Concentration method of alkylbenzene peroxide and alkylbenzene peroxide

Abstract

The invention relates to the technical field of concentration of alkylbenzene peroxide, in particular to a concentration method of alkylbenzene peroxide and the alkylbenzene peroxide. The concentration method comprises the step of contacting an alkylbenzene peroxide solution with gel type acidic resin. The alkyl benzene peroxide solution is concentrated through the gel type acidic resin, so that the concentration method is low in device requirement, simple and safe to operate and low in cost, fed materials can be regenerated and recycled, and the method is suitable for concentration of alkyl benzene peroxide solutions with any concentration, especially 10-20 wt%. Meanwhile, the alkylbenzene peroxide obtained after concentration does not contain phenol cyclohexanone and / or phenyl cyclohexanol; strong-acid resin in traditional cognition is often used for decomposition of peroxide, while gel type strong-acid resin used in the method does not decompose alkylbenzene peroxide, which is found out except for expectations.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of alkylbenzene peroxide concentration, in particular to an alkylbenzene peroxide concentration method and alkylbenzene peroxide. BACKGROUND

[0002] Peroxide concentration has always been a difficulty in peroxide synthesis process, and the common methods for purifying peroxide mainly include the following two methods: 1. using an extractant to extract peroxide, and then distilling the solvent to achieve the purpose of concentration; 2. using an aqueous alkali solution to extract peroxide into the water phase, and then using a weak acid to re-acidify the peroxide, and separating the organic phase to obtain high-concentration peroxide. However, for the first method, the operations such as reduced pressure and heating in the distillation process are easy to cause the decomposition of peroxide, resulting in the decrease of peroxide purity, and if there are trace amounts of acidic substances and metal ions and other impurities in the device, the peroxide is easy to explode, which has great safety hazards in industrial applications. The latter method has a complex reaction process, complicated operation, and high cost, and a large amount of waste alkali and waste water are generated in the concentration process, polluting the environment. At present, there is an urgent need for a safe, environmentally friendly and convenient peroxide concentration process in industrial applications to obtain high-concentration peroxide for subsequent reactions. SUMMARY

[0003] The purpose of the present application is to overcome the problems of high device requirements, complicated operation and high cost in the prior art, and to provide an alkylbenzene peroxide concentration method and alkylbenzene peroxide, which has the characteristics of low device requirements, simple operation, low cost, and recycled use of feedstock.

[0004] In order to achieve the above-mentioned purpose, the present application provides an alkylbenzene peroxide concentration method in the first aspect, which comprises: contacting an alkylbenzene peroxide solution with a gel-type acidic resin.

[0005] The present application provides an alkylbenzene peroxide obtained by the concentration method of the first aspect in the second aspect.

[0006] Through the above technical solution, the present application has the following advantages:

[0007] The present application uses a gel-type acidic resin to concentrate the alkylbenzene peroxide solution, so that the concentration method has low device requirements, simple and safe operation, low cost, and recycled use of feedstock, and is suitable for the concentration of alkylbenzene peroxide solutions of any concentration, especially 10-20wt%. The alkylbenzene peroxide obtained after concentration has no phenol cyclohexanone and / or phenylcyclohexanol. In traditional cognition, strong acid resin is often used for peroxide decomposition, but the gel-type strong acid resin used in the present application does not cause decomposition of alkylbenzene peroxide, which is an unexpected discovery. BRIEF DESCRIPTION OF THE DRAWINGS

[0008] Figure 1 The present invention is a preferred embodiment of the process for concentrating alkylbenzene peroxide. DETAILED DESCRIPTION

[0009] 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.

[0010] The invention provides a method for concentrating an alkylbenzene peroxide. The method comprises: contacting an alkylbenzene peroxide solution with a gel-type acidic resin.

[0011] The present invention uses a gel-type acidic resin to concentrate alkylbenzene peroxide, resulting in a concentration method that has low equipment requirements, simple and safe operation, and low cost. The feed can be regenerated and recycled, making it suitable for concentrating alkylbenzene peroxide of any concentration. Furthermore, the alkylbenzene peroxide obtained after concentration is free of phenol, cyclohexanone, and / or phenylcyclohexanol. Traditionally, strong acidic resins are commonly used to decompose peroxides, but the gel-type strong acidic resin used in the present invention does not decompose the alkylbenzene peroxide, an unexpected discovery.

[0012] According to a preferred embodiment of the present invention, the particle size of the gel-type acidic resin is 0.4-0.7 mm, for example, 0.4 mm, 0.5 mm, 0.6 mm and 0.7 mm. By adopting the above preferred solution, the concentration effect can be further enhanced.

[0013] In order to further enhance the concentration effect, according to a preferred embodiment of the present invention, the crosslinking degree of the gel-type acidic resin is 5-20%, for example, 5%, 7%, 9%, 11%, 13%, 15%, 17% and 19%.

[0014] According to a preferred embodiment of the present invention, the gel-type acidic resin is a gel-type strong acidic resin, preferably a styrene-based gel-type strong acidic resin, more preferably a sulfonic acid group-substituted styrene-based gel-type strong acidic resin. By adopting the above preferred embodiment, the concentration effect can be further enhanced.

[0015] In order to further enhance the concentration effect, according to a preferred embodiment of the present application, the gel-type acidic resin is selected from at least one of 001X7 strong acidic resin, 001X8 strong acidic resin and 001X12 gel-type strong acidic resin, preferably at least two, more preferably a mixture of 001X7 strong acidic resin and 001X12 gel-type strong acidic resin with a mass ratio of 1-2:2-1, for example, the mass ratio can be 1:2, 1:1 and 2:1.

[0016] According to a preferred embodiment of the present application, the concentration method comprises: sequentially contacting the alkylbenzene peroxide solution with the gel-type acidic resin for at least two steps, preferably, contacting the alkylbenzene peroxide solution with the gel-type acidic resin for 2-4 times, more preferably, the cross-linking degree of the gel-type acidic resin in the former step of any two adjacent steps is less than 3-10% of the cross-linking degree of the gel-type acidic resin in the latter step, for example, it can be 3%, 5%, 8% and 10%. By adopting the foregoing preferred scheme, the concentration effect can be further enhanced.

[0017] In order to further enhance the concentration effect, according to a preferred embodiment of the present application, the concentration method comprises: sequentially contacting the alkylbenzene peroxide solution with the first gel-type acidic resin with a cross-linking degree of 5-17% and the second gel-type acidic resin with a cross-linking degree of 8-20% to obtain the concentrated alkylbenzene peroxide solution, for example, the cross-linking degree of the first gel-type acidic resin can be 5%, 7%, 9%, 12%, 15%, 17%, and the cross-linking degree of the second gel-type acidic resin can be 8%, 10%, 12%, 15%, 18%, 20%.

[0018] According to a preferred embodiment of the present application, the first gel-type acidic resin is 001X7 gel-type strong acidic resin, and the second gel-type acidic resin is 001X12 gel-type strong acidic resin. By adopting the foregoing preferred scheme, the concentration effect can be further enhanced.

[0019] In order to further enhance the concentration effect, according to a preferred embodiment of the present application, the mass ratio of 001X7 strong acidic resin to 001X12 gel-type strong acidic resin is 1-2:2-1, for example, 1:2, 1:1 and 2:1.

[0020] In the present application, as long as the purpose of the present application can be achieved, the concentration of the alkylbenzene peroxide solution is not particularly required, according to a preferred embodiment of the present application, the concentration of the alkylbenzene peroxide solution is 10-20wt%, and the rest mainly contains a solvent.

[0021] In the present application, the alkylbenzene peroxide in the alkylbenzene peroxide solution can be selected according to the conventional selection in the art as long as the object of the present application can be achieved. According to a preferred embodiment of the present application, the alkylbenzene peroxide (alkylbenzene hydroperoxide) is at least one of C9-C16 alkylbenzene peroxide, preferably at least one of cyclohexylbenzene peroxide, cyclopentylbenzene peroxide, cumene peroxide, di-cumene peroxide and cyclooctylbenzene peroxide, and more preferably cyclohexylbenzene peroxide and / or cyclopentylbenzene peroxide.

[0022] In the present application, the solvent in the alkylbenzene peroxide solution is not particularly required as long as the object of the present application can be achieved. According to a preferred embodiment of the present application, the solvent in the alkylbenzene peroxide solution is at least one of alkylbenzene solvents, preferably at least one of cyclohexylbenzene, cyclopentylbenzene, cumene and di-cumene, and cyclooctylbenzene.

[0023] According to a preferred embodiment of the present application, the contacting condition includes that the weight percentage of the gel-type acidic resin to the alkylbenzene peroxide solution is 0.1-5:1, for example, can be 0.1:1, 0.25:1, 0.5:1, 1:1, 2:1, 3:1, 4:1 and 5:1, preferably 0.5-4:1, and more preferably 1-2:1. By using the foregoing preferred scheme, the gel-type acidic resin can be ensured to be fully contacted with the alkylbenzene peroxide raw material, thereby improving the concentration effect of the alkylbenzene peroxide.

[0024] In order to further ensure the gel-type acidic resin to be fully contacted with the alkylbenzene peroxide raw material, thereby further improving the concentration effect of the alkylbenzene peroxide, according to a preferred embodiment of the present application, the contacting condition includes that the temperature is 0-80℃, for example, can be 0℃, 10℃, 20℃, 30℃, 40℃, 50℃, 60℃, 70℃ and 80℃, preferably 10-60℃, and more preferably 20-55℃.

[0025] In the present application, the contacting time is not particularly required, and the contacting time is adjusted according to the temperature, and the sufficient contacting can be ensured. According to a preferred embodiment of the present application, the contacting condition includes that the time is 0.1-6h, for example, can be 0.1h, 0.5h, 1h, 1.5h, 2h, 3h, 4h, 5h and 6h, preferably 0.5-4h, and more preferably 2-3h.

[0026] According to a preferred embodiment of the present application, the gel-type acidic resin is reused after being eluted by an eluent; and the eluent is recycled after being purified. By using the foregoing preferred scheme, the gel-type acidic resin and the eluent can be regenerated and recycled, thereby saving resources and reducing costs.

[0027] In the present application, the eluent is not particularly limited as long as the object of the present application can be achieved, and according to a preferred embodiment of the present application, the eluent is at least one of methanol, ethanol, isopropanol, and acetone.

[0028] In the present application, the purification method can be a conventional selection in the art as long as the object of the present application can be achieved, and according to a preferred embodiment of the present application, the purification method is fractionation and / or distillation.

[0029] In the present application, the feeding method and the contacting method and device are not particularly limited as long as the object of the present application can be achieved, and according to a preferred embodiment of the present application, the raw material feeding method is feeding by a peristaltic pump, and the contacting is in a fixed bed.

[0030] The present application provides an alkylbenzene peroxide obtained by the concentration method.

[0031] According to a preferred embodiment of the present application, the concentration of the alkylbenzene peroxide is 25-60 wt%, and the content of phenol cyclohexanone and / or phenylcyclohexanol is 0.

[0032] According to an embodiment of the present application, one-step concentration is carried out according to the route map shown in Figure 1 The specific steps are as follows: a low-concentration peroxide solution is treated by a container containing gel-type strong acid resin to obtain a high-concentration peroxide solution, and the gel-type strong acid resin in the container is optionally eluted for in-situ regeneration, an eluent and alkylbenzene mixture is obtained by elution, the mixture is purified, for example, fractionated, to obtain regenerated eluent and alkylbenzene, the regenerated eluent is recycled as eluent, and the alkylbenzene is recycled into the raw material.

[0033] The present application will be described in detail by examples below. In the following examples:

[0034] The concentration of the peroxide is measured by iodometry;

[0035] Unless otherwise specified, the raw materials are commercially available.

[0036] Example 1

[0037] According to the route map shown in Figure 1 In a fixed bed, 10 g of 001X7 gel-type strong acid resin with a particle size of 0.5 mm is added, 20 g of a cyclohexylbenzene solution of cyclohexylbenzene peroxide (peroxide concentration of 15 wt%) is passed into the fixed bed by a peristaltic pump, the temperature of the fixed bed is 50°C, the contact time is 3 hours, and the product is sampled and detected at the outlet of the fixed bed, and the peroxide concentration in the product is 25.3 wt%.

[0038] Example 2

[0039] Example 1 except that the cyclohexylbenzene solution of cyclohexylbenzene hydroperoxide was 40 g and the concentration of the hydroperoxide solution was 21.9 wt% as determined by sampling.

[0040] Example 3

[0041] Example 1 except that the 001X7 gel-type strongly acidic resin was added at 20 g and the concentration of the hydroperoxide solution was 30.7 wt% as determined by sampling.

[0042] Example 4

[0043] Example 1 except that the fixed bed temperature was 30°C and the concentration of the hydroperoxide solution was 24.3 wt% as determined by sampling.

[0044] Example 5

[0045] Example 1 except that the fixed bed temperature was 70°C and the concentration of the hydroperoxide solution was 23.6 wt% as determined by sampling.

[0046] Example 6

[0047] Example 1 except that the gel-type strongly acidic resin was 001X8 strongly acidic resin and the concentration of the hydroperoxide solution was 24.6 wt% as determined by sampling.

[0048] Example 7

[0049] Example 1 except that after the completion of the contact, the gel-type strongly acidic resin was eluted with acetone and then the cyclohexylbenzene hydroperoxide cyclohexylbenzene solution 20 g (15 wt% hydroperoxide concentration) was injected into the reactor for concentration, the concentration of the hydroperoxide solution was 24.9 wt% as determined by sampling, the mixture of acetone and cyclohexylbenzene was fractionated to obtain regenerated acetone and cyclohexylbenzene, the regenerated acetone was recycled as the eluent and the cyclohexylbenzene was recycled into the raw material.

[0050] Example 8

[0051] Example 1 except that the cyclohexylbenzene hydroperoxide cyclohexylbenzene solution was replaced by cyclopentylbenzene hydroperoxide cyclopentylbenzene solution and the concentration of the hydroperoxide solution was 25.0 wt% as determined by sampling.

[0052] Example 9

[0053] In a fixed bed, 5 g of 001X7 gel-type strongly acidic resin with a particle size of 0.5 mm was added, and 20 g of a cyclohexylbenzene solution of cyclohexylbenzene peroxide (peroxide concentration was 15 wt %) was fed into the fixed bed by a peristaltic pump. The fixed bed temperature was 50° C., and the contact time was 1.5 hours. The product was then contacted with 5 g of 001X12 gel-type strongly acidic resin with a particle size of 0.5 mm at a temperature of 50° C. for 1.5 hours. Sampling and detection were performed at the fixed bed outlet, and the peroxide concentration in the product was 34.2 wt %.

[0054] Example 10

[0055] In a fixed bed, 5g of 001X7 gel-type strongly acidic resin with a particle diameter of 0.5mm was added, 20g of a cyclohexylbenzene solution of cyclohexylbenzene peroxide (peroxide concentration was 15wt%) was fed in the fixed bed by a peristaltic pump, the fixed bed temperature was 50°C, and the contact time was 1.5 hours. Then, 5g of 001X7 gel-type strongly acidic resin with a particle diameter of 0.5mm was contacted at 50°C for 1.5h. Sampling and detection were performed at the fixed bed outlet, and the peroxide concentration in the product was 26.8wt%.

[0056] Example 11

[0057] according to Figure 1 The route diagram shown in FIG5 was carried out, and 10 g of a mixture of 001X7 gel-type strong acid resin with a particle size of 0.5 mm and 001X12 gel-type strong acid resin with a particle size of 0.5 mm in a mass ratio of 1 was added to the fixed bed. 20 g of a cyclohexylbenzene solution of cyclohexylbenzene peroxide (peroxide concentration of 15 wt %) was introduced into the fixed bed by a peristaltic pump. The fixed bed temperature was 50° C., the contact time was 3 hours, and sampling was performed at the fixed bed outlet. The peroxide concentration in the product was 27.3 wt %.

[0058] Comparative Example 1

[0059] The method is the same as Example 1, except that the resin used is DuPont IRA458. After sampling and testing, the concentration of the peroxide solution is 8.6 wt %.

[0060] Comparative Example 2

[0061] The method is the same as Example 1, except that the resin used is the macroporous resin Amberlyst 15. After the addition of the peroxide, the peroxide decomposes with a decomposition conversion rate of 99%, and the products are phenol and cyclohexanone, which cannot achieve the concentration effect.

[0062] Comparative Example 3

[0063] According to the example 1, except that the cyclohexylbenzene solution of cyclohexylbenzene peroxide is replaced by the cyclohexane solution of cyclohexane peroxide, the concentration of the peroxide solution is 4.3wt% by sampling detection, and there is a certain decomposition.

[0064] The above describes the preferred embodiments of the present application in detail, 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, and these simple modifications and combinations should also be considered as the disclosed content of the present application, and all fall within the protection scope of the present application.

Claims

1. A method for concentration of alkylbenzene peroxides, characterized in that, The concentration method comprises contacting the alkylbenzene peroxide solution with a gel-type acidic resin.

2. The concentration method according to claim 1, wherein, the particle size of the gel-type acidic resin is 0.4-0.7 mm; and / or the cross-linking degree of the gel-type acidic resin is 5-20%.

3. The concentration process according to claim 1 or 2, wherein, the gel-type acidic resin is a gel-type strong acidic resin, preferably a styrene-based gel-type strong acidic resin, more preferably a sulfonic acid group-substituted styrene-based gel-type strong acidic resin.

4. The concentration process according to any one of claims 1 to 3, wherein, the gel-type acidic resin is selected from at least one, preferably at least two, of 001X7 strong acidic resin, 001X8 strong acidic resin and 001X12 gel-type strong acidic resin, more preferably a mixture of 001X7 strong acidic resin and 001X12 gel-type strong acidic resin in a mass ratio of 1-2:2-1.

5. The concentration method according to any one of claims 1-4, wherein, the concentration method comprises contacting the alkylbenzene peroxide solution with the gel-type acidic resin in at least two steps, preferably 2-4 steps, more preferably the cross-linking degree of the gel-type acidic resin in any two adjacent steps is less than 3-10% of the cross-linking degree of the gel-type acidic resin in the next step; preferably, the concentration method comprises contacting the alkylbenzene peroxide solution with a first gel-type acidic resin having a cross-linking degree of 5-17%, and a second gel-type acidic resin having a cross-linking degree of 8-20% to obtain the concentrated alkylbenzene peroxide solution; more preferably, the first gel-type acidic resin is 001X7 gel-type strong acidic resin, and the second gel-type acidic resin is 001X12 gel-type strong acidic resin; and / or the mass ratio of 001X7 strong acidic resin to 001X12 gel-type strong acidic resin is 1-2:2-1.

6. The concentration process according to any one of claims 1 to 5, wherein, the concentration of the alkylbenzene peroxide solution is 10-20 wt%; preferably, the alkylbenzene peroxide in the alkylbenzene peroxide solution is C9-C16 alkylbenzene peroxide, preferably at least one of cyclohexylbenzene peroxide, cyclopentylbenzene peroxide, cumene peroxide, dicumene peroxide and cyclooctylbenzene peroxide, more preferably cyclohexylbenzene peroxide and / or cyclopentylbenzene peroxide; and / or the solvent in the alkylbenzene peroxide solution is an alkylbenzene solvent, preferably at least one of cyclohexylbenzene, cyclopentylbenzene, cumene and dicumene, and cyclooctylbenzene.

7. The concentration process according to any one of claims 1 to 6, wherein, the contacting conditions comprise: the weight percentage of the gel-type acidic resin to the alkylbenzene peroxide solution is 0.1-5:1, preferably 0.5-4:1, more preferably 1-2:1; and / or the temperature is 0-80℃, preferably 10-60℃, more preferably 20-55℃; and / or the time is 0.1-6h, preferably 0.5-4h, more preferably 2-3h.

8. The concentration process according to any one of claims 1 to 7, wherein, the gel-type acidic resin is eluted with an eluent after the contacting is completed and reused; the eluent is recycled after being purified; preferably, the eluent is at least one of methanol, ethanol, isopropanol and acetone.

9. Alkylbenzene peroxide obtainable by the concentration process according to any one of claims 1 to 8.

10. Alkylbenzene peroxide according to claim 9, having a concentration of 25 to 60 wt.-% and a content of phenol cyclohexanone and / or phenylcyclohexanol of 0.

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