CN1117056C - Process for synthesizing benzaldehyde by gas-phase hydrogenation of benzoate - Google Patents
Process for synthesizing benzaldehyde by gas-phase hydrogenation of benzoate Download PDFInfo
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- CN1117056C CN1117056C CN99105263A CN99105263A CN1117056C CN 1117056 C CN1117056 C CN 1117056C CN 99105263 A CN99105263 A CN 99105263A CN 99105263 A CN99105263 A CN 99105263A CN 1117056 C CN1117056 C CN 1117056C
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- 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
- C07C45/41—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by hydrogenolysis or reduction of carboxylic groups or functional derivatives thereof
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Abstract
The present invention relates to a method for synthesizing benzaldehyde by gas-phase hydrogenation of benzoic acid ester, which prepare benzaldehyde by gas-phase hydrogenation of benzoic acid ester under the existence of a MnO-Al2 O3-Cu catalyst prepared by an attaching precipitation method, wherein the main component of the catalyst is Al2 O3, MnO and Cu; active constituents of manganese oxide and copper are distributed on aluminum oxide in a single layer mode; the temperature range of a hydrogenation reaction is from 350 to 500 DEG C; the molar ratio of hydrogen gas to the benzoic acid ester is from 10 to 200; the conversion rate per pass of the benzoic acid ester reaches 98%, and the selectivity of the benzaldehyde reaches 87.5%.
Description
The invention relates to a method for synthesizing benzaldehyde by gas-phase hydrogenation of benzoate.
Benzaldehyde is an important organic chemical product and an important synthetic raw material of fine chemical products such as medicines, spices and resin additives, and the chlorine-free benzaldehyde has important application in the food additive industry of spices.
The traditional benzaldehyde production process adopts a dichlorobenzylidene method, which is mainly an organic synthesis process of adding extra equivalent of auxiliary raw materials such as halogen and the like, and the benzaldehyde product necessarily contains chlorine. In addition, there are a formylation method of benzene and a chlorination method, which are limited by the reaction substrate and the use thereof is limited to a specific case. European patent EPO 150,961 describes a process for the catalytic hydrogenation of benzoates to benzaldehyde, In which a ZrO catalyst is used and the modifying component is selected from one or more of the following elements Al, Se, Ga, In, La, Ce, Pr and Nd. U.S. Pat. No. 4, 4,585,900 describes a process for the catalytic hydrogenation of benzoic acid to benzaldehyde, in which process a-Al is used2O3Y as a carrier2O3The reaction temperature 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. European patent EP0573087 and US5336810 describe 1MK2Adding CO solution into manganese nitrate, aluminum nitrate, copper nitrate and zinc nitrate solution to form mixed solution, coprecipitating at pH 4-10, filtering, drying, reducing, screening and roasting to obtain the catalyst, wherein the optimal component is MnO2/ZnO-ZnAl2O4. US patent US4987265 mentions the preparation of catalysts by coprecipitation of Mn salts with acidic salts (Al, Zr, Ti, Hf, Nb) at PH 7-10.
The invention aims to provide a method for synthesizing benzaldehyde by gas-phase hydrogenation of benzoate.
Embodiments of the invention relate to MnO-Al prepared in an attached precipitation process2O3-preparing benzaldehyde by gas phase hydrogenation of benzoate in the presence of a Cu catalyst. The reaction formula is as follows:
wherein ARCOOR 'is benzoate and R' is alkyl.
The invention uses Al2O3MnO and Cu are distributed in the upper monolayer as a catalyst, and the main component of the catalyst is Al2O3MnO and Cu are prepared by an adhesion precipitation method, reduction and activation are carried out under hydrogen or a hydrogen-nitrogen mixed gas, the reduction temperature is slowly raised to 420 ℃ from 120 ℃, benzoate and hydrogen are continuously preheated and mixed to enter a catalyst bed for reaction after reduction, the hydrogenation reaction temperature range is 350-500 ℃, the molar ratio of hydrogen to benzoate is 10-200, and the liquid hourly space velocity of benzoate is 0.08-0.8/hr.
The hydrogenation reaction temperature is preferably 380 to 420 ℃, the molar ratio of hydrogen to benzoate is preferably 20 to 100, and the liquid hourly space velocity of benzoate is preferably 0.1 to 0.4/hr.
The catalyst used in the invention is MnO-Al prepared by an adhesion precipitation method2O3The Cu catalyst is prepared by firstly loading manganese ions and copper ions on an aluminum hydroxide precipitate toform single-layer distribution, and then adding ammonia water to form a manganese and copper hydroxide precipitate, wherein the preparation method comprises the following steps: (1) dissolving aluminum nitrate in deionized water, and dropwise adding ammonia water to adjust the pH value to 7-9 to obtain an aluminum hydroxide precipitate; (2) dissolving manganese nitrate and copper nitrate in deionized water, precipitating and mixing the obtained solution with aluminum hydroxide to ensure that manganese ions and copper ions are attached to the aluminum hydroxide to form single-layer distribution; (3) adjusting pH of the mixture to 8-10 with ammonia water, washing the precipitate with deionized water to neutrality, oven drying at 120-150 deg.C, and calcining at 450-500 deg.C for 1.5-3.5 hr.(4) The above-mentioned roasted MnO-Al2O3And (4) reducing and activating the Cu mixture by using reducing gas hydrogen or a hydrogen-nitrogen mixed gas to obtain the catalyst for synthesizing benzaldehyde by gas-phase hydrogenation of benzoate.
The content (weight ratio) of manganese oxide in the catalyst is 10-50%, the content (weight ratio) of copper is 1-10%, and the rest is alumina. Experiments prove that the catalyst manganese and copper prepared in the range can form single-layer distribution, and the effect of catalyzing gas-phase hydrogenation of benzoate to synthesize benzaldehyde is good.
The reaction is carried out by gas phase hydrogenation, so that the benzoate needs to be gasified to participate in the reaction, the gasification of the benzoate is realized by heating the raw material to be above or below the boiling point by adopting a saturated steam method, and then the raw material and preheated hydrogen are mixed and superheated and enter a reactor to carry out hydrogenation reaction on a catalyst.
The invention adopts an adhesion precipitation method to prepare MnO-Al2O3-a process for the preparation of benzaldehyde by gas phase hydrogenation of a benzoate in the presence of a Cu catalyst. The method is characterized in that the catalytic hydrogenation reaction is continuously carried out, the benzoate hydrogenation is completed in one step, the process is simple, the conversion rate and the selectivity of the catalytic hydrogenation are high, and the product is the chlorine-free benzaldehyde which can be used as a raw material and an additive in various industries of chemical industry, spice and food.
Example 15 g MnO-Al prepared by attachment precipitation2O3The Cu catalyst is loaded in a stainless steel reactor with a diameter of 14mm, the manganese oxide content (weight ratio) of the catalyst being 20%, the copper content (weight ratio) 2% and the alumina content (weight ratio) 78%. Firstly, reducing by using mixed gas of hydrogen and nitrogen, and slowly raising the reduction temperature from 120 ℃ to 420 ℃. After reduction, the methyl benzoate is injected into a gasifier by a metering device, mixed with preheated hydrogen, heated and then enters a catalytic bed for reaction, and the methyl benzoate enters a reactorThe material amount is 4.0ml/hr, the hydrogen feeding amount flow is 0.02m/h, the reaction temperature is 410-420 ℃, the conversion rate of the methyl benzoate is 98 percent, and the selectivity of the benzaldehyde is 87.9 percent.
2. In this example, the catalyst prepared in example 1 was used, 5 g of the catalyst was charged in a stainless steel reactor having a diameter of 14mm, and the catalyst reduction and ethyl benzoate raw material were fed in the same manner as in example 1, wherein the feeding amount of ethyl benzoate was 3.5ml/hr, the feeding flow rate of hydrogen was 0.021m/h, the reaction temperature was 410 ℃ to 420 ℃, the conversion rate of ethyl benzoate was 98%, and the selectivity of benzaldehyde was 86.5%.
3.5 g of MnO-Al prepared by an adhesion precipitation method2O3The Cu catalyst was loaded in a stainless steel reactor having a diameter of 14mm, the manganese oxide content (weight ratio) of the catalyst was 35%, the copper content was 5%, and the alumina content was 60%, and the catalyst reduction method was the same as in example 1, ethyl benzoateThe ester is fed by saturated steam, the evaporation temperature is controlled at 120 ℃, and the feeding flow of hydrogen is 0. 0040m/h, the reaction temperature is 390-400 ℃, the conversion rate of ethyl benzoate is 99%, and the selectivity of benzaldehyde is 85.9%.
4.5 g of MnO-Al prepared by an adhesion precipitation method2O3The Cu catalyst was charged into a stainless steel reactor having a diameter of 14mm, the manganese oxide content (weight ratio) of the catalyst was 32%, the copper content was 8%, and the alumina content was 60%, and the catalyst reduction and raw material methyl benzoate feeding method were the same as in example 1, the feeding amount of methyl benzoate was 4.5ml/hr, the feeding amount of hydrogen was 0.045m/h, the reaction temperature was 385 ℃ to 395 ℃, the conversion rate of methyl benzoate was 100%, and the selectivity of benzaldehyde was 81.9%.
Claims (6)
1. A process for synthesizing benzaldehyde by gas-phase hydrogenation of benzoate features that the MnO-Al prepared by adhesion precipitation method is used2O3In the presence of a Cu catalyst, gasified benzoate and hydrogen are mixed and then continuously enter a catalytic bed for hydrogenation reaction, and the activation and reaction conditions are as follows: (1) the reduction temperature of the catalyst is 120-420 ℃; (2) the molar ratio of hydrogen to benzoate is 10-200, and the liquid hourly space velocity of benzoate is 0.08-0.8/hr; (3) the hydrogenation reaction temperature range is 350-500 ℃.
2. The method for synthesizing benzaldehyde by vapor-phase hydrogenation of benzoate as claimed in claim 1, wherein the molar ratio of hydrogen to benzoate is 20-100, the liquid hourly space velocity of benzoate is 0.1-0.4/hr, and the reaction temperature is 380-420 ℃.
3. The method for synthesizing benzaldehyde by gas-phase hydrogenation of benzoate according to claim 1, wherein the catalyst comprises MnO and Al as main components2O3Cu in Al2O3MnO and Cu are distributed on the upper single layer.
4. The benzoate vapor phase according to claim 1The method for synthesizing benzaldehyde by hydrogen is characterized in that the catalyst is MnO-Al prepared by an adhesion precipitation method2O3The Cu catalyst is prepared by firstly loading manganese ions and copper ions on an aluminum hydroxide precipitate to form single-layer distribution, and then adding ammonia water to form a manganese and copper hydroxide precipitate, wherein the preparation method comprises the following steps: (1) dissolving aluminum nitrate in deionized water, and dropwise adding ammonia water to adjust the pH value to 7-9 to obtain an aluminum hydroxide precipitate; (2) dissolving manganese nitrate and copper nitrate in deionized water, precipitating and mixing the obtained solution with aluminum hydroxide to ensure that manganese ions and copper ions are attached to the aluminum hydroxide to form single-layer distribution;(3) adjusting the pH value of the mixed solution to 8-10 with ammonia water, washing the obtained precipitate with deionized water to neutrality, drying at the temperature of 120-150 ℃, and roasting at the temperature of 450-500 ℃ for 1.5-3.5/hr; (4) the above-mentioned roasted MnO-Al2O3And (4) reducing and activating the Cu mixture by using reducing gas hydrogen or hydrogen-nitrogen mixed gas to obtain the catalyst for synthesizing benzaldehyde by gas-phase hydrogenation of benzoate.
5. The method for synthesizing benzaldehyde by gas-phase hydrogenation of benzoate according to claim 1 or 4, wherein the catalyst contains manganese oxide 10-50 wt%, copper 1-10 wt%, and alumina in balance.
6. The method for synthesizing benzaldehyde by gas-phase hydrogenation of benzoate according to claim 1, wherein the gasification of benzoate is carried out by heating the feedstock to a temperature above or below the boiling point with saturated steam.
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| CN99105263A CN1117056C (en) | 1999-04-28 | 1999-04-28 | Process for synthesizing benzaldehyde by gas-phase hydrogenation of benzoate |
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| CN99105263A CN1117056C (en) | 1999-04-28 | 1999-04-28 | Process for synthesizing benzaldehyde by gas-phase hydrogenation of benzoate |
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| CN1271717A CN1271717A (en) | 2000-11-01 |
| CN1117056C true CN1117056C (en) | 2003-08-06 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101538655B (en) * | 2009-04-28 | 2011-11-23 | 合肥工业大学 | MnO recovery from waste lithium manganate battery positive electrode material 2 And applications thereof |
| CN103204767B (en) * | 2013-04-25 | 2015-12-09 | 江苏理工学院 | Phenylformic acid gas-phase catalytic hydrogenation prepares the method without chlorobenzaldehyde |
| 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 |
| CN106588607B (en) * | 2016-11-25 | 2019-04-05 | 湖南中岭化工有限责任公司 | A kind of methyl benzoate adds hydrogen to prepare the process of benzaldehyde |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4585899A (en) * | 1985-01-22 | 1986-04-29 | Chem Systems Inc. | Hydrogenation of carboxylic acid compounds to aldehydes using MnO2 on gamma alumina as catalyst |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4585899A (en) * | 1985-01-22 | 1986-04-29 | Chem Systems Inc. | Hydrogenation of carboxylic acid compounds to aldehydes using MnO2 on gamma alumina as catalyst |
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