CN102382979B - Technique for extracting rare earth from rare earth tailing and preparing calcium sulfate whiskers - Google Patents
Technique for extracting rare earth from rare earth tailing and preparing calcium sulfate whiskers Download PDFInfo
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- CN102382979B CN102382979B CN2011103428830A CN201110342883A CN102382979B CN 102382979 B CN102382979 B CN 102382979B CN 2011103428830 A CN2011103428830 A CN 2011103428830A CN 201110342883 A CN201110342883 A CN 201110342883A CN 102382979 B CN102382979 B CN 102382979B
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- calcium sulfate
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Abstract
The invention relates to a separation and extraction technique for rare earth and calcium resources, in particular to a technique for extracting rare earth from a rare earth tailing and preparing calcium sulfate whiskers. The invention provides an organic solvent crystallization process for extracting rare earth from the rare earth tailing and preparing the calcium sulfate whiskers, which consists of three technical operations to realize the chemical purpose of extracting and separating rare earth and calcium elements. The three technical operations include: 1, a process of leaching sulfuric acid and diluted hydrochloric acid from the rare earth tailing; 2, a process of removing Fe2+ from hydrochloric acid leaching solution; and 3, a process of preparing calcium sulfate whiskers by adopting the organic solvent crystallization. The technique is applicable to extraction and separation of the calcium elements from various calciferous minerals and industrial wastes and has high feasibility, high product purity, simple process operation and low cost. Therefore, the technique has great significance in realizing the comprehensive utilization of the tailings and industrial wastes and reducing the environmental pollution and resource waste.
Description
Technical field
The present invention relates to a kind of rare earth-calcium resource separation extractive technique, particularly relate to a kind of rare-earth tailing rare earth-calcium resource separation extractive technique.
Background technology
The dressing-works produces a large amount of flotation rare-earth tailings in process of production, calcium contents is higher in this mine tailing, past, more domestic scholars and R﹠D institution, recovery to Baogang's dressing-works flotation rare-earth tailing middle-weight rare earths, niobium and iron is studied, and obtained certain achievement, but aspect recovery calcium mineral, the correlative study report is also rare.Therefore, take mine tailing and trade waste as the research that raw material prepares calcium sulfate crystal whiskers, be the needs of protection of the environment, the needs of socio-economic development especially.
Calcium sulfate crystal whiskers (crystal whisker of gypsum) is divided into half water, anhydrous and Dihydrate gypsum whiskers, and it has uniform structure, complete profile, specific cross section, stable size.Compare with other staple fibres, it have resist chemical, good toughness, intensity high, easily carry out surface treatment, with the advantages such as the avidity of the polymkeric substance such as rubber plastic is strong.Calcium sulfate crystal whiskers is a kind of excellent property, cheap green material, has the very strong market competitiveness, so the researchist has carried out comparatively widely research to preparation and the application thereof of calcium sulfate crystal whiskers both at home and abroad.The preparation method of calcium sulfate crystal whiskers is raw material mainly with plaster of paris ore deposit at present, and preparation calcium sulfate crystal whiskers method has hydrothermal method, ion exchange method, reverse micelle method and the hot method of micro emulsion etc.
1. industrial residue prepares calcium sulfate crystal whiskers
Take industrial residues such as halogen slag, carbide slag, desulfurated plaster and phosphogypsums as raw material, adopt the Hydrothermal Synthesis technology to prepare calcium sulfate crystal whiskers.Namely in the hydraulic pressure hot vessel, under the saturated vapor pressure effect, make gypsum be converted into the process of tiny needle-like whisker.Under the hydrothermal condition, water works as chemical composition and participates in reaction, be solvent be again expanded promotor, simultaneously can also be as pressure transfer medium, realize formation and the modification of whisker by the physical chemical factor that accelerates the dialysis reaction and control its process.The hydrothermal method temperature of reaction requires between 120-130 ℃.This method rests on laboratory stage basically at present, and large-scale production and application also have one section gap.
2. ion exchange method prepares calcium sulfate crystal whiskers
Take ion exchange resin as template, vitriol prepares calcium sulfate crystal whiskers through mechanical stirring and heating in water bath for causing precipitation agent, can prepare that pattern is regular, the hemihydrate calcium sulfate crystal whisker of homogeneous.This method equipment is simple, and prepared product need not washing.The advantages such as ion exchange resin can be recycled, this method require raw material purer, and preparation cost is higher.
3. the research for preparing calcium sulfate crystal whiskers with the plaster of paris
Take the plaster of paris as raw material, adopt hydrothermal method to prepare calcium sulfate crystal whiskers.Diameter and the length-to-diameter ratio and suitable take pure gypsum as the raw material products obtained therefrom of the calcium sulfate crystal whiskers of preparation take the plaster of paris as raw material found in research, but therefore the pattern of contained impurity effect calcium sulfate crystal whiskers in the plaster of paris need remove some impurity in the plaster of paris raw material.Production cost is high, but also is subject to the restriction in zone.
Summary of the invention
The object of the present invention is to provide the technology of a kind of rare-earth tailing Extraction of rare earth-preparation calcium sulfate crystal whiskers, for from rare-earth tailing, extracting and prepare the organic solvent effect Steppecd crystallization of calcium sulfate crystal whiskers.The present invention extracts from rare-earth tailing and prepares the calcium sulfate crystal whiskers technology, has realized technical reasonable, viable economically, the purpose that is easy to realize suitability for industrialized production.
The objective of the invention is to be achieved through the following technical solutions:
Rare-earth tailing Extraction of rare earth-preparation calcium sulfate crystal whiskers technology, this technology comprise that three technical operations form: i.e. rare-earth tailing dilute sulphuric acid-dilute hydrochloric acid extract technology; The dilute hydrochloric acid leach liquor is removed Fe
2+Technique; Organic solvent effect crystalline calcium sulfate crystal whiskers technique; The Ore Leaching technique of its rare-earth tailing needs to grind before the rare-earth tailing Ore Leaching, and the acid-leaching reaction temperature is between 90 ~ 100 ℃, and the solid phase of sulfuric acid leaching leaches with dilute hydrochloric acid again; Sulfuric acid soaks the concentration 40% ~ 50% of the selected acid of process; The crystalline calcium sulfate crystal whiskers is removed before its crystallization in the liquid phase+divalent iron; Its technological line is: rare-earth tailing is after dilute sulphuric acid leaching, solid-liquid separation, and 90% rare earth is present in the solid phase in the mine tailing, and the sulfuric acid leaching acid non-soluble substance leaches through dilute hydrochloric acid, and the gained immersion liquid is at the lower Fe of oxygenant effect
2+Oxidation, oxidation solution is the crystalline calcium sulfate crystal whiskers under the monohydroxy-alcohol effect, after filtration, crystallisation by cooling and oven dry, obtains calcium sulfate crystal whiskers and rare earth ore concentrate.
Described rare-earth tailing Extraction of rare earth-preparation calcium sulfate crystal whiskers technology, its described crystalline calcium sulfate crystal whiskers, the iron before the crystallization in the liquid phase is+3 valencys, and organic solvent is the alcohols of methyl alcohol, ethanol, and organic solvent is recycle.
Advantage of the present invention and effect are:
1. the present invention is the processing method of Extraction of rare earth from rare-earth tailing-preparation calcium sulfate crystal whiskers, compared with prior art, the present invention has the working method uniqueness, calcium and rare earth extract altogether, production technique is simple, flow process is short, low equipment investment, and raw material consumption is few, discharging without waste liquid is easy to the characteristics such as suitability for industrialized production.
2. the present invention prepares rare earth ore concentrate and calcium sulfate crystal whiskers by acidleach-organic solvent effect crystallization process, the product ferrous sulfate is the raw material of preparation high added value irony product, have the economic worth height, the characteristics such as purposes is wide, rare earth ore concentrate can be directly used in the Extraction of rare earth element.
3. this technique is not only applicable to rare-earth tailing, also can be applicable to other mineral and the industrial residue of calcic.Make the different various calcium ore deposit of calcium content height really possess extraction value.
The present invention not only can extract and the rare-earth separating mine tailing in calcium constituent and prepare calcium sulfate crystal whiskers, but also can make in the rare-earth tailing the rare earth element enrichment, and separated the real comprehensive utilization of having accomplished resource according to the difference of product physicochemical property.
Embodiment
Embodiment 1
The main component (%) of Baotou rare earth mine tailing I: CaO:20.98%, REO:7.43%, TFe:13.46%
This is low-grade rare-earth tailing, and content of rare earth is lower, and the content of calcium is higher, thus the separation of the compound of calcium to the material impact that is enriched with of rare earth, and the preparation of calcium sulfate crystal whiskers has realized the maximum using of resource.
Preparation process is: rare-earth tailing is dried 10h in 50 ℃ baking oven, grinds, and makes granularity as far as possible little, can be by the standard sub-sieve of 120 order/inches.Accurately take by weighing rare-earth tailing that 15.00g oven dry ground in round-bottomed flask, the sulfuric acid of adding 60mL47% places 90 ℃ of water bath with thermostatic control heated and stirred 5h, leaves standstill, and is cooled to room temperature, suction filtration.With the sulfuric acid insolubles on the diluted hydrochloric acid dissolution filter cake of (1+9), suction filtration is regulated the pH of filtrate between 1.00～1.50 again, adds an amount of dehydrated alcohol, makes the percent crystallization in massecuite of calcium sulfate maximum.Leave standstill 2h under room temperature, suction filtration, filter cake place 35 ℃ baking oven to dry 60min, just can obtain calcium sulfate crystal whiskers, and percent crystallization in massecuite can reach more than 90%, and purity is distilled filtrate more than 96%, Recycled ethanol, and ethanol can recycle.
Embodiment 2
The main component (%) of Baotou rare earth mine tailing II: CaO:16.1%, REO:6.69%, TFe:18.20%
This is low-grade rare-earth tailing, and content of rare earth is lower, and the content of calcium is higher, so the separation of the compound of calcium is to the material impact that is enriched with of rare earth.
Preparation process is: rare-earth tailing is dried 5h in 70 ℃ baking oven, grinds, and makes granularity as far as possible little, can be by the standard sub-sieve of 120 order/inches.Accurately take by weighing rare-earth tailing that 15.00g oven dry ground in round-bottomed flask, the sulfuric acid that adds 50mL47%, place 90 ℃ ~ 100 ℃ water bath with thermostatic control heated and stirred 4h, leave standstill, be cooled to room temperature, the dissolved ferric iron more than 90%, enter solution, and rare earth and calcium constituent be still in solid phase, and suction filtration makes solid-liquid separation.In solid phase, add hydrochloric acid, make the solid phase dissolving, then the pH value of regulator solution.In the filtrate that mixes up the pH value, add an amount of dehydrated alcohol, make the percent crystallization in massecuite of calcium sulfate maximum.2h is left standstill in cooling under room temperature, and suction filtration, filter cake place 30 ℃ baking oven to dry 1h, just can obtain calcium sulfate crystal whiskers, and percent crystallization in massecuite can reach more than 95%, with the filtrate distillation, and Recycled ethanol, ethanol can recycle.
Claims (2)
1. rare-earth tailing Extraction of rare earth-prepare the method for calcium sulfate crystal whiskers is characterized in that, the method comprises that three technical operations form: i.e. rare-earth tailing dilute sulphuric acid-dilute hydrochloric acid extract technology; The dilute hydrochloric acid leach liquor is removed Fe
2+Technique; Organic solvent effect crystalline calcium sulfate crystal whiskers technique; The Ore Leaching technique of its rare-earth tailing needs to grind before the rare-earth tailing Ore Leaching, and the acid-leaching reaction temperature is between 90 ~ 100 ℃, and the solid phase of sulfuric acid leaching leaches with dilute hydrochloric acid again; Sulfuric acid soaks the concentration 40% ~ 50% of the selected acid of process; The crystalline calcium sulfate crystal whiskers is removed before its crystallization in the liquid phase+divalent iron; Its technological line is: rare-earth tailing is after dilute sulphuric acid leaching, solid-liquid separation, and 90% rare earth is present in the solid phase in the mine tailing, and the sulfuric acid leaching acid non-soluble substance leaches through dilute hydrochloric acid, and the gained immersion liquid is at the lower Fe of oxygenant effect
2+Oxidation, oxidation solution is the crystalline calcium sulfate crystal whiskers under the monohydroxy-alcohol effect, after filtration, crystallisation by cooling and oven dry, obtains calcium sulfate crystal whiskers and rare earth ore concentrate.
2. rare-earth tailing Extraction of rare earth according to claim 1-the prepare method of calcium sulfate crystal whiskers, it is characterized in that, described crystalline calcium sulfate crystal whiskers, the iron before the crystallization in the liquid phase is+3 valencys, organic solvent is the alcohols of methyl alcohol, ethanol, and organic solvent is recycle.
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| CN102382979B true CN102382979B (en) | 2013-04-03 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| RU2528573C1 (en) * | 2013-03-05 | 2014-09-20 | Открытое акционерное общество "Объединенная химическая компания "УРАЛХИМ" | Method of extracting rare-earth metals and producing gypsum plaster from phosphogypsum hemihydrate |
| RU2528576C1 (en) * | 2013-03-05 | 2014-09-20 | Открытое акционерное общество "Объединенная химическая компания "УРАЛХИМ" | Method of extracting rare-earth metals and producing gypsum plaster from phosphogypsum hemihydrate |
| CN104630877B (en) * | 2015-01-28 | 2017-05-03 | 江苏理工学院 | Method for preparing calcium sulfate dihydrate whisker from tin-smelting waste slag |
| CN104724746B (en) * | 2015-02-15 | 2017-01-11 | 潍坊学院 | Method for recycling ardealite |
| CN106430273B (en) * | 2016-09-30 | 2018-11-02 | 四川什邡市星天丰科技有限公司 | A method of preparing dead plaster filler with ardealite |
| WO2021116742A1 (en) * | 2019-12-13 | 2021-06-17 | Scarab Chile Spa | Method for obtaining an alkaline earth metal compound |
| CN112408452B (en) * | 2020-11-16 | 2023-04-21 | 湖南科技大学 | Solution system for efficiently separating rare earth from phosphogypsum and preparing high-strength gypsum and application of solution system |
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| AU2008201945B2 (en) * | 2008-05-02 | 2014-03-06 | Arafura Resources Limited | Recovery of rare earth elements |
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