CN1141914A - Refining technology of high-purity sodium bromaminate - Google Patents
Refining technology of high-purity sodium bromaminate Download PDFInfo
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- CN1141914A CN1141914A CN 94114113 CN94114113A CN1141914A CN 1141914 A CN1141914 A CN 1141914A CN 94114113 CN94114113 CN 94114113 CN 94114113 A CN94114113 A CN 94114113A CN 1141914 A CN1141914 A CN 1141914A
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- bromaminate
- sodium bromaminate
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Abstract
The technological process for refining dye intermediate sodium bromaminate is characterized by combining synthesis and refining process together, making crude sodium bromaminate pass through such processes as dissolving, filtering and direct cooling treatment to make sodium bromaminate separate from, and using brominating process or refining process to obtain the refined sodium bromaminate. Said process is low in cost, high in yield and free from environmental pollution.
Description
The present invention relates to a kind of refining purifying technique of dyestuff intermediate sodium bromaminate.
Sodium bromaminate (chemical name is 1-amino-4-bromo anthraquinone-2-sulfonic acid) generally exists with the form of sodium salt, but still be called bromamine acid traditionally, when cubage, sometimes pressing free acid calculates, promptly pressing molecular weight 382 calculates, sometimes press sodium salt and calculate, promptly press molecular weight 404 and calculate, sodium bromaminate content involved in the present invention all calculates by molecular weight 404.Sodium bromaminate is synthetic high-grade activity, acidity, disperses and the indispensable intermediate of other class dyestuff, because the sodium bromaminate quality is very big to synthetic dyestuff quality influence, the directly synthetic requirement that can not satisfy synthetic dyestuff without the purified sodium bromaminate, therefore, the synthetic sodium bromaminate must be refining through one or many.Currently used sodium bromaminate process for refining mainly is that the sodium bromaminate crude product is dissolved in the hot water, remove by filter insolubles, the inorganic salt such as sodium sulfate of adding about 2% salt out sodium bromaminate, there is following shortcoming in this process for refining: owing to add a large amount of inorganic salt when the crystallization of sodium bromaminate impurity is separated out simultaneously, refining effect is poor; Have a lot of salt in the product, sodium bromaminate content is difficult to improve, and existing goods sodium bromaminate content is seldom more than 96%; Each mother liquor of discharging contains a certain amount of sodium bromaminate, and refining yield is lower; Owing to, refining cost is increased with salt; Each making with extra care will be discharged a large amount of waste water, and three wastes treatment capacity is bigger.
The objective of the invention is to overcome the shortcoming and defect that existing sodium bromaminate process for refining exists, thus proposed a kind of with the sodium bromaminate crude product through hot water dissolving, filtration, do not add inorganic salt or add the high-purity sodium bromaminate process for refining that small amounts of inorganic salt crystallisation by cooling is separated out.
The present invention realizes like this, the bromination technology of bromamine acid mainly contains dual mode, a kind of mode be 1-aminoanthraquinone-2-sulfonic acid in water medium, (generally at 0-5 ℃) and bromizating agent reaction at low temperatures will add hypochlorite or oxymuriate in order to make full use of bromizating agent; Another kind of bromination mode is that 1-aminoanthraquinone-2-sulfonic acid is in sulfuric acid or oleum medium, (generally at 80-85 ℃) and bromizating agent reaction under higher temperature, will dilute after the reaction: be diluted to sulfuric acid concentration 50-60%, bromamine acid is separated out with the form of vitriol; Perhaps be diluted to sulfuric acid concentration and neutralize below 30% or saltout, bromamine acid is separated out with the form of an alkali metal salt.It is refining that the bromination mode that The present invention be directed to above two kinds of bromamine acids commonly used is carried out sodium bromaminate, and treating process and bromination process combined, concrete grammar is the synthetic method according to existing sodium bromaminate, promptly the sodium bromaminate crude product that obtains through sulfonation and bromination with the 1-aminoanthraquinone is at 60-105 ℃, preferably in 80-95 ℃ hot water, dissolve, the concentration of bromamine acid is 2-15% in the solution, preferably at 5-10%, filtered while hot is removed insoluble impurities (if with activated carbon filtration or better with chlorobenzene or other water-insoluble organic solvents effect of extracting while hot), and with small amount of thermal water washing insolubles filter cake, allow filtering mother liquor and washing lotion not add the direct crystallisation by cooling of inorganic salt, sodium bromaminate is separated out, perhaps add the following inorganic salt of cumulative volume %, preferably sodium bromaminate is separated out in the cooling of the sodium sulfate below 0.3%, separate out temperature generally at 0-50 ℃, be preferably in 5-30 ℃, the sodium bromaminate of separating out filters, filter cake is the sodium bromaminate elaboration, contain a small amount of sodium bromaminate and less water insoluble impurities in the filtrate, but the amount of its impurity is with respect to thick sodium bromaminate, almost can ignore, can overlap fully and be used for bromo chemical skill.For first kind of bromination technology, filtrated stock is as the medium of bromination, and for second kind of bromination technology, filtrated stock adds water as the dilution after the bromination, filtrated stock cover for secondary refining is used for once making with extra care, and applies mechanically the quality that filtrated stock does not influence thick propylhomoserin sodium basically.
The present invention since in the precipitation process of sodium bromaminate not with salt or add small amounts of salts, be equivalent to recrystallization process, impurity can not separated out simultaneously, refining effect is good, the product quality height; Owing to do not saltout, in the product saliferous seldom, the content of sodium bromaminate is very high, once refining sodium bromaminate content can reach more than 98%, twice refining sodium bromaminate content can reach more than 99%; Because treating process is not discharged mother liquor, does not have the loss of sodium bromaminate, refining yield reaches more than 99%; Owing to, reduced refining cost not with salt; There are not " three wastes " to produce in the treating process.
Below with embodiment specific implementation process of the present invention is described.
Embodiment 1
In the sulfuric acid of 80g100%, be dissolved with 1-aminoanthraquinone-2-sulfonic acid 100% amount of amounting to and be warming up to 80 ℃ for 30.3g, 80-85 ℃ added 28g liquid bromine in 12 hours after, react 2 hours more to terminal, then material is diluted in batch refinement mother liquor and (contains the about 2g of bromamine acid sodium in the mother liquor, the about 600ml of volume), adding 30% liquid caustic soda, to be neutralized to pH value be 7, be cooled to 40 ℃ of filtrations, filter cake is the sodium bromaminate crude product, dry back weight is 49.2g, sodium bromaminate content is 82%, and amounting to 100% weight is 40.4g, and the bromination yield is 95%.
The sodium bromaminate crude product adds in the 600ml water, heating 95 ℃ makes sodium bromaminate molten entirely, filtered while hot, with small amount of thermal water washing filter cake, filter cake is with 1-amino-2, and the 4-dibromo-anthraquinone is main water-insoluble impurity, merge mother liquor and washing lotion, add the 2g gac, stir the 15min filtered while hot in 95 ℃ and remove gac, use small amount of thermal water washing gac again, merge mother liquor and washing lotion, be cooled to 20 ℃ sodium bromaminate is separated out fully, filter, filter cake is a purified sodium bromaminate product, the heavy 38.8g in dry back, sodium bromaminate content is 98.2%, 1-amino-2 wherein, 4-dibromo-anthraquinone content 0.2%, 1-aminoanthraquinone-2-sulfonic acid content 0.2%, contain the about 2g of sodium bromaminate in the mother liquor, serve as down the dilution of batch bromination reaction, refining yield 99.3%.
Embodiment 2
On 500ml, criticize in the refinement mother liquor, get its 150ml as the bromination medium, amount to 1-aminoanthraquinone-2-sulfonic acid 30.3g of 100% at 20 ℃ to wherein adding, being neutralized to pH value with aqueous sodium hydroxide solution is 6, be cooled to 0-5 ℃, under this temperature, dripped 9.2g liquid bromine in 2 hours, make the pH value of system remain on 5.5-6.5 with dilute sodium hydroxide aqueous solution during this period, then under same temperature, dripped 25.8g content and be 12% aqueous sodium hypochlorite solution in 3 hours, keep the pH value of system at 5.5-6.5 with dilute sulfuric acid aqueous solution during this period, remove unnecessary bromine with S-WAT, the remainder of batch refinement mother liquor on adding, the after-filtration that stirs, filter cake is thick sodium bromaminate.The heavy 45.7g in dry back, sodium bromaminate content 87.5%, on criticize mother liquor and contain the about 3g of bromamine acid sodium, bromination yield 91.5%.
The sodium bromaminate crude product is dissolved in the 500ml water, heating 95 ℃ makes sodium bromaminate molten entirely, filtered while hot, with small amount of thermal water washing filter cake, filter cake is with 1-amino-2, and the 4-dibromo-anthraquinone is main water-insoluble impurity, merge mother liquor and washing lotion, add the 2g gac, stir the 15min filtered while hot in 95 ℃ and remove gac, use small amount of thermal water washing gac again, merge mother liquor and washing lotion, be cooled to 20 ℃ sodium bromaminate is separated out fully, filter, filter cake is a purified sodium bromaminate product, the heavy 37.2g in dry back, sodium bromaminate content is 98.6%, 1-amino-2 wherein, and the 4-dibromo is feared quinone content 0.2%, 1-aminoanthraquinone-2-sulfonic acid content 0.3%, contain the about 3g of bromamine acid in the mother liquor, serve as down the dilution of batch bromination reaction, refining yield 99.1%.
Embodiment 3
Bromination obtains the thick sodium bromaminate of 49.2g with embodiment 1, crowd secondary refining mother liquor 600ml in the adding, wherein contain sodium bromaminate 6g, be heated to 95 ℃, filtered while hot is removed insolubles, use the small amount of thermal water washing again, merge mother liquor and washing lotion, add the 200g chlorobenzene, in 95 ℃ of stirring extractions 1 hour, separate dechlorination benzene, water layer is cooled to room temperature, sodium bromaminate is separated out, and filters, and filter cake is purified product of sodium bromaminate, the product weight of giving money as a gift 42.9g, content 98.2%.The about 600ml of mother liquor contains the about 2g of sodium bromaminate, the diluting water of bromination when being used for synthesizing sodium bromaminate next time.
A purified sodium bromaminate filter cake, add in the 600ml water, add the 2g gac again, be warming up to 95 ℃, make sodium bromaminate molten entirely, filtered while hot is removed gac, adds small amount of thermal water washing gac again, merges mother liquor and washing lotion, be cooled to room temperature, sodium bromaminate is separated out, filter, filter cake is the sodium bromaminate of secondary refining, the heavy 37.9g in dry back, sodium bromaminate content is 99.6%, 1-amino-2,4-dibromo-anthraquinone content 0.05%, 1-aminoanthraquinone-2-sulfonic acid content 0.1%, the about 600ml of mother liquor contains the about 6g of bromamine acid sodium, as following batch of purified dissolving water.Twice purified total recovery is 98.4%.
Embodiment 4
In the sulfuric acid of 80g100%, be dissolved with 1-aminoanthraquinone-2-sulfonic acid 100% amount of amounting to and be warming up to 80 ℃ for 30.3g, added 28g liquid bromine in 12 hours at 80-85 ℃, react 2 hours more to terminal, be cooled to 60 ℃, drip 60ml water, use the sulfuric acid scrubbing of 100g55% again, filter cake is used the dissolving of batch refinement mother liquor, on criticize mother liquor volume 600ml, wherein be dissolved with the about 3g of sodium bromaminate, being neutralized to PH with NaOH is 7, is cooled to 30 ℃, filters, filter cake is the sodium bromaminate crude product, heavy 43.5g, sodium bromaminate content 90.5%, bromination yield 89.8%.
The sodium bromaminate crude product adds in the 600ml water, be warming up to 90 ℃ and make it molten entirely, add the 2g gac, stir 10min, filtered while hot is removed insolubles, use small amount of thermal water washing filter cake again, merge mother liquor and washing lotion, be cooled to 20 ℃, the sodium bromaminate crystallization is separated out, filter, filter cake is the highly finished product of sodium bromaminate, the heavy 36.3g in dry back, sodium bromaminate content is 98.8%, 1-amino-2,4-dibromo-anthraquinone content 0.2%, 1-aminoanthraquinone-2-sulfonic acid content 0.25%, mother liquor volume 600ml, wherein contain the about 3g of sodium bromaminate, as the neutralization medium of following batch bromination, refining yield 98.6%.
Comparative Examples 1
Bromination is with embodiment 1, bromination is to terminal point, material is diluted in the 600ml water, and adding 30% liquid caustic soda, to be neutralized to pH value be 7, is cooled to 40 ℃, filter, filter cake is the sodium bromaminate crude product, and dry back weight is 46.8g, and sodium bromaminate content is 82%, amounting to 100% weight is 38.4g, and the bromination yield is 95%.
The sodium bromaminate crude product adds in the 600ml water, heating 95 ℃ makes sodium bromaminate molten entirely, filtered while hot, with small amount of thermal water washing filter cake, filter cake is with 1-amino-2, and the 4-dibromo-anthraquinone is main water-insoluble impurity, merge mother liquor and washing lotion, add the 2g gac, stir the 15min filtered while hot in 95 ℃ and remove gac, use small amount of thermal water washing gac again, merge mother liquor and washing lotion, add the 12g anhydrous sodium sulphate at 80 ℃, be cooled to 20 ℃ sodium bromaminate is separated out fully, filter, filter cake washs with the sodium sulfate of 600ml2%, filter cake is a purified sodium bromaminate product, the heavy 39.5g in dry back, and sodium bromaminate content is 92.6%, 1-amino-2 wherein, 4-dibromo-anthraquinone content 0.7%, 1-aminoanthraquinone-2-sulfonic acid content 1.2%, refining yield 95.2%.
Comparative Examples 2
Bromination is used 500ml water with embodiment 2, and goes up batch refinement mother liquor as bromination medium and diluting water without 500ml, heavy 42.4g after the thick sodium bromaminate drying that obtains, sodium bromaminate content 87.5%, bromination yield 91.5%.
The sodium bromaminate crude product is dissolved in the 500ml water, heating 95 ℃ makes sodium bromaminate molten entirely, filtered while hot, with small amount of thermal water washing filter cake, filter cake is with 1-amino-2, and the 4-dibromo-anthraquinone is main water-insoluble impurity, merge mother liquor and washing lotion, add the 2g gac, stir the 15min filtered while hot in 95 ℃ and remove gac, use small amount of thermal water washing gac again, merge mother liquor and washing lotion, add the 10g anhydrous sodium sulphate at 80 ℃, be cooled to 20 ℃ sodium bromaminate is separated out fully, filter, sulphuric acid soln with 500ml2% washs again, filter cake is a purified sodium bromaminate product, the heavy 37.5g in dry back, and sodium bromaminate content is 93.3%, refining yield 94.6%, contain 1-amino-2 in the sodium bromaminate, 4-dibromo-anthraquinone 0.75%, 1-aminoanthraquinone-2-sulfonic acid 1.3%.
Claims (5)
1, a kind of by 1-aminoanthraquinone-2-sulfonic acid and bromizating agent through bromination, after thick sodium bromaminate is made in filtration, the heat that thick sodium bromaminate is added 60-105 ℃ is held middle dissolving, sodium bromaminate concentration reaches 2-15% in the solution, filtered while hot is removed insoluble impurity, with hot wash insolubles filter cake, filtrated stock and washing lotion, technology at 0-50 ℃ of following crystallisation by cooling purifying high-purity sodium bromaminate, after it is characterized in that in filtrated stock and washing lotion, adding the 0-1% inorganic salt, crystallisation by cooling is separated out the sodium bromaminate after-filtration, and filtrate cover is used for bromo chemical skill or cover, and to be used for repeatedly purified last time refining.
2, the process for refining of a kind of high-purity sodium bromaminate according to claim 1, it is characterized in that filtrated stock and washing lotion together directly crystallisation by cooling separate out sodium bromaminate.
3, the process for refining of a kind of high-purity sodium bromaminate according to claim 1, it is characterized in that filtrated stock and washing lotion add 1% following inorganic salt after, crystallisation by cooling is separated out sodium bromaminate.
4, the process for refining of a kind of high-purity sodium bromaminate according to claim 1 is characterized in that the filtered liquid cover that crystallisation by cooling is separated out behind the sodium bromaminate is used for the bromo chemical skill.
5, the process for refining of a kind of high-purity sodium bromaminate according to claim 1, it is characterized in that separating out the filtered liquid cover of sodium bromaminate by crystallisation by cooling, to be used for repeatedly purified last time refining.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94114113 CN1141914A (en) | 1994-09-24 | 1994-09-24 | Refining technology of high-purity sodium bromaminate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94114113 CN1141914A (en) | 1994-09-24 | 1994-09-24 | Refining technology of high-purity sodium bromaminate |
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| CN1141914A true CN1141914A (en) | 1997-02-05 |
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| CN 94114113 Pending CN1141914A (en) | 1994-09-24 | 1994-09-24 | Refining technology of high-purity sodium bromaminate |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103880713A (en) * | 2014-04-16 | 2014-06-25 | 南京大学盐城环保技术与工程研究院 | Method for recycling bromaminic acid from production wastewater of reactive brilliant blue KN-R of vinyl sulfone type dye |
| CN106083660A (en) * | 2016-06-12 | 2016-11-09 | 南通市争妍颜料化工有限公司 | A kind of preparation technology of 1 amino 4 bromo anthraquinone 2 sodium sulfonate |
| CN106565547A (en) * | 2016-10-19 | 2017-04-19 | 烟台安诺其精细化工有限公司 | Preparation method of bromaminic acid sodium salt and intermediate of bromaminic acid sodium salt and solvent recovery method |
| CN107400071A (en) * | 2017-05-25 | 2017-11-28 | 盐城市瓯华化学工业有限公司 | A kind of bromamine acid production method |
| CN113105371A (en) * | 2019-12-12 | 2021-07-13 | 林齐坤 | Production method of bromamine acid bromination workshop section |
-
1994
- 1994-09-24 CN CN 94114113 patent/CN1141914A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103880713A (en) * | 2014-04-16 | 2014-06-25 | 南京大学盐城环保技术与工程研究院 | Method for recycling bromaminic acid from production wastewater of reactive brilliant blue KN-R of vinyl sulfone type dye |
| CN103880713B (en) * | 2014-04-16 | 2015-05-13 | 南京大学盐城环保技术与工程研究院 | Method for recycling bromaminic acid from production wastewater of reactive brilliant blue KN-R of vinyl sulfone type dye |
| CN106083660A (en) * | 2016-06-12 | 2016-11-09 | 南通市争妍颜料化工有限公司 | A kind of preparation technology of 1 amino 4 bromo anthraquinone 2 sodium sulfonate |
| CN106083660B (en) * | 2016-06-12 | 2018-06-26 | 南通市争妍新材料科技有限公司 | A kind of preparation process of 1- amino -4- bromo anthraquinone -2- sodium sulfonates |
| CN106565547A (en) * | 2016-10-19 | 2017-04-19 | 烟台安诺其精细化工有限公司 | Preparation method of bromaminic acid sodium salt and intermediate of bromaminic acid sodium salt and solvent recovery method |
| CN107400071A (en) * | 2017-05-25 | 2017-11-28 | 盐城市瓯华化学工业有限公司 | A kind of bromamine acid production method |
| CN113105371A (en) * | 2019-12-12 | 2021-07-13 | 林齐坤 | Production method of bromamine acid bromination workshop section |
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