CN111410218A - Method for separating magnesium, lithium and boron from brine based on precipitation-ion imprinting coupling - Google Patents
Method for separating magnesium, lithium and boron from brine based on precipitation-ion imprinting coupling Download PDFInfo
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- CN111410218A CN111410218A CN202010233479.9A CN202010233479A CN111410218A CN 111410218 A CN111410218 A CN 111410218A CN 202010233479 A CN202010233479 A CN 202010233479A CN 111410218 A CN111410218 A CN 111410218A
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- 239000011777 magnesium Substances 0.000 title claims abstract description 71
- 239000012267 brine Substances 0.000 title claims abstract description 62
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 title claims abstract description 55
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 53
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 51
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 51
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 51
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 40
- 230000008878 coupling Effects 0.000 title claims abstract description 15
- 238000010168 coupling process Methods 0.000 title claims abstract description 15
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 36
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 33
- 239000000706 filtrate Substances 0.000 claims abstract description 29
- 239000000243 solution Substances 0.000 claims abstract description 23
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 18
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 239000003063 flame retardant Substances 0.000 claims abstract description 12
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004327 boric acid Substances 0.000 claims abstract description 11
- -1 boron anions Chemical class 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000005516 engineering process Methods 0.000 claims abstract description 9
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000005342 ion exchange Methods 0.000 claims abstract description 8
- 239000012716 precipitator Substances 0.000 claims abstract description 8
- 150000002500 ions Chemical class 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 230000001376 precipitating effect Effects 0.000 claims abstract 2
- 229920000642 polymer Polymers 0.000 claims description 25
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 20
- 238000000605 extraction Methods 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 11
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- 238000000909 electrodialysis Methods 0.000 claims description 8
- 239000012528 membrane Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000010008 shearing Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 239000010410 layer Substances 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 230000020477 pH reduction Effects 0.000 claims description 4
- 239000000779 smoke Substances 0.000 claims description 4
- 230000001629 suppression Effects 0.000 claims description 4
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims description 2
- 239000012065 filter cake Substances 0.000 claims description 2
- 239000011229 interlayer Substances 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 230000008929 regeneration Effects 0.000 claims description 2
- 238000011069 regeneration method Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000001694 spray drying Methods 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims 1
- 229920002678 cellulose Polymers 0.000 claims 1
- 239000012295 chemical reaction liquid Substances 0.000 claims 1
- 238000002955 isolation Methods 0.000 claims 1
- 229910000000 metal hydroxide Inorganic materials 0.000 claims 1
- 150000004692 metal hydroxides Chemical class 0.000 claims 1
- 230000006911 nucleation Effects 0.000 claims 1
- 238000010899 nucleation Methods 0.000 claims 1
- 230000000717 retained effect Effects 0.000 claims 1
- 239000012266 salt solution Substances 0.000 claims 1
- 238000001035 drying Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract 1
- 239000000463 material Substances 0.000 description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 8
- 229910052700 potassium Inorganic materials 0.000 description 8
- 239000011591 potassium Substances 0.000 description 8
- 230000018109 developmental process Effects 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 3
- 229910000861 Mg alloy Inorganic materials 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000005188 flotation Methods 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- 229910001148 Al-Li alloy Inorganic materials 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 208000027697 autoimmune lymphoproliferative syndrome due to CTLA4 haploinsuffiency Diseases 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- DBDNZCBRIPTLJF-UHFFFAOYSA-N boron(1-) monohydride Chemical compound [BH-] DBDNZCBRIPTLJF-UHFFFAOYSA-N 0.000 description 1
- 229910052599 brucite Inorganic materials 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000001640 fractional crystallisation Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000002680 magnesium Chemical class 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 150000002681 magnesium compounds Chemical class 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
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/78—Compounds containing aluminium and two or more other elements, with the exception of oxygen and hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
- C01B35/10—Compounds containing boron and oxygen
- C01B35/1045—Oxyacids
- C01B35/1054—Orthoboric acid
- C01B35/109—Purification; Separation; Concentration
-
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention belongs to the technical field of salt lake brine resource utilization, and provides a method for separating magnesium, lithium and boron from brine based on precipitation-ion imprinting coupling, which mainly comprises the steps of taking salt lake brine as a raw material, adding an aluminum source and a precipitator, allowing boron anions to enter layers while precipitating magnesium to obtain boron-rich magnesium-based layered double hydroxide (MgAl-B-L DHs), filtering and washing, drying, directly using as a high smoke-suppression flame retardant, and performing ion exchange with a sodium carbonate solution to prepare boric acid, wherein lithium ions in the brine are left in the filtrate, and lithium is enriched and extracted by using an ion imprinting technology.
Description
Technical Field
The invention belongs to the technical field of salt lake brine resource utilization, and particularly provides a method for separating magnesium, lithium and boron from brine based on precipitation-ion imprinting coupling.
Background
The salt lake brine contains abundant potassium, lithium, boron, magnesium and other resources. The utilization of potassium resources in China reaches a considerable scale, only the Qinghai salt lake industrial group has the production capacity of 230 ten thousand tons of potassium fertilizers, but lithium, magnesium, boron and the like in the old brine after potassium extraction are not fully utilized, and how to realize the efficient separation of the lithium, the boron, the magnesium and the like in the salt lake brine is one of the endeavors of salt lake workers.
Lithium has an important strategic position in the development of energy storage materials and clean nuclear energy, and is widely applied to the fields of high-energy batteries, aerospace, nuclear power generation and the like. Lithium is the main negative electrode material of high-energy batteries; aluminum lithium and magnesium lithium alloys are used in the aerospace industry, automotive industry, etc. to replace aluminum magnesium alloys;6l i is an important material for controllable thermonuclear fusion reaction, high purity7L i are the essential materials for thorium-based nuclear reactors currently in the neighborhood of China the demand for lithium in the international market is continuously increasing at a rate of 7% -11% per year.
The lithium resource of the salt lake accounts for more than 69 percent of the industrial reserve of the lithium resource in the world, the reserve of the lithium resource of China is the fifth world, wherein the lithium resource of the salt lake accounts for 71 percent, and the lithium salt of the Qinghai salt lake (L i)2O) reserves 1392 ten thousand tons, which is the first place in China, and is different from the south America lithium-rich salt lake, the Qinghai salt lake is magnesium-rich, and has the obvious characteristics that the Mg/L i ratio is high, the Mg/L i ratio of the Carr sweat salt lake which is developed earlier and developed to a higher degree is up to 1837, the chai salt lake is 114, the Mg/Li ratio of the east-Tai Ginner salt lake brine is 40-60, which is dozens or even thousands of times of abroadThe lithium industry is obviously not applicable to Qinghai salt lakes. For decades, the vast salt lake science and technology workers in China are always dedicated to the technical development and engineering work of extracting lithium from the Qinghai salt lake brine, and great progress is made. Multiple technologies such as brine calcining and leaching technology, brine adsorption lithium extraction technology, brine ion selective migration separation and extraction technology, extraction lithium extraction technology and the like are developed successively.
The effective separation of boron in the lithium extraction process is also an essential link for the comprehensive utilization of salt lake resources. The method for extracting boron from brine comprises acidification precipitation method, borate precipitation method, solvent extraction method, fractional crystallization method, ion exchange method, flotation method, etc. The acid precipitation method and the flotation method are suitable for raw materials with high boron content, the process operation is simple, the equipment investment is low, the raw material cost is low, and the recovery rate is low. The extraction method and the ion exchange method can be used for raw materials with low boron content, the recovery rate is high, the process is long, and the reagent consumption is high. In the extraction and back extraction processes of the extraction method, an extractant is partially dissolved and damaged in water, so that the equipment is seriously corroded, and environmental pollution to a certain degree is easily caused.
At present, the utilization of magnesium resources is mainly concentrated on primary magnesium compounds (magnesium hydroxide, magnesium oxide, magnesium carbonate and the like), magnesium building materials, magnesium refractory materials, magnesium alloy and the like, and the magnesium resources are few in variety and low in additional value. The capacity of the high-value magnesium-based functional material is relatively low, but the expected capacity and demand increase is the largest in the future 5-10 years.
Layered Double Hydroxides (L-hydrated Hydroxides, abbreviated as L DHs) are anionic layered materials which have been developed rapidly in recent years and have a chemical general formula of M2+ 1–xM3+ x(OH)2(An– x/n)·yH2And O. Its structure is similar to brucite Mg (OH)2The structure is similar: with Mg2+Divalent and trivalent metal ions (Al) of similar radii3+、Co3+、Fe3+、In3+、Ga3+Etc.) partial or complete isomorphous substitution and covalent bonding to form a host laminate; interlayer anion (CO)3 2-、NO3 -、Cl-、OH-、SO4 2-、PO4 3-、B4O7 2-Etc.) are uniformly distributed, the positive charges of the host layer plate are balanced by electrostatic acting force, so that the crystal is in electric neutrality, and meanwhile, hydrogen bonds and intermolecular acting force exist among the host and the guest, and a large class of hydrotalcite-like magnesium-based functional material with a supermolecular structure is formed.
The developed series of magnesium-based L DHs functional materials comprise a lead-free heat stabilizer, a halogen-free high-smoke-suppression flame retardant, a selective infrared absorption material, an ultraviolet blocking material, a selective adsorption material, a fluorine-containing water treatment agent, a soil remediation agent and the like, and if the research and the industrial implementation of the key scientific and technical problems of the macro-preparation of the magnesium-based L DHs are actively promoted, the total demand is expected to exceed 100 million tons per year, and the effective and high-value utilization of the magnesium resources in the salt lake can be greatly promoted.
The utilization of the Qinghai salt lake brine resources currently exists:
(1) the Qinghai lake brine has rich magnesium and lithium resources, but has high magnesium-lithium ratio which is ten to thousands of times higher than that of the Qinghai lake brine abroad, is difficult to separate magnesium and lithium, is a worldwide problem, and has low utilization rate of the magnesium and lithium resources.
(2) Because the development of salt lake resources is too comprehensive for a long time, the development and utilization of single resources are concentrated, and the long-term heavy potassium and light magnesium cause magnesium harm to the huge amount of magnesium resources in the salt lake brine. The cost for extracting potassium is increased year by year, the natural environment and the mining environment of the salt lake are gradually worsened, the economy and resource balance mining of the utilization of resources such as potassium, lithium, boron and the like are seriously influenced, and the method becomes a bottleneck of the comprehensive development and utilization of the salt lake resources.
(3) In the process of preparing lithium carbonate by using salt lake brine, the defects of high energy consumption, secondary pollution, high lithium loss, easiness in shunting, low concentration rate, high cost and the like exist in several methods for concentrating and enriching lithium solution.
(4) The boron resource in the existing brine is used as the early-stage impurity in the lithium extraction process, the removal means is complex, and the lithium extraction process and the production cost are increased.
According to the chemical composition characteristics of salt lake brine in China, aiming at the scientific and technical problems faced by the separation of magnesium, lithium and boron in high-magnesium brine at present, the invention discloses a method for separating magnesium, lithium and boron resources in brine based on precipitation-ion imprinting coupling, wherein a magnesium-based functional material and lithium carbonate are obtained while the resources are separated, so that the high-efficiency and balanced utilization of the resources is really realized, and the method has great significance for improving the technical level of salt lake chemical industry in China, vigorously developing the salt lake industry in China and promoting the economic and sustainable development of the salt lake in China.
Disclosure of Invention
The invention aims to provide a method for separating magnesium, lithium and boron from brine based on precipitation-ion imprinting coupling.
The method uses magnesium in brine as a raw material, aluminum source and precipitator are added to enable magnesium and aluminum to be rapidly precipitated, boron anions enter interlamination to obtain boron-rich magnesium base L DHs, and the boron-rich magnesium base L DHs can be directly used as a high smoke suppression fire retardant after being filtered, washed and dried, or the boron anion and sodium carbonate solution are subjected to ion exchange, interlamination anion borate is exchanged into the solution, boric acid is obtained after acidification, lithium ions in brine are remained in the filtrate, and lithium is enriched and extracted by using a lithium ion imprinted polymer.
In order to achieve the purpose, the invention adopts the following technical scheme:
adding an aluminum source and a precipitator into salt lake brine, quickly nucleating, isolating and crystallizing to ensure that magnesium is precipitated and boron anions enter interlamination to obtain boron-rich magnesium-based L DHs, filtering, washing, drying, and then directly using as a high smoke suppression fire retardant, or performing ion exchange with a sodium carbonate solution, exchanging interlamination borate anions into the solution, acidifying to obtain boric acid, and remaining lithium ions in brine in filtrate to enrich and extract lithium by using a lithium ion imprinted polymer.
The method comprises the following specific steps:
(1) magnesium deposition rich in boron
Weighing a certain amount of aluminum source, adding the aluminum source into salt lake brine, fully stirring and uniformly mixing, then weighing a certain amount of alkali to be dissolved in water to prepare a precipitator, quickly nucleating the brine solution and the precipitator under high-speed shearing and stirring, then keeping a certain temperature, stirring speed and system pH value for crystallization for 1-12 h, then filtering the reaction solution, washing a filter cake to be alkalescent or neutral by pure water, and performing spray drying to obtain a high smoke-suppression flame retardant (MgAl-B-L DHs), reserving lithium ions in the filtrate, and enriching and extracting lithium by an ion imprinting technology;
(2) extracting boron
Adding the solid obtained in the step (1) into a sodium carbonate solution for ion exchange, exchanging borate anions between layers of boron-rich magnesium base L DHs out of the layers by carbonate, realizing boron enrichment, and then acidifying, concentrating and crystallizing to obtain boric acid;
(3) lithium extraction by ion imprinting technology
And (2) adding a proper amount of lithium ion imprinted polymer into the filtrate obtained in the step (1), fully trapping lithium ions in the filtrate, filtering and separating, desorbing the lithium ions by using bipolar membrane electrodialysis on the lithium ion-trapped imprinted polymer to obtain a lithium chloride concentrated solution, realizing the regeneration of the lithium ion imprinted polymer and the enrichment of the lithium ions, and adding sodium carbonate into the obtained lithium chloride concentrated solution to precipitate lithium carbonate.
The brine in the method is old brine obtained by extracting potassium from brine in Qinghai salt lake in China, and has higher magnesium-lithium ratio.
The aluminum source in the method is one or a mixture of two of aluminum chloride, aluminum nitrate, aluminum hydroxide and pseudo-boehmite.
The precipitant is one of sodium hydroxide and potassium hydroxide.
In the method, the added amount of the aluminum is Mg in brine2+The amount of the substance is 1/5-1/2.
In the step (1) in the method, the pH value of the crystallization reaction is 8-12, the reaction time is 1-12 h, and the reaction temperature is 25-100 ℃.
In the step (1) of the above method, the crystallization temperature is 50 deg.CoC~100oC。
In the step (1) of the above process, the amount of the base is Mg2+And Al3+1.5 to 4 times the sum of the amounts of the substances.
In the step (2) in the method, the concentration of the sodium carbonate solution is 1-5 mol/L.
In the step (3) of the above method, the lithium ion imprinted polymer is a cellulose-modified cross-linked ion imprinted polymer.
The method has the advantages that through the precipitation-ion imprinting coupling separation technology, magnesium, lithium and boron in brine can be directly separated, the boron-rich magnesium-based L DHs which are high smoke suppression flame retardants are obtained, boric acid and lithium carbonate products are further obtained, and the comprehensive utilization of magnesium, lithium and boron resources is realized.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
Weigh 1.030KgAlCl3·6H2Brine containing O dissolved in 10L (Mg is measured)2+The concentration is 1.28 mol/L i+0.032 mol/L of boron 0.021 mol/L), weighing 1.365Kg of NaOH, dissolving in 5L pure water to prepare a precipitant, quickly mixing brine added with aluminum salt and the precipitant under high-speed shearing and stirring within 5-30 min, adjusting pH =10, crystallizing for 8h at 100 ℃, filtering and washing to obtain MgAl-B-L DHs1.188 Kg., and determining Mg in the obtained filtrate2+The residue ratio was 0.009%, L i+The retention rate is 96.98%, the boron residual rate is 0.020%, 100g of lithium ion imprinted polymer is added into the filtrate, the mixture is fully stirred, adsorbed and filtered, and L i is added into the filtrate+It is hardly detectable. And then the imprinted polymer after trapping lithium ions is subjected to electrodialysis by using a bipolar membrane to separate out lithium chloride, and sodium carbonate is added to obtain 11.5g of lithium carbonate precipitate.
Example 2
Weigh 0.773KgAlCl3·6H2Brine containing O dissolved in 10L (Mg is measured)2+The concentration is 1.28 mol/L i+0.032 mol/L, 0.021 mol/L) and 1.285KgNaOH, dissolving in 5L pure water to prepare precipitant, adding aluminum salt into brine and precipitant, quickly mixing under high-speed shearing and stirring within 5-30 min, adjusting pH =11, crystallizing at 65 ℃ for 12h, filtering and washing to obtain MgAl-B-L DHs1.115 Kg., and determining Mg in the obtained filtrate2+The residual ratio was 0.001%, L i+The retention rate is 98.18%, the boron residual rate is 0.012%, 75g of lithium ion imprinted polymer is added into the filtrate, the mixture is fully stirred, adsorbed and filtered, and L i is added into the filtrate+It is hardly detectable. And then the imprinted polymer after trapping lithium ions is subjected to electrodialysis by using a bipolar membrane to separate out lithium chloride, and sodium carbonate is added to obtain 11.6g of lithium carbonate precipitate.
Example 3
Weigh 1.546KgAlCl3·6H2Brine containing O dissolved in 10L (Mg is measured)2+The concentration is 1.28 mol/L i+0.032 mol/L, 0.021 mol/L) and 1.556KgNaOH, dissolving in 5L pure water to prepare a precipitant, adding aluminum salt brine and the precipitant, quickly mixing under high-speed shearing and stirring within 5-30 min, adjusting pH =12, crystallizing at 60 ℃ for 12h, filtering and washing to obtain MgAl-B-L DHs1.442 Kg., and determining Mg in the obtained filtrate2+The residual ratio was 0.001%, L i+The retention rate is 98.18%, the boron residual rate is 0.012%, 75g of lithium ion imprinted polymer is added into the filtrate, the mixture is fully stirred, adsorbed and filtered, and L i is added into the filtrate+It is hardly detectable. And then the imprinted polymer after trapping lithium ions is subjected to electrodialysis by using a bipolar membrane to separate out lithium chloride, and sodium carbonate is added to obtain 11.6g of lithium carbonate precipitate.
Example 4
Weigh 1.345Kg Al (NO)3)·9H2Brine containing O dissolved in 10L (Mg is measured)2+The concentration is 1.28 mol/L i+0.032 mol/L of boron 0.021 mol/L), weighing 1.365Kg of NaOH, dissolving in 5L pure water to prepare a precipitant, quickly mixing brine added with aluminum salt and the precipitant under high-speed shearing and stirring within 5-30 min, adjusting pH =10, crystallizing at 100 ℃ for 6h, filtering and washing to obtain MgAl-B-L DHs1.228 Kg., and determining Mg in the obtained filtrate2+The residual ratio was 0.012%, L i+The retention rate is 95.67%, the boron residual rate is 0.025%, 50g of lithium ion imprinted polymer is added into the filtrate, the mixture is fully stirred, adsorbed and filtered, and L i is added into the filtrate+It is hardly detectable. And then the imprinted polymer after trapping lithium ions is subjected to electrodialysis by using a bipolar membrane to separate out lithium chloride, and sodium carbonate is added to obtain 11.3g of lithium carbonate precipitate.
Example 5
Weighing 0.333Kg Al (OH)3Brine (determined to be Mg) added to 10L2+The concentration is 1.28 mol/L i+0.032 mol/L, 0.021 mol/L) into emulsion, weighing 1.125KgNaOH, dissolving in 5L pure water to prepare precipitant, quickly mixing the aluminium-containing brine and precipitant under high-speed shearing and stirring within 5-30 min, adjusting pH =12, crystallizing at 100 ℃ for 12h, filtering and washing to obtain MgAl-B-L DHs1.222 Kg., and determining Mg in the obtained filtrate2+The residual ratio was 0.001%, L i+The retention rate was 95.23% and the boron residue rate was 0.012%, 75g of lithium ion imprinted polymer was added to the filtrate, and the mixture was sufficiently stirred, adsorbed and filtered to obtain L i+It is hardly detectable. And then the imprinted polymer after trapping lithium ions is subjected to electrodialysis by using a bipolar membrane to separate out lithium chloride, and sodium carbonate is added to obtain 11.2g of lithium carbonate precipitate.
Example 6
0.250Kg of pseudoboehmite was weighed into 10L brine (Mg was measured)2+The concentration is 1.28 mol/L i+0.032 mol/L, 0.021 mol/L) to form emulsion, weighing 1.050KgNaOH, dissolving in 5L pure water to prepare precipitant, quickly mixing aluminum-containing brine and precipitant under high-speed shearing and stirring within 5-30 min, adjusting pH =11, crystallizing at 80 ℃ for 12h, filtering and washing to obtain MgAl-B-L DHs1.111 Kg., and determining Mg in the obtained filtrate2+The residual ratio was 0.001%, L i+The retention rate is 94.29%, the boron residual rate is 0.010%, 50g of lithium ion imprinted polymer is added into the filtrate, the mixture is fully stirred, adsorbed and filtered, and L i is added into the filtrate+It is hardly detectable. And then the imprinted polymer after trapping lithium ions is subjected to electrodialysis by using a bipolar membrane to separate out lithium chloride, and sodium carbonate is added to obtain 11.1g of lithium carbonate precipitate.
Example 7
MgAl-B-L DHs obtained in example 1 was added to 100ml of 1 mol/L sodium carbonate solution, ion-exchanged, filtered, and the filtrate was made acidic with hydrochloric acid to obtain a boric acid solution, which was then concentrated to crystallize 1.2g of boric acid.
Example 8
MgAl-B-L DHs obtained in example 5 was added to 75ml of 5 mol/L sodium carbonate solution, ion-exchanged, filtered, and the filtrate was made acidic with hydrochloric acid to obtain a boric acid solution, and then 1.2g of crystallized boric acid was concentrated.
Example 9
The high smoke-suppression flame retardant MgAl-B-L DHs obtained in the embodiments 1-6 is added into PP, and the prepared flame-retardant PP composite material has a good smoke-suppression flame-retardant effect, and the flame-retardant effect reaches V0 level.
Claims (8)
1. A method for separating magnesium, lithium and boron from brine based on precipitation-ion imprinting coupling is characterized in that salt lake brine is used as a raw material, an aluminum source and a precipitator are added, after rapid nucleation, isolation and crystallization are carried out, magnesium is precipitated while boron anions enter between layers, boron-rich magnesium-based layered double metal hydroxide (MgAl-B-L DHs) is obtained, the obtained product is filtered, washed and dried and can be directly used as a high smoke suppression fire retardant, or the obtained product is subjected to ion exchange with a sodium carbonate solution, interlayer anion borate is exchanged into the solution to obtain a concentrated solution, boric acid is obtained after acidification, lithium ions in the brine are remained in the filtrate, and the lithium is enriched and extracted by an ion imprinting technology, and the specific steps are as follows:
(1) magnesium deposition rich in boron
Weighing a certain amount of aluminum source, adding the aluminum source into brine, fully stirring and uniformly mixing, weighing a certain amount of alkali, dissolving the alkali in water to prepare a precipitator, quickly nucleating brine salt solution and the precipitator under high-speed shearing and stirring, keeping a certain temperature, stirring speed and system pH value, crystallizing for 1-12 hours, filtering reaction liquid, washing a filter cake to be alkalescent or neutral by pure water, and performing spray drying to obtain a high smoke-suppression flame retardant (MgAl-B-L DHs), wherein lithium ions are retained in a filtrate, and lithium is enriched and extracted by a lithium ion imprinted polymer;
(2) extracting boron
Adding the undried solid obtained in the step (1) into a sodium carbonate solution with a certain concentration for ion exchange, exchanging borate anions between layers of boron-rich magnesium L DHs by carbonate ions out of the layers to realize boron enrichment, and then carrying out acidification, concentration and crystallization to obtain boric acid;
(3) lithium extraction by ion imprinting technology
And (2) adding a proper amount of lithium ion imprinted polymer into the filtrate obtained in the step (1), fully trapping lithium ions in the filtrate, filtering and separating, desorbing the lithium ions by using bipolar membrane electrodialysis on the lithium ion-trapped imprinted polymer to obtain a lithium chloride concentrated solution, realizing the regeneration of the lithium ion imprinted polymer and the enrichment of the lithium ions, and adding sodium carbonate into the obtained lithium chloride concentrated solution to precipitate lithium carbonate.
2. The method for separating magnesium, lithium and boron from brine based on precipitation-ion imprinting coupling as claimed in claim 1, wherein the aluminum source is one or a mixture of aluminum chloride, aluminum nitrate, aluminum hydroxide and pseudo-boehmite.
3. The method for separating magnesium, lithium and boron from brine based on precipitation-ion imprinting coupling as claimed in claim 1, wherein the precipitating agent is one of sodium hydroxide and potassium hydroxide.
4. The method for separating magnesium, lithium and boron from brine based on precipitation-ion imprinting coupling as claimed in claim 1, wherein in step (1), Al is added as aluminum source3+The amount of the substance is Mg in brine2+The amount of the substance is 1/5-1/2.
5. The method for separating magnesium, lithium and boron from brine based on precipitation-ion imprinting coupling as claimed in claim 1, wherein in step (1), the crystallization temperature is 50%oC~100oC。
6. The method for separating magnesium, lithium and boron from brine based on precipitation-ion imprinting coupling as claimed in claim 1, wherein in step (1), the amount of alkali is Mg2+And Al3+1.5 to 4 times the sum of the amounts of the substances.
7. The method for separating magnesium, lithium and boron from brine based on precipitation-ion imprinting coupling as claimed in claim 1, wherein the concentration of sodium carbonate solution in step (1) is 1-5 mol/L.
8. The method for separating magnesium, lithium and boron from brine based on precipitation-ion imprinting coupling as claimed in claim 1, wherein in step (3), the lithium ion imprinted polymer is cellulose modified cross-linked ion imprinted polymer.
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