CN100471963C - Ultrasonic leaching-extracting separation method for sulphating roasting rare earth mine - Google Patents
Ultrasonic leaching-extracting separation method for sulphating roasting rare earth mine Download PDFInfo
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- CN100471963C CN100471963C CNB2007100199405A CN200710019940A CN100471963C CN 100471963 C CN100471963 C CN 100471963C CN B2007100199405 A CNB2007100199405 A CN B2007100199405A CN 200710019940 A CN200710019940 A CN 200710019940A CN 100471963 C CN100471963 C CN 100471963C
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Abstract
The invention discloses an ultrasonic leaching-extracting separating method of rare earth ore sintered by sulfuric acid, which comprises the following steps: adopting sulfuric acid solution as leaching liquid; allocating extracting liquid through P204, P507 and kerosene; proceeding leaching-extracting separating operation for rare earth ore through ultrasound with strength at 0.2-20.0W/cm2 and frequency at 19-80kHz under 5-60 deg.c; obtaining the enriched product of middle heavy rare earth (yttrium group rare earth element) sulfate as extracting phase and light rare earth (cerium group rare earth element) sulfate as residual phase.
Description
Technical field:
The present invention relates to the separation method of sulphating roasting rare earth mine, belong to the hydrometallurgy field.
Background technology:
Bastnasite, bastnasite, monazite and mishmetal ore deposit thereof are the raw materials of producing sulphating roasting rare earth mine, the common separation method of sulphating roasting rare earth mine is at present: rare-earth mine sulfuric acid baking-rare earth leaching-solvent extraction, it is a mature and stable operational path in the existing Rare Earth Separation industrial production.This technology is raw material with above-mentioned rare-earth mineral and sulfuric acid, changes rare earth into water-soluble vitriol through roasting, leaches as solvent with water then, and the gained leach liquor carries out extracting and separating after neutralization, removal of impurities etc. are handled, obtain rare-earth products.In this process, at present leaching operation normally directly adds the thermal bake-out product water furnishing pulpous state, squeezes into leaching tanks through pump then, leaches under stirring condition.The main drawback of this leaching operation is that the rare earth leaching efficiency is low, leaching time is long, energy expenditure is big.Because existing Rare Earth Production flow process is to be combined by leaching, separation, impurity removal, the different separating step of extraction, wherein between leaching and extraction, extraction and the continuous inter process divergence in front and back are not mated.Except the linking of extracting phase as feed liquid, the solubleness of sulphating roasting rare earth mine in sulfuric acid is certain, after extracting in extraction phase the content of the separate targets thing state that can not reach capacity; In extracting phase, do not reach state of saturation equally yet.Raffinate and extract rare earth concentration are lower, the acidity height.
The main drawback that this separation method exists is:
1. the separating technology route is long, should leach equipment extraction equipment again, and the production capacity of equipment is low;
2. along with the carrying out that extracts, yttrium group rare-earth element is constantly transferred to the extraction phase from water, the yttrium group rare-earth concentration of element of aqueous phase is reduced, thereby make extraction rate slack-off, the content of yttrium group rare-earth element is lower in the gained extraction phase, the concentration that can not reach capacity, the concentration that reach capacity must increase the spissated load of subsequent evaporation; The content of the cerium subgroup of rare earth elements concentration that also do not reach capacity in the same gained extracting phase, in separation process, the material treatment capacity is big, the removal of impurities separation difficulty.Not only the comprehensive yield of yttrium group rare-earth element and cerium subgroup of rare earth elements is lower, and the feed liquid treating capacity is very big in the follow-up extractive process, if will realize the production that cleans of zero-emission, then processing cost is very high, if not treatedly then can aggravate environmental pollution;
3. leaching, extraction rate and the efficient in the existing separation process is low, and economic benefit and social benefit are not high.
Summary of the invention:
In order to overcome the deficiency of existing isolation technique, the ultrasonic leaching-extracting separation method that the purpose of this invention is to provide a kind of sulphating roasting rare earth mine, it can therefrom isolate cerium subgroup of rare earth elements enriched substance and yttrium group rare-earth enrichment of element thing economical, fast, up hill and dale, and reduces treating material for follow-up refining realization cleans to produce.
Separation method of the present invention is as follows:
With sulphating roasting rare earth mine, leaching liquid and extract in 1000g:(5～50) L:(0.1～20) the L ratio puts into same leaching-extracting separation equipment, sulphating roasting rare earth mine leaches extract and separate simultaneously in the leaching-extracting separation equipment, operating temperature is 5-60 ℃, separate through leaching-extracting, get extraction phase (organic phase), raffinate phase (water) and solid phase, the extraction phase rare earth sulfate enriched substance of attaching most importance to is mainly yttrium group rare-earth element, comprises Sm
2O
3, Eu
2O
3, Gd
2O
3, Tb
4O
7, Dy
2O
3, Y
2O
3Deng in heavy rare earth; Raffinate phase is light rare earth sulfate enriched substance, is mainly cerium subgroup of rare earth elements, comprises La
2O
3, Ce
2O
3, Pr
2O
3, Nd
2O
3Deng light rare earth, take out respectively extraction phase and raffinate phase, remove solid-phase, described leaching liquid is aqueous sulfuric acid, contains extractant and diluent in the described extract, and described extractant is P204 or P507 or N1923 or TBP or P350, and described diluent is kerosene.
In above-mentioned separation method, service temperature is 25-45 ℃.
In above-mentioned separation method, described leaching-extracting separation equipment is ultrasonic leaching-extracting equipment, and it comprises leaching-extracting container and ultrasonic generator, and the supersonic frequency of ultrasonic generator is 19-80kHz, and ultrasonication intensity is 0.2-20.0W/cm
2
Further, the supersonic frequency of described ultrasonic generator is that 19-25kHz ultrasonication intensity is 2.0-5.0W/cm
2
Further, the structure of described leaching-extracting container is still formula leaching-extracting container or slot type leaching-extracting container or tubular type leaching-extracting container, described ultrasonic generating unit is any in probe type ultrasonic producer, vibrator type ultra-sonic generator, the vibration plate formula ultra-sonic generator, or their combination.
Described extractant is P204 or P507.
Adopt advantage of the present invention:
Created the leaching-extracting coupling technique. the leaching of finishing rare earth element in same ultrasonic leaching-extracting separation equipment separates with extraction, with P204[two-(2-ethylhexyl) phosphoric acid] or P507 (di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester) or N1923 or TBP or P350 be as extractant, carry out simultaneously the grouping of Nd-Sm or Gd-Tb, separate through leaching-extracting, get extraction phase and the raffinate phase of high concentration, extraction phase is middle heavy rare earth (yttrium group rare-earth element) sulfate enriched substance, and raffinate phase is light rare earth (cerium subgroup of rare earth elements) sulfate enriched substance; Adopt ultrasound-enhanced isolation technics: the leaching-extracting process is used ultrasonic wave, improves the dispersiveness of liquid-solid leaching process and liquid-liquid extraction process by ultrasonication, improves the mass transfer rate of leaching-extracting process, improves the efficient of leaching-extracting process.As long as on existing leaching container, set up ultrasonic generator, need not extraction container, not only reduce Nd-Sm or Gd-Tb grouping extracting and separating cell arrangement, shortened technical process, and in sepn process, the concentration of solution middle-weight rare earths element remains on higher level, help the separation and the enrichment of rare earth element, help the removal of impurity in the sulphating roasting rare earth mine, alleviated the material treatment capacity, alleviate the segregational load of rare earth and non-rare earth impurity, rare earth and water, reduced the treatment capacity of evaporation concentration in the consumption of chemical reagent and the subsequent technique process.
Description of drawings:
Fig. 1 is the process chart of invention;
Fig. 2-5 is several structure formations of described ultrasonic leaching-extracting equipment;
Fig. 2 is a probe type ultrasonic leaching-extracting still, comprises probe type ultrasonic producer 1 and still formula container 4;
Fig. 3 is a vibrator type ultrasonic leaching-extracting groove, comprises that slot type container 5 and several are arranged on the vibrator type ultra-sonic generator 2 on the wall of container;
Fig. 4 is a vibration plate formula ultrasonic leaching-extracting groove, comprises slot type container 5 and places the interior vibration plate formula ultra-sonic generator 3 of container;
Fig. 5 is a tubular ultrasonic leaching-extracting equipment, comprises tube container 6 and places the interior vibration plate formula ultra-sonic generator 3 of container;
Below the invention will be further described in more detail with embodiment, but the present invention is not subjected to the restriction of these embodiment.
Embodiment 1: main production equipments: probe type ultrasonic producer, 1L stirring tank, analytical and testing instrument;
Main raw material: water, sulfuric acid, P204 extraction agent, sulphating roasting rare earth mine;
Separating step is: sulphating roasting rare earth mine, leaching liquid, extract are put into the 1L stirred tank in the 1000g:5L:0.1L ratio, sulphating roasting rare earth mine material 100g, the mixed solution 0.01L of aqueous sulfuric acid 0.5L and extract P204 and kerosene, the probe of probe type ultrasonic generator is placed this mixed material, the control operation temperature is 5 ℃, supersonic frequency is transferred to 19kHz, and ul-trasonic irradiation intensity is 0.2W/cm
2, under ul-trasonic irradiation, carry out the ultrasonic leaching-extracting lock out operation, after ultrasonic leaching-extracting separated 30min, getting raffinate phase was light rare earth sulfate enriched substance, is mainly La
2O
3, Ce
2O
3, Pr
2O
3, Nd
2O
3Deng the sulfate enriched substance; Extraction phase is middle heavy rare earth sulfate enriched substance, wherein is mainly yttrium group rare-earth element, comprises Sm
2O
3, Eu
2O
3, Gd
2O
3, Tb
4O
7, Dy
2O
3, Y
2O
3Deng in the sulfate enriched substance of heavy rare earth.
Embodiment 2: main production equipments: probe type ultrasonic producer, 5L stirring tank, analytical and testing instrument;
Main raw material: water, sulfuric acid, P204 extraction agent, sulphating roasting rare earth mine;
Separating step is: sulphating roasting rare earth mine, leaching liquid, extract are put into the 5L stirred tank in the 1000g:20L:5L ratio, sulphating roasting rare earth mine material 150g, the mixed solution 0.75L of aqueous sulfuric acid 3L and extract P204 and kerosene, the probe of probe type ultrasonic generator is placed this mixed material, the control operation temperature is 40 ℃, supersonic frequency is transferred to 25kHz, and ultrasonication intensity is 2.0W/cm
2, under ultrasonication, carry out the ultrasonic leaching-extracting lock out operation, after ultrasonic leaching-extracting separated 15min, getting raffinate phase was light rare earth sulfate enriched substance, is mainly La
2O
3, Ce
2O
3, Pr
2O
3, Nd
2O
3Deng the sulfate enriched substance; Extraction phase (organic phase) is middle heavy rare earth sulfate enriched substance, wherein is mainly yttrium group rare-earth element, comprises Sm
2O
3, Eu
2O
3, Gd
2O
3, Tb
4O
7, Dy
2O
3, Y
2O
3Deng middle heavy rare earth sulfate enriched substance.
Embodiment 3: main production equipments: probe type ultrasonic producer, 10L stirring tank, analytical and testing instrument;
Main raw material: water, sulfuric acid, P204 extraction agent, sulphating roasting rare earth mine;
Separating step is: sulphating roasting rare earth mine, leaching liquid, extract are put into the 10L stirred tank in the 1000g:50L:10L ratio, sulphating roasting rare earth mine material 100g, the mixed solution 1L of aqueous sulfuric acid 5L and extract P204 and kerosene, the probe of probe type ultrasonic wave producer is placed this mixed material, the control operation temperature is 60 ℃, supersonic frequency is transferred to 80kHz, and ultrasonication intensity is 20.0W/cm
2, under ultrasonication, carry out the ultrasonic leaching-extracting lock out operation, after ultrasonic leaching-extracting separated 30min, getting raffinate phase was light rare earth sulfate enriched substance, is mainly La
2O
3, Ce
2O
3, Pr
2O
3, Nd
2O
3Deng the sulfate enriched substance; Extraction phase is middle heavy rare earth sulfate enriched substance, wherein is mainly yttrium group rare-earth element, comprises Sm
2O
3, Eu
2O
3, Gd
2O
3, Tb
4O
7, Dy
2O
3, Y
2O
3Deng middle heavy rare earth sulfate enriched substance.
In above-mentioned each example, what the leaching-extracting structure of container form in the described ultrasonic leaching-extracting separation equipment was selected is autoclave, also can select slot type or tube container, ultrasonic generator can be selected any in probe type ultrasonic generator, vibrator type supersonic generator, the vibration plate type supersonic generator, or their combination, select different equipment little to the impact that separates; The supersonic frequency adjustable range of ultrasonic generator is 19-80kHz, and ultrasonication intensity is at 0.2-20.0W/cm
2Interior adjusting, the height of intensity, frequency has considerable influence to the efficient of separating, and the best supersonic frequency of separative efficiency is 19-25kHz, increases and can reduce separating rate and separative efficiency, and the optimum range of ul-trasonic irradiation intensity is 2.0-5.0W/cm
2
The isolating optimum operating temperature of leaching-extracting is 25-40 ℃, and its span is 5-60 ℃, and temperature height is influential to velocity of separation, too high or too low for temperaturely all can reduce velocity of separation.
Described leaching liquid is an aqueous sulfuric acid; The preferred P204 of extraction agent in the extraction liquid, thinner are kerosene, and extraction agent also can be selected P507 or N1923 or TBP or P350 for use, with economy for selecting principle for use.
Adopt the ultrasonic leaching-extracting technology, can significantly improve leaching and the speed of extraction grouping and the separative efficiency of rare earth, as long as its leaching-extracting grouping is 15～30min.
Embodiment of the present invention are a lot; can't be exhaustive; as long as adopt and in same container, sulphating roasting rare earth mine carried out isolating all technical schemes of leaching-extracting with leaching liquid, extraction liquid; all belong to protection scope of the present invention, especially protection utilizes the ultrasonic wave isolation technique that sulphating roasting rare earth mine in the same container is carried out the isolating technical scheme of leaching-extracting.
Claims (5)
1, the ultrasonic leaching-extracting separation method of sulphating roasting rare earth mine, its sepn process is as follows: with sulphating roasting rare earth mine, leaching liquid and extraction liquid are in 1000g:(5～50) L:(0.1～20) the L ratio puts into same leaching-extracting separating device, sulphating roasting rare earth mine carries out leaching-extracting simultaneously in the leaching-extracting separating device separates, service temperature is 5-60 ℃, separate through leaching-extracting, get extraction phase, extracting phase and solid phase, the extraction phase rare earth sulfate enriched substance of attaching most importance to, be mainly yttrium group rare-earth element, extracting phase is a light rare earths vitriol enriched substance, be mainly cerium subgroup of rare earth elements, take out extraction phase and extracting phase respectively, remove the solid phase, described leaching liquid is an aqueous sulfuric acid, contain extraction agent and thinner in the described extraction liquid, described extraction agent is P204 or P507 or N1923 or TBP or P350, and described thinner is a kerosene.
2, according to the ultrasonic leaching-extracting separation method of the described sulphating roasting rare earth mine of claim 1, it is characterized in that: service temperature is 25-40 ℃.
3, according to the ultrasonic leaching-extracting separation method of the described sulphating roasting rare earth mine of claim 1, it is characterized in that: described leaching-extracting separation equipment is ultrasonic leaching-extracting equipment, it comprises leaching-extracting container and ultrasonic generator, the supersonic frequency of ultrasonic generator is 19-80kHz, and ultrasonication intensity is 0.2-20.0W/cm
2
4, according to the ultrasonic leaching-extracting separation method of the described sulphating roasting rare earth mine of claim 3, it is characterized in that: the supersonic frequency of described ultrasonic generator is 19-25kHz, and ultrasonication intensity is 2.0-5.0W/cm
2
5, according to the ultrasonic leaching-extracting separation method of the described sulphating roasting rare earth mine of claim 3, it is characterized in that: the structure of described leaching-extracting container is still formula or slot type or tube container, described ultrasonic generating unit is any in probe type ultrasonic producer, vibrator type ultra-sonic generator, the vibration plate formula ultra-sonic generator, or their combination.
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| CNB2007100199405A CN100471963C (en) | 2007-02-05 | 2007-02-05 | Ultrasonic leaching-extracting separation method for sulphating roasting rare earth mine |
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| CN100471963C true CN100471963C (en) | 2009-03-25 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20130040765A (en) * | 2010-09-14 | 2013-04-24 | 자크리토에 액시오네르노에 오브쉐스트보 ˝트윈 트레이딩 컴퍼니˝ | Method for extracting rare earth elements from phosphogypsum |
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| RU2412265C1 (en) * | 2009-07-16 | 2011-02-20 | Закрытое Акционерное Общество "Твин Трейдинг Компани" | Procedure for extraction of rare earth elements from phospho-gypsum |
| KR101183579B1 (en) * | 2012-02-17 | 2012-09-17 | 한국지질자원연구원 | High efficient neodymium leaching method using ultrasonic wave |
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| CN103225023A (en) * | 2013-04-26 | 2013-07-31 | 连云港市丽港稀土实业有限公司 | Method for leaching and recovering rare earth element from rare earth slag |
| KR101420117B1 (en) * | 2014-01-29 | 2014-07-17 | 한국지질자원연구원 | Leaching method of rare-earth metals using hydrochloric acid from manganese nodule |
| CN114752768A (en) * | 2022-04-02 | 2022-07-15 | 中国科学院过程工程研究所 | Method for recovering metal molybdenum in waste hydrogenation catalyst through leaching and extraction integration |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20130040765A (en) * | 2010-09-14 | 2013-04-24 | 자크리토에 액시오네르노에 오브쉐스트보 ˝트윈 트레이딩 컴퍼니˝ | Method for extracting rare earth elements from phosphogypsum |
| KR101690819B1 (en) | 2010-09-14 | 2016-12-28 | 오브쉐스트보 에스 오그라니쉐노이 오?스트베노스트유 ˝트윈 테크놀로지 컴퍼니˝ | Method for extracting rare earth elements from phosphogypsum |
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