CN115976337A - Method for extracting lithium ions from clay-type lithium ore with extremely low lithium grade by ion replacement - Google Patents
Method for extracting lithium ions from clay-type lithium ore with extremely low lithium grade by ion replacement Download PDFInfo
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 164
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 164
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 84
- 238000000034 method Methods 0.000 title claims abstract description 45
- 150000002500 ions Chemical class 0.000 title claims abstract description 30
- 239000004927 clay Substances 0.000 claims abstract description 47
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims description 61
- 238000002386 leaching Methods 0.000 claims description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 238000010438 heat treatment Methods 0.000 claims description 35
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 34
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 33
- 235000011152 sodium sulphate Nutrition 0.000 claims description 33
- 238000002156 mixing Methods 0.000 claims description 27
- 239000000706 filtrate Substances 0.000 claims description 21
- 238000000227 grinding Methods 0.000 claims description 20
- 238000001354 calcination Methods 0.000 claims description 17
- 238000005342 ion exchange Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 10
- 238000006467 substitution reaction Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 7
- 238000004090 dissolution Methods 0.000 claims description 6
- 150000002642 lithium compounds Chemical class 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 4
- 238000012216 screening Methods 0.000 claims description 4
- 230000000630 rising effect Effects 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 abstract description 21
- 238000000605 extraction Methods 0.000 abstract description 19
- 239000012752 auxiliary agent Substances 0.000 abstract description 13
- 239000012535 impurity Substances 0.000 abstract description 11
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 abstract description 10
- 239000005995 Aluminium silicate Substances 0.000 abstract description 9
- 235000012211 aluminium silicate Nutrition 0.000 abstract description 9
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 9
- 239000007864 aqueous solution Substances 0.000 abstract description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical group O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 abstract description 7
- 238000000926 separation method Methods 0.000 abstract description 7
- 238000011161 development Methods 0.000 abstract description 6
- 239000011229 interlayer Substances 0.000 abstract description 5
- 238000003860 storage Methods 0.000 abstract description 5
- 238000006073 displacement reaction Methods 0.000 abstract description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 13
- 239000011707 mineral Substances 0.000 description 13
- 238000001878 scanning electron micrograph Methods 0.000 description 12
- 229910052622 kaolinite Inorganic materials 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 239000000919 ceramic Substances 0.000 description 8
- 239000002734 clay mineral Substances 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 230000009286 beneficial effect Effects 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 description 6
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 6
- 229910001947 lithium oxide Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000018109 developmental process Effects 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910000323 aluminium silicate Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 4
- 239000011435 rock Substances 0.000 description 4
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 4
- -1 Al and Fe Chemical class 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052656 albite Inorganic materials 0.000 description 2
- 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 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052642 spodumene Inorganic materials 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical group [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000005906 dihydroxylation reaction Methods 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
Images
Classifications
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- 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
Abstract
The invention discloses a method for extracting lithium ions from clay-type lithium ores with extremely low lithium grade by ion replacement, which is a method for extracting lithium ions from clay-type lithium ores with extremely low lithium grade by using sodium salts as roasting aids and displacement aids, firstly destroying the kaolin interlayer aluminosilicate structure in the clay-type lithium ores with extremely low lithium grade by high-temperature programmed roasting, fully exposing the lithium ions, then replacing the lithium ions with sodium ions in the sodium salts to realize the separation of lithium and aluminum silicon, and then extracting the lithium ions from the clay-type lithium ores with extremely low lithium grade by subsequent aqueous solution dissolving treatment. The method used in the invention is to leach the roasting auxiliary agent and the displacement auxiliary agent from the aqueous solution after high-temperature roasting, and the method has the characteristics of high extraction rate of lithium ions, less silicon-aluminum impurity ions, recyclable auxiliary agent and the like. The clay type lithium ore used in the invention has the potential storage capacity of 489 ten thousand tons, is thin in ore bed and easy to develop, can effectively improve the current situation of shortage of Yunnan lithium resources, promotes the development of new energy industry and has good application prospect.
Description
Technical Field
The invention relates to the field of extracting lithium ions from minerals, in particular to a method for extracting lithium ions from clay-type lithium ores with extremely low lithium grade by using ion replacement.
Background
Lithium and compounds thereof are widely applied to emerging fields of medicine, aerospace, new energy automobiles and the like, and are indispensable raw materials of modern high-tech industries. In recent years, the supply and demand conditions of the lithium resource market have changed newly, and the main product lithium battery is in short supply and demand. The potential storage capacity of the clay type lithium ore in Yunnan reaches 489 ten thousand tons, the ore bed is thin, the development is easy, the current situation of the shortage of Yunnan lithium resources can be effectively improved, and the development of new energy industry is promoted.
In order to extract lithium ions in clay-type lithium ores, because the grade of lithium ions in clay-type lithium ores is extremely low, the traditional ore method for extracting high-grade lithium cannot be applied, and researchers also put forward a plurality of strategies. Some researchers can achieve 72.34% of lithium ion extraction rate by using sulfuric acid leaching, but the leaching solution contains a large amount of impurity ions such as Al and Fe, which is not beneficial to the preparation of subsequent lithium carbonate; other researchers use ferric sulfate leaching to achieve 73.6% of lithium ion extraction rate, but the leaching solution contains more iron ions, which is also not beneficial to the preparation of subsequent lithium carbonate.
In view of the above, a method for extracting lithium ions from clay-type lithium ores with extremely low lithium grade is urgently needed to solve the defect that high-purity lithium cannot be extracted from the existing clay-type lithium ores with extremely low lithium grade.
Disclosure of Invention
The method comprises the steps of taking sodium salt as a roasting aid and a replacement aid, firstly, destroying the kaolin interlayer aluminosilicate structure in the clay type lithium ore with extremely low lithium grade by high-temperature roasting, exposing lithium ions, then, replacing the lithium ions by sodium ions in the sodium salt, realizing the separation of lithium and aluminum silicon, and then, extracting the lithium ions in the clay type lithium ore with extremely low lithium grade by subsequent aqueous solution dissolution treatment. The method used in the invention is to leach the roasting auxiliary agent and the displacement auxiliary agent in the aqueous solution after high-temperature roasting, and the method has the characteristics of high lithium ion extraction rate, less silicon-aluminum impurity ions, recyclable auxiliary agent and the like. The clay type lithium ore used in the invention has the potential storage capacity of 489 ten thousand tons, is thin in ore bed and easy to develop, can effectively improve the current situation of the shortage of the present Yunnan lithium resource, promotes the development of new energy industry and has good application prospect.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
a method for extracting lithium ions from clay-type lithium ores with extremely low lithium grade by ion replacement comprises the following steps:
step S1: crushing, grinding and screening the clay type lithium ore with extremely low lithium grade;
step S2: respectively weighing the clay type lithium ore and the sodium salt prepared in the step S1; uniformly mixing clay type lithium ore and sodium salt to obtain a mixture A;
and step S3: calcining the mixture A obtained in the step S2, continuously stirring in the calcining process to promote ion exchange, and grinding and screening the calcined mixture to obtain a mixture B;
and step S4: and (4) mixing the calcined mixture B in the step (S3) with water, dissolving and leaching for a certain time at a certain temperature, performing suction filtration after leaching is finished to obtain filtrate and filter residue, wherein lithium ions exist in the filtrate, and the filtrate can be directly used for preparing other subsequent lithium compounds after being concentrated.
Further, the calcination treatment process in step S3 specifically includes:
a preheating stage: preheating the mixture A at 95-110 deg.c for 10-30min to eliminate free water, most adsorbed water and small amount of interlayer water from the mineral;
a temperature rising and preserving stage: slowly heating to 400-450 ℃ at the heating rate of 5-7 ℃/min for 10-30min, slowly removing colloidal water and crystal water in the minerals, continuously heating to 700-800 ℃ at the heating rate of 5-7 ℃/min for 60-90min, and slowly removing structural water and other residual water in the minerals to form a loose and porous mineral structure with increased surface area, which is favorable for ion exchange extraction.
Further, in the step S1, the clay-type lithium ore having an extremely low lithium grade is crushed, ground, and sieved so as to have a particle size of less than 74 μm, and in the step S3, the calcined mixture is ground, and sieved so as to have a particle size of less than 74 μm.
Further, in the step S2, the mass fraction of the clay type lithium ore is 55.14-88.89%, the mass fraction of the sodium salt is 11.11-44.86%, and the sum of the mass fractions is 100%.
Further, the lithium ion grade in the clay-type lithium ore with extremely low lithium grade is lower than 0.5%.
Further, the sodium salt is preferably sodium sulfate.
Further, the dissolving and leaching time in the step S4 is 0.5-2 h; the dissolution leaching temperature in the step S4 is 70-100 ℃.
Further, the mass ratio of the mixture B calcined in the step S4 to water is 1:8 to 15 g/ml.
Furthermore, the method for extracting lithium ions can be applied to directly extracting the lithium ions with extremely high purity by an aqueous solution method in the clay type lithium ores with extremely low lithium grade.
The clay type lithium ore leached by using sulfuric acid can reach 90.5 percent of lithium ion extraction rate, but the impurity ions are too much, the concentration of Al ions reaches over 10g/L, the concentration of Fe ions reaches over 0.5g/L, and more lithium ions can be taken away during impurity removal, so that the subsequent lithium carbonate preparation test is not facilitated. The clay type lithium ore leached by adopting ferric sulfate achieves the extraction rate of 73.6 percent of lithium ions, but Fe ions in the leaching solution reach more than 5g/L, and are difficult to remove in the impurity removal process, and the subsequent lithium carbonate preparation test is also not facilitated. And mixing sodium sulfate with clay-type lithium ore in a ratio of 44.86:55.14, the extraction rate of lithium ions in the leachate obtained by mixing, roasting and leaching reaches 78.5 percent, and the content of impurity ions (such as Al, fe and Mg ions) is lower than 0.04g/L, which is superior to that of the leachate of clay-type lithium ores obtained by leaching with sulfuric acid and leaching with ferric sulfate.
The main innovation point of the invention is that sodium sulfate and clay type lithium ore are mixed and roasted through temperature programming, and water leaching is used, so that the extraction rate of lithium ions can be increased, and the extraction rate of other ions can be reduced.
The invention has the beneficial effects that:
the invention provides a method for extracting lithium ions from clay-type lithium ores with extremely low lithium grade by ion replacement, which has the advantages that compared with the prior method:
1) Compared with sulfuric acid leaching, the water leaching used in the invention is more environment-friendly, has lower requirements on equipment and can reduce the construction cost;
2) The clay type lithium ore has the potential storage capacity of 489 ten thousand tons, is thin in ore bed and easy to develop, can effectively improve the current situation of the shortage of the lithium resources in Yunnan, promotes the development of new energy industry and has good application prospect;
3) Compared with sulfuric acid leaching, the leaching solution leached by the method has higher lithium ion extraction rate and lower impurity ion extraction rate;
4) The method for extracting lithium ions from clay-type lithium ores with extremely low lithium grade by ion replacement can overcome the defect that high-purity lithium cannot be extracted by the traditional process in the existing clay-type lithium ores with extremely low lithium grade, creatively adopts a programmed heating mode, fully exposes and combines lithium ions, and then extracts and combines the lithium ions by ion exchange, thereby solving the technical problem that the combined lithium ions in kaolin cannot be extracted.
Drawings
FIG. 1 is an XRD pattern of clay-type lithium ore in an example of the present invention;
FIG. 2 is an XRD pattern of leach residue from examples 3-6 of the present invention;
FIG. 3 is an SEM image of clay-type lithium ore after roasting;
FIG. 4 is an SEM image of clay after mixed roasting with 43% sodium sulfate;
FIG. 5 is an SEM image of leaching residues after mixing and roasting by adding 43% sodium sulfate;
FIG. 6 is an SEM image of leaching residues after mixing and roasting by adding 34% sodium sulfate;
FIG. 7 is an SEM image of leaching residues after mixing and roasting by adding 23% sodium sulfate;
FIG. 8 is an SEM image of leaching residues after mixing and roasting with 12% sodium sulfate;
fig. 9 is a crystal structure of kaolinite (projection of kaolinite layer in directions of a and b axes);
fig. 10 is a crystal structure of kaolinite (projection of kaolinite in the direction of the c-axis).
Detailed Description
The following are specific embodiments given by the inventor, and it should be noted that these examples are only for better explaining the present invention and are not intended to limit the scope of the present invention. All the parameter selections within the technical scheme of the invention belong to the protection scope of the invention.
The embodiment of the invention adopts clay type lithium ore as the ore raw material for extracting lithium ions, the XRD pattern of the ore raw material is shown as figure 1, the concrete mineral composition of the clay type lithium ore raw ore is analyzed by combining the process mineralogy, and the mineral composition of the clay type lithium ore raw ore is shown as the table 1:
TABLE 1 mineral composition of raw ores
As can be seen from fig. 1 and table 1, 83% of the raw ore materials of the clay-type lithium ore used in the present invention are kaolinite, 9.1% of boehmite, 5.2% of limonite, which is greatly different from the hard-rock-type lithium ore, the hard-rock-type lithium ore consists of spodumene, quartz, albite, etc., the lithium grade of the hard-rock-type lithium ore is above 5%, and the lithium oxide in the hard-rock-type lithium ore can be extracted by a method of roasting to generate lithium sulfate through the reaction of the lithium oxide and the roasting aid, but the lithium exists in the ore in the form of lithium ions after the test of the clay-type lithium ore by the ICP method, which is only 0.28% of the grade of the lithium oxide, and the lithium sulfate cannot be generated by the conventional roasting aid to be extracted, and a new extraction method must be found to extract the high-purity lithium ions.
Example 1:
crushing and grinding the clay type lithium ore until the powder can pass through a 200-mesh sieve, respectively weighing 55.14g of the clay type lithium ore and 44.86g of sodium sulfate, pouring the raw materials into a beaker, and uniformly mixing to obtain a mixture; preheating the mixture in a calcining furnace at 110 ℃ for 10min, slowly heating to 450 ℃ at a heating rate of 7 ℃/min, keeping for 10min, continuously slowly heating to 800 ℃ at a heating rate of 7 ℃/min, keeping for 60min, programming to heat for about 178.5min, and grinding the calcined mixture until the calcined mixture can pass through a 200-mesh sieve; mixing the ground mixture with 1L of water, pouring into a 1L conical flask, putting into an oil bath kettle, stirring at 95 deg.C for 1h, and filtering with a ceramic filter to obtain filtrate and filter residue.
Example 2:
crushing and grinding the clay type lithium ore until the powder can pass through a 200-mesh sieve, respectively weighing 55.14g of the clay type lithium ore and 44.86g of sodium sulfate, pouring the raw materials into a beaker, and uniformly mixing to obtain a mixture; preheating the mixture in a calcining furnace at the temperature of 95 ℃ for 30min, slowly heating to 400 ℃ at the heating rate of 5 ℃/min, keeping for 30min, continuously slowly heating to 700 ℃ at the heating rate of 5 ℃/min, keeping for 90min, programming the temperature to rise for about 271min, and grinding the calcined mixture until the calcined mixture can pass through a 200-mesh sieve; mixing the ground mixture with 1L of water, pouring into a 1L conical flask, putting into an oil bath pan, stirring at 95 ℃ for 1h, and filtering with a ceramic filter to obtain filtrate and filter residue.
Comparative example 1:
crushing and grinding clay type lithium ore until the powder can pass through a 200-mesh sieve, respectively weighing 55.14g of clay type lithium ore and 44.86g of sodium sulfate, pouring the raw materials into a beaker, and uniformly mixing to obtain a mixture; directly calcining the mixture in a calcining furnace at 800 ℃ for 178.5min, and grinding the calcined mixture until the calcined mixture can pass through a 200-mesh sieve; mixing the ground mixture with 1L of water, pouring into a 1L conical flask, putting into an oil bath kettle, stirring at 95 deg.C for 1h, and filtering with a ceramic filter to obtain filtrate and filter residue.
Comparative example 2:
crushing and grinding clay type lithium ore until the powder can pass through a 200-mesh sieve, respectively weighing 55.14g of clay type lithium ore and 44.86g of sodium sulfate, pouring the raw materials into a beaker, and uniformly mixing to obtain a mixture; rapidly heating the mixture to 800 ℃ in a calcining furnace at a heating rate of 50 ℃/min, keeping the temperature for 162.5min, wherein the total calcining time is 178.5min, and grinding the calcined mixture until the calcined mixture can pass through a 200-mesh sieve; mixing the ground mixture with 1L of water, pouring into a 1L conical flask, putting into an oil bath kettle, stirring at 95 deg.C for 1h, and filtering with a ceramic filter to obtain filtrate and filter residue.
The filtrate materials described in examples 1-2 and comparative examples 1-2 above were tested for lithium ion concentration using icp, and the results are shown in table 2.
TABLE 2 influence of the roasting procedure on the lithium leaching rate
From the test results of examples 1-2, it can be seen that, through a temperature programming manner, kaolin, which is a main component in the ore, is slowly dehydrated (in various water forms) through slow temperature rise, the structure of aluminosilicate is compacted and destroyed, the slow dehydration inhibits the escape speed of water, so that different structural parts and different water forms are slowly and orderly removed, the collapse phenomenon of the ore is inhibited, a loose and porous structure is formed on the surface and inside of the ore, lithium ions combined with the structure are fully exposed, sodium sulfate and lithium ions in clay minerals undergo an ion exchange reaction, lithium between layers and in crystal lattices is released, and then, separation of lithium and aluminum silicon is realized through water leaching.
From the test results of comparative examples 1-2, it can be seen that a temperature programming manner is not adopted, but direct high-temperature calcination or rapid temperature rise calcination is adopted, various water forms are rapidly escaped and ejected out of the interior of the ore due to high temperature or rapid temperature rise, the compression degree of the ore is large due to short-time lack of support, the structure of aluminosilicate is seriously damaged at high temperature, compression and collapse among kaolin layers are serious, after moisture is removed, lithium ions are not available to perform ion exchange with sodium ions, namely, the lithium ions are closed again or buried and masked, so that the replacement rate of the lithium ions is low, and the extraction efficiency is low.
The highest roasting temperature of the method cannot exceed 800 ℃, and after the highest roasting temperature exceeds 800 ℃, the kaolinite can be recrystallized to form mullite, which is not beneficial to subsequent ion exchange reaction and subsequent leaching.
The invention uses sodium salt as roasting auxiliary agent and replacement auxiliary agent, firstly destroys and opens the aluminum silicate structure between kaolin layers in clay type lithium ore with extremely low lithium grade by temperature programming and high temperature roasting, fully exposes lithium ion, then replaces lithium ion by sodium ion in sodium salt, realizes the separation of lithium and aluminum silicon, and extracts lithium ion in clay type lithium ore with extremely low lithium grade by subsequent aqueous solution dissolving treatment. In examples 1-2, the extraction rates of aluminum, iron and magnesium were all lower than 1%, which is beneficial for the subsequent preparation of lithium compounds such as lithium carbonate.
Example 3:
crushing and grinding clay type lithium ore until the powder can pass through a 200-mesh sieve, respectively weighing 88g of clay type lithium ore and 12g of sodium sulfate, pouring the raw materials into a beaker, and uniformly mixing to obtain a mixture; preheating the mixture in a calcining furnace at 110 ℃ for 10min, slowly heating to 450 ℃ at a heating rate of 7 ℃/min, keeping for 10min, continuously slowly heating to 800 ℃ at a heating rate of 7 ℃/min, keeping for 60min, programming to heat for about 178.5min, and grinding the calcined mixture until the calcined mixture can pass through a 200-mesh sieve; mixing the ground mixture with 1L of water, pouring into a 1L conical flask, putting into an oil bath kettle, stirring at 95 deg.C for 1h, and filtering with a ceramic filter to obtain filtrate and filter residue.
Example 4:
crushing and grinding the clay type lithium ore until the powder can pass through a 200-mesh sieve, respectively weighing 77g of the clay type lithium ore and 23g of sodium sulfate, pouring the raw materials into a beaker, and uniformly mixing to obtain a mixture; preheating the mixture in a calcining furnace at 110 ℃ for 10min, slowly heating to 450 ℃ at a heating rate of 7 ℃/min, keeping for 10min, continuously slowly heating to 800 ℃ at a heating rate of 7 ℃/min, keeping for 60min, programming to heat for about 178.5min, and grinding the calcined mixture until the calcined mixture can pass through a 200-mesh sieve; mixing the ground mixture with 1L of water, pouring into a 1L conical flask, putting into an oil bath kettle, stirring at 95 deg.C for 1h, and filtering with a ceramic filter to obtain filtrate and filter residue.
Example 5:
crushing and grinding clay type lithium ore until the powder can pass through a 200-mesh sieve, respectively weighing 66g of clay type lithium ore and 34g of sodium sulfate, pouring the raw materials into a beaker, and uniformly mixing to obtain a mixture; preheating the mixture in a calcining furnace at 110 ℃ for 10min, slowly heating to 450 ℃ at a heating rate of 7 ℃/min, keeping for 10min, continuously slowly heating to 800 ℃ at a heating rate of 7 ℃/min, keeping for 60min, programming to heat for about 178.5min, and grinding the calcined mixture until the calcined mixture can pass through a 200-mesh sieve; mixing the ground mixture with 1L of water, pouring into a 1L conical flask, putting into an oil bath kettle, stirring at 95 deg.C for 1h, and filtering with a ceramic filter to obtain filtrate and filter residue.
Example 6:
crushing and grinding the clay type lithium ore until the powder can pass through a 200-mesh sieve, respectively weighing 57g of the clay type lithium ore and 43g of sodium sulfate, pouring the raw materials into a beaker, and uniformly mixing to obtain a mixture; preheating the mixture in a calcining furnace at 110 ℃ for 10min, slowly heating to 450 ℃ at a heating rate of 7 ℃/min, keeping for 10min, continuously slowly heating to 800 ℃ at a heating rate of 7 ℃/min, keeping for 60min, programming to heat for about 178.5min, and grinding the calcined mixture until the calcined mixture can pass through a 200-mesh sieve; mixing the ground mixture with 1L of water, pouring into a 1L conical flask, putting into an oil bath kettle, stirring at 95 deg.C for 1h, and filtering with a ceramic filter to obtain filtrate and filter residue.
The filtrate materials described in examples 3-6 above were tested for lithium ion concentration using icp, and the results are shown in table 3.
TABLE 3 influence of sodium sulfate addition on lithium leaching rate
From the test results of examples 3-6, it can be seen that the leaching rate of lithium ions increases with the increase of the addition amount of sodium sulfate, and when the addition amount of sodium sulfate reaches 43%, the leaching rate of lithium ions reaches 77.23%, and the extraction rates of aluminum, iron and magnesium are all lower than 1%, which is beneficial to the subsequent preparation of lithium carbonate.
The leaching residue of examples 3-6 was tested, as figure 2 is the XRD pattern of the leaching residue of examples 3-6, and comparing figure 2 with table 3, it can be seen that the leaching rates of lithium ions by water leaching were different at different sodium sulphate addition levels, but the leaching residues had similar phase composition, which means that the main mineral phase did not decompose when lithium was extracted. That is, lithium is leached into a solution through ion exchange rather than mineral dissolution, and sodium ions and lithium ions are subjected to ion substitution during high-temperature roasting, thereby extracting low-grade lithium ions.
The raw ores and the leached residues in examples 3 to 6 were tested, fig. 3 is an SEM image of clay-type lithium ore raw ore after roasting according to the temperature-raising procedure in example 3, fig. 4 is an SEM image of clay after mixed roasting with 43% sodium sulfate in example 6, fig. 5 is an SEM image of leached residue after mixed roasting with 43% sodium sulfate in example 6, fig. 6 is an SEM image of leached residue after mixed roasting with 34% sodium sulfate in example 5, fig. 7 is an SEM image of leached residue after mixed roasting with 23% sodium sulfate in example 4, and fig. 8 is an SEM image of leached residue after mixed roasting with 12% sodium sulfate in example 3. As described in fig. 3 to 8, it was confirmed from the leaching slag of various sodium sulfate addition amounts and the images before leaching under optimum conditions and SEM of raw ore that the layered structure of the clay mineral was not broken. Thus, lithium ions are leached into solution by ion exchange rather than mineral dissolution, which explains why other mineral components are present in the leach filtrate in very small amounts. The interlayer spacing of the clay mineral is compacted as interlayer/adsorbed water is lost, and structural collapse occurs in the clay mineral, releasing lithium and reacting with dehydroxylation, and smaller ions (sodium ions) enter. This behavior is a particular ion exchange process. In order to ensure the ion exchange process, the invention adopts a programmed temperature manner creatively, through slow temperature rise, kaolin which accounts for the main component in the ore is slowly dehydrated (various water forms), the structure of aluminosilicate is compacted and destroyed, the slow dehydration inhibits the escape speed of water, different structural parts and different water forms are slowly and orderly removed, the collapse phenomenon of the ore is inhibited, a loose and porous structure is formed on the surface and in the ore, lithium ions combined with the structure are fully exposed, sodium sulfate and the lithium ions in the clay minerals are subjected to ion exchange reaction, lithium between layers and crystal lattices is released, and then the separation of lithium and aluminum silicon is realized through water immersion, on the other hand, the residual layered structure of the clay minerals (shown in figures 5-8) indicates that the clay minerals are not dissolved in the acid immersion process.
The filter residue in example 1 was repeatedly washed with a small amount of deionized water several times to obtain a total filtrate and an eluate, and the total filtrate and the eluate were subjected to icp analysis, as shown in table 4, the filtrate contained 73.8g/L of sodium ions, and the amount of sodium sulfate was 44.28g, which means that only a small amount of sodium ions were exchanged with lithium ions. It was demonstrated that sodium sulfate did not react with the ore.
TABLE 4 composition of the filtrate
And (3) mechanism analysis:
due to Li + With Al 3+ The difference between the ionic radii is large, and the two can only form limited isomorphic substitution at high temperature, so that lithium cannot directly replace aluminum in kaolinite. Thus lithium in kaolinite does not belong to the homogeneous isomorphic form.
In an ideal model of the kaolinite structure (fig. 9 and 10), the silicon-oxygen tetrahedra is a regular tetrahedron and the aluminous octahedron is a regular octahedron. Hydroxyl (-OH) is exposed on the crystal surface and fracture, and under the action of mineralization, hydrogen ions may be ionized to exhibit electronegativity, and attract Li + With or other ions - Combine to compensate for electronegativity caused by hydrogen ion ionization, and maintain the electroneutrality of the molecule. Thus, the presence of Li in kaolinite + The receiving space of (2). The lithium element is therefore bound in kaolinite mainly in the form of lithium ions to the hydroxyl groups of aluminum oxide or to sites in the silicon tetrahedron where the positive charge is deficient.
The data of the above examples show that, for the hard rock type lithium ore, the hard rock type lithium ore consists of spodumene, quartz, albite and the like, the lithium grade of the hard rock type lithium ore is above 5%, and the lithium oxide in the hard rock type lithium ore can be extracted by adopting a roasting mode to realize the reaction of the lithium oxide and a roasting auxiliary agent to generate the lithium sulfate, but the lithium exists in the ore in a lithium ion form after the ICP method test is adopted in the clay type lithium ore raw ore of the invention, the grade converted into the lithium oxide is only 0.28%, the lithium sulfate cannot be generated by a traditional direct roasting auxiliary agent mode to extract, and a new extraction mode must be found to extract the high-purity lithium ions. The invention extracts high-purity lithium ions in clay type lithium ore with the lithium grade of only 0.28% through a creative new mode, and because the lithium ions in the clay type lithium ore exist on the lattice surface of minerals such as kaolinite of the clay type lithium ore and cannot be extracted through the traditional roasting mode, the invention innovatively discovers that the technical problem can be solved through the temperature programming of the ore and obtains the excellent technical effect.
Through a temperature programming mode, kaolin which accounts for the main component in the ore is slowly dehydrated (in various water forms) through slow temperature rise, the structure of aluminosilicate is compacted and destroyed, the escape speed of water is inhibited through slow dehydration, different structural parts and different water forms are slowly and orderly removed, the collapse phenomenon of the ore is inhibited, a loose and porous structure is formed on the surface and inside the ore, lithium ions combined with the structure are fully exposed, sodium sulfate and the lithium ions in clay minerals are subjected to ion exchange reaction, lithium between layers and crystal lattices are released, then the separation of lithium and aluminum silicon is realized through water leaching, the extraction rate of the lithium ions in leachate obtained by mixing roasting water leaching of the sodium sulfate and the clay type lithium ores is extremely high, the content of impurities of other metal ions is extremely low, and the preparation and the production of subsequent lithium compounds are very facilitated.
Therefore, the programmed temperature rise fully exposes lithium ions, and then the lithium ions in the clay type lithium ore with extremely low lithium grade are extracted through the special ion exchange process, and the mode only relates to the ion exchange process, so that compared with the mode of acid leaching and the like, the lithium ions have higher purity, no other impurities such as silicon, aluminum, iron and the like, and are beneficial to the direct preparation of the subsequent lithium compound.
The invention discloses a method for extracting lithium ions from clay-type lithium ores with extremely low lithium grade by ion replacement, which is a method for extracting lithium ions from clay-type lithium ores with extremely low lithium grade by using sodium salts as roasting aids and replacement aids, firstly destroying aluminosilicate structures among kaolin layers in the clay-type lithium ores with extremely low lithium grade by high-temperature programmed roasting to fully expose the lithium ions, then replacing the lithium ions by the sodium ions in the sodium salts to realize the separation of lithium and aluminum silicon, and then extracting the lithium ions from the clay-type lithium ores with extremely low lithium grade by subsequent aqueous solution dissolving treatment. The method used in the invention is to leach the roasting auxiliary agent and the displacement auxiliary agent from the aqueous solution after high-temperature roasting, and the method has the characteristics of high extraction rate of lithium ions, less silicon-aluminum impurity ions, recyclable auxiliary agent and the like. The clay type lithium ore used in the invention has the potential storage capacity of 489 ten thousand tons, is thin in ore bed and easy to develop, can effectively improve the current situation of the shortage of the present Yunnan lithium resource, promotes the development of new energy industry and has good application prospect.
Thus, while embodiments of the present invention have been described, the above description is intended to be illustrative, not exhaustive, and not limited to the described embodiments. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (9)
1. A method for extracting lithium ions from clay-type lithium ores with extremely low lithium grade by ion replacement is characterized by comprising the following steps:
step S1: crushing, grinding and screening the clay type lithium ore with extremely low lithium grade;
step S2: respectively weighing the clay type lithium ore and the sodium salt prepared in the step S1; uniformly mixing clay type lithium ore and sodium salt to obtain a mixture A;
and step S3: calcining the mixture A obtained in the step S2, continuously stirring in the calcining process to promote ion exchange, and grinding and screening the calcined mixture to obtain a mixture B;
and step S4: and (4) mixing the calcined mixture B in the step (S3) with water, dissolving and leaching for a certain time at a certain temperature, performing suction filtration after leaching is finished to obtain filtrate and filter residue, wherein lithium ions exist in the filtrate, and the filtrate is concentrated and then used for preparing other subsequent lithium compounds.
2. The method for extracting lithium ions from clay-type lithium ores with extremely low lithium grade by ion substitution as claimed in claim 1, wherein the calcination treatment in step S3 comprises the steps of:
a preheating stage: preheating the mixture A at 95-110 ℃ for 10-30min;
a temperature rising and preserving stage: slowly heating to 400-450 ℃ at the heating rate of 5-7 ℃/min, keeping the temperature for 10-30min, continuously heating to 700-800 ℃ at the heating rate of 5-7 ℃/min, and keeping the temperature for 60-90min.
3. The method for extracting lithium ions from clay-type lithium ores with extremely low lithium grade by ion substitution as claimed in claim 1, wherein the clay-type lithium ores with extremely low lithium grade are crushed, ground and sieved to have a particle size of less than 74 μm in step S1, and the calcined mixture is ground and sieved to have a particle size of less than 74 μm in step S3.
4. The method for extracting lithium ions from clay-type lithium ore having an extremely low lithium grade by ion substitution as claimed in claim 1, wherein the mass fraction of the clay-type lithium ore in the step S2 is 55.14 to 88.89%, the mass fraction of the sodium salt is 11.11 to 44.86%, and the sum of the mass fractions is 100%.
5. The method for extracting lithium ions from very low lithium grade clay-type lithium ores as claimed in claim 1 wherein the lithium ion grade in said very low lithium grade clay-type lithium ores is less than 0.5%.
6. The method for extracting lithium ions from very low lithium grade clay-type lithium ores using ion substitution as claimed in claim 1, wherein said sodium salt is sodium sulfate.
7. The method for extracting lithium ions from clay-type lithium ores having an extremely low lithium grade by ion substitution as claimed in claim 1, wherein the dissolution leaching time in said step S4 is 0.5 to 2 hours.
8. The method for extracting lithium ions from clay-type lithium ores having an extremely low lithium grade by ion substitution as claimed in claim 1, wherein the dissolution leaching temperature in said step S4 is 70 to 100 ℃.
9. The method for extracting lithium ions from clay-type lithium ores with extremely low lithium grade by ion substitution according to claim 1, wherein the ratio of the mixture B calcined in the step S4 to water is 1:8 to 15 g/ml.
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