Catalyst for hydroperoxide acidolysis, process for its preparation and use

Abstract

The present application provides a catalyst for hydrogen peroxide acidolysis, a preparation method and application thereof, which comprises a solid catalyst modified by a strong acid and a salt aqueous solution; wherein the solid catalyst is at least one selected from natural white clay, activated white clay, bentonite or diatomite, and the salt aqueous solution contains at least one inorganic salt selected from sodium salt, potassium salt, magnesium salt and calcium salt. When the catalyst of the present application is used for hydrogen peroxide acidolysis, it has high hydrogen peroxide conversion rate and product selectivity.

Description

Technical Field

[0001] This invention relates to catalysts for the acidolysis of hydrogen peroxides, their preparation methods, and applications. Background Technology

[0002] Phenol and cyclohexanone are both important organic chemical raw materials. Specifically, phenol is an important intermediate in the preparation of phenolic resins, bisphenol A, and pharmaceuticals, with a global demand exceeding 10 Mt / a; while cyclohexanone is an important intermediate in the preparation of caprolactam and nylon, and also an important chemical solvent, with a global demand reaching 4.8 Mt / a. The main industrial production method for phenol is the cumene process (HOCK process), but its byproduct acetone has low added value, reducing overall economic efficiency. The main industrial production methods for cyclohexanone are the cyclohexane oxidation method and the cyclohexene hydration-dehydrogenation method, but both suffer from low conversion rates, poor selectivity, and high levels of waste.

[0003] In the early 1950s, scientists discovered that phenol and cyclohexanone could be co-produced from cyclohexylbenzene using a process similar to the HOCK process, which had high industrial application value. This route includes the following three steps: oxidation of cyclohexylbenzene to prepare cyclohexylbenzene hydroperoxide—acid hydrolysis of the hydroperoxide—separation and purification to obtain phenol and cyclohexanone. Although the process route for preparing phenol and cyclohexanone from cyclohexylbenzene is similar to that of the HOCK process for phenol and acetone, the actual reaction process differs significantly due to the different substrate structures. For example, because the cyclohexyl molecule is large and has many reactive sites, the oxidation reaction of cyclohexylbenzene is difficult to occur, resulting in low reaction efficiency and more byproducts.

[0004] The hydroperoxide acidolysis reaction of cyclohexylbenzene typically uses strong inorganic acids such as sulfuric acid as catalysts to prepare phenol and cyclohexanone. Although the reaction efficiency is relatively high, it also has its own drawbacks. The addition of liquid acid makes the reaction system more complex, increasing the difficulty of separating and purifying the phenol and cyclohexanone products. The use of acid also inevitably causes corrosion of the reaction apparatus and equipment. After the reaction, a certain amount of alkali needs to be added to neutralize the catalyst, increasing waste and production costs. Moreover, the separation and treatment of the generated salt is also a problem. At the same time, some patent literature reports the use of molecular sieves or superacids as acidolysis catalysts, but these all have certain disadvantages such as high cost and poor selectivity, resulting in less than ideal reaction effects. Therefore, the exploration and application of new acidolysis catalytic systems is of great significance. Summary of the Invention

[0005] In view of this, the purpose of this invention is to address the technical problems existing in the prior art by providing a catalyst for the acidolysis of hydroperoxides, its preparation method, and its application. When the catalyst of this invention is used for the acidolysis of hydroperoxides, it exhibits high hydroperoxide conversion rate and product selectivity.

[0006] The objective of this invention is achieved through the following technical solutions.

[0007] In a first aspect, the present invention provides a catalyst for the acidolysis of hydroperoxides, wherein the catalyst comprises a solid catalyst modified by a strong acid and a salt solution; wherein the solid catalyst is selected from at least one of natural clay, activated clay, bentonite or diatomaceous earth, and the salt solution contains at least one inorganic salt selected from sodium salt, potassium salt, magnesium salt and calcium salt.

[0008] The inventors of this application have discovered that by sequentially modifying a solid catalyst selected from natural clay, activated clay, bentonite, or diatomaceous earth with a strong acid and a salt solution containing at least one inorganic salt selected from sodium, potassium, magnesium, and calcium salts, the resulting catalyst exhibits high hydroperoxide conversion rate and product selectivity in the hydroperoxide acidolysis process.

[0009] According to the catalyst provided by the present invention, examples of strong acids suitable for use in the present invention include, but are not limited to, hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid. In some embodiments, the strong acid is selected from at least one of hydrochloric acid and sulfuric acid.

[0010] According to the catalyst provided by the present invention, the concentration of the strong acid is 0.1 to 40% by weight. For example, the concentration of the strong acid can be 0.1% by weight, 0.5% by weight, 1% by weight, 2% by weight, 5% by weight, 8% by weight, 10% by weight, 12% by weight, 15% by weight, 20% by weight, 25% by weight, 30% by weight, 35% by weight, 40% by weight, or a range thereof. In some embodiments, the concentration of the strong acid is 2% to 15% by weight.

[0011] According to the catalyst provided by the present invention, the inorganic salt may be a halide or a sulfate. Examples of suitable inorganic salts for use in the present invention include, but are not limited to, sodium chloride, sodium sulfate, potassium chloride, potassium sulfate, magnesium chloride, magnesium sulfate, calcium chloride, and calcium sulfate. In some embodiments, the inorganic salt is selected from at least one of sodium chloride, sodium sulfate, and potassium chloride.

[0012] According to the catalyst provided by the present invention, the concentration of the brine solution is 0.1% to 40% by weight. For example, the concentration of the brine solution can be 0.1% by weight, 0.5% by weight, 1% by weight, 2% by weight, 5% by weight, 8% by weight, 10% by weight, 12% by weight, 15% by weight, 18% by weight, 20% by weight, 25% by weight, 30% by weight, 35% by weight, 40% by weight, or a range thereof. In some embodiments, the concentration of the brine solution is 1% to 18% by weight.

[0013] According to the catalyst provided by the present invention, the catalyst is prepared by a method comprising the following steps: soaking a solid catalyst in a strong acid and then removing and drying it to obtain a pre-modified catalyst; and soaking the pre-modified catalyst in a brine solution and then removing and drying it.

[0014] Secondly, the present invention provides a method for preparing a catalyst for the acidolysis of hydroperoxides, wherein the preparation method includes the following steps:

[0015] S100. The solid catalyst is soaked in a strong acid, separated, and dried to obtain a pre-modified catalyst; wherein the solid catalyst is selected from at least one of natural clay, activated clay, bentonite, or diatomaceous earth.

[0016] S200: The pre-modified catalyst obtained in step S100 is soaked in a brine solution, separated, and dried to obtain the target product; wherein the brine solution contains at least one inorganic salt selected from sodium salt, potassium salt, magnesium salt, and calcium salt.

[0017] In the preparation method of the present invention, the strong acid and its concentration, the inorganic salt and the salt solution are as described above, and will not be repeated here.

[0018] According to the preparation method provided by the present invention, the mass ratio of the strong acid to the solid catalyst in step S100 is 1.5 to 10:1. For example, the mass ratio of the strong acid to the solid catalyst in step S100 can be 1.5:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, or a range thereof. In some embodiments, the mass ratio of the strong acid to the solid catalyst in step S100 is 2 to 6:1.

[0019] According to the preparation method provided by the present invention, in step S100, the solid catalyst is soaked in a strong acid for 0.5 to 24 hours. For example, the soaking time of the solid catalyst in the strong acid in step S100 can be 0.5 hours, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 14 hours, 13 hours, 14 hours, 15 hours, 16 hours, 18 hours, 20 hours, 24 hours, or a range thereof. In some embodiments, the solid catalyst is soaked in a strong acid for 1 to 12 hours in step S100.

[0020] According to the preparation method provided by the present invention, the drying temperature in step S100 is 80–150°C. For example, the drying temperature in step S100 is 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C, 120°C, 130°C, 140°C, 150°C, or a range thereof. In some embodiments, the drying temperature in step S100 is 90–130°C; in some embodiments, it is 95–120°C; and in some embodiments, it is 100–120°C.

[0021] According to the preparation method provided by the present invention, the drying time in step S100 is 1 to 12 hours. For example, the drying time in step S100 can be 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, or a range thereof. In some embodiments, the drying time in step S100 is 2 to 8 hours; and in some embodiments, it is 3 to 8 hours.

[0022] According to the preparation method provided by the present invention, the mass ratio of the salt solution to the solid catalyst in step S200 is 1.5 to 10:1. For example, the mass ratio of the salt solution to the solid catalyst in step S200 can be 1.5:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, or a range thereof. In some embodiments, the mass ratio of the salt solution to the solid catalyst in step S200 is 4 to 10:1.

[0023] According to the preparation method provided by the present invention, the pre-modified catalyst in step S200 is soaked in the brine solution for 0.5 to 24 hours. For example, the soaking time of the pre-modified catalyst in the brine solution in step S200 can be 0.5 hours, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 14 hours, 13 hours, 14 hours, 15 hours, 16 hours, 18 hours, 20 hours, 24 hours, or a range thereof. In some embodiments, the pre-modified catalyst in step S200 is soaked in the brine solution for 1 to 6 hours.

[0024] According to the preparation method provided by the present invention, the drying temperature in step S200 is 80–150°C. For example, the drying temperature in step S200 is 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C, 120°C, 130°C, 140°C, 150°C, or a range thereof. In some embodiments, the drying temperature in step S200 is 90–130°C; in some embodiments, it is 95–120°C; and in some embodiments, it is 105–120°C.

[0025] According to the preparation method provided by the present invention, the drying time in step S200 is 1 to 12 hours. For example, the drying time in step S200 can be 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, or a range thereof. In some embodiments, the drying time in step S200 is 2 to 8 hours; and in some embodiments, it is 4 to 6 hours.

[0026] According to the preparation method provided by the present invention, separation can be performed by filtration or centrifugation in steps S100 and S200.

[0027] Thirdly, the present invention provides a catalyst prepared by the above-described preparation method.

[0028] Fourthly, the present invention provides the application of the catalyst in the acidolysis of tertiary alkyl-substituted benzene hydroperoxides.

[0029] According to the application provided by the present invention, wherein the tertiary alkyl-substituted benzene hydroperoxide is as shown in formula A1 or A2:

[0030]

[0031] Wherein, R is selected from C1 to C2. 10 One of the hydrocarbon groups; R' is selected from C1 to C2. 10 One of the hydrocarbon groups; R2' is selected from hydrogen and C1-C2. 10 One of the hydrocarbon groups; n is an integer from 0 to 5, and x is an integer from 2 to 11.

[0032] Tertiary alkyl-substituted benzene hydroperoxides will be further described later.

[0033] Fifthly, the present invention provides an acid hydrolysis method for tertiary alkyl-substituted benzene hydroperoxides, wherein the acid hydrolysis method includes the following steps: adding the catalyst to the tertiary alkyl-substituted benzene hydroperoxide and reacting therewith.

[0034] According to the acidolysis method provided by the present invention, the tertiary alkyl-substituted benzene hydroperoxide is as shown in formula A1 or A2:

[0035]

[0036] Wherein, R is selected from C1 to C2. 10 One of the hydrocarbon groups; R' is selected from C1 to C2. 10 One of the hydrocarbon groups; R2' is selected from hydrogen and C1-C2. 10 One of the hydrocarbon groups; n is an integer from 0 to 5, and x is an integer from 2 to 11.

[0037] According to the acid hydrolysis method provided by the present invention, in formulas A1 and A2, R is selected from C1 to C2. 10 One of the alkyl groups, preferably one of C1 to C6 alkyl groups; and / or R' is selected from C1 to C6 alkyl groups. 10 One of the alkyl groups, preferably one of C1 to C6 alkyl groups; and / or R2' is selected from hydrogen and C1 to C6 alkyl groups. 10 One of the alkyl groups, preferably one of hydrogen and C1 to C6 alkyl groups.

[0038] Examples of C1-C6 alkyl groups suitable for use in this invention include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, and hexyl.

[0039] In this invention, n can be 0, 1, 2, 3, 4 or 5; and / or x can be 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11.

[0040] In some embodiments, the tertiary alkyl-substituted benzene hydroperoxide is cyclohexylbenzene hydroperoxide. The cyclohexylbenzene hydroperoxide may be pure cyclohexylbenzene hydroperoxide or a solution of cyclohexylbenzene oxidation products containing 10–90% by weight, preferably 10–70% by weight, more preferably 10–30% by weight of cyclohexylbenzene hydroperoxide.

[0041] According to the acidolysis method provided by the present invention, the reaction may be carried out in the presence or absence of another solvent.

[0042] In this invention, the solvent is selected from at least one of aromatic compounds and ketone compounds.

[0043] In this invention, the molecular structure of the aromatic compound is shown in Formula B.

[0044]

[0045] In formula B, R” is selected from one of the C1 to C8 alkyl groups; m is an integer from 0 to 6.

[0046] Examples of aromatic compounds suitable for use in this invention include, but are not limited to, benzene, toluene, and p-xylene.

[0047] In this invention, the ketone compound is a ketone compound having 3 to 8 carbon atoms. Examples of ketone compounds suitable for use in this invention include, but are not limited to, acetone and cyclohexanone.

[0048] In some embodiments, the acidolysis method includes mixing and reacting a tertiary alkyl-substituted benzene hydroperoxide, a catalyst, and a solvent. In some preferred embodiments, the mass ratio of the tertiary alkyl-substituted benzene hydroperoxide to the solvent is 1:1 to 9; and in some preferred embodiments, it is 1:2 to 4.

[0049] According to the acidolysis method provided by the present invention, the amount of catalyst added is 0.01% to 50% of the mass of the tertiary alkyl-substituted benzene hydroperoxide. For example, the amount of catalyst added is 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, 5.7%, 10%, 12%, 16.7%, 20%, 25%, 30%, 40%, 50% or a range thereof, of the mass of the tertiary alkyl-substituted benzene hydroperoxide. In some embodiments, the amount of catalyst added is 0.1% to 20% of the mass of the tertiary alkyl-substituted benzene hydroperoxide; and in some embodiments, it is 5% to 20%.

[0050] According to the acidolysis method provided by the present invention, the reaction temperature is 0–100°C. For example, the reaction temperature can be 0°C, 10°C, 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 75°C, 80°C, 90°C, 100°C, or a range thereof. In some embodiments, the reaction temperature is 40–80°C; and in some embodiments, it is 60–80°C.

[0051] According to the acidolysis method provided by the present invention, the reaction time is 0.5 to 24 hours. For example, the reaction time can be 0.5 hours, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours, 21 hours, 22 hours, 23 hours, 24 hours, or a range thereof. In some embodiments, the reaction time is 1 to 10 hours; and in some embodiments, it is 1 to 8 hours.

[0052] All of the above-mentioned raw materials used in this invention can be prepared in-house or purchased commercially; this invention does not impose any particular limitations on them.

[0053] The present invention has the following advantages: (1) When the catalyst of the present invention is used for hydroperoxide acidolysis, it has high hydroperoxide conversion rate and product selectivity; in particular, it effectively improves the hydroperoxide acidolysis reaction efficiency of cyclohexylbenzene hydroperoxide, reduces the occurrence of side reactions in the acidolysis reaction, and improves the product selectivity of the acidolysis reaction; (2) Compared with the prior art, the catalyst of the present invention reduces the impact on equipment corrosion, environmental pollution, etc., and has the advantages of high efficiency, low cost and easy operation. Detailed Implementation

[0054] The present invention will be further described below with reference to specific embodiments, but this does not constitute any limitation on the present invention.

[0055] All publications, patent applications, patents, and other references mentioned in this specification are incorporated herein by reference. Unless otherwise defined, all technical and scientific terms used in this specification have the meanings commonly understood by those skilled in the art. In case of conflict, the definitions in this specification shall prevail.

[0056] When this specification uses the prefixes “known to those skilled in the art,” “prior art,” or similar terms to derive materials, substances, methods, steps, apparatus, or components, the objects derived from such prefixes cover those commonly used in the art at the time of this application, but also include those that are not currently commonly used but will become generally recognized in the art as suitable for similar purposes.

[0057] It should be noted that the two or more aspects (or embodiments) disclosed in the context of this specification can be arbitrarily combined with each other, and the resulting technical solutions (such as methods or systems) are part of the original disclosure of this specification and also fall within the protection scope of this invention.

[0058] Unless otherwise specified, all percentages, parts, ratios, etc. mentioned in this specification are based on weight, unless being based on weight would not be in accordance with the common understanding of those skilled in the art.

[0059] The main raw materials used in the following examples and comparative examples are shown in Table 1.

[0060] Table 1 Raw Materials

[0061] Natural clay Purchased from Sinopharm Bentonite Purchased from Sinopharm diatomite Purchased from Sinopharm Activated clay Purchased from Aladdin Amberlyst15 resin catalyst Purchased from Sinopharm Acidic Y-type molecular sieve catalyst Purchased from Nankai University Catalyst Factory Commercially available activated clay Purchased from Aladdin

[0062] In addition, unless otherwise specified, all reagents and raw materials used in the embodiments and comparative examples of this invention are conventional products that can be obtained commercially, and all reagents are of analytical grade or chemically pure grade.

[0063] Example 1

[0064] 1. Preparation of catalysts

[0065] Take 50g of natural white clay and place it in a beaker. Add 100g of 10% hydrochloric acid and soak for 3 hours. Filter the mixture and dry the residue in a constant temperature oven at 110℃ for 3 hours. Then, soak the residue in 200g of 1% sodium chloride solution for 1 hour. After filtration, dry the solid in a constant temperature oven at 105℃ for 5 hours for later use.

[0066] 2. Acid hydrolysis reaction

[0067] 100g of cyclohexylbenzene oxidation solution containing 25% by weight of cyclohexylbenzene hydroperoxide was added to a reaction flask, along with 3g of the prepared catalyst. The reaction was carried out at 60°C for 4 hours. Referring to Table 1, the conversion rate of cyclohexylbenzene hydroperoxide was 90%, the selectivity for phenol was 89%, and the selectivity for cyclohexanone was 87%.

[0068] Example 2

[0069] 1. Preparation of catalysts

[0070] Take 50g of natural white clay and place it in a beaker. Add 100g of 10% hydrochloric acid and soak for 6 hours. Filter the residue and dry it in a 100℃ constant temperature oven for 5 hours. Then, soak the residue in 200g of 5% potassium chloride solution for 1 hour. After filtration, dry the solid in a 105℃ constant temperature oven for 5 hours for later use.

[0071] 2. Acid hydrolysis reaction

[0072] 100g of cyclohexylbenzene oxidation solution containing 25% by weight of cyclohexylbenzene hydroperoxide was added to a reaction flask, along with 5g of the prepared catalyst. The reaction was carried out at 80°C for 1 hour. Referring to Table 1, the conversion rate of cyclohexylbenzene hydroperoxide was 98%, the selectivity for phenol was 91%, and the selectivity for cyclohexanone was 90%.

[0073] Example 3

[0074] 1. Preparation of catalysts

[0075] Take 50g of bentonite and place it in a beaker. Add 150g of 5% sulfuric acid and soak for 2 hours. Filter the solution and dry the residue in a constant temperature oven at 130℃ for 8 hours. Then, soak the residue in 250g of 5% sodium sulfate solution for 3 hours. After filtration, dry the solid in a constant temperature oven at 110℃ for 5 hours for later use.

[0076] 2. Acid hydrolysis reaction

[0077] 100g of cyclohexylbenzene oxidation solution containing 25% by weight of cyclohexylbenzene hydroperoxide was added to a reaction flask, along with 5g of the prepared catalyst. The reaction was carried out at 80°C for 1 hour. Referring to Table 1, the conversion rate of cyclohexylbenzene hydroperoxide was 92%, the selectivity for phenol was 90%, and the selectivity for cyclohexanone was 90%.

[0078] Example 4

[0079] 1. Preparation of catalysts

[0080] Place 50g of diatomaceous earth in a beaker, add 150g of 8% hydrochloric acid, soak for 4 hours, filter, dry the filter residue in a 130℃ constant temperature oven for 8 hours, soak in 250g of 8% magnesium chloride solution for 3 hours, filter, and dry the solid in a 110℃ constant temperature oven for 4 hours for later use.

[0081] 2. Acid hydrolysis reaction

[0082] 100g of cyclohexylbenzene oxidation solution containing 30% by weight of cyclohexylbenzene hydroperoxide was added to a reaction flask, along with 5g of the prepared catalyst. The reaction was carried out at 60°C for 8 hours. Referring to Table 1, the conversion rate of cyclohexylbenzene hydroperoxide was 91%, the selectivity for phenol was 88%, and the selectivity for cyclohexanone was 87%.

[0083] Example 5

[0084] 1. Preparation of catalysts

[0085] Place 50g of diatomaceous earth in a beaker, add 300g of 2% hydrochloric acid, soak for 12 hours, filter, dry the filter residue in a 120℃ constant temperature oven for 5 hours, soak in 500g of 8% sodium chloride solution for 4 hours, filter, dry the solid in a 110℃ constant temperature oven for 5 hours for later use.

[0086] 2. Acid hydrolysis reaction

[0087] 50g of a cyclohexylbenzene oxidation solution containing 70% by weight of cyclohexylbenzene hydroperoxide was added to a reaction flask, along with 50g of acetone and 2g of the prepared catalyst. The reaction was carried out at 75°C for 5 hours. Referring to Table 1, the conversion rate of cyclohexylbenzene hydroperoxide was 93%, the selectivity for phenol was 89%, and the selectivity for cyclohexanone was 87%.

[0088] Example 6

[0089] 1. Preparation of catalysts

[0090] Place 50g of activated clay in a beaker, add 300g of 15% hydrochloric acid, soak for 1 hour, filter, dry the filter residue in a 120℃ constant temperature oven for 5 hours, remove it, soak it in 500g of 8% sodium chloride solution for 6 hours, filter, dry the solid in a 120℃ constant temperature oven for 5 hours for later use.

[0091] 2. Acid hydrolysis reaction

[0092] 20g of cyclohexylbenzene hydroperoxide crystals were added to a reaction flask, along with 80g of toluene and 2g of the prepared catalyst. The reaction was carried out at 75°C for 6 hours. Referring to Table 1, the conversion rate of cyclohexylbenzene hydroperoxide was 91%, the selectivity for phenol was 86%, and the selectivity for cyclohexanone was 85%.

[0093] Example 7

[0094] 1. Preparation of catalysts

[0095] Take 50g of activated clay and place it in a beaker. Add 100g of 15% hydrochloric acid and soak for 3 hours. Filter the residue and dry it in a constant temperature oven at 120℃ for 8 hours. Then, soak the residue in 300g of 10% sodium chloride solution for 6 hours. After filtration, dry the solid in a constant temperature oven at 120℃ for 5 hours for later use.

[0096] 2. Acid hydrolysis reaction

[0097] 100g of cyclohexylbenzene oxidation solution containing 30% by weight of cyclohexylbenzene hydroperoxide was added to a reaction flask, along with 5g of the prepared catalyst. The reaction was carried out at 60°C for 6 hours. Referring to Table 1, the conversion rate of cyclohexylbenzene hydroperoxide was 95%, the selectivity for phenol was 89%, and the selectivity for cyclohexanone was 87%.

[0098] Example 8

[0099] 1. Preparation of catalysts

[0100] Place 50g of activated clay in a beaker, add 100g of 15% hydrochloric acid, soak for 3 hours, filter, dry the filter residue in a 120℃ constant temperature oven for 6 hours, remove it, soak it in 300g of 10% calcium chloride solution for 6 hours, filter, dry the solid in a 120℃ constant temperature oven for 6 hours for later use.

[0101] 2. Acid hydrolysis reaction

[0102] 100g of cyclohexylbenzene oxidation solution containing 30% by weight of cyclohexylbenzene hydroperoxide was added to a reaction flask, along with 5g of the prepared catalyst. The reaction was carried out at 30°C for 10 hours. Referring to Table 1, the conversion rate of cyclohexylbenzene hydroperoxide was 92%, the selectivity for phenol was 88%, and the selectivity for cyclohexanone was 86%.

[0103] Example 9

[0104] 1. Preparation of catalysts

[0105] Take 50g of activated clay and place it in a beaker. Add 250g of 12% hydrochloric acid and soak for 3 hours. Filter the residue and dry it in a constant temperature oven at 110℃ for 5 hours. Then, soak the residue in 250g of 18% sodium chloride solution for 3 hours. After filtration, dry the solid in a constant temperature oven at 110℃ for 5 hours for later use.

[0106] 2. Acid hydrolysis reaction

[0107] 100g of cyclohexylbenzene oxidation solution containing 30% by weight of cyclohexylbenzene hydroperoxide was added to a reaction flask, along with 6g of the prepared catalyst. The reaction was carried out at 75°C for 2 hours. Referring to Table 1, the conversion rate of cyclohexylbenzene hydroperoxide was 98%, the selectivity for phenol was 95%, and the selectivity for cyclohexanone was 92%.

[0108] Comparative Example 1

[0109] 100g of cyclohexylbenzene oxidation solution containing 30% by weight of cyclohexylbenzene hydroperoxide was added to a reaction flask, followed by 6g of Amberlyst 15 resin catalyst. The reaction was carried out at 75°C for 2 hours. Referring to Table 1, the conversion rate of cyclohexylbenzene hydroperoxide was 52%, the selectivity for phenol was 88%, and the selectivity for cyclohexanone was 83%.

[0110] Comparative Example 2

[0111] 100g of cyclohexylbenzene oxidation solution containing 30% by weight of cyclohexylbenzene hydroperoxide was added to a reaction flask, followed by 6g of acidic Y-type molecular sieve catalyst. The reaction was carried out at 75°C for 2 hours. Referring to Table 1, the conversion rate of cyclohexylbenzene hydroperoxide was 40%, the selectivity for phenol was 87%, and the selectivity for cyclohexanone was 85%.

[0112] Comparative Example 3

[0113] 100g of cyclohexylbenzene oxidation solution containing 30% by weight of cyclohexylbenzene hydroperoxide was added to a reaction flask, along with 6g of commercially available activated clay. The reaction was carried out at 75°C for 2 hours. Referring to Table 1, the conversion rate of cyclohexylbenzene hydroperoxide was 82%, the selectivity for phenol was 80%, and the selectivity for cyclohexanone was 65%.

[0114] Comparative Example 4

[0115] 100g of cyclohexylbenzene oxidation solution containing 30% by weight of cyclohexylbenzene hydroperoxide was added to a reaction flask, along with 0.6g of 98% concentrated sulfuric acid catalyst. The reaction was carried out at 60°C for 1 hour. Referring to Table 1, the conversion rate of cyclohexylbenzene hydroperoxide was 98%, the selectivity for phenol was 92%, and the selectivity for cyclohexanone was 84%.

[0116] Table 2 Comparison of results from relevant examples and comparative examples.

[0117]

[0118] As shown in Table 2, especially in Examples 9 and Comparative Examples 1-3, the catalyst of this invention effectively improved the acid hydrolysis oxidation efficiency of cyclohexylbenzene. Under the same reaction conditions, compared with Amberlyst 15 resin, Y-type molecular sieve, and commercially available activated clay reaction systems, the conversion rate was significantly improved, and the product selectivity was also higher. Compared with the commonly used inorganic acid catalyst sulfuric acid (Comparative Example 4), the hydroperoxide conversion rate was similar, but the selectivity for phenol and cyclohexanone was more advantageous, and the product post-processing was simpler.

[0119] It should be noted that the embodiments described above are only for explaining the present invention and do not constitute any limitation on the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory terms, not limiting terms. Modifications can be made to the present invention within the scope of the claims, and revisions can be made to the present invention without departing from the scope and spirit of the present invention. Although the present invention described herein relates to specific methods, materials, and embodiments, it does not mean that the present invention is limited to the specific examples disclosed herein; on the contrary, the present invention can be extended to all other methods and applications with the same function.

Claims

1. Catalyst for hydroperoxide acidolysis, wherein, The catalyst comprises a solid catalyst modified by a strong acid and a salt aqueous solution; wherein the solid catalyst is at least one selected from natural clay, activated clay, bentonite or diatomite, and the salt aqueous solution contains at least one inorganic salt selected from sodium salt, potassium salt, magnesium salt and calcium salt, The inorganic salt is a halide salt or a sulfate salt, The catalyst is prepared by a method comprising the following steps: the solid catalyst is taken out and dried after being soaked in a strong acid to obtain a pre-modified catalyst; and the pre-modified catalyst is taken out and dried after being soaked in a salt aqueous solution.

2. The catalyst according to claim 1, characterized in that, The strong acid is at least one selected from hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid; and / or The concentration of the strong acid is 0.1-40% by weight; and / or The inorganic salt is at least one selected from sodium chloride, sodium sulfate, potassium chloride, potassium sulfate, magnesium chloride, magnesium sulfate, calcium chloride and calcium sulfate; and / or The concentration of the salt aqueous solution is 0.1-40% by weight.

3. The catalyst of claim 2, wherein The strong acid is at least one selected from hydrochloric acid and sulfuric acid; and / or The concentration of the strong acid is 2-15% by weight; and / or The inorganic salt is at least one selected from sodium chloride, sodium sulfate and potassium chloride; and / or The concentration of the salt aqueous solution is 1-18% by weight.

4. A process for the preparation of a catalyst for hydroperoxide acidolysis, wherein, The preparation method comprises the following steps: S100, soaking a solid catalyst in a strong acid, and drying after separation to obtain a pre-modified catalyst; wherein the solid catalyst is at least one selected from natural clay, activated clay, bentonite or diatomite; S200, soaking the pre-modified catalyst obtained in step S100 in a salt aqueous solution, and drying after separation to obtain a target product; wherein the salt aqueous solution contains at least one inorganic salt selected from sodium salt, potassium salt, magnesium salt and calcium salt; The inorganic salt is a halide salt or a sulfate salt.

5. The preparation method according to claim 4, characterized in that, The strong acid is at least one selected from hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid; and / or The concentration of the strong acid is 0.1-40% by weight; and / or The mass ratio of the strong acid to the solid catalyst in step S100 is 1.5-10:1; and / or The solid catalyst is soaked in the strong acid for 0.5-24 hours in step S100; and / or The drying temperature in step S100 is 80-150°C; and / or The drying time in step S100 is 1-12 hours.

6. The preparation method according to claim 5, characterized in that, The strong acid is at least one selected from hydrochloric acid and sulfuric acid; and / or The concentration of the strong acid is 2-15% by weight; and / or The mass ratio of the strong acid to the solid catalyst in step S100 is 2-6:1; and / or The solid catalyst is soaked in the strong acid for 1-12 hours in step S100; and / or The drying temperature in step S100 is 90-130°C; and / or The drying time in step S100 is 2-8 hours.

7. The preparation method according to claim 6, characterized in that, The drying temperature in step S100 is 95-120°C; and / or The drying time in step S100 is 3-8 hours.

8. The preparation method according to claim 7, characterized in that, The drying temperature in step S100 is 100-120°C.

9. The production method according to any one of claims 4 to 8, characterized by, The inorganic salt is at least one selected from sodium chloride, sodium sulfate, potassium chloride, potassium sulfate, magnesium chloride, magnesium sulfate, calcium chloride and calcium sulfate; and / or The concentration of the salt aqueous solution is 0.1-40% by weight; and / or The mass ratio of the salt water solution to the solid catalyst in step S200 is 1.5-10:1; and / or The pre-modified catalyst in step S200 is soaked in the salt water solution for 0.5-24 hours; and / or The drying temperature in step S200 is 80-150℃; and / or The drying time in step S200 is 1-12 hours.

10. The method of claim 9, wherein, The inorganic salt is at least one of sodium chloride, sodium sulfate and potassium chloride; and / or The concentration of the salt water solution is 1-18% by weight; and / or The mass ratio of the salt water solution to the solid catalyst in step S200 is 4-10:1; and / or The pre-modified catalyst in step S200 is soaked in the salt water solution for 1-6 hours; and / or The drying temperature in step S200 is 90-130℃; and / or The drying time in step S200 is 2-8 hours.

11. The method of claim 10, wherein, The drying temperature in step S200 is 95-120℃; and / or The drying time in step S200 is 4-6 hours.

12. The method of claim 11, wherein, The drying temperature in step S200 is 105-120℃.

13. The catalyst prepared by the preparation method in any one of claims 4-12.

14. The use of the catalyst in any one of claims 1-3 and 13 in acidolysis of a tertiary alkyl-substituted benzene hydroperoxide.

15. Use according to claim 14, characterized in that, The tertiary alkyl-substituted benzene hydroperoxide is represented by formula A1 or A2: Wherein, R is selected from C1~C 10 One of the hydrocarbon groups; R' is selected from C1~C 10 One of the hydrocarbon groups; R2' is selected from hydrogen and C1~C 10 One of the hydrocarbon groups; n is an integer from 0 to 5, and x is an integer from 2 to 11.

16. A process for the acidolysis of tertiary alkyl substituted benzene hydroperoxides wherein, The acidolysis method comprises the following steps: adding the catalyst in any one of claims 1-3 and 13 to the tertiary alkyl-substituted benzene hydroperoxide and reacting.

17. The acid hydrolysis method of claim 16, wherein, The tertiary alkyl-substituted benzene hydroperoxide is represented by formula A1 or A2: wherein R is selected from the group consisting of C1-C 10 one of a C1-C4alkyl group; R' is selected from the group consisting of C1-C 10 one of a C1-C4alkyl group; R2' is selected from the group consisting of hydrogen and C1-C 10 one of a C1-C4alkyl group; n is an integer from 0 to 5 and x is an integer from 2 to 11.

18. The acid hydrolysis method of claim 17, wherein, In formulae A1 and A2, R is selected from one of C1-C 10 alkyl; and / or R' is selected from one of C1-C 10 alkyl; and / or R2' is selected from one of hydrogen and C1-C 10 alkyl.

19. The acid hydrolysis method of claim 18, wherein, In formula A1 and A2, R is selected from one of C1-C6 alkyl; and / or R' is selected from one of C1-C6 alkyl; and / or R2' is selected from one of hydrogen and C1-C6 alkyl.

20. The acid hydrolysis method of claim 19, wherein, The tertiary alkyl-substituted benzene hydroperoxide is cyclohexylbenzene hydroperoxide.

21. The acid hydrolysis method according to any one of claims 16-20, characterized in that, The reaction is carried out in the presence of a solvent.

22. The acid hydrolysis method of claim 21, wherein, The solvent is at least one selected from aromatic compounds and ketone compounds.

23. The acid hydrolysis method of claim 22, wherein, The molecular structure of the aromatic compound is represented by formula B, B In formula B, R'' is selected from one of C1-C8 alkyl; and m is an integer of 0-6.

24. The acid hydrolysis method of claim 23, wherein, The aromatic compound is at least one selected from benzene, toluene and p-xylene.

25. The acid hydrolysis method of claim 22, wherein, The ketone compound is a ketone compound with a carbon atom number of 3-8.

26. The acid hydrolysis method of claim 25, wherein, The ketone compound is acetone and / or cyclohexanone.

27. The acid hydrolysis method of claim 21, wherein, The acidolysis method comprises: mixing the tertiary alkyl-substituted benzene hydroperoxide, the catalyst and the solvent and reacting.

28. The acid hydrolysis method of claim 27, wherein, The mass ratio of the tertiary alkyl-substituted benzene hydroperoxide to the solvent is 1:1-9.

29. The acid hydrolysis method of claim 28, wherein, The mass ratio of the tertiary alkyl-substituted benzene hydroperoxide to the solvent is 1:2-4.

30. The acid hydrolysis method of any one of claims 16 to 20, wherein, The amount of the catalyst added is 0.01%-50% of the mass of the tertiary alkyl-substituted benzene hydroperoxide; and / or The reaction temperature is 0-100℃; and / or The reaction time is 0.5-24 hours.

31. The acid hydrolysis method of claim 30, wherein, The amount of the catalyst added is 0.1%-20% of the mass of the tertiary alkyl-substituted benzene hydroperoxide; and / or The reaction temperature is 40-80℃; and / or The reaction time is 1-10 hours.

32. The acid hydrolysis method of claim 31, wherein, The amount of the catalyst is 5-20% of the mass of the tertiary alkyl-substituted benzene hydroperoxide; and / or The reaction temperature is 60-80℃; and / or The reaction time is 1-8 hours.

Images