CN1455009A - Preparation of rare earth chloride from long-chain fatty acid extracting transformation and back-extraction process thereof - Google Patents
Preparation of rare earth chloride from long-chain fatty acid extracting transformation and back-extraction process thereof Download PDFInfo
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- CN1455009A CN1455009A CN03136171A CN03136171A CN1455009A CN 1455009 A CN1455009 A CN 1455009A CN 03136171 A CN03136171 A CN 03136171A CN 03136171 A CN03136171 A CN 03136171A CN 1455009 A CN1455009 A CN 1455009A
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Abstract
The present invention uses rare earth sulfate obtained by using sulfuric acid to roast immersion liquor magnesia to regulate pH value to 3-4 and removing iron and impurity as raw material, and uses long-chain fatty acid, cosolvent and sulfonated kerosene to form orgnaic phase, the long-chain fatty acid is dehydrated on non-dehydrated ricinus oil fatty acid, and uses ammonia water, sodium hydroxide, ammonium hydrogen carbonate or sodium carbonate to make saponficiation, and adopts multi-stage extraction and washing processes to obtain the invented rare earth chloride solution whose concentration is greater than 200 g/l, acidity pH is 1-2 and sulfuric acid radical is less than 0.02%, and the rare earth yield is greater than 99%.
Description
One, technical field:
The invention belongs to the process field of metallurgical rare earth metal, relate to a kind of longer chain fatty acid abstraction and type-reverting specifically and prepare rare earth chloride and anti-extraction process thereof.
Two, background technology:
80,000 tons of Baotou rare earth ore concentrate yearly capacities, rare-earth industry mainly adopts vitriol oil high-temperature roasting decomposition technique at present, roasted ore goes out to obtain to contain rare earth and iron through water logging, the leach liquor of impurity such as calcium, with obtaining rare earth sulfate solution behind the impurity such as magnesium oxide accent PH3-4 deironing, to the present industrial two kinds of subsequent technique flow preparation rare earth chlorides that have of this rare earth sulfate solution, first kind of flow process is to use ammonium bicarbonate precipitation, obtain the carbonated rare earth product through centrifugation, obtain re chloride with dissolving with hydrochloric acid more as required then and be used to separate the single rare earth product, this technology periodical operation is discontinuous, the sulfate radical content height is unfavorable for the later separation operation in the carbonated rare earth, and produce the acid water pollution environment that contains a large amount of ammonium salt classes, second kind of technology is to extract with P204, the hydrochloric acid back extraction prepares re chloride, this technology needs higher back extraction acidity to come back extraction rare earth and a spot of iron on the one hand, the re chloride acidity that obtains is higher, can not be directly as the feed liquid of later separation single rare earth, need carry out the acidity allotment, technology is discontinuous, iron accumulation after production run for some time in the extraction agent, reduce the loading capacity of organic phase, on the other hand, P204 is an acid phosphatase lipid extraction agent, be difficult for degraded at occurring in nature, have certain toxicity, the contaminated wastewater environment that contains organophosphorus in a large number of generation, technical process is discontinuous.
Chinese patent (publication number CN1394971A) discloses a kind of technology from sulfo-phosphoric mixed acid system extracting and separating thorium and extraction rare earth chloride, this technology is to be raw material with sulfuric acid low temperature roasting infusion, directly with behind the primary amine extracting and separating thorium, add iron(ic) chloride and transfer iron phosphorus ratio, magnesium oxide is transferred PH3-4 deironing phosphorus, prepare rare earth chloride with the P507 abstraction and type-reverting then, P507 preparation transition rare earth chloride has identical weak point with the P204 transformation process.
Three, summary of the invention:
The objective of the invention is to adopt a kind ofly directly after the removal of impurity of acid adjustment degree, to prepare rare earth chloride and anti-extraction process thereof, do not need the heavy or follow-up acidity of allocating again of carbon, to overcome above-mentioned deficiency with the longer chain fatty acid abstraction and type-reverting by sulfuric acid high-temperature roasting infusion.
The objective of the invention is to realize by following technical scheme:
A kind of longer chain fatty acid abstraction and type-reverting prepares rare earth chloride and anti-extraction process thereof, be characterized in that with rare earth ore concentrate roasting infusion or sulfuric acid rare earth be raw material, rare earth concentration 30-40g/l acidity PH2-4, iron level is less than 200PPM, extraction agent is a longer chain fatty acid, with alcohol mixture or petrolenum sulfoxide is solubility promoter, make thinner with alkane, form longer chain fatty acid-solubility promoter-alkane extraction agent system, organic phase is 0.3-1.0M longer chain fatty acid-10-25%V/V alcohol mixture or petrolenum sulfoxide-alkane, the saponification degree of longer chain fatty acid is 40-100%, with above-mentioned organic phase rare earth feed liquid is extracted, the sour water washing, reextraction obtains re chloride, organic phase: feed liquid: the stream of washing lotion is than being 1-2: 1: 0.2-1, dehydrated castor oil fatty acid that described extraction agent longer chain fatty acid is C18 or longer chain fatty acid are the not dehydrated castor oil fatty acid of C18, and selected solubility promoter is an isooctyl alcohol, secondary octanol, in primary isoamyl alcohol or the petrolenum sulfoxide one or more; Selected saponifying agent is ammoniacal liquor, sodium hydroxide, bicarbonate of ammonia or yellow soda ash, and strip liquor is the acid of two kinds of different concns, and strip liquor 1 acidity is the hydrochloric acid of 1-3M, and strip liquor 2 acidity are the hydrochloric acid of 5-6M; The strip liquor 1 of lower concentration adds from the organic exit of blank, and high density strip liquor 2 adds from the intermediate stage of the section of stripping.
Adopt the present invention to obtain to contain the anti-stripping agent reduction extraction liquid acidity of high concentration rare earth and remove partial impurities with lower reextraction acidity, this invention mainly is that solution current technology flow process is discontinuous, the waste water pollution problem that contains organophosphorus, longer chain fatty acid reextraction acidity is low, through adopting a kind of new anti-extraction process system, the re chloride rare earth concentration of abstraction and type-reverting is greater than 180g/l, acidity is PH1-2, sulfate radical content is less than 0.02%, the rare earth yield is greater than 99%, can be directly as the raw material of follow-up extracting and separating single rare earth, technical process is simple, continuously, chemical reagent consumption is few, reduced environmental pollution, belong to the pollution-free technology flow process, the longer chain fatty acid of selecting for use is the straight chain fatty acid of the C18 that extracts from plant, the zero pour height, water-soluble little, break through traditional view and thought the low mistaken ideas that are unfit to do extraction agent of longer chain fatty acid zero pour.
Four, description of drawings:
Fig. 1 is an anti-extraction process schema of the present invention.
Five, embodiment:
At first with the lipid acid of volume ratio 20-40%, add the alcohol mixture of 7-20%, thinner is that kerosene is formed organic phase, and organic phase is 0.2-0.8M with strong aqua or bicarbonate of ammonia saponification, the saponification deg of organic phase, washings is the hydrochloric acid subacidity water of PH2-4, extraction 2-7 level, washing 1-3 level, organic phase: rare earth feed liquid: the stream of washings is than being 1-2: 1: 0.2-1, raffinate middle-weight rare earths concentration is less than 0.03g/l, and the rare earth yield is greater than 99%.
Saturated organic phase is stripped with the hydrochloric acid strip liquor, strip liquor 1 acidity is 1-3M hydrochloric acid, strip liquor 2 acidity are 5-6M hydrochloric acid, strip liquor 1 adds from organic phase outlet level, strip liquor 2 is from centre one-level or what adding of the section of stripping, through the back extraction of 5-9 level, organic phase: strip liquor 1: the stream of strip liquor 2 is than being 15-25: 1: 0.1-0.5, the re chloride concentration that obtains is greater than 180g/l, acidity PH1-2, sulfate radical content is less than 0.02%, and the rare earth yield can be recycled after the organic phase washing greater than 99%.
Concrete enforcement is as follows:
Embodiment 1: packet header rare earth enterprise vitriol oil high-temperature roasting infusion, rare earth sulfate solution after the magnesium oxide removal of impurity, be that former technology is used for the heavy feed liquid of carbon, rare earth concentration 38g/l, acidity PH4, organic phase consists of lipid acid 1.0M-isooctyl alcohol 15%V/V-sulfonated kerosene, the strong aqua saponification, and saponification deg is 0.4M, 3 grades of extractions, 2 grades of washings, 5 grades of back extractions, organic phase: feed liquid: washings: strip liquor 1: the stream ratio of strip liquor 2 is 3: 1: 0.5: 0.18: 0.06, the re chloride concentration that obtains is 205g/l, acidity is PH1, and sulfate radical content is less than 0.02%, and the rare earth yield is greater than 99%.
Embodiment 2: packet header rare earth enterprise vitriol oil high-temperature roasting infusion, rare earth sulfate solution after the magnesium oxide removal of impurity, it is the feed liquid that former technology is used for the P204 abstraction and type-reverting, rare earth concentration 36g/l, acidity PH2, other conditions are with example 1, the re chloride concentration that obtains is 203g/l, acidity is PH1, and sulfate radical content is less than 0.02%, and the rare earth yield is greater than 99%.
Embodiment 3: feed liquid is with example 1, and organic phase consists of lipid acid 0.85M-isooctyl alcohol 15%V/V-sulfonated kerosene, the strong aqua saponification, and saponification deg is 0.4M.3 grades of extractions, 2 grades of washings, 5 grades of back extractions, organic phase: feed liquid: washings: strip liquor 1: the stream ratio of strip liquor 2 is 4: 1: 1: 0.18: 0.04, the re chloride concentration that obtains was 184g/l, and acidity is PH2, sulfate radical content is less than 0.02%, and the rare earth yield is greater than 99%.
Embodiment 4: feed liquid is with example 1, and organic phase consists of lipid acid 1.0M-isooctyl alcohol 15%V/V-sulfonated kerosene, the saponification of unsaturated carbonate hydrogen ammonium solution, and saponification deg is 0.4M.3 grades of extractions, 2 grades of washings, 5 grades of back extractions, organic phase: feed liquid: washings: strip liquor 1: the stream ratio of strip liquor 2 is 3: 1: 1: 0.18: 0.07, the re chloride concentration that obtains was 212g/l, and acidity is PH2, sulfate radical content is less than 0.02%, and the rare earth yield is greater than 99%.
Claims (4)
1, a kind of longer chain fatty acid abstraction and type-reverting prepares rare earth chloride and anti-extraction process thereof, it is characterized in that with rare earth ore concentrate roasting infusion or sulfuric acid rare earth be raw material, rare earth concentration 30-40g/l acidity PH2-4, iron level is less than 200PPM, extraction agent is a longer chain fatty acid, with alcohol mixture or petrolenum sulfoxide is solubility promoter, make thinner with alkane, form longer chain fatty acid-solubility promoter-alkane extraction agent system, organic phase is 0.3-1.0M longer chain fatty acid-10-25%V/V alcohol mixture or petrolenum sulfoxide-alkane, the saponification degree of longer chain fatty acid is 40-100%, with above-mentioned organic phase rare earth feed liquid is extracted, the sour water washing, reextraction obtains re chloride, organic phase: feed liquid: the stream of washing lotion is than being 1-2: 1: 0.2-1.
2, according to claim 1 fast a kind of longer chain fatty acid abstraction and type-reverting prepare rare earth chloride and anti-extraction process thereof, it is characterized in that: dehydrated castor oil fatty acid that described extraction agent longer chain fatty acid is C18 or longer chain fatty acid are the not dehydrated castor oil fatty acid of C18.
3, a kind of longer chain fatty acid abstraction and type-reverting according to claim 1 prepares rare earth chloride and anti-extraction process thereof, it is characterized in that: selected solubility promoter is one or more in isooctyl alcohol, secondary octanol, primary isoamyl alcohol or the petrolenum sulfoxide; Selected saponifying agent is ammoniacal liquor, sodium hydroxide, bicarbonate of ammonia or yellow soda ash.
4, a kind of longer chain fatty acid abstraction and type-reverting according to claim 1 prepares rare earth chloride and anti-extraction process thereof, it is characterized in that: strip liquor is the acid of two kinds of different concns, and strip liquor 1 acidity is the hydrochloric acid of 1-3M, and strip liquor 2 acidity are the hydrochloric acid of 5-6M; The strip liquor 1 of lower concentration adds from the organic exit of blank, and high density strip liquor 2 adds from the intermediate stage of the section of stripping.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100351315C (en) * | 2005-11-04 | 2007-11-28 | 安徽建筑工业学院 | Method for preparing processinga id for rare earths of a sort of polyvinyl chloride |
| CN100404706C (en) * | 2005-09-05 | 2008-07-23 | 有研稀土新材料股份有限公司 | Process for extracting rare earth element by non-saponifiable phosphorous mixing extractant |
| CN100451140C (en) * | 2004-07-01 | 2009-01-14 | 包头市京瑞新材料有限公司 | Self protection process for preparing fluorescent grade europium oxide extractor by reducing extracting method |
| CN102505071A (en) * | 2011-12-29 | 2012-06-20 | 清华大学 | Glass fiber reinforced plastic centrifugal extractor and method for implementing extraction transformation of metal compounds |
| CN104878202A (en) * | 2014-02-28 | 2015-09-02 | 中国石油化工股份有限公司 | Method for extracting rare earth from rare earth-containing sludge |
| CN106916948A (en) * | 2017-03-07 | 2017-07-04 | 四川省冕宁县方兴稀土有限公司 | A kind of saponification agent and its application process of rare earth organic extractant |
| CN110408777A (en) * | 2019-07-25 | 2019-11-05 | 厦门熙途科技有限公司 | A kind of method of fatty acid extracting metals ion |
| CN113716757A (en) * | 2021-09-24 | 2021-11-30 | 内蒙古科技大学 | Method for removing zinc from extraction liquid and application of rare earth saponification wastewater |
-
2003
- 2003-05-17 CN CN03136171A patent/CN1455009A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100451140C (en) * | 2004-07-01 | 2009-01-14 | 包头市京瑞新材料有限公司 | Self protection process for preparing fluorescent grade europium oxide extractor by reducing extracting method |
| CN100404706C (en) * | 2005-09-05 | 2008-07-23 | 有研稀土新材料股份有限公司 | Process for extracting rare earth element by non-saponifiable phosphorous mixing extractant |
| CN100351315C (en) * | 2005-11-04 | 2007-11-28 | 安徽建筑工业学院 | Method for preparing processinga id for rare earths of a sort of polyvinyl chloride |
| CN102505071A (en) * | 2011-12-29 | 2012-06-20 | 清华大学 | Glass fiber reinforced plastic centrifugal extractor and method for implementing extraction transformation of metal compounds |
| CN104878202A (en) * | 2014-02-28 | 2015-09-02 | 中国石油化工股份有限公司 | Method for extracting rare earth from rare earth-containing sludge |
| CN104878202B (en) * | 2014-02-28 | 2017-04-26 | 中国石油化工股份有限公司 | Method for extracting rare earth from rare earth-containing sludge |
| CN106916948A (en) * | 2017-03-07 | 2017-07-04 | 四川省冕宁县方兴稀土有限公司 | A kind of saponification agent and its application process of rare earth organic extractant |
| CN106916948B (en) * | 2017-03-07 | 2019-07-09 | 四川省冕宁县方兴稀土有限公司 | A kind of saponification agent and its application method of rare earth organic extractant |
| CN110408777A (en) * | 2019-07-25 | 2019-11-05 | 厦门熙途科技有限公司 | A kind of method of fatty acid extracting metals ion |
| CN113716757A (en) * | 2021-09-24 | 2021-11-30 | 内蒙古科技大学 | Method for removing zinc from extraction liquid and application of rare earth saponification wastewater |
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