CN103539705B - The process for cleanly preparing of a kind of urea groups anilinechloride - Google Patents
The process for cleanly preparing of a kind of urea groups anilinechloride Download PDFInfo
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- CN103539705B CN103539705B CN201310505565.0A CN201310505565A CN103539705B CN 103539705 B CN103539705 B CN 103539705B CN 201310505565 A CN201310505565 A CN 201310505565A CN 103539705 B CN103539705 B CN 103539705B
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Abstract
The invention discloses the process for cleanly preparing of a kind of urea groups anilinechloride, comprise the steps: mphenylenediamine to be dissolved in sodium chloride brine reaction system, add auxiliary agent, controlling temperature of reaction is-5 DEG C-25 DEG C, and then add Zassol and hydrochloric acid reacts, after reacting completely, through aftertreatment obtain described between urea groups anilinechloride; Described auxiliary agent is nitric acid or nitrate.This generating process adopts salt solution to replace pure water as end water, utilize the salting out of sodium-chlor, between enabling to generate in reaction, urea groups anilinechloride is separated out timely, prevent the generation of by product two urea, between obtaining, urea groups anilinechloride purity can reach more than 98%, and yield is more than 95%, and content is 75%-80%, sewage quantity reduces 50%, and technique is simple, level of automation is high.
Description
Technical field
The present invention relates to a kind of production method of dyestuff intermediate, be specifically related to the process for cleanly preparing referring to urea groups anilinechloride between a kind of high purity.
Background technology
Between urea groups anilinechloride, structure is as shown in formula I, be a kind of important dyestuff intermediate, be mainly used in the production of the fine chemical product such as activity, matching stain, the reactive dyestuffs 4RFN being raw material production with it is golden yellow is monogenetic dyestuff maximum in reactive dyestuffs yellow cultivars.
The synthetic method that at present, urea groups anilinechloride is the most frequently used is: take mphenylenediamine as raw material, react in aqueous phase with hydrochloric acid and Zassol and form, its reaction equation is as follows:
Because between reaction generation, urea groups anilinechloride is dissolved in reaction system in a large number, can continue to react with hydrochloric acid and Zassol to generate allophanamide, so, between generally commercially available, urea groups anilinechloride finished product purity can only accomplish 96%, and owing to there being a certain amount of mphenylenediamine not yet to react in reaction system, in the middle of mother liquor, urea groups anilinechloride dissolves the reasons such as residual, general yield only has about 88%, the high salt high-COD waste water of urea groups anilinechloride appointment generation about 7 tons between simultaneously often producing a ton, between traditional method synthesis, urea groups anilinechloride solid content is low in addition, content only has 60% ~ 70%, during for the synthesis of dyestuff, content detection deviation is large, easily cause feed intake inaccurate, cause dyestuff quality unstable.
Summary of the invention
The invention provides the process for cleanly preparing of a kind of urea groups anilinechloride, this production technique yield be high, pollute little, and between obtaining the content of urea groups anilinechloride and purity high.
The process for cleanly preparing of a kind of urea groups anilinechloride, comprise the steps: mphenylenediamine to be dissolved in sodium chloride brine reaction system, add auxiliary agent, controlling temperature of reaction is-5 DEG C ~ 25 DEG C, and then add Zassol and hydrochloric acid reacts, after reacting completely, through aftertreatment obtain described between urea groups anilinechloride.
In the present invention, replace pure water as end water using sodium chloride brine, make reaction generate between urea groups anilinechloride separate out from reaction system due to salting out, thus the further reaction of urea groups aniline between stoping, prevent the generation of allophanamide, improve the purity of this production technique yield and a urea groups anilinechloride.
The concentration of described sodium chloride brine has a significant impact product purity and reaction efficiency, and sodium chloride concentration is too low, and salting out is weak, and between reaction generates, urea groups anilinechloride is difficult to timely precipitation, can react generation two urea further; Excessive concentration, can reduce the solubleness of mphenylenediamine, and reduce reaction efficiency, the concentration expressed in percentage by weight of described sodium chloride brine is 5% ~ 25%, is preferably 10% ~ 20%, most preferably is 12% ~ 16%.
The solid content acting as raising product of described auxiliary agent, described auxiliary agent is nitric acid or nitrate, is preferably SODIUMNITRATE; The consumption of described auxiliary agent is 0.5% ~ 3% of mphenylenediamine quality.
Described temperature of reaction is preferably 0 DEG C ~ 15 DEG C.
In the present invention, described hydrochloric acid and Zassol consumption excessive a little, unsuitable too much, too much can cause increasing of the waste of raw material and by product two urea, as preferably, with molar amount, described mphenylenediamine: hydrochloric acid: Zassol is 1:2.2 ~ 2.5:1.05 ~ 1.08.
In the present invention, described Zassol is added by piecewise uniform, and hydrochloric acid adopts the mode dripped continuously to add, and the pH value of reaction system is controlled by the add-on of described Zassol and the speed that adds of hydrochloric acid.
Before adding described Zassol, first add below the pH to 0.8 that hydrochloric acid regulates reaction system, described Zassol is fed in raw material by automatic feeding device piecewise uniform.
As further preferably, in described Zassol and the adition process of hydrochloric acid, controlled the pH value (program set) of reaction by on-line system, the segmentation add-on of Zassol and pH control as follows:
Add the Zassol of total amount 40 ~ 55% in (1) 1 ~ 3 hour, control pH is 0.8-1.0;
Add the Zassol of total amount 15 ~ 25% in (2) 0.5 ~ 1.5 hours, control pH is 1.0-1.3;
Add the Zassol of total amount 15 ~ 30% in (3) 1 ~ 3 hours, control pH is 1.1-1.4;
Add the Zassol of total amount 1 ~ 10% in (4) 0.5 ~ 1.5, control pH is 1.2-1.5;
After described Zassol adds, continuing control pH is that 1.2-1.5 is until reaction terminates.Adopt above-mentioned feed way, the concentration of the Zassol in reaction system and pH value can be made to remain on suitable scope, this scope can reduce the generation of by product two urea to greatest extent, thus reaches the object improving product yield and purity.
As further preferred, reinforced process is as follows:
On-line system control pH=0.8-1.0, by automatic feeding device evenly add in 2 hours account for total amount 50% Zassol; Control at pH=1.0-1.3, evenly add in 1 hour account for total amount 23% Zassol; Control at pH=1.1-1.4, evenly add in 2 hours account for total amount 25% Zassol; Control at pH=1.2-1.5, evenly add in 1 hour account for total amount 2% Zassol; After adding, at pH=1.2-1.5, reaction sampled after half an hour, and detect the content of mphenylenediamine, liquid chromatographic detection mphenylenediamine≤2.5% is reaction end.
Described aftertreatment comprises: cool to 20 DEG C ~ 40 DEG C recrystallizations again after being warmed up to 60 DEG C ~ 100 DEG C dissolvings, the press filtration of entrance pressure filter, is product after filter cake press dry, and after filtrate collection, next batch used by cover, as the end water of next batch reaction.
As preferably, described filtrate is lowered the temperature 0 DEG C ~ 10 DEG C and is separated out by-product impurities, and the secondary filtrate obtained after filtration is applied mechanically after regulating concentration again.Described by-product impurities is allophanamide, after allophanamide being separated out, filtrate can be made directly to apply mechanically, reduce the discharge of sewage.
Compared with the existing technology, beneficial effect of the present invention is embodied in:
(1) replace pure water as end water using sodium chloride brine, by the salting out of sodium-chlor, product is separated out in time from reaction system, thus the further reaction of urea groups aniline between stoping, prevent the generation of allophanamide, improve more than this production technique yield to 95%, make the purity of product reach more than 98%;
(2) adopt nitric acid or nitrate as auxiliary agent, improve the solid content of product, make solid content reach 75%-80%;
(3) by by filtrate recovery, reduce the discharge of sewage, make sewage quantity decrease 50%.
Embodiment
Embodiment 1
In reactor, put pure water 1600L, start stirring.Industrial chlorinations sodium 300kg is dropped in reactor.Sealing Arrangement, opens vacuum and sucks mphenylenediamine 220kg, add SODIUMNITRATE 1.1 kilograms, add 30% salt acid for adjusting pH value to less than 0.8, after material all dissolves, after cooling to 0 DEG C, open automatic feeding device to start to add Zassol powder, open hydrochloric acid automatic dripping system simultaneously and drip hydrochloric acid.On-line system control pH=0.8-1.0, by automatic feeding device add in 2 hours account for total amount 50% Zassol, control at pH=1.0-1.3, add in 1 hour account for total amount 23% Zassol, control at pH=1.1-1.4, add in 2 hours account for total amount 25% Zassol, control at pH=1.2-1.5, add in 1 hour account for total amount 2% Zassol, after adding, react after half an hour at pH=1.2-1.5 and sample, detect the content of mphenylenediamine, liquid chromatographic detection mphenylenediamine≤2.5% is reaction end, and this process consumes hydrochloric acid 570kg, Zassol 142kg.
After reaction terminates, after being warmed up to 100 DEG C of dissolvings, be cooled to 20 DEG C of-40 DEG C of recrystallizations again.After filter cake press dry, filtrate carries out follow-up applying mechanically, and going out filter cake is 360kg, and detecting filter cake HPLC purity is 98.51%, and filter cake solid content is 74.7%, and yield is 87.45%.
Embodiment 2
Allophanamide is separated out by lowering the temperature after the filtrate collection of embodiment 15 DEG C, after filtering and impurity removing, collection salt solution is 2800kg, get its 1500kg 400kg that adds water to regulate after brine concentration and squeeze in reactor, Sealing Arrangement, opens vacuum and sucks mphenylenediamine 220kg, add SODIUMNITRATE 6 kilograms, add Zassol and hydrochloric acid by the method for embodiment 1, this process consumes hydrochloric acid 573kg, Zassol 139kg.
After reaction terminates, after being warmed up to 100 DEG C of dissolvings, be cooled to 20 DEG C of recrystallizations again.After filter cake press dry, going out filter cake is 374kg, and detecting filter cake HPLC purity is 98.64%, and filter cake solid content is 80.0%, and yield is 97.36%.
Embodiment 3
Allophanamide is separated out by lowering the temperature after the filtrate collection of embodiment 20 DEG C, after filtering and impurity removing, collection salt solution is 2800kg, get its 1400kg 500kg that adds water to regulate after brine concentration and squeeze into Sealing Arrangement in reactor, open vacuum and suck mphenylenediamine 220kg, suck 3 kilograms, nitric acid, add Zassol and hydrochloric acid by the method for embodiment 1, this process consumes hydrochloric acid 569kg, Zassol 140kg.
After reaction terminates, after being warmed up to 100 DEG C of dissolvings, be cooled to 40 DEG C of recrystallizations again.After filter cake press dry, going out filter cake is 378kg, and detecting filter cake HPLC purity is 98.63%, and filter cake solid content is 77.9%, and yield is 95.78%.
Comparative example 1
In reactor, put pure water 1600L, start stirring.Suck mphenylenediamine 220kg toward reactor, add SODIUMNITRATE 1.1 kilograms, add 30% salt acid for adjusting pH value to less than 0.8, after material all dissolves, after cooling to 0 DEG C of temperature, open automatic feeding device and start to add Zassol powder, open hydrochloric acid automatic dripping system simultaneously and drip hydrochloric acid.On-line system control pH=0.8-1.0, by automatic feeding device add in 2 hours account for total amount 50% Zassol, control at pH=1.0-1.3, add in 1 hour account for total amount 23% Zassol, control at pH=1.1-1.4, add in 2 hours account for total amount 25% Zassol, control at pH=1.2-1.5, add in 1 hour account for total amount 2% Zassol, after adding, sample after pH=1.2-1.5 reacts half an hour, this process consumes hydrochloric acid 570kg, Zassol 142kg.Detection filter cake HPLC purity is 63.3%, two urea HPLC purity is 35.9%.
Comparative example 2
By the method for embodiment 1, do not add urea hydrochloride between SODIUMNITRATE synthesis, detecting filter cake HPLC purity is 98.42%, and filter cake solid content is 60.1%, and yield is 86.35%.
Comparative example 3
In reactor, put pure water 1600L, start stirring.Suck mphenylenediamine 220kg toward reactor, add SODIUMNITRATE 1.1 kilograms, add 30% salt acid for adjusting pH value to less than 0.8, after material all dissolves, after cooling to 0 DEG C of temperature, open automatic feeding device and start to add Zassol powder, open hydrochloric acid automatic dripping system simultaneously and drip hydrochloric acid.On-line system is control pH=0.8-1.0 all the time, adds the Zassol of example 1 a great deal of, and it is 6.47% that sampling detects mphenylenediamine content, and detecting filter cake HPLC purity is 99.31%, and filter cake solid content is 75.1%, and yield is 76.23%.
Comparative example 4
In reactor, put pure water 1600L, start stirring.Suck mphenylenediamine 220kg toward reactor, add SODIUMNITRATE 1.1 kilograms, add 30% salt acid for adjusting pH value to 1.2-1.5, after material all dissolves, after cooling to 0 DEG C of temperature, open automatic feeding device and start to add Zassol powder, open hydrochloric acid automatic dripping system simultaneously and drip hydrochloric acid.On-line system is control pH=1.2-1.5 all the time, adds the Zassol of embodiment 1 a great deal of, and it is 0.5% that sampling detects mphenylenediamine content, and detecting filter cake HPLC purity is 92.02%, and filter cake solid content is 70.0%, and yield is 90.1%.
Purity in above-described embodiment and comparative example refers to HPLC purity, and product is completely the same by the retention time of the HPLC of HPLC and commercial standard substance, and content adopts the method in standard GB/T/T25807-2010 to measure.
Claims (6)
1. the process for cleanly preparing of urea groups anilinechloride between a kind, it is characterized in that, comprise the steps: mphenylenediamine to be dissolved in sodium chloride brine reaction system, add auxiliary agent, controlling temperature of reaction is-5 DEG C ~ 25 DEG C, and then add Zassol and hydrochloric acid reacts, after reacting completely, through aftertreatment obtain described between urea groups anilinechloride;
Described auxiliary agent is nitric acid or nitrate;
Zassol is added by piecewise uniform, and hydrochloric acid adopts the mode dripped continuously to add, and the pH value of reaction system is controlled by the add-on of described Zassol and the speed that adds of hydrochloric acid;
In described Zassol and the adition process of hydrochloric acid, controlled the pH value of reaction by on-line system, the add-on of Zassol and pH control as follows:
Add the Zassol of total amount 40 ~ 55% in (1) 1 ~ 3 hour, control pH is 0.8-1.0;
Add the Zassol of total amount 15 ~ 25% in (2) 0.5 ~ 1.5 hours, control pH is 1.0-1.3;
Add the Zassol of total amount 15 ~ 30% in (3) 1 ~ 3 hours, control pH is 1.1-1.4;
Add the Zassol of total amount 1 ~ 10% in (4) 0.5 ~ 1.5, control pH is 1.2-1.5;
After described Zassol adds, continuing control pH is that 1.2-1.5 is until reaction terminates.
2. the process for cleanly preparing of according to claim 1 urea groups anilinechloride, is characterized in that, the concentration expressed in percentage by weight of described sodium chloride brine is 5% ~ 25%.
3. the process for cleanly preparing of according to claim 1 urea groups anilinechloride, is characterized in that, the consumption of described auxiliary agent is 0.5% ~ 3% of described mphenylenediamine quality.
4. the process for cleanly preparing of according to claim 1 urea groups anilinechloride, is characterized in that, with molar amount, and described mphenylenediamine: hydrochloric acid: Zassol is 1:2.2 ~ 2.5:1.05 ~ 1.08.
5. the process for cleanly preparing of according to claim 1 urea groups anilinechloride, it is characterized in that, described aftertreatment comprises: cool to 20 DEG C ~ 40 DEG C recrystallizations again after being warmed up to 60 DEG C ~ 100 DEG C dissolvings, the press filtration of entrance pressure filter, product is after filter cake press dry, after filtrate collection, next batch used by cover, as the end water of next batch reaction.
6. the process for cleanly preparing of according to claim 5 urea groups anilinechloride, is characterized in that, described filtrate is lowered the temperature 0 DEG C ~ 10 DEG C and separated out by-product impurities, and the secondary filtrate obtained after filtration is applied mechanically after regulating concentration again.
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| CN104817477A (en) * | 2015-03-31 | 2015-08-05 | 杭州海虹精细化工有限公司 | Technology for synthesis of biurea from hydrazine hydrate and cyanate |
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