CN116262948A - Method for activating clay type lithium ore and extracting lithium ions - Google Patents
Method for activating clay type lithium ore and extracting lithium ions Download PDFInfo
- Publication number
- CN116262948A CN116262948A CN202310408105.XA CN202310408105A CN116262948A CN 116262948 A CN116262948 A CN 116262948A CN 202310408105 A CN202310408105 A CN 202310408105A CN 116262948 A CN116262948 A CN 116262948A
- Authority
- CN
- China
- Prior art keywords
- leaching
- lithium
- clay
- activating
- lithium ions
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 83
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 81
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 35
- 230000003213 activating effect Effects 0.000 title claims abstract description 28
- 239000004927 clay Substances 0.000 title claims abstract description 21
- 238000002386 leaching Methods 0.000 claims abstract description 68
- 230000004913 activation Effects 0.000 claims abstract description 43
- 239000000843 powder Substances 0.000 claims abstract description 40
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 36
- 239000011707 mineral Substances 0.000 claims abstract description 36
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000000243 solution Substances 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 17
- 235000019253 formic acid Nutrition 0.000 claims abstract description 17
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 2
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 claims 1
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 10
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 abstract description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract 1
- 235000010755 mineral Nutrition 0.000 description 29
- 239000002893 slag Substances 0.000 description 13
- 238000001816 cooling Methods 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 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 6
- 238000000605 extraction Methods 0.000 description 6
- 229910052642 spodumene Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910001868 water Inorganic materials 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000012190 activator Substances 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052629 lepidolite Inorganic materials 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 239000004115 Sodium Silicate Substances 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 description 2
- 235000011151 potassium sulphates Nutrition 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- LDMOEFOXLIZJOW-UHFFFAOYSA-N 1-dodecanesulfonic acid Chemical compound CCCCCCCCCCCCS(O)(=O)=O LDMOEFOXLIZJOW-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 229910000503 Na-aluminosilicate Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 description 1
- 229910001760 lithium mineral Inorganic materials 0.000 description 1
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000429 sodium aluminium silicate Substances 0.000 description 1
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/16—Extraction of metal compounds from ores or concentrates by wet processes by leaching in organic solutions
- C22B3/1608—Leaching with acyclic or carbocyclic agents
- C22B3/1616—Leaching with acyclic or carbocyclic agents of a single type
- C22B3/165—Leaching with acyclic or carbocyclic agents of a single type with organic acids
-
- 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)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a method for activating clay type lithium ores and extracting lithium ions, and relates to the technical field of lithium ore exploitation. The invention is that clay type lithium ore is dried, crushed and sieved to obtain mineral powder; then activating the mineral powder by adopting a cyclic heating activation technology, and leaching by utilizing a low-concentration formic acid aqueous solution to obtain leaching solution containing lithium ions. The leaching solution prepared by the invention has high lithium ion content and few impurity types, and is convenient for purification and preparation of battery grade lithium carbonate.
Description
Technical Field
The invention belongs to the technical field of lithium ore exploitation, and particularly relates to a method for activating clay-type lithium ore and extracting lithium ions.
Background
The development of new energy materials puts higher demands on the development and utilization of lithium resources, and metal lithium and compounds thereof are core raw materials of lithium ion batteries, so that the problem of source of lithium metal needs to be solved. The sources of lithium metal are mainly lithium ores and lithium brine, wherein spodumene and lepidolite have been developed at present due to higher lithium elements.
The lithium extraction process aiming at spodumene and lepidolite mainly comprises the following steps: the production process of sulfuric acid method includes roasting spodumene at high temperature, cooling, grinding, mixing with sulfuric acid and leaching. The sulfate mixed sintering production process comprises the following steps: adding auxiliary agents of potassium sulfate or calcium sulfate or a mixture of the potassium sulfate and the calcium sulfate into minerals, mixing and sintering at a certain temperature, and leaching and separating the sintered clinker by sulfuric acid. The sodium carbonate pressure leaching production process comprises the following steps: heating spodumene to perform crystal form transformation, adding sodium carbonate, mixing, pressurizing and leaching in a reactor, and introducing carbon dioxide gas to generate soluble lithium bicarbonate. The chloridizing roasting production process mixes spodumene with limestone and calcium chloride, roasting at high temperature to produce lithium chloride sublimate, feeding the sublimate and dust into kiln gas, and collecting chloridizing solution in dust collector and washing tower.
With the increasing demand for metallic lithium, the technology of exploiting and extracting lithium from deposited lithium-poor resources is urgent. Because the content of lithium elements in the poor lithium resources is low, the green efficient lithium-rich flotation, the efficient leaching purification, the efficient comprehensive utilization of solid wastes and other integrated processes and technology development become key factors influencing the market trend of the lithium resources.
Clay-type lithium ores belong to a kind of lithium-poor resource. At present, research on lithium extraction of lithium-containing clay minerals at home and abroad mainly uses spodumene and lepidolite process technologies, but the lithium extraction technology cannot improve the extraction rate and has higher treatment cost. Based on this, researchers have developed an activation and leaching process for clay-type lithium ores: for example, patent CN202210353260.1 developed a lithium extraction technique for clay ore, clay is mixed with alkali and a melting agent, and calcined at high temperature, the obtained calcined clinker is leached in water, and sodium aluminate or sodium silicate is added into the obtained reaction solution to adjust the sodium aluminate and the melting agentThe concentration of sodium silicate, obtain water immersion liquid and sodium aluminosilicate precipitate, add carbon dioxide gas, wash the precipitate with water, add into drier, dry and get lithium carbonate product; mixing clay type lithium ore, sodium bicarbonate and water in a patent CN202210866437.8 to obtain raw ore pulp; leaching the raw ore pulp, performing solid-liquid separation to obtain solid phase slag and lithium-containing leaching solution, and performing high-temperature roasting on washed lithium aluminum hydrotalcite to obtain lithium aluminate (Li) 2 Al 4 O 7 ) The method comprises the steps of carrying out a first treatment on the surface of the In patent CN202210867554.6, lithium clay powder and a lithium ion exchange solution are mixed to prepare slurry, then an ultrasonic enhanced leaching reaction is performed, a lithium extracting solution and filter residues are obtained through separation, a lithium extractant is used for extracting the lithium extracting solution, a lithium loaded organic phase and a raffinate are obtained through separation, a stripping agent is used for stripping the lithium loaded organic phase, a lithium-rich solution and a stripping organic phase are obtained through separation, and then oil removal and purification operations are performed on the lithium-rich solution to obtain a lithium chloride refined solution.
The technology of the patent mainly adopts an activator to carry out mixed roasting on clay type lithium ores, and the activator mainly has the function of carrying out chemical reaction with the lithium-containing ores, so that lithium elements are changed into soluble salts, the subsequent leaching is convenient, the leaching rate of the lithium elements is improved, and in addition, the lattice structure of the lithium ores is changed through high-temperature roasting, and the leaching rate of lithium is improved.
Since the lithium taste in clay-type lithium ores is low, generally, the production of 1 ton of lithium carbonate produces more than 100 tons of slag. The use of the above-described patent technology to treat low-grade lithium ores (using a large amount of activator) further exacerbates the increase in slag content. Meanwhile, the high-temperature treatment not only can cause the increase of energy consumption, but also can cause the change of the ore structure after the high-temperature treatment, so that a large amount of soluble metal ions are brought in the subsequent acid leaching process, and great risks are brought to the recycling of solid wastes and the environment. Therefore, the development of a green lithium extraction technology, the research of a novel clay type lithium ore activation technology and a leaching technology become the key of exploitation and utilization of the lithium ore.
Disclosure of Invention
In view of the shortcomings of the prior art, the technical purpose of the invention is to provide a method for activating clay-type lithium ores and extracting lithium ions. The method is characterized in that organic matters in mineral powder are carbonized and cracked by a cyclic heating activation technology, so that a channel is opened for volatilization of free water and crystallization water of the mineral powder in sudden temperature change. Meanwhile, partial polar groups are left in the pore canal after the organic matter is carbonized and cracked, so that a microchemical environment is created for formic acid molecules of the subsequent leaching solution to enter a microporous structure and exchange ions with lithium ions, and the leaching rate of the lithium ions is improved. The technical scheme of the invention does not damage the phases of minerals and the main components of minerals, reduces the damage to the environment, and lays an important foundation for the harmless and recycling utilization of slag. The technology is suitable for large-scale industrial production.
In order to achieve the above object, the technical scheme of the present invention is as follows:
a method of activating clay-type lithium ores and extracting lithium ions, comprising the steps of:
(1) Drying, crushing and sieving clay type lithium ore to obtain mineral powder for later use;
(2) Circularly heating and activating mineral powder to obtain activated mineral powder, wherein the single heating time is 10 s-10 min, and the heating temperature is 350-800 ℃;
(3) Placing activated mineral powder into a leaching agent according to a solid-liquid ratio of 1g to 1mL to 1g to 20mL, then adding a surfactant accounting for 0.05 to 0.5 percent of the mass ratio of the activated mineral powder, finally leaching at a temperature of between 40 and 100 ℃, and carrying out solid-liquid separation after leaching to obtain leaching solution containing lithium ions;
the leaching agent is formic acid aqueous solution.
Preferably, the particle size of the mineral powder in the step (1) is 100-300 meshes.
Preferably, the cycle number of the cyclic heating activation in the step (2) is 2-4.
Preferably, the concentration of formic acid in the formic acid aqueous solution in the step (3) is 0.05mol/L to 0.8mol/L.
Preferably, the surfactant in the step (3) is at least one of cetyltrimethylammonium bromide, triethanolamine and dodecyl sulfonate.
Preferably, the leaching temperature in step (3) is 40-80 ℃.
It is further preferred that the leaching time in step (3) is 0.5 to 10 hours.
Preferably, the content of lithium ions in the leaching solution in the step (3) is 80 mg/L-1000 mg/L.
Compared with the prior art, the invention has the following beneficial effects:
compared with the prior art which uses a strong acid leaching method such as adding a chemical activator or sulfuric acid, the method for activating clay type lithium ore and extracting lithium ions has the characteristics of short activation time, low temperature and energy consumption, no great change on the phase structure and chemical composition of minerals and avoidance of generating a large amount of slag. The invention adopts formic acid aqueous solution to leach, has small dissolution to chemical components of mineral powder, does not damage the porous structure of the mineral powder, effectively improves the leaching rate of lithium elements, has low impurity ion content in leaching solution, and is favorable for subsequent refining and preparing battery-grade lithium carbonate.
The method has high production efficiency, is beneficial to large-scale mass production and has little negative influence on the ecological environment.
Drawings
FIG. 1 is an SEM image before activation of clay-type lithium ore powder of example 1;
FIG. 2 is an SEM image of clay-type lithium ore powder after activation of example 1;
FIG. 3 is a XRD comparison of slag before activation of clay-type lithium ore powder according to the present invention and after leaching in examples 1, 4 and 10;
FIG. 4 is a BET plot of clay-type lithium ore powder of example 3 prior to activation;
FIG. 5 is a BET plot of the clay-type lithium ore powder of example 3 after activation;
wherein in fig. 3, the number 4 is clay type lithium mineral powder XRD;3# is slag XRD after leaching of example 1; 2# is slag XRD after leaching of example 4; 1# is slag XRD after leaching in example 10.
Detailed Description
The invention will be further illustrated with reference to specific examples. Wherein, the clay type lithium ore used in the invention is Guizhou clay ore.
Example 1
A method for activating clay-type lithium ores and extracting lithium ions, comprising the following steps:
(1) Weighing 20g of clay type lithium ore, drying at 120 ℃ for 4 hours, crushing, and sieving with a 200-mesh sieve; obtaining mineral powder;
(2) Heating mineral powder at 550 ℃ for a first activation pretreatment, wherein the time of the first activation treatment is 6min, cooling to 40 ℃, heating to 400 ℃, and performing a second activation treatment, wherein the time of the second activation treatment is 3min, and cooling to room temperature to obtain activated mineral powder;
(3) The activated mineral powder is placed in a leaching agent, wherein the solid-liquid ratio is 1g to 15mL, the formic acid concentration in the leaching agent is 0.4mol/L, then cetyltrimethylammonium bromide accounting for 0.06% of the mass of the activated mineral powder is added, magnetic stirring is carried out at 80 ℃, the rotating speed is 60r/min, solid-liquid separation is carried out after leaching for 4 hours, and leaching liquid containing lithium ions and solid slag are obtained.
Table 1 shows the mass percentages of the components in clay-type lithium ore powder and leached slag according to example 1.
TABLE 1
Example 2
A method for activating clay-type lithium ores and extracting lithium ions, refer to example 1. The difference is that the first activation temperature in the step (2) is 450 ℃ and the activation time is 3min;
the leaching temperature in step (3) was 70 ℃.
The remainder was the same as in example 1.
Example 3
A method for activating clay-type lithium ores and extracting lithium ions, refer to example 1. The difference is that the first activation temperature in step (2) was 530℃and the activation time was 3min.
The leaching time of the step (3) is 3h.
The remainder was the same as in example 1.
Example 4
A method for activating clay-type lithium ores and extracting lithium ions, refer to example 1. The difference is that the second activation temperature in the step (2) is 420 ℃ and the activation time is 4min.
The leaching temperature of the step (3) is 40 ℃, and the concentration of formic acid in the leaching agent is 0.1mol/L.
The remainder was the same as in example 1.
Example 5
A method for activating clay-type lithium ores and extracting lithium ions, refer to example 1. Except that the second activation temperature in step (2) was 470℃and the activation time was 5min.
The leaching temperature of the step (2) is 40 ℃, and the concentration of formic acid in the leaching agent is 0.2mol/L.
The remainder was the same as in example 1.
Example 6
A method for activating clay-type lithium ores and extracting lithium ions, refer to example 1. The difference is that the second activation temperature in the step (2) is 370 ℃ and the activation time is 5min.
The leaching temperature of the step (2) is 50 ℃, and the concentration of formic acid in the leaching agent is 0.2mol/L.
The remainder was the same as in example 1.
Example 7
A method for activating clay type lithium ore and extracting lithium ions comprises the following specific steps:
(1) Weighing 20g of clay type lithium ore, drying at 120 ℃ for 4 hours, crushing and sieving with a 200-mesh sieve; obtaining mineral powder;
(2) Heating mineral powder at 550 ℃ for a first activation pretreatment, wherein the time of the first activation treatment is 6min, cooling to 40 ℃, heating to 460 ℃ and performing a second activation treatment, wherein the time of the second activation treatment is 3min, cooling to 70 ℃, heating to 430 ℃ for a third activation treatment, and cooling to room temperature for 5min to obtain activated mineral powder;
(3) Placing activated mineral powder into a leaching agent, wherein the solid-liquid ratio is 1g to 10mL, the concentration of formic acid in the leaching agent is 0.1mol/L, then adding triethanolamine accounting for 0.1% of the mass of the activated mineral powder, magnetically stirring at 80 ℃, leaching at the rotating speed of 60r/min, and performing solid-liquid separation after leaching for 4 hours to obtain leaching solution containing lithium ions and solid slag.
Example 8
A method of activating clay-type lithium ores and extracting lithium ions, see example 7. The difference is that the third activation temperature in the step (2) is 350 ℃ and the activation time is 2min.
The leaching temperature of the step (3) is 70 ℃, and the concentration of formic acid in the leaching agent is 0.15mol/L.
The remainder was the same as in example 7.
Example 9
A method of activating clay-type lithium ores and extracting lithium ions, see example 7. The difference is that the second activation temperature in step (2) was 480℃and the activation time was 4min.
The leaching temperature of the step (3) is 65 ℃, and the concentration of formic acid in the leaching agent is 0.1mol/L.
The remainder was the same as in example 7.
Example 10
A method for activating clay type lithium ore and extracting lithium ions comprises the following specific steps:
(1) Weighing 20g of clay type lithium ore, drying at 120 ℃ for 4 hours, crushing and sieving with a 200-mesh sieve; obtaining mineral powder;
(2) Heating mineral powder at 750 ℃ for a first activation pretreatment, wherein the time of the first activation treatment is 6min, cooling to 40 ℃, heating to 460 ℃, and performing a second activation treatment, wherein the time of the second activation treatment is 3min, cooling to 70 ℃, heating to 430 ℃ for a third activation treatment, the activation time is 5min, cooling to 70 ℃, heating to 400 ℃ for a fourth activation treatment, the activation time is 30s, and cooling to room temperature to obtain activated mineral powder;
(3) The activated mineral powder is placed in a leaching agent, wherein the solid-liquid ratio is 1g to 10mL, the formic acid concentration in the leaching agent is 0.1mol/L, then sodium dodecyl benzene sulfonate accounting for 0.2% of the mass of the activated mineral powder is added, magnetic stirring is carried out at 80 ℃, the rotating speed is 60r/min, solid-liquid separation is carried out after leaching for 4 hours, and leaching liquid containing lithium ions and solid slag are obtained.
The concentrations of the respective elements in the lithium ion-containing leaching solutions prepared in examples 1 to 10 of the present invention are shown in table 2.
Table 2 ion content in the leachate containing lithium ions in examples
It should be noted that the above-mentioned embodiments are only a few specific embodiments of the present invention, and it is obvious that the present invention is not limited to the above embodiments, but other modifications are possible. All modifications directly or indirectly derived from the disclosure of the present invention will be considered to be within the scope of the present invention.
Claims (8)
1. A method for activating clay-type lithium ores and extracting lithium ions, comprising the steps of:
(1) Drying, crushing and sieving clay type lithium ore to obtain mineral powder for later use;
(2) Circularly heating and activating mineral powder to obtain activated mineral powder, wherein the single heating time is 10 s-10 min, and the heating temperature is 350-800 ℃;
(3) Placing activated mineral powder into a leaching agent according to a solid-liquid ratio of 1g to 1mL to 1g to 20mL, then adding a surfactant accounting for 0.05 to 0.5 percent of the mass ratio of the activated mineral powder, finally leaching at a temperature of between 40 and 100 ℃, and carrying out solid-liquid separation after leaching to obtain leaching solution containing lithium ions;
the leaching agent is formic acid aqueous solution.
2. The method for activating and extracting lithium ions from clay-type lithium ore according to claim 1, wherein the particle size of the ore powder in step (1) is 100 mesh to 300 mesh.
3. The method for activating and extracting lithium ions from clay-type lithium ore according to claim 1, wherein the number of cycles of the cyclic heat activation in step (2) is 2 to 4.
4. The method for activating and extracting lithium ions from clay-type lithium ore according to claim 1, wherein the concentration of formic acid in the aqueous formic acid solution in step (3) is 0.05mol/L to 0.8mol/L.
5. The method for activating and extracting lithium ions from clay-type lithium ore according to claim 4, wherein the surfactant in step (3) is at least one of cetyltrimethylammonium bromide, triethanolamine, and dodecylbenzene sulfonate.
6. The method for activating and extracting lithium ions from clay-type lithium ores according to claim 1, wherein the leaching temperature in step (3) is 40 to 80 ℃.
7. The method for activating and extracting lithium ions from clay-type lithium ore according to claim 6, wherein the leaching time in step (3) is 0.5 to 10 hours.
8. The method for activating and extracting lithium ions from clay-type lithium ore according to claim 1, wherein the content of lithium ions in the leaching solution in the step (3) is 80mg/L to 1000mg/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310408105.XA CN116262948A (en) | 2023-04-17 | 2023-04-17 | Method for activating clay type lithium ore and extracting lithium ions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310408105.XA CN116262948A (en) | 2023-04-17 | 2023-04-17 | Method for activating clay type lithium ore and extracting lithium ions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116262948A true CN116262948A (en) | 2023-06-16 |
Family
ID=86723181
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310408105.XA Pending CN116262948A (en) | 2023-04-17 | 2023-04-17 | Method for activating clay type lithium ore and extracting lithium ions |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116262948A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117107073A (en) * | 2023-09-15 | 2023-11-24 | 唐山鑫丰锂业有限公司 | Method for extracting lithium from lithium-containing ore |
-
2023
- 2023-04-17 CN CN202310408105.XA patent/CN116262948A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117107073A (en) * | 2023-09-15 | 2023-11-24 | 唐山鑫丰锂业有限公司 | Method for extracting lithium from lithium-containing ore |
| CN117107073B (en) * | 2023-09-15 | 2024-03-12 | 唐山鑫丰锂业有限公司 | Method for extracting lithium from lithium-containing ore |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103145158B (en) | Method for preparing lithium carbonate from lepidolite through sulfuric acid roasting method | |
| CN102244309B (en) | Method for recovering lithium from lithium power battery of electric automobile | |
| CN110885090A (en) | Method for preparing battery-grade lithium carbonate by using lepidolite as raw material through one-step method | |
| CN104876250B (en) | Method for extracting lithium and removing aluminum by treating lepidolite with sulfuric acid | |
| CN103614547B (en) | Method for separating iron, aluminum and silicon from diasporic bauxite | |
| CN107017444A (en) | A kind of method of metal recovery in waste lithium iron phosphate battery | |
| CN115216645B (en) | Method for extracting lithium from electrolytic aluminum waste residue by mixed salt calcination | |
| CN102531002A (en) | Method for purifying lithium carbonate | |
| CN108584994A (en) | A kind of method of lepidolite calcined by rotary kiln lithium carbonate | |
| CN113930619A (en) | Method for preferentially extracting lithium from waste ternary lithium ion battery anode material and recovering valuable metal | |
| CN104131167A (en) | Method for recovering selenium and manganese in manganese anode slime by using microwaves | |
| CN110510642A (en) | A kind of method that low-grade α spodumene economy mentions lithium | |
| CN112095000A (en) | Method for recovering cobalt and lithium metals from waste lithium cobalt oxide batteries | |
| CN108677006B (en) | Method for extracting rubidium chloride from kaolin tailings | |
| CN116262948A (en) | Method for activating clay type lithium ore and extracting lithium ions | |
| CN114436300A (en) | Method for acidifying and leaching lithium by spodumene | |
| CN113562770B (en) | Method for recycling iron and sodium resources in red mud in gradient manner and fully utilizing tailings | |
| CN108063295A (en) | The method that lithium is extracted in the clinker generated from pyrogenic process recycling lithium battery | |
| CN217202898U (en) | Lithium extraction system for lithium ore leaching slag | |
| CN113060741B (en) | Method for comprehensively utilizing boron-extracted iron tailings from ludwigite | |
| CN113387377A (en) | Method for preparing sulfuric acid system brine from low-grade lithium ore and extracting lithium | |
| CN114369729A (en) | Process for removing potassium from leaching solution by using lithium slag | |
| CN113562771A (en) | Full-quantization integral utilization method for recycling iron, sodium and tailings from Bayer process red mud step by step | |
| CN113816354A (en) | Method for preparing iron phosphate by using wastes in titanium dioxide production process | |
| CN217536121U (en) | Lithium leaching system for lithium-containing clay |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |