A method for simultaneously producing n-butyl ether and phenyl butyl ether by etherification reaction

Abstract

The application belongs to the technical field of organic synthesis, and discloses a method for preparing n-butyl ether and butyl phenyl ether simultaneously through etherification reaction. Phenol, n-butanol and a phosphoric acid catalyst are mixed, and then etherification reaction is carried out under a protective gas to obtain n-butyl ether and butyl phenyl ether. The method can prepare n-butyl ether and butyl phenyl ether simultaneously, the combined selectivity of n-butyl ether and butyl phenyl ether can reach 98-99%, the reaction has few by-products, the conversion efficiency of raw materials is high, the products obtained by the reaction are important chemical raw materials, and the method has high economic benefits. The preparation method does not need to add strong acid and strong base, the reaction condition is mild, the safety coefficient of the preparation process is high, there is no defect of damage and corrosion to the equipment, and the method belongs to a more green and environmental protection organic synthesis method.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of organic synthesis, and particularly relates to a method for preparing n-butyl ether and butyl phenyl ether simultaneously through etherification. BACKGROUND

[0002] Butyl phenyl ether, also known as butyl phenyl ether or butyl phenyl ether, is a colorless liquid with an aromatic odor. CAS: 1126-79-0, molecular formula is C 10 H 14 O, molecular weight is 150.22, melting point is -19.4℃, boiling point is 206.8℃, relative density is 0.9351g / cm 3 . Butyl phenyl ether is an important raw material and organic solvent in organic synthesis, which is often used to manufacture perfumes and pesticides, and is also used as a raw material for preparing local anesthetic drug dyclonine hydrochloride.

[0003] n-Butyl ether, also known as dibutyl ether, is a colorless liquid with an ether odor. CAS: 142-96-1, molecular formula is C8H 18 O, molecular weight is 130.23, melting point is -98℃, boiling point is 142℃. n-Butyl ether is an excellent organic extractant, which can be used as an inert medium and solvent in organic synthesis. At the same time, as a liquid ether, it can improve the cetane number of diesel oil, promote complete combustion of diesel oil, and reduce tail gas smoke, which is an ideal diesel engine oxygen-containing fuel.

[0004] The preparation of n-butyl ether generally adopts the traditional Williamson method, dehydration method under the catalysis of concentrated sulfuric acid, organic acid or concentrated phosphoric acid, high-temperature dehydration method under the catalysis of solid catalyst, and microwave normal pressure method.

[0005] The Williamson method is to react sodium with ethanol to form sodium ethoxide, then react sodium phenoxide with BuBr (or BuI) to form, or to reflux solid NaOH with ethanol, then react with phenol, and finally reflux with BuBr. The former uses sodium with high cost and high risk, and the latter has a long reaction time. In addition to the Williamson method, the raw materials and catalysts used in other methods involve strong acid, toxic and harmful compounds, which have problems of corroding equipment and polluting the environment.

[0006] Therefore, the current methods for preparing butyl phenyl ether and n-butyl ether have problems of long reaction time, low yield, high cost, and the use of raw materials involving strong acid and strong base, which has problems of high risk coefficient and high hazard in the preparation process. There is an urgent need in the field to develop a method for preparing butyl phenyl ether and n-butyl ether with fast reaction rate, high reaction efficiency, simple and convenient reaction, and low reaction cost. SUMMARY

[0007] The present application aims to provide a method for simultaneously preparing n-butyl ether and phenyl butyl ether through etherification reaction, so as to solve the problems of long reaction time, low yield, high cost, corrosion of equipment, high risk and great harm in the preparation of phenyl butyl ether and n-butyl ether.

[0008] In order to achieve the above-mentioned purpose, the present application adopts the following technical solutions:

[0009] The present application provides a method for simultaneously preparing n-butyl ether and phenyl butyl ether through etherification reaction, comprising the following steps:

[0010] The phenol, n-butanol and catalyst are mixed and then subjected to etherification reaction to obtain n-butyl ether and phenyl butyl ether.

[0011] Preferably, the catalyst is one or more of aluminum phosphate, lanthanum phosphate, zirconium phosphate, cerium phosphate, zinc phosphate, calcium phosphate and magnesium phosphate.

[0012] Preferably, the molar ratio of the phenol to n-butanol is 1:1.5-5, and the mass of the catalyst is 2-5% of the total mass of the phenol and n-butanol.

[0013] Preferably, the etherification reaction is carried out in a continuous flow fixed bed reactor.

[0014] Preferably, the specific steps of the etherification reaction are as follows: the catalyst is placed in the catalyst bed layer of the fixed bed reactor, and the mixture of the phenol and n-butanol is subjected to etherification reaction by passing through the catalyst bed layer.

[0015] Preferably, the mixture of the phenol and n-butanol passes through the catalyst bed layer at a speed of 0.04-0.5 mL / min.

[0016] Preferably, the etherification reaction is carried out under a protective gas, and the protective gas is nitrogen or hydrogen.

[0017] Preferably, the temperature of the etherification reaction is 240-260℃.

[0018] Through the above technical solutions, the present application has the following advantages compared with the prior art:

[0019] (1) The present application can simultaneously prepare phenyl butyl ether and n-butyl ether, and the combined selectivity of phenyl butyl ether and n-butyl ether can reach 98-99%, the reaction has less by-products, the conversion efficiency of the reaction raw materials is high, and the obtained products are important chemical raw materials, which have high economic benefits.

[0020] (2) The preparation method of the present application does not need to add strong acid and strong base, and the required reaction condition is mild, the safety factor of the preparation process is high, there is no problem of damage and corrosion to the equipment, and it belongs to a green and environmentally-friendly organic synthesis method. DETAILED DESCRIPTION

[0021] The present application provides a method for preparing n-butyl ether and phenyl butyl ether simultaneously through etherification reaction, comprising the following steps:

[0022] The phenol, n-butanol and catalyst are mixed and then subjected to etherification reaction to obtain n-butyl ether and phenyl butyl ether.

[0023] In the present application, the catalyst is preferably one or more of aluminum phosphate, lanthanum phosphate, zirconium phosphate, cerium phosphate, zinc phosphate, calcium phosphate and magnesium phosphate, is further preferably one or more of aluminum phosphate, lanthanum phosphate and magnesium phosphate, and is more preferably aluminum phosphate and / or magnesium phosphate.

[0024] In the present application, the molar ratio of the phenol to n-butanol is preferably 1:1.5-5, is further preferably 1:2-4, and is more preferably 1:3; and the mass of the catalyst is preferably 2-5% of the total mass of the phenol and n-butanol, is further preferably 2.5-4.5% of the total mass of the phenol and n-butanol, and is more preferably 3-4% of the mass of the phenol and n-butanol.

[0025] In the present application, the etherification reaction is preferably carried out in a continuous flow fixed bed reactor.

[0026] In the present application, the specific steps of the etherification reaction are as follows: the catalyst is placed in the catalyst bed layer of the fixed bed reactor, and the mixed solution of the phenol and n-butanol is subjected to etherification reaction through the catalyst bed layer.

[0027] In the present application, the mixed solution of the phenol and n-butanol is preferably passed through the catalyst bed layer at a speed of 0.04-0.5 mL / min, is further preferably passed through the catalyst bed layer at a speed of 0.08-0.4 mL / min, and is more preferably passed through the catalyst bed layer at a speed of 0.1-0.3 mL / min.

[0028] In the present application, the mixed solution of the phenol and n-butanol is passed through the catalyst bed layer by using a laminar flow pump.

[0029] In the present application, the etherification reaction is preferably carried out under a protective gas; and the protective gas is preferably nitrogen or hydrogen.

[0030] In the present application, the temperature of the etherification reaction is preferably 240-260℃, is further preferably 245-255℃, and is more preferably 250℃.

[0031] In the present application, the product obtained by etherification reaction is distilled, and the fraction of 145-150°C and the fraction of 215-220°C are collected to obtain n-butyl ether and phenyl butyl ether; wherein the fraction of 145-150°C is n-butyl ether; and the fraction of 215-220°C is phenyl butyl ether.

[0032] The technical solutions provided by the present application are described in detail below in combination with examples, but they should not be understood as limiting the scope of protection of the present application.

[0033] Example 1

[0034] 1 mol of phenol and 3 mol of n-butanol are mixed to obtain a reaction liquid, 10 g of aluminum phosphate catalyst is placed in the catalyst bed of a continuous flow fixed bed reactor, then the continuous flow fixed bed reactor is heated to 240°C under a nitrogen atmosphere, the reaction liquid is sent into the catalyst bed of the continuous flow fixed bed reactor at a speed of 0.15 mL / min through a laminar flow pump, the reaction liquid is subjected to etherification reaction under the action of the aluminum phosphate catalyst, and the product is collected at the outlet of the continuous flow fixed bed reactor, the product is phenyl butyl ether, n-butyl ether and other by-products, the product is distilled to collect the fraction of 143°C and the fraction of 212°C to obtain n-butyl ether and phenyl butyl ether.

[0035] It is determined that in the present example, the conversion rate of phenol is 30%, the selectivity to phenyl butyl ether is 39%, the selectivity to n-butyl ether is 59%, the combined selectivity to phenyl butyl ether and n-butyl ether is 98%, and the content of other by-products is 2%.

[0036] Example 2

[0037] 1 mol of phenol and 5 mol of n-butanol are mixed to obtain a reaction liquid, 10 g of magnesium phosphate catalyst is placed in the catalyst bed of a continuous flow fixed bed reactor, then the continuous flow fixed bed reactor is heated to 250°C under a nitrogen atmosphere, the reaction liquid is sent into the catalyst bed of the continuous flow fixed bed reactor at a speed of 0.04 mL / min through a laminar flow pump, the reaction liquid is subjected to etherification reaction under the action of the magnesium phosphate catalyst, and the product is collected at the outlet of the continuous flow fixed bed reactor, the product is phenyl butyl ether, n-butyl ether and other by-products, the product is distilled to collect the fraction of 143°C and the fraction of 212°C to obtain n-butyl ether and phenyl butyl ether.

[0038] It is determined that in the present example, the conversion rate of phenol is 50%, the selectivity to phenyl butyl ether is 24%, the selectivity to n-butyl ether is 74%, the combined selectivity to phenyl butyl ether and n-butyl ether is 98%, and the content of other by-products is 2%.

[0039] Example 3

[0040] Mix 1 mol of phenol and 4 mol of n-butanol to obtain a reaction liquid, place 18 g of lanthanum phosphate catalyst in the catalyst bed of a continuous flow fixed bed reactor, then heat the continuous flow fixed bed reactor to 255 ℃ under a nitrogen atmosphere, send the reaction liquid into the catalyst bed of the continuous flow fixed bed reactor at a speed of 0.2 mL / min through a laminar flow pump, make the reaction liquid undergo etherification under the action of the lanthanum phosphate catalyst, and then collect the product at the outlet of the continuous flow fixed bed reactor, wherein the product is phenyl butyl ether, n-butyl ether and other by-products, and the product is subjected to distillation to collect a fraction at 143 ℃ and a fraction at 212 ℃, thereby obtaining n-butyl ether and phenyl butyl ether.

[0041] It is determined that in the embodiment, the conversion rate of phenol is 60%, the selectivity to phenyl butyl ether is 31%, the selectivity to n-butyl ether is 68%, the combined selectivity to phenyl butyl ether and n-butyl ether is 99%, and the content of other by-products is 1.8%.

[0042] Example 4

[0043] Mix 1 mol of phenol and 4.5 mol of n-butanol to obtain a reaction liquid, place 17 g of calcium phosphate catalyst in the catalyst bed of a continuous flow fixed bed reactor, then heat the continuous flow fixed bed reactor to 260 ℃ under a nitrogen atmosphere, send the reaction liquid into the catalyst bed of the continuous flow fixed bed reactor at a speed of 0.3 mL / min through a laminar flow pump, make the reaction liquid undergo etherification under the action of the calcium phosphate catalyst, and then collect the product at the outlet of the continuous flow fixed bed reactor, wherein the product is phenyl butyl ether, n-butyl ether and other by-products, and the product is subjected to distillation to collect a fraction at 143 ℃ and a fraction at 212 ℃, thereby obtaining n-butyl ether and phenyl butyl ether.

[0044] It is determined that in the embodiment, the conversion rate of phenol is 55%, the selectivity to phenyl butyl ether is 28%, the selectivity to n-butyl ether is 70%, the combined selectivity to phenyl butyl ether and n-butyl ether is 98%, and the content of other by-products is 2%.

[0045] It can be known from Examples 1-4 that phenyl butyl ether and n-butyl ether can be prepared simultaneously according to the application, the combined selectivity to phenyl butyl ether and n-butyl ether can reach 98-99%, the by-products obtained in the reaction are few (the content of by-products is 1.8-2%), the conversion efficiency of raw materials in the reaction is high (the conversion rate of phenol can reach 30-60%), and both phenyl butyl ether and n-butyl ether obtained in the reaction are important chemical raw materials, and have high economic benefits.

[0046] The above only describes the preferred embodiments of the application, and it should be noted that those of ordinary skill in the art can make several improvements and refinements without departing from the principles of the application, and these improvements and refinements should also be considered as the protection scope of the application.

Claims

1. A process for the simultaneous production of n-butyl ether and phenyl butyl ether by etherification, characterized in that, The method comprises the following steps: The phenol, n-butanol and catalyst are mixed and then subjected to etherification reaction to obtain n-butyl ether and butyl phenyl ether; The molar ratio of the phenol to the n-butanol is 1:1.5-5; the mass of the catalyst is 2-5% of the total mass of the phenol and the n-butanol; The catalyst is one or more of aluminum phosphate, lanthanum phosphate, calcium phosphate and magnesium phosphate; The etherification reaction is performed in a continuous flow fixed bed reactor; The temperature of the etherification reaction is 240-260℃.

2. The method of claim 1, wherein the etherification reaction is carried out simultaneously to produce n-butyl ether and butyl phenyl ether. The etherification reaction is performed in a continuous flow fixed bed reactor.

3. The method of claim 2, wherein the etherification reaction is carried out simultaneously to produce n-butyl ether and butyl phenyl ether. The mixture of the phenol and the n-butanol is fed into the catalyst bed at a speed of 0.04-0.5 mL / min.

4. The process according to claim 1, 2 or 3, characterized in that the etherification reaction is carried out simultaneously for the production of n-butyl ether and butyl phenyl ether. The etherification reaction is performed under a protective gas, which is nitrogen or air.