CN116409804B - Method for extracting lithium salt from low-grade lithium ore raw material - Google Patents
Method for extracting lithium salt from low-grade lithium ore raw material Download PDFInfo
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- CN116409804B CN116409804B CN202310156447.7A CN202310156447A CN116409804B CN 116409804 B CN116409804 B CN 116409804B CN 202310156447 A CN202310156447 A CN 202310156447A CN 116409804 B CN116409804 B CN 116409804B
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 86
- 239000002994 raw material Substances 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 43
- 229910003002 lithium salt Inorganic materials 0.000 title claims abstract description 35
- 159000000002 lithium salts Chemical class 0.000 title claims abstract description 35
- 239000007864 aqueous solution Substances 0.000 claims abstract description 70
- 238000002386 leaching Methods 0.000 claims abstract description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 51
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000000227 grinding Methods 0.000 claims abstract description 45
- 238000005406 washing Methods 0.000 claims abstract description 45
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 39
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 37
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 37
- 239000000843 powder Substances 0.000 claims abstract description 37
- 238000001914 filtration Methods 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 239000012535 impurity Substances 0.000 claims abstract description 20
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims abstract description 20
- 238000004321 preservation Methods 0.000 claims abstract description 20
- 238000001816 cooling Methods 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 159000000007 calcium salts Chemical class 0.000 claims abstract description 14
- 230000001376 precipitating effect Effects 0.000 claims abstract description 7
- 238000003825 pressing Methods 0.000 claims abstract description 6
- 229920002401 polyacrylamide Polymers 0.000 claims description 38
- 239000000243 solution Substances 0.000 claims description 35
- 239000008367 deionised water Substances 0.000 claims description 34
- 229910021641 deionized water Inorganic materials 0.000 claims description 34
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 31
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 31
- 235000011152 sodium sulphate Nutrition 0.000 claims description 31
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 28
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 28
- 235000011151 potassium sulphates Nutrition 0.000 claims description 28
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 26
- 239000012778 molding material Substances 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical class [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 19
- 239000003513 alkali Substances 0.000 claims description 14
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 11
- 239000000706 filtrate Substances 0.000 claims description 10
- 238000001704 evaporation Methods 0.000 claims description 9
- 229910052629 lepidolite Inorganic materials 0.000 claims description 9
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 7
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 7
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 5
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 5
- HEHRHMRHPUNLIR-UHFFFAOYSA-N aluminum;hydroxy-[hydroxy(oxo)silyl]oxy-oxosilane;lithium Chemical compound [Li].[Al].O[Si](=O)O[Si](O)=O.O[Si](=O)O[Si](O)=O HEHRHMRHPUNLIR-UHFFFAOYSA-N 0.000 claims description 3
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052670 petalite Inorganic materials 0.000 claims description 3
- 229910052642 spodumene Inorganic materials 0.000 claims description 3
- 235000011132 calcium sulphate Nutrition 0.000 claims description 2
- 229910052573 porcelain Inorganic materials 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- 238000000748 compression moulding Methods 0.000 abstract description 3
- 238000000605 extraction Methods 0.000 abstract description 3
- 238000010923 batch production Methods 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 238000009740 moulding (composite fabrication) Methods 0.000 abstract 2
- -1 for example Chemical compound 0.000 description 12
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 10
- 229910001424 calcium ion Inorganic materials 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 238000005245 sintering Methods 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 4
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 229910001448 ferrous ion Inorganic materials 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 229910001425 magnesium ion Inorganic materials 0.000 description 4
- 229910001437 manganese ion Inorganic materials 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical group [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 229960004887 ferric hydroxide Drugs 0.000 description 3
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 239000003082 abrasive agent Substances 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical group 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
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
- C01D15/08—Carbonates; Bicarbonates
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The application relates to the technical field of lithium carbonate extraction from lithium ore raw materials, and particularly discloses a method for extracting lithium salt from low-grade lithium ore raw materials, which comprises the following steps: crushing to obtain powder; mixing and forming: adding sulfate, calcium salt and polyvinyl butyral into the powder, mixing, adding absolute ethyl alcohol, mixing, pressing, forming, heating to 80-90 ℃, carrying out heat preservation, cooling to (-10) - (-5) DEG C, and carrying out heat preservation to obtain a formed material; roasting and grinding to obtain an abrasive; acidifying and leaching to obtain a mixture; filtering and washing to obtain leaching liquid; removing impurities and precipitating lithium to obtain lithium carbonate. According to the method for extracting lithium salt, polyvinyl butyral and absolute ethyl alcohol are added into powder, compression molding is carried out, roasting and grinding are carried out, the 200-mesh screen allowance of the grinding material is less than 2%, and the lithium leaching rate is more than 92% by combining the synergistic effect of sulfuric acid aqueous solution and water, so that the yield of lithium carbonate is increased, and the industrial batch production and the application are facilitated.
Description
Technical Field
The application relates to the technical field of lithium carbonate extraction from lithium ore raw materials, in particular to a method for extracting lithium salt from low-grade lithium ore raw materials.
Background
The lithium salt is a salt containing a lithium element, for example, lithium carbonate, lithium hydroxide, lithium phosphate, lithium chloride, or the like, and can be applied to glass, alloys, medicines, lithium batteries, or the like. With the continuous development of national science and technology, lithium battery new energy is widely concerned and researched, and the demand of lithium carbonate as an important raw material of the lithium battery new energy is continuously increased.
Currently, lithium carbonate is mainly extracted from liquid ore or solid ore. The liquid ore mainly comprises salt lake brine, and the solid ore mainly comprises lepidolite, hectorite, spodumene, tantalite, petalite and the like. The traditional method for extracting lithium salt from solid ore mainly comprises a limestone sintering method, a chloridizing roasting method, a sulfuric acid method and a sulfate method. In the sulfate process, solid ore is generally crushed to obtain powder. And then mixing the powder with sulfate, and roasting at high temperature to enable the solid ore to react with the sulfate to obtain a roasting material. And grinding the roasting material to obtain the grinding material. And adding water into the grinding material to leach out the lithium, and further removing impurities and precipitating the lithium, thereby obtaining the lithium carbonate. In actual processing, the applicant finds that the powder and sulfate are easy to sinter after being roasted at high temperature, so that not only the roasting effect is affected, but also the roasted material is not easy to grind, the 200-mesh screen allowance of the grinding material is more than 10%, and the leaching of lithium in the grinding material is affected.
Disclosure of Invention
In order to reduce the sintering condition of powder and sulfate at high temperature, increase the roasting effect and facilitate grinding, the application provides a method for extracting lithium salt from low-grade lithium ore raw materials, which adopts the following technical scheme:
a method for extracting lithium salts from low-grade lithium ore raw materials, comprising the steps of:
s1, crushing: crushing a lithium ore raw material to obtain powder;
s2, mixing and forming: adding sulfate, calcium salt and polyvinyl butyral into the powder, mixing, adding absolute ethyl alcohol, mixing, pressing, heating to 80-90 ℃, carrying out heat preservation for 1-2h, cooling to (-10) - (-5) DEG C, and carrying out heat preservation for 3-5h to obtain a molding material;
s3, roasting and grinding: heating the molding material to 240-260 ℃, carrying out heat preservation treatment for 1-2h, heating to 940-960 ℃, carrying out roasting treatment for 2-4h, cooling, and grinding to obtain an abrasive;
s4, acidizing and leaching: adding sulfuric acid aqueous solution into the grinding material, heating to 110-130 ℃, stirring for 1-3h, then adding deionized water, heating to 60-70 ℃, and stirring for 1-3h to obtain a mixture;
s5, filtering and washing: filtering the mixture to obtain filtrate and filter residue, washing the filter residue to obtain a washing liquid, and mixing the washing liquid and the filtrate to obtain a leaching solution;
s6, removing impurities and precipitating lithium: removing impurities from the leaching solution, heating to 90-100 ℃, adding saturated carbonate aqueous solution, filtering, washing and drying to obtain lithium carbonate.
In the lithium salt extraction method, powder, sulfate, calcium salt and polyvinyl butyral are mixed and matched with absolute ethyl alcohol to be pressed and molded to obtain a molding material, the molding material is synchronous and is subjected to heat preservation treatment at the temperature of 80-90 ℃, at this time, the absolute ethyl alcohol is cooperated with water to volatilize, pore channels can be formed in the molding material, heat transfer is facilitated, and then the molding material is cooled, water is solidified, sublimated further and the water in the molding material is reduced effectively. Further, the temperature of the molding material is raised to 240-260 ℃, at this time, the polyvinyl butyral is decomposed, pore channels in the molding material are increased, heat transfer is facilitated, roasting effect is increased, sintering is reduced, grinding is facilitated, and 200-mesh screen residue of the grinding material obtained after grinding is less than 2%.
Meanwhile, in the method for extracting lithium salt, sulfuric acid aqueous solution is added into the grinding material, then water is added, the lithium is leached by utilizing the cooperation of the sulfuric acid aqueous solution and the water, the lithium leaching rate is more than 92%, the lithium leaching rate is improved, the yield of lithium carbonate is further improved, and the method is convenient for industrial batch production and application.
Further, in the compression molding, the pressure is 0.12-0.14MPa, and the compression time is 5-15s. In one embodiment, the pressure is 0.13MPa and the pressing time is 10s. The pressure may be adjusted to 0.12MPa and the pressing time may be adjusted to 5s, or the pressure may be adjusted to 0.14MPa and the pressing time may be adjusted to 15s, as required.
Optionally, the lithium oxide content in the lithium ore raw material is 0.5-1.5%; the raw material of the lithium ore is one or more of lepidolite, lithium porcelain stone, spodumene, tantalite and petalite.
By adopting the technical scheme, the lithium ore raw materials are optimized, and the selection of the lithium ore raw materials is facilitated.
Optionally, in the step S2, the weight ratio of the powder, the sulfate, the calcium salt, the polyvinyl butyral and the absolute ethyl alcohol is 20 (9-11) (1.5-2.5) (0.5-0.7) (0.9-1.1).
By adopting the technical scheme, the consumption of sulfate, calcium salt, polyvinyl butyral and absolute ethyl alcohol is optimized, the reaction of lithium ore raw materials and sulfate is facilitated, the grinding after high-temperature roasting is also facilitated, namely, the mixing forming and the roasting grinding control are facilitated.
Optionally, the sulfate is one or more of potassium sulfate, sodium sulfate and calcium sulfate.
The potassium sulfate, the sodium sulfate and the calcium sulfate can react with the lithium ore raw materials, thereby facilitating the leaching of lithium.
Optionally, the sulfate is potassium sulfate and sodium sulfate, and the weight ratio of the potassium sulfate to the sodium sulfate is 1 (1-3).
The cost of the potassium sulfate is higher than that of the sodium sulfate, if the sulfate is all potassium sulfate, the cost is increased, if the sulfate is all sodium sulfate, the cost is reduced, however, the melting point of the sodium sulfate is lower than that of the potassium sulfate, and the sodium sulfate and the lithium ore raw materials are easy to separate out in the high-temperature roasting reaction, so that the condition of sintering of the molding materials occurs, and the subsequent grinding is unfavorable.
In the application, the sulfate adopts two types of potassium sulfate and sodium sulfate, and a small amount of potassium sulfate is added into the sodium sulfate, so that the use amount of the sodium sulfate is reduced, the condition that the molding material is sintered at high temperature is also reduced, and the subsequent grinding is facilitated. Meanwhile, the polyvinyl butyral and the absolute ethyl alcohol are matched, so that the mixture is molded, the high-temperature sintering condition of the molding material is reduced, and the leaching of lithium in the follow-up grinding material is facilitated.
Optionally, in the step S1, the 100-mesh screening allowance of the powder is less than or equal to 1%; in the step S3, the 200-mesh screen residue of the grinding material is less than or equal to 2 percent.
By adopting the technical scheme, the granularity of the powder is optimized, and the mixing and reaction of the powder and sulfate are affected due to overlarge granularity of the powder. The granularity of the grinding material is also optimized, so that the leaching of lithium is facilitated.
Optionally, in the step S4, the weight ratio of the powder, the sulfuric acid aqueous solution and the deionized water is 20 (25-35) (30-50), and the mass concentration of sulfuric acid in the sulfuric acid aqueous solution is 60-70%;
in the step S6, the weight ratio of the powder and the saturated carbonate aqueous solution is 20 (4-5), and the temperature of the saturated carbonate aqueous solution is 20-30 ℃.
By adopting the technical scheme, the usage amount of the sulfuric acid aqueous solution and the deionized water is optimized, so that the leaching of lithium in the abrasive is facilitated, and the leaching rate of lithium is increased. The use amount of the saturated carbonate aqueous solution is optimized, so that lithium ions are fully precipitated to form lithium carbonate, and the yield of the lithium carbonate is improved.
In step S5, deionized water is used for washing, the washing times are 2-5 times, and the total amount of the deionized water used for each washing is 1.5-2.5 times of the total amount of the powder.
Optionally, in step S6, the following method is used for removing impurities: adding alkali into the leaching solution under continuous stirring to adjust the pH value to 7-8, filtering, adding polyacrylamide aqueous solution for mixing, adding alkali to adjust the pH value to 13-14, filtering, evaporating for concentration, adding disodium ethylenediamine tetraacetate aqueous solution for mixing, cooling, filtering, and removing impurities.
The leaching solution contains aluminum ions, iron ions, calcium ions, ferrous ions, magnesium ions and manganese ions besides lithium ions. At this time, the pH value is regulated to 7-8 by alkali, at this time, aluminum ions and iron ions can combine with hydroxide ions to form aluminum hydroxide and ferric hydroxide precipitates, and the aluminum hydroxide and the ferric hydroxide also have flocculation effect, so that the precipitates are formed and removed conveniently. And continuously adjusting the pH value to 13-14 by using alkali, wherein at the moment, calcium ions, ferrous ions, magnesium ions and manganese ions can be combined with hydroxide ions to form calcium hydroxide, ferrous hydroxide, magnesium hydroxide and manganese hydroxide precipitates, and at the same time, the ferrous hydroxide is further oxidized into ferric hydroxide. Because the polyacrylamide aqueous solution is synchronously added, the polyacrylamide enhances the polymerization and flocculation of the precipitate, and the compactness of the precipitate is also increased, so that the precipitation rate is accelerated, and the impurity removal of the leaching solution is facilitated. Further, because calcium hydroxide is slightly soluble in water, a small amount of calcium ions are inevitably contained, and at the moment, disodium ethylenediamine tetraacetate is added, so that the disodium ethylenediamine tetraacetate can chelate the calcium ions, and the influence of the calcium ions on the quality of lithium carbonate is reduced. Meanwhile, the contents of potassium sulfate and sodium sulfate are effectively increased after evaporation and concentration, the solubility of the potassium sulfate and the sodium sulfate in water is reduced along with the reduction of the temperature, and the temperature reduction treatment is carried out to separate out the potassium sulfate and the sodium sulfate for recycling.
In the impurity removal treatment, the pH value is adjusted twice by alkali, and the polyacrylamide and the disodium ethylenediamine tetraacetate are matched for use, so that the method has the advantages of simplicity and convenience in operation and convenience in control, and can effectively remove aluminum ions, iron ions, calcium ions, ferrous ions, magnesium ions, manganese ions and the like in the leaching solution, increase the purity of lithium carbonate, improve the quality of lithium carbonate and ensure that the purity of lithium carbonate is more than 99 percent.
Optionally, in step S6, the alkali is a saturated sodium hydroxide aqueous solution, and the temperature of the saturated sodium hydroxide aqueous solution is 20-30 ℃;
the usage amount of the polyacrylamide aqueous solution is 0.05-0.1wt% of the total amount of the leaching solution, and the mass concentration of the polyacrylamide in the polyacrylamide aqueous solution is 0.05-0.1%;
the use amount of the disodium edetate aqueous solution is 0.01-0.05wt% of the total amount of the leaching solution, and the mass concentration of the disodium edetate in the disodium edetate aqueous solution is 0.01-0.05%.
By adopting the technical scheme, the usage amount of alkali, polyacrylamide and disodium ethylenediamine tetraacetate is optimized, and the impurity removal operation is convenient to control.
Further, in step S6, the mixture is concentrated to 1/30-1/10 of the original volume by evaporation. In one embodiment, the evaporation concentration is 1/20 of the original volume, and the multiple can be adjusted to one of 1/30 and 1/10 according to the requirement.
Optionally, in step S6, deionized water with the temperature of 90-100 ℃ is used for washing, the washing times are 2-5 times, and the total amount of the deionized water used for each washing is 0.5-1.5 times of the total amount of the powder.
The solubility of lithium carbonate in water is reduced along with the temperature rise, deionized water with the temperature of 90-100 ℃ is adopted for washing, the loss of lithium carbonate caused by washing is reduced, and the yield of lithium carbonate is increased.
In summary, the application has at least the following advantages:
1. according to the method for extracting lithium salt from the low-grade lithium ore raw material, sulfate is added into powder, polyvinyl butyral is synchronously added, absolute ethyl alcohol is matched for compression molding, a molding material is obtained, the temperature of the molding material is raised, the absolute ethyl alcohol is cooperated with water to volatilize, the temperature is lowered, the water is sublimated directly from solid, the water in the molding material is lowered, meanwhile, pore channels are increased, the temperature is raised further, the polyvinyl butyral is decomposed, the pore channel quantity is increased, the heat transfer is facilitated, the roasting effect is increased, the sintering condition is reduced, the grinding is facilitated, and the 200-mesh screen residue of the grinding material is less than 2%. And the grinding material lithium is leached by combining the synergistic effect of the sulfuric acid aqueous solution and water, so that the lithium leaching rate is more than 92%, the lithium leaching rate is improved, the yield of lithium carbonate is further increased, and the industrial mass production and the application are facilitated.
2. In the impurity removal treatment of the leaching solution, the pH value is adjusted by twice alkali, and the polyacrylamide and the disodium ethylenediamine tetraacetate are matched for use, so that aluminum ions, iron ions, calcium ions, ferrous ions, magnesium ions, manganese ions and the like in the leaching solution are effectively removed, the impurity removal effect is improved, the influence of the calcium ions on the quality of lithium carbonate is reduced, the purity of the lithium carbonate is more than 99%, and the market demand is met.
Detailed Description
In order that the application may be more readily understood, the application will be further described in detail with reference to the following examples, which are given by way of illustration only and are not limiting in scope of application. The starting materials or components used in the present application may be prepared by commercial or conventional methods unless specifically indicated.
Examples
Example 1
A method for extracting lithium salts from low-grade lithium ore raw materials, comprising the steps of:
s1, crushing: crushing the lithium ore raw material to obtain powder, wherein the 100-mesh sieve residue of the powder is 0.5%.
Wherein the raw material of the lithium ore is lepidolite, and the content of lithium oxide in the lepidolite is 0.83wt%.
S2, mixing and forming: 100g of sulfate, 20g of calcium salt and 6g of polyvinyl butyral are added into 200g of powder, stirred for 30min, then 10g of absolute ethyl alcohol is added, and stirred for 1h. Then, the mixture was subjected to a press treatment under a pressure of 0.13MPa for 10s. Then heating to 85 ℃, carrying out heat preservation treatment for 1.5h, cooling to-8 ℃, and carrying out heat preservation treatment for 4h to obtain the molding material.
Wherein, the sulfate is potassium sulfate and sodium sulfate, and the weight ratio of the potassium sulfate to the sodium sulfate is 1:1; the calcium salt is calcium oxide; the polyvinyl butyral is selected from Lifan chemical Co., ltd.
S3, roasting and grinding: heating the molding material to 250 ℃, and carrying out heat preservation treatment for 1.5h. Then heating to 950 ℃, and roasting for 3 hours. Then cooling to 25 ℃, and grinding for 4 hours to obtain the grinding material.
S4, acidizing and leaching: to the millbase, 300g of an aqueous sulfuric acid solution were added, the temperature was raised to 120℃and the mixture was stirred for 2 hours. Then 400g of deionized water is added, the temperature is raised to 65 ℃, and the mixture is obtained after stirring treatment for 2 hours.
Wherein the mass concentration of sulfuric acid in the sulfuric acid aqueous solution is 65%.
S5, filtering and washing: and filtering the mixture to obtain filtrate and filter residue. And then washing the filter residue for 3 times by adopting deionized water, wherein the deionized water used for each washing is 400g, so as to obtain a washing liquid, and then mixing the washing liquid and the filtrate to obtain the leaching liquid.
S6, removing impurities and precipitating lithium: at the rotating speed of 500r/min, saturated sodium hydroxide aqueous solution with the temperature of 25 ℃ is added into the leaching solution to adjust the pH value to 8, and the leaching solution is filtered. Then adding the polyacrylamide aqueous solution, and stirring for 30min. Saturated aqueous sodium hydroxide solution at 25℃was added to adjust the pH to 13, and the mixture was filtered. Then evaporating and concentrating to 1/20 of the original volume, adding the disodium edetate aqueous solution, stirring for 30min, cooling to 15 ℃, and filtering. Then, the temperature was raised to 95℃and 45g of a saturated carbonate aqueous solution at 25℃was added thereto, followed by stirring for 1.5 hours and filtration. Then, the washing was performed 3 times with deionized water at 95℃and 200g of deionized water was used for each washing. And then drying the mixture to constant weight at the temperature of 50 ℃ to obtain the lithium carbonate.
Wherein the mass concentration of the polyacrylamide in the polyacrylamide aqueous solution is 0.07%, the polyacrylamide is anionic polyacrylamide, the average molecular weight of the polyacrylamide is 1000 kilodaltons, and the usage amount of the polyacrylamide aqueous solution is 0.08wt% of the total amount of the leaching solution; the mass concentration of the disodium edetate aqueous solution is 0.02%, and the use amount of the disodium edetate aqueous solution is 0.03 weight percent of the total amount of the leaching solution.
Example 2
A method for extracting lithium salts from low-grade lithium ore raw materials, comprising the steps of:
s1, crushing: crushing the lithium ore raw material to obtain powder, wherein the 100-mesh sieve residue of the powder is 0.5%.
Wherein the raw material of the lithium ore is lepidolite, and the content of lithium oxide in the lepidolite is 0.83wt%.
S2, mixing and forming: 90g of sulfate, 15g of calcium salt and 7g of polyvinyl butyral are added into 200g of powder, stirred for 30min, then 11g of absolute ethyl alcohol is added, and stirred for 1h. Then, the mixture was subjected to a press treatment under a pressure of 0.13MPa for 10s. Then heating to 80 ℃, carrying out heat preservation treatment for 2 hours, cooling to-10 ℃, and carrying out heat preservation treatment for 3 hours to obtain the molding material.
Wherein, the sulfate is potassium sulfate and sodium sulfate, and the weight ratio of the potassium sulfate to the sodium sulfate is 1:1; the calcium salt is calcium oxide; the polyvinyl butyral is selected from Lifan chemical Co., ltd.
S3, roasting and grinding: heating the molding material to 240 ℃, and carrying out heat preservation treatment for 2h. Then heating to 940 ℃, and roasting for 4 hours. Then cooling to 25 ℃, and grinding to obtain the grinding material.
S4, acidizing and leaching: 250g of sulfuric acid aqueous solution was added to the abrasive, the temperature was raised to 110℃and the mixture was stirred for 3 hours. Then 500g of deionized water is added, the temperature is raised to 60 ℃, and the mixture is obtained after stirring treatment for 3 hours.
Wherein the mass concentration of sulfuric acid in the sulfuric acid aqueous solution is 70%.
S5, filtering and washing: and filtering the mixture to obtain filtrate and filter residue. And then washing the filter residue for 3 times by adopting deionized water, wherein the deionized water used for each washing is 500g, so as to obtain a washing liquid, and then mixing the washing liquid and the filtrate to obtain the leaching liquid.
S6, removing impurities and precipitating lithium: at a rotation speed of 500r/min, adding saturated sodium hydroxide aqueous solution with a temperature of 25 ℃ into the leaching solution to adjust the pH value to 7.5, and filtering. Then adding the polyacrylamide aqueous solution, and stirring for 30min. Saturated aqueous sodium hydroxide solution at 25℃was added to adjust the pH to 13.5, and the mixture was filtered. Then evaporating and concentrating to 1/20 of the original volume, adding the disodium edetate aqueous solution, stirring for 30min, cooling to 10 ℃, and filtering. Then, the temperature was raised to 95℃and 40g of a saturated carbonate aqueous solution at 25℃was added thereto, followed by stirring for 1.5 hours and filtration. Then, the washing was performed 3 times with deionized water at 95℃and 200g of deionized water was used for each washing. And then drying the mixture to constant weight at the temperature of 50 ℃ to obtain the lithium carbonate.
Wherein the mass concentration of the polyacrylamide in the polyacrylamide aqueous solution is 0.05%, the polyacrylamide is anionic polyacrylamide, the average molecular weight of the polyacrylamide is 1000 kilodaltons, and the usage amount of the polyacrylamide aqueous solution is 0.1wt% of the total amount of the leaching solution; the mass concentration of the disodium edetate aqueous solution is 0.01%, and the use amount of the disodium edetate aqueous solution is 0.05wt% of the total amount of the leaching solution.
Example 3
A method for extracting lithium salts from low-grade lithium ore raw materials, comprising the steps of:
s1, crushing: crushing the lithium ore raw material to obtain powder, wherein the 100-mesh sieve residue of the powder is 0.5%.
Wherein the raw material of the lithium ore is lepidolite, and the content of lithium oxide in the lepidolite is 0.83wt%.
S2, mixing and forming: 110g of sulfate, 25g of calcium salt and 5g of polyvinyl butyral are added into 200g of powder, stirred for 30min, then 9g of absolute ethyl alcohol is added, and stirred for 1h. Then, the mixture was subjected to a press treatment under a pressure of 0.13MPa for 10s. Then heating to 90 ℃, carrying out heat preservation treatment for 1h, cooling to-5 ℃, and carrying out heat preservation treatment for 3h to obtain the molding material.
Wherein, the sulfate is potassium sulfate and sodium sulfate, and the weight ratio of the potassium sulfate to the sodium sulfate is 1:1; the calcium salt is calcium oxide; the polyvinyl butyral is selected from Lifan chemical Co., ltd.
S3, roasting and grinding: heating the molding material to 260 ℃, and carrying out heat preservation treatment for 1h. Then heating to 960 ℃, and roasting for 2 hours. Then cooling to 25 ℃, and grinding to obtain the grinding material.
S4, acidizing and leaching: 350g of an aqueous sulfuric acid solution was added to the abrasive, the temperature was raised to 130℃and the mixture was stirred for 1 hour. Then 300g of deionized water is added, the temperature is raised to 70 ℃, and stirring treatment is carried out for 1h, thus obtaining a mixture.
Wherein the mass concentration of sulfuric acid in the sulfuric acid aqueous solution is 60%.
S5, filtering and washing: and filtering the mixture to obtain filtrate and filter residue. And then washing the filter residue for 3 times by adopting deionized water, wherein the deionized water used for each washing is 300g, so as to obtain a washing liquid, and then mixing the washing liquid and the filtrate to obtain the leaching liquid.
S6, removing impurities and precipitating lithium: at the rotating speed of 500r/min, saturated sodium hydroxide aqueous solution with the temperature of 25 ℃ is added into the leaching solution to adjust the pH value to 7, and the leaching solution is filtered. Then adding the polyacrylamide aqueous solution, and stirring for 30min. Saturated aqueous sodium hydroxide solution at 25℃was added to adjust the pH to 14, and the mixture was filtered. Then evaporating and concentrating to 1/20 of the original volume, adding the disodium edetate aqueous solution, stirring for 30min, cooling to 20 ℃, and filtering. Then, the temperature was raised to 95℃and 50g of a saturated carbonate aqueous solution at 25℃was added thereto, followed by stirring for 1.5 hours and filtration. Then, the washing was performed 3 times with deionized water at 95℃and 200g of deionized water was used for each washing. And then drying the mixture to constant weight at the temperature of 50 ℃ to obtain the lithium carbonate.
Wherein the mass concentration of the polyacrylamide in the polyacrylamide aqueous solution is 0.1%, the polyacrylamide is anionic polyacrylamide, the average molecular weight of the polyacrylamide is 1000 kilodaltons, and the usage amount of the polyacrylamide aqueous solution is 0.05wt% of the total amount of the leaching solution; the mass concentration of the disodium edetate aqueous solution is 0.05%, and the use amount of the disodium edetate aqueous solution is 0.01 weight percent of the total amount of the leaching solution.
Example 4
A method for extracting lithium salt from low-grade lithium ore raw material, which is different from example 1 in that sulfate is different in step S2. The sulfate is potassium sulfate and sodium sulfate, and the weight ratio of the potassium sulfate to the sodium sulfate is 1:2.
Example 5
A method for extracting lithium salt from low-grade lithium ore raw material, which is different from example 1 in that sulfate is different in step S2. The sulfate is potassium sulfate and sodium sulfate, and the weight ratio of the potassium sulfate to the sodium sulfate is 1:3.
Example 6
A method for extracting lithium salt from low-grade lithium ore raw material, which is different from example 1 in that sulfate is different in step S2. The sulfate is potassium sulfate and sodium sulfate, and the weight ratio of the potassium sulfate to the sodium sulfate is 1:4.
Example 7
A method for extracting lithium salt from low-grade lithium ore raw material, which is different from example 1 in that in step S6, the aqueous polyacrylamide solution is replaced with an equal amount of deionized water.
Example 8
A method for extracting lithium salt from low-grade lithium ore raw material, which is different from example 1 in that the disodium edetate aqueous solution is replaced with an equal amount of deionized water in step S6.
Example 9
A method for extracting lithium salt from low-grade lithium ore raw material, which is different from example 1 in step S6.
The step S6 specifically comprises the following steps: adding an aqueous solution of polyacrylamide into the leaching solution at the rotating speed of 500r/min, and stirring for 30min. Saturated aqueous sodium hydroxide solution at 25℃was added to adjust the pH to 13, and the mixture was filtered. Then evaporating and concentrating to 1/20 of the original volume, adding the disodium edetate aqueous solution, stirring for 30min, cooling to 15 ℃, and filtering. Then, the temperature was raised to 95℃and 40g of a saturated carbonate aqueous solution at 25℃was added thereto, followed by stirring for 1.5 hours and filtration. Then, the washing was performed 3 times with deionized water at 95℃and 200g of deionized water was used for each washing. And then drying the mixture to constant weight at the temperature of 50 ℃ to obtain the lithium carbonate.
Comparative example
Comparative example 1
A method for extracting lithium salts from low-grade lithium ore raw materials, which is different from example 1 in step S2.
The step S2 specifically comprises the following steps: 100g of sulfate and 20g of calcium salt are added into 200g of powder, stirring treatment is carried out for 30min, then the temperature is raised to 85 ℃, the heat preservation treatment is carried out for 1.5h, the temperature is lowered to-8 ℃, and the heat preservation treatment is carried out for 4h, thus obtaining the molding material.
Comparative example 2
A method for extracting lithium salts from low grade lithium ore raw materials, which is different from example 1 in that in step S2, polyvinyl butyral is replaced with an equal amount of deionized water.
Comparative example 3
A method for extracting lithium salt from low-grade lithium ore raw material, which is different from example 1 in step S4.
The step S4 specifically comprises the following steps: 300g of deionized water is added into the grinding material, the temperature is raised to 100 ℃, and the grinding material is stirred for 2 hours. Then 400g of deionized water is added, the temperature is raised to 65 ℃, and the mixture is obtained after stirring treatment for 2 hours.
Performance test
(1) The abrasives obtained in step S3 of examples 1 to 6 and comparative examples 1 to 2 were each taken as a sample, and the sample was passed through a 200 mesh sieve, and the 200 mesh sieve residue of the abrasives was calculated, and the detection results are shown in Table 1. And, the lower the mill base 200 mesh screen allowance, the easier the milling, the smaller the sintering.
(2) The leachate obtained in step S5 of examples 1 to 6 and comparative examples 1 to 3 was taken as a sample, and the lithium ion content in the sample was detected by ICP-AES, and the lithium leaching rate was calculated, and the detection results are shown in Table 1.
(3) Lithium carbonate obtained in step S6 of example 1 and examples 7 to 9 was taken as a sample, and the lithium ion content in the sample was detected by ICP-AES, and the purity of lithium carbonate was calculated, and the detection results are shown in Table 1.
TABLE 1 detection results
As can be seen from Table 1, in the method for extracting lithium salt from low-grade lithium ore raw material of the present application, the grinding material 200 mesh screen allowance is 0.83-1.86%, which indicates that the easier grinding, the smaller the occurrence of sintering. Moreover, the lithium leaching rate is 92.32-98.46%, so that the lithium leaching rate is increased, and the lithium carbonate product is further improved. Meanwhile, the purity of the lithium carbonate is 93.45-99.46%, so that the lithium carbonate has good quality and meets the market demand.
Comparing comparative example 1 with comparative example 2, it can be seen that the use of water to press the lithium ore raw material not only does not reduce the 200 mesh screen allowance of the abrasive, but also increases the 200 mesh screen allowance of the abrasive, and also reduces the lithium leaching rate, mainly because the volatilization of water increases the combination of the lithium ore raw material and sulfate, and the occurrence of the sintering aggravation is unfavorable for grinding. In combination with the embodiment 1, the polyvinyl butyral and the absolute ethyl alcohol are used for matching, and the lithium ore raw material and the sulfate are pressed and molded, so that the 200-mesh screen allowance of the grinding material is obviously reduced, and the lithium leaching rate is further increased. In combination with comparative example 3, the lithium leaching rate of the abrasive can be remarkably increased by adopting the combination of sulfuric acid aqueous solution and water.
Comparing example 1 with examples 4-6, it can be seen that, in sulfate, as the 200 mesh screen allowance of the abrasive is increased with the increase of sodium sulfate, the lithium leaching rate is reduced continuously, and when the weight ratio of potassium sulfate to sodium sulfate is 1 (1-3), the lithium leaching rate is more than 95%, and better effect is shown.
Comparing example 1 with examples 7-8, it can be seen that adding an aqueous solution of polyacrylamide and an aqueous solution of disodium edetate to the leachate can significantly increase the purity of lithium carbonate, mainly because polyacrylamide increases the impurity removal effect, disodium edetate chelates calcium ions, and reduces the influence of calcium ions on the quality of lithium carbonate. In combination with example 8, the leaching solution adopts alkali to adjust the pH value once, although the step is saved, the purity of the lithium carbonate is obviously reduced, mainly because part of generated aluminum hydroxide precipitate is dissolved in alkali again, the impurity removing effect is reduced, and the quality of the lithium carbonate is reduced, and also shows that the application adopts alkali to adjust the pH value twice, thereby effectively increasing the quality of the lithium carbonate.
It should be noted that the above-described embodiments are only for explaining the present application and do not constitute any limitation of the present application. The application has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the application as defined in the appended claims, and the application may be modified without departing from the scope and spirit of the application. Although the application is described herein with reference to particular means, materials and embodiments, the application is not intended to be limited to the particulars disclosed herein, as the application extends to all other means and applications which perform the same function.
Claims (10)
1. A method for extracting lithium salt from low-grade lithium ore raw materials, which is characterized in that: the method comprises the following steps:
s1, crushing: crushing a lithium ore raw material to obtain powder;
s2, mixing and forming: adding sulfate, calcium salt and polyvinyl butyral into the powder, mixing, adding absolute ethyl alcohol, mixing, pressing, heating to 80-90 ℃, carrying out heat preservation for 1-2h, cooling to (-10) - (-5) DEG C, and carrying out heat preservation for 3-5h to obtain a molding material;
s3, roasting and grinding: heating the molding material to 240-260 ℃, carrying out heat preservation treatment for 1-2h, heating to 940-960 ℃, carrying out roasting treatment for 2-4h, cooling, and grinding to obtain an abrasive;
s4, acidizing and leaching: adding sulfuric acid aqueous solution into the grinding material, heating to 110-130 ℃, stirring for 1-3h, then adding deionized water, heating to 60-70 ℃, and stirring for 1-3h to obtain a mixture;
s5, filtering and washing: filtering the mixture to obtain filtrate and filter residue, washing the filter residue to obtain a washing liquid, and mixing the washing liquid and the filtrate to obtain a leaching solution;
s6, removing impurities and precipitating lithium: removing impurities from the leaching solution, heating to 90-100 ℃, adding saturated carbonate aqueous solution, filtering, washing and drying to obtain lithium carbonate.
2. A method of extracting lithium salts from low grade lithium ore raw materials according to claim 1, characterized by: the lithium oxide content in the lithium ore raw material is 0.5-1.5%; the raw material of the lithium ore is one or more of lepidolite, lithium porcelain stone, spodumene, tantalite and petalite.
3. A method of extracting lithium salts from low grade lithium ore raw materials according to claim 1, characterized by: in the step S2, the weight ratio of the powder, the sulfate, the calcium salt, the polyvinyl butyral and the absolute ethyl alcohol is 20 (9-11) (1.5-2.5) (0.5-0.7) (0.9-1.1).
4. A method of extracting lithium salts from low grade lithium ore raw materials according to claim 3, characterized by: the sulfate is one or more of potassium sulfate, sodium sulfate and calcium sulfate.
5. A method of extracting lithium salts from low grade lithium ore raw materials according to claim 3, characterized by: the sulfate is potassium sulfate and sodium sulfate, and the weight ratio of the potassium sulfate to the sodium sulfate is 1 (1-3).
6. A method of extracting lithium salts from low grade lithium ore raw materials according to claim 1, characterized by: in the step S1, the 100-mesh screen allowance of the powder is less than or equal to 1%; in the step S3, the 200-mesh screen residue of the grinding material is less than or equal to 2 percent.
7. A method of extracting lithium salts from low grade lithium ore raw materials according to claim 2, characterized by: in the step S4, the weight ratio of the powder, the sulfuric acid aqueous solution and the deionized water is 20 (25-35) (30-50), and the mass concentration of sulfuric acid in the sulfuric acid aqueous solution is 60-70%;
in the step S6, the weight ratio of the powder and the saturated carbonate aqueous solution is 20 (4-5), and the temperature of the saturated carbonate aqueous solution is 20-30 ℃.
8. A method of extracting lithium salts from low grade lithium ore raw materials according to claim 1, characterized by: in the step S6, the following method is adopted for removing impurities: adding alkali into the leaching solution under continuous stirring to adjust the pH value to 7-8, filtering, adding polyacrylamide aqueous solution for mixing, adding alkali to adjust the pH value to 13-14, filtering, evaporating for concentration, adding disodium ethylenediamine tetraacetate aqueous solution for mixing, cooling, filtering, and removing impurities.
9. A method of extracting lithium salts from low grade lithium ore raw materials according to claim 8, wherein: in the step S6, the alkali is saturated sodium hydroxide aqueous solution, and the temperature of the saturated sodium hydroxide aqueous solution is 20-30 ℃;
the usage amount of the polyacrylamide aqueous solution is 0.05-0.1wt% of the total amount of the leaching solution, and the mass concentration of the polyacrylamide in the polyacrylamide aqueous solution is 0.05-0.1%;
the use amount of the disodium edetate aqueous solution is 0.01-0.05wt% of the total amount of the leaching solution, and the mass concentration of the disodium edetate in the disodium edetate aqueous solution is 0.01-0.05%.
10. A method of extracting lithium salts from low grade lithium ore raw materials according to claim 8, wherein: in the step S6, deionized water with the temperature of 90-100 ℃ is adopted for washing, the washing times are 2-5 times, and the total amount of the deionized water used for each washing is 0.5-1.5 times of the total amount of the powder.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1256646A (en) * | 1960-02-11 | 1961-03-24 | Saint Gobain | Lithium extraction process from lepidolite |
| CN113999970A (en) * | 2021-11-03 | 2022-02-01 | 江西金辉锂业有限公司 | Method for extracting lithium from lithium porcelainite minerals through mixed sulfate roasting |
| DE102021132918A1 (en) * | 2020-12-14 | 2022-06-15 | Ceska Geologicka Sluzba | Anhydrous process for preparing activated, defluorinated, sintered concentrates of lithium-containing aluminosilicates |
| CN115520884A (en) * | 2022-10-24 | 2022-12-27 | 唐山鑫丰锂业有限公司 | Process for producing lithium carbonate from spodumene by sulfuric acid method |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MX2021015987A (en) * | 2019-06-21 | 2022-04-06 | Xerion Advanced Battery Corp | Methods for extracting lithium from spodumene. |
| US11673812B2 (en) * | 2019-08-15 | 2023-06-13 | Scandium International Mining Corporation | Countercurrent process for recovering high purity copper sulfate values from low grade ores |
-
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- 2023-02-23 CN CN202310156447.7A patent/CN116409804B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1256646A (en) * | 1960-02-11 | 1961-03-24 | Saint Gobain | Lithium extraction process from lepidolite |
| DE102021132918A1 (en) * | 2020-12-14 | 2022-06-15 | Ceska Geologicka Sluzba | Anhydrous process for preparing activated, defluorinated, sintered concentrates of lithium-containing aluminosilicates |
| CN113999970A (en) * | 2021-11-03 | 2022-02-01 | 江西金辉锂业有限公司 | Method for extracting lithium from lithium porcelainite minerals through mixed sulfate roasting |
| CN115520884A (en) * | 2022-10-24 | 2022-12-27 | 唐山鑫丰锂业有限公司 | Process for producing lithium carbonate from spodumene by sulfuric acid method |
Non-Patent Citations (2)
| Title |
|---|
| 采用硫酸化焙烧—水浸工艺从锂云母 精矿中提取锂;柳林 等;《湿法冶金》;第40卷(第1期);全文 * |
| 锂辉石/碳化硅复相陶瓷材料的制备与性能;鲁媛媛;鹿桂花;周恒为;黄以能;;物理学报;69(11);全文 * |
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