CN1944368A - Process for atmospheric gas phase catalytically synthesizing p-tertiary butyl benz-aldehy through hydrogenating method p-tertiary butyl benzoate - Google Patents
Process for atmospheric gas phase catalytically synthesizing p-tertiary butyl benz-aldehy through hydrogenating method p-tertiary butyl benzoate Download PDFInfo
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- CN1944368A CN1944368A CN 200610117178 CN200610117178A CN1944368A CN 1944368 A CN1944368 A CN 1944368A CN 200610117178 CN200610117178 CN 200610117178 CN 200610117178 A CN200610117178 A CN 200610117178A CN 1944368 A CN1944368 A CN 1944368A
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- tert
- acid methyl
- benzoic acid
- methyl esters
- butyl benzoic
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Abstract
The present invention relates to atmospheric gas phase catalytic methyl p-tertiary butyl benzoate hydrogenating process to synthesize p-tertiary butyl benzaldehyde. During the synthesis, MnO/gamma-Al2O3, ZnO, ZnO/gamma-Al2O3, ZrO2 or CeO2/ZrO2 is used as the catalyst. When MnO/gamma-Al2O3 is used and under the conditions of reaction temperature 440 deg.c, H2/ methyl p-tertiary butyl benzoate molar ratio of 70 and LHSV of 0.4/hr, the present invention has single pass methyl p-tertiary butyl benzoate converting rate up to 93.6 % and p-tertiary butyl benzaldehyde selectivity of 76.2 %.
Description
Technical field
The invention belongs to technical field of chemistry and chemical engineering, be specifically related to a kind of method by the synthetic p-t-Butylbenzaldehyde of p-tert-butyl benzoic acid methyl esters normal pressure gas-phase catalytic hydrogenation.
Background technology
P-t-Butylbenzaldehyde is a kind of typical aromatic aldehyde compound, is important fine chemical product and reaction intermediate, is widely used in fields such as medicine, dyestuff, spices, agricultural chemicals, particularly can be used as the precursor compound of synthetic perfume Ling Lanquan.
The synthesis technique of p-t-Butylbenzaldehyde is more, and traditional synthesis technique mainly is the 4 tert butylbenzyl chloride hydrolysis method, but this technology exists seriously polluted and product in chloride, limited its application in spices, medicine and other fields.
Summary of the invention
The purpose of this invention is to provide a kind ofly can carry out continuously, the synthetic method of technology is simple, the raw material recovery rate is high no chlorine p-t-Butylbenzaldehyde.
The purpose of this invention is to provide the Preparation of catalysts method of the synthetic p-t-Butylbenzaldehyde of a kind of above-mentioned p-tert-butyl benzoic acid methyl esters shortening and the synthetic method of p-t-Butylbenzaldehyde.
P-tert-butyl benzoic acid methyl esters shortening of the present invention is a synthetic method to trimethylphenylmethane formaldehyde in the presence of metal oxide or load type double-metal oxide catalyst, and its reaction formula is:
The present invention is a raw material with the p-tert-butyl benzoic acid methyl esters, after vaporization, mixes by certain mol proportion with hydrogen after the preheating, enters catalytic bed and reacts, and carries out the hydrogenating reduction of gas phase, promptly obtains p-t-Butylbenzaldehyde, and its actual conditions is:
(1) mol ratio of hydrogen and p-tert-butyl benzoic acid methyl esters is 10-200: 1;
(2) reaction pressure is 0.01-0.1MPa;
(3) liquid hourly space velocity of p-tert-butyl benzoic acid methyl esters is 0.1-1.2hr
-1
(4) temperature of reaction is 300-500 ℃;
(5) catalyzer is MnO/ γ-Al
2O
3, ZnO, ZnO/ γ-Al
2O
3, ZrO
2Or CeO
2/ ZrO
2
The preferable reaction conditions of the present invention is:
(1) mol ratio of hydrogen and p-tert-butyl benzoic acid methyl esters is: 50-150: 1;
(2) liquid hourly space velocity of p-tert-butyl benzoic acid methyl esters is 0.2-1.0hr
-1
(3) the hydrogenation reaction temperature is 400-450 ℃.
(4) reaction pressure is 0.01-0.05Mpa.
The present invention adopts the gas-phase catalytic hydrogenation method.The p-tert-butyl benzoic acid methyl esters needs to participate in reaction after vaporizing.The vaporization of p-tert-butyl benzoic acid methyl esters adopts heating raw to the method more than the boiling point to realize, enters reactor then with after mixing through pre-hot hydrogen, and carry out hydrogenation reaction on catalyzer.
The used catalyzer of the present invention is metal oxide catalyst and load type double-metal oxide catalyst, and wherein metal oxide catalyst is ZnO, ZrO
2, load type bimetal catalyst is MnO/ γ-Al
2O
3, ZnO/ γ-Al
2O
3And CeO
2/ ZrO
2，
Wherein:
(1) ZnO catalyst adopts the thermolysis process preparation, is about to ZnCO
3Powder made in 550 ℃ of roasting 4-5 hours after drying.
(2) ZrO
2The preparation of the employing precipitator method is about to a certain amount of ZrOCl
28H
2O is dissolved in the deionized water, stirs down, slowly drips Na
2CO
3Solution is complete to precipitation.Continue to stir after 1 hour and left standstill 10-12 hour.Suspension liquid behind suction filtration solid particulate with deionized water wash to pH to 7-8, under 120 ℃ of conditions, dry then.In air atmosphere, presoma was promptly got catalyzer after 550 ℃ of roasting 4-5 hours.
(3) MnO/ γ-Al
2O
3The catalyzer employing is adhered to the precipitator method and is made, and promptly is with a certain amount of γ-Al
2O
3With Mn (NO
3)
2Aqueous solution, fully stirring down, dropping ammonia extremely precipitates fully, control pH value is at 10-11, continue to stir after 1 hour and left standstill 10-12 hour, behind the suspension liquid suction filtration solid particulate with deionized water wash to pH be 7-8,120 ℃ of oven dry down, make catalyst precursor then, in air atmosphere, presoma was promptly got catalyzer after 550 ℃ of roasting 4-5 hours.
(4) ZnO/ γ-Al
2O
3The catalyzer employing is adhered to the precipitator method and is made, and promptly is with a certain amount of γ-Al
2O
3With Zn (NO
3)
2Aqueous solution, dropping ammonia is to precipitating fully under fully stirring, and control pH value is at 10-11, and lasting the stirring after 1 hour left standstill 10-12 hour, and solid particulate is 7-8 with deionized water wash to pH behind the suspension liquid suction filtration, oven dry under 120 ℃ then.Make catalyst precursor and in air atmosphere, presoma was promptly got catalyzer after 550 ℃ of roasting 4-5 hours.
(5) CeO/ZrO
2Catalyzer adopts coprecipitation method to make, and is about to a certain amount of Ce (NO
3)
36H
2O and Zr (NO
3)
45H
2O is dissolved in the deionized water, and fully under the stirring, extremely precipitation is complete to add ammoniacal liquor, and control PH is 10-11, and lasting the stirring 1 hour left standstill 10-12 hour.Suspension liquid solid particulate behind suction filtration is 7-8 with deionized water wash to pH, and oven dry under 120 ℃ then makes catalyst precursor.Presoma is through 550 ℃ of roasting 4-5 hour postforming in air atmosphere.
Above-mentioned catalyzer has commercially available, and its preparation method is a prior art.
Catalyzer MnO/ γ-Al of the present invention
2O
3, ZnO/ γ-Al
2O
3In preferably MnO or ZnO content be 1% to 25% (wt%), γ-Al
2O
3Content be 75% to 99%.Catalyzer CeO
2/ ZrO
2In CeO preferably
2Content be 1% to 25% (wt%), ZrO
2Content be 75% to 99%.
The inventive method can be carried out shortening continuously, one step of p-tert-butyl benzoic acid methyl esters gas phase hydrogenation finishes, reaction conditions is gentle relatively, equipment requirements is lower, technical process is simple, and environmental pollution is less, and the transformation efficiency of no chlorine shortening can reach 93.6% in the product, and selectivity reaches 76.2%.
Embodiment
Embodiment 1:
With 3ml MnO/ γ-Al
2O
3Catalyzer is packed in the reactor, and reaction tube diameter is 5mm.Catalyzer before reaction in hydrogen atmosphere 450 ℃ of reduction activations 2 hours.The p-tert-butyl benzoic acid methyl esters squeezed in the vaporizer with volume pump gasify, mix with hydrogen through preheating, entering catalytic bed again after heating reacts, the inlet amount of p-tert-butyl benzoic acid methyl esters is 1.2ml/hr, the hydrogen feed flow is 40ml/hr, temperature of reaction is 440 ℃, and the transformation efficiency of p-tert-butyl benzoic acid methyl esters is 93.6%, is 76.2% to the selectivity of tertiary butyl formaldehyde.
Embodiment 2:
Adopt the ZnO catalyst of thermolysis process preparation to pack in the reactor 3ml, reaction tube diameter is 5mm.The feed process of the activation method of catalyzer and p-tert-butyl benzoic acid methyl esters is with example 1, the inlet amount of p-tert-butyl benzoic acid methyl esters is 1.2ml/hr, the feed rate of hydrogen is 40ml/hr, the temperature of hydrogenation reaction is 420 ℃, the transformation efficiency of p t butylbenzoic acid methyl esters is 81.4%, and the selectivity of p-t-Butylbenzaldehyde is 51.2%.
Embodiment 3:
3ml is adopted the ZnO/ γ-Al that adheres to precipitator method preparation
2O
3Catalyzer is packed in the reactor, and reaction tube diameter is 5mm.The feed process of the activation method of catalyzer and p-tert-butyl benzoic acid methyl esters is with example 1, the inlet amount of p-tert-butyl benzoic acid methyl esters is 1.2ml/hr, the feed rate of hydrogen is 40ml/hr, the temperature of hydrogenation reaction is 420 ℃, the transformation efficiency of p-tert-butyl benzoic acid methyl esters is 88.9%, and the selectivity of p-t-Butylbenzaldehyde is 73.0%.
Embodiment 4:
3ml is adopted the ZrO of precipitator method preparation
2Catalyzer is packed in the reactor, and reaction tube diameter is 5mm.The feed process of the activation method of catalyzer and p-tert-butyl benzoic acid methyl esters is with example 1, the inlet amount of p-tert-butyl benzoic acid methyl esters is 1.2ml/hr, the feed rate of hydrogen is 40ml/hr, the temperature of hydrogenation reaction is 430 ℃, the transformation efficiency of p-tert-butyl benzoic acid methyl esters is 93.7%, and the selectivity of p-t-Butylbenzaldehyde is 73.4%.
Embodiment 5:
3ml is adopted the CeO of coprecipitation method preparation
2/ ZrO
2Catalyzer is packed in the reactor, and reaction tube diameter is 5mm.The feed process of the activation method of catalyzer and p-tert-butyl benzoic acid methyl esters is with example 1, the inlet amount of p-tert-butyl benzoic acid methyl esters is 1.2ml/hr, the feed rate of hydrogen is 40ml/hr, the temperature of hydrogenation reaction is 400 ℃, the transformation efficiency of p-tert-butyl benzoic acid methyl esters is 87.4%, and the selectivity of p-t-Butylbenzaldehyde is 62.7%.
Claims (8)
1, the method for the synthetic p-t-Butylbenzaldehyde of a kind of p-tert-butyl benzoic acid methyl esters normal pressure gas-phase catalytic hydrogenation, it is characterized in that: with the p-tert-butyl benzoic acid methyl esters is raw material, after vaporization, mix by certain mol proportion with the hydrogen after the preheating, enter the catalytic bed reaction, in the presence of metal oxide or load metal oxide catalyzer, carry out normal pressure gas-phase catalytic hydrogenation one-step synthesis p-t-Butylbenzaldehyde, its reaction conditions is:
(1) mol ratio of hydrogen and p-tert-butyl benzoic acid methyl esters is 10-200: 1;
(2) reaction pressure is 0.01-0.1MPa;
(3) liquid hourly space velocity of p-tert-butyl benzoic acid methyl esters is 0.1-1.2hr
-1
(4) temperature of reaction is 300-500 ℃;
(5) catalyzer is MnO/ γ-Al
2O
3, ZnO, ZnO/ γ-Al
2O
3, ZrO
2Or CeO
2/ ZrO
2
2, method according to claim 1 is characterized in that reaction conditions is:
(1) mol ratio of hydrogen and p-tert-butyl benzoic acid methyl esters is 50-150: 1;
(2) reaction pressure is 0.01-0.05MPa;
(3) liquid hourly space velocity of p-tert-butyl benzoic acid methyl esters is 0.2-1.0hr
-1
(4) temperature of hydrogenation reaction is 400-450 ℃.
3, method according to claim 1 is characterized in that raw material p-tert-butyl benzoic acid methyl esters is heated to more than the boiling point vaporization fully and reacts.
4, method according to claim 1 is characterized in that catalyst system therefor is ZnO.
5, method according to claim 1 is characterized in that catalyst system therefor is ZrO
2
6, method according to claim 1 is characterized in that catalyst system therefor is MnO/ γ-Al
2O
3
7, method according to claim 1 is characterized in that catalyst system therefor is ZnO/ γ-Al
2O
3
8, method according to claim 1 is characterized in that catalyst system therefor is CeO
2/ ZrO
2
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610117178 CN1944368A (en) | 2006-10-16 | 2006-10-16 | Process for atmospheric gas phase catalytically synthesizing p-tertiary butyl benz-aldehy through hydrogenating method p-tertiary butyl benzoate |
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|---|---|---|---|
| CN 200610117178 CN1944368A (en) | 2006-10-16 | 2006-10-16 | Process for atmospheric gas phase catalytically synthesizing p-tertiary butyl benz-aldehy through hydrogenating method p-tertiary butyl benzoate |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101440028B (en) * | 2008-11-06 | 2012-10-31 | 浙江工业大学 | Process for synthesizing p-tertiary butyl benzaldehyde |
| CN106964343A (en) * | 2017-04-11 | 2017-07-21 | 北京恩泽福莱科技有限公司 | A kind of methyl benzoate Hydrogenation is for catalyst of benzaldehyde and preparation method thereof |
-
2006
- 2006-10-16 CN CN 200610117178 patent/CN1944368A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101440028B (en) * | 2008-11-06 | 2012-10-31 | 浙江工业大学 | Process for synthesizing p-tertiary butyl benzaldehyde |
| CN106964343A (en) * | 2017-04-11 | 2017-07-21 | 北京恩泽福莱科技有限公司 | A kind of methyl benzoate Hydrogenation is for catalyst of benzaldehyde and preparation method thereof |
| CN106964343B (en) * | 2017-04-11 | 2020-06-02 | 北京恩泽福莱科技有限公司 | Catalyst for preparing benzaldehyde by methyl benzoate hydrogenation and preparation method thereof |
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