CN102001952A - Preparation method of high-purity paranitroaniline - Google Patents
Preparation method of high-purity paranitroaniline Download PDFInfo
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- CN102001952A CN102001952A CN200910034221XA CN200910034221A CN102001952A CN 102001952 A CN102001952 A CN 102001952A CN 200910034221X A CN200910034221X A CN 200910034221XA CN 200910034221 A CN200910034221 A CN 200910034221A CN 102001952 A CN102001952 A CN 102001952A
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Abstract
The invention belongs to the field of fine chemical engineering, relating to a method for preparing high-purity paranitroaniline from paranitrochlorobenzene. The invention is characterized in that the paranitrochlorobenzene, ammonia water and a phase transfer catalyst are taken as raw materials; the paranitroaniline is prepared by carrying out an ammonolysis reaction on the raw materials; the amount ratio of the paranitrochlorobenzene to the ammonia water substance is 1:5-1:50; the additive amount of the phase transfer catalyst is 0 to 15% of the mass of the raw material paranitrochlorobenzene; the temperature is 100 to 200 DEG C, the pressure is 1.0 to 6.0MPa, and the reaction time is 5 to 10h; and the ammonolysis is carried out on the raw materials to prepare the paranitroaniline. The method of the invention has the advantages that the reaction conditions are mild; the amount of the generated waste water is less; the purity of the prepared paranitroaniline can reach above 98.0% with no need of purification treatment, and the yield is larger than 96.0%; and the integral process course has the advantages of safety, environment protection, low energy consumption, low cost and high yield.
Description
Technical field: the invention belongs to field of fine chemical, relate to the method for p-Nitrophenyl chloride amination production high purity p-Nitroaniline.
Background technology: p-Nitroaniline is a kind of important Organic Chemicals, mainly is used as the intermediate of azoic dyestuff intermediate, agricultural chemicals and veterinary drug, and can be used for making Ursol D, and the latter is as the intermediate of high-strength polymer.At present domestic production producer generally adopts ammonolysis process to produce p-Nitroaniline: para-nitrochloro-benzene, strong aqua are reacted 15～20h under 140～175 ℃, the condition of 4.0～5.5MPa in autoclave, generate p-Nitroaniline, after crystallization, filtration, washing, oven dry, make finished product.This production technique exists unstable product quality, and reaction time is long, the production energy consumption height, and equipment performance requires high shortcoming.
The secondary grade by the emperor himself of woods studied with copper sulfate and sodium-acetate to be catalyzer, to be solvent with the methane amide that the method for the logical ammonia of employing normal pressure is carried out ammonification to single nitro halogeno-benzene, and temperature of reaction is 135 ℃, though reaction conditions is comparatively gentle, per pass conversion is not high.And this technology with more expensive methane amide as solvent, increased reaction cost.
It is synthetic that people such as the Wu Licheng of University Of Xiangtan have studied the catalysis of single N-methyl-p-nitroaniline compounds under phase transfer catalysis condition.At phase-transfer catalyst (tetrabutylammonium chloride, Tetrabutyl amonium bromide, palmityl trimethyl ammonium chloride, the phenyl triethyl ammonium chloride, Polyethylene Glycol-600) under the existence condition, with ammoniacal liquor or low-grade amine (methane amide, diformamide, diethylamide) the aqueous solution is raw material, the aminating reaction that carries out single nitro-chlorobenzene prepares the research of single N-methyl-p-nitroaniline, this technology has relaxed the aminating reaction condition to a certain extent, but the reaction times still needs 10～14h, and the whole yield of this technology p-Nitroaniline is not high, the highest by 92.7%, minimum 16.7%, the single nitro Benzene Chloride of whole technological process does not transform fully, the para-nitrochloro-benzene that generates also needs to use alkali cleaning, washing, series of processes such as steam distillation are removed unreacted single nitro Benzene Chloride.
People such as Wu Xinjian have also studied the technology of the synthetic p-Nitroaniline of phase transfer catalysis process.In autoclave, drop into para-nitrochloro-benzene, ammoniacal liquor, phase-transfer catalyst and the promotor of specified amount, reaction mixture is warming up to test pressure to the specified time reacts, reaction finishes the back and obtains the product p-Nitroaniline by operations such as cooling filtration, washing, oven dry.Phase-transfer catalyst is chosen as TBAB, TBAC, BTEAC, BTMAB.Reaction times and reaction pressure have been reduced to a certain extent by discovering being added in of phase-transfer catalyst, relaxed reaction conditions, but the best yield of whole technological process p-Nitroaniline just reaches about 94%, purity is about 96%, and also needing to add catalyst aid in this technology, this has increased the Separation and Recovery difficulty of production cost and catalyzer to a certain extent.
Summary of the invention: the objective of the invention is to overcome above technical deficiency, provide a kind of reaction conditions to relax that easy handling, product yield height, purity are good, to produce wastewater flow rate minimum environment amenable, and the high purity p-Nitroaniline preparation method that produces of suitable large-scale industrialization.
The present invention is achieved like this: with p-Nitrophenyl chloride, ammoniacal liquor, phase-transfer catalyst is raw material, prepare p-Nitroaniline by ammonolysis reaction, it is characterized in that: under the phase-transfer catalyst existence condition, p-Nitrophenyl chloride, ammoniacal liquor are raw material generation ammonolysis reaction, the ratio of p-Nitrophenyl chloride and ammoniacal liquor amount of substance is 1: 5～1: 50, and the addition of phase-transfer catalyst is 0～15% of a raw material p-Nitrophenyl chloride quality; It is 100～200 ℃ that ammonia is separated temperature, and reaction pressure is 1.0～6.0Mpa, and the reaction times is 5～10h; Ammonia is separated the generation p-Nitroaniline, and reaction solution makes p-Nitroaniline through separation.
Usually, preparation method of the present invention adds p-Nitrophenyl chloride, ammoniacal liquor (weight percentage is 18%～35%) and phase-transfer catalyst in autoclave, can feed the concentration of a certain amount of ammonia increase ammoniacal liquor, be heated to the temperature of reaction reaction under stirring; The kind of phase-transfer catalyst is one or several the mixture in four butyl bromation amine, tetrabutylammonium chloride, 4-propyl bromide, cetyltriethylammonium bromide, palmityl trimethyl ammonium chloride, TBAH, the etamon chloride; Reaction finishes the logical water coolant in back makes the reaction solution cooling, by crystallisation by cooling p-Nitroaniline is separated with mother liquor, and Tc is controlled at 0～50 ℃; Crystalline mother solution and being dissolved in is reused as reaction solution ammoniacal liquor after wherein phase-transfer catalyst fills ammonia, and multiplicity is 2～10 times, and the mother liquor after reusing for several times is through activated carbon decolorizing, condensing crystal Processing of Preparation ammonium chloride industrial goods.
The inventive method is the reaction conditions gentleness not only, and the wastewater flow rate of generation is few, and the p-Nitroaniline that makes do not need purification processes purity can reach more than 98.0%, and yield is greater than 96.0%.Whole technological process is safety and environmental protection not only, and energy consumption is low, cost is low, income is high.
Embodiment: detailed preparation method of the present invention is described below in conjunction with embodiment.
Embodiment 1
In autoclave, add 31.5g p-Nitrophenyl chloride, 3.2g Tetrabutyl amonium bromide, 400mL ammoniacal liquor (concentration is 26%), heated and stirred, temperature of reaction is controlled at 160 ℃～180 ℃, reaction 10h, reaction finishes the logical water quench to 5 in back ℃, crystallization filter p-Nitroaniline, 80 ℃ dry the p-Nitroaniline finished product, gas chromatographic analysis p-Nitroaniline purity is 99.5%, and yield is 97.4%.
Embodiment 2
In autoclave, add 63.0g p-Nitrophenyl chloride, 300mL ammoniacal liquor (concentration is 30%), heated and stirred, temperature of reaction is controlled at 170 ℃～180 ℃, reaction 8h, reaction finishes the logical water coolant in back and reduces to normal temperature, crystallization filter p-Nitroaniline, 80 ℃ dry the p-Nitroaniline finished product, gas chromatographic analysis p-Nitroaniline purity is 99.7%, and yield is 96.5%.
Embodiment 3
In autoclave, add 31.5g p-Nitrophenyl chloride, 1.6g tetrabutylammonium chloride, 400mL ammoniacal liquor (concentration is 25%), heated and stirred, temperature of reaction is controlled at 160 ℃～180 ℃, reaction 10h, reaction finishes the logical water quench to 5 in back ℃, crystallization filter p-Nitroaniline, 80 ℃ dry the p-Nitroaniline finished product, gas chromatographic analysis p-Nitroaniline purity is 98.5%, and yield is 97.0%.
Embodiment 4
Add 47.3g p-Nitrophenyl chloride, 300mL filtered liquid (applying mechanically liquid for the third time) in autoclave, fill ammonia, the control ammonia pressure is 0.2MP, feeding ammonia to pressure does not only reduce to, after filling the ammonia end, heated and stirred, temperature of reaction are controlled at 160 ℃～180 ℃, reaction 10h, reaction finishes the logical water coolant in back and reduces to normal temperature, crystallization filter p-Nitroaniline, 80 ℃ dry the p-Nitroaniline finished product, gas chromatographic analysis p-Nitroaniline purity is 99.9%, and yield is 99.8%.
Claims (5)
1. the preparation method of a high purity p-Nitroaniline, be to be raw material with p-Nitrophenyl chloride, ammoniacal liquor, phase-transfer catalyst, prepare p-Nitroaniline by ammonolysis reaction, it is characterized in that: under the phase-transfer catalyst existence condition, p-Nitrophenyl chloride, ammoniacal liquor are raw material generation ammonolysis reaction, the ratio of p-Nitrophenyl chloride and ammoniacal liquor amount of substance is 1: 5～1: 50, and the addition of phase-transfer catalyst is 0～15% of a raw material p-Nitrophenyl chloride quality; It is 100～200 ℃ that ammonia is separated temperature, and reaction pressure is 1.0～6.0Mpa, and the reaction times is 5～10h; Ammonia is separated the generation p-Nitroaniline, and reaction solution makes p-Nitroaniline through separation.
2. preparation method according to claim 1 is characterized in that phase-transfer catalyst is one or several the mixture in four butyl bromation amine, tetrabutylammonium chloride, 4-propyl bromide, cetyltriethylammonium bromide, palmityl trimethyl ammonium chloride, TBAH, the etamon chloride.
3. preparation method according to claim 1 is characterized in that reaction solution adopts cooling crystallization method to isolate p-Nitroaniline, and Tc is controlled at 0～50 ℃.
4. preparation method according to claim 1 is characterized in that crystalline mother solution and is dissolved in and reuses as reaction solution ammoniacal liquor after wherein phase-transfer catalyst fills ammonia that multiplicity is 2～10 times
5. preparation method according to claim 4, the crystalline mother solution after it is characterized in that reusing for several times prepares the ammonium chloride industrial goods through activated carbon decolorizing, condensing crystal.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102617361A (en) * | 2012-03-12 | 2012-08-01 | 苏州市罗森助剂有限公司 | Preparation method of paranitroaniline |
| CN103420850A (en) * | 2013-07-19 | 2013-12-04 | 浙江闰土股份有限公司 | Continuous production method of paranitroaniline |
| CN104130138A (en) * | 2014-07-04 | 2014-11-05 | 河南洛染股份有限公司 | 2,4-dinitraniline continuous ammonification production technology |
| CN107619372A (en) * | 2016-07-14 | 2018-01-23 | 中国石油化工股份有限公司 | A kind of continuous producing method of paranitroanilinum |
| CN107619373A (en) * | 2016-07-14 | 2018-01-23 | 中国石油化工股份有限公司 | A kind of method for continuously synthesizing of high-purity paranitroaniline |
| CN113511975A (en) * | 2021-06-25 | 2021-10-19 | 宁夏中盛新科技有限公司 | Safe and environment-friendly preparation process of 2, 4-dinitroaniline |
| CN113663727A (en) * | 2021-09-18 | 2021-11-19 | 黔南高新区绿色化工技术研究院有限公司 | Preparation method of supported catalyst with high specific surface area and application of supported catalyst in p-nitroaniline synthesis |
| CN113666828A (en) * | 2021-09-22 | 2021-11-19 | 黔南高新区绿色化工技术研究院有限公司 | Method for preparing p-nitroaniline by catalyzing aminolysis of p-nitrochlorobenzene |
| CN113694916A (en) * | 2021-09-17 | 2021-11-26 | 黔南高新区绿色化工技术研究院有限公司 | Method for synthesizing p-nitroaniline based on hierarchical porous carbon fiber supported phase transfer catalyst |
| CN115160150A (en) * | 2022-06-30 | 2022-10-11 | 国药集团化学试剂有限公司 | Preparation method of high-purity p-phenylenediamine |
| CN117126057A (en) * | 2023-08-29 | 2023-11-28 | 定远县尚时新材料有限公司 | Synthesis process and synthesis system for continuously synthesizing paranitroaniline |
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102617361B (en) * | 2012-03-12 | 2014-03-26 | 苏州市罗森助剂有限公司 | Preparation method of paranitroaniline |
| CN102617361A (en) * | 2012-03-12 | 2012-08-01 | 苏州市罗森助剂有限公司 | Preparation method of paranitroaniline |
| CN103420850A (en) * | 2013-07-19 | 2013-12-04 | 浙江闰土股份有限公司 | Continuous production method of paranitroaniline |
| CN104130138A (en) * | 2014-07-04 | 2014-11-05 | 河南洛染股份有限公司 | 2,4-dinitraniline continuous ammonification production technology |
| CN104130138B (en) * | 2014-07-04 | 2016-03-16 | 河南洛染股份有限公司 | The continuous ammonification production technique of a kind of 2,4-dinitraniline |
| CN107619372A (en) * | 2016-07-14 | 2018-01-23 | 中国石油化工股份有限公司 | A kind of continuous producing method of paranitroanilinum |
| CN107619373A (en) * | 2016-07-14 | 2018-01-23 | 中国石油化工股份有限公司 | A kind of method for continuously synthesizing of high-purity paranitroaniline |
| CN113511975A (en) * | 2021-06-25 | 2021-10-19 | 宁夏中盛新科技有限公司 | Safe and environment-friendly preparation process of 2, 4-dinitroaniline |
| CN113694916A (en) * | 2021-09-17 | 2021-11-26 | 黔南高新区绿色化工技术研究院有限公司 | Method for synthesizing p-nitroaniline based on hierarchical porous carbon fiber supported phase transfer catalyst |
| CN113694916B (en) * | 2021-09-17 | 2024-02-20 | 黔南高新区绿色化工技术研究院有限公司 | Method for synthesizing paranitroaniline based on hierarchical pore carbon fiber supported phase transfer catalyst |
| CN113663727A (en) * | 2021-09-18 | 2021-11-19 | 黔南高新区绿色化工技术研究院有限公司 | Preparation method of supported catalyst with high specific surface area and application of supported catalyst in p-nitroaniline synthesis |
| CN113663727B (en) * | 2021-09-18 | 2024-02-20 | 黔南高新区绿色化工技术研究院有限公司 | Preparation method of supported catalyst with high specific surface area and application of supported catalyst in synthesis of p-nitroaniline |
| CN113666828B (en) * | 2021-09-22 | 2023-12-05 | 黔南高新区绿色化工技术研究院有限公司 | Method for preparing p-nitroaniline by catalyzing ammonolysis of p-nitrochlorobenzene |
| CN113666828A (en) * | 2021-09-22 | 2021-11-19 | 黔南高新区绿色化工技术研究院有限公司 | Method for preparing p-nitroaniline by catalyzing aminolysis of p-nitrochlorobenzene |
| CN115160150A (en) * | 2022-06-30 | 2022-10-11 | 国药集团化学试剂有限公司 | Preparation method of high-purity p-phenylenediamine |
| CN117126057A (en) * | 2023-08-29 | 2023-11-28 | 定远县尚时新材料有限公司 | Synthesis process and synthesis system for continuously synthesizing paranitroaniline |
| CN117126057B (en) * | 2023-08-29 | 2024-03-15 | 定远县尚时新材料有限公司 | Synthesis process and synthesis system for continuously synthesizing paranitroaniline |
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Application publication date: 20110406 |