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Method for preparing aromatic acid by direct carboxylation of CO2

A technology of aromatic acid and carboxylation method, which is applied in the field of CO2 direct carboxylation method to prepare aromatic acid, which can solve the problems of harsh operating conditions, high catalyst cost, and strong Lewis corrosion of equipment, so as to improve reaction selectivity and shorten reaction time , the effect of excellent solvency

Active Publication Date: 2018-03-23
SHAANXI COAL & CHEM TECH INST
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  • Claims
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Problems solved by technology

However, these catalysts still have disadvantages such as large dosage, low efficiency, poor substrate adaptability, high cost and poor safety, making CO 2 Direct carboxylation method is difficult to industrialize
[0004] In 2002, Olah et al. (J.Am.Chem.Soc., 2002,124:11379-11391) reported that AlCl 3 / The Al system can realize the highly selective synthesis of a variety of aromatic acids under relatively mild conditions. This method has the advantages of mild reaction conditions, high yield and good selectivity, and is expected to be used in CO 2 The industrialization of the preparation of aromatic acids by direct carboxylation method, but the system still has the disadvantages of large amount of catalyst, severe corrosion of equipment by strong Lewis, and potential explosion hazard of Al in contact with water, which needs to be further optimized
However, chloroaluminate ionic liquids usually need to be operated under vacuum conditions, and there are problems such as complicated preparation process, harsh operating conditions, and high cost, which restrict its industrialization.
[0006] Therefore, how to overcome the existing CO 2 The disadvantages of high catalyst cost, harsh operating conditions, and poor safety in the preparation of aromatic acids by direct carboxylation are still a challenging work, and the development of new CO 2 The preparation of aromatic acids by direct carboxylation can not only realize the transformation and upgrading of the aromatic acid industry, but also enrich CO 2 The content of chemical utilization, and at the same time of obtaining important chemicals, realizes the chemical cycle of carbon, making it a powerful supplement to the natural carbon cycle, and improving the deteriorating global greenhouse effect

Method used

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  • Method for preparing aromatic acid by direct carboxylation of CO2
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  • Method for preparing aromatic acid by direct carboxylation of CO2

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preparation example Construction

[0039] In the preparation method of the present invention: aromatic hydrocarbon is benzene, alkyl substituted benzene (alkyl substituted benzene is toluene, 1,2-xylene, 1,3-xylene, 1,4-xylene, 1,3,5- trimethylbenzene, ethylbenzene, propylbenzene or tert-butylbenzene), halogenated benzene, naphthalene or alkyl-substituted naphthalene;

[0040] Lewis acid is AlCl 3 , AlBr 3 , FeCl 3 , FeBr 3 , BF 3 , SbF 5 , NbCl 5 and La(CF 3 SO 3 ) 3 One of, preferably AlCl 3 , less preferably AlBr 3 , FeCl 3 or FeBr 3 ;

[0041] Organic bases include alkylamines (alkylamines are primary amines R-NH 2 , secondary amine R 1 R 2 -NH or tertiary amine R 1 R 2 R 3 -N, where R 1 , R 2 and R 3 Both are C 1 ~C 18 Alkyl, allyl and various secondary or tertiary alkyl groups), imidazole / N-alkyl substituted imidazole (in imidazole / N-alkyl substituted imidazole, the alkyl is C 1 ~C 18 Alkyl, allyl and various secondary or tertiary alkyl groups), pyridine / alkyl substituted pyridin...

Embodiment 1

[0043] Under argon atmosphere, quickly add 40mL of dry 1,3,5-trimethylbenzene and 2.5g of anhydrous AlCl to a 250mL autoclave lined with PTFE 3 , 1.76g of dry N-methyldicyclohexylamine, and the reaction kettle was sealed after the feeding was completed. Then CO 2 The cylinder is connected to the autoclave through the pipeline, and the valve is opened to control the CO 2 The pressure was 6MPa, and at the same time, the stirring was started at a stirring rate of 1000rpm, and finally heating was started and kept at 40°C for 30h. After the reaction was completed, 150 mL of water was added to the reaction system, and the reaction was carried out for 30 min under stirring conditions, and then extracted three times with 50 mL of ether, and the extracts were combined and concentrated to dryness to obtain 2.72 g of off-white solid. Dissolve the above-mentioned off-white solid in 20mL of 10%wt sodium hydroxide solution, filter the insoluble matter to obtain the filtrate, then adjust t...

Embodiment 2

[0045] Under argon atmosphere, quickly add 40mL of dry 1,3,5-trimethylbenzene and 2.5g of anhydrous AlCl to a 250mL autoclave lined with PTFE 3 , 0.54g of dry 1-allylimidazole, and the reaction kettle was sealed after the feeding was completed. Then CO 2 The cylinder is connected to the autoclave through the pipeline, and the valve is opened to control the CO 2 The pressure was 6MPa, and at the same time, the stirring was started at a stirring rate of 1000rpm, and finally heating was started and kept at 40°C for 24h. After the reaction was completed, 150 mL of water was added to the reaction system, and the mixture was reacted for 30 min under stirring, and then extracted three times with 50 mL of ether. The extracts were combined, concentrated and dried to obtain 2.85 g of off-white solid. Dissolve the above-mentioned off-white solid in 20mL of 10%wt sodium hydroxide solution, filter the insoluble matter to obtain the filtrate, then adjust the pH value of the filtrate to 1 ...

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Abstract

The invention discloses a method for preparing aromatic acid by direct carboxylation of CO2. The method comprises the following steps: (1) adding aromatic hydrocarbon, organic alkali and lewis acid into a high pressure reaction kettle under an inert gas atmosphere, then feeding CO2 gas into the high pressure reaction kettle for reaction, and obtaining reaction liquid with aromatic acid at the endof the reaction; (2) adding water into the reaction liquid obtained in the step (1), then extracting the aromatic acid in the reaction liquid with an extracting agent to enable the aromatic acid in the reaction liquid to enter an extracting phase, separating the extracting phase from raffinate, and concentrating the extracting phase to obtain the aromatic acid. According to the method, complicatedpreparation of ionic liquid is avoided, and organic alkali is timely neutralized with halogen hydride produced by the reaction, so that the balance moves rightwards; at the end of the reaction, the organic alkali also can be recycled through alkali treatment. The method has the advantages of simple operation, mild conditions, green process, low cost and the like, and is expected to be applied toindustrial production.

Description

technical field [0001] The invention belongs to the field of fine chemical technology, in particular to a CO 2 A method for preparing aromatic acids by direct carboxylation. Background technique [0002] Aromatic acids are an important class of chemical products with a wide range of uses, and are widely used in the production of medicines, food additives, dyes, photosensitizers, plasticizers, spices and cosmetics. At present, the vast majority of aromatic acids are obtained through oxidation reactions and multi-step organic synthesis reactions, which have disadvantages such as low atom economy, complicated operations, harsh reaction conditions, many by-products, and serious environmental pollution. [0003] Compared with traditional methods, CO 2 The preparation of aromatic acids by direct carboxylation has the advantages of high atom economy, short reaction process, simple operation, low raw material cost, green and high efficiency, etc. But due to CO 2 It has strong th...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C63/04C07C63/06C07C51/15C07C63/08C07C51/41C07C51/02
CPCC07C51/02C07C51/15C07C51/412C07C63/04C07C63/06C07C63/08Y02P20/141
Inventor 王文涛田士东戚文博薛其才张生军郑化安殷海龙
Owner SHAANXI COAL & CHEM TECH INST
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