CN102070235A - Water-soluble organic thiamine heavy metal chelating agent and preparation method thereof - Google Patents
Water-soluble organic thiamine heavy metal chelating agent and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a water-soluble organic thiamine heavy metal chelating agent and a preparation method thereof. The molecular formula of the heavy metal chelating agent is C2H4N2S4. The preparation method comprises the following steps: dissolving 100-500mL of polyamine in 100mL of purified water, dissolving 50-200mL of organic sulfur in 100mL of absolute alcohol, then adding 5-10mL of emulsifier, mixing the two solutions, heating the solutions with 40-50 DEG C of water bath, adding 5-20g of solid inorganic base while keeping stirring, reacting for 6-8h, cooling to less than 10 DEG C to crystallize, separating out the solid, and washing with absolute alcohol. The chelating agent of the invention can rapidly react with various heavy metal ions in wastewater and chelating heavy metal ions; precipitation can be performed rapidly; and heavy metals can be recycled easily from the generated precipitate and secondary pollutions can be reduced. The heavy metal chelating agent has cheap raw materials and simple equipment and is suitable for the wastewater treatment in the industries such as printed circuit boards, electroplating, pigments, metal surface treatment and battery production.
Description
Technical field
The present invention relates to the removal technology of heavy metal ion in the trade effluent, is a kind of water-soluble organic thiamines heavy metal chelating agent and preparation method thereof specifically.Cu in this trapping agent and the waste water at normal temperatures
2+, Ni
2+, Cd
2+, Hg
2+, Pb
2+, Cr
3+Etc. heavy metal ion and complexation heavy metal ion generation rapid reaction, generate infusible precipitate, thereby heavy metal ion is removed from water.
Background technology
Often contain heavy metal ion or complexation heavy metal ions such as chromium, cadmium, nickel, copper, lead, zinc in the trade effluent.In water body, because the refractory organics and the toxic of heavy metal ion have a strong impact on generations such as fishery and agriculturals, and heavy metal ion can also be at human body and biological cylinder accumulation, and can't be degraded by microorganisms, and is detrimental to health directly or indirectly.
The neutralization precipitation method is the method for a kind of development processing heavy metal ion the earliest, also is the most general, one of the simplest method.It is by adding basic agents such as lime, soda, mineral alkali, and the pH value of waste water is adjusted to the scope that makes heavy metal ion have minimal solubility, and its form with oxyhydroxide or carbonate is precipitated.When containing both sexes heavy metal ion such as aluminium, zinc in the waste water, the neutralization precipitation method needs strict control pH value, otherwise the precipitate metal hydroxides of generation is dissolved under the situation of high pH once more.In addition, the neutralization precipitation method can not be removed the complexation heavy metal ion in the water.
Sulphide precipitation is to add vulcanizing agent in containing the waste water of heavy metal ion, because heavy metal ion and sulfonium ion have very strong avidity, can generate the very little sulfide precipitation of solubility product, thereby reaches the purpose of removing heavy metal ion.Compare with the neutralization precipitation method, the advantage that sulphide precipitation has is: heavy metal sulfide solubleness is lower than the solubleness of its oxyhydroxide, thereby improve removal of heavy metal ions efficient, and reaction pH value is between 7-9, the waste water after the processing generally need not neutralize.Yet the shortcoming that sulphide precipitation has is: the sulfide precipitation composition granule is little, easily forms colloid, is not easy precipitation; The sulfide precipitation agent is originally residual in water, meets acid and generates hydrogen sulfide, produces secondary pollution.
The heavy metal chelating agent precipitator method are to utilize the N of heavy metal chelating agent own, S ligating atom and heavy metal intensive sequestering action, generate water-fast metallo-chelate, thereby reach the purpose of removing heavy metal ion.The heavy metal chelating agent precipitator method are compared with sulphide precipitation, and its advantage is: floc particle is big and closely knit, and sedimentation function is good, and the heavy metal ion residual concentration is low, can use in pH scope widely, and can not produce hydrogen sulfide.But also there is defective in the heavy metal chelating agent precipitator method, and present most of heavy metal chelating agents water-soluble relatively poor influences the efficient that it removes heavy metal ion.
Summary of the invention
The objective of the invention is to: the defective that overcomes prior art, a kind of water-soluble organic thiamines heavy metal chelating agent and preparation method thereof is provided, the present invention is in the aqueous solution of alkalescence, by polyamines and organosulfur reaction, generate the organosulfur amine compound, by crystallisation by cooling and absolute ethanol washing, purify at last, make a kind of water-soluble organic thiamines heavy metal chelating agent.Water-soluble organic thiamines heavy metal chelating agent of the present invention at normal temperatures can with the Cu in the waste water
2+, Ni
2+, Cd
2+, Hg
2+, Pb
2+, Cr
3+Etc. heavy metal ion and complexation heavy metal ion rapid reaction, generate the heavy metal precipitation thing, by solid-liquid separation, reach the purpose of removing heavy metal ion in the water.
Purpose of the present invention is achieved through the following technical solutions:
A kind of water-soluble organosulfur ammonium heavy metal chelating agent, its molecular formula is C
2H
4N
2S
4, structural formula is:
The preparation method of above-mentioned water-soluble organosulfur ammonium heavy metal chelating agent comprises the steps:
(1) the 100-500mL polyamines is dissolved in during 100mL purifies waste water, is mixed with polyamines-aqueous solution;
(2) the 50-200mL organosulfur is dissolved in the 100mL dehydrated alcohol, adds the 5-10mL mass concentration again and be 100% emulsifying agent, be mixed with organosulfur-ethanol solution;
(3) polyamines-aqueous solution is mixed with organosulfur-ethanol solution be placed on 40-50 ℃ of water bath with thermostatic control heating, and under whipped state, add 5-20g mineral alkali solid, under agitation react 6-8h;
(4) be cooled to below 10 ℃ after the crystallization, isolate solid by suction filtration, use absolute ethanol washing 2 times again after, drying can obtain water-soluble organic thiamines heavy metal chelating agent.
The used emulsifying agent of above-mentioned preparation method is an ethoxylated dodecyl alcohol.
The used polyamines of above-mentioned preparation method is a hydrazine hydrate.
The used organosulfur of above-mentioned preparation method is a dithiocarbonic anhydride.
The used mineral alkali solid of above-mentioned preparation method is sodium hydroxide or potassium hydroxide.
The used drying means of above-mentioned preparation method is vacuum-drying, and drying temperature is 25-45 ℃.
The trapping agent of method for preparing is used for removing the heavy metal ion of waste water.
The trapping agent of method for preparing and flocculation agent polyacrylamide are used.
Concentration and kind at heavy metal ions in wastewater, can add appropriate amount water-soluble organic thiamines heavy metal chelating agent of the present invention separately, also can wait other water conditioner to be used with flocculation agent polyacrylamide (being called for short PAM), pass through stirring reaction, generate the big and closely knit flco of particle, rapid subsidence.The concentration of heavy metal ion is lower than discharging standards in the processed waste water, and the throw out that produces is easy to reclaim heavy metal, can not produce secondary pollution.This water-soluble organic thiamines heavy metal chelating agent also can be used for noble metal in the recycle-water solution, can turn waste into wealth to a certain extent.
The present invention compared with prior art has following advantage and beneficial effect:
(1) trapping agent of the present invention is water-soluble better, reaches 15g100g water 20 ℃ of following solubleness
-1Thereby, trapping agent can fully be reacted with various heavy metal ions in waste water.
(2) heavy metal ion in the waste water and complexation heavy metal ion are reacted rapidly, the heavy metal precipitation composition granule of generation is big, and settling property is good, is easy to solid-liquid separation.
(3) trapping agent of the present invention can use under the condition of strong acid, compares with existing technology, reduces the dosage of alkali.
(4) trapping agent Cu of the present invention
2+, Ni
2+, Cd
2+, Hg
2+, Pb
2+, Cr
3+Clearance etc. heavy metal ion and complexation heavy metal ion all can reach more than 99%.
(5) cost of material required for the present invention is cheap, and preparation technology and equipment are simple, and is easy to operate, applicable to the wastewater treatment of industries such as printed-wiring board (PWB), plating, pigment, metal finishing and battery production.
Embodiment
Below in conjunction with specific embodiment the present invention is done further concrete detailed description the in detail, but embodiments of the present invention are not limited thereto, the processing parameter for not indicating especially can carry out with reference to routine techniques.
Below in conjunction with embodiment, the present invention is elaborated
Embodiment 1
The 100mL hydrazine hydrate is dissolved in during 100mL purifies waste water, and is mixed with hydrazine hydrate-aqueous solution; 50mL dithiocarbonic anhydride is dissolved in the 100mL dehydrated alcohol, adds the 5mL ethoxylated dodecyl alcohol again, is mixed with dithiocarbonic anhydride-ethanol solution; After above-mentioned two kinds of solution mixing, 40 ℃ of waters bath with thermostatic control heating, under agitation, add 5g sodium hydroxide, reaction 6h, be cooled to 10 ℃ of following crystallizations after, suction filtration 30 ℃ of following vacuum-dryings, obtains water-soluble organic thiamines heavy metal chelating agent crystal of white with absolute ethanol washing crystal 2 time back.
Embodiment 2
The difference of present embodiment and embodiment 1 is: proportioning raw materials and processing parameter, specifically see table 1 for details.
Embodiment 3
The difference of present embodiment and embodiment 1 is: proportioning raw materials and processing parameter, specifically see table 1 for details.
Embodiment 4
The difference of present embodiment and embodiment 1 is: proportioning raw materials and processing parameter, specifically see table 1 for details.
Table 1
| Processing parameter | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Polyamines/mL | ?100 | ?200 | ?300 | ?500 |
| Purify waste water/mL | ?100 | ?100 | ?100 | ?100 |
| Dehydrated alcohol/mL | ?100 | ?100 | ?100 | ?100 |
| Organosulfur/mL | ?50 | ?100 | ?150 | ?200 |
| Mineral alkali/g | ?5 | ?10 | ?15 | ?20 |
| Emulsifying agent/mL | ?5 | ?7 | ?9 | ?10 |
| Water bath with thermostatic control/℃ | ?40 | ?45 | ?45 | ?50 |
| Reaction times/h | ?6 | ?7 | ?8 | ?8 |
Select Guangzhou company electronics waste water for use, recording EDTA complex copper ion concentration is 105.32mgL
-1, the pH value is 4.2, adds water-soluble organic thiamines heavy metal chelating agent 300mgL of embodiment 1-4 respectively
-1, stir speed (S.S.) is 60rmin
-1, reaction is static behind the 3min, gets supernatant liquor and measures its copper ion concentration and be respectively 0.42mgL
-1, 0.38mgL
-1, 0.31mgL
-1And 0.26mgL
-1, copper ion concentration all reaches discharging standards, and adds non-water-soluble organic thiamines heavy metal chelating agent DTC (EDA) of same amount, and after handling above-mentioned waste water under the identical condition, getting supernatant liquor, to measure its copper ion concentration be 5.38mgL
-1, copper ion concentration is higher than discharging standards.
Select Guangzhou company printed-wiring board (PWB) waste water for use, recording nickel ion concentration is 25.16mgL
-1, the pH value is 5.3, adds water-soluble organic thiamines heavy metal chelating agent 80mgL of embodiment 1-4 respectively
-1, stir speed (S.S.) is 60rmin
-1, reaction is static behind the 3min, gets supernatant liquor and measures its copper ion concentration and be respectively 0.72mgL
-1, 0.58mgL
-1, 0.45mgL
-1And 0.39mgL
-1, nickel ion concentration all reaches discharging standards, and adds non-water-soluble organic thiamines heavy metal chelating agent DTC (EDA) of same amount, and after handling above-mentioned waste water under the identical condition, getting supernatant liquor, to measure its nickel ion concentration be 1.17mgL
-1, nickel ion concentration is higher than discharging standards.
Select somewhere, Guangdong mine wastewater for use, record Cd
2+, Hg
2+, Pb
2+, Cr
3+Concentration is respectively 5.6mgL
-1, 2.7mgL
-1, 14.3mgL
-1, 7.3mgL
-1, the pH value is 2.3, adds water-soluble organic thiamines heavy metal chelating agent 60mgL of embodiment 1-4 respectively
-1, stir speed (S.S.) is 60rmin
-1, static behind the reaction 3min, get supernatant liquor and measure its Cd
2+, Hg
2+, Pb
2+, Cr
3+Concentration is respectively 0.08mgL
-1, 0.02mgL
-1, 0.5mgL
-1And 0.9mgL
-10.07mgL
-1, 0.04mgL
-1, 0.4mgL
-1And 0.3mgL
-10.05mgL
-1, 0.03mgL
-1, 0.5mgL
-1And 0.3mgL
-10.02mgL
-1, 0.01mgL
-1, 0.75mgL
-1And 0.69mgL
-1Each ionic concn all reaches discharging standards, and adds non-water-soluble organic thiamines heavy metal chelating agent DTC (EDA) of same amount, after handling above-mentioned waste water under the identical condition, gets supernatant liquor and measures its Cd
2+, Hg
2+, Pb
2+, Cr
3+Concentration is respectively 0.18mgL
-1, 0.22mgL
-1, 1.5mgL
-1And 2.9mgL
-1, each ionic concn all is higher than discharging standards.
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (9)
1. a water-soluble organosulfur ammonium heavy metal chelating agent is characterized in that its molecular formula is C
2H
4N
2S
4, structural formula is:
2. the preparation method of water-soluble organosulfur ammonium heavy metal chelating agent according to claim 1 is characterized in that, comprises the steps:
(1) the 100-500mL polyamines is dissolved in during 100mL purifies waste water, is mixed with polyamines-aqueous solution;
(2) the 50-200mL organosulfur is dissolved in the 100mL dehydrated alcohol, adds the 5-10mL mass concentration again and be 100% emulsifying agent, be mixed with organosulfur-ethanol solution;
(3) polyamines-aqueous solution is mixed with organosulfur-ethanol solution be placed on 40-50 ℃ of water bath with thermostatic control heating, and under whipped state, add 5-20g mineral alkali solid, under agitation react 6-8h;
(4) be cooled to below 10 ℃ after the crystallization, isolate solid by suction filtration, use absolute ethanol washing 2 times again after, drying promptly obtains water-soluble organic thiamines heavy metal chelating agent.
3. preparation method according to claim 2 is characterized in that, described emulsifying agent is an ethoxylated dodecyl alcohol.
4. preparation method according to claim 1 is characterized in that, described polyamines is a hydrazine hydrate.
5. preparation method according to claim 1 is characterized in that, described organosulfur is a dithiocarbonic anhydride.
6. preparation method according to claim 1 is characterized in that, described mineral alkali solid is sodium hydroxide or potassium hydroxide.
7. preparation method according to claim 1 is characterized in that, described drying means is vacuum-drying, and drying temperature is 25-45 ℃.
8. according to the application of the described trapping agent of claim 1, it is characterized in that this trapping agent is used for removing the heavy metal ion of waste water.
9. the application of described trapping agent according to Claim 8 is characterized in that, this trapping agent and flocculation agent polyacrylamide are used.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102942512A (en) * | 2012-11-21 | 2013-02-27 | 南京师范大学 | Preparation method of sulfide heavy metal trapping agent C2H4N2S4 |
| CN104128159A (en) * | 2014-08-13 | 2014-11-05 | 陕西科技大学 | Wastewater treatment material with photocatalysis and heavy metal adsorption functions and capable of being recycled and preparation method thereof |
| CN104528910A (en) * | 2014-12-18 | 2015-04-22 | 淄博金鼎光电科技有限公司 | Synthetic process of heavy metal chelating agent |
| CN104610972A (en) * | 2014-12-18 | 2015-05-13 | 淄博金鼎光电科技有限公司 | Heavy metal polluted soil treatment processing agent and preparation method thereof |
| CN106914205A (en) * | 2015-12-28 | 2017-07-04 | 沈阳中科环境工程科技开发有限公司 | The preparation method and special purpose device of a kind of novel heavy metal agent for capturing |
| CN111282317A (en) * | 2020-03-11 | 2020-06-16 | 吕文广 | Method for removing solid particles in nickel-cobalt-manganese lithium salt and lithium battery material |
| CN115772106A (en) * | 2022-11-04 | 2023-03-10 | 西北矿冶研究院 | Diamine bisdithiocarbamic acid sodium salt and preparation method thereof |
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| WO2002049967A2 (en) * | 2000-12-06 | 2002-06-27 | University Of Kentucky Research Foundation | Novel multidentate sulfur-containing ligands |
| CN101628750A (en) * | 2009-09-10 | 2010-01-20 | 南京师范大学 | Sulfide heavy metal chelating agent and preparation method thereof |
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2010
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| DE19956726A1 (en) * | 1999-11-25 | 2001-05-31 | Wieland Edelmetalle | Removing heavy metal, especially nickel, ions from waste water in the metal processing industries by further treating the hydroxide precipitate with an excess of sulfide and then filtering and oxidizing the sulfide |
| WO2002049967A2 (en) * | 2000-12-06 | 2002-06-27 | University Of Kentucky Research Foundation | Novel multidentate sulfur-containing ligands |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102942512A (en) * | 2012-11-21 | 2013-02-27 | 南京师范大学 | Preparation method of sulfide heavy metal trapping agent C2H4N2S4 |
| CN104128159A (en) * | 2014-08-13 | 2014-11-05 | 陕西科技大学 | Wastewater treatment material with photocatalysis and heavy metal adsorption functions and capable of being recycled and preparation method thereof |
| CN104128159B (en) * | 2014-08-13 | 2016-04-20 | 陕西科技大学 | There is wastewater treatment material that photocatalysis and heavy metal adsorption function can be recycled and preparation method thereof |
| CN104528910A (en) * | 2014-12-18 | 2015-04-22 | 淄博金鼎光电科技有限公司 | Synthetic process of heavy metal chelating agent |
| CN104610972A (en) * | 2014-12-18 | 2015-05-13 | 淄博金鼎光电科技有限公司 | Heavy metal polluted soil treatment processing agent and preparation method thereof |
| CN106914205A (en) * | 2015-12-28 | 2017-07-04 | 沈阳中科环境工程科技开发有限公司 | The preparation method and special purpose device of a kind of novel heavy metal agent for capturing |
| CN111282317A (en) * | 2020-03-11 | 2020-06-16 | 吕文广 | Method for removing solid particles in nickel-cobalt-manganese lithium salt and lithium battery material |
| CN115772106A (en) * | 2022-11-04 | 2023-03-10 | 西北矿冶研究院 | Diamine bisdithiocarbamic acid sodium salt and preparation method thereof |
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