CN111072464A - Method for directly introducing aldehyde group on aromatic ring - Google Patents

Method for directly introducing aldehyde group on aromatic ring Download PDF

Info

Publication number
CN111072464A
CN111072464A CN201811214146.0A CN201811214146A CN111072464A CN 111072464 A CN111072464 A CN 111072464A CN 201811214146 A CN201811214146 A CN 201811214146A CN 111072464 A CN111072464 A CN 111072464A
Authority
CN
China
Prior art keywords
replacing
weight
ionic liquid
aromatic
carrier
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201811214146.0A
Other languages
Chinese (zh)
Inventor
王艳红
肖忠斌
杨运信
查晓钟
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
Original Assignee
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp, Sinopec Shanghai Research Institute of Petrochemical Technology filed Critical China Petroleum and Chemical Corp
Priority to CN201811214146.0A priority Critical patent/CN111072464A/en
Publication of CN111072464A publication Critical patent/CN111072464A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/32—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of manganese, technetium or rhenium
    • 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
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
    • 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
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/36—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of vanadium, niobium or tantalum

Abstract

The invention relates to a method for directly introducing aldehyde groups on aromatic rings. The invention mainly solves the problems of low aromatic hydrocarbon conversion rate and low aromatic aldehyde selectivity in the prior art, adopts a method for directly introducing aldehyde groups on aromatic rings, and comprises the step of carrying out carbonylation reaction on aromatic hydrocarbons and CO under the catalysis of a catalyst to obtain aromatic aldehydes, wherein the catalyst comprises a carrier, ionic liquid and a chemical compound auxiliary agentThe carrier is a silicon-based material, the ionic liquid comprises aluminum halide and imidazole salt shown in a chemical formula I, wherein R is1And R2Independently selected from alkyl of C1-C8, and X is selected from chlorine or bromine; the aluminum halide is expressed as AlY3Y is selected from chlorine or bromine; the compound auxiliary metal comprises at least one of Cu, Fe, Cr, V or Mn.

Description

Method for directly introducing aldehyde group on aromatic ring
Technical Field
The invention relates to a method for directly introducing aldehyde groups on aromatic rings.
Background
The synthesis method of aromatic aldehyde mainly comprises a direct high-temperature oxidation method, an indirect electrosynthesis method and a carbonylation method. p-Tolualdehyde is one of 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. 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, takes one of a B-L composite liquid acid catalyst, a solid super acid catalyst and an ionic liquid catalyst as a catalyst, and the reaction is essentially electrophilic substitution reaction of CO to toluene under the catalysis of acid, which is called as Gattermann-Koch synthesis reaction. The method has the advantages of high atom utilization rate, simple process,The raw material CO is low in cost and has 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
The invention aims to solve the technical problems of low aromatic hydrocarbon conversion rate and low aromatic aldehyde selectivity, and provides a novel method for directly introducing aldehyde groups on aromatic rings.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the method for directly introducing aldehyde groups on aromatic rings comprises the step of carrying out carbonylation reaction on aromatic hydrocarbons and CO under the catalysis of a catalyst to obtain aromatic aldehydes, wherein the catalyst comprises a carrier, ionic liquid and a compound auxiliary metal, the carrier is a silicon-based material, and the ionic liquid comprises aluminum halide and imidazolium salt shown in a chemical formula I:
Figure BDA0001833121130000021
wherein R is1And R2Independently selected from alkyl of C1-C8, and X is selected from chlorine or bromine; the aluminum halide is expressed as AlY3Y is selected from chlorine or bromine; the compound assistant metal comprises Cu,Fe. At least one of Cr, V and Mn.
In the above technical scheme, the molar ratio of the imidazolium salt to the aluminum halide is preferably 1 (1-5).
For convenience of comparison, the ionic liquid adopted in the embodiment of the invention is [ mmim]Cl-AlCl3Wherein [ mmim]Cl and AlCl3In a molar ratio of 1:2, [ mmim ]]Cl, i.e. R in formula I1And R2Both are the case when methyl and X is chlorine.
In the technical scheme, the reaction temperature is preferably 30-120 ℃.
In the technical scheme, the pressure of the reaction is preferably 1-6 MPa.
In the technical scheme, the reaction time is preferably 2-10 h.
In the above-mentioned embodiment, the silica-based material is preferably at least one selected from the group consisting of silica gel, MCM-41, MCM-48, MCM-50 and SBA-15.
In the above technical solution, the weight of the ionic liquid is preferably 5% to 50% of the weight of the carrier, and more preferably 21% to 29% of the weight of the carrier.
In the above technical solution, the compound auxiliary metal preferably includes at least one selected from the group consisting of metal oxides, chlorides, acetates or trifluoroacetates.
In the above technical solution, the weight of the compound auxiliary metal is preferably 0.1 to 5 times, and more preferably 1.0 to 2.5 times of the weight of the aluminum halide based on the Al element.
In the above technical solution, the aromatic hydrocarbon is preferably at least one selected from the group consisting of benzene, naphthalene and alkyl monosubstituted aromatic hydrocarbons.
In the above technical solution, the compound auxiliary metal preferably includes both Cr and V, and both of them have a synergistic effect in improving the conversion rate of aromatic hydrocarbons.
In the above technical solution, the compound auxiliary metal preferably includes both Cr and Mn, and both of them have a synergistic effect in improving the conversion rate of aromatic hydrocarbons.
In the above technical solution, it is more preferable that the compound auxiliary metal simultaneously includes Cr, V and Mn, and V and Mn have a synergistic effect in increasing the conversion rate of aromatic hydrocarbon, and Cr, V and Mn have a synergistic effect in increasing the conversion rate of aromatic hydrocarbon.
In the above technical solutions, another technical key of the present invention is the selection of the metal species in the compound auxiliary metal rather than the change of the specific amount, and thus the ratio among Cr, V and Mn is not particularly limited.
For example: the ratio of Cr and V is not particularly limited, but is, for example, not limited to, 0.1 to 10 in terms of the weight ratio of Cr to V, and more specific non-limiting ratios within this range are 0.16, 0.36, 0.46, 0.66, 0.76, 0.86, 0.96, 1.06, 1.16, 1.26, 1.36, 1.46, 1.56, 2.06, 2.36, 3.16, 3.46, 4.26, 4.76, 5.46, 5.86, 6.36, 7.26, 8.86, 9.76, and the like.
For another example: the ratio of Cr and Mn is not particularly limited, but is, for example, not limited to, 0.1 to 10 in terms of the weight ratio of Cr to Mn, and more specific non-limiting ratios within this range are 0.16, 0.36, 0.46, 0.66, 0.76, 0.86, 0.96, 1.06, 1.16, 1.26, 1.36, 1.46, 1.56, 2.06, 2.36, 3.16, 3.46, 4.26, 4.76, 5.46, 5.86, 6.36, 7.26, 8.86, 9.76, and the like.
As specific compound forms from which the combined auxiliary metal is taken, by way of non-limiting example, Cr may be Cr2O3、Cr(CH3COO)3、Cr(CF3COO)3And CrCl3V may be V2O5And VCl3Mn may be MnO2、Mn(CH3COO)2And MnCl2At least one of (1).
In the above technical scheme, the preparation method of the IL/carrier comprises the following steps: the desired vector is in N2Calcining for 4-6 h at 300-400 ℃ in the atmosphere, cooling to room temperature, and storing in a glove box for later use; n is a radical of2In the atmosphere, adding ionic liquid into the pretreated carrier, and stirring at 100-400 rpm for 10-23 h; to which CH is added2Cl2Solution, washing-offWashing for 0.5-1 h with loaded ionic liquid; and drying the washed IL/carrier in a vacuum drying oven at the temperature of 35-45 ℃ for 2-4 h at 0.1-0.3 kpa.
In the technical scheme, the load amount of the ionic liquid is represented by the weight fraction of Al element in the IL/carrier, and the weight fraction of the Al element in the IL/carrier is measured by an ICP-AES characterization means.
In the above technical scheme, the aromatic hydrocarbon is at least one selected from benzene, naphthalene or alkyl monosubstituted aromatic hydrocarbon, the alkyl group in the alkyl monosubstituted aromatic hydrocarbon is preferably an alkyl group having C1-C6, for example, but not limited to, the alkyl monosubstituted aromatic hydrocarbon is a single compound of toluene, ethylbenzene, cumene, n-butylbenzene, tert-butylbenzene, n-hexylbenzene, 2-methylnaphthalene, etc., or a mixture thereof.
As known to those skilled in the art, the carbonylation reaction is electrophilic substitution, and alkyl monosubstituted aromatic hydrocarbon and CO carbonylation reaction according to the positioning rule of alkyl monosubstituted aromatic hydrocarbon, the obtained predominant positioning product is para-alkyl aromatic aldehyde, which is the target product of the present invention.
In the above technical scheme, the key to the application is the choice of the catalyst, and under the catalyst condition of the present invention, the skilled person knows how to determine other process conditions for preparing aromatic aldehyde.
The specific steps for preparing the 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 aromatic hydrocarbon, and then replacing for 3 times with CO gas;
(4) and (3) heating to the reaction temperature, keeping constant reaction pressure, stirring, and reacting to obtain a mixture containing the target product aromatic aldehyde.
In the present invention, unless otherwise specified, the pressure refers to gauge pressure.
The sample processing and analysis methods were as follows:
centrifuging to separate catalyst component from the product mixture, collecting upper liquid phase, washing the product mixture with ice water of 2 times volume of the liquid phase mixture, standing for separation to obtain organic phase and water phase. Extracting the water phase with cyclohexane for three times, wherein the volume of the cyclohexane adopted in each extraction is 20% of the volume of the water phase, combining the cyclohexane extraction liquid and the organic phase for three times, performing rotary evaporation to obtain a residue, namely a crude product of aromatic aldehyde, performing gas chromatography analysis on the crude product, and calculating the conversion rate of aromatic hydrocarbon and the selectivity of target aromatic aldehyde according to the analysis result, wherein the calculation formula is as follows:
Figure BDA0001833121130000041
Figure BDA0001833121130000051
by adopting the technical scheme of the invention, the conversion rate of toluene can reach 90.3%, the selectivity of corresponding p-tolualdehyde can reach 93.6%, beneficial technical effects are obtained, and the method can be used for preparing aromatic aldehyde by carbonylation of aromatic hydrocarbon and CO.
Detailed Description
Preparation of IL/silica gel: in N2Calcining 100g of silica gel for 6 hours at 400 ℃ in the atmosphere, cooling to room temperature, and storing in a glove box for later use; n is a radical of2In the atmosphere, 25g of ionic liquid is added into the pretreated silica gel, and the mixture is stirred for 20 hours at 200 rpm; thereto was added 200ml of CH2Cl2Washing off the ionic liquid which is not loaded, and washing for 0.5 h; drying the washed IL/silica gel in a vacuum drying oven at 40 ℃ for 2h at 0.1 kpa; storing in a glove box for later use; the weight fraction of Al in the IL/silica gel was found to be 2.66% by means of ICP-AES characterization.
Preparation of IL/SBA-15: in N2Calcining 100g of SBA-15 for 6h at 400 ℃ in an atmosphere, cooling to room temperature, and storing in a glove box for later use; n is a radical of2In the atmosphere, 25g of ionic liquid is added into the pretreated SBA-15, and the mixture is stirred for 20 hours at 200 rpm; thereto was added 200ml of CH2Cl2Washing off the ionic liquid which is not loaded, and washing for 0.5 h; drying the washed IL/SBA-15 in a vacuum drying oven at 0.1kpa for 2h at 40 ℃; glove boxStoring the intermediate product for later use; the weight fraction of Al in IL/SBA-15 was found to be 2.58% by means of ICP-AES characterization.
Preparation of IL/MCM-41: in N2Calcining 100g MCM-41 for 4h at 300 ℃ in the atmosphere, cooling to room temperature, and storing in a glove box for later use; n is a radical of2In the atmosphere, 25g of ionic liquid is added into the pretreated MCM-41, and the mixture is stirred for 20 hours at 200 rpm; thereto was added 200ml of CH2Cl2Washing off the ionic liquid which is not loaded, and washing for 0.5 h; drying the washed IL/MCM-41 in a vacuum drying oven at 0.1kpa for 2 hours at 40 ℃; storing in a glove box for later use; the weight fraction of Al in IL/MCM-41 was found to be 2.61% by ICP-AES characterization.
Comparative example 1
IL/silica gel containing 5g of Al and 200ml of cyclohexane are added into a high-pressure reaction kettle, and the air in the kettle is firstly added with N2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; adding 20g 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 4h 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 1 ]
IL/silica gel containing 5g of Al, 200ml of cyclohexane and CrCl containing 6g of Cr are added into a high-pressure reaction kettle3The air in the kettle is firstly N2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; adding 20g 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 4h 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 ]
The autoclave was charged with IL/silica gel containing 5g Al, 200ml cyclohexane, VCl containing 6g V3The air in the kettle is firstly N2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; 20g of toluene was added, and CO gas was used againBody replacement was performed 3 times; heating to 50 ℃, keeping CO pressure at 2.0MPa, stirring at 500rpm, and reacting for 4h 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 ]
IL/silica gel containing 5g of Al, 200ml of cyclohexane and MnO containing 3g of Mn are added into a high-pressure reaction kettle2The air in the kettle is firstly N2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; adding 20g 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 4h 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 ]
IL/silica gel containing 5g of Al, 200ml of cyclohexane and CrCl containing 3g of Cr are added into a high-pressure reaction kettle3And VCl containing 3g V3The air in the kettle is firstly N2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; adding 20g 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 4h 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 ]
IL/silica gel containing 5g of Al, 200ml of cyclohexane and CrCl containing 3g of Cr are added into a high-pressure reaction kettle3And MnO containing 3g of Mn2The air in the kettle is firstly N2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; adding 20g 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 4h 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 ]
The autoclave was charged with IL/silica gel containing 5g Al, 200ml cyclohexane, VCl containing 3g V3And MnO containing 3g of Mn2The air in the kettle is firstly N2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; adding 20g 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 4h 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 ]
IL/silica gel containing 5g of Al, 200ml of cyclohexane and CrCl containing 2g of Cr are added into a high-pressure reaction kettle3VCl containing 2g V3And MnO containing 2g of Mn2The air in the kettle is firstly N2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; adding 20g 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 4h 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 ]
IL/SBA-15 containing 5g of Al, 200ml of cyclohexane and CrCl containing 3g of Cr are added into a high-pressure reaction kettle3And VCl containing 3g V3The air in the kettle is firstly N2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; adding 20g 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 4h 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 ]
IL/SBA-15 containing 5g of Al, 200ml of cyclohexane and CrCl containing 3g of Cr are added into a high-pressure reaction kettle3And MnO containing 3gMn2The air in the kettle is firstly N2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; adding 20g 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 4h 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 ]
The autoclave was charged with IL/SBA-15 containing 5g of Al, 200ml of cyclohexane, VCl containing 3g V3And MnO containing 3g of Mn2The air in the kettle is firstly N2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; adding 20g 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 4h 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 ]
IL/SBA-15 containing 5g of Al, 200ml of cyclohexane and CrCl containing 2g of Cr are added into a high-pressure reaction kettle3VCl containing 2g V3And MnO containing 2g of Mn2The air in the kettle is firstly N2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; adding 20g 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 4h 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 ]
IL/MCM-41 containing 5g of Al, 200ml of cyclohexane and CrCl containing 3g of Cr are added into a high-pressure reaction kettle3And VCl containing 3g V3The air in the kettle is firstly N2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; adding 20g of toluene, and then replacing for 3 times by using CO gas; heating to 50 deg.CKeeping CO pressure at 2.0MPa, stirring at 500rpm, and reacting for 4h 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 ]
IL/MCM-41 containing 5g of Al, 200ml of cyclohexane and CrCl containing 3g of Cr are added into a high-pressure reaction kettle3And MnO containing 3gMn2The air in the kettle is firstly N2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; adding 20g 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 4h 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 ]
The autoclave was charged with IL/MCM-41 containing 5g of Al, 200ml of cyclohexane, VCl containing 3g V3And MnO containing 3g of Mn2The air in the kettle is firstly N2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; adding 20g 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 4h 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 ]
IL/MCM-41 containing 5g of Al, 200ml of cyclohexane and CrCl containing 2g of Cr are added into a high-pressure reaction kettle3VCl containing 2g V3And MnO containing 2g of Mn2The air in the kettle is firstly N2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; adding 20g 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 4h 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 ]
IL/silica gel containing 5g of Al, 200ml of cyclohexane and CrCl containing 2g of Cr are added into a high-pressure reaction kettle3VCl containing 2g V3And MnO containing 2g of Mn2The air in the kettle is firstly N2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; adding 20g of ethylbenzene, 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 4h 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 17 ]
IL/silica gel containing 5g of Al, 200ml of cyclohexane and CrCl containing 2g of Cr are added into a high-pressure reaction kettle3VCl containing 2g V3And MnO containing 2g of Mn2The air in the kettle is firstly N2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; adding 20g 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 4h 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 18 ]
IL/silica gel containing 5g of Al, 200ml of cyclohexane and CrCl containing 2g of Cr are added into a high-pressure reaction kettle3VCl containing 2g V3And MnO containing 2g of Mn2The air in the kettle is firstly N2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; adding 20g of benzene, and then replacing for 3 times by CO gas; heating to 50 ℃, keeping the CO pressure at 2.0MPa, stirring at 500rpm, and reacting for 4 hours to obtain a product mixture containing benzaldehyde.
For ease of comparison and illustration, the catalyst formulation, benzene conversion and benzaldehyde selectivity are listed in table 1.
[ example 19 ]
High pressureIL/silica gel containing 5g of Al, 200ml of cyclohexane and CrCl containing 2g of Cr are added into a reaction kettle3VCl containing 2g V3And MnO containing 2g of Mn2The air in the kettle is firstly N2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; adding 20g of naphthalene, 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 4h to obtain a product mixture containing 1-naphthaldehyde.
For ease of comparison and illustration, the catalyst formulation, naphthalene conversion, and 1-naphthaldehyde selectivity are listed in table 1.
[ example 20 ]
IL/silica gel containing 5g of Al, 200ml of cyclohexane and CrCl containing 2g of Cr are added into a high-pressure reaction kettle3VCl containing 2g V3And MnO containing 2g of Mn2The air in the kettle is firstly N2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; adding 20g of 2-methylnaphthalene, and then replacing for 3 times by CO gas; heating to 50 ℃, keeping CO pressure at 2.0MPa, stirring at 500rpm, and reacting for 4h to obtain a product mixture containing 2-methyl-6-naphthaldehyde.
For ease of comparison and illustration, the catalyst formulation, the conversion of 2-methylnaphthalene, and the selectivity to 2-methyl-6-naphthaldehyde are listed in table 1.
TABLE 1
Figure BDA0001833121130000121
Note: the ionic liquid IL is [ mmim]Cl-AlCl3Wherein [ mmim]Cl and AlCl3In a molar ratio of 1: 2.
Both the SBA-15 and MCM-41 molecular sieves are all silicon molecular sieves.
The alkylaromatic hydrocarbon used in examples 1 to 15 was toluene, ethylbenzene in example 16, cumene in example 17, benzene in example 18, naphthalene in example 19 and 2-methylnaphthalene in example 20. TABLE 2
Examples Conversion of aromatic hydrocarbons/%) Selectivity of aromatic aldehydes/%)
Comparative example 1 66.5 77.0
Example 1 73.5 78.8
Example 2 75.7 79.2
Example 3 82.8 74.0
Example 4 81.3 86.7
Example 5 83.0 89.3
Example 6 89.1 90.6
Example 7 90.3 93.6
Example 8 79.3 84.7
Example 9 81.3 83.5
Example 10 83.7 85.0
Example 11 85.0 88.4
Example 12 78.5 84.7
Example 13 81.0 83.3
Example 14 82.3 85.4
Example 15 86.9 89.3
Example 16 87.7 90.8
Example 17 84.5 86.7
Example 18 89.0 92.8
Example 19 85.3 87.1
Example 20 74.0 73.4

Claims (10)

1. The method for directly introducing aldehyde groups on aromatic rings comprises the step of carrying out carbonylation reaction on aromatic hydrocarbons and CO under the catalysis of a catalyst to obtain aromatic aldehydes, wherein the catalyst comprises a carrier, ionic liquid and a compound auxiliary metal, the carrier is a silicon-based material, and the ionic liquid comprises aluminum halide and imidazolium salt shown in a chemical formula I:
Figure FDA0001833121120000011
wherein R is1And R2Independently selected from alkyl of C1-C8, and X is selected from chlorine or bromine; the aluminum halide is expressed as AlY3Y is selected from chlorine or bromine; the compound auxiliary metal comprises at least one of the substances consisting of Cu, Fe, Cr, V and Mn.
2. The process according to claim 1, wherein the molar ratio of imidazolium salt to aluminum halide is 1 (1-5).
3. The method according to claim 1, wherein the reaction temperature is preferably 30 to 120 ℃. The pressure of the reaction is preferably 1-6 MPa. The reaction time is preferably 2-10 h.
4. The method as set forth in claim 1, wherein said silica-based material is at least one selected from the group consisting of silica gel, MCM-41, MCM-48, MCM-50 and SBA-15.
5. The method according to claim 1, wherein the weight of the ionic liquid is 5 to 50% of the weight of the carrier. More preferably, the weight of the ionic liquid is 21-29% of the weight of the carrier.
6. The method of claim 1, wherein said compounding aid metal comprises at least one member selected from the group consisting of metal oxides, chlorides, acetates, or trifluoroacetates.
7. The method of claim 1, wherein the weight of the combined adjuvant metal is 0.1-5 times of the weight of Al element in the aluminum halide.
8. The method of claim 1, wherein said compound adjuvant metal comprises Cr and V. The ratio of Cr and V is not particularly limited, but is, for example, not limited to, 0.1 to 10 in terms of the weight ratio of Cr to V, and more specific non-limiting ratios within this range are 0.16, 0.36, 0.46, 0.66, 0.76, 0.86, 0.96, 1.06, 1.16, 1.26, 1.36, 1.46, 1.56, 2.06, 2.36, 3.16, 3.46, 4.26, 4.76, 5.46, 5.86, 6.36, 7.26, 8.86, 9.76, and the like.
9. The method of claim 1, wherein said compound adjuvant metal comprises Cr and Mn. The ratio of Cr and Mn is not particularly limited, but is, for example, not limited to, 0.1 to 10 in terms of the weight ratio of Cr to Mn, and more specific non-limiting ratios within this range are 0.16, 0.36, 0.46, 0.66, 0.76, 0.86, 0.96, 1.06, 1.16, 1.26, 1.36, 1.46, 1.56, 2.06, 2.36, 3.16, 3.46, 4.26, 4.76, 5.46, 5.86, 6.36, 7.26, 8.86, 9.76, and the like.
10. The method of claim 1, wherein said compound adjuvant metal comprises Cr, V and Mn.
CN201811214146.0A 2018-10-18 2018-10-18 Method for directly introducing aldehyde group on aromatic ring Pending CN111072464A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811214146.0A CN111072464A (en) 2018-10-18 2018-10-18 Method for directly introducing aldehyde group on aromatic ring

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811214146.0A CN111072464A (en) 2018-10-18 2018-10-18 Method for directly introducing aldehyde group on aromatic ring

Publications (1)

Publication Number Publication Date
CN111072464A true CN111072464A (en) 2020-04-28

Family

ID=70308702

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811214146.0A Pending CN111072464A (en) 2018-10-18 2018-10-18 Method for directly introducing aldehyde group on aromatic ring

Country Status (1)

Country Link
CN (1) CN111072464A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113372208A (en) * 2021-05-20 2021-09-10 山东盛华电子新材料有限公司 Preparation method of trans-4- (trans-4-alkylcyclohexyl) cyclohexanecarboxaldehyde
CN114560759A (en) * 2021-08-02 2022-05-31 南京偌赛医药科技有限公司 Method for catalytically synthesizing aromatic aldehyde

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0512345D0 (en) * 2005-06-17 2005-07-27 Johnson Matthey Plc Oxidation process
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
CN107866284A (en) * 2016-09-26 2018-04-03 中国石油化工股份有限公司 Methylbenzene selective carbonylating catalyst
CN107913739A (en) * 2016-10-09 2018-04-17 中国石油化工股份有限公司 Catalyst for synthesis of alkyl aromatic aldehyde

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0512345D0 (en) * 2005-06-17 2005-07-27 Johnson Matthey Plc Oxidation process
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
CN107866284A (en) * 2016-09-26 2018-04-03 中国石油化工股份有限公司 Methylbenzene selective carbonylating catalyst
CN107913739A (en) * 2016-10-09 2018-04-17 中国石油化工股份有限公司 Catalyst for synthesis of alkyl aromatic aldehyde

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113372208A (en) * 2021-05-20 2021-09-10 山东盛华电子新材料有限公司 Preparation method of trans-4- (trans-4-alkylcyclohexyl) cyclohexanecarboxaldehyde
CN114560759A (en) * 2021-08-02 2022-05-31 南京偌赛医药科技有限公司 Method for catalytically synthesizing aromatic aldehyde

Similar Documents

Publication Publication Date Title
JP6800206B2 (en) Use of a renium-containing supported heterogeneous catalyst for direct dehydrogenation and dehydrogenation of glycerol to allyl alcohol
CN111072464A (en) Method for directly introducing aldehyde group on aromatic ring
CN109704900A (en) The method of one-step method from syngas alkene
CN109420517A (en) A kind of method that methane low temperature conversion prepares higher hydrocarbon
CN107913739B (en) Catalyst for synthesizing alkyl aromatic aldehyde
CN109701627A (en) Composite catalyst containing spinel structure and its application in one-step method from syngas alkene
CN104693016B (en) Method for preparing 4-methylbenzaldehyde from isoprene and acrolein
RU2185368C2 (en) Method of oxidation of aromatic compounds to hydroxyaromatic compounds
CN101838198A (en) Method for preparing carboxylic ester
CN103272644A (en) Schiff base metal catalyst used in liquid phase epoxidation reaction and preparation method of schiff base metal catalyst
CN101210194B (en) Catalytic hydrogenation method for olefin
CN109651113B (en) Process for synthesizing alkyl aromatic aldehyde
CN109651124B (en) Method for synthesizing p-tolualdehyde
CN107866284B (en) Catalyst for selective carbonylation of toluene
CN101544587B (en) Preparation method of alpha, alpha'-bis(tert-butyl peroxy) diisopropylbenzene
CN104230643A (en) Preparation method of isopropyl benzene
CN103977839B (en) A kind of ionic organic metal tungstates epoxidation catalyst and preparation method thereof
CN109651114B (en) Method for synthesizing alkyl aromatic aldehyde
CN109647508B (en) Catalyst for synthesizing p-methyl benzaldehyde
CN102964230A (en) Method for preparing benzaldehyde from methylbenzene through liquid-phase catalytic oxidation
CN107866283B (en) Catalyst for synthesizing p-methyl benzaldehyde
CN110538678B (en) Catalyst for preparing aromatic aldehyde
CN110540490B (en) Process for preparing aromatic aldehydes
CN109647509B (en) Catalyst for synthesizing alkyl aromatic aldehyde
CN111203267B (en) Solid acid catalyst for catalyzing decarboxylation of gamma-valerolactone to prepare butene, and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination