CN101244843B - Method for recycling zirconium oxide and yttrium oxide from yttrium oxide steady zirconium oxide solid fused mass waste matter - Google Patents
Method for recycling zirconium oxide and yttrium oxide from yttrium oxide steady zirconium oxide solid fused mass waste matter Download PDFInfo
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- CN101244843B CN101244843B CN2008100735017A CN200810073501A CN101244843B CN 101244843 B CN101244843 B CN 101244843B CN 2008100735017 A CN2008100735017 A CN 2008100735017A CN 200810073501 A CN200810073501 A CN 200810073501A CN 101244843 B CN101244843 B CN 101244843B
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- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000002699 waste material Substances 0.000 title claims abstract description 15
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 title claims description 26
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 title claims description 6
- 229910001928 zirconium oxide Inorganic materials 0.000 title claims description 6
- 239000007787 solid Substances 0.000 title description 4
- 238000004064 recycling Methods 0.000 title description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 38
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 23
- 239000012452 mother liquor Substances 0.000 claims abstract description 22
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 20
- 239000006104 solid solution Substances 0.000 claims abstract description 18
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims abstract description 12
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 11
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 11
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 claims abstract description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims abstract description 10
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 claims abstract description 9
- IBSDADOZMZEYKD-UHFFFAOYSA-H oxalate;yttrium(3+) Chemical compound [Y+3].[Y+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O IBSDADOZMZEYKD-UHFFFAOYSA-H 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 238000002386 leaching Methods 0.000 claims abstract description 6
- 239000006227 byproduct Substances 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims description 23
- 239000013078 crystal Substances 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000002671 adjuvant Substances 0.000 claims description 8
- 230000020477 pH reduction Effects 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- DEXZEPDUSNRVTN-UHFFFAOYSA-K yttrium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Y+3] DEXZEPDUSNRVTN-UHFFFAOYSA-K 0.000 claims description 6
- GNKHOVDJZALMGA-UHFFFAOYSA-N [Y].[Zr] Chemical compound [Y].[Zr] GNKHOVDJZALMGA-UHFFFAOYSA-N 0.000 claims description 5
- 239000012141 concentrate Substances 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 239000002910 solid waste Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- 239000012065 filter cake Substances 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- -1 yttrium ion Chemical class 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract description 2
- 230000001376 precipitating effect Effects 0.000 abstract 4
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 abstract 3
- 230000003472 neutralizing effect Effects 0.000 abstract 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 9
- 229910052742 iron Inorganic materials 0.000 description 9
- 238000011084 recovery Methods 0.000 description 9
- 239000010987 cubic zirconia Substances 0.000 description 5
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- 150000002910 rare earth metals Chemical class 0.000 description 4
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000010437 gem Substances 0.000 description 3
- 229910001751 gemstone Inorganic materials 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052845 zircon Inorganic materials 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- 229910006501 ZrSiO Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- KAQHZJVQFBJKCK-UHFFFAOYSA-L potassium pyrosulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OS([O-])(=O)=O KAQHZJVQFBJKCK-UHFFFAOYSA-L 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to a method for recovering zirconia and yttria from the yttria-stabilized zirconia solid solution waste, which comprises the following steps: mixing the solid solution waste powder, sulfate and salt; acidizing and calcining at 200 to 320 DEG C; leaching the acidizing water and/or mother liquor under self-heating conditions; concentrating the leaching solution to leach zirconium sulfate; dissolving the zirconium sulfate in the water and purifying; neutralizing the zirconium hydroxide with alkali and precipitating; calcining the zirconium hydroxide to obtain zirconia; precipitating zirconium mother liquor to produce by-product of ammonium sulfate; neutralizing yttrium rich mother liquor and precipitating to obtain yttrium; dissolving yttrium rich residue with acid and purifying; precipitating oxalate to obtain yttrium oxalate; calcining to obtain the yttria. The method has the advantages of effectively separating the yttria from the zirconia in stable zirconia solid solution waste with optional yttrium ion under low temperature condition, changing the zirconia solid solution waste into valuables and utilizing the resources.
Description
One, technical field
The present invention relates to a kind of method that from yttria-stabilized zirconia Solid solution refuse, reclaims zirconium white and yttrium oxide, reclaim the method for zirconium white and yttrium oxide the zirconium matter grinding element that particularly a kind of Solid solution refuse of the cubic zirconia jewel from stabilized with yttrium oxide and yttrium oxide are partially stabilized and the discarded object of zirconium matter Work tool.
Two, background technology
The production method of existing zirconium white and zirconium series compound is a raw material with zircon sand concentrate or baddeleyite all, be prepared into by processing methodes such as alkali or alkaline earth metal oxide sintering decomposition method, carbonization chlorination process, plasma thermal decomposition methods, yttrium oxide then is to smelt through series such as removing of the grouping separation of enrichment, rare earth constituent element and non-rare earth to process and obtain from rare-earth mineral.No matter the compound of zirconium and yttrium is to adopt which kind of processing method to produce, and its raw material all is taken from the nature Mineral resources.Because head grade is low, become the ore deposit occurrence status special, it is required to need a large amount of primary ore of exploitation to satisfy social development, causes resource exhausted day by day, and environmental disruption is on the rise.
Meanwhile, a large amount of zirconium whites and yttrium oxide are used for synthetic zirconium gem crystal and zirconium matrix goods, and its discarded amount of abandoning is sizable in manufacturing process, as the utilization ratio of zirconium gem crystal only about 25～30%.To the processing such as the Chinese patent application number 200610161270.6 described methods of this type of solid waste, need to add than relatively large alkalimetal oxide and carry out the high-temperature calcination decomposition, pyrolysis time is long, the energy consumption height, the soda acid consumption is big, has increased the treatment capacity of discard solution, is unfavorable for energy-saving and emission-reduction.
Three, summary of the invention
The object of the present invention is to provide a kind of method that from yttria-stabilized zirconia Solid solution refuse, reclaims zirconium white and yttrium oxide.Improve resource utilization with this, cut down the consumption of energy, reduce three wastes discharge amount, the protection environment.
To achieve these goals, the present invention reclaims zirconium white and yttrium oxide by the following technical programs from yttria-stabilized zirconia Solid solution refuse.Comprise the Solid solution refuse is prepared powder, acidizing fired, frit leaches, condensing crystal, and water-soluble precipitation, operations such as calcining:
1.1 preparation powder
With the zirconium white Solid solution refuse drying and dehydrating of stabilized with yttrium oxide, reject inclusion, be crushed to-0.175mm, make powder;
1.2 it is acidizing fired
Is 1: 2.5～3.5: 1.25～1.50 to pack into and mix in the reactor described powder and sulfuric acid and acidification adjuvant ammonium sulfate by solid-to-liquid ratio, and acidizing fired 30～50min under 200～320 ℃ of temperature makes acidifying frit material;
1.3 frit leaches
Or/and the mother liquor that step 1.4 crystallization obtains leaches, solid-to-liquid ratio is 1: 2.5～3 with described acidifying frit material water, and temperature is 85～95 ℃, and extraction time 45～60min carries out solid-liquid separation after leaching finishes and gets zirconium yttrium clear liquid;
1.4 concentrated, crystallization
Described zirconium yttrium clear liquid is carried out evaporation concentration, and control concentrates feed liquid and contains Zr
+ 42.5～2.8mol/L acidity [H
+] 5.8～6.5mol/L, crystallisation by cooling separates mother liquor and obtains the zirconium sulfate crystal, and yttrium is stayed in the mother liquor;
1.5 water-soluble, precipitate, calcine zirconium white
With the zirconium sulfate deionized water dissolving that purifies, be prepared into and contain Zr
+ 41.3～1.5mol/L presoma salts solution, presoma salts solution and ammoniacal liquor neutralization, zirconium is separated out with the zirconium hydroxide precipitation, control condition is pH6.5～7.5, in and time 1～1.5h, the zirconium hydroxide slurry removes mother liquor and washing leaching cake after filtration, and filter cake obtains zirconium white at 850～900 ℃ of temperature lower calcination 1.5～2.0h;
1.6 preparation yttrium oxide
The mother liquor of step 1.4 is neutralized to pH 8～9 with ammoniacal liquor, after filtration, wash thick yttrium hydroxide, make yttrium solution with the thick yttrium hydroxide of dissolving with hydrochloric acid, after the yttrium solution purification is purified, be heated to 80～90 ℃, control pH 1～2 adds 2.5 times to Y
2O
3The oxalic acid of amount, precipitate yttrium oxalate, yttrium oxalate at 800～900 ℃ of following calcining 2～3h, is obtained yttrium oxide.
Wherein, described yttria-stabilized zirconia Solid solution refuse is the waste residue waste product of synthetic cubic crystal of zirconium oxide process output or cubic crystal of zirconium oxide at solid waste that the cutting and grinding course of processing abandons or produces the useless part of the waste product that produces in zirconium matter grinding element and the zirconium matter Work tool process.
Described acidification adjuvant ammonium sulfate is the byproduct of heavy zirconium mother liquor.
The present invention compared with prior art has following outstanding characteristics and obvious improvement:
1, adopts the method that from yttria-stabilized zirconia sosoloid refuse, reclaims zirconium white and yttrium oxide of the present invention, the zirconia solid refuse is turned waste into wealth, reach the effect of recycling.
Because the present invention is raw materials used to be yttria-stabilized zirconia Solid solution refuse, it is different with the physical properties and the chemical ingredients of zircon sand and rare-earth mineral, and zircon sand is with zirconium silicate ZrSiO
4Form exist, under the high temperature more than 1450 ℃, can be decomposed.The cubic zirconia Solid solution is under the high temperature more than 2700 ℃, yttrium oxide is fused to fully becomes cube phase composite crystal completely in the zirconia crystal lattice, in addition, in order to obtain the crystal of various different colours ornaments, in zirconium white and yttria-base material, oxide compounds such as Ce, Ti, Nd, Co, Cu, Ni, Nb have also been added, have that hardness is big, toughness is strong, fine and close, wear-and corrosion-resistant, physicochemical property is very stable, with to the utmost point difficult by hydrofluoric acid, sulfuric acid, hydrochloric acid, nitric acid and reagent etches such as fusion potassium pyrosulfate and caustic soda.Zirconium matter grinding element and Work tool waste product thereof the part that gives up belongs to the PSZ sintered article, and its fusing point has higher toughness and wear resisting property than cubic phase zircite height.Therefore, the utilization of zirconia solid changing waste into resources there is suitable difficulty.
2, characteristics of the present invention also are to become impurity composition in the sepn process of solid waste initial conversion does not need to be added in the product of production and a large amount of alkaline-earth metal ions and the alkalimetal ion that must remove, the acidifying invert point is low, time is short, acidization produces a large amount of reaction heat, only need to replenish a small amount of thermal source and can keep required invert point, greatly saved the energy, reduced and pollute.
3, raw and auxiliary material consumption is few, and the helping agent ammonium sulfate of use is directly produced by the technological process mother liquor.The metal recovery rate height improves 3～8% than former technology,
4, do not need high temperature service, so facility investment is few, technological process is controlled easily, easy realization of industrialization.
Four, embodiment
Below in conjunction with embodiment technical scheme of the present invention is further described:
Embodiment 1
(1) will be crushed to-0.175mm cubic zirconia powder (contains ZrO
276.45%, Y
2O
318.54%, SiO
22.86%, Fe
2O
30.58%) is pack reactor in to mix at 1: 2.5: 1.25 with sulfuric acid and acidification adjuvant ammonium sulfate by solid-to-liquid ratio, under 200～320 ℃ of temperature, reacts 30min, make acidifying frit material.
(2) be 1: 2.5 by the mother liquor and the leacheate of step (4) institute output by solid-to-liquid ratio with gained acidifying frit material dilute with water, leach down that extraction time 45～60min leaches and carries out solid-liquid separation after finishing and get zirconium yttrium clear liquid at 85～95 ℃.
(3) above-mentioned clear liquid is carried out evaporation concentration, control concentrates feed liquid and contains ZrO
22.5～2.8mol/L, acidity [H
+] 5.8～6.5mol/L, the zirconium sulfate crystal is separated out in cooling.
(4) the zirconium sulfate crystal with above-mentioned (3) gained goes out mother liquor with centrifuging, and crystal removes the impurity of absorption with the drip washing of 5～5.5mol/L sulphuric acid soln, obtains pure zirconium sulfate crystal.
(5), be prepared into and contain ZrO with above-mentioned zirconium sulfate crystal deionized water dissolving
21.3～1.5mol/L presoma salts solution is adjusted to the presoma salts solution and is contained ZrO
20.7～0.8mol/L uses NH
3Concentration is the neutralization of 15%～18% ammoniacal liquor, in and churning time be 1～1.5h, control pH6.5～7.5, zirconium precipitates with zirconium hydroxide, with the zirconium hydroxide slurries filtration, isolates mother liquor, use the water wash filter cake, the acquisition zirconium hydroxide.
(6) above-mentioned zirconium hydroxide is placed calcining furnace calcine 1.5～2h down, the acquisition zirconium white in 850～900 ℃.
(7) with the mother liquor of above-mentioned (4) output, be neutralized to pH 8～9 with ammoniacal liquor, yttrium is with Y (OH)
3Precipitation, after filtration, isolate mother liquor, water washing makes thick yttrium hydroxide.
(8) with above-mentioned thick yttrium hydroxide dissolving with hydrochloric acid, control pH4～5, solids removed by filtration impurity obtains the yttrium clear liquid.The yttrium clear liquid is heated to 80～90 ℃, and control pH 1～2 adds 2.5 times to Y
2O
3The oxalic acid of amount, precipitate yttrium oxalate, place calcining furnace in 800～900 ℃ of following calcining 2～3h yttrium oxalate, obtain yttrium oxide.
(9) mother liquor with above-mentioned (5) and (7) output concentrates, and by-product goes out ammonium sulfate.
Zirconium white product by the embodiment of the invention 1 described technical scheme preparation contains ZrO
2＞99.9%, SiO
2＜0.012%, Fe
2O
3＜0.001%, the zirconium rate of recovery 96.1%, yttrium oxide composition Y
2O
3/ Re
2O
3＞99.95%, ZrO
2＜0.001%, SiO
2＜0.0004%, Fe
2O
3＜0.0022%.The yttrium rate of recovery 92.3%.
Embodiment 2
To be crushed to-0.175mm cubic zirconia powder (chemical ingredients is with embodiment 1) and sulfuric acid and acidification adjuvant ammonium sulfate are pack reactor in to mix at 1: 1.75: 1.25 by solid-to-liquid ratio, acidifying conversion reaction 30min under 200～320 ℃ of temperature makes acidifying frit material.
All the other method stepss are with embodiment 1.
The zirconium white product that the technical scheme that is provided by the embodiment of the invention 2 obtains contains ZrO
2＞99.9%, SiO
2＜0.010%, Fe
2O
3＜0.001%, the zirconium rate of recovery 95.86%, yttrium oxide product composition Y
2O
3/ Re
2O
3＞99.95%, ZrO
2＜0.001%, SiO
2＜0.0013%, Fe
2O
3＜0.0022%.The yttrium rate of recovery 94.5%.
Embodiment 3
To be crushed to-0.175mm cubic zirconia powder (chemical ingredients is with embodiment 1) and sulfuric acid and acidification adjuvant ammonium sulfate are pack reactor in to mix at 1: 1.3: 1.5 by solid-to-liquid ratio, acidifying conversion reaction 50min under 200～300 ℃ of temperature makes acidifying frit material.
All the other method stepss are with embodiment 1.
The zirconium white product that the technical scheme that is provided by the embodiment of the invention 3 obtains contains ZrO
2＞99.9%, SiO
2＜0.001%, Fe
2O
3＜0.001%, the zirconium rate of recovery 92.98%, yttrium oxide product composition Y
2O
3/ Re
2O
3＞99.9%, ZrO
2＜0.001%, SiO
2＜0.0002%, Fe
2O
3＜0.0022%.The yttrium rate of recovery 91.4%.
Embodiment 4
To be crushed to-0.175mm zirconium matter grinding element and Work tool refuse powder (contain ZrO
294.5%, Y
2O
35.15%) be pack reactor in to mix at 1: 2: 1.25 with sulfuric acid and acidification adjuvant ammonium sulfate by solid-to-liquid ratio, acidifying conversion reaction 45min under 200～320 ℃ of temperature makes acidifying frit material.
All the other method stepss are with embodiment 1.
The zirconium white product that the technical scheme that is provided by the embodiment of the invention 4 obtains contains ZrO
2＞99.9%, SiO
2＜0.0001%, Fe
2O
3＜0.0005%, the zirconium rate of recovery 98.15%, yttrium oxide product composition Y
2O
3/ Re
2O
3＞99.99%, ZrO
2＜0.001%, SiO
2＜0.001%, Fe
2O
3＜0.0005%.The yttrium rate of recovery 95.02%.
Claims (3)
1. a method that reclaims zirconium white and yttrium oxide from the zirconium white Solid solution refuse of stabilized with yttrium oxide comprises the Solid solution refuse is prepared powder, and is acidizing fired, and frit leaches, condensing crystal, and water-soluble precipitation, calcination process is characterized in that:
1.1 preparation powder
With the zirconium white Solid solution refuse drying and dehydrating of stabilized with yttrium oxide, reject inclusion, be crushed to-0.175mm, make powder;
1.2 it is acidizing fired
Is 1: 2.5～3.5: 1.25～1.50 to pack into and mix in the reactor described powder and sulfuric acid and acidification adjuvant ammonium sulfate by solid-to-liquid ratio, and acidizing fired 30～50min under 200～320 ℃ of temperature makes acidifying frit material;
1.3 frit leaches
Or/and the mother liquor that step 1.4 crystallization obtains leaches, solid-to-liquid ratio is 1: 2.5～3 with described acidifying frit material water, and temperature is 85～95 ℃, and extraction time 45～60min carries out solid-liquid separation after leaching finishes and gets zirconium yttrium clear liquid;
1.4 concentrated, crystallization
Described zirconium yttrium clear liquid is carried out evaporation concentration, and control concentrates feed liquid and contains Zr
+ 42.5～2.8mol/L, acidity [H
+] 5.8～6.5mol/L, crystallisation by cooling separates mother liquor and obtains the zirconium sulfate crystal, and yttrium is stayed in the mother liquor;
1.5 water-soluble, precipitate, calcine zirconium white
With the zirconium sulfate deionized water dissolving that purifies, be prepared into and contain Zr
+ 41.3～1.5mol/L presoma salts solution, presoma salts solution and ammoniacal liquor neutralization, zirconium is separated out with the zirconium hydroxide precipitation, control condition is pH6.5～7.5, in and time 1～1.5h, the zirconium hydroxide slurry removes mother liquor and washing leaching cake after filtration, and filter cake obtains zirconium white at 850～900 ℃ of temperature lower calcination 1.5～2.0h;
1.6 preparation yttrium oxide
The mother liquor of step 1.4 is neutralized to pH 8～9 with ammoniacal liquor, after filtration, wash thick yttrium hydroxide, make yttrium solution with the thick yttrium hydroxide of dissolving with hydrochloric acid, after the yttrium solution purification is purified, be heated to 80～90 ℃, control pH 1～2 adds 2.5 times to Y
2O
3The oxalic acid of amount, precipitate yttrium oxalate, yttrium oxalate at 800～900 ℃ of following calcining 2～3h, is obtained yttrium oxide.
2. the method for claim 1 is characterized in that described yttria-stabilized zirconia Solid solution refuse is the waste residue waste product of synthetic cubic crystal of zirconium oxide process output or cubic crystal of zirconium oxide at solid waste that the cutting and grinding course of processing abandons or produces the useless part of the waste product that produces in zirconium matter grinding element and the zirconium matter Work tool process.
3. the method for claim 1 is characterized in that described acidification adjuvant ammonium sulfate is the byproduct of heavy zirconium mother liquor.
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| CN102583532A (en) * | 2011-06-15 | 2012-07-18 | 淄博市周村磊宝耐火材料有限公司 | Method for preparing high-purity zirconium oxide through purification from corundum-zirconia brick |
| US8940256B2 (en) * | 2011-12-07 | 2015-01-27 | Xylon Technical Ceramics, Inc. | Method for recycling of rare earth and zirconium oxide materials |
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