CN105289455A - Method for prolonging service life of lithium ion sieve adsorbent through limiting practical use capacity - Google Patents
Method for prolonging service life of lithium ion sieve adsorbent through limiting practical use capacity Download PDFInfo
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- CN105289455A CN105289455A CN201510839970.5A CN201510839970A CN105289455A CN 105289455 A CN105289455 A CN 105289455A CN 201510839970 A CN201510839970 A CN 201510839970A CN 105289455 A CN105289455 A CN 105289455A
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Abstract
The invention discloses a method for prolonging the service life of a lithium ion sieve adsorbent through limiting the practical use capacity. The method comprises the following steps: step 1, pretreatment: adding a substance which has a pH buffer capacity and controls the solution environment into a to-be-adsorbed lithium-containing solution; step 2, adsorption: fully mixing the to-be-adsorbed lithium-containing solution subjected to pretreatment with the lithium ion sieve adsorbent, so as to complete the exchange adsorption of lithium ions; step 3, desorption: soaking the adsorbent completing adsorption in an acid solution. According to the method, the solution environment where the lithium ion sieve adsorbent exists is adjusted, and the practical adsorption capacity of the adsorbent is limited, so that the service life of the adsorbent can be prolonged on the precondition that the microstructure of the adsorbent is not improved, the total lithium element adsorption and transmission amount in the whole service life is increased, the production cost is reduced, the adsorbent and the adsorption-desorption technology are applied to occasions where the lithium element concentration is relatively low, and the resource utilization rate during the lithium mineral resource exploitation and waste lithium battery recycling processes is increased.
Description
Technical field
The invention belongs to mining mineral resource and solid waste recovery field, relate to a class LMO(lithium metal oxide) using method of lithium ion sieve adsorbant in lithium resource exploitation or recovery, specifically, a kind of method being improved its service life by the actual use capacity of limiting lithium ion sieve adsorbant is related to.
Background technology
Along with the arrival in digitlization imformation age and new forms of energy epoch, lithium secondary battery has become best, the most widely used portable and packaged type energy storage device of combination property, especially the extensive stored energy application demand outburst such as electric automobile, hybrid vehicle and energy-accumulating power station in recent years, lithium secondary battery output is doubled and redoubled, and battery has become the topmost consumption direction of lithium resource.Lithium resource equals to over the strategic position of an oil over 100 years in the strategic importance in new forms of energy epoch, but the exploitation rate of lithium resource has been difficult to meet the demand that lithium battery industry increases fast at present, and the main countermeasure for this problem has three:
One is the technology that Improvement extracts elemental lithium from liquid lithium mineral resources because on the earth in minable lithium resource liquid form account for over half, on Chinese territory, this ratio is especially up to more than 80%.
Two are exploitations from existing lithium ore deposit (comprising solid-state and liquid) exploitation, production line for refining discharge tail washings the technology of the elemental lithium reclaiming loss because existing exploitation, production line for refining discharge the elemental lithium run off in tail washings at most can up to 40% of total amount.
Three is that the technology of elemental lithium is reclaimed in exploitation from waste lithium cell, and existing waste lithium cell recovery technology is immature, and main purpose is the cobalt element in Call Provision acid lithium battery, to the recovery technology of elemental lithium in all kinds waste lithium cell still under study for action.
Lithium ion sieve adsorbant all has wide practical use in above-mentioned three kinds of lithium resources exploitation and recovery technology, wherein LMO(lithium metal oxide) type lithium ion sieve adsorbant has good selective adsorption capacity especially, extraction elemental lithium and these two processes of removing impurities (refining) can be solved in the lump.This is wherein studied the most deep, selective adsorption capacity it is preferred that manganese based lithium-ion sieve adsorbant, as LiMnO
2.5(be usually also designated as Li
1.6mn
1.6o
4), Li
4mn
5o
12(be usually also designated as Li
1.33mn
1.67o
4) etc., but they have a common weakness, are exactly slowly dissolve in the process used at adsorption-desorption cycle.
Summary of the invention
The object of the invention is to alleviate LMO type lithium ion sieve adsorbant dissolution in actual use, make it have longer service life, thus Loss reducing, reduce costs, increase the benefit.
For achieving the above object, the invention provides and a kind ofly limit actual use capacity to improve the method in lithium ion sieve adsorbant life-span, the method comprises:
Step 1, pretreatment: the material of access control solution environmental carries out pretreatment in lithium-containing solution upon adsorption; The material of described control solution environmental has pH buffer capacity;
Step 2, absorption: pretreated lithium-containing solution upon adsorption is fully mixed with lithium ion sieve adsorbant, completes the exchange adsorption to lithium ion under the material restriction of institute's access control solution environmental;
Step 3, desorption: soak the adsorbent having completed adsorption step with acid solution, make lithium ion exchanged desorption enter solution, obtains the lithium ion sieve adsorbant after desorption in order to again adsorbing.
The key component of described lithium ion sieve adsorbant uses the increase of capacity to have aggravation to dissolve the characteristic of loss with reality, " actual use capacity " herein, refer in the adsorption and desorption circulation technology flow process of actual production, each circulation is discharged into the lithium ion gross mass of acid desorption liquid except the total dry mass of lithium ion sieve adsorbant pure substance for exchange adsorption, disregards adhesive, excipient quality (if there is).
Described lithium ion sieve adsorbant is LMO type lithium ion sieve adsorbant, wherein, " M " represents metallic element, select any one or the multiple mixing in Al, Sn, Ti, V, Cr, Mn, Fe, Co, Ni, Zr, Mo, " L " represent Li or Li and other alkali metal, alkaline-earth metal ions mix that (berthollide is as Li
xmg
1.33-xmn
1.67o
4), " O " represention oxygen atom; The variable-scale of " L " " M " " O " and need not be integer.
Described lithium-containing solution upon adsorption needs the material adding to control solution environmental in preprocessing process, as having the material of pH buffer capacity, select carbonate, bicarbonate, ammonia (containing organic amine), any one or multiple mixing in acylate (acetate, edetate).Amount of substance final concentration (mol/L) sum of these materials in pretreated solution should be greater than 50% of lithium ion final concentration.
The adsorption and desorption step of described lithium ion sieve adsorbant can complete in solution constantly flows the dynamic process changed, according to dynamic process, then at the end of lithium-containing solution pre-treatment step upon adsorption, the material final concentration sum with pH buffer capacity should be 50% or higher of lithium ion final concentration.Described dynamic process refers to that solution constantly flows through from the one or several adsorbent equipments being filled with lithium ion sieve adsorbant, and the artificial or each adsorbent equipment of procedure auto-control switches between adsorption step and desorption simultaneously.Adsorbent equipment can adsorption selection post, adsorption tower, any one or a few combination in flowing bed reactor.
The adsorption and desorption step of described lithium ion sieve adsorbant also can complete in the static process that solution is not changed in each one step, according to static process, then at the end of lithium-containing solution pre-treatment step upon adsorption, the material final concentration sum with pH buffer capacity should be 100% or higher of lithium ion final concentration.
The acid solution of described desorption selects acid or acid salt solution, and described acid comprises hydrochloric acid or sulfuric acid, and described acid salt comprises niter cake or ammonium hydrogen sulfate.
The present invention by control absorption or desorption time solution environmental as conditions such as pH value, temperature, assisting ion concentration, restriction LMO(lithium metal oxide) type lithium ion sieve adsorbant makes it only give play to a part for maximum adsorption ability, like this can in the prerequisite not improving adsorbent microstructure service life of downward long adsorbent, improve the elemental lithium absorption migration total amount of total life cycle, reduce production cost, improve efficiency-cost ratio.
Accompanying drawing explanation
Fig. 1 is lithium ion sieve adsorbant HMnO
2.5mn stripping quantity with adsorbent actual use volume change curve, wherein ordinate is logarithmic coordinates, illustrate with reality use capacitance linearity decline, Mn stripping quantity exponentially declines.
Fig. 2 is lithium ion sieve adsorbant HMnO
2.5li
+h is released in exchange
+measure the curve changed with the change of solution (during balance) pH value, illustrate with pH value decline, adsorbent HMnO
2.5with Li
+exchange the H discharged
+reduce, namely the actual adsorption capacity played declines.
Detailed description of the invention
The present invention limits LMO type lithium ion sieve adsorbant by controlling solution environmental, makes it only give play to a part for maximum adsorption ability in actual use, thus increases the service life.Adsorbent mainly experiences following operational sequence in actual use:
1. desorption first.LMO type lithium ion sieve such as LiMnO
2.5(be usually also designated as Li
1.6mn
1.6o
4), different according to preparation method, lithium ion saturation state often time obtained, need exchange with acid soak before using and lithium ion desorption is obtained not containing the lithium ion sieve adsorbant of lithium.Following steps are for the absorbent particles static adsorptive method in laboratory: get the LiMnO that heap volume is about 100mL
2.5absorbent particles, adds 300mL0.5mol/L hydrochloric acid, places 10 ~ 12 hours, stir once in a while therebetween after stirring.Topple over and fall liquid part, with clear water washing 2 ~ 3 times, then add 200mL0.5mol/L hydrochloric acid, place 24 hours after stirring, stir once in a while therebetween.Topple over and fall liquid part, with clear water washing 2 ~ 3 times, add and be more than or equal to 500mL clear water and soak more than 24 hours, change water therebetween at least 2 times.So obtain the lithium ion sieve adsorbant HMnO after desorption
2.5.
2. adsorb.Lithium-containing solution upon adsorption is regulated pH to 8.0 ~ 8.4 as salt lake bittern NaOH or KOH, then adds a certain amount of NaHCO
3or NaHCO
3+ Na
2cO
3mixture, make carbonate final concentration [CO wherein
3 2-]+bicarbonate radical final concentration [HCO
3 -] sum (unit mol/L) is a little more than the lithium ion final concentration in solution, ratio can be 110% ~ 120%, (then can be lower slightly as 70% ~ 80% in dynamic adsorption method.) by the lithium ion sieve adsorbant HMnO of desorption process
2.5add this solution, be interrupted shake mixing, soak 24 hours.This soak time can detect known absorption situation by real time sample and determine, also can generally be estimated as 12 ~ 24 hours.
3. desorption.Above-mentioned lithium ion sieve adsorbant HMnO
2.5liMnO is become after absorption lithium ion
2.5, it is separated with the lithium-containing solution after adsorption treatment, with clear water washing 2 ~ 3 times, then adds 300mL0.5mol/L hydrochloric acid, place more than 4 hours after stirring, occasional agitation therebetween.Acid solution is separated with adsorbent, namely containing the lithium ion obtained after adsorption-desorption cycle process in this acid solution.Again with clear water washing adsorbent 2 ~ 3 times, add and be more than or equal to 500mL clear water and soak more than 24 hours, change water therebetween at least 2 times, so obtain the lithium ion sieve adsorbant HMnO after desorption
2.5.Repeat above-mentioned steps 2 and 3, can adsorption-desorption cycle be realized.
As shown in Figure 1, after the capacity that limiting lithium ion sieve adsorbant is played in actual use, the stripping quantity of Mn element is approximate with the minimizing of reality use capacity exponentially to be reduced, and the stripping quantity direct quantitative of Mn element describes HMnO
2.5chemical wear in use.Therefore, the capacity played in actual use by limiting lithium ion sieve adsorbant can reduce the chemical wear of each circulation, improves cycle life.While considering that capacitance linearity reduces, loss exponentially reduces, also namely cycle life exponentially increases, equal to standard of comparison with lithium ion sieve adsorbant accumulative dissolving loss, the method significantly can increase during adsorbent repeatedly circulates the elemental lithium total amount shifted when stack loss is equal, be equivalent to extend actual life, unit use cost declines.
As shown in Figure 2, lithium ion sieve adsorbant HMnO
2.5li
+h is released in exchange
+amount changes with the change of solution (during balance) pH value, by controlling pH value of solution during absorption (balance), and can limiting lithium ion sieve adsorbant HMnO
2.5absorption Li
+actual use capacity.Due to HMnO
2.5exchange adsorption Li
+while the H of amount of substance such as to discharge
+, these H
+with specially to add in solution and material as OH
-, HCO
3 -reaction, after adsorption equilibrium, pH≤7 run out of with material in illustrating, now there is concentration relationship Δ [Li
+]=[OH
-]
initially+ 10
-pH end, or Δ [Li
+]=[HCO
3 -]
initially+ 10
-pH end; During pH>7 illustrates and material still have surplus, during adsorption capacity is now no more than and initially adds and amount of substance.As can be seen here, buffer HCO is used
3 -or HCO
3 -with CO
3 2-the buffering of composition is right, can limit and maintain the solution ph in adsorption process, thus limiting lithium ion sieve adsorbant HMnO
2.5only play partial adsorbates capacity, finally reach the object of the use cost that increases the service life, reduces.
Technical scheme of the present invention is described in detail below in conjunction with embodiment.
Embodiment 1
Get the LiMnO that heap volume is about 1L
2.5bond the particle after figuration granulation through PVC, pour in Plastic Drum and add 3L0.5mol/L hydrochloric acid, place after soft stirring 12 hours (occasional agitation).Topple over and fall liquid part, wash 3 times with clear water, then add 2L0.5mol/L hydrochloric acid, after stirring, place 24 hours (occasional agitation).Topple over and fall liquid part, wash 3 times with clear water, add 5L clear water and soak 24 hours, change water 2 each 5L therebetween.So obtain the lithium ion sieve adsorbant HMnO after desorption
2.5-PVC granule.
Absorption: regulate about pH to 8.4 by upon adsorption containing lithium salts lake bittern water NaOH, then add a certain amount of NaHCO according to lithium content
3---the solution of such as this example containing lithium 1000ppm, then add NaHCO
3make final concentration [HCO
3 -]=0.17mol/L, adds this solution by the lithium ion sieve adsorbant of desorption process, is interrupted and stirs mixing, soak 24 hours.Lithium ion sieve adsorbant HMnO
2.5liMnO is become after absorption lithium ion
2.5.
Desorption: by the particle (LiMnO after absorption
2.5) be separated with processed bittern, with clear water washing granule 3 times, then add 3L0.5mol/L hydrochloric acid, place more than 4 hours after stirring, be interrupted therebetween and stir mixing.Acid solution is separated with adsorbent, namely containing the lithium ion obtained after adsorption-desorption cycle process in this acid solution, the follow-up processing step preparing lithium carbonate can be sent to and uses, or also can again for adsorbent desorption (obtaining the desorption solution that lithium concentration is higher).Wash absorbent particles 3 times with clear water again, add 5L clear water and soak 24 hours, change water 2 each 5L therebetween.So obtain the lithium ion sieve adsorbant HMnO after desorption
2.5-PVC granule.Repeat adsorption step and desorption, can adsorption-desorption cycle be realized.
The method is compared adjustment in use in traditional handicraft and, to the bittern of pH=9.2 ~ 10, under adsorbent dissolves the roughly equal standard of comparison of loss, is extracted elemental lithium total amount and improve 1 ~ 5 times.
Embodiment 2
According to the actual volume of adsorption tower, get a certain amount of through acid exchange desorption and cleaned HMnO
2.5-PVC granule, load adsorption tower, tower top reserve about 1/10 cushion space and keep and air unimpeded.
Absorption: regulate pH to 7 ~ 8 by upon adsorption containing lithium salts lake bittern water carbonate or NaOH in pretreatment pool, then add a certain amount of NaHCO according to lithium content
3---the solution of such as this example containing lithium 1000ppm, then add NaHCO
3make final concentration [HCO
3 -]=0.11mol/L; Because reality implements the price of saturated Lithium carbonate solution and dilution heat of sulfuric acid in the factory of this technique far below sodium acid carbonate, the actual process on production line adds Li by amount of substance than 2:1
2cO
3and H
2sO
4, make final concentration [HCO
3 -]=0.1 ~ 0.11mol/L.The bittern upon adsorption handled well is slowly continuously pumped into adsorption tower, the lithium concentration of monitoring tower outlet, adsorption step can be stopped when adsorption rate drops to 50 ~ 60% according to specific requirement.First order entrance lithium concentration 1000ppm in this example, then monitor when efflux lithium concentration is increased to about 500ppm and stop adsorption step.Now lithium ion sieve adsorbant HMnO
2.5absorption lithium ion becomes LiMnO
2.5.
Desorption: the adsorption tower clear water quick wash terminated by adsorption step 5 ~ 10 minutes, slowly pumps into 0.25mol/L sulfuric acid eluent (actual for containing low concentration lithium reuse eluent), the lithium concentration of monitoring tower outlet or acid concentration subsequently.According to specific requirement after the lithium concentration that desorption goes out drops to certain value---when lithium content drops to 300 ~ 350ppm in such as this example, oral fluid will be gone out and be recovered to sour holding vessel, reuse for during follow-up wash-out; Treat that lithium content continues to drop to <100ppm again, stop desorption.The eluent of higher li content (not reusing) can be sent to the follow-up processing step use preparing lithium carbonate before.
Adsorption tower clear water quick wash desorption terminated 10 minutes, now adsorption tower is in standby just state, can enter adsorption step.Repeat adsorption step and desorption, can adsorption-desorption cycle be realized.
The method is the dynamic method that the actual production line put into trial operation is implemented, case of comparative examples 1, and the dissolving loss of adsorbent is more remarkable than traditional handicraft equally to alleviate, life; And the method is faster than the static method adsorption and desorption speed of example 1, often circulate shortening consuming time.
Embodiment 3
Step with reference to embodiment 2 is carried out, but only in pretreatment pool, contains lithium bittern Ca (OH) by upon adsorption
2or NaOH regulates pH to about 8.5, and do not add NaHCO
3deng carbonic acid (hydrogen) salt buffer.The method is applicable to the working condition that cannot obtain cheap carbonate, bicarbonate, and owing to not having buffer, adsorption rate declines rapidly at the very start, therefore needs to reuse liquid upon adsorption until wherein lithium content is reduced to certain value.
The initial upon adsorption bittern of this example containing lithium 1000ppm, slowly pump into adsorption tower after pretreatment, the lithium concentration in monitoring stream fluid, lithium concentration rises to >800ppm very soon.Efflux is expelled back into pretreatment pool, uses self-checking device to supplement Ca (OH) simultaneously in pretreatment pool
2or NaOH, make the solution in pretreatment pool remain at the state of pH about 8.5.Bittern iterative cycles upon adsorption is made to flow, until go out oral fluid drop to <500ppm containing lithium amount time (single stage adsorption, as first order outlet <500ppm during multi-stage absorption), stop adsorption step, oral fluid will be gone out and directly discharge; If or bittern upon adsorption contains lithium far more than this adsorption plant single adsorptions capacity, then iterative cycles flows to out differing with entrance containing lithium amount of oral fluid and is no more than 20ppm, stops adsorption step.
Cleaning and desorption are with reference to embodiment 2.
The method is under the working condition that cannot obtain cheap carbonate, bicarbonate, and to a kind of alternative of embodiment 2, its rate of adsorption comparatively example 2 is much lower, and therefore the increase consuming time of each adsorption-desorption cycle is more.In the method, the dissolving loss of adsorbent is more remarkable than traditional handicraft equally alleviates, life.
In sum, the present invention by control absorption or desorption time solution environmental as conditions such as pH value, temperature, assisting ion concentration, restriction LMO(lithium metal oxide) type lithium ion sieve adsorbant makes it only give play to a part for maximum adsorption ability, under the prerequisite not improving adsorbent microstructure, significantly extend the service life of adsorbent, substantially increase the elemental lithium absorption migration total amount of total life cycle; Being particularly useful for key component uses the increase of capacity to have aggravation to dissolve the lithium ion sieve adsorbant of the characteristic of loss with reality.
Although content of the present invention has done detailed introduction by above preferred embodiment, will be appreciated that above-mentioned description should not be considered to limitation of the present invention.After those skilled in the art have read foregoing, for multiple amendment of the present invention and substitute will be all apparent.Therefore, protection scope of the present invention should be limited to the appended claims.
Claims (10)
1. limit actual use capacity to improve the method in lithium ion sieve adsorbant life-span, it is characterized in that, the method comprises:
Step 1, pretreatment: the material of access control solution environmental carries out pretreatment in lithium-containing solution upon adsorption; The material of described control solution environmental has pH buffer capacity;
Step 2, absorption: pretreated lithium-containing solution upon adsorption is fully mixed with lithium ion sieve adsorbant, completes the exchange adsorption to lithium ion under the material restriction of institute's access control solution environmental;
Step 3, desorption: soak the adsorbent having completed adsorption step with acid solution, make lithium ion exchanged desorption enter solution, obtains the lithium ion sieve adsorbant after desorption in order to again adsorbing.
2. the method for claim 1, it is characterized in that, described lithium ion sieve adsorbant is LMO type lithium ion sieve adsorbant, wherein, " M " represents metallic element, selects any one or multiple mixing in Al, Sn, Ti, V, Cr, Mn, Fe, Co, Ni, Zr, Mo, and " L " represents Li or Li and other alkali metal, the mixing of alkaline-earth metal ions, " O " represention oxygen atom, the ratio of " L " " M " " O " is not restricted to 1:1:1.
3. method as claimed in claim 2, is characterized in that, described LMO type lithium ion sieve adsorbant is used for adsorption and desorption step with the form of pure substance powder, or, with form of mixtures form with adhesive, excipient for adsorption and desorption step.
4. the method for claim 1, is characterized in that, the material of described control solution environmental selects any one or multiple mixing in carbonate, bicarbonate, ammonia, organic amine, acetate, edetate.
5. the method for claim 1, is characterized in that, the acid solution of described desorption selects acid or acid salt solution, and described acid comprises hydrochloric acid or sulfuric acid, and described acid salt comprises niter cake or ammonium hydrogen sulfate.
6. the method for claim 1, is characterized in that, the adsorption and desorption step of lithium ion sieve adsorbant completes in solution constantly flows the dynamic process changed, or completes in the static process that solution is not changed in each one step.
7. method as claimed in claim 6, is characterized in that, when adopting dynamic process to carry out adsorption and desorption, the amount of substance final concentration sum of material in pretreated lithium-containing solution upon adsorption of described control solution environmental is greater than 50% of lithium ion final concentration.
8. method as claimed in claim 6, it is characterized in that, when adopting static process to carry out adsorption and desorption, the amount of substance final concentration sum of material in pretreated lithium-containing solution upon adsorption of described control solution environmental should be 100% or higher of lithium ion final concentration.
9. method as claimed in claim 6, it is characterized in that, described dynamic process refers to that solution constantly flows through from the one or several adsorbent equipments being filled with lithium ion sieve adsorbant, and the artificial or each adsorbent equipment of procedure auto-control switches between adsorption step and desorption simultaneously.
10. method as claimed in claim 9, is characterized in that, any one or a few the combination in described adsorbent equipment adsorption selection post, adsorption tower, flowing bed reactor.
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| US11964876B2 (en) | 2020-06-09 | 2024-04-23 | Lilac Solutions, Inc. | Lithium extraction in the presence of scalants |
| US11377362B2 (en) | 2020-11-20 | 2022-07-05 | Lilac Solutions, Inc. | Lithium production with volatile acid |
| CN115029564A (en) * | 2022-08-12 | 2022-09-09 | 矿冶科技集团有限公司 | Co-production process for extracting lithium from salt lake brine and preparing acid from sulfur-containing material and application |
| CN117101599A (en) * | 2023-08-04 | 2023-11-24 | 香港中文大学（深圳） | Lithium ion sieve adsorbent material and preparation method and application thereof |
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