CN1077546C - Method for producing mixed rare-earth chloride - Google Patents
Method for producing mixed rare-earth chloride Download PDFInfo
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- CN1077546C CN1077546C CN98112044A CN98112044A CN1077546C CN 1077546 C CN1077546 C CN 1077546C CN 98112044 A CN98112044 A CN 98112044A CN 98112044 A CN98112044 A CN 98112044A CN 1077546 C CN1077546 C CN 1077546C
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- alkali
- hydrochloric acid
- acid leaching
- rare earth
- roasting
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Abstract
The present invention relates to a method for producing mixed rare-earth chloride. The method of the present invention comprises the ordinal steps that hamartite or mixed ore mainly containing the hamartite is roasted for 1 hour at the temperature of 470 to 550 DEG C; diluted hydrochloric acid is added tp leach and remove calcium and magnesium impurities from the mixed ore; concentrated hydrochloric acid is added to leaching and filtration, and acid leaching solution is reserved; sodium hydroxide is added into acid dipping slag for alkali conversion; alkali slag is washed by water for filtration, and waste water is removed; the alkali slag is neutralized with the acid leaching solution; sulphuric acid is added to remove plumbum and barium, H2 O2 assist dissolves are added to remove iron, and BaCI2 is added to remove redundant SO4 <2->; solution is reserved after filtration. The filter solution is fabricated into mixed rare earth chloride products via negative pressure heating, concentration and crystallization.
Description
The present invention is relevant with the method for making of mixed chlorinated rare earth, and especially to prepare the production method of mixed chlorinated rare earth relevant with Sichuan Mianning hamartite.
The method for making of existing mixed chlorinated rare earth is Sichuan Mianning rare earth ore concentrate to be carried out pickling with the hydrochloric acid of 0.5N is capable as described in the Chinese invention patent ublic specification of application of CN1078498A as publication number, temperature is controlled at 80-90 ℃, filter then, and the first step is mixed liquid, get filter cake, the hydrochloric acid that adds 7-8N carries out acidleach, temperature is 85-95 ℃, filter, keep filtrate, filter cake adds 50-70% sodium hydroxide solution and transforms, and pressure is 0.1-0.5MPa, temperature is 150-250 ℃, the pickling liquor and the alkali commentaries on classics filter cake that keep are reacted, and temperature is 85-95 ℃, and reaction adds a small amount of sulfuric acid simultaneously and aqua ammonia accent pH is 4 removal of impurities, filter, filtrate is carried out condensing crystal and is promptly got product.This method is directly soaked the ore deposit with hydrochloric acid, and leaching yield is too low, and is about 15%, and the quantity of slag is big, consumption alkali height, and the technology total recovery is low.Because hydrochloric acid leaching temperature height, the time is long, and equipment corrosion is serious, and facility investment is big, the production cost height.
It is few to the purpose of this invention is to provide a kind of consumption alkali, and facility investment is few, technology total recovery height, productivity height, the production method of the mixed chlorinated rare earth that production cost is low.
The present invention is achieved in that
The production method of mixed chlorinated rare earth, its steps in sequence is as follows:
1) select raw material for use:
Select hamartite for use or based on the mixing ore deposit of hamartite,
2) roasting raw material:
470-550 ℃ of fusing sintering temperatures, time 〉=1h adopts oxidizing roasting or reducing atmosphere roasting to make hamartite be decomposed into rare earth oxide.
3) hydrochloric acid leaching:
(1) for the rare earth oxide in the raw material hamartite (TREO) 45-60%, through the dilute hydrochloric acid washing, acidity 0.2-0.5N removes the calcium magnesium addition to the roasted ore of roasting gained earlier, again by (2) described condition hydrochloric acid leaching;
(2) for the roasted ore of the rare earth oxide in the raw material hamartite (TREO) 〉=60% roasting gained or the pickling ore deposit of the rapid gained of previous step, use the concentrated hydrochloric acid acidleach, acidity 2-11N, hydrochloric acid consumption: (weight ratio) REO: concentrated hydrochloric acid 31% 〉=1: 2.5-2.75, temperature temperature normal temperature (reducing roasting) or 〉=80 ℃ (oxidizing roasting), time 〉=2h needs add H under less than 60 ℃ temperature to the roasted ore of oxidizing roasting
2O
2The hydrogen peroxide hydrotropy is to CeO
2Ce in/TREO 〉=45% or the slag
4+=0, time 2-4h filters, and keeps pickling liquor,
4) acid leaching residue alkali changes: acid leaching residue is added hydroxide bases to be changeed,
Alkali: roasted ore REO=0.4-0.8: 1 (weight ratio), basicity 20～55%, temperature 〉=95 ℃, time 2-4h, washing terminal point pH7-8 removes waste water, alkali is changeed acid leaching residue and pickling liquor enters next step jointly:
5) in and removal of impurities:
Alkali changes acid leaching residue and neutralization reaction is carried out in pickling liquor, and pH is 1.5-2.5 adding H
2SO
4Deleading, barium, adding H
2O
2Hydrotropy and deironing add BaCl
2Remove unnecessary SO
4 2-Transferring pH is 4.0-4.5 deironing thoriums, filters to keep filtrate.
6) concentrate: negative pressure adds the hot filtrate condensing crystal, promptly gets the mixed chlorinated rare earth product to rare earth chloride TREO 〉=45%.
The acid leaching residue alkali of step 3) hydrochloric acid leaching of the present invention and step 4) transforms in the same acid and alkali-resistance retort and carries out.
Can in same acid and alkali-resistance retort, carry out with removal of impurities in the acid leaching residue alkali conversion of step 4) of the present invention and the step 5).
The present invention uses hydrochloric acid leaching after the roasting of Mianning hamartite is decomposed again, and the leaching rate height generally can reach 60-70%, and the quantity of slag is few, and the physical sedimentation performance is good.Acid leaching residue alkali changes easily, and consumption alkali is few, and the technology total recovery can reach 88-93%.The present invention is all not high to the acidity and the temperature requirement of used hydrochloric acid, and when having reductive agent to exist to the roasted ore of reducing roasting or oxidizing roasting ore deposit, salt acidacidity＞2N gets final product, and temperature is that normal temperature also can carry out.The present invention carries out hydrochloric acid leaching and the commentaries on classics of acid leaching residue alkali in same equipment (acid and alkali-resistance retort), facility investment is few, and throughput is big, and production cost is low.
Following is embodiments of the invention:
To contain and mix rare earth oxide is 60% Sichuan Mianning fluorine carbon decorations concentrate 470-550 ℃ roasting temperature 1 hour, roasted ore.
1 ton of roasted ore is added 2000 liters of technical hydrochloric acid thin ups to 7N, be heated to 80 ℃, be incubated 2 hours, filter, keep pickling liquor, the slag that soaks after filtering is added 1000 liter of 30% sodium hydroxide solution, controlled temperature is 95 ℃, and soaking time washed with water after 2 hours, make its pH7-8, remove washing waste water.Acid leaching residue after the washing is added the pickling liquor that keeps, and to pH2.0, the content according to lead in the roasted ore and barium adds 10 kilograms of industrial sulphuric acids simultaneously, is incubated 0.5 hour, removes delead and barium, adds H down at＜60 ℃
2O
2Remove de-iron and hydrotropy, add BaCl
4 2-Remove unnecessary SO
4 2-Adding ammoniacal liquor accent pH is 4-4.5, filters and abandons filter residue, then filtrate is carried out the negative pressure condensing crystal and promptly gets mixed chlorinated rare earth product of the present invention.
Embodiment 2:
To contain and mix rare earth oxide is that 45% Sichuan Mianning fluoro-carbon-cerium ore concentrate is as raw material, the calcining process condition is identical with embodiment 1, after the roasting, with 2000 liters of pickling of dilute hydrochloric acid of 0.3N, remove the calcium magnesium addition of roasted ore, enter the concentrated hydrochloric acid leaching again, acid leaching residue alkali changes, in and removal of impurities, the condensing crystal operation, processing condition are identical with the condition of the same processes of embodiment 1.
Claims (3)
1, a kind of production method of mixed chlorinated rare earth, its steps in sequence is as follows:
1) select raw material for use:
Select hamartite for use or based on the mixing ore deposit of hamartite,
2) roasting raw material:
470-550 ℃ of maturing temperatures, time 〉=1h adopts oxidizing roasting or reducing atmosphere roasting to make hamartite be decomposed into rare earth oxide,
3) hydrochloric acid leaching:
(1) for the rare earth oxide TREO45-60% in the raw material hamartite, through the dilute hydrochloric acid washing, acidity 0.2-0.5N removes the calcium magnesium addition to the roasted ore of roasting gained earlier, again by (2) described condition hydrochloric acid leaching;
(2) for the pickling ore deposit of the roasted ore or the rapid gained of previous step of the rare earth oxide TREO in the raw material hamartite 〉=60% roasting gained, use the concentrated hydrochloric acid acidleach, acidity 6-11N, hydrochloric acid consumption: weight ratio, roasted ore REO: concentrated hydrochloric acid 31% 〉=1: 2.5-2.75, reducing roasting ore deposit: temperature normal temperature, or oxidizing roasting ore deposit: temperature 〉=80 ℃, time 〉=2h needs add H under less than 60 ℃ temperature to the roasted ore of oxidizing roasting
2O
2The hydrogen peroxide hydrotropy is to CeO
2Ce in/TREO 〉=45% or the slag
4+=0, filter the reservation pickling liquor,
4) acid leaching residue alkali changes: acid leaching residue is added hydroxide bases to be changeed,
Alkali: roasted ore REO=0.4-0.8: 1, weight ratio, basicity are 20-55%, temperature 〉=95 ℃, time 2-4h, washing terminal point pH7-8 removes waste water, alkali is changeed acid leaching residue and pickling liquor enters next step jointly:
5) in and removal of impurities:
Alkali changes acid leaching residue and neutralization reaction is carried out in pickling liquor, and pH is 1.5-2.5, adds H
2SO
4Deleading, barium add H
2O
2Hydrotropy and deironing add BaCl
2Remove unnecessary SO
4 2-, transferring pH is 4.0-4.5 deironing, thorium, filter to keep filtrate,
6) concentrate: negative pressure adds the hot filtrate condensing crystal, promptly gets the mixed chlorinated rare earth product to rare earth chloride TREO 〉=45%.
2, production method according to claim 1, the acid leaching residue alkali that it is characterized in that the hydrochloric acid leaching of step 3 and step 4 transforms and carries out in same acid and alkali-resistance retort.
3, production method according to claim 1 and 2, the acid leaching residue alkali that it is characterized in that step 4 transform with step 5 in and removal of impurities in same acid and alkali-resistance retort, carry out.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98112044A CN1077546C (en) | 1998-06-04 | 1998-06-04 | Method for producing mixed rare-earth chloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98112044A CN1077546C (en) | 1998-06-04 | 1998-06-04 | Method for producing mixed rare-earth chloride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1202460A CN1202460A (en) | 1998-12-23 |
| CN1077546C true CN1077546C (en) | 2002-01-09 |
Family
ID=5221923
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98112044A Expired - Fee Related CN1077546C (en) | 1998-06-04 | 1998-06-04 | Method for producing mixed rare-earth chloride |
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| CN (1) | CN1077546C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103184332A (en) * | 2013-03-29 | 2013-07-03 | 四川省彭山宇力化工有限公司 | Method for roasting, converting and resolving fluorocarbon cerium rare earth mine by adding covering agent to calcium compound |
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| CN1081241C (en) * | 1999-06-25 | 2002-03-20 | 清华大学 | Ammonium chloride process for extracting rare-earth chloride from bastnaesite fine ore |
| JP4236857B2 (en) * | 2002-03-22 | 2009-03-11 | 三井金属鉱業株式会社 | Cerium-based abrasive and method for producing the same |
| CN100587090C (en) * | 2007-11-20 | 2010-02-03 | 中国地质科学院矿产综合利用研究所 | Comprehensive utilization process of bastnaesite and celestite paragenic ore |
| CN102399983A (en) * | 2010-09-10 | 2012-04-04 | 周毅 | Bastnaesite (bastnasite) separation method |
| CN102277483B (en) * | 2011-07-28 | 2012-11-14 | 内蒙古科技大学 | Method for preparing rare earth chloride by using Baiyunebo rare earth concentrate |
| CN103172102A (en) * | 2013-04-08 | 2013-06-26 | 包头华美稀土高科有限公司 | Process for producing granular rare earth chloride crystals by using rare earth chloride solution |
| CN103572064B (en) * | 2013-11-19 | 2015-03-11 | 乐山盛和稀土股份有限公司 | Method for enriching lead and recovering rare earth from rare earth lead slag |
| CN104278164B (en) * | 2014-09-29 | 2016-05-18 | 乐山盛和稀土股份有限公司 | Grade is at the fluorine carbonated rare earth ore deposit of 62%-72% treatment process |
| CN104313318A (en) * | 2014-09-29 | 2015-01-28 | 乐山盛和稀土股份有限公司 | 45-60%-grade rare-earth cerium fluorocarbonate ore leaching technique |
| CN104593622B (en) * | 2014-12-29 | 2017-01-18 | 乐山盛和稀土股份有限公司 | Technology for obtaining cerium enrichment with a partition larger than 99% by optimal extraction of fluoride carbonate rare earths by hydrochloric acid |
| CN110512098A (en) * | 2019-08-29 | 2019-11-29 | 包头钢铁（集团）有限责任公司 | A kind of method that bastnaesite wet process prepares rare earth chloride |
| WO2021097693A1 (en) * | 2019-11-20 | 2021-05-27 | 包头稀土研究院 | Smelting method for bastnaesite and use of carbon powder |
| CN111559755B (en) * | 2020-06-08 | 2022-08-05 | 四川省冕宁县方兴稀土有限公司 | Production method of low-calcium lanthanum carbonate |
| CN111876599A (en) * | 2020-07-24 | 2020-11-03 | 乐山盛和稀土股份有限公司 | Rare earth feed liquid value adjusting process |
| CN113667842B (en) * | 2021-07-14 | 2022-09-20 | 四川省冕宁县方兴稀土有限公司 | Method for removing non-rare earth impurities in rare earth hydrometallurgy |
| CN113621809B (en) * | 2021-08-09 | 2023-03-17 | 四川省乐山锐丰冶金有限公司 | Method for reducing and leaching bastnaesite by utilizing neodymium iron boron reclaimed materials |
| CN113604672B (en) * | 2021-08-09 | 2022-10-04 | 四川省乐山锐丰冶金有限公司 | Method for recovering lead chloride and rare earth from lead-barium slag |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6065721A (en) * | 1983-09-20 | 1985-04-15 | Mitsubishi Chem Ind Ltd | Purification of rare earth element |
| CN1078498A (en) * | 1993-05-08 | 1993-11-17 | 袁哲儒 | The new preparation method of mixed chlorinated rare earth |
| CN1109103A (en) * | 1994-03-25 | 1995-09-27 | 颜克昌 | Impregnation process for separation of cerium oxide and mixed low-cerium rare earth elements |
| 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 |
-
1998
- 1998-06-04 CN CN98112044A patent/CN1077546C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6065721A (en) * | 1983-09-20 | 1985-04-15 | Mitsubishi Chem Ind Ltd | Purification of rare earth element |
| CN1078498A (en) * | 1993-05-08 | 1993-11-17 | 袁哲儒 | The new preparation method of mixed chlorinated rare earth |
| CN1109103A (en) * | 1994-03-25 | 1995-09-27 | 颜克昌 | Impregnation process for separation of cerium oxide and mixed low-cerium rare earth elements |
| 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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103184332A (en) * | 2013-03-29 | 2013-07-03 | 四川省彭山宇力化工有限公司 | Method for roasting, converting and resolving fluorocarbon cerium rare earth mine by adding covering agent to calcium compound |
| CN103184332B (en) * | 2013-03-29 | 2015-04-22 | 四川省彭山宇力化工有限公司 | Method for roasting, converting and resolving fluorocarbon cerium rare earth mine by adding covering agent to calcium compound |
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| Publication number | Publication date |
|---|---|
| CN1202460A (en) | 1998-12-23 |
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