阅读说明：本技术 一种联苯醚的制备方法 (Preparation method of diphenyl ether ) 是由 詹石玉 刘东东 高双庆 南彦冬 于 2020-12-18 设计创作，主要内容包括：本发明涉及一种联苯醚的制备方法,采用连续流动固定床反应器,苯酚在氮气氛环境中与装填在反应器中的氧化镁/沸石催化剂接触并进行反应生成联苯醚,本发明以苯酚为原料,经固定床反应器高温催化反应再精馏分离制得联苯醚,本发明专利具有反应步骤少、成本低、污染小等优点,实现了工业生产联苯醚的绿色催化。(The invention relates to a preparation method of diphenyl ether, which adopts a continuous flow fixed bed reactor, wherein phenol contacts with a magnesium oxide/zeolite catalyst filled in the reactor in a nitrogen atmosphere environment and reacts to generate diphenyl ether.)

1. A process for producing diphenyl ether, characterized in that a continuous flow fixed bed reactor is used, phenol is brought into contact with a magnesium oxide/zeolite catalyst packed in the reactor in a nitrogen atmosphere and reacted to produce diphenyl ether.

2. The process according to claim 1, wherein the amount of magnesium oxide in the magnesium oxide/zeolite catalyst is 60 to 77% by mass, and the amount of zeolite is 23 to 40% by mass.

3. The process according to claim 1, wherein said zeolite is a 4A zeolite.

4. The process according to claim 1, wherein said phenol is preheated to 80 to 120 ℃ before being fed into the fixed bed reactor.

5. The process according to claim 1, wherein the temperature in the reactor is 300 to 500 ℃ and the pressure in the reactor is 0.05 to 0.2 MPa.

6. The process according to claim 1, wherein the residence time of said phenol in said fixed reactor is 5 to 30 seconds.

7. The process for producing a diphenyl ether according to claim 1, wherein the produced diphenyl ether, water and unreacted raw phenol are discharged from the fixed bed reactor in a gaseous state, and are cooled to a liquid in a multistage condenser, and then the liquid is fed into a rectifying still to be rectified and separated, and the diphenyl ether is collected, and the unreacted phenol is recycled to the fixed bed reactor.

Technical Field

The invention belongs to the technical field of chemical industry, and particularly relates to a preparation method of diphenyl ether.

Background

The diphenyl ether is also called diphenyl ether, is an important chemical intermediate, can be used for producing flame retardant, essence, perfume, dye and the like, can also be used as a high-temperature heat carrier, and has wide application. The traditional biphenyl ether synthesis method is that chlorobenzene and phenol are condensed in caustic soda solution in the presence of copper oxide catalyst to obtain finished products, and the finished products are obtained through alkali washing and distillation refining.

CN102146024A discloses a preparation method of a diphenyl ether, which comprises the steps of generating a salt solution of phenol by using phenol and alkali, refluxing and removing water in a system by using chlorobenzene, and then carrying out U11mann reaction by dropwise adding chlorobenzene in the presence of a catalyst to generate a target compound; in the method, phenol is taken as a raw material and also taken as a solvent, a catalyst is copper sulfate pentahydrate or copper chloride wet material or a mixture of the copper sulfate pentahydrate and the copper chloride wet material, the whole process needs at least 12.5 hours, and the defects of long reaction time and complex process are overcome.

In view of the above, the invention provides the method for preparing the diphenyl ether, which is environment-friendly, simple in production process and low in production cost.

Disclosure of Invention

The invention aims to overcome the defects in the prior art and provide the preparation method of the diphenyl ether, which is environment-friendly, simple in production process and low in production cost.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

the invention provides a preparation method of diphenyl ether, which adopts a continuous flow fixed bed reactor, and phenol contacts with a magnesium oxide/zeolite catalyst filled in the reactor in a nitrogen atmosphere environment and reacts to generate diphenyl ether.

In some preferred embodiments of the present invention, the magnesium oxide/zeolite catalyst comprises 60 to 77% by mass of magnesium oxide and 23 to 40% by mass of zeolite.

As some preferred embodiments of the invention, the zeolite is a 4A zeolite.

As some preferred embodiments of the present invention, the phenol is preheated to 80-120 ℃ before entering the fixed bed reactor.

As some preferred embodiments of the present invention, the temperature in the reactor is 300 to 500 ℃ and the pressure is 0.05 to 0.2 MPa.

As some preferred embodiments of the present invention, the residence time of the phenol in the fixed reactor is 5 to 30 seconds.

As some preferred embodiments of the invention, the generated diphenyl ether, water and unreacted raw material phenol are discharged from the fixed bed reactor in a gaseous state, enter a multi-stage condenser to be cooled into liquid, then enter a rectifying still to be rectified and separated, the diphenyl ether is collected, and the unreacted phenol is recycled to the fixed bed reactor.

Adopt the produced beneficial effect of above-mentioned technical scheme to lie in:

the invention takes phenol as raw material, and biphenyl ether is prepared by high-temperature catalytic reaction and rectification separation of a fixed bed reactor.

The invention breaks the bottleneck in the prior art and fills the domestic blank.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail and fully with reference to the following embodiments.

Example 1

Opening a nitrogen purging pipeline and a fixed bed reactor to replace air in the nitrogen purging pipeline, preheating the raw material phenol to 100 ℃, pumping the mixture into a fixed bed reactor by a pump, filling a catalyst of magnesia (68 mass%)/4A zeolite (32 mass%), heating the fixed bed reactor to 400 ℃, controlling the pressure in the reactor to be 0.1MPa, adjusting the nitrogen flow to ensure that the material stays in the fixed bed reactor for 15 seconds, discharging the biphenyl ether, water and unreacted raw material phenol generated by the reaction out of the fixed bed reactor in a gaseous state, feeding the biphenyl ether, the water and the unreacted raw material phenol into a multistage condenser to be cooled into liquid, then the product enters a rectifying still for rectification separation, the collected water is used as circulating water for supplement, the phenol enters a reaction system again for recycling, the finished product enters a finished product large tank, and the purity of the finished product is 99.96 percent and the yield is 18.2 percent after the finished product is analyzed by gas chromatography.

Example 2

Opening a nitrogen purging pipeline and a fixed bed reactor to replace air in the nitrogen purging pipeline, preheating the raw material phenol to 120 ℃, pumping the mixture into a fixed bed reactor by a pump, filling a catalyst of magnesium oxide (60 mass%)/4A zeolite (40 mass%) in the fixed bed reactor, heating the fixed bed reactor to 500 ℃, controlling the pressure level in the reactor to be 0.2MPa, adjusting the nitrogen flow to ensure that the material stays in the fixed bed reactor for 5 seconds, discharging the biphenyl ether, water and unreacted raw material phenol generated by the reaction out of the fixed bed reactor in a gaseous state, feeding the biphenyl ether, the water and the unreacted raw material phenol into a multistage condenser to be cooled into liquid, then the product enters a rectifying still for rectification separation, the collected water is used as circulating water for supplement, the phenol enters a reaction system again for recycling, the finished product enters a finished product large tank, and the purity of the finished product is 99.98% and the yield is 13.9% after the finished product is analyzed by gas chromatography.

Example 3

Opening a nitrogen purging pipeline and a fixed bed reactor to replace air in the nitrogen purging pipeline, preheating the raw material phenol to 80 ℃, pumping into a fixed bed reactor by a pump, filling a catalyst of 77 mass percent/4A zeolite 23 mass percent in the fixed bed reactor, heating the fixed bed reactor to 300 ℃, controlling the pressure level in the reactor to be 0.05MPa, adjusting the nitrogen flow to ensure that the material stays in the fixed bed reactor for 30 seconds, discharging the biphenyl ether, water and unreacted raw material phenol generated by the reaction out of the fixed bed reactor in a gaseous state, feeding into a multistage condenser to be cooled into liquid, then the product enters a rectifying still for rectification separation, the collected water is used as circulating water for supplement, the phenol enters a reaction system again for recycling, the finished product enters a finished product large tank, and the purity of the finished product is 99.97 percent and the yield is 17.4 percent after the finished product is analyzed by gas chromatography.

Comparative example 1

Opening a nitrogen purging pipeline and a fixed bed reactor to replace air in the fixed bed reactor, preheating raw material phenol to 100 ℃, pumping the raw material phenol into the fixed bed reactor by a pump, filling a 4A zeolite catalyst in the fixed bed reactor, heating the fixed bed reactor to 400 ℃, controlling the pressure level in the reactor to be 0.1MPa, adjusting the flow of nitrogen to ensure that the retention time of the material in the fixed bed reactor is 15 seconds, discharging biphenyl ether, water and unreacted raw material phenol generated by reaction out of the fixed bed reactor in a gaseous state, feeding the biphenyl ether, the water and the unreacted raw material phenol into a multistage condenser to be cooled into liquid, feeding the liquid into a rectifying kettle to be rectified and separated, supplementing the collected water as circulating water, feeding the phenol into a reaction system again for recycling, feeding the finished product into a finished product large tank, analyzing the finished product by gas chromatography, wherein the.

Comparative example 2

Opening a nitrogen purging pipeline and a fixed bed reactor to replace air in the nitrogen purging pipeline, preheating the raw material phenol to 100 ℃, pumping the mixture into a fixed bed reactor by a pump, filling a tungsten oxide (77 mass%)/4A zeolite (23 mass%) catalyst in the fixed bed reactor, heating the fixed bed reactor to 400 ℃, controlling the pressure level in the reactor to be 0.1MPa, adjusting the nitrogen flow to ensure that the material stays in the fixed bed reactor for 15 seconds, discharging the biphenyl ether, water and unreacted raw material phenol generated by the reaction out of the fixed bed reactor in a gaseous state, feeding the biphenyl ether, the water and the unreacted raw material phenol into a multistage condenser to be cooled into liquid, then the product enters a rectifying still for rectification separation, the collected water is used as circulating water for supplement, the phenol enters a reaction system again for recycling, the finished product enters a finished product large tank, and the purity of the finished product is 99.96 percent and the yield is 9.3 percent through gas chromatography analysis.

Comparative example 3

Opening a nitrogen purging pipeline and a fixed bed reactor to replace air in the fixed bed reactor, preheating raw material phenol to 100 ℃, pumping the raw material phenol into the fixed bed reactor by a pump, filling a magnesium oxide catalyst in the fixed bed reactor, heating the fixed bed reactor to 400 ℃, controlling the pressure level in the reactor to be 0.1MPa, adjusting the nitrogen flow to ensure that the retention time of the material in the fixed bed reactor is 15 seconds, discharging biphenyl ether, water and unreacted raw material phenol generated by reaction out of the fixed bed reactor in a gaseous state, feeding the biphenyl ether, the water and the unreacted raw material phenol into a multistage condenser to be cooled into liquid, feeding the liquid into a rectifying kettle to be rectified and separated, supplementing the collected water as circulating water, feeding the phenol into a reaction system again for recycling, feeding the finished product into a finished product large tank, analyzing the finished product by gas chromatography, wherein the purity.

Comparative example 4

Opening a nitrogen purging pipeline and a fixed bed reactor to replace air in the nitrogen purging pipeline, preheating the raw material phenol to 100 ℃, pumping the mixture into a fixed bed reactor by a pump, filling a titanium oxide (77 mass%)/4A zeolite (23 mass%) catalyst in the fixed bed reactor, heating the fixed bed reactor to 400 ℃, controlling the pressure in the reactor to be 0.1MPa, adjusting the nitrogen flow to ensure that the material stays in the fixed bed reactor for 15 seconds, discharging the biphenyl ether, water and unreacted raw material phenol generated by the reaction out of the fixed bed reactor in a gaseous state, feeding the biphenyl ether, the water and the unreacted raw material phenol into a multistage condenser to be cooled into liquid, then the product enters a rectifying still for rectification separation, the collected water is used as circulating water for supplement, the phenol enters a reaction system again for recycling, the finished product enters a finished product large tank, and the purity of the finished product is 99.96 percent and the yield is 7.1 percent after the finished product is analyzed by gas chromatography.

Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.