CN100506724C - RE waste water treating complete circulation process - Google Patents
RE waste water treating complete circulation process Download PDFInfo
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- CN100506724C CN100506724C CNB2007100182461A CN200710018246A CN100506724C CN 100506724 C CN100506724 C CN 100506724C CN B2007100182461 A CNB2007100182461 A CN B2007100182461A CN 200710018246 A CN200710018246 A CN 200710018246A CN 100506724 C CN100506724 C CN 100506724C
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Abstract
The present invention discloses process of treating RE producing waste water for reuse, and aims at eliminating ammonia nitrogen, acid, high hardness and salt from RE producing waste water for reuse. One to three of alkali earth metal oxide, sulfide, carbonate and hydroxide are used in treating RE producing waste water, and the treated waste water has less RE production harmful impurity and may be reused completely. The present invention has the advantages of low cost, easy operation, etc.
Description
Technical field the present invention relates to a kind of method of RE waste water treating complete circulation.
The background technology rare earth element is the general name of lanthanon and yttrium, 17 kinds of elements of scandium, owing to their similar performance is difficult to separate.Rare-earth mineral has: hamartite, solitary stone ore, mixing ore deposit (baiyuneboite promptly belongs to this type of), rare earth ion ore deposit.One, alkaline process and sulfuric acid process are adopted in solitary stone ore of present industrial processing and mixing ore deposit.Grade can adopt alkaline process or sulfuric acid process greater than 60% mineral, and sulfuric acid process is decomposed mixed type concentrate technology (Xu Guangxian chief editor, rare earth by the vitriol intensified roasting of Beijing Non-Ferrous Metal Research General Academy's exploitation at the beginning of the eighties, the second edition first volume, metallurgical industry press, 2002, P401, P408); Grade adopts sulfuric acid process mostly less than 50% mineral, as the most of sulfuric acid process that adopts of area, packet header Rare Earth Production factory.This technology is mixed the back with rare earth ore concentrate and is carried out the High-Temperature Strengthening roasting at 400 ℃～500 ℃ with the excessive vitriol oil, calcining matter goes out through water logging, aqueous solution acidity is 0.05～0.5mol/L, and the rare earth soluble sulphate enters the aqueous solution, and non-rare earth impurity such as Ca, Mg, Fe etc. also enter the aqueous solution.Two, the neutralization of rare earth calcining matter leach liquor.Rare earth calcining matter leach liquor makes the rare earth infusion through alkaline earth metal oxide or carbonate pH3～4 that neutralize.In the beginning of the eighties rare earth calcining matter leach liquor and the main CaCO that adopts
3, cause to produce a large amount of CaSO
42H
2The O precipitation, the quantity of slag is too big, has a strong impact on the rare earth yield.The reason that does not adopt alkali metal hydroxide or salt is that alkali metal sulfates and rare earth metal vitriol generate double salt precipitation, influences the rare earth yield.Use the MgO neutralization instead to the end of the eighties, because of MgSO
4The solubleness height also can not generate double salt with rare earth sulfate and cause the rare earth loss in water, and this technology is used till today always.Be to improve the leaching yield and the strength of solution of rare earth infusion, can adopt the way that adds hydrochloric acid or nitric acid in the leaching process, obtain sulfur-bearing hydrochlorate, muriate, nitrate is a kind of or the re dip solution of 2-3 kind.Rare earth calcining matter leach liquor is infusion after neutralizing, consist of: REO15～60g/L, CaSO
4(in CaO) 0.5～1g/L is actual to be CaSO
4Saturated solution, MgSO
4(in MgO) 1～10g/L.
Three, wastewater source.
Infusion through making is a sulphuric acid soln, forwards hydrochloric acid, nitric acid system in the production mostly as required to.Three kinds of technologies of industrial main employing also just have three kinds of processing wastewaters to produce at present.
The first kind: rare earth element separates with rare earth element
Adopt the non-saponified P204 in Beijing Non-Ferrous Metal Research General Academy Rare Earth Separation technology.Through non-saponified P204 Nd/Sm grouping, raffinate is through MgO neutralization, clarification, again through non-saponified P204 extracting and separating light rare earths and non-rare earth impurity earlier for infusion.
Waste water results from sulfuric acid process and handles the sulfur-bearing hydrochlorate that rare earths material obtains, muriate, one or more rare earth infusion of nitrate, through non-saponified P204 (D2EHPA, two (ethylhexyl dihydrogen phosphates) and non-saponified P507 (DEH/EHA, di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester) C272 (two (2,4,4 tri-methyl-amyls) phosphonic acids, C301 (two (2,4, the 4-tri-methyl-amyl) phosphonothionic acid, C302 (two (2,4, the 4-tri-methyl-amyl) single phosphonothionic acid, kerosene, the waste water that the single or composite extractant extracting and separating of one or more configurations in the sulfonated kerosene produces.
Second class: rare earth element separates with non-rare earth
Waste water results from sulfuric acid process and handles one or more rare earth infusion of sulfur-bearing hydrochlorate that rare earths material obtains, muriate, nitrate, and rare earth the infusion directly single or composite extractant extraction of one or more configurations in non-saponified P204 and non-saponified P507, C272, C301, C302, HEOPPA, kerosene, sulfonated kerosene makes rare earth element separate the waste water of generation with non-rare earth.
The first kind and the second class wastewater source, extraction back waste water composition is: [H
+] 0.1～0.5mol/L, MgSO
4(in MgO) 1～8g/L, CaSO
4(in CaO) 0.5～1g/L is actual to be CaSO
4Saturated solution and SO
4 2-, Cl
-, NO
3 -In one or more.This part waste water is because of containing a large amount of MgSO
4, easily enrichment can't recycle.After simply neutralizing, CaO discharges or is stored in tailing dam at present.Because of containing extraction agent 20～100mg/L in the waste water, (belonging to petroleum-type, national secondary discharge standard: petroleum-type≤10mg/L), high rigidity, high salinity, contaminate environment, a large amount of waste water resources.
The 3rd class: waste water results from sulfuric acid process and handles one or more rare earth infusion of sulfur-bearing hydrochlorate that rare earths material obtains, muriate, nitrate, produces the waste water that mixed rare earth carbonate produces through carbonic acid (hydrogen) ammonium precipitation.
With infusion NH
4HCO
3, (NH
4)
2CO
3Precipitation is produced mixed rare earth carbonate, then with hydrochloric acid or nitric acid dissolve, through the various single rare earth oxide compounds of P507 separation of produced.In precipitation process, non-rare earth impurity Ca also with the rare earth coprecipitation reaction formula that comes out is:
CaSO
4+2N
H4HCO
3＝Ca?CO
3↓+CO
2+H
2O+(NH
4)
2SO
4
MgSO
4Deposition condition does not possess and major part is stayed in the solution.Therefore in precipitation waste water, be rich in (NH
4)
2SO
4, MgSO
4Its concentration is respectively MgSO
4(in MgO) 1～8g/L, ammonia nitrogen is (with NH
3Meter) 2000～20000mg/L.
Because of NH
4HCO
3(agricultural carbon ammonium) cheap and easy to get and a large amount of uses to produce the mixed rare earth carbonate of 75000 tons (with REO) year, need 125000 tons of agricultural carbon ammoniums, year 6000000 to 1,000 ten thousand tons of waste water of waste discharge, and year discharging ammonia nitrogen is (with NH
3Meter) 26000 ton.This part waste water is because of containing (NH
4)
2SO
4, MgSO
4Deng impurity, easily enrichment can't recycle.Not carrying out any processing at present enters rivers or is stored in tailing dam.NH
3Emission concentration is 2000～20000mg/L, surpasses national secondary discharge standard (NH
380～800 times of :≤25mg/L).
Four, waste water treatment process
To the 3rd class lower concentration and high density ammonium salt wastewater treatment method.Lower concentration ammonium salt waste water adopts on the similar soda industry in the hydrazine method technology commonly used gas formulation technology (prior art) to remove the NH3 operation, and high density ammonium salt waste water adopts and concentrates way and reclaim.Lower concentration ammonium salt method of wastewater treatment away from feasible, but also have some not enough: 1. lower concentration ammonium salt waste water generation is huge, and gas is carried the huge equipment that needs, invest huge, need to consume a large amount of energy and resource, with high costs, this is that rare-earth trade is unacceptable; 2. lower concentration ammonium salt waste water especially contains MgSO in the mixed rare earth carbonate factory effluent of generation maximum
4(in MgO) 1～8g/L with enrichment, can't circulate; 3. not polluting from the control of technology source, do not adopt raw material, the technology of cleaning, do not meet the cleaner production requirement, is a kind of passive treating method.High density ammonium salt wastewater treatment way is feasible, industrial existing use.But this part waste water generation very little (accounting for rare-earth trade wastewater flow rate 5%～10%) and be scattered in each rare earth enterprise; 4. high density ammonium salt waste water can adopt gas formulation or method of enrichment to remove NH
3
To containing the method for ammonium chloride Rare Earth Separation waste liquid.This technology adds the MgO or the vitriol oil in waste water or ammonia chloride crystal.In MgO technology, adopt MgO replaced C aO, also adopted in the hydrazine method technology commonly used on the similar soda industry gas formulation technology to remove NH
3Operation.This technology is feasible, and rare-earth industry also has use, can handle high density ammonium salt waste water.But the MgO price is than high many of CaO, and industrial whole employing CaO carry out gas and carry except that NH
3Operation.Especially mixed rare earth carbonate waste water is then infeasible for this art breading lower concentration ammonium salt waste water.Adopt solid NH in the vitriol oil technology
4Cl and strong sulfuric acid response make NH
3And HCl.
Precipitate the waste water of producing mixed rare earth carbonate and infusion directly being produced through extracting and separating owing to produce a large amount of waste water, especially infusion in the Rare Earth Production process.Mixed rare earth carbonate is produced because of a large amount of NH of use
4HCO
3, (NH
4)
2CO
3Deng, discharge contains low-concentration ammonia-nitrogen, Mg
2+Waste water, the production cost height, wherein low-concentration ammonia-nitrogen is difficult for handling.Contain Mg in the waste water that infusion produces through extracting and separating
2+, this is the principal element that restriction waste water recycles.Infusion precipitation production mixed rare earth carbonate is just progressively replaced by the method for the direct extracting and separating of infusion at present.
Summary of the invention the purpose of this invention is to provide a kind of method that can change the RE waste water treating complete circulation of rare-earth trade pollution, to solve the problems that the medium-term and long-term a large amount of dischargings of Rare Earth Production contain ammonia nitrogen, acidity, high rigidity, high salinity waste water.
First kind of embodiment of the present invention is to be the first kind rare earth element waste water that separates generation with rare earth element and the second class rare earth element separate generation with non-rare earth waste water at wastewater source,
It comprises the following steps,
(1) in and operation
Rare earth acid waste water flows into neutralizing well and neutralizes through neutralizing agent, and neutralization back pH is 5～11; Neutralizing agent is a kind of or 2-3 kind neutralizing agent compound, and is compound in the 1-99% ratio.Neutralizing agent is selected from the oxide compound of alkaline-earth metal (Ca, Mg, Sr, Ba), the sulfide of (Ca, Mg, Sr, Ba), the carbonate of (Ca, Mg, Sr, Ba), the oxyhydroxide of (Ca, Mg, Sr, Ba), add-on is in 100% oxide compound pure substance, and per 1000 milliliters of waste water add neutralizing agent 2g～55g.
(2), degree of depth precipitation process operation
Waste water enters the clarifying tank clarification or directly enters degree of depth precipitation process groove, and this operation is provided with the two-stage steel basin, i.e. degree of depth precipitation process groove and precipitation clarifying tank, waste water and degree of depth precipitation agent all enter degree of depth precipitation process groove, enter the precipitation clarifying tank again, it is 9～13 that precipitation finishes back pH, makes Mg
2+Become Mg (OH) fully
2Precipitation is separated out; Mg
2+(in MgO)≤0.1%.Degree of depth precipitation agent is a kind of or 2-3 kind degree of depth precipitation agent compound, and is compound in the 1-99% ratio.Degree of depth precipitation agent is selected from the oxide compound of alkaline-earth metal (Ca, Mg, Sr, Ba), the sulfide of (Ca, Mg, Sr, Ba), the carbonate of (Ca, Mg, Sr, Ba), the oxyhydroxide of (Ca, Mg, Sr, Ba), add-on is in 100% oxide compound pure substance, and per 1000 milliliters of waste water add neutralizing agent 0.5g～30g.
Degree of depth precipitation process operation is a critical process of the present invention, has solved waste water and recycle restraining factors in this operation.The factor that restriction waste water recycles is mainly Mg
2+, contain Mg in the waste water
2+(in MgO) 0.1%～0.8% is with MgSO
4Be present in the aqueous solution, do not remove this material, Mg
2+Concentration can be with 2
n(n is the waste water cycle index) doubly speed increases, and has a strong impact on water quality.For removing this material, must add degree of depth precipitation agent.Principal reaction is following (with Ca (OH)
2Be example):
Mg
2++Ca(OH)
2＝Mg(OH)
2↓+Ca
2+
Mg (OH)
2Precipitation is separated out.
Ca
2+(in CaO) 0.05%～0.1% is with CaSO
4Saturated solution exist, actual saturated in handle the infusion that rare earths material obtains with sulfuric acid process, the CaSO that in the first operation N-process, produces
4Also precipitation is separated out, and concentration can not increase.Clarification back waste water is removed most of non-rare earth impurity in the waste water through degree of depth precipitation agent precipitation; Generate Mg (OH) in second operation
2Precipitation is separated out, CaSO
4Supersaturation is separated out.Here first, second operation is separately carried out, the Mg (OH) that generates in the time of can avoiding first, second operation to finish in a groove
2Precipitation stops the milk of lime particulate further to react attached to the milk of lime particle surface, increases milk of lime consumption.Waste water is Mg after degree of depth precipitation process operation is handled
2+(in MgO)≤0.1%.
(3), adjust operation, adding acid waste water readjustment pH to 6-9.
It is pH to be adjusted into 6～9 backs use that readjustment is handled; Waste water also can be clarified the back and directly use.The waste water of handling through the 3rd operation has following purposes 1. to be used for the water logging operation; 2. be used to modulate neutralizing agent, degree of depth precipitation agent 3. suitably dilution back conduct greening, landscape water.
Second kind of embodiment of the present invention is to be the 3rd class at wastewater source, waste water results from sulfuric acid process and handles one or more rare earth infusion of sulfur-bearing hydrochlorate that rare earths material obtains, muriate, nitrate, produces the waste water that mixed rare earth carbonate produces through carbonic acid (hydrogen) ammonium precipitation.Because of containing NH in the waste water
4 +(with NH
3Meter) 0.2～2%, NH in the working cycle
4 +With 2
n(n is the waste water cycle index) must take measures, and can adopt gas to put forward technology and reclaim, removes NH
4 +Treatment step comprises that (2) degree of depth precipitation process operation and (3) adjust operation, in not having and operation.The wastewater pH of handling through degree of depth precipitation process operation is 9～13, and ammonia nitrogen is by NH in this moment waste water
4 +Change NH into
3, both changed free ammonia into by fixed ammonia, just in time meet ammonia and carry arts demand.
The present invention adopts the advanced treatment technology, has removed the unfavorable factor of restriction cycling utilization of wastewater, makes waste water reach the Rare Earth Production demanding criteria fully, reaches 100% and recycles, and reaches the cleaner production requirement.Waste water recycles after treatment fully, does not efflux, and guarantees not enrichment of impurity in the waste water, and treated water quality reaches the production service requirements.Thoroughly change rare-earth trade and pollute image.The used starting material of the present invention are easy to get, and material price is cheap, and technology is simple, so processing costs is very low.About 1～2 yuan of cost for wastewater treatment per ton as calculated.
Description of drawings
Fig. 1 is the schema of first kind of embodiment of the present invention.
Embodiment
The following examples can make those skilled in the art more fully understand the present invention, but do not limit the present invention in any way.
The selection of treatment step, neutralizing agent and degree of depth precipitation agent and concentration, consumption, flow velocity are referring to table 1 among each embodiment.
[embodiment 1] wastewater source is second class: rare earth element separates with non-rare earth
Principal element in the waste water: [H
+] 0.3mol/L, Mg
2+(in MgO) 4g/L, Ca
2+(in CaO) 0.6～0.8g/L, 1.0L/min, actual is CaSO
4Saturated solution.
(1) in and operation
Configuration concentration is 20% Ca (OH)
2Milk sap is standby, and rare earth acid waste water flows into neutralizing well, neutralizing agent Ca (OH) with the flow velocity of 1.0L/min
2Milk sap flows into neutralizing well with the flow velocity of 0.05L/min, and CaSO is arranged in the N-process
4Generate, and supersaturation is separated out.Neutralization back pH is 5～11.
(2), degree of depth precipitation process operation
Waste water enters clarifying tank clarification or directly enters degree of depth precipitation process groove, and this operation is provided with the two-stage steel basin, i.e. degree of depth precipitation process groove and precipitation clarifying tank, and waste water and concentration are 20% Ca (OH)
2Milk sap enters degree of depth precipitation process groove with the flow velocity of 0.04L/min, enters the precipitation clarifying tank again, and it is 9～13 that precipitation finishes back pH, generates Mg (OH) in this operation
2Precipitation is separated out, CaSO
4Supersaturation is separated out.Here separately carry out with operation and degree of depth precipitation process operation in, in the time of can avoiding two-step in a groove, to finish, the Mg of generation (OH)
2Precipitation stops the milk of lime particulate further to react attached to the milk of lime particle surface, increases milk of lime consumption.Make Mg
2+Become Mg (OH) fully
2Precipitation is separated out; Mg
2+(in MgO)≤0.1%,
(3), adjust operation
Directly use after adding acid waste water readjustment pH to 6-9.
[embodiment 2] wastewater source is the first kind: rare earth element separates with rare earth element
Treatment step is with embodiment 1.
[embodiment 3] wastewater source is the first kind: rare earth element separates with rare earth element
Treatment step is with embodiment 1.
[embodiment 4] wastewater source is second class: rare earth element separates with non-rare earth
(1) in and operation
Get 1.0L rare earth acid waste water, adding principal constituent content is 96% CaCO
320g neutralizes, and neutralization back pH is 5～11.
(2), degree of depth precipitation process operation
Above-mentioned waste water is after clarification, and it is that 92% CaO 1g and principal constituent content are 96% Ba (OH) that waste, supernatant liquor add principal constituent content
2The compound degree of depth precipitation agent of 2g makes Mg
2+Become Mg (OH) fully
2Precipitation is separated out; Mg
2+(in MgO)≤0.1%.
(3), adjust operation
Directly use after adding acid waste water readjustment pH to 6-9.
[embodiment 5] wastewater source is second class: rare earth element separates with non-rare earth
Treatment step is with embodiment 4.
[embodiment 6] wastewater source is the 3rd class: waste water results from sulfuric acid process and handles one or more rare earth infusion of sulfur-bearing hydrochlorate that rare earths material obtains, muriate, nitrate, produces the waste water that mixed rare earth carbonate produces through carbonic acid (hydrogen) ammonium precipitation.
Treatment step is that operation is adjusted in (2) degree of depth precipitation process operation and (3), in not having and operation.
[embodiment 7] wastewater source is second class: rare earth element separates with non-rare earth
Treatment step is with embodiment 4.Neutralizing agent is composited by two kinds, and degree of depth precipitation agent is composited by two kinds.
[embodiment 8] wastewater source is the first kind: rare earth element separates with rare earth element
Treatment step is with embodiment 4.Neutralizing agent is composited by three kinds, and degree of depth precipitation agent is composited by three kinds.
[embodiment 9] wastewater source is second class: rare earth element separates with non-rare earth
Treatment step is with embodiment 4.Neutralizing agent is composited by two kinds, and degree of depth precipitation agent is composited by two kinds.
[embodiment 10] wastewater source is the first kind: rare earth element separates with rare earth element
Treatment step is with embodiment 4.Neutralizing agent is composited by two kinds, and degree of depth precipitation agent is composited by three kinds.
[embodiment 11] wastewater source is second class: rare earth element separates with non-rare earth
Treatment step is with embodiment 4.Neutralizing agent is composited by two kinds, and degree of depth precipitation agent is composited by two kinds.
[embodiment 12] wastewater source is second class: rare earth element separates with non-rare earth
Treatment step is with embodiment 4.Neutralizing agent is composited by two kinds, and degree of depth precipitation agent is composited by a kind of.
Claims (6)
1, rare earth element separates generation with rare earth element waste water and rare earth element separates the waste water of generation with non-rare earth method is handled in a kind of recycle to extinction, it is characterized in that: it comprises the following steps,
(1) in and operation
Rare earth acid waste water flows into neutralizing well and neutralizes through neutralizing agent, and neutralization back pH is 5～11;
(2), degree of depth precipitation process operation
Waste water enters degree of depth precipitation process groove again or directly enters degree of depth precipitation process groove after entering the clarifying tank clarification, this operation is provided with the two-stage steel basin---degree of depth precipitation process groove and precipitation clarifying tank, waste water and degree of depth precipitation agent all enter degree of depth precipitation process groove, enter the precipitation clarifying tank again, it is 9～13 that precipitation finishes back pH;
(3), adjust operation
Add acid waste water readjustment pH to 6-9.
2, the method that the rare earth infusion is produced the waste water that mixed rare earth carbonate produces through the volatile salt precipitation is handled in a kind of recycle to extinction, it is characterized in that: it comprises the following steps,
A, degree of depth precipitation process operation
Waste water enters degree of depth precipitation process groove again or directly enters degree of depth precipitation process groove after entering the clarifying tank clarification, this operation is provided with the two-stage steel basin, be degree of depth precipitation process groove and precipitation clarifying tank, waste water and degree of depth precipitation agent all enter degree of depth precipitation process groove, enter the precipitation clarifying tank again, it is 9～13 that precipitation finishes back pH;
B, adjustment operation
Add acid waste water readjustment pH to 6-9.
3, the method for RE waste water treating complete circulation according to claim 1 is characterized in that: described neutralizing agent is a kind of or 2-3 kind neutralizing agent compound, and is compound in the 1-99% ratio; Neutralizing agent is selected from oxide compound, sulfide, carbonate, the oxyhydroxide of alkaline-earth metal, and add-on is in 100% oxide compound pure substance, and per 1000 milliliters of waste water add neutralizing agent 2g～55g.
4, the method for RE waste water treating complete circulation according to claim 3 is characterized in that: described neutralizing agent is selected from calcium oxide, magnesium oxide, strontium oxide, barium oxide, sulfurated lime, magnesium sulfide, strontium sulfide, barium sulphide, lime carbonate, magnesiumcarbonate, Strontium carbonate powder, barium carbonate, calcium hydroxide, magnesium hydroxide, strontium hydroxide, hydrated barta.
5, according to the method for claim 2 or 4 described RE waste water treating complete circulations, it is characterized in that: described degree of depth precipitation agent is a kind of or 2-3 kind degree of depth precipitation agent compound, and is compound in the 1-99% ratio; Degree of depth precipitation agent is selected from oxide compound, sulfide, carbonate, the oxyhydroxide of alkaline-earth metal, and add-on is in 100% oxide compound pure substance, and per 1000 milliliters of waste water add neutralizing agent 0.5g～30g.
6, the method for RE waste water treating complete circulation according to claim 5 is characterized in that: described degree of depth precipitation agent is selected from calcium oxide, magnesium oxide, strontium oxide, barium oxide, sulfurated lime, magnesium sulfide, strontium sulfide, barium sulphide, lime carbonate, magnesiumcarbonate, Strontium carbonate powder, barium carbonate, calcium hydroxide, magnesium hydroxide, strontium hydroxide, hydrated barta.
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|---|---|---|---|
| CNB2007100182461A CN100506724C (en) | 2007-06-26 | 2007-06-26 | RE waste water treating complete circulation process |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102079601B (en) * | 2009-11-30 | 2012-06-27 | 中国科学院广州地球化学研究所 | Resource recovery and zero discharge process for treating rare-earth wet-method smelting wastewater |
| CN101967559A (en) * | 2010-07-20 | 2011-02-09 | 包头市京瑞新材料有限公司 | Self recycling method of waste water in rare earth carbonate precipitation |
| CN102041389B (en) * | 2010-11-05 | 2012-08-29 | 内蒙古包钢稀土(集团)高科技股份有限公司 | Method for producing rare earth carbonate by recycling rare earth carbonate precipitation waste liquid |
| CN102260000B (en) * | 2011-07-22 | 2012-12-12 | 内蒙古介电电泳应用技术研究院 | Process for treating and recycling ammonium chloride rare earth wastewater |
| CN102260002B (en) * | 2011-07-22 | 2013-01-30 | 内蒙古介电电泳应用技术研究院 | Process for treating and recycling rare earth wastewater containing high-concentration sodium chloride and ammonium chloride |
| WO2015184592A1 (en) * | 2014-06-03 | 2015-12-10 | 中国科学院福建物质结构研究所 | Method of purifying rare earths from rare earth refined industrial waste water |
| CN105293558B (en) * | 2014-06-03 | 2017-02-22 | 中国科学院福建物质结构研究所 | Method for purifying rare earth from rare earth extracting and purifying industrial wastewater |
| CN104211106B (en) * | 2014-09-01 | 2016-08-24 | 赣州鑫隆康稀土有限公司 | A kind of carbonated rare earth preparation method not producing ammonia nitrogen waste water |
| CN105948695B (en) * | 2015-01-31 | 2018-02-27 | 王明华 | A kind of purposes of sewage purification material |
| CN105439220B (en) * | 2016-01-19 | 2018-04-17 | 山东广景环境科技有限公司 | A kind of sewage-treating agent and preparation method thereof |
| CN105836918A (en) * | 2016-04-12 | 2016-08-10 | 包头稀土研究院 | Technological method of rare earth industrial wastewater treatment and cyclic utilization |
| CN109207732B (en) * | 2018-09-26 | 2020-06-09 | 绍兴文理学院 | Rare earth extraction system and method for rare earth tricolor fluorescent powder wastewater for lamp |
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