CN108285157A - A kind of technique preparing lithium carbonate with carbonate type bittern - Google Patents
A kind of technique preparing lithium carbonate with carbonate type bittern Download PDFInfo
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- CN108285157A CN108285157A CN201810243519.0A CN201810243519A CN108285157A CN 108285157 A CN108285157 A CN 108285157A CN 201810243519 A CN201810243519 A CN 201810243519A CN 108285157 A CN108285157 A CN 108285157A
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- brine
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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
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- 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 preparing lithium carbonate with carbonate type bittern, includes the following steps：（1）Remove carbanion；（2）Concentration, enrichment lithium ion；（3）The enrichment of carbanion；（4）Sinker；（5）Crude lithium Carbonate product is washed with water, obtains lithium carbonate product.The advantage of the invention is that：（1）It is simple for process, raw material sources are wide, at low cost.（2）Li+Yield is higher, and one time sinker rate is high.（3）Production efficiency is high, with short production cycle.（4）Product purity is higher.（5）Gained lithium carbonate product meets 2003 industrial goods requirements of GB/T11075.
Description
Technical field
The present invention relates to a kind of with making from brine for the technique of lithium carbonate, and in particular to a kind of to prepare carbon with carbonate type bittern
The technique of sour lithium.
Background technology
As country is to the pay attention to day by day of environmental protection, new energy, substantially see that lithium salts is opened in the case of rising in current lithium market
Fermentation faces fabulous opportunity to develop, it is contemplated that lithium salts will enter 10 years gold lead-times.China is a lithium resource big country,
The lithium resource commercial reserves verified occupies the second in the world, especially liquid lithium ore resources and enriches very much, and brine lithium accounts for 79%.But
It is higher that there are Mg/Li ratios in most salt lakes, puies forward lithium complex process, the shortcomings of cost is higher, constrains the industrialization that saline lakes of China carries lithium
Development.And carbonate type salt lake brine Li+Concentration is higher, Ca2+、Mg2+Concentration is relatively low, is easy to extract Li2CO3, but then
CO in liquid phase3 2-A large amount of presence of ion greatly restrict Li again+High concentration enrichment in brine, to low cost, height
Li is efficient extracted from brine2CO3Bring obstacle.
CN99105828.3 discloses a kind of method for extracting lithium salts from carbonate type bittern.This method is using multistage cold
Freeze solarization diving pond-control pond-crystallizing pond-mother liquor pond, halite, saltcake is made to be precipitated in pond is dived under water in solarization, and lithium is then in halogen
Reach pre-concentration in water, then concentrate on control pond, the lithium content in brine is made to reach 1.5 ~ 2.8g/L, and temperature 5 DEG C with
On, control falls halogen to crystallizing pond, makes to be enriched with the big high lithium mixed salt of high-grade, thickness in crystallizing pond, carbonic acid grade lithium 5% with
On, but this method needs to build multiple salt pans, and cost is higher, and to pass through multistage freezing, and the production cycle is longer.
CN02129355.4 propose it is a kind of using solar pond as crystallizing pond and crystallize from carbonate type bittern carbonic acid is precipitated
The method of lithium.Solar pond is directly surrounded with clay, and bottom of pond is the interlayer structure of plastic film and hydromagnesite, and pond body inner wall is covered with brown
Geomembrane and high density polyethylene (HDPE), polyvinyl chloride etc. are as liner, by the heat accumulation process of solar pond and the precipitation process of lithium carbonate
It combines together, lithium carbonate mixed salt of the grade 60% or so can be obtained.CN200620172864.2 discloses one kind and carrying lithium for brine
Sun pool device.Pond body includes thematic structure layer, makes into be sequentially distributed waterproof upwards along the side wall of pond body and bottom anti-
Damp layer, insulating layer, anti-corrosion waterproof heat-sink shell.Device is made of four layers or five-layer structure, and top layer is anti-corrosion waterproof heat-sink shell,
The good anticorrosion material of effective heat absorption capacity and special insulation construction are selected, keeps solar pond heat preservation heat accumulation effect more preferable, through 20 ~
After 40 days absorb solar energy heat-storages, winter-spring season bottom of pond temperature up to 30 ~ 50 DEG C, summer and autumn bottom of pond temperature up to 50 ~ 80 DEG C,
To accelerate the crystallization from carbonate type bittern that lithium carbonate is precipitated.Both methods is all to prepare lithium carbonate using solar pond, should
Method not only requires height, but also CO to salt pan3 2-And Li+Always in a kind of solution, concentrating degree is limited, single sinker efficiency
It is low, the production cycle is longer.
Invention content
The technical problem to be solved by the present invention is to overcome the deficiencies of the prior art and provide that a kind of period is short, efficient, work
Skill route simply prepares the technique of lithium carbonate with carbonate type bittern, and gained lithium carbonate product purity is high.
The technical solution adopted by the present invention to solve the technical problems is, a kind of to prepare lithium carbonate with carbonate type bittern
Technique specifically includes following steps：
（1）Remove carbanion：A part of carbonate type bittern raw material is taken, chemical reagent is added and removes carbanion, makes
Obtain CO in brine3 2-Mass concentration≤0.2%, the brine of carbanion must be removed；
The chemical reagent being added is preferably at least one of magnesium chloride, bischofite, calcium chloride, quick lime.
The chemical reagent being added in brine carbanion reaction generate precipitation, detach, in mother liquor carbonate from
Sub- concentration substantially reduces；And obtained precipitation is easy filtering, and entrainment is few.
Instant invention is especially suited for CO3 2-Mass concentration >=1% carbonate type bittern.If in carbonate type bittern
CO3 2-Mass concentration ＜ 1%, be the especially low carbonate type bittern of concentration, water content is excessively high, and it is higher to deal with energy consumption,
CO can be waited for after salt Tanaka's natural evaporation concentration3 2-Mass concentration >=1%, then method using the present invention processing.
（2）Concentration, enrichment lithium ion：By step（1）Gained removes the bittern evaporation concentration of carbanion, not to be precipitated
Lithium salts is boundary, Li in brine after concentration+Content>0.25wt%（It is preferred that 0.5-1wt%）, obtain rich lithium brine；
The concentration of lithium ion is more than 1% in brine, and water evaporation is more, also can guarantee yield, but energy consumption is too high, cost is higher.Lithium from
Sub- concentration is too low, and inferior separating effect when follow-up sinker, yield can decline.
It can be that evaporations and concentration is tedded in forced evaporation concentration or salt pan naturally to be concentrated by evaporation, and lithium ion is dense in raising brine
Degree.
（3）The enrichment of carbanion：Another part carbonate type bittern raw material is taken directly to be concentrated by evaporation, lithium is not precipitated
Salt is boundary so that CO in brine3 2-A concentration of 2-6wt%（It is preferred that 4-5wt%）, obtain the brine of enrichment carbanion；
If the concentration of carbanion is more than 6% in brine, water evaporation is excessive, and energy consumption is too high, and cost is higher.If brine
The concentration of middle carbanion is too low, and inferior separating effect when follow-up sinker, yield can decline.
It can be that evaporation and concentration is tedded in forced evaporation concentration or salt pan naturally to be concentrated by evaporation, and improve carbanion in mother liquor
Concentration.
（4）Sinker：Step（2）Gained richness lithium brine and step（3）The brine mixing of gained enrichment carbanion is stirred
It mixes, the lithium ion in rich lithium brine is 1 with the ratio between the amount of substance of carbanion in the brine of enrichment carbanion：1-
1.5（Carbanion is excessive herein, and its object is to recycle lithium as far as possible）, it is separated by filtration, obtains Crude lithium Carbonate product, mother liquor
Return to step（3）；
Further, step（4）The temperature of middle mixing is 25 DEG C -75 DEG C, preferably 50-55 DEG C；Time, which is subject to, to be uniformly mixed；
（5）Washing：Crude lithium Carbonate product is washed with water, obtains lithium carbonate product.
The present invention, using the method handled respectively, reduces CO during brewed brine3 2-Concentration in brine creates Li+
High enrichment environment, the purity of obtained lithium carbonate product is more than or equal to 98.5%.In carbonate type bittern raw material of the present invention in itself
Carbanion and lithium ion are there is, if not using the method handled respectively, precipitation can be slowly precipitated in brine itself, but heavy
99% or more is the impurity such as sodium chloride in shallow lake, and the purity of lithium carbonate is less than 1%, is unable to get the higher lithium carbonate product of purity.
The present invention removes the carbanion in the brine of part, re-evaporation enrichment method lithium；Another part brine directly steams
Lithium carbonate product, energy is made then two parts brine sinker under certain condition in hair enrichment carbanion after washing
The problems such as solving complex process, low production efficiency, production cycle long, of high cost, product purity is low in the prior art.
The advantage of the invention is that：
（1）It is simple for process, raw material sources are wide, at low cost.
（2）Li+Yield is higher, and one time sinker rate is high.
（3）Production efficiency is high, with short production cycle.
（4）Product purity is higher.
（5）Gained lithium carbonate product meets GB/T11075-2003 industrial goods requirements.
Specific implementation mode
With reference to embodiment, the invention will be further described.
Embodiment 1
CO in the present embodiment carbonate type bittern raw material3 2-Content is 1.6 wt%, and the present embodiment is used carbonate type bittern preparation
The technique of lithium carbonate specifically includes following operating procedure：
（1）Remove carbanion：A part of carbonate type bittern raw material is taken, the carbonic acid in magnesium chloride, with raw brine is added
Radical ion reaction generates carbonic acid magnesium precipitate, then detaches, the CO in brine3 2-Content is 0.13wt%, Li+Content is 0.03wt%,
The brine of carbanion must be removed；
（2）Concentration, enrichment lithium ion：By step（1）Gained removes the brine forced evaporation concentration of carbanion, not to be precipitated
Lithium salts is boundary, and evaporation is equivalent to the water of brine weight 50%, obtains rich lithium brine, Li in brine after concentration+Content reaches
0.26wt%, while the salts such as a large amount of sodium chloride are precipitated；
（3）The enrichment of carbanion：The direct forced evaporation concentration of another part carbonate type bittern raw material is taken, lithium is not precipitated
Salt is boundary, CO in the brine after concentration3 2-Content is 4.7 wt%, obtains the brine of enrichment carbanion；
（4）Sinker：Step（2）Gained richness lithium brine and step（3）The brine that gained is enriched with carbanion mixes at 50 DEG C
Stirring 30min is closed, the amount of the lithium ion in rich lithium brine and the substance of the carbanion in the brine of enrichment carbanion
The ratio between be 1：1, it is then separated by filtration, obtains Crude lithium Carbonate product, mother liquor return to step（3）；One time sinker rate reaches 85 wt%；
（5）Washing：Crude lithium Carbonate product is washed with water, lithium carbonate product is obtained by filtration, the purity of product is 99.10 wt%.
Embodiment 2
CO in the present embodiment carbonate type bittern raw material3 2-Content is 2.4wt%, and the present embodiment is used carbonate type bittern and prepares carbon
The technique of sour lithium specifically includes following operating procedure：
（1）Remove carbanion：A part of carbonate type bittern raw material is taken, the carbon in bischofite, with raw brine is added
Acid ion reaction generates carbonic acid magnesium precipitate, is then separated by filtration, the CO in brine3 2-Content is 0.10wt%, Li+Content is
0.08wt% must remove the brine of carbanion；
（2）Concentration, enrichment lithium ion：By step（1）The brine that gained removes carbanion carries out forced evaporation concentration, with not
Precipitation lithium salts is boundary, and evaporation is equivalent to the water of brine weight 48%, Li in brine after concentration+Content is 0.7wt%, obtains rich lithium
Brine；The salts such as a large amount of sodium chloride are precipitated simultaneously.
（3）The enrichment of carbanion：The direct forced evaporation concentration of another part carbonate type bittern raw material is taken, not analyse
It is boundary to go out lithium salts so that CO in brine3 2-A concentration of 4.1%, obtain the brine of enrichment carbanion；
（4）Sinker：Step（2）Gained richness lithium brine and step（3）The brine that gained is enriched with carbanion mixes at 55 DEG C
Stirring 30min is closed, the amount of the lithium ion in rich lithium brine and the substance of the carbanion in the brine of enrichment carbanion
The ratio between be 1：1.5 obtaining Crude lithium Carbonate product after being then separated by filtration, mother liquor return to step（3）；Sinker rate is 83%；
（5）Washing：Crude lithium Carbonate product is washed with water, lithium carbonate product is obtained by filtration.The purity of product is 99.20%.
Embodiment 3
CO in the present embodiment carbonate type bittern raw material3 2-Content is 2.4wt%, and the present embodiment is used carbonate type bittern and prepares carbon
The technique of sour lithium specifically includes following operating procedure：
（1）Remove carbanion：Take a part of carbonate type bittern raw material, be added carbonate in calcium chloride, with brine from
Son reaction generates precipitation of calcium carbonate, is then separated by filtration, must remove the brine of carbanion, the CO in brine3 2-Content is
0.08wt%, Li+Content is 0.07wt%；
（2）Concentration, enrichment lithium ion：By step（1）Gained removes the brine forced evaporation concentration of carbanion, not to be precipitated
Lithium salts is boundary, and evaporation is equivalent to the water of brine weight 55%, Li in brine after concentration+Content reaches 1.0wt%, obtains rich lithium halogen
Water；The salts such as a large amount of sodium chloride are precipitated simultaneously.
（3）The enrichment of carbanion：The direct forced evaporation concentration of another part carbonate type bittern raw material is taken, not analyse
It is boundary to go out lithium salts so that CO in brine3 2-A concentration of 4.2wt% obtains the brine of enrichment carbanion；
（4）Sinker：Step（2）Gained richness lithium brine and step（3）The brine that gained is enriched with carbanion mixes at 60 DEG C
Stirring 40min is closed, the amount of the lithium ion in rich lithium brine and the substance of the carbanion in the brine of enrichment carbanion
The ratio between be 1：1.2, it is separated by filtration, obtains Crude lithium Carbonate product, mother liquor return to step（3）；Sinker rate is 82%；
（5）Washing：Crude lithium Carbonate product is washed with water, lithium carbonate product is obtained by filtration, the purity of product is 99.00%.
Claims (7)
1. a kind of technique preparing lithium carbonate with carbonate type bittern, which is characterized in that include the following steps：
（1）Remove carbanion：A part of carbonate type bittern raw material is taken, chemical reagent is added and removes carbanion, makes
Obtain CO in brine3 2-Mass concentration≤0.2%, the brine of carbanion must be removed；
（2）Concentration, enrichment lithium ion：By step（1）Gained removes the bittern evaporation concentration of carbanion, lithium salts is not precipitated
For boundary, Li in brine after concentration+Content>0.25wt% obtains rich lithium brine；
（3）The enrichment of carbanion：It takes another part carbonate type bittern raw material to be directly concentrated by evaporation, is so that lithium salts is not precipitated
Boundary so that CO in brine3 2-A concentration of 2-6wt% obtains the brine of enrichment carbanion；
（4）Sinker：Step（2）Gained richness lithium brine and step（3）The brine that gained is enriched with carbanion is mixed, rich
Lithium ion in lithium brine and the ratio between the amount of substance of carbanion in the brine of enrichment carbanion are 1：1-1.5
It is separated by filtration, obtains Crude lithium Carbonate product, mother liquor return to step（3）；
（5）Washing：Crude lithium Carbonate product is washed with water, obtains lithium carbonate product.
2. the technique according to claim 1 for preparing lithium carbonate with carbonate type bittern, which is characterized in that step（1）In,
When removing carbanion, the chemical reagent being added is at least one of magnesium chloride, bischofite, calcium chloride, quick lime.
3. the technique according to claim 1 or 2 for preparing lithium carbonate with carbonate type bittern, which is characterized in that step（1）
In, raw material CO3 2-Mass concentration >=1% carbonate type bittern.
4. the technique according to claim 1 or 2 for preparing lithium carbonate with carbonate type bittern, which is characterized in that step（2）
In, Li in brine after concentration+Content is 0.5-1wt%.
5. the technique according to claim 1 or 2 for preparing lithium carbonate with carbonate type bittern, which is characterized in that step（3）
In, CO in brine after evaporation and concentration3 2-A concentration of 4-5wt%.
6. the technique according to claim 1 or 2 for preparing lithium carbonate with carbonate type bittern, which is characterized in that step（4）
The temperature of middle mixing is 25 DEG C -75 DEG C.
7. the technique according to claim 6 for preparing lithium carbonate with carbonate type bittern, which is characterized in that mixing
Temperature is 50-55 DEG C.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113336250A (en) * | 2021-05-28 | 2021-09-03 | 中国地质科学院矿产资源研究所 | Lithium carbonate solar cell and lithium carbonate extraction method |
| CN115571926A (en) * | 2022-09-30 | 2023-01-06 | 广东邦普循环科技有限公司 | Method for removing carbonate from lithium precipitation mother liquor |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102491378A (en) * | 2011-10-14 | 2012-06-13 | 陈兆华 | Producing method for preparing lithium carbonate by taking carbonate type brine and sulphate type brine as raw material and by repeatedly mixing brine |
-
2018
- 2018-03-23 CN CN201810243519.0A patent/CN108285157A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102491378A (en) * | 2011-10-14 | 2012-06-13 | 陈兆华 | Producing method for preparing lithium carbonate by taking carbonate type brine and sulphate type brine as raw material and by repeatedly mixing brine |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113336250A (en) * | 2021-05-28 | 2021-09-03 | 中国地质科学院矿产资源研究所 | Lithium carbonate solar cell and lithium carbonate extraction method |
| CN113336250B (en) * | 2021-05-28 | 2022-03-08 | 中国地质科学院矿产资源研究所 | Lithium carbonate solar cell and lithium carbonate extraction method |
| CN115571926A (en) * | 2022-09-30 | 2023-01-06 | 广东邦普循环科技有限公司 | Method for removing carbonate from lithium precipitation mother liquor |
| CN115571926B (en) * | 2022-09-30 | 2024-02-09 | 广东邦普循环科技有限公司 | Method for removing carbonate radical from lithium precipitation mother liquor |
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