A solid acid catalyst, its preparation method and application

Abstract

This invention belongs to the field of catalyst technology, specifically relating to a solid acid catalyst, its preparation method, and its application. The invention provides a method for preparing a solid acid catalyst, comprising the following steps: mixing a dichlorohydrin solution, N-methylpyrrolidone, and silica sol, and sequentially aging and calcining them to obtain a ZrO2-SiO2 support; mixing the ZrO2-SiO2 support with a sulfuric acid solution, and sequentially impregnating and calcining them to obtain the solid acid catalyst. The preparation method provided by this invention, through a sequential sol-gel method and sulfuric acid solution impregnation, prepares SO4 with uniform size and dispersion. 2‑ The ZrO2-SiO2 solid acid catalyst has widely available and low-cost raw materials, and its preparation process is safe and easy to control, allowing for large-scale production. Furthermore, the obtained solid acid catalyst exhibits excellent performance in treating tail gas from acetylenic diol production, making it suitable for the industrial production of acetylenic diol.

Description

Technical Field

[0001] This invention belongs to the field of catalyst technology, specifically relating to a solid acid catalyst, its preparation method, and its application. Background Technology

[0002] Currently, the production of acetylenic diols generally employs modified Reppe, slurry bed, or suspension bed processes, with the reaction carried out under normal or low-pressure conditions. The process uses acetylene and methyl ketones as raw materials, methyl tert-butyl ether as a solvent, and a Reppe reaction occurs under the catalysis of a large amount of KOH, producing a viscous acetylenic diol. However, during the reaction, a side reaction occurs: methyl ketones undergo an aldol condensation reaction under alkaline conditions, producing dimers and polymers of methyl ketones. Due to the characteristics of this Reppe reaction, this side reaction is difficult to avoid, and the resulting polymers are primarily treated as waste.

[0003] The polymer is mainly formed by the aldol condensation of methyl ketones under alkaline conditions. This reaction is reversible, and theoretically, under certain conditions, it can be converted back into the raw material ketone. To reduce the production cost of acetylenic diol products and effectively treat the resulting polymer, a catalyst suitable for the catalytic decomposition of the polymer obtained from the aldol condensation of methyl ketones is urgently needed to catalyze the polymer in the acetylenic diol reaction, converting it back into the raw material ketone, thereby improving the utilization rate of the raw material and reducing production costs. Summary of the Invention

[0004] The purpose of this invention is to provide a solid acid catalyst, its preparation method, and its application. The preparation method provided by this invention can prepare a solid acid catalyst suitable for the catalytic decomposition of polymers obtained by methyl ketone aldol condensation.

[0005] To achieve the objectives of this invention, the following technical solutions are provided:

[0006] This invention provides a method for preparing a solid acid catalyst, comprising the following steps:

[0007] A solution of dichlorohydrin, N-methylpyrrolidone and silica sol were mixed and then aged and calcined sequentially to obtain a ZrO2-SiO2 support.

[0008] The ZrO2-SiO2 support was mixed with sulfuric acid solution, and then impregnated and calcined sequentially to obtain the solid acid catalyst.

[0009] Preferably, the concentration of oxachlor dichloride in the oxachlor dichloride solution is 0.1–1 mol / L.

[0010] Preferably, the mass of the N-methylpyrrolidone is 1 to 5% of the mass of the dichlorohydrin solution.

[0011] Preferably, the aging time is 6-12 hours and the pH value is 8-13.

[0012] Preferably, the calcination temperature is 300–800°C and the time is 3–8 hours.

[0013] Preferably, the Zr-Si molar ratio in the ZrO2-SiO2 support is 1:2 to 8.

[0014] Preferably, the concentration of the sulfuric acid solution is 0.5–3 mol / L;

[0015] The soaking time is 8 to 16 hours.

[0016] Preferably, the roasting temperature is 100–300°C and the time is 4–10 hours.

[0017] The present invention also provides a solid acid catalyst prepared by the preparation method described in the above technical solution.

[0018] The present invention also provides the application of the solid acid catalyst described in the above technical solution in the catalytic decomposition of polymers obtained by methyl ketone aldol condensation.

[0019] This invention provides a method for preparing a solid acid catalyst, comprising the following steps: mixing a dichlorohydrin solution, N-methylpyrrolidone, and silica sol, and sequentially aging and calcining the mixture to obtain a ZrO2-SiO2 support; mixing the ZrO2-SiO2 support with a sulfuric acid solution, and sequentially impregnating and calcining the mixture to obtain the solid acid catalyst. The preparation method provided by this invention, through a sequential sol-gel method and sulfuric acid solution impregnation, prepares SO4 with uniform size and dispersion. 2- The ZrO2-SiO2 solid acid catalyst has widely available and low-cost raw materials, and its preparation process is safe and easy to control, allowing for large-scale production. Furthermore, the obtained solid acid catalyst exhibits excellent performance in treating tail gas from acetylenic diol production, making it suitable for the industrial production of acetylenic diol. Detailed Implementation

[0020] This invention provides a method for preparing a solid acid catalyst, comprising the following steps:

[0021] A solution of dichlorohydrin, N-methylpyrrolidone and silica sol were mixed and then aged and calcined sequentially to obtain a ZrO2-SiO2 support.

[0022] The ZrO2-SiO2 support was mixed with sulfuric acid solution, and then impregnated and calcined sequentially to obtain the solid acid catalyst.

[0023] In this invention, unless otherwise specified, all raw material components are commercially available products well known to those skilled in the art.

[0024] This invention involves mixing dichlorohydrin solution, N-methylpyrrolidone, and silica sol, followed by aging and calcination to obtain a ZrO2-SiO2 support.

[0025] In this invention, the concentration of oxachloride in the oxachloride solution is preferably 0.1 to 1 mol / L, more preferably 0.2 to 0.8 mol / L, and most preferably 0.3 to 0.5 mol / L.

[0026] In this invention, the mass of the N-methylpyrrolidone is preferably 1 to 5% of the mass of the dichlorohydrin solution, more preferably 2 to 4%, and most preferably 2 to 3%.

[0027] In this invention, the Zr-Si molar ratio of the dichlorodichlorodichlorosol and silica sol is preferably 1:2 to 8, more preferably 1:3 to 7, and most preferably 1:4 to 6.

[0028] In this invention, the mixing is preferably performed by first mixing the dichlorohydrin solution and N-methylpyrrolidone, and then adding the silica sol; the silica sol is preferably added dropwise.

[0029] In this invention, the aging time is preferably 6-12 hours, more preferably 8-10 hours; the pH value is preferably 8-13, more preferably 9-12, and most preferably 10-11; the method of adjusting the pH value is preferably by adding ammonia water; the addition of ammonia water is preferably carried out at the same time as adding silica sol; this invention does not impose any special limitations on the process of adding ammonia water, and any method known to those skilled in the art can be used to make the pH value of the aging process reach the above range.

[0030] In this invention, the aging process preferably includes sequential washing and drying; the washing reagent is deionized water; this invention does not impose any special limitations on the washing process, and any process well known to those skilled in the art can be used to ensure that the aging product is free of chloride ions; this invention does not impose any special limitations on the drying process, and any process well known to those skilled in the art can be used to ensure that the aging product is fully dried.

[0031] In this invention, the calcination temperature is preferably 300-800℃, more preferably 400-700℃, and most preferably 500-600℃; the calcination time is preferably 3-8h, more preferably 4-7h, and most preferably 5-6h.

[0032] In this invention, the Zr-Si molar ratio in the ZrO2-SiO2 support is preferably 1:2 to 8, more preferably 1:3 to 7, and most preferably 1:4 to 6.

[0033] After obtaining the ZrO2-SiO2 support, the present invention mixes the ZrO2-SiO2 support with sulfuric acid solution, and then impregnates and calcines it sequentially to obtain the solid acid catalyst.

[0034] In this invention, the concentration of the sulfuric acid solution is preferably 0.5-3 mol / L, more preferably 1-2.5 mol / L, and most preferably 1.5-2 mol / L; the sulfuric acid solution is preferably an aqueous solution of sulfuric acid.

[0035] In this invention, the soaking time is preferably 8 to 16 hours, more preferably 10 to 14 hours, and most preferably 12 to 14 hours.

[0036] In this invention, the impregnation process preferably includes sequential filtration and drying. The filtration process is not particularly limited and can be performed using a process well-known to those skilled in the art. The drying temperature is preferably 20–100°C, more preferably 30–60°C, and most preferably 50°C. The drying process is not particularly limited and can be performed using a process well-known to those skilled in the art to ensure the impregnated product is fully dried.

[0037] In this invention, the roasting temperature is preferably 100-300℃, more preferably 150-250℃, and most preferably 150-200℃; the roasting time is preferably 4-10h, more preferably 5-9h, and most preferably 6-8h.

[0038] The preparation method provided by this invention prepares SO4 with uniform size and uniform dispersion by sequentially performing a sol-gel method and impregnation with sulfuric acid solution. 2- The ZrO2-SiO2 solid acid catalyst has widely available and low-cost raw materials, and its preparation process is safe and easy to control, allowing for large-scale production. Furthermore, the obtained solid acid catalyst exhibits excellent performance in treating tail gas from acetylenic diol production, making it suitable for the industrial production of acetylenic diol.

[0039] The present invention also provides a solid acid catalyst prepared by the preparation method described in the above technical solution.

[0040] The present invention also provides the application of the solid acid catalyst described in the above technical solution in the catalytic decomposition of polymers obtained by methyl ketone aldol condensation.

[0041] In this invention, the polymer obtained by the methyl ketone aldol condensation is preferably a polymer obtained from the acetylide diol reaction.

[0042] In this invention, the method for catalytically decomposing the polymer in the acetylenic diol reaction into the raw material ketone using the solid acid catalyst preferably includes the following steps:

[0043] The solid acid catalyst was placed in a tubular reactor, and acetylsadiol polymer and nitrogen were introduced to carry out catalytic decomposition to obtain the raw material ketone.

[0044] In this invention, the flow rate of the acetylenic diol polymer is preferably 1 to 10 L / min, more preferably 2 to 5 L / min, and most preferably 3 L / min.

[0045] In this invention, the flow rate of nitrogen is preferably 0.01 to 0.05 m / s, more preferably 0.02 to 0.04 m / s, and most preferably 0.03 m / s.

[0046] In this invention, the nitrogen gas is used as a carrier gas to carry the product raw material ketone out from the top of the tubular reactor.

[0047] In this invention, the temperature of the catalytic decomposition is preferably 100-250°C, more preferably 150-200°C, and most preferably 180°C.

[0048] This invention catalyzes the polymer in the reaction of acetylenic diol to produce ketone as a raw material using a solid acid catalyst. The catalytic efficiency is high, the reaction process is pollution-free, the catalyst is recyclable, the production process is safe, the reaction temperature is easily controlled, the cost is low, and it is easy to industrialize. This effectively solves the problem of polymer disposal in the acetylenic diol reaction, successfully reducing the cost of the acetylenic diol reaction and meeting national and industry requirements for industrial waste treatment, thus achieving a green and environmentally friendly acetylenic diol project.

[0049] To further illustrate the present invention, the solid acid catalyst, its preparation method, and its application provided by the present invention are described in detail below with reference to the embodiments, but these should not be construed as limiting the scope of protection of the present invention.

[0050] Example 1

[0051] ZrOCl2 was dissolved in deionized water to obtain a 0.4 mol / L solution of oxachlor dichloride. 3% N-methylpyrrolidone was added. Ammonia and silica sol were simultaneously added dropwise to the oxachlor dichloride solution at a Zr-Si molar ratio of 1:2. The titration ended when the pH of the oxachlor dichloride solution reached 10. The solution was aged for 8 hours, washed with deionized water until chloride ions were removed, dried, and calcined at 500℃ for 5 hours to obtain a ZrO2-SiO2 support. The ZrO2-SiO2 support was impregnated in a 1.5 mol / L sulfuric acid aqueous solution for 12 hours, filtered, dried at 50℃, and then calcined at 150℃ for 6 hours to obtain SO42-. 2- / ZrO2-SiO2 solid acid catalyst.

[0052] Examples 2-7

[0053] Solid acid catalysts were prepared according to the technical solution provided in Example 1, with the only difference being that the Zr-Si molar ratios were 1:3, 1:4, 1:5, 1:6, 1:7, and 1:8, respectively.

[0054] Examples 8-11

[0055] Solid acid catalysts were prepared according to the technical solution provided in Example 3, with the only difference being that the mass of N-methylpyrrolidone was 1%, 2%, 4%, and 5% of the mass of the dichlorohydrin solution, respectively.

[0056] Examples 12-16

[0057] The solid acid catalyst was prepared according to the technical solution provided in Example 9, except that the titration was stopped when the ammonia solution was titrated to a pH value of 8, 9, 11, 12 and 13 respectively.

[0058] Examples 17-22

[0059] Solid acid catalysts were prepared according to the technical solution provided in Example 9, with the only difference being that the aging times were 6h, 7h, 9h, 10h, 11h and 12h, respectively.

[0060] Examples 23-27

[0061] Solid acid catalysts were prepared according to the technical solution provided in Example 9, with the only difference being that the calcination temperatures were 300℃, 400℃, 600℃, 700℃ and 800℃, respectively.

[0062] Examples 28-32

[0063] Solid acid catalysts were prepared according to the technical solution provided in Example 9, with the only difference being that the calcination times were 3h, 4h, 6h, 7h and 8h, respectively.

[0064] Examples 33-37

[0065] Solid acid catalysts were prepared according to the technical solution provided in Example 9, with the only difference being that the concentrations of the sulfuric acid aqueous solution were 0.5 mol / L, 1 mol / L, 2 mol / L, 2.5 mol / L, and 3 mol / L, respectively.

[0066] Examples 38-41

[0067] Solid acid catalysts were prepared according to the technical solution provided in Example 9, with the only difference being that the impregnation times were 8h, 10h, 14h and 16h, respectively.

[0068] Examples 42-45

[0069] Solid acid catalysts were prepared according to the technical solution provided in Example 9, with the only difference being that the calcination temperatures were 100°C, 200°C, 250°C, and 300°C, respectively.

[0070] Examples 46-49

[0071] Solid acid catalysts were prepared according to the technical solution provided in Example 9, with the only difference being that the calcination times were 4h, 8h, 10h, and 12h, respectively.

[0072] Test Example 1

[0073] The solid acid catalysts obtained in Examples 1-7 were transferred to a tubular reactor, and a protective gas N2 was introduced into the bottom of the apparatus. A polymer of acetylenic diol was introduced into the middle of the tubular reactor at a flow rate of 3 L / min. The reaction temperature was controlled at 180°C. N2 gas was introduced at the bottom at a velocity of 0.03 m / s to carry the product from the upper end of the tubular reactor out. The resulting primary product was analyzed by liquid chromatography, and the results are shown in Table 1.

[0074] Table 1 Effect of Zr-Si molar ratio on polymer catalytic decomposition in the acetylenic diol reaction

[0075] Zr-Si molar ratio Polymer conversion rate / % Methyl ketone yield / % Example 1 1:2 91.4 80.6 Example 2 1:3 92.3 82.3 Example 3 1:4 93.5 83.9 Example 4 1:5 92.3 77.6 Example 5 1:6 91.1 76.1 Example 6 1:7 90.8 75.5 Example 7 1:8 88.8 72.6

[0076] As shown in Table 1, the Zr-Si molar ratios of 1:2 to 1:8 all exhibit good catalytic decomposition effects on the polymers in the alkynyldiol reaction. Among them, the catalyst with a Zr-Si molar ratio of 1:4 shows better catalytic decomposition effects on the polymers in the alkynyldiol reaction. Therefore, a Zr-Si molar ratio of 1:4 is selected as the optimal value.

[0077] Test Example 2

[0078] According to the technical solution described in Test Example 1, the solid acid catalysts obtained in Examples 3 and 8-11 were used to catalytically decompose the polymer in the acetylacetonate reaction. The resulting initial product was detected by liquid chromatography, and the detection results are shown in Table 2.

[0079] Table 2 Effect of N-methylpyrrolidone dosage on polymer catalytic decomposition in the acetylenide reaction.

[0080]

[0081]

[0082] As shown in Table 2, N-methylpyrrolidone can effectively catalyze the decomposition of polymers in the acetylenic diol reaction when the dosage is between 1% and 5%. Among them, when the proportion of N-methylpyrrolidone is 2%, the catalyst prepared has a better effect on the catalytic decomposition of polymers in the acetylenic diol reaction. Therefore, the effect is best when the proportion of N-methylpyrrolidone is 2%.

[0083] Test Example 3

[0084] According to the technical solution described in Test Example 1, the solid acid catalysts obtained in Examples 9 and 12-16 were used to catalytically decompose the polymer in the reaction of acetylacetonate diol. The resulting primary product was detected by liquid chromatography, and the detection results are shown in Table 3.

[0085] Table 3 Effect of pH on polymer catalytic decomposition in the acetylacetonate reaction

[0086] pH Polymer conversion rate / % Methyl ketone yield / % Example 12 8 94.6 84.3 Example 13 9 96.7 86.5 Example 9 10 97.6 89.4 Example 14 11 95.3 87.7 Example 15 12 90.2 83.3 Example 16 13 88.3 78.3

[0087] As shown in Table 3, the catalyst can effectively catalyze the decomposition of polymers in the acetylenic diol reaction at pH values ​​ranging from 8 to 13. Among these, the catalyst with a pH of 10 exhibits the best catalytic decomposition effect on polymers in the acetylenic diol reaction, thus pH 10 is the optimal choice.

[0088] Test Example 4

[0089] According to the technical solution described in Test Example 1, the solid acid catalysts obtained in Examples 9 and 17-22 were used to catalytically decompose the polymer in the reaction of acetylacetonate diol. The resulting primary product was detected by liquid chromatography, and the detection results are shown in Table 4.

[0090] Table 4. Effect of aging time on polymer catalytic decomposition in the acetylacetonate reaction.

[0091]

[0092]

[0093] As shown in Table 4, aging times of 6–12 h can all have a good catalytic decomposition effect on the polymer in the acetylenic diol reaction. Among them, when the aging time is 8 h, the catalyst prepared has a better catalytic decomposition effect on the polymer in the acetylenic diol reaction. Therefore, the best effect is achieved when the aging time is 8 h.

[0094] Test Example 5

[0095] According to the technical solution described in Test Example 1, the solid acid catalysts obtained in Examples 9 and 23-27 were used to catalytically decompose the polymer in the reaction of acetylacetonate diol. The resulting primary product was detected by liquid chromatography, and the detection results are shown in Table 5.

[0096] Table 5. Effect of calcination temperature on the polymer catalytic decomposition in the acetylacetonate reaction.

[0097] Calcination temperature / °C Polymer conversion rate / % Methyl ketone yield / % Example 23 300 82.5 77.6 Example 24 400 88.4 83.5 Example 9 500 97.6 89.4 Example 25 600 86.4 86.7 Example 26 700 74.2 82.2 Example 27 800 66.8 73.2

[0098] As shown in Table 5, calcination temperatures ranging from 300 to 800℃ can all effectively catalyze the decomposition of polymers in the acetylenic diol reaction. Among these, the catalyst prepared at a calcination temperature of 500℃ exhibits the best catalytic decomposition effect on polymers in the acetylenic diol reaction. Therefore, a calcination temperature of 500℃ is selected as the optimal temperature.

[0099] Test Example 6

[0100] According to the technical solution described in Test Example 1, the solid acid catalysts obtained in Examples 9 and 28-32 were used to catalytically decompose the polymer in the acetylenic diol reaction. The resulting primary product was detected by liquid chromatography, and the detection results are shown in Table 6.

[0101] Table 6. Effect of calcination time on polymer catalytic decomposition in the acetylacetonate reaction.

[0102]

[0103]

[0104] As shown in Table 6, calcination times of 3–8 h can all achieve good catalytic decomposition of polymers in the acetylenic diol reaction. Among them, when the calcination time is 5 h, the catalyst prepared has a better catalytic decomposition effect on polymers in the acetylenic diol reaction. Therefore, the best effect is achieved when the calcination time is 5 h.

[0105] Test Example 7

[0106] According to the technical solution described in Test Example 1, the solid acid catalysts obtained in Examples 9 and 33-37 were used to catalytically decompose the polymer in the acetylacetonate reaction. The resulting primary product was detected by liquid chromatography, and the detection results are shown in Table 7.

[0107] Table 7. Effect of sulfuric acid aqueous solution concentration on polymer catalytic decomposition in the acetylenol reaction.

[0108] sulfuric acid aqueous solution concentration / mol / L Polymer conversion rate / % Methyl ketone yield / % Example 33 0.5 81.3 79.6 Example 34 1 89.5 83.2 Example 9 1.5 97.6 89.4 Example 35 2 96.3 82.4 Example 36 2.5 93.1 79.6 Example 37 3 88.3 73.1

[0109] As shown in Table 7, sulfuric acid aqueous solution concentrations of 0.5–3 mol / L can all exhibit good catalytic decomposition effects on polymers in the acetylenic diol reaction. Among them, when the sulfuric acid aqueous solution concentration is 1.5 mol / L, the prepared catalyst has a better catalytic decomposition effect on polymers in the acetylenic diol reaction. Therefore, the effect is best when the sulfuric acid aqueous solution concentration is 1.5 mol / L.

[0110] Test Example 8

[0111] According to the technical solution described in Test Example 1, the solid acid catalysts obtained in Examples 9 and 38-41 were used to catalytically decompose the polymer in the reaction of acetylacetonate diol. The resulting primary product was detected by liquid chromatography, and the detection results are shown in Table 8.

[0112] Table 8 Effect of immersion time on polymer catalytic decomposition in the acetylacetonate reaction.

[0113]

[0114]

[0115] As shown in Table 8, impregnation times of 8–16 h can all achieve good catalytic decomposition of polymers in the acetylenic diol reaction. Among them, when the impregnation time is 12 h, the prepared catalyst has a better catalytic decomposition effect on polymers in the acetylenic diol reaction. Therefore, the optimal impregnation time is 12 h.

[0116] Test Example 9

[0117] According to the technical solution described in Test Example 1, the solid acid catalysts obtained in Examples 9 and 42-45 were used to catalytically decompose the polymer in the reaction of acetylacetonate diol. The resulting primary product was detected by liquid chromatography, and the detection results are shown in Table 9.

[0118] Table 9. Effect of calcination temperature on polymer catalytic decomposition in the acetylacetonate reaction.

[0119] Calcination temperature / °C Polymer conversion rate / % Methyl ketone yield / % Example 42 100 83.1 79.6 Example 9 150 97.6 89.4 Example 43 200 91.3 82.6 Example 44 250 89.6 81.5 Example 45 300 82.3 77.9

[0120] As shown in Table 9, calcination temperatures ranging from 100 to 300°C can all effectively catalyze the decomposition of polymers in the acetylenic diol reaction. Among these, the catalyst prepared at a calcination temperature of 150°C exhibits the best catalytic decomposition effect on polymers in the acetylenic diol reaction. Therefore, a calcination temperature of 150°C is selected as the optimal temperature.

[0121] Test Case 10

[0122] According to the technical solution described in Test Example 1, the solid acid catalysts obtained in Examples 9 and 46-49 were used to catalytically decompose the polymer in the reaction of acetylacetonate diol. The resulting primary product was detected by liquid chromatography, and the detection results are shown in Table 10.

[0123] Table 10 Effect of calcination time on polymer catalytic decomposition in the acetylacetonate reaction

[0124] Calcination time / h Polymer conversion rate / % Methyl ketone yield / % Example 46 4 95.5 82.6 Example 9 6 97.6 89.4 Example 47 8 96.1 83.7 Example 48 10 91.3 81.6 Example 49 12 86.4 80.8

[0125] As shown in Table 10, calcination times of 4–12 h can all achieve good catalytic decomposition of polymers in the acetylenic diol reaction. Among them, when the calcination time is 6 h, the catalyst prepared has a better catalytic decomposition effect on polymers in the acetylenic diol reaction. Therefore, the best effect is achieved when the calcination time is 6 h.

[0126] Test Example 11

[0127] According to the technical solution described in Test Example 1, the solid acid catalyst obtained in Example 9, the ZrO2-SiO2 catalyst, and the catalyst-free method were used to catalytically decompose the polymer in the reaction of acetylacetonate diol. The resulting initial product was detected by liquid chromatography, and the detection results are shown in Table 11.

[0128] Table 11 Effect of catalysts on polymer catalytic decomposition in the reaction of acetylgyndiol

[0129] Catalyst categories Polymer conversion rate / % Methyl ketone yield / % solid acid catalysts 97.6 89.4 <![CDATA[ZrO2-SiO2 catalyst]]> 16.8 10.1 Catalyst-free 2 1.3

[0130] As can be seen from Table 11, when the solid acid catalyst prepared by the present invention is used, the catalyst is more effective in catalytically decomposing the polymer in the reaction of acetylenic diol. Therefore, the solid acid catalyst of the present invention has a better catalytic effect.

[0131] Although the above embodiments have provided a detailed description of the present invention, they are only some embodiments of the present invention, and not all embodiments. People can obtain other embodiments based on these embodiments without creative effort, and these embodiments all fall within the protection scope of the present invention.

Claims

1. The application of a solid acid catalyst in the catalytic decomposition of polymers obtained from the condensation of methyl ketone aldol; the method for preparing the solid acid catalyst, characterized in that, Includes the following steps: A zirconium oxychloride solution was mixed with N-methylpyrrolidone, and ammonia and silica sol were added dropwise. The mixture was then aged and calcined sequentially to obtain a ZrO2-SiO2 support. The mass of the N-methylpyrrolidone was 1-5% of the mass of the zirconium oxychloride solution. The Zr-Si molar ratio in the ZrO2-SiO2 support was 1:2-8. The ZrO2-SiO2 support is mixed with sulfuric acid solution, and then impregnated and calcined sequentially to obtain the solid acid catalyst; the calcination temperature is 100~300℃.

2. The application according to claim 1, characterized in that, The concentration of zirconium oxychloride in the zirconium oxychloride solution is 0.1~1 mol / L.

3. The application according to claim 1, characterized in that, The aging time is 6-12 hours, and the pH value is 8-13.

4. The application according to claim 1, characterized in that, The calcination temperature is 300~800℃, and the time is 3~8h.

5. The application according to claim 1, characterized in that, The concentration of the sulfuric acid solution is 0.5~3 mol / L; The soaking time is 8 to 16 hours.

6. The application according to claim 1, characterized in that, The roasting time is 4 to 10 hours.

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