CN101318670A - Processing technique for extracting lithium salt from lithium containing salt lake bittern water - Google Patents
Processing technique for extracting lithium salt from lithium containing salt lake bittern water Download PDFInfo
- Publication number
- CN101318670A CN101318670A CNA2008100317764A CN200810031776A CN101318670A CN 101318670 A CN101318670 A CN 101318670A CN A2008100317764 A CNA2008100317764 A CN A2008100317764A CN 200810031776 A CN200810031776 A CN 200810031776A CN 101318670 A CN101318670 A CN 101318670A
- Authority
- CN
- China
- Prior art keywords
- salt
- lithium
- flotation
- lithium salts
- time
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a production process for extracting lithium salt from lake brine containing lithium salt which comprises the following steps: 1) brine is sunned and concentrated in a salt pan until a salt mixture with lithium salt (or lithium double salt) and magnesium salt or the mixture of lithium salt (or lithium double salt), magnesium salt and sodium salt is obtained by crystallization; 2) grinding: the salt mixture is ground into the powder less than or equal to 100 meshes; 3) flotation: flotation is performed in the saturated mother liquor at the normal temperature and normal pressure, the flotation reagents are alkyl derivatives with 4 to 8 carbon atoms and methyl radical such as alcohol or aldehyde, the floatation process is composed of once roughing, at least twice cleaning and once scavenging; the dosage of the floatation agent and the time are as follows: the dosage of the roughing reagent is 80g to 300g for each ton of the crude ore, the floatation time is 5 to 7 minutes, the scavenging reagent is 45g to 65g for each ton of the crude ore and the flotation time is 5 to 7 minutes, no reagent is needed for the cleaning, and the time for each cleaning is 2 to 4 minutes; the lithium salt, the sodium salt and the magnesium salt are separated to obtain a crude lithium salt product. The production process for extracting lithium salt from lithium-bearing salt lake brine is characterized by short process, low energy consumption, simple operation, is applicable to extraction of lithium salt from various lake brines containing lithium salt, in particular to the extraction of lithium from brine with high magnesium-lithium ratio.
Description
Technical field
The present invention relates to a kind of production technique of from contain the lithium salts lake bittern water, extracting lithium salts.
Background technology
Lithium is the lightest metal of nature, can keep afloat and water reacts.Lithium makes number one in alkali metal, has the common chemical property with alkali metal.Common lithium salts has LiCl, Li
2SO
4, LiNO
3, LiBr, Li
2CO
3Deng.Metallic lithium and lithium salts have important strategic position in the development of the national economy.Lithium and compound thereof are widely used in the production of aerospace industry, nuclear energy field, smelting and production, IT industry and daily necessities.
70% lithium resource derives from bittern in the world, at present, the Zha Buye salt lake of 4 super-huge bittern lithium deposites Uyuni sabkha that is Bolivia, the Atacama sabkha of Chile, Argentinian HombreMuerto sabkha, China contains lithium all more than 100,000 t in the world.Wherein the lithium reserves occupy first in the Uyuni sabkha bittern, reach 9,800,000 t.The lithium resource of China mainly is distributed in Tibet, Qinghai and Xinjiang.Zha Buye salt lake, Tibet and salt lake, the Caidamu Basin, Qinghai are the salt lake brine resources of two maximums of China.The Zha Buye salt lake is that 3 lithium resources surpass one of ultra-large type salt lake of 1,000,000 t in the world, and these lake solid-liquid phase lithium reserves are totally 153 ten thousand t, liquid phase lithium reserves 250,000 t wherein, and lithium content is up to 1000～2000mgL in the bittern
-1Salt lake, Caidamu Basin lithium salts (by LiCl) reserves 15,207 ten thousand t, the lithium salts ore deposit is mainly composed and is stored in the face of land, salt lake bittern and the intercrystalline bittern, large-scale brine deposit mainly contain Yi Liping, East Platform Ji like this with West Platform gill salt lake; Medium-sized brine deposit has big bavin dawn salt lake; In the salt lakes such as Cha Er sweat, billow beach bigger lithium salts reserves are arranged; But content is lower, dispersion distributes.
China since later stage the 1950's, has just carried out lithium salts is extracted in Sichuan from Gongjing halogen research for exploitation bittern lithium resource.Once be engaged in the experiment of extracting method such as aluminate coprecipitation method, solvent extration, calcination method, and once reached the limited-production scale.Qinghai Yanhu Inst., Chinese Academy of Sciences has carried out the research of multiple lithium salts extracting method at big bavin dawn salt lake, Cha Er sweat salt lake, thing platform Ji a salt lake and a Li Ping salt lake etc. like this.Big bavin dawn salt lake is positioned at Caidamu Basin Da Qaidam Zhen, the about 240km of salt lake area
2This salt lake brine belongs to the sea-water type magnesium sulfate that is rich in boron, lithium, and lake water contains lithium ion 0.02%, can not directly extract, and the saturated magnesium chloride bittern of salt lake saline after solar evaporation separates a small amount of salt, boron, lithium obtain enrichment.
From salt lake brine, carry lithium, many diverse ways are arranged, evaporative crystallization partition method, the precipitator method, solvent extration, ion exchange adsorption etc. are arranged respectively.Wherein evaporative crystallization method, the precipitator method, solvent extration have been applied to the industrial production of lithium salts.The key of ion exchange method is to find a kind of lithium to be had special optionally material, can optionally extract lithium from the dilute solution of lithium.
1, evaporative crystallization partition method.Earlier from bittern, reclaim useful components such as sodium, potassium, boron, bromine, iodine, from last mother liquor, carry lithium again.The key of putting forward lithium technology is calcium, the magnesium of removing in the mother liquor.Traditional method is to use the caustic soda demagging, then solution dilution to lithium chloride is lower than 13.8g/l, adds the soda ash precipitated calcium again, and last concentrated mother liquor precipitates Quilonum Retard with soda ash.Since a large amount of caustic soda and soda ash of using, and increase steam output, cause the lithium salts product cost higher.
2, the precipitator method.In containing the higher bittern of lithium, add precipitation agent lithium is separated with other salts.PH6.8～7.0, when temperature was 90 ℃, amorphous hydroted alumina can generate stable aluminium lithium compound (LiCl2Al (OH) with the lithium ion in the bittern
3NH
2O) precipitation.Yellow flourish levels etc. are produced Li direct separation the from the intercrystalline bittern of basic carbonate type salt lake
2CO
3Make precipitation agent with Sodium phosphate dibasic, precipitation is all dissolved with hydrochloric acid, make the feed liquid that contains lithium 0.5～1.5g/L, by hydrogen (or sodium) type resin cation (R.C.) separating Li and phosphate anion, precipitate Quilonum Retard the elutriant after concentrating, the total recovery of lithium is 75%, and the production cost of Quilonum Retard is about 6000 yuan/t.The shortcoming of present method is that first method only is applicable to and contains the higher bittern of lithium, and product LiCl2Al (OH)
3NH
2O is a double salt, is not final Li
2CO
3Product, the second method resin is reused, and the life-span is limited, and scale operation is difficult, long flow path, plastic resin treatment is limited in one's ability.
3, ion exchange adsorption.The lithium that utilizes ion exchange technique to separate in the bittern has in recent years had bigger progress, and groundwork is at low-grade oil-gas field bittern, seawater and geothermal brine.It is actually rare that the organic ion exchange resin is directly used in the bittern separating Li, and major cause is that the organic ion exchange resin is relatively poor to lithium and other cationic separating effects.Usually in exchange solution, allocate 80%～95% methyl alcohol into and suppress other cationic exchanges.Because a large amount of methyl alcohol that use are difficult to realize suitability for industrialized production technically.The data introduction is arranged,, can from bittern, extract lithium in conjunction with MS type flotation machine separation resin and solution with IR-120B type cationic exchange resin adsorption lithium.The shortcoming of present method is that organic ion exchange resin processing power and work-ing life are limited, uses methyl alcohol in a large number, makes extensive difficult suitability for industrialized production to realize.
4, resin adsorption method.It is to adhere to a large amount of LiX2Al (OH) in the space of weak base anion-exchange resin
3NH
2O (X is a halogen) has two layers or trilaminar structure, i.e. the parallel two-layer Al (OH) that joins of lithium salts
3Between, its interplanar distance value is with containing reducing and slightly increasing of LiX amount.The shortcoming of present method is a raw material weak base anion-exchange resin source difficulty, and processing power is limited, and scale operation is impossible, and product remains double salt.
In addition, U.S.'s potash and chemical company adopt flotation process to reclaim lithium from the Searles salt lake brine, when way is the double salt of separating out in digestion triple effect evaporation process, there is the less lithium salts of many solubleness to be suspended in the solution, digestion liquid is sent into flotation cell, add these lithiumation things of pore forming material flotation, obtain the concentrate of main phosphoric acid lithium sodium, concentrate is produced phosphoric acid and Quilonum Retard after the vitriol oil decomposes, the operation yield of lithium is 88%, and this flotation process is common higher by about 20% than perfectly crystallization process yield, shortcoming is that the auxiliary material vitriol oil is participated in reaction, the processing requirement height, digestion triple effect evaporation energy consumption height, Production Flow Chart is long.
United States Patent (USP) discloses a kind of anion-exchange resin method that reclaims lithium from bittern for No. 4221767, and the new resin of making is to suspend, be dispersed with LiX2Al (OH) in the space of matrix or little pore
3The LiX2Al of crystallite (OH)
3/ resin compound.The resin of this method preparation is longer work-ing life.Experiment shows, alternately flows, recycles 140 all after dates through bittern, and resin does not significantly reduce the exchange capacity of lithium.It not only can be used for reclaiming lithium from bittern, even can also be used for reclaiming magnesium from bittern, and the shortcoming of this method is: though its resin long service life, source difficulty, and the resin absorption is that the double salt of Li is resin compound, the scale operation difficulty is big.
Summary of the invention
The object of the present invention is to provide a kind of facility investment little, floor space is little, is convenient to operation, is easy to realize large-scale industrial production, and energy consumption is low, the production technique of extracting lithium salts from contain the lithium salts lake bittern water that production cost is low.
The objective of the invention is to be achieved through the following technical solutions: it may further comprise the steps: shine on beach, (1) bittern salt pan, concentrates, and goes out to contain the mixing salt of lithium salts and magnesium salts, perhaps lithium salts and magnesium salts, sodium salt three's mixing salt until crystallization; (2) ore grinding is worn into mixing salt≤100 purpose powderies; (3) flotation, according to lithium salts and magnesium salts, the difference of sodium salt surface chemical property, separate by method for floating, flotation is carried out in saturated mother liquor at normal temperatures and pressures, flotation reagent is generally 4～8 carbon atoms and has the alkane derivatives alcohol or the aldehyde (for example CB-1) of methyl group, adopt one roughing, at least recleaning, the flotation process of once purging selection, flotation reagent consumption and time are: roughly select dosing 80-380 gram/ton raw ore (preferred 180-300 gram/ton raw ore), flotation time 5-7 minute, scan and add dose 45-65 gram/ton raw ore, flotation time 5-7 minute, selected not dosing, each selected time is 2-4 minute, with lithium salts and magnesium salts, sodium salt separates, and obtains the thick product of lithium salts.
The thick product of gained lithium salts can directly come into the market to sell, and also can use known chemical industry method further to make with extra care, to obtain the lithium salts product of better quality.
Lithium salts floatation process of the present invention both can be at Cl
-Carry out in the type bittern, also can be at SO
4 2-Carry out in the type bittern.
High, medium and low grade (Li in the old halogen is shone on the beach, salt pan
+Grade 0.1%～0.7%) lithium salts, Mg/Li ratio 5～40 all can adopt floatation process of the present invention to carry out the extraction of lithium, and concrete grammar is, scrape the bubble time and promptly can reach the purpose of carrying lithium by increasing selected number of times, adjustment flotation reagent consumption and flotation.
The saturated mother liquor that uses in the flotation of the present invention can recycle, can not pollute environment.
Plurality of advantages such as the present invention has energy consumption low (normal temperature and pressure), and facility investment is little, and floor space is little, is convenient to operation, is easy to realize large-scale industrial production, and production cost is low.
The present invention is applicable to that from containing negatively charged ion be Cl
-Or SO
4 2-The lithium metal is reclaimed in containing of type in the lithium salts lake bittern water.
Embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment 1
(1) certain salt lake brine (chloride type contains Li0.06% in the original bittern), former halogen through reeve shine, concentrate, crystallization, obtaining main component is the mixing salt of chlorination lithium salts and bischofite, this mixing salt chemical constitution be Li
+0.88%, Cl
-31.418%, Mg
2+9.497%; (2), cross 100 mesh sieves with the mixing salt pulverize; (3) to powdered mixing salt, adopt saturated bittern to carry out direct flotation at normal temperatures and pressures, flotation reagent is CB-1, floatation process is one roughing, recleaning, once purging selection (is roughly selected dosing 300 gram/ton raw ores, flotation time 6 minutes is scanned and is added dose 50 gram/ton raw ores, flotation time 6 minutes, primary cleaning and twice selected not dosing, flotation time is 3 minutes, and lithium salts is separated with magnesium salts, sodium salt, promptly obtains the thick product of lithium salts.The lithium concentrate grade is that Li3.637% (is LiCl.H
2O grade 31.65%), the rate of recovery 85.10% of lithium.
Embodiment 2
(1) certain salt lake brine (chloride type contains Li0.06% in the original bittern), former halogen through reeve shine, concentrate, crystallization, obtaining main component is the mixing salt of chlorination lithium salts and bischofite, this mixing salt chemical constitution be Li
+0.88%, Cl
-31.418%, Mg
2+9.497%; (2), cross 100 mesh sieves with the mixing salt pulverize; (3) to powdered mixing salt, adopt saturated bittern to carry out direct flotation at normal temperatures and pressures, flotation reagent is CB-1, floatation process is one roughing, recleaning, once purging selection is roughly selected dosing 180 gram/ton raw ores, flotation time 6 minutes, scan and add dose 50 gram/ton raw ores, flotation time 6 minutes, primary cleaning and twice selected not dosing, flotation time is 3 minutes, lithium salts is separated with magnesium salts, sodium salt, promptly obtain the thick product of lithium salts.The lithium concentrate grade is Li3.437%, the rate of recovery 84.30% of lithium.
Embodiment 3
(1) certain salt lake brine (chloride type contains Li0.06% in the original bittern), former halogen through reeve shine, concentrate, crystallization, obtaining main component is the mixing salt of chlorination lithium salts and bischofite, this mixing salt chemical constitution be Li
+0.88%, Cl
-31.418%, Mg
2+9.497%; (2), cross 100 mesh sieves with the mixing salt pulverize; (3) to powdered mixing salt, adopt saturated bittern to carry out direct flotation at normal temperatures and pressures, flotation reagent is CB-1, floatation process is one roughing, recleaning, once purging selection (is roughly selected dosing 280 gram/ton raw ores, flotation time 6 minutes is scanned and is added dose 60 gram/ton raw ores, flotation time 6 minutes, primary cleaning and twice selected not dosing, flotation time is 3 minutes, and lithium salts is separated with magnesium salts, sodium salt, promptly obtains the thick product of lithium salts.The lithium concentrate grade is Li3.237%, the rate of recovery 85.50% of lithium.
Claims (2)
1, a kind of production technique of from contain the lithium salts lake bittern water, extracting lithium salts, it is characterized in that, may further comprise the steps: shine on beach, (1) bittern salt pan, concentrate, go out to contain the mixing salt of lithium salts (or double salt of lithium) and magnesium salts, perhaps lithium salts (or double salt of lithium) and magnesium salts, sodium salt three's mixing salt until crystallization; (2) ore grinding is worn into mixing salt≤100 purpose powderies; (3) flotation.Flotation is carried out in saturated mother liquor at normal temperatures and pressures, flotation reagent is 4～8 carbon atoms and alkane derivatives alcohol or the aldehyde that has methyl group, floatation process adopts one roughing, at least recleaning, once purging selection, flotation reagent consumption and time are: roughly select dosing 80-380 gram/ton raw ore, flotation time 5-7 minute, scan and add dose 45-65 gram/ton raw ore, flotation time 5-7 minute, selected not dosing, each selected time is 2-4 minute, lithium salts is separated with magnesium salts, sodium salt, obtain the thick product of lithium salts.
2, the production technique of from contain the lithium salts lake bittern water, extracting lithium salts according to claim 1, the described dosing of roughly selecting is 180 gram/ton raw ores, flotation time 6 minutes is scanned and is added dose 50 gram/ton raw ores, flotation time 6 minutes, each selected time is 3 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100317764A CN101318670A (en) | 2008-07-16 | 2008-07-16 | Processing technique for extracting lithium salt from lithium containing salt lake bittern water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100317764A CN101318670A (en) | 2008-07-16 | 2008-07-16 | Processing technique for extracting lithium salt from lithium containing salt lake bittern water |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101318670A true CN101318670A (en) | 2008-12-10 |
Family
ID=40178981
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2008100317764A Pending CN101318670A (en) | 2008-07-16 | 2008-07-16 | Processing technique for extracting lithium salt from lithium containing salt lake bittern water |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101318670A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102154563A (en) * | 2010-12-09 | 2011-08-17 | 江南大学 | Flotation method for enriching lithium from brine of salt lake brine |
| CN102921553A (en) * | 2012-11-23 | 2013-02-13 | 化工部长沙设计研究院 | Method for flotation of lithium potassium sulfate in mixture of lithium potassium sulfate and sodium chloride |
| CN114949893A (en) * | 2022-06-01 | 2022-08-30 | 启东神农机械有限公司 | Evaporative crystallization process and device for producing lithium chloride from salt lake brine |
-
2008
- 2008-07-16 CN CNA2008100317764A patent/CN101318670A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102154563A (en) * | 2010-12-09 | 2011-08-17 | 江南大学 | Flotation method for enriching lithium from brine of salt lake brine |
| CN102921553A (en) * | 2012-11-23 | 2013-02-13 | 化工部长沙设计研究院 | Method for flotation of lithium potassium sulfate in mixture of lithium potassium sulfate and sodium chloride |
| CN114949893A (en) * | 2022-06-01 | 2022-08-30 | 启东神农机械有限公司 | Evaporative crystallization process and device for producing lithium chloride from salt lake brine |
| CN114949893B (en) * | 2022-06-01 | 2024-04-19 | 启东神农机械有限公司 | Evaporation crystallization process and device for producing lithium chloride from salt lake brine |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100528753C (en) | Method for combined extracting boron, magnesium and lithium from salt lake bittern | |
| Rioyo et al. | Lithium extraction from spodumene by the traditional sulfuric acid process: A review | |
| JP5406955B2 (en) | Method for producing lithium carbonate | |
| CN102020294B (en) | Lithium hydroxide monohydrate and preparation method thereof | |
| CN114105171B (en) | Method for comprehensively utilizing lepidolite resources and lithium hydroxide prepared by method | |
| CN104745823B (en) | Method for recycling lithium from waste lithium ion battery | |
| CN103958412A (en) | Process for producing lithium carbonate from concentrated lithium brine | |
| CN111960445B (en) | Method for preparing battery-grade lithium carbonate by using lithium sulfate coarse ore and recycling by-products | |
| CN102491378B (en) | Producing method for preparing lithium carbonate by taking carbonate type brine and sulphate type brine as raw material and by repeatedly mixing brine | |
| CN101318845B (en) | Process for preparing potash magnesium sulphate fertilizer with kalium containing sulfate | |
| CN103924258B (en) | The method utilizing salt lake bittern electrolytic preparation lithium hydroxide | |
| CN103570043A (en) | Method for producing high-purity potassium chloride solution for preparation of potassium carbonate and co-producing low sodium salt | |
| CN101691231A (en) | Method for preparing lithium carbonate by using high boric bittern saturated solution | |
| CN111115665A (en) | Method for recycling lithium-potassium-rich aluminum electrolyte | |
| CN106517263A (en) | Method of carrying out double decomposition on hydrochloric acid leachate of phosphate tailings to prepare magnesium hydroxide and calcium sulfate | |
| CN101905897A (en) | Method for extracting magnesium and lithium from brine | |
| CN108584995B (en) | Method for comprehensively extracting lithium, potassium and boron from oil field brine | |
| CN102372295A (en) | Method for separating magnesium and concentrating lithium in brine | |
| CN101318670A (en) | Processing technique for extracting lithium salt from lithium containing salt lake bittern water | |
| CN1886339A (en) | Process for recovery of potassium sulphate | |
| WO2024036697A1 (en) | Method for enrichment of lithium from lithium clay ore | |
| CN100368298C (en) | Method for preparing strontium carbonate in high purity from celestite ore in mid and low grades | |
| CN108017074A (en) | Salt lake carries the recovery method of lithium solid by-product | |
| Dahlkamp et al. | Production processes for LiOH–A review | |
| CN102336418A (en) | Method for extracting potassium salt from potassium-ion-containing brine |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20081210 |