CN102417986A - Preparation method of high-purity low-zirconium hafnium oxide - Google Patents
Preparation method of high-purity low-zirconium hafnium oxide Download PDFInfo
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- CN102417986A CN102417986A CN2010102948975A CN201010294897A CN102417986A CN 102417986 A CN102417986 A CN 102417986A CN 2010102948975 A CN2010102948975 A CN 2010102948975A CN 201010294897 A CN201010294897 A CN 201010294897A CN 102417986 A CN102417986 A CN 102417986A
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- zirconium
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- hafnium oxide
- hafnium
- purity low
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- 229910052726 zirconium Inorganic materials 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- 229910000449 hafnium oxide Inorganic materials 0.000 title claims abstract description 37
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000007788 liquid Substances 0.000 claims abstract description 73
- 238000000605 extraction Methods 0.000 claims abstract description 63
- 239000012074 organic phase Substances 0.000 claims abstract description 61
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 30
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000001556 precipitation Methods 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- NXKAMHRHVYEHER-UHFFFAOYSA-J hafnium(4+);disulfate Chemical compound [Hf+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O NXKAMHRHVYEHER-UHFFFAOYSA-J 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 17
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003350 kerosene Substances 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 238000002425 crystallisation Methods 0.000 claims abstract description 10
- 230000008025 crystallization Effects 0.000 claims abstract description 10
- 238000002386 leaching Methods 0.000 claims abstract description 10
- 238000000746 purification Methods 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 48
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 26
- 229910021529 ammonia Inorganic materials 0.000 claims description 24
- 239000000284 extract Substances 0.000 claims description 17
- HNNUVNCHWLBGRE-UHFFFAOYSA-F hafnium(4+) zirconium(4+) tetrasulfate Chemical compound S(=O)(=O)([O-])[O-].[Hf+4].[Zr+4].S(=O)(=O)([O-])[O-].S(=O)(=O)([O-])[O-].S(=O)(=O)([O-])[O-] HNNUVNCHWLBGRE-UHFFFAOYSA-F 0.000 claims description 17
- 230000008929 regeneration Effects 0.000 claims description 15
- 238000011069 regeneration method Methods 0.000 claims description 15
- 239000001117 sulphuric acid Substances 0.000 claims description 15
- 235000011149 sulphuric acid Nutrition 0.000 claims description 15
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 12
- INIGCWGJTZDVRY-UHFFFAOYSA-N hafnium zirconium Chemical compound [Zr].[Hf] INIGCWGJTZDVRY-UHFFFAOYSA-N 0.000 claims description 11
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 239000003923 scrap metal Substances 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 2
- 230000001351 cycling effect Effects 0.000 claims description 2
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 3
- 230000003287 optical effect Effects 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 238000005272 metallurgy Methods 0.000 abstract description 2
- 239000012071 phase Substances 0.000 abstract description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 2
- 235000011114 ammonium hydroxide Nutrition 0.000 abstract 2
- 238000001035 drying Methods 0.000 abstract 2
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 abstract 1
- 239000002699 waste material Substances 0.000 abstract 1
- 229910001928 zirconium oxide Inorganic materials 0.000 abstract 1
- 238000002156 mixing Methods 0.000 description 30
- 239000002253 acid Substances 0.000 description 24
- 235000011167 hydrochloric acid Nutrition 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 12
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 10
- 241000588731 Hafnia Species 0.000 description 7
- 238000007599 discharging Methods 0.000 description 6
- 230000001172 regenerating effect Effects 0.000 description 6
- 235000011182 sodium carbonates Nutrition 0.000 description 5
- 239000000126 substance Substances 0.000 description 3
- 230000003044 adaptive effect Effects 0.000 description 1
- -1 alkyl tertiary amine Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000031068 symbiosis, encompassing mutualism through parasitism Effects 0.000 description 1
Classifications
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- 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
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a preparation method of high-purity low-zirconium hafnium oxide, belonging to the technical field of wet metallurgy. The preparation method comprises the steps of dissolving waste metal hafnium serving as a raw material in a sulfuric acid solution, filtering, and adjusting H in the hafnium sulfate solution+The concentration is 2.4 mol/L-2.8 mol/L, HfO2The concentration is 50 g/L-80 g/L; the volume composition of the extractant is as follows: n is a radical of235：12％～20％，A1416: 7%, sulfonated kerosene: 81% -73%; taking the extracting agent as an organic phase and the hafnium sulfate liquid as a water phase, and performing multi-stage countercurrent extraction to obtain a low-zirconium hafnium sulfate raffinate; then ammonia water precipitation, rinsing, drying, hydrochloric acid leaching, crystallization and purification, ammonia water precipitation, rinsing, drying and calcination are sequentially carried out to obtain the product. The method can prepare high-purity hafnium oxide with the zirconium oxide content of less than 0.5 wt%, has low impurity content, belongs to ultraviolet-grade hafnium oxide, and can be used for high-end optical coating materials.
Description
Technical field
The present invention relates to a kind of preparation method of high-purity low-zirconium hafnium oxide, belong to technical field of wet metallurgy.
Background technology
Zirconium is two kinds of extremely similar elements of chemical property with hafnium.Zirconium and hafnium all are the HMP rare metals, in the periodic table of elements, belong to IVB family, owing to they similar outer electronic structure (Zr:4D
25S
2, Hf:5D
26S
2), the especially influence of lanthanide contraction, their atomic radius, ionic radius, crystalline texture are all very approaching, therefore on chemical property, show closely similarly.At occurring in nature, zirconium with hafnium symbiosis always be in the same place, do not have independent zirconium ore or hafnium ore deposit, general zirconium ore contains hafnium 2-6%, so the zirconium hafnium must separate.But the chemical conduct that zirconium is extremely similar with hafnium makes ten minutes detached from each other difficult.
Though the separate study work of China's zirconium and hafnium starts from the sixties in last century, mainly be supporting with the nuclear power application, the hafnium content requirement is less than 0.01% in the atomic level zirconium, and the atomic level hafnium requires zirconium content will be lower than 3%.Whole zirconium hafnium separate study work, last century, late nineteen seventies was in halted state basically.In the general zirconium hafnium separation of produced line, in the hafnia zirconic content equal to be less than 3% product qualified.Therefore for the development of adaptive technique, the preparation method of the high-purity low-zirconium hafnium oxide that zirconic content is littler in a kind of hafnia is provided, becomes the problem that those skilled in the art's urgent need will solve.
Summary of the invention
The purpose of this invention is to provide in a kind of hafnia zirconic content less than the preparation method of the high-purity low-zirconium hafnium oxide of 0.5wt%.
For realizing above-mentioned purpose, the present invention takes following technical scheme:
A kind of preparation method of high-purity low-zirconium hafnium oxide, step is following:
(1) preparation hafnium sulfate feed liquid: with the scrap metal hafnium is raw material, through the sulphuric acid soln dissolving, filters, and adjusts H in the hafnium sulfate feed liquid again
+Concentration is 2.4mol/L～2.8mol/L, HfO
2Concentration is 50g/L～80g/L;
(2) extraction agent is by N
235(three (suffering-last of the ten Heavenly stems) alkyl tertiary amine) composite A
1416(isomery β-branched-chain primary alcohol) and sulfonated kerosene form, and the volumn concentration of each component is following: N
235: 12%～20%, A
1416: 7%, sulfonated kerosene: 81%～73%;
(3) extraction agent is as organic phase, and the hafnium sulfate feed liquid is carried out multi-stage counter current extraction as water, and the zirconium hafnium in the extracting and separating hafnium sulfate feed liquid obtains low zirconium hafnium sulfate and extracts surplus liquid;
(4) the zirconium hafnium sulfate extracts surplus liquid successively through ammonia precipitation process, rinsing, oven dry, hydrochloric acid leaching, crystallization and purification, ammonia precipitation process, rinsing, oven dry, calcining, obtains the high-purity low-zirconium hafnium oxide product.
A kind of optimized technical scheme is characterized in that: said organic phase and water volume ratio are 1: 1, and promptly the volume ratio of extraction agent and hafnium sulfate feed liquid is 1: 1, and organic phase churning time mixed with water is 30 minutes.
A kind of optimized technical scheme; It is characterized in that: said extraction agent is through the four-stage counter-current extraction; After the zirconium in the extraction hafnium sulfate feed liquid, adopting hydrochloric acid soln to carry out two-stage back extraction zirconium, is that regenerated liquid makes extraction agent (organic phase) regeneration then with the aqueous sodium carbonate; After the acidifying of extraction agent after the regeneration (organic phase) process two-stage sulphuric acid soln, carry out next cycling extraction operation.
A kind of optimized technical scheme is characterized in that: the volume ratio of said extraction agent and hydrochloric acid soln is 1: 1, and the volume ratio of said extraction agent and aqueous sodium carbonate is 1: 1, and the volume ratio of said extraction agent and sulphuric acid soln is 1: 1.Promptly in above-mentioned extraction process, organic phase and water volume ratio are 1: 1; Organic phase churning time mixed with water is 30 minutes.
A kind of optimized technical scheme is characterized in that: the volumn concentration of said each component of extraction agent is following: N
235: 20%, A
1416: 7%, sulfonated kerosene: 73%.
H in the said sulphuric acid soln (acidifying acid)
+Concentration is 2.5mol/L.
H in the said hydrochloric acid soln (strip liquor)
+Concentration is 2mol/L.
The concentration mass percent of said aqueous sodium carbonate (organic phase regenerated liquid) is 5%.
Said N
235, A
1416, sulfonated kerosene is commercially available technical grade product.
Extraction agent, hafnium sulfate feed liquid, sulphuric acid soln, hydrochloric acid soln, five kinds of solution of aqueous sodium carbonate are respectively charged into each solution header tank, control feed rate, reinforced inlet formula mixed settler extractor; Carry out the continuous countercurrent extraction reaction; The acidifying section is a two-stage, and acidifying acid is got into by second stage mixing section, and flow out first step clarifying chamber; After the adjustment acidity is qualified acidifying acid solution, reuses; Organic phase is got into by first step mixing section, after the two-stage acidifying, is flowed out by clarifying chamber, the second stage; Flow into third stage extraction section, after the level Four extraction, flow out extraction section; Get into the 7th grade of anti-zirconium section, behind the anti-zirconium of two-stage, flow out anti-zirconium section; Flow into the 9th grade of organic phase RS Regenerator Section, after the regeneration of one-level organic phase, flow into storage tank.Feed liquid is got into by the 6th grade of mixing section; Carry out flowing out by third stage clarifying chamber behind the four-stage counter-current extractive reaction with organic phase; The low zirconium hafnium sulfate of inflow extracts surplus liquid and connects liquid bath; Low zirconium hafnium sulfate extracts surplus liquid successively through ammonia precipitation process, rinsing, oven dry, hydrochloric acid leaching, crystallization and purification, ammonia precipitation process, rinsing, oven dry, calcining, obtains the high-purity low-zirconium hafnium oxide product.Strip liquor is got into by the 8th grade of mixing section, and flow out into anti-raffinate and connect liquid bath the 7th grade of clarifying chamber, and anti-raffinate reclaims zirconium hafnium wherein after with ammonia precipitation process; The organic phase regenerated liquid is added by the 9th grade of mixing section, and flow out the 9th grade of clarifying chamber, and the surplus liquid of regenerating is with discharging with the back in the spent acid.
Beneficial effect of the present invention is: the inventive method can prepare in the hafnia zirconic content less than the high-purity hafnium oxide of 0.5wt%.Gained high-purity hafnium oxide foreign matter content is lower, belongs to ultraviolet level hafnia, can be used for high-end optical filming material.
Through embodiment the present invention is further specified below, but and do not mean that restriction protection domain of the present invention.
Embodiment
Embodiment 1
(1) the qualified hafnium sulfate feed liquid of preparation: with the scrap metal hafnium is raw material, through the sulphuric acid soln dissolving, filters, and adjusts H in the hafnium sulfate feed liquid again
+Concentration is 2.5mol/L, HfO
2Concentration is 54g/L, 12 liters;
(2) the qualified organic extractant phase agent (volumn concentration) of preparation: 20%N
235+ 7%A
1416+ 73% sulfonated kerosene, 12 liters;
(3) the qualified acidifying acid solution of preparation: 2.5mol/L aqueous sulfuric acid, 12 liters;
(4) the qualified anti-zirconium solution of preparation: 2.0mol/L aqueous hydrochloric acid, 12 liters;
(5) the qualified organic phase regeneration soln of preparation: 5 quality % aqueous sodium carbonates, 12 liters;
Above five kinds of solution are respectively charged into each solution header tank, move 100 minutes, feed rate is 120 ml/min; Reinforced inlet formula mixed settler extractor carries out the continuous countercurrent extraction reaction, and the acidifying section is a two-stage; Acidifying acid is got into by second stage mixing section; Flow out first step clarifying chamber, is qualified acidifying acid solution after the adjustment acidity, reuses; Organic phase is got into by first step mixing section, after the two-stage acidifying, is flowed out by clarifying chamber, the second stage; Flow into third stage extraction section, after the level Four extraction, flow out extraction section; Get into the 7th grade of anti-zirconium section, behind the anti-zirconium of two-stage, flow out anti-zirconium section; Flow into the 9th grade of organic phase RS Regenerator Section, after the regeneration of one-level organic phase, flow into storage tank.Feed liquid is got into by the 6th grade of mixing section; Carry out flowing out by third stage clarifying chamber behind the four-stage counter-current extractive reaction with organic phase; The low zirconium hafnium sulfate of inflow extracts surplus liquid and connects liquid bath; Low zirconium hafnium sulfate extracts surplus liquid successively through ammonia precipitation process, rinsing, oven dry, hydrochloric acid leaching, crystallization and purification, ammonia precipitation process, rinsing, oven dry, calcining, obtains the high-purity low-zirconium hafnium oxide product.Strip liquor is got into by the 8th grade of mixing section, and flow out into anti-raffinate and connect liquid bath the 7th grade of clarifying chamber, and anti-raffinate reclaims zirconium hafnium wherein after with ammonia precipitation process; The organic phase regenerated liquid is added by the 9th grade of mixing section, and flow out the 9th grade of clarifying chamber, and the surplus liquid of regenerating is with discharging with the back in the spent acid.In the extraction process, organic phase and water volume ratio are 1: 1, promptly the volume of volume ratio, extraction agent and the aqueous sodium carbonate of volume ratio, extraction agent and the hydrochloric acid soln of extraction agent and hafnium sulfate feed liquid when the volume ratio of extraction agent and sulphuric acid soln be 1: 1; Organic phase churning time mixed with water is 30 minutes.
Analytical results shows that the zirconia content in the prepared high-purity low-zirconium hafnium oxide product is 0.019wt%.
Embodiment 2
(1) the qualified hafnium sulfate feed liquid of preparation: with the scrap metal hafnium is raw material, through the sulphuric acid soln dissolving, filters, and adjusts H in the hafnium sulfate feed liquid again
+Concentration is 2.46mol/L, HfO
2Concentration is 51.8g/L, 12 liters;
(2) the qualified organic phase (volumn concentration) of preparation: 20%N
235+ 7%A
1416+ 73% sulfonated kerosene, 12 liters;
(3) the qualified acidifying acid solution of preparation: 2.5mol/L aqueous sulfuric acid, 12 liters;
(4) the qualified anti-zirconium solution of preparation: 2.0mol/L aqueous hydrochloric acid, 12 liters;
(5) the qualified organic phase regeneration soln of preparation: 5 quality % aqueous sodium carbonates, 12 liters;
Above five kinds of solution are respectively charged into each solution header tank, move 95 minutes, the control feed rate is 125 ml/min; Reinforced inlet formula mixed settler extractor carries out the continuous countercurrent extraction reaction, and the acidifying section is a two-stage; Acidifying acid is got into by second stage mixing section; Flow out first step clarifying chamber, is qualified acidifying acid solution after the adjustment acidity, reuses; Organic phase is got into by first step mixing section, after the two-stage acidifying, is flowed out by clarifying chamber, the second stage; Flow into third stage extraction section, after the level Four extraction, flow out extraction section; Get into the 7th grade of anti-zirconium section, behind the anti-zirconium of two-stage, flow out anti-zirconium section; Flow into the 9th grade of organic phase RS Regenerator Section, after the regeneration of one-level organic phase, flow into storage tank.Feed liquid is got into by the 6th grade of mixing section; Carry out flowing out by third stage clarifying chamber behind the four-stage counter-current extractive reaction with organic phase; The low zirconium hafnium sulfate of inflow extracts surplus liquid and connects liquid bath; Low zirconium hafnium sulfate extracts surplus liquid successively through ammonia precipitation process, rinsing, oven dry, hydrochloric acid leaching, crystallization and purification, ammonia precipitation process, rinsing, oven dry, calcining, obtains the high-purity low-zirconium hafnium oxide product.Strip liquor is got into by the 8th grade of mixing section, and flow out into anti-raffinate and connect liquid bath the 7th grade of clarifying chamber, and anti-raffinate reclaims zirconium hafnium wherein after with ammonia precipitation process; The organic phase regenerated liquid is added by the 9th grade of mixing section, and flow out the 9th grade of clarifying chamber, and the surplus liquid of regenerating is with discharging with the back in the spent acid.In the extraction process, organic phase and water volume ratio are 1: 1; Organic phase churning time mixed with water is 30 minutes.
Analytical results shows that the zirconia content in the prepared high-purity low-zirconium hafnium oxide product is 0.018wt%.
Embodiment 3
(1) the qualified hafnium sulfate feed liquid of preparation: with the scrap metal hafnium is raw material, through the sulphuric acid soln dissolving, filters, and adjusts H in the hafnium sulfate feed liquid again
+Concentration is 2.46mol/L, HfO
2Concentration is 52.2g/L, 12 liters;
(2) the qualified organic phase (volumn concentration) of preparation: 20%N
235+ 7%A
1416+ 73% sulfonated kerosene, 12 liters;
(3) the qualified acidifying acid solution of preparation: 2.5mol/L aqueous sulfuric acid, 12 liters;
(4) the qualified anti-zirconium solution of preparation: 2.0mol/L aqueous hydrochloric acid, 12 liters;
(5) the qualified organic phase regeneration soln of preparation: 5 quality % aqueous sodium carbonates, 12 liters;
Above five kinds of solution are respectively charged into each solution header tank, move 96 minutes, feed rate is 135 ml/min; Reinforced inlet formula mixed settler extractor carries out the continuous countercurrent extraction reaction, and the acidifying section is a two-stage; Acidifying acid is got into by second stage mixing section; Flow out first step clarifying chamber, is qualified acidifying acid solution after the adjustment acidity, reuses; Organic phase is got into by first step mixing section, after the two-stage acidifying, is flowed out by clarifying chamber, the second stage; Flow into third stage extraction section, after the level Four extraction, flow out extraction section; Get into the 7th grade of anti-zirconium section, behind the anti-zirconium of two-stage, flow out anti-zirconium section; Flow into the 9th grade of organic phase RS Regenerator Section, after the regeneration of one-level organic phase, flow into storage tank.Feed liquid is got into by the 6th grade of mixing section; Carry out flowing out by third stage clarifying chamber behind the four-stage counter-current extractive reaction with organic phase; The low zirconium hafnium sulfate of inflow extracts surplus liquid and connects liquid bath; Low zirconium hafnium sulfate extracts surplus liquid successively through ammonia precipitation process, rinsing, oven dry, hydrochloric acid leaching, crystallization and purification, ammonia precipitation process, rinsing, oven dry, calcining, obtains the high-purity low-zirconium hafnium oxide product.Strip liquor is got into by the 8th grade of mixing section, and flow out into anti-raffinate and connect liquid bath the 7th grade of clarifying chamber, and anti-raffinate reclaims zirconium hafnium wherein after with ammonia precipitation process; The organic phase regenerated liquid is added by the 9th grade of mixing section, and flow out the 9th grade of clarifying chamber, and the surplus liquid of regenerating is with discharging with the back in the spent acid.In the extraction process, organic phase and water volume ratio are 1: 1; Organic phase churning time mixed with water is 30 minutes.
Analytical results shows that the zirconia content in the prepared high-purity low-zirconium hafnium oxide product is 0.020wt%.
Embodiment 4
(1) the qualified hafnium sulfate feed liquid of preparation: with the scrap metal hafnium is raw material, through the sulphuric acid soln dissolving, filters, and adjusts H in the hafnium sulfate feed liquid again
+Concentration is 2.6mol/L, HfO
2Concentration is 68g/L, 12 liters;
(2) the qualified organic phase (volumn concentration) of preparation: 15%N
235+ 7%A
1416+ 78% sulfonated kerosene, 12 liters;
(3) the qualified acidifying acid solution of preparation: 2.5mol/L aqueous sulfuric acid, 12 liters;
(4) the qualified anti-zirconium solution of preparation: 12 liters of 2.0mol/L aqueous hydrochloric acids;
(5) the qualified organic phase regeneration soln of preparation: 5 quality % aqueous sodium carbonates, 12 liters;
Above five kinds of solution are respectively charged into each solution header tank, move 96 minutes, feed rate is 135 ml/min; Reinforced inlet formula mixed settler extractor carries out the continuous countercurrent extraction reaction, and the acidifying section is a two-stage; Acidifying acid is got into by second stage mixing section; Flow out first step clarifying chamber, is qualified acidifying acid solution after the adjustment acidity, reuses; Organic phase is got into by first step mixing section, after the two-stage acidifying, is flowed out by clarifying chamber, the second stage; Flow into third stage extraction section, after the level Four extraction, flow out extraction section; Get into the 7th grade of anti-zirconium section, behind the anti-zirconium of two-stage, flow out anti-zirconium section; Flow into the 9th grade of organic phase RS Regenerator Section, after the regeneration of one-level organic phase, flow into storage tank.Feed liquid is got into by the 6th grade of mixing section; Carry out flowing out by third stage clarifying chamber behind the four-stage counter-current extractive reaction with organic phase; The low zirconium hafnium sulfate of inflow extracts surplus liquid and connects liquid bath; Low zirconium hafnium sulfate extracts surplus liquid successively through ammonia precipitation process, rinsing, oven dry, hydrochloric acid leaching, crystallization and purification, ammonia precipitation process, rinsing, oven dry, calcining, obtains the high-purity low-zirconium hafnium oxide product.Strip liquor is got into by the 8th grade of mixing section, and flow out into anti-raffinate and connect liquid bath the 7th grade of clarifying chamber, and anti-raffinate reclaims zirconium hafnium wherein after with ammonia precipitation process; The organic phase regenerated liquid is added by the 9th grade of mixing section, and flow out the 9th grade of clarifying chamber, and the surplus liquid of regenerating is with discharging with the back in the spent acid.In the extraction process, organic phase and water volume ratio are 1: 1; Organic phase churning time mixed with water is 30 minutes.
Analytical results shows that the zirconia content in the prepared high-purity low-zirconium hafnium oxide product is 0.023wt%.
Embodiment 5
(1) the qualified hafnium sulfate feed liquid of preparation: with the scrap metal hafnium is raw material, through the sulphuric acid soln dissolving, filters, and adjusts H in the hafnium sulfate feed liquid again
+Concentration is 2.4mol/L, HfO
2Concentration is 75g/L, 12 liters;
(2) the qualified organic phase (volumn concentration) of preparation: 12%N
235+ 7%A
1416+ 81% sulfonated kerosene, 12 liters;
(3) the qualified acidifying acid solution of preparation: 2.5mol/L aqueous sulfuric acid, 12 liters;
(4) the qualified anti-zirconium solution of preparation: 2.0mol/L aqueous hydrochloric acid, 12 liters;
(5) the qualified organic phase regeneration soln of preparation: 5 quality % aqueous sodium carbonates, 12 liters;
Above five kinds of solution are respectively charged into each solution header tank, move 96 minutes, feed rate is 135 ml/min; Reinforced inlet formula mixed settler extractor carries out the continuous countercurrent extraction reaction, and the acidifying section is a two-stage; Acidifying acid is got into by second stage mixing section; Flow out first step clarifying chamber, is qualified acidifying acid solution after the adjustment acidity, reuses; Organic phase is got into by first step mixing section, after the two-stage acidifying, is flowed out by clarifying chamber, the second stage; Flow into third stage extraction section, after the level Four extraction, flow out extraction section; Get into the 7th grade of anti-zirconium section, behind the anti-zirconium of two-stage, flow out anti-zirconium section; Flow into the 9th grade of organic phase RS Regenerator Section, after the regeneration of one-level organic phase, flow into storage tank.Feed liquid is got into by the 6th grade of mixing section; Carry out flowing out by third stage clarifying chamber behind the four-stage counter-current extractive reaction with organic phase; The low zirconium hafnium sulfate of inflow extracts surplus liquid and connects liquid bath; Low zirconium hafnium sulfate extracts surplus liquid successively through ammonia precipitation process, rinsing, oven dry, hydrochloric acid leaching, crystallization and purification, ammonia precipitation process, rinsing, oven dry, calcining, obtains the high-purity low-zirconium hafnium oxide product.Strip liquor is got into by the 8th grade of mixing section, and flow out into anti-raffinate and connect liquid bath the 7th grade of clarifying chamber, and anti-raffinate reclaims zirconium hafnium wherein after with ammonia precipitation process; The organic phase regenerated liquid is added by the 9th grade of mixing section, and flow out the 9th grade of clarifying chamber, and the surplus liquid of regenerating is with discharging with the back in the spent acid.In the extraction process, organic phase and water volume ratio are 1: 1; Organic phase churning time mixed with water is 30 minutes.
Analytical results shows that the zirconia content in the prepared high-purity low-zirconium hafnium oxide product is 0.032wt%.
Table 1 obtains the impurity analysis result of high-purity low-zirconium hafnium oxide product for low zirconium hafnium sulfate extracts surplus liquid successively through ammonia precipitation process, rinsing, oven dry, hydrochloric acid leaching, crystallization and purification, ammonia precipitation process, rinsing, oven dry, calcining.
Table 1 high-purity low-zirconium hafnium oxide product analysis result
| Foreign matter content % | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Si％ | 0.0060 | 0.0065 | 0.0080 | 0.0090 | 0.015 |
| Fe％ | 0.0011 | 0.00050 | 0.00032 | 0.00028 | 0.00030 |
| Mn％ | ＜0.0001 | ＜0.0003 | ＜0.0003 | ＜0.0003 | ＜0.0003 |
| Cu％ | 0.00027 | 0.00040 | 0.00030 | 0.00045 | 0.00015 |
| Mg％ | 0.00025 | 0.00040 | 0.00040 | 0.0013 | 0.00060 |
| Ni％ | 0.00014 | 0.00030 | 0.00030 | 0.00030 | 0.00030 |
| Al％ | 0.00050 | ||||
| Co％ | ＜0.0003 | ＜0.0003 | ＜0.0003 | ＜0.0003 | ＜0.0003 |
| Pb％ | 0.00020 | ＜0.0001 | 0.00018 | 0.00010 | |
| Sn％ | ＜0.0003 | ＜0.0003 | ＜0.0003 | ＜0.0003 | ＜0.0003 |
| Bi％ | ＜0.0003 | ＜0.0003 | ＜0.0003 | ＜0.0003 | ＜0.0003 |
| Cd％ | ＜0.0003 | ＜0.0003 | ＜0.0003 | ＜0.0003 | ＜0.0003 |
| V％ | ＜0.001 | ＜0.001 | ＜0.001 | ＜0.001 | ＜0.001 |
| Ti％ | 0.0009 | ＜0.001 | ＜0.001 | ＜0.001 | ＜0.001 |
| Mo％ | ＜0.001 | ＜0.001 | ＜0.001 | ＜0.001 | ＜0.001 |
| Ca％ | 0.0014 | 0.0034 | 0.0032 | 0.0080 | 0.0055 |
| Sb％ | ＜0.0003 | ＜0.0003 | ＜0.0003 | ＜0.0003 | ＜0.0003 |
| Cr％ | ＜0.001 | ||||
| Zr％ | 0.019 | 0.018 | 0.020 | 0.023 | 0.032 |
The inventive method prepares that zirconic content is less than 0.5wt% in the hafnia of gained, and gained high-purity hafnium oxide foreign matter content is lower, belongs to ultraviolet level hafnia, can be used for high-end optical filming material.
Claims (9)
1. the preparation method of a high-purity low-zirconium hafnium oxide, step is following:
(1) preparation hafnium sulfate feed liquid: with the scrap metal hafnium is raw material, through the sulphuric acid soln dissolving, filters, and adjusts H in the hafnium sulfate feed liquid again
+Concentration is 2.4mol/L～2.8mol/L, HfO
2Concentration is 50g/L～80g/L;
(2) extraction agent is by N
235Composite A
1416Form with sulfonated kerosene, the volumn concentration of each component is following: N
235: 12%～20%, A
1416: 7%, sulfonated kerosene: 81%～73%;
(3) extraction agent is as organic phase, and the hafnium sulfate feed liquid is carried out multi-stage counter current extraction as water, and the zirconium hafnium in the extracting and separating hafnium sulfate feed liquid obtains low zirconium hafnium sulfate and extracts surplus liquid;
(4) the zirconium hafnium sulfate extracts surplus liquid successively through ammonia precipitation process, rinsing, oven dry, hydrochloric acid leaching, crystallization and purification, ammonia precipitation process, rinsing, oven dry, calcining, obtains the high-purity low-zirconium hafnium oxide product.
2. the preparation method of high-purity low-zirconium hafnium oxide according to claim 1, it is characterized in that: said organic phase and water volume ratio are 1: 1, organic phase churning time mixed with water is 30 minutes.
3. the preparation method of high-purity low-zirconium hafnium oxide according to claim 1; It is characterized in that: said extraction agent is through after the four-stage counter-current extraction; Adopt hydrochloric acid soln to carry out two-stage back extraction zirconium; Be that regenerated liquid makes extractant regeneration then with the aqueous sodium carbonate, after the extraction agent process two-stage sulphuric acid soln acidifying after the regeneration, carry out next cycling extraction operation.
4. the preparation method of high-purity low-zirconium hafnium oxide according to claim 3; It is characterized in that: the volume ratio of said extraction agent and hydrochloric acid soln is 1: 1; The volume ratio of said extraction agent and aqueous sodium carbonate is 1: 1; The volume ratio of said extraction agent and sulphuric acid soln is 1: 1, mixes churning time and is 30 minutes.
5. the preparation method of high-purity low-zirconium hafnium oxide according to claim 1, it is characterized in that: the volumn concentration of said each component of extraction agent is following: N
235: 20%, A
1416: 7%, sulfonated kerosene: 73%.
6. the preparation method of high-purity low-zirconium hafnium oxide according to claim 3 is characterized in that: H in the said sulphuric acid soln
+Concentration is 2.5mol/L.
7. the preparation method of high-purity low-zirconium hafnium oxide according to claim 3 is characterized in that: H in the said hydrochloric acid soln
+Concentration is 2mol/L.
8. the preparation method of high-purity low-zirconium hafnium oxide according to claim 3, it is characterized in that: the concentration of said aqueous sodium carbonate is 5 quality %.
9. the preparation method of high-purity low-zirconium hafnium oxide according to claim 1, it is characterized in that: zirconic content is less than 0.5wt% in the prepared high-purity low-zirconium hafnium oxide product.
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| CN103833077A (en) * | 2014-03-17 | 2014-06-04 | 山东理工大学 | Method of preparing hafnium oxide hollow powder by water quenching method |
| CN107686898A (en) * | 2017-09-11 | 2018-02-13 | 西北有色金属研究院 | A kind of method that hafnium oxide is prepared from recovery in waste material containing hafnium |
| CN113234923A (en) * | 2021-03-23 | 2021-08-10 | 广东先导稀材股份有限公司 | Method for preparing high-purity hafnium oxide by extracting and separating zirconium and hafnium with solvent |
| CN113563069A (en) * | 2021-07-26 | 2021-10-29 | 巨玻固能(苏州)薄膜材料有限公司 | HfO for high-purity deep ultraviolet coating2Material and sintering purification process thereof |
| CN115094250A (en) * | 2022-06-30 | 2022-09-23 | 深圳中铪科技有限公司 | Method for recovering hafnium and other metals from hafnium-containing waste residues |
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| CN103833077A (en) * | 2014-03-17 | 2014-06-04 | 山东理工大学 | Method of preparing hafnium oxide hollow powder by water quenching method |
| CN107686898A (en) * | 2017-09-11 | 2018-02-13 | 西北有色金属研究院 | A kind of method that hafnium oxide is prepared from recovery in waste material containing hafnium |
| CN113234923A (en) * | 2021-03-23 | 2021-08-10 | 广东先导稀材股份有限公司 | Method for preparing high-purity hafnium oxide by extracting and separating zirconium and hafnium with solvent |
| CN113563069A (en) * | 2021-07-26 | 2021-10-29 | 巨玻固能(苏州)薄膜材料有限公司 | HfO for high-purity deep ultraviolet coating2Material and sintering purification process thereof |
| CN113563069B (en) * | 2021-07-26 | 2022-06-17 | 巨玻固能(苏州)薄膜材料有限公司 | HfO for high-purity deep ultraviolet coating2Material and sintering purification process thereof |
| CN115094250A (en) * | 2022-06-30 | 2022-09-23 | 深圳中铪科技有限公司 | Method for recovering hafnium and other metals from hafnium-containing waste residues |
| WO2024000614A1 (en) * | 2022-06-30 | 2024-01-04 | 深圳中铪科技有限公司 | Method for recovering hafnium and other metals from hafnium-containing waste residues |
| CN115637337A (en) * | 2022-11-01 | 2023-01-24 | 广东先导稀材股份有限公司 | Method for purifying and deironing high-purity hafnium tetrachloride |
| CN115637337B (en) * | 2022-11-01 | 2024-05-24 | 广东先导稀材股份有限公司 | Method for purifying and deironing high-purity hafnium tetrachloride |
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Application publication date: 20120418 |