CN102312110B - 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 from lower concentration 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.
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 to the early autumn of the energy along with the fast development of human economic society, 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, the cost height, 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 producing lithium from solution 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.Based on Qinghai and salt lake, Tibet, 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 Mg/Li ratio value height in the salt lake brine, are about 40~1200: 1, and separating difficulty is big, and feasible technology is few.
Very unstable, the very easily ionization of the outermost electron of rubidium and caesium atom, the dielectric medium that can be used as solid state battery, make the main sensitive materials of phototube, at present carrying out rubidium energetically at ion engine, magnetohydrodynamic generator and two kinds of brand-new generation modes of thermoelectric power generation, 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.Can find the signal that should not find night with the infrared radiation lamp that the compound of caesium is made, 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, biotite, 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 with ionic species, 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.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 very important 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 at 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 at 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, US Patent No. 538934 and US5599516 disclose the ionic adsorption method and have extracted the bittern lithium, successfully prepared LiCl content and be 012%~0133% LiCl/Al (OH) 3 sorbent materials, extract the LiCl experiment with being used for after its granulation from containing the higher solution of NaCl, the about 30min of each circulation, the rate of 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, at last with the elutriant of purifying LiCl is converted into LiOH at electrolytic agent tray of containers and electrodialyzer, 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, but molten loss rate is still a great problem to be solved more greatly.This shows that resin cost height, the loading capacity that the ionic adsorption method is used 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, precipitation 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 the energy consumption height, and equipment requirements height, environmental pollution are big.
Chinese patent CN1335263A discloses carborization and produced Quilonum Retard from the high Mg/Li ratio salt lake brine, 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 precipitation is carried out calcining and decomposing, by carbonization or carbonation, make Li
+Pass into solution, Mg
2+Still keep in the precipitation, separate thereby reach the magnesium lithium, should carry out deep impurity-removing by richness lithium solution again, subsequently evaporation concentration or with soda ash precipitation preparation Quilonum Retard, this method cost is also very high.
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, the process complexity.Chinese patent CN1485273A and US Patent No. 2004/0074774A1 disclose a kind of method that concentrates lithium from bittern and seawater: this method is concentrated to the lithium concentration in the bittern about 1.5% by number ppm in conjunction with absorption method and two kinds of extractive techniques of electroosmose process; At first make the bittern of 1200~1500ppm with granular oxides of manganese sorbent with absorption method, through the electrodialysis process in two stages, the concentration of lithium is brought up to 1.5% then.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 to contain Mg
2+, Ca
2+Deng positively charged ion and SO
4 2-, B
xOy
N-Salt pan evaporation gained Deng negatively charged ion contains lithium bittern, wherein Li
+Concentration 0.1~11.5g/L, magnesium lithium weight ratio 1: 1~200: 1 is separated and enrichment wherein lithium by nanofiltration 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 performance that the pollution of film brings reduces and because the poor stability of the mould material that matting causes, in addition, also need extract lithium, production cost height through additive method through the low magnesium lithium liquid after the nanofiltration.
Solvent extration is put forward the lithium new technology as current very popular salt lake both at home and abroad, is characterized in utilizing organic solvent to the special extraction ability of lithium, can separate basic metal and alkaline-earth metal effectively and reach and put forward the lithium purpose.US Patent No. 3537813 has proposed a kind of iron trichloride that adds in bittern, make extraction system extraction lithium with diisobutyl ketone 80%-tributyl phosphate 20%, enters the lithium water back extraction of organic phase, owing to contain LiCl and FeCl in anti-stripping agent
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 diisobutyl ketone solubleness in water is big, and the price height, 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%.At these problems, Chinese patent CN87103431A has taked a kind ofly directly to extract the processing 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, although this method has a clear superiority in than additive method, also be difficult to realize industrialization on the rate of recovery.
At the shortcoming of solvent extraction technology, the liquid-film method isolation technique has appearred, and wherein carrier promotes immobilized liquid membrane performance brilliance in metal separation of transmission, spent organic extraction liquid is few, effective contact area height of extraction system and raw material liq, the extraction efficiency height, cost is low; But because the immobilized liquid membrane that the loss of organic extraction liquid causes transmits performance and select performance to reduce, namely 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, this system can extract lithium, Li effectively
+Permeability coefficient 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 with pH=8-9 effect of extracting the best.Tetraphenyl borate receives-and nitroethane mainly extracts rubidium ion.Hexanitrodiphenylamine and derivative, 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, although this method has a clear superiority in than additive method, also be difficult to realize industrialization on the rate of recovery.
Chinese patent CN93104780.3 discloses the method for rubidium in a kind of ion exchange method separation and concentration bittern, used ion-exchanger is synthetic by cupric nitrate and the Tripotassium iron hexacyanide, ion-exchange instigator activates with the 1mol/L nitric acid dousing with preceding, enrichment the rare nitric acid dousing of exchange column of rubidium, use H
2O drip washing, the primary sorption rate reaches 70%, and this method is because of reagent molten loss rate height 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 etc. (Gay R L et al.Studies of the volatility of cesiumand iodine[J] .Wastes Manage, 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, 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 to operate under high temperature, high radioactivity condition, to the requirement height 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 extracting alkali-metal method from contain lithium bittern 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 height of rubidium, caesium.
Purpose of the present invention can reach by 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: the ion-exchange blend film is fixed in the membrane module, at first, contacted with the salt lake brine that contains alkalimetal ion or seawater feed liquid by first ion-exchange membrane by the organic solution that contains extraction agent, metal ion is combined with the organic solution that contains extraction agent through ion-exchange membrane and is generated metal complex; Then, second ion-exchange membrane is delivered in the transmission of the organic solution of metal complex, contacts with strip liquor by second ion-exchange membrane, and metal 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.Metal 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: the ion-exchange blend film is fixed in the membrane module, at first, the saturated metal ion of organic solution that will contain extraction agent, then, with strip liquor and saturated after organic solution send into 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, metal complex then passes through the film decomplexing in strip liquor in the organic solution, metal 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 acetic acid, citric acid 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: namely after membrane extraction-stripping method of continous way operation or interval type extracts lithium again membrane extraction-the stripping method with continous way operation or interval type extract rubidium or caesium, or lithium, rubidium or caesium are extracted in feed liquid two to the operation of level Four continous way or interval type membrane extraction-stripping method 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 will be in salt lake brine and the seawater lithium of number ppm, at first, make the bittern of 1200~1500ppm with granular oxides of manganese sorbent with absorption method, then, through the electrodialysis process in two stages, the concentration of lithium brought up to 1.5% rich lithium bittern; Or extract 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 described 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), diisobutyl ketone (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, dodecane, n-Octanol, nonylcarbinol, n-dodecanol, orthodichlorobenzene, diethylbenzene, dimethylbenzene, tetracol phenixin, oil of mirbane, nitroethane, its concentration range 20-95%.Described 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.
Described 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 described process are alkaline metal salt, comprising: lithium chloride, Quilonum Retard, lithium hydroxide, 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 extracted the alkali-metal new milestone of high value from salt lake brine and seawater, compares with traditional method, has kept the high advantage of the solvent extration rate of 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, the product purity height.
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, experimental results show that through different membrane extraction-back extractions: the present invention extracts basic metal from salt lake brine and seawater feasible fully.
Description of drawings
Fig. 1 is 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, N-two (1-methylheptyl) ethanamide (N503) 10%-tributyl phosphate 20%, be 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
2The organic solution 100mL that get above-mentioned mother liquor 200mL, contains extraction agent is sent to the ion-exchange membrane both sides respectively, 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 ℃, Li in the feed liquid constantly forms metal complex by the extraction agent in film and the organic phase, after moving a few hours, organic solution is retained in film one side, after taking the feed liquid of opposite side away and cleaning feed liquid side pipe road several, replace feed liquid (strip liquor) with 4mol/L hydrochloric acid soln 200mL, 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 dodecane or dimethylbenzene, 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 present application people proposes; Mould material is dense structure or microvoid structure, superpolymer blend by the superpolymer with ion-exchange performance and nonionic switching performance forms, and can adopt the mass ratio between the superpolymer of the superpolymer of ion-exchange performance and nonionic switching 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 of extraction agent that contains in ground tool plug separating funnel, organic solution consists of with diisobutyl ketone 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, 4mol/L hydrochloric acid soln 500mL sends into the back extraction side, strip liquor and organic solution in two film both sides respectively with the circulation of the speed of 1m/s and 0.6m/s, back extraction side Li
+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 and 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+Be enriched in the feed liquid, with the magnesium formation magnesium hydroxide of sodium hydroxide precipitation feed liquid lateral enrichment, can further calcine products such as producing high-purity magnesium oxide or highly-purity magnesite after sedimentation, washing, the drying.
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 as 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 concentrated solution, the composition that takes off behind the boron sees Table 1, adds FeCl in above-mentioned salt lake brine concentrated solution
36H
2O 113g, making iron lithium mol ratio wherein is 1.5, solution colour is 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 concentrated solution 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 is very fast to become faint yellow and continuous intensification from colourless, 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 sees 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 rate of recovery is 96.8%.Strip liquor separates hydrochloric acid with the dialysis of film nature after the back extraction, adds LiOHH
2Among the O and 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 barium sulfate 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 sees Table 2 (g/L): pH=11, strip liquor is 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 dodecane.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 sees 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 barium sulfate 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 sees 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 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 sees 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 barium sulfate 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 of t-BAMBP itself determines and need extract in alkaline medium, so it is 11~12 that the potential of hydrogen of regulating mother liquor with the sodium hydroxide solution of 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; With 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 sees 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
Above-mentioned example does not represent the present invention and is only applicable in the parameter condition that above-mentioned example limits, professional person in any industry can both encourage the scope of application and operation format enlarges according to foregoing invention, but its technological core is appointed and so is limited within the scope that the present invention summarizes.Method of the present invention can be generalized to the operate continuously process simply.
Embodiment 8
Present embodiment is the integrated process that extracts high value alkali metal lithium, rubidium, caesium from salt lake brine or seawater, except the composition of the bittern behind potassium, sodium, the boron sees 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, demagging, alkali precipitation, separate, washing is dry, and to obtain purity be lithium carbonate product more than 99.8, isolated lithium clear liquid is also got back in the partial membrane extraction back extraction device as feed liquid, 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, it is cesium chloride product more than 99.6 that evaporative crystallization obtains purity, the residue feed liquid of the third stage is as the feed liquid of fourth stage membrane extraction-back extraction extraction rubidium, and the strip liquor of quadravalence section concentrates roasting, dissolution filter, it is rubidium chloride product more than 99.6 that evaporative crystallization obtains purity.Reverse-extraction agent is 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 dimethylbenzene, 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 sees 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 feature comprises following mode:
Continous way operation: the ion-exchange blend film is fixed in the membrane module, at first, contacted with the salt lake brine that contains alkalimetal ion or seawater feed liquid by first ion-exchange membrane by the organic solution that contains extraction agent, alkalimetal ion is combined with the organic solution that contains extraction agent through ion-exchange membrane and is generated metal complex; Then, the organic solution of metal complex is transmitted delivers to second ion-exchange membrane, contacts with strip liquor by second ion-exchange membrane, and metal 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; Metal 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: the ion-exchange blend film is fixed in the membrane module, at first, the organic solution that will contain extraction agent obtains the organic solution that contains extraction agent of saturated metal ion, then, with strip liquor and saturated after organic solution send into 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, metal complex then passes through the film decomplexing in strip liquor in the organic solution, metal ion by back extraction in strip liquor, after reaching finite concentration, with the precipitator method with lithium, rubidium or caesium precipitate and isolate the finished product;
The organic solution that employing contains extraction agent combines realization extraction and back extraction by membrane extraction obtains saturated metal ion from salt lake brine or seawater feed liquid the organic solution that contains extraction agent and film back extraction process, forms a continuous process; Or step operating process; Used ion-exchange 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 metal ion, or adopt contain extraction agent organic solution by membrane extraction to obtaining the organic solution that contains extraction agent of saturated metal 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 by membrane extraction the organic solution that contains extraction agent that obtains saturated metal 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 continuous process; Also can be that the used ion-exchange blend film of step operating process 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 will be in salt lake brine and the seawater lithium of number ppm, at first, make the bittern of 1200~1500ppm with granular oxides of manganese sorbent with absorption method, then, through the electrodialysis process in two stages, the concentration of lithium brought up to 1.5% rich lithium bittern; Or extract 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. membrane extraction-reverse extraction technology as claimed in claim 1 or 2 is extracted the alkali-metal method of high value from salt lake brine and seawater, it is characterized in that m (K in salt lake brine or the seawater feed liquid
+)/m (Li
+)=1:1~100:1, m (Mg
2+)/m (Li
+)=40:1~1200:1, m (Na
+)/m (Li
+)=10:1~200:1, the pH value is 1~10.
6. membrane extraction-reverse extraction technology as claimed in claim 1 or 2 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), diisobutyl ketone (DIBK), N, N-two (1-methylheptyl) ethanamide (N503), 1-phenyl-azo bisnaphthol (HA), trioctylphosphine alkyl ammomium chloride (QCl) or dodecylphenyl-methyl-beta-diketon (LIX54), the extraction agent of extraction rubidium and caesium is 4-sec-butyl-2 (α-Jia Bianji) phenol, the 4-tertiary butyl-2-(α-Jia Bianji) phenol, hexanitrodiphenylamine, Tetraphenyl sodium borate or isopropoxy cup [4] hat-6 (iPr-[4] C6), its concentration range 5-80% weight ratio; Thinner is kerosene, aviation kerosene, sulfonated kerosene, hydrogenation kerosene, normal hexane, octane, decane, dodecane, n-Octanol, nonylcarbinol, n-dodecanol, orthodichlorobenzene, diethylbenzene, dimethylbenzene, tetracol phenixin, oil of mirbane or nitroethane, its concentration range 20-95% weight ratio.
7. membrane extraction-reverse extraction technology as claimed in claim 1 or 2 is extracted the alkali-metal method of high value from salt lake brine and seawater, it is characterized in that described strip liquor is 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 as claim 1 or 3 described membrane extraction-reverse extraction technology, it is characterized in that described 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. extract the alkali-metal method of high value as claim 1 or 3 described membrane extraction-reverse extraction technology from salt lake brine and seawater, it is characterized in that described feed liquid and strip liquor flow rates are 1~4m/s, the organic phase flow is 0.4~2m/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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