CN104003427B - A kind of preparation method with spodumene Concentrate sheet Lithium hydroxide - Google Patents
A kind of preparation method with spodumene Concentrate sheet Lithium hydroxide Download PDFInfo
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Abstract
The present invention relates to the preparation field of the High Purity compound in chemical technology field, be specially a kind of preparation method with spodumene Concentrate sheet Lithium hydroxide. The method is dissolved the thick product of the monohydrate lithium hydroxide obtaining, and makes Li2The mass concentration of O is: 65-70g/L, then carry out condensing crystallizing by organic solution, and finally liquid-solid separation is dried and obtained the high-purity monohydrate lithium hydroxide product of sheet. This preparation method can process dissimilar ore, and inspissation has been played in organic solvent hydration reaction, and lithium hydroxide is more easily separated out sooner, impurity can not crystallize out with lithium hydroxide, improved the purity of lithium hydroxide, purity is all more than 99.8%, and light transmittance reaches 99%. The distribution of particles crystallizing out is narrow and easy to control, constant product quality, and super GB electron level standard, crystallization is sheet, and organic solvent is convenient to repeatedly apply, and operation, has reduced energy consumption at normal temperatures.
Description
Technical field
The present invention relates to the preparation field of the High Purity compound in chemical technology field, be specially a kind of lithium brightness of usingThe preparation method of stone Concentrate sheet Lithium hydroxide.
Background technology
Monohydrate lithium hydroxide is white crystalline powder, can be water-soluble, be slightly soluble in the organic solvents such as alcohol. Can be from skyAbsorbing carbon dioxide in gas and going bad. Be strong basicity. can not burn, but have severe corrosive. Conventionally with a waterThe form of thing occurs. Purposes is comparatively extensive at present, in equal extensive uses in field such as chemical industry, national defence, electronics.The method of traditional manufacture order water lithium hydroxide is taking spodumene as raw material, makes the transition through high-temperature calcination, and sulfuric acidChange roasting, freezing separation sodium sulphate, evaporation, low temperature recrystallization method manufacture order water lithium hydroxide. Now generalThe commercial run adopting has long historical, domestic technique refinement has been applied for to several patents. Mark according to countryAccurate GB/T26008-2010, LITHIUM BATTERY LiOH.H2O purity is minimum is not less than 95%, adopts above-mentioned technique to reachTo national standard, but traditional technique ubiquity technological process is long, selective to raw material, comprehensively returnsYield is low, and yield is low, and not higher than 90%, water consumption is large, and particle is spherical, and in order to improve yield, water must notDo not have open circuit, pollute, equipment capacity is low, energy consumption is high, automaticity is not high, particularly producesProduct purity is not high, and light transmittance is low, and light transmittance is no more than 90%, and grain size number distributes undesirable, can not output sheetThe problems such as shape crystal.
Along with scientific and technical development and progress, the especially requirement of environmental protection, the competition in market, need to be to formerSome technique is optimized, simplifies, and improves equipment automatization level, reforming equipment, in order to meet national defence workMany high and new technologies fields such as industry, atomic energy industry, aerospace industry, electronics industry are to single water hydroxideThe requirement of lithium quality, the high-purity monohydrate lithium hydroxide of preparation sheet is very important, along with the consumption of resource,Also need to develop the technique that uses different material.
Summary of the invention
The present invention, just based on above technical problem, provides a kind of various different materials, utilization rate of equipment and installations of being applicable toHeight, automatic controlling level is high, low energy consumption, pollution-free and can produce sheet high-purity, good transmittance,Size distribution becomes the controlled preparation method with spodumene Concentrate sheet Lithium hydroxide.
Technical scheme of the present invention is:
By a preparation method for spodumene Concentrate sheet Lithium hydroxide, the method is: will obtainThe thick product with deionized water of monohydrate lithium hydroxide dissolve, make Li2The mass concentration of OFor 65-70g/L, then carry out condensing crystallizing by organic solution, finally by liquid-solid separation, filter and at 60 DEG CThe pure washing secondary of lower use obtains crystal, then makes crystal carry out vacuum drying under the condition of 70 DEG C-90 DEG C and obtainsTo ultra-pure monohydrate lithium hydroxide product, liquid after the filtration obtaining, separates with ionic membrane, obtainsOrganic solution return to re-using. Described organic solvent can be alcohols: as methyl alcohol, ethanol, propyl alcoholDeng, ketone: butanone, the tertiary butanone of formaldehyde etc., ethers: first, the tertiary fourth ethylether of aldehyde, the tertiary fourth ethylether of acetaldehydeDeng, also have petrochemicals, as some aromatic hydrocarbons, these organic matter general character are, lithium hydroxide insoluble orSlightly soluble, and water dissolves each other, and has certain affinity with water, together with water time, useful molecules sieve membrane carries out separation,The collaborative result of use of these organic compounds is better, and the wt% of the organic solvent of selecting is 30-45%, at normal temperatureUnder stir, organic solvent slowly adds, precipitation 30-50min after completing. Its general principle is due to hydrogenLithia is insoluble or be slightly soluble in these organic matters, can not cause the solution loss of lithium hydroxide in organic phase, thisA little organic matters and water have affinity, and the water of polar molecule will be by Adsorption of Organic, makes original lithium hydroxideIn solution, reach supersaturation and separate out, lithium hydroxide is purified, and being flaky crystal, after crystallizationFiltrate is carried out separating of organic phase and water with ionic membrane, and the water of organic phase absorption is filtered and returns to use.Have no report both at home and abroad.
By a preparation method for spodumene Concentrate sheet Lithium hydroxide, specifically comprise following stepRapid:
1) by levigate calcining transition of carrying out α Li-β Li to 160-180 object spodumene concentrate in rotary kiln,Calcining heat is 900-1200 DEG C. The spodumene concentrate using can come from different mines, and structure canDifferent. Before entering rotary kiln, particle diameter is that 160-180 object spodumene concentrate account for total spodumene concentrateMore than 80, the tail gas producing in rotary kiln, is first used for material to give heat, then by dividing plate gravitational settling, two-stageCyclone dust collection, bag collection, gas is up to standard rear emptying.
2) by step 1) obtain in sulfating roasting rotary kiln, carry out sulphation roasting containing the oxidate for lithium of β LiBurn, reinforced under hermetically sealed condition, return brickkiln and dust collecting system and adopt micro-negative pressure≤-10mmH2O column operation,Temperature is controlled at 480～～550 DEG C, automation mechanized operation.
3) by step 2) neutralization of sizing mixing in size-mixing tank of the acidifying ore deposit of the sulfur acid lithium that obtains, its pH value is arrived10-12, then carries out Pyatyi adverse current, and cross-flow is moved in slot type leaching pond and leached, and must contain through plate compressionLi2The lithium sulfate solution of O:45-55g/L.
4) by step 3) the lithium sulfate solution NaOH that obtains carries out neutralization reaction, OH-During for 60-70g/LBe cooled to-1 to-10 DEG C, carry out liquid-solid separation and obtain 10 aqueous sodium persulfates and lithium hydroxide solution;
5) by step 4) 10 aqueous sodium persulfates that obtain are broad, and evaporative crystallization dehydration, dries and obtains anhydrous sodium sulfate and produceProduct;
6) by step 4) obtain containing the lithium hydroxide solution of Li2O:45-55g/L, efficient at 100-120 DEG CEvaporimeter evaporates, and makes it to reach Li2O:110-150g/L; Total consolidates: liquid=1:3, leaching tanks operation speedDegree 0.01m/min, leachate is containing Li for the first time2O40-50g/L, Li in waste2O≤0.1％。
7) by step 6) the evaporation and concentration solution that obtains carries out crystallisation by cooling at the temperature of 40-60 DEG C, containedLi2The thick product of the monohydrate lithium hydroxide of O:52-54%.
8) by step 7) the thick product of monohydrate lithium hydroxide that obtains dissolves again, makes Li2The content of O reaches 65-70g/L,Carry out condensing crystallizing with organic solvent, Separation of Solid and Liquid, dries and obtains the high-purity monohydrate lithium hydroxide product of sheet.
9) by step 8) the crystalline mother solution ionic membrane that obtains separates, the organic solvent obtaining returns to step 8)Again recycle, inorganic mother liquor turns back to step 7).
Compared with prior art, beneficial effect of the present invention is:
(1), can process dissimilar ore.
(2), two all dustless discharges of rotary kiln, discharge without sulfide, accomplish cleaner production, closure is automatically rawProduce, improved efficiency, negative-pressure operation has reduced reaction temperature.
(3), cross-flow counterflow leaching, improved leaching rate, improved productivity ratio, make the diffusion in leaching processJourney is accelerated, and has reduced water consumption more than 40%, makes the Li of leachate2O content carried 23%, reduced liquidEvaporation capacity, has completed the closed cycle of 100% water, accomplishes that environmental protection produces, and has reduced energy consumption.
(4), organic solvent hydration reaction played inspissation, and lithium hydroxide is more easily separated out sooner, impurity is notCan crystallize out with lithium hydroxide, improve the purity of lithium hydroxide, purity all more than 99.8%, light transmittanceReach 99%. The distribution of particles crystallizing out is narrow and easy to control, constant product quality, and super GB electron level standard,Crystallization is sheet, and organic solvent is convenient to repeatedly apply, and operation, has reduced energy consumption at normal temperatures.
Brief description of the drawings
Fig. 1 is process chart of the present invention;
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is further described in detail, the embodiment providing alsoDo not limit the scope of the invention, the present invention expands to any new feature disclosing in this manual or any newCombination.
By about 160-180 order, content reaches gross mass more than 80% spodumene concentrate and reclaims at kiln hoodFlue dust mixes from the kiln hood of rotary kiln and adds, and kiln tail is by controlling mobile coal injection pipe, by pulverized coal injectionEnter in the rotary kiln of burning, control the effective high-temperature region of rotary kiln at 12-16m, depending on the different high temperature of controlling of ore structureThe temperature in district is 900-1200 DEG C of variation, and by the material calcining that makes the transition, the material after calcining rolls by circleCylinder carries out cooling, and the grinding machine of then scoring carries out ball milling.
After being milled to-200 orders, the roasting material of gained carries out nitration mixture, roasted ore and H2SO4Mass ratio be 1:0.3, compound enters in the rotary kiln of sulfating roasting and carries out sulfating roasting, obtains sulfating roasting material.Reinforced, roasting in calcination rotary kiln and gather dust and be closed automatic operation. Gathering dust in calcination rotary kilnSystem adopts-1 low vacuum to-10mm water column, and the furnace temperature of controlling roaster is 480-5500 DEG C, uses cylinderFormula cooling device is cooled to 60-80 DEG C.
The sulfating roasting material obtaining, sizes mixing with once leaching water, in and adjust pH reach 10-12,This ore pulp carries out counterflow leaching on belt cross-flow filtration machine, and gross mass liquid-solid ratio is 1.5-1.8:1, lastOne-level adds clear water, after leaching, in liquid phase, contains Li2O is 3-10g/L, counterflow leaching first order leachate Li2O：45-50g/L adds NaOH and is adjusted to, OH-: 60-70g/L, it is freezing that leachate carries out secondary refrigerated cylinder, temperature controlIn <-1 DEG C with <-10 DEG C, allow Na2SO4.10H2O crystallization, Na after Separation of Solid and Liquid2SO4.10H2O is heavy againMolten recrystallization, dries to obtain anhydrous sodium sulfate product.
The liquid that liquid-solid separation obtains carries out evaporative crystallization after by conventional purification, obtains monohydrate lithium hydroxideContent is the crude product of 93-94%, and mother liquor returns freezing.
By the crude product LiOH.H obtaining2O product is dissolved in pure deionized water, adds that to account for lithium hydroxide solution totalThe 30-45%'s of quality, the wherein mixture of 20% methyl alcohol, 20% butanone, requires slowly in stirring, to add,The parameter that adds of controlling organic solvent can obtain varigrained lithium hydroxide, dries to obtain the pure single water hydrogen-oxygen of sheetChange crystalline lithium.
Embodiment 1:
Domestic certain spodumene concentrate, Li in its concentrate2The shared quality percentage composition of O is 5.2%, by spodumeneConcentrate is levigate, the particle diameter more than-200 orders account for total content 80% time, and reclaim from kiln hood containing Li2O'sDirt mixes, and adds from kiln hood, and kiln tail sprays into combustion by controlling mobile coal injection pipe by-200 object coal dustsIn the rotary kiln burning, the temperature of controlling rotary kiln high-temperature region is 950 DEG C, and high-temperature region length is controlled at 12m,The high-temperature region time of staying is 22min, and kiln tail calcining material is out cooled to 40 DEG C, then enters ball mill and entersRow is milled to-200 orders and reaches 80% of gross mass content, whole-course automation control.
By the levigate ore containing β Li, to mix with smokeless sulfuric acid, the quality that adds of sulfuric acid is theoretical amount113%, at the temperature of 450 DEG C, carry out sulfating roasting, from the recovery of reinforced, discharging, roasting, dirtAll under airtight condition, carry out the H of the recovery system employing-5mm of roasting and dirt2The micro-negative pressure operation of O post,All automation control, calcination time 40min, calcining materials is cooled to 60 DEG C by circular drum.
By the sulphation material that contains lithium sulfate obtaining, carry out slurrying, the liquid of the use of sizing mixing is in counterflow leachingThe solution of the sulfur acid lithium of first level leaching, the content of lithium hydroxide is 1.4g/cm3, then add containing OH-Alkali compounds carry out neutralization reaction, controlling pH value is 12, then continues stirring 20min. The material obtainingOn portable slot type filter, carry out water logging through the cross-flow of Pyatyi adverse current, every one-level infusion all drench from top into,After adopting vacuum filtration by filter cake, enter into wet tank, and then squeeze into the water logging groove of upper level with pump,Total quality liquid-solid ratio is 1.5:1, Li in last leachate2The mass concentration of O is 45-50g/L, in filter residueLi2The mass concentration of O is 0.1%, can be used as clinker.
In the leachate obtaining, add NaoH, KOH, adjusts solution O H-Concentration reach 60-70g/L, adjustPH and OH-When concentration, play purification and impurity removal effect, be also conducive to lower step and remove sulfate radical. The solution obtaining carries outSecondary is cooling, and the first order is controlled at-2 DEG C, and the second level is controlled at-10 DEG C. Make Na2SO4.10H2O crystal is separated out,Crystal after separating out is through overweight molten, and recrystallization, produces anhydrous sodium sulfate byproduct. Remove the molten of sodium sulphateLiquid carries out evaporative crystallization, monohydrate lithium hydroxide content 93.5%, SO4 2-The monohydrate lithium hydroxide crude product of < 1%.
The crude product dissolving crystallized obtaining, in pure water, is controlled Li2The mass concentration of O is 68-75g/L,In the situation that stirring, the mixing organic matter of 20% methyl alcohol, 20% butanone is joined in LiOH solution to crystallizationAfter filtering, wash twice with pure water at 60 DEG C, vacuum drying obtains the high-purity monohydrate lithium hydroxide of sheet.
Liquid after crystallization separates with molecular screen membrane, and the yield of organic solvent is 95%, in organic solventWater content is 6% can return to use, and raffinate turns back to evaporimeter crystallization and produces thick Li2O.H2In O operation.
Embodiment 2:
Ore deposit, external Australia spodumene concentrate, wherein Li2The quality percentage composition of O is 6.13%, by spodumene essenceOre deposit is levigate reaches the more than 80% of total content to-180 orders, and from the Li of the kiln hood rate of recovery2The dirt of O mixes, by spiral shellRevolve batcher and add from kiln hood, kiln tail is by controlling mobile coal injection pipe, by levigate extremely-200 object pulverized coal injectionsEnter in the rotary kiln of burning, high-temperature region temperature is 1100 DEG C, and high-temperature region length is controlled at 13.5M, materialBe 25min in the high-temperature region time of staying, kiln tail calcining material is out cooled to 40 DEG C of <, then enters ballGrinding machine is milled to-200 orders and reaches 80% left and right of total content, the whole automation control of this process.
The levigate mineral containing β li, mix with smokeless sulfuric acid, and sulphuric acid is theoretical amount additionWt135%, after mixing, add and in sulfating roasting kiln, carry out sulfating roasting, controlling sintering temperature is 500 DEG C,Overall process is airtight, and automation control, the recovery system employing-5mmH of roasting and dirt2The micro-negative pressure operation of O post,Material is at kiln residence time 40min, and the material of having calcined is cooled to 60 DEG C in circular scrolling cylinder.
The material of the sulfating roasting obtaining is carried out to slurrying, and the liquid that slurrying is used is leachate for the first time, slurryDensity be 1.4g/cm3, then add containing OH-Alkali compounds carry out neutralization reaction, controlling pH value is 12,Continue again to stir 20min.
The material obtaining is carried out to the cross-flow of Pyatyi adverse current and on portable slot type filter, carries out water logging, filtration,While carrying out adverse current water logging, every one-level infusion all drench from top into, through filter cake, adopt vacuum filtration to enterWet tank, then squeezes in the water logging groove of upper level with pump, and the mass ratio of total liquid-solid ratio is controlled at 1.5:1,Be controlled at Li to leachate eventually2The mass concentration of O is 45-50g/L, Li in slag2The mass concentration of O is 0.1%,Can be used as clinker.
In the leachate obtaining, add NaOH.KOH, adjust the OH of solution-Concentration, makes OH-Concentration reach60-70g/L。
The solution obtaining is carried out to secondary cooling, the chilling temperature of cooling control is for the first time-2 DEG C, the second levelThe chilling temperature of controlling is-10 DEG C, makes NaSO4.10H2O separates out, and the crystal after separating out is molten by weighing, then tiesCrystalline substance, produces anhydrous sodium sulfate byproduct.
The solution of removing sodium sulphate is carried out to evaporative crystallization, monohydrate lithium hydroxide content 93,7%, SO4 2-<'s 1%Monohydrate lithium hydroxide crude product.
The crude product dissolving crystallized obtaining, in pure water, is controlled to Li2The mass concentration of O is 68-75g/L,Obtain with example 1 recovery, the mass concentration of methyl alcohol and butanone reaches respectively more than 94% organic solvent, is stirringIn the situation of mixing, organic solvent is joined in LiOH solution, filter at 60 DEG C with pure washing secondary, veryEmpty oven dry obtains the high-purity monohydrate lithium hydroxide of sheet.
Liquid after crystallization separates with molecular screen membrane, and the yield of organic solvent is 95%, in organic solvent, containsThe water yield is 6%, can return to use, and remaining liquid turns back to evaporative crystallization and produces thick LiOH.H2In O operation.
Also select methyl alcohol, ethanol, propyl alcohol, butanone, the tertiary butanone of formaldehyde, the tertiary fourth of formaldehyde base ether, acetaldehyde uncleEight organic matters such as the ethylbenzene of fourth ethylether, aromatic hydrocarbons, have carried out above-mentioned eight kinds of a kind of organic matters wherein, matterThe totally 24 groups of tests of amount concentration 30%, 40%, 45%, alcohols one adds ketone one, and alcohols one adds ethers oneKind, alcohols one adds aromatic hydrocarbons one, and organic mass concentration is 45%, and alcohols adds ketone and adds ethers eachThe mixture of planting, organic concentration is 45%, test of many times has all obtained higher than GB/T26008-2010The experimental result of the standard of battery-stage monohydrate lithium hydroxide.
Claims (5)
1. by a preparation method for spodumene Concentrate sheet Lithium hydroxide, it is characterized in that: the method is dissolved the thick product of the monohydrate lithium hydroxide obtaining, and makes Li2The mass concentration of O is: 65-70g/L, then carry out condensing crystallizing by organic solution, and finally liquid-solid separation is dried and obtained the ultra-pure monohydrate lithium hydroxide product of sheet; The wt% of organic solvent is 30-45%, stirs at normal temperatures; Organic solution is carried out after condensing crystallizing with the filtrate after plate compression, separates with ionic membrane, and the organic solution obtaining is returned to re-using.
2. the preparation method with spodumene Concentrate sheet Lithium hydroxide according to claim 1, is characterized in that:
The preparation method of the thick product of described monohydrate lithium hydroxide is:
1) by levigate calcining transition of carrying out α type-β type to 160-180 object spodumene concentrate in rotary kiln, calcining heat is 900-1200 DEG C;
2) oxidate for lithium containing β type obtaining from step 1) is carried out to sulfating roasting in sulfating roasting rotary kiln, sintering temperature is controlled at 480-580 DEG C, 290 DEG C of material temperatures--and 310 DEG C;
3) by step 2) in the neutralization of sizing mixing in size-mixing tank of the acidifying ore deposit of the sulfur acid lithium that obtains, first adding agstone to be adjusted to pH is 5-6, add again pulverized limestone, make pH value for 10-12, then carry out Pyatyi counterflow leaching, the structure of leaching tanks is that solid material filter cake is with 0.01-0.03 m/min of movement, leachate sprays from solid filter cake top, the vacuum sucking-off of filter cake bottom, forms cross-flow, must contain Li through plate compression2The lithium sulfate solution of O:45-55g/L;
4) lithium sulfate solution being obtained by step 3) carries out neutralization reaction with NaOH again, works as OH-During for 60-70g/L, be cooled to-1 to-10 DEG C, then carry out liquid-solid separation and obtain sal glauberi and lithium hydroxide solution;
5) sal glauberi obtaining in step 4) is dissolved again, then evaporative crystallization dehydration, dries and obtains anhydrous sodium sulfate product;
6) obtained by step 4) containing Li2O is the lithium hydroxide solution of 45-55g/L, evaporates at the high-efficiency evaporator of 100-120 DEG C, makes Li2The content of O reaches 110-150g/L;
7) evaporation and concentration solution step 6) being obtained carries out crystallisation by cooling at the temperature of 40-60 DEG C, obtains containing Li2O content is the thick product of the monohydrate lithium hydroxide of 52-54%.
3. the preparation method with spodumene Concentrate sheet Lithium hydroxide according to claim 1, it is characterized in that: the general character of described organic solvent is: lithium hydroxide is insoluble to this solvent or is slightly soluble in this solvent, dissolve each other with water, and there is certain affinity with water, together with water time, carry out separation with molecular screen membrane.
4. the preparation method with spodumene Concentrate sheet Lithium hydroxide according to claim 1, is characterized in that: described organic solvent is one or more the mixture in alcohols, ketone, ethers or aromatic hydrocarbons.
5. the preparation method with spodumene Concentrate sheet Lithium hydroxide according to claim 1, is characterized in that: described organic solvent is one or more the mixture in methyl alcohol, ethanol, propyl alcohol, butanone, the tertiary butanone of formaldehyde, the tertiary fourth ethylether of formaldehyde or the tertiary fourth ethylether of acetaldehyde.
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| CN107200338A (en) * | 2017-07-15 | 2017-09-26 | 汕头市泛世矿产资源股份有限公司 | The technique that a kind of acidization extracts lithium hydroxide from amblygonite |
| CN107188204A (en) * | 2017-07-15 | 2017-09-22 | 汕头市泛世矿产资源股份有限公司 | The technique that a kind of lime method extracts lithium hydroxide from amblygonite |
| CN107381605A (en) * | 2017-07-18 | 2017-11-24 | 昊青薪材（北京）技术有限公司 | A kind of NaOH decomposes the method that spodumene prepares lithium carbonate by-product analcime |
| CN109461924B (en) * | 2018-10-23 | 2022-02-01 | 四川万邦胜辉新能源科技有限公司 | Method for preparing NCA precursor by lithium cycle |
| KR102164661B1 (en) * | 2018-12-06 | 2020-10-12 | 주식회사 에코프로이노베이션 | Preparation method of lithium hydroxide from lithium concentration by calcination with sodium sulfate |
| CN110117019A (en) * | 2019-05-27 | 2019-08-13 | 四川思达能环保科技有限公司 | Lithium hydroxide production technology |
| CN113149039B (en) * | 2021-04-30 | 2023-03-03 | 四川万邦胜辉新能源科技有限公司 | Method for preparing lithium oxide by thermal reduction of spodumene |
| CN113735139A (en) * | 2021-10-08 | 2021-12-03 | 江苏瑞升华能源科技有限公司 | Preparation and purification method of battery-grade lithium hydroxide |
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