CN102459665A - Process for separating hafnium and zirconium - Google Patents

Process for separating hafnium and zirconium Download PDF

Info

Publication number
CN102459665A
CN102459665A CN2010800257665A CN201080025766A CN102459665A CN 102459665 A CN102459665 A CN 102459665A CN 2010800257665 A CN2010800257665 A CN 2010800257665A CN 201080025766 A CN201080025766 A CN 201080025766A CN 102459665 A CN102459665 A CN 102459665A
Authority
CN
China
Prior art keywords
metal
zirconium
hafnium
mixture
molten metal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN2010800257665A
Other languages
Chinese (zh)
Other versions
CN102459665B (en
Inventor
肖艳萍
安东尼·范·桑迪维克
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Technische Universiteit Delft
Original Assignee
Technische Universiteit Delft
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Technische Universiteit Delft filed Critical Technische Universiteit Delft
Publication of CN102459665A publication Critical patent/CN102459665A/en
Application granted granted Critical
Publication of CN102459665B publication Critical patent/CN102459665B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/26—Electrolytic production, recovery or refining of metals by electrolysis of melts of titanium, zirconium, hafnium, tantalum or vanadium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/14—Obtaining zirconium or hafnium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C22B34/129—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds by dissociation, e.g. thermic dissociation of titanium tetraiodide, or by electrolysis or with the use of an electric arc

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Electrolytic Production Of Metals (AREA)

Abstract

The invention is directed to a process for separating a mixture comprising hafnium and zirconium. The process of the present invention comprises a step in which a molten metal phase comprising zirconium and hafnium dissolved in a first metal M1 and a second metal M2 is contacted with a molten salt phase comprising at least one metal halide M3Z, wherein M3 is a metal that is less electropositive than zirconium and hafnium, and at least one salt of one or more metals M4, wherein M4 is a metal from Group 1 or Group 2 of the Periodic Table, whereby at least part of said hafnium is transported from said molten metal phase to said molten salt phase.

Description

The technology of separating hafnium and zirconium
Technical field
The present invention relates to the technology that a kind of separation comprises the mixture of hafnium and zirconium.Zirconium and alloy thereof have HMP and high corrosion resistance.Therefore, zirconium is applied to especially nuclear reactor of chemical industry.Zirconium has low-down uptake factor to neutron, and this makes this metal extremely be suitable in nuclear reactor, being used as material of construction.
Background technology
At occurring in nature, the zirconium of being found almost always combines with hafnium.Opposite with zirconium, hafnium has higher uptake factor to neutron, and this makes hafnium be adapted at being used as in the nuclear reactor neutron-absorbing material.Chemically, metal zirconium is extremely similar each other with hafnium.Metal zirconium is applied to nuclear reactor as material of construction, and neutron uptake factor low in nuclear reactor is necessary, and the hafnium content in the metal zirconium should be low as much as possible.
On the contrary, the zirconium of trace does not almost have influence to the neutron uptake factor of hafnium in the hafnium.
Zirconium has good intensity to weight balancing.To good this intensity of weight balancing containing the oxygen ratio and just can obtain in enough low in metal zirconium or its associated alloys only.If the ratio of dissolved oxygen is too high in metal or its alloy, this material can become too crisp and cause its technical operability to reduce so usually.
US-A-4072506 described a kind of from the mixture that contains hafnium and zirconium with hafnium and zirconium separation processes.In known this technology, this mixture be dissolved in contain the single solvent metal molten metal mutually in.Though copper is classified as one of several kinds of suitable solvent metals in cadmium, lead, bismuth and tin, US-A-4072506 proposes: in fact, the metal that is suitable as solvent metal most is a zinc.Molten metal contacts with melting salt, thus hafnium from the molten metal phase transition to the fusion salt face.The fusion salt face also contains zirconates, and it can be reduced to zirconium and be transferred to the molten metal phase.Technology among the US-A-4072506 further comprises distilation steps, and wherein zinc is from being to be distilled out the metallographic phase of staple with the zirconium.Reclaim zinc, obtain the product flow of zirconium.
Summary of the invention
The present invention attempts to improve the technology of US-A-4072506; Especially through being provided, purifying process finally obtains higher separation factor β; It can carry out under lower temperature; And can combine with the electrorefining step, and be applied to produce the step of intermediates and/or reclaim in the step of zirconium and/or hafnium.
Therefore, of the present inventionly relate in one aspect to the purifying process that a kind of separation comprises the mixture of hafnium and zirconium, may further comprise the steps:
The molten metal phase is provided, and said molten metal comprises first metal M mutually 1And second metal M 2
The fusion salt face is provided, and said fusion salt face comprises at least a metal halide M 3Z and one or more metal M 4One or more salt, wherein, M 3Be the metal of positive polarity less than zirconium and hafnium, M 4Metal for first family in the periodictable or second family;
The said mixture that comprises hafnium and zirconium is joined said molten metal mutually; And
Make said molten metal mutually and said fusion salt face contact, thus at least the said hafnium of part from said molten metal phase transition to said fusion salt face.
Preferably, select metal M 1And M 2Make it more stable than zirconium (and hafnium).In principle; All 5-15 family and 4-6 all metals in the cycle all can be used in the above-mentioned technology in the periodictable (all family and cycles all define according to IUPAC in the periodictable that the present invention relates to); Because their positive polarity is all low than zirconium, considerably, has higher electronegativity.The electronegativity of zirconium is 1.33 Paulings (Pauling), hafnium be 1.3 Paulings.Therefore, to be higher than 1.33 metal all be suitable to electronegativity.In fact, preferably, M 1And M 2Be independently selected from respectively in Cu, Sn, Ag, Sb, Zn, Pb, Bi, Fe, Ni, Cd, Si and Co.Preferably, select M 2Make it can reduce M 1Fusing point, be favourable like this with regard to the energy waste of technology.Carry out this technology at a lower temperature and have superiority, promptly reduced the infusibility problem, prolonged the life-span of device simultaneously and reduced operational cost.
The fusion salt face comprises at least a metal halide M 3Z is preferably metal chloride M 3Cl x, wherein x representes corresponding to M 3Valent integer.Metal halide is preferably corresponding with the metallographic phase of molten metal in mutually, just, and M 3With M 1And/or M 2Identical.Especially preferably, use metal halide M 3The mixture of Z, the total M that wherein exists 3A part be equivalent to M 1, another part is equal to M 2In a preferred embodiment, molten metal comprises Cu and Sn mutually, and the fusion salt face comprises CuCl 2And SnCl 2
The fusion salt face further comprises one or more metal M 4At least a salt, wherein, M 4Be first family (basic metal) metal in the periodictable, be preferably Na or K; Or the second family in the periodictable (earth alkali metal) metal, be preferably Mg or Ca.The adding of this salt can reduce the fusing point of fusion salt face, is favourable like this with regard to the energy waste of technology.For this reason, using halogenide is preferably, especially muriate.M 4Be preferably selected from Na, K, Ba, Sr and Ca.Preferably, M 4Salt be the muriate of Ca, Na and/or K or the mixture of fluorochemical.That best is CaCl 2, it can at random replenish with NaCl and/or KCl.In order to obtain meeting the metal zirconium of examining application requiring, can use the liquid metal mixture, this liquid metal mixture can be employed in the technology of hereinafter describing and obtain.At first, hereinafter will combine accompanying drawing that aforesaid separating technology is elaborated.
Description of drawings
Fig. 1 to Fig. 8 has schematically shown different embodiments of the invention.Said embodiment shows the pre-treatment of the starting materials that is added to purification step 2 and is obtained by purification step 2 and the post-treatment of the product that obtained by purification step 2 carries out respectively in a different manner.
Embodiment
Fig. 1 has schematically described the operational path of producing the purifying zirconium.In this embodiment, will contain HfO 2ZrO 2Material is incorporated into electrolyzer 1.The mixture that negative electrode in the electrolyzer 1 is made up of liquid copper and/or tin and other possible precious metal.The mixture that use is made up of fused alkaline earth metal chloride and/or alkali metal chloride is as electrolytic solution, and when technology begins to wherein adding number of C aO.Use graphite as anode.Whole technology is carried out under 500 ℃ to 1250 ℃ temperature usually, and this temperature depends on the accurate composition and the liquid cathode of liquid electrolyte.When containing HfO 2ZrO 2Be added in the electrolyzer 1, and the potential difference that between anode and negative electrode, applies enough big in, contain HfO 2ZrO 2Be reduced and can enter into the molten metal negative electrode and dissolve, generate CO at anode along with corresponding metal (Zr and Hf).
Molten metal in the electrolyzer 1 is incorporated into the purifying compartment 2 that contains the mixture of forming by fusion alkaline earth metal chloride and/or alkali metal chloride.Then, add CuCl 2/ SnCl 2Mixture.At this moment, the optionally oxidation of metal Hf quilt in the molten metal, and be transferred in the mixture of forming by fusion alkaline earth metal chloride and/or alkali metal chloride.Fusion alkaline earth metal chloride in the purifying compartment 2 and/or alkali metal chloride are joined oxidation compartment 3.In oxidation compartment 3, add oxygen (just pure or pure basically oxygen), and the Hf in the mixture that will be made up of fusion alkaline earth metal chloride and/or alkali metal chloride is converted into impure HfO 2Molten metal in the purifying compartment 2 is joined electrorefining pond 4.
Liquid metal mixture from purifying compartment 2 to electrorefining pond 4 is used as liquid anodes.Can use the molten mixture of forming by alkaline earth metal chloride and/or alkali metal chloride as electrolytic solution.When the electrorefining step begins, in electrolytic solution, add some ZrCl 4Perhaps ZrCl 2The starting sheet that can use the solid zirconium is as negative electrode.Therefore, have from bottom to top in the electrorefining pond 4: as anodic fusion zirconium, copper and/or tin and other possible precious metal; Added ZrCl 4Perhaps ZrCl 2The mixture of forming by fusion alkaline earth metal chloride and/or alkali metal chloride as electrolytic solution; The starting sheet of solid zirconium is as negative electrode.Generate very pure zirconium at negative electrode.
Fig. 2 has schematically described the operational path of another production purifying zirconium.In this embodiment, will contain HfCl 4ZrCl 4Material is incorporated into electrolyzer 1.In the embodiment of Fig. 2, the negative electrode in the electrolyzer 1 and anode, purifying compartment 2 and oxidation compartment 3 basically can with Fig. 1 in identical, and have identical functions with Fig. 1.To join chlorinating step 5 from the molten metal flow of compartment 2, and feed chlorine.Zr in the molten metal flow is converted to and is very pure ZrCl 4, ZrCl 4Can pass through Ke Laoer (Kroll) method and generate very pure zirconium.
Fig. 3 schematically shows the operational path of another production purifying zirconium.In this embodiment, will contain HfO 2ZrO 2Material is incorporated into electrolyzer 1.Purifying compartment 2, oxidation compartment 3 and chlorination 5 basically can with aforementioned figures in identical, and have and the aforementioned figures identical functions.Final product is very pure ZrCl 4, ZrCl 4Can generate very pure zirconium through gram Raul method.
Fig. 4 schematically shows the operational path of another production purifying zirconium.In this embodiment, will contain HfCl 4ZrCl 4Material is incorporated into electrolyzer 1.Purifying compartment 2, oxidation compartment 3 and electrorefining pond 4 basically can with aforementioned figures in identical, and have and the aforementioned figures identical functions.Generate very pure zirconium at negative electrode.
Fig. 5 schematically shows the operational path of another production purifying zirconium.In this embodiment, Zr/Hf resistates material is incorporated into dissolving compartment 6.Resistates is dissolved in the mixture of being made up of liquid copper and/or tin and other possible precious metal in the dissolving compartment 1.To be incorporated into purifying compartment 2 from the molten metal in the dissolving compartment 1.Purifying compartment 2, oxidation compartment 3 and electrorefining pond 4 basically can with aforementioned figures in identical, and have and the aforementioned figures identical functions.Generate very pure zirconium at negative electrode.
Fig. 6 schematically shows the operational path of another production purifying zirconium.In this embodiment, Zr/Hf resistates material is incorporated into dissolving compartment 6.Resistates is dissolved in the mixture of being made up of liquid copper and/or tin and other possible precious metal in the dissolving compartment 1.To be incorporated into purifying compartment 2 from the molten metal in the dissolving compartment 1.Purifying compartment 2, oxidation compartment 3 and chlorination 5 basically can with aforementioned figures in identical, and have and the aforementioned figures identical functions.Final product is very pure ZrCl 4, ZrCl 4Can generate very pure zirconium through gram Raul method.
At Fig. 1 in Fig. 6; If desired; The liquid metal mixture that can the technology through purifying compartment 2 be obtained carries out second technology subsequently, and this second technology is identical with Fig. 1 technology in the purifying compartment 2 in Fig. 6 basically, and purpose is further to improve the purity of zirconium.
Fig. 7 schematically shows another purifying HfO 2Operational path, HfO wherein 2Be to generate to the technology described in Fig. 6 according to Fig. 1 to obtain.First electrolyzer 1, purifying compartment 2 and electrorefining pond 4 basically can with aforementioned figures in identical, and have and the aforementioned figures identical functions.Have another electrolyzer 7, the class of operation of the electrolyzer 7 and first electrolyzer seemingly, still, the molten metal bath that electrolyzer 7 generates flow into another electrorefining pond 8, thereby generates very pure Hf at negative electrode.
Fig. 8 schematically shows another purifying HfO 2Operational path, HfO wherein 2Be to generate to the technology described in Fig. 6 according to Fig. 1 to obtain.Electrolyzer 1, purifying compartment 2, chlorination 5 and another electrolyzer 7 basically can with aforementioned figures in identical, and have and the aforementioned figures identical functions.Generate very pure HfCl with another chlorinating step 9 4, HfCl 4Can generate very pure hafnium through gram Raul method.
According to the present invention, the liquid non-pure metal mixture by Zr/Hf and common Cu and/or Sn form can comprise that other precious metal is to carry out purification step 2.Molten metal solutions contacts under the temperature of (700 ℃ according to appointment) between 500 ℃ and 1250 ℃ with fused salt mixture usually, and fused salt mixture contains by alkaline earth metal chloride and/or alkali metal chloride and metal chloride M 3Z is (such as CuCl 2) mixture formed.Do not use CuCl 2Perhaps CuCl, and be to use SnCl 2The perhaps mixture of these compounds.Preferably, purification step 2 carries out under protective atmosphere, particularly under inert gas atmosphere (just, not can with or the gas that can not react with any metal that exists or salt basically), such as rare gas element, such as argon gas.
The kinetics of Hf from the molten metal phase transition to salt face is very fast, causes the biphase equilibrium composition almost to be confirmed in moment.
Have been found that Zr/Hf in the liquid metal mixture that obtains through purification step 2 than improving greatly, will exceed much than what estimate based on the difference of the small electronegativity of Hf (1.3 Pauling) and Zr (1.33 Pauling).
In one embodiment, the mixture that contains hafnium and zirconium in the technology of the present invention obtains from electrolysis process, ZrO in this electrolysis process 2And HfO 2Contact with electrolytic solution.This electrolytic solution contacts with negative electrode so that electric charge can shift.This negative electrode is preferably the molten metal negative electrode.Electrolytic solution also carries out mass exchange and electrically contacts with anode, is preferably graphite anode.Poor through between anode and negative electrode, applying proper voltage, can produce Zr and Hf metal.
In another embodiment, the mixtures of materials that contains zirconium and hafnium also can originate from non-pure ZrCl 4, just contain HfCl 4ZrCl 4
Product from refinement step 2 is molten metal bath and fusion saline solution, and both can be further processed, such as, it is carried out another refinement step 2.
The fused salt mixture that obtains can be by optionally oxidation.The oxidation products that contains hafnium and zirconium can further be processed with standard technique.
Can use the electrorefining pond to obtain high-purity Zr product.In electrorefining step 3, have zirconium, copper and/or the tin of high density and the liquid metal mixture of other possible precious metal and be used as liquid anodes.Can be with the fused salt mixture that contains the mixture of forming by alkaline earth metal chloride and/or alkali metal chloride as electrolytic solution.When electrorefining technology began, electrolytic solution must contain some zirconium chlorides usually.The starting sheet that can use solid-state zirconium is as negative electrode.Therefore, the electrorefining pond has from bottom to top: the fusion zirconium that contains the possible precious metal of copper and/or tin and other as anodic; As the adding of electrolytic solution the mixture of forming by fusion alkaline earth metal chloride and/or alkali metal chloride of zirconium chloride; Starting sheet as the solid zirconium of negative electrode.At the molten metal anode, zirconium atom is oxidized to zirconium ion.And at solid state cathode, zirconium ion is reduced to the zirconium metal.
During high temperature, at metal especially liquid metal place, exchange current density is huge.Because big exchange current density during high temperature, think at the anode place not or almost do not have a Zr 3+Perhaps Zr 4+Generate.When the potential difference that applies between anode and negative electrode when not being very high, copper and/or tin and other possible precious metal can be at anode dissolutions, because selected copper and other metal do not have zirconium active.
When the potential difference that applies between anode and negative electrode when not being very high, can not be reduced to corresponding metal at negative electrode from the basic metal and the alkaline earth metal chloride of electrolytic solution, because basic metal and earth alkali metal are active more than zirconium.The zirconium that negative electrode produces in said electrorefining technology can fully satisfy the requirement that nuclear industry is used.Because zirconium is in the continuous generation of negative electrode, the distance between anode and the negative electrode can reduce, and causes strength of current to increase steadily.
In electrorefining technology,, can make current density keep constant through controllably upwards promoting negative electrode.In this technology, in fact, negative electrode is upwards drawn from electrolytic solution lentamente.The ohmic resistance of electrolytic solution combines with the current density that applies and has caused the generation of heat.Utilize the good geometry in electrorefining pond, almost just can make the electrorefining pond keep temperature required without any need for extra energy.Usually, temperature is between 500 ℃ to 1250 ℃, and this temperature depends on the accurate composition and the liquid anodes of liquid electrolyte.Possible impurity in the liquid anodic material can period be removed, such as, through selective oxidation, controlled chilling or other treatment process.
In addition, having zirconium, copper and/or the tin of high density and the liquid metal mixture of other possible precious metal contacts with chlorine.Preferably, zirconium is converted into gaseous state ZrCl 4Through standard technique, can distill gaseous state ZrCl 4Carrying out other purifying, and produce zirconium through gram Raul method with low hafnium content as material.In gram Raul method, with suitable metal, such as magnesium, with ZrCl 4Reduction becomes Zr.
The material that is used for technology of the present invention, the metal mixture that promptly contains Zr and Hf can obtain from a lot of sources.Such as, can be from ZrO 2HfO (is contained in the ore deposit 2), ZrSiO 4HfSiO (is contained in the ore deposit 4) and composition thereof obtain.
Such as, can use electrolyzer, wherein M 1And M 2The liquid metal mixture, such as, copper and tin and other possible precious metal can be used as negative electrode, can adopt melting salt, preferred CaCl 2, as electrolytic solution, if possible, add alkali metal chloride, also can be to wherein adding number of C aO when technology begins.Graphite is as anode.
Usually between 500 ℃ and 1250 ℃, this temperature depends on the accurate composition and the liquid anodes of liquid electrolyte to temperature.When the potential difference that applies between anode and the negative electrode is enough big,, make Ca because CaO has high-dissolvability in electrolytic solution 2+Therefore ion is reduced to calcium metal at negative electrode, uses CaO but not uses ZrO separately 2The calcium metal that generates is dissolved in the molten metal mixture, also is dissolved in the melting salt.At anode, reaction: O below taking place 2-+ C → CO+2e.
The CO that generates is as gas evolution.Graphite anode is by slow consumption, and is replaced every now and then.Subsequently, make molten metal mixture and fused salt mixture and the solid ZrO that is dissolved with calcium metal 2The ore deposit contacts.Reaction: ZrO below taking place 2+ 2Ca → 2CaO+Zr.Usually, ZrO 2Some HfO are contained in the ore deposit 2Be present in ZrO 2HfO in the ore deposit 2Character and ZrO 2Consistent.The zirconium that generates is dissolved in liquid metal mutually with hafnium.The liquid metal mixture that obtains can be used as the separating technology that material is used for addressing claim 1.
Behind calcium reduction, ZrO 2Pollutent in the ore deposit also can finish being made up of in the liquid form mixt copper and/or tin and other possible precious metal.Yet except hafnium, other metal does not all have zirconium active, and therefore, other metal can not produce any immediate problem in electrorefining technology.At above-mentioned ZrO 2The CaO that generates in the reaction of ore deposit is dissolved in by fusion CaCl 2In the mixture that/CaO and possible alkali metal chloride are formed.Preferably, whole equipment place rare gas element, under the little high pressure such as argon gas, to prevent air infiltration.Except ZrO 2ZrSiO also can be used in the ore deposit 4The ore deposit.But using ZrSiO 4The time, the silicon that adopts calcium generation reduction reaction to produce is dissolved in the liquid metal mixture.
In addition, the mixtures of materials that contains zirconium and hafnium also can originate from pure relatively ZrCl through electrolyzer 4(just, mainly comprise ZrCl 4, HfCl 4And other few relatively impurity such as the mixture of titanium).
In this embodiment, above-mentioned two kinds of metal M 1And M 2Liquid form mixt as negative electrode, wherein contain other possible precious metal.The preferred CaCl of melting salt 2As electrolytic solution.Preferably, possibly there is alkali metal chloride in the melting salt.Graphite is as anode.Be not limited to theory constraint, think when the potential difference that applies between anode and the negative electrode is enough big, at negative electrode Ca 2+Can be reduced into and be calcium.
The calcium metal that generates at negative electrode is dissolved in the mixture of being made up of liquid copper and/or tin and other possible precious metal, also is dissolved in by CaCl 2In the molten mixture of forming with possible alkali metal chloride.Yet when not having calcium as intermediate product, this technology can go on too.
Reaction: 2Cl below anode takes place -→ Cl 2+ 2e.
The Cl that generates 2Overflow with gas form.According to prior art, can be from ZrO 2Ore deposit or ZrSiO 4The ore deposit produces required ZrCl 4
Subsequently, make molten metal mixture and fused salt mixture and gaseous state ZrCl 4Contact.Reaction: ZrCl below taking place 4+ 2Ca → Zr+2CaCl 2And ZrCl 4In HfCl 4Same reaction also takes place.According to the present invention, except gaseous state ZrCl 4, also can use the solid-state ZrCl that is dissolved in the melting salt 2
Zirconium that generates and hafnium are dissolved in the liquid form mixt of being made up of copper and/or tin and other possible precious metal, and it can be used as material and is used for refinery practice and produces zirconium, as stated.
In above-mentioned reaction, the CaCl of generation 2With by CaCl 2The molten mixture of forming with possible alkali metal chloride mixes mutually.The temperature of carrying out whole technology is between 500 ℃ to 1200 ℃, and this temperature depends on the accurate composition and the liquid anodes of liquid electrolyte.In addition, whole equipment should place rare gas element, under the little high pressure such as argon gas, to prevent air infiltration.
Alternatively, the material in the technology of the present invention also can be provided by the Zr/Hf resistates.
Resistates can be dissolved in the above-mentioned liquid metal mixture simply, and the mixture that contains hafnium and zirconium that obtains can be processed, as stated.
Considerable advantage of the present invention is from Zr, to remove Hf efficiently.Embodiment through following further describes the present invention, and said embodiment is used for limiting scope of the present invention.
Embodiment
Balance test
Starting material
Carry out balance test with the laboratory-scale chemical.Metal-powder: Zr, Hf, Cu and Sn, its purity is higher than 99.9%.Hydrochloride: CuCl 2, NaCl and CaCl 2, its purity is 99.9%.
The preparation of mother alloy and salt
Under pure argon atmosphere, adopt pre-melt salt NaCl-CaCl in the time of 850 ℃ 2Mixture prepares Zr and the Hf that contains the Sn-Cu mother alloy in alumina crucible, duration 6 hours.Main salt mixture is with NaCl, CaCl 2And CuCl 2Powdered preparation.After the mixing, at 750 ℃ to salt mixture fusion 4 hours, cool to room temperature then.CuCl in the main salt 2Content is 2.956wt%.
Balance test
For balance test, will put in the alumina crucible by definite mixture that main salt and mother alloy are formed, and place the carbolite resistance tube furnace under the pure argon atmosphere.
Principal reaction is:
[Hf] Metal+ 2 (CuCl 2) Salt=2 [Cu] Metal+ (HfCl 4) Salt
In theory, the 1g Hf reaction with in the metallographic phase needs 1.596g CuCl 2Balance test is carried out under different control conditions.Having found influences salt and two principal elements of alloy reaction equilibrated are temperature (750 ℃ and 850 ℃), and the CuCl that is added in the salt 2Stoichiometric ratio (1,2 and 3) to the Hf in the alloy.Starting time kept 4 hours.After the balance test, analyze the composition of metallographic phase with inductively coupled plasma (ICP) spectrometer.
Result and discussion
Table 1 has been listed the condition and the experimental result of balance test.Balance test has provided very positive result, like Fig. 9 and shown in Figure 10.Under 850 ℃, CuCl 2The stoichiometric ratio of/Hf equals at 1 o'clock, and the clearance of Hf changes to 99.9% from 76.0% among the Zr, and Hf/Zr is than reducing to 0.0002 from 0.128, and removing the factor is 640 (0.128/0.0002=640).
Table 1: (response sample is with the CuCl in temperature of reaction and the salt for experiment condition and result 2Stoichiometric ratio name to the Hf in the mother alloy)
Figure BDA0000118293560000101
In the metallographic phase of reaction, the content of Sn and Cu does not have noticeable change.Yet, at 850 ℃, the CuCl that is added in the main salt 2During to the stoichiometric ratio S/M=1 of Hf in the mother alloy, the clearance of Hf is up to 99.9% among the Zr.Figure 10 shows when 750 ℃ and 850 ℃, the CuCl that adds in the salt 2Different chemical metering than and temperature all the Hf clearance is had significant positively effect.In addition, advance icp analysis based on the salt sample to reaction, the Cu content in the salt of reaction back is very low usually.
Above-mentioned experimental result and observation have proved the technical feasibility of production of the present invention and refinery practice.

Claims (15)

1. a separation comprises the technology of the mixture of zirconium and hafnium, it is characterized in that, may further comprise the steps:
The molten metal phase is provided, and said molten metal comprises first metal M mutually 1And second metal M 2
The fusion salt face is provided, and said fusion salt face comprises at least a metal halide M 3Z and one or more metal M 4One or more salt, wherein, M 3Be the metal of positive polarity less than zirconium and hafnium, M 4Metal for first family in the periodictable or second family;
The said mixture that comprises hafnium and zirconium is joined said molten metal mutually; And
Make said molten metal mutually and said fusion salt face contact, thus at least the said hafnium of part from said molten metal phase transition to said fusion salt face.
2. technology according to claim 1 is characterized in that, said M 1With said M 3In at least a portion be identical metal.
3. according to the described technology of aforementioned arbitrary claim, it is characterized in that said M 3With said M 3In at least a portion be identical metal.
4. according to the described technology of aforementioned arbitrary claim, it is characterized in that, do not add zirconates in the said fusion salt face, preferably, said fusion salt face does not contain zirconates basically.
5. according to the described technology of aforementioned arbitrary claim, it is characterized in that said M 1With said M 2Be independently selected from respectively in Cu, Sn, Ag, Sb, Zn, Pb, Bi, Fe, Ni, Cd, Si and Co, preferably, said M 2For reducing said M 1The metal of fusing point.
6. according to the described technology of aforementioned arbitrary claim, it is characterized in that said M 1Be Cu, said M 2Be Sn.
7. according to the described technology of aforementioned arbitrary claim, it is characterized in that said M 4Salt be halogenide or halid mixture.
8. according to the described technology of aforementioned arbitrary claim, it is characterized in that said M 4Be selected from Na, K, Ba, Sr and Ca, preferably, said M 4Salt be the muriate of Ca, Na and/or K or the mixture of fluorochemical, be preferably CaCl 2
9. according to the described technology of aforementioned arbitrary claim, it is characterized in that the said metal of said molten metal in mutually exists with mutual mol ratio, basic and said metal M 3Mutual mol ratio in said fusion salt face is identical.
10. according to the described technology of aforementioned arbitrary claim, it is characterized in that, join the said M in the said fusion salt face 3The amount of Z is with proportional from the said amount that comprises the hafnium of removing the mixture of zirconium and hafnium.
11. according to the described technology of aforementioned arbitrary claim, it is characterized in that the temperature of said molten metal and said melting salt remains between 500 ℃ to 1250 ℃, be preferably between 700 ℃ to 1000 ℃.
12., it is characterized in that the said mixture that comprises hafnium and zirconium is obtained by electrolysis process according to the described technology of aforementioned arbitrary claim, zirconium hafnium source contacts with electrolytic solution in said electrolysis process, said zirconium hafnium source is selected from contains HfO 2ZrO 2, contain HfSiO 4ZrSiO 4And composition thereof; Said electrolytic solution and molten metal negative electrode are in contact with one another with the mode of electricity and mass exchange; And said electrolytic solution and anode are in contact with one another with the mode of electricity and mass exchange; Thus, the zirconium ion in the said zirconium hafnium source and hafnium ion are reduced to metal zirconium with hafnium and be transferred to said molten metal mutually, and the said molten metal of part is transferred so that the said mixture that comprises hafnium and zirconium to be provided mutually at least.
13., it is characterized in that the said mixture that comprises hafnium and zirconium is obtained by electrolysis process, in said electrolysis process, contains HfCl according to the described technology of aforementioned arbitrary claim 4ZrCl 4Be added in the electrolyzer.
14. according to the described technology of aforementioned arbitrary claim; It is characterized in that the said molten metal of part is transferred and gets into refinement step mutually at least, wherein; Said molten metal forms anode mutually and contacts with refining electrolytic solution; Said refining electrolytic solution contacts with the cathodic electricity that contains metal zirconium, and said refining electrolytic solution and said molten metal mass exchange take place mutually and electrically contact, and metal zirconium deposits on said negative electrode thus.
15., it is characterized in that the said molten metal of part is transferred and gets into refinement step is rich in hafnium with production stream mutually at least according to the described technology of aforementioned arbitrary claim.
CN201080025766.5A 2009-05-15 2010-05-17 Process for separating hafnium and zirconium Expired - Fee Related CN102459665B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP09160442 2009-05-15
EP09160442.1 2009-05-15
PCT/NL2010/050289 WO2010131970A1 (en) 2009-05-15 2010-05-17 Process for separating hafnium and zirconium

Publications (2)

Publication Number Publication Date
CN102459665A true CN102459665A (en) 2012-05-16
CN102459665B CN102459665B (en) 2013-08-28

Family

ID=41168575

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201080025766.5A Expired - Fee Related CN102459665B (en) 2009-05-15 2010-05-17 Process for separating hafnium and zirconium

Country Status (2)

Country Link
CN (1) CN102459665B (en)
WO (1) WO2010131970A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115305514A (en) * 2021-05-08 2022-11-08 中南大学 Method for refining hafnium through molten salt electrolysis

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115305515A (en) * 2021-05-08 2022-11-08 郑州大学 Electrochemical method for zirconium-hafnium separation

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4021531A (en) * 1973-11-14 1977-05-03 Ugine Aciers Process for the separation of zirconium and hafnium tetrachlorides from mixtures thereof
US4072506A (en) * 1975-10-17 1978-02-07 Teledyne Industries, Inc. Method of separating hafnium from zirconium
US4749448A (en) * 1986-12-18 1988-06-07 Westinghouse Electric Corp. Zirconium and hafnium tetrachloride separation by extractive distillation with molten zinc chloride calcium and/or magnesium chloride solvent
CN1052148A (en) * 1989-11-29 1991-06-12 泰利达因工业有限公司 High-purity zirconium and Hf metals and method for making thereof
CN1993295A (en) * 2004-07-09 2007-07-04 欧洲塞扎斯“锆”公司 Method for separating and purifying hafnium and zirconium

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4021531A (en) * 1973-11-14 1977-05-03 Ugine Aciers Process for the separation of zirconium and hafnium tetrachlorides from mixtures thereof
US4072506A (en) * 1975-10-17 1978-02-07 Teledyne Industries, Inc. Method of separating hafnium from zirconium
US4749448A (en) * 1986-12-18 1988-06-07 Westinghouse Electric Corp. Zirconium and hafnium tetrachloride separation by extractive distillation with molten zinc chloride calcium and/or magnesium chloride solvent
CN1052148A (en) * 1989-11-29 1991-06-12 泰利达因工业有限公司 High-purity zirconium and Hf metals and method for making thereof
CN1993295A (en) * 2004-07-09 2007-07-04 欧洲塞扎斯“锆”公司 Method for separating and purifying hafnium and zirconium

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115305514A (en) * 2021-05-08 2022-11-08 中南大学 Method for refining hafnium through molten salt electrolysis
CN115305514B (en) * 2021-05-08 2023-11-17 中南大学 Method for refining hafnium through molten salt electrolysis

Also Published As

Publication number Publication date
WO2010131970A1 (en) 2010-11-18
CN102459665B (en) 2013-08-28

Similar Documents

Publication Publication Date Title
Mohandas et al. FFC Cambridge process and removal of oxygen from metal-oxygen systems by molten salt electrolysis: an overview
Fray et al. Reduction of titanium and other metal oxides using electrodeoxidation
JP5719972B2 (en) Metal recovery method and electrolysis apparatus for performing the method
NZ508686A (en) Removal of oxygen from metal oxides and solid soultions by electrolysis in a fused salt
WO2003076690A1 (en) Reduction of metal oxides in an electrolytic cell
JP2008531854A (en) Method and apparatus for removing oxygen from a compound or metal
CN113981491B (en) Method for preparing metallic beryllium by low-temperature molten salt electrolysis
KR101793471B1 (en) Refining Method of Metal Using Electroreduction and Electrorefining process
CN104561550B (en) A kind of method that aluminothermic reduction ilmenite prepares Al Ti Fe alloys in ice crystal ground mass fused salt
WO2004033760A2 (en) Electrochemical reduction of metal oxides
US20100006448A1 (en) Method, apparatus and means for production of metals in a molten salt electrolyte
JP3718691B2 (en) Titanium production method, pure metal production method, and pure metal production apparatus
Li et al. Preparation of zirconium metal by electrolysis
Akolkar Perspective—is sustainable electrowinning of neodymium metal achievable?
CN102459665B (en) Process for separating hafnium and zirconium
CN102433572A (en) Production process for preparing magnesium-gadolinium alloy by fused salt electrolysis method
JP2012136766A (en) Method for producing metal by electrolysis
JP6502805B2 (en) Method of manufacturing rare earth metal
CN113279022B (en) Reducing molten salt medium and preparation method thereof
CN108018465A (en) A kind of method that aluminothermic reduction ilmenite prepares Al-Ti-Fe alloys in ice crystal ground mass fused salt
CN115305517A (en) Method for preparing metal titanium by molten salt electrolysis
JP6234160B2 (en) Method for producing rare earth metal
WO2023276440A1 (en) Method for manufacturing titanium-containing electrodeposit, and metal titanium electrodeposit
CN114016083B (en) Method for regenerating alkali metal reducing agent in process of preparing metal by alkali metal thermal reduction of metal oxide
Shamsuddin Electrometallurgy

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
ASS Succession or assignment of patent right

Owner name: ZR-HF-TI METALLURGY LTD.

Free format text: FORMER OWNER: TECHNISCHE UNIVERSITEIT DELFT

Effective date: 20120712

C41 Transfer of patent application or patent right or utility model
TA01 Transfer of patent application right

Effective date of registration: 20120712

Address after: Holland Hague

Applicant after: Univ Delft Tech

Address before: Delft

Applicant before: Technische Universiteit Delft

C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20130828

Termination date: 20170517

CF01 Termination of patent right due to non-payment of annual fee