A synthesis system and method for producing butyl butyrate from butyraldehyde in one step

Abstract

The invention discloses a synthesis system for producing butyl butyrate by a one-step butyraldehyde method. The system comprises the following steps: a butyraldehyde feed pump is connected to a butyraldehyde raw material tank, a catalyst delivery pump is connected to a catalyst dissolution tank, the butyraldehyde feed pump and the catalyst delivery pump are connected to a mixer inlet, a mixer outlet is connected to an external circulation cooler pipe inlet, the pipe outlet is connected to a reactor, a bottom of the reactor is connected to a circulation pump, a circulation pump outlet is connected to an external circulation cooler pipe inlet and a crude product storage tank inlet, and the crude product storage tank is connected to an inactivator storage tank and a separation system. The system comprises the following steps: a raw material butyraldehyde and a catalyst are premixed, enter an external circulation cooler for cooling, are delivered to a reactor for reaction, most of a solution enters the external circulation cooler pipe as a circulating reaction liquid, the remaining part is extracted to a crude product storage tank, an inactivator is added to the crude product storage tank to deactivate the catalyst, the crude butyl butyrate enters the separation system, and the inactivator is discharged from a sewage outlet of the crude product storage tank.

Description

Technical Field

[0001] The invention relates to the technical field of chemical production, and more specifically to a synthesis system and method for producing butyl butyrate by a one-step process of butyraldehyde. Background Art

[0002] Butyl butyrate, also known as n-butyl butyrate, is a colorless transparent liquid with a fruity aroma, widely used in food additives and organic solvents. In the field of coatings and paints, butyl butyrate has mild solubility and excellent anti-whitening performance; in the field of coatings for plastic products, it can better solve the "burned bottom" phenomenon; in wood coatings, it has good color development for pigments; in the formulation of metallic glitter paint, it has good protection for metallic pigments. According to information feedback from the paint industry, the potential demand for butyl butyrate in China is about 500,000 tons / year.

[0003] The traditional butyl butyrate production process is to react n-butyric acid and n-butanol to produce an ester under the catalysis of concentrated sulfuric acid. This process has the disadvantages of long production route, many side reactions, dark product color, complex post-processing process, serious equipment corrosion, and waste acid pollution. In addition, butyric acid and butanol, the raw materials of this process, are obtained from butyraldehyde in industry through oxidation and hydrogenation processes respectively. The synthesis of butyl butyrate using the traditional production process requires the removal of water molecules, resulting in a waste of resources.

[0004] Wang Haijing (Wang Haijing, Duan Qiwei, One-step synthesis of butyl butyrate from n-butanol, Fine Petrochemicals, 2013, 1, 20-22) reported that n-butanol was used to catalyze the preparation of butyl butyrate at 260±5℃ and ≥0.4MPa, with a n-butanol conversion rate of 64% and a butyl butyrate selectivity of 73.8%. Pan Weixiong (Pan Weixiong, One-step synthesis of butyl butyrate from n-butanol or n-butyraldehyde, Petrochemicals, 1993, 22(2), 111-114) reported that n-butyraldehyde was catalyzed at 255℃ and 0.7MPa, with a conversion rate of about 60% and a very low butyl butyrate selectivity. Other research reports on the preparation of butyl butyrate from butyraldehyde all have problems with low conversion rate and selectivity, and are basically in the laboratory research stage, with no pilot or industrial application cases.

[0005] Tianjin Bohai Yongli Chemical Co., Ltd. (hereinafter referred to as Yongli Chemical) and the Dalian Institute of Chemical Physics of the Chinese Academy of Sciences have jointly developed a production process for preparing butyl butyrate from butyraldehyde in one step. This process uses butyraldehyde as the raw material and catalytically disproportionates under mild conditions to produce butyl butyrate. The reaction route is simple, the raw material cost and energy consumption are low, there is no equipment corrosion and environmental pollution, and the atom economy is high. The small-scale test has completed the screening of high-efficiency catalysts, the optimization of production routes and the purification plan of products. In order to promote the transformation of this scientific and technological achievement to industrialization as soon as possible, it is necessary to carry out pilot tests, further optimize the production process, and obtain a set of scientific and complete industrial parameters for preparing butyl butyrate from butyraldehyde in one step. Summary of the invention

[0006] The purpose of the present invention is to overcome the deficiencies in the prior art and provide a synthesis system and method for producing butyl butyrate by a one-step butyraldehyde method. The process for preparing butyl butyrate by a one-step butyraldehyde method is adopted, and the raw material butyraldehyde is subjected to a catalytic disproportionation reaction in a synthesis system. After the reaction is completed, a deactivator is added to the reaction solution to deactivate the catalyst, so as to obtain a crude butyl butyrate product.

[0007] The purpose of the present invention can be achieved through the following technical solutions.

[0008] The invention discloses a one-step butyraldehyde synthesis system for producing butyl butyrate, comprising a butyraldehyde raw material tank, a butyraldehyde feed pump, a catalyst dissolution tank, a catalyst delivery pump, a mixer, an external circulation cooler, a reactor, a circulation pump, a crude product storage tank, and an inactivator storage tank;

[0009] The inlet of the butyraldehyde feed pump is connected to the butyraldehyde raw material tank through a pipeline, the inlet of the catalyst delivery pump is connected to the catalyst dissolution tank through a pipeline, the outlet of the butyraldehyde feed pump and the outlet of the catalyst delivery pump are respectively connected to the inlet of the mixer through pipelines, the outlet of the mixer is connected to the inlet of the external circulation cooler pipe side through a pipeline, the outlet of the external circulation cooler pipe side is connected to the reactor through a pipeline, the bottom discharge port of the reactor is connected to the inlet of the circulation pump through a pipeline, the outlet of the circulation pump is respectively connected to the inlet of the external circulation cooler pipe side and the inlet of the crude product storage tank through a circulation pipeline and a production pipeline, the crude product storage tank is connected to the deactivator storage tank through a pipeline, a discharge pipe is provided at the bottom of the crude product storage tank, and the discharge pipe is connected to the separation system through a pipeline.

[0010] The butyraldehyde feed pump and the catalyst delivery pump are both pumps with flow metering function, or the outlets of the butyraldehyde feed pump and the catalyst delivery pump are both provided with regulating valves for regulating flow.

[0011] The outer walls of the mixer and the reactor are both provided with cooling jackets; the catalyst dissolution tank, the reactor and the crude product storage tank are all provided with stirring devices.

[0012] The butyraldehyde raw material tank, catalyst dissolution tank, reactor, crude product storage tank and deactivator storage tank are all provided with back pressure valves; the catalyst dissolution tank has a heating device, and a catalyst feeding hopper is provided on the top of the catalyst dissolution tank.

[0013] The circulation pipeline and the extraction pipeline are both provided with flow regulating valves, and the pipeline connecting the inactivator storage tank and the crude product storage tank is provided with a valve.

[0014] The inactivator storage tank is located above the crude product storage tank, a sewage outlet is provided at the bottom of the crude product storage tank, a sight glass is provided on the lower side of the crude product storage tank, the upper part of the discharge pipe extends into the crude product storage tank and is perpendicular to the inner wall of the tank bottom, and the height of the upper port of the discharge pipe is within the field of view of the sight glass.

[0015] The purpose of the present invention can also be achieved through the following technical solutions.

[0016] The synthetic method for producing butyl butyrate from butyraldehyde in one step of the present invention comprises the following steps:

[0017] Step 1: The butyraldehyde raw material tank, catalyst dissolution tank, reactor, crude product storage tank and deactivator storage tank are pressurized with nitrogen through a back pressure valve, and the pressure range is 10-20 kPa; chilled water is used in the cooling jackets of the mixer and reactor, and chilled water is introduced into the shell side of the external circulation cooler;

[0018] Step 2: Dissolve the catalyst at high temperature

[0019] The catalyst is added into the catalyst dissolving tank, and the catalyst is heated to 60-100°C and then kept warm under stirring to dissolve the catalyst into a solution state;

[0020] Step 3: Butyraldehyde catalytic disproportionation to prepare butyl butyrate

[0021] The raw material butyraldehyde and the catalyst of a certain ratio are premixed in a mixer, and then enter the external circulation cooler tube for cooling after mixing, and then transported to the reactor for sufficient reaction. Most of the crude butyl butyrate solution obtained by the reaction enters the external circulation cooler tube as a circulating reaction liquid, and the heat released by the reaction is removed. The remaining part is extracted into the crude product storage tank to maintain the balance of the inflow and outflow of the reactor materials;

[0022] Step 4: Deactivate the catalyst

[0023] Add the deactivator to the crude product storage tank at a mass ratio of 80:1 to 100:1 of crude butyl butyrate to the deactivator to deactivate the catalyst. After mixing and stirring for 15 to 30 minutes, let the solution stand until the solution is completely separated. The upper layer of crude butyl butyrate enters the separation system, and the deactivator is discharged from the sewage outlet at the bottom of the crude product storage tank.

[0024] In the second step, the stirring rate of the catalyst dissolving tank is controlled at 200-400 rpm; the catalyst is POP-Ru, which has a porous organic polymer rich in hydroxyl groups as a substrate and forms a Ru complex structure on its surface.

[0025] In the third step, the raw material butyraldehyde and the catalyst solution are respectively delivered to the mixer by a butyraldehyde feed pump and a catalyst delivery pump in a mass ratio of 4:1 to 12:1; the stirring rate of the reactor is controlled at 200 to 400 rpm, and the temperature in the reactor is controlled at 10 to 25°C; the outlet temperature of the external circulation cooler tube side is controlled at 8 to 20°C; the mass ratio of the crude butyl butyrate solution obtained by the reaction that enters the external circulation cooler tube side as the circulating reaction liquid and the part extracted to the crude product storage tank is controlled at 100:1 to 150:1.

[0026] In the fourth step, the stirring rate of the crude product storage tank is controlled at 200-400 rpm; the solution standing time is controlled at 15-30 minutes; and the inactivator is deionized water or a dilute alkaline solution.

[0027] Compared with the prior art, the technical solution of the present invention has the following beneficial effects:

[0028] (1) The present invention realizes the continuous production of 100 tons / year of butyraldehyde in one step to produce butyl butyrate. It is the first pilot-scale production test of butyl butyrate prepared with butyraldehyde as raw material in China and abroad, and provides a set of scientific and complete industrialization parameters for the industrialization promotion of butyl butyrate.

[0029] (2) The present invention can realize the catalytic disproportionation of butyraldehyde to produce butyl butyrate at normal temperature and pressure, with the raw material butyraldehyde conversion rate ≥90% and the reaction selectivity ≥95%. Compared with the existing research results and butyl butyrate production devices, the present invention has the advantages of simple route, mild reaction conditions, high raw material conversion rate and reaction selectivity, good atom economy and green environmental protection.

[0030] (3) The present invention is of general applicability and has guiding significance for the research field of producing corresponding fatty esters (or aromatic esters) by one-step method using fatty aldehydes (or aromatic aldehydes), which is beneficial to the development of green production technology for ester products, and further promotes the popularization and application of ester products in industries such as paints and coatings. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 The present invention is a schematic diagram of a synthesis system for producing butyl butyrate from butyraldehyde in one step.

[0032] The attached figure is marked with: 1-butyraldehyde raw material tank; 2-butyraldehyde feed pump; 3-catalyst dissolution tank; 4-catalyst delivery pump; 5-mixer; 6-external circulation cooler; 7-reactor; 8-circulation pump; 9-circulation pipeline; 10-production pipeline; 11-crude product storage tank; 12-inactivator storage tank; 13-valve; 14-discharge pipe; 15-catalyst hopper; 16-sight glass; 17-drain outlet; 18-flow regulating valve. DETAILED DESCRIPTION

[0033] The present invention will be further described below in conjunction with the accompanying drawings.

[0034] In order to further understand the content, features and effects of the present invention, the following embodiments are given as examples and described in detail with reference to the accompanying drawings.

[0035] The synthesis system of producing butyl butyrate by butyraldehyde one-step method of the present invention is as follows: Figure 1 As shown, it includes a butyraldehyde raw material tank 1, a butyraldehyde feed pump 2, a catalyst dissolution tank 3, a catalyst delivery pump 4, a mixer 5, an external circulation cooler 6, a reactor 7, a circulation pump 8, a crude product storage tank 11, and an inactivator storage tank 12.

[0036] The inlet of the butyraldehyde feed pump 2 is connected to the butyraldehyde raw material tank 1 through a pipeline, the inlet of the catalyst delivery pump 4 is connected to the catalyst dissolution tank 3 through a pipeline, and the outlet of the butyraldehyde feed pump 2 and the outlet of the catalyst delivery pump 4 are respectively connected to the inlet of the mixer 5 through a pipeline. The outlet of the mixer 5 is connected to the inlet of the outer circulation cooler 6 pipe side through a pipeline, and the outlet of the outer circulation cooler 6 pipe side is connected to the reactor 7 through a pipeline, and the bottom discharge port of the reactor 7 is connected to the inlet of the circulation pump 8 through a pipeline, and the outlet of the circulation pump 8 is respectively connected to the inlet of the outer circulation cooler 6 pipe side and the inlet of the crude product storage tank 11 through a circulation pipeline 9 and a production pipeline 10, and a flow regulating valve 18 is provided on the circulation pipeline 9 and the production pipeline 10. The crude product storage tank 11 is connected to the inactivator storage tank 12 through a pipeline, and the inactivator storage tank 12 is located above the crude product storage tank 11, and a valve 13 is provided on the pipeline connected between the inactivator storage tank 12 and the crude product storage tank 11. A sight glass 16 is arranged on the lower side of the crude product storage tank 11, and a sewage outlet 17 and a discharge pipe 14 are arranged on the bottom 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 perpendicular to the inner wall of the tank bottom. The height of the upper end of the discharge pipe 14 is within the field of view of the sight glass 16, and the lower end of the discharge pipe 14 is connected to the separation system through a pipeline.

[0037] Wherein, the butyraldehyde feed pump 2 and the catalyst delivery pump 4 are both pumps with flow metering function, or the outlets of the butyraldehyde feed pump 2 and the catalyst delivery pump 4 are both provided with regulating valves for adjusting the flow. The outer walls of the mixer 5 and the reactor 7 are both provided with cooling jackets. The catalyst dissolution tank 3, the reactor 7 and the crude product storage tank 11 are all provided with stirring devices. The butyraldehyde raw material tank 1, the catalyst dissolution tank 3, the reactor 7, the crude product storage tank 11 and the deactivator storage tank 12 are all provided with back pressure valves. The catalyst dissolution tank 3 has a heating device, and a catalyst feeding hopper 15 is provided at the top of the catalyst dissolution tank 3.

[0038] The raw material butyraldehyde and the catalyst are respectively delivered to the mixer 5 for premixing by the butyraldehyde feed pump 2 and the catalyst delivery pump 4, and then enter the external circulation cooler 6 for cooling after mixing, and then enter the reactor 7 for full reaction. The reaction liquid extracted from the bottom of the reactor 7 passes through the circulation pump 8, and most of it enters the external circulation cooler 6 through the circulation pipeline 9, and the remaining part enters the crude product storage tank 11 through the extraction pipeline 10. The deactivator is added to the crude product storage tank 11 to deactivate the catalyst, and the resulting butyl butyrate crude product enters the separation system for product purification. After the deactivator accumulates to a certain liquid level at the bottom of the crude product storage tank 11, the deactivator is discharged through the sewage outlet 17.

[0039] The method for producing butyl butyrate from butyraldehyde in one step can complete the synthesis of butyl butyrate from butyraldehyde in one step, and the production process is safe, the raw material conversion rate is high, and the reaction selectivity is good. The specific implementation process is as follows:

[0040] The first step: the butyraldehyde raw material tank 1, the catalyst dissolution tank 3, the reactor 7, the crude product storage tank 11 and the deactivator storage tank 12 are pressurized with nitrogen through a back pressure valve, and the pressure range is 10 to 20 kPa; the cooling jackets of the mixer 5 and the reactor 7 are put into chilled water, and the shell side of the external circulation cooler 6 is introduced with chilled water.

[0041] Step 2: Dissolve the catalyst at high temperature

[0042] The catalyst is added into the catalyst dissolving tank 3, and the catalyst is heated to 60-100° C. and then kept warm under stirring to dissolve the catalyst into a solution state.

[0043] Wherein, the stirring rate of the catalyst dissolution tank 3 is controlled at 200-400 rpm.

[0044] Among them, the catalyst is POP-Ru, which takes a hydroxyl-rich porous organic polymer (POP) as a substrate and forms a Ru complex structure on its surface. The catalyst has been patented, and the patent application number is 201710967038.X.

[0045] Step 3: Butyraldehyde catalytic disproportionation to prepare butyl butyrate

[0046] The raw material butyraldehyde and the catalyst in a certain ratio are premixed in the mixer 5, and then enter the external circulation cooler 6 for cooling after mixing. The cooled solution is transported to the reactor 7 for sufficient mixing reaction, and the temperature in the reactor 7 is controlled at 10-25°C; the crude butyl butyrate solution obtained by the reaction enters the circulation pump 8 from the bottom of the reactor 7, and most of it enters the external circulation cooler 6 as a circulating reaction liquid to remove the heat released by the reaction, and the remaining part is extracted into the crude product storage tank 11 to keep the material in and out of the reactor 7 balanced.

[0047] The raw material butyraldehyde and the catalyst solution are respectively delivered to the mixer 5 through the butyraldehyde feed pump 2 and the catalyst delivery pump 4 at a mass ratio of 4:1 to 12:1.

[0048] Wherein, the stirring rate of the reactor 7 is controlled at 200-400 rpm.

[0049] Wherein, the outlet temperature of the tube side of the external circulation cooler 6 is controlled at 8-20°C.

[0050] The mass ratio of the crude butyl butyrate solution obtained by the reaction that enters the outer circulation cooler 6 as the circulating reaction liquid and the crude product storage tank 11 is controlled at 100:1 to 150:1.

[0051] Step 4: Deactivate the catalyst

[0052] The deactivator is added to the crude product storage tank 11 at a mass ratio of 80:1 to 100:1 of crude butyl butyrate to deactivator to deactivate the catalyst. After mixing and stirring for 15 to 30 minutes, the solution is allowed to stand until the solution is completely stratified, and the upper layer of crude butyl butyrate enters the separation system, and the deactivator is discharged from the sewage outlet 17 at the bottom of the crude product storage tank 11.

[0053] Wherein, the stirring rate of the crude product storage tank 11 is controlled at 200-400 rpm.

[0054] Wherein, the solution is allowed to stand for 15 to 30 minutes.

[0055] Wherein, the inactivator is deionized water or a dilute alkaline solution.

[0056] The components and composition of crude butyl butyrate in the crude product storage tank were tested by gas chromatography according to the method of "GB 1886.286-2016 National Food Safety Standard Food Additive Butyrate".

[0057] Butyraldehyde conversion rate X = butyraldehyde conversion amount / butyraldehyde initial amount;

[0058] Reaction selectivity S=amount of butyraldehyde consumed to produce butyl butyrate / conversion amount of butyraldehyde.

[0059] Embodiment 1:

[0060] The first step: the butyraldehyde raw material tank 1, the catalyst dissolution tank 3, the reactor 7, the crude product storage tank 11 and the deactivator storage tank 12 are pressurized with nitrogen through a back pressure valve, and the pressure is maintained at 10kPa; chilled water is used in the cooling jackets of the mixer 5 and the reactor 7, and chilled water is introduced into the shell side of the external circulation cooler 6.

[0061] Step 2: Dissolve the catalyst at high temperature

[0062] The catalyst is added into the catalyst dissolving tank 3, the stirring rate of the catalyst dissolving tank is controlled at 200 rpm, the catalyst is heated to 60° C. and then kept warm, and the catalyst is dissolved into a solution state.

[0063] Step 3: Butyraldehyde catalytic disproportionation to prepare butyl butyrate

[0064] The raw material butyraldehyde and the catalyst solution are respectively delivered to the mixer 5 by the butyraldehyde feed pump 2 and the catalyst delivery pump 4 in a mass ratio of 4:1 for premixing, and then enter the outer circulation cooler 6 tube pass for cooling after mixing, and the outlet temperature of the outer circulation cooler 6 tube pass is controlled at 20°C. The cooled solution is delivered to the reactor 7 for full mixing reaction, and the stirring rate of the reactor 7 is controlled at 200rpm, and the temperature in the reactor 7 is controlled to be 25°C; the crude butyl butyrate solution obtained by the reaction enters the circulation pump 8 from the bottom of the reactor 7, and most of it enters the outer circulation cooler 6 tube pass as a circulating reaction liquid, and the heat released by the reaction is removed, and the remaining part is extracted into the crude product storage tank 11, and the material in and out of the reactor 7 is kept balanced. Among them, the mass ratio of the part of the crude butyl butyrate solution obtained by the reaction that enters the outer circulation cooler 6 tube pass as a circulating reaction liquid to the part extracted into the crude product storage tank 11 is 100:1.

[0065] Step 4: Deactivate the catalyst

[0066] Deionized water is added to the crude product storage tank 11 at a mass ratio of 80:1 between the crude butyl butyrate and the deactivator to deactivate the catalyst. The stirring rate of the crude product storage tank 11 is controlled at 200 rpm. After 15 minutes of mixing and stirring, the mixture is stopped and allowed to stand for 15 minutes to allow the solution to completely separate. The upper layer of crude butyl butyrate enters the separation system, and the deionized water is discharged from the drain outlet 17 at the bottom of the crude product storage tank 11.

[0067] The detection of crude butyl butyrate showed that when the feed mass flow rate of raw material butyraldehyde to catalyst was 4:1, full load production operation was achieved, the butyraldehyde conversion rate was 91.35%, and the reaction selectivity was 98.17%.

[0068] Embodiment 2:

[0069] The first step: the butyraldehyde raw material tank 1, the catalyst dissolution tank 3, the reactor 7, the crude product storage tank 11 and the deactivator storage tank 12 are pressurized with nitrogen through a back pressure valve, and the pressure is maintained at 15kPa; chilled water is used in the cooling jackets of the mixer 5 and the reactor 7, and chilled water is introduced into the shell side of the external circulation cooler 6.

[0070] Step 2: Dissolve the catalyst at high temperature

[0071] The catalyst is added into the catalyst dissolving tank 3, the stirring rate of the catalyst dissolving tank is controlled at 300 rpm, the catalyst is heated to 80° C. and then kept warm, and the catalyst is dissolved into a solution state.

[0072] Step 3: Butyraldehyde catalytic disproportionation to prepare butyl butyrate

[0073] The raw material butyraldehyde and the catalyst solution are respectively delivered to the mixer 5 by the butyraldehyde feed pump 2 and the catalyst delivery pump 4 in a mass ratio of 8:1 for premixing, and then enter the outer circulation cooler 6 tube pass for cooling after mixing, and the outlet temperature of the outer circulation cooler 6 tube pass is controlled at 15°C. The cooled solution is delivered to the reactor 7 for full mixing reaction, and the stirring rate of the reactor 7 is controlled at 400rpm, and the temperature in the reactor 7 is controlled to be 18°C; the crude butyl butyrate solution obtained by the reaction enters the circulation pump 8 from the bottom of the reactor 7, and most of it enters the outer circulation cooler 6 tube pass as a circulating reaction liquid, and the heat released by the reaction is removed, and the remaining part is extracted into the crude product storage tank 11, and the material in and out of the reactor 7 is kept balanced. Among them, the mass ratio of the part of the crude butyl butyrate solution obtained by the reaction that enters the outer circulation cooler 6 tube pass as a circulating reaction liquid to the part extracted into the crude product storage tank 11 is 130:1.

[0074] Step 4: Deactivate the catalyst

[0075] 5 wt% NaOH solution was added to the crude product storage tank 11 at a mass ratio of 90:1 between the crude butyl butyrate and the deactivator to deactivate the catalyst. The stirring rate of the crude product storage tank 11 was controlled at 400 rpm. The mixing and stirring was stopped after 20 minutes. The solution was allowed to stand for 30 minutes to allow the solution to be completely stratified. The upper layer of crude butyl butyrate entered the separation system, and the NaOH solution was discharged from the sewage outlet 17 at the bottom of the crude product storage tank 11.

[0076] The detection of crude butyl butyrate showed that when the feed mass flow rate of raw material butyraldehyde to catalyst was 8:1, full load production operation was achieved, the butyraldehyde conversion rate was 92.03%, and the reaction selectivity was 98.57%.

[0077] Embodiment 3:

[0078] The first step: the butyraldehyde raw material tank 1, the catalyst dissolution tank 3, the reactor 7, the crude product storage tank 11 and the deactivator storage tank 12 are pressurized with nitrogen through a back pressure valve, and the pressure is maintained at 20kPa; chilled water is used in the cooling jackets of the mixer 5 and the reactor 7, and chilled water is introduced into the shell side of the external circulation cooler 6.

[0079] Step 2: Dissolve the catalyst at high temperature

[0080] The catalyst is added into the catalyst dissolving tank 3, the stirring rate of the catalyst dissolving tank is controlled at 400 rpm, the catalyst is heated to 100° C. and then kept warm, and the catalyst is dissolved into a solution state.

[0081] Step 3: Butyraldehyde catalytic disproportionation to prepare butyl butyrate

[0082] The raw material butyraldehyde and the catalyst solution are respectively delivered to the mixer 5 by the butyraldehyde feed pump 2 and the catalyst delivery pump 4 in a mass ratio of 12:1 for premixing, and then enter the outer circulation cooler 6 tube pass for cooling after mixing, and the outlet temperature of the outer circulation cooler 6 tube pass is controlled at 8°C. The cooled solution is delivered to the reactor 7 for full mixing reaction, and the stirring rate of the reactor 7 is controlled at 300rpm, and the temperature in the reactor 7 is controlled to be 10°C; the crude butyl butyrate solution obtained by the reaction enters the circulation pump 8 from the bottom of the reactor 7, and most of it enters the outer circulation cooler 6 tube pass as a circulating reaction liquid, and the heat released by the reaction is removed, and the remaining part is extracted into the crude product storage tank 11, and the material in and out of the reactor 7 is kept balanced. Among them, the mass ratio of the part of the crude butyl butyrate solution obtained by the reaction that enters the outer circulation cooler 6 tube pass as a circulating reaction liquid to the part extracted into the crude product storage tank 11 is 150:1.

[0083] Step 4: Deactivate the catalyst

[0084] 3 wt % KOH solution was added to the crude product storage tank 11 at a mass ratio of 100:1 between the crude butyl butyrate and the deactivator to deactivate the catalyst. The stirring rate of the crude product storage tank 11 was controlled at 320 rpm. After 30 minutes of mixing and stirring, the mixture was stopped and allowed to stand for 20 minutes to allow the solution to be completely stratified. The upper layer of crude butyl butyrate entered the separation system, and the KOH solution was discharged from the sewage outlet 17 at the bottom of the crude product storage tank 11.

[0085] The detection of crude butyl butyrate showed that when the feed mass flow rate of raw material butyraldehyde to catalyst was 12:1, full load production operation was achieved, the butyraldehyde conversion rate was 91.50%, and the reaction selectivity was 98.22%.

[0086] Embodiment 4:

[0087] The first step: the butyraldehyde raw material tank 1, the catalyst dissolution tank 3, the reactor 7, the crude product storage tank 11 and the deactivator storage tank 12 are pressurized with nitrogen through a back pressure valve, and the pressure is maintained at 15kPa; chilled water is used in the cooling jackets of the mixer 5 and the reactor 7, and chilled water is introduced into the shell side of the external circulation cooler 6.

[0088] Step 2: Dissolve the catalyst at high temperature

[0089] The catalyst is added into the catalyst dissolving tank 3, the stirring rate of the catalyst dissolving tank is controlled at 320 rpm, the catalyst is heated to 80° C. and then kept warm, and the catalyst is dissolved into a solution state.

[0090] Step 3: Butyraldehyde catalytic disproportionation to prepare butyl butyrate

[0091] The raw material butyraldehyde and the catalyst solution are respectively delivered to the mixer 5 by the butyraldehyde feed pump 2 and the catalyst delivery pump 4 in a mass ratio of 12:1 for premixing, and then enter the outer circulation cooler 6 tube pass for cooling after mixing, and the outlet temperature of the outer circulation cooler 6 tube pass is controlled at 12°C. The cooled solution is delivered to the reactor 7 for full mixing reaction, and the stirring rate of the reactor 7 is controlled at 320rpm, and the temperature in the reactor 7 is controlled to be 16°C; the crude butyl butyrate solution obtained by the reaction enters the circulation pump 8 from the bottom of the reactor 7, and most of it enters the outer circulation cooler 6 tube pass as a circulating reaction liquid, and the heat released by the reaction is removed, and the remaining part is extracted into the crude product storage tank 11, and the material in and out of the reactor 7 is kept balanced. Among them, the mass ratio of the part of the crude butyl butyrate solution obtained by the reaction that enters the outer circulation cooler 6 tube pass as a circulating reaction liquid to the part extracted into the crude product storage tank 11 is 130:1.

[0092] Step 4: Deactivate the catalyst

[0093] Deionized water is added to the crude product storage tank 11 at a mass ratio of 100:1 between the crude butyl butyrate and the deactivator to deactivate the catalyst. The stirring rate of the crude product storage tank 11 is controlled at 350 rpm. The mixing and stirring is stopped after 25 minutes. The solution is allowed to stand for 18 minutes to allow the solution to be completely stratified. The upper layer of crude butyl butyrate enters the separation system, and the deionized water is discharged from the sewage outlet 17 at the bottom of the crude product storage tank 11.

[0094] The detection of crude butyl butyrate showed that when the feed mass flow rate of raw material butyraldehyde to catalyst was 12:1, full load production operation was achieved, the butyraldehyde conversion rate was 91.83%, and the reaction selectivity was 98.62%.

[0095] Embodiment 5:

[0096] The first step: the butyraldehyde raw material tank 1, the catalyst dissolution tank 3, the reactor 7, the crude product storage tank 11 and the deactivator storage tank 12 are pressurized with nitrogen through a back pressure valve, and the pressure is maintained at 15kPa; chilled water is used in the cooling jackets of the mixer 5 and the reactor 7, and chilled water is introduced into the shell side of the external circulation cooler 6.

[0097] Step 2: Dissolve the catalyst at high temperature

[0098] The catalyst is added into the catalyst dissolving tank 3, the stirring rate of the catalyst dissolving tank is controlled at 360 rpm, the catalyst is heated to 80° C. and then kept warm, and the catalyst is dissolved into a solution state.

[0099] Step 3: Butyraldehyde catalytic disproportionation to prepare butyl butyrate

[0100] The raw material butyraldehyde and the catalyst solution are respectively delivered to the mixer 5 by the butyraldehyde feed pump 2 and the catalyst delivery pump 4 in a mass ratio of 10:1 for premixing, and then enter the outer circulation cooler 6 tube pass for cooling after mixing, and the outlet temperature of the outer circulation cooler 6 tube pass is controlled at 8°C. The cooled solution is delivered to the reactor 7 for full mixing reaction, and the stirring rate of the reactor 7 is controlled at 360rpm, and the temperature in the reactor 7 is controlled to be 12°C; the crude butyl butyrate solution obtained by the reaction enters the circulation pump 8 from the bottom of the reactor 7, and most of it enters the outer circulation cooler 6 tube pass as a circulating reaction liquid, and the heat released by the reaction is removed, and the remaining part is extracted into the crude product storage tank 11, and the material in and out of the reactor 7 is kept balanced. Among them, the mass ratio of the part of the crude butyl butyrate solution obtained by the reaction that enters the outer circulation cooler 6 tube pass as a circulating reaction liquid to the part extracted into the crude product storage tank 11 is 150:1.

[0101] Step 4: Deactivate the catalyst

[0102] Deionized water is added to the crude product storage tank 11 at a mass ratio of 90:1 between the crude butyl butyrate and the deactivator to deactivate the catalyst. The stirring rate of the crude product storage tank 11 is controlled at 320 rpm. The mixing and stirring is stopped after 20 minutes. The solution is allowed to stand for 20 minutes to allow the solution to be completely stratified. The upper layer of crude butyl butyrate enters the separation system, and the deionized water is discharged from the sewage outlet 17 at the bottom of the crude product storage tank 11.

[0103] The detection of crude butyl butyrate showed that when the feed mass flow rate of raw material butyraldehyde to catalyst was 10:1, full load production operation was achieved, the butyraldehyde conversion rate was 92.03%, and the reaction selectivity was 98.59%.

[0104] Although the functions and working processes of the present invention have been described above in conjunction with the accompanying drawings, the present invention is not limited to the above-mentioned specific functions and working processes. The above-mentioned specific implementation methods are merely illustrative rather than restrictive. Under the guidance of the present invention, ordinary technicians in this field can also make many forms without departing from the scope of protection of the purpose of the present invention and the claims, which are all within the protection of the present invention.

Claims

1. A synthesis system for producing butyl butyrate from butyraldehyde in one step, characterized in that: It comprises a butyraldehyde raw material tank (1), a butyraldehyde feed pump (2), a catalyst dissolution tank (3), a catalyst delivery pump (4), a mixer (5), an external circulation cooler (6), a reaction kettle (7), a circulation pump (8), a crude product storage tank (11), and an inactivator storage tank (12); The inlet of the butyraldehyde feed pump (2) is connected to the butyraldehyde raw material tank (1) through a pipeline, the inlet of the catalyst delivery pump (4) is connected to the catalyst dissolution tank (3) through a pipeline, the outlet of the butyraldehyde feed pump (2) and the outlet of the catalyst delivery pump (4) are respectively connected to the inlet of the mixer (5) through pipelines, the outlet of the mixer (5) is connected to the pipe side inlet of the external circulation cooler (6) through a pipeline, and the pipe side outlet of the external circulation cooler (6) is connected to the reactor (7) through a pipeline. The bottom discharge port of the reactor (7) is connected to the inlet of a circulation pump (8) through a pipeline, the outlet of the circulation pump (8) is connected to the pipe inlet of an external circulation cooler (6) and the inlet of a crude product storage tank (11) through a circulation pipeline (9) and a production pipeline (10), respectively, the crude product storage tank (11) is connected to the inactivator storage tank (12) through a pipeline, and a discharge pipe (14) is provided at the bottom of the crude product storage tank (11), and the discharge pipe (14) is connected to a separation system through a pipeline; The outer walls of the mixer (5) and the reactor (7) are both provided with cooling jackets; the catalyst dissolution tank (3), the reactor (7) and the crude product storage tank (11) are all provided with stirring devices; the butyraldehyde raw material tank (1), the catalyst dissolution tank (3), the reactor (7), the crude product storage tank (11) and the deactivator storage tank (12) are all provided with back pressure valves; the catalyst dissolution tank (3) has a heating device, and a catalyst feeding hopper (15) is provided on the top of the catalyst dissolution tank (3).

2. The synthesis system for producing butyl butyrate from butyraldehyde in one step according to claim 1, characterized in that: The butyraldehyde feed pump (2) and the catalyst delivery pump (4) are both pumps with flow metering function, or the outlets of the butyraldehyde feed pump (2) and the catalyst delivery pump (4) are both provided with regulating valves for regulating flow.

3. The synthesis system for producing butyl butyrate from butyraldehyde in one step according to claim 1, characterized in that: The circulation pipeline (9) and the extraction pipeline (10) are both provided with flow regulating valves (18), and the pipeline connecting the inactivator storage tank (12) and the crude product storage tank (11) is provided with a valve (13).

4. The synthesis system for producing butyl butyrate from butyraldehyde in one step according to claim 1, characterized in that: The inactivator storage tank (12) is located above the crude product storage tank (11); a sewage outlet (17) is provided at the bottom of the crude product storage tank (11); a sight glass (16) is provided on the side 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 perpendicular to the inner wall of the tank bottom; and the height of the upper end of the discharge pipe (14) is within the field of view of the sight glass (16).

5. A method for synthesizing a synthesis system for producing butyl butyrate by a one-step process of butyraldehyde according to any one of claims 1 to 4, characterized in that: The following steps are involved: The first step is to maintain the butyraldehyde raw material tank (1), the catalyst dissolution tank (3), the reactor (7), the crude product storage tank (11) and the deactivator storage tank (12) with nitrogen pressure through a back pressure valve, and the pressure range is 10 to 20 kPa; chilled water is used in the cooling jackets of the mixer (5) and the reactor (7), and chilled water is introduced into the shell side of the external circulation cooler (6); Step 2: Dissolve the catalyst at high temperature The catalyst is added into the catalyst dissolving tank (3), and the catalyst is heated to 60-100° C. and then kept warm under stirring to dissolve the catalyst into a solution state; The stirring rate of the catalyst dissolving tank (3) is controlled at 200-400 rpm; the catalyst is POP-Ru, which is based on a porous organic polymer rich in hydroxyl groups and forms a Ru complex structure on its surface; Step 3: Butyraldehyde catalytic disproportionation to prepare butyl butyrate The raw material butyraldehyde and the catalyst in a certain ratio are premixed in a mixer (5), and after mixing, they are cooled in an external circulation cooler (6) tube side, and then transported to a reactor (7) for sufficient reaction. Most of the crude butyl butyrate solution obtained by the reaction is entered into the external circulation cooler (6) tube side as a circulating reaction liquid, and the heat released by the reaction is removed. The remaining part is extracted into a crude product storage tank (11), and the material inflow and outflow of the reactor (7) are kept balanced; Step 4: Deactivate the catalyst The deactivator is added to the crude product storage tank (11) at a mass ratio of 80:1 to 100:1 of crude butyl butyrate to deactivator to inactivate the catalyst. After mixing and stirring for 15 to 30 minutes, the solution is allowed to stand until the solution is completely separated into layers. The upper layer of crude butyl butyrate enters the separation system, and the deactivator is discharged from the sewage outlet (17) at the bottom of the crude product storage tank (11).

6. The method for producing butyl butyrate from butyraldehyde in one step according to claim 5, characterized in that: In the third step, the raw material butyraldehyde and the catalyst solution are respectively delivered to the mixer (5) by a butyraldehyde feed pump (2) and a catalyst delivery pump (4) in a mass ratio of 4:1 to 12:1; the stirring rate of the reactor (7) is controlled at 200 to 400 rpm, and the temperature inside the reactor (7) is controlled at 10 to 25° C.; the outlet temperature of the tube side of the external circulation cooler (6) is controlled at 8 to 20° C.; and the mass ratio of the crude butyl butyrate solution obtained by the reaction that enters the tube side of the external circulation cooler (6) as a circulating reaction liquid to the part withdrawn to the crude product storage tank (11) is controlled at 100:1 to 150:

1.

7. The method for producing butyl butyrate from butyraldehyde in one step according to claim 5, characterized in that: In the fourth step, the stirring rate of the crude product storage tank (11) is controlled at 200-400 rpm; the solution standing time is controlled at 15-30 minutes; and the inactivator is deionized water or a dilute alkaline solution.

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