CN103387244B - Method for enriching lithium in carbonate type salt lake brine - Google Patents
Method for enriching lithium in carbonate type salt lake brine Download PDFInfo
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- CN103387244B CN103387244B CN201310320903.3A CN201310320903A CN103387244B CN 103387244 B CN103387244 B CN 103387244B CN 201310320903 A CN201310320903 A CN 201310320903A CN 103387244 B CN103387244 B CN 103387244B
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- 238000000034 method Methods 0.000 title claims abstract description 89
- 239000012267 brine Substances 0.000 title claims abstract description 70
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 title claims abstract description 70
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 27
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 title claims abstract description 17
- 239000007791 liquid phase Substances 0.000 claims abstract description 161
- 238000001704 evaporation Methods 0.000 claims abstract description 146
- 230000008020 evaporation Effects 0.000 claims abstract description 143
- 239000007790 solid phase Substances 0.000 claims abstract description 84
- 150000003839 salts Chemical class 0.000 claims abstract description 81
- 239000007788 liquid Substances 0.000 claims abstract description 48
- 238000000926 separation method Methods 0.000 claims abstract description 46
- 238000007710 freezing Methods 0.000 claims abstract description 36
- 230000008014 freezing Effects 0.000 claims abstract description 36
- 241001131796 Botaurus stellaris Species 0.000 claims description 158
- 230000008569 process Effects 0.000 claims description 47
- 229920006395 saturated elastomer Polymers 0.000 claims description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 19
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 19
- 230000007613 environmental effect Effects 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000001816 cooling Methods 0.000 description 10
- 238000012544 monitoring process Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 5
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical group [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 229910001760 lithium mineral Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000010446 mirabilite Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- NIAGBSSWEZDNMT-UHFFFAOYSA-M tetraoxidosulfate(.1-) Chemical compound [O]S([O-])(=O)=O NIAGBSSWEZDNMT-UHFFFAOYSA-M 0.000 description 1
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- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
Abstract
The invention relates to a method for enriching lithium in carbonate type salt lake brine, which comprises the following steps of: alternately performing low-temperature evaporation and freezing placing treatment on the salt lake brine; and after each evaporation or placing treatment, performing solid-liquid separation to remove solid-phase salt mine to obtain Li<+>-enriched liquid-phase brine. According to the method provided by the invention, lithium ions are enriched in the liquid-phase brine by a variable-temperature evaporation method; the method can make use of natural energy and has the advantages of environmental friendliness and low energy consumption; and the concentration of the enriched lithium ions can exceed 30g/L.
Description
[technical field]
The present invention relates to salt lake brine and utilize field, particularly relate to the method from carbonate type salt lake brine enriching lithium.
[background technology]
The lithium resource of China is mainly distributed in the salt lake of Qinghai-Tibet Platean, and wherein the lithium resource in Tibet is mainly in carbonate type, and mainly concentrate on and hide the Salt Lake Zabuye of Northwestern Part and Bange-Du family's lithium lake of east, lithium resource accounts for 8,370,000 t and 500,000 t respectively.Tibetan Salt Lakes resource is mainly present in liquid bittern, and after natural solar evaporation, lithium ion is mainly with KLiSO
4, NaLiSO
4, 3Li
2sO
4h
2o form exists.
In prior art, isothermal evaporation method evaporation concentration bittern is used in the enrichment for lithium usually.After in evaporative process, lithium ion reaches capacity in the liquid phase, separate out constantly in solid phase.There are some defects in the method for this enriching lithium, such as, because lithium is separated out in solid phase, separates out and compare dispersion, be unfavorable for the extraction processing and utilization of lithium.Therefore, if can in liquid phase bittern enriching lithium, then more can be conducive to extraction and the processing and utilization of lithium.
In addition, at present from the method for salt lake brine enriching lithium mainly for sulfate type salt lake brine, the lithium ion enrichment for carbonate type salt lake brine is still the problem needing solution badly.
[summary of the invention]
The object of the present invention is to provide a kind of method from carbonate type salt lake brine enriching lithium.
Technical scheme of the present invention is: a kind of method of enriching lithium from carbonate type salt lake brine, comprising: carry out low-temperature evaporation alternately and freezing placement process to salt lake brine; And after each evaporation or placing, carry out solid-liquid separation, to remove solid phase salt mine, obtain Li
+the liquid phase bittern of enrichment, wherein said low-temperature evaporation carries out in the condition that liquid phase brine temperature is 4 DEG C to 6 DEG C; And in described freezing placement, the temperature of liquid phase bittern is down to the temperature of-10.0 DEG C to-4.0 DEG C.
In some embodiments, in described low-temperature evaporation process, Li in solid phase salt mine and liquid phase bittern can be monitored
+mass concentration, until Li in liquid phase bittern
+mass concentration reach Li in solid phase salt mine
+during 10 to 20 times of mass concentration, complete a low-temperature evaporation process.
Described low-temperature evaporation can also be attended by air draft operation, and the wind speed of described air draft operation can be 2.8m/s to 3.8m/s.
Described freezing placement can carry out 4h to 5h.
In described freezing placement process, the rate of temperature fall of liquid phase bittern can be 0.2 DEG C/min to 0.5 DEG C/min.
In some embodiments, the low-temperature evaporation that at least two-wheeled replaces, freezing placement process can be carried out to salt lake brine.
In some embodiments, described method can also comprise: before low-temperature evaporation first, carry out first time evaporation process, Li to liquid phase to liquid phase bittern
+content reaches capacity; And/or the last time after low-temperature evaporation or freezing placement process, second time evaporation process is carried out to liquid phase bittern, Li to liquid phase
+content reaches capacity, and solid-liquid separation, removes the step of solid phase salt mine.
Wherein, described first time evaporation is carried out in the condition that liquid phase brine temperature is 15.0 DEG C to 30.0 DEG C, and the evaporation of described second time is carried out in the condition that liquid phase brine temperature is 10.0 DEG C to 15.0 DEG C
In some embodiments, said method comprising the steps of: S1 first time high temperature evaporation, makes salt lake brine evaporate, until Li in liquid phase the temperature of 10.0 DEG C to 30.0 DEG C
+content reaches or close to saturated, solid-liquid separation obtains the first solid phase salt mine and the first liquid phase bittern; S2 first time low-temperature evaporation, makes the first liquid phase bittern evaporate, until Li in liquid phase bittern the temperature of 4 DEG C to 6 DEG C
+mass concentration rise to 0.40% to 0.50%, solid-liquid separation obtains second solid phase salt mine and second liquid phase bittern; S3 first time freezing placement, makes second liquid phase bittern be cooled to-8.0 DEG C to-4.5 DEG C, and place 4h to 5h, solid-liquid separation obtains the 3rd solid phase salt mine and the 3rd liquid phase bittern; S4 second time low-temperature evaporation, makes the 3rd liquid phase bittern evaporate, until Li in liquid phase bittern the temperature of 4.6 DEG C to 4.8 DEG C
+mass concentration reach 10 to 20 times of mass concentration in solid phase salt mine, solid-liquid separation obtains the 4th solid phase salt mine and the 4th liquid phase bittern; The freezing placement of S5 second time, make the 4th liquid phase bittern be cooled to-9.5 DEG C to-8.0 DEG C, place 4h to 5h, solid-liquid separation obtains the 5th solid phase salt mine and the 5th liquid phase bittern; S6 third time low-temperature evaporation, makes the 5th liquid phase bittern evaporate, until Li in liquid phase bittern the temperature of 4.6 DEG C to 4.8 DEG C
+mass concentration reach 10 to 20 times of mass concentration in solid phase salt mine, solid-liquid separation obtains the 6th solid phase salt mine and the 6th liquid phase bittern; S7 second time high temperature evaporation, makes the 6th liquid phase bittern evaporate, until Li in liquid phase the temperature of 10.0 DEG C to 15.0 DEG C
+content reaches or close to saturated, solid-liquid separation, obtains the 7th solid phase salt mine and the 7th liquid phase bittern, Li in wherein said 7th liquid phase bittern
+mass concentration be more than or equal to 30g/L.
Advantage of the present invention and beneficial effect are: method of the present invention, from carbonate type salt lake brine enriching lithium, can utilize the salt lake brine in China Tibet targetedly; Utilize alternating temperature evaporation technique, the enrichment of lithium ion in liquid phase bittern can be realized, be conducive to the extraction processing of lithium and utilize; The method can be applied to salt pan, field, utilizes the natural energy of climate change, enriching method environmental protection, less energy-consumption.
[accompanying drawing explanation]
The method flow of Fig. 1 illustrates according to one embodiment of the invention, from the method steps of carbonate type salt lake brine enriching lithium.
The technical process of Fig. 2 illustrates according to the present invention with embodiment, from the technical process of carbonate type salt lake brine enriching lithium.
[embodiment]
Ultimate principle of the present invention utilizes the solubleness of vitriol when low temperature less, and the solubleness of lithium minerals raises and the character of reduction along with temperature simultaneously, evaporates the lithium ion in enriched carbonate type salt lake brine in alternating temperature mode.By controlling the concentration of sulfate radical and lithium ion in liquid phase bittern in evaporation and freezing put procedure, make lithium ion enrichment in liquid phase bittern.
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, but not limit the scope of the invention.
Fig. 1 and Fig. 2 illustrates according to a preferred embodiment of the invention respectively, from method steps and the technical process of carbonate type salt lake brine enriching lithium.
Composition graphs 1 and Fig. 2 visible, method of the present invention mainly comprises carries out low-temperature evaporation alternately and freezing placement process to salt lake brine; And after each evaporation or placing, carry out solid-liquid separation, to remove solid phase salt mine, obtain Li
+the liquid phase bittern of enrichment.In low-temperature evaporation operation, liquid phase brine temperature controls the scope at 4 DEG C to 6 DEG C, Li at such temperature
+can enrichment in the liquid phase effectively.In freezing placement operation, the temperature controlling liquid phase bittern is down to the scope of-10.0 DEG C to-4.0 DEG C.Because the solubleness of vitriol in this freezing scope is very little, mainly with the form crystallization of sodium sulfate.Place in such temperature, sulphate crystal can be made to separate out, and so, in liquid phase, the concentration of sulfate radical is effectively controlled, and also reduces Li when again evaporating
+with sulfate radical in conjunction with probability, make Li
+can enrichment in the liquid phase better.
In low-temperature evaporation process, Li in solid phase salt mine and liquid phase bittern can also be monitored
+mass concentration, control low-temperature evaporation carry out.Such as when Li in liquid phase bittern being detected
+mass concentration reach Li in solid phase salt mine
+during 10 to 20 times of mass concentration, this low-temperature evaporation operation can be terminated, Li
+reach capacity at the process conditions.In practice, produce from actual industrialization and consider, simultaneously in conjunction with weather condition, in low-temperature evaporation process, detect the Li in liquid phase
+concentration, content, again close to after reaching capacity, carries out next step operation.
In order to make low-temperature evaporation more effective, and in order to shorten the time of low-temperature evaporation, can operate with air draft in low-temperature evaporation process, such as can with the wind speed air draft of 2.8m/s to 3.8m/s.
Described freezing placement can carry out 4h to 5h usually, and with the rate of temperature fall of 0.2 DEG C/min to 0.5 DEG C/min, liquid phase bittern can be cooled to suitable temperature in this process, cooling rate is slower, is about conducive to Li
+enrichment in the liquid phase.But in practice, those skilled in the art according to actual needs, can consider the factors such as efficiency cost, select suitable rate of temperature fall.
Low-temperature evaporation alternately and freezing placement process also can be cycled to repeat according to actual needs.Such as can first low-temperature evaporation salt lake brine, the liquid phase brine freezing that then will obtain is placed, afterwards alternately low-temperature evaporation, freezing placement again, etc.Or also can after last freezing placement, low-temperature evaporation etc. again.
The number of times of low-temperature evaporation and freezing placement equally can according to practical situation, by those skilled in the art according to salt lake brine concrete composition, required for the consideration of lithium ion enriched concentration, efficiency and cost aspect that reaches select.Such as, and in the method from salt lake brine enriching lithium ion, between different low-temperature evaporation steps, or between different freezing placement steps, the actual conditions adopted, temperature, time etc. can be identical or different.
Such as, in certain situation, consider efficiency and cost, the low-temperature evaporation that at least two-wheeled replaces, freezing placement process can be carried out to salt lake brine.
Before low-temperature evaporation first, first time evaporation process can also be carried out to liquid phase bittern, Li to liquid phase
+content reaches capacity.Such as, the condition that can be preferably 10.0 DEG C to 30.0 DEG C at liquid phase brine temperature carries out first time high temperature evaporation process.
The object that first time evaporates is unsaturated salt lake brine raw materials evaporate to Li
+to reach in the liquid phase or close to saturated.When Li in liquid phase being detected
+content, close to time saturated, stops this evaporative process, enters low-temperature evaporation step.Adopt high temperature evaporation that vaporator rate can be made to accelerate, treat that stock liquid needs control temperature, because the solubleness of lithium salts is to temperature sensitive after saturated.Certain first time evaporation also can adopt low-temperature evaporation, but evaporation required time can corresponding prolongation.
In addition, the last time after low-temperature evaporation or freezing placement process, also second time evaporation process can be carried out to liquid phase bittern, Li to liquid phase
+content reaches capacity, and solid-liquid separation, removes the step of solid phase salt mine.The condition that second time evaporation is preferably 10.0 DEG C to 15.0 DEG C at liquid phase brine temperature is carried out.Second time evaporation is in order to as best one can by the moisture evaporate to dryness in liquid phase, the weight of the mineral and liquid phase being rich in Li is reduced, the content increase of Li, for commercial scale production, decreases processing and extract and transportation cost.Because now Li concentration in the liquid phase has reached higher content, experiment proves, more can not have been met the object of enrichment Li by the mode of alternating temperature, therefore adopts high temperature evaporation, can save time, raise the efficiency, and is conducive to industrial scale and produces.Certainly, also can use low temperature or constant-temperature evaporation, but evaporation required time can corresponding prolongation.
Preferred embodiment shown in composition graphs 1 and Fig. 2, visible, seven steps can be comprised according to the present invention from the method for carbonate type salt lake brine enriching lithium:
First before low-temperature evaporation and cooling place the process that hockets, the first time high temperature evaporation of step S1 is carried out: salt lake brine is evaporated, until Li in liquid phase the temperature of 10.0 DEG C to 30.0 DEG C
+content reaches or close to saturated, obtains the first liquid phase bittern.This step can get rid of most moisture in former halogen, concentrated salt concentration.Because now salt concentration is still lower, there is no the solid phase salt mine of separating out, therefore can not carry out solid-liquid separation operation.
Then be that process is placed in the low-temperature evaporation that replaces the first round and cooling, in the first time low-temperature evaporation of step S2, the first liquid phase bittern evaporated, until Li in liquid phase bittern the temperature of 4 DEG C to 6 DEG C
+mass concentration rise to 0.40% to 0.50%, solid-liquid separation obtains second solid phase salt mine and second liquid phase bittern.And in the freezing placement of the first time of step S3, make second liquid phase bittern be cooled to-8.0 DEG C to-4.5 DEG C, place 4h to 5h, solid-liquid separation obtains the 3rd solid phase salt mine and the 3rd liquid phase bittern.
This low-temperature evaporation evaporates the moisture in liquid phase bittern further, and the second solid phase salt mine of separating out is mainly mirabilite ore (Na
2sO
410H
2o).In this freezing put procedure, solid phase salt mine is separated out under cryogenic further, and main component is sodium-chlor and glaserite (K
3na (SO
4)
2).
Second takes turns in low-temperature evaporation alternately and freezing placement process, in the second time low-temperature evaporation of step S4, the 3rd liquid phase bittern is evaporated, until Li in liquid phase bittern the temperature of 4.6 DEG C to 4.8 DEG C
+mass concentration reach 10 to 20 times of mass concentration in solid phase salt mine, solid-liquid separation obtains the 4th solid phase salt mine and the 4th liquid phase bittern.And in the freezing placement of the second time of step S5, make the 4th liquid phase bittern be cooled to-9.5 DEG C to-8.0 DEG C, place 4h to 5h, solid-liquid separation obtains the 5th solid phase salt mine and the 5th liquid phase bittern.
This takes turns the freezing placement that temperature range that alternately low-temperature evaporation and freezing placement adopt is different from the low-temperature evaporation of the first round.The solid phase salt mine main component separated out is sodium-chlor and Repone K.
Again carry out the third time low-temperature evaporation of step S6 subsequently, the 5th liquid phase bittern is evaporated, until Li in liquid phase bittern the temperature of 4.6 DEG C to 4.8 DEG C
+mass concentration reach 10 to 20 times of mass concentration in solid phase salt mine, solid-liquid separation obtains the 6th solid phase salt mine and the 6th liquid phase bittern.
The solid phase salt mine main component of this low-temperature evaporation precipitation is still sodium-chlor and Repone K.
Finally, place after process completes at the low-temperature evaporation replaced and cooling, carry out the second time high temperature evaporation of step S7, the 6th liquid phase bittern is evaporated, until Li in liquid phase the temperature of 10.0 DEG C to 15.0 DEG C
+content reaches again or close to saturated, solid-liquid separation, obtains the 7th solid phase salt mine and the 7th liquid phase bittern, Li in wherein said 7th liquid phase bittern
+mass concentration be more than or equal to 30g/L.
This further transpiring moisture of high temperature evaporation, the solid phase salt mine that to separate out with sodium-chlor and Repone K be main component, and the concentration of concentrated lithium ion.Make it possible to, in liquid phase bittern, the mass concentration of lithium ion is enriched to more than 30g/L.
The liquid phase bittern obtained after each step and the main component of solid phase salt mine and content thereof see the following form 1:
Table 1: according to the method for one embodiment of the invention from carbonate type salt lake brine enriching lithium, each step gained liquid phase bittern and solid phase salt lake composition
According to method of the present invention, in the liquid phase bittern in the end obtained, the yield of lithium ion is more than or equal to 60.0%, and final quality concentration is more than or equal to 30g/L.Prior art of comparing continues the method separated out dispersedly containing lithium salts ore deposit in solid phase, and enriching method of the present invention is more conducive to the extraction processing and utilization of lithium.
Evaporate lithium ion in enriched carbonate type salt lake brine owing to make use of alternating temperature mode, method of the present invention can be applied in the evaporation experiment of salt pan, field, utilize the natural energy enriching lithium ion of climate change, enrichment process environmental protection, less energy-consumption.
In order to clearly set forth advantage of the present invention, following examples are carried out in environmental chamber, and in each embodiment, solid phase and the liquid product composition of each step are recorded in the form after corresponding embodiment.
embodiment 1
S101 first time high temperature evaporation: after Tibet salt lake brine is mixed, be placed in evaporation tank high temperature evaporation (condition being about 25 DEG C in salt lake brine temperature is carried out), obtain the first liquid phase bittern.
S102 first time low-temperature evaporation: get 400kg first liquid phase bittern, be placed in environmental chamber, regulate simulating chamber temperature, make brine temperature control at 4.0 DEG C, electric fan is interrupted air draft, and blast velocity control is at 2.80m/s.Li in evaporative process monitoring bittern
+concentration, works as Li
+during mass concentration 0.4000%, the salt mine that bittern and evaporation are separated out is carried out solid-liquid separation, obtains solid phase 26kg second solid phase salt mine, 13.58kg second liquid phase bittern.
S103 first time cools placement: second liquid phase bittern is placed in the moderate evaporation tank of volume, and adjustment environment analog room temperature degree, measure brine temperature, make its temperature at-8.0 DEG C, bittern liquidus temperature places 5h after reaching this scope, cooling rate 0.5 DEG C.Carry out solid-liquid separation, obtain 2.44kg the 3rd solid phase salt mine, 7.45kg the 3rd liquid phase bittern.
S104 second time low-temperature evaporation, is placed in the moderate evaporation tank of volume by the 3rd liquid phase bittern, and adjustment environment analog room temperature degree, measure brine temperature, make its temperature at 4.60 DEG C, wind speed and ambient relative humidity remain unchanged, and evaporate bittern.Evaporative process monitoring bittern and evaporation separate out Li in solid phase
+concentration, as the Li in liquid phase
+when mass concentration reaches 10 times of concentration in solid phase, the salt mine that bittern and evaporation are separated out is carried out solid-liquid separation, obtains 0.50kg the 4th solid phase salt mine, 7.50kg the 4th liquid phase bittern.
S105 second time cools placement: the 4th liquid phase bittern is placed in the moderate evaporation tank of volume, adjustment environment analog room temperature degree, measure brine temperature, make its temperature at-9.5 DEG C, bittern liquidus temperature places 5h after reaching this scope, cooling rate 0.30 DEG C, carries out solid-liquid separation, obtains 0.44kg the 5th solid phase salt mine, 6.89kg the 5th liquid phase bittern.
S106 third time low-temperature evaporation: the 5th liquid phase bittern is placed in the moderate evaporation tank of volume, adjustment environment analog room temperature degree, measure brine temperature, make its temperature at 4.60 DEG C, wind speed and ambient relative humidity remain unchanged, and evaporate bittern.Evaporative process monitoring bittern and evaporation separate out Li in solid phase
+concentration, as the Li in liquid phase
+when mass concentration reaches 10 times of concentration in solid phase, the salt mine that bittern and evaporation are separated out is carried out solid-liquid separation, obtains 0.64kg the 6th solid phase salt mine, 4.29kg the 6th liquid phase bittern.
S107 second time high temperature evaporation: the 6th liquid phase bittern is placed in the moderate evaporation tank of volume, adjustment environment analog room temperature degree, measure brine temperature, make its temperature at 10.0 DEG C, wind speed and ambient relative humidity remain unchanged, and evaporate bittern.The salt mine that bittern and evaporation are separated out is carried out solid-liquid separation, obtains the 7th solid phase salt mine 1.14kg, the 7th liquid phase bittern 0.87kg.
The total recovery 62.49% of lithium ion.
Table 2: in the method for embodiment 1, each step products component list
embodiment 2
S201 first time high temperature evaporation: after Tibet salt lake brine is mixed, be placed in evaporation tank high temperature evaporation (condition being about 10 DEG C in salt lake brine temperature is carried out), obtain the first liquid phase bittern.
S202 first time low-temperature evaporation: get 400kg first liquid phase bittern, be placed in environmental chamber, regulate simulating chamber temperature, make brine temperature control at 5.5 DEG C, electric fan is interrupted air draft, and blast velocity control is at 3.50m/s.Li in evaporative process monitoring bittern
+concentration, works as Li
+during mass concentration 0.4500%, the salt mine that bittern and evaporation are separated out is carried out solid-liquid separation, obtains solid phase 30.0kg second solid phase salt mine, 13.28kg second liquid phase bittern.
S203 first time cools placement: second liquid phase bittern is placed in the moderate evaporation tank of volume, and adjustment environment analog room temperature degree, measure brine temperature, make its temperature at-6.5 DEG C, bittern liquidus temperature places 4.5h after reaching this scope, cooling rate 0.2 DEG C.Carry out solid-liquid separation, obtain 2.46kg the 3rd solid phase salt mine, 7.33kg the 3rd liquid phase bittern.
S204 second time low-temperature evaporation, is placed in the moderate evaporation tank of volume by the 3rd liquid phase bittern, and adjustment environment analog room temperature degree, measure brine temperature, make its temperature at 4.70 DEG C, wind speed and ambient relative humidity remain unchanged, and evaporate bittern.Evaporative process monitoring bittern and evaporation separate out Li in solid phase
+concentration, as the Li in liquid phase
+when mass concentration reaches 15 times of concentration in solid phase, the salt mine that bittern and evaporation are separated out is carried out solid-liquid separation, obtains 0.60kg the 4th solid phase salt mine, 7.25kg the 4th liquid phase bittern.
S205 second time cools placement: the 4th liquid phase bittern is placed in the moderate evaporation tank of volume, adjustment environment analog room temperature degree, measure brine temperature, make its temperature at-9.0 DEG C, bittern liquidus temperature places 4.5h after reaching this scope, cooling rate 0.20 DEG C, carries out solid-liquid separation, obtains 0.44kg the 5th solid phase salt mine, 6.86kg the 5th liquid phase bittern.
S206 third time low-temperature evaporation: the 5th liquid phase bittern is placed in the moderate evaporation tank of volume, adjustment environment analog room temperature degree, measure brine temperature, make its temperature at 4.70 DEG C, wind speed and ambient relative humidity remain unchanged, and evaporate bittern.Evaporative process monitoring bittern and evaporation separate out Li in solid phase
+concentration, as the Li in liquid phase
+when mass concentration reaches 20 times of concentration in solid phase, the salt mine that bittern and evaporation are separated out is carried out solid-liquid separation, obtains 0.63kg the 6th solid phase salt mine, 4.27kg the 6th liquid phase bittern.
S207 second time high temperature evaporation: the 6th liquid phase bittern is placed in the moderate evaporation tank of volume, adjustment environment analog room temperature degree, measure brine temperature, make its temperature at 15.0 DEG C, wind speed and ambient relative humidity remain unchanged, and evaporate bittern.The salt mine that bittern and evaporation are separated out is carried out solid-liquid separation, obtains solid phase 1.15kg salt mine, liquid phase 0.89kg bittern.
The total recovery 60.01% of lithium ion.
Table 3: in the method for embodiment 2, each step products component list
embodiment 3
S301 first time high temperature evaporation: after Tibet salt lake brine is mixed, be placed in evaporation tank high temperature evaporation (condition being about 30 DEG C in salt lake brine temperature is carried out), obtain the first liquid phase bittern.
S302 first time low-temperature evaporation: get 400kg first liquid phase bittern, be placed in environmental chamber, regulate simulating chamber temperature, make brine temperature control at 6.0 DEG C, electric fan is interrupted air draft, and blast velocity control is at 3.80m/s.Li in evaporative process monitoring bittern
+concentration, works as Li
+during mass concentration 0.5000%, the salt mine that bittern and evaporation are separated out is carried out solid-liquid separation, obtains solid phase 27.5kg second solid phase salt mine, 13.4kg second liquid phase bittern.
S303 first time cools placement: second liquid phase bittern is placed in the moderate evaporation tank of volume, and adjustment environment analog room temperature degree, measure brine temperature, make its temperature at-4.5 DEG C, bittern liquidus temperature places 4h after reaching this scope, cooling rate 0.35 DEG C.Carry out solid-liquid separation, obtain 2.45kg the 3rd solid phase salt mine, 7.40kg the 3rd liquid phase bittern.
S304 second time low-temperature evaporation, is placed in the moderate evaporation tank of volume by the 3rd liquid phase bittern, and adjustment environment analog room temperature degree, measure brine temperature, make its temperature at 4.80 DEG C, wind speed and ambient relative humidity remain unchanged, and evaporate bittern.Evaporative process monitoring bittern and evaporation separate out Li in solid phase
+concentration, as the Li in liquid phase
+when mass concentration reaches 20 times of concentration in solid phase, the salt mine that bittern and evaporation are separated out is carried out solid-liquid separation, obtains 0.70kg the 4th solid phase salt mine, 7.00kg the 4th liquid phase bittern.
S305 second time cools placement: the 4th liquid phase bittern is placed in the moderate evaporation tank of volume, adjustment environment analog room temperature degree, measure brine temperature, make its temperature at-8.0 DEG C, bittern liquidus temperature places 4h after reaching this scope, cooling rate 0.5 DEG C, carries out solid-liquid separation, obtains 0.45kg the 5th solid phase salt mine, 6.84kg the 5th liquid phase bittern.
S306 third time low-temperature evaporation: the 5th liquid phase bittern is placed in the moderate evaporation tank of volume, adjustment environment analog room temperature degree, measure brine temperature, make its temperature at 4.80 DEG C, wind speed and ambient relative humidity remain unchanged, and evaporate bittern.Evaporative process monitoring bittern and evaporation separate out Li in solid phase
+concentration, as the Li in liquid phase
+when mass concentration reaches 15 times of concentration in solid phase, the salt mine that bittern and evaporation are separated out is carried out solid-liquid separation, obtains 0.62kg the 6th solid phase salt mine, 4.28kg the 6th liquid phase bittern.
S307 second time high temperature evaporation: the 6th liquid phase bittern is placed in the moderate evaporation tank of volume, adjustment environment analog room temperature degree, measure brine temperature, make its temperature at 12.5 DEG C, wind speed and ambient relative humidity remain unchanged, and evaporate bittern.The salt mine that bittern and evaporation are separated out is carried out solid-liquid separation, obtains solid phase 1.16kg salt mine, liquid phase 0.88kg bittern.
The total recovery 64.95% of lithium ion.
Table 4: in the method for embodiment 3, each step products component list
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (9)
1. the method for enriching lithium from carbonate type salt lake brine, comprising:
Low-temperature evaporation alternately and freezing placement process are carried out to salt lake brine; And
After each evaporation or placing, carry out solid-liquid separation, to remove solid phase salt mine, obtain Li
+the liquid phase bittern of enrichment, wherein
Described low-temperature evaporation carries out in the condition that liquid phase brine temperature is 4 DEG C to 6 DEG C;
And in described freezing placement, the temperature of liquid phase bittern is down to the temperature of-10.0 DEG C to-4.0 DEG C;
In described low-temperature evaporation process, monitor Li in solid phase salt mine and liquid phase bittern
+mass concentration, until Li in liquid phase bittern
+mass concentration reach Li in solid phase salt mine
+during 10 to 20 times of mass concentration, complete a low-temperature evaporation process.
2. the method for claim 1, wherein described low-temperature evaporation is also attended by air draft operation.
3. method as claimed in claim 2, wherein, the wind speed of described air draft operation is 2.8m/s to 3.8m/s.
4. the method for claim 1, wherein described freezing placement carry out 4h to 5h.
5., during the method for claim 1, wherein described freezing placement processes, the rate of temperature fall of liquid phase bittern is 0.2 DEG C/min to 0.5 DEG C/min.
6. the method for claim 1, wherein the low-temperature evaporation that at least two-wheeled replaces, freezing placement process are carried out to salt lake brine.
7. the method for claim 1, also comprises: before low-temperature evaporation first, carry out first time evaporation process, Li to liquid phase to liquid phase bittern
+content reaches capacity; And/or the last time after low-temperature evaporation or freezing placement process, second time evaporation process is carried out to liquid phase bittern, Li to liquid phase
+content reaches capacity, and solid-liquid separation, removes the step of solid phase salt mine.
8. method as claimed in claim 7, wherein, described first time evaporation is carried out in the condition that liquid phase brine temperature is 10.0 DEG C to 30.0 DEG C, and the evaporation of described second time is carried out in the condition that liquid phase brine temperature is 10.0 DEG C to 15.0 DEG C.
9. the method for claim 1, wherein said method comprising the steps of:
S1 first time high temperature evaporation, makes salt lake brine evaporate, until Li in liquid phase the temperature of 10.0 DEG C to 30.0 DEG C
+content reaches or close to saturated, solid-liquid separation obtains the first solid phase salt mine and the first liquid phase bittern;
S2 first time low-temperature evaporation, makes the first liquid phase bittern evaporate, until Li in liquid phase bittern the temperature of 4 DEG C to 6 DEG C
+mass concentration rise to 0.40% to 0.50%, solid-liquid separation obtains second solid phase salt mine and second liquid phase bittern;
S3 first time freezing placement, makes second liquid phase bittern be cooled to-8.0 DEG C to-4.5 DEG C, and place 4h to 5h, solid-liquid separation obtains the 3rd solid phase salt mine and the 3rd liquid phase bittern;
S4 second time low-temperature evaporation, makes the 3rd liquid phase bittern evaporate, until Li in liquid phase bittern the temperature of 4.6 DEG C to 4.8 DEG C
+mass concentration reach 10 to 20 times of mass concentration in solid phase salt mine, solid-liquid separation obtains the 4th solid phase salt mine and the 4th liquid phase bittern;
The freezing placement of S5 second time, make the 4th liquid phase bittern be cooled to-9.5 DEG C to-8.0 DEG C, place 4h to 5h, solid-liquid separation obtains the 5th solid phase salt mine and the 5th liquid phase bittern;
S6 third time low-temperature evaporation, makes the 5th liquid phase bittern evaporate, until Li in liquid phase bittern the temperature of 4.6 DEG C to 4.8 DEG C
+mass concentration reach 10 to 20 times of mass concentration in solid phase salt mine, solid-liquid separation obtains the 6th solid phase salt mine and the 6th liquid phase bittern;
S7 second time high temperature evaporation, makes the 6th liquid phase bittern evaporate, until Li in liquid phase the temperature of 10.0 DEG C to 15.0 DEG C
+content reaches or close to saturated, solid-liquid separation, obtains the 7th solid phase salt mine and the 7th liquid phase bittern, wherein
Li in described 7th liquid phase bittern
+mass concentration be more than or equal to 30g/L.
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| CN107337217B (en) * | 2016-04-28 | 2020-03-06 | 中国地质科学院盐湖与热水资源研究发展中心 | System and method for concentrating and separating light salt lake brine |
| CN106435227B (en) * | 2016-09-09 | 2018-10-02 | 中国科学院青海盐湖研究所 | The enrichment method of uranium element in a kind of brine |
| CN110194471B (en) * | 2019-06-19 | 2020-11-06 | 中国科学院青海盐湖研究所 | Method for desulfurizing sodium sulfate subtype salt lake brine and enriching lithium |
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