Method for co-producing phenolic compounds and ketone compounds
By using a mixed system of N-hydroxy cationic surfactant and polyether surfactant to catalyze the oxidation and acidolysis of cycloalkylbenzene compounds, the problems of complex post-treatment of heterogeneous catalyst NHPI and cyclohexanone self-condensation were solved, achieving highly selective and efficient production of phenolic and ketone compounds.
Patent Information
- Application Number
- CN202410491559.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-04-23
- Publication Date
- 2025-10-24
AI Technical Summary
In the prior art, the post-processing of heterogeneous catalyst NHPI is complicated, and cyclohexanone is prone to self-condensation during the acidolysis process, affecting the selective production of phenol and cyclohexanone.
A mixed system of N-hydroxy cationic surfactant and polyether surfactant is used to catalyze the oxidation and acidolysis of cycloalkylbenzene compounds, avoiding intermediate separation and post-processing steps, and using an inorganic anionic catalyst to directly carry out acidolysis under mild conditions.
It achieves highly selective production of phenolic and ketone compounds under mild reaction conditions, with fast reaction speed and low cost, avoids self-condensation side reactions, and simplifies the process flow.
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Figure CN120829341A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of organic conversion reaction, in particular to a method for co-production of phenolic compounds and ketone compounds. BACKGROUND
[0002] The conventional preparation of phenol and cyclohexanone from cyclohexylbenzene needs to go through a peroxidation step and then an acidolysis, a total of two steps to obtain phenol and cyclohexanone. The oxidation of cyclohexylbenzene to 1-hydrocyclohexylbenzene peroxide often needs to increase the reaction temperature and use a catalyst. The common peroxidation catalyst is a heterogeneous catalyst NHPI (N-hydroxyphthalimide) and similar structures. The catalyst can dissociate nitrogen-oxygen free radicals at high temperature, and then generate 1-hydrocyclohexylbenzene peroxide with cyclohexylbenzene under the action of oxygen. However, the post-treatment of the catalyst is relatively complex, and if the content of the catalyst in the oxidation solution is high, it will affect the yield of the subsequent acidolysis reaction. At the same time, in the acidolysis step, the sulfuric acid catalyst used is easy to cause self-condensation of cyclohexanone, so the application of this method in industry is limited, and phenol and cyclohexanone cannot be obtained with good selectivity at the same time. An important goal of the latest research is to find a catalyst that can simultaneously oxidize and acidolysis cyclohexylbenzene, avoid the separation process of peroxide, and improve the selectivity of the target product in the oxidation and acidolysis reaction. SUMMARY
[0003] The purpose of the present application is to overcome the problems of complex post-treatment of the heterogeneous catalyst NHPI and easy self-condensation of cyclohexanone in the acidolysis process in the prior art, and to provide a method for co-production of phenolic compounds and ketone compounds. The method has the characteristics of mild reaction conditions, fast reaction speed, no easy self-condensation and ring-opening side reactions, and no intermediate separation and post-treatment steps. In addition, the catalyst has high solubility, and after the oxidation reaction is completed, the temperature is reduced to directly perform the acidolysis reaction.
[0004] In order to achieve the above-mentioned purpose, the present application provides a method for co-production of phenolic compounds and ketone compounds, which comprises: contacting a mixture of cycloalkylbenzene compound raw material, N-hydroxy cationic surfactant and optional polyether surfactant in an optional solvent under oxidation conditions to perform an oxidation reaction; and performing an acidolysis reaction on the material after the oxidation reaction under non-oxidation conditions. The cycloalkylbenzene compound has the following structure:
[0005]
[0006] Wherein, A is a cycloalkyl group;
[0007] The N-hydroxy cationic surfactant has the following structure:
[0008]
[0009] wherein R1, R2 and R3 are each independently selected from hydrogen, an alkyl group or an alkyl-substituted phenyl functional group and are not hydrogen at the same time; X - It is an inorganic anion.
[0010] Through the above technical solution, the present invention has the following advantages:
[0011] The present invention uses a surfactant having an N-hydroxy cation having the structural composition of the present invention as a catalyst to catalyze the oxidation and acidolysis of cycloalkylbenzene compounds. The method has mild reaction conditions, a fast reaction speed, low cost, is not prone to side reactions such as self-condensation and ring opening, and does not require intermediate separation and post-processing steps. The method has high application value. In addition, the catalyst has high solubility, and the acidolysis reaction can be directly carried out by lowering the temperature after the oxidation reaction process is completed.
[0012] The method for co-producing phenolic compounds and ketone compounds of the present invention has high selectivity for phenolic compounds and high selectivity for ketone compounds. DETAILED DESCRIPTION
[0013] The endpoints of the ranges and any values disclosed herein are not limited to the precise ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, the endpoints of each range, the endpoints of each range and individual point values, and the individual point values can be combined with each other to obtain one or more new numerical ranges, which should be considered to be specifically disclosed herein.
[0014] The present invention provides a method for co-producing phenolic compounds and ketone compounds. The oxidation method comprises: contacting a cycloalkylbenzene compound raw material with a mixed system of an N-hydroxy cationic surfactant and an optional polyether surfactant in an optional solvent under oxidizing conditions to carry out an oxidation reaction; and subjecting the material after the oxidation reaction to an acid hydrolysis reaction under non-oxidizing conditions. The cycloalkylbenzene compound has the following structure:
[0015]
[0016] wherein A is a cycloalkyl group;
[0017] The N-hydroxy cationic surfactant has the following structure:
[0018]
[0019] wherein R1, R2 and R3 are each independently selected from hydrogen, an alkyl group or an alkyl-substituted phenyl functional group and are not hydrogen at the same time; X - It is an inorganic anion; the N-hydroxy cationic surfactant satisfies the conservation of anions and cations.
[0020] The present application catalyzes the oxidation and acidolysis of cycloalkyl benzene compounds by using N-hydroxy cationic surfactant with the structural composition of the present application as catalyst, which has mild reaction condition, fast reaction speed, low cost, is not easy to cause side reactions such as self-condensation ring opening, and does not exist intermediate separation and post-treatment steps, has high application value, and the catalyst has high solubility, and can directly perform acidolysis reaction after the temperature is reduced at the end of the oxidation reaction.
[0021] According to a preferred embodiment of the present application, R1 is a C6-C20 alkyl or a C6-C20 alkyl-substituted phenyl functional group, preferably a C12-C16 alkyl or a C12-C16 alkyl-substituted phenyl functional group.
[0022] According to a preferred embodiment of the present application, R2 is hydrogen, a C1-C4 alkyl or a benzyl, preferably at least one of methyl, ethyl and benzyl. By adopting the foregoing preferred scheme, the catalytic effect can be further improved.
[0023] In order to further improve the catalytic effect, according to a preferred embodiment of the present application, R3 is hydrogen, a C1-C4 alkyl or a benzyl, preferably at least one of methyl, ethyl and benzyl.
[0024] According to a preferred embodiment of the present application, X - is at least one of sulfate, bisulfate, phosphate, hydrogen phosphate, acetate, halogen ion, preferably one of sulfate and chloride. By adopting the foregoing preferred scheme, the catalytic effect can be further enhanced.
[0025] In order to further enhance the catalytic effect, according to a preferred embodiment of the present application, the N-hydroxy cationic surfactant is selected from at least one of N-hydroxy dodecyl dimethyl sulfate, N-hydroxy hexadecyl dimethyl sulfate, N-hydroxy dodecyl dimethyl hydrochloride and N-hydroxy, N, N-dimethyl dodecyl aniline bisulfate, preferably a mixture of N-hydroxy dodecyl dimethyl hydrochloride and N-hydroxy dodecyl dimethyl sulfate with a molar ratio of 1-2:2-1, for example, the molar ratio can be 1:2, 1:1 and 2:1.
[0026] According to a preferred embodiment of the present application, the polyether surfactant has the following structure:
[0027] R-(PO)m(EO)n-H;
[0028] wherein R is a C8-C20 alkyl group or a C8-C20 alkyl group substituted phenyl group; and / or PO is a polypropylene oxide chain; and / or EO is a polyethylene oxide chain; and / or m is 0-10, for example, can be 0, 2, 4, 6, 8 and 10, preferably 2-6; and / or n is 4-20, for example, can be 4, 8, 12, 16 and 20, preferably 7-14, more preferably 10-12.
[0029] According to a preferred embodiment of the present application, the cycloalkyl benzene compound is a C5-C8 cycloalkyl benzene compound, preferably at least one of cyclohexane, cyclopentane and cycloheptane, more preferably cyclohexane.
[0030] In the present application, cyclohexyl benzene is used as an example, and the reaction formula of the reaction involved is as follows:
[0031]
[0032] In the present application, the oxidation conditions are conventional choices in the art as long as the purpose of the present application can be achieved, according to a preferred embodiment of the present application, the oxidation conditions are provided by an oxygen-containing gas, preferably the oxygen content in the oxygen-containing gas is not less than 15% by volume, more preferably oxygen and / or air.
[0033] In order to further improve the catalytic effect, according to a preferred embodiment of the present application, the oxidation reaction conditions include that the oxidation reaction temperature is 60-110℃, for example, can be 60℃, 70℃, 80℃, 90℃, 100℃ and 110℃, preferably 65-100℃, more preferably 85-95℃.
[0034] In the present application, the oxidation reaction time is not particularly required, the oxidation reaction time is adjusted accordingly with the change of temperature, and the oxidation reaction can be ensured to be sufficient, according to a preferred embodiment of the present application, the oxidation reaction time is 2-10h, for example, can be 2h, 4h, 6h, 8h and 10h, preferably 3-8h, more preferably 4-6h.
[0035] In the present application, the gas flow of the oxygen-containing gas in the oxidation reaction is not particularly required, and the oxidation reaction can be ensured to be sufficient, according to a preferred embodiment of the present application, the gas flow of the oxygen-containing gas is 20-1000mL / min, for example, can be 20mL / min, 100mL / min, 300mL / min, 500mL / min, 700mL / min, 900mL / min and 1000mL / min.
[0036] In order to further improve the catalytic effect, according to a preferred embodiment of the present application, the acidolysis reaction conditions include that the acidolysis reaction temperature is 15-35℃, for example, it can be 15℃, 20℃, 25℃, 30℃ and 35℃.
[0037] In the present application, the acidolysis reaction time is not particularly required, and the acidolysis reaction time is adjusted according to the temperature change, and the acidolysis reaction can be ensured to be sufficient. According to a preferred embodiment of the present application, the acidolysis reaction time is 1-4h, for example, it can be 1h, 2h, 3h and 4h.
[0038] In the present application, the acidolysis reaction is carried out under dynamic conditions, for example, under stirring conditions.
[0039] In the present application, the molar ratio of the solvent to the raw material calculated based on the naphthenyl benzene compound is not particularly required, and according to a preferred embodiment of the present application, the molar ratio of the solvent to the raw material calculated based on the naphthenyl benzene compound is 0.1-10:1, for example, it can be 0.1:1, 1:1, 3:1, 5:1, 7:1, 9:1 and 10:1.
[0040] In the present application, as long as the purpose of the present application can be achieved, the molar ratio of the N-hydroxy cationic surfactant to the raw material calculated based on the naphthenyl benzene compound is not particularly required, and according to a preferred embodiment of the present application, the molar ratio of the N-hydroxy cationic surfactant to the raw material calculated based on the naphthenyl benzene compound is 0.1-10:1, for example, it can be 0.1:1, 1:1, 2:1, 4:1, 6:1, 8:1 and 10:1.
[0041] In the present application, the molar ratio of the N-hydroxy cationic surfactant to the optional polyether surfactant is not particularly required, and according to a preferred embodiment of the present application, the molar ratio of the N-hydroxy cationic surfactant to the optional polyether surfactant is 1-10:1, for example, it can be 0.1:1, 1:1, 3:1, 5:1, 7:1, 9:1 and 10:1.
[0042] According to a preferred embodiment of the present application, the solvent is an aprotic solvent.
[0043] In the present application, as long as the purpose of the present application can be achieved, the aprotic solvent can be a conventional selection in the art, and according to a preferred embodiment of the present application, the aprotic solvent is selected from at least one of benzene, toluene, cyclohexyl benzene, acetonitrile, dichloromethane, trichloromethane, methanol, ethanol and tert-butanol.
[0044] The present application will be described in detail by examples below. In the following examples:
[0045] The conversion rate of cyclohexylbenzene was determined by a standard curve method of gas chromatography.
[0046] The selectivity of phenol was determined by a standard curve method of gas chromatography.
[0047] The selectivity of cyclohexanone was determined by a standard curve method of gas chromatography.
[0048] Unless otherwise specified, the raw materials were commercially available.
[0049] Example 1
[0050] Into a three-necked flask, 1 mol of cyclohexylbenzene was added, followed by 0.1 mol of N-hydroxydodecyl dimethyl hydrogen sulfate, stirred uniformly, kept at 95°C, then oxygen was continuously injected at a gas flow rate of 100 mL / min, after 4 h of reaction, the injection of oxygen was stopped and the temperature was lowered to 25°C, then continuous stirring was carried out for 2 h, and gas chromatography was used for detection, the conversion rate of cyclohexylbenzene was 19.8%, the selectivity of phenol was 96.0%, and the selectivity of cyclohexanone was 95.7%.
[0051] Example 2
[0052] According to Example 1, except that the oxidation reaction temperature was kept at 85°C, gas chromatography was used for detection, the conversion rate of cyclohexylbenzene was 18.2%, the selectivity of phenol was 97.0%, and the selectivity of cyclohexanone was 96.7%.
[0053] Example 3
[0054] According to Example 1, except that the oxidation reaction temperature was kept at 105°C, gas chromatography was used for detection, the conversion rate of cyclohexylbenzene was 22.5%, the selectivity of phenol was 91.0%, and the selectivity of cyclohexanone was 88.7%.
[0055] Example 4
[0056] According to Example 1, except that the oxygen was replaced by air, gas chromatography was used for detection, the conversion rate of cyclohexylbenzene was 14.5%, the selectivity of phenol was 97.8%, and the selectivity of cyclohexanone was 96.4%.
[0057] Example 5
[0058] According to Example 4, except that the oxidation reaction was carried out for 10 h, gas chromatography was used for detection, the conversion rate of cyclohexylbenzene was 18.5%, the selectivity of phenol was 93.8%, and the selectivity of cyclohexanone was 90.4%.
[0059] Example 6
[0060] According to the example 1, except that N-hydroxydodecyl dimethyl sulfate is replaced by N-hydroxyhexadecyl dimethyl sulfate, the conversion rate of cyclohexylbenzene is 20.2%, the selectivity of phenol is 96.2%, and the selectivity of cyclohexanone is 95.3% by gas chromatography.
[0061] Example 7
[0062] According to the example 1, except that N-hydroxydodecyl dimethyl sulfate is replaced by N-hydroxydodecyl dimethyl acetate, the conversion rate of cyclohexylbenzene is 17.2%, the selectivity of phenol is 94.2%, and the selectivity of cyclohexanone is 92.5% by gas chromatography.
[0063] Example 8
[0064] According to the example 1, except that N-hydroxydodecyl dimethyl sulfate is replaced by N-hydroxydodecyl dimethyl hydrochloride, the conversion rate of cyclohexylbenzene is 18.0%, the selectivity of phenol is 95.4%, and the selectivity of cyclohexanone is 95.1% by gas chromatography.
[0065] Example 9
[0066] According to the example 1, except that cyclohexylbenzene is replaced by cyclopentylbenzene, the conversion rate of cyclohexylbenzene is 20.1%, the selectivity of phenol is 82%, and the selectivity of cyclopentanone is 78.5% by gas chromatography.
[0067] Example 10
[0068] According to the example 1, except that N-hydroxydodecyl dimethyl sulfate is replaced by N-hydroxy, N.N-dimethyl dodecyl aniline hydrogen sulfate, the conversion rate of cyclohexylbenzene is 21.3%, the selectivity of phenol is 96.4%, and the selectivity of cyclohexanone is 95.5% by gas chromatography.
[0069] Example 11
[0070] According to the example 1, except that 5 mol of acetonitrile solvent is added at the same time as cyclohexylbenzene, the conversion rate of cyclohexylbenzene is 20.1%, the selectivity of phenol is 95.7%, and the selectivity of cyclohexanone is 94.9% by gas chromatography.
[0071] Example 12
[0072] According to the example 1, except that 0.1 mol of polyether surfactant is added at the same time as N-hydroxy cationic surfactant, the conversion rate of cyclohexylbenzene is 21.0%, the selectivity of phenol is 96.7%, and the selectivity of cyclohexanone is 95.9% by gas chromatography.
[0073] The polyether surfactant has the following structure:
[0074] R-(PO)m(EO)n-H;
[0075] wherein R is decyl group, m is 4; n is 11.
[0076] Example 13
[0077] In a three-necked flask, 1 mol of cyclohexylbenzene was added, followed by 0.05 mol of N-hydroxydodecyl dimethyl hydrochloride, 0.05 mol of N-hydroxydodecyl dimethyl sulfate and 0.1 mol of polyether surfactant, stirred uniformly, kept at 95°C, followed by continuous oxygen injection at a gas flow rate of 100 mL / min, after 4 h of reaction, oxygen injection was stopped and the temperature was lowered to 25°C, then continuous stirring was carried out for 2 h, gas chromatography detection showed that the conversion rate of cyclohexylbenzene was 21.8%, the selectivity of phenol was 98.0%, and the selectivity of cyclohexanone was 97.2%.
[0078] wherein the polyether surfactant has the following structure:
[0079] R-(PO)m(EO)n-H;
[0080] wherein R is decyl group, m is 4; n is 11.
[0081] Example 14
[0082] In a three-necked flask, 1 mol of cyclohexylbenzene was added, followed by 0.05 mol of N-hydroxydodecyl dimethyl hydrochloride and 0.05 mol of N-hydroxydodecyl dimethyl sulfate, stirred uniformly, kept at 95°C, followed by continuous oxygen injection at a gas flow rate of 100 mL / min, after 4 h of reaction, oxygen injection was stopped and the temperature was lowered to 25°C, then continuous stirring was carried out for 2 h, gas chromatography detection showed that the conversion rate of cyclohexylbenzene was 21.4%, the selectivity of phenol was 97.5%, and the selectivity of cyclohexanone was 96.6%.
[0083] Comparative Example 1
[0084] In a three-necked flask, 1 mol of cyclohexylbenzene was added, followed by 0.1 mol of NHPI, stirred uniformly, kept at 95°C, followed by continuous oxygen injection at a gas flow rate of 100 mL / min, after 4 h of reaction, oxygen injection was stopped and the temperature was lowered to 25°C, then continuous stirring was carried out for 2 h, gas chromatography detection showed that the conversion rate of cyclohexylbenzene was 18.6%, the selectivity of phenol was 3.0%, and the selectivity of cyclohexanone was 2.4%.
[0085] The preferred embodiments of the present application are described in detail above, but the present application is not limited thereto. Within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, including that each technical feature is combined in any other suitable manner. These simple modifications and combinations should also be considered as disclosed by the present application and fall within the protection scope of the present application.
Claims
1. A method for co-producing a phenolic compound and a ketonic compound, characterized by, The method comprises: mixing the raw material of the cycloalkyl benzene compound with a mixed system of the N-hydroxy cationic surfactant and the polyether surfactant in an optional solvent, and carrying out the oxidation reaction under the oxidation condition; carrying out the acidolysis reaction on the material after the oxidation reaction under the non-oxidation condition; the cycloalkyl benzene compound has the following structure: wherein A is a cycloalkyl group; the N-hydroxy cationic surfactant has the following structure: wherein R1, R2and R3are each independently selected from hydrogen, an alkyl group or an alkyl substituted phenyl functional group and are not simultaneously hydrogen; X - is an inorganic anion.
2. The method according to claim 1, wherein, R1 is a C6-C20 alkyl group or a C6-C20 alkyl-substituted phenyl functional group; and / or R2 is hydrogen, a C1-C4 alkyl group or a benzyl group; and / or R3 is hydrogen, a C1-C4 alkyl group or a benzyl group.
3. The method according to claim 1 or 2, wherein, R1 is a C12-C16 alkyl group or a C12-C16 alkyl-substituted phenyl functional group; and / or R2 is at least one of a methyl group, an ethyl group and a benzyl group; and / or R3 is at least one of a methyl group, an ethyl group and a benzyl group; and / or X- is at least one of a sulfate ion, a hydrogen sulfate ion, a phosphate ion, a hydrogen phosphate ion, an acetate ion and a halide ion, preferably one of a sulfate ion, a hydrogen sulfate ion and a chloride ion.
4. The method of any of claims 1-3, wherein, the N-hydroxy cationic surfactant is selected from at least one of N-hydroxy dodecyl dimethyl sulfate, N-hydroxy hexadecyl dimethyl sulfate, N-hydroxy dodecyl dimethyl hydrochloride and N-hydroxy, N, N-dimethyl dodecyl aniline hydrogen sulfate, preferably a mixture of N-hydroxy dodecyl dimethyl hydrochloride and N-hydroxy dodecyl dimethyl sulfate in a molar ratio of 1-2:2-1.
5. The method of any of claims 1-4, wherein, the polyether surfactant has the following structure: R-(PO)m(EO)n-H wherein R is a C8-C20 alkyl group or a C8-C20 alkyl-substituted phenyl group; and / or m is 0-10, preferably 2-6; and / or n is 4-20, preferably 7-14, more preferably 10-12.
6. The method of any of claims 1-5, wherein, A is a C5-C8 cycloalkyl group, preferably at least one of cyclohexane, cyclopentane and cycloheptane, more preferably cyclohexane.
7. The method of any of claims 1-6, wherein, the oxidation condition is provided by an oxygen-containing gas, preferably the oxygen content of the oxygen-containing gas is not less than 15% by volume, more preferably oxygen and / or air.
8. The method according to any one of claims 1-7, wherein, the conditions of the oxidation reaction comprise: the oxidation reaction temperature is 60-110°C, preferably 65-100°C; and / or the oxidation reaction time is 2-10h, preferably 3-8h; and / or the gas flow of the oxygen-containing gas is 20-1000mL / min in terms of oxygen; and / or the conditions of the acidolysis reaction comprise: the acidolysis reaction temperature is 15-35°C; and / or the acidolysis reaction time is 1-4h. in the mixed system, 9. The method of any of claims 1-8, wherein, the molar ratio of the solvent to the raw material in terms of the cycloalkyl benzene compound is 0.1-10:1; and / or the molar ratio of the N-hydroxy cationic surfactant to the raw material in terms of the cycloalkyl benzene compound is 0.1-10:1; and / or the molar ratio of the N-hydroxy cationic surfactant to the polyether surfactant is 1-10:
1. 10. The method of any of claims 1-8, wherein, The solvent is an aprotic solvent; Preferably, the aprotic solvent is selected from at least one of benzene, toluene, cyclohexylbenzene, acetonitrile, dichloromethane, trichloromethane, methanol, ethanol and tert-butanol.