CN105502440A - Method for purifying lithium sulfate crude ore - Google Patents
Method for purifying lithium sulfate crude ore Download PDFInfo
- Publication number
- CN105502440A CN105502440A CN201510881141.3A CN201510881141A CN105502440A CN 105502440 A CN105502440 A CN 105502440A CN 201510881141 A CN201510881141 A CN 201510881141A CN 105502440 A CN105502440 A CN 105502440A
- Authority
- CN
- China
- Prior art keywords
- solid
- lithium
- solution
- rough
- lithium sulphate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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 invention provides a method for purifying lithium sulfate crude ore. The method comprises the following steps: step I, mixing the lithium sulfate crude ore S0 with excessive water to ensure that soluble ingredients in the lithium sulfate crude ore are just dissolved completely, and carrying out solid-liquid separation to obtain a solution L0; step II, freezing the solution L0 to separate out mirabilite, and carrying out solid-liquid separation to obtain a solution L1 and a solid S1; step III, evaporating the solution L1 to separate out a solid phase, and carrying out solid-liquid separation to obtain a solution L2 and a solid S2; step IV, allowing the solution L2 to stand still in a sealed condition for 7 to 50 days at 0 to 40 DEG C to separate out borate, and carrying out solid-liquid separation to obtain a solution L3; step V, mixing the solid S1 obtained in the freezing process in the step II with the solution L3, and evaporating the mixture at 0 to 40 DEG C to separate lithium sulfate concentrate.
Description
Technical field
The present invention relates to the method utilizing vitriolate type bittern to prepare Lithium Sulphate, particularly relate to the process for purification that a kind of Lithium Sulphate is rough.
Background technology
China Qinghai-Tibet Platean there is the salt lake of One's name is legion.Wherein salt lake, Chaidamu of Qinghai Province is as Cha Er Han Salt Lake, large bavin dawn salt lake, eastern West Taijinar Salt Lake, a Li Ping salt lake, small Si Kule salt lake etc., through the great amount of investment of country's decades, Infrastructure is as better in conditions such as highway, railway, electric power, water resourcess, develop or possess exploit condition, wherein Cha Er Han Salt Lake has become the maximum Salt Lake Potash production base of China.In the exploitation in these salt lakes, people attempt the comprehensive utilization realizing the resources such as potassium, lithium, boron, magnesium, sodium by persistence, some technology successfully realizes industrialness trial production, but what really realize large-scale commercial production only has potash fertilizer, the production of sodium salt, magnesium salts series product begins to take shape, but the production of boron, lithium is still difficult.
Salt lake, Tibet region exploit condition is abnormal severe, even to this day except salt lake solid boron rock and Zha Buye carbonate type bittern lithium ore deposit obtain except Part Development, also there is no the examples of many successful of bittern comprehensive exploitation, major cause is: height above sea level, the general height above sea level of Tibetan Salt Lakes is in 4000 ~ 5000m scope, and high person reaches more than 5000m, and physical environment is extremely severe, ecotope is very fragile, and environmental requirement is high; Have inconvenient traffic, salt lake, Tibet region transportation condition extreme difference, away from national highway, what condition was best also only has sandstone road to arrive, and away from produce market consumption area, haul distance is the shortest also 2000km, and major part is at more than 3000km; Infrastructure is substantially blank, away from electrical network, does not build the condition of large-scale factory, and circumference several hundred kilometers does not have chemical enterprise and can supply the off-set facility of utilization.
The applicant utilizes Tibetan Salt Lakes area sunshine duration long, year temperature difference and the favourable natural condition such as day and night temperature is large, drought, wind are large, develop the technique of " salt pan Exposure to Sunlight enrichment → freezing obtains boron rock → evaporation precipitation lithium salts ore deposit except nitre → return converts demagging → dilution salify ", obtain Li at scene, Cha Bocuo salt lake, Tibet
2sO
4h
2o massfraction be about 17% ~ 36% Lithium Sulphate rough, other composition in this ore deposit is NaCl, MgSO
47H
2o and carnallitite (KClMgCl
26H
2water miscible salt and a small amount of sandstone such as O).Because the rough grade of this Lithium Sulphate is lower, for improving its economic value added further, applicant has carried out the research and probe that employing chemical process prepares lithium salts product from this ore deposit early stage, successively remove impurity by the mode of demagging, sulfate radical, deliming, obtain rich lithium solution, then obtain Li respectively through different process
2cO
3, Li
2sO
4h
2o and LiOHH
2o product.But because this operational path is longer, introduce new chemical reagent in multiple removal step, purity and the yield of Lithium Sulphate product are unsatisfactory.
For this reason, provide a kind of process for purification without the need to introducing chemical reagent, the simple Lithium Sulphate of operational path rough very necessary.
Summary of the invention
For this reason, the invention provides a kind of without the need to introducing the rough process for purification of chemical reagent, the simple Lithium Sulphate of operational path.
The process for purification that sulfuric acid lithium salts is rough, it comprises step:
The first step, mixed with excessive water by rough for sulfuric acid lithium salts S0, the soluble ingredient in making Lithium Sulphate rough dissolves just completely, obtains solution L0 and water-fast solid after solid-liquid separation;
Second step, carries out freezing under the temperature condition of-30 DEG C ~ 0 DEG C by solution L0, separate out saltcake, obtain solution L1 and solid S1 after solid-liquid separation, the major ingredient of solid S1 is saltcake;
3rd step, evaporates solution L1 under the temperature condition of 0 DEG C ~ 40 DEG C, and separate out solid phase, obtain solution L2 and solid S2 after solid-liquid separation, the major ingredient of solid S2 is NaCl and KClMgCl
26H
2o;
4th step, placed 7 ~ 50 days at the temperature condition lower seal of 0 DEG C ~ 40 DEG C by solution L2, separate out borate, obtain solution L3 and solid S3 after solid-liquid separation, solid S3 major ingredient is the borate of Li and Mg;
5th step, the solid S1 obtained by second step refrigerating process mixes with solution L3, evaporates under the temperature condition of 0 DEG C ~ 40 DEG C, separates out Lithium Sulphate concentrate, obtains Lithium Sulphate concentrate and solution L4 after solid-liquid separation.
Preferably, the Lithium Sulphate concentrate major ingredient that described 5th step obtains is NaCl and Li of mass ratio close to 1:1
2sO
4h
2the mixture of O.
Preferably, relative to the rough S0 of the Lithium Sulphate in the first step, in the Lithium Sulphate concentrate that described 5th step obtains, Li content improves more than 1 times.
Preferably, relative to the rough S0 of the Lithium Sulphate in the first step, 20% ~ 0.1%, the K content that in the Lithium Sulphate concentrate that described 5th step obtains, Mg content is reduced to Mg content in the rough S0 of Lithium Sulphate is reduced to 20% ~ 0.1% of the rough middle K content of Lithium Sulphate.
Preferably, Li in the Lithium Sulphate concentrate that obtains of described 5th step
2sO
4h
2o mass percentage is about 35% ~ 50%.
Preferably, in described second step, carry out freezing under the temperature condition of-30 DEG C ~ 0 DEG C, in the solution L1 obtained, the content of sulfate ion reduces more than 90% relative to solution L0.
Preferably, evaporate under the temperature condition of 0 DEG C ~ 40 DEG C in described 3rd step, after evaporating the water going to account for system total mass 40% ~ 60%, carry out solid-liquid separation.
Preferably, after the described the first step a to technical process of the 5th step terminates, the yield of Lithium Sulphate is 35% ~ 65%.
The described the first step returns the first step to the solution L4 obtained after a technical process of the 5th step terminates, and replacement part carries out next step circulation for the water dissolving the rough S0 of Lithium Sulphate, through fully circulating, obtains Lithium Sulphate concentrate.
In described abundant working cycle, in the solid S2 of carnallitite precipitation phase, the lithium loss of exist along with the precipitation of a small amount of lithium borate salts in the lithium loss of 15% ~ 25% and the solid S3 at borate precipitation phase about 1% is only there is along with the precipitation of a small amount of lithium double salt, separately have the lithium of about 10% ~ 15% reside in mother liquor and circulate in system, in system, remaining lithium is all separated out with Lithium Sulphate concentrate.
Compared with prior art, the present invention has the following advantages:
First, process for purification of the present invention does not introduce any chemical reagent, utilizes natural energy to adopt physical method completely, environment friendly and pollution-free, belongs to green clean energy technique.
Secondly, process for purification operational path of the present invention is simple, adopt " molten ore deposit---freezing---evaporation---analysing boron---convert nitre evaporation " technological line, adopt five core procedures just can complete to refine rough, operational path is short, removal step is very simple, but but reaches Lithium Sulphate height yield.According to this five step process route, a flow process terminates, and the yield of Lithium Sulphate is 35% ~ 65%.
Again, in treating process of the present invention, the first step turns back to the first step to the solution L4 obtained after a technical process of the 5th step terminates, replacement part is for dissolving the water of the rough S0 of Lithium Sulphate, enter second circulation of the rough process for purification of sulfuric acid lithium salts, according to this mode, the rough dissolved water of the first step Lithium Sulphate of working cycle is each time made up of the front L4 solution that obtains and the fresh water of once circulating, two-part ratio forms relevant with L4, can make in this way in the rough separating-purifying process of Lithium Sulphate, the Lithium Sulphate be dissolved in mother liquor L4 is utilized, the solution loss of Lithium Sulphate in second time and following cycle can be reduced simultaneously, in the solid S2 of carnallitite precipitation phase, only there is the lithium loss of exist along with the precipitation of a small amount of lithium borate salts in the lithium loss of about 25% and the solid S3 at borate precipitation phase about 1% along with the precipitation of a small amount of lithium double salt in whole process, separately have the lithium of about 10% ~ 15% to reside in mother liquor to circulate in system, in system, remaining lithium is all separated out with Lithium Sulphate concentrate, improve the yield of Lithium Sulphate concentrate.
Finally, the simple operational path of employing of the present invention, the impurity such as potassium, magnesium, boron in effectively utilizing natural energy removing Lithium Sulphate rough, obtaining principal constituent is Li
2sO
4h
2the concentrate of O and NaCl, Li in concentrate
2sO
4h
2the mass percentage of O is about 35% ~ 50%.Nearly 1 times of the more rough raising of Li content in concentrate, and Mg content is reduced to 17%, K rough content is reduced to rough 1/3, reaches very good purification effect.
Accompanying drawing explanation
Fig. 1 is the rough process for purification schema of Lithium Sulphate of the present invention.
Embodiment
For making object of the present invention, technical scheme and advantage clearly understand, below in conjunction with specific embodiment, the present invention is described in detail.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
The present invention's Lithium Sulphate used is rough be utilize the applicant before patented technology, see Chinese patent 201310124971.2, name is called " adopting the method for beneficial element in natural energy concentration and separation sulfate type shielding bittern ".Key step comprises: will look into ripple and arrange original bittern evaporation to sodium-chlor state of saturation, freeze nitre in the winter time, then in evaporation spring and summer successively precipitated sodium chloride, sylvite, carnallitite, epsom salt, control lithium concentration >=6g/L in bittern and carry out solid-liquid separation, obtain the bittern of high content of magnesium chloride; Itself and saltcake hybrid reaction are separated out sodium salt and magnesium salts, controls to carry out solid-liquid separation when Mg/Li ratio is less than or equal to 8:1 in solution, obtain boron-rich lithium bittern; When boron-rich lithium bittern evaporation is reached preset value to the content of boron or elemental lithium and water or original bittern hybrid reaction, separate out boron rock, liquid phase is rich lithium bittern, and continuing evaporation, to separate out Lithium Sulphate rough.
As shown in Figure 1, the process for purification that Lithium Sulphate of the present invention is rough comprises five steps:
The first step, is dissolved in the water rough for Lithium Sulphate S0.
Mix rough for vitriol with excessive water, the soluble ingredient in making vitriol rough dissolves just completely, obtains solution L0 and water-fast solid, the insolubless such as such as silt after solid-liquid separation.
Second step, carries out freezing precipitation saltcake by solution L0, obtains solution L1 and solid after solid-liquid separation.
Solution L0 carries out freezing treatment under the temperature condition of-30 DEG C ~ 0 DEG C, separates out saltcake, no longer continues to carry out solid-liquid separation when separating out, obtain solution L1 and solid S1 through the fully freezing solid that makes.
In this refrigerating process, the SO of 90% ~ 99% (mass percent)
4 2-frozen with the form of saltcake, reached the effect removing sulfate radical preferably.Due in sulfate type salt lake brine, a large amount of existence of sulfate ion, make the potassium in bittern separate out with the form of potassium mixed salt, are difficult to be separated with lithium.Therefore, in this step, a large amount of removals of sulfate radical make potassium become easy with being separated of lithium.
Solid S1 main component is saltcake, also comprises a small amount of lithium double salt.When the causa essendi of a small amount of lithium double salt is solid-liquid separation, in solid phase, entrainment mother liquor amount is about 10% ~ 25%.
Solid S1 also will be used for converting halogen and separate out Lithium Sulphate in back segment test, make lithium can get back to unlikely loss in system.
3rd step, carries out evaporation process by solution L1 under the temperature condition of 0 DEG C ~ 40 DEG C.
Along with the evaporation of solution L1, the Li in solution
+, Mg
2+ion and B
2o
3concentration is increase trend with density, and saturated rear beginning of liquid phase separates out new solid phase, carries out solid-liquid separation, obtain solution L2 and solid S2 after evaporating the water going to account for system total mass 40% ~ 60%.
The main component of solid S2 is NaCl and KClMgCl
26H
2o (carnallitite).Obviously, the potassium in solution L1, magnesium are separated out with the form of carnallitite, reach the separation of lithium magnesium, lithium potassium.Because sulfate brine is prepared in Lithium Sulphate salt mine process, the existence of magnesium, potassium makes to analyse salt process and becomes very complicated, thus adds the enrichment difficulty of lithium.And in this step, magnesium, potassium are removed simultaneously, the concentration of lithium ion in solution L2 is promoted greatly, and the process of follow-up precipitation Lithium Sulphate salt mine becomes comparatively easy.In addition, due to the removal of magnesium, potassium, B in solution L2
2o
3concentration also gets a promotion, and in order to finally obtain Lithium Sulphate salt mine, next step will remove B
2o
3.
4th step, solution L2 is under the temperature condition of 0 DEG C ~ 40 DEG C, and sealing placement 7 ~ 50 days, separates out borate, obtain solution L3 and solid S3 after solid-liquid separation.
Solution L2 is positioned in Glass Containers, to place about 7 ~ 50 days after preservative film sealing, occurs white flock precipitate in container, after solid-liquid separation, obtain solid S3 (white filter cake) and solution L3.Solid S3 is mainly the borate of Li and Mg.XRD analysis display solid components is Li
4b
2o
5, NaB
5o
6(OH)
4, Mg
2b
12o
205H
2o.
5th step, the solid S1 obtained by second step refrigerating process adds in solution L3, evaporates under the temperature condition of 0 DEG C ~ 40 DEG C, separates out Lithium Sulphate concentrate.
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 can be come back in system.The mixture of solid S1 and solution L3 is at room temperature evaporated, to be evaporated to moisture removal amount to calculated value time, obtain the particle of square and needle-like two kinds of crystal formations, after solid-liquid separation, obtain solid S4 and solution L4.Through XRD analysis display, solid S4 is NaCl and Li
2sO
4h
2the mixture of O, that is, Lithium Sulphate concentrate.Relative to rough, in concentrate, Li content improves about 1 times, and the yield of lithium is 35% ~ 65%, Li
2sO
4h
2o mass percentage is about 35% ~ 50%.20% ~ 0.1%, the K content that in concentrate, Mg content is reduced to Mg content in the rough S0 of Lithium Sulphate is reduced to 20% ~ 0.1% of the rough middle K content of Lithium Sulphate, reaches good lithium magnesium, lithium potassium separating effect and rough refining effect.
The rough process for purification of above-mentioned Lithium Sulphate have passed through 5 steps, and the solid composition qualification result obtained after each step solid-liquid separation is as shown in table 1.
Table 1 Lithium Sulphate rough Refining tests solid phase XRD qualification result
The Lithium Sulphate concentrate main component finally obtained is NaCl and Li of mass ratio close to 1:1
2sO
4h
2o.Flotation Li can be adopted
2sO
4, or the method for reverse flotation removal NaCl obtains the higher Lithium Sulphate of purity, and obtain Lithium Sulphate product salt in conjunction with recrystallization; Also after can being dissolved, again adopt " " molten ore deposit---freezing---evaporation---analysing boron---convert nitre evaporation " route purify further.
In Lithium Sulphate delicate procedure of the present invention, comprise the operational path of five steps, after a flow process terminates, the yield of Lithium Sulphate is 35% ~ 65%, all the other most of lithiums along with the solution L4 obtained after the 5th step solid-liquid separation again for the next one circulation the rough dissolution process of Lithium Sulphate and be again utilized.Specifically, in treating process of the present invention, the first step turns back to the first step to the solution L4 obtained after a technical process of the 5th step terminates, replacement part is for dissolving the water of the rough S0 of Lithium Sulphate, enter second circulation of the rough process for purification of sulfuric acid lithium salts, according to this mode, the rough dissolved water of the first step Lithium Sulphate of working cycle is each time made up of the front L4 solution that obtains and the fresh water of once circulating, two-part ratio forms relevant with L4, can make in this way in the rough separating-purifying process of Lithium Sulphate, the Lithium Sulphate be dissolved in mother liquor L4 is utilized, the solution loss of Lithium Sulphate in second time and following cycle can be reduced simultaneously, in the solid S2 of carnallitite precipitation phase, only there is the lithium loss of exist along with the precipitation of a small amount of lithium borate salts in the lithium loss of about 15 ~ 25% and the solid S3 at borate precipitation phase about 1% along with the precipitation of a small amount of lithium double salt in whole process, separately have the lithium of about 10% ~ 15% to reside in mother liquor to circulate in system, remaining lithium is all separated out with the form of Lithium Sulphate concentrate, the yield of Lithium Sulphate concentrate arrives lifting thereupon greatly.
Compared with prior art, the present invention has the following advantages:
First, process for purification of the present invention does not introduce any chemical reagent, utilizes natural energy to adopt physical method completely, environment friendly and pollution-free, belongs to green clean energy technique.
Secondly, process for purification operational path of the present invention is simple, adopt " molten ore deposit---freezing---evaporation---analysing boron---convert nitre evaporation " technological line, adopt five core procedures just can complete to refine rough, operational path is short, removal step is very simple, but but reaches Lithium Sulphate height yield.According to this five step process route, a flow process terminates, and the yield of Lithium Sulphate is 35% ~ 65%.
Again, in treating process of the present invention, the first step turns back to the first step to the solution L4 obtained after a technical process of the 5th step terminates, replacement part is for dissolving the water of the rough S0 of Lithium Sulphate, enter second circulation of the rough process for purification of sulfuric acid lithium salts, according to this mode, the rough dissolved water of the first step Lithium Sulphate of working cycle is each time made up of the front L4 solution that obtains and the fresh water of once circulating, two-part ratio forms relevant with L4, can make in this way in the rough separating-purifying process of Lithium Sulphate, the Lithium Sulphate be dissolved in mother liquor L4 is utilized, the solution loss of Lithium Sulphate in second time and following cycle can be reduced simultaneously, in the solid S2 of carnallitite precipitation phase, only there is the lithium loss of exist along with the precipitation of a small amount of lithium borate salts in the lithium loss of about 15% ~ 25% and the solid S3 at borate precipitation phase about 1% along with the precipitation of a small amount of lithium double salt in whole process, separately have the lithium of about 10% ~ 15% to reside in mother liquor to circulate in system, in system, remaining lithium is all separated out with the form of Lithium Sulphate concentrate, increase substantially the yield of Lithium Sulphate concentrate.
Finally, the simple operational path of employing of the present invention, the impurity such as potassium, magnesium, boron in effectively utilizing natural energy removing Lithium Sulphate rough, obtaining principal constituent is Li
2sO
4h
2the concentrate of O and NaCl, Li in concentrate
2sO
4h
2the mass percentage of O is about 35% ~ 50%.Nearly 1 times of the more rough raising of Li content in concentrate, and 20% ~ 0.1%, the K content that Mg content is reduced to Mg content in the rough S0 of Lithium Sulphate is reduced to 20% ~ 0.1% of the rough middle K content of Lithium Sulphate, reaches very good purification effect.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. the process for purification that sulfuric acid lithium salts is rough, it comprises step:
The first step, mixed with excessive water by rough for sulfuric acid lithium salts S0, the soluble ingredient in making Lithium Sulphate rough dissolves just completely, obtains solution L0 and water-fast solid after solid-liquid separation;
Second step, carries out freezing under the temperature condition of-30 DEG C ~ 0 DEG C by solution L0, separate out saltcake, obtain solution L1 and solid S1 after solid-liquid separation, the major ingredient of solid S1 is saltcake;
3rd step, evaporates solution L1 under the temperature condition of 0 DEG C ~ 40 DEG C, and separate out solid phase, obtain solution L2 and solid S2 after solid-liquid separation, the major ingredient of solid S2 is NaCl and KClMgCl
26H
2o;
4th step, placed 7 ~ 50 days at the temperature condition lower seal of 0 DEG C ~ 40 DEG C by solution L2, separate out borate, obtain solution L3 and solid S3 after solid-liquid separation, solid S3 major ingredient is the borate of Li and Mg;
5th step, the solid S1 obtained by second step refrigerating process mixes with solution L3, evaporates under the temperature condition of 0 DEG C ~ 40 DEG C, separates out Lithium Sulphate concentrate, obtains Lithium Sulphate concentrate and solution L4 after solid-liquid separation.
2. the method for claim 1, is characterized in that: the Lithium Sulphate concentrate major ingredient that described 5th step obtains is NaCl and Li of mass ratio close to 1:1
2sO
4h
2the mixture of O.
3. the method for claim 1, is characterized in that: relative to the rough S0 of the Lithium Sulphate in the first step, and in the Lithium Sulphate concentrate that described 5th step obtains, Li content improves more than 1 times.
4. method as claimed in claim 3, it is characterized in that: relative to the rough S0 of the Lithium Sulphate in the first step, 20% ~ 0.1%, the K content that in the Lithium Sulphate concentrate that described 5th step obtains, Mg content is reduced to Mg content in the rough S0 of Lithium Sulphate is reduced to 20% ~ 0.1% of K content in the rough S0 of Lithium Sulphate.
5. the method for claim 1, is characterized in that: Li in the Lithium Sulphate concentrate that described 5th step obtains
2sO
4h
2o mass percentage is about 35% ~ 50%.
6. the method for claim 1, is characterized in that: in described second step, carries out freezing under the temperature condition of-30 DEG C ~ 0 DEG C, and in the solution L1 obtained, the content of sulfate ion reduces more than 90% relative to solution L0.
7. the method for claim 1, is characterized in that: evaporate under the temperature condition of 0 DEG C ~ 40 DEG C in described 3rd step, carries out solid-liquid separation after evaporating the water going to account for system total mass 40% ~ 60%.
8. the method for claim 1, is characterized in that: after the described the first step a to technical process of the 5th step terminates, the yield of Lithium Sulphate is 35% ~ 65%.
9. method as claimed in claim 8, it is characterized in that: the described the first step returns the first step to the solution L4 obtained after a technical process of the 5th step terminates, replacement part carries out next step circulation for the water dissolving the rough S0 of Lithium Sulphate, through fully circulating, obtains Lithium Sulphate concentrate.
10. method as claimed in claim 9, it is characterized in that: in described abundant working cycle, in the solid S2 of carnallitite precipitation phase, the lithium loss of exist along with the precipitation of a small amount of lithium borate salts in the lithium loss of 15% ~ 25% and the solid S3 at borate precipitation phase about 1% is only there is along with the precipitation of a small amount of lithium double salt, separately have the lithium of about 10% ~ 15% to reside in mother liquor to circulate in system, in system, remaining lithium is all separated out with Lithium Sulphate concentrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510881141.3A CN105502440B (en) | 2015-12-04 | 2015-12-04 | The rough refining methd of sulfuric acid lithium salts |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510881141.3A CN105502440B (en) | 2015-12-04 | 2015-12-04 | The rough refining methd of sulfuric acid lithium salts |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105502440A true CN105502440A (en) | 2016-04-20 |
| CN105502440B CN105502440B (en) | 2019-03-26 |
Family
ID=55710826
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510881141.3A Active CN105502440B (en) | 2015-12-04 | 2015-12-04 | The rough refining methd of sulfuric acid lithium salts |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105502440B (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107739042A (en) * | 2017-11-22 | 2018-02-27 | 中国科学院青海盐湖研究所 | The method that high-purity magnesium sulfate is prepared by magnesium sulfate discarded object |
| CN108383140A (en) * | 2018-05-09 | 2018-08-10 | 天津二八科技股份有限公司 | A kind of clearer production technology and method of lithium sulfate |
| CN108439436A (en) * | 2018-04-10 | 2018-08-24 | 中蓝长化工程科技有限公司 | A kind of preparation process of sulfuric acid monohydrate lithium |
| CN108640130A (en) * | 2018-06-26 | 2018-10-12 | 中国科学院青海盐湖研究所 | By the rough method for preparing lithium sulfate of salt lake sulfuric acid lithium salts |
| CN109824067A (en) * | 2018-12-22 | 2019-05-31 | 魏万仁 | Natural evaporation crystallization analysis lithium, joint heating crystallization analysis lithium+dissolution wash lithium and extract lithium concentrate |
| CN112456520A (en) * | 2020-12-23 | 2021-03-09 | 广西天源新能源材料有限公司 | Process for producing lithium hydroxide monohydrate by mixing spodumene, lithium polymer and salt lake ore |
| CN112479234A (en) * | 2020-12-23 | 2021-03-12 | 中南大学 | Process for producing lithium hydroxide monohydrate from salt lake ore |
| CN112551555A (en) * | 2020-12-30 | 2021-03-26 | 广西天源新能源材料有限公司 | Preparation method of anhydrous sodium sulphate based on salt lake ore and lithium polymer |
| CN112591772A (en) * | 2020-12-23 | 2021-04-02 | 广西天源新能源材料有限公司 | Process for producing lithium hydroxide monohydrate by mixing spodumene and salt lake ores |
| CN112607754A (en) * | 2020-12-23 | 2021-04-06 | 中南大学 | Environment-friendly process for producing lithium hydroxide monohydrate by mixing spodumene and salt lake ores |
| CN112661175A (en) * | 2021-01-21 | 2021-04-16 | 广西天源新能源材料有限公司 | Lithium carbonate preparation method based on combination of salt lake ore, lithium polymer and spodumene |
| CN112661176A (en) * | 2021-01-21 | 2021-04-16 | 广西天源新能源材料有限公司 | Environment-friendly process for producing lithium carbonate by mixing spodumene and salt lake ores |
| CN114405060A (en) * | 2022-02-09 | 2022-04-29 | 中国科学院过程工程研究所 | Method for synchronously separating lithium, boron and magnesium in salt lake brine through three-liquid-phase extraction |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1249272A (en) * | 1998-09-25 | 2000-04-05 | 青海省柴达木综合地质勘查大队 | Process for precipitating B and Li in bittern at same time |
| CN102910652A (en) * | 2012-10-18 | 2013-02-06 | 中国科学院青海盐湖研究所 | Clean production process of plateau sulfate type boron-lithium salt lake brine |
| CN103898341A (en) * | 2014-03-06 | 2014-07-02 | 中国科学院青海盐湖研究所 | Method for separating and extracting lithium from lithium sulfate coarse ore |
| JP2014189892A (en) * | 2013-03-28 | 2014-10-06 | Sumitomo Metal Mining Co Ltd | Separation method of double sulfate, precipitation method of double sulfate, and recovery method of valuable metal from used battery |
-
2015
- 2015-12-04 CN CN201510881141.3A patent/CN105502440B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1249272A (en) * | 1998-09-25 | 2000-04-05 | 青海省柴达木综合地质勘查大队 | Process for precipitating B and Li in bittern at same time |
| CN102910652A (en) * | 2012-10-18 | 2013-02-06 | 中国科学院青海盐湖研究所 | Clean production process of plateau sulfate type boron-lithium salt lake brine |
| CN103224244A (en) * | 2012-10-18 | 2013-07-31 | 中国科学院青海盐湖研究所 | Method for enriching and separating beneficial elements in sulfate type salt lake brine by using nature energy |
| JP2014189892A (en) * | 2013-03-28 | 2014-10-06 | Sumitomo Metal Mining Co Ltd | Separation method of double sulfate, precipitation method of double sulfate, and recovery method of valuable metal from used battery |
| CN103898341A (en) * | 2014-03-06 | 2014-07-02 | 中国科学院青海盐湖研究所 | Method for separating and extracting lithium from lithium sulfate coarse ore |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN107739042B (en) * | 2017-11-22 | 2019-09-17 | 中国科学院青海盐湖研究所 | The method that high-purity magnesium sulfate is prepared by magnesium sulfate waste |
| CN107739042A (en) * | 2017-11-22 | 2018-02-27 | 中国科学院青海盐湖研究所 | The method that high-purity magnesium sulfate is prepared by magnesium sulfate discarded object |
| CN108439436A (en) * | 2018-04-10 | 2018-08-24 | 中蓝长化工程科技有限公司 | A kind of preparation process of sulfuric acid monohydrate lithium |
| CN108383140A (en) * | 2018-05-09 | 2018-08-10 | 天津二八科技股份有限公司 | A kind of clearer production technology and method of lithium sulfate |
| CN108640130B (en) * | 2018-06-26 | 2020-07-24 | 中国科学院青海盐湖研究所 | Method for preparing lithium sulfate from salt lake lithium sulfate salt crude ore |
| CN108640130A (en) * | 2018-06-26 | 2018-10-12 | 中国科学院青海盐湖研究所 | By the rough method for preparing lithium sulfate of salt lake sulfuric acid lithium salts |
| CN109824067A (en) * | 2018-12-22 | 2019-05-31 | 魏万仁 | Natural evaporation crystallization analysis lithium, joint heating crystallization analysis lithium+dissolution wash lithium and extract lithium concentrate |
| CN112456520A (en) * | 2020-12-23 | 2021-03-09 | 广西天源新能源材料有限公司 | Process for producing lithium hydroxide monohydrate by mixing spodumene, lithium polymer and salt lake ore |
| CN112479234A (en) * | 2020-12-23 | 2021-03-12 | 中南大学 | Process for producing lithium hydroxide monohydrate from salt lake ore |
| CN112591772A (en) * | 2020-12-23 | 2021-04-02 | 广西天源新能源材料有限公司 | Process for producing lithium hydroxide monohydrate by mixing spodumene and salt lake ores |
| CN112607754A (en) * | 2020-12-23 | 2021-04-06 | 中南大学 | Environment-friendly process for producing lithium hydroxide monohydrate by mixing spodumene and salt lake ores |
| CN112551555A (en) * | 2020-12-30 | 2021-03-26 | 广西天源新能源材料有限公司 | Preparation method of anhydrous sodium sulphate based on salt lake ore and lithium polymer |
| CN112661175A (en) * | 2021-01-21 | 2021-04-16 | 广西天源新能源材料有限公司 | Lithium carbonate preparation method based on combination of salt lake ore, lithium polymer and spodumene |
| CN112661176A (en) * | 2021-01-21 | 2021-04-16 | 广西天源新能源材料有限公司 | Environment-friendly process for producing lithium carbonate by mixing spodumene and salt lake ores |
| CN114405060A (en) * | 2022-02-09 | 2022-04-29 | 中国科学院过程工程研究所 | Method for synchronously separating lithium, boron and magnesium in salt lake brine through three-liquid-phase extraction |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105502440B (en) | 2019-03-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105502440A (en) | Method for purifying lithium sulfate crude ore | |
| CN103194622B (en) | Method for enriching boron and lithium elements in sulfate type salt lake brine | |
| CN102963914B (en) | Method for preparing high-purity lithium carbonate from salt lake brine | |
| WO2013053165A1 (en) | Method for production of lithium carbonate by applying multi-bittern-adding method, and using carbonate type bittern and sulfate type bittern as raw material | |
| CN103058232A (en) | Method for separating carbonate from carbonate bittern containing lithium and potassium to prepare sylvinite ore and lithium carbonate concentrate | |
| CN108439436B (en) | Preparation process of lithium sulfate monohydrate | |
| CN108640130B (en) | Method for preparing lithium sulfate from salt lake lithium sulfate salt crude ore | |
| CN114906864A (en) | Method for extracting lithium from high-calcium chloride type salt lake brine | |
| CN103553090B (en) | Method for extracting Mg, K, B and Li from mixed brine by utilizing natural energy | |
| CN1270927A (en) | Lithium salt extraction process from carbonate type bittern | |
| CN111362731B (en) | Potassium magnesium sulfate fertilizer, potassium chloride and preparation method of potassium sulfate | |
| CN103553088B (en) | Method of preparing lithium borate ores from mixed brine by utilizing natural energy | |
| CN103539142A (en) | Method for combined extraction of potassium-magnesium fertilizer, boric acid and lithium carbonate from sodium sulfate subtype salt lake | |
| CN103553087B (en) | Method of preparing lithium sulfate ores from mixed brine by utilizing natural energy | |
| CN115159546A (en) | Method for improving evaporation efficiency of salt lake brine | |
| CN103553065B (en) | Method for preparing boron ore from mixed brine by using natural energy | |
| CN103553091B (en) | Method for extracting Mg, K, B and Li from mixed brine by utilizing natural energy | |
| CN103750265B (en) | Solar energy greenhouse Exposure to Sunlight natural seaweed iodine sodium salt production method | |
| CN1482063A (en) | Process for preparing potassium sulfate | |
| CN103539161B (en) | Method for preparing sylvite ore from mixed brine by use of natural energy | |
| CN105858693B (en) | The method that high-purity magnesium carbonate is prepared from the carbonate type bittern of plateau | |
| CN103588227B (en) | The production technique of nitre evaporation de-magging converted by the old halogen in a kind of salt lake | |
| CN103553092B (en) | Method for preparing carnallite ore from mixed brine by using natural energy | |
| CN108069444A (en) | A kind of method of comprehensive utilization of sulfate type bittern | |
| CN115786734A (en) | Method for recovering lithium from brine concentrated crystal salt |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |