel sulfate hexahydrate, nickel sulfate heptahydrate, and nickel chloride hexahydrate; wherein the auxiliary agent is polyvinylpyrrolidone; (c) The mixed aqueous solution is added dropwise to the SiO2 support, mixed evenly, and then dried to obtain a powdered precursor, such that the mass ratio of nickel in the mixed aqueous solution to the mass of the SiO2 support is 20-50 wt%. (d) The powdered precursor was calcined at high temperature and then ground to obtain the calcined product; supported Ni-based catalyst powder; (e) The calcination product is reduced by hydrogen to obtain the reduction product; (f) The reduction product is passivated in a mixed atmosphere of oxygen and nitrogen, wherein the volume fraction of oxygen in the mixed atmosphere is 1-5%, to obtain a nickel-based catalyst.
[0007] Further, the drying conditions in step (a) are as follows: the oven drying temperature is 100-120℃, more preferably 120℃; the drying time is 5-6h, more preferably 6h; the high-temperature calcination treatment conditions are as follows: the high-temperature calcination atmosphere is preferably air, the calcination temperature is 500-600℃, more preferably 600℃, and the calcination time is 6-8h, more preferably 8h.
[0008] Furthermore, the nickel salt mentioned in step (b) is preferably nickel nitrate hexahydrate.
[0009] Furthermore, the polyvinylpyrrolidone mentioned in step (b) is polyvinylpyrrolidone of type K30.
[0010] Further, in step (b), the concentration of nickel salt in the mixed aqueous solution is 0.1-1.0 mol / L, preferably 0.2-0.3 mol / L; the mass of polyvinylpyrrolidone is 10-20% of the mass of Ni in the nickel salt, preferably 14-16%.
[0011] Furthermore, the uniform mixing in step (c) is carried out in the following manner: first, ultrasonic treatment is performed, followed by stirring at room temperature. The ultrasonic treatment conditions are: ultrasonic temperature is 20-50℃, more preferably 30℃, ultrasonic time is 0.5-1h, more preferably 0.5h; and stirring time is 12-14h.
[0012] Furthermore, the drying conditions in step (c) are as follows: the drying temperature of the oven is 80-120°C, more preferably 80°C; the drying time is 10-14 hours, more preferably 12 hours.
[0013] Furthermore, in step (d), the high-temperature calcination conditions are: calcination temperature of 400-600℃, more preferably 550℃, and calcination time of 4-5h, more preferably 4h.
[0014] Furthermore, in step (d), the particle size range of the calcined product is preferably 140 to 160 mesh.
[0015] Furthermore, in step (e), the hydrogen reduction conditions are: a reduction temperature of 350-500℃, preferably 400℃, and a reduction time of 2-4 h, preferably 2 h.
[0016] Further, in step (e), the passivation conditions are: passivation at room temperature for 3-5 h; more preferably, the volume fraction of oxygen in the mixed atmosphere is 1%, and the passivation time is 4 h.
[0017] In a second aspect, the present invention provides a nickel-based catalyst prepared according to the preparation method described in the first aspect.
[0018] Thirdly, the present invention provides the application of the nickel-based catalyst described in the second aspect in the hydrogenation reaction of C9 petroleum resin.
[0019] Compared with the prior art, the present invention has the following advantages: (1) In this invention, polyvinylpyrrolidone (PVP) is added during the preparation of the nickel-based catalyst. The addition of PVP effectively prevents the aggregation of nickel nanoparticles, thereby reducing the particle size of Ni particles. At the same time, the addition of PVP significantly improves its catalytic activity in the hydrogen reaction of C9 petroleum resin.
[0020] (2) The preparation process of the supported Ni-based catalyst reported in this invention does not use toxic and environmentally hazardous strong reducing reagents, and the preparation process is green and environmentally friendly.
[0021] (3) The supported Ni catalyst reported in this invention exhibits excellent reactivity in the hydrogen reaction of C9 petroleum resin. Attached Figure Description
[0022] Figure 1 The image shows the XRD pattern of the Ni-based catalyst prepared in Example 1.
[0023] Figure 2 The image shows the XRD pattern of the Ni-based catalyst prepared by Comparative Example 1.
[0024] Figure 3 The image shows the XRD pattern of the Ni-based catalyst prepared by Comparative Example 2. Detailed Implementation
[0025] The technical solution of the present invention will be further described below with reference to specific embodiments, but the scope of protection of the present invention is not limited by the following embodiments.
[0026] Example 1
[0027] Weigh out 50 g of SiO2 powder (specific surface area: 337.0 m²). 2 / g) was added to 500 mL of dilute nitric acid (1 mol / L) solution and stirred for 3 h. The mixed solution was filtered and washed with deionized water, and the process was repeated several times until the mixed solution was neutral. Then, the washed SiO2 powder was placed in a muffle furnace and calcined at 600 ℃ for 8 h to obtain acid-washed SiO2.
[0028] Weigh 2.907 g Ni(NO3)2·6H2O and 0.0872 g polyvinylpyrrolidone K30 (PVP K30), dissolve them in 40 mL deionized water, and then add 2.345 g acid-washed SiO2. Sonicate the mixture at 30 °C for 30 min, stir the resulting solution at room temperature for 12 h, and then dry it in an oven at 80 °C for 12 h. Finally, calcine the mixture in air at 550 °C for 4 h, grind it, and pass it through a 140-160 mesh sieve to obtain the original catalyst powder.
[0029] 0.3500 g of the original catalyst powder was placed in a fixed-bed reactor and reduced with H2 at 400℃ for 2 h. Then, it was passivated with 1% O2 / N2 at room temperature for 4 h to obtain the supported Ni-based catalyst.
[0030] The XRD pattern of the catalyst is attached. Figure 1 As shown in the figure. XRD characterization indicates that the catalyst mainly contains the Ni crystalline phase, and the particle size of Ni in the catalyst is estimated to be approximately ~7.5 nm using the Scherer equation. The above XRD characterization demonstrates that the method reported in this invention can be used to prepare supported Ni-based catalysts with smaller particle sizes.
[0031] Example 2
[0032] The hydrogenation reaction of C9 petroleum resin was carried out using the catalyst prepared in Example 1. The specific method is as follows: 15g of C9 petroleum resin (bromine value 23.4gBr / 100g) was dissolved in 100g of cyclohexane. After stirring for 1 hour, 10g of diatomaceous earth was added, and stirring was continued for 2 hours. After sedimentation and centrifugation, a 15% C9 petroleum resin solution was obtained. The color of the unhydrogenated C9 petroleum resin solution was measured to be 13 using a petroleum product colorimeter.
[0033] 0.3500 g of the supported Ni-based catalyst prepared in Example 1 and 70 g of 15% C9 petroleum resin solution were placed together in a micro high-temperature and high-pressure reactor. The air in the micro high-temperature and high-pressure reactor was replaced with H2, and then H2 was introduced. The C9 petroleum resin hydrogenation reaction was carried out under the reaction conditions of 220°C, initial pressure of 6 MPa, reaction time of 4 h, and rotation speed of 600 r / min. After the reaction temperature dropped to room temperature, the reaction solution was discharged and sampled for analysis.
[0034] Bromine value determination method: The bromine value of petroleum resins was determined according to the method for determining bromine value in the People's Republic of China National Standard GB / T 24138-2009.
[0035] Colorimetric testing method: The colorimetry of hydrogenated petroleum resin was measured using a petroleum product colorimeter (SS-1) manufactured by Shanghai Pengpu Refrigeration Co., Ltd.
[0036] The hydrogenation activity test results are shown in Table 1. The experimental results indicate that the supported Ni-based catalyst prepared in Example 1 has good hydrogenation performance of C9 petroleum resin.
[0037] Comparative Example 1
[0038] Weigh 2.907 g Ni(NO3)2·6H2O and dissolve it in 40 mL of deionized water. After dissolution, add 2.345 g of acid-washed SiO2 obtained according to Example 1. Sonicate at 30 °C for 30 min. Stir the ultrasonicated mixture at room temperature for 12 h. Dry the stirred solution in an oven at 80 °C for 12 h. Then calcine at 550 °C for 4 h in air atmosphere. Grind and pass through a 140-160 mesh sieve to obtain the original powder catalyst.
[0039] 0.3500 g of the original catalyst powder was placed in a fixed-bed reactor and reduced with H2 at 400℃ for 2 h. Then, it was passivated with 1% O2 / N2 at room temperature for 4 h to obtain the supported Ni-based catalyst.
[0040] The XRD pattern of the catalyst is attached. Figure 2 As shown in the figure. XRD characterization indicates that the catalyst mainly contains the Ni crystalline phase, and the particle size of Ni in the catalyst is estimated to be approximately ~10.2 nm using the Scherer equation. The above XRD characterization demonstrates that the addition of polyvinylpyrrolidone (PVP) can effectively prevent the aggregation of nickel nanoparticles.
[0041] The C9 petroleum resin hydrogenation reaction was carried out using the catalyst prepared in Comparative Example 1, and the specific method was the same as in Example 2. The results are shown in Table 1.
[0042] Comparative Example 2
[0043] Weigh 2.907 g Ni(NO3)2·6H2O and 2.0 g PEG-1000, dissolve them in 40 mL deionized water, and add 2.345 g of acid-washed SiO2 prepared according to Example 1. Sonicate the mixture at 30 °C for 30 min, stir the resulting solution at room temperature for 12 h, and then dry it in an oven at 80 °C for 12 h. Finally, calcine the solution at 550 °C for 4 h in air, grind it, and pass it through a 140-160 mesh sieve to obtain the original catalyst powder.
[0044] 0.3500 g of the original catalyst powder was placed in a fixed-bed reactor and reduced with H2 at 400℃ for 2 h. Then, it was passivated with 1% O2 / N2 at room temperature for 4 h to obtain the supported Ni-based catalyst.
[0045] The XRD pattern of the catalyst is attached. Figure 3 As shown in the figure. XRD characterization indicates that the catalyst mainly contains the Ni crystalline phase, and the particle size of Ni in the catalyst is estimated to be approximately ~7.8 nm using the Scherer equation. The above XRD characterization shows that the catalyst prepared by the method reported in Comparative Example 2, with the addition of the dispersant PEG, has a similar particle size to the catalyst prepared by the method reported in Example 1, but its activity on C9 petroleum resin is poor. This indicates that reducing the particle size of Ni particles has a limited effect on improving the catalytic performance of the catalyst in the hydrogenation reaction of C9 petroleum resin. We speculate that the N in PVP may promote the hydrogenation activity of Ni-based catalysts on C9 petroleum resin.
[0046] The catalyst prepared in Comparative Example 2 was used to carry out the hydrogenation reaction of C9 petroleum resin. The specific method was the same as in Example 2, and the results are shown in Table 1.
[0047] Table 1
[0048] The above experimental results show that the Ni-based catalyst obtained by the preparation method described in this invention has strong hydrogenation activity for C9 petroleum resin, and the hydrogenated petroleum resin produced by this Ni-based catalyst has a color of 0 and a bromine value of 5.2. Therefore, the Ni-based catalyst reported in this invention exhibits excellent catalytic performance and superior reactivity in the hydrogenation reaction of C9 petroleum resin.
Claims
1. A method for preparing a nickel-based catalyst for the hydrogenation of C9 petroleum resin, characterized in that: The preparation method includes the following steps: (a) A surface area of not less than 300 m² 2 / g of SiO2 powder was added to a nitric acid solution and stirred. Then, the SiO2 support was obtained by filtration, washing, drying and high-temperature calcination. (b) Dissolve the nickel salt and the auxiliary agent in deionized water to obtain a mixed aqueous solution; wherein the nickel salt is one of nickel nitrate hexahydrate, anhydrous nickel sulfate, nickel sulfate hexahydrate, nickel sulfate heptahydrate, and nickel chloride hexahydrate; wherein the auxiliary agent is polyvinylpyrrolidone; (c) The mixed aqueous solution is added dropwise to the SiO2 support, mixed evenly, and then dried to obtain a powdered precursor, such that the mass ratio of nickel in the mixed aqueous solution to the mass of the SiO2 support is 20-50 wt%. (d) The powdered precursor was subjected to high-temperature calcination and then ball milled to obtain the calcined product; supported Ni-based catalyst powder; (e) The calcination product is reduced by hydrogen to obtain the reduction product; (f) The reduction product is passivated in a mixed atmosphere of oxygen and nitrogen, wherein the volume fraction of oxygen in the mixed atmosphere is 1-5%, to obtain a nickel-based catalyst.
2. The preparation method according to claim 1, characterized in that: The drying conditions described in step (a) are: oven drying temperature of 100-120℃ and drying time of 5-6h; high-temperature calcination conditions are: high-temperature calcination atmosphere of air, calcination temperature of 500-600℃ and calcination time of 6-8h.
3. The preparation method according to claim 1, characterized in that: The polyvinylpyrrolidone mentioned in step (b) is polyvinylpyrrolidone of type K30.
4. The preparation method according to claim 1, characterized in that: In step (b), the concentration of nickel salt in the mixed aqueous solution is 0.1-1.0 mol / L, and the mass of polyvinylpyrrolidone is 10-20% of the mass of Ni in the nickel salt.
5. The preparation method according to claim 1, characterized in that: The drying conditions in step (c) are: oven drying temperature of 80-120℃ and drying time of 10-14h.
6. The preparation method according to claim 1, characterized in that: In step (d), the high-temperature calcination conditions are: calcination temperature of 500-600℃ and calcination time of 4-5h.
7. The preparation method according to claim 1, characterized in that: In step (e), the hydrogen reduction conditions are: reduction temperature of 350-500℃ and reduction time of 2-4 h.
8. The preparation method according to claim 1, characterized in that: In step (e), the passivation conditions are: passivation at room temperature for 3-5 h.
9. A nickel-based catalyst prepared by any one of claims 1-8.
10. The application of the nickel-based catalyst as described in claim 9 in the hydrogenation reaction of C9 petroleum resin.