Method for synthesizing isononyl alcohol
By using rhodium-based catalysts complexed with two or more phosphine ligands, the isononol synthesis process was optimized, solving the problem of insufficient activity of rhodium-based catalysts and achieving efficient isononol synthesis, which is suitable for large-scale industrial production.
Patent Information
- Application Number
- CN202511191675.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-08-25
- Publication Date
- 2025-12-16
AI Technical Summary
In existing methods for synthesizing isononol, rhodium-based catalysts have insufficient activity in the catalysis of high-carbon-number olefins and require high-pressure environments, resulting in high pressure requirements for equipment and harsh reaction conditions.
Isononanal was prepared by hydroformylation using a rhodium-based catalyst complexed with two or more phosphine ligands, and then converted to isononol under a hydrogenation catalyst. Mixed octene was used as a raw material, and the reaction conditions were optimized to improve the conversion rate and yield.
It improves the conversion rate of mixed octene and the selectivity of isononal, increases the yield of isononol, and has mild reaction conditions, making it suitable for large-scale industrial production and reducing the risk of high pressure.
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Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of organic alcohol synthesis, and particularly relates to a method for synthesizing isononyl alcohol. BACKGROUND
[0002] Isononyl alcohol (INA) is an important plasticizer alcohol, which is mainly used for synthesizing diisononyl phthalate (DINP) and other high molecular weight phthalate plasticizers. DINP has excellent compatibility with polyvinyl chloride (PVC), low volatility, low migration and high plasticizing efficiency, and is significantly superior to traditional dioctyl phthalate (DOP) in performance. In addition, DINP also shows excellent heat resistance, light resistance, aging resistance and electrical insulation. With the deepening of market awareness of DINP safety, as an environmentally friendly plasticizer, it is used as a substitute for low molecular weight phthalate plasticizer, and the market demand shows a rapid growth trend, and is widely used in toy film, wire and cable, automobile manufacturing, floor material, building engineering and other industrial fields, thereby driving the rapid growth of isononyl alcohol market consumption.
[0003] At present, the mainstream production method of isononyl alcohol is to use 1-butene as raw material, generate mixed octene through condensation reaction, prepare isononyl aldehyde through carbonyl synthesis reaction, and finally obtain isononyl alcohol through hydrogenation reaction. In this method, the olefin hydroformylation technology is the core link, and the research and development of the catalyst is the key to the technical breakthrough. In industrial production practice, although cobalt-based catalysts are often used for olefin hydroformylation reaction, they are prone to decomposition due to poor stability, and in order to ensure catalytic activity, the reaction needs to be carried out in a high-pressure environment, which undoubtedly puts high requirements on the pressure resistance of the reaction equipment. At the same time, rhodium-based catalysts have the problem of insufficient activity in the catalytic process of high-carbon number olefins. Therefore, developing a new type of rhodium-based heterogeneous catalyst system has become an urgent need to improve the conversion rate of olefins and optimize the synthesis process of isononyl alcohol. SUMMARY
[0004] The purpose of the present application is to overcome the problem of insufficient activity of rhodium-based catalysts in the catalytic process of high-carbon number olefins in the existing method for synthesizing isononyl alcohol, and to provide a method for synthesizing isononyl alcohol. The method uses mixed octene as raw material, and uses rhodium-based catalysts complexed with two or more phosphine ligands to prepare isononyl aldehyde through hydroformylation reaction. The isononyl aldehyde is then prepared into isononyl alcohol through hydrogenation reaction. The method has the characteristics of high conversion rate of mixed octene, high selectivity and yield of isononyl aldehyde, high yield of isononyl alcohol and mild reaction conditions. The method is simple and convenient to operate, highly meets the needs of large-scale industrial production, and shows significant economic value and broad industrial application prospect.
[0005] In order to achieve the above purpose, the present application provides a method for synthesizing isononyl alcohol, which comprises the following steps: (1) mixing mixed octenes, a rhodium-based catalyst and a phosphine ligand, and then introducing synthesis gas into the obtained mixture to perform a hydroformylation reaction, thereby obtaining iso-nonyl aldehyde; (2) mixing the iso-nonyl aldehyde with hydrogen in the presence of a hydrogenation catalyst to perform a hydrogenation reaction; The phosphine ligand is selected from two or more of triphenyl phosphite, tris(2,4-di-tert-butylphenyl)phosphite, triphenylphosphine, 6,6'-{[5,5'-dimethoxy-3,3'-bis(2-methyl-2-propyl)-2,2'-biphenyldiyl]bis(oxy)}bis[dibenzo(d,f)(1,3,2)dioxaphosphepin] and 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene.
[0006] Preferably, the phosphine ligand comprises a first phosphine ligand and a second phosphine ligand, wherein the first phosphine ligand is selected from at least one of tris(2,4-di-tert-butylphenyl)phosphite, triphenylphosphine and 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, the second phosphine ligand is triphenyl phosphite and / or 6,6'-{[5,5'-dimethoxy-3,3'-bis(2-methyl-2-propyl)-2,2'-biphenyldiyl]bis(oxy)}bis[dibenzo(d,f)(1,3,2)dioxaphosphepin], and the weight ratio of the amount of the first phosphine ligand to the amount of the second phosphine ligand is 1-100:1.
[0007] Preferably, in step (1), the weight ratio of the amount of the mixed octenes to the amount of the rhodium-based catalyst is 1-5:1.
[0008] Preferably, the rhodium-based catalyst is selected from at least one of rhodium trichloride hydrate, acetylacetone dicarbonyl rhodium, tris(triphenylphosphine trisodium sulfonate) carbonyl chloro rhodium and acetylacetone diethylene rhodium.
[0009] Preferably, in step (1), the molar ratio of the amount of the rhodium-based catalyst to the amount of the phosphine ligand is 1:3-20.
[0010] Preferably, in step (1), the initial pressure of the reaction system is 1-3 MPa when the synthesis gas is introduced.
[0011] Preferably, in the synthesis gas, the volume ratio of CO to H2 is 1:0.5-1.5.
[0012] Preferably, in step (1), the mixed octenes contain 60-80 wt% of 2,4,4-trimethyl-1-pentene and 20-40 wt% of 2,4,4-trimethyl-2-pentene.
[0013] Preferably, the mixed octenes have an acid value less than 0.014 mgKOH / g and a moisture content less than 0.002 wt%.
[0014] Preferably, in step (1), the conditions of the hydroformylation reaction include a temperature of 80-120℃, a pressure of 1-5 MPa, and a time of 2-10 h.
[0015] Preferably, in step (2), the molar ratio of the hydrogen to the amount of the isononyl aldehyde is 100-1000:1.
[0016] Preferably, the liquid hourly space velocity of the isononyl aldehyde is 1-5 hr -1 .
[0017] Preferably, in step (2), the hydrogenation catalyst needs to be reduced with hydrogen before use.
[0018] Preferably, the hydrogenation catalyst is selected from at least one of copper-zinc catalyst, nickel-based catalyst, and palladium-based catalyst.
[0019] Preferably, the conditions of the reduction include a temperature of 200-250℃ and a time of 4-8 h.
[0020] Preferably, in step (2), the conditions of the hydrogenation reaction include a temperature of 50-150℃, a pressure of 1-5 MPa, and a time of 1-8 h.
[0021] The method of the present application uses mixed octenes as raw materials, and adopts a rhodium-based catalyst complexed with two or more phosphine ligands to prepare isononyl aldehyde through a hydroformylation reaction. The isononyl aldehyde is subjected to a hydrogenation reaction under the action of a hydrogenation catalyst. Since the rhodium-based catalyst complexed with two or more phosphine ligands has high reactivity, it can significantly improve the conversion rate of the mixed octenes in the hydroformylation reaction, effectively inhibit the generation of by-products, improve the selectivity of isononyl aldehyde, realize the efficient conversion of mixed octenes to isononyl aldehyde, further improve the yield of the isononyl aldehyde, and thus greatly improve the yield of isononyl alcohol in the subsequent hydrogenation reaction. In addition, this method has mild reaction conditions, can avoid the explosion risk of high-pressure systems, reduce the problems of decomposition of reactants or deactivation of catalysts caused by high temperature, has stronger process stability, and is simple and convenient to operate, highly consistent with the needs of large-scale industrial production, and exhibits significant economic value and broad industrial application prospects. DETAILED DESCRIPTION
[0022] The specific embodiments of the present application are described in detail below. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present application, and are not used to limit the present application.
[0023] The endpoints of the ranges and any values disclosed herein are not limited to the precise values recited as the exact dimensions are not considered critical for the purposes of the application. The ranges should be interpreted as being inclusive of the recited values and the ranges between the recited values, and the ranges should be interpreted as being inclusive of the recited values and the ranges between the recited values.
[0024] The method for synthesizing isononyl alcohol according to the present application comprises the following steps: (1) mixing mixed octenes, a rhodium-based catalyst and a phosphine ligand, and then introducing synthesis gas into the obtained mixture to perform a hydroformylation reaction, thereby obtaining isononyl aldehyde; (2) mixing the isononyl aldehyde with hydrogen in the presence of a hydrogenation catalyst to perform a hydrogenation reaction.
[0025] In the method according to the present application, the active center of the rhodium-based catalyst can be coordinated with an olefin to form an intermediate, which is converted into an alkyl-Rh intermediate through an oxidative addition reaction, and then CO is added to the intermediate to form an acyl intermediate, followed by the addition of H2 to make the intermediate undergo a reductive elimination reaction, thereby obtaining the product aldehyde. In a preferred case, the rhodium-based catalyst is selected from at least one of rhodium trichloride hydrate, acetylacetone dicarbonyl rhodium, tris(triphenylphosphine trisodium sulfonate) carbonyl rhodium chloride and acetylacetone diethylene rhodium. In a further preferred case, the rhodium-based catalyst is acetylacetone dicarbonyl rhodium.
[0026] In some embodiments, in step (1), the mixed octenes contain 2,4,4-trimethyl-1-pentene represented by formula (I) and 2,4,4-trimethyl-2-pentene represented by formula (II). In a preferred case, the mixed octenes contain 60-80 wt% of 2,4,4-trimethyl-1-pentene and 20-40 wt% of 2,4,4-trimethyl-2-pentene. In a more preferred case, the mixed octenes contain 62-78 wt% of 2,4,4-trimethyl-1-pentene and 22-38 wt% of 2,4,4-trimethyl-2-pentene. In a further preferred case, the mixed octenes contain 65-75 wt% of 2,4,4-trimethyl-1-pentene and 25-35 wt% of 2,4,4-trimethyl-2-pentene. When the content of 2,4,4-trimethyl-1-pentene and 2,4,4-trimethyl-2-pentene in the mixed octenes is within the above-mentioned preferred ranges, the hydroformylation reaction is more likely to proceed smoothly.
[0027]
[0028] Formula (I)
[0029] Formula (II) In some embodiments, in step (1), in order to ensure the smooth progress of the hydroformylation reaction, and further improve the conversion of the mixed octene and the yield and selectivity of the isoneral, thereby further improving the yield of the isoneral, it is necessary to limit the acid value and moisture content of the mixed octene. Specifically, the acid value of the mixed octene is less than 0.014 mgKOH / g, and the moisture content of the mixed octene is less than 0.002 wt%. In the present application, the mixed octene can be obtained by dimerization of butene.
[0030] In some embodiments, in step (1), in order to ensure the smooth progress of the hydroformylation reaction, and further improve the conversion of the mixed octene and the yield and selectivity of the isoneral, thereby further improving the yield of the isoneral, it is necessary to limit the weight ratio of the amount of use of the mixed octene to the rhodium-based catalyst. Specifically, the weight ratio of the amount of use of the mixed octene to the rhodium-based catalyst is preferably 1-5:1, more preferably 1-3:1, and further preferably 1-2:1.
[0031] In the method of the present application, when the phosphine ligand with large steric hindrance is present in the system, it will promote the alkyl-Rh intermediate to form a straight-chain alkyl-Rh intermediate with smaller steric hindrance, which is more prone to reaction. In a preferred case, the phosphine ligand is selected from two or more of triphenyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, triphenyl phosphine, 6,6'-{[5,5'-dimethoxy-3,3'-bis(2-methyl-2-propyl)-2,2'-biphenyldiyl]bis(oxy)}bis[dibenzo(d,f)(1,3,2)dioxaphosphepin] and 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene. In a further preferred case, the phosphine ligand comprises a first phosphine ligand and a second phosphine ligand, wherein the first phosphine ligand is selected from at least one of tris(2,4-di-tert-butylphenyl) phosphite, triphenyl phosphine and 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, and the second phosphine ligand is triphenyl phosphite and / or 6,6'-{[5,5'-dimethoxy-3,3'-bis(2-methyl-2-propyl)-2,2'-biphenyldiyl]bis(oxy)}bis[dibenzo(d,f)(1,3,2)dioxaphosphepin].
[0032] In some preferred embodiments, in step (1), in order to further improve the conversion rate of the mixed octene and the yield and selectivity of the isoneral, and further improve the yield of the isonanol, the weight ratio of the amount of the first phosphine ligand to the second phosphine ligand needs to be limited. Specifically, the weight ratio of the amount of the first phosphine ligand to the second phosphine ligand is preferably 1-100:1, more preferably 1.5-60:1, and further preferably 2-50:1. As specific examples, the weight ratio of the amount of the first phosphine ligand to the second phosphine ligand can be 2:1, 5:1, 15:1, 20:1, 25:1, 30:1, 35:1, 40:1, 45:1 or 50:1.
[0033] In some particularly preferred embodiments, in step (1), the first phosphine ligand is tris(2,4-di-tert-butylphenyl)phosphite, the second phosphine ligand is triphenyl phosphite, and the weight ratio of the amount of tris(2,4-di-tert-butylphenyl)phosphite to triphenyl phosphite is 19-50:1, preferably 20-49.5:1. Under this condition, the conversion rate of the mixed octene in the hydroformylation reaction can be significantly improved, the generation of by-products can be effectively inhibited, the selectivity of the isoneral can be improved, the efficient conversion of the mixed octene to the isoneral can be achieved, the yield of the isoneral can be further improved, and thus the yield of the isonanol in the subsequent hydrogenation reaction process can be greatly improved.
[0034] In some embodiments, in step (1), in order to further improve the conversion rate of the mixed octene, inhibit the generation of by-products, and further improve the yield of the isoneral, and thus the yield of the isonanol, the molar ratio of the amount of the rhodium-based catalyst to the phosphine ligand needs to be limited. Specifically, the molar ratio of the amount of the rhodium-based catalyst to the phosphine ligand is preferably 1:3-20, more preferably 1:4-15, and further preferably 1:5-10. As specific examples, the molar ratio of the amount of the rhodium-based catalyst to the phosphine ligand can be 1:5, 1:6, 1:7, 1:8, 1:9 or 1:10.
[0035] In some embodiments, in step (1), in order to ensure the smooth progress of the hydroformylation reaction, and further improve the conversion rate of the mixed octene, the yield and selectivity of the isoneral, thereby further improving the yield of the isoneral, the amount of the synthesis gas needs to be limited. In the present application, the amount of the synthesis gas is limited by limiting the initial pressure of the reaction system after the synthesis gas is introduced. Specifically, the initial pressure of the reaction system after the synthesis gas is introduced is preferably 1-3 MPa, more preferably 1.5-2.5 MPa. As a specific example, the initial pressure of the reaction system after the synthesis gas is introduced can be 1.5 MPa, 1.6 MPa, 1.7 MPa, 1.8 MPa, 1.9 MPa, 2 MPa, 2.1 MPa, 2.2 MPa, 2.3 MPa, 2.4 MPa or 2.5 MPa. In the present application, the pressure is absolute pressure.
[0036] In some specific embodiments, in step (1), in order to ensure the smooth progress of the hydroformylation reaction, and further improve the conversion rate of the mixed octene, the yield and selectivity of the isoneral, thereby further improving the yield of the isoneral, the volume ratio of CO and H2 in the synthesis gas needs to be limited. Specifically, in the synthesis gas, the volume ratio of CO and H2 is preferably 1:0.5-1.5, more preferably 1:0.7-1.3, and further preferably 1:0.8-1.2. As a specific example, in the synthesis gas, the volume ratio of CO and H2 can be 1:0.8, 1:0.9, 1:1, 1:1.1 or 1:1.2.
[0037] In some specific embodiments, in step (1), the conditions of the hydroformylation reaction include: the temperature is 80-120℃, preferably 85-100℃; the pressure is 1-5 MPa, preferably 2-4 MPa; the time is 2-10 h, preferably 3-8 h. Specifically, the temperature of the hydroformylation reaction can be 85℃, 90℃, 95℃ or 100℃; the pressure of the hydroformylation reaction can be 2 MPa, 2.5 MPa, 3 MPa, 3 MPa or 4 MPa; the time of the hydroformylation reaction can be 3 h, 4 h, 5 h, 6 h, 7 h or 8 h.
[0038] In some specific embodiments, the specific process of step (1) further comprises: delivering the product obtained by the hydroformylation reaction to a thin film evaporator for separation to obtain isoneral. And the operating pressure of the thin film evaporator is 5-15 KPa, and the operating temperature is 60-70℃.
[0039] In the method of the present application, in step (2), the isoneraldehyde can be mixed with hydrogen gas and subjected to hydrogenation reaction under the action of the hydrogenation catalyst to generate isonanol. In order to further improve the yield and selectivity of the isonanol, the liquid hourly space velocity of the isoneraldehyde needs to be limited. Specifically, the liquid hourly space velocity of the isoneraldehyde is preferably 1-5 hr -1 , more preferably 1.5-3 hr -1 . As a specific example, the liquid hourly space velocity of the isoneraldehyde can be 1.5 hr -1 , 1.6 hr -1 , 1.7 hr -1 , 1.8 hr -1 , 1.9 hr -1 , 2 hr -1 , 2.1 hr -1 , 2.2 hr -1 , 2.3 hr -1 , 2.4 hr -1 , 2.5 hr -1 or 3 hr -1 .
[0040] In the method of the present application, the type of the hydrogenation catalyst is not limited, and various hydrogenation catalysts commonly used in the art can be used. In a preferred case, the hydrogenation catalyst is selected from at least one of copper-zinc catalyst, nickel-based catalyst and palladium-based catalyst. In a further preferred case, the hydrogenation catalyst is a nickel-based catalyst.
[0041] In some embodiments, in step (2), in order to further improve the yield and selectivity of the isonanol, the molar ratio of the amount of hydrogen gas to the amount of isoneraldehyde needs to be limited. Specifically, the molar ratio of the amount of hydrogen gas to the amount of isoneraldehyde is preferably 100-1000:1, more preferably 200-800:1, and further preferably 300-600:1. As a specific example, the molar ratio of the amount of hydrogen gas to the amount of isoneraldehyde can be 300:1, 400:1, 500:1 or 600:1.
[0042] In some embodiments, in step (2), the hydrogenation catalyst needs to be reduced with hydrogen gas before use, so as to convert metal oxides into active metal elements, optimize the dispersion, electronic structure and surface properties thereof, and thus achieve high-efficiency hydrogenation catalytic performance.
[0043] In some specific embodiments, in step (2), the conditions for reducing the hydrogenation catalyst with hydrogen gas include: temperature of 200-250°C, preferably 210-240°C; and time of 4-8h, preferably 5-7h.
[0044] In some specific embodiments, in step (2), the conditions of the hydrogenation reaction include: temperature of 50-150°C, preferably 90-140°C; pressure of 1-5 MPa, preferably 2-4 MPa; time of 1-8 h, preferably 2-5 h. Specifically, the temperature of the hydrogenation reaction can be 90°C, 100°C, 110°C, 120°C, 130°C or 140°C; the pressure of the hydrogenation reaction can be 2 MPa, 2.5 MPa, 3 MPa, 3.5 MPa or 4 MPa; and the time of the hydrogenation reaction can be 2 h, 3 h, 4 h or 5 h.
[0045] The method for synthesizing isononyl alcohol according to the present application is further illustrated by examples below. The examples are implemented on the premise of the technical solutions of the present application, and detailed implementation modes and specific operation processes are given, but the protection scope of the present application is not limited to the examples below.
[0046] In the experimental methods in the examples below, the methods are all conventional methods in the art unless otherwise specified. The experimental materials used in the examples below are all commercially available unless otherwise specified.
[0047] In the examples and comparative examples below, the mixed octenes contain 68 wt% of 2,4,4-trimethyl-1-pentene and 32 wt% of 2,4,4-trimethyl-2-pentene, and the acid value of the mixed octenes is 0.013 mgKOH / g, and the moisture content is 0.0018 wt%.
[0048] Example 1 (1) The mixed octenes, acetylacetone dicarbonyl rhodium, tris(2,4-di-tert-butylphenyl) phenyl phosphite and triphenyl phosphite were added into a high-pressure reaction kettle, then the synthetic gas with a volume ratio of CO to H2 of 1:1 was introduced until the pressure in the kettle was 2 MPa, the temperature in the kettle was increased, and the reaction was started when the temperature in the kettle reached 90°C. The reaction pressure was controlled to maintain at 2 MPa, and the reaction was carried out for 5 h. After the reaction was completed, the reaction product was transported to a thin film evaporator for separation under the conditions of an operating pressure of 10 KPa and an operating temperature of 65°C to obtain a separation product A1; wherein the weight ratio of the amount of the mixed octenes to the amount of acetylacetone dicarbonyl rhodium was 1:1, the molar ratio of the amount of acetylacetone dicarbonyl rhodium to the amount of the combination of tris(2,4-di-tert-butylphenyl) phenyl phosphite and triphenyl phosphite was 1:7, and the weight ratio of the amount of tris(2,4-di-tert-butylphenyl) phenyl phosphite to the amount of triphenyl phosphite was 49:1; (2) The nickel-magnesium hydrogenation catalyst was reduced by hydrogen at 220°C for 6h to obtain a reduced nickel active body, and then the separation product A1 obtained in step (1) was delivered into a fixed-bed hydrogenation reactor by a feeding pump, and hydrogenated under the action of the reduced nickel active body at a temperature of 120°C and a pressure of 3 MPa for 3h to obtain a hydrogenation reaction product S1. The liquid hourly space velocity of the separation product A1 was 2.5 hr -1 , and the molar ratio of the amount of hydrogen to the amount of the separation product A1 was 400:1.
[0049] Example 2 (1) The mixed octene, acetylacetone dicarbonyl rhodium, tris(2,4-di-tert-butylphenyl) phenyl phosphite and triphenyl phosphite were added into a high-pressure reactor, and then a synthetic gas with a volume ratio of CO to H2 of 1:1 was introduced until the pressure in the reactor was 1.5 MPa, and then the temperature was increased, and when the temperature in the reactor reached 85°C, the reaction was started, and the reaction pressure was controlled to be maintained at 2 MPa, and the reaction was carried out for 8h, and after the reaction was completed, the reaction product was delivered into a thin film evaporator and separated at an operating pressure of 10 KPa and an operating temperature of 65°C to obtain a separation product A2; wherein the weight ratio of the amount of the mixed octene to the amount of acetylacetone dicarbonyl rhodium was 2:1, the molar ratio of the amount of acetylacetone dicarbonyl rhodium to the amount of the combination of tris(2,4-di-tert-butylphenyl) phenyl phosphite and triphenyl phosphite was 1:5, and the weight ratio of the amount of tris(2,4-di-tert-butylphenyl) phenyl phosphite to the amount of triphenyl phosphite was 20:1; (2) The nickel-magnesium hydrogenation catalyst was reduced by hydrogen at 220°C for 6h to obtain a reduced nickel active body, and then the separation product A2 obtained in step (1) was delivered into a fixed-bed hydrogenation reactor by a feeding pump, and hydrogenated under the action of the reduced nickel active body at a temperature of 90°C and a pressure of 2 MPa for 5h to obtain a hydrogenation reaction product S2. The liquid hourly space velocity of the separation product A2 was 1.5 hr -1 , and the molar ratio of the amount of hydrogen to the amount of the separation product A2 was 300:1.
[0050] Example 3 (1) mixed octene, acetylacetone dicarbonyl rhodium, tri(2,4-di-tert-butylphenyl) phosphite and triphenyl phosphite are added into a high-pressure reactor, then a synthetic gas with a volume ratio of CO and H2 of 1:1 is introduced until the pressure in the reactor is 2.5 MPa, the temperature is raised, when the temperature in the reactor rises to 100℃, the reaction is started, the reaction pressure is controlled to maintain at 4 MPa, the reaction is carried out for 3 h, after the reaction is completed, the reaction product is transported to a thin film evaporator, and is separated under the conditions of an operating pressure of 10 KPa and an operating temperature of 65℃, to obtain a separation product A3; wherein the weight ratio of the use amount of the mixed octene to acetylacetone dicarbonyl rhodium is 1:1, the molar ratio of the use amount of the combination of acetylacetone dicarbonyl rhodium, tri(2,4-di-tert-butylphenyl) phosphite and triphenyl phosphite is 1:10, and the weight ratio of the use amount of tri(2,4-di-tert-butylphenyl) phosphite to triphenyl phosphite is 49.5:1; (2) the nickel-magnesium hydrogenation catalyst is reduced with hydrogen at 220℃ for 6 h to obtain a reduced nickel active body, then the separation product A3 obtained in step (1) is transported to a fixed-bed hydrogenation reactor through a feeding pump, and is hydrogenated under the action of the reduced nickel active body at a temperature of 140℃ and a pressure of 4 MPa for 2 h to obtain a hydrogenation reaction product S3. The liquid hourly space velocity of the separation product A3 is 3 h-1 -1 , and the molar ratio of the use amount of hydrogen to the separation product A3 is 600:1.
[0051] Example 4 (1) mixed octene, acetylacetone dicarbonyl rhodium, triphenyl phosphine and triphenyl phosphite are added into a high-pressure reactor, then a synthetic gas with a volume ratio of CO and H2 of 1:1 is introduced until the pressure in the reactor is 2 MPa, the temperature is raised, when the temperature in the reactor rises to 90℃, the reaction is started, the reaction pressure is controlled to maintain at 2 MPa, the reaction is carried out for 5 h, after the reaction is completed, the reaction product is transported to a thin film evaporator, and is separated under the conditions of an operating pressure of 10 KPa and an operating temperature of 65℃, to obtain a separation product A4; wherein the weight ratio of the use amount of the mixed octene to acetylacetone dicarbonyl rhodium is 1.5:1, the molar ratio of the use amount of the combination of acetylacetone dicarbonyl rhodium, triphenyl phosphine and triphenyl phosphite is 1:7, and the weight ratio of the use amount of triphenyl phosphine to triphenyl phosphite is 7:3; (2) the nickel-magnesium hydrogenation catalyst is reduced with hydrogen at 220℃ for 6 h to obtain a reduced nickel active body, then the separation product A4 obtained in step (1) is transported to a fixed-bed hydrogenation reactor through a feeding pump, and is hydrogenated under the action of the reduced nickel active body at a temperature of 120℃ and a pressure of 3 MPa for 2 h to obtain a hydrogenation reaction product S4. The liquid hourly space velocity of the separation product A4 is 3 h-1 -1hydrogen and the separated product A4 is 400: 1.
[0052] Example 5 The synthesis was performed according to the method described in Example 4, except that in step (1), an equimolar amount of rhodium trichloride hydrate was used instead of acetylacetone dicarbonyl rhodium to obtain the separated product A5 and the hydrogenation reaction product S5.
[0053] Example 6 The synthesis was performed according to the method described in Example 1, except that in step (1), the reaction temperature was 85°C to obtain the separated product A6 and the hydrogenation reaction product S6.
[0054] Example 7 The synthesis was performed according to the method described in Example 1, except that in step (1), the reaction temperature was 100°C to obtain the separated product A7 and the hydrogenation reaction product S7.
[0055] Example 8 The synthesis was performed according to the method described in Example 1, except that in step (1), the molar ratio of the amount used of acetylacetone dicarbonyl rhodium to the combination of tris(2,4-di-tert-butylphenyl) phosphite and triphenyl phosphite was 1:10 to obtain the separated product A8 and the hydrogenation reaction product S8.
[0056] Example 9 The synthesis was performed according to the method described in Example 1, except that in step (1), the weight ratio of the amount used of tris(2,4-di-tert-butylphenyl) phosphite to triphenyl phosphite was 19:1 to obtain the separated product A9 and the hydrogenation reaction product S9.
[0057] Example 10 The synthesis was performed according to the method described in Example 1, except that in step (1), the molar ratio of the amount used of acetylacetone dicarbonyl rhodium to the combination of tris(2,4-di-tert-butylphenyl) phosphite and triphenyl phosphite was 1:5 to obtain the separated product A10 and the hydrogenation reaction product S10.
[0058] Example 11 (1) mixed octene, acetylacetone dicarbonyl rhodium, tri(2,4-di-tert-butylphenyl) phosphite and 6,6'-{[5,5'-dimethoxy-3,3'-bis(2-methyl-2-propyl)-2,2'-biphenyl diyl]bis(oxy)}bis[dibenzo(d,f)(1,3,2)dioxaphosphepin] were added into a high-pressure reactor, then a synthetic gas with a volume ratio of CO and H2 of 1:1 was introduced until the pressure in the reactor was 2 MPa, the temperature was raised, when the temperature in the reactor reached 90°C, the reaction was started, the pressure was controlled to maintain at 2 MPa, the reaction was carried out for 5 h, after the reaction was completed, the reaction product was transported to a thin film evaporator, and was separated under the conditions of an operating pressure of 10 KPa and an operating temperature of 65°C to obtain a separation product A11; wherein the weight ratio of the use amount of the mixed octene to acetylacetone dicarbonyl rhodium was 1:1, the molar ratio of the use amount of the combination of acetylacetone dicarbonyl rhodium, tri(2,4-di-tert-butylphenyl) phosphite and triphenyl phosphite was 1:7, and the weight ratio of the use amount of tri(2,4-di-tert-butylphenyl) phosphite to triphenyl phosphite was 5:1; (2) the nickel magnesium hydrogenation catalyst was reduced with hydrogen at 220°C for 6 h to obtain a reduced nickel active body, then the separation product A11 obtained in step (1) was transported into a fixed bed hydrogenation reactor by a feeding pump, and was hydrogenated under the action of the reduced nickel active body at a temperature of 120°C and a pressure of 3 MPa for 2 h to obtain a hydrogenation reaction product S11. Wherein the liquid hourly space velocity of the separation product A11 was 3 h-1 -1 , and the molar ratio of the use amount of hydrogen to the separation product A11 was 400:1.
[0059] Example 12 (1) mixed octene, hydrated rhodium trichloride, triphenylphosphine and 6,6'-{[5,5'-dimethoxy-3,3'-bis(2-methyl-2-propyl)-2,2'-biphenyldiyl]bis(oxy)}bis[dibenzo(d,f)(1,3,2)dioxaphosphepin] were added into a high-pressure reactor, then a synthetic gas with a volume ratio of CO to H2 of 1:1 was introduced until the pressure in the reactor was 2 MPa, then the temperature was raised, when the temperature in the reactor reached 90°C, the reaction was started, the pressure was controlled to be 2 MPa, the reaction was carried out for 5 h, after the reaction was completed, the reaction product was transported to a thin film evaporator, and was separated under the conditions that the operating pressure was 10 KPa and the operating temperature was 65°C, to obtain a separation product A12; wherein the weight ratio of the use amount of the mixed octene to the hydrated rhodium trichloride was 1:2, the molar ratio of the combined use amount of the hydrated rhodium trichloride to triphenylphosphine and 6,6'-{[5,5'-dimethoxy-3,3'-bis(2-methyl-2-propyl)-2,2'-biphenyldiyl]bis(oxy)}bis[dibenzo(d,f)(1,3,2)dioxaphosphepin] was 1:7, and the weight ratio of the use amount of triphenylphosphine to 6,6'-{[5,5'-dimethoxy-3,3'-bis(2-methyl-2-propyl)-2,2'-biphenyldiyl]bis(oxy)}bis[dibenzo(d,f)(1,3,2)dioxaphosphepin] was 49:1; (2) the nickel-magnesium hydrogenation catalyst was reduced with hydrogen at 220°C for 6 h to obtain a reduced nickel active body, then the separation product A12 obtained in step (1) was transported into a fixed-bed hydrogenation reactor through a feeding pump, and was subjected to hydrogenation reaction under the action of the reduced nickel active body at a temperature of 120°C and a pressure of 3 MPa for 2 h to obtain a hydrogenation reaction product S12. Wherein the liquid hourly space velocity of the separation product A12 was 3 h-1 -1 , and the molar ratio of the use amount of hydrogen to the separation product A12 was 400:1.
[0060] Comparative Example 1 (1) mixed octenes, dicobalt octacarbonyl and 6,6'-{[5,5'-dimethoxy-3,3'-bis(2-methyl-2-propyl)-2,2'-biphenyldiyl]bis(oxy)}bis[dibenzo(d,f)(1,3,2)dioxaphosphepin] were added into a high-pressure reactor, then a synthetic gas with a volume ratio of CO to H2 of 1:1 was introduced until the pressure in the reactor was 6 MPa, then the temperature was raised, when the temperature in the reactor reached 150°C, the reaction was started, the pressure was controlled to be 5 MPa, the reaction was carried out for 5 h, after the reaction was completed, the reaction product was transported to a thin film evaporator, a primary evaporator was operated at normal pressure with an operating temperature of 40°C, a secondary evaporator was operated at a pressure of 10 KPa with an operating temperature of 65°C, to obtain a separation product D1. In the method, the weight ratio of the amount of the mixed octenes to the amount of the dicobalt octacarbonyl was 1:1, and the molar ratio of the amount of the dicobalt octacarbonyl to the amount of 6,6'-{[5,5'-dimethoxy-3,3'-bis(2-methyl-2-propyl)-2,2'-biphenyldiyl]bis(oxy)}bis[dibenzo(d,f)(1,3,2)dioxaphosphepin] was 1:50.
[0061] Comparative Example 2 The synthesis was carried out according to the method described in Example 5, except that in step (1), no triphenyl phosphite was added, to obtain a separation product D2 and a hydrogenation reaction product M2.
[0062] Comparative Example 3 The synthesis was carried out according to the method described in Example 1, except that in step (1), no triphenyl phosphite was added, to obtain a separation product D3 and a hydrogenation reaction product M3.
[0063] Comparative Example 4 The synthesis was carried out according to the method described in Example 1, except that in step (1), no tris(2,4-di-tert-butylphenyl) phenyl phosphite was added, to obtain a separation product D4 and a hydrogenation reaction product M4.
[0064] Test Example The composition of the separation products and the hydrogenation reaction products obtained in the examples and the comparative examples were analyzed by using a gas chromatograph (purchased from Shimadzu Corporation, Japan, model GC-2014), and the conversion rate of the mixed octenes in step (1), the selectivity and the yield of isononyl aldehyde, and the conversion rate of isononyl aldehyde in step (2), the selectivity and the yield of isononyl alcohol were calculated by using the following formula, and the results are shown in Table 1.
[0065] A = [(A1-A2) / A1]×100% B = [B1 / (B1+B2)]×100% In the formula, A represents the conversion rate of mixed olefins, A1 represents the mass fraction of mixed olefins in the raw material before reaction, and A2 represents the mass fraction of unreacted olefins in the reactor outlet product; B represents the selectivity of isononyl aldehyde, B1 represents the mass fraction of isononyl aldehyde in the outlet product, and B2 represents the mass fraction of by-products in the reactor outlet product; C = [(C1-C2) / C1]x100% D = [D1 / (D1+D2)]x100% In the formula, C represents the conversion rate of aldehyde, C1 represents the mass fraction of isononyl aldehyde in the aldehyde raw material before reaction, and C2 represents the mass fraction of unreacted isononyl aldehyde in the reactor outlet product; D represents the selectivity of isononyl alcohol, D1 represents the mass fraction of isononyl alcohol in the outlet product, and D2 represents the mass fraction of by-products in the reactor outlet product.
[0066] Table 1
[0067] As can be seen from the results in Table 1, the method described in the present application can significantly improve the conversion rate of the mixed octene in the hydroformylation reaction, effectively inhibit the generation of by-products, improve the selectivity of isononyl aldehyde, realize the efficient conversion of mixed octene to isononyl aldehyde, further improve the yield of isononyl aldehyde, and thus greatly improve the yield of isononyl alcohol in the subsequent hydrogenation reaction process. In addition, the method has mild reaction conditions and simple and convenient operation, and is highly consistent with the needs of large-scale industrial production, showing significant economic value and broad industrial application prospects.
[0068] The above describes the preferred embodiments of the present application in detail, but the present application is not limited thereto. Within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be considered as disclosed by the present application and fall within the protection scope of the present application.
Claims
1. A method of synthesizing isononyl alcohol, characterized by, The method comprises the following steps: (1) mixing mixed octene, a rhodium-based catalyst and a phosphine ligand, and then introducing synthesis gas into the obtained mixture to perform a hydroformylation reaction to obtain isononyl aldehyde; (2) mixing the isononyl aldehyde with hydrogen in the presence of a hydrogenation catalyst to perform a hydrogenation reaction; The phosphine ligand is selected from two or more of triphenyl phosphite, tris(2,4-di-tert-butylphenyl)phosphite, triphenylphosphine, 6,6'-{[5,5'-dimethoxy-3,3'-bis(2-methyl-2-propyl)-2,2'-biphenyldiyl]bis(oxy)}bis[dibenzo(d,f)(1,3,2)dioxaphosphepin] and 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene.
2. The method of claim 1, wherein, The phosphine ligand comprises a first phosphine ligand and a second phosphine ligand, wherein the first phosphine ligand is selected from at least one of tris(2,4-di-tert-butylphenyl)phosphite, triphenylphosphine and 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, the second phosphine ligand is triphenyl phosphite and / or 6,6'-{[5,5'-dimethoxy-3,3'-bis(2-methyl-2-propyl)-2,2'-biphenyldiyl]bis(oxy)}bis[dibenzo(d,f)(1,3,2)dioxaphosphepin], and the weight ratio of the amount of the first phosphine ligand to the amount of the second phosphine ligand is 1-100:
1.
3. The method of claim 1, wherein, In step (1), the weight ratio of the amount of the mixed octene to the amount of the rhodium-based catalyst is 1-5:1; and / or The rhodium-based catalyst is selected from at least one of hydrated rhodium trichloride, acetylacetone dicarbonyl rhodium, tris(triphenylphosphine trisodium sulfonate) carbonyl rhodium chloride and acetylacetone diethylene rhodium.
4. The method according to any one of claims 1 to 3, characterized in that, In step (1), the molar ratio of the amount of the rhodium-based catalyst to the amount of the phosphine ligand is 1:3-20.
5. The method according to any one of claims 1 to 4, characterized in that, In step (1), the initial pressure of the reaction system is 1-3 MPa when the synthesis gas is introduced; and / or In the synthesis gas, the volume ratio of CO to H2 is 1:0.5-1.
5.
6. The method according to any one of claims 1-5, characterized in that, In step (1), the mixed octene contains 60-80 wt% of 2,4,4-trimethyl-1-pentene and 20-40 wt% of 2,4,4-trimethyl-2-pentene; Preferably, the acid value of the mixed octene is less than 0.014 mgKOH / g, and the moisture content is less than 0.002 wt%.
7. The method according to any one of claims 1 to 6, characterized in that, In step (1), the conditions of the hydroformylation reaction include a temperature of 80-120℃, a pressure of 1-5 MPa and a time of 2-10 h.
8. The method of claim 1, wherein, In step (2), the molar ratio of the amount of the hydrogen to the amount of the isononyl aldehyde is 100-1000:1; and / or said isonitroaldehyde has a liquid hourly space velocity of 1-5 hr -1 .
9. The method according to claim 1 or 8, characterized in that, In step (2), the hydrogenation catalyst needs to be reduced with hydrogen before use; Preferably, the hydrogenation catalyst is selected from at least one of copper-zinc catalyst, nickel-based catalyst and palladium-based catalyst; Preferably, the conditions of the reduction include a temperature of 200-250℃ and a time of 4-8 h.
10. The method according to any one of claims 1, 8 and 9, characterized in that, In step (2), the conditions of the hydrogenation reaction include a temperature of 50-150℃, a pressure of 1-5 MPa and a time of 1-8 h.