CN1073542C - Method for synthesizing aromatic aldehyde by continuous catalytic hydrogenation of aromatic acid or aromatic ester - Google Patents
Method for synthesizing aromatic aldehyde by continuous catalytic hydrogenation of aromatic acid or aromatic ester Download PDFInfo
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- CN1073542C CN1073542C CN98122074A CN98122074A CN1073542C CN 1073542 C CN1073542 C CN 1073542C CN 98122074 A CN98122074 A CN 98122074A CN 98122074 A CN98122074 A CN 98122074A CN 1073542 C CN1073542 C CN 1073542C
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- C07—ORGANIC CHEMISTRY
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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
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Abstract
The present invention relates to a method for catalyzing and synthesizing corresponding aromatic aldehyde by aromatic acid or aromatic ester, and the corresponding aromatic aldehyde is prepared by gas-phase hydrogenation of the aromatic acid or the aromatic ester at normal pressure under the existence of manganese oxide which is modified by using gamma-Al2O3 as a carrier, and the activation and the hydrogenation reaction of a catalyst are continuously carried out. Modifier of the catalyst is one or several kinds of Zn, Zr and Cu, and the reaction temperature is 350 to 500 DEG C; additionally, when the molar ratio of hydrogen and the aromatic acid or the aromatic ester is 10 to 200, products of aromatic aldehyde with content higher than 98% can be prepared, and the reaction yield is higher than 80%.
Description
The invention relates to a method for synthesizing aromatic aldehyde by gas-phase continuous catalytic hydrogenation of aromatic acid or ester thereof.
Aromatic aldehyde is an important organic chemical product, is an important synthetic raw material of fine chemical products such as medicines, spices, resin additives and the like, and chlorine-free aromatic aldehyde can also be used for essence and food additives.
The traditional preparation process of aromatic aldehyde is toluene branched methyl halogenation, which is mainly an organic synthesis process of adding extra equivalent of halogen accessory raw materials, and the aromatic aldehyde product contains chlorine. In addition, there are a formylation method and an oxidation method of benzene, which are limited by the reaction substrate and the use thereof is limited to a specific case. European patent EP0,150,961 describes a process for the catalytic hydrogenation of aromatic acids or esters thereof to aromatic aldehydes, in which ZrO is used2Catalysts and modifying components one or more of Al, Sc, Ga, In, La, Ce, Pr, Nd. U.S. Pat. No. 3, 4,585,900 describes the synthesis of aromatic aldehydes by catalytic hydrogenation of aromatic acids using α -Al2O3Y as a carrier2O3The reaction temperature of the CuO catalyst is 420 ℃, and when the hydrogen-acid ratio (mol ratio) is 50, the conversion rate of the benzoic acid is 87.5 percent, and the selectivity of the benzaldehyde is 92.9 percent. The above methods have disadvantages such as high catalyst cost, environmental pollution, etc., and thus, there is a continuing need for improvement.
The invention aims to provide a method for continuously synthesizing aromatic aldehyde by aromatic acid or ester under normal pressure gas phase catalysis.
Embodiments of the invention relate to the use of gamma-Al2O3In the presence of a manganese oxide catalyst modified as a carrier, aromatic acid or ester thereof is subjected to normal-pressure gas-phase hydrogenation to prepare corresponding aromatic aldehyde. The reaction formula is as follows:
The invention uses gamma-Al2O3Manganese oxide modified as carrier as catalystThe catalyst can be modified by one or more elements of Cu, Zn and Zr, and is reduced and activated under hydrogen or a hydrogen-nitrogen mixed gas, the reduction temperature is slowly increased from 120 ℃ to 420 ℃, and after reduction, the aromatic acid or ester and the hydrogen are continuously preheated, mixed and enter a catalytic bed for reaction. The hydrogenation temperature is 350-500 ℃, the molar ratio of hydrogen to the aromatic acid or ester is 10-200, and the liquid hourly space velocity of the aromatic acid or ester is 0.05-0.5hr-1。
In the present invention, the aromatic acid or ester is a benzoic acid or a derivative of benzoic acid ester such as benzoic acid, hydroxybenzoic acid, methylbenzoic acid, methyl benzoate, methyl hydroxybenzoate, methyl methylbenzoate and the like.
The better conditions of the reaction are as follows: the hydrogenation reaction temperature is 380 ℃ to 420 ℃, the molar ratio of the hydrogen to the aromatic acid or ester is 20 to 100, and the liquid hourly space velocity of the aromatic acid or ester is 0.1 to 0.3hr-1。
The catalyst used in the invention is gamma-Al2O3The manganese oxide is modified by a carrier, and the modified elements are one or more of Cu, Zn and Zr. Dissolving nitrate or acetate of manganese and aluminum nitrate in water solution at 50-70 deg.C, adding nitrate of copper, zirconium or zinc, adjusting pH with ammonia water to pH =9-11 to obtain coprecipitate, leaching the coprecipitate with deionized water to neutrality, oven drying, calcining at 400-500 deg.C for 1.5-3.5 hr to obtain gamma-Al2O3The modified manganese oxide catalyst used as the carrier can be filled into a reactor for reduction and activation and then used for catalytic hydrogenation reaction.
Roasting the reduced gamma-Al2O3The modified manganese oxide catalyst used as the carrier is marked as MnO-M/gamma-Al2O3A catalyst. Wherein M is a modifier metal element.
The manganese content in the catalyst is 10-50% (wt%), and the modifier content is 0.1-5.0% (wt%). Experiments prove that the catalyst prepared in the range has better catalytic effect.
The reaction adopts a normal pressure gas phase hydrogenation method, so that the aromatic acid or ester thereof needs to be gasified to participate in the reaction, the gasification of the aromatic acid or ester thereof is realized by heating the raw material to be above the boiling point or below the boiling point and adopting a saturated steam method, and then the aromatic acid or ester thereof is mixed with preheated hydrogen to enter a reactor for reaction.
The invention uses gamma-Al2O3The method is used forpreparing corresponding aromatic aldehyde by the normal pressure gas phase hydrogenation of aromatic acid or ester in the presence of a manganese oxide catalyst with a modified carrier. The method has the characteristics that the reduction of the catalyst and the hydrogenation reaction can be continuously carried out, the process is simple, the conversion rate and the selectivity of the catalytic hydrogenation are high, the reaction yield is kept above 80%, the product purity is high, no chlorine is contained, the chlorine-free aromatic aldehyde with the content of more than 98% can be prepared, and the method can be used as a raw material and an additive in various industries of chemical industry, spice and food.
Example (b):
1. one preparation method of the catalyst is to dissolve manganese nitrate and aluminum nitrate in an aqueous solution, adjust the solution to be alkaline by ammonia water, generally adjust the pH to be =10-11, preferably the solution temperature is 50 ℃ when dissolving, obtain a coprecipitate, rinse the coprecipitate to be neutral by deionized water, dry, bake in a muffle furnace at 500 ℃ for 3 hours, obtain the catalyst containing gamma-Al2O3The modified manganese oxide catalyst used as the carrier can be filled into a reactor for reduction and activation and then used for catalytic hydrogenation reaction.
2. The second preparation method of the catalyst is to dissolve manganese acetate and aluminum nitrate in aqueous solution, adjust the solution to be alkaline by ammonia water, generally adjust the pH to =9-10, the solution temperature is preferably 50 ℃ when dissolving, obtain coprecipitate, rinse the coprecipitate by deionized water to be neutral, dry, then bake for 3 hours in muffle furnace at 450 ℃, obtain the catalyst containing gamma-Al2O3The modified manganeseoxide catalyst used as the carrier can be filled into a reactor for reduction and activation and then used for catalytic hydrogenation reaction.
3. In this example, MnO/gamma-Al prepared by the method of example 1 was used2O3A catalyst.
Adding 5 g of Mn2O3/γ-Al2O3The catalyst was loaded into a stainless steel reactor with a diameter of 14mm and reduced first with a mixture of hydrogen and nitrogen, the reduction temperature rising slowly from 120 ℃ to 420 ℃. After reduction, pumping methyl benzoate into a gasifier by using a metering pump, mixing with preheated hydrogen, heating, and allowing the mixture to enter a catalytic bed for reaction, wherein the feeding amount of the methyl benzoate is 3.5ml/hr, and the feeding flow of the hydrogen is 0.021M3The reaction temperature is 410 ℃, the conversion rate of methyl benzoate is 97 percent, and the selectivity of benzaldehyde is 86 percent.
4. In this example, the catalyst of example 1 was used, and 2% of Zr element was added for modification.
Adding 5 g of Mn2O3-Zr/γ-Al2O3The catalyst was loaded into a stainless steel reactor having a diameter of 14mm, the catalyst reduction and feeding method was the same as in example 3, the feeding amount of methyl benzoate was 3.5ml/hr, and the feeding flow of hydrogen was 0.021M3The reaction temperature is 395 ℃, the conversion rate of the methyl benzoate is 100 percent, and the selectivity of the benzaldehyde is 87.5 percent.
5. In this example, the catalyst prepared by the method of example 2 was used.
Adding 5 g of Mn2O3/γ-Al2O3The catalyst was loaded into a stainless steel reactor with a diameter of 14mm, the catalyst reduction method wasthe same as in example 3, benzoic acid was fed in saturated steam, the evaporation temperature was controlled at 160 ℃, and the hydrogen feed flow was 0.040M3H, reaction temperature 420 ℃, benzoic acid conversion rate 100 percent and benzoic acidThe selectivity to aldehyde was 95%.
6. In this example, the catalyst prepared by the method of example 2 was used.
Adding 5 g of Mn2O3/γ-Al2O3The catalyst is filled into a stainless steel reactor with the diameter of 14mm, the catalyst reduction and feeding method is the same as that in example 3, the raw material of the o-hydroxybenzoic acid methyl ester is pumped into a gasifier by a metering pump, is mixed with preheated hydrogen, enters a catalytic bed after being heated for reaction, the feeding amount of the o-hydroxybenzoic acid methyl ester is 3.2ml/hr, and the feeding flow of the hydrogen is 0.025M3The reaction temperature is 400 ℃, the conversion rate of the methyl o-hydroxybenzoate is 100 percent, and the selectivity of the benzaldehyde is 85 percent％。
7. In this example, the catalyst prepared by the method of example 1 was modified by adding 3% of Zn element. Adding 5 g of Mn2O3/γ-Al2O3The catalyst was loaded into a stainless steel reactor having a diameter of 14mm, the catalyst reduction and feeding method was as in example 3, the feeding amount of methyl benzoate was 3.5ml/hr, and the feeding amount of hydrogen was 0.021M3The reaction temperature is 405 ℃, the conversion rate of the methyl benzoate is 100 percent, and the selectivity of the benzaldehyde is 87.0 percent.
8. In this example, the catalyst prepared by the method of example 2 was modified by adding 5% of Cu element.
Adding 5 g of Mn2O3-Cu/γ-Al2O3The catalyst was loaded into a stainless steel reactor having a diameter of 14mm, the catalyst reduction and feeding method was the same as in example 3, the feeding amount of methyl benzoate was 3.5ml/hr, and the feeding flow of hydrogen was 0.021M3The reaction temperature is 400 ℃, the conversion rate of the methyl benzoate is 100 percent, and the selectivity of the benzaldehyde is 85 percent.
Claims (4)
1. A process for synthesizing aromatic aldehyde by continuous hydrogenation of aromatic acid ester or gas phase catalyst features use of gamma-Al2O3Manganese oxide modified by a carrier is used as a catalyst, a modifying element of the catalyst is one or more of Zn, Zr and Cu, the content (weight percentage content) of manganese in the catalyst is 10-50%, the content (weight percentage content) of a modifying agent is 0.1-5.0%, reducing gas hydrogen or a hydrogen-nitrogen mixed gas is used for reduction and activation, gasified aromatic acid or ester is mixed with the hydrogen and then continuously enters a catalyst bed for hydrogenation reaction, and the activation and reaction conditions are as follows:
(1) the reduction activation temperature of the catalyst is 120-420 ℃;
(2) the molar ratio of hydrogen to aromatic acid or its ester is 10-200, and the liquid hourly space velocity of aromatic acid or its ester is 0.05-0.5hr-1；
(3) The hydrogenation reaction temperature is 350-500 ℃.
2. The method of claim 1The gas phase continuous hydrogenation process of synthesizing aromatic aldehyde with aromatic acid or ester features the molar ratio of hydrogen to aromatic acid or ester of 20-100 and the liquid hourly space velocity of aromatic acid or ester of 0.1-0.3hr-1The reaction temperature is 380-420 ℃.
3. The method for synthesizing aromatic aldehyde by gas-phase continuous hydrogenation of aromatic acid or ester according to claim 1, wherein the catalyst is prepared by dissolving nitrate or acetate of manganese and aluminum nitrate in water, adding nitrate of copper, zirconium or zinc after dissolving, adjusting the solution to be alkaline to obtain coprecipitate, washing the precipitate to be neutral, drying, roasting at 400-500 ℃ for 1.5-3.5 hours, and then putting the precipitate into a reactor for reduction treatment.
4. The method for synthesizing aromatic aldehyde by the gas-phase continuous hydrogenation of aromatic acid or ester according to claim 1, wherein the gasification of aromatic acid or ester is carried out by heating the raw material to a temperature above or below the boiling point with saturated steam.
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| Application Number | Priority Date | Filing Date | Title |
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| CN98122074A CN1073542C (en) | 1998-12-07 | 1998-12-07 | Method for synthesizing aromatic aldehyde by continuous catalytic hydrogenation of aromatic acid or aromatic ester |
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| CN98122074A CN1073542C (en) | 1998-12-07 | 1998-12-07 | Method for synthesizing aromatic aldehyde by continuous catalytic hydrogenation of aromatic acid or aromatic ester |
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| CN1225353A CN1225353A (en) | 1999-08-11 |
| CN1073542C true CN1073542C (en) | 2001-10-24 |
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| CN98122074A Expired - Fee Related CN1073542C (en) | 1998-12-07 | 1998-12-07 | Method for synthesizing aromatic aldehyde by continuous catalytic hydrogenation of aromatic acid or aromatic ester |
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| CN107954840B (en) * | 2016-10-14 | 2020-07-28 | 中国石油化工股份有限公司 | Method for preparing benzaldehyde and benzyl alcohol |
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| US458900A (en) * | 1891-09-01 | Car-coupling |
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| US458900A (en) * | 1891-09-01 | Car-coupling |
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