Method for decomposing peroxide generated by oxidation of m-diisopropylbenzene into resorcinol
By using a supported solid acid catalyst, the peroxide produced by the oxidation of m-diisopropylbenzene is decomposed into resorcinol, which solves the problems of low decomposition efficiency and many by-products in the prior art, and achieves high selectivity and efficient resorcinol production.
Patent Information
- Application Number
- CN202311694467.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2023-12-11
- Publication Date
- 2025-06-13
AI Technical Summary
The prior art is difficult to efficiently decompose the peroxide produced by the oxidation of m-diisopropylbenzene into resorcinol, and traditional catalysts are difficult to control during the decomposition process, making it easy to produce oily by-products.
The supported solid acid is used as a catalyst to decompose the highly selective resorcinol by reacting with the peroxide extract produced by oxidation of m-diisopropylbenzene. This catalyst has a small amount of use, good stability and low corrosion, and achieves high selective conversion under low temperature conditions.
High selective conversion of peroxides is achieved, the selectivity of the product resorcinol is as high as more than 85%, the catalyst usage is small and stable, and the generation of oily by-products is avoided.
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Figure CN120136677A_ABST
Abstract
Description
Technical Field
[0001] The present application relates to a method for decomposing peroxides generated by the oxidation of m - diisopropylbenzene into resorcinol, belonging to the field of chemical engineering. Background Art
[0002] Resorcinol, also known as 1,3 - benzenediol and m - dihydroxybenzene, commonly known as resorcin, is an important fine chemical raw material. Its chemical formula is C 6 H 6 O 2 , and it appears as a white crystalline powder. Its melting point is 109 to 112 °C, boiling point is 281 °C, flash point is 127 °C, and density is 1.276 g / cm. It turns pink when exposed to light, air or in contact with iron, and has a sweet taste. It is soluble in water, ethanol, amyl alcohol, easily soluble in ether, glycerol, slightly soluble in chloroform, carbon disulfide, and slightly soluble in benzene.
[0003] Resorcinol is mainly used in rubber adhesives, synthetic resins, dyes, preservatives, pharmaceuticals and analytical reagents, etc. Resorcinol is similar to phenol and cresol, and forms a condensate with formaldehyde, which can be used to make tire cord adhesives for viscose silk and nylon, prepare wood adhesives, and be used for the adhesion of vinyl materials to metals. Resorcinol is an intermediate for many azo dyes and fur dyes, and is also the raw material for the pharmaceutical intermediate p - aminosalicylic acid. Resorcinol has a bactericidal effect and can be used as a preservative, added to cosmetics and dermatological drug pastes and ointments, etc. The derivative of resorcinol, β - methylumbelliferone, is an intermediate for optical bleaching agents, and trinitroresorcinol is a detonator for detonators. A considerable amount of resorcinol is also used in the production of benzophenone - type ultraviolet absorbers. Summary of the Invention
[0004] For the experiment on the oxidation decomposition of m - diisopropylbenzene into resorcinol, the present application provides a catalyst for decomposing peroxides into resorcinol. Under the action of the catalyst, the conversion rate of the peroxide solution is as high as 80%, and the selectivity of resorcinol is more than 85%.
[0005] In one aspect of the present application, a method for decomposing peroxides generated by the oxidation of m - diisopropylbenzene into resorcinol is provided. This method uses a supported solid acid as a catalyst and the peroxide extraction solution generated by the oxidation of m - diisopropylbenzene as a reaction substrate, and obtains resorcinol with high selectivity through decomposition. The catalyst of this method has the advantages of less dosage, relatively stable, less corrosive, and can achieve high - selectivity conversion of peroxides under low - temperature conditions.
[0006] The method includes:
[0007] Mix catalyst I with an aqueous solution containing peroxides and react to obtain resorcinol;
[0008] Among them, the catalyst I includes catalyst A and catalyst B;
[0009] The catalyst A is selected from at least one of iron dichloride (FeCl 2 ), boron trifluoride (BF 3 ), aluminum trichloride (AlCl 3 ), tin dichloride (SnCl 2 );
[0010] The catalyst B is selected from at least one of ZrO 2 , Al 2 O 3 , ZnO;
[0011] The peroxide is obtained by oxidizing m - diisopropylbenzene.
[0012] The catalyst I used in this application is a relatively mild Lewis acid, achieving a very high catalytic cracking effect. Traditional commonly used catalysts include H 2 SO 4 , H 3 PO 4 , perchloric acid, benzenesulfonic acid, p - toluenesulfonic acid, strongly acidic ion - exchange resins and other acids with relatively strong acidity. Traditional catalysts, especially concentrated sulfuric acid, make the decomposition process more violent and difficult to control, and will produce more oily by - products.
[0013] The reaction equation of this application is shown in Formula 1:
[0014]
[0015] Optionally, in the negative catalyst I, the mass ratio of catalyst A to catalyst B is 1:1 to 1:10.
[0016] Optionally, in the catalyst I, the mass ratio of catalyst A to catalyst B is 1:5.
[0017] Optionally, in the catalyst I, the mass ratio of catalyst A to catalyst B independently selects any value from 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:8, 1:10 or any range value between any two of the above.
[0018] Optionally, the preparation method of the catalyst I includes:
[0019] Mix catalyst A, catalyst B with water, impregnate, and dry to obtain the catalyst I.
[0020] Optionally, the temperature of the reaction is 30 - 80 °C.
[0021] Optionally, the temperature of the reaction is 40 °C.
[0022] Optionally, the temperature of the reaction is independently selected from any value among 30°C, 40°C, 50°C, 60°C, 70°C, 80°C or any range value between any two of the above.
[0023] Optionally, the reaction time is 0.5 - 3 h.
[0024] Optionally, the reaction time is 1 h.
[0025] Optionally, the reaction time is independently selected from any value among 0.5 h, 1 h, 1.5 h, 2 h, 2.5 h, 3 h or any range value between any two of the above.
[0026] Optionally, the mass - volume ratio of the catalyst I to the aqueous solution containing peroxide is 1:300 - 1:60 g / ml.
[0027] Optionally, the mass - volume ratio of the catalyst I to the aqueous solution containing peroxide is independently selected from any value among 1:300 g / ml, 1:250 g / ml, 1:200 g / ml, 1:150 g / ml, 1:100 g / ml, 1:60 g / ml or any range value between any two of the above.
[0028] Optionally, in the aqueous solution containing peroxide, the concentration of peroxide is 1 mmol / g - 2 mmol / g.
[0029] Optionally, in the aqueous solution containing peroxide, the concentration of peroxide is independently selected from any value among 1 mmol / g, 1.5 mmol / g, 2 mmol / g or any range value between any two of the above.
[0030] As a specific embodiment, the reaction is carried out in a 100 - ml round - bottom flask, heated by an oil bath, under atmospheric pressure reaction, the dosage of the catalyst is 0.1 - 1 g, preferably 0.5 g.
[0031] The beneficial effects that can be produced by this application include:
[0032] (1) Through the catalyst provided by this application, peroxides with lower added value can be converted into resorcinol products with higher added value. This catalyst has the characteristics of high catalytic efficiency and simple preparation method, and has high popularization value.
[0033] (2) This method has the characteristics of simple process steps and high product added value. Compared with traditional catalysts, the dosage of the catalyst in this method is less, and the service life is extended while ensuring good catalyst stability. Description of the Drawings
[0034] Figure 1This is the gas chromatogram of Example 5 of the present application. Detailed implementation manners
[0035] The present application will be described in detail below with reference to examples, but the present application is not limited to these examples.
[0036] Unless otherwise specified, the raw materials and catalysts in the examples of the present application are purchased through commercial channels.
[0037] In the examples, the peroxide is:
[0038]
[0039] Preparation of Catalyst I in Example 1
[0040] Weigh 0.1 g of catalyst A, ferric dichloride, and 0.1 g of catalyst B, aluminum oxide, dissolve them in water, stir for 1 h by the impregnation method under normal pressure and normal temperature. After the reaction ends, perform rotary evaporation to evaporate the water, and place it in an 80 °C oven to dry overnight.
[0041] Preparation of Catalyst II in Example 2
[0042] Weigh 0.1 g of catalyst A, ferric dichloride, and 0.5 g of catalyst B, aluminum oxide, dissolve them in water, stir for 1 h by the impregnation method under normal pressure and normal temperature. After the reaction ends, perform rotary evaporation to evaporate the water, and place it in an 80 °C oven to dry overnight.
[0043] Preparation of Catalyst III in Example 3
[0044] Weigh 0.1 g of catalyst A, ferric dichloride, and 1 g of catalyst B, aluminum oxide, dissolve them in water, stir for 1 h by the impregnation method under normal pressure and normal temperature. After the reaction ends, perform rotary evaporation to evaporate the water, and place it in an 80 °C oven to dry overnight.
[0045] Example 4
[0046] Add 0.5 g of the catalyst synthesized in Example 1 to 50 ml of an oxide solution with a concentration of 1 mmol / g, heat it to 50 °C in an oil bath, and react for 0.5 h. After the reaction ends, the conversion rate of the peroxide is measured by titration, and the selectivity of the product is analyzed by GC. In this example, the conversion rate of the peroxide is 50%, and the selectivity of the product is 30%.
[0047] Example 5
[0048] Add 0.5 g of the catalyst synthesized in Example 1 to 50 ml of a peroxide solution with a concentration of 1 mmol / g, heat it to 50 °C in an oil bath, and react for 1 h. After the reaction ends, the conversion rate of the peroxide is measured by titration, and the selectivity of the product is analyzed by GC. In this example, the conversion rate of the peroxide is 85%, and the selectivity of the product is 86%.
[0049] Example 6
[0050] 0.5 g of the catalyst synthesized in Example 1 was added to 50 ml of a peroxide solution with a concentration of 1 mmol / g, and the mixture was heated to 50 °C in an oil bath and reacted for 1.5 h. After the reaction, the conversion of the peroxide was determined by titration, and the selectivity of the product was analyzed by GC. In this example, the conversion of the peroxide was 80%, and the selectivity of the product was 75%.
[0051] Example 7
[0052] 0.5 g of the catalyst synthesized in Example 1 was added to 50 ml of a peroxide solution with a concentration of 1 mmol / g, and the mixture was heated to 50 °C in an oil bath and reacted for 2 h. After the reaction, the conversion of the peroxide was determined by titration, and the selectivity of the product was analyzed by GC. In this example, the conversion of the peroxide was 75%, and the selectivity of the product was 65%.
[0053] Test Example 1
[0054] Example 5 was tested by GC, and the test results are as Figure 1 shown. It can be seen from Figure 1 that the peak at 5.514 is the internal standard (1,4-dichlorobenzene) peak, and the peak at 22.197 is the product resorcinol peak.
[0055] As described above, the above are only several embodiments of the present application, and do not impose any form of limitation on the present application. Although the present application is disclosed above with preferred embodiments, it is not intended to limit the present application. Any person skilled in the art, without departing from the scope of the technical solution of the present application, makes some changes or modifications using the technical content disclosed above, which are equivalent to equivalent embodiments and all fall within the scope of the technical solution.
Claims
1. A method for decomposing the peroxide produced by the oxidation of m - diisopropylbenzene into resorcinol, characterized in that, the method comprises: mixing catalyst I with an aqueous solution containing peroxide, and reacting to obtain resorcinol; wherein, the catalyst I comprises catalyst A and catalyst B; the catalyst A is selected from at least one of ferric dichloride, boron trifluoride, aluminum trichloride, selenium dichloride; The catalyst B is selected from at least one of ZrO 2 , Al 2 O 3 , and ZnO; the peroxide is obtained by the oxidation of m - diisopropylbenzene.
2. The method according to claim 1, characterized in that, in the catalyst I, the mass ratio of catalyst A to catalyst B is 1:1 to 1:
10.
3. The method according to claim 1, characterized in that, the preparation method of the catalyst I comprises: mixing catalyst A, catalyst B with water, impregnating, and drying to obtain the catalyst I.
4. The method according to claim 3, characterized in that, the temperature of the reaction is 30 - 80 °C.
5. The method according to claim 3, characterized in that, the time of the reaction is 0.5 - 3 h.
6. The method according to claim 1, characterized in that, the mass - volume ratio of the catalyst I to the aqueous solution containing peroxide is 1:300 - 1:60 g / ml.
7. The method according to claim 1, characterized in that, in the aqueous solution containing peroxide, the concentration of peroxide is 1 mmol / g - 2 mmol / g.