阅读说明：本技术 制备芳醛的方法 (Process for preparing aromatic aldehydes ) 是由 王艳红 肖忠斌 杨运信 于 2018-05-29 设计创作，主要内容包括：本发明涉及制备芳醛的方法。主要解决现有技术中存在的芳烃转化率以及芳醛收率低的问题,本发明通过采用制备芳醛的方法,包括在催化剂催化下芳烃与CO进行羰基化反应获得芳醛,其中所述催化剂包括离子液体、化合态活性金属和化合态助剂金属,所述的离子液体为季铵盐型离子液体,所述化合态活性金属包括Zr,所述化合态助剂金属包括Ru的技术方案,较好的解决了该技术问题,可用于芳醛的工业生产中。(The present invention relates to a process for preparing aromatic aldehydes. The method for preparing the aromatic aldehyde comprises the step of carrying out carbonylation reaction on aromatic hydrocarbon and CO under the catalysis of a catalyst to obtain the aromatic aldehyde, wherein the catalyst comprises ionic liquid, compound active metal and compound auxiliary agent metal, the ionic liquid is quaternary ammonium salt type ionic liquid, the compound active metal comprises Zr, and the compound auxiliary agent metal comprises Ru.)

1. the method for preparing the aromatic aldehyde comprises the step of carrying out carbonylation reaction on aromatic hydrocarbon and CO under the catalysis of a catalyst to obtain the aromatic aldehyde, wherein the catalyst comprises ionic liquid, compound active metal and compound auxiliary agent metal, the ionic liquid is quaternary ammonium salt type ionic liquid, the compound active metal comprises Zr, and the compound auxiliary agent metal comprises Ru.

2. The method as set forth in claim 1, wherein the weight ratio of said catalyst to said aromatic hydrocarbon is 1 to 12.

3. The method according to claim 1, wherein the reaction temperature is 20 to 150 ℃.

4. The method according to claim 1, wherein the pressure of the reaction is 1 to 8 MPa.

5. The method according to claim 1, wherein the reaction time is 1 to 12 hours.

6. The process of claim 1 wherein the combined reactive metal and combined adjuvant metal are independently selected from at least one of acetate, chloride, cyanide or trifluoroacetate.

7. The method as set forth in claim 1, wherein the weight ratio of the ionic liquid to the combined active metal is 100 (5-50).

8. The method as set forth in claim 7, wherein the weight ratio of the ionic liquid to the combined active metal is 100 (10-25).

9. The method as set forth in claim 1, wherein the weight ratio of the ionic liquid to the compound auxiliary metal is 100 (1-10).

10. The method as set forth in claim 9, wherein the weight ratio of the ionic liquid to the compound auxiliary metal is 100 (2-6).

Technical Field

The present invention relates to a process for preparing aromatic aldehydes.

Background

The 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.

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 used for preparing 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, so that the industrial development of the method is restricted (Tang dynasty, royal red, Liyanwei. the process improvement of indirect electrosynthesis of benzaldehyde/p-tolualdehyde by external-bath online ultrasound [ J ]. university of Tai rationality 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, 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 uses [ emim ] Cl/AlCl3(xAlCl3 is 0.75) as a catalyst, the mass ratio of IL/toluene is 8.5/1.8, CO partial pressure is kept at 8.2MPa at room temperature, and the reaction is carried out for 1h, so that the toluene conversion rate of 66% and the PTAL selectivity of 89.1% are realized (Saleh RY, Rouge B. process for making aromatic aldehyde using 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 arene conversion rate and low aromatic aldehyde yield, and provides a novel method for synthesizing aromatic aldehyde, which has the characteristics of high arene conversion rate and high aromatic aldehyde yield.

In order to solve the problems, the technical scheme adopted by the invention is as follows:

The method for preparing the aromatic aldehyde comprises the step of carrying out carbonylation reaction on aromatic hydrocarbon and CO under the catalysis of a catalyst to obtain the aromatic aldehyde, wherein the catalyst comprises ionic liquid, compound active metal and compound auxiliary agent metal, the ionic liquid is quaternary ammonium salt type ionic liquid, the compound active metal comprises compound Zr, and the compound auxiliary agent metal comprises compound Ru.

In the technical scheme, the weight ratio of the catalyst to the alkyl aromatic hydrocarbon is preferably 1-12.

In the technical scheme, the reaction temperature is preferably 20-150 ℃.

In the technical scheme, the pressure of the reaction is preferably 1-8 MPa.

In the technical scheme, the reaction time is preferably 1-12 h.

In the technical scheme, the quaternary ammonium salt type ionic liquid is preferably Me3NCl-AlCl3, wherein the molar ratio of Me3NCl to AlCl3 is 1 (1-4), and more preferably 1: 2.

In the above technical solution, the combined active metal and the combined auxiliary metal are independently and preferably selected from at least one of acetate, chloride, cyanide or trifluoroacetate.

In the above technical solution, the compound active metal preferably includes Zr and Rh at the same time, and the two have a synergistic effect in improving the conversion rate of the aromatic hydrocarbon.

In the above technical solution, the compound active metal preferably includes both Zr and Co, and the two have a synergistic effect in improving the conversion rate of aromatic hydrocarbons.

In the above technical solution, it is more preferable that the combined active metal includes Rh, Co and Zr at the same time, and Rh and Co have a synergistic effect in improving conversion rate of aromatic hydrocarbon, and Rh, Co and Zr have a synergistic effect in improving conversion rate of aromatic hydrocarbon.

In the above-described embodiments, the selection of the metal species is not particularly limited, and the ratio of Rh, Co, and Zr is not particularly limited, since the technical key of the present invention is the change of the specific amount.

For example: the ratio of Zr to Rh is not particularly limited, but is, for example, not limited to, 0.1 to 10 in terms of metal weight ratio, and more specific non-limiting ratios within this range are 0.28, 0.48, 0.58, 0.68, 0.78, 0.88, 0.98, 1.08, 1.18, 1.28, 1.38, 1.48, 1.58, 2.08, 2.58, 3.08, 3.58, 4.08, 4.58, 5.08, 5.58, 6.08, 7.08, 8.08, 9.08, and the like.

For another example: the ratio of Zr to Co is not particularly limited, but is not limited to, for example, 0.1 to 10 in terms of metal weight ratio, and more specific non-limiting ratios within this range are 0.28, 0.48, 0.58, 0.68, 0.78, 0.88, 0.98, 1.08, 1.18, 1.28, 1.38, 1.48, 1.58, 2.08, 2.58, 3.08, 3.58, 4.08, 4.58, 5.08, 5.58, 6.08, 7.08, 8.08, 9.08, and the like.

As specific compound forms from which the combined active metal is taken, non-limiting examples, Rh may be at least one of Rh (CH3COO)3, Rh (CF3COO)3 and RhCl3, Co may be at least one of Co (CH3COO)2, Co (CF3COO)2 and CoCl2, and Zr may be at least one of Zr (CH3COO)4, Zr (CF3COO)4, ZrCl 4.

In the technical scheme, the compound auxiliary metal preferably simultaneously comprises Ru and Zn, and the Ru and the Zn have synergistic effect on the aspect of improving the yield of aromatic aldehyde. In this case, the ratio between the two is not particularly limited, and for example, but not limited to, the weight ratio of Ru to Zn is 0.1 to 10, and more specific non-limiting ratios within this range are 0.28, 0.48, 0.58, 0.68, 0.78, 0.88, 0.98, 1.08, 1.18, 1.28, 1.38, 1.48, 1.58, 2.08, 2.58, 3.08, 3.58, 4.08, 4.58, 5.08, 5.58, 6.08, 7.08, 8.08, 9.08 and the like.

as specific compound forms from which the combined state promoter metal is taken, by way of non-limiting example, Ru may be RuCl3 and Zn may be Zn (CN) 2.

In the technical scheme, the weight ratio of the ionic liquid to the combined active metal is 100 (5-50), and preferably 100 (10-25).

In the technical scheme, the weight ratio of the ionic liquid to the compound auxiliary metal is 100 (1-10), and preferably 100 (2-6).

In the above technical scheme, the preparation method of the catalyst is not particularly limited, and the catalyst may be mixed according to the required components; the reaction system may also be added separately or simultaneously in accordance with the desired components at the time of the reaction for synthesizing the 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 the above technical scheme, the 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 from C1 to C6, and examples of the monoalkyl-substituted benzene include, but are not limited to, toluene, ethylbenzene, cumene, n-butylbenzene, tert-butylbenzene, n-hexylbenzene, and the like, which are a single compound 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 scheme, the key to the application is the choice of the catalyst, and under the catalyst conditions of the present invention, the skilled person knows how to determine other process conditions for preparing aromatic aldehydes.

The specific steps for preparing the aromatic aldehyde may be:

(1) Adding the components of the catalyst into the high-pressure reaction kettle;

(2) Replacing the air in the kettle for 3 times by N2, replacing for 3 times by CO gas, stirring and mixing;

(3) Adding 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 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:

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 diethyl ether extracts, performing rotary evaporation to obtain a residue, namely a crude aromatic aldehyde product, performing gas chromatography analysis on the crude aromatic aldehyde product, and calculating the conversion rate of aromatic hydrocarbon and the yield of target aromatic aldehyde according to the analysis result, wherein the calculation formula is as follows:

By adopting the technical scheme of the invention, the conversion rate of toluene can reach 95.7%, the yield of corresponding p-tolualdehyde can reach 80.5%, beneficial technical effects are obtained, and the method can be used for preparing aromatic aldehyde by carbonylation of aromatic hydrocarbon and CO.

Detailed Description

[ example 1 ]

Adding Me3NCl-AlCl381g, Rh (CH3COO)3 containing 15g of Rh and RuCl3 containing 4gRu into a 250mL high-pressure reaction kettle, and replacing the air in the kettle with N2 for 3 times and then with CO gas for 3 times; 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 of p-tolualdehyde are shown in table 1.

[ example 2 ]

Adding Me3NCl-AlCl381g, Rh (CH3COO)3 containing 15g of Rh and Zn (CN)2 containing 4gZn into a 250mL high-pressure reaction kettle, and replacing the air in the kettle with N2 for 3 times and then with CO gas for 3 times; 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 of p-tolualdehyde are shown in table 1.

[ example 3 ]

Adding Me3NCl-AlCl381g, Co (CH3COO)2 containing 15g of Co and RuCl3 containing 4g of Ru into a 250mL high-pressure reaction kettle, and replacing the air in the kettle with N2 for 3 times and then with CO gas for 3 times; 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 of p-tolualdehyde are shown in table 1.

[ example 4 ]

Adding Me3NCl-AlCl381g, Co (CH3COO)215g containing 15g of Co and Zn (CN)2 containing 4g of Zn into a 250mL high-pressure reaction kettle, and replacing the air in the kettle with N2 for 3 times and then with CO gas for 3 times; 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 of p-tolualdehyde are shown in table 1.

[ example 5 ]

Adding Me3NCl-AlCl381g, Zr (CH3COO)4 containing 15g of Zr and RuCl3 containing 4g of Ru into a 250mL high-pressure reaction kettle, and replacing the air in the kettle with N2 for 3 times and then with CO gas for 3 times; 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 of p-tolualdehyde are shown in table 1.

[ example 6 ]

Adding Me3NCl-AlCl381g, Zr (CH3COO)4 containing 15g of Zr and Zn (CN)2 containing 4g of Zn into a 250mL high-pressure reaction kettle, and replacing the air in the kettle with N2 for 3 times and then with CO gas for 3 times; 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 of p-tolualdehyde are shown in table 1.

[ example 7 ]

Adding Me3NCl-AlCl381g, Rh (CH3COO)3 containing 7.5g of Rh, Co (CH3COO)2 containing 7.5g of Co and RuCl3 containing 4g of Zr into a 250mL high-pressure reaction kettle, and replacing air in the kettle for 3 times by N2 and then 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-methyl benzaldehyde.

For convenience of comparison and explanation, the catalyst formulation, the conversion of toluene and the selectivity of p-tolualdehyde are shown in table 1.

[ example 8 ]

Adding Me3NCl-AlCl381g, Rh (CH3COO)3 containing 7.5g of Rh, Co (CH3COO)2 containing 7.5g of Co and Zn (CN)2 containing 4g of Zn into a 250mL high-pressure reaction kettle, and replacing air in the kettle with N2 for 3 times and then with CO gas for 3 times; 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-methyl benzaldehyde.

For convenience of comparison and explanation, the catalyst formulation, the conversion of toluene and the selectivity of p-tolualdehyde are shown in table 1.

[ example 9 ]

Adding Me3NCl-AlCl381g, Co (CH3COO)2 containing 7.5g of Co, Zr (CH3COO)4 containing 7.5g of Zr and RuCl3 containing 4g of Ru into a 250mL high-pressure reaction kettle, and replacing air in the kettle for 3 times by N2 and then 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-methyl benzaldehyde.

For convenience of comparison and explanation, the catalyst formulation, the conversion of toluene and the selectivity of p-tolualdehyde are shown in table 1.

[ example 10 ]

adding Me3NCl-AlCl381g, Co (CH3COO)2 containing 7.5g of Co, Zr (CH3COO)4 containing 7.5g of Zr and Zn (CN)2 containing 4g of Zn into a 250mL high-pressure reaction kettle, and replacing the air in the kettle with N2 for 3 times and then with CO gas for 3 times; 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-methyl benzaldehyde.

For convenience of comparison and explanation, the catalyst formulation, the conversion of toluene and the selectivity of p-tolualdehyde are shown in table 1.

[ example 11 ]

Adding Me3NCl-AlCl381g, Rh (CH3COO)3 containing 7.5g of Rh, Zr (CH3COO)4 containing 7.5g of Zr and RuCl3 containing 4g of Ru into a 250mL high-pressure reaction kettle, and replacing the air in the kettle with N2 for 3 times and then with CO gas for 3 times; 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-methyl benzaldehyde.

For convenience of comparison and explanation, the catalyst formulation, the conversion of toluene and the selectivity of p-tolualdehyde are shown in table 1.

[ example 12 ]

Adding Me3NCl-AlCl381g, Rh (CH3COO)37.5g containing 7.5g of Rh, Zr (CH3COO)47.5g containing 7.5g of Zr and Zn (CN)2 containing 4g of Zn into a 250mL high-pressure reaction kettle, and replacing the air in the kettle with N2 for 3 times and then with CO gas for 3 times; 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 of p-tolualdehyde are shown in table 1.

[ example 13 ]

Adding Me3NCl-AlCl381g, Rh (CH3COO)35g containing 5g of Rh, Co (CH3COO)25g containing 5g of Co, Zr (CH3COO)45g containing 5g of Zr and RuCl3 containing 4g of Ru into a 250mL high-pressure reaction kettle, and replacing the air in the kettle with N2 for 3 times and then with CO gas for 3 times; 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 of p-tolualdehyde are shown in table 1.

[ example 14 ]

Adding Me3NCl-AlCl381g, Rh (CH3COO)35g containing 5g of Rh, Co (CH3COO)25g containing 5g of Co, Zr (CH3COO)45g containing 5g of Zr and Zn (CN)2 containing 4g of Zn into a 250mL high-pressure reaction kettle, and replacing the air in the kettle with N2 for 3 times and then with CO gas for 3 times; 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 of p-tolualdehyde are shown in table 1.

[ example 15 ]

adding Me3NCl-AlCl381g, Rh (CH3COO)3 containing 7.5g of Rh, Co (CH3COO)2 containing 7.5g of Co, RuCl3 containing 2g of Ru and Zn (CN)2 containing 2g of Zn into a 250mL high-pressure reaction kettle, and replacing air in the kettle for 3 times by N2 and then 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 of p-tolualdehyde are shown in table 1.

[ example 16 ]

Adding Me3NCl-AlCl381g, Rh (CH3COO)3 containing 7.5g of Rh, Co (CH3COO)2 containing 7.5g of Co, RuCl3 containing 2g of Ru and Zn (CN)2 containing 2g of Zn into a 250mL high-pressure reaction kettle, and replacing air in the kettle for 3 times by N2 and then 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 of p-tolualdehyde are shown in table 1.

[ example 17 ]

Adding Me3NCl-AlCl381g, Co (CH3COO)2 containing 7.5g of Co, Zr (CH3COO)4 containing 7.5g of Zr, RuCl3 containing 2g of Ru and Zn (CN)2 containing 2g of Zn into a 250mL high-pressure reaction kettle, and replacing the air in the kettle with N2 for 3 times and then with CO gas for 3 times; stirring at 500rpm for 1 h; adding 50g of toluene, 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 p-tolualdehyde.

For convenience of comparison and explanation, the catalyst formulation, the conversion of toluene and the selectivity of p-tolualdehyde are shown in table 1.

[ example 18 ]

Adding Me3NCl-AlCl381g, Co (CH3COO)2 containing 7.5g of Co, Zr (CH3COO)4 containing 7.5g of Zr, RuCl3 containing 2g of Ru and Zn (CN)2 containing 2g of Zn into a 250mL high-pressure reaction kettle, and replacing the air in the kettle with N2 for 3 times and then with CO gas for 3 times; stirring at 500rpm for 1 h; adding 50g of toluene, 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 p-tolualdehyde.

For convenience of comparison and explanation, the catalyst formulation, the conversion of toluene and the selectivity of p-tolualdehyde are shown in table 1.

[ example 19 ]

Adding Me3NCl-AlCl381g, Rh (CH3COO)3 containing 7.5g of Rh, Zr (CH3COO)4 containing 7.5g of Zr, RuCl3 containing 2g of Ru and Zn (CN)2 containing 2g of Zn into a 250mL high-pressure reaction kettle, and replacing the air in the kettle with N2 for 3 times and then with CO gas for 3 times; stirring at 500rpm for 1 h; adding 50g of toluene, 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 p-tolualdehyde.

For convenience of comparison and explanation, the catalyst formulation, the conversion of toluene and the selectivity of p-tolualdehyde are shown in table 1.

[ example 20 ]

Adding Me3NCl-AlCl381g, Rh (CH3COO)3 containing 7.5g of Rh, Zr (CH3COO)4 containing 7.5g of Zr, RuCl3 containing 2g of Ru and Zn (CN)2 containing 2g of Zn into a 250mL high-pressure reaction kettle, and replacing the air in the kettle with N2 for 3 times and then with CO gas for 3 times; stirring at 500rpm for 1 h; adding 50g of toluene, 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 p-tolualdehyde.

For convenience of comparison and explanation, the catalyst formulation, the conversion of toluene and the selectivity of p-tolualdehyde are shown in table 1.

[ example 21 ]

Adding Me3NCl-AlCl381g, Rh (CH3COO)3 containing 5g of Rh, Co (CH3COO)2 containing 5g of Co, Zr (CH3COO)4 containing 5g of Zr, RuCl3 containing 2g of Ru and Zn (CN)2 containing 2g of Zn into a 250mL high-pressure reaction kettle, and replacing the air in the kettle for 3 times by N2 and then 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 of p-tolualdehyde are shown in table 1.

[ example 22 ]

Adding Me3NCl-AlCl381g, Rh (CH3COO)3 containing 5g of Rh, Co (CH3COO)2 containing 5g of Co, Zr (CH3COO)4 containing 5g of Zr, RuCl3 containing 2g of Ru and Zn (CN)2 containing 2g of Zn into a 250mL high-pressure reaction kettle, and replacing the air in the kettle for 3 times by N2 and then 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-tolualdehyde.

For convenience of comparison and illustration, the catalyst formulation, the conversion of ethylbenzene and the selectivity to p-ethylbenzaldehyde are listed in table 1.

[ example 23 ]

Adding Me3NCl-AlCl381g, Rh (CH3COO)3 containing 5g of Rh, Co (CH3COO)2 containing 5g of Co, Zr (CH3COO)4 containing 5g of Zr, RuCl3 containing 2g of Ru and Zn (CN)2 containing 2g of Zn into a 250mL high-pressure reaction kettle, and replacing the air in the kettle for 3 times by N2 and then 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 p-tolualdehyde.

for ease of comparison and illustration, the catalyst formulation, cumene conversion and selectivity to p-isopropylbenzaldehyde are listed in table 1.

[ example 24 ]

Adding Me3NCl-AlCl381g, Rh (CH3COO)3 containing 5g of Rh, Co (CH3COO)2 containing 5g of Co, Zr (CH3COO)4 containing 5g of Zr, RuCl3 containing 2g of Ru and Zn (CN)2 containing 2g of Zn into a 250mL high-pressure reaction kettle, and replacing the air in the kettle for 3 times by N2 and then 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-tolualdehyde.

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

Note: the molar ratio of Me3NCl to AlCl3 was 1: 2.