CN110041042A - Magnesium fluoride Electrochemical separation and method is utilized in a kind of Zinc hydrometallurgy process - Google Patents
Magnesium fluoride Electrochemical separation and method is utilized in a kind of Zinc hydrometallurgy process Download PDFInfo
- Publication number
- CN110041042A CN110041042A CN201910333815.4A CN201910333815A CN110041042A CN 110041042 A CN110041042 A CN 110041042A CN 201910333815 A CN201910333815 A CN 201910333815A CN 110041042 A CN110041042 A CN 110041042A
- Authority
- CN
- China
- Prior art keywords
- magnesium
- fluoride
- zinc
- magnesium fluoride
- added
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 43
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 title claims abstract description 41
- 229910001635 magnesium fluoride Inorganic materials 0.000 title claims abstract description 41
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 239000011701 zinc Substances 0.000 title claims abstract description 25
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 25
- 238000009854 hydrometallurgy Methods 0.000 title claims abstract description 20
- 238000000926 separation method Methods 0.000 title claims abstract description 17
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 32
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 29
- 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
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 claims abstract description 25
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims abstract description 24
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims abstract description 16
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 14
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 14
- 239000002244 precipitate Substances 0.000 claims abstract description 13
- 239000013078 crystal Substances 0.000 claims abstract description 12
- 239000011698 potassium fluoride Substances 0.000 claims abstract description 12
- 235000003270 potassium fluoride Nutrition 0.000 claims abstract description 12
- 239000000654 additive Substances 0.000 claims abstract description 9
- 230000000996 additive effect Effects 0.000 claims abstract description 9
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract description 9
- 229910001862 magnesium hydroxide Inorganic materials 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
- 238000003682 fluorination reaction Methods 0.000 claims abstract description 8
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims abstract description 8
- 235000019341 magnesium sulphate Nutrition 0.000 claims abstract description 8
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 8
- 239000003381 stabilizer Substances 0.000 claims abstract description 8
- OLZDXDPSDUSGIS-UHFFFAOYSA-N sulfinylmagnesium Chemical compound [Mg].S=O OLZDXDPSDUSGIS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000010440 gypsum Substances 0.000 claims description 7
- 229910052602 gypsum Inorganic materials 0.000 claims description 7
- 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
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 5
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 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
- 229920001577 copolymer Polymers 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
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 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
- 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
- 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
- 239000007788 liquid Substances 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
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 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
- 229920002126 Acrylic acid copolymer Polymers 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 239000000047 product Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000004568 cement Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 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
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 210000002421 cell wall Anatomy 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
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 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
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 150000002680 magnesium Chemical class 0.000 description 1
- WRUGWIBCXHJTDG-UHFFFAOYSA-L magnesium sulfate heptahydrate Chemical class O.O.O.O.O.O.O.[Mg+2].[O-]S([O-])(=O)=O WRUGWIBCXHJTDG-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
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 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
- 239000002023 wood Substances 0.000 description 1
- 238000009858 zinc metallurgy Methods 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
Abstract
This patent discloses magnesium fluoride Electrochemical separation in a kind of Zinc hydrometallurgy process and utilize method, it is characterised in that magnesium fluoride crystal seed, zinc fluoride are added in the solution of zinc sulfate containing magnesium, obtains coarse grains fluorination magnesium precipitate, solid-liquor separation；Potassium hydroxide solution is added in fluorination magnesium precipitate, obtains magnesium hydrate precipitate and potassium fluoride solution, is separated by filtration；Potassium fluoride solution and stabilizer are added in diaphragm cell and are electrolysed, potassium hydroxide and zinc fluoride are obtained；Magnesium hydroxide is burnt fastly and obtains magnesia；Magnesium sulfate, organic admixture, inorganic additive, reinforcing agent, whisker are added in magnesia, obtains magnesium oxysulfide concrete after mixing.The characteristics of compared with prior art scheme, this method process flow is short, and reaction is mild, high production efficiency, good product quality.
Description
Technical field
The present invention relates to the resource utilization fields of industrial residue, and in particular to the removing and benefit of magnesium in zinc hydrometallurgy solution
With.
Background technique
Magnesium is accompanying impurities element common in zinc ore, in zinc hydrometallurgical processes, magnesium after roasting and leaching,
Most of to enter Zinc hydrometallurgy process in the form of sulfate, the magnesium in zinc concentrate is only opened a way with solution and slag on a small quantity, exhausted big portion
The magnesium divided is not opened a way in the circulation of electrolyte, and is difficult to remove during purification, this will cause magnesium and refines in wet process
Enrichment during zinc；Contain a large amount of sulfate radical in solution of zinc sulfate simultaneously, when solution system temperature reduces, magnesium can go out
Existing salting-out phenomenon, is crystallized in the form of two Magnesium sulfate heptahydrates and is precipitated, lead to line clogging and cell wall fouling in Zinc Hydrometallurgy Process
Phenomena such as, it also will affect the current efficiency of electrolytic deposition process, increase the energy consumption of zinc hydrometallurgy by [Wu Haiyan. zinc hydrometallurgy demagging row
For research [D] Kunming University of Science and Technology, 2016].At present both at home and abroad commonly except magnesium method includes pretreatment removal method, fluoride
Five major class such as chemical precipitation method, open circuit solwution method, crystallisation by cooling method, solvent extraction, but the magnesium removed from solution of zinc sulfate
Value added applications report it is less.
Magnesium oxysulfide concrete is the magnesium gelatinous material similar with Properties of Magnesium Oxychloride Cement, by active MgO with it is certain density
The MgO-MgSO of MgSO4 solution composition4-H2O ternary system air hardening cementitious materials.Its raw material is main are as follows: light calcined magnesia,
Epsom salt, water, additive.Magnesium oxysulfide concrete product is with thermal expansivity is low, is unlikely to deform, cracks, being bent, nothing is got damp
Halogen returns phenomena such as frost, water resistance, frost resistance, impervious good feature, can be used for concrete, plate, embossment, coating, pipeline etc.
Aspect [Wang Lei magnesium oxysulfide concrete modification technology research [D] University Of Chongqing, 2016].The industrial impurity of this patent, prepares material
Material has the characteristics that the cyclic utilization of waste.
Summary of the invention
In order to solve the problems existing in the prior art, the present invention provides magnesium fluoride electrification credits in a kind of Zinc hydrometallurgy process
From and using method, compared with prior art scheme, this method can save production cost, reduce energy consumption, improve efficiency；And it can show
It writes and improves magnesium oxysulfide concrete quality, there is significant economic benefit and social benefit.
Magnesium fluoride Electrochemical separation and method is utilized in a kind of Zinc hydrometallurgy process, comprising the following steps:
Magnesium fluoride crystal seed, zinc fluoride are added in the solution of zinc sulfate containing magnesium, obtains coarse grains fluorination magnesium precipitate, liquid divides admittedly
From；Potassium hydroxide solution is added in fluorination magnesium precipitate, obtains magnesium hydrate precipitate and potassium fluoride solution, is separated by filtration；By fluorine
Change potassium solution and stabilizer is added in diaphragm cell and is electrolysed, obtains potassium hydroxide and zinc fluoride；Magnesium hydroxide is burnt fastly and is obtained
Magnesia；Magnesium sulfate, organic admixture, inorganic additive, reinforcing agent, whisker are added in magnesia, obtains after mixing
Magnesium oxysulfide concrete.
The additional amount of the potassium hydroxide is the 150-200% of magnesium fluoride quality.
In the diaphragm cell, diaphragm is ionic membrane, and anode is metal zine plate, and cathode is inert electrode.
The stabilizer is one of polyvinyl alcohol, citric acid, maleic acid, and additional amount is magnesium fluoride quality
0.1-1%。
It is 400-600 DEG C that the magnesium hydroxide burns temperature fastly, and fast to burn the time for 10-30s, fast equipment of burning is that drying is broken up
Machine.
The organic admixture is one of malic acid, tartaric acid, oxalic acid, and additional amount is the 0.1- of magnesium fluoride quality
1%。
The inorganic additive is one of high strength gypsum, building gypsum, kaolin, and additional amount is magnesium fluoride quality
1-10%。
The reinforcing agent is copolymer, the vinyl acetate/versatic acid ethylene copolymer, acrylic acid of ethylene/vinyl acetate
One of copolymer, additional amount are the 1-10% of magnesium fluoride quality.
The whisker is one of mullite crystal whisker, aluminium borate whisker, magnesium borate crystal whisker, and additional amount is magnesium fluoride quality
1-10%.
Compared with the existing technology, the invention has the following advantages that
Magnesium fluoride crystal seed is added in solution of zinc sulfate, is conducive to magnesium fluoride crystallization, obtains the coarse particle of partial size, magnesium fluoride is brilliant
The partial size of body is all larger than 20 μm, is conducive to solid-liquor separation；Wherein, the additional amount of magnesium fluoride crystal seed is the 0.1- for being fluorinated magnesium precipitate
2%.Impurity content is less in obtained magnesium fluoride, and lower than national standard, " GB/30760-2014 cement kiln synergic processing solid is useless
Enter kiln raw material content of beary metal refers to limit value 1/10th required by object technical specification " table 1, is provided for the recycling of magnesium
It ensures.
Fluorine is provided with zinc fluoride, outside fluorine removal, other impurity will not be brought in solution of zinc sulfate, are conducive to the purification of solution.
Wherein, zinc fluoride additional amount is the 50-100mol% of magnesium mole in solution, and solution of zinc sulfate temperature is 50-98 DEG C.
Since the solubility of magnesium hydroxide is lower than magnesium fluoride, so potassium hydroxide is added in magnesium fluoride can be obtained hydroxide
Magnesium and potassium fluoride.Potassium fluoride is soluble easily in water, is conducive to magnesium hydroxide and potassium fluoride separation.
Diaphragm in diaphragm cell is ionic membrane, and ionic membrane allows fluorine ion to pass through.Cathode can is added in potassium fluoride solution
In, it is potassium hydroxide solution in slot, potassium hydroxide is used for and magnesium fluoride that hydrogen ion, which obtains electronics, in cathode can, which becomes hydrogen spilling,
Circulation is realized in reaction.Anode slot Anodic metallic zinc, which loses electronics, becomes zinc ion, forms fluorine with the fluorine ion for passing through ionic membrane
Change zinc solution, zinc fluoride realizes circulation for precipitating magnesium.Stabilizer is added in anode slot and zinc fluoride forms complex compound, improves
Zinc fluoride solubility advantageously reduces the amount of aqueous solvent, avoids the operation for influencing zinc metallurgy system.Decomposition voltage is 1-60V,
It is electrolysed potassium fluoride.The method of present invention electrochemistry decomposes potassium fluoride, reaction easily controlled spy mild with reaction condition
Point.
Magnesium hydroxide is burnt fastly obtains magnesia, and fast equipment of burning is drying beater, and drying beater is hammer resistant to high temperature
Crusher and hot-blast stove composition, have the characteristics that fireballing.
Magnesium sulfate is added in magnesia, wherein the additional amount of magnesium sulfate is the 10-35% of magnesium fluoride quality, is conducive to
To high-intensitive cement.
Organic admixture is added in magnesia can improve the pattern of hydrolysis product of cement, obtain needle-shaped and intermesh
Hydrated product, obtain high strength cement.
The setting time of the adjustable cement of inorganic additive is added in magnesia, and improves strength of cement.High-strength stone
Cream and building gypsum are prepared by ardealite, titanium gypsum and desulfurized gypsum, have the characteristics that resource circulation utilization.
Reinforcing agent is that organic matter is filled in cement hole, improves the workability of cement, can further improve strength of cement.
Mullite crystal whisker is prepared for raw material with molten-salt growth method by flyash, and aluminium borate whisker bauxite and tincal are former
Material is prepared with molten-salt growth method, and magnesium borate crystal whisker boromagnesite and tincal are that raw material is prepared with molten-salt growth method；Whisker of the present invention has
Feature at low cost.
The magnesium oxysulfide concrete that this patent obtains meets relevant national standard, can sell on the market.Using magnesium as Building wood
Material, purposes is wider, is conducive to magnesium resource recycling on the spot, it is ensured that the popularization of the art of this patent.
Specific embodiment
Below in conjunction with specific embodiment, invention is further described in detail.
(1) magnesium fluoride crystal seed, zinc fluoride are added in the solution of zinc sulfate containing magnesium, obtains coarse grains fluorination magnesium precipitate,
Solid-liquor separation；Potassium hydroxide solution is added in fluorination magnesium precipitate, obtains magnesium hydrate precipitate and potassium fluoride solution, filtering point
From；Potassium fluoride solution and stabilizer are added in diaphragm cell and are electrolysed, potassium hydroxide and zinc fluoride are obtained；Magnesium hydroxide is fast
Burning obtains magnesia.
Potassium hydroxide additional amount, stabilizer additional amount, the temperature and time that magnesia is burnt fastly are shown in Table 1 in magnesium fluoride.
Table 1.
(2) be added in magnesia the magnesium sulfate of magnesium fluoride quality 30%, organic admixture, inorganic additive, reinforcing agent,
Whisker obtains magnesium oxysulfide concrete after mixing.Organic admixture, inorganic additive, reinforcing agent, whisker additional amount, are shown in Table 2.
From embodiment 1- embodiment 15, it can be concluded that, obtained cement 28d compression strength is all larger than 80MPa.
The embodiment of the present invention can be implemented and can reach goal of the invention.The present invention is not limited to these Examples.
Claims (9)
1. in a kind of Zinc hydrometallurgy process magnesium fluoride Electrochemical separation and utilize method, which is characterized in that successively include following steps
It is rapid:
Magnesium fluoride crystal seed, zinc fluoride are added in the solution of zinc sulfate containing magnesium, obtains coarse grains fluorination magnesium precipitate, liquid divides admittedly
From；Potassium hydroxide solution is added in fluorination magnesium precipitate, obtains magnesium hydrate precipitate and potassium fluoride solution, is separated by filtration；By fluorine
Change potassium solution and stabilizer is added in diaphragm cell and is electrolysed, obtains potassium hydroxide and zinc fluoride；Magnesium hydroxide is burnt fastly and is obtained
Magnesia；Magnesium sulfate, organic admixture, inorganic additive, reinforcing agent, whisker are added in magnesia, obtains after mixing
Magnesium oxysulfide concrete.
2. in a kind of Zinc hydrometallurgy process according to claim 1 magnesium fluoride Electrochemical separation and utilize method, feature
It is, the additional amount of the potassium hydroxide is the 150-200% of magnesium fluoride quality.
3. in a kind of Zinc hydrometallurgy process according to claim 1 magnesium fluoride Electrochemical separation and utilize method, feature
It is, in the diaphragm cell, diaphragm is ionic membrane, and anode is metal zine plate, and cathode is inert electrode.
4. in a kind of Zinc hydrometallurgy process according to claim 1 magnesium fluoride Electrochemical separation and utilize method, feature
It is, the stabilizer is one of polyvinyl alcohol, citric acid, maleic acid, and additional amount is the 0.1- of magnesium fluoride quality
1%。
5. in a kind of Zinc hydrometallurgy process according to claim 1 magnesium fluoride Electrochemical separation and utilize method, feature
It is, it is 400-600 DEG C that the magnesium hydroxide burns temperature fastly, and fast to burn the time for 10-30s, fast equipment of burning is drying beater.
6. in a kind of Zinc hydrometallurgy process according to claim 1 magnesium fluoride Electrochemical separation and utilize method, feature
It is, the organic admixture is one of malic acid, tartaric acid, oxalic acid, and additional amount is the 0.1-1% of magnesium fluoride quality.
7. in a kind of Zinc hydrometallurgy process according to claim 1 magnesium fluoride Electrochemical separation and utilize method, feature
It is, the inorganic additive is one of high strength gypsum, building gypsum, kaolin, and additional amount is the 1- of magnesium fluoride quality
10%。
8. in a kind of Zinc hydrometallurgy process according to claim 1 magnesium fluoride Electrochemical separation and utilize method, feature
It is, the reinforcing agent is copolymer, the vinyl acetate/versatic acid ethylene copolymer, acrylic acid copolymer of ethylene/vinyl acetate
One of object, additional amount are the 1-10% of magnesium fluoride quality.
9. in a kind of Zinc hydrometallurgy process according to claim 1 magnesium fluoride Electrochemical separation and utilize method, feature
It is, the whisker is one of mullite crystal whisker, aluminium borate whisker, magnesium borate crystal whisker, and additional amount is magnesium fluoride quality
1-10%。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910333815.4A CN110041042B (en) | 2019-04-24 | 2019-04-24 | Electrochemical separation and utilization method of magnesium fluoride in zinc hydrometallurgy process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910333815.4A CN110041042B (en) | 2019-04-24 | 2019-04-24 | Electrochemical separation and utilization method of magnesium fluoride in zinc hydrometallurgy process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110041042A true CN110041042A (en) | 2019-07-23 |
| CN110041042B CN110041042B (en) | 2021-11-12 |
Family
ID=67278996
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910333815.4A Active CN110041042B (en) | 2019-04-24 | 2019-04-24 | Electrochemical separation and utilization method of magnesium fluoride in zinc hydrometallurgy process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110041042B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112301381A (en) * | 2020-10-16 | 2021-02-02 | 云南驰宏锌锗股份有限公司 | Method for removing magnesium ions from zinc electrolyte |
| CN114956620A (en) * | 2022-05-30 | 2022-08-30 | 常熟理工学院 | Method for preparing modified magnesium oxychloride cement by using bischofite and waste incineration fly ash |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102502724A (en) * | 2011-11-02 | 2012-06-20 | 中国科学院青海盐湖研究所 | Method for preparing magnesia for magnesium cement by using bischofite and dolomite |
| CN106747240A (en) * | 2016-12-29 | 2017-05-31 | 内蒙古中鼎工正环保有限公司 | A kind of alkaline magnesium oxysulfide concrete and preparation method thereof |
-
2019
- 2019-04-24 CN CN201910333815.4A patent/CN110041042B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102502724A (en) * | 2011-11-02 | 2012-06-20 | 中国科学院青海盐湖研究所 | Method for preparing magnesia for magnesium cement by using bischofite and dolomite |
| CN106747240A (en) * | 2016-12-29 | 2017-05-31 | 内蒙古中鼎工正环保有限公司 | A kind of alkaline magnesium oxysulfide concrete and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| J.L.BOOSTER 等: "Magnesium removal in the electrolytic zinc industry", 《MINERALS ENGINEERING》 * |
| 中国菱镁行业协会组: "《镁质胶凝材料及制品技术》", 31 January 2016, 中国建材工业出版社 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112301381A (en) * | 2020-10-16 | 2021-02-02 | 云南驰宏锌锗股份有限公司 | Method for removing magnesium ions from zinc electrolyte |
| CN112301381B (en) * | 2020-10-16 | 2023-06-09 | 云南驰宏锌锗股份有限公司 | Method for removing magnesium ions from zinc electrolyte |
| CN114956620A (en) * | 2022-05-30 | 2022-08-30 | 常熟理工学院 | Method for preparing modified magnesium oxychloride cement by using bischofite and waste incineration fly ash |
| CN114956620B (en) * | 2022-05-30 | 2023-01-31 | 常熟理工学院 | Method for preparing modified magnesium oxychloride cement by using bischofite and waste incineration fly ash |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110041042B (en) | 2021-11-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107653378A (en) | The recovery method of valuable metal in a kind of waste and old nickel cobalt manganese lithium ion battery | |
| CN104831064B (en) | Acidleach-cyclone electrolytic cell technology technique of high efficiente callback copper from lead copper matte is pressed with oxygen | |
| CN109867463A (en) | A kind of method that magnesium resource utilizes in Zinc hydrometallurgy process | |
| CN109665501A (en) | A kind of sulfate liquor fluorine circulation de-magging technique and system | |
| CN110041042A (en) | Magnesium fluoride Electrochemical separation and method is utilized in a kind of Zinc hydrometallurgy process | |
| CN100417475C (en) | Production of metal zinc powder from zinc dust and zinc dross | |
| CN106745137A (en) | A kind of method for producing ice crystal with cell cathode carbon block alkaline leaching liquid | |
| CN104233370B (en) | A kind of method utilizing copper-contained sludge to produce electrolytic copper | |
| WO2017080244A1 (en) | Method for preparing high-purity strontium chloride by using strontium slag | |
| CN103482680A (en) | Process for producing nano zinc oxide by using crude zinc oxide | |
| CN106400051A (en) | Method for achieving copper, nickel and tin separation through low-copper, high-nickel and high-tin anode electrolysis | |
| CN109338105A (en) | A method of valuable metal is efficiently separated from the mixed solution of nickel and cobalt containing manganese lithium | |
| CN102817041A (en) | Method for preparing magnesium hydroxide, magnesium and magnesium aluminate spinel by bischofite | |
| CN1772963A (en) | Common-battery deposition producing method for Mg La Pr Ce intermediate alloy | |
| CN109911909A (en) | The recovery and treatment method of saggar is discarded in a kind of lithium cobaltate cathode material preparation process | |
| CN105755296B (en) | The method of calcium is removed from the solution of zinc sulfate that zinc hydrometallurgy produces | |
| CN113699560B (en) | Method for preparing metallic titanium by soluble anode electrolysis of fluorine-chlorine mixed molten salt system | |
| CN1644719A (en) | Method for fire refining lead | |
| CN108950218A (en) | A method of recycling gold, silver and copper from waste printed circuit board | |
| CN109913652A (en) | The integrated conduct method of waste refractory materials in a kind of tertiary cathode material preparation process | |
| CN110104972A (en) | Magnesium clean separation and method is utilized in a kind of Zinc hydrometallurgy process | |
| CN101054686A (en) | Process for purifying zinc from casting zinc residue | |
| CN107840357A (en) | A kind of method that ice crystal is produced using cell cathode carbon block alkaline leaching liquid | |
| CN103221557B (en) | Method for producing nickel-ontaining acidic solution | |
| CN110923468A (en) | Method for recovering metallic lead from lead-containing materials such as lead sulfate slag |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20221223 Address after: 230000 B-1015, wo Yuan Garden, 81 Ganquan Road, Shushan District, Hefei, Anhui. Patentee after: HEFEI MINGLONG ELECTRONIC TECHNOLOGY Co.,Ltd. Address before: 621010, No. 59, Qinglong Avenue, Fucheng District, Sichuan, Mianyang Patentee before: Southwest University of Science and Technology |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240502 Address after: Room 101, Building 3, No. 1, Minye Street, Tangxia Town, Dongguan, Guangdong 523000 Patentee after: Guangdong Zhijie Supply Chain Management Co.,Ltd. Country or region after: China Address before: 230000 B-1015, wo Yuan Garden, 81 Ganquan Road, Shushan District, Hefei, Anhui. Patentee before: HEFEI MINGLONG ELECTRONIC TECHNOLOGY Co.,Ltd. Country or region before: China |