CN1283612A - Catalytic hydrogenation process for preparing p-aminophenol from nitrobenzene - Google Patents
Catalytic hydrogenation process for preparing p-aminophenol from nitrobenzene Download PDFInfo
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- CN1283612A CN1283612A CN 99114992 CN99114992A CN1283612A CN 1283612 A CN1283612 A CN 1283612A CN 99114992 CN99114992 CN 99114992 CN 99114992 A CN99114992 A CN 99114992A CN 1283612 A CN1283612 A CN 1283612A
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- aminophenol
- reaction
- oil
- mirbane
- nitrobenzene
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
In an intermittent stirring reactor, the nitrobenzene is dissolved in acidic medium under the disperse action of surfactant. The Pt/gamma-Al2O3-MED is used as catalysis to prepared p-aminophenol by catalytic hydrogenation of nitrobenzene. Its advantages are high output rate up to 83% (increased by 10%), and simple prrparing process and high stability of catalyst (its activity is basically constant after cyclic use 10 times).
Description
The present invention relates to prepare the catalyzer and the synthesis technique of p-aminophenol by oil of mirbane.
P-aminophenol (p-Aminophenol is called for short PAP) is a kind of important organic intermediate that is widely used in medicine, the dye well organic synthesis.
China's major part is equipped with p-aminophenol with the iron powder reducing legal system at present, environmental pollution is very serious, shortening method catalytic hydrogenation of nitrobenzene technology was proposed by Henke in 1940, employing be the way that repeatedly adds oil of mirbane, the mol ratio that generates PAP and aniline is 3: 1.People such as Lain-tze add organic acid (as formic acid) in reaction system, yield and selectivity all increase.This method has reduced pollution, has reduced energy consumption, thereby gains great popularity.Its production principle is as follows:
From reaction principle as can be seen, it is a complicated competing reaction that the oil of mirbane shortening prepares PAP, at first oil of mirbane is reduced to oxybenzene amine intermediate under catalyst action, if the further hydrogenation of intermediate generates by product aniline, resets in sour environment and generates PAP.Therefore, improve the yield of PAP, both require catalyzer to have appropriate activity to be beneficial to and generated oxybenzene amine, simultaneously again under suitable condition, make intermediate be rearranged into target product PAP rapidly.For improving the yield of target product, United States Patent (USP) 4,307, in the acid-reaction liquid of making catalyzer with Pt/C, add dimethyl dodecyl chlorination ammonium in 249, Benner adopts dimethyl dodecyl amine oxide to make tensio-active agent, once drop into oil of mirbane, and before transforming fully termination reaction, the separation of realization catalyzer and applying mechanically.Tensio-active agent plays emulsification, dispersion, the role of phase transfer herein, and water is fully contacted with organic phase, fast reaction speed, and its consumption is generally 0.01～0.05% of reaction solution total amount.
The existence of thiophene and other sulfide will have a strong impact on activity of such catalysts and life-span in the raw material oil of mirbane, use H
2O
2Handle sulfuric acid and be beneficial to reaction.But the existence of some sulfide can improve the selectivity of reaction, reduces the generation of by product aniline.United States Patent (USP) 3,715 is in 397, with PtO
2Be catalyzer, the oxybenzene amine that generates in the reaction transformed rapidly to p-aminophenol by in solution, adding methyl-sulphoxide, improve p-aminophenol yield.But the large usage quantity of methyl-sulphoxide in the reaction, the volume ratio of aqueous sulfuric acid and oil of mirbane is higher, and the utilization ratio of reactor is very low.
The shape of reactor, stirring velocity also can influence reaction yield.Kao etc. explicitly call for power of agitator, temperature of reaction, hydrogen pressure, reaction unit and feed way in patent.When agitating vane be positioned at liquid depth 40～60% the time, to the reaction the most favourable, transformation efficiency is 75～80%, product purity 〉=99%.Adopt the two-step reaction method of double-reactor, the oil of mirbane shortening generates hydroxyanilines in first reactor, remove catalyzer after, hydroxyanilines is reset and is generated PAP under sour environment in second reactor, improve the selectivity of reaction, but increased the complicacy of technology.
Discoveries such as Norman, Pt-Ru/C makes catalyzer, can prevent the oil of mirbane excessive hydrogenation, improves the selectivity of reaction.Chinese patent CN85,103,667 propose Pt among the Pt-Ru/C: Ru=5: 1 o'clock, temperature of reaction is between 94～96 ℃, and 14% sulfuric acid is made medium, adds a small amount of dodecyl trimethylammonium amine bromide, keep hydrogen pressure 0.2MPa, behind the reaction 1.2h, the yield of PAP can reach 80%.
The objective of the invention is to: in acidic solution, filter out a kind of have high stability, high reactivity and novel hydrogenation catalyzer optionally, improve the yield of p-aminophenol, for industrialization provides certain basis.
Activity of such catalysts is investigated and is carried out under the following conditions among the present invention: under the normal pressure, in the certain temperature range, utilize tensio-active agent and stirring action that oil of mirbane is dispersed in the acidic medium, hydrogen is made reductive agent, support precious metal and make catalyzer, optionally catalysis oil of mirbane generates oxybenzene amine, generates p-aminophenol after Bamberger resets.
Under this test conditions, through hydrazine reductive Pt/ modification γ-Al
2O
3Catalyzer has good catalytic performance, selectivity of catalyst and active higher.The peak rate of conversion of reaction is greater than 95%, and the yield of p-aminophenol is higher than 80%, and the reaction times is about 1～1.5h.
Temperature of reaction of the present invention is 50～120 ℃, 85～90 ℃ of suitable temperature of reaction, and vitriolic concentration is 8～25%, optimum concn is 10～15%, and dosage of surfactant accounts for 0.5～5% of solution total amount, and sufficient quantity is 1%, properties-correcting agent accounts for 1～10% of carrier total amount, and sufficient quantity is 2～5%.The present invention is simple, convenient, suitability for industrialized production.
Embodiment one
In stirred reactor, add 35ml distilled water, the 3.5ml vitriol oil, 10ml trimethylammonium hexadecyl brometo de amonio solution, Pt/ γ-Al of 0.1g
2O
3Catalyzer under the normal pressure, adds 1ml oil of mirbane and reacts when temperature is 90 ℃ of left and right sides, add 1ml oil of mirbane behind the 0.5h again, and reaction utilizes gas chromatographic analysis to know that the yield of p-aminophenol and aniline is respectively 69% and 28% after finishing.Example two
In stirred reactor, add 35ml distilled water, the 3.5ml vitriol oil, 10ml trimethylammonium hexadecyl brometo de amonio solution, Pt/ γ-Al of 0.1g
2O
3-TiO
2Catalyzer under the normal pressure, adds 1ml oil of mirbane and reacts when temperature is 90 ℃ of left and right sides, add 1ml oil of mirbane behind the 0.5h again, and reaction utilizes gas chromatographic analysis to know that the yield of p-aminophenol and aniline is respectively 83% and 17% after finishing.Example three
In stirred reactor, add 35ml distilled water, the 3.5ml vitriol oil, 10ml trimethylammonium hexadecyl brometo de amonio solution, Pt/ γ-Al of 0.1g
2O
3-CeO
2Catalyzer under the normal pressure, adds 1ml oil of mirbane and reacts when temperature is 90 ℃ of left and right sides, 0.5h back again adds 1ml oil of mirbane, and reaction utilizes gas chromatographic analysis to know that the yield of p-aminophenol and aniline is respectively 79% and 21% after finishing.Example four
In stirred reactor, add 35ml distilled water, the 3.5ml vitriol oil, 10ml trimethylammonium hexadecyl brometo de amonio solution, 5mlBF
3(OC
2H
5) 2, Pt/ γ-Al of 0.1g
2O
3-TiO
2Catalyzer under the normal pressure, adds 1ml oil of mirbane and reacts when temperature is 90 ℃ of left and right sides, add 1ml oil of mirbane behind the 0.5h again, and reaction utilizes gas chromatographic analysis to know that the yield of p-aminophenol and aniline is respectively 86% and 13% after finishing.Example five
Used catalyzer in the example 2 under same reaction conditions, after 9 circulations, is measured the yield of p-aminophenol and aniline in the 10th secondary response liquid, and the two is respectively 80% and 14%.Example six
In stirred reactor, add 35ml distilled water, 3.5ml the vitriol oil, 10ml trimethylammonium hexadecyl brometo de amonio solution, 0.1g the Pt/C catalyzer, under the normal pressure, add 1ml oil of mirbane when temperature is 90 ℃ of left and right sides and react, 0.5h after add 1ml oil of mirbane again, utilize gas chromatographic analysis to know that the yield of p-aminophenol and aniline is respectively 72% and 19% after reaction finishes.
Claims (6)
1 one kinds prepare the new catalyst of p-aminophenol by the oil of mirbane shortening, and its active ingredient is Pt, and carrier is the γ-Al of modification
2O
3
2 according to the requirement in the claim 1, it is characterized in that altered contents is a metal oxide, comprises titanium dioxide and rare earth oxide.
3 according to the requirement in the claim 2, and the content that it is characterized in that altered contents is 0.5～10%.
4 according to the requirement in the claim 1, it is characterized in that catalyzer makes reductive agent with hydrazine.
5 according to the requirement in the claim 1, and the temperature range that it is characterized in that preparation feedback is 50～120 ℃, and optimum temperature range is 85～90 ℃.
6 according to the requirement in the claim 1, and the content of active ingredient is 0.5～5%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB991149920A CN1183099C (en) | 1999-07-08 | 1999-07-08 | Catalytic hydrogenation process for preparing p-aminophenol from nitrobenzene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB991149920A CN1183099C (en) | 1999-07-08 | 1999-07-08 | Catalytic hydrogenation process for preparing p-aminophenol from nitrobenzene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1283612A true CN1283612A (en) | 2001-02-14 |
| CN1183099C CN1183099C (en) | 2005-01-05 |
Family
ID=5278015
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB991149920A Expired - Fee Related CN1183099C (en) | 1999-07-08 | 1999-07-08 | Catalytic hydrogenation process for preparing p-aminophenol from nitrobenzene |
Country Status (1)
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|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1325159C (en) * | 2004-03-22 | 2007-07-11 | 四川大学 | Catalyzer for preparing p-aminophenol by using hydrogenation rearrangement through selection of nitrobenzene |
| CN1328244C (en) * | 2002-03-15 | 2007-07-25 | 南京工业大学 | Production process of p-aminophenol |
| CN108722417A (en) * | 2017-04-17 | 2018-11-02 | 中国科学院成都有机化学有限公司 | A kind of C for being catalyzed hydrogenation of chloronitrobenzene60Immobilized Ni bases catalyst and preparation method thereof |
| CN113200876A (en) * | 2021-05-20 | 2021-08-03 | 安徽东至广信农化有限公司 | Synthesis process of p-aminophenol |
| CN115636758A (en) * | 2022-10-18 | 2023-01-24 | 海南新澜科技有限公司 | Preparation method of p-aminophenol |
-
1999
- 1999-07-08 CN CNB991149920A patent/CN1183099C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1328244C (en) * | 2002-03-15 | 2007-07-25 | 南京工业大学 | Production process of p-aminophenol |
| CN1325159C (en) * | 2004-03-22 | 2007-07-11 | 四川大学 | Catalyzer for preparing p-aminophenol by using hydrogenation rearrangement through selection of nitrobenzene |
| CN108722417A (en) * | 2017-04-17 | 2018-11-02 | 中国科学院成都有机化学有限公司 | A kind of C for being catalyzed hydrogenation of chloronitrobenzene60Immobilized Ni bases catalyst and preparation method thereof |
| CN113200876A (en) * | 2021-05-20 | 2021-08-03 | 安徽东至广信农化有限公司 | Synthesis process of p-aminophenol |
| CN115636758A (en) * | 2022-10-18 | 2023-01-24 | 海南新澜科技有限公司 | Preparation method of p-aminophenol |
| CN115636758B (en) * | 2022-10-18 | 2024-06-04 | 海南新澜科技有限公司 | Preparation method of p-aminophenol |
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| Publication number | Publication date |
|---|---|
| CN1183099C (en) | 2005-01-05 |
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| PB01 | Publication | ||
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| C14 | Grant of patent or utility model | ||
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| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Changzhou Yinsheng Pharmaceutical Co.,Ltd. Assignor: Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences Contract record no.: 2011320000292 Denomination of invention: Catalytic hydrogenation process for preparing p-aminophenol from nitrobenzene Granted publication date: 20050105 License type: Exclusive License Open date: 20010214 Record date: 20110316 |
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| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20050105 Termination date: 20110708 |