CN108034817A - Lime substitutes the technique that liquid caustic soda carries out alkali reaction in a kind of rare-earth smelting - Google Patents
Lime substitutes the technique that liquid caustic soda carries out alkali reaction in a kind of rare-earth smelting Download PDFInfo
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- CN108034817A CN108034817A CN201711047030.8A CN201711047030A CN108034817A CN 108034817 A CN108034817 A CN 108034817A CN 201711047030 A CN201711047030 A CN 201711047030A CN 108034817 A CN108034817 A CN 108034817A
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- recrement
- rare earth
- lime
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- caustic soda
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- 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
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/10—Hydrochloric acid, other halogenated acids or salts thereof
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- 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
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- 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
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- 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
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- 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)
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- Geochemistry & Mineralogy (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
Lime substitutes the technique that liquid caustic soda carries out alkali reaction in a kind of rare-earth smelting, includes the following steps：(1) bastnaesite after oxidizing roasting or mixed type Rare Earth Mine are reacted under 0.3 0.5N hydrochloric acid systems, obtain rare earth chloride liquid and No. I recrement；(2) No. I recrement is transferred in reaction kettle, adds lime, water and catalyst and reacted, obtain No. II recrement；(3) toward hydrochloric acid is added in reaction kettle, No. II recrement is reacted under 0.8 1N hydrochloric acid systems, obtain rare earth chloride liquid and No. III recrement.(4) No. III recrements obtain fluorite and cerium enriched substance through FLOTATION SEPARATION.The present invention substitutes liquid caustic soda using lime, fluorine is set to be converted into fluorite, the step of washing defluorinate can be saved, realize anhydrous discharge, solve the problems, such as in existing Rare Earth Mine smelting process that wastewater discharge is big, fluorine is difficult to recycling, meanwhile can also realize fluorine comprehensive utilization of resources, greatly improve the overall economic efficiency of bastnaesite or mixed type Rare Earth Mine.
Description
Technical field
The invention belongs to field of rare earth hydrometallurgy, and in particular to it is anti-to substitute liquid caustic soda progress alkali for lime in a kind of rare-earth smelting
The technique answered.
Background technology
Hydrometallurgy be exactly metalliferous mineral raw material be chemically treated in the aqueous solution of acid medium or alkaline medium or
Organic solvent extraction, separation impurity, the process for extracting metal and its compound.At present, the fluorine carbon after rare-earth trade oxidizing roasting
Cerium ore deposit and mixed type Rare Earth Mine are smelted using hydrochloric acid leaching, alkali reaction, water elution F, hydrochloric acid leaching technique substantially.But should
Technique has the drawback that, after carrying out alkali reaction using liquid caustic soda, need to pass through massive laundering defluorinate, and wastewater discharge is big, fluorine recycling
Intractability is big.
The content of the invention
It is an object of the invention to：For in above-mentioned existing bastnaesite or mixed type Rare Earth Mine smelting process because of water elution
Fluorine and cause the problem of wastewater discharge is big, fluorine is difficult to recycling, the present invention provide lime in a kind of rare-earth smelting substitute liquid caustic soda into
The technique of row alkali reaction.
The technical solution adopted by the present invention is as follows：
Lime substitutes the technique that liquid caustic soda carries out alkali reaction in a kind of rare-earth smelting, and step is as follows：
(1) bastnaesite after oxidizing roasting or mixed type Rare Earth Mine are reacted under 0.3-0.5N hydrochloric acid systems, are obtained
Rare earth chloride liquid and No. I recrement；
(2) No. I recrement is transferred in reaction kettle, adds lime, water and catalyst and reacted, obtain No. II recrement；
(3) toward hydrochloric acid is added in reaction kettle, No. II recrement is reacted under 0.8-1N hydrochloric acid systems, obtain rare earth chloride material
Liquid and No. III recrement.
(4) No. III recrements obtain fluorite and cerium enriched substance through FLOTATION SEPARATION.
Bastnaesite after oxidizing roasting or mixed type Rare Earth Mine are being used 0.3-0.5N hydrochloric acid leachings by the present invention
During, cerium is converted into ceria, remaining rare earth part obtains rare earth chloride liquid, remainder with chloropexia
Divide and then generate rare earth fluoride, rare earth fluoride not soluble in water forms No. I recrement (reaction 1) with ceria, then makes No. I recrement
Reacted with lime, water under conditions of catalyst, rare earth fluoride can be made to be converted into calcirm-fluoride, meanwhile, generate the hydrogen of rare earth
Oxide precipitation (reaction 2), finally adds hydrochloric acid, precipitates the hydroxide of rare earth and is converted into rare earth chloride liquid (reaction
3), so as to obtain No. III recrement of the component for calcirm-fluoride and ceria, No. III recrement is carried out FLOTATION SEPARATION obtain fluorite and
Cerium enriched substance.
Reaction 1：REOF+HCl→REF3+RECl3+H2O+CeO2
Reaction 2：
Reaction 3：CaF2+RE(OH)3+HCl+CeO2→CaF2+RECl3+H2O+CeO2
Further, in the step (1), when the reaction time is 2-3 small.Bastnaesite or mixing after oxidizing roasting
Type Rare Earth Mine and 0.3-0.5N hydrochloric acid reaction 2-3 can ensure that the reaction was complete when small, i.e., cerium is completely converted into ceria, together
When, remaining rare earth is also completely converted into rare earth fluoride, or obtains rare earth chloride liquid with chloropexia.
Further, in the step (2), the dosage of lime is bastnaesite or the 10- of mixed type Rare Earth Mine weight
15%.Lime content is too low, and rare earth fluoride cannot be completely converted into calcirm-fluoride, causes last cerium enriched substance to contain fluorine and other dilute
Native impurity, on the one hand reduces grade, and on the other hand, other rare earths are difficult to recycle, and cause the wasting of resources.Lime content mistake
It is high so as to contain calcium hydroxide precipitation in No. II recrement, after last hydrochloric acid leaching, chlorination can be introduced in rare earth chloride liquid
Calcium impurities, are unfavorable for rare earth chloride liquid subsequent smelting.
Further, in the step (2), catalyst is potassium chloride.Potassium chloride can accelerate reaction 2 to carry out, and be conducive to carry
High efficiency.
Further, in the step (2), the dosage of potassium chloride is bastnaesite or the 1- of mixed type Rare Earth Mine weight
1.5‰。
Further, the step (2) is reacted under stirring, when the reaction time is 8-10 small.Stirring is favourable
It is uniformly mixed in raw material, improves reaction efficiency, reaction 8-10 can ensures that rare earth fluoride is completely converted into calcirm-fluoride, avoids cerium when small
Enriched substance contains the impurity such as fluorine.
Further, in the step (3), when the reaction time is 2-3 small.Finally carry out hydrochloric acid leaching purpose be make it is dilute
The hydroxide precipitation of soil is converted into rare earth chloride liquid, and reaction 2-3 can ensure that the reaction was complete when small.
In conclusion by adopting the above-described technical solution, the beneficial effects of the invention are as follows：
1. the present invention substitutes liquid caustic soda using lime, and under the action of catalyst, fluorine is converted into fluorite, through flotation and cerium
Enriched substance separates, and can save the step of washing defluorinate, realize anhydrous discharge, solve existing bastnaesite or mixed type Rare Earth Mine
In smelting process because wash defluorinate and caused by wastewater discharge is big, fluorine is difficult to recycling the problem of；
On the one hand 2. the present invention can shorten technological process, reduce production cost, separately due to the step of eliminating washing defluorinate
On the one hand, water resource is saved；
3. by the present invention in that fluorine is converted into fluorite, fluorite can be used for producing hydrofluoric acid, or be used as fluxing agent, mineralizer
, it can be achieved that the comprehensive utilization of fluorine resource, greatly improves bastnaesite or mixed type in the building materials industries such as glass, ceramics, cement
The overall economic efficiency of Rare Earth Mine；
4. the technique of the present invention is simple, operating cost is low, and operates succinct, environmentally protective.
Embodiment
All features disclosed in this specification, can be with any in addition to mutually exclusive feature and/or step
Mode combines.
Embodiment 1
Take the bastnaesite after 200g oxidizing roastings or mixed rare earth concentrate to be placed in 2L flat bottom beakers, add at the same time
When the hydrochloric acid reaction 2 of 0.3N is small, rare earth chloride liquid and No. I recrement are obtained, No. I recrement is transferred in reaction kettle, add 20g
Lime and 0.2g potassium chloride, when stirring reaction 8 is small after obtain No. II recrement, then the hydrochloric acid of 0.8N is added in No. II recrement, instead
Answer 2 it is small when after obtain rare earth chloride liquid and No. III recrement, after No. III recrement FLOTATION SEPARATION, obtain fluorite 30g (purity
92.8%), cerium enriched substance 102g (REO60%), fluorite and cerium enriched substance meet quality standard (purity, appearance, chemical index).
Embodiment 2
Take the bastnaesite after 300g oxidizing roastings or mixed rare earth concentrate to be placed in 2L flat bottom beakers, add at the same time
When the hydrochloric acid reaction 2 of 0.3N is small, rare earth chloride liquid and No. I recrement are obtained, No. I recrement is transferred in reaction kettle, add 36g
Lime and 0.4g potassium chloride, when stirring reaction 8 is small after obtain No. II recrement, then the hydrochloric acid of 0.8N is added in No. II recrement, instead
Answer 2 it is small when after obtain rare earth chloride liquid and No. III recrement, after No. III recrement FLOTATION SEPARATION, obtain fluorite 45g (purity
92.5%), cerium enriched substance 156g (REO60%), fluorite and cerium enriched substance meet quality standard (purity, appearance, chemical index).
Embodiment 3
Take the bastnaesite after 400g oxidizing roastings or mixed rare earth concentrate to be placed in 2L flat bottom beakers, add at the same time
When the hydrochloric acid reaction 2 of 0.3N is small, rare earth chloride liquid and No. I recrement are obtained, No. I recrement is transferred in reaction kettle, add 60g
Lime and 0.4g potassium chloride, when stirring reaction 8 is small after obtain No. II recrement, then the hydrochloric acid of 0.8N is added in No. II recrement, instead
Answer 2 it is small when after obtain rare earth chloride liquid and No. III recrement, after No. III recrement FLOTATION SEPARATION, obtain fluorite 59g (purity
93.2%), cerium enriched substance 198g (REO60%), fluorite and cerium enriched substance meet quality standard (purity, appearance, chemical index).
Embodiment 4
Take the bastnaesite after 500g oxidizing roastings or mixed rare earth concentrate to be placed in 2L flat bottom beakers, add at the same time
When the hydrochloric acid reaction 2 of 0.3N is small, rare earth chloride liquid and No. I recrement are obtained, No. I recrement is transferred in reaction kettle, add 70g
Lime and 0.7g potassium chloride, when stirring reaction 8 is small after obtain No. II recrement, then the hydrochloric acid of 0.8N is added in No. II recrement, instead
Answer 2 it is small when after obtain rare earth chloride liquid and No. III recrement, after No. III recrement FLOTATION SEPARATION, obtain fluorite 78g (purity
91.9%), cerium enriched substance 254g (REO60%), fluorite and cerium enriched substance meet quality standard (purity, appearance, chemical index).
It is the embodiment of the present invention as described above.The present invention is not limited to the above-described embodiments, anyone should learn that
The structure change made under the enlightenment of the present invention, the technical schemes that are same or similar to the present invention, each fall within this
Within the protection domain of invention.
Claims (7)
1. lime substitutes the technique that liquid caustic soda carries out alkali reaction in a kind of rare-earth smelting, it is characterised in that step is as follows：
(1) bastnaesite after oxidizing roasting or mixed type Rare Earth Mine are reacted under 0.3-0.5N hydrochloric acid systems, obtain chlorination
Rare earth feed liquid and No. I recrement；
(2) No. I recrement is transferred in reaction kettle, adds lime, water and catalyst and reacted, obtain No. II recrement；
(3) toward hydrochloric acid is added in reaction kettle, No. II recrement is reacted under 0.8-1N hydrochloric acid systems, obtain rare earth chloride liquid and
No. III recrement.
(4) No. III recrements obtain fluorite and cerium enriched substance through FLOTATION SEPARATION.
2. lime substitutes the technique that liquid caustic soda carries out alkali reaction in a kind of rare-earth smelting according to claim 1, its feature exists
In in the step (1), when the reaction time is 2-3 small.
3. lime substitutes the technique that liquid caustic soda carries out alkali reaction in a kind of rare-earth smelting according to claim 1, its feature exists
In in the step (2), the dosage of lime is bastnaesite or the 10-15% of mixed type Rare Earth Mine weight.
4. lime substitutes the technique that liquid caustic soda carries out alkali reaction, its feature in a kind of rare-earth smelting according to claim 1 or 3
It is, in the step (2), catalyst is potassium chloride.
5. lime substitutes the technique that liquid caustic soda carries out alkali reaction in a kind of rare-earth smelting according to claim 4, its feature exists
In in the step (2), the dosage of potassium chloride is bastnaesite or the 1-1.5 ‰ of mixed type Rare Earth Mine weight.
6. lime substitutes the technique that liquid caustic soda carries out alkali reaction, its feature in a kind of rare-earth smelting according to claim 1 or 3
It is, the step (2) is reacted under stirring, when the reaction time is 8-10 small.
7. lime substitutes the technique that liquid caustic soda carries out alkali reaction in a kind of rare-earth smelting according to claim 1, its feature exists
In in the step (3), when the reaction time is 2-3 small.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711047030.8A CN108034817B (en) | 2017-10-31 | 2017-10-31 | The technique that lime substitution liquid alkaline carries out alkali reaction in a kind of rare-earth smelting |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711047030.8A CN108034817B (en) | 2017-10-31 | 2017-10-31 | The technique that lime substitution liquid alkaline carries out alkali reaction in a kind of rare-earth smelting |
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| CN108034817A true CN108034817A (en) | 2018-05-15 |
| CN108034817B CN108034817B (en) | 2019-08-27 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109022796A (en) * | 2018-08-17 | 2018-12-18 | 中山大学 | A kind of low-temperature environment-friendly method from polished waste material recovering rare earth |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102146512A (en) * | 2010-02-08 | 2011-08-10 | 北京有色金属研究总院 | Hamartite smelting separation process |
| CN103014334A (en) * | 2012-07-02 | 2013-04-03 | 周毅 | Method for replacement dissolution of bastnaesite (bastnasite) |
| CN104278164A (en) * | 2014-09-29 | 2015-01-14 | 乐山盛和稀土股份有限公司 | Treatment technique of rare earth fluorocarbonate ores with grade of 62-72% |
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2017
- 2017-10-31 CN CN201711047030.8A patent/CN108034817B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102146512A (en) * | 2010-02-08 | 2011-08-10 | 北京有色金属研究总院 | Hamartite smelting separation process |
| CN103014334A (en) * | 2012-07-02 | 2013-04-03 | 周毅 | Method for replacement dissolution of bastnaesite (bastnasite) |
| CN104278164A (en) * | 2014-09-29 | 2015-01-14 | 乐山盛和稀土股份有限公司 | Treatment technique of rare earth fluorocarbonate ores with grade of 62-72% |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109022796A (en) * | 2018-08-17 | 2018-12-18 | 中山大学 | A kind of low-temperature environment-friendly method from polished waste material recovering rare earth |
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