CN114314626B - Method for reducing sodium content in fluorine-containing raw material - Google Patents
Method for reducing sodium content in fluorine-containing raw material Download PDFInfo
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- 239000011734 sodium Substances 0.000 title claims abstract description 62
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 61
- 239000011737 fluorine Substances 0.000 title claims abstract description 61
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 title claims abstract description 59
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 59
- 239000002994 raw material Substances 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 238000002386 leaching Methods 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000005243 fluidization Methods 0.000 claims abstract description 10
- 230000001105 regulatory effect Effects 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 229910001610 cryolite Inorganic materials 0.000 claims description 30
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 26
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 23
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 239000002893 slag Substances 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract description 3
- 125000004122 cyclic group Chemical group 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 23
- 229910052782 aluminium Inorganic materials 0.000 description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 14
- 239000007787 solid Substances 0.000 description 12
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 11
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- 238000000926 separation method Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 239000002699 waste material Substances 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 6
- 238000005868 electrolysis reaction Methods 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- -1 hexafluoro sodium aluminate Chemical compound 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910018626 Al(OH) Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 150000004673 fluoride salts Chemical class 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 3
- 229910001948 sodium oxide Inorganic materials 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000006071 cream Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000010413 mother solution Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000011775 sodium fluoride Substances 0.000 description 2
- 235000013024 sodium fluoride Nutrition 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- LVYZJEPLMYTTGH-UHFFFAOYSA-H dialuminum chloride pentahydroxide dihydrate Chemical compound [Cl-].[Al+3].[OH-].[OH-].[Al+3].[OH-].[OH-].[OH-].O.O LVYZJEPLMYTTGH-UHFFFAOYSA-H 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002221 fluorine Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 229910000405 sodium aluminium phosphate Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Processing Of Solid Wastes (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
A process for reducing the content of Na in raw material containing F includes such steps as mixing raw material containing F in water, regulating pH value with acid solution, cyclic fluidization, heating and pressure leaching in reactor, cooling and pressure reducing, and filtering. The sodium content of the fluorine-containing raw material treated by the method can be reduced to 0.48 percent, the sodium removal rate is up to 98.56 percent, and the yields of fluorine and aluminum oxide are respectively up to 90.23 percent and 90.40 percent.
Description
Technical Field
The invention particularly relates to a method for reducing sodium content in a fluorine-containing raw material.
Background
The fluorine-containing raw materials comprise cryolite and electrolytic aluminum waste residues, and the electrolytic aluminum waste residues comprise carbon residues, overhaul residues and the like.
Cryolite is also called hexafluoro sodium aluminate or sodium aluminum fluoride, the cryolite is white and fine crystal, the cryolite is odorless and slightly soluble in water, the solubility is larger than that of natural cryolite, and the molecular formula is as follows: na (Na) 3 AlF 6 Molecular weight: 209.94 with density of 2.95-3.0 and melting point of about 1000 deg.C, is easy to absorb water and wet, and can be decomposed by strong acid such as sulfuric acid and hydrochloric acid to produce hydrofluoric acid and corresponding aluminium salt and sodium salt. The cryolite is mainly used as a cosolvent for aluminum electrolysis and also used as an abrasion-resistant additive for grinding products, so that abrasion resistance and cutting force of the grinding wheel can be effectively improved, and the service life and storage time of the grinding wheel can be prolonged; can also be used as flux of iron alloy, boiling steel and nonferrous metal, deoxidizer for casting and olefin polymerization catalyst; for use inGlass anti-reflection coating, enamel cream, glass float cream, soldering flux, filler in ceramic industry, resin, wear-resistant filler in rubber industry, pesticide and the like.
When cryolite is used as the auxiliary solvent for aluminum electrolysis, or carbon slag and overhaul slag are used as the auxiliary solvent or fuel, if the sodium content in the fluorine-containing raw material is too high, the cryolite can be even higher than 25 percent, so as to maintain the proper molecular ratio (AlF) in the process of aluminum electrolysis 3 The mole ratio of NaF) can lead to great increase of aluminum fluoride (reducing the primary crystal temperature of electrolyte and optimizing the additive of electrolyte components), thereby increasing the production cost of electrolytic aluminum, and meanwhile, as the alumina raw material added into the electrolytic tank usually contains 0.3-0.4% of sodium oxide, about 12-15 kg of aluminum fluoride is needed to be supplemented for each ton of electrolytic aluminum produced, part of aluminum fluoride and sodium oxide in the aluminum oxide are combined into sodium fluoride or sodium fluoroaluminate, also called cryolite, so that cryolite or electrolyte in the electrolytic tank is continuously increased, and only the electrolytic tank can be fished out, thereby causing waste of cryolite and larger cost of electrolytic aluminum. The molecular ratio is reduced, namely the sodium content in the fluorine-containing raw material is reduced, so that the aluminum fluoride with very low sodium content or without sodium oxide is obtained, and the aluminum fluoride can be returned to the electrolytic tank for reuse, so that the consumption of the aluminum fluoride can be reduced, and the production cost of the electrolytic aluminum is reduced. The prior art can only reduce the sodium content in cryolite to 8-10%, and has great obstacle to industrial utilization, and for industrial practice, deeper sodium removal is particularly important, and the circulating cryolite proportion can be greatly reduced, so that the production cost is reduced.
CN109721090a discloses a method for reducing cryolite molecular ratio, which is to mix cryolite raw material or cryolite raw material with additive, wherein the additive is any one or more of aluminum sulfate, aluminum nitrate and aluminum chloride, to obtain mixed calcined material, the mixed calcined material is calcined for 0.5-100 hours at 300-1000 ℃ to obtain calcined product, the calcined product is added with water, water soluble matters are dissolved out, and then the mixture is filtered, and filter residues are cryolite with low molecular ratio. However, the removal rate of sodium in cryolite is not high, the sodium content is still about 10%, and aluminum ions are hydrolyzed to cause higher aluminum hydroxide content.
CN111485252a discloses a method for reutilizing fluorine-containing materials by dry treatment, which comprises the following steps: 1) Uniformly mixing a fluorine-containing material to be treated with aluminum salt in a solid powder state, and then heating and reacting for 20-180 minutes at 150-770 ℃ to obtain a reactant; 2) Adding hot water at 35-60 ℃ into the reactant obtained in the step 1), stirring for 10-60 minutes, dissolving out soluble salt, then carrying out solid-liquid separation, and fully washing the separated solid with the hot water at 35-60 ℃; 3) And 2) washing the solid after solid-liquid separation, and then drying and burning at 100-700 ℃ to obtain a fluoride salt product taking aluminum fluoride as a main component. However, since the calcination is required at high temperature, the equipment requirement and the energy consumption are high, and the sodium salt content in the obtained aluminum fluoride product is lower than 0.5%.
CN112299462a discloses a method for directly innocent treatment and utilization of waste carbon residue generated by aluminum electrolysis, which comprises the following steps: 1) Mixing waste carbon slag generated by aluminum electrolysis after wet grinding with soluble aluminum salt, and then placing the mixture into water for stirring reaction or directly placing the mixture into soluble aluminum salt solution for stirring reaction, wherein the weight of the soluble aluminum salt is 25-300% of that of the carbon slag, the solid content in stirring reaction liquid is 4-40%, the reaction temperature is controlled within the range of 4-100 ℃, and the reaction time is controlled for 60-600 minutes; then, carrying out solid-liquid separation on the reactant to obtain a solid and a solution; 2) Fully washing the solid matters after solid-liquid separation, and mixing the washing liquid with the solution after solid-liquid separation in the step 1); the solid obtained after washing is directly used as fuel; adding solid alkaline matter or alkaline solution into the mixed solution of the solution after the washing solution and the solid-liquid separation, adjusting the pH value to 5-7, carrying out precipitation separation on substances in the mixed solution, and respectively washing, drying and roasting the precipitate to obtain the fluoride salt taking aluminum fluoride as a main component. However, the method is mainly aimed at separating fluoride and alkali metal in waste carbon residue, and does not involve reducing sodium in fluoride, nor does it disclose sodium content in fluoride.
CN110194478A discloses a method for preparing fluorine salt with aluminum fluoride as main component by using electrolyte-containing material generated by aluminum electrolysis, comprising the following steps: 1) Firstly, mixing electrolyte-containing materials to be treated with soluble aluminum salt or an aluminum salt solution, wherein the weight of the soluble aluminum salt is 25-500% of that of the electrolyte, diluting until the solid content is 2-90%, and reacting at 50-100 ℃ to obtain a reactant; 2) Carrying out solid-liquid separation on the reactant, washing the separated solid, and drying to obtain fluoride salt taking aluminum fluoride as a main component; 3) Adding strong alkaline hydroxide or solution thereof into the liquid obtained after the solid-liquid separation in the step 2) and the solid washing liquid obtained after the solid washing to remove calcium and iron impurities in the solution; 4) Evaporating, concentrating and desalting the solution after removing calcium and iron impurities, and separating to obtain concentrated mother solution; 5) And adding carbonate or a solution thereof into the concentrated mother solution to remove lithium ion impurities in the solution, wherein the solution after impurity removal is used for dilution in the step 1) or washing in the step 2). However, the method is mainly aimed at separating fluoride and alkali metal in waste carbon residue, and does not involve reducing sodium in fluoride, nor does it disclose sodium content in fluoride.
Therefore, a method for reducing the sodium content in the fluorine-containing raw material, which has the advantages of low sodium content, high sodium removal rate, high fluorine and aluminum yield, simple process and low cost, of the treated product and is suitable for industrial production, is needed to be found.
Disclosure of Invention
The invention aims to solve the technical problems of the prior art, and provides a method for reducing the sodium content in fluorine-containing raw materials, which has the advantages of low sodium content, high sodium removal rate, high fluorine and aluminum yield, simple process, low cost and suitability for industrial production.
The technical scheme adopted for solving the technical problems is as follows: a process for reducing the content of Na in raw material containing F includes such steps as mixing raw material containing F in water, regulating pH value with acid solution, cyclic fluidization, heating and pressure leaching in reactor, cooling and pressure reducing, and filtering.
The technical idea of the invention is as follows: a proper amount of water can promote the dissolution of impurities in the fluorine-containing raw material; the acid solution is added to keep acidity, so that the dissolution balance of sodium can be promoted to right; the heating and pressurizing can promote the reduction of the sodium content, and further enhance the rightward inclination of the dissolution balance of sodium.
Preferably, the mass ratio of the fluorine-containing raw material to water is 1:1-100 (more preferably 1:15-70). If the amount of water is too large, the fluorine-containing raw material is largely dissolved, and if the amount of water is too small, the concentration is too high, which is not favorable for leaching sodium.
Preferably, the main components and mass fractions of the fluorine-containing raw material are as follows: fluorine 30.0-54.0%, alumina 9.0-32.0%, sodium 3.0-30.0%, and total mass fraction less than 100%.
Preferably, the fluorine-containing raw material is one or more of protogenic cryolite, carbon slag, regenerated cryolite or overhaul slag and the like. The primary cryolite used in the method is derived from natural minerals, the regenerated cryolite is derived from fluxing of an alumina factory, and after the primary cryolite is used, the carbon slag or the overhaul slag is recovered from an electrolytic tank.
Preferably, the pH is adjusted to 1.0 to 5.0. The speed and the total amount of sodium dissolution can be improved by adjusting the pH value to be acidic; when aluminum salt is added for reaction, the hydrolysis of aluminum ions can be inhibited, and the reaction equation is as follows: al (Al) 3+ + 3H 2 O → Al(OH) 3 + 3H + 。
Preferably, the mass fraction of the acid solution is 1-36% (more preferably 20-35%).
Preferably, the acid solution is one or more of hydrochloric acid solution, sulfuric acid solution, nitric acid solution and the like.
Preferably, the aluminum salt is added while the fluorine-containing starting material is mixed with water. The aluminum salt is used to leach sodium from the fluorine-containing feedstock. Taking aluminum chloride as an example, chloride ions are consumed as the reaction proceeds, the pH value is increased, aluminum chloride is changed into polyaluminum chloride or aluminum chlorohydrate, the performance of dissolving out sodium ions is reduced, when an acid solution is added to adjust the pH value to be acidic, the hydrolysis of aluminum ions can be inhibited, the dissolution of sodium in fluorine-containing raw materials is further ensured, and the aluminum chloride can be regarded as a catalyst in the whole reaction. Aluminum salt as AlCl 3 Acid is exemplified by hydrochloric acid, which is given by the reaction equation: 3Na + + AlCl 3 → Al 3+ + 3NaCl，Al 3+ + 3H 2 O → Al(OH) 3 + 3H + ，Al(OH) 3 + 3HCl → AlCl 3 + 3H 2 O。
Preferably, the mass ratio of the aluminum salt to the fluorine-containing raw material is 1:1.0 to 5.0 (more preferably 1.0 to 2.0). And under the condition of the using amount of the aluminum salt, sodium in the fluorine-containing raw material can be fully leached.
Preferably, the aluminum salt is one or more of aluminum chloride, aluminum sulfate, aluminum nitrate or a polymeric aluminum salt and the like.
More preferably, the aluminum chloride is orthorhombic crystalline aluminum chloride. The crystalline aluminum chloride is able to more fully leach the fluorine-containing feedstock.
Preferably, the circulating fluidized heating pressure leaching means: the reaction is carried out at a temperature of 101 to 200 ℃ (more preferably 120 to 180 ℃), a pressure of 0.1 to 0.6MPa (more preferably 0.3 to 0.4 MPa), a flow rate of 0.01 to 10m/s (more preferably 0.5 to 5.0 m/s) for 0.2 to 10 hours (more preferably 1 to 8 hours). Heating and pressurizing are carried out under the parameters, so that the full leaching of sodium in the fluorine-containing raw material is more facilitated. If the temperature, pressure and flow rate are too high, the contact reaction is insufficient, and scouring corrosion is generated on pipelines, equipment and the like; if the temperature, pressure and flow rate are too small, the pipeline is easy to be blocked, and the reaction efficiency is low. Therefore, the proper circulating fluidization heating and pressurizing leaching is more beneficial to sodium removal.
Preferably, the above operation is repeated for not less than 1 time for the obtained filter residue.
The beneficial effects of the invention are as follows:
(1) The sodium content of the fluorine-containing raw material treated by the method can be reduced to 0.48 percent, the sodium removal rate is up to 98.56 percent, and the yields of fluorine and aluminum oxide are respectively up to 90.23 percent and 90.40 percent;
(2) The method has simple process and low cost, and is suitable for industrial production.
Detailed Description
The invention is further illustrated below with reference to examples.
The regenerated cryolite used in the embodiment of the invention is derived from the dissolution-assisting use of a certain alumina factory in Shandong, wherein the carbon slag 1 comprises the following main components in percentage by mass: 31.4% of fluorine, 9.8% of alumina and 16.5% of sodium, and the carbon slag 2 comprises the following main components in percentage by mass: fluorine 30.9%, alumina 10.2%, sodium 16.7%, and regenerated cryolite 1 comprises the following main components in percentage by mass: 50.1% of fluorine, 15.3% of alumina, 26.1% of sodium, and the main components and mass fractions of the regenerated cryolite 2 are as follows: fluorine 50.6%, alumina 15.9%, sodium 26.7%; the materials or chemicals used in the examples of the present invention, unless otherwise specified, were obtained by conventional commercial means.
Example 1
Mixing 30g of carbon residue 1 in 450mL of water, regulating the pH value to 2.0 by using sulfuric acid solution (mass fraction is 30%), placing in a pressurized reaction kettle, performing circulating fluidization, heating and pressure leaching for 5h at 150 ℃ and 0.35MPa and flow rate of 2.0m/s, cooling and reducing pressure, filtering, and repeating the operation for 2 times on the obtained filter residue to obtain 25.25g of filter residue 1.
Through detection, in the filter residue 1 obtained in the embodiment of the invention, the main components and mass fractions are as follows: 29.23% of fluorine, 9.01% of alumina and 10.23% of sodium; the removal rate of sodium was 47.82%, and the yields of fluorine and alumina were 78.35% and 77.38%, respectively.
Example 2
Mixing 20kg of carbon residue 2 in 1000L of water, regulating the pH value to 1.0 by using hydrochloric acid solution (mass fraction is 32%), placing in a pressurized reaction kettle, performing circulating fluidization heating and pressurizing leaching for 8 hours at 160 ℃ and 0.4MPa and a flow rate of 1.0m/s, cooling and depressurizing, filtering, and repeating the operation for 2 times on the obtained filter residue to obtain 16.14kg of filter residue 2.
Through detection, in the filter residue 2 obtained in the embodiment of the invention, the main components and mass fractions are as follows: 29.76 percent of fluorine, 9.67 percent of alumina and 10.01 percent of sodium; the removal rate of sodium was 51.63%, and the yields of fluorine and alumina were 77.72% and 76.51%, respectively.
Example 3
Mixing 36kg of carbon slag 1 and 30kg of orthorhombic crystal system crystalline aluminum chloride in 2400L of water, regulating the pH value to 1.0 by using hydrochloric acid solution (mass fraction is 35%), placing the mixture in a pressurized reaction kettle, performing circulating fluidization heating and pressure leaching for 2 hours at 120 ℃ and 0.35MPa with the flow rate of 2.0m/s, cooling and depressurization, filtering, and repeatedly performing the operation on the obtained filter residues for 2 times to obtain 26.53kg of filter residues 3.
Through detection, in the filter residue 3 obtained in the embodiment of the invention, the main components and mass fractions are as follows: 38.54% of fluorine, 11.89% of alumina and 1.54% of sodium; the removal rate of sodium was 93.12%, and the yields of fluorine and alumina were 90.45% and 89.41%, respectively.
Example 4
3.3kg of regenerated cryolite 1 and 3kg of orthorhombic crystal system crystalline aluminum chloride are mixed in 150L of water, the pH value is regulated to 2.0 by sulfuric acid solution (mass fraction is 30%), the mixture is placed in a pressurized reaction kettle, the mixture is subjected to circulating fluidization, heating, pressurizing and leaching for 1.8 hours at 150 ℃ and 0.3MPa and at a flow rate of 1.0m/s, the mixture is cooled and depressurized, the mixture is filtered, and the obtained filter residue is repeatedly subjected to the operation for 3 times, so as to obtain 2.583kg of filter residue 4.
Through detection, in the filter residue 4 obtained in the embodiment of the invention, the main components and mass fractions are as follows: 57.70% of fluorine, 17.64% of alumina and 0.48% of sodium; the removal rate of sodium is 98.56%, and the yields of fluorine and alumina are 90.15% and 90.24%, respectively.
Example 5
Mixing 30kg of regenerated cryolite 2 and 30kg of orthorhombic crystal system crystalline aluminum chloride in 600L of water, regulating the pH value to 3.0 by using hydrochloric acid solution (mass fraction is 32%), placing the mixture in a pressurized reaction kettle, performing circulating fluidization heating and pressurizing leaching for 1.5h at 180 ℃ and 0.4MPa and flow rate of 0.5m/s, filtering after cooling and depressurization, and repeatedly performing the operation on the obtained filter residues for 3 times to obtain 24.64kg of filter residues 5.
Through detection, in the filter residue 5 obtained in the embodiment of the invention, the main components and mass fractions are as follows: 55.59% of fluorine, 17.50% of alumina and 0.51% of sodium; the removal rate of sodium was 98.43%, and the yields of fluorine and alumina were 90.23% and 90.40%, respectively.
Claims (8)
1. A method for reducing sodium content in a fluorine-containing raw material, which is characterized by comprising the following steps: mixing fluorine-containing raw materials in water, regulating the pH value by using an acid solution, placing the mixture in a pressurized reaction kettle for circulating fluidization, heating, pressurizing and leaching, cooling, reducing the pressure, and filtering to obtain the fluorine-containing raw materials; the circulating fluidization heating and pressurizing leaching means that: the reaction is carried out for 0.2 to 10 hours at the temperature of 101 to 200 ℃ and the pressure of 0.1 to 0.6MPa and the flow rate of 0.01 to 10 m/s.
2. The method for reducing sodium content in a fluorine-containing raw material according to claim 1, wherein: the mass ratio of the fluorine-containing raw material to the water is 1:1-100; the fluorine-containing raw material comprises the following main components in percentage by mass: 30.0 to 54.0 percent of fluorine, 9.0 to 32.0 percent of alumina, 3.0 to 30.0 percent of sodium and the total mass fraction is less than 100 percent; the fluorine-containing raw material is one or more of primary cryolite, carbon slag, regenerated cryolite and overhaul slag.
3. The method for reducing sodium content in a fluorine-containing raw material according to claim 1 or 2, characterized in that: the pH value is regulated to 1.0-5.0; the mass fraction of the acid solution is 1-36%; the acid solution is one or more of hydrochloric acid solution, sulfuric acid solution or nitric acid solution.
4. The method for reducing sodium content in a fluorine-containing raw material according to claim 1 or 2, characterized in that: adding aluminum salt when the fluorine-containing raw material is mixed with water; the mass ratio of the aluminum salt to the fluorine-containing raw material is 1:1.0-5.0; the aluminum salt is one or more of aluminum chloride, aluminum sulfate, aluminum nitrate or polymeric aluminum salt.
5. A method of reducing sodium content in a fluorine-containing feedstock according to claim 3, wherein: adding aluminum salt when the fluorine-containing raw material is mixed with water; the mass ratio of the aluminum salt to the fluorine-containing raw material is 1:1.0-5.0; the aluminum salt is one or more of aluminum chloride, aluminum sulfate, aluminum nitrate or polymeric aluminum salt.
6. The method for reducing sodium content in a fluorine-containing raw material according to claim 1 or 2, characterized in that: and repeating the above operation for more than or equal to 1 time on the obtained filter residue.
7. A method of reducing sodium content in a fluorine-containing feedstock according to claim 3, wherein: and repeating the above operation for more than or equal to 1 time on the obtained filter residue.
8. The method for reducing sodium content in a fluorine-containing raw material according to claim 4, wherein: and repeating the above operation for more than or equal to 1 time on the obtained filter residue.
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