CN1172072A - Process for concentration of lithium salt in high-magnesian bittern by using mirabilite circulating method - Google Patents
Process for concentration of lithium salt in high-magnesian bittern by using mirabilite circulating method Download PDFInfo
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- CN1172072A CN1172072A CN 96109138 CN96109138A CN1172072A CN 1172072 A CN1172072 A CN 1172072A CN 96109138 CN96109138 CN 96109138 CN 96109138 A CN96109138 A CN 96109138A CN 1172072 A CN1172072 A CN 1172072A
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- bittern
- saltcake
- mirabilite
- liquid phase
- lithium
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Abstract
The present invention discloses a process for enriching lithium salt in magnium-enriched bittern by using mirabilite circulation method. Said technological process includes the following steps: adding mirabilite in magnesium-enriched bittern, mixing and stirring them, separating solid-liquid mixture resulted from reaction to obtain liquid phase and solid phase, air-drying, naturally evaporating separated liquid phase, precipitating solid phase so as to obtain liquid phase material, i.e, concentrated lithium-enriched solution. Its integrative technological process is implemented under the condition of ambient temp., and the large part of mirabilite can be obtained by circulation method, so that it can save energy source and easy to implement.
Description
The present invention relates to the enriching method of lithium salts in the Chemical Manufacture bittern, specifically provide a kind of new processing method of utilizing lithium salts in the high magnesium bittern of saltcake circulation method enrichment.
In natural salt lake or underground containing in the potassium bittern, contain a small amount of lithium salts usually, contain lithium as the northern subsurface brine in Cha Erhan salt lake, China Qinghai and Lop Nur, Xinjiang and be approximately the 15-20 mg/litre.In order from these bittern, to extract sylvite, generally be after salt Tanaka separates halite by Exposure to Sunlight, to separate out sylvite.The old halogen that solarization is got behind the sylvite is that the bittern that is rich in magnesium chloride (contains MgCl
2Generally more than 30%).Lithium salts has been concentrated more than ten times in bittern, and general lithium content can reach the 150-250 mg/litre.
Lithium has important purposes, is called as following metal.With suitable method, can from bittern, extract lithium salts, be expected to obtain remarkable economic efficiency.
From salt lake brine, extract lithium salts at present both at home and abroad, mainly contain ion-exchange-resin process and solvent extration etc., facts have proved, for containing the bittern aforesaid method that lithium is higher, Mg/Li ratio is not really high is feasible, yet, not high for containing lithium, and the very high bittern of Mg/Li ratio, aforesaid method also is difficult to reach a standard economically.
How removing magnesium salts a large amount of in the bittern, and make the lithium enrichment, is this reserves of the development and use key problem in technology that contain lithium bittern resource huge but of low quality.
Once the someone attempted to make old halogen continue evaporation salt Tanaka, by constantly separating out bischofite (MgCl
2.6H
2O) make the Li enrichment, but because the ratio factor of evaporation of old halogen is very little, and velocity of evaporation is slow, suitability for industrialized production is difficult for realizing.
Human alkali (Na was also once arranged
2CO
3) method removes magnesium salts.Obviously alkali charge is too big, is difficult to economically reach a standard.
The object of the present invention is to provide a kind of on Principles of Chemical Engineering, in technological design and all feasible economically saltcake circulation method processing method of coming lithium salts in the high magnesium bittern of enrichment.
Processing method provided by the present invention comprises: get former rich magnesium bittern and add the saltcake mixing, stir, reacted solidliquid mixture is separated, the solid phase that must wet, natural air drying is with the spontaneous evaporation once more of isolated liquid phase, separate out solid phase, get liquid phase substance, be the rich lithium solution after concentrating.
The present invention is according to the phasor principle, utilizes the saltcake circulation method, makes the lithium salts enrichment.Principle is as follows:
In Fig. 1, the composition of bittern is represented with the E point, add saltcake (Na in bittern
2SO
410H
2O), the MgCl in the bittern
2With the saltcake reaction, generate epsom salt (MgSO
47H
2) and halite (NaCl), separate this part epsom salt and halite after, the composition of bittern is developed near the C point by E, evaporate salt Tanaka consisting of the bittern that C selects, separate out halite and epsom salt with continuing, the bittern composition is changed to the E point by the C point in the evaporative process, gets back to the E point at last again.By once circulation, can remove the MgCl of 65-75% in the former halogen
2And water, 100 parts of promptly original bitterns are reduced into 25-35 part.Like this, just made Li enrichment in the bittern about 3 times.
Above-mentionedly add the reaction of saltcake and the evaporative process of salt Tanaka bittern is all carried out under physical environment temperature (10-20 ℃).Saltcake can recycle: obtain and evaporate in the epsom salt of separating out and the halite mixture adding an amount of fresh water in reaction, utilize winter freezing (below 0 ℃), can obtain saltcake (method that epsom salt adds the freezing saltcake of halite is a mature technology) again.
The salt lake brine place of production generally all is in dry cold district, helps utilizing sun power to carry out the salt pan evaporation, and cold weather can make saltcake recycle again.
By the saltcake circulation method triple bittern that made the lithium salts enrichment, when extracting lithium salts with ion exchange method, solvent extration or additive method again, its technological effect will improve greatly.
If after carrying out circulation technology, lithium salt is still not high enough in the bittern, the circular treatment that can also try again, Li concentration reaches suitable degree in bittern.
Fig. 1 is Na, Mg/Cl, SO among the present invention
4-H
215 ℃ of dissolubility pictures of O system (metastable equilibrium)
Fig. 2 is the process flow sheet of lithium salts in the saltcake circulation method enrichment bittern among the present invention.
Wherein each symbol is expressed as respectively: bittern was formed the differentiation direction when arrow represented to add the saltcake reaction obliquely; Oblique arrow down represents that solar evaporation process bittern composition develops direction; On behalf of saltcake, Ep, M represent epsom salt, H to represent halite, Bi to represent bischofite.
Describe below the technology of lithium salts in the saltcake round-robin method enrichment bittern of the present invention in detail with process chart shown in Figure 2.
Technological process shown in Figure 2 is explained as follows:
1. the reaction of former halogen and saltcake is carried out in the reactor that band stirs, and the granularity that adds saltcake is unsuitable excessive, and the saltcake granularity (during 5mm, can react completely in 10 minutes (saltcake all disappears, and forms halite+epsomite).
2. reacted mother liquor is put into salt Tanaka, natural Exposure to Sunlight, and halite+epsomite mixture is separated out in evaporation. Mother liquor forms more close E point in the evaporation process, and mathematical mode is littler, and evaporation rate is slower.
3. mother liquid evaporation was analysed the salt process after bittern added saltcake course of reaction and reaction, all belonged to a kind of metastable equilibrium state. Certain one-phase that carries out in process, in the resulting solid phase amount of halite and epsomite than may changing, but in total recycle process overall and, the molal quantity of halite and epsomite is the (2NaCl: MgSO that equates in the solid phase that obtains4·7H
2O=1: 1). The halite of this equimolar ratio+epsomite mixture just in time is again the freezing suitable material of producing saltcake.
Therefore, the characteristics of visible process provided by the present invention are:
1. add saltcake (NaSO4·10H
2O), make MgCl in the bittern2Form epsomite (MgSO with saltcake4·7H
2) and halite (NaCl) and separated removing;
2. according to Na, Mg/Cl, SO4-H
2The design of O quaternary system solubility the principle of phase diagram, except the Mg process is finished in two steps:
1. bittern is formed as E point among Fig. 1, under agitation adds saltcake, by solid-liquid reaction, forms halite and epsom salt, and mother liquor is formed to C point direction evolution.Through solid-liquid separation process, reacted mother liquor is separated with solid phase;
2. reacted mother liquor by at salt Tanaka solar evaporation, is separated out halite and epsom salt, and the mother liquor composition is got back to the E point from the C point again;
Adding saltcake reaction and evaporative process makes the bittern composition pass through circulation change one time.Bittern is formed forward and reverse change procedure all is a process of separating out halite and epsom salt;
3. under natural temperature, carry out.
4. after two steps finished except that Mg salt process, last bittern (mother liquor) volume was about 1/4.5 of former bittern volume, and the Li ion content can increase about 3 times in the last bittern.
5. because partial L i runs off with wet solid phase, the rate of collecting of the inventive method lithium is 60%-65%.
The present invention carries the lithium salts in the old halogen of high magnesium behind the potassium in order to fully utilize, and makes lithium salts enrichment in the bittern, and Mg/Li ratio descends, and makes this reserves big and the low lithium resource of grade might be exploited, and feasible economically.Whole technology is all carried out at ambient temperature, makes full use of natural temperature differential, because most of saltcake can be obtained with circulation method.Technology utilization of the present invention sun power and natural low temperature condition, except that mix stirring and solid-liquid separation needs with the energy, required input mainly be work, operate.Thereby method of the present invention is a kind of method that works easily economically.
Embodiment 1
The technological process of lithium salts is to carry out under 10-20 ℃ in envrionment temperature in the present embodiment saltcake circulation method enrichment bittern, and the concrete operations step is as follows:
1. get 3.78 liters in former rich magnesium bittern (containing Li 159 mg/litre), add saltcake 3210 grams, mix, stir the 10-20 branch and plant;
2. reacted solidliquid mixture is separated (suction filtration), the solid phase that must wet (epsom salt+halite mixture) 3300 grams are 2915 grams behind the natural air drying; Isolating liquid phase volume is 3.57 liters;
3. with (10-15 ℃) spontaneous evaporation at room temperature of isolated liquid phase, separate out epsom salt+halite mixture, slow until epsom salt+halite speed of separating out, bischofite or be about to separate out.
4. the solidliquid mixture of evaporation being analysed after the salt separates (suction filtration), and the solid phase that must wet (epsom salt+halite mixture) 1325 grams are 1250 grams behind the natural air drying, and obtaining liquid phase volume is 0.80 liter, measures and knows that it is 471 mg/litre that liquid phase contains lithium.
Through once circulation, make that Li content increases to 471 mg/litre by 159 mg/litre in the bittern, concentration increases 2.96 times.
In the cyclic process, some Li runs off with wet solid phase, and the rate of collecting of knowing Li as calculated is 62.7%.
Claims (1)
1, the processing method of lithium salts in the high magnesium bittern of saltcake circulation method enrichment, comprise: get former rich magnesium bittern and add the saltcake mixing, stir, reacted solidliquid mixture is separated the solid phase that to wet, natural air drying, with the spontaneous evaporation once more of isolated liquid phase, separate out solid phase, get liquid phase substance, be the rich lithium solution after concentrating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96109138 CN1172072A (en) | 1996-07-30 | 1996-07-30 | Process for concentration of lithium salt in high-magnesian bittern by using mirabilite circulating method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96109138 CN1172072A (en) | 1996-07-30 | 1996-07-30 | Process for concentration of lithium salt in high-magnesian bittern by using mirabilite circulating method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1172072A true CN1172072A (en) | 1998-02-04 |
Family
ID=5120247
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 96109138 Pending CN1172072A (en) | 1996-07-30 | 1996-07-30 | Process for concentration of lithium salt in high-magnesian bittern by using mirabilite circulating method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100408705C (en) * | 2003-04-30 | 2008-08-06 | 中国科学院青海盐湖研究所 | Nano-filtration method for separating magnesium and enriching lithium from salt lake brine |
| US11180369B2 (en) | 2019-07-30 | 2021-11-23 | Qinghai Institute Of Salt Lakes, Chinese, Academy Of Sciences | Renewable magnesium removing agent and its use in preparation of low-magnesium lithium-rich brine |
-
1996
- 1996-07-30 CN CN 96109138 patent/CN1172072A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100408705C (en) * | 2003-04-30 | 2008-08-06 | 中国科学院青海盐湖研究所 | Nano-filtration method for separating magnesium and enriching lithium from salt lake brine |
| US11180369B2 (en) | 2019-07-30 | 2021-11-23 | Qinghai Institute Of Salt Lakes, Chinese, Academy Of Sciences | Renewable magnesium removing agent and its use in preparation of low-magnesium lithium-rich brine |
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