阅读说明：本技术 过氧化氢异丙苯与碱反应的方法 (Method for reacting cumene hydroperoxide with alkali ) 是由 孙峰 徐伟 周明川 石宁 于 2020-04-10 设计创作，主要内容包括：本发明涉及过氧化氢异丙苯与碱反应的领域,公开了一种过氧化氢异丙苯与碱反应的方法,该方法包括：(1)将部分过氧化氢异丙苯溶液与碱溶液进行第一接触反应,得到第一物料；(2)将剩余部分的过氧化氢异丙苯溶液引入所述第一物料中进行第二接触反应,得到第二物料；所述第一接触反应不生成沉淀；所述第二接触反应过程中,过氧化氢异丙苯的累积率不大于20重量％。本发明的方法能够保障过氧化氢异丙苯与碱反应的安全,降低反应失控的风险。(The invention relates to the field of reaction of cumene hydroperoxide and alkali, and discloses a method for reacting cumene hydroperoxide with alkali, which comprises the following steps: (1) carrying out a first contact reaction on part of cumene hydroperoxide solution and an alkali solution to obtain a first material; (2) introducing the rest part of cumene hydroperoxide solution into the first material to carry out a second contact reaction to obtain a second material; the first contact reaction does not generate precipitate; the cumyl hydroperoxide accumulation rate during the second contact reaction is no greater than 20 wt%. The method can ensure the safety of the reaction of the cumene hydroperoxide and the alkali and reduce the risk of reaction out of control.)

1. A process for reacting cumene hydroperoxide with a base, the process comprising:

(1) carrying out a first contact reaction on part of cumene hydroperoxide solution and an alkali solution to obtain a first material;

(2) introducing the rest part of cumene hydroperoxide solution into the first material to carry out a second contact reaction to obtain a second material;

the first contact reaction does not generate precipitate;

the cumyl hydroperoxide accumulation rate during the second contact reaction is no greater than 20 wt%.

2. The process according to claim 1, wherein the weight ratio of the alkali solution to the total amount of cumene hydroperoxide solution used is from 0.05 to 0.3: 1.

3. the process according to claim 2, wherein the weight ratio of the alkali solution to the total amount of cumene hydroperoxide solution used is from 0.08 to 0.18: 1.

4. the process according to any one of claims 1 to 3, wherein the weight ratio of the partial cumene hydroperoxide solution to the base solution of step (1) is from 0.5 to 3: 1, preferably 1-2: 1.

5. a process according to any one of claims 1 to 4, wherein the concentration of the alkali solution is greater than 20% by weight, preferably 40 to 60% by weight.

6. The method of any one of claims 1-5, wherein the base is selected from at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium carbonate, ammonium bicarbonate, and ammonia.

7. The process according to any one of claims 1 to 6, wherein the cumene hydroperoxide solution has a concentration of 40 to 80 wt. -%, preferably of 45 to 65 wt. -%.

8. The process according to any one of claims 1 to 7, wherein the solvent of the cumene hydroperoxide solution is selected from at least one of cumene, chlorobenzene, ethanol and acetone.

9. The process of any of claims 1-8, wherein the cumene hydroperoxide accumulation during the second contacting reaction is no greater than 12 wt%.

10. The method of any one of claims 1-9, wherein the first contact reaction conditions comprise: under the condition of stirring, the temperature is 40-120 ℃.

11. The method of claim 10, wherein the first contact reaction conditions comprise: under the condition of stirring, the temperature is 60-80 ℃.

12. The method of any one of claims 1-11, wherein the second contact reaction conditions comprise: under the condition of stirring, the temperature is 50-100 ℃.

13. The method of claim 12, wherein the second contact reaction conditions comprise: under the condition of stirring, the temperature is 60-80 ℃.

14. The method of any one of claims 1-13, wherein the method further comprises performing interlock control during the first contact reaction and/or the second contact reaction.

15. The method of claim 14, wherein the interlock control comprises: stopping the first contact reaction and/or the second contact reaction when the temperature in the first contact reaction and/or the second contact reaction is higher than the termination temperature, and simultaneously reducing the temperature of the first material and/or the second material to be below 50 ℃ within 1-10 min; the termination temperature is 70-95 ℃.

Technical Field

The invention relates to the field of reaction of cumene hydroperoxide and alkali, in particular to a method for reacting cumene hydroperoxide and alkali.

Background

The process of preparing dimethylbenzyl alcohol (CA) from Cumene Hydroperoxide (CHP) is a key step in the process of synthesizing dicumyl peroxide (DCP) from cumene. At present, sodium sulfide (NaS) is widely used in industry₂Or Na₂SO₃) Cumene hydroperoxide is reduced to produce dimethylbenzyl alcohol. Although the method has simple process and high selectivity, the atom utilization rate of the reaction is low, a large amount of sulfur-containing wastewater can be generated, the environmental pollution is caused, the subsequent environmental protection treatment is usually required, and the method is not economical and also meets the aim of green chemistry.

The dimethyl benzyl alcohol is prepared by the reaction of sodium hydroxide and cumene hydroperoxide, and the problem of environmental pollution can be effectively solved. However, cumene hydroperoxide has a molecular structure in which an unstable "-O-" bond exists, so that it can undergo radical or ion decomposition through various routes, and has high reactivity. Cumene hydroperoxide can react violently when being subjected to alkali, and if the conditions are not controlled properly, the cumene hydroperoxide has the danger of explosion caused by runaway, and serious results can be caused.

Jinman et al (report of chemical industry, influence of water and weak acid on thermal risk of cumene hydroperoxide, 2012,63: 4096-. The yellow army and the like (the science of safety of china, the study on the thermal stability and the thermal safety of cumene hydroperoxide, 2011) studied the thermal stability and the thermal safety of the cumene hydroperoxide, calculated the self-accelerated decomposition temperature (SADT) of the cumene hydroperoxide in different packages, but did not study the reaction characteristics of the cumene hydroperoxide and alkali.

The prior literature only aims at the research of the decomposition risk of the cumene hydroperoxide, provides the safe conditions of the cumene hydroperoxide during storage and transportation, does not systematically research the dangerous characteristics of the reaction of the cumene hydroperoxide and alkali, and does not disclose the safe operating conditions and the safe operating method of the reaction of the cumene hydroperoxide and the alkali.

Disclosure of Invention

The invention aims to provide a method for reacting cumene hydroperoxide with alkali aiming at the dangerous characteristic of the reaction of the cumene hydroperoxide with the alkali, which can ensure the safety of the reaction and reduce the risk of reaction runaway.

In order to achieve the above object, the present invention provides a method for reacting cumene hydroperoxide with a base, the method comprising:

(1) carrying out a first contact reaction on part of cumene hydroperoxide solution and an alkali solution to obtain a first material;

(2) introducing the rest part of cumene hydroperoxide solution into the first material to carry out a second contact reaction to obtain a second material;

the first contact reaction does not generate precipitate;

the cumyl hydroperoxide accumulation rate during the second contact reaction is no greater than 20 wt%.

Preferably, the weight ratio of the alkali solution to the total amount of the cumene hydroperoxide solution is 0.05-0.3: 1, preferably 0.08 to 0.18: 1.

preferably, the cumene hydroperoxide solution has a concentration of 40 to 80 wt.%, preferably 45 to 65 wt.%.

Preferably, the cumene hydroperoxide accumulation rate during the second contact reaction is not greater than 12 wt%.

Through the technical scheme, the method for reacting the cumene hydroperoxide with the alkali, which is provided by the invention, not only avoids the production of precipitate due to excessive alkali, but also avoids the decomposition of the cumene hydroperoxide due to excessive alkali, thereby ensuring the safe operation of the reaction. In addition, by controlling the proper accumulation rate, the danger of secondary decomposition of the cumene hydroperoxide when the reaction is out of control is reduced. Even when the reaction is out of control, the invention preferably takes the mode of linkage control to process emergently, thereby avoiding further expansion of accidents. The method effectively controls the risk of runaway reaction of the cumene hydroperoxide and the alkali, and ensures the safety of the reaction of the cumene hydroperoxide and the alkali.

Detailed Description

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

In the present invention, the cumyl hydroperoxide accumulation rate refers to the weight content of unreacted cumyl hydroperoxide in the reaction mixture.

Unless otherwise specified, in the present invention, the semi-batch operation, also referred to as semi-continuous operation, is to add one reactant at a time, then continuously add the other reactant, and when the reaction reaches a certain requirement, stop the operation and discharge the material.

The invention provides a method for reacting cumene hydroperoxide with alkali, which comprises the following steps:

(1) carrying out a first contact reaction on part of cumene hydroperoxide solution and an alkali solution to obtain a first material;

(2) introducing the rest part of cumene hydroperoxide solution into the first material to carry out a second contact reaction to obtain a second material;

the first contact reaction does not generate precipitate;

the cumyl hydroperoxide accumulation rate during the second contact reaction is no greater than 20 wt%.

The cumene hydroperoxide is dangerous to decompose, so the inventor of the invention finds that if a mode of adding alkali into excessive cumene hydroperoxide is adopted, the cumene hydroperoxide is easy to decompose to cause reaction runaway; when cumene hydroperoxide is added to an excess amount of alkali, a solid precipitate is easily formed, which is not favorable for further reaction.

In the invention, when the cumyl hydroperoxide accumulation rate is not more than 20 weight percent in the second contact reaction process, not only can solid precipitates not be easily produced in the reaction process be ensured, but also the reaction runaway caused by the decomposition of the cumyl hydroperoxide can be avoided.

According to the present invention, preferably, the weight ratio of the partial cumene hydroperoxide solution to the alkali solution in the step (1) is 0.5 to 3: 1, more preferably 1 to 2: 1. in this preferred case, it is more advantageous to control the first contact reaction without producing a precipitate and to ensure that the reaction proceeds safely.

In the present invention, the weight ratio of the total amount of the alkali solution to the cumene hydroperoxide solution is selected from a wide range, and preferably, the weight ratio of the alkali solution to the total amount of the cumene hydroperoxide solution is 0.05 to 0.3: 1.

according to a preferred embodiment of the present invention, the weight ratio of the alkali solution to the total amount of cumene hydroperoxide solution used is 0.08 to 0.18: 1. in this preferred case, it is advantageous to increase the conversion of cumene hydroperoxide by reaction with alkali.

According to the invention, by measuring the relationship between the heat flow and the reaction temperature when the cumene hydroperoxide solution reacts with the sodium hydroxide solution under different weight ratios of the sodium hydroxide solution and the cumene hydroperoxide solution, the reaction of the cumene hydroperoxide with the sodium hydroxide has a first exothermic peak at about 40-120 ℃ and a second exothermic peak at about 120-250 ℃. The first peak corresponds to the reaction of cumene hydroperoxide with sodium hydroxide to form benzyl alcohol and the second peak corresponds to the decomposition of cumene hydroperoxide.

Under the premise that the concentration of the cumene hydroperoxide is fixed, the higher the weight ratio of the sodium hydroxide solution to the cumene hydroperoxide solution is, the higher the conversion rate of the reaction of the cumene hydroperoxide and the sodium hydroxide is in the temperature range corresponding to the first exothermic peak. The weight ratio of the sodium hydroxide solution to the cumene hydroperoxide solution is increased in a certain range, which is beneficial to improving the conversion rate of the reaction of the cumene hydroperoxide and the sodium hydroxide.

In the present invention, the heat flow, which refers to the amount of heat released per unit of time, is measured in real time by a microcalorimeter, model C80, from satalm, france; what is needed isThe calorimetric pool is a hastelloy high-pressure pool, the reference substance is alpha-alumina, and the heating rate is 1 ℃ min^-1The scanning temperature range is 30-300 ℃.

The concentration of the alkali solution in the present invention is selected from a wide range as long as cumene hydroperoxide can react with alkali, and specifically, for example, the concentration may be 5 wt%, 10 wt%, 15 wt%, 20 wt%, 30 wt%, 40 wt%, 50 wt%, 60 wt%, 70 wt%, 80 wt%, or a concentration between any of the above.

According to the invention, preferably, the concentration of the alkali solution is greater than 20% by weight.

According to a preferred embodiment of the invention, the concentration of the alkali solution is 40-60% by weight. In this preferred embodiment, the conversion of cumene hydroperoxide is advantageously increased.

The present invention has a wide range of selection of the base, and preferably, the base is at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium carbonate, ammonium bicarbonate and ammonia. The base is more preferably sodium hydroxide from the viewpoint of reducing the reaction cost.

The concentration of the cumene hydroperoxide solution in the present invention is selected from a wide range as long as the cumene hydroperoxide can react with the alkali, and specifically, for example, the concentration may be 5 wt%, 10 wt%, 15 wt%, 20 wt%, 30 wt%, 40 wt%, 50 wt%, 60 wt%, 70 wt%, 80 wt%, 90 wt%, or a concentration between any of the above.

From the viewpoint of facilitating the increase of the reaction conversion, it is preferable that the cumene hydroperoxide solution has a concentration of 40 to 80% by weight.

In a preferred embodiment, the cumene hydroperoxide solution preferably has a concentration of 45 to 65 weight percent. Under the condition that the weight ratio of the alkali solution to the cumene hydroperoxide solution is the same, the conversion rate of the reaction of the cumene hydroperoxide and the alkali is more favorably improved in the preferred embodiment.

In the present invention, the solvent of the cumene hydroperoxide solution can be selected from a wide range, and can be a polar solvent or a nonpolar solvent. Preferably, the solvent of the cumene hydroperoxide solution is selected from at least one of cumene, chlorobenzene, ethanol and acetone. The solvent is preferably cumene from the viewpoint of facilitating the reaction with the alkali solution.

According to a preferred embodiment of the present invention, the cumene hydroperoxide accumulation rate during the second contact reaction is not greater than 12% by weight. In this preferred embodiment, it is more advantageous to avoid the risk of runaway reactions. The accumulation rate can be determined by titration.

The method adopts semi-batch operation, namely, firstly, carrying out a first reaction on part of cumene hydroperoxide solution and an alkali solution to obtain a first material; then introducing the rest part of the cumene hydroperoxide solution into the first material for second contact reaction.

According to the present invention, preferably, the first contacting is performed by introducing the alkali solution into a part of the cumene hydroperoxide solution.

The conditions for the first contact reaction are selected from a wide range, and preferably, the conditions for the first contact reaction comprise: under the condition of stirring, the temperature is 40-120 ℃.

According to the present invention, preferably, the first contact reaction condition further comprises: the pressure is 0.01-1MPa, and the time is 0.2-2 h.

In the present invention, the manner of controlling the first contact reaction temperature is not particularly limited, and may be selected conventionally in the art, and specifically, for example, in order to avoid the first contact reaction temperature being too high, the first contact reaction process may be placed under the condition of circulating cooling water.

According to a preferred embodiment of the present invention, the first contact reaction conditions comprise: under the condition of stirring, the temperature is 60-80 ℃. Under the preferable condition, the first contact reaction process is more favorably controlled not to produce precipitates, and the conversion rate of the reaction of the cumene hydroperoxide and the alkali is improved.

According to a preferred embodiment of the present invention, the first contact reaction condition further comprises: the pressure is 0.1-0.2MPa, and the time is 0.5-1.5 h.

According to the present invention, preferably, the second contact reaction is carried out by introducing the remaining part of the cumene hydroperoxide solution into the first material. Preferably, the second contact reaction is introduced dropwise.

According to the present invention, preferably, the second contact reaction conditions include: under the condition of stirring, the temperature is 50-100 ℃.

According to the present invention, preferably, the second contact reaction condition further comprises: the pressure is 0.01-1MPa, and the time is 1-5 h.

In the present invention, the manner of controlling the temperature of the second contact reaction is not particularly limited, and may be selected conventionally in the art, and specifically, for example, in order to avoid the second contact reaction temperature being too high, the second contact reaction process may be placed under the condition of circulating cooling water.

According to a preferred embodiment of the present invention, the second contact reaction condition comprises: under the condition of stirring, the temperature is 60-80 ℃. In this preferred case, it is more advantageous to increase the conversion of cumene hydroperoxide reacted with alkali.

According to a preferred embodiment of the present invention, the second contact reaction condition further comprises: the pressure is 0.01-0.2MPa, and the time is 2-4 h.

According to the present invention, preferably, the method further comprises performing interlock control during the first contact reaction and/or the second contact reaction.

Preferably, the interlock control includes: when the temperature in the first contact reaction and/or the second contact reaction process is higher than the alarm temperature, alarming; the alarm temperature is 65-90 ℃. According to the invention, the temperature of the first contact reaction and/or the second contact reaction fluctuates within a certain range, and in the actual production process, a person skilled in the art can select a specific value of the alarm temperature according to the actual situation.

The present invention is not particularly limited to the implementation of the interlock control, and preferably, the interlock control is implemented by at least one of a Distributed Control System (DCS), a Safety Instrumented System (SIS), and a Programmable Logic Controller (PLC). The person skilled in the art can select the required ones according to the actual situation.

In one embodiment, the temperature during the first contact reaction and/or the second contact reaction is monitored by a temperature sensor disposed in the first material and/or the second material, and the interlock system alarms when the temperature is higher than an alarm temperature. The temperature sensor is not particularly limited in the present invention, and those skilled in the art can select the temperature sensor as needed according to actual situations. Preferably, at least two temperature sensors are arranged at different positions in the first material and/or the second material, and the temperature of the reaction process is monitored in real time.

Preferably, the interlock control further includes: stopping the first contact reaction and/or the second contact reaction when the temperature in the first contact reaction and/or the second contact reaction is higher than the termination temperature, and simultaneously reducing the temperature of the first material and/or the second material to be below 50 ℃ within 1-10 min; the termination temperature is 70-95 ℃. According to the present invention, the temperature of the first contact reaction and/or the second contact reaction fluctuates within a certain range, and a person skilled in the art can select a specific value of the termination temperature in an actual production process according to actual conditions. The termination temperature is higher than the alarm temperature.

The interlock control is realized as described above. In one embodiment, the temperature during the first contact reaction and/or the second contact reaction is monitored by a temperature sensor disposed in the first stream and/or the second stream, and when the temperature is above the termination temperature, the interlock system shuts off the feed to the first contact reaction and/or the second contact reaction while emergency cooling water is introduced into the reaction. The emergency cooling water is not particularly limited in the present invention, and may be selected conventionally in the art, for example, the temperature of the emergency cooling water may be normal temperature.

In the invention, the reaction of the cumene hydroperoxide and the alkali belongs to a strong exothermic reaction, and the cumene hydroperoxide is easy to decompose, so that the reaction of the cumene hydroperoxide and the alkali has higher risk of reaction runaway. The method can effectively control the over-temperature and over-pressure phenomena easily occurring in the reaction process of the cumene hydroperoxide and the alkali, and prevent the reaction from being out of control.

The present invention will be described in detail below by way of examples.

Unless otherwise specified, the normal temperature is 25 ℃;

in the following examples, cumene hydroperoxide, cumene and sodium hydroxide are analytically pure;

two temperature sensors are arranged in a liquid phase reaction system of the reactor, and the temperature in the reaction process is monitored in real time;

the cumyl hydroperoxide accumulation rate is analyzed and measured by a titration method;

the conversion of cumene hydroperoxide reaction and the selectivity of dimethylbenzyl alcohol (CA) as a reaction product were measured by gas chromatography.

Example 1

The method provided by the invention is adopted to carry out the reaction of the cumene hydroperoxide and the alkali, and the concentration of the alkali solution is c₁The concentration of the cumene hydroperoxide solution (the solvent is cumene) is c₂The weight ratio of part of the cumene hydroperoxide solution added in the step (1) to the alkali solution is X₁And the weight ratio of the alkali solution to the total dosage of the cumene hydroperoxide solution is X. The method comprises the following specific steps:

(1) adding part of cumene hydroperoxide solution into a reactor, heating to 65 ℃, and placing the reactor under the condition of circulating water (normal temperature); then slowly adding sodium hydroxide solution under the stirring condition to perform a first contact reaction for 0.5h on the premise that no precipitate appears to obtain a first material;

(2) continuously stirring and circulating cooling water, slowly adding the residual cumene hydroperoxide solution into the first material, and carrying out a second contact reaction at a temperature T₂The adding time is 3.5h at about 70 ℃, and the on-line monitoring accumulation rate is controlled to be below 10 weight percent to obtain a second material;

(3) monitoring the temperature in the reaction process through a temperature sensor, and alarming when the temperature in the first contact reaction and/or the second contact reaction process is higher than an alarm temperature, wherein the alarm temperature is set to be 90 ℃; the termination temperature is set to be 95 ℃, when the temperature in the first contact reaction and/or the second contact reaction process is higher than the termination temperature, the feeding of the first contact reaction and/or the second contact reaction is cut off, meanwhile, emergency cooling water is introduced into the reactor for cooling, the temperature of the first material and/or the second material is reduced to be below 50 ℃ within 5min, and the specific reaction conditions are listed in table 1;

the conversion of cumene hydroperoxide reaction and the selectivity of dimethylbenzyl alcohol which is a reaction product were measured, and the results are shown in table 1;

wherein, the cumyl hydroperoxide accumulation rate is equal to the cumyl hydroperoxide weight in the reactor/the total weight of the reaction mixed liquid in the reactor multiplied by 100 percent;

the conversion of cumene hydroperoxide (total weight of cumene hydroperoxide solution added in the reaction product-weight of unreacted cumene hydroperoxide in the product)/total weight of cumene hydroperoxide solution added in the reaction product × 100%;

selectivity to dimethylbenzyl alcohol ═ weight of cumene hydroperoxide converted to dimethylbenzyl alcohol/(total weight of cumene hydroperoxide solution charged to the reaction product-weight of unreacted cumene hydroperoxide in the product) × 100%.

Examples 2 to 9

Cumene hydroperoxide was reacted with base according to the procedure of example 1 except that the reaction conditions were changed, and the specific reaction conditions and results are shown in table 1.

Comparative example 1

The procedure of example 1 was followed except that cumene hydroperoxide was accumulated at a rate of 25% by weight, and the specific reaction conditions and results are shown in Table 1.

TABLE 1

Note: x represents the weight ratio of the alkali solution to the total consumption of the cumene hydroperoxide solution;

X₁representing the weight ratio of part of the cumene hydroperoxide solution added in the step (1) to the alkali solution;

c₁denotes the concentration of sodium hydroxide, c₂The concentration of cumene hydroperoxide;

CHP conversion represents the conversion of cumene hydroperoxide reaction;

CA selectivity refers to the selectivity of the reaction product dimethylbenzyl alcohol.

The results of the embodiment show that, by adopting the method provided by the invention, the reaction of cumene hydroperoxide and sodium hydroxide has higher reactant conversion rate and higher reaction product selectivity, and meanwhile, the safety of the reaction of cumene hydroperoxide and alkali can be ensured, the risk of reaction runaway is reduced, and the method has obvious application value in industrial production. From the characteristic of the reaction of cumene hydroperoxide and alkali, the method can effectively prevent the reaction from further runaway when the reaction is runaway under the optimal condition.

From the results of comparative example 1, it is known that a certain degree of temperature runaway occurs during the second contact reaction, and the temperature rises from 70 ℃ to 81 ℃, which has a high potential safety hazard. At the same time, the selectivity of the reaction product dimethylbenzyl alcohol is reduced.

The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.