CN112500265B - Preparation method of diphenyl ether - Google Patents

Preparation method of diphenyl ether Download PDF

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CN112500265B
CN112500265B CN202011506361.5A CN202011506361A CN112500265B CN 112500265 B CN112500265 B CN 112500265B CN 202011506361 A CN202011506361 A CN 202011506361A CN 112500265 B CN112500265 B CN 112500265B
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fixed bed
bed reactor
phenol
diphenyl ether
reactor
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CN112500265A (en
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詹石玉
刘东东
高双庆
南彦冬
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Hebei Jindong Technology Group Co.,Ltd.
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Shexian Jindong Economic And Trade Co ltd
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01Preparation of ethers
    • C07C41/09Preparation of ethers by dehydration of compounds containing hydroxy groups

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Abstract

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.

Description

Preparation method of diphenyl ether
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
Figure 12950DEST_PATH_IMAGE001
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
Figure 24899DEST_PATH_IMAGE001
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
Figure 756095DEST_PATH_IMAGE002
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
Figure 218300DEST_PATH_IMAGE001
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 purity of the finished product is 99.96%, and the yield is 6.7%.
Comparative example 2
Figure 316837DEST_PATH_IMAGE001
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
Figure 788270DEST_PATH_IMAGE002
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 is 99.96%, and the yield is 8.7%.
Comparative example 4
Figure 780497DEST_PATH_IMAGE002
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.

Claims (2)

1. A process for producing a diphenyl ether, characterized in that, in a continuous flow fixed bed reactor, phenol is brought into contact with a magnesium oxide/zeolite catalyst charged in the reactor in a nitrogen atmosphere and reacted to produce a diphenyl ether:
the magnesium oxide/zeolite catalyst comprises, by mass, 60-77% of magnesium oxide, 23-40% of zeolite and 4A zeolite;
preheating the phenol to 80-120 ℃ before the phenol enters the fixed bed reactor;
the temperature in the reactor is 300-500 ℃, and the pressure is 0.05-0.2 MPa;
and the retention time of the phenol in the fixed reactor is 5-30 seconds.
2. 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.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5288922A (en) * 1992-07-16 1994-02-22 The Dow Chemical Company Process of preparing diaryl ethers over a dealuminated zeolite catalyst
JP2002138062A (en) * 2000-10-31 2002-05-14 Sumitomo Chem Co Ltd Method for producing alkyl etherate of naphthol
CN104364226A (en) * 2012-05-31 2015-02-18 陶氏环球技术有限责任公司 Catalytic dehydration of aryl alcohols to diaryl ethers
WO2016187773A1 (en) * 2015-05-25 2016-12-01 高化学株式会社 Catalyst for preparing glycol ether and preparation method and application thereof
CN109277114A (en) * 2017-07-19 2019-01-29 中国科学院大连化学物理研究所 The preparation method of catalyst for etherification and the method for producing methyl phenyl ethers anisole

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5288922A (en) * 1992-07-16 1994-02-22 The Dow Chemical Company Process of preparing diaryl ethers over a dealuminated zeolite catalyst
JP2002138062A (en) * 2000-10-31 2002-05-14 Sumitomo Chem Co Ltd Method for producing alkyl etherate of naphthol
CN104364226A (en) * 2012-05-31 2015-02-18 陶氏环球技术有限责任公司 Catalytic dehydration of aryl alcohols to diaryl ethers
WO2016187773A1 (en) * 2015-05-25 2016-12-01 高化学株式会社 Catalyst for preparing glycol ether and preparation method and application thereof
CN109277114A (en) * 2017-07-19 2019-01-29 中国科学院大连化学物理研究所 The preparation method of catalyst for etherification and the method for producing methyl phenyl ethers anisole

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
甲醇脱水制二甲醚催化剂的研究;黄亮 等;《沈阳化工大学学报》;20101231;第24卷(第4期);P321-323 *

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