CN100451000C - Process of preparing high quality sodium salt of DSD acid with industrial DSD acid - Google Patents
Process of preparing high quality sodium salt of DSD acid with industrial DSD acid Download PDFInfo
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- CN100451000C CN100451000C CNB2007100576228A CN200710057622A CN100451000C CN 100451000 C CN100451000 C CN 100451000C CN B2007100576228 A CNB2007100576228 A CN B2007100576228A CN 200710057622 A CN200710057622 A CN 200710057622A CN 100451000 C CN100451000 C CN 100451000C
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- diaminobenzil
- disulfonic acid
- filter cake
- dsd acid
- sodium salt
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Abstract
The process of preparing high quality sodium salt of DSD acid with industrial DSD acid includes the following steps: adding industrial DSD acid into deionized water in lucifugous condition, dropping alkali solution to react at 80-83 deg.c and pH 6-7 to obtain DSD acid sodium salt solution; cooling to 20-30 deg.c to crystallize, filtering to obtain filter cake of DSD acid sodium salt; dissolving the filter cake in deionized water at 80-83 deg.c, cooling to 20-30 deg.c to crystallize again, filtering to obtain filter cake; washing the filter cake with anhydrous alcohol and lucifugous stoving at 30-60 deg.c to obtain DSD acid sodium salt product of purity over 99.5 %. The process is simple and practical.
Description
Technical field
The present invention relates to a kind of method, belong to DSD acid sodium-salt technology of preparing by the high-quality DSD acid sodium-salt of industrial goods DSD acid preparation.
Background technology
4,4 '-diaminobenzil-2,2 '-disulfonic acid (be called for short DSD acid) is the important intermediate of producing dyestuff, is widely used in synthetic toluylene type white dyes, stilbene is substantive dyestuff, reactive dyestuffs.The annual production of China DSD acid at present reaches more than 30,000 tons, has become main in the world DSD acid producing country and export State.
The synthetic of DSD acid generally is made up of sulfonation, oxidative condensation, reduction three parts.At first prepare sodium p-nitrotoluene-2-sulfonic acid (NTS) by para-nitrotoluene (PNT) sulfonation, NTS oxidative condensation in alkaline medium obtains 4,4 '-dinitrobenzene toluylene-2, and 2 '-disulfonic acid (DNS), DNS prepares DSD acid with iron powder reducing.
The industry standard regulation of industrial goods DSD acid, in the DSD acid 4,4 '-diamino diphenylethane-2,2 '-disulfonic acid (benzyl thing) is that major impurity and content should be below 1.5%, yet industrial application shows that in the industrial goods DSD acid also is the important impurity that influences DSD acid derived product quality to amino ortho-sulfonic acid phenyl aldehyde and cis DSD acid.These impurity that generate in building-up process have had a strong impact on the fluorescence of DSD acid, cause DSD acid product and derived product thereof to lack international competitiveness.
The process for purification of traditional industrial goods DSD acid is that industrial goods DSD acid is made saturated solution with alkali dissolution, crystallisation by cooling obtains DSD acid sodium-salt filter cake then, the shortcoming of this method is owing to do not carry out under the lucifuge condition, cause the basic solution and the aqueous DSD acid sodium-salt filter cake of DSD acid sodium-salt within a short period of time the red impurity of generation to take place to decompose, thereby influence product purity.
Summary of the invention
The object of the present invention is to provide a kind of method by the high-quality DSD acid sodium-salt of industrial goods DSD acid preparation.This method technology is simple, and economic serviceability is strong, the product purity height that obtains.
The present invention is realized that by the following technical programs a kind of method by the high-quality DSD acid sodium-salt of industrial goods DSD acid preparation is characterized in that comprising following process:
1. under the lucifuge condition, press industrial goods 4,4 '-diaminobenzil-2,2 '-disulfonic acid (DSD acid) is 1 with the mass ratio of water: 1.5-2.5, DSD acid is added in the deionized water, slowly add alkaline solution, controlled temperature 80-83 ℃, pH6-7, make industrial goods DSD acid dissolving, obtain DSD acid sodium-salt solution.
2. under the lucifuge condition, the DSD acid sodium-salt solution of step 1 is cooled to 20-30 ℃, crystallization, filtration obtains DSD acid sodium-salt filter cake.
3. under the lucifuge condition, be 1 with the DSD acid sodium-salt filter cake of step 2 by the mass ratio with water: 1-1.25 adds DSD acid sodium-salt filter cake in the deionized water, controlled temperature 80-83 ℃, make DSD acid sodium-salt solution, be cooled to 20-30 ℃ and carry out secondary crystal, filter and obtain DSD acid sodium-salt filter cake.
4. under the lucifuge condition, colourless until washings with the DSD acid sodium-salt filter cake that dehydrated alcohol thorough washing step 3 obtains, then in the oven dry of 30-60 ℃ of lucifuge, obtain purity and be the DSD acid sodium-salt more than 99.5%.
Above-mentioned alkali lye is sodium hydroxide, potassium hydroxide, yellow soda ash or their mixture.
Principle of Process of the present invention:
1.DSD the rising of the solubility with temperature of acid sodium-salt in water enlarges markedly.Under 80-83 ℃, make DSD acid sodium-salt solution postcooling to 20-30 ℃, crystal can be separated out in a large number, and separates out seldom with the reduction impurity crystallization of temperature, removes impurity thereby reached, and improves the purpose of purity.
2. in the DSD of pH＞7 acid sodium-salt solution, the DSD acid sodium-salt is subjected to illumination effect easily to be transformed into cis DSD acid sodium-salt, and then is oxidized into red to amino ortho-sulfonic acid phenyl aldehyde sodium salt.Under the lucifuge condition and control pH6-7 carry out crystallization and purification, can reduce the generation of above-mentioned impurity.
3. contain a spot of water in the DSD acid sodium-salt crystal after the crystallization, under illumination condition easily oxidized be transformed into red to amino ortho-sulfonic acid phenyl aldehyde sodium salt.With dehydrated alcohol thorough washing DSD acid sodium-salt filter cake, replace wherein a spot of water, can prevent that the DSD acid sodium-salt is rotten.
Technical progress of the present invention shows the following aspects:
With the DSD acid sodium-salt filter cake of dehydrated alcohol thorough washing secondary crystal gained, can prevent that the DSD acid sodium-salt is rotten; DSD acid sodium-salt purity after the purification reaches more than 99.5%; Technology is simple, and is easy to operate, the economy height.
Embodiment
Embodiment 1
Under the lucifuge condition, the industrial goods DSD acid (dry product, purity about 95%) of 50g is placed the 500ml beaker, add 100ml distilled water, open and stir; Drip mass concentration and be 20% aqueous sodium hydroxide solution, be warming up to 83 ℃ gradually, to the pH value be 6-7; Treat that solution is transparence, continue stirring, constant temperature 5-10min, naturally cool to 25 ℃ under sealing, the lucifuge condition, suction filtration separates, and obtains filter cake 60g.The gained filter cake adds 75ml distilled water, be warming up to 83 ℃ of dissolvings gradually, naturally cool to 25 ℃ under sealing, the lucifuge condition and carry out secondary crystal, suction filtration separates, and the filter cake of secondary crystal is at every turn with dehydrated alcohol 50mL washing 6 times, and is colourless until washings, then in 45 ℃ of lucifuge oven dry, obtain DSD acid sodium-salt dry product 43g, product reaches 99.7% through the high performance liquid chromatograph purity assay, is 78% in the yield of dry product.
Embodiment 2
Under the lucifuge condition, the industrial goods DSD acid (dry product, purity about 95%) of 50g is placed the 500ml beaker, add 125ml distilled water, open and stir; Drip mass concentration and be 20% aqueous sodium hydroxide solution, be warming up to 80 ℃ gradually, to the pH value be 6-7; Treat that solution is transparence, continue stirring, constant temperature 5-10min, naturally cool to 22 ℃ under sealing, the lucifuge condition, suction filtration separates, and obtains filter cake 55g.The gained filter cake adds 70ml distilled water, be warming up to 82 ℃ of dissolvings gradually, naturally cool to 22 ℃ under sealing, the lucifuge condition and carry out secondary crystal, suction filtration separates, and the filter cake of secondary crystal is at every turn with dehydrated alcohol 50mL washing 6 times, and is colourless until washings, then in 40 ℃ of lucifuge oven dry, obtain DSD acid sodium-salt dry product 38g, product reaches 99.7% through the high performance liquid chromatograph purity assay, is 68.9% in the yield of dry product.
Embodiment 3
Under the lucifuge condition, the industrial goods DSD acid (dry product, purity about 95%) of 50g is placed the 500ml beaker, add 100ml distilled water, open and stir; Drip mass concentration and be 20% potassium hydroxide aqueous solution, be warming up to 83 ℃ gradually, to the pH value be 6-7; Treat that solution is transparence, continue stirring, constant temperature 5-10min, naturally cool to 25 ℃ under sealing, the lucifuge condition, suction filtration separates, and obtains filter cake 63g.The gained filter cake adds 75ml distilled water, be warming up to 80 ℃ of dissolvings gradually, naturally cool to 25 ℃ under sealing, the lucifuge condition and carry out secondary crystal, suction filtration separates, and the filter cake of secondary crystal is at every turn with dehydrated alcohol 50mL washing 6 times, and is colourless until washings, then in 35 ℃ of lucifuge oven dry, obtain DSD acid sodium-salt dry product 45g, product reaches 99.7% through the high performance liquid chromatograph purity assay, is 81.6% in the yield of dry product.
Embodiment 4
Under the lucifuge condition, the industrial goods DSD acid (dry product, purity about 95%) of 60g is placed the 500ml beaker, add 110ml distilled water, open and stir; Drip mass concentration and be 10% aqueous sodium hydroxide solution, be warming up to 83 ℃ gradually, to the pH value be 6-7; Treat that solution is transparence, continue stirring, constant temperature 5-10min, naturally cool to 25 ℃ under sealing, the lucifuge condition, suction filtration separates, and obtains filter cake 70g.The gained filter cake adds 80ml distilled water, be warming up to 82 ℃ of dissolvings gradually, naturally cool to 25 ℃ under sealing, the lucifuge condition and carry out secondary crystal, suction filtration separates, and the filter cake of secondary crystal is at every turn with dehydrated alcohol 50mL washing 6 times, and is colourless until washings, then in 55 ℃ of lucifuge oven dry, obtain DSD acid sodium-salt dry product 53g, product reaches 99.6% through the high performance liquid chromatograph purity assay, is 83% in the yield of dry product.
Embodiment 5
Under the lucifuge condition, the industrial goods DSD acid (dry product, purity about 95%) of 55g is placed the 500ml beaker, add 110ml distilled water, open and stir; Drip mass concentration and be 20% aqueous sodium carbonate, be warming up to 83 ℃ gradually, to the pH value be 6-7; Treat that solution is transparence, continue stirring, constant temperature 5-10min, naturally cool to 25 ℃ under sealing, the lucifuge condition, suction filtration separates, and obtains filter cake 66g.The gained filter cake adds 70ml distilled water, be warming up to 83 ℃ of dissolvings gradually, naturally cool to 25 ℃ under sealing, the lucifuge condition and carry out secondary crystal, suction filtration separates, and the filter cake of secondary crystal is at every turn with dehydrated alcohol 50mL washing 6 times, and is colourless until washings, then in 60 ℃ of lucifuge oven dry, obtain DSD acid sodium-salt dry product 47.3g, product reaches 99.5% through the high performance liquid chromatograph purity assay, is 78% in the yield of dry product.
Comparative Examples 1
Under illumination condition, the industrial goods DSD acid (dry product, purity about 95%) of 50g is placed the 500ml beaker, add 100ml distilled water, open and stir; Drip mass concentration and be 20% aqueous sodium hydroxide solution, be warming up to 83 ℃ gradually, to the pH value be 6-7; Treat that solution is transparence, continue stirring, constant temperature 5-10min, naturally cool to 25 ℃, suction filtration separates, and collects filter cake.The gained filter cake adds 75ml distilled water, be warming up to 83 ℃ of dissolvings gradually, naturally cool to 25 ℃ and carry out secondary crystal, suction filtration separates, the filter cake of secondary crystal is in 45 ℃ of oven dry, and the surface has red material to generate, and obtains DSD acid sodium-salt dry product 43g, product is 95.7% through the high performance liquid chromatograph purity assay, is 78% in the yield of dry product.
Comparative Examples 2
Under the lucifuge condition, the industrial goods DSD acid (dry product, purity about 95%) of 50g is placed the 500ml beaker, add 100ml distilled water, open and stir; Drip mass concentration and be 20% aqueous sodium hydroxide solution, be warming up to 83 ℃ gradually, to the pH value be 6-7; Treat that solution is transparence, continue stirring, constant temperature 5-10min, naturally cool to 25 ℃ under sealing, the lucifuge condition, suction filtration separates, and collects filter cake.The gained filter cake adds 75ml distilled water, be warming up to 83 ℃ of dissolvings gradually, naturally cool to 25 ℃ under sealing, the lucifuge condition and carry out secondary crystal, suction filtration separates, the filter cake of secondary crystal is dried in 45 ℃ of lucifuges, obtain DSD acid sodium-salt dry product 43g, product reaches 98.9% with the high performance liquid chromatograph purity assay immediately, this product sees that in air light placement rear surface reddens gradually, after being respectively 0.5 hour, 1 hour, 5 hours, 24 hours storage period, product purity is respectively 96.9%, 95.7%, 94.8%, 93.2%.
Comparative Examples 3
Under illumination condition, the industrial goods DSD acid (dry product, purity about 95%) of 50g is placed the 500ml beaker, add 100ml distilled water, open and stir; Drip mass concentration and be 20% aqueous sodium hydroxide solution, be warming up to 83 ℃ gradually, to the pH value be 6-7; Treat that solution is transparence, continue stirring, constant temperature 5-10min, naturally cool to 25 ℃, suction filtration separates, and filtrate takes on a red color, and collects filter cake.The gained filter cake adds 75ml distilled water, be warming up to 83 ℃ of dissolvings gradually, naturally cool to 25 ℃ and carry out secondary crystal, suction filtration separates, the filter cake of secondary crystal is at every turn with dehydrated alcohol 50mL washing 6 times, colourless until washings, then in 45 ℃ of oven dry, obtain DSD acid sodium-salt dry product 43g, product reaches 98.2% with the high performance liquid chromatograph purity assay immediately, and this product is under encapsulation situations, the product surface nondiscoloration, be respectively 0.5 hour when storage period, 1 hour, 5 hours, after 24 hours, product purity is respectively 98.2%, 98.1%, 98.1%, 98.0%, its purity changes small.
Claims (2)
1. one kind by industrial goods 4, and it is high-quality 4 that 4 '-diaminobenzil-2,2 '-disulfonic acid prepare, 4 '-diaminobenzil-2, and the method for 2 '-disulfonic acid sodium salt is characterized in that comprising following process:
1) under the lucifuge condition, presses Industrial products 4,4 '-diaminobenzil-2, the mass ratio of 2 '-disulfonic acid and water is 1: 1.5-2.5, and with 4,4 '-diaminobenzil-2,2 '-disulfonic acid adds in the deionized water, slowly adds alkaline solution, controlled temperature 80-83 ℃, pH6-7, make industrial goods 4,4 '-diaminobenzil-2, the dissolving of 2 '-disulfonic acid obtains 4,4 '-diaminobenzil-2,2 '-sodium disulfonate salts solution;
2) under the lucifuge condition, with 4 of step 1), 4 '-diaminobenzil-2,2 '-sodium disulfonate salts solution are cooled to 20-30 ℃, crystallization, filtration and obtain 4,4 '-diaminobenzil-2,2 '-disulfonic acid sodium salt filter cake;
3) under the lucifuge condition, with step 2) 4,4 '-diaminobenzil-2,2 '-disulfonic acid sodium salt filter cake is 1 by the mass ratio with water: 1-1.25, and with 4,4 '-diaminobenzil-2,2 '-disulfonic acid sodium salt filter cake adds in the deionized water, controlled temperature 80-83 ℃, makes 4,4 '-diaminobenzil-2,2 '-sodium disulfonate salts solution is cooled to 20-30 ℃ and carries out secondary crystal, filters and obtains 4,4 '-diaminobenzil-2,2 '-disulfonic acid sodium salt filter cake;
4) under the lucifuge condition, with dehydrated alcohol thorough washing step 3) obtain 4,4 '-diaminobenzil-2,2 '-disulfonic acid sodium salt filter cake, colourless until washings, 30-60 ℃ of lucifuge oven dry, obtaining purity is 4 more than 99.5% then, 4 '-diaminobenzil-2,2 '-disulfonic acid sodium salt.
2. described by industrial goods 4 by claim 1,4 '-diaminobenzil-2,2 '-disulfonic acid prepare high-quality 4,4 '-diaminobenzil-2, the method of 2 '-disulfonic acid sodium salt is characterized in that, alkali lye is sodium hydroxide, yellow soda ash or their mixture.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100576228A CN100451000C (en) | 2007-06-14 | 2007-06-14 | Process of preparing high quality sodium salt of DSD acid with industrial DSD acid |
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| CNB2007100576228A CN100451000C (en) | 2007-06-14 | 2007-06-14 | Process of preparing high quality sodium salt of DSD acid with industrial DSD acid |
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| CN101066942A CN101066942A (en) | 2007-11-07 |
| CN100451000C true CN100451000C (en) | 2009-01-14 |
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| CNB2007100576228A Expired - Fee Related CN100451000C (en) | 2007-06-14 | 2007-06-14 | Process of preparing high quality sodium salt of DSD acid with industrial DSD acid |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06172295A (en) * | 1992-05-13 | 1994-06-21 | Nippon Kayaku Co Ltd | Production of 4,4'-diaminostilbene-2,2'-disulfonic acid or its salt |
| US5583252A (en) * | 1994-05-26 | 1996-12-10 | Bayer Aktiengesellschaft | Process for preparing 4,4'-dinitrostilbene-2,2'-disulphonic acid and its salts |
| CN1156407C (en) * | 2001-01-05 | 2004-07-07 | 南京大学 | Treatment and rediaimation of waste water in production of 4,4'-dinitrobistyrene-2,2'-bisulfonic acid |
| CN1249028C (en) * | 2003-05-31 | 2006-04-05 | 周恒德 | 4.4'-diaminobenzil-2.2'-disulphonate and producing method |
| CN1762991A (en) * | 2005-10-08 | 2006-04-26 | 天津大学 | Adsorption treating method for resinifying sulfonated waste acid in DSD acid production |
-
2007
- 2007-06-14 CN CNB2007100576228A patent/CN100451000C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06172295A (en) * | 1992-05-13 | 1994-06-21 | Nippon Kayaku Co Ltd | Production of 4,4'-diaminostilbene-2,2'-disulfonic acid or its salt |
| US5583252A (en) * | 1994-05-26 | 1996-12-10 | Bayer Aktiengesellschaft | Process for preparing 4,4'-dinitrostilbene-2,2'-disulphonic acid and its salts |
| CN1156407C (en) * | 2001-01-05 | 2004-07-07 | 南京大学 | Treatment and rediaimation of waste water in production of 4,4'-dinitrobistyrene-2,2'-bisulfonic acid |
| CN1249028C (en) * | 2003-05-31 | 2006-04-05 | 周恒德 | 4.4'-diaminobenzil-2.2'-disulphonate and producing method |
| CN1762991A (en) * | 2005-10-08 | 2006-04-26 | 天津大学 | Adsorption treating method for resinifying sulfonated waste acid in DSD acid production |
Non-Patent Citations (4)
| Title |
|---|
| 4,4'-二硝基二苯乙烯-2,2'-二磺酸合成工艺改进. 黄小波等.精细化工，第17卷第3期. 2000 |
| 4,4'-二硝基二苯乙烯-2,2'-二磺酸合成工艺改进. 黄小波等.精细化工，第17卷第3期. 2000 * |
| DSD酸合成新工艺的研究. 周海滨.大连理工大学硕士学位论文. 2002 |
| DSD酸合成新工艺的研究. 周海滨.大连理工大学硕士学位论文. 2002 * |
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| CN101066942A (en) | 2007-11-07 |
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