CN105836918A - Technological method of rare earth industrial wastewater treatment and cyclic utilization - Google Patents

Technological method of rare earth industrial wastewater treatment and cyclic utilization Download PDF

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Publication number
CN105836918A
CN105836918A CN201610225278.8A CN201610225278A CN105836918A CN 105836918 A CN105836918 A CN 105836918A CN 201610225278 A CN201610225278 A CN 201610225278A CN 105836918 A CN105836918 A CN 105836918A
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CN
China
Prior art keywords
rare earth
waste water
magnesium
rare
calcium chloride
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
CN201610225278.8A
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Chinese (zh)
Inventor
候少春
赵永志
马莹
丁艳蓉
张文娟
李二斗
谢军
李�赫
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Baotou Rare Earth Research Institute
Santoku Corp
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Baotou Rare Earth Research Institute
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Priority to CN201610225278.8A priority Critical patent/CN105836918A/en
Publication of CN105836918A publication Critical patent/CN105836918A/en
Pending legal-status Critical Current

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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
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/20—Halides
    • C01F11/24—Chlorides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F5/00—Compounds of magnesium
    • C01F5/14—Magnesium hydroxide
    • C01F5/22—Magnesium hydroxide from magnesium compounds with alkali hydroxides or alkaline- earth oxides or hydroxides
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The invention relates to a technological method of rare earth industrial wastewater treatment and cyclic utilization. The method includes using magnesium sulfate waste water generated by rare earth production technology as raw material, adding a precipitating agent to remove sulfate radical, and recycling magnesium from the used precipitating agent quicklime, slaked lime or calcium chloride to obtain magnesium hydroxide product with the purity more than 90% and calcium chloride solution. The magnesium hydroxide product can be used for performing saponification of extractant, and thecalcium chloride solution can be used for leaching rare earth roasted ore. The leached rare earth immersion liquid enters P507 full extraction transformation technology, and the obtained rare earth solution enters the next process of rare earth extraction separation. The generated waste water can be treated by the method of the present invention. The zero discharge of the waste water in full extraction transformation technology can be realized, the magnesium resource can be recycled, and the REO recovery rate is as same as the rate of new water-leach.

Description

The process that a kind of rare-earth industry waste water processes and recycles
Technical field:
The present invention relates to the process that a kind of rare-earth industry waste water processes and recycles, belong to hydrometallurgy and industrial environment Resist technology field.
Background technology:
Bayan Obo rare earth ore concentrate is the composite ore of bastnaesite and monazite, at present, and the Bayan Obo rare earth ore concentrate of more than 90% Concentrated sulfuric acid strengthening roasting technique is used to decompose.Concentrate after decomposition is referred to as roasted ore, and roasted ore water logging goes out, the biggest portion Point rare earth enters in aqueous phase with the form of sulfate, and the foreign ion such as the most a small amount of calcium, magnesium, thorium, iron, manganese is also with sulfate Form enters in solution, and this solution is referred to as infusion.In order to reduce the foreign ion impact on subsequent technique, generally by water Immersion liquid is neutralized to pH value about 4.5, to remove thorium, iron.Because potassium, sodium, ammonium etc. can form double salt precipitation with sulfuric acid rare earth, use more Oxide or the hydroxide of calcium and magnesium make nertralizer.Due in calcium and calcium sulfate precipitation can be formed, at follow-up and organic extractant In contact process, the loss of organic phase can be increased, reduce the yield of rare earth, so enterprise's many employings magnesia neutralization at present removes Miscellaneous.The filtrate being filtrated to get after neutralization is referred to as qualified water immersion liquid, and filter residue is water logging slag, and usual REO content is about 3-5%.Water logging Liquid uses solvent-extracted method to realize the separation of rare earth element.The extractant that rare-earth extraction separating process is conventional at present has P507、 P204Deng.Because of the P after saponification507There is loading capacity consumption high, organic little, the features such as equipment takes up an area few, easy back extraction, thus industrial Use P more507Make extractant.Magnesia is generally used to make saponification agent.Saponification P507Rare earth after mixing with infusion, in infusion Ion and the magnesium ion exchange in saponification P507, rare earth ion is extracted in the extractant of organic phase, and magnesium ion enters water Phase, this aqueous phase, as rare-earth industry waste water, mainly contains the calcium magnesium element that neutralization, the magnesium of saponification process addition and mineral carry. The most more common Processing tecchnics is to use lime neutralisation, and the method principle is as follows
H2O+CaO=Ca(OH)2 (1)
MgSO4+Ca(OH)2=CaSO4↓+ Mg(OH)2↓(2)
Being joined by lime in waste water, generate the mixture of a large amount of magnesium hydroxide and calcium sulfate, this mixture generation amount is big and nothing Economic worth, becomes solid waste.Because calcium ions and magnesium ions Nature comparison is close, for the waste water of calcium-magnesium-containing ion, generally by calcium ions and magnesium ions Remove from waste water as same class impurity.Higher for magnesium ion concentration, that calcium ion concentration is relatively low waste water, conventional method is neglected Recovery depending on magnesium resource.
Summary of the invention:
It is an object of the invention to provide one can be used by waste water circulation, to solve at traditional rare earth process for treating industrial waste water Reason is not thorough, and secondary residue generation amount is big, and without economic worth, causes a kind of rare-earth industry waste water of the wasting of resources process and follow The process that ring utilizes.
Technical solution:
The process that a kind of rare-earth industry waste water processes and recycles, method is as follows: rare earth metallurgy is through going sulfuric acid After root, magnesium addition, with calcium chloride solution leach roasted ore, the waste water that leachate obtains after entirely dragging for rare earth obtain circular treatment, Use.
Rare earth metallurgy of the present invention is the containing magnesium sulfate of generation, magnesium chloride, aluminium chloride, iron chloride during rare-earth smelting Waste water.
The present invention removes rare earth metallurgy impurity and uses the method for fractional steps: the first step uses calcic, barium compounds or solution Removing the sulfate ion in rare earth metallurgy, the rare earth metallurgy removing sulfate ion is used ripe stone by second step again Ash removes magnesium ion, obtains magnesium hydroxide waste water after reuse, process and becomes calcium chloride solution；3rd step is with processing waste water The calcium chloride solution obtained is back to roasted ore and leaches, and leachate continues extraction and processes, and circulation above-mentioned steps can realize waste water Complete alternation use and magnesium resourceization utilize.
The magnesium hydroxide products that demagging process of the present invention obtains, MgO >=85%, can be back to use in rare-earth smelting technical process.
Cl in waste water after present invention process->=10g/l, Ca >=5g/l, SO4 2-≤ 2g/l, Mg2+≤1g/l。
The present invention uses in calcium chloride solution leaching process, extraction temperature >=35 DEG C, extraction time >=30min.
The present invention entirely drag for rare earth transformation process produce waste water as raw material, first sulfate radical, recycling magnesium obtains pure Magnesium hydroxide products and the calcium chloride solution that degree is more than 90%, obtaining magnesium hydroxide can be with reuse.Waste water after process becomes chlorination Calcium solution, uses this calcium chloride solution to leach for roasted ore, and leachate continues extraction and processes, and the waste water obtained uses same Mode processes.Realize this operation waste water complete alternation use and magnesium resourceization utilizes.
The invention have the advantage that improving conventional waste water technique processes as same pollutant together using calcium and magnesium, produce a large amount of The shortcoming of waste residue, not only realizes waste water circulation use but also makes magnesium resourceization utilize, have preferable economic worth, the value of environmental protection.
Detailed description of the invention:
Embodiment 1: taking 1L waste water (rare-earth industry waste water) and join in 2L beaker, its analysis result is as shown in table 1.
The chemical composition of table 1 waste water and content (g/l)
Composition CaO MgO CL- SO42-
Content 1.18 16.9 2.35 28.2
Adding solid calcium chloride under stirring, filter after continuously stirred 30 minutes, filter residue is abandoned, and filtrate component is as shown in table 2.
Table 2 example 1 analysis result (g/l)
Composition CaO MgO CL- SO42-
Content 1.31 16.32 22.96 1.86
This solution being added white lime, reacts 30min, filter, filtrate filter residue sample presentation respectively, filtrate is as shown in table 3, filter residue is dried As shown in table 4
Table 3 example 1 analysis result (g/l)
Composition CaO MgO CL- SO42-
Content 16.3 0.06 22.96 1.24
Table 4 example 1 analysis result (g/l)
Composition CaO MgO
Content 2.37 90.12
By the filtrate shown in example 1 table 3, leaching for roasted ore, water logging slag sample presentation is analyzed, and result is as shown in table 5
Table 5 example 1 analysis result (g/l)
Composition REO
Content 2.37
Embodiment 2: taking 1L waste water (rare-earth industry waste water), its analysis result is as shown in table 6
The chemical composition of table 6 waste water and content (g/l)
Composition CaO MgO CL- SO42-
Content 0.87 21.23 21.45 48.24
This waste water adds quick lime and removes SO42-, and reaction 30min filtration, filter residue is abandoned, filtrate result is as shown in table 7
Table 7 example 2 analysis result (g/l)
Composition CaO MgO CL- SO42-
Content 1.15 8.77 21.45 1.44
This waste water adds white lime demagging, obtains filtrate, filter residue sample presentation respectively.Filtrate result is as shown in table 8, filter residue is dried and sent Sample, result is as shown in table 9
Table 8 example 2 analysis result (g/l)
Composition CaO MgO CL- SO42-
Content 10.96 0.06 20.17 0.41
Table 9 example 2 analysis result (g/l)
Composition CaO MgO
Content 2.47 90.17
By the filtrate shown in example 2 table 8, leaching for roasted ore, water logging slag sample presentation is analyzed, and result is as shown in table 10
Table 10 example 2 analysis result (g/l)
Composition REO
Content 2.19
Embodiment 3: take 1L waste water (rare-earth industry waste water), its analysis result is as shown in table 11,
The chemical composition of table 11 waste water and content (g/l)
Composition CaO MgO CL- SO42-
Content 0.96 20.13 21.32 44.36
This waste water adds quick lime and removes SO42-, and reaction 30min filtration, filter residue is abandoned, filtrate result is as shown in table 12
Table 12 example 3 analysis result (g/l)
Composition CaO MgO CL- SO42-
Content 1.03 9.87 22.43 0.86
This waste water adds white lime demagging, obtains filtrate, filter residue sample presentation respectively.Filtrate result is as shown in table 13, filter residue is dried and sent Sample, result is as shown in table 14
Table 13 example 2 analysis result (g/l)
Composition CaO MgO CL- SO42-
Content 10.96 0.06 21.36 0.41
Table 14 example 2 analysis result (g/l)
Composition CaO MgO
Content 2.17 90.32
By the filtrate shown in example 3 table 13, doing roasted ore according to solid-to-liquid ratio 1:8 and leach, water logging slag sample presentation is analyzed, result such as table 10 Shown in
Table 15 example 2 analysis result (g/l)
Composition REO
Content 2.09
Using present invention process, can realize internal process circulation containing magnesium waste water, without outer row, the magnesium simultaneously obtaining MgO >=85% produces Product.Water after process returns roasted ore water logging operation, REO content≤2.5% in gained water logging slag, and REO yield goes out roasting with new water logging Burn ore deposit rare-earth yield suitable.

Claims (6)

1. the process that rare-earth industry waste water processes and recycles, is primarily characterized in that: rare earth metallurgy, warp After removing sulfate radical, magnesium addition, leaching roasted ore with calcium chloride solution, the waste water that leachate obtains after entirely dragging for rare earth is followed Ring processes, uses.
Method the most according to claim 1, it is characterised in that rare earth metallurgy is containing of producing during rare-earth smelting Magnesium sulfate, magnesium chloride, aluminium chloride, the waste water of iron chloride.
Method the most according to claim 1, it is characterised in that the removal rare earth metallurgy impurity employing method of fractional steps: first Step uses calcic, barium compounds or solution to remove the sulfate ion in rare earth metallurgy, and second step is to going sulfuric acid The rare earth metallurgy of radical ion removes magnesium ion with white lime again, obtains magnesium hydroxide waste water after reuse, process and becomes For calcium chloride solution；The calcium chloride solution that 3rd step process waste water obtains is back to roasted ore and leaches, and leachate continues extraction Processing, circulation above-mentioned steps can realize waste water complete alternation use and magnesium resourceization utilizes.
Method the most according to claim 3, it is characterised in that the magnesium hydroxide products that demagging process obtains, MgO >=85%, Can be back to use in rare-earth smelting technical process.
Method the most according to claim 3, it is characterised in that Cl in the waste water after process->=10g/l, Ca >=5g/l, SO4 2-≤ 2g/l, Mg2+≤1g/l。
Method the most according to claim 3, it is characterised in that use in calcium chloride solution leaching process, extraction temperature >= 35 DEG C, extraction time >=30min.
CN201610225278.8A 2016-04-12 2016-04-12 Technological method of rare earth industrial wastewater treatment and cyclic utilization Pending CN105836918A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109574174A (en) * 2018-12-13 2019-04-05 中南大学 A kind of method that rare-earth smelting technical process chlorine-contained wastewater is administered
CN112456620A (en) * 2020-11-02 2021-03-09 龙南县南裕稀土资源综合利用有限责任公司 Method for treating wastewater after ore leaching and closing of ionic rare earth ore
CN115896490A (en) * 2022-11-18 2023-04-04 包头华美稀土高科有限公司 Resource utilization method for waste residues generated in rare earth concentrate smelting process
CN116282118A (en) * 2022-12-28 2023-06-23 广西国盛稀土新材料有限公司 Method for producing industrial calcium chloride by utilizing rare earth smelting high-salt wastewater

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Publication number Priority date Publication date Assignee Title
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CN101172627A (en) * 2007-10-11 2008-05-07 河北科技大学 Method of producing magnesium hydroxide
CA2899377A1 (en) * 2013-01-28 2014-07-31 Paul Mcwilliams Methods and systems for water recovery
CN104232949A (en) * 2014-10-14 2014-12-24 包头稀土研究院 Recycling method for rare earth leaching and leaching water of sulfuric acid roasted rare earth ore concentrate

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101088935A (en) * 2007-06-26 2007-12-19 张凌云 RE waste water treating complete circulation process
CN101172627A (en) * 2007-10-11 2008-05-07 河北科技大学 Method of producing magnesium hydroxide
CA2899377A1 (en) * 2013-01-28 2014-07-31 Paul Mcwilliams Methods and systems for water recovery
CN104232949A (en) * 2014-10-14 2014-12-24 包头稀土研究院 Recycling method for rare earth leaching and leaching water of sulfuric acid roasted rare earth ore concentrate

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109574174A (en) * 2018-12-13 2019-04-05 中南大学 A kind of method that rare-earth smelting technical process chlorine-contained wastewater is administered
CN112456620A (en) * 2020-11-02 2021-03-09 龙南县南裕稀土资源综合利用有限责任公司 Method for treating wastewater after ore leaching and closing of ionic rare earth ore
CN115896490A (en) * 2022-11-18 2023-04-04 包头华美稀土高科有限公司 Resource utilization method for waste residues generated in rare earth concentrate smelting process
CN116282118A (en) * 2022-12-28 2023-06-23 广西国盛稀土新材料有限公司 Method for producing industrial calcium chloride by utilizing rare earth smelting high-salt wastewater

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