Production device and production method for preparing acetoxypropionaldehyde through hydroformylation reaction and application of acetoxypropionaldehyde

Abstract

The invention provides a production device and a production method for preparing acetoxypropionaldehyde through hydroformylation reaction and application of acetoxypropionaldehyde. Under the hydroformylation condition, vinyl acetate, synthesis gas and a hydroformylation catalyst are fed into a first reaction unit for a contact reaction, part of a first liquid-phase product is cooled and then circulated, and part of the first liquid-phase product passes through all separation units to separate out unreacted synthesis gas, a circulating catalyst solution, a crude product and an unreacted material flow in sequence; unreacted material flow and the other stream of synthesis gas are fed into a second reaction unit for continuous contact reaction, and after light components are separated from a liquid-phase product, the catalyst solution is returned to the front separation unit. According to the technical scheme provided by the invention, the material flow direction is reasonably arranged, energy consumption and material consumption are saved, the reaction efficiency of the reaction units is effectively improved, the scale of the reaction unit devices is reduced, side reactions are reduced, and the catalyst proportion of each reaction unit can be flexibly regulated.

Description

Technical Field

[0001] The invention belongs to the field of acetoxypropionaldehyde preparation, and specifically relates to a production device, a production method and an application of acetoxypropionaldehyde prepared by hydroformylation reaction. Background Art

[0002] Polytrimethylene terephthalate (PTT) can be synthesized from 1,3-propylene glycol as raw material. PTT is a new polyester material that combines the high performance of polyethylene terephthalate (PET) and the easy processing of polybutylene terephthalate (PBT). The raw material acrolein for the acrolein hydration hydrogenation process developed by Evonik in Germany is highly toxic, flammable and explosive, difficult to store and transport, and difficult to obtain at a high price. The hydroformylation ethylene oxide (EO) process developed by Shell requires high-pressure equipment, high technical difficulty, complex catalytic system, harsh and unstable process, and difficult to control the reaction. The bio-enzyme catalysis method developed by Du Pont has low production efficiency and complex purification process. Therefore, the process of synthesizing propylene glycol and hydroxypropionic acid compounds with vinyl acetate hydroformylation as the key step has been widely studied in recent years, and the preparation technology of its catalyst has become increasingly mature. In this process, vinyl acetate is first hydroformylated to produce the intermediate product acetoxypropionaldehyde, which is then hydrogenated to produce acetoxypropanol, and then hydrolyzed to produce 1,3-propylene glycol and 1,2-propylene glycol, with acetic acid as a by-product.

[0003] In order to improve the conversion rate of olefins, a commonly used technical solution is to use two or more reactors in series. For example, this method is mentioned in patents CN102826973A, CN86101063A, and US5105018A. This method allows the unconverted raw materials or the solution containing the raw materials in the first reaction unit to enter the second reaction unit together with the synthesis gas to continue the reaction, ensuring the residence time and improving the overall conversion rate of vinyl acetate. The above patents usually involve the use of solvents, introduce new substances, and the separation of products and solvents requires precise control; at the same time, the recycling of catalyst solutions is not flexible enough; the reaction unit usually uses two reactors of the same size. Since the unconverted raw materials are mainly present in the liquid phase under normal reaction conditions, the reaction liquid phase flow of the first reaction unit is sent to the second reaction unit, and the reaction flow contains a large amount of acetoxypropionaldehyde products, which will reduce the efficiency of the second reaction zone. Summary of the invention

[0004] The present invention provides a production device and a production method for preparing acetoxypropionaldehyde by hydroformylation reaction. In order to improve the efficiency of the second reaction unit, the setting of the separation unit is improved between the first reaction unit and the second reaction unit, the crude product and the logistics containing unreacted raw materials are separated, and the separated catalyst solution is recycled back to the first reaction unit and the second reaction unit respectively. The method can effectively improve the efficiency of the second reaction unit, reduce the scale of the second reaction unit device, reduce side reactions, and flexibly adjust the catalyst ratio of the first reaction unit and the second reaction unit.

[0005] One of the purposes of the present invention is to provide a production device for preparing acetoxypropionaldehyde by hydroformylation reaction, comprising a first reaction unit, a first gas-liquid separation system, a second reaction unit, and a second gas-liquid separation system connected in sequence by pipelines, wherein the liquid phase outlet of the first reaction unit is connected to the material inlet of the first gas-liquid separation system by a pipeline, and a branch is arranged on the pipeline to connect the liquid phase inlet of the first reaction unit, the outlet of the catalyst solution separated by the first gas-liquid separation system is connected to the first reaction unit and the second reaction unit by a pipeline, and the outlet of the catalyst solution obtained by the second gas-liquid separation system is connected to the first gas-liquid separation system by a pipeline. The first gas-liquid separation system comprises a first separation unit, a second separation unit, and a third separation unit, and the second gas-liquid separation system comprises a fourth separation unit and a fifth separation unit.

[0006] According to the present invention, in the production device for preparing acetoxypropionaldehyde by hydroformylation reaction:

[0007] The first reaction unit may be any synthesis reactor known in the art. The first reaction unit is provided with a raw material inlet, a synthesis gas inlet, an optional hydrogen inlet, a gas phase outlet, and a liquid phase outlet. The gas phase outlet is connected to the first separation unit by a pipeline, and the liquid phase outlet is connected to the material inlet of the first separation unit by a pipeline, and a branch is provided on the pipeline to be connected to the material inlet of the first reaction unit, so that part of the liquid phase product is circulated and sent to the first reaction unit; the first reaction unit is provided with a cooling system, preferably a cooling coil;

[0008] The first separation unit is also provided with a gas phase outlet and a liquid phase outlet, and the liquid phase outlet is connected to the material inlet of the second separation unit by a pipeline; the first separation unit can adopt a combination of a decompression gas-liquid separation tank commonly used in the art;

[0009] The second separation unit is also provided with a liquid phase outlet and a catalyst solution outlet, the liquid phase outlet is connected to the material inlet of the third separation unit by a pipeline, and the catalyst solution outlet is connected to the first reaction unit and the second reaction unit by a pipeline, and the catalyst solution is respectively sent to the first reaction unit and the second reaction unit for recycling; the second separation unit can adopt various separation equipment or combinations commonly used in the art, for example, a tower separation equipment can be adopted;

[0010] The third separation unit is also provided with an unreacted stream outlet and an acetoxypropionaldehyde crude product outlet, and the unreacted stream outlet is connected to the material inlet of the second reaction unit by a pipeline; the third separation unit can be various separation equipment known in the art, for example, the third separation unit can be a tower separation equipment;

[0011] The second reaction unit may be any synthesis reactor known in the art. The second reaction unit is further provided with a synthesis gas inlet, a gas phase outlet, a liquid phase outlet, and an optional hydrogen inlet. The gas phase outlet is connected to the first separation unit by a pipeline, and the liquid phase outlet is connected to the material inlet of the fourth separation unit by a pipeline. The second reaction unit is provided with a cooling system, preferably a jacketed cooling system.

[0012] The fourth separation unit is further provided with a gas phase outlet and a liquid phase outlet, and the liquid phase outlet is connected to the material inlet of the fifth separation unit by a pipeline; the fourth separation unit can be various separation devices known in the art, for example, a combination of a decompression gas-liquid separation tank;

[0013] The fifth separation unit is also provided with a light component outlet and a liquid phase outlet, and the liquid phase outlet is connected to the material inlet of the second separation unit by a pipeline; the fifth separation unit can be various separation equipment known in the art, for example, a tower separation equipment.

[0014] The second object of the present invention is to provide a production method for preparing acetoxypropionaldehyde by hydroformylation reaction, which is implemented on the production device for preparing acetoxypropionaldehyde by hydroformylation reaction.

[0015] According to the present invention, the production method for preparing acetoxypropionaldehyde by hydroformylation reaction comprises: reacting raw materials, synthesis gas, catalyst, and solvent in a first reaction unit, dividing the obtained liquid product into two parts, one part is recycled back to the first reaction unit, and the other part is sent to a first gas-liquid separation system for separation treatment to obtain a crude acetoxypropionaldehyde product, an unreacted logistics and a catalyst solution, the catalyst solution is circulated to the first reaction unit and the second reaction unit, the unreacted logistics is sent to the second reaction unit for further reaction, and the product obtained in the second reaction unit is sent to a second gas-liquid separation system for separation treatment to obtain a light component and a liquid component.

[0016] Furthermore, the production method specifically comprises the following steps:

[0017] 1) Vinyl acetate, catalyst, synthesis gas S1, and solvent are fed into a first reaction unit for contact reaction, and the gas phase G1 obtained after the reaction is fed into a first separation unit;

[0018] 2) The liquid phase component L1 (including reaction products, unreacted raw materials, catalyst, and solvent) obtained after the reaction in the first reaction unit is divided into two parts, one part of the liquid phase L1-1 is sent to the liquid phase inlet of the first reaction unit, and the other part of the liquid phase L1-2 is sent to the first separation unit;

[0019] 3) The liquid phase component L1-2 enters the first separation unit, the separated gas phase G2 is discharged, and the liquid phase L2 continues to enter the second separation unit, and is further separated in the second separation unit to obtain the liquid phase L3 and the catalyst solution, and the catalyst solution is circulated to the first reaction unit and the second reaction unit; the liquid phase L3 is sent to the third separation unit to separate the unreacted stream L4 and the crude acetoxypropionaldehyde product;

[0020] 4) sending the unreacted stream L4 and the synthesis gas S2 to the second reaction unit for contact reaction, and sending the gas phase G5 obtained by the reaction to the first separation unit;

[0021] 5) The liquid phase L5 obtained after the reaction in the second reaction unit is sent to the fourth separation unit, the separated gas phase G6 is discharged, and the liquid phase L6 continues to enter the fifth separation unit, and is further separated in the fifth separation unit to obtain light components and liquid phase L7. The liquid phase L7 is sent to the second separation unit, and the light components are discharged for recovery.

[0022] According to the present invention, in step 1) of the production method for preparing acetoxypropionaldehyde by hydroformylation reaction:

[0023] The synthesis gas S1 may be any synthesis gas of various specifications in the art. For example, the synthesis gas S1 is a gas component containing hydrogen and carbon monoxide. Preferably, the molar ratio of hydrogen to carbon monoxide in the synthesis gas S1 is (0.5-6):1, preferably (0.5-2):1. In a continuous industrial production process, hydrogen may be optionally introduced into the first reaction unit according to the gas composition of the synthesis gas to adjust the ratio of hydrogen to carbon monoxide in the synthesis gas to be within the above range.

[0024] The molar ratio of vinyl acetate to synthesis gas S1 is 1:(1-23), preferably 1:(1-10), wherein the molar amount of synthesis gas S1 is calculated based on the total molar amount of hydrogen and carbon monoxide therein;

[0025] The catalyst is selected from at least one of the compounds containing the metal component rhodium, and can be a compound and / or complex of rhodium commonly used in the art. The catalyst can be used alone without a ligand and a co-catalyst, and without adding a reaction accelerator; further, the catalyst is preferably L-coordinated tricarbonyl hydride rhodium (HRh(CO)3L); the amount of the catalyst can be within the commonly used range in the art, for example, in terms of molar amount, the amount of the catalyst is 0.2-10 mol%, preferably 0.5-5 mol% of vinyl acetate;

[0026] The solvent is an acetoxypropionaldehyde compound, preferably acetoxypropionaldehyde, such as 3-acetoxypropionaldehyde, or a mixture containing 2-acetoxypropionaldehyde and 3-acetoxypropionaldehyde, wherein the mixture containing 2-acetoxypropionaldehyde and 3-acetoxypropionaldehyde can be a crude product of a hydroformylation reaction; according to a specific embodiment of the present invention, the solvent is most preferably a solvent containing an acetoxypropionaldehyde compound (3-acetoxypropionaldehyde, or a mixture containing 2-acetoxypropionaldehyde and 3-acetoxypropionaldehyde); using the product of the hydroformylation reaction of vinyl acetate as a solvent can avoid the introduction of other substances, improve the separation efficiency of the product and the catalyst solution, and improve the recovery rate;

[0027] The catalyst and solvent can be added to the reaction system in the form of a catalyst solution, wherein the content of the catalyst can be varied in a wide range, preferably, based on the total amount of the catalyst and solvent being 100wt%, the catalyst is 0.5-30wt% of the total amount of the catalyst and solvent, preferably 10-20wt%;

[0028] The reaction conditions of the first reaction unit are: reaction temperature of 50-150°C, reaction pressure of 0.5-8MPa, and reaction residence time of 30-180min; preferably, the reaction temperature is 80-130°C, the reaction pressure is 0.5-7.5MPa, and the reaction residence time is 30-120min.

[0029] According to the present invention, in the production method for preparing acetoxypropionaldehyde by hydroformylation reaction:

[0030] In the step 2), the liquid phase L1-1 circulated to the first reaction unit accounts for 7 to 90% of the liquid phase L1, preferably 10 to 50%; preferably, the liquid phase component L1-1 is cooled and circulated to the first reaction unit to control the reaction temperature of the first reaction unit; further, the temperature of the liquid phase component L1-1 after cooling is 30 to 95°C, preferably 30 to 80°C;

[0031] In the step 3), the ratio of the catalyst solution obtained by the second separation unit to be circulated to the first reaction unit and the second reaction unit is not particularly limited and can be adjusted within a wide range. Preferably, the catalyst solution circulated to the first reaction unit is 50-99% of the total amount of the catalyst solution obtained by the second separation unit, preferably 60-99%; the catalyst solution circulated to the second reaction unit is 1-50% of the total amount of the catalyst solution obtained by the second separation unit, preferably 1-40%; in actual production, part or all of the catalyst solution can be returned to the first reaction unit and the second reaction unit as needed, and the remaining part can be discharged for recovery;

[0032] The operating conditions of the first separation unit are not particularly limited, and the separation conditions commonly used in the art may be adopted, for example, flash evaporation at a pressure of 0.5 to 2.5 MPa, cooling separation at 45 to 80° C., or a combination thereof;

[0033] The second separation unit can be any separation device or combination known in the art, as long as it can separate the catalyst solution and other liquid component materials. For example, a separation tower can be used. The operating conditions of the separation tower can be any conditions known in the art. Preferably, the separation conditions of the second separation unit are: tower top temperature of 80-120°C, tower bottom temperature of 90-150°C, pressure of 10-201Kpa, number of plates of 5-40, and reflux ratio of 0.1-10.

[0034] The third separation unit can be various separation equipment or combinations known in the art, as long as it can separate the crude acetoxypropionaldehyde product and the logistics containing unreacted materials. For example, a separation tower can be used, and the operating conditions of the separation tower can be various conditions known in the art. Preferably, the separation conditions of the third separation unit are: 80-120°C, tower bottom temperature of 90-150°C, pressure of 10-200Kpa, number of plates of 5-40, and reflux ratio of 0.1-10; the crude acetoxypropionaldehyde product includes 2-acetoxypropionaldehyde and 3-acetoxypropionaldehyde.

[0035] According to the present invention, in step 4) of the production method for preparing acetoxypropionaldehyde by hydroformylation reaction:

[0036] The synthesis gas S2 can be synthesis gas of various specifications in the art. For example, the synthesis gas S2 is a gas component containing hydrogen and carbon monoxide. Preferably, the molar ratio of hydrogen to carbon monoxide in the synthesis gas S2 is (0.5-6):1, preferably (0.5-3):1. In the continuous industrial production process, hydrogen is optionally introduced into the second reaction unit according to the gas composition of the synthesis gas, so as to adjust the ratio of hydrogen to carbon monoxide in the synthesis gas within the above range.

[0037] The molar ratio of the synthesis gas S2 to the vinyl acetate in the unreacted stream L4 is (1-23):1, preferably (1-10):1, wherein the molar amount of the synthesis gas S2 is calculated based on the total molar amount of hydrogen and carbon monoxide therein;

[0038] In the second reaction unit, the amount of the catalyst is 0.2 to 20 wt %, preferably 1 to 18 wt % of the vinyl acetate in the unreacted stream L4;

[0039] The reaction conditions of the second reaction unit are: reaction temperature of 50-150°C, reaction pressure of 0.5-8MPa, and reaction residence time of 30-180min; preferably, the reaction temperature is 80-130°C, the reaction pressure is 0.5-7.5MPa, and the reaction residence time is 30-120min.

[0040] According to the present invention, in step 5) of the production method for preparing acetoxypropionaldehyde by hydroformylation reaction:

[0041] The operating conditions of the fourth separation unit are not particularly limited, and the separation conditions commonly used in the art may be adopted, for example, flash evaporation at a pressure of 0.5 to 2.5 MPa, cooling separation at 45 to 80° C., or a combination thereof;

[0042] The fifth separation unit can be any separation device or combination known in the art, as long as it can separate the light component from other liquid component materials. For example, a separation tower can be used. The operating conditions of the separation tower can be any conditions known in the art. Preferably, the operating conditions of the fifth separation unit are: the tower top temperature is 60-110°C, the tower bottom temperature is 90-150°C, the pressure is 10-201 kPa, the number of plates is 5-40, and the reflux ratio is 0.1-10; the light component mainly contains acetic acid and ethyl acetate;

[0043] The liquid components except the light components obtained in the fifth separation unit are sent to the second separation unit for component separation and then the subsequent separation operations and other continuous production processes are continued.

[0044] The third object of the present invention is to provide a production device for preparing acetoxypropionaldehyde by the above-mentioned hydroformylation reaction or a production method for preparing acetoxypropionaldehyde by the above-mentioned hydroformylation reaction, and an application of the device in preparing acetoxypropionaldehyde by the hydroformylation reaction.

[0045] The present invention provides a production device for preparing acetoxypropionaldehyde by hydroformylation reaction. By setting a plurality of reaction units and a gas-liquid separation unit and rationally arranging the material flow direction, the method can save material consumption, effectively improve the reaction efficiency of the reaction unit, reduce the equipment size, and reduce the scale of the reaction unit device. In the production method provided by the present invention, the product of the first reaction unit is preliminarily separated to separate the unreacted raw material with increased concentration, which can reduce side reactions and improve the reaction efficiency of the second reaction unit. In addition, in the present invention, the catalyst solution obtained by the separation unit is circulated to the first reaction unit and the second reaction unit by splitting, and the yield of the raw material vinyl acetate is improved by flexibly adjusting the catalyst ratio in each reaction unit, and the residence time and reaction effect are guaranteed. BRIEF DESCRIPTION OF THE DRAWINGS

[0046] Figure 1 This is a schematic diagram of a hydroformylation reaction device used in an embodiment of the present invention.

[0047] Description of reference numerals:

[0048] 1-first reaction unit, 2-second reaction unit, 3-first separation unit, 4-second separation unit, 5-catalyst solution circulation pipeline, 6-unreacted logistics L4 pipeline, 7-synthesis gas S1 pipeline, 8-vinyl acetate pipeline, 9-hydrogen pipeline, 10-synthesis gas S2 pipeline, 11-fourth separation unit, 12-fifth separation unit, 13-liquid component L1-1 circulation pipeline, 14-third separation unit, 15-crude product discharge pipeline, 16-light component discharge pipeline. DETAILED DESCRIPTION

[0049] The present invention is described in detail below in conjunction with specific embodiments. It is necessary to point out that the following embodiments are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made to the present invention by those skilled in the art based on the contents of the present invention still fall within the scope of protection of the present invention.

[0050] The raw materials used in the examples and comparative examples, unless otherwise specified, are disclosed in the prior art, for example, they can be directly purchased or prepared according to the preparation methods disclosed in the prior art.

[0051] The production device for preparing acetoxypropionaldehyde by hydroformylation reaction in the embodiment of the present invention is as follows Figure 1As shown, it includes a first reaction unit 1, a first separation unit 3, a second separation unit 4, a third separation unit 14, a second reaction unit 2, a fourth separation unit 11, and a fifth separation unit 12 connected in sequence by pipelines, wherein the first reaction unit 1 and the second reaction unit 2 are connected to the first separation unit 3 by pipelines respectively; the first reaction unit 1 is provided with a raw material inlet 8, a synthesis gas S1 inlet 7, a hydrogen inlet 9, a gas phase G1 outlet, and a liquid phase L1 outlet, the gas phase G1 outlet is connected to the first separation unit 3 by a pipeline, the liquid phase L1 outlet is connected to the material inlet of the first separation unit 3 by a pipeline, and a branch 13 is arranged on the pipeline to connect to the first reaction unit 1, so that part of the liquid phase product is circulated into the first reaction unit; the first separation unit 3 is also provided with a gas phase G2 outlet and a liquid phase L2 outlet, and the liquid phase L2 outlet is connected to the material inlet of the second separation unit 4 by a pipeline; the second separation unit 4 is also provided with a liquid phase L3 outlet, a catalyst solution outlet Port 5, the liquid phase L3 outlet is connected to the material inlet of the third separation unit 14 by a pipeline, and the catalyst solution outlet 5 is connected to the first reaction unit and the second reaction unit by a pipeline; the third separation unit 14 is also provided with an unreacted flow L4 outlet and an acetoxypropionaldehyde crude product outlet 15, and the unreacted flow L4 outlet is connected to the material inlet of the second reaction unit 2 by a pipeline 6; the second reaction unit 2 is also provided with a synthesis gas S2 inlet 10, a gas phase G5 outlet, a liquid phase L5 outlet, and a hydrogen inlet 9, the gas phase G5 outlet is connected to the first separation unit 3 by a pipeline, and the liquid phase L5 outlet is connected to the material inlet of the fourth separation unit 11 by a pipeline; the fourth separation unit 11 is also provided with a gas phase G6 outlet and a liquid phase L6 outlet, and the liquid phase L6 outlet is connected to the material inlet of the fifth separation unit 12 by a pipeline; the fifth separation unit 12 is also provided with a light component outlet 16 and a liquid phase L7 outlet, and the liquid phase L7 outlet is connected to the material inlet of the second separation unit 4 by a pipeline.

[0052] Example 1

[0053] Vinyl acetate, synthesis gas S1 and catalyst solution (the solvent is 3-acetoxypropionaldehyde, and the amount of rhodium compound in the solution is 16.58% based on HRh(CO)3L) are fed into the first reaction unit 1, wherein the introduction rate of vinyl acetate is 2829 kg / h, the introduction rate of catalyst solution is 723.26 kg / h, the introduction rate of synthesis gas S1 is 760 kg / h (the molar ratio of hydrogen to carbon monoxide in the synthesis gas is 1.19:1), and the feed molar ratio of synthesis gas S1 to vinyl acetate in the reactor is maintained at about 1.67:1; a part L1-1 of the bottom liquid phase in the first reaction unit 1 is cooled to 45°C and then returned to the first reaction unit 1, and the other part L1-2 is fed to the first separation unit 3, and the ratio of the liquid phase L1-1 returned to the first reaction unit 1 to the total extracted liquid phase L1 from the bottom of the first reaction unit 1 is 0.1.

[0054] In the first separation unit 3, the components including the liquid phase components L1-2, the gas phase G1 and the gas phase G5 are flash-evaporated after the pressure is reduced to 1.0 MPa, and the obtained gas phase G2 is discharged, and the obtained liquid phase component L2 is sent to the second separation unit 4 (separation tower) for separation, wherein the tower top temperature of the second separation unit 4 is 97.7°C, the tower bottom temperature is 123.4°C, the pressure is 30 kPa, the number of plates is 23, and part of the crude acetoxypropionaldehyde product is refluxed at the top of the tower, and the reflux ratio is 1, so that the crude acetoxypropionaldehyde product and unreacted vinyl acetate are mainly extracted from the top of the tower, and the top extraction rate is 3822.839 kg / h, and the catalyst solution 5 is extracted from the bottom of the second separation unit 4, and the extraction rate is 841 kg / h. The extracted catalyst solution is partially or completely returned to the first reaction unit 1 and sent to the second reaction unit 2 as a catalyst solution as needed, which are 723.26 kg / h and 117.74 kg / h respectively, and the remaining part is discharged for recovery.

[0055] The liquid phase L3 extracted from the top of the second separation unit 4 is sent to the third separation unit 14 (separation tower). The top temperature of the separation tower in the third separation unit 14 is 53.6°C, the bottom temperature is 103.8°C, the pressure is 30kPa, the number of plates is 18, and the unreacted reactants are refluxed at the top of the tower, and the reflux ratio is 8, so that the unreacted vinyl acetate and the like L4 are extracted from the top of the tower and sent to the second reaction unit 2 to participate in the subsequent reaction, and the extraction rate is 397.4kg / h. The reaction product acetoxypropionaldehyde product is extracted from the bottom of the tower, and the extraction rate is 3422.86kg / h.

[0056] Another stream of synthesis gas S2 (the molar ratio of hydrogen to carbon monoxide in the synthesis gas S2 is 1:1) and the produced stream L4 from the top of the third separation unit 14 are fed into the second reaction unit 2, wherein the feeding rate of the stream L4 is 397.4 kg / h, and the feeding rate of the synthesis gas S2 is 131 kg / h, and the feeding molar ratio of the synthesis gas S2 of the second reaction unit 2 to the vinyl acetate in the stream L4 is maintained at 3.98:1; the top gas phase G5 of the second reaction unit 2 is fed into the first separation unit 3, and the bottom liquid phase L5 is fed into the fourth separation unit 11, and the pressure is reduced to 1.0 MPa and then flash separated, and the unreacted part of the synthesis gas gas phase G6 is separated and discharged, and the liquid phase L6 is fed into the fifth separation unit 12 (separation tower) for separation;

[0057] The liquid phase component L6 obtained by the fourth separation unit 11 is sent to the fifth separation unit 12 for gas-liquid separation, wherein the top temperature of the fifth separation unit 12 is 86°C, the bottom temperature is 126°C, the pressure is 60kPa, the number of plates is 23, and part of the light component is refluxed at the top of the tower, and the reflux ratio is 1, so that the light component 16 obtained by the reaction is mainly extracted from the top of the tower, and the extraction rate is 207.56kg / h, and the bottom liquid phase L7 is extracted from the bottom of the fifth separation unit 12, and the extraction rate is 360kg / h. All the extracted bottom liquid phase L7 is returned to the second separation unit 4 for further separation.

[0058] The reaction temperature in the first reaction unit 1 is 109°C, the pressure is 6.5 MPa, and the reaction residence time is 60 min; the reaction temperature in the second reaction unit 2 is 103°C, the pressure is 5.5 MPa, and the reaction residence time is 80 min. The conversion rate of vinyl acetate is 99%, and the yield is 88.8%.

[0059] Example 2

[0060] The process of Example 1 was followed, except that:

[0061] Vinyl acetate, synthesis gas S1 and catalyst solution (the solvent is 3-acetoxypropionaldehyde, and the amount of rhodium compound in the solution is 15.52% based on HRh(CO)3L) are fed into the first reaction unit 1, wherein the introduction rate of vinyl acetate is 3100 kg / h, and the introduction rate of catalyst solution is 698.03 kg / h, and the feed molar ratio of synthesis gas to vinyl acetate in the reactor is maintained at about 1.83:1; a part of the bottom liquid phase L1-1 in the first reaction unit 1 is cooled to 45°C and then returned to the first reaction unit 1, and the other part L1-2 is fed to the first separation unit 3, and the ratio of the liquid phase L1-1 returned to the first reaction unit 1 to the total extracted liquid phase L1 from the bottom of the first reaction unit is 0.17.

[0062] The liquid phase component L2 obtained from the first separation unit 3 is sent to the second separation unit 4 for separation, wherein the top temperature of the second separation unit 4 is 95.3°C, the bottom temperature is 116.4°C, the pressure is 25kPa, the number of plates is 23, and part of the crude acetoxypropionaldehyde product is refluxed at the top of the tower, and the reflux ratio is 1, so that the crude acetoxypropionaldehyde product and unreacted vinyl acetate are mainly extracted from the top of the tower, and the top extraction rate is 4430.38kg / h. The catalyst solution 5 is extracted from the bottom of the second separation unit 4, and the extraction rate is 841kg / h. The extracted catalyst solution is partially or completely returned to the first reaction unit 1 and sent to the second reaction unit 2 as a catalyst solution as needed, at 698.03kg / h and 142.97kg / h, respectively, and the remaining part is discharged for recovery.

[0063] The liquid phase L3 extracted from the top of the second separation unit 4 is sent to the third separation unit 14. The top temperature of the separation tower in the third separation unit 14 is 59.9°C, the bottom temperature is 97°C, the pressure is 25kPa, the number of plates is 18, and the unreacted reactants are refluxed at the top of the tower, and the reflux ratio is 10, so that the unreacted vinyl acetate and the like L4 are extracted from the top of the tower and sent to the second reaction unit 2 to participate in the subsequent reaction, and the extraction rate is 491.87kg / h. The reaction product acetoxypropionaldehyde product is extracted from the bottom of the tower, and the extraction rate is 3935.68kg / h.

[0064] Another stream of synthesis gas S2 (the molar ratio of hydrogen to carbon monoxide in the synthesis gas S2 is 1.27:1) and the produced stream L4 from the top of the third separation unit 14 are fed into the second reaction unit 2, wherein the feeding rate of the stream L4 is 634.84 kg / h, the feeding rate of the synthesis gas S2 is 131 kg / h, and the feeding molar ratio of the synthesis gas S2 of the second reaction unit 2 to the vinyl acetate in the stream L4 is maintained at 3.94:1; the liquid phase L5 at the bottom of the kettle of the second reaction unit 2 is fed into the fourth separation unit 11, the unreacted part of the synthesis gas gas phase G6 is discharged, and the liquid phase L6 is fed into the fifth separation unit 12 (separation tower) for separation;

[0065] The liquid phase component L6 obtained by the fourth separation unit 11 is sent to the fifth separation unit 12 for gas-liquid separation, wherein the top temperature of the fifth separation unit 12 is 59.0°C, the bottom temperature is 89.4°C, the pressure is 25kPa, the number of plates is 23, and part of the light component is refluxed at the top of the tower, and the reflux ratio is 1, so that the light component 16 obtained by the reaction is mainly extracted from the top of the tower, with an extraction rate of 207.56kg / h, and the bottom liquid phase L7 is extracted from the bottom of the fifth separation unit 12, with an extraction rate of 133.02kg / h. All the extracted bottom liquid phase L7 is returned to the second separation unit 4 for further separation.

[0066] The reaction temperature in the first reaction unit 1 is 109°C, the pressure is 6.5 MPa, and the reaction residence time is 70 minutes; the reaction temperature in the second reaction unit 2 is 115°C, the pressure is 7.5 MPa, and the reaction residence time is 90 minutes. The conversion rate of vinyl acetate is 99%, and the yield is 89%.

[0067] Example 3

[0068] The process of Example 1 was followed, except that:

[0069] Vinyl acetate, synthesis gas S1 and catalyst solution (the solvent is 3-acetoxypropionaldehyde, and the amount of rhodium compound in the solution is 14.84% based on HRh(CO)3L) are fed into the first reaction unit 1, wherein the introduction rate of vinyl acetate is 3100 kg / h, and the introduction rate of catalyst solution is 730.4 kg / h, and the feed molar ratio of synthesis gas to vinyl acetate in the reactor is maintained at about 1.17:1; a part of the bottom liquid phase L1-1 in the first reaction unit 1 is cooled to 45°C and then returned to the first reaction unit 1, and the other part L1-2 is fed to the first separation unit 3, and the ratio of the liquid phase L1-1 returned to the first reaction unit 1 to the total extracted liquid phase L1 from the bottom of the first reaction unit is 0.5.

[0070] The liquid phase component L2 obtained from the first separation unit 3 is sent to the second separation unit 4 for separation, wherein the top temperature of the second separation unit 4 is 95.7°C, the bottom temperature is 116.4°C, the pressure is 25kPa, the number of plates is 23, and part of the crude acetoxypropionaldehyde product is refluxed at the top of the tower, and the reflux ratio is 1, so that the crude acetoxypropionaldehyde product and unreacted vinyl acetate are mainly extracted from the top of the tower, and the top extraction rate is 4251.89kg / h. The catalyst solution 5 is extracted from the bottom of the second separation unit 4, and the extraction rate is 880kg / h. The extracted catalyst solution is partially or completely returned to the first reaction unit 1 and sent to the second reaction unit 2 as a catalyst solution as needed, at 730.4kg / h and 149.6kg / h, respectively, and the remaining part is discharged for recovery.

[0071] The liquid phase L3 extracted from the top of the second separation unit 4 is sent to the third separation unit 14. The top temperature of the separation tower in the third separation unit 14 is 62.2°C, the bottom temperature is 96.7°C, the pressure is 25kPa, the number of plates is 18, and the unreacted reactants are refluxed at the top of the tower, and the reflux ratio is 10, so that the unreacted vinyl acetate and the like L4 are extracted from the top of the tower and sent to the second reaction unit 2 to participate in the subsequent reaction, and the extraction rate is 411.81kg / h. The reaction product acetoxypropionaldehyde product is extracted from the bottom of the tower, and the extraction rate is 3837.76kg / h.

[0072] Another stream of synthesis gas S2 (the molar ratio of hydrogen to carbon monoxide in the synthesis gas S2 is 1.28:1) and the produced stream L4 from the top of the third separation unit 14 are fed into the second reaction unit 2, wherein the feeding rate of the stream L4 is 561.41 kg / h, the feeding rate of the synthesis gas S2 is 131 kg / h, and the feeding molar ratio of the synthesis gas S2 of the second reaction unit 2 to the vinyl acetate in the stream L4 is maintained at 6.28:1;

[0073] The liquid phase L5 at the bottom of the second reaction unit 2 is sent to the fourth separation unit 11, the unreacted part of the synthesis gas gas phase G6 is discharged, and the liquid phase L6 is sent to the fifth separation unit 12 (separation tower) for separation;

[0074] The liquid phase component L6 obtained by the fourth separation unit 11 is sent to the fifth separation unit 12 for gas-liquid separation, wherein the top temperature of the fifth separation unit 12 is 55.1°C, the bottom temperature is 88.0°C, the pressure is 25kPa, the number of plates is 23, and part of the light component is refluxed at the top of the tower, and the reflux ratio is 1, so that the light component 16 obtained by the reaction is mainly extracted from the top of the tower, with an extraction rate of 205.09kg / h, and the bottom liquid phase L7 is extracted from the bottom of the fifth separation unit 12, with an extraction rate of 300kg / h. All the extracted bottom liquid phase L7 is returned to the second separation unit 4 for further separation.

[0075] The reaction temperature in the first reaction unit 1 is 101°C, the pressure is 6.5 MPa, and the reaction residence time is 50 min; the reaction temperature in the second reaction unit 2 is 105°C, the pressure is 6.0 MPa, and the reaction residence time is 80 min. The conversion rate of vinyl acetate is 99%, and the yield is 89.1%.

[0076] The embodiments of the present invention have been described above, and the above description is exemplary, not exhaustive, and is not limited to the disclosed embodiments. Many modifications and changes will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments.

Claims

1. A production device for preparing acetoxypropionaldehyde by hydroformylation reaction, comprising a first reaction unit, a first gas-liquid separation system, a second reaction unit, and a second gas-liquid separation system connected in sequence by pipelines, wherein: The liquid phase outlet of the first reaction unit is connected to the material inlet of the first gas-liquid separation system by a pipeline, and a branch is arranged on the pipeline to connect the liquid phase inlet of the first reaction unit. The outlet of the catalyst solution obtained by separation by the first gas-liquid separation system is connected to the first reaction unit and the second reaction unit by a pipeline, and the outlet of the catalyst solution obtained by the second gas-liquid separation system is connected to the first gas-liquid separation system by a pipeline.

2. The production device according to claim 1, characterized in that: The first gas-liquid separation system comprises a first separation unit, a second separation unit, and a third separation unit; and / or, The second gas-liquid separation system includes a fourth separation unit and a fifth separation unit.

3. The production device according to claim 2, characterized in that: The first reaction unit is provided with a raw material inlet, a synthesis gas inlet, an optional hydrogen inlet, a gas phase outlet, and a liquid phase outlet, the gas phase outlet is connected to the first separation unit by a pipeline, the liquid phase outlet is connected to the material inlet of the first separation unit by a pipeline, and a branch is provided on the pipeline to be connected to the material inlet of the first reaction unit; and / or, The first reaction unit is provided with a cooling system, preferably a cooling coil; and / or, The first separation unit is further provided with a gas phase outlet and a liquid phase outlet, and the liquid phase outlet is connected to the material inlet of the second separation unit by a pipeline; and / or, The second separation unit is further provided with a liquid phase outlet and a catalyst solution outlet, the liquid phase outlet is connected to the material inlet of the third separation unit by a pipeline, and the catalyst solution outlet is connected to the first reaction unit and the second reaction unit by a pipeline; and / or, The third separation unit is further provided with an unreacted stream outlet and an acetoxypropionaldehyde crude product outlet, and the unreacted stream outlet is connected to the material inlet of the second reaction unit by a pipeline; and / or, The second reaction unit is further provided with a synthesis gas inlet, a gas phase outlet, a liquid phase outlet, and an optional hydrogen inlet, the gas phase outlet is connected to the first separation unit by a pipeline, and the liquid phase outlet is connected to the material inlet of the fourth separation unit by a pipeline; and / or, The second reaction unit is provided with a cooling system, preferably a jacket cooling system; and / or, The fourth separation unit is further provided with a gas phase outlet and a liquid phase outlet, and the liquid phase outlet is connected to the material inlet of the fifth separation unit by a pipeline; and / or, The fifth separation unit is also provided with a light component outlet and a liquid phase outlet, and the liquid phase outlet is connected to the material inlet of the second separation unit by a pipeline.

4. A method for preparing acetoxypropionaldehyde by hydroformylation reaction, which is implemented on the production device for preparing acetoxypropionaldehyde by hydroformylation reaction according to any one of claims 1 to 3.

5. The production method according to claim 4, characterized in that: The production method comprises: reacting raw materials, synthesis gas, catalyst and solvent in a first reaction unit, dividing the obtained liquid phase product into two parts, one part is circulated back to the first reaction unit, and the other part is sent to a first gas-liquid separation system for separation treatment to obtain a crude acetoxypropionaldehyde product, an unreacted logistics and a catalyst solution, the catalyst solution is circulated to the first reaction unit and the second reaction unit, the unreacted logistics is sent to the second reaction unit for further reaction, and the product obtained in the second reaction unit is sent to a second gas-liquid separation system for separation treatment to obtain a light component and a liquid phase component.

6. The production method according to claim 5, characterized in that The production method specifically comprises the following steps: 1) Vinyl acetate, catalyst, synthesis gas S1, and solvent are fed into a first reaction unit for contact reaction, and the gas phase G1 obtained after the reaction is fed into a first separation unit; 2) The liquid phase L1 obtained after the reaction in the first reaction unit is divided into two parts, one part of the liquid phase L1-1 is sent to the liquid phase inlet of the first reaction unit, and the other part of the liquid phase L1-2 is sent to the first separation unit; 3) The liquid phase L1-2 enters the first separation unit, the separated gas phase G2 is discharged, and the liquid phase L2 continues to enter the second separation unit, and is further separated in the second separation unit to obtain the liquid phase L3 and the catalyst solution, and the catalyst solution is circulated to the first reaction unit and the second reaction unit; the liquid phase L3 is sent to the third separation unit to separate the unreacted stream L4 and the crude acetoxypropionaldehyde product; 4) sending the unreacted stream L4 and the synthesis gas S2 to the second reaction unit for contact reaction, and sending the gas phase G5 obtained by the reaction to the first separation unit; 5) The liquid phase L5 obtained after the reaction in the second reaction unit is sent to the fourth separation unit, the separated gas phase G6 is discharged, and the liquid phase L6 continues to enter the fifth separation unit, and is further separated in the fifth separation unit to obtain light components and liquid phase L7. The liquid phase L7 is sent to the second separation unit, and the light components are discharged for recovery.

7. The production method according to claim 6, characterized in that: In the step 1): The synthesis gas S1 is a gas component containing hydrogen and carbon monoxide. Preferably, the molar ratio of hydrogen to carbon monoxide in the synthesis gas S1 is (0.5-6):1; and / or, The molar ratio of vinyl acetate to synthesis gas S1 is 1:(1-23), preferably 1:(1-10); and / or, The catalyst is selected from at least one compound containing a metal component rhodium, preferably L-coordinated tricarbonyl rhodium hydride; and / or, In terms of molar dosage, the amount of the catalyst is 0.3 to 10 mol%, preferably 0.5 to 5 mol%, of vinyl acetate; and / or, The solvent is an acetoxypropionaldehyde compound, preferably acetoxypropionaldehyde; and / or, Based on the total amount of the catalyst and the solvent being 100 wt %, the catalyst is 0.5 to 30 wt %, preferably 10 to 20 wt % of the total amount of the catalyst and the solvent; and / or, The reaction conditions of the first reaction unit are: reaction temperature of 50-150° C., reaction pressure of 0.5-8 MPa; preferably, reaction temperature of 80-130° C., reaction pressure of 0.5-7.5 MPa.

8. The production method according to claim 6, characterized in that: In the step 2), the liquid phase L1-1 recycled to the first reaction unit accounts for 7 to 90% of the liquid phase L1, preferably 10 to 50%; and / or, In the step 3), the catalyst solution circulated to the first reaction unit is 50-99% of the total catalyst solution obtained in the second separation unit, preferably 60-99%; the catalyst solution circulated to the second reaction unit is 1-50% of the total catalyst solution obtained in the second separation unit, preferably 1-40%.

9. The production method according to claim 6, characterized in that: In the step 4): The synthesis gas S2 is a gas component containing hydrogen and carbon monoxide. Preferably, the molar ratio of hydrogen to carbon monoxide in the synthesis gas S2 is (0.5-6):1; and / or, The molar ratio of the synthesis gas S2 to the vinyl acetate in the unreacted stream L4 is (1-23):1, preferably (1-10):1; and / or, In the second reaction unit, the amount of the catalyst is 0.2 to 20 wt%, preferably 1 to 18 wt%, of the vinyl acetate in the unreacted stream L4; and / or The reaction conditions of the second reaction unit are: reaction temperature of 50-150° C., reaction pressure of 0.5-8 MPa; preferably, reaction temperature of 80-130° C., reaction pressure of 0.5-7.5 MPa.

10. The production device for preparing acetoxypropionaldehyde by hydroformylation reaction according to any one of claims 1 to 3 or the production method for preparing acetoxypropionaldehyde by hydroformylation reaction according to any one of claims 4 to 9, and use thereof in preparing acetoxypropionaldehyde by hydroformylation reaction.

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