Hydroformylation reaction device, hydroformylation reaction method and application thereof

Abstract

The invention provides a hydroformylation reaction device, a hydroformylation reaction method and application of the hydroformylation reaction device. Under the hydroformylation condition, vinyl acetate and synthesis gas react in a first reaction unit, an obtained liquid phase part is cooled and then returns to the first reaction unit, the remaining part and another strand of synthesis gas are fed into a second reaction unit for continuous reaction, a liquid phase obtained after continuous reaction enters a gas-liquid separation unit, and the separated synthesis gas is discharged. The liquid phase enters a separation unit for separation, the catalyst, a crude product and the solvent are separated out, and the catalyst and the solvent are circulated back to the first reaction unit and the second reaction unit respectively. According to the hydroformylation reaction method provided by the invention, the catalyst and the solvent are respectively circulated, the return amount of the catalyst and the solvent can be controlled, the catalyst concentration of the two reaction zones can be respectively regulated and controlled, and the retention time and the reaction effect are ensured.

Description

Technical Field

[0001] The invention belongs to the technical field of hydroformylation reaction, and specifically relates to a hydroformylation reaction device, a hydroformylation reaction method and applications thereof. Background Art

[0002] Polytrimethylene terephthalate (PTT) synthesized from 1,3-propylene glycol is a new polyester material that combines the high performance of polyethylene terephthalate (PET) and the easy processing of polybutylene terephthalate (PBT). The current mature industrial processes all have their own shortcomings. The raw material acrolein for the acrolein hydration hydrogenation process developed by Evonik (formerly Degussa) 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 this process, the hydroformylation of vinyl acetate to prepare aldehyde is a key synthesis step. In order to improve the conversion rate of the raw materials, the reaction generally adopts two or more reactors in series. 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, ensure the residence time, and improve the total conversion rate of vinyl acetate. Patents CN102826973, CN86101063, and US5105018 all mention this method, but the catalysts in the above patents are mostly reused in the form of solutions. Patent CN103012089B provides a method for carbonyl synthesis of propylene, which sends the foam components containing catalysts in each reaction unit into a separator, returns part of the obtained gas phase components, and continues to enter the second reaction unit for reaction, and separates the catalyst foam components of the second reaction unit into gas and liquid, and then discharges the gas phase and reuses the liquid phase respectively. This method sets gas-liquid separation equipment for each reaction unit, which increases equipment investment. Summary of the invention

[0004] The present invention provides a hydroformylation reaction device and a hydroformylation reaction method using the device. The technical solution provided by the present invention is applicable to the continuous process of the hydroformylation reaction, wherein the catalyst and the solvent are recycled separately, an inert solvent or a product can be selected as the solvent, and when the product is used as the solvent, the separation energy consumption can be further reduced, the solvent circulation amount can be flexibly controlled to regulate the catalyst concentration, and the separation energy consumption can be saved. Moreover, the present invention sends the gas phase obtained by each reaction unit to the same separation unit for treatment, thereby reducing the number of equipment and simplifying the process flow.

[0005] One of the purposes of the present invention is to provide a hydroformylation reaction device, comprising: a first reaction unit, a second reaction unit, a first separation unit, and a second separation unit connected in sequence by pipelines, wherein a liquid phase circulation branch connected to the first reaction unit is arranged on the pipeline between the first reaction unit and the second reaction unit, the first reaction unit and the second reaction unit are respectively provided with branches connected to the first separation unit, and a catalyst circulation pipeline and a solvent circulation pipeline are arranged between the second separation unit and the first reaction unit and / or the second reaction unit.

[0006] According to the present invention, in the hydroformylation reaction device:

[0007] The first reaction unit is provided with a raw material inlet, a synthesis gas S1 inlet, and an optional hydrogen inlet; the first reaction unit is provided with a cooling system, preferably a cooling coil;

[0008] The second reaction unit is provided with a synthesis gas S2 inlet and an optional hydrogen inlet; the second reaction unit is provided with a cooling system, preferably a jacketed cooling system; the first reaction unit and the second reaction unit can be various synthesis reactors known in the art, as long as the conditions for the hydroformylation reaction are met;

[0009] The first separation unit is provided with a non-condensable gas component discharge pipeline and a liquid component pipeline connected to the second separation unit; the first separation unit can be any separator known in the art, as long as it can effectively separate the non-condensable gas component from the liquid component;

[0010] The second separation unit is provided with a crude product discharge pipeline, a catalyst circulation pipeline, and a solvent circulation pipeline; the second separation unit can be a combination of various separation equipment known in the art, as long as the crude product, the catalyst, and the solvent can be separated; the crude product includes 2-acetoxypropionaldehyde and 3-acetoxypropionaldehyde; the second separation unit is also provided with an oxidizing gas inlet.

[0011] The second object of the present invention is to provide a hydroformylation reaction method, which is implemented on the hydroformylation reaction device provided in the first object of the present invention.

[0012] According to the present invention, the method comprises: reacting the raw material and the synthesis gas in the first reaction unit and the second reaction unit in sequence, and then passing through the first separation unit and the second separation unit in sequence for separation treatment, wherein the liquid product obtained by the reaction in the first reaction unit is partially recycled back to the first reaction unit, and the catalyst and the solvent separated by the second separation unit are respectively recycled back to the first reaction unit and the second reaction unit. Further, the hydroformylation reaction method specifically comprises the following steps:

[0013] 1) sending vinyl acetate, synthesis gas S1, catalyst and solvent into the first reaction unit for contact reaction;

[0014] 2) The gas phase component G1 obtained in the first reaction unit is sent to the first separation unit for treatment; the liquid phase component L1 obtained in the first reaction unit is divided into two parts, one part of the liquid phase component L1-1 is sent to the second reaction unit to continue to contact and react with the synthesis gas S2, and the other part of the liquid phase component L1-2 is circulated back to the first reaction unit;

[0015] 3) The gaseous component G2 obtained by the reaction in the second reaction unit is sent to the first separation unit for treatment; the liquid component L2 obtained by the second reaction unit enters the first separation unit, the separated gas G3 is discharged, and the separated liquid component L3 is sent to the second separation unit;

[0016] 4) Passing the oxidizing gas S3 into the second separation unit to precipitate the catalyst, separating the catalyst and the liquid phase, and further separating the separated liquid phase to obtain a crude product and a solvent, wherein the separated catalyst is circulated to the first reaction unit and the second reaction unit, and the obtained solvent is circulated to the first reaction unit and the second reaction unit.

[0017] According to the present invention, in step 1) of the hydroformylation reaction method:

[0018] The synthesis gas S1 can be synthesis gas of various specifications in the art. Preferably, 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 (0.5-5):1, preferably (0.5-3):1; in step 1), in the continuous industrial production process, hydrogen is optionally introduced into the first reaction unit according to the gas composition of the synthesis gas introduced, so as to adjust the ratio of hydrogen to carbon monoxide in the synthesis gas to be within the above range;

[0019] The feed molar ratio of vinyl acetate to synthesis gas S1 is 1:(1-20), 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;

[0020] The catalyst is selected from at least one of compounds containing the metal component cobalt, and can be a cobalt compound and / or complex commonly used in the art; preferably, the catalyst is octacarbonyl cobalt;

[0021] In terms of molar dosage, the amount of the catalyst is 0.5 to 10 mol%, preferably 0.5 to 5 mol% of vinyl acetate;

[0022] The solvent is selected from at least one of aromatic hydrocarbon solvents and acyloxyaldehyde compounds, preferably at least one of toluene, o-dichlorobenzene, and acetoxypropionaldehyde compounds; according to the present invention, the solvent can be an inert medium such as toluene and o-dichlorobenzene, or a solvent containing acetoxypropionaldehyde compounds, such as 3-acetoxypropionaldehyde, or a mixture containing 2-acetoxypropionaldehyde and 3-acetoxypropionaldehyde, wherein the mixture containing 2-acetoxypropionaldehyde and 3-acetoxypropionaldehyde can directly use the crude product of the hydroformylation reaction; according to a specific embodiment of the present invention, the solvent is most preferably a solvent containing acetoxypropionaldehyde compounds (3-acetoxypropionaldehyde, or a mixture containing 2-acetoxypropionaldehyde and 3-acetoxypropionaldehyde);

[0023] The catalyst content is 1 to 30 wt %, preferably 10 to 20 wt %, based on the total weight of the catalyst and the solvent;

[0024] 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 1-7 MPa.

[0025] According to the present invention, in step 2) of the hydroformylation reaction method:

[0026] In the step of sending the gas phase component G1 obtained by the first reaction unit to the first separation unit for treatment, the gas phase component G1 can be directly sent to the first separation unit for treatment, or the gas phase component G1 can be first cooled and then subjected to gas-liquid separation, and the separated liquid phase is sent to the first separation unit for treatment, for example, the liquid phase after gas-liquid separation is cooled to 20-80° C. and sent to the first separation unit;

[0027] The liquid component L1-2 circulated to the first reaction unit accounts for 10 to 90% of the liquid component L1, preferably 10 to 50%; preferably, the liquid component L1-2 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 component L1-2 after cooling is 20 to 100° C., preferably 40 to 100° C.;

[0028] The synthesis gas S2 can be synthesis gas of various specifications in the art. Preferably, 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 (0.5-5):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.

[0029] The feed molar ratio of vinyl acetate to synthesis gas S2 in the liquid phase component L1-1 is 1:(1-20), preferably 1:(1-10), wherein the molar amount of synthesis gas S2 is calculated based on the total molar amount of hydrogen and carbon monoxide therein;

[0030] The reaction conditions of the second reaction unit are: reaction temperature of 50-150° C., reaction pressure of 0.5-8 MPa. Preferably, the reaction temperature is 80-130° C., and the reaction pressure is 1-7 MPa.

[0031] According to the present invention, in step 3) of the hydroformylation reaction method:

[0032] In the step of sending the gas phase component G2 obtained by the second reaction unit to the first separation unit for treatment, the gas phase component G2 can be directly sent to the first separation unit for treatment, or the gas phase component G2 can be first cooled and then subjected to gas-liquid separation, and the separated liquid phase is sent to the first separation unit for treatment, for example, the liquid phase after gas-liquid separation is cooled to 20-80° C. and sent to the first separation unit;

[0033] 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 0.5 to 2.5 MPa, cooling separation at 20 to 80°C, or a combination thereof. The gas G3 obtained after separation mainly comprises unreacted synthesis gas and low-boiling point by-products such as acetic acid, ethyl acetate, ethylene, etc.; the liquid component L3 mainly comprises reaction products 2-acetoxypropionaldehyde and 3-acetoxypropionaldehyde, catalysts, solvents, etc.

[0034] According to the present invention, in step 4) of the hydroformylation reaction method:

[0035] The oxidizing gas S3 is a gas atmosphere containing oxygen. Preferably, the oxygen content in the oxidizing gas is 0.5-25 wt %; specifically, it can be air, oxygen, or a mixed gas containing the above gases; an excess of oxidizing gas is introduced into the second separation unit to precipitate the catalyst and separate it from the product system; the amount of the oxidizing gas is not particularly limited, as long as the catalyst can be completely precipitated and recovered. For example, the molar ratio of the oxidizing gas S3 to the catalyst is 1-100, preferably 1-90, wherein the molar amount of the oxidizing gas is calculated based on the molar amount of oxygen therein;

[0036] The operation process of the second separation unit is not particularly limited, and a separation method commonly used in the art can be used. Specifically, the liquid phase component L3 enters the second separation unit, and an excess of oxidizing gas is introduced to precipitate the catalyst. When the solvent used is an acetoxypropionaldehyde compound, a portion of the liquid phase obtained after filtering the catalyst is directly separated and circulated to the first reaction unit and the second reaction unit as a solvent, and the other portion is used as a crude product of the hydroformylation reaction; when the solvent used is an aromatic hydrocarbon solvent, the liquid phase obtained after filtering the catalyst is further separated by a separation tower to obtain a solvent and a crude product of the hydroformylation reaction, and the separated solvent can be partially or completely circulated to the first reaction unit and the second reaction unit for use, wherein the separation tower equipment can adopt the separation tower equipment and operating conditions commonly used in the art; wherein the second separation unit can adopt a separation tower with a top temperature of 80 to 120°C, a bottom temperature of 90 to 150°C, a pressure of 10 to 200 KPa, and a plate number of 5 to 40;

[0037] The recycled catalyst is 0.5-20wt% of the total weight of the recycled catalyst and the solvent, preferably 1-18wt%, wherein the recycled catalyst is the total amount of the catalyst circulated to the first reaction unit and the second reaction unit, and the recycled solvent is the total amount of the solvent circulated to the first reaction unit and the second reaction unit;

[0038] The catalyst obtained from the second separation unit is circulated to the first reaction unit and the second reaction unit. The ratio of the catalyst circulation amount is not particularly limited and can be adjusted within a wide range. Preferably, the catalyst circulated to the first reaction unit is 50-99% of the total amount of the catalyst obtained from the second separation unit, preferably 60-99%; the catalyst circulated to the second reaction unit is 1-50% of the total amount of the catalyst obtained from the second separation unit, preferably 1-40%; the circulated catalyst can be partially or completely returned to the first reaction unit and the second reaction unit according to actual needs, and the remaining part is discharged for recovery;

[0039] The solvent obtained from the second separation unit is circulated to the first reaction unit and the second reaction unit. The ratio of the solvent circulation amount is not particularly limited and can be adjusted within a wide range. Preferably, the solvent circulated to the first reaction unit is 50-99% of the total amount of the solvent obtained from the second separation unit, preferably 60-99%; the solvent circulated to the second reaction unit is 1-50% of the total amount of the solvent obtained from the second separation unit, preferably 1-40%; the circulated solvent can be partially or completely returned to the first reaction unit and the second reaction unit according to actual needs, and the remaining part is discharged for recovery.

[0040] The third object of the present invention is to provide the use of the hydroformylation reaction device described in the first object of the present invention or the hydroformylation reaction method described in the second object of the present invention in the preparation of aldehyde compounds.

[0041] The technical solution provided by the present invention is applicable to the continuous industrial production operation of the hydroformylation reaction. During the initial reaction, an appropriate amount of catalyst and solvent are added to the first reaction unit. During the continuous production process, the catalyst is precipitated by passing an excessive amount of oxidizing gas into the second separation unit, and then the catalyst and solvent separated by the second separation unit are adjusted to an appropriate circulation ratio and circulated to the first reaction unit and the second reaction unit respectively, so as to regulate the catalyst concentration of the two reaction zones and improve the conversion efficiency of the reactants. Therefore, during the continuous production process, the reaction raw materials (vinyl acetate) and synthesis gas can be added to the first reaction unit and the second reaction unit in a timely manner to ensure the residence time of the reactants and the reaction effect.

[0042] The hydroformylation reaction device or the hydroformylation reaction method provided by the present invention provides a plurality of reaction units and a gas-liquid separation unit, reasonably arranges the material flow direction, saves energy consumption, improves the yield of the raw material vinyl acetate, realizes the recycling of the catalyst and the solvent, and is suitable for the continuous industrial production of aldehyde compounds. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] Figure 1 This is a schematic diagram of a hydroformylation reaction device used in an embodiment of the present invention.

[0044] Description of reference numerals:

[0045] 1-first reaction unit, 2-second reaction unit, 3-first separation unit, 4-second separation unit, 5-oxidation gas S3 pipeline, 6-crude product discharge pipeline, 7-synthesis gas S1 pipeline, 8-raw material pipeline, 9-hydrogen pipeline, 10-synthesis gas S2 pipeline, 11-liquid component L1-2 circulation pipeline, 12-catalyst circulation pipeline, 13-solvent circulation pipeline. DETAILED DESCRIPTION

[0046] 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.

[0047] 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.

[0048] The hydroformylation reaction device used in the embodiment of the present invention is as follows Figure 1As shown, it includes a first reaction unit 1, a second reaction unit 2, a first separation unit 3, and a second separation unit 4 connected in sequence by pipelines. A liquid phase circulation branch 11 connected to the first reaction unit 1 is arranged on the pipeline between the first reaction unit 1 and the second reaction unit 2, and a catalyst circulation pipeline 12 and a solvent circulation pipeline 13 are arranged between the second separation unit 4 and the first reaction unit 1 and the second reaction unit 2. Among them, the first reaction unit 1 is provided with a raw material inlet 8, a synthesis gas S1 inlet 7, and a hydrogen inlet 9; the second reaction unit 2 is provided with a synthesis gas S2 inlet and a hydrogen inlet 9; the first separation unit 3 is provided with a non-condensable gas component G3 external discharge pipeline, and a liquid phase component L3 pipeline connected to the second separation unit 4, the second separation unit 4 is provided with a crude product external discharge pipeline 6, a catalyst circulation pipeline 12, and a solvent circulation pipeline 13; the second separation unit 4 is also provided with an oxidation gas inlet 5; the first reaction unit 1 is provided with a gas phase component G1 pipeline connected to the first separation unit 3; the second reaction unit 2 is provided with a gas phase component G2 pipeline connected to the first separation unit 3.

[0049] The following is combined with Figure 1 The present invention is described in further detail:

[0050] 1) under hydroformylation conditions, vinyl acetate (containing a hydroformylation catalyst) 8, optional hydrogen 9 and synthesis gas 7 are fed into a first reaction unit 1 for contact reaction, and a gas phase component G1 in the reaction product is fed into a first separation unit 3;

[0051] 2) The product liquid phase L1 in the first reaction unit 1 (including the hydroformylation catalyst, the reaction product, and the unreacted reactants) is divided into two parts, one part L1-1 is sent to the second reaction unit 2 for reaction, and the other part L1-2 is circulated back to the first reaction unit 1 as a liquid phase product to control the temperature of the first reaction unit;

[0052] 3) Part of the liquid phase L1-1 of the first reaction unit 1 is fully contacted and reacted with the optional hydrogen 9 and another synthesis gas S2 in the second reaction unit 2, and the gas phase component G2 in the reaction product is sent to the first separation unit 3, and the product liquid phase L2 in the second reaction unit 2 enters the first separation unit 3, and part of the unreacted synthesis gas G3 in the reaction system is discharged, and the liquid phase L3 in the first separation unit 3 is sent to the second separation unit 4;

[0053] 4) After the oxidation gas is introduced into the second separation unit, the catalyst is separated from the liquid phase, and the crude product and the circulating solvent flow are separated from the liquid phase. The catalyst and the circulating solvent are respectively returned to the first reaction unit 1 and the second reaction unit 2 for reuse.

[0054] Example 1

[0055] 2829 kg / h of vinyl acetate, 925.2 kg / h of synthesis gas (the molar ratio of hydrogen to carbon monoxide in the synthesis gas is 1.02:1), 139.72 kg / h of octacarbonyl cobalt catalyst, and 617.13 kg / h of circulating solvent (3-acetoxypropionaldehyde) solution are fed into the first reaction unit 1, and the molar ratio of the synthesis gas to the vinyl acetate in the reactor is maintained at about 2:1. A portion L1-2 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 portion L1-1 is fed into the second reaction unit 2, and the ratio of the liquid phase returned to the first reaction unit 1 to the total liquid phase produced from the first reaction unit is 0.12;

[0056] Another stream of synthesis gas S2 (the molar ratio of hydrogen to carbon monoxide in the synthesis gas is 1:1) and part of the liquid phase L1-1 of the first reaction unit are fed into the second reaction unit 2, wherein the feeding rate of the liquid phase is 4432.29 kg / h, the feeding rate of the synthesis gas is 102.8 kg / h, and the feeding molar ratio of the synthesis gas to vinyl acetate of the second reaction unit 2 is maintained at 2:1;

[0057] The gas phase G1 fed into the first reaction unit is combined with the gas phase G2 fed into the second reaction unit, cooled to 39°C, and then subjected to gas-liquid separation. The separated liquid phase and the product liquid phase L2 of the second reaction unit 2 are fed into the first separation unit 3, depressurized to 1.0 MPa for flash evaporation, and the unreacted partial synthesis gas gas phase G3 is separated and discharged, and the liquid phase L3 is fed into the second separation unit 4 for separation;

[0058] In the second separation unit 4, 100 kg / h of air is introduced into the liquid phase component L3 obtained in the first separation unit 3, and the catalyst and the liquid phase are separated by centrifugation. The liquid phase is separated by the second separation unit 4 (separation tower). The separation tower has 23 plates, an operating pressure of 20 Kpa, a reflux ratio of 1, and 685.7 kg / h of 3-acetoxypropionaldehyde is extracted from the bottom of the tower as a solvent cycle, and 3647.15 kg / h is extracted from the top of the tower as a crude product. The extracted solvent is partially or completely returned to the first reaction unit 1 and the second reaction unit 2 as needed, which are 617.13 kg / h and 68.57 kg / h respectively, and the remaining part is discharged for recovery. The separated catalyst is partially or completely returned to the first reaction unit 1 and the second reaction unit 2 as needed, which are 139.72 kg / h and 15.52 kg / h respectively, and the remaining part is discharged for recovery.

[0059] The reaction temperature in the first reaction unit 1 and the second reaction unit 2 is 109°C and the pressure is 6.5 MPa. The residence time in the first reaction unit is 60 minutes and the residence time in the second reaction unit is 70 minutes. The conversion rate of vinyl acetate is 99% and the yield is 89.7%.

[0060] Example 2

[0061] The process of Example 1 was followed, except that:

[0062] 2829kg / h of vinyl acetate, 964kg / h of synthesis gas S1 and 132.62kg / h of catalyst are fed into the first reaction unit 1 with 657kg / h of solution of a part of the hydroformylation reaction product obtained in the continuous production process as a circulating solvent (containing 2-acetoxypropionaldehyde and 3-acetoxypropionaldehyde), and the molar ratio of the synthesis gas to the vinyl acetate in the reactor is maintained at about 2:1; a part of the bottom liquid phase L1-2 in the first reaction unit 1 is cooled to 45°C and then returned to the first reaction unit 1, and the other part L1-1 is fed into the second reaction unit 2, and the ratio of the liquid phase L1-2 returned to the first reaction unit 1 to the total liquid phase L1 produced from the first reaction unit is 0.20;

[0063] Another stream of synthesis gas S2 (the molar ratio of hydrogen to carbon monoxide in the synthesis gas S2 is 1:1) and part of the liquid phase L1-1 of the first reaction unit 1 are fed into the second reaction unit 2, wherein the feeding rate of the liquid phase L1-1 is 4454.9 kg / h, the feeding rate of the synthesis gas S2 is 107.2 kg / h, and the feeding molar ratio of the synthesis gas S2 of the second reaction unit 2 to the vinyl acetate in L1-1 is 2.95:1;

[0064] The gas phase G1 fed into the first reaction unit is combined with the gas phase G2 fed into the second reaction unit, cooled to 39°C, and then subjected to gas-liquid separation. The separated liquid phase and the product liquid phase L2 of the second reaction unit 2 are fed into the first separation unit 3, depressurized to 1.0 MPa for flash evaporation, and the unreacted partial synthesis gas gas phase G3 is separated and discharged, and the liquid phase L3 is fed into the second separation unit 4 for separation;

[0065] In the second separation unit 4, 150 kg / h of air is introduced into the liquid phase component L3 obtained by the gas-liquid separation unit 3, and the catalyst and the liquid phase are separated by centrifugation. A portion of 780 kg / h of the liquid phase is separated, and the light components are removed by the separation tower. The separation tower has 23 plates, an operating pressure of 0.05 MPa, a reflux ratio of 20, and 730 kg / h of the tower bottom is extracted as a solvent cycle, and another portion of 3626.95 kg / h is used as a crude product. The extracted solvent is partially or completely returned to the first reaction unit 1 and the second reaction unit 2 as needed, which are 657 kg / h and 73 kg / h respectively, and the remaining part is discharged for recovery. The separated catalyst is partially or completely returned to the first reaction unit 1 and the second reaction unit 2 as needed, which are 132.61 kg / h and 14.73 kg / h respectively, and the remaining part is discharged for recovery.

[0066] The reaction temperature in the first reaction unit 1 and the second reaction unit 2 is 112°C and the pressure is 6.0 MPa. The residence time in the first reaction unit is 60 minutes and the residence time in the second reaction unit is 70 minutes. The conversion rate of vinyl acetate is 99% and the yield is 89.5%.

[0067] Example 3

[0068] 2829 kg / h of vinyl acetate, 934 kg / h of synthesis gas (the molar ratio of hydrogen to carbon monoxide in the synthesis gas is 1.16:1), 77.84 kg / h of octacarbonyl cobalt catalyst, and 636.96 kg / h of circulating solvent (3-acetoxypropionaldehyde) solution are fed into the first reaction unit 1, and the molar ratio of the synthesis gas to the vinyl acetate in the reactor is maintained at about 2.02:1. A portion L1-2 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 portion L1-1 is fed into the second reaction unit 2, and the ratio of the liquid phase returned to the first reaction unit 1 to the total liquid phase produced from the first reaction unit is 0.50;

[0069] Another stream of synthesis gas S2 (the molar ratio of hydrogen to carbon monoxide in the synthesis gas is 1.16:1) and part of the liquid phase L1-1 of the first reaction unit are fed into the second reaction unit 2, wherein the feeding rate of the liquid phase is 4392.2 kg / h, the feeding rate of the synthesis gas is 103.8 kg / h, and the feeding molar ratio of the synthesis gas to vinyl acetate of the second reaction unit 2 is maintained at 4.96:1;

[0070] The gas phase G1 fed into the first reaction unit is combined with the gas phase G2 fed into the second reaction unit, cooled to 45°C, and then subjected to gas-liquid separation. The separated liquid phase and the product liquid phase L2 of the second reaction unit 2 are fed into the first separation unit 3, depressurized to 1.0 MPa for flash evaporation, and the unreacted partial synthesis gas gas phase G3 is separated and discharged, and the liquid phase L3 is fed into the second separation unit 4 for separation;

[0071] In the second separation unit 4, 300 kg / h of air is introduced into the liquid phase component L3 obtained in the first separation unit 3, and the catalyst and the liquid phase are separated by centrifugation. The liquid phase is separated by the second separation unit 4 (separation tower). The separation tower has 23 plates, an operating pressure of 20 Kpa, a reflux ratio of 1, and 749.37 kg / h of 3-acetoxypropionaldehyde is extracted from the bottom of the tower as a solvent cycle, and 3655.02 kg / h is extracted from the top of the tower as a crude product. The extracted solvent is partially or completely returned to the first reaction unit 1 and the second reaction unit 2 as needed, which are 636.96 kg / h and 112.41 kg / h respectively, and the remaining part is discharged for recovery. The separated catalyst is partially or completely returned to the first reaction unit 1 and the second reaction unit 2 as needed, which are 77.84 kg / h and 13.74 kg / h respectively, and the remaining part is discharged for recovery.

[0072] The reaction temperature in the first reaction unit 1 is 109°C and the pressure is 6.5 MPa, and the reaction temperature in the second reaction unit 2 is 105°C and the pressure is 5.5 MPa. The residence time in the first reaction unit is 80 minutes, and the residence time in the second reaction unit is 90 minutes. The conversion rate of vinyl acetate is 99%, and the yield is 89.9%.

[0073] 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 hydroformylation reaction device, comprising: A first reaction unit, a second reaction unit, a first separation unit, and a second separation unit are connected in sequence by pipelines, wherein a liquid phase circulation branch connected to the first reaction unit is arranged on the pipeline between the first reaction unit and the second reaction unit, the first reaction unit and the second reaction unit are respectively provided with branches connected to the first separation unit, and a catalyst circulation pipeline and a solvent circulation pipeline are arranged between the second separation unit and the first reaction unit and / or the second reaction unit.

2. The hydroformylation reaction device according to claim 1, characterized in that: The first reaction unit is provided with a raw material inlet, a synthesis gas S1 inlet, and an optional hydrogen inlet; and / or, The first reaction unit is provided with a cooling system, preferably a cooling coil; and / or, The second reaction unit is provided with a synthesis gas S2 inlet and an optional hydrogen inlet; and / or, The second reaction unit is provided with a cooling system, preferably a jacketed cooling system.

3. The hydroformylation reaction device according to claim 1, characterized in that: The first separation unit is provided with a non-condensable gas component discharge pipeline and a liquid component pipeline connected to the second separation unit; and / or, The second separation unit is provided with a crude product discharge pipeline, a catalyst circulation pipeline, and a solvent circulation pipeline; and / or, The second separation unit is also provided with an oxidizing gas inlet.

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

5. The hydroformylation reaction method according to claim 4, characterized in that: The method comprises: reacting raw materials and synthesis gas in a first reaction unit and a second reaction unit in sequence, and then passing through a first separation unit and a second separation unit in sequence for separation treatment, wherein a portion of a liquid product obtained by the reaction in the first reaction unit is recycled back to the first reaction unit, and a catalyst and a solvent separated by the second separation unit are recycled back to the first reaction unit and the second reaction unit, respectively.

6. The hydroformylation reaction method according to claim 5, characterized in that: The method specifically comprises the following steps: 1) sending vinyl acetate, synthesis gas S1, catalyst and solvent into the first reaction unit for contact reaction; 2) The gas phase component G1 obtained in the first reaction unit is sent to the first separation unit for treatment; the liquid phase component L1 obtained in the first reaction unit is divided into two parts, one part of the liquid phase component L1-1 is sent to the second reaction unit to continue to contact and react with the synthesis gas S2, and the other part of the liquid phase component L1-2 is circulated back to the first reaction unit; 3) The gaseous component G2 obtained by the reaction in the second reaction unit is sent to the first separation unit for treatment; the liquid component L2 obtained by the second reaction unit enters the first separation unit, the separated gas G3 is discharged, and the separated liquid component L3 is sent to the second separation unit; 4) Passing the oxidizing gas S3 into the second separation unit to precipitate the catalyst, separating the catalyst and the liquid phase, and further separating the separated liquid phase to obtain a crude product and a solvent, wherein the separated catalyst is circulated to the first reaction unit and the second reaction unit, and the obtained solvent is circulated to the first reaction unit and the second reaction unit.

7. The hydroformylation reaction 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 (0.5-5):1; and / or, The feed molar ratio of vinyl acetate to synthesis gas S1 is 1:(1-20), preferably 1:(1-10); and / or, The catalyst is selected from at least one compound containing the metal component cobalt, preferably octacarbonyl cobalt; and / or, In terms of molar dosage, the amount of the catalyst is 0.5 to 10 mol%, preferably 0.5 to 5 mol%, of vinyl acetate; and / or, The solvent is selected from at least one of aromatic hydrocarbon solvents and acyloxyaldehyde compounds, preferably at least one of toluene, o-dichlorobenzene, and acetoxypropionaldehyde compounds; and / or, The catalyst content is 1 to 30 wt%, preferably 10 to 20 wt%, based on the total weight 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 1-7 MPa.

8. The hydroformylation reaction method according to claim 6, characterized in that: In the step 2): The liquid phase component L1-2 recycled to the first reaction unit accounts for 10 to 90%, preferably 10 to 50%, of the liquid phase component L1; and / or, 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 S1 is (0.5-5):1; and / or, The feed molar ratio of vinyl acetate to synthesis gas S2 in the liquid phase component L1-1 is 1:(1-20), preferably 1:(1-10); 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 1-7 MPa.

9. The hydroformylation reaction method according to claim 6, characterized in that: In the step 4): The oxidizing gas S3 is a gas atmosphere containing oxygen, preferably, the oxygen content in the oxidizing gas is 0.5-25wt%; and / or, The molar ratio of the oxidizing gas S3 to the catalyst is 1 to 100, preferably 1 to 90, wherein the molar amount of the oxidizing gas is calculated based on the molar amount of oxygen therein; and / or, The recycled catalyst is 0.5-20 wt %, preferably 1-18 wt % of the total weight of the recycled catalyst and solvent; and / or, The catalyst recycled to the first reaction unit is 50-99%, preferably 60-99%, of the total amount of catalyst obtained in the second separation unit; and / or, The catalyst recycled to the second reaction unit is 1 to 50%, preferably 1 to 40%, of the total amount of catalyst obtained in the second separation unit; and / or, The solvent recycled to the first reaction unit is 50-99%, preferably 60-99%, of the total amount of solvent obtained in the second separation unit; and / or, The solvent recycled to the second reaction unit is 1 to 50%, preferably 1 to 40%, of the total amount of the solvent obtained in the second separation unit.

10. Use of the hydroformylation reaction device according to any one of claims 1 to 3 or the hydroformylation reaction method according to any one of claims 4 to 9 in the preparation of aldehyde compounds.

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