CN106148691B - A kind of technique that alkaline process handles monazite and extracting and separating rear earth - Google Patents
A kind of technique that alkaline process handles monazite and extracting and separating rear earth Download PDFInfo
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- CN106148691B CN106148691B CN201510188991.5A CN201510188991A CN106148691B CN 106148691 B CN106148691 B CN 106148691B CN 201510188991 A CN201510188991 A CN 201510188991A CN 106148691 B CN106148691 B CN 106148691B
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Abstract
The present invention provides the techniques of a kind of alkaline process processing monazite and extracting and separating rear earth; concrete scheme is that alkaline process processing monazite is carried out under non-oxidizable protective atmosphere; obtain hydroxide containing trivalent rare earth; it directly carries out reacting the organic phase for obtaining supported rare earth with acidic extractant; trivalent cerium hydroxide has characteristic that is readily soluble and saving acid consumption relative to the hydroxide of quadrivalent cerium; rare earth is preferentially dissolved for subsequent faintly acid extractant, realizes and is created condition with the separation of the impurity such as indissoluble thorium dioxide；Trivalent rare earth hydroxide directlys adopt acidic extractant dissolution, is saponified the excessively high problem of mode rare-earth separating bring acid and alkali consumption using organic liquid alkaline or ammonium hydroxide, process simplifies.
Description
Technical field
The present invention relates to a kind of alkaline process processing monazite and the techniques of rare earth extraction separation, and specifically one kind is non-oxygen
Alkaline process is carried out under the property changed protective atmosphere and handles monazite, obtains trivalent rare earth hydroxide, is directly carried out with acidic extractant anti-
The organic phase that supported rare earth should be obtained belongs to Rare Earth Mine and smelts production field
Background technique
Monazite is a kind of industrial Ree-phospeate Minerals, is easy to sort, monazite minerals content can in obtained concentrate
Up to 95% or more.It is industrial that monazite concentrate is generally handled using caustic soda decomposition method.[" rare earth ", the first edition first volume, metallurgical industry
Publishing house 1978, P221-237.)] industrially, traditional handicraft is proportionally prepared using caustic lye of soda and concentrate into decomposition
Slot, decomposer carry out reaction at relatively high temperatures using steam jacket heating.Continuous charging and discharging, guarantee decomposition temperature
Lower reaction achievees the purpose that rare earth is separated with phosphorus by alkali conversion, obtains the mixed serum of rare earth hydrate and tertiary sodium phosphate, so
Enter afterwards and be filtered, washed process acquisition rare earth hydrate, then the preferential dissolution process of hydrochloric acid produces mixed chlorinated rare earth, then using acid
Property extractant carry out extraction and separation, obtain single rare earth.
During traditional handicraft caustic digestion, rare earth except cerium forms rare-earth hydroxide:
REPO4+3OH-=RE (OH)3+PO4 3-
Cerium is oxidized by oxygen in this process, generates the ceric hydroxide being poorly soluble:
The thorium of association forms thorium dioxide:
Th3(PO4)4+12OH-=3Th (OH)4+4PO4 3-
Traditional rare earth extraction separate mode is generally in rare-earth chlorination objects system using saponification P507 extracting and separating rear earth member
Plain (rare earth chemistry collection of thesis, Changchun Institute of Applied Chemistry's nineteen eighty-two, Science Press), this method extracting and separating rear earth effect is good, application
Extensively.Extraction process is using rare earth chloride as feed liquid, it is necessary to and it is organic using the saponification such as ammonium hydroxide or sodium hydroxide, pass through fractional extraction
Mode carries out Rare Earth Separation by extraction section, washing section and back extraction section, which generates a large amount of ammonia nitrogens or high-salt wastewater, to ring
Cause biggish pollution in border.
The present invention provides a kind of under non-oxidizable protective atmosphere, airtight heating carries out the work that alkaline process handles monazite
Skill, rare earth forms trivalent rare earth hydroxide during caustic digestion, then is directly dissolved using acid organic extractant, is born
Carry the organic phase of rare earth.
Wherein alkali conversion reaction is as follows
REPO4+3OH-=RE (OH)3+PO4 3-
CePO4+3OH-=Ce (OH)3+PO4 3-
Th3(PO4)4+12OH-=3Th (OH)4+4PO4 3-
And trivalent rare earth hydroxide is as follows in the dissolution reaction of acidic extractant:
RE(OH)3+ 3HA=REA3+H+
HA --- --- acidic extractant
Summary of the invention
The present invention provides a kind of under non-oxidizable protective atmosphere, airtight heating carries out the work that alkaline process handles monazite
Skill, rare earth form trivalent rare earth hydroxide during caustic digestion, the technical solution of the present invention is as follows:
Liquid alkaline and monazite mixture are heated into progress instead in closed container during the alkaline process processing monazite
Answer, protected under non-oxidizing atmosphere, the rare earth in monazite caustic digestion process formed trivalent rare earth hydroxide and
Sodium radio-phosphate,P-32 solution, after filtration washing separates, trivalent rare earth hydroxide is dissolved using acidic extractant, obtains loading dilute
The organic phase of soil is used for the extraction and separation of rare earth.
It is as follows that alkaline process handles monazite reaction
REPO4+3OH-=RE (OH)3+PO4 3-
CePO4+3OH-=Ce (OH)3+PO4 3-
Th3(PO4)4+12OH-=3Th (OH)4+4PO4 3-
The technique of a kind of alkaline process processing monazite and extracting and separating rear earth, which is characterized in that the monazite
For the monazite concentrate of 30%REO-65%REO.
The technique of a kind of described alkaline process processing monazite and extracting and separating rear earth, which is characterized in that the liquid alkaline is
The liquid-solid ratio of at least one of sodium hydroxide, potassium hydroxide, alkali concentration 20%-75%, liquid alkaline and monazite is 1.5:1-
10:1, reaction temperature are 80 DEG C -350 DEG C.
The technique of a kind of alkaline process processing monazite and extracting and separating rear earth, which is characterized in that described is non-oxide
Property gas includes but is not limited at least one of nitrogen, argon gas, helium, hydrogen.
The technique of a kind of alkaline process processing monazite and extracting and separating rear earth, which is characterized in that the closed appearance
Device uses but is not limited to enclosed reaction kettle.
The technique of a kind of alkaline process processing monazite and extracting and separating rear earth, which is characterized in that described is heated
At least one of steam heating, oil bath heating, Far-infrared Heating, vortex electric heating heating method can be used in journey, preferential to use
Far-infrared Heating or vortex Electric heating.
The technique of a kind of alkaline process processing monazite and extracting and separating rear earth, which is characterized in that the trivalent is dilute
Cerium exists in the form of+trivalent state rare-earth hydroxide in native hydroxide, wherein Ce3+/ Σ Ce is 80%-100%.
The technique of a kind of alkaline process processing monazite and extracting and separating rear earth, which is characterized in that the acid extract
Taking agent includes but is not limited at least one of P204, P507, aphthenic acids, C272.
The technique of a kind of alkaline process processing monazite and extracting and separating rear earth, which is characterized in that the acid extract
Taking agent solution temperature is 20-50 DEG C, and the organic concentrations are 0.2-1.8mol/L, is 0.02- according to organic load rare earth content
0.2mol/L carries out the reaction that feeds intake.
The technique of a kind of alkaline process processing monazite and extracting and separating rear earth, which is characterized in that the acid extract
Agent is taken store up obtained a small amount of insoluble matter as excellent molten slag in course of dissolution, for recycling thorium therein, uranium.
The technique of a kind of alkaline process processing monazite and extracting and separating rear earth, which is characterized in that the acid extract
It takes agent to carry out in course of dissolution, in the case that preferential selection rare-earth yield is less than 99%, obtained a small amount of insoluble matter is subjected to salt
After sour preferential dissolution, filtration washing, rare earth carries out extraction and separation in filtrate, excellent molten slag stockpiling, for recycling thorium therein, uranium.
The trivalent rare earth hydroxide can directly adopt hydrochloric acid and carry out excellent molten formation rare earth chloride to it, realize rare earth
With the separation of thorium.
The process program is equally applicable to other terres rares mines such as alkaline process processing xenotime, bastnaesite.
Beneficial effects of the present invention are as follows:
(1) it uses non-oxidizable protective atmosphere to handle, avoids and account for 50% or so cerium member in monazite in rare earth partition
Element is converted into tetravalence cerium hydroxide, reduces alkaline consumption during caustic digestion.
(2) hydroxide (Ce (OH) of the trivalent cerium hydroxide relative to quadrivalent cerium4) with readily soluble and saving acid consumption
Characteristic directly dissolves for subsequent faintly acid extractant and preferentially dissolves rare earth, realizes the separation with impurity such as indissoluble thorium dioxides
It creates condition.
(3) it preferentially dissolves with traditional hydrochloric acid and obtains rare earth chloride, then separated using organic liquid alkaline or ammonium hydroxide saponification mode
Rare-earth process compares, and trivalent rare earth hydroxide directlys adopt acidic extractant dissolution, carries out extraction and separation, has process letter
The advantages of changing, saving acid and alkali consumption.
(4) it decomposes hydrochloric acid with traditional alkaline process and preferentially dissolves and compare, trivalent cerium hydroxide acidic extractant preferentially dissolves
In the process, will not because in quadrivalent cerium and system the redox reaction of chlorine root due to generate toxic chlorine, it is raw to realize safely cleaning
It produces.
(5) non-oxidizable protective atmosphere, airtight heating processing are used, whole system is in the state that is isolated from the outside, puts
Radioactive pollution and harm problem are inhibited to greatest extent.
Specific embodiment
Embodiment 1
REO content is placed in for 51.2% monazite (ThO2 content 3.9%) and 40% liquid alkaline with liquid-solid ratio for 3:1
In the reaction kettle of nitrogen protection atmosphere, using Far-infrared Heating to 140 DEG C of decomposition reactions, reaction paste is solitary through filtration washing
Stone resolution ratio is 97.9%, wherein in rare earth hydrate in the form of+trivalent state cerium hydroxide existing for cerium ratio Ce3+/Σ Ce be
89%, recycle of alkali liquor recycles in filtrate, and ton mine consumes 0.57 ton of sodium hydroxide.
Rare earth hydrate alkali cake is dissolved with the P204 of 0.2mol/L at 20 DEG C, during dissolving above-mentioned filter cake
Scene is generated without chlorine, obtains the organic phase that supported rare earth concentration is 0.02mol/L, and the extraction yield of rare earth reaches 99.1%,
The extraction yield 0.035% of thorium realizes thorium and Rare Earth Separation.
Load it is organic separated with insoluble matter after, the rare earth material of the organic extraction and separation as single rare earth of supported rare earth is straight
Capable separation is tapped into, a small amount of insoluble matter is stored up as excellent molten slag, thorium therein to be recycled, uranium.
Embodiment 2
REO content is set for 31.1% monazite (ThO2 content 3.1%) and 65% liquid alkaline with liquid-solid ratio for 1.5:1
In the reaction kettle of argon atmosphere, after vortex electric heating to 80 DEG C of decomposition reactions, reaction paste is through filtration washing, solely
Occupying stone resolution ratio is 96.5%, wherein in rare earth hydrate in the form of+trivalent state cerium hydroxide existing for cerium ratio Ce3+/Σ Ce
It is 95%, recycle of alkali liquor recycles in filtrate, and ton mine consumes 0.42 ton of sodium hydroxide.
Rare earth hydrate alkali cake is dissolved with the C272 of 0.5mol/L at 50 DEG C, during dissolving above-mentioned filter cake
Scene is generated without chlorine, obtains the organic phase that supported rare earth concentration is 0.05mol/L, and the extraction yield of rare earth reaches 99.0%,
The extraction yield of thorium realizes thorium and Rare Earth Separation less than 0.01%.
Load it is organic separated with insoluble matter after, rare earth material of the supported rare earth organic phase as the extraction and separation of single rare earth
It is directly separated, a small amount of insoluble matter carries out hydrochloric acid and preferentially dissolves, after filtration washing, and rare earth carries out extraction and separation in filtrate, excellent
Molten slag stockpiling, thorium therein to be recycled, uranium.
Embodiment 3
REO content is set for 64.9% monazite (ThO2 content 4.3%) and 20% liquid alkaline with liquid-solid ratio for 10:1
In the tubular reactor of helium protective atmosphere, after being steam heated to 345 DEG C of decomposition reactions, reaction paste passes through diafiltration
Wash, monazite resolution ratio is 98.5%, wherein in rare earth hydrate in the form of+trivalent state cerium hydroxide existing for cerium ratio Ce3+/
Σ Ce is 85%, and recycle of alkali liquor recycles in filtrate, and ton mine consumes 0.71 ton of sodium hydroxide.
Rare earth hydrate alkali cake is dissolved with the aphthenic acids of 0.9mol/L at 30 DEG C, during dissolving above-mentioned filter cake
Scene is generated without chlorine, obtains the organic phase that supported rare earth concentration is 0.09mol/L, and the extraction yield of rare earth reaches 92.5%,
The extraction yield 0.014% of thorium realizes thorium and Rare Earth Separation.
Load it is organic separated with insoluble matter after, rare earth material of the supported rare earth organic phase as the extraction and separation of single rare earth
It is directly separated, a small amount of insoluble matter carries out hydrochloric acid and preferentially dissolves, after filtration washing, and rare earth carries out extraction and separation in filtrate, excellent
Molten slag stockpiling, thorium therein to be recycled, uranium.
Embodiment 4
REO content is placed in for 51.3% monazite (ThO2 content 3.9%) and 50% liquid alkaline with liquid-solid ratio for 3:1
In the tubular reactor of nitrogen protection atmosphere, after oil bath heating to 170 DEG C of decomposition reactions, reaction paste through filtration washing,
Monazite resolution ratio is 98.7%, wherein in rare earth hydrate in the form of+trivalent state cerium hydroxide existing for cerium ratio Ce3+/Σ
Ce is 100%, and recycle of alkali liquor recycles in filtrate, and ton mine consumes 0.55 ton of sodium hydroxide.
Rare earth hydrate alkali cake is dissolved with the P204 of 1.5mol/L at 30 DEG C, it is existing in the process to dissolve above-mentioned filter cake
Field is generated without chlorine, obtains the organic phase that supported rare earth concentration is 0.17mol/L, and the extraction yield of rare earth reaches 99.5%, thorium
Extraction yield 0.011%, realize thorium and Rare Earth Separation.
Load it is organic separated with insoluble matter after, rare earth material of the supported rare earth organic phase as the extraction and separation of single rare earth
It is directly separated, a small amount of insoluble matter is directly stored up as excellent molten slag, thorium therein to be recycled, uranium.
Claims (11)
1. the technique of a kind of alkaline process processing monazite and extracting and separating rear earth, which is characterized in that the alkaline process handles monazite
Liquid alkaline and monazite mixture are heated in closed container in the process and reacted, is protected under non-oxidizing atmosphere,
Rare earth in monazite forms trivalent rare earth hydroxide and sodium radio-phosphate,P-32 solution in caustic digestion process, after filtration washing separates,
Trivalent rare earth hydroxide is dissolved using acidic extractant, obtains extraction point of the organic phase for rare earth of supported rare earth
From cerium exists in the form of+trivalent state rare-earth hydroxide in the trivalent rare earth hydroxide, wherein Ce3+/ Σ Ce is 80%-
100%.
2. the technique of a kind of alkaline process processing monazite according to claim 1 and extracting and separating rear earth, which is characterized in that institute
The monazite stated is the monazite concentrate of 30%REO-65%REO.
3. the technique of a kind of alkaline process processing monazite according to claim 1 and extracting and separating rear earth, which is characterized in that institute
The liquid alkaline stated is at least one of sodium hydroxide, potassium hydroxide, and the liquid of alkali concentration 20%-75%, liquid alkaline and monazite are solid
Mass ratio is 1.5:1-10:1, and reaction temperature is 80 DEG C -350 DEG C.
4. the technique of a kind of alkaline process processing monazite according to claim 1 and extracting and separating rear earth, which is characterized in that institute
The non-oxidizing gas stated includes but is not limited at least one of nitrogen, argon gas, helium, hydrogen.
5. the technique of a kind of alkaline process processing monazite according to claim 1 and extracting and separating rear earth, which is characterized in that institute
The closed container stated uses but is not limited to enclosed reaction kettle.
6. the technique of a kind of alkaline process processing monazite according to claim 1 and extracting and separating rear earth, which is characterized in that institute
At least one of steam heating, oil bath heating, Far-infrared Heating, vortex electric heating heating side can be used in the heating process stated
Formula.
7. the technique of a kind of alkaline process processing monazite according to claim 1 and extracting and separating rear earth, which is characterized in that institute
The acidic extractant stated includes but is not limited at least one of P204, P507, aphthenic acids, C272.
8. the technique of a kind of alkaline process processing monazite according to claim 1 and extracting and separating rear earth, which is characterized in that institute
The acidic extractant solution temperature stated is 20-50 DEG C, and the acidic extractant concentration is 0.2-1.8mol/L, according to organic negative
Carrying rare earth content is that 0.02-0.2mol/L carries out the reaction that feeds intake.
9. the technique of a kind of alkaline process processing monazite according to claim 1 and extracting and separating rear earth, which is characterized in that institute
The acidic extractant stated store up obtained a small amount of insoluble matter as excellent molten slag in course of dissolution, therein for recycling
Thorium, uranium.
10. the technique of a kind of alkaline process processing monazite according to claim 1 and extracting and separating rear earth, which is characterized in that
The acidic extractant carries out in course of dissolution, a small amount of by what is obtained in the case that preferential selection rare-earth yield is less than 99%
Insoluble matter carries out hydrochloric acid and preferentially dissolves, after filtration washing, and rare earth carries out extraction and separation, excellent molten slag stockpiling, for recycling in filtrate
Thorium therein, uranium.
11. the technique of a kind of alkaline process processing monazite according to claim 1 and extracting and separating rear earth, which is characterized in that
The trivalent rare earth hydroxide can directly adopt hydrochloric acid and carry out excellent molten formation rare earth chloride to it, realize point of rare earth and thorium
From.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1142542A (en) * | 1995-07-04 | 1997-02-12 | 山东微山华能稀土总公司 | Process and apparatus for preparing chlorinated rare-earth from fine rare-earth minerals by alkali water heating process |
| CN102212674A (en) * | 2011-05-12 | 2011-10-12 | 包头稀土研究院 | Process for comprehensively recovering liquid alkali roasting resource of mixed rare earth concentrate |
| CN103014333A (en) * | 2012-11-27 | 2013-04-03 | 益阳鸿源稀土有限责任公司 | Separation and recovery method of uranium, thorium and rare earth in monazite slag |
| CN103103349A (en) * | 2013-02-05 | 2013-05-15 | 内蒙古科技大学 | Method for decomposing bayan obo rare earth ore concentrate by acid and alkali combination at low temperature |
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- 2015-04-21 CN CN201510188991.5A patent/CN106148691B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1142542A (en) * | 1995-07-04 | 1997-02-12 | 山东微山华能稀土总公司 | Process and apparatus for preparing chlorinated rare-earth from fine rare-earth minerals by alkali water heating process |
| CN102212674A (en) * | 2011-05-12 | 2011-10-12 | 包头稀土研究院 | Process for comprehensively recovering liquid alkali roasting resource of mixed rare earth concentrate |
| CN103014333A (en) * | 2012-11-27 | 2013-04-03 | 益阳鸿源稀土有限责任公司 | Separation and recovery method of uranium, thorium and rare earth in monazite slag |
| CN103103349A (en) * | 2013-02-05 | 2013-05-15 | 内蒙古科技大学 | Method for decomposing bayan obo rare earth ore concentrate by acid and alkali combination at low temperature |
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