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CN116459873B - A catalyst for carbonylation of olefinic unsaturated compounds and its preparation method and application - Google Patents

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

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CN116459873B
CN116459873B CN202210036542.9A CN202210036542A CN116459873B CN 116459873 B CN116459873 B CN 116459873B CN 202210036542 A CN202210036542 A CN 202210036542A CN 116459873 B CN116459873 B CN 116459873B
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CN116459873A (en
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纪勇强
易光铨
殷艳欣
王昀
孙康
黎源
华卫琦
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Wanhua Chemical Group Co Ltd
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
    • C07C67/38—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by addition to an unsaturated carbon-to-carbon bond
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/824—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/828—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/842—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/847—Nickel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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    • Y02P20/584—Recycling of catalysts

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Abstract

The invention provides a carbonylation catalyst, a preparation method and application thereof, wherein the catalyst takes VIB or VIIIB metal as an active site, takes a large-steric-hindrance bidentate ligand as a metal complex, can show high reaction rate and product selectivity when being used for the carbonylation reaction of an olefinically unsaturated compound under the action of an organic sodium salt and a stearate auxiliary agent, and meanwhile, active components have better stability in the reaction process, so that the catalyst can show excellent long-period stability.

Description

Olefinically unsaturated compound carbonylation catalyst and preparation method and application thereof
Technical Field
The invention relates to the field of carbonylation of olefinically unsaturated compounds, in particular to a catalyst for carbonylation of olefinically unsaturated compounds, a preparation method and application thereof.
Background
At present, carbonylation reaction researches are mature, mainly, under the action of a transition metal catalyst, synthesis gas is used as a carbonyl source to realize the hydroformylation of unsaturated hydrocarbon and fatty acid, and meanwhile, a plurality of domestic and foreign patent researches report that in an alcohol or water system, only CO is used as a carbonyl source to enable an olefinically unsaturated compound to be carbonylated to obtain corresponding ester or carboxylic acid, carbonylation and esterification processes are realized in one step, a catalyst system mainly uses VI, VIII, IX or an X group element as an active site, and monodentate or bidentate phosphine is used as a ligand, such as alkyl, aryl, cycloalkyl or pyridylphosphine, and the catalytic carbonylation reaction process is realized after coordination complexing.
WO96/19434 discloses a bidentate phosphine ligand structure in which aryl groups are used as bridging groups and adjacent carbon atoms of the aryl groups are connected with phosphorus, so that the carbonylation reaction rate of an olefinically unsaturated compound is obviously improved, federico et al find that the dissociation between an alkoxy group of an ester-forming precursor alcohol and proton hydrogen is the rate limiting step of the reaction when the dynamics of the system is studied, but do not mention an effective solution for improving the alcoholysis rate. In addition, for the reaction of carbonylation of olefinically unsaturated compounds to esters, the bidentate phosphine ligand catalyst system disclosed in EP-A-0227160 and the like can effectively improve the catalyst activity, but has the problem of poor stability caused by reduction, precipitation and inactivation of active sites in the reaction process, and has the problem of higher cost in industrialization.
Disclosure of Invention
In order to solve the above problems, an object of the present invention is to provide an olefinically unsaturated compound carbonylation catalyst and a method for preparing the same, by which the carbonylation reaction rate can be further increased, and the loss of active metal sites during the carbonylation of the olefinically unsaturated compound can be effectively suppressed, thereby remarkably improving the stability thereof and reducing the catalyst cost.
It is another object of the present invention to provide a method for preparing a carboxylic acid ester thereof by catalyzing an olefinically unsaturated compound with the catalyst, which is applied to the carbonylation of the olefinically unsaturated compound, has substantially no other by-products, has high selectivity and has excellent catalytic activity.
In order to achieve the above purpose, the present invention adopts the following scheme.
An olefinically unsaturated compound carbonylation catalyst comprising a main catalyst and an adjunct, the main catalyst comprising the following components:
① A group VIB or group VIIIB metal active component;
② A ligand;
③ An acid;
Wherein the group VIB or group VIIIB metal comprises one or more of metal Cr, mo, W, fe, co, ni, ru, rh, os, ir, pt and Pd, preferably selected from Ni, pt and Pd, and the ligand is bidentate phosphine, arsine or antimony ligand.
The ligand is preferably a bidentate phosphine ligand of the following general formula (1),
Wherein X is a substituted bridging group and X is selected from the group consisting of a substitutable aryl, cyclopentadienyl, indenyl, or cycloalkyl group, preferably cyclopentadienyl. R 1、R2、R3 and R 4 are substituents attached to a phosphorus atom, R 1、R2、R3 and R 4 are the same or different, and R 1、R2、R3 and R 4 are each selected from substituents having a large steric hindrance as t-butyl groups, including but not limited to t-butyl groups, adamantyl groups, and substituents thereof.
The molar ratio of the ligand to the active component of the metal in the VIB group or the VIIIB group is 1:1-100:1, preferably 1:1-50:1, so as to ensure the saturated coordination of the active site of the metal and enhance the binding force of the ligand and the active site of the metal.
The acid is a compound derived from weak coordination anions, low carbon chain alkanoic acid, sulfonic acid, phosphonic acid, and the like, and sulfonic acid and phosphonic acid are preferred. The molar ratio of the acid to the active component of the metal of group VIB or group VIIIB is from 2:1 to 500:1, preferably from 20:1 to 400:1.
Components ① to ③ can be added to an organic solvent in situ to react to form a main catalyst required by carbonylation reaction, or can be synthesized in any order to form a catalyst system, or can be synthesized in a specific order, three components can be combined in any form to form intermediate components and then react with a third component to form a final main catalyst, for example, components ② and ③ are firstly mixed to form a protonated ligand and then are complexed with ① to form the catalyst system, or ① and ② are firstly complexed to form a chelated metal compound and then are added with acid to carry out protonation to form the catalyst system.
The auxiliary agent comprises an auxiliary agent M and/or an auxiliary agent N, wherein the auxiliary agent M is sodium salt, preferably organic sodium salt, more preferably one or more of sodium salicylate, sodium p-aminobenzoate, sodium o-hydroxybenzoate, sodium M-hydroxybenzoate or sodium p-hydroxybenzoate.
Preferably, the auxiliary agent N is stearate, including but not limited to one or more of barium stearate, zinc stearate, calcium stearate, cadmium stearate, magnesium stearate or copper stearate.
The order of addition of the auxiliaries M and N to the components ① to ③ may be arbitrary, preference being given to adding the reaction system after the components ① to ③ have reacted to give the catalyst system.
Preferably, the auxiliary agent comprises an auxiliary agent M and an auxiliary agent N which are used simultaneously, wherein the mass ratio of the auxiliary agent M to the auxiliary agent N is 1:10-10:1, preferably 2:1-1:2. The catalyst system prepared by the method can show excellent catalytic activity and stability in catalyzing the carbonylation reaction of the olefinically unsaturated compound, can reduce the generation of isomerism products and multi-carbonyl products under the effect of a space restriction effect after a ligand modifies a large steric hindrance group, and realizes high selectivity of single-carbonyl linear products, thereby simplifying the subsequent product separation process.
On the other hand, the introduction of the auxiliary agent can effectively improve the gas-liquid mass transfer rate in the reaction process of the olefinically unsaturated compound and the carbonylation reagent, and unexpectedly, the auxiliary agent can further improve the rate of dissociating the alcoholic hydroxyl group into protons and alkoxy groups in the esterification process of the acyl palladium, and effectively improve the carbonylation reaction rate of the olefinically unsaturated compound under the conditions of high mass transfer rate and high alcoholic hydroxyl group dissociation rate.
The invention also provides application of the catalyst, and specifically relates to a method for carbonylating an olefinically unsaturated compound in the presence of a hydroxyl-containing compound by using carbon monoxide as a carbonylation reagent under the condition of the catalyst.
The olefinically unsaturated compound is a linear or branched olefin or alkyne containing one or more unsaturated bonds, preferably 1 to 3 unsaturated bonds, which may be unsubstituted or substituted with alkyl, aryl, heteroatom-containing groups and the like, preferably a C1 to C4 linear olefin or alkyne, more preferably ethylene.
The hydroxyl-containing compound is an organic molecule comprising water or a hydroxyl-containing group, which may be linear or branched, and may be substituted by one or more substituents of lower alkyl, halogen, nitro or cyano, preferably an alkanol, particularly preferably methanol or ethanol. The amount of the hydroxyl-containing compound to be added is not critical and can be reasonably adjusted according to the actual reactivity, and preferably, the molar ratio of the hydroxyl-containing compound to the ethylenically unsaturated compound is 10:1 to 1:10, more preferably 2:1 to 1:2.
The carbon monoxide is generally in a pure state, can also contain inert gases such as nitrogen, argon and the like which do not influence the activity of the catalyst, can also simultaneously contain a small amount of hydrogen with the volume of less than 5 percent, and has no strict requirement on the dosage of the carbon monoxide, and the molar ratio of the carbon monoxide to the olefinically unsaturated compound is preferably 1:100-1:1.
The catalyst may be added in an amount according to common general knowledge in the art, preferably the molar concentration of the active component of the group VIB or group VIIIB metal in the catalyst in the reaction system is 1-200 x 10 -5 mol/Kg, more preferably 2-100 x 10 -5 mol/Kg. I.e. the molar number of active components of the metal of group VIB or group VIIIB contained in each kilogram of solution (comprising inert solvent and hydroxyl compound) is 1-200 x 10 -5 mol, the mass content of the auxiliary M in the reaction system (comprising inert solvent and hydroxyl compound) is 0.01-2.0 wt%, preferably 0.1-1.0 wt%, and the mass content of the auxiliary N in the reaction system (comprising inert solvent and hydroxyl compound) is 0.01-5 wt%, preferably 0.1-2.0 wt%.
In addition to the starting hydroxyl-containing compounds in the reaction solution, the reaction according to the invention may be carried out in one or more inert solvents, suitable solvents include ketones, ethers, esters, amides and aromatic compounds and derivatives thereof, preferably aprotic solvents having a dielectric constant in the range 3-8 at 298.15K and 1 x 10 5Nm-2, more preferably anisole. The amount of the inert solvent is not critical, and the mass ratio of the inert solvent to the hydroxyl-containing compound is preferably 100:1 to 1:100, more preferably 20:1 to 1:20.
The carbonylation reaction is carried out at 50-150 ℃, preferably at 70-100 ℃, and at 0-5MPa, preferably at 0.5-3.5MPa.
The catalyst prepared according to the invention is applied to the carbonylation reaction of the olefinically unsaturated compound, on one hand, the carbonylation reaction rate of the olefinically unsaturated compound can be effectively improved, and on the other hand, the stability of active metal in the reaction process can be effectively improved by improving the interaction between the ligand and the active metal, so that the catalyst is more stable in the long-period operation process.
Detailed description of the preferred embodiments
The following examples further illustrate preferred embodiments within the scope of the present invention, which are intended to be illustrative only and not limiting in any way, and are therefore intended to further describe and illustrate the embodiments within the scope of the present invention.
The invention quantitatively analyzes the metal content in the reaction liquid by an inductively coupled plasma emission spectrometer (ICP-OES).
The invention analyzes the composition of the reaction liquid through gas chromatography GC-2014, calculates the conversion number TON through a formula (1) to compare the stability of the catalyst, calculates TOF through a formula (2) to compare the reaction rate of the catalyst, and calculates the reaction selectivity through a formula (3):
(1) Ton=mol of methyl propionate accumulated during the reaction/mol of total addition of metal;
(2) TOF = mole of methyl propionate produced per unit time/mole of metal required for the reaction;
(3) Selectivity = mol of reactant consumed to form the desired product/mol of reactant involved in the reaction
The raw materials comprise 1,1' -bis (di-tert-butylphosphino) ferrocene which is purchased from Aladin, the purity of the reagent is 98 percent, and triphenylphosphine which is purchased from Aladin, and the purity of the reagent is 99 percent.
Example 1
0.1827G of nickel nitrate, 9.488g of 1,1' -bis (di-tert-butylphosphino) ferrocene and 29.4g of phosphonic acid were added to 1000g of anisole solution under anaerobic conditions, stirred at room temperature for 1h and transferred to a nitrogen-substituted 5L reaction vessel.
10G of sodium salicylate and 10g of zinc stearate are added into 1000g of methanol under the anaerobic condition, stirred for 1h at normal temperature, transferred into the catalyst solution and uniformly mixed.
The mixed gas of ethylene and carbon monoxide with the ratio of 1:1 is used for replacing a reaction kettle, the temperature is raised to 90 ℃ after replacement, the mixed gas is stamped to 2MPa for reaction, the mixed gas is continuously supplemented along with the reaction, the 2MPa in the kettle is guaranteed for reaction, sampling analysis and TOF calculation are carried out after the reaction is carried out for 1h, the reaction is stopped after the reaction is carried out for 8h, the product composition is analyzed through gas chromatography, the accumulated TON and the catalyst selectivity in 8h are obtained through calculation, and the accumulated TON in the whole process is calculated to be used as the catalyst activity evaluation basis through the application until the catalyst is deactivated.
Calculated, the TOF of the catalyst is 82541molMeP/molPd/h, the accumulated TON is 253wmolMeP/molPd, and the selectivity of methyl propionate is as high as 99.9%.
Example 2
0.1827G of nickel nitrate, 0.474g of 1,1' -bis (di-tert-butylphosphino) ferrocene and 1.96g of phosphonic acid were added to 312.5g of anisole solution under anaerobic conditions, stirred at room temperature for 1h and transferred to a nitrogen-substituted 2L reactor.
Under the anaerobic condition, 1.25g of sodium p-aminobenzoate and 2.5g of barium stearate are added into 937.5g of methanol and stirred for 1h at normal temperature, and transferred into the catalyst solution, and uniformly mixed.
The mixed gas of ethylene and carbon monoxide with the ratio of 1:1 is used for replacing a reaction kettle, the temperature is raised to 100 ℃ after replacement, the mixed gas is stamped to 1MPa for reaction, the mixed gas is continuously supplemented to ensure that the reaction is carried out under the condition of 1MPa in the kettle, sampling analysis and TOF calculation are carried out after the reaction is carried out for 1h, the reaction is stopped after the reaction is carried out for 8h, the product composition is analyzed through gas chromatography, the accumulated TON and the catalyst selectivity in 8h are obtained through calculation, and the accumulated TON in the whole process is calculated to be used as the catalyst activity evaluation basis through the application until the catalyst is deactivated.
Calculated, the TOF of the catalyst is 76416molMeP/molPd/h, the accumulated TON is 248wmolMeP/molPd, and the selectivity of methyl propionate is as high as 99.9%.
Example 3
0.1827G of nickel nitrate, 23.721g of 1,1' -bis (di-tert-butylphosphino) ferrocene and 39.2g of phosphonic acid were added to 3000g of anisole solution under anaerobic conditions, stirred at room temperature for 1h and transferred to a nitrogen-substituted 5L reaction vessel.
Under the anaerobic condition, 40g of sodium o-hydroxybenzoate and 20g of magnesium stearate are added into 1000g of methanol, stirred for 1h at normal temperature, transferred into the catalyst solution and uniformly mixed.
The mixed gas of ethylene and carbon monoxide with the ratio of 1:1 is used for replacing a reaction kettle, the temperature is raised to 70 ℃ after replacement, the mixed gas is stamped to 3MPa for reaction, along with the reaction, the mixed gas is continuously supplemented to ensure the 3MPa in the kettle for reaction, sampling analysis and TOF calculation are carried out after the reaction is carried out for 1h, the reaction is stopped after the reaction is carried out for 8h, the product composition is analyzed through gas chromatography, the accumulated TON and the catalyst selectivity in 8h are obtained through calculation, and the accumulated TON in the whole process is calculated to be used as the catalyst activity evaluation basis through the application until the catalyst is deactivated.
Calculated, the TOF of the catalyst is 80128molMeP/molPd/h, the accumulated TON is 240wmolMeP/molPd, and the selectivity of methyl propionate is as high as 99.9%.
Example 4
0.3191G of platinum nitrate, 9.488g of 1,1' -bis (di-tert-butylphosphino) ferrocene and 60.0g of trifluoromethanesulfonic acid were added to 1000g of anisole solution under anaerobic conditions, stirred at room temperature for 1 hour and transferred to a nitrogen-substituted 5L reaction vessel.
10G of sodium metahydroxybenzoate and 40g of calcium stearate were added to 1000g of methanol under anaerobic conditions and stirred at normal temperature for 1 hour, and transferred to the above catalyst solution, and mixed uniformly.
The mixed gas of ethylene and carbon monoxide with the ratio of 1:1 is used for replacing a reaction kettle, the temperature is raised to 90 ℃ after replacement, the mixed gas is stamped to 2MPa for reaction, the mixed gas is continuously supplemented along with the reaction, the 2MPa in the kettle is guaranteed for reaction, sampling analysis and TOF calculation are carried out after the reaction is carried out for 1h, the reaction is stopped after the reaction is carried out for 8h, the product composition is analyzed through gas chromatography, the accumulated TON and the catalyst selectivity in 8h are obtained through calculation, and the accumulated TON in the whole process is calculated to be used as the catalyst activity evaluation basis through the application until the catalyst is deactivated.
Calculated, the TOF of the catalyst is 78238molMeP/molPd/h, the accumulated TON is 235wmolMeP/molPd, and the selectivity of methyl propionate is as high as 99.9%.
Example 5
0.2304G of palladium nitrate, 9.488g of 1,1' -bis (di-tert-butylphosphino) ferrocene and 60.0g of trifluoromethanesulfonic acid were added to 1000g of anisole solution under anaerobic conditions, stirred at room temperature for 1 hour and transferred to a nitrogen-substituted 5L reaction vessel.
Under the anaerobic condition, 10g of sodium p-hydroxybenzoate and 10g of cadmium stearate are added into 1000g of methanol, stirred for 1h at normal temperature, transferred into the catalyst solution and uniformly mixed.
The mixed gas of ethylene and carbon monoxide with the ratio of 1:1 is used for replacing a reaction kettle, the temperature is raised to 90 ℃ after replacement, the mixed gas is stamped to 2MPa for reaction, the mixed gas is continuously supplemented along with the reaction, the 2MPa in the kettle is guaranteed for reaction, sampling analysis and TOF calculation are carried out after the reaction is carried out for 1h, the reaction is stopped after the reaction is carried out for 8h, the product composition is analyzed through gas chromatography, the accumulated TON and the catalyst selectivity in 8h are obtained through calculation, and the accumulated TON in the whole process is calculated to be used as the catalyst activity evaluation basis through the application until the catalyst is deactivated.
Calculated, the TOF of the catalyst is 76002molMeP/molPd/h, the accumulated TON is 234wmolMeP/molPd, and the selectivity of methyl propionate is as high as 99.9%.
Example 6
0.1827G of nickel nitrate, 9.488g of 1,1' -bis (di-tert-butylphosphino) ferrocene and 29.4g of phosphonic acid were added to 1000g of anisole solution under anaerobic conditions, stirred at room temperature for 1h and transferred to a nitrogen-substituted 5L reaction vessel.
10G of sodium salicylate is added into 1000g of methanol under the anaerobic condition, stirred for 1h at normal temperature, transferred into the catalyst solution and uniformly mixed.
The mixed gas of ethylene and carbon monoxide with the ratio of 1:1 is used for replacing a reaction kettle, the temperature is raised to 90 ℃ after replacement, the mixed gas is stamped to 2MPa for reaction, the mixed gas is continuously supplemented along with the reaction, the 2MPa in the kettle is guaranteed for reaction, sampling analysis and TOF calculation are carried out after the reaction is carried out for 1h, the reaction is stopped after the reaction is carried out for 8h, the product composition is analyzed through gas chromatography, the accumulated TON and the catalyst selectivity in 8h are obtained through calculation, and the accumulated TON in the whole process is calculated to be used as the catalyst activity evaluation basis through the application until the catalyst is deactivated.
Calculated, the TOF of the catalyst is 70541molMeP/molPd/h, the accumulated TON is 228wmolMeP/molPd, and the selectivity of methyl propionate is as high as 99.9%.
Example 7
0.1827G of nickel nitrate, 9.488g of 1,1' -bis (di-tert-butylphosphino) ferrocene and 29.4g of phosphonic acid were added to 1000g of anisole solution under anaerobic conditions, stirred at room temperature for 1h and transferred to a nitrogen-substituted 5L reaction vessel.
Under the anaerobic condition, 10g of zinc stearate is added into 1000g of methanol and stirred for 1h at normal temperature, and then is transferred into the catalyst solution to be uniformly mixed.
The mixed gas of ethylene and carbon monoxide with the ratio of 1:1 is used for replacing a reaction kettle, the temperature is raised to 90 ℃ after replacement, the mixed gas is stamped to 2MPa for reaction, the mixed gas is continuously supplemented along with the reaction, the 2MPa in the kettle is guaranteed for reaction, sampling analysis and TOF calculation are carried out after the reaction is carried out for 1h, the reaction is stopped after the reaction is carried out for 8h, the product composition is analyzed through gas chromatography, the accumulated TON and the catalyst selectivity in 8h are obtained through calculation, and the accumulated TON in the whole process is calculated to be used as the catalyst activity evaluation basis through the application until the catalyst is deactivated.
Calculated, the TOF of the catalyst is 68941molMeP/molPd/h, the accumulated TON is 210wmolMeP/molPd, and the selectivity of methyl propionate is as high as 99.9%.
Comparative example 1
0.1827G of nickel nitrate, 9.488g of 1,1' -bis (di-tert-butylphosphino) ferrocene and 29.4g of phosphonic acid were added to 1000g of anisole solution under anaerobic conditions, stirred at room temperature for 1h and transferred to a nitrogen-substituted 5L reaction vessel.
10G of sodium carbonate is added into 1000g of methanol under the anaerobic condition, stirred for 1h at normal temperature, transferred into the catalyst solution and uniformly mixed.
The mixed gas of ethylene and carbon monoxide with the ratio of 1:1 is used for replacing a reaction kettle, the temperature is raised to 90 ℃ after replacement, the mixed gas is stamped to 2MPa for reaction, the mixed gas is continuously supplemented along with the reaction, the 2MPa in the kettle is guaranteed for reaction, sampling analysis and TOF calculation are carried out after the reaction is carried out for 1h, the reaction is stopped after the reaction is carried out for 8h, the product composition is analyzed through gas chromatography, the accumulated TON and the catalyst selectivity in 8h are obtained through calculation, and the accumulated TON in the whole process is calculated to be used as the catalyst activity evaluation basis through the application until the catalyst is deactivated.
Calculated, the TOF of the catalyst is 52800molMeP/molPd/h, the accumulated TON is 196wmolMeP/molPd, and the selectivity of methyl propionate is as high as 99.9%.
Comparative example 2
0.1827G of nickel nitrate, 5.246g of triphenylphosphine and 29.4g of phosphonic acid were added to 1000g of anisole solution under anaerobic conditions, stirred at room temperature for 1h and transferred to a nitrogen-substituted 5L reactor.
10G of sodium salicylate is added into 1000g of methanol under the anaerobic condition, stirred for 1h at normal temperature, transferred into the catalyst solution and uniformly mixed.
The mixed gas of ethylene and carbon monoxide with the ratio of 1:1 is used for replacing a reaction kettle, the temperature is raised to 90 ℃ after replacement, the mixed gas is stamped to 2MPa for reaction, the mixed gas is continuously supplemented along with the reaction, the 2MPa in the kettle is guaranteed for reaction, sampling analysis and TOF calculation are carried out after the reaction is carried out for 1h, the reaction is stopped after the reaction is carried out for 8h, the product composition is analyzed through gas chromatography, the accumulated TON and the catalyst selectivity in 8h are obtained through calculation, and the accumulated TON in the whole process is calculated to be used as the catalyst activity evaluation basis through the application until the catalyst is deactivated.
Calculated, the TOF of the catalyst is 56250molMeP/molPd/h, the accumulated TON is 201wmolMeP/molPd, and the selectivity of methyl propionate is as high as 99.9%.
Comparative example 3
0.1827G of nickel nitrate, 9.488g of 1,1' -bis (di-tert-butylphosphino) ferrocene and 29.4g of phosphonic acid were added to a mixed solution of 1000g of anisole and 1000g of methanol under anaerobic conditions, stirred at room temperature for 1 hour and then transferred to a nitrogen-substituted 5L reaction vessel.
The mixed gas of ethylene and carbon monoxide with the ratio of 1:1 is used for replacing a reaction kettle, the temperature is raised to 90 ℃ after replacement, the mixed gas is stamped to 2MPa for reaction, the mixed gas is continuously supplemented along with the reaction, the 2MPa in the kettle is guaranteed for reaction, sampling analysis and TOF calculation are carried out after the reaction is carried out for 1h, the reaction is stopped after the reaction is carried out for 8h, the product composition is analyzed through gas chromatography, the accumulated TON and the catalyst selectivity in 8h are obtained through calculation, and the accumulated TON in the whole process is calculated to be used as the catalyst activity evaluation basis through the application until the catalyst is deactivated.
Calculated, the TOF of the catalyst is 44127molMeP/molPd/h, the accumulated TON is 180wmolMeP/molPd, and the selectivity of methyl propionate is as high as 99.9%.
By comparing the activity and stability of the olefinically unsaturated compounds prepared in the above examples and comparative examples, it is possible to obtain catalysts prepared by the present patent which can exhibit high reaction rates and product selectivities. Furthermore, unexpectedly, the active metals are more stable during the above reaction, exhibiting excellent long-cycle stability.

Claims (33)

1.一种烯属不饱和化合物羰基化催化剂，其特征在于，所述催化剂包括主催化剂和助剂，所述主催化剂包括以下组分：1. A catalyst for carbonylation of olefinic unsaturated compounds, characterized in that the catalyst comprises a main catalyst and a promoter, wherein the main catalyst comprises the following components: ①ⅥB族或ⅧB族金属活性组分；① Group VIB or Group VIIIB metal active components; ②配体；② Ligand; ③酸；③ Acid; 其中，ⅥB族或ⅧB族金属包括金属Cr、Mo、W、Fe、Co、Ni、Ru、Rh、Os、Ir、Pt和Pd中的一种或多种，配体为二齿膦、二齿胂或二齿锑配体；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; 所述助剂包括助剂M和助剂N；The auxiliary agent includes auxiliary agent M and auxiliary agent N; 所述助剂M为有机钠盐，选自水杨酸钠、对氨基苯甲酸钠、邻羟苯甲酸钠、间羟苯甲酸钠或对羟苯甲酸钠中的一种或几种；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; 所述助剂N包括硬脂酸钡、硬脂酸锌、硬脂酸钙、硬脂酸镉、硬脂酸镁或硬脂酸铜中的一种或几种。The auxiliary agent N includes one or more of barium stearate, zinc stearate, calcium stearate, cadmium stearate, magnesium stearate or copper stearate. 2.根据权利要求1所述的催化剂，其特征在于，ⅥB族或ⅧB族金属选自Ni、Pt和Pd。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.根据权利要求1所述的催化剂，其特征在于，所述配体具有如下通式(1)的二齿膦配体，3. The catalyst according to claim 1, characterized in that the ligand is a bidentate phosphine ligand having the following general formula (1): 其中X为取代桥连基，X选自可取代的芳基、环戊二烯基、茚基或环烷基；R1、R2、R3和R4为与磷原子相连的取代基团，R1、R2、R3和R4相同或不同，R1、R2、R3和R4分别选自具有大空间位阻的取代基团，所述大空间位阻的取代基团包括叔丁基、金刚烷基及其取代物基团。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; R 1 , R 2 , R 3 and R 4 are substituent groups connected to the phosphorus atom, R 1 , R 2 , R 3 and R 4 are the same or different, and R 1 , R 2 , R 3 and R 4 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.根据权利要求3所述的催化剂，其特征在于，X为环戊二烯基。The catalyst according to claim 3 , characterized in that X is a cyclopentadienyl group. 5.根据权利要求1所述的催化剂，其特征在于，所述配体与ⅥB族或ⅧB族金属活性组分摩尔比为1：1-100：1。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.根据权利要求5所述的催化剂，其特征在于，所述配体与ⅥB族或ⅧB族金属活性组分摩尔比为1：1-50：1。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.根据权利要求1所述的催化剂，其特征在于，所述酸为包括弱配位阴离子衍生的化合物、低碳链烷酸、磺酸和膦酸。7. The catalyst according to claim 1, characterized in that the acid is a compound derived from a weakly coordinating anion, a low-carbon chain alkanoic acid, a sulfonic acid and a phosphonic acid. 8.根据权利要求7所述的催化剂，其特征在于，所述酸选自磺酸和膦酸。8. The catalyst according to claim 7, characterized in that the acid is selected from sulfonic acid and phosphonic acid. 9.根据权利要求1所述的催化剂，其特征在于，所述酸与ⅥB族或ⅧB族金属活性组分摩尔比为2：1-500：1。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.根据权利要求9所述的催化剂，其特征在于，所述酸与ⅥB族或ⅧB族金属活性组分摩尔比为20：1-400：1。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.根据权利要求1所述的催化剂，其特征在于，所述助剂包括助剂M和助剂N，助剂M和N质量比为1：10-10：1。11 . The catalyst according to claim 1 , characterized in that the auxiliary agent comprises auxiliary agent M and auxiliary agent N, and the mass ratio of auxiliary agent M to N is 1:10-10:1. 12.根据权利要求11所述的催化剂，其特征在于，助剂M和N质量比为2：1-1：2。12. The catalyst according to claim 11, characterized in that the mass ratio of the additives M and N is 2:1-1:2. 13.一种权利要求1-12任一项所述的催化剂在羰基化反应中的应用，其特征在于，在该催化剂存在条件下，以一氧化碳作为羰基化试剂，在含羟基化合物存在下，使烯属不饱和化合物羰基化的方法。13. Use of the catalyst according to any one of claims 1 to 12 in a carbonylation reaction, characterized in that, in the presence of the catalyst, carbon monoxide is used as a carbonylation agent in the presence of a hydroxyl-containing compound to carbonylate an olefinically unsaturated compound. 14.根据权利要求13所述的应用，其特征在于，所述烯属不饱和化合物为含有一个或多个不饱和键的直链或含支链的烯烃或炔烃。14. The use according to claim 13, characterized in that the olefinic unsaturated compound is a straight-chain or branched olefin or alkyne containing one or more unsaturated bonds. 15.根据权利要求14所述的应用，其特征在于，所述烯属不饱和化合物为含有1-3个不饱和键的直链或含支链的烯烃或炔烃。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.根据权利要求13所述的应用，其特征在于，所述烯属不饱和化合物为C1-C4直链烯烃或炔烃。16. The use according to claim 13, characterized in that the olefinic unsaturated compound is a C1-C4 straight-chain olefin or alkyne. 17.根据权利要求16所述的应用，其特征在于，所述烯属不饱和化合物为乙烯。17. The use according to claim 16, characterized in that the olefinically unsaturated compound is ethylene. 18.根据权利要求13所述的应用，其特征在于，所述含羟基化合物为包括水或含羟基基团的有机分子。18. The use according to claim 13, characterized in that the hydroxyl-containing compound is an organic molecule including water or a hydroxyl group. 19.根据权利要求18所述的应用，其特征在于，所述含羟基化合物为链烷醇。19. The use according to claim 18, characterized in that the hydroxyl-containing compound is an alkanol. 20.根据权利要求19所述的应用，其特征在于，所述含羟基化合物为甲醇或乙醇。20. The use according to claim 19, characterized in that the hydroxyl-containing compound is methanol or ethanol. 21.根据权利要求13所述的应用，其特征在于，所述含羟基化合物的加入量与烯属不饱和化合物的摩尔比为10：1-1：10。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.根据权利要求21所述的应用，其特征在于，所述含羟基化合物的加入量与烯属不饱和化合物的摩尔比为2：1-1：2。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.根据权利要求13所述的应用，其特征在于，一氧化碳与烯属不饱和化合物摩尔比为1：100-1：1。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.根据权利要求14所述的应用，其特征在于，反应在溶剂中进行，适合的溶剂包括酮类、醚类、酯类、酰胺类和芳香化合物及其衍生化合物。24. The use according to claim 14, characterized in that the reaction is carried out in a solvent, and suitable solvents include ketones, ethers, esters, amides, aromatic compounds and derivatives thereof. 25.根据权利要求24所述的应用，其特征在于，所述溶剂为在298.15K和1*105Nm-2下介电常数介于3-8范围内的非质子溶剂。25. The use according to claim 24, characterized in that the solvent is an aprotic solvent having a dielectric constant in the range of 3-8 at 298.15K and 1* 105Nm -2 . 26.根据权利要求25所述的应用，其特征在于，所述溶剂为苯甲醚。26. The use according to claim 25, characterized in that the solvent is anisole. 27.根据权利要求24所述的应用，其特征在于，溶剂与含羟基化合物质量比为100：1-1：100。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.根据权利要求27所述的应用，其特征在于，溶剂与含羟基化合物质量比为20：1-1：20。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.根据权利要求24所述的应用，其特征在于，所述催化剂中ⅥB族或ⅧB族金属活性组分在反应体系中的摩尔浓度为每千克溶液中所含ⅥB族或ⅧB族金属活性组分的摩尔数为1-200*10-5mol，所述溶液包括溶剂和羟基化合物。29. The use according to claim 24, characterized in that the molar concentration of the active component of the Group VIB or Group VIB metal in the catalyst in the reaction system is 1-200* 10-5 mol per kilogram of solution, and the solution comprises a solvent and a hydroxyl compound. 30.根据权利要求24所述的应用，其特征在于，所述助剂M在反应体系中的质量含量为0.01wt％-2.0wt％，所述助剂N在反应体系中的质量含量为0.01wt％-5wt％，所述反应体系包括溶剂和羟基化合物。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 comprises a solvent and a hydroxyl compound. 31.根据权利要求30所述的应用，其特征在于，所述助剂M在反应体系中的质量含量为0.1wt％-1.0wt％，所述助剂N在反应体系中的质量含量为0.1wt％-2.0wt％，所述反应体系包括溶剂和羟基化合物。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 comprises a solvent and a hydroxyl compound. 32.根据权利要求13-31任一项所述的应用，其特征在于，所述羰基化反应在50-150℃下进行；反应压力为0-5MPa。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 0-5 MPa. 33.根据权利要求32所述的应用，其特征在于，所述羰基化反应在70-100℃下进行；反应压力为0.5-3.5MPa。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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