CN104355559A - Method for separating magnesium and lithium from old brine of salt lake - Google Patents
Method for separating magnesium and lithium from old brine of salt lake Download PDFInfo
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- CN104355559A CN104355559A CN201410554977.8A CN201410554977A CN104355559A CN 104355559 A CN104355559 A CN 104355559A CN 201410554977 A CN201410554977 A CN 201410554977A CN 104355559 A CN104355559 A CN 104355559A
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- lithium
- magnesium
- salt lake
- pyrolysis
- old halogen
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Abstract
The invention provides a method for separating magnesium and lithium from an old brine of a salt lake. The old brine of the salt lake is firstly subjected to pyrolysis to obtain incomplete-pyrolysis magnesium chloride, the incomplete-pyrolysis magnesium chloride is stirred uniformly with water to prepare a magnesium cement product, the magnesium cement product is soaked in water to obtain a lithium-containing solution, and the lithium-containing solution is concentrated and then precipitated with sodium carbonate to obtain lithium carbonate. The old brine of the salt lake is dehydrated and decomposed into magnesium oxide and hydrogen chloride at 400-800 DEG C, the lithium chloride is not composed under the condition, therefore, the lithium salt is easily dissolved in water and enters the solution, but magnesium oxide and magnesium chloride not decomposed are all put into the magnesium cement, the purpose of comprehensively utilizing the magnesium and lithium separated from the old brine of the salt lake is fulfilled, and the process is simple.
Description
[technical field]
The present invention relates to the method that the invention belongs to the old halogen comprehensive utilization in salt lake, particularly relate to a kind of method being separated magnesium lithium in the old halogen in salt lake.
[background technology]
Lithium is a kind of important strategic resources, applies very extensive.Be mainly used in the fields such as glass, pottery and lithium cell.Because lithium ion battery energy is high, lightweight, become the important component part of aerospace operations.Quilonum Retard is as one of most important lithium salts of one, its demand constantly increases along with the growth of global economy, price is also raised on the way, under the powerful drive of global lithium cell market growth, grow up steadily in lithium cell novel material market, the annual average incremental 5% ~ 6% of the demand of world market to Quilonum Retard.
China is lithium resource big country, and explored lithium ore resources industrial reserves occupies the whole world the second, but wherein bittern lithium accounts for 79% of total reserves, and is mainly distributed in the salt lake in Qinghai and Tibet.The solid lithium ore resources of China is along with the decline of ore grade, and production cost sharply rises, and seriously constrains production and the development of lithium salts enterprise, and some lithium salts manufacturing enterprises close down.The lithium salts such as the nineties in last century, China is lithium salts export State, and at present, the required Quilonum Retard of industry have been had to a large amount of import, meet the market requirement of domestic lithium salts industrial development.The disadvantages such as the extraction process of scientific and technical personnel to ground Lithium from Salt Lake Brines such as Qinghai of domestic units concerned has carried out large quantifier elimination and unremitting effort, have breakthrough, but still it is immature to there is technique, and production cost is high.
Because salt lake brine lithium resource reserves account for 70 ~ 80% of lithium resource total amount, therefore salt lake brine carries the Main Means that lithium has become lithium salts production.。
Generally speaking, the technique of extraction and isolation lithium salts from salt lake brine, is summed up both at home and abroad, mainly contains evaporative crystallization method, the precipitator method, extraction process, ion exchange adsorption, calcining leaching method, Xu Shi method and electroosmose process etc.Wherein the precipitator method, extraction process, ion exchange adsorption and carborization are studied extensively and profoundly, are that main salt lake brine puies forward lithium method, and from bittern, extract lithium salts the finished product is all generally Quilonum Retard.
The precipitator method: the precipitator method comprise the method such as carbonate precipitation method, hydrated sulfuric acid lithium crystalline deposit method from extracting lithium from salt lake brine.Carbonate precipitation method is the method studied the earliest and industrially apply from extracting lithium from salt lake brine, and the method is added by calcined soda for industry in concentrated salt lake brine lithium is separated out with Quilonum Retard form.The salt lake brine that this method is suitable for low Mg/Li ratio carries lithium.U.S.'s Sears lake, lithium ore deposit, silver-colored peak and Chilean Atacama salt lake all adopt this method to develop Li
2cO
3product.Hydrated sulfuric acid lithium crystalline deposit method has reported in literature the eighties in last century, but gained Li
2sO
4h
2o purity <95%, rate of recovery <76%.Recently, obtain two kinds of different bittern formed by people by Atacama salt lake brine evaporation concentration, the Lithium Sulphate after mixing in bittern exceedes its solubleness, then divides three phases to be settled out Li
2sO
4h
2o crystal.Li
2sO
4h
2o purity can reach 98.97%, and the total yield of lithium reaches 73.3%.The method does not need separately to add chemical feedstocks, is comparatively suitable for the sulfate type salt lake brine of low Mg/Li ratio, is not suitable for carrying lithium from salt lake brine with high magnesium-lithium ratio.
[summary of the invention]
The defect such as the technical problem to be solved in the present invention to be to overcome in prior art magnesium lithium complex process in the old halogen in preparative separation salt lake, yield poorly, provides the method for magnesium lithium in the old halogen in separation salt lake that a kind of technique is simple, cost is low.
For solving the problems of the technologies described above, the present invention adopts following technical proposals:
Be separated a method for magnesium lithium in the old halogen in salt lake, comprise the steps:
Step S110: the old halogen in pyrolysis salt lake obtains incomplete pyrolysis magnesium chloride;
Step S120: described incomplete pyrolysis magnesium chloride water uniform stirring is made magnesium cement product;
Step S130: described magnesium cement product is soaked in water, obtains lithium-containing solution;
Step S140: described lithium-containing solution is obtained Quilonum Retard by sodium carbonate precipitation after concentrated.
In embodiment provided by the invention, in step S110, the old halogen in described salt lake is that salt lake produces potash fertilizer, carries the mother liquor after boron.
In embodiment provided by the invention, in step S110, the device of described pyrolysis is spray pyrolysis stove, revolution pyrolysis oven, fluidization pyrolysis installation, eddy flow pyrolysis oven.
In embodiment provided by the invention, in step S110, the temperature of described pyrolysis is 200 DEG C-600 DEG C.
In embodiment provided by the invention, in step S110, the rate of decomposition of the magnesium chloride in described incomplete pyrolysis magnesium chloride is between 60% ~ 90%.
In embodiment provided by the invention, in step S130, in described lithium-containing solution, lithium ion leaching yield is more than 95%.
In embodiment provided by the invention, in step S130, the mass ratio of described magnesium cement product and water is 1:1-1:2.
Adopt technique scheme, beneficial effect of the present invention is:
The method of magnesium lithium in the old halogen in separation salt lake that the above embodiment of the present invention provides, first the old halogen in pyrolysis salt lake obtains incomplete pyrolysis magnesium chloride, described incomplete pyrolysis magnesium chloride water uniform stirring is made magnesium cement product, described magnesium cement product is soaked in water, obtain lithium-containing solution, described lithium-containing solution is obtained Quilonum Retard by sodium carbonate precipitation after concentrated, the present invention utilize the old halogen in salt lake 400 DEG C of-800 DEG C of kinetics become magnesium oxide and hydrogenchloride with this understanding lithium chloride do not decompose, therefore lithium salts is soluble in water enters solution and magnesium oxide and undecomposed magnesium chloride all enter magnesium cement phase, reach the object that magnesium lithium is separated the old halogen comprehensive utilization in salt lake, technique is simple.
In addition, the present invention takes full advantage of the old halogen of the unserviceable final product of Salt Lake Potash manufacturing enterprise, makes old halogen obtain effective comprehensive utilization, not only reduces the impact of potash fertilizer enterprise subsequent production and can bring economic benefit for potash fertilizer manufacturing enterprise.
[accompanying drawing explanation]
The flow chart of steps of the method for magnesium lithium in the old halogen in separation salt lake that Fig. 1 provides for the embodiment of the present invention.
[embodiment]
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and the specific embodiments, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
Refer to Fig. 1, the flow chart of steps of the method for magnesium lithium in the old halogen in separation salt lake that Fig. 1 provides for the embodiment of the present invention, as can be seen from Fig. 1, the method being separated magnesium lithium in the old halogen in salt lake comprises the steps:
Step S110: the old halogen in pyrolysis salt lake obtains incomplete pyrolysis magnesium chloride;
Preferably, the old halogen in described salt lake is that salt lake produces potash fertilizer, carries the mother liquor after boron.
Preferably, the device of described pyrolysis is spray pyrolysis stove, revolution pyrolysis oven, fluidization pyrolysis installation, eddy flow pyrolysis oven.
Preferably, the temperature of described pyrolysis is 200 DEG C-600 DEG C.
Preferably, the rate of decomposition of the magnesium chloride in described incomplete pyrolysis magnesium chloride is between 60% ~ 90%.
Step S120: described incomplete pyrolysis magnesium chloride water uniform stirring is made magnesium cement product;
Be appreciated that, the mass ratio of above-mentioned incomplete pyrolysis magnesium chloride and water is particularly important, incomplete pyrolysis magnesium chloride water mix carries out the processing of magnesium cement product in strict accordance with the proportioning of the rate of decomposition of magnesium chloride, the magnesian activity of gained and magnesium cement, in reality, only needing to determine according to the magnesium chloride in pyrolysis product and magnesian content, only needing the water yield added that pyrolysis product can be made shaping through stirring.
Step S130: described magnesium cement product is soaked in water, obtains lithium-containing solution.
Preferably, the mass ratio of described magnesium cement product and water is 1:1-1:2.
Be appreciated that one of object that in above-mentioned steps, magnesium cement product is soaked is that the activated magnesia in magnesium cement product is converted into magnesium cement phase completely, thus improve the performance of magnesium cement product.
On the other hand, the lithium in magnesium cement product is entered by solid phase the object that liquid phase reaches the separation of magnesium lithium by two of the object that in above-mentioned steps, magnesium cement product is soaked completely, and preferably, in described lithium-containing solution, lithium ion leaching yield is more than 95%.
Be appreciated that, soak time determines according to different magnesium cement products, and the soak time that surface-area is large is short, and the magnesium cement product soak time of different fillings is different, key is the intensity that can not affect magnesium cement product, does not affect the use properties of magnesium cement product.
Step S140: described lithium-containing solution is obtained Quilonum Retard by sodium carbonate precipitation after concentrated.
The method of magnesium lithium in the old halogen in separation salt lake that the above embodiment of the present invention provides, first the old halogen in pyrolysis salt lake obtains incomplete pyrolysis magnesium chloride, described incomplete pyrolysis magnesium chloride water uniform stirring is made magnesium cement product, described magnesium cement product is soaked in water, obtain lithium-containing solution, described lithium-containing solution is obtained Quilonum Retard by sodium carbonate precipitation after concentrated, the present invention utilize the old halogen in salt lake 400 DEG C of-800 DEG C of kinetics become magnesium oxide and hydrogenchloride with this understanding lithium chloride do not decompose, therefore lithium salts is soluble in water enters solution and magnesium oxide and undecomposed magnesium chloride all enter magnesium cement phase, reach the object that magnesium lithium is separated the old halogen comprehensive utilization in salt lake, technique is simple.
In addition, the present invention takes full advantage of the old halogen of the unserviceable final product of Salt Lake Potash manufacturing enterprise, makes old halogen obtain effective comprehensive utilization, not only reduces the impact of potash fertilizer enterprise subsequent production and can bring economic benefit for potash fertilizer manufacturing enterprise.
Set forth the present invention further by the following examples, these embodiments are only presented for purposes of illustration, do not limit the scope of the invention.Except the actual conditions indicated, the test method in embodiment all conveniently condition is carried out.
Embodiment 1
The old halogen in salt lake pumps into pyrolysis installation, pyrolysis temperature 400 DEG C, residence time 90min, obtain incomplete pyrolysis product, analyze wherein magnesium chloride rate of decomposition 60%, add a certain amount of sawdust water and mix pasty state in 2 × 2 × 2 die for molding, after the demoulding soaked one day, the leaching yield of lithium ion is 96%, seven days rear side magnesium strengths of cement is 20MPa.
Embodiment 2
The old halogen in salt lake pumps into pyrolysis installation, pyrolysis temperature 550 DEG C, residence time 20min, obtain incomplete pyrolysis product, analyze wherein magnesium chloride rate of decomposition 70%, add a certain amount of sawdust water and mix pasty state in 2 × 2 × 2 die for molding, after the demoulding soaked two days, the leaching yield of lithium ion is that within 97%, seven days, to survey magnesium strength of cement be afterwards 22MPa.
Embodiment 3
The old halogen in salt lake pumps into pyrolysis installation, pyrolysis temperature 650 DEG C, residence time 10min, obtain incomplete pyrolysis product, analyze wherein magnesium chloride rate of decomposition 85%, add a certain amount of sawdust water and mix pasty state in 2 × 2 × 2 die for molding, after the demoulding soaked three days, the leaching yield of lithium ion is that within 95%, seven days, to survey magnesium strength of cement be afterwards 20MPa.
Embodiment 4
The old halogen in salt lake pumps into pyrolysis installation, pyrolysis temperature 800 DEG C, residence time 2min, obtain incomplete pyrolysis product, analyze wherein magnesium chloride rate of decomposition 90%, add a certain amount of marine alga use water and mix pasty state in 2 × 2 × 2 die for molding, after the demoulding soaked five days, the leaching yield of lithium ion is 100%, seven days rear side magnesium strengths of cement is 20MPa.
Embodiment 5
The old halogen in salt lake pumps into pyrolysis installation, pyrolysis temperature 800 DEG C, residence time 2min, obtain incomplete pyrolysis product, analyze wherein magnesium chloride rate of decomposition 90%, add a certain amount of river sand water and mix pasty state in 2 × 2 × 2 die for molding, after the demoulding soaked five days, the leaching yield of lithium ion is 98%, seven days rear side magnesium strengths of cement is 30MPa.
Embodiment 6
The old halogen in salt lake pumps into pyrolysis installation, pyrolysis temperature 800 DEG C, residence time 2min, obtain incomplete pyrolysis product, analyze wherein magnesium chloride rate of decomposition 90%, add a certain amount of sawdust and add a certain amount of whipping agent, pasty state is mixed in 2 × 2 × 2 die for molding with water, after the demoulding soaked five days, the leaching yield of lithium ion is 100%, seven days rear side magnesium strengths of cement was 19MPa.
The above, it is only preferred embodiment of the present invention, not any pro forma restriction is done to the present invention, although the present invention discloses as above with preferred embodiment, but and be not used to limit the present invention, any those skilled in the art, do not departing within the scope of technical solution of the present invention, make a little change when the technology contents of above-mentioned announcement can be utilized or be modified to the Equivalent embodiments of equivalent variations, in every case be do not depart from technical solution of the present invention content, according to any simple modification that technical spirit of the present invention is done above embodiment, equivalent variations and modification, all still belong in the scope of technical solution of the present invention.
Claims (7)
1. be separated a method for magnesium lithium in the old halogen in salt lake, it is characterized in that, comprise the steps:
Step S110: the old halogen in pyrolysis salt lake obtains incomplete pyrolysis magnesium chloride;
Step S120: described incomplete pyrolysis magnesium chloride water uniform stirring is made magnesium cement product;
Step S130: described magnesium cement product is soaked in water, obtains lithium-containing solution;
Step S140: described lithium-containing solution is obtained Quilonum Retard by sodium carbonate precipitation after concentrated.
2. the method for magnesium lithium in the old halogen in separation salt lake according to claim 1, is characterized in that, in step S110, the old halogen in described salt lake be salt lake produce potash fertilizer, carry boron after mother liquor.
3. the method for magnesium lithium in the old halogen in separation salt lake according to claim 1, is characterized in that, in step S110, the device of described pyrolysis is spray pyrolysis stove, revolution pyrolysis oven, fluidization pyrolysis installation, eddy flow pyrolysis oven.
4. the method for magnesium lithium in the old halogen in separation salt lake according to claim 1, it is characterized in that, in step S110, the temperature of described pyrolysis is 200 DEG C-600 DEG C.
5. the method for magnesium lithium in the old halogen in separation salt lake according to claim 1, it is characterized in that, in step S110, the rate of decomposition of the magnesium chloride in described incomplete pyrolysis magnesium chloride is between 60% ~ 90%.
6. the method for magnesium lithium in the old halogen in separation salt lake according to claim 1, it is characterized in that, in step S130, in described lithium-containing solution, lithium ion leaching yield is more than 95%.
7. the method for magnesium lithium in the old halogen in separation salt lake according to claim 1, it is characterized in that, in step S130, the mass ratio of described magnesium cement product and water is 1:1-1:2.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1335263A (en) * | 2001-09-07 | 2002-02-13 | 中信国安锂业科技有限责任公司 | Carbonization process of separating Mg and Li salt and preparing lithium carbonate from salt lake bittern with high Mg/Li ratio |
| US20030228251A1 (en) * | 1998-07-16 | 2003-12-11 | Boryta Daniel Alfred | Production of lithium compounds directly from lithium containing brines |
| US20040005267A1 (en) * | 1998-07-16 | 2004-01-08 | Boryta Daniel Alfred | Production of lithium compounds directly from lithium containing brines |
| CN101117225A (en) * | 2007-07-17 | 2008-02-06 | 陈兆华 | Process for producing high-purity magnesium oxide and lithium salt by using salt lake old brine |
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2014
- 2014-10-17 CN CN201410554977.8A patent/CN104355559B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030228251A1 (en) * | 1998-07-16 | 2003-12-11 | Boryta Daniel Alfred | Production of lithium compounds directly from lithium containing brines |
| US20040005267A1 (en) * | 1998-07-16 | 2004-01-08 | Boryta Daniel Alfred | Production of lithium compounds directly from lithium containing brines |
| CN1335263A (en) * | 2001-09-07 | 2002-02-13 | 中信国安锂业科技有限责任公司 | Carbonization process of separating Mg and Li salt and preparing lithium carbonate from salt lake bittern with high Mg/Li ratio |
| CN101117225A (en) * | 2007-07-17 | 2008-02-06 | 陈兆华 | Process for producing high-purity magnesium oxide and lithium salt by using salt lake old brine |
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