High-carbon olefin hydroformylation continuous circulation process and system

Abstract

The invention relates to a high-carbon olefin hydroformylation continuous cycle process and system, the method comprises the following steps: mixing a catalyst aqueous solution and olefin to obtain a first mixture, the catalyst aqueous solution comprising a rhodium catalyst, a ligand and an aqueous solution of N-methyl pyrrolidone; under the first synthesis gas pressure, the first mixture is subjected to a hydroformylation reaction, and a first reaction solution is obtained; performing phase splitting on the first reaction liquid to obtain a first water phase containing a catalyst water solution and a first organic phase containing crude aldehyde; the first water phase returns to the first mixture for continuous reaction, and the first organic phase is treated to obtain a hydroformylation reaction product. According to the present invention, the aqueous solution of N-methyl pyrrolidone is adopted as the solvent, such that the hydroformylation reaction rate of the long-chain olefin can be improved, the reaction condition is milder, the catalyst phase and the product phase can be well separated after the hydroformylation reaction is completed, and the separated catalyst aqueous solution can be fed into the hydroformylation reaction again so as to achieve the long-chain olefin hydroformylation reaction. And the reaction cost is effectively reduced.

Description

Technical Field

[0001] The invention relates to the technical field of olefin hydroformylation, and in particular to a continuous circulation reaction process and a continuous circulation reaction system for high carbon olefin hydroformylation. Background Art

[0002] Olefin hydroformylation is the reaction of olefins with synthesis gas (CO / H 2 ) is used as a substrate to synthesize an aldehyde with one more carbon. In the olefin hydroformylation reaction, rhodium catalysts have become a widely used catalyst in industrial devices due to their excellent catalytic activity and selectivity. However, the high price of rhodium catalysts requires the separation, recovery, and recycling of rhodium catalysts to be focused on in industrial applications in order to reduce the production cost of olefin hydroformylation reactions.

[0003] Water-soluble rhodium phosphine catalysts are a promising strategy to solve the problem of catalyst separation and recycling. For example, the successful application of water-soluble rhodium phosphine complexes in the industrial production process of propylene hydroformylation to synthesize butyraldehyde (RCH-RP process) shows that the introduction of water-soluble rhodium phosphine complex catalysts into the water / organic two-phase olefin hydroformylation reaction can effectively solve the problem of difficult separation of products and catalysts in homogeneous catalytic systems and achieve continuous separation and recycling of catalysts.

[0004] However, the existing water-soluble rhodium phosphine catalyzed olefin hydroformylation reaction is mainly aimed at low-carbon olefins such as propylene. For high-carbon olefins (>C5), due to their poor solubility in water, the rate of water-soluble rhodium phosphine catalyzed high-carbon olefin hydroformylation reaction is slow, and the reaction temperature is higher, and the loss of rhodium ligand is greater, resulting in the difficulty of industrializing the water-soluble rhodium phosphine catalyzed high-carbon olefin hydroformylation reaction. Summary of the invention

[0005] One object of the present invention is to provide a continuous circulation process for the hydroformylation of high-carbon olefins, which uses nitrogen methyl pyrrolidone that is miscible with water and olefins as a co-solvent, can effectively increase the reaction rate of the hydroformylation of long-chain olefins, and make the reaction conditions milder. At the same time, the catalyst phase and the product phase can be recycled and reused after separation, which effectively reduces the reaction cost and is conducive to industrial application.

[0006] The present invention is achieved through the following technical solutions:

[0007] A continuous cycle process for hydroformylation of higher carbon olefins comprises the following steps:

[0008] Mixing a catalyst aqueous solution and an olefin to obtain a first mixture, wherein the catalyst aqueous solution includes an aqueous solution of a rhodium catalyst, a ligand, and nitrogen-methylpyrrolidone;

[0009] Under a first synthesis gas pressure, the first mixture undergoes a hydroformylation reaction to obtain a first reaction liquid;

[0010] The first reaction liquid is separated into phases to obtain a first aqueous phase containing an aqueous catalyst solution and a first organic phase containing a crude aldehyde;

[0011] The first aqueous phase is returned to the first mixture to continue the reaction, and the first organic phase is treated to obtain a hydroformylation reaction product.

[0012] In the technical scheme, the catalyst aqueous solution used includes a rhodium catalyst, a ligand, and an aqueous solution of nitrogen methyl pyrrolidone. Among them, nitrogen methyl pyrrolidone is also called N-methyl pyrrolidone (NMP). In the catalyst aqueous solution, nitrogen methyl pyrrolidone acts as a co-solvent and acts as an intermediary for mass transfer in the substrate between the organic phase of olefins and the aqueous phase containing the catalyst, thereby effectively improving the hydroformylation reaction rate of long-chain olefins and making the reaction conditions milder. At the same time, nitrogen methyl pyrrolidone will not have side reactions with olefins, aldehydes, and acids.

[0013] In the technical scheme, the rhodium catalyst and the ligand can adopt the existing water-soluble rhodium phosphine catalyst and water-soluble phosphorus ligand. In some preferred embodiments, the rhodium catalyst is at least one of rhodium trichloride, rhodium acetate, rhodium nitrate, tris(triphenylphosphine trisodium meta-sulfonate) carbonyl rhodium hydride, bis(triphenylphosphine trisodium meta-sulfonate) carbonyl rhodium chloride, tris(triphenylphosphine trisodium meta-sulfonate) rhodium chloride and acetylacetonato carbonyl rhodium. In some preferred embodiments, the ligand is at least one of mono(sodium meta-sulfonate phenyl) diphenylphosphine, bis(sodium meta-sulfonate phenyl) phenylphosphine and tris(sodium meta-sulfonate phenyl) phosphine.

[0014] In the technical scheme, after the catalyst aqueous solution and olefin are mixed, the first synthesis gas is used to replace oxygen, and a hydroformylation reaction is carried out under the pressure of the first synthesis gas to obtain a first reaction liquid. Subsequently, the first reaction liquid obtains a first aqueous phase and a first organic phase after phase separation. Among them, the first aqueous phase contains the catalyst aqueous solution and can be directly returned to the first mixture to continue the hydroformylation reaction. The first organic phase mainly contains crude aldehyde containing a hydroformylation reaction product, and the crude aldehyde is treated in subsequent steps to obtain a hydroformylation reaction product.

[0015] In the technical solution, by using an aqueous solution of nitrogen-methylpyrrolidone as a solvent, the hydroformylation reaction rate of long-chain olefins can be increased and the reaction conditions can be made milder. At the same time, after the hydroformylation reaction is completed, the catalyst phase and the product phase can be better separated, eliminating the complicated separation process. The separated catalyst aqueous solution can be put into the hydroformylation reaction again, effectively reducing the cost of the reaction.

[0016] As a preferred embodiment of the catalyst aqueous solution of the present invention, in the aqueous solution of nitrogen-methylpyrrolidone, the mass concentration of nitrogen-methylpyrrolidone is in the range of 30% to 90%.

[0017] As a co-solvent, the higher the mass concentration of nitrogen-methyl pyrrolidone in its aqueous solution, the more conducive it is to the mutual dissolution of the organic phase and the aqueous phase, thereby increasing the rate of the hydroformylation reaction. However, the inventor team found that when the content of nitrogen-methyl pyrrolidone exceeds 90%, the solubility of olefins and aldehydes in the aqueous phase increases, making the separation of the catalyst phase (aqueous phase) and the product phase (organic phase) more difficult. For example, 24.5% of 1-nonanal can be dissolved in 90% of the nitrogen-methyl pyrrolidone aqueous solution. In addition, the inventor team's kinetic experiments also found that when the mass concentration of nitrogen-methyl pyrrolidone in the aqueous solution is less than 30%, the start-up of the olefin hydroformylation reaction requires a certain induction period, which is caused by the mass transfer effect between the gas-liquid-liquid-three phases. When the mass concentration of nitrogen-methyl pyrrolidone is greater than 30%, the mass transfer resistance between the gas-liquid-liquid-three phases can be eliminated to a certain extent, further improving the reaction efficiency. Therefore, in the technical solution, the mass concentration range of nitrogen methyl pyrrolidone is set to 30% to 90%. In some preferred embodiments, the mass concentration range of nitrogen methyl pyrrolidone is 40% to 80%, and further preferably, the mass concentration range of nitrogen methyl pyrrolidone is 60% to 80%. In this range, the catalyst phase and the product phase can be better separated, and the gas-liquid-liquid three-phase can be basically eliminated, thereby significantly improving the catalytic activity.

[0018] In the present technical solution, the use of a co-solvent to promote the mutual dissolution of the aqueous phase and the organic phase can effectively increase the reaction rate of long-chain olefins and obtain milder reaction conditions that are more suitable for industrial applications. However, compared with traditional solvents such as polyethylene glycol and methanol, more rhodium catalyst, for example, 2 ppm, will be immersed in the product phase, causing the loss of rhodium catalyst.

[0019] Therefore, as a preferred embodiment of the present invention, the first organic phase after phase separation is further subjected to washing and extraction treatment to reduce the loss of the water-soluble rhodium catalyst.

[0020] The treatment method of the first organic phase comprises the following steps:

[0021] mixing the first organic phase with the ligand aqueous solution to obtain a second mixture;

[0022] Under a second synthesis gas pressure, the second mixture reacts to obtain a second reaction liquid;

[0023] The second reaction liquid is separated into phases to obtain a second aqueous phase and a second organic phase. The second aqueous phase is returned to the first mixture after treatment to continue the reaction. The second organic phase is a hydroformylation reaction product.

[0024] Through experiments, it is found that the amount of rhodium catalyst recovered is low when the first organic phase is directly washed with deionized water, indicating that the coordination form of rhodium lost to the first organic phase is not completely hydrophilic, but lipophilic to a certain extent. Therefore, in the technical solution, a water-soluble ligand is used to change the coordination form of rhodium in the atmosphere of the second synthesis gas, so that it becomes hydrophilic rhodium again, and then the rhodium catalyst is recovered.

[0025] Specifically, the first organic phase after phase separation is mixed with the ligand aqueous solution to obtain a second mixture. The ligand used in the ligand aqueous solution may be the same as or different from the water-soluble phosphorus ligand used in the hydroformylation reaction. In some preferred embodiments, the ligand is selected from at least one of mono(sodium meta-sulfonate phenyl)diphenylphosphine, di(sodium meta-sulfonate phenyl)phenylphosphine, and tri(sodium meta-sulfonate phenyl)phosphine. More preferably, the ligand is tri(sodium meta-sulfonate phenyl)phosphine.

[0026] After adding the ligand aqueous solution, the second mixture reacts under the pressure of the second synthesis gas, and the coordination form of the rhodium catalyst in the organic phase changes to obtain a hydrophilic rhodium catalyst. Next, the second reaction liquid is phase-separated to obtain a second aqueous phase and a second organic phase. The rhodium catalyst originally present in the organic phase is dissolved in the second aqueous phase after the reaction, and the rhodium catalyst in the second organic phase is greatly reduced. Finally, after the second aqueous phase is treated, it is returned to the first mixture for reaction again, thereby realizing the recovery of the rhodium catalyst.

[0027] In the technical scheme, in view of the characteristics of the catalyst aqueous solution with nitrogen methyl pyrrolidone as a co-solvent, the first organic phase is further treated with a ligand aqueous solution, so that the coordination form of the lipophilic rhodium catalyst contained in the first organic phase is transformed to obtain a hydrophilic rhodium catalyst, which enters the second aqueous phase after phase separation and is finally returned to the first mixture for recycling, thereby greatly improving the recovery rate of the rhodium catalyst, reducing the entrainment of crude aldehyde and the dissolved rhodium catalyst, realizing an efficient and economical production process, and facilitating the industrialization of long-chain olefin hydroformylation reaction.

[0028] Furthermore, in the ligand aqueous solution, the concentration of the ligand is 0.1% to 3.0%. Too high or too low a concentration of the ligand in the ligand aqueous solution will affect the coordination form of the rhodium catalyst. Experimental studies have shown that during extraction, the concentration of the ligand in the ligand aqueous solution is preferably 0.1% to 3.0%, and more preferably 0.5 to 1.5%, so as to reduce the rhodium catalyst in the second organic phase to 24 ppb and achieve efficient recovery of the rhodium catalyst.

[0029] Furthermore, the volume ratio of the first organic phase to the ligand aqueous solution is 1:1 to 1:3. After the ligand of the ligand aqueous solution coordinates a small amount of rhodium in the first organic phase, a water-soluble rhodium phosphine complex is formed, which is insoluble in the first organic phase but soluble in the ligand aqueous solution. If the volume of the ligand aqueous solution is too low, the recovery rate of rhodium in the first organic phase will be low due to the low content of the ligand. However, if the volume of the ligand aqueous solution is too high, although it does not affect the recovery rate, the excess ligand will not only increase the production cost, but also the subsequent concentration treatment of excessive ligand aqueous solution will increase the production energy consumption. Therefore, in the present technical solution, the volume of the ligand aqueous solution needs to be greater than or equal to the volume of the first organic phase to further improve the recovery rate of rhodium. At the same time, considering the amount of ligand and the processing energy consumption, the volume ratio of the first organic phase to the ligand aqueous solution is preferably set to 1:1 to 1:3.

[0030] Furthermore, in the second synthesis gas, H 2 / CO is 0.5 to 2. Through experiments, it is found that H 2 The partial pressure of H and CO also affects the recovery of rhodium from crude aldehyde. 2 When H / CO is 0.5-2, the rhodium content in the second organic phase will drop below 100 ppb. 2 When the partial pressure is 1, the rhodium content in the second organic phase drops below 40 ppb.

[0031] Furthermore, the pressure of the second synthesis gas is 0.5-2.5 MPa. When the pressure of the second synthesis gas is controlled at 0.5-2.5 MPa, the content of rhodium in the second organic phase is 28-54 ppb, and the difference in the amount of rhodium recovered is maintained in a good range. Therefore, in some preferred embodiments, in order to further reduce the production cost, the pressure of the second synthesis gas is set to 0.5-1.0 MPa.

[0032] Further, the second aqueous phase is treated by an evaporator, and the recovered catalyst aqueous solution obtained is returned to the first mixture, and the evaporated water is returned to the second mixture. After the second reaction liquid is separated, the ligand aqueous solution contained in the obtained second aqueous phase contains a large amount of water, and directly returning it to the first mixture will affect the hydroformylation reaction of the first mixture. Therefore, in the present technical solution, an evaporator is used to remove most of the water in the second aqueous phase to obtain a recovered catalyst aqueous solution, and the recovered catalyst aqueous solution is added to the first mixture for hydroformylation reaction. At the same time, the water obtained by evaporation is treated, for example, a ligand is added as a ligand aqueous solution, and then added to the second mixture again, so as to achieve recycling, reduce emissions, and further reduce the cost of the continuous cycle reaction process.

[0033] Another object of the present invention is to provide a continuous circulation system for the hydroformylation of higher carbon olefins, the system comprising:

[0034] A first reactor is used for performing a hydroformylation reaction between a catalyst aqueous solution and olefins under a first synthesis gas pressure to obtain a first reaction liquid, wherein the catalyst aqueous solution comprises a rhodium catalyst, a ligand and an aqueous solution of nitrogen-methylpyrrolidone;

[0035] The first phase separator is used to separate the first reaction liquid into a first aqueous phase and a first organic phase. The first phase separator includes a first outlet end and a second outlet end. The first outlet end is used to output the first aqueous phase to the first reactor, and the second outlet end is used to output the first organic phase.

[0036] In the technical solution, the first reactor can be at least one of a kettle stirred reactor, a non-stirred reactor, a packed tower, a jet loop reactor and a pipeline reactor. The first reactor is used for the hydroformylation reaction of the catalyst aqueous solution and the olefin under the first synthesis gas pressure, wherein the catalyst aqueous solution comprises a rhodium catalyst, a ligand and an aqueous solution of nitrogen methyl pyrrolidone.

[0037] In some embodiments, the reaction time in the first reactor is 0.5 to 6 hours, preferably 1 to 5 hours, and more preferably 2 to 4 hours.

[0038] After the hydroformylation reaction is completed, the first reaction liquid enters the first phase separator to separate into a first aqueous phase and a first organic phase. The first aqueous phase is pumped to the first reactor through the first outlet end to continue the hydroformylation reaction as part of the catalyst aqueous solution. The first organic phase is discharged through the second outlet end to a subsequent treatment device.

[0039] In some embodiments, the first reaction liquid coming out of the first reactor is statically phase-separated in the first phase separator for 0.5 to 5 hours, preferably 1 to 3 hours.

[0040] Furthermore, the high carbon olefin hydroformylation continuous circulation system also includes:

[0041] A second reactor, used for reacting the first organic phase and the ligand aqueous solution under a second synthesis gas pressure to obtain a second reaction solution;

[0042] a second phase separator, used for separating the second reaction liquid into a second aqueous phase and a second organic phase;

[0043] an evaporator, used to process the second aqueous phase into a recovered catalyst aqueous solution and water, the evaporator comprising a third outlet and a fourth outlet, the third outlet being used to output the recovered catalyst aqueous solution to the first reactor, and the fourth outlet being used to output water to the container;

[0044] The container is used to prepare the ligand aqueous solution, adjust the concentration of the ligand aqueous solution, and output the ligand aqueous solution to the second reactor.

[0045] In the technical scheme, the second reactor can be at least one of a kettle stirred reactor, an unstirred reactor, a packed tower, a jet loop reactor and a pipeline reactor. After the first organic phase discharged from the second outlet of the first phase separator enters the second reactor, it is mixed with the ligand aqueous solution and reacted under the second synthesis gas pressure to obtain the second reaction liquid. After the second reaction liquid is statically separated in the second phase separator, the second organic phase on the upper layer is collected to obtain the hydroformylation reaction product, and the second aqueous phase on the lower layer enters the evaporator. After the evaporator removes most of the water in the second aqueous phase, the recovered catalyst aqueous solution is obtained, and the recovered catalyst aqueous solution is circulated to the first reactor through the third outlet, and the water separated by the evaporator is used as a solvent for preparing the ligand aqueous solution and input into the container. Water or ligand can be added to the container according to the concentration requirement of the ligand aqueous solution. After obtaining the ligand aqueous solution of the desired concentration, it is output to the second reactor, or the separated water can be directly circulated back to the second reactor without adding.

[0046] The above-mentioned equipment can improve the reaction rate of long-chain olefins, making the hydroformylation reaction conditions of long-chain olefins milder, and can also be carried out with high activity and high selectivity under lower temperature and pressure conditions than traditional processes; not only that, by setting up a second reactor and an evaporator, the rhodium catalyst in the first organic phase can be converted and recovered, minimizing the loss of rhodium, allowing the catalyst to circulate for a long time at a lower cost, and has excellent industrial application prospects.

[0047] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0048] 1. The present invention uses an aqueous solution of nitrogen-methylpyrrolidone as a solvent, thereby increasing the hydroformylation reaction rate of long-chain olefins and making the reaction conditions milder. At the same time, after the hydroformylation reaction is completed, the catalyst phase and the product phase can be better separated, eliminating the complicated separation process. The separated catalyst aqueous solution can be put into the hydroformylation reaction again, effectively reducing the reaction cost;

[0049] 2. The present invention sets the mass concentration range of nitrogen methyl pyrrolidone to 30% to 90%, so that the catalyst phase and the product phase can be better separated, and the gas-liquid-liquid three-phase can be basically eliminated, thereby significantly improving the catalytic activity;

[0050] 3. The present invention further treats the first organic phase with a ligand aqueous solution, so that the coordination form of the lipophilic rhodium catalyst contained in the first organic phase changes, and a hydrophilic rhodium catalyst is obtained, which enters the second aqueous phase after phase separation, and finally returns to the first mixture for recycling, thereby greatly improving the recovery rate of the rhodium catalyst, reducing the rhodium catalyst entrained and dissolved in the crude aldehyde, realizing an efficient and economical production process, and facilitating the industrialization of the long-chain olefin hydroformylation reaction;

[0051] 4. The continuous circulation process system of the present invention can increase the reaction rate of long-chain olefins, making the hydroformylation reaction conditions of long-chain olefins milder, and can also carry out the hydroformylation reaction with high activity and high selectivity under lower temperature and pressure conditions than traditional processes; not only that, by setting up a second reactor and an evaporator, the rhodium catalyst in the first organic phase can be converted and recovered, minimizing the loss of rhodium, so that the catalyst can be circulated for a long time at a lower cost, and has excellent industrial application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0052] The drawings described herein are used to provide a further understanding of the embodiments of the present invention, constitute a part of this application, and do not constitute a limitation of the embodiments of the present invention. In the drawings:

[0053] Figure 1 It is a flowchart of a continuous cycle process in a specific embodiment of the present invention;

[0054] Figure 2 It is a flowchart of a continuous cycle process in a specific embodiment of the present invention;

[0055] Figure 3 It is a structural schematic diagram of a continuous circulation system in a specific embodiment of the present invention;

[0056] Marks and corresponding parts names in the attached drawings:

[0057] 1-first reactor, 2-first phase separator, 3-second reactor, 4-second phase separator, 5-evaporator, 6-container;

[0058] 10-first reaction liquid, 11-first aqueous phase, 12-first organic phase, 13-ligand aqueous solution, 14-second reaction liquid, 15-product, 16-second aqueous phase, 17-recovered catalyst aqueous solution, 18-water. DETAILED DESCRIPTION

[0059] In order to make the objectives, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with embodiments and drawings. The exemplary embodiments of the present invention and their description are only used to explain the present invention and are not intended to limit the present invention.

[0060] All raw materials of the present invention have no particular restrictions on their sources, and can be purchased on the market or prepared according to conventional methods well known to those skilled in the art. All raw materials of the present invention have no particular restrictions on their purity, and the present invention preferably adopts analytically pure or conventional purity requirements in the field of olefin hydroformylation. All raw materials of the present invention, their brands and abbreviations are conventional brands and abbreviations in the field, and each brand and abbreviation is clear and definite in the field of its related use. Those skilled in the art can purchase them from the market or prepare them by conventional methods according to the brands, abbreviations and corresponding uses.

[0061] Embodiment 1:

[0062] like Figure 1 A continuous cycle process for hydroformylation of high carbon olefins shown comprises the following steps:

[0063] Mixing a catalyst aqueous solution and an olefin to obtain a first mixture, wherein the catalyst aqueous solution includes an aqueous solution of a rhodium catalyst, a ligand, and nitrogen-methylpyrrolidone;

[0064] Under a first synthesis gas pressure, the first mixture undergoes a hydroformylation reaction to obtain a first reaction liquid;

[0065] The first reaction liquid is separated into phases to obtain a first aqueous phase containing an aqueous catalyst solution and a first organic phase containing a crude aldehyde;

[0066] The first aqueous phase is returned to the first mixture to continue the reaction, and the first organic phase is treated to obtain a hydroformylation reaction product.

[0067] In some preferred embodiments, the rhodium catalyst is at least one of rhodium trichloride, rhodium acetate, rhodium nitrate, tris(sodium triphenylphosphine tris-metasulfonate) carbonyl rhodium hydride, bis(sodium triphenylphosphine tris-metasulfonate) carbonyl rhodium chloride, tris(sodium triphenylphosphine tris-metasulfonate) rhodium chloride and acetylacetonato carbonyl rhodium.

[0068] In some preferred embodiments, the ligand is at least one of mono(sodium meta-phenyl sulfonate)diphenylphosphine, di(sodium meta-phenyl sulfonate)phenylphosphine and tri(sodium meta-phenyl sulfonate)phosphine.

[0069] In one or more embodiments, the volume ratio of the catalyst aqueous solution to the olefin is 1:1 to 6:1. If the catalyst aqueous solution is too much, the olefin will dissolve to form a homogeneous phase. If the catalyst aqueous solution is too little, the reaction efficiency will be low. Preferably, the volume ratio of the catalyst aqueous solution to the olefin is 2:1 to 4:1.

[0070] In one or more embodiments, the pressure of the first synthesis gas of the hydroformylation reaction is 0.5-3.5 MPa. Preferably, the pressure of the first synthesis gas is 1.5-2.5 MPa.

[0071] In one or more embodiments, the first synthesis gas includes hydrogen and carbon monoxide, and the volume ratio of hydrogen to carbon monoxide is 1.0-2.0. Preferably, the volume ratio of hydrogen to carbon monoxide is 1.01-1.1.

[0072] In one or more embodiments, the reaction temperature of the hydroformylation reaction is 60-120°C, preferably, the reaction temperature is 70-110°C, and more preferably, the reaction temperature is 85-105°C.

[0073] In one or more embodiments, the content of rhodium catalyst in the catalyst aqueous solution is 20-300 ppm, preferably 30-150 ppm. The concentration of water-soluble phosphorus ligand is 3%-15%, preferably 7%-12%, to obtain higher reaction efficiency.

[0074] In some preferred embodiments, the mass concentration of nitrogen methyl pyrrolidone in the aqueous solution of nitrogen methyl pyrrolidone is in the range of 30% to 90%. In some preferred embodiments, the mass concentration of nitrogen methyl pyrrolidone is in the range of 40% to 80%, and further preferably, the mass concentration of nitrogen methyl pyrrolidone is in the range of 60% to 80%. Within this range, the catalyst phase and the product phase can be better separated, and the gas-liquid-liquid three-phase can be basically eliminated, thereby significantly improving the catalytic activity.

[0075] Embodiment 2:

[0076] On the basis of Example 1, Figure 2 As shown, the treatment method of the first organic phase comprises the following steps:

[0077] mixing the first organic phase with the ligand aqueous solution to obtain a second mixture;

[0078] Under a second synthesis gas pressure, the second mixture reacts to obtain a second reaction liquid;

[0079] The second reaction liquid is separated into phases to obtain a second aqueous phase and a second organic phase. The second aqueous phase is returned to the first mixture after treatment to continue the reaction. The second organic phase is a hydroformylation reaction product.

[0080] In this embodiment, in view of the characteristics of the catalyst aqueous solution with nitrogen-methylpyrrolidone as a co-solvent, the first organic phase is further treated with a ligand aqueous solution, so that the coordination form of the lipophilic rhodium catalyst contained in the first organic phase is transformed to obtain a hydrophilic rhodium catalyst, which enters the second aqueous phase after phase separation and is finally returned to the first mixture for recycling, thereby greatly improving the recovery rate of the rhodium catalyst, reducing the entrainment of crude aldehyde and the dissolved rhodium catalyst, realizing an efficient and economical production process, and facilitating the industrialization of long-chain olefin hydroformylation reaction.

[0081] In some preferred embodiments, the concentration of the ligand in the aqueous ligand solution is 0.1% to 3.0%, and more preferably 0.5 to 1.5%.

[0082] In some preferred embodiments, the volume ratio of the first organic phase to the ligand aqueous solution is 1:1 to 1:3.

[0083] In some preferred embodiments, the second synthesis gas contains H 2 The partial pressure of H is 1-2 MPa. 2 When the partial pressure is 1.5 MPa, the rhodium content in the second organic phase drops below 40 ppb.

[0084] In some preferred embodiments, the pressure of the second synthesis gas is 0.5-2.5 MPa. In one or more embodiments, in order to further reduce the production cost, the pressure of the second synthesis gas is set to 0.5-1.0 MPa.

[0085] In some preferred embodiments, the second aqueous phase is treated by an evaporator, and the recovered catalyst aqueous solution is returned to the first mixture, and the evaporated water is returned to the second mixture. In this embodiment, the evaporator is used to remove most of the water in the second aqueous phase to obtain a recovered catalyst aqueous solution, and the recovered catalyst aqueous solution is added to the first mixture for hydroformylation reaction. At the same time, the evaporated water is treated, for example, a ligand is added as a ligand aqueous solution, and then added to the second mixture again, so as to achieve recycling, reduce emissions, and further reduce the cost of the continuous cycle reaction process.

[0086] Embodiment 3:

[0087] Based on the above embodiments, Figure 3 A high carbon olefin hydroformylation continuous cycle system is shown, comprising:

[0088] A first reactor 1 is used for performing a hydroformylation reaction of a catalyst aqueous solution and olefins under a first synthesis gas pressure to obtain a first reaction liquid, wherein the catalyst aqueous solution comprises a rhodium catalyst, a ligand and an aqueous solution of nitrogen-methylpyrrolidone;

[0089] The first phase separator 2 is used for separating the first reaction liquid into a first aqueous phase and a first organic phase. The first phase separator 2 includes a first outlet end and a second outlet end. The first outlet end is used for outputting the first aqueous phase to the first reactor 1, and the second outlet end is used for outputting the first organic phase.

[0090] In some preferred embodiments, the high carbon olefin hydroformylation continuous cycle system further comprises:

[0091] A second reactor 3, used for reacting the first organic phase and the ligand aqueous solution under a second synthesis gas pressure to obtain a second reaction solution;

[0092] A second phase separator 4, used for separating the second reaction liquid into a second aqueous phase and a second organic phase;

[0093] an evaporator 5, for processing the second aqueous phase into a recovered catalyst aqueous solution and water, the evaporator 5 comprising a third outlet and a fourth outlet, the third outlet being used to output the recovered catalyst aqueous solution to the first reactor 1, and the fourth outlet being used to output water to the container 6;

[0094] The container 6 is used to prepare the ligand aqueous solution, adjust the concentration of the ligand aqueous solution, and output the ligand aqueous solution to the second reactor 3 .

[0095] In one or more embodiments, the temperature of the second reactor is 50-110° C., preferably 60-100° C. In some preferred embodiments, the residence time of the first organic phase and the ligand aqueous solution entering the second reactor is 0.5-2 hours, and the static phase separation time of the second phase separator is 0.5-3 hours, preferably 1-2 hours.

[0096] This embodiment can increase the reaction rate of long-chain olefins, making the hydroformylation reaction conditions of long-chain olefins milder, and can also carry out the hydroformylation reaction with high activity and high selectivity under lower temperature and pressure conditions than the traditional process; moreover, by setting up the second reactor and the evaporator, the rhodium catalyst in the first organic phase can be converted and recovered, thereby minimizing the loss of rhodium, so that the catalyst can be circulated for a long time at a lower cost, and has excellent industrial application prospects.

[0097] Embodiment 4:

[0098] In this example, 1-decene was used as the raw material olefin for the hydroformylation reaction, and the mass concentration of the aqueous solution of nitrogen-methylpyrrolidone was changed to test the effect of different mass concentrations of nitrogen-methylpyrrolidone on the reaction activity.

[0099] The volume of the reactor is 50 mL, and magnetic stirring is adopted. 10 mL of 1-decene and 30 mL of aqueous phase are added to the reactor, wherein the aqueous phase includes [Rh]=150 μg / mL, TPPTS / Rh=60, nitrogen methyl pyrrolidone, and water, wherein the rhodium catalyst is tris(triphenylphosphine tris-sodium metasulfonate) carbonyl rhodium hydride, and the ligand TPPTS is tris(sodium metasulfonate phenyl)phosphine. The reaction temperature is 95°C, the reaction time is 1 hour, the synthesis gas pressure is 2.5 MPa, and the synthesis gas composition is H 2 / CO=1.0~1.1.

[0100] The experimental results are shown in Table 1. The catalytic activity can be effectively improved by increasing the amount of nitrogen methyl pyrrolidone added to the catalyst aqueous solution. When 80% NMP is added, the conversion rate of 1-decene is as high as 98.3% in 30 minutes, and the selectivity of aldehydes reaches 97.3%. Olefin isomerization, hydrogenation, and hydrogenation of aldehydes are all very low, within 2%. Therefore, in some preferred embodiments, depending on the different raw material olefins, the mass concentration range of nitrogen methyl pyrrolidone is preferably 60% to 80%.

[0101] Table 1:

[0102]

[0103]

[0104] Embodiment 5:

[0105] In this example, the hydroformylation activity of various long chain olefins was tested.

[0106] The reactor volume is 50 mL, and magnetic stirring is adopted at a speed of 800 rpm. The reactor is added with 10 mL of raw olefin and 30 mL of aqueous phase, wherein the aqueous phase includes [Rh]=150 μg / mL, TPPTS / Rh=60, 80% of nitrogen methyl pyrrolidone, and 20% of water, wherein the rhodium catalyst is tris(triphenylphosphine tris-sodium meta-sulfonate) carbonyl rhodium hydride, and the ligand TPPTS is tris(sodium meta-sulfonate phenyl)phosphine. The synthesis gas pressure is 2.5 MPa, and the synthesis gas composition is H 2 / CO=1.0~1.1.

[0107] The experimental results are shown in Table 2. The conversion rates of α-olefins from octene to octadecene are all high. Among them, the conversion rate of octadecene can reach about 85% at a relatively low temperature of 105°C for 1 hour. If the reaction time is appropriately extended, the conversion rate can reach more than 95%. Other special olefins such as styrene and dicyclopentadiene also have good reaction activity. It shows that the catalyst aqueous solution with nitrogen methyl pyrrolidone as a co-solvent can significantly increase the reaction rate of long-chain olefin hydroformylation and make the reaction conditions milder.

[0108] Table 2:

[0109]

[0110]

[0111] Embodiment 6:

[0112] This example tests the effect of rhodium concentration on the activity of hydroformylation reaction. The reactor volume is 50mL, magnetic stirring is adopted, and the rotation speed is 800rpm. 10mL of 1-nonene and 30mL of aqueous phase are added to the reactor, and the aqueous phase includes [Rh]=150μg / mL, TPPTS / Rh=60, 80% of nitrogen methyl pyrrolidone, and 20% of water, wherein the rhodium catalyst is tris(triphenylphosphine tris-sodium meta-sulfonate) carbonyl rhodium hydride, and the ligand TPPTS is tris(sodium meta-sulfonate phenyl)phosphine. The reaction temperature is 90°C, the reaction time is 1 hour, the synthesis gas pressure is 2.5MPa, and the synthesis gas composition is H 2 / CO=1.0~1.1.

[0113] Table 3:

[0114]

[0115] The experimental results are shown in Table 3. When the rhodium concentration increases from 30 μg / mL to 300 μg / mL, after 1 hour of reaction, the conversion rate is above 95%. The conversion rate increases slightly with the increase of rhodium concentration, and the selectivity and iso-ratio of aldehydes also do not change much. This shows that the hydroformylation reaction of long-chain olefins can be carried out at a lower rhodium concentration, which is beneficial to reduce the loss of rhodium, reduce the reaction cost, and improve the reaction cycle capacity.

[0116] Embodiment 7:

[0117] This example tests the effect of the first synthesis gas pressure on the activity of the long-chain olefin hydroformylation reaction. The reactor volume is 50 mL, magnetic stirring is used, and the rotation speed is 800 rpm. The reactor is added with 10 mL of 1-octene and 30 mL of aqueous phase, wherein the aqueous phase includes [Rh] = 150 μg / mL, TPPTS / Rh = 60, 80% nitrogen methyl pyrrolidone, and 20% water, wherein the rhodium catalyst is tris (triphenylphosphine tris-sodium metasulfonate) carbonyl rhodium hydride, and the ligand TPPTS is tris (sodium metasulfonate phenyl) phosphine. The reaction temperature is 85 ° C, the reaction time is 1 hour, and the synthesis gas composition is H 2 / CO=1.0~1.1.

[0118] The experimental results are shown in Table 4. When the reaction pressure is between 0.5 MPa and 3.0 MPa, the hydroformylation reaction of 1-octene has good reactivity, the conversion rate is maintained at more than 96%, the selectivity of aldehydes and the normal-iso ratio are also good, and the normal-iso ratio increases slightly with the increase of the reaction pressure, but the increase is not large. It can be seen that the catalyst aqueous solution of this embodiment can make the reaction conditions of long-chain olefins milder, and the pressure of the first synthesis gas can be reduced to 0.5 MPa at most, which is conducive to reducing the cost of the cycle reaction and improving safety.

[0119] Table 4:

[0120]

[0121] Embodiment 8:

[0122] In this example, 1-octene was used as the raw material olefin and a 1L kettle continuous catalytic test was carried out.

[0123] Specifically, 1-octene feed 2.5mL / min, water phase feed 6mL / min, synthesis gas pressure 2.5MPa, reactor is 1L reactor, reactor overflow port corresponding volume 700mL, reactor feed water phase 540mL, phase separator feed water phase 300mL. Water phase composition: [Rh] = 150μg / mL, TPPTS / Rh = 60, 80% NMP, 20% water, rhodium catalyst is tris (triphenylphosphine tris-sulfonate sodium) carbonyl rhodium hydride. The average residence time is about 85min. The reaction temperature is 85℃, and the synthesis gas composition H 2 / CO=1.0-1.1, and the intake air volume is CO / 1-octene=0.9-1.0. After the reaction is completed, the first organic phase in the first phase separator is taken for composition analysis.

[0124] The experimental results are shown in Table 5. The hydroformylation reaction cycle was run for 240 hours, the conversion rate of aldehyde was maintained at about 85%, and the selectivity and normal-to-iso ratio of aldehyde remained basically stable, indicating that the catalytic activity of the catalyst aqueous solution can be well maintained.

[0125] Table 5:

[0126]

[0127] Embodiment 9:

[0128] In this example, the use of an aqueous ligand solution to wash and recover the rhodium catalyst in the crude aldehyde in the second reactor was tested.

[0129] The reaction conditions are 30 mL of TPPTS aqueous solution, 10 mL of crude aldehyde, magnetic stirring at room temperature (20°C-30°C), 800 rpm, 1 hour, then phase separation, and taking the upper layer of crude aldehyde to analyze the rhodium content in the crude aldehyde.

[0130] The content of rhodium in the crude aldehyde before washing is 215ppb. The experimental results are shown in Table 6. Even if a ligand is added to the water, the recovery efficiency of rhodium is only within 10% when a simple washing is carried out at room temperature. Even if the stirring time is extended to 24 hours, the recovery efficiency does not change significantly. This shows that the rhodium catalyst lost into the first organic phase is not caused by incomplete phase separation, but may be caused by a change in coordination form, and the lipophilic rhodium is dissolved in the crude aldehyde.

[0131] Table 6:

[0132]

[0133] Embodiment 10:

[0134] In this embodiment, the temperature and gas atmosphere for recovering rhodium are adjusted, and the amount of rhodium recovered in the crude aldehyde is increased by using the ligand aqueous solution.

[0135] Specifically, the reactor volume was 50 mL, magnetic stirring was used, and the rotation speed was 800 rpm. 30 mL of 1.0% TPPTS aqueous solution was used to wash 10 mL of crude aldehyde, the second synthesis gas pressure was 2.5 MPa, and the composition of the second synthesis gas was H 2 / CO=1.0~1.1. After 1 hour of reaction, the phases were separated and the crude aldehyde in the upper layer was taken to analyze the rhodium content in the crude aldehyde. Before washing with water, the rhodium content in the crude aldehyde was 215 ppb. The washing results are shown in Table 7.

[0136] Table 7:

[0137]

[0138] It can be seen from Table 7 that the recovery rate of rhodium under the syngas atmosphere is significantly higher than that of N 2 Atmosphere. Under the syngas atmosphere, the reaction temperature is selected to be above 70°C, and the extraction is carried out for 1 hour, and the rhodium content in the crude aldehyde can be reduced to less than 50 ppb. It can be seen that the use of ligand aqueous solution, under the syngas pressure, at a temperature of 60-80°C, can effectively improve the recovery rate of rhodium in crude aldehyde.

[0139] Embodiment 11:

[0140] In this example, the effect of different ligand concentrations in the ligand aqueous solution on the recovery of rhodium from crude aldehyde was investigated.

[0141] Specifically, the reactor volume was 50 mL, magnetic stirring was used, and the rotation speed was 800 rpm. 30 mL of TPPTS aqueous solution of different concentrations was used to wash 10 mL of crude aldehyde, the pressure of the second synthesis gas was 2.5 MPa, and the composition of the second synthesis gas was H 2 / CO=1.0~1.1, reaction temperature is 80℃. After 1 hour of reaction, phase separation was carried out, and the upper crude aldehyde was taken to analyze the rhodium content in the crude aldehyde. The rhodium content in the crude aldehyde before water washing was 215ppb. The experimental results are shown in Table 8.

[0142] Table 8:

[0143]

[0144] It can be seen that, in the ligand aqueous solution, when the concentration of the ligand decreases, the recovery rate of rhodium also decreases to a certain extent. Therefore, in some preferred embodiments, in order to ensure the recovery rate of rhodium, the better ligand concentration is 0.5-1.5%.

[0145] Embodiment 12:

[0146] In this example, the effect of the pressure of the second synthesis gas on the recovery of rhodium in crude aldehyde was investigated.

[0147] Specifically, the reactor volume was 50 mL, magnetic stirring was used, and the rotation speed was 800 rpm. 10 mL of crude aldehyde was washed with 30 mL of 0.5% TPPTS aqueous solution, and the composition of the second synthesis gas was H 2 / CO=1.0~1.1, reaction temperature is 80℃. After 1 hour of reaction, phase separation was carried out, and the upper crude aldehyde was taken to analyze the rhodium content in the crude aldehyde. The rhodium content in the crude aldehyde before water washing was 215ppb. The experimental results are shown in Table 9.

[0148] Table 9:

[0149]

[0150] It can be seen from Table 9 that when the pressure of the second synthesis gas is in the range of 0.5 MPa to 2.5 MPa, the extraction results are basically the same. Therefore, the entire extraction process can be controlled at a lower pressure. For example, in some preferred embodiments, the pressure of the second synthesis gas is set to 0.5 to 1.0 MPa.

[0151] Embodiment 13:

[0152] This example discusses the effect of different compositions of the second synthesis gas on the recovery of rhodium in crude aldehyde.

[0153] Specifically, the reactor volume was 50 mL, magnetic stirring was used, and the rotation speed was 800 rpm. 10 mL of crude aldehyde was washed with 30 mL of 0.5% TPPTS aqueous solution, and the total pressure of the second synthesis gas was 3.0 MPa, H 2 The reaction temperature was 80°C. After 1 hour of reaction, the phases were separated and the upper crude aldehyde was taken to analyze the rhodium content in the crude aldehyde. The rhodium content in the crude aldehyde before water washing was 215 ppb. The experimental results are shown in Table 10.

[0154] Table 10:

[0155]

[0156] It can be seen that H 2 Or the partial pressure of CO is too high, the recovery rate of rhodium is not high. Therefore, in some preferred embodiments, H 2 The partial pressure of H is 1 to 2 MPa, more preferably, 2 Or the partial pressure of CO is 1.5 MPa, that is, H 2 When / CO=1.0, the rhodium recovery efficiency is the highest.

[0157] Embodiment 14:

[0158] In this embodiment, the rhodium catalyst in the first organic phase is recovered by using a second reactor, a second phase separator, an evaporator, a container and other devices.

[0159] The reaction conditions were: crude aldehyde (first organic phase) feed 2 mL / min, aqueous phase feed 6 mL / min, second synthesis gas 50 mL / min, H 2 / CO=1.0~1.1, pressure 2.5MPa, reactor is 1L reactor, the reactor overflow port corresponds to a volume of 700mL, 540mL of water phase is added to the reactor, 300mL of water phase is added to the phase separator, and the water phase is 1% TPPTS aqueous solution. The extraction temperature is 90°C, and the average residence time is about 90min. The rhodium content in the crude aldehyde is 215ppb. After the extraction is completed, the oil phase in the phase separator is taken to analyze the rhodium content. The extraction results are shown in Table 11.

[0160] Table 11:

[0161]

[0162]

[0163] It can be seen that after the entire recycling process was continuously operated for 240 hours, the rhodium content in the recovered crude aldehyde was less than 100 ppb. The slight decrease in the amount of recovery in the later period was mainly caused by the partial oxidation of the ligand in the system.

[0164] The terms "first", "second", etc. (e.g., first reactor, second reactor, first phase separator, second phase separator, etc.) used herein are only used to distinguish the corresponding components for the sake of clarity of description, and are not intended to limit any order or emphasize importance, etc. In addition, the term "connected" used herein, unless otherwise specified, may refer to direct connection or indirect connection via other components.

[0165] The specific implementation methods described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above description is only a specific implementation method of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A continuous cycle process for hydroformylation of higher carbon olefins, characterized in that: The following steps are involved: Mixing a catalyst aqueous solution and an olefin to obtain a first mixture, wherein the catalyst aqueous solution includes an aqueous solution of a rhodium catalyst, a ligand, and nitrogen-methylpyrrolidone; Under a first synthesis gas pressure, the first mixture undergoes a hydroformylation reaction to obtain a first reaction liquid; The first reaction liquid is separated into phases to obtain a first aqueous phase containing an aqueous catalyst solution and a first organic phase containing a crude aldehyde; The first aqueous phase is returned to the first mixture to continue the reaction, and the first organic phase is treated to obtain a hydroformylation reaction product.

2. A continuous cycle process for hydroformylation of higher carbon olefins according to claim 1, characterized in that: In the aqueous solution of nitrogen methyl pyrrolidone, the mass concentration of nitrogen methyl pyrrolidone ranges from 30% to 90%.

3. A continuous cycle process for hydroformylation of higher carbon olefins according to claim 1, characterized in that: The treatment method of the first organic phase comprises the following steps: mixing the first organic phase with the ligand aqueous solution to obtain a second mixture; Under a second synthesis gas pressure, the second mixture reacts to obtain a second reaction liquid; The second reaction liquid is separated into phases to obtain a second aqueous phase and a second organic phase. The second aqueous phase is returned to the first mixture after treatment to continue the reaction. The second organic phase is a hydroformylation reaction product.

4. A continuous cycle process for hydroformylation of higher carbon olefins according to claim 3, characterized in that: In the ligand aqueous solution, the concentration of the ligand is 0.1% to 3.0%.

5. A continuous cycle process for hydroformylation of higher carbon olefins according to claim 3, characterized in that: The volume ratio of the first organic phase to the ligand aqueous solution is 1:1 to 1:

3.

6. A continuous cycle process for hydroformylation of higher carbon olefins according to claim 3, characterized in that: In the second synthesis gas, H2 / CO is 0.5-2.

7. A continuous cycle process for hydroformylation of higher carbon olefins according to claim 3, characterized in that: The pressure of the second synthesis gas is 0.5-2.5 MPa.

8. A continuous cycle process for hydroformylation of higher carbon olefins according to claim 3, characterized in that: The second aqueous phase is treated by an evaporator, and the recovered catalyst aqueous solution obtained is returned to the first mixture, and the evaporated water is returned to the second mixture.

9. A continuous circulation system for hydroformylation of higher carbon olefins, characterized in that: include: A first reactor (1) is used for carrying out a hydroformylation reaction between a catalyst aqueous solution and an olefin under a first synthesis gas pressure to obtain a first reaction liquid, wherein the catalyst aqueous solution comprises an aqueous solution of a rhodium catalyst, a ligand and nitrogen methyl pyrrolidone; The first phase separator (2) is used to separate the first reaction liquid into a first aqueous phase and a first organic phase. The first phase separator (2) comprises a first outlet end and a second outlet end. The first outlet end is used to output the first aqueous phase to the first reactor (1), and the second outlet end is used to output the first organic phase.

10. A high carbon olefin hydroformylation continuous circulation system according to claim 9, characterized in that: Also includes: A second reactor (3) is used for reacting the first organic phase and the ligand aqueous solution under a second synthesis gas pressure to obtain a second reaction solution; A second phase separator (4), used for separating the second reaction liquid into a second aqueous phase and a second organic phase; an evaporator (5) for treating the second aqueous phase into a recovered catalyst aqueous solution and water, the evaporator (5) comprising a third outlet and a fourth outlet, the third outlet being used to output the recovered catalyst aqueous solution to the first reactor (1), and the fourth outlet being used to output water to the container (6); The container (6) is used to prepare the ligand aqueous solution, adjust the concentration of the ligand aqueous solution, and output the ligand aqueous solution to the second reactor (3).

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