CN105461002A - Method for removing calcium and magnesium in rare-earth industrial wastewater - Google Patents
Method for removing calcium and magnesium in rare-earth industrial wastewater Download PDFInfo
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- CN105461002A CN105461002A CN201511015062.0A CN201511015062A CN105461002A CN 105461002 A CN105461002 A CN 105461002A CN 201511015062 A CN201511015062 A CN 201511015062A CN 105461002 A CN105461002 A CN 105461002A
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- extraction
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/26—Treatment of water, waste water, or sewage by extraction
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/04—Surfactants, used as part of a formulation or alone
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention relates to a method for removing calcium and magnesium in rare-earth industrial wastewater, which is characterized by comprising the following steps: carrying out extraction under the conditions that the volume ratio of the organic phase to the liquid phase is 1-2 and the saponification degree is 45-60%, wherein ammonium sulfate wastewater generated by a rare-earth acid-process smelting technique is used as a treatment object, and 50 vol% P507+50 vol% sulfonated coal oil is used as an organic extractant; and after the extraction, standing to stratify. The treatment method is simple: after a plurality of stages of extraction tanks are connected to the wastewater outlet, wastewater at the outlet can directly enter the ammonia evaporation system; and after the extraction and standing for stratification, the removal rates of calcium and magnesium ions in ammonium ortho-sulfate wastewater can respectively reach 90% or above, thereby solving the problem of severe blockage in the ammonia evaporation system pipeline. The method can implement continuous production, and has the advantages of high treatment capacity, high reaction speed, favorable separating effect and recyclable extractant. Meanwhile, the method reduces the impurity ion content in the ammonium sulfate product, and enhances the quality of the product.
Description
Technical field
The present invention relates to a kind of method of removing calcium-magnesium removing in rare-earth industry waste water, belong to hydrometallurgy and industry environmental protection technical field.
Background technology
The present invention be directed to the removal that the ammonium sulfate waste water produced in rare-earth smelting process carries out calcium magnesium.In rare-earth smelting process, there are two places in the source of ammonium sulfate waste water:
First source sinks waste water for mixing carbon.Baiyunebo concentrate is a kind of composite ore of hamartite and monazite, and at present, the Bayan Obo rare earth ore concentrate of more than 90% adopts vitriol oil strengthening sinter process to decompose.After roasting, water logging operation terminate, a part of infusion enters mixing carbon and sinks operation, flows to into carbon deep gouge, form carbonated rare earth slurries with ammonium bicarbonate soln.Carbonated rare earth slurries are after Plate Filtration, and filtrate is referred to as mixing carbon and sinks waste water, and main component is ammonium sulfate.
Second source is extracting and separating saponification waste-water.Removing enters mixing carbon and sinks operation, and residue infusion all enters extracting and separating operation.The mixture adopting P507 and kerosene is extraction agent, ammoniacal liquor is saponifying agent, saponification is organic mix with rare earth sulfate solution after entirely drag for abstraction and type-reverting, take hydrochloric acid as reverse-extraction agent, through Ce/Pr grouping, La/Ce grouping and Nd/Sm grouping, obtain Lanthanum trichloride, Cerium II Chloride, praseodymium chloride neodymium and chlorination sm-eu-gd four kinds of feed liquids respectively.Produce saponification waste-water, main component is ammonium sulfate simultaneously.
The processing mode of current ammonium sulfate waste water carries out ammonia still process process for entering between environment-friendly vehicle, but due to calcium ion content too high, be combined with sulfate ion in ammonia still process process, form sl. sol. calcium sulfate precipitation, cause the regular blocking of ammonia steaming system.For slight blocking, can with the mode process tamper beaing pipeline, and for the blocking of seriousness, then pipeline can be caused all blocked, need to stop production and could process.Meanwhile, magnesium ion content is high, and the ammonium sulfate product foreign ion produced also can be caused to exceed standard.
Tradition calcium-magnesium removing adopts chemical-agent technique, but experiment proves, for ammonium sulfate waste water, take bicarbonate of ammonia as precipitation agent, magnesium ion clearance is 0, and calcium ion clearance is 56.25%; Take ammonium phosphate as precipitation agent, magnesium ion clearance is 45.15%, and calcium ion clearance is 4.17%, and experimental result is in table 1.Visible by result, adopt chemical precipitation method to remove calcium ions and magnesium ions, not only consume a large amount of chemical reagent, cost for wastewater treatment increases, and calcium ions and magnesium ions removal effect is not good enough, does not reach the problem solving line clogging.
Therefore, for this problem, ammonium sulfate waste water is carried out to the research of calcium-magnesium removing.
Summary of the invention
The object of this invention is to provide a kind of method of carrying out the removal of calcium magnesium and separation for rare-earth industry waste water, block serious problem to solve equipment in wastewater treatment process.
Method of the present invention is: the ammonium sulfate waste water produced with rare earth acid system smelting technology is for handling object, add that the sulfonated kerosene of 50% volume ratio is as organic extractant using the P507 of 50% volume ratio, be 1 ~ 2 in organic phase and LVT, saponification degree is extract under the condition of 45% ~ 60%, stratification after extraction.
After extraction stratification, in ortho-sulfuric acid ammonium waste water, calcium, magnesium ion clearance all can reach more than 90%, effectively can reduce ammonia steaming system line clogging problem.Solvent extraction and separation refers to the aqueous solution containing separated material and immiscible organic solvent exposure, makes one or more components enter organic solvent, and remaining stays in aqueous, thus reaches a kind of method of the object of separation.Compared with traditional separation method, it is large that solvent extration has process capacity, and speed of response is fast, good separating effect, can consecutive production, and extraction agent such as to can be recycled at the advantage.
Advantage of the present invention is: treatment process is simple, only need connect what extraction tank at wastewater outlet place, the waste water of outlet directly can enter ammonia steaming system, and after extraction stratification, in ortho-sulfuric acid ammonium waste water, calcium, magnesium ion clearance all can reach more than 90%, solve the problem that ammonia steaming system line clogging is serious, can realize consecutive production, process capacity is large, and speed of response is fast, good separating effect, and extraction agent can be recycled.Meanwhile, decrease the impurity ion content in ammonium sulfate product, the quality of product is got a promotion.
Embodiment
Embodiment 1: be 2:1 in organic phase and LVT, saponification degree is under the condition of 30%, after extraction stratification, measures calcium magnesium density in raffinate.In ortho-sulfuric acid ammonium waste water, magnesium ion content is 8.55g/L, and in raffinate, content is 3.49g/L, and clearance reaches 59.18%; In ortho-sulfuric acid ammonium waste water, calcium ion content is 0.48g/L, content 0.01g/L in raffinate, clearance 97.92%.As can be seen from above-mentioned example, when saponification degree lower than 45% time, in ortho-sulfuric acid ammonium waste water, the clearance of magnesium ion is lower.Experimental result is in table 2.
Embodiment 2: be 2:1 in organic phase and LVT, saponification degree is under the condition of 45%, after extraction stratification, measures calcium magnesium density in raffinate.In ortho-sulfuric acid ammonium waste water, magnesium ion content is 8.55g/L, and in raffinate, content is 0.74g/L, and clearance reaches 91.35%; In ortho-sulfuric acid ammonium waste water, calcium ion content is 0.48g/L, and in raffinate, content is less than 0.01g/L, and clearance is greater than 97.92%.Experimental result is in table 2.
Embodiment 3: be 2:1 in organic phase and LVT, saponification degree is under the condition of 60%, after extraction stratification, measures calcium magnesium density in raffinate.In ortho-sulfuric acid ammonium waste water, magnesium ion content is 8.55g/L, and in raffinate, content is 0.27g/L, and clearance reaches 96.84%; In ortho-sulfuric acid ammonium waste water, calcium ion content is 0.48g/L, content < 0.01g/L, clearance > 97.92% in raffinate.Experimental result is in table 2.
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Claims (1)
1. in a rare-earth industry waste water, go the method for calcium-magnesium removing, it is characterized in that: the ammonium sulfate waste water produced with rare earth acid system smelting technology is for handling object, add that the sulfonated kerosene of 50% volume ratio is as organic extractant using the P507 of 50% volume ratio, be 1 ~ 2 in organic phase and LVT, saponification degree is extract under the condition of 45% ~ 60%, stratification after extraction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511015062.0A CN105461002A (en) | 2015-12-31 | 2015-12-31 | Method for removing calcium and magnesium in rare-earth industrial wastewater |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511015062.0A CN105461002A (en) | 2015-12-31 | 2015-12-31 | Method for removing calcium and magnesium in rare-earth industrial wastewater |
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| Publication Number | Publication Date |
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| CN105461002A true CN105461002A (en) | 2016-04-06 |
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| CN201511015062.0A Pending CN105461002A (en) | 2015-12-31 | 2015-12-31 | Method for removing calcium and magnesium in rare-earth industrial wastewater |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113699376A (en) * | 2021-08-18 | 2021-11-26 | 中国北方稀土（集团）高科技股份有限公司 | Method for separating calcium ions in rare earth transformation type calcium magnesium containing rare earth sulfate solution by extraction method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB986591A (en) * | 1962-06-08 | 1965-03-17 | Gen Mills Inc | Separative process |
| CN103539242A (en) * | 2013-10-15 | 2014-01-29 | 包头稀土研究院 | Method used for reducing calcium content of rare earth industrial wastewater |
-
2015
- 2015-12-31 CN CN201511015062.0A patent/CN105461002A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB986591A (en) * | 1962-06-08 | 1965-03-17 | Gen Mills Inc | Separative process |
| CN103539242A (en) * | 2013-10-15 | 2014-01-29 | 包头稀土研究院 | Method used for reducing calcium content of rare earth industrial wastewater |
Non-Patent Citations (1)
| Title |
|---|
| 刘久苗 等: "用P507从硫酸镍溶液中萃取分离钙镁的研究", 《上海有色金属》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113699376A (en) * | 2021-08-18 | 2021-11-26 | 中国北方稀土（集团）高科技股份有限公司 | Method for separating calcium ions in rare earth transformation type calcium magnesium containing rare earth sulfate solution by extraction method |
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Application publication date: 20160406 |