CN106517260B - A kind of technique for preparing lithium carbonate with lake bittern water containing lithium salts - Google Patents

A kind of technique for preparing lithium carbonate with lake bittern water containing lithium salts Download PDF

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CN106517260B
CN106517260B CN201710000559.8A CN201710000559A CN106517260B CN 106517260 B CN106517260 B CN 106517260B CN 201710000559 A CN201710000559 A CN 201710000559A CN 106517260 B CN106517260 B CN 106517260B
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water containing
containing lithium
lithium salts
lake bittern
gained
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CN106517260A (en
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谢超
夏适
高文远
汤建良
郑贤福
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China Bluestar Chonfar Engineering and Technology Co Ltd
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China Bluestar Changsha Design and Research Institute
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/08—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D3/00—Halides of sodium, potassium or alkali metals in general
    • C01D3/04—Chlorides
    • C01D3/06—Preparation by working up brines; seawater or spent lyes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/46—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F5/00—Compounds of magnesium
    • C01F5/14—Magnesium hydroxide
    • C01F5/22—Magnesium hydroxide from magnesium compounds with alkali hydroxides or alkaline- earth oxides or hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity

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Abstract

A kind of technique that lithium carbonate is prepared with lake bittern water containing lithium salts, comprises the following steps：（1）Preparing lime milk suspension, lime cream soliquoid is well mixed with lake bittern water containing lithium salts；（2）The moisture equivalent to the mixture quality of lake bittern water containing lithium salts 10 ~ 70% is evaporated, then carries out separation of solid and liquid；（3）Continue to evaporate the moisture equivalent to 35 ~ 60%, then carry out separation of solid and liquid；（4）Continue the moisture of evaporation 35 ~ 60%, carry out separation of solid and liquid again；（5）Add the solution of alkali or alkali, adjustment pH value to 11 ~ 14, filtering；（6）Oxalic acid or oxalate solution are added, deliming, filtering, leaves and takes filtrate；（7）Carbon dioxide is passed through into filtrate, or adds carbonate, separation of solid and liquid, filter residue is lithium carbonate.The present invention realizes that the salt lake bittern of high Mg/Li ratio puies forward lithium, the technique for preparing industrial level lithium carbonate；Technological process is short, and equipment is simple, and production cost is low.

Description

A kind of technique for preparing lithium carbonate with lake bittern water containing lithium salts
Technical field
The invention belongs to exploit resources of salt lakes to utilize field, and lithium carbonate is prepared with lake bittern water containing lithium salts more particularly, to one kind Technique.
Background technology
China's lithium resource 80% is contained in salt lake bittern, but wherein saline lake lithium resource Exploitation degree is very low, is only capable of carrying at present For 20% or so lithium salts yield, meanwhile, external most lithium salts products come from salt lake, and it is most to be primarily due to China salt lake Number belongs to chloride and sulfate type, and magnesium ion content is generally higher in this two classes salt lake, causes Mg/Li ratio higher, magnesium lithiumation Physical property is veryed close, and must remove magnesium ion during lithium is carried, and magnesium ion content is high, greatly improves salt lake bittern In put forward the cost of lithium.Part lithium can be lost during demagging simultaneously, makes the reduction of lithium yield, part magnesium ion is will also result in and enters production In product, make product quality not up to standard.As more than Mg/Li ratio in Qinghai Salt Lake 50:More than 1, Mg/Li ratio also more in Tibetan Salt Lakes exists 10：More than 1, these are the main reason for lithium resource for causing Qinghai to be enriched with Tibetan Salt Lakes do not obtain large-scale development.With The development of New Energy Industry, are increased severely requirement and the day of lithium carbonate, therefore, research and development lake bittern water containing lithium salts prepares lithium carbonate Technique, it appears it is particularly important, put forward lithium technology in particular for salt lake brine with high magnesium-lithium ratio.
At present, the salt lake bittern exploitation of high Mg/Li ratio, also has successful example, as absorption method carries lithium, calcination method carries lithium, electricity Dialysis carries lithium, extraction carries lithium etc..Wherein, selective absorption will be helpful to solve this problem, but this is crucial for adsorbent Technology fails effectively to be broken through, and calcination method carries lithium because its energy consumption and the problems such as pollution are not also promoted, electroosmose process Need special device and permeable membrane, the serious development for limiting salt lake and putting forward lithium industry of the presence of these problems.At present, salt lake It is more from the relatively low salt lake of Mg/Li ratio to produce lithium carbonate, such as the Salt Lake Zabuye in China, the salt lake is calcareous type salt lake, magnesium from Sub- content is very low（Only 0.004wt% or so）, lithium ion content is 0.13wt% or so, and Mg/Li ratio is about 0.003:1；And for example intelligence Sharp and Argentine Atacama salt lakes and Hombre Muerto salt lakes, although being that sulfate type Mg/Li ratio one is 6.5:1, One is 1.3:1, belong to the salt lake of the low high lithium of magnesium.
The A of CN 102432044, which are disclosed, extracts ultra-high purity lithium carbonate in a kind of chloride type bittern from high Mg/Li ratio Method, lithium chloride concentrate is produced by absorption-desorption and evaporating and concentrating process, precipitated after purification using ammonium hydrogen carbonate water slurry Go out lithium carbonate, be then converted to lithia water, filter simultaneously decarburization.But absorption method often may require that substantial amounts of polymeric adsorbent with The devices such as adsorption tower, while technological process is complicated, and strict dedoping step is needed, operation inconvenience.
CN101698488A discloses a kind of method that lithium carbonate is prepared using salt lake brine with high magnesium-lithium ratio, but it has been used Solvent extraction, it has several defects, first, organic solution has certain toxicity and corrosivity, easily causes environmental pollution；Two It is that extractant has loss in extraction process, causes cost higher；Third, extraction frequently includes extraction, back extraction, concentration, extraction The processes such as the recovery of agent so that the flow of this method is longer；Fourth, extraction equipment is complex, construction investment is big.
The above all limits the utilization of lithium resource in salt lake brine with high magnesium-lithium ratio.
The content of the invention
The technical problem to be solved in the present invention is overcome the deficiencies in the prior art, there is provided a kind of cost is relatively low, and operation is simpler It is single, the higher technique for preparing lithium carbonate with lake bittern water containing lithium salts of yield.
It is a kind of work that lithium carbonate is prepared with lake bittern water containing lithium salts that the present invention, which solves the technical scheme that its technical problem uses, Skill, comprise the following steps：
（1）The lime cream soliquoid that mass concentration is 5 ~ 40% is prepared, lime cream soliquoid and lake bittern water containing lithium salts are pressed into matter Than being well mixed for 0.5 ~ 6 ︰ 100 ratio, the dosage of the lime cream soliquoid obtains amount in terms of being come by calcium oxide contained therein The compound of lake bittern water containing lithium salts；
The lime cream soliquoid, it can suit measures to local conditions, by the lime stone of locality, firing obtains CaO, then preparing lime milk hangs Supernatant liquid（If directly calcium oxide solid is added in lake bittern water containing lithium salts, it will not react, be unable to reach purpose）, lime Stone fires gained carbon dioxide and can be applied to subsequent step of the present invention（7）In, to reduce cost.
The lake bittern water containing lithium salts, it is lithium ion content >=0.01wt% lake bittern water containing lithium salts；The present invention is suitable to Mg/Li ratio ≤200:1 lake bittern water containing lithium salts, the ︰ 1 of the Mg/Li ratio that is particularly suitable for use in >=10（The particularly ︰ 1 of Mg/Li ratio >=30）High Mg/Li ratio Lake bittern water containing lithium salts；
The purpose of this step is that the sulfate ion in salt lake bittern is removed using the calcium of milk of lime, utilizes the alkali of milk of lime Property is settled out Mg（OH）2And demagging；Reduce Mg/Li ratio, simplification of flowsheet.
（2）By step（1）Gained lake bittern water containing lithium salts compound is tedded using salt pan or forced evaporation technique, and evaporation is suitable In the moisture of the mixture quality of lake bittern water containing lithium salts 10 ~ 70%（Control lithium ion content ＜ 0.2wt%）, then separation of solid and liquid is carried out, Gained solid is Mg (OH)2With CaSO4Precipitation, magnesium and gypsum is prepared available for carrying；Gained liquid is bittern I；
In the prior art, conventional method is all not evaporate direct separation of solid and liquid, and demagging is less, subsequent step complex operation, The present invention has broken this routine.Separation of solid and liquid after the evaporation of this step, leading demagging, can simplify subsequent process flow, demagging More, lithium loss is also less.
（3）By step（2）Gained bittern I continues moisture of the evaporation equivalent to the mass 35 ~ 60% of bittern I（Control lithium ion contains Measure ＜ 1.0%）, then separation of solid and liquid is carried out, gained solid is NaCl；Gained liquid is bittern II；
（4）Continue evaporation equivalent to step（3）The moisture of the mass 35 ~ 60% of gained bittern II（Control lithium ion content ＞ 2.0%）, separation of solid and liquid is carried out again；Obtain solid containing potassium and clear liquid containing lithium；Gained solid containing potassium can use floatation to prepare KCl；
（5）By step（4）Clear liquid containing lithium obtained by separation of solid and liquid adds the solution of alkali or alkali, adjustment pH value to 11 ~ 14（Control Magnesium ion content ＜ 0.01wt%）, filtering, filter residue is magnesium hydrate precipitate, leaves and takes filtrate I；
Described alkali preferred NaOH, Na2CO3, at least one of KOH；
The purpose of this operating procedure is depth demagging, and the magnesium of early stage removes not totally, adds this step further to remove surplus Remaining a small amount of magnesium, ensure the grade of lithium salts.
（6）Toward step（5）Oxalic acid or oxalate solution are added in gained filtrate I（The preferred sodium oxalate of the oxalates, oxalic acid At least one of potassium）, deliming（Calcium ion content is controlled to be less than 0.01%）, filtering, filter residue is calcium oxalate, leaves and takes filtrate II；
The addition of the oxalic acid or oxalates, depending on calcium ion content, in general, oxalic acid or oxalates and filter The mass ratio of liquid I is 0.1 ~ 1:100.
（7）Toward step（6）Carbon dioxide is passed through in gained filtrate II and [step can be used（1）Lime stone fires what is obtained CO2], or carbonate is added, lithium ion content ＜ 0.2wt% in solution are controlled, separation of solid and liquid, filter residue is lithium carbonate（Technical grade）, Filtrate return to step（4）Continue concentration and evaporation.
The carbonate is at least one of sodium carbonate, ammonium carbonate, potassium carbonate.
The advantage of the invention is that：
1st, realize that the salt lake bittern of high Mg/Li ratio puies forward lithium, the technique for preparing industrial level lithium carbonate；
2nd, technological process of the present invention is short, and equipment is simple, and investment is low；
3rd, present invention process lithium ion yield is more than 80%, and purity is more than 98.9%；
4th, lithium carbonate production cost of the present invention is low.
The present invention uses traditional depositing technology, for salt lake feature, by the way of demagging early stage, obtains low Mg/Li ratio Bittern, ternary phase diagrams is used during bittern evaporation to instruct, obtains preferably technological parameter, product yield is high, product matter Measure.
Embodiment
The invention will be further described with reference to embodiments.
The purity detecting of gained lithium carbonate in each embodiment, using existing national standard（GB/T 11075-2003）Defined side Method is detected.
Embodiment 1
The present embodiment comprises the following steps：
（1）The CaO 53g that lime stone is fired to obtain, the lime cream soliquoid that mass concentration is 30% is tuned into, with 1000g The lake bittern water containing lithium salts of high Mg/Li ratio 5.3 ︰ 100 in mass ratio ratio is well mixed, and obtains the compound of lake bittern water containing lithium salts；
In terms of the dosage of the lime cream soliquoid is come by calcium oxide contained therein；The halogen of lake containing lithium salts of the high Mg/Li ratio Water Mg/Li ratio is 30:1, lithium ion content 0.07wt%.
Lime stone fires gained carbon dioxide and can be applied to the present embodiment subsequent step（7）In, to reduce cost.
（2）By step（1）Gained lake bittern water containing lithium salts compound is tedded using salt pan, is evaporated equivalent to lake bittern water containing lithium salts The moisture of mixture quality 50%（Control lithium ion content ＜ 0.2wt%）, then separation of solid and liquid is carried out, gained solid is Mg (OH)2 With CaSO4Precipitation, magnesium and gypsum is prepared available for carrying；Gained liquid is bittern I；
（3）By step（2）Gained bittern I continues 50% moisture of the evaporation equivalent to the mass of bittern I（Control lithium ion contains Measure ＜ 1.0%）, separation of solid and liquid is carried out again, and gained solid is NaCl；Gained liquid is bittern II；
（4）Continue evaporation equivalent to step（3）The moisture of the mass 50% of gained bittern II（Control lithium ion content ＞ 2.0%）, separation of solid and liquid is carried out again；Obtain solid containing potassium and clear liquid containing lithium；Gained solid containing potassium is prepared using floatation KCl；
（5）By step（4）Clear liquid containing lithium obtained by separation of solid and liquid adds highly basic NaOH solution, adjustment pH value to 13（Control magnesium Ion concentration ＜ 0.01wt%）, filtering, filter residue magnesium hydrate precipitate is removed, leaves and takes filtrate I；
（6）Toward step（5）Oxalic acid, deliming are added in gained filtrate I（Calcium ion content is controlled to be less than 0.01%）, filter off Except filter residue calcium oxalate, filtrate II is left and taken；
（7）Toward step（6）Carbon dioxide is passed through in gained filtrate II and [uses step（1）Lime stone fires obtained CO2], Lithium ion content ＜ 0.2wt% in solution are controlled, separation of solid and liquid is industrial level lithium carbonate 3.14g after filter residue and drying, and filtrate returns Step（4）Continue concentration and evaporation.
Purity is 99.1% after the present embodiment lithium carbonate is dried, yield 84%.
Embodiment 2
The present embodiment comprises the following steps：
（1）The 13g CaO that lime stone is fired to obtain, the lime cream soliquoid that mass concentration is 40% is tuned into, by milk of lime The lake bittern water containing lithium salts of suspension and 1000g high Mg/Li ratios 1.3 ︰ 100 in mass ratio ratio is well mixed, and obtains the halogen of lake containing lithium salts Water mixture；
In terms of the dosage of the lime cream soliquoid is come by calcium oxide contained therein；The halogen of lake containing lithium salts of the high Mg/Li ratio Water Mg/Li ratio is 10:1, lithium ion content 0.05wt%.
Lime stone fires gained carbon dioxide and can be applied to the present embodiment subsequent step（7）In, to reduce cost.
（2）By step（1）Gained lake bittern water containing lithium salts compound is tedded using salt pan, is evaporated equivalent to lake bittern water containing lithium salts The moisture of mixture quality 60%（Control lithium ion content ＜ 0.2wt%）, separation of solid and liquid is carried out, gained solid is Mg (OH)2With CaSO4Precipitation, magnesium and gypsum is prepared available for carrying；Gained liquid is bittern I；
（3）By step（2）Gained bittern I continues moisture of the evaporation equivalent to the mass 40% of bittern I（Control lithium ion content ＜ 1.0%）, separation of solid and liquid is carried out again, and gained solid is NaCl；Gained liquid is bittern II；
（4）Continue evaporation equivalent to step（3）The moisture of the mass 55% of gained bittern II（Control lithium ion content ＞ 2.0%）, separation of solid and liquid is carried out again；Obtain solid containing potassium and clear liquid containing lithium；Gained solid containing potassium can use floatation to prepare KCl；
（5）By step（4）Clear liquid containing lithium obtained by separation of solid and liquid adds highly basic NaOH solution, adjustment pH value to 14（Control magnesium Ion concentration ＜ 0.01wt%）, filter off except magnesium hydrate precipitate, leave and take filtrate I；
（6）Toward step（5）Oxalic acid, deliming are added in gained filtrate I（Calcium ion content is controlled to be less than 0.01%）, filter off Except calcium oxalate, filtrate II is left and taken；
（7）Toward step（6）Carbon dioxide is passed through in gained filtrate II and [uses step（1）Lime stone fires obtained CO2], Lithium ion content ＜ 0.2wt% in solution are controlled, separation of solid and liquid is industrial level lithium carbonate 2.18g after filter residue and drying, and filtrate returns Step（4）Continue concentration and evaporation.
Purity is 99.4% after the present embodiment lithium carbonate is dried, yield 82%.
Embodiment 3
The present embodiment comprises the following steps：
（1）The 55g CaO that lime stone is fired to obtain, the lime cream soliquoid that mass concentration is 40% is tuned into, by milk of lime The lake bittern water containing lithium salts of suspension and 1000g high Mg/Li ratios 5.5 ︰ 100 in mass ratio ratio is well mixed, and the milk of lime hangs The dosage of supernatant liquid obtains the compound of lake bittern water containing lithium salts in terms of coming by calcium oxide contained therein；The lake containing lithium salts of the high Mg/Li ratio Bittern Mg/Li ratio is 200:1, lithium ion content 0.01wt%.
Lime stone fires gained carbon dioxide and can be applied to the present embodiment subsequent step（7）In, to reduce cost.
（2）By step（1）Gained lake bittern water containing lithium salts compound is tedded using salt pan, is evaporated equivalent to lake bittern water containing lithium salts The moisture of mixture quality 60%（Control lithium ion content ＜ 0.2wt%）, then carry out separation of solid and liquid；Gained solid is Mg (OH)2 With CaSO4Precipitation, magnesium and gypsum is prepared available for carrying；Gained liquid is bittern I；
（3）By step（2）Gained bittern I continues moisture of the evaporation equivalent to the mass 55% of bittern I（Control lithium ion content ＜ 1.0%）, separation of solid and liquid is carried out again, and gained solid is NaCl；Gained liquid is bittern II；
（4）Continue evaporation equivalent to step（3）The moisture of the mass 60% of gained bittern II（Control lithium ion content ＞ 2.0%）, separation of solid and liquid is carried out again；Obtain solid containing potassium and clear liquid containing lithium；Gained solid containing potassium can use floatation to prepare KCl；
（5）By step（4）Clear liquid containing lithium adds highly basic NaOH solution obtained by separation of solid and liquid, adjusts pH value 14（Control magnesium from Sub- content ＜ 0.01wt%）, filtering, filter residue is magnesium hydrate precipitate, leaves and takes filtrate I；
（6）Toward step（5）Oxalic acid, deliming are added in gained filtrate I（Calcium ion content is controlled to be less than 0.01%）, filter off Except calcium oxalate, filtrate II is left and taken；
（7）Toward step（6）Carbon dioxide is passed through in gained filtrate II and [uses step（1）Lime stone fires obtained CO2], Lithium ion content ＜ 0.2wt% in solution are controlled, separation of solid and liquid, are lithium carbonate after filter residue and drying（Technical grade）0.42g, filtrate are returned Return step（4）Continue concentration and evaporation.
Purity is 99.6% after lithium carbonate is dried obtained by the present embodiment, yield 80%.
Embodiment 4
The present embodiment comprises the following steps：
（1）The 22g CaO that lime stone is fired to obtain, the lime cream soliquoid that mass concentration is 40% is tuned into, by milk of lime Suspension is well mixed with 1000g salt lake brine with high magnesium-lithium ratio 2.2 ︰ 100 in mass ratio ratio, the lime cream soliquoid Dosage come by calcium oxide contained therein in terms of, obtain the compound of lake bittern water containing lithium salts；The lake bittern water containing lithium salts of the high Mg/Li ratio Mg/Li ratio is 20:1, lithium ion content 0.04wt%.
Lime stone fires gained carbon dioxide and can be applied to the present embodiment subsequent step（7）In, to reduce cost.
（2）By step（1）Gained lake bittern water containing lithium salts is tedded using salt pan, is evaporated equivalent to the compound of lake bittern water containing lithium salts The moisture of quality 50%（Control lithium ion content ＜ 0.2wt%）, carry out separation of solid and liquid；Gained solid is Mg (OH)2With CaSO4It is heavy Form sediment, magnesium and gypsum is prepared available for carrying；Gained liquid is bittern I；
（3）By step（2）Gained bittern I continues moisture of the evaporation equivalent to the mass 45% of bittern I（Control lithium ion content ＜ 1.0%）, separation of solid and liquid is carried out again；Gained solid is NaCl；Gained liquid is bittern II；
（4）Continue evaporation equivalent to step（3）The moisture of the mass 50% of gained bittern II（Control lithium ion content ＞ 2.0%）, separation of solid and liquid is carried out again, obtains solid containing potassium and clear liquid containing lithium；Gained solid containing potassium can use floatation to prepare KCl；
（5）By step（4）Clear liquid containing lithium adds highly basic NaOH solution obtained by separation of solid and liquid, adjusts pH value 11（Control magnesium from Sub- content ＜ 0.01wt%）, filtering, filter residue is magnesium hydrate precipitate, leaves and takes filtrate I；
（6）Toward step（5）Oxalic acid, deliming are added in gained filtrate I（Calcium ion content is controlled to be less than 0.01%）, filter off Except calcium oxalate, filtrate II is left and taken；
（7）Toward step（6）Carbon dioxide is passed through in gained filtrate II and [uses step（1）Lime stone fires obtained CO2], Lithium ion content ＜ 0.2wt% in solution are controlled, separation of solid and liquid, are lithium carbonate after filter residue and drying（Technical grade）1.75g, filtrate are returned Return step（4）Continue concentration and evaporation.
Purity is 98.9% after the present embodiment lithium carbonate is dried, yield 82%.
Embodiment 5
The present embodiment comprises the following steps：
（1）The 43g CaO that lime stone is fired to obtain, the lime cream soliquoid that mass concentration is 30% is tuned into, by milk of lime Suspension is well mixed with 4.3 ︰ 100 in mass ratio of the lake bittern water containing lithium salts with 1000g high Mg/Li ratios ratio, the milk of lime The dosage of suspension obtains the compound of lake bittern water containing lithium salts in terms of coming by calcium oxide contained therein；The high Mg/Li ratio contains lithium salts Lake bittern water Mg/Li ratio is 50:1, lithium ion content 0.03wt%.
Lime stone fires gained carbon dioxide and can be applied to the present embodiment subsequent step（7）In, to reduce cost.
（2）By step（1）Gained lake bittern water containing lithium salts compound is tedded using salt pan, is evaporated equivalent to lake bittern water containing lithium salts The moisture of mixture quality 70%（Control lithium ion content ＜ 0.2wt%）, carry out separation of solid and liquid；Gained solid is Mg (OH)2With CaSO4Precipitation, magnesium and gypsum is prepared available for carrying；Gained liquid is bittern I；
（3）By step（2）Gained bittern I continues moisture of the evaporation equivalent to the mass 35% of bittern I（Control lithium ion content ＜ 1.0%）, then separation of solid and liquid is carried out, gained solid is NaCl；Gained liquid is bittern II；
（4）Continue evaporation equivalent to step（3）The moisture of the mass 35% of gained bittern II（Control lithium ion content ＞ 2.0%）, separation of solid and liquid is carried out again；Obtain solid containing potassium and clear liquid containing lithium；Gained solid containing potassium can use floatation to prepare KCl；
（5）By step（4）The highly basic NaOH solution of clear liquid containing lithium obtained by separation of solid and liquid, adjust pH value 13（Control magnesium ion contains Measure ＜ 0.01wt%）, filtering, filter residue magnesium hydrate precipitate is removed, leaves and takes filtrate I；
（6）Toward step（5）Oxalic acid, deliming are added in gained filtrate I（Calcium ion content is controlled to be less than 0.01%）, filter off Except calcium oxalate, filtrate II is left and taken；
（7）Toward step（6）Carbon dioxide is passed through in gained filtrate II and [uses step（1）Lime stone fires obtained CO2], Lithium ion content ＜ 0.2wt% in solution are controlled, separation of solid and liquid, are lithium carbonate after filter residue and drying（Technical grade）1.33g, filtrate are returned Return step（4）Continue concentration and evaporation.
In the present embodiment, purity is 99.0% after lithium carbonate is dried, yield 83%.
Embodiment 6
The present embodiment comprises the following steps：
（1）The 52.6g CaO that lime stone is fired to obtain, the lime cream soliquoid that mass concentration is 30% is tuned into, by lime Milk suspension is well mixed with 5.26 ︰ 100 in mass ratio of the lake bittern water containing lithium salts with 1000g high Mg/Li ratios ratio, the stone The dosage of grey milk suspension obtains the compound of lake bittern water containing lithium salts in terms of coming by calcium oxide contained therein；The high Mg/Li ratio contains Lithium salts lake bittern water Mg/Li ratio is 100:1, lithium ion content 0.02wt%.
Lime stone fires gained carbon dioxide and can be applied to the present embodiment subsequent step（7）In, to reduce cost.
（2）By step（1）Gained lake bittern water containing lithium salts compound is tedded using salt pan, is evaporated equivalent to lake bittern water containing lithium salts The moisture of mixture quality 10%（Control lithium ion content ＜ 0.2wt%）, carry out separation of solid and liquid；Gained solid is Mg (OH)2With CaSO4Precipitation, magnesium and gypsum is prepared available for carrying；Gained liquid is bittern I；
（3）By step（2）Gained bittern I continues moisture of the evaporation equivalent to the mass 60% of bittern I（Control lithium ion content ＜ 1.0%）, separation of solid and liquid is carried out again；Gained solid is NaCl；Gained liquid is bittern II；
（4）Continue evaporation equivalent to step（3）The moisture of the mass 60% of gained bittern II（Control lithium ion content ＞ 2.0%）, separation of solid and liquid is carried out again；Obtain solid containing potassium and clear liquid containing lithium；Gained solid containing potassium can use floatation to prepare KCl；
（5）By step（4）Clear liquid containing lithium adds highly basic NaOH solution obtained by separation of solid and liquid, adjusts pH value 13（Control magnesium from Sub- content ＜ 0.01wt%）, filtering, filter residue is magnesium hydrate precipitate, leaves and takes filtrate I；
（6）Toward step（5）Oxalic acid, deliming are added in gained filtrate I（Calcium ion content is controlled to be less than 0.01%）, filter, filter Slag is calcium oxalate, leaves and takes filtrate II；
（7）Toward step（6）Carbon dioxide is passed through in gained filtrate II and [uses step（1）Lime stone fires obtained CO2], Lithium ion content ＜ 0.2wt% in solution are controlled, separation of solid and liquid, are lithium carbonate after filter residue and drying（Technical grade）0.91g, filtrate are returned Return step（4）Continue concentration and evaporation.
Purity is 99.1% after lithium carbonate is dried in the present embodiment, yield 85%.

Claims (10)

1. a kind of technique for preparing lithium carbonate with lake bittern water containing lithium salts, it is characterised in that comprise the following steps：
（1）The lime cream soliquoid that mass concentration is 5 ~ 40% is prepared, by lime cream soliquoid and lake bittern water containing lithium salts in mass ratio Ratio for 0.5 ~ 6 ︰ 100 is well mixed, and the dosage of the lime cream soliquoid is obtained containing lithium in terms of being come by calcium oxide contained therein Salt lake bittern compound；
The lake bittern water containing lithium salts, it is lithium ion content >=0.01wt% lake bittern water containing lithium salts；
（2）By step（1）Gained lake bittern water containing lithium salts compound is tedded using salt pan or forced evaporation technique, evaporate equivalent to containing The moisture of lithium salts lake bittern water mixture quality 10 ~ 70%, then separation of solid and liquid is carried out, gained solid is Mg (OH)2With CaSO4Precipitation； Gained liquid is bittern I；
（3）By step（2）Gained bittern I continues moisture of the evaporation equivalent to the mass 35 ~ 60% of bittern I, then carries out separation of solid and liquid, Gained solid is NaCl；Gained liquid is bittern II；
（4）Continue evaporation equivalent to step（3）The moisture of the mass 35 ~ 60% of gained bittern II, carries out separation of solid and liquid again；Obtain Solid containing potassium and clear liquid containing lithium；
（5）By step（4）Clear liquid containing lithium obtained by separation of solid and liquid adds the solution of alkali or alkali, adjustment pH value to 11 ~ 14, filters, filter Slag is magnesium hydrate precipitate, leaves and takes filtrate I；
（6）Toward step（5）Oxalic acid or oxalate solution are added in gained filtrate I, deliming, filtering, filter residue is calcium oxalate, leaves and takes filter Liquid II；
（7）Toward step（6）Carbon dioxide is passed through in gained filtrate II, or adds carbonate, controls lithium ion content ＜ in solution 0.2wt%, separation of solid and liquid, filter residue are lithium carbonate, filtrate return to step（4）Continue concentration and evaporation；
The carbonate is at least one of sodium carbonate, ammonium carbonate, potassium carbonate.
2. the technique according to claim 1 for preparing lithium carbonate with lake bittern water containing lithium salts, it is characterised in that step（1）In, The lime cream soliquoid, by lime stone, firing obtains CaO, then preparing lime milk suspension, and lime stone fires gained titanium dioxide Carbon is applied to subsequent step（7）In.
3. the technique according to claim 1 or 2 for preparing lithium carbonate with lake bittern water containing lithium salts, it is characterised in that step（1） In, the lake bittern water containing lithium salts, Mg/Li ratio≤200:1.
4. the technique according to claim 3 for preparing lithium carbonate with lake bittern water containing lithium salts, it is characterised in that step（1）In, The lake bittern water containing lithium salts, the ︰ 1 of Mg/Li ratio >=10.
5. the technique according to claim 4 for preparing lithium carbonate with lake bittern water containing lithium salts, it is characterised in that step（1）In, The lake bittern water containing lithium salts, the ︰ 1 of Mg/Li ratio >=30.
6. the technique according to claim 1 or 2 for preparing lithium carbonate with lake bittern water containing lithium salts, it is characterised in that step（2） In, evaporate the moisture equivalent to the mixture quality of lake bittern water containing lithium salts 10 ~ 70%, control lithium ion content ＜ 0.2wt%.
7. the technique according to claim 1 or 2 for preparing lithium carbonate with lake bittern water containing lithium salts, it is characterised in that step（3） In, evaporate the moisture equivalent to the mass 35 ~ 60% of bittern I, control lithium ion content ＜ 1.0%.
8. the technique according to claim 1 or 2 for preparing lithium carbonate with lake bittern water containing lithium salts, it is characterised in that step（4） In, continue evaporation equivalent to step（3）The moisture of the mass 35 ~ 60% of gained bittern II, control lithium ion content ＞ 2.0%.
9. the technique according to claim 1 or 2 for preparing lithium carbonate with lake bittern water containing lithium salts, it is characterised in that step（5） In, adjustment pH value to 11 ~ 14, control magnesium ion content ＜ 0.01wt%；Step（6）In, deliming, control calcium ion content is less than 0.01%。
10. the technique according to claim 1 or 2 for preparing lithium carbonate with lake bittern water containing lithium salts, it is characterised in that step （5）In, the alkali is NaOH, Na2CO3, at least one of KOH；Step（6）In, the oxalates is sodium oxalate, potassium oxalate At least one of.
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