CN112607753A - Environment-friendly process for producing lithium hydroxide monohydrate by mixing spodumene and lithium polymer - Google Patents
Environment-friendly process for producing lithium hydroxide monohydrate by mixing spodumene and lithium polymer Download PDFInfo
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- CN112607753A CN112607753A CN202011537343.3A CN202011537343A CN112607753A CN 112607753 A CN112607753 A CN 112607753A CN 202011537343 A CN202011537343 A CN 202011537343A CN 112607753 A CN112607753 A CN 112607753A
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- shell
- lithium hydroxide
- spodumene
- stirring
- flow guide
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- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910052642 spodumene Inorganic materials 0.000 title claims abstract description 41
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 36
- 229920000642 polymer Polymers 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000002156 mixing Methods 0.000 title claims abstract description 29
- 230000008569 process Effects 0.000 title claims abstract description 28
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 title claims abstract description 25
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 title claims abstract description 25
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 title claims abstract description 25
- 239000000428 dust Substances 0.000 claims abstract description 30
- 238000001816 cooling Methods 0.000 claims abstract description 26
- 238000001914 filtration Methods 0.000 claims abstract description 20
- 238000001354 calcination Methods 0.000 claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 238000001704 evaporation Methods 0.000 claims abstract description 11
- 238000002386 leaching Methods 0.000 claims abstract description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 5
- 230000007246 mechanism Effects 0.000 claims description 156
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 90
- 238000003756 stirring Methods 0.000 claims description 86
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 57
- 239000007788 liquid Substances 0.000 claims description 47
- 239000000463 material Substances 0.000 claims description 39
- 239000000843 powder Substances 0.000 claims description 32
- 239000002002 slurry Substances 0.000 claims description 27
- 238000007789 sealing Methods 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 18
- 239000000292 calcium oxide Substances 0.000 claims description 18
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 15
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 12
- 239000012452 mother liquor Substances 0.000 claims description 12
- 238000003860 storage Methods 0.000 claims description 11
- 230000008020 evaporation Effects 0.000 claims description 10
- 238000007710 freezing Methods 0.000 claims description 10
- 230000008014 freezing Effects 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 9
- 239000012065 filter cake Substances 0.000 claims description 9
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000012670 alkaline solution Substances 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 6
- 229910001424 calcium ion Inorganic materials 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 238000004806 packaging method and process Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- 238000007259 addition reaction Methods 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 230000002457 bidirectional effect Effects 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 3
- 230000003139 buffering effect Effects 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 238000009993 causticizing Methods 0.000 claims description 3
- 239000012043 crude product Substances 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 238000009434 installation Methods 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000008237 rinsing water Substances 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 3
- 239000000779 smoke Substances 0.000 claims description 3
- 239000008399 tap water Substances 0.000 claims description 3
- 235000020679 tap water Nutrition 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 239000012257 stirred material Substances 0.000 claims description 2
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 4
- 239000011707 mineral Substances 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 4
- 238000000605 extraction Methods 0.000 abstract description 3
- 238000000498 ball milling Methods 0.000 abstract description 2
- 230000020477 pH reduction Effects 0.000 abstract description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 abstract description 2
- 235000011152 sodium sulphate Nutrition 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract 1
- 239000008213 purified water Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 2
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 230000001360 synchronised effect Effects 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 210000005069 ears Anatomy 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003500 flue dust Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/02—Oxides; Hydroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F27/00—Mixers with rotary stirring devices in fixed receptacles; Kneaders
- B01F27/05—Stirrers
- B01F27/11—Stirrers characterised by the configuration of the stirrers
- B01F27/19—Stirrers with two or more mixing elements mounted in sequence on the same axis
- B01F27/191—Stirrers with two or more mixing elements mounted in sequence on the same axis with similar elements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F27/00—Mixers with rotary stirring devices in fixed receptacles; Kneaders
- B01F27/80—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis
- B01F27/90—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis with paddles or arms
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Mixers Of The Rotary Stirring Type (AREA)
Abstract
The invention relates to a process for producing lithium hydroxide monohydrate by using spodumene and a lithium polymer, which comprises the following steps: sequentially calcining spodumene at high temperature in a rotary kiln, cooling in a cooling kiln, adding a lithium polymer, carrying out ball milling in a jaw crusher together with the calcined spodumene, carrying out acidification kiln roasting, cooling, size mixing, leaching, press filtering and separation in a press filter, carrying out freeze separation on sodium sulfate, evaporating, recrystallizing at low temperature, drying and the like to obtain the spodumene. The invention selects spodumene and lithium polymer as raw materials, wherein the lithium polymer is a novel mineral source, has high grade, high extraction value and great economic benefit, solves the dilemma of insufficient lithium ore resources, and increases the risk of resisting insufficient resources of a production line. Meanwhile, a double-shaft humidifying stirrer is additionally arranged at the dust collecting position, the dust is humidified, the risk of dust emission is reduced, and the problem of environmental protection is effectively solved.
Description
Technical Field
The invention relates to the technical field of lithium hydroxide production, in particular to a process for producing lithium hydroxide monohydrate by mixing spodumene and a lithium polymer in an environment-friendly manner.
Background
The lithium hydroxide is widely applied to industries such as chemical raw materials, metallurgy, battery industry, ceramics, national defense, atomic energy, aerospace and the like, is used as an alkaline storage battery additive in the battery industry, can prolong the service life of the alkaline storage battery additive and increase the storage capacity of the alkaline storage battery additive. The main method for producing lithium hydroxide monohydrate at present is to grade 5.5% -6% (Li)2O) spodumene is taken as a raw material, and the spodumene is obtained by the process steps of high-temperature calcination transformation, cooling, ball milling, acidification roasting, cooling, size mixing, leaching, squeezing and separation, freezing separation of sodium sulfate, evaporation, low-temperature recrystallization and the like.
However, spodumene is insufficient in resources, and a new mineral source needs to be searched to meet the production requirement.
When the lithium hydroxide is produced by the traditional process, spodumene needs to be calcined at a high temperature of 950-1200 ℃, dust is easily generated in the calcining process, the problem of environmental protection is caused, meanwhile, the dust also contains effective components, and the utilization rate of raw materials is not high.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an environment-friendly process for producing lithium hydroxide monohydrate by mixing spodumene and a lithium polymer, wherein the process selects the spodumene and the lithium polymer as raw materials, the lithium polymer is a novel mineral source, has high grade and high extraction value, has great economic benefit, solves the dilemma when the spodumene resources are insufficient, and increases the risk of resisting the resource insufficiency of a production line. Meanwhile, a double-shaft humidifying stirrer is additionally arranged at the dust collecting position, the dust is humidified, the risk of dust emission is reduced, the environmental protection problem is effectively solved, meanwhile, effective components are recycled, and the utilization rate of raw materials is improved.
The purpose of the invention is realized by the following technical scheme:
an environment-friendly process for producing lithium hydroxide monohydrate by mixing spodumene and a lithium polymer comprises the following steps:
s1, sequentially calcining and cooling spodumene to obtain a spodumene roasted material, adding a lithium polymer, wherein the weight of the lithium polymer accounts for 0-60% of the weight of the spodumene roasted material, mixing the lithium polymer and the spodumene roasted material, crushing, finely grinding, adding acid for reaction, cooling the product of the acid addition reaction to be less than or equal to 90 ℃, and then mixing the product with water to obtain slurry, wherein the solid content of the slurry is 10-70%; the calcination process is carried out in a rotary kiln, the smoke dust generated by the rotary kiln passes through a tail gas treatment system, the dust is recycled to a double-shaft humidifying stirrer for humidification treatment, and then the dust flows to the rotary kiln for calcination;
s2, adding calcium carbonate slurry into the slurry obtained in the step S1, stirring and leaching, adjusting the temperature in a leaching tank to be less than or equal to 60 ℃ and the pH value to be 5.5-6, then adding calcium oxide to adjust the pH value to be 8-9, then filtering by using a filter press, purifying the filtered clear liquid by using lithium hydroxide mother liquor or calcium oxide, adjusting the pH value to be 9-12, and removing impurities of iron, manganese, aluminum and calcium in the filtered clear liquid;
s3, filtering the clear filtrate obtained in the step S2 again to obtain purified liquid and purified filter residues, causticizing the purified liquid by using 50% alkaline solution or crude product mother liquor, wherein the pH value of the causticized solution is 11-14, and the temperature is normal temperature;
s4, filtering the solution causticized in the step S3 to obtain a causticized liquid and causticized filter residues, wherein the equivalent content of lithium hydroxide Li2O in the causticized liquid is controlled to be 30-75 g/L, and the causticized liquid is filtered by a precision filter to remove part of calcium ions;
s5, freezing and separating the filtered causticized liquid into sodium sulfate decahydrate and lithium hydroxide solution in a freezing workshop, wherein the freezing temperature is-5 to-20 ℃;
s6, purifying sodium sulfate decahydrate through evaporation concentration, heating to take out crystal water to obtain anhydrous sodium sulfate, heating at the temperature of 200-800 ℃, filtering a lithium hydroxide solution through a precision filter to remove a part of calcium ions, then performing evaporation concentration, crystallizing, centrifuging, re-melting, filtering through the precision filter, performing evaporation concentration after filtering, cooling, crystallizing and separating to obtain lithium hydroxide crystals, heating through a disc dryer to obtain lithium hydroxide monohydrate, and heating at the temperature of 50-150 ℃;
s7, conveying the lithium hydroxide monohydrate obtained by heating the disc dryer to a vibrating screen through an air conveying device for particle screening, conveying the screened material to a vacuum feeding system for buffering, intermittently feeding the material to a weighing system through a spiral feeder, and then discharging the material to a pre-mixer;
s8, conveying the materials from the pre-mixer to a raw material distribution system, conveying one path of the materials to a vacuum feeding system, stacking the materials after passing through an automatic packaging system, and entering a finished product warehouse; and the other path is sent to a vacuum feeding system, is stacked through an airflow crushing system and an automatic packaging system and enters a finished product warehouse, and the finished product controls the magnetic substance not to exceed 30 PPb.
Further, in step S1, the calcination temperature is 950-1200 ℃ during calcination; during crushing, the particle size is required to be 1-5 cm; when in fine grinding, the granularity of the powder is required to be 200 meshes; and (3) adding sulfuric acid with the concentration of 98% during acid adding reaction, wherein the acid-material ratio is 2-5: 1, adding acid for reaction, and cooling to below 60 ℃; and during cooling, the cooling is carried out in a water cooling mode.
Further, in step S2, the solid content of the calcium carbonate slurry is 10% to 55%; adjusting the pH value of the added calcium oxide into powder with the mass fraction of more than 75% or slurry with the solid content of 10-55%; rinsing the filter cake filtered by the filter press by using tap water or process water, blowing the filter cake by using compressed air to ensure that the water content of the filter cake is less than or equal to 20%, and returning rinsing water to be used for size mixing in the step S1; during purification, if lithium hydroxide mother liquor is added, the concentration of the lithium hydroxide mother liquor is 10-50%, and if calcium oxide is added, the calcium oxide is powder with the mass fraction of more than 75% or calcium oxide slurry with the solid content of 10-55%.
Further, in the step S3, adding water into the purified filter residue to prepare slurry with the solid content of 10-70%, and returning to the step S1; the alkaline solution is sodium hydroxide solution, lithium hydroxide solution or the mixed solution of the sodium hydroxide solution and the lithium hydroxide solution.
Further, in step S4, after adding water to the causticized filter residue to prepare slurry with a solid content of 10% to 70%, the process returns to the step S2 for purification.
Furthermore, the double-shaft humidifying stirrer comprises a rack, a shell, a stirring mechanism, a reciprocating driving mechanism, a flow guide sliding block, a sealing piece, a sliding mechanism, a rotary driver and a humidifying mechanism, wherein the shell is arranged on the rack, the cross section of the shell is of a waist-round structure, the center of the shell is rectangular, and the two sides of the shell are semicircular and used for containing powder; the stirring mechanisms are provided with a pair of stirring mechanisms which are symmetrically arranged in the shell, and the upper end and the lower end of each stirring mechanism respectively penetrate through the top end and the bottom of the shell and are used for stirring powder; the reciprocating driving mechanism is arranged at the top end of the shell, the working end of the reciprocating driving mechanism is simultaneously connected with the pair of flow guide sliding blocks in a sliding manner, and the driving direction of the reciprocating driving mechanism is horizontally arranged and used for driving the pair of flow guide sliding blocks to be symmetrically and horizontally close to or far away from the shell; the guide sliding blocks are provided with a pair of guide sliding blocks, the guide sliding blocks are sleeved on a pair of working ends of the reciprocating driving mechanism, convex circles which are in sliding connection with the working ends of the reciprocating driving mechanism are arranged on the inner walls of the guide sliding blocks, the guide sliding blocks are hollow inside, the liquid inlet ends are communicated with the output end of the humidifying mechanism, and the liquid outlet ends are rotatably connected with the top end of the stirring mechanism and are communicated with each other; the sealing element is arranged at the position where the stirring mechanism penetrates through the shell and used for ensuring the internal sealing property of the shell when the stirring mechanism moves horizontally; the sliding mechanism is arranged at the bottom of the shell in a horizontally sliding manner and is rotationally connected with one end of the stirring mechanism, which extends out of the bottom of the shell; the rotary driver is arranged on the working end of the sliding mechanism, and an output shaft of the rotary driver is connected with the bottom end of the stirring mechanism and used for driving the stirring mechanism to rotate.
Further, the shell is provided with a feeding pipe, a discharging pipe and a waist-shaped via hole; the feeding pipe is arranged on the outer wall of the shell and used for feeding powder into the shell, the discharging pipe is arranged at the bottom of the shell and used for guiding out the stirred materials in the shell, the number of the waist-shaped through holes is four, the waist-shaped through holes are symmetrically arranged at the top end and the bottom end of the shell respectively, and the waist-shaped through holes are fixedly connected with the sealing piece and used for enabling the top end and the bottom end of the pair of stirring mechanisms to extend out of the shell to be connected with the flow guide sliding block; the stirring mechanism comprises a hollow rotating shaft and stirring blades, the upper end and the lower end of the hollow rotating shaft respectively penetrate through the upper end and the bottom end of the shell, the upper end of the hollow rotating shaft is rotatably connected with the liquid outlet end of the flow guide sliding block, the lower end of the hollow rotating shaft is rotatably connected with the working end of the sliding mechanism, a plurality of water spray holes are uniformly distributed on the outer wall, and the bottom end of the hollow rotating shaft is communicated with the interior of the shell; the stirring fan blades are uniformly distributed on the outer wall of the hollow rotating shaft and are used for stirring powder in the shell, and the diameter of the circumscribed circle of the cross section of each stirring fan blade is the same as the inner diameter of the semicircular structures on the two sides of the shell; the reciprocating driving mechanism comprises a first cylindrical cam, a second cylindrical cam, a two-way motor and a guide rod, wherein the axes of the first cylindrical cam and the second cylindrical cam are horizontally and symmetrically arranged at the upper end of the shell, two ends of the first cylindrical cam and the second cylindrical cam are rotationally connected with the shell and are respectively connected with a flow guide sliding block in a sliding manner, and the driving directions are coaxially and reversely arranged and are used for driving a pair of flow guide sliding blocks to symmetrically approach or depart from each other; the bidirectional motor is arranged in the center of the top end of the shell, and the pair of output shafts are respectively fixedly connected with the end parts of the first cylindrical cam and the second cylindrical cam and used for synchronously driving the pair of first cylindrical cam and the second cylindrical cam to rotate; the guide rods are arranged on two sides of the first cylindrical cam and the second cylindrical cam in pairs, two ends of each guide rod are fixedly connected with the shell, and the guide rods are in clearance fit with two sides of the flow guide sliding block and used for limiting the movement direction of the flow guide sliding block.
Furthermore, the flow guide sliding block comprises a sleeving part, a mounting lug, a first sleeve and a second sleeve, the sleeving part is sleeved on the working end of the reciprocating driving mechanism, the sleeving part is connected with the working end of the reciprocating driving mechanism in a sliding mode, and the inner part of the flow guide sliding block is of a hollow structure; the mounting lugs are symmetrically arranged on two sides of the sleeving part and are in clearance fit with the reciprocating driving mechanism so as to guide and limit the movement direction of the sleeving part; the one end of first sleeve is installed on installation ear top to with cup joint the inside intercommunication of portion, the other end is connected with humidification mechanism output for to leading-in pure water in the portion of cup jointing, the second sleeve is installed in the portion bottom of cup jointing, the second sleeve rotates with the rabbling mechanism top to be connected, and with the inside intercommunication of rabbling mechanism, be used for the leading-in rabbling mechanism of pure water that will get into in the portion of cup jointing.
Further, the sealing member is including fixed frame, go-between and flexible seal membrane, and fixed frame setting is on waist type via hole inner wall, and agrees with waist type via hole inner wall structure, and the go-between cover is established on rabbling mechanism, and rotates with rabbling mechanism and be connected, the outside inboard of flexible seal membrane respectively with fixed frame, go-between fixed connection for keep casing inside seal nature.
Furthermore, the sliding mechanism comprises a pair of guide rails and a pair of sliding mounting plates, the pair of guide rails are symmetrically arranged at the bottom of the shell and used for guiding and limiting the movement direction of the sliding mounting plates, the pair of sliding mounting plates are symmetrically arranged at the bottom of the shell, the top ends of the sliding mounting plates are attached to the bottom of the shell to move, two sides of the sliding mounting plates are slidably connected with the inner sides of the guide rails, the sliding mounting plates are rotatably connected with the bottom end of the stirring mechanism, and the bottoms of the sliding mounting plates are fixedly connected with the rotary driver; the humidifying mechanism comprises a liquid storage tank and a hydraulic pump, wherein the discharge end of the liquid storage tank is connected with the input end of the hydraulic pump, and the output end of the hydraulic pump is connected with the liquid inlet end of the flow guide sliding block.
The invention has the following advantages:
1. the process for producing the lithium hydroxide monohydrate by mixing the spodumene and the lithium polymer takes the spodumene and the lithium polymer as raw materials, wherein the grade of the lithium polymer reaches 8.5 to 12 percent (Li)2O), 25.05 percent of Al, 1.23 percent of Mg, 0.84 percent of Si, 0.69 percent of Mn, high grade and less impurity content, is a novel mineral source, has great extraction value and great economic benefit, also solves the dilemma when the lithium ore resources are insufficient, and increases the risk of insufficient resisting resources of the production line.
2. According to the invention, a special double-shaft humidifying stirrer is additionally arranged at the dust collecting position to humidify the dust, so that the risk of dust emission is reduced, and the problem of environmental protection is effectively solved.
3. Realize the synchronous drive to a pair of water conservancy diversion slider through reciprocating drive mechanism to realize the synchronous motion of a pair of rabbling mechanism on the horizontal direction, the even degree of stirring has been improved, and then work efficiency has been improved, and is concrete, the guide way isomorphism that sets up on first cylinder cam and the second cylinder cam outer wall and the cooperation of water conservancy diversion slider inner wall bulge circle, it is spacing to the water conservancy diversion slider to combine the guide bar, play drive water conservancy diversion slider along first cylinder cam and second cylinder cam axis reciprocating motion's effect. The periodic reciprocating motion of the flow guide sliding block can be realized under the condition that the rotating directions and the speeds of the first cylindrical cam and the second cylindrical cam are not changed, and then a pair of stirring mechanisms is driven to synchronously move.
4. The structure of rabbling mechanism can effectively reduce the work blind area, further improves stirring effect, and is specific, and stirring fan blade cross section circumscribed circle diameter is the same with casing both sides semi-circular structure internal diameter, and when stirring fan blade moved to the stroke end along with hollow rotating shaft to casing both sides, stirring fan blade periphery rotating surface and shells inner wall laminating. So can realize the intensive mixing to the powder in the casing, improve stirring effect.
5. The intake pipe and the force pump through with the casing are connected, have improved the ejection of compact speed of casing, and is concrete, and the staff is connected intake pipe input and force pump output, when needs are derived the material in the casing, opens the casing discharge end earlier, then the force pump passes through the intake pipe and pressurizes in to the casing, improves the ejection of compact speed of casing, improves production efficiency.
6. The leakproofness is good, has eliminated the effusion of dust in the course of the work through the sealing member, and the environmental friendliness is high, avoids causing adverse effect to staff's health.
7. Can collect tail gas and the material that the fish scale leaked through the biax humidifier, greatly reduced the loss of raw materials.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is a flow chart of the flue dust recycling process of the present invention;
FIG. 3 is a first perspective view of the present invention;
FIG. 4 is a perspective view of the housing of the present invention in a transparent state;
FIG. 5 is a second perspective view of the present invention;
FIG. 6 is a top view of the present invention;
FIG. 7 is a sectional view taken along line A-A of FIG. 6;
FIG. 8 is a perspective view of the housing of the present invention;
FIG. 9 is a perspective view of the reciprocating drive mechanism of the present invention;
FIG. 10 is a perspective view of the deflector slide of the present invention;
FIG. 11 is a perspective view of the seal of the present invention;
fig. 12 is a bottom view of the present invention.
The reference numbers in the figures are:
1-a frame;
2-a shell; 2 a-a feed pipe; 2 b-a discharge pipe; 2 c-a kidney via; 2 d-air inlet pipe;
3-a stirring mechanism; 3 a-a hollow rotating shaft; 3 b-stirring fan blades;
4-reciprocating drive mechanism; 4 a-a first cylindrical cam; 4 b-a second cylindrical cam; 4 c-a bi-directional motor; 4 d-a guide bar;
5-a flow guide sliding block; 5 a-a socket joint; 5 b-mounting ears; 5 c-a first sleeve; 5 d-a second sleeve;
6-a seal; 6 a-a fixed frame; 6 b-connecting ring; 6 c-a flexible sealing film;
7-a glide mechanism; 7 a-a guide rail; 7 b-a slide mounting plate;
8-rotary drive.
Detailed Description
The invention will be further described with reference to the accompanying drawings, but the scope of the invention is not limited to the following.
As shown in fig. 1 and 2, an environment-friendly process for producing lithium hydroxide monohydrate by mixing spodumene and a lithium polymer comprises the following steps:
s1, sequentially calcining and cooling spodumene to obtain a spodumene roasted material, adding a lithium polymer, wherein the weight of the lithium polymer accounts for 0-60% of the weight of the spodumene roasted material, mixing the lithium polymer and the spodumene roasted material, crushing, finely grinding, adding acid for reaction, cooling the product of the acid addition reaction to be less than or equal to 90 ℃, and then mixing the product with water to obtain slurry, wherein the solid content of the slurry is 10-70%; the calcination process is carried out in a rotary kiln, the smoke dust generated by the rotary kiln passes through a tail gas treatment system, the dust is recycled to a double-shaft humidifying stirrer for humidification treatment, and then the dust flows to the rotary kiln for calcination;
s2, adding calcium carbonate slurry into the slurry obtained in the step S1, stirring and leaching, adjusting the temperature in a leaching tank to be less than or equal to 60 ℃ and the pH value to be 5.5-6, then adding calcium oxide to adjust the pH value to be 8-9, then filtering by using a filter press, purifying the filtered clear liquid by using lithium hydroxide mother liquor or calcium oxide, adjusting the pH value to be 9-12, and removing impurities of iron, manganese, aluminum and calcium in the filtered clear liquid;
s3, filtering the clear filtrate obtained in the step S2 again to obtain purified liquid and purified filter residues, causticizing the purified liquid by using 50% alkaline solution or crude product mother liquor, wherein the pH value of the causticized solution is 11-14, and the temperature is normal temperature;
s4, filtering the solution causticized in the step S3 to obtain a causticized liquid and causticized filter residues, wherein the equivalent content of lithium hydroxide Li2O in the causticized liquid is controlled to be 30-75 g/L, and the causticized liquid is filtered by a precision filter to remove part of calcium ions;
s5, freezing and separating the filtered causticized liquid into sodium sulfate decahydrate and lithium hydroxide solution in a freezing workshop, wherein the freezing temperature is-5 to-20 ℃;
s6, purifying sodium sulfate decahydrate through evaporation concentration, heating to take out crystal water to obtain anhydrous sodium sulfate, heating at the temperature of 200-800 ℃, filtering a lithium hydroxide solution through a precision filter to remove a part of calcium ions, then performing evaporation concentration, crystallizing, centrifuging, re-melting, filtering through the precision filter, performing evaporation concentration after filtering, cooling, crystallizing and separating to obtain lithium hydroxide crystals, heating through a disc dryer to obtain lithium hydroxide monohydrate, and heating at the temperature of 50-150 ℃;
s7, conveying the lithium hydroxide monohydrate obtained by heating the disc dryer to a vibrating screen through an air conveying device for particle screening, conveying the screened material to a vacuum feeding system for buffering, intermittently feeding the material to a weighing system through a spiral feeder, and then discharging the material to a pre-mixer;
s8, conveying the materials from the pre-mixer to a raw material distribution system, conveying one path of the materials to a vacuum feeding system, stacking the materials after passing through an automatic packaging system, and entering a finished product warehouse; and the other path is sent to a vacuum feeding system, is stacked through an airflow crushing system and an automatic packaging system and enters a finished product warehouse, and the finished product controls the magnetic substance not to exceed 30 PPb.
Further, in step S1, the calcination temperature is 950-1200 ℃ during calcination; during crushing, the particle size is required to be 1-5 cm; when in fine grinding, the granularity of the powder is required to be 200 meshes; and (3) adding sulfuric acid with the concentration of 98% during acid adding reaction, wherein the acid-material ratio is 2-5: 1, adding acid for reaction, and cooling to below 60 ℃; and during cooling, the cooling is carried out in a water cooling mode.
Further, in step S2, the solid content of the calcium carbonate slurry is 10% to 55%; adjusting the pH value of the added calcium oxide into powder with the mass fraction of more than 75% or slurry with the solid content of 10-55%; rinsing the filter cake filtered by the filter press by using tap water or process water, blowing the filter cake by using compressed air to ensure that the water content of the filter cake is less than or equal to 20%, and returning rinsing water to be used for size mixing in the step S1; during purification, if lithium hydroxide mother liquor is added, the concentration of the lithium hydroxide mother liquor is 10-50%, and if calcium oxide is added, the calcium oxide is powder with the mass fraction of more than 75% or calcium oxide slurry with the solid content of 10-55%.
Further, in the step S3, adding water into the purified filter residue to prepare slurry with the solid content of 10-70%, and returning to the step S1; the alkaline solution is sodium hydroxide solution, lithium hydroxide solution or the mixed solution of the sodium hydroxide solution and the lithium hydroxide solution.
Further, in step S4, after adding water to the causticized filter residue to prepare slurry with a solid content of 10% to 70%, the process returns to the step S2 for purification.
Further, as shown in fig. 3 to 12, the double-shaft humidifying agitator includes a frame 1, a housing 2, an agitating mechanism 3, a reciprocating driving mechanism 4, a flow guide slider 5, a sealing member 6, a sliding mechanism 7, a rotary driver 8 and a humidifying mechanism, the housing 2 is mounted on the frame 1, the cross section of the housing 2 is a waist-round structure, the center is a rectangle, and the two sides are semicircles for accommodating powder; the stirring mechanisms 3 are provided with a pair and symmetrically arranged in the shell 2, and the upper end and the lower end of each stirring mechanism respectively penetrate through the top end and the bottom of the shell 2 and are used for stirring powder; the reciprocating driving mechanism 4 is arranged at the top end of the shell 2, the working end of the reciprocating driving mechanism 4 is simultaneously connected with the pair of flow guide sliding blocks 5 in a sliding manner, and the driving direction of the reciprocating driving mechanism 4 is horizontally arranged and used for driving the pair of flow guide sliding blocks 5 to be symmetrically and horizontally close to or far away from the shell 2; the flow guide sliding blocks 5 are provided with a pair of flow guide sliding blocks 5, the flow guide sliding blocks 5 are sleeved on a pair of working ends of the reciprocating driving mechanism 4, convex circles which are in sliding connection with the working ends of the reciprocating driving mechanism 4 are arranged on the inner walls of the flow guide sliding blocks 5, the inner parts of the flow guide sliding blocks are hollow structures, the liquid inlet ends of the flow guide sliding blocks are communicated with the output ends of the humidifying mechanism, and the liquid outlet ends of the flow guide sliding blocks are; the sealing element 6 is arranged at the position where the stirring mechanism 3 penetrates through the shell 2 and used for ensuring the internal sealing property of the shell 2 when the stirring mechanism 3 moves horizontally; the sliding mechanism 7 is horizontally arranged at the bottom of the shell 2 in a sliding way, and the sliding mechanism 7 is rotationally connected with one end of the stirring mechanism 3 extending out of the bottom of the shell 2; the rotary driver 8 is arranged on the working end of the sliding mechanism 7, and the output shaft of the rotary driver 8 is connected with the bottom end of the stirring mechanism 3 and used for driving the stirring mechanism 3 to rotate.
The reciprocating drive mechanism 4, the rotary driver 8 and the humidifying mechanism are all electrically connected with the controller. A humidity sensor electrically connected with the controller and used for detecting the humidity of the powder is also arranged in the shell 2 and used for accurately controlling the water feeding amount of the humidifying mechanism. The worker drops the powder into the housing 2 from the feed end of the housing 2 and then sends signals to the reciprocating drive mechanism 4, the rotary driver 8 and the humidifying mechanism through the controller. The reciprocating driving mechanism 4 receives the signal and simultaneously drives the pair of flow guide sliding blocks 5 to approach or separate from each other, so as to drive the pair of stirring mechanisms 3 which are rotatably connected with the liquid outlet ends of the flow guide sliding blocks 5 to approach or separate from each other. The rotary driver 8 receives the signal and drives the pair of stirring mechanisms 3 to rotate, thereby realizing the stirring of the powder in the shell 2. The humidifying mechanism pressurizes the purified water after receiving the signal and then sends the pressurized purified water into the flow guide sliding block 5, and the water enters the stirring mechanism 3 through the liquid outlet end of the flow guide sliding block 5 and is finally sprayed into the shell 2 to humidify the powder. The reciprocating driving mechanism 4, the rotary driver 8 and the humidifying mechanism are matched together to fully mix the materials. After the stirring is completed, the material is discharged by opening the discharge end at the bottom of the shell 2. The flow guide sliding block 5 and the sliding mechanism 7 are matched with each other, so that the stirring mechanism 3 is limited, and the central axis of the stirring mechanism 3 is vertical all the time in the motion process.
Further, the shell 2 is provided with a feeding pipe 2a, a discharging pipe 2b and a waist-shaped via hole 2 c; the feeding pipe 2a is arranged on the outer wall of the shell 2 and used for feeding powder into the shell 2, the discharging pipe 2b is arranged at the bottom of the shell 2 and used for guiding out materials which are stirred in the shell 2, four waist-shaped through holes 2c are arranged, the waist-shaped through holes 2c are symmetrically arranged at the top end and the bottom end of the shell 2 respectively, and the waist-shaped through holes 2c are fixedly connected with a sealing element 6 and are used for respectively extending the top end and the bottom end of the stirring mechanism 3 out of the shell 2 to be connected with a flow guide sliding block 5 and a sliding mechanism 7; the feed pipe 2a and the discharge pipe 2b are provided with control valves electrically connected with the controller. The operator opens the control valve on the feed pipe 2a and introduces the powder to be stirred into the housing 2. After the stirring has been completed, the material is removed from the outlet pipe 2b by opening the control valve at the outlet pipe 2 b. Through the waist-shaped via hole 2c, the upper end and the lower end of the stirring mechanism 3 can be respectively connected with the flow guide sliding block 5 and the sliding mechanism 7. Casing 2 still is equipped with intake pipe 2d, intake pipe 2d install on casing 2 outer wall and with the inside intercommunication of casing 2, the staff is connected intake pipe 2d input and force pump output, when the material of needs in to casing 2 is derived, opens 2 discharge ends of casing earlier, then the force pump passes through intake pipe 2d and pressurizes in to casing 2, improves casing 2's ejection of compact speed, improves production efficiency. The stirring mechanism 3 comprises a hollow rotating shaft 3a and stirring fan blades 3b, the upper end and the lower end of the hollow rotating shaft 3a respectively penetrate through the upper end and the bottom end of the shell 2, the upper end is rotatably connected with the liquid outlet end of the flow guide sliding block 5, the lower end is rotatably connected with the working end of the sliding mechanism 7, a plurality of water spray holes are uniformly distributed on the outer wall, and the bottom end is connected with the rotary driver 8; stirring fan blade 3b evenly distributed is on hollow rotating shaft 3a outer wall for stir the powder in the casing 2, and hollow rotating shaft 3a is through the intercommunication of top and water conservancy diversion slider 5, and the pure water that the leading-in humidification mechanism sent into humidifies the powder through the water jet hole of seting up on the outer wall. The humidification is monitored by a humidity sensor in the housing 2 to accurately control the amount of water delivered by the humidification mechanism. The water spraying holes of the hollow rotating shaft 3a are subjected to anti-clogging treatment. The diameter of the circumscribed circle of the cross section of the stirring fan blade 3b is the same as the inner diameter of the semicircular structures at the two sides of the shell 2, when the stirring fan blade 3b moves to the two sides of the shell 2 along with the hollow rotating shaft 3a to the tail end of the stroke, the peripheral rotating surface of the stirring fan blade 3b is attached to the inner wall of the shell 2, so that the powder in the shell 2 can be fully mixed, and the stirring effect is improved; the reciprocating driving mechanism 4 comprises a first cylindrical cam 4a, a second cylindrical cam 4b, a two-way motor 4c and a guide rod 4d, the axes of the first cylindrical cam 4a and the second cylindrical cam 4b are horizontally and symmetrically arranged at the upper end of the shell 2, two ends of the first cylindrical cam 4a and the second cylindrical cam 4b are rotatably connected with the shell 2 and are respectively in sliding connection with one flow guide sliding block 5, the driving direction is coaxially and reversely arranged and used for driving the pair of flow guide sliding blocks 5 to symmetrically approach or leave each other; the bidirectional motor 4c is arranged at the center of the top end of the shell 2, and a pair of output shafts are respectively fixedly connected with the end parts of the first cylindrical cam 4a and the second cylindrical cam 4b and used for synchronously driving the first cylindrical cam 4a and the second cylindrical cam 4b to rotate; guide bar 4d sets up in first cylindrical cam 4a and second cylindrical cam 4b both sides in pairs, guide bar 4d both ends and 2 fixed connection of casing, guide bar 4d and 5 both sides clearance fit of water conservancy diversion slider, be used for spacing to the direction of motion of water conservancy diversion slider 5, two-way motor 4c is connected with the controller electricity, the cooperation of the guide way isomorphism of seting up on first cylindrical cam 4a and the second cylindrical cam 4b outer wall and the protruding circle of 5 inner walls of water conservancy diversion slider, combine guide bar 4d to the spacing of water conservancy diversion slider 5, play the effect of drive water conservancy diversion slider 5 along first cylindrical cam 4a and second cylindrical cam 4b axis reciprocating motion. The periodic reciprocating motion of the flow guide sliding block 5 can be realized under the condition that the rotating directions and the speeds of the first cylindrical cam 4a and the second cylindrical cam 4b are not changed, and then the pair of stirring mechanisms 3 is driven to synchronously move.
Further, the flow guide sliding block 5 comprises a sleeving part 5a, a mounting lug 5b, a first sleeve 5c and a second sleeve 5d, the sleeving part 5a is sleeved on the working end of the reciprocating driving mechanism 4, the sleeving part 5a is connected with the working end of the reciprocating driving mechanism 4 in a sliding mode, and the inner part of the flow guide sliding block is of a hollow structure; the mounting lugs 5b are symmetrically arranged at two sides of the sleeving part 5a, and the mounting lugs 5b are in clearance fit with the reciprocating driving mechanism 4 and used for guiding and limiting the movement direction of the sleeving part 5 a; the one end of first sleeve 5c is installed on installation ear 5b top to with the inside intercommunication of portion 5a that cup joints, the other end is connected with humidification mechanism output, for leading-in pure water in to the portion 5a that cup joints, second sleeve 5d is installed in the portion 5a bottom that cup joints, and second sleeve 5d rotates with 3 tops of rabbling mechanism to be connected, and with 3 inside intercommunications of rabbling mechanism, be used for the leading-in rabbling mechanism 3 of pure water that will get into in the portion 5a that cup joints.
The convex circle of the flow guide sliding block 5 is arranged on the inner wall of the outer wall laminating of the outer wall of the first cylindrical cam 4a and the outer wall laminating of the outer wall of the second cylindrical cam 4b of the reciprocating driving mechanism 4 and matched with the guide grooves on the outer wall of the first cylindrical cam 4a and the outer wall of the second cylindrical cam 4b to realize reciprocating motion. The guide rod 4d performs a limiting and guiding function on the mounting lug 5b so as to limit and guide the movement direction of the socket 5 a. The joints of the first sleeve 5c and the second sleeve 5d with the top ends of the humidifying mechanism and the stirring mechanism 3 are provided with sealing bearings, which are not shown in the figure.
Further, the sealing element 6 comprises a fixing frame 6a, a connecting ring 6b and a flexible sealing film 6c, the fixing frame 6a is arranged on the inner wall of the waist-shaped via hole 2c and is matched with the inner wall structure of the waist-shaped via hole 2c, the connecting ring 6b is sleeved on the stirring mechanism 3 and is rotatably connected with the stirring mechanism 3, and the inner side of the outer side of the flexible sealing film 6c is fixedly connected with the fixing frame 6a and the connecting ring 6b respectively to keep the internal sealing performance of the shell 2.
The flexible sealing film 6c has better extensibility. When the connecting ring 6b moves horizontally along with the stirring mechanism 3, the flexible sealing film 6c is subjected to recoverable tensile deformation, and the sealing performance of the interior of the shell 2 is always ensured.
Furthermore, the sliding mechanism 7 comprises a guide rail 7a and a sliding mounting plate 7b, the guide rail 7a has a pair of guide rails 7a, the pair of guide rails 7a is symmetrically arranged at the bottom of the housing 2 for guiding and limiting the moving direction of the sliding mounting plate 7b, the sliding mounting plate 7b has a pair of sliding mounting plates 7b, the pair of sliding mounting plates 7b is symmetrically arranged at the bottom of the housing 2, the top end of the sliding mounting plate 7b is attached to the bottom of the housing 2 to move, two sides of the sliding mounting plate 7b are slidably connected with the inner sides of the guide rails 7a, the sliding mounting plate 7b is rotatably connected with the bottom end of the stirring mechanism 3, the bottom end is fixedly connected with the rotary driver 8, the moving direction of the sliding mounting plate 7b is limited by the guide rails 7a, when the stirring mechanism 3 moves horizontally along with the guide slider 5, the bottom end of the stirring mechanism 3 drives the sliding mounting plate 7, not shown in the figures. The slide mounting plate 7b also supports the rotary drive 8; the humidifying mechanism comprises a liquid storage tank and a hydraulic pump, the discharge end of the liquid storage tank is connected with the input end of the hydraulic pump, the output end of the hydraulic pump is connected with the liquid inlet end of the flow guide sliding block 5, and the hydraulic pump is electrically connected with the controller. The controller pressurizes the purified water stored in the liquid storage tank through the hydraulic pump, then sends the pressurized purified water into the flow guide sliding block 5, and finally sprays the pressurized purified water into the shell 2 through the stirring mechanism 3 to humidify the powder. The fluid reservoir and the hydraulic pump are not shown in the figures.
The working steps of the double-shaft humidifying stirrer are as follows:
firstly, putting the dust into the shell 2 from the feeding end of the shell 2, and then sending signals to the reciprocating driving mechanism 4, the rotary driver 8 and the humidifying mechanism through the controller.
And step two, the reciprocating driving mechanism 4 simultaneously drives the pair of flow guide sliding blocks 5 to approach or separate from each other after receiving the signal, and further drives the pair of stirring mechanisms 3 which are rotatably connected with the liquid outlet ends of the flow guide sliding blocks 5 to approach or separate from each other.
And step three, the rotary driver 8 drives the pair of stirring mechanisms 3 to rotate after receiving the signals, so that the powder in the shell 2 is stirred.
And step four, pressurizing the purified water by the humidifying mechanism after receiving the signal, sending the pressurized purified water into the flow guide sliding block 5, enabling the water to enter the stirring mechanism 3 through the liquid outlet end of the flow guide sliding block 5, and finally spraying the water into the shell 2 to humidify the powder.
And step five, the reciprocating driving mechanism 4, the rotary driver 8 and the humidifying mechanism are matched together to fully mix the materials, and after stirring is completed, the materials are discharged by opening the discharge end at the bottom of the shell 2 and then transferred into the rotary kiln for calcination again.
The double-shaft humidifying stirrer is additionally arranged at the tail gas treatment working section of the rotary kiln, after the tail gas of the rotary kiln is treated by the multi-tube ceramic dust remover and the bag-type dust remover to reach the standard, the tail gas is discharged in an organized manner through a chimney of 50 meters, and the dust collected by the multi-tube ceramic dust remover and the bag-type dust remover is conveyed to the double-shaft humidifying stirrer through the pipeline conveyor, the screw conveyor and the scraper conveyor, so that the dust is humidified, on one hand, the dust pollution is reduced, on the other hand, the raw material components in the dust are collected and utilized again, and the.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. An environment-friendly process for producing lithium hydroxide monohydrate by mixing spodumene and a lithium polymer, which is characterized by comprising the following steps: the method comprises the following steps:
s1, sequentially calcining and cooling spodumene to obtain a spodumene roasted material, adding a lithium polymer, wherein the weight of the lithium polymer accounts for 0-60% of the weight of the spodumene roasted material, mixing the lithium polymer and the spodumene roasted material, crushing, finely grinding, adding acid for reaction, cooling the product of the acid addition reaction to be less than or equal to 90 ℃, and then mixing the product with water to obtain slurry, wherein the solid content of the slurry is 10-70%; the calcination process is carried out in a rotary kiln, the smoke dust generated by the rotary kiln passes through a tail gas treatment system, the dust is recycled to a double-shaft humidifying stirrer for humidification treatment, and then the dust flows to the rotary kiln for calcination;
s2, adding calcium carbonate slurry into the slurry obtained in the step S1, stirring and leaching, adjusting the temperature in a leaching tank to be less than or equal to 60 ℃ and the pH value to be 5.5-6, then adding calcium oxide to adjust the pH value to be 8-9, then filtering by using a filter press, purifying the filtered clear liquid by using lithium hydroxide mother liquor or calcium oxide, adjusting the pH value to be 9-12, and removing impurities of iron, manganese, aluminum and calcium in the filtered clear liquid;
s3, filtering the clear filtrate obtained in the step S2 again to obtain purified liquid and purified filter residues, causticizing the purified liquid by using 50% alkaline solution or crude product mother liquor, wherein the pH value of the causticized solution is 11-14, and the temperature is normal temperature;
s4, filtering the solution causticized in the step S3 to obtain causticized liquid and causticized filter residue, wherein lithium hydroxide Li in the causticized liquid2Controlling the equivalent content of O to be 30-75 g/L, and filtering the causticized liquid through a precision filter to remove part of calcium ions;
s5, freezing and separating the filtered causticized liquid into sodium sulfate decahydrate and lithium hydroxide solution in a freezing workshop, wherein the freezing temperature is-5 to-20 ℃;
s6, purifying sodium sulfate decahydrate through evaporation concentration, heating to take out crystal water to obtain anhydrous sodium sulfate, heating at the temperature of 200-800 ℃, filtering a lithium hydroxide solution through a precision filter to remove a part of calcium ions, then performing evaporation concentration, crystallizing, centrifuging, re-melting, filtering through the precision filter, performing evaporation concentration after filtering, cooling, crystallizing and separating to obtain lithium hydroxide crystals, heating through a disc dryer to obtain lithium hydroxide monohydrate, and heating at the temperature of 50-150 ℃;
s7, conveying the lithium hydroxide monohydrate obtained by heating the disc dryer to a vibrating screen through an air conveying device for particle screening, conveying the screened material to a vacuum feeding system for buffering, intermittently feeding the material to a weighing system through a spiral feeder, and then discharging the material to a pre-mixer;
s8, conveying the materials from the pre-mixer to a raw material distribution system, conveying one path of the materials to a vacuum feeding system, stacking the materials after passing through an automatic packaging system, and entering a finished product warehouse; and the other path is sent to a vacuum feeding system, is stacked through an airflow crushing system and an automatic packaging system and enters a finished product warehouse, and the finished product controls the magnetic substance not to exceed 30 PPb.
2. The process for producing lithium hydroxide monohydrate by mixing spodumene and lithium polymer according to claim 1, which comprises the following steps: in the step S1, the calcining temperature is 950-1200 ℃ during calcining; during crushing, the particle size is required to be 1-5 cm; when in fine grinding, the granularity of the powder is required to be 200 meshes; and (3) adding sulfuric acid with the concentration of 98% during acid adding reaction, wherein the acid-material ratio is 2-5: 1, adding acid for reaction, and cooling to below 60 ℃; and during cooling, the cooling is carried out in a water cooling mode.
3. The process for producing lithium hydroxide monohydrate by mixing spodumene and lithium polymer according to claim 1, which comprises the following steps: in step S2, the solid content of the calcium carbonate slurry is 10-55%; adjusting the pH value of the added calcium oxide into powder with the mass fraction of more than 75% or slurry with the solid content of 10-55%; rinsing the filter cake filtered by the filter press by using tap water or process water, blowing the filter cake by using compressed air to ensure that the water content of the filter cake is less than or equal to 20%, and returning rinsing water to be used for size mixing in the step S1; during purification, if lithium hydroxide mother liquor is added, the concentration of the lithium hydroxide mother liquor is 10-50%, and if calcium oxide is added, the calcium oxide is powder with the mass fraction of more than 75% or calcium oxide slurry with the solid content of 10-55%.
4. The process for producing lithium hydroxide monohydrate by mixing spodumene and lithium polymer according to claim 1, which comprises the following steps: in the step S3, adding water into the purified filter residue to prepare slurry with the solid content of 10-70%, and returning to the step S1; the alkaline solution is sodium hydroxide solution, lithium hydroxide solution or the mixed solution of the sodium hydroxide solution and the lithium hydroxide solution.
5. The process for producing lithium hydroxide monohydrate by mixing spodumene and lithium polymer according to claim 1, which comprises the following steps: in step S4, adding water into the causticized filter residue to prepare slurry with solid content of 10-70%, and returning to the step S2 for purification.
6. The process for producing lithium hydroxide monohydrate by mixing spodumene and lithium polymer according to claim 1, which comprises the following steps: the double-shaft humidifying stirrer comprises a rack (1), a shell (2), a stirring mechanism (3), a reciprocating driving mechanism (4), a flow guide sliding block (5), a sealing element (6), a sliding mechanism (7), a rotary driver (8) and a humidifying mechanism, wherein the shell (2) is installed on the rack (1), the cross section of the shell (2) is of a waist-round structure, the center of the shell is rectangular, and the two sides of the shell are semicircular and used for containing powder; the stirring mechanisms (3) are provided with a pair and symmetrically arranged in the shell (2), and the upper end and the lower end of each stirring mechanism respectively penetrate through the top end and the bottom of the shell (2) and are used for stirring powder; the reciprocating driving mechanism (4) is installed at the top end of the shell (2), the working end of the reciprocating driving mechanism (4) is simultaneously in sliding connection with the pair of flow guide sliding blocks (5), and the driving direction of the reciprocating driving mechanism (4) is horizontally arranged and used for driving the pair of flow guide sliding blocks (5) to be symmetrically and horizontally close to or far away from the shell (2); the flow guide sliding blocks (5) are provided with a pair of pairs, the flow guide sliding blocks (5) are sleeved on a pair of working ends of the reciprocating driving mechanism (4), convex circles which are in sliding connection with the working ends of the reciprocating driving mechanism (4) are arranged on the inner walls of the flow guide sliding blocks (5), the flow guide sliding blocks are hollow inside, a liquid inlet end is communicated with an output end of the humidifying mechanism, and a liquid outlet end is rotatably connected with the top end of the stirring mechanism (3) and communicated with each other; the sealing element (6) is arranged at the position where the stirring mechanism (3) penetrates through the shell (2) and is used for ensuring the internal sealing property of the shell (2) when the stirring mechanism (3) moves horizontally; the sliding mechanism (7) is arranged at the bottom of the shell (2) in a horizontally sliding manner, and the sliding mechanism (7) is rotatably connected with one end, extending out of the bottom of the shell (2), of the stirring mechanism (3); the rotary driver (8) is arranged on the working end of the sliding mechanism (7), and the output shaft of the rotary driver (8) is connected with the bottom end of the stirring mechanism (3) and used for driving the stirring mechanism (3) to rotate.
7. The process for preparing lithium hydroxide monohydrate by mixing spodumene and lithium polymer according to claim 6, which comprises the following steps: the shell (2) is provided with a feeding pipe (2a), a discharging pipe (2b) and a waist-shaped via hole (2 c); the feeding pipe (2a) is arranged on the outer wall of the shell (2) and used for feeding powder into the shell (2), the discharging pipe (2b) is arranged at the bottom of the shell (2) and used for guiding out the stirred material in the shell (2), the number of the waist-shaped through holes (2c) is four, the waist-shaped through holes (2c) are respectively symmetrically arranged at the top end and the bottom of the shell (2), the waist-shaped through holes (2c) are fixedly connected with the sealing element (6) and are respectively used for enabling the top end and the bottom end of the pair of stirring mechanisms (3) to extend out of the shell (2) to be connected with the flow guide sliding block (5) and the sliding mechanism (7); the shell (2) is also provided with an air inlet pipe (2d), the air inlet pipe (2d) is installed on the outer wall of the shell (2) and is communicated with the interior of the shell (2), the stirring mechanism (3) comprises a hollow rotating shaft (3a) and stirring fan blades (3b), the upper end and the lower end of the hollow rotating shaft (3a) respectively penetrate through the upper end and the bottom end of the shell (2), the upper end is rotatably connected with the liquid outlet end of the flow guide sliding block (5), the lower end is rotatably connected with the working end of the sliding mechanism (7), a plurality of water spray holes are uniformly distributed on the outer wall, and the bottom end is; the stirring fan blades (3b) are uniformly distributed on the outer wall of the hollow rotating shaft (3a) and are used for stirring powder in the shell (2), and the diameter of the circumscribed circle of the cross section of each stirring fan blade (3b) is the same as the inner diameter of the semicircular structures at the two sides of the shell (2); the reciprocating driving mechanism (4) comprises a first cylindrical cam (4a), a second cylindrical cam (4b), a two-way motor (4c) and a guide rod (4d), the axes of the first cylindrical cam (4a) and the second cylindrical cam (4b) are horizontally and symmetrically arranged at the upper end of the shell (2), two ends of the first cylindrical cam and the second cylindrical cam are rotatably connected with the shell (2) and are respectively in sliding connection with one flow guide sliding block (5), the driving directions are coaxially and reversely arranged and used for driving the pair of flow guide sliding blocks (5) to be symmetrically close to or far away from each other; the bidirectional motor (4c) is arranged at the center of the top end of the shell (2), and a pair of output shafts are respectively fixedly connected with the end parts of the first cylindrical cam (4a) and the second cylindrical cam (4b) and used for synchronously driving the first cylindrical cam (4a) and the second cylindrical cam (4b) to rotate; guide bar (4d) set up in first cylinder cam (4a) and second cylinder cam (4b) both sides in pairs, guide bar (4d) both ends and casing (2) fixed connection, guide bar (4d) and water conservancy diversion slider (5) both sides clearance fit for carry on spacingly to the direction of motion of water conservancy diversion slider (5).
8. The process for preparing lithium hydroxide monohydrate by mixing spodumene and lithium polymer according to claim 7, which comprises the following steps: the flow guide sliding block (5) comprises a sleeving part (5a), a mounting lug (5b), a first sleeve (5c) and a second sleeve (5d), the sleeving part (5a) is sleeved on the working end of the reciprocating driving mechanism (4), the sleeving part (5a) is in sliding connection with the working end of the reciprocating driving mechanism (4), and the inner part of the flow guide sliding block is of a hollow structure; the mounting lugs (5b) are symmetrically arranged at two sides of the sleeving part (5a), and the mounting lugs (5b) are in clearance fit with the reciprocating driving mechanism (4) and used for guiding and limiting the movement direction of the sleeving part (5 a); the one end of first sleeve (5c) is installed on installation ear (5b) top to with cup joint portion (5a) inside intercommunication, the other end is connected with humidification mechanism output, be used for to leading-in pure water in cup joint portion (5a), second sleeve (5d) are installed in cup joint portion (5a) bottom, second sleeve (5d) are rotated with rabbling mechanism (3) top and are connected, and with rabbling mechanism (3) inside intercommunication, be used for leading-in rabbling mechanism (3) of the pure water that will get into in cup joint portion (5 a).
9. The process for preparing lithium hydroxide monohydrate by mixing spodumene and lithium polymer according to claim 7, which comprises the following steps: sealing member (6) are including fixed frame (6a), go-between (6b) and flexible seal membrane (6c), fixed frame (6a) set up on waist type via hole (2c) inner wall, and agree with waist type via hole (2c) inner wall structure, go-between (6b) cover is established on rabbling mechanism (3), and rotate with rabbling mechanism (3) and be connected, the outside inboard of flexible seal membrane (6c) respectively with fixed frame (6a), go-between (6b) fixed connection, be used for keeping casing (2) internal seal nature.
10. The process for preparing lithium hydroxide monohydrate by mixing spodumene and lithium polymer according to claim 6, which comprises the following steps: the sliding mechanism (7) comprises a guide rail (7a) and a sliding mounting plate (7b), the guide rail (7a) is provided with a pair of guide rails (7a), the pair of guide rails (7a) is symmetrically arranged at the bottom of the shell (2) and used for guiding and limiting the movement direction of the sliding mounting plate (7b), the sliding mounting plate (7b) is provided with a pair of sliding mounting plates (7b), the pair of sliding mounting plates (7b) is symmetrically arranged at the bottom of the shell (2), the top end of the sliding mounting plate (7b) is attached to the bottom of the shell (2) to move, two sides of the sliding mounting plate (7b) are in sliding connection with the inner sides of the guide rails (7a), the sliding mounting plate (7b) is rotatably connected with the bottom end of the stirring mechanism (3; the humidifying mechanism comprises a liquid storage tank and a hydraulic pump, the discharge end of the liquid storage tank is connected with the input end of the hydraulic pump, and the output end of the hydraulic pump is connected with the liquid inlet end of the flow guide sliding block (5).
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|---|---|---|---|---|
| CN1229059A (en) * | 1999-03-05 | 1999-09-22 | 四川省绵阳锂盐厂 | Technology for producing single water lithium hydroxide using spodumene |
| CN102701239A (en) * | 2012-03-19 | 2012-10-03 | 江西赣锋锂业股份有限公司 | Method for preparing lithium hydroxide monohydrate by extracting lithium from spodumene |
| CN102838140A (en) * | 2012-09-14 | 2012-12-26 | 四川国润新材料有限公司 | Method for directly producing environment-friendly lithium hydroxide monohydrate from spodumene |
| CN208066208U (en) * | 2018-01-17 | 2018-11-09 | 青岛华晨电力环保设备有限公司 | A kind of twin shaft wetting stirrer |
| CN111439760A (en) * | 2019-12-24 | 2020-07-24 | 广西天源新能源材料有限公司 | Production process of micro-powder lithium hydroxide monohydrate |
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- 2020-12-23 CN CN202011537343.3A patent/CN112607753A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1229059A (en) * | 1999-03-05 | 1999-09-22 | 四川省绵阳锂盐厂 | Technology for producing single water lithium hydroxide using spodumene |
| CN102701239A (en) * | 2012-03-19 | 2012-10-03 | 江西赣锋锂业股份有限公司 | Method for preparing lithium hydroxide monohydrate by extracting lithium from spodumene |
| CN102838140A (en) * | 2012-09-14 | 2012-12-26 | 四川国润新材料有限公司 | Method for directly producing environment-friendly lithium hydroxide monohydrate from spodumene |
| CN208066208U (en) * | 2018-01-17 | 2018-11-09 | 青岛华晨电力环保设备有限公司 | A kind of twin shaft wetting stirrer |
| CN111439760A (en) * | 2019-12-24 | 2020-07-24 | 广西天源新能源材料有限公司 | Production process of micro-powder lithium hydroxide monohydrate |
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Address after: Room A212-017, Public Service Center, No. 1, Zhongma Avenue, Zhongma Qinzhou Industrial Park, Qinzhou Port Area, Qinzhou, China (Guangxi) Free Trade Pilot Zone, Qinzhou, Guangxi Zhuang Autonomous Region, 535000 (business site: No. 6, Dolphin Road, Qinzhou Port Economic and Technological Development Zone, Qinzhou City) Applicant after: Guangxi Yabao Lithium Industry Co.,Ltd. Address before: No.6, dolphin Road, Qinzhou port, Qinzhou City, Guangxi Zhuang Autonomous Region Applicant before: Guangxi Tianyuan new energy materials Co.,Ltd. |
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Application publication date: 20210406 |