CN104261703B - A kind of resource utilization method of magnesium-rare earth smelting slag - Google Patents
A kind of resource utilization method of magnesium-rare earth smelting slag Download PDFInfo
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- CN104261703B CN104261703B CN201410517419.4A CN201410517419A CN104261703B CN 104261703 B CN104261703 B CN 104261703B CN 201410517419 A CN201410517419 A CN 201410517419A CN 104261703 B CN104261703 B CN 104261703B
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- 238000003723 Smelting Methods 0.000 title claims abstract description 125
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 123
- 239000002893 slag Substances 0.000 title claims abstract description 121
- 238000000034 method Methods 0.000 title claims abstract description 49
- 239000000463 material Substances 0.000 claims abstract description 208
- 238000000926 separation method Methods 0.000 claims abstract description 172
- 239000007788 liquid Substances 0.000 claims abstract description 160
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 125
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 78
- 238000002386 leaching Methods 0.000 claims abstract description 76
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 71
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 57
- 238000002425 crystallisation Methods 0.000 claims abstract description 51
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 46
- PALNZFJYSCMLBK-UHFFFAOYSA-K magnesium;potassium;trichloride;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-].[Cl-].[K+] PALNZFJYSCMLBK-UHFFFAOYSA-K 0.000 claims abstract description 45
- 239000012535 impurity Substances 0.000 claims abstract description 44
- 239000011449 brick Substances 0.000 claims abstract description 43
- 239000000203 mixture Substances 0.000 claims abstract description 37
- 238000001816 cooling Methods 0.000 claims abstract description 36
- 230000008025 crystallization Effects 0.000 claims abstract description 34
- 238000010276 construction Methods 0.000 claims abstract description 26
- 230000033228 biological regulation Effects 0.000 claims abstract description 12
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 107
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 74
- 239000007790 solid phase Substances 0.000 claims description 72
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 63
- 239000000243 solution Substances 0.000 claims description 50
- 239000007791 liquid phase Substances 0.000 claims description 48
- 239000001103 potassium chloride Substances 0.000 claims description 41
- 239000007864 aqueous solution Substances 0.000 claims description 40
- 239000002994 raw material Substances 0.000 claims description 40
- 238000004090 dissolution Methods 0.000 claims description 36
- 239000011780 sodium chloride Substances 0.000 claims description 32
- 229910000861 Mg alloy Inorganic materials 0.000 claims description 28
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 claims description 21
- 238000001556 precipitation Methods 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 16
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- 238000001704 evaporation Methods 0.000 claims description 12
- 230000008020 evaporation Effects 0.000 claims description 11
- 230000004927 fusion Effects 0.000 claims description 9
- 238000000746 purification Methods 0.000 claims description 9
- 239000008346 aqueous phase Substances 0.000 claims description 8
- 239000012267 brine Substances 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 8
- 238000005868 electrolysis reaction Methods 0.000 claims description 8
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 8
- 235000010755 mineral Nutrition 0.000 claims description 8
- 239000011707 mineral Substances 0.000 claims description 8
- 239000010413 mother solution Substances 0.000 claims description 8
- 238000012216 screening Methods 0.000 claims description 8
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000002525 ultrasonication Methods 0.000 claims description 8
- 239000000523 sample Substances 0.000 claims description 5
- 238000007654 immersion Methods 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 abstract description 16
- 239000002699 waste material Substances 0.000 abstract description 16
- 239000000047 product Substances 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 2
- 239000011777 magnesium Substances 0.000 description 52
- 229910052749 magnesium Inorganic materials 0.000 description 43
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 41
- 238000002844 melting Methods 0.000 description 26
- 230000008018 melting Effects 0.000 description 26
- 230000008569 process Effects 0.000 description 24
- 230000004907 flux Effects 0.000 description 23
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 14
- 239000007787 solid Substances 0.000 description 14
- 239000007789 gas Substances 0.000 description 13
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 11
- 238000013467 fragmentation Methods 0.000 description 11
- 238000006062 fragmentation reaction Methods 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 150000002500 ions Chemical class 0.000 description 10
- -1 KCl and NaCl Chemical compound 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 7
- 235000019341 magnesium sulphate Nutrition 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000002923 metal particle Substances 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 238000007499 fusion processing Methods 0.000 description 5
- 229910001629 magnesium chloride Inorganic materials 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000007493 shaping process Methods 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 239000012452 mother liquor Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 150000002910 rare earth metals Chemical class 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 239000013589 supplement Substances 0.000 description 3
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 2
- 241001131796 Botaurus stellaris Species 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 206010020843 Hyperthermia Diseases 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 241001062472 Stokellia anisodon Species 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000013016 damping Methods 0.000 description 2
- 230000009970 fire resistant effect Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000036031 hyperthermia Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000003265 pulping liquor Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 2
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 2
- 235000019830 sodium polyphosphate Nutrition 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 2
- 241000370738 Chlorion Species 0.000 description 1
- 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 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 231100000045 chemical toxicity Toxicity 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- C04B5/00—Treatment of metallurgical slag ; Artificial stone from molten metallurgical slag
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
-
- 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
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a kind of resource utilization method of magnesium-rare earth smelting slag, particularly with magnesium-rare earth smelting slag for waste Snow Agent, MAGNESIUM METAL, the preparation method of sintered magnesia brick material of construction and synthetic carnallite, in turn include the following steps: (1) supersonic leaching, (2) solid-liquid separation, (3) Gu solid-separation, (4) dissolving with hydrochloric acid, (5) solid-liquid separation, (6) composition regulation and control, (7) evaporative crystallization, (8) solid-liquid separation, (9) in and removal of impurities, (10) solid-liquid separation, (11) crystallisation by cooling and (12) solid-liquid separation.This method can solve magnesium-rare earth smelting slag resource recycling problem, can reach protection of the environment again, avoid secondary pollution.This preparation method's rational technology is convenient, safe preparation process is reliable, preparing product quality is good.
Description
Technical field
The invention belongs to Chemical Engineering and Technology and environment protection comprehensive utilization of resources field, particularly a kind of resource utilization method of magnesium-rare earth smelting slag.
Background technology
Magnesium and magnesium-rare earth: from the eighties of last century later stage eighties so far, along with magnesium alloy is in the application in Aeronautics and Astronautics field, the research that rare earth element is applied to magnesium alloy comes into one's own again, magnesium-rare earth can overcome the shortcoming that traditional magnesium alloy materials exists, and meets modern industry and realizes lightweight, energy-saving and environmental protection, safe, comfortable, Sustainable development etc. to material proposed requirement.Rare earth plays more and more important effect as main alloying element or micro alloying element in magnesium alloy research field.Magnesium-rare earth is structural metallic materials the lightest in current engineer applied, and magnesium-rare earth has high specific rigidity and specific tenacity, good damping and amortization and damping property, excellent electromagnetic shielding, electromagnetism interference performance.
The flux melting of magnesium-rare earth: in order to prepare the magnesium-rare earth met the demands, must carry out preparation and the melting of magnesium-rare earth.But magnesium alloy is relatively active, when magnesium alloy in an atmosphere melting time, in order to prevent magnesium liquid surface oxidation, burning, the normal smelting agent that uses is protected.Therefore; smelting agent protection still has a wide range of applications in modern industry as a kind of traditional magnesium alloy smelting mode; smelting agent prevents except the oxidizing fire of liquid magnesium alloy in fusion process except playing isolated air; also use as smelting agent; the non-metallic inclusion generated due to oxidation with removing, to purify alloy melt, improves magnesium-alloy material performance.
In the fusion process of magnesium-rare earth, the impurity in flux melting removing crude magnesium must be carried out to crude magnesium.Reason is that nonmetallic impurity (as oxide compound, nitride etc.) in crude magnesium and the Effect on Mechanical Properties of metallic impurity (as Mn, Zn, Al, Si) to the magnesium-rare earth product formed are very large, magnesium-rare earth is become fragile, limit expansion intensity diminishes, and causes magnesium-rare earth to be difficult to adapt to the needs of press working; Metallic impurity Fe, Cu, Ni make the erosion resistance of magnesium-rare earth be deteriorated.Therefore, to reduce as far as possible and remove these impurity in crude magnesium, to obtain the rare earth magnesium alloy material of high-quality.
The characteristic of flux and flux composition in magnesium fusion process: containing metallic impurity and nonmetallic impurity in crude magnesium, the smelting fusing agent therefore as crude magnesium should meet following condition:
(1) producing, using, preserving and do not having in transportation of materials process chemical toxicity and severe corrosive.
(2) there is certain melting, insoluble slag can be generated with impurity generation physics in magnesium or chemical reaction.
(3) lower than magnesium-rare earth or magnesium of fusing point.
(4) in the molten state, fused salt density should be larger than magnesium-rare earth, and have suitable density difference, and fused salt and magnesium liquid can layerings very well.
(5) in melting and sepn process, flux fused salt should have less viscosity, and magnesium-rare earth liquid can thoroughly be clarified in fusion process.
(6) flux has suitable interfacial tension with magnesium-rare earth liquid in whole fusion process.In smelt stage, less interfacial tension can protect preferably magnesium-rare earth not burned or oxidation.Leaving standstill the stage in melting has larger interfacial tension that magnesium-rare earth can be made to fuse better and be separated with flux.
(7) flux cationic not with molten metal magnesium-rare earth generation replacement(metathesis)reaction, in order to avoid polluted for the second time.
Smelting fusing agent has two effects, and one is the impurity in removing magnesium-rare earth, and another covers molten rare earth magnesium alloy do not contact with air and prevent oxidizing fire.At the covering flux that the fusion stage of magnesium-rare earth uses, require that its fusing point is low, density is little, good to the wettability of magnesium-rare earth.At the smelting fusing agent that smelt stage uses, require that its fusing point is low, good fluidity, good to the wettability of oxide compound, nitride, density ratio magnesium-rare earth is large, poor to the wettability of magnesium-rare earth, is beneficial to the separation of impurity.
In the flux that production uses, MgCl
2, KCl can improve the wettability of flux to rare earth oxide magnesium alloy, therefore these two kinds of components content in smelting fusing agent is higher.
The operation of flux melting: first the residue on crucible and oxide skin are removed, reexamining crucible has leakless.If occur that on sidewall of crucible depression or the thickness at its wall and the end are less than the half of original thickness, then crucible can not use.Crucible after passed examination is placed on crucible oven, then by crucible oven electrified regulation.Treat that crucible heating arrives bolarious red heat, first in crucible, end flux is added, flux total amount is the 15-20% of thick magnesium-rare earth quality, then thick magnesium-rare earth is loaded, heat fused at 1023K temperature, slowly add thick magnesium-rare earth and smelting fusing agent again, when magnesium-rare earth in crucible reaches the height of crucible useful volume, magnesium-rare earth liquid temp is made to remain on 983K, then smelting fusing agent is added, add-on is magnesium-rare earth 20kg per ton, and limit edged stirs, and flux is fully mixed with magnesium-rare earth liquid and reaches decontamination effect improving.The melting operation time is 10-20min, then controls at 1013-1023K by temperature, leaves standstill 10-15min, impurity is fully separated with magnesium-rare earth.Because the iron level in molten magnesium-rare earth can increase with the rising of temperature, thus leave standstill after terminating and the temperature of magnesium-rare earth liquid is down to 983K from 1013K, be incubated at this temperature.In above process, the magnesium-rare earth in crucible often burns, and can sprinkle covering flux to stop the burning of magnesium-rare earth, prevent the oxidational losses of magnesium-rare earth.
Flux melting can only remove the nonmetal and a part of metallic impurity in magnesium-rare earth, and most metallic impurity are difficult to be got rid of by melting, melting.To the high magnesium-rare earth ingot of some purity requirements while adding flux melting, then add some additives and carry out degree of depth melting.After melting by the magnesium-rare earth hydraulic control in crucible when the 983K, then carry out ingot casting.
China is magnesium-rare earth resource big country, and reserves occupy first place in the world; Be again magnesium-rare earth big producing country at present, output accounts for the whole world more than 2/3; Magnesium-rare earth also emerges rapidly; Magnesium-rare earth smelting slag surges year by year, processes bad meeting and causes serious environmental pollution.Current process magnesium-rare earth smelting slag has following methods:
(1) strengthen flux consumption and carry out melting extraction metal-rare-earth magnesium alloy again, cause both increasing power consumption, continue again to produce containing hypertoxic waste residue.
(2) with diluted hydrochloric acid dissolution magnesium-rare earth smelting slag carnallitite and rare earth chloride magnesium alloy (sea lake salt and chemical industry, 1st phase in 2006,16-18 page), the technological process producing carnallitite and magnesium chloride from Melting Magnesium slag is broken powder process (particle diameter l-2mm), rare HC1 (concentration 10-15%) dissolves, and adopts NaCO
3in and excess acid, filtering and impurity removing, neutralization, cooling, Crystallization Procedure.Design preparation technology, and discuss the Influential Factors in production, final production goes out qualified product up to standard.
MgCl
26H
2the production method of O: by the filtrate refined, temperature controls 165-170 DEG C of evaporation concentration to MgCl
2content is 550-750g/L, is cooled to crystallization 8h under 25-30 DEG C of condition, and through centrifugation, obtained magnesium chloride mother liquor enters subsequent processing.
Carnallitite is produced: composition is the haloid deposit (KClMgCl of potassium, magnesium
26H
2o).Molecular weight 277.87.Colourless rhombic system (rhombic system) particulate state or compact mass thing aggregate output, crystal is rare.Pure person is colourless to white, is clear to opaque.Very easily deliquescence in atmosphere, soluble in water.Impure rear pinkiness.Bitter.There is greasy luster.Taste is salty, and property is crisp, without cleavage, and tool fluorescent both.Mohs hardness 2-3, proportion 1.602.Be heated to 110-120 DEG C and be decomposed into magnesium chloride four water thing and Repone K.Be heated to 176 DEG C to dewater completely, have a small amount of hydrolysis phenomena simultaneously.When being heated to 750-800 DEG C, dehydration melting, is settled out magnesium oxide.Carnallitite is the magnesian important source material of preparation.
Adopt and produce MgC1
26H
2mother liquor after O, also containing KCl, MgCl in analytical solution
2, NaCl, SO
4 2-, CO
3 2-; By KCl:MgCl
2: CaCl
2=1:2:0.15 proportioning quantitatively supplements MgCl
26H
2o and CaCl
2, add CaCl
2remove the SO in solution exactly
4 2-, CO
3 2-, evaporating after everything is ready, through being fully uniformly mixed dissolving, filtering out CaSO
4, CaCO
3precipitation, is then heated to about 750 DEG C, makes 3 kinds of muriate meltings, insulation 15-20min, and precipitate completely until calcium sulfate, calcium carbonate, oxide impurity, filtering separation, melt naturally cools to 30-50 DEG C, then through fragmentation, obtained carnallitite finished product.This technique need consume a large amount of hydrochloric acid and sodium carbonate, on the contrary the magnesium-rare earth grain of very high value is generated the magnesium chloride of low value, and still produces waste residue.
(3) with sulfuric acid dissolution magnesium alloy smelting slag carnallitite and magnesium sulfate (World Nonferrous Metals, the 10th phase in 2002,29-31 page), first adopt sulfuric acid to be leached by magnesium alloy smelting slag, then carry out removal of impurities, neutralization obtains magnesium sulfate; In carnallitite production process, adopted by the mother liquor produced after magnesium sulfate and quantitatively supplement MgCl
2h
2o and CaCl
2kCl and MgCl in adjustment solution
2mol ratio, meet the component relationship preparing carnallitite, through removing the impurity in solution further, then evaporate, through being fully uniformly mixed dissolving, until micro-calcium sulfate, magnesium sulfate, magnesium oxide contamination precipitation completely after, filtering separation, melt naturally cooling, again through fragmentation, obtains carnallitite finished product.This technique need consume a large amount of sulfuric acid and magnesium sulfate.Supplement MgCl
2h
2o and CaCl
2adjustment solution consumption MgCl
2h
2o and CaCl
2.
These two kinds of methods both increased power consumption, wasted resource again, can't utterly destroy waste residue.The unique method that China produces flux now makes of the moisture carnallitite raw material dehydration in the Cha Er Han Salt Lake of Ge-ermu, Qinghai Province of China.Moisture carnallitite raw material is very valuable, main as potash fertilizer raw material, secondly can as electrolytic metal magnesium-rare earth raw material.
(4) Chinese patent (2009101689364, CN101704010, a kind of Melting Magnesium slag substep produces the method for crude magnesium grain, flux, magnesia brick).Disclose and carry crude magnesium grain from the dry separation of Melting Magnesium slag, the mother liquor flux of water dissolution residuum, the method for waste residue magnesia brick.Collect the Melting Magnesium slag that metal Mg-based hydrogen storage factory is discarded, go out crude magnesium grain by fragmentation, powder process, selection by winnowing.The raw material of magnesium powder processed or magnesium ingot can be made.Residuum dissolves, filter, by mother liquid evaporation, concentrated, dehydration, melting, cooling, fragmentation, and obtained dehydration carnallitite (production metal Mg-based hydrogen storage flux) finished product.Useless magnesium slag under filtering makes Chemical bond and the fire-resistant magnesia brick of sintering high temperature.
The subject matter that this method exists is that Melting Magnesium ground-slag is broken and selection by winnowing difficult, Gu be solid-separation, efficiency is low; In Melting Magnesium slag, Mg content is few, and selection by winnowing amount is large, and energy consumption is large; Useless magnesium slag under filtering makes Chemical bond and the fire-resistant magnesia brick of sintering high temperature, serious waste of resources.
Summary of the invention
The object of this invention is to provide a kind of resource utilization method of magnesium-rare earth smelting slag, to solve the recycling problem of magnesium-rare earth smelting slag.
For achieving the above object, the present invention is by the following technical solutions:
A resource utilization method for magnesium-rare earth smelting slag, in turn includes the following steps:
(1) supersonic leaching: in supersonic leaching equipment, adopts water and/or synthetic carnallite crystalline mother solution to be leaching agent, and the water miscible chlorate leaching in magnesium-rare earth smelting slag is entered in aqueous phase the aqueous solution obtained containing chlorate;
(2) solid-liquid separation: in solid-liquid separation equipment, carries out solid-liquid separation by the material that step (1) obtains, and the liquid phase material obtained removes step (6) separation and purification, and the solid-phase material obtained enters step (3);
(3) Gu solid-separation: Gu in solid-separating device, using step (2) Gu the solid-phase material obtained obtains MAGNESIUM METAL solid-phase material as the raw material use preparing magnesium-rare earth through broken, solid-separation, other colony's solid-phase material enters step (4);
(4) dissolving with hydrochloric acid: in dissolution equipment, adopting mass concentration to be 5-10% hydrochloric acid is solvent, and dissolved by the solid-phase material that step (3) obtains, the aqueous solution obtained containing chlorate enters step (5);
(5) solid-liquid separation: in solid-liquid separation equipment, the material that step (4) obtains is carried out solid-liquid separation, the solid-phase material obtained is as the raw material preparing sintered magnesia brick material of construction, and the liquid phase material obtained is that the chlorate aqueous solution enters step (6);
(6) composition regulation and control: liquid phase material step (5) obtained is separated with step (2) and obtains the chlorate aqueous solution and mix, and adds carnallitite mineral in mixed chlorinated salt brine solution, make the composition of the aqueous solution regulate and control at MgCl
2be 1.05-1.10:1 with the mol ratio of KCl, meet the requirement of carnallite crystalliser pan composition;
(7) evaporative crystallization: in evaporation crystallization equipment, is evaporated to water-content in material and, at 35-50%, evaporates the supplementary use of water except anhydrating as step (1), making the sodium-chlor crystallization in solution simultaneously;
(8) solid-liquid separation: in solid-liquid separation equipment, carries out solid-liquid separation by the material that step (7) obtains at 100-120 DEG C, and the solid-phase material sodium-chlor obtained uses as Snow Agent, and the liquid phase material obtained enters step (9);
(9) in and removal of impurities: adopt magnesium oxide as in and cleaner, between regulator solution pH value to 9-11, make the impurity F e in solution
2+, Fe
3+, Mn
2+, Cu
2+produce precipitation in the basic conditions;
(10) solid-liquid separation: in solid-liquid separation equipment, carries out solid-liquid separation by the material that step (9) obtains, and the liquid phase material obtained enters step (11), and the solid-phase material that separation obtains is as the raw material preparing sintered magnesia brick material of construction;
(11) crystallisation by cooling: in cooling crystallizing equipment, by material from 100-120 DEG C of cooling down to 10-40 DEG C, obtains the MgCl that quality group becomes 31-33%
2, the NaCl of KCl, 4-6% of 25-28% and other be H
2the synthetic carnallite of O;
(12) solid-liquid separation: in solid-liquid separation equipment, the material that step (11) obtains is carried out solid-liquid separation, the liquid phase material obtained goes step (1) to recycle as the leaching agent of supersonic leaching, and being separated the solid-phase material obtained is that synthetic carnallite prepares the raw material of MAGNESIUM METAL or magnesium alloy smelting reagent as fusion electrolysis.
Further, in described step (1), supersonic leaching carries out in the supersonic leaching equipment of ultrasonic generator, leaching vessels is autoclave or slot type or tube container, and described ultrasonic generator is any one in groove type ultrasonic wave producer, probe type ultrasonic wave producer, immersion ultrasonic generator.
Further, the ultrasonication intensity of described ultrasonic generator is 0.2-20.0W/cm
2, ultrasonic frequency is 19-80kHz, and the solid-to-liquid ratio of magnesium-rare earth smelting slag and leaching liquid is 100g:200-600mL, and service temperature is 10-60 DEG C.
Further, in described step (3), Gu Gu-be separated be screening be separated or wet concentration be separated or selection by winnowing separation method in one.
Further, described sintered magnesia brick material of construction be in raw material containing magnesium slag through pulverizing, preparing burden, mix, shaping after to burn till with high temperature and make sintered magnesia brick.
Further, described solid-liquid separation equipment is any one in decanter type, filtering type, centrifugal, vane-type solid-liquid separation device.
Further, described magnesium-rare earth is the magnesium alloy containing rare earth element.Rare earth element has dehydrogenation, deoxygenation, sulphur removal, deironing, effect except inclusion in magnesium alloy fused mass, reaches the effect of degasification melting, purification melt.
Further, described dissolution equipment is autoclave stirring and dissolving equipment.
Further, Gu described solid-separating device be screening separating device, selection by winnowing separating device, wet concentration separating device one.
Know-why of the present invention is:
(1) characteristic of smelting slag is made full use of
Smelting slag is black or dark gray solid, comparatively hard, not easily broken.But smelting slag easily absorbs water, make moist, after water suction, smelting slag becomes loose shape solid, and fragmentation is easier.During with water dissolution magnesium-rare earth smelting slag, have a little gas to produce, smelting slag is partially soluble in water, and dissolution rate is slower.Main containing MgCl in magnesium alloy smelting slag
2, the chlorate such as KCl and NaCl, this waste residue mainly contains following characteristics:
1. negatively charged ion mainly chlorion, chlorate is soluble in water, if arbitrarily stacked, is dissolved under rainwater effect, infiltrates soil thus makes saline Land, and to buildings and highway.Therefore first should consider the comprehensive utilization of chlorate during process, otherwise by producing a large amount of muriate waste materials, cause secondary pollution.
2. positively charged ion is mainly the alkali and alkaline earth metal ions ions such as magnesium, potassium, sodium, and more difficult separation, therefore pays the utmost attention to the comprehensive utilization of its mixture.
3. the sodium-chlor source in waste residue is wide, and be worth low, if by its single separating-purifying, it is low in economic efficiency, and the potassium in waste residue and magnesium resource are the materials having application and economic worth most.
(2) characteristic that chlorination hydrochloric acid is soluble in water is made full use of
In utilizing the chlorates such as magnesium chloride in smelting slag, Repone K, sodium-chlor soluble in water, and the characteristic that the solubleness of these salt in water is large, the principle particularly utilizing the chlorate solution of smelting slag to produce synthetic carnallite is:
Based on MgCl during temperature variation
2, the different solubility of KCl and NaCl in water.Along with MgCl in solution
2the rising of concentration, the solubleness of KCl and NaCl then declines; Along with the rising of temperature, NaCl solubleness than KCl solubleness decline faster.
Therefore, at high MgCl
2under concentration and hot conditions, make sodium-chlor from mixed solution, form crystal and separate out, the sodium-chlor obtained as Snow Agent, the MgCl of removing sodium-chlor
2carry out crystallisation by cooling again with KCl solution and obtain synthetic carnallite.
(3) characteristic that the dissolution rate of MAGNESIUM METAL in water is slower is made full use of
Make full use of the dissolution rate of MAGNESIUM METAL in water slow, and there is reduction MAGNESIUM METAL and the slow feature of water speed of response after metallic magnesium surface generates oxide compound.Therefore, after making smelting slag water logging take out chlorate, MAGNESIUM METAL remaining in smelting slag is recycled.
(4) material making full use of indissoluble water in smelting slag is soluble in the characteristic in hydrochloric acid
Make full use of and be remainingly insoluble in the material of water, the characteristic be soluble in hydrochloric acid, the material reclaimed after remaining MAGNESIUM METAL is adopted dissolving with hydrochloric acid, obtain chlorate by product in smelting slag.
(5) making full use of synthetic carnallite is preparation MAGNESIUM METAL or the characteristic preparing smelting agent important source material
The preparation method of Snow Agent, MAGNESIUM METAL, sintered magnesia brick material of construction and synthetic carnallite must be produced respectively according to the characteristic of raw material in order to fully utilize smelting slag.Particularly utilize that carnallitite main component is potassium, the haloid deposit (KClMgCl of magnesium
26H
2o), the synthetic carnallite of preparation be preparation MAGNESIUM METAL and the important source material of magnesium alloy smelting agent.Namely realize high-quality high use, the low use of low-quality, the thinking that utilizes respectively, realize the comprehensive utilization of smelting slag.
(6) making full use of useless magnesium slag is the characteristic preparing sintered magnesia brick important source material
Useless magnesium slag can make magnesia brick by two kinds of methods: one, in useless magnesium slag, add suitable chemical bond (having water glass, spent pulping liquor, bittern, magnesium sulfate, Sodium hexametaphosphate 99 and sodium polyphosphate etc.), through mixing, shaping, dry and make Chemical bond magnesia brick (also known as not burning magnesia brick); Two, useless magnesium slag through pulverizing, preparing burden, mix, shaping after, burn till under the high temperature of 1550-1750 DEG C with hyperthermia tunnel Kiln, make sintered magnesia brick (also known as burned-magnesia brick).This product belongs to highiy refractory brick and can be used for electricity and protect side wall, glass melter regenerator grid room and cement kiln lining etc.
Advantage of the present invention is:
(1) M is made full use of
+, M
2+and Cl
-the source of salt formed, compositing characteristic and economic benefit characteristic, namely realize high-quality height, the thinking that utilizes respectively.Realize the comprehensive utilization of smelting slag.
(2) make full use of the dissolution rate of MAGNESIUM METAL in water slow, after therefore making smelting slag water logging take out chlorate, adopt and the MAGNESIUM METAL of remnants recycled after chlorate is taken out in water logging, recovery value is high.
(3) characteristic of fully large, the easy crystallization of application chlorate solubleness in water, to obtain that the chlorate water capacity easily adopts evaporation after removal of impurities, concentrated, crystallisation by cooling obtains alkali and alkaline earth metal ions chlorate, the chlorate obtained uses as the salt of defrost.
(4) make full use of the salt be insoluble in water and be soluble in characteristic in hydrochloric acid, make full use of and be remainingly insoluble in the material of water, the characteristic be soluble in hydrochloric acid, remaining thing material is adopted dissolving with hydrochloric acid leaching, obtain chlorate by product.
(5) useless magnesium slag can make magnesia brick by two kinds of methods, one adds suitable chemical bond (having water glass, spent pulping liquor, bittern, magnesium sulfate, Sodium hexametaphosphate 99 and sodium polyphosphate etc.) in useless magnesium slag, through mixing, shaping, dry and make Chemical bond magnesia brick (also known as not burning magnesia brick); Its two useless magnesium slag through pulverizing, preparing burden, mix, shaping after, burn till under the high temperature of 1550-1750 DEG C with hyperthermia tunnel Kiln, make sintered magnesia brick (also known as burned-magnesia brick).
(6) adopt magnesium oxide as in and cleaner, regulator solution pH value, makes the impurity F e in solution
2+, Fe
3+, Mn
2+, Cu
2+produce precipitation in the basic conditions, make the metallic impurity ion in solution produce precipitation, process efficiency is high, and removal of impurities is thorough.
The invention solves classical production process Problems existing; and magnesium-rare earth smelting slag total integration can be utilized; both the effect of save energy, comprehensive utilization of resources, protection of the environment had been reached; the raw material of Snow Agent, MAGNESIUM METAL, sintered magnesia brick material of construction and synthetic carnallite can be produced again, also solve high, the heavy-polluted technical barrier of cost that traditional smelting slag treatment process exists simultaneously.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described.
embodiment 1
Major process unit is: Gu supersonic leaching equipment, dissolution equipment, solid-liquid separation, solid-separating device, evaporative crystallizer, cooling crystallizer etc.
(mainly MgCl is consisted of with magnesium-rare earth smelting slag
2, KCl, NaCl, Mg and MgO etc.) (mainly consist of MgCl for waste Snow Agent (mainly consisting of NaCl etc.), MAGNESIUM METAL (mainly consisting of Mg), sintered magnesia brick (mainly consisting of MgO) material of construction and synthetic carnallite
2and KCl) preparation method, in turn include the following steps:
(1) supersonic leaching: in the supersonic leaching equipment of groove type ultrasonic wave producer, adopts water and synthetic carnallite crystalline mother solution (mainly to consist of mass percentage 32.8%MgCl
2, 0.9%KCl and 0.8%NaCl, other is mainly H
2o) be leaching agent, ultrasonication intensity is 0.2W/cm
2, ultrasonic frequency is 19kHz, and the solid-to-liquid ratio of magnesium-rare earth smelting slag and leaching liquid is 100g:200mL, and service temperature is 10 DEG C, and the water miscible chlorate leaching in magnesium-rare earth smelting slag is entered in aqueous phase the aqueous solution obtained containing chlorate.Some phenomenons magnesium-rare earth smelting slag is observed in the processes such as leaching dissolving: magnesium-rare earth smelting slag is black or dark gray solid, comparatively hard, not easily broken.But smelting slag easily absorbs water, make moist, after water suction, smelting slag becomes loose shape solid, and fragmentation is easier; During with water dissolution magnesium-rare earth smelting slag, have a little gas to produce, smelting slag is partially soluble in water, and dissolution rate is slower;
(2) solid-liquid separation: in decanter type solid-liquid separation equipment, the material that step (1) obtains is carried out solid-liquid separation, remove step (6) separation and purification further at the liquid phase material obtained, in the solid-phase material obtained, enter step (3) containing MAGNESIUM METAL particle and magnesium oxide etc.;
(3) Gu solid-separation: in screening separating device, solid-phase material step (2) obtained is through broken (particle diameter <lmm), then screening and separating obtains MAGNESIUM METAL solid-phase material as the raw material use preparing magnesium-rare earth, and other solid-phase material enters step (4);
(4) dissolving with hydrochloric acid: in autoclave stirring and dissolving equipment, adopt mass concentration be 5% hydrochloric acid be solvent, the solid-phase material that step (3) obtains is dissolved, during with diluted hydrochloric acid dissolution residue, gas is had to produce, have exothermic phenomenon, smelting slag major part is dissolved, and the aqueous solution obtained containing chlorate enters step (5);
(5) solid-liquid separation: in filtering type solid-liquid separation equipment, the material that step (4) obtains is carried out solid-liquid separation, the solid-phase material obtained is as the raw material preparing sintered magnesia brick material of construction, and the liquid phase material obtained is that the chlorate aqueous solution enters step (6);
(6) composition regulation and control: liquid phase material step (5) obtained is separated with step (2) the chlorate aqueous solution obtained and mixes in autoclave stirring tank, adds carnallitite mineral in mixed chlorinated salt brine solution, make the composition regulation and control of the aqueous solution at MgCl
2with the mol ratio of KCl at 1.05:1, meet the requirement of carnallite crystalliser pan composition;
(7) evaporative crystallization: in evaporation crystallization equipment, adopts steam heating to 110 DEG C, is evaporated to water-content in material and, 50%, evaporates the supplementary use of water except anhydrating as step (1), making the sodium-chlor crystallization in solution simultaneously;
(8) solid-liquid separation: in filtering type solid-liquid separation equipment, carries out solid-liquid separation by the material that step (7) obtains at 100 DEG C, and the solid-phase material sodium-chlor obtained uses as Snow Agent, and the liquid phase material obtained enters lower step (9);
(9) in and removal of impurities: adopt magnesium oxide as in and cleaner, regulator solution pH value, to 9, makes the impurity F e in solution
2+, Fe
3+, Mn
2+, Cu
2+produce precipitation in the basic conditions, make the metallic impurity ion in solution produce precipitation;
(10) solid-liquid separation: in vane-type solid-liquid separation device, carries out solid-liquid separation by the material that step (9) obtains, and the liquid phase material obtained enters step (11), and the solid-phase material that separation obtains is as the raw material preparing sintered magnesia brick material of construction;
(11) crystallisation by cooling: in cooling crystallizing equipment, crystallisation by cooling can divide two sections to carry out; First in vacuum crystallization groove, make slip cool to about 60 DEG C from 100 DEG C, then in water-cooled crystallizer tank, slurry temperature is dropped to 10 DEG C, institute's synthetic carnallite is roughly composed as follows: 31.7%MgCl
2, 26.3%KCl, 5.5%NaCl, other is H
2o;
(12) solid-liquid separation: in filtering type solid-liquid separation equipment, the material that step (11) obtains is carried out solid-liquid separation, the liquid phase material obtained goes step (1) to recycle as the leaching agent of supersonic leaching, and being separated the solid-phase material obtained is that synthetic carnallite prepares the raw material of MAGNESIUM METAL or magnesium alloy smelting reagent as fusion electrolysis.
embodiment 2
Major process unit is: Gu supersonic leaching equipment, dissolution equipment, solid-liquid separation, solid-separating device, evaporative crystallizer, cooling crystallizer etc.
(mainly MgCl is consisted of with magnesium-rare earth smelting slag
2, KCl, NaCl, Mg and MgO etc.) (mainly consist of MgCl for waste Snow Agent (mainly consisting of NaCl etc.), MAGNESIUM METAL (mainly consisting of Mg), sintered magnesia brick (mainly consisting of MgO) material of construction and synthetic carnallite
2and KCl) preparation method, in turn include the following steps:
(1) supersonic leaching: in the supersonic leaching equipment of probe type ultrasonic wave producer, adopts water and synthetic carnallite crystalline mother solution (mainly to consist of mass percentage 34.6%MgCl
2, 1.2%KCl and 0.8%NaCl, other is mainly H
2o) be leaching agent, ultrasonication intensity is 20.0W/cm
2, ultrasonic frequency is 80kHz, and the solid-to-liquid ratio of magnesium-rare earth smelting slag and leaching liquid is 100g:200mL, and service temperature is 10 DEG C, and the water miscible chlorate leaching in magnesium-rare earth smelting slag is entered in aqueous phase the aqueous solution obtained containing chlorate.Some phenomenons magnesium-rare earth smelting slag is observed in the processes such as leaching dissolving: magnesium-rare earth smelting slag is black or dark gray solid, comparatively hard, not easily broken.But smelting slag easily absorbs water, make moist, after water suction, smelting slag becomes loose shape solid, and fragmentation is easier; During with water dissolution magnesium-rare earth smelting slag, have a little gas to produce, smelting slag is partially soluble in water, and dissolution rate is slower;
(2) solid-liquid separation: in filtering type solid-liquid separation equipment, the material that step (1) obtains is carried out solid-liquid separation, remove step (6) separation and purification further at the liquid phase material obtained, in the solid-phase material obtained, enter step (3) containing MAGNESIUM METAL particle and magnesium oxide etc.;
(3) Gu solid-separation: in selection by winnowing separating device, solid-phase material step (2) obtained is through broken (particle diameter <lmm), then selection by winnowing is separated and obtains MAGNESIUM METAL solid-phase material as the raw material use preparing magnesium-rare earth, and other solid-phase material enters step (4);
(4) dissolving with hydrochloric acid: in autoclave stirring and dissolving equipment, adopting mass concentration to be 10% hydrochloric acid is solvent, the solid-phase material that step (3) obtains is dissolved, during with diluted hydrochloric acid dissolution residue, gas is had to produce, have exothermic phenomenon, smelting slag major part is dissolved, and the aqueous solution obtained containing chlorate enters step (5);
(5) solid-liquid separation: in decanter type solid-liquid separation equipment, the material that step (4) obtains is carried out solid-liquid separation, the solid-phase material obtained is as the raw material preparing sintered magnesia brick material of construction, and the liquid phase material obtained is that the chlorate aqueous solution enters step (6);
(6) composition regulation and control: liquid phase material step (5) obtained is separated with step (2) and obtains the chlorate aqueous solution and carry out mixing in autoclave stirring tank, adds carnallitite mineral in mixed chlorinated salt brine solution, make the composition of the aqueous solution regulate and control at MgCl
2and the mol ratio of KCl is between 1.10:1, meet the requirement of carnallite crystalliser pan composition;
(7) evaporative crystallization: in evaporation crystallization equipment, adopts steam heating to 120 DEG C, is evaporated to water-content in material and, between 35%, evaporates the supplementary use of water except anhydrating as step (1), making the sodium-chlor crystallization in solution simultaneously;
(8) solid-liquid separation: in filtering type solid-liquid separation equipment, carries out solid-liquid separation by the material that step (7) obtains at 120 DEG C, and the solid-phase material sodium-chlor obtained uses as Snow Agent, and the liquid phase material obtained enters step (9);
(9) in and removal of impurities: adopt magnesium oxide as in and cleaner, between regulator solution pH value to 11, make the impurity F e in solution
2+, Fe
3+, Mn
2+, Cu
2+produce precipitation in the basic conditions, make the metallic impurity ion in solution produce precipitation;
(10) solid-liquid separation: in decanter type solid-liquid separation equipment, carries out solid-liquid separation by the material that step (9) obtains, and the liquid phase material obtained enters step (11), and the solid-phase material that separation obtains is as the raw material preparing sintered magnesia brick material of construction;
(11) crystallisation by cooling: in cooling crystallizing equipment, crystallisation by cooling can divide two sections to carry out; First in vacuum crystallization groove, make slip cool to about 60 DEG C from 120 DEG C, then in water-cooled crystallizer tank, slurry temperature is dropped to 40 DEG C, institute's synthetic carnallite is roughly composed as follows: 32.1%MgCl
2, 25.9%KCl, 5.2%NaCl, other is H
2o;
(12) solid-liquid separation: in decanter type solid-liquid separation equipment, the material that step (11) obtains is carried out solid-liquid separation, the liquid phase material obtained goes step (1) to recycle as the leaching agent of supersonic leaching, and being separated the solid-phase material obtained is that synthetic carnallite prepares the raw material of MAGNESIUM METAL or magnesium alloy smelting reagent as fusion electrolysis.
embodiment 3
Major process unit is: Gu supersonic leaching equipment, dissolution equipment, solid-liquid separation, solid-separating device, evaporative crystallizer, cooling crystallizer etc.
(mainly MgCl is consisted of with magnesium-rare earth smelting slag
2, KCl, NaCl, Mg and MgO etc.) be the preparation method of waste Snow Agent (mainly consisting of NaCl etc.), MAGNESIUM METAL (mainly consisting of Mg), sintered magnesia brick (mainly consisting of MgO) material of construction and synthetic carnallite, in turn include the following steps:
(1) supersonic leaching: in the supersonic leaching equipment of immersion ultrasonic generator, adopts water and synthetic carnallite crystalline mother solution (mainly to consist of mass percentage 36.0%MgCl
2, 0.6%KCl and 1.8%NaCl, other is mainly H
2o) be leaching agent, ultrasonication intensity is 5.0W/cm
2, ultrasonic frequency is 24kHz, and the solid-to-liquid ratio of magnesium-rare earth smelting slag and leaching liquid is 100g:600mL, and service temperature is 20 DEG C, and the water miscible chlorate leaching in magnesium-rare earth smelting slag is entered in aqueous phase the aqueous solution obtained containing chlorate.Some phenomenons magnesium-rare earth smelting slag is observed in the processes such as leaching dissolving: magnesium-rare earth smelting slag is black or dark gray solid, comparatively hard, not easily broken.But smelting slag easily absorbs water, make moist, after water suction, smelting slag becomes loose shape solid, and fragmentation is easier; During with water dissolution magnesium-rare earth smelting slag, have a little gas to produce, smelting slag is partially soluble in water, and dissolution rate is slower.
(2) solid-liquid separation: in vane-type solid-liquid separation device, the material that step (1) obtains is carried out solid-liquid separation, remove step (6) separation and purification further at the liquid phase material obtained, in the solid-phase material obtained, enter step (3) containing MAGNESIUM METAL particle and magnesium oxide etc.;
(3) Gu solid-separation: in wet concentration separating device, solid-phase material step (2) obtained is through broken (particle diameter <3mm), Gu then solid-separation obtains MAGNESIUM METAL solid-phase material as the raw material use preparing magnesium-rare earth, other solid-phase material enters step (4);
(4) dissolving with hydrochloric acid: in autoclave stirring and dissolving equipment, adopt mass concentration be 6% hydrochloric acid be solvent, the solid-phase material that step (3) obtains is dissolved, during with diluted hydrochloric acid dissolution residue, gas is had to produce, have exothermic phenomenon, smelting slag major part is dissolved, and the aqueous solution obtained containing chlorate enters step (5);
(5) solid-liquid separation: in centrifugal solid-liquid separation equipment, the material that step (4) obtains is carried out solid-liquid separation, the solid-phase material obtained is as the raw material preparing sintered magnesia brick material of construction, and the liquid phase material obtained is that the chlorate aqueous solution enters step (6);
(6) composition regulation and control: liquid phase material step (5) obtained is separated with step (2) and obtains the chlorate aqueous solution and mix, and adds carnallitite mineral in mixed chlorinated salt brine solution, make the composition of the aqueous solution regulate and control at MgCl
2with the mol ratio of KCl at 1.05:1, meet the requirement of carnallite crystalliser pan composition;
(7) evaporative crystallization: in evaporation crystallization equipment, adopts steam heating to 115 DEG C, is evaporated to water-content in material and, 40%, evaporates the supplementary use of water except anhydrating as step (1), making the sodium-chlor crystallization in solution simultaneously;
(8) solid-liquid separation: in filtering type solid-liquid separation equipment, carries out solid-liquid separation by the material that step (7) obtains at 115 DEG C, and the solid-phase material sodium-chlor obtained uses as Snow Agent, and the liquid phase material obtained enters lower step (9);
(9) in and removal of impurities: adopt magnesium oxide as in and cleaner, regulator solution pH value, to 10, makes the impurity F e in solution
2+, Fe
3+, Mn
2+, Cu
2+produce precipitation in the basic conditions, make the metallic impurity ion in solution produce precipitation;
(10) solid-liquid separation: in vane-type solid-liquid separation, carries out solid-liquid separation by the material that step (9) obtains, and the liquid phase material obtained enters step (11), and the solid-phase material that separation obtains is as the raw material preparing sintered magnesia brick material of construction;
(11) crystallisation by cooling: in cooling crystallizing equipment, crystallisation by cooling can divide two sections to carry out; First in vacuum crystallization groove, make slip cool to about 60 DEG C from 115 DEG C, then in water-cooled crystallizer tank, slurry temperature is dropped to 30 DEG C, institute's synthetic carnallite is roughly composed as follows: 33.0%MgCl
2, 26.8%KCl, 5.2%NaCl, other is H
2o.
(12) solid-liquid separation: in centrifugal solid-liquid separation equipment, the material that step (11) obtains is carried out solid-liquid separation, the liquid phase material obtained goes step (1) to recycle as the leaching agent of supersonic leaching, and being separated the solid-phase material obtained is that synthetic carnallite prepares the raw material of MAGNESIUM METAL or magnesium alloy smelting reagent as fusion electrolysis.
embodiment 4
Major process unit is: Gu supersonic leaching equipment, dissolution equipment, solid-liquid separation, solid-separating device, evaporative crystallizer, cooling crystallizer etc.
(mainly MgCl is consisted of with magnesium-rare earth smelting slag
2, KCl, NaCl, Mg and MgO etc.) (mainly consist of MgCl for waste Snow Agent (mainly consisting of NaCl etc.), MAGNESIUM METAL (mainly consisting of Mg), sintered magnesia brick (mainly consisting of MgO) material of construction and synthetic carnallite
2and KCl) preparation method, in turn include the following steps:
(1) supersonic leaching: in the supersonic leaching equipment of probe type ultrasonic wave producer, adopts water and synthetic carnallite crystalline mother solution (mainly to consist of mass percentage 34.2%MgCl
2, 1.6%KCl and 1.4%NaCl, other is mainly H
2o) be leaching agent, ultrasonication intensity is 12.0W/cm
2, ultrasonic frequency is 40kHz, and the solid-to-liquid ratio of magnesium-rare earth smelting slag and leaching liquid is 100g:400mL, and service temperature is 30 DEG C, and the water miscible chlorate leaching in magnesium-rare earth smelting slag is entered in aqueous phase the aqueous solution obtained containing chlorate.Some phenomenons magnesium-rare earth smelting slag is observed in the processes such as leaching dissolving: magnesium-rare earth smelting slag is black or dark gray solid, comparatively hard, not easily broken.But smelting slag easily absorbs water, make moist, after water suction, smelting slag becomes loose shape solid, and fragmentation is easier; During with water dissolution magnesium-rare earth smelting slag, have a little gas to produce, smelting slag is partially soluble in water, and dissolution rate is slower;
(2) solid-liquid separation: in centrifugal solid-liquid separation equipment, the material that step (1) obtains is carried out solid-liquid separation, remove step (6) separation and purification further at the liquid phase material obtained, in the solid-phase material obtained, enter step (3) containing MAGNESIUM METAL particle and oxidation magnesia mixture;
(3) Gu solid-separation: in wet concentration separating device, solid-phase material step (2) obtained is through broken (particle diameter <lmm), Gu then admittedly remaining-separation obtains MAGNESIUM METAL solid-phase material as the raw material use preparing magnesium-rare earth, other solid-phase material enters step (4);
(4) dissolving with hydrochloric acid: in autoclave stirring and dissolving equipment, adopt mass concentration be 8% hydrochloric acid be solvent, the solid-phase material that step (3) obtains is dissolved, during with diluted hydrochloric acid dissolution residue, gas is had to produce, have exothermic phenomenon, smelting slag major part is dissolved, and the aqueous solution obtained containing chlorate enters step (5);
(5) solid-liquid separation: in decanter type solid-liquid separation equipment, the material that step (4) obtains is carried out solid-liquid separation, the solid-phase material obtained is as the raw material preparing sintered magnesia brick material of construction, and the liquid phase material obtained is that the chlorate aqueous solution enters step (6);
(6) composition regulation and control: liquid phase material step (5) obtained is separated the chlorate aqueous solution obtained to carry out mixing in autoclave stirring tank with step (2), adds carnallitite mineral in mixed chlorinated salt brine solution, make the composition regulation and control of the aqueous solution at MgCl
2and the mol ratio of KCl is between 1.10:1, meet the requirement of carnallite crystalliser pan composition;
(7) evaporative crystallization: in evaporation crystallization equipment, adopts steam heating to 112 DEG C, is evaporated to water-content in material and, 48%, evaporates the supplementary use of water except anhydrating as step (1), making the sodium-chlor crystallization in solution simultaneously;
(8) solid-liquid separation: in vane-type solid-liquid separation device, carries out solid-liquid separation by the material that step (7) obtains at 112 DEG C, and the solid-phase material sodium-chlor obtained uses as Snow Agent, and the liquid phase material obtained enters step (9);
(9) in and removal of impurities: adopt magnesium oxide as in and cleaner, regulator solution pH value, to 11, makes the impurity F e in solution
2+, Fe
3+, Mn
2+, Cu
2+produce precipitation in the basic conditions, make the metallic impurity ion in solution produce precipitation;
(10) solid-liquid separation: in decanter type solid-liquid separation device, carries out solid-liquid separation by the material that step (9) obtains, and the liquid phase material obtained enters step (11), and the solid-phase material that separation obtains is as the raw material preparing sintered magnesia brick material of construction;
(11) crystallisation by cooling: in cooling crystallizing equipment, crystallisation by cooling can divide two sections to carry out.First in vacuum crystallization groove, make slip cool to about 50 DEG C from 112 DEG C, then in water-cooled crystallizer tank, slurry temperature is dropped between 30-40 DEG C, institute's synthetic carnallite is roughly composed as follows: 31.5%MgCl
2, 27.3%KCl, 4.8%NaCl, other is H
2o.
(12) solid-liquid separation: in filtering type solid-liquid separation equipment, the material that step (11) obtains is carried out solid-liquid separation, the liquid phase material obtained goes step (1) to recycle as the leaching agent of supersonic leaching, and being separated the solid-phase material obtained is that synthetic carnallite prepares the raw material of MAGNESIUM METAL or magnesium alloy smelting reagent as fusion electrolysis.
embodiment 5
Major process unit is: Gu supersonic leaching equipment, dissolution equipment, solid-liquid separation, solid-separating device, evaporative crystallizer, cooling crystallizer etc.
(mainly MgCl is consisted of with magnesium-rare earth smelting slag
2, KCl, NaCl, Mg and MgO etc.) (mainly consist of MgCl for waste Snow Agent (mainly consisting of NaCl etc.), MAGNESIUM METAL (mainly consisting of Mg), sintered magnesia brick (mainly consisting of MgO) material of construction and synthetic carnallite
2and KCl) preparation method, in turn include the following steps:
(1) supersonic leaching: in the supersonic leaching equipment of probe type ultrasonic wave producer, adopts water and synthetic carnallite crystalline mother solution (mainly to consist of mass percentage 32.4%MgCl
2, 1.8%KCl and 1.5%NaCl, other is mainly H
2o) be leaching agent, ultrasonication intensity is 20.0W/cm
2, ultrasonic frequency is 19kHz, and the solid-to-liquid ratio of magnesium-rare earth smelting slag and leaching liquid is 100g:600mL, and service temperature is 50 DEG C, and the water miscible chlorate leaching in magnesium-rare earth smelting slag is entered in aqueous phase the aqueous solution obtained containing chlorate.Some phenomenons magnesium-rare earth smelting slag is observed in the processes such as leaching dissolving: magnesium-rare earth smelting slag is black or dark gray solid, comparatively hard, not easily broken.But smelting slag easily absorbs water, make moist, after water suction, smelting slag becomes loose shape solid, and fragmentation is easier; During with water dissolution magnesium-rare earth smelting slag, have a little gas to produce, smelting slag is partially soluble in water, and dissolution rate is slower.
(2) solid-liquid separation: in decanter type solid-liquid separation device, the material that step (1) obtains is carried out solid-liquid separation, the liquid phase material obtained removes step (6) separation and purification further, enters step (3) in the solid-phase material obtained containing MAGNESIUM METAL particle and magnesium oxide etc.;
(3) Gu solid-separation: in screening separating device, solid-phase material step (2) obtained is through broken (particle diameter <2mm), then screening and separating obtains MAGNESIUM METAL solid-phase material as the raw material use preparing magnesium-rare earth, and other solid-phase material enters step (4);
(4) dissolving with hydrochloric acid: in autoclave stirring and dissolving equipment, adopt mass concentration be 5% hydrochloric acid be solvent, the solid-phase material that step (3) obtains is dissolved, during with diluted hydrochloric acid dissolution residue, gas is had to produce, have exothermic phenomenon, smelting slag major part is dissolved, and the aqueous solution obtained containing chlorate enters step (5);
(5) solid-liquid separation: in decanter type solid-liquid separation device, the material that step (4) obtains is carried out solid-liquid separation, the solid-phase material obtained is as the raw material preparing sintered magnesia brick material of construction, and the liquid phase material obtained is that the chlorate aqueous solution enters step (6);
(6) composition regulation and control: in autoclave stirring tank, liquid phase material step (5) obtained is separated with step (2) and obtains the chlorate aqueous solution and mix, and adds carnallitite mineral in mixed chlorinated salt brine solution, and the composition of the aqueous solution is regulated and controled at MgCl
2with the mol ratio of KCl at 1.10:1, meet the requirement of carnallite crystalliser pan composition;
(7) evaporative crystallization: in evaporation crystallization equipment, adopts steam heating to 120 DEG C, is evaporated to water-content in material and, 40%, evaporates the supplementary use of water except anhydrating as step (1), making the sodium-chlor crystallization in solution simultaneously;
(8) solid-liquid separation: in decanter type solid-liquid separation equipment, carries out solid-liquid separation by the material that step (7) obtains at 120 DEG C, and the solid-phase material sodium-chlor obtained uses as Snow Agent, and the liquid phase material obtained enters lower step (9);
(9) in and removal of impurities: adopt magnesium oxide as in and cleaner, regulator solution pH value, to 9, makes the impurity F e in solution
2+, Fe
3+, Mn
2+, Cu
2+produce precipitation in the basic conditions, make the metallic impurity ion in solution produce precipitation;
(10) solid-liquid separation: in decanter type solid-liquid separation device, carries out solid-liquid separation by the material that step (9) obtains, and the liquid phase material obtained enters step (11), and the solid-phase material that separation obtains is as the raw material preparing sintered magnesia brick material of construction;
(11) crystallisation by cooling: in cooling crystallizing equipment, crystallisation by cooling can divide two sections to carry out; First in vacuum crystallization groove, make slip cool to about 40 DEG C from 120 DEG C, then in water-cooled crystallizer tank, slurry temperature is dropped to 10 DEG C, synthetic carnallite is roughly composed as follows: 32.5%MgCl
2, 26.3%KCl, 5.3%NaCl, other is H
2o;
(12) solid-liquid separation: in centrifugal solid-liquid separation equipment, the material that step (11) obtains is carried out solid-liquid separation, the liquid phase material obtained goes step (1) to recycle as the leaching agent of supersonic leaching, and being separated the solid-phase material obtained is that synthetic carnallite prepares the raw material of MAGNESIUM METAL or magnesium alloy smelting reagent as fusion electrolysis.
embodiment 6
Major process unit is: Gu supersonic leaching equipment, dissolution equipment, solid-liquid separation, solid-separating device, evaporative crystallizer, cooling crystallizer etc.
(mainly MgCl is consisted of with magnesium-rare earth smelting slag
2, KCl, NaCl, Mg and MgO etc.) (mainly consist of MgCl for waste Snow Agent (mainly consisting of NaCl etc.), MAGNESIUM METAL (mainly consisting of Mg), sintered magnesia brick (mainly consisting of MgO) material of construction and synthetic carnallite
2and KCl) preparation method, in turn include the following steps:
(1) supersonic leaching: in the supersonic leaching equipment of immersion ultrasonic generator, adopts water and synthetic carnallite crystalline mother solution (mainly to consist of mass percentage 34.2%MgCl
2, 1.6%KCl and 1.2%NaCl, other is mainly H
2o) be leaching agent, ultrasonication intensity is 10.0W/cm
2, ultrasonic frequency is 60kHz, and the solid-to-liquid ratio of magnesium-rare earth smelting slag and leaching liquid is 100g:400mL, and service temperature is 60 DEG C, and the water miscible chlorate leaching in magnesium-rare earth smelting slag is entered in aqueous phase the aqueous solution obtained containing chlorate.Some phenomenons magnesium-rare earth smelting slag is observed in the processes such as leaching dissolving: magnesium-rare earth smelting slag is black or dark gray solid, comparatively hard, not easily broken.But smelting slag easily absorbs water, make moist, after water suction, smelting slag becomes loose shape solid, and fragmentation is easier; During with water dissolution magnesium-rare earth smelting slag, have a little gas to produce, smelting slag is partially soluble in water, and dissolution rate is slower.
(2) solid-liquid separation: in filtering type solid-liquid separation equipment, the material that step (1) obtains is carried out solid-liquid separation, remove step (6) separation and purification further at the liquid phase material obtained, in the solid-phase material obtained, enter step (3) containing MAGNESIUM METAL particle and oxidation magnesia mixture;
(3) Gu solid-separation: in selection by winnowing separating device, solid-phase material step (2) obtained is through broken (particle diameter <lmm), Gu then selection by winnowing must consolidate-be separated obtain MAGNESIUM METAL solid-phase material as prepare magnesium-rare earth raw material use, other solid-phase material enters step (4);
(4) dissolving with hydrochloric acid: in autoclave stirring and dissolving equipment, adopt mass concentration be 6% hydrochloric acid be solvent, the solid-phase material that step (3) obtains is dissolved, during with diluted hydrochloric acid dissolution residue, gas is had to produce, have exothermic phenomenon, smelting slag major part is dissolved, and the aqueous solution obtained containing chlorate enters step (5);
(5) solid-liquid separation: in filtering type solid-liquid separation equipment, the material that step (4) obtains is carried out solid-liquid separation, the solid-phase material obtained is as the raw material preparing sintered magnesia brick material of construction, and the liquid phase material obtained is that the chlorate aqueous solution enters step (6);
(6) composition regulation and control: liquid phase material step (5) obtained is separated with step (2) and obtains the chlorate aqueous solution and carry out mixing in autoclave stirring tank, adds carnallitite mineral in mixed chlorinated salt brine solution, make the composition of the aqueous solution regulate and control at MgCl
2with the mol ratio of KCl at 1.08:1, meet the requirement of carnallite crystalliser pan composition;
(7) evaporative crystallization: in evaporation crystallization equipment, adopts steam heating to 118 DEG C, is evaporated to water-content in material and, between 45%, evaporates the supplementary use of water except anhydrating as step (1), making the sodium-chlor crystallization in solution simultaneously;
(8) solid-liquid separation: in decanter type solid-liquid separation equipment, carries out solid-liquid separation by the material that step (7) obtains at 118 DEG C, and the solid-phase material sodium-chlor obtained uses as Snow Agent, and the liquid phase material obtained enters step (9);
(9) in and removal of impurities: adopt magnesium oxide as in and cleaner, regulator solution pH value, to 11, makes the impurity F e in solution
2+, Fe
3+, Mn
2+, Cu
2+produce precipitation in the basic conditions, make the metallic impurity ion in solution produce precipitation;
(10) solid-liquid separation: in vane-type solid-liquid separation device, carries out solid-liquid separation by the material that step (9) obtains, and the liquid phase material obtained enters step (11), and the solid-phase material that separation obtains is as the raw material preparing sintered magnesia brick material of construction;
(11) crystallisation by cooling: in cooling crystallizing equipment, crystallisation by cooling can divide two sections to carry out; First in vacuum crystallization groove, make slip cool to about 70 DEG C from 118 DEG C, then in water-cooled crystallizer tank, slurry temperature is dropped to 40 DEG C, institute's synthetic carnallite is roughly composed as follows: 31.8%MgCl
2, 26.2%KCl, 5.6%NaCl, other is H
2o.
(12) solid-liquid separation: in vane-type solid-liquid separation device, the material that step (11) obtains is carried out solid-liquid separation, the liquid phase material obtained goes step (1) to recycle as the leaching agent of supersonic leaching, and being separated the solid-phase material obtained is that synthetic carnallite prepares the raw material of MAGNESIUM METAL or magnesium alloy smelting reagent as fusion electrolysis.
The invention is not restricted to above-described embodiment, the technical scheme that all employings are equal to replacement or equivalence replacement formation all belongs to the scope of protection of present invention.Except the various embodiments described above, embodiment of the present invention also have a lot, the technical scheme that all employings are equal to or equivalence is replaced, all protection scope of the present invention it.
Claims (7)
1. a resource utilization method for magnesium-rare earth smelting slag, is characterized in that: in turn include the following steps:
(1) supersonic leaching: in supersonic leaching equipment, adopts water and/or synthetic carnallite crystalline mother solution to be leaching agent, and the water miscible chlorate leaching in magnesium-rare earth smelting slag is entered in aqueous phase the aqueous solution obtained containing chlorate;
(2) solid-liquid separation: in solid-liquid separation equipment, carries out solid-liquid separation by the material that step (1) obtains, and the liquid phase material obtained removes step (6) separation and purification, and the solid-phase material obtained enters step (3);
(3) Gu solid-separation: Gu in solid-separating device, using step (2) Gu the solid-phase material obtained obtains MAGNESIUM METAL solid-phase material as the raw material use preparing magnesium-rare earth through broken, solid-separation, other solid-phase material enters step (4);
(4) dissolving with hydrochloric acid: in dissolution equipment, adopting mass concentration to be 5-10% hydrochloric acid is solvent, and dissolved by the solid-phase material that step (3) obtains, the aqueous solution obtained containing chlorate enters step (5);
(5) solid-liquid separation: in solid-liquid separation equipment, the material that step (4) obtains is carried out solid-liquid separation, the solid-phase material obtained is as the raw material preparing sintered magnesia brick material of construction, and the liquid phase material obtained is that the chlorate aqueous solution enters step (6);
(6) composition regulation and control: liquid phase material step (5) obtained is separated with step (2) and obtains the chlorate aqueous solution and mix, and adds carnallitite mineral in mixed chlorinated salt brine solution, make the composition of the aqueous solution regulate and control at MgCl
2be 1.05-1.10:1 with the mol ratio of KCl, meet the requirement of carnallite crystalliser pan composition;
(7) evaporative crystallization: in evaporation crystallization equipment, is evaporated to water-content in material and, at 35-50%, evaporates the water supplementary use of water as step (1) of removing, make the sodium-chlor crystallization in solution simultaneously;
(8) solid-liquid separation: in solid-liquid separation equipment, the material that step (7) obtains is carried out solid-liquid separation at 100-120 DEG C, the solid-phase material sodium-chlor obtained uses as Snow Agent, and the liquid phase material obtained enters step (9);
(9) in and removal of impurities: adopt magnesium oxide as in and cleaner, between regulator solution pH value to 9-11, make the impurity F e in solution
2+, Fe
3+, Mn
2+, Cu
2+produce precipitation in the basic conditions;
(10) solid-liquid separation: in solid-liquid separation equipment, the material that step (9) obtains is carried out solid-liquid separation, the liquid phase material obtained enters step (11), and the solid-phase material that separation obtains is as the raw material preparing sintered magnesia brick material of construction;
(11) crystallisation by cooling: in cooling crystallizing equipment, by material from 100-120 DEG C of cooling down to 10-40 DEG C, obtains the MgCl that quality group becomes 31-33%
2, the NaCl of KCl, 4-6% of 25-28% and other be H
2the synthetic carnallite of O;
(12) solid-liquid separation: in solid-liquid separation equipment, the material that step (11) obtains is carried out solid-liquid separation, the liquid phase material obtained goes step (1) to recycle as the leaching agent of supersonic leaching, and being separated the solid-phase material obtained is that synthetic carnallite prepares the raw material of MAGNESIUM METAL or magnesium alloy smelting reagent as fusion electrolysis.
2. the resource utilization method of magnesium-rare earth smelting slag according to claim 1, it is characterized in that: in described step (1), supersonic leaching carries out in the supersonic leaching equipment of ultrasonic generator, leaching vessels is autoclave or slot type or tube container, and described ultrasonic generator is any one in groove type ultrasonic wave producer, probe type ultrasonic wave producer, immersion ultrasonic generator.
3. the resource utilization method of magnesium-rare earth smelting slag according to claim 2, is characterized in that: the ultrasonication intensity of described ultrasonic generator is 0.2-20.0W/cm
2, ultrasonic frequency is 19-80kHz, and the solid-to-liquid ratio of magnesium-rare earth smelting slag and leaching liquid is 100g:200-600mL, and service temperature is 10-60 DEG C.
4. the resource utilization method of magnesium-rare earth smelting slag according to claim 1, is characterized in that: in described step (3), Gu Gu-be separated be screening be separated or wet concentration be separated or selection by winnowing separation method in one.
5. the resource utilization method of magnesium-rare earth smelting slag according to claim 1, is characterized in that: described solid-liquid separation equipment is any one in decanter type, filtering type, centrifugal, vane-type solid-liquid separation device.
6. the resource utilization method of magnesium-rare earth smelting slag according to claim 1, is characterized in that: described dissolution equipment is autoclave stirring and dissolving equipment.
7. the resource utilization method of magnesium-rare earth smelting slag according to claim 1, is characterized in that: Gu described solid-separating device be screening separating device, selection by winnowing separating device, wet concentration separating device one.
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