CN101481524A - Preparation of reactive red 3G dye - Google Patents
Preparation of reactive red 3G dye Download PDFInfo
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- CN101481524A CN101481524A CNA2008101541127A CN200810154112A CN101481524A CN 101481524 A CN101481524 A CN 101481524A CN A2008101541127 A CNA2008101541127 A CN A2008101541127A CN 200810154112 A CN200810154112 A CN 200810154112A CN 101481524 A CN101481524 A CN 101481524A
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Abstract
The invention provides an improved method for preparing vital red 3G dye used for fur. Process improvement is carried out on the method in that the film processing technology is adopted, transformation ratio is improved by adding phase transfer catalyst, the central control method is adopted to control key links and improve stability of products, the membrane technology is adopted to improve strength of products and reduce waste liquor.
Description
Technical field
The present invention relates to the reactive dye for wool field, particularly a kind of mao of preparation method with reactive red 3G.
Background technology
Reactive dye for wool has lovely luster, application performance excellence, characteristics such as easy to use.For example hair is with reactive red 3G dyestuff, and the call number of this dyestuff is Reactive Red 136, and chemical structural formula is:
Hair commonly used at present is as follows with the preparation method and the defective thereof of reactive red 3G dyestuff:
A, two an activators preparation: (1) adds 2 in water, the dissolving of 4-diamino benzene sulfonic acid sodium is standby.(2) in above-mentioned solution, add trash ice and make temperature reach 0-5 ℃, pH=6-6.5, time length 3-4 hour, add 2 then, 3-two bromo propionyl chloros, reaction reach home filter semi-finished product for standby.
The shortcoming of this step is that filter produced a large amount of faint yellow waste water, can't handle after reaction end arrived.
B, condensation reaction: (1) adds γ acid in water, transfer pH=7 with yellow soda ash, and is complete molten standby; (2) add 8-12 ℃ of trash ice cooling in solution, added 2 in 2-3 hour, 3-two bromo propionyl chloros are controlled at 5.5-6.5 with pH, react 1-2 hour, and its transformation efficiency is 96%, and the product that obtains is standby.
C, diazotization reaction: two activators making beating between in water, adding, add trash ice, hydrochloric acid, sodium nitrite solution in 0-5 ℃ of reaction 2-3 hour, keep the potassium iodide starch paper blueness.
D, coupled reaction: add an amount of thionamic acid to above-mentioned from the product of C step, remove excessive nitrite sodium, join then and stir among the B after 10 minutes, it is standby to transfer pH=6-7 to stir after 1-2 hour with yellow soda ash.
E, saltout: in above-mentioned D, add the press filtration after 2 hours of 4%-5% sodium-chlor.
The shortcoming of above-mentioned steps is to produce a large amount of red waste water, and the COD value of waste water is higher a lot.
F, drying: will add the dust-proofing agent making beating among the above-mentioned E, pH=6-7, big tower temperature out is controlled at 100-110 ℃ and carries out drying.
Aforesaid method is original production method, wherein has a large amount of problems, kind, the quality of producing be can not get 100% hold, and the waste water that produces in the whole process is very big, and environment is caused very big harm.
The present invention has carried out process modification to this method, and employing membrane technology, improve transformation efficiency by adding phase-transfer catalyst, control key link by middle control method, improve the stability of product, intensity by membrane technique raising product has reduced the waste liquid generation by above several method.
Summary of the invention
For solving the problems of the technologies described above, the invention provides a kind of mao of improvement preparation method with reactive red 3G dyestuff, this preparation method comprises the steps:
(a) two activators preparations and diazotization between: (1) adds 2 in water, the dissolving of 4-diamino benzene sulfonic acid sodium, add trolamine and EDTA fully stir mixing solutions; (2) adding trash ice in this mixing solutions makes temperature reach 0-5 ℃.In 1.5-3 hour, add 2, the mixed solution of 3-two bromo propionyl chloros and acetone, and control pH=6.0-6.5 with 15% sodium carbonate solution and react; (3) reaction is finished the back and is added hydrochloric acid, and 20-30 ℃ sodium nitrite solution, and controlled temperature is in 8-18 ℃ of reaction 2-4 hour, during the maintenance Sodium Nitrite little excessive, obtain diazonium liquid;
(b) condensation reaction: (1) adds γ acid in water, transfer pH=7 with yellow soda ash, gets solution for standby; (2) in this solution, add trash ice and cool to 8-12 ℃, in 2-3 hour, add 2,3-two bromo propionyl chloros and acetone mixed solution, pH is 4.5-6.5 reaction 1-2 hour with the yellow soda ash regulation and control, obtains condensation reaction solution.
(c) coupled reaction: in the product diazonium liquid of above-mentioned (a) reaction, add an amount of thionamic acid and remove excessive nitrite sodium, then this solution is joined in 18-30 ℃, 1-2 hour in the condensation reaction solution that (b) step obtains, transferring pH with 15% sodium carbonate solution during this time is 5.5-7, stir sampling in per 10 minutes, survey terminal point, OV method and liquid phase method are synchronous in the measurement, and products therefrom is reactive red 3G behind the reaction end.
Preferably, method of the present invention can also comprise following purification step:
(d) press filtration: after terminal point is qualified, with filter filter, mother liquor collects in another retort, filter cake is packed into standby in the bag;
(e) film is saturating: collect mother liquor in the retort, cross film, film and see through in the journey the saturating temperature of controlling diaphragm below 30 ℃, cross behind the film in bag the filter cake dispersion of pulling an oar;
(f) drying: behind the product adding dust-proofing agent with (e) step, control pH=6.5, temperature are carried out the spray tower drying for 105 ℃.
In the aforesaid method, (a) temperature of reaction in (2) is preferably 5 ℃ in the step, and the time is preferably 1.5 hours, and the pH value is preferably 6.0-6.3, and (a) reaction times in (3) is preferably 3 hours in the step.
In the aforesaid method, (b) pH in (2) in the step is preferably 5.0-6.0, and the reaction times is preferably 2 hours.
In the aforesaid method, (c) reaction pH value is preferably 6 in the step, and temperature is preferably 20 ℃ ± 1 ℃.
In the aforesaid method, (f) amount of dust-proofing agent is preferably 1% of product weight in the step.
The beneficial effect of aforesaid method is as follows:
(a) beneficial effect of step is for adding phase-transfer catalyst trolamine, acetone, makes its transformation efficiency bring up to 99.5% by former 98%.And add EDTA and make metal ion in its water obtain covering to keep away, make its finished product coloured light more bright-coloured, and the no waste water generation of two an activators preparation.
(b) condensation reaction of step also is to add by phase-transfer catalyst acetone to bring up to 98.5% transformation efficiency by original 96% transformation efficiency.
(c) step reaction passes through to temperature control and has improved diazotization reaction effect transformation efficiency and also increase.
(c) step is the terminal point controlled step, in order to make terminal point equal theoretical value better, terminal point must reach consistent with liquid chromatography by UV, just can be that terminal point is qualified.
(e) in the step, the mother liquor in the holding tank is improved mother liquor intensity by the saturating technology desalination of film, mother liquor intensity by film by original 80%-85%, intensity is brought up to 100%-110%, reduce the step saltout like this, the cost that economizes in raw materials, and avoided the generation of colorful wastewater.
Embodiment
For specifying technical scheme of the present invention, enumerate embodiment below and describe technical scheme of the present invention in detail, this embodiment does not form any limitation of the invention.
Embodiment
The concrete preparation process of reactive red 3G dyestuff of the present invention is as follows:
(a) two activators and diazotization reaction between: in 20 tons of retort, add and add 2 of 254Kg under 3.5 tons of stirrings of end water, 4-diamino benzene sulfonic acid sodium, make it molten entirely, add the trolamine of 33Kg and the EDTA of 60Kg, abundant stirring and dissolving, complete molten back adds trash ice, controlled temperature 0-5 ℃ added 2 of 280Kg with 1.5 hours, 3-two bromo propionyl chloros and acetone 30Kg mixed solution, and control pH=6.0-6.3 with 15% sodium carbonate solution, after reaction is finished, the hydrochloric acid that adds 112.3Kg, and 25 ℃ sodium nitrite solution, controlled temperature was in 14 ℃ of reactions 3 hours, keep Sodium Nitrite little excessive during this time, obtain diazonium liquid.
(b) condensation reaction: in 20 tons of retort, add 3.5 tons in end water, stir the γ acid that adds 240.3Kg down, transfer pH=7.0 with 15% sodium carbonate solution, complete molten back adds trash ice and cools to 12 ℃, in 3 hours, at the uniform velocity add 2 of 260Kg, the mixed solution of 3-two bromo propionyl chloros and 25Kg acetone, during with 15% sodium carbonate solution control pH=5.0-6.0, finish afterreaction 2 hours, and got condensation reaction solution.
(c) coupled reaction: the Sodium Nitrite in above-mentioned (a) is removed with an amount of thionamic acid, then in 1 hour, simultaneously 20 ℃ ± 1 ℃ of controlled temperature joins it in (b), with 15% yellow soda ash control pH=6, after finishing, stir sampling in per 10 minutes, survey terminal point, OV method and liquid phase method are synchronous in the measurement.
(d) press filtration: after terminal point was qualified, filter, mother liquor were collected in another 20 tons of retort, and filter cake is packed into standby in the bag.
(e) film is saturating: mother liquor is 15 tons in the holding tank, crosses film, film and sees through in the journey the saturating temperature of controlling diaphragm below 30 ℃, crosses behind the film in bag the filter cake dispersion of pulling an oar.
(f) drying: after above-mentioned product being added the dust-proofing agent of product 1% weight, control pH=6.5, temperature are carried out the spray tower drying for 105 ℃.
Present embodiment aspect waste water, output, cost with the correlated beneficial effect of old technology as follows:
| Project | Old technology | Novel process |
| Waste water | 25 tons | 0 ton |
| Output | 1 ton | 1.2 ton |
| Cost | Reduce by 10% |
The method of present embodiment obviously has improvement than the old technology described in the background technology in many-side, at first the waste water generation produces 25 tons of waste water by the finished product of 1 ton of original every generation, then productive rate has improved 20% now, and wastewater flow rate but has been reduced to 0 ton, technology to diverted via effect very obvious.
Dyestuff of the present invention and dyestuff preparation method are described by specific embodiment.Those skilled in the art can use for reference links such as content appropriate change raw material of the present invention, processing condition and realize corresponding other purpose, its relevant change does not all break away from content of the present invention, all similar replacements and change will become apparent to those skilled in the art that and all be regarded as comprising within the scope of the present invention.
Claims (1)
1, a kind of preparation method of reactive red 3G dyestuff is characterized in that this preparation method comprises the steps:
(a) two activators and diazotization reaction between: in 20 tons of retort, add and add 2 of 254Kg under 3.5 tons of stirrings of end water, 4-diamino benzene sulfonic acid sodium, make it molten entirely, add the trolamine of 33Kg and the EDTA of 60Kg, abundant stirring and dissolving, complete molten back adds trash ice, controlled temperature 0-5 ℃ added 2 of 280Kg with 1.5 hours, 3-two bromo propionyl chloros and acetone 30Kg mixed solution, and control pH=6.0-6.3 with 15% sodium carbonate solution, after reaction is finished, the hydrochloric acid that adds 112.3Kg, and 25 ℃ sodium nitrite solution, controlled temperature was in 14 ℃ of reactions 3 hours, keep Sodium Nitrite little excessive during this time, obtain diazonium liquid;
(b) condensation reaction: in 20 tons of retort, add 3.5 tons in end water, stir the γ acid that adds 240.3Kg down, transfer pH=7.0 with 15% sodium carbonate solution, complete molten back adds trash ice and cools to 12 ℃, in 3 hours, at the uniform velocity add 2 of 260Kg, the mixed solution of 3-two bromo propionyl chloros and 25Kg acetone, during with 15% sodium carbonate solution control pH=5.0-6.0, finish afterreaction 2 hours, and got condensation reaction solution;
(c) coupled reaction: the Sodium Nitrite in above-mentioned (a) is removed with an amount of thionamic acid, then in 1 hour, simultaneously 20 ℃ ± 1 ℃ of controlled temperature joins it in (b), with 15% yellow soda ash control pH=6, after finishing, stir sampling in per 10 minutes, survey terminal point, OV method and liquid phase method are synchronous in the measurement;
(d) press filtration: after terminal point was qualified, filter, mother liquor were collected in another 20 tons of retort, and filter cake is packed into standby in the bag;
(e) film is saturating: mother liquor is 15 tons in the holding tank, crosses film, film and sees through in the journey the saturating temperature of controlling diaphragm below 30 ℃, crosses behind the film in bag the filter cake dispersion of pulling an oar;
(f) drying: after above-mentioned product being added the dust-proofing agent of product 1% weight, control pH=6.5, temperature are carried out the spray tower drying for 105 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008101541127A CN101481524A (en) | 2008-12-12 | 2008-12-12 | Preparation of reactive red 3G dye |
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2008101541127A CN101481524A (en) | 2008-12-12 | 2008-12-12 | Preparation of reactive red 3G dye |
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| CN101481524A true CN101481524A (en) | 2009-07-15 |
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| CNA2008101541127A Pending CN101481524A (en) | 2008-12-12 | 2008-12-12 | Preparation of reactive red 3G dye |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105542511A (en) * | 2015-12-22 | 2016-05-04 | 浙江亿得化工有限公司 | A composite active red dye used for wool and a preparing method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5092903A (en) * | 1989-09-22 | 1992-03-03 | Ciba-Geigy Corporation | Process for dyeing or printing blends of cellulosic fibre materials and silk with dihalo-propionamido or halo-acryl amido reactive dyes |
| DE19527365A1 (en) * | 1995-07-26 | 1997-01-30 | Ciba Geigy Ag | Dyeing wool, including carbonated wool in level deep hue with good fastness - comprises dyeing with reactive dye contg. di:halo-propionyl-amino or halo-acryloyl-amino gp. in acid medium |
| CN101215425A (en) * | 2008-01-22 | 2008-07-09 | 天津市德凯化工有限公司 | Red reactive dyestuffs and preparation method thereof |
| CN101215427A (en) * | 2008-01-22 | 2008-07-09 | 天津市德凯化工有限公司 | Method of preparing navy blue active dyestuff |
| CN101585975A (en) * | 2008-12-12 | 2009-11-25 | 天津市德凯化工有限公司 | Method for preparing reactive red 3G for wool |
-
2008
- 2008-12-12 CN CNA2008101541127A patent/CN101481524A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5092903A (en) * | 1989-09-22 | 1992-03-03 | Ciba-Geigy Corporation | Process for dyeing or printing blends of cellulosic fibre materials and silk with dihalo-propionamido or halo-acryl amido reactive dyes |
| DE19527365A1 (en) * | 1995-07-26 | 1997-01-30 | Ciba Geigy Ag | Dyeing wool, including carbonated wool in level deep hue with good fastness - comprises dyeing with reactive dye contg. di:halo-propionyl-amino or halo-acryloyl-amino gp. in acid medium |
| CN101215425A (en) * | 2008-01-22 | 2008-07-09 | 天津市德凯化工有限公司 | Red reactive dyestuffs and preparation method thereof |
| CN101215427A (en) * | 2008-01-22 | 2008-07-09 | 天津市德凯化工有限公司 | Method of preparing navy blue active dyestuff |
| CN101585975A (en) * | 2008-12-12 | 2009-11-25 | 天津市德凯化工有限公司 | Method for preparing reactive red 3G for wool |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105542511A (en) * | 2015-12-22 | 2016-05-04 | 浙江亿得化工有限公司 | A composite active red dye used for wool and a preparing method thereof |
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Application publication date: 20090715 |