CN105502440B - The rough refining methd of sulfuric acid lithium salts - Google Patents
The rough refining methd of sulfuric acid lithium salts Download PDFInfo
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- CN105502440B CN105502440B CN201510881141.3A CN201510881141A CN105502440B CN 105502440 B CN105502440 B CN 105502440B CN 201510881141 A CN201510881141 A CN 201510881141A CN 105502440 B CN105502440 B CN 105502440B
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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
- C01D15/06—Sulfates; Sulfites
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
- C01B35/10—Compounds containing boron and oxygen
- C01B35/12—Borates
- C01B35/121—Borates of alkali metal
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
- C01B35/10—Compounds containing boron and oxygen
- C01B35/12—Borates
- C01B35/126—Borates of alkaline-earth metals, beryllium, aluminium or magnesium
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- 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
- C01D3/08—Preparation by working up natural or industrial salt mixtures or siliceous minerals
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
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- 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
- C01F5/26—Magnesium halides
- C01F5/30—Chlorides
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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
Abstract
The present invention provides a kind of refining methd that sulfuric acid lithium salts is rough, comprising steps of the first step, the rough S0 of sulfuric acid lithium salts is mixed with excessive water, so that the soluble ingredient during lithium sulfate is rough is completely dissolved just, solution L0 is obtained after separation of solid and liquid；Solution L0 is carried out freezing and saltcake is precipitated, obtains solution L1 and solid S1 after separation of solid and liquid by second step；Solution L1 is evaporated by third step, and solid phase is precipitated, obtains solution L2 and solid S2 after separation of solid and liquid；Solution L2 is sealed under the conditions of 0 DEG C~40 DEG C of temperature and places 7~50 days precipitation borates, obtains solution L3 after separation of solid and liquid by the 4th step；5th step mixes the solid S1 that second step refrigerating process obtains with solution L3, and sulfuric acid lithium concentrate is precipitated in evaporation under the conditions of 0 DEG C~40 DEG C of temperature.
Description
Technical field
Sulfate type making from brine be the present invention relates to the use of for the method more particularly to a kind of essence that lithium sulfate is rough of lithium sulfate
Method processed.
Background technique
There is large number of salt lake in China on Qinghai-Tibet Platean.Wherein Chaidamu of Qinghai Province salt lake such as Cha Er Han Salt Lake, big
Bavin denier salt lake, eastern West Taijinar Salt Lake, a salt lake Li Ping, the salt lake small Si Kule etc., by the great amount of investment of national decades,
The conditions such as infrastructure such as highway, railway, electric power, water resource are preferable, developed or had exploit condition, wherein Cha Er Han
Salt lake has become the maximum Salt Lake Potash production base in China.In the exploitation in these salt lakes, people attempt reality by persistence
The comprehensive utilization of the resources such as existing potassium, lithium, boron, magnesium, sodium, some technologies successfully realize industrialness trial production, but really realize big
The only potash fertilizer of technical scale production, the production of sodium salt, magnesium salts series of products begins to take shape, but the production of boron, lithium is still difficult
It is heavy.
Tibet region salt lake exploit condition is extremely severe, removes salt lake solid boron rock and Zha Buye carbonate-type halogen even to this day
Water lithium mine obtains outside Part Development, and there are no the successful examples of brine comprehensive exploitation, main reason is that: height above sea level, Tibet salt
The general height above sea level in lake is in 4000~5000m range, and Gao Zheda 5000m or more, natural environment is extremely severe, and ecological environment is highly brittle
Weak, environmental requirement is high；Have inconvenient traffic, Tibet region salt lake transportation condition is very poor, far from national highway, condition it is best also there was only sandstone
Road can reach, and far from product market comsupton region, haul distance is most short also 2000km, and major part is in 3000km or more；Base
The basic blank of Infrastructure does not build the condition of large-scale factory far from power grid, circumference several hundred kilometers do not have chemical company and
For the auxiliary equipment utilized.
The applicant's long, annual range of temperature and day and night temperature is big, drought, wind are big etc. using the Tibetan Salt Lakes regional sunshine-duration
Advantageous natural conditions, develop that " salt pan solarization enrichment → freezing, which removes nitre → return convert demagging → and is diluted to salt, obtains boron rock → evaporation analysis
The technique of lithium salts mine out " obtains Li at the Tibet salt lake Cha Bocuo scene2SO4·H2O mass fraction is about 17%~36%
Lithium sulfate is rough, and other ingredients of the mine are NaCl, MgSO4·7H2O and carnallite (KClMgCl2·6H2The water solubilitys such as O)
Salt and a small amount of sandstone.Since the rough grade of the lithium sulfate is lower, to further increase its economic value added, applicant is opened early period
The research and probe for preparing lithium salts product from the mine using chemical method has been opened up, the side of demagging, sulfate radical, deliming is successively passed through
Formula removes impurity, obtains rich lithium solution, has respectively obtained Li using different process2CO3、Li2SO4·H2O and LiOHH2O is produced
Product.But since the process route is longer, new chemical reagent, the purity and receipts of lithium sulfate product are introduced in multiple removal steps
Rate is unsatisfactory.
For this purpose, providing a kind of without introducing the rough refining methd of the simple lithium sulfate of chemical reagent, process route very
It is necessary.
Summary of the invention
For this purpose, the present invention provide it is a kind of without introducing the rough purification side of the simple lithium sulfate of chemical reagent, process route
Method.
A kind of refining methd that sulfuric acid lithium salts is rough comprising step:
The first step mixes the rough S0 of sulfuric acid lithium salts with excessive water, so that the soluble ingredient during lithium sulfate is rough is just complete
Fully dissolved obtains solution L0 and solid not soluble in water after separation of solid and liquid；
Second step freezes solution L0 under the conditions of -30 DEG C~0 DEG C of temperature, and saltcake is precipitated, after separation of solid and liquid
To solution L1 and solid S1, the main ingredient of solid S1 is saltcake；
Solution L1 is evaporated by third step under the conditions of 0 DEG C~40 DEG C of temperature, and solid phase is precipitated, after separation of solid and liquid
To solution L2 and solid S2, the main ingredient of solid S2 is NaCl and KClMgCl2·6H2O；
Solution L2 is sealed placement 7~50 days by the 4th step under the conditions of 0 DEG C~40 DEG C of temperature, and borate, solid-liquid is precipitated
Solution L3 and solid S3 are obtained after separation, solid S3 main ingredient is the borate of Li and Mg；
5th step mixes the solid S1 that second step refrigerating process obtains with solution L3, in 0 DEG C~40 DEG C of temperature
Under the conditions of evaporate, sulfuric acid lithium concentrate is precipitated, obtains sulfuric acid lithium concentrate and solution L4 after separation of solid and liquid.
Preferably, the sulfuric acid lithium concentrate main ingredient that the 5th step obtains be mass ratio close to 1:1 NaCl and
Li2SO4·H2The mixture of O.
Preferably, relative to the rough S0 of lithium sulfate in the first step, Li contains in the sulfuric acid lithium concentrate that the 5th step obtains
Amount improves 1 times or more.
Preferably, relative to the rough S0 of lithium sulfate in the first step, Mg contains in the sulfuric acid lithium concentrate that the 5th step obtains
Amount is reduced to 20%~0.1%, the K content of Mg content in the rough S0 of lithium sulfate to be reduced to the 20% of the rough middle K content of lithium sulfate
~0.1%.
Preferably, Li in the sulfuric acid lithium concentrate that the 5th step obtains2SO4·H2O mass percentage is about 35%~
50%.
Preferably, it in the second step, is freezed under the conditions of -30 DEG C~0 DEG C of temperature, sulphur in obtained solution L1
The content of acid ion reduces 90% or more relative to solution L0.
Preferably, it is evaporated under the conditions of 0 DEG C~40 DEG C of temperature in the third step, evaporation goes to account for system gross mass
It is separated by solid-liquid separation after 40%~60% water.
Preferably, the first step to the 5th step a process flow after, the yield of lithium sulfate is 35%~
65%.
The first step to the 5th step a process flow after obtained solution L4 return to the first step, replace part
Water for dissolving the rough S0 of lithium sulfate carries out next step circulation and obtains sulfuric acid lithium concentrate by sufficiently recycling.
In the abundant cyclic process, only along with the analysis of a small amount of lithium double salt in the solid S2 of carnallite precipitation phase
It loses and in the solid S3 of borate precipitation phase there are 15%~25% lithium along with a small amount of lithium borate salts out
It is precipitated and the loss of existing 1% or so lithium, separately there is 10%~15% or so lithium to reside in mother liquor and recycle in system, body
Remaining lithium is all with the precipitation of sulfuric acid lithium concentrate in system.
Compared with prior art, the invention has the following advantages that
Firstly, refining methd of the invention is not introduced into any chemical reagents, full utilization natural energy uses physical method, ring
It protects pollution-free, belongs to green clean energy resource technique.
Secondly, refining methd process route of the invention is simple, using " molten mine --- freezing --- evaporation --- analysis
Boron --- convert nitre evaporation " technology path, can be completed using five core procedures to rough purification, process route is short, removes
Miscellaneous step is very simple, but has reached lithium sulfate in high yield.According to this five step process route, a process terminates, sulfuric acid
The yield of lithium is 35%~65%.
Again, in subtractive process of the invention, the solution that is obtained after a process flow of the first step to the 5th step
L4 returns to the first step, replaces part for dissolving the water of the rough S0 of lithium sulfate, into the of the rough refining methd of sulfuric acid lithium salts
Two circulations, according in this way, the rough dissolution water of the first step lithium sulfate of cyclic process each time is obtained by preceding one cycle
L4 solution and the fresh water composition arrived, two-part ratio is related with L4 composition, can make in this way thick in lithium sulfate
During mine separating-purifying, the lithium sulfate being dissolved in mother liquor L4 is utilized, while can reduce by second and following cycle
The solution loss of middle lithium sulfate, whole process is only along with the analysis of a small amount of lithium double salt in the solid S2 of carnallite precipitation phase
It loses and in the solid S3 of borate precipitation phase there are 25% or so lithium along with the analysis of a small amount of lithium borate salts out
Existing 1% or so lithium loss out, separately has 10%~15% or so lithium to reside in mother liquor and recycle in system, body
Remaining lithium improves the yield of sulfuric acid lithium concentrate all with the precipitation of sulfuric acid lithium concentrate in system.
Finally, of the invention using simple process route, efficiently use natural energy remove lithium sulfate it is rough in potassium,
The impurity such as magnesium, boron, obtaining principal component is Li2SO4·H2The concentrate of O and NaCl, Li in concentrate2SO4·H2The mass percentage of O
About 35%~50%.Nearly 1 times of the more rough raising of Li content in concentrate, and Mg content is reduced to rough 17%, K content drop
Down to rough 1/3, very good purification effect is reached.
Detailed description of the invention
Fig. 1 is the rough refining methd flow chart of lithium sulfate of the present invention.
Specific embodiment
To make the objectives, technical solutions, and advantages of the present invention more comprehensible, below in conjunction with specific embodiment, to this hair
It is bright to be described in detail.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to limit
The present invention.
Rough lithium sulfate used in the present invention is using the patented technology before the applicant, referring to Chinese patent
201310124971.2, it is entitled " using the method for beneficial element in natural energy concentration and separation sulfate type shielding brine ".It is main
Wanting step includes: that will look into wave to arrange original bittern evaporation to sodium chloride saturation state, freezes nitre in winter, is then evaporated first in spring and summer
Precipitated sodium chloride, sylvite, carnallite, epsomite afterwards control lithium concentration >=6g/L in brine and are separated by solid-liquid separation, obtained
The brine of high content of magnesium chloride；Sodium salt and magnesium salts is precipitated with saltcake hybrid reaction in it, Mg/Li ratio in solution is controlled and is less than or waits
It is separated by solid-liquid separation when 8:1, obtains boron-rich lithium brine；The content of boron-rich lithium bittern evaporation to boron or elemental lithium is reached predetermined
Boron rock is precipitated in value Shi Yushui or original brine hybrid reaction, and liquid phase is rich lithium brine, and it is rough to continue evaporation precipitation lithium sulfate.
As shown in Figure 1, the rough refining methd of lithium sulfate of the present invention includes five steps:
The rough S0 of lithium sulfate is dissolved in the water by the first step.
It is mixed with excessive water by sulfate is rough, so that the soluble ingredient during sulfate is rough is completely dissolved just, solid-liquid
The insoluble matters such as solution L0 and solid not soluble in water, such as silt are obtained after separation.
Solution L0 is carried out freezing and saltcake is precipitated, obtains solution L1 and solid after separation of solid and liquid by second step.
Solution L0 carries out freezing processing under the conditions of -30 DEG C~0 DEG C of temperature, and saltcake is precipitated, by sufficiently freezing so that
Solid does not continue to be separated by solid-liquid separation when being precipitated, and obtains solution L1 and solid S1.
In the refrigerating process, the SO of 90%~99% (mass percent)4 2-Be frozen out in the form of saltcake, reached compared with
The good effect for removing sulfate radical.Due in sulfate type salt lake brine, a large amount of presence of sulfate ion, so that in brine
Potassium is precipitated in the form of potassium mixed salt, it is difficult to be separated with lithium.Therefore, a large amount of of sulfate radical remove point so that potassium and lithium in this step
From becoming easy.
Solid S1 main component is saltcake, further includes a small amount of lithium double salt.The causa essendi of a small amount of lithium double salt is to be separated by solid-liquid separation
When, entrainment mother liquor amount is about 10%~25% in solid phase.
Solid S1 will also be used to convert halogen in back segment test and lithium sulfate is precipitated, so that lithium, which may return in system, to be damaged
It loses.
Solution L1 is evaporated processing under the conditions of 0 DEG C~40 DEG C of temperature by third step.
Li with the evaporation of solution L1, in solution+、Mg2+Ion and B2O3Concentration is in increase trend, liquid with density
After being mutually saturated start that new solid phase is precipitated, is separated by solid-liquid separation, is obtained after the water for accounting for system gross mass 40%~60% is removed in evaporation
To solution L2 and solid S2.
The main component of solid S2 is NaCl and KClMgCl2·6H2O (carnallite).Obviously, the potassium in solution L1, magnesium
It is precipitated in the form of carnallite, has reached the separation of lithium magnesium, lithium potassium.During preparing lithium sulfate salt mine due to sulfate brine,
The presence of magnesium, potassium makes analysis salt process become very complicated, to increase the enrichment difficulty of lithium.And it is in this step that magnesium, potassium is same
When remove so that the concentration of lithium ion greatly promotes in solution L2, the subsequent process that lithium sulfate salt mine is precipitated becomes to be relatively easy to.
In addition, due to the removal of magnesium, potassium, B in solution L22O3Concentration also gets a promotion, in order to finally obtain lithium sulfate salt mine, in next step
B will be removed2O3。
4th step, solution L2 under the conditions of 0 DEG C~40 DEG C of temperature, place 7~50 days by sealing, and borate, solid-liquid is precipitated
Solution L3 and solid S3 are obtained after separation.
Solution L2 is placed in glass container, is placed 7~50 days or so after being sealed with preservative film, occurs white in container
Flocculent deposit obtains solid S3 (white filter cake) and solution L3 after separation of solid and liquid.Solid S3 is mainly the borate of Li and Mg.
XRD analysis shows that solid phase components are Li4B2O5、NaB5O6(OH)4、Mg2B12O20·5H2O。
5th step, the solid S1 that second step refrigerating process is obtained is added in solution L3, in 0 DEG C~40 DEG C of temperature condition
Sulfuric acid lithium concentrate is precipitated in lower evaporation.
The solid S1 main component that second step refrigerating process obtains is saltcake and a small amount of lithium double salt, returns and converts in solution L3,
The lithium carried secretly in solid S1 is come back in system.The mixture of solid S1 and solution L3 are steamed at room temperature
Hair, it is to be evaporated to moisture removal amount to calculated value when, the particle of square block and needle-shaped two kinds of crystal forms is obtained, after separation of solid and liquid
Obtain solid S4 and solution L4.It is shown by XRD analysis, solid S4 is NaCl and Li2SO4·H2The mixture of O, that is, lithium sulfate
Concentrate.Relative to rough, Li content improves about 1 times in concentrate, and the yield of lithium is 35%~65%, Li2SO4·H2O mass percentage
Content is about 35%~50%.Mg content is reduced to 20%~0.1%, the K content of Mg content in the rough S0 of lithium sulfate in concentrate
It is reduced to the 20%~0.1% of the rough middle K content of lithium sulfate, has reached preferable lithium magnesium, lithium potassium separating effect and rough purification
Effect.
The rough refining methd of above-mentioned lithium sulfate have passed through 5 steps, the solid group that each step obtains after being separated by solid-liquid separation
It is as shown in table 1 at qualification result.
The rough Refining tests solid phase XRD qualification result of 1 lithium sulfate of table
Finally obtained sulfuric acid lithium concentrate main component is NaCl and Li of the mass ratio close to 1:12SO4·H2O.It can be used
Flotation Li2SO4Or the method for reverse flotation removal NaCl obtains the higher lithium sulfate of purity, and combines and be recrystallized to give sulfuric acid lithium salts
Product；After can also being dissolved, again using the route of " " molten mine --- nitre evaporation is converted in freezing --- evaporation --- analysis boron --- "
Further purification.
In lithium sulfate delicate procedure of the invention, the process route including five steps, after a process, lithium sulfate
Yield be 35%~65%, the solution L4 that remaining most of lithium obtains after being separated by solid-liquid separation with the 5th step is re-used for next
The rough course of dissolution of the lithium sulfate of circulation and be utilized again.Specifically, in subtractive process of the invention, the first step to the 5th
The solution L4 obtained after one process flow of step replaces part for dissolving the rough S0's of lithium sulfate back to the first step
Water, into second of the rough refining methd of sulfuric acid lithium salts circulation, according in this way, the first step sulfuric acid of cyclic process each time
The L4 solution and fresh water that the rough dissolution water of lithium is obtained by preceding one cycle form, and two-part ratio has with L4 composition
It closes, can make during lithium sulfate rough separating-purifying in this way, the lithium sulfate being dissolved in mother liquor L4 obtains benefit
With, while the solution loss of lithium sulfate in second and following cycle can be reduced, only rank is precipitated in carnallite in whole process
It is salted out along with the precipitation of a small amount of lithium double salt there are the loss of 15~25% or so lithium and in boric acid in the solid S2 of section
Existing 1% or so the lithium loss along with the precipitation of a small amount of lithium borate salts, separately there is 10%~15% in the solid S3 in stage
The lithium of left and right is resided in mother liquor and is recycled in system, remaining lithium is all precipitated in the form of sulfuric acid lithium concentrate, lithium sulfate
The yield of concentrate greatly arrives promotion therewith.
Compared with prior art, the invention has the following advantages that
Firstly, refining methd of the invention is not introduced into any chemical reagents, full utilization natural energy uses physical method, ring
It protects pollution-free, belongs to green clean energy resource technique.
Secondly, refining methd process route of the invention is simple, using " molten mine --- freezing --- evaporation --- analysis
Boron --- convert nitre evaporation " technology path, can be completed using five core procedures to rough purification, process route is short, removes
Miscellaneous step is very simple, but has reached lithium sulfate in high yield.According to this five step process route, a process terminates, sulfuric acid
The yield of lithium is 35%~65%.
Again, in subtractive process of the invention, the solution that is obtained after a process flow of the first step to the 5th step
L4 returns to the first step, replaces part for dissolving the water of the rough S0 of lithium sulfate, into the of the rough refining methd of sulfuric acid lithium salts
Two circulations, according in this way, the rough dissolution water of the first step lithium sulfate of cyclic process each time is obtained by preceding one cycle
L4 solution and the fresh water composition arrived, two-part ratio is related with L4 composition, can make in this way thick in lithium sulfate
During mine separating-purifying, the lithium sulfate being dissolved in mother liquor L4 is utilized, while can reduce by second and following cycle
The solution loss of middle lithium sulfate, whole process is only along with the analysis of a small amount of lithium double salt in the solid S2 of carnallite precipitation phase
It loses out and there are 15%~25% or so lithium and in the solid S3 of borate precipitation phase along with a small amount of lithium boron acid
The precipitation of salt and existing 1% or so lithium loss, separately there is 10%~15% or so lithium to reside in mother liquor and in system
It recycles, remaining lithium is all precipitated in the form of sulfuric acid lithium concentrate in system, and the yield of sulfuric acid lithium concentrate is greatly improved.
Finally, of the invention using simple process route, efficiently use natural energy remove lithium sulfate it is rough in potassium,
The impurity such as magnesium, boron, obtaining principal component is Li2SO4·H2The concentrate of O and NaCl, Li in concentrate2SO4·H2The mass percentage of O
About 35%~50%.Nearly 1 times of the more rough raising of Li content in concentrate, and Mg content is reduced to Mg in the rough S0 of lithium sulfate to contain
20%~0.1%, the K content of amount is reduced to the 20%~0.1% of the rough middle K content of lithium sulfate, has reached very good purification essence
Effect processed.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. a kind of refining methd that sulfuric acid lithium salts is rough comprising step:
The first step mixes the rough S0 of sulfuric acid lithium salts with water, so that the soluble ingredient during lithium sulfate is rough is completely dissolved just, Gu
Solution L0 and solid not soluble in water are obtained after liquid separation；
Second step freezes solution L0 under the conditions of -30 DEG C~0 DEG C of temperature, and saltcake is precipitated, obtains after separation of solid and liquid molten
The main ingredient of liquid L1 and solid S1, solid S1 are saltcake；
Solution L1 is evaporated by third step under the conditions of 0 DEG C~40 DEG C of temperature, and solid phase is precipitated, obtains after separation of solid and liquid molten
The main ingredient of liquid L2 and solid S2, solid S2 are NaCl and KClMgCl2·6H2O；
Solution L2 is sealed placement 7~50 days by the 4th step under the conditions of 0 DEG C~40 DEG C of temperature, and borate is precipitated, and is separated by solid-liquid separation
After obtain solution L3 and solid S3, solid S3 main ingredient is the borate of Li and Mg；
5th step mixes the solid S1 that second step refrigerating process obtains with solution L3, in 0 DEG C~40 DEG C of temperature condition
Lower evaporation is precipitated sulfuric acid lithium concentrate, obtains sulfuric acid lithium concentrate and solution L4 after separation of solid and liquid.
2. the method as described in claim 1, it is characterised in that: the sulfuric acid lithium concentrate main ingredient that the 5th step obtains is matter
Amount is than the NaCl and Li for 1:12SO4·H2The mixture of O.
3. the method as described in claim 1, it is characterised in that: relative to the lithium sulfate rough S0 in the first step, the described 5th
It walks Li content in obtained sulfuric acid lithium concentrate and improves 1 times or more.
4. method as claimed in claim 3, it is characterised in that: relative to the lithium sulfate rough S0 in the first step, the described 5th
Walking Mg content in obtained sulfuric acid lithium concentrate is reduced to 20%~0.1%, the K content of Mg content in the rough S0 of lithium sulfate to be reduced to
The 20%~0.1% of K content in the rough S0 of lithium sulfate.
5. the method as described in claim 1, it is characterised in that: Li in the sulfuric acid lithium concentrate that the 5th step obtains2SO4·H2O
Mass percentage is 35%~50%.
6. the method as described in claim 1, it is characterised in that: in the second step, under the conditions of -30 DEG C~0 DEG C of temperature
It is freezed, the content of sulfate ion reduces 90% or more relative to solution L0 in obtained solution L1.
7. the method as described in claim 1, it is characterised in that: in the third step under the conditions of 0 DEG C~40 DEG C of temperature into
Row evaporation, evaporation are separated by solid-liquid separation after removing the water for accounting for system gross mass 40%~60%.
8. the method as described in claim 1, it is characterised in that: a process flow of the first step to the 5th step terminates
Afterwards, the yield of lithium sulfate is 35%~65%.
9. method according to claim 8, it is characterised in that: after a process flow of the first step to the 5th step
Obtained solution L4 returns to the first step, replaces part to carry out next step circulation for dissolving the water of the rough S0 of lithium sulfate, through overcharging
Divide circulation, obtains sulfuric acid lithium concentrate.
10. method as claimed in claim 9, it is characterised in that: in the abundant cyclic process, only carnallite precipitation phase
Solid S2 in along with the precipitation of a small amount of lithium double salt and there are the lithium of 15%-25% loss and borate precipitation phase solid
The existing 1% lithium loss along with the precipitation of a small amount of lithium borate salts, separately has the lithium of 10%-15% to reside in mother liquor in S3
And recycled in system, remaining lithium is all with the precipitation of sulfuric acid lithium concentrate in system.
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| CN107188205A (en) * | 2017-07-15 | 2017-09-22 | 汕头市泛世矿产资源股份有限公司 | The technique that a kind of acidization extracts lithium sulfate from amblygonite |
| CN107200338A (en) * | 2017-07-15 | 2017-09-26 | 汕头市泛世矿产资源股份有限公司 | The technique that a kind of acidization extracts lithium hydroxide from amblygonite |
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