CN121109779A - Multi-product co-production methods and systems for carbon-reduced lithium ore - Google Patents
Multi-product co-production methods and systems for carbon-reduced lithium oreInfo
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Abstract
The invention discloses a multi-product co-production method and a multi-product co-production system for carbon reduction lithium ores, which solve the technical problems of high energy consumption, large amount of waste residues and low resource utilization rate in the traditional lithium ore treatment. The method comprises the steps of treating flue gas and/or treating a solution, wherein the step of treating the flue gas comprises the steps of reducing the temperature of the flue gas to 500-700 ℃ and collecting solids to obtain primary solids and first clean gas, reducing the temperature of the first clean gas to below 50 ℃ and collecting solids to obtain secondary solids and second clean gas, carrying out water quenching treatment on the primary solids, filtering a generated first solid-liquid mixture to obtain a first solution, carrying out water quenching treatment on the secondary solids to obtain third clean gas and a second solution, and treating the solution comprises the steps of cooling the high-density solution to obtain the first solids, cooling the medium-density solution to obtain the second solids, and cooling the low-density solution to obtain the third solids.
Description
Technical Field
The invention relates to the technical field of ore high-temperature smelting, in particular to a multi-product co-production method and a multi-product co-production system of carbon reduction lithium ores.
Background
The traditional main process of lithium ore treatment is to extract and utilize lithium in minerals, and generally, the mineral structure is reconstructed through high-temperature calcination and then acidizing and roasting (such as spodumene), or the minerals and sulfate are mixed and calcined at high temperature (such as lepidolite), so that lithium oxide in the minerals generates water-soluble lithium sulfate, and then the processes of deslagging, impurity removal, purification and the like are carried out through a wet process, and finally, the product lithium carbonate or lithium hydroxide is obtained.
The smelting furnace adopted in the traditional ore calcination and roasting occupies a very large area, usually 1 melt discharge port is arranged, and the melt is required to be condensed and crushed after being integrally discharged and then enters a wet process. Because the components of the melt formed by all minerals and additives are complex, the melt enters the wet process, so that the processing capacity of the wet process is huge, the energy consumption is high, a large amount of waste residues can be generated, the resource utilization rate of lithium ores is low, and the generated economic benefit is low.
Since valuable substances in minerals are singly utilized, a large amount of resources become waste residues, and only a part of the valuable substances are utilized with low value. Taking spodumene sulfuric acid method for producing lithium carbonate as an example, more than 8 tons of concentrate containing 5% of lithium oxide (about 7 tons of waste residues) or more than 33 tons of ore with 1.25% of grade (Li 2O content) are needed to be selected (more than 25 tons of tailings generated during ore dressing) per ton of lithium carbonate produced. If lithium carbonate is produced by lepidolite sulfate method, about 30 tons of concentrate containing 1.5% of lithium oxide (about 40 tons of waste residue produced) is needed for each ton of lithium carbonate production, and ore with a grade of 0.4% is needed to be selected to be more than 100 tons (tailings produced by ore dressing is more than 70 tons).
Therefore, the traditional lithium ore treatment mainly aims at wet extraction of lithium resources, has high energy consumption, generates a large amount of waste residues, and basically does not recycle other resources. However, lithium ores contain many alkali metals and non-metals in addition to lithium, which are valuable mineral resources.
Disclosure of Invention
In order to solve the technical problems of high energy consumption, large amount of waste residues and low resource utilization rate in the traditional lithium ore treatment in the prior art, the invention provides a smelting furnace, a molten liquid treatment system, a flue gas treatment system, a multi-product co-production system and a multi-product co-production method of carbon reduction lithium ores, which have the following technical scheme:
The smelting furnace comprises a furnace body and a discharging assembly, wherein the discharging assembly comprises a high-density molten liquid discharging mechanism, a medium-density molten liquid discharging mechanism and a low-density molten liquid discharging mechanism, the high-density molten liquid discharging mechanism is sequentially arranged on the furnace body from bottom to top and comprises a lower discharging hole arranged on the furnace body, the medium-density molten liquid discharging mechanism comprises a medium discharging hole arranged on the furnace body, and the low-density molten liquid discharging mechanism comprises an upper discharging hole arranged on the furnace body.
The smelting furnace provided by the invention is provided with three discharge ports, and can correspondingly discharge molten liquid layers distributed at different elevations according to layering phenomena of different density components in the molten liquid, so that different mineral molten liquids are properly separated, various products with higher enrichment degree or purer products can be directly obtained, or the subsequent material purification and purification process can be obviously simplified, the co-production of various products is realized, and the natural resource utilization rate of ores is obviously improved. Particularly, the three discharge ports of the smelting furnace can be used as required, namely, the discharge ports with corresponding quantity and positions can be opened according to different melt compositions and production requirements, and the smelting furnace can be used for smelting lithium ores, silicon ores, waste residues of lithium salt factories, tailings of lithium ore dressing factories, nonferrous smelting lithium-containing waste residues and the like, and has extremely strong practicability.
As a further improvement of the smelting furnace, the lower discharge port, the middle discharge port and the upper discharge port are arranged along the circumferential direction of the furnace body. Preferably, the horizontal projection included angle of the lower discharge port and the middle discharge port is not smaller than 10 degrees. Therefore, the arrangement and the use of the valves of the related pipelines of the liquid discharging mechanism are facilitated.
As a further improvement of the smelting furnace, the smelting furnace also comprises a heating component, a blanking component and an air duct which are connected with the inside of the furnace body. Preferably, the heating assembly comprises at least three heating electrodes distributed annularly. The blanking assembly comprises at least three blanking pipes which are at least uniformly distributed on the periphery of the heating mechanism. Therefore, uniform heating and uniform blanking are facilitated.
As a further improvement of the smelting furnace, the discharging pipe comprises an upper inclined pipe section and a lower vertical pipe section. Therefore, the charging bins are conveniently arranged around the upper part of the smelting furnace, and the mutual obstruction of the charging bins and the heating components is avoided.
As a further improvement of the smelting furnace, the smelting furnace further comprises an executing mechanism and a power mechanism, wherein the vibrating structure is arranged in the furnace body and used for breaking the crust of furnace burden, and the power mechanism is arranged outside the furnace body and used for driving the executing mechanism (such as vibrating and rotating). Therefore, the furnace burden crust can be broken by the executing mechanism, and unstable furnace conditions caused by large material treading in the furnace body can be avoided.
As a further improvement of the smelting furnace, the inner space of the furnace body is cylindrical, the diameter D is 1-12 m, and the height H of the inner space is 0.8-1.5 times of the diameter D. Preferably, the furnace body comprises an outer carbon steel shell, an inner refractory brick lining and a water cooling coil. Compared with the traditional smelting furnace with the diameter of more than 8 meters, the smelting furnace provided by the invention can be miniaturized (D is 1-3 m, H is 0.8-3 m), and can be integrated with skid-mounted equipment to move to a working condition that a small amount of mineral aggregate (such as waste residue, tailings and the like of a lithium mill or a nonferrous mill) is required to be smelted, so that the use is more convenient.
The molten liquid treatment system for reducing the lithium carbonate ore comprises a first cooling device, a second cooling device and a third cooling device, wherein the first cooling device is used for cooling high-density molten liquid output by a smelting furnace and outputting first solid containing ferrosilicon alloy, the second cooling device is used for cooling medium-density molten liquid output by the smelting furnace and outputting second solid containing simple substances of silicon, and the third cooling device is used for cooling low-density molten liquid output by the smelting furnace and outputting third solid containing silicon dioxide and metal oxide.
The traditional melt treatment flow is that after being integrally discharged, the melt is condensed and crushed, and then enters the subsequent procedures such as wet process, and finally the resource utilization rate of lithium ores is low. In the melt processing system, the smelting furnace with three discharge ports is combined, and the independent recovery and co-production of three melt components are realized according to the density difference of ferromanganese silicon alloy (high density, more than 4g/cm 3), elemental silicon (medium density, about 2.3-2.4 g/cm 3) and scum (low density, about 2.1-2.2 g/cm 3, mainly silicon dioxide and metal oxide).
In actual production, the theoretical value of the height/volume of each melt layer in the smelting furnace is calculated according to the quality of raw materials and the reaction condition, and then the melt layer higher than the theoretical value or lower than the theoretical value is discharged according to the economic value of each melt layer. For example, for the molten liquid generated by the reduction reaction of carbon, lithium ore and slag forming agent at high temperature, if the expected product is simple substance silicon, the medium density molten liquid with 5-10% of theoretical value can flow into the third cooling device along with the low density molten liquid, then the medium density molten liquid with 80-90% of theoretical value flows into the second cooling device, then the medium density molten liquid with 5-10% of theoretical value flows into the first cooling device along with the high density molten liquid, so that the pure simple substance silicon flows into the second cooling device, and further the pure simple substance silicon product can be directly obtained.
The flue gas treatment system comprises a first heat exchange device, a first gas-solid separation device, a first water quenching device, a first liquid-solid separation device, a second heat exchange device, a second water quenching device and a second water quenching device, wherein the first heat exchange device is used for carrying out cooling and pre-dedusting treatment on the flue gas and outputting a first gas-solid mixture and first dust, the first gas-solid separation device is used for carrying out gas-solid separation treatment on the first gas-solid mixture and outputting a first clean gas and second dust, the first water quenching device is used for carrying out water quenching treatment on primary solids formed by the first dust and the second dust and outputting a first solid-liquid mixture, the first liquid-solid separation device is used for carrying out liquid-solid separation treatment on the first solid-liquid mixture and outputting insoluble slag and a first solution containing lithium hydroxide, the second heat exchange device is used for carrying out cooling and pre-dedusting treatment on the first clean gas and outputting a second gas-solid mixture and third dust, the second gas-solid separation device is used for carrying out gas-solid separation treatment on the second gas-solid mixture and outputting a second clean gas containing carbon monoxide and a fourth dust, and the second water quenching device is used for carrying out water quenching treatment on the second clean gas containing carbon monoxide and a third water quenching dust and a second water quenching dust containing the second clean gas and a third water containing the second dust.
The traditional flue gas treatment process is cooling, dedusting, purifying and discharging, and the resources in the flue gas are not recycled. In the flue gas treatment system, the obtained insoluble slag can be returned to the smelting furnace for deep smelting, the obtained first solution and the obtained second solution can be used for producing lithium hydroxide and potassium hydroxide, and because the smelting furnace operates under positive pressure, external air cannot enter the smelting furnace, the obtained second clean gas is mainly carbon monoxide, the carbon monoxide can be used as high-quality gas, the third clean gas is mainly acetylene gas, the investment and the operation cost of the used equipment are low, the operation and the control are easy, the co-production of various products is finally realized, valuable resources of the flue gas are efficiently recovered, the economic benefit is improved, and the flue gas treatment system has extremely strong practicability.
As a further improvement of the flue gas treatment system, the flue gas treatment system further comprises a first separation device, wherein the first separation device is used for separating and treating the first solution and outputting an alkali solution and lithium hydroxide solids. The separation of lithium hydroxide and potassium hydroxide can be realized according to the solubility difference, the operation is simple, and higher economic benefit can be created.
The flue gas treatment system is further improved by the aid of a first evaporation crystallization device, a second liquid-solid separation device and a first drying device, wherein the first evaporation crystallization device is used for performing evaporation crystallization treatment on an alkali solution and outputting a first crystal dispersion liquid, the second liquid-solid separation device is used for performing liquid-solid separation treatment on the first crystal dispersion liquid and outputting solid alkali and reuse water, and the first drying device is used for drying the solid alkali to obtain an alkali product.
The flue gas treatment system is further improved by further comprising a second evaporation crystallization device, a third liquid-solid separation device and a second drying device, wherein the second evaporation crystallization device is used for performing evaporation crystallization treatment on the second solution and outputting second crystal dispersion liquid, the third liquid-solid separation device is used for performing liquid-solid separation treatment on the second crystal dispersion liquid and outputting lithium hydroxide solids and reuse water, and the second drying device is used for performing drying treatment on the lithium hydroxide solids to obtain a lithium hydroxide product.
As a further improvement of the flue gas treatment system, the flue gas treatment system further comprises third drying equipment and granulating equipment which are used for sequentially carrying out drying treatment and granulating treatment on insoluble slag. Therefore, the insoluble slag is granulated and then put back into the smelting furnace for reaction, so that the conversion rate can be improved, and the reactivity of the raw materials is not affected.
As a further improvement of the flue gas treatment system, the flue gas treatment system further comprises a first powder tank for storing primary solids, a second powder tank for storing secondary solids, a first gas tank for storing second clean gas and a second gas tank for storing third clean gas.
The flue gas treatment system is further improved in that the first heat exchange device and the first gas-solid separation device form an integrated first heat exchange dust removal device, and/or the second heat exchange device and the second gas-solid separation device form an integrated second heat exchange dust removal device.
The multi-product co-production system comprises a smelting furnace, wherein the smelting furnace is used for carrying out reduction reaction on carbon, lithium ores and slag formers and generating smoke and molten liquid;
The flue gas treatment system comprises a first heat exchange device, a second heat exchange device and a first dust collection device, wherein the first heat exchange device is used for cooling and pre-dedusting flue gas and outputting a first gas-solid mixture and first dust; the first gas-solid separation equipment is used for carrying out gas-solid separation treatment on the first gas-solid mixture and outputting first clean gas and second dust; the first water quenching equipment is used for carrying out water quenching treatment on primary solid formed by the first dust and the second dust and outputting a first solid-liquid mixture; the device comprises a first liquid-solid separation device, a second heat exchange device, a second gas-solid separation device, a second water quenching device and a third water quenching device, wherein the first liquid-solid separation device is used for carrying out liquid-solid separation treatment on a first solid-liquid mixture and outputting insoluble slag and a first solution containing lithium hydroxide;
The molten liquid treatment system comprises a first cooling device, a second cooling device and a third cooling device, wherein the first cooling device is used for cooling high-density molten liquid output by a smelting furnace and outputting first solid containing ferrosilicon alloy, the second cooling device is used for cooling medium-density molten liquid output by the smelting furnace and outputting second solid containing simple substances of silicon, and the third cooling device is used for cooling low-density molten liquid output by the smelting furnace and outputting third solid containing silicon dioxide and metal oxide.
The smelting furnace comprises a furnace body and a discharging assembly, wherein the discharging assembly comprises a high-density melt discharging mechanism, the high-density melt discharging mechanism is sequentially arranged on the furnace body from bottom to top and comprises a lower discharging hole arranged on the furnace body, the lower discharging hole is connected with first cooling equipment, the medium-density melt discharging mechanism comprises a medium discharging hole arranged on the furnace body, the medium discharging hole is connected with second cooling equipment, the low-density melt discharging mechanism comprises an upper discharging hole arranged on the furnace body, and the upper discharging hole is connected with third cooling equipment.
The multi-product co-production method of the carbon reduced lithium ore comprises the steps of carrying out reduction reaction on carbon, the lithium ore and a slag former to generate smoke and melt;
The method comprises the steps of reducing the temperature of flue gas to 500-700 ℃ and collecting solids to obtain primary solids and first clean gas, continuously reducing the temperature of the first clean gas to below 50 ℃ and collecting solids to obtain secondary solids and second clean gas containing carbon monoxide, carrying out water quenching treatment on the primary solids, and then filtering a generated first solid-liquid mixture to obtain a first solution containing lithium hydroxide and insoluble slag;
The method comprises the steps of discharging high-density melt, medium-density melt and low-density melt in the melt in a segmented mode according to layering of different density components in the melt, cooling the high-density melt to obtain a first solid containing ferromanganese silicon alloy, cooling the medium-density melt to obtain a second solid containing elemental silicon, and cooling the low-density melt to obtain a third solid containing silicon dioxide and metal oxide.
As a further improvement of the multi-product co-production method, the method also comprises the step of separating the first solution to obtain an alkali solution and lithium hydroxide solids.
The separation treatment comprises the steps of evaporating and concentrating the first solution to a supersaturated state, cooling to room temperature, adding absolute ethyl alcohol to precipitate lithium hydroxide, and filtering to obtain an alkali solution and lithium hydroxide solid.
As a further improvement of the multi-product co-production method, the method also comprises the steps of evaporating and crystallizing the alkali solution, filtering and drying to obtain an alkali product and reuse water.
As a further improvement of the multi-product co-production method, the method further comprises the steps of evaporating and crystallizing, filtering and drying the second solution to obtain a lithium hydroxide product and reuse water.
As a further improvement of the multi-product co-production method, the method also comprises the steps of sequentially drying and granulating the insoluble slag.
As a further improvement of the multi-product co-production method, the slag former is CaO-SiO 2-CaF2 composite slag former. Therefore, silicon dioxide and various metal oxides are enriched on the surface of the molten liquid, the purity of the simple substance of silicon is improved, and the sectional discharge of the molten liquid is conveniently controlled.
The multi-product co-production system and the multi-product co-production method for the carbon reduction lithium ores have the advantages of being combination of the smelting furnace, the melt processing system and the flue gas processing system, and are not repeated.
The invention is further described below with reference to the drawings and detailed description. Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The accompanying drawings, which form a part hereof, are shown by way of illustration and not of limitation, and in which are shown by way of illustration and description of the invention. In the drawings:
FIG. 1 is a schematic side view of a smelting furnace of the present invention.
FIG. 2 is a schematic top view of the smelting furnace of the present invention.
Fig. 3 is a schematic structural diagram of a melt processing system, a flue gas processing system and a multi-product co-production system of the carbon-reduced lithium ores of the present invention.
The relevant marks in the drawings are as follows:
110-furnace body, 121-lower discharge port, 122-middle discharge port, 123-upper discharge port, 130-heating electrode, 140-discharge pipe, 150-air duct, 160-power mechanism, 210-first cooling device, 220-second cooling device, 230-third cooling device, 311-first heat exchange device, 312-first gas-solid separation device, 313-first water quenching device, 314-first liquid-solid separation device, 315-first separation device, 316-first evaporative crystallization device, 317-second liquid-solid separation device, 318-first drying device, 321-second heat exchange device, 322-second gas-solid separation device, 323-second water quenching device, 325-second evaporative crystallization device, 326-third liquid-solid separation device, 327-second drying device, 331-third drying device, 332-granulation device, 341-first powder tank, 342-second powder tank, 343-first gas tank, 344-second gas tank.
Detailed Description
The present invention will now be described more fully hereinafter with reference to the accompanying drawings. Those of ordinary skill in the art will be able to implement the invention based on these descriptions. Before describing the present invention with reference to the accompanying drawings, it should be noted in particular that:
the technical solutions and technical features provided in the sections including the following description in the present invention may be combined with each other without conflict.
In addition, the embodiments of the present invention referred to in the following description are typically only some, but not all, embodiments of the present invention. Therefore, all other embodiments, which can be made by one of ordinary skill in the art without undue burden, are intended to be within the scope of the present invention, based on the embodiments of the present invention.
Terms and units in relation to the present invention. The terms "comprising," "having," and any variations thereof in the description and claims of the invention and in the relevant sections are intended to cover a non-exclusive inclusion.
Lepidolite is a lithium-containing layered silicate mineral belonging to the family of minerals and has a general chemical formula generally designated K (Li, al) 3(Si,Al)4O10(F,OH)3, with the main elements, expressed in mass fractions of oxides, being silicon (about 54.7%), aluminum (about 25.7%), potassium (about 6.5%), fluorine (about 4.5%), lithium (about 3.5%), sodium (about 2.7%), and other very low levels of metallic elements such as calcium, magnesium, manganese, iron, rubidium, cesium, respectively.
Spodumene is a lithium-containing chain silicate mineral with a relatively stable composition and a chemical formula of liaalsi 2O6, and the main elements are silicon (about 64.5%), aluminum (about 26.5%), lithium (about 5.6%), sodium (about 1.17%), potassium (about 1%) and other metal elements with very low contents such as calcium, magnesium, manganese and iron, respectively, in terms of mass fraction of oxides.
The lepidolite, spodumene and carbon powder are subjected to reduction reaction at 1300-1900 ℃ in a smelting furnace, and besides being decomposed into oxides of various elements, the reaction of silicon dioxide and carbon to generate elemental silicon and carbon monoxide, (2) alloying reaction of manganese, iron and silicon, and (3) reaction of alkali metal oxide and carbon to generate elemental alkali metal and carbon monoxide can also occur.
The flue gas thus formed mainly contains unreacted raw material dust (such as mineral powder, carbon powder), unreacted oxide powder, alkali metal simple substance and carbon monoxide. Particularly, as the temperature of the flue gas is reduced to 500-700 ℃, carbon powder in the flue gas reacts with a lithium simple substance to generate gaseous lithium carbide (namely, lithium acetylene).
The formed melt mainly comprises a silicon simple substance, various reactive oxides and a manganese-iron-silicon alloy, and layering is complex at the moment, so that the melt is not easy to be discharged in sections. In order to obtain purer silicon simple substance melt, the invention adopts a slag-making process, and most silicon dioxide and metal oxides are enriched on the surface of the melt in a form of scum, so that the formed melt is mainly composed of the scum of silicon dioxide and various metal oxides at the upper part, the silicon simple substance melt at the middle part and the ferromanganese alloy melt at the lower part. The slag-making process comprises the steps of adding CaO-SiO 2-CaF2 composite slag-making agent into raw materials, wherein the adding amount of the slag-making agent is enough to enable the pH value of the melt to be slightly alkaline or close to neutral (the binary alkalinity R=0.8-1.2, and R represents the mass ratio of CaO to SiO 2 in the melt), and the non-decomposed silicon dioxide and metal oxide can be effectively enriched in the scum.
Aiming at the molten liquid and the flue gas generated by the reduction reaction of the carbon, the lithium ore and the slag former in the smelting furnace at 1300-1900 ℃, the smelting furnace and the molten liquid treatment system, the flue gas treatment system, the multi-product co-production system and the multi-product co-production method of the carbon reduced lithium ore provided by the invention have the following specific embodiments:
FIG. 1 is a schematic side view of a smelting furnace of the present invention. FIG. 2 is a schematic top view of the smelting furnace of the present invention.
The smelting furnace shown in fig. 1-2 includes a furnace body 110, and a discharge assembly, a heating assembly, a blanking assembly, an air duct 150, an actuator (not shown) and a power mechanism 160 connected to the furnace body 110.
The discharging assembly comprises a high-density melt discharging mechanism, a medium-density melt discharging mechanism, a low-density melt discharging mechanism and corresponding pipelines and valves which are sequentially arranged on the furnace body 110 from bottom to top. The high-density melt discharge mechanism includes a lower discharge port 121 provided on the furnace body 110. The medium density melt discharge includes a medium discharge port 122 provided in the furnace body 110. The low density melt discharge mechanism includes an upper discharge port 123 provided on the furnace body 110. The setting heights of the lower discharge port 121, the middle discharge port 122 and the upper discharge port 123 are set according to the composition of the melt produced in actual production.
The lower discharge port 121, the middle discharge port 122 and the upper discharge port 123 are arranged along the circumferential direction of the furnace body 110, and the horizontal projection included angle theta 1 of the lower discharge port 121 and the middle discharge port 122 and the horizontal projection included angle theta 2 of the middle discharge port 122 and the upper discharge port 123 are not smaller than 10 degrees.
The heating assembly comprises three heating electrodes 130 which are annularly distributed, the blanking assembly comprises seven blanking pipes 140, six blanking pipes 140 are uniformly distributed on the periphery of the heating mechanism, one blanking pipe 140 is positioned at the center of the heating mechanism, and the blanking pipes 140 comprise upper inclined pipe sections and lower vertical pipe sections.
The vibrating structure is arranged inside the furnace body 110 and used for breaking the crust of furnace burden, and the power mechanism 160 is arranged outside the furnace body 110 and used for driving the executing mechanism to move.
The furnace body 110 is cylindrical, the diameter D is 1-12 m, the height H of the inner space is 0.8-1.5 times of that of the direct D, and the furnace body 110 comprises an outer carbon steel shell, an inner refractory brick lining and a water cooling coil.
Fig. 3 is a schematic structural diagram of a melt processing system, a flue gas processing system and a multi-product co-production system of the carbon-reduced lithium ores of the present invention.
As shown in fig. 3, the melt processing system includes a first cooling device 210, a second cooling device 220, and a third cooling device 230.
The first cooling device 210 is used for cooling the high-density melt output by the smelting furnace and outputting a first solid containing ferromanganese, and the lower discharge hole 121 is connected with the first cooling device 210. The second cooling device 220 is used for cooling the medium density melt output by the smelting furnace, outputting a second solid containing elemental silicon, and the medium discharge port 122 is connected with the second cooling device 220. The third cooling device 230 is used for cooling the low-density melt output by the smelting furnace, outputting a third solid containing silicon dioxide and metal oxide, and the upper discharge hole 123 is connected with the third cooling device 230.
The flue gas treatment system comprises a first heat exchange device 311, a first gas-solid separation device 312, a first water quenching device 313, a first liquid-solid separation device 314, a second heat exchange device 321, a second gas-solid separation device 322, a second water quenching device 323, a first separation device 315, a first evaporative crystallization device 316, a second liquid-solid separation device 317, a first drying device 318, a second evaporative crystallization device 325, a third liquid-solid separation device 326, a second drying device 327, a third drying device 331 and a granulation device 332.
The first heat exchange device 311 is used for cooling and pre-dedusting the flue gas and outputting a first gas-solid mixture and first dust, the first gas-solid separation device 312 is used for performing gas-solid separation on the first gas-solid mixture and outputting first clean gas and second dust, the first water quenching device 313 is used for performing water quenching on primary solids formed by the first dust and the second dust and outputting a first solid-liquid mixture, and the first liquid-solid separation device 314 is used for performing liquid-solid separation on the first solid-liquid mixture and outputting insoluble slag and a first solution containing lithium hydroxide.
The second heat exchange device 321 is used for cooling and pre-dedusting the first clean gas and outputting a second gas-solid mixture and third dust, the second gas-solid separation device 322 is used for performing gas-solid separation on the second gas-solid mixture and outputting a second clean gas and fourth dust containing carbon monoxide, and the second water quenching device 323 is used for performing water quenching on a second-stage solid formed by the third dust and the fourth dust and outputting a third clean gas containing acetylene gas and a second solution containing lithium hydroxide.
The first separation device 315 performs separation treatment on the first solution, and outputs an alkaline solution and lithium hydroxide solids.
The first evaporation and crystallization device 316 is used for performing evaporation and crystallization treatment on the alkali solution and outputting a first crystal dispersion liquid, the second liquid-solid separation device 317 is used for performing liquid-solid separation treatment on the first crystal dispersion liquid and outputting solid alkali and reuse water, and the first drying device 318 is used for performing drying treatment on the solid alkali to obtain an alkali product.
The second evaporation and crystallization device 325 is used for performing evaporation and crystallization treatment on the second solution to output a second crystal dispersion liquid, the third liquid-solid separation device 326 is used for performing liquid-solid separation treatment on the second crystal dispersion liquid to output lithium hydroxide solids and reuse water, and the second drying device 327 is used for performing drying treatment on the lithium hydroxide solids (from the first separation device 315 and the third liquid-solid separation device 326) to obtain a lithium hydroxide product.
The third drying device 331 is used for drying the insoluble slag, and the granulating device 332 is used for granulating the dried insoluble slag and the third solid.
Also included are a first powder tank 341 storing primary solids, a second powder tank 342 storing secondary solids, a first gas tank 343 storing a second clean gas, and a second gas tank 344 storing a third clean gas.
Preferably, the first heat exchange device 311 and the first gas-solid separation device 312 form an integrated first heat exchange dust removal device, and the second heat exchange device 321 and the second gas-solid separation device 322 form an integrated second heat exchange dust removal device, which can specifically be a heat exchange dust removal device disclosed in the application number 2021101312443, the patent name of which is a heat exchange dust removal structure, a heat exchange dust removal device and a high-temperature dust-containing gas treatment method.
The multi-product co-production system of the carbon reduction lithium ore comprises the melt processing system and the flue gas processing system.
The multi-product co-production method of the carbon reduction lithium ore comprises the steps of treating flue gas and treating a molten solution. Wherein:
The steps of treating the flue gas comprise the steps 11-14, and specifically the steps are as follows:
In the operation, in the process that the flue gas stays in the first heat exchange equipment 311, carbon powder reacts with a lithium simple substance to generate gaseous lithium carbide, unreacted lithium simple substance and other alkali metal simple substances such as sodium simple substance and potassium simple substance are condensed and attached to dust, and the unreacted lithium simple substance and the other alkali metal simple substance are collected in the first solid through natural sedimentation of the first heat exchange equipment 311 and physical interception of the first gas-solid separation equipment 312, and the obtained first clean gas is mainly carbon monoxide and lithium carbide.
In step 12, the temperature of the first clean gas is continuously reduced to below 50 ℃ and solids are collected to obtain secondary solids and second clean gas containing carbon monoxide, and in the operation, gaseous lithium carbide is condensed and separated out and is collected in the secondary solids through natural sedimentation of the second heat exchange equipment 321 and physical interception of the second gas-solid separation equipment 322, and the obtained second clean gas is mainly carbon monoxide.
And 13, performing water quenching treatment on the primary solid by adopting first water quenching equipment 313, and filtering the generated first solid-liquid mixture to obtain a first solution containing lithium hydroxide and insoluble slag, wherein in the operation, alkali metal simple substances react with water to generate an alkaline first solution, and insoluble matters such as mineral powder, carbon powder and the like are collected in the insoluble slag.
The first solution is separated by a first separation device 315 to obtain an alkali solution and lithium hydroxide solids, specifically, the first solution is evaporated and concentrated to a supersaturated state, then cooled to room temperature, and then absolute ethyl alcohol is added to separate out lithium hydroxide, and then filtration is carried out to obtain the alkali solution and lithium hydroxide solids. In this operation, lithium hydroxide is precipitated due to low solubility in absolute ethanol, and a relatively pure lithium hydroxide solid can be obtained by filtration, while sodium hydroxide and potassium hydroxide are still dissolved in a liquid phase, so that an alkali solution can be obtained.
And further carrying out evaporative crystallization treatment, filtration treatment and drying treatment on the alkali solution to obtain an alkali product and reuse water.
In the step 14, the second water quenching equipment 323 is adopted to carry out water quenching treatment on the secondary solid to obtain third clean gas containing acetylene gas and second solution containing lithium hydroxide, in the operation, lithium carbide in the secondary solid reacts with water to generate lithium hydroxide and acetylene gas, the obtained second solution is a relatively pure lithium hydroxide solution, and the third clean gas is mainly acetylene gas.
And further carrying out evaporation crystallization, filtration treatment and drying treatment on the second solution to obtain a lithium hydroxide product and reuse water.
The step of treating the melt comprises steps 21-24, which are specifically as follows:
Step 21, according to the layering of different density components in the melt, discharging the high-density melt, the medium-density melt and the low-density melt in the melt in a segmented manner.
In step 22, the high-density melt is cooled by using the first cooling device 210 to obtain a first solid containing the ferromanganese alloy, and the first solid can be further purified to obtain a ferromanganese alloy product.
And step 23, cooling the medium density melt by using a second cooling device 220 to obtain a second solid containing the simple substance of silicon, and further purifying to obtain a simple substance of silicon product.
In step 24, the low-density melt is cooled by a third cooling device 230 to obtain a third solid containing silica and metal oxide. The third solid and the dried insoluble slag may be simultaneously subjected to granulation treatment for other process treatments.
The content of the present invention is described above. Those of ordinary skill in the art will be able to implement the invention based on these descriptions. Based on the foregoing, all other embodiments that may be obtained by one of ordinary skill in the art without undue burden are within the scope of the present invention.
Claims (9)
1. The multi-product co-production method of the carbon reduced lithium ore comprises the steps of carrying out reduction reaction on carbon, the lithium ore and a slag former to generate smoke and melt, and is characterized by further comprising the steps of treating the smoke and/or treating the melt, wherein:
the step of treating the flue gas comprises the following steps:
reducing the temperature of the flue gas to 500-700 ℃ and collecting solids to obtain primary solids and first clean gas;
Continuing to reduce the temperature of the first clean gas to below 50 ℃ and collecting solids to obtain secondary solids and second clean gas containing carbon monoxide;
Carrying out water quenching treatment on the primary solid, and then filtering the generated first solid-liquid mixture to obtain a first solution containing lithium hydroxide and insoluble residues;
Carrying out water quenching treatment on the secondary solid to obtain third clean gas containing acetylene gas and second solution containing lithium hydroxide;
The step of treating the melt comprises:
According to the layering of different density components in the molten liquid, discharging the high-density molten liquid, the medium-density molten liquid and the low-density molten liquid in the molten liquid in a sectional manner;
Cooling the high-density melt to obtain a first solid containing ferromanganese silicon alloy;
Cooling the medium-density melt to obtain a second solid containing a simple substance of silicon;
And (3) cooling the low-density melt to obtain a third solid containing silicon dioxide and metal oxide.
2. The method for co-production of multiple products of claim 1, further comprising separating the first solution to obtain an alkaline solution and lithium hydroxide solids.
3. The method for co-production of multiple products according to claim 2, wherein the separation treatment comprises the steps of evaporating and concentrating the first solution to a supersaturated state, cooling to room temperature, adding absolute ethyl alcohol to precipitate lithium hydroxide, and filtering to obtain an alkali solution and lithium hydroxide solid.
4. The method for co-production of multiple products according to claim 2, further comprising subjecting the alkaline solution to evaporative crystallization, filtration and drying to obtain an alkaline product and reuse water.
5. The method for co-production of multiple products of claim 2, further comprising subjecting the second solution to evaporative crystallization, filtration and drying to obtain a lithium hydroxide product and reuse water.
6. The method for co-production of multiple products according to claim 1, further comprising sequentially drying and granulating the insoluble residue.
7. The method for co-production of multiple products according to claim 1, wherein said slag former is CaO-SiO2-CaF2 composite slag former.
8. A multi-product co-production system used in the multi-product co-production method as claimed in any one of claims 1 to 7, comprising a smelting furnace for reducing carbon, lithium ores and slag formers and generating flue gas and molten liquid, characterized in that the multi-product co-production system further comprises a flue gas treatment system for treating the flue gas and/or a molten liquid treatment system for treating the molten liquid, wherein:
the flue gas treatment system comprises:
The first heat exchange equipment (311) is used for cooling and pre-dedusting the flue gas and outputting a first gas-solid mixture and first dust;
The first gas-solid separation equipment (312) is used for performing gas-solid separation treatment on the first gas-solid mixture and outputting first clean gas and second dust;
The first water quenching equipment (313) is used for carrying out water quenching treatment on primary solid formed by the first dust and the second dust and outputting a first solid-liquid mixture;
a first liquid-solid separation device (314) for performing liquid-solid separation treatment on the first solid-liquid mixture, and outputting insoluble slag and a first solution containing lithium hydroxide;
the second heat exchange device (321) is used for cooling and pre-dedusting the first clean gas and outputting a second gas-solid mixture and third dust;
a second gas-solid separation device (322) for performing gas-solid separation treatment on the second gas-solid mixture, and outputting a second clean gas containing carbon monoxide and a fourth dust;
the second water quenching equipment (323) is used for carrying out water quenching treatment on the secondary solid formed by the third dust and the fourth dust, and outputting a third clean gas containing acetylene gas and a second solution containing lithium hydroxide;
The melt processing system includes:
a first cooling device (210) for cooling the high-density melt output from the smelting furnace and outputting a first solid containing ferromanganese alloy;
A second cooling device (220) for cooling the medium density melt output from the smelting furnace and outputting a second solid containing elemental silicon;
and a third cooling device (230) for cooling the low-density melt output from the smelting furnace and outputting a third solid containing silica and metal oxide.
9. The multi-product co-production system of claim 8, wherein the smelting furnace comprises a furnace body (110) and a discharging assembly, and the discharging assembly comprises a plurality of materials sequentially arranged on the furnace body (110) from bottom to top:
the high-density melt discharge mechanism comprises a lower discharge hole (121) arranged on the furnace body (110), wherein the lower discharge hole (121) is connected with first cooling equipment (210);
The medium density melt discharge mechanism comprises a medium discharge hole (122) arranged on the furnace body (110), wherein the medium discharge hole (122) is connected with a second cooling device (220);
The low-density melt discharge mechanism comprises an upper discharge hole (123) arranged on the furnace body (110), and the upper discharge hole (123) is connected with a third cooling device (230).
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