Production process of antioxidant 330

Abstract

The present invention relates to the field of antioxidant production technology, and in particular to a production process for antioxidant 330. The production process comprises the following steps: adding dichloromethane, mesitylene and a solid acid catalyst into a reactor and mixing and stirring evenly, then dropping a dichloromethane solution of 3,5-di-tert-butyl-4-hydroxybenzyl methyl ether at room temperature; S2, heating the reactor after completion of the dropwise addition and continuing the reaction, and obtaining a reaction completion liquid after completion of the reaction; S3, filtering and separating the solid acid catalyst and a crude organic phase from the reaction completion liquid, and refining the crude organic phase to obtain antioxidant 330. The present invention extends the service life of equipment, improves reaction efficiency and the yield and purity of antioxidant 330, and the solid acid catalyst is easy to separate and recycle, has little environmental pollution, and has a long service life.

Description

Technical Field

[0001] The present invention relates to the technical field of antioxidant production, and in particular to a production process of antioxidant 330. Background Art

[0002] Antioxidant 330 is an antioxidant widely used in rubber, plastics, lubricants, and other fields. It effectively prevents oxidation-related performance degradation during processing, storage, and use. The current mainstream industrial production method for antioxidant 330 involves reacting 2,6-di-tert-butylphenol with an excess of paraformaldehyde in the presence of an alkaline catalyst to produce 3,5-di-tert-butyl-4-hydroxybenzyl methyl ether (benzyl ether). This ether is then reacted with mesitylene to produce antioxidant 330. Existing techniques often use concentrated sulfuric acid as a catalyst for the reaction between benzyl ether and mesitylene. This sulfuric acid is added dropwise to the reaction system to catalyze the reaction. This requires a significant excess of benzyl ether and produces a large amount of antioxidant 702, reducing economic efficiency. Furthermore, this method suffers from long reaction times, low product yield and purity, complex post-processing, and environmental pollution.

[0003] The invention patent with authorization announcement number CN108503512B discloses a method for synthesizing antioxidant 330 using a novel catalyst. A ferroferric oxide-molecular sieve-supported phosphoric acid catalyst is prepared. In the presence of the ferroferric oxide-molecular sieve-supported phosphoric acid catalyst, 3,5-di-tert-butyl-4-hydroxybenzyl ether and mesitylene are reacted to produce antioxidant 330. In this synthesis process, the catalyst is easy to separate and recover, and post-processing is simple. However, the catalytic efficiency of the catalyst and the yield and purity of the antioxidant 330 prepared using the catalyst need to be improved.

[0004] In summary, there is an urgent need to provide a production process for antioxidant 330 that is non-corrosive to equipment, has high catalytic efficiency, is easy to separate and recover the catalyst, has little environmental pollution, has a long service life, and can obtain high yield and high purity. Summary of the Invention

[0005] To solve at least one of the above problems, the present invention provides a production process of an antioxidant 330, comprising the following steps:

[0006] S1, adding dichloromethane, mesitylene and a solid acid catalyst into a reaction kettle and mixing them evenly, then adding dropwise a dichloromethane solution of 3,5-di-tert-butyl-4-hydroxybenzyl methyl ether at room temperature; the solid acid catalyst comprises aminosulfonic acid / ZSM-5 molecular sieve and sulfated zirconium oxide / ZSM-5 molecular sieve in a mass ratio of 1:(1-2); the aminosulfonic acid content in the aminosulfonic acid / ZSM-5 molecular sieve is 20-40wt%, and the sulfated zirconium oxide content in the sulfated zirconium oxide / ZSM-5 molecular sieve is 15-35wt%;

[0007] S2, after the dropwise addition is completed, the reactor is heated to continue the reaction, and a reaction complete liquid is obtained after the reaction is completed;

[0008] S3, filtering and separating the solid acid catalyst and the crude organic phase from the reaction completed liquid, and refining the crude organic phase to obtain the antioxidant 330.

[0009] In the above technical solution, the reaction system adopts a solid acid catalyst to replace the traditional concentrated sulfuric acid catalyst, which avoids the corrosion of concentrated sulfuric acid on the equipment and the pollution to the environment, greatly improves the service life of the equipment, is green and environmentally friendly, and the solid acid catalyst is composed of aminosulfonic acid / ZSM-5 molecular sieve and sulfated zirconium oxide / ZSM-5 molecular sieve. The aminosulfonic acid, sulfated zirconium oxide and ZSM-5 molecular sieve work synergistically to greatly improve the reaction efficiency, improve the yield and purity of the antioxidant 330, and the solid acid catalyst has a long service life, is easy to separate and recover, has a simple post-processing, and improves production efficiency. The present invention adopts a feeding method of dropwise adding a dichloromethane solution of 3,5-di-tert-butyl-4-hydroxybenzyl methyl ether. According to the formula, the molar ratio of mesitylene to 3,5-di-tert-butyl-4-hydroxybenzyl methyl ether in the reaction can be reduced to 1:(3.1-3.5). In the prior art, when the reaction is carried out by dropwise addition of concentrated sulfuric acid, the molar ratio of mesitylene to 3,5-di-tert-butyl-4-hydroxybenzyl methyl ether is 1:3.9. The present invention not only greatly reduces the amount of 3,5-di-tert-butyl-4-hydroxybenzyl methyl ether used and improves the yield of antioxidant 330, but also reduces the purity requirement for 3,5-di-tert-butyl-4-hydroxybenzyl methyl ether. Using 3,5-di-tert-butyl-4-hydroxybenzyl methyl ether with a purity of 92-98% can achieve better reaction results and increase atom utilization.

[0010] Preferably, in step S1, the dropwise addition time is 1 to 2 hours; in step S2, the reaction temperature is 40 to 45° C., and the reaction time is 1 to 3 hours; in step S3, the refining includes: adding n-heptane to the crude organic phase, distilling and displacing the dichloromethane to obtain a displaced organic phase, cooling the displaced organic phase for crystallization, filtering the precipitated crystals, eluting with methanol, and finally drying to obtain antioxidant 330; the distillation temperature is 60 to 80° C., the mass of the added n-heptane is 1.5 to 3 times the mass of the crude organic phase; the crystallization temperature is 10 to 15° C., and the crystallization time is 1 to 1.5 hours.

[0011] In the above technical solution, since a solid acid catalyst is used instead of concentrated sulfuric acid, there is no need to neutralize the crude organic phase to remove residual concentrated sulfuric acid, the post-processing efficiency is greatly improved, and environmental pollution is also avoided; in the prior art, when the crude organic phase is refined, dichloromethane is first distilled off to obtain a concentrated crude organic phase, and then n-heptane is added to the concentrated crude organic phase, which is heated to reflux for a certain period of time and then cooled to room temperature for crystallization. The process steps are many and the production efficiency is low. In the present invention, n-heptane is first added to the crude organic phase, and then the dichloromethane is displaced by distillation to obtain a displaced organic phase, and then the displaced organic phase is cooled for crystallization. The process steps are few and the production efficiency is high; the precipitated crystals are rinsed with methanol to remove trace impurities remaining in the crystals, thereby further improving the purity of the antioxidant 330.

[0012] Preferably, in step S1, the mass ratio of dichloromethane, solid acid catalyst, mesitylene and 3,5-di-tert-butyl-4-hydroxybenzyl methyl ether is (450-550): (5-10):12: (78-88); the concentration of the dichloromethane solution of 3,5-di-tert-butyl-4-hydroxybenzyl methyl ether is (15-20) wt%.

[0013] Preferably, in step S1, the ZSM-5 molecular sieve in the aminosulfonic acid / ZSM-5 molecular sieve and the sulfated zirconium oxide / ZSM-5 molecular sieve is pretreated, and the pretreatment comprises: uniformly mixing the ZSM-5 molecular sieve with a urea aqueous solution having a concentration of (5-10) wt%, heating to 80-100° C. for reflux reaction for 5-10 hours under stirring, and after the reaction is completed, filtering, washing, drying at 110° C., and calcining at 550° C. for 6 hours to obtain the pretreated ZSM-5 molecular sieve; the mass ratio of the ZSM molecular sieve to the urea aqueous solution is 1:(100-200).

[0014] In the above technical solution, the ZSM-5 molecular sieve is desiliconized using ammonia generated in situ by hydrolysis of urea aqueous solution as an alkali source, thereby obtaining a ZSM-5 molecular sieve with multi-level pores, thereby improving the loading capacity and catalytic performance of ZSM-5.

[0015] Preferably, in step S1, the preparation of the aminosulfonic acid / ZSM-5 molecular sieve comprises the following steps: uniformly mixing urea, ethanol and ZSM-5 molecular sieve in a mass ratio of 2: (20-50): (5-10), stirring at 55-65° C. for 1-2 hours, then removing ethanol by reduced pressure distillation under stirring, and drying at 100-110° C. for 1-2 hours to obtain urea / ZSM-5 molecular sieve; adding urea / ZSM-5 molecular sieve to 65% fuming sulfuric acid in a molar ratio of urea to sulfuric acid of 1: (1.2-1.5), mixing and stirring uniformly, reacting at 40-45° C. for 12-15 hours, cooling to room temperature after the reaction, crystallizing, filtering the crystals and drying at 100-120° C. for 4-5 hours to obtain aminosulfonic acid / ZSM-5 molecular sieve.

[0016] In the above technical solution, urea is dissolved in ethanol to form an ethanol solution of urea. Heating and stirring can not only increase the solubility of urea in ethanol, but also increase the penetration rate of urea into the internal pores of the ZSM-5 molecular sieve, thereby obtaining a uniformly dispersed urea / ZSM-5 molecular sieve. Finally, the urea / ZSM-5 molecular sieve is sulfonated with 65% fuming sulfuric acid to obtain a uniformly dispersed aminosulfonic acid / ZSM-5 molecular sieve.

[0017] Preferably, in step S1, the preparation of sulfated zirconium oxide / ZSM-5 molecular sieve comprises the following steps: uniformly mixing zirconium oxychloride, ethanol and ZSM-5 molecular sieve in a mass ratio of 2: (20-50): (5-10), stirring at 55-65°C for 1-2 hours, then removing ethanol by reduced pressure distillation under stirring, drying at 100-110°C for 1-2 hours, and then calcining at 350-550°C for 4-6 hours to obtain zirconium oxide / ZSM-5 molecular sieve, impregnating the zirconium oxide / ZSM-5 molecular sieve in a 0.4-0.6 mol / L sulfuric acid solution in a mass ratio of 1: (100-200), stirring for 25-35 minutes, filtering, and drying at 150-200°C for 3-4 hours to obtain sulfated zirconium oxide / ZSM-5 molecular sieve.

[0018] In the above technical solution, zirconium oxychloride is dissolved in ethanol to form an ethanol solution of zirconium oxychloride. Heating and stirring can not only increase the solubility of zirconium oxychloride in ethanol, but also increase the penetration rate of zirconium oxychloride into the internal pores of the ZSM-5 molecular sieve, thereby obtaining a uniformly dispersed zirconium oxychloride / ZSM-5 molecular sieve. After the zirconium oxychloride / ZSM-5 molecular sieve is calcined, a uniformly dispersed zirconium oxide / ZSM-5 molecular sieve is obtained. Finally, the zirconium oxide / ZSM-5 molecular sieve is reacted with sulfuric acid to obtain a uniformly dispersed sulfated zirconium oxide / ZSM-5 molecular sieve.

[0019] Preferably, in step S1, the solid acid catalyst is in the shape of a hollow strip, the inner layer is sulfamic acid / ZSM-5 molecular sieve, the outer layer is sulfated zirconium oxide / ZSM-5 molecular sieve, the length of the catalyst is 10 to 30 mm, the inner layer thickness is 1 to 3 mm, and the outer layer thickness is 1 to 3 mm.

[0020] In the above technical solution, the solid acid catalyst is prepared into a hollow strip, which is conducive to the filtration and separation of the solid acid catalyst. The sulfated zirconium oxide / ZSM-5 molecular sieve of the outer layer of the solid acid catalyst can improve the compressive strength and wear resistance of the solid acid catalyst. The inner layer of the aminosulfonic acid / ZSM-5 molecular sieve has a hollow structure, which can increase the contact area between the aminosulfonic acid / ZSM-5 molecular sieve and the reaction material, thereby improving the catalytic efficiency.

[0021] Preferably, the inner sidewall of the inner layer is corrugated, and the outer sidewall of the outer layer is corrugated. In the above technical solution, the inner and outer sidewalls of the solid acid catalyst are both corrugated, which can increase the specific surface area of ​​the sulfated zirconium oxide / ZSM-5 molecular sieve and the aminosulfonic acid / ZSM-5 molecular sieve, further improving the catalytic effect.

[0022] Preferably, the preparation of the hollow strip-shaped solid acid catalyst comprises the following steps:

[0023] S11, mixing sulfamic acid / ZSM-5 molecular sieve and aluminum sol to obtain an inner layer extrudate;

[0024] S12, mixing the sulfated zirconium oxide / ZSM-5 molecular sieve and the aluminum sol to obtain an outer layer extrudate;

[0025] S13, placing the inner layer extrudate and the outer layer extrudate into an extruder, extruding, and drying to obtain a hollow strip-shaped solid acid catalyst.

[0026] In the above technical solution, by adjusting the shape of the extruder head, a hollow strip-shaped solid acid catalyst with smooth inner and outer sidewalls and a hollow strip-shaped solid acid catalyst with corrugated inner and outer sidewalls can be obtained.

[0027] Preferably, in step S11, the mass ratio of sulfamic acid / ZSM-5 molecular sieve to aluminum sol is 100:(40-50), and the solid content of aluminum sol is 20wt%; in step S12, the mass ratio of sulfated zirconium oxide / ZSM-5 molecular sieve to aluminum sol is 100:(40-50), and the solid content of aluminum sol is 20wt%; in step S13, the drying temperature is 120-160°C, and the drying time is 2-3h.

[0028] Compared with the prior art, the present invention has the following beneficial technical effects:

[0029] 1. The present invention adopts solid acid catalyst for catalysis, which avoids corrosion to equipment and pollution to the environment and improves post-processing efficiency;

[0030] 2. The solid acid catalyst is composed of sulfamic acid / ZSM-5 molecular sieve and sulfated zirconium oxide / ZSM-5 molecular sieve. The synergistic effect of sulfamic acid, sulfated zirconium oxide, and ZSM-5 molecular sieve can significantly improve the reaction efficiency and increase the yield and purity of antioxidant 330. In addition, the solid acid catalyst has a long service life, is easy to separate and recover, and has simple post-processing, making it environmentally friendly.

[0031] 3. The present invention adopts a method of adding a dichloromethane solution of 3,5-di-tert-butyl-4-hydroxybenzyl methyl ether dropwise, which not only greatly reduces the amount of 3,5-di-tert-butyl-4-hydroxybenzyl methyl ether used and improves the yield of antioxidant 330, but also reduces the purity requirement for 3,5-di-tert-butyl-4-hydroxybenzyl methyl ether. Using 3,5-di-tert-butyl-4-hydroxybenzyl methyl ether with a purity of 92-98% can achieve better reaction results and increase atom utilization;

[0032] 4. The solid acid catalyst is prepared into a hollow strip shape, with an inner layer of sulfamic acid / ZSM-5 molecular sieve and an outer layer of sulfated zirconium oxide / ZSM-5 molecular sieve. The hollow strip-shaped solid acid catalyst is easier to filter and separate. The sulfated zirconium oxide / ZSM-5 molecular sieve on the outer layer of the solid acid catalyst can improve the compressive strength and wear resistance of the solid acid catalyst. The hollow structure of the sulfamic acid / ZSM-5 molecular sieve on the inner layer can increase the contact area between the sulfamic acid / ZSM-5 molecular sieve and the reaction materials, thereby improving the catalytic efficiency.

[0033] 5. The inner and outer walls of the hollow strip-shaped solid acid catalyst are both corrugated, which can increase the specific surface area of ​​sulfated zirconia / ZSM-5 molecular sieve and sulfamic acid / ZSM-5 molecular sieve, further improving the catalytic effect;

[0034] In summary, the present invention adopts a solid acid catalyst for catalysis, avoids equipment corrosion, and extends the service life of the equipment. The feeding method adopts the method of dropwise adding a dichloromethane solution of 3,5-di-tert-butyl-4-hydroxybenzyl methyl ether, which reduces the amount of 3,5-di-tert-butyl-4-hydroxybenzyl methyl ether, improves the reaction efficiency and the yield and purity of the antioxidant 330. The solid acid catalyst is easy to separate and recycle, has little environmental pollution, and has a long service life. DETAILED DESCRIPTION

[0035] In order to more clearly understand the above-mentioned objects, features and advantages of the present invention, the present invention is further described in detail below in conjunction with specific embodiments. It should be noted that, in the absence of conflict, the embodiments of the present application and the features therein can be combined with each other.

[0036] In the following description, many specific details are set forth to facilitate a full understanding of the present invention. However, the present invention may also be implemented in other ways different from those described herein. Therefore, the scope of protection of the present invention is not limited to the specific embodiments disclosed below.

[0037] Example 1-1

[0038] In this embodiment, solid acid catalyst A is prepared, comprising the following steps:

[0039] Urea, ethanol and ZSM-5 molecular sieve were uniformly mixed in a mass ratio of 2:20:5, stirred at 60°C for 1.5 hours, and then ethanol was distilled off under reduced pressure under stirring. The mixture was dried at 100°C for 1 hour to obtain urea / ZSM-5 molecular sieve. Urea / ZSM-5 molecular sieve was added to 65% fuming sulfuric acid in three times at a molar ratio of urea to sulfuric acid of 1:1.5, mixed and stirred uniformly, reacted at 40°C for 15 hours, cooled to room temperature after the reaction, crystallized, filtered the crystals, and dried at 100°C for 5 hours to obtain aminosulfonic acid / ZSM-5 molecular sieve with an aminosulfonic acid content of 31wt%.

[0040] Zirconium oxychloride, ethanol and ZSM-5 molecular sieve were uniformly mixed in a mass ratio of 2:20:5, stirred at 60°C for 1.5 hours, and then ethanol was removed by reduced pressure distillation under stirring. The mixture was dried at 100°C for 1 hour and then calcined at 450°C for 5 hours to obtain zirconium oxide / ZSM-5 molecular sieve. The zirconium oxide / ZSM-5 molecular sieve was immersed in a 0.6 mol / L sulfuric acid solution in a mass ratio of 1:100, stirred for 35 minutes, filtered, and dried at 200°C for 3 hours to obtain sulfated zirconium oxide / ZSM-5 molecular sieve, wherein the content of sulfated zirconium oxide was 25 wt%.

[0041] The sulfamic acid / ZSM-5 molecular sieve and the sulfated zirconium oxide / ZSM-5 molecular sieve were uniformly mixed in a mass ratio of 1:2 to obtain a solid acid catalyst A.

[0042] Example 1-2

[0043] In this embodiment, solid acid catalyst B is prepared, comprising the following steps:

[0044] The ZSM-5 molecular sieve was evenly mixed with a 5wt% urea aqueous solution in a mass ratio of 1:100, and heated to 90°C for reflux reaction for 6 hours under stirring. After the reaction, the mixture was filtered, washed with water, dried at 110°C for 2 hours, and calcined at 550°C for 6 hours to obtain a pretreated ZSM-5 molecular sieve.

[0045] Urea, ethanol and pretreated ZSM-5 molecular sieve were uniformly mixed in a mass ratio of 2:20:5, stirred at 60°C for 1.5 hours, and then ethanol was removed by reduced pressure distillation under stirring. The mixture was dried at 100°C for 1 hour to obtain urea / ZSM-5 molecular sieve. Urea / ZSM-5 molecular sieve was added to 65% fuming sulfuric acid in three times at a molar ratio of urea to sulfuric acid of 1:1.5, mixed and stirred uniformly, reacted at 40°C for 15 hours, cooled to room temperature after the reaction, crystallized, filtered the crystals and dried at 100°C for 5 hours to obtain aminosulfonic acid / ZSM-5 molecular sieve with a sulfamic acid content of 34wt%.

[0046] Zirconium oxychloride, ethanol and pretreated ZSM-5 molecular sieve were uniformly mixed in a mass ratio of 2:20:5, stirred at 60°C for 1.5 hours, and then ethanol was removed by reduced pressure distillation under stirring. The mixture was dried at 100°C for 1 hour and then calcined at 450°C for 5 hours to obtain zirconium oxide / ZSM-5 molecular sieve. The zirconium oxide / ZSM-5 molecular sieve was immersed in a 0.6 mol / L sulfuric acid solution in a mass ratio of 1:100, stirred for 35 minutes, filtered, and dried at 200°C for 3 hours to obtain sulfated zirconium oxide / ZSM-5 molecular sieve, with a sulfated zirconium oxide content of 28 wt%.

[0047] The sulfamic acid / ZSM-5 molecular sieve and the sulfated zirconium oxide / ZSM-5 molecular sieve were uniformly mixed in a mass ratio of 1:2 to obtain a solid acid catalyst B.

[0048] Examples 1-3

[0049] In this embodiment, solid acid catalyst C is prepared, comprising the following steps:

[0050] The ZSM-5 molecular sieve was evenly mixed with a 10wt% urea aqueous solution in a mass ratio of 1:200, and heated to 90°C for reflux reaction for 6 hours under stirring. After the reaction, the mixture was filtered, washed with water, dried at 110°C for 2 hours, and calcined at 550°C for 6 hours to obtain a pretreated ZSM-5 molecular sieve.

[0051] Urea, ethanol and pretreated ZSM-5 molecular sieve were uniformly mixed in a mass ratio of 2:20:5, stirred at 60°C for 1.5 hours, and then ethanol was removed by reduced pressure distillation under stirring. The mixture was dried at 100°C for 1 hour to obtain urea / ZSM-5 molecular sieve. Urea / ZSM-5 molecular sieve was added to 65% fuming sulfuric acid in three times at a molar ratio of urea to sulfuric acid of 1:1.5, mixed and stirred uniformly, reacted at 40°C for 15 hours, cooled to room temperature after the reaction, crystallized, filtered the crystals and dried at 100°C for 5 hours to obtain sulfamic acid / ZSM-5 molecular sieve with a sulfamic acid content of 36wt%.

[0052] Zirconium oxychloride, ethanol and pretreated ZSM-5 molecular sieve were uniformly mixed in a mass ratio of 2:20:5, stirred at 60°C for 1.5 hours, and then the ethanol was removed by reduced pressure distillation under stirring. The mixture was dried at 100°C for 1 hour and then calcined at 450°C for 5 hours to obtain zirconium oxide / ZSM-5 molecular sieve. The zirconium oxide / ZSM-5 molecular sieve was immersed in a 0.6 mol / L sulfuric acid solution in a mass ratio of 1:100, stirred for 35 minutes, filtered, and dried at 200°C for 3 hours to obtain sulfated zirconium oxide / ZSM-5 molecular sieve, wherein the content of sulfated zirconium oxide was 30 wt%.

[0053] The sulfamic acid / ZSM-5 molecular sieve and the sulfated zirconium oxide / ZSM-5 molecular sieve were uniformly mixed in a mass ratio of 1:2 to obtain a solid acid catalyst C.

[0054] Examples 1-4

[0055] In this example, solid acid catalyst D was prepared, comprising the following steps:

[0056] The ZSM-5 molecular sieve was evenly mixed with a 10wt% urea aqueous solution in a mass ratio of 1:200, and heated to 90°C for reflux reaction for 6 hours under stirring. After the reaction, the mixture was filtered, washed with water, dried at 110°C for 2 hours, and calcined at 550°C for 6 hours to obtain a pretreated ZSM-5 molecular sieve.

[0057] Urea, ethanol and pretreated ZSM-5 molecular sieve were mixed uniformly in a mass ratio of 2:20:10, stirred at 60°C for 1.5 hours, and then ethanol was distilled off under reduced pressure under stirring. The mixture was dried at 100°C for 1 hour to obtain urea / ZSM-5 molecular sieve. Urea / ZSM-5 molecular sieve was added to 65% fuming sulfuric acid in three times at a molar ratio of urea to sulfuric acid of 1:1.5, mixed and stirred uniformly, reacted at 40°C for 15 hours, cooled to room temperature after the reaction, crystallized, filtered the crystals, and dried at 100°C for 5 hours to obtain sulfamic acid / ZSM-5 molecular sieve with a sulfamic acid content of 21wt%.

[0058] Zirconium oxychloride, ethanol and pretreated ZSM-5 molecular sieve were uniformly mixed in a mass ratio of 2:20:10, stirred at 60°C for 1.5 hours, and then the ethanol was removed by reduced pressure distillation under stirring. The mixture was dried at 100°C for 1 hour and then calcined at 450°C for 5 hours to obtain zirconium oxide / ZSM-5 molecular sieve. The zirconium oxide / ZSM-5 molecular sieve was immersed in a 0.6 mol / L sulfuric acid solution in a mass ratio of 1:100, stirred for 35 minutes, filtered, and dried at 200°C for 3 hours to obtain sulfated zirconium oxide / ZSM-5 molecular sieve, with the content of sulfated zirconium oxide being 18 wt%.

[0059] The sulfamic acid / ZSM-5 molecular sieve and the sulfated zirconium oxide / ZSM-5 molecular sieve were uniformly mixed in a mass ratio of 1:2 to obtain a solid acid catalyst D.

[0060] Examples 1-5

[0061] In this example, solid acid catalyst E was prepared. Based on Examples 1-3, sulfamic acid / ZSM-5 molecular sieve and sulfated zirconium oxide / ZSM-5 molecular sieve were uniformly mixed in a mass ratio of 1:1 to obtain solid acid catalyst E.

[0062] Examples 1-6

[0063] This example prepares a hollow strip-shaped solid acid catalyst F, comprising the following steps:

[0064] The sulfamic acid / ZSM-5 molecular sieve in Example 1-3 and the aluminum sol with a solid content of 20 wt% were mixed and stirred at a mass ratio of 100:40 to obtain an inner layer extrudate;

[0065] The sulfated zirconium oxide / ZSM-5 molecular sieve in Example 1-3 and the aluminum sol with a solid content of 20 wt % were mixed and stirred at a mass ratio of 100:40 to obtain an outer layer extrudate;

[0066] The inner layer extrudate and the outer layer extrudate were placed into an extruder at a mass ratio of 1:2 and extruded, and dried at 120°C for 3 hours to obtain a hollow strip of solid acid catalyst F. The solid acid catalyst F had a length of 10 mm, an inner layer thickness of 2.5 mm, and an outer layer thickness of 3 mm.

[0067] Examples 1-7

[0068] In this example, a hollow strip-shaped solid acid catalyst G was prepared. Based on Examples 1-6, the inner layer extrudate and the outer layer extrudate were placed in an extruder at a mass ratio of 1:1.5 and extruded. The extrudates were dried at 120°C for 3 hours to obtain a hollow strip-shaped solid acid catalyst G. The solid acid catalyst G had a length of 10 mm, an inner layer thickness of 3 mm, and an outer layer thickness of 2 mm.

[0069] Examples 1-8

[0070] In this example, a hollow strip-shaped solid acid catalyst H was prepared. Based on Examples 1-6, the inner layer extrudate and the outer layer extrudate were placed in an extruder at a mass ratio of 1:1 and extruded. The extrudates were dried at 120°C for 3 hours to obtain a hollow strip-shaped solid acid catalyst H. The solid acid catalyst H had a length of 10 mm, an inner layer thickness of 2 mm, and an outer layer thickness of 1 mm.

[0071] Examples 1-9

[0072] In this example, a hollow strip-shaped solid acid catalyst I was prepared. Based on Examples 1-6, the inner layer extrudate and the outer layer extrudate were placed in an extruder at a mass ratio of 1:2 and extruded. The extrudates were dried at 120°C for 3 hours to obtain a hollow strip-shaped solid acid catalyst I. The solid acid catalyst I had a length of 10 mm, an inner sidewall of the inner layer was corrugated, and the thickness at the inner layer trough was 2 mm. The outer sidewall of the outer layer was corrugated, and the thickness at the outer layer trough was 2 mm.

[0073] Example 2-1

[0074] This embodiment provides a production process of an antioxidant 330, comprising the following steps:

[0075] 120 parts by mass of dichloromethane, 12 parts by mass of mesitylene, and 5 parts by mass of solid acid catalyst A were added to a reaction kettle and mixed and stirred uniformly. Then, 415 parts by mass of a 20 wt% dichloromethane solution of 3,5-di-tert-butyl-4-hydroxybenzyl methyl ether was added dropwise at room temperature for 1.5 hours. 3,5-di-tert-butyl-4-hydroxybenzyl methyl ether was synthesized using a conventional route in the prior art, by reacting 2,6-di-tert-butylphenol and excess paraformaldehyde in the presence of an alkaline catalyst, and had a purity of 92%.

[0076] After the addition was complete, the reactor was heated to 45°C and the reaction was continued for 1 hour. After the reaction was complete, a reaction solution was obtained;

[0077] Solid acid catalyst A and a crude organic phase were separated by filtration from the reaction mixture, and the crude organic phase was refined to obtain antioxidant 330. The refining process included adding n-heptane in an amount twice the mass of the crude organic phase to the crude organic phase, displacing dichloromethane by distillation at 60°C to obtain a displaced organic phase, cooling the displaced organic phase to 10°C for crystallization for 1 hour, filtering the precipitated crystals, eluting with methanol, and finally drying to obtain antioxidant 330. The yield of antioxidant 330 was 89.1%, and the purity was 99.3%.

[0078] Example 2-2

[0079] This embodiment provides a production process for antioxidant 330. Based on Example 2-1, solid acid catalyst A is replaced with solid acid catalyst B. The rest is the same as Example 2-1. The yield of antioxidant 330 is 89.7% and the purity is 99.4%.

[0080] Example 2-3

[0081] This embodiment provides a production process for antioxidant 330. Based on Example 2-1, solid acid catalyst A is replaced with solid acid catalyst C. The rest is the same as Example 2-1. The yield of antioxidant 330 is 90.5% and the purity is 99.6%.

[0082] Examples 2-4

[0083] This embodiment provides a production process for antioxidant 330. Based on Example 2-1, solid acid catalyst A is replaced with solid acid catalyst D. The rest is the same as Example 2-1. The yield of antioxidant 330 is 89.1% and the purity is 99.2%.

[0084] Examples 2-5

[0085] This embodiment provides a production process for antioxidant 330. Based on Example 2-1, solid acid catalyst A is replaced with solid acid catalyst E. The rest is the same as Example 2-1. The yield of antioxidant 330 is 89.5% and the purity is 99.5%.

[0086] Examples 2-6

[0087] This embodiment provides a production process for antioxidant 330. Based on Example 2-1, solid acid catalyst A is replaced with solid acid catalyst F. The rest is the same as Example 2-1. The yield of antioxidant 330 is 90.7% and the purity is 99.6%.

[0088] Examples 2-7

[0089] This embodiment provides a production process for antioxidant 330. Based on Example 2-1, solid acid catalyst A is replaced with solid acid catalyst G. The rest is the same as Example 2-1. The yield of antioxidant 330 is 90.1% and the purity is 99.4%.

[0090] Examples 2-8

[0091] This embodiment provides a production process for antioxidant 330. Based on Example 2-1, solid acid catalyst A is replaced with solid acid catalyst H. The rest is the same as Example 2-1. The yield of antioxidant 330 is 89.8% and the purity is 99.4%.

[0092] Examples 2-9

[0093] This embodiment provides a production process for antioxidant 330. Based on Example 2-1, solid acid catalyst A is replaced with solid acid catalyst I. The remaining steps are the same as in Example 2-1. The yield of antioxidant 330 is 90.9% and the purity is 99.6%.

[0094] Example 2-10

[0095] This embodiment provides a production process of an antioxidant 330, comprising the following steps:

[0096] 150 parts by mass of dichloromethane, 12 parts by mass of mesitylene, and 10 parts by mass of solid acid catalyst I were added to a reaction kettle and mixed and stirred uniformly, and then 390 parts by mass of a 20 wt% dichloromethane solution of 3,5-di-tert-butyl-4-hydroxybenzyl methyl ether was added dropwise at room temperature for 1 hour; wherein, 3,5-di-tert-butyl-4-hydroxybenzyl methyl ether was synthesized by a conventional route in the prior art, by reacting 2,6-di-tert-butylphenol and excess paraformaldehyde in the presence of an alkaline catalyst, and had a purity of 96%;

[0097] After the addition was complete, the reactor was heated to 40°C and the reaction was continued for 3 hours. After the reaction was complete, a reaction solution was obtained;

[0098] The solid acid catalyst I and the crude organic phase were separated by filtration from the reaction mixture, and the crude organic phase was purified to obtain antioxidant 330. The purification process included adding n-heptane in an amount twice the mass of the crude organic phase to the crude organic phase, displacing the dichloromethane by distillation at 60°C to obtain a displaced organic phase, cooling the displaced organic phase to 10°C for crystallization for 1 hour, filtering the precipitated crystals, eluting with methanol, and finally drying to obtain antioxidant 330. The yield of antioxidant 330 was 91.2%, and the purity was 99.4%.

[0099] Example 2-11

[0100] This embodiment provides a production process of an antioxidant 330, comprising the following steps:

[0101] 140 parts by mass of dichloromethane, 12 parts by mass of mesitylene, and 8 parts by mass of solid acid catalyst I were added to a reaction kettle and mixed and stirred uniformly, and then 440 parts by mass of a 20 wt% dichloromethane solution of 3,5-di-tert-butyl-4-hydroxybenzyl methyl ether was added dropwise at room temperature for 1.5 hours; wherein, 3,5-di-tert-butyl-4-hydroxybenzyl methyl ether was synthesized by a conventional route in the prior art, by reacting 2,6-di-tert-butylphenol and excess paraformaldehyde in the presence of an alkaline catalyst, and had a purity of 98%;

[0102] After the addition was complete, the reactor was heated to 45°C and the reaction was continued for 1 hour. After the reaction was complete, a reaction solution was obtained;

[0103] The solid acid catalyst I and the crude organic phase were separated by filtration from the reaction mixture, and the crude organic phase was purified to obtain antioxidant 330. The purification process included adding n-heptane in an amount twice the mass of the crude organic phase to the crude organic phase, displacing the dichloromethane by distillation at 60°C to obtain a displaced organic phase, cooling the displaced organic phase to 10°C for crystallization for 1 hour, filtering the precipitated crystals, eluting with methanol, and finally drying to obtain antioxidant 330. The yield of antioxidant 330 was 91.6%, and the purity was 99.6%.

[0104] The above embodiments are preferred implementations of the present invention, but the implementation of the present invention is not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be considered equivalent replacement methods and are included in the scope of protection of the present invention.

Claims

1. A production process of antioxidant 330, characterized in that: The following steps are involved: S1, adding dichloromethane, mesitylene and a solid acid catalyst into a reaction kettle and mixing and stirring uniformly, then adding a dichloromethane solution of 3,5-di-tert-butyl-4-hydroxybenzyl methyl ether dropwise at room temperature for 1 to 2 hours; the solid acid catalyst comprises aminosulfonic acid / ZSM-5 molecular sieve and sulfated zirconium oxide / ZSM-5 molecular sieve in a mass ratio of 1:(1 to 2); the aminosulfonic acid content in the aminosulfonic acid / ZSM-5 molecular sieve is 20 to 40 wt%, and the sulfated zirconium oxide / ZSM-5 molecular sieve has a sulfated zirconium oxide content of 15 to 35 wt%; the solid acid catalyst is in the shape of a hollow strip, with an inner layer of the aminosulfonic acid / ZSM-5 molecular sieve and an outer layer of the sulfated zirconium oxide / ZSM-5 molecular sieve; S2, after the dropwise addition is completed, the reactor is heated to 40-45°C and the reaction is continued for 1-3 hours to obtain a reaction solution after the reaction is completed; S3. The solid acid catalyst and the crude organic phase are separated by filtration from the reaction mixture. n-heptane in an amount 1.5 to 3 times the mass of the crude organic phase is added to the crude organic phase. The dichloromethane is displaced by distillation at 60 to 80° C. to obtain a displaced organic phase. The displaced organic phase is cooled to 10 to 15° C. for crystallization for 1 to 1.5 hours. The precipitated crystals are filtered, rinsed with methanol, and finally dried to obtain antioxidant 330.

2. The production process of an antioxidant 330 according to claim 1, characterized in that: In step S1, the mass ratio of dichloromethane, solid acid catalyst, mesitylene and 3,5-di-tert-butyl-4-hydroxybenzyl methyl ether is (450-550): (5-10):12: (78-88); the concentration of the dichloromethane solution of 3,5-di-tert-butyl-4-hydroxybenzyl methyl ether is (15-20) wt%.

3. The production process of an antioxidant 330 according to claim 1, characterized in that: In step S1, the ZSM-5 molecular sieve in the aminosulfonic acid / ZSM-5 molecular sieve and the sulfated zirconium oxide / ZSM-5 molecular sieve is pretreated, and the pretreatment includes: uniformly mixing the ZSM-5 molecular sieve with a urea aqueous solution with a concentration of (5-10) wt%, heating to 80-100° C. for reflux reaction for 5-10 hours under stirring, filtering after the reaction, washing with water, drying at 110° C., and calcining at 550° C. for 6 hours to obtain the pretreated ZSM-5 molecular sieve; the mass ratio of the ZSM molecular sieve to the urea aqueous solution is 1:(100-200).

4. The production process of an antioxidant 330 according to claim 1, characterized in that: In step S1, the preparation of the aminosulfonic acid / ZSM-5 molecular sieve comprises the following steps: Urea, ethanol and ZSM-5 molecular sieve are uniformly mixed in a mass ratio of 2: (20-50): (5-10), stirred at 55-65°C for 1-2 hours, and then ethanol is removed by reduced pressure distillation under stirring. The mixture is dried at 100-110°C for 1-2 hours to obtain urea / ZSM-5 molecular sieve. Urea / ZSM-5 molecular sieve is added to 65% fuming sulfuric acid in a molar ratio of urea to sulfuric acid of 1: (1.2-1.5), mixed and stirred uniformly, reacted at 40-45°C for 12-15 hours, cooled to room temperature for crystallization after the reaction, filtered the crystals and dried at 100-120°C for 4-5 hours to obtain aminosulfonic acid / ZSM-5 molecular sieve.

5. The production process of an antioxidant 330 according to claim 1, characterized in that: In step S1, the preparation of sulfated zirconium oxide / ZSM-5 molecular sieve comprises the following steps: Zirconium oxychloride, ethanol and ZSM-5 molecular sieve are uniformly mixed in a mass ratio of 2: (20-50): (5-10), stirred at 55-65°C for 1-2 hours, and then the ethanol is removed by reduced pressure distillation under stirring. The mixture is dried at 100-110°C for 1-2 hours and then calcined at 350-550°C for 4-6 hours to obtain zirconium oxide / ZSM-5 molecular sieve. The zirconium oxide / ZSM-5 molecular sieve is immersed in a 0.4-0.6 mol / L sulfuric acid solution in a mass ratio of 1: (100-200), stirred for 25-35 minutes, filtered, and dried at 150-200°C for 3-4 hours to obtain sulfated zirconium oxide / ZSM-5 molecular sieve.

6. The production process of an antioxidant 330 according to claim 1, characterized in that: In step S1, the length of the catalyst is 10 to 30 mm, the thickness of the inner layer is 1 to 3 mm, and the thickness of the outer layer is 1 to 3 mm.

7. The production process of an antioxidant 330 according to claim 6, characterized in that: The inner side wall of the inner layer is corrugated, and the outer side wall of the outer layer is corrugated.

8. The production process of an antioxidant 330 according to claim 6, characterized in that: The preparation of the hollow strip-shaped solid acid catalyst comprises the following steps: S11, mixing sulfamic acid / ZSM-5 molecular sieve and aluminum sol to obtain an inner layer extrudate; S12, mixing the sulfated zirconium oxide / ZSM-5 molecular sieve and the aluminum sol to obtain an outer layer extrudate; S13, placing the inner layer extrudate and the outer layer extrudate into an extruder, extruding, and drying to obtain a hollow strip-shaped solid acid catalyst.

9. The production process of an antioxidant 330 according to claim 8, characterized in that: In step S11, the mass ratio of sulfamic acid / ZSM-5 molecular sieve to aluminum sol is 100:(40-50), and the solid content of aluminum sol is 20wt%; in step S12, the mass ratio of sulfated zirconium oxide / ZSM-5 molecular sieve to aluminum sol is 100:(40-50), and the solid content of aluminum sol is 20wt%; in step S13, the drying temperature is 120-160°C, and the drying time is 2-3h.