CN102285891B - 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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- CN102285891B CN102285891B CN201110182658.5A CN201110182658A CN102285891B CN 102285891 B CN102285891 B CN 102285891B CN 201110182658 A CN201110182658 A CN 201110182658A CN 102285891 B CN102285891 B CN 102285891B
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Abstract
本发明公开了一种由芳香硝基化合物催化加氢制备芳胺的方法，所述的方法为：在抑制剂铵类化合物的存在下，式(II)所示的芳香硝基化合物和氢气在催化剂作用下通过催化加氢反应得到式(I)所示的芳胺。本发明所述方法可显著减少偶氮类化合物的生成，提高产品的收率和品质。 The invention discloses a method for preparing aromatic amines by catalytic hydrogenation of aromatic nitro compounds. The method is as follows: in the presence of inhibitor ammonium compounds, aromatic nitro compounds represented by formula (II) and hydrogen are The arylamine represented by the formula (I) is obtained by catalytic hydrogenation under the action of a catalyst. The method of the invention can significantly reduce the generation of azo compounds, and improve the yield and quality of products.
Description
(1) technical field
The present invention relates to a kind of method by 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 the fields such as preparation medicine, material, dyestuff, agricultural chemicals.
Catalysis nitryl aromatic compounds hydrogenating reduction is prepared 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, while adopting catalytic hydrogenating reduction method to prepare arylamine by aromatic nitro compound, under alkaline condition, can produce the azo compounds such as a certain amount of azo, azoxy, hydrodiazo, and can stably exist under alkaline environment.For example, Chinese patent CN201010223741.8 discloses a kind of with NaOH, KOH, (CH
3)
3cONa or (CH
3)
3when COK is alkaline assistant, prepared the preparation method of azobenzene derivatives by nitrobenzene derivative, while adopting the method, in final reacting product, azo compound content can be up to more than 90%.Although the pH value that reduces reaction system can reduce the generation of azo compound, under sour environment, there are again a large amount of diphenyl amine compounds to generate.Reaction by 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, taking Ni as catalyzer, taking oil of mirbane as reactant, during taking ethanol as solvent, in final reaction product, contain 0.3～2.9% azo compound.Although azo compound can catalytic hydrogenolysis be also arylamine, but (for example need higher hydroconversion condition, high temperature and/or high pressure), and can and be difficult to its complete hydrogenolysis compared with stable existence under the popular response condition of aromatic nitro compound preparing aromatic amine by catalytic hydrogenation.This not only affects the yield of product, but also has reduced 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 by generating azo compound by the method for catalytic hydrogenolysis.For example Chinese patent CN99807892.1 discloses a kind of method that by-product nitrogen benzide catalytic hydrogenolysis is generated to aniline in the time preparing 4-aminodiphenylamine, the method has adopted through acetic acid or the acid-treated acid carbon of phosphorus as promotor, taking Pd/C as catalyzer, taking aniline as solvent, temperature of reaction is 175 DEG C, reaction pressure while being 17.6bar, and the complete hydrogenolysis of nitrogen benzide that can be 51～58% by content is aniline.But the method does not have effect while being applied to by aromatic nitro compound preparing aromatic amine by catalytic hydrogenation, in the time that the acid charcoal consumption of promotor is less or the acidity of acid charcoal is weak, suppress the DeGrain that azo generates, and in the time that the acidity of acid charcoal consumption increase or acid charcoal strengthens, can cause again the generation of p-diaminodiphenyl.The method is similar with the method for adjusting pH value of reaction system in essence.
Before the present invention provides, also do not solve and in the time of 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 is to provide a kind of method by aromatic nitro compound preparing aromatic amine by catalytic hydrogenation, can significantly reduce the generation of azo compound, improves 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 aromatic nitro compound preparing aromatic amine by catalytic hydrogenation, described method is: under the existence of inhibitor ammonium compounds, the aromatic nitro compound shown in formula (II) and hydrogen obtain the arylamine shown in formula (I) by catalytic hydrogenation reaction under catalyst action;
In formula (I) or 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, by adding ammonium compounds as inhibitor, can significantly reduce the generation of azo compound.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 if Pd, Pt, Ru, Ni etc. are as catalyzer, 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.The consumption of described catalyzer is 0.1～3.0wt% of aromatic nitro compound quality.
Catalytic hydrogenation reaction of the present invention can be taking methyl alcohol, ethanol or water as reaction solvent, or carry out under condition of no solvent.In the time adding reaction solvent, the volume that adds 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 DEG C, preferably 60～120 DEG C.
Catalytic hydrogenation reaction of the present invention, 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: after stopped reaction, temperature of reaction system is down to room temperature, from reactor, take out reaction solution, remove by filter catalyzer, filtrate obtains respectively solvent and target product through distillation or rectification and purification, and the solvent obtaining of purifying can continue on for hydrogenation reaction solvent.
The described method by aromatic nitro compound preparing aromatic amine by catalytic hydrogenation, carry out in accordance with the 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%, off-response still, with the air in nitrogen replacement reactor, use again hydrogen exchange, then reactor temperature is risen to 60～120 DEG C and to control hydrogen pressure be 0.8～2MPa, stirring reaction; Reaction finishes rear separation and obtains arylamine.
Adopt inhibitor of the present invention, in the product obtaining under above-mentioned reaction conditions, the content of azo compound can be down to below 0.05%.
The present invention compared with prior art, has the following advantages:
1) significantly reduce the content of azo compound in product after adopting inhibitor of the present invention, promoted yield and the quality of product.
2) inhibitor of the present invention is applied widely, azo compound is all had to inhibition 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 ammonium compounds is heated and easily decomposes, and in arylamine product rectification and purification process, inhibitor is easy to decomposes volatilization, therefore in the arylamine product after rectifying containing inhibitor.
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
With specific embodiment, technical scheme of the present invention is described below, but protection scope of the present invention is not limited to this:
Embodiment mono-to five
Embodiment mono-to five has investigated the impact of inhibitor kind on azo compound inhibition.In 500ml stainless steel cauldron, add 100ml oil of mirbane, 200ml ethanol, 0.5g 5%Pd/C catalyzer (production of Deqing County, Zhejiang De Gong Chemical Co., Ltd.), without inhibitor or add 0.01g inhibitor, off-response still, with the air in nitrogen replacement reactor three times, then use hydrogen exchange three times; It is 2MPa that temperature is risen to 60 DEG C, hydrogen pressure, starts to stir stir speed (S.S.) 900r/min, reaction 1h; Stopped reaction, after temperature is down to room temperature, takes out reaction solution, removes by filter catalyzer, filtrate gas chromatographic analysis.Experimental result is as shown in table 1.
The impact of table 1 inhibitor kind on azo compound inhibition
Embodiment six to ten
Embodiment six to ten has investigated the impact of inhibitor consumption on azo compound inhibition.In 500ml stainless steel cauldron, add 100ml Ortho Nitro Toluene, 200ml methyl alcohol, 2g Raney-Ni catalyzer (Zhejiang can damping alloy Manufacturing Co., Ltd produce), add the inhibitor of different amounts, off-response still, with the air in nitrogen replacement reactor three times, then use hydrogen exchange three times; It is 1MPa that temperature is risen to 70 DEG C, hydrogen pressure, starts to stir stir speed (S.S.) 900r/min, reaction 1.5h; Stopped reaction, after temperature is down to room temperature, takes out reaction solution, removes by filter catalyzer, filtrate gas chromatographic analysis.Experimental result is as shown in table 2.
The impact of table 2 inhibitor consumption on azo compound inhibition
Embodiment 11 to 20
When embodiment six to ten has investigated distinct fragrance nitro-compound and has been raw material, the impact of inhibitor on azo compound inhibition.In 500ml stainless steel cauldron, add 100ml aromatic nitro compound, 200ml ethanol, 1g 5%Pt/C catalyzer (production of Deqing County, Zhejiang De Gong Chemical Co., Ltd.), add inhibitor, off-response still, with the air in nitrogen replacement reactor three times, then use hydrogen exchange three times; It is 1.5MPa that temperature is risen to 100 DEG C, hydrogen pressure, starts to stir stir speed (S.S.) 900r/min, reaction 2h; Stopped reaction, after temperature is down to room temperature, takes out reaction solution, removes by filter catalyzer, filtrate gas chromatographic analysis.Experimental result is as shown in table 3.
The impact of the inhibition of table 3 inhibitor on distinct fragrance nitro-compound
Claims (9)
1. the method by aromatic nitro compound preparing aromatic amine by catalytic hydrogenation, it is characterized in that described method is: under the existence of inhibitor ammonium compounds, the aromatic nitro compound shown in formula (II) and hydrogen obtain the arylamine shown in formula (I) by catalytic hydrogenation reaction under catalyst action; The consumption of described ammonium compounds is 0.0009～0.5% of aromatic nitro compound quality;
In formula (I) or 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 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 aromatic nitro compound preparing aromatic amine by catalytic hydrogenation as claimed in claim 1 or 2, 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.
4. the method by aromatic nitro compound preparing aromatic amine by catalytic hydrogenation as claimed in claim 3, is characterized in that: the consumption of described catalyzer is 0.1～3.0% of aromatic nitro compound quality.
5. the method by aromatic nitro compound preparing aromatic amine by catalytic hydrogenation as claimed in claim 1 or 2, is characterized in that: described catalytic hydrogenation reaction is taking methyl alcohol, ethanol or water as reaction solvent.
6. the method by aromatic nitro compound preparing aromatic amine by catalytic hydrogenation as claimed in claim 1 or 2, it is characterized in that: described catalytic hydrogenation reaction is taking methyl alcohol, ethanol or water as reaction solvent, and the volumetric usage of reaction solvent is 0.5～3 times of aromatic nitro compound volume.
7. the method by aromatic nitro compound preparing aromatic amine by catalytic hydrogenation as claimed in claim 1 or 2, is characterized in that: the temperature of described catalytic hydrogenation reaction is 50～150 DEG C, and control hydrogen pressure is 0.4～3MPa.
8. the method by aromatic nitro compound preparing aromatic amine by catalytic hydrogenation as claimed in claim 1 or 2, is characterized in that: the temperature of described catalytic hydrogenation reaction is 60～120 DEG C, and control hydrogen pressure is 0.8～2MPa.
9. the method by aromatic nitro compound preparing aromatic amine by catalytic hydrogenation as claimed in claim 1, it is characterized in that: described method is carried out in accordance with the following steps: in reactor, add aromatic nitro compound, reaction solvent, catalyzer and inhibitor, described aromatic nitro compound, the mass ratio that feeds intake of catalyzer and inhibitor is 1:0.001～0.03:0.000009～0.005, off-response still, with the air in nitrogen replacement reactor, use again hydrogen exchange, then reactor temperature is risen to 60～120 DEG C and to control hydrogen pressure be 0.8～2MPa, stirring reaction, reaction finishes rear separation and obtains arylamine.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11851387B2 (en) | 2021-08-18 | 2023-12-26 | Yuanhan Materials Inc. | Para-phenylenediamine derivative, 1,4-cyclohexyldiamine derivative, and fabricating method for 1,4-diamine cyclic compound derivative |
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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 |
| CN102786424B (en) * | 2012-08-22 | 2014-09-03 | 中国中化股份有限公司 | Method for preparing 3-chloro-4-methylaniline through catalytic hydrogenation |
| 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 |
| CN106699611B (en) * | 2016-12-30 | 2018-11-13 | 沈阳化工研究院有限公司 | A kind of continuously hydrogen adding reduction prepares the production method of sodium m-aminobenzene sulfonate |
| 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 |
| 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 |
| 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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Cited By (1)
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|---|---|---|---|---|
| US11851387B2 (en) | 2021-08-18 | 2023-12-26 | Yuanhan Materials Inc. | Para-phenylenediamine derivative, 1,4-cyclohexyldiamine derivative, and fabricating method for 1,4-diamine cyclic compound derivative |
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