CN101195579A - Method for synthesizing chloro-aniline by chloronitrobenzene selective hydrogenation in alcohol-water system - Google Patents
Method for synthesizing chloro-aniline by chloronitrobenzene selective hydrogenation in alcohol-water system Download PDFInfo
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- CN101195579A CN101195579A CNA2006101443445A CN200610144344A CN101195579A CN 101195579 A CN101195579 A CN 101195579A CN A2006101443445 A CNA2006101443445 A CN A2006101443445A CN 200610144344 A CN200610144344 A CN 200610144344A CN 101195579 A CN101195579 A CN 101195579A
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Abstract
Provided is a method for synthesizing chlorophenylamine, which adopts chloronitrobenzene as raw material to react under the temperature of 40-140 DEG C and the pressure of 0.2-4 Mpa and the existence of composite solution of alcohol and water and catalyst, wherein the chloronitrobenzene is selectively hydrogenated to produce chlorophenylamine. The method uses alcohol water as solvent and is directly applied in the chloronitrobenzene which is selectively hydrogenated to produce chlorophenylamine, thereby the method has the advantages of high catalyst activity, milder reaction condition and high the yield.
Description
Technical field
The present invention relates to a kind of chloronitrobenzene and select the method for the synthetic chloro aminobenzen of hydrogenation.Particularly, relate to a kind of method of using the synthetic chloro aminobenzen of alcohol-water system selective reduction chloronitrobenzene.
Background technology
Chloro aminobenzen is important organic intermediate, is widely used in synthetic rubber, sensitive materials, dyestuff, medicine, agricultural chemicals etc.As, p-Chlorobenzoic acid amide (p-CAN) is azoic dyestuff and the intermediate of making Naphthol AS-LB, also is the intermediate of not evil medicine (favorable to the people peaceful, Phenacetin), can also be as the coupler of producing colour cinefilm; M-chloro aniline (m-CAN) can be used as the color base of glacial dye, pharmaceutically can make chlorpromazine, Promazine Phosphoricum, chloroquini phosphas etc., also can be as the preparation [CN 1660774] [CN 1762588] of sterilant.Halo aniline is generally generated by the parachloronitrobenzene reduction.Yet the stoichiometry reduction reaction that the traditional industry method is to use iron powder, Sodium Sulphide and hydroborate [GB 873866] etc. to carry out.This method flow is long, and the three wastes are many, poor product quality, and operating environment is poor.With respect to the traditional industry method, catalytic reduction method has the technology advanced person, product purity height, yield height, advantages of environment protection.
The chloronitrobenzene catalysis selective hydrogenation carries out in methyl alcohol or ethanol usually, because the existence of strong adsorption group such as amino and halogen in the reaction system, the solid catalyst activity of ordinary method preparation is lower, as people such as Tijani (Appl.Catal., 1991,76,255～256) reported a kind of supported ruthenium catalyst, its transformation efficiency is difficult to reach 30%.Nanometer metal particle catalyst comparatively effectively.Nanometer ruthenium (J.Mol.Catal.A:Chem., 2001,170,203～208 as polymer protection; J.Mol.Catal.A:Chem., 1999,138,295～303), platinum (J.Mol.Catal.A:Chem., 2003,193,103～108; React.Kinet.Catal.Lett., 2004,81,1～7), rhodium and palladium (Chem.Commum., 2005,924～926) all are catalyzer preferably.In addition, in the reaction process of hydrogenation, because a series of side reactions such as easy generation dehalogenation in order to improve catalyst activity and selectivity, are added additives such as a certain amount of sodium hydroxide, inorganic salt, complexing metal usually to the reaction system kind.Yet the hydrogenation of such material makes that reaction product is difficult to separate, and using to industrial production has increased certain difficulty.
Summary of the invention
The object of the present invention is to provide the method for the synthetic chloro aminobenzen of chloronitrobenzene selection hydrogenation in a kind of alcohol-water system.
For achieving the above object, chloronitrobenzene is selected the method for the synthetic chloro aminobenzen of hydrogenation in the alcohol-water system provided by the invention, with the chloronitrobenzene is raw material, under the condition of alcoholic solvent and catalyzer existence thereof, in temperature of reaction 40-140 ℃, reaction pressure 0.2-4MPa reacts, and obtains chloro aminobenzen;
Described catalyzer is metal or metal supported catalyst, and wherein, metal active constituent is one or several of ruthenium, nickel, iron, cobalt, copper, silver, and the carrier of catalyzer is SiO
2, Al
2O
3, TiO
2, MnO
2, ZnO and Fe
2O
3One or several mixture;
Described method, wherein, chloronitrobenzene is that parachloronitrobenzene, o-chloronitrobenzene are or/and m-chloro-nitrobenzene.
Described method, wherein, chloro aminobenzen is that p-Chlorobenzoic acid amide, Ortho-Chloro aniline are or/and m-chloro aniline.
Described method, wherein, alcoholic solvent is the mixed solvent of alcohol and water, the volume content of water is 0.5-70%.
Described method, wherein, reaction pressure is 0.6-1MPa.
Described method, wherein, temperature of reaction is 80-100 ℃.
The method of the synthetic chloro aminobenzen of simple and effective chloronitrobenzene compounds catalysis selective hydrogenation provided by the invention, concrete is exactly by add water in alcohol, form alcohol-water mixed solvent, utilize the absorption of water at catalyst surface, quicken the desorption of product and stop its absorption reaction again, improved reactive activity and selectivity.This method biggest advantage is exactly not metal ion additives such as (complex compounds) of reaction product, and the contained component of product is simple and easy to separate.Use alcohol-water miscellany as solvent, active and selectivity obviously improves, and cheapness is easily gone, and comparatively environmental protection of low toxicity.
Beneficial effect that the present invention reached and benefit:
1. alcohol-water system is significantly improved than the selectivity and the reactive activity of pure pure system to reaction product in the chloronitrobenzene hydrogenation, and the chloronitrobenzene that this system can apply on the multiple catalyzer is selected hydrogenation.
2. use method of the present invention, can under relatively mild condition, catalysis efficiently select the synthetic chloro aminobenzen of hydrogenation, be easy to industrial applications, and effect is obvious chloronitrobenzene.
3. water is as additive, and is nontoxic, economical, feasible.
Embodiment
Embodiment 1
Be reflected in the 500ml stainless steel autoclave and carry out the Ru/SiO of 0.4g immersion process for preparing
2After catalyzer uses the solution of potassium borohydride reduction, use adding 1.5g parachloronitrobenzene, 105ml dehydrated alcohol and 45ml water in reactor through water and the centrifugal back of washing with alcohol, the off-response device, replace 3 times with excluding air, under stirring condition, be heated to 100 ℃, begin reaction.Finish in the reaction 25min, each components contents of gas chromatographic analysis reaction solution, transformation efficiency is 99.9%, and yield is 98.6%, and TOF is 3.20 * 10
-2S
-1
Embodiment 2
Be reflected in the 500ml stainless steel autoclave and carry out 0.4g Ru/SiO
2After catalyzer uses the solution of potassium borohydride reduction, use through water and the centrifugal back of washing with alcohol, add 1.5g parachloronitrobenzene, 150ml methyl alcohol in reactor, the off-response device is replaced 3 times with excluding air, is heated to 100 ℃ under stirring condition, begins to react.Behind the reaction 120min, each components contents of gas chromatographic analysis reaction solution.Reaction result is as shown in table 1.
Embodiment 3
Except using the 150ml butanols as the solvent, other step is identical with embodiment 3, and reaction result is as shown in table 1.
Embodiment 4
Except using the 150ml amylalcohol as the solvent, other step is identical with embodiment 6, and reaction result is as shown in table 1.
Embodiment 5
Except using the 150ml tetrahydrofuran (THF) as the solvent, other step is identical with embodiment 6, and reaction result is as shown in table 1.
Embodiment 6
Except using the 150ml cyclohexane give as the solvent, other step is identical with embodiment 6, and reaction result is as shown in table 1.
Embodiment 7
Except using 150ml ethanol as the solvent, other step is identical with embodiment 1, and reaction result is as shown in table 1.
Embodiment 8
Except using 7.5ml water and 142.5ml ethanol as the solvent, other step is identical with embodiment 1, and reaction result is as shown in table 1.
Embodiment 9
Except using 15ml water and 135ml ethanol as the solvent, other step is identical with embodiment 1, and reaction result is as shown in table 1.
Embodiment 10
Except using 30ml water and 120ml ethanol as the solvent, other step is identical with embodiment 1, and reaction result is as shown in table 1.
Embodiment 11
Except using 60ml water and 90ml ethanol as the solvent, other step is identical with embodiment 1, and reaction result is as shown in table 1.
Embodiment 12-14
Except temperature of reaction is changed into 60 ℃ respectively, beyond 80 ℃ and 120 ℃, other step is identical with embodiment 1, and reaction result is as shown in table 2.
Embodiment 15-20
Except reaction pressure was changed into 0.2Mpa, 0.4MPa, 0.8MPa and 2MPa respectively, other step was identical with embodiment 1, and reaction result is as shown in table 3.
Embodiment 21-25
Except catalyzer is changed into the Fe/SiO that charge capacity is 5wt%
2, Co/SiO
2, Ni/SiO
2, Cu/SiO
2, Ag/SiO
2In addition, other step is identical with embodiment 1, and reaction result is as shown in table 4.
Comparative example 1-5
Except reaction pressure is changed into the Fe/SiO that charge capacity is 5wt% respectively
2, Co/SiO
2, Ni/SiO
2, Cu/SiO
2, Ag/SiO
2, use 150ml ethanol as outside the solvent, other step is identical with embodiment 1, and reaction result is as shown in table 4.
Embodiment 26
Except using the 1.5g o-chloronitrobenzene as the reaction substrate, other step is shown in embodiment 1.Reaction 30min finishes gas chromatographic analysis, o-chloronitrobenzene transformation efficiency 99.8%, Ortho-Chloro aniline yield 95.7%, catalyst activity 2.67 * 10
-2S
-1
Embodiment 27
Except using the 1.5g m-chloro-nitrobenzene as the reaction substrate, other step is shown in embodiment 1.Reaction 25min finishes gas chromatographic analysis, o-chloronitrobenzene transformation efficiency 99.7%, Ortho-Chloro aniline yield 97.4%, catalyst activity 3.20 * 10
-2S
-1
The influence of table 1 solvent
The influence of table 2 temperature of reaction
The influence of table 3 reaction pressure
Parachloronitrobenzene hydrogenation on the table 4 different metal catalyzer
In the table 4, the mixture of Y:105ml ethanol and 45ml water is as solvent; N:150ml ethanol is as solvent.
Claims (6)
1. chloronitrobenzene is selected the method for the synthetic chloro aminobenzen of hydrogenation in the alcohol-water system, with the chloronitrobenzene is raw material, under the condition of alcoholic solvent and catalyzer existence thereof, in temperature of reaction 40-140 ℃, reaction pressure 0.2-4MPa reacts, and obtains chloro aminobenzen;
Described catalyzer is metal or metal supported catalyst, and wherein, metal active constituent is one or several of ruthenium, nickel, iron, cobalt, copper, silver, and the carrier of catalyzer is SiO
2, Al
2O
3, TiO
2, MnO
2, ZnO and Fe
2O
3One or several mixture.
2. method according to claim 1, wherein, chloronitrobenzene is that parachloronitrobenzene, o-chloronitrobenzene are or/and m-chloro-nitrobenzene.
3. method according to claim 1, wherein, chloro aminobenzen is that p-Chlorobenzoic acid amide, Ortho-Chloro aniline are or/and m-chloro aniline.
4. method according to claim 1, wherein, alcoholic solvent is the mixed solvent of alcohol and water, the volume content of water is 0.5-70%.
5. method according to claim 1, wherein, reaction pressure is 0.6-1MPa.
6. method according to claim 1, wherein, temperature of reaction is 80-100 ℃.
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| CN101863777A (en) * | 2010-05-23 | 2010-10-20 | 青岛科技大学 | Preparation method for solvent-free 2, 4-dimethylaniline and 2, 6-dimethylaniline |
| CN101376634B (en) * | 2008-09-22 | 2011-05-11 | 淮安嘉诚高新化工股份有限公司 | Non-polluted method for producing o-chloroaniline with ferrous powder as reducer |
| CN102701995A (en) * | 2011-12-20 | 2012-10-03 | 山东凯盛新材料股份有限公司 | Preparation method of p-phenylene diamine |
| CN103044268A (en) * | 2012-12-29 | 2013-04-17 | 安徽八一化工股份有限公司 | Application of ammonia gas to preparation of o-chloroaniline by catalytic hydrogenation of ortho-nitrochlorobenzene |
| CN101706485B (en) * | 2009-11-23 | 2013-06-26 | 北京联合大学生物化学工程学院 | Doped nano sensitive material for monitoring benzene |
| CN103524357A (en) * | 2013-09-18 | 2014-01-22 | 葫芦岛天启晟业化工有限公司 | Parachloroaniline production method without using anti-dechlorination agent |
| CN104418756A (en) * | 2013-08-28 | 2015-03-18 | 中国科学院烟台海岸带研究所 | Method and catalyst for synthesizing chloroaniline from chloronitrobenzene by virtue of selective catalytic hydrogenation |
| CN105669338A (en) * | 2014-11-21 | 2016-06-15 | 中国科学院大连化学物理研究所 | Method of preparing aromatic amine by reducing aromatic nitro-compound with hydrazine hydrate |
| CN107417568A (en) * | 2017-05-26 | 2017-12-01 | 长春工业大学 | The method that nitroaromatic catalytic hydrogenation prepares amino aromatic compound |
| CN107456969A (en) * | 2017-08-22 | 2017-12-12 | 兰州大学 | A kind of preparation method and applications of simple substance cobalt load carbon nano-fiber catalyst |
| CN108855126A (en) * | 2017-05-11 | 2018-11-23 | 中国石油化工股份有限公司 | A kind of shell core formula catalyst and preparation method synthesizing m-phenylene diamine (MPD) |
| CN109939713A (en) * | 2019-03-20 | 2019-06-28 | 江苏扬农化工集团有限公司 | A kind of preparation method of the loaded catalyst for chloronitrobenzene catalytic hydrogenation synthesis chloro aminobenzen |
| CN112121802A (en) * | 2020-10-28 | 2020-12-25 | 杭州瑞思新材料有限公司 | Supported nickel-based catalyst, preparation method and application in catalytic hydrogenation reaction of chloronitrobenzene |
| CN114904523A (en) * | 2022-02-22 | 2022-08-16 | 华北电力大学 | Method for preparing N-dimethyl arylamine by catalyzing nitroaromatic hydrocarbon and methanol |
| CN114931967A (en) * | 2022-06-30 | 2022-08-23 | 浙江师范大学 | Preparation method and application of catalyst for preparing arylamine by selective hydrogenation of aromatic nitro compound |
| CN115282956A (en) * | 2022-08-11 | 2022-11-04 | 台州学院 | Titanium dioxide loaded ruthenium metal catalyst and preparation method and application thereof |
| CN115709102A (en) * | 2022-11-10 | 2023-02-24 | 榆林中科洁净能源创新研究院 | Bimetallic nickel-ruthenium catalyst and preparation method and application thereof |
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2006
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101376634B (en) * | 2008-09-22 | 2011-05-11 | 淮安嘉诚高新化工股份有限公司 | Non-polluted method for producing o-chloroaniline with ferrous powder as reducer |
| CN101706485B (en) * | 2009-11-23 | 2013-06-26 | 北京联合大学生物化学工程学院 | Doped nano sensitive material for monitoring benzene |
| CN101863777B (en) * | 2010-05-23 | 2013-08-21 | 青岛科技大学 | Preparation method for solvent-free 2, 4-dimethylaniline and 2, 6-dimethylaniline |
| CN101863777A (en) * | 2010-05-23 | 2010-10-20 | 青岛科技大学 | Preparation method for solvent-free 2, 4-dimethylaniline and 2, 6-dimethylaniline |
| CN102701995A (en) * | 2011-12-20 | 2012-10-03 | 山东凯盛新材料股份有限公司 | Preparation method of p-phenylene diamine |
| CN103044268A (en) * | 2012-12-29 | 2013-04-17 | 安徽八一化工股份有限公司 | Application of ammonia gas to preparation of o-chloroaniline by catalytic hydrogenation of ortho-nitrochlorobenzene |
| CN104418756B (en) * | 2013-08-28 | 2017-04-12 | 中国科学院烟台海岸带研究所 | Method and catalyst for synthesizing chloroaniline from chloronitrobenzene by virtue of selective catalytic hydrogenation |
| CN104418756A (en) * | 2013-08-28 | 2015-03-18 | 中国科学院烟台海岸带研究所 | Method and catalyst for synthesizing chloroaniline from chloronitrobenzene by virtue of selective catalytic hydrogenation |
| CN103524357A (en) * | 2013-09-18 | 2014-01-22 | 葫芦岛天启晟业化工有限公司 | Parachloroaniline production method without using anti-dechlorination agent |
| CN103524357B (en) * | 2013-09-18 | 2015-11-25 | 葫芦岛天启晟业化工有限公司 | Anti-dechlorinating agent is not used to produce p-Chlorobenzoic acid amide method |
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| CN108855126B (en) * | 2017-05-11 | 2021-06-01 | 中国石油化工股份有限公司 | Shell-core catalyst for synthesizing m-phenylenediamine and preparation method thereof |
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| CN109939713A (en) * | 2019-03-20 | 2019-06-28 | 江苏扬农化工集团有限公司 | A kind of preparation method of the loaded catalyst for chloronitrobenzene catalytic hydrogenation synthesis chloro aminobenzen |
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| CN114904523A (en) * | 2022-02-22 | 2022-08-16 | 华北电力大学 | Method for preparing N-dimethyl arylamine by catalyzing nitroaromatic hydrocarbon and methanol |
| CN114931967A (en) * | 2022-06-30 | 2022-08-23 | 浙江师范大学 | Preparation method and application of catalyst for preparing arylamine by selective hydrogenation of aromatic nitro compound |
| CN114931967B (en) * | 2022-06-30 | 2023-12-08 | 浙江师范大学 | Preparation method and application of catalyst for preparing aromatic amine by selective hydrogenation of aromatic nitro compound |
| CN115282956A (en) * | 2022-08-11 | 2022-11-04 | 台州学院 | Titanium dioxide loaded ruthenium metal catalyst and preparation method and application thereof |
| CN115709102A (en) * | 2022-11-10 | 2023-02-24 | 榆林中科洁净能源创新研究院 | Bimetallic nickel-ruthenium catalyst and preparation method and application thereof |
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