CN102260174B - Application of solid acid catalyst in preparation of 2,5-dichloronitrobenzene - Google Patents
Application of solid acid catalyst in preparation of 2,5-dichloronitrobenzene Download PDFInfo
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- CN102260174B CN102260174B CN2011101768518A CN201110176851A CN102260174B CN 102260174 B CN102260174 B CN 102260174B CN 2011101768518 A CN2011101768518 A CN 2011101768518A CN 201110176851 A CN201110176851 A CN 201110176851A CN 102260174 B CN102260174 B CN 102260174B
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Abstract
The invention discloses application of a solid acid catalyst to preparation of 2,5-dichloronitrobenzene. The preparation method comprises the following steps of: fully mixing p-toluenesulfonic acid serving as a catalyst and a p-dichlorobenzene solution in a kettle, dripping 98 mass percent concentrated nitric acid, performing nitration reaction at certain temperature, keeping the temperature after the reaction is finished, and standing; performing solid-liquid separation to obtain a crude product of 2,5-dichloronitrobenzene; and neutralizing the obtained crude product to reach a certain pH value range by using caustic soda, washing with water, and separating to obtain pure 2,5-dichloronitrobenzene. The p-toluenesulfonic acid is used as the catalyst, reaction steps are effectively simplified, and the emission of wastewater and waste liquor is reduced; materials are reacted completely and the utilization rate is high when the 2,5-dichloronitrobenzene is prepared by external circulation nitration reaction; and the finished product prepared by the method has the yield of 125 percent, and the content is more than or equal to 99.8 percent.
Description
Technical field
The present invention relates to the preparation that a kind of solid acid catalyst is applied to 2,5-dichloronitrobenzene.
Background technology
2,5-dichloronitrobenzene, as nitrogen fertilizer potentiating agent, have the fixed nitrogen function of fertilizer retention, also can be used as the intermediate of dyestuff, agricultural chemicals, antiseptic-germicide.At dye industry, for glacial dye large red-based g G, red base 3GL, Fast Red RC base etc., also can prepare 2, the 5-dichlorphenamide bulk powder is as dyestuff intermediate.At pesticide industry, as pesticide intermediate, be the intermediate of herbicide dicamba and quizalofop.The main raw material of 2,5-dichloronitrobenzene or synthetic antibacterial agents triclosan, therefore, domestic 2, the production of 5-dichloronitrobenzene and development prospect are still good.
At present, produce 2,5-dichloronitrobenzene both at home and abroad and be the mixed acid process that utilizes nitric acid or nitric acid, sulfuric acid to form, but traditional reaction system utilizes the stirring tank stirring reaction time long, reaction is incomplete, and yield is low, and product purity is not high.
Summary of the invention
Main task of the present invention is to provide a kind of outer circulation reaction method to be applied to the nitration processes of 2,5-dichloronitrobenzene, is specifically related to the preparation that a kind of solid acid catalyst that is conducive to improve the product yield is applied to 2,5--dichloronitrobenzene.
In order to solve above technical problem, a kind of solid acid catalyst of the present invention is applied to 2, the preparation of 5--dichloronitrobenzene, it is characterized in that: using p-methyl benzenesulfonic acid as catalyzer, after fully mixing in still with santochlor solution, it is 110 ℃ that the concentrated nitric acid that the dropping mass concentration is 98% carries out nitration reaction control temperature of reaction, react completely latter standing 1 hour, after temperature is down to 100 ℃, carry out solid-liquid separation, obtain 2, 5-dichloronitrobenzene crude product, by 2, after 5-dichloronitrobenzene crude product is neutralized to Ph=12-13 with caustic soda, water cleans, separate, obtain sterling 2, the 5-dichloronitrobenzene.
Further, in described nitration reaction, the nitric acid mass concentration is 98%.
Further, the temperature of described nitration reaction is 110 ℃, treats that nitration reaction is complete, is incubated 1-2 hour.
Further, described p-methyl benzenesulfonic acid, concentrated nitric acid, santochlor mol ratio are 1:1.3:1.25.
Further, in described nitration reaction, material adopts outer circulation mode circulating reaction.
The invention has the advantages that: 1. adopt p-methyl benzenesulfonic acid as catalyzer, effectively simplified reactions steps, and reduced the discharge of waste water and waste liquid, and adopt the high feature of zero pour of p-methyl benzenesulfonic acid, carry out effective physical sepn, and the effect of environmental protection has also been played in recycling in cost-saving; 2. utilize the outer circulation nitration reaction, while preparing 2,5-dichloronitrobenzene, material reaction is complete, and utilization ratio is high; 3. the finished product that present method obtains, product content >=99.8%.
The accompanying drawing explanation
Figure is structural representation of the present invention.
Embodiment
Embodiment 1
By p-methyl benzenesulfonic acid 1 molar part, santochlor 1.25 molar part, be placed in reactor and fully be uniformly mixed, after evenly; Above-mentioned material is at the temperature of 110 ℃, and concentrated nitric acid 1.3 molar part that the dropping mass concentration is 98%, carry out nitration reaction.
In above-mentioned nitration reaction, material is the outer circulation reaction, and reactor is special.The structure of its reactor as shown in the figure.
Set out mouth 2 at kettle 1 top of reactor, import 3 is established in bottom, between outlet 2 and import 3, with pipeline 4, connects, and is provided with lift pump 5 on pipeline 4.During use, raw material enters pipeline 4 by lift pump from exporting 2 flows with 5T/h, and then is back to kettle 1 from import 3, and reciprocation cycle reaction 6-8 hour, guarantee that material fully reacts 6-8 hour like this.
Treat that nitration reaction is complete, temperature is controlled to 110 ℃ and is incubated 1-2 hour.Afterwards, standing 0.5 hour, after temperature is down to 100 ℃, p-methyl benzenesulfonic acid reached zero pour, formed solid, and 2,5-dichloronitrobenzene crude product is liquid state, utilizes the zero pour difference of two kinds of products, carries out solid-liquid separation, obtains 2,5-dichloronitrobenzene crude product.
Neutralized with caustic soda in 2,5-dichloronitrobenzene crude product, make 2,5-dichloronitrobenzene Ph reach 11-13, finally with conventional water, clean and realize that impurity separates, and obtains sterling 2, the 5-dichloronitrobenzene.Gained sterling 2,5-dichloronitrobenzene product content 99.8%.
Embodiment 2
By p-methyl benzenesulfonic acid 0.8 molar part, santochlor 1.25 molar part, be placed in reactor and fully be uniformly mixed, after evenly; Above-mentioned material is at the temperature of 105 ℃, and concentrated nitric acid 1.3 molar part that the dropping mass concentration is 98%, carry out nitration reaction.
In above-mentioned nitration reaction, material is the outer circulation reaction, and reactor is special.The structure of its reactor is identical with embodiment 1.Raw material enters pipeline 4 by lift pump from exporting 2 flows with 5T/h, and reciprocation cycle reaction 4-6 hour, guarantee that material fully reacts 5 hours.
Treat that nitration reaction is complete, temperature is controlled to 105 ℃ and is incubated 1-2 hour.Afterwards, standing 0.5 hour, after temperature is down to 100 ℃, p-methyl benzenesulfonic acid reached zero pour, formed solid, and 2,5-dichloronitrobenzene crude product is liquid state, utilizes the zero pour difference of two kinds of products, carries out solid-liquid separation, obtains 2,5-dichloronitrobenzene crude product.
Neutralized with caustic soda in 2,5-dichloronitrobenzene crude product, make 2,5-dichloronitrobenzene Ph reach 11-13, finally with conventional water, clean and realize that impurity separates, and obtains sterling 2, the 5-dichloronitrobenzene.Gained sterling 2,5-dichloronitrobenzene product content 99.3%%.
Embodiment 3
By p-methyl benzenesulfonic acid 1.2 molar part, santochlor 1.25 molar part, be placed in reactor and fully be uniformly mixed, after evenly; Above-mentioned material is at the temperature of 110 ℃, and concentrated nitric acid 1.3 molar part that the dropping mass concentration is 98%, carry out nitration reaction.
In above-mentioned nitration reaction, material is the outer circulation reaction, and reactor is special.The structure of its reactor is identical with embodiment 1.Raw material enters pipeline 4 by lift pump from exporting 2 flows with 5T/h, and reciprocation cycle reaction 8-10 hour, guarantee that material fully reacts 8 hours.
Treat that nitration reaction is complete, temperature is controlled to 110 ℃ and is incubated 1-2 hour.Afterwards, standing 0.5 hour, after temperature is down to 100 ℃, p-methyl benzenesulfonic acid reached zero pour, formed solid, and 2,5-dichloronitrobenzene crude product is liquid state, utilizes the zero pour difference of two kinds of products, carries out solid-liquid separation, obtains 2,5-dichloronitrobenzene crude product.
Neutralized with caustic soda in 2,5-dichloronitrobenzene crude product, make 2,5-dichloronitrobenzene Ph reach 11-13, finally with conventional water, clean and realize that impurity separates, and obtains sterling 2, the 5-dichloronitrobenzene.
Claims (3)
1. a solid acid catalyst is applied to 2, the preparation of 5-dichloronitrobenzene, it is characterized in that: using p-methyl benzenesulfonic acid as catalyzer, after fully mixing in still with santochlor solution, the concentrated nitric acid that the dropping mass concentration is 98%, carry out nitration reaction 6-8 hour at the temperature of 110 ℃, be incubated after completion of the reaction 1-2 hour, then standing 1 hour, carry out solid-liquid separation, obtain 2,5-dichloronitrobenzene crude product; After 2,5-dichloronitrobenzene crude product is neutralized to pH=11-13 with caustic soda, water cleans, separates, and obtains sterling 2, the 5-dichloronitrobenzene.
2. a kind of solid acid catalyst according to claim 1 is applied to the preparation of 2,5-dichloronitrobenzene, it is characterized in that: described p-methyl benzenesulfonic acid, concentrated nitric acid, santochlor mol ratio are 1:1.3:1.25.
3. described a kind of solid acid catalyst is applied to the preparation of 2,5-dichloronitrobenzene according to claim 1, it is characterized in that: in described nitration reaction, material adopts outer circulation mode circulating reaction, speed of circulation 5T/h.
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102675120A (en) * | 2012-05-24 | 2012-09-19 | 江苏隆昌化工有限公司 | Preparation method of 3, 4-dichloronitrobenzene by solid acid catalyst |
| CN102731313A (en) * | 2012-05-24 | 2012-10-17 | 江苏隆昌化工有限公司 | Application of a green nitrating agent N2O5-HNO3in 2, 5-dichloronitrobenzene nitration |
| CN103044262A (en) * | 2013-01-27 | 2013-04-17 | 厦门大学 | Synthesis method for 2,5-dichloronitrobenzene |
| CN103450025A (en) * | 2013-09-18 | 2013-12-18 | 葫芦岛天启晟业化工有限公司 | Application of anti-isomer additive in 2,5-dichloronitrobenzene production nitration reaction |
| CN104230716A (en) * | 2014-08-28 | 2014-12-24 | 厦门大学 | Method for enhancing nitration reaction rate of 2,5-dichloronitrobenzene |
| CN105152936B (en) * | 2015-09-14 | 2017-10-10 | 江苏隆昌化工有限公司 | A kind of method that solid acid catalysis nitrifies paracide |
| CN106008223B (en) * | 2016-05-31 | 2018-08-31 | 江苏隆昌化工有限公司 | A kind of method of nitrofying aromatic hydrocarbon chloride |
| CN110560084A (en) * | 2018-06-06 | 2019-12-13 | 中国石油化工股份有限公司 | Preparation method and application of nitration catalyst |
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