CN100427549C - Process for removing heavy metals in dye by companion method - Google Patents
Process for removing heavy metals in dye by companion method Download PDFInfo
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- CN100427549C CN100427549C CNB2004100657166A CN200410065716A CN100427549C CN 100427549 C CN100427549 C CN 100427549C CN B2004100657166 A CNB2004100657166 A CN B2004100657166A CN 200410065716 A CN200410065716 A CN 200410065716A CN 100427549 C CN100427549 C CN 100427549C
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- dye
- organic amine
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- iron
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Abstract
The present invention relates to a method for removing heavy metals in dye by a matching method. The method relates to a technology for reducing the content of heavy metals in dye, particularly for reducing the content of copper and iron in anthraquinoid dye. The method comprises the steps: 1) organic amine or organic amine salts are dissolved in 1% to 5% diluted sulfuric acid according to a mass ratio of the organic amine or the organic amine salt to the dye of 1:1 to 1:100; 2) the dye is immerged in the mixture to be stirred for 3 to 10 hours at 60 to 100 DEG C; 3) the hot dye is filtered and is washed with water till a pH value is from 6 to 7; 4) the washed dye is dried at 100 to 150 DEG C; and 5) the dye is pulverized. By using the organic amine or the organic amine salt, the organic amine or the organic amine salts react with various salts of metals, such as copper, iron, etc. which are dissolved in the solution to generate a water solubility coordination compound with a maximal stability constant. Then, the coordination compound is filtered to achieve the purpose of reducing the content of the heavy metals. Thus, the copper content of the dye can be reduced to about 10 ppm, and the iron content of the dye can be reduced to about 100 ppm.
Description
Technical field
The present invention is a kind of technology that reduces heavy metal content in the dyestuff that relates to, and particularly reduces the content of copper in the dyes of anthraquinone, iron.
Background technology
At present, dark dye, especially high-grade light-resistant dye, anthraquinone dye are first-selected objects.Anthraquinone dye has two big advantages: the one, and light fastness is good, and the 2nd, can produce chromatic colour, in red, purple, blue, green dark dye, anthraquinone dye occupies irreplaceable critical role.Anthraquinone dye synthesis technique complexity, " three wastes " are seriously polluted, and " three wastes " amount is big, is difficult to administer, and external anthraquinone dye is the reduce or stop production state, for favourable condition has been created in China's dyes of anthraquinone outlet, a lot of dyes of anthraquinone outlet becoming product that sell well.Along with the increasing of market demand, strict day by day to the specification of quality of dyes of anthraquinone, especially strict more requirement has been proposed heavy metal content in the dyestuff.
In the production process of anthraquinone dyes, because the location of reacting on the anthraquinone is complicated, some reaction needs to locate with heavy metal, normal copper or the mantoquita of using is (as cupric oxide in the reaction, neutralized verdigris, cuprous chloride etc.) make catalyzer, therefore often there is mantoquita to be mingled in the dyestuff.In the production process of anthraquinone class vat dyes, the source of iron is because some reaction needed iron powder is made catalyzer on the one hand, is because iron and oxide compound thereof in the conversion unit are sneaked in process of production on the other hand.
For the anthraquinone type vat dyes, owing to be insoluble in water, so adopt the precipitator method, that extraction process is removed metal ion is improper, more satisfactory is that the impurity in the dyestuff is generated material soluble in water, dyestuff is mixed with water again, and impurity is by the filtration removal.Remove the most widely now that the method for heavy metal is a dilute sulfuric acid process in the dyestuff.Dilute sulphuric acid can react with metal oxide and metallic iron, generates ferric sulfate, ferrous sulfate, the ferrous sulfate of generation, and ferric sulfate, water soluble can reduce the content of iron in the dyestuff after filtration greatly.Dilute sulphuric acid can also react with mantoquitas such as cupric oxide, neutralized verdigriss, and the copper sulfate water soluble of generation can reduce the content of copper in the dyestuff after filtration.But the dyestuff that adopts dilute sulphuric acid to handle, its copper iron level can not be satisfactory.General copper content is about 200ppm, and iron level is about 1000ppm.
Adopt Japanese Patent distillation, the method for sublimating reduce the content of iron, copper in the vat dyes, but for the difficult dyestuff that distils of great majority, this method is inapplicable.
Summary of the invention
Technical problem: the purpose of this invention is to provide the method that a kind of companion method is removed heavy metal in the dyestuff, this method is simple, can make that copper content is reduced in the 50ppm in the dyestuff, and iron level is reduced to about 250ppm.
Technical scheme: method provided by the invention is to use organic amine or organic amine salt, make organic amine or organic amine salt and be dissolved in multiple reacting metal salts such as copper in the water, iron, generate the great water-soluble coordination compound of stability constant, by filtering and dye separation, to reach the purpose that reduces heavy metal content.Used organic amine or organic amine salt are ethylenediamine tetraacetic acid (EDTA), triacetamide, trolamine, disodium ethylene diamine tetraacetate, wherein the disodium ethylene diamine tetraacetate best results.
Its technical scheme is as follows:
1) be that 1: 1～1: 100 ratio is dissolved in organic amine or organic amine salt in 1%～5% dilute sulphuric acid according to organic amine or organic amine salt and dyestuff mass ratio,
2) with dye-impregnated in above-mentioned solution, in 60～100 ℃, stir 3～10h,
3) above-mentioned dyestuff is taken advantage of ripe filtration, is washed to pH value 6～7,
4) will wash 100～150 ℃ of oven dry of back dyestuff,
5) dyestuff is pulverized.
Beneficial effect: the present invention compares with background technology, and heavy metal content such as copper, iron are further reduced, and copper content is reduced in the 50ppm, and iron level is reduced to about 250ppm.Method therefor is simple, easily realizes industrialization, and required cost is low.
Embodiment
By the following examples the present invention is described in further detail:
Embodiment 1
1 gram disodium ethylene diamine tetraacetate is joined in 1% the dilution heat of sulfuric acid of 200ml, be mixed with concentration and be 0.5% solution, add the former powder of 6 gram anthraquinone class vat dyes vat red browns, in 90 ℃, stirred 3 hours.Filtered while hot then.Be washed to pH value 6～7.To wash the back dyestuff 100～150 ℃ of oven dry.Products obtained therefrom coloured light is not affected.With the content of its copper of aas determination, iron, the gained result is as follows:
Embodiment 2
Implementation step is identical with embodiment 1 with method.Reaction conditions and reaction result are as showing down
Embodiment 3
Implementation step is identical with embodiment 1 with method.Reaction conditions and reaction result are as follows
Embodiment 4
Implementation step is identical with embodiment 1 with method.Reaction conditions and reaction result are as follows
Embodiment 5
Implementation step is identical with embodiment 1 with method.Reaction conditions and reaction result are as follows
Embodiment 6
Implementation step is identical with embodiment 1 with method.Reaction conditions and reaction result are as follows
Embodiment 7
Implementation step is identical with embodiment 1 with method.Change organic amine, organic amine concentration is 0.5%, and organic amine and dyestuff mass ratio are 1: 6,90 ℃ of dipping temperatures, and dipping time 3 hours, reaction conditions and reaction result are as follows
Embodiment 8
Implementation step is identical with embodiment 1 with method.Organic amine salt adopts disodium ethylene diamine tetraacetate, and reaction conditions is with embodiment 1, and dyestuff is selected vat golden orange for use, and reaction result is as follows
Claims (1)
1. a companion method is removed the method for heavy metal in the dyestuff, it is characterized in that the step that adopts is:
1) a kind of in triacetamide, trolamine, the disodium ethylene diamine tetraacetate is dissolved in to be made into concentration in 1%～5% dilute sulphuric acid be 0.01～1% organic amine or organic amine salt solution,
2) according to organic amine or organic amine salt and dyestuff mass ratio be 1: 1～1: 100 ratio with dye-impregnated in organic amine or organic amine salt solution, in 60～100 ℃, stirred 3～10 hours,
3) with above-mentioned dyestuff filtered while hot, be washed to pH value 6～7,
4) will wash 100～150 ℃ of oven dry of back dyestuff,
5) dyestuff is pulverized.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100657166A CN100427549C (en) | 2004-11-15 | 2004-11-15 | Process for removing heavy metals in dye by companion method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100657166A CN100427549C (en) | 2004-11-15 | 2004-11-15 | Process for removing heavy metals in dye by companion method |
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| CN1631988A CN1631988A (en) | 2005-06-29 |
| CN100427549C true CN100427549C (en) | 2008-10-22 |
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| CNB2004100657166A Expired - Fee Related CN100427549C (en) | 2004-11-15 | 2004-11-15 | Process for removing heavy metals in dye by companion method |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102689923B (en) * | 2011-03-24 | 2017-10-13 | 杨春晓 | The preparation method of lead-acid battery PbO nano-powder |
| CN102689921B (en) * | 2011-03-24 | 2017-08-08 | 杨春晓 | The preparation method for the Pb nm-class oxide powders for reclaiming and manufacturing for lead-acid accumulator |
| CN102689922B (en) * | 2011-03-24 | 2017-04-19 | 杨春晓 | Lead compound nano-powder preparation method for recovery and manufacture of lead-acid battery |
| CN104448890B (en) * | 2014-11-29 | 2016-07-06 | 萧县凯奇化工科技有限公司 | A kind of low heavy metal vat olive MW dyestuff and preparation method thereof |
| CN111662746A (en) * | 2019-03-07 | 2020-09-15 | 中国科学院过程工程研究所 | Method for synchronously demetallizing, desalting and dehydrating coal tar |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4963660A (en) * | 1987-09-02 | 1990-10-16 | Hoechst Aktiengesellschaft | Process for the reduction of heavy metal ions in excess from aqueous synthesis solutions of water soluble heavy metal complex dyestuffs |
| DE4213163A1 (en) * | 1992-04-22 | 1993-10-28 | Bayer Ag | Zeolite use for removing heavy metal ions from dyestuff soln. - e.g. from metal complex prodn., catalyst or reagent to reduce pollution or contamination or increase stability of soln. |
| JPH0827390A (en) * | 1994-07-13 | 1996-01-30 | Mitsui Toatsu Chem Inc | Method for purifying vat dye and intermediate thereof |
| US6177571B1 (en) * | 1997-05-13 | 2001-01-23 | Zambon Group S.P.A. | Method for removing heavy metals from organic compounds |
| CN1478825A (en) * | 2003-05-01 | 2004-03-03 | 马世金 | Phthalocyanine dye deep processing technology |
-
2004
- 2004-11-15 CN CNB2004100657166A patent/CN100427549C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4963660A (en) * | 1987-09-02 | 1990-10-16 | Hoechst Aktiengesellschaft | Process for the reduction of heavy metal ions in excess from aqueous synthesis solutions of water soluble heavy metal complex dyestuffs |
| DE4213163A1 (en) * | 1992-04-22 | 1993-10-28 | Bayer Ag | Zeolite use for removing heavy metal ions from dyestuff soln. - e.g. from metal complex prodn., catalyst or reagent to reduce pollution or contamination or increase stability of soln. |
| JPH0827390A (en) * | 1994-07-13 | 1996-01-30 | Mitsui Toatsu Chem Inc | Method for purifying vat dye and intermediate thereof |
| US6177571B1 (en) * | 1997-05-13 | 2001-01-23 | Zambon Group S.P.A. | Method for removing heavy metals from organic compounds |
| CN1478825A (en) * | 2003-05-01 | 2004-03-03 | 马世金 | Phthalocyanine dye deep processing technology |
Non-Patent Citations (2)
| Title |
|---|
| 蒽醌类还原染料除铜的研究. 张进等.化工时刊，第17卷第10期. 2003 |
| 蒽醌类还原染料除铜的研究. 张进等.化工时刊，第17卷第10期. 2003 * |
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| CN1631988A (en) | 2005-06-29 |
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