CN102583685B - Method for removing trace mercury in water solution - Google Patents
Method for removing trace mercury in water solution Download PDFInfo
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- CN102583685B CN102583685B CN201210033299.1A CN201210033299A CN102583685B CN 102583685 B CN102583685 B CN 102583685B CN 201210033299 A CN201210033299 A CN 201210033299A CN 102583685 B CN102583685 B CN 102583685B
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Abstract
The invention discloses a method for removing trace mercury in water solution, which comprises the following steps of: culturing and analyzing plants grown under mercury environment, utilizing an adsorption and coprecipitation principle to adjust a pH value of water solution containing mercury, adding a coordination complex or a composite formed by a sulphur-containing substance and one or more than two of a zinc-containing reagent, a copper-containing reagent or an iron-containing reagent; and after standing and precipitating, extracting water containing mercury slags, wherein the content of mercury is less than 0.01mg/L. The method is characterized in that: through selection of appropriate sulphur-containing substance, the adding amount of the sulphur-containing substance and the zinc-containing reagent, the copper-containing reagent or the iron-containing reagent, and the pH value of the solution are controlled, so that trace mercury elements in the water solution can be removed; and the materials are economic and easy to get, no any harmful element is added in a system, so that the method is an environmental-friendly and economical processing process. The process can be widely used for treating wastewater containing mercury discharged by the fields such as metallurgy, chemistry, pesticides, pigments, papermaking and leatherworking.
Description
[technical field]
The present invention relates to the field of waste water treatment in environment, particularly a kind of method that removes trace mercury in water solution.
[background technology]
Along with increasing sharply of trade waste, the heavy metal in water mercury pollution causing is more and more serious.In trade effluent, usually find mercury, maximum mercury pollution source is from industries such as metallurgy, chemical industry, agricultural chemicals, pigment, fuel, papermaking, process hides.In these industrial effluent liquid, usually contain the poisonous mercuride of a great deal of.
Traditional method that removes mercury is suitable for processing the waste liquid that mercury content is higher, but removal effect is undesirable for the lower liquid waste disposal of mercury content, and produces a large amount of waste residues, but also may in water body, introduce undesirable ion.
[summary of the invention]
The object of the invention is for protection of the environment, meet the needs of economical and efficient simultaneously, and a kind of method that removes micro-Trace Hg in the aqueous solution is provided.The method comprises the pH value that regulates pending mercurous waste liquid with acid or alkali, adds title complex or the mixture of S-contained substance and copper, zinc or iron, through standing, after precipitation, isolates mercurous precipitation.
The invention discloses a kind of method that removes trace mercury in water solution, it is characterized in that: in the pending aqueous solution that contains mercury, add S-contained substance and contain zincon, contain α-benzoinoxime or contain one or more title complexs that form on the spot or the mixture in ferron, or add S-contained substance with containing zincon, containing α-benzoinoxime or containing title complex or the mixture of one or more formation in ferron, with acid or alkali, regulate the pH value 5-8 of the pending aqueous solution, then standing solution, separates out precipitation; Finally separate mercurous precipitation.
Also can be before aforesaid method operation, first the described pending mercurous aqueous solution is added to one or both in phosphoric acid salt and calcium salt or magnesium salts under violent stirring, then filter or centrifugation goes out mercurous precipitation.Or carry out with aforesaid method simultaneously.
The pending aqueous temperature of described method treating processes is 10-150 ℃, and the pending aqueous solution pH of described method treating processes is 5-8.
Said S-contained substance is Gelucystine, halfcystine, dimercaptosuccinic acid or DMSA, or two or more mixture in them.The consumption of said sulfur-bearing regent is that the mol ratio of sulphur and mercury is 1-50:1.
Said is zinc chloride containing zincon source, zinc phosphate, zinc nitrate, zinc sulfate, zinc carbonate, zinc acetate, zinc sulphide or zinc hydroxide, or two or more mixture in them.The consumption in described zinc source is that the mol ratio of zinc and sulphur is 1-5:1.
Said cupric reagent source is cupric nitrate, copper sulfate, cupric chloride, cupric sulfide, copper hydroxide, copper carbonate, neutralized verdigris or cupric oxalate, or two or more mixture in them.Or their mixture; The consumption in described copper source is that the mol ratio of copper and sulphur is 1-5:1.
Said iron content reagent source is iron trichloride, iron protochloride, iron nitrate, ferric sulfate, ferrous sulfate, iron carbonate, iron protocarbonate, iron acetate, Iron diacetate, Iron sulfuret or ironic hydroxide, or two or more mixture in them.The consumption of described source of iron is that the mol ratio of iron and sulphur is 1-6:1.
Described calcium salt is calcium chloride, nitrocalcite, and calcium phosphate, calcium sulfate, the mixture of one or more in caoxalate or calcium acetate, the mol ratio that described calcium salt consumption is calcium and mercury is 1-50:1.
Described magnesium salts is magnesium chloride, magnesium nitrate, and trimagnesium phosphate, magnesium sulfate, the mixture of one or more in magnesium oxalate or magnesium acetate, the mol ratio that described magnesium salts consumption is magnesium and mercury is 1-50:1.
Described phosphoric acid salt is sodium phosphate, SODIUM PHOSPHATE, MONOBASIC, Sodium phosphate dibasic, ammonium phosphate, primary ammonium phosphate, ammonium hydrogen phosphate, calcium phosphate, or one or more the mixture in trimagnesium phosphate.The mol ratio that described phosphoric acid salt consumption is phosphorus and mercury is 1-50:1.
The present invention has developed a kind of method that removes trace mercury in water solution, can be used for administering trade effluent.This method is taken into account economy and environment protection simultaneously.It can cut the waste, and improves the decreasing ratio of Low Concentration Mercury, reduces costs, and reduces environmental pollution simultaneously.
Feature of the present invention is by cultivation and anatomy to growing plant under mercury environment, utilize co-precipitation principle, by controlling pH, and sulfur-bearing regent and the title complex of zinc, copper or iron or the add-on of mixture, substantially remove the mercury in mercurous waste liquid completely.The raw materials used economy of the present invention is easy to get, and reagent dosage is few, and waste residue generation is few.In the aqueous solution after treatment, mercury content is less than 0.01mg/L, can enter secondary network.Therefore be a kind of environmentally friendly treatment process.This technique can be widely used in the processing of the mercury-containing waste water discharging in the fields such as metallurgy, chemical industry, agricultural chemicals, pigment, fuel, papermaking, process hides.
[embodiment]
Embodiment 1: take 0.5 g Cys, add 50 mL water to dissolve completely to it.Take in addition 1.0g nitrate trihydrate copper or 1.0g cupric sulfate pentahydrate, add 20mL water that it is dissolved completely.Then under violent stirring and room temperature, this copper solutions is dropwise joined in Cys solution.Treat that copper solutions dropwises, continue reaction 1 hour.Afterwards, filtration or centrifugation, the dry mixture that obtains yellowish green Cys and copper.Measuring mercury content is the aqueous solution 50 mL of 5 mg/L, regulates pH to 6-7, adds Cys that 0.1 g obtains and the mixture of copper, exchanges 24 h under room temperature, and interrupted oscillation fully acts on it during this time.Afterwards, standing, sedimentation also removes by filter mercurous throw out.Mercury content through icp analysis filtrate is less than 0.01mg/L.
Embodiment 2: measuring mercury content is the aqueous solution 100 mL of 5 mg/L, the pH 5-6 of regulator solution.Under violent stirring, add 0.1g dimercaptosuccinic acid, 0.1 g tri-water cupric oxalates and 0.2g iron vitriol.Controlling pH value of solution 7-8(can add sodium hydroxide or hydrochloric acid to regulate), under room temperature, continue to stir 2 hours.Afterwards, standing 24 hours, sedimentation was also centrifugally removed mercurous throw out.Mercury content through icp analysis filtrate is less than 0.01mg/L.
Embodiment 3: put into 0.6g dimercaptosuccinic acid and 0.9g zinc nitrate hexahydrate or 0.4g zinc chloride in reactor, react 24 h at 120～140 ℃.Afterwards, standing cooling, filtration or centrifugation are precipitated product.This product is through energy spectrum analysis: this product is through energy spectrum analysis: S:Zn=1:1(mol ratio), shown to obtain title complex or the mixture of a sulfur-bearing regent and zinc.The product that 0.1g is obtained joins in the aqueous solution that 50mL mercury content is 2 mg/L, the pH 6-7 of regulator solution, and to control aqueous temperature be 45 ℃.Continue to stir 2 hours.Afterwards, standing, sedimentation also removes by filter mercurous throw out.Mercury content through icp analysis filtrate is less than 0.01mg/L.
Embodiment 4: measuring mercury content is the aqueous solution 100 mL of 5 mg/L, controlling aqueous temperature is 40 ℃.Under the condition of violent stirring hierarchy of control pH 7-8, (while needing, with sodium hydroxide or hydrochloric acid, regulate), add 0.1g Gelucystine and 0.1g zinc sulphide, continue to stir 2 hours.Afterwards, standing, sedimentation is also centrifugally removed mercurous throw out.Mercury content through icp analysis filtrate is less than 0.01mg/L.
Embodiment 5: measuring mercury content is the aqueous solution 250 mL of 50 mg/L, controlling aqueous temperature is 80 ℃.Under the condition of violent stirring hierarchy of control pH 7-8, (while needing, with sodium hydroxide or hydrochloric acid, regulate), add 0.2 g four water-calcium nitrate, 0.2 g magnesium acetate and 50 mg Sodium phosphate dibasics.Continue to stir 2 hours.Afterwards, standing, sedimentation also removes by filter mercurous throw out.In filtrate, add the Cys that obtains in 0.1g embodiment 1 and the mixture of copper, absorption 24h, interrupted oscillation fully acts on it during this time.Afterwards, standing, sedimentation also removes by filter mercurous throw out.Mercury content through icp analysis filtrate is less than 0.01mg/L.
Embodiment 6: measuring mercury content is the aqueous solution 250 mL of 50 mg/L, controlling aqueous temperature is 30 ℃.Under the condition of violent stirring hierarchy of control pH 6-7, add 0.1 g calcium phosphate and 0.1g trimagnesium phosphate.Continue to stir 2 hours.Afterwards, standing, sedimentation also removes by filter mercurous throw out.In filtrate, add the Cys that obtains in 0.1 gram of embodiment 3 and the mixture of zinc, absorption 24h, interrupted oscillation fully acts on it during this time.Afterwards, standing, sedimentation also removes by filter mercurous throw out.Mercury content through icp analysis filtrate is less than 0.01mg/L.
Embodiment 7: measuring mercury content is the aqueous solution 50 mL of 5 mg/L, controlling aqueous temperature is 20 ℃.Under the condition of violent stirring hierarchy of control pH 5-6, (while needing, with sodium hydroxide or hydrochloric acid, regulate), add 0.1g Gelucystine and 0.1g ironic hydroxide, continue to stir 2 hours.Afterwards, standing 24 hours, sedimentation was also centrifugally removed mercurous throw out.Mercury content through icp analysis filtrate is less than 0.01mg/L.
Embodiment 8: measuring mercury content is the aqueous solution 100 mL of 50 mg/L, controlling aqueous temperature is 20 ℃.Under the condition of violent stirring hierarchy of control pH 5-6, (while needing, with sodium hydroxide or hydrochloric acid, regulate), add 0.1 g caoxalate, 50 m g Cys and 0.1 g copper carbonate, continue to stir 2 hours.Afterwards, standing 24 hours, sedimentation was also centrifugally removed mercurous throw out.Mercury content through icp analysis filtrate is less than 0.01mg/L.
Claims (9)
1. one kind removes the method for trace mercury in water solution, it is characterized in that: in the pending aqueous solution that contains mercury, add S-contained substance with containing zincon, containing α-benzoinoxime or containing title complex or the mixture of one or more formation in ferron, with acid or alkali, regulate the pH value 5-8 of the pending aqueous solution, then standing solution, separates out precipitation; Finally separate mercurous precipitation; Before the operation of described method, first the described pending mercurous aqueous solution is added to one or both in phosphoric acid salt and calcium salt or magnesium salts under violent stirring, then filter or centrifugation goes out mercurous precipitation; In present method, described S-contained substance source is Gelucystine, halfcystine, dimercaptosuccinic acid or DMSA, or two or more mixture in them; Described is zinc chloride containing zincon source, zinc nitrate, zinc sulfate, zinc carbonate, zinc phosphate, zinc acetate, zinc oxalate, zinc sulphide or zinc hydroxide, or two or more mixture in them; Described cupric reagent source is cupric nitrate, copper sulfate, cupric chloride, cupric sulfide, copper hydroxide, copper carbonate, neutralized verdigris or cupric oxalate, or two or more mixture in them; Described iron content reagent source is iron trichloride, iron protochloride, iron nitrate, ferric sulfate, ferrous sulfate, iron carbonate, iron protocarbonate, iron acetate, Iron diacetate, ironic oxalate, Ferrox, Iron sulfuret or ironic hydroxide, or two or more mixture in them; Described calcium salt is calcium chloride, nitrocalcite, calcium phosphate, calcium sulfate, caoxalate or calcium acetate, or two or more mixture in them; Described magnesium salts is magnesium chloride, magnesium nitrate, trimagnesium phosphate, magnesium sulfate, magnesium oxalate or magnesium acetate, or two or more mixture in them; Described phosphoric acid salt is sodium phosphate, SODIUM PHOSPHATE, MONOBASIC, Sodium phosphate dibasic, ammonium phosphate, primary ammonium phosphate, ammonium hydrogen phosphate, calcium phosphate or trimagnesium phosphate, or two or more mixture in them.
2. the pending aqueous temperature that in accordance with the method for claim 1, it is characterized in that described method treating processes is 10-150 ℃.
3. according to the method described in claim 1 or 2, the consumption that it is characterized in that described S-contained substance is that the mol ratio of sulphur and mercury is 1-50:1.
4. according to the method described in claim 1 or 2, it is characterized in that the mol ratio that the described consumption containing zincon is zinc and sulphur is 1-5:1.
5. according to the method described in claim 1 or 2, it is characterized in that the mol ratio that the described consumption containing α-benzoinoxime is copper and sulphur is 1-5:1.
6. according to the method described in claim 1 or 2, it is characterized in that the mol ratio that the described consumption containing ferron is iron and sulphur is 1-6:1.
7. according to the method described in claim 1 or 2, it is characterized in that the mol ratio that described calcium salt consumption is calcium and mercury is 1-50:1.
8. according to the method described in claim 1 or 2, it is characterized in that the mol ratio that described magnesium salts consumption is magnesium and mercury is 1-50:1.
9. according to the method described in claim 1 or 2, it is characterized in that the mol ratio that described phosphoric acid salt consumption is phosphorus and mercury is 1-50:1.
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| CN110902803A (en) * | 2019-12-10 | 2020-03-24 | 佛山科学技术学院 | Oxidant for sewage treatment and preparation method thereof |
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| CN104190362B (en) * | 2014-08-18 | 2016-05-18 | 天津理工大学 | A kind of preparation method of the composite that contains cysteine and ferrous compound |
| CN104478060B (en) * | 2014-11-27 | 2016-06-15 | 长沙矿冶研究院有限责任公司 | A kind of process contains medicament and the technique of thallium and other heavy metal wastewater therebies |
| CN108404849A (en) * | 2018-04-18 | 2018-08-17 | 常州大学 | A kind of natural gas mercury-removing adsorbent and preparation method thereof |
| CN110801803B (en) * | 2019-11-28 | 2022-04-26 | 江西理工大学 | Method for preparing mercury removal adsorbent by utilizing wet zinc smelting oxygen pressure acid leaching residue |
| CN111545174A (en) * | 2020-04-15 | 2020-08-18 | 济南大学 | Preparation method of modified fiber balls for adsorbing and separating trifluoro-benzene pyrimidine |
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| CN1287887A (en) * | 1999-08-27 | 2001-03-21 | 拜尔公司 | Prepn. art and application of monodisperse ion exchange agent contg. chelate functional group |
| CN1589240A (en) * | 2000-10-03 | 2005-03-02 | 约瑟夫G·哈林顿 | Metal in situ immobilization within density variant bodies of water |
| CN1478731A (en) * | 2003-06-30 | 2004-03-03 | 雁北师范学院 | Preparation method of triazene polymer chelant and its application |
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Effective date of registration: 20151225 Address after: 100124 Beijing city Chaoyang District Dajiaoting Street Huateng international No. 2 Building 9 layer Patentee after: Beijing Nengtai Hi-Tech Environmental Protection Technology Co., Ltd. Address before: 300384 Tianjin city Xiqing District West Binshui Road No. 391 Patentee before: Tianjin University of Technology |
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Address after: 100124 Beijing city Chaoyang District Dajiaoting Street Huateng international No. 2 Building 9 layer Patentee after: Nengtai Gaoke Environment Protection Co., Ltd., Beijing Address before: 100124 Beijing city Chaoyang District Dajiaoting Street Huateng international No. 2 Building 9 layer Patentee before: Beijing Nengtai Hi-Tech Environmental Protection Technology Co., Ltd. |