CN1390888A - Process for preparing indigo and its intermediate - Google Patents
Process for preparing indigo and its intermediate Download PDFInfo
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- CN1390888A CN1390888A CN 02138012 CN02138012A CN1390888A CN 1390888 A CN1390888 A CN 1390888A CN 02138012 CN02138012 CN 02138012 CN 02138012 A CN02138012 A CN 02138012A CN 1390888 A CN1390888 A CN 1390888A
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- salt
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- anilinoacetic acid
- sodium
- anilinoacetic
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Abstract
An indigo is prepared from anilinoacetonitrile as main raw material, anhydrous K-Na alkali mixture as solvent, and aminosodium as condensating agent through adding potassium sodium (or potassium) anilinoacetate, cyclyzing the potassium sodium anilinoacetate to become the indolol potassium (or sodium) at high temp and pressure, oxidizing, press filtering and drying. Said potassium sodium (or potassium) anilinoacetate as intermediate is prepared through proportionally mixing anilinoacetonitrile with the liquid K-Na alkali mixture or liquid K alkali.
Description
Affiliated field
The present invention relates to the aniline-acetonitrile is that main raw material prepares indigo method.
Background technology
The indigo synthetic middle industrial goods liquefied ammonia that uses of tradition, make the condensing agent sodium amide with the sodium Metal 99.5 reaction, use for alkali fusion, the mixed base that alkali fusion uses is solid industrial goods sodium hydroxide and the potassium hydroxide that market is bought, in 1: 1.5 ratio solvent as alkali fusion after melting, anilinoacetic acid sylvite generates indolol potassium after the alkali fusion cyclization, again through oxidation, press filtration, drying and make indigo product.The synthetic of intermediate anilinoacetic acid sylvite is raw material with aniline, Mono Chloro Acetic Acid: the ferrous sulfate crystal is dissolved the back make ferrous sulfate, liquid caustic soda, aniline, chloroacetate reaction make the anilinoacetic acid molysite in synthesis tank, to make the anilinoacetic acid potassium salt soln with the liquid nak response then, again through press filtration, the concentrated and dry dry powder anilinoacetic acid sylvite that gets.Because a large amount of ferrous sulfate, aniline etc. of using in the manufacturing processed, not only the manufacturing cycle long, and molysite filter cake treatment capacity is big, pollution problem is difficult to solution.
Summary of the invention
The present invention is workout cost and pollution problem, provide a kind of employing with the aniline-acetonitrile main raw material, prepare anilinoacetic acid k-na salt or anilinoacetic acid sylvite, and prepare indigo method as liquefied ammonia, the anhydrous mixed base of potassium sodium of intermediate and recycling use.
A kind of indigo preparation method of the present invention: after quantitative sodium Metal 99.5 intensification fusing, at a certain temperature, feeding liquefied ammonia fresh or that reclaim reacts, produce sodium amide, be added to then in the anhydrous mixed base of potassium sodium of fresh or recovery, at a certain temperature, make solvent with anhydrous mixed base fresh or that reclaim, sodium amide is made condensing agent, the gap adds a collection of anilinoacetic acid k-na salt or anilinoacetic acid sylvite, at high temperature, in the highly compressed environment anilinoacetic acid k-na salt or the cyclization of anilinoacetic acid sylvite are become indolol potassium (sodium), again through oxidation, press filtration, dry and make indigo.
The removal process of liquefied ammonia is: the ammonia that ring-closure reaction is emitted enters ice maker and becomes high temperature, high pressure gas after the removal of impurity, again through oil separator, removes impurity, at last through becoming liquefied ammonia after the condenser cooling; The removal process of potassium sodium mixed base is: with about 10% the alkali waste water in oxidation post with heat-conducting oil furnace or steam heating, carry out single-action or multiple-effect evaporation (method of also available direct heating evaporation concentration) and be concentrated into 40%～50%, again under the effect of auxiliary agent, remove impurity, through the decolouring after, direct heating dewater qualified anhydrous mixed base.
The preparation method of intermediate anilinoacetic acid k-na salt anilinoacetic acid sylvite is: aniline-acetonitrile is joined in the mother liquor that has certain temperature; after treating its dissolving; liquid mixing alkali (the NaOH that adds suitable proportioning at a certain temperature; KOH) or potassium hydroxide alkali lye; under 39～60 ℃ temperature, carry out acylation reaction; determine the reaction times according to the acylation reaction terminal point; reaction times is about 7～9 hours; evenly be warming up to 60～75 ℃ then; be incubated 1 hour; continue evenly to be warming up to 80～96 ℃ and be incubated 1h; and then be warmed up to 100～110 ℃ the insulation ammonia excretions; it is 2～6g/l that ammonia has been arranged cooling back adjustment basicity, and final drying gets anilinoacetic acid k-na salt or anilinoacetic acid sylvite.
The preferred acidylate temperature of the preparation method of anilinoacetic acid k-na salt or anilinoacetic acid sylvite is 40～50 ℃, and the acylation reaction time is 7.5～8.5 hours.It is sulfuric acid that terminal point is transferred the basicity volume ratio: water=1: 3 adds and a kind ofly generates sedimentary salt and participate in adjustment basicity.Liquid base is potassium, the compound alkali of sodium type, and the weight ratio of compound alkali is potassium hydroxide: sodium hydroxide=60-75: 40-25.
It is main raw material that the present invention adopts aniline-acetonitrile, relatively reduce raw materials cost 10% in old technology aniline, Mono Chloro Acetic Acid, production time and cycle shorten 1/3rd, do not adopt molysite, have got rid of the molysite jar, mother liquor need not concentrate and press filtration, save the energy, reduced the equipment input cost, reduced labour intensity, improve Working environment, thoroughly solved the governing problem of aniline waste water.
Embodiment
A kind of indigo preparation method of the present invention adds quantitative sodium Metal 99.5 in the retort, after the intensification fusing, under the temperature of regulation, feed liquefied ammonia fresh or that reclaim and react the production sodium amide, be added to then and fill anhydrous potassium sodium mixed base (NaOH fresh or that reclaim in advance, KOH) in the retort, at a certain temperature, make solvent with fresh or recovery alkali, sodium amide is made condensing agent, the gap adds a collection of anilinoacetic acid k-na salt or anilinoacetic acid sylvite, through high temperature, high pressure becomes indolol potassium (sodium) with anilinoacetic acid k-na salt or the cyclization of anilinoacetic acid sylvite, again through oxidation, press filtration, dry and make indigo.
The preparation of intermediate anilinoacetic acid k-na salt or anilinoacetic acid sylvite is aniline-acetonitrile to be joined temperature be lower than in 65 ℃ the mother liquor; after treating its dissolving; be cooled in 50 ℃; calculate the quantitative liquid mixing alkali (KOH of adding according to raw material; the NaOH ratio is: 60-75: 40-25) or liquid potassium hydroxide; drop into quantitative lime simultaneously; carry out acylation reaction after about 7.5～8.5 hours in insulation under 39～50 ℃ the temperature; the terminal point in acidylate stage is surveyed in sampling; if terminal point does not reach; then proceed insulation; if to terminal point then temperature is risen to 65～75 ℃; and after being incubated 1 hour; continue evenly to be warming up to 90～96 ℃; discharge ammoniacal liquor simultaneously; and be incubated 0.5 hour; continue to be warming up to 110 ℃ again; under this temperature, carry out end-point alkalinity; the ammonia excretion of the follow-up continuation of insurance temperature of the mensuration of mother liquid concentration is about 2 hours; cooling when waiting not have the ammonia flavor; with volume ratio is sulfuric acid: the diluted acid of water=1: 3; add again a kind of generate sedimentary salt participate in adjust basicity to 2～6g/l after, dry anilinoacetic acid k-na salt or anilinoacetic acid sylvite.
The anhydrous mixed base recovery method of NaOH, KOH is: the filtrate after the oxidation (10% mixed buck) is joined in rare single-effect evaporator, utilize the waste heat of dense effect to concentrate, after treating that rare effect solution reaches finite concentration, squeeze in the dense effect with pump, replenish the material liquid level of dense effect, constantly in rare effect, replenish diluted alkaline water simultaneously.So move in circles, when dense effect temperature reaches 150～160 ℃, sampling analysis when dense effect internal pressure is 0.05Mpa～0.06Mpa, when material concentration reaches 40%～50% in the dense effect, (also can adopt the method for direct heating evaporation concentration to get 40～50% dense mixed base), put into retort, add auxiliary agent, after fully stirring, be cooled to below 50 ℃ and remove impurity through press filtration, and then strong lye is made in decolouring, deliver at last in the solid caustic soda pot of mending a certain amount of solid potassium in advance, qualified anhydrous mixed base is made in direct heating, dehydration.
Claims (6)
1, a kind of indigo preparation method: after quantitative sodium Metal 99.5 intensification fusing, at a certain temperature, feed fresh or reclaim liquefied ammonia and react, produce sodium amide, be added to then in the anhydrous mixed base of potassium sodium of fresh or recovery, at a certain temperature, make solvent with fresh or recovery alkali, sodium amide is made condensing agent, the gap adds a collection of anilinoacetic acid k-na salt or anilinoacetic acid sylvite, at high temperature, in the highly compressed environment anilinoacetic acid k-na salt or the cyclization of anilinoacetic acid sylvite are become indolol potassium (sodium), again through oxidation, press filtration, dry and make indigo.
2, a kind of indigo preparation method according to claim 1 is characterized in that the removal process of liquefied ammonia is: the ammonia that ring-closure reaction is emitted enters the ice maker system compresses and is condensed into liquefied ammonia after the removal of impurity; The removal process of anhydrous potassium sodium mixed base is: with about 10% the alkali waste water in oxidation post with heat-conducting oil furnace or steam heating, carry out single-action or multiple-effect evaporation (also can adopt the method for direct heating evaporation concentration) and be concentrated into 40%～50%, again under the effect of auxiliary agent, remove impurity, through the decolouring after, direct heating dewater qualified anhydrous mixed base.
3; a kind of indigo preparation method according to claim 1; the preparation method who it is characterized in that anilinoacetic acid k-na salt or anilinoacetic acid sylvite is: aniline-acetonitrile is joined in the mother liquor that has certain temperature; after treating its dissolving; the potassium sodium liquid mixing alkali or the liquid potash lye that add suitable proportioning at a certain temperature; under 39～60 ℃ temperature, carry out acylation reaction; determine the reaction times according to the acylation reaction terminal point; reaction times is about 7～9 hours; evenly be warming up to 60～75 ℃ then; be incubated 1 hour; continuing evenly to be warming up to 80～96 ℃ again is incubated; evenly be warming up to 100～110 ℃ of insulation ammonia excretions then; adjusting basicity after cooling is 2～6g/l, and final drying gets anilinoacetic acid k-na salt or anilinoacetic acid sylvite.
4, a kind of indigo preparation method according to claim 1, the acidylate temperature is 40～50 ℃ when it is characterized in that the preparation of anilinoacetic acid k-na salt or anilinoacetic acid sylvite, the acylation reaction time is 7.5～8.5 hours.
5, a kind of indigo preparation method according to claim 1 is a sulfuric acid with volume ratio when it is characterized in that the preparation of anilinoacetic acid k-na salt or anilinoacetic acid sylvite: water=1: 3 adds and a kind ofly generates sedimentary salt and participate in adjustment basicity.
6, a kind of indigo preparation method according to claim 1, the weight ratio of potassium sodium mixed base is potassium hydroxide: sodium hydroxide=60-75: 40-25 when it is characterized in that the preparation of anilinoacetic acid k-na salt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021380120A CN1191307C (en) | 2002-07-26 | 2002-07-26 | Process for preparing indigo and its intermediate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021380120A CN1191307C (en) | 2002-07-26 | 2002-07-26 | Process for preparing indigo and its intermediate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1390888A true CN1390888A (en) | 2003-01-15 |
| CN1191307C CN1191307C (en) | 2005-03-02 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021380120A Expired - Lifetime CN1191307C (en) | 2002-07-26 | 2002-07-26 | Process for preparing indigo and its intermediate |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004058898A1 (en) * | 2002-12-25 | 2004-07-15 | Beijing Wisdom Yingli Pharmaceutical Technology Developing Co., Ltd. | A process for dyeing directly a textile fabric in situ |
| CN100365071C (en) * | 2006-03-01 | 2008-01-30 | 浙江闰土股份有限公司 | Method for producing idigo by cyclic utilization of non-reacted raw materials |
| CN101591286B (en) * | 2009-04-23 | 2011-04-13 | 江苏泰丰化工有限公司 | Preparation method for synthesizing indigotin continuously without alkali |
| CN102127307A (en) * | 2010-12-29 | 2011-07-20 | 梅剑平 | Recovered mixed alkali solution from production of indigo, and recovering method and use thereof |
-
2002
- 2002-07-26 CN CNB021380120A patent/CN1191307C/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004058898A1 (en) * | 2002-12-25 | 2004-07-15 | Beijing Wisdom Yingli Pharmaceutical Technology Developing Co., Ltd. | A process for dyeing directly a textile fabric in situ |
| CN100365071C (en) * | 2006-03-01 | 2008-01-30 | 浙江闰土股份有限公司 | Method for producing idigo by cyclic utilization of non-reacted raw materials |
| CN101591286B (en) * | 2009-04-23 | 2011-04-13 | 江苏泰丰化工有限公司 | Preparation method for synthesizing indigotin continuously without alkali |
| CN102127307A (en) * | 2010-12-29 | 2011-07-20 | 梅剑平 | Recovered mixed alkali solution from production of indigo, and recovering method and use thereof |
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| Publication number | Publication date |
|---|---|
| CN1191307C (en) | 2005-03-02 |
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Decision date of declaring invalidation: 20071001 Decision number of declaring invalidation: 10385 |
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Granted publication date: 20050302 |