CN102649996A - Circular acid leaching extraction process for lepidolite - Google Patents
Circular acid leaching extraction process for lepidolite Download PDFInfo
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Abstract
The invention relates to a circular acid leaching extraction process for lepidolite, which comprises the following steps of: firstly, adding lepidolite mineral powder to acid leaching liquid to react; then, performing filtering separation on reaction liquid to obtain preliminarily-leached filter residues and preliminarily-leached filtrate, cooling to crystallize the preliminarily-leached filtrate, and performing the filtering separation to obtain preliminarily-leached crystals and preliminarily-leached crystal spent acid liquid; adding the preliminarily-leached filter residues to the acid leaching liquid, and then, adding a fluosilicic acid solution to react; performing the filtering separation on the reaction liquid to obtain re-leached filter residues and re-leached filtrate; cooling to crystallize the re-leached filtrate, and performing the filtering separation to obtain re-leached crystals and re-leached crystal spent acid liquid; washing the re-leached filter residues, and drying to obtain silicon dioxide of which the purity exceeds 98 percent; mixing the preliminarily-leached crystals with the re-leached crystals, dissolving by water, performing recrystallization and filtering to remove mixed alum to obtain recrystallization mother liquid; and adding sodium hydroxide to the recrystallization mother liquid to regulate the pH value to be 7-10 so as to precipitate aluminum, filtering to remove aluminum hydroxide, adding sodium carbonate to the filtrate, and filtering to obtain lithium carbonate.
Description
Technical field
The present invention relates to the decomposition method of lithionite; Relate in particular to a kind of from lithionite high efficiency extraction lithium, potassium, aluminium, fluorine, rubidium, cesium element; Obtain the method for the WHITE CARBON BLACK of high added value simultaneously; Specifically be applicable to the extraction yield that improves lithium, potassium, aluminium, fluorine, rubidium, cesium element in the lithionite, thereby improve acidleach filter residue purity, obtain the WHITE CARBON BLACK of high added value.
Background technology
A large amount of lithionite Mineral resources are contained the Yichuan in China.Lithionite is the mine tailing of tantalum niobium exploitation, Li in the lithionite
2O content is up to 4.5%, K
2O content is up to 8.6%, and contains elements such as aluminium, fluorine and expensive rubidium, caesium." 21 century is the century of lithium ", along with the application of lithium in high energy green energy resource field, its demand heightens, and price is surging.And rubidium and caesium are because its unique photoelectric characteristic and reactive behavior have irreplaceable application in technical fields such as photoelectricity and catalysis.China's general potassium deficiency of ploughing simultaneously, the demand of potash fertilizer is very big, and the water-soluble potassium salt ore resources of China seldom, far can not satisfy the demands, thereby comprehensive development and utilization lithionite resource how, has important economy and strategic importance.
Contain in the lithionite and surpass 50% SiO
2, the octahedron in its crystalline structure is full of by Li, Al plasma.This structure is difficult to destroy, thereby valuable components wherein is difficult to fully extract.Extraction process for lithionite mainly contains high-temperature roasting method, high temperature pressing immersion method at present.These method conditions are harsh, have the energy consumption height, defectives such as by product is many, equipment requirements is high, the recrement utilization ratio is low, cost height.
The patented claim of one Chinese patent application numbers 201010235150.2 discloses a kind of lithionite fluorine chemistry extraction process, and this application adopts an acidleach, because after the stripping of most soluble thing; System ionic concentration is higher, has reduced ion-exchanging efficiency, has hindered the leaching of residue soluble material in the breeze; Therefore leaching rate is lower, causes the waste of valuable constituent, obtains a large amount of filter residues simultaneously at last because its purity is not high; Can't commercialization, pile up and cause waste and pollute.In addition,, adopt to regulate the method for pH then and remove impurity such as aluminium owing to only adopt an acidleach in this patent, therefore need to use a large amount of alkali come in and unnecessary sulfuric acid in the system.And in order to reduce the usage quantity of alkali; Must reduce the vitriolic usage quantity during acidleach; To cause acid-leaching reaction later stage sulfuric acid concentration not high enough, influence the acidleach effect, also be unfavorable for that the fluorine in the system is discharged with the form of gas simultaneously; Therefore the latter stage in acidleach has adopted the method for HTHP (150-350 degree) to arrange fluorine in this application, to equipment requirements than higher.
Summary of the invention
The objective of the invention is to overcome the energy consumption that exists in the prior art high, add that material is many, by product is many, comprehensive utilization ratio is lower, complex operation step, equipment requirements height, production cost is higher, extraction effect is relatively poor defective and problem; What provide that a kind of cyclic utilization rate is higher, operation steps is simple and easy, extraction effect is better, production cost is lower extracts elements such as lithium, potassium, aluminium, rubidium, caesium, fluorine from lithionite, obtain the lithionite recycle acid lixiviate access method of purer WHITE CARBON BLACK.
For realizing above purpose, technical solution of the present invention is:
A kind of lithionite recycle acid lixiviate taking technique may further comprise the steps:
First soaking technology: is that 150 –, 300 purpose lithionite breezes are added in the pickling liquor with granularity earlier, the mass ratio of lithionite breeze and pickling liquor is 1:3 – 5, stirring reaction 2 – 4 hours under normal pressure then, and temperature of reaction is 120 ℃ of 100 ℃ –; Then reacting liquid filtering is separated obtaining just leaching slag and first lixivium, to first lixivium carry out crystallisation by cooling successively, filtering separation obtains just soaking crystallization and just soaking crystallization spent acid liquid.
Multiple soaking technology: earlier above-mentioned leaching slag just is added in the pickling liquor; Just the mass ratio of leaching slag and pickling liquor is 1:2 – 5; The silicate fluoride solution that adds mass percent concentration then and be 10%-40% is as the acidleach auxiliary agent; Make that fluorine content is the 1%-6% of lithionite powdered ore quality in the system, under normal pressure, stirred 1 – 4 hours then, temperature of reaction is 120 ℃ of 100 ℃ –; Again reacting liquid filtering is separated obtaining multiple leaching slag and multiple lixivium, then multiple lixivium is carried out crystallisation by cooling, filtering separation successively and soaked crystallization again and soak crystallization spent acid liquid again.
Acidleach aftertreatment technology: earlier above-mentioned multiple leaching slag is carried out water washing, carry out drying then and obtain purity and surpass 98% silicon-dioxide; Can be directly as the WHITE CARBON BLACK product.Accomplish extraction this moment to element silicon in the lithionite.Just soak crystallization and soak crystallized mixed again what obtain in first soaking technology, the multiple soaking technology, use water dissolution then, the water of adding is 1:1.5-2.5 with just soaking crystallization with the mass ratio that soaks the crystallization total amount again, carries out recrystallization again, removes by filter the mixing alum and obtains recrystallization mother liquor.Under agitation in recrystallization mother liquor, add then sodium hydroxide regulate its pH value to 7 – 10 with precipitation of aluminium, remove by filter white lake then, then in filtrating, add yellow soda ash, filter and promptly obtain Quilonum Retard.Accomplish extraction this moment to elemental lithium in the lithionite.
First the soaking and the crystallization of multiple lixivium of filtering in the said acidleach aftertreatment technology that filtrating being used for produce after the Quilonum Retard dissolve the next round acidleach is to reclaim lithium in small amounts, potassium, rubidium, the caesium in the filtrating; When sodium sulfate concentration is too high in this filtrating, can carry out condensing crystal and remove sodium sulfate, and then the recovery mother liquor is used for dissolving the acidleach crystallization.
The difference of above-mentioned mixing alum each components dissolved degree capable of using is carried out the precision work of potassium, rubidium, caesium, aluminium with the method for fractional crystallization.
Said pickling liquor is by just soaking crystallization spent acid liquid, soak in sulfuric acid that crystallization spent acid liquid, mass percent concentration are 90% – 98% and the acidleach aftertreatment technology and multiple leaching slag to be carried out the first washing lotion allotment that water washing obtains form again, and each amounts of components is so that H in the pickling liquor
2SO
4Mass percent concentration be 30% – 60%.
The fluoro-gas that in first soaking technology, generates in lithionite breeze and pickling liquor reaction process is derived and the water absorption; Gas to producing in the multiple soaking technology reaction process carries out condensing reflux, and reaction stops condensing reflux after finishing, and takes low pressure to extract the fluoro-gas that produces in the reaction out, and water absorbs, with the fluorine in the system of removing; Low pressure was separated reacting liquid filtering after bleeding 0.5-2 hour again.
The fluoro-gas water of deriving in said soaking technology just and the multiple soaking technology absorbs, and carries out filter operation then, obtains silica gel and silicate fluoride solution.Silica gel can be processed and obtain high-purity WHITE CARBON BLACK.Silicate fluoride solution can be directly as product, and the part silicofluoric acid is used for soaking again the acidleach auxiliary agent of reaction.
Saidly just soak crystallization spent acid liquid and soak crystallization spent acid liquid again and reclaim and get into next round acidleach circulation.
The follow-up washing lotion of said water washing operation is used for carrying out the water washing operation of lower whorl acidleach aftertreatment technology.
Compared with prior art, beneficial effect of the present invention is:
1, owing in two steps lithionite is carried out acidleach among the present invention, promptly earlier the lithionite breeze is carried out just soaking reaction, the composition that major part is prone to leach leaches, and through removing by filter the composition of stripping, then first leaching slag is soaked reaction again; Soak again add simultaneously in the reaction silicofluoric acid with utilize fluorine further with slag in pasc reaction, destroy the crystalline structure of its composition, promote the stripping of other composition of its coating.Owing to just soak the back through having removed by filter the composition of most of stripping; Reduced and soaked the ionic concn in the reaction again; Thereby improved and soaked the ion-exchanging efficiency in the reaction again, reaching the effect that improves leaching rate, twice acidleach can make more than the extraction rate reached to 99% of elements such as lithium, potassium, aluminium; The purity of silicon-dioxide reaches more than 98% in the filter residue simultaneously, obtains the higher WHITE CARBON BLACK of added value.
2, in the reaction process fluoro-gas that produces is derived and water absorbs just soaking, filter then and obtain silicofluoric acid and high-purity WHITE CARBON BLACK.Above-mentioned steps reaches the purpose of extracting fluorine in the breeze on the one hand, and the silicofluoric acid of gained can be used as the acidleach auxiliary agent that soaks again in the reaction on the other hand, and unnecessary silicofluoric acid can be directly as product.Add silicofluoric acid as the acidleach auxiliary agent soaking again in the reaction process, the leaching of the solvable composition that further promotes to be coated by silicon structure, adopt simultaneously the method for condensing reflux make fluorine in reaction system constantly circulation work, improved the utilization ratio of material.And after soaking the reaction end again, stopping condensing reflux, the fluoro-gas of generation also imported in the water during low pressure was extracted out and reacted then, so that the fluorine in the system is driven out of and reclaimed.More than operation had both improved leaching efficiency, made fluorine obtain good recycle again, had improved leaching rate, had reduced cost.
3, because twice acidleach of the present invention all added excessive sulfuric acid; Can improve leaching rate on the one hand; Also be beneficial to of the form discharge of the bleed stage of fluorine element after just soaking the stage and soaking reaction again on the other hand with fluoro-gas; Improved the yield of fluorine, avoided fluorine to get among the subsequent step simultaneously, made troubles for follow-up separation.Acidleach filtrating to twice is carried out Crystallization Separation, reclaims acidleach residual acid liquid, and is used to prepare the pickling liquor of next round circulation acidleach; This mode that reclaims residual sulfuric acid through Crystallization Separation has carried out recycling fully to sulfuric acid, and not waste also not be used in and adds a large amount of soda-lime in the follow-up process or calcium hydroxide waits the excessive sulfuric acid that neutralizes; Reduced the use of raw material; Reduce production of by-products simultaneously, simplified operating procedure greatly, reduced production cost.
4, reach more than 98% through its dioxide-containing silica of the filter residue after twice acidleach; And because a large amount of solvable compositions leach from the lithionite raw ore; Therefore the silicon-dioxide of acidleach gained has the porous short texture; Can also be beneficial to further precision work and produce the higher WHITE CARBON BLACK product of added value directly as the WHITE CARBON BLACK product.Therefore not only extraction effect is better in the present invention, and because the silicon-dioxide in the lithionite also obtains utilization, so comprehensive utilization degree is high, has eliminated the pollution of waste residue, has improved economic benefit.
The present invention carries out just soaking reaction to the lithionite breeze earlier, and the composition that major part is prone to leach leaches, and through removing by filter the composition of stripping, then first leaching slag is soaked reaction again; Owing to soaking again in the reaction; Ionic concn is lower; Improved the efficient of IX, helped remaining the leaching of a small amount of soluble material, simultaneously soak again add in the reaction silicofluoric acid with utilize fluorine further with slag in pasc reaction; Destroy the crystalline structure of its composition, promote the stripping of other composition of its coating.Therefore the present invention is through twice acidleach; Has different purpose separately; Just soaking is in order to leach almost soluble material, and these species distribution leach than being easier in the surface portion of breeze; Through the crystalline method composition that leaches is separated with pickling liquor simultaneously, and then soak reaction again.The purpose of soaking again is further to extract the difficult part solvend that leaches; Ionic concn in pickling liquor this moment is lower, therefore helps the leaching of the difficult material that leaches, and adds fluorine-containing auxiliary agent simultaneously; Further destroy the crystalline structure that silicon is formed in the breeze, reach the effect that improves leaching rate.Twice acidleach can make more than the extraction rate reached to 99% of elements such as lithium, potassium, aluminium, and the purity of silicon-dioxide reaches more than 98% in the filter residue simultaneously, obtains the higher WHITE CARBON BLACK of added value.Advantage of the present invention is to have fully utilized each composition in the breeze, has utilized particularly that content reaches 50% silica flour in the breeze, obtains added value than higher WHITE CARBON BLACK, has reduced scoriaceous accumulation and pollution.
Therefore the present invention helps improving the acidleach effect owing to be just to soak or soak again reaction to add excessive sulfuric acid all the time, in the presence of excess sulfuric acid, helps fluorine form with gas under lower temperature and discharges simultaneously.And, make that excessive sulfuric acid obtains reclaiming and recycling because the present invention has adopted crystallization excessive separation sulfuric acid and acidleach crystalline method.Therefore not only comprehensive utilization degree is high in the present invention, and the recycle degree is high, and cost is low, and is low for equipment requirements.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
Below in conjunction with description of drawings and embodiment the present invention is done further detailed explanation.
Referring to Fig. 1, a kind of lithionite recycle acid lixiviate taking technique, this technology in turn includes the following steps:
First soaking technology: be that 150 –, 300 purpose lithionite breezes (the lithionite composition is seen table 1) under agitation are added in the pickling liquor with granularity earlier, the mass ratio of lithionite breeze and pickling liquor is 1:3 – 5, and pickling liquor contains the sulfuric acid of 30%-60%.Stirring reaction 2 – 4 hours are to carry out just soaking reaction under normal pressure then, and temperature of reaction is 120 ℃ of 100 ℃ –, in the reaction process fluoro-gas that generates derived and water absorbs.After reaction finishes, again reacting liquid filtering is separated to obtain just leaching slag and first lixivium, then to first lixivium carry out crystallisation by cooling successively, filtering separation is operated to obtain crystallization and crystallization spent acid liquid.
Multiple soaking technology: earlier above-mentioned leaching slag just is added in the pickling liquor, the mass ratio of first leaching slag and pickling liquor is 1:2 – 5, and pickling liquor contains the sulfuric acid that mass percent concentration is 30%-60%.The silicate fluoride solution that adds mass percent concentration then and be 10%-40% is as the acidleach auxiliary agent, makes that fluorine content is the 1%-6% of powdered ore quality in the system, under normal pressure, stirs 1 – 4 hours then to soak reaction again, and temperature of reaction is 120 ℃ of 100 ℃ –.The gas that produces in the process carries out condensing reflux.After reacting end, stop condensing reflux, take low pressure to extract the gas that produces in the reaction out, and the water absorption, with the fluorine in the system of removing.After low pressure was bled 0.5-2 hour, again reacting liquid filtering is separated to obtain multiple leaching slag and multiple lixivium, then to lixivium carries out crystallisation by cooling successively again, filtering separation is operated to obtain crystallization and crystallization spent acid liquid.
The acidleach aftertreatment technology: earlier above-mentioned multiple leaching slag is carried out the water washing operation, carry out drying operation then and obtain purity and surpass 98% silicon-dioxide, can be directly as the WHITE CARBON BLACK product.Accomplish extraction this moment to element silicon in the lithionite.With the crystallized mixed that obtains in first soaking technology, the multiple soaking technology; Use water dissolution then; The water and the crystalline mass ratio that add are 1:1.5-2.5; Carry out recrystallization again, filter, obtain containing the recrystallization mother liquor of lithium, aluminium and little potassium, rubidium, caesium to remove the mixing alum that major part contains potassium, rubidium, caesium, aluminium.Under agitation in recrystallization mother liquor, add then sodium hydroxide regulate the pH value to 7 – 10 with precipitation of aluminium; Filter the solution that obtains white lake and sulfur acid lithium, sodium sulfate, a small amount of vitriolate of tartar, rubidiurn sulfate and cesium sulfate then; In this mixing solutions, add yellow soda ash then, filter and promptly obtain Quilonum Retard and filtrating.Accomplish extraction this moment to elemental lithium in the lithionite.Last filtrating is used for the crystallization of dissolving acid lixivium, to reclaim lithium in small amounts, potassium, rubidium, caesium wherein.When sodium sulfate concentration is too high in this filtrating, can carry out condensing crystal and remove sodium sulfate, and then reclaim mother liquor and be used for the crystallization of dissolving acid lixivium.The difference of above-mentioned mixing alum each components dissolved degree capable of using is carried out the precision work of potassium, rubidium, caesium, aluminium with the method for fractional crystallization.
Said pickling liquor is that mass percent concentration is the sulfuric acid of 30% – 60%.
Said pickling liquor is that the sulfuric acid of 90% – 98% and the first washing lotion allotment of water washing operation form by crystallization spent acid liquid and mass percent concentration.
The follow-up washing lotion of said water washing operation is used for carrying out the water washing operation of lower whorl acidleach aftertreatment technology.
In the said soaking technology just and the multiple soaking technology fluoro-gas water of deriving in the follow-up stage of bleeding absorb, carry out filter operation then, obtain silica gel and silicate fluoride solution.Silica gel can obtain high-purity WHITE CARBON BLACK through washing, drying, grinding processing.Silicate fluoride solution can be directly as product, and the part silicofluoric acid is used for soaking again the acidleach auxiliary agent of reaction.
Embodiment 1:
First soaking technology: be that 150 purpose lithionite breezes under agitation are added in the pickling liquor with granularity earlier, the mass ratio of lithionite breeze and pickling liquor is 1:5.Pickling liquor contains 30% sulfuric acid of (mass percent concentration, down with) is that the first washing lotion of 98% sulfuric acid and multiple leaching pulp water washing operation is allocated and formed by the crystallization spent acid liquid and the mass percent concentration of last round of acidleach.Stirring reaction 4 hours is to carry out just soaking reaction under normal pressure then, and temperature of reaction is 120 ℃, in the reaction process fluoro-gas that generates is derived and water absorbs.After reaction finishes, again reacting liquid filtering is separated to obtain just leaching slag and first lixivium, then to first lixivium carry out crystallisation by cooling successively, filtering separation is operated to obtain crystallization and crystallization spent acid liquid.
Multiple soaking technology: earlier above-mentioned leaching slag just is added in the pickling liquor, the mass ratio of first leaching slag and pickling liquor is 1:5.Pickling liquor contains 30% sulfuric acid, is that 98% the sulfuric acid and the first washing lotion allotment of multiple leaching pulp water washing operation form by the crystallization spent acid liquid of last round of acidleach and mass percent concentration.Add acidleach auxiliary agent silicate fluoride solution then, make that fluorine content is 6% of powdered ore quality in the system, under normal pressure, stir 4 hours then to soak reaction again, temperature of reaction is 120 ℃.The gas that produces in the process carries out condensing reflux.After the reaction end, stop condensing reflux, adopt low pressure to extract the gas that produces in the reaction out, and the water absorption, with the fluorine in the system of removing.After low pressure was bled 2 hours, again reacting liquid filtering is separated to obtain multiple leaching slag and multiple lixivium, then to lixivium carries out crystallisation by cooling successively again, filtering separation is operated to obtain crystallization and crystallization spent acid liquid.
Acidleach aftertreatment technology: earlier above-mentioned multiple leaching slag is carried out the water washing operation; Carrying out drying operation then is 98.3% silicon dioxide powder (detection method is with reference to GB YS/T 509.3-2008) to obtain purity, and the leaching rate of valuable constituent is 99.1% in the lithionite breeze.This silicon dioxide powder can be directly as the WHITE CARBON BLACK product.Accomplish extraction this moment to element silicon in the lithionite.With the crystallized mixed that obtains in first soaking technology, the multiple soaking technology; Use hot water (30-100 ℃) dissolving then; Adding entry and crystalline mass ratio is 1:2, cools off recrystallization again, filters to remove the mixing alum that major part contains potassium, rubidium, caesium, aluminium; Obtain containing the recrystallization mother liquor of lithium, aluminium and little potassium, rubidium, caesium, wherein Li
+Concentration is 29.8g/L (annotate: other constituent concentrations are saturation concentration).Under agitation in recrystallization mother liquor, add sodium hydroxide then and regulate its pH value to 7 to precipitate remaining aluminium; Filtration obtains the solution of white lake and sulfur acid lithium, sodium sulfate, a small amount of vitriolate of tartar, rubidiurn sulfate and cesium sulfate; In this mixing solutions, add concentration then and be 20% sodium carbonate solution, make Li
2SO
4With Na
2CO
3Mol ratio be 1:1, filter and promptly to obtain Quilonum Retard and filtrating.Accomplish extraction this moment to elemental lithium in the lithionite.Last filtrating is used for the crystallization (crystallization that promptly replaces in the step circulation step down aforementioned water dissolution just to obtain in soaking technology, the multiple soaking technology) of dissolving acid lixivium, to reclaim lithium in small amounts, potassium, rubidium, caesium wherein.Can carry out condensing crystal when sodium sulfate concentration in this filtrating too high (greater than 15%) and remove sodium sulfate, and then reclaim mother liquor and be used for dissolving the acidleach crystallization.The difference of above-mentioned mixing alum each components dissolved degree capable of using is carried out the precision work of potassium, rubidium, caesium, aluminium with the method for fractional crystallization.
In the said soaking technology just and the multiple soaking technology fluoro-gas water of deriving in the follow-up stage of bleeding absorb, carry out filter operation then, obtain silica gel and silicate fluoride solution.Silica gel can be processed and obtain high-purity WHITE CARBON BLACK.Silicate fluoride solution can be directly as product, and the part silicofluoric acid is used for soaking again the acidleach auxiliary agent of reaction.
Embodiment 2:
First soaking technology: be that 200 purpose lithionite breezes under agitation are added in the pickling liquor with granularity earlier, the mass ratio of lithionite breeze and pickling liquor is 1:4.Pickling liquor contains 40% sulfuric acid, is that 98% the sulfuric acid and the first washing lotion allotment of multiple leaching pulp water washing operation form by the crystallization spent acid liquid of last round of acidleach and mass percent concentration.Stirring reaction 3 hours is to carry out just soaking reaction under normal pressure then, and temperature of reaction is 110 ℃, in the reaction process fluoro-gas that generates is derived and water absorbs.After reaction finishes, again reacting liquid filtering is separated to obtain just leaching slag and first lixivium, then to first lixivium carry out crystallisation by cooling successively, filtering separation is operated to obtain crystallization and crystallization spent acid liquid.
Multiple soaking technology: earlier above-mentioned leaching slag just is added in the pickling liquor, the mass ratio of first leaching slag and pickling liquor is 1:4.Pickling liquor contains 40% sulfuric acid, is that 98% the sulfuric acid and the first washing lotion allotment of multiple leaching pulp water washing operation form by the crystallization spent acid liquid of last round of acidleach and mass percent concentration.Add acidleach auxiliary agent silicate fluoride solution then, make that fluorine content is 4% of powdered ore quality in the system, under normal pressure, stir 3 hours then to soak reaction again, temperature of reaction is 110 ℃.The gas that produces in the process carries out condensing reflux.After the reaction end, stop condensing reflux, adopt low pressure to extract the gas that produces in the reaction out, and the water absorption, with the fluorine in the system of removing.After low pressure was bled 1.5 hours, again reacting liquid filtering is separated to obtain multiple leaching slag and multiple lixivium, then to lixivium carries out crystallisation by cooling successively again, filtering separation is operated to obtain crystallization and crystallization spent acid liquid.
Acidleach aftertreatment technology: earlier above-mentioned multiple leaching slag is carried out the water washing operation; Carrying out drying operation then is 98.8% silicon dioxide powder (detection method is with reference to GB YS/T 509.3-2008) to obtain purity, and the leaching rate of valuable constituent is 99.4% in the lithionite breeze.This silicon dioxide powder can be directly as the WHITE CARBON BLACK product.Accomplish extraction this moment to element silicon in the lithionite.With the crystallized mixed that obtains in first soaking technology, the multiple soaking technology; Use hot water (30-100 ℃) dissolving then; Adding entry and crystalline mass ratio is 1:1.5, cools off recrystallization again, filters to remove the mixing alum that major part contains potassium, rubidium, caesium, aluminium; Obtain containing the recrystallization mother liquor of lithium, aluminium and little potassium, rubidium, caesium, wherein Li
+Concentration is 23.6g/L (annotate: other constituent concentrations are saturation concentration).Under agitation in recrystallization mother liquor, add sodium hydroxide then and regulate its pH value to 7 to precipitate remaining aluminium; Filter the solution that obtains white lake and sulfur acid lithium, sodium sulfate, a small amount of vitriolate of tartar, rubidiurn sulfate and cesium sulfate then; In this mixing solutions, add concentration then and be 20% sodium carbonate solution, make Li
2SO
4With Na
2CO
3Mol ratio be 1:1, filter and promptly to obtain Quilonum Retard and filtrating.Accomplish extraction this moment to elemental lithium in the lithionite.Last filtrating is used for the crystallization of dissolving acid lixivium, to reclaim a spot of lithium, potassium, rubidium, caesium wherein.Can carry out condensing crystal when sodium sulfate concentration in this filtrating too high (greater than 15%) and remove sodium sulfate, and then reclaim mother liquor and be used for dissolving the acidleach crystallization.The difference of above-mentioned mixing alum each components dissolved degree capable of using is carried out the precision work of potassium, rubidium, caesium, aluminium with the method for fractional crystallization.
In the said soaking technology just and the multiple soaking technology fluoro-gas water of deriving in the follow-up stage of bleeding absorb, carry out filter operation then, obtain silica gel and silicate fluoride solution.Silica gel can be processed and obtain high-purity WHITE CARBON BLACK.Silicate fluoride solution can be directly as product, and the part silicofluoric acid is used for soaking again the acidleach auxiliary agent of reaction.
Embodiment 3:
First soaking technology: be that 250 purpose lithionite breezes under agitation are added in the pickling liquor with granularity earlier, the mass ratio of lithionite breeze and pickling liquor is 1:3.Pickling liquor contains 35% sulfuric acid, is that 98% the sulfuric acid and the first washing lotion allotment of multiple leaching pulp water washing operation form by the crystallization spent acid liquid of last round of acidleach and mass percent concentration.Stirring reaction 2 hours is to carry out just soaking reaction under normal pressure then, and temperature of reaction is 100 ℃, in the reaction process fluoro-gas that generates is derived and water absorbs.After reaction finishes, again reacting liquid filtering is separated to obtain just leaching slag and first lixivium, then to first lixivium carry out crystallisation by cooling successively, filtering separation is operated to obtain crystallization and crystallization spent acid liquid.
Multiple soaking technology: earlier above-mentioned leaching slag just is added in the pickling liquor, the mass ratio of first leaching slag and pickling liquor is 1:3.Pickling liquor contains 35% sulfuric acid, is that 98% the sulfuric acid and the first washing lotion allotment of multiple leaching pulp water washing operation form by the crystallization spent acid liquid of last round of acidleach and mass percent concentration.Add acidleach auxiliary agent silicate fluoride solution then, make that fluorine content is 3% of powdered ore quality in the system, under normal pressure, stir 2 hours then to soak reaction again, temperature of reaction is 100 ℃.The gas that produces in the process carries out condensing reflux.After the reaction end, stop condensing reflux, adopt low pressure to extract the gas that produces in the reaction out, and the water absorption, with the fluorine in the system of removing.After low pressure was bled 1 hour, again reacting liquid filtering is separated to obtain multiple leaching slag and multiple lixivium, then to lixivium carries out crystallisation by cooling successively again, filtering separation is operated to obtain crystallization and crystallization spent acid liquid.
Acidleach aftertreatment technology: earlier above-mentioned multiple leaching slag is carried out the water washing operation; Carrying out drying operation then is 98.9% silicon dioxide powder (detection method is with reference to GB YS/T 509.3-2008) to obtain purity, and the leaching rate of valuable constituent is 99.4% in the lithionite breeze.This silicon dioxide powder can be directly as the WHITE CARBON BLACK product.Accomplish extraction this moment to element silicon in the lithionite.With the crystallized mixed that obtains in first soaking technology, the multiple soaking technology; Use hot water (30-100 ℃) dissolving then; Adding entry and crystalline mass ratio is 1:1.8, cools off recrystallization again, filters to remove the mixing alum that major part contains potassium, rubidium, caesium, aluminium; Obtain containing the recrystallization mother liquor of lithium, aluminium and little potassium, rubidium, caesium, wherein Li
+Concentration is 27.6g/L (annotate: other constituent concentrations are saturation concentration).Under agitation in recrystallization mother liquor, add sodium hydroxide then and regulate its pH value to 7 to precipitate remaining aluminium; Filter the solution that obtains white lake and sulfur acid lithium, sodium sulfate, a small amount of vitriolate of tartar, rubidiurn sulfate and cesium sulfate then; In this mixing solutions, add concentration then and be 20% sodium carbonate solution, make Li
2SO
4With Na
2CO
3Mol ratio be 1:1, filter and promptly to obtain Quilonum Retard and filtrating.Accomplish extraction this moment to elemental lithium in the lithionite.Last filtrating is used for the crystallization of dissolving acid lixivium, to reclaim lithium in small amounts, potassium, rubidium, caesium wherein.Can carry out condensing crystal when sodium sulfate concentration in this filtrating too high (greater than 15%) and remove sodium sulfate, and then reclaim mother liquor and be used for dissolving the acidleach crystallization.The difference of above-mentioned mixing alum each components dissolved degree capable of using is carried out the precision work of potassium, rubidium, caesium, aluminium with the method for fractional crystallization.
In the said soaking technology just and the multiple soaking technology fluoro-gas water of deriving in the follow-up stage of bleeding absorb, carry out filter operation then, obtain silica gel and silicate fluoride solution.Silica gel can be processed and obtain high-purity WHITE CARBON BLACK.Silicate fluoride solution can be directly as product, and the part silicofluoric acid is used for soaking again the acidleach auxiliary agent of reaction.
Embodiment 4:
First soaking technology: be that 200 purpose lithionite breezes under agitation are added in the pickling liquor with granularity earlier, the mass ratio of lithionite breeze and pickling liquor is 1:4.Pickling liquor contains 30% sulfuric acid, is that 98% the sulfuric acid and the first washing lotion allotment of multiple leaching pulp water washing operation form by the crystallization spent acid liquid of last round of acidleach and mass percent concentration.Stirring reaction 3 hours is to carry out just soaking reaction under normal pressure then, and temperature of reaction is 100 ℃, in the reaction process fluoro-gas that generates is derived and water absorbs.After reaction finishes, again reacting liquid filtering is separated to obtain just leaching slag and first lixivium, then to first lixivium carry out crystallisation by cooling successively, filtering separation is operated to obtain crystallization and crystallization spent acid liquid.
Multiple soaking technology: earlier above-mentioned leaching slag just is added in the pickling liquor, the mass ratio of first leaching slag and pickling liquor is 1:4.Pickling liquor contains 30% sulfuric acid, is that 98% the sulfuric acid and the first washing lotion allotment of multiple leaching pulp water washing operation form by the crystallization spent acid liquid of last round of acidleach and mass percent concentration.Add acidleach auxiliary agent silicate fluoride solution then, make that fluorine content is 4% of powdered ore quality in the system, under normal pressure, stir 3 hours then to soak reaction again, temperature of reaction is 100 ℃.The gas that produces in the process carries out condensing reflux.After the reaction end, stop condensing reflux, adopt low pressure to extract the gas that produces in the reaction out, and the water absorption, with the fluorine in the system of removing.After low pressure was bled 1.5 hours, again reacting liquid filtering is separated to obtain multiple leaching slag and multiple lixivium, then to lixivium carries out crystallisation by cooling successively again, filtering separation is operated to obtain crystallization and crystallization spent acid liquid.
Acidleach aftertreatment technology: earlier above-mentioned multiple leaching slag is carried out the water washing operation; Carrying out drying operation then is 98.5% silicon dioxide powder (detection method is with reference to GB YS/T 509.3-2008) to obtain purity, and the leaching rate of valuable constituent is 99.2% in the lithionite breeze.This silicon dioxide powder can be directly as the WHITE CARBON BLACK product.Accomplish extraction this moment to element silicon in the lithionite.With the crystallized mixed that obtains in first soaking technology, the multiple soaking technology; Use hot water (30-100 ℃) dissolving then; Adding entry and crystalline mass ratio is 1:2.3, cools off recrystallization again, filters to remove the mixing alum that major part contains potassium, rubidium, caesium, aluminium; Obtain containing the recrystallization mother liquor of lithium, aluminium and little potassium, rubidium, caesium, wherein Li
+Concentration is 33.4g/L (annotate: other constituent concentrations are saturation concentration).Under agitation in recrystallization mother liquor, add sodium hydroxide then and regulate its pH value to 7 to precipitate remaining aluminium; Filter the solution that obtains white lake and sulfur acid lithium, sodium sulfate, a small amount of vitriolate of tartar, rubidiurn sulfate and cesium sulfate then; In this mixing solutions, add concentration then and be 20% sodium carbonate solution, make Li
2SO
4With Na
2CO
3Mol ratio be 1:1, filter and promptly to obtain Quilonum Retard and filtrating.Accomplish extraction this moment to elemental lithium in the lithionite.Last filtrating is used for the crystallization of dissolving acid lixivium, to reclaim lithium in small amounts, potassium, rubidium, caesium wherein.Can carry out condensing crystal when sodium sulfate concentration in this filtrating too high (greater than 15%) and remove sodium sulfate, and then reclaim mother liquor and be used for dissolving the acidleach crystallization.The difference of above-mentioned mixing alum each components dissolved degree capable of using is carried out the precision work of potassium, rubidium, caesium, aluminium with the method for fractional crystallization.
In the said soaking technology just and the multiple soaking technology fluoro-gas water of deriving in the follow-up stage of bleeding absorb, carry out filter operation then, obtain silica gel and silicate fluoride solution.Silica gel can be processed and obtain high-purity WHITE CARBON BLACK.Silicate fluoride solution can be directly as product, and the part silicofluoric acid is used for soaking again the acidleach auxiliary agent of reaction.
Claims (8)
1. lithionite recycle acid lixiviate taking technique is characterized in that may further comprise the steps:
First soaking technology: is that 150 –, 300 purpose lithionite breezes are added in the pickling liquor with granularity earlier, the mass ratio of lithionite breeze and pickling liquor is 1:3 – 5, stirring reaction 2 – 4 hours under normal pressure then, and temperature of reaction is 120 ℃ of 100 ℃ –; Then reacting liquid filtering is separated obtaining just leaching slag and first lixivium, to first lixivium carry out crystallisation by cooling successively, filtering separation obtains just soaking crystallization and just soaking crystallization spent acid liquid;
Multiple soaking technology: earlier above-mentioned leaching slag just is added in the pickling liquor; Just the mass ratio of leaching slag and pickling liquor is 1:2 – 5; The silicate fluoride solution that adds mass percent concentration then and be 10%-40% is as the acidleach auxiliary agent; Make that fluorine content is the 1%-6% of lithionite powdered ore quality in the system, under normal pressure, stirred 1 – 4 hours then, temperature of reaction is 120 ℃ of 100 ℃ –; Again reacting liquid filtering is separated obtaining multiple leaching slag and multiple lixivium, then multiple lixivium is carried out crystallisation by cooling, filtering separation successively and soaked crystallization again and soak crystallization spent acid liquid again;
Acidleach aftertreatment technology: earlier above-mentioned multiple leaching slag is carried out water washing, carry out drying then and obtain purity and surpass 98% silicon-dioxide; Just soak crystallization and soak crystallized mixed again what obtain in first soaking technology, the multiple soaking technology, use water dissolution then, the water of adding is 1:1.5-2.5 with just soaking crystallization with the mass ratio that soaks the crystallization total amount again, carries out recrystallization again, removes by filter the mixing alum and obtains recrystallization mother liquor; Under agitation in recrystallization mother liquor, add then sodium hydroxide regulate its pH value to 7 – 10 with precipitation of aluminium, remove by filter white lake then and obtain mixing solutions, in this mixing solutions, add yellow soda ash then, filter and promptly obtain Quilonum Retard.
2. lithionite recycle acid lixiviate taking technique according to claim 1 is characterized in that: said pickling liquor is that mass percent concentration is the sulfuric acid of 30% – 60%.
3. lithionite recycle acid lixiviate taking technique according to claim 1; It is characterized in that: said pickling liquor is by just soaking crystallization spent acid liquid, soak in sulfuric acid that crystallization spent acid liquid, mass percent concentration are 90% – 98% and the acidleach aftertreatment technology and multiple leaching slag to be carried out the first washing lotion allotment that water washing obtains form again, and each amounts of components is so that H in the pickling liquor
2SO
4Mass percent concentration be 30% – 60%.
4. lithionite recycle acid lixiviate taking technique according to claim 1 is characterized in that: the fluoro-gas that in first soaking technology, generates in lithionite breeze and pickling liquor reaction process is derived and the water absorption; Gas to producing in the multiple soaking technology reaction process carries out condensing reflux, and reaction stops condensing reflux after finishing, and takes low pressure to extract the fluoro-gas that produces in the reaction out, and water absorbs, with the fluorine in the system of removing; Low pressure was separated reacting liquid filtering after bleeding 0.5-2 hour again.
5. lithionite recycle acid lixiviate taking technique according to claim 4 is characterized in that: the fluoro-gas water of deriving in said soaking technology just and the multiple soaking technology absorbs, and carries out filter operation then, obtains silica gel and silicate fluoride solution.
6. a kind of lithionite recycle acid lixiviate taking technique according to claim 1 is characterized in that: saidly just soak crystallization spent acid liquid and soak crystallization spent acid liquid again and reclaim and get into next round acidleach circulation.
7. a kind of lithionite recycle acid lixiviate taking technique according to claim 1; It is characterized in that: first the soaking and the crystallization of multiple lixivium of filtering in the said acidleach aftertreatment technology that filtrating being used for produce after the Quilonum Retard dissolve the next round acidleach, to reclaim lithium in small amounts, potassium, rubidium, the caesium in the filtrating; When sodium sulfate concentration is too high in this filtrating, can carry out condensing crystal and remove sodium sulfate, and then the recovery mother liquor is used for dissolving the acidleach crystallization.
8. a kind of lithionite recycle acid lixiviate taking technique according to claim 1, it is characterized in that: the mixing alum in the said acidleach aftertreatment technology carries out the precision work of potassium, rubidium, caesium, aluminium with the method for fractional crystallization through the difference of utilizing each components dissolved degree.
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