CN104975192A - Method for extracting scandium from scandium-containing material - Google Patents
Method for extracting scandium from scandium-containing material Download PDFInfo
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Abstract
The invention discloses a method for extracting scandium from a scandium-containing material, which mainly comprises the steps of acid leaching and leach solution treatment. The method is characterized in that the acid leaching step adopts a two-step acid leaching process, which sequentially comprises the steps of atmospheric-pressure acid leaching and high-pressure acid leaching. Compared with the prior art, the method disclosed by the invention can extract the scandium product with higher purity and higher leaching rate under the conditions of lower acidity, lower temperature and lower pressure.
Description
Technical field
The present invention relates to a kind of rare metal extracting method, particularly extract the method for scandium by two step pickling process from containing leaching scandium material.
Background technology
Scandium (Sc) is a kind of typical rare loose rare earth element, and few at the content of occurring in nature, the abundance in the earth's crust is 5 ~ 6 × 10
-6.There is due to scandium the features such as chemically reactive is high, good conductivity, fusing point are high, proportion is low, the soft easy cutting of matter, it is all obtained a wide range of applications in the key areas such as electric light source, aerospace, electronic industry, nuclear technique, superconductor technology.Along with the expanding day of scandium and compound range of application thereof, the demand of scandium is also constantly increased.The worldwide consumption of scandium in 1985 be 100 kilograms (with Sc
2o
3meter), nineteen ninety reaches 350 kilograms, within 2007, has then increased to 1000 kilograms, and within 2010, global consumption just reaches 10 tons.And the price of scandium is just every kilogram of Sc(99.99% in year in last century 90) 7500 dollars, rise steadily afterwards.Remain on about 4 times of the price of gold recent years always, your time once reached 10 times of gold.The quotation on April 17th, 2012 is every kilogram of Sc
2o
3(99.9999%) 32,000 dollar.The market demand cumulative year after year of scandium, quality product requires also day by day to improve, and along with the developing of novelty teabag, the research for scandium extracting method receives publicity day by day.
Scandium belongs to rare earth element, but the independent deposit of scandium is very rare, and seldom have scandium association in the mineral of lanthanon, it is not high to add content, and because the reasons such as chemical reaction make scandium more disperse in production technique, so the more difficult centralized recovery of scandium in the mineral of lanthanon.Therefore, in the industrial-scale production of producing rare earth, the product of scandium is not generally all had.At occurring in nature, scandium is lived and loose to be present in other mineral so that the form of associated mineral is rare.The scandium of association has been found in the ore of many elements, such as in the ores such as colliery, titanium ore, tungsten ore, navajoite, tin ore, rare-earth mineral, uranium ore and zirconium ore, find the scandium of trace, in the leaching process of these elements, scandium does not generally participate in the reaction in technique, finally focuses in the slag producing the discharge of these elements.Like this, the extraction process of principal element has also just become the process of enriching of scandium element, scandium element all concentrates in the processing waste (waste residue, waste liquid, slag mud, waste gas etc.) of essential mineral, so reclaim scandium-enriched element from these waste water or waste residue, often than directly having more economic worth from containing extracting scandium scandium ore deposit, can say that reclaiming scandium is the very abundant by-product technique that these essential minerals are produced, scandium is the byproduct having very much recovery value.
The annual scandium amount with exploiting out is very large, but the overwhelming majority is not recovered, and thus, seeks effective separation method, set up rational recovery process flow process, is realize the industrial key of scandium.Rational flow process should be set up during scandium-enriched and not destroy main technique.Complete processing containing scandium ore deposit is different, and the trend of scandium alters a great deal, and therefore the extraction of scandium is reclaimed and respectively had feature.
Current scandium is synthetical recovery from the byproduct in the ore deposits such as process titanium, aluminium, tungsten, tin, uranium, rare earth mainly, and therefore the extraction approach of scandium mainly contains following five kinds.
1. from aluminium by product (red mud), extract scandium
Red mud is the solid, powdery waste of discharge during plumbous oxide is produced, because its outward appearance is for red and gain the name, therefore also known as red soil.Main chemical compositions in red mud has CaO, SiO
2, Fe
2o
3, Al
2o
3, Na
2o, TiO
2, MgO, K
2o, Re
2o
3deng.Its thing phase main component has the mineral such as cancrinite, diaspore, rhombohedral iron ore, sodalite, calcite, rutile, calcium aluminosilicate hydrate.Scandium in red mud is not ion adsorption type, be not present in yet the new aluminium silicate mineral formed mutually in, and to be mainly present in the lattice of the mineral such as bauxite and accessory minerals such as rutile, ilmenite, sharp iron ore, zircon and monazite with isomorph form.The former Russian scholar has done much work to the research of reclaiming scandium from red mud, and the main method reclaiming scandium from red mud has: 1. reducing smelting process process red mud; 2. sulfurization roasting process red mud; 3. waste pickle liquor leaches process red mud; 4. leach with sodium carbonate solution; 5. the sulfuric acid leaching of concentration 50% is directly used; And 6. leach with concentrated hydrochloric acid.
Wherein, 5. be directly in red mud, add the sulfuric acid that concentration is 50% with the sulfuric acid leaching of concentration 50%, make red mud and sulfuric acid reaction, go out various useful component with water logging, extracted by leach liquor organic extractant, the metallic elements such as scandium, iron, aluminium enter in extraction phase, with sulfuric acid, back extraction is carried out to remove ferro element to extraction phase, finally precipitate from strip liquor with oxalic acid and obtain oxalic acid scandium, the at high temperature calcination of oxalic acid scandium is obtained Scium trioxide powder, and the rate of recovery of scandium is greater than 80%.6. concentrated hydrochloric acid leaching method leaches with concentrated hydrochloric acid, the leaching yield of scandium can reach 92.48%, the precipitation of hydroxide dissolving with hydrochloric acid that obtains after octanol+kerosene extraction, HC1 washing impurity-removing, NaOH solution are stripped, then extracts, precipitates, calcination, obtains Scium trioxide product.
Such as, CN101182601 discloses a kind of method extracting metal scandium, titanium from red mud, for extracting metal scandium in red mud and metal titanium.CN102061392 discloses a kind of method that composite extractant extracts scandium from changed red mud, wherein needs to carry out modification to red mud, and needs to adopt composite extractant.
2. from titanium by product, extract scandium
At present, the Scium trioxide of domestic market sales mainly obtains from Ti white hydrolyzed pregnant solution and tungsten slag.The method mainly comprises to be extracted scandium and extract scandium from chlorination flue dust from titanium white waste liquid.
Such as, CN101824555A discloses a kind of method extracting scandium, wherein the v-ti magnetite concentrate containing scandium is obtained chloride slag through superchlorination, chloride slag is leached in leaching liquid, then the filtrate filtered out is extracted, is isolated organic phase, obtain Scium trioxide by steps such as reextraction, filtration, calcinings afterwards.CN102796876A discloses a kind of method that titanium slag chlorination waste extracts Scium trioxide, belongs to vanadium titano-magnetite comprehensive utilization of resources field.The method comprises the steps such as leaching, reduction, precipitation, acidolysis, filtration, extraction, washing, reextraction, precipitation, calcining, finally obtains the Scium trioxide that grade is about 95%.CN103194609A disclose a kind of with titanium white waste acid water for the method for Scium trioxide prepared by raw material, comprising steps such as sulfuric acid dissolution, alkali precipitation, dissolving with hydrochloric acid, extraction, reextraction, oxalic acid precipitation and calcinations, obtained Scium trioxide purity can up to more than 99.9%, and the rate of recovery can up to 80-90%.
3. from tungsten by product, extract scandium
The wolframite residue of alkali roasting again after sodium wolframate is extracted in water logging, is referred to as tungsten slag usually.Tungsten slag is another valuable source extracting Scium trioxide.Scandium in wolframite mainly exists with the form of homomorphism impurity, also has some the rare loose districts containing scandium amorphous phase simultaneously, and the scandium in tungsten slag exists with the form of wolframic acid scandium and hydroxyl scandium.
According to the difference of its composition, the research of tungsten residues processing technique is carried out in the two directions: one is hydrometallurgy (utilizing hydrochloric acid, sulfuric acid and nitric acid); Two is pyrometallurgy.Wherein, hydrometallurgy scheme transfers in solution with acid by scandium, violent and iron etc., and all the other compositions are stayed in solid residue, and recycling solution extraction method can obtain the scandium concentrate that Scium trioxide content is 2-4%.
Such as, CN102676830A discloses a kind of method of scandium from tungsten steel slag.First the meticulous ball mill of slag is pulverized, then with main process such as mineral acid leaching, organic solvent extraction, oxalic acid precipitations.With the scandium in sulfuric acid leaching tungsten steel slag, pickling liquor separates out titanyl sulfate through leaving standstill, removed by filtration titanyl sulfate, the feed liquid (I) of mother liquor as extraction scandium after slag washing water dilution, the titanyl sulfate solids leached also dissolves with slag washing water, leaches the filtrate after insoluble impurity as the feed liquid (II) extracting scandium, extraction feed liquid (I) and feed liquid (II), load organic phases NaOH solution back extraction, the oxyhydroxide that back extraction obtains uses sulfuric acid dissolution again, and hydrolysis is except titanium.Except the rich scandium liquid organic solvent after titanium, carry out reextraction, load organic phases is with containing NaCl and H
2o
2sulphuric acid soln wash, then use NaOH solution back extraction, the scandium hydroxide throw out that back extraction obtains after filtration, after calcination with dissolving with hydrochloric acid, oxalic acid precipitation goes out oxalic acid scandium, then calcination changes into Scium trioxide.
4. from manganese by product, extract scandium
The mineral constituent of manganese ore is based on the violent ore deposit of water, and the pyrolusite of minute quantity, gangue mineral is based on quartz, and secondary is the calcedony and zircon etc. of clay and minute quantity.Because scandium is mainly distributed in manganese matrix, if do not leached by manganese, then scandium is also difficult leaches, and will improve scandium leaching yield, only has and first destroys manganese matrix, can be improved the leaching yield of scandium by the method for reducing leaching.Such as, add reductive agent-sulfuric acid leaching, the leaching yield of 86% can be reached.
5. from silt, extract scandium
River course silt is the new scandium resource of one found in recent years, scandium-containing mineral mainly ilmenite and ferrosilite in silt.With based on the rough concentrate of silt or the scandium concentrate of enrichment for raw material, leached by hydrochloric acid, nitric acid, sulfuric acid or hydrochloric acid adding consolvent and the method such as chlorinate-roast-leach, the scandium in recyclable silt.
In addition, the method for multiple extraction scandium is also reported in recent years in the patent literature.Such as, CN102653820A discloses a kind of method extracting scandium from Bayan Obo mine tailing, it is characterized in that first mine tailing being mixed in certainweight ratio with activator, then high-temperature roasting, hot wash, recovery activator, use inorganic acid solution, thus obtain containing scandium solution.CN102030355A discloses a kind of processing method extracting scandium oxide from spent acid, wherein leaching the leach liquor of zinc oxide ore with spent acid is raw material, add milk of lime adjusted to ph and make the scandium hydrolysis in infusion solution produce precipitation, be separated with iron with the zinc in solution after filtration, then repeat this process, finally make the scandium oxalic scandium postprecipitation in solution separate out, through twice dissolving and precipitation repeatedly, finally calcine, can scandium oxide be obtained.
CN102899485A disclose a kind of by resin-in-pulp process from containing the method extracting scandium scandium material.Will broken containing scandium material, add water levigate, add sulfuric acid, hydrochloric acid or nitric acid, acidleach under normal pressure, Zeo-karb is put in multiple stage continuous adverse current reactive tank, leaching limit, limit is adsorbed, and through multiple stage continuous adverse current acidleach and absorption, loaded resin extracts at regular time and quantity from first step reactive tank, resin equivalent vibration forward successively in later reaction groove, regenerating resin or new resin are added in last step reactive tank; The ore pulp leached after absorption enters tailings comprehensive treatment system.This invention adopts leaching limit, the limit absorption of normal temperature and pressure continuous countercurrent, the multistage leaching of scandium and absorption is concentrated in set of device and carries out simultaneously.
CN103215439A discloses a kind of method extracting scandium from scandium enriched substance, first the scandium enriched substance ~ 100 orders being accounted for more than 90% and alkali metal hydroxide are in mass ratio for the ratio of 1:0.6 ~ 1.8 mixes, roasting is carried out at 300 DEG C ~ 650 DEG C, washing this roasted ore again with water to pH is 7 ~ 9, water lotion is for reclaiming silicon, aluminium and alkali-metal oxyhydroxide, Leaching in Hydrochloric Acid is adopted to washing slag, the leached mud that filtration obtains is as the raw material reclaiming silicon, leach liquor is containing the thick solution of scandium, as the raw material extracting scandium further.The method is mainly used for extracting scandium from scandium enriched substance.
From finding out above, because scandium-containing mineral kind is more, the composition containing scandium ore and material is complicated, and scandium content is very low again, and the difficulty of its dispersion and extraction is very high.Therefore, there is no a kind of general extraction process at present, often several methods will be combined in studying and producing and carry out a large amount of trials and exploration, see the people such as Dai Huixin, the recovery of scandium and extraction present situation, " rare metal ", 36th volume the 3rd phase, 501-506 page, in May, 2012.But the common ground of above-mentioned most of method is, leaching operation is very crucial.The leaching yield of scandium directly affects the rate of recovery of scandium, usually determines best leaching agent, extract material granularity according to the feature of handling object, leaches solid-to-liquid ratio, extraction time, extraction temperature etc.
In leaching method, modal is acidleach, but the common compounds Scium trioxide of occurring in nature scandium is insoluble to diluted acid, can only dissolve in high temperature and/or concentrated acid.But the use of a large amount of concentrated acid can cause environmental pollution, and the use of high temperature increases energy consumption on the one hand, increases cost, and another aspect high temperature, peracid operation can improve the requirement to equipment etc.
CN102312090A discloses a kind of method of pressure leaching extraction scandium from scandium-containing mineral.According to the method, will containing scandium ore reduction, be levigately less than 200 order breezes to granularity and size mixing, ore pulp is injected autoclave, and directly stir high pressure acidleach, leaching yield is greater than 85%, and the ore pulp after leaching after filtration, obtains containing scandium solution; Through extraction, washing, back extraction, obtain the elementary enriched substance of scandium; Carry out secondary acid-soluble, obtain scandium precipitation; Scandium throw out is placed in High Temperature Furnaces Heating Apparatus calcine, obtain thick Scium trioxide, purity is greater than 99%, thus achieves the efficient directly leaching of scandium under low sour condition.But, the method is realizing while scandium efficiently directly leaches under low sour condition, in turn introducing pressure controlled processing condition, needing to implement under the condition of 2 ~ 5Mpa in autoclave, which not only improves the requirement to equipment etc., and add cost and not easy to operate.
To sum up, in prior art, the method for traditional extraction scandium normally operates under the condition of peracid, high temperature and/or high pressure, and production cost is high, also high to the requirement of equipment, is therefore difficult to satisfied extensive, long-term industrial requirement.
Summary of the invention
For above-mentioned deficiency of the prior art, the object of the present invention is to provide a kind of relative to prior art, under more Low acid, lower temperature and power at low pressure, extract the method for more high purity scandium with higher leaching yield.
For containing scandium material, achieve above-mentioned purpose by two following step pickling process, described method, primarily of acid leaching process part and leach liquor treatment process part composition, is characterized in that, described acid leaching process part adopts first normal pressure acidleach, two step pickling process of high pressure acidleach afterwards.
According to the preferred embodiment of the present invention, in described two step pickling process, described containing the Scium trioxide of scandium material containing 50ppm or more high-content.
According to the preferred embodiment of the present invention, in described two step pickling process, described containing scandium material, to be that Bayan Obo is rare select mine tailing, and preferred Bayan Obo selects niobium mine tailing.
According to the preferred embodiment of the present invention, in described two step pickling process, ground before acidleach by described containing scandium material, grinding particle size is-200 order ~-325 orders, preferably-250 order ~-325 orders, and percent of pass is 80% to 99%, preferably 85% to 99%.
According to the preferred embodiment of the present invention, in described two step pickling process, described acid is sulfuric acid or hydrochloric acid, preferably sulfuric acid.
According to preferred implementations more of the present invention, in described two step pickling process, described normal pressure acidleach is carried out at the temperature of envrionment temperature to 100 DEG C, preferably 70 DEG C to 100 DEG C.
According to the preferred embodiment of the present invention, in described two step pickling process, described high pressure acidleach 150 DEG C to 300 DEG C, preferably carry out at the temperature of 150 DEG C to 250 DEG C.
According to the preferred embodiment of the present invention, in described two step pickling process, described high pressure acidleach lower than 3MPa, preferably lower than 2MPa, particularly lower than the pressure of 1MPa under carry out.
According to the preferred embodiment of the present invention, in described two step pickling process, described is 1:1 ~ 3.5 containing scandium material and the weight ratio of acid, is preferably 1:1 ~ 2.5.
According to the preferred embodiment of the present invention, in described two step pickling process, the described weight ratio containing scandium material and water is 1:1 ~ 5, preferred 1:1 ~ 3.
According to the preferred embodiment of the present invention, in described two step pickling process, after described acid leaching process part, the slip after leaching is obtained containing scandium solution after filtration, then carry out enrichment and refine to obtain highly purified Scium trioxide product.
According to the preferred embodiment of the present invention, in described two step pickling process, thick scandium product will be obtained containing scandium solution after extraction, washing, back extraction process in described enrichment process.
According to the preferred embodiment of the present invention, in described two step pickling process, in described extraction treatment, use P
204with TBP two kinds of extraction agents.
According to the preferred embodiment of the present invention, in described two step pickling process, in described back extraction process, use NaOH solution as reverse-extraction agent.
According to the preferred embodiment of the present invention, in described two step pickling process, described refinement treatment comprises the steps:
Make to obtain the dissolving of thick scandium product by described enrichment process by adding hydrochloric acid;
In filtrate, add oxalic acid obtain oxalic acid scandium throw out;
High temperature sintering, obtains Scium trioxide; And
Optionally repeat above-mentioned technological process, obtain highly purified Scium trioxide product.
In highly preferred embodiment of the present invention, described two step pickling process comprise the steps:
A. at the temperature of envrionment temperature to 100 DEG C, preferably 70 DEG C to 100 DEG C, use acid, preferably sulfuric acid selects niobium mine tailing to carry out normal pressure acidleach to optionally levigate containing scandium material, preferably Bayan Obo, wherein said is 1:1 ~ 3.5, preferably 1:1 ~ 2.5 containing scandium material and the weight ratio of acid, and the described weight ratio containing scandium material and water is 1:1 ~ 5, preferred 1:1 ~ 3;
B. 150 DEG C to 300 DEG C, preferably 150 DEG C to the temperature of 250 DEG C and lower than 3MPa, preferably lower than under the pressure of 1MPa, high pressure acidleach is carried out to the mixture through above-mentioned normal pressure acidleach process; With
C. the slip after leaching is obtained containing scandium solution after filtration, then carry out enrichment and refine to obtain highly purified Scium trioxide product.
In highly preferred embodiment of the present invention, niobium mine tailing is selected for Bayan Obo, obtain purity be more than 99.9% Scium trioxide and purity be the niobium oxides of more than 99.9%.In whole technological process, the leaching yield of scandium is greater than 90%, and the total yield of scandium is greater than 70%; The leaching yield of niobium is greater than 65%, and the total yield of niobium is greater than 50%, effectively realizes the niobium of Baotou Steel's tailings, the comprehensive utilization of scandium resource.
Accompanying drawing explanation
Fig. 1. according to the process flow sheet of the specific embodiment of the invention.
Detailed Description Of The Invention
Method of the present invention is applicable to extract scandium from multiple containing scandium material, such as, extract scandium from primary ore or from mine tailing, slag.
Baiyuneboite is the comprehensive mineral deposit of the rare large-scale rare earth in the world and the symbiosis of the metallic element such as iron, thorium, and its total amount of rare earth accounts for 43% of world's total reserves.All generally contain scandium in all kinds of ore of baiyuneboite and rock, and contain scandium in ore than high in rock, the Sc of various ore
2o
3content is 40 to 160ppm, is enriched 3 to 10 times relative to earth's surface, Sc in rock in mining area
2o
3average content is 50ppm.Monomineralic Sc
2o
3content is generally 100 to 450ppm, reaches 2000ppm individually, higher than the content in domestic similar mineral deposit.Especially, the present invention is suitable for extracting scandium from baiyuneboite.
In the product of ore dressing separation operation, the part that useful target components content is minimum is commonly referred to mine tailing.Under current condition of technology and economy, should not further this portion of product of sorting again.But along with the development of Manufacturing science technology, useful target components also may have the economic worth recycled further.Mine tailing is not completely written-off waste material, but needs the precious deposits of taping the latent power, and it often containing the component can making other purposes, can fully utilize.In the context of the present invention, select niobium mine tailing refer to all can in order to recycle the mine tailing of niobium.
In current ore-dressing technique, scandium element is mainly enriched in and rarely selects in mine tailing, and rare scandium in niobium mine tailing that selects selecting mine tailing to obtain after selecting niobium obtains further enrichment, and the content of scandium can reach 300-500ppm.Essential mineral form in mine tailing is the mineral of riebeckite and the contour silicon of achmatite achmite, and scandium element is dispersed in wherein, does not have the independent mineral of scandium, this mineral with have very large difference for other mineralogical compositions extracting scandium at present.Method of the present invention is particularly useful for selecting mine tailing from the rare of Bayan Obo, particularly selects in niobium mine tailing and extracts scandium.
The present invention some preferred embodiment in, use select niobium mine tailing be derive from baiyuneboite select niobium mine tailing.What method of the present invention was specially adapted to following content selects niobium mine tailing, and this content is (with Sc
2o
3meter) be 50ppm or higher, preferred 70ppm or higher, particularly preferably 100ppm or higher, very particularly preferably 200ppm or higher, and particularly 300ppm or higher.
For selecting niobium mine tailing, the present invention have employed following technical process substantially: select niobium mine tailing → fine grinding → size mixing, normal pressure acidleach → pressure leaching → extracting and enriching → washing → oxalic acid precipitation → calcining → Scium trioxide product.
The first step extracting scandium from mineral is the decomposition of ore, namely chemical reagent and rare-earth mineral effect is utilized, by the chemical destruction of mineral, rare earth element is separated from the basement rock of other element of association, they are enriched in solution or precipitation, rare earth element and associated element is made to obtain initial gross separation, then by the further separation purification of rare earth element of extraction.
For the ease of Leaching of Scandium effectively in step of acid dipping subsequently, preferably will be broken containing scandium material before acidleach, more preferably will be levigate containing scandium material.But, grind meticulously can increase production cost.Inventors have investigated the relation between grinding particle size and scandium leaching yield, find that the leaching yield of scandium improves along with the reduction of grinding particle size, volume particle size ore grinding and sour contact area little, granule interior is difficult to contact with acid, reaction is not thorough, and grinding particle size less contact acid area is larger, reacts more abundant, leaching yield is higher, but particle is too small can increase grinding cost.Therefore, based on the consideration of cost savings, the present invention preferably containing the grinding particle size of scandium material be-200 orders to-500 orders, be preferably-200 orders to-400 orders, be more preferably-200 orders to-325 orders, percent of pass is about more than 50%, preferably about 85%, particularly preferably about 99%.In a preferred embodiment of the present invention, described grinding particle size is-250 order ~-325 orders, and percent of pass is about 99%.In a particularly preferred embodiment of the present invention, described grinding particle size is-325 orders, and percent of pass is 99%.
Before carrying out acidleach, in prior art usually by described containing scandium material or above-mentionedly levigate carry out breeze containing scandium material and size mixing, but for the present invention, in the process that breeze is sized mixing, to normal pressure acidleach be carried out simultaneously.When preparing mineral, water, sour mixed slurry, the ratio of three kinds of materials carefully to be controlled.The concentration of described slip or the described degree of scatter containing scandium material or breeze of water content impact of described slip, the leaching yield then after impact, also affects the acidity in step of acid dipping.And the acidity leaching yield of impact acid to scandium on the one hand, affect the pollution level of the method to environment on the other hand.Usually, leaching yield increases along with the reduction of liquid-solid ratio, and the frequency that tailings particles collides under the effect of stirring when liquid-solid ratio is larger can significantly improve, and plays the effect of ore grinding, tailings particles mean particle size is declined, is conducive to the leaching of scandium under long-time reaction.Preferably, the liquid-solid ratio in present invention process process is 1 ~ 6:1, preferably 2 ~ 5:1, more preferably 2 ~ 4:1, particularly preferably 2 ~ 3:1, particularly about 2 ~ 1.In addition, based on considering and selecting suitable Acidity Range between efficiency and environmental protection, significant.Contriver finds, the leaching yield of scandium improves along with the increase of acidity, but acidity is crossed ambassador's pulp viscosity and increased, and more easily produces liquid film layer and increases the diffusional resistance of scandium, being unfavorable for the leaching of scandium.Preferably, the acidity in present invention process process is 4.5 to 5.5mol/L.In particularly preferred embodiments, the acidity in present invention process process is about 5mol/L.In a preferred embodiment of the invention, in described slip, the weight ratio containing scandium material and water is generally 1:1 ~ 5, and preferred 1:1 ~ 3, are particularly preferably 1:1 ~ 2.5.
Select niobium mine tailing ore pulp for Xuan Ni factory, preferably, first concentrate, the prime cement then by concentrated is levigate, the slurry of milled is carried out press filtration, sizes mixing afterwards again.Such as, one selects niobium mine tailing ore pulp slag inclusion about 5 to 55%, moisture about 45 to 95%, carry out the concentrated prime cement slag inclusion about 50%, moisture about 50% of concentrated rear gained, this concentrated prime cement is sent to grinding plant, such as vertical grinder is milled to-200 orders to-325 orders about 95% to be passed through; After the slurry press filtration of milled to slag inclusion 70 to 80%, moisture 20 to 30%, then size mixing.
In the particularly preferred embodiment of one, the described solid content selecting niobium mine tailing ore pulp is about 30%, i.e. slag inclusion about 30%, and after concentrated, the solid content of concentrated prime cement is about 50%.Yield can reach 95% or higher, and preferably 98% or higher.
In the particularly preferred embodiment of one, the slag particle degree of concentrated prime cement charging is about-200 orders, and about 80% passes through, and after fine grinding, the slag particle degree of discharging is about-300 to about 325-orders, and 90% to 99%, preferably 95 to 99% pass through.
For being strong acid to the acid carrying out acidleach containing scandium material, such as sulfuric acid, hydrochloric acid, nitric acid etc., preferably sulfuric acid and hydrochloric acid, more preferably sulfuric acid, also can use their mixture.
In step of acid dipping of the present invention, the consumption of acid affects the leaching yield of scandium.In embodiments of the present invention, be 1:1 ~ 3.5 containing scandium material and the weight ratio of acid, be preferably 1:1 ~ 2.5, be particularly preferably 1:1 ~ 1.5.
In the process of carrying out acidleach, by adopting the sulfuric acid of suitable concn, the balance between required leaching efficiency, required leaching yield, low cost, liquid waste disposal can be realized.In a preferred embodiment of the invention, the concentration for the acid of acidleach is such as 90 to 98%, preferably 90 to 95%, more preferably 92.5 to 93.5%.
In the first normal pressure step of acid dipping, during preparation mixed slurry, the weight ratio of mineral and water is 1:1 ~ 5, and preferred 1:1 ~ 3, are particularly preferably 1:1 ~ 2.5; Mineral are 1:1 ~ 3.5 with the weight ratio of acid, are preferably 1:1 ~ 2.5, are particularly preferably 1:1 ~ 1.5.Contriver finds, when stirring velocity reaches 100 ~ 500 revs/min, and the scandium leaching yield that can realize ideal.But, based on energy saving and the consideration reducing equipment requirements, in normal pressure step of acid dipping of the present invention, preferably stir with the speed of 100 to 400 revs/min, preferably stir under the speed of 100 to 300 revs/min, stir particularly preferably under the speed of 100 to 200 revs/min.Normal pressure acidleach carries out 1 ~ 5 hour usually, preferably carries out 1 ~ 3 hour, more preferably carries out 1 ~ 2.5 hour, particularly preferably carries out 1 ~ 2 hour.
Usually, leaching yield improves along with the increase of temperature, but the too high meeting of extraction temperature significantly increases energy consumption, brings impact to equipment material selection, safety problem etc.Take suitable temperature describedly sizing mixing, in normal pressure acidleach process, such as envrionment temperature to 100 DEG C, preferably about 70 DEG C to 100 DEG C, preferably about 80 DEG C are to 100 DEG C, particularly preferably 85 DEG C to 95 DEG C.Optionally, used vapour direct heating is to described suitable temperature.
For the first normal pressure step of acid dipping, preferably, a certain proportion of Baotou Steel's tailings, water and sulfuric acid (such as, the sulfuric acid of 98%) can be added to reactor, leach under preferred processing condition above.
According to the present invention, after normal pressure acidleach, subsequently the described mixture through the process of normal pressure step of acid dipping is injected autoclave and carry out high pressure acidleach.
Preferably, just reaction mass is injected autoclave when carrying out normal pressure acidleach, after carrying out normal pressure acidleach, original position carries out high pressure acidleach.
Contriver finds, in described high pressure step of acid dipping, the leaching yield of scandium improves along with the increase of temperature.But, based on the consideration for factors such as equipment requirements raisings of energy saving and high temperature, the present invention preferably carries out described high pressure acidleach at the temperature of 150 DEG C to 300 DEG C, preferably carry out at the temperature of 150 to 250 DEG C, carry out particularly preferably at the temperature of 150 to 200 DEG C, the leaching yield being greater than 90% can be realized in this temperature range, be preferably greater than 92%, particularly preferably be greater than 95%, be especially preferably greater than the leaching yield of 97%.
The leaching yield of Sc calculates by following formula:
Sc leaching yield (%)=(M1 × ω 1-M2 × ω 2)/(M1 × ω 1) × 100%
Wherein: M1---experiment mine tailing weight;
M2---slag weight;
ω 1---Sc content in mine tailing;
ω 2---Sc content in slag.
According to the present invention, in described high pressure step of acid dipping, the leaching yield of scandium improves along with the increase in reaction times substantially, but, based on the consideration of energy saving and time, cost savings, according to the embodiment of the present invention, in described high pressure step of acid dipping, reaction times is preferably 0.5 to 4 hour, is more preferably 1 to 4 hour, is particularly preferably about 1 to 3 hour.
According to the present invention, in described high pressure step of acid dipping, the leaching yield of scandium improves along with the quickening of reactor stirring velocity substantially.Contriver finds, when stirring velocity reaches 100 to 500 revs/min, the scandium leaching yield that can realize ideal, but, based on energy saving and the consideration reducing equipment requirements, in high pressure step of acid dipping of the present invention, preferably stir with the speed of 100 to 400 revs/min, preferably stir under the speed of 100 to 300 revs/min, stir particularly preferably under the speed of 100 to 200 revs/min.
In high pressure step of acid dipping of the present invention, the leaching yield of scandium improves along with the rising of pressure.But high top pressure operation improves the requirement to equipment etc., increase cost and not easy to operate.Therefore, based on considering of the factors such as efficiency, equipment requirements, operability and cost control, high pressure step of acid dipping of the present invention, is particularly preferably implemented lower than under the pressure of 1Mpa preferably lower than 2MPa lower than 3MPa preferably.On the other hand, consider from the angle of theory, as long as the pressure in described high pressure step of acid dipping is just conducive to the leaching of scandium higher than normal pressure, but based on the consideration of efficiency, the pressure in described high pressure step of acid dipping is unsuitable too low.Usually, high pressure step of acid dipping of the present invention greater than or equal to 0.5MPa, preferably greater than or equal to the pressure of 0.6MPa under implement.In a preferred embodiment of the invention, the pressure in described high pressure step of acid dipping is 0.6MPa to 1MPa, preferred 0.7MPa to 0.9MPa, such as about 0.7MPa, about 0.8MPa, about 0.9MPa etc.
In addition, by the prolongation reaction times under the condition of not carrying out stirring, the scandium leaching yield can realized ideal equally.Such as, in the particularly preferred embodiment of one, other condition is identical with mentioned above, under not carrying out agitation condition, by 4 to 10 hours will be extended to the reaction times, preferably 4 to 8 hours, particularly preferably 4.5 to 6 hours, achieve desirable scandium leaching yield equally.
It should be noted that in addition, fine grinding mentioned above, to size mixing and various parameters in normal pressure acidleach and high pressure acidleach must not meet simultaneously.Such as, when the grain graininess of fine milling step is larger, by the leaching time that extends in step of acid dipping and/or raise acidleach temperature and/or improve stir speed (S.S.), the leaching effect identical with fine granulation in fine milling step can be realized.Similar, between other parameter, there is such relation equally.
Each in above-mentioned preferred feature all can be applied separately, also can combine one or more in above-mentioned preferred feature.Preferably, above-mentioned all preferred features are applied simultaneously in one embodiment.
According to the present invention, after above-mentioned two step acidleach process, by the slurry filtration leached, obtain the solution containing scandium.In multiple embodiment of the present invention, at the described niobium mine tailing that selects after acid leaching process process, the leaching yield of scandium can reach and be greater than 90%, is preferably greater than 92%, is particularly preferably greater than 95%.
Depend on different from scandium material, above-mentionedly also may can contain other element multiple containing in scandium solution.Such as, for selecting niobium mine tailing, wherein also the elements such as Si, Fe, Mg, Al, Ca, Mn, rare earth may be contained.In this case, after above-mentioned two step method acidleach, need carry out enrichment to the scandium in solution and refine.
The domestic enrichment to Scium trioxide at present adopts extraction process substantially with refining, and application more widely extraction agent is P
204(two (2-ethylhexyl phosphonic acid)) and TBP(phosphonic acids tri-n-butyl).
Extraction about Scium trioxide is according to association's extraction reaction mechanism, such as, can utilize P
204with TBP two kinds of extraction agents, make extraction solvent with kerosene, the scandium in feed liquid is extracted with ligand form, obtain smart scandium through back extraction, repeatedly purification.
At employing P mentioned above
204with TBP two kinds of extraction agents, make extraction solvent with kerosene when, principal reaction step is represented by following reaction formula:
Extraction: Sc
3++ 3 (HA)
2+ xH
2o → Sc (HA
2)
3xH
2o+3H
+
Sc(HA
2)
3·xH
2O+xTBP→Sc(HA
2)
3·xTBP+xH
2O
Back extraction: Sc (HA
2)
3xTBP+NaOH → Sc (OH)
3↓+3Na (HA)
2+ xTBP
Purify: Sc (OH)
3+ 3HCl → ScCl
3+ 3H
2o
ScCl
3+3H
2C
2O
4→Sc
2(C
2O
4)
3+6HCl
Sc
2(C
2O
4)
3→Sc
2O
3+3CO↑+3CO
2↑
In formula: (HA)
2represent P
204.
In one embodiment of the invention, have employed the operational path of following enrichment and refining scandium:
Enrichment section: P
204+ TBP extraction-washing-back extraction, obtains thick scandium product.
Refining stage: HCl dissolving-oxalic acid precipitation-calcination, repeatedly this process, obtains High-purity Sc Oxide.
According to one embodiment of the present invention, in described extraction treatment, by upper one treatment stage obtain feed liquid mixing, be separated after phase-splitting.Organic phase before extraction and aqueous phase configure respectively, determine to compare V (O): V (A) (V (O) and V (A) represents the volume of organic phase and aqueous phase respectively) according to the concentration of scandium in leach liquor, and determine that the best of enrichment section organic phase forms processing parameters such as (volume fractions).In one embodiment of the invention, P is used
204+ TBP implements described extraction treatment, and in raffinate, the concentration of scandium is less than 2ppm, and the percentage extraction of scandium is greater than 98%.
In another embodiment of the invention, after carrying out back extraction process to raffinate, filter, wash the enriched substance obtaining scandium, wherein scandium oxide content is about 30%.
According to another embodiment of the invention, in described enrichment process, take sulphuric leachate as raw material, use P
204, TBP, kerosene is mixed with organic phase, compare 1:5 ~ 15, preferred 1:10, extract in Kang Shi vibrator, during extraction, the set of frequency of vibrator is 200 ~ 300Hz, preferred 250Hz, and the concussion time is 5 ~ 15 minutes, preferably 10 minutes.Then, to extract the organic phase of acquisition for raw material, preparation hydrogen peroxide-sulphuric acid soln is for washing titanium liquid, and preparation dilute hydrochloric acid is washed metal liquid.Carry out respectively washing titanium, washed metal in the condition being in a ratio of about 1:1.Use equipment is Kang Shi vibrator, and the set of frequency of vibrator is 200 ~ 300Hz, preferred 250Hz, and the concussion time is 5 ~ 15 minutes, preferably 10 minutes.Afterwards, get the sodium hydroxide (volume: about 1:1, such as, be 1000ml) that the organic phase after washed metal adds about 3mol/L, under the water bath condition of about 70 DEG C, stir back extraction be about 1h.By the alkali cake that obtains after the back extraction dissolving with hydrochloric acid with about 6mol/L, then regulate pH to 1.5 ~ 2.5, preferably 2, obtaining filtrate after filtration is thick scandium liquid, and filter cake is the enriched substance of niobium.
About the progression washing titanium and washed metal, the eluting rate that higher washing progression just can be realized ideal, but the loss of Sc or Nb time too high, may be caused.Therefore, suitable washing progression should be selected.By repetition test, contriver finds, wash titanium progression when being set to 20 grades, the eluting rate of titanium reaches more than 99.5%, wherein causes the loss of Sc hardly, but the Nb of about 6% can be caused to enter wash titanium liquid and lose; Washed metal progression is set to 15 grades, and the eluting rate of iron reaches more than 99%, and this process can cause the loss of a small amount of Sc, Nb, Sc wherein be lost in about 0.5%, Nb be lost in about 2%.
Then, refinement treatment is carried out to the thick scandium product obtained through above-mentioned enrichment process.According to one embodiment of the present invention, will obtain thick scandium product HCl dissolve by described enrichment process, regulate pH to about 1.2 ~ 2.0 with sodium hydroxide, filtration washing several times, obtain the enriched substance of niobium, and wherein the content of niobium oxide is greater than 80%; Filtrate adds excessive oxalic acid precipitation and obtains oxalic acid scandium, calcination about 1 hour under 800 DEG C or higher temperature, obtains the Scium trioxide product of about 98%; Process cycle 2 ~ 3 times herein, obtains the Scium trioxide product of qualified 99.9%.
Embodiment according to another preferred, uses P
350(extraction) purifies to thick scandium liquid: organic phase composition is P
350about 40%, kerosene about 60%; [the H of thick scandium liquid (wherein the concentration of Sc is about 6g/L) is regulated with hydrochloric acid
+] to about 6.5mol/L; Extraction: O/A=is about 2:1, extracts 3 grades, vibrates about 10 minutes under about 250Hz, leaves standstill about 10 minutes.Then, carry out back extraction with the HCl of about 1.2mol/L, O/A=is about 1:1,3 stage countercurrent back extractions; Vibrate under about 250Hz about 10 minutes, leave standstill about 10 minutes.Thick scandium liquid obtains smart scandium liquid after purifying, the scandium precipitation making wherein with about 50% excessive oxalic acid.Filter the oxalic acid be precipitated with about 1% repeatedly to rinse.
In the calcining/calcination step of oxalic acid scandium, preferably, slowly point gradient increased temperature calcining precipitation, avoids Sc
2o
3loss.
Those of ordinary skill in the art also can use other enrichment known in the art and process for refining and/or parameter to processing, to obtain required Scium trioxide product containing scandium leach liquor of obtaining through two step pickling process process of the present invention.
Compared with prior art, the present invention is characterised in that two step acid leaching process: first carry out normal pressure acidleach, carry out high pressure acidleach more afterwards.After high pressure step of acid dipping of the present invention, those of ordinary skill in the art easily can select suitable extracting and enriching, stir the techniques such as back extraction, abstraction purification, oxalic acid precipitation, oven dry, calcining, comprise and select suitable equipment, to extract highly purified scandium product.As shown in Figure 1, wherein the step of " routine techniques means " part is only exemplary, those of ordinary skill in the art also can easily select other technique means any well known in the prior art to realize leaching the extraction after step, obtain highly purified product.
Extraction process of the present invention, first through the process of normal pressure step of acid dipping, can realize the acidleach effect of wishing at lower pressures like this in high pressure step of acid dipping afterwards, thus the requirement reduced equipment, reduce production cost, conserve energy, handled easily and raising processing safety.The leaching yield of scandium is stabilized in more than 90%, finally obtains the high-purity mangesium oxide scandium product of 99.9%.Niobium mine tailing is selected for Bayan Obo, while acquisition purity is the Scium trioxide of more than 99.9%, have also obtained the niobium oxides that purity is more than 99.9%.In whole technological process, the leaching yield of scandium is greater than 90%, and the total yield of scandium is greater than 70%; The leaching yield of niobium is greater than 65%, and the total yield of niobium is greater than 50%, effectively realizes the niobium of Baotou Steel's tailings, the comprehensive utilization of scandium resource.
In above-mentioned technical process, such as, the niobium mine tailing that selects coming free niobium factory enters thickening equipment, and concentrated prime cement enters grinding plant and carries out fine grinding, the slurry of milled enters surge tank acid adding and water is sized mixing, and the slurry transport after sizing mixing is carried out two step impregnations to pressure leaching equipment; Afterwards, extracting and enriching is carried out to filtrate; Through washing, acid-soluble, return after tunes, filtration etc. process, filtrate is extracted, washs, strip liquor that back extraction obtains scandium; This strip liquor can precipitate with oxalic acid, and oxalic acid scandium precipitation obtains Scium trioxide product through calcining.
The present invention is explained by specific embodiment below in conjunction with accompanying drawing.It should be noted that, described embodiment is only come by way of example more clearly to explain the present invention, and embodiment should be considered as any restriction to the claimed scope of the application.
Embodiment
In the specific embodiment of the present invention, the major equipment of use is high-temperature high-pressure reaction kettle, (model GCF-10L Weihai Jing Da chemical machinery company limited); Kang Shi vibrator (KS-2 type, Jiaxing Zhongxin Medical Instrument Co., Ltd.); Reinforcement electric mixer (JJ-1 type, huge port, Binhai New Area in Tianjin Hong Bin testing installation factory); Retort furnace (TSX1700 type, western nit (Beijing) electric furnace company limited).
Main agents used in embodiment: vitriol oil massfraction 98%, analytical pure (Beijing Chemical Plant); Concentrated hydrochloric acid massfraction 35%, analytical pure (Tianjin Xiang Zhuo Chemical Co., Ltd.); P
204, chemical pure (Luoyang Aoda Chemical Co., Ltd.); TBP, analytical pure (Luoyang Aoda Chemical Co., Ltd.); Kerosene, technical grade; P
350, technical grade; Hydrogen peroxide, analytical pure (Tianjin makes chemical preparations company limited into); Oxalic acid, analytical pure, (Beijing Chemical Plant).
In the specific embodiment of the present invention, adopt the content of the element such as scandium, niobium in ICP-MS and ICP-AES detection by quantitative solution, adopt the content of each composition in X-fluorescence detection by quantitative solid phase.
Described embodiment adopts Bayan Obo mine tailing as the extraction carrying out scandium containing scandium material.Niobium mine tailing is selected for the Bayan Obos of multiple batches that take at random, composition analysis result (by weight percentage) as shown in table 1:
The chemical composition of table 1. Bayan Obo mine tailing
a: the sample of lot number 1, be called for short sample 1, lower same.
Embodiment 1
Scandium is extracted containing scandium material in accordance with the following steps from described:
slurry concentrating, fine grinding
By the above-mentioned ore pulp of niobium mine tailing (slag inclusion about 30%, moisture about 70%) that selects of free niobium factory concentrates, concentrated prime cement (slag inclusion about 50%, moisture about 50%) is sent to vertical grinder and is milled to about-200 orders about 80% and passes through; After the slurry press filtration of milled to slag inclusion 75%, moisture 25%, carry out the size mixing technology of lower step.
size mixing, normal pressure acidleach
The ore pulp immigration surge tank of milled, adds water and the sulfuric acid of concentration 93% carries out sizing mixing and acidleach, heats to about 90 DEG C.Wherein, the time of sizing mixing is about 2 hours, selects the weight of material of niobium mine tailing and sulfuric acid than being about 1:1, and select the weight of material of niobium mine tailing and water than being about 1:1, stirring velocity is about 500 revs/min.
pressurized acid leaching
Proceeded in pressurized acid leaching still by slurry through upper step process, react under being heated to the temperature of about 150 DEG C, wherein, the reaction times is about 1 hour, and stirring velocity is about 400 revs/min, and pressure is about 3MPa.
From the multielement analysis result of mine tailing, main containing elements such as Si, Fe, Mg, Al, Ca, Mn, rare earths in mine tailing.Elected niobium mine tailing is after acidleach in a kettle., and these element major parts have all entered into solution.Carry out composition analysis to leached mud, leach liquor, the leaching yield of each component of sample 1 to 5 is as shown in table 2:
The leaching yield of each component of table 2. different batches sample
Can draw from upper table, select niobium mine tailing for sample 1 to 5, after the process of acid leaching process, the leaching yield of scandium can up to more than 90%, but in immersion liquid, the constituent content such as titanium, iron, manganese is also higher.Therefore, emphasis is needed to consider the impact of the elements such as iron, manganese, titanium when carrying scandium.
enrichment, refining
Afterwards, carry out extracting, washing (washing titanium, washed metal), back extraction, P
350the steps such as purification, oxalic acid precipitation, calcining are to extract scandium.
Wherein, the percentage extraction of Sc along with the change of extraction progression little, the percentage extraction of Nb improves obviously along with the increase of progression.In this embodiment, slective extraction progression is 5 grades, and the percentage extraction that the percentage extraction of Sc is greater than 99%, Nb reaches 99%.
Ti (IV) and H
2o
2stable title complex pertitanic acid can be formed, so add H in feed liquid in sulfuric acid medium
2o
2-H
2sO
4solution, makes titanium participate in reaction and generates pertitanic acid, thus directly removed from organic phase by titanium.Wash titanium progression and be set to 20 grades.
In the process of extracting scandium, part Fe
3+, a small amount of Mn
3+enter organic phase, add acid solution to organic phase, countercurrent washing can remove most of iron manganese impurity.Wash organic mutual-assistance iron with dilute hydrochloric acid solution and enter washing lotion, avoid scandium to lose by Controlled acidity.Washed metal progression is set to 15 grades.
After washing, after testing, the back extraction ratio of scandium, niobium is greater than 97%, and in excellent molten experiment, scandium, niobium are separated substantially completely.The niobium enriched substance composition obtained is as shown in table 3:
Table 3. niobium enriched substance composition
Purify after the niobium enriched substance saturated oxalic acid solubilize of acquisition, obtain high-purity oxalic acid niobium as shown in table 4 through calcining after product composition:
Impurity in table 4. niobium oxides
Can draw from upper table, niobium oxides product purity is greater than 99.9%, and completely not fluorine-containing.Product also has fine size, good fluidity, without igloss, is not afraid of the premium propertiess such as tide.
In this embodiment, application P
350the excellent properties of impurity in Separation of Scandium liquid, purifies to obtained thick scandium liquid, and in purification process, scandium loss is less than 0.5%.Oxalic acid precipitation: once add 50% excessive oxalic acid, after heated and stirred, cooling precipitation, filtrate is again through heating concentrated post crystallization, and oxalic acid circulation is returned with realizing closed cycle.
The foreign matter content of the Scium trioxide product that oxalic acid scandium obtains after calcining is in shown in table 5 and table 6:
Table 5. Rare Earth Impurities In Scandium Oxide
Non-rare earth impurity in table 6. Scium trioxide
From result, for sample 1, the purity obtaining Scium trioxide is greater than 99.9%(99.91%), yield 72.60%.
For sample 2-5, the scandium leaching yield realized is also all as shown in table 3 higher than 90%(), the purity obtaining Scium trioxide is all greater than 99.9%, and yield is all greater than 70%.
Embodiment 2
In high pressure step of acid dipping, do not stir, will extend to 8 hours the reaction times, other step is identical with embodiment 1.
In this embodiment, for sample 1, achieve the scandium leaching yield of 91.50%, the purity of gained Scium trioxide is 99.90%, yield 71.23%.For sample 2-5, the scandium leaching yield of realization is all higher than 90%, and the purity obtaining Scium trioxide is all greater than 99.9%, and yield is all greater than 70%.
Embodiment 3
In slurry concentrating, fine grinding process, concentrated prime cement is milled to about-275 orders about 90% and passes through; In normal pressure acidleach (sizing mixing) step, select the weight of material of niobium mine tailing and this sulfuric acid than being about 1:3.5, select the weight of material of niobium mine tailing and water than being about 1:5, stirring velocity is about 300 revs/min; In high pressure step of acid dipping, temperature of reaction is about 180 DEG C, and the reaction times is about 4 hours, and stirring velocity is about 300 revs/min, and pressure is about 1MPa; Other step is identical with embodiment 1.
In this embodiment, for sample 1, achieve the scandium leaching yield of 96.20%, the purity of gained Scium trioxide is 99.92%, yield 74.20%.For sample 2-5, the scandium leaching yield of realization is all higher than 90%, and the purity obtaining Scium trioxide is all greater than 99.9%, and yield is all greater than 70%.
Embodiment 4
In slurry concentrating, fine grinding process, concentrated prime cement is milled to about-325 orders about 99% and passes through; In normal pressure acidleach (sizing mixing) step, select the weight of material of niobium mine tailing and this sulfuric acid than being about 1:2.5, select the weight of material of niobium mine tailing and water than being about 1:3, stirring velocity is about 200 revs/min; In high pressure step of acid dipping, the reaction times is about 3 hours, and stirring velocity is about 200 revs/min, and pressure is about 1.0MPa; Other step is identical with embodiment 1.
In this embodiment, for sample 1, achieve the scandium leaching yield of 96.67%, the purity of gained Scium trioxide is 99.93%, yield 74.98%.For sample 2-5, the scandium leaching yield of realization is all higher than 90%, and the purity obtaining Scium trioxide is all greater than 99.9%, and yield is all greater than 70%.
Embodiment 5
In slurry concentrating, fine grinding process, concentrated prime cement is milled to about-325 orders about 99% and passes through; In normal pressure acidleach (sizing mixing) step, select the weight of material of niobium mine tailing and this sulfuric acid than being about 1:1.7, select the weight of material of niobium mine tailing and water than being about 1:2, stirring velocity is about 100 revs/min; In high pressure step of acid dipping, the reaction times is about 2 hours, and stirring velocity is about 100 revs/min, and pressure is about 0.9MPa; Other step is identical with embodiment 1.
In this embodiment, for sample 1, achieve the scandium leaching yield of 96.59%, the purity of gained Scium trioxide is 99.93%, yield 75.06%.For sample 2-5, the scandium leaching yield of realization is all higher than 90%, and the purity obtaining Scium trioxide is all greater than 99.9%, and yield is all greater than 70%.
Embodiment 6
In slurry concentrating, fine grinding process, concentrated prime cement is milled to about-325 orders about 99% and passes through; In normal pressure acidleach (sizing mixing) step, select the weight of material of niobium mine tailing and this sulfuric acid than being about 1:1.2, select the weight of material of niobium mine tailing and water than being about 1:8, stirring velocity is about 200 revs/min; In high pressure step of acid dipping, the reaction times is about 2.5 hours, and stirring velocity is about 250 revs/min, and pressure is about 0.8MPa; Other step is identical with embodiment 1.
In this embodiment, for sample 1, achieve the scandium leaching yield of 97.11%, the purity of gained Scium trioxide is 99.93%, yield 74.66%.For sample 2-5, the scandium leaching yield of realization is all higher than 90%, and the purity obtaining Scium trioxide is all greater than 99.9%, and yield is all greater than 70%.
Compared with embodiment 1, although embodiment 3-6 reduce further the pressure of high pressure step of acid dipping, but still obtain with embodiment 1 quite or even higher scandium leaching yield, Scium trioxide purity and Scium trioxide yield.
Embodiment 7(comparative example)
Sizing mixing, in normal pressure acidleach process, do not add acid, identical (that is, the replacing the sizing mixing of embodiment 1, normal pressure acidleach process with process of sizing mixing) of other parameter in this step and other step and embodiment 1.
In this embodiment, for sample 1, the leaching yield of scandium only reaches 80.39%, and the purity of gained Scium trioxide is 99.90%, yield 64.91%.For sample 2-5, the scandium leaching yield of realization does not all reach 90%, although can reach the purity of 99.9%, yield all significantly reduces.
Summarize embodiment 1(the present invention in table 7) and embodiment 7(prior art) comparing result (leaching yield of scandium and the productive rate of gained high-purity mangesium oxide scandium):
Table 7. is the leaching yield of scandium and the productive rate of Scium trioxide under embodiment 1 and embodiment 7 condition
To sum up, two step pickling process of the present invention, reduce the requirement to equipment, reduce production cost, saved energy, facilitate operation and improve processing safety etc., simultaneously the leaching yield of scandium can be stabilized in more than 90%, and the scandium product that purity reaches 99.9% or higher can be extracted under more Low acid, lower temperature and power at low pressure.
Applicant has disclosed as possible can the embodiment meeting institute's inventive concept of reasonable prediction and application.But, still may there is the improvement of unpredictalbe, the unsubstantiality as equivalents.Although describe the present invention with reference to concrete illustrative embodiments of the present invention, but significantly, under the condition not deviating from the subject or scope of the present invention, according to the above description, describedly multiplely to substitute, to improve and change is apparent to those skilled in the art.Therefore, what the present invention was intended to comprise the claimed technical scheme of the present invention all thisly substitutes, improve and variant.
Claims (23)
1., from containing the method extracting scandium scandium material, described method is primarily of acid leaching process part and leach liquor treatment process part composition, and it is characterized in that, described acid leaching process part adopts first normal pressure acidleach, two step pickling process of high pressure acidleach afterwards.
2. method according to claim 1, is characterized in that, described containing the Scium trioxide of scandium material containing 50ppm or more high-content.
3. method according to claim 1, is characterized in that, described containing scandium material, to be that Bayan Obo is rare select mine tailing.
4. method according to claim 3, is characterized in that, described is that Bayan Obo selects niobium mine tailing containing scandium material.
5. the method according to any one of claim 1-4, is characterized in that, ground described containing scandium material before acidleach, grinding particle size is-200 order ~-325 orders, and percent of pass is 80% to 99%.
6. the method according to any one of claim 1-4, is characterized in that, described acid is sulfuric acid or hydrochloric acid.
7. method according to claim 6, is characterized in that, described acid is sulfuric acid.
8. the method according to any one of claim 1-4, is characterized in that, described normal pressure acidleach is carried out at the temperature of envrionment temperature to 100 DEG C.
9. method according to claim 8, is characterized in that, described normal pressure acidleach is carried out at the temperature of 70 DEG C to 100 DEG C.
10. the method according to any one of claim 1-4, is characterized in that, described high pressure acidleach is carried out at the temperature of 150 DEG C to 300 DEG C.
11. methods according to claim 10, is characterized in that, described high pressure acidleach is carried out at the temperature of 150 DEG C to 250 DEG C.
12. methods according to any one of claim 1-4, it is characterized in that, described high pressure acidleach is carried out under lower than the pressure of 3MPa.
13. methods according to claim 12, is characterized in that, described high pressure acidleach is carried out under lower than the pressure of 2Ma.
14. methods according to claim 12, is characterized in that, described high pressure acidleach is carried out under lower than the pressure of 1MPa.
15. methods according to any one of claim 1-4, is characterized in that, in described two step pickling process, described is 1:1 ~ 3.5 containing scandium material and the weight ratio of acid.
16. methods according to claim 15, is characterized in that, in described two step pickling process, described is 1:1 ~ 2.5 containing scandium material and the weight ratio of acid.
17., according to the method for any one of claim 1-4, is characterized in that, in described two step pickling process, the described weight ratio containing scandium material and water is 1:1 ~ 5.
18. methods according to claim 17, is characterized in that, in described two step pickling process, the described weight ratio containing scandium material and water is 1:1 ~ 3.
19. methods according to any one of claim 1-4, is characterized in that, obtain containing scandium solution after filtration by the slip after leaching, and then carry out enrichment and refining to obtain highly purified Scium trioxide product.
20. methods according to claim 19, is characterized in that, described enrichment process comprises extraction, washing, back extraction process containing scandium solution, obtains thick scandium product.
21. methods according to claim 20, is characterized in that, in described extraction treatment, use P
204with TBP two kinds of extraction agents.
22. methods according to claim 20, is characterized in that, in described back extraction process, use NaOH solution as reverse-extraction agent.
23. methods according to claim 19, is characterized in that, described refinement treatment comprises the steps:
Make to obtain the dissolving of thick scandium product by described enrichment process by adding hydrochloric acid;
In filtrate, add oxalic acid obtain oxalic acid scandium throw out;
High temperature sintering, obtains Scium trioxide; And
Circulate above-mentioned technological process, obtains highly purified Scium trioxide product.
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