CN102285891A - Method for preparing arylamine by catalytic hydrogenation of aromatic nitro compound - Google Patents
Method for preparing arylamine by catalytic hydrogenation of aromatic nitro compound Download PDFInfo
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- CN102285891A CN102285891A CN2011101826585A CN201110182658A CN102285891A CN 102285891 A CN102285891 A CN 102285891A CN 2011101826585 A CN2011101826585 A CN 2011101826585A CN 201110182658 A CN201110182658 A CN 201110182658A CN 102285891 A CN102285891 A CN 102285891A
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- catalytic hydrogenation
- nitro compound
- aromatic nitro
- reaction
- ammonium
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Abstract
The invention discloses a method for preparing arylamine by catalytic hydrogenation of an aromatic nitro compound. The method is to obtain the arylamine of a formula (I) by the catalytic hydrogenation of an aromatic nitro compound shown by a formula (II) and hydrogen in the presence of a catalyst and an ammonium compound serving as an inhibitor. The method disclosed by the invention can obviously reduce the generation of azo compounds and improve the yield and quality of the product.
Description
(1) technical field
The present invention relates to a kind of method by the aromatic nitro compound preparing aromatic amine by catalytic hydrogenation.
(2) background technology
Arylamine is the important organic chemical industry's intermediate of a class, is widely used in fields such as preparation medicine, material, dyestuff, agricultural chemicals.
Catalysis nitryl aromatic compounds hydrogenating reduction prepares the method for aromatic amine compounds, enjoys and payes attention to and be widely used because have the recyclable advantage such as apply mechanically of environmental friendliness, catalyzer.But, when adopting the catalytic hydrogenating reduction method to prepare arylamine, under alkaline condition, can produce azo compounds such as a certain amount of azo, azoxy, hydrodiazo, and under alkaline environment, can stably exist by aromatic nitro compound.For example, Chinese patent CN201010223741.8 discloses a kind of with NaOH, KOH, (CH
3)
3CONa or (CH
3)
3When COK is alkaline assistant, prepare the preparation method of azobenzene derivatives by nitrobenzene derivative, when adopting this method, azo compound content can be up to more than 90% in the final reacting product.Though the pH value that reduces reaction system can reduce the generation of azo compound, under sour environment, there are a large amount of diphenyl amine compounds to generate again.Reaction by the aromatic nitro compound preparing aromatic amine by catalytic hydrogenation is generally all carried out under neutral environment, but still there is a small amount of azo compound to generate document [Zhaoyin Hou, et al, Ind.Eng.Chem.Res., 2010,49,4664-4669] report, with Ni is catalyzer, with oil of mirbane is reactant, when being solvent with ethanol, contains 0.3～2.9% azo compound in the final reaction product.Though azo compound can catalytic hydrogenolysis be an arylamine also, but (for example need higher hydroconversion condition, high temperature and/or high pressure), and under the popular response condition of aromatic nitro compound preparing aromatic amine by catalytic hydrogenation, can and be difficult to its complete hydrogenolysis than stable existence.This not only influences the yield of product, but also has reduced the purity and the quality of product.Therefore, must seek a kind of method that azo compound generates that suppresses.
Existing research only rests on and is translated into arylamine with generating the method for azo compound by catalytic hydrogenolysis.For example Chinese patent CN99807892.1 discloses a kind of method that by-product nitrogen benzide catalytic hydrogenolysis is generated aniline when preparing RT training department, this method has adopted the acid carbon of handling through acetate or phosphoric acid as promotor, be catalyzer with Pd/C, be solvent with aniline, temperature of reaction is 175 ℃, when reaction pressure is 17.6bar, can is that 51～58% the complete hydrogenolysis of nitrogen benzide is an aniline with content.But this method does not have effect when being applied to by the aromatic nitro compound preparing aromatic amine by catalytic hydrogenation, when the acid charcoal consumption of promotor acidity less or acid charcoal is more weak, suppress the DeGrain that azo generates, and when the acidity of acid charcoal consumption increase or acid charcoal strengthens, can cause the generation of p-diaminodiphenyl again.This method method with the conditioned reaction system pH in essence is similar.
Before the present invention provides, also do not have to solve and when preparing aromatic amine by catalytic hydrogenation, suppress the method that azo compound generates.
(3) summary of the invention
The technical problem to be solved in the present invention provides a kind of method by the aromatic nitro compound preparing aromatic amine by catalytic hydrogenation, can significantly reduce the generation of azo compound, improves the yield and the quality of product.
For solving the problems of the technologies described above, the present invention adopts following technical scheme:
A kind of method by the aromatic nitro compound preparing aromatic amine by catalytic hydrogenation, described method is: in the presence of inhibitor ammonium compounds, aromatic nitro compound shown in the formula (II) and hydrogen obtain the arylamine shown in the formula (I) by catalytic hydrogenation reaction under catalyst action;
In formula (I) or the formula (II) ,-R
1,-R
2,-R
3,-R
4,-R
5Independently be selected from separately one of following groups :-H ,-F ,-Cl ,-Br ,-I ,-CH
3,-CH
2CH
3,-OH ,-NH
2,-OCH
3,-COOCH
3,-SO
3H ,-NHCH
2CH
3,-N (CH
3)
2
The present invention can significantly reduce the generation of azo compound by adding the ammonium compounds as inhibitor.Described ammonium compounds can be selected from following a kind of or several combination arbitrarily: ammonium chloride, Neutral ammonium fluoride, brometo de amonio, ammonium sulfate, ammonium nitrate, ammonium phosphate, ammonium formiate, ammonium acetate, volatile salt.The consumption of described ammonium compounds is 0.0009～0.5wt% of aromatic nitro compound quality, is preferably 0.002～0.2wt%.
The present invention can use conventional hydrogenation catalyst such as Pd, Pt, Ru, Ni etc. as catalyzer, and is concrete, and it is one of following that described catalyzer can be selected from: Pd/C, Pt/C, Ru/C, Ni/C, Pd/Al
2O
3, Pt/Al
2O
3, Ru/Al
2O
3, Ni/Al
2O
3, Pd/SiO
2, Pt/SiO
2, Ru/SiO
2, Ni/SiO
2, Raney-Ni.Described catalyst consumption is 0.1～3.0wt% of aromatic nitro compound quality.
Catalytic hydrogenation reaction of the present invention can be a reaction solvent with methyl alcohol, ethanol or water, or carries out under condition of no solvent.When adding reaction solvent, the adding volume of reaction solvent is 0.5～3.0 times of volume of aromatic nitro compound.
The temperature of catalytic hydrogenation reaction of the present invention is 50～150 ℃, preferred 60～120 ℃.
Catalytic hydrogenation reaction of the present invention, the control hydrogen pressure is 0.4～3MPa, preferably controlling hydrogen pressure is 0.8～2MPa.
The present invention is after catalytic hydrogenation reaction finishes, can obtain target product by conventional separation method, as: behind the stopped reaction, temperature of reaction system is reduced to room temperature, from reactor, take out reaction solution, remove by filter catalyzer, filtrate obtains solvent and target product respectively through distillation or rectification and purification, and the solvent that obtains of purifying can continue on for the hydrogenation reaction solvent.
Described method by the aromatic nitro compound preparing aromatic amine by catalytic hydrogenation, carry out according to following steps: in reactor, add aromatic nitro compound, reaction solvent, catalyzer and inhibitor, the mass ratio that feeds intake of described aromatic nitro compound, catalyzer and inhibitor is 1: 0.1～3.0wt%: 0.0009～0.5wt%, the off-response still, with the air in the nitrogen replacement reactor, use hydrogen exchange again, then reactor temperature is risen to 60～120 ℃ and to control hydrogen pressure be 0.8～2MPa, stirring reaction; Reaction finishes the back separation and obtains arylamine.
Adopt inhibitor of the present invention, the content of azo compound can be reduced to below 0.05% in the product that obtains under above-mentioned reaction conditions.
The present invention compared with prior art has the following advantages:
1) significantly reduces the content of azo compound in the product behind the employing inhibitor of the present invention, promoted the yield and the quality of product.
2) inhibitor of the present invention is applied widely, azo compound is all had the inhibition effect for aromatic nitro compound when the preparing aromatic amine by catalytic hydrogenation.
3) addition of inhibitor of the present invention in catalytic hydrogenation reaction is few, and the ammonium compounds is heated and easily decomposes, and inhibitor is easy to the decomposes volatilization in arylamine product rectification and purification process, so does not contain inhibitor in the arylamine product after the rectifying.
4) inhibitor of the present invention is with low cost, and this inhibitor using method is simple, and easy handling is suitable for applying.
(4) embodiment
Below with specific embodiment technical scheme of the present invention is described, but protection scope of the present invention is not limited thereto:
Embodiment one to five
Embodiment one to five has investigated the influence of inhibitor kind to azo compound inhibition effect.In the 500ml stainless steel cauldron, add 100ml oil of mirbane, 200ml ethanol, 0.5g 5%Pd/C catalyzer (production of Deqing, Zhejiang county moral worker chemical industry company limited), unconstrained dose or adding 0.01g inhibitor, the off-response still, with the air in the nitrogen replacement reactor three times, use hydrogen exchange again three times; It is 2MPa that temperature is risen to 60 ℃, hydrogen pressure, begins to stir stir speed (S.S.) 900r/min, reaction 1h; Stopped reaction, treat that temperature is reduced to room temperature after, take out reaction solution, remove by filter catalyzer, filtrate is used gas chromatographic analysis.Experimental result is as shown in table 1.
Table 1 inhibitor kind suppresses the influence of effect to azo compound
Embodiment six to ten
Embodiment six to ten has investigated the influence of inhibitor consumption to azo compound inhibition effect.In the 500ml stainless steel cauldron, add 100ml Ortho Nitro Toluene, 200ml methyl alcohol, 2g Raney-Ni catalyzer (but damping alloy Manufacturing Co., Ltd in Zhejiang produces), the inhibitor that adds different amounts, the off-response still, with the air in the nitrogen replacement reactor three times, use hydrogen exchange again three times; It is 1MPa that temperature is risen to 70 ℃, hydrogen pressure, begins to stir stir speed (S.S.) 900r/min, reaction 1.5h; Stopped reaction, treat that temperature is reduced to room temperature after, take out reaction solution, remove by filter catalyzer, filtrate is used gas chromatographic analysis.Experimental result is as shown in table 2.
Table 2 inhibitor consumption suppresses the influence of effect to azo compound
Embodiment 11 to 20
When embodiment six to ten had investigated the distinct fragrance nitro-compound and is raw material, inhibitor suppressed the influence of effect to azo compound.In the 500ml stainless steel cauldron, add 100ml aromatic nitro compound, 200ml ethanol, 1g 5%Pt/C catalyzer (production of Deqing, Zhejiang county moral worker chemical industry company limited), add inhibitor, the off-response still, with the air in the nitrogen replacement reactor three times, use hydrogen exchange again three times; It is 1.5MPa that temperature is risen to 100 ℃, hydrogen pressure, begins to stir stir speed (S.S.) 900r/min, reaction 2h; Stopped reaction, treat that temperature is reduced to room temperature after, take out reaction solution, remove by filter catalyzer, filtrate is used gas chromatographic analysis.Experimental result is as shown in table 3.
Table 3 inhibitor is to the influence of the inhibition effect of distinct fragrance nitro-compound
Claims (10)
1. method by the aromatic nitro compound preparing aromatic amine by catalytic hydrogenation, it is characterized in that described method is: in the presence of inhibitor ammonium compounds, aromatic nitro compound shown in the formula (II) and hydrogen obtain the arylamine shown in the formula (I) by catalytic hydrogenation reaction under catalyst action;
In formula (I) or the formula (II) ,-R
1,-R
2,-R
3,-R
4,-R
5Independently be selected from separately one of following groups :-H ,-F ,-Cl ,-Br ,-I ,-CH
3,-CH
2CH
3,-OH ,-NH
2,-OCH
3,-COOCH
3,-SO
3H ,-NHCH
2CH
3,-N (CH
3)
2
2. the method by the aromatic nitro compound preparing aromatic amine by catalytic hydrogenation as claimed in claim 1 is characterized in that: described ammonium compounds is selected from following a kind of or several combination arbitrarily: ammonium chloride, Neutral ammonium fluoride, brometo de amonio, ammonium sulfate, ammonium nitrate, ammonium phosphate, ammonium formiate, ammonium acetate, volatile salt.
3. the method by the aromatic nitro compound preparing aromatic amine by catalytic hydrogenation as claimed in claim 1 is characterized in that: the consumption of described ammonium compounds is 0.0009～0.5wt% of aromatic nitro compound quality.
4. as the described method by the aromatic nitro compound preparing aromatic amine by catalytic hydrogenation of one of claim 1～3, it is characterized in that: described catalyzer is selected from one of following: Pd/C, Pt/C, Ru/C, Ni/C, Pd/Al
2O
3, Pt/Al
2O
3, Ru/Al
2O
3, Ni/Al
2O
3, Pd/SiO
2, Pt/SiO
2, Ru/SiO
2, Ni/SiO
2, Raney-Ni.
5. the method by the aromatic nitro compound preparing aromatic amine by catalytic hydrogenation as claimed in claim 4 is characterized in that: described catalyst consumption is 0.1～3.0wt% of aromatic nitro compound quality.
6. as the described method by the aromatic nitro compound preparing aromatic amine by catalytic hydrogenation of one of claim 1～3, it is characterized in that: described catalytic hydrogenation reaction is a reaction solvent with methyl alcohol, ethanol or water, or carries out under condition of no solvent.
7. as the described method of one of claim 1～3 by the aromatic nitro compound preparing aromatic amine by catalytic hydrogenation, it is characterized in that: described catalytic hydrogenation reaction is a reaction solvent with methyl alcohol, ethanol or water, and the volumetric usage of reaction solvent is 0.5～3 times of aromatic nitro compound volume.
8. as the described method by the aromatic nitro compound preparing aromatic amine by catalytic hydrogenation of one of claim 1～3, it is characterized in that: the temperature of described catalytic hydrogenation reaction is 50～150 ℃, and the control hydrogen pressure is 0.4～3MPa.
9. as the described method by the aromatic nitro compound preparing aromatic amine by catalytic hydrogenation of one of claim 1～3, it is characterized in that: the temperature of described catalytic hydrogenation reaction is 60～120 ℃, and the control hydrogen pressure is 0.8～2MPa.
10. the method by the aromatic nitro compound preparing aromatic amine by catalytic hydrogenation as claimed in claim 7, it is characterized in that: described method is carried out according to following steps: add aromatic nitro compound in reactor, reaction solvent, catalyzer and inhibitor, described aromatic nitro compound, the mass ratio that feeds intake of catalyzer and inhibitor is 1: 0.1～3.0wt%: 0.0009～0.5wt%, the off-response still, with the air in the nitrogen replacement reactor, use hydrogen exchange again, then reactor temperature is risen to 60～120 ℃ and to control hydrogen pressure be 0.8～2MPa, stirring reaction; Reaction finishes the back separation and obtains arylamine.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102766055A (en) * | 2012-06-26 | 2012-11-07 | 长春工业大学 | Hydrogenation phenylamine production method by nitrobenzene hydrogen transfer with ruthenium acetylacetonate as catalyst |
| CN102786424A (en) * | 2012-08-22 | 2012-11-21 | 中国中化股份有限公司 | Method for preparing 3-chloro-4-methylaniline through catalytic hydrogenation |
| CN103664641A (en) * | 2012-09-10 | 2014-03-26 | 中国石油化工股份有限公司 | Method for preparing o-chloroaniline by virtue of solvent-free catalytic hydrogenation |
| CN103664642A (en) * | 2012-09-10 | 2014-03-26 | 中国石油化工股份有限公司 | Method for preparing o-chloroaniline by adopting microchannel reaction device |
| CN104525264A (en) * | 2014-12-16 | 2015-04-22 | 中国科学院宁波材料技术与工程研究所 | Amino metal organic framework material containing active metal component as well as preparation method and application of amino metal organic framework material |
| CN105618055A (en) * | 2014-10-29 | 2016-06-01 | 中国科学院大连化学物理研究所 | Application of nickel-based catalyst in selective hydrogenation reaction of aromatic nitro compound |
| CN106699611A (en) * | 2016-12-30 | 2017-05-24 | 沈阳化工研究院有限公司 | Production method for preparing sodium m-aminobenzene sulfonate by means of continuous hydrogenation reduction |
| CN108947850A (en) * | 2018-07-23 | 2018-12-07 | 蚌埠中实化学技术有限公司 | A kind of preparation method of 3,4,5- trifluoromethyl aniline |
| CN108997138A (en) * | 2018-08-17 | 2018-12-14 | 济南和润化工科技有限公司 | A kind of method of solvent-free catalytic hydrogenation production para-fluoroaniline |
| CN110396046A (en) * | 2019-08-02 | 2019-11-01 | 河北建新化工股份有限公司 | A kind of method of the preparing aromatic amine by catalytic hydrogenation of stability and high efficiency |
| CN114933535A (en) * | 2022-06-10 | 2022-08-23 | 万华化学（宁波）有限公司 | Preparation method of membrane reactor and method for coproducing aniline and 4-aminodiphenylamine from nitrobenzene |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101037393A (en) * | 2007-04-26 | 2007-09-19 | 南京工业大学 | Synthesizing technique of aromatic amines preparation by reducing aromatic nitro-compound |
| WO2007116111A1 (en) * | 2006-04-10 | 2007-10-18 | Consejo Superior De Investigaciones Científicas | Method for preparing amino compounds using gold catalysts |
| EP2123627A1 (en) * | 2007-01-19 | 2009-11-25 | Ube Industries, Ltd. | Process for producing aromatic amine having aralkyloxy or heteroaralkyloxy group |
-
2011
- 2011-06-30 CN CN201110182658.5A patent/CN102285891B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007116111A1 (en) * | 2006-04-10 | 2007-10-18 | Consejo Superior De Investigaciones Científicas | Method for preparing amino compounds using gold catalysts |
| EP2123627A1 (en) * | 2007-01-19 | 2009-11-25 | Ube Industries, Ltd. | Process for producing aromatic amine having aralkyloxy or heteroaralkyloxy group |
| CN101037393A (en) * | 2007-04-26 | 2007-09-19 | 南京工业大学 | Synthesizing technique of aromatic amines preparation by reducing aromatic nitro-compound |
Non-Patent Citations (2)
| Title |
|---|
| D.CHANNE GOWDA等: "Catalytic transfer hydrogenation of aromatic nitro compounds by employing ammonium formate and 5% platinum on carbon", 《SYNTHETIC COMMUNICATIONS》 * |
| 张群峰等: "催化加氢法绿色合成N-(3-氨基-4-甲氧基苯基)乙酰胺", 《精细化工中间体》 * |
Cited By (17)
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| CN102766055A (en) * | 2012-06-26 | 2012-11-07 | 长春工业大学 | Hydrogenation phenylamine production method by nitrobenzene hydrogen transfer with ruthenium acetylacetonate as catalyst |
| CN102786424A (en) * | 2012-08-22 | 2012-11-21 | 中国中化股份有限公司 | Method for preparing 3-chloro-4-methylaniline through catalytic hydrogenation |
| CN103664641A (en) * | 2012-09-10 | 2014-03-26 | 中国石油化工股份有限公司 | Method for preparing o-chloroaniline by virtue of solvent-free catalytic hydrogenation |
| CN103664642A (en) * | 2012-09-10 | 2014-03-26 | 中国石油化工股份有限公司 | Method for preparing o-chloroaniline by adopting microchannel reaction device |
| CN103664642B (en) * | 2012-09-10 | 2016-01-06 | 中国石油化工股份有限公司 | A kind of method adopting microchannel reaction unit to prepare Ortho-Chloro aniline |
| CN103664641B (en) * | 2012-09-10 | 2016-01-20 | 中国石油化工股份有限公司 | A kind of method of solvent-free preparing o-chloroaniline by catalytic hydrogenation |
| CN105618055A (en) * | 2014-10-29 | 2016-06-01 | 中国科学院大连化学物理研究所 | Application of nickel-based catalyst in selective hydrogenation reaction of aromatic nitro compound |
| CN104525264B (en) * | 2014-12-16 | 2017-08-25 | 中国科学院宁波材料技术与工程研究所 | Ammonobase organic framework material, its preparation method and application comprising active metal component |
| CN104525264A (en) * | 2014-12-16 | 2015-04-22 | 中国科学院宁波材料技术与工程研究所 | Amino metal organic framework material containing active metal component as well as preparation method and application of amino metal organic framework material |
| CN106699611A (en) * | 2016-12-30 | 2017-05-24 | 沈阳化工研究院有限公司 | Production method for preparing sodium m-aminobenzene sulfonate by means of continuous hydrogenation reduction |
| CN108947850A (en) * | 2018-07-23 | 2018-12-07 | 蚌埠中实化学技术有限公司 | A kind of preparation method of 3,4,5- trifluoromethyl aniline |
| CN108947850B (en) * | 2018-07-23 | 2021-05-18 | 蚌埠中实化学技术有限公司 | Preparation method of 3,4, 5-trifluoroaniline |
| CN108997138A (en) * | 2018-08-17 | 2018-12-14 | 济南和润化工科技有限公司 | A kind of method of solvent-free catalytic hydrogenation production para-fluoroaniline |
| CN110396046A (en) * | 2019-08-02 | 2019-11-01 | 河北建新化工股份有限公司 | A kind of method of the preparing aromatic amine by catalytic hydrogenation of stability and high efficiency |
| CN110396046B (en) * | 2019-08-02 | 2022-03-18 | 河北建新化工股份有限公司 | Method for preparing arylamine by stable and efficient catalytic hydrogenation |
| CN114933535A (en) * | 2022-06-10 | 2022-08-23 | 万华化学（宁波）有限公司 | Preparation method of membrane reactor and method for coproducing aniline and 4-aminodiphenylamine from nitrobenzene |
| CN114933535B (en) * | 2022-06-10 | 2023-12-19 | 万华化学（宁波）有限公司 | Preparation method of membrane reactor and method for co-producing aniline and 4-aminodiphenylamine from nitrobenzene |
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