Catalyst composition, application thereof and method for preparing high-carbon alcohol through olefin hydroformylation
By combining salts containing halogen ions, triorganophosphines and specific compounds with ruthenium catalysts, and using CO2 as the carbonyl source, the "one-pot method" of olefin hydroformylation-aldehyde hydrogenation reaction is achieved, solving the problems of complex reactions and low catalytic activity in the prior art, and improving the preparation efficiency and safety of high carbon alcohols.
Patent Information
- Application Number
- CN202410006892.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-01-02
- Publication Date
- 2025-07-04
AI Technical Summary
In the prior art, the reaction process of preparing high-carbon alcohols by hydroformylation of olefins is complicated, the side reaction is difficult to inhibit, the catalytic activity is low, and the traditional method uses toxic and flammable CO as the carbonyl source, which poses production risks.
The "one-pot method" of olefin hydrogenation reaction of olefin hydrogenation reaction is achieved by combining olefin hydrogenation-aldehyde with a salt containing halogen ion, triorganophosphine and/or oxidized triorganophosphine compounds and compounds with specific structures as additives, combined with a carbonyl-containing ruthenium catalyst, and CO2 is used as a carbonyl source. The catalyst also has the functions of reverse water gas conversion, olefin hydrogenation and aldehyde hydrogenation.
It realizes efficient preparation of high-carbon alcohols, simplifies the reaction process, improves catalytic activity and olefin conversion, reduces side reactions, avoids the use of toxic and flammable CO, and reduces production risks.
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Abstract
Description
Technical Field
[0001] The present invention relates to the field of hydroformylation reactions, and particularly to a catalyst composition, its application, and a method for preparing higher alcohols by hydroformylation of olefins. Background Art
[0002] Higher alcohols are a general term for monohydric alcohols containing more than six carbon atoms. They are important basic chemical raw materials and can be used in the synthesis of various fine chemicals such as plasticizers, detergents, surfactants, and stabilizers. Their downstream products also cover various fields such as petrochemical industry, daily chemical industry, food, and medicine, and are highly concerned due to their high added value and large product demand.
[0003] Hydroformylation of olefins, also known as the oxo reaction, is a reaction in which olefins react with syngas (CO / H2) in the presence of a catalyst to form aldehydes with one more carbon atom. Generally, the ultimate goal of the process involving the hydroformylation reaction step is to produce alcohols. It is highly desirable to obtain the final product alcohol through a one-step hydroformylation-hydrogenation process to reduce reaction time, process flow, and equipment investment. However, since the catalysts and reaction conditions used in the two reactions are often different, currently, two reaction processes of hydroformylation-hydrogenation are still adopted in industrial production to obtain higher alcohols. For example, the typical process flow for hydroformylation of C6-C 16 olefins proposed by Evonik includes a homogeneous hydroformylation reaction unit, a catalyst decomposition unit, a separation unit, and a heterogeneous aldehyde hydrogenation unit.
[0004] For the one-step hydroformylation-hydrogenation of olefins to prepare alcohols, the selection of the catalyst system is the most crucial. The catalyst needs to simultaneously possess the catalytic effects of hydroformylation and aldehyde hydrogenation reactions, and both can occur under the same reaction conditions. The side reaction of olefin hydrogenation is often easier to proceed than aldehyde hydrogenation, which requires the catalyst to have excellent selective hydrogenation effects. Under normal conditions, using carbon monoxide (CO) as the carbonyl source can only obtain hydroformylation product aldehydes because CO will poison the hydrogenation catalyst and cause it to lose its hydrogenation effect. Therefore, choosing a green carbonyl source other than CO is also an effective approach, which can also avoid the use of toxic and flammable CO and reduce production risks. Summary of the Invention
[0005] The purpose of the present invention is to overcome the problems in the prior art for preparing alcohols, such as complex reaction procedures, difficult suppression of side reactions, and low catalytic activity. A catalyst composition, its application, and a method for preparing higher alcohols by hydroformylation of olefins are provided. When this catalyst composition participates in the reaction for preparing higher alcohols by hydroformylation of olefins, using CO2 as the carbonyl source, it can realize the "one-pot" preparation of higher alcohols through the coupling of homogeneous reverse water gas shift-hydroformylation of olefins-aldehyde hydrogenation reactions, and this catalytic system has high catalytic reaction activity.
[0006] To achieve the above object, a first aspect of the present invention provides a catalyst composition, wherein the catalyst composition comprises a catalyst active component, as well as a first promoter, a second promoter, and a third promoter;
[0007] Among them, the first promoter is a salt containing halogen ions, the second promoter is a triorganophosphine and / or an oxidized triorganophosphine compound, and the third promoter is a compound having the structure shown in formula (I) and / or a compound having the structure shown in formula (II),
[0008]
[0009] In formula (I) or formula (II), R1, R2, and R3 are each independently hydrogen or a substituted or unsubstituted hydrocarbon group, and in formula (I), X is a monovalent cation.
[0010] Preferably, in formula (I), X is selected from the group consisting of H + , Li + , Na + , K + , NH4 + , Cu + , and Ag + and at least one of them, and X is preferably selected from the group consisting of H + , Li + , Na + , and K + and at least one of them.
[0011] Preferably, in formula (I) or formula (II), R1, R2, and R3 are each independently hydrogen or a substituted or unsubstituted C1-C24 hydrocarbon group, and are preferably each independently hydrogen or at least one selected from the group consisting of substituted or unsubstituted methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopentyl, cyclohexyl, cycloheptyl, phenyl, benzyl, and naphthyl.
[0012] A second aspect of the present invention provides the use of the catalyst composition described in the first aspect in a hydroformylation reaction.
[0013] A third aspect of the present invention provides a method for preparing higher alcohols by hydroformylation of olefins, the method comprising: in the presence of a catalyst composition, using carbon dioxide and hydrogen as reaction gas sources, and using olefins as reaction substrates to carry out a hydroformylation reaction;
[0014] The catalyst composition is the catalyst composition described in the first aspect.
[0015] Through the above technical solutions, the beneficial effects achieved by the present invention are as follows:
[0016] (1) In the present invention, by using the catalyst active component in combination with three kinds of promoters, the catalyst composition simultaneously has the catalytic functions of carbon dioxide reverse water gas shift, olefin hydroformylation reaction and aldehyde hydrogenation reaction, has high catalytic activity, and can realize obtaining the final product alcohol by "one-pot method".
[0017] (2) The catalyst composition provided by the present invention, when applied in the olefin hydroformylation reaction, has a high olefin conversion rate, can effectively inhibit the occurrence of side reactions of olefin hydrogenation, has a high conversion rate of reaction raw materials, and a high yield of product alcohol. Detailed implementation mode
[0018] In the ranges disclosed herein, the endpoints and any values of the ranges are not limited to the exact ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, between the endpoint values of each range, between the endpoint values of each range and individual point values, and between individual point values, they can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed herein.
[0019] The first aspect of the present invention provides a catalyst composition, wherein the catalyst composition includes a catalyst active component and a first promoter, a second promoter and a third promoter;
[0020] Wherein, the first promoter is a salt containing halogen ions, the second promoter is a triorganophosphine and / or an oxidized triorganophosphine compound, and the third promoter is a compound having the structure shown in formula (Ⅰ) and / or a compound having the structure shown in formula (Ⅱ),
[0021]
[0022] In formula (Ⅰ) or formula (Ⅱ), R1, R2, and R3 are each independently hydrogen or a substituted or unsubstituted hydrocarbon group, and in formula (Ⅰ), X is a monovalent cation.
[0023] In the present invention, the catalyst composition uses the first promoter, the second promoter and the third promoter in combination with the catalyst active component. While catalyzing the reverse water gas shift reaction to convert CO2 into CO, it catalyzes the olefin hydroformylation reaction and the aldehyde hydrogenation reaction, and prepares alcohol by "one-pot method", which is beneficial to simplifying the reaction process.
[0024] In the present invention, the third promoter is selected as the compound described in the above structural formula, and in combination with the catalyst active component, the first promoter and the second promoter, it can effectively improve the catalytic activity of the reaction and obtain an alcohol with one more carbon atom at a faster reaction rate.
[0025] According to the present invention, preferably, the catalyst active component is a ruthenium catalyst containing a carbonyl group, preferably selected from Ru3(CO) 12, H4Ru4(CO) 12 and at least one of Ru2Cl4(CO)6.
[0026] In the present invention, preferably, a ruthenium catalyst containing carbonyl is used as the catalyst active component, and in combination with the above three selected additives, the catalyst system can simultaneously have the catalytic effects of reverse water gas shift, olefin hydroformylation, and aldehyde hydrogenation reactions.
[0027] According to the present invention, preferably, the cation in the first additive is an organic or inorganic cation. Preferably, the cation is selected from + Li + Na + K + NH4
[0028] and at least one of them. - According to the present invention, preferably, the halogen ion in the first additive is Cl - or F
[0029] According to a preferred embodiment of the present invention, the first additive is selected from at least one of LiCl, KF, and NaCl.
[0030] According to the present invention, preferably, the molar ratio of the first additive to the catalyst active component calculated as ruthenium is 0.1 - 500:1, preferably 1 - 100:1, such as 1:1, 5:1, 10:1, 20:1, 30:1, 40:1, 50:1, 60:1, 70:1, 80:1, 90:1, 100:1, or the range between any two of them, and more preferably 5 - 50:1.
[0031] In the present invention, preferably, adding the above types and specific amounts of the first additive in combination with the catalyst active component, the second additive, and the third additive can further suppress the side reactions of olefin hydrogenation and olefin isomerization.
[0032] According to the present invention, preferably, in formula (I), X is selected from + H + Li + Na + K + NH4 + Cu + Ag + and at least one of them. X is preferably selected from + H + Li + Na
[0033] According to the present invention, preferably, in formula (I) or formula (II), R1, R2, and R3 are each independently hydrogen or a substituted or unsubstituted C1-C24 hydrocarbon group.
[0034] In the present invention, the C1-C24 hydrocarbon group refers to a hydrocarbon group having 1 to 24 carbon atoms in total.
[0035] According to the present invention, preferably, R1, R2, and R3 are each independently selected from hydrogen or at least one of substituted or unsubstituted methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopentyl, cyclohexyl, cycloheptyl, phenyl, benzyl, and naphthyl.
[0036] In the present invention, preferably, the substituents are each independently selected from at least one of C1-C6 alkyl, halogen, C1-C6 alkoxy, hydroxyl, and carboxyl.
[0037] According to a preferred embodiment of the present invention, the third auxiliary agent is selected from at least one of acetic anhydride, benzoic acid, acetic acid, lithium acetate, sodium benzoate, and benzoic anhydride. By adopting this preferred embodiment, the hydroformylation reaction rate can be further stably increased.
[0038] According to the present invention, preferably, the molar ratio of the third auxiliary agent to the catalyst active component calculated as ruthenium is 0.1-1000:1, preferably 1-100:1, such as 1:1, 5:1, 10:1, 20:1, 30:1, 40:1, 50:1, 60:1, 70:1, 80:1, 90:1, 100:1, or the range between any two of them, and more preferably 5-50:1.
[0039] According to the present invention, preferably, the second auxiliary agent is a compound having the structure shown in formula (III) and / or a compound having the structure shown in formula (IV).
[0040]
[0041] In formula (III) or formula (IV), R1, R2, R3, R4, R5, and R6 are each independently selected from substituted or unsubstituted C1-C24 hydrocarbon groups, for example, each independently selected from at least one of substituted or unsubstituted methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopentyl, cyclohexyl, cycloheptyl, phenyl, benzyl, and naphthyl.
[0042] According to the present invention, preferably, the molar ratio of the second auxiliary agent to the catalyst active component calculated as ruthenium is 0.01-100:1, preferably 0.1-10:1, such as 0.1:1, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, or the range between any two of them, and more preferably 1-5:1.
[0043] In the present invention, a tri-organic phosphine and / or an oxidized tri-organic phosphine compound is used as the second auxiliary agent, which, in combination with the catalyst active component, the first auxiliary agent, and the third auxiliary agent, can improve the catalytic effect of the olefin hydroformylation reaction.
[0044] According to a preferred embodiment of the present invention, the second auxiliary agent is a substituted or unsubstituted triphenylphosphine and / or triphenylphosphine oxide.
[0045] In the present invention, preferably, the above-mentioned types and specific amounts of the first auxiliary agent, the second auxiliary agent, and the third auxiliary agent are combined with the catalyst active component, which can improve the activity of the hydroformylation reaction in the catalytic system, effectively inhibit the occurrence of side reactions of olefin hydrogenation, and have a high conversion rate of reaction raw materials and a high alcohol yield.
[0046] The second aspect of the present invention provides an application of the catalyst composition described in the first aspect in the hydroformylation reaction.
[0047] The third aspect of the present invention provides a method for preparing higher alcohols by olefin hydroformylation, which includes: in the presence of a catalyst composition, using carbon dioxide and hydrogen as reaction gas sources, and an olefin as a reaction substrate to carry out a hydroformylation reaction;
[0048] The catalyst composition is the catalyst composition described in the first aspect.
[0049] In the present invention, when the above-mentioned catalyst composition is used to catalyze the hydroformylation reaction of olefins, it has good catalytic activity and reduction performance. The aldehyde generated by the hydroformylation reaction can be further reduced to form an alcohol, and there are few side reaction products.
[0050] According to the present invention, preferably, the reaction is carried out in the presence of a solvent, and the solvent can be selected from conventional solvents in the art as long as it has good solubility for the reaction substrate, the catalyst active component, and the auxiliary agent. Preferably, the solvent is selected from at least one of aromatic hydrocarbons, ethers, alcohols, amines, and ketones, and preferably selected from at least one of toluene, tetrahydrofuran, N,N-dimethylformamide, and N-methylpyrrolidone.
[0051] According to the present invention, preferably, based on the total mass of the reaction solution, the mass concentration of the catalyst active component in terms of ruthenium is 0.001%-5%, such as 0.001%, 0.005%, 0.01%, 0.05%, 0.1%, 0.15%, 0.3%, 0.5%, 0.75%, 1%, 2%, 3%, 4%, 5%, or any range between any two of them, and preferably 0.01%-1%.
[0052] According to the present invention, preferably, in the reaction, the molar ratio of carbon dioxide to hydrogen is 0.1 - 10:1, for example, 0.1:1, 0.5:1, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, or the range between any two of them, and preferably 0.5 - 5:1.
[0053] In the present invention, preferably, controlling the molar ratio of carbon dioxide to hydrogen within the above range can avoid the side reaction of hydrogenation between excessive hydrogen and the olefin of the reaction raw material, and excessive carbon dioxide will reduce the reaction rate.
[0054] According to the present invention, preferably, the olefin is an olefin with 2 - 30 carbon atoms, preferably an olefin with 5 - 15 carbon atoms, and more preferably at least one selected from the group consisting of pentene, octene, nonene, decene, undecene, dodecene, and tetradecene.
[0055] According to a preferred embodiment of the present invention, the mass ratio of the olefin to the solvent is 0.01 - 5:1, for example, 0.01:1, 0.1:1, 0.5:1, 1:1, 2:1, 3:1, 4:1, 5:1, or the range between any two of them, and preferably 0.1 - 2:1.
[0056] In the present invention, preferably, the addition amounts of carbon dioxide and hydrogen are controlled by pressure, as long as the pressure of the mixed gas of carbon dioxide and hydrogen introduced reaches the pressure at which the hydroformylation reaction can proceed.
[0057] According to the present invention, preferably, the pressure of the reaction is 0.5 - 50 MPa, preferably 2 - 15 MPa, for example, 2 MPa, 3 MPa, 4 MPa, 5 MPa, 6 MPa, 7 MPa, 8 MPa, 9 MPa, 10 MPa, 11 MPa, 12 MPa, 13 MPa, 14 MPa, 15 MPa, or the range between any two of them, and more preferably 4 - 10 MPa.
[0058] According to the present invention, preferably, the reaction temperature is 50 - 250 °C, preferably 100 - 180 °C, for example, 100 °C, 110 °C, 120 °C, 130 °C, 140 °C, 150 °C, 160 °C, 170 °C, 180 °C, or the range between any two of them, and more preferably 120 - 160 °C.
[0059] In the present invention, there is no special limitation on the hydroformylation reaction vessel, and it can be a conventional reactor in the art. Preferably, the hydroformylation reaction can be carried out in a reaction kettle.
[0060] In the present invention, the product of the hydroformylation reaction is a mixture of aldehyde and alcohol, and the product is mainly alcohol.
[0061] Preferably, in the present invention, the hydroformylation reaction is carried out under the above reaction conditions, which can reduce the formation of by-products isomerized olefins and alkanes in the hydroformylation reaction and improve the catalytic activity of the catalyst composition and the yield of alcohol products.
[0062] According to a particularly preferred embodiment of the present invention, the present invention provides a catalyst composition, which comprises a catalyst active component, a first promoter, a second promoter and a third promoter;
[0063] The catalyst active component is Ru3(CO) 12 and / or H4Ru4(CO) 12 ;
[0064] The first promoter is selected from at least one of LiCl, KF and NaCl, and the molar ratio of the first promoter to the catalyst active component calculated as ruthenium is 5-50:1;
[0065] The second promoter is substituted or unsubstituted triphenylphosphine and / or triphenylphosphine oxide, and the molar ratio of the second promoter to the catalyst active component calculated as ruthenium is 1-5:1;
[0066] The third promoter is selected from at least one of acetic anhydride, benzoic acid, acetic acid, lithium acetate and sodium benzoate, and the molar ratio of the third promoter to the catalyst active component calculated as ruthenium is 5-50:1.
[0067] The present invention will be described in detail below through examples and comparative examples. In the following examples and comparative examples,
[0068] The product components were qualitatively and quantitatively analyzed by Agilent-6890 gas chromatography with a microinjector, and the product quantification method was calculated by normalization using the peak area and correction factor. Among them:
[0069]
[0070]
[0071] Unless otherwise specified, the reagents used in the present invention are all of analytical grade, and all the reagents used are commercially available.
[0072] Specific experimental operation: Weigh a certain amount of the catalyst active component and the promoter, place them in a 100 mL reaction kettle, then add 25 g of N-methylpyrrolidone as the solvent and 4.5 g of 1-octene as the reaction substrate, and mix them evenly with the catalyst active component and the promoter.
[0073] After installing the reactor, first introduce carbon dioxide gas to displace the air in the system, repeat 3 - 5 times, start stirring, and introduce carbon dioxide gas during stirring until the pressure in the reactor reaches 2.5 MPa, then introduce hydrogen until the pressure in the reactor reaches 5 MPa, and stop gas injection. Set the reaction temperature to 140 °C, start heating, record the reaction time after the temperature rises to 140 °C, turn off the heating after the reaction ends, cool down the reactor through an ice - water bath, then release the pressure, and take the liquid phase after the reaction for component analysis.
[0074] Example 1
[0075] In the reaction system, Ru3(CO) 12 is used as the catalyst active component. Based on the total mass of the reaction solution, the mass concentration of ruthenium is 0.15%, LiCl is the first additive, the molar ratio of the first additive to ruthenium is 20:1, triphenylphosphine oxide is the second additive, the molar ratio of the second additive to ruthenium is 2:1, acetic acid is the third additive, and the molar ratio of the third additive to ruthenium is 20:1;
[0076] The reaction time is 6 h. After measurement, the conversion rate of 1 - octene is 99.2%, the yield of aldehyde alcohol is 73.6% (alcohol 72.0%), the yield of isomerized olefins is 7.2%, and the yield of alkanes obtained by hydrogenation of olefins is 18.4%.
[0077] Example 2
[0078] In the reaction system, H2Ru4(CO) 12 is used as the catalyst active component. Based on the total mass of the reaction solution, the mass concentration of ruthenium is 0.15%, LiCl is the first additive, the molar ratio of the first additive to ruthenium is 20:1, triphenylphosphine oxide is the second additive, the molar ratio of the second additive to ruthenium is 1.5:1, benzoic acid is the third additive, and the molar ratio of the third additive to ruthenium is 8:1;
[0079] The reaction time is 6 h. After measurement, the conversion rate of 1 - octene is 99.0%, the yield of aldehyde alcohol is 74.1% (alcohol 72.3%), the yield of isomerized olefins is 7.6%, and the yield of alkanes obtained by hydrogenation of olefins is 17.3%.
[0080] Example 3
[0081] In the reaction system, Ru3(CO) 12 is used as the catalyst active component. Based on the total mass of the reaction solution, the mass concentration of ruthenium is 0.15%, LiCl is the first additive, the molar ratio of the first additive to ruthenium is 20:1, triphenylphosphine oxide is the second additive, the molar ratio of the second additive to ruthenium is 1.5:1, benzoic acid is the third additive, and the molar ratio of the third additive to ruthenium is 8:1;
[0082] The reaction time was 6 h. It was determined that the conversion rate of 1-octene was 99.3%, the yield of aldol was 73.5% (72.0% for alcohol), the yield of isomerized olefins was 6.7%, and the yield of alkanes obtained by hydrogenation of olefins was 19.1%.
[0083] Example 4
[0084] In the reaction system, Ru3(CO) 12 was used as the active component of the catalyst. Based on the total mass of the reaction solution, the mass concentration of ruthenium was 0.15%. LiCl was the first auxiliary agent, and the molar ratio of the first auxiliary agent to ruthenium was 20:1. Triphenylphosphine was the second auxiliary agent, and the molar ratio of the second auxiliary agent to ruthenium was 1.8:1. Lithium acetate was the third auxiliary agent, and the molar ratio of the third auxiliary agent to ruthenium was 10:1;
[0085] The reaction time was 6 h. It was determined that the conversion rate of 1-octene was 99.0%, the yield of aldol was 71.9% (70.6% for alcohol), the yield of isomerized olefins was 8.4%, and the yield of alkanes obtained by hydrogenation of olefins was 18.7%.
[0086] Example 5
[0087] In the reaction system, Ru3(CO) 12 was used as the active component of the catalyst. Based on the total mass of the reaction solution, the mass concentration of ruthenium was 0.15%. LiCl was the first auxiliary agent, and the molar ratio of the first auxiliary agent to ruthenium was 18:1. Triphenylphosphine was the second auxiliary agent, and the molar ratio of the second auxiliary agent to ruthenium was 1.5:1. Acetic anhydride was the third auxiliary agent, and the molar ratio of the third auxiliary agent to ruthenium was 5:1;
[0088] The reaction time was 6 h. It was determined that the conversion rate of 1-octene was 98.9%, the yield of aldol was 69.3% (68.5% for alcohol), the yield of isomerized olefins was 9.9%, and the yield of alkanes obtained by hydrogenation of olefins was 19.7%.
[0089] Example 6
[0090] In the reaction system, Ru3(CO) 12 was used as the active component of the catalyst. Based on the total mass of the reaction solution, the mass concentration of ruthenium was 0.15%. LiCl was the first auxiliary agent, and the molar ratio of the first auxiliary agent to ruthenium was 20:1. Triphenylphosphine was the second auxiliary agent, and the molar ratio of the second auxiliary agent to ruthenium was 1.5:1. Sodium benzoate was the third auxiliary agent, and the molar ratio of the third auxiliary agent to ruthenium was 7:1;
[0091] The reaction time was 6 h. It was determined that the conversion rate of 1-octene was 99.2%, the yield of aldol was 70.4% (69.0% for alcohol), the yield of isomerized olefins was 9.6%, and the yield of alkanes obtained by hydrogenation of olefins was 19.2%.
[0092] Example 7
[0093] In the reaction system, Ru3(CO) 12 is used as the catalyst active component. Based on the total mass of the reaction solution, the mass concentration of ruthenium is 0.15%, KF is the first auxiliary agent, the molar ratio of the first auxiliary agent to ruthenium is 20:1, triphenylphosphine oxide is the second auxiliary agent, the molar ratio of the second auxiliary agent to ruthenium is 1.5:1, and benzoic acid is the third auxiliary agent, and the molar ratio of the third auxiliary agent to ruthenium is 6:1;
[0094] The reaction time is 6 h. After measurement, the conversion rate of 1-octene is 99.2%, the yield of aldehyde alcohol is 70.2% (alcohol 69.0%), the yield of isomerized olefin is 9.7%, and the yield of alkane obtained by hydrogenation of olefin is 19.3%.
[0095] Example 8
[0096] The same catalyst composition as in Example 1 is used, except that the molar ratio of the first auxiliary agent to ruthenium is 1:1;
[0097] The reaction time is 6 h. After measurement, the conversion rate of 1-octene is 99.8%, the yield of aldehyde alcohol is 19.2% (alcohol 18.5%), the yield of isomerized olefin is 14.5%, and the yield of alkane obtained by hydrogenation of olefin is 66.1%.
[0098] Example 9
[0099] The same catalyst composition as in Example 1 is used, except that the molar ratio of the second auxiliary agent to ruthenium is 15:1;
[0100] The reaction time is 6 h. After measurement, the conversion rate of 1-octene is 93.6%, the yield of aldehyde alcohol is 21.5% (alcohol 12.1%), the yield of isomerized olefin is 58.1%, and the yield of alkane obtained by hydrogenation of olefin is 14.0%.
[0101] Example 10
[0102] The same catalyst composition as in Example 1 is used, except that the molar ratio of the third auxiliary agent to ruthenium is 1:1;
[0103] The reaction time is 6 h. After measurement, the conversion rate of 1-octene is 99.4%, the yield of aldehyde alcohol is 40.5% (alcohol 28.8%), the yield of isomerized olefin is 30.3%, and the yield of alkane obtained by hydrogenation of olefin is 28.6%.
[0104] Comparative Example 1
[0105] In the reaction system, Ru3(CO) 12 is used as the catalyst active component. Based on the total mass of the reaction solution, the mass concentration of ruthenium is 0.15%, LiCl is the first auxiliary agent, and the molar concentration ratio of the first auxiliary agent to ruthenium is 18:1;
[0106] The reaction time was 12 h. After measurement, the conversion rate of 1-octene was 98.5%, the yield of aldehyde alcohol was 28.3% (alcohol 16.0%), the yield of isomerized olefins was 36.5%, and the yield of alkanes obtained by hydrogenation of olefins was 33.7%.
[0107] Comparative Example 2
[0108] Ru3(CO) was selected as the catalyst active component in the reaction system. Based on the total mass of the reaction solution, the mass concentration of ruthenium was 0.15%. LiCl was the first auxiliary agent, and the molar concentration ratio of the first auxiliary agent to ruthenium was 19:1. Triphenylphosphine was the second auxiliary agent, and the molar concentration ratio of the second auxiliary agent to ruthenium was 2:1; 12 Based on the total mass of the reaction solution, the mass concentration of ruthenium was 0.15%. LiCl was the first auxiliary agent, and the molar concentration ratio of the first auxiliary agent to ruthenium was 19:1. Triphenylphosphine was the second auxiliary agent, and the molar concentration ratio of the second auxiliary agent to ruthenium was 2:1;
[0109] The reaction times were 6 h and 12 h respectively. The raw material conversion rates and product yields obtained by measurement are shown in the following table.
[0110] Reaction time 1-Octene conversion rate % Aldol yield % Isomerization yield % Alkane yield % 6h 98.5 27.9 (alcohol 16.6) 39.6 31.0 12h 98.3 46.7 (alcohol 35.8) 20.8 30.8
[0111] Comparative Example 3
[0112] Ru3(CO) was selected as the catalyst active component in the reaction system. 12 Based on the total mass of the reaction solution, the mass concentration of ruthenium was 0.15%. LiCl was the first auxiliary agent, and the molar concentration ratio of the first auxiliary agent to ruthenium was 17:1. Triphenylphosphine oxide was the second auxiliary agent, and the molar concentration ratio of the second auxiliary agent to ruthenium was 1.5:1;
[0113] The reaction times were 6 h and 12 h respectively. The raw material conversion rates and product yields obtained by measurement are shown in the following table.
[0114] Reaction time 1-Octene conversion rate % Aldol yield % Isomerization yield % Alkane yield % 6h 98.5 28.2 (alcohol 17.5) 40.2 30.1 12h 98.6 49.8 (alcohol 36.5) 19.9 28.9
[0115] From the comparison of the results obtained from the examples and comparative examples of the hydroformylation reaction using carbon dioxide as the carbonyl source above, it can be seen that when the catalyst composition described in Examples 1-7 is used for the hydroformylation reaction, by combining the ruthenium catalyst with three catalytic auxiliary agents, the reaction activity of the catalytic system can be improved, the conversion rate of olefins is high, and the yield of alcohol in the product is above 68%, and a relatively high yield of the target product alcohol can be obtained.
[0116] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention, including any other suitable combination of each technical feature. These simple modifications and combinations should also be regarded as the content disclosed by the present invention and fall within the protection scope of the present invention.
Claims
1. A catalyst composition, characterized in that, The catalyst composition comprises a catalyst active component, as well as a first promoter, a second promoter and a third promoter; Wherein, the first promoter is a salt containing halogen ions, the second promoter is a triorganophosphine and / or an oxidized triorganophosphine compound, and the third promoter is a compound having the structure shown in formula (Ⅰ) and / or a compound having the structure shown in formula (Ⅱ), In formula (Ⅰ) or formula (Ⅱ), R1, R2, and R3 are each independently hydrogen or a substituted or unsubstituted hydrocarbon group, and in formula (Ⅰ), X is a monovalent cation.
2. The catalyst composition according to claim 1, wherein, The active component of the catalyst is a ruthenium catalyst containing carbonyl groups, preferably selected from at least one of Ru3(CO) 12 , H4Ru4(CO) 12 and Ru2Cl4(CO)6.
3. The catalyst composition according to claim 1 or 2, wherein, The cation in the first auxiliary agent is an organic or inorganic cation. Preferably, the cation is selected from at least one of Li + , Na + , K + , and NH4 + ; Preferably, the halogen ion is Cl - or F - ; Preferably, the molar ratio of the first promoter to the catalyst active component calculated as ruthenium is 0.1 - 500:1, 1 - 100:1, more preferably 5 - 50:
1.
4. The catalyst composition according to any one of claims 1-3, wherein, In formula (I), X is selected from at least one of H + , Li + , Na + , K + , NH4 + , Cu + and Ag + , and X is preferably selected from at least one of H + , Li + , Na + and K + ; Preferably, in formula (Ⅰ) or formula (Ⅱ), R1, R2, and R3 are each independently hydrogen or a substituted or unsubstituted C1 - C24 hydrocarbon group, preferably each independently hydrogen or at least one selected from substituted or unsubstituted methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopentyl, cyclohexyl, cycloheptyl, phenyl, benzyl, and naphthyl; Preferably, the molar ratio of the third promoter to the catalyst active component calculated as ruthenium is 0.1 - 1000:1, preferably 1 - 100:1, more preferably 5 - 50:
1.
5. The catalyst composition according to any one of claims 1-4, wherein, The second promoter is a compound having the structure shown in formula (Ⅲ) and / or a compound having the structure shown in formula (Ⅳ), In formula (Ⅲ) or formula (Ⅳ), R1, R2, R3, R4, R5, and R6 are each independently selected from substituted or unsubstituted C1 - C24 hydrocarbon groups, more preferably at least one selected from substituted or unsubstituted methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopentyl, cyclohexyl, cycloheptyl, phenyl, benzyl, and naphthyl; Preferably, the second promoter is a substituted or unsubstituted triphenylphosphine and / or triphenylphosphine oxide; Preferably, the molar ratio of the second promoter to the catalyst active component calculated as ruthenium is 0.01 - 100:1, preferably 0.1 - 10:1, more preferably 1 - 5:
1.
6. Use of the catalyst composition according to any one of claims 1 - 5 in a hydroformylation reaction.
7. A method for preparing higher alcohols by hydroformylation of olefins, the method comprising: In the presence of the catalyst composition, using carbon dioxide and hydrogen as reaction gas sources, and an olefin as a reaction substrate to carry out a hydroformylation reaction; The catalyst composition is the catalyst composition according to any one of claims 1 - 5.
8. The method according to claim 7, wherein, The reaction is carried out in the presence of a solvent, and the solvent is selected from at least one of aromatic hydrocarbons, ethers, alcohols, amines, and ketones, preferably at least one selected from toluene, tetrahydrofuran, N,N-dimethylformamide, and N-methylpyrrolidone; Preferably, based on the total mass of the reaction solution, the mass concentration of the catalyst active component calculated as ruthenium is 0.001% - 5%, preferably 0.01% - 1%.
9. The method according to claim 7, wherein In the reaction, the molar ratio of carbon dioxide to hydrogen is 0.1 - 10:1, preferably 0.5 - 5:1; Preferably, the olefin is a C2 - C30 olefin, preferably a C5 - C15 olefin, and the mass ratio of the olefin to the solvent is 0.01 - 5:1, preferably 0.1 - 2:
1.
10. The method according to any one of claims 7-9, wherein, The pressure of the reaction is 0.5 - 50 MPa, preferably 2 - 15 MPa; the reaction temperature is 50 - 250 °C, preferably 100 - 180 °C.