CN103044950A - Method for producing acidic black 172 by using industrial waste chromium slag - Google Patents
Method for producing acidic black 172 by using industrial waste chromium slag Download PDFInfo
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- CN103044950A CN103044950A CN2013100256649A CN201310025664A CN103044950A CN 103044950 A CN103044950 A CN 103044950A CN 2013100256649 A CN2013100256649 A CN 2013100256649A CN 201310025664 A CN201310025664 A CN 201310025664A CN 103044950 A CN103044950 A CN 103044950A
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Abstract
The invention relates to a method for producing acidic black 172 by using industrial waste chromium slag. The method is characterized by comprising the following steps of: (1) dissolving and filtering, i.e., placing waste chromium slag of methylene blue BB into diluted sulfuric acid, heating, stirring and dissolving, filtering to remove insoluble substances, and collecting mother solution for reduction; (2) reducing and precipitating, i.e., adding glucose into the solution, heating for reduction, and then adding pure alkali till precipitating completely to obtain chromium carbonate sediment; (3) preparing chromium sulfate solution, i.e., dissolving the obtained chromium carbonate into the diluted sulfuric acid to obtain the chromium sulfate solution; and (4) preparing the acidic black 172, i.e., adding the chromium sulfate solution of step (3). According to the production process disclosed by the invention, the environmental pollution caused by large amounts of the chromium slag produced by the production of the methylene blue BB is successfully solved, the chromium slag is eliminated, the production cost of the acidic black 172 is reduced, the load of a three-waste treatment workshop is alleviated, and the competitiveness of the methylene blue BB and the acidic black 172 in the market is enhanced.
Description
Technical field
The invention belongs to chemical field, especially a kind of method of utilizing Industry Waste chromium slag to produce acid black 172.
Background technology
The alkalescence acid blue is not only the important slag dye species for acrylic fiber dyeing, and also is applicable to paper coloring and pharmaceutical.Its chemical structure belongs to the derivative of thiophene piperazine (Thiazine) or sulphur acridine, the general commodity title: methylene blue (Methylene Blue), and the synthetic of this dyestuff is take DMA as raw material, prepares through following each step reaction:
From reaction process as seen, material N, accelerine is through nitrosification, and reduction reaction is made to amino N accelerine; In the presence of sodium dichromate 99, generate thiophene phenol piperazine sulfate derivative with the Sulfothiorine effect, again in the presence of sodium dichromate 99 with N, accelerine carries out oxidative dimerization, generate purple quinonimine compound, at last under catalysis of cupric sulphate with the sodium dichromate 99 effect, through the oxidation closed loop, saltout, obtain the finished product Methylene Blue BB.
Obviously, the sodium dichromate 99 that three phases adds in reaction process only uses as oxygenant, make oxidation operation, and metal chromium ions is reduced to positive trivalent from positive sexavalence:
Cr
2O
7 -2+14H
++6e→2Cr
+3+7H
2O
Therefore as can be known, metal chromium ions is not introduced in the finished product processed, all with useless chromium slag form discharging, directly caused the pollution of environment.Estimate the Methylene Blue BB of one ton of every production, consume 1.4 tons sodium dichromate 99.
On the other hand, produce in C.I. acid black 172 (neutral black S-RL) process, at first need to carry out complex reaction with chromium sulphate (chromic salts complexing agent) again by 6-nitro oxysome and the synthetic parent dyestuff of 2-Naphthol, generate 1:2 shaped metal complexing neutral black S-RL dyestuff:
C.I. acid black 172; Neutral black S-RL
With reacted acid black 172 slurries, spray-dried, obtain the acid black 172 finished product, can be directly used in the dyeing of nylon or wool.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, provides a kind of Industry Waste chromium slag new treatment process, and the chromic salts that obtains after the processing is applied in the dyestuff manufacturing, has played the effect of recycling economy.
The objective of the invention is to be achieved through the following technical solutions:
A kind of method of utilizing Industry Waste chromium slag to produce acid black 172, step is as follows:
⑴ dissolving, filtration: the useless chromium slag of Methylene Blue BB is put into dilute sulphuric acid, and the intensification stirring and dissolving removes by filter insolubles, and it is to be restored to collect mother liquor;
⑵ reduction, precipitation: will add glucose in the mentioned solution, heat up and reduce, then add soda ash, to precipitating fully, obtain the chromium carbonate precipitation;
⑶ prepare chromium sulfate solution: the chromium carbonate that obtains is dissolved in the dilute sulphuric acid, makes chromium sulfate solution;
⑷ prepare acid black 172: with 6-nitro-1,2-diazoxy naphthalene-4-sulfonic acid and beta naphthal add formic acid after the alkaline medium coupling, adjust pH=5.5-6.0, the chromium sulfate solution that adds step ⑶ makes monoazo-dyes and chromium form stable comple, namely obtains acid black 172.
And described insolubles reusable heat water washing merges to water lotion in the mother liquor.
And the weight percent concentration of described dilute sulphuric acid is 10-30%
And the reductive condition of described adding glucose is: be warming up to boiling, be incubated 20-50 minute.
And described adding soda ash is adjusted pH=8.5-9.0.
Advantage of the present invention and positively effect are:
1, the present invention adopts chemical process to extract the chromium in the useless chromium slag in the Methylene Blue BB, be converted into chromium sulphate be applied directly to dyestuff synthetic in, solved on the one hand the emission problem of the useless chromium slag of Methylene Blue BB, effectively avoid insoluble chromium that environment is caused secondary pollution, reduce on the other hand the production cost of producing acid black 172, had certain Social benefit and economic benefit.
2, the present invention utilizes reductive agent (glucose) that drop hexavalent chromium fully is reduced to trivalent chromium, thoroughly removes poisonous sexavalent chrome, and guarantees the acid black 172 steady quality produce.
3, the chromium sulfate solution of the present invention's preparation substitutes the basic chromium sulfate that uses in the acid black 172 technique, directly is used as the chromaking agent of neutral black, has reduced the production cost of acid black 172.
The environmental pollution that a large amount of useless chromium slags that produced when 4, production technique of the present invention has successfully solved the production Methylene Blue BB cause, eliminated useless chromium slag, reduced the acid black 172 production cost, alleviate the burden in disposal of three wastes workshop, improved Methylene Blue BB, the competitive power of acid black 172 product on market.
Embodiment
Below in conjunction with embodiment, the present invention is further described, and following embodiment is illustrative, is not determinate, can not limit protection scope of the present invention with following embodiment.
What following examples adopted is to produce the industrial chromium waste residue that Methylene Blue BB reclaims.
That mentions in following examples is weight percentage, special indicate except.
Invention thought of the present invention is:
⑴ dissolving: the useless chromium slag of Methylene Blue BB being produced by-product (contains H at dilute sulphuric acid first
2SO
424%) dissolving in after the rising temperature for dissolving, is filtered the impurity that discards in the solution;
With the sulfuric acid lattice damage in the chromium slag of will giving up, chromium is all dissolved in this step.
⑵ reduction: filtrate is put into to a reduction tank, add reductive agent, the boiling reduction is reduced into Cr3 with the Cr6+ of trace remaining in the solution
+, with soda ash (yellow soda ash) neutralization, with Cr3
+Separate out, until till all separating out;
Be trivalent chromium with the sexavalent chrome Restore All that may exist in the solution in this step, again the trivalent chromium in the solution separated out fully with the form of chromium carbonate, make the content of chromium from waste chromium less than 1.5ppm, reach discharging standards.
⑶ prepare chromium sulfate solution: filter filter cake with about 70% sulfuric acid dissolution, make chromium sulfate solution;
This step changes the chromium that obtains into purity higher chromium sulphate again, in order to synthesize qualified product neutral black 172.
⑷ prepare acid black 172: solution is applied on neutral black 172 products.
Concrete operational instances is as follows:
Embodiment 1
A kind of method of utilizing Industry Waste chromium slag to produce acid black 172, step is as follows:
⑴ dissolving, filtration: 200g acid blue chromium waste residue is added in the sulfuric acid of 300g24%, be warming up to 80 ℃, stirred 1 hour, remove by filter insolubles, collect mother liquor, insolubles is washed with 100ml80 ℃ of hot water, mother liquor and water lotion are merged, put into the 1000ml beaker, to be restored;
⑵ reduction, precipitation: mentioned solution is added 10g glucose, be warming up to boiling, be incubated 30 minutes, then be cooled to room temperature, slowly add soda ash and adjust pH=8.5-9.0, continue to stir after 1 hour, filter and obtain the chromium carbonate filter cake;
⑶ prepare chromium sulfate solution: add the dilute sulphuric acid of 250g70% in four-hole bottle, stir the lower 150g of adding chromium carbonate filter cake, and be warming up to 60 ℃, be stirred to entirely moltenly, obtain chromium sulfate solution;
⑷ prepare acid black 172: with the 6-nitro-1 of 29.5g, 2-diazoxy naphthalene-4-sulfonic acid and 15.1g2-naphthols are after the alkaline medium coupling, the formic acid that adds about 10g85%, adjust PH=5.5-6.0, add the chromium sulfate solution of step ⑶, continue to be warming up to 100 ℃, insulated and stirred 4 hours, obtain acid black 172 dyestuff slurries, obtain neutral black 172 dry products after spray-dried.
Embodiment 2
A kind of method of utilizing Industry Waste chromium slag to produce acid black 172, step is as follows:
⑴ dissolving, filter: 100g acid blue chromium waste residue is added in the hydrochloric acid of 250g30%, be stirred to entirely moltenly, remove by filter insolubles, and collect mother liquor, insolubles merges mother liquor and water lotion with 100ml80 ℃ of hot water washing, puts into the 1000ml beaker, and is to be restored;
⑵ reduction, precipitation: mentioned solution is added 10g glucose, be warming up to and boil and be incubated 30 minutes, then be cooled to room temperature, slowly add soda ash and adjust PH=8.5-9.0, continue to stir after 1 hour, filter and obtain the chromium carbonate filter cake;
⑶ prepare chromium sulfate solution: add the dilute sulphuric acid of 250g65% in four-hole bottle, stir the lower 150g of adding chromium carbonate filter cake, and be warming up to 60 ℃, be stirred to entirely moltenly, obtain chromium sulfate solution;
⑷ prepare acid black 172: with the 6-nitro-1 of 29.5g, 2-diazoxy naphthalene-4-sulfonic acid and 15.1g2-naphthols are after the alkaline medium coupling, add about 10g85% formic acid, adjust PH=5.5-6.0, add above-mentioned chromium sulfate solution, continue to be warming up to 100 ℃, insulated and stirred 4 hours, obtain acid black 172 dyestuff slurries, obtain the acid black 172 dry product after spray-dried.
Embodiment 3
A kind of method of utilizing Industry Waste chromium slag to produce acid black 172, step is as follows:
⑴ dissolving, filtration: 200g acid blue chromium waste residue is added in the sulfuric acid of 300g24%, be warming up to 80 ℃, stirred 1 hour, remove by filter insolubles, and collect mother liquor, insolubles is washed with 100ml80 ℃ of hot water, mother liquor and water lotion are merged, put into the 1000ml beaker, to be restored;
⑵ reduction: mentioned solution is added the 5g ferrous sulfate, be warming up to and boil and be incubated 30 minutes, then be cooled to room temperature, slowly add 30% sodium hydroxide and adjust PH=8.5-9.0.Continue to stir after 1 hour, filter and obtain the chromium carbonate filter cake;
⑶ prepare chromium sulfate solution: add the dilute sulphuric acid of 250g75% in four-hole bottle, stir the lower 150g of adding chromium carbonate filter cake, and be warming up to 60 ℃, be stirred to entirely moltenly, obtain chromium sulfate solution;
⑷ prepare acid black 172: with the 6-nitro-1 of 29.5g, 2-diazoxy naphthalene-4-sulfonic acid and 15.1g2-naphthols are after the alkaline medium coupling, add about 10g85% formic acid, adjust PH=5.5-6.0, add above-mentioned chromium sulfate solution, continue to be warming up to 100 ℃, insulated and stirred 4 hours, obtain acid black 172 dyestuff slurries, obtain the acid black 172 dry product after spray-dried.
Two, the concrete preparation method of acid black 172 is as follows:
⑴ add 1000L water in retort, stir lower adding 295kg6-nitro-1,2-diazoxy naphthalene-4-sulfonic acid, and after stirring, the liquid caustic soda that adds about 100L30% is adjusted PH=2.0, and all dissolving is rear for subsequent use to be stirred to material.
⑵ add 500L water in another retort, add the 144kg2-naphthols, and the liquid caustic soda of 145kg30% is warming up to 60 ℃, be stirred to fully dissolving after, for subsequent use.
⑶ will dissolve good beta naphthal solution and put into 6-nitro-1, in 2-diazoxy naphthalene-4-sulfonic acid solutions, liquid caustic soda with 30% keeps PH=8.5-9.0, temperature 20-25oC insulated and stirred 6 hours, add the 196kg chromium sulphate and (be the chromium sulfate solution of above step preparation, 196 refer in the chromium sulfate solution, the weight of pure chromium sulphate.) 100 ℃, insulated and stirred 8 hours with dyestuff slurry spraying drying, obtains 895kg dried dye powder, yield 92%.
The concrete preparation method's of acid black 172 reference is as follows:
Claims (5)
1. method of utilizing Industry Waste chromium slag to produce acid black 172, it is characterized in that: step is as follows:
⑴ dissolving, filtration: the useless chromium slag of Methylene Blue BB is put into dilute sulphuric acid, and the intensification stirring and dissolving removes by filter insolubles, and it is to be restored to collect mother liquor;
⑵ reduction, precipitation: will add glucose in the mentioned solution, heat up and reduce, then add soda ash, to precipitating fully, get the chromium carbonate precipitation;
⑶ prepare chromium sulfate solution: the chromium carbonate that obtains is dissolved in the dilute sulphuric acid, makes chromium sulfate solution;
⑷ prepare acid black 172: with 6-nitro-1,2-diazoxy naphthalene-4-sulfonic acid and beta naphthal add formic acid after the alkaline medium coupling, adjust pH=5.5-6.0, the chromium sulfate solution that adds step ⑶ makes monoazo-dyes and chromium form stable comple, namely obtains acid black 172.
2. the method for utilizing Industry Waste chromium slag to produce acid black 172 according to claim 1, it is characterized in that: described insolubles is washed with hot water, and water lotion is merged in the mother liquor.
3. the method for utilizing Industry Waste chromium slag to produce acid black 172 according to claim 1, it is characterized in that: the weight percent concentration of described dilute sulphuric acid is 10-30%
4. the method for utilizing Industry Waste chromium slag to produce acid black 172 according to claim 1 is characterized in that: described adding glucose is as reductive agent: being warming up to boiling, being incubated 20-50 minute, is trivalent chromium with a small amount of hexavalent chrome reduction.
5. the method for utilizing Industry Waste chromium slag to produce acid black 172 according to claim 1 is characterized in that: described adding soda ash adjustment pH=8.5-9.0.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101519537A (en) * | 2008-02-26 | 2009-09-02 | 文擘科技股份有限公司 | Asymmetric azo complex dye and manufacturing method thereof |
| CN101538414A (en) * | 2008-03-17 | 2009-09-23 | 天津三环化学有限公司 | Method for preparing acid black 172 |
| CN102432067A (en) * | 2011-09-23 | 2012-05-02 | 无锡市霄鹰环境科技有限公司 | Process for preparing basic chromium sulfate by using waste chromium material |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101519537A (en) * | 2008-02-26 | 2009-09-02 | 文擘科技股份有限公司 | Asymmetric azo complex dye and manufacturing method thereof |
| CN101538414A (en) * | 2008-03-17 | 2009-09-23 | 天津三环化学有限公司 | Method for preparing acid black 172 |
| CN102432067A (en) * | 2011-09-23 | 2012-05-02 | 无锡市霄鹰环境科技有限公司 | Process for preparing basic chromium sulfate by using waste chromium material |
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Effective date of registration: 20200303 Address after: 300000 67 dagangshi street, Binhai New District, Tianjin Patentee after: Tianjin Sanhuan Chemical Co., Ltd Address before: Jin Lai Road 300384 Tianjin city Xiqing district north of the village. Patentee before: Tianjin Sanhuan Chemical Co., Ltd. |