CN117718135A - Method for efficiently extracting lithium and high-purity quartz from low-grade hydrothermal alteration type lithium ore - Google Patents
Method for efficiently extracting lithium and high-purity quartz from low-grade hydrothermal alteration type lithium ore Download PDFInfo
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 199
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 199
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 62
- 239000010453 quartz Substances 0.000 title claims abstract description 51
- 230000004075 alteration Effects 0.000 title claims abstract description 37
- 238000002386 leaching Methods 0.000 claims abstract description 135
- 238000000605 extraction Methods 0.000 claims abstract description 64
- 239000002253 acid Substances 0.000 claims abstract description 62
- 238000003756 stirring Methods 0.000 claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000010433 feldspar Substances 0.000 claims abstract description 36
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000010445 mica Substances 0.000 claims abstract description 32
- 229910052618 mica group Inorganic materials 0.000 claims abstract description 32
- 238000005188 flotation Methods 0.000 claims abstract description 31
- 238000000227 grinding Methods 0.000 claims abstract description 27
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 22
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Abstract
The invention discloses a method for efficiently extracting lithium and high-purity quartz from low-grade hydrothermal alteration type lithium ores, belonging to the technical field of lithium ore dressing and smelting processing and comprehensive utilization, and comprising the following steps of: s1, crushing ores; s2, screening pretreatment materials; s3, grinding the oversize products; s4, stirring, scrubbing, settling and desliming; s5, carrying out weak magnetic separation; s6, strong magnetic separation; s7, reverse flotation separation; s8, hot-pressing acid leaching; s9, mixing mud; s10, lower Wen Dili; s11, slag soaking detection; s12, detecting high-purity quartz sand. Raw ore is pre-screened to coarse fraction and 40 meshes, and enters grinding, so that grinding cost is reduced, the separated total mud, mica and feldspar are respectively added with a lithium extraction reagent, pretreatment such as high-temperature roasting, adding salt roasting auxiliary agents and the like is not needed, concentrated sulfuric acid is also not needed, low-temperature low-pressure low-concentration acid and normal-temperature water immersion stirring are adopted, lithium can be directly and efficiently extracted, the corrosion to equipment is small, energy conservation and environmental protection are realized, the adaptability to raw materials is strong, the environment is clean, the lithium leaching rate is up to 90%, and the comprehensive utilization level of lithium ore is remarkably improved.
Description
Technical Field
The invention belongs to the field of dressing and smelting processing and comprehensive utilization of lithium ores, and particularly relates to a method for efficiently extracting lithium and high-purity quartz from low-grade hydrothermal alteration type lithium ores.
Background
Lithium is a rare earth metal element with the smallest atomic radius, the lightest mass and the largest ionization potential, is currently known in the world, is listed as a key metal by countries such as the United states, japan, australia and the like, is widely applied to the fields such as glass ceramics, lubricating grease, nonferrous metallurgy, clinical medicine, air treatment, high-energy batteries, atomic energy thermonuclear fusion, aerospace and the like, and enjoys the reputation of industrial monosodium glutamate, metal with the most application potential in the 21 st century and the like.
Lithium in nature is often produced in two forms, namely solid mineral resources and liquid mineral resources, wherein the solid mineral resources mainly comprise spodumene, lepidolite, petalite and the like, the hard rock type solid ore accounts for about 29%, the sedimentary lithium mineral deposit accounts for about 7%, and the liquid brine type lithium mineral accounts for about 64%. The external dependence of the lithium resource in China exceeds 80 percent. According to the current classification of the main flow of lithium mineral resources in the world, lithium mineral deposits are mainly divided into three major categories of hard rock type, salt lake brine type and sedimentary type, wherein the hard rock type lithium mineral is mainly divided into a pegmatite type and a granite type, the sedimentary type lithium mineral is mainly divided into a volcanic sedimentary type and a carbonate weathering-sedimentary type, the salt lake brine type is mainly produced in a salt lake, and the basic characteristics of various lithium minerals are respectively discussed below according to the mineral deposit types:
(1) Features of the pegmatite lithium deposit: the mineral-forming parent rock is pegmatite, the lithium element-bearing mineral is spodumene, the mineral deposit causes mainly magma differential evolution, and the high-differential pegmatite is rich in incompatible elements such as lithium, beryllium and the like, so that the mineral-forming parent rock has high differential evolution degree. (2) granite lithium deposit characteristics: the mineral-forming parent rock is granite rock, the lithium element-bearing mineral is mainly lepidolite, the mineral deposit causes mainly magma differential evolution, and the high-differential pegmatite is rich in lithium, so that the mineral-forming parent rock has high differential evolution degree. (3) volcanic deposit type lithium ore characteristics: the mineral-forming parent rock mainly comprises volcaniclastic rock such as tuff, the occurrence mineral of lithium element mainly comprises clay mineral such as hectorite and hectorite, and the mineral deposit is mainly formed by interaction between volcanic substances and hot water solution or evaporated brine to form unconventional lithium-containing mineral, thereby forming lithium ore. (4) weathering-depositing type lithium ore characteristics of carbonate rock: the mineral-forming parent rock mainly comprises carbonate rock such as limestone, the occurrence mineral of lithium element mainly comprises clay mineral such as hectorite, and the mineral deposit is formed by secondary enrichment of lithium-containing mineral through weathering deposition.
Recently, the low-grade hydrothermal alteration type lithium ore found in China is obviously different from the lithium ore resources reported in the world: firstly, the ore-forming parent rock in the Anhui prayer is prayer body granite amphibole, the lithium element-bearing mineral is mainly hydrothermal alteration mineral such as lithium chlorite, the mineral deposit is mainly the deep lithium-rich hydrothermal solution upwelling along a fracture construction channel, the mineral such as feldspar in the surrounding rock is mineralized and altered to generate lithium-rich mineral such as lithium chlorite, so that corresponding lithium ore resources are formed, the evolution degree of the prayer body parent rock is not high, and the method belongs to low-evolution granite amphibole.
Currently, there are two main materials for extracting lithium, one is extracting lithium from spodumene ore and lepidolite, and the other is extracting lithium from liquid resources such as salt lake brine and well brine. The spodumene lithium extraction process mainly comprises a sulfuric acid method, an alkaline method, a sulfate roasting method and a chloridizing roasting method; the lepidolite extraction method mainly comprises a sulfuric acid method, a limestone sintering method, a sulfate roasting method, an autoclaving method and a chloridizing roasting method. The main processes of the method are that firstly, the minerals are roasted, activated and transformed at the high temperature of 800-1200 ℃, and then, the lithium is leached by sulfuric acid to generate lithium salt. The method for extracting lithium from salt lake brine mainly comprises an evaporation crystallization method, a precipitation method, a solvent extraction method, an ion exchange adsorption method, a calcination leaching method, a salting-out method, a 'schwann' method and the like.
Patent CN 115161496A discloses a method for extracting lithium from lithium clay, which comprises roasting lithium clay powder at 500-800 ℃ for 1-5 hours, grinding the roasted clinker, mixing with leaching agent and water, leaching at 150-300 ℃ and 1.4-2.5 MPa. According to the method, all clay lithium is ground into powder and is subjected to high-temperature roasting, and the calcined and agglomerated clay lithium is required to be ground and then reacts with a leaching agent, so that the short plate with high ore grinding and high energy consumption is provided.
Patent CN 109022722A discloses a method for leaching lepidolite ore by curing sulfuric acid, which comprises the steps of mixing 90-98% of concentrated sulfuric acid into ground lepidolite concentrate, curing for 2-20 h at 100-250 ℃, curing the lepidolite concentrate by using 90-98% of concentrated sulfuric acid at a temperature of more than 100 ℃, heating the concentrated sulfuric acid to generate acid gas, corroding equipment, consuming a large amount of alkali, converting the redundant sulfuric acid into sulfate after alkali treatment, and extracting lithium with high cost.
Patent CN 115198109A discloses a method for extracting lithium from lithium-containing clay by mixed acid, which comprises the steps of fully mixing lithium-containing clay mineral powder with mixed acid of concentrated sulfuric acid and concentrated phosphoric acid according to a solid-liquid ratio of 1:3-1:8, leaching for 2-6 h at 50-150 ℃, wherein the leaching rate of lithium is 52.12%, 55.96%, 60.58%, 77.83% and 91.02%. The lithium ore is directly ground into powder and then mixed with concentrated sulfuric acid and concentrated phosphoric acid, so that equipment is strongly corroded by strong acid, the cost for extracting lithium is increased by alkali treatment, and the produced tailings are large.
CN 109593974B discloses a method for extracting lithium from lithium ore, which comprises mixing lithium ore with calcium oxide and powdered coal uniformly, reacting at 1200-1500deg.C for 0.5-3 h, quenching the reaction product with water, rapidly cooling to obtain water quenching slag, finely grinding the water quenching slag, adding sulfuric acid solution, leaching to obtain lithium-containing solution, and obtaining lithium salt from the solution by chemical precipitation.
The lithium extraction process is mature, namely grinding the lithium ore into powder, then adopting concentrated acid and the ground powder sample to mix and pretreat, calcining at high temperature or adding a calcining auxiliary agent to calcine at high temperature, and the non-metal ore such as quartz, mica and feldspar in the lithium ore is not recovered, so that the grinding cost is high, the produced tailings are large, the resource waste is caused, the equipment investment is large, and the energy consumption is high. For low-grade hydrothermal alteration type lithium ores, the cost for treating the low-grade lithium ores by adopting a high-temperature calcination method is too high, so that the development and utilization values of the lithium ores are possibly low, and therefore, the spodumene and lepidolite lithium extraction method is not suitable for the low-grade hydrothermal alteration type lithium ores.
The present invention has been made in view of this.
Disclosure of Invention
The invention aims to solve the technical problems of overcoming the defects of the prior art and providing a method for efficiently extracting lithium and high-purity quartz from low-grade hydrothermal alteration type lithium ore, which adopts a pre-screening +40 mesh coarse particle part to enter the ore grinding, preferentially enriches the lithium-containing ore after pre-discarding the tail, simultaneously adopts a novel flotation reagent to efficiently separate feldspar and quartz in the lithium ore, and the separated products are respectively added with dilute acid of a lithium extraction reagent, and adopts a low-temperature roasting-water leaching method, wherein the lithium comprehensive leaching rate is up to 90.07 percentThe use of materials, aerated bricks and the like reduces the discharge amount of tailings, and the obtained quartz concentrate SiO 2 The content is 99.94%, the Fe content is 4.38mg/kg, the standard requirement of a high-purity quartz low-end product is met, and the comprehensive utilization level of the low-grade hydrothermal alteration type lithium ore is integrally improved.
In order to solve the technical problems, the invention adopts the basic conception of the technical scheme that:
a method for efficiently extracting lithium and high-purity quartz from low-grade hydrothermal alteration type lithium ore comprises the following steps:
(1) Crushing ore: pretreating low-grade hydrothermal alteration lithium ore by a jaw crushing-twin roll crusher to obtain pretreated material with granularity of-1 mm;
(2) And (3) pretreatment material screening: performing screening and screening on the pretreated material with the diameter of-1 mm obtained in the step (1);
(3) Grinding the oversize products: grinding the +40 mesh oversize product obtained in the step (2), and sieving out-200 mesh fine mud product;
(4) Stirring, scrubbing-settling and desliming: classifying the ground ore product obtained in the step (3) to obtain-40+200 mesh coarse sand, combining the-40+200 mesh coarse sand obtained in the step (2) to obtain qualified size fraction, and stirring, scrubbing and sedimentation desliming;
(5) And (3) low-intensity magnetic separation: carrying out wet weak magnetic separation on the desliming coarse sand product obtained in the step (4) to remove iron;
(6) And (3) strong magnetic separation: carrying out strong magnetic separation on the product obtained in the step (5) after the magnetic iron is removed under a high-gradient magnetic field of 1.2-1.8T to obtain mica concentrate and nonmagnetic substances;
(7) Reverse flotation separation: carrying out reverse flotation separation on the nonmagnetic substance obtained in the step (6) under the condition of pH value of 2-3 by adopting a novel collector to obtain quartz concentrate and feldspar concentrate;
(8) Hot-pressing acid leaching: carrying out hot-pressing acid leaching, washing and drying on the flotation quartz concentrate obtained in the step (7) to obtain high-purity quartz concentrate;
(9) Combining the-200 mesh products obtained in the steps (2), (3) and (4) to obtain a total mud product;
(10) Low Wen Dili: respectively adding the mica concentrate obtained in the step (6), the feldspar concentrate obtained in the step (7) and the total mud obtained in the step (9) into a lithium extraction reagent for carrying out low Wen Dili;
(11) And (3) slag leaching detection: detecting the mica leaching residue, the feldspar leaching residue and the total mud leaching residue obtained in the step (10) by ICP-AES respectively, calculating the accumulated leaching rate of lithium on raw ore, and simultaneously carrying out SiO on the mica leaching residue and the feldspar leaching residue 2 、Al 2 O 3 、Fe 2 O 3 、K 2 O、Na 2 O analysis, examining the application in the aspects of building materials and the like;
(12) And (3) high-purity quartz sand detection: and (3) carrying out ICP-MS detection on 13 trace elements on the high-purity quartz refined sand obtained in the step (8), and checking whether the high-purity quartz index requirement can be met.
Further, in the step (1), the ore crushing equipment is a jaw crusher-twin-roll crusher-double-layer vibrating screen for a laboratory, and the requirement of-1 mm of the granularity of the pre-treated material sample after crushing is met.
In the step (2), pre-treated material with the diameter of-1 mm is used as an ore to be screened, screening equipment is a laboratory standard screening, 25 meshes, 40 meshes, 60 meshes, 80 meshes, 120 meshes, 140 meshes and 200 meshes, and the requirement of particle size classification is met.
Further, in the step (3), coarse particles on the raw ore screening plus 40 mesh sieve are ground by a three-roller four-drum rod mill for 3 to 15 minutes, and after grinding, fine mud products with the mesh of-200 are screened out, and the rest products with the mesh of-40 plus 200 are qualified.
Further, in the step (4), stirring, scrubbing and sedimentation desliming are that raw ore screening-40+200 mesh coarse sand and regrinding-40+200 mesh coarse sand, stirring, scrubbing in an XFD12 type scrubbing machine, scrubbing the ore pulp for 50% of the concentration, scrubbing for 30 minutes, and removing fine mud by a siphon sedimentation method until the ore pulp is clear.
Further, in the step (5), the weak magnetic separation is a section of wet weak magnetic separation, and the magnetic field strength is 1500-2000 Oe;
further, in the step (6), the strong magnetic separation is a section of high-gradient magnetic separation, and the magnetic field strength is 1.2-1.8T.
Further, in the step (7), the reverse flotation separation is aerated flotation, the flotation machine is an XFD12 type multi-tank flotation machine, and the process conditions are as follows: the pH value of ore pulp is regulated to 2-3, the acid is one or a mixture of sulfuric acid, oxalic acid, nitric acid and hydrochloric acid, the concentration of reverse flotation ore pulp is 15-30%, the dosage of the novel separation collector is 400-600 g/t, the dosage of the foaming agent is 50-100 g/t, the stirring rate is 800-1200 r/min, and the flotation time is 2-5 min. The novel collector is a mixture of compound amine, fatty acid and silicate inhibitor, and the foaming agent is a mixture of hydrocarbon oil and pine oil.
Further, in the step (8), the hot-press acid leaching process is at least one of ultrasonic acid leaching, stirring acid leaching and heating acid leaching, the acid is mixed acid, the mixed acid is a combination of two or more of hydrofluoric acid, nitric acid, hydrochloric acid, sulfuric acid and oxalic acid, and the leaching time is 4-24 hours.
Further, in the step (9), the mud is combined: and (3) mixing and scrubbing the fine mud of-200 meshes and the fine mud of-200 meshes which is generated after regrinding of +40 meshes and qualified size fractions of-40+200 meshes obtained from raw ore, and combining the three products into total mud.
Further, in the step (10), the low-temperature lithium extraction is as follows: the treatment temperature is 100-200 ℃, the lithium extraction reagent AC is an acid diluent, the concentration is 30-75%, the heat preservation time is 1-5 h, the water immersion stirring time is 0.5-1 h, the water immersion stirring temperature is 20-90 ℃, and the leaching residue is filtered and then washed to be neutral.
Further, in the step (11), the leaching residue detection is to weigh leaching residue sample solution, and according to the regional geochemical sample analysis method, each index detection is carried out by adopting an inductively coupled plasma atomic emission spectrometry (ICP-AES) and a colorimetry.
Further, in the step (12), the high-purity quartz sand is detected as 13 trace elements by inductively coupled plasma mass spectrometry (ICP-MS) in an ultra-clean laboratory.
The hydrothermal alteration type lithium ore Li 2 The O content is low, and the morphological analysis result of the lithium ore is that: 99.23 percent of residue state, 0.33 percent of ion adsorption state, 0.22 percent of strong organic bonding state, 0.18 percent of ferromanganese oxidation state and 0.04 percent of carbonate bonding state; only 0.65% of Li was exchanged into the solution by the cation exchange amount testIn the method, lithium is mainly added in the chlorite in a lattice form, the chlorite is easy to mud in crushing and grinding, and gangue minerals are in mineral separation, so that the lithium cannot be directly extracted by conventional mineral separation means such as gravity separation, flotation and magnetic separation, and the conventional method is to directly grind the ore into powder and add concentrated sulfuric acid or a mixture of several concentrated acids to extract lithium, so that the grinding cost is too high.
According to the invention, the lithium mineral components are obtained according to XRD, the total mud product, the mica product and the feldspar product which are enriched with lithium are obtained by a mineral separation process, the pretreatment such as high-temperature roasting, adding of salt roasting auxiliary agents and the like is not needed, and concentrated sulfuric acid, high-temperature and high-pressure are also not needed.
The low-temperature lithium extraction is to acidify and bake the hydrothermal alteration type lithium ore and acid liquor with a certain concentration at a low temperature (100-200 ℃) to obtain acidified clinker, and then add water to stir and leach lithium. The principle is that after acid treatment at a certain temperature, the structure of the hydrothermal alteration type lithium-containing chlorite becomes loose, H + The ion volume is small, and the lithium ions easily enter the lithium chlorite structure to occupy Li + 、Al 3+ 、Fe 3 + 、Mg 2+ 、Fe 2+ The position of the metal ion is thus made to be Li + 、Al 3+ 、Fe 3+ 、Mg 2+ 、Fe 2+ And the metal ions are dissolved out, and finally, the lithium sulfate solution is formed.
The novel medicament adopted by the invention can efficiently separate and recycle feldspar and quartz in the low-grade lithium ore to obtain quartz concentrate with the yield of 10-15 percent and SiO 2 The content of Fe4.82 mug/g can be used as high-purity quartz concentrate with 99.94%, and the low-iron high-purity quartz sand price at presentThe value is 2000-4000 yuan/ton, and the economic benefit of mines is obviously increased.
The yield of the mica leaching residue and the feldspar leaching residue obtained after lithium extraction is 45% -55%, the mica leaching residue and the feldspar leaching residue can be cleaned to be neutral after filtration, and the mica leaching residue and the feldspar leaching residue can be used as siliceous raw materials for cement ingredients, aerated bricks and the like, so that the tailing discharge amount is reduced, the comprehensive utilization level of lithium ores is obviously improved, and the method has good social benefit, economic benefit and environmental benefit. In addition, the invention has strong applicability and wide applicability range, can be applied to industrial production, and has wider applicable market.
The invention belongs to comprehensive utilization of low-grade ore resources, and the coarse grain part enters an ore grinding system, so that the ore grinding cost can be greatly reduced, the lithium-containing minerals are preferentially enriched to improve the grade, lithium ions are efficiently converted by low-temperature dilute acid, quartz in the lithium ores is comprehensively recovered to meet the requirement of high-purity quartz, meanwhile, mica and feldspar are separated, the leached slag after lithium extraction can be used for building materials, the economic benefit is increased, the tailing piling is reduced, the thought of a green mine is met, and the development trend of the era is met.
By adopting the technical scheme, compared with the prior art, the invention has the following beneficial effects.
According to the method, raw ore is pre-screened to be in coarse fraction and +40 meshes, the coarse fraction and the +40 meshes are fed into ore grinding, the ore grinding cost is reduced, the separated total mud, mica and feldspar are respectively added with a lithium extraction reagent, the pretreatment such as high-temperature roasting and the addition of salt roasting auxiliary agents is not needed, concentrated sulfuric acid is also not needed, and lithium can be directly and efficiently extracted by adopting low-temperature low-pressure low-concentration acid and normal-temperature water immersion stirring. The invention has the advantages of small corrosiveness to equipment, energy conservation, environmental protection, strong adaptability to raw materials, green and clean performance and high lithium leaching rate up to 90 percent.
The novel medicament adopted by the invention can efficiently separate and recycle feldspar and quartz in the hydrothermal alteration lithium ore to obtain quartz concentrate SiO 2 The content of Fe is 99.94%, fe 4.38 mug/g can be used as high-purity quartz concentrate, mica leaching residue and feldspar leaching residue can be used as siliceous raw materials, and the method can be used for cement ingredients, aerated bricks and the like, reduces the discharge amount of tailings, obviously improves the comprehensive utilization level of lithium ores, and has good social benefit, economic benefit and environmental benefit.
The following describes the embodiments of the present invention in further detail with reference to the accompanying drawings.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this application, illustrate embodiments of the invention and together with the description serve to explain the invention, without limitation to the invention. It is evident that the drawings in the following description are only examples, from which other drawings can be obtained by a person skilled in the art without the inventive effort. In the drawings:
FIG. 1 is a schematic flow chart of the method of the invention.
It should be noted that these drawings and the written description are not intended to limit the scope of the inventive concept in any way, but to illustrate the inventive concept to those skilled in the art by referring to the specific embodiments.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments will be clearly and completely described with reference to the accompanying drawings in the embodiments of the present invention, and the following embodiments are used to illustrate the present invention, but are not intended to limit the scope of the present invention.
The raw ores adopted in the following examples and comparative examples are low-grade hydrothermal alteration type lithium ores, which are novel lithium ore forming types found in Anhui province, mineralization of lithium ores is caused by hydrothermal alteration minerals, chlorite is used as the occurrence minerals of lithium, and not lepidolite and spodumene of traditional lithium ores, and lepidolite and spodumene are the results of magma evolution. Raw ore chemical analysis results: siO (SiO) 2 64.47％，Al 2 O 3 19.60％，Fe 2 O 3 3.55％，K 2 O 3.48％，CaO 1.62％，Na 2 0.85% of O and 0.98% of MgO. Raw ore XRD analysis results: 30.47% of quartz, 23.07% of orthoclate, 9.04% of albite, 17.66% of muscovite and 19.77% of chlorite.
Example 1 Low Wen Dili
As shown in fig. 1, the method for efficiently extracting lithium and high-purity quartz from low-grade hydrothermal alteration type lithium ore in the embodiment comprises the following steps:
(1) Taking crushing-sieving pretreatment until the particle size reaches-1 mm and Li is contained 2 500 g of raw ore with O0.22 percent. Sieving with 40 mesh, 60 mesh, 80 mesh, 120 mesh, 140 mesh and 200 mesh sieve to obtain three-grade products of +40 mesh, -40+200 mesh and-200 mesh.
(2) And (3) carrying out large-barrel rod grinding on the +40 mesh grade obtained in the step (1) for 4 minutes, wherein the grinding concentration is 50%, removing fine mud of-200 meshes by wet screening, drying, checking and screening, and then carrying out screening analysis by using a screen of 40 meshes, 60 meshes, 80 meshes, 120 meshes, 140 meshes and 200 meshes to obtain three grade products of +40 meshes, -40+200 meshes and-200 meshes.
(3) And (3) merging the qualified-40+200-mesh fractions obtained in the step (1) and the step (2), pouring the mixture into an XFD12 type scrubbing machine, stirring and scrubbing for 30 minutes, wherein the concentration of ore pulp is 50%, and removing the ore mud by siphon sedimentation until water is clear.
(4) And (3) feeding coarse sand obtained after desliming in the step (3) into a wet type weak magnetic separator, and removing magnetic iron by using the magnetic field strength 1700 Oe.
(5) And (3) feeding the nonmagnetic substance obtained in the step (4) into a wet type strong magnetic separator, wherein the magnetic field strength is 1.4T, and obtaining the magnetic mica concentrate and the nonmagnetic substance.
(6) Weighing a certain amount of non-magnetic matters obtained in the step (5), adding the non-magnetic matters into a 0.5L flotation tank of an XFD12 type flotation machine, wherein the concentration of flotation ore pulp is 20%, the pH value of the ore pulp is regulated to 2-3 by sulfuric acid, adding 400g/t of novel reverse flotation feldspar medicament, 50g/t of foaming agent, and the flotation and foam scraping time is 2 minutes, the stirring speed is 1500r/min, the one-coarse three-sweep foam product is feldspar concentrate, and the product in the tank is quartz concentrate. The novel collector is a mixture of compound amine, fatty acid and silicate inhibitor, and the foaming agent is a mixture of hydrocarbon oil and pine oil.
(7) Mixing the fine mud with 200 meshes obtained in the steps (1), 2) and (3), weighing 3 g of the mica concentrate and the feldspar concentrate in the step (5), respectively, adding a 45% concentration dilute acid lithium extraction reagent, uniformly stirring, placing into a 150 ℃ oven for preserving heat for 4 hours, adding a 3:1 liquid-solid ratio water for soaking, stirring at 28 ℃ for 1 hour, filtering the soaked slag, and flushing to neutrality.
(8) And (3) carrying out hot-pressing acid leaching on the quartz concentrate obtained in the step (6), wherein the hot-pressing acid leaching process is at least one of ultrasonic acid leaching, stirring acid leaching and heating acid leaching. Adding mixed acid which is at least one of hydrochloric acid, nitric acid and hydrofluoric acid or a mixture according to a liquid-solid ratio of 1:2, carrying out hot-pressing acid leaching for 24 hours at 70 ℃, washing with ultra-pure water to be neutral, and carrying out 13 trace element detection.
(9) And (3) respectively carrying out liquid-solid separation on the mica leaching residue, the feldspar leaching residue and the total mud leaching residue after the stirring leaching is finished in the step (7) to obtain leaching liquid and leaching residue. And (5) analyzing the lithium content by ICP-AES (inductively coupled plasma-atomic emission spectrometry) for drying the leaching residue, and calculating the lithium leaching rate. The low temperature lithium extraction results of example 1 are shown in table 1, and the analysis results of the high purity quartz concentrate are shown in table 2.
Table 1 example 1 low temperature lithium extraction results
TABLE 2 analysis results of high purity quartz concentrate
| Element(s) | SiO 2 (％) | Fe | Mn | Cr | Ni | Cu | Mg |
| Content mu g/g | 99.94 | 4.38 | 0.36 | 0.19 | 0.05 | 0.12 | 0.70 |
| Element(s) | Ca | Al | Na | Li | K | Ti | |
| Content mu g/g | 51.89 | 390.98 | 15.65 | 40.21 | 12.07 | 64.76 |
Example 2 Low Wen Dili
As shown in fig. 1, the method of the present embodiment includes the following steps:
(1) Taking crushing-sieving pretreatment until the particle size reaches-1 mm and Li is contained 2 500 g of raw ore with O0.20 percent is screened and analyzed by a sieve with 40 meshes, 60 meshes, 80 meshes, 120 meshes, 140 meshes and 200 meshes to obtain +40 meshes, -40+20 meshesThree grades of products of 0 mesh and 200 mesh.
(2) And (3) carrying out medium-drum rod grinding on the +40 mesh grade obtained in the step (1) for 15 minutes, wherein the grinding concentration is 50%, removing fine mud of-200 meshes by wet screening, drying, checking and screening, and then carrying out screening analysis by using a screen of 40 meshes, 60 meshes, 80 meshes, 120 meshes, 140 meshes and 200 meshes to obtain three grade products of +40 meshes, -40+200 meshes and-200 meshes.
(3) And (3) merging the qualified-40+200-mesh fractions obtained in the step (1) and the step (2), pouring the mixture into an XFD12 type scrubbing machine, stirring and scrubbing for 30 minutes, wherein the concentration of ore pulp is 50%, and removing the ore mud by siphon sedimentation until water is clear.
(4) Weighing a certain amount of coarse sand obtained in the step (3), adding the coarse sand into a 0.5L flotation tank of an XFD12 type flotation machine, floating the ore pulp with the concentration of 25%, regulating the pH value of the ore pulp with sulfuric acid to be 2-3, adding the novel reverse flotation mica agent with the dosage of 300g/t and the foaming agent with the dosage of 40g/t, adding the primary three-sweep foam product into the ore pulp to obtain mica concentrate, adding the direct flotation agent with the dosage of 200g/t, and carrying out direct flotation to obtain quartz concentrate, wherein the product in the tank is feldspar concentrate. The positive flotation reagent is a polymer of alkaline earth metal cations and alkyl sulfonate.
(5) Mixing the fine mud with 200 meshes obtained in the steps (1), 2) and (3), weighing 3 g of samples of mica concentrate and feldspar concentrate in the step (4), respectively adding 35% concentration dilute acid lithium extraction reagent in a liquid-solid ratio of 2:1, uniformly stirring, placing into a 130 ℃ oven for heat preservation for 5 hours, adding liquid-solid ratio of 4:1 for water leaching after finishing, leaching and stirring at 25 ℃ for 0.5 hour, filtering the leached slag, and flushing to neutrality.
(6) And (3) carrying out hot-pressing acid leaching on the quartz concentrate obtained in the step (4), wherein the hot-pressing acid leaching process is at least one of ultrasonic acid leaching, stirring acid leaching and heating acid leaching. Adding mixed acid which is at least one of hydrochloric acid, nitric acid and hydrofluoric acid or a mixture according to a liquid-solid ratio of 2:1, carrying out hot-pressing acid leaching for 23 hours at 70 ℃, washing with ultra-pure water to be neutral, and carrying out 13 trace element detection.
(7) And (5) respectively carrying out liquid-solid separation on the mica leaching residue, the feldspar leaching residue and the total mud leaching residue after the stirring leaching is finished to obtain leaching liquid and leaching residue. And (5) analyzing the lithium content by ICP-AES (inductively coupled plasma-atomic emission spectrometry) for drying the leaching residue, and calculating the lithium leaching rate. The low temperature lithium extraction results of example 2 are shown in table 3, and the analysis results of the high purity quartz concentrate are shown in table 4.
TABLE 3 Low temperature lithium extraction results for example 2
TABLE 4 analysis results of high purity quartz concentrate
The high-purity quartz concentrate is analyzed, and the Fe content is 29.94mg/kg, the Al content is 315.5mg/kg and the SiO content is 2 The total impurity content is 490.03mg/kg and is less than or equal to 1000mg/kg, and the acid leaching concentrate obtained by the invention reaches the high-purity quartz low-end product.
Example 3 Low Wen Dili
The difference between this embodiment and the first embodiment is that:
will contain Li 2 And (3) carrying out regrinding on a product with more than +40 meshes separated out by an O0.21% raw ore sieve by a 5-minute large-barrel rod mill, respectively weighing 3 g of prepared total mud, feldspar and mica, adding a 55% concentration dilute acid lithium extraction reagent, uniformly stirring the mixture according to a liquid-solid ratio of 1.3:1, then placing the mixture into a 140 ℃ for heat preservation for 4 hours, adding water according to a liquid-solid ratio of 3:1 after finishing, soaking the mixture into water, stirring the mixture at a temperature of 30 ℃, stirring the mixture for 45 minutes, and extracting lithium at a low temperature, wherein the result is shown in Table 5.
Table 5 example 3 low Wen Dili
Example 4 Low Wen Dili
The difference between this embodiment and the first embodiment is that:
taking Li 2 Hydrothermal alteration lithium ore with O content of 0.12% is directly ground to-200 meshes to account for 90%, 3 g of sample is weighed and added with 75%Uniformly stirring a dilute acid lithium extraction reagent with concentration and liquid-solid ratio of 1.3:1, putting into a 135 ℃ oven for heat preservation for 6 hours, adding water with liquid-solid ratio of 4:1 after finishing, and leaching at stirring temperature of 50 ℃ for 1 hour, wherein the index of low-temperature lithium extraction is Li 2 The leaching rate of O is 93.51 percent.
Example 5 Low Wen Dili
The difference between this embodiment and the first embodiment is that:
taking Li 2 The hydrothermal alteration type lithium ore with the O content of 0.17 percent is directly ground to 90 percent with the mesh of-200, 3 g of sample is weighed, 75 percent of dilute acid lithium extraction reagent is added, the mixture is uniformly stirred according to the liquid-solid ratio of 1.3:1, the mixture is put into a 135 ℃ oven for heat preservation for 6 hours, after the completion, the mixture is added with water according to the liquid-solid ratio of 4:1 for leaching, the water leaching stirring temperature is 50 ℃, the stirring time is 1 hour, and the low-temperature lithium extraction index is Li 2 The leaching rate of O is 94.57 percent.
Example 6 Low Wen Dili
The difference between this embodiment and the first embodiment is that:
taking Li 2 The hydrothermal alteration type lithium ore with the O content of 0.2 percent is directly ground to 90 percent with the mesh of-200, 3 g of sample is weighed, 75 percent of dilute acid lithium extraction reagent is added, the mixture is uniformly stirred according to the liquid-solid ratio of 1.3:1, the mixture is put into a 135 ℃ oven for heat preservation for 6 hours, after the completion, the mixture is added with water according to the liquid-solid ratio of 4:1 for leaching, the water leaching stirring temperature is 50 ℃, the stirring time is 1 hour, and the low-temperature lithium extraction index is Li 2 The leaching rate of O is 96.10 percent.
Example 7 Low Wen Dili
The difference between this embodiment and the first embodiment is that:
taking Li 2 The hydrothermal alteration type lithium ore with the O content of 0.25 percent is directly ground to 90 percent with the mesh of-200, 3 g of sample is weighed, 75 percent of dilute acid lithium extraction reagent is added, the mixture is uniformly stirred according to the liquid-solid ratio of 1.3:1, the mixture is put into a 135 ℃ oven for heat preservation for 6 hours, after the completion, the mixture is added with water according to the liquid-solid ratio of 4:1 for leaching, the water leaching stirring temperature is normal temperature of 20 ℃, the stirring time is 1 hour, and the low-temperature lithium extraction index is Li 2 The leaching rate of O is 94.59 percent.
Example 8 Low Wen Dili
The difference between this embodiment and the first embodiment is that:
taking Li 2 The hydrothermal alteration type lithium ore with the O content of 0.31 percent is directly ground to 90 percent with the mesh of-200, 3 g of sample is weighed, 75 percent of dilute acid lithium extraction reagent is added, the mixture is uniformly stirred according to the liquid-solid ratio of 1.3:1, the mixture is put into a 135 ℃ oven for heat preservation for 6 hours, after the completion, the mixture is added with water according to the liquid-solid ratio of 4:1 for leaching, the water leaching stirring temperature is heated to 50 ℃, the stirring time is 1 hour, and the low-temperature lithium extraction index is Li 2 The leaching rate of O is 96.35%; other conditions are unchanged, the mixture is immersed in water at normal temperature and stirred at 20 ℃, li 2 The leaching rate of O is 95.14 percent.
Example 9 Low Wen Dili
The difference between this embodiment and the first embodiment is that:
taking Li 2 The hydrothermal alteration type lithium ore with the O content of 0.30 percent is directly ground to 90 percent with the mesh of-200, 3 g of sample is weighed, 35 percent of dilute acid lithium extraction reagent is added, the mixture is evenly stirred according to the liquid-solid ratio of 1.3:1, the mixture is put into a 135 ℃ oven for heat preservation for 6 hours, after the completion, water leaching according to the liquid-solid ratio of 4:1 is added, the water leaching stirring temperature is 24 ℃, the stirring time is 1 hour, li 2 The leaching rate of O is 91.76 percent.
Example 10 Low Wen Dili
The difference between this embodiment and the first embodiment is that:
taking Li 2 The hydrothermal alteration type lithium ore with the O content of 0.30 percent is directly ground to 90 percent with the mesh of-200, 3 g of sample is weighed, 45 percent of dilute acid lithium extraction reagent with the concentration is added, the mixture is evenly stirred according to the liquid-solid ratio of 1.3:1, the mixture is put into a baking oven with the temperature of 135 ℃ for heat preservation for 4 hours, after the completion, the mixture is added with water according to the liquid-solid ratio of 3:1 for leaching, the water leaching stirring temperature is 24 ℃, the stirring time is 1 hour, and Li 2 The leaching rate of O is 95.92 percent.
Comparative example 1 high temperature lithium extraction
High-temperature lithium extraction conditions: weighing the total mud, feldspar and mica products respectively, roasting in a muffle furnace at 700 ℃ for 1 hour, adding the dilute acid with the concentration and the volume of the lithium extraction reagent of 45% in the same concentration and the volume of the embodiment 1, stirring and leaching in a magnetic stirring water bath kettle at the water temperature of 90 ℃ for 1 hour, filtering and washing for multiple times to neutrality, drying filter residues, measuring the content of lithium in slag by using ICP-AES, and calculating the operation leaching rate of lithium. The leaching rate of high temperature lithium extraction is shown in Table 6.
Table 6 comparative example 1 high temperature lithium extraction results
Example 1 and comparative example 1, by comparing the low temperature lithium extraction and high temperature lithium extraction schemes, the low Wen Dili integrated leaching rate of 88.78% for the raw ore, the high temperature lithium extraction integrated leaching rate of 79.73% for the raw ore, the low Wen Bigao temperature integrated leaching rate of 9.05%, the green low temperature lithium extraction technique of example 1 shows great advantages over the high temperature lithium extraction technique of comparative example 1, namely saving cost and using lithium as much as possible as Li + The form is transferred to the solution.
Comparative example 2 high temperature lithium extraction
High-temperature lithium extraction conditions: weighing the total mud, feldspar and mica products respectively, roasting in a muffle furnace at 700 ℃ for 1 hour, adding the diluted acid with the concentration and the volume of the lithium extraction reagent which are the same as those of the embodiment 2, stirring and leaching in a magnetic stirring water bath kettle at the water temperature of 90 ℃ for 1 hour, filtering and washing for many times to neutrality, drying filter residues, measuring the content of lithium in slag by using ICP-AES, and calculating the operation leaching rate of lithium. The leaching rate of high temperature lithium extraction is shown in Table 7.
Table 7 comparative example 2 high temperature lithium extraction leaching rate
Example 2 and comparative example 2 illustrate that compared with the low temperature lithium extraction and high temperature lithium extraction schemes, the method has the advantages that the accumulated leaching rate of the low Wen Dili to the raw ore is 90.07 percent, the accumulated leaching rate of the high temperature lithium extraction to the raw ore is 67.17 percent, and the accumulated temperature of the high temperature lithium extraction is 22.90 percent higher than that of the low Wen Bigao; the green low-temperature lithium extraction technology of the embodiment 2 has great advantages over the high-temperature lithium extraction technology of the comparative embodiment 2, the invention not only saves cost and has high leaching rate, but also the low-temperature lithium extraction technology is not influenced by mineral separation flow and mineral granularity, and is relatively stable in lithium leaching rate.
Comparative example 3 high temperature lithium extraction
High-temperature lithium extraction conditions: weighing the total mud, feldspar and mica products respectively, roasting in a muffle furnace at 700 ℃ for 1 hour, adding the lithium extraction reagent with the same concentration and volume as in the embodiment 3 and with the dilute acid concentration of 55%, stirring and leaching in a magnetic stirring water bath kettle with the water temperature of 90 ℃ for 1 hour, filtering and washing for many times to be neutral, drying filter residues, measuring the lithium content in slag by using ICP-AES, and calculating the operation leaching rate of lithium. The leaching rate of high temperature lithium extraction is shown in Table 8.
Table 8 comparative example 3 high temperature lithium extraction leaching rate
Example 3 and comparative example 3 show that the cumulative leaching rate of low Wen Dili to raw ore is 89.75%, the cumulative leaching rate of high-temperature lithium extraction to raw ore is 80.37%, and the cumulative leaching rate of low Wen Dili to high-temperature lithium extraction is 9.38%, which shows that the method is relatively stable to lithium leaching rate.
The feldspar leaching residue and the mica leaching residue are leached to be neutral for many times, so that the granularity of the product is coarser at-40+200 meshes, and the application of the product in the aspect of building materials is examined by chemical analysis. The analysis results are shown in Table 9.
TABLE 9 analysis results of feldspar leaching residue and mica leaching residue
The feldspar leaching residue and the mica leaching residue can be used as siliceous raw materials and used for cement ingredients, aerated bricks and the like, so that good economic benefits can be generated, the yield of the two parts is 50-55%, the total mud yield is 30-40%, the method can be used for clay for bricks and tiles, the quartz concentrate yield is 10-15%, ore products do not need to be discharged into a tailing pond, the invention really realizes comprehensive utilization of mineral resources, and tailing-free mountain production is realized.
The foregoing description is only illustrative of the preferred embodiment of the present invention, and is not to be construed as limiting the invention, but is to be construed as limiting the invention to any and all simple modifications, equivalent variations and adaptations of the embodiments described above, which are within the scope of the invention, may be made by those skilled in the art without departing from the scope of the invention.
Claims (10)
1. The method for efficiently extracting lithium and high-purity quartz from low-grade hydrothermal alteration type lithium ore is characterized by comprising the following steps of:
(1) Crushing ore: crushing and preprocessing low-grade hydrothermal alteration lithium ores to obtain preprocessed materials with granularity of-1 mm;
(2) And (3) pretreatment material screening: performing screening and screening on the pretreated material with the diameter of-1 mm obtained in the step (1);
(3) Grinding the oversize products: grinding the +40 mesh oversize product obtained in the step (2), and screening out-200 mesh fine mud products by a wet screen and a dry screen;
(4) Stirring, scrubbing-settling and desliming: classifying the ground ore product obtained in the step (3) to obtain-40+200 mesh coarse sand, combining the-40+200 mesh coarse sand obtained in the step (2) to obtain qualified size fraction, and stirring, scrubbing and sedimentation desliming;
(5) And (3) low-intensity magnetic separation: carrying out wet weak magnetic separation on the desliming coarse sand product obtained in the step (4) to remove iron;
(6) And (3) strong magnetic separation: carrying out strong magnetic separation on the product obtained in the step (5) after the magnetic iron is removed under a high gradient magnetic field to obtain mica concentrate and nonmagnetic substances;
(7) Reverse flotation separation: carrying out reverse flotation separation on the nonmagnetic substance obtained in the step (6) under the condition of pH value of 2-3 by adopting a novel collector to obtain feldspar concentrate and quartz concentrate;
(8) Hot-pressing acid leaching: carrying out hot-pressing acid leaching, washing and drying on the flotation quartz concentrate obtained in the step (7) to obtain high-purity quartz concentrate;
(9) Combining mud: combining the-200 mesh products obtained in the steps (2), (3) and (4) to obtain a total mud product;
(10) Low Wen Dili: respectively adding the mica concentrate obtained in the step (6), the feldspar concentrate obtained in the step (7) and the total mud obtained in the step (9) into a lithium extraction reagent for carrying out low Wen Dili;
(11) And (3) slag leaching detection: detecting lithium content of the mica leaching residue, the feldspar leaching residue and the total mud leaching residue obtained in the step (10) by ICP-AES respectively, and carrying out chemical analysis on the mica leaching residue and the feldspar leaching residue;
(12) And (3) high-purity quartz sand detection: and (3) carrying out 13 trace element ICP-MS detection on the high-purity quartz refined sand obtained in the step (8) in an ultra-clean laboratory, and examining the index requirement of the high-purity quartz.
2. The method for efficiently extracting lithium and high-purity quartz from low-grade hydrothermal alteration type lithium ore according to claim 1, wherein in the step (1), the crushing equipment is a jaw crusher-twin roll crusher-double-layer vibrating screen for laboratory use; in the step (2), the screening equipment is a standard laboratory screening equipment, namely 25 meshes, 40 meshes, 60 meshes, 80 meshes, 120 meshes, 140 meshes and 200 meshes.
3. The method for efficiently extracting lithium and high-purity quartz from low-grade hydrothermal alteration type lithium ore according to claim 1, wherein in the step (3), three-roller four-drum rod mill is adopted for ore grinding, the ore grinding time is 3-15 minutes, fine mud products with-200 meshes are screened out after ore grinding, and the rest products with-40+200 meshes are qualified.
4. The method for efficiently extracting lithium and high-purity quartz from low-grade hydrothermal alteration type lithium ores according to claim 1, wherein in the step (4), stirring scrubbing-sedimentation desliming is performed on raw ore screening-40+200 mesh coarse sand and regrinding-40+200 mesh coarse sand, stirring scrubbing is performed in an XFD12 type scrubbing machine, scrubbing pulp concentration is 50%, scrubbing time is 30 minutes, and fine mud is extracted by a siphon sedimentation method until the pulp is clear.
5. The method for efficiently extracting lithium and high-purity quartz from low-grade hydrothermal alteration type lithium ore according to claim 1, wherein in the step (5), the weak magnetic separation is a wet weak magnetic separation with a magnetic field strength of 1500-2000 Oe; in the step (6), the strong magnetic separation is a section of high-gradient magnetic separation, and the magnetic field strength is 1.2-1.8T.
6. The method for efficiently extracting lithium and high-purity quartz from low-grade hydrothermal alteration type lithium ore according to claim 1, wherein in the step (7), reverse flotation separation is aerated flotation, and the flotation machine is an XFD12 type multi-tank flotation machine, and the process conditions are as follows: the pH value of the ore pulp is regulated to 2-3, the acid for regulating the pH value is one or a mixture of sulfuric acid, oxalic acid, nitric acid and hydrochloric acid, the concentration of reverse flotation ore pulp is 15-30%, the dosage of the novel collecting agent is 400-600 g/t, the dosage of the foaming agent is 50-100 g/t, the stirring rate is 800-1200 r/min, and the flotation time is 2-5 min; the novel collector is a mixture of compound amine, fatty acid and silicate inhibitor, and the foaming agent is a mixture of hydrocarbon oil and pine oil.
7. The method for efficiently extracting lithium and high-purity quartz from low-grade hydrothermal alteration type lithium ore according to claim 1, wherein in the step (8), the hot-press acid leaching process is at least one of ultrasonic acid leaching, stirring acid leaching and heating acid leaching, the acid is mixed acid, the mixed acid is a composition of two or more of hydrofluoric acid, nitric acid, hydrochloric acid, sulfuric acid and oxalic acid, and the leaching time is 4-24 hours.
8. The method for efficiently extracting lithium and high-purity quartz from low-grade hydrothermal alteration type lithium ore according to claim 1, wherein in the step (9), the sludge is combined: and (3) mixing and scrubbing the fine mud of-200 meshes and the fine mud of-200 meshes which is generated after regrinding of +40 meshes and qualified size fractions of-40+200 meshes obtained from raw ore, and combining the three products into total mud.
9. The method for efficiently extracting lithium and high-purity quartz from low-grade hydrothermal alteration type lithium ore according to claim 1, wherein in the step (10), the low-temperature lithium extraction is as follows: the treatment temperature is 100-200 ℃, the lithium extraction reagent is diluted by acid, the concentration is 30-75%, the heat preservation time is 1-5 h, the water immersion stirring time is 0.5-1 h, the water immersion stirring temperature is 20-90 ℃, and the leaching residue is filtered and then washed to be neutral.
10. According to claimThe method for efficiently extracting lithium and high-purity quartz from low-grade hydrothermal alteration type lithium ore as described in claim 1, which is characterized in that in the step (11), lithium leaching rate is calculated by measuring lithium by ICP-AES respectively, and SiO is detected by mica leaching residue and feldspar leaching residue 2 、Al 2 O 3 、Fe 2 O 3 、K 2 O、Na 2 And O index.
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