CN104961143A - Method for extracting lithium from salt lake brine - Google Patents
Method for extracting lithium from salt lake brine Download PDFInfo
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- CN104961143A CN104961143A CN201510392024.0A CN201510392024A CN104961143A CN 104961143 A CN104961143 A CN 104961143A CN 201510392024 A CN201510392024 A CN 201510392024A CN 104961143 A CN104961143 A CN 104961143A
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- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
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Abstract
A method for extracting lithium from salt lake brine comprises the steps: (1) acidizing to removing boron: adding acids into the brine to precipitate boric acid, and performing solid liquid separation, to obtain first liquor; (2) preprocessing: removing partial sulfate radicals and magnesium ions in the first liquor in a precipitating way to obtain second liquor; (3) performing lithium magnesium separation: separating the lithium and magnesium in the second liquor by adopting a lithium magnesium separation membrane to obtain high-magnesium low-lithium product water and high-lithium low-magnesium product water; (4) lithium concentrating: adopting a lithium concentration membrane to concentrate the low-magnesium and high-lithium product water obtained in the step 3 to obtain a concentrated solution and a thin solution; (5) refining to precipitate the lithium, rising pH of the concentrated solution obtained in the step 4, removing Mg <2+> in a form of Mg(OH)2 sediment to obtain third liquor, inducing CO3<2-> and Li<+> into the third liquor for precipitation in a form of Li2CO3, separating, washing and drying the sediment to obtain the cell grade Li2CO3 product.
Description
Technical field
The disclosure relates to technical field of membrane separation, particularly relates to chemical precipitation method and membrane separation process and combines the method extracting lithium from salt lake saline.
Background technology
The mankind are striving to find the new forms of energy of alternative fossil energy always in recent decades, and the most general Land use systems of new forms of energy is electrical power storage by various forms of Conversion of energy.The outstanding advantage such as specific storage is high, operating temperature range is wide, self-discharge rate is low owing to possessing for lithium ion battery, have extended cycle life, safety performance is good, be widely applied in mobile communication equipment and various digital product, and be acknowledged as the ideal source of electromobile.Thus, even if global economy slowdown in growth in recent years, the performance of lithium industry is but especially outstanding, and lithium product is one of minority industrial goods of price increase, and thus the acquisition of lithium resource also becomes the focus that countries in the world are paid close attention to.
In explored world lithium resource, bittern lithium resource accounts for 61%, ore lithium resource accounts for 34%, oil field and GEOTHERMAL WATER lithium resource account for 5%.With regard to current economy, the state of the art, from salt lake brine, extract lithium on cost and scale, no matter be all better than ore carry lithium, there is the lithium product of 70% in the whole world from salt lake brine.China's salt lake brine lithium reserves account for more than 80% of total reserves, but the lithium extracted from salt lake brine but only accounts for 8% of total extracted amount, and reason is many-sided.Wherein topmost reason is, saline lakes of China bittern is the bittern of high Mg/Li ratio mostly, due to Mg
2+with Li
+closely similar in physicochemical property, cause magnesium lithium separation difficulty, cannot with simple chemical process (as the precipitator method) extracting directly lithium, the existing method extracting lithium from high Mg/Li ratio bittern comprises organic solvent extractionprocess, ion exchange method, electroosmose process, Nanofiltering membrane etc. at present.Organic solvent extractionprocess production cost is high, serious to equipment corrosion, at present also in experimental stage; The sorbent material price that ion exchange method adopts is very high, and productivity is low, and very easily contaminated, cannot scale operation; Electrodialysis rule needs to consume a large amount of electric energy, and produces chlorine poisonous in a large number in production process; Nanofiltering membrane has very large advantage relative to aforesaid method.From principle, nanofiltration membrane is a kind of pressure drive membrane, with charged group on film, by electrostatic interaction, produces Donnan effect, has different selective penetrated property, thus realize the separation of different valence state ion to the ion of different valence state.In general, nanofiltration membrane is 10% ~ 80% to the rejection of univalent ion, have sizable perviousness, and the rejection of divalence and a polyvalent salt is all more than 90%, thus realizes being separated of monovalence lithium ion and divalence magnesium ion.Domestic existing enterprise utilizes this technology to extract lithium from salt lake brine, but still there is some problem and cause that production efficiency is low, cost remains high.
Summary of the invention
Embodiments of the invention provide a kind of method of separation and Extraction lithium from bittern, comprising:
1) acidifying is except boron, and acid adding in bittern, is settled out boric acid, solid-liquid separation, obtains the first clear liquid;
2) pre-treatment, removes part sulfate radical and magnesium ion in described first clear liquid in the mode precipitated, obtains the second clear liquid;
3) Separation of Li and Mg, adopts the lithium in the second clear liquid described in Separation of Li and Mg membrane sepn and magnesium, obtains the low lithium of high magnesium and produces water and high lithium low magnesium product water;
4) lithium concentrates, and the low magnesium of described high lithium adopting lithium to concentrate membrane concentration step 3 gained produces water, obtains concentrated solution and light liquid;
5) refining sinker, the pH of ascending step 4 gained concentrated solution, by Mg
2+with Mg (OH)
2the form of precipitation is removed, and obtains the 3rd clear liquid, in described 3rd clear liquid, introduces CO
3 2-, Li
+with Li
2cO
3form precipitation, isolate throw out and obtain battery-level lithium carbonate product after washing drying.
In one embodiment of the invention, such as at least one that the low lithium of high magnesium of above-mentioned steps 3 produces in the light liquid of water, step 4 can be returned and merges with described second clear liquid of step 2.
In one embodiment of the invention, such as, pretreated step 2 comprises step 2A and step 2B,
Step 2A comprises: the pH to 7-9 of described first clear liquid of regulating step 1, the SO in bittern
4 2-and Mg
2+a part with the form of calcium sulfate and magnesium hydroxide precipitation, obtain clear liquid 2A after solid-liquid separation and enter step 2B and continue process or enter step 3 to continue process;
Step 2B comprises: with subsequent step return after clear liquid merges, remaining SO in bittern
4 2-and Mg
2+a part continue with the form of calcium sulfate and magnesium hydroxide precipitation, obtain clear liquid 2B after solid-liquid separation and enter step 3 and continue process.
In one embodiment of the invention, such as, the step 3 of Separation of Li and Mg comprises step 3A and step 3B,
Step 3A comprises: in step 2 gained clear liquid, add acid, regulate pH to 7-8.5, utilize Separation of Li and Mg membrane sepn clear liquid to obtain the low lithium of high magnesium and produce water 3A and high lithium low magnesium product water 3A, after wherein high magnesium low lithium product water 3A returns salt pan enrichment method, merge with raw brine, the low magnesium of high lithium produces water 3A and then enters step 3B continuation process or enter step 4 continuation process again;
Step 3B comprises: produce in water 3A at the low magnesium of high lithium and add complexing agent, utilize the low magnesium of Separation of Li and Mg membrane sepn height lithium to produce water 3A and obtain high magnesium low lithium product water 3B and high lithium low magnesium product water 3B, wherein high magnesium low lithium product water 3B returns and merges with the clear liquid of step 2A, and the low magnesium of high lithium produces water 3B and then enters step 4 continuation process.
In one embodiment of the invention, such as, the step 4 that lithium concentrates comprises step 4A, step 4B and step 4C,
Step 4A comprises: adopt lithium to concentrate the high lithium of film to step 3 low magnesium product water and concentrate, obtain concentrated solution 4A and light liquid 4A, wherein light liquid 4A returns and merges with the clear liquid of step 2A, and concentrated solution 4A then enters step 4B to be continued process or enter step 5 to continue process;
Step 4B comprises: adopt lithium to concentrate the concentrated solution 4A of film to step 4A and concentrate, obtain concentrated solution 4B and light liquid 4B, wherein light liquid 4B returns and merges with the clear liquid of step 2A, and concentrated solution 4B then enters step 4C to be continued process or enter step 5 to continue process;
Step 4C comprises: adopt lithium to concentrate the concentrated solution 4B of film to step 4B and concentrate, obtain concentrated solution 4C and light liquid 4C, wherein light liquid 4C returns and merges with the clear liquid of step 2A, and concentrated solution 4C then enters step 5 and continues process.
In one embodiment of the invention, such as, above-mentioned steps 1 acidifying comprises except boron: acid adding regulate salt lake brine pH be 2-4 to boric acid crystallization, solid-liquid separation obtains clear liquid and thick boric acid.
In one embodiment of the invention, such as, above-mentioned steps 2B comprises: in clear liquid 2A, add flocculating aids, with subsequent step return after clear liquid merges, remaining SO in bittern
4 2-and Mg
2+a part continue, with the form of calcium sulfate and magnesium hydroxide precipitation, to adopt tetrafluoroethylene microfiltration membrane by CaSO
4, Mg (OH)
2floss obtains clear liquid 2B and enters step 3 continuation process after being separated.
In one embodiment of the invention, such as, the low lithium of above-mentioned high magnesium produces lithium concentration in water 3A and is less than 150ppm, and the low magnesium of high lithium produces lithium concentration in water 3A and is greater than 300ppm; The low magnesium of high lithium produces lithium concentration in water 3B and is greater than 300ppm and lithium magnesium mass ratio is greater than 1.
In one embodiment of the invention, such as, in above-mentioned concentrated solution 4A, lithium concentration is greater than 1000ppm and lithium magnesium mass ratio is greater than 1; In concentrated solution 4B, lithium concentration is greater than 2000ppm and lithium magnesium mass ratio is greater than 1; In concentrated solution 4C, lithium concentration is greater than 16000ppm and lithium magnesium mass ratio is greater than 1.
In one embodiment of the invention, such as, in step 2A, the mode of the pH of described first clear liquid of described regulating step 1 comprises: add NaOH, NH
4oH, KOH or Ca (OH)
2.
In one embodiment of the invention, such as, described flocculating aids is perlite, diatomite or Mierocrystalline cellulose, and the add-on of described flocculating aids is 30-50ppm.
In one embodiment of the invention, such as, in step 3A, the acid added in step 2 gained clear liquid comprises one in hydrochloric acid, sulfuric acid, nitric acid or its combination.
In one embodiment of the invention, such as, in step 3B, producing at the low magnesium of high lithium the complexing agent added in water 3A is composite EDETATE SODIUM salt, ethylenediamine tetraacetic acid (EDTA), edetate, Amino Trimethylene Phosphonic Acid, divinyl triammonium pentamethylene phosphonic acids, hydroxy ethylene diphosphonic acid or Sodium hexametaphosphate 99, and concentration is 3-6ppm.
In one embodiment of the invention, such as, the method wherein obtaining clear liquid in step 5 is: in the concentrated solution of step 4, add sodium hydroxide, obtain slip, part Mg in this slip
2+with Mg (OH)
2form precipitation, above-mentioned slip solid-liquid separation is obtained magnesium hydrate precipitate and a lixivium, magnesium hydrate precipitate carries out once above leaching with water or filtrate again, solid-liquid separation obtains magnesium hydrate precipitate and filtrate, is configured sodium hydroxide this filtrate being used for and continue reuse, a lixivium filters and obtains clear liquid.
In one embodiment of the invention, such as, the method for described solid-liquid separation comprises: high speed centrifugation separation, sheet frame solid-liquid separation, tetrafluoroethylene microfiltration membrane are separated and/or filter.
Accompanying drawing explanation
In order to be illustrated more clearly in the technical scheme of the embodiment of the present invention, be briefly described below by the accompanying drawing of embodiment, apparently, the accompanying drawing in the following describes only relates to some embodiments of the present invention, but not limitation of the present invention.
The method flow diagram of a kind of separation and Extraction lithium from bittern that Fig. 1 provides for one embodiment of the invention;
The method flow diagram of a kind of separation and Extraction lithium from bittern that Fig. 2 provides for further embodiment of this invention;
The method flow diagram of a kind of separation and Extraction lithium from bittern that Fig. 3 provides for third embodiment of the invention;
The method flow diagram of a kind of separation and Extraction lithium from bittern that Fig. 4 provides for fourth embodiment of the invention.
Embodiment
For making the object of the embodiment of the present invention, technical scheme and advantage clearly, below in conjunction with the accompanying drawing of the embodiment of the present invention, the technical scheme of the embodiment of the present invention is clearly and completely described.Obviously, described embodiment is a part of embodiment of the present invention, instead of whole embodiments.Based on described embodiments of the invention, other embodiments all that those of ordinary skill in the art obtain under without the need to the prerequisite of creative work, all belong to the scope of protection of the invention.
Unless otherwise defined, technical term used herein or scientific terminology should be in field belonging to the present invention the ordinary meaning that the personage with general technical ability understands." first ", " second " that use in patent application specification of the present invention and claims and similar word do not represent any order, quantity or importance, and are only used to distinguish different integral parts.Equally, the similar word such as " " or " " does not represent quantity limitation yet, but represents to there is at least one.
Unless otherwise defined, ppm is mass ratio herein, and it is identical that Chinese and chemical formula state implication, such as magnesium ion and Mg
2+, sulfate ion and SiO
4 2-deng.
There is the technology of some nanofiltration membrane separation and Extraction lithium from bittern in this area, the Chinese Patent Application No. 0310808088.X of Qinghai Lake institute of the Chinese Academy of Sciences is by commercial multistage nanofiltration membrane separating magnesium and enriching lithium from salt lake brine, but bittern is not removed sulfate radical before entering nanofiltration membrane separation, the foreign ions such as borate, cause membrane sepn efficiency low, and the duct of nanofiltration membrane is often blocked by flocculent precipitate in use procedure, impact is produced and cost raises, the rich lithium bittern using this technology to purify to obtain does not reach concentration and the purity of practical application in industry yet, the raw brine of the Chinese Patent Application No. 201010295933.X first dilute with water height saliferous of Wang Hui, then by one or more levels nanofiltration membrane separation magnesium and lithium, concentrate finally by reverse osmosis membrane or membrane distillation system, this technology does not consider the impact of other ion pair sepn processes beyond demagging equally, membrane sepn efficiency is not high, and this method is by nanofiltration membrane plural serial stage in addition, and the dense water of next stage returns upper level charging, Mg/Li ratio so can be caused to raise, reduce membrane sepn efficiency.
For the above-mentioned problems in the prior art, embodiments of the invention provide a kind of comprehensive lithium ion (Li combining the methods such as chemical method, physics impurity removal method, nanofiltration membrane separation method, concentrated embrane method
+) extracting method, by the additive method beyond the membrane separation processes such as chemical method, physics impurity removal method, before membrane sepn, remove the most of foreign ion existed in salt lake brine in advance, as Mg
2+, SO
4 2-, B
2+deng, for membrane sepn creates good condition, substantially increase membrane sepn efficiency, optimize separating effect; In membrane separating process and after membrane sepn, equally in conjunction with aforesaid method, further increase the efficiency and purity of extracting lithium.Before the present invention occurs, adopt membrane separation process to extract lithium from salt lake and generally only can reach technical grade, and due to the existence of a large amount of foreign ion, often produce a large amount of precipitation in membrane separating process and cause the dirt of film to block up, affect production schedule on the one hand, too increase production cost on the other hand.Adopt method of the present invention to extract from salt lake brine purity that lithium then can reach cell-grade, namely a large amount of foreign ion was removed before membrane sepn simultaneously, the dirt problem of blocking up in membrane separating process have also been obtained solution, substantially prolongs the production cycle, reduces production cost.
It should be noted that, in this article, " the low lithium of high magnesium produces water " in Separation of Li and Mg step does not mean that the concentration ratio lithium of wherein magnesium is high, " the low magnesium of high lithium produces water " does not mean that the concentration ratio magnesium of wherein lithium is high yet, but say in same step (as step 3A), the lithium magnesium ratio (mass ratio) in " the low lithium of high magnesium produces water " will lower than the lithium magnesium ratio (mass ratio) in " the low magnesium of high lithium produces water ".
Embodiment 1
As shown in Figure 1, raw material be from salt lake containing lithium bittern or other sources containing lithium bittern.The salt lake brine adopted in the embodiment of the present invention is all the salt lake brine of high Mg/Li ratio, Mg/Li ratio (Mg
2+: Li
+mass ratio) general more than 20.
Acid adding in raw brine, regulate bittern pH be 2-4 to boric acid crystallization, solid-liquid separation obtains clear liquid and thick boric acid.Thick boric acid can process sale further, and clear liquid then enters step 2 and carries out pre-treatment.
In pre-treatment step, remove part sulfate radical and magnesium ion (sulfate radical clearance about 90%, magnesium ion clearance about 10-15%) in bittern, solid-liquid separation in the mode precipitated, clear liquid enters next step and continues process.The mode of precipitation comprises conventional chemistry or physical sedimentation method, as added alkali lye, magnesium ion being precipitated with the form of magnesium hydroxide, adding barium ion and sulfate ion is precipitated, or change solution temperature makes calcium sulfate solubleness change thus precipitation etc.
Adopt Separation of Li and Mg film to carry out Separation of Li and Mg to the clear liquid of pre-treatment step, obtain the low lithium of high magnesium and produce water and high lithium low magnesium product water, wherein the low magnesium of high lithium produces water and enters next step continuation process.The lithium ion content that the low magnesium of described high lithium produces in water is greater than 300PPM, and lithium magnesium mass ratio is greater than 1:1.Described Separation of Li and Mg film can adopt and can be separated monovalent ion and bivalent ions nanofiltration membrane.Nanofiltration membrane is a kind of pressure drive membrane, due to normal with charged group on film or in film, by electrostatic interaction, produce Donnan effect, to the ion of different valence state, has different selectivity, thus realize the separation of different valence state ion.There is commercial Separation of Li and Mg film in this area, as there are relevant product line in the companies such as Membrane Products, Nitto, Osmonics.Certainly, the above-mentioned technique that the embodiment of the present invention provides also can utilize the Separation of Li and Mg film prepared voluntarily.
Produce water to the low magnesium of the high lithium of previous step gained to concentrate, obtain concentrated solution and light liquid, wherein concentrated solution enters next step continuation process.Concentrated method can adopt lithium to concentrate the low magnesium of film process height lithium and produce water.Described lithium concentrates film and is generally reverse osmosis membrane, commercial product can be adopted, as the series product in Tao Shi (DOW), Coriolis (KOCH), Hydranautics (HYDRANAUTICS), GE, east beautiful (TORAY) etc.The above-mentioned technique that the embodiment of the present invention provides also can utilize the lithium prepared voluntarily to concentrate film.In the concentrated concentrated solution obtained, lithium content is greater than 16000PPM, and lithium magnesium mass ratio is greater than 1:1.
Refining sinker, raises the pH of the concentrated solution of previous step, by Mg
2+with Mg (OH)
2the form of precipitation is removed, and obtains clear liquid, in clear liquid, introduces CO
3 2-, Li
+with Li
2cO
3form precipitation, isolate throw out and wash drying and obtain battery-level lithium carbonate product, purity >99.5%.
Embodiment 2
As shown in Figure 2, another embodiment of the present invention provides a kind of method of separation and Extraction lithium from bittern, and compared with the method provided with embodiment 1, the method that the present embodiment provides has the step of more segmentations, comprising:
1) acidifying is except boron, and clear liquid enters next step and continues process;
2) pre-treatment, removes part sulfate radical and magnesium ion in bittern in the mode precipitated; Pre-treatment step 2 comprises step 2A and step 2B, and step 2A comprises: the pH of the clear liquid of ascending step 1, regulates pH to 7-9, the SO in bittern
4 2-and Mg
2+a part with the form of calcium sulfate and magnesium hydroxide precipitation, obtain clear liquid 2A after solid-liquid separation and enter step 2B and continue process; Step 2B comprises: in clear liquid 2A, add flocculating aids (as equal grain perlite, add-on is 30-50ppm), remaining SO in bittern
4 2-and Mg
2+a part continue with the form of calcium sulfate and magnesium hydroxide precipitation, obtain clear liquid 2B after solid-liquid separation and enter step 3 and continue process.
3) Separation of Li and Mg, adopts Separation of Li and Mg membrane sepn lithium and magnesium, obtains the low lithium of high magnesium and produces water and high lithium low magnesium product water; Step 3 comprises step 3A and step 3B, step 3A comprises: in step 2B gained clear liquid, add acid, regulate pH to 7-8.5, utilize Separation of Li and Mg membrane sepn clear liquid to obtain the low lithium of high magnesium and produce water 3A and high lithium low magnesium product water 3A, the low magnesium of high lithium produces water 3A and enters step 3B continuation process; Step 3B comprises: produce in water 3A at the low magnesium of high lithium and add the complexing agent (Scale inhibitors that described complexing agent can adopt water treatment field conventional, can be such as composite EDETATE SODIUM salt, ethylenediamine tetraacetic acid (EDTA), edetate, Amino Trimethylene Phosphonic Acid, divinyl triammonium pentamethylene phosphonic acids, hydroxy ethylene diphosphonic acid or Sodium hexametaphosphate 99, concentration is 3-6ppm), utilize the low magnesium of Separation of Li and Mg membrane sepn height lithium to produce water 3A and obtain high magnesium low lithium product water 3B and high lithium low magnesium product water 3B, the low magnesium of high lithium produces water 3B and enters step 4 continuation process.
4) lithium concentrates, and the low magnesium of high lithium adopting lithium to concentrate membrane concentration step 3 gained produces water, obtains concentrated solution and light liquid, and wherein concentrated solution enters next step continuation process; The concentrated step 4 of lithium comprises step 4A, step 4B and step 4C, and step 4A comprises: adopt lithium to concentrate the low magnesium of the high lithium of film to step 3 and produce water and concentrate, and obtains concentrated solution 4A and light liquid 4A, concentrated solution 4A and enters step 4B and continue process; Step 4B comprises: adopt lithium to concentrate the concentrated solution 4A of film to step 4A and concentrate, and obtains concentrated solution 4B and light liquid 4B, concentrated solution 4B and enters step 4C and continue process; Step 4C comprises: adopt lithium to concentrate the concentrated solution 4B of film to step 4B and concentrate, and obtains concentrated solution 4C and light liquid 4C, concentrated solution 4C and enters step 5 and continue process.
5) refining sinker, the pH of the concentrated solution of ascending step 4, by Mg
2+with Mg (OH)
2the form of precipitation is removed, and obtains clear liquid, in clear liquid, introduces CO
3 2-, Li
+with Li
2cO
3form precipitation, isolate throw out and drying obtains battery-level lithium carbonate product, purity >99.7%.The above-mentioned method obtaining clear liquid is: in the concentrated solution of step 4, add sodium hydroxide, obtain slip, part Mg in this slip
2+with Mg (OH)
2form precipitation, above-mentioned slip solid-liquid separation is obtained magnesium hydrate precipitate and a lixivium, magnesium hydrate precipitate carries out once above leaching with water or filtrate again, solid-liquid separation obtains magnesium hydrate precipitate and filtrate, by this filtrate recycle in configuration sodium hydroxide solution, a lixivium filters and obtains clear liquid.
The aforesaid method that embodiment 2 provides has more fine division step, Separation of Li and Mg effect can be made better on the one hand, and the purity obtaining the finished product Quilonum Retard is also higher; Removed by throw out in bittern more thorough on the other hand, situation is blocked up in the dirt decreased in membrane separating process, and the time that the method is run continuously extends greatly, improves the level of automation of whole technique.For pre-treatment step 2, adopt 2A and 2B two pre-treatment step, can the sulfate ion in bittern and magnesium ion be reduced more, decrease the throw out entering next step, thus reduce dirty stifled probability in membrane separating process, be conducive to follow-up Separation of Li and Mg.It should be noted that, step 2,3,4 does not need to segment simultaneously, and can segment certain some step according to actual needs, other a steps then step complete.The Quilonum Retard purity >99.6% that the present embodiment finally obtains.
Embodiment 3
As shown in Figure 3, another embodiment of the present invention provides a kind of method of separation and Extraction lithium from bittern, and compared with the method provided with embodiment 2, the method that the present embodiment provides reclaims the Li that each step produces
+the solution that content is lower, to improve overall lithium ion extraction rate.Content identical with embodiment 2 in the present embodiment will be omitted, and emphasis describes not identical part.As shown in Figure 3, after the high magnesium that step 3A obtains low lithium product water 3A returns salt pan enrichment method, merge with raw brine again, the high magnesium that step 3B obtains low lithium product water 3B returns and merges with the clear liquid of step 2A, the light liquid 4A that step 4A obtains returns and merges with the clear liquid of step 2A, the light liquid 4B that step 4B obtains returns and merges with the clear liquid of step 2A, and the light liquid 4C that step 4C obtains returns and merges with the clear liquid of step 2A.Due to the Li that each step produces
+the solution that content is lower obtains recycling, Li in bittern
+overall extraction yield is improved, and can bring up to more than 80% by 40%.It should be noted that, above-mentioned Li
+the solution that content is lower does not need to reclaim simultaneously, in actual production can according to circumstances choose reasonable wherein a part recycle, to take into account cost and lithium ion extraction rate.The Quilonum Retard purity >99.7% that the present embodiment finally obtains, in bittern, the lithium rate of recovery is more than 80%.
Embodiment 4
As shown in Figure 4, another embodiment of the present invention provides a kind of method of separation and Extraction lithium from bittern, and compared with the method provided with embodiment 3, the method that the present embodiment provides adds auxiliary agent, to optimize the treatment effect of each step further.Content identical with previous embodiment in the present embodiment will be omitted, and emphasis describes not identical part.As shown in Figure 4, step 2A comprises: the pH to 7-9 of the clear liquid of ascending step 1, the SO in bittern
4 2-and Mg
2+a part with the form of calcium sulfate and magnesium hydroxide precipitation.The mode raising pH includes but not limited to, adds NaOH, KOH, Ca (OH) in solution
2or ammoniacal liquor, pass through high speed centrifugation or sheet frame solid-liquid separation after forming precipitation, solid substance can process further as the raw material of magnesium products.The rising of pH can promote the place to go of magnesium, and this process can remove the magnesium of 20 ~ 30%.
As shown in Figure 4, in pre-treatment 2B, flocculating aids is introduced.In clear liquid 2A, add flocculating aids, as equal grain perlite, add-on is 30-50ppm, remaining SO in bittern
4 2-and Mg
2+a part continue, with the form of calcium sulfate and magnesium hydroxide precipitation, to adopt tetrafluoroethylene microfiltration membrane by CaSO
4, Mg (OH)
2floss obtains clear liquid 2B and enters step 3 continuation process after being separated.Flocculating aids is the material that can improve filtrate filtration efficiency.Generally speaking, too closely knit for preventing filter residue from piling up, filtration is carried out smoothly, the insoluble inert material that flocculating aids can adopt granularity different.In the present invention, the example of above-mentioned flocculating aids includes but not limited to perlite, diatomite, Mierocrystalline cellulose etc.
As shown in Figure 4, complexing agent can be introduced in step 3B.Produce in water 3A at the low magnesium of high lithium and add complexing agent, as composite EDETATE SODIUM salt, 3-6ppm, utilize the low magnesium of Separation of Li and Mg membrane sepn height lithium to produce water 3A and obtain high magnesium low lithium product water 3B and high lithium low magnesium product water 3B, wherein high magnesium low lithium product water 3B returns and merges with the clear liquid of step 2A, and the low magnesium of high lithium produces water 3B and then enters step 4 continuation process.The effect of above-mentioned complexing agent is and the complexings such as calcium, barium, strontium prevent calcium sulfate, calcium carbonate, Strontium Sulphate, barium sulfate etc. at film surface scale, damage film.In the present invention, the example of above-mentioned complexing agent includes but not limited to composite EDETATE SODIUM salt, ethylenediamine tetraacetic acid (EDTA), edetate, Amino Trimethylene Phosphonic Acid, divinyl triammonium pentamethylene phosphonic acids, hydroxy ethylene diphosphonic acid or Sodium hexametaphosphate 99 etc.
The above is only exemplary embodiment of the present invention, but not for limiting the scope of the invention, protection scope of the present invention is determined by appended claim.
Claims (16)
1. the method for separation and Extraction lithium from bittern, comprising:
1) acidifying is except boron, and acid adding in bittern, is settled out boric acid, then carries out solid-liquid separation, obtains the first clear liquid;
2) pre-treatment, removes part sulfate radical and magnesium ion in described first clear liquid in the mode precipitated, obtains the second clear liquid;
3) Separation of Li and Mg, adopts the lithium in the second clear liquid described in Separation of Li and Mg membrane sepn and magnesium, obtains the low lithium of high magnesium and produces water and high lithium low magnesium product water;
4) lithium concentrates, and the low magnesium of described high lithium adopting lithium to concentrate membrane concentration step 3 gained produces water, obtains concentrated solution and light liquid;
5) refining sinker, the pH value of ascending step 4 gained concentrated solution, by Mg
2+with Mg (OH)
2the form of precipitation is removed, and obtains the 3rd clear liquid, in described 3rd clear liquid, introduces CO
3 2-, Li
+with Li
2cO
3form precipitation, isolate throw out and obtain battery-level lithium carbonate product after washing drying.
2. method according to claim 1, wherein, at least one of being produced by the low lithium of high magnesium of step 3 in the light liquid of water, step 4 returns and merges with described second clear liquid of step 2.
3. method according to claim 1 and 2, wherein, step 2 comprises step 2A and step 2B,
Step 2A comprises: the pH value of described first clear liquid of regulating step 1, to 7-9, makes the SO in described bittern
4 2-and Mg
2+a part with the form of calcium sulfate and magnesium hydroxide precipitation, obtain clear liquid 2A after carrying out solid-liquid separation, described clear liquid 2A entered step 2B and continue process or enter step 3 to continue process;
Step 2B comprises: remaining SO in bittern
4 2-and Mg
2+a part continue, with the form of calcium sulfate and magnesium hydroxide precipitation, after solid-liquid separation, to obtain clear liquid 2B, described clear liquid 2B is entered step 3 and continues process.
4. method according to claim 3, wherein, step 3 comprises step 3A and step 3B,
Step 3A comprises: in step 2 gained clear liquid, add acid, adjust ph is to 7-8.5, utilize described Separation of Li and Mg membrane sepn clear liquid to obtain the low lithium of high magnesium and produce water 3A and high lithium low magnesium product water 3A, after wherein high magnesium low lithium product water 3A returns salt pan enrichment method, merge with raw brine, the low magnesium of described high lithium produces water 3A and then enters step 3B continuation process or enter step 4 continuation process again;
Step 3B comprises: produce in water 3A at the low magnesium of described high lithium and add complexing agent, the low magnesium of high lithium described in the film of Separation of Li and Mg described in step 3A or new Separation of Li and Mg membrane sepn is utilized to produce water 3A, obtain the low lithium of high magnesium and produce water 3B and high lithium low magnesium product water 3B, wherein said high magnesium low lithium product water 3B returns and merges with the clear liquid of step 2A, and the low magnesium of described high lithium produces water 3B and then enters step 4 continuation process.
5. method according to claim 3, wherein, step 4 comprises step 4A, step 4B and step 4C,
Step 4A comprises: adopt described lithium to concentrate the high lithium of film to step 3 low magnesium product water and concentrate, obtain concentrated solution 4A and light liquid 4A, wherein said light liquid 4A returns and merges with the clear liquid of step 2A, and described concentrated solution 4A then enters step 4B to be continued process or enter step 5 to continue process;
Step 4B comprises: adopt lithium described in step 4A to concentrate film or new lithium and concentrate the concentrated solution 4A of film to step 4A and concentrate, obtain concentrated solution 4B and light liquid 4B, wherein said light liquid 4B returns and merges with the clear liquid of step 2A, and described concentrated solution 4B then enters step 4C to be continued process or enter step 5 to continue process;
Step 4C comprises: adopt lithium described in step 4A to concentrate lithium described in film or step 4B and concentrate film or new lithium and concentrate the concentrated solution 4B of film to step 4B and concentrate, obtain concentrated solution 4C and light liquid 4C, wherein said light liquid 4C returns and merges with the clear liquid of step 2A, and described concentrated solution 4C then enters step 5 and continues process.
6. method according to claim 1 and 2, wherein, in step 1, adds described acid and regulates the pH value of described bittern to be 2-4 extremely described boric acid crystallization, then carry out described solid-liquid separation and obtain described first clear liquid and thick boric acid.
7. method according to claim 3, wherein, in described step 2B, adds flocculating aids, then merges with the clear liquid that subsequent step returns, remaining SO in the treatment solution obtained in described clear liquid 2A
4 2-and Mg
2+a part continue with the form of calcium sulfate and magnesium hydroxide precipitation, after then adopting tetrafluoroethylene microfiltration membrane to be separated with magnesium hydroxide floss by the calcium sulfate be settled out, obtain clear liquid 2B and enter step 3 and continue to process.
8. method according to claim 4, wherein, the low lithium of described high magnesium produces lithium concentration in water 3A and is less than 150ppm, and the low magnesium of described high lithium produces lithium concentration in water 3A and is greater than 300ppm; The low magnesium of described high lithium produces lithium concentration in water 3B and is greater than 300ppm and lithium magnesium mass ratio is greater than 1.
9. method according to claim 5, wherein, in described concentrated solution 4A, lithium concentration is greater than 1000ppm and lithium magnesium mass ratio is greater than 1; In described concentrated solution 4B, lithium concentration is greater than 2000ppm and lithium magnesium mass ratio is greater than 1; In described concentrated solution 4C, lithium concentration is greater than 16000ppm and lithium magnesium mass ratio is greater than 1.
10. method according to claim 3, wherein, in step 2A, the mode of the pH value of described first clear liquid of described regulating step 1 comprises: add NaOH, NH
4oH, KOH or Ca (OH)
2.
11. methods according to claim 7, wherein, described flocculating aids is perlite, diatomite or Mierocrystalline cellulose, and the add-on of described flocculating aids is 30-50ppm.
12. methods according to claim 4, wherein, in step 3A, the acid added in step 2 gained clear liquid comprises one in hydrochloric acid, sulfuric acid, nitric acid or its combination.
13. methods according to claim 4, wherein, in step 3B, produce at the low magnesium of high lithium the complexing agent added in water 3A and comprise composite EDETATE SODIUM salt, ethylenediamine tetraacetic acid (EDTA), edetate, Amino Trimethylene Phosphonic Acid, divinyl triammonium pentamethylene phosphonic acids, hydroxy ethylene diphosphonic acid or Sodium hexametaphosphate 99, the concentration of described complexing agent is 3-6ppm.
14. methods according to claim 1 and 2, wherein, in steps of 5, add sodium hydroxide, obtain slip in the concentrated solution of step 4, by part Mg in described slip
2+with Mg (OH)
2form precipitation, above-mentioned slip is carried out solid-liquid separation and obtains magnesium hydrate precipitate and immersion liquid, described immersion liquid is filtered and obtains described 3rd clear liquid.
15. methods according to claim 14, wherein, described magnesium hydrate precipitate is carried out once above leaching with water or immersion liquid again, and solid-liquid separation obtains magnesium hydrate precipitate and filtrate, is configured sodium hydroxide described filtrate being used for and continues reuse.
16. methods according to claim 1 and 2, the method for wherein said solid-liquid separation comprises: high speed centrifugation separation, sheet frame solid-liquid separation, tetrafluoroethylene microfiltration membrane are separated and/or filter.
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