CN100418943C - Production method of 3,4-dichloro aniline - Google Patents
Production method of 3,4-dichloro aniline Download PDFInfo
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- CN100418943C CN100418943C CNB2005100505948A CN200510050594A CN100418943C CN 100418943 C CN100418943 C CN 100418943C CN B2005100505948 A CNB2005100505948 A CN B2005100505948A CN 200510050594 A CN200510050594 A CN 200510050594A CN 100418943 C CN100418943 C CN 100418943C
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- dichloronitrobenzene
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Abstract
The present invention relates to a method for preparing 3, 4-dichloroaniline. 3, 4-dichloronitrobenzene as raw material is reduced at 130 to 180 DEG C in the presence of alcoholic solution and a catalyst, and after complete reaction, products are treated to obtain 3, 4-dichloroaniline, wherein the catalyst is Ru-Fe/Al2O3, and the dosage of the catalyst is 1% to 40% of the weight of 3, 4-dichloronitrobenzene. Hydrogen is directly obtained from the catalytic cracking of alcoholic solution, and the hydrogen can be directly used in the catalytic hydrogenation of o-chloronitrobenzene, so that the method of the present invention has the advantages of high yield and low cost and can effectively inhibit dehydrogenation.
Description
(1) technical field
The present invention relates to a kind ofly 3, the preparation method of 4-dichlorphenamide bulk powder relates in particular to 3,4-dichloronitrobenzene liquid phase catalytic hydrogenation system 3, the method for 4-dichlorphenamide bulk powder.
(2) background technology
3, the 4-dichlorphenamide bulk powder is the important chemical intermediate of medicine, agricultural chemicals, dyestuff, spices etc., and purposes is very extensive.3, the synthetic method of 4-dichlorphenamide bulk powder has iron powder reducing method, sodium sulfide reducing method and shortening method usually, preceding two kinds of synthetic method serious environment pollutions, the subject matter that the shortening method exists is to use hydrogen, because hydrogen is inflammable gas, danger is very big aborning, and stores, transports difficulty, and most of medium-sized and small enterprises do not have hydrogen source, directly have influence on applying of this vanguard technology of shortening.The hydrogen transference method can reach 3 without hydrogen, 4-dichloronitrobenzene reduction is synthetic 3, the purpose of 4-dichlorphenamide bulk powder, but must use higher alcohols as hydrogen donor, and each pure molecule can only utilize a hydrogen atom, thus increase production cost greatly.
Another problem that the shortening method exists is a hydrodechlorination.Address this problem two approach are arranged usually: (1) adds the dechlorination inhibitor in the shortening system: (2) improve the performance of catalyzer, reach the purpose that suppresses dechlorination, for example U.S. Pat 4070401 discloses the chloronitrobenzene catalytic hydrogenation process, in reaction system, add polyamine, it at 100 ℃, hydrogen pressure reaction 150 minutes under the condition of 5.0Mpa, dechlorination rate is 0.4%, owing in reaction system, introduced the dechlorination inhibitor, increase identity and produced cost, and reduced quality product; US5554573 is with improved Renay-Ni hydrogenation catalyst, in the alloy of Ni/Al=1, add Mo, make the Renay-Ni/Mo hydrogenation catalyst, remaining Al has bigger influence to catalytic activity and selectivity, this patent is the hydrogenation object with 3-chlorine 4-fluoronitrobenzene, be to react under the condition of 1.8Mpa at 60 ℃, hydrogen pressure, dechlorination rate is between 0.4-3.5%, this hydrogenation catalyst is subjected to the influence of Al, catalytic activity is littler than Renay-Ni, and high active of hydrogenation catalysis descends comparatively fast in reaction process, so the catalyzer usage quantity of unit product is higher.Increase production cost, and dechlorination is still relatively serious, reduces quality product.
(3) summary of the invention
In order to overcome in the prior art 3,4-dichloronitrobenzene shortening synthetic 3, the 4-dichlorphenamide bulk powder must provide hydrogen source and the higher deficiency of dechlorination rate outside reactive system, the invention provides a kind of reactive system confession hydrogen source and dechlorination rate low 3, the preparation method of 4-dichlorphenamide bulk powder.
The technical solution adopted for the present invention to solve the technical problems is:
A kind of 3,4-dichlorphenamide bulk powder production method, with 3, the 4-dichloronitrobenzene is a raw material, 3, the 4-dichloronitrobenzene carries out reduction reaction under 130 ℃～180 ℃ in the presence of alcoholic solution and catalyzer, the aftertreatment that reacts completely gets 3, the 4-dichlorphenamide bulk powder, and wherein said catalyzer is: Ru-Fe/Al
2O
3, described catalyst consumption is 1%～40% of a raw materials quality, better catalyst consumption is 1%～20% of a raw materials quality.
Preferred alcoholic solution is an aqueous ethanolic solution in this reaction, and in the aqueous ethanolic solution, alcoholic acid quality percentage composition is 70%～98% preferably, and better alcoholic acid quality percentage composition is 92%～97%.
Preferably, described reduction reaction is carried out in fixed-bed reactor, and the flow of described reduction reaction is 0.1～1.0ml/min, and better reacting flow is 0.2～0.4ml/min.
When carrying out reduction reaction in other closed reactors, the reaction times is 3～8 hours preferably, and better the reaction times is 5～6 hours.
Described 3, be made into reaction solution in the molten and described aqueous ethanolic solution of 4-dichloronitrobenzene, in the described reaction solution 3, the quality percentage composition of 4-dichloronitrobenzene is preferably 1%-20%, and better the quality percentage composition is 2%-12%, most preferably is 5%-10%.
Especially, recommend according to following steps preparation 3 the 4-dichlorphenamide bulk powder:
1. in fixed-bed reactor, add Ru-Fe/Al
2O
3Catalyzer;
2. with 3, the 4-dichloronitrobenzene joins in the aqueous ethanolic solution, is made into 3,4-dichloronitrobenzene reaction solution;
3. the temperature of reaction with fixed-bed reactor is elevated to 130 ℃～180 ℃, simultaneously the reaction solution for preparing is carried out ethanol cracking hydrogen production and 3 by reactor, 4-dichloronitrobenzene hydrogenation reaction with the flow of 0.2～0.4ml/min;
4. collect reaction solution, distillation promptly gets 3, the 4-dichlorphenamide bulk powder.
Of the present invention 3, the beneficial effect of the production method of 4-dichlorphenamide bulk powder mainly shows: reaction directly obtains hydrogen from the solvent alcohol catalytic pyrolysis, this hydrogen can be directly used in the o-chloronitrobenzene catalytic hydrogenation reaction, and yield height, cost are low, and can effectively suppress dechlorination.
(4) embodiment
Below in conjunction with the drawings and specific embodiments the present invention is further described.
Embodiment one
At long 10cm, add 3 gram Ru-Fe/Al in the fixed-bed reactor of diameter 1.0cm
2O
3Catalyzer.With 20 grams 3, it is in 95% the aqueous ethanolic solution, to be made into 3 of 5% quality percentage composition, 4-dichloronitrobenzene reaction solution that the 4-dichloronitrobenzene joins 490ml alcoholic acid mass percent.The temperature of reaction of fixed-bed reactor is elevated to 180 ℃, simultaneously the reaction solution for preparing is carried out ethanol cracking hydrogen production and 3 by reactor, 4-dichloronitrobenzene reduction hydrogenation reaction with the flow of 0.2ml/min.Collection is from the effusive reaction solution of fixed-bed reactor, and with each components contents of gas chromatographic analysis, the result shows, and 3,4-dichloronitrobenzene transformation efficiency is 100%, 3, the selectivity of 4-dichlorphenamide bulk powder is 96.8%.The reaction solution distillation promptly gets 3, the 4-dichlorphenamide bulk powder.
Embodiment two
At long 10cm, add 3 gram Ru-Fe/Al in the fixed-bed reactor of diameter 1.0cm
2O
3Catalyzer.With 40 grams 3, it is in 95% the aqueous ethanolic solution, to be made into 3 of 9.2% quality percentage composition, 4-dichloronitrobenzene reaction solution that the 4-dichloronitrobenzene joins 490ml alcoholic acid mass percent.The temperature of reaction of fixed-bed reactor is elevated to 180 ℃, simultaneously the reaction solution for preparing is carried out ethanol cracking hydrogen production and 3 by reactor, 4-dichloronitrobenzene reduction hydrogenation reaction with the flow of 0.5ml/min.Collection is from the effusive reaction solution of fixed-bed reactor, and with each components contents of gas chromatographic analysis, the result shows, and 3,4-dichloronitrobenzene transformation efficiency is 88.6%, 3, the selectivity of 4-dichlorphenamide bulk powder is 97.2%.The reaction solution distillation promptly gets 3, the 4-dichlorphenamide bulk powder.
Embodiment three
At long 10cm, add 3 gram Ru-Fe/Al in the fixed-bed reactor of diameter 1.0cm
2O
3Catalyzer.With 20 grams 3, it is in 95% the aqueous ethanolic solution, to be made into 3 of 5% quality percentage composition, 4-dichloronitrobenzene reaction solution for the alcoholic acid mass percent that the 4-dichloronitrobenzene joins 490ml alcoholic acid mass percent.The temperature of reaction of fixed-bed reactor is elevated to 150 ℃, simultaneously the reaction solution for preparing is carried out ethanol cracking hydrogen production and 3 by reactor, 4-dichloronitrobenzene reduction hydrogenation reaction with the flow of 0.3ml/min.Collection is from the effusive reaction solution of fixed-bed reactor, and with each components contents of gas chromatographic analysis, the result shows, and 3,4-dichloronitrobenzene transformation efficiency is 99.3%, 3, the selectivity of 4-dichlorphenamide bulk powder is 99.3%.The reaction solution distillation promptly gets 3, the 4-dichlorphenamide bulk powder.
Embodiment four
At long 10cm, add 3 gram Ru-Fe/Al in the fixed-bed reactor of diameter 1.0cm
2O
3Catalyzer.With 20 grams 3, it is in 95% the aqueous ethanolic solution, to be made into 3 of 5% quality percentage composition, 4-dichloronitrobenzene reaction solution that the 4-dichloronitrobenzene joins 490ml alcoholic acid mass percent.The temperature of reaction of fixed-bed reactor is elevated to 130 ℃, simultaneously the reaction solution for preparing is carried out ethanol cracking hydrogen production and 3 by reactor, 4-dichloronitrobenzene reduction hydrogenation reaction with the flow of 0.1ml/min.Collection is from the effusive reaction solution of fixed-bed reactor, and with each components contents of gas chromatographic analysis, the result shows, and 3,4-dichloronitrobenzene transformation efficiency is 88.2%, 3, the selectivity of 4-dichlorphenamide bulk powder is 99.7%.The reaction solution distillation promptly gets 3, the 4-dichlorphenamide bulk powder.
Embodiment five
At long 10cm, add 3 gram Ru-Fe/Al in the fixed-bed reactor of diameter 1.0cm
2O
3Catalyzer.With 20 grams 3, it is in 92% the aqueous ethanolic solution, to be made into 3 of 5% quality percentage composition, 4-dichloronitrobenzene reaction solution that the 4-dichloronitrobenzene joins 490ml alcoholic acid mass percent.The temperature of reaction of fixed-bed reactor is elevated to 150 ℃, simultaneously the reaction solution for preparing is carried out ethanol cracking hydrogen production and 3 by reactor, 4-dichloronitrobenzene reduction hydrogenation reaction with the flow of 0.2ml/min.Collection is from the effusive reaction solution of fixed-bed reactor, and with each components contents of gas chromatographic analysis, the result shows, and 3,4-dichloronitrobenzene transformation efficiency is 98.7%, 3, the selectivity of 4-dichlorphenamide bulk powder is 99.7%.The reaction solution distillation promptly gets 3, the 4-dichlorphenamide bulk powder.
Embodiment six
At long 10cm, add 3 gram Ru-Fe/Al in the fixed-bed reactor of diameter 1.0cm
2O
3Catalyzer.With 40 grams 3, it is in 92% the aqueous ethanolic solution, to be made into 3 of 10% quality percentage composition, 4-dichloronitrobenzene reaction solution that the 4-dichloronitrobenzene joins 490ml alcoholic acid mass percent.The temperature of reaction of fixed-bed reactor is elevated to 150 ℃, simultaneously the reaction solution for preparing is carried out ethanol cracking hydrogen production and 3 by reactor, 4-dichloronitrobenzene reduction hydrogenation reaction with the flow of 0.4ml/min.Collection is from the effusive reaction solution of fixed-bed reactor, and with each components contents of gas chromatographic analysis, the result shows, and 3,4-dichloronitrobenzene transformation efficiency is 93.6%, 3, the selectivity of 4-dichlorphenamide bulk powder is 99.5%.The reaction solution distillation promptly gets 3, the 4-dichlorphenamide bulk powder.
Embodiment seven
At long 10cm, add 3 gram Ru-Fe/Al in the fixed-bed reactor of diameter 1.0cm
2O
3Catalyzer.With 40 grams 3, it is in 92% the aqueous ethanolic solution, to be made into 3 of 10% quality percentage composition, 4-dichloronitrobenzene reaction solution that the 4-dichloronitrobenzene joins 490ml alcoholic acid mass percent.The temperature of reaction of fixed-bed reactor is elevated to 180 ℃, simultaneously the reaction solution for preparing is carried out ethanol cracking hydrogen production and 3 by reactor, 4-dichloronitrobenzene reduction hydrogenation reaction with the flow of 0.6ml/min.Collection is from the effusive reaction solution of fixed-bed reactor, and with each components contents of gas chromatographic analysis, the result shows, and 3,4-dichloronitrobenzene transformation efficiency is 96.5%, 3, the selectivity of 4-dichlorphenamide bulk powder is 97.6%.The reaction solution distillation promptly gets 3, the 4-dichlorphenamide bulk powder.
Embodiment eight
With 20 grams 3, it is in 80% the aqueous ethanolic solution, to be made into 3 of 15% quality percentage composition, 4-dichloronitrobenzene reaction solution that the 4-dichloronitrobenzene is dissolved in 138ml alcoholic acid mass percent.With reaction solution, 6 gram Ru-Fe/Al
2O
3Catalyzer joins in the 1000ml stainless steel high-pressure reactor, and the off-response device starts stirring, be warming up to 160 ℃, reacted stopped reaction 4 hours, take out reaction solution, filter out catalyzer, filtrate is with each components contents of gas chromatographic analysis, and the result shows, 3,4-dichloronitrobenzene transformation efficiency is 95.7%, 3, and the selectivity of 4-dichlorphenamide bulk powder is 97.3%.The reaction solution distillation promptly gets 3, the 4-dichlorphenamide bulk powder.
Embodiment nine
With 20 grams 3, it is in 70% the aqueous ethanolic solution, to be made into 3 of 20% quality percentage composition, 4-dichloronitrobenzene reaction solution that the 4-dichloronitrobenzene is dissolved in 95ml alcoholic acid mass percent.With reaction solution, 8 gram Ru-Fe/Al
2O
3Catalyzer joins in the 500ml stainless steel high-pressure reactor, and the off-response device starts stirring, be warming up to 150 ℃, reacted stopped reaction 8 hours, take out reaction solution, filter out catalyzer, filtrate is with each components contents of gas chromatographic analysis, and the result shows, 3,4-dichloronitrobenzene transformation efficiency is 93.1%, 3, and the selectivity of 4-dichlorphenamide bulk powder is 94.2%.The reaction solution distillation promptly gets 3, the 4-dichlorphenamide bulk powder.
Embodiment ten
With 20 grams 3, it is in 98% the aqueous ethanolic solution, to be made into 3 of 2% quality percentage composition, 4-dichloronitrobenzene reaction solution that the 4-dichloronitrobenzene is dissolved in 1236ml alcoholic acid mass percent.With reaction solution, 4 gram Ru-Fe/Al
2O
3Catalyzer joins in the 3000ml stainless steel high-pressure reactor, and the off-response device starts stirring, be warming up to 140 ℃, reacted stopped reaction 5 hours, take out reaction solution, filter out catalyzer, filtrate is with each components contents of gas chromatographic analysis, and the result shows, 3,4-dichloronitrobenzene transformation efficiency is 92.1%, 3, and the selectivity of 4-dichlorphenamide bulk powder is 93.4%.The reaction solution distillation promptly gets 3, the 4-dichlorphenamide bulk powder.
Embodiment 11
With 20 grams 3, the mass percent that the 4-dichloronitrobenzene is dissolved in 2423ml methyl alcohol is in 85% the methanol aqueous solution, to be made into 3 of 1% quality percentage composition, 4-dichloronitrobenzene reaction solution.With reaction solution, 0.2 gram Ru-Fe/Al
2O
3Catalyzer joins in the 5000ml stainless steel high-pressure reactor, and the off-response device starts stirring, be warming up to 180 ℃, reacted stopped reaction 3 hours, take out reaction solution, filter out catalyzer, filtrate is with each components contents of gas chromatographic analysis, and the result shows, 3,4-dichloronitrobenzene transformation efficiency is 88.7%, 3, and the selectivity of 4-dichlorphenamide bulk powder is 91.6%.The reaction solution distillation promptly gets 3, the 4-dichlorphenamide bulk powder.
Embodiment 12
With 20 grams 3, the mass percent that the 4-dichloronitrobenzene is dissolved in the 95ml Virahol is in 70% the isopropanol water solution, to be made into 3 of 20% quality percentage composition, 4-dichloronitrobenzene reaction solution.With reaction solution, 8 gram Ru-Fe/Al
2O
3Catalyzer joins in the 500ml stainless steel high-pressure reactor, and the off-response device starts stirring, be warming up to 150 ℃, reacted stopped reaction 8 hours, take out reaction solution, filter out catalyzer, filtrate is with each components contents of gas chromatographic analysis, and the result shows, 3,4-dichloronitrobenzene transformation efficiency is 90.1%, 3, and the selectivity of 4-dichlorphenamide bulk powder is 93.2%.The reaction solution distillation promptly gets 3, the 4-dichlorphenamide bulk powder.
Embodiment 13
With 20 grams 3, the mass percent that the 4-dichloronitrobenzene is dissolved in the 1202ml propyl carbinol is in 98% the n-butanol aqueous solution, to be made into 3 of 2% quality percentage composition, 4-dichloronitrobenzene reaction solution.With reaction solution, 4 gram Ru-Fe/Al
2O
3Catalyzer joins in the 3000ml stainless steel high-pressure reactor, and the off-response device starts stirring, be warming up to 140 ℃, reacted stopped reaction 5 hours, take out reaction solution, filter out catalyzer, filtrate is with each components contents of gas chromatographic analysis, and the result shows, 3,4-dichloronitrobenzene transformation efficiency is 91.1%, 3, and the selectivity of 4-dichlorphenamide bulk powder is 93.1%.The reaction solution distillation promptly gets 3, the 4-dichlorphenamide bulk powder.
Embodiment 14
With 20 grams 3, the 4-dichloronitrobenzene is dissolved in 146ml1, and the mass percent of 3 butyleneglycols is in 97% 1, the 3 butyleneglycol aqueous solution, to be made into 3 of 12% quality percentage composition, 4-dichloronitrobenzene reaction solution.With reaction solution, 3 gram Ru-Fe/Al
2O
3Catalyzer joins in the 1000ml stainless steel high-pressure reactor, and the off-response device starts stirring, be warming up to 180 ℃, reacted stopped reaction 6 hours, take out reaction solution, filter out catalyzer, filtrate is with each components contents of gas chromatographic analysis, and the result shows, 3,4-dichloronitrobenzene transformation efficiency is 95.2%, 3, and the selectivity of 4-dichlorphenamide bulk powder is 96.2%.The reaction solution distillation promptly gets 3, the 4-dichlorphenamide bulk powder.
Embodiment 15
With 20 grams 3, the mass percent that the 4-dichloronitrobenzene is dissolved in the 136ml tertiary amyl alcohol is in 80% the tertiary amyl alcohol aqueous solution, to be made into 3 of 15% quality percentage composition, 4-dichloronitrobenzene reaction solution.With reaction solution, 6 gram Ru-Fe/Al
2O
3Catalyzer joins in the 1000ml stainless steel high-pressure reactor, and the off-response device starts stirring, be warming up to 160 ℃, reacted stopped reaction 4 hours, take out reaction solution, filter out catalyzer, filtrate is with each components contents of gas chromatographic analysis, and the result shows, 3,4-dichloronitrobenzene transformation efficiency is 90.7%, 3, and the selectivity of 4-dichlorphenamide bulk powder is 91.1%.The reaction solution distillation promptly gets 3, the 4-dichlorphenamide bulk powder.
Embodiment 16
With 20 grams 3, the 4-dichloronitrobenzene is dissolved in the 145ml ethanol, is made into 3 of 15% quality percentage composition, 4-dichloronitrobenzene reaction solution.With reaction solution, 6 gram Ru-Fe/Al
2O
3Catalyzer joins in the 500ml stainless steel high-pressure reactor, and the off-response device starts stirring, be warming up to 180 ℃, reacted stopped reaction 5.5 hours, take out reaction solution, filter out catalyzer, filtrate is with each components contents of gas chromatographic analysis, and the result shows, 3,4-dichloronitrobenzene transformation efficiency is 88.9%, 3, and the selectivity of 4-dichlorphenamide bulk powder is 90.0%.The reaction solution distillation promptly gets 3, the 4-dichlorphenamide bulk powder.
Embodiment 17
At long 10cm, add 7 gram Ru-Fe/Al in the fixed-bed reactor of diameter 1.0cm
2O
3Catalyzer.With 40 grams 3, the 4-dichloronitrobenzene joins in the 455ml methyl alcohol, is made into 3 of 10% quality percentage composition, 4-dichloronitrobenzene reaction solution.The temperature of reaction of fixed-bed reactor is elevated to 170 ℃, simultaneously the reaction solution for preparing is carried out ethanol cracking hydrogen production and 3 by reactor, 4-dichloronitrobenzene reduction hydrogenation reaction with the flow of 0.5ml/min.Collection is from the effusive reaction solution of fixed-bed reactor, and with each components contents of gas chromatographic analysis, the result shows, and 3,4-dichloronitrobenzene transformation efficiency is 94.3%, 3, the selectivity of 4-dichlorphenamide bulk powder is 95.4%.The reaction solution distillation promptly gets 3, the 4-dichlorphenamide bulk powder.
Claims (9)
1. one kind 3,4-dichlorphenamide bulk powder production method, with 3, the 4-dichloronitrobenzene is a raw material, it is characterized in that: 3, and the 4-dichloronitrobenzene is in the presence of alcoholic solution and catalyzer, under 130 ℃～180 ℃, carry out reduction reaction, the aftertreatment that reacts completely gets 3, the 4-dichlorphenamide bulk powder, and wherein said catalyzer is: Ru-Fe/Al
2O
3, described catalyst consumption is 3,1%～40% of 4-dichloronitrobenzene quality.
2. as claimed in claim 13,4-dichlorphenamide bulk powder production method is characterized in that: described catalyst consumption is 3,1%～20% of 4-dichloronitrobenzene quality.
3. as claimed in claim 23,4-dichlorphenamide bulk powder production method is characterized in that: described 3, the 4-dichloronitrobenzene is dissolved in and is made into reaction solution in the aqueous ethanolic solution, and in the described reaction solution 3, the quality percentage composition of 4-dichloronitrobenzene is 1%-20%.
4. as claimed in claim 33,4-dichlorphenamide bulk powder production method is characterized in that: alcoholic acid quality percentage composition is 70%～98% in the described aqueous ethanolic solution.
5. as claimed in claim 43,4-dichlorphenamide bulk powder production method is characterized in that: the described reduction reaction time is 3～8 hours.
6. as claimed in claim 53,4-dichlorphenamide bulk powder production method is characterized in that: the described reduction reaction time is 5～6 hours.
7. as claimed in claim 43,4-dichlorphenamide bulk powder production method is characterized in that: described reduction reaction is carried out in fixed-bed reactor, and the flow of described reduction reaction is 0.1～1.0ml/min.
8. as claimed in claim 73,4-dichlorphenamide bulk powder production method is characterized in that: the flow of described reduction reaction is 0.2～0.4ml/min.
9. as claimed in claim 83,4-dichlorphenamide bulk powder production method is characterized in that: described method is carried out as follows: 1. add Ru-Fe/Al in fixed-bed reactor
2O
3Catalyzer;
2. with 3, the 4-dichloronitrobenzene joins in the aqueous ethanolic solution, is made into 3,4-dichloronitrobenzene reaction solution;
3. the temperature of reaction with fixed-bed reactor is elevated to 130 ℃～180 ℃, simultaneously the reaction solution for preparing is carried out ethanol cracking hydrogen production and 3 by reactor, 4-dichloronitrobenzene reduction hydrogenation reaction with the flow of 0.2～0.4ml/min;
4. collect reaction solution, distillation promptly gets 3, the 4-dichlorphenamide bulk powder.
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| CNB2005100505948A CN100418943C (en) | 2005-07-06 | 2005-07-06 | Production method of 3,4-dichloro aniline |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100369673C (en) * | 2006-03-21 | 2008-02-20 | 浙江工业大学 | Production of 3,4-dichloroaniline catalyst with 3,4-mirbane oil dichloride hydrogenation |
| CN101475515B (en) * | 2009-01-24 | 2012-07-11 | 温州大学 | Method for preparing 5-amino-2-chloro-N-(2,4-xylyl)-benzene sulfonic amide in water phase |
| CN103694124B (en) * | 2012-09-28 | 2016-06-01 | 中国石油化工股份有限公司 | A kind of highly selective prepares the method for 3,4-dichlorphenamide bulk powder |
| CN103113233A (en) * | 2013-01-11 | 2013-05-22 | 山东富原化工有限公司 | Production method for preparing chlorinated aniline via chlorination of nitrobenzene hydrogenation by utilizing solvent-free process |
| CN113563201B (en) * | 2021-07-12 | 2023-10-03 | 浙江迪邦化工有限公司 | Method for continuously and efficiently synthesizing 3, 4-dichloroaniline based on fixed bed microreactor |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0073105A1 (en) * | 1981-08-14 | 1983-03-02 | E.I. Du Pont De Nemours And Company | Hydrogenation process |
| EP0398542A2 (en) * | 1989-05-15 | 1990-11-22 | E.I. Du Pont De Nemours And Company | Process for preparing 3,4-dichloroaniline |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0073105A1 (en) * | 1981-08-14 | 1983-03-02 | E.I. Du Pont De Nemours And Company | Hydrogenation process |
| EP0398542A2 (en) * | 1989-05-15 | 1990-11-22 | E.I. Du Pont De Nemours And Company | Process for preparing 3,4-dichloroaniline |
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