CN102312110A - Method for extracting alkali metal from salt lake brine and seawater through membrane extraction-back extraction - Google Patents
Method for extracting alkali metal from salt lake brine and seawater through membrane extraction-back extraction Download PDFInfo
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Abstract
The invention discloses a method for extracting high-value alkali metal from salt lake brine or seawater through membrane extraction-back extraction. The method is implemented through continuous operation and comprises the following steps of: fixing an ion exchange blend membrane in a membrane component, allowing an organic solution containing an extracting agent to contact salt lake brine or seawater which contains alkali metal ions by a first ion exchange membrane, and allowing alkali metal ions to pass through the ion exchange membrane and be combined with the organic solution containing the extracting agent to obtain metal complex; then transmitting an organic solution of the metal complex to a second ion exchange membrane and allowing the organic solution of the metal complex to contact a back extraction solution by the second ion exchange membrane, and allowing the metal ions to pass through the ion exchange membrane to enter the back extraction solution; during membrane extraction-back extraction, and circulating feed liquid, the back extraction solution and the organic solution containing the extracting agent on one side of the first ion exchange membrane, on one side of the second ion exchange membrane and between the first and second ion exchange membranes; and performing back extraction until a certain concentration of the back extraction solution is reached, and separating lithium, rubidium or caesium precipitates to obtain the final product. The invention provides a high-efficiency, low-cost and feasible route for industrial production of alkali metal salts.
Description
Technical field
The present invention relates to a kind of alkali-metal technology of high value of from solution, extracting; Be specially adapted to contain lithium seawater or the high Mg/Li ratio salt lake brine and extract high value basic metal such as lithium, rubidium, caesium, and be high value alkaline metal salts such as raw material production lithium, rubidium, caesium with seawater or salt lake brine from lower concentration.
Background technology
High value basic metal mainly refers to lithium, rubidium, caesium, owing to have characteristics such as density is little, fusing point is low, its Application Areas is also more and more wider, enjoys people's attention.Lithium is widely used in ceramics, glass industry, aluminium industry, lubricant, refrigeration agent, high tension battery, controlled nuclear fusion reactor and photoelectricity industry.In recent years, increasing along with the fast development of human economic society to the early autumn of the energy, and traditional energy resources such as coal, oil, Sweet natural gas constantly reduce.So the application of lithium in high tension battery and controlled nuclear fusion reactor quite paid close attention to, and is called as " energy metal ".20th century in the world the production of lithium salts mainly to contain the lithium ore with solid be raw material, yield poorly, cost is high; Far can not satisfy the demand of Economic development; And solid contains, and the lithium ore constantly reduces, grade descends gradually, and lithium resource is abundant in salt lake and the seawater, and the technology of from solution, producing lithium is simple, the solid mineral cost is lower relatively; So salt lake brine and seawater become the research focus of domestic and international extraction lithium gradually.China is salt lake resources big country, and the salt lake lithium resource is China's superior resources, and wherein lithium resource accounts for 1/3rd of salt lake resources reserves.With Qinghai and salt lake, Tibet is main, and present explored lithium resource industrial reserves accounts for the second in the world, is only second to Bolivia.Yet the characteristics of the salt lake resources of China are that the Mg/Li ratio value is high in the salt lake brine, are about 40～1200: 1, and separating difficulty is big, and feasible technology is few.
The outermost electron of rubidium and caesium atom is very unstable, very easily ionization; The dielectric medium that can be used as solid state battery; Make the main sensitive materials of vacuum photocell, carrying out rubidium energetically at ion engine, magnetohydrodynamic generator and two kinds of brand-new generation modes of thermoelectric power generation at present, heat energy directly becomes electric energy; Mechanical rotation part when having saved waterpower and thermal power generation, thus energy utilization ratio improved greatly.The widespread use in this respect of rubidium and caesium is bound to bring a new great technological revolution to generation technology and energy utilization.In addition, the oxide compound of caesium also can be made propellant of high energy, but caesium manufacture of intraocular cesium ion cloud, cesium ion accelerator, and reaction system material and pyrotechnics manufactured materials, be to make atomic clock and Global Positioning System indispensable material.Infrared radiation lamp with the compound of caesium is processed can be found the signal that should not find night; Be used for military reconnaissance, frontier defense patrol, warship night flight etc.; Radiocesium is used for the irradiation of radiation chemistry, medical science, food and medicine etc., also can make chemical catalyst, special glass etc.
Rubidium and caesium distributed in nature are very wide, but do not find simple rubidium and cesium mineral so far as yet, and exist in the mineral such as the lithionite of being everlasting, blotite, carnallitite,, its leaching process is complicated, cost is high, energy consumption is big.Yet also have in salt lake brine and the seawater more to have rubidium and caesium, thereby it extracts, and rubidium, caesium technology are simple relatively, cost is low, power consumption is few, is present rubidium caesium industrial technology development trend with ionic species.Rubidium, caesium normal with element symbiosis such as potassium, sodium, lithium, calcium, magnesium, these symbiosis element physics, chemical property are all very approaching with rubidium, caesium, so bring certain difficulty to separation and Extraction.For a long time, utilize lake bittern water extraction rubidium, caesium fully not to be paid attention to, cause the serious waste of resource.Therefore, rationally utilize rubidium in the salt lake, caesium resource that crucial meaning is arranged, also become the research focus on circle, present China salt lake.
At present; The bittern that abroad is applied is put forward the lithium technology and is only limited to contain the low bittern of magnesium density, and the Mg/Li ratio value is lower than 6: 1, and the Mg/Li ratio value is very high in China's salt lake brine; Can not directly use the lithium method of putting forward of low Mg/Li ratio value, otherwise can cause lithium salts to lose the raising of serious and cost.Put forward the existing many methods of lithium to high Mg/Li ratio value bittern in the world, such as the precipitator method, ionic adsorption method, calcining leaching method, electrodialysis, solvent extration, liquid-film method etc.The method of rubidium and caesium mainly contains the precipitator method, ion exchange method, solvent extration and volatilization method in the separation and Extraction bittern.
High Mg/Li ratio characteristics to China salt lake; Chinese patent CN01128815.9 discloses the method for producing Quilonum Retard in a kind of high Mg/Li ratio salt lake brine: the bittern after potassium magnesium mixed salt is separated out is through the salt pan de-magging; Add precipitation agent then and produce the co-precipitation of boron magnesium; Mother liquor adds saturated NaOH solution and carries out degree of depth demagging, and the last precipitator method are produced Quilonum Retard.This method is owing to need to add a large amount of precipitation agents, and production cost is very high, and product purity is not high enough simultaneously, also needs degree of depth purifying.
After the nineties in last century; U.S. Pat 538934 discloses the ionic adsorption method with US5599516 and has extracted the bittern lithium, has successfully prepared LiCl content and be 012%～0133% LiCl/Al (OH) 3 sorbent materials, extracts the LiCl experiment with being used for after its granulation from containing the higher solution of NaCl; The about 30min of each circulation; The recovery of LiCl can reach 26%, and is difficult for by other ionic soil, not cracky.Industrial experiment shows that loading capacity is 1g LiCl/Al (OH)
32～3mgLi, but because the resin cost is higher, and the regeneration expense is big, thereby be not suitable for salt lake brine scale operation extraction LiCl.Russ P RU1665581 is at first with LiCl2Al (OH)
3NH
2O is applied to the absorption of natural bittern Li+, makes MgCl
2, CaCl
2Deng foreign matter content≤0105g/L; Than low 100～1000 times of original bittern foreign matter content; And then with elutriant foreign matter content is reduced to 01001～01003g/L, last on electrolytic agent tray of containers and electrodialyzer the elutriant with purifying LiCl is converted into LiOH, obtain the LiOH solution of 80～120g/L; It is turned back in the LiCl solution of desalination, obtain only 0.003% LiOHH of foreign matter content
2O is still a great problem to be solved more greatly but dissolve loss rate.This shows that resin cost that the ionic adsorption method is used is high, loading capacity is lower etc., and problem has also limited its development and application.
Chinese patent CN1724372A and CN1724373A disclose a kind of method that the leaching method is produced Quilonum Retard of calcining; The technical process of this method is spraying drying, obtain lithium carbonate product after calcining, add water washing, evaporation concentration, deposition operation; Calcining temperature is 554～1200 ℃, Li after the evaporation concentration
+Content is 14～21g/L, and this method can be effectively from high-Mg Li-contained bittern separation of produced Quilonum Retard, but energy consumption is high, and equipment requirements is high, environmental pollution is big.
Chinese patent CN1335263A discloses carborization and from the high Mg/Li ratio salt lake brine, has produced Quilonum Retard, and this method is to separate out potassium magnesium mixed salt, again in the old saltwater brine after taking off boron, add precipitation agent and make Mg through salt pan evaporation at the magnesium sulfate salt lake brine
2+, Li
+Be precipitated out with oxyhydroxide, carbonate, phosphoric acid salt or oxalate form respectively; This deposition is carried out calcining and decomposing,, make Li through carbonization or carbonation
+Pass into solution, Mg
2+Still keep in the deposition, separate, should carry out deep impurity-removing by richness lithium solution again, subsequently evaporation concentration or with soda ash deposition preparation Quilonum Retard, this method cost is also very high thereby reach the magnesium lithium.
Chinese patent CN1485273A discloses a kind of one-level or multistage osmosis dialysis method taked and has concentrated lithium, and employed parting material is monovalent cation selective ion exchange membrane and monovalent cation selective ion exchange membrane.Mg/Li ratio in its salt lake brine (weight) was up to 300: 1, and the concentration of lithium ion is 0.02～20g/L.The single extraction yield of lithium is more than 80%, and the extrusion rate of magnesium is not less than 95%.This method extraction efficiency is low, and energy consumption is big, and process is complicated.Chinese patent CN1485273A and U.S. Pat 2004/0074774A1 disclose a kind of method that from bittern and seawater, concentrates lithium: this method combines absorption method and two kinds of extractive techniques of electroosmose process, and the lithium concentration in the bittern is concentrated to about 1.5% by number ppm; At first make the bittern of 1200～1500ppm with absorption method, through the electrodialysis process in two stages, the concentration of lithium is brought up to 1.5% then with granular oxides of manganese sorbent.This method and Russ P RU2157338 are close with the WO03/037794A1 disclosed method.
Chinese patent CN1542147A discloses a kind of nano filtering process to be separated and enrichment the lithium in the salt lake brine, produces Quilonum Retard or lithium chloride with the rich lithium bittern of gained.This method is with containing Mg
2+, Ca
2+Deng positively charged ion and SO
4 2-, B
xOy
N-Contain lithium bittern etc. anionic salt pan evaporation gained, wherein Li
+Concentration 0.1～11.5g/L, magnesium lithium weight ratio 1: 1～200: 1 is separated and enrichment wherein lithium through nf membrane, separates the rich lithium bittern magnesium lithium weight ratio that obtains 0.6: 1～5: 1, contains Li
+Concentration 0.6～20g/L.This method is used one macromolecular nano filtering mould material; Maximum problem is that the performance that pollution brought of film reduces and because the poor stability of the mould material that matting causes; In addition, also need pass through additive method through the low magnesium lithium liquid after the nanofiltration and extract lithium, production cost is high.
Solvent extration is put forward the lithium new technology as current very popular both at home and abroad salt lake, is characterized in utilizing the special extraction ability of organic solvent to lithium, can separate basic metal and earth alkali metal effectively and reach and put forward the lithium purpose.U.S. Pat 3537813 has proposed a kind of iron trichloride that in bittern, adds, and makes extraction system extraction lithium with DIBK 80%-tributyl phosphate 20%, gets into the lithium water back extraction of organic phase, owing in anti-stripping agent, contain LiCl and FeCl
3, need to add NaCl and replenish the chlorine root, with two-(2-ethylhexyl) phosphoric acid-tributyl phosphate extraction FeCl
3, reclaim molysite, the lithium salts of in LiCl and NaCl solution, turning one's head again in the water reextraction.The problem that this method exists is that DIBK solubleness in water is big, and price is high, and molysite reclaims that technical process is loaded down with trivial details, and the lithium percentage extraction is low, the percentage extraction of seven grades of lithiums only about 80%.To these problems, Chinese patent CN87103431A has taked a kind ofly directly to extract the process method of lithium chloride from the high-magnesium brine highly selective, makes extraction agent with tributyl phosphate, 200
#Kerosene is thinner, and this extraction agent extraction ability is stable, and selectivity is good, and the percentage extraction of lithium remains between 97～99% in repeatedly circulating, and coexistent impurity almost all separates in the bittern, and magnesium lithium separation factor reaches 1.87 * 10
5But solvent extration extraction solvent consumption is big, and extraction solvent is because dissolving or bigger with the strong acid and strong base loss of reaction directly causes expensive; Extraction process flow is long, and is hierarchical segmented, is difficult to realize automatic control; Etch factor; Organic extractant directly contacts to produce inevitably with raw water and mixes, and additional sepn process is the weakness of whole technology.So,, also be difficult to realize industriallization although this method has a clear superiority in than additive method on the recovery.
To the shortcoming of solvent extraction technology, the liquid-film method stripping technique has appearred, and wherein carrier promotes that immobilized liquid membrane performance in metal separation of transmitting is remarkable; Spent organic extraction liquid is few; Effective contact area of extraction system and raw material liq is high, and extraction efficiency is high, and cost is low; But because the immobilized liquid membrane that loss caused of organic extraction liquid transmits performance and selects performance to reduce, promptly poor stability has restricted the immobilized liquid membrane Industrial Application of Technology.(PAULMA at el.LithiumExtraction from a Multicomponent Mixture Using Supported Liquid Membranes.SEPARATIONSCIENCE AND TECHNOLOGY such as Ma; 35 (15): 2513-2533; 2000) adopt the immobilized liquid membrane technology from bittern, GEOTHERMAL WATER and sea water mixing solution, to extract lithium; The composition of organic extract liquid is that LIX54 and TOPO are dissolved in the kerosene, and this system can extract lithium, Li effectively
+PQ can reach 2 * 10
-6M/s, this penetrating quality stable maintenance 2d is reduced to below 50% behind the 4d.
Chinese patent CN86101311A extracts rare earth, scandium, rubidium, caesium mother liquor with ammonium sulfate or sodium chloride aqueous solution leaching; In extracting rare earth, scandium process; With precipitator method such as condensing crystal, perchloric acid, hexanitrodiphenylamine, tartrate, or hexanitrodiphenylamine, tetraphenyl borate receive-extraction processs such as nitroethane comprehensively reclaim caesium rubidium oxide compound, muriate and oxyhydroxide.Rubidium chloride, caesium solution concentration crystalline deposit method: rubidium chloride or contain the hydrochloric acid soln of rubidium, cesium ion; Heat hydrochloric acid evaporation and cooling are reclaimed; When rubidium in the solution, crystalline deposit went out cesium chloride, rubidium chloride product when caesium concentration was increased to suitable degree, or evaporate dried residual these products that go out that make it.The nitrobenzene solution of hexanitrodiphenylamine can extract caesium, rubidium ion as extraction agent in hydrochloric acid, nitric acid, sodium hydroxide, ammonium chloride, volatile salt medium, but best with the pH=8-9 effect of extracting.Tetraphenyl borate receives-and nitroethane mainly extracts rubidium ion.Hexanitrodiphenylamine and verivate, passive compound etc. are because many difficulties that self are difficult to overcome; Therefore, application in recent years seldom, and solvent extration extraction solvent consumption is big; Extraction solvent is because dissolving or bigger with the strong acid and strong base loss of reaction directly causes expensive; Extraction process flow is long, and is hierarchical segmented, is difficult to realize automatic control; Etch factor; Organic extractant directly contacts to produce inevitably with raw water and mixes, and additional sepn process is the weakness of whole technology.So,, also be difficult to realize industriallization although this method has a clear superiority in than additive method on the recovery.
Chinese patent CN93104780.3 discloses the method for rubidium in a kind of ion exchange method separation and concentration bittern; Used ionite is synthetic by the cupric nitrate and the Tripotassium iron hexacyanide; IX instigator with preceding with the activation of 1mol/L nitric acid dousing, enrichment the exchange column of rubidium use rare nitric acid dousing, use H
2O drip washing, the primary sorption rate reaches 70%, and this method is dissolved the loss rate height because of reagent in bittern, and the saturated capacity of loading capacity is limited, thereby can't be used for large-scale production process.
Volatilization method is based on the vaporization at high temperature characteristic of caesium.(Gay R L et al.Studies of the volatility of cesiumand iodine [J] .Wastes Manage such as Gay; V (2): 357-361,1985.) at first reported caesium 10% volatilization that under 265 ℃, is fixed on the powdery resin in 1985.Subsequently; Tranter and Brewer have studied the volatilization behavior of caesium at high temperature of idaho chemical treatment factory caesium waste liquid; The result shows: handle 6h down at 900 ℃, the maximum volatile quantity of caesium can reach 90%, 1994 year; The experiment of Del Debbio shows: under 1000 ℃, the evaporation rate of caesium in actual waste is 96%; Time and temperature increase, and evaporation rate increases, and under 1170 ℃, the treatment time increases 5h, and the evaporation rate of caesium can reach more than 99%.But because this method needs under high temperature, high radioactivity condition, to operate, high to the requirement of experimental installation, the security of method is not good, is difficult to apply.
Summary of the invention
The objective of the invention is: provide a kind of membrane extraction-reverse extraction technology from salt lake brine or seawater, to extract the alkali-metal method of high value; This method overcomes the existing shortcoming of from contain lithium bittern, extracting alkali-metal method well; Can contain lithium seawater or the high Mg/Li ratio salt lake brine from lower concentration effectively and extract high value basic metal such as lithium, rubidium, caesium, and be high value alkaline metal salts such as raw material production lithium, rubidium, caesium with seawater or salt lake brine.Its technical process simply, at room temperature to carry out, need not impressed pressure, non-secondary pollution, energy consumption low; Organic phase is brought in constant renewal in the process, and is low-cost, efficient is high, and the finished product LiCl and/or LiCO
3Or the grade salt of rubidium, caesium is high.
The object of the invention can reach through following measure: membrane extraction-reverse extraction technology is extracted the alkali-metal method of high value from salt lake brine or seawater; Continous way operation: be fixed on the IX blend film in the membrane module; At first; Contacted with salt lake brine that contains alkalimetal ion or seawater feed liquid through first ion-exchange membrane by the organic solution that contains extraction agent, metals ion sees through ion-exchange membrane and combines to generate metal complex with the organic solution that contains extraction agent; Then, second ion-exchange membrane is delivered in the transmission of the organic solution of metal complex, contacts with strip liquor through second ion-exchange membrane, and metals ion sees through ion-exchange membrane and enters into strip liquor.In membrane extraction-back extraction system (device), feed liquid, strip liquor and the organic solution that contains extraction agent circulate between first ion-exchange membrane, second ion-exchange membrane, one side and two films respectively.Metals ion precipitates and isolates the finished product with the precipitator method with lithium, rubidium or caesium after being reached finite concentration by back extraction in the strip liquor.
Batch operation: be fixed on the IX blend film in the membrane module; At first; The saturated metals ion of organic solution that will contain extraction agent, then, with strip liquor and saturated after organic solution send into the back extraction side and the organic phase side of membrane extraction-back extraction device respectively; Strip liquor and organic solution circulate in the ion-exchange membrane both sides respectively; In the organic solution metal complex then through the film decomplexing in strip liquor, metals ion precipitates and isolates the finished product with the precipitator method with lithium rubidium or caesium after being reached finite concentration by back extraction in the strip liquor.Described strip liquor comprises hydrochloric acid, sulfuric acid, nitric acid or acetate, Hydrocerol A etc., its concentration range 0.2～10mol/L.
The present invention adopts the operation of multistage continous way or interval type membrane extraction-stripping method to extract lithium and rubidium or caesium respectively: promptly after membrane extraction-stripping method of continous way operation or interval type extracts lithium, extract rubidium or caesium with membrane extraction-stripping method of continous way operation or interval type again, or feed liquid two to level Four continous way is operated or interval type membrane extraction-stripping method extracts lithium, rubidium or caesium respectively.
It is that 0.1g～50g/L, rubidium concentration are that 0.01～10g/L, caesium concentration are 0.01～10g/L that described salt lake brine contains lithium concentration; Salt lake brine is salt lake Yuan Shui; Or the magnesium sulfate salt lake brine separated out potassium magnesium mixed salt, again in the old saltwater brine after taking off boron, adds precipitation agent and make Mg through salt pan evaporation
2+, Li
+Respectively with oxyhydroxide, carbonate, phosphoric acid salt or oxalate form be precipitated out, through the concentrated brine after the carboniogenesis; Or, at first, make the bittern of 1200～1500ppm with absorption method with granular oxides of manganese sorbent with the lithium of number ppm in salt lake brine and the seawater, then,, the concentration of lithium brought up to 1.5% rich lithium bittern through the electrodialysis process in two stages; Or extract the mother liquor behind lithium, the potassium etc., or extract the mother liquor behind lithium, boron, the potassium etc., with ion exchange method will wherein rubidium, the caesium of several ppm be concentrated to 1～10g/L.
M (K in said salt lake brine or the seawater feed liquid
+)/m (Li
+)=1: 1～100: m (Mg
2+)/m (Li
+)=40: 1～1200: 1, m (Na
+)/m (Li
+)=10: 1～200: 1, pH value are 1～10.
The described organic phase system that contains extraction agent is made up of extraction agent and thinner; The extraction agent of extraction lithium has tributyl phosphate (TBP), trioctyl phosphine oxide (TOPO), butyl phosphonic acids dibutyl ester (DBBP);, diphenylpropane-1,3-dione(DPPO) (DBM), two pivaloyl methane (DPM), DIBK (DI BK), N; N-two (1-methylheptyl) ethanamide (N503), 1-phenyl-azo bisnaphthol (HA), trioctylphosphine alkyl ammomium chloride (QCl), dodecylphenyl-methyl-beta-diketon (LIX54); The extraction agent of extraction rubidium and caesium is 4-sec.-butyl-2 (α-Jia Bianji) phenol (BAMBP), the 4-tertiary butyl-2-(α-Jia Bianji) phenol (t-BAMBP), hexanitrodiphenylamine (hexyl), Tetraphenyl sodium borate, isopropoxy cup [4] hat-6 (iPr-c [4] C6); Its concentration range (W%) 5-80%; Thinner (organic solvent) comprising: kerosene, aviation kerosene, sulfonated kerosene, hydrogenation kerosene, octane, decane, dodecyl, n-Octanol, nonylcarbinol, n-dodecanol, orthodichlorobenzene, diethylbenzene, YLENE; Tetracol phenixin, oil of mirbane, nitroethane, its concentration range 20-95%.Said process is at room temperature carried out, and need not impressed pressure, and organic phase is brought in constant renewal in, low-cost, less energy-consumption.
Said feed liquid and strip liquor flow are 0.2～10L/min, and the organic phase flow is 0.1～5L/min.
The finished product of said process are alkaline metal salt, comprising: lithium chloride, Quilonum Retard, Lithium Hydroxide MonoHydrate, lithium nitrate, cesium chloride, rubidium chloride, cesium nitrate, rubidium chloride, rubidium nitrate etc.
The present invention has compared following advantage with existing method:
1, the invention provides extraction and the alkali-metal technology of enrichment high value from salt lake brine or seawater effectively.
2, the present invention has opened up and from salt lake brine and seawater, has extracted the alkali-metal new milestone of high value, compares with traditional method, has kept the high advantage of the solvent extration recovery, has overcome the instable shortcoming of immobilized liquid membrane.
3, technical process of the present invention is simple, is easy to extension, need not impressed pressure, energy consumption is low, organic phase is renewable, and is environmentally friendly, and production cost is low, and product purity is high.
4, feed liquid of the present invention directly comes from salt lake brine or seawater, and the feed liquid aboundresources has a extensive future.
5, through different membrane extractions-back extraction experiment proof: the present invention extracts basic metal from salt lake brine and seawater feasible fully.
Description of drawings
Fig. 1 is the membrane extraction and the film back extraction process apparatus synoptic diagram of flat sheet membrane of the present invention.
Fig. 2 is the membrane extraction-back extraction process apparatus figure of flat sheet membrane of the present invention.
Fig. 3 is the membrane extraction-back extraction process apparatus figure of hollow-fibre membrane of the present invention
Fig. 4 is that the present invention extracts alkali-metal process flow sheet
Among Fig. 1: 1-ion-exchange membrane 2-plate film assembly 3-feed liquid or strip liquor 4-organic phase 5,6-recycle pump,
Among Fig. 2: 2-plate and frame module or plate film assembly 3-strip liquor 4--1 feed liquid,
Among Fig. 3: 1-tubular fibre ion-exchange membrane, 2-membrane module.
Embodiment
Salt lake brine takes off boron mother liquor extraction lithium through the saturated magnesium chloride of Exposure to Sunlight, and its mother liquor is formed (g/L): Li
+1.5～2.4, Na
+1.8, Mg
2+100～140, Cl
-300, K
+1.4, SO
4 2-20; Adopt the intermittent film extracting-back extraction process to extract lithium; Organic solution consists of N, and N-two (1-methylheptyl) ethanamide (N503) 10%-tributyl phosphate 20% is dissolved in the n-Octanol; A sulfonated polyether-ether-ketone/polyethersulfone blended anion-exchange membrane is fixed in the plate film assembly, and membrane area is 30cm
2, the organic solution 100mL that get above-mentioned mother liquor 200mL, contains extraction agent is sent to the ion-exchange membrane both sides respectively, and the feed liquid flow velocity is 3m/s; The organic solution flow velocity is 1m/s; Carry out membrane extraction and film back extraction experiment under 30 ℃, the Li in the feed liquid constantly forms metal complex through the extraction agent in film and the organic phase, moves after several hours; Organic solution is retained in film one side; After taking the feed liquid of opposite side away and cleaning feed liquid duct several, with 4mol/L hydrochloric acid soln 200mL replacement feed liquid (strip liquor), the strip liquor flow velocity is 3m/s.Calculate feed liquid side Li
+Flux is 8.4 * 10
-8Mol/cm
2S, back extraction side Li
+Flux is 1.0 * 10
-7Mol/cm
2S,
Other selection of the organic solution of lithium extraction agent: extraction agent is trioctyl phosphine oxide (TOPO) or butyl phosphonic acids dibutyl ester (DBBP), and organic solution is dodecyl or YLENE, and concentration weight ratio 10-20% all can.And for example isopropoxy cup [4] is preced with-6/ n-Octanol system, and concentration weight ratio 10-20% also gets identical result.
Ion-exchange membrane is fixed in (flat board or cylindricality) membrane module, also can adopt other functional film material, and the mould material of ion-exchange performance can be applied for referring to the CN200810025542. that the application contriver proposes; Mould material is dense structure or microvoid structure; Superpolymer blend by superpolymer with ion-exchange performance and nonionic switching performance forms, and can adopt the mass ratio between the superpolymer of superpolymer and nonionic switching performance of ion-exchange performance is 5%/95%～95%/5%.
Salt lake brine takes off boron mother liquor extraction lithium through the saturated magnesium chloride of Exposure to Sunlight, and its mother liquor is formed (g/L): Li
+1.5～2.4, Na
+1.8, Mg
2+100～140, Cl
-300, K
+1.4, SO
4 2-20, adopt intermittently membrane extraction-back extraction process separating Li, at first; Get this mother liquor 200mL and isopyknic organic solution that contains extraction agent in ground tool plug separating funnel; Organic solution consists of with DIBK 80%-tributyl phosphate 20%, is dissolved in No. 200 kerosene abundant concussion 10min under the room temperature; Treat complete layering about static phase-splitting 30min, isolate the organic solution that contains extraction agent of saturated lithium.A sulfonated polyether sulphone ketone/polyethersulfone blended anion-exchange membrane is fixed in the plate film assembly, and membrane area is 30cm
2, the organic solution 200mL of saturated lithium has sent into pusher side, and 4mol/L hydrochloric acid soln 500mL sends into the back extraction side, and strip liquor and organic solution circulate back extraction side Li with the speed of 1m/s and 0.6m/s respectively in two film both sides
+Flux is 7.1 * 10
-8Mol/cm
2S.
In this process, Li
+Constantly move to the strip liquor from saturated organic solution side, the back extraction side obtains containing the hydrochloric acid soln of lithium, adds hydrochloric acid evaporation and cooling are reclaimed, and adds LiOHH
2Among the O with remaining hydrochloric acid and precipitate Mg
2+, the solution heating evaporation, elimination magnesium residue, last, the concentration of lithium reaches 20～100g/L in the solution, produces Quilonum Retard with carbonate precipitation method, and purity reaches more than 99.4%.Na
+And Mg
2+Enrichment with the magnesium formation Marinco H of sodium hydroxide deposition feed liquid lateral enrichment, can further be calcined products such as producing high-purity magnesium oxide or highly-purity magnesite after sedimentation, washing, the drying in feed liquid.
Carry out the extraction of rubidium and caesium behind the extraction lithium; Extraction agent is that 4-sec.-butyl-2 (α-Jia Bianji) phenol (BAMBP) or the 4-tertiary butyl-2-(α-Jia Bianji) phenol (t-BAMBP), organic solvent are n-dodecanol or orthodichlorobenzene, and the scope 40-70% of the percentage composition of organic solvent concentration all can.Also adopt above-mentioned identical ionic membrane, and in the scope of normal temperature and pressure, feed liquid or flow velocity and pH value all do not have particular requirement, reverse-extraction agent adopts dilute sulphuric acid, can obtain rubidiurn sulfate and cesium sulfate at last.Adopt rare nitric acid like reverse-extraction agent, can obtain rubidium nitrate and cesium nitrate at last.
The present invention can adopt P507 and Cyanex 272 extraction agents according to above-mentioned technology, Cyanex 272 extraction agents than the efficient Senior Three of P507 extraction agent doubly about.
Lithium chloride type salt lake brine liquid concentrator, the composition that takes off behind the boron is seen table 1, in above-mentioned salt lake brine liquid concentrator, adds FeCl
36H
2O 113g, making iron lithium mol ratio wherein is 1.5, solution colour is a reddish-brown; PH is about 1, adopts continuous film extracting-back extraction process separating Li, and homo(io)thermism is 25 ℃; Organic phase consists of tributyl phosphate TBP 50%; 50%, two sulfonated polyether sulphone ketone of No. 260 solvent oils of thinner/polyethersulfone blended anion-exchange membrane is fixed in the plate and frame module, and membrane area is 30cm
2Lithium chloride type salt lake brine takes off the both sides that boron liquid concentrator 800mL and 6mol/L hydrochloric acid soln 200mL are sent to two ion-exchange membranees respectively; And constantly circulate in the film both sides with the speed of 4m/s and 3m/s, organic solution 100mL circulates between two films with the speed of 2m/s.After the experiment beginning, the organic phase color becomes faint yellow and continuous intensification from colourless very soon, will remain unchanged behind the 3h; The feed liquid color also shoals gradually; Strip liquor hydrochloric acid is faint yellow, and the strip liquor composition is seen table 1 behind the end of run.
Feed liquid side Li
+Flux is 9 * 10
-8Mol/cm
2S, strip liquor side Li
+Flux is 1.1 * 10
-7Mol/cm
2S, Li
+The recovery is 96.8%.Strip liquor separates hydrochloric acid with the dialysis of film nature after the back extraction, adds LiOHH
2Among the O with remaining hydrochloric acid and precipitate Mg
2+And Fe
3+, the solution heating evaporation, and be evacuated to the solution boiling point more than 150 ℃, get rid of oven dry, and 450 ℃ of following calcinations, the cooling back forms the magnesium borate residue with water extraction boron and residual magnesium, adds barium chloride solution and removes SO
4 2-, elimination permanent white and boron magnesium residue, the residue clear liquid continues evaporation, discharges, dries, and 250～280 ℃ of dehydrations, obtains the Lithium chloride (anhydrous) product, and purity is more than 99.5%.
Table 1
Present embodiment is under about 22 ℃ of room temperatures; Adopt continuous film extracting-back extraction process separating Li; Use sulfonated polyether sulphone ketone/polyethersulfone blended tubular fibre anion-exchange membrane, the feed liquid composition is seen table 2 (g/L): pH=11, strip liquor are 1mol/L sulfuric acid; Organic solution is formed: the trioctyl phosphine oxide of 0.05mol/L (TOPO) and 0.15mol/L dodecylphenyl-methyl-beta-diketon (LIX54), thinner is a dodecyl.Two tubular fibre ion-exchange membrane assemblies are fixed on the device, and effective outer surface area of film is 72cm in each assembly
2, effectively internal surface area is 51cm
2, the speed with 1m/s circulates in the film outside respectively for feed liquid and strip liquor, and material liquid volume is 0.5L, and the strip liquor volume is the speed circulation with 0.4m/s in film of 0.1L organic solution, and volume is 0.1L.
Feed liquid and strip liquor composition is seen table 2, feed liquid side Li before and after the test
+Flux is 9 * 10
-8Mol/cm
2S, back extraction side Li
+Flux is 7.5 * 10
-8Mol/cm
2S, 99.8% Li of feed liquid side
+Be extracted, and strip liquor is to Li
+Back extraction near 96%, show the Li that also has part
+Still in organic solution.Add barium chloride solution to strip liquor and remove SO
4 2-, add LiOHH
2O precipitates Mg
2+,, elimination permanent white and magnesium residue, the clear liquid heating is concentrated to about 30g/L, produces Quilonum Retard with the saturated sodium carbonate solution precipitator method, and purity is 99.6%.
Table 2
Present embodiment is under 30 ℃, adopts continuous film extracting-back extraction process separating Li, uses sulfonated polyether-ether-ketone/polysulfones blend tubular fibre anion-exchange membrane, and the feed liquid composition is seen table 2 (g/L): Li+2, Na
+5, K
+3, Mg
2+180, pH=12, strip liquor are 3mol/L hydrochloric acid, and organic solution is formed: 0.25mol/L1-phenyl-azo bisnaphthol (HA), 0.125mol/L trioctylphosphine alkyl ammomium chloride (QCl), thinner is an orthodichlorobenzene.Two tubular fibre ion-exchange membrane assemblies are fixed on the device, and effective outer surface area of film is 95cm in each assembly
2, effectively internal surface area is 68cm
2, the speed with 4m/s circulates in the film outside respectively for feed liquid and strip liquor, and the equal 1L of material liquid volume, strip liquor volume are the speed circulation with 0.4m/s in film of 0.2L organic solution, and volume is 70mL.
Feed liquid and strip liquor composition is seen table 3, feed liquid side Li before and after the test
+Flux is 9 * 10
-8Mol/cm
2S, back extraction side Li
+Flux is 1 * 10
-7Mol/cm
2S adds LiOHH to strip liquor
2O precipitates Mg
2+, elimination permanent white and magnesium residue, clear liquid are heated to 150 ℃ Li+ are concentrated into about 30g/L, produce Quilonum Retard with the solid sodium carbonate precipitator method, and purity is 99.8%.
Table 3
Embodiment 7
Present embodiment is to carry rubidium and caesium in lithium, the potassium mother liquor with the intermittent film extracting-back extraction process, carries lithium, potassium mother liquor and forms and see table 4, adopts intermittently membrane extraction-back extraction process separating Li; Organic solution is that the 1mol/L4-tertiary butyl-2-(α-Jia Bianji) phenol (t-BAMBP) is dissolved in the normal hexane; The character decision of t-BAMBP itself need extract in alkaline medium; So it is 11～12 that the potential of hydrogen of the sodium hydroxide solution adjusting mother liquor of use 0.5mol/L makes its pH; At first, get organic solution 100mL that alkalescence carries lithium, potassium mother liquor 200mL and contain extraction agent in ground tool plug separating funnel, organic phase is 0.5 with the ratio of water; Fully shake 3min under the room temperature, treat complete layering about static phase-splitting 10min, isolate the organic solution that contains extraction agent of saturated caesium; Percentage extraction is more than 98%; The get raffinate of collection behind the caesium is to extract rubidium under 1.5 the condition at the ratio of organic phase and water, and other conditions are the same, and percentage extraction is 97.3%; A sulfonated polyether sulphone ketone/polyethersulfone blended anion-exchange membrane is fixed in the plate film assembly, and membrane area is 30cm
2, the organic solution 70mL of saturated caesium has sent into pusher side, and 0.5mol/L hydrochloric acid soln 150mL sends into the back extraction side, and respectively with the speed circulation of 3m/s and 1m/s, the flux of back extraction side caesium is 7 * 10 in two film both sides for strip liquor and organic solution
-8Mol/cm
2S; Use the method back extraction rubidium identical with the back extraction caesium, the flux of back extraction side rubidium is 6.5 * 10
-8Mol/cm
2S, the composition of back extraction side caesium, rubidium strip liquor is seen table 3.
Strip liquor evaporation concentration to the concentration that contains rubidium, caesium is about 20g/L, and evaporative crystallization obtains cesium chloride, rubidium chloride, and xln is removed residual acid at 500～550 ℃ of following roasting 2h, obtains cesium chloride, rubidium chloride product, and its purity is 99.2%.
Table 4
On behalf of the present invention, above-mentioned instance be only applicable in the parameter condition that above-mentioned example limits; Professional person in any industry can both encourage the scope of application according to foregoing invention and enlarge with operation format, but its technological core appoint so be limited in the present invention within the generalized scope.Method of the present invention can be generalized to the operate continuously process simply.
Present embodiment is the integrated process that from salt lake brine or seawater, extracts high value alkali metal lithium, rubidium, caesium; Except that the composition of the bittern behind potassium, sodium, the boron is seen table 5; Under about 22 ℃ of room temperatures; Adopt level Four series connection continuous film extracting-back extraction process separating Li, rubidium, caesium, prepare highly purified high value an alkali metal salt product.After the residue feed liquid demagging of first step membrane extraction-back extraction as the feed liquid of second stage membrane extraction-back extraction process; Strip liquor further concentrates, to obtain purity be the lithium carbonate product more than 99.8 for demagging, alkali precipitation, separation, washing drying; Isolated lithium clear liquid is also got back in the partial membrane extraction back extraction device as feed liquid; The strip liquor in second stage membrane extraction-back extraction process and the strip liquor of the first step are done same processing; Partial residue feed liquid is as the feed liquid of the extraction caesium of third stage membrane extraction-back extraction process; The strip liquor of the third stage concentrates roasting, dissolution filter, evaporative crystallization, and to obtain purity be the cesium chloride product more than 99.6; The residue feed liquid of the third stage is extracted the feed liquid of rubidium as fourth stage membrane extraction-back extraction, and the strip liquor of stage concentrates roasting, dissolution filter, evaporative crystallization, and to obtain purity be the rubidium chloride product more than 99.6.Reverse-extraction agent is a dilute hydrochloric acid solution, also can be dilution heat of sulfuric acid.
Adopt sulfonated polyether sulphone ketone/polyethersulfone blended dull and stereotyped anion-exchange membrane in the process, the area of every film is 50cm2, in each membrane extraction-back extraction process; Two ion-exchange membranees are fixed in the plate and frame module; Feed liquid and strip liquor circulate in two films side separately with the speed of 3m/s respectively, and organic phase circulates between two films with 1m/s speed, and material liquid volume is 1L; The strip liquor volume is 0.2L, and the organic phase volume is 0.15L.
In the first step and the second stage membrane extraction-back extraction process, organic phase consists of: 50% tributyl phosphate (TBP), dilute No. 220 kerosene, and strip liquor is 6mol/L HCl.In third stage membrane extraction-back extraction process, organic phase consists of the 1.2mol/L 4-tertiary butyl-2-(α-Jia Bianji) phenol (t-BAMBP) and is dissolved in normal hexane, and strip liquor is 1mol/LHCl.In fourth stage membrane extraction-back extraction process, organic phase consists of the 1.0mol/L4-tertiary butyl-2-(α-Jia Bianji) phenol (t-BAMBP) and is dissolved in YLENE, and strip liquor is 0.5mol/L HCl.
After the experiment of level Four series connection continuous film extracting-back extraction, the composition of strip liquors at different levels is seen table 5.
Table 5
Claims (10)
1. the alkali-metal method of high value is extracted in a membrane extraction-back extraction from salt lake brine or seawater, and its characteristic comprises following mode:
Continous way operation: be fixed on the IX blend film in the membrane module; At first; Contacted with salt lake brine that contains alkalimetal ion or seawater feed liquid through first ion-exchange membrane by the organic solution that contains extraction agent, alkalimetal ion sees through ion-exchange membrane and combines to generate metal complex with the organic solution that contains extraction agent; Then, the organic solution of metal complex is transmitted delivers to second ion-exchange membrane, contacts with strip liquor through second ion-exchange membrane, and metals ion sees through ion-exchange membrane and enters into strip liquor; In membrane extraction-back extraction process, feed liquid, strip liquor and the organic solution that contains extraction agent circulate between first ion-exchange membrane, second ion-exchange membrane, one side and two films respectively.Metals ion obtains the finished product with lithium, rubidium or caesium precipitate and separate after being reached finite concentration by back extraction in the strip liquor;
Or take batch operation: be fixed on the IX blend film in the membrane module; At first; The saturated metals ion of organic solution that will contain extraction agent, then, with strip liquor and saturated after organic solution send into the back extraction side and the organic phase side of membrane extraction-back extraction device respectively; Strip liquor and organic solution circulate in the ion-exchange membrane both sides respectively; In the organic solution metal complex then through the film decomplexing in strip liquor, metals ion precipitates and isolates the finished product with the precipitator method with lithium, rubidium or caesium after being reached finite concentration by back extraction in the strip liquor.
The organic solution that employing contains extraction agent combines realization extraction and back extraction through membrane extraction to organic solution that contains extraction agent and the film back extraction process that obtains saturated metals ion in salt lake brine or the seawater feed liquid, forms a successive process; Or step operating process.Used IX blend film is the anionresin blend film.
2. membrane extraction-reverse extraction technology as claimed in claim 1 is extracted the alkali-metal method of high value from salt lake brine and seawater; It is characterized in that the saturated organic solution that contains extraction agent is to adopt solvent extration to obtain the organic solution that contains extraction agent of saturated metals ion, or adopt contain extraction agent organic solution through membrane extraction to obtaining the organic solution that contains extraction agent of saturated metals ion in salt lake brine or the seawater feed liquid.
3. membrane extraction-reverse extraction technology as claimed in claim 1 is extracted the alkali-metal method of high value from salt lake brine and seawater; It is characterized in that adopting the organic solution that contains extraction agent the organic solution that contains extraction agent that obtains saturated metals ion in salt lake brine or the seawater feed liquid and film back extraction process to be combined and realize that extraction and back extraction carry out simultaneously, form a successive process through membrane extraction; It also can be step operating process.Used IX blend film is the anionresin blend film.
4. membrane extraction-reverse extraction technology as claimed in claim 1 is extracted the alkali-metal method of high value from salt lake brine and seawater; It is characterized in that it is that 0.1g～50g/L, rubidium concentration are that 0.01～10g/L, caesium concentration are 0.01～10g/L that described salt lake brine contains lithium concentration; Salt lake brine is salt lake Yuan Shui; Or the magnesium sulfate salt lake brine separated out potassium magnesium mixed salt, again in the old saltwater brine after taking off boron, adds precipitation agent and make Mg through salt pan evaporation
2+, Li
+Respectively with oxyhydroxide, carbonate, phosphoric acid salt or oxalate form be precipitated out, through the concentrated brine after the carboniogenesis; Or, at first, make the bittern of 1200～1500ppm with absorption method with granular oxides of manganese sorbent with the lithium of number ppm in salt lake brine and the seawater, then,, the concentration of lithium brought up to 1.5% rich lithium bittern through the electrodialysis process in two stages; Or extract the mother liquor behind lithium, the potassium etc., or extract the mother liquor behind lithium, boron, the potassium etc., with ion exchange method will wherein rubidium, the caesium of several ppm be concentrated to 1～10g/L.
5. according to claim 1 or claim 2 membrane extraction-reverse extraction technology is extracted valuable alkali-metal method from salt lake brine and seawater, it is characterized in that m (K in salt lake brine or the seawater feed liquid
+)/m (Li
+)=10: 1～1000: 1, m (Mg
2+)/m (Li
+)=40: 1～1800: 1, m (Na
+)/m (Li
+)=10: 1～2000: 1, pH value are 1～10.
6. according to claim 1 or claim 2 membrane extraction-reverse extraction technology is extracted the high value metals novel method from salt lake brine and seawater; It is characterized in that the described organic phase system that contains extraction agent is made up of extraction agent and thinner; The extraction agent of extraction lithium has tributyl phosphate (TBP), trioctyl phosphine oxide (TOPO), butyl phosphonic acids dibutyl ester (DBBP);, diphenylpropane-1,3-dione(DPPO) (DBM), two pivaloyl methane (DPM), DIBK (D I BK), N; N-two (1-methylheptyl) ethanamide (N503), 1-phenyl-azo bisnaphthol (HA), trioctylphosphine alkyl ammomium chloride (QCl), dodecylphenyl-methyl-beta-diketon (LIX54); Collection 4-sec.-butyl-2 (α-Jia Bianji) phenol (BAMBP) of extraction rubidium and caesium, the 4-tertiary butyl-2-(α-Jia Bianji) phenol (t-BAMBP), hexanitrodiphenylamine (hexyl), Tetraphenyl sodium borate, isopropoxy cup [4] hat-6 (iPr-[4] C6), its concentration range 5-80% weight ratio; Organic solvent comprises: kerosene, aviation kerosene, sulfonated kerosene, hydrogenation kerosene, normal hexane, octane, decane, dodecyl, n-Octanol, nonylcarbinol, n-dodecanol, orthodichlorobenzene, diethylbenzene, YLENE; Tetracol phenixin, oil of mirbane, nitroethane, its concentration range 20-95% weight ratio.
7. according to claim 1 or claim 2 membrane extraction-reverse extraction technology is extracted the alkali-metal method of high value from salt lake brine and seawater, it is characterized in that described strip liquor comprises hydrochloric acid, sulfuric acid or nitric acid, its concentration range 0.2～10mol/L.
8. from salt lake brine and seawater, extract the alkali-metal method of lithium high value like claim 1 or 3 described membrane extraction-reverse extraction technology; It is characterized in that said process at room temperature carries out; Need not impressed pressure, organic phase is brought in constant renewal in, the high and low cost of product purity, less energy-consumption.
9. from salt lake brine and seawater, extract the alkali-metal method of high value like claim 1 or 3 described membrane extraction-reverse extraction technology, it is characterized in that said feed liquid and strip liquor flow rates are 0.02～10m/s, the organic phase flow is 0.01～5m/s.
10. the alkali-metal method of high value is extracted in membrane extraction-back extraction as claimed in claim 1 from salt lake brine and seawater, it is characterized in that adopting multistage continous way operation or interval type membrane extraction-stripping method to extract lithium and rubidium or caesium respectively.
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