CN109293048A - A kind of method of RE waste water resource reutilization - Google Patents

A kind of method of RE waste water resource reutilization Download PDF

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Publication number
CN109293048A
CN109293048A CN201811218582.5A CN201811218582A CN109293048A CN 109293048 A CN109293048 A CN 109293048A CN 201811218582 A CN201811218582 A CN 201811218582A CN 109293048 A CN109293048 A CN 109293048A
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China
Prior art keywords
waste water
rare earth
oxalic acid
acid
solid
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Inventor
韦世强
娄战荒
吴忠何
张亮玖
莫国荣
龙江志
周慧荣
江泽佐
卢阶主
杨金涛
庄辉
羊多彦
李飞龙
况涛
许旭升
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Chalco Guangxi Guosheng Rare Earth Development Co Ltd
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Chalco Guangxi Guosheng Rare Earth Development Co Ltd
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Priority to CN201811218582.5A priority Critical patent/CN109293048A/en
Publication of CN109293048A publication Critical patent/CN109293048A/en
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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
    • 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
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • 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
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • 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
    • C02F2001/007—Processes including a sedimentation step

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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)
  • Manufacture And Refinement Of Metals (AREA)
  • Removal Of Specific Substances (AREA)

Abstract

The present invention relates to a kind of method of RE waste water resource reutilization, this method includes wastewater collection, detection, carbonic acid-oxalic acid precipitation, separation of solid and liquid, ore leachate preparation, leaching mine, by that will contain NH4 +Ammonium carbonate precipitating rare earth waste water, the acid oxalic acid precipitation RE waste water containing oxalic acid and the extraction wastewater containing rare earth element carbonic acid-oxalic acid precipitation reaction occur remove CO3 2‑/HCO3 ‑, oxalic acid, then be separated by solid-liquid separation obtain hydrochloric, NH4Cl is free of CO3 2‑/HCO3 ‑, oxalic acid acid waste water, adjust acid waste water in NH4Cl mass percent and pH value obtain leaching mine of the acid ore leachate for Rare Earth Mine.The present invention is realized containing NH simultaneously4 +Ammonium carbonate precipitating rare earth waste water, the acid oxalic acid precipitation RE waste water containing oxalic acid and the extraction wastewater containing rare earth element recycling, avoid the wasting of resources and contaminated wastewater, the purchase cost of ore leachate, with good economic efficiency, social benefit and environmental benefit have been saved simultaneously.

Description

A kind of method of RE waste water resource reutilization
Technical field
The invention belongs to RE waste water process fields, and in particular to a kind of method of RE waste water resource reutilization.
Background technique
China is rare earth resources big country, and yield ranks first in the world.Rare earth element has excellent due to its special structure of matter Different physics, chemistry, magnetic, light and electric property has extremely wide purposes, the referred to as strategic element of 21 century.With People are abundant and cheap to the continuous research of rare earth element performance and application and understanding and by China's rare earth resources Advantage, rare earth are just protected in China's household electrical appliance, daily-use chemical industry, Ferrous Metallurgy, petrochemical industry, laser technology, superconductor, medical treatment Strong, agriculture and forestry and environmental protection etc. have been more and more widely used in fields.Rare-earth extraction separating process process can be divided into three A aspect, i.e. feed liquid pre-treatment, solvent extraction and separation process and product finishing post-processing.Feed liquid pre-treatment is to be put into concentrate Acidleach is carried out in sulfuric acid, then through processes such as dissolution, separation, purification, concentration or calcinations, various mixed rare earth compounds is made and produce Product；Solvent extraction and separation be mixed rare earth solution is separated, is enriched with, extract obtain required purity and yield rare earth produce Product；Post-processing is to obtain extraction separation process single rare earth product obtained finally by processes such as precipitating, filtering, roastings Solid product, i.e. rare earth oxide.
During Rare Earth Production, the waste water that ammonium carbonate precipitating rare earth technique generates contains NH4 +、CO3 2-/HCO3 -Deng belonging to Ammoniated wastewater, general processing method are unable to reach NH4 +、CO3 2-/HCO3 -The requirement sufficiently recycled；Oxalic acid precipitation rare earth The waste water that technique generates contains oxalic acid, hydrochloric acid etc., belongs to peracidity waste water, general processing method is unable to reach oxalic acid, hydrochloric acid The requirement sufficiently recycled.Ammonium carbonate precipitating rare earth waste water and the processing of oxalic acid precipitation RE waste water not up to standard can cause water body Very big pollution.
Rare Earth Mine generallys use NH4Cl slightly puts forward rare earth element as ore leachate, and rare earth element ion is in acid item Under part by with NH4 +Exchange occurs and is leached in ore leachate.Enterprise generally take addition be commercialized ammonium sulfate, sulfuric acid, The acid NH of the reagents such as hydrochloric acid preparation4Cl ore leachate, virtually increases production cost.
Therefore, NH will be contained4 +、CO3 2-/HCO3 -RE waste water recycling removal CO3 2-/HCO3 -, recycle NH4 +Preparation acid Property NH4Cl ore leachate not only can solve the processing problem of waste water, can also save enterprise's production cost, have good open Hair prospect.
Summary of the invention
The purpose of the present invention is overcome the deficiencies of the prior art and provide a kind of method of RE waste water resource reutilization.
The present invention realizes in the following way:
A kind of method of RE waste water resource reutilization, comprising the following steps:
(1) NH wastewater collection: will be contained4 +Ammonium carbonate precipitating rare earth waste water, the acid oxalic acid precipitation RE waste water containing oxalic acid, Extraction wastewater containing rare earth element is collected into different ground catch basins respectively；
(2) detect: detection contains NH respectively4 +Ammonium carbonate precipitating rare earth waste water in CO3 2-/HCO3 -Substance withdrawl syndrome, containing grass The object of rare earth element in the substance withdrawl syndrome of oxalic acid precipitation RE waste water mesoxalic acid of acid and the extraction wastewater containing rare earth element The amount concentration of matter；
(3) oxalic acid-carbonic acid precipitating: according to the testing result of step (2), NH will be contained by controlling volume ratio4 +Ammonium carbonate precipitating rare earth Waste water, the oxalic acid precipitation RE waste water containing oxalic acid and the extraction wastewater containing rare earth element import agitating reaction pond, open stirring 10- 30 min, make CO3 2-/HCO3 -, oxalic acid respectively with rare earth element occur precipitation reaction make in composite waste after the reaction was completed CO3 2-/HCO3 -Substance withdrawl syndrome be 0-0.0001 mol/L, the substance withdrawl syndrome of oxalic acid is 0-0.0001 mol/L, dilute The substance withdrawl syndrome of earth elements is 0.0005-0.001 mol/L, realizes CO in removal RE waste water3 2-/HCO3 -, oxalic acid mesh 's；
(4) it is separated by solid-liquid separation: the composite waste after the completion of precipitation reaction being introduced into solid-liquid separation tank, composite waste is in solid-liquid separation tank It is inside separated by solid-liquid separation from top to bottom, the first drainage plate is flowed by skirt first, has filter cartridge, composite waste on the first drainage plate Filter cartridge carry out first time separation of solid and liquid, then through the second drainage plate flow into filter mechanism, composite waste filter mechanism into Second of separation of solid and liquid of row realizes that solid-liquid is kept completely separate, filter residue is heavy for oxalic acid finally by being separated by solid-liquid separation the filter plate of bottom of pond portion Shallow lake rare earth and carbonic acid precipitating rare earth, are used to prepare rare-earth products, and filtrate is containing NH4 +、H+、Cl-, be free of CO3 2-/HCO3 -And oxalic acid Acid waste water；
(5) prepared by ore leachate: adjusting NH in acid waste water4 +Mass percent be 2-5%, pH value 4-5, obtain acid NH4Cl ore leachate；
(6) mine is soaked: by acid NH4Cl ore leachate soaks mine, under acid condition, rare earth element ion and NH for Rare Earth Mine4 +Hair Life is exchanged and is leached in ore leachate, is realized and is contained NH4 +Ammonium carbonate precipitating rare earth waste water reuse.
Preferably, described to contain NH4 +Ammonium carbonate precipitating rare earth waste water in CO3 2-/HCO3 -Substance withdrawl syndrome be 0.5- 1.0 mol/L, NH4 +Mass percent be 0.5-3%.
Preferably, the substance withdrawl syndrome 0.05-0.3 mol/ of the oxalic acid precipitation RE waste water mesoxalic acid containing oxalic acid L, pH 1-2.
Preferably, described to contain NH4 +Ammonium carbonate precipitating rare earth waste water include ammonium carbonate precipitating rare earth mother liquor waste water, ammonium carbonate Precipitating rare earth washes.
Preferably, the oxalic acid precipitation RE waste water containing oxalic acid includes oxalic acid precipitation rare earth mother solution waste water, oxalic acid precipitation Rare earth washes.
Preferably, in the extraction wastewater containing rare earth element rare earth element substance withdrawl syndrome 0.008-0.01 mol/L。
Preferably, in step (3), after the reaction was completed, make CO in composite waste3 2-/HCO3 -Substance withdrawl syndrome be 0- The substance withdrawl syndrome of 0.00005 mol/L, oxalic acid are 0-0.00005 mol/L, and the substance withdrawl syndrome of rare earth element is 0.0008-0.001 mol/L。
Preferably, the NH4NH in Cl ore leachate4 +Mass percent be 4%.
Preferably, the NH4The pH value of Cl ore leachate is 4.
The beneficial effects of the present invention are:
1. the present invention can be to containing NH4 +Ammonium carbonate precipitating rare earth waste water in NH4 +、CO3 2-/HCO3 -It reuses, avoids again NH4 +、CO3 2-/HCO3 -The wasting of resources and contaminated wastewater.
2. the present invention can to containing oxalic acid oxalic acid precipitation RE waste water mesoxalic acid and hydrochloric acid reuse again, avoid The acid solution wasting of resources and contaminated wastewater
3. the present invention can precipitate again recycling to the rare earth element in the extraction wastewater containing rare earth element, rare earth resources are avoided Waste and extraction wastewater pollution.
4. reducing Rare Earth Production cost present invention saves the buying of ore leachate reagent.
5. solid-liquid separating method of the invention is Dynamic Separation method, avoid in traditional settled process solid-liquid layering low efficiency, The defect of inferior separating effect, and be automatically separated from high to low using gravitional force, save energy consumption.
6. the present invention improves the recycling and utilization rate of each resource in Rare Earth Production, mitigate waste water treatment cost, and operate Simply, low in cost, with good economic efficiency and social benefit.
Specific embodiment
The invention will be further described combined with specific embodiments below, but does not limit the scope of the invention and apply Range.
Embodiment 1
A kind of method of RE waste water resource reutilization, comprising the following steps:
(1) NH wastewater collection: will be contained4 +Ammonium carbonate precipitating rare earth waste water, the acid oxalic acid precipitation RE waste water containing oxalic acid, Extraction wastewater containing rare earth element is collected into different ground catch basins respectively；It is described to contain NH4 +Carbonated rare earth it is useless in NH4 +'s Mass percent is 0.5-3%, including ammonium carbonate precipitating rare earth mother liquor waste water, ammonium carbonate precipitating rare earth washes；It is described to contain grass PH is 2 in the oxalic acid precipitation RE waste water of acid, including oxalic acid precipitation rare earth mother solution waste water, oxalic acid precipitation rare earth washes；
(2) detect: detection contains NH respectively4 +Ammonium carbonate precipitating rare earth waste water in CO3 2-/HCO3 -Substance withdrawl syndrome, containing grass The object of rare earth element in the substance withdrawl syndrome of oxalic acid precipitation RE waste water mesoxalic acid of acid and the extraction wastewater containing rare earth element The amount concentration of matter；Wherein CO3 2-/HCO3 -Substance withdrawl syndrome be 0.8 mol/L, 0.3 mol/ of substance withdrawl syndrome of oxalic acid L, 0.01 mol/L of substance withdrawl syndrome of rare earth element；
(3) oxalic acid-carbonic acid precipitating: according to the testing result of step (2), NH will be contained by controlling volume ratio4 +Ammonium carbonate precipitating rare earth Waste water, the oxalic acid precipitation RE waste water containing oxalic acid and the extraction wastewater containing rare earth element import agitating reaction pond, open stirring 20 Min makes CO3 2-/HCO3 -, oxalic acid respectively with rare earth element occur precipitation reaction make CO in composite waste after the reaction was completed3 2-/ HCO3 -Substance withdrawl syndrome be 0.00001 mol/L, the substance withdrawl syndrome of oxalic acid is 0.00001 mol/L, rare earth element Substance withdrawl syndrome be 0.0008 mol/L, realize removal RE waste water in CO3 2-/HCO3 -, oxalic acid purpose；
(4) it is separated by solid-liquid separation: the composite waste after the completion of precipitation reaction being introduced into solid-liquid separation tank, composite waste is in solid-liquid separation tank It is inside separated by solid-liquid separation from top to bottom, the first drainage plate is flowed by skirt first, has filter cartridge, composite waste on the first drainage plate Filter cartridge carry out first time separation of solid and liquid, then through the second drainage plate flow into filter mechanism, composite waste filter mechanism into Second of separation of solid and liquid of row realizes that solid-liquid is kept completely separate, filter residue is heavy for oxalic acid finally by being separated by solid-liquid separation the filter plate of bottom of pond portion Shallow lake rare earth and carbonic acid precipitating rare earth, are used to prepare rare-earth products, and filtrate is containing NH4 +、H+、Cl-, be free of CO3 2-/HCO3 -And oxalic acid Acid waste water；
(5) prepared by ore leachate: adjusting NH in acid waste water4 +Mass percent be 4%, pH value 4 obtains acid NH4Cl leaching Mine liquid；
(6) mine is soaked: by acid NH4Cl ore leachate soaks mine, under acid condition, rare earth element ion and NH for Rare Earth Mine4 +Hair Life is exchanged and is leached in ore leachate, is realized and is contained NH4 +Ammonium carbonate precipitating rare earth waste water reuse.
Embodiment 2
A kind of method of RE waste water resource reutilization, comprising the following steps:
(1) NH wastewater collection: will be contained4 +Ammonium carbonate precipitating rare earth waste water, the acid oxalic acid precipitation RE waste water containing oxalic acid, Extraction wastewater containing rare earth element is collected into different ground catch basins respectively；It is described to contain NH4 +Carbonated rare earth it is useless in NH4 +'s Mass percent is 0.5%, including ammonium carbonate precipitating rare earth mother liquor waste water, ammonium carbonate precipitating rare earth washes；It is described to contain oxalic acid Oxalic acid precipitation RE waste water in pH be 1, including oxalic acid precipitation rare earth mother solution waste water, oxalic acid precipitation rare earth washes；
(2) detect: detection contains NH respectively4 +Ammonium carbonate precipitating rare earth waste water in CO3 2-/HCO3 -Substance withdrawl syndrome, containing grass The object of rare earth element in the substance withdrawl syndrome of oxalic acid precipitation RE waste water mesoxalic acid of acid and the extraction wastewater containing rare earth element The amount concentration of matter；Wherein CO3 2-/HCO3 -Substance withdrawl syndrome be 0.5 mol/L, 0.05 mol/ of substance withdrawl syndrome of oxalic acid L, 0.01 mol/L of substance withdrawl syndrome of rare earth element；
(3) oxalic acid-carbonic acid precipitating: according to the testing result of step (2), NH will be contained by controlling volume ratio4 +Ammonium carbonate precipitating rare earth Waste water, the oxalic acid precipitation RE waste water containing oxalic acid and the extraction wastewater containing rare earth element import agitating reaction pond, open stirring 30 Min makes CO3 2-/HCO3 -, oxalic acid respectively with rare earth element occur precipitation reaction make CO in composite waste after the reaction was completed3 2-/ HCO3 -Substance withdrawl syndrome be 0.00005 mol/L, the substance withdrawl syndrome of oxalic acid is 0.00005 mol/L, rare earth element Substance withdrawl syndrome be 0.0005 mol/L, realize removal RE waste water in CO3 2-/HCO3 -, oxalic acid purpose；
(4) it is separated by solid-liquid separation: the composite waste after the completion of precipitation reaction being introduced into solid-liquid separation tank, composite waste is in solid-liquid separation tank It is inside separated by solid-liquid separation from top to bottom, the first drainage plate is flowed by skirt first, has filter cartridge, composite waste on the first drainage plate Filter cartridge carry out first time separation of solid and liquid, then through the second drainage plate flow into filter mechanism, composite waste filter mechanism into Second of separation of solid and liquid of row realizes that solid-liquid is kept completely separate, filter residue is heavy for oxalic acid finally by being separated by solid-liquid separation the filter plate of bottom of pond portion Shallow lake rare earth and carbonic acid precipitating rare earth, are used to prepare rare-earth products, and filtrate is containing NH4 +、H+、Cl-, be free of CO3 2-/HCO3 -And oxalic acid Acid waste water；
(5) prepared by ore leachate: adjusting NH in acid waste water4 +Mass percent be 3%, pH value 5 obtains acid NH4Cl leaching Mine liquid；
(6) mine is soaked: by acid NH4Cl ore leachate soaks mine, under acid condition, rare earth element ion and NH for Rare Earth Mine4 +Hair Life is exchanged and is leached in ore leachate, is realized and is contained NH4 +Ammonium carbonate precipitating rare earth waste water reuse.
Embodiment 3
A kind of method of RE waste water resource reutilization, comprising the following steps:
(1) NH wastewater collection: will be contained4 +Ammonium carbonate precipitating rare earth waste water, the acid oxalic acid precipitation RE waste water containing oxalic acid, Extraction wastewater containing rare earth element is collected into different ground catch basins respectively；It is described to contain NH4 +Carbonated rare earth it is useless in NH4 +'s Mass percent is 3%, including ammonium carbonate precipitating rare earth mother liquor waste water, ammonium carbonate precipitating rare earth washes；It is described containing oxalic acid PH is 2 in oxalic acid precipitation RE waste water, including oxalic acid precipitation rare earth mother solution waste water, oxalic acid precipitation rare earth washes；
(2) detect: detection contains NH respectively4 +Ammonium carbonate precipitating rare earth waste water in CO3 2-/HCO3 -Substance withdrawl syndrome, containing grass The object of rare earth element in the substance withdrawl syndrome of oxalic acid precipitation RE waste water mesoxalic acid of acid and the extraction wastewater containing rare earth element The amount concentration of matter；Wherein CO3 2-/HCO3 -Substance withdrawl syndrome be 1.0 mol/L, 0.1 mol/ of substance withdrawl syndrome of oxalic acid L, 0.008 mol/L of substance withdrawl syndrome of rare earth element；
(3) oxalic acid-carbonic acid precipitating: according to the testing result of step (2), NH will be contained by controlling volume ratio4 +Ammonium carbonate precipitating rare earth Waste water, the oxalic acid precipitation RE waste water containing oxalic acid and the extraction wastewater containing rare earth element import agitating reaction pond, open stirring 10 Min makes CO3 2-/HCO3 -, oxalic acid respectively with rare earth element occur precipitation reaction make CO in composite waste after the reaction was completed3 2-/ HCO3 -Substance withdrawl syndrome be 0.0001 mol/L, the substance withdrawl syndrome of oxalic acid is 0.0001 mol/L, rare earth element Substance withdrawl syndrome is 0.0005 mol/L, realizes CO in removal RE waste water3 2-/HCO3 -, oxalic acid purpose；
(4) it is separated by solid-liquid separation: the composite waste after the completion of precipitation reaction being introduced into solid-liquid separation tank, composite waste is in solid-liquid separation tank It is inside separated by solid-liquid separation from top to bottom, the first drainage plate is flowed by skirt first, has filter cartridge, composite waste on the first drainage plate Filter cartridge carry out first time separation of solid and liquid, then through the second drainage plate flow into filter mechanism, composite waste filter mechanism into Second of separation of solid and liquid of row realizes that solid-liquid is kept completely separate, filter residue is heavy for oxalic acid finally by being separated by solid-liquid separation the filter plate of bottom of pond portion Shallow lake rare earth and carbonic acid precipitating rare earth, are used to prepare rare-earth products, and filtrate is containing NH4 +、H+、Cl-, be free of CO3 2-/HCO3 -And oxalic acid Acid waste water；
(5) prepared by ore leachate: adjusting NH in acid waste water4 +Mass percent be 5%, pH value 5 obtains acid NH4Cl leaching Mine liquid；
(6) mine is soaked: by acid NH4Cl ore leachate soaks mine, under acid condition, rare earth element ion and NH for Rare Earth Mine4 +Hair Life is exchanged and is leached in ore leachate, is realized and is contained NH4 +Ammonium carbonate precipitating rare earth waste water reuse.
Embodiment 4
A kind of method of RE waste water resource reutilization, comprising the following steps:
(1) NH wastewater collection: will be contained4 +Ammonium carbonate precipitating rare earth waste water, the acid oxalic acid precipitation RE waste water containing oxalic acid, Extraction wastewater containing rare earth element is collected into different ground catch basins respectively；It is described to contain NH4 +Carbonated rare earth it is useless in NH4 +'s Mass percent is 1.5%, including ammonium carbonate precipitating rare earth mother liquor waste water, ammonium carbonate precipitating rare earth washes；It is described to contain oxalic acid Oxalic acid precipitation RE waste water in pH be 1, including oxalic acid precipitation rare earth mother solution waste water, oxalic acid precipitation rare earth washes；
(2) detect: detection contains NH respectively4 +Ammonium carbonate precipitating rare earth waste water in CO3 2-/HCO3 -Substance withdrawl syndrome, containing grass The object of rare earth element in the substance withdrawl syndrome of oxalic acid precipitation RE waste water mesoxalic acid of acid and the extraction wastewater containing rare earth element The amount concentration of matter；Wherein CO3 2-/HCO3 -Substance withdrawl syndrome be 0.6 mol/L, 0.2 mol/ of substance withdrawl syndrome of oxalic acid L, 0.009 mol/L of substance withdrawl syndrome of rare earth element；
(3) oxalic acid-carbonic acid precipitating: according to the testing result of step (2), NH will be contained by controlling volume ratio4 +Ammonium carbonate precipitating rare earth Waste water, the oxalic acid precipitation RE waste water containing oxalic acid and the extraction wastewater containing rare earth element import agitating reaction pond, open stirring 15 Min makes CO3 2-/HCO3 -, oxalic acid respectively with rare earth element occur precipitation reaction make CO in composite waste after the reaction was completed3 2-/ HCO3 -Substance withdrawl syndrome be 0.00001 mol/L, the substance withdrawl syndrome of oxalic acid is 0.00001 mol/L, rare earth element Substance withdrawl syndrome be 0.0005 mol/L, realize removal RE waste water in CO3 2-/HCO3 -, oxalic acid purpose；
(4) it is separated by solid-liquid separation: the composite waste after the completion of precipitation reaction being introduced into solid-liquid separation tank, composite waste is in solid-liquid separation tank It is inside separated by solid-liquid separation from top to bottom, the first drainage plate is flowed by skirt first, has filter cartridge, composite waste on the first drainage plate Filter cartridge carry out first time separation of solid and liquid, then through the second drainage plate flow into filter mechanism, composite waste filter mechanism into Second of separation of solid and liquid of row realizes that solid-liquid is kept completely separate, filter residue is heavy for oxalic acid finally by being separated by solid-liquid separation the filter plate of bottom of pond portion Shallow lake rare earth and carbonic acid precipitating rare earth, are used to prepare rare-earth products, and filtrate is containing NH4 +、H+、Cl-, be free of CO3 2-/HCO3 -And oxalic acid Acid waste water；
(5) prepared by ore leachate: adjusting NH in acid waste water4 +Mass percent be 2%, pH value 4 obtains acid NH4Cl leaching Mine liquid；
(6) mine is soaked: by acid NH4Cl ore leachate soaks mine, under acid condition, rare earth element ion and NH for Rare Earth Mine4 +Hair Life is exchanged and is leached in ore leachate, is realized and is contained NH4 +Ammonium carbonate precipitating rare earth waste water reuse.

Claims (9)

1. a kind of method of RE waste water resource reutilization, which comprises the following steps:
(1) NH wastewater collection: will be contained4 +Ammonium carbonate precipitating rare earth waste water, the acid oxalic acid precipitation RE waste water containing oxalic acid contains The extraction wastewater of rare earth element is collected into different ground catch basins respectively；
(2) detect: detection contains NH respectively4 +Ammonium carbonate precipitating rare earth waste water in CO3 2-/HCO3 -Substance withdrawl syndrome, contain oxalic acid The substance withdrawl syndrome of oxalic acid precipitation RE waste water mesoxalic acid and the extraction wastewater containing rare earth element in rare earth element substance Amount concentration；
(3) oxalic acid-carbonic acid precipitating: according to the testing result of step (2), NH will be contained by controlling volume ratio4 +Ammonium carbonate precipitating rare earth Waste water, the oxalic acid precipitation RE waste water containing oxalic acid and the extraction wastewater containing rare earth element import agitating reaction pond, open stirring 10- 30 min, make CO3 2-/HCO3 -, oxalic acid respectively with rare earth element occur precipitation reaction make in composite waste after the reaction was completed CO3 2-/HCO3 -Substance withdrawl syndrome be 0-0.0001 mol/L, the substance withdrawl syndrome of oxalic acid is 0-0.0001 mol/L, dilute The substance withdrawl syndrome of earth elements is 0.0005-0.001 mol/L, realizes CO in removal RE waste water3 2-/HCO3 -, oxalic acid mesh 's；
(4) it is separated by solid-liquid separation: the composite waste after the completion of precipitation reaction being introduced into solid-liquid separation tank, composite waste is in solid-liquid separation tank It is inside separated by solid-liquid separation from top to bottom, the first drainage plate is flowed by skirt first, has filter cartridge, composite waste on the first drainage plate Filter cartridge carry out first time separation of solid and liquid, then through the second drainage plate flow into filter mechanism, composite waste filter mechanism into Second of separation of solid and liquid of row realizes that solid-liquid is kept completely separate, filter residue is heavy for oxalic acid finally by being separated by solid-liquid separation the filter plate of bottom of pond portion Shallow lake rare earth and carbonic acid precipitating rare earth, are used to prepare rare-earth products, and filtrate is containing NH4 +、H+、Cl-, be free of CO3 2-/HCO3 -And oxalic acid Acid waste water；
(5) prepared by ore leachate: adjusting NH in acid waste water4 +Mass percent be 2-5%, pH value 4-5, obtain acid NH4Cl ore leachate；
(6) mine is soaked: by acid NH4Cl ore leachate soaks mine, under acid condition, rare earth element ion and NH for Rare Earth Mine4 +Hair Life is exchanged and is leached in ore leachate, is realized and is contained NH4 +Ammonium carbonate precipitating rare earth waste water reuse.
2. the method for RE waste water resource reutilization according to claim 1, which is characterized in that described to contain NH4 +Carbonic acid CO in the RE waste water of ammonia-sinking shallow lake3 2-/HCO3 -Substance withdrawl syndrome be 0.5-1.0 mol/L, NH4 +Mass percent be 0.5- 3%。
3. the method for RE waste water resource reutilization according to claim 1, which is characterized in that the grass containing oxalic acid Substance withdrawl syndrome 0.05-0.3 mol/L, the pH 1-2 of sour precipitating rare earth waste water mesoxalic acid.
4. the method for RE waste water resource reutilization according to claim 2, which is characterized in that described to contain NH4 +Carbonic acid Ammonia-sinking shallow lake RE waste water includes ammonium carbonate precipitating rare earth mother liquor waste water, ammonium carbonate precipitating rare earth washes.
5. the method for RE waste water resource reutilization according to claim 3, which is characterized in that the oxalic acid containing oxalic acid Precipitating rare earth waste water includes oxalic acid precipitation rare earth mother solution waste water, oxalic acid precipitation rare earth washes.
6. the method for RE waste water resource reutilization according to claim 1, which is characterized in that described to contain rare earth element Extraction wastewater in rare earth element substance withdrawl syndrome 0.008-0.01 mol/L.
7. the method for RE waste water resource reutilization according to claim 1, which is characterized in that in step (3), reaction After the completion, make CO in composite waste3 2-/HCO3 -Substance withdrawl syndrome be 0-0.00005 mol/L, the amount of the substance of oxalic acid is dense Degree is 0-0.00005 mol/L, and the substance withdrawl syndrome of rare earth element is 0.0008-0.001 mol/L.
8. the method for RE waste water resource reutilization according to claim 1, which is characterized in that the NH4In Cl ore leachate NH4 +Mass percent be 4%.
9. the method for RE waste water resource reutilization according to claim 8, which is characterized in that the NH4Cl ore leachate PH value is 4.
CN201811218582.5A 2018-10-19 2018-10-19 A kind of method of RE waste water resource reutilization Pending CN109293048A (en)

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