CN110041042B - Electrochemical separation and utilization method of magnesium fluoride in zinc hydrometallurgy process - Google Patents
Electrochemical separation and utilization method of magnesium fluoride in zinc hydrometallurgy process Download PDFInfo
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- fluoride
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- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 title claims abstract description 42
- 229910001635 magnesium fluoride Inorganic materials 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 31
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000011701 zinc Substances 0.000 title claims abstract description 18
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 18
- 238000009854 hydrometallurgy Methods 0.000 title claims abstract description 12
- 238000000926 separation method Methods 0.000 title claims abstract description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 32
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 28
- 239000011777 magnesium Substances 0.000 claims abstract description 28
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims abstract description 28
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 claims abstract description 28
- 239000013078 crystal Substances 0.000 claims abstract description 21
- 239000004568 cement Substances 0.000 claims abstract description 20
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 15
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims abstract description 14
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 14
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract description 14
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims abstract description 14
- 239000011698 potassium fluoride Substances 0.000 claims abstract description 14
- 235000003270 potassium fluoride Nutrition 0.000 claims abstract description 14
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002244 precipitate Substances 0.000 claims abstract description 13
- 239000003381 stabilizer Substances 0.000 claims abstract description 9
- CENHPXAQKISCGD-UHFFFAOYSA-N trioxathietane 4,4-dioxide Chemical compound O=S1(=O)OOO1 CENHPXAQKISCGD-UHFFFAOYSA-N 0.000 claims abstract description 9
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims abstract description 9
- 229960001763 zinc sulfate Drugs 0.000 claims abstract description 9
- 229910000368 zinc sulfate Inorganic materials 0.000 claims abstract description 9
- 239000000654 additive Substances 0.000 claims abstract description 8
- 230000000996 additive effect Effects 0.000 claims abstract description 8
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 8
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims abstract description 7
- 235000019341 magnesium sulphate Nutrition 0.000 claims abstract description 7
- 239000006259 organic additive Substances 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 5
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 239000010440 gypsum Substances 0.000 claims description 8
- 229910052602 gypsum Inorganic materials 0.000 claims description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000012528 membrane Substances 0.000 claims description 4
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 claims description 3
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052863 mullite Inorganic materials 0.000 claims description 3
- NFMWFGXCDDYTEG-UHFFFAOYSA-N trimagnesium;diborate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]B([O-])[O-].[O-]B([O-])[O-] NFMWFGXCDDYTEG-UHFFFAOYSA-N 0.000 claims description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- OAOABCKPVCUNKO-UHFFFAOYSA-N 8-methyl Nonanoic acid Chemical compound CC(C)CCCCCCC(O)=O OAOABCKPVCUNKO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 claims description 2
- 229920001038 ethylene copolymer Polymers 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- -1 fluorine ions Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910021538 borax Inorganic materials 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000004328 sodium tetraborate Substances 0.000 description 2
- 235000010339 sodium tetraborate Nutrition 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- IQYKECCCHDLEPX-UHFFFAOYSA-N chloro hypochlorite;magnesium Chemical compound [Mg].ClOCl IQYKECCCHDLEPX-UHFFFAOYSA-N 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- WRUGWIBCXHJTDG-UHFFFAOYSA-L magnesium sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Mg+2].[O-]S([O-])(=O)=O WRUGWIBCXHJTDG-UHFFFAOYSA-L 0.000 description 1
- 229940061634 magnesium sulfate heptahydrate Drugs 0.000 description 1
- QSOMFNQEXNFPNU-UHFFFAOYSA-L magnesium;hydrogen sulfate;hydroxide;hydrate Chemical compound O.O.[Mg+2].[O-]S([O-])(=O)=O QSOMFNQEXNFPNU-UHFFFAOYSA-L 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/30—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing magnesium cements or similar cements
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B9/00—Magnesium cements or similar cements
- C04B9/04—Magnesium cements containing sulfates, nitrates, phosphates or fluorides
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/18—Alkaline earth metal compounds or magnesium compounds
- C25B1/20—Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/24—Halogens or compounds thereof
- C25B1/245—Fluorine; Compounds thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Structural Engineering (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The patent discloses a method for electrochemically separating and utilizing magnesium fluoride in a zinc hydrometallurgy process, which is characterized in that magnesium fluoride seed crystal and zinc fluoride are added into a zinc sulfate solution containing magnesium to obtain magnesium fluoride precipitate with coarse grains, and liquid-solid separation is carried out; adding a potassium hydroxide solution into the magnesium fluoride precipitate to obtain a magnesium hydroxide precipitate and a potassium fluoride solution, and filtering and separating; adding a potassium fluoride solution and a stabilizing agent into a diaphragm electrolytic cell for electrolysis to obtain potassium hydroxide and zinc fluoride; quickly burning magnesium hydroxide to obtain magnesium oxide; magnesium sulfate, organic additive, inorganic additive, reinforcing agent and crystal whisker are added into magnesium oxide and are uniformly mixed to obtain the magnesium oxysulfate cement. Compared with the prior art, the method has the characteristics of short process flow, mild reaction, high production efficiency and good product quality.
Description
Technical Field
The invention relates to the field of resource utilization of industrial waste residues, in particular to removal and utilization of magnesium in a zinc hydrometallurgy solution.
Background
Magnesium is a common associated impurity element in zinc ores, in a zinc hydrometallurgy process, most of magnesium enters a zinc hydrometallurgy process in the form of sulfate after roasting and leaching, only a small amount of magnesium in zinc concentrate is opened along with solution and slag, most of magnesium is not opened in circulation of electrolyte, and is difficult to remove in a purification process, so that the magnesium is enriched in the zinc hydrometallurgy process; meanwhile, the zinc sulfate solution contains a large amount of sulfate radicals, when the temperature of a solution system is reduced, magnesium can be salted out and crystallized and separated out in the form of magnesium sulfate dihydrate, so that the phenomena of pipeline blockage, tank wall scaling and the like in the zinc hydrometallurgy process are caused, the current efficiency of the electrodeposition process is also influenced, and the energy consumption of the zinc hydrometallurgy is increased [ Wuhaiyan. At present, the magnesium removal methods commonly used at home and abroad comprise five major methods such as a pretreatment removal method, a fluoride chemical precipitation method, an open-circuit solution method, a cooling crystallization method, a solvent extraction method and the like, but the high-added-value application reports of magnesium removed from a zinc sulfate solution are less.
The magnesium oxysulfate cement is a magnesium cementing material with similar performance to magnesium oxychloride cement, and is MgO-MgSO composed of active MgO and MgSO4 solution with certain concentration4-H2O ternary system air hardening cementing material. The raw materials mainly comprise: light-burned magnesium oxide, magnesium sulfate heptahydrate, water and an additive. The magnesium oxysulfate cement product has the characteristics of low thermal expansibility, difficult deformation, cracking, bending, no phenomena of moisture regain, halogen regain, frost regain and the like, and good water resistance, frost resistance and impermeability, and can be used for concrete, plates, embossments and coatingsResearch on modification technique of magnesium oxysulfate cement in pipeline]Chongqing university, 2016]. The industrial impurities and the preparation materials for the patent have the characteristic of recycling waste.
Disclosure of Invention
Compared with the prior art, the method can save the production cost, reduce the energy consumption and improve the efficiency; and can obviously improve the quality of the magnesium oxysulfate cement, and has obvious economic and social benefits.
A method for electrochemically separating and utilizing magnesium fluoride in a zinc hydrometallurgy process comprises the following steps:
adding magnesium fluoride seed crystal and zinc fluoride into magnesium-containing zinc sulfate solution to obtain magnesium fluoride precipitate with coarse crystal grains, and performing liquid-solid separation; adding a potassium hydroxide solution into the magnesium fluoride precipitate to obtain a magnesium hydroxide precipitate and a potassium fluoride solution, and filtering and separating; adding a potassium fluoride solution and a stabilizing agent into a diaphragm electrolytic cell for electrolysis to obtain potassium hydroxide and zinc fluoride; quickly burning magnesium hydroxide to obtain magnesium oxide; magnesium sulfate, organic additive, inorganic additive, reinforcing agent and crystal whisker are added into magnesium oxide and are uniformly mixed to obtain the magnesium oxysulfate cement.
The addition amount of the potassium hydroxide is 150-200% of the mass of the magnesium fluoride.
In the diaphragm electrolytic cell, a diaphragm is an ionic membrane, an anode is a metal zinc plate, and a cathode is an inert electrode.
The stabilizer is one of polyvinyl alcohol, citric acid and maleic acid, and the addition amount of the stabilizer is 0.1-1% of the mass of magnesium fluoride.
The quick burning temperature of the magnesium hydroxide is 400-.
The organic additive is one of malic acid, tartaric acid and oxalic acid, and the addition amount is 0.1-1% of the mass of magnesium fluoride.
The inorganic additive is one of high-strength gypsum, building gypsum and kaolin, and the addition amount is 1-10% of the mass of the magnesium fluoride.
The reinforcing agent is one of ethylene/vinyl acetate copolymer, vinyl acetate/versatic acid ethylene copolymer and acrylic acid copolymer, and the adding amount is 1-10% of the mass of magnesium fluoride.
The whisker is one of mullite whisker, aluminum borate whisker and magnesium borate whisker, and the adding amount of the whisker is 1-10% of the mass of magnesium fluoride.
Compared with the prior art, the invention has the following advantages:
adding magnesium fluoride crystal seeds into a zinc sulfate solution to facilitate crystallization of magnesium fluoride and obtain coarse particles, wherein the particle sizes of the magnesium fluoride crystals are larger than 20 mu m, and liquid-solid separation is facilitated; wherein the addition amount of the magnesium fluoride seed crystal is 0.1-2% of the magnesium fluoride precipitate. The obtained magnesium fluoride has less impurity content which is lower than one tenth of the reference limit value of the heavy metal content of the raw materials entering the kiln, which is required by the national standard GB/30760-2014 cement kiln synergic treatment solid waste technical specification, shown in the table 1, and provides guarantee for the resource utilization of magnesium.
The zinc fluoride is used for providing fluorine, and besides fluorine, other impurities cannot be brought in the zinc sulfate solution, so that the purification of the solution is facilitated. Wherein, the adding amount of zinc fluoride is 50-100mol% of the mol amount of magnesium in the solution, and the temperature of the zinc sulfate solution is 50-98 ℃.
Since magnesium hydroxide has a lower solubility than magnesium fluoride, magnesium hydroxide and potassium fluoride can be obtained by adding potassium hydroxide to magnesium fluoride. The potassium fluoride is easy to dissolve in water, and is beneficial to the separation of magnesium hydroxide and potassium fluoride.
The diaphragm in the diaphragm electrolyzer is an ionic membrane which allows fluorine ions to pass through. The potassium fluoride solution is added into the cathode tank, hydrogen ions in the cathode tank obtain electrons and become hydrogen to overflow, the potassium hydroxide solution is in the cathode tank, and the potassium hydroxide is used for reacting with magnesium fluoride to realize circulation. The anode metal zinc in the anode tank loses electrons and becomes zinc ions, and the zinc ions and fluorine ions penetrating through the ionic membrane form a zinc fluoride solution, and the zinc fluoride is used for precipitating magnesium to realize circulation. The stabilizer is added into the anode tank to form a complex with the zinc fluoride, so that the solubility of the zinc fluoride is improved, the amount of solvent water is reduced, and the operation of a zinc smelting system is prevented from being influenced. The electrolytic voltage is 1-60V, and the potassium fluoride can be electrolyzed. The invention decomposes potassium fluoride by an electrochemical method and has the characteristics of mild reaction conditions and easy control of reaction.
The magnesium hydroxide is quickly burnt to obtain magnesium oxide, the quick burning equipment is a drying and scattering machine, and the drying and scattering machine consists of a high-temperature resistant hammer crusher and a hot blast stove and has the characteristic of high speed.
Magnesium sulfate is added into the magnesium oxide, wherein the addition amount of the magnesium sulfate is 10-35% of the mass of the magnesium fluoride, and the high-strength cement is favorably obtained.
The appearance of cement hydration products can be improved by adding the organic additive into the magnesium oxide, so that needle-shaped and mutually staggered hydration products are obtained, and the high-strength cement is obtained.
The addition of inorganic additive to magnesia can regulate the setting time of cement and raise the strength of cement. The high-strength gypsum and the building gypsum are prepared from phosphogypsum, titanium gypsum and desulfurized gypsum, and have the characteristic of resource recycling.
The reinforcing agent is organic matter filled in cement pores, improves the construction performance of cement and can further improve the strength of the cement.
The mullite whisker is prepared by a molten salt method by taking fly ash as a raw material, the aluminum borate whisker is prepared by a molten salt method by taking bauxite and natural borax as raw materials, and the magnesium borate whisker is prepared by a molten salt method by taking boromagnesite and natural borax as raw materials; the crystal whisker has the characteristic of low cost.
The magnesium oxysulfate cement obtained by the method meets the national relevant standards and can be sold in the market. The magnesium is used as a building material, has wide application, is beneficial to the on-site recycling of magnesium resources, and ensures the popularization of the patent technology.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
(1) Adding magnesium fluoride seed crystal and zinc fluoride into magnesium-containing zinc sulfate solution to obtain magnesium fluoride precipitate with coarse crystal grains, and performing liquid-solid separation; adding a potassium hydroxide solution into the magnesium fluoride precipitate to obtain a magnesium hydroxide precipitate and a potassium fluoride solution, and filtering and separating; adding a potassium fluoride solution and a stabilizing agent into a diaphragm electrolytic cell for electrolysis to obtain potassium hydroxide and zinc fluoride; and (3) quickly burning the magnesium hydroxide to obtain the magnesium oxide.
The addition amount of potassium hydroxide, the addition amount of stabilizer, and the temperature and time for quick burning of magnesium oxide in magnesium fluoride are shown in Table 1.
Table 1.
(2) Magnesium sulfate accounting for 30 percent of the mass of magnesium fluoride, an organic additive, an inorganic additive, a reinforcing agent and crystal whiskers are added into magnesium oxide and uniformly mixed to obtain the magnesium oxysulfate cement. The addition amounts of the organic admixture, the inorganic admixture, the reinforcing agent and the crystal whisker are shown in Table 2.
TABLE 2
As can be seen from examples 1 to 15, the resulting cements had 28d compressive strengths of greater than 80 MPa.
The embodiments of the invention can be implemented and achieve the aim of the invention. The present invention is not limited to these examples.
Claims (2)
1. The method for electrochemically separating and utilizing magnesium fluoride in the zinc hydrometallurgy process is characterized by sequentially comprising the following steps of: adding magnesium fluoride seed crystal and zinc fluoride into magnesium-containing zinc sulfate solution to obtain magnesium fluoride precipitate with coarse crystal grains, and performing liquid-solid separation; adding a potassium hydroxide solution into the magnesium fluoride precipitate to obtain a magnesium hydroxide precipitate and a potassium fluoride solution, and filtering and separating; adding a potassium fluoride solution and a stabilizing agent into a diaphragm electrolytic cell for electrolysis to obtain potassium hydroxide and zinc fluoride; quickly burning magnesium hydroxide to obtain magnesium oxide; adding magnesium sulfate, an organic additive, an inorganic additive, a reinforcing agent and crystal whiskers into magnesium oxide, and uniformly mixing to obtain magnesium oxysulfate cement; wherein the addition amount of the potassium hydroxide is 150-200% of the mass of the magnesium fluoride; the stabilizer is one of citric acid and maleic acid, and the addition amount is 0.1-1% of the mass of magnesium fluoride; the quick burning temperature of the magnesium hydroxide is 400-; the organic additive is one of malic acid, tartaric acid and oxalic acid, and the addition amount is 0.1-1% of the mass of magnesium fluoride; the inorganic additive is one of high-strength gypsum, building gypsum and kaolin, and the addition amount is 1-10% of the mass of the magnesium fluoride; the reinforcing agent is one of ethylene/vinyl acetate copolymer, vinyl acetate/versatic acid ethylene copolymer and acrylic acid copolymer, and the addition amount is 1-10% of the mass of magnesium fluoride; the crystal whisker is one of mullite crystal whisker, aluminum borate crystal whisker and magnesium borate crystal whisker, and the adding amount of the crystal whisker is 1-10% of the mass of magnesium fluoride.
2. The method for electrochemically separating and utilizing magnesium fluoride in a zinc hydrometallurgy process according to claim 1, wherein in the diaphragm electrolytic cell, a diaphragm is an ionic membrane, an anode is a metal zinc plate, and a cathode is an inert electrode.
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