CN109647508B - Catalyst for synthesizing p-methyl benzaldehyde - Google Patents
Catalyst for synthesizing p-methyl benzaldehyde Download PDFInfo
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- CN109647508B CN109647508B CN201710934647.5A CN201710934647A CN109647508B CN 109647508 B CN109647508 B CN 109647508B CN 201710934647 A CN201710934647 A CN 201710934647A CN 109647508 B CN109647508 B CN 109647508B
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- 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
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0285—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
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- 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
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Abstract
The present invention relates to a catalyst for synthesizing p-tolualdehyde. Mainly solves the problems of toluene conversion rate and low yield of the p-tolualdehyde in the prior art, and the invention adopts a catalyst for synthesizing the p-tolualdehyde, wherein the catalyst comprises ionic liquid and rare earth salt, the ionic liquid is selected from the ionic liquid with the structural formula shown in the specification, and R is R1And R2Independently selected from C1-C4 alkyl, and X is selected from PF6、SbF6、AlCl4、BF4、PF4、CF3COO、CF3SO3And (CF)3SO2)2At least one of N, which can be used in the industrial production of p-tolualdehyde.
Description
Technical Field
The present invention relates to a catalyst for synthesizing p-tolualdehyde.
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 synthesis method of p-tolualdehyde mainly includes direct high-temperature oxidation method, indirect electrosynthesis method and carbonylation method.
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, 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 yield of methylbenzaldehyde.
Disclosure of Invention
The invention aims to solve the technical problems of high toluene conversion rate and low yield of p-tolualdehyde and provides a novel catalyst for synthesizing p-tolualdehyde, which has the characteristics of high toluene conversion rate and high yield of p-tolualdehyde.
The second technical problem to be solved by the invention is the application of the catalyst.
In order to solve one of the problems, the technical scheme adopted by the invention is as follows:
a catalyst for synthesizing p-tolualdehyde, said catalyst comprising an ionic liquid and a rare earth salt, said ionic liquid being selected from ionic liquids having the formula:
wherein R is1And R2Independently selected from C1-C4 alkyl, and X is selected from PF6、SbF6、AlCl4、BF4、PF4、CF3COO、CF3SO3And (CF)3SO2)2And N.
In the above technical scheme, R1And R2Preferably different alkyl groups. Such as but not limited to R1Is methyl and R2At least one selected from ethyl and butyl.
In the above technical scheme, X is selected from PF6And SbF6More preferably both PF6And SbF6Two anions have synergistic effect in improving toluene conversion rate. At this time, the PF6And SbF6The ratio therebetween is not particularly limited, such as but not limited to PF6And SbF6The molar ratio of (a) is 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.
The ionic liquid may be, by way of non-limiting example, one of 1-butyl-3-methylimidazolium hexafluorophosphate, 1-N-propyl-3-methylimidazolium hexafluorophosphate, 1-ethyl-3-methylimidazolium hexafluorophosphate, N-dimethylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium hexafluoroantimonate, 1-N-propyl-3-methylimidazolium hexafluoroantimonate, 1-ethyl-3-methylimidazolium hexafluoroantimonate and N, N-dimethylimidazolium hexafluoroantimonate. More preferably, the ionic liquid is at least one of 1-butyl-3-methylimidazolium hexafluoroantimonate and 1-butyl-3-methylimidazolium hexafluorophosphate.
In the above technical scheme, the rare earth salt is preferably a rare earth perfluoroalkyl sulfonate.
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 and cerium.
In the above technical solution, the rare earth preferably includes two of scandium and cerium, and the perfluoroalkyl sulfonate salts of the two rare earth elements have a synergistic effect in improving the toluene conversion rate. In this case, the ratio between the perfluoroalkylsulfonic acid salts of the two rare earth elements is not particularly limited, but is, for example, not limited to, 0.1 to 10 in terms of moles, 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 molar ratio of the ionic liquid to the rare earth salt is preferably 1 (0.1-2).
In the above technical solution, the catalyst preferably further comprises an accelerator, and further preferably the molar ratio of the ionic liquid, the rare earth salt and the accelerator is 1 (0.1-2) to (0-0.5).
In the above technical solution, the accelerator is preferably at least one of a nitrogen heterocyclic compound and an organic phosphine compound. More preferably, the method comprises the nitrogen heterocyclic compound and the organic phosphine compound simultaneously, and the nitrogen heterocyclic compound and the organic phosphine compound have synergistic effect on improving the yield of p-tolualdehyde. In this case, the ratio between the two promoters is not particularly limited, and examples thereof include, but are not limited to, a molar ratio of the nitrogen heterocyclic compound to the organophosphine compound of 0.1 to 10, 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 above technical solution, the nitrogen heterocyclic compound is at least one selected from azacyclo-carbene, alkyl pyridine and phenanthroline, and more preferably phenanthroline.
In the above technical solution, the organic phosphine compound is preferably at least one of triphenylphosphine and tricyclohexylphosphine.
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.
The specific steps for synthesizing p-tolualdehyde 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 toluene, 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 p-tolualdehyde.
To solve the second technical problem of the present invention, the technical solution of the present invention is as follows:
the use of a catalyst according to any one of the preceding technical solutions for the synthesis of p-tolualdehyde by carbonylation of toluene with CO.
The technical key of the invention is the selection of the catalyst, and based on the disclosure of the invention, the skilled person can reasonably select the method for specific application without creative efforts, such as:
the method for synthesizing p-methylbenzaldehyde comprises the step of carrying out carbonylation reaction on toluene and CO under the catalysis of a catalyst to obtain the p-methylbenzaldehyde.
In the technical scheme, the weight ratio of the catalyst to the toluene 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 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, rotary evaporating to obtain a residue, namely a p-tolualdehyde crude product, carrying out gas chromatography analysis on the crude product, and calculating the conversion rate of toluene and the yield of p-tolualdehyde 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 83.9%, the yield of p-tolualdehyde can reach 76.8%, and beneficial technical effects are obtained, so that the method can be used for preparing p-tolualdehyde by carbonylation of toluene and CO.
Detailed Description
[ example 1 ]
1-butyl-3-methylimidazolium hexafluoroantimonate (0.5mol, 187g) and Sc (CF) are added into a titanium material high-pressure reaction kettle3SO3)3(0.5mol, 246g), the 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 110g of toluene; replacing the air in the kettle with CO gas for 3 times; heating to 50 ℃, keeping CO pressure at 2.0MPa, stirring at 300rpm, and reacting for 5h to obtain a product mixture containing p-tolualdehyde.
For convenience of comparison and explanation, the catalyst formulation is shown in table 1, and the conversion of toluene and the yield of p-tolualdehyde are shown in table 2.
[ example 2 ]
Adding 1-butyl-3-methylimidazolium hexafluorophosphate (0.5mol, 142g) and Sc (CF) into a titanium high-pressure reaction kettle3SO3)3(0.5mol, 246g), the 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 110g of toluene; replacing the air in the kettle with CO gas; heating to 50 ℃, keeping CO pressure at 2.0MPa, stirring at 300rpm, and reacting for 5h to obtain a product mixture containing p-tolualdehyde.
For convenience of comparison and explanation, the catalyst formulation is shown in table 1, and the conversion of toluene and the yield of p-tolualdehyde are shown in table 2.
[ example 3 ]
1-butyl-3-methylimidazolium hexafluoroantimonate (0.5mol, 187g) and Ce (CF) are added into a titanium high-pressure reaction kettle3SO3)3(0.5mol, 299 g); 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 110g of toluene; replacing the air in the kettle with CO gas for 3 times; heating to 50 ℃, keeping CO pressure at 2.0MPa, stirring at 300rpm, and reacting for 5h to obtain a product mixture containing p-tolualdehyde.
For convenience of comparison and explanation, the catalyst formulation is shown in table 1, and the conversion of toluene and the yield of p-tolualdehyde are shown in table 2.
[ example 4 ]
Adding 1-butyl-3-methylimidazolium hexafluorophosphate (0.5mol, 1) into a titanium high-pressure reaction kettle42g) And Ce (CF)3SO3)3(0.5mol, 299 g); 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 110g of toluene; replacing the air in the kettle with CO gas for 3 times; heating to 50 ℃, keeping CO pressure at 2.0MPa, stirring at 300rpm, and reacting for 5h to obtain a product mixture containing p-tolualdehyde.
For convenience of comparison and explanation, the catalyst formulation is shown in table 1, and the conversion of toluene and the yield of p-tolualdehyde are shown in table 2.
[ example 5 ]
Adding 1-butyl-3-methylimidazolium hexafluoroantimonate (0.25mol, 94g), 1-butyl-3-methylimidazolium hexafluorophosphate (0.25mol, 71g) and Sc (CF) into a titanium high-pressure reaction kettle3SO3)3(0.5mol, 246 g); 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 110g of toluene; replacing the air in the kettle with CO gas for 3 times; heating to 50 ℃, keeping CO pressure at 2.0MPa, stirring at 300rpm, and reacting for 5h to obtain a product mixture containing p-tolualdehyde.
For convenience of comparison and explanation, the catalyst formulation is shown in table 1, and the conversion of toluene and the yield of p-tolualdehyde are shown in table 2.
[ example 6 ]
Adding 1-butyl-3-methylimidazolium hexafluoroantimonate (0.25mol, 94g), 1-butyl-3-methylimidazolium hexafluorophosphate (0.25mol, 71g) and Ce (CF) into a titanium high-pressure reaction kettle3SO3)3(0.5mol, 299 g); 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 110g of toluene; replacing the air in the kettle with CO gas for 3 times; heating to 50 ℃, keeping CO pressure at 2.0MPa, stirring at 300rpm, and reacting for 5h to obtain a product mixture containing p-tolualdehyde.
For convenience of comparison and explanation, the catalyst formulation is shown in table 1, and the conversion of toluene and the yield of p-tolualdehyde are shown in table 2.
[ example 7 ]
Adding 1-butyl-3-methylimidazole into a titanium material high-pressure reaction kettleHexafluoroantimonate (0.5mol, 187g), Sc (CF)3SO3)3(0.25mol, 123g) and Ce (CF)3SO3)3(0.25mol, 147 g); 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 110g of toluene; replacing the air in the kettle with CO gas for 3 times; heating to 50 ℃, keeping CO pressure at 2.0MPa, stirring at 300rpm, and reacting for 5h to obtain a product mixture containing p-tolualdehyde.
For convenience of comparison and explanation, the catalyst formulation is shown in table 1, and the conversion of toluene and the yield of p-tolualdehyde are shown in table 2.
[ example 8 ]
Adding 1-butyl-3-methylimidazolium hexafluorophosphate (0.5mol, 142g) and Sc (CF) into a titanium high-pressure reaction kettle3SO3)3(0.25mol, 123g) and Ce (CF)3SO3)3(0.25mol, 147 g); 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 110g of toluene; replacing the air in the kettle with CO gas for 3 times; heating to 50 ℃, keeping CO pressure at 2.0MPa, stirring at 300rpm, and reacting for 5h to obtain a product mixture containing p-tolualdehyde.
For convenience of comparison and explanation, the catalyst formulation is shown in table 1, and the conversion of toluene and the yield of p-tolualdehyde are shown in table 2.
[ example 9 ]
1-butyl-3-methylimidazolium hexafluoroantimonate (0.25mol, 94g), 1-butyl-3-methylimidazolium hexafluorophosphate (0.25mol, 71g), Sc (CF) are added into a titanium high-pressure reaction kettle3SO3)3(0.25mol, 123g) and Ce (CF)3SO3)3(0.25mol, 147 g); 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 110g of toluene; replacing the air in the kettle with CO gas for 3 times; heating to 50 ℃, keeping CO pressure at 2.0MPa, stirring at 300rpm, and reacting for 5h to obtain a product mixture containing p-tolualdehyde.
For convenience of comparison and explanation, the catalyst formulation is shown in table 1, and the conversion of toluene and the yield of p-tolualdehyde are shown in table 2.
[ example 10 ]
1-butyl-3-methylimidazolium hexafluoroantimonate (0.25mol, 94g), 1-butyl-3-methylimidazolium hexafluorophosphate (0.25mol, 71g), Sc (CF) are added into a titanium high-pressure reaction kettle3SO3)3(0.25mol，123g)、Ce(CF3SO3)3(0.25mol, 147g) and phenanthroline (0.10mol, 19.8 g); 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 110g of toluene; replacing the air in the kettle with CO gas for 3 times; heating to 50 ℃, keeping CO pressure at 2.0MPa, stirring at 300rpm, and reacting for 5h to obtain a product mixture containing p-tolualdehyde.
For convenience of comparison and explanation, the catalyst formulation is shown in table 1, and the conversion of toluene and the yield of p-tolualdehyde are shown in table 2.
[ example 11 ]
1-butyl-3-methylimidazolium hexafluoroantimonate (0.25mol, 94g), 1-butyl-3-methylimidazolium hexafluorophosphate (0.25mol, 71g), Sc (CF) are added into a titanium high-pressure reaction kettle3SO3)3(0.25mol，123g)、Ce(CF3SO3)3(0.25mol, 147g) and triphenylphosphine (0.10mol, 26 g); 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 110g of toluene; replacing the air in the kettle with CO gas for 3 times; heating to 50 ℃, keeping CO pressure at 2.0MPa, stirring at 300rpm, and reacting for 5h to obtain a product mixture containing p-tolualdehyde.
For convenience of comparison and explanation, the catalyst formulation is shown in table 1, and the conversion of toluene and the yield of p-tolualdehyde are shown in table 2.
[ example 12 ]
1-butyl-3-methylimidazolium hexafluoroantimonate (0.25mol, 94g), 1-butyl-3-methylimidazolium hexafluorophosphate (0.25mol, 71g), Sc (CF) are added into a titanium high-pressure reaction kettle3SO3)3(0.25mol，123g)、Ce(CF3SO3)3(0.25mol, 147g), phenanthroline (0.05mol, 10g) and triphenylphosphine (0).05mol, 13 g); 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 110g of toluene; replacing the air in the kettle with CO gas for 3 times; heating to 50 ℃, keeping CO pressure at 2.0MPa, stirring at 300rpm, and reacting for 5h to obtain a product mixture containing p-tolualdehyde.
For convenience of comparison and explanation, the catalyst formulation is shown in table 1, and the conversion of toluene and the yield of p-tolualdehyde are shown in table 2.
TABLE 1
TABLE 2
| Conversion of toluene/%) | Yield of p-tolualdehyde/%) | |
| Example 1 | 68.6 | 51.9 |
| Example 2 | 65.8 | 50.0 |
| Example 3 | 64.0 | 46.7 |
| Example 4 | 63.2 | 45.8 |
| Example 5 | 71.5 | 52.3 |
| Example 6 | 70.2 | 50.1 |
| Example 7 | 73.0 | 61.8 |
| Example 8 | 71.9 | 63.0 |
| Example 9 | 80.5 | 62.4 |
| Example 10 | 81.2 | 68.7 |
| Example 11 | 81.7 | 71.0 |
| Example 12 | 83.9 | 76.8 |
Claims (5)
1. A catalyst for synthesizing p-tolualdehyde, said catalyst comprising an ionic liquid and a rare earth salt, said ionic liquid being selected from ionic liquids having the formula:
wherein R1 and R2 are independently selected from C1-C4 alkyl, and X is selected from PF6And/or SbF6；
The rare earth perfluoroalkyl sulfonate is rare earth triflate;
the molar ratio of the ionic liquid to the rare earth salt is 1 (0.1-2);
the rare earth salt is selected from scandium and cerium.
2. The catalyst of claim 1, wherein the catalyst comprises a promoter.
3. The catalyst of claim 2, wherein the molar ratio of the ionic liquid, the rare earth salt and the promoter is 1 (0.1-2) to (0-0.5).
4. The catalyst of claim 2, wherein the promoter is at least one of a nitrogen heterocyclic compound and an organophosphinic compound.
5. Use of the catalyst according to any one of claims 1 to 4 in the synthesis of p-tolualdehyde by carbonylation of toluene with CO.
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| JPH06157391A (en) * | 1992-11-25 | 1994-06-03 | Nippon Steel Corp | Method for formylating aromatic compound |
| CN1594258A (en) * | 2004-06-29 | 2005-03-16 | 浙江大学 | Process for preparing benzaldehyde by benzene oxidation and carbonylation |
| CN101225028A (en) * | 2007-01-17 | 2008-07-23 | 中国石油化工股份有限公司 | Preparation method of alkyl aromatic aldehyde |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06157391A (en) * | 1992-11-25 | 1994-06-03 | Nippon Steel Corp | Method for formylating aromatic compound |
| CN1594258A (en) * | 2004-06-29 | 2005-03-16 | 浙江大学 | Process for preparing benzaldehyde by benzene oxidation and carbonylation |
| CN101225028A (en) * | 2007-01-17 | 2008-07-23 | 中国石油化工股份有限公司 | Preparation method of alkyl aromatic aldehyde |
Non-Patent Citations (1)
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| 甲苯羰基化法合成对甲基苯甲醛用催化剂的研究进展;王艳红 等;《聚酯工业》;20160731;第29卷(第4期);摘要、3 离子液体类催化剂 * |
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