CN108034817B - The technique that lime substitution liquid alkaline carries out alkali reaction in a kind of rare-earth smelting - Google Patents

The technique that lime substitution liquid alkaline carries out alkali reaction in a kind of rare-earth smelting Download PDF

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Publication number
CN108034817B
CN108034817B CN201711047030.8A CN201711047030A CN108034817B CN 108034817 B CN108034817 B CN 108034817B CN 201711047030 A CN201711047030 A CN 201711047030A CN 108034817 B CN108034817 B CN 108034817B
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recrement
lime
rare earth
rare
technique
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CN108034817A (en
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不公告发明人
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Sichuan Emtronix Environmental Technology Co Ltd
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Sichuan Emtronix Environmental Technology Co Ltd
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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
    • 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
    • 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
    • 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

Abstract

Lime substitution liquid alkaline carries out the technique of alkali reaction in a kind of rare-earth smelting, and bastnaesite or mixed type Rare Earth Mine after including the following steps: (1) oxidizing roasting react under 0.3-0.5N hydrochloric acid system, obtains rare earth chloride liquid and No. I recrement；(2) No. I recrement is transferred in reaction kettle, lime, water and catalyst is added and is reacted, No. II recrement is obtained；(3) hydrochloric acid is added into reaction kettle, reacts No. II recrement under 0.8-1N hydrochloric acid system, obtains 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 alkaline 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 recycle, meanwhile can also be achieved fluorine comprehensive utilization of resources, greatly improve the overall economic efficiency of bastnaesite or mixed type Rare Earth Mine.

Description

The technique that lime substitution liquid alkaline carries out alkali reaction in a kind of rare-earth smelting
Technical field
The invention belongs to field of rare earth hydrometallurgy, and in particular to it is anti-to carry out alkali for lime substitution liquid alkaline in a kind of rare-earth smelting The technique answered.
Background technique
Hydrometallurgy be exactly metalliferous mineral raw material carried out in the aqueous solution of acid medium or alkaline medium chemical treatment or Organic solvent extraction, separation impurity, the process for extracting metal and its compound.Currently, the fluorine carbon after rare-earth trade oxidizing roasting Cerium mine and mixed type Rare Earth Mine use hydrochloric acid leaching, alkali reaction, water elution F, hydrochloric acid leaching technique to be smelted substantially.But it should Technique has the drawback that, after carrying out alkali reaction using liquid alkaline, need to pass through massive laundering defluorinate, and wastewater discharge is big, fluorine recycling Processing difficulty is big.
Summary of the invention
It is an object of the invention to: it is directed in above-mentioned existing bastnaesite or mixed type Rare Earth Mine smelting process because of water elution Fluorine and cause that wastewater discharge is big, fluorine is difficult to the problem of recycling, the present invention provide lime in a kind of rare-earth smelting substitute liquid alkaline into The technique of row alkali reaction.
The technical solution adopted by the invention is as follows:
Lime substitution liquid alkaline carries out the technique of alkali reaction in a kind of rare-earth smelting, and steps are as follows:
(1) bastnaesite after oxidizing roasting or mixed type Rare Earth Mine are reacted under 0.3-0.5N hydrochloric acid system, are obtained Rare earth chloride liquid and No. I recrement；
(2) No. I recrement is transferred in reaction kettle, lime, water and catalyst is added and is reacted, No. II recrement is obtained；
(3) hydrochloric acid is added into reaction kettle, reacts No. II recrement under 0.8-1N hydrochloric acid system, obtains rare earth chloride material Liquid and No. III recrement.
(4) No. III recrements obtain fluorite and cerium enriched substance through FLOTATION SEPARATION.
The present invention by after oxidizing roasting bastnaesite or mixed type Rare Earth Mine using 0.3-0.5N hydrochloric acid leaching In the process, cerium is converted into ceria, remaining rare earth a part and chloropexia obtain rare earth chloride liquid, remainder Divide and then generate rare earth fluoride, rare earth fluoride not soluble in water constitutes No. I recrement (reacting 1) with ceria, then makes No. I recrement It is reacted under conditions of catalyst with lime, water, 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), to obtain No. III recrement that ingredient is calcirm-fluoride and ceria, to No. III recrement carry out FLOTATION SEPARATION obtain fluorite and Cerium enriched substance.
React 1:REOF+HCl → REF3+RECl3+H2O+CeO2
Reaction 2:
React 3:CaF2+RE(OH)3+HCl+CeO2→CaF2+RECl3+H2O+CeO2
Further, in the step (1), the reaction time is 2-3 hours.Bastnaesite or mixing after oxidizing roasting Type Rare Earth Mine reacts certifiable fully reacting in 2-3 hours with 0.3-0.5N hydrochloric acid, 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 the 10- of bastnaesite or mixed type Rare Earth Mine weight 15%.Lime content is too low, and rare earth fluoride cannot be completely converted into calcirm-fluoride, and last cerium enriched substance is caused to contain fluorine and other dilute On the one hand native impurity reduces grade, on the other hand, other rare earths are difficult to recycle, result in waste of resources.Lime content mistake Height after last hydrochloric acid leaching, can introduce chlorination so that containing calcium hydroxide precipitation in No. II recrement 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 mention High efficiency.
Further, in the step (2), the dosage of potassium chloride is the 1- of bastnaesite or mixed type Rare Earth Mine weight 1.5‰。
Further, the step (2) is reacted under stirring, and the reaction time is 8-10 hours.Stirring is advantageous It is uniformly mixed in raw material, improves reaction efficiency, 8-10 hours certifiable rare earth fluorides of reaction are completely converted into calcirm-fluoride, avoid cerium Enriched substance contains the impurity such as fluorine.
Further, in the step (3), the reaction time is 2-3 hours.Finally carry out hydrochloric acid leaching purpose be make it is dilute The hydroxide precipitating of soil is converted into rare earth chloride liquid, can guarantee fully reacting within reaction 2-3 hours.
In conclusion by adopting the above-described technical solution, the beneficial effects of the present invention are:
1. the present invention substitutes liquid alkaline using lime, and under the effect of the catalyst, so that fluorine is converted into fluorite, through flotation and cerium Enriched substance separation, can save the step of washing defluorinate, realize anhydrous discharge, solve existing bastnaesite or mixed type Rare Earth Mine Cause because washing defluorinate that wastewater discharge is big, fluorine is difficult to the problem of recycling in smelting process；
2. on the one hand the present invention can shorten process flow, reduce production cost, separately due to the step of eliminating washing defluorinate On the one hand, water resource is saved；
3. fluorite can be used for producing hydrofluoric acid, or use as fluxing agent, mineralizer by the present invention in that fluorine is converted into fluorite , 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. simple process of the invention, operating cost are low, and operate succinct, environmentally protective.
Specific embodiment
All features disclosed in this specification can be with any other than mutually exclusive feature and/or step Mode combines.
Embodiment 1
Bastnaesite or mixed rare earth concentrate after taking 200g oxidizing roasting are placed in 2L flat bottom beaker, are added simultaneously The hydrochloric acid of 0.3N reacts 2 hours, obtains rare earth chloride liquid and No. I recrement, No. I recrement is transferred in reaction kettle, and 20g is added Lime and 0.2g potassium chloride obtain No. II recrement after being stirred to react 8 hours, then the hydrochloric acid of 0.8N is added in No. II recrement, instead It obtains rare earth chloride liquid and No. III recrement after answering 2 hours, after No. III recrement FLOTATION SEPARATION, obtains fluorite 30g (purity 92.8%), cerium enriched substance 102g (REO60%), fluorite and cerium enriched substance meet the quality standard (purity, appearance, chemical index).
Embodiment 2
Bastnaesite or mixed rare earth concentrate after taking 300g oxidizing roasting are placed in 2L flat bottom beaker, are added simultaneously The hydrochloric acid of 0.3N reacts 2 hours, obtains rare earth chloride liquid and No. I recrement, No. I recrement is transferred in reaction kettle, and 36g is added Lime and 0.4g potassium chloride obtain No. II recrement after being stirred to react 8 hours, then the hydrochloric acid of 0.8N is added in No. II recrement, instead It obtains rare earth chloride liquid and No. III recrement after answering 2 hours, after No. III recrement FLOTATION SEPARATION, obtains fluorite 45g (purity 92.5%), cerium enriched substance 156g (REO60%), fluorite and cerium enriched substance meet the quality standard (purity, appearance, chemical index).
Embodiment 3
Bastnaesite or mixed rare earth concentrate after taking 400g oxidizing roasting are placed in 2L flat bottom beaker, are added simultaneously The hydrochloric acid of 0.3N reacts 2 hours, obtains rare earth chloride liquid and No. I recrement, No. I recrement is transferred in reaction kettle, and 60g is added Lime and 0.4g potassium chloride obtain No. II recrement after being stirred to react 8 hours, then the hydrochloric acid of 0.8N is added in No. II recrement, instead It obtains rare earth chloride liquid and No. III recrement after answering 2 hours, after No. III recrement FLOTATION SEPARATION, obtains fluorite 59g (purity 93.2%), cerium enriched substance 198g (REO60%), fluorite and cerium enriched substance meet the quality standard (purity, appearance, chemical index).
Embodiment 4
Bastnaesite or mixed rare earth concentrate after taking 500g oxidizing roasting are placed in 2L flat bottom beaker, are added simultaneously The hydrochloric acid of 0.3N reacts 2 hours, obtains rare earth chloride liquid and No. I recrement, No. I recrement is transferred in reaction kettle, and 70g is added Lime and 0.7g potassium chloride obtain No. II recrement after being stirred to react 8 hours, then the hydrochloric acid of 0.8N is added in No. II recrement, instead It obtains rare earth chloride liquid and No. III recrement after answering 2 hours, after No. III recrement FLOTATION SEPARATION, obtains fluorite 78g (purity 91.9%), cerium enriched substance 254g (REO60%), fluorite and cerium enriched substance meet the quality standard (purity, appearance, chemical index).
It is as described above the embodiment of the present invention.The present invention is not limited to the above-described embodiments, anyone should learn that The structure change made under the inspiration of the present invention, the technical schemes that are same or similar to the present invention each fall within this Within the protection scope of invention.

Claims (6)

1. the technique that lime substitution liquid alkaline carries out alkali reaction in a kind of rare-earth smelting, which is characterized in that steps are as follows:
(1) bastnaesite after oxidizing roasting or mixed type Rare Earth Mine are reacted under 0.3-0.5N hydrochloric acid system, obtain chlorination Rare-earth liquid and No. I recrement；
(2) No. I recrement is transferred in reaction kettle, lime, water and catalyst is added and is reacted, No. II recrement is obtained；Wherein, Catalyst is potassium chloride；
(3) hydrochloric acid is added into reaction kettle, reacts No. II recrement under 0.8-1N hydrochloric acid system, obtain rare earth chloride liquid and No. III recrement；
(4) No. III recrements obtain fluorite and cerium enriched substance through FLOTATION SEPARATION.
2. lime substitution liquid alkaline carries out the technique of alkali reaction in a kind of rare-earth smelting according to claim 1, feature exists In in step (1), the reaction time is 2-3 hours.
3. lime substitution liquid alkaline carries out the technique of alkali reaction in a kind of rare-earth smelting according to claim 1, feature exists In in step (2), the dosage of lime is the 10-15% of bastnaesite or mixed type Rare Earth Mine weight.
4. lime substitution liquid alkaline carries out the technique of alkali reaction in a kind of rare-earth smelting according to claim 1, feature exists In in step (2), the dosage of potassium chloride is the 1-1.5 ‰ of bastnaesite or mixed type Rare Earth Mine weight.
5. lime substitution liquid alkaline carries out the technique of alkali reaction, feature in a kind of rare-earth smelting according to claim 1 or 3 It is, step (2) is reacted under stirring, and the reaction time is 8-10 hours.
6. lime substitution liquid alkaline carries out the technique of alkali reaction in a kind of rare-earth smelting according to claim 1, feature exists In in step (3), the reaction time is 2-3 hours.
CN201711047030.8A 2017-10-31 2017-10-31 The technique that lime substitution liquid alkaline carries out alkali reaction in a kind of rare-earth smelting Expired - Fee Related CN108034817B (en)

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CN109022796B (en) * 2018-08-17 2020-10-02 中山大学 Low-temperature environment-friendly method for recycling rare earth from polishing waste

Citations (3)

* Cited by examiner, † Cited by third party
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%

Patent Citations (3)

* Cited by examiner, † Cited by third party
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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