CN108707753A - A kind of technique of the solvent extraction recycling containing rare earth waste - Google Patents
A kind of technique of the solvent extraction recycling containing rare earth waste Download PDFInfo
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- CN108707753A CN108707753A CN201810733043.9A CN201810733043A CN108707753A CN 108707753 A CN108707753 A CN 108707753A CN 201810733043 A CN201810733043 A CN 201810733043A CN 108707753 A CN108707753 A CN 108707753A
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 79
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000002699 waste material Substances 0.000 title claims abstract description 26
- 238000000638 solvent extraction Methods 0.000 title claims abstract description 11
- 238000004064 recycling Methods 0.000 title description 3
- 238000000605 extraction Methods 0.000 claims abstract description 80
- 239000012074 organic phase Substances 0.000 claims abstract description 75
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 73
- 239000012071 phase Substances 0.000 claims abstract description 40
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 22
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 22
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 22
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 22
- 229910052775 Thulium Inorganic materials 0.000 claims abstract description 22
- 238000000926 separation method Methods 0.000 claims abstract description 21
- 238000005245 sintering Methods 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims description 41
- 238000002156 mixing Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000011347 resin Substances 0.000 claims description 17
- 229920005989 resin Polymers 0.000 claims description 17
- -1 N- methylimidazole anion Chemical class 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000008346 aqueous phase Substances 0.000 claims description 14
- 238000005191 phase separation Methods 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims description 10
- 238000007127 saponification reaction Methods 0.000 claims description 10
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 5
- 241000370738 Chlorion Species 0.000 claims description 5
- 239000001110 calcium chloride Substances 0.000 claims description 5
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000003350 kerosene Substances 0.000 claims description 5
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 5
- 229910021536 Zeolite Inorganic materials 0.000 claims description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 239000002893 slag Substances 0.000 claims description 4
- 239000010457 zeolite Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 6
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 150000002632 lipids Chemical class 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- 239000002253 acid Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- JJEJDZONIFQNHG-UHFFFAOYSA-N [C+4].N Chemical compound [C+4].N JJEJDZONIFQNHG-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
- C22B1/08—Chloridising roasting
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/40—Mixtures
- C22B3/409—Mixtures at least one compound being an organo-metallic compound
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B59/00—Obtaining rare earth metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The present invention relates to a kind of solvent extractions to recycle the technique containing rare earth waste, rare earth waste containing Ce, Pr, Dy, Er, Tm is subjected to high temperature sintering, hydrochloric acid acidleach and adjustment pH value, organic phase is mixed with traditional extraction agent P507 compositions by Novel Extractant P227 again, matching tree lipid phase is carried out without saponifiable extraction, and it is stripped activity using the extraction of different rare earth elements, control the separation order of each rare earth element.The advantages such as the present invention has Tm product purities height, yield high, can be used for mass producing, and entire technique entirety chemical reagent consumption is small, be easy to automation, easy to operate, production cost is low.
Description
Technical field
The present invention relates to valuable metal recovery fields, in particular to a kind of solvent extraction recycling contains rare earth waste
Technique.
Background technology
Rare earth element plays important role in 21 th Century modern industrialization construction, this has with it
The characteristics such as excellent magnetic, light, electricity are inseparable.Just because of this, rare earth metal is to the faster industry of some development in the world to pass
It is important, such as catalyst, magnetic material, glass, metallurgy, electronics and fluorescent powder, it is upgrading conventional industries, development science and techniques of defence work
Industry and the foundation indispensable key element of new industry and important non-renewable strategic resources.As rare earth is being catalyzed
Application in agent, magnet, rare earth alloy, global rare earth demand will be increased before 2020 with annual 6% speed.
Rare Earth Mine is after leaching agent leaches, using obtaining rare earth oxide primary product after carbon ammonium precipitation and roasting.Again through HCl
Enter Rare Earth Separation program after dissolving, the separation method of rare earth include chemical precipitation method, ion exchange, organic solvent extractionprocess,
Chromes, liquid-film method etc..Solvent extraction is because its extraction and separative efficiency are high, processing capacity is big, reaction
The advantages that speed is fast is as the current widely used Rare Earth Separation method of rare-earth wet method smelter both at home and abroad.
Extractant can be realized by complex reaction selectively enters organic phase by metal ion by water phase, and also wanting can
It is realized by another kind of complex reaction and metal ion is gone into water phase by organic phase, to reach metal enrichment and detach.Extraction
Agent had not only needed the reaction active groups with complexing of metal ion, but also needed and increase oil-soluble hydrophobic grouping.According to extraction
The difference of agent type, extraction system can be divided into phosphorous extraction system, amine phosphorous extraction system, chelating type extraction system etc..This
Kind sorting technique is especially suitable for the uncertain system of extraction mechanism；According to the difference of aqueous phase acidity to be extracted, extraction system can
To be divided into acid extract system and neutral extraction system；According to the difference of spe medium, extraction system can be divided into sulfuric acid extraction
System, hydrochloric acid extraction system and nitric acid system；Common extraction system is according to the extraction generated in extraction mechanism or extraction process
What the property of conjunction object was classified, extraction system can be divided into Types Below：Simple molecules extraction system, Neutral complex extraction
System, acid complexometric extraction system, ion association extraction system, synergistic system and high-temperature extraction system.
Alkaline matters saponification P507 and P204 the extractant extracting and separating rear earths such as ammonium hydroxide are mainly used in industrial production at present
Element generates the NH containing high concentration in extraction separation process4+、Na+Or Ca2+Saponification waste-water can seriously endanger environment, ammonia nitrogen
Wastewater problem is the most scabrous environmental problem that Rare Earth Separation factory faces in recent years, moreover, traditional extraction rare-earth separating member
The problems such as process of element is there is also long flow path, component is changeable, mass transfer lag, organic phase consumption are big and security risk
Invention content
In order to solve the above technical problem, the present invention provides a kind of solvent extractions to recycle the technique containing rare earth waste, the technique
Can high efficiente callback containing the rare earth element in rare earth waste, belong to rare earth extraction industry there is an urgent need to, really can reduce extraction
Agent consumption, the extraction and separation new technology increase extraction efficiency, reduce the reaction time, reducing solvent consumption and low cost.
The step of technique of the present invention, is specific as follows：
1）, by pretreated 0.4~0.5 ratio containing rare earth waste and caustic soda and 0.75~0.85 ︰ of calcium chloride 1 ︰ in mass ratio
Mixing is then heated to 350~450 DEG C of 1~2h of heat preservation, is further continued for being heated to 700~800 DEG C of 2~3h of heat preservation, obtains sintering feed；
The sintering feed is reacted with excessive hydrochloric acid solution, is obtained by filtration after reaction containing Ce, Pr, Dy, Er, Tm feed liquid and insoluble matter；
2）, in the reactor sequentially add P227 and P507 sulfonated kerosene mixing organic phase, the feed liquid containing Ce, Pr, Dy, Er, Tm
With N- methylimidazole anion exchanger resin phases；It is stirred to react 0.5~1h at 25~35 DEG C, stands 30min or so；From upper layer
Organic phase obtains load DyErTm organic phases, and CePr feed liquids are obtained from water phase；
3）, the CePr feed liquids conventional saponification P507 organic phases are added, after extraction and separation, obtaining water phase products C e and load Pr has
Machine phase；The load Pr organic phases are stripped using a concentration of 3~5mol/L hydrochloric acid, product Pr is obtained from aqueous phase separation；
4）, be added to the back extraction of 1.0~1.5mol/L hydrochloric acid, separating obtained product Dy and load by the load DyErTm is organic
ErTm organic phases；The load ErTm organic phases are subjected to secondary back extraction using a concentration of 3~5mol/L hydrochloric acid again, from water phase point
From acquisition ErTm feed liquids；
5）, P507 organic phases and N- methylimidazole anion exchanger resin phases is added in the ErTm feed liquids, after extraction and separation, obtain
Obtain water phase product E r and load Tm organic phases；The load Tm organic phases are carried out two using a concentration of 4~5 mol/L hydrochloric acid again
Secondary back extraction obtains product Tm from aqueous phase separation.
Step 2）, in the mixing organic phase, P507 a concentration of 1~1.5mol/L, P227 a concentration of 0.25~
0.50mol/L。
Step 2）, the N- methylimidazole anions exchanger resin average grain diameter is 0.2~0.4mm, opposite chlorion
Effective exchange capacity is 3.5~5.0mol/kg.
Step 2）, rare earth in the feed liquid containing Ce, Pr, Dy, Er, Tm is 0.2 with the molar ratio for mixing organic phase
~0.3 ︰ 1.
A concentration of 0.6~the 0.8mol/L containing Ce, Pr, Dy, Er, Tm feed liquid rare earth elements, pH value range 2~3.
Step 4）, control the ratio between the hydrochloric acid of secondary back extraction and molal quantity of load ErTm organic phase middle rare earth for 3.7~
3.9 ︰ 1.
Step 5）, the ratio between molal quantity of the hydrochloric acid and load Tm organic phase middle rare earth that control secondary back extraction is 3.7~3.9 ︰
1。
The product Tm purity is 99.9995% or more, and yield is 93.8~95.2%.
The pretreatment is, is crushed described containing rare earth waste, grinds, washs pretreatment.
The rare earth waste that contains is rare earth containing zeolite production process slag, FCC dead catalyst, vehicle exhaust dead catalyst and contains
It is one or more in the special cermacis waste material of rare earth.
It is an advantage of the invention that：Rare earth waste containing Ce, Pr, Dy, Er, Tm is subjected to high temperature sintering, hydrochloric acid acidleach and tune
Whole pH value, then organic phase is mixed with traditional extraction agent P507 compositions by Novel Extractant P227, matching tree lipid phase is carried out without soap
Change extraction, and activity is stripped using the extraction of different rare earth elements, controls the separation order of each rare earth element.The present invention has Tm
Product purity is high, yield is high, can be used for mass producing, and entire technique entirety chemical reagent consumption is small, is easy to automation, operation
The easy, advantages such as production cost is low.
Specific implementation mode
Solvent extraction is the dissolubility difference using solute between two kinds of immiscible liquid phases to reach separation and richness
Collect the method for solute, and can be described as liquid-liquid extraction.Currently, the extractant that mainly uses of the rare-earth trade in China for P204 and
The acidity phosphine extractant such as P507, extraction system have P507-HCl systems, P507-HNO3System and P204-H2SO4System etc..This
A little extraction systems common more sensitive to acidity variation is susceptible to and declines to rare earth extraction performance when acidity is higher
Phenomenon, thus usually need to increase saponifying process.
The target advanced side by side for realization industrial production and environmental protection, it is necessary to rare earth extraction saponification is solved from source
The problem of ammonia nitrogen of link, high-salt wastewater amount big pollution environment, develops more green clean solvent extraction technology rare-earth separating
Element is extremely urgent.In recent years, numerous researchers dissipate thinking, it is proposed that the new direction of rare earth " no saponification " extraction and separation, i.e.,
The technique that extractant does not need the direct extracting and separating rear earth of saponification.
In addition, there is the more other isolation technics of extration resin technology the highly selective and ion of solvent extraction to hand over simultaneously
The equipment of changing method is simple, high efficiency two-fold advantage, can be used as a kind of side for efficiently separating and producing single high pure rare earth product
Method is referred to as second generation extraction system.
This patent is further described with reference to embodiment and comparative example.
Embodiment 1：
It will be broken containing rare earth waste containing rare earth containing zeolite production process slag, FCC dead catalyst, vehicle exhaust dead catalyst
Broken, grinding, washing pretreatment.It is pretreated mixed containing rare earth waste and caustic soda and 0.75 ︰ of calcium chloride 1 ︰ in mass ratio, 0.4 ratios
It is even, 450 DEG C of heat preservation 2h are then heated to, is further continued for being heated to 700 DEG C of heat preservation 2h, obtains sintering feed.
The sintering feed is reacted with excessive hydrochloric acid solution, be obtained by filtration after reaction containing Ce, Pr, Dy, Er, Tm feed liquid and
Insoluble matter.The sulfonated kerosene mixing organic phase of P227 and P507, the feed liquid containing Ce, Pr, Dy, Er, Tm are sequentially added in the reactor
With N- methylimidazole anion exchanger resin phases.In the mixing organic phase, P507 a concentration of 1mol/L, P227 is a concentration of
0.25mol/L.The N- methylimidazole anions exchanger resin average grain diameter is 0.2mm, and effective exchange of opposite chlorion is held
Amount is 5.0mol/kg.Rare earth in the feed liquid containing Ce, Pr, Dy, Er, Tm is 0.3 ︰ with the molar ratio for mixing organic phase
1.A concentration of 0.6mol/L containing Ce, Pr, Dy, Er, Tm feed liquid rare earth elements, pH value 2.It is stirred to react at 25 DEG C
1h stands 30min or so.Load DyErTm organic phases are obtained from upper organic phase, CePr feed liquids are obtained from water phase.
Conventional saponification P507 organic phases are added in the CePr feed liquids, after extraction and separation, obtain water phase products C e and load Pr
Organic phase；The load Pr organic phases are stripped using a concentration of 3mol/L hydrochloric acid, product Pr is obtained from aqueous phase separation.
The organic 1.0mol/L hydrochloric acid that is added to of the load DyErTm is stripped, separating obtained product Dy and load ErTm have
Machine phase.The load ErTm organic phases are subjected to secondary back extraction using a concentration of 3mol/L hydrochloric acid again, control the salt of secondary back extraction
The ratio between acid and the molal quantity of load ErTm organic phase middle rare earth are 3.7 ︰ 1.ErTm feed liquids are obtained from aqueous phase separation.
P507 organic phases and N- methylimidazole anion exchanger resin phases is added in the ErTm feed liquids, after extraction and separation,
Obtain water phase product E r and load Tm organic phases.The load Tm organic phases are carried out using a concentration of 4mol/L hydrochloric acid again secondary
The ratio between molal quantity of back extraction, the hydrochloric acid and load Tm organic phase middle rare earth that control secondary back extraction is 3.7 ︰ 1.It is obtained from aqueous phase separation
Product Tm, the product Tm purity are 99.9995%, yield 93.8%.
Embodiment 2：
By containing rare earth containing zeolite production process slag, FCC dead catalyst, special cermacis waste material containing rare earth containing rare earth waste into
Row is broken, grinding, washs pretreatment.It is pretreated to compare containing rare earth waste and caustic soda and 0.85 ︰ 0.5 of calcium chloride 1 ︰ in mass ratio
Example mixing is then heated to 450 DEG C of heat preservation 1h, is further continued for being heated to 800 DEG C of heat preservation 2h, obtains sintering feed.
The sintering feed is reacted with excessive hydrochloric acid solution, be obtained by filtration after reaction containing Ce, Pr, Dy, Er, Tm feed liquid and
Insoluble matter.The sulfonated kerosene mixing organic phase of P227 and P507, the feed liquid containing Ce, Pr, Dy, Er, Tm are sequentially added in the reactor
With N- methylimidazole anion exchanger resin phases.In the mixing organic phase, P507 a concentration of 1mol/L, P227 is a concentration of
0.50mol/L.The N- methylimidazole anions exchanger resin average grain diameter is 0.4mm, and effective exchange of opposite chlorion is held
Amount is 4.0mol/kg.Rare earth in the feed liquid containing Ce, Pr, Dy, Er, Tm is 0.3 ︰ with the molar ratio for mixing organic phase
1.A concentration of 0.7mol/L containing Ce, Pr, Dy, Er, Tm feed liquid rare earth elements, pH value 2.It is stirred to react at 35 DEG C
1h stands 30min or so.Load DyErTm organic phases are obtained from upper organic phase, CePr feed liquids are obtained from water phase.
Conventional saponification P507 organic phases are added in the CePr feed liquids, after extraction and separation, obtain water phase products C e and load Pr
Organic phase；The load Pr organic phases are stripped using a concentration of 5mol/L hydrochloric acid, product Pr is obtained from aqueous phase separation.
The organic 1.5mol/L hydrochloric acid that is added to of the load DyErTm is stripped, separating obtained product Dy and load ErTm have
Machine phase；The load ErTm organic phases are subjected to secondary back extraction using a concentration of 5mol/L hydrochloric acid again, control the salt of secondary back extraction
The ratio between acid and the molal quantity of load ErTm organic phase middle rare earth are 3.9 ︰ 1.ErTm feed liquids are obtained from aqueous phase separation.
P507 organic phases and N- methylimidazole anion exchanger resin phases is added in the ErTm feed liquids, after extraction and separation,
Obtain water phase product E r and load Tm organic phases；The load Tm organic phases are carried out two using a concentration of 5 mol/L hydrochloric acid again
The ratio between molal quantity of secondary back extraction, the hydrochloric acid and load Tm organic phase middle rare earth that control secondary back extraction is 3.9 ︰ 1.It is obtained from aqueous phase separation
Product Tm is obtained, the product Tm purity is 99.9999%, yield 95.2%.
Embodiment 3：
It will be broken containing rare earth waste containing FCC dead catalyst, vehicle exhaust dead catalyst, special cermacis waste material containing rare earth
Broken, grinding, washing pretreatment.Pretreated 0.45 ratio containing rare earth waste and caustic soda and 0.80 ︰ of calcium chloride 1 ︰ in mass ratio
Mixing is then heated to 400 DEG C of heat preservation 1h, is further continued for being heated to 750 DEG C of heat preservation 3h, obtains sintering feed.
The sintering feed is reacted with excessive hydrochloric acid solution, be obtained by filtration after reaction containing Ce, Pr, Dy, Er, Tm feed liquid and
Insoluble matter.The sulfonated kerosene mixing organic phase of P227 and P507, the feed liquid containing Ce, Pr, Dy, Er, Tm are sequentially added in the reactor
With N- methylimidazole anion exchanger resin phases.In the mixing organic phase, P507 a concentration of 1.2mol/L, P227 is a concentration of
0.40mol/L.The N- methylimidazole anions exchanger resin average grain diameter is 0.3mm, and effective exchange of opposite chlorion is held
Amount is 4.0mol/kg.Rare earth in the feed liquid containing Ce, Pr, Dy, Er, Tm is 0.25 ︰ with the molar ratio for mixing organic phase
1.A concentration of 0.6mol/L containing Ce, Pr, Dy, Er, Tm feed liquid rare earth elements, pH value 3.It is stirred to react at 35 DEG C
0.5h stands 30min or so.Load DyErTm organic phases are obtained from upper organic phase, CePr feed liquids are obtained from water phase.
Conventional saponification P507 organic phases are added in the CePr feed liquids, after extraction and separation, obtain water phase products C e and load Pr
Organic phase；The load Pr organic phases are stripped using a concentration of 4mol/L hydrochloric acid, product Pr is obtained from aqueous phase separation.
The organic 1.0mol/L hydrochloric acid that is added to of the load DyErTm is stripped, separating obtained product Dy and load ErTm have
Machine phase；The load ErTm organic phases are subjected to secondary back extraction using a concentration of 4mol/L hydrochloric acid again, control the salt of secondary back extraction
The ratio between acid and the molal quantity of load ErTm organic phase middle rare earth are 3.8 ︰ 1.ErTm feed liquids are obtained from aqueous phase separation.
P507 organic phases and N- methylimidazole anion exchanger resin phases is added in the ErTm feed liquids, after extraction and separation,
Obtain water phase product E r and load Tm organic phases；The load Tm organic phases are carried out using a concentration of 4mol/L hydrochloric acid again secondary
The ratio between molal quantity of back extraction, the hydrochloric acid and load Tm organic phase middle rare earth that control secondary back extraction is 3.8 ︰ 1.It is obtained from aqueous phase separation
Product Tm, the product Tm purity are 99.9995%, yield 94.6%.
Comparative example 1：
In the recovery process of the present invention, when changing the ingredient and proportioning of extraction system, especially organic phase and resin phase contains
Amount is excessive or insufficient, and the priority of the extraction reaction efficiency and different rare earth elements that influence rare earth element is extracted order, is caused dilute
The native rate of recovery and purity decline.
Comparative example 2：
When pretreated sintering and step of acid dipping or parameter change, the addition of especially different raw materials for sintering and
The pH value of acidleach after sintering controls, and will lead to excessive or rare earth element is lost in containing impurity in rare earth feed liquid, and then drop
The efficiency and yield of low subsequent extraction and separation step.
The present invention will contain rare earth waste progress high temperature sintering, hydrochloric acid acid it can be seen from embodiment 1-3 and comparative example 1 and 2
Leaching and adjustment pH value, then organic phase is mixed with traditional extraction agent composition by Novel Extractant P227, matching tree lipid phase carries out nothing
Saponifiable extraction, and it is stripped activity using the extraction of different rare earth elements, control the separation order of each rare earth element.The present invention has
Tm product purities are high, yield is high, can be used for mass producing, and entire technique entirety chemical reagent consumption is small, is easy to automation, behaviour
Make the advantages such as easy, production cost is low.
While there has been shown and described that the embodiment of this patent, it will be understood by those skilled in the art that：Not
In the case of being detached from the principle and objective of this patent a variety of change, modification, replacement and modification can be carried out to these embodiments, this
The range of patent is limited by claim and its equivalent.
Claims (10)
1. the technique containing rare earth waste is recycled in a kind of solvent extraction, it is characterized in that：The step of technique, is specific as follows：
1）, by pretreated 0.4~0.5 ratio containing rare earth waste and caustic soda and 0.75~0.85 ︰ of calcium chloride 1 ︰ in mass ratio
Mixing is then heated to 350~450 DEG C of 1~2h of heat preservation, is further continued for being heated to 700~800 DEG C of 2~3h of heat preservation, obtains sintering feed；
The sintering feed is reacted with excessive hydrochloric acid solution, is obtained by filtration after reaction containing Ce, Pr, Dy, Er, Tm feed liquid and insoluble matter；
2）, in the reactor sequentially add P227 and P507 sulfonated kerosene mixing organic phase, the feed liquid containing Ce, Pr, Dy, Er, Tm
With N- methylimidazole anion exchanger resin phases；It is stirred to react 0.5~1h at 25~35 DEG C, stands 30min or so；From upper layer
Organic phase obtains load DyErTm organic phases, and CePr feed liquids are obtained from water phase；
3）, the CePr feed liquids conventional saponification P507 organic phases are added, after extraction and separation, obtaining water phase products C e and load Pr has
Machine phase；The load Pr organic phases are stripped using a concentration of 3~5mol/L hydrochloric acid, product Pr is obtained from aqueous phase separation；
4）, be added to the back extraction of 1.0~1.5mol/L hydrochloric acid, separating obtained product Dy and load by the load DyErTm is organic
ErTm organic phases；The load ErTm organic phases are subjected to secondary back extraction using a concentration of 3~5mol/L hydrochloric acid again, from water phase point
From acquisition ErTm feed liquids；
5）, P507 organic phases and N- methylimidazole anion exchanger resin phases is added in the ErTm feed liquids, after extraction and separation, obtain
Obtain water phase product E r and load Tm organic phases；The load E organic phases are carried out two using a concentration of 4~5 mol/L hydrochloric acid again
Secondary back extraction obtains product Tm from aqueous phase separation.
2. technique according to claim 1, it is characterized in that：Step 2）, in the mixing organic phase, P507 a concentration of 1~
A concentration of 0.25~0.50mol/L of 1.5mol/L, P227.
3. technique according to claim 1 or 2, it is characterized in that：Step 2）, the N- methylimidazole anions exchanger resin
Average grain diameter is 0.2~0.4mm, and effective exchange capacity of opposite chlorion is 3.5~5.0mol/kg.
4. technique according to claim 1, it is characterized in that：Step 2）, dilute in the feed liquid containing Ce, Pr, Dy, Er, Tm
Native with the molar ratio for mixing organic phase is 0.2~0.3 ︰ 1.
5. technique according to claim 4, it is characterized in that：It is described containing the dense of Ce, Pr, Dy, Er, Tm feed liquid rare earth elements
Degree is 0.6~0.8mol/L, pH value range 2~3.
6. technique according to claim 1, it is characterized in that：Step 4）, the hydrochloric acid and load ErTm that control secondary back extraction have
The ratio between molal quantity of machine phase middle rare earth is 3.7~3.9 ︰ 1.
7. technique according to claim 1, it is characterized in that：Step 5）, control secondary back extraction hydrochloric acid and load Tm it is organic
The ratio between molal quantity of phase middle rare earth is 3.7~3.9 ︰ 1.
8. according to the technique described in claim 1 to 7, it is characterized in that：The product Tm purity is 99.9995% or more, and yield is
93.8~95.2%.
9. technique according to claim 1, it is characterized in that：The pretreatment is, by it is described be crushed containing rare earth waste,
Grinding, washing pretreatment.
10. according to the technique described in claim 1 to 9, it is characterized in that：The rare earth waste that contains is rare earth containing zeolite production process
It is one or more in slag, FCC dead catalyst, vehicle exhaust dead catalyst and special cermacis waste material containing rare earth.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109680169A (en) * | 2019-02-22 | 2019-04-26 | 东北大学 | A kind of solid extracting agent and its extraction light rare earth method of P204 doped polyaniline |
| CN111961856A (en) * | 2020-07-06 | 2020-11-20 | 廖乐 | Device for separating vanadium and rare earth elements from waste FCC catalyst |
| CN113337739A (en) * | 2021-06-03 | 2021-09-03 | 赣州有色冶金研究所有限公司 | Desorption method of rare earth loaded resin and recovery method of rare earth |
| CN114890450A (en) * | 2022-05-11 | 2022-08-12 | 湖南东方钪业股份有限公司 | Method for preparing scandium oxide |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1237539A (en) * | 1999-04-29 | 1999-12-08 | 清华大学 | Method for recovering rare earth carbonate by bastnaesite decomposition through ammonium chloride baking process |
| CN1936034A (en) * | 2006-09-15 | 2007-03-28 | 中国科学院长春应用化学研究所 | Method for preparing embedding ion liquid and neutral phosphor (phosphine) extractant composite material and its use |
| CN102660688A (en) * | 2012-05-10 | 2012-09-12 | 北京科技大学 | Method for recovering rare earth from waste rare earth luminescent material |
| CN104087750A (en) * | 2014-07-14 | 2014-10-08 | 厦门稀土材料研究所 | Rare earth extraction and separation method |
| CN105177322A (en) * | 2015-09-07 | 2015-12-23 | 中国科学院上海有机化学研究所 | Extracting agent, extraction system and application |
| WO2018028543A1 (en) * | 2016-08-08 | 2018-02-15 | 有研稀土新材料股份有限公司 | Method for extraction, enrichment and recovery of rare earths from low-concentration rare earth solution |
| CN108220596A (en) * | 2018-02-08 | 2018-06-29 | 深圳万佳互动科技有限公司 | A kind of praseodymium neodymium extracting and enriching separation method |
-
2018
- 2018-07-06 CN CN201810733043.9A patent/CN108707753B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1237539A (en) * | 1999-04-29 | 1999-12-08 | 清华大学 | Method for recovering rare earth carbonate by bastnaesite decomposition through ammonium chloride baking process |
| CN1936034A (en) * | 2006-09-15 | 2007-03-28 | 中国科学院长春应用化学研究所 | Method for preparing embedding ion liquid and neutral phosphor (phosphine) extractant composite material and its use |
| CN102660688A (en) * | 2012-05-10 | 2012-09-12 | 北京科技大学 | Method for recovering rare earth from waste rare earth luminescent material |
| CN104087750A (en) * | 2014-07-14 | 2014-10-08 | 厦门稀土材料研究所 | Rare earth extraction and separation method |
| CN105177322A (en) * | 2015-09-07 | 2015-12-23 | 中国科学院上海有机化学研究所 | Extracting agent, extraction system and application |
| WO2018028543A1 (en) * | 2016-08-08 | 2018-02-15 | 有研稀土新材料股份有限公司 | Method for extraction, enrichment and recovery of rare earths from low-concentration rare earth solution |
| CN108220596A (en) * | 2018-02-08 | 2018-06-29 | 深圳万佳互动科技有限公司 | A kind of praseodymium neodymium extracting and enriching separation method |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109680169A (en) * | 2019-02-22 | 2019-04-26 | 东北大学 | A kind of solid extracting agent and its extraction light rare earth method of P204 doped polyaniline |
| CN111961856A (en) * | 2020-07-06 | 2020-11-20 | 廖乐 | Device for separating vanadium and rare earth elements from waste FCC catalyst |
| CN113337739A (en) * | 2021-06-03 | 2021-09-03 | 赣州有色冶金研究所有限公司 | Desorption method of rare earth loaded resin and recovery method of rare earth |
| CN114890450A (en) * | 2022-05-11 | 2022-08-12 | 湖南东方钪业股份有限公司 | Method for preparing scandium oxide |
| CN114890450B (en) * | 2022-05-11 | 2024-03-26 | 湖南东方钪业股份有限公司 | Method for preparing scandium oxide |
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