A process for the preparation of dicumyl peroxide

Abstract

The application provides a preparation method of dihydroperoxy cumene, comprising the following steps: continuously feeding diisopropylbenzene into a reactor, and performing an oxidation reaction in the presence of a base to obtain dihydroperoxy cumene; wherein the reactor comprises N reaction sections distributed along the flow direction of the diisopropylbenzene, and N is an integer greater than or equal to 2; and the base is added into the reactor from at least two reaction sections in the process of the oxidation reaction. By using the above method and device for preparing dihydroperoxy cumene, dihydroperoxy cumene with high selectivity can be obtained.

Description

TECHNICAL FIELD

[0001] The application relates to a preparation method of dihydroperoxy cumene, and belongs to the technical field of organic chemistry. BACKGROUND

[0002] Preparation of dihydroperoxy cumene from cumene oxidation is an important link in the resorcinol industrial chain, and downstream products can cover four products of acetone, resorcinol, BIPB and diisopropenyl benzene.

[0003] When cumene is subjected to oxidation reaction, an alpha-carbon on an isopropyl group of cumene is oxidized by oxygen to form a peroxide bond to obtain a corresponding peroxide product such as dihydroperoxy cumene and dihydroperoxy cumene. In the process of generating dihydroperoxy cumene, benzyl alcohol impurities will also appear in the system. Too much benzyl alcohol impurities will not only cause system blockage, affect production efficiency, but also reduce the selectivity of peroxide dihydroperoxy cumene and reduce the reaction economy.

[0004] Therefore, how to effectively inhibit the generation of benzyl alcohol impurities and improve the production efficiency and reaction economy is a technical problem to be solved by those skilled in the art. SUMMARY

[0005] The main purpose of the present application is to provide a preparation method of dihydroperoxy cumene, which can effectively inhibit the generation of benzyl alcohol, improve the selectivity of dihydroperoxy cumene, and thus improve the production efficiency and reaction economy in actual industry.

[0006] The present application provides a preparation method of dihydroperoxy cumene, comprising the following steps:

[0007] The cumene raw material is continuously introduced into the reactor, and oxidation reaction is carried out in the presence of alkali to obtain dihydroperoxy cumene;

[0008] The reactor comprises N reaction sections distributed along the flow direction of the cumene raw material, and N is an integer greater than or equal to 2.

[0009] During the oxidation reaction, the alkali is added to the reactor from at least two of the N reaction sections.

[0010] The preparation method of dihydroperoxy cumene as described above, the process of adding the alkali to the reactor from at least two of the N reaction sections comprises: for any reaction section, alkali liquor containing the alkali is continuously added to the reaction section to realize the addition of the alkali to the reactor from the reaction section.

[0011] The method for preparing dihydroperoxide cumene as described above, wherein the diisopropylbenzene-based raw material comprises at least one of diisopropylbenzene and dihydroperoxide cumene.

[0012] The method for preparing dihydroperoxide cumene as described above, wherein during the oxidation reaction, for any reaction section, the amount of substance m of the base added to the reactor per hour through the reaction section satisfies:

[0013] 0.3A≤m≤3A,

[0014] wherein, ,

[0015] T is the reaction temperature of the reaction section, in ℃;

[0016] C is 2-3.5, in mol / L;

[0017] Z is the anion charge number of the base added to the reactor through the reaction section;

[0018] t is the residence time of the reaction section, in h.

[0019] The method for preparing dihydroperoxide cumene as described above, wherein for any reaction section, the residence time t of the reaction section is 3-40 h.

[0020] The method for preparing dihydroperoxide cumene as described above, wherein the reaction temperature T of the oxidation reaction in each reaction section is 80-100 ℃; and / or,

[0021] The reaction pressure of the oxidation reaction in each reaction section is 200-600 kPa.

[0022] The method for preparing dihydroperoxide cumene as described above, wherein N is an integer of 2-9.

[0023] The method for preparing dihydroperoxide cumene as described above, wherein in each reaction section, the diisopropylbenzene-based raw material is contacted with a gas containing oxygen to perform the oxidation reaction.

[0024] The method for preparing dihydroperoxide cumene as described above,

[0025] The gas containing oxygen comprises air;

[0026] After the oxidation reaction, the reactor produces tail gas, and the mass percentage of oxygen in the tail gas is 5-8 wt%.

[0027] The method for preparing dihydroperoxide cumene as described above, wherein the reactor comprises N sub-reactors connected in sequence, and the reaction sections are the sub-reactors.

[0028] The preparation method of the cumene hydroperoxide provided by the present application continuously reacts raw materials in multiple reactors in series, which is beneficial to reduce the generation of by-product benzyl alcohol impurities, improve the production equipment blockage problem caused by by-products, and improve the reaction economy and production efficiency. BRIEF DESCRIPTION OF DRAWINGS

[0029] The accompanying drawings, which are incorporated into and form part of the specification, illustrate embodiments consistent with the present application and, together with the description, serve to explain the principles of the application.

[0030] Figure 1 The preparation device structure diagram of the cumene hydroperoxide provided by the present application.

[0031] BRIEF DESCRIPTION OF DRAWINGS

[0032] 1 - first reactor;

[0033] 11 - feeding port;

[0034] 12 - feeding port;

[0035] 13 - reaction liquid outlet;

[0036] 14 - feeding port;

[0037] 2 - second reactor;

[0038] 21 - feeding port;

[0039] 22 - feeding port;

[0040] 23 - reaction liquid outlet;

[0041] 24 - feeding port;

[0042] 3 - third reactor;

[0043] 31 - feeding port;

[0044] 32 - feeding port;

[0045] 33 - product outlet;

[0046] 34 - feeding port.

[0047] Through the above drawings, the specific embodiments of the present application have been shown, and will be described in more detail hereinafter. These drawings and written descriptions are not intended to limit the scope of the concept of the present application in any way, but to illustrate the concept of the present application to those skilled in the art by referring to specific embodiments. DETAILED DESCRIPTION

[0048] In order to make the objects, technical solutions and advantages of the present application clearer, the following will combine the embodiments of the present application to make a clear and complete description of the technical solutions in the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all the other embodiments obtained by those skilled in the art without creative work fall within the protection scope of the present application.

[0049] At present, in the process of preparing dihydroperoxy cumene by oxidizing cumene, the hydrogen peroxide groups will decompose to produce small molecule acids, and the continuous existence of the small molecule acids will inhibit the occurrence of the oxidation reaction. In addition, the small molecule acids will also be produced in the process of the side reaction of producing aldehyde and alcohol by oxidizing cumene, and these small molecule acids will cause more side reactions to occur. Therefore, alkali liquor is often added to the raw material system to absorb the small molecule acids produced in the reaction liquid to maintain the oxidation reaction. However, the addition of the alkali liquor will cause a large amount of benzyl alcohol impurities to be generated, which not only blocks the pipeline of the reaction equipment, shortens the equipment maintenance cycle, and causes the production efficiency to be reduced, but also reduces the yield of dihydroperoxy cumene.

[0050] Therefore, accurately controlling the addition amount of the alkali liquor so that the alkali liquor can just react with the small molecule acids in the reaction system is a key problem for reducing the generation of the byproduct benzyl alcohol impurities and improving the generation of the product dihydroperoxy cumene.

[0051] Based on this, the first aspect of the present application provides a preparation method of dihydroperoxy cumene, comprising the following steps:

[0052] The cumene type raw material is continuously introduced into the reactor, and an oxidation reaction is carried out in the presence of alkali to obtain dihydroperoxy cumene.

[0053] The reactor comprises N reaction sections distributed along the flow direction of the cumene type raw material, and N is an integer greater than or equal to 2.

[0054] In the process of the oxidation reaction, the alkali is added to the reactor from at least two reaction sections of the N reaction sections.

[0055] The present application uses cumene or cumene and dihydroperoxy cumene as raw materials, uses alkali as a catalyst, and carries out an oxidation reaction under the catalysis of the alkali to finally obtain dihydroperoxy cumene. In the above preparation method, the cumene type raw material is continuously introduced into the reactor to carry out an oxidation reaction, which realizes mass production in industry.

[0056] In the reaction process, the specific amount of the raw material can be determined according to the target yield of dihydroperoxy cumene, and the amount of the alkali can be determined according to the specific amount of the raw material.

[0057] The base includes at least one of sodium hydroxide, potassium hydroxide, potassium carbonate, and sodium carbonate. It can be understood that the base can be diluted into a base solution and added to at least two of the N reaction sections. The mass percentage of the base solution is not particularly limited in the present application and can be selected according to actual needs. For example, the mass percentage of the base solution can be 0.1-4 wt%, including but not limited to 0.1 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, or a range consisting of any two of them.

[0058] During the oxidation reaction of the raw material in the reactor, the raw material is divided into N reaction sections distributed along the flow direction of the raw material, N is an integer greater than or equal to 2, and the base is added to the reactor from at least two of the N reaction sections. In detail, the base can be added to each of the N reaction sections, or only to at least two of the N reaction sections, and no base is added to the remaining reaction sections.

[0059] As described above, the process of adding the base from at least two of the N reaction sections to the reactor includes: for any reaction section, continuously adding a base solution containing the base to the reaction section to achieve the addition of the base from the reaction section to the reactor.

[0060] Specifically, taking an example of 3 reaction sections distributed along the flow direction of the raw material, the diisopropylbenzene raw material is oxidized with the base solution introduced into the first reaction section to obtain a first reaction liquid, the first reaction liquid is oxidized with the base solution in the second reaction section to obtain a second reaction liquid, and the second reaction liquid is oxidized with the base solution in the third reaction section to obtain a reaction liquid containing the diisopropylbenzene hydroperoxide product.

[0061] Since the amount of the base solution in the first reaction section is not enough to completely react with all the raw material added, a large amount of unreacted raw material is included in the first reaction liquid in addition to a small amount of diisopropylbenzene hydroperoxide generated. Then, the first reaction liquid and the base solution in the second reaction section are subjected to a second oxidation reaction after the introduction of an oxidizing agent, and part of the raw material in the first reaction liquid is oxidized again to diisopropylbenzene hydroperoxide to obtain a second reaction liquid. In this way, with the reaction liquid in the previous oxidation reaction continuously entering the next oxidation reaction, the oxidation reaction is carried out under the condition of supplementing a portion of the base solution until the Nth reaction section is reached, at which time the last oxidation reaction of the raw material is completed under the catalysis of the base solution in the Nth reaction section.

[0062] In detail, in the process of the oxidation reaction, the total amount of alkali (i.e. the total of the alkali used in the N reaction stages) is divided into multiple portions, and is added in different stages of the reaction, avoiding the current process of adding all the alkali liquid at once in the first reaction stage, which leads to excessive alkali content in the first few reaction stages, and further makes the selectivity of the hydrogen peroxide group in the first few reaction stages low. Therefore, the preparation method of the present application can ensure that the acidic small molecules generated by oxidation are fully removed, and the reaction rate can be maintained at a normal level, on the premise that, on the one hand, the selectivity of the cumene hydroperoxide is increased, and the generation of benzyl alcohol impurities is reduced, thereby improving the economy of the reaction, and on the other hand, the phenomenon of device plugging due to excessive benzyl alcohol impurities is alleviated, and the generation efficiency is improved, and the maintenance cost is reduced.

[0063] After detection, in the Nth reaction stage, the reaction liquid includes a large amount of cumene hydroperoxide, and the content of benzyl alcohol impurities is extremely low, therefore, the preparation method of the present application can significantly improve the selectivity of cumene hydroperoxide, and reduce the generation of benzyl alcohol impurities, thereby ensuring that the device operates normally for a long time without plugging, and producing more cumene hydroperoxide, therefore, the production efficiency and reaction economy are significantly improved.

[0064] In the present application, the raw materials include at least one of diisopropylbenzene and diisopropylbenzene hydroperoxide. The diisopropylbenzene hydroperoxide in the present application is single-side diisopropylbenzene hydroperoxide, which is an intermediate product in the oxidation of diisopropylbenzene to cumene hydroperoxide. The present application uses at least one of diisopropylbenzene and diisopropylbenzene hydroperoxide to synthesize cumene hydroperoxide, which has a high raw material conversion rate.

[0065] In order to further ensure that the alkali can neutralize the small molecule acid generated in the oxidation reaction, and inhibit the generation of benzyl alcohol impurities from the catalytic decomposition of cumene hydroperoxide by alkali, the present application controls that, in the process of the above-mentioned oxidation reaction, for any reaction stage, the amount of substance m of the alkali added to the reactor per hour through the reaction stage satisfies:

[0066] 0.3A≤m≤3A,

[0067] wherein, ,

[0068] T is the reaction temperature of the reaction stage, in units of ℃;

[0069] C is 2-3.5, in units of mol / L;

[0070] Z is the charge number of the anion of the alkali added to the reactor through the reaction stage;

[0071] t is the residence time of the material of the reaction stage, in units of h.

[0072] In detail, T is the temperature of the oxidation reaction in any of the reaction stages, and the temperature of each oxidation reaction is generally controlled to be the same, and if there is a deviation, the average temperature of the oxidation reactions in the N reaction stages can be used; the inventors have found that C represents the concentration of the hydrogen peroxide substance in the reaction liquid in the reaction stage at the inlet of the reaction stage, and the hydrogen peroxide substance is mainly derived from the product cumene hydroperoxide (diisopropylbenzene hydroperoxide), diisopropylbenzene peroxide and other impurity components in the oxidation reaction, and the concentration of the hydrogen peroxide substance is calculated by adding the concentration of the cumene hydroperoxide to twice the concentration of the diisopropylbenzene peroxide, and the concentration of the hydrogen peroxide substance can also be represented by the concentration of active oxygen in the reaction liquid in the reaction stage, and the active oxygen is the oxygen atom with oxidation activity in the hydrogen peroxide group, and the concentration of active oxygen in the reaction liquid can be determined by the iodometric method; Z is the anion charge number of the base, for example, when the base is sodium hydroxide, Z is 1, and when the base is sodium carbonate, Z is 2.

[0073] When the amount of substance of the base added to the reactor per hour through the reaction stage is determined according to the above formula 1, the selectivity of diisopropylbenzene peroxide can be further improved, and the generation of benzyl alcohol impurities can be reduced.

[0074] In addition, the inventors have found that the residence time is also a key factor for improving the selectivity of diisopropylbenzene peroxide and reducing the selectivity of benzyl alcohol impurities. For any reaction stage, the residence time t of the material in the reaction stage is 3-20 h, for example, the residence time t of the material in the reaction stage includes but is not limited to 3 h, 10 h, 20 h or a range formed by any two of them.

[0075] The present application improves the selectivity of diisopropylbenzene peroxide and reduces the generation of benzyl alcohol impurities by further limiting the temperature and pressure of the oxidation reaction. In a specific embodiment, the temperature of the oxidation reaction is 80-100°C. For example, the temperature of the oxidation reaction includes but is not limited to 80°C, 85°C, 90°C, 95°C, 100°C or a range formed by any two of them.

[0076] In a specific embodiment, the pressure of the oxidation reaction is 200-600 kPa. For example, the pressure of the oxidation reaction includes but is not limited to 200 kPa, 300 kPa, 400 kPa, 500 kPa, 600 kPa or a range formed by any two of them.

[0077] Further, the present application is not additionally limited to the number of reaction stages N, and exemplarily, N is 2-9. Specifically, the number of reaction stages can be determined according to the amount of raw material, and the larger the raw material system, the more the number of reaction stages. In the above preparation method of dicumyl peroxide, the diisopropyl benzene-based raw material and the gas containing oxygen are contacted to perform the oxidation reaction in each reaction stage.

[0078] In the process of the oxidation reaction, the present application is not limited to the specific selection of the oxidant, but in order to avoid introducing too many impurities into the reaction system, air or oxygen can be used as the oxidant. It can be understood that when air is selected as the oxidant, it helps to further reduce the cost.

[0079] It should be clear that because the gas is introduced to participate in the oxidation reaction during the oxidation reaction, tail gas is generated in the reactor after the oxidation reaction. Since the oxidation reaction is carried out at a certain temperature, the mass percentage of oxygen in the tail gas discharged from the reactor after the oxidation reaction can be controlled to be 5-8%, which ensures the continuity and safety of the reaction, avoids the risk of incomplete oxidation reaction or explosion and fire due to too low or too high oxygen concentration in the system.

[0080] After the reaction is completed, a reaction system including dicumyl peroxide is obtained, and by post-treating the reaction system generated in the Nth reaction stage, the dicumyl peroxide can be separated from the remaining components in the reaction system.

[0081] Specifically, the post-treatment includes sequentially extracting the reaction system.

[0082] Among them, the extraction treatment first uses a 3%-15% sodium hydroxide solution for one extraction treatment, at this time the product enters the sodium hydroxide solution, and a sodium hydroxide solution including the product is obtained, and the remaining phase is reused in the above oxidation reaction. Next, at least one of a ketone with 4-10 carbon atoms, an ether with 4-10 carbon atoms, and an alcohol with 4-8 carbon atoms is used as an extractant to perform secondary extraction treatment on the above obtained sodium hydroxide solution including the product, and methyl isobutyl ketone is most preferably used as the extractant. Through the extraction treatment, the dicumyl peroxide is dissolved in the extractant to separate from the sodium hydroxide solution to obtain the product dicumyl peroxide with higher purity. The secondary extraction temperature includes low-temperature extraction treatment and high-temperature extraction treatment. The above low-temperature extraction is carried out at a temperature of about 10-40°C, and the high-temperature extraction is carried out at a temperature of 7-80°C.

[0083] As described above, the reactor includes N sub-reactors sequentially connected, and the reaction stage is the sub-reactor.

[0084] Specifically, the above-mentioned method for preparing cumene hydrogen peroxide is carried out by a preparation apparatus including a reactor. The reactor includes N sub-reactors connected in series. Each sub-reactor is filled with the reaction liquid in the reaction section. The reaction liquid outlet of the previous sub-reactor is connected to the reaction liquid inlet of the next sub-reactor.

[0085] The sub-reactor includes a reaction liquid outlet and a reaction liquid inlet. The reaction liquid outlet is used to output the reaction liquid in the current sub-reactor, and the reaction liquid inlet is used to receive the reaction liquid from the previous reactor.

[0086] Each sub-reactor also includes a feed port for adding raw materials and alkali solution to the reactor. The invention does not limit the number of feed ports; there can be one or more. Taking the first reactor as an example, when it includes one feed port, both the raw materials and alkali solution can be added to the reactor through this feed port; when it includes multiple feed ports, the diisopropylbenzene raw materials and alkali solution can be added to the reactor through different feed ports. Of course, an oxidant can also enter the reactor through the feed port.

[0087] This invention does not impose any special limitation on the volume of each sub-reactor in the series of sub-reactors; the volume can be selected according to the actual situation, and the volumes of each sub-reactor can be the same or different.

[0088] Taking N=2 as an example, such as Figure 1 As shown, the apparatus of the present invention includes a first sub-reactor 1, a second sub-reactor 2, and a third sub-reactor 3 connected in series. The reaction liquid outlet 13 of the first sub-reactor 1 is connected to the feed port 22 of the second sub-reactor 2, and the reaction liquid outlet 13 is used to output the reaction liquid in the first sub-reactor to the second sub-reactor 2. The reaction liquid outlet 23 of the second sub-reactor 2 is connected to the feed port 32 of the third sub-reactor 3, and the reaction liquid outlet 23 is used to output the reaction liquid in the second sub-reactor 2 to the third sub-reactor 3. The product outlet 33 is used to output the reaction liquid in the third sub-reactor.

[0089] The first sub-reactor 1 includes three feed ports: feed port 11 is used to add diisopropylbenzene raw materials to the sub-reactor, feed port 12 is used to add alkaline solution to the sub-reactor, and feed port 14 is used to introduce oxidant into the sub-reactor.

[0090] The second sub-reactor 2 includes three feed ports: feed port 21 is used to add alkaline solution to the second sub-reactor, feed port 22 is used to add reaction liquid from the first sub-reactor to the second sub-reactor, and feed port 24 is used to introduce oxidant into the second sub-reactor.

[0091] The third sub-reactor 3 includes three feeding ports, the feeding port 31 is used for feeding alkali liquor into the third sub-reactor, the feeding port 32 is used for feeding the reaction liquor from the second sub-reactor into the third sub-reactor, and the feeding port 34 is used for feeding oxidant into the second sub-reactor.

[0092] Specifically, the continuous preparation process of cumene hydroperoxide using the preparation device is as follows: the raw material of diisopropylbenzene is fed into the first sub-reactor 1 from the feeding port 11 of the first sub-reactor, the first portion of alkali liquor is fed into the first sub-reactor 1 from the feeding port 12 of the first sub-reactor, and then the oxidant is fed into the first sub-reactor from the feeding port 14 of the first sub-reactor, so that the oxidant, the raw material and the alkali liquor perform the first-stage oxidation reaction in the first sub-reactor 1, and the reaction liquor of the first-stage oxidation reaction is obtained at the outlet 13 of the reactor;

[0093] The reaction liquor of the first-stage oxidation reaction can be directly fed into the second sub-reactor from the reaction liquor outlet 13 of the first sub-reactor through the feeding port 22 of the second sub-reactor, while the second portion of alkali liquor is continuously fed into the feeding port 21 of the second sub-reactor, and air is fed into the feeding port 23 of the second sub-reactor to perform the second-stage oxidation reaction, and the reaction liquor of the second-stage oxidation reaction is obtained at the outlet 23 of the reactor;

[0094] The second reaction liquor is directly fed into the third sub-reactor 3 from the reaction liquor outlet 23 of the second sub-reactor through the feeding port 32 of the second sub-reactor, while the alkali liquor is continuously fed into the feeding port 31 of the third sub-reactor, and the oxidant is fed into the feeding port 34 of the third sub-reactor to continue the third-stage oxidation reaction, and the reaction liquor including cumene hydroperoxide is obtained in the third sub-reactor 3 after the reaction is completed, and the reaction liquor including cumene hydroperoxide is collected from the product outlet 33 of the third sub-reactor.

[0095] The continuous generation of the raw material and the continuous output of the product greatly reduce the non-reaction time in the reaction process, thereby significantly improving the reaction efficiency. Moreover, in the continuous reaction process, the raw material can be fully utilized, thereby reducing the waste of resources.

[0096] By using the above preparation device to prepare cumene hydroperoxide, the reaction can be controlled to generate the target product cumene hydroperoxide by controlling the amount of alkali liquor, which is beneficial to the selectivity of cumene hydroperoxide preparation, and further improves the economy of the reaction. In addition, by using the above preparation device to prepare cumene hydroperoxide, the raw material can be continuously oxidized, which is beneficial to realize mass production, and further improves the production efficiency.

[0097] Further, the preparation device further comprises a post-treatment assembly, the post-treatment assembly comprising extraction towers connected in sequence, wherein the extraction towers are in communication with the reaction liquid outlet of the Nth sub-reactor. By using the post-treatment assembly to post-treat the reaction liquid, the purity of the cumene dihydroperoxide obtained is higher.

[0098] The technical solutions of the present application are further described below in combination with specific examples.

[0099] The reagents used in this example are as follows:

[0100] m,p-Dicumene, purity 98%;

[0101] The equipment used in this example is as follows:

[0102] Reaction kettle, Yantai Ailang Machinery Technology Co., Ltd., design pressure: 1 Mpa;

[0103] Example 1

[0104] The reaction assembly in the preparation device used in this example comprises two sub-reactors connected in series, wherein the reaction liquid outlet of the first sub-reactor is in communication with the feeding port of the second sub-reactor. Both the first sub-reactor and the second sub-reactor comprise three feeding ports for adding raw materials, alkali solution and oxidizing agent into the sub-reactor.

[0105] The preparation method of this example comprises the following steps:

[0106] 1) The raw materials and alkali solution are added into the first sub-reactor, and air is introduced into the first sub-reactor to perform an oxidation reaction (i.e., the first reaction section), thereby obtaining a first reaction liquid;

[0107] The volume of the diisopropylbenzene raw material is 1 m 3 The molar concentration of the diisopropylbenzene hydroperoxide in the raw material is 2.5 mol / L, and the molar concentration of the diisopropylbenzene is 3 mol / L;

[0108] The alkali solution is sodium hydroxide with a mass percentage of 0.1%;

[0109] The reaction pressure of the oxidation reaction in the first sub-reactor is 300 kpa;

[0110] The reaction temperature of the oxidation reaction in the first sub-reactor is 90℃, and the reaction time is 3 h;

[0111] In the oxidation reaction in the first sub-reactor, the amount of substance m of the alkali added into the sub-reactor per hour through the reaction section is calculated by the following formula:

[0112] m = 0.3A,

[0113] wherein, T is 80℃; C=2.5mol / L; Z is 1; t is 3h, C is 2.5mol / L. And the calculation can get the outlet active oxygen molar concentration of 3.1mol / L

[0114] The calculation can get m=0.2325, i.e. the average amount of substance of the base added to the reactor per hour through the reaction section is m=0.2325mol.

[0115] In the oxidation reaction in the first sub-reactor, the tail oxygen concentration is controlled to be 5%.

[0116] 2) The above first reaction liquid and the base solution are subjected to an oxidation reaction in the second sub-reactor to obtain the product cumene dihydroperoxide;

[0117] Wherein,

[0118] The volume of the first reaction liquid in the second sub-reactor is 1m 3 The reaction pressure of the oxidation reaction in the second sub-reactor is 300kpa;

[0119] The reaction temperature of the oxidation reaction in the second sub-reactor is 80℃, and the reaction time is 3h;

[0120] In the oxidation reaction in the second sub-reactor, the average amount of substance of the base added to the reactor per hour through the reaction section m is calculated by the following formula:

[0121] m=0.3A,

[0122] Wherein, T is 80℃; C is 3.1mol / L; Z is 1; t is 3h. Get m=0.2775, i.e. the average amount of substance of the base added to the reactor per hour through the reaction section is 0.2775mol.

[0123] In the oxidation reaction in the second sub-reactor, the tail oxygen concentration is controlled to be 5%.

[0124] Example 2

[0125] This example is basically the same as Example 1, the difference is that in step 1), the average amount of substance of the base added to the reactor per hour through the reaction section m=A;

[0126] In step 2), the average amount of substance of the base added to the reactor per hour through the reaction section m=2A.

[0127] Example 3

[0128] This example is substantially the same as Example 1, except that in step 1), the average molar amount of the base added to the reactor per hour through the reaction section is m = 8A.

[0129] In step 2), the average molar amount of the base added to the reactor per hour through the reaction section is m = 6A.

[0130] Example 4

[0131] This example is substantially the same as Example 1, except that in this example, the residence time t in step 1) and step 2) is 6h.

[0132] Example 5

[0133] This example is substantially the same as Example 1, except that in this example, the residence time t in step 1) and step 2) is 25h.

[0134] Example 6

[0135] This example is substantially the same as Example 1, except that in this example, C = 3 in step 1) and step 2).

[0136] Example 7

[0137] This example is substantially the same as Example 1, except that in this example, C = 4 in step 1) and step 2).

[0138] Comparative Example 1

[0139] This comparative example is substantially the same as Example 1, except that in this comparative example, the total amount of base used in step 1) and step 2) of Example 1 is added at once in the first reaction section.

[0140] Test Example

[0141] The reaction liquid collected at the reactor product outlet in the examples and comparative examples, including the product diisopropylbenzene hydroperoxide, was subjected to liquid phase analysis. Specifically, the diisopropylbenzene hydroperoxide molar amount in the reaction liquid was obtained by liquid phase analysis using a Shimadzu LC20A liquid chromatograph and a Shimadzu phenyl column under the following conditions: the ratio of water to acetonitrile in the mobile phase was 1:1, the analysis temperature was 30°C, and the analysis time was 2h.

[0142] The selectivity of diisopropylbenzene hydroperoxide in the examples and comparative examples was calculated according to the following formula, and the results are shown in Table 1.

[0143] The selectivity calculation formula: diisopropylbenzene hydroperoxide molar amount selectivity = (diisopropylbenzene hydroperoxide molar amount in the reaction liquid) / (diisopropylbenzene molar amount in the raw material + diisopropylbenzene hydroperoxide in the raw material - diisopropylbenzene molar amount in the outflow - diisopropylbenzene hydroperoxide in the outflow).

[0144] The selective calculation results are shown in Table 1.

[0145] Table 1

[0146]

[0147] As shown in the table, examples 1-7 have higher cumene hydroperoxide selectivity than comparative example 1. In addition, examples 1-2, 4, 6 also have higher cumene hydroperoxide selectivity than examples 3, 5, 7 by further controlling the average amount of substance of the base added to the reactor per hour in the oxidation reaction, the residence time of the material, and the concentration of active oxygen in the reaction solution in the reaction section. Therefore, the present application is beneficial to the selectivity of the cumene hydroperoxide reaction solution and reduces the generation of side reactions by setting multiple sub-reactors in series and adding base solution to each sub-reactor for the oxidation reaction of the cumene hydroperoxide reaction solution.

[0148] Finally, it should be noted that: the above examples are only used to illustrate the technical solutions of the present application, and not to limit it; although the present application has been described in detail with reference to the foregoing examples, those skilled in the art should understand that: it can still modify the technical solutions recorded in the foregoing examples, or make equivalent replacement for part or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present application.

Claims

1. A method for preparing cumene hydrogen peroxide, characterized in that, Includes the following steps: The diisopropylbenzene raw material is continuously fed into the reactor and oxidized in the presence of alkali to obtain diisopropylbenzene dihydroperoxide; The reactor comprises N reaction sections distributed along the flow direction of the diisopropylbenzene raw material, where N is an integer greater than or equal to 2. During the oxidation reaction, the alkali is added to the reactor from at least two of the N reaction sections; During the oxidation reaction, for any given reaction segment, the average amount m of the alkali added to the reactor per hour through that reaction segment satisfies the following: 0.3A≤m≤3A in, , T is the reaction temperature of this reaction section, expressed in °C. C is 2-3.5, in mol / L. Z represents the charge number of the anions of the base added to the reactor through this reaction section; t represents the residence time of the material in this reaction section, expressed in hours (h).

2. The method for preparing cumene hydrogen peroxide according to claim 1, characterized in that, The process of adding the alkali from at least two of the N reaction sections into the reactor includes: for any one of the reaction sections, continuously adding an alkali solution containing the alkali into that reaction section to achieve the addition of the alkali from that reaction section into the reactor.

3. The method for preparing cumene dihydroperoxide according to claim 1 or 2, characterized in that, The diisopropylbenzene raw materials include at least one of diisopropylbenzene and diisopropylbenzene peroxide.

4. The method for preparing cumene dihydroperoxide according to claim 1 or 2, characterized in that, For any reaction section, the material residence time t in that reaction section is 3~20h.

5. The method for preparing cumene dihydroperoxide according to claim 1 or 2, characterized in that, The reaction temperature T of the oxidation reaction in each of the aforementioned reaction sections is 80~100℃; and / or, The reaction pressure of the oxidation reaction in each of the reaction sections is 200~600 kPa.

6. The method for preparing cumene hydrogen peroxide according to claim 1 or 2, characterized in that, N is an integer from 2 to 9.

7. The method for preparing cumene dihydroperoxide according to claim 1 or 2, characterized in that, In each of the reaction sections, the diisopropylbenzene raw material is brought into contact with an oxygen-containing gas to carry out the oxidation reaction.

8. The method for preparing cumene hydrogen peroxide according to claim 7, characterized in that, The oxygen-containing gas includes air; And / or, after the oxidation reaction, the reactor produces tail gas, the tail gas containing 5 to 8 wt% oxygen.

9. The method for preparing cumene hydrogen peroxide according to claim 1 or 2, characterized in that, The reactor comprises N sequentially connected sub-reactors, and the reaction section is one of the sub-reactors.

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