CN104195355A - Zirconium and method for preparing zirconium - Google Patents
Zirconium and method for preparing zirconium Download PDFInfo
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- CN104195355A CN104195355A CN201410397353.XA CN201410397353A CN104195355A CN 104195355 A CN104195355 A CN 104195355A CN 201410397353 A CN201410397353 A CN 201410397353A CN 104195355 A CN104195355 A CN 104195355A
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Abstract
The invention provides zirconium and a method for preparing the zirconium. The method comprises the following steps: metallothermic reduction, namely promoting zirconium oxide and alkaline-earth metal or alkaline-earth metal hydride to perform a metallothermic reduction reaction, and removing impurities to obtain primary zirconium; molten salt refining, namely promoting the primary zirconium and mixed molten salt to perform a molten salt refining reaction so as to obtain secondary zirconium; vacuum distillation, namely performing vacuum distillation on the secondary zirconium so as to obtain tertiary zirconium; and combined melting, namely sequentially performing smelting in suspension and electron beam zone melting on the tertiary zirconium so as to obtain the product zirconium, wherein the mixed molten salt consists of CaCl2 and Ca. According to the method, the zirconium oxide is used as a raw material, metallothermic reduction, molten salt refining, vacuum distillation and combined melting methods are sequentially adopted, the primary zirconium obtained after the metallothermic reduction is subjected to molten salt refining, the oxygen content of the intermediate product zirconium can be effectively reduced, and the mixed molten salt used in the method can be easily removed by means of water washing, and the purity of zirconium cannot be influenced.
Description
Technical field
The present invention relates to preparation of metals field, especially, relate to a kind of method and gained zirconium of preparing zirconium.
Background technology
The thermal-neutron capture cross-section small intensity of Zr is high thereby be widely used in nuclear reactor material, and the good physics-chem characteristic of Zr makes it also be used to reactor in chemical industry in addition, the parts such as valve, the additive of killed steel, non-ferrous alloy etc.Along with the particularly fast development of nuclear industry in recent years of scientific and technological progress, more and more higher to the purity requirement of Zr.The method that at present preparation purity is greater than 99.9% zirconium mainly contains Kroll process, fused salt electrolysis process, halogenide thermal dissociation method, metallothermic reduction ZrO
2method.
Kroll process: Ke Laoer has invented the method for magnesium reduction titanium tetrachloride since the forties in 20th century, and use it for reduction zirconium tetrachloride and prepare vesicular metal zirconium, Kroll process zirconium processed is still the main method of industrial extensive preparation metal zirconium at present so far.The method adopts magnesiothermic reduction distillation to produce zirconium sponge after zirconium tetrachloride is purified.The CEZUS company of France obtains atomic level zirconium sponge impurity mean value all lower than U.S.'s product standard prescribed value by the method melting, and the product obtaining approaches 3N.Yet for the high-purity core level metal zirconium of preparation, this technical process is long, needs special equipment, and all kinds of control devices are invested higher; Because muriate is more active, in the process of preparation metal zirconium, be easy to introduce impurity, be the preparation increase difficulty of high purity zirconium; The quality of product changes along with the difference of production batch, and this can badly influence the selection of subsequent purification technique, finally affects the quality of product.
Fused salt electrolysis process: fused salt electrolysis process is by preparation alkali metal chloride (NaCl, KCl, LiCl) and K2ZrF6 fused salt, applies voltage, zirconium ion obtains electronics and the principle separated out at negative electrode.The negative electrode zirconium that electrolysis obtains is Powdered or dendritic crystal state.The method equipment requirements is low, processing ease, and cost is lower, and weak point is that production efficiency is low, and the factors such as molten salt system and zirconium concentration are larger to electrolytic production quality influence, need further research aspect high purity zirconium preparing.
FCC method: preparation metal zirconium is that employing solid zirconium dioxide is negative electrode, utilizes oxonium ion to enter fused salt and migrates to anodic reaction, leaves the principle of pure metal zirconium at negative electrode, the zirconium white of take generates metal zirconium as raw material carrys out one-step electrolysis.This technique has shortened technical process, does not also have chlorine to emit in reaction process, but owing to existing ion to spread in solid phase in reaction process, thus electrolytic reaction speed and current efficiency lower, and due to the existence of solid solution oxygen, oxygen can not remove completely.Although there is bibliographical information can obtain oxygen level lower than the zirconium sponge of 400ppm abroad, yet because impurity is easily introduced in fused salt electrolysis, and the bad control of condition, this research method is under test in the majority.
Metallothermic reduction ZrO
2method: because its thermodynamics of reactions is lower than metallothermic reduction halogenide, and the slag in product is difficult to separated with metal zirconium thereby studies less.
Summary of the invention
The object of the invention is to provide method and gained zirconium and the prepared zirconium thereof of preparing zirconium, to solve prior art moderate purity, higher than 99.9% zirconium, is difficult to simple and effective, is suitable for the technical problem of suitability for industrialized production.
For achieving the above object, according to an aspect of the present invention, provide the method for preparing zirconium, comprised the following steps: metallothermic reduction: zirconium white has reacted with alkaline-earth metal and/or alkaline earth metal hydride generation metallothermic reduction, obtains elementary zirconium after removing impurities; Fused salt refining: elementary zirconium and fused salt mixt send fused salt purifying reaction, obtain secondary zirconium; Vacuum distilling: secondary zirconium is carried out to vacuum distilling, obtain three grades of zirconiums; Combination Smelting: three grades of zirconiums are sequentially carried out to suspended smelting and electron beam zone melting, obtain product zirconium; Fused salt mixt is comprised of the fused salt of CaCl2 and Ca.
Further, before metallothermic reduction reaction, add basic metal villaumite or alkaline-earth metal villaumite.
Further, basic metal villaumite is KCl and/or NaCl, is preferably NaCl; Alkaline-earth metal villaumite is MgCl2 and/or CaCl2, is preferably CaCl.
Further, the addition of basic metal villaumite or alkaline-earth metal villaumite be in metallothermic reduction reaction in mole 0.02～2 times of theoretical oxide growing amount.
Further, hafnium content < 100ppm in zirconium white, zirconic particle diameter < 10 orders.
Further, metallothermic reduction reaction conditions is: 800～1050 ℃, react 1～4 hour in inert atmosphere.
Further, the method according to claim 6, is characterized in that, fused salt purifying reaction temperature is 900～1050 ℃, and the reaction times is 2～10 hours; Preferably fused salt mixt is 50～40: 1 CaCl by weight ratio
2form with Ca.
Further, the condition of vacuum distilling is: vacuum tightness 10
-4～10
-6pa, temperature is 650～950 ℃, is incubated 3～8 hours.
A kind of product zirconium is also provided according to a further aspect in the invention, and product zirconium is prepared from by the method for any one in claim 1 to 9, purity >=99.9% of product zirconium.
The present invention has following beneficial effect:
Method provided by the invention be take zirconium white and is sequentially adopted metallothermic reduction, fused salt refining, vacuum distilling and Combination Smelting method as raw material, the elementary zirconium obtaining after metallothermic reduction reaction is carried out to fused salt refining, can effectively reduce the oxygen level of gained intermediate product zirconium, and fused salt mixt used is not easily removed and can be impacted the purity of zirconium by washing.
Except object described above, feature and advantage, the present invention also has other object, feature and advantage.Below with reference to figure, the present invention is further detailed explanation.
Accompanying drawing explanation
The accompanying drawing that forms the application's a part is used to provide a further understanding of the present invention, and schematic description and description of the present invention is used for explaining the present invention, does not form inappropriate limitation of the present invention.In the accompanying drawings:
Fig. 1 is the process flow diagram of the preferred embodiment of the present invention.
Embodiment
Below in conjunction with accompanying drawing, embodiments of the invention are elaborated, but the multitude of different ways that the present invention can be defined by the claims and cover is implemented.
Referring to Fig. 1, prepare method and the gained zirconium of zirconium, comprise the following steps: metallothermic reduction: zirconium white reacts with alkaline-earth metal and/or alkaline earth metal hydride generation metallothermic reduction, obtains elementary zirconium after removing impurities; Fused salt refining: elementary zirconium and fused salt mixt send fused salt purifying reaction, obtain secondary zirconium; Vacuum distilling: secondary zirconium is carried out to vacuum distilling, obtain three grades of zirconiums; Combination Smelting: three grades of zirconiums are sequentially carried out to suspended smelting and electron beam zone melting, obtain product zirconium; Fused salt mixt is by CaCl
2form with the fused salt of Ca.
The equation that reacts: 2Me+ZrO in metallothermic reduction reaction
2=2MeO+Zr.The Me wherein adding is the metal with reductibility.The metal of reductibility can be better than zirconium metal for the bonding force of same oxygen is as Ca, Mg, CaH
2deng.In this reaction, be alkaline-earth metal and/or alkaline earth metal hydride.Reducing metal reduction ZrO
2standard gibbs generate and can be negative, therefore on thermodynamics, can carry out.Research in the past shows if zirconium reduction is carried out thoroughly can not causing too high oxygen level in product.Its reason is that the metal oxide fusing point of reduction generation is higher, and after reaction, reducing metal oxide wraps up unreacted ZrO
2, cause reaction not thorough.Improve in theory temperature of reaction and can avoid the generation of parcel over the fusing point of the metal oxide of reduction generation, yet this reduction reaction is thermopositive reaction, improve temperature and be unfavorable for the carrying out reacting, and then cause the halfway problem of reaction.
The present invention finds first to add after the muriate of alkali-metal muriate or alkaline-earth metal before metallothermic reduction reaction by research, carry out again metallothermic reduction reaction, can make the metal oxide (MeO) that reaction generates form the eutectic of low melting point, and avoid unreacted ZrO
2coated.To add CaCl
2for example describes.The CaCl that adds reactant 16.9Wt%
2the fusing point of rear CaO is down to 593 ℃.Thereby avoided the metal oxide generating in reaction process to be coated unreacted is zirconic, do not improved under the prerequisite of temperature of reaction, guaranteed zirconium white reaction thoroughly.
It may be noted that basic metal refers to the metallic element of periodic table of elements ZhongIA family.Alkaline-earth metal refers to the metallic element of periodic table of elements ZhongIIA family.Preferred basic metal villaumite used or alkaline-earth metal villaumite are KCl, NaCl, MgCl
2, CaCl
2in the mixture of one or more compositions.Employing such alkaline-earth metal after calcined dehydration separation reacts, and can not increase the content of impurity in products therefrom.
More preferably basic metal villaumite or alkaline-earth metal villaumite are NaCl and/or CaCl.This muriate can farthest promote reaction thoroughly to carry out, and makes the purity of gained zirconium reach simultaneously and is greater than 99.9%.。
The add-on of basic metal villaumite or alkaline-earth metal villaumite can be identical with the add-on of reducing metal.The addition of preferred as alkali villaumite or alkaline-earth metal villaumite be in metallothermic reduction reaction in mole 0.02～2 times of theoretical oxide growing amount.By this amount, add, what can make that reaction carries out is the most thorough, makes the purity of gained zirconium reach simultaneously and is greater than 99.9%.
Hafnium content < 100ppm in preferential oxidation zirconium, zirconic particle diameter < 10 orders.Adopt pulverous zirconium white of this particle diameter can increase calcium with zirconic reaction area, increased reaction kinetics, promote reaction to carry out.Avoided not exclusively producing CaZrO because reacting
3, cause product purity lower.Adopt the zirconium white of this particle diameter, can avoid CaZrO
3generation, further improve the purity of gained zirconium.Preferable alloy thermal reduction reaction condition is: 800～1050 ℃, react 1～4 hour in inert atmosphere.By this condition, carry out metallothermic reduction reaction, can guarantee to react and carry out more thoroughly.Preferably also comprise metallothermic reduction reaction products therefrom is carried out obtaining elementary zirconium after removing impurities.In metallothermic reduction, removing impurities step can be removed according to the character of added Me.Take and add calcium as example, removing impurities step can comprise: metallothermic reduction reactants water is washed till without Bubble formation, to washing the solid materials that rear filtration obtains, carry out successively after acid solution washing and water washing filtered filtration residue dehydrated alcohol suction filtration, the elementary zirconium of dry acquisition afterwards.
First be washed to without bubble, the unreacted alkaline-earth metal in product or basic metal reaction can be removed.After overpickling, washing, can reduce afterwards the amount of impurity MeO in product.Make subsequent reactions be easier to carry out, the appearance of avoiding unknown difficulty to remove material.But in elementary zirconium, oxygen level is higher after removing impurities.Take and add calcium as example explanation, often need to add calcareous material, thereby in products therefrom, calcium contents is higher in reduction reaction, the avidity of zirconium and oxygen is very large, and in the product of reduction reaction, unreacted calcium is more, in water logging process heat release violent, and acceleration zirconium oxygen uptake process.Thereby in the elementary zirconium of gained, oxygen level is higher.Can remove by follow-up fused salt refining.
The elementary zirconium of metallothermic reduction reaction gained is carried out to fused salt refining.In fused salt refinement step, fused salt mixt used is by CaCl
2form with the fused salt of Ca.By fused salt refining, can cause the ZrO that sintering causes because of local superheating by what may occur in metallothermic reduction process
2, CaO residuals content significantly reduces, reduce reduzate water washing process zirconium oxygen uptake and the higher oxygen level of elementary zirconium that causes, thereby improve product purity.It is mainly the oxygen of removing wherein that the elementary zirconium obtaining through washing is carried out to fused salt refining.In refining process, calcium and oxygen have extremely strong avidity, can utilize fused salt mixt that the unnecessary oxygen in elementary zirconium is taken away.And the oxygen concn in oxygen level and elementary zirconium exists compared with big difference in fused salt mixt, this difference makes the oxygen in elementary zirconium at high temperature with the form of CaO, enter fused salt.Meanwhile, the CaCl in fused salt mixt
2can dilute CaO and reduce the activity of CaO, promote that the oxygen in elementary zirconium spreads in fused salt mixt.
Preferably gained secondary zirconium is washed to the impurity such as fused salt mixt of removing wherein and carry out again Combination Smelting.In the product obtaining after fused salt refining, the concentration of calcium is far below calcium concn in reduzate, when therefore water logging is washed, can avoid calcium to react a large amount of heat of generation with water and promote a large amount of oxygen uptakes of zirconium, therefore after washing, oxygen level in secondary zirconium is starkly lower than through the oxygen level in the elementary zirconium of washing, thereby can be easily by secondary zirconium washes clean.
Preferably fused salt mixt is 50～40: 1 CaCl by weight ratio
2form with Ca.In this ratio fused salt mixt, can make elementary zirconium after fused salt refining, the oxygen level in elementary zirconium is reduced to 1/10th of original oxygen level.
Treated secondary zirconium is carried out to vacuum distilling.The vapour pressure of zirconium is lower, in secondary zirconium, the vapour pressure of partial impurities is higher, vacuum distilling is to utilize the difference of the two to carry out separating impurity, the secondary zirconium that method provided by the present invention makes is powdery, the zirc sponge that its specific surface area obtains than Kroll process is large, shortened the evolving path of volatile impunty, thereby it has been carried out to vacuum distilling, can the more effective impurity of removing wherein.Vacuum distilling is condition according to a conventional method, and preferably the condition of vacuum distilling is: vacuum tightness 10
-4～10
-6pa, temperature is 650～950 ℃, is incubated 3～8 hours.By this condition, carry out the purity that vacuum distilling can effectively improve gained zirconium, its purity is more than 99.9%.Vacuum distilling condition provided by the invention adopts condition of high vacuum degree and low-temperature distillation to combine, and the impurity such as Ca, Mg in secondary zirconium, Mn are obviously reduced, and has avoided the secondary pollution to product of crucible and distillation plant simultaneously.
Three grades of zirconiums of gained are carried out obtaining product zirconium after Combination Smelting.Combination Smelting is for sequentially carrying out suspended smelting and electron beam zone melting to three grades of zirconiums.No matter being vacuum carbothermal reduction, metallothermic reduction or hydrogen reduction, produces rare refractory metal, always the Powdered or spongy metal obtaining needs further densification just can obtain ingot metal, to further process and use.The process of this densification is generally carried out under vacuum condition, and this process is exactly Refining process simultaneously.Suspended smelting is densification and the deimpurity process that reduces vapour pressure.The impurity that after suspended smelting, vapour pressure is high is evaporated.For the vacuum system of follow-up electron beam zone melting has lowered burden.Suspended smelting generally adopts water jacketed copper crucible, can avoid the pollution of crucible, through suspended smelting, can obtain the compact metal zirconium that purity is higher.Electron beam zone melting is to have combined electron beam melting and zone-melting a kind of associating method of purification, utilized in fusion process vacuum tightness high, the feature that temperature is high can further remove the impurity high with respect to zirconium vapour pressure, can also realize the deoxidation to three grades of zirconiums by the suboxide volatilization of zirconium simultaneously.Zone melting technology utilization be the effect of segregation (metallic impurity solidify with melting process in, impurity is different with the equilibrium composition in solid phase in liquid phase) and purify metals, zone melting can be removed independent use suspended smelting and electron beam melting while purifying, the problem of the impurity that the vapour pressure that cannot remove is lower.Suspended smelting and electron beam zone melting are all according to a conventional method.
The present invention also provides a kind of purity >=99.9% for preparing as stated above zirconium on the other hand.
Embodiment
In following examples and comparative example, raw materials used and equipment is commercially available.Suspended smelting by [Xiong Ping Kun. zirconium hafnium metallurgical [M]. Beijing: metallurgical industry press, 2012] in disclosed method carry out.Electron beam melting by [Xiong Ping Kun. zirconium hafnium metallurgical [M]. Beijing: metallurgical industry press, 2012] in disclosed method carry out.
Embodiment 1
By the method, carry out the preparation of zirconium, first by the metal Ca of 180g, the ZrO of 200g
2(zirconium white particle diameter is 20 orders, hafnium content is 95ppm), the Calcium Chloride Powder Anhydrous of 300g, after mixing, at 950 ℃, react 3 hours, calcium chloride used is processed through 500 ℃ of calcinings for 8 hours, after coming out of the stove, metallothermic reduction reaction product is washed with water to removing calcium oxide without Bubble formation, make unreacted metal Ca be converted into Ca (OH)
2, obtain washing mixture.Then sequentially washing mixture is adopted the acetum washing three times of 0.8mol/L, then adopt pure water to wash pH value to solution for neutral, filter after removing moisture and use again dehydrated alcohol suction filtration twice, finally in argon gas atmosphere, be dried.The elementary zirconium obtaining after dry.
Elementary zirconium is joined to 500gCaCl
2in the melting salt of 10gCa, under argon gas atmosphere, 950 ℃ of insulations, after 8 hours, product, through being washed to neutrality, obtains secondary zirconium after filtration drying.
Secondary zirconium is placed in vacuum oven and is greater than 10 in vacuum tightness
-4under condition, be heated to 750 ℃, be incubated 3 hours, after cooling coming out of the stove, obtain three grades of zirconiums.Three grades of zirconiums that obtain are put into suspension smelting furnace and be melt into zirconium ingot, zirconium ingot surface is put into after treatment electron beam melting furnace and is further purified, and obtains fine and close product zirconium after purification.
In embodiment 1, in each stage product, each substances content is listed in table 1.List in table 1.
Contained amount of element in elementary zirconium in table 1 embodiment 1, secondary zirconium, three grades of zirconiums and product zirconium
| Title | Al/％ | Ca/％ | Fe/％ | Cu/％ | W/％ | Mg/％ | Ti/％ | O/％ | Mn/％ | Hf/％ | Zr |
| Elementary zirconium | 0.0038 | 0.0860 | 0.0040 | 0.0025 | 0.0031 | 0.0075 | 0.0054 | 0.9500 | 0.0020 | 0.0075 | Matrix |
| Secondary zirconium | 0.0035 | 0.0790 | 0.0035 | 0.0030 | 0.0022 | 0.0081 | 0.0039 | 0.0730 | 0.0021 | 0.0071 | Matrix |
| Three grades of zirconiums | 0.0021 | 0.0011 | 0.0029 | 0.0027 | 0.0013 | 0.0009 | 0.0024 | 0.0480 | 0.0005 | 0.0070 | Matrix |
| Product | 0.0018 | 0.0006 | 0.0017 | 0.0016 | 0.0005 | 0.0003 | 0.0008 | 0.0400 | 0.0002 | 0.0068 | Matrix |
Embodiment 2
By the method, carry out the preparation of zirconium, by the metal M g of 200g, the ZrO of 200g
2(its ZrO
2particle diameter is 50 orders, hafnium content is 70ppm), the sodium-chlor of 360g, after mixing, at 1000 ℃, react 2 hours, after coming out of the stove, to metallothermic reduction reaction product, adopt the HCl of 0.2mol/L to wash three times, then it is neutral to adopt pure water to wash to the pH value of solution, after filtering removal moisture, use dehydrated alcohol suction filtration twice, finally in argon gas atmosphere, dry method is carried out removing impurities again.The elementary zirconium obtaining after dry.
Elementary zirconium is joined to 500gCaCl
2in the melting salt of 20gCa, under argon gas atmosphere, 900 ℃ of insulations, after 8 hours, product, through being washed to neutrality, obtains secondary zirconium after filtration drying.
Secondary zirconium is placed in vacuum oven and is greater than 10 in vacuum tightness
-5under condition, be heated to 800 ℃, be incubated 5 hours, after cooling coming out of the stove, obtain three grades of zirconiums.
Three grades of zirconiums that obtain are put into suspension smelting furnace and be melt into zirconium ingot, zirconium ingot surface is put into after treatment electron beam melting furnace and is further purified, and obtains fine and close product zirconium after purification.
In embodiment 2, in each stage product, each substances content is listed in table 2.List in table 2.
In elementary zirconium in table 2 embodiment 2, secondary zirconium, three grades of zirconiums and product zirconium contained amount of element each
| Title | Al/％ | Ca/％ | Fe/％ | Cu/％ | W/％ | Mg/％ | Ti/％ | O/％ | Mn/％ | Hf/％ | Zr |
| Elementary zirconium | 0.0028 | 0.0060 | 0.0035 | 0.0019 | 0.0021 | 0.0975 | 0.0045 | 1.0500 | 0.0018 | 0.0068 | Matrix |
| Secondary zirconium | 0.0029 | 0.0070 | 0.0030 | 0.0018 | 0.0018 | 0.0481 | 0.0035 | 0.980 | 0.0015 | 0.0059 | Matrix |
| Three grades of zirconiums | 0.0015 | 0.0011 | 0.0019 | 0.0015 | 0.0013 | 0.0019 | 0.0024 | 0.0780 | 0.0006 | 0.0058 | Matrix |
| Product | 0.0010 | 0.0005 | 0.0017 | 0.0016 | 0.0010 | 0.0003 | 0.0008 | 0.0560 | 0.0003 | 0.0059 | Matrix |
Embodiment 3
By the method, carry out the preparation of zirconium, by the metal CaH of 80g
2, the ZrO of 200g
2(its particle diameter is 100 orders, hafnium content is 55ppm), the calcium chloride of 160g, after mixing, 900 ℃ of reactions 3 hours, after coming out of the stove, metallothermic reduction reaction product is washed with water to no longer including bubble and emerged, obtain washing mixture, then with the acetic acid of 1mol/L, wash three times, adopt pure water to wash to the pH value of solution neutral, filtration is used dehydrated alcohol suction filtration twice after removing moisture more again, finally dry in argon gas atmosphere.The elementary zirconium obtaining after dry.
Elementary zirconium is joined to 400gCaCl
2in the melting salt of 10gCa, under argon gas atmosphere, 1000 ℃ of insulations, after 5 hours, product, through being washed to neutrality, obtains secondary zirconium after filtration drying.
Secondary zirconium is placed in vacuum oven and is greater than 10 in vacuum tightness
-5under condition, be heated to 900 ℃, be incubated 3 hours, after cooling coming out of the stove, obtain three grades of zirconiums.
Three grades of zirconiums that obtain are put into suspension smelting furnace and be melt into zirconium ingot, zirconium ingot surface is put into after treatment electron beam melting furnace and is further purified, and obtains densification product zirconium after purification.
In embodiment 3, in each stage product, each substances content is listed in table 3.List in table 3.
Contained amount of element in elementary zirconium in table 3 embodiment 3, secondary zirconium, three grades of zirconiums and product zirconium:
| Title | Al/％ | Ca/％ | Fe/％ | Cu/％ | W/％ | Mg/％ | Ti/％ | O/％ | Mn/％ | Hf/％ | Zr |
| Elementary zirconium | 0.0030 | 0.0260 | 0.0042 | 0.0031 | 0.0027 | 0.0065 | 0.0047 | 0.8600 | 0.0021 | 0.0054 | Matrix |
| Secondary zirconium | 0.0028 | 0.0190 | 0.0035 | 0.0028 | 0.0021 | 0.0061 | 0.0037 | 0.0620 | 0.0019 | 0.0052 | Matrix |
| Three grades of zirconiums | 0.0010 | 0.0010 | 0.0016 | 0.0013 | 0.0011 | 0.0008 | 0.0015 | 0.0460 | 0.0003 | 0.0049 | Matrix |
| Product | 0.0008 | 0.0005 | 0.0007 | 0.0011 | 0.0005 | 0.0002 | 0.0006 | 0.0330 | 0.0001 | 0.0050 | Matrix |
Embodiment 4
Be with the difference of embodiment 3: in metallothermic reduction step, temperature of reaction is 800 ℃, and the reaction times is 1 hour, add 280gKCl (800g is not in the scope of claim);
The fused salt purifying reaction time is 10 hours;
In vacuum distilling step: vacuum tightness is 10
-6pa, temperature is 950 ℃.The purity of products obtained therefrom zirconium is 99.9%.
Embodiment 5
Be with the difference of embodiment 3: in metallothermic reduction step, temperature of reaction is 1050 ℃, and the reaction times is 4 hours, adds 8g magnesium chloride;
Fused salt purifying reaction temperature is 1050 ℃, and the reaction times is 2 hours;
In vacuum distilling step: vacuum tightness is 10
-6pa, temperature is 650 ℃.The purity of products obtained therefrom zirconium is 99.9%.
Embodiment 6
Be with the difference of embodiment 3: in metallothermic reduction step, add 160g lithium chloride.The purity of products obtained therefrom zirconium is 99.9%.
Embodiment 7
Be with the difference of embodiment 3: in metallothermic reduction step, add 280gKCl.The purity of products obtained therefrom zirconium is 99.9%.
From table 1～3, by adopting method provided by the invention to purify to zirconium white, oxygen level continuous decrease, especially after fused salt refinement step, an order of magnitude of oxygen level decline, has fully demonstrated method provided by the invention for the removal effect of oxygen in zirconium white.And it is lower to adopt method provided by the invention to prepare in product zirconium all kinds of impurity contents, the purity of zirconium can reach more than 99.9%.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (9)
1. a method of preparing zirconium, is characterized in that, comprises the following steps:
Metallothermic reduction: described zirconium white reacts with alkaline-earth metal and/or alkaline earth metal hydride generation metallothermic reduction, obtains elementary zirconium after removing impurities;
Fused salt refining: described elementary zirconium and fused salt mixt send fused salt purifying reaction, obtain secondary zirconium;
Vacuum distilling: described secondary zirconium is carried out to vacuum distilling, obtain three grades of zirconiums;
Combination Smelting: described three grades of zirconiums are sequentially carried out to suspended smelting and electron beam zone melting, obtain product zirconium;
Described fused salt mixt is by CaCl
2form with the fused salt of Ca.
2. method according to claim 1, is characterized in that, before described metallothermic reduction reaction, adds basic metal villaumite or alkaline-earth metal villaumite.
3. method according to claim 2, is characterized in that, described basic metal villaumite is KCl and/or NaCl, is preferably NaCl; Described alkaline-earth metal villaumite is MgCl
2and/or CaCl
2, be preferably CaCl.
4. method according to claim 3, is characterized in that, the addition of described basic metal villaumite or alkaline-earth metal villaumite be in described metallothermic reduction reaction in mole 0.02～2 times of theoretical oxide growing amount.
5. according to the method described in any one in claim 1～4, it is characterized in that hafnium content < 100ppm in described zirconium white, described zirconic particle diameter < 10 orders.
6. method according to claim 5, is characterized in that, described metallothermic reduction reaction conditions is: 800～1050 ℃, react 1～4 hour in inert atmosphere.
7. method according to claim 5, is characterized in that, described fused salt purifying reaction temperature is 900～1050 ℃, and the reaction times is 2～10 hours; Preferred described fused salt mixt is 50～40: 1 CaCl by weight ratio
2form with Ca.
8. method according to claim 5, is characterized in that, the condition of described vacuum distilling is: vacuum tightness 10
-4～10
-6pa, temperature is 650～950 ℃, is incubated 3～8 hours.
9. a product zirconium, is characterized in that, described product zirconium is prepared from by the method described in any one in claim 1 to 8, purity >=99.9% of described product zirconium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410397353.XA CN104195355B (en) | 2014-08-13 | 2014-08-13 | Prepare the method for zirconium |
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| CN108213452A (en) * | 2018-01-12 | 2018-06-29 | 锦州市金属材料研究所 | The production method of electric igniter superfine metal zirconium powder |
| CN109252057A (en) * | 2018-09-25 | 2019-01-22 | 李梅 | A kind of fused salt chlorimation extracting method of low-grade zircon concentrate |
| CN109628763A (en) * | 2018-12-21 | 2019-04-16 | 有研工程技术研究院有限公司 | A kind of method that calcium original position distillation-deoxidation prepares high purity zirconium |
| CN110093515A (en) * | 2019-04-16 | 2019-08-06 | 北京科技大学 | A method of the brilliant directly distillation-melting of folder salt titanium prepares hypoxemia high purity titanium ingot |
| CN110802237A (en) * | 2019-09-29 | 2020-02-18 | 中南大学 | Preparation method of high-purity zirconium metal powder |
| CN112458308A (en) * | 2020-11-25 | 2021-03-09 | 清远先导材料有限公司 | Method for preparing ultra-high pure cadmium |
| CN115044785A (en) * | 2022-05-31 | 2022-09-13 | 中国恩菲工程技术有限公司 | Method and device for preparing metal scandium |
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| CN108213452A (en) * | 2018-01-12 | 2018-06-29 | 锦州市金属材料研究所 | The production method of electric igniter superfine metal zirconium powder |
| CN109252057A (en) * | 2018-09-25 | 2019-01-22 | 李梅 | A kind of fused salt chlorimation extracting method of low-grade zircon concentrate |
| CN109628763A (en) * | 2018-12-21 | 2019-04-16 | 有研工程技术研究院有限公司 | A kind of method that calcium original position distillation-deoxidation prepares high purity zirconium |
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| CN110802237A (en) * | 2019-09-29 | 2020-02-18 | 中南大学 | Preparation method of high-purity zirconium metal powder |
| CN110802237B (en) * | 2019-09-29 | 2021-06-15 | 中南大学 | Preparation method of high-purity zirconium metal powder |
| CN112458308A (en) * | 2020-11-25 | 2021-03-09 | 清远先导材料有限公司 | Method for preparing ultra-high pure cadmium |
| CN115044785A (en) * | 2022-05-31 | 2022-09-13 | 中国恩菲工程技术有限公司 | Method and device for preparing metal scandium |
| CN115044785B (en) * | 2022-05-31 | 2024-04-02 | 中国恩菲工程技术有限公司 | Preparation method and device of scandium metal |
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