Production system and method for preparing high-carbon aldehyde through high-carbon olefin carbonyl synthesis

Abstract

The invention discloses a production system and method for preparing high-carbon aldehyde through carbonyl synthesis of high-carbon olefin. The system comprises a reaction device, a separation device, an aldehyde condensing device, a product tank, a polymer supplementing unit and a recycling unit, the polymer supplementing unit is connected with the separating device; the cyclic utilization unit comprises an extraction separation device connected with a liquid phase outlet of the separation device, a polymer recovery device connected with a water phase outlet of the extraction separation device, and a catalyst regeneration device connected with an organic phase outlet of the extraction separation device. According to the method, a carbonyl metal catalytic system is adopted to catalyze reaction of high-carbon olefin and synthesis gas, and heating separation of reaction liquid is performed by introducing an organic polymer protection catalyst; the separated catalyst liquid phase is subjected to water extraction separation and post-treatment, and the organic polymer and the catalyst are recycled. Recycling of the catalyst and efficient separation of the product are realized, and the stability of the catalyst separation section is enhanced.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of carbonyl synthesis method, and particularly relates to a production system and method for preparing high-carbon aldehyde through high-carbon olefin carbonyl synthesis. BACKGROUND

[0002] In the existing industrial production of high-carbon aldehyde prepared through high-carbon olefin carbonyl synthesis, efficient separation of the catalyst from the product and stability of the catalytic system are the core bottlenecks restricting the technical economy. The mainstream process currently adopts a dissolved carbonyl metal complex catalyst (such as a rhodium-phosphite system), and realizes continuous production through continuous carbonyl synthesis and catalyst recycling (such as US4,599,206). However, the process has the following significant defects: (1) Complexity and high cost of the separation process: In order to reduce catalyst loss, the separation of the product aldehyde from the catalyst needs to rely on multi-stage precision separation equipment (such as stripping tower, distillation tower, etc.), which leads to a substantial increase in equipment investment and energy consumption (see US8,404,903, WO2016 / 089602); (2) Severe catalyst activity attenuation: In the separation process, the metal (such as rhodium) is easy to precipitate in the form of metal or cluster, and the organic ligand is also degraded synchronously, which forces frequent addition of catalyst in the production process, significantly increasing the cost; It has been reported that adding a polymer in the evaporation separation stage can improve the catalytic stability, but there are still limitations: US4,774,361 proposes adding a polymer containing a polar group (amide group, ketone group, etc.) to stabilize the catalyst, but such polymers have poor solubility in non-polar reaction systems, and their practical application is limited; CN111344274B reports that a specific polymer can improve the stability of the catalyst, but it does not solve the problem of efficient recovery and recycling of the polymer. Residual polymer will interfere with the reaction system, coordinate with the catalyst, and reduce the reactivity of the catalyst. When the concentration of the polymer is too high, it will change the saturated vapor pressure of the reaction system, making it difficult to vaporize the target product, increasing the difficulty of separation, and the continuous addition of new polymers will lead to cost accumulation and reduce the technical and economic benefits.

[0003] Therefore, it is of urgent significance to develop a carbonyl synthesis process that can efficiently protect the catalyst, simplify the separation, reduce the cost, and realize closed-loop recycling of the polymer, in order to promote the large-scale production of high-carbon aldehyde. SUMMARY

[0004] The application is proposed to solve the problems of poor stability of the catalytic system in the separation process, large loss of the metal and ligand in the catalytic system, and high cost in the prior art, and aims to provide a production system and method for preparing high-carbon aldehyde through high-carbon olefin carbonyl synthesis.

[0005] The application is realized by the following technical solutions: The application discloses a production system for preparing high-carbon aldehyde by high-carbon olefin carbonyl synthesis, which comprises a reaction device, a separation device, an aldehyde condensing device and a product tank connected in sequence, and further comprises a polymer supplement unit and a recycling unit; the polymer supplement unit is connected with the separation device; the recycling unit comprises an extraction separation device connected with a liquid phase outlet of the separation device, a polymer recovery device connected with a water phase outlet of the extraction separation device, and a catalyst regeneration device connected with an organic phase outlet of the extraction separation device; a gas phase outlet or a liquid phase outlet of the polymer recovery device is connected with a water condensing device, and an outlet of the water condensing device is connected with the extraction separation device; a solid phase outlet of the polymer recovery device is connected with the polymer supplement unit; and an outlet of the catalyst regeneration device is connected with the reaction device.

[0006] In the technical scheme, the polymer supplement unit comprises a polymer preparation tank.

[0007] In the technical scheme, the polymer supplement unit further comprises a buffer tank arranged between the polymer preparation tank and the separation device.

[0008] In the technical scheme, a solid phase outlet of the polymer recovery device is connected with the polymer preparation tank.

[0009] In the technical scheme, the polymer preparation tank and the product tank are connected.

[0010] A production method for preparing high-carbon aldehyde by high-carbon olefin carbonyl synthesis by using a production system, which comprises the following steps: S1, a catalyst solution, high-carbon olefin and synthesis gas are respectively introduced into a reaction device, the high-carbon olefin and the synthesis gas are subjected to carbonyl synthesis reaction under the action of the catalyst to generate a reaction liquid containing high-carbon aldehyde product; S2, the reaction liquid of the reaction device is transferred to a separation device, and an organic polymer aldehyde solution is introduced into the separation device; S3, aldehyde gas separated by the separation device is collected after being cooled by an aldehyde condensing device; S4, a liquid phase of the separation device is introduced into an extraction separation device to perform extraction by using water as an extractant; S5, a water phase of the extraction separation device is transferred to an organic polymer recovery device, the organic polymer recovery device converts the organic polymer into a solid state, and the solid-state organic polymer is transferred to a polymer supplement unit for recycling; water vapor or liquid phase water in the organic polymer recovery device is cooled by a water condensing device and then returned to the extraction separation device for recycling; S6, an organic phase of the extraction separation device is transferred to a catalyst regeneration device to perform catalyst activation, and the activated catalyst is returned to the reaction device for recycling.

[0011] In the technical scheme, the reaction temperature of the reaction device is 60-200 DEG C, and the reaction pressure is 0.5-20 MPa; the synthesis gas is a mixture of hydrogen and carbon monoxide, and the molar ratio of hydrogen to carbon monoxide is (0.5-4):1; The catalyst is a rhodium carbonyl catalyst, a cobalt carbonyl catalyst, a catalyst system of rhodium carbonyl catalyst coordinated with an organic ligand or a catalyst system of cobalt carbonyl catalyst coordinated with an organic ligand; the organic ligand is a phosphine ligand or a nitrogen-containing ligand; the phosphine ligand is an alkyl phosphine, an aryl phosphine or a phosphinate; the nitrogen-containing ligand is a monodentate nitrogen-containing ligand, a bidentate nitrogen-containing ligand and a polydentate nitrogen-containing ligand; The solvent of the catalyst solution is a high-carbon aldehyde; the solvent of the catalyst solution is a high-carbon aldehyde consistent with the target product; the high-carbon aldehyde can be nonanal, decanal, undecanal, dodecanal or tridecanal, etc. The concentration of rhodium or cobalt in the catalyst solution is 60-15000 ppm; When the catalyst is a catalyst system of rhodium carbonyl catalyst coordinated with an organic ligand or a catalyst system of cobalt carbonyl catalyst coordinated with an organic ligand, the concentration of the organic ligand in the catalyst solution is 0.5-60%; The molar ratio of the high-carbon olefin to the synthesis gas is (0.1-2):1; The concentration of the catalyst in the reaction system (reaction device) is 60-5000 ppm.

[0012] In the technical scheme, the solute of the organic polymer aldehyde solution is an organic polymer, and the organic polymer is polyvinylpyrrolidone, polyacrylamide, polyethylene glycol, polyvinyl alcohol or polyacrylic acid; The solvent of the organic polymer aldehyde solution is the same as the solvent of the catalyst solution; The mass concentration of the organic polymer in the organic polymer aldehyde solution is 0.01%-20%; The flow rate of the organic polymer aldehyde solution into the separation device is 1%-50% of the flow rate of the reaction liquid of the reaction device into the separation device; The separation conditions of the separation device are that the evaporation temperature is 80-200 DEG C, and the pressure is 0.00001-2 MPa.

[0013] In the technical scheme, the cooling conditions of the aldehyde condensing device are that the cooling temperature is 0-150 DEG C, and the pressure is 0.01-2 MPa; The method for converting the organic polymer into a solid state is evaporation concentration and / or crystallization; The conditions of the evaporation concentration are that the temperature is 80-200 DEG C, and the pressure is 0.01-2 MPa; The crystallization adopts temperature reduction crystallization or constant temperature crystallization; the temperature reduction crystallization is under the condition that the initial temperature is 60-150 DEG C, the final temperature is 5-25 DEG C, and the temperature reduction rate is 1-10 DEG C / h; and the constant temperature crystallization is under the condition that the temperature is 30-80 DEG C.

[0014] In the above technical scheme, the activation condition of the catalyst regeneration device is that the same synthesis gas as in step S1 is introduced into the catalyst regeneration device, and the reaction temperature of the catalyst regeneration device is set to 60-200 DEG C, and the reaction pressure is set to 0.5-20 MPa.

[0015] The present application has the following advantages: The present application provides a production system and method for preparing high-carbon aldehyde from high-carbon olefins by carbonyl synthesis, and the whole process is relatively simple, the organic polymer is added in the evaporation and separation stage to effectively protect the catalyst, reduce the aggregation and evaporation entrainment loss of the catalyst in the separation process, prolong the service life of the catalyst, and reduce the replacement cost of the catalyst; at the same time, water is used for multi-stage extraction and separation to recover the organic polymer, realize the recycling of the organic polymer, inhibit the loss of metal and phosphine complex, and further reduce the production cost; the recycling of the organic polymer realizes the timely removal of the polymer in the reaction system, avoids the accumulation of the polymer in the reaction system, and interferes with the reaction system; the water-soluble polymer selected in the present application has good solvent compatibility and water phase separation characteristics, can significantly inhibit the loss of catalyst metal-phosphine complex, greatly simplify the separation process, reduce complex equipment and operation steps, ensure the stability of the reaction system, significantly improve the production efficiency and technical economy, and has outstanding industrial application value. BRIEF DESCRIPTION OF DRAWINGS

[0016] Figure 1 is a structural schematic diagram of the production system for preparing high-carbon aldehyde from high-carbon olefins by carbonyl synthesis.

[0017] Among them: 1, reaction device; 2, separation device; 3, aldehyde condensing device; 4, extraction and separation device; 5, polymer recovery device; 6, polymer preparation tank; 7, buffer tank; 8, water condensing device; 9, catalyst regeneration device; 10, product tank.

[0018] For ordinary skilled persons in the art, other related drawings can be obtained according to the above drawings without creative labor. DETAILED DESCRIPTION

[0019] In order to enable personnel in the art to better understand the technical scheme of the present application, the technical scheme of the present application will be further described below in combination with the drawings of the specification and through specific embodiments.

[0020] As Figure 1The production system for preparing high-carbon aldehyde by high-carbon olefin carbonyl synthesis includes a reaction device 1, a separation device 2, an aldehyde condensing device 3 and a product tank 10 connected in sequence, and further includes a polymer supplement unit and a recycling unit. The polymer supplement unit includes a polymer preparation tank 6 and a buffer tank 7 connected with each other, and the outlet of the buffer tank 7 is connected with the polymer inlet of the separation device 2. The recycling unit includes an extraction separation device 4 connected with the liquid phase outlet of the separation device 2, a polymer recovery device 5 connected with the water phase outlet of the extraction separation device 4, and a catalyst regeneration device 9 connected with the organic phase outlet of the extraction separation device 4. The gas phase outlet or the liquid phase outlet of the polymer recovery device 5 is connected with a water condensing device 8, and the solid phase outlet of the polymer recovery device 5 is connected with the polymer preparation tank 6; the outlet of the water condensing device 8 is connected with the extraction separation device 4; and the outlet of the catalyst regeneration device 9 is connected with the reaction device 1.

[0021] The reaction device 1 is used for the carbonyl synthesis reaction of high-carbon olefin and synthesis gas under the action of a carbonyl metal catalyst system to generate high-carbon aldehyde; the reaction device 1 adopts a reactor capable of bearing high pressure, and a stirring device is arranged inside the reaction device 1 to ensure that the reactants are fully mixed; the reaction device 1 is equipped with an accurate temperature control system and a pressure monitoring system, and the reaction conditions can be accurately regulated according to the reaction requirements; The reaction device 1 is provided with a high-carbon olefin inlet, a synthesis gas inlet, a catalyst inlet and a reaction liquid outlet. The separation device 2 is used for vaporizing the aldehyde product in the reaction liquid of the reaction device 1, while the catalyst remains in the liquid phase. The separation device 2 is provided with a liquid inlet, a polymer inlet, a gas phase outlet and a liquid phase outlet; the liquid inlet of the separation device 2 is connected with the reaction liquid outlet of the reaction device 1. The separation device 2 is an evaporation separator or a rectification separator. The aldehyde condensing device 3 is used for cooling and liquefying the high-carbon aldehyde gas separated by the separation device 2, so as to be collected subsequently, and is connected with the product tank 10 through a pipeline.

[0022] The product tank 10 is used for collecting the liquid phase high-carbon aldehyde.

[0023] The polymer preparation tank 6 is filled with an aldehyde solution of organic polymer; The polymer preparation tank 6 is connected with the product tank 10 through a pipeline and a valve, so as to realize the mixing and preparation of the polymer solution by introducing part of the high-carbon aldehyde and the polymer; The extraction separation device 4 extracts the organic polymer in the reaction liquid into the water phase through multi-stage extraction, and the catalyst remains in the organic phase, so as to realize the separation of the organic polymer and the catalyst, that is, the extraction separation device 4 separates to obtain the water phase containing the organic polymer and the organic phase containing the catalyst; The extraction separation device 4 adopts a multi-stage extraction tower, and the extractant of the extraction separation device 4 is water; The polymer recovery device 5 is used for recovering the organic polymer from the water phase separated by the extraction separation device 4; The recovery method of the organic polymer in the organic polymer recovery device 5 is evaporation concentration or crystallization; When the recovery method of the organic polymer in the organic polymer recovery device 5 is evaporation concentration, the organic polymer recovery device 5 is an evaporator, the gas phase outlet of the polymer recovery device 5 is connected to the polymer preparation tank 6, the organic polymer solid is dissolved in aldehyde again in the polymer preparation tank 6, and is recycled through the buffer tank 7 for the evaporation separation process of the separation device 2; the water vapor separated from the gas phase outlet of the organic polymer recovery device 5 enters the water condensing device 8 to be cooled into water, and is returned to the extraction separation device 4 to be used as the extractant again; When the recovery method of the organic polymer in the organic polymer recovery device 5 is crystallization, the organic polymer recovery device 5 includes a crystallizer and a filter, the water phase separated by the extraction separation device 4 passes through the crystallizer to obtain solid-phase organic polymer and liquid-phase water; the solid-phase outlet is connected to the polymer preparation tank 6, and the liquid-phase water is cooled by the water condensing device 8 and then returned to the extraction separation device 4 to be used as the extractant again; The catalyst regeneration device 9 is used for activating the catalyst and returning the activated catalyst to the reaction device 1, so as to realize the recycling use of the catalyst.

[0024] The catalyst regeneration device 9 can adopt a reaction kettle, the catalyst regeneration device 9 is provided with a synthesis gas inlet, the synthesis gas enters the catalyst regeneration device 9 to react with the organic phase containing the catalyst transferred from the extraction separation device 4, so as to realize the activation of the catalyst.

[0025] A production method of preparing high-carbon aldehyde from high-carbon olefin carbonyl, comprising the following steps: S1, the catalyst solution, high-carbon olefin and synthesis gas are respectively introduced into the reaction device 1, the high-carbon olefin and the synthesis gas react under the action of the catalyst to generate a reaction liquid containing high-carbon aldehyde product; The reaction temperature of the reaction device 1 is 60-200℃, and the reaction pressure is 0.5-20 MPa; The high-carbon olefin is C6-C20 terminal olefin, internal olefin or linear olefin; The synthesis gas is a mixture of hydrogen and carbon monoxide, and the molar ratio of hydrogen to carbon monoxide is (0.5-4):1; The catalyst is a rhodium carbonyl catalyst, a cobalt carbonyl catalyst, a catalytic system of rhodium carbonyl catalyst coordinated with an organic ligand, or a catalytic system of cobalt carbonyl catalyst coordinated with an organic ligand; The organic ligand is a phosphine ligand or a nitrogen-containing ligand; The phosphine ligand is an alkyl phosphine, an aryl phosphine, or a phosphinate; The alkyl phosphine is trimethyl phosphine, triethyl phosphine, tri-n-butyl phosphine, trihexyl phosphine, or tri-n-octyl phosphine, etc. The aryl phosphine is triphenyl phosphine, diphenyl phosphine, 4-methoxy triphenyl phosphine, 2-diphenyl phosphino biphenyl, or 1,3-bis(diphenyl phosphino)ethane, etc. The phosphinate is triphenyl phosphinate, triethyl phosphite, tributyl phosphite, 2-diphenyl phosphino-1,1'-binaphthyl, or tri(2,4-di-tert-butyl phenyl) phosphite, etc. The nitrogen-containing ligand is a monodentate nitrogen-containing ligand, a bidentate nitrogen-containing ligand, and a polydentate nitrogen-containing ligand; The monodentate nitrogen-containing ligand is ammonia, pyridine, methylamine, or pyrrole, etc. The bidentate nitrogen-containing ligand is ethylenediamine, o-phenanthroline, 2,2'-bipyridine, 8-hydroxyquinoline, or 1,10-phenanthroline, etc. The polydentate nitrogen-containing ligand is ethylenediaminetetraacetic acid, diethylenetriamine, triethylenetetramine, porphyrin, 1,4,7,10-tetraazacyclododecane (cyclododecane tetraamine), etc. The rhodium carbonyl catalyst is acetylacetone dicarbonyl rhodium, rhodium chloride-carbon monoxide complex, or octacarbonyl dirhodium; The cobalt carbonyl catalyst is octacarbonyl dicobalt, tetracarbonyl cobaltate, or hexadecacarbonyl hexacobalt; The preparation method of the rhodium carbonyl catalyst, the cobalt carbonyl catalyst, the catalytic system of rhodium carbonyl catalyst coordinated with an organic ligand, or the catalytic system of cobalt carbonyl catalyst coordinated with an organic ligand is prepared according to CN118289825A, CN111333683B, CN106674285B, and CN102391310B; The concentration of rhodium or cobalt in the catalyst solution is 60 ppm-15000 ppm; When the catalyst is a catalytic system of rhodium carbonyl catalyst coordinated with an organic ligand or a catalytic system of cobalt carbonyl catalyst coordinated with an organic ligand, the concentration of the organic ligand in the catalyst solution is 0.5%-60%; The solvent of the catalyst solution is a high-carbon aldehyde; the high-carbon aldehyde is any one of nonanal, decanal, undecanal, dodecanal, or tridecanal; The molar ratio of the high-carbon olefin to the synthesis gas is 0.1-2:1; The concentration of the catalyst in the reaction system is 60-5000 ppm; S2, the reaction liquid of the reaction device 1 is transferred to the separation device 2, and an organic polymer aldehyde solution is introduced into the separation device 2 at the same time; the catalyst is entrained in the reaction liquid, and the addition of the organic polymer can protect the catalyst and prevent the catalyst from being aggregated and entrained in the evaporation process; The solute of the organic polymer aldehyde solution is an organic polymer; The organic polymer is any one of polyvinylpyrrolidone (PVP), polyacrylamide (PAM), polyethylene glycol (PEG), polyvinyl alcohol (PVA), or polyacrylic acid (PAA); The traditional oil-soluble polymer is affected by its own organic solubility and high boiling point characteristics, and is easy to form a homogeneous system with the circulating reaction liquid, which makes it difficult to realize effective separation and recycling by conventional separation methods such as distillation and filtration, and becomes a key technical bottleneck restricting the continuity and economy of the process; although the traditional oil-soluble polymer can form a homogeneous system with the reaction liquid and can protect the catalyst, it has the technical pain point of difficult separation and recovery; the organic polymer selected by the application is a water-soluble polymer with good solvent compatibility and water phase separation characteristics, which can be dissolved in aldehyde reaction liquid and water phase, effectively inhibits catalyst aggregation and evaporation entrainment loss by forming a homogeneous system, prolongs the service life and reduces the replenishment cost, and realizes efficient separation of the polymer and the circulating reaction liquid by water phase extraction, and realizes recycling of the polymer by evaporation or crystallization process; The solvent of the organic polymer aldehyde solution is the same as the solvent of the catalyst solution; The mass concentration of the organic polymer in the organic polymer aldehyde solution is 0.01%-20%; The flow rate of the organic polymer aldehyde solution introduced into the separation device 2 is 1%-50% of the flow rate of the reaction liquid of the reaction device 1 introduced into the separation device 2; The separation conditions of the separation device 2 are: the evaporation temperature is 80-200°C, and the pressure is 0.00001-2 MPa; S3, the aldehyde gas separated from the separation device 2 is cooled by an aldehyde condensing device 3 and then collected; The cooling conditions of the aldehyde condensing device 3 are: the cooling temperature is 0-150°C, and the pressure is 0.01-2 MPa; S4, the liquid phase of the separation device 2 is introduced into an extraction separation device 4, and water is used as an extractant for extraction; in the extraction process, the organic polymer is dissolved in the water phase, and the catalyst is separated to obtain a water phase rich in organic polymer and an organic phase containing the catalyst; The extraction method is preferably multi-stage countercurrent. The polymer accumulates in the reaction system, the polymer can be coordinated with the catalyst, the reaction activity of the catalyst is reduced, when the concentration of the polymer is too high, the saturated vapor pressure of the reaction system is changed, which causes the difficulty in gasification of the target product, increases the difficulty in separation, and the continuous addition of new polymer will cause the accumulation of cost and reduce the technical and economic benefits; therefore, in the process of the present application, the polymer is timely introduced into the extraction separation device 4 for extraction separation, realizing recycling while avoiding the accumulation of polymer in the reaction system; and avoiding the cost accumulation caused by continuous addition of new polymer, reducing the technical and economic benefits; S5, the water phase of the extraction separation device 4 is transferred to the organic polymer recovery device 5, the organic polymer recovery device 5 converts the organic polymer into a solid state, and the solid organic polymer is transferred to the polymer supplement unit for recycling; the water vapor or liquid phase water in the organic polymer recovery device 5 is cooled by the water condensing device 8 and then returned to the extraction separation device 4 for recycling; The method for converting the organic polymer into a solid state is evaporation concentration and / or crystallization; The evaporation concentration is carried out at a temperature of 80℃ to 200℃ and a pressure of 0.01MPa to 2MPa; The crystallization adopts cooling crystallization or constant-temperature crystallization; The cooling crystallization is carried out at an initial temperature of 60℃ to 150℃, a final temperature of 5℃ to 25℃, and a cooling rate of 1℃ / h to 10℃ / h; The constant-temperature crystallization is carried out at a temperature of 30℃ to 80℃ to maintain a saturated state; S6, the organic phase of the extraction separation device 4 is transferred to the catalyst regeneration device 9, and then synthesis gas is introduced into the catalyst regeneration device 9 for catalyst activation, and the activated catalyst is returned to the reaction device 1 for recycling.

[0026] The activation conditions of the catalyst regeneration device 9 are as follows: the same synthesis gas as in step S1 is introduced into the catalyst regeneration device 9, the reaction temperature of the catalyst regeneration device 9 is set to 60℃ to 200℃, and the reaction pressure is 0.5MPa to 20MPa, which is realized by introducing the synthesis gas.

[0027] Example 1

[0028] A production method for preparing high-carbon aldehyde by carbonyl synthesis of high-carbon olefin, comprising the following steps: S1, high-carbon olefin and synthesis gas, catalyst solution are introduced into reaction device 1 respectively, high-carbon olefin and synthesis gas occur carbonyl synthesis reaction under the action of catalyst, and reaction liquid containing high-carbon aldehyde product is generated; The reaction device 1 is a 5L high-pressure reaction kettle; The reaction temperature of the reaction device 1 is 120℃, and the reaction pressure is 3MPa; The high carbon olefin is 1-octene; the flow rate of the high carbon olefin is 200 mL / h; The synthesis gas is a mixer of hydrogen and carbon monoxide, and the molar ratio of hydrogen to carbon monoxide is 1:1; the flow rate of the synthesis gas is 30 L / h; The catalyst solution takes acetylacetone dicarbonyl rhodium / triphenylphosphine as active ingredients, and the solvent is nonanal, wherein the concentration of rhodium is 600 ppm, and the concentration of triphenylphosphine is 30%; the amount of the catalyst solution added is 1000 mL; S2, the reaction liquid of the reaction device 1 is transferred to the separation device 2, and an organic polymer aldehyde solution is introduced into the separation device 2 at the same time; the catalyst is entrained in the reaction liquid, and the addition of the organic polymer can protect the catalyst and prevent the catalyst from being aggregated and entrained during evaporation; The solute of the organic polymer aldehyde solution is an organic polymer, and the organic polymer is PVP; The solvent of the organic polymer aldehyde solution is an aldehyde solvent, and the aldehyde solvent is nonanal; The mass concentration of the organic polymer in the organic polymer aldehyde solution is 10%; The flow rate of the organic polymer aldehyde solution introduced into the separation device 2 is 20% of the flow rate of the reaction liquid of the reaction device 1 introduced into the separation device 2; The separation condition of the separation device 2 is that the evaporation temperature is 120℃, and the pressure is 0.3 MPa; S3, the aldehyde gas separated by the separation device 2 is collected after being cooled by an aldehyde condensing device 3, The cooling condition of the aldehyde condensing device 3 is that the cooling temperature is 20℃ and the pressure is 0.1 MPa; S4, the liquid phase of the separation device 2 is introduced into an extraction separation device 4, and multi-stage countercurrent extraction is carried out with water as an extractant; in the extraction process, the organic polymer is dissolved in the water phase, and the catalyst is separated to obtain a water phase rich in the organic polymer and an organic phase containing the catalyst; S5, the water phase of the extraction separation device 4 is transferred to an organic polymer recovery device 5, the organic polymer is converted into a solid state, and is transferred to a polymer supplement unit for recycling; the water vapor in the organic polymer recovery device 5 is cooled by a water condensing device 8 and then returned to the extraction separation device 4 for recycling; The method for converting the organic polymer into a solid state is evaporation concentration; The condition of the evaporation concentration is that the temperature is 120℃ and the pressure is 0.1 MPa; S6, the organic phase of the extraction separation device 4 is transferred to a catalyst regeneration device 9, and synthesis gas is introduced into the catalyst regeneration device 9 to activate the catalyst; the activated catalyst is returned to the reaction device 1 for recycling.

[0029] The activation conditions of the catalyst regeneration device 9 are: 120 DEG C, 3 MPa of the synthetic gas, and 2 h of reactivation; The flow rate of the activated catalyst returning to the reaction device 1 is 20 mL / h. The long-period evaluation of 500 h is performed, the average conversion rate of 1-octene is 92%, the average selectivity of nonanal is 94%, and the loss rate of the catalyst is only 0.5%.

[0030] Comparative Example 1 The conditions are the same as those in Example 1, except that the nonanal solution without organic polymers is added in the separation stage.

[0031] The long-period evaluation of 500 h is performed, the average conversion rate of 1-octene is 83%, the average selectivity of nonanal is 90%, and the loss rate of the catalyst is 10%.

[0032] Example 2

[0033] The conditions are the same as those in Example 1, except that the catalytically active component is different, which is octacarbonyldicobalt and triphenylphosphine.

[0034] The long-period evaluation of 500 h is performed, the average conversion rate of 1-octene is 88%, the average selectivity of nonanal is 92%, and the loss rate of the catalyst is 1.5%.

[0035] Comparative Example 2 The conditions are the same as those in Example 2, except that the nonanal solution without organic polymers is added in the separation stage.

[0036] The long-period evaluation of 500 h is performed, the average conversion rate of 1-octene is 77%, the average selectivity of nonanal is 85%, and the loss rate of the catalyst is 20%.

[0037] It can be seen from the above examples that the production system and method for preparing high-carbon aldehydes from high-carbon olefins by carbonylation can effectively realize the recycling use of the catalyst and the efficient separation of the product, reduce the production cost, and has a good industrial application prospect.

[0038] The applicant declares that the above description is only a specific embodiment of the present application, but the protection scope of the present application is not limited thereto, and those skilled in the art should understand that any changes or replacements within the technical scope disclosed by the present application can be easily thought by those skilled in the art, and all fall within the protection scope and disclosure scope of the present application.

Claims

1. A method for preparing high-carbon aldehydes via carbonyl synthesis of high-carbon olefins, characterized in that: Includes the following steps: S1. The catalyst solution, high carbon olefins and synthesis gas are respectively introduced into the reaction device (1). The high carbon olefins and synthesis gas undergo carbonyl synthesis reaction under the action of the catalyst to generate a reaction liquid containing high carbon aldehyde products. S2. Transfer the reaction liquid from the reaction device (1) to the separation device (2), and simultaneously introduce an organic polymer aldehyde solution into the separation device (2); the solute of the organic polymer aldehyde solution is an organic polymer, which is polyvinylpyrrolidone, polyacrylamide, polyethylene glycol, polyvinyl alcohol or polyacrylic acid; S3. The aldehyde gas separated by the separation device (2) is cooled by the aldehyde condenser (3) and then collected. S4. The liquid phase of the separation device (2) is introduced into the extraction separation device (4) and water is used as the extractant for extraction. S5. The aqueous phase of the extraction and separation device (4) is transferred to the organic polymer recovery device (5). The organic polymer recovery device (5) converts the organic polymer into a solid state. The solid organic polymer is transferred to the polymer replenishment unit for recycling. The water vapor or liquid phase water in the organic polymer recovery device (5) is cooled by the water condensation device (8) and returned to the extraction and separation device (4) for recycling. S6. The organic phase of the extraction and separation device (4) is transferred to the catalyst regeneration device (9) for catalyst activation. The activated catalyst is returned to the reaction device (1) for recycling.

2. The method for preparing high-carbon aldehydes by high-carbon olefin carbonyl synthesis according to claim 1, characterized in that: The reaction temperature of the reaction device (1) is 60℃~200℃ and the reaction pressure is 0.5MPa~20MPa; the synthesis gas is a mixture of hydrogen and carbon monoxide, and the molar ratio of hydrogen to carbon monoxide is (0.5~4):

1. The catalyst is a rhodium carbonyl catalyst, a cobalt carbonyl catalyst, a catalytic system in which a rhodium carbonyl catalyst is coordinated with an organic ligand, or a catalytic system in which a cobalt carbonyl catalyst is coordinated with an organic ligand; the organic ligand is a phosphine ligand or a nitrogen-containing ligand; the phosphine ligand is an alkylphosphine, an arylphosphine, or a phosphonite ester; the nitrogen-containing ligand is a monodentate nitrogen-containing ligand, a bidentate nitrogen-containing ligand, or a multidentate nitrogen-containing ligand; The solvent of the catalyst solution is a high-carbon aldehyde that is consistent with the target product; The concentration of rhodium or cobalt in the catalyst solution is 100ppm to 15000ppm; When the catalyst is a catalytic system of rhodium carbonyl catalyst coordinated with organic ligands or a cobalt carbonyl catalyst coordinated with organic ligands, the concentration of organic ligands in the catalyst solution is 0.5% to 60%. The molar ratio of the high-carbon olefins to the syngas is (0.1~2):1; The concentration of the catalyst in the reaction system is 60ppm to 5000ppm.

3. The method for preparing high-carbon aldehydes by carbonyl synthesis of high-carbon olefins according to claim 1, characterized in that: The solvent of the organic polymer aldehyde solution is the same as the solvent of the catalyst solution; The organic polymer aldehyde solution has a mass concentration of 0.01% to 20%; The flow rate of the organic polymer aldehyde solution into the separation device (2) is 1% to 50% of the flow rate of the reaction liquid from the reaction device (1) into the separation device (2); The separation conditions of the separation device (2) are: evaporation temperature of 80℃~200℃ and pressure of 0.00001MPa~2MPa.

4. The method for preparing high-carbon aldehydes by high-carbon olefin carbonyl synthesis according to claim 1, characterized in that: The cooling conditions of the aldehyde condensation device (3) are: cooling temperature of 0℃~150℃ and pressure of 0.01MPa~2MPa; The method for converting the organic polymer into a solid state is evaporation concentration and / or crystallization; The conditions for evaporation and concentration are: temperature of 80℃~200℃ and pressure of 0.01MPa~2MPa; The crystallization is carried out by cooling crystallization or isothermal crystallization; the conditions for cooling crystallization are: initial temperature 60℃~150℃, final temperature 5℃~25℃, and cooling rate 1℃ / h~10℃ / h; the temperature for isothermal crystallization is 30℃~80℃.

5. The method for preparing high-carbon aldehydes by carbonyl synthesis of high-carbon olefins according to claim 1, characterized in that: The activation conditions for the catalyst regeneration device (9) are as follows: the same synthesis gas as in step S1 is introduced into the catalyst regeneration device (9), and the reaction temperature of the catalyst regeneration device (9) is set to 60℃~200℃ and the reaction pressure is 0.5MPa~20MPa.

6. A production system for preparing high-carbon aldehydes by high-carbon olefin carbonyl synthesis using the production method described in any one of claims 1 to 5, comprising a reaction device (1), a separation device (2), an aldehyde condensation device (3), and a product tank (10) connected in sequence, characterized in that: It also includes a polymer replenishment unit and a recycling unit; the polymer replenishment unit is connected to the separation device (2); the recycling unit includes an extraction separation device (4) connected to the liquid phase outlet of the separation device (2), a polymer recovery device (5) connected to the aqueous phase outlet of the extraction separation device (4), and a catalyst regeneration device (9) connected to the organic phase outlet of the extraction separation device (4). The gas phase outlet or liquid phase outlet of the polymer recovery device (5) is connected to a water condensation device (8), and the outlet of the water condensation device (8) is connected to the extraction separation device (4); the solid phase outlet of the polymer recovery device (5) is connected to the polymer replenishment unit; the outlet of the catalyst regeneration device (9) is connected to the reaction device (1).

7. The production system for preparing high-carbon aldehydes by high-carbon olefin carbonyl synthesis according to claim 6, characterized in that: The polymer replenishment unit includes a polymer preparation tank (6).

8. The production system for preparing high-carbon aldehydes from high-carbon olefin carbonyl groups according to claim 7, characterized in that: The polymer replenishment unit also includes a buffer tank (7) disposed between the polymer preparation tank (6) and the separation device (2).

9. The production system for preparing high-carbon aldehydes by high-carbon olefin carbonyl synthesis according to claim 6, characterized in that: The solid phase outlet of the polymer recovery device (5) is connected to the polymer preparation tank (6).

10. The production system for preparing high-carbon aldehydes by high-carbon olefin carbonyl synthesis according to claim 7, characterized in that: The polymer preparation tank (6) and the product tank (10) are connected.

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