CN103964588A - Method for separating calcium ions and magnesium ions from ammonium chloride wastewater - Google Patents
Method for separating calcium ions and magnesium ions from ammonium chloride wastewater Download PDFInfo
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- CN103964588A CN103964588A CN201410180131.2A CN201410180131A CN103964588A CN 103964588 A CN103964588 A CN 103964588A CN 201410180131 A CN201410180131 A CN 201410180131A CN 103964588 A CN103964588 A CN 103964588A
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- ammonium chloride
- calcium
- phosphate
- magnesium
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Abstract
The invention relates to a method for separating calcium ions and magnesium ions from ammonium chloride wastewater, and belongs to the wastewater treatment technical field in the rare earth hydrometallurgy field. The method adopts a chemical precipitation method and comprises the following steps: adding a soluble phosphate into the wastewater to introduce phosphate groups and further generate crystal precipitates of calcium phosphate and magnesium ammonium phosphate; carrying out solid-liquid separation to remove the calcium ions and the magnesium ions from the ammonium chloride wastewater. The method is suitable for treating ammonium chloride wastewater of various ionic concentrations; as the solubility product constants of calcium phosphate and magnesium ammonium phosphate are very small, the phosphate is used for generating precipitation for removing the calcium ions and the magnesium ions, and the processing parameters are controlled strictly, the separation of the calcium ions and the magnesium ions in the ammonium chloride wastewater can be realized, and the removal rates of the calcium ions and the magnesium ions are high; as the generated precipitates are crystal, the solid-liquid separation is easy; moreover, the method is simple in technology, easy to operate and control, and low in chemical agent consumption and wastewater treatment cost.
Description
Technical field
The present invention relates to a kind of method of calcium, magnesium ion in separating ammonium chloride waste water, belong to the wastewater processing technology part in rare-earth wet method field of metallurgy.
Background technology
The waste water producing in the process of producing single rare earth oxide compound by rare earth ore concentrate separating-purifying mainly contains two classes: the one, and the saponification waste-water producing in Rare Earths Countercurrent Extraction Process; The 2nd, the heavy waste water of carbon producing in the heavy transformation process of carbon.Some Rare Earth Separation producer, for realizing trade effluent recycle, adopts following production model at present: the heavy transformation process of carbon adopts bicarbonate of ammonia to make precipitation agent, adopts ammoniacal liquor to make saponifying agent in extraction separation process, and the waste water of generation is mainly NH
4cl waste water, in these waste water, ammonium chloride content higher (12-16%), can carry out recycling, but contains a large amount of calcium, magnesium ion in waste water, can affect efficiency and the work-ing life of nanofiltration membrane used in subsequent technique in treating processes, needs separating treatment.
Summary of the invention
Object of the present invention: the present invention proposes a kind of method of calcium, magnesium ion in separating ammonium chloride waste water, by adding soluble phosphate reagent, can realize high calcium, magnesium ion clearance.
technical solution:
A kind of method of calcium, magnesium ion in separating ammonium chloride waste water, the method adopts chemical precipitation method, adds soluble phosphate to introduce phosphate radical in waste water, produces the crystalline precipitation of calcium phosphate, magnesium ammonium phosphate, carry out solid-liquid separation, and then calcium, magnesium ion in waste water are removed.
In separating ammonium chloride waste water, a method for calcium, magnesium ion, comprises the steps:
(1) first with bicarbonate of ammonia and ammoniacal liquor or ammoniacal liquor, adjusting ammonium chloride waste-water pH value is 7-9;
(2) selecting soluble phosphate is precipitation agent, according to calcium, magnesium ion concentration in raw wastewater, precipitation agent is joined in (1) ammonium chloride waste-water by adding the reinforced formation of dry powder, stirs 15 ~ 60min in reactive tank; Principal reaction is:
3Ca
2++2PO
4 3-=Ca
3(PO
4)
2↓
Mg
2++NH
4 ++PO
4 3-=MgNH
4PO
4↓
(3) carry out solid-liquid separation, filtrate proceeds to subsequent treatment process.
Described soluble phosphate precipitation agent is (NH
4)
2hPO
4or Na
3pO
4.
Further: will with coefficient of discharge, to be the precipitation agent of 0.9 ~ 1.10 times, and by adding the reinforced formation of dry powder, to join in (1) ammonium chloride waste-water.
beneficial effect:
The present invention is applicable to the ammonium chloride waste-water of various ionic concns and processes, the present invention is very little according to calcium phosphate, magnesium ammonium phosphate solubility product constant, adopts phosphoric acid salt to precipitate removal, and strictly controls processing parameter, realize the separation of calcium in ammonium chloride waste-water, magnesium ion, reach high calcium, magnesium ion clearance, generation be precipitated as crystalline precipitation, be easy to solid-liquid separation, Technology is simple, easy handling is controlled, and chemical reagent consumption is few, and cost for wastewater treatment is low.
Embodiment
Embodiment 1
Reactive tank adds ammonium chloride waste-water 19 m
3, CaO:0.0318 mol/L in waste water, MgO:0.008 mol/L, pH value is 6, under whipped state, with bicarbonate of ammonia, adjusting waste water ph is 7, then is 7.5 with strong aqua adjust pH.Add (the NH with 1.1 times of coefficient of discharges
4)
2hPO
4precipitation agent, stirring reaction 30min, stops stirring, and gets clear liquid analysis, CaO:0.0007mol/L in waste water, MgO:0.0001mol/L, the clearance 97.80% of calcium, the clearance 98.75% of magnesium.After solid-liquid separation, filtrate proceeds to subsequent treatment process.
Embodiment 2
Reactive tank adds ammonium chloride waste-water 18 m
3, CaO:0.0132mol/L in waste water, MgO:0.0065 mol/L, pH value is 6, under whipped state, with bicarbonate of ammonia, adjusting waste water ph is 7, then is 7.5 with strong aqua tune pH value.Add (the NH with 1.0 times of coefficient of discharges
4)
2hPO
4precipitation agent, stirring reaction 30min, stops stirring, and gets clear liquid analysis, CaO:0.0011 mol/L in waste water, MgO:0.0002 mol/ L, the clearance 91.67% of calcium, the clearance 96.92% of magnesium.After solid-liquid separation, filtrate proceeds to subsequent treatment process.
Embodiment 3
Reactive tank adds ammonium chloride waste-water 19m
3, CaO:0.0212 mol/L in waste water, MgO:0.0077mol/L, pH value is 6, under whipped state, with bicarbonate of ammonia, adjusting waste water ph is 7, then is 7.5 with strong aqua tune pH value.Add (the NH with 0.9 times of coefficient of discharge
4)
2hPO
4precipitation agent, stirring reaction 30min, stops stirring, and gets clear liquid analysis, CaO:0.0005 mol/L in waste water, MgO:0.0001mol/L, the clearance 97.64% of calcium, the clearance 98.70% of magnesium.After solid-liquid separation, filtrate proceeds to subsequent treatment process.
Embodiment 4
Reactive tank adds ammonium chloride waste-water 19m
3, CaO:0.0132 mol/L in waste water, MgO:0.0067mol/L, pH value is 6, under whipped state, with bicarbonate of ammonia, adjusting waste water ph is 7, then is 7.5 with strong aqua tune pH value.Add the NH with 1.0 times of coefficient of discharges
4h
2pO
4precipitation agent, stirring reaction 30min, stops stirring, and gets clear liquid analysis, CaO:0.0012 mol/L in waste water, MgO:0.0003mol/L, the clearance 90.91% of calcium, the clearance 95.52% of magnesium.After solid-liquid separation, filtrate proceeds to subsequent treatment process.
Embodiment 5
Reactive tank adds ammonium chloride waste-water 19m
3, CaO:0.0132mol/L in waste water, MgO:0.0067mol/L, pH value is 6, under whipped state, with strong aqua adjust pH, is 7, adds (the NH with 1.0 times of coefficient of discharges
4)
3pO
4precipitation agent, stirring reaction 30min, stops stirring, and gets clear liquid analysis, CaO:0.0013 mol/L in waste water, MgO:0.0002mol/L, the clearance 90.15% of calcium, the clearance 97.01% of magnesium.After solid-liquid separation, filtrate proceeds to subsequent treatment process.
Embodiment 6
Reactive tank adds ammonium chloride waste-water 19m
3, CaO:0.0132 mol/L in waste water, MgO:0.0067mol/L, pH value is 6, under whipped state, with strong aqua adjust pH, is 7, adds the Na with 1.0 times of coefficient of discharges
3pO
4precipitation agent, stirring reaction 30min, stops stirring, and gets clear liquid analysis, CaO:0.0015 mol/L in waste water, MgO:0.0002mol/L, the clearance 88.64% of calcium, the clearance 97.01% of magnesium.After solid-liquid separation, filtrate proceeds to subsequent treatment process.
Embodiment 7
Reactive tank adds ammonium chloride waste-water 19m
3, CaO:0.0132 mol/L in waste water, MgO:0.0067mol/L, pH value is 6, under whipped state, with strong aqua adjust pH, is 7.5, adds the Na with 1.0 times of coefficient of discharges
2hPO
4precipitation agent, stirring reaction 30min, stops stirring, and gets clear liquid analysis, CaO:0.0007 mol/L in waste water, MgO:0.0001mol/L, the clearance 94.70% of calcium, the clearance 98.51% of magnesium.After solid-liquid separation, filtrate proceeds to subsequent treatment process.
Embodiment 8
Reactive tank adds ammonium chloride waste-water 19m
3, CaO:0.0132 mol/L in waste water, MgO:0.0067mol/L, pH value is 6, under whipped state, with strong aqua adjust pH, is 7.5, adds the NaH with 1.0 times of coefficient of discharges
2pO
4precipitation agent, stirring reaction 30min, stops stirring, and gets clear liquid analysis, CaO:0.0016 mol/L in waste water, MgO:0.0002mol/L, the clearance 87.88% of calcium, the clearance 97.01% of magnesium.After solid-liquid separation, filtrate proceeds to subsequent treatment process.
Claims (4)
1. a method for calcium, magnesium ion in separating ammonium chloride waste water, is characterized in that, adopts chemical precipitation method, in waste water, add soluble phosphate to introduce phosphate radical, the crystalline precipitation that produces calcium phosphate, magnesium ammonium phosphate, carries out solid-liquid separation, and then calcium, magnesium ion in waste water are removed.
2. the method for calcium, magnesium ion in a kind of separating ammonium chloride waste water according to claim 1, is characterized in that, comprises the steps:
(1) first with bicarbonate of ammonia and ammoniacal liquor or ammoniacal liquor, adjusting ammonium chloride waste-water pH value is 7-9;
(2) selecting soluble phosphate is precipitation agent, according to calcium, magnesium ion concentration in raw wastewater, precipitation agent is joined in (1) ammonium chloride waste-water by adding the reinforced formation of dry powder, stirs 15 ~ 60min in reactive tank; Principal reaction is:
3Ca
2++2PO
4 3-=Ca
3(PO
4)
2↓
Mg
2++NH
4 ++PO
4 3-=MgNH
4PO
4↓
(3) carry out solid-liquid separation, filtrate proceeds to subsequent treatment process.
3. the method for calcium, magnesium ion in a kind of separating ammonium chloride waste water according to claim 2, is characterized in that, soluble phosphate precipitation agent is (NH
4)
2hPO
4or Na
3pO
4.
4. the method for calcium, magnesium ion in a kind of separating ammonium chloride waste water according to claim 2, is characterized in that, will with coefficient of discharge, be the precipitation agent of 0.9 ~ 1.10 times, by adding the reinforced formation of dry powder, joins in (1) ammonium chloride waste-water.
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| CN201410180131.2A CN103964588B (en) | 2014-04-30 | 2014-04-30 | A kind of method of calcium and magnesium ion in separating ammonium chloride waste water |
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| CN103964588B CN103964588B (en) | 2016-04-06 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112158931A (en) * | 2020-10-12 | 2021-01-01 | 包头稀土研究院 | Method for removing calcium and magnesium in ammonium chloride wastewater |
| CN113462909A (en) * | 2020-03-30 | 2021-10-01 | 厦门稀土材料研究所 | Method for enriching rare earth in rare earth ore leaching solution by adopting organic phosphonic (phosphoric) acid precipitator |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101654238A (en) * | 2009-09-11 | 2010-02-24 | 华东理工大学 | Method for recovering phosphonium compound from phosphorous excess sludge of urban sewage treatment plant |
| CN102765834A (en) * | 2012-08-13 | 2012-11-07 | 铜陵化学工业集团有限公司 | Method for treating industrial nitrogenous waste water through chemical precipitation method |
| CN102898213A (en) * | 2012-10-12 | 2013-01-30 | 常州大学 | Method for recovering nitrogen and phosphorus from biogas slurry from pig farms |
-
2014
- 2014-04-30 CN CN201410180131.2A patent/CN103964588B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101654238A (en) * | 2009-09-11 | 2010-02-24 | 华东理工大学 | Method for recovering phosphonium compound from phosphorous excess sludge of urban sewage treatment plant |
| CN102765834A (en) * | 2012-08-13 | 2012-11-07 | 铜陵化学工业集团有限公司 | Method for treating industrial nitrogenous waste water through chemical precipitation method |
| CN102898213A (en) * | 2012-10-12 | 2013-01-30 | 常州大学 | Method for recovering nitrogen and phosphorus from biogas slurry from pig farms |
Non-Patent Citations (1)
| Title |
|---|
| 王浩 等: "化学沉淀法去除稀土湿法冶炼废水中钙与高浓度氨氮研究", 《环境科学》, vol. 34, no. 7, 31 July 2013 (2013-07-31), pages 2718 - 2727 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113462909A (en) * | 2020-03-30 | 2021-10-01 | 厦门稀土材料研究所 | Method for enriching rare earth in rare earth ore leaching solution by adopting organic phosphonic (phosphoric) acid precipitator |
| CN112158931A (en) * | 2020-10-12 | 2021-01-01 | 包头稀土研究院 | Method for removing calcium and magnesium in ammonium chloride wastewater |
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|---|---|
| CN103964588B (en) | 2016-04-06 |
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Address after: 014030 No. 83 704 Huanghe Road, Baotou Rare Earth Development Zone, Inner Mongolia Autonomous Region Patentee after: China north rare earth (Group) hi tech Limited by Share Ltd Address before: 014030 No. 83 704 Huanghe Road, Baotou Rare Earth Development Zone, Inner Mongolia Autonomous Region Patentee before: Inner Mongolia Baogang Rare Earth (Group) High Technology Co., Ltd. |
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