CN104195355B - Prepare the method for zirconium - Google Patents

Prepare the method for zirconium Download PDF

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CN104195355B
CN104195355B CN201410397353.XA CN201410397353A CN104195355B CN 104195355 B CN104195355 B CN 104195355B CN 201410397353 A CN201410397353 A CN 201410397353A CN 104195355 B CN104195355 B CN 104195355B
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zirconium
fused salt
alkaline
earth metal
metallothermic reduction
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CN104195355A (en
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黄美松
贾帅广
王志坚
成维
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HUNAN RESEARCH INSTITUTE OF RARE EARTH METAL MATERIALS
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Abstract

The invention provides a kind of method and the gained zirconium of preparing zirconium, the method comprises the following steps: metallothermic reduction: impel zirconium white and alkaline-earth metal or alkaline earth metal hydride generation metallothermic reduction to react, obtain elementary zirconium after removing impurities; Fused salt refining: impel elementary zirconium and the purifying reaction of fused salt mixt generation fused salt, obtain secondary zirconium; Vacuum distilling: carry out vacuum distilling to secondary zirconium, obtains three grades of zirconiums; Combination Smelting: sequentially suspended smelting and electron beam zone melting are carried out to three grades of zirconiums, obtains product zirconium; Fused salt mixt is made up of the fused salt of CaCl2 and Ca.Method provided by the invention take zirconium white as raw material, sequentially adopt metallothermic reduction, fused salt refining, vacuum distilling and Combination Smelting method, fused salt refining is carried out to the elementary zirconium obtained after metallothermic reduction reaction, effectively can reduce the oxygen level of gained intermediate product zirconium, and fused salt mixt used is easily removed and can not be impacted the purity of zirconium by washing.

Description

Prepare the method for zirconium
Technical field
The present invention relates to preparation of metals field, especially, relate to a kind of method preparing zirconium.
Background technology
Thus the thermal-neutron capture cross-section small intensity height of Zr is widely used in nuclear reactor material, and the good physical-chemical characteristic of Zr makes it also be used to reactor in chemical industry, the parts such as valve in addition, the additive etc. of killed steel, non-ferrous alloy.Along with the fast development of the progress particularly nuclear industry in recent years of science and technology, more and more higher to the purity requirement of Zr.The method that current preparation purity is greater than the zirconium of 99.9% mainly contains Kroll process, fused salt electrolysis process, halogenide thermal dissociation method, metallothermic reduction ZrO 2method.
Kroll process: since the forties in 20th century Ke Laoer invented the method for magnesium reduction titanium tetrachloride, and use it for reduction zirconium tetrachloride prepare vesicular metal zirconium, Kroll process zirconium is still the main method of current industrial extensive preparation metal zirconium so far.The method adopts magnesiothermic reduction-distillation to produce zirconium sponge after being purified by zirconium tetrachloride.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 obtained is close to 3N.But for preparing high-purity core level metal zirconium, this technical process is long, needs special equipment, all kinds of control device, invests higher; Because muriate is relatively more active, be easy to introduce impurity in the process of preparation metal zirconium, for the preparation of high purity zirconium increases difficulty; 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, the principle that zirconium ion obtains electronics at negative electrode and separates out.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 comparatively large to electrolytic production quality influence, to need research further preparing in high purity zirconium.
FCC method: preparation metal zirconium adopts solid zirconium dioxide to be negative electrode, utilizes oxonium ion to enter fused salt and migrate to anodic reaction, leaving the principle of pure metal zirconium at negative electrode is that raw material carrys out one-step electrolysis generation metal zirconium with zirconium white.The technical process of this process shortens, does not have chlorine to release yet, but spreads in solid phase owing to there is ion in reaction process in reaction process, therefore 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 the zirconium sponge of oxygen level lower than 400ppm, but easily introduce impurity due to fused salt electrolysis abroad, 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 slag in product and metal zirconium be difficult to be separated thus study less.
Summary of the invention
The object of the invention is to provide the method and gained zirconium of preparing zirconium, with solve prior art moderate purity higher than 99.9% zirconium be difficult to simple and effective, be 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 preparing zirconium, comprise the following steps: metallothermic reduction: zirconium white and alkaline-earth metal and/or alkaline earth metal hydride generation metallothermic reduction are reacted, and obtain elementary zirconium after removing impurities; Fused salt refining: elementary zirconium and fused salt mixt send fused salt purifying reaction, obtain secondary zirconium; Vacuum distilling: carry out vacuum distilling to secondary zirconium, obtains three grades of zirconiums; Combination Smelting: sequentially suspended smelting and electron beam zone melting are carried out to three grades of zirconiums, obtains product zirconium; Fused salt mixt is made up of the fused salt of CaCl2 and Ca.
Further, before metallothermic reduction reaction, basic metal villaumite or alkaline-earth metal villaumite is added.
Further, basic metal villaumite is KCl and/or NaCl, is preferably NaCl; Alkaline-earth metal villaumite is MgCl 2and/or CaCl 2, be preferably CaCl 2.
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 order.
Further, metallothermic reduction reaction conditions is: 800 ~ 1050 DEG C, reacts 1 ~ 4 hour in inert atmosphere.
Further, method according to claim 6, is characterized in that, fused salt purifying reaction temperature is 900 ~ 1050 DEG C, and the reaction times is 2 ~ 10 hours; Preferred fused salt mixt is the CaCl of 50 ~ 40:1 by weight ratio 2form with Ca.
Further, the condition of vacuum distilling is: vacuum tightness 10 -4~ 10 -6pa, temperature is 650 ~ 950 DEG C, is incubated 3 ~ 8 hours.
Additionally provide a kind of product zirconium according to a further aspect in the invention, the method for product zirconium any one of claim 1 to 9 is prepared from, purity >=99.9% of product zirconium.
The present invention has following beneficial effect:
Method provided by the invention is that raw material sequentially adopts metallothermic reduction, fused salt refining, vacuum distilling and Combination Smelting method with zirconium white, fused salt refining is carried out to the elementary zirconium obtained after metallothermic reduction reaction, effectively can reduce the oxygen level of gained intermediate product zirconium, and fused salt mixt used is easily removed and can not 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 forming a application's part is used to provide a further understanding of the present invention, and schematic description and description of the present invention, 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 described in detail, but the multitude of different ways that the present invention can be defined by the claims and cover is implemented.
See Fig. 1, prepare method and the gained zirconium of zirconium, comprise the following steps: metallothermic reduction: zirconium white and alkaline-earth metal and/or alkaline earth metal hydride generation metallothermic reduction are reacted, and obtain elementary zirconium after removing impurities; Fused salt refining: elementary zirconium and fused salt mixt send fused salt purifying reaction, obtain secondary zirconium; Vacuum distilling: carry out vacuum distilling to secondary zirconium, obtains three grades of zirconiums; Combination Smelting: sequentially suspended smelting and electron beam zone melting are carried out to three grades of zirconiums, obtains 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 added is the metal with reductibility.The metal of reductibility can be better than the metal of zirconium as Ca, Mg, CaH for the bonding force with oxygen 2deng.Be alkaline-earth metal and/or alkaline earth metal hydride in this reaction.Reducing metal reduction ZrO 2standard Gibbs generate can be negative, therefore thermodynamically can carry out.Research in the past shows if zirconium reduction is carried out thoroughly causing too high oxygen level in product.Its reason is that the metal oxide fusing point that reduction generates is higher, and after reaction, reducing metal oxide wraps up unreacted ZrO 2, cause reaction not thorough.Improve temperature of reaction in theory and exceed the generation that the fusing point of metal oxide that reduction generates can avoid wrapping up, but this reduction reaction is thermopositive reaction, improves the carrying out that temperature is unfavorable for reacting, and then cause the halfway problem of reaction.
After the present invention finds first to add the muriate of alkali-metal muriate or alkaline-earth metal before metallothermic reduction reaction by research, carry out metallothermic reduction reaction again, the metal oxide (MeO) that reaction can be made to generate forms the eutectic of low melting point, and avoids unreacted ZrO 2coated.To add CaCl 2for example is described.Add the CaCl of reactant 16.9Wt% 2the fusing point of rear CaO is down to 593 DEG C.Thus it is zirconic coated to unreacted to avoid the metal oxide generated in reaction process, under the prerequisite not improving temperature of reaction, ensure zirconium white reaction thoroughly.
It may be noted that basic metal refers to the metallic element of I A race in the periodic table of elements.Alkaline-earth metal refers to the metallic element of II A race in the periodic table of elements.Preferred basic metal villaumite used or alkaline-earth metal villaumite are KCl, NaCl, MgCl 2, CaCl 2in one or more composition mixtures.Adopt such alkaline-earth metal after calcined dehydration is separated to react, the content of impurity in products therefrom can not be increased.
More preferably basic metal villaumite or alkaline-earth metal villaumite are NaCl and/or CaCl 2.This muriate farthest can promote that reaction is thoroughly carried 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.Add by this amount, can make to react carry out the most thorough, make the purity of gained zirconium reach simultaneously and be greater than 99.9%.
Hafnium content <100ppm in preferential oxidation zirconium, zirconic particle diameter <10 order.Adopt pulverous zirconium white of this particle diameter can increase calcium with zirconic reaction area, add reaction kinetics, promote that reaction is carried out.Avoid and produce CaZrO because reacting incomplete 3, cause product purity lower.Adopt the zirconium white of this particle diameter, can CaZrO be avoided 3generation, improve further the purity of gained zirconium.Preferable alloy thermal reduction reaction condition is: 800 ~ 1050 DEG C, reacts 1 ~ 4 hour in inert atmosphere.Carry out metallothermic reduction reaction by this condition, can ensure that reaction is carried out more thoroughly.Preferably also comprise after removing impurities is carried out to metallothermic reduction reaction products therefrom and obtain elementary zirconium.In metallothermic reduction, removing impurities step can be removed according to the character of added Me.To add calcium, removing impurities step can comprise: metallothermic reduction reactants water is washed till bubble-free and produces, filter after the solid materials obtained carries out acid solution washing and water washing successively afterwards to washing, filtered filtration residue dehydrated alcohol suction filtration, the elementary zirconium of dry acquisition afterwards.
First bubble-free is washed to, can by the unreacted alkaline-earth metal in product or basic metal reaction removing.The amount of impurity MeO in product can be reduced afterwards after overpickling, washing.Make subsequent reactions be easier to carry out, avoid unknown difficulty except the appearance of material.But in elementary zirconium, oxygen level is higher after removing impurities.Illustrate to add calcium, often need add calcareous material in reduction reaction, thus in products therefrom, calcium contents is higher, and the avidity of zirconium and oxygen is very large, and in the product of reduction reaction, unreacted calcium is more, and in water logging process, heat release is violent, and accelerates zirconium oxygen uptake process.Thus in the elementary zirconium of gained, oxygen level is higher.Remove by follow-up fused salt refining.
Fused salt refining is carried out to the elementary zirconium of metallothermic reduction reaction gained.In fused salt refinement step, fused salt mixt used is by CaCl 2form with the fused salt of Ca.By the ZrO caused because local superheating causes sintering that fused salt refining can may will 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 the elementary zirconium that causes, thus improve product purity.Carry out fused salt refining mainly remove oxygen wherein to through washing the elementary zirconium that obtains.In refining process, calcium and oxygen have extremely strong avidity, and fused salt mixt can be utilized to be taken away by the unnecessary oxygen in elementary zirconium.And the oxygen concn in fused salt mixt in oxygen level and elementary zirconium exists comparatively big difference, this difference makes the oxygen in elementary zirconium at high temperature enter fused salt with the form of CaO.Meanwhile, the CaCl in fused salt mixt 2caO can be diluted to reduce the activity of CaO, promote that the oxygen in elementary zirconium spreads in fused salt mixt.
Preferably gained secondary zirconium is carried out washing the impurity such as removing fused salt mixt wherein and carry out Combination Smelting again.In the product obtained after fused salt refining, the concentration of calcium is far below calcium concn in reduzate, therefore can avoid calcium and water when water logging is washed to react and produce a large amount of heat and promote a large amount of oxygen uptake of zirconium, therefore after washing, oxygen level in secondary zirconium is starkly lower than the oxygen level in the elementary zirconium of washing, thus can easily by secondary zirconium washes clean.
Preferred fused salt mixt is the CaCl of 50 ~ 40:1 by weight ratio 2form with Ca.Can make elementary zirconium after fused salt refining in this ratio fused salt mixt, the oxygen level in elementary zirconium is reduced to 1/10th of original oxygen level.
Vacuum distilling is carried out to treated secondary zirconium.The vapour pressure of zirconium is lower, in secondary zirconium, the vapour pressure of partial impurities is higher, vacuum distilling is that the difference of both utilizations carrys out separating impurity, the secondary zirconium that method provided by the present invention obtains is powdery, the zirc sponge that its specific surface area obtains than Kroll process is large, shorten the evolving path of volatile impunty, thus vacuum distilling is carried out to it, can more effective removing impurity wherein.Vacuum distilling according to a conventional method condition is carried out, and the condition of preferred vacuum distilling is: vacuum tightness 10 -4~ 10 -6pa, temperature is 650 ~ 950 DEG C, is incubated 3 ~ 8 hours.Carry out by this condition the purity that vacuum distilling effectively can improve gained zirconium, its purity can reach 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, Mn in secondary zirconium are obviously reduced, and avoids crucible and distillation plant to the secondary pollution of product simultaneously.
Product zirconium is obtained after Combination Smelting is carried out to gained three grades of zirconiums.Combination Smelting is for sequentially to carry out suspended smelting and electron beam zone melting to three grades of zirconiums.Produce no matter rare refractory metal is vacuum carbothermal reduction, metallothermic reduction or hydrogen reduction, always the Powdered or spongy metal obtained, need further densification just can obtain ingot metal, so that processing and use further.The process of this densification is generally carried out under vacuum, and this process is exactly Refining process simultaneously.Suspended smelting is densification and the deimpurity process reducing 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 reduces burden.Suspended smelting generally adopts water jacketed copper crucible, can be avoided the pollution of crucible, can obtain the higher compact metal zirconium of purity through suspended smelting.Electron beam zone melting has combined electron beam melting and zone-melting one associating method of purification, make use of vacuum tightness in fusion process high, the feature that temperature is high can remove the impurity high relative to zirconium vapour pressure further, the deoxidation simultaneously also realized three grades of zirconiums by the suboxide volatilization of zirconium.Zone melting technology utilization be that (metallic impurity is solidifying with in melting process the effect of segregation, impurity is different with the equilibrium composition in solid phase in liquid phase) and purify metals, when zone melting can be removed and is used alone suspended smelting and electron beam melting purification, the problem of the impurity that the vapour pressure that cannot remove is lower.Suspended smelting and electron beam zone melting carry out all according to a conventional method.
The present invention additionally provides a kind of purity >=99.9% preparing zirconium as stated above 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 metallurgy [M]. Beijing: metallurgical industry press, 2012] disclosed in method carry out.Electron beam melting by [Xiong Ping Kun. zirconium hafnium metallurgy [M]. Beijing: metallurgical industry press, 2012] disclosed in method carry out.
Embodiment 1
The preparation of zirconium is carried out, first by the metal Ca of 180g, the ZrO of 200g by the method 2(zirconium white particle diameter is 20 orders, hafnium content is 95ppm), the Calcium Chloride Powder Anhydrous of 300g, 950 DEG C of reactions 3 hours after mixing, calcium chloride used is through 500 DEG C of calcinings process in 8 hours, after coming out of the stove, metallothermic reduction reaction product is washed with water and produces removal calcium oxide to bubble-free, make unreacted metal Ca be converted into Ca (OH) 2, obtain washing mixture.Then sequentially adopt the acetum of 0.8mol/L to wash three times to washing mixture, then adopt pure water to the pH value of solution for neutral, filtration uses dehydrated alcohol suction filtration twice after removing moisture again, finally dry in argon gas atmosphere.The elementary zirconium obtained after drying.
Elementary zirconium is joined 500gCaCl 2with in the melting salt of 10gCa, under an argon atmosphere, 950 DEG C 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 DEG C, be incubated 3 hours, cooling obtains three grades of zirconiums after coming out of the stove.Obtain three grades of zirconiums are put into suspension smelting furnace and is melt into zirconium ingot, zirconium ingot surface is put into electron beam melting furnace after treatment and is purified further, 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, secondary zirconium, three grades of zirconiums and product zirconium in table 1 embodiment 1
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
The preparation of zirconium is carried out, by the ZrO of the metal M g of 200g, 200g by the method 2(its ZrO 2particle diameter is 50 orders, hafnium content is 70ppm), the sodium-chlor of 360g, 1000 DEG C of reactions 2 hours after mixing, after coming out of the stove, adopt the HCl of 0.2mol/L to wash three times to metallothermic reduction reaction product, then adopt pure water neutral to the pH value of solution, filter after removing moisture and use dehydrated alcohol suction filtration twice again, finally dry in argon gas atmosphere method carries out removing impurities.The elementary zirconium obtained after drying.
Elementary zirconium is joined 500gCaCl 2with in the melting salt of 20gCa, under an argon atmosphere, 900 DEG C 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 DEG C, be incubated 5 hours, cooling obtains three grades of zirconiums after coming out of the stove.
Obtain three grades of zirconiums are put into suspension smelting furnace and is melt into zirconium ingot, zirconium ingot surface is put into electron beam melting furnace after treatment and is purified further, 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 table 2 embodiment 2, in elementary zirconium, secondary zirconium, three grades of zirconiums and product zirconium, contained amount of element is 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
The preparation of zirconium is carried out, by the metal CaH of 80g by the method 2, the ZrO of 200g 2(its particle diameter is 100 orders, hafnium content is 55ppm), the calcium chloride of 160g, 900 DEG C of reactions 3 hours after mixing, after coming out of the stove, metallothermic reduction reaction product is washed with water and emerge to no longer including bubble, obtain washing mixture, then three times are washed with the acetic acid of 1mol/L, adopt pure water neutral to the pH value of solution again, filter after removing moisture and use dehydrated alcohol suction filtration twice again, finally dry in argon gas atmosphere.The elementary zirconium obtained after drying.
Elementary zirconium is joined 400gCaCl 2with in the melting salt of 10gCa, under an argon atmosphere, 1000 DEG C 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 DEG C, be incubated 3 hours, cooling obtains three grades of zirconiums after coming out of the stove.
Obtain three grades of zirconiums are put into suspension smelting furnace and is melt into zirconium ingot, zirconium ingot surface is put into electron beam melting furnace after treatment and is purified further, 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, secondary zirconium, three grades of zirconiums and product zirconium in table 3 embodiment 3:
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 DEG C, and the reaction times is 1 hour, adds 280gKCl;
The fused salt purifying reaction time is 10 hours;
In vacuum distilling step: vacuum tightness is 10 -6pa, temperature is 950 DEG C.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 DEG C, and the reaction times is 4 hours, adds 8g magnesium chloride;
Fused salt purifying reaction temperature is 1050 DEG C, and the reaction times is 2 hours;
In vacuum distilling step: vacuum tightness is 10 -6pa, temperature is 650 DEG C.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 continues to reduce, especially after fused salt refinement step, oxygen level declines an order of magnitude, has fully demonstrated the removal effect of method provided by the invention for oxygen in zirconium white.And it is lower to adopt method provided by the invention to prepare all kinds of impurity content in product zirconium, 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 amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.

Claims (8)

1. prepare a method for zirconium, it is characterized in that, comprise the following steps:
Metallothermic reduction: zirconium white and alkaline-earth metal and/or alkaline earth metal hydride generation metallothermic reduction are reacted, and obtain 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: carry out vacuum distilling to described secondary zirconium, obtains three grades of zirconiums;
Combination Smelting: sequentially suspended smelting and electron beam zone melting are carried out to described three grades of zirconiums, obtains product zirconium;
Described fused salt mixt is by CaCl 2form with the fused salt of Ca;
Basic metal villaumite or alkaline-earth metal villaumite is added before described metallothermic reduction reaction.
2. method according to claim 1, is characterized in that, described basic metal villaumite is KCl and/or NaCl; Described alkaline-earth metal villaumite is MgCl 2and/or CaCl 2.
3. method according to claim 2, 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.
4. method according to claim 2, is characterized in that, described basic metal villaumite is NaCl; Described alkaline-earth metal villaumite is CaCl 2.
5. the method according to any one of Claims 1 to 4, is characterized in that, hafnium content <100ppm in described zirconium white, described zirconic particle diameter <10 order.
6. method according to claim 5, is characterized in that, described metallothermic reduction reaction conditions is: 800 ~ 1050 DEG C, reacts 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 DEG C, and the reaction times is 2 ~ 10 hours; Preferred described fused salt mixt is the CaCl of 50 ~ 40:1 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 DEG C, is incubated 3 ~ 8 hours.
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CN108213452B (en) * 2018-01-12 2021-01-26 锦州市金属材料研究所 Production method of superfine metal zirconium powder for electric igniter
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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
CN110093515B (en) * 2019-04-16 2020-11-13 北京科技大学 Method for preparing low-oxygen high-purity titanium ingot by direct distillation-smelting of salt-sandwiched titanium crystal
CN110802237B (en) * 2019-09-29 2021-06-15 中南大学 Preparation method of high-purity zirconium metal powder
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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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