CN101898824B - Sulfide heavy metal chelating trapping agent and preparation method thereof - Google Patents
Sulfide heavy metal chelating trapping agent and preparation method thereof Download PDFInfo
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- CN101898824B CN101898824B CN201010144140A CN201010144140A CN101898824B CN 101898824 B CN101898824 B CN 101898824B CN 201010144140 A CN201010144140 A CN 201010144140A CN 201010144140 A CN201010144140 A CN 201010144140A CN 101898824 B CN101898824 B CN 101898824B
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Abstract
The invention discloses a sulfide heavy metal chelating trapping agent. The trapping agent is prepared by a method of: dissolving 550g of mercaptoethylamine hydrochloric acid into 3L of chloroform; adding 900g of triethylamine as an acid binding agent; adding 400g of 3,3',5,5'-biphenyl 4-formyl chloride into 2L of chloroform; stirring and mixing the two kinds of solution, wherein the stirring velocity is between 30 and 100 r.min<-1>; performing a condensation reaction in an ice bath for 3 to 8 hours under protection of nitrogen; filtering the mixture, and extracting with water and the chloroform respectively; and distilling out redundant solvent with a rotary evaporator to obtain a white precipitate, namely a target product. The trapping agent fast reacts with various heavy metal ions in waste water at the normal temperature and generates a water-insoluble sulfide precipitate. The sulfide heavy metal chelating trapping agent has the advantages of simple preparation process and convenient use. The particle size of the produced sulfide precipitate is large, the floc is compact, the precipitation time is reduced, the concentration of heavy metal ions in the waste water below the national discharging standard, generated residue can be used for recycling heavy metal, and no secondary pollution is generated, The trapping agent can also be used for recycling precious metal in aqueous solution.
Description
Technical field
The present invention relates to removal, purification or the trapping technique of heavy metal ion in the water body, is a kind of preparation of sulfide heavy metal chelating trapping agent and the application method in water treatment thereof specifically.
Background technology
Heavy metal is meant that proportion is greater than 4 or 5 metal; Like copper (Cu), zinc (Zn), plumbous (Pb), cobalt (Co), nickel (Ni), chromium (Cr), cadmium (Cd), mercury (Hg) etc.; There are 45 kinds approximately; Arsenic (As) though do not belong to heavy metal, similar because of its source and harm with heavy metal, also list arsenic in the heavy metal class usually.Above-mentioned heavy metal ion has under physical environment stable in properties, accumulation in vivo, lower concentration and has characteristics such as secular toxic side effect, if can not get dealing carefully with, will cause severe contamination to environment.
Traditional pH regulator precipitator method are handled the waste water that contains heavy metal ion, promptly through adding alkaline chemical such as sodium hydroxide, yellow soda ash, lime, the pH value of waste water are transferred to about 11, form corresponding heavy metal hydroxide deposition to remove heavy metal ion.The pH regulator precipitator method need accurately control pH value, and to guarantee best removal effect, if contain zwitter-ions such as zine ion, aluminum ion in the waste water, the precipitation of hydroxide of formation is dissolved when high pH, needs to change different pH values, carries out multi stage precipitation and handles.Because the pH value of processed waste water is too high, supernatant liquid must pump into neutralization tank, adds acid readjustment pH to 6～9, could discharge, and treatment step is comparatively loaded down with trivial details.
Another kind of treatment process is to adopt the Sodium Sulphide precipitator method to handle heavy metal wastewater thereby, and sodium sulphite that utilization adds and heavy metal ion form the sulfide precipitation of indissoluble to remove heavy metal ion.The solubleness of heavy metal ion sulfide precipitation in water is than the low 3-5 one magnitude of corresponding metal precipitation of hydroxide, and it is less to remain in the aqueous solution concentration of heavy metal ion, and multiple metals ion can be removed in a step precipitation process.Compare advantage such as that deposition has is easily separated, be prone to filter, subsequent disposal is simple with the pH regulator precipitator method.But sodium sulphite can produce the peculiar smell of hydrogen sulfide in the use, during dissolving the oxidation side reaction can take place, and heavy metal sulfide deposition floc particle is tiny, the settling time waits so long very much, has reduced the removal effect of heavy metal ion.
In addition; Carry out the control of heavy metal contaminants with precipitation of hydroxide or sulfide precipitation; Especially administer for the electroplating wastewater that contains chelating state heavy metal ion; All have certain limitation in practice: at first the acid of the precipitation of hydroxide of heavy metal or sulfide precipitation chance all can be dissolved again, or the generation secondary pollution is decomposed in oxidation by air; The sludge moisture content that secondly above-mentioned two heavy metal species deposition is produced is bigger, and deposition not exclusively is difficult to guarantee the complete qualified discharge of heavy metal wastewater thereby.
Summary of the invention
The objective of the invention is to, overcome the defective that prior art exists, a kind of sulfide heavy metal chelating trapping agent is provided, can be at normal temperatures with waste water in Hg
2+, Cd
2+, Pb
2+, Mn
2+, Cu
2+, Ni
2+, Zn
2+, Cr
3+, Hg
2+, Cr
6+React rapidly etc. various heavy metal ion, generate stable water-insoluble heavy metal chelate deposition.Simultaneously, the present invention also provides the preparation method of sulfide heavy metal chelating trapping agent.
In order to address the above problem, the present invention through with 3,3 '; 5,5 '-chloroformic solution of biphenyl tetracarboxylic acyl chlorides and the chloroformic solution of mercaptoethylamine hydrochloride (being referred to as Mercaptamine again) react in ice-water bath, are acid binding agent with the triethylamine; Obtain title product, heavy metal chelating agent is used to handle the trade effluent that contains complexation heavy metal ion efficiently; Present technique invention has suppressed the generation of hydrogen sulfide effectively, at normal temperatures with waste water in Hg
2+, Cd
2+, Pb
2+, Mn
2+, Cu
2+, Ni
2+, Zn
2+, Cr
3+, Cr
6+React rapidly etc. various complexation heavy metal ions, generate water-insoluble sulfide precipitate.
3,3 ', 5,5 '-chloroformic solution of biphenyl tetracarboxylic acyl chlorides and the chloroformic solution of mercaptoethylamine hydrochloride react in ice-water bath, are acid binding agent with the triethylamine, obtain title product.Reaction equation is following:
With M is heavy metal ion (M=Cu, Zn, Ni, the Pb of representative; Hg, Cd, Cr; Et al) with sulfide heavy metal chelating trapping agent of the present invention or its sodium salt, sylvite through chelatropic reaction, generates stable water-insoluble heavy metal sulfide and precipitates, its molecular structural formula is as follows.
Realize that the technical scheme that the object of the invention is taked is:
A kind of sulfide heavy metal chelating trapping agent, its reaction raw materials set of dispense ratio is:
Make as follows:
550 gram mercaptoethylamine hydrochlorides are dissolved in the 3L chloroform, add 900 gram triethylamines as acid binding agent; 3,3 of 400 grams ', 5,5 '-the biphenyl tetracarboxylic acyl chlorides is dissolved in the 2L chloroform; Above-mentioned two solution are under agitation slowly mixed, and the control stir speed (S.S.) is 30-100r.min
-1Under nitrogen protection, under ice bath, carry out condensation reaction 3～8 hours, filter then, water and chloroform extract respectively, with Rotary Evaporators unnecessary solvent are distilled out, and obtain white precipitate, are title product, sulfide heavy metal chelating trapping agent.
According to heavy metal ion kind and the concentration in the waste water; Add an amount of sulfide heavy metal chelating trapping agent of the present invention or its sodium salt, sylvite, also can wait other water conditioner to be used with SEPIGEL 305 (PAM), the heavy metal precipitation particle of generation be big, flco is closely knit; Settling time is short; Concentration of heavy metal ion in the processed waste water reaches discharging standards, and the recyclable heavy metal of the residue of generation is difficult for producing secondary pollution; This trapping agent also can be used for the noble metal in the recycle-water solution.
Sulfide heavy metal chelating trapping agent of the present invention is used to handle the trade effluent that contains complexation heavy metal ion, can effectively suppress the generation of hydrogen sulfide, at normal temperatures with waste water in Hg
2+, Cd
2+, Pb
2+, Mn
2+, Cu
2+, Ni
2+, Zn
2+, Cr
3+, Cr
6+React rapidly etc. various heavy metal ion, generate water-insoluble sulfide precipitate.Sulfide heavy metal chelating trapping agent of the present invention, preparation technology is simple, and is easy to use, and treatment effect is good.Can use separately, also can be used with other water conditioner.The sulfide precipitation particle of producing is big, flco is closely knit, has shortened the settling time, is prone to make the concentration of heavy metal ion in the waste water to reach below the national specified discharge standard, and the recyclable heavy metal of the residue of generation is difficult for producing secondary pollution; This trapping agent also can be used for the noble metal in the recycle-water solution.Required equipment is simple, and is easy to operate, and cost performance is higher, goes for circuit card, plating, metal finishing, film manufacturing, coal-fired plant, municipal administration or industry wastewater treatments such as industrial refuse and incineration, battery production.
Embodiment
Below in conjunction with embodiment, the present invention is elaborated.
Embodiment 1
550 gram mercaptoethylamine hydrochlorides are dissolved in the 3L chloroform, add 900 gram triethylamines as acid binding agent, 3,3 of 400 grams ', 5,5 '-the biphenyl tetracarboxylic acyl chlorides is dissolved in the 2L chloroform control stir speed (S.S.) 30-100r.min
-1(the best is 50r.min
-1), above-mentioned two solution are under agitation slowly mixed, under nitrogen protection; Under ice bath, carry out condensation reaction 3～8 hours, filter then, water and chloroform extract respectively; With Rotary Evaporators unnecessary solvent is distilled away, obtain white precipitate, be title product; Sulfide heavy metal chelating trapping agent, reaction yield 87%.
Embodiment 2
Select the board wastewater of Suzhou company for use, recording copper ion concentration is 206mg.L
-1, pH is 5.1.Add 950mg.L
-1The sulfide heavy metal chelating trapping agent of embodiment 1, stir speed (S.S.) are 30r.min
-1, reaction is left standstill filtration after stirring 5min, gets supernatant, measures its copper ion concentration with atomic (Australian GBC company) and is respectively 0.041mg.L
-1, copper ion concentration is far smaller than the special emission limit 0.30mg.L of water pollutant that electroplates among the pollutent discharging standards GB21900-2008
-1
Embodiment 3
Select the electroplating wastewater of Danyang, Jiangsu Province company for use, record Zn
2+Concentration is 5.52mg/L, Ni
2+Concentration is 4.37mg/L.Add 60mg.L
-1The sodium salt of the sulfide heavy metal chelating agent of embodiment 1, stir speed (S.S.) are 30r.min
-1, reaction is left standstill filtration after stirring 5min, gets supernatant and measures Ni
2+And Zn
2+Concentration is respectively 0.044mg.L
-1, 0.097mg.L
-1, be far smaller than the special emission limit 0.10mg.L of water pollutant that electroplates among the pollutent discharging standards GB21900-2008
-1And 1.0mg.L
-1
Patent of the present invention has the same performance that similarly captures to other heavy metal ion.
Claims (2)
1. sulfide heavy metal chelating trapping agent, its reaction raw materials set of dispense ratio is:
Make as follows:
550 gram mercaptoethylamine hydrochlorides are dissolved in the 3L chloroform, add 900 gram triethylamines as acid binding agent; With 3,3 of 400 grams ', 5,5 '-the biphenyl tetracarboxylic acyl chlorides is dissolved in the 2L chloroform; Above-mentioned two solution stirring are mixed, and stir speed (S.S.) is 30-100r.min
-1Under nitrogen protection, under ice bath, carry out condensation reaction 3～8 hours, filter then, water and chloroform extract respectively, with Rotary Evaporators unnecessary solvent are distilled out, and obtain white precipitate, are title product.
2. the preparation method of the said a kind of sulfide heavy metal chelating trapping agent of claim 1 the steps include:
550 gram mercaptoethylamine hydrochlorides are dissolved in the 3L chloroform, add 900 gram triethylamines as acid binding agent; With 3,3 of 400 grams ', 5,5 '-the biphenyl tetracarboxylic acyl chlorides is dissolved in the 2L chloroform; Above-mentioned two solution stirring are mixed, and stir speed (S.S.) is 30-100r.min
-1Under nitrogen protection, under ice bath, carry out condensation reaction 3～8 hours, filter then, water and chloroform extract respectively, with Rotary Evaporators unnecessary solvent are distilled out, and obtain white precipitate, are title product.
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| CN101898824B true CN101898824B (en) | 2012-10-24 |
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| CN102309956A (en) * | 2011-04-04 | 2012-01-11 | 上海丰信环保科技有限公司 | Reagent for removing heavy metal Cr (VI) and Pb<2+> in waste water |
| JP5899085B2 (en) * | 2011-09-22 | 2016-04-06 | アークレイ株式会社 | Heavy metal recovery method and heavy metal recovery reagent used therefor |
| CN102531137B (en) * | 2012-01-04 | 2014-01-22 | 南京师范大学 | Sulfide heavy metal chelating agent and preparation method thereof |
| US9802889B2 (en) | 2014-12-02 | 2017-10-31 | Covalent Research Technologies, LLC | Solid supported trithiol compounds for removing heavy metals from solution, and filtration systems utilizing the compounds |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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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Effective date of registration: 20180427 Address after: 211124 Jinqiao Road 111, Chunhua Road, Jiangning District, Nanjing, Jiangsu Patentee after: Nanjing Zheng Long Environmental Protection Engineering Co., Ltd. Address before: No. 1, Wen Yuan Road, Xianlin new town, Nanjing, Jiangsu Patentee before: Nanjing Normal University |
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