CN102557222B - Method for removing trace arsenic from aqueous solution - Google Patents
Method for removing trace arsenic from aqueous solution Download PDFInfo
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- CN102557222B CN102557222B CN 201210033300 CN201210033300A CN102557222B CN 102557222 B CN102557222 B CN 102557222B CN 201210033300 CN201210033300 CN 201210033300 CN 201210033300 A CN201210033300 A CN 201210033300A CN 102557222 B CN102557222 B CN 102557222B
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Abstract
The invention discloses a method for removing trace arsenic from an aqueous solution. The method comprises the steps of: adjusting the pH value of an arsenic-containing aqueous solution with an acid or a base by utilizing the adsorption and coprecipitation principle through culturing and analyzing the plants growing in arsenic environment, adding a copper-containing reagent, an iron-containing reagent or a zinc-containing reagent or simultaneously or respectively adding a mixture of two or more of the copper-containing reagent, the iron-containing reagent and the zinc-containing reagent in the presence of calcium salts, magnesium salts and carbonate, and precipitating, wherein the arsenic content in the water, from which arsenic containing slag is separated, is detected to be less than 0.01mg/L. The method has the characteristics that the trace arsenic element in the aqueous solution can be removed by controlling the addition amounts of the copper-containing reagent, the iron-containing reagent and the zinc-containing reagent as well as the pH value of the solution; the use raw materials are economical and easily available, and harmful elements are not introduced to the system, thus the method is an environment-friendly and economical treatment process; and the process can be widely applied to treatment of arsenic-containing wastewater discharged in the fields of metallurgy, chemical industry, pesticide, pigment, fuel, papermaking, leather manufacture and the like.
Description
[technical field]
The present invention relates to the field of waste water treatment of environmental technology, particularly a kind of method that removes trace arsenic from aqueous solution.
[background technology]
Along with increasing sharply of trade waste, the heavy metal in water arsenic contamination that causes is more and more serious.Usually find arsenic in trade effluent, maximum arsenic contamination source is from industries such as metallurgy, chemical industry, agricultural chemicals, pigment, fuel, papermaking, process hides.Usually contain the poisonous arsenide of a great deal of in these industrial effluent liquid.
Traditional method that removes arsenic is suitable for processing the higher waste liquid of arsenic content, but removal effect is undesirable for the lower liquid waste disposal of arsenic content, and produces a large amount of waste residues, but also may introduce undesirable ion in water body.
[summary of the invention]
The objective of the invention is for protection of the environment, satisfy simultaneously the needs of economical and efficient, and a kind of method that removes micro content arsenic in the aqueous solution is provided.The method comprises with acid or alkali regulates the pending pH value that contains arsenic waste solution, and under the existence of calcium salt, magnesium salts and carbonate, add at the same time or separately and contain α-benzoinoxime, contain ferron and contain zincon, or their both above mixtures.Through standing, after precipitation, isolate and contain the arsenic precipitation.
The invention discloses a kind of method that removes trace arsenic from aqueous solution, it is characterized in that: intersect in containing the pending aqueous solution of pentavalent arsenic or carry out simultaneously following interpolation reagent and regulate the pH Value Operations: add under the existence of calcium salt, magnesium salts and carbonate and contain α-benzoinoxime, contain ferron and contain zincon, or simultaneously or both above mixtures that successively add them.PH value with acid or the pending aqueous solution of alkali adjusting; Then standing solution, separate out precipitation; Separate at last and contain the arsenic precipitation.Described adjusting pH value is 4-7.
The invention also discloses the method that another kind removes micro amount of arsenic in aqueous solution, it is characterized in that also can first the trivalent arsenic that contains in the pending aqueous solution of arsenic being oxidized to pentavalent arsenic, oxygenant is hydrogen peroxide, Manganse Dioxide or Fenton reagent; Intersect in containing the pending aqueous solution of pentavalent arsenic again or carry out simultaneously following interpolation reagent and regulate the pH Value Operations: add under the existence of calcium salt, magnesium salts and carbonate and contain α-benzoinoxime, contain ferron and contain zincon, or simultaneously or both above mixtures that successively add them.PH value with acid or the pending aqueous solution of alkali adjusting; Then standing solution, separate out precipitation; Separate at last and contain the arsenic precipitation.Described adjusting pH value is 4-7.
Cupric reagent source preferably sulfuric acid copper of the present invention, cupric nitrate, copper hydroxide, copper carbonate, neutralized verdigris, cupric oxalate, cupric chloride, cupric sulfide, the resin-carried type copper of halfcystine copper or weak-type, or their mixture.
The preferred iron trichloride of iron content reagent source of the present invention, iron protochloride, iron nitrate, ferric sulfate, ferrous sulfate, iron carbonate, iron protocarbonate, iron acetate, Iron diacetate, ironic oxalate, Ferrox, Iron sulfuret, iron sulphide, the resin-carried sections of ironic hydroxide or weak-type, or their mixture.
The preferred zinc chloride in zincon source, zinc phosphate, zinc nitrate, zinc sulfate, zinc carbonate, zinc acetate, zinc oxalate, zinc sulphide, the resin-carried type zinc of zinc hydroxide or weak-type, or their mixture of containing of the present invention.
The above contains α-benzoinoxime, contain ferron and contain molar weight sum that the zincon consumption is copper, iron and zinc and the mol ratio of arsenic is 1-30:1.
Calcium salt preferably calcium chloride of the present invention, nitrocalcite, the mixture of one or more in calcium sulfate or calcium acetate.The preferred magnesium chloride of described magnesium salts, magnesium nitrate, the mixture of one or more in sal epsom or magnesium acetate.Described calcium salt and magnesium salts consumption are that the molar weight sum of calcium and magnesium and the mol ratio of arsenic are 1-30:1.
The preferred sodium carbonate of carbonate of the present invention, sodium bicarbonate, salt of wormwood, the mixture of one or more in saleratus or calcium carbonate; The mol ratio that described carbonate consumption is carbon and arsenic is 1-30:1.
The method that removes trace arsenic from aqueous solution of the present invention's exploitation 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 arsenic, reduces costs, simultaneously environmental contamination reduction.
Characteristics of the present invention are by cultivation and anatomy to growing plant under arsenic environment, utilize absorption and co-precipitation principle, by controlling pH, and calcium salt, magnesium salts, carbonate, contain α-benzoinoxime, contain ferron or contain the add-on of zincon, basically remove the arsenic that contains in arsenic waste solution fully.The raw materials used economy of the present invention is easy to get, and reagent dosage is few, and the waste residue generation is few.In the aqueous solution after processing, arsenic content 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 arsenic-containing waste water that discharges in the fields such as metallurgy, chemical industry, agricultural chemicals, pigment, fuel, papermaking, process hides.
[embodiment]
Embodiment 1: measuring arsenic (pentavalent) content is the aqueous solution 1L of 16.9mg/L, adds 2 mg sodium carbonate, 0.5 g Calcium Chloride Powder Anhydrous, and 5 mg magnesium nitrate hexahydrates, and controlling aqueous temperature is 25 ℃.(regulate with sodium hydroxide or hydrochloric acid when needing) under the condition of violent stirring and hierarchy of control pH4-5, add 1.0 gram ferric chloride (FeCl36H2O)s.After dropwising, continue to stir 1 hour.Afterwards, be cooled to room temperature, standing, sedimentation also removes by filter and contains the arsenic throw out.Through ICP(inductively coupled plasma emmission spectrum, lower same) analyze the arsenic content of filtrate less than 0.01mg/L.
Embodiment 2: measuring arsenic (pentavalent) content is the aqueous solution 1L of 16.9mg/L, adds 0.12 g sodium bicarbonate, 50 mg four water-calcium nitrates, and 0.6 g magnesium chloride hexahydrate, and controlling aqueous temperature is 15 ℃.(regulate with sodium hydroxide or hydrochloric acid when needing) under the condition of violent stirring and hierarchy of control pH5-6, add 20 mg cupric nitrates.After dropwising, continue to stir 1 hour.Afterwards, be cooled to room temperature, standing, sedimentation and centrifugal removing contain the arsenic throw out.Through the arsenic content of icp analysis filtrate less than 0.01mg/L.
Embodiment 3: measuring arsenic content is the aqueous solution 1L of 16.9mg/L, adds 0.1 g magnesium chloride, adds 0.5 g sodium bicarbonate, the pH4-5 of regulator solution.Under violent stirring, add 50 mg cupric sulfate pentahydrates and 150 mg iron vitriols, continue to stir 1 hour.Afterwards, standing, sedimentation and centrifugal removing contain the arsenic throw out.Through the arsenic content of icp analysis filtrate less than 0.01mg/L.
Embodiment 4: measuring arsenic content is the aqueous solution 1L of 16mg/L, adds 30 mg salt of wormwood and 0.1g zinc sulphide, with its with hcl acidifying to pH～6, under 30 ℃ and violent stirring, add 0.2 g Iron diacetate, and to control aqueous temperature be 45 ℃.Continue to stir .2 hour.Afterwards, standing, sedimentation is also centrifugal or remove by filter and contain the arsenic throw out.Through the arsenic content of icp analysis filtrate less than 0.01mg/L.
Embodiment 5: measuring arsenic content is the aqueous solution 1L of 16mg/L, adds the 0.5g magnesium acetate, with its pH6-7, under violent stirring, adds 50 mg copper carbonates, 30 mg zinc carbonates, and 1 g nine water iron nitrates, and controlling aqueous temperature is 10 ℃.Continue to stir 2 hours.Afterwards, standing, sedimentation is also centrifugal or remove by filter and contain the arsenic throw out.Through the arsenic content of icp analysis filtrate less than 0.01mg/L.
Embodiment 6: measuring trivalent arsenic content is the aqueous solution 1L of 16mg/L, add 500mL 30% hydrogen peroxide solution, stir after 2 hours, add sodium bicarbonate, 0.1 g four water-calcium nitrate and 0.1g magnesium nitrate hexahydrate are with its pH4.5～6, under violent stirring, add 0.5 g venus crystals, 0.1g zinc chloride and 0.5 g ferric sulfate, and the control aqueous temperature is 80 ℃.Continue to stir 2 hours.Afterwards, standing, sedimentation is also centrifugal or remove by filter and contain the arsenic throw out.Through the arsenic content of icp analysis filtrate less than 0.01mg/L.
Claims (3)
1. method that removes trace arsenic from aqueous solution, it is characterized in that: intersect in containing the pending aqueous solution of pentavalent arsenic or carry out simultaneously following interpolation reagent and regulate the pH Value Operations: add under the existence of calcium salt, magnesium salts and carbonate and contain α-benzoinoxime, contain ferron or contain zincon, or simultaneously or both above mixtures that successively add them; Regulate the pH value of the pending aqueous solution to 4-7 with acid or alkali; Then standing solution, separate out precipitation; Separate at last and contain the arsenic precipitation; Wherein:
Described cupric reagent source is copper sulfate, cupric nitrate, copper hydroxide, copper carbonate, neutralized verdigris, cupric oxalate, cupric chloride, cupric sulfide, or halfcystine copper, or their mixture;
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 their mixture;
The described zincon source of containing is zinc chloride, zinc phosphate, zinc nitrate, zinc sulfate, zinc carbonate, zinc acetate, zinc oxalate, zinc sulphide, or zinc hydroxide, or their mixture;
Describedly contain α-benzoinoxime, contain ferron and contain molar weight sum that the zincon consumption is copper, iron and zinc and the mol ratio of arsenic is 1-30:1;
Described calcium salt is calcium chloride, nitrocalcite, and the mixture of one or more in calcium sulfate or calcium acetate, described magnesium salts is magnesium chloride, magnesium nitrate, the mixture of one or more in sal epsom or magnesium acetate; Described calcium salt and magnesium salts consumption are that the molar weight sum of calcium and magnesium and the mol ratio of arsenic are 1-30:1;
Described carbonate is sodium carbonate, sodium bicarbonate, salt of wormwood, or one or more the mixture in saleratus; The mol ratio that described carbonate consumption is carbon and arsenic is 1-30:1.
2. a method that removes trace arsenic from aqueous solution, is characterized in that the trivalent arsenic that will contain in the pending aqueous solution of arsenic passes through hydrogen peroxide, and Manganse Dioxide or Fenton reagent oxidation are pentavalent arsenic; Intersect in containing the pending aqueous solution of pentavalent arsenic again or carry out simultaneously following interpolation reagent and regulate the pH Value Operations: add under the existence of calcium salt, magnesium salts and carbonate and contain α-benzoinoxime, contain ferron or contain zincon, or simultaneously or both above mixtures that successively add them; Regulate the pH value of the pending aqueous solution to 4-7 with acid or alkali; Then standing solution, separate out precipitation; Separate at last and contain the arsenic precipitation; Wherein:
Described cupric reagent source is copper sulfate, cupric nitrate, copper hydroxide, copper carbonate, neutralized verdigris, cupric oxalate, cupric chloride, cupric sulfide, or halfcystine copper, or their mixture;
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 their mixture;
The described zincon source of containing is zinc chloride, zinc phosphate, zinc nitrate, zinc sulfate, zinc carbonate, zinc acetate, zinc oxalate, zinc sulphide, or zinc hydroxide, or their mixture;
Describedly contain α-benzoinoxime, contain ferron and contain molar weight sum that the zincon consumption is copper, iron and zinc and the mol ratio of arsenic is 1-30:1;
Described calcium salt is calcium chloride, nitrocalcite, and the mixture of one or more in calcium sulfate or calcium acetate, described magnesium salts is magnesium chloride, magnesium nitrate, the mixture of one or more in sal epsom or magnesium acetate; Described calcium salt and magnesium salts consumption are that the molar weight sum of calcium and magnesium and the mol ratio of arsenic are 1-30:1;
Described carbonate is sodium carbonate, sodium bicarbonate, salt of wormwood, or one or more the mixture in saleratus; The mol ratio that described carbonate consumption is carbon and arsenic is 1-30:1.
3. according to the described method of claim 1 or 2, the pending aqueous temperature that it is characterized in that described method treating processes is 10～80 ℃.
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| CN104085903B (en) * | 2014-06-27 | 2015-12-09 | 锡矿山闪星锑业有限责任公司 | A kind of from the method containing separating-purifying sodium hydroxide arsenic sodium hydroxide solution |
| CN106390355B (en) * | 2016-08-31 | 2019-07-12 | 航天凯天环保科技股份有限公司 | A kind of preparation method and application of modification secondary zinc oxide slag composite particles that consolidating arsenic for arsenic alkaline slag |
| CN107840480A (en) * | 2016-09-20 | 2018-03-27 | 张家港格林台科环保设备有限公司 | A kind of method for waste acid of being given up using industrial ferrous contained useless mud processing containing arsenic |
| CN108217895B (en) * | 2018-03-02 | 2022-03-01 | 武汉理工大学 | Method for efficiently treating arsenic-containing wastewater |
| CN110075896B (en) * | 2019-04-09 | 2021-12-07 | 重庆大学 | FeS2/g-C3N4Preparation method and application of heterojunction material |
| CN110592806B (en) * | 2019-07-29 | 2021-09-07 | 同济大学 | Double-nanometer functional core-loaded arsenic-removing nanofiber membrane and preparation method thereof |
| CN110627179B (en) * | 2019-11-05 | 2022-02-22 | 深圳市长隆科技有限公司 | Method for treating arsenic-containing wastewater by using recyclable composite salt precipitator |
| CN115140768B (en) * | 2022-02-11 | 2023-03-24 | 江西省裕仁信科技发展有限公司 | Method for extracting arsenic by copper smelting sulfuric acid purification waste acid leaching |
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| CN1329320C (en) * | 2004-08-11 | 2007-08-01 | 巨化集团公司 | Processing method of waste water containing fluorine arsenic and lead |
| US20080011686A1 (en) * | 2006-07-13 | 2008-01-17 | Rajiv Manohar Banavalie | Method and composition for removing contaminants from an aqueous solution |
| CN101492181B (en) * | 2009-02-20 | 2011-07-27 | 中南大学 | Method for removing tungsten, vanadium, phosphor and arsenic from molybdate solution by deposition |
| CN102188948B (en) * | 2011-04-12 | 2013-01-16 | 哈尔滨工业大学 | Method for removing arsenic (As) from water by using MnO2/Fe3O4 composite adsorbent |
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