CN109647507B - Catalyst for selective carbonylation of alkylaromatic hydrocarbons - Google Patents

Catalyst for selective carbonylation of alkylaromatic hydrocarbons Download PDF

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CN109647507B
CN109647507B CN201710933997.XA CN201710933997A CN109647507B CN 109647507 B CN109647507 B CN 109647507B CN 201710933997 A CN201710933997 A CN 201710933997A CN 109647507 B CN109647507 B CN 109647507B
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CN109647507A (en
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王艳红
肖忠斌
杨运信
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • 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
    • B01J31/0215—Sulfur-containing compounds
    • B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
    • B01J31/0227—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts being perfluorinated, i.e. comprising at least one perfluorinated moiety as substructure in case of polyfunctional compounds
    • 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
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
    • B01J35/19—
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions

Abstract

The present invention relates to a catalyst for the selective carbonylation of alkylaromatic hydrocarbons. The invention solves the problems of low conversion rate of alkyl aromatics and low selectivity of para-alkyl aromatic aldehyde in the prior art, better solves the technical problem by adopting the technical scheme that the catalyst for selective carbonylation of alkyl aromatics comprises halogenated alkyl imidazole salt and rare earth salt, and can be used for industrial production of alkyl aromatic aldehyde.

Description

Catalyst for selective carbonylation of alkylaromatic hydrocarbons
Technical Field
The invention relates to a catalyst for selective carbonylation of alkyl aromatic hydrocarbon and application thereof.
Background
p-Tolualdehyde is one of alkyl aromatic aldehydes, namely 4-Tolualdehyde (PTAL), is colorless or light yellow transparent liquid, has mild flower fragrance and almond fragrance, and has certain irritation to eyes and skin. P-tolualdehyde can be used for oxidizing and synthesizing terephthalic acid with high selectivity, is an important organic synthesis intermediate, and is widely applied in the fields of fine chemical engineering and medicines.
The alkyl aromatic aldehyde is synthesized mainly by direct high-temperature oxidation, indirect electrosynthesis and carbonylation. Synthesis of PTAL as an example:
the direct high-temperature oxidation method is to prepare the PTAL by taking p-xylene as a raw material and carrying out photobromination, alkaline hydrolysis and oxidation of a hydrogen peroxide/hydrobromic acid mixed solution. Although the process has the advantages of easily obtained raw materials and simple operation, the process has low aromatic utilization rate, complicated process and lower total conversion rate (26.7 percent) (the synthesis research of p-tolualdehyde [ J ] proceedings of Zhejiang university, 1999,27 (4); 334-.
The indirect electrosynthesis method is to prepare PTAL by catalytic oxidation of p-xylene in an electrolytic bath, and has the advantages of simple process, high yield, less side reaction, less pollution discharge, environmental protection and resource saving, but the cost of the catalyst is high, and the equipment is complex, which restricts the industrial development (Tangdang, royal red, Liyanwei. process improvement of the indirect electrosynthesis of benzaldehyde/p-tolualdehyde by using on-line ultrasound outside the cell [ J ]. university of Tai principle, 2015,46(1): 6-10.).
The carbonylation method is to synthesize PTAL by catalyzing and carbonylating toluene and CO. The process takes CO as a carbonylation reagent, a B-L composite liquid acid catalyst and a solid super-strong acid catalystOne of the catalyst and the ionic liquid catalyst is a catalyst, and the reaction is essentially electrophilic substitution reaction of CO to toluene under the catalysis of acid, which is called Galtmann-Koch (Gattermann-Koch) synthesis reaction. The method has the advantages of high atom utilization rate, simple process, low cost of raw material CO and good market prospect. The process was successively investigated by DuPont, Mitsubishi gas, Inc., and Exxon Mobil, USA. Compared with B-L composite liquid acid and solid super strong acid catalysts, the catalytic activity of the selective carbonylation reaction of toluene and CO catalyzed by the ionic liquid is obviously improved. Saleh to [ emim]Cl/AlCl3(xAlCl30.75) as catalyst, IL/toluene mass ratio of 8.5/1.8, CO partial pressure of 8.2Mpa maintained at room temperature, reaction time of 1h, achieved 66% toluene conversion and 89.1% PTAL selectivity (Saleh RY, Rouge b. process for making aromatic aldehyde using ionic liquids [ P)]US 6320083,2001-11-20.). The further application is that the PTAL obtained by separation is oxidized to synthesize terephthalic acid, and the terephthalic acid is used as a monomer in the production of industrial polyester, and the demand is large. However, the above patents have problems of large amount of catalyst, low toluene conversion rate, and low selectivity to methylbenzaldehyde.
Disclosure of Invention
One of the technical problems to be solved by the invention is the problem of low conversion rate of alkyl aromatics and low selectivity of para-alkyl aromatic aldehyde, and provides a novel catalyst for synthesizing alkyl aromatic aldehyde, which has the characteristics of high conversion rate of alkyl aromatics and high selectivity of para-alkyl aromatic aldehyde.
The second technical problem to be solved by the present invention is to use the catalyst described in the first technical problem.
In order to solve one of the problems, the technical scheme adopted by the invention is as follows:
catalysts for the selective carbonylation of alkylaromatic hydrocarbons include haloalkylimidazolium salts and rare earth salts.
In the technical scheme, the rare earth salt is preferably rare earth perfluoroalkyl sulfonate.
In the above technical scheme, the halogenated alkyl imidazolium salt is preferably selected from imidazolium salt A with the following structural formula A and/or imidazolium salt B with the following structural formula B:
Figure BDA0001429402480000021
wherein R is1And R2Independently selected from C1-C4 alkyl, R3Selected from C1-C6 alkylene radicals, R4And R5Independently selected from C1-C4 alkyl, and X and Y are independently selected from at least one of chlorine or bromine.
In the above technical scheme, R3C1-C6 alkylene or C6-C10 arylene is preferred. Such as but not limited to R3Is- (CH)2)k- (k ═ 1 to 6) or-C6H4- (wherein two substituents may be in ortho, meta or para positions in the phenyl ring).
In the above technical scheme, R1And R2Preferably the same alkyl group, more preferably both methyl groups.
In the above technical solution, the halogenated alkyl imidazolium salt preferably includes two of imidazolium salt a and imidazolium salt B, and the two halogenated alkyl imidazolium salts have a synergistic effect in improving conversion rate of alkyl aromatic hydrocarbon. In this case, the ratio between the imidazolium salt A and the imidazolium salt B is not particularly limited, and examples thereof include, but are not limited to, a weight ratio of the imidazolium salt A to the imidazolium salt B of 0.1 to 10, and more specific non-limiting ratios within this range are 0.2, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 7.0, 8.0, 9.0, and the like.
In the above technical scheme, the imidazolium salt a is, for example, but not limited to, at least one of the compounds represented by the following structures:
Figure BDA0001429402480000031
more preferably, the halogenoimidazolium salt a is an imidazolium salt (a).
In the above embodiment, the imidazole salt B may be one selected from 1-butyl-3-ethylimidazolium chloride, 1-butyl-3-methylimidazolium chloride, 1-N-propyl-3-methylimidazolium chloride, 1-ethyl-3-methylimidazolium chloride, N-dimethylimidazolium chloride, 1-butyl-3-methylimidazolium bromide, 1-N-propyl-3-methylimidazolium bromide, 1-ethyl-3-methylimidazolium bromide, and N, N-dimethylimidazolium bromide, and more preferably 1-ethyl-3-methylimidazolium bromide.
In the above technical scheme, the rare earth perfluoroalkyl sulfonate is preferably rare earth triflate.
In the above technical solution, the rare earth preferably includes at least one selected from scandium, cerium, and yttrium.
In the above technical solution, the rare earth preferably includes at least two of scandium, cerium and yttrium at the same time, and the perfluoroalkyl sulfonate salts of the two rare earth elements have a synergistic effect in improving the selectivity of the para-alkyl aromatic aldehyde. In this case, the ratio between the perfluoroalkylsulfonic acid salts of the two rare earth elements (for example, between scandium perfluoroalkylsulfonate and cerium perfluoroalkylsulfonate, scandium perfluoroalkylsulfonate and yttrium perfluoroalkylsulfonate, and cerium perfluoroalkylsulfonate and yttrium perfluoroalkylsulfonate) is not particularly limited, and examples thereof include, but are not limited to, 0.1 to 10 by weight, and more specific, non-limiting ratios within the range of 0.2, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 7.0, 8.0, 9.0, and the like.
In the technical scheme, the weight ratio of the halogenated alkyl imidazole salt to the rare earth perfluoroalkyl sulfonate is preferably 100 (50-300).
In the above technical scheme, the preparation method of the catalyst is not particularly limited, and the catalyst can be mixed according to the required components; the reaction system may be added separately or simultaneously with the desired components in the reaction for synthesizing the alkyl aromatic aldehyde, and if added separately, the order of addition of the components is not particularly limited.
By way of non-limiting example, in the preparation of the catalyst, when mixed according to the desired components, the skilled person knows that it is preferable to work in a CO atmosphere to increase the solubility of CO; the mixing and stirring speed of each component of the catalyst is preferably 100-800 rpm; the mixing time of the components of the catalyst is preferably 0.5 h-2 h.
In order to solve the second problem, the invention adopts the following technical scheme:
the application of the catalyst in the selective carbonylation of alkyl aromatic hydrocarbon to synthesize alkyl aromatic aldehyde is disclosed.
In the above technical scheme, the alkyl aromatic hydrocarbon is preferably selected from monoalkyl substituted benzene.
In the above technical scheme, the alkyl group in the monoalkyl substituted benzene is preferably an alkyl group having 1-6, such as but not limited to, the monoalkyl substituted benzene is a single compound of toluene, ethylbenzene, cumene, n-butylbenzene, tert-butylbenzene, n-hexylbenzene, etc., or a mixture thereof.
As known to those skilled in the art, the carbonylation reaction is electrophilic substitution, and alkyl mono-substituted aromatic hydrocarbon and CO are carbonylated according to the positioning rule of alkyl mono-substituted aromatic hydrocarbon, and the obtained product with predominant positioning is para-alkyl aromatic aldehyde, which is the target product of the present invention.
In the above technical solutions, the key to the application is the choice of catalyst, and the process conditions for a specific application can be reasonably selected by those skilled in the art without inventive effort, such as but not limited to:
the method for synthesizing the alkyl aromatic aldehyde comprises the step of synthesizing the alkyl aromatic aldehyde by carrying out carbonylation reaction on alkyl aromatic hydrocarbon and CO under the catalysis of the catalyst in one technical scheme of the technical problem.
The weight ratio of the catalyst to the alkylaromatic hydrocarbon is not particularly limited, and may be, for example, (1-12): 1;
the reaction temperature is preferably 20-150 ℃;
the reaction pressure is preferably 1-8 MPa;
the reaction time is preferably 1-12 h.
The specific steps for synthesizing the alkyl aromatic aldehyde may be:
(1) adding the components of the catalyst into the high-pressure reaction kettle;
(2) the air in the kettle is firstly used by N2Replacing for 3 times, then replacing for 3 times by CO gas, stirring and mixing;
(3) adding alkyl aromatic hydrocarbon, and then replacing for 3 times by CO gas;
(4) heating to reaction temperature, keeping constant reaction pressure, stirring, and reacting to obtain a mixture containing the product alkyl aromatic aldehyde.
In the present invention, unless otherwise specified, the pressure refers to gauge pressure.
The sample processing and analysis methods were as follows:
the product mixture was washed with 2 volumes of ice water, the aqueous phase was discarded and the organic phase was extracted three times with ether, the volume of ether used for each extraction being equal to the volume of the organic phase. Combining the three times of ether extraction liquid, performing rotary evaporation to obtain a residue, namely a crude product of the alkyl aromatic aldehyde, performing gas chromatography analysis on the crude product, and calculating the conversion rate of the alkyl aromatic hydrocarbon and the selectivity of para-alkyl aromatic aldehyde according to an analysis result, wherein the calculation formula is as follows:
Figure BDA0001429402480000051
Figure BDA0001429402480000052
after the technical scheme of the invention is adopted, the conversion rate of toluene can reach 87.8%, the selectivity of corresponding p-tolualdehyde can reach 94.2%, beneficial technical effects are obtained, and the method can be used for preparing alkyl aromatic aldehyde by carbonylation of alkyl aromatic hydrocarbon and CO.
Detailed Description
Preparation of imidazole salt (a): preparation of imidazole salts (a) the preparation described in the literature (Yanhong Wang, dyeing Zhang, Bin Li, et al Synthesis, chromatography, electrochemical properties and catalytic reactivity of the N-heterocyclic carbon-containing compounds [ J ]. RSC Advances,2015,5(37):29022-29031.) is specifically carried out as follows:
under the atmosphere of nitrogen, CH is added into a 1000mL three-neck flask in sequence3CN (400mL), 1-methylimidazole (49.8g, 0.6mol) and 1, 2-dibromoethane (56.4g, 0.3mol) were reacted at 80 ℃ with stirring for 72 h. Cooled to room temperature, filtered, the solid washed with THF (3X 200 mL/sec) and dried in vacuo at 30 ℃ to give the above imidazolium salt (a) (100.6g, 95.3%).
[ example 1 ]
40g of the imidazole salt (a) and 80g of cerium trifluoromethanesulfonate were put into a 250mL autoclave, and N was used as an air in the autoclave2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; adding 50g of toluene, and then replacing for 3 times by using CO gas; heating to 50 ℃, keeping CO pressure at 2.0MPa, stirring at 500rpm, and reacting for 5h to obtain a product mixture containing p-tolualdehyde.
For convenience of comparison and explanation, the catalyst formulation, the conversion of toluene and the selectivity to p-tolualdehyde are shown in table 1.
[ example 2 ]
40g of 1-ethyl-3-methyl imidazole bromide and 80g of cerium trifluoromethanesulfonate are added into a 250mL high-pressure reaction kettle, and N is firstly used as air in the kettle2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; adding 50g of toluene, and then replacing for 3 times by using CO gas; heating to 50 ℃, keeping CO pressure at 2.0MPa, stirring at 500rpm, and reacting for 5h to obtain a product mixture containing p-tolualdehyde.
For convenience of comparison and explanation, the catalyst formulation, the conversion of toluene and the selectivity to p-tolualdehyde are shown in table 1.
[ example 3 ]
40g of the imidazole salt (a) and 80g of yttrium trifluoromethanesulfonate were put into a 250mL autoclave, and N was used as an air in the autoclave2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; adding 50g of toluene, and then replacing for 3 times by using CO gas; heating to 50 ℃, keeping CO pressure at 2.0MPa, stirring at 500rpm, and reacting for 5h to obtain a product mixture containing p-tolualdehyde.
For convenience of comparison and explanation, the catalyst formulation, the conversion of toluene and the selectivity to p-tolualdehyde are shown in table 1.
[ example 4 ]
40g of 1-ethyl-3-methyl imidazole bromide and 80g of yttrium trifluoromethanesulfonate are added into a 250mL high-pressure reaction kettle, and N is firstly used as air in the kettle2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; adding 50g of toluene, and then replacing for 3 times by using CO gas; heating to 50 ℃, keeping CO pressure at 2.0MPa, stirring at 500rpm, and reacting for 5h to obtain a product mixture containing p-tolualdehyde.
For convenience of comparison and explanation, the catalyst formulation, the conversion of toluene and the selectivity to p-tolualdehyde are shown in table 1.
[ example 5 ]
40g of the imidazole salt (a) and 80g of scandium trifluoromethanesulfonate were put into a 250mL autoclave, and N was used as an air in the autoclave2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; adding 50g of toluene, and then replacing for 3 times by using CO gas; heating to 50 ℃, keeping CO pressure at 2.0MPa, stirring at 500rpm, and reacting for 5h to obtain a product mixture containing p-tolualdehyde.
For convenience of comparison and explanation, the catalyst formulation, the conversion of toluene and the selectivity to p-tolualdehyde are shown in table 1.
[ example 6 ]
40g of 1-ethyl-3-methyl imidazole bromide and 80g of scandium trifluoromethanesulfonate are added into a 250mL high-pressure reaction kettle, and N is firstly used as air in the kettle2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; adding 50g of toluene, and then replacing for 3 times by using CO gas; heating to 50 ℃, keeping CO pressure at 2.0MPa, stirring at 500rpm, and reacting for 5h to obtain a product mixture containing p-tolualdehyde.
For convenience of comparison and explanation, the catalyst formulation, the conversion of toluene and the selectivity to p-tolualdehyde are shown in table 1.
[ example 7 ]
20g of the imidazole salt (a), 20g of 1-ethyl-3-methyl imidazole bromide and 80g of cerium trifluoromethanesulfonate were added to a 250mL autoclave, and the atmosphere in the autoclave was replaced with N2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; adding 50g of toluene, and then replacing for 3 times by using CO gas; heating to 50 deg.C, maintaining CO pressure at 2.0MPa,stirring at 500rpm, and reacting for 5h to obtain a product mixture containing p-tolualdehyde.
For convenience of comparison and explanation, the catalyst formulation, the conversion of toluene and the selectivity to p-tolualdehyde are shown in table 1.
[ example 8 ]
20g of the imidazole salt (a), 20g of 1-ethyl-3-methyl imidazole bromide and 80g of yttrium trifluoromethanesulfonate were added to a 250mL autoclave, and the atmosphere in the autoclave was purged with N2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; adding 50g of toluene, and then replacing for 3 times by using CO gas; heating to 50 ℃, keeping CO pressure at 2.0MPa, stirring at 500rpm, and reacting for 5h to obtain a product mixture containing p-tolualdehyde.
For convenience of comparison and explanation, the catalyst formulation, the conversion of toluene and the selectivity to p-tolualdehyde are shown in table 1.
[ example 9 ]
20g of the imidazole salt (a), 20g of 1-ethyl-3-methyl imidazole bromide and 80g of scandium trifluoromethanesulfonate were added to a 250mL autoclave, and the atmosphere in the autoclave was replaced with N2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; adding 50g of toluene, and then replacing for 3 times by using CO gas; heating to 50 ℃, keeping CO pressure at 2.0MPa, stirring at 500rpm, and reacting for 5h to obtain a product mixture containing p-tolualdehyde.
For convenience of comparison and explanation, the catalyst formulation, the conversion of toluene and the selectivity to p-tolualdehyde are shown in table 1.
[ example 10 ]
40g of the imidazole salt (a), 40g of cerium trifluoromethanesulfonate and 40g of scandium trifluoromethanesulfonate were added to a 250mL autoclave, and N was used as an air in the autoclave2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; adding 50g of toluene, and then replacing for 3 times by using CO gas; heating to 50 ℃, keeping CO pressure at 2.0MPa, stirring at 500rpm, and reacting for 5h to obtain a product mixture containing p-tolualdehyde.
For convenience of comparison and explanation, the catalyst formulation, the conversion of toluene and the selectivity to p-tolualdehyde are shown in table 1.
[ example 11 ]
40g of 1-ethyl-3-methyl imidazole bromide, 40g of cerium trifluoromethanesulfonate and 40g of scandium trifluoromethanesulfonate are added into a 250mL high-pressure reaction kettle, and the air in the kettle is firstly used by N2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; adding 50g of toluene, and then replacing for 3 times by using CO gas; heating to 50 ℃, keeping CO pressure at 2.0MPa, stirring at 500rpm, and reacting for 5h to obtain a product mixture containing p-tolualdehyde.
For convenience of comparison and explanation, the catalyst formulation, the conversion of toluene and the selectivity to p-tolualdehyde are shown in table 1.
[ example 12 ]
40g of the imidazole salt (a), 40g of cerium trifluoromethanesulfonate and 40g of yttrium trifluoromethanesulfonate were added to a 250mL autoclave, and N was used as an air in the autoclave2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; adding 50g of toluene, and then replacing for 3 times by using CO gas; heating to 50 ℃, keeping CO pressure at 2.0MPa, stirring at 500rpm, and reacting for 5h to obtain a product mixture containing p-tolualdehyde.
For convenience of comparison and explanation, the catalyst formulation, the conversion of toluene and the selectivity to p-tolualdehyde are shown in table 1.
[ example 13 ]
40g of 1-ethyl-3-methyl imidazole bromide, 40g of cerium trifluoromethanesulfonate and 40g of yttrium trifluoromethanesulfonate are added into a 250mL high-pressure reaction kettle, and the air in the kettle is firstly used by N2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; adding 50g of toluene, and then replacing for 3 times by using CO gas; heating to 50 ℃, keeping CO pressure at 2.0MPa, stirring at 500rpm, and reacting for 5h to obtain a product mixture containing p-tolualdehyde.
For convenience of comparison and explanation, the catalyst formulation, the conversion of toluene and the selectivity to p-tolualdehyde are shown in table 1.
[ example 14 ]
40g of the imidazole salt (a), 40g of scandium trifluoromethanesulfonate and 40g of yttrium trifluoromethanesulfonate were added to a 250mL autoclave, and N was used as an air in the autoclave2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; 50g of toluene was added, and the mixture was further reusedCO gas is replaced for 3 times; heating to 50 ℃, keeping CO pressure at 2.0MPa, stirring at 500rpm, and reacting for 5h to obtain a product mixture containing p-tolualdehyde.
For convenience of comparison and explanation, the catalyst formulation, the conversion of toluene and the selectivity to p-tolualdehyde are shown in table 1.
[ example 15 ]
40g of 1-ethyl-3-methyl imidazole bromide, 40g of scandium trifluoromethanesulfonate and 40g of yttrium trifluoromethanesulfonate are added into a 250mL high-pressure reaction kettle, and the air in the kettle is firstly used by N2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; adding 50g of toluene, and then replacing for 3 times by using CO gas; heating to 50 ℃, keeping CO pressure at 2.0MPa, stirring at 500rpm, and reacting for 5h to obtain a product mixture containing p-tolualdehyde.
For convenience of comparison and explanation, the catalyst formulation, the conversion of toluene and the selectivity to p-tolualdehyde are shown in table 1.
[ example 16 ]
20g of the imidazole salt (a), 20g of 1-ethyl-3-methylimidazolium bromide, 40g of cerium trifluoromethanesulfonate and 40g of scandium trifluoromethanesulfonate were put into a 250mL autoclave, and N was used as an air in the autoclave2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; adding 50g of toluene, and then replacing for 3 times by using CO gas; heating to 50 ℃, keeping CO pressure at 2.0MPa, stirring at 500rpm, and reacting for 5h to obtain a product mixture containing p-tolualdehyde.
For convenience of comparison and explanation, the catalyst formulation, the conversion of toluene and the selectivity to p-tolualdehyde are shown in table 1.
[ example 17 ]
20g of the imidazole salt (a), 20g of 1-ethyl-3-methylimidazole bromide, 40g of cerium trifluoromethanesulfonate and 40g of yttrium trifluoromethanesulfonate were put into a 250mL autoclave, and N was used as an air in the autoclave2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; adding 50g of toluene, and then replacing for 3 times by using CO gas; heating to 50 ℃, keeping CO pressure at 2.0MPa, stirring at 500rpm, and reacting for 5h to obtain a product mixture containing p-tolualdehyde.
For convenience of comparison and explanation, the catalyst formulation, the conversion of toluene and the selectivity to p-tolualdehyde are shown in table 1.
[ example 18 ]
20g of the imidazole salt (a), 20g of 1-ethyl-3-methylimidazolium bromide, 40g of scandium trifluoromethanesulfonate and 40g of yttrium trifluoromethanesulfonate were put into a 250mL autoclave, and N was used as an air in the autoclave2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; adding 50g of toluene, and then replacing for 3 times by using CO gas; heating to 50 ℃, keeping CO pressure at 2.0MPa, stirring at 500rpm, and reacting for 5h to obtain a product mixture containing p-tolualdehyde.
For convenience of comparison and explanation, the catalyst formulation, the conversion of toluene and the selectivity to p-tolualdehyde are shown in table 1.
[ example 19 ]
20g of the imidazole salt (a), 20g of 1-ethyl-3-methylimidazolium bromide, 40g of cerium trifluoromethanesulfonate and 40g of scandium trifluoromethanesulfonate were put into a 250mL autoclave, and N was used as an air in the autoclave2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; 50g of ethylbenzene is added, and then CO gas is used for replacing for 3 times; heating to 50 ℃, keeping CO pressure at 2.0MPa, stirring at 500rpm, and reacting for 5h to obtain a product mixture containing p-ethylbenzaldehyde.
For convenience of comparison and illustration, the catalyst formulation, the conversion of ethylbenzene and the selectivity to p-ethylbenzaldehyde are shown in table 1.
[ example 20 ]
20g of the imidazole salt (a), 20g of 1-ethyl-3-methylimidazolium bromide, 40g of cerium trifluoromethanesulfonate and 40g of scandium trifluoromethanesulfonate were put into a 250mL autoclave, and N was used as an air in the autoclave2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; adding 50g of isopropyl benzene, and then replacing for 3 times by CO gas; heating to 50 ℃, keeping CO pressure at 2.0MPa, stirring at 500rpm, and reacting for 5h to obtain a product mixture containing the p-isopropyl benzaldehyde.
For ease of comparison and illustration, the catalyst formulation, cumene conversion and selectivity to p-isopropylbenzaldehyde are listed in table 1.
[ example 21 ]
High pressure of 250mL20g of the imidazole salt (a), 20g of 1-ethyl-3-methylimidazole bromide, 40g of cerium trifluoromethanesulfonate and 40g of scandium trifluoromethanesulfonate were added to a reaction kettle, and N was used as an air in the kettle2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; adding 50g of tert-butylbenzene, and then replacing for 3 times with CO gas; heating to 50 ℃, keeping CO pressure at 2.0MPa, stirring at 500rpm, and reacting for 5h to obtain a product mixture containing p-tert-butyl benzaldehyde.
For ease of comparison and illustration, the catalyst formulation, the conversion of t-butylbenzene and the selectivity to p-t-butylbenzaldehyde are listed in table 1.
TABLE 1
Figure BDA0001429402480000121
Note: the alkylaromatic hydrocarbon used in examples 1 to 18 was toluene, ethylbenzene in example 19, cumene in example 20, and tert-butylbenzene in example 21.

Claims (7)

1. A catalyst for selective carbonylation of alkyl aromatic hydrocarbons comprises a haloalkyl imidazolium salt and a rare earth salt, and is characterized in that the haloalkyl imidazolium salt comprises an imidazolium salt A with a structural formula A and an imidazolium salt B with a structural formula B:
Figure DEST_PATH_IMAGE002
，（A）
Figure DEST_PATH_IMAGE004
，（B）；
wherein R is1And R2Independently selected from C1-C4 alkyl, R3Selected from C1-C6 alkylene, R4And R5Independently selected from C1-C4 alkyl, X and Y are independently selected from at least one of chlorine or bromine; the rare earth salt is rare earth triflate.
2. The catalyst of claim 1, wherein R is1And R2Are the same alkyl groups.
3. The catalyst according to claim 1, characterized in that the imidazolium salt B is selected from at least one of 1-butyl-3-methylchloroimidazole, 1-N-propyl-3-methylchloroimidazole, 1-ethyl-3-methylchloroimidazole, N-dimethylchloroimidazole, 1-butyl-3-methylbrominated imidazole, 1-N-propyl-3-methylbrominated imidazole, 1-ethyl-3-methylbrominated imidazole and N, N-dimethylbrominated imidazole.
4. The catalyst according to claim 1, wherein the weight ratio of the haloalkylimidazolium salt to the rare earth salt is 100 (50-300).
5. Use of the catalyst of any one of claims 1 to 4 in the selective carbonylation of alkylaromatic hydrocarbons to produce alkylaromatic aldehydes.
6. The method of claim 5, wherein the alkyl aromatic hydrocarbon is a monoalkyl substituted benzene.
7. The method as set forth in claim 6, wherein the monoalkyl group in the monoalkyl-substituted benzene is a C1-C6 alkyl group.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06157391A (en) * 1992-11-25 1994-06-03 Nippon Steel Corp Method for formylating aromatic compound
CN101209959A (en) * 2006-12-26 2008-07-02 中国石油化工股份有限公司 Method for preparing and separating alkyl aromatic aldehyde

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06157391A (en) * 1992-11-25 1994-06-03 Nippon Steel Corp Method for formylating aromatic compound
CN101209959A (en) * 2006-12-26 2008-07-02 中国石油化工股份有限公司 Method for preparing and separating alkyl aromatic aldehyde

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