TW201006964A - Method - Google Patents

Abstract

The present invention relates to a method for determining the extent of electrochemical extraction of a metal (M) from a metal (M) oxide caused by a voltage applied between a cathode comprising (or consisting essentially of) or in contact with the metal (M) oxide and an inert metal alloy anode in an oxygen-dissolving molten electrolyte.

Description

201006964 VI. Description of the Invention: [Technical Field to Which the Invention Is Applicable] [0001] The present invention relates to a method for determining a cathode that is applied to a metal comprising (or substantially consisting of) or contacting the metal (M) oxide And a voltage between one of the inert metal alloy anodes in the dissolved oxygen molten electrolyte, and one metal (M) is electrochemically extracted from a metal (M) oxide. [Prior Art] [0002] It is known that, in general, a range of metal (M) is electrochemically extracted from a metal (M) oxide in a molten oxygen molten electrolyte extract, Measurements are taken after the reaction is completed, and this measurement is mostly by (for example) microsl analysis (microsl rue t analysis) (for example, X-ray diffraction), or a weight loss technique (weight loss) Technique). However, none of these techniques provide an immediate assessment of the extent of the extract that has been produced while the extraction is ongoing. / ' ¥

^ [0003] The conditions for chemically extracting a metal (M) from a metal (M) oxide in a dissolved oxygen electrolyte are quite severe and, usually, near the height at which the extraction process is completed. Under reducing conditions, the extraction procedure may result in the formation of aggressive, or corrosive by-products that are not conducive to the use of sensitive instruments in situ. [0004] The basis of the present invention is that a current versus time diagram is generally effective and reproducibly characterized by the progression of electrochemical extraction in a dissolved oxygen molten electrolyte, and in particular, the current versus time graph. Available 0981216&2 Form No. A0101 Page 3 of 35 pages 0893285549-0 201006964 The range of mosquito extracts that are used to instantly convert while the extraction is in progress. SUMMARY OF THE INVENTION In the concept of the first aspect of the present invention, a method is provided for determining whether - including a range of a metal (M) that is applied between a cathode of a metal (4) oxide and an inert metal alloy anode in a dissolved oxygen-dissolved electrolyte, and electrochemically extracted from the metal (4) oxide, The method comprises the following steps: (a) measuring the current between the cathode and the inert metal alloy during a short period; a friend: . . . circle m (b) making the cathode and the情 'έ金' belongs to 佥阳槿, a current concealment during a short period of time from the metal (() oxide electrochemically extracted from the range of the metal (Μ) produces a correlation β It is possible to determine the range of electrochemical extraction in an instant, and the gif ifr ' ft ιΠ' system of the present invention has made it impossible to achieve the electricity in the present 无-free ϋ electrolyte. a ^ ] \ Range control during chemical extraction is possible . Step (a) may be carried out in a discontinuous or continuous manner (e.g., to produce a current versus time graph), and preferably step (a) is carried out in a continuous manner. Preferably, the current between the cathode and the inert metal alloy anode during the short range includes a turning point, followed by a current swell after the turning point, and this is due to the use of the utilization range. The result of the inert alloy anode which is quite useful in the measurement is β 098121662 Form No. 1010101 Page 4 / Total 35 Page 0983285549-0 201006964 [0009] Preferably, the cathode and the inert metal alloy anode are in the short range This current during the period is substantially as exemplified in Figure 2 below. [0013] [0013] In step (b), the characteristic of the current between the cathode and the inert metal alloy anode during the transient range may be a quantitative characteristic. . The amount of the current between the cathode and the inert metal alloy anode during the short range may be characterized by a turning point, the amount of the current between the cathode and the inert metal alloy anode during the short range Or a current other than a turning point (eg, a predetermined amount), the amount of the current between the cathode and the inert metal alloy anode during the short range may also be that the current is increasing. Situation (for example, a predetermined amount). In step (b), the characteristic of the current between the cathode and the inert metal alloy anode during the short range may be a quantity of quant i tative characteri st i c . Preferably, the amount of features is different < a turning point of the current during the short range. [0014] The use of an amount of the current different from the inflection point is more advantageous for utilizing a swell caused by the use of the inert alloy anode, wherein the amount of the characteristic different from the turning point has a height Time correlation, and the correct measurement of this current is to help to accurately determine the range of the metal (M) that is electrochemically extracted from the metal (M) oxide. For example, it is possible to determine the metal from the M) An extraction rate (%) of the metal of the oxide (098121662 Form No. A0101, page 5/35 pages 0893285549-0 201006964), with high accuracy. [0015] Preferably, in the step (b), the amount of the current is characterized by the measured current outside a turning point of the current during the short range, particularly preferably Yes, the step (b) includes: correlating the measured current with the extraction rate (%) of the metal (Μ) from the metal (M) telluride, or alternatively, The measured current is related to the oxygen content of the metal (Μ). Preferably, the amount of current is characterized by a critical current other than a turning point of the current during the short range. [0017] Particularly preferably, the method further comprises the step of: (c) terminating the electrochemical reduction upon reaching the critical current. .

[0018] Particularly preferably, the step (b) comprises: bringing the critical current to - before the formation of unwanted by-products (eg, potentially toxic, or gaseous by-products that are harmful to the environment, eg, chlorine) An extraction range is relevant. [0019] Particularly preferably, the step (b) comprises correlating the critical current with an extraction range prior to the onset of a corrosive condition (e.g., a cathodic corrosion condition). [0020] Particularly preferably, the step (b) comprises correlating the critical current with a target extraction rate (%) of the metal (M) from the metal (M) oxide. 5%以上或以上。 [0021] The target extraction rate is generally 99%, or higher, preferably, 99.5%, or higher. 0983285549-0 098121662 Form No. A0101 Page 6 of 35201006964 阙Specially good is 'This (4)(b) includes: making the secret current related to the metal (M)-target oxygen content, where The target oxygen content is generally less than 2500 ppm 〇 2 (metal (μ) weight), preferably less than 1500 ppm 〇 2 (metal (M) weight). [0023] This characteristic of the current during the short period of the step (b) + 'the cathode and the inert metal alloy anode may also be related to the quality of the metal electrochemically extracted from the metal (M) oxide. The range above. [0025] [0026] The quality of the metal (M) electrochemically extracted from the metal (M) oxide may range from before the formation of the sonar product is required, or the corrosion condition is not required. An extraction range before the onset of occurrence in the step (b), the characteristic of the current between the anodes of the alloy at the ephemeral range may also be related to the electrochemical extraction of the metal from the metal (M) oxide. The quality of the scope. “ "π, Prooertv The metal (M) from the metal (M) oxide may be of a quality range of an extraction rate (%) of the metal (μ) from the metal (M) oxide, metal An oxygen content of (M), a target extraction ratio (%) of the metal (μ) from the metal (M) oxide, and a target oxygen content of the metal (M). [0027] In a preferred embodiment In the example, the metal (M) is Ti〇2, and the molten electrolyte contains calcium carbonate (CaCl2), and the electrochemical extraction is carried out in the presence of an alkali metal (Ma) oxide. [0028] The method of the present invention is carried out at a high temperature, generally in the range of 600 098121662 Form No. A0101 Page 7 / Total 35 Page 0893285549-0 201006964 -1 000 ° C, preferably at 850 In the method of the present invention, the transient range may be less than 20 hours, preferably less than 10 hours (for example, 8 hours), particularly preferably, less than 4 hours. [0030] In general, the voltage will be less than the metal in the molten electrolyte. Electric potential (discharge potential), for example, the voltage may be less than 3. 5 V (e.g., about 3. 1 V).

[0031] In a preferred embodiment, the method of the invention is practiced in an oxygen-free atmosphere (eg, an inert atmosphere, such as argon 1).

[0032] The cathode and the electrochemical cell to which the one or more inert metal alloy anodes belong may be directly calibrated to obtain a characteristic of the current between the cathode and the inert metal alloy anode and from the metal ( M) a relationship between the range of the metal (M) by electrochemical extraction of the oxide, and for the determination, the range of electrochemical extraction may be by conventional techniques such as microstructure analysis or by measurement Weight loss is measured. [0033] In a preferred embodiment, the electrochemical extraction will be in an alkali metal (

Ma) is carried out in the presence of an oxide, wherein the metal (Ma) oxide may be a caesium, a rubidium, a lithium, a sodium, or a potassium oxide. Preferably, the metal (Ma) oxide is a clock, nano, or potassium oxide, and particularly preferably, the alkali metal (Ma) oxide is oxygen 098121662 Form No. A0101 Page 8 of 35 0983285549-0 201006964 Potassium. [0036] [0038] [0038] 098121662 The metal (Ma) oxide may be an additive or may be dissociated into the alkali metal (Ma) oxide The alkali metal (Ma) salt is formed by dissociation from the original. Preferably, the alkali metal (Ma) oxide is derived from the alkali metal (Ma) oxide and a metal (M") metallization (M). Forming the alkali metal (Ma) metallization (M) phase in one reaction is particularly preferably, the metal (M") metallization (M) phase is a solid phase, and particularly preferably, the metal M,,) The metallization (M) phase is a stable perovskite (or perovskite-type) phase, wherein, preferably, the M" system is a soil tester. Particularly preferably, the most ruthless is calcium. _ 广. · Preferably, the oxygen diffusion rate in the alkali metal (Ma) metallization (M) phase is higher than that in the metal (Μ) ") The diffusivity of oxygen in the gold compound (Μ) phase" rel household, preferably, the alkali metal preparation cold (Μ) phase is a liquid, and preferably, the gold test i-( One species (M) phase Is a transition phase. In a preferred embodiment, the alkali metal (Ma) oxide is an additive. The metal (Ma) oxide can be phased with the metal (M) oxide in the cathode. Mixing (or contacting) The alkali metal (Ma) oxide and the metal (M) oxide may form a self-supporting mixture (eg, a pellet, a slab, Sheet (form number A0101, page 9/35 pages 0893285549-0 201006964 sheet), wire, foil, basket, or tube, where the self-supply The mixture may be a cathode or may be in contact with the cathode. [0042] The alkali metal (Ma) oxide may exhibit a trace amount in the self-feeding mixture. Preferably, it is more than 5% by weight, particularly preferably more than 10% by weight, more preferably more than 20% by weight, and further preferably, the alkali metal (Ma) oxide is The amount present in the self-feeding mixture may be between 10 and 70 wt%, particularly preferably Yes, between 20 and 50 wt%. In a preferred embodiment, the alkali metal (Ma) oxide is formed in situ by dissociating a dissociable alkali metal (Ma) salt, wherein The dissociable alkali metal (Ma) salt may be thermally dissociable. Preferably, the dissociable alkali metal (Ma) oxide may be mixed (or contacted) with the metal (M) oxide in the cathode. Particularly preferably, the mixture of the dissociable alkali metal (Ma) oxide and the metal (M) oxide is a self-supporting mixture (for example, a pellet, a slab) (slab), sheet, wire, foil, basket, or tube. The dissociable alkali metal (Ma) oxide may be present in the self-feeding mixture in an amount exceeding a trace amount, preferably, more than 5 wt%, particularly preferably, more than 10 wt%, more Preferably, it is more than 20% by weight. Further, preferably, the amount of the dissociable alkali metal (Ma) oxide present in the self-feeding mixture is between 10 098,121,662 Form No. A0101 Page 10 of 35 Page 0083285549-0 201006964 Between one wt% is particularly preferably between 20 and 50 wt%. [0043] Preferably, the dissociable metal (Ma) can be dissociated into one or more kinds of gases, and the gas species can be selected from the group consisting of water and carbon dioxide, and more advantageous. The dissociation of the alkali metal (Ma) salt into one or more species of gas can promote the occurrence of electrochemical reduction by forming a porous hole in the cathode, wherein the continuous formation of the pore system causes the molten electrolyte Species (eg, Ca 〇 and 气 [0044] gasification about (CaC12)) enable rapid transport, thus accelerating chemical reduction. The dissociable alkali metal (Ma) table can be ginseng gold. (*43) halide, carbonate, bicarbonate, hydrogen. sulfur: (hy4^〇ken sulph-ide) 'hydrogen sulfate (hydrogen sulphate), nitride, gas salt, or sulphate, preferably, the detachable metal Ua) salt is one heavy, sacrifice [0045] ❹ the catering meal (Ma) a salt of caesium, rubidium, chain (1 iVfll, sodium, or potassium), preferably, the dissociable alkali metal (Ma) salt is lithium or sodium. Or a potassium salt, particularly preferably, the dissociable alkali metal (Ma) salt is a potassium salt. [0046] In a preferred embodiment, the dissociable alkali metal (Ma) salt system It may be present together with a certain amount of endogenous hydroxide ions. In a preferred embodiment, the dissociable alkali metal (Ma) salt may be associated with an exogenous (ex〇gen〇us) nitrogen. Oxygen ions are present together. 098121662 Form No. A0101 Page 11 of 35 pages 0893285549-0 [0047] 201006964 Preferably, the exogenous hydrogen hydroxide ion is added by an assay Provided as a substance, wherein the alkaline additive may be an alkali metal hydroxide (eg, a clock, nano, or unloaded hydroxide), a metal hydride (eg, chain, sodium, or hydrazine) An argon compound or a soil metal hydroxide, and the test additive may be added to the dissolved oxygen molten electrolyte. [0048] The metal (M) may be an active metal element ( Reactive metal element) 'Semi-metal ele- [0049] ment, metal alloy 'or class, metal element: (metalloid element) ° per perovskite-type phase 'where' The solid-state stable titanium phase can be a soil test metal (for example, a 'about> metallization (M) phase. Preferably, the metal (M) ... :* - solid Dechu perovskite (Per solution) Medium-shaped I-type perovskite type [0050] 098121662 The metal (M) can be a group of metals, including: II Group A metal '11丨A metal-IV IV group metal, B long:::: : fi WT? The transition metal, the 靡 master tastes 'to squabble|. Preferably, the metal (M) can be one or more Metals selected from the following groups, including: Qian, Ming, Meng, Xu, IV Group B transition metal 'V β group transition metal' VI Β group transition metal, VII Β group of excessive metal ' VIII Β group transition metal, Elements, radiating elements, and alloys thereof. Particularly preferably, the metal (Μ) may be one or more metals selected from the group consisting of: IV lan transition metal, V 过渡 transition metal 'VI Β transition metal, VI11 Β transition Metal, radiation element 'and its alloys. More preferably, the metal (Μ) may be one or more selected from the group group number Α 101 0101, page 12 / total 35 pages 098 201006964 [0051] ❹ [0054] ❹ [0054] Metals including: titanium (Ti), sharp (Nb), group (Ta), shaft (U), stove (Th), chromium (Cr), iron (Fe), steel (steel), and zirconium (Zr And, more particularly preferably, one or more metals selected from the group consisting of titanium (Ti), niobium (Nb), tantalum (Ta), and niobium (Zr), and most The good place is titanium. During electrochemical extraction, it is advantageous that titanium forms sub-oxides (eg, Magneli phases, titanium oxide, and titanium), which is beneficial for A sudden rise in current is caused beyond a turning point. The alkali metal (Ma) metallization (M) phase may be Ma2M〇3, or Sia4M〇4, preferably, Ma4M〇4, for example, when tantalum is titanium, the preferred phase is M'TiO ,. 4 4 The metal (M) oxide may serve as a cathode, or the metal (M) oxide and the alkali metal (Ma) oxide, or the alkali gold which may be dissociated into the alkali metal (Ma) oxide: The mixture of the genus (Ma) salt may serve as a cathode, preferably the metal (M) oxide and the alkali metal (Ma) oxide, or the alkali metal which may be dissociated into the alkali metal (Ma) oxide ( A mixture of salts of Ma) acts as a cathode. Alternatively, alternatively, the metal (M) oxide may be implemented in contact with a cathode. In this embodiment, the metal (M) oxide may be mixed with the alkali metal (Ma) oxide, or with the alkali metal (Ma) salt dissociable into the alkali metal (Ma) oxide; or Alternatively, the metal (M) oxide may be in contact with the cathode in the electrolyte, the alkali metal (Ma) oxide, or the alkali metal may be dissociated (098121662 Form No. A0101, page 13 / 35 pages 0893285549-0 201006964 a) The alkali metal (Ma) salt of an oxide may be in contact with the cathode in the electrolyte, wherein the cathode may be a metal species, such as steel, which may be implemented in the form of a Cathode bath, crucible, or basket. [0055] The dissolved oxygen molten electrolyte may be (or include) a metal such as lithium, a bell, or a crucible (Cs), a soil (for example, magnesium, mum, sr), or strontium. a compound of (Ba), grammar, ming, or y (or a mixture thereof), preferably, the dissolved oxygen molten electrolyte comprises a compound of #5. [0056] The dissolved oxygen molten electrolyte may be (or comprising) hydrogen phosphate, dihydrogen phosphate, or monoterpene, preferably monohalide (eg, vapor, or fluoride), particularly Preferably, the monochloride; and the dissolved oxygen electrolyte may comprise calcium chloride (CaCl2) or cryolite. [0057] Preferably, the molten electrolyte comprises (eg The composition is substantially vaporized calcium (CaCI2), and particularly preferably, the molten electrolyte comprises calcium carbonate (CaCI2) and an alkali metal halide (preferably, a gasification), preferably gasification. Calcium (CaCI2) and potassium carbonate (KCI), or chlorinated #5 (CaCI2) and gasification A mixture of bells (LiCI). It is preferred to use an inert metal alloy anode that does not substantially react with oxygen, preferably an inert metal alloy anode that is substantially insoluble in the molten electrolyte. Preferably, the anode is composed of an alloy based on A-E-Cu, and the alloy includes an intermetallic compound having the following molecular formula (in- 098121662 Form No. A0101 Page 14 of 35 [0063] ter [0063] [0065] termetallic phase: A1 E Cu xyz where: E represents one or more metal elements; X series is between 1 and 5 An integer between them; y is an integer of 1, or 2; and z is an integer of 1, or 2. The alloy system based on A1_E-Cu may be substantially single-phase or multi-phase. Yes, the intermetallic phase is present in the AE-Cu based alloy in an amount of 50% by weight, or more (e.g., in the range of 50 to 99 wt%) * preferably The Al-E-Cu based alloy further includes a high temperature intermetallic phase of E and aluminum (ordered high-temperature inte) Rmetal 1ic phase ), particularly preferably A13E, of course, other intermetallic phases may also occur. In a preferred embodiment, the alloy system based on A1-E-Cu is substantially not There is CuAI2 because CuAI2 has a tendency to melt at high temperatures, and high temperature is a general configuration in the method according to the present invention, so 'preferably, CuAIg forms a complex. In a preferred embodiment, the Al-E-Cu based alloy system will fall on a region other than the low E content side of the A1 E and the ECi^i tie line (for example, falling on The combination of A1J and ECu is connected to the high E content side of the 3 4 junction. In a preferred embodiment, the alloy system based on A-E-Cu will be 098121662. Form No. A0101, page 15 / total 35 pages 0893285549-0 201006964 [0066] including an intermetallic compound phase in the combination A13E and ECu4i are connected on or near the line. In a preferred embodiment, the alloy system based on Al-E-Cu may fall in a region 〇L region other than the low E content side of the connecting line of A1 E and AlECu (for example, falling on the bond) The high E content side of the connecting line of A13E and A1ECu2). [0070] In a preferred embodiment, the Al-E-Cu based alloy system will include an intermetallic compound phase falling on the bonded A1E and AlECu. The link is on the line, or near the line. Q In a preferred embodiment, the Al-E-Cu based alloy system will fall on ruthenium, AlJJu, EAlCu. And a region other than the low E content side of the connecting line of the 114 phase (wherein the lanthanum is between Ai, Ti, and A1 Ti 6 L, having 3 at%, or less (for example, 2 - 3 at%) of the phase of Cu. In a preferred embodiment, the alloy system based on A-E-Cu will comprise an intermetallic compound phase falling on ruthenium, Al5E2Cu, EA1Cu2 and no- q ECu, the phase of the connection is on or near the line. 4 Preferably, the intermetallic compound is AlKE9Cu, particularly preferably DL, and the alloy based on A-E-Cu further comprises A13E. Yes, the intermetallic compound is EA1Cu2, and particularly preferably, the Al-E-Cu based alloy further comprises y5-ECu4. The anode may be homogenous, or partially homogenous, or non-homogenous. Al-E-Cu is composed of a base alloy. 098121662 Form No. A0101 Page 16 of 35 0983285549-0 [0072] 201006964 [0074] In general, the potential of E in the anode is higher than that of The potential in the molten electrode is low. In the preferred embodiment, the anode forms a purification layer (Pas_S1Vating layer), preferably, the passivation layer acts as an anode. In a preferred embodiment, E is a separate metal element 'and the individual metal element is preferably titanium. [0076] ❹ In the alternative to the preferred embodiment Wherein E is a plurality of (for example, two L, four, five, six, or seven) metal elements. In this embodiment, a first metal element is the first metal metal element of a metal element. Other metal elements in

The plurality of plural, each of the other metal elements may be present in a trace amount, each of the other metal elements may be a dopant, and each of the other metal elements may replace Ai, Cu, or the presence of such other metal elements, may change stability (eg, from 1200 ° C to 1400 ° C). - In a preferred embodiment, E is a pair of metallic elements. In this embodiment, a first metal element is preferably titanium. Generally, the first metal element of the pair of metal elements is substantially one of the second metal elements of the pair of metal elements. The content is higher (for example, about 9:1 by weight). In addition, the second metal element may be present in a trace amount, and the first metal element may be a dopant, and the second metal element may replace Al, Cu, Or the first metal element, in addition, the second metal 098121662 Form No. A0101 Page 17 of 35 pages 0893285549-0 201006964 [0078] The presence of an element can improve the high temperature stability of the alloy (for example, from 1200 ° C Up to 1400 ° C). Preferably, the pair of metal elements have a similar atomic radius, wherein 'preferably, the atomic radius of the second metal element is similar to the atomic radius of ^, preferably, the atom of the second metal element Half _ is like the atomic radius of A1. [0079] In a preferred embodiment, the 'E system is one or more selected from the group consisting of: Group B transition metal elements (eg, column-to-column transition metal elements), and lanthanides, Preferably, the E is - or a plurality of metals, particularly preferably - a plurality of U^, vu B or VII IB transition metals.

[0080] In a preferred embodiment, E is one or more metal elements having a valence of π in, iv, or v, preferably, the valence is π,

III, or IV

[0081] In a preferred embodiment, the metal, or a plurality of metal halogens selected from the group consisting of ruthenium (Ru), titanium (Ti), zirconium (Zr), and chromium (Cr) , niobium (Nb), vanadium (V), cobalt (c), button (Ta), iron (Fe) 'nickel (Ni), lanthanum (La) and manganese (Mn), and in a particularly preferred embodiment Among them, Ε is one or more metal elements selected from the group consisting of: titanium, iron, chromium, and recorded.

Preferably, the ruthenium may or may include a metal element capable of reducing the tendency of the CuA 12 to grain boundary segregation at high temperatures. In this embodiment, the form of the CuA j 2 098121662 can be lowered. No. A0101 Page 18 of 35 page 0893285549-0 [0082] 201006964 A metal element that tends to segregate toward a grain boundary at a high temperature (grain.b〇undary segrega_ ticm) may be a plurality of (for example, a pair of) metal elements. The second metal element, in addition, particularly preferably, E is or may include a metal element capable of forming a complex of CuA12 and is suitable for the surface element selected from the group of the lower layer. Including: iron, nickel, and chromium 'particularly, preferably, and iron, especially preferably, recorded. [0083] 较佳 is preferably ' Ε may or may include a metal element capable of reducing the dissolution tendency of the first metal lanthanum or Cu in the molten extractant' The metal element may be a plurality of (eg, a pair of) metal elements of the second precursor: a preferred metal element suitable for the group is selected from the group consisting of iron, nickel, cobalt, manganese, and Chromium, particularly preferably the following group, includes "·: iron and nickel (optionally with chromium). [0084] 较佳 Preferably, E, or the face wheel is integrated into the surface of the anode a metal element of a molten electrolyte, because the metal element is a gas-turning film, in this embodiment, the metal element may be a plurality of (for example, a pair of) metal elements. The second metal element, preferably a preferred metal element suitable for the group, is selected from the group consisting of ruthenium, iron, nickel, and chromium. Particularly preferably, E can be titanium, iron, nickel, And chromium, wherein the combination with an oxide, for example, iron oxide, chromium oxide, nickel telluride Friends with alumina, the Department may have an advantage in promoting passivation. Preferably, E may or may include a metal element selected from the group consisting of zirconium (Zr) 'Nb, and vanadium (V), particularly preferably 098121662 0983285549-0 Form No. A0101 19 pages / total 35 pages [0085] 201006964 [0086] [0089] [0090] [0091] is vanadium or niobium. And these second metal elements are more advantageous as strong intermetallic formers. In this embodiment, the metal element may be a plurality of (for example, a pair of) metal elements. Two metal elements. Preferably, the vE may or may include a metal element capable of forming a uniform high temperature intermetallic phase having a metal, and particularly preferably, E may or may include a metal element capable of forming A13E. . Preferably, E may or may include titanium (Ti), and a titanium containing alloy will typically have a resistivity between 3 and 15 " ohm at room temperature. Preferably, the intermetallic phase may be AlRTi, Cu9, particularly preferably ο ZZ. Preferably, the Al-Ti-Cu based alloy further comprises Al3Ti. Preferably, the intermetallic phase It may be TiAlCu, and particularly preferably, the Al-Ti-Cu based alloy further includes S-TiCiij. In a preferred embodiment, E may be, or may include, a second metal element selected from the group consisting of iron, chromium, nickel, vanadium, niobium, tantalum, and niobium. Preferably, the group comprises iron, chromium, and nickel, and further, the second metal element is more advantageous for enhancing the high temperature stability of the Al-Ti-Cu phases. The anode may be composed of an alloy based on AE-Cu, and it may be by 35 atomic % or more (preferably, 50 atomic %, Or more), 35 atomic %, or more E (where E is the first metal element previously defined), and the remaining proportion of copper, and optional E' (its 098121662 Form No. A0101 No. 20 Page / Total 35 pages 0893285549-0 201006964 [0094] In [0094], E' is obtained by treating a mixture of one or more previously defined additional metal elements). In a preferred embodiment, the anode may be composed of an alloy based on AE-Cu, and it may be by (65 + X) atomic % (atomic percent), 20 + y) atomic % of E (where E is the first metal element previously defined), and (15 -X - y) atomic % of copper, and optionally z atomic.% of E' (where , E' is obtained by treating a mixture of one or more previously defined additional metal elements, wherein E' is substituted for copper, inscription, or E. In this embodiment, the alloy may be obtained by casting, preferably in an anaerobic atmosphere (e.g., a quiet atmosphere), for example, a mixture may be in an argon atmosphere. Next, melting in an air arc electric furnace, and then curing under an argon atmosphere, or alternatively, in this embodiment, the alloy can be assisted by a flux. . . . . -assisted) melted, vacuumed electric bees, or vacuum melted using a resistive electric furnace to minimize contamination of oxygen, carbon, nitrogen, sulfur, or phosphorus. In a preferred embodiment, the anode has the same conductivity as a carbon electrode at least at elevated temperatures (e.g., at 900 ° C), preferably, the anode is at a high temperature (e.g., at 900) At °C), it has better conductivity than a carbon electrode. It is known that the process of separating gas from molten calcium (CaCl 2 ) electrolyte is generally extracted from a metal (M) oxide to obtain a desired degree 098121662 Form No. A0101 Page 21 / Total 35 Page 0983285549-0 [0095 The process of metal (Μ) of 201006964 occurs simultaneously. [0099] According to a still further development, the present invention provides a method for determining whether a (including a substantial constituent) or a metal (Μ) oxide is involved Applying a voltage between the cathode and an inert metal alloy anode in a molten calcium carbide (CaCl 2 ), and electrochemically extracting a range of one metal (M) from the metal (M) oxide, The method comprises the steps of: (A) measuring the amount of gas released during a brief range; and (B) determining the onset, or extent, of the release of chlorine during the transient range from the metal (M) oxide. The range of the metal (M) extracted is related. By making it possible to immediately determine the extent of electrochemical extraction, the present invention makes it possible to control the range during electrochemical extraction in molten calcium carbide (CaCl2) which has hitherto been impossible. Step (A) may be carried out in such a manner that the interval is not continuous, or even it is (e.g., to generate a gas release versus time map), and preferably, step (A) is carried out in a continuous manner. Particularly preferably, the step (B) comprises: correlating the onset of the gas release, or the degree to the extraction rate (%) of the metal (M) from the metal (M) oxide, or Alternatively, step (B) may be to correlate the onset or extent of release of the gas with the oxygen content of the metal (M). Preferably, the method further comprises the following steps: (C) terminating the electrochemistry when a critical degree of gas evolution is reached, 098121662 Form No. A0101 Page 22 of 35 pages 0893285549-0 [01 (8)] 201006964 [ 0101] [0102] [0106] [0107] 098121662 original. Particularly preferably, the step (?) comprises: correlating the degree of the release of the gas with a target extraction rate (%) of the metal (Μ) from the metal (Μ) oxide. The target extraction rate is generally 99% or higher, preferably 99.5%, or higher. Particularly preferably, the step (b) comprises: correlating the critical degree of gas release with a target oxygen content of the metal (M), wherein the target oxygen content is generally less than 2500 ppm. 2 (metal (M) weight), preferably less than 1500 ppm 〇 2 (gold .3⁄4 U) by weight). [Examples] Example 1 Method 1 The pellets were prepared by mixing 1 - 2 g of titanium dioxide (Ti〇2) and 0.2"0.5 g of potassium hydrogencarbonate (KHCOq) in different weight ratios. Next, the mixture was heated at 1073 K for 1 hour, pressurized in a steel mold at a pressure of 3643 atm, and then a hole was drilled in the pellet using a 2 mm drill bit, and the pellet was suspended in a cathode and had a Among the steel electrodes of the molybdenum wire, the Al-Ti_Cu intermetallic anode is suspended on a steel electrode having a molybdenum wire, and the two electrodes are connected to a constant voltage. 3. IV power supply. Calcified potassium-calcium carbonate (KC1 - CaCl.) and vaporized lithium-calcified calcium

L Form No. A0101 Page 23 of 35 pages 0893285549-0 201006964 (UC1 ~ CaCl2) The molten electrolytic mixture is prepared by mixing 180 grams of Cacip with 2 grams of KC1 and LiCl, respectively, and then /tc * Place the compound in the zircon crucible' and place it in a 32 (TC furnace, keep the mixture heated for 24 hours) and then put the mixture into an alumina crucible. And heated to 80 (TC) at 0_5 ° C per minute, then increased to 92 (TC) at 2 ° C per minute, and during heating, argon through at a rate of 500 1 Into the furnace, once the electrolyte is completely melted, the temperature of the furnace drops to 900 ° C. Then, two electrodes will be placed in the furnace * and use A*glient 6651 a DC power supply Apply a level of 3. ^, and the test is performed for 8 - 24 hours. [0108]

The particles will be removed by electrolysis at 30 and 6 minute intervals and rinsed with water for 24 hours. Then, using a mortar and pestle, the particles will be ground into finely divided [0109] for X-ray powder diffraction analysis. Diffrac_ „ ί * ί I " f! J *1 ft ion analysis), Mo Zhong 1 shot is Li Qi Cu-K α... recognize * horse standard and carry it, and sweep the cat speed motorcycle - φ;·02./sec-1 Results 〇[0110] In the case where KHC〇3 is present in Ti〇2, an increase in internal porosity can be achieved immediately in situ. When KHCO3 is decomposed, it is produced. Gasification of potassium, carbon dioxide, and water, and the release of carbon dioxide (c〇, 2; and water (Η /) mixed gas can increase the porosity in the particle, because it enhances CaClg and Ti〇2 The contact surface area also helps to quickly dissociate Ti〇2 from the cathode. 098121662 Form No. A0101 Page 24 of 35 Page 0983285549-0 201006964 [0111] In addition to the formation of holes, the more important reaction occurs in Κ9ϋ Between L· and CaTi〇3, Κ+ ions diffuse into the perovskite lattice (lat_tic e) and by forming a more stable liquid potassium titanate (po-tassiumtitanates) (as shown by the equation [丨]) (based on the balance calculation performed using FACTSAGE, see c Bale et al., FACTSAFE (Ecole Polytechnique CRCT, Montreal, Quebec Canada)) destroys its structure. In this reaction, the formed calcium oxide dissolves in the molten salt bath until it reaches

❹ Saturated: [0113] The reduction of the metal can occur rapidly without the need for major recombination of the Ti〇2 crystal. 'It: 中满义|^议|CTi4〇7, T iq 0 5 ) have a Retorted rutile structure that will include a larger amount of g {oxygen vacant ^ ^ rr! sites). According to the results of a phase equilibrium analysis, the liquid phase can be balanced with the Magneli phase 'and the equilibrium will continue to decrease toward the direction of the metal phase. 'The formation of another liquid phase will increase the reaction kinetics. This is evidence that Ti metal was observed in the one-and-a-half-hour electrolysis at the beginning of the ^, and that the K+ ion produced by the dissociation of potassium citrate would react with the molten electrolyte and form KCaCl3.

CaTi〇3+ 2 Κ20 = Κ4Τί〇Λ+ Ca〇 AG 334349. 6 J mole-1 in T

When the diffusion force of the y ion is faster in the liquid 1* than in the solid CaTi 0, the KJi〇4 to the Magneli Phases and then to the Ti by controlling the wave phase of the potassium titanate Volume, you can avoid the loss of Ti in the molten salt, but if the liquid phase is extracted from the solid particles 098121662 Form No. A0101 25th true / Hing 35 pages deleted: [0114] 201006964 and enter the vaporized calcium (CaCiy bath Among them, ^〇2 will produce irreversible loss in the vaporized calcium (CaCl2) bath. [0115] The La diagram and the lb diagram show that the pellet is in the 〇. 5 hours (Fig. 3) and 1 hour (Fig. lb) XRD pattern during electrolysis, showing Ti (ICDD 5-682), CaTi〇3 (ICDD 42-423), CaTi2〇4 (ICDD 1 Bu 29), and TiO (ICDD 8-) The phase ' of 117) is shown by the comparison of the first and the lb, and that the stable perovskite peak is suppressed when the stabilized perovskite is dissociated, and after 20 hours of electrolysis, the xrd pattern ( Figure 6) shows the appearance of titanium. aj : - .ϊ...

Example 2 'β Λ [01ΓΠ Number 侪 The experimental system for changing the ratio of pdtassium bicarbonate in the granules was carried out, with a variation range of 10 _ 50 wt %. Similarly, 'stupidity is to combine the two different types of CaCl-KC1 and CaCl2-ClCl's molten salt iK:i_3li900t: the next conduction is a 3. IV constant voltage, and both will change from %*〇 particles to完整 Complete reduction of the metal, after which the residual oxygen concentration in the Qin genus is determined by X-ray diffraction analysis (see M. Dechamps et al., Scripta Metallurgica 11 (11), 941 (1977)). And the result is 1350 ppm by weight [0118] The first experiment was to immerse a particle containing 20 wt% potassium bicarbonate in

In the CaCl2-KC1 bath for 8 hours, a Ti metal layer with a thickness of 500 will be formed. In addition, it will have a high concentration of mother, titanium, oblique, 098121662 Form No. A0101 Page 26 / Total 35 Page 0893$ 201006964 [0119] and gas. When the concentration of potassium bicarbonate is increased from 20 wt% to 50 wt% and electrolysis is carried out for 20 hours, it can be found that a uniform microstructure of a Ti metal is formed on the cross section of the region where the particles are mainly metallized. Furthermore, when the salt bath is replaced by LiCl-CaCl and 50 wt% of potassium bicarbonate is mixed with 1 〇2 and electrolyzed for 20 hours, it also leads to overall metallization. Therefore, the reduction system in the two molten salts confirmed that the formation of the liquid phase of KJiOe is important for increasing the reaction kinetics, and that the formation of the system is irrelevant to the molten salt used. In addition, during the electrolysis, all experiments showed an increase in the current at the inert metal anode, which is quite different from previous observations (ica Acta 51 (1), 66 (2005) » M Ma et al.,

Journal of Alloys and Compounds 420 (1-2), ❹ [0120] [0121] 37 (2006); and R. 0. Suzuki et al,, Metallurgical and Materials Transactions B-Process Metallurgy and Materials Processing Science 34, 287 ( 2003)). Current-time analysis Figure 2 shows the current-time relationship of the experiment 2, wherein, although a smooth curve is observed, the current system has a variation of ± 0.1 amp during the electrolysis. . As can be seen from Fig. 2, during the first half hour of the program, the current continuously drops to a turning point, after which the current increases rapidly, and after about 2 hours, the current increases slowly, about 4.0. Ampere's steady rise. 098121662 Form No. A0101 Page 27 of 35 Page 0893285549-0 201006964 [0122] Here, the 'large initial current is because the inert anode used has a souther conductivity, thus reducing the resistance of the battery. In Fig. 2, the initial current decrease is the cause % - the formation of a stable per-ovskite phase (confirmed by X-ray diffraction analysis), and the XRD data of the electrolysis for half an hour shows CaTi〇, 3

The appearance of CaTi2〇4, Ti3〇5' TiO ’ and Ti metal phases, and then, after 4 hours, almost 95% of Ti〇2 has been reduced to Ti. Importantly, in the previous experiment (Pills 16 fork 811 (16 "61; 31., people (^3 1|!&- terialia 54 (11), 2933 (2006) and Schwandt [spura]) The formation of titanium metal was not observed within 3 minutes of the beginning of the program...

According to the HG phase: bitmap, g is balanced, so it can be concluded that there are two reactions occurring simultaneously (in the flood phase), wherein the first reaction is to form CaTiO, CaTi 0 , and 3 2 4 *^3〇5' and this is the dominant phase (Phase: constitu-tion), the second reaction is: 3⁄4 decomposition of Oi'O, "to form TiO, *. 4 f and Ti metal has better electrochemical conductivity due to the 择' phase (-M. county neli phases), and the Ti metal is formed within the first hour of electrolysis, so the current increase will change. It is quite remarkable, which is also the phenomenon found in Fig. 2. In addition, the diffraction pattern after one hour of electrolysis shows a small peak of CaTi0Q, and a main peak of Ti, CaTi2〇4 and Ti3〇. 5. Here, it is important to note that the XRD does not show the presence of potassium titanate because it exhibits a transitional liquid phase during electrolysis. 098121662 Form bat number A0101 Page 28 of 35 pages 201006964 [0124] ❹ [0126] The resulting Ti metal This is confirmed by microstructure analysis and by measuring the weight loss after electrolysis (as in the previous example of electroreduction of Cr2〇3 in molten calcium (CaCl2) (GZ Chen et al., Metallurgical and Materials Transactions B-Process Metallurgy and Materials Processing Science 35 (2), 223 (2004)). After the electrolysis of the 7 丨〇 2 granules of i gram for 20 hours, the granules were first washed with water 24 After an hour, the weight of the granule was measured again to obtain a weight of 605605g. Since the theoretical yield of Ti which can be produced from 1 gram of Ti〇2 is 0.6 gram, the error falls into the experimental observation error, so Indeed: these measurements can be used to calibrate ^chemical cells to obtain a relationship between the temporarily measured current and the ratio of Ti〇2 to Ti metal. TiO. Current and time of the sample

The L diagram, with a high degree of correctness, determines the conversion rate of the chemical reduction reaction of the show (when the extraction is still at the end of each period of ήφ篆2) (A a Property is generally Τι metal approximately).

Similarly, an electrochemical cell can be calibrated to obtain a relationship between a temporarily measured current and a condition that begins to corrode, or a condition in which the gas begins to be released from the molten state. Thus, it is possible to use the current versus time graph of a new Ti〇2 sample to determine when electrochemical reduction should be terminated to avoid corrosion and/or gas generation. BRIEF DESCRIPTION OF THE DRAWINGS [The present invention will now be described with reference to the example of the non-limiting example and the drawing as 098121662 Form No. A0101, page 29/35 pages 0893285549-0 [0127] 201006964, wherein: [_ "La map and the first _ •• The system respectively shows that the dioxin + chlorinated chlorine (TiO〆KHC〇3) particles are baked for 1 hour and electrolyzed for 5 hours (see figure la), and One gasification about - gasified lithium (caci _ 2

LiC1) xrd in a molten bath for 1 hour (see Figure 1b) showing Ti (ICDD 5-682), CaTi〇3 (ICDD 42-423), CaTiJ/ICDD 11-29), and TiO ( L 4 phases of ICDD 8-117); and Fig. 2: showing a plot of current versus time measured by applying a voltage of 3.1 V according to the method of the present invention*

[Main component symbol description] [0129] None

«s 缺缺 AD101 0983285549-0

Claims (1)

201006964 VII. Patent Application Range 1. A method for determining the range of electrochemical extraction of a metal (M) which is a metal (M) oxide caused by a voltage applied to a cathode and at a Between an inert metal alloy anode in a dissolved oxygen molten electrolyte, the cathode comprises or consists essentially of, or is in contact with, the metal (M) oxide, the method comprising the steps of: (a) Measuring a current between the cathode and the inert metal alloy anode over a time range; and ❹ (b) oxidizing a characteristic of the current between the cathode and the inert metal alloy anode over the time range and the metal (M) The range of electrochemical extraction of the metal (M) is related. '* M. 2 . As described in claim 1 of the patent application; in the method b, the electrical current system of the donor pole and the inert metal alloy anode at the time range g includes a turning point. The production method described in claim 1 or 2, and thereafter, in the step (匕> the cathode and the idleness. Nightmare), the current in the time range The method of the present invention is the method of claim 3, wherein the quantity is characterized by a turning point of the current exceeding the time range. . 5. The method of claim 3, wherein the quantitative characteristic of the current at a turning point of the current exceeding the time range is the measured current, and the step (b) ) is: correlating the measured current with the extraction rate (%) of the metal of the metal (M) oxide. 098121662 Form No. A0101 Page 31 / Total 35 Page 0893285549-0 201006964 6 . μ Please patent (4) The fourth rhyme method, wherein the comparison characteristic is a critical current 'the critical current in the time range exceeds one of the current turning points Where. 7. The method of any of the preceding claims, wherein the step (b) comprises: causing the characteristic of the current between the cathode and the inert metal alloy anode during the time range to be formed at the beginning A by-product of the need or an extraction range prior to the appearance of a corrosive condition. 8. If you apply for a patent scope! The method according to any one of the preceding claims, wherein the step (b) comprises: a target extraction of the rate (1), or the force of the metal (4), - ???, η Θ The gamma method described in the patent scope, wherein the time range is less than 8 hours. The method of claim 10, wherein the electrochemical extraction is carried out in a metal (Ma) oxygen. A winter method according to any one of the preceding claims, M) is one or more selected from the group consisting of titanium (Ti), the metal (Nb), tantalum (Ta), touch αο, 钍 (Th), A metal of the group consisting of chromium (Cr), iron (F〇, steel (steei), and zirconium (Zr). The method of claim 1, wherein the metal (M) is Titanium (Ti). 13 098121662 , 令 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , - Alkali metal (Μ) salt phase mixed * 京编后第32页 / 35 pages ^; ^ 0983285549-0 201006964 The object is the cathode. 14. The method of the above-mentioned application-- The method of claim 1, wherein the anode is composed of an alloy of -Al-E-Cu as a base, and wherein the anode is composed of an alloy of -Al-E-Cu. The M_E_Cu base alloy includes an intermetai Uc phase having the following molecular formula: A1xEyCuz : 16 . E represents one or more metal elements; ® :J-1|.| HH1II X is an integer between 1 and 5; y is an integer 1 or 2; and Z is an integer 1 or 2. The method of claim 15, wherein the e is one or more selected from the group consisting of nails (Ru), strontium (Ti), strontium (Zr), chromium (Cr), sharp (Nb), bismuth ( ν)::ϊ::,:;_, iron (Fe), nickel (Νι), 镧 (La), the metal that makes up the group. 17 If you apply for the patent scope! The method according to the item, wherein the metal (μ) is oxidized (Ti〇2), the molten electrolyte comprises calcium carbonate (CaCl2), and the electrochemical extraction is in an alkali metal (Ma) oxide Executed in the presence of. 098121662 Form No. A0101 Page 33 of 35 0983285549-0