阅读说明：本技术 一种n-正丁基乙醇胺的合成方法及装置 (Synthesis method and device of N-N-butyl ethanolamine ) 是由 钱莉苹 黄勇 吴世刚 于 2019-10-23 设计创作，主要内容包括：本发明公开了一种N-正丁基乙醇胺的合成方法及装置,合成装置包括如下组成部分：部件1)、再沸器配有加热温控和搅拌装置；部件2)、精馏柱配有回流冷凝管和分馏接收装置；部件3)、环氧乙烷加入装置,合成方法的化学反应式为：<Image he="165" wi="700" file="DDA0002244507790000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>第一步：材料、仪器准备：将环氧乙烷和正丁胺分取出备用,将需要用到的四口烧瓶、温度计、精馏柱和冷凝管清洁烘干后备用试。本发明采用环氧乙烷和正丁胺合成N-正丁基乙醇胺的路线,由于两个原材料价格相对比较便宜,原子经济效益高,同时采用特殊设备后可以提高了产品的选择性,反应过程中也不产生太多的废弃物,对环保压力也比较小,综合成本显著降低。所以本文采用该路线合成N-正丁基乙醇胺。(The invention discloses a method and a device for synthesizing N-N-butyl ethanolamine, wherein the synthesizing device comprises the following components: the part 1) and the reboiler are provided with a heating temperature control and stirring device; the component 2) and the rectification column are provided with a reflux condenser pipe and a fractionation receiving device; part 3), ethylene oxide adding device, the chemical reaction formula of the synthetic method is: the first step is as follows: preparing materials and instruments: the ethylene oxide and the n-butylamine are separated for standby use, and a four-neck flask which is needed to be used is usedAnd cleaning and drying the thermometer, the rectifying column and the condensing tube for standby test. The invention adopts a route of synthesizing the N-N-butyl ethanolamine by the ethylene oxide and the N-butylamine, and has the advantages of high atom economic benefit due to the relative low price of the two raw materials, improved product selectivity by adopting special equipment, no generation of too much waste in the reaction process, low environmental protection pressure and remarkably reduced comprehensive cost. This route is therefore used herein for the synthesis of N-N-butyl ethanolamine.)

1. A synthetic device of N-N-butyl ethanolamine is characterized in that: the method comprises the following components:

the part 1) and the reboiler are provided with a heating temperature control and stirring device;

the component 2) and the rectification column are provided with a reflux condenser pipe and a fractionation receiving device;

part 3), ethylene oxide addition apparatus.

2. A method and a device for synthesizing N-N-butyl ethanolamine are characterized in that: the chemical reaction formula of the synthesis method is as follows:

the first step is as follows: preparing materials and instruments: taking out ethylene oxide and n-butylamine for later use, cleaning and drying a four-mouth flask, a thermometer, a rectifying column and a condensing tube which are required to be used for later use, taking out a magnetic stirrer and an electric heater for power-on debugging, and finally completing construction of used processing equipment after debugging is completed;

the second step is that: air replacement: firstly, 300-400mL of n-butylamine is added into a 500mL four-neck flask provided with a reflux condenser tube, a thermometer, a rectifying column, a circulating pump and an ethylene oxide gas-guide tube, the air of the system is replaced by nitrogen, then the system is vacuumized to-0.03-0.08 MPa, and a vacuum valve is closed;

the third step: collecting and detecting: placing an oil bath device below a four-mouth bottle, wherein the bottom of the four-mouth bottle extends into the oil bath device, adjusting the temperature of the oil bath device to be 75-81 ℃, then opening a circulating pump with two ends respectively communicated with a condenser pipe and the four-mouth bottle, then opening an ethylene oxide valve, slowly introducing the metered ethylene oxide into a system, wherein the system pressure is 0.05-0.06 MPa, continuously stirring by a magnetic stirrer in the process of introducing the ethylene oxide, detecting the temperature of a reactant at any time by a thermometer (the testing end of the thermometer is inserted into n-butylamine), maintaining the reaction temperature at 134-140 ℃ after the introduction is finished, continuously reacting for a certain time, carrying out gas chromatography controlled reaction, and stopping the reaction when the increase of a product is basically not detected;

the fourth step: after the reaction is finished, keeping the temperature for 1-1.5 hours, closing the magnetic stirrer and the oil bath equipment, when the temperature of substances in the quality of four ports is reduced to room temperature, finally transferring the materials into a rectifying device, recovering N-butylamine under normal pressure, then carrying out vacuum rectification to obtain N-N-butylethanolamine, combining high-boiling N, N-di-N-butylethanolamine for many times, and then rectifying and recovering again;

the fifth step: and respectively storing 5-10mL of the N-N-butyl ethanolamine which is recovered for many times, and then respectively determining the purity of the N-N-butyl ethanolamine.

3. The synthesis apparatus according to claim 1, wherein the stirring accompanying the reboiler of part 1) is stirring, and the temperature is controlled to a range from room temperature to 150 ℃ by using an oil bath.

4. The synthesis device as claimed in claim 1, wherein the rectification column in the part 2) is provided with a reflux condenser and a fractional distillation receiving device, and can reflux and rectify and separate out the raw material N-butylamine and the product N-N-butylethanolamine.

5. The method for synthesizing N-N-butyl ethanolamine according to claim 2, wherein the method comprises the following steps: in the third step, the molar ratio of the raw materials of n-butylamine to ethylene oxide is 1:1.6 to 1.8.

6. The method for synthesizing N-N-butyl ethanolamine according to claim 2, wherein the method comprises the following steps: the velocity and flow rate of the valve arranged on the surface of the gas guide tube between the ethylene oxide and the rectification column are set to be 4-7cm³The time for introducing is 5-6 hours.

7. The method for synthesizing N-N-butyl ethanolamine according to claim 2, wherein the method comprises the following steps: and a pressure gauge is arranged at the top of the condensation pipe, the pressure ranges of the four-mouth bottle, the rectifying column and the condensation pipe are 0.05MPa-0.06MPa, in the third step, n-butylamine is added into a reboiler container, air is replaced by nitrogen, a reaction system is vacuumized to-0.08 MPa, and ethylene oxide is sucked at uniform speed after the reaction system is heated to the reaction temperature.

8. The method for synthesizing N-N-butyl ethanolamine according to claim 2, wherein the method comprises the following steps: and in the third step, after the ethylene oxide is added, the reaction is carried out in a heat preservation way until the product in the reaction liquid is not increased, the temperature is reduced to room temperature, and in the third step, the temperature of the kettle is gradually increased in the reaction process, initially, the temperature of n-butylamine in the system is basically controlled to be 78 ℃, the product is more and more along with the reaction, the boiling point of the product is 198 ℃, so that the temperature of the material in the kettle is gradually increased.

9. The method for synthesizing N-N-butyl ethanolamine according to claim 2, wherein the method comprises the following steps: and in the second step, the operation of adding n-butylamine into the four-mouth bottle is carried out in a fume hood, the adding time is 1-2 minutes, and a thermometer, a rectifying column, a condensing pipe and a circulating pump pipeline are quickly connected after the adding is finished.

Technical Field

The invention relates to the technical field of chemical synthesis, in particular to a method and a device for synthesizing N-N-butyl ethanolamine.

Background

N-N-butyl ethanolamine and N, N-di-N-butyl ethanolamine are two important fine chemical intermediates, have wide application in the aspects of textile, medicine, agricultural chemicals and the like, can be used for producing medicines, coatings, surfactants and the like, and can also be used as decarbonization agents, desulfurizing agents and the like. In recent years, N-N-butyl ethanolamine is developed and utilized as an auxiliary ingredient and a coating regulator of a metal cutting fluid, and with the rapid development of the processing and building industries of China industry, the market demand of the N-N-butyl ethanolamine is rapidly expanded. Therefore, studies have been made to increase the yield of N-N-butylethanolamine and to reduce the synthesis cost of N-N-butylethanolamine.

The existing production modes of N-N-butylethanolamine are divided into two major types, namely firstly, hydroxyethylation synthesis is carried out by taking N-butylamine as a raw material, and secondly, amine alkylation synthesis is carried out by taking ethanolamine as a raw material, wherein the following synthesis routes are provided:

route of ethanolamine, n-butyl bromide:

the reaction of ethanolamine and N-butyl bromide belongs to nucleophilic substitution reaction of alkyl halide, N-butyl bromide firstly reacts with one molecule of ethanolamine to generate a target product N-N-butyl ethanolamine, but the nucleophilicity of the N-N-butyl ethanolamine is greater than that of the ethanolamine, and the N-N-butyl ethanolamine can continuously perform further nucleophilic substitution reaction with unreacted N-butyl bromide in a system to generate the N, N-di-N-butyl ethanolamine. In order to increase the yield of N-N-butyl ethanolamine, the molar ratio of ethanolamine must be greatly increased to suppress the production of N, N-di-N-butyl ethanolamine, and therefore the cost is high.

Chlorohydrin, n-butylamine route:

the reaction produces di-substituted by-products in a ratio related to the molar ratio of the reaction raw materials, and the higher the ratio of n-butylamine, the higher the proportion of the main product obtained, but the by-products cannot be completely suppressed. From the viewpoint of each raw material and product, N-butylamine has a boiling point of 77 ℃, chlorohydrin needs to be completely converted without consideration of separation, a main product N-butylethanolamine has a boiling point of 200 ℃, a byproduct N-butyldiethanolamine has a boiling point of 274 ℃, and ethanolamine for the reaction has a boiling point of 170.5 ℃, so that a higher distillation column is required for product separation. And the chloroethanol belongs to a highly toxic chemical, needs special license for purchase and use, is not bought from the raw material after being heard from many aspects, considers the convenience of final large-scale production, and abandons the route finally.

Ethanolamine, n-butyraldehyde route:

in the first step, n-butyraldehyde reacts with ethanolamine to form enamine, which is an equilibrium reaction and is reversible in the presence of water, and a five-membered ring by-product is formed while the enamine is formed.

In the second step, enamine hydrogenation reaction, as can be seen from the following table, a small amount of water can be tested 2b and returned to 2a again, and then hydrogenated to generate the target product N-N-butyl ethanolamine, but enamine formation after excessive water is affected, and yield is also reduced.

Combining the above reaction results, method one: the route for synthesizing the N-N-butyl ethanolamine from the N-butyl chlorohydrate and the ethanolamine needs a great excess of ethanolamine, so that the required reaction equipment is large, the productivity is low, the ethanolamine recovery needs a great deal of energy, meanwhile, a great deal of dichloromethane is needed in the post-treatment process to extract products, the boiling point of the dichloromethane is low, only about 40 ℃, the volatility is very high, the recovery rate is very low, the cost is high, and meanwhile, a great deal of wastewater containing salt and ethanolamine is generated during neutralization, and the additional treatment cost is needed, so the comprehensive cost is higher; the second method comprises the following steps: in the route for synthesizing the N-N-butyl ethanolamine from the chloroethanol and the N-butylamine, the chloroethanol as a raw material has high toxicity and is not easy to purchase; the third method comprises the following steps: the synthesis route of N-N-butyl ethanolamine from N-butyraldehyde and ethanolamine has low yield due to the production of a large amount of by-products, and meanwhile, a high-pressure reaction kettle is required for hydrogenation reaction, and the equipment investment is large because of being inappropriate.

Disclosure of Invention

The invention aims to provide a method and a device for synthesizing N-N-butyl ethanolamine, which have the advantages of not generating too much waste in the reaction process, having smaller pressure on environmental protection and low comprehensive cost, and solve the problems in the background technology.

In order to achieve the purpose, the invention provides the following technical scheme: a synthetic device of N-N-butyl ethanolamine is characterized in that: the method comprises the following components:

the part 1) and the reboiler are provided with a heating temperature control and stirring device;

the component 2) and the rectification column are provided with a reflux condenser pipe and a fractionation receiving device;

part 3), ethylene oxide addition apparatus.

A method and a device for synthesizing N-N-butyl ethanolamine are characterized in that: the chemical reaction formula of the synthesis method is as follows:

the first step is as follows: preparing materials and instruments: taking out ethylene oxide and n-butylamine for later use, cleaning and drying a four-mouth flask, a thermometer, a rectifying column and a condensing tube which are required to be used for later use, taking out a magnetic stirrer and an electric heater for power-on debugging, and finally completing construction of used processing equipment after debugging is completed;

the second step is that: air replacement: firstly, 300-400mL of n-butylamine is added into a 500mL four-neck flask provided with a reflux condenser tube, a thermometer, a rectifying column, a circulating pump and an ethylene oxide gas-guide tube, the air of the system is replaced by nitrogen, then the system is vacuumized to-0.03-0.08 MPa, and a vacuum valve is closed;

the third step: collecting and detecting: placing an oil bath device below a four-mouth bottle, wherein the bottom of the four-mouth bottle extends into the oil bath device, adjusting the temperature of the oil bath device to be 75-81 ℃, then opening a circulating pump with two ends respectively communicated with a condenser pipe and the four-mouth bottle, then opening an ethylene oxide valve, slowly introducing the metered ethylene oxide into a system, wherein the system pressure is 0.05-0.06 MPa, continuously stirring by a magnetic stirrer in the process of introducing the ethylene oxide, detecting the temperature of a reactant at any time by a thermometer (the testing end of the thermometer is inserted into n-butylamine), maintaining the reaction temperature at 134-140 ℃ after the introduction is finished, continuously reacting for a certain time, carrying out gas chromatography controlled reaction, and stopping the reaction when the increase of a product is basically not detected;

the fourth step: after the reaction is finished, keeping the temperature for 1-1.5 hours, closing the magnetic stirrer and the oil bath equipment, when the temperature of substances in the quality of four ports is reduced to room temperature, finally transferring the materials into a rectifying device, recovering N-butylamine under normal pressure, then carrying out vacuum rectification to obtain N-N-butylethanolamine, combining high-boiling N, N-di-N-butylethanolamine for many times, and then rectifying and recovering again;

the fifth step: and respectively storing 5-10mL of the N-N-butyl ethanolamine which is recovered for many times, and then respectively determining the purity of the N-N-butyl ethanolamine.

Preferably, the stirring accompanying the reboiler of part 1) is stirring, and the temperature is controlled to room temperature to 150 ℃ by using an oil bath.

Preferably, the rectifying column of the part 2) is provided with a reflux condenser pipe and a fractional distillation receiving device, and can reflux and rectify and separate out the raw material N-butylamine and the product N-N-butylethanolamine.

Preferably, the molar ratio of the raw n-butylamine to the ethylene oxide in the third step is 1:1.6 to 1.8.

Preferably, the flow rate of the valve speed arranged on the surface of the gas guide pipe between the ethylene oxide and the rectification column is set to be 4-7cm³The time for introducing is 5-6 hours.

Preferably, a pressure gauge is arranged at the top of the condensation pipe, the pressure ranges of the four-mouth bottle, the rectifying column and the condensation pipe are 0.05MPa-0.06MPa, in the third step, n-butylamine is added into a reboiler container, air is replaced by nitrogen, the reaction system is vacuumized to-0.08 MPa, and ethylene oxide is sucked at uniform speed after the reaction system is heated to the reaction temperature.

Preferably, after the ethylene oxide is added in the third step, the reaction is carried out under a heat preservation condition until the product in the reaction liquid is not increased, and the temperature is reduced to room temperature, and the temperature of the kettle is gradually increased in the third step in the reaction process, wherein initially, the temperature of n-butylamine in the system is basically controlled to 78 ℃, the product is more and more along with the reaction, and the boiling point of the product is 198 ℃, so that the temperature of the material in the kettle is gradually increased.

Preferably, the third step of adding the n-butylamine into the four-mouth bottle is carried out in a fume hood, the adding time is between 1 and 2 minutes, and a thermometer, a rectifying column, a condensing pipe and a circulating pump pipeline are quickly connected after the adding is finished.

Compared with the prior art, the invention has the following beneficial effects:

1. the invention adopts a route of synthesizing the N-N-butyl ethanolamine by the ethylene oxide and the N-butylamine, and has the advantages of high atom economic benefit due to the relative low price of the two raw materials, improved product selectivity by adopting special equipment, no generation of too much waste in the reaction process, low environmental protection pressure and remarkably reduced comprehensive cost. This route is therefore used herein for the synthesis of N-N-butyl ethanolamine.

Drawings

FIG. 1 is a diagram of the chemical reaction equation of the present invention;

FIG. 2 is a diagram of a chemical reaction apparatus according to the present invention;

FIG. 3 is a graph showing the relationship between N-N-butylethanolamine obtained at different N-butylamine addition amounts;

FIG. 4 is a graph showing the influence of the ethylene oxide introduction rate on the production of N-N-butylethanolamine;

FIG. 5 is a graph showing the effect of reaction temperature and pressure on the formation of N-N-butylethanolamine.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Referring to the drawings, the present invention provides a technical solution: a synthetic device of N-N-butyl ethanolamine is characterized in that: the method comprises the following components:

the part 1) and the reboiler are provided with a heating temperature control and stirring device;

the component 2) and the rectification column are provided with a reflux condenser pipe and a fractionation receiving device;

part 3), ethylene oxide addition apparatus.

A method and a device for synthesizing N-N-butyl ethanolamine are characterized in that: the chemical reaction formula of the synthesis method is as follows:

the first step is as follows: preparing materials and instruments: taking out ethylene oxide and n-butylamine for later use, cleaning and drying a four-mouth flask, a thermometer, a rectifying column and a condensing tube which are required to be used for later use, taking out a magnetic stirrer and an electric heater for power-on debugging, and finally completing construction of used processing equipment after debugging is completed;

the second step is that: air replacement: firstly, 300-400mL of n-butylamine is added into a 500mL four-neck flask provided with a reflux condenser tube, a thermometer, a rectifying column, a circulating pump and an ethylene oxide gas-guide tube, the air of the system is replaced by nitrogen, then the system is vacuumized to-0.03-0.08 MPa, and a vacuum valve is closed;

the third step: collecting and detecting: placing an oil bath device below a four-mouth bottle, wherein the bottom of the four-mouth bottle extends into the oil bath device, adjusting the temperature of the oil bath device to be 75-81 ℃, then opening a circulating pump with two ends respectively communicated with a condenser pipe and the four-mouth bottle, then opening an ethylene oxide valve, slowly introducing the metered ethylene oxide into a system, wherein the system pressure is 0.05-0.06 MPa, continuously stirring by a magnetic stirrer in the process of introducing the ethylene oxide, detecting the temperature of a reactant at any time by a thermometer (the testing end of the thermometer is inserted into n-butylamine), maintaining the reaction temperature at 134-140 ℃ after the introduction is finished, continuously reacting for a certain time, carrying out gas chromatography controlled reaction, and stopping the reaction when the increase of a product is basically not detected;

the fourth step: after the reaction is finished, keeping the temperature for 1-1.5 hours, closing the magnetic stirrer and the oil bath equipment, when the temperature of substances in the quality of four ports is reduced to room temperature, finally transferring the materials into a rectifying device, recovering N-butylamine under normal pressure, then carrying out vacuum rectification to obtain N-N-butylethanolamine, combining high-boiling N, N-di-N-butylethanolamine for many times, and then rectifying and recovering again;

the fifth step: and respectively storing 5-10mL of the N-N-butyl ethanolamine which is recovered for many times, and then respectively determining the purity of the N-N-butyl ethanolamine.

In the invention: part 1) stirring attached to the reboiler was controlled to room temperature to 150 ℃ using an oil bath.

In the invention: the component 2) rectification column is provided with a reflux condenser pipe and a fractionation receiving device, and can reflux and rectify and separate out the raw material N-butylamine and the product N-N-butylethanolamine.

In the invention: in the third step, the molar ratio of the raw materials of n-butylamine to ethylene oxide is 1:1.6 to 1.8.

In the invention: the velocity and flow rate of the valve arranged on the surface of the gas guide tube between the ethylene oxide and the rectification column are set to be 4-7cm³The time for introducing is 5-6 hours.

In the invention: and a pressure gauge is arranged at the top of the condensation pipe, the pressure ranges of the four-mouth bottle, the rectifying column and the condensation pipe are 0.05MPa-0.06MPa, in the third step, n-butylamine is added into a reboiler container, air is replaced by nitrogen, a reaction system is vacuumized to-0.08 MPa, and ethylene oxide is sucked at uniform speed after the reaction system is heated to the reaction temperature.

In the invention: and in the third step, after the ethylene oxide is added, the reaction is carried out in a heat preservation way until the product in the reaction liquid is not increased, the temperature is reduced to room temperature, and in the third step, the temperature of the kettle is gradually increased in the reaction process, initially, the temperature of n-butylamine in the system is basically controlled to be 78 ℃, the product is more and more along with the reaction, the boiling point of the product is 198 ℃, so that the temperature of the material in the kettle is gradually increased.

In the invention: and the third step, adding n-butylamine into the four-mouth bottle in a fume hood for 1-2 minutes, and quickly connecting a thermometer, a rectifying column, a condensation pipe and a circulating pump pipeline after the addition is finished.

From the relation chart of N-N-butylethanolamine obtained under different N-butylamine addition amounts in FIG. 3, it can be seen that with the increase of N-butylamine addition amount, the conversion rate of N-butylamine is lower and lower but the selectivity of N-N-butylethanolamine generation is gradually improved, the recovery cost of N-butylamine is comprehensively considered, the process determines that the mol ratio of N-butylamine to ethylene oxide is preferably 1: 1.6-1.8, and the optimal ratio is 1: 1.8;

FIG. 4 shows the influence of the ethylene oxide introduction rate on the production of N-N-butylethanolamine, and it can be seen that the ethylene oxide content in the reaction region is too high due to too high introduction rate, which results in a low molar ratio of N-butylamine to ethylene oxide in the reaction region, increased by-products and poor product selectivity. The feeding speed is too low, the product selectivity is not increased much and tends to be stable, but the energy consumption is increased, and the production cost is not controlled easily, so that the process is suitable for finishing the feeding at the uniform speed for 5-6 hours, and the optimal time is 6 hours;

FIG. 5 shows the influence of the reaction temperature and pressure on the formation of N-N-butylethanolamine, and it can be seen that the control of the temperature is mainly determined by the vaporized amount of N-butylamine, and that the larger the vaporized amount of N-butylamine is, the larger the molar ratio of N-butylamine in the reaction zone is, so that the higher the selectivity is. The system pressure is directly indicative of the vaporized amount of n-butylamine, so the control of the system pressure is used herein to control the vaporized amount of n-butylamine, and fig. 5 shows the pressure as a function of selectivity. As can be seen from the figure, the reaction pressure is low, the product selectivity is poor, the reaction pressure is too high, the requirement on equipment is high, and the energy consumption cost is correspondingly increased, so that the optimal reaction pressure determined by the process is between 0.05MPa and 0.06MPa, and the optimal reaction pressure is 0.06 MPa.

In summary, the following steps: according to the method and the device for synthesizing the N-N-butylethanolamine, a route for synthesizing the N-N-butylethanolamine by using the ethylene oxide and the N-butylamine is adopted, and as the two raw materials are relatively cheap, the atom economic benefit is high, and meanwhile, special equipment is adopted, the product selectivity can be improved, too much waste is not generated in the reaction process, the environmental protection pressure is relatively low, and the comprehensive cost is remarkably reduced. Therefore, the route is adopted to synthesize the N-N-butyl ethanolamine, through experiments, the favorable factors and the unfavorable factors of each route for synthesizing the N-butyl ethanolamine are analyzed and compared, the yield conditions of each route under different schemes and the consumption of raw and auxiliary materials are analyzed and compared, the most economical route and scheme for synthesizing the N-butyl ethanolamine by using the ethylene oxide and the N-butylamine are finally determined, the product quality index reaches over 99.0 percent and exceeds the content of the original sample.

It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.

Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.