CN109607578A - A method of extracting battery-level lithium carbonate from magnesium sulfate salt lake bittern - Google Patents
A method of extracting battery-level lithium carbonate from magnesium sulfate salt lake bittern Download PDFInfo
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Abstract
The old brine of primary purification is obtained by filtration method includes the following steps: (1) mentioning flyash addition in the old halogen of potassium in the method that the present invention relates to a kind of to extract battery-level lithium carbonate from magnesium sulfate salt lake bittern；(2) it is pumped into ultrafiltration apparatus after the old brine dilution of primary purification, obtains the old brine of secondary refining；(3) the old brine of secondary refining is pumped into three-level high pressure nano filter membrance device, and pressure obtains rich lithium liquid and dope；(4) rich lithium liquid carries out the concentration of RO film+MVR forced evaporation two-stage, respectively obtains high lithium solution and pure water；(5) high lithium solution is squeezed into boron resin exchange column, obtains the high lithium solution of boron removal；(6) the high lithium solution of boron removal filters after adjusting pH value, obtains refining high lithium solution；(7) refine and sodium carbonate liquor reaction is added in high lithium solution, respectively obtain Crude lithium Carbonate and sinker mother liquor through filtering；(8) Crude lithium Carbonate sediment is washed, filtering, drying, crushes up to battery-level lithium carbonate product.Present invention process is simple, water consume is low, small investment, excellent product quality.
Description
Technical field
The present invention relates to chemical industry of inorganic salt fields, more particularly to one kind to extract LITHIUM BATTERY from magnesium sulfate salt lake bittern
The method of lithium carbonate.
Background technique
Lithium is the metal that silvery white, matter is soft, most light in periodic table, have highest electrochemical potential, excellent ductility and
Catalytic property, special property make lithium and its compound in national economy, war industry and each department of aerospace
It is used widely.In recent years, under the international big factory electric car new product such as Tesla Moto, GM, TOYOTA, BMW
Line, lithium increasingly show huge market application prospect as strategic resource.
Lithium does not have elemental form in nature, but is primarily present in granite pegmatite deposit (lithium brightness with compound form
Stone, lepidolite, petalite etc.) and brine and seawater in.According to disclosed document report, 60% or more lithium in world wide
In salt lake bittern, sulfate type salt lake brine especially magnesium sulfate brine is all boracic lakes containing lithium salts for resource distribution
In it is most representative, the lithium resource reserves contained account for about the 30% of whole world gross reserves.
So far, the process that lithium carbonate is extracted from salt lake bittern is more, mainly has step-by-step precipitation method, aluminium salt to inhale
Attached method, solvent extraction, calcination method and membrane separation process.Wherein, membrane separation process and solvent extraction have preferable development prospect,
But solvent extraction limits its large-scale industrial application since the toxicity of organic solvent has greater environmental impacts.UF membrane
It is owned by France in physical separation method (electric field driven or pressure-driven), separation system do not introduce chemicals, it is environmental-friendly and separation effect
Rate is higher, thus has stronger development prospect.Chinese patent CN104961143A, Chinese patent CN100408705C and China
Patent CN103074502A, which is disclosed, is used for the method that salt lake bittern mentions lithium using nanofiltration membrane separation process, in China's Qinghai Salt Lake
Industrial scale applications are obtained, but current nanofiltration membrane process mentions lithium there are problems that several aspects need to improve: first is that existing
Nanofiltration membrane separation process cannot produce battery-level lithium carbonate product since process combination is not perfect, and market application is limited.Second is that receiving
Filter membrane is low-pressure membrane, and tolerable highest operating pressure must not be higher than 4.0MPa, and brine extension rate is caused to be up to 14 ~ 20
Times, water consume is especially big.Third is that current nanofiltration technique is higher to ingredient requirement, the lithium ion mass concentration in old brine must not be low
In 4.0g ﹒ L-1, it is larger to lead to propose the lithium ion loss in enrichment process of the old brine of potassium.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of low water consumption, product quality is controllable, production cost it is low from
The method of battery-level lithium carbonate is extracted in magnesium sulfate salt lake bittern.
To solve the above problems, one kind of the present invention extracts battery-level lithium carbonate from magnesium sulfate salt lake bittern
Method, comprising the following steps:
(1) flyash addition is mentioned in the old halogen of potassium, be pumped into plate and frame filter press filtering through slurry, obtain the old brine of primary purification；It is described
The additional amount of flyash mentions the 0.1 ~ 10% of the old halogen weight of potassium described in being；
(2) the primary purification old brine production water is diluted 4 ~ 10 times, be pumped into ultrafiltration apparatus, obtain the old halogen of secondary refining
Water；
(3) the old brine of the secondary refining is pumped into three-level high pressure nano filter membrance device, applies 3.8 ~ 8.0MPa pressure, obtain richness
Lithium liquid and dope；[Li in the richness lithium liquid+] between 240 ~ 1250 mgL-1；
(4) the rich lithium liquid is carried out two-stage concentration: the first order is concentrated using RO film, [Li+] from 240 ~ 1250 mgL-1Enrichment
To 3500 ~ 7000 mgL-1；The second level is concentrated using MVR forced evaporation, [Li+] from 3500 ~ 7000mgL-1Enrichment to 25 ~
42g·L-1, [B2O3] between 6.5 ~ 8.5 gL-1, respectively obtain high lithium solution and pure water；Two-stage is concentrated to get pure
Water returns to the step and is (2) recycled；
(5) the high lithium solution is squeezed into boron resin exchange column, remove the boron element in high lithium solution, obtain [B2O3] between
0.5~100mg·L-1The high lithium solution of boron removal；
(6) the high lithium solution of the boron removal uses mass concentration to adjust pH value to after 12 ~ 14 for 25% sodium hydroxide solution, is pumped into plate
The filtering of frame filter press, obtains refining high lithium solution；
(7) sodium carbonate liquor is added by 125 ~ 135% of lithium ion mole in the high lithium solution of purification, is being warded off in 85 ~ 95 DEG C
In porcelain reaction kettle after 60 ~ 120min of successive reaction, slurry is pumped into centrifuge filtering, respectively obtains Crude lithium Carbonate and sinker mother liquor；
The sinker mother liquor returns to the step and is (1) recycled；After the Crude lithium Carbonate sediment pure water, is filtered, done
It is dry, crush up to battery-level lithium carbonate product.
The step (1) in mention the old halogen of potassium and refer to the old brine after the extracted sylvite of magnesium sulfate brine, [Li in brine+] between 1.3 ~ 4.0gL-1, [Mg2+] between 98 ~ 125 gL-1, [SO4 2-] between 25 ~ 74 gL-1。
The step (1) in flyash additional amount be the old brine weight 1.5 ~ 3.5%.
The step (2) in old brine extension rate be 8 ~ 9 times.
(2) middle ultrafiltration apparatus refers to hollow-fibre membrane ultrafiltration apparatus, material PVDF, 0.05 ~ 0.5 μ of membrane aperture to the step
M, preferably membrane aperture are 0.05 ~ 0.1 μm.
(3) middle three-level high pressure nano filter membrance device refers to three groups of concatenated NF4040 type high pressure nanofiltration UF membranes dresses to the step
It sets, can tolerate highest operating pressure is 8.0MPa.
(3) middle three-level membrane separating process refers to that first order lock out operation pressure is 5.5 ~ 7.5MPa, preferred scope to the step
It is 5.5 ~ 6.5MPa；The second level and third level operating pressure are 3.7 ~ 4.5MPa, and preferred scope is 3.7 ~ 4.0MPa.
(4) middle RO film concentration is sea water desalination membrane to the step, and primary concentration operating pressure is 4.0 ~ 8.0MPa, is preferably grasped
It is 6.5 ~ 6.9MPa as pressure.
The step (5) in borohydride exchange resin be a kind of styrene and divinylbenzene crosslink, there is N- methyl glucose osamine
The macroporous structure chelating resin of base.
The step (7) in sinker Recycling Mother Solution in use, the sinker mother liquor and the mass ratio for mentioning the old halogen of potassium are 1:
5 ~ 1:20, preferred proportion are 1:15 ~ 1:18.
Compared with the prior art, the present invention has the following advantages:
1, the present invention mentions the old brine of potassium as raw material, using " three-level high pressure nanofiltration UF membrane, RO+MVR are dense using magnesium sulfate salt lake
Contracting, boron-specific chelating resin efficiently remove boron group technology ", it obtains refining high lithium solution, adds sodium carbonate liquor in enamel reaction still
Middle progress precipitation reaction and rate controlling crystallization, crystallization of lithium carbonate are made battery-level lithium carbonate after repeatedly washing, dry, crushing and produce
Product.
2, the present invention carries out separating magnesium and lithium operation using the high pressure nanofiltration membrane of special construction, high with tolerance operating pressure,
The feature that water yield is big, separative efficiency is high, old halogen extension rate are reduced to 8 ~ 9 times by original 14 ~ 20 times, significantly reduce
Water consume has expanded the method in the application of salt lake water-deficient area.
3, the present invention is using " three-level high pressure nanofiltration UF membrane, RO+MVR concentration, boron-specific chelating resin efficiently remove boron combination work
Skill " obtains refining high lithium solution by enamel reaction still " precipitation reaction and rate controlling crystallization ", directly produces battery-level lithium carbonate production
Product." hydrogenation-reprecipitation " the prepared calcium carbonate lithium workshop section in traditional handicraft is avoided, equipment investment is largely reduced,
Investment is saved.
4, the present invention has applicable raw materials Li+Concentration is low, simple process, the advantage that product quality is controllable, production cost is low.
Detailed description of the invention
Specific embodiments of the present invention will be described in further detail with reference to the accompanying drawing.
Fig. 1 is process flow chart of the invention.
Specific embodiment
As shown in Figure 1, a kind of method that battery-level lithium carbonate is extracted from magnesium sulfate salt lake bittern, including following step
It is rapid:
(1) flyash addition is mentioned in the old halogen of potassium, be pumped into plate and frame filter press filtering through slurry, obtain the old brine of primary purification.
Wherein: mentioning the old halogen of potassium and refer to the old brine after the extracted sylvite of magnesium sulfate brine, [Li in brine+] between
1.3~4.0g·L-1, [Mg2+] between 98 ~ 125 gL-1, [SO4 2-] between 25 ~ 74 gL-1。
The additional amount of flyash is propose the old halogen weight of potassium 0.1 ~ 10%, preferably 1.5 ~ 3.5%.
There are two the purposes that flyash is added, first is that organic matter remaining in absorption brine, second is that there is silt etc. in brine
Suspended matter, it is not easy to filter, flyash is added and plays the role of drainage.
(2) primary purification old brine production water is diluted 4 ~ 10 times, be pumped into ultrafiltration apparatus, obtain the old halogen of secondary refining
Water.
Wherein: the old preferred extension rate of brine is 8 ~ 9 times.Dilution water used is to produce water, including step is (4) concentrated
The pure water of journey circulating and recovering.
Ultrafiltration apparatus refers to hollow-fibre membrane ultrafiltration apparatus, material PVDF, 0.05 ~ 0.5 μm of membrane aperture, preferably membrane aperture
It is 0.05 ~ 0.1 μm.
The purpose that the old brine of primary purification carries out ultrafiltration is in order to reach UF membrane water inlet index, in general, after ultrafiltration
Turbidity NTU < 1, SDI < 5.
(3) the old brine of secondary refining is pumped into three-level high pressure nano filter membrance device, applies 3.8 ~ 8.0MPa pressure, obtain richness
Lithium liquid and dope；[Li in rich lithium liquid+] between 240 ~ 1250 mgL-1。
Wherein: three-level high pressure nano filter membrance device refers to three groups of concatenated NF4040 type high pressure nanofiltration membrane separation devices, can
Tolerance highest operating pressure is 8.0MPa.
Three-level membrane separating process refers to that first order lock out operation pressure is 5.5 ~ 7.5MPa, preferred scope is 5.5 ~
6.5MPa；The second level and third level operating pressure are 3.7 ~ 4.5MPa, and preferred scope is 3.7 ~ 4.0MPa.
The old brine lithium ion percent of pass > 90%, SO of high pressure membrane separating process secondary refining4 2-Rejection > 99%, Mg2+Rejection
>90%。
High pressure nanofiltration membrane main function is the element for separating monovalence and divalent, and univalent element has lithium, potassium, sodium, chlorine, divalent member
Element is mainly calcium and magnesium and sulfate radical, and for the production water after separation mainly containing lithium, potassium, sodium, chlorine, boron and a small amount of magnesium, concentrated water is to be trapped
Calcium, magnesium boron and sulfate.
(4) rich lithium liquid is carried out two-stage concentration: the first order is concentrated using RO film, and the concentration of RO film is sea water desalination membrane, and level-one is dense
Contracting operating pressure is 4.0 ~ 8.0MPa, and preferred operations pressure is 6.5 ~ 6.9MPa [Li+] from 240 ~ 1250 mgL-1Enrichment is extremely
3500~7000 mg·L-1.The second level is concentrated using MVR forced evaporation, [Li+] from 3500 ~ 7000mgL-1Enrichment to 25 ~
42g·L-1, [B2O3] between 6.5 ~ 8.5 gL-1, respectively obtain high lithium solution and pure water；Two-stage is concentrated to get pure
(2) water return step is recycled.
(5) high lithium solution is squeezed into boron resin exchange column, remove the boron element in high lithium solution, obtain [B2O3] between
0.5~100mg·L-1The high lithium solution of boron removal.
Borohydride exchange resin is a kind of styrene and divinylbenzene crosslink, the macroporous structure with N- methyl glucoside amido
Chelating resin.N- methyl glucoside amidine functional group has fabulous selectivity to boron in resin.Boron is in battery-level lithium carbonate
The critical impurities, [B in the high lithium mother liquor of purification2O3] when reaching 200ppm, very big influence will be caused to product.Resin is de-
High lithium solution [B after boron2O3] between 0.5 ~ 100mgL-1, more preferably [B2O3] between 0.5 ~ 3.0mgL-1。
(6) the high lithium solution of boron removal uses mass concentration to adjust pH value to after 12 ~ 14 for 25% sodium hydroxide solution, is pumped into plate
The filtering of frame filter press, obtains refining high lithium solution.
(7) sodium carbonate liquor is added by refine lithium ion mole in high lithium solution 125 ~ 135%, is being warded off in 85 ~ 95 DEG C
In porcelain reaction kettle after 60 ~ 120min of successive reaction, slurry is pumped into the filtering of siphon horizontal type scraper centrifuger, respectively obtains Crude lithium Carbonate
With sinker mother liquor.
Wherein: precipitation reaction is continuous crystallisation control reaction, and feed liquid is distinguished rate controlling atomizing spray by distributor and fed, slurry
Expect in enamel reaction still complete lithium carbonate precipitation reaction and rate controlling crystallize two stages, rate controlling crystallization purpose, be in order to
The Crude lithium Carbonate particle of low impurity content is obtained, the impurity content of lithium carbonate crude product entrainment is further decreased.
(1) sinker mother liquor return step is recycled.In use, sinker mother liquor is 1:5 ~ 1 with the mass ratio for mentioning the old halogen of potassium:
20, preferred proportion is 1:15 ~ 1:18.Sinker mother liquor is mixed according to a certain volume with the old halogen of potassium is mentioned, and the purpose mixed is using heavy
Carbonate and hydroxyl in lithium mother liquor, removal mention the magnesium ion in the old brine of potassium, reduce the Mg/Li ratio of old brine, recycle simultaneously
Lithium ion in sinker mother liquor.
After Crude lithium Carbonate sediment pure water, through filtering, drying, crush up to battery-level lithium carbonate product.
Embodiment 1
Raw material is derived from Chaidamu Basin, Qinghai Province big bavin denier salt lake and mentions the old brine after potassium, has chemical composition as shown in Table 1, from
Brine system hydrochemical type is analyzed on composition belongs to magnesium sulfate.
1 Chaidamu Basin, Qinghai Province of table big bavin denier salt lake mentions potassium Brine Chemistry composition
(1) 1.00m is extracted3Table 1 mentions the old halogen of potassium, and flyash is added by the 1% of old halogen weight ratio, opens stirring, uses slag after ten minutes
Stock pump squeezes into plate and frame filter press filtering, obtains filter residue 40Kg, 0.96 m of primary purification filtrate3, control filtrate NTU < 20, SDI <
200。
(2) with the production water dilution old brine 10 of primary purification again to 9.6m3, squeezed into ultrafiltration apparatus and filtered with centrifugal pump, closed
Concentrated water valve is closed, controls filtrate NTU < 1, SDI < 5 obtain secondary refining brine 9.56m3, it is placed in spare in PP storage tank.Ultrafiltration membrane
Selection PVDF doughnut material, 0.1 μm of membrane aperture.
(3) secondary refining brine is squeezed into three groups of concatenated NF4040 type high pressure nanofiltration membrane separation devices, control level-one is received
Filter membrane intake pressure 55Bar, second level and three-level nanofiltration membrane intake pressure 38Bar, three-level high pressure nanofiltration membrane concentrated water successively return
Grade influent side produces water and sequentially enters next stage influent side.It is rich lithium liquid that third level nanofiltration membrane, which produces water, and three-level separation is total to obtain richness
6.24 m of lithium liquid3, [Li+] = 296 mg·L-1, 3.32 m of concentrated water3, [Li+] = 110 mg·L-1, lithium ion is calculated and returns
Yield is 79.10%.
(4) obtained rich lithium liquid pump is squeezed into 4040 type RO film condensing devices, control intake pressure 69Bar, enrichment 22
Times, obtain [Li+] 6.67g·L-1RO concentrate 277L continues to be concentrated to get [Li with MVR forced evaporation device+]
40.26g·L-1High lithium solution 46L, while obtaining pure water 6.19m3(2) return step dilutes brine, be recycled, the pure water by
RO produces water and MVR condensed water mixing gained.
(5) boron resin first uses 2molL-1The NaOH solution regeneration treatment of sulfuric acid and 10% concentration, squeezes into pure water respectively
To neutrality.It is added to high lithium solution after the NaOH adjusting pH to 8.0 of 10% concentration and high lithium solution 46L is squeezed into 50L with metering pump
× 2 series connection boron resin columns, control [the B in efflux2O3]<1mg·L-1, the high lithium solution 45L of boron removal is obtained, pure water is then used
Boron resin is eluted, washing lotion return step is obtained and reuse is (4) concentrated.
(6) 25% soda bath is added into the high lithium solution of boron removal and adjusts pH value to 14, is pumped into plate and frame filter press with Pulp pump
Filtering, filter cake is magnesium hydroxide, by weight 1:1 plus pure water pulp washing, filtering and after drying as flame retardant of magnesium hydroxide
Sale.Filtrate refines high lithium solution.
(7) sodium carbonate liquor, two kinds of solution metering gears are added by refine lithium ion mole in high lithium solution 125%
It pumps while being pumped into enamel reaction still, after 85 DEG C of successive reaction 90min, slurry enters centrifuge from head tank gravity flow and filters, and obtains
To Crude lithium Carbonate and sinker mother liquor, after Crude lithium Carbonate sediment washs 2 times by weight 1:4 with high purity water, through centrifugal filtration, dodge
Battery-level lithium carbonate product 7.67Kg is obtained after being evaporated dry, air-flow crushing, the sinker Recycling Mother Solution uses, and test obtains battery
The main content of level lithium carbonate product is 99.61%.
Embodiment 2
Raw material is derived from Chaidamu Basin, Qinghai Province East taigener salt-lake and mentions the old brine after potassium, has chemical group as shown in Table 2
At analysis brine system hydrochemical type belongs to magnesium sulfate, the method phase that the present embodiment is provided with embodiment 1 from composition
Than, raw material and the operating condition difference of selection, the main adaptability for investigating this method under different material and operating condition.
2 Chaidamu Basin, Qinghai Province East taigener salt-lake of table mentions potassium Brine Chemistry composition
(1) 1.00m is extracted3Table 2 mentions the old halogen of potassium, and flyash is added by the 1% of old halogen weight ratio, opens stirring, uses slag after ten minutes
Stock pump squeezes into plate and frame filter press filtering, obtains filter residue 38Kg, 0.98 m of primary purification filtrate3, control filtrate NTU < 20, SDI <
200。
(2) with the production water dilution old brine 8 of primary purification again to 7.84m3, squeezed into ultrafiltration apparatus and filtered with centrifugal pump, closed
Concentrated water valve is closed, controls filtrate NTU < 1, SDI < 5 obtain secondary refining brine 7.82m3, it is placed in spare in PP storage tank.Ultrafiltration
Film selection PVDF doughnut material, 0.05 μm of membrane aperture.
(3) secondary refining brine is squeezed into three groups of concatenated NF4040 type high pressure nanofiltration membrane separation devices, control level-one is received
Filter membrane intake pressure 75Bar, second level and three-level nanofiltration membrane intake pressure 45Bar, three-level high pressure nanofiltration membrane concentrated water successively return
Grade influent side produces water and sequentially enters next stage influent side.It is rich lithium liquid that third level nanofiltration membrane, which produces water, and three-level separation is total to obtain richness
4.22 m of lithium liquid3, [Li+] = 1220 mg·L-1, concentrated water 3.60m3, [Li+] = 95 mg·L-1, lithium ion is calculated and returns
Yield is 94.46%.
(4) obtained rich lithium liquid pump is squeezed into 4040 type RO film condensing devices, control intake pressure 65Bar, enrichment 5.8
Times, obtain [Li+] 7.12g·L-1RO concentrate 719L continues to be concentrated to get [Li with MVR forced evaporation device+]
35.10g·L-1High lithium solution 146L, while obtaining pure water 4.07m3(2) return step dilutes brine, be recycled, the pure water by
RO produces water and MVR condensed water mixing gained.
(5) boron resin first uses 2molL-1The NaOH solution regeneration treatment of sulfuric acid and 10% concentration, squeezes into pure water respectively
To neutrality.The NaOH that 10% concentration is added to high lithium solution is squeezed into high lithium solution 146L with metering pump after adjusting pH to 8.3
The series connection boron resin column of 50L × 2, controls [the B in efflux2O3]<3mg·L-1, the high lithium solution 142L of boron removal is obtained, is then used
Pure water elutes boron resin, obtains washing lotion return step and reuse is (4) concentrated.
(6) 25% soda bath is added into the high lithium solution of boron removal and adjusts pH value to 14, is pumped into plate and frame filter press with Pulp pump
Filtering, filter cake is magnesium hydroxide, by weight 1:1 plus pure water pulp washing, filtering and after drying as flame retardant of magnesium hydroxide
Sale.Filtrate refines high lithium solution.
(7) sodium carbonate liquor, two kinds of solution metering gears are added by refine lithium ion mole in high lithium solution 130%
It pumps while being pumped into enamel reaction still, after 85 DEG C of successive reaction 90min, slurry enters centrifuge from head tank gravity flow and filters, and obtains
To Crude lithium Carbonate and sinker mother liquor, after Crude lithium Carbonate sediment washs 2 times by weight 1:4 with high purity water, through centrifugal filtration, dodge
Battery-level lithium carbonate product 20.82Kg is obtained after being evaporated dry, air-flow crushing, the sinker Recycling Mother Solution uses, and test obtains electricity
Level lithium carbonate product main content in pond is 99.73%.
Embodiment 3
Raw material is derived from Chaidamu Basin, Qinghai Province West Taijinar Salt Lake and mentions the old brine after potassium, has chemical group as shown in table 3
At analysis brine system hydrochemical type belongs to magnesium sulfate, the method phase that the present embodiment is provided with embodiment 2 from composition
Than, raw material and the operating condition difference of selection, the main adaptability for investigating this method under different material and operating condition.
3 Chaidamu Basin, Qinghai Province West Taijinar Salt Lake of table mentions potassium Brine Chemistry composition
(1) 1.00m is extracted3Table 3 mentions the old halogen of potassium, and flyash is added by the 1% of old halogen weight ratio, opens stirring, uses slag after ten minutes
Stock pump squeezes into plate and frame filter press filtering, obtains filter residue 44Kg, 0.97 m of primary purification filtrate3, control filtrate NTU < 20, SDI <
200。
(2) with the production water dilution old brine 9 of primary purification again to 8.73m3, squeezed into ultrafiltration apparatus and filtered with centrifugal pump, closed
Concentrated water valve is closed, controls filtrate NTU < 1, SDI < 5 obtain secondary refining brine 8.70m3, it is placed in spare in PP storage tank.Ultrafiltration membrane
Selection PVDF doughnut material, 0.1 μm of membrane aperture.
(3) secondary refining brine is squeezed into three groups of concatenated NF4040 type high pressure nanofiltration membrane separation devices, control level-one is received
Filter membrane intake pressure 60Bar, second level and three-level nanofiltration membrane intake pressure 38Bar, three-level high pressure nanofiltration membrane concentrated water successively return
Grade influent side produces water and sequentially enters next stage influent side.It is rich lithium liquid that third level nanofiltration membrane, which produces water, and three-level separation is total to obtain richness
5.39 m of lithium liquid3, [Li+] = 596 mg·L-1, concentrated water 3.30m3, [Li+] = 96 mg·L-1, lithium ion recycling is calculated
Rate is 90.21%.
(4) obtained rich lithium liquid pump is squeezed into 4040 type RO film condensing devices, control intake pressure 68Bar, enrichment 11.7
Times, obtain [Li+] 7.01g·L-1RO concentrate 457L continues to be concentrated to get [Li with MVR forced evaporation device+]
30.25g·L-1High lithium solution 105L, while obtaining pure water 5.28m3(2) return step dilutes brine, be recycled, the pure water by
RO produces water and MVR condensed water mixing gained.
(5) boron resin first uses 2molL-1The NaOH solution regeneration treatment of sulfuric acid and 10% concentration, squeezes into pure water respectively
To neutrality.The NaOH that 10% concentration is added to high lithium solution is squeezed into high lithium solution 105L with metering pump after adjusting pH to 8.4
The series connection boron resin column of 50L × 2, controls [the B in efflux2O3]<2mg·L-1, the high lithium solution 104L of boron removal is obtained, is then made
Boron resin is eluted with pure water, washing lotion return step is obtained and reuse is (4) concentrated.
(6) 25% soda bath is added into the high lithium solution of boron removal and adjusts pH value to 14, is pumped into plate and frame filter press with Pulp pump
Filtering, filter cake is magnesium hydroxide, by weight 1:1 plus pure water pulp washing, filtering and after drying as flame retardant of magnesium hydroxide
Sale.Filtrate refines high lithium solution.
(7) sodium carbonate liquor, two kinds of solution metering gears are added by refine lithium ion mole in high lithium solution 135%
It pumps while being pumped into enamel reaction still, after 90 DEG C of successive reaction 90min, slurry enters centrifuge from head tank gravity flow and filters, and obtains
To Crude lithium Carbonate and sinker mother liquor, after Crude lithium Carbonate sediment washs 2 times by weight 1:4 with high purity water, through centrifugal filtration, dodge
Battery-level lithium carbonate product 13.23Kg is obtained after being evaporated dry, air-flow crushing, the sinker Recycling Mother Solution uses, and test obtains electricity
Level lithium carbonate product main content in pond is 99.65%.
Embodiment 4
The present embodiment and embodiment 1 ~ 3 are different, it is therefore an objective to further recycle the sinker mother liquor of output in embodiment 1 ~ 3.It will
Sinker the mother liquor 570L, [Li that embodiment 1 ~ 3 is collected into+] = 1.34g·L-1, the old halogen of potassium is mentioned according to volume ratio 1:18 and West Platform
Water converts halogen, mentions potassium old halogen composition and is shown in Table 3, mixes slurry and is obtained by filtration with plate and frame filter press and mixes old halogen 10.46m3, sheet frame wet slag
It discards, test data such as table 4.
4 sinker mother liquor of table and West Platform mention the old halogen of potassium and mix test data table
It is learnt by table 4, is mixed using the old halogen of potassium is mentioned with sinker mother liquor, lithium ion most in sinker mother liquor can be recycled,
The lithium ion of sheet frame wet slag loss only accounts for the 4.84% of sinker mother liquor lithium ion total amount, and the sinker mother liquor lithium ion rate of recovery reaches
95.15%。
It should be understood that embodiment discussed here and embodiment simply to illustrate that, can be with to person skilled in the art
It is proposed various modifications and variations, such modifications and variations are included within spirit herein spirit and scope and appended right
In claimed range.
Claims (10)
1. a kind of method for extracting battery-level lithium carbonate from magnesium sulfate salt lake bittern, comprising the following steps:
(1) flyash addition is mentioned in the old halogen of potassium, be pumped into plate and frame filter press filtering through slurry, obtain the old brine of primary purification；It is described
The additional amount of flyash mentions the 0.1 ~ 10% of the old halogen weight of potassium described in being；
(2) the primary purification old brine production water is diluted 4 ~ 10 times, be pumped into ultrafiltration apparatus, obtain the old halogen of secondary refining
Water；
(3) the old brine of the secondary refining is pumped into three-level high pressure nano filter membrance device, applies 3.8 ~ 8.0MPa pressure, obtain richness
Lithium liquid and dope；[Li in the richness lithium liquid+] between 240 ~ 1250 mgL-1；
(4) the rich lithium liquid is carried out two-stage concentration: the first order is concentrated using RO film, [Li+] from 240 ~ 1250 mgL-1Enrichment
To 3500 ~ 7000 mgL-1；The second level is concentrated using MVR forced evaporation, [Li+] from 3500 ~ 7000mgL-1Enrichment to 25 ~
42g·L-1, [B2O3] between 6.5 ~ 8.5 gL-1, respectively obtain high lithium solution and pure water；Two-stage is concentrated to get pure
Water returns to the step and is (2) recycled；
(5) the high lithium solution is squeezed into boron resin exchange column, remove the boron element in high lithium solution, obtain [B2O3] between
0.5~100mg·L-1The high lithium solution of boron removal；
(6) the high lithium solution of the boron removal uses mass concentration to adjust pH value to after 12 ~ 14 for 25% sodium hydroxide solution, is pumped into plate
The filtering of frame filter press, obtains refining high lithium solution；
(7) sodium carbonate liquor is added by 125 ~ 135% of lithium ion mole in the high lithium solution of purification, is being warded off in 85 ~ 95 DEG C
In porcelain reaction kettle after 60 ~ 120min of successive reaction, slurry is pumped into centrifuge filtering, respectively obtains Crude lithium Carbonate and sinker mother liquor；
The sinker mother liquor returns to the step and is (1) recycled；After the Crude lithium Carbonate sediment pure water, is filtered, done
It is dry, crush up to battery-level lithium carbonate product.
2. a kind of method for extracting battery-level lithium carbonate from magnesium sulfate salt lake bittern as described in claim 1, special
Sign is: the step (1) in mention the old halogen of potassium and refer to the old brine after the extracted sylvite of magnesium sulfate brine, [Li in brine+]
Between 1.3 ~ 4.0gL-1, [Mg2+] between 98 ~ 125 gL-1, [SO4 2-] between 25 ~ 74 gL-1。
3. a kind of method for extracting battery-level lithium carbonate from magnesium sulfate salt lake bittern as described in claim 1, special
Sign is: the step (1) in flyash additional amount be the old brine weight 1.5 ~ 3.5%.
4. a kind of method for extracting battery-level lithium carbonate from magnesium sulfate salt lake bittern as described in claim 1, special
Sign is: the step (2) in old brine extension rate be 8 ~ 9 times.
5. a kind of method for extracting battery-level lithium carbonate from magnesium sulfate salt lake bittern as described in claim 1, special
Sign is: (2) middle ultrafiltration apparatus refers to hollow-fibre membrane ultrafiltration apparatus, material PVDF, 0.05 ~ 0.5 μ of membrane aperture to the step
M, preferably membrane aperture are 0.05 ~ 0.1 μm.
6. a kind of method for extracting battery-level lithium carbonate from magnesium sulfate salt lake bittern as described in claim 1, special
Sign is: (3) middle three-level high pressure nano filter membrance device refers to three groups of concatenated NF4040 type high pressure nanofiltration UF membranes dresses to the step
It sets, can tolerate highest operating pressure is 8.0MPa.
7. a kind of method for extracting battery-level lithium carbonate from magnesium sulfate salt lake bittern as described in claim 1, special
Sign is: (3) middle three-level membrane separating process refers to that first order lock out operation pressure is 5.5 ~ 7.5MPa, preferred scope to the step
It is 5.5 ~ 6.5MPa；The second level and third level operating pressure are 3.7 ~ 4.5MPa, and preferred scope is 3.7 ~ 4.0MPa.
8. a kind of method for extracting battery-level lithium carbonate from magnesium sulfate salt lake bittern as described in claim 1, special
Sign is: (4) middle RO film concentration is sea water desalination membrane to the step, and primary concentration operating pressure is 4.0 ~ 8.0MPa, preferred operations
Pressure is 6.5 ~ 6.9MPa.
9. a kind of method for extracting battery-level lithium carbonate from magnesium sulfate salt lake bittern as described in claim 1, special
Sign is: the step (5) in borohydride exchange resin be a kind of styrene and divinylbenzene crosslink, there is N- methyl glucose osamine
The macroporous structure chelating resin of base.
10. a kind of method for extracting battery-level lithium carbonate from magnesium sulfate salt lake bittern as described in claim 1, special
Sign is: the step (7) in sinker Recycling Mother Solution in use, the sinker mother liquor and the mass ratio for mentioning the old halogen of potassium are 1:5
~ 1:20, preferred proportion are 1:15 ~ 1:18.
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| CN112624155A (en) * | 2021-02-02 | 2021-04-09 | 江西赣锋锂业股份有限公司 | Method for preparing battery-grade anhydrous lithium chloride by purifying old brine |
| WO2021092013A1 (en) * | 2019-11-06 | 2021-05-14 | Fluid Technology Solutions (Fts), Inc. | Methods and systems for reducing magnesium in high salinity salar brines by nanofiltration and forward osmosis |
| CN114381614A (en) * | 2021-12-20 | 2022-04-22 | 恒信润丰科技开发（北京）有限公司 | Method for extracting lithium from salt lake and brine |
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