CN103145263B - Method for removing trace manganese in aqueous solution - Google Patents
Method for removing trace manganese in aqueous solution Download PDFInfo
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- CN103145263B CN103145263B CN201310060173.8A CN201310060173A CN103145263B CN 103145263 B CN103145263 B CN 103145263B CN 201310060173 A CN201310060173 A CN 201310060173A CN 103145263 B CN103145263 B CN 103145263B
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Abstract
The invention discloses a method for removing trace manganese in aqueous solution. By cultivating and analyzing a plant which grows in a manganese environment, acid or alkali is used for adjusting the pH value of a manganese-contained aqueous solution, calcium reagent, phosphate and carbonate are respectively added into the manganese-contained aqueous solution, then the manganese-contained aqueous solution stands and deposits to separate water containing manganese residues, and the content of the manganese in the water is detected to be less than 0.01mg/L. The method is characterized in that by controlling the addition quantity of the calcium reagent, the phosphate and the carbonate as well as the pH value of the solution, trace manganese in the aqueous solution can be removed; and moreover, the water treatment time is short, raw materials used in the method are economical and easily gotten, and no harmful element is added to the system, so that the method is an environment-friendly and economical treatment process. The process can be widely used for treating manganese-contained waste water discharged in the fields such as the metal machining industry, the electroplating industry, the machine building industry, the catalyzing industry, the tannery industry and the textile industry.
Description
[technical field]
The present invention relates to the field of waste water treatment in environmental technology, particularly a kind of method that removes trace manganese in industrial wastewater.
[background technology]
Along with increasing sharply of trade waste, the heavy metal in water pollution by manganese causing is more and more serious.In trade effluent, usually find manganese, maximum pollution by manganese is from the exploitation of manganese ore and smelting, metal processing, machinofacture, Iron and Steel Production, battery, dyestuff, catalyzer etc.In these industrial effluent liquid, usually contain the poisonous manganese compound of a great deal of.
Traditional method that removes manganese is suitable for processing the waste liquid that manganese content is higher, but for liquid waste disposal that manganese content is lower, removal effect is undesirable, when processing, agents useful for same consumption is large, produces thus 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, to meet the needs of economical and efficient simultaneously, and a kind of method that removes micro-Trace Amount Manganese in the aqueous solution is provided.The method comprises by acid or the pending pH value containing manganese waste liquid of alkali adjusting, adds containing calcon, phosphoric acid salt, carbonate, through leaving standstill, after precipitation, isolates containing manganese and precipitates.
The invention discloses a kind of method that removes trace manganese in the aqueous solution, it is characterized in that: in the pending aqueous solution that contains bivalent manganese, intersect or add as follows reagent simultaneously and regulate pH Value Operations: adding containing calcon, add phosphoric acid salt, add carbonate, regulate the pH value of the pending aqueous solution with acid or alkali; Then leave standstill solution, separate out precipitation, finally separate containing manganese precipitation; Described adjusting pH value is 6-8, and calcic reagent dosage is that the mol ratio of calcium and manganese is 0.1-10:1, and phosphoric acid salt consumption is that the mol ratio of phosphorus and manganese is 0.1-10:1, and carbonate consumption is that the mol ratio of carbon and manganese is 0.1-10:1.
The method that removes trace manganese in the aqueous solution of the present invention, can be used for administering trade effluent, takes into account economy and environment protection simultaneously.It can cut the waste, and improves the decreasing ratio of lower concentration manganese, reduces costs, and reduces environmental pollution simultaneously.Be characterized in by cultivation and anatomy to growing plant under manganese environment, by controlling pH, and add containing calcon, phosphoric acid salt, carbonate etc., substantially remove the manganese containing manganese waste liquid completely.The raw materials used economy of the present invention is easy to get, and in system, does not add any harmful element, and the wastewater treatment time is short, reagent dosage water, and waste residue generation is few, and in the aqueous solution after treatment, manganese 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 Mn-bearing waste water discharging in the fields such as metal-processing industry, Electroplating Operations, machinery manufacturing industry, curriery and textile industry.
[embodiment]
The method that removes aqueous solution trace manganese of the present invention, in the pending aqueous solution that contains bivalent manganese, to add as follows reagent first, afterwards or simultaneously and regulate pH Value Operations: add containing calcon, add phosphoric acid salt, add carbonate, regulate the pH value of the pending aqueous solution with acid or alkali; Then leave standstill solution, separate out precipitation, finally separate containing manganese precipitation; Described adjusting pH value is 6-8, and calcic reagent dosage is that the mol ratio of calcium and manganese is 0.1-10:1, and phosphoric acid salt consumption is that the mol ratio of phosphorus and manganese is 0.1-10:1, and carbonate consumption is that the mol ratio of carbon and manganese is 0.1-10:1.
In described method treating processes, the temperature of the pending aqueous solution is 0～80 ℃.The better temperature of described method treating processes is 10～45 ℃.
Described is calcium chloride containing calcon, nitrocalcite, the mixture of one or more in calcium sulfate or calcium acetate.
Described phosphoric acid salt is sodium phosphate, SODIUM PHOSPHATE, MONOBASIC, Sodium phosphate dibasic, ammonium phosphate, the mixture of one or more in primary ammonium phosphate or ammonium hydrogen phosphate.
Described carbonate is sodium carbonate, sodium bicarbonate, salt of wormwood, saleratus, volatile salt, the mixture of one or more in bicarbonate of ammonia or calcium carbonate.
Embodiment 1: measuring manganese content is the aqueous solution 1L of 13mg/L, adds 30mg calcium chloride, and 0.6g Sodium phosphate dibasic, controlling aqueous temperature is 20 ℃.Under the condition of violent stirring hierarchy of control pH7-7.2, (while needs, regulate with sodium hydroxide and hydrochloric acid), drip 50mL containing 20mg sodium bicarbonate aqueous solution.After dropwising, continue to stir 1 hour.Afterwards, be cooled to room temperature, leave standstill, sedimentation also removes by filter containing manganese throw out.Through ICP(inductively coupled plasma emmission spectrum, lower with) analyze the manganese content of filtrate and be less than 0.01mg/L.
Embodiment 2: measuring manganese content is the aqueous solution 1L of 13mg/L, adds 4mg calcium sulfate, and 60mg Sodium phosphate dibasic, controlling aqueous temperature is 30 ℃.Under the condition of violent stirring hierarchy of control pH7-7.2, (while needs, regulate with sodium hydroxide and hydrochloric acid), drip 30mL containing 20mg ammonium bicarbonate aqueous solution.After dropwising, continue to stir 1 hour.Afterwards, be cooled to room temperature, leave standstill, sedimentation also removes by filter containing manganese throw out.Through ICP(inductively coupled plasma emmission spectrum, lower with) analyze the manganese content of filtrate and be less than 0.01mg/L.
Embodiment 3: measuring manganese content is the aqueous solution 1L of 13mg/L, under 40 ℃ and violent stirring, adds 20mg ammonium hydrogen phosphate and 0.2g nitrocalcite, then will be under the condition of control system pH6-6.5, drip the aqueous solution of 20mL containing 0.3g volatile salt.After dropwising, continue to stir 1 hour.Afterwards, be cooled to room temperature, leave standstill, sedimentation centrifugal removing containing manganese throw out.Manganese content through icp analysis filtrate is less than 0.01mg/L.
Embodiment 4: measuring manganese content is the aqueous solution 1L of 13mg/L, by its with hcl acidifying to pH～6, under violent stirring, add 0.4g calcium acetate, 20mg sodium bicarbonate and 3mg sodium phosphate, then pH value of solution is adjusted to 7.5～8, and to control aqueous temperature be 45 ℃.Continue to stir 2 hours.Afterwards, leave standstill, sedimentation also removes by filter containing manganese throw out.Manganese content through icp analysis filtrate is less than 0.01mg/L.
Embodiment 5: measuring manganese content is the aqueous solution 1L of 13mg/L, under violent stirring, adds 30mg ammonium phosphate, 40mg calcium sulfate and 10mg salt of wormwood, then pH value of solution is adjusted to 7～7.5, and to control aqueous temperature be 10 ℃.Continue to stir 2 hours.Afterwards, leave standstill, sedimentation also filters out containing manganese throw out.Manganese content through icp analysis filtrate is less than 0.01mg/L.
Embodiment 6: measuring manganese content is the aqueous solution 1L of 13mg/L, pH～7 of the adjusting aqueous solution.Under 30 ℃ and violent stirring, add 30mg ammonium hydrogen phosphate and 40mg calcium carbonate.Controlling solution～7(can add sodium hydroxide or hydrochloric acid to regulate), continue to stir 1 hour.Afterwards, leave standstill sedimentation centrifugal removing containing manganese throw out.Manganese content through icp analysis filtrate is less than 0.01mg/L.
Embodiment 7: measuring manganese content is the aqueous solution 1L of 13mg/L, adds 0.6g four water-calcium nitrate and 80mg primary ammonium phosphate, then uses pH～7 of sodium hydroxide solution regulator solution, and to control aqueous temperature be 10 ℃.Under the condition of violent stirring control system pH7.2-7.5, drip the aqueous solution of 6mL containing 3mg sodium carbonate.After dropwising, continue to stir 1 hour.Afterwards, be cooled to room temperature, leave standstill, sedimentation centrifugal removing containing manganese throw out.Manganese content through icp analysis filtrate is less than 0.01mg/L.
Claims (3)
1. one kind removes the method for trace manganese in the aqueous solution, it is characterized in that: in the pending aqueous solution that contains bivalent manganese, intersect or add as follows reagent simultaneously and regulate pH Value Operations: adding containing calcon, add phosphoric acid salt, add carbonate, regulate the pH value of the pending aqueous solution with acid or alkali; Then leave standstill solution, separate out precipitation, finally separate containing manganese precipitation; Described is calcium chloride containing calcon, nitrocalcite, the mixture of one or more in calcium sulfate or calcium acetate; Described phosphoric acid salt is sodium phosphate, SODIUM PHOSPHATE, MONOBASIC, Sodium phosphate dibasic, ammonium phosphate, the mixture of one or more in primary ammonium phosphate or ammonium hydrogen phosphate; Described carbonate is sodium carbonate, sodium bicarbonate, salt of wormwood, saleratus, volatile salt, the mixture of one or more in bicarbonate of ammonia or calcium carbonate; Described adjusting pH value is 6-8; Calcic reagent dosage is that the mol ratio of calcium and manganese is 0.1-10:1; Phosphoric acid salt consumption is that the mol ratio of phosphorus and manganese is 0.1-10:1; Carbonate consumption is that the mol ratio of carbon and manganese is 0.1-10:1.
2. the pending aqueous temperature that in accordance with the method for claim 1, it is characterized in that described method treating processes is 0～80 ℃.
3. according to the method described in claim 1 or 2, the pending aqueous temperature that it is characterized in that described method treating processes is 10～45 ℃.
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104690080B (en) * | 2015-03-28 | 2016-08-24 | 重庆大学 | The directly method of harmless treatment electrolytic manganese residues in filtrating-pressing plate frame |
| CN114457241B (en) * | 2022-01-05 | 2024-01-30 | 重庆大学 | Method for reducing soluble manganese and water content of electrolytic manganese slag |
| CN114457240A (en) * | 2022-01-05 | 2022-05-10 | 重庆大学 | Method for harmlessly treating electrolytic manganese slag leachate |
| CN115583740A (en) * | 2022-09-09 | 2023-01-10 | 昆山三一环保科技有限公司 | Manganese removal method and system for iron phosphate wastewater |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87106661A (en) * | 1987-09-28 | 1988-04-06 | 湖北工业建筑设计院 | A kind of underground water deferrization and demanganization equipment |
| JP3659383B2 (en) * | 1998-03-30 | 2005-06-15 | 株式会社荏原製作所 | Method and apparatus for treating manganese-containing water |
| CN102139973A (en) * | 2011-02-18 | 2011-08-03 | 南京大学 | Method for treating micro-polluted and eutrophicated water body by utilizing coprecipitation method |
| CN102153187A (en) * | 2011-05-11 | 2011-08-17 | 天津理工大学 | Method for removing trace chromium in aqueous solution |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87106661A (en) * | 1987-09-28 | 1988-04-06 | 湖北工业建筑设计院 | A kind of underground water deferrization and demanganization equipment |
| JP3659383B2 (en) * | 1998-03-30 | 2005-06-15 | 株式会社荏原製作所 | Method and apparatus for treating manganese-containing water |
| CN102139973A (en) * | 2011-02-18 | 2011-08-03 | 南京大学 | Method for treating micro-polluted and eutrophicated water body by utilizing coprecipitation method |
| CN102153187A (en) * | 2011-05-11 | 2011-08-17 | 天津理工大学 | Method for removing trace chromium in aqueous solution |
Non-Patent Citations (2)
| Title |
|---|
| 仿骨盐吸附剂的合成及其在脱除重金属方面的应用;田惠芸等;《天津理工大学学报》;20110430;第27卷(第2期);第76-81页 * |
| 田惠芸等.仿骨盐吸附剂的合成及其在脱除重金属方面的应用.《天津理工大学学报》.2011,第27卷(第2期), |
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