A catalyst for carbonylation of olefinic unsaturated compounds and its preparation method and application

Abstract

The present invention provides a carbonylation catalyst and a preparation method and application thereof. The catalyst uses a group VIB or group VIIIB metal as an active site and a large sterically hindered bidentate ligand as a metal complex. When used for the carbonylation reaction of olefinic unsaturated compounds under the action of organic sodium salt and stearate additives, the catalyst can exhibit high reaction rate and product selectivity. At the same time, the active component has good stability during the reaction process, so that the catalyst can exhibit excellent long-term stability.

Description

Technical Field

[0001] The invention relates to the field of carbonylation of olefinic unsaturated compounds, and in particular to a catalyst for carbonylation of olefinic unsaturated compounds and a preparation method and application thereof. Background Art

[0002] At present, the research on carbonylation reaction is relatively mature. It mainly uses synthesis gas as a carbonyl source to achieve the hydroformylation of unsaturated hydrocarbons and fatty acids under the action of transition metal catalysts. At the same time, many domestic and foreign patent studies have reported that in an alcohol or water system, only CO can be used as a carbonyl source to carbonylate olefinic unsaturated compounds to obtain corresponding esters or carboxylic acids, realizing the carbonylation and esterification process in one step. The catalyst system mainly uses VI, VIII, IX or X group elements as active sites and monodentate or bidentate phosphines as ligands, such as alkyl, aryl, cycloalkyl or pyridyl phosphines, to achieve the catalytic carbonylation reaction process after coordination and complexation.

[0003] WO96 / 19434 discloses a bidentate phosphine ligand structure in which a substitutable aryl group is used as a bridging group and the adjacent carbon atoms of the aryl group are connected to phosphorus, which can significantly improve the carbonylation reaction rate of olefinic unsaturated compounds. Federico et al. found in a kinetic study of the above system that the dissociation between the alkoxy group and the proton hydrogen of the alcohol before esterification is the rate-limiting step of the reaction, but did not mention an effective solution to improve the alcohol dissociation rate. In addition, for the carbonylation reaction of olefinic unsaturated compounds to esters, the bidentate phosphine ligand catalyst system disclosed in EP-A-0227160 can effectively improve the catalyst activity, but faces the problem of poor stability caused by the reduction and precipitation deactivation of the active site during the reaction, and industrialization is bound to face the problem of high cost. Summary of the invention

[0004] To solve the above problems, an object of the present invention is to provide a catalyst for the carbonylation of olefinic unsaturated compounds and a method for preparing the same. The catalyst system prepared by the present invention can further increase the carbonylation reaction rate, and in the process of catalyzing the carbonylation of olefinic unsaturated compounds, the loss of metal active sites can be effectively suppressed, thereby significantly improving its stability and reducing the catalyst cost.

[0005] Another object of the present invention is to provide a method for preparing carboxylic acid esters of olefinic unsaturated compounds by using the catalyst. The catalyst is applied to the carbonylation reaction of olefinic unsaturated compounds, substantially generates no other by-products, has high selectivity and excellent catalytic activity.

[0006] To achieve the above object, the present invention adopts the following scheme.

[0007] A catalyst for carbonylation of olefinic unsaturated compounds, comprising a main catalyst and an auxiliary agent, wherein the main catalyst comprises the following components:

[0008] ① Group VIB or Group VIIIB metal active components;

[0009] ② Ligand;

[0010] ③Acid;

[0011] Among them, the Group VIB or Group VIB metal includes one or more of metals Cr, Mo, W, Fe, Co, Ni, Ru, Rh, Os, Ir, Pt and Pd, preferably selected from Ni, Pt and Pd; the ligand is a bidentate phosphine, arsine or antimony ligand.

[0012] The ligand is preferably a bidentate phosphine ligand having the following general formula (1),

[0013]

[0014] Wherein X is a substituted bridging group, X is selected from a substitutable aryl, cyclopentadienyl, indenyl or cycloalkyl, preferably cyclopentadienyl. R1, R2, R3 and R4 are substituent groups connected to the phosphorus atom, R1, R2, R3 and R4 are the same or different, R1, R2, R3 and R4 are selected from large steric hindrance substituent groups such as tert-butyl, and the large steric hindrance substituent groups include but are not limited to tert-butyl, adamantyl and substituent groups thereof.

[0015] The molar ratio of the ligand to the Group VIB or Group VIB metal active component is 1:1-100:1, preferably 1:1-50:1, to ensure saturated coordination of the metal active site and enhance the binding force between the ligand and the metal active site.

[0016] The acid includes compounds derived from weakly coordinated anions, low carbon chain alkanoic acids, sulfonic acids and phosphonic acids, preferably sulfonic acids and phosphonic acids. The molar ratio of the acid to the Group VIB or Group VIB metal active component is 2:1-500:1, preferably 20:1-400:1.

[0017] Components ① to ③ can be reacted by adding them to an organic solvent in situ to generate the main catalyst required for the carbonylation reaction, or they can form a catalyst system in any order, or they can be synthesized in a specific order. The three components can be combined in any form to form intermediate components and then react with the third component to form the final main catalyst. For example, components ② and ③ are first mixed to form a protonated ligand and then complexed with ① to form a catalyst system, or ① and ② are first complexed to form a chelated metal compound and then an acid is added for protonation to form a catalyst system.

[0018] The auxiliary agent includes auxiliary agent M and / or auxiliary agent N, and auxiliary agent M is a sodium salt, preferably an organic sodium salt, more preferably one or more of sodium salicylate, sodium p-aminobenzoate, sodium o-hydroxybenzoate, sodium m-hydroxybenzoate or sodium p-hydroxybenzoate.

[0019] Preferably, the auxiliary agent N is a stearate, including but not limited to one or more of barium stearate, zinc stearate, calcium stearate, cadmium stearate, magnesium stearate or copper stearate.

[0020] The order of adding the auxiliary agents M and N and components ① to ③ can be arbitrary, and they are preferably added to the reaction system after components ① to ③ react to form the catalyst system.

[0021] Preferably, the auxiliary agent includes auxiliary agent M and auxiliary agent N used simultaneously, and the mass ratio of auxiliary agent M to N is 1:10-10:1, preferably 2:1-1:2. The catalyst system prepared according to the method of the present invention can show excellent catalytic activity and stability in catalyzing the carbonylation reaction of olefinic unsaturated compounds. After the ligand is modified with a large steric hindered group, the generation of isomeric products and polycarbonyl products can be reduced under the action of its spatial confinement effect, and high selectivity of single carbonyl straight-chain products can be achieved, thereby simplifying the subsequent product separation process. At the same time, the ligand of the present invention has a strong coordination ability with the active metal, which can effectively improve the stability of the catalyst during the reaction and reduce the catalyst cost.

[0022] On the other hand, the introduction of additives can effectively increase the gas-liquid mass transfer rate during the reaction of olefinically unsaturated compounds and carbonylation agents. Unexpectedly, the additives can further increase the rate at which alcohol hydroxyl groups dissociate into protons and alkoxy groups during acyl palladium esterification, effectively increasing the carbonylation reaction rate of olefinically unsaturated compounds at high mass transfer rates and high alcohol hydroxyl group dissociation rates.

[0023] The present invention also provides the application of the above catalyst, specifically a method for carbonylating an olefinic unsaturated compound using carbon monoxide as a carbonylation agent in the presence of a hydroxyl-containing compound under the catalyst conditions of the present invention.

[0024] The olefinic unsaturated compound is a straight-chain or branched olefin or alkyne containing one or more unsaturated bonds, preferably 1-3 unsaturated bonds, and may be unsubstituted or substituted by alkyl, aryl, or heteroatom-containing groups, preferably C1-C4 straight-chain olefin or alkyne, and more preferably ethylene.

[0025] The hydroxyl-containing compound is an organic molecule including water or a hydroxyl group, which may be linear or branched, and may be substituted by one or more substituents of a lower alkyl, halogen, nitro or cyano group, preferably an alkanol, and particularly preferably methanol or ethanol. There is no strict requirement for the amount of the hydroxyl-containing compound added, and it can be reasonably adjusted according to the actual reaction activity. Preferably, the molar ratio of the hydroxyl-containing compound added to the olefinic unsaturated compound is 10:1-1:10, and more preferably 2:1-1:2.

[0026] The carbon monoxide is generally in pure form, and may also contain inert gases that do not affect the activity of the catalyst, such as nitrogen, argon, etc., and may also contain a small amount of hydrogen less than 5% by volume. There is no strict requirement for the amount of carbon monoxide used, and the molar ratio of carbon monoxide to the olefinic unsaturated compound is preferably 1:100-1:1.

[0027] The amount of the catalyst can be added according to common knowledge in the art. Preferably, the molar concentration of the active metal component of Group VIB or Group VIIIB in the catalyst in the reaction system is 1-200*10 -5 mol / Kg, more preferably 2-100*10 -5 mol / Kg. That is, the number of moles of active metal components of Group VIB or Group VIB contained in each kilogram of solution (including inert solvent and hydroxyl compound) is 1-200*10 -5 mol, the mass content of the auxiliary agent M in the reaction system (including the inert solvent and the hydroxyl compound) is 0.01wt%-2.0wt%, preferably 0.1wt%-1.0wt%, and the mass content of the auxiliary agent N in the reaction system (including the inert solvent and the hydroxyl compound) is 0.01wt%-5wt%, preferably 0.1wt%-2.0wt%.

[0028] In addition to the raw material hydroxyl compound in the reaction solution, the reaction of the present invention can be carried out in one or more inert solvents. Suitable solvents include ketones, ethers, esters, amides and aromatic compounds and their derivatives. Preferably, the reaction is carried out at 298.15K and 1*10 5 Nm -2 The non-protonic solvent with a dielectric constant in the range of 3-8 is preferably anisole. The amount of the inert solvent is not strictly required, preferably the mass ratio of the inert solvent to the hydroxyl-containing compound is 100:1-1:100, more preferably 20:1-1:20.

[0029] The carbonylation reaction is carried out at 50-150°C, preferably 70-100°C; and at a pressure of 0-5MPa, preferably 0.5-3.5MPa.

[0030] The catalyst prepared according to the present invention is applied to the above-mentioned carbonylation reaction of olefinic unsaturated compounds. On the one hand, it can effectively increase the carbonylation reaction rate of olefinic unsaturated compounds. On the other hand, by increasing the interaction between the ligand and the active metal, it can effectively increase the stability of the active metal during the reaction, making the catalyst more stable during long-term operation. Specific implementation methods

[0031] The following examples further illustrate preferred specific embodiments within the scope of the present invention. These examples are merely illustrative and are not intended to limit the scope of the present invention. The following examples are intended to further introduce and demonstrate specific embodiments within the scope of the present invention. Therefore, the examples should be understood as being only used to illustrate the present invention in more detail, and are not intended to limit the content of the present invention in any way.

[0032] The present invention uses an inductively coupled plasma optical emission spectrometer (ICP-OES) to quantitatively analyze the metal content in the reaction solution.

[0033] The present invention analyzes the composition of the reaction solution by gas chromatography GC-2014, calculates the reaction conversion number TON by formula (1) to compare the catalyst stability, calculates TOF by formula (2) to compare the catalyst reaction rate, and calculates the reaction selectivity by formula (3):

[0034] (1) TON = the amount of methyl propionate generated during the reaction in mol / the total amount of metal added in mol;

[0035] (2) TOF = molar amount of methyl propionate generated per unit time / molar amount of metal required for the reaction;

[0036] (3) Selectivity = the amount of reactants consumed to produce the target product in mol / the amount of reactants involved in the reaction in mol

[0037] Sources of raw materials: 1,1'-bis(di-tert-butylphosphino)ferrocene was purchased from Aladdin with a reagent purity of 98%; triphenylphosphine was purchased from Aladdin with a reagent purity of 99%.

[0038] Example 1

[0039] Under anaerobic conditions, 0.1827 g of nickel nitrate, 9.488 g of 1,1'-bis(di-tert-butylphosphino)ferrocene and 29.4 g of phosphonic acid were added to 1000 g of anisole solution, stirred at room temperature for 1 h, and then transferred to a 5 L reactor purged with nitrogen.

[0040] Under anaerobic conditions, 10 g of sodium salicylate and 10 g of zinc stearate were added to 1000 g of methanol and stirred at room temperature for 1 h, and then transferred to the above catalyst solution and mixed evenly.

[0041] The reactor was replaced with a 1:1 mixed gas of ethylene and carbon monoxide. After replacement, the temperature was raised to 90°C and the pressure was pressed to 2MPa for reaction. As the reaction proceeded, the mixed gas was continuously replenished to ensure the reaction at 2MPa in the reactor. After 1h of reaction, samples were taken for analysis and TOF was calculated. After 8h of reaction, the reaction was stopped and the product composition was analyzed by gas chromatography. The cumulative TON and catalyst selectivity within 8h were calculated. The cumulative TON of the whole process was calculated by applying until the catalyst was deactivated, which was used as the basis for evaluating the catalyst activity.

[0042] After calculation, the TOF of the catalyst was 82541 molMeP / molPd / h, the cumulative TON was 253wmolMeP / molPd, and the selectivity of methyl propionate was as high as 99.9%.

[0043] Example 2

[0044] Under anaerobic conditions, 0.1827 g of nickel nitrate, 0.474 g of 1,1'-bis(di-tert-butylphosphino)ferrocene and 1.96 g of phosphonic acid were added to 312.5 g of anisole solution, stirred at room temperature for 1 h, and then transferred to a 2 L reactor purged with nitrogen.

[0045] Under anaerobic conditions, 1.25 g of sodium p-aminobenzoate and 2.5 g of barium stearate were added to 937.5 g of methanol and stirred at room temperature for 1 h. The mixture was transferred to the above catalyst solution and mixed evenly.

[0046] The reactor was replaced with a 1:1 mixed gas of ethylene and carbon monoxide. After replacement, the temperature was raised to 100°C and the pressure was pressed to 1MPa for reaction. As the reaction proceeded, the mixed gas was continuously replenished to ensure the reaction at 1MPa in the reactor. After 1h of reaction, samples were taken for analysis and TOF was calculated. After 8h of reaction, the reaction was stopped and the product composition was analyzed by gas chromatography. The cumulative TON and catalyst selectivity within 8h were calculated. The cumulative TON of the whole process was calculated by applying until the catalyst was deactivated, which was used as the basis for evaluating the catalyst activity.

[0047] After calculation, the TOF of the catalyst was 76416 molMeP / molPd / h, the cumulative TON was 248 wmolMeP / molPd, and the selectivity of methyl propionate was as high as 99.9%.

[0048] Example 3

[0049] Under anaerobic conditions, 0.1827 g of nickel nitrate, 23.721 g of 1,1'-bis(di-tert-butylphosphino)ferrocene and 39.2 g of phosphonic acid were added to 3000 g of anisole solution, stirred at room temperature for 1 h, and then transferred to a 5 L reactor purged with nitrogen.

[0050] Under anaerobic conditions, 40 g of sodium o-hydroxybenzoate and 20 g of magnesium stearate were added to 1000 g of methanol and stirred at room temperature for 1 h, and then transferred to the above catalyst solution and mixed evenly.

[0051] The reactor was replaced with a 1:1 mixed gas of ethylene and carbon monoxide. After replacement, the temperature was raised to 70°C and the pressure was pressed to 3MPa for reaction. As the reaction proceeded, the mixed gas was continuously replenished to ensure the reaction at 3MPa in the reactor. After 1h of reaction, samples were taken for analysis and TOF was calculated. After 8h of reaction, the reaction was stopped and the product composition was analyzed by gas chromatography. The cumulative TON and catalyst selectivity within 8h were calculated. The cumulative TON of the whole process was calculated by applying it until the catalyst was deactivated, which was used as the basis for evaluating the catalyst activity.

[0052] After calculation, the TOF of the catalyst was 80128 molMeP / molPd / h, the cumulative TON was 240 wmolMeP / molPd, and the selectivity of methyl propionate was as high as 99.9%.

[0053] Example 4

[0054] Under anaerobic conditions, 0.3191 g of platinum nitrate, 9.488 g of 1,1'-bis(di-tert-butylphosphino)ferrocene and 60.0 g of trifluoromethanesulfonic acid were added to 1000 g of anisole solution, stirred at room temperature for 1 h, and then transferred to a 5 L reactor purged with nitrogen.

[0055] Under anaerobic conditions, 10 g of sodium m-hydroxybenzoate and 40 g of calcium stearate were added to 1000 g of methanol and stirred at room temperature for 1 h, and then transferred to the above catalyst solution and mixed evenly.

[0056] The reactor was replaced with a 1:1 mixed gas of ethylene and carbon monoxide. After replacement, the temperature was raised to 90°C and the pressure was pressed to 2MPa for reaction. As the reaction proceeded, the mixed gas was continuously replenished to ensure the reaction at 2MPa in the reactor. After 1h of reaction, samples were taken for analysis and TOF was calculated. After 8h of reaction, the reaction was stopped and the product composition was analyzed by gas chromatography. The cumulative TON and catalyst selectivity within 8h were calculated. The cumulative TON of the whole process was calculated by applying until the catalyst was deactivated, which was used as the basis for evaluating the catalyst activity.

[0057] After calculation, the TOF of the catalyst was 78238 molMeP / molPd / h, the cumulative TON was 235wmolMeP / molPd, and the selectivity of methyl propionate was as high as 99.9%.

[0058] Example 5

[0059] Under anaerobic conditions, 0.2304 g of palladium nitrate, 9.488 g of 1,1'-bis(di-tert-butylphosphino)ferrocene and 60.0 g of trifluoromethanesulfonic acid were added to 1000 g of anisole solution, stirred at room temperature for 1 h, and then transferred to a 5 L reactor purged with nitrogen.

[0060] Under anaerobic conditions, 10 g of sodium p-hydroxybenzoate and 10 g of cadmium stearate were added to 1000 g of methanol, stirred at room temperature for 1 h, and then transferred to the above catalyst solution and mixed evenly.

[0061] The reactor was replaced with a 1:1 mixed gas of ethylene and carbon monoxide. After replacement, the temperature was raised to 90°C and the pressure was pressed to 2MPa for reaction. As the reaction proceeded, the mixed gas was continuously replenished to ensure the reaction at 2MPa in the reactor. After 1h of reaction, samples were taken for analysis and TOF was calculated. After 8h of reaction, the reaction was stopped and the product composition was analyzed by gas chromatography. The cumulative TON and catalyst selectivity within 8h were calculated. The cumulative TON of the whole process was calculated by applying until the catalyst was deactivated, which was used as the basis for evaluating the catalyst activity.

[0062] After calculation, the TOF of the catalyst was 76002 molMeP / molPd / h, the cumulative TON was 234wmolMeP / molPd, and the selectivity of methyl propionate was as high as 99.9%.

[0063] Example 6

[0064] Under anaerobic conditions, 0.1827 g of nickel nitrate, 9.488 g of 1,1'-bis(di-tert-butylphosphino)ferrocene and 29.4 g of phosphonic acid were added to 1000 g of anisole solution, stirred at room temperature for 1 h, and then transferred to a 5 L reactor purged with nitrogen.

[0065] Under anaerobic conditions, 10 g of sodium salicylate was added to 1000 g of methanol and stirred at room temperature for 1 h, and then transferred to the above catalyst solution and mixed evenly.

[0066] The reactor was replaced with a 1:1 mixed gas of ethylene and carbon monoxide. After replacement, the temperature was raised to 90°C and the pressure was pressed to 2MPa for reaction. As the reaction proceeded, the mixed gas was continuously replenished to ensure the reaction at 2MPa in the reactor. After 1h of reaction, samples were taken for analysis and TOF was calculated. After 8h of reaction, the reaction was stopped and the product composition was analyzed by gas chromatography. The cumulative TON and catalyst selectivity within 8h were calculated. The cumulative TON of the whole process was calculated by applying until the catalyst was deactivated, which was used as the basis for evaluating the catalyst activity.

[0067] After calculation, the TOF of the catalyst was 70541 molMeP / molPd / h, the cumulative TON was 228wmolMeP / molPd, and the selectivity of methyl propionate was as high as 99.9%.

[0068] Example 7

[0069] Under anaerobic conditions, 0.1827 g of nickel nitrate, 9.488 g of 1,1'-bis(di-tert-butylphosphino)ferrocene and 29.4 g of phosphonic acid were added to 1000 g of anisole solution, stirred at room temperature for 1 h, and then transferred to a 5 L reactor purged with nitrogen.

[0070] Under anaerobic conditions, 10 g of zinc stearate was added to 1000 g of methanol and stirred at room temperature for 1 h, and then transferred to the above catalyst solution and mixed evenly.

[0071] The reactor was replaced with a 1:1 mixed gas of ethylene and carbon monoxide. After replacement, the temperature was raised to 90°C and the pressure was pressed to 2MPa for reaction. As the reaction proceeded, the mixed gas was continuously replenished to ensure the reaction at 2MPa in the reactor. After 1h of reaction, samples were taken for analysis and TOF was calculated. After 8h of reaction, the reaction was stopped and the product composition was analyzed by gas chromatography. The cumulative TON and catalyst selectivity within 8h were calculated. The cumulative TON of the whole process was calculated by applying until the catalyst was deactivated, which was used as the basis for evaluating the catalyst activity.

[0072] After calculation, the TOF of the catalyst was 68941 molMeP / molPd / h, the cumulative TON was 210 wmolMeP / molPd, and the selectivity of methyl propionate was as high as 99.9%.

[0073] Comparative Example 1

[0074] Under anaerobic conditions, 0.1827 g of nickel nitrate, 9.488 g of 1,1'-bis(di-tert-butylphosphino)ferrocene and 29.4 g of phosphonic acid were added to 1000 g of anisole solution, stirred at room temperature for 1 h, and then transferred to a 5 L reactor purged with nitrogen.

[0075] Under anaerobic conditions, 10 g of sodium carbonate was added to 1000 g of methanol and stirred at room temperature for 1 h, and then transferred to the above catalyst solution and mixed evenly.

[0076] The reactor was replaced with a 1:1 mixed gas of ethylene and carbon monoxide. After replacement, the temperature was raised to 90°C and the pressure was pressed to 2MPa for reaction. As the reaction proceeded, the mixed gas was continuously replenished to ensure the reaction at 2MPa in the reactor. After 1h of reaction, samples were taken for analysis and TOF was calculated. After 8h of reaction, the reaction was stopped and the product composition was analyzed by gas chromatography. The cumulative TON and catalyst selectivity within 8h were calculated. The cumulative TON of the whole process was calculated by applying until the catalyst was deactivated, which was used as the basis for evaluating the catalyst activity.

[0077] After calculation, the TOF of the catalyst was 52800 molMeP / molPd / h, the cumulative TON was 196wmolMeP / molPd, and the selectivity of methyl propionate was as high as 99.9%.

[0078] Comparative Example 2

[0079] Under anaerobic conditions, 0.1827 g of nickel nitrate, 5.246 g of triphenylphosphine and 29.4 g of phosphonic acid were added to 1000 g of anisole solution, stirred at room temperature for 1 h, and then transferred to a 5 L reactor substituted with nitrogen.

[0080] Under anaerobic conditions, 10 g of sodium salicylate was added to 1000 g of methanol and stirred at room temperature for 1 h, and then transferred to the above catalyst solution and mixed evenly.

[0081] The reactor was replaced with a 1:1 mixed gas of ethylene and carbon monoxide. After replacement, the temperature was raised to 90°C and the pressure was pressed to 2MPa for reaction. As the reaction proceeded, the mixed gas was continuously replenished to ensure the reaction at 2MPa in the reactor. After 1h of reaction, samples were taken for analysis and TOF was calculated. After 8h of reaction, the reaction was stopped and the product composition was analyzed by gas chromatography. The cumulative TON and catalyst selectivity within 8h were calculated. The cumulative TON of the whole process was calculated by applying until the catalyst was deactivated, which was used as the basis for evaluating the catalyst activity.

[0082] After calculation, the TOF of the catalyst was 56250 molMeP / molPd / h, the cumulative TON was 201wmolMeP / molPd, and the selectivity of methyl propionate was as high as 99.9%.

[0083] Comparative Example 3

[0084] Under anaerobic conditions, 0.1827 g of nickel nitrate, 9.488 g of 1,1'-bis(di-tert-butylphosphino)ferrocene and 29.4 g of phosphonic acid were added to a mixed solution of 1000 g of anisole and 1000 g of methanol, stirred at room temperature for 1 h, and then transferred to a 5 L reactor purged with nitrogen.

[0085] The reactor was replaced with a 1:1 mixed gas of ethylene and carbon monoxide. After replacement, the temperature was raised to 90°C and the pressure was pressed to 2MPa for reaction. As the reaction proceeded, the mixed gas was continuously replenished to ensure the reaction at 2MPa in the reactor. After 1h of reaction, samples were taken for analysis and TOF was calculated. After 8h of reaction, the reaction was stopped and the product composition was analyzed by gas chromatography. The cumulative TON and catalyst selectivity within 8h were calculated. The cumulative TON of the whole process was calculated by applying until the catalyst was deactivated, which was used as the basis for evaluating the catalyst activity.

[0086] After calculation, the TOF of the catalyst was 44127 molMeP / molPd / h, the cumulative TON was 180wmolMeP / molPd, and the selectivity of methyl propionate was as high as 99.9%.

[0087] By comparing the activity and stability of the olefinic unsaturated compound catalysts prepared in the above examples and comparative examples, it can be seen that the catalyst prepared by this patent can exhibit high reaction rate and product selectivity. In addition, unexpectedly, the active metal is more stable during the above reaction process, showing excellent long-term stability.

Claims

1. An olefinically unsaturated compound carbonylation catalyst, characterized in that: The catalyst comprises a main catalyst and an auxiliary agent, and the main catalyst comprises the following components: ① Group VIB or Group VIIIB metal active components; ② Ligand; ③Acid; Wherein, the Group VIB or Group VIB metal includes one or more of metals Cr, Mo, W, Fe, Co, Ni, Ru, Rh, Os, Ir, Pt and Pd, and the ligand is a bidentate phosphine, bidentate arsenide or bidentate antimony ligand; The auxiliary agents include auxiliary agent M and auxiliary agent N; The auxiliary agent M is an organic sodium salt, selected from one or more of sodium salicylate, sodium p-aminobenzoate, sodium o-hydroxybenzoate, sodium m-hydroxybenzoate or sodium p-hydroxybenzoate; The auxiliary agent N includes one or more of barium stearate, zinc stearate, calcium stearate, cadmium stearate, magnesium stearate or copper stearate.

2. The catalyst according to claim 1, characterized in that The Group VIB or Group VIB metal is selected from Ni, Pt and Pd.

3. The catalyst according to claim 1, characterized in that The ligand is a bidentate phosphine ligand having the following general formula (1): Wherein X is a substituted bridging group, X is selected from a substitutable aryl group, a cyclopentadienyl group, an indenyl group or a cycloalkyl group; R1, R2, R3 and R4 are substituent groups connected to the phosphorus atom, R1, R2, R3 and R4 are the same or different, and R1, R2, R3 and R4 are respectively selected from substituent groups with large steric hindrance, and the substituent groups with large steric hindrance include tert-butyl group, adamantyl group and substituent groups thereof.

4. The catalyst according to claim 3, characterized in that X is cyclopentadienyl.

5. The catalyst according to claim 1, characterized in that The molar ratio of the ligand to the Group VIB or Group VIB metal active component is 1:1-100:

1.

6. The catalyst according to claim 5, characterized in that The molar ratio of the ligand to the Group VIB or Group VIB metal active component is 1:1-50:

1.

7. The catalyst according to claim 1, characterized in that The acids include compounds derived from weakly coordinating anions, lower alkanoic acids, sulfonic acids and phosphonic acids.

8. The catalyst according to claim 7, characterized in that The acid is selected from sulfonic acid and phosphonic acid.

9. The catalyst according to claim 1, characterized in that The molar ratio of the acid to the Group VIB or Group VIB metal active component is 2:1-500:

1.

10. The catalyst according to claim 9, characterized in that The molar ratio of the acid to the Group VIB or Group VIB metal active component is 20:1-400:

1.

11. The catalyst according to claim 1, characterized in that The auxiliary agent includes auxiliary agent M and auxiliary agent N, and the mass ratio of auxiliary agent M to N is 1:10-10:

1.

12. The catalyst according to claim 11, characterized in that The mass ratio of additives M and N is 2:1-1:

2.

13. Use of the catalyst according to any one of claims 1 to 12 in a carbonylation reaction, characterized in that: A method for carbonylating an olefinically unsaturated compound in the presence of the catalyst using carbon monoxide as a carbonylating agent in the presence of a hydroxyl-containing compound.

14. The use according to claim 13, characterized in that The olefinically unsaturated compound is a straight-chain or branched olefin or alkyne containing one or more unsaturated bonds.

15. The use according to claim 14, characterized in that The olefinic unsaturated compound is a straight-chain or branched olefin or alkyne containing 1 to 3 unsaturated bonds.

16. The use according to claim 13, characterized in that: The olefinically unsaturated compound is a C1-C4 straight chain olefin or alkyne.

17. The use according to claim 16, characterized in that The ethylenically unsaturated compound is ethylene.

18. The use according to claim 13, characterized in that: The hydroxyl-containing compound is an organic molecule including water or a hydroxyl-containing group.

19. The use according to claim 18, characterized in that The hydroxyl-containing compound is an alkanol.

20. The use according to claim 19, characterized in that The hydroxyl-containing compound is methanol or ethanol.

21. The use according to claim 13, characterized in that: The molar ratio of the added amount of the hydroxyl-containing compound to the olefinically unsaturated compound is 10:1-1:

10.

22. The use according to claim 21, characterized in that The molar ratio of the added amount of the hydroxyl-containing compound to the olefinically unsaturated compound is 2:1-1:

2.

23. The use according to claim 13, characterized in that: The molar ratio of carbon monoxide to the olefinic unsaturated compound is 1:100-1:

1.

24. The use according to claim 14, characterized in that: The reaction is carried out in a solvent. Suitable solvents include ketones, ethers, esters, amides, aromatic compounds and their derivatives.

25. The use according to claim 24, characterized in that The solvent is at 298.15K and 1*10 5 Nm -2 Aprotic solvents with dielectric constants in the range of 3-8.

26. The use according to claim 25, characterized in that The solvent is anisole.

27. The use according to claim 24, characterized in that The mass ratio of the solvent to the hydroxyl-containing compound is 100:1-1:

100.

28. The use according to claim 27, characterized in that The mass ratio of the solvent to the hydroxyl-containing compound is 20:1-1:

20.

29. The use according to claim 24, characterized in that The molar concentration of the active metal component of group VIB or group VIB in the catalyst in the reaction system is 1-200*10 -5 mol, the solution comprises a solvent and a hydroxyl compound.

30. The use according to claim 24, characterized in that The mass content of the auxiliary agent M in the reaction system is 0.01wt%-2.0wt%, the mass content of the auxiliary agent N in the reaction system is 0.01wt%-5wt%, and the reaction system includes a solvent and a hydroxyl compound.

31. The use according to claim 30, characterized in that The mass content of the auxiliary agent M in the reaction system is 0.1wt%-1.0wt%, the mass content of the auxiliary agent N in the reaction system is 0.1wt%-2.0wt%, and the reaction system includes a solvent and a hydroxyl compound.

32. The use according to any one of claims 13 to 31, characterized in that: The carbonylation reaction is carried out at 50-150°C and the reaction pressure is 0-5MPa.

33. The use according to claim 32, characterized in that The carbonylation reaction is carried out at 70-100° C. and the reaction pressure is 0.5-3.5 MPa.

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