Cobalt-doped catalyst and preparation method thereof, and preparation method of aldehyde compound

Abstract

The present invention relates to a cobalt-doped catalyst used as a catalyst for hydroformylation reaction, wherein the cobalt-doped catalyst comprises a modified carrier and an active component loaded on the modified carrier; wherein the modified carrier is a metal oxide carrier modified by unsaturated fatty acid; and the active component is a complex formed by a cobalt salt, a co-metal salt and a thiazole carbene ligand, wherein the general structural formula of the thiazole carbene ligand is as shown in formula (1) and / or formula (2), wherein R1, R2, R3 and R4 are independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, phenyl or benzyl. The present invention also relates to a method for preparing the cobalt-doped catalyst and a method for preparing an aldehyde compound. When the cobalt-doped catalyst of the present invention is used as a catalyst for hydroformylation reaction, it has high activity, high selectivity and stable performance. In addition, the preparation method of the cobalt-doped catalyst of the present invention is simple, mild and environmentally friendly.

Description

Technical Field

[0001] The invention relates to the technical field of organic synthesis, in particular to a cobalt-doped catalyst and a preparation method thereof, and a preparation method of an aldehyde compound. Background Art

[0002] The hydroformylation reaction is a reaction in which H2 and CO are added to olefin molecules in the presence of an appropriate catalyst to produce aldehydes with high economic added value. The product aldehydes can be further reacted to obtain chemical products such as alcohols, amines, carboxylic acids, and esters, and are widely used in the fields of flavors and fragrances, medicine, etc.

[0003] At present, about 75% of the hydroformylation reactions in industry are completed with Rh catalysts. The widely used Rh catalysts are homogeneous rhodium catalysts synthesized from Rh and organic phosphine ligands (such as tris(triphenylphosphine)carbonyl rhodium), which have the characteristics of high catalytic activity and mild reaction conditions. However, the homogeneous rhodium catalysts have serious problems in industrial application, namely, the homogeneous rhodium catalysts are difficult to separate from the organic phase, and the phosphine ligands are easily oxidized and deactivated, and the phosphine-containing wastewater is difficult to treat. Therefore, researchers began to focus on the research of solid rhodium catalysts, such as patents CN111822045A, CN104710288A, CN109876847A, CN109847741A and CN113385205A, which all disclose solid rhodium catalysts. Although they can solve the problem of catalyst separation, they have the problems of easy loss of rhodium metal and inferior activity and selectivity to homogeneous rhodium catalysts.

[0004] In recent years, the price of rhodium metal has soared, more than 1,000 times that of metallic cobalt, so cobalt catalysts have the advantage of low price. In addition, cobalt catalysts are insensitive to poisons in raw materials and have isomerization activity, and have gradually become a research hotspot.

[0005] For example, patent CN115304649A discloses a cobalt catalyst for hydroformylation reaction, which is composed of cobalt salt, phosphine ligand and complex ligand, and is applied to the hydroformylation reaction of C2-C20 straight-chain and branched olefins, but the preparation process of the cobalt catalyst is demanding and needs to be prepared in a strict anhydrous and oxygen-free environment, which is not conducive to industrial large-scale production and use. Patent CN114426469A discloses a cobalt-phosphine catalyst, and is applied to the hydroformylation reaction of C8-C30 olefins, but the cobalt-phosphine catalyst selectivity of the method is poor, and the generated aldehyde is further hydrogenated, and the final product is a mixture of alcohol and aldehyde. Patent CN103561869A discloses a catalyst composition for hydroformylation and a hydroformylation method using the catalyst composition, the catalyst composition includes a monodentate phosphine ligand and a transition metal catalyst, but the catalyst composition still has the problem of low activity and poor selectivity of the cobalt catalyst.

[0006] It can be seen that the introduction of phosphine ligands can increase the stability and selectivity of the catalyst. However, the introduction of phosphine ligands increases the electron cloud density of the central metal, enhances the hydrogenation activity of the catalyst, intensifies the side reactions, and reduces the selectivity of aldehydes.

[0007] Patent CN115433064A discloses a cobalt precatalyst for hydroformylation reaction, the structural formula of which is [Co(acac)(C4H8O2)4] + [BF4]-, the cobalt precatalyst catalyzes the reaction of 1-octene at 140°C and 50 bar for 3 hours, with a yield between 62.7% and 69.3%, which has a large room for improvement.

[0008] It can be seen that traditional cobalt catalysts still have shortcomings such as low activity, poor selectivity and harsh production conditions, which are not conducive to large-scale industrial production and use. Summary of the invention

[0009] Based on this, it is necessary to provide a cobalt-doped catalyst to address the above problems. When the cobalt-doped catalyst is used as a catalyst for the hydroformylation reaction, it has high activity, high selectivity and stable performance. In addition, the preparation method of the cobalt-doped catalyst is simple, the conditions are mild and it is environmentally friendly.

[0010] In order to achieve the above object, the technical solution adopted by the present invention is: a cobalt-doped catalyst, the cobalt-doped catalyst is used as a catalyst for hydroformylation reaction, the cobalt-doped catalyst comprises a modified carrier and an active component loaded on the modified carrier;

[0011] Wherein, the modified carrier is a metal oxide carrier modified with unsaturated fatty acid;

[0012] The active component is a complex formed by a cobalt salt, a co-metal salt and a thiazole carbene ligand, and the general structural formula of the thiazole carbene ligand is shown in formula (1) and / or formula (2):

[0013]

[0014] In formula (1) and formula (2), R1, R2, R3 and R4 are independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, phenyl or benzyl.

[0015] In one embodiment, the metal oxide support is selected from at least one of a TiO2 support, a ZnO support, a CuO support, a Cu2O support, a Fe2O3 support, and a BiVO4 support;

[0016] And / or, the unsaturated fatty acid is at least one selected from oleic acid and linoleic acid;

[0017] And / or, the cobalt salt is selected from at least one of chloride or its hydrate, nitrate or its hydrate, sulfate or its hydrate, acetylacetonate or its hydrate;

[0018] And / or, the auxiliary metal salt is selected from iron-containing salts and / or nickel-containing salts, the iron-containing salt is selected from at least one of chlorides or hydrates thereof, nitrates or hydrates thereof, sulfates or hydrates thereof, and acetylacetonates or hydrates thereof, and the nickel-containing salt is selected from at least one of chlorides or hydrates thereof, nitrates or hydrates thereof, sulfates or hydrates thereof, and acetylacetonates or hydrates thereof;

[0019] And / or, R1, R2, R3 and R4 are independently selected from tert-butyl, phenyl or benzyl.

[0020] In one embodiment, the metal oxide support is selected from at least one of a Cu2O support, a Fe2O3 support, and a BiVO4 support;

[0021] And / or, the thiazole carbene ligand is selected from at least one of L1 to L4,

[0022]

[0023] In one embodiment, the mass ratio of the unsaturated fatty acid to the metal oxide carrier is 1:1-7:1;

[0024] And / or, the mass ratio of the metal element in the auxiliary metal salt to the metal oxide carrier is 0.01:1-0.07:1;

[0025] And / or, the mass ratio of the cobalt element in the cobalt salt to the metal oxide support is 0.01:1-0.1:1;

[0026] And / or, the molar ratio of the thiazole carbene ligand to the cobalt element in the cobalt salt is 3:1-10:1.

[0027] In one embodiment, the mass ratio of the unsaturated fatty acid to the metal oxide carrier is 3:1-7:1;

[0028] And / or, the mass ratio of the metal element in the auxiliary metal salt to the metal oxide carrier is 0.03:1-0.05:1;

[0029] And / or, the mass ratio of the cobalt element in the cobalt salt to the metal oxide support is 0.05:1-0.07:1;

[0030] And / or, the molar ratio of the thiazole carbene ligand to the cobalt element in the cobalt salt is 3:1-7:1.

[0031] The present invention also provides a method for preparing the cobalt-doped catalyst as described above, comprising the following steps:

[0032] S1, placing a metal oxide carrier and an unsaturated fatty acid in an organic solvent to obtain a suspension;

[0033] S2, adding cobalt salt, auxiliary metal salt and thiazole carbene ligand to the suspension, and performing heat preservation adsorption;

[0034] S3, after the adsorption is completed, the cobalt-doped catalyst is obtained by filtration.

[0035] In one embodiment, step S1 comprises: first dispersing the metal oxide carrier in the organic solvent, then adding the unsaturated fatty acid and heating to 40° C.-60° C., and continuously stirring for 4 hours-6 hours.

[0036] In one embodiment, step S2 comprises:

[0037] First, the cobalt salt and the auxiliary metal salt are prepared into a solution;

[0038] then adding the solution to the suspension to obtain a formulation;

[0039] The preparation is heated to 40° C.-60° C., the thiazole carbene ligand is added to the preparation, and the mixture is kept warm for adsorption for 4 hours-6 hours.

[0040] The present invention also provides a method for preparing an aldehyde compound, comprising:

[0041] Under the action of the cobalt-doped catalyst, the compound containing carbon-carbon double bonds undergoes a hydroformylation reaction with synthesis gas in a solvent to obtain aldehyde compounds, wherein the synthesis gas is a mixed gas of H2 and CO.

[0042] In one embodiment, the compound containing a carbon-carbon double bond is selected from olefins or 2,5-dihydrofuran;

[0043] And / or, in the synthesis gas, the molar ratio of H2 to CO is 1:0.5-1:2.

[0044] In one embodiment, the mass ratio of the cobalt-doped catalyst to the compound containing a carbon-carbon double bond is 0.005:1-0.1:1;

[0045] And / or, the mass ratio of the solvent to the compound containing a carbon-carbon double bond is 1:1-1:2;

[0046] And / or, the temperature of the hydroformylation reaction is 60°C-100°C;

[0047] And / or, the total pressure of the synthesis gas is 1.0 MPa-5.0 MPa.

[0048] In the cobalt-doped catalyst of the present invention, firstly, the active component is a complex formed by a cobalt salt, a metal-assisted salt and a thiazole carbene ligand, wherein the bond energy of the carbene-metal bond is large and is not easy to dissociate under heating, so that the active component of the cobalt-doped catalyst is more stable and not easy to lose. At the same time, the electron-donating ability of the thiazole carbene ligand is stronger, which increases the electron density of the central metal, has better stereo effect and electronic effect, and makes the cobalt-doped catalyst have stronger spatial selectivity and activity, overcomes the steric hindrance in the compound containing carbon-carbon double bond, and makes the compound containing carbon-carbon double bond react under mild reaction conditions. Secondly, the metal oxide carrier modified by unsaturated fatty acid has good dispersibility, so that the cobalt-doped catalyst can be better dispersed in the compound containing carbon-carbon double bond, avoids the phenomenon of overreaction due to excessive concentration of local cobalt-doped catalyst, effectively reduces the occurrence of side reactions, and improves the selectivity of the reaction.

[0049] In addition, the preparation method of the cobalt-doped catalyst of the present invention is simple, the conditions are mild and the catalyst is environmentally friendly. Therefore, the cobalt-doped catalyst of the present invention has a high industrial application prospect. BRIEF DESCRIPTION OF THE DRAWINGS

[0050] Figure 1 This is the gas chromatogram of Preparation Example 5 of the aldehyde compound of the present invention. DETAILED DESCRIPTION

[0051] For ease of understanding of the present invention, the present invention will be described more fully below with reference to relevant embodiments. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present invention more thorough and comprehensive.

[0052] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used herein in the specification of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention. The term "and / or" used herein includes any and all combinations of one or more related listed items.

[0053] The invention provides a cobalt-doped catalyst, which is used as a catalyst for a hydroformylation reaction. The cobalt-doped catalyst comprises a modified carrier and an active component loaded on the modified carrier.

[0054] Among them, the modified carrier is a metal oxide carrier modified with unsaturated fatty acids, which can effectively improve the dispersibility of the cobalt-doped catalyst, so that the cobalt-doped catalyst can be better dispersed in compounds containing carbon-carbon double bonds, avoiding the phenomenon of overreaction due to excessive local cobalt-doped catalyst concentration, effectively reducing the occurrence of side reactions, and improving the selectivity of the reaction.

[0055] Optionally, the metal oxide support is selected from at least one of a TiO2 support, a ZnO support, a CuO support, a Cu2O support, a Fe2O3 support, and a BiVO4 support, and is further preferably selected from at least one of a Cu2O support, a Fe2O3 support, and a BiVO4 support.

[0056] Optionally, the unsaturated fatty acid is selected from at least one of oleic acid and linoleic acid.

[0057] Optionally, the mass ratio of the unsaturated fatty acid to the metal oxide carrier is preferably 1:1-7:1, more preferably 3:1-7:1, and more preferably 4:1-7:1.

[0058] Wherein, the active component is a complex formed by a cobalt salt, a metal salt and a thiazole carbene ligand, and the general structural formula of the thiazole carbene ligand is as shown in formula (1) and / or formula (2):

[0059]

[0060] In formula (1) and formula (2), R1, R2, R3 and R4 are independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, phenyl or benzyl.

[0061] The active component is a complex formed by a cobalt salt, a co-metal salt and a thiazole carbene ligand. The carbene-metal bond formed by the thiazole carbene ligand, the cobalt metal and the co-metal has a large bond energy and is not easy to dissociate when heated, so that the active components of the cobalt-doped catalyst are more stable and not easy to lose. This not only improves the stability of the cobalt-doped catalyst, but also solves the problem of easy loss of cobalt and co-metal to a certain extent.

[0062] At the same time, the thiazole carbene ligand has a stronger electron donating ability, which increases the electron density of the central metal cobalt and the auxiliary metal, has better stereo effect and electronic effect, and makes the cobalt-doped catalyst have stronger spatial selectivity and activity, overcomes the steric hindrance in the compounds containing carbon-carbon double bonds, and enables the compounds containing carbon-carbon double bonds to react under mild reaction conditions, which can effectively improve the conversion rate of the compounds containing carbon-carbon double bonds, and greatly reduce the polymerization of the compounds containing carbon-carbon double bonds and the further hydrogenation of the aldehyde products, thereby effectively improving the reaction selectivity.

[0063] Optionally, the cobalt salt is selected from at least one of chloride or its hydrate, nitrate or its hydrate, sulfate or its hydrate, acetylacetonate or its hydrate, such as: Co(NO3)2·6H2O, Co(NO3)2, CoSO4·7H2O, CoSO4, CoCl2, CoCl2·6H2O, Co(OAc)2·4H2O, Co(OAc)2, Co(acac)3(III), Co(acac)2(II), etc.

[0064] Optionally, the mass ratio of the cobalt element in the cobalt salt to the metal oxide carrier is 0.01:1-0.1:1, preferably 0.05:1-0.07:1.

[0065] In the cobalt-doped catalyst of the present invention, the auxiliary metal salt can regulate the selectivity of the reaction. Considering that the physical and chemical properties of iron and nickel are similar to those of cobalt, they are generally referred to as iron-based elements and can better coordinate with thiazole carbene ligands. Optionally, the auxiliary metal salt is selected from iron-containing salts and / or nickel-containing salts, wherein the iron-containing salt is selected from at least one of chlorides or hydrates thereof, nitrates or hydrates thereof, sulfates or hydrates thereof, acetylacetonates or hydrates thereof, such as: FeCl3, FeCl2·4H2O, Fe(acac)3(III), Fe(NO3)3·9H2O, FeSO4, Fe(OAc)2, etc., and the nickel-containing salt is selected from at least one of chlorides or hydrates thereof, nitrates or hydrates thereof, sulfates or hydrates thereof, acetylacetonates or hydrates thereof, such as: Ni(NO3)2·6H2O, nickel acetylacetonate, NiCl2·6H2O, NiCl2, NiSO4·6H2O, NiSO4, Ni(OAc) 2· 4H2O, etc.

[0066] Optionally, the mass ratio of the metal element in the auxiliary metal salt to the metal oxide carrier is 0.01:1-0.07:1, preferably 0.03:1-0.05:1.

[0067] Preferably, in formula (1) and formula (2), R1, R2, R3 and R4 are independently selected from tert-butyl, phenyl or benzyl, and further, the thiazole carbene ligand is selected from at least one of L1 to L4,

[0068]

[0069] Optionally, the molar ratio of the thiazole carbene ligand to the cobalt element in the cobalt salt is 3:1-10:1, preferably 3:1-7:1.

[0070] The present invention also provides a method for preparing the cobalt-doped catalyst, comprising the following steps:

[0071] S1, placing a metal oxide carrier and an unsaturated fatty acid in an organic solvent to obtain a suspension;

[0072] S2, adding cobalt salt, auxiliary metal salt and thiazole carbene ligand to the suspension, and performing heat preservation adsorption;

[0073] S3, after the adsorption is completed, the cobalt-doped catalyst is obtained by filtration.

[0074] In order to better modify the unsaturated fatty acid on the metal oxide carrier, step S1 includes: first dispersing the metal oxide carrier in the organic solvent, then adding the unsaturated fatty acid and heating to 40°C-60°C, and stirring for 4 hours-6 hours. Optionally, the organic solvent is selected from at least one of methanol, ethanol, and dioxane.

[0075] The metal oxide carrier itself has adsorption capacity. The present invention first modifies the surface of the metal oxide carrier with unsaturated fatty acids. The hydroxyl groups in the unsaturated fatty acids can form hydrogen bonds with the thiazole carbene ligands, thereby further enhancing the adsorption capacity and binding strength.

[0076] In order to make the cobalt salt, the auxiliary metal salt and the thiazole carbene ligand form a complex better and adsorb on the modified carrier, step S2 includes:

[0077] S21, first preparing the cobalt salt and the auxiliary metal salt into a solution; wherein the solvent is a solvent that can dissolve the cobalt salt and the auxiliary metal salt, including but not limited to water.

[0078] S22, then adding the solution to the suspension to obtain a preparation; optionally, the solution is added to the suspension in a manner of dropwise addition or the like.

[0079] S23, heating the preparation to 40°C-60°C, adding the thiazole carbene ligand to the preparation, and adsorbing the mixture at the temperature for 4 hours-6 hours.

[0080] The cobalt-doped catalyst obtained by filtration in step S3 may be further dried.

[0081] The preparation method of the cobalt-doped catalyst of the present invention is simple, and the preparation process does not require harsh conditions such as high temperature, high pressure, anhydrous, and oxygen-free. The conditions are mild and the preparation process is environmentally friendly.

[0082] The present invention also provides a method for preparing an aldehyde compound, comprising:

[0083] Under the action of the cobalt-doped catalyst, the compound containing carbon-carbon double bonds undergoes a hydroformylation reaction with synthesis gas in a solvent to obtain aldehyde compounds, wherein the synthesis gas is a mixed gas of H2 and CO.

[0084] Optionally, the compound containing a carbon-carbon double bond is selected from olefins or 2,5-dihydrofuran, and the olefin is selected from any one of propylene, 1-butene, 2-butene, isobutylene, 1-pentene, 2-pentene, 1-octene, 1,3-butadiene, 1,3-pentadiene, isoprene, 2,6-dimethyl-1,5-heptadiene, and 5-methyl-1,4-hexadiene.

[0085] Optionally, in the synthesis gas, the molar ratio of H2 to CO is preferably 1:0.5-1:2, and more preferably 1:1. The total pressure of the synthesis gas is preferably 1.0 MPa-5.0 MPa, and more preferably 1.0 MPa-3.0 MPa.

[0086] Optionally, the mass ratio of the cobalt-doped catalyst to the compound containing a carbon-carbon double bond is 0.005:1-0.1:1.

[0087] Optionally, the mass ratio of the solvent to the compound containing a carbon-carbon double bond is 1:1-1:2, and the solvent is selected from at least one of water, isopropanol, ethanol, methanol, and toluene.

[0088] Optionally, the temperature of the hydroformylation reaction is 60°C-100°C.

[0089] The cobalt-doped catalyst of the present invention is used to prepare aldehyde compounds. The cobalt-doped catalyst has high activity and stable performance. At the same time, the reaction conditions of the preparation process are mild, which can effectively improve the conversion rate of compounds containing carbon-carbon double bonds, and greatly reduce the polymerization of compounds containing carbon-carbon double bonds and further hydrogenation of aldehyde products, thereby effectively improving the selectivity of the reaction.

[0090] Hereinafter, the cobalt-doped catalyst and its preparation method, and the preparation method of the aldehyde compound will be further described through the following specific examples.

[0091] Metal mass = metal salt mass * metal element mass / metal salt molecular weight * 100%;

[0092] Theoretical loading = metal mass / support mass*100%.

[0093] Cobalt-doped catalyst preparation example 1

[0094] Weigh 10.0 g of dry Fe2O3, disperse it in 20.0 g of dioxane, stir evenly, add 40.0 g of oleic acid, heat to 40°C, continue stirring for 4 hours, and obtain a suspension.

[0095] Dissolve 2.47g of Co(NO3)2·6H2O (MW 291.03) and 0.87g of FeCl3 (MW 162.2) in 5.0g of purified water, stir evenly until completely dissolved, and then drop the solution into the above suspension. After the addition is complete, raise the temperature to 50°C, then add L1 (0.025mol) and keep warm for adsorption for 4 hours.

[0096] After the adsorption, the catalyst precursor was filtered to obtain the catalyst precursor, which was placed in a drying oven at 80°C and dried to constant weight to obtain a cobalt-doped catalyst, which was expressed as (5.0% Co~3.0% Fe)L1 / Fe2O 3-油酸 , labeled as catalyst A-1.

[0097] Cobalt-doped catalyst preparation example 2

[0098] 10.0 g of dry BiVO4 was weighed and dispersed in 20.0 g of dioxane. After stirring evenly, 30.0 g of oleic acid was added. The temperature was raised to 40° C. and stirring was continued for 4 hours to obtain a suspension.

[0099] Dissolve 3.05 g of Co(acac)2(II) (MW 257.15) and 2.19 g of nickel acetylacetonate (MW 256.91) in 10.0 g of ethanol, stir until completely dissolved, and then drop the solution into the above suspension. After the addition is complete, raise the temperature to 40°C, then add L1 (0.059 mol) and keep warm for adsorption for 4 hours.

[0100] After the adsorption, the catalyst precursor was filtered to obtain the catalyst precursor, which was placed in a drying oven at 80°C and dried to constant weight to obtain a cobalt-doped catalyst, which was expressed as (7.0% Co~5.0% Ni)L1 / BiVO 4-油酸 , labeled as catalyst A-2.

[0101] Cobalt-doped catalyst preparation example 3

[0102] 10.0 g of dry BiVO4 was weighed and dispersed in 20.0 g of dioxane. After stirring evenly, 40.0 g of linoleic acid was added. The temperature was raised to 50° C. and stirring was continued for 6 hours to obtain a suspension.

[0103] Dissolve 1.27g of Co(OAc)2·4H2O (MW 249.08) and 2.48g of Ni(NO3)2·6H2O (MW290.79) in 10.0g of purified water, stir evenly until completely dissolved, and then drop the solution into the above suspension. After the addition is completed, raise the temperature to 40°C, then add L1 (0.036mol) and keep warm for adsorption for 4 hours.

[0104] After the adsorption, the catalyst precursor was filtered to obtain the catalyst precursor, which was placed in a drying oven at 80°C and dried to constant weight to obtain a cobalt-doped catalyst, which was expressed as (3.0% Co~5.0% Ni)L1 / BiVO 4-亚油酸 , labeled as catalyst A-3.

[0105] Cobalt-doped catalyst preparation example 4

[0106] Weigh 10.0 g of dry Fe2O3, disperse it in 20.0 g of dioxane, stir evenly, add 50.0 g of oleic acid, heat to 40°C, and continue stirring for 4 hours to obtain a suspension.

[0107] Dissolve 4.23 g of Co(acac)3(III) (MW 356.26) and 1.90 g of Fe(acac)3(III) (MW 353.17) in 10.0 g of ethanol, stir evenly until completely dissolved, and then drop the solution into the above suspension. After the addition is complete, raise the temperature to 50°C, then add L2 (0.059 mol) and keep warm for adsorption for 4 hours.

[0108] After the adsorption, the catalyst precursor was filtered and placed in a drying oven at 80°C to dry to constant weight to obtain a cobalt-doped catalyst, which was expressed as (7.0% Co~3.0% Fe)L2 / Fe2O 3-油酸 , labeled as catalyst A-4.

[0109] Cobalt-doped catalyst preparation example 5

[0110] Weigh 10.0 g of dry TiO2, disperse it in 20.0 g of dioxane, stir evenly, add 50.0 g of oleic acid, heat to 40°C, and continue stirring for 4 hours to obtain a suspension.

[0111] Dissolve 4.23 g of Co(acac)3(III) (MW 356.26) and 1.90 g of Fe(acac)3(III) (MW 353.17) in 10.0 g of ethanol, stir evenly until completely dissolved, and then drop the solution into the above suspension. After the addition is complete, raise the temperature to 50°C, then add L3 (0.059 mol) and keep warm for adsorption for 4 hours.

[0112] After the adsorption, the catalyst precursor was filtered to obtain the catalyst precursor, which was placed in a drying oven at 80°C and dried to constant weight to obtain a cobalt-doped catalyst, which was expressed as (7.0% Co~3.0% Fe)L2 / TiO 2-油酸 , labeled as catalyst A-5.

[0113] Cobalt-doped catalyst preparation example 6

[0114] Weigh 10.0 g of dry Fe2O3, disperse it in 20.0 g of dioxane, stir evenly, add 50.0 g of oleic acid, heat to 40°C, and continue stirring for 4 hours to obtain a suspension.

[0115] Dissolve 0.40g of CoCl2·6H2O (MW 237.93) and 5.06g of Fe(NO3)3·9H2O (MW 404) in 5.0g of purified water, stir evenly until completely dissolved, and then drop the solution into the above suspension. After the addition is complete, raise the temperature to 50°C, then add L1 (0.017mol) and keep warm for adsorption for 4 hours.

[0116] After the adsorption, the catalyst precursor was filtered to obtain the catalyst precursor, which was placed in a drying oven at 80°C and dried to constant weight to obtain a cobalt-doped catalyst, which was expressed as (1.0% Co~7.0% Fe)L1 / Fe2O 3-油酸 , labeled as catalyst A-6.

[0117] Cobalt-doped catalyst preparation example 7

[0118] 10.0 g of dry ZnO was weighed and dispersed in 20.0 g of dioxane. After stirring evenly, 70.0 g of linoleic acid was added. The temperature was raised to 40° C. and stirring was continued for 6 hours to obtain a suspension.

[0119] Dissolve 2.02g of CoCl2·6H2O (MW 237.93) and 3.61g of Fe(NO3)3·9H2O (MW 404) in 8.0g of purified water, stir evenly until completely dissolved, and then drop the solution into the above suspension. After the addition is complete, raise the temperature to 45°C, then add L4 (0.068mol) and keep warm for adsorption for 6 hours.

[0120] After the adsorption is completed, the catalyst precursor is filtered to obtain the catalyst precursor, and the catalyst precursor is placed in a drying oven at 80°C and dried to constant weight to obtain a cobalt-doped catalyst, which is expressed as (5.0% Co~5.0% Fe)L4 / ZnO -亚油酸 , labeled as catalyst A-7.

[0121] Cobalt-doped catalyst preparation example 8

[0122] Weigh 10.0 g of dry Cu2O, disperse it in 20.0 g of dioxane, stir evenly, add 40.0 g of oleic acid, heat to 40°C, and continue stirring for 6 hours to obtain a suspension.

[0123] Dissolve 1.84 g of CoSO4 (MW 155) and 3.61 g of FeCl2·4H2O (MW 198.81) in 10.0 g of purified water, stir evenly until completely dissolved, and then drop the solution into the above suspension. After the addition is complete, raise the temperature to 45°C, then add L4 (0.083 mol) and keep warm for adsorption for 6 hours.

[0124] After the adsorption, the catalyst precursor was filtered to obtain the catalyst precursor, and the catalyst precursor was placed in a drying oven at 80°C and dried to constant weight to obtain a cobalt-doped catalyst, which was expressed as (7.0% Co~5.0% Fe)L4 / Cu2O -油酸 , labeled as catalyst A-8.

[0125] Cobalt-doped catalyst preparation example 9

[0126] 10.0 g of dried CuO was weighed and dispersed in 20.0 g of dioxane. After stirring evenly, 50.0 g of oleic acid was added. The temperature was raised to 40° C. and stirring was continued for 6 hours to obtain a suspension.

[0127] Dissolve 4.23 g of Co(acac)3(III) (MW 356.26) and 3.16 g of Fe(acac)3(III) (MW 353.17) in 10.0 g of ethanol, stir evenly until completely dissolved, and then drop the solution into the above suspension. After the addition is complete, raise the temperature to 50°C, then add L2 (0.083 mol) and keep warm for adsorption for 6 hours.

[0128] After the adsorption is completed, the catalyst precursor is filtered to obtain the catalyst precursor, and the catalyst precursor is placed in a drying oven at 80°C and dried to constant weight to obtain a cobalt-doped catalyst, which is expressed as (7.0% Co~5.0% Fe)L4 / CuO -油酸 , labeled as catalyst A-9.

[0129] Cobalt-doped catalyst preparation example 10

[0130] 10.0 g of dry BiVO4 was weighed and dispersed in 20.0 g of dioxane. After stirring evenly, 10.0 g of oleic acid was added, the temperature was raised to 40° C., and stirring was continued for 6 hours to obtain a suspension.

[0131] Dissolve 4.23 g of Co(acac)3(III) (MW 356.26) and 3.16 g of Fe(acac)3(III) (MW 353.17) in 10.0 g of ethanol, stir evenly until completely dissolved, and then drop the solution into the above suspension. After the addition is complete, raise the temperature to 50°C, then add L2 (0.083 mol) and keep warm for adsorption for 6 hours.

[0132] After the adsorption, the catalyst precursor was filtered and placed in a drying oven at 80°C to dry to constant weight to obtain a cobalt-doped catalyst, which was expressed as (7.0% Co~5.0% Fe)L2 / Cu2O -油酸 , labeled as catalyst A-10.

[0133] Cobalt-doped catalyst preparation example 11

[0134] 10.0 g of dry BiVO4 was weighed and dispersed in 20.0 g of dioxane. After stirring evenly, 50.0 g of oleic acid was added, the temperature was raised to 40° C., and stirring was continued for 6 hours to obtain a suspension.

[0135] Dissolve 4.23 g of Co(acac)3(III) (MW 356.26) and 3.16 g of Fe(acac)3(III) (MW 353.17) in 10.0 g of ethanol, stir evenly until completely dissolved, and then drop the solution into the above suspension. After the addition is complete, raise the temperature to 50°C, then add L2 (0.083 mol) and keep warm for adsorption for 6 hours.

[0136] After the adsorption, the catalyst precursor was filtered to obtain the catalyst precursor, which was placed in a drying oven at 80°C and dried to constant weight to obtain a cobalt-doped catalyst, which was expressed as (7.0% Co~5.0% Fe)L2 / BiVO 4-油酸 , labeled as catalyst A-11.

[0137] Cobalt-doped catalyst preparation example 12

[0138] 10.0 g of dry BiVO4 was weighed and dispersed in 20.0 g of dioxane. After stirring evenly, 50.0 g of oleic acid was added, the temperature was raised to 40° C., and stirring was continued for 6 hours to obtain a suspension.

[0139] Dissolve 6.04 g of Co(acac)3(III) (MW 356.26) and 3.16 g of Fe(acac)3(III) (MW 353.17) in 15.0 g of ethanol, stir evenly until completely dissolved, and then drop the solution into the above suspension. After the addition is complete, raise the temperature to 50°C, then add L2 (0.107 mol) and keep warm for adsorption for 6 hours.

[0140] After the adsorption, the catalyst precursor was filtered to obtain the catalyst precursor, which was placed in a drying oven at 80°C and dried to constant weight to obtain a cobalt-doped catalyst, which was expressed as (10.0% Co~5.0% Fe)L2 / BiVO 4-油酸 , labeled as catalyst A-12.

[0141] Catalyst Preparation Comparative Example 1

[0142] 10.0 g of dry BiVO4 was weighed and dispersed in 20.0 g of dioxane. After stirring evenly, 50.0 g of oleic acid was added, the temperature was raised to 40° C., and stirring was continued for 6 hours to obtain a suspension.

[0143] Dissolve 4.23 g of Co(acac)3(III) (MW 356.26) in 10.0 g of ethanol, stir evenly until completely dissolved, and then drop the solution into the above suspension. After the addition is complete, raise the temperature to 50°C, then add L2 (0.083 mol) and keep warm for adsorption for 6 hours.

[0144] After the adsorption, the catalyst precursor was filtered to obtain the catalyst precursor, which was placed in a drying oven at 80°C and dried to constant weight to obtain the catalyst, which was expressed as (7.0% Co) L2 / BiVO 4-油酸 , labeled as catalyst B.

[0145] Catalyst Preparation Comparative Example 2

[0146] 10.0 g of dry BiVO4 was weighed and dispersed in 20.0 g of dioxane. After stirring evenly, 50.0 g of oleic acid was added, the temperature was raised to 40° C., and stirring was continued for 6 hours to obtain a suspension.

[0147] Dissolve 3.16 g of Fe(acac)3(III) (MW 353.17) in 10.0 g of ethanol, stir evenly until completely dissolved, and then drop the solution into the above suspension. After the addition is complete, raise the temperature to 50°C, then add L2 (0.083 mol) and keep warm for adsorption for 6 hours.

[0148] After the adsorption, the catalyst precursor was filtered to obtain the catalyst precursor, which was placed in a drying oven at 80°C and dried to constant weight to obtain the catalyst, which was expressed as (5.0% Fe)L2 / BiVO 4-油酸 , marked as catalyst C.

[0149] Catalyst Preparation Comparative Example 3

[0150] Dissolve 4.23 g of Co(acac)3(III) (MW 356.26) and 3.16 g of Fe(acac)3(III) (MW 353.17) in 10.0 g of ethanol, stir evenly until completely dissolved, raise the temperature to 50°C, then add L2 (0.083 mol) and 50.0 g of oleic acid, and keep warm for adsorption for 6 hours.

[0151] After the adsorption is completed, the catalyst precursor is filtered to obtain a catalyst precursor, and the catalyst precursor is placed in a drying oven at 80°C and dried to constant weight to obtain a catalyst, which is expressed as (7.0% Co~5.0% Fe)L2-oleic acid and is marked as catalyst D.

[0152] Catalyst Preparation Comparative Example 4

[0153] 10.0 g of dry BiVO4 was weighed and dispersed in 20.0 g of dioxane. After stirring evenly, the mixture was heated to 40° C. and stirred for 6 hours to obtain a suspension.

[0154] Dissolve 4.23 g of Co(acac)3(III) (MW 356.26) and 3.16 g of Fe(acac)3(III) (MW 353.17) in 10.0 g of ethanol, stir evenly until completely dissolved, and then drop the solution into the above suspension. After the addition is complete, raise the temperature to 50°C, then add L2 (0.083 mol) and keep warm for adsorption for 6 hours.

[0155] After the adsorption is completed, the catalyst precursor is filtered to obtain a catalyst precursor, and the catalyst precursor is placed in a drying oven at 80°C and dried to constant weight to obtain a catalyst, expressed as (7.0% Co~5.0% Fe)L2 / BiVO4, marked as catalyst E.

[0156] Aldehyde compound preparation example 1

[0157] 9.53 g of catalyst A-11 was uniformly dispersed in 100 g of toluene to obtain a catalyst suspension.

[0158] The autoclave was replaced with nitrogen and synthesis gas (CO / H2=1:1, molar ratio) for 3 times, and then the autoclave was filled with synthesis gas. The catalyst suspension and 2 mol (136.2 g) of 1,3-pentadiene (MW 68.12) were pumped into the autoclave, and then the synthesis gas was passed to a pressure of 4.0 MPa and the temperature was raised to 100°C. After heating and stirring for 4.5 hours, the pressure was released after cooling to room temperature, and the reaction liquid was detected by gas chromatography. The results showed that the conversion rate of 1,3-pentadiene was 99.6%, and the selectivity of 3-hexenal was 99.5%.

[0159] Aldehyde compound preparation example 2

[0160] 7.85 g of catalyst A-2 was uniformly dispersed in 100 g of toluene to obtain a catalyst suspension.

[0161] The autoclave was replaced with nitrogen and synthesis gas (CO / H2=1:1, molar ratio) for 3 times, and then the autoclave was filled with synthesis gas. The catalyst suspension and 2 mol (112.2 g) of 1-butene were pumped into the autoclave, and then the synthesis gas was passed to a pressure of 5 MPa and the temperature was raised to 100°C. After heating and stirring for 5 hours, the pressure was released after cooling to room temperature, and the reaction liquid was detected by gas chromatography. The results showed that the conversion rate of 1-butene was 98.7%, and the selectivity of n-valeraldehyde was 99.2%.

[0162] Aldehyde compound preparation example 3

[0163] 7.85 g of catalyst A-4 was uniformly dispersed in 100 g of toluene to obtain a catalyst suspension.

[0164] The autoclave was replaced with nitrogen and synthesis gas (CO / H2=1:1, molar ratio) for 3 times, and then the autoclave was filled with synthesis gas. The catalyst suspension and 2 mol (112.2 g) of isobutylene were pumped into the autoclave, and then the synthesis gas was passed to a pressure of 5.0 MPa and the temperature was raised to 100°C. After heating and stirring for 5 hours, the pressure was released after cooling to room temperature, and the reaction liquid was detected by gas chromatography. The results showed that the conversion rate of isobutylene was 98.6%, and the selectivity of isovaleraldehyde was 99.1%.

[0165] Aldehyde compound preparation example 4

[0166] 7.57 g of catalyst A-3 was uniformly dispersed in 100 g of toluene to obtain a catalyst suspension.

[0167] The autoclave was replaced with nitrogen and synthesis gas (CO / H2=1:1, molar ratio) for 3 times, and then the autoclave was filled with synthesis gas. The catalyst suspension and 2 mol (108.2 g) of 1,3-butadiene were pumped into the autoclave, and then the synthesis gas was passed to a pressure of 4.0 MPa, and the temperature was raised to 100°C. After heating and stirring for 6 hours, the pressure was released after cooling to room temperature, and the reaction liquid was detected by gas chromatography. The results showed that the conversion rate of 1,3-butadiene was 98.4%, and the selectivity of 2-methyl-3-butenal was 89.8%.

[0168] Aldehyde compound preparation example 5

[0169] At room temperature, 9.92 g of catalyst A-8 was uniformly dispersed in 100 g of ethanol to obtain a catalyst suspension.

[0170] The autoclave was replaced with nitrogen and synthesis gas (CO / H2=1:1, molar ratio) three times, and then the autoclave was filled with synthesis gas. The catalyst suspension and 1 mol (110.2 g) of 5-methyl-1,4-hexadiene were pumped into the autoclave, and then the synthesis gas was introduced to a pressure of 35.0 MPa and the temperature was raised to 110°C. After heating and stirring for 54 hours, the temperature was lowered to room temperature and the pressure was released, and the reaction liquid was detected by gas chromatography. The results are as follows Figure 1 As shown: the conversion rate of 5-methyl-1,4-hexadiene is 98.6%, and the selectivity of 6-methyl-5-heptenal is 97.2%.

[0171] Gas chromatography test conditions: Foley gas chromatograph model GC 9790plus; SE-30 capillary column, model 30m×0.25mm×0.25μm; vaporization chamber: 200°C, detector: 220°C; column temperature: 90°C for 8min.

[0172] Aldehyde compound preparation example 6

[0173] At room temperature, 6.22 g of catalyst A-12 was uniformly dispersed in 100 g of toluene to obtain a catalyst suspension.

[0174] The autoclave was replaced with nitrogen and synthesis gas (CO / H2=1:1, molar ratio) for 3 times, and then the autoclave was filled with synthesis gas. The catalyst suspension and 1 mol (124.4 g) of 2,6-dimethyl-1,5-heptadiene were pumped into the autoclave, and then the synthesis gas was passed to a pressure of 4.0 MPa and the temperature was raised to 100°C. After heating and stirring for 5 hours, the pressure was released after cooling to room temperature, and the reaction liquid was detected by gas chromatography. The results showed that the conversion rate of 2,6-dimethyl-1,5-heptadiene was 98.6%, and the selectivity of citronellal was 98.4%.

[0175] Aldehyde compound preparation example 7

[0176] 7.02 g of catalyst A-1 was uniformly dispersed in 100 g of toluene to obtain a catalyst suspension.

[0177] The autoclave was replaced with nitrogen and synthesis gas (CO / H2=1:1, molar ratio) for 3 times, and then the autoclave was filled with synthesis gas. The catalyst suspension and 2 mol (140.4 g) of 1-pentene were pumped into the autoclave, and then the synthesis gas was passed to a pressure of 5.0 MPa, and the temperature was raised to 100°C. After heating and stirring for 6.5 hours, the temperature was lowered to room temperature and the pressure was released, and the reaction liquid was detected by gas chromatography. The results showed that the conversion rate of 1-pentene was 92.1%, and the selectivity of n-hexanal was 94.3%.

[0178] Aldehyde compound preparation example 8

[0179] 5.61 g of catalyst A-3 was uniformly dispersed in 100 g of toluene to obtain a catalyst suspension.

[0180] The autoclave was replaced with nitrogen and synthesis gas (CO / H2=1:1, molar ratio) for 3 times, and then the autoclave was filled with synthesis gas. The catalyst suspension and 1 mol (112.2 g) of 1-octene were pumped into the autoclave, and then the synthesis gas was passed to a pressure of 6.0 MPa, and the temperature was raised to 120°C. After heating and stirring for 6.0 hours, the temperature was lowered to room temperature and the pressure was released, and the reaction liquid was detected by gas chromatography. The results showed that the conversion rate of 1-octene was 89.2%, and the selectivity of n-nonanal was 90.4%.

[0181] Aldehyde compound preparation example 9

[0182] Catalyst A-5 was uniformly dispersed in 100 g of toluene to obtain a catalyst suspension.

[0183] The autoclave was replaced with nitrogen and synthesis gas (CO / H2=1:1, molar ratio) three times, and then the autoclave was filled with synthesis gas. The catalyst suspension and 2 mol (136.2 g) of isoprene were pumped into the autoclave, and then the synthesis gas was passed to a pressure of 5.0 MPa, and the temperature was raised to 100°C. After heating and stirring for 5 hours, the temperature was lowered to room temperature and the pressure was released, and the reaction liquid was detected by gas chromatography. The results showed that the conversion rate of isoprene was 95.7%, and the selectivity of 3-methyl-3-pentenal was 98.1%.

[0184] Aldehyde compound preparation example 10

[0185] Catalyst A-5 was uniformly dispersed in 100 g of toluene to obtain a catalyst suspension.

[0186] The autoclave was replaced with nitrogen and synthesis gas (CO / H2=1:1, molar ratio) three times, and then the autoclave was filled with synthesis gas. The catalyst suspension and 2 mol (136.2 g) of isoprene were pumped into the autoclave, and then the synthesis gas was passed to a pressure of 5.0 MPa, and the temperature was raised to 100°C. After heating and stirring for 5 hours, the temperature was lowered to room temperature and the pressure was released, and the reaction liquid was detected by gas chromatography. The results showed that the conversion rate of isoprene was 95.7%, and the selectivity of 3-methyl-3-pentenal was 98.1%.

[0187] Aldehyde compound preparation example 11

[0188] 7.85 g of catalyst A-6 was uniformly dispersed in 100 g of toluene to obtain a catalyst suspension.

[0189] The autoclave was replaced with nitrogen and synthesis gas (CO / H2=1:1, molar ratio) for 3 times, and then the autoclave was filled with synthesis gas. The catalyst suspension and 2 mol (112.2 g) of 1-butene were pumped into the autoclave, and then the synthesis gas was passed to a pressure of 5.0 MPa and the temperature was raised to 100°C. After heating and stirring for 6 hours, the pressure was released after cooling to room temperature, and the reaction liquid was detected by gas chromatography. The results showed that the conversion rate of 1-butene was 88.7%, and the selectivity of n-valeraldehyde was 89.2%.

[0190] Aldehyde compound preparation example 12

[0191] 7.85 g of catalyst A-7 was uniformly dispersed in 100 g of toluene to obtain a catalyst suspension.

[0192] The autoclave was replaced with nitrogen and synthesis gas (CO / H2=1:1, molar ratio) for 3 times, and then the autoclave was filled with synthesis gas. The catalyst suspension and 2 mol (112.2 g) of 1-butene were pumped into the autoclave, and then the synthesis gas was passed to a pressure of 5.0 MPa, and the temperature was raised to 100°C. After heating and stirring for 6 hours, the pressure was released after cooling to room temperature, and the reaction liquid was detected by gas chromatography. The results showed that the conversion rate of 1-butene was 91.7%, and the selectivity of n-valeraldehyde was 94.5%.

[0193] Aldehyde compound preparation example 13

[0194] 7.85 g of catalyst A-9 was uniformly dispersed in 100 g of toluene to obtain a catalyst suspension.

[0195] The autoclave was replaced with nitrogen and synthesis gas (CO / H2=1:1, molar ratio) for 3 times, and then the autoclave was filled with synthesis gas. The catalyst suspension and 2 mol (112.2 g) of 1-butene were pumped into the autoclave, and then the synthesis gas was passed to a pressure of 5.0 MPa and the temperature was raised to 100°C. After heating and stirring for 6 hours, the pressure was released after cooling to room temperature, and the reaction liquid was detected by gas chromatography. The results showed that the conversion rate of 1-butene was 92.6%, and the selectivity of n-valeraldehyde was 95.3%.

[0196] Aldehyde compound preparation example 14

[0197] 7.85 g of catalyst A-10 was uniformly dispersed in 100 g of toluene to obtain a catalyst suspension.

[0198] The autoclave was replaced with nitrogen and synthesis gas (CO / H2=1:1, molar ratio) for 3 times, and then the autoclave was filled with synthesis gas. The catalyst suspension and 2 mol (112.2 g) of 1-butene were pumped into the autoclave, and then the synthesis gas was passed to a pressure of 5.0 MPa and the temperature was raised to 100°C. After heating and stirring for 6 hours, the pressure was released after cooling to room temperature, and the reaction liquid was detected by gas chromatography. The results showed that the conversion rate of 1-butene was 96.8%, and the selectivity of n-valeraldehyde was 97.7%.

[0199] Aldehyde compound preparation example 15

[0200] 12.62 g of catalyst A-11 was uniformly dispersed in 100 g of toluene to obtain a catalyst suspension.

[0201] The autoclave was replaced with nitrogen and synthesis gas (CO / H2=1:1, molar ratio) for 3 times, and then the autoclave was filled with synthesis gas. The catalyst suspension and 2 mol (140.2 g) of 2,5-dihydrofuran were pumped into the autoclave in sequence, and then the synthesis gas was passed to a pressure of 3.0 MPa, the temperature was raised to 90°C, heated and stirred for 5 hours, and then the temperature was lowered to room temperature and the pressure was released, and the reaction liquid was detected by gas chromatography. The results showed that the conversion rate of 2,5-dihydrofuran was 93.1%, and the selectivity of tetrahydrofuran-3-carboxaldehyde was 96.4%.

[0202] Comparative Example 1 for Preparation of Aldehyde Compounds

[0203] 9.81 g of catalyst B was uniformly dispersed in 100 g of toluene to obtain a catalyst suspension.

[0204] The autoclave was replaced with nitrogen and synthesis gas (CO / H2=1:1, molar ratio) for 3 times, and then the autoclave was filled with synthesis gas. The catalyst suspension and 2 mol (136.2 g) of 1,3-pentadiene (MW 68.12) were pumped into the autoclave, and then the synthesis gas was passed to a pressure of 5.0 MPa and the temperature was raised to 100°C. After heating and stirring for 6 hours, the pressure was released after cooling to room temperature, and the reaction liquid was detected by gas chromatography. The results showed that the conversion rate of 1,3-pentadiene was 69.7%, and the selectivity of 3-hexenal was 56.4%.

[0205] Comparative Example 2 for Preparation of Aldehyde Compounds

[0206] 9.81 g of catalyst C was uniformly dispersed in 100 g of toluene to obtain a catalyst suspension.

[0207] The autoclave was replaced with nitrogen and synthesis gas (CO / H2=1:1, molar ratio) for 3 times, and then the autoclave was filled with synthesis gas. The catalyst suspension and 2 mol (136.2 g) of 1,3-pentadiene (MW 68.12) were pumped into the autoclave, and then the synthesis gas was passed to a pressure of 5.0 MPa and the temperature was raised to 110°C. After heating and stirring for 7 hours, the pressure was released after cooling to room temperature, and the reaction liquid was detected by gas chromatography. The results showed that the conversion rate of 1,3-pentadiene was 49.1%, and the selectivity of 3-hexenal was 51.3%.

[0208] Comparative Example 3 of Preparation of Aldehyde Compounds

[0209] 9.81 g of catalyst D was uniformly dispersed in 100 g of toluene to obtain a catalyst suspension.

[0210] The autoclave was replaced with nitrogen and synthesis gas (CO / H2=1:1, molar ratio) for 3 times, and then the autoclave was filled with synthesis gas. The catalyst suspension and 2 mol (136.2 g) of 1,3-pentadiene (MW 68.12) were pumped into the autoclave, and then the synthesis gas was passed to a pressure of 5.0 MPa and the temperature was raised to 120°C. After heating and stirring for 7 hours, the temperature was lowered to room temperature and the pressure was released, and the reaction liquid was detected by gas chromatography. The results showed that the conversion rate of 1,3-pentadiene was 32.4%, and the selectivity of 3-hexenal was 56.3%.

[0211] Comparative Example 4 of Preparation of Aldehyde Compounds

[0212] 9.81 g of Catalyst E was uniformly dispersed in 100 g of toluene to obtain a catalyst suspension.

[0213] The autoclave was replaced with nitrogen and synthesis gas (CO / H2=1:1, molar ratio) for 3 times, and then the autoclave was filled with synthesis gas. The catalyst suspension and 2 mol (136.2 g) of 1,3-pentadiene (MW 68.12) were pumped into the autoclave, and then the synthesis gas was passed to a pressure of 5.0 MPa and the temperature was raised to 100°C. After heating and stirring for 6 hours, the pressure was released after cooling to room temperature, and the reaction liquid was detected by gas chromatography. The results showed that the conversion rate of 1,3-pentadiene was 72.5%, and the selectivity of 3-hexenal was 78.4%.

[0214] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0215] The above-mentioned embodiments only express several implementation methods of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A cobalt-doped catalyst, which is used as a catalyst for a hydroformylation reaction, characterized in that: The cobalt-doped catalyst comprises a modified carrier and an active component supported on the modified carrier; Wherein, the modified carrier is a metal oxide carrier modified with an unsaturated fatty acid, and the unsaturated fatty acid is selected from at least one of oleic acid and linoleic acid; The active component is a complex formed by a cobalt salt, a metal auxiliary salt and a thiazole carbene ligand, wherein the metal auxiliary salt is selected from an iron-containing salt and / or a nickel-containing salt, and the general structural formula of the thiazole carbene ligand is as shown in formula (1) and / or formula (2): In formula (1) and formula (2), R1, R2, R3 and R4 are independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, phenyl or benzyl.

2. The cobalt-doped catalyst according to claim 1, characterized in that The metal oxide carrier is selected from at least one of a TiO2 carrier, a ZnO carrier, a CuO carrier, a Cu2O carrier, a Fe2O3 carrier, and a BiVO4 carrier; And / or, the cobalt salt is selected from at least one of chloride or its hydrate, nitrate or its hydrate, sulfate or its hydrate, acetylacetonate or its hydrate; And / or, the iron-containing salt is selected from at least one of chlorides or hydrates thereof, nitrates or hydrates thereof, sulfates or hydrates thereof, and acetylacetonates or hydrates thereof, and the nickel-containing salt is selected from at least one of chlorides or hydrates thereof, nitrates or hydrates thereof, sulfates or hydrates thereof, and acetylacetonates or hydrates thereof; And / or, R1, R2, R3 and R4 are independently selected from tert-butyl, phenyl or benzyl.

3. The cobalt-doped catalyst according to claim 2, characterized in that The metal oxide carrier is selected from at least one of a Cu2O carrier, a Fe2O3 carrier, and a BiVO4 carrier; and / or, the thiazole carbene ligand is selected from at least one of L1 to L4, 4. The cobalt-doped catalyst according to claim 1, characterized in that The mass ratio of the unsaturated fatty acid to the metal oxide carrier is 1:1-7:1; And / or, the mass ratio of the metal element in the auxiliary metal salt to the metal oxide carrier is 0.01:1-0.07:1; And / or, the mass ratio of the cobalt element in the cobalt salt to the metal oxide support is 0.01:1-0.1:1; And / or, the molar ratio of the thiazole carbene ligand to the cobalt element in the cobalt salt is 3:1-10:

1.

5. The cobalt-doped catalyst according to claim 1, characterized in that The mass ratio of the unsaturated fatty acid to the metal oxide carrier is 3:1-7:1; And / or, the mass ratio of the metal element in the auxiliary metal salt to the metal oxide carrier is 0.03:1-0.05:1; And / or, the mass ratio of the cobalt element in the cobalt salt to the metal oxide support is 0.05:1-0.07:1; And / or, the molar ratio of the thiazole carbene ligand to the cobalt element in the cobalt salt is 3:1-7:

1.

6. A method for preparing a cobalt-doped catalyst according to any one of claims 1 to 5, characterized in that: The following steps are involved: S1, placing a metal oxide carrier and an unsaturated fatty acid in an organic solvent to obtain a suspension; S2, adding cobalt salt, auxiliary metal salt and thiazole carbene ligand to the suspension, and performing heat preservation adsorption; S3, after the adsorption is completed, the cobalt-doped catalyst is obtained by filtration.

7. The method for preparing a cobalt-doped catalyst according to claim 6, characterized in that: Step S1 comprises: first dispersing the metal oxide carrier in the organic solvent, then adding the unsaturated fatty acid and heating to 40° C.-60° C., and continuously stirring for 4 hours-6 hours.

8. The method for preparing a cobalt-doped catalyst according to claim 6, characterized in that: Step S2 includes: First, the cobalt salt and the auxiliary metal salt are prepared into a solution; then adding the solution to the suspension to obtain a formulation; The preparation is heated to 40° C.-60° C., the thiazole carbene ligand is added to the preparation, and the mixture is kept warm for adsorption for 4 hours-6 hours.

9. A method for preparing an aldehyde compound, characterized in that: include: Under the action of the cobalt-doped catalyst as described in any one of claims 1 to 5, the compound containing a carbon-carbon double bond undergoes a hydroformylation reaction with synthesis gas in a solvent to obtain an aldehyde compound, wherein the synthesis gas is a mixed gas of H2 and CO.

10. The method for preparing an aldehyde compound according to claim 9, characterized in that: The compound containing a carbon-carbon double bond is selected from olefins or 2,5-dihydrofuran; And / or, in the synthesis gas, the molar ratio of H2 to CO is 1:0.5-1:

2.

11. The method for preparing an aldehyde compound according to claim 9, characterized in that: The mass ratio of the cobalt-doped catalyst to the compound containing a carbon-carbon double bond is 0.005:1-0.1:1; And / or, the mass ratio of the solvent to the compound containing a carbon-carbon double bond is 1:1-1:2; And / or, the temperature of the hydroformylation reaction is 60°C-100°C; And / or, the total pressure of the synthesis gas is 1.0 MPa-5.0 MPa.

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