CN109705609A - A kind of industrialized preparing process of the low aniline value paratonere 57:1 of mother liquid coming - Google Patents
A kind of industrialized preparing process of the low aniline value paratonere 57:1 of mother liquid coming Download PDFInfo
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- CN109705609A CN109705609A CN201811593857.3A CN201811593857A CN109705609A CN 109705609 A CN109705609 A CN 109705609A CN 201811593857 A CN201811593857 A CN 201811593857A CN 109705609 A CN109705609 A CN 109705609A
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Abstract
The invention discloses the industrialized preparing process of the low aniline value paratonere 57:1 of mother liquid coming a kind of, including diazo reaction, coupling reaction and color lake reaction and etc..The present invention uses the mode of falling diazonium diazonium, prevents from forming molecule inner salt, is more advantageous to the diazo-reaction of 4- aminotoluene-3-sulfonic acid and impurity aromatic amine.Emulsifier is added in the on the basis of of falling diazonium, is a variation route, can effectively prevent the aggregation between diazonium molecules of salt, be more advantageous to the progress of coupling reaction.Using the method for falling diazonium, technique is easier, reduces reaction treatment step, and energy volume production, reduces costs.The paratonere 57:1 mother liquid coming aniline value concentration synthesized through the invention can control in < 5mg/L, reaches discharge standard, without carrying out aniline processing, solves the high environmental problem of sewage aniline value, be greatly reduced production cost.
Description
Technical field
The invention belongs to technical field of fine chemical synthesis, and in particular to a kind of low aniline value paratonere 57:1's of mother liquid coming
Industrialized preparing process.
Background technique
Aniline is a kind of important Organic Chemicals and chemical products.It is widely used in dyestuff, agricultural, medicine, military project
Etc. industries, while be also a kind of serious pollution environment, the harmful substance that is detrimental to health, China has been included in " Chinese ring
Border priority pollutant blacklist ", the industrialized production of existing paratonere 57:1 is more to be adopted as cis- heavy nitrogen production, generation
Mother liquid coming aniline category matter concentration is higher, reaches 100-200mg/L, brings bigger difficulty to sewage treatment and increase processing
Cost.
Summary of the invention
Aiming at the problems existing in the prior art, the purpose of the present invention is to provide a kind of high-environmental and the mothers of economic benefit
The industrialized preparing process of the low aniline value paratonere 57:1 of liquid water.
To achieve the above object, the invention adopts the following technical scheme:
The industrialized preparing process of the low aniline value paratonere 57:1 of mother liquid coming a kind of, includes the following steps:
1) 4- aminotoluene-3-sulfonic acid, water and liquid alkaline are added in common response kettle, be warming up to 40-50 DEG C of stirring makes for 0.5 hour
It is dissolved, and sodium nitrite solution is added and on the rocks is cooled to 15-25 DEG C；
2) hydrochloric acid, water and emulsifier are added in diazo reaction kettle, stirring is beaten, on the rocks to be cooled to 0-5 DEG C；
3) it falls diazo-reaction: under the conditions of 0-20 DEG C, step 1) products therefrom being added to step 2 in 10-20 minutes
Diazo reaction is carried out down in diazo reaction kettle, diazotization solution is obtained, is detected as blue with KI test paper after stirring 1-1.5 hours；
4) 2- hydroxyl -3- naphthoic acid, liquid alkaline and water are added in coupling reaction kettle, being warming up to 40-50 DEG C of stirring makes it in 0.5 hour
Dissolution；
5) under the conditions of 20-25 DEG C, the diazotization solution that step 3) obtains coupling reaction: is added to step in 10-30 minutes
Coupling reaction is carried out in rapid coupling reaction kettle 4), is stirred 0.5-1 hours after reaction, temperature is controlled at 20-25 DEG C；
6) color lake is reacted: being warming up to 30-40 DEG C of annesl, calcium chloride solution is added in 10-20 minutes；
7) it is warming up to 60-65 DEG C of insulation reaction 10-30 minutes, then is down to room temperature, filter, dry and obtain under the conditions of 85-90 DEG C
Paratonere 57:1.
A kind of industrialized preparing process of the low aniline value paratonere 57:1 of the mother liquid coming, the sodium nitrite solution
Concentration is 30%, and the mass ratio that feeds intake of the 4- aminotoluene-3-sulfonic acid and sodium nitrite solution is 100:(150-200).
The industrialized preparing process of the low aniline value paratonere 57:1 of mother liquid coming a kind of, the 4- amino toluene -3-
The mass ratio that feeds intake of sulfonic acid and 2- hydroxyl -3- naphthoic acid is 100:(110-150).
The industrialized preparing process of the low aniline value paratonere 57:1 of mother liquid coming a kind of, the 4- amino toluene -3-
The mass ratio 100:(10-20 that feeds intake of sulfonic acid and emulsifier).
A kind of industrialized preparing process of the low aniline value paratonere 57:1 of the mother liquid coming, the calcium chloride solution it is dense
Degree is 37%, and the mass ratio that feeds intake of the 4- aminotoluene-3-sulfonic acid and calcium chloride solution is 100:(300-500).
The industrialized preparing process of the low aniline value paratonere 57:1 of mother liquid coming a kind of, the emulsifier are anion
Type surfactant.
The industrialized preparing process of the low aniline value paratonere 57:1 of mother liquid coming a kind of, the emulsifier are sulfonation castor
Sesame oil or sodium sulfate of polyethenoxy ether of fatty alcohol.
The industrialized preparing process of the low aniline value paratonere 57:1 of mother liquid coming a kind of, the emulsifier are nonionic
Type surfactant.
The industrialized preparing process of the low aniline value paratonere 57:1 of mother liquid coming a kind of, the emulsifier are OS-15
Or MOA-4.
The industrialized preparing process of the low aniline value paratonere 57:1 of mother liquid coming a kind of, coupling reaction in step 5)
PH value is controlled in 9-12.
Key reaction formula of the invention is as follows:
Diazo reaction:
Coupling reaction:
Color lake reaction:
Main feature reaction of the invention is as follows:
4- aminotoluene-3-sulfonic acid, water, liquid alkaline, sodium nitrite solution is added in I, in a kettle, starts stirring, is warming up to 40-
50 DEG C of stirringizations are clear, obtain 4- aminotoluene-3-sulfonic acid sodium solution, and hydrochloric acid is added on the rocks be cooled in 15-25 DEG C, 10-20 minutes
Diazo liquid is prepared in the liquid of bottom.
2- hydroxyl -3- naphthoic acid, water, liquid alkaline is added in II, in coupling reaction kettle, starts stirring, is warming up to 40-50 DEG C and stirs
Mixing is clear, obtains 2- hydroxyl -3- naphthoic acid sodium clear liquid, on the rocks to be cooled to 20-25 DEG C, and the diazo liquid that step I obtains is added, and the time is
10-30 minutes, temperature was controlled at 20-25 DEG C.
III, is warming up to 30-40 DEG C of annesl, and calcium chloride solution is added in 10-20 minutes, is warming up to 60-65 DEG C of insulation reaction
10-30 minutes, then it is down to room temperature, it filters, drying obtains paratonere 57:1 at 85-90 DEG C.
The industrialized preparing process of the red 57:1 of the low aniline pigment of the mother liquid coming, it is characterised in that described in step I
Quality and 2- hydroxyl -3- naphthoic acid mass ratio after the cooling of 2- hydroxyl -3- naphthoic acid sodium solution are 100:200~500, it is ensured that no
It is precipitated.
Compared with the prior art, beneficial effects of the present invention are as follows:
(1) present invention use the mode of falling diazonium diazonium, prevent from forming molecule inner salt, be more advantageous to 4- aminotoluene-3-sulfonic acid and
The diazo-reaction of impurity aromatic amine.
(2) present invention in the on the basis of of falling diazonium adds emulsifier, is a variation route, can effectively prevent diazonium molecules of salt it
Between aggregation, be more advantageous to the progress of coupling reaction.
(3) present invention uses the method for falling diazonium, and technique is easier, reduces reaction treatment step, and energy volume production, reduces
Cost.
(4) the paratonere 57:1 mother liquid coming aniline value concentration synthesized through the invention can control in < 5mg/L, reach discharge
Standard solves the high environmental problem of sewage aniline value, has been greatly reduced production cost without carrying out aniline processing.
Specific embodiment
The present invention is described further combined with specific embodiments below, but protection scope of the present invention is not limited in
This.
Embodiment 1
1) 115Kg 4- aminotoluene-3-sulfonic acid is added in common response kettle, adds 1600Kg water, adds the liquid of 90Kg content 30%
Alkali is warming up to 45 DEG C and is stirred and dissolved into salt 0.5 hour, rapidly joins 30% sodium nitrite solution 137Kg；Add in diazonium bucket
The hydrochloric acid for entering 200Kg content 30% adds 500Kg water, on the rocks to be cooled to 0 DEG C, adds MOA-4 10Kg；Additionization is clear in 10 minutes
4- aminotoluene-3-sulfonic acid sodium solution carries out down diazotising and is stirred to react 1 hour, obtains diazo liquid；
2) 115Kg 2- hydroxyl -3- naphthoic acid is added in coupling reaction kettle, adds 1000Kg water, adds the liquid of 230Kg content 30%
Alkali, 45 DEG C extremely dissolve for stirring 30 minutes；
3) diazo liquid is added in coupling reaction kettle under the conditions of 20-25 DEG C and carries out coupling reaction, Coupling time 10 minutes, coupling
Process keeps pH > 9, and coupling terminates diazonium salt not excessively, stirs 30 minutes；
4) 35 DEG C of annesls of post-processing heating are added the calcium chloride solution that concentration is 37% in 10 minutes, keep the temperature 10 minutes, be warming up to 60
DEG C heat preservation 10 minutes, cooling filter, dried under the conditions of 85-90 DEG C, obtain paratonere, the application performance of the paratonere: resistance to move
5 grades of shifting property, 4 grades of alkali resistance, 4 grades of weatherability, heat-resisting 230 DEG C, squeezes mother liquid coming aniline value: 4mg/L by 3 grades of acid resistance.
Embodiment 2
1) 115Kg 4- aminotoluene-3-sulfonic acid is added in common response kettle, adds 1600Kg water, adds the liquid of 90Kg content 30%
Alkali is warming up to 45 DEG C and is stirred and dissolved into salt 0.5 hour, rapidly joins 30% sodium nitrite solution 137Kg；Add in diazonium bucket
The hydrochloric acid for entering 200Kg content 30% adds 500Kg water, on the rocks to be cooled to 0 DEG C, adds sulfonated castor oil 20Kg；Additionization in 10 minutes
Clear 4- aminotoluene-3-sulfonic acid sodium solution carries out down diazotising and is stirred to react 1.5 hours, obtains diazo liquid；
2) 120Kg 2- hydroxyl -3- naphthoic acid is added in coupling reaction kettle, adds 1000Kg water, adds the liquid of 235Kg content 30%
Alkali, 45 DEG C extremely dissolve for stirring 30 minutes；
3) diazo liquid is added in coupling reaction kettle under the conditions of 20-25 DEG C and carries out coupling reaction, Coupling time 15 minutes, coupling
Process keeps pH > 9, and coupling terminates diazonium salt not excessively, stirs 60 minutes；
4) 37 DEG C of annesls of post-processing heating are added the calcium chloride solution that concentration is 37% in 15 minutes, keep the temperature 10 minutes, be warming up to 60
DEG C heat preservation 15 minutes, cooling filter, dried under the conditions of 85-90 DEG C, obtain paratonere, the application performance of the paratonere: resistance to move
4 grades of shifting property, 4 grades of alkali resistance, 4 grades of weatherability, heat-resisting 240 DEG C, squeezes mother liquid coming aniline value: 3.5mg/L by 3 grades of acid resistance.
Embodiment 3
1) 120Kg 4- aminotoluene-3-sulfonic acid is added in common response kettle, adds 1600Kg water, adds the liquid of 95Kg content 30%
Alkali is warming up to 45 DEG C and is stirred and dissolved into salt 0.5 hour, rapidly joins 30% sodium nitrite solution 140Kg；Add in diazonium bucket
The hydrochloric acid for entering 220Kg content 30% adds 800Kg water, on the rocks to be cooled to 0 DEG C, adds MOA-4 15Kg；Additionization is clear in 10 minutes
4- aminotoluene-3-sulfonic acid sodium solution carries out down diazotising and is stirred to react 1 hour, obtains diazo liquid；
2) 118Kg 2- hydroxyl -3- naphthoic acid is added in coupling reaction kettle, adds 1000Kg water, adds the liquid of 235Kg content 30%
Alkali, 45 DEG C extremely dissolve for stirring 30 minutes；
3) diazo liquid is added in coupling reaction kettle at 25 DEG C and carries out coupling reaction, Coupling time 30 minutes, coupled processes were protected
PH > 9 is held, coupling terminates diazonium salt not excessively, stirs 30 minutes；
4) 37 DEG C of annesls of post-processing heating are added the calcium chloride solution that concentration is 37% in 20 minutes, keep the temperature 10 minutes, be warming up to 60
DEG C heat preservation 20 minutes, cooling filter, dried under the conditions of 85-90 DEG C, obtain paratonere, the application performance of the paratonere: resistance to move
5 grades of shifting property, 4 grades of alkali resistance, 4 grades of weatherability, heat-resisting 230 DEG C, squeezes mother liquid coming aniline value: 3.5mg/L by 4 grades of acid resistance.
Claims (10)
1. the industrialized preparing process of the low aniline value paratonere 57:1 of mother liquid coming a kind of, it is characterised in that include the following steps:
1) 4- aminotoluene-3-sulfonic acid, water and liquid alkaline are added in common response kettle, be warming up to 40-50 DEG C of stirring makes for 0.5 hour
It is dissolved, and sodium nitrite solution is added and on the rocks is cooled to 15-25 DEG C；
2) hydrochloric acid, water and emulsifier are added in diazo reaction kettle, stirring is beaten, on the rocks to be cooled to 0-5 DEG C；
3) it falls diazo-reaction: under the conditions of 0-20 DEG C, step 1) products therefrom being added to step 2 in 10-20 minutes
Diazo reaction is carried out down in diazo reaction kettle, diazotization solution is obtained, is detected as blue with KI test paper after stirring 1-1.5 hours；
4) 2- hydroxyl -3- naphthoic acid, liquid alkaline and water are added in coupling reaction kettle, being warming up to 40-50 DEG C of stirring makes it in 0.5 hour
Dissolution；
5) under the conditions of 20-25 DEG C, the diazotization solution that step 3) obtains coupling reaction: is added to step in 10-30 minutes
Coupling reaction is carried out in rapid coupling reaction kettle 4), is stirred 0.5-1 hours after reaction, temperature is controlled at 20-25 DEG C；
6) color lake is reacted: being warming up to 30-40 DEG C of annesl, calcium chloride solution is added in 10-20 minutes；
7) it is warming up to 60-65 DEG C of insulation reaction 10-30 minutes, then is down to room temperature, filter, dry and obtain under the conditions of 85-90 DEG C
Paratonere 57:1.
2. the industrialized preparing process of the low aniline value paratonere 57:1 of mother liquid coming according to claim 1 a kind of, feature
The concentration for being the sodium nitrite solution is 30%, the quality that feeds intake of the 4- aminotoluene-3-sulfonic acid and sodium nitrite solution
Than for 100:(150-200).
3. the industrialized preparing process of the low aniline value paratonere 57:1 of mother liquid coming according to claim 1 a kind of, feature
The mass ratio that feeds intake for being the 4- aminotoluene-3-sulfonic acid and 2- hydroxyl -3- naphthoic acid is 100:(110-150).
4. the industrialized preparing process of the low aniline value paratonere 57:1 of mother liquid coming according to claim 1 a kind of, feature
It is the mass ratio 100:(10-20 that feeds intake of the 4- aminotoluene-3-sulfonic acid and emulsifier).
5. the industrialized preparing process of the low aniline value paratonere 57:1 of mother liquid coming according to claim 1 a kind of, feature
The concentration for being the calcium chloride solution is 37%, and the mass ratio that feeds intake of the 4- aminotoluene-3-sulfonic acid and calcium chloride solution is
100:(300-500)。
6. the industrialized preparing process of the low aniline value paratonere 57:1 of mother liquid coming according to claim 1 a kind of, feature
It is that the emulsifier is anionic surfactant.
7. the industrialized preparing process of the low aniline value paratonere 57:1 of mother liquid coming according to claim 6 a kind of, feature
It is that the emulsifier is sulfonated castor oil or sodium sulfate of polyethenoxy ether of fatty alcohol.
8. the industrialized preparing process of the low aniline value paratonere 57:1 of mother liquid coming according to claim 1 a kind of, feature
It is that the emulsifier is nonionic surface active agent.
9. the industrialized preparing process of the low aniline value paratonere 57:1 of mother liquid coming according to claim 8 a kind of, feature
It is that the emulsifier is OS-15 or MOA-4.
10. the industrialized preparing process of the low aniline value paratonere 57:1 of mother liquid coming according to claim 1 a kind of, feature
It is that the pH value of coupling reaction in step 5) is controlled in 9-12.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113698792A (en) * | 2021-09-10 | 2021-11-26 | 百合花集团股份有限公司 | Preparation method of azo lake organic pigment capable of reducing aromatic amine residues |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004083312A2 (en) * | 2003-03-18 | 2004-09-30 | Ciba Specialty Chemicals Holding Inc. | Cationic dimeric dyes |
| CN104130590A (en) * | 2014-07-25 | 2014-11-05 | 嘉兴科隆化工有限公司 | Industrial production method for migration-resistant bright red pigment 150 used for PU |
| CN104592787A (en) * | 2014-12-25 | 2015-05-06 | 上虞舜联化工有限公司 | Preparation method of C.I. pigment yellow 181 |
| CN106479215A (en) * | 2016-10-14 | 2017-03-08 | 吴江市屯村颜料厂 | A kind of polymolecularity high coloring power 57:1 pigment and preparation method thereof |
-
2018
- 2018-12-25 CN CN201811593857.3A patent/CN109705609A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004083312A2 (en) * | 2003-03-18 | 2004-09-30 | Ciba Specialty Chemicals Holding Inc. | Cationic dimeric dyes |
| CN104130590A (en) * | 2014-07-25 | 2014-11-05 | 嘉兴科隆化工有限公司 | Industrial production method for migration-resistant bright red pigment 150 used for PU |
| CN104592787A (en) * | 2014-12-25 | 2015-05-06 | 上虞舜联化工有限公司 | Preparation method of C.I. pigment yellow 181 |
| CN106479215A (en) * | 2016-10-14 | 2017-03-08 | 吴江市屯村颜料厂 | A kind of polymolecularity high coloring power 57:1 pigment and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 化学工业部人事教育司等组织编写: "《有机化学反应（三）》", 31 December 1997, 化学工业出版社 * |
| 陈亚庆编著: "《有机中间体的工业分析法》", 31 January 1997, 化学工业出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113698792A (en) * | 2021-09-10 | 2021-11-26 | 百合花集团股份有限公司 | Preparation method of azo lake organic pigment capable of reducing aromatic amine residues |
| CN113698792B (en) * | 2021-09-10 | 2022-05-10 | 百合花集团股份有限公司 | Preparation method of azo lake organic pigment capable of reducing aromatic amine residues |
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