CN103539680B - Clean production process of 6-chloro-2,4-dinitroaniline - Google Patents
Clean production process of 6-chloro-2,4-dinitroaniline Download PDFInfo
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Abstract
The invention discloses a clean production process of 6-chloro-2,4-dinitroaniline. The clean production process of 6-chloro-2,4-dinitroaniline comprises the following steps: 1, dispersing 2,4-dinitroaniline into hydrochloric acid solution for pulping, then introducing chlorine gas into the solution for reacting, and thus obtaining intermediate reaction solution; and 2, adding the intermediate reaction solution obtained in the step 1 into sodium chlorate solution for reacting, after the reaction is completed, processing the reaction solution to obtain the 6-chloro-2,4-dinitroaniline and mother solution, and returning the mother solution to the step 1 to serve as the hydrochloric acid solution. According to the production process, the chlorine gas and the sodium chlorate are sequentially employed as chloride agents for chlorinating in steps, so that the product purity and yield are improved and the cost of material is reduced; and the quantity of hydrochloric acid after the reaction is completed is kept stable basically, so that the mother solution is convenient to recycle for use and the pollution to environment is reduced.
Description
Technical field
The invention belongs to dyestuff intermediate synthesis field, be specifically related to the process for cleanly preparing of chloro-2, the 4-dinitranilines of a kind of 6-.
Background technology
6-chloro-2,4-dinitraniline, have another name called 2-chloro-4,6-dinitraniline, structure is as shown in formula I, and No. CAS is 3531-19-9, it is a kind of important dyestuff intermediate, as diazo component, be mainly used in the synthesis of EX-SF DISPERSE BLUE EX-SF 300 270,264,259,125 and 130 etc., be widely used in the printing and dyeing industry of synthon by the dispersed dye made it.
The synthetic method of chloro-2, the 4-dinitranilines of current 6-mainly contains four kinds, is described below respectively:
(1), 2,4-dinitranilines pull an oar in hydrochloric acid, the sodium chlorate of wiring solution-forming are joined at leisure in making beating material and carry out chlorination reaction, obtain product.Reaction formula is as follows:
The method reality is relatively more complete, and product purity is more than 98%, and the reaction times is shorter, and yield in unit time is high, stable processing technique, is a kind of reasonable production method.But need a large amount of hydrochloric acid, and mother liquor acidity is lower can not apply mechanically production continuously, produces a large amount of waste water.
(2), by 2,4-dinitraniline be placed in the water medium of iron trichloride or elemental iodine existence, slowly pass into chlorinated with chlorine, obtain product.Reaction formula is as follows:
This production method raw materials cost is lower, but product particle is comparatively large, easily lumps, matt.And foreign matter content is high, fusing point is low, and product yield is low.And also require 2,4-dinitraniline to grind in production process very thin, long reaction time, equipment productivity is not high.
(3), by 2,4-dinitraniline join in acetic acid or methyl alcohol, logical chlorinated with chlorine, obtains product.Reaction formula is as follows:
The method of logical chlorine in acetic aid medium, technological process is fairly simple, and product crystalline form is better, and color and luster is good, and product purity is high, and yield is also better, but needs Dichlorodiphenyl Acetate to regenerate, and increases production cost relatively largely.
(4), by 2,4-dinitraniline be placed in hydrochloric acid, slowly add clorox, obtain product.Reaction formula is as follows:
The method clorox is as chlorizating agent, and reaction process has more by product to produce, poor product quality, and color and luster is dark, and time of chlorinating is longer, and equipment productivity is lower, and aftertreatment is cumbersome.
Summary of the invention
The invention provides the process for cleanly preparing of chloro-2, the 4-dinitranilines of a kind of 6-, this production technique yield is high, and chloro-2, the 4-dinitraniline purity of the 6-obtained are high, and environmental pollution is little.
The process for cleanly preparing of chloro-2, the 4-dinitranilines of a kind of 6-, comprises the steps:
(1) 2,4-dinitraniline is scattered in hydrochloric acid soln pulls an oar, then pass into chlorine and react, obtain intermediate reaction liquid;
(2) the intermediate reaction liquid obtained to step (1) adds sodium chlorate solution and reacts, and after reacting completely, the reaction solution obtained obtains described 6-chlorine 2,4-dinitraniline and mother liquor through aftertreatment;
Described mother liquor turns back in step (1) and applies mechanically as hydrochloric acid soln.
Chlorination reaction of the present invention adopts chlorine and sodium chlorate to carry out successively as chlorination reagent, and when reaction starts, the concentration of 2,4-dinitraniline is high, uses chlorine that reaction just can be made to occur well; Reaction proceeds to the later stage, adopts active higher sodium chlorate to carry out chlorination, reacts more stable, the product purity obtained and yield high; And when adopting chlorine to carry out chlorination reaction, can HCl be produced, and when adopting sodium chlorate to carry out chlorination, HCl can be consumed, after whole reaction terminates, the amount of HCl can be made to keep stable, make mother liquor be convenient to recycle, reduce the pollution to environment.
As preferably, with molar amount, described 2,4-dinitraniline: chlorine: sodium chlorate is 1:0.3 ~ 0.8:0.06 ~ 0.28, now, the HCl concentration after reaction starts and terminates can keep stable, hydrochloric acid mother liquor recycled can be realized easily, reach the object of cleaner production.
In step (1), described 2,4-dinitranilines are pulled an oar in hydrochloric acid, and to form hydrochloride protection amino, and as preferably, in step (1), the mass concentration of described hydrochloric acid soln is 10% ~ 18%;
2,4-described dinitranilines and mass ratio=1:3 ~ 9 of hydrochloric acid soln, now effectively can reduce the amino side reaction reaction occurred, improve the yield of 6-chlorine 2,4-dinitraniline.
In step (1), pulping process can release heat, and temperature is unsuitable too high, and as preferably, in step (1), the temperature of making beating is 20 ~ 60 DEG C.
As preferably, in step (1), passing into the temperature that chlorine carries out reacting is 20 ~ 45 DEG C, and temperature of reaction is too low, and reaction can be made to be difficult to carry out completely, and temperature of reaction is too high, can cause the increase of side reaction.
As preferably, in step (2), the mass percent concentration of described sodium chlorate solution is 20% ~ 40%; The excessive concentration of described sodium chlorate solution, side reaction can increase, and concentration is too low, and reaction is difficult to carry out completely.
As preferably, in step (2), the temperature of reaction is 40 ~ 55 DEG C, and temperature of reaction is too low, and reaction can be made to be difficult to carry out completely, and temperature of reaction is too high, can cause the increase of side reaction.
As preferably, in step (2), described aftertreatment comprises: filtered by described reaction solution, and the solid washing obtained obtains chloro-2, the 4-dinitranilines of described 6-;
The filtrate obtained, directly as mother liquor, is back to step (1).
The reaction times of step (1) is 2 ~ 3 hours, and the reaction times of step (2) is 2 ~ 2.5 hours, now, can make Cl
2substantially run out of, sodium chlorate continues oxidation unreacted raw material completely.
Compared with the existing technology, beneficial effect of the present invention is embodied in:
(1) 2,4-dinitraniline is pulled an oar and is formed hydrochloride protection amino in hydrochloric acid, and first logical chlorine speed of response under a large amount of existence condition of 2,4-dinitraniline is fast, and side reaction is few; Drip sodium chlorate solution's chlorination reaction more more stable, so both ensure that the quality of product and yield also reduce the raw materials cost of product.
(2) produce hydrochloric acid by chlorinated with chlorine, and consume hydrochloric acid with sodium chlorate chlorination, the present invention regulates the acidity of hydrochloric acid mother liquor by the consumption of control 2,4-dinitraniline, chlorine and sodium chlorate, realizes hydrochloric acid mother liquor recycled, reaches the object of cleaner production.
Embodiment
Embodiment 1
In with the 500ml flask of agitator, thermometer, add the hydrochloric acid 350g that mass percent concentration is 12%, add 2,4-dinitraniline 54.9g.After 20 DEG C of making beating half an hour, slowly pass into chlorine 10.65g, the logical chlorine time is 2 hours, logical chlorine temperature is 20 ~ 40 DEG C, logical Bi Baowen is slowly warmed up to 40 DEG C after half an hour, drip the sodium chlorate solution 21.3g of mass percent concentration 30%, time for adding is 1 hour, and temperature of reaction is 40 ~ 55 DEG C.Drip Bi Baowen half an hour, filter, wash to obtain 6-chlorine 2,4-dinitraniline, purity 98.4%, yield 96.5%.Mother liquor is collected lower batch and is all applied mechanically.Mother liquor applies mechanically 10 batches continuously, average purity 97.2%, yield 96.9%.
Embodiment 2
In with the 500ml flask of agitator, thermometer, add the hydrochloric acid 350g that mass percent concentration is 18%, add 2,4-dinitraniline 54.9g.After 30 DEG C of making beating half an hour, slowly pass into chlorine 6.39g, the logical chlorine time is 1 hour, logical chlorine temperature is 20 ~ 40 DEG C, logical Bi Baowen is slowly warmed up to 40 DEG C after half an hour, drip 30% sodium chlorate solution 29.8g, time for adding is 1.5 hours, and temperature of reaction is 40 ~ 55 DEG C.Drip Bi Baowen half an hour, filter, wash to obtain 6-chlorine 2,4-dinitraniline, purity 97.8%, yield 96.2%.Mother liquor is collected lower batch and is all applied mechanically.Mother liquor applies mechanically 10 batches continuously, average purity 96.8%, yield 96.5%.
Embodiment 3
In with the 1000ml flask of agitator, thermometer, add the hydrochloric acid 490g that mass percent concentration is 15%, add 2,4-dinitraniline 54.9g.After 30 DEG C of making beating half an hour, slowly pass into chlorine 8.52g, the logical chlorine time is 2 hours, logical chlorine temperature is 20 ~ 40 DEG C, logical Bi Baowen is slowly warmed up to 40 DEG C after half an hour, drip 30% sodium chlorate solution 25.56g, time for adding is 1.5 hours, and temperature of reaction is 40 ~ 55 DEG C.Drip Bi Baowen half an hour, filter, wash to obtain 6-chlorine 2,4-dinitraniline, purity 98.5%, yield 96.1%.Mother liquor is collected lower batch and is all applied mechanically.Mother liquor applies mechanically 10 batches continuously, average purity 97.1%, yield 95.8%.
Comparative example 1
The NK-505 agitator (rotating speed 11000 revs/min ~ 22000 revs/min) 54.9g2,4-dinitraniline and 100g water being put into dragon stirs into suspension, stand-by.Add in the 1000ml flask of agitator, thermometer mass percent concentration be 10% hydrochloric acid 250g and iron trichloride 0.5g(mother liquid recycle after often criticize add iron trichloride 0.15g), 2,4-stand-by dinitraniline suspension and 23.4g chlorine is added when 25 DEG C as follows.The joining day of 2,4-dinitraniline suspension is 4 hours, and the time that passes into of chlorine is 5 hours, leads to Bi Baowen half an hour, filters, wash to obtain 6-chlorine 2,4-dinitraniline, purity 92.5%, yield 94%.Mother liquor is collected lower batch and is applied mechanically, and residue 50 ~ 70g needs process containing the hydrochloric acid mother liquor that mass percent concentration is 10%.Mother liquor applies mechanically 10 batches continuously, average purity 88.1%, yield 92.8%.
Claims (5)
1. the process for cleanly preparing of chloro-2, the 4-dinitranilines of 6-, is characterized in that, comprise the steps:
(1) 2,4-dinitraniline is scattered in hydrochloric acid soln pulls an oar, then pass into chlorine and react, obtain intermediate reaction liquid;
In step (1), the mass concentration of described hydrochloric acid soln is 10% ~ 18%;
(2) the intermediate reaction liquid obtained to step (1) adds sodium chlorate solution and reacts, and after reacting completely, the reaction solution obtained obtains described 6-chlorine 2,4-dinitraniline and mother liquor through aftertreatment; Described mother liquor turns back in step (1) and applies mechanically as hydrochloric acid soln;
In step (2), the mass percent concentration of described sodium chlorate solution is 20% ~ 40%;
In step (2), described aftertreatment comprises: filtered by described reaction solution, and the solid washing obtained obtains chloro-2, the 4-dinitranilines of described 6-;
The filtrate obtained, directly as mother liquor, is back to step (1);
2,4-described dinitranilines: chlorine: the mol ratio of sodium chlorate is 1:0.3 ~ 0.8:0.06 ~ 0.28.
2. the process for cleanly preparing of chloro-2, the 4-dinitranilines of 6-according to claim 1, is characterized in that, in step (1), and 2,4-described dinitranilines and mass ratio=1:3 ~ 9 of hydrochloric acid soln.
3. the process for cleanly preparing of chloro-2, the 4-dinitranilines of 6-according to claim 1, is characterized in that, in step (1), the temperature of making beating is 20 ~ 60 DEG C.
4. the process for cleanly preparing of chloro-2, the 4-dinitranilines of 6-according to claim 1, is characterized in that, in step (1), passing into the temperature that chlorine carries out reacting is 20 ~ 45 DEG C.
5. the process for cleanly preparing of chloro-2, the 4-dinitranilines of 6-according to claim 1, is characterized in that, in step (2), the temperature of reaction is 40 ~ 55 DEG C.
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| CN104003888B (en) * | 2014-06-05 | 2016-09-14 | 浙江洪翔化学工业有限公司 | 2,4-dinitro-6-chloroaniline preparation method |
| CN104592042A (en) * | 2014-12-29 | 2015-05-06 | 浙江龙盛集团股份有限公司 | Clean technology for continuously synthesizing 2,4-binitro-6-chloroaniline |
| CN104592043A (en) * | 2014-12-29 | 2015-05-06 | 浙江龙盛集团股份有限公司 | Clean process for continuously synthesizing 2,6-dichloro-paranitroaniline |
| CN104592044B (en) * | 2015-01-30 | 2016-07-06 | 江苏艾科维科技有限公司 | The low temperature synthetic method of 2,6-Dichloro-4-nitroaniline |
| CN105367428B (en) * | 2015-11-10 | 2018-05-11 | 浙江龙盛集团股份有限公司 | A kind of synthesis technique of 2,4- dinitros -6- chloroanilines |
| CN106187787B (en) * | 2016-06-29 | 2019-01-22 | 浙江闰土研究院有限公司 | A kind of preparation method of 2- amino -4- chlorodiphenyl ether |
| CN111039797B (en) * | 2019-12-25 | 2020-10-27 | 莱州市积美盐化有限公司 | Preparation system of 2, 4-dinitro-6 bromaniline |
| CN110981737A (en) * | 2019-12-25 | 2020-04-10 | 莱州市积美盐化有限公司 | Preparation method of 2, 4-dinitro-6-bromoaniline |
| CN110981735A (en) * | 2019-12-30 | 2020-04-10 | 河南洛染股份有限公司 | 6-chloro-2, 4-dinitroaniline mother liquor recycling method |
| CN111620785B (en) * | 2020-06-22 | 2023-03-28 | 浙江迪邦化工有限公司 | Continuous chlorination method of nitroaniline |
| CN112321439B (en) * | 2020-10-15 | 2022-08-05 | 浙江迪邦化工有限公司 | Method for high-pressure assisted synthesis of 6-chloro-2, 4-dinitroaniline |
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Effective date of registration: 20210520 Address after: 312369 Hangzhou Shangyu economic and Technological Development Zone, Shaoxing, Zhejiang Patentee after: ZHEJIANG DAJING CHEMICAL Co.,Ltd. Address before: Daoxu Town, Shangyu City, Shaoxing City, Zhejiang Province Patentee before: ZHEJIANG RUNTU INSTITUTE Co.,Ltd. |