阅读说明：本技术 一种丁醛一步法生产丁酸丁酯的合成系统及方法 (Synthesis system and method for producing butyl butyrate by butyraldehyde one-step method ) 是由 李越 张波 李云辉 苗淳 杨志波 郝金明 李满枝 李治水 于 2020-12-21 设计创作，主要内容包括：本发明公开了一种丁醛一步法生产丁酸丁酯的合成系统：丁醛进料泵连接丁醛原料罐,催化剂输送泵连接催化剂溶解罐,丁醛进料泵和催化剂输送泵连接混合器入口,混合器出口连接外循环冷却器管程入口,管程出口连接反应釜,反应釜底部连接循环泵,循环泵出口与外循环冷却器管程入口和粗品储罐入口连接,粗品储罐连接灭活剂储罐与分离系统；方法：原料丁醛和催化剂预混,进入外循环冷却器冷却,输送至反应釜反应,溶液大部分作为循环反应液进入外循环冷却器管程,剩余部分采出至粗品储罐,向粗品储罐加入灭活剂,使催化剂失活,丁酸丁酯粗品进入分离系统,灭活剂从粗品储罐排污口排出。(The invention discloses a synthesis system for producing butyl butyrate by a butyraldehyde one-step method, which comprises the following steps: the butyraldehyde feeding pump is connected with a butyraldehyde raw material tank, the catalyst delivery pump is connected with the catalyst dissolving tank, the butyraldehyde feeding pump and the catalyst delivery pump are connected with an inlet of a mixer, an outlet of the mixer is connected with a tube pass inlet of an external circulation cooler, a tube pass outlet is connected with a reaction kettle, the bottom of the reaction kettle is connected with a circulating pump, an outlet of the circulating pump is connected with a tube pass inlet of the external circulation cooler and an inlet of a crude product storage tank, and the crude product storage tank is connected with an inactivating agent storage tank; the method comprises the following steps: premixing raw material butyraldehyde and a catalyst, cooling the mixed solution in an external circulation cooler, conveying the cooled mixed solution to a reaction kettle for reaction, taking most of the solution as a circulating reaction solution, introducing the circulating reaction solution into the tube side of the external circulation cooler, extracting the rest of the solution to a crude product storage tank, adding an inactivating agent into the crude product storage tank to inactivate the catalyst, introducing the crude butyl butyrate into a separation system, and discharging the inactivating agent from a drain outlet of the crude product storage tank.)

1. A synthesis system for producing butyl butyrate by a butyraldehyde one-step method is characterized by comprising a butyraldehyde raw material tank (1), a butyraldehyde feeding pump (2), a catalyst dissolving tank (3), a catalyst conveying pump (4), a mixer (5), an external circulation cooler (6), a reaction kettle (7), a circulating pump (8), a crude product storage tank (11) and an inactivating agent storage tank (12);

the butyraldehyde feeding pump (2) is connected with butyraldehyde feed tank (1) through a pipeline, catalyst delivery pump (4) is connected with catalyst dissolving tank (3) through a pipeline, butyraldehyde feeding pump (2) is exported and catalyst delivery pump (4) export respectively through pipeline and blender (5) entry linkage, blender (5) export is through pipeline and extrinsic cycle cooler (6) tube side entry linkage, extrinsic cycle cooler (6) tube side export is connected with reation kettle (7) through a pipeline, reation kettle (7) bottom discharge gate passes through pipeline and circulating pump (8) entry linkage, circulating pump (8) export is respectively through circulating line (9), production line (10) and extrinsic cycle cooler (6) tube side entry and crude product storage tank (11) entry linkage, crude product storage tank (11) is connected with inactivator storage tank (12) through a pipeline, the bottom of the crude product storage tank (11) is provided with a discharge pipe (14), and the discharge pipe (14) is connected with a separation system through a pipeline.

2. The synthesis system for producing butyl butyrate by using a butyraldehyde one-step method according to claim 1, wherein a pump with a flow metering function is adopted for the butyraldehyde feeding pump (2) and the catalyst conveying pump (4), or regulating valves for regulating the flow are arranged at the outlets of the butyraldehyde feeding pump (2) and the catalyst conveying pump (4).

3. The synthesis system for producing butyl butyrate by using a butyraldehyde one-step method according to claim 1, wherein the outer walls of the mixer (5) and the reaction kettle (7) are provided with cooling jackets; and the catalyst dissolving tank (3), the reaction kettle (7) and the crude product storage tank (11) are all provided with stirring devices.

4. The synthesis system for producing butyl butyrate by using a butyraldehyde one-step method according to claim 1, wherein a back pressure valve is arranged on each of the butyraldehyde raw material tank (1), the catalyst dissolving tank (3), the reaction kettle (7), the crude product storage tank (11) and the inactivator storage tank (12); the catalyst dissolving tank (3) is provided with a heating device, and the top of the catalyst dissolving tank (3) is provided with a catalyst feeding hopper (15).

5. The synthesis system for producing butyl butyrate by using a butyraldehyde one-step method according to claim 1, wherein a flow regulating valve (18) is arranged on each of the circulating pipeline (9) and the extraction pipeline (10), and a valve (13) is arranged on a pipeline connected between the inactivating agent storage tank (12) and the crude product storage tank (11).

6. The synthesis system for producing butyl butyrate by using a butyraldehyde one-step method according to claim 1, wherein the inactivating agent storage tank (12) is positioned above the crude product storage tank (11), a drain outlet (17) is formed in the bottom of the crude product storage tank (11), a sight glass (16) is arranged on the side surface of the lower part of the crude product storage tank (11), the upper part of the discharge pipe (14) extends into the crude product storage tank (11) and is vertical to the inner wall of the bottom of the tank, and the height of the upper end opening of the discharge pipe (14) is within the visual field of the sight glass (16).

7. A synthesis method of a synthesis system for producing butyl butyrate based on the butyraldehyde one-step method in any one of the claims 1 to 6, which is characterized by comprising the following steps:

the first step is as follows: performing nitrogen pressure maintaining on a butyraldehyde raw material tank (1), a catalyst dissolving tank (3), a reaction kettle (7), a crude product storage tank (11) and an inactivating agent storage tank (12) through a backpressure valve, wherein the pressure range is 10-20 kPa; chilled water is fed into cooling jackets of the mixer (5) and the reaction kettle (7), and the chilled water is introduced into the shell pass of the external circulation cooler (6);

the second step is that: high temperature dissolution of catalyst

Adding a catalyst into a catalyst dissolving tank (3), heating the catalyst to raise the temperature in a stirring state, keeping the temperature after heating to 60-100 ℃, and dissolving the catalyst into a solution state;

the third step: reaction for preparing butyl butyrate by catalyzing and disproportionating butyraldehyde

Premixing raw material butyraldehyde and a catalyst in a certain ratio in a mixer (5), mixing, cooling in an external circulation cooler (6) in a tube pass, conveying to a reaction kettle (7) for full reaction, taking most of crude butyl butyrate solution obtained by reaction as a circulating reaction liquid, entering the external circulation cooler (6) in the tube pass, removing heat released by reaction, extracting the rest into a crude product storage tank (11), and keeping the material inlet and outlet balance of the reaction kettle (7);

the fourth step: deactivated catalyst

Adding a deactivating agent into a crude product storage tank (11) according to the mass ratio of the butyl butyrate crude product to the deactivating agent of 80: 1-100: 1 to deactivate the catalyst, mixing and stirring for 15-30 minutes, standing the solution until the solution is completely layered, allowing the butyl butyrate crude product on the upper layer to enter a separation system, and discharging the deactivating agent from a drain outlet (17) at the bottom of the crude product storage tank (11).

8. The synthesis method for producing butyl butyrate by using a butyraldehyde one-step method according to claim 7, wherein in the second step, the stirring speed of the catalyst dissolving tank (3) is controlled to be 200-400 rpm; the catalyst is POP-Ru, a porous organic polymer rich in hydroxyl is used as a substrate, and a Ru complex structure is formed on the surface of the porous organic polymer.

9. The synthesis method for producing butyl butyrate by using butyraldehyde one-step method according to claim 7, wherein in the third step, the raw material butyraldehyde and the catalyst solution are respectively conveyed to the mixer (5) by a butyraldehyde feeding pump (2) and a catalyst conveying pump (4) according to a mass ratio of 4: 1-12: 1; the stirring speed of the reaction kettle (7) is controlled to be 200-400 rpm, and the temperature in the reaction kettle (7) is controlled to be 10-25 ℃; the temperature of the tube pass outlet of the external circulation cooler (6) is controlled to be 8-20 ℃; the mass ratio of the part of the butyl butyrate crude product solution obtained by the reaction, which is taken as a circulating reaction solution, entering the tube pass of the external circulating cooler (6) to the part of the butyl butyrate crude product solution extracted to the crude product storage tank (11) is controlled to be 100: 1-150: 1.

10. The synthesis method for producing butyl butyrate by using a butyraldehyde one-step method according to claim 7, wherein in the fourth step, the stirring speed of the crude product storage tank (11) is controlled to be 200-400 rpm; the standing time of the solution is controlled to be 15-30 minutes; the inactivating agent is desalted water or dilute alkali solution.

Technical Field

The invention relates to the technical field of chemical production, in particular to a synthesis system and a method for producing butyl butyrate by a butyraldehyde one-step method.

Background

Butyl butyrate, also known as n-butyl butyrate, is a colorless transparent liquid with fruit flavor and is widely applied to food additives and organic solvents. In the field of paint and coating, butyl butyrate has mild solubility and excellent whitening resistance; in the coating field of plastic products, the problem of 'bottom burning' can be better solved, and the coating has good color development property on pigments in the wood coatings; in the formula of the metallic flashing paint, the metallic flashing paint has good protection to metallic pigment. According to the information feedback of the paint industry, the potential demand of butyl butyrate in China is about 50 ten thousand tons per year.

The traditional butyl butyrate production process is that n-butyric acid and n-butanol are subjected to ester synthesis reaction under the catalysis of concentrated sulfuric acid. In addition, the butyric acid and the butanol which are used as production raw materials of the process are industrially obtained by respectively using butyraldehyde as a raw material through oxidation and hydrogenation processes, and water molecules need to be removed in the process of synthesizing the butyl butyrate by utilizing the traditional production process, so that resource waste is caused.

Wanghai Jing (Wanghai Jing, Chuanwei, butyl butyrate synthesized by n-butanol in one step, fine petrochemical industry, 2013,1, 20-22) reports that under the conditions of 260 +/-5 ℃ and not less than 0.4MPa, the n-butanol is catalyzed to prepare the butyl butyrate, the conversion rate of the n-butanol is 64 percent, and the selectivity of the butyl butyrate is 73.8 percent. Panwei male (Panwei male, one-step synthesis of butyl butyrate from n-butanol or n-butyraldehyde, petrochemical, 1993,22(2),111-114) reports that the conversion of n-butyraldehyde is catalyzed at 255 ℃ and 0.7MPa, the conversion rate is about 60%, and the selectivity of butyl butyrate is very low. Other research reports on the preparation of butyl butyrate by using butyraldehyde all have the problems of low conversion rate and selectivity, and are basically in the laboratory research stage, and no pilot-scale or industrial application cases are seen.

The production process for preparing butyl butyrate by using butyraldehyde in one step is developed by cooperation of Tianjin Bohai chemical engineering Yongli chemical industry Limited company (hereinafter, Yongli chemical industry for short) and the institute of chemical and physical research of the college of Chinese academy of sciences, the process takes butyraldehyde as a raw material, and the butyl butyrate is generated by catalytic disproportionation under mild conditions, so that the reaction route is simple, the raw material cost and energy consumption are low, equipment corrosion and environmental pollution are avoided, and the atom economy is high. Small-scale tests have completed the screening of high-efficiency catalysts, the optimization of production routes and the purification scheme of products. In order to promote the technological achievement to be converted into industrialization as soon as possible, a pilot test needs to be developed, the production process needs to be further optimized, and a set of scientific and complete industrial parameters for preparing butyl butyrate by using the butyraldehyde one-step method are obtained.

Disclosure of Invention

The invention aims to overcome the defects in the prior art and provides a synthesis system and a method for producing butyl butyrate by a butyraldehyde one-step method.

The purpose of the invention can be realized by the following technical scheme.

The invention relates to a synthesis system for producing butyl butyrate by a butyraldehyde one-step method, which comprises a butyraldehyde raw material tank, a butyraldehyde feeding pump, a catalyst dissolving tank, a catalyst delivery pump, a mixer, an external circulation cooler, a reaction kettle, a circulating pump, a crude product storage tank and an inactivating agent storage tank;

butyraldehyde feed pump entry is connected with butyraldehyde head tank through the pipeline, catalyst delivery pump entry passes through the pipeline and is connected with the catalyst dissolving tank, butyraldehyde feed pump export and catalyst delivery pump export respectively through pipeline and blender entry linkage, the blender export passes through pipeline and outer circulation cooler tube side entry linkage, outer circulation cooler tube side export is connected with reation kettle through the pipeline, reation kettle bottom discharge gate passes through the pipeline and circulating pump entry linkage, the circulation pump export respectively through circulation pipeline, extraction pipeline and outer circulation cooler tube side entry and crude product storage tank entry linkage, the crude product storage tank passes through the pipeline and is connected with the inactivator storage tank, crude product storage tank bottom is provided with the discharging pipe, the discharging pipe passes through the pipeline and is connected with piece-rate system.

The butyraldehyde feeding pump and the catalyst delivery pump both adopt pumps with flow metering functions, or outlets of the butyraldehyde feeding pump and the catalyst delivery pump are both provided with regulating valves for regulating flow.

Cooling jackets are arranged on the outer walls of the mixer and the reaction kettle; and the catalyst dissolving tank, the reaction kettle and the crude product storage tank are all provided with stirring devices.

The butyraldehyde raw material tank, the catalyst dissolving tank, the reaction kettle, the crude product storage tank and the inactivating agent storage tank are all provided with back pressure valves; the catalyst dissolving tank is provided with a heating device, and the top of the catalyst dissolving tank is provided with a catalyst feeding hopper.

And flow regulating valves are arranged on the circulating pipeline and the extraction pipeline, and valves are arranged on pipelines connected between the inactivating agent storage tank and the crude product storage tank.

The inactivator storage tank is located crude product storage tank top, crude product storage tank bottom is provided with the drain, crude product storage tank lower part side sets up the sight glass, discharging pipe upper portion extends to in the crude product storage tank and perpendicular to tank bottoms inner wall, and the port height is in the sight glass field of vision on the discharging pipe.

The purpose of the invention can be realized by the following technical scheme.

The invention discloses a synthesis method for producing butyl butyrate by a butyraldehyde one-step method, which comprises the following steps:

the first step is as follows: performing nitrogen pressure maintaining on a butyraldehyde raw material tank, a catalyst dissolving tank, a reaction kettle, a crude product storage tank and an inactivating agent storage tank through a back pressure valve, wherein the pressure range is 10-20 kPa; the cooling jackets of the mixer and the reaction kettle are filled with chilled water, and the shell side of the external circulation cooler is filled with chilled water;

the second step is that: high temperature dissolution of catalyst

Adding a catalyst into a catalyst dissolving tank, heating the catalyst to raise the temperature in a stirring state, keeping the temperature after heating to 60-100 ℃, and dissolving the catalyst into a solution state;

the third step: reaction for preparing butyl butyrate by catalyzing and disproportionating butyraldehyde

Premixing raw material butyraldehyde and a catalyst in a certain ratio in a mixer, mixing, cooling in an external circulation cooler tube pass, conveying to a reaction kettle for full reaction, taking most of crude butyl butyrate solution obtained by reaction as a circulation reaction liquid to enter the external circulation cooler tube pass, removing heat released by reaction, extracting the rest into a crude product storage tank, and keeping the balance of material inlet and outlet of the reaction kettle;

the fourth step: deactivated catalyst

Adding an inactivating agent into a crude product storage tank according to the mass ratio of the butyl butyrate crude product to the inactivating agent of 80: 1-100: 1 to inactivate the catalyst, mixing and stirring for 15-30 minutes, standing the solution until the solution is completely layered, allowing the upper layer butyl butyrate crude product to enter a separation system, and discharging the inactivating agent from a drain outlet at the bottom of the crude product storage tank.

In the second step, the stirring speed of the catalyst dissolving tank is controlled to be 200-400 rpm; the catalyst is POP-Ru, a porous organic polymer rich in hydroxyl is used as a substrate, and a Ru complex structure is formed on the surface of the porous organic polymer.

In the third step, the raw material butyraldehyde and the catalyst solution are respectively conveyed to a mixer through a butyraldehyde feeding pump and a catalyst conveying pump according to the mass ratio of 4: 1-12: 1; the stirring speed of the reaction kettle is controlled to be 200-400 rpm, and the temperature in the reaction kettle is controlled to be 10-25 ℃; the pipe outlet temperature of the external circulation cooler is controlled to be 8-20 ℃; and the mass ratio of the part of the butyl butyrate crude product solution obtained by the reaction, which is taken as a circulating reaction solution, entering the tube pass of the external circulating cooler to the part of the butyl butyrate crude product solution extracted to the crude product storage tank is controlled to be 100: 1-150: 1.

In the fourth step, the stirring speed of the crude product storage tank is controlled to be 200-400 rpm; the standing time of the solution is controlled to be 15-30 minutes; the inactivating agent is desalted water or dilute alkali solution.

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

(1) the invention realizes the continuous production of 100 tons/year butyl aldehyde by one-step method to produce butyl butyrate, is the first pilot scale production test for preparing butyl butyrate by using butyl aldehyde as a raw material domestically and internationally, and provides a set of scientific and complete industrialization parameters for the industrialized popularization of butyl butyrate.

(2) The method can realize the catalytic disproportionation of the butyraldehyde to produce the butyl butyrate at normal temperature and normal pressure, the conversion rate of the butyraldehyde serving as the raw material is more than or equal to 90 percent, and the reaction selectivity is more than or equal to 95 percent.

(3) The method has popularization, has guiding significance in the research field of producing corresponding aliphatic ester (or aromatic ester) by utilizing the aliphatic aldehyde (or aromatic aldehyde) one-step method, is beneficial to the development of green production technology of ester products, and further promotes the popularization and application of the ester products in the industries of paint, coating and the like.

Drawings

FIG. 1 is a schematic diagram of a synthesis system for producing butyl butyrate by a butyraldehyde one-step method.

The attached drawings are marked as follows: a 1-butyraldehyde feed tank; a 2-butyraldehyde feed pump; 3-catalyst dissolving tank; 4-a catalyst transfer pump; 5-a mixer; 6-external circulation cooler; 7-a reaction kettle; 8-a circulating pump; 9-a recycle line; 10-a production line; 11-a crude product storage tank; 12-a deactivator tank; 13-a valve; 14-a discharge pipe; 15-catalyst hopper; 16-view mirror; 17-a sewage draining outlet; 18-flow regulating valve.

Detailed Description

The invention is further described below with reference to the accompanying drawings.

For further understanding of the contents, features and effects of the present invention, the following embodiments are exemplified and described in detail with reference to the accompanying drawings.

The invention discloses a synthesis system for producing butyl butyrate by a butyraldehyde one-step method, which comprises a butyraldehyde raw material tank 1, a butyraldehyde feeding pump 2, a catalyst dissolving tank 3, a catalyst conveying pump 4, a mixer 5, an external circulation cooler 6, a reaction kettle 7, a circulating pump 8, a crude product storage tank 11 and an inactivating agent storage tank 12, as shown in figure 1.

The inlet of the butyraldehyde feeding pump 2 is connected with the butyraldehyde raw material tank 1 through a pipeline, the inlet of the catalyst delivery pump 4 is connected with the catalyst dissolving tank 3 through a pipeline, and the outlet of the butyraldehyde feeding pump 2 and the outlet of the catalyst delivery pump 4 are respectively connected with the inlet of the mixer 5 through pipelines. The outlet of the mixer 5 is connected with the tube pass inlet of the external circulation cooler 6 through a pipeline, the tube pass outlet of the external circulation cooler 6 is connected with the reaction kettle 7 through a pipeline, the discharge port at the bottom of the reaction kettle 7 is connected with the inlet of the circulating pump 8 through a pipeline, the outlet of the circulating pump 8 is connected with the tube pass inlet of the external circulation cooler 6 and the inlet of the crude product storage tank 11 through a circulating pipeline 9 and an extraction pipeline 10 respectively, and the circulating pipeline 9 and the extraction pipeline 10 are both provided with flow regulating valves 18. The crude product storage tank 11 is connected with an inactivating agent storage tank 12 through a pipeline, the inactivating agent storage tank 12 is positioned above the crude product storage tank 11, and a valve 13 is arranged on the pipeline connected between the inactivating agent storage tank 12 and the crude product storage tank 11. The side of the lower part of the crude product storage tank 11 is provided with a sight glass 16, the bottom of the crude product storage tank 11 is provided with a drain outlet 17 and a discharge pipe 14, the upper part of the discharge pipe 14 extends into the crude product storage tank 11 and is vertical to the inner wall of the bottom of the tank, the height of the upper port of the discharge pipe 14 is in the visual field of the sight glass 16, and the lower port of the discharge pipe 14 is connected with a separation system through a pipeline.

The butyraldehyde feeding pump 2 and the catalyst delivery pump 4 are pumps with flow metering functions, or the outlets of the butyraldehyde feeding pump 2 and the catalyst delivery pump 4 are provided with regulating valves for regulating flow. And cooling jackets are arranged on the outer walls of the mixer 5 and the reaction kettle 7. And the catalyst dissolving tank 3, the reaction kettle 7 and the crude product storage tank 11 are all provided with stirring devices. Butyraldehyde head tank 1, catalyst dissolving tank 3, reation kettle 7, crude storage tank 11 and inactivator storage tank 12 all are provided with the back pressure valve. The catalyst dissolving tank 3 is provided with a heating device, and a catalyst feeding hopper 15 is arranged at the top of the catalyst dissolving tank 3.

The raw materials of butyraldehyde and catalyst are respectively conveyed to a mixer 5 through a butyraldehyde feeding pump 2 and a catalyst conveying pump 4 for premixing, and the mixed raw materials enter an external circulation cooler 6 for cooling and then enter a reaction kettle 7 for full reaction. Reaction liquid extracted from the bottom of the reaction kettle 7 passes through a circulating pump 8, most of the reaction liquid enters an external circulation cooler 6 through a circulating pipeline 9, and the rest of the reaction liquid enters a crude product storage tank 11 through an extraction pipeline 10. Adding the inactivating agent into a crude product storage tank 11 to inactivate the catalyst, and feeding the obtained butyl butyrate crude product into a separation system for product purification. After the inactivator is accumulated to a certain liquid level at the bottom of the crude product storage tank 11, the inactivator is discharged through a sewage discharge port 17.

The synthesis method for producing the butyl butyrate by the butyraldehyde one-step method can complete the synthesis of the butyl butyrate by the butyraldehyde one-step method, and has the advantages of safe production process, high raw material conversion rate and good reaction selectivity. The specific implementation process is as follows:

the first step is as follows: performing nitrogen pressure maintaining on a butyraldehyde raw material tank 1, a catalyst dissolving tank 3, a reaction kettle 7, a crude product storage tank 11 and an inactivating agent storage tank 12 through a back pressure valve, wherein the pressure range is 10-20 kPa; chilled water is fed into cooling jackets of the mixer 5 and the reaction kettle 7, and the chilled water is introduced into the shell side of the external circulation cooler 6.

The second step is that: high temperature dissolution of catalyst

Adding the catalyst into a catalyst dissolving tank 3, heating the catalyst to 60-100 ℃ under stirring, and then preserving the temperature to dissolve the catalyst into a solution state.

Wherein the stirring speed of the catalyst dissolving tank 3 is controlled to be 200-400 rpm.

The catalyst is POP-Ru, a Porous Organic Polymer (POP) rich in hydroxyl is used as a substrate, and a complex structure of Ru is formed on the surface of the substrate, and the catalyst is applied for a patent with the patent application number of 201710967038. X.

The third step: reaction for preparing butyl butyrate by catalyzing and disproportionating butyraldehyde

Premixing raw material butyraldehyde and a catalyst in a certain ratio in a mixer 5, cooling the mixture in an external circulation cooler 6 in a tube pass after mixing, conveying the cooled solution to a reaction kettle 7 for full mixing reaction, and controlling the temperature in the reaction kettle 7 to be 10-25 ℃; the butyl butyrate crude product solution obtained by the reaction enters a circulating pump 8 from the bottom of a reaction kettle 7, most of the butyl butyrate crude product solution is taken as a circulating reaction solution and enters a tube pass of an external circulation cooler 6, the heat released by the reaction is removed, and the rest part of the butyl butyrate crude product solution is extracted into a crude product storage tank 11 to keep the material inlet and outlet balance of the reaction kettle 7.

The raw material butyraldehyde and the catalyst solution are respectively conveyed to a mixer 5 through a butyraldehyde feeding pump 2 and a catalyst conveying pump 4 according to the mass ratio of 4: 1-12: 1.

Wherein the stirring speed of the reaction kettle 7 is controlled to be 200-400 rpm.

Wherein the temperature of the tube side outlet of the external circulation cooler 6 is controlled to be 8-20 ℃.

Wherein the mass ratio of the part of the butyl butyrate crude product solution obtained by the reaction, which is taken as a circulating reaction liquid and enters the tube side of the external circulating cooler 6, to the part of the butyl butyrate crude product solution extracted to the crude product storage tank 11 is controlled to be 100: 1-150: 1.

The fourth step: deactivated catalyst

Adding an inactivating agent into the crude product storage tank 11 according to the mass ratio of the butyl butyrate crude product to the inactivating agent of 80: 1-100: 1 to inactivate the catalyst, mixing and stirring for 15-30 minutes, standing the solution until the solution is completely layered, allowing the butyl butyrate crude product on the upper layer to enter a separation system, and discharging the inactivating agent from a drain outlet 17 at the bottom of the crude product storage tank 11.

Wherein the stirring speed of the crude product storage tank 11 is controlled at 200-400 rpm.

Wherein the standing time of the solution is controlled to be 15-30 minutes.

Wherein the inactivating agent is desalted water or dilute alkali solution.

The components and the compositions of the butyl butyrate crude product in the crude product storage tank are detected by gas chromatography according to the method of GB 1886.286-2016 food safety national standard food additive butyl butyrate.

Butyraldehyde conversion X ═ butyraldehyde conversion/butyraldehyde starting amount;

the reaction selectivity S is the amount of butyraldehyde consumed to form butyl butyrate per the amount of butyraldehyde converted.

Example 1:

the first step is as follows: performing nitrogen pressure maintaining on a butyraldehyde raw material tank 1, a catalyst dissolving tank 3, a reaction kettle 7, a crude product storage tank 11 and an inactivating agent storage tank 12 through a backpressure valve, wherein the pressure is maintained at 10 kPa; chilled water is fed into cooling jackets of the mixer 5 and the reaction kettle 7, and the chilled water is introduced into the shell side of the external circulation cooler 6.

The second step is that: high temperature dissolution of catalyst

The catalyst is added into a catalyst dissolving tank 3, the stirring speed of the catalyst dissolving tank is controlled at 200rpm, the temperature of the catalyst is kept after the catalyst is heated to 60 ℃, and the catalyst is dissolved into a solution state.

The third step: reaction for preparing butyl butyrate by catalyzing and disproportionating butyraldehyde

Respectively conveying raw material butyraldehyde and a catalyst solution to a mixer 5 for premixing through a butyraldehyde feeding pump 2 and a catalyst conveying pump 4 according to a mass ratio of 4:1, cooling the mixed solution in a pipe pass of an external circulation cooler 6, controlling the temperature of an outlet of the pipe pass of the external circulation cooler 6 to be 20 ℃, conveying the cooled solution to a reaction kettle 7 for full mixing reaction, controlling the stirring speed of the reaction kettle 7 to be 200rpm, and controlling the temperature in the reaction kettle 7 to be 25 ℃; the butyl butyrate crude product solution obtained by the reaction enters a circulating pump 8 from the bottom of a reaction kettle 7, most of the butyl butyrate crude product solution is taken as a circulating reaction solution and enters a tube pass of an external circulation cooler 6, the heat released by the reaction is removed, and the rest part of the butyl butyrate crude product solution is extracted into a crude product storage tank 11 to keep the material inlet and outlet balance of the reaction kettle 7. Wherein the mass ratio of the part of the butyl butyrate crude product solution obtained by the reaction, which is taken as the circulating reaction liquid and enters the tube side of the external circulating cooler 6 to the part of the butyl butyrate crude product solution extracted to the crude product storage tank 11 is 100: 1.

The fourth step: deactivated catalyst

Adding demineralized water into the crude product storage tank 11 according to the mass ratio of the butyl butyrate crude product to the inactivator of 80:1 to inactivate the catalyst, controlling the stirring speed of the crude product storage tank 11 at 200rpm, mixing and stirring for 15 minutes, stopping, standing for 15 minutes to completely stratify the solution, allowing the butyl butyrate crude product on the upper layer to enter a separation system, and discharging the demineralized water from a drain outlet 17 at the bottom of the crude product storage tank 11.

The detection of the butyl butyrate crude product shows that when the mass flow of the raw material butyraldehyde and the catalyst is 4:1, the full-load production operation is achieved, the butyraldehyde conversion rate is 91.35%, and the reaction selectivity is 98.17%.

Example 2:

the first step is as follows: performing nitrogen pressure maintaining on a butyraldehyde raw material tank 1, a catalyst dissolving tank 3, a reaction kettle 7, a crude product storage tank 11 and an inactivating agent storage tank 12 through a backpressure valve, and maintaining the pressure at 15 kPa; chilled water is fed into cooling jackets of the mixer 5 and the reaction kettle 7, and the chilled water is introduced into the shell side of the external circulation cooler 6.

The second step is that: high temperature dissolution of catalyst

The catalyst is added into a catalyst dissolving tank 3, the stirring speed of the catalyst dissolving tank is controlled at 300rpm, the temperature of the catalyst is kept after the catalyst is heated to 80 ℃, and the catalyst is dissolved into a solution state.

The third step: reaction for preparing butyl butyrate by catalyzing and disproportionating butyraldehyde

Respectively conveying raw material butyraldehyde and a catalyst solution to a mixer 5 for premixing through a butyraldehyde feeding pump 2 and a catalyst conveying pump 4 according to a mass ratio of 8:1, cooling the mixed solution in a tube pass of an external circulation cooler 6, controlling the temperature of an outlet of the tube pass of the external circulation cooler 6 to be 15 ℃, conveying the cooled solution to a reaction kettle 7 for full mixing reaction, controlling the stirring speed of the reaction kettle 7 to be 400rpm, and controlling the temperature in the reaction kettle 7 to be 18 ℃; the butyl butyrate crude product solution obtained by the reaction enters a circulating pump 8 from the bottom of a reaction kettle 7, most of the butyl butyrate crude product solution is taken as a circulating reaction solution and enters a tube pass of an external circulation cooler 6, the heat released by the reaction is removed, and the rest part of the butyl butyrate crude product solution is extracted into a crude product storage tank 11 to keep the material inlet and outlet balance of the reaction kettle 7. Wherein the mass ratio of the part of the butyl butyrate crude product solution obtained by the reaction, which is taken as the circulating reaction liquid and enters the tube side of the external circulating cooler 6 to the part of the butyl butyrate crude product solution extracted to the crude product storage tank 11 is 130: 1.

The fourth step: deactivated catalyst

Adding 5 wt% of NaOH solution into a crude product storage tank 11 according to the mass ratio of the butyl butyrate crude product to the inactivator of 90:1 to inactivate the catalyst, controlling the stirring speed of the crude product storage tank 11 at 400rpm, mixing and stirring for 20 minutes, stopping, standing for 30 minutes to completely stratify the solution, allowing the butyl butyrate crude product on the upper layer to enter a separation system, and discharging the NaOH solution from a drain outlet 17 at the bottom of the crude product storage tank 11.

The detection of the butyl butyrate crude product shows that when the mass flow of the raw material butyraldehyde and the catalyst is 8:1, the full-load production operation is achieved, the butyraldehyde conversion rate is 92.03%, and the reaction selectivity is 98.57%.

Example 3:

the first step is as follows: performing nitrogen pressure maintaining on a butyraldehyde raw material tank 1, a catalyst dissolving tank 3, a reaction kettle 7, a crude product storage tank 11 and an inactivating agent storage tank 12 through a backpressure valve, wherein the pressure is maintained at 20 kPa; chilled water is fed into cooling jackets of the mixer 5 and the reaction kettle 7, and the chilled water is introduced into the shell side of the external circulation cooler 6.

The second step is that: high temperature dissolution of catalyst

The catalyst is added into a catalyst dissolving tank 3, the stirring speed of the catalyst dissolving tank is controlled at 400rpm, the temperature of the catalyst is kept after the catalyst is heated to 100 ℃, and the catalyst is dissolved into a solution state.

The third step: reaction for preparing butyl butyrate by catalyzing and disproportionating butyraldehyde

Respectively conveying raw material butyraldehyde and a catalyst solution to a mixer 5 for premixing through a butyraldehyde feeding pump 2 and a catalyst conveying pump 4 according to a mass ratio of 12:1, cooling the mixed solution in a pipe pass of an external circulation cooler 6, controlling the temperature of an outlet of the pipe pass of the external circulation cooler 6 to be 8 ℃, conveying the cooled solution to a reaction kettle 7 for full mixing reaction, controlling the stirring speed of the reaction kettle 7 to be 300rpm, and controlling the temperature in the reaction kettle 7 to be 10 ℃; the butyl butyrate crude product solution obtained by the reaction enters a circulating pump 8 from the bottom of a reaction kettle 7, most of the butyl butyrate crude product solution is taken as a circulating reaction solution and enters a tube pass of an external circulation cooler 6, the heat released by the reaction is removed, and the rest part of the butyl butyrate crude product solution is extracted into a crude product storage tank 11 to keep the material inlet and outlet balance of the reaction kettle 7. Wherein the mass ratio of the part of the butyl butyrate crude product solution obtained by the reaction, which is taken as the circulating reaction liquid and enters the tube side of the external circulating cooler 6 to the part of the butyl butyrate crude product solution extracted to the crude product storage tank 11 is 150: 1.

The fourth step: deactivated catalyst

Adding 3 wt% of KOH solution into a crude product storage tank 11 according to the mass ratio of the butyl butyrate crude product to the inactivator of 100:1 to inactivate the catalyst, controlling the stirring speed of the crude product storage tank 11 at 320rpm, mixing and stirring for 30 minutes, stopping, standing for 20 minutes to completely stratify the solution, allowing the butyl butyrate crude product on the upper layer to enter a separation system, and discharging the KOH solution from a drain outlet 17 at the bottom of the crude product storage tank 11.

The detection of the butyl butyrate crude product shows that when the mass flow of the raw material butyraldehyde and the catalyst is 12:1, the full-load production operation is achieved, the butyraldehyde conversion rate is 91.50%, and the reaction selectivity is 98.22%.

Example 4:

the first step is as follows: performing nitrogen pressure maintaining on a butyraldehyde raw material tank 1, a catalyst dissolving tank 3, a reaction kettle 7, a crude product storage tank 11 and an inactivating agent storage tank 12 through a backpressure valve, and maintaining the pressure at 15 kPa; chilled water is fed into cooling jackets of the mixer 5 and the reaction kettle 7, and the chilled water is introduced into the shell side of the external circulation cooler 6.

The second step is that: high temperature dissolution of catalyst

The catalyst is added into a catalyst dissolving tank 3, the stirring speed of the catalyst dissolving tank is controlled at 320rpm, the temperature of the catalyst is kept after the catalyst is heated to 80 ℃, and the catalyst is dissolved into a solution state.

The third step: reaction for preparing butyl butyrate by catalyzing and disproportionating butyraldehyde

Respectively conveying raw material butyraldehyde and a catalyst solution to a mixer 5 for premixing through a butyraldehyde feeding pump 2 and a catalyst conveying pump 4 according to the mass ratio of 12:1, cooling the mixed solution in a pipe pass of an external circulation cooler 6, controlling the temperature of an outlet of the pipe pass of the external circulation cooler 6 to be 12 ℃, conveying the cooled solution to a reaction kettle 7 for full mixing reaction, controlling the stirring speed of the reaction kettle 7 to be 320rpm, and controlling the temperature in the reaction kettle 7 to be 16 ℃; the butyl butyrate crude product solution obtained by the reaction enters a circulating pump 8 from the bottom of a reaction kettle 7, most of the butyl butyrate crude product solution is taken as a circulating reaction solution and enters a tube pass of an external circulation cooler 6, the heat released by the reaction is removed, and the rest part of the butyl butyrate crude product solution is extracted into a crude product storage tank 11 to keep the material inlet and outlet balance of the reaction kettle 7. Wherein the mass ratio of the part of the butyl butyrate crude product solution obtained by the reaction, which is taken as the circulating reaction liquid and enters the tube side of the external circulating cooler 6 to the part of the butyl butyrate crude product solution extracted to the crude product storage tank 11 is 130: 1.

The fourth step: deactivated catalyst

Adding demineralized water into the crude product storage tank 11 according to the mass ratio of the butyl butyrate crude product to the inactivator of 100:1 to inactivate the catalyst, controlling the stirring speed of the crude product storage tank 11 at 350rpm, mixing and stirring for 25 minutes, stopping, standing the solution for 18 minutes to completely stratify the solution, allowing the butyl butyrate crude product on the upper layer to enter a separation system, and discharging the demineralized water from a drain outlet 17 at the bottom of the crude product storage tank 11.

The detection of the butyl butyrate crude product shows that when the mass flow of the raw material butyraldehyde and the catalyst is 12:1, the full-load production operation is achieved, the butyraldehyde conversion rate is 91.83%, and the reaction selectivity is 98.62%.

Example 5:

the first step is as follows: performing nitrogen pressure maintaining on a butyraldehyde raw material tank 1, a catalyst dissolving tank 3, a reaction kettle 7, a crude product storage tank 11 and an inactivating agent storage tank 12 through a backpressure valve, and maintaining the pressure at 15 kPa; chilled water is fed into cooling jackets of the mixer 5 and the reaction kettle 7, and the chilled water is introduced into the shell side of the external circulation cooler 6.

The second step is that: high temperature dissolution of catalyst

The catalyst is added into a catalyst dissolving tank 3, the stirring speed of the catalyst dissolving tank is controlled at 360rpm, the temperature of the catalyst is kept after the catalyst is heated to 80 ℃, and the catalyst is dissolved into a solution state.

The third step: reaction for preparing butyl butyrate by catalyzing and disproportionating butyraldehyde

Respectively conveying raw material butyraldehyde and a catalyst solution to a mixer 5 for premixing through a butyraldehyde feeding pump 2 and a catalyst conveying pump 4 according to a mass ratio of 10:1, cooling the mixed solution in a pipe pass of an external circulation cooler 6, controlling the temperature of an outlet of the pipe pass of the external circulation cooler 6 to be 8 ℃, conveying the cooled solution to a reaction kettle 7 for full mixing reaction, controlling the stirring speed of the reaction kettle 7 to be 360rpm, and controlling the temperature in the reaction kettle 7 to be 12 ℃; the butyl butyrate crude product solution obtained by the reaction enters a circulating pump 8 from the bottom of a reaction kettle 7, most of the butyl butyrate crude product solution is taken as a circulating reaction solution and enters a tube pass of an external circulation cooler 6, the heat released by the reaction is removed, and the rest part of the butyl butyrate crude product solution is extracted into a crude product storage tank 11 to keep the material inlet and outlet balance of the reaction kettle 7. Wherein the mass ratio of the part of the butyl butyrate crude product solution obtained by the reaction, which is taken as the circulating reaction liquid and enters the tube side of the external circulating cooler 6 to the part of the butyl butyrate crude product solution extracted to the crude product storage tank 11 is 150: 1.

The fourth step: deactivated catalyst

Adding demineralized water into the crude product storage tank 11 according to the mass ratio of the butyl butyrate crude product to the inactivating agent of 90:1 to inactivate the catalyst, controlling the stirring speed of the crude product storage tank 11 at 320rpm, mixing and stirring for 20 minutes, stopping, standing the solution for 20 minutes to completely stratify the solution, allowing the butyl butyrate crude product on the upper layer to enter a separation system, and discharging the demineralized water from a drain outlet 17 at the bottom of the crude product storage tank 11.

The detection of the butyl butyrate crude product shows that when the mass flow of the raw material butyraldehyde and the catalyst is 10:1, the full-load production operation is achieved, the butyraldehyde conversion rate is 92.03%, and the reaction selectivity is 98.59%.

While the present invention has been described in terms of its functions and operations with reference to the accompanying drawings, it is to be understood that the invention is not limited to the precise functions and operations described above, and that the above-described embodiments are illustrative rather than restrictive, and that various changes and modifications may be effected therein by one skilled in the art without departing from the scope or spirit of the invention as defined by the appended claims.