CN101538414A - Method for preparing acid black 172 - Google Patents
Method for preparing acid black 172 Download PDFInfo
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- CN101538414A CN101538414A CN200810052455A CN200810052455A CN101538414A CN 101538414 A CN101538414 A CN 101538414A CN 200810052455 A CN200810052455 A CN 200810052455A CN 200810052455 A CN200810052455 A CN 200810052455A CN 101538414 A CN101538414 A CN 101538414A
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Abstract
The invention relates to a method for preparing acid black 172. The method comprises the following steps that: (1) 6-nitro-1 and 2-diazoxynaphthalene-4-sulfonic acid are put into a dissolution tank, added with water for dissolution, added with a sodium hydroxide solution and stirred. (2) 2-naphthol is put into the dissolution tank, added with water for dissolution, added with the sodium hydroxide solution, stirred, heated, added with a dispersant and aliphatic diol or ether and stirred again; (3) a prepared 2-naphthol solution is rapidly put into and coupled with a solution with 6-nitro-1 and 2-diazoxynaphthalene-4-sulfonic acid so as to obtain coupled liquid; and (4) the coupled liquid is added with formic acid, ammonium bicarbonate or sodium bicarbonate and basic chromium sulfate, heated to be between 100 and 102 DEG C, thermally insulated and stirred so as to obtain an acid black 172 serous finished product. The method for preparing acid black 172 has the advantages of simple production process, scientific reasonable control on reaction conditions, short production cycle of produces, high yield, good quality, friction resistance, obviously raised fastness of resisting rinse and sunshine, obviously reduced side reaction and impurities, low production cost, high production efficiency and better environment-friendly property.
Description
Technical field
The invention belongs to the metal complex azo dye field, especially a kind of preparation method of acid black 172.
Background technology
Acid black 172 is a kind of matching stain by the name of international dyestuff numbering, its trade name is neutral black S-RL, it is to wool, tynex has the high dyeing fastness, and price is lower, use very extensively in dye field, the demand in market becomes the trend that increases year by year, and the demand of estimating whole world this year reaches 30,000 tons.The principal reaction of producing acid black 172 at present is as follows:
1.6-nitro-1, the dissolving of 2-diazoxy naphthalene-4-sulfonic acid:
2.2-the dissolving of naphthols:
3. coupled reaction:
4. chromaking reaction:
The production method of above-mentioned reaction mainly is with 6-nitro-1,2-diazoxy naphthalene-4-sulfonic acid is put into dissolving vessel, liquid caustic soda dissolving with 30%, liquid after the dissolving is put into the coupled reaction jar, under stirring condition, to pour in the coupled reaction jar with the beta naphthal solution after the liquid caustic soda dissolving and react, after coupled reaction finished, adjusting reaction solution with formic acid was slightly acidic, added basic chromium sulfate, 100-102 ℃ of chromaking 12 hours, be cooled to room temperature then, add sodium-chlor and Repone K and saltout, filter, dry, pulverize and obtain the finished product.Though aforementioned production method can access acid black 172, still there are the following problems: (1). complex manufacturing: after product reacted completely, step such as also needed to saltout; (2). life cycle of the product is long: mainly by the coupling time and the decision of chromaking time of reaction, general coupled reaction needs 8 hours, and the chromaking reaction needed just can reach reaction end in 12 hours, and the concentration of general reaction solution is very low has only 8-10%; (3). product yield is lower, and side reaction and impurity are more; (4). the wear-resisting wiping of product, water-fastly wash, light fastness is lower; (5). production cost is higher, and production efficiency is lower; (6). the discharging of waste liquid amount is big, and environmental pollution is serious, and treatment cost is higher; Wherein mainly be to saltout to produce a large amount of saliferous waste water from dyestuff in the step, isolated dyestuff filter cake also will be dried operations such as pulverizing simultaneously.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, provide that a kind of production technique is simple, reaction conditions control is scientific and reasonable, life cycle of the product is short and yield is high, wear-resisting wiping, water-fastly wash, the preparation method of the acid black 172 of light fastness height, environmental protection.
The technical problem that the present invention solves is achieved through the following technical solutions:
A kind of preparation method of acid black 172, the step of its preparation method is:
(1). with 6-nitro-1,2-diazoxy naphthalene-4-sulfonic acid is put into dissolving vessel A and is added the water making beating, under stirring condition, in the A jar, add concentration and be 30% sodium hydroxide solution the pH value of solution is controlled between the 4-6, and to control solution temperature simultaneously be 10-20 ℃;
(2). beta naphthal is put into dissolving vessel B add the water making beating, the concentration that adds beta naphthal weight 83.7% in the B jar is 30% sodium hydroxide solution, stirs and is warming up to 75-85 ℃, after beta naphthal dissolves fully, add dispersion agent and aliphatic diol or ether, stir;
(3). under stirring condition, the liquid among the dissolving vessel B is put into dissolving vessel A carry out coupling, the temperature of control mixed solution is 40-45 ℃, and the PH of control mixed solution is 11.0-11.5, reaction solution is stirred 1-2h obtain coupling solution;
(4). add formic acid in coupling solution, control PH is 5.8-6.0, adds bicarbonate of ammonia or sodium bicarbonate, adds basic chromium sulfate again, coupling solution is warming up to 100-102 ℃ is incubated and stirred 2-4 hour, obtains acid black 172 slurries finished product.
And, described 6-nitro-1, the weight ratio that 2-diazoxy naphthalene-4-sulfonic acid, beta naphthal and basic chromium sulfate add is 590: 302: 335.
And described dispersion agent is anionic dispersing agents or non-ionic dispersing agent, and its addition is the 1-5% of beta naphthal weight in the reaction system.
And described anionic dispersing agents is Dispersant MF or dispersion agent beta-naphthalenesulfonic-acid and formaldehyde condensation products or dispersing agent NNO and sodium lignosulfonate, and non-ionic dispersing agent is ethoxylated nonylphenol or ethoxylation unsaturated fatty acids.
And described aliphatic diol or ether are the wherein a kind of of ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether or ethylene glycol monobutyl ether, and its addition is the 3-8% of beta naphthal weight in the reaction system.
And, with described acid black 172 slurries finished product spraying drying, promptly obtain dry product.
Advantage of the present invention and beneficial effect are:
1. dispersion agent and aliphatic diol or ether have been added among the preparation method of this acid black 172, the viscosity of coupled reaction is obviously reduced, the concentration of coupled reaction liquid is improved, accelerated the probability of diazo component (6-nitro) and the intermolecular collision of coupling component (beta naphthal), speed of response is obviously accelerated, coupled reaction only needed to react completely in 1 hour now, 7 hours have been shortened fully than coupling in original 8 hours, the chromaking reaction only needed get final product in 3 hours now, shortened 9 hours than original 12 hours, the life cycle of the product cocondensation has been lacked 16 hours, has saved a large amount of energy, reduce production cost, improved production efficiency.
2. the preparation method of this acid black 172 has had tangible improvement in the control of coupled reaction temperature condition, change 40-45 ℃ into by 20-25 ℃ of original coupled reaction temperature, coupled reaction speed is obviously accelerated, product yield improves, side reaction and impurity obviously reduce, and quality product is further improved.
3. the preparation method of this acid black 172 is in the chromaking reaction process, the H that adds in a spot of bicarbonate of ammonia or the sodium bicarbonate and emit during the chromaking reaction
+The chromaking speed of response is obviously accelerated; and product slurry concentration is increased to 25-30% by original 8-10%, production efficiency is significantly improved, and has realized spraying drying; saved salting-out procedures; saved a large amount of Repone K and sodium-chlor, avoided of the pollution of saliferous dyestuff waste liquid, protected environment environment; reduce treatment cost, improved economic benefit.
4. production technique of the present invention is simple, reaction conditions control is scientific and reasonable, life cycle of the product is short, yield is high, good, the wear-resisting wiping of quality, water-fastly wash, the light fastness height, side reaction and impurity obviously reduce, and production cost is lower, production efficiency is higher, is a kind of preparation method of acid black 172 of more environmental protection.
Embodiment
The present invention is described in further detail by following examples.Need to prove: following embodiment is illustrative, is not determinate, can not limit protection scope of the present invention with following embodiment.
Embodiment 1
A kind of preparation method of acid black 172, wherein this preparation method's step is:
(1). with the 6-nitro-1 of 295g100%, 2-diazoxy naphthalene-4-sulfonic acid is put into dissolving vessel A and is added the 1000ml water dissolution, under stirring condition, adding concentration is that 30% sodium hydroxide solution is 5 with the control pH value in the A jar, and to control solution temperature simultaneously be 18 ℃, and the method for specifically controlling the solution cooling can adopt mode on the rocks;
(2). the 151g2-naphthols is put into dissolving vessel B add the 400ml water dissolution, adding 95ml concentration is 30% sodium hydroxide solution in the B jar, stirring is warming up to 80 ℃, after beta naphthal dissolves fully, add 3g dispersion agent NSO (beta-naphthalenesulfonic-acid and formaldehyde condensation products) and 8g ethylene glycol monobutyl ether, stir;
(3). under quick stirring condition, the liquid among the dissolving vessel B poured into rapidly among the dissolving vessel A form mixed solution, the temperature of control mixed solution is 40 ℃, and the PH of control mixed solution is 11.0, mixed solution is stirred 1h obtain coupling solution;
(4). add 90g formic acid in coupling solution, control PH is 5.8, adds the 20g sodium bicarbonate, add the 167.5g basic chromium sulfate again, coupling solution was warming up to 100 ℃ of insulated and stirred 3 hours, and obtaining solid content is the acid black 172 slurries finished product of 25-30%, is used for the dyeing of wool or tynex.
With above-mentioned acid black 172 slurries finished product spraying drying, obtain dry product.
Embodiment 2
A kind of preparation method of acid black 172, wherein this preparation method's step is:
(1). with the 6-nitro-1 of concentration 295g100%, 2-diazoxy naphthalene-4-sulfonic acid is put into dissolving vessel A and is added the 1000ml water dissolution, under stirring condition, adding concentration is 30% sodium hydroxide solution in the A jar, the control pH value is 4, and to control solution temperature simultaneously be 20 ℃, and the method for specifically controlling the solution cooling can adopt mode on the rocks;
(2). the 151g2-naphthols is put into dissolving vessel B add the 400ml water dissolution, adding 95ml concentration is 30% sodium hydroxide solution in the B jar, stirs and is warming up to 85 ℃, after beta naphthal dissolves fully, add 3g dispersion agent ethoxylated nonylphenol and 8g propylene glycol, stir;
(3). under quick stirring condition, the liquid among the dissolving vessel B poured into rapidly among the dissolving vessel A form mixed solution, the temperature of control mixed solution is 45 ℃, and the PH of control mixed solution is 11.5, mixed solution is stirred 2h obtain coupling solution;
(4). add 90g formic acid in coupling solution, control PH is 6, adds 20g bicarbonate of ammonia, add the 167.5g basic chromium sulfate again, coupling solution was warming up to 102 ℃ of insulated and stirred 4 hours, and obtaining solid content is the acid black 172 slurries finished product of 25-30%, is used for the dyeing of wool or tynex.
With above-mentioned acid black 172 slurries finished product spraying drying, obtain dry product.
Embodiment 3
A kind of preparation method of acid black 172, wherein this preparation method's step is:
(1). with the 6-nitro-1 of concentration 295g100%, 2-diazoxy naphthalene-4-sulfonic acid is put into dissolving vessel A and is added the 1000ml water dissolution, under stirring condition, adding concentration is 30% sodium hydroxide solution in the A jar, the control pH value is 6, and to control solution temperature simultaneously be 12 ℃, and the method for specifically controlling the solution cooling can adopt mode on the rocks;
(2). the 151g2-naphthols is put into dissolving vessel B add the 400ml water dissolution, adding 95ml concentration is 30% sodium hydroxide solution in the B jar, stirs and is warming up to 75 ℃, after beta naphthal dissolves fully, add 3g dispersion agent sodium lignosulfonate and 8g ethylene glycol monomethyl ether, stir;
(3). under quick stirring condition, the liquid among the dissolving vessel B poured into rapidly among the dissolving vessel A form mixed solution, the temperature of control mixed solution is 43 ℃, and the PH of control mixed solution is 11.3, mixed solution is stirred 1.5h obtain coupling solution;
(4). add 90g formic acid in coupling solution, control PH is 5.9, adds 20g bicarbonate of ammonia, add the 167.5g basic chromium sulfate again, coupling solution was warming up to 101 ℃ of insulated and stirred 2.5 hours, and obtaining solid content is the acid black 172 slurries finished product of 25-30%, is used for the dyeing of wool or tynex.
With above-mentioned acid black 172 slurries finished product spraying drying, obtain dry product.
In addition, the dispersion agent that the embodiment of the invention adopted can also adopt Dispersant MF or dispersing agent NNO or ethoxylation unsaturated fatty acids except above-mentioned points.
Aliphatic dialcohol that the embodiment of the invention adopted or ether can also adopt ethylene glycol, ethylene glycol monoethyl ether except above-mentioned points.
Claims (6)
1. the preparation method of an acid black 172, it is characterized in that: the step of its preparation method is:
(1). with 6-nitro-1,2-diazoxy naphthalene-4-sulfonic acid is put into dissolving vessel A and is added the water making beating, under stirring condition, in the A jar, add concentration and be 30% sodium hydroxide solution the pH value of solution is controlled between the 4-6, and to control solution temperature simultaneously be 10-20 ℃;
(2). beta naphthal is put into dissolving vessel B add the water making beating, the concentration that adds beta naphthal weight 83.7% in the B jar is 30% sodium hydroxide solution, stirs and is warming up to 75-85 ℃, after beta naphthal dissolves fully, add dispersion agent and aliphatic diol or ether, stir;
(3). under stirring condition, the liquid among the dissolving vessel B is put into dissolving vessel A carry out coupling, the temperature of control mixed solution is 40-45 ℃, and the PH of control mixed solution is 11.0-11.5, reaction solution is stirred 1-2h obtain coupling solution;
(4). add formic acid in coupling solution, control PH is 5.8-6.0, adds bicarbonate of ammonia or sodium bicarbonate, adds basic chromium sulfate again, coupling solution is warming up to 100-102 ℃ is incubated and stirred 2-4 hour, obtains acid black 172 slurries finished product.
2. the preparation method of acid black 172 according to claim 1 is characterized in that: described 6-nitro-1, the weight ratio that 2-diazoxy naphthalene-4-sulfonic acid, beta naphthal and basic chromium sulfate add is 590: 302: 335.
3. the preparation method of acid black 172 according to claim 1, it is characterized in that: described dispersion agent is anionic dispersing agents or non-ionic dispersing agent, its addition is the 1-5% of beta naphthal weight in the reaction system.
4. the preparation method of acid black 172 according to claim 3, it is characterized in that: described anionic dispersing agents is Dispersant MF or dispersion agent beta-naphthalenesulfonic-acid and formaldehyde condensation products or dispersing agent NNO and sodium lignosulfonate, and non-ionic dispersing agent is ethoxylated nonylphenol or ethoxylation unsaturated fatty acids.
5. the preparation method of acid black 172 according to claim 1, it is characterized in that: described aliphatic diol or ether are the wherein a kind of of ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether or ethylene glycol monobutyl ether, and its addition is the 3-8% of beta naphthal weight in the reaction system.
6. the preparation method of acid black 172 according to claim 1 is characterized in that: with described acid black 172 slurries finished product spraying drying, promptly obtain dry product.
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| CN2008100524552A CN101538414B (en) | 2008-03-17 | 2008-03-17 | Method for preparing acid black 172 |
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| CN2008100524552A CN101538414B (en) | 2008-03-17 | 2008-03-17 | Method for preparing acid black 172 |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101906258A (en) * | 2010-06-30 | 2010-12-08 | 杭州下沙恒升化工有限公司 | Method for producing acid dye |
| CN103044950A (en) * | 2013-01-24 | 2013-04-17 | 天津三环化学有限公司 | Method for producing acidic black 172 by using industrial waste chromium slag |
| CN103756362A (en) * | 2013-12-28 | 2014-04-30 | 浙江龙盛染料化工有限公司 | Acidic black dye composition |
| CN104194382A (en) * | 2014-09-04 | 2014-12-10 | 恒升化工有限公司 | Preparation method of azo type acidic dye |
| CN104327535A (en) * | 2014-10-11 | 2015-02-04 | 辽宁精化科技有限公司 | Preparation method of acid black 172 |
| CN105694524A (en) * | 2016-01-28 | 2016-06-22 | 江苏盛吉化工有限公司 | Preparation method of acid black 172 |
| CN109370256A (en) * | 2018-11-20 | 2019-02-22 | 恒升化工有限公司 | A kind of mixed type black dyes and preparation method thereof |
| CN111073336A (en) * | 2019-12-30 | 2020-04-28 | 浙江大学滨海产业技术研究院 | Preparation and application of high-strength acidic 172 black liquid dye |
| CN111171594A (en) * | 2019-12-31 | 2020-05-19 | 恒升化工有限公司 | Preparation method of metal complex dye with low residual chromium ions |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5376151A (en) * | 1993-04-16 | 1994-12-27 | North Carolina State University | Environmentally friendly method for producing lightfast black shades on natural and synthetic substrates |
-
2008
- 2008-03-17 CN CN2008100524552A patent/CN101538414B/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101906258A (en) * | 2010-06-30 | 2010-12-08 | 杭州下沙恒升化工有限公司 | Method for producing acid dye |
| CN103044950A (en) * | 2013-01-24 | 2013-04-17 | 天津三环化学有限公司 | Method for producing acidic black 172 by using industrial waste chromium slag |
| CN103044950B (en) * | 2013-01-24 | 2014-06-11 | 天津三环化学有限公司 | Method for producing acidic black 172 by using industrial waste chromium slag |
| CN103756362A (en) * | 2013-12-28 | 2014-04-30 | 浙江龙盛染料化工有限公司 | Acidic black dye composition |
| CN103756362B (en) * | 2013-12-28 | 2015-09-02 | 浙江龙盛染料化工有限公司 | A kind of acid black dye composition |
| CN104194382A (en) * | 2014-09-04 | 2014-12-10 | 恒升化工有限公司 | Preparation method of azo type acidic dye |
| CN104327535A (en) * | 2014-10-11 | 2015-02-04 | 辽宁精化科技有限公司 | Preparation method of acid black 172 |
| CN105694524A (en) * | 2016-01-28 | 2016-06-22 | 江苏盛吉化工有限公司 | Preparation method of acid black 172 |
| CN105694524B (en) * | 2016-01-28 | 2019-09-20 | 江苏盛吉化工有限公司 | A kind of preparation method of acid black 172 |
| CN109370256A (en) * | 2018-11-20 | 2019-02-22 | 恒升化工有限公司 | A kind of mixed type black dyes and preparation method thereof |
| CN111073336A (en) * | 2019-12-30 | 2020-04-28 | 浙江大学滨海产业技术研究院 | Preparation and application of high-strength acidic 172 black liquid dye |
| CN111171594A (en) * | 2019-12-31 | 2020-05-19 | 恒升化工有限公司 | Preparation method of metal complex dye with low residual chromium ions |
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| CN101538414B (en) | 2012-07-04 |
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