阅读说明：本技术 一种无溶剂法合成溴乙酸酯的绿色环保工艺 (Green and environment-friendly process for synthesizing bromoacetate by solvent-free method ) 是由 徐善泉 储宇锋 季敏 周雪华 于 2021-10-08 设计创作，主要内容包括：本发明公开了一种无溶剂法合成溴乙酸酯的绿色环保工艺,包括如下步骤：1)混合：在反应釜投入一定量的混合物,开动搅拌,打开真空泵系统调节压力,并缓慢加热至指定温度；2)反应：反应开始后,在一定反应时间内缓慢将反应温度升至指定温度,并保持一段时间,取样分析；3)成品：反应完毕后,降温至室温,将反应液密闭过滤,转入脱水釜用高真空在一定温度下保持一段时间,得到黄棕色油状液体即为产物。本发明避免使用溶剂过程中带来的安全问题和职业健康危害,催化剂使用硫酸氢钠,反应完毕经过滤可以分离,可以套用数批；符合当前的绿色工艺发展方向,提高生产效率,促进反应进行,省去洗涤过程,不产生废水。(The invention discloses a green environment-friendly process for synthesizing bromoacetate by a solvent-free method, which comprises the following steps: 1) mixing: putting a certain amount of mixture into a reaction kettle, starting stirring, starting a vacuum pump system to adjust the pressure, and slowly heating to a specified temperature; 2) reaction: after the reaction starts, slowly raising the reaction temperature to the specified temperature within a certain reaction time, keeping for a period of time, and sampling and analyzing; 3) and (3) finished product: after the reaction is finished, cooling to room temperature, sealing and filtering the reaction liquid, transferring the reaction liquid into a dehydration kettle, and keeping the reaction liquid at a certain temperature for a period of time under high vacuum to obtain yellowish-brown oily liquid, namely the product. The invention avoids the safety problem and occupational health hazard brought by using the solvent, the catalyst uses sodium bisulfate, can be separated by filtration after the reaction is finished, and can be applied for a plurality of batches; the method conforms to the current green process development direction, improves the production efficiency, promotes the reaction to be carried out, omits the washing process and does not generate wastewater.)

1. A green environment-friendly process for synthesizing bromoacetate by a solvent-free method is characterized by comprising the following steps: the method comprises the following steps:

1) mixing: putting a certain amount of mixture into a reaction kettle, starting stirring, starting a vacuum pump system to adjust the pressure, and slowly heating to a specified temperature; 2) Reaction: after the reaction starts, slowly raising the reaction temperature to the specified temperature within a certain reaction time, keeping for a period of time, and sampling and analyzing; 3) And (3) finished product: after the reaction is finished, cooling to room temperature, sealing and filtering the reaction liquid, transferring the reaction liquid into a dehydration kettle, and keeping the reaction liquid at a certain temperature for a period of time under high vacuum to obtain yellowish-brown oily liquid, namely the product.

2. The green and environment-friendly process for synthesizing bromoacetate by the solvent-free method according to claim 1, characterized in that: in the mixing step, the mixture is 695kg of bromoacetic acid, 220kg of 1, 4-butylene glycol and 2kg of sodium bisulfate, and in the finished product step, the product is 820kg of 1, 4-bis (bromoethanone oxygen) -2-butylene.

3. The green and environment-friendly process for synthesizing bromoacetate by the solvent-free method according to claim 1, characterized in that: in the mixing step, the mixture is 695kg of bromoacetic acid, 155kg of ethylene glycol and 2kg of sodium bisulfate, and in the finished product step, the product is 750kg of 1, 4-bis (bromoethanone oxygen) -2-butene.

4. The green and environment-friendly process for synthesizing bromoacetate by the solvent-free method according to claim 1, characterized in that: the pressure of the vacuum pump in the mixing step is-0.085 Mpa, and the temperature is 50 ℃.

5. The green and environment-friendly process for synthesizing bromoacetate by the solvent-free method according to claim 1, characterized in that: in the reaction step, the reaction time is 3-7h, the temperature is 95 ℃, and the holding time is 1-2 h.

6. The green and environment-friendly process for synthesizing bromoacetate by the solvent-free method according to claim 1, characterized in that: in the step of preparing the finished product, the pressure of high vacuum is-0.098 Mpa, the temperature is 70-80 ℃, and the holding time is 1-2 h.

Technical Field

The invention relates to the field of chemical manufacturing, in particular to a green environment-friendly process for synthesizing bromoacetate by a solvent-free method.

Background

The water systems of industrial circulating cooling water, oil field reinjection water, paper making industry and the like have special and complex ecological environments and are suitable for the growth and propagation of various bacteria and algae microorganisms. The mass propagation of the microorganisms can form slime, which causes the problems of pipeline blockage, equipment corrosion, water quality deterioration and the like, and causes huge economic loss for industrial production. Therefore, an excellent industrial water treatment antibacterial agent needs to be selected for sterilization treatment.

The 1, 4-bis (bromoethanoloxy) -2-butene (BBAB) and the 2, 2-bis (bromoacetoxy) ethane (BBAE) are efficient and environment-friendly disinfection antibacterial agents, have the characteristics of wide antibacterial spectrum, small toxic and side effects, rapid degradation, no environmental pollution, capability of effectively inhibiting the formation of slime and the like, and are widely applied to industrial water treatment systems as antibacterial agents.

The existing preparation method of BBAB and BBAE basically reacts in a large amount of organic inert solvents, alcohol and bromoacetic acid are subjected to esterification reaction under the action of catalysts, most of the catalysts are inorganic salts, p-toluenesulfonic acid, sulfuric acid and the like, the production efficiency is low, the catalyst recovery difficulty is high, the cost is high, the energy consumption is high, the safety is poor, the wastewater is large, biochemical treatment is difficult (a large amount of reaction solvents need to be removed after the reaction), and the final yield of BBAB is only 66.75%.

Disclosure of Invention

The invention mainly solves the technical problem of providing a green environment-friendly process for synthesizing bromoacetate by a solvent-free method, which avoids the safety problem and occupational health hazard brought by using a solvent, wherein the catalyst uses sodium bisulfate, and can be separated by filtration after the reaction is finished and can be applied for multiple batches; the method has the advantages that COD (chemical oxygen demand) influence on wastewater treatment by catalysts such as toluenesulfonic acid is avoided, the method accords with the current green process development direction, the production efficiency is improved, water generated by reaction is taken away as soon as the water is generated under the negative pressure condition, the reaction is promoted, the washing process is omitted, and no wastewater is generated.

In order to solve the technical problems, the invention adopts a technical scheme that: provides a green environment-friendly process for synthesizing bromoacetate by a solvent-free method, which comprises the following steps:

1) mixing: putting a certain amount of mixture into a reaction kettle, starting stirring, starting a vacuum pump system to adjust the pressure, and slowly heating to a specified temperature; 2) Reaction: after the reaction starts, slowly raising the reaction temperature to the specified temperature within a certain reaction time, keeping for a period of time, and sampling and analyzing; 3) And (3) finished product: after the reaction is finished, cooling to room temperature, sealing and filtering the reaction liquid, transferring the reaction liquid into a dehydration kettle, and keeping the reaction liquid at a certain temperature for a period of time under high vacuum to obtain yellowish-brown oily liquid, namely the product.

In a preferred embodiment of the present invention, the mixture in the mixing step is 695kg of bromoacetic acid, 220kg of 1, 4-butylene glycol and 2kg of sodium bisulfate, and the product in the final step is 820kg of 1, 4-bis (bromoethanoloxy) -2-butene.

In a preferred embodiment of the present invention, the mixture in the mixing step is 695kg of bromoacetic acid, 155kg of ethylene glycol and 2kg of sodium bisulfate, and the product in the final step is 750kg of 1, 4-bis (bromoethanoloxy) -2-butene.

In a preferred embodiment of the present invention, the pressure of the vacuum pump in the mixing step is-0.085 MPa and the temperature is 50 ℃.

In a preferred embodiment of the present invention, in the reaction step, the reaction time is 3-7h, the temperature is 95 ℃, and the holding time is 1-2 h.

In a preferred embodiment of the invention, in the step of preparing the finished product, the pressure of the high vacuum is-0.098 Mpa, the temperature is 70-80 ℃, and the holding time is 1-2 h.

The invention has the beneficial effects that: the invention avoids the safety problem and occupational health hazard brought by using the solvent, the catalyst uses sodium bisulfate, can be separated by filtration after the reaction is finished, and can be applied for a plurality of batches; the method has the advantages that COD (chemical oxygen demand) influence on wastewater treatment by catalysts such as toluenesulfonic acid is avoided, the method accords with the current green process development direction, the production efficiency is improved, water generated by reaction is taken away as soon as the water is generated under the negative pressure condition, the reaction is promoted, the washing process is omitted, and no wastewater is generated.

Detailed Description

The following detailed description of the preferred embodiments of the present invention is provided to enable those skilled in the art to more readily understand the advantages and features of the present invention, and to clearly and unequivocally define the scope of the present invention.

The embodiment of the invention comprises the following steps:

a green environment-friendly process for synthesizing bromoacetate by a solvent-free method comprises the following steps:

1) mixing: adding 695kg of bromoacetic acid, 220kg of 1, 4-butylene glycol and 2kg of sodium bisulfate into a reaction kettle, starting stirring, starting a vacuum pump system to adjust the pressure to be 0.085Mpa, and slowly heating to 50 ℃; 2) Reaction: after the reaction starts, slowly raising the reaction temperature to 95 ℃ within 3-7h, keeping the temperature for 1-2h, and sampling and analyzing; 3) And (3) finished product: after the reaction is finished, cooling to room temperature, sealing and filtering the reaction liquid, transferring the reaction liquid into a dehydration kettle, and keeping the dehydration kettle at 70-80 ℃ for 1-2h under high vacuum of-0.098 Mpa to obtain 820kg of 1, 4-bis (bromoethanoloxy) -2-butene as yellowish brown oily liquid.

Example one

A green environment-friendly process for synthesizing bromoacetate by a solvent-free method comprises the following steps:

1) mixing: adding 695kg of bromoacetic acid, 220kg of 1, 4-butylene glycol and 2kg of sodium bisulfate into a reaction kettle, starting stirring, starting a vacuum pump system to adjust the pressure to be 0.085Mpa, and slowly heating to 50 ℃; 2) Reaction: after the reaction is started, slowly raising the reaction temperature to 95 ℃ within 4.5h, keeping the temperature for 1.4h, and sampling and analyzing; 3) And (3) finished product: after the reaction, the temperature is reduced to room temperature, the reaction liquid is filtered in a closed mode, and the reaction liquid is transferred to a dehydration kettle and kept for 1.3 hours at the temperature of 75 ℃ under the high vacuum of-0.098 Mpa, so that 820kg of 1, 4-bis (bromoethanoloxy) -2-butene serving as brown oily liquid is obtained, and the yield is 90.46%.

Example two

A green environment-friendly process for synthesizing bromoacetate by a solvent-free method comprises the following steps:

1) mixing: adding 695kg of bromoacetic acid, 220kg of 1, 4-butylene glycol and 2kg of sodium bisulfate into a reaction kettle, starting stirring, starting a vacuum pump system to adjust the pressure to be 0.085Mpa, and slowly heating to 50 ℃; 2) Reaction: after the reaction is started, slowly raising the reaction temperature to 95 ℃ within 5.5h, keeping the temperature for 1.8h, and sampling and analyzing; 3) And (3) finished product: after the reaction, the temperature is reduced to room temperature, the reaction liquid is filtered in a closed mode, and the reaction liquid is transferred to a dehydration kettle and kept for 1.6 hours at 78 ℃ under high vacuum of-0.098 Mpa to obtain 820kg of 1, 4-bis (bromoethanoloxy) -2-butene as brown oily liquid, wherein the yield is 90.28%.

The parameter indexes of the first and second examples are shown in the following table.

A green environment-friendly process for synthesizing bromoacetate by a solvent-free method comprises the following steps:

1) mixing: adding 695kg of bromoacetic acid, 155kg of ethylene glycol and 2kg of sodium bisulfate into a reaction kettle, starting stirring, starting a vacuum pump system to adjust the pressure to be 0.085Mpa, and slowly heating to 50 ℃; 2) Reaction: after the reaction starts, slowly raising the reaction temperature to 95 ℃ within 3-7h, keeping the temperature for 1-2h, and sampling and analyzing; 3) And (3) finished product: after the reaction is finished, cooling to room temperature, carrying out closed filtration on the reaction solution, transferring the reaction solution into a dehydration kettle, and keeping the dehydration kettle at 70-80 ℃ for 1-2h under high vacuum of-0.098 Mpa to obtain 750kg of brown oily liquid 1, 4-bis (bromoethanoloxy) -2-butene.

EXAMPLE III

A green environment-friendly process for synthesizing bromoacetate by a solvent-free method comprises the following steps:

1) mixing: adding 695kg of bromoacetic acid, 155kg of ethylene glycol and 2kg of sodium bisulfate into a reaction kettle, starting stirring, starting a vacuum pump system to adjust the pressure to be 0.085Mpa, and slowly heating to 50 ℃; 2) Reaction: after the reaction is started, slowly raising the reaction temperature to 95 ℃ within 5 hours, keeping the temperature for 1.5 hours, and sampling and analyzing; 3) And (3) finished product: after the reaction is finished, cooling to room temperature, sealing and filtering the reaction solution, transferring the reaction solution into a dehydration kettle, and keeping the dehydration kettle at 75 ℃ for 1.5h under high vacuum of-0.098 Mpa to obtain 750kg of 1, 4-bis (bromoethanoloxy) -2-butene as brown oily liquid with the yield of 93%.

The parameter indexes of the second example are shown in the following table.

The invention is a green environment-friendly process for synthesizing bromoacetate by a solvent-free method, an inert organic reaction solvent is not needed, a step of removing the reaction solvent is not needed, safety problems and occupational health hazards brought by the use of the solvent are avoided, a catalyst uses sodium bisulfate, and the catalyst can be separated by filtration after the reaction is finished and can be applied in batches; the method has the advantages that COD (chemical oxygen demand) influence on wastewater treatment by catalysts such as toluenesulfonic acid is avoided, the method accords with the current green process development direction, the production efficiency is improved, water generated by reaction is taken away as soon as the water is generated under the negative pressure condition, the reaction is promoted, the washing process is omitted, and no wastewater is generated.

The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by the present specification, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.