Catalyst composition, application thereof and olefin hydroformylation method

Abstract

The invention relates to the field of hydroformylation reaction, and discloses a catalyst composition and application thereof, and an olefin hydroformylation method, the catalyst composition comprises a catalyst active component, a first auxiliary agent, a second auxiliary agent and a third auxiliary agent; wherein the first auxiliary agent is salt containing halide ions, the second auxiliary agent is a tri-organic phosphite ester compound, the third auxiliary agent is a compound with a structure shown in a formula (I) and / or a compound with a structure shown in a formula (II), in the formula (I) or the formula (II), R1, R2 and R3 are respectively and independently hydrogen or substituted or unsubstituted alkyl, and X in the formula (I) is monovalent cation. The catalyst composition is used for olefin hydroformylation reaction taking carbon dioxide as a carbonyl source, and has high catalytic reaction activity and aldehyde alcohol product yield. # imgabs0 #

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 the hydroformylation of olefins. Background Art

[0002] The hydroformylation of olefins is one of the important organic synthesis reactions, which is widely used in industrial production and the synthesis of fine chemicals. Its main products are aldehydes and alcohols, and the annual total output in China can reach tens of millions of tons. At present, industrially, toxic and flammable CO is mainly used as the carbonyl source. If non-toxic and easily available CO2 can be used instead of CO as the carbonyl source, it has important value for developing a green and efficient synthesis process for the hydroformylation of olefins and realizing the efficient resource utilization of carbon dioxide.

[0003] The reverse water-gas shift (RWGS) reaction can convert CO2 into CO, which is more valuable for organic synthesis. This conversion process is also one of the most promising CO2 conversion pathways currently recognized. In industrial processes, RWGS is mainly used to adjust the carbon / hydrogen ratio of the syngas used in Fischer-Tropsch synthesis. Heterogeneous catalysts such as Cu-Ni and Cu-Zn / Al2O3 are commonly used, and the reaction temperature mostly exceeds 250 °C, which does not match the temperature and other process conditions required for the subsequent hydroformylation reactions of CO and olefins.

[0004] CN102933537A discloses a method for synthesizing aliphatic aldehydes from alkanes and carbon dioxide, dehydrogenating the alkanes to produce a mixture of olefins and hydrogen, adding carbon dioxide and hydrogen to the mixture, and performing hydroformylation to obtain at least one aldehyde. CN106278786A discloses a method for producing hydroformylation raw materials from alkanes and carbon dioxide, reacting the alkanes with carbon dioxide to produce a mixed product including olefins, carbon monoxide, and hydrogen, separating the mixed product, and performing hydroformylation on the separated product including olefins, carbon monoxide, hydrogen, and unreacted raw materials.

[0005] Currently, in research and process reports, catalytic reforming of alkanes and carbon dioxide is mostly used to generate hydroformylation reaction raw materials, which are then fed into the hydroformylation reaction unit for hydroformylation reactions. Such multi-stage reaction processes are relatively complex, the matching of process conditions is relatively poor, and the process design requirements for equipment are relatively high. Summary of the Invention

[0006] The object of the present invention is to overcome the problems in the prior art that the process for the hydroformylation of olefins using CO2 as the carbonyl source is complex and the matching of process conditions is relatively poor. The present invention provides a catalyst composition, its application, and a method for the hydroformylation of olefins. This catalyst composition simultaneously has the catalytic functions of carbon dioxide reverse water-gas shift and olefin hydroformylation reactions, can effectively inhibit the side reaction of olefin hydrogenation, and realizes the synchronous coupling of reverse water-gas shift and hydroformylation reactions.

[0007] 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;

[0008] Wherein, the first promoter is a salt containing halogen ions, the second promoter is a tri-organic phosphite 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),

[0009]

[0010] 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.

[0011] Preferably, 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 + .

[0012] 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 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.

[0013] A second aspect of the present invention provides the use of the catalyst composition described in the first aspect in a hydroformylation reaction.

[0014] A third aspect of the present invention provides a method for hydroformylating an olefin, the method comprising: in the presence of a catalyst composition, using carbon dioxide and hydrogen as reaction gas sources, and using an olefin as a reaction substrate to carry out a hydroformylation reaction;

[0015] The catalyst composition is the catalyst composition described in the first aspect.

[0016] Through the above technical solutions, the beneficial effects obtained by the present invention are as follows:

[0017] (1) In the present invention, by using the catalyst active component in combination with the first promoter, the second promoter, and the third promoter, the catalyst composition simultaneously has the catalytic functions of the reverse water-gas shift of carbon dioxide and the hydroformylation reaction of olefins, realizing the synchronous coupling of the reverse water-gas shift and the hydroformylation reaction, and preparing the aldehyde alcohol product by a one-pot method, which has important industrial application prospects;

[0018] (2) The catalyst composition provided by the present invention can further improve the activity of the hydroformylation reaction in the catalytic system, and can also effectively inhibit the occurrence of side reactions of olefin hydrogenation, with high conversion rate of reaction raw materials and high product yield. Detailed implementation mode

[0019] In the ranges disclosed herein, the endpoints and any values 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, the endpoint values of each range, between the endpoint values of each range and individual point values, and between individual point values 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.

[0020] In the first aspect of the present invention, a catalyst composition is provided, wherein the catalyst composition includes a catalyst active component, a first promoter, a second promoter, and a third promoter;

[0021] Among them, the first promoter is a salt containing halogen ions, the second promoter is a tri-organic phosphite 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),

[0022]

[0023] 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.

[0024] In the present invention, by using the first promoter, the second promoter, and the third promoter in combination with the catalyst active component, the obtained catalyst composition can simultaneously have the functions of catalyzing the reverse water-gas shift of carbon dioxide and the hydroformylation reaction of olefins, realizing the synchronous coupling of the reverse water-gas shift and the hydroformylation reaction.

[0025] 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 further accelerate the hydroformylation reaction rate.

[0026] According to the present invention, preferably, in formula (I), X is selected from H + 、Li + 、Na + 、K+ 、 NH4 + 、 Cu + and Ag + and at least one of X is preferably selected from H + 、 Li + 、 Na + and K + and at least one of them.

[0027] 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.

[0028] In the present invention, the C1-C24 hydrocarbon group refers to a hydrocarbon group having 1-24 carbon atoms in total.

[0029] 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.

[0030] 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.

[0031] 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, benzoic anhydride, and sodium benzoate. Adopting this preferred embodiment can further stably increase the hydroformylation reaction rate.

[0032] According to the present invention, preferably, the cation in the first auxiliary agent is an organic or inorganic cation. Preferably, the cation is selected from Li + 、 Na + 、 K + and NH4 + and at least one of them.

[0033] According to the present invention, preferably, the halogen ion in the first auxiliary agent is Cl - or F - .

[0034] According to a preferred embodiment of the present invention, the first auxiliary agent is selected from at least one of LiCl, KF, and NaCl.

[0035] In the present invention, adding the first auxiliary agent of the above preferred scheme in combination with the catalyst active component, the second auxiliary agent, and the third auxiliary agent can inhibit the side reaction of olefin hydrogenation and reduce the generation of inert by-product alkanes.

[0036] According to the present invention, preferably, the second auxiliary agent has the structure shown in formula (III).

[0037]

[0038] In formula (III), R1, R2, and R3 are each independently selected from substituted or unsubstituted hydrocarbon groups, preferably 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.

[0039] In the present invention, the substituents are each independently selected from at least one of C1-C6 alkyl groups, halogens, C1-C6 alkoxy groups, hydroxyl groups, and carboxyl groups.

[0040] In the present invention, using the tri-organic phosphite compound as the second auxiliary agent, in combination with the catalyst active component, the first auxiliary agent, and the third auxiliary agent, can promote the hydroformylation reaction, has high catalytic reaction activity, improves the olefin conversion rate, and obtains a higher yield of aldehyde-alcohol products.

[0041] According to a preferred embodiment of the present invention, the second auxiliary agent is selected from at least one of tributyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, triphenyl phosphite, and triethyl phosphite.

[0042] According to the present invention, preferably, the catalyst active component is a ruthenium catalyst containing a carbonyl group, preferably selected from at least one of Ru3(CO) 12 , H4Ru4(CO) 12 and Ru2Cl4(CO)6.

[0043] In the present invention, preferably, using the above-mentioned preferred catalyst active component, in combination with the above-mentioned three selected auxiliary agents, can simultaneously have the effects of catalyzing the reverse water gas shift of CO2 and the hydroformylation reaction of olefins.

[0044] According to the present invention, preferably, the molar ratio of the first auxiliary agent to the catalyst active component calculated by ruthenium is 0.1-500:1, preferably 1-100:1, for example, 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, more preferably 5-50:1.

[0045] According to the present invention, preferably, the molar ratio of the second promoter to the catalyst active component in terms of 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.

[0046] According to the present invention, preferably, the molar ratio of the third promoter to the catalyst active component in terms of 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.

[0047] In the present invention, preferably, the combination of the first promoter, the second promoter and the third promoter of the above types and specific amounts with the catalyst active component can improve the activity of the hydroformylation reaction in the catalytic system, effectively inhibit the occurrence of side reactions of olefin hydrogenation, and has a high conversion rate of reaction raw materials and a high product yield.

[0048] The second aspect of the present invention provides the application of the catalyst composition described in the first aspect in the hydroformylation reaction.

[0049] The third aspect of the present invention provides a method for 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;

[0050] The catalyst composition is the catalyst composition described in the first aspect.

[0051] 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 promoter. Preferably, the solvent is selected from at least one of aromatic hydrocarbons, ethers, alcohols, amines and ketones, and more preferably from at least one of toluene, tetrahydrofuran, N,N - dimethylformamide and N - methylpyrrolidone.

[0052] 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 the range between any two of them, and preferably 0.01% - 1%.

[0053] According to the present invention, preferably, in the reaction, the molar ratio of carbon dioxide to hydrogen is 0.1 - 10:1, such as 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, preferably 0.5 - 5:1.

[0054] In the present invention, preferably, controlling the molar ratio of carbon dioxide to hydrogen within the above range can avoid the hydrogenation side reaction of the olefin of the reaction raw material with excessive hydrogen, and excessive carbon dioxide will reduce the reaction rate.

[0055] According to the present invention, preferably, the olefin is an olefin having 2 - 30 carbon atoms, preferably a monoolefin having 2 - 12 carbon atoms, and more preferably at least one selected from ethylene, propylene, butene, and octene.

[0056] According to a preferred embodiment of the present invention, the mass ratio of the olefin to the solvent is 0.01 - 5:1, such as 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, preferably 0.1 - 2:1.

[0057] 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.

[0058] According to the present invention, preferably, the pressure of the reaction is 0.5 - 50 MPa, preferably 2 - 15 MPa, such as 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, more preferably 4 - 10 MPa.

[0059] According to the present invention, preferably, the reaction temperature is 50 - 250 °C, preferably 100 - 180 °C, such as 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, more preferably 120 - 160 °C.

[0060] In the present invention, the product of the hydroformylation reaction is a mixture of aldehyde and alcohol, and the aldehyde - alcohol yield is the sum of the yields of aldehyde and alcohol.

[0061] In the present invention, preferably, carrying out the hydroformylation reaction under the above reaction conditions can reduce the formation of by - product isomerized olefins and alkanes in the hydroformylation reaction, and improve the catalytic activity of the catalyst composition and the aldehyde - alcohol product yield.

[0062] According to a particularly preferred embodiment of the present invention, the present invention provides a catalyst composition, which comprises a catalyst active component, as well as 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 by ruthenium is 5 - 50:1;

[0065] The second promoter is selected from at least one of tributyl phosphite, tris(2,4 - di - tert - butylphenyl) phosphite, triphenyl phosphite and triethyl phosphite, and the molar ratio of the second promoter to the catalyst active component calculated by 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 benzoic anhydride, and the molar ratio of the third promoter to the catalyst active component calculated by 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 components of the product are qualitatively and quantitatively analyzed by Agilent - 6890 gas chromatography with micro - injection. The product quantitative method is calculated by normalization using 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 promoters, place them in a 100 mL autoclave, 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 promoters.

[0073] After installing the reactor, first introduce carbon dioxide gas to displace the air in the system, repeat 3 - 5 times, start stirring, 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 introduction. 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 relieve 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 auxiliary agent, the molar ratio of the first auxiliary agent to ruthenium is 20:1, tris(2,4 - di - tert - butylphenyl) phosphite is the second auxiliary agent, the molar ratio of the second auxiliary agent to ruthenium is 1.5:1, acetic anhydride is the third auxiliary agent, and the molar ratio of the third auxiliary agent to ruthenium is 6:1;

[0076] The reaction time is 6 h. After measurement, the conversion rate of 1 - octene is 99.5%, the yield of aldol is 77.3%, the yield of isomerized olefins is 6.6%, and the yield of alkanes obtained by hydrogenation of olefins is 15.6%.

[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 auxiliary agent, the molar ratio of the first auxiliary agent to ruthenium is 20:1, tributyl phosphite is the second auxiliary agent, the molar ratio of the second auxiliary agent to ruthenium is 1.3:1, benzoic anhydride is the third auxiliary agent, and the molar ratio of the third auxiliary agent to ruthenium is 9:1;

[0079] The reaction time is 6 h. After measurement, the conversion rate of 1 - octene is 99.5%, the yield of aldol is 78.0%, the yield of isomerized olefins is 6.8%, and the yield of alkanes obtained by hydrogenation of olefins is 14.7%.

[0080] Example 3

[0081] 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 auxiliary agent, the molar ratio of the first auxiliary agent to ruthenium is 20:1, tris(2,4 - di - tert - butylphenyl) phosphite is the second auxiliary agent, the molar ratio of the second auxiliary agent to ruthenium is 1.5:1, benzoic acid is the third auxiliary agent, and the molar ratio of the third auxiliary agent to ruthenium is 8:1;

[0082] The reaction time was 6 h. The conversion of 1-octene was determined to be 99.5%, the yield of aldehyde alcohol was 78.2%, the yield of isomerized olefins was 6.9%, and the yield of alkanes obtained by olefin hydrogenation was 14.8%.

[0083] Example 4

[0084] Select Ru3(CO) in the reaction system 12 The catalyst is an active component, based on the total mass of the reaction solution, the mass concentration of ruthenium is 0.15%, LiCl is a first auxiliary agent, the molar ratio of the first auxiliary agent to ruthenium is 20:1, tris(2,4-di-tert-butylphenyl)phosphite is a second auxiliary agent, the molar ratio of the second auxiliary agent to ruthenium is 1.5:1, and lithium acetate is a third auxiliary agent, the molar ratio of the third auxiliary agent to ruthenium is 15:1;

[0085] The reaction time was 6 h. The conversion of 1-octene was determined to be 99.6%, the yield of aldehyde alcohol was 77.9%, the yield of isomerized olefins was 6.6%, and the yield of alkanes obtained by olefin hydrogenation was 15.1%.

[0086] Example 5

[0087] Select Ru3(CO) in the reaction system 12 The catalyst is an active component, based on the total mass of the reaction solution, the mass concentration of ruthenium is 0.15%, LiCl is a first auxiliary agent, the molar ratio of the first auxiliary agent to ruthenium is 20:1, tris(2,4-di-tert-butylphenyl)phosphite is a second auxiliary agent, the molar ratio of the second auxiliary agent to ruthenium is 1.5:1, and benzoic acid is a third auxiliary agent, the molar ratio of the third auxiliary agent to ruthenium is 8:1;

[0088] The reaction time was 6 h. The conversion of 1-octene was determined to be 99.5%, the yield of aldehyde alcohol was 75.9%, the yield of isomerized olefins was 8.3%, and the yield of alkanes obtained by olefin hydrogenation was 15.3%.

[0089] Example 6

[0090] Select Ru3(CO) in the reaction system 12 The catalyst is an active component, based on the total mass of the reaction solution, the mass concentration of ruthenium is 0.15%, LiCl is a first auxiliary agent, the molar ratio of the first auxiliary agent to ruthenium is 20:1, tris(2,4-di-tert-butylphenyl)phosphite is a second auxiliary agent, the molar ratio of the second auxiliary agent to ruthenium is 1.5:1, sodium benzoate is a third auxiliary agent, and the molar ratio of the third auxiliary agent to ruthenium is 5:1;

[0091] The reaction time was 6 h. The conversion of 1-octene was determined to be 99.5%, the yield of aldehyde alcohol was 73.6%, the yield of isomerized olefins was 7.9%, and the yield of alkanes obtained by olefin hydrogenation was 18.0%.

[0092] Example 7

[0093] Ru3(CO) is selected as the catalyst active component in the reaction system. Based on the total mass of the reaction solution, the mass concentration of ruthenium is 0.15%, LiCl is the first auxiliary agent, the molar ratio of the first auxiliary agent to ruthenium is 20:1, tributyl phosphite is the second auxiliary agent, the molar ratio of the second auxiliary agent to ruthenium is 1.3:1, acetic acid is the third auxiliary agent, and the molar ratio of the third auxiliary agent to ruthenium is 15:1; 12

[0094] The reaction time is 6 h. It is measured that the conversion rate of 1-octene is 99.5%, the yield of aldol is 73.4%, the yield of isomerized olefins is 8.8%, and the yield of alkanes obtained by hydrogenation of olefins is 17.3%.

[0095] Example 8

[0096] Ru3(CO) is used as the catalyst active component in the reaction system. 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, tris(2,4-di-tert-butylphenyl) phosphite is the second auxiliary agent, the molar ratio of the second auxiliary agent to ruthenium is 1.3:1, acetic acid is the third auxiliary agent, and the molar ratio of the third auxiliary agent to ruthenium is 15:1; 12

[0097] The reaction time is 6 h. It is measured that the conversion rate of 1-octene is 99.4%, the yield of aldol is 75.1%, the yield of isomerized olefins is 7.9%, and the yield of alkanes obtained by hydrogenation of olefins is 16.4%.

[0098] Example 9

[0099] The same catalyst composition as in Example 2 is used, except that the molar ratio of the first auxiliary agent to ruthenium is 1:1.

[0100] The reaction time is 6 h. It is measured that the conversion rate of 1-octene is 99.7%, the yield of aldol is 16.8%, the yield of isomerized olefins is 13.6%, and the yield of alkanes obtained by hydrogenation of olefins is 69.3%.

[0101] Example 10

[0102] The same catalyst composition as in Example 2 is used, except that the molar ratio of the second auxiliary agent to ruthenium is 12:1.

[0103] The reaction time is 6 h. It is measured that the conversion rate of 1-octene is 94.2%, the yield of aldol is 26.5%, the yield of isomerized olefins is 51.9%, and the yield of alkanes obtained by hydrogenation of olefins is 15.8%.

[0104] Example 11

[0105] ​​The same catalyst composition as in Example 2 was used, except that the molar ratio of the third promoter to ruthenium was 1:1.

[0106] The reaction time was 6 h. It was determined that the conversion rate of 1-octene was 99.7%, the yield of aldol was 50.1%, the yield of isomerized olefins was 21.2%, and the yield of alkanes obtained by hydrogenation of olefins was 28.3%.

[0107] Comparative Example 1

[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%, the mass concentration of ruthenium was 0.15%, LiCl was the first promoter, and the molar concentration ratio of the first promoter to ruthenium was 18:1; 12 The reaction time was 12 h. It was determined that the conversion rate of 1-octene was 98.5%, the yield of aldol was 28.3%, the yield of isomerized olefins was 36.5%, and the yield of alkanes obtained by hydrogenation of olefins was 33.7%.

[0109] Comparative Example 2

[0110] 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 promoter, the molar concentration ratio of the first promoter to ruthenium was 20:1, tributyl phosphite was the second promoter, and the molar concentration ratio of the second promoter to ruthenium was 1.5:1;

[0111] The reaction times were 6 h and 12 h respectively. The raw material conversion rates and product yields determined are shown in the following table. 12 Comparative Example 3

[0112] 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 promoter, the molar concentration ratio of the first promoter to ruthenium was 20:1, tris(2,4-di-tert-butylphenyl) phosphite was the second promoter, and the molar concentration ratio of the second promoter to ruthenium was 1.5:1;

[0113] Reaction time Conversion rate of 1-octene % Yield of aldol % Yield of isomerization % Yield of alkane % 6h 98.4 35.9 23.9 25.8 12h 98.6 51.7 19.0 27.9

[0114] The reaction times were 6 h and 12 h respectively. The raw material conversion rates and product yields determined are shown in the following table.

[0115] 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 promoter, the molar concentration ratio of the first promoter to ruthenium was 20:1, tris(2,4-di-tert-butylphenyl) phosphite was the second promoter, and the molar concentration ratio of the second promoter to ruthenium was 1.5:1; 12 The reaction times were 6 h and 12 h respectively. The raw material conversion rates and product yields determined are shown in the following table.

[0116]

[0117] Reaction time Conversion rate of 1-octene % Yield of aldol % Yield of isomerization % Yield of alkane % 6h 98.8 40.6 32.2 26.0 12h 98.7 54.9 16.6 27.2

[0118] ​From the test results, it can be seen that when the catalyst compositions described in Embodiments 1-8 of the present invention are used for hydroformylation reaction, the olefin conversion rate is above 99%, the aldehyde-alcohol yield of the reaction product is also above 73%, the yield of isomerized olefins formed by side reactions is below 9%, and the olefin hydrogenation yield is below 20%. It has higher hydroformylation reaction activity and can obtain a higher aldehyde-alcohol yield of hydroformylation products.

[0119] In the catalyst composition of Comparative Example 1, only the catalyst active component and the first promoter LiCl were added. During the hydroformylation reaction of olefins, after 12 hours of reaction, the conversion rate of 1-octene was 98.5%, the aldehyde-alcohol yield was only 28.3%, the yield of isomerized olefins was as high as 36.5%, and the yield of alkanes formed by olefin hydrogenation was as high as 33.7%. There were too many side reaction products.

[0120] In the catalyst composition of Comparative Example 2, after the catalyst active component was combined with LiCl and tributyl phosphite for a 6-hour hydroformylation reaction, the conversion rate of 1-octene was 98.4%, the aldehyde-alcohol yield was only 35.9%, the yield of isomerized olefins reached 23.9%, and the yield of alkanes formed by olefin hydrogenation was 25.8%. There were still many side reaction products, the aldehyde-alcohol yield was low, and the catalytic effect of the hydroformylation reaction was worse than that of the catalyst compositions of Embodiments 1-8.

[0121] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited thereto. Within the technical concept scope 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 all fall within the protection scope of the present invention.

Claims

1. A catalyst composition, characterized in that, The catalyst composition includes 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 tri-organic phosphite 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, In formula (I), X is selected from H + , Li + , Na + , K + , NH4 + , Cu + and Ag + , and at least one of them. X is preferably selected from H + , Li + , Na + and K + , and at least one of them; 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.

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 + ; The halogen ion is Cl - or F - .

4. The catalyst composition according to any one of claims 1-3, wherein, The second promoter has the structure shown in formula (III), in formula (III), R1, R2, and R3 are each independently selected from substituted or unsubstituted hydrocarbon groups, preferably each independently a substituted or unsubstituted C1-C24 hydrocarbon group, more preferably each independently at least one selected from substituted or unsubstituted methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopentyl, cyclohexyl, cycloheptyl, phenyl, benzyl, and naphthyl.

5. The catalyst composition according to any one of claims 1-4, 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 6. The catalyst composition according to any one of claims 1-5, wherein, The molar ratio of the first promoter to the catalyst active component calculated as ruthenium is 0.1-500:1, preferably 1-100:1, more preferably 5-50:1; 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; 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.

7. Use of the catalyst composition according to any one of claims 1-6 in a hydroformylation reaction.

8. A method for the 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 1-6.

9. The method according to claim 8, 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%; Preferably, 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 C2-C12 monoolefin, 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 claim 8 or 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.

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