JP4190519B2 - Method and apparatus for producing metallic calcium by molten salt electrolysis - Google Patents

Description

  The present invention relates to the recovery of metals from metal chlorides, and more particularly to a method for producing metals by molten salt electrolysis.

  Conventionally, single metal titanium has been produced by a crawl method in which titanium tetrachloride is reduced with molten magnesium to obtain sponge titanium, and production costs have been reduced by accumulating various improvements. However, since the crawl method is a batch process that repeats a series of operations discontinuously, there is a limit to the efficiency.

  For the above situation, a method of directly producing titanium metal by reducing titanium oxide with metallic calcium in molten salt (for example, see Patent Documents 1 and 2), or a reduction including a metal or alloy such as calcium An EMR method (see, for example, Patent Document 3) is disclosed in which an agent is produced and a titanium compound is reduced by electrons emitted from the reducing agent to obtain titanium metal. In these methods, calcium oxide by-produced by the electrolytic reaction is dissolved in calcium chloride, and then metal calcium is recovered and reused by performing molten salt electrolysis. However, the metal calcium produced by the electrolytic reaction has a problem that it has a high solubility in calcium chloride because it is in a liquid state, easily dissolves and dissipates, and the yield decreases.

  Furthermore, an attempt to deposit metallic calcium on a cathode in a solid state using a composite molten salt having a melting point lower than that of metallic calcium has been disclosed (for example, see Patent Document 4). However, this method requires special preparation of the composite molten salt, and the problem of increased cost has not been solved.

  As described above, the conventional method has a problem that it is difficult to efficiently recover an active metal such as metallic calcium, or the cost is high even if it is possible.

WO99 / 064638 JP 2003-129268 A JP 2003-306725 A US3226311

  The present invention has been made in view of the above circumstances, and for example, the metal used for reducing oxides or chlorides of titanium metal can be efficiently recovered, and is implemented by an inexpensive method. It aims at providing the manufacturing method of the metal by molten salt electrolysis which can be performed.

The method for producing metallic calcium by molten salt electrolysis according to the present invention is a method for producing metallic calcium by molten salt electrolysis performed by filling an electrolytic cell equipped with an anode and a cathode with a molten salt containing calcium chloride , wherein the cathode is a metal It consists of a molten alloy of calcium and tin, zinc or lead . The precipitated metallic calcium is dissolved in the molten alloy, and this molten alloy is transferred to the elution tank and brought into contact with the calcium chloride provided in the elution tank. The metallic calcium in the molten alloy is eluted and recovered in calcium chloride .

The apparatus for producing metallic calcium by molten salt electrolysis according to the present invention is an electrolytic cell filled with a molten salt containing calcium chloride, in which a cathode, an anode, and a plurality of bipolar electrodes are immersed in a vertical direction, and the electrolytic cell produced in this electrolytic cell. An apparatus for producing metallic calcium by molten salt electrolysis comprising an elution tank for collecting metallic calcium , wherein the cathode is made of a molten alloy of metallic calcium and tin, zinc or lead, and the bipolar electrode is made of a molten alloy The molten alloy is composed of a supporting portion of the molten alloy and an overflow pipe for dropping the molten alloy to the pole immediately below when the supported amount of the molten alloy exceeds a predetermined amount, and the molten alloy is transferred to the elution tank, It is characterized in that it is brought into contact with pre-filled calcium chloride and the metallic calcium in the molten alloy is eluted and recovered in the calcium chloride .

  According to the present invention, the metal deposited on the surface of the cathode made of a molten alloy is immediately dissolved in the molten alloy to form an alloy, so that dissolution of the deposited metal in the electrolytic bath can be suppressed. Therefore, the metal can be efficiently recovered at a low cost.

  Embodiments of the present invention will be described below with reference to the drawings. Hereinafter, a case where the metal is calcium metal and the metal chloride is calcium chloride will be described as an example.

  1 to 4 show a preferred apparatus configuration example for carrying out the present invention. FIG. 1 is a schematic sectional view showing a first embodiment of the present invention. Reference numeral 1 denotes an electrolytic cell, which is filled with an electrolytic bath 2 made of calcium chloride (melting point 780 ° C.) and heated to a melting point or higher by a heating means (not shown) and kept in a molten state. Yes. Reference numeral 3 denotes an anode. Reference numeral 4 denotes a cathode made of an alloy having a higher density than calcium chloride, a melting point lower than that of calcium chloride, and a solubility in metallic calcium. Since the melting point of the cathode 4 is lower than that of calcium chloride, the cathode 4 is in a molten state, and since the density is higher than that of calcium chloride, the cathode 4 settles at the bottom of the electrolytic cell 1. Reference numeral 6 is an elution tank for recovering metallic calcium, and reference numeral 7 is a calcium chloride bath, which is in a molten state by a heating means (not shown).

  When the anode 3 and the cathode 4 are connected to a DC power source (not shown) and electrolysis is started, molten metallic calcium is deposited on the surface of the cathode 4. Since calcium metal has a solubility in the molten alloy constituting the cathode 4, it immediately dissolves into the cathode 4 after the precipitation to form an alloy. On the other hand, chlorine gas 8 is generated at the anode 3, and this chlorine gas 8 can be separately collected and reused for the chlorination reaction of titanium ore. Or you may utilize for another use.

  After performing the electrolytic reaction for a predetermined time, the cathode 4 is taken out from the electrolytic cell 1 and transferred to the elution tank 6 as indicated by reference numeral 9. Since metallic calcium has solubility in the calcium chloride bath 7, the metallic calcium in the cathode 4 is eluted into the calcium chloride bath 7 while being settled in the elution tank 6, and the metallic calcium is concentrated. . Calcium chloride enriched with metallic calcium can be used by supplying it to a reduction reaction step of titanium oxide or titanium chloride, for example, as indicated by reference numeral 10.

  The cathode 4 after the metal calcium is eluted with respect to the calcium chloride bath 7 is recovered again and supplied to the electrolytic cell 1 as indicated by reference numeral 11. Further, the calcium metal supplied to the titanium oxide or titanium chloride reduction step is converted into calcium chloride by the reaction with titanium oxide or titanium chloride, and is returned to the electrolytic cell 1 and the elution cell 6 again through the path indicated by reference numeral 12. The ratio of calcium chloride returned to the electrolysis tank 1 and the elution tank 6 is adjusted as appropriate, so that the liquid level in both tanks can be kept at a constant level. By repeating the above steps, metallic calcium can be continuously recovered.

  The material of the anode 3 is required to be conductive and not to dissolve in the electrolytic bath and to withstand high-temperature chlorine gas. Such a material is preferably carbon. Moreover, as a structure of an anode, it is preferable that the anode is immersed in the electrolytic bath 2 and extends in the horizontal direction. By setting it as such a structure, the area facing the cathode 4 arrange | positioned at the bottom part of the electrolytic cell 1 can be ensured widely, and reaction can be advanced efficiently. Furthermore, by coating the portion exposed from the electrolytic bath surface of the anode 3 with a conductive ceramic, oxidation wear of the anode 3 can be suppressed. As such a conductive ceramic, an alumina paste is preferable.

  The cathode 4 is required to be composed of an alloy having solubility with respect to metallic calcium generated by the electrolytic reaction. By using such an alloy for the cathode, metallic calcium produced at the cathode can be instantaneously taken into this alloy, so that dissolution of metallic calcium into the electrolytic bath 2 is suppressed and metallic calcium is efficiently recovered. can do.

  Although the installation location of the cathode 4 is not particularly limited, it is preferably disposed at the bottom of the electrolytic cell 1 and can be achieved by configuring the cathode 4 with a calcium alloy having a density higher than that of the electrolytic bath 2. Chlorine gas floats upward from the electrolytic bath after it is generated. Therefore, by disposing the cathode 4 at the bottom of the electrolytic cell, generation of chlorine gas and diffusion of metallic calcium to the residence location can be suppressed, so that the reverse reaction can be suppressed. It is preferable. Further, as compared with a method in which the cathode is disposed on the bath surface or in the bath, a partition wall is unnecessary, and contamination of impurities can be avoided.

  As an alloy satisfying these conditions, a Ca—Zn, Ca—Pb, or Ca—Sn alloy is preferable. Furthermore, since these alloys have a melting point lower than that of calcium chloride, these alloys can be maintained in a molten state as long as they are within a temperature range in which calcium chloride is melted.

  The electrolytic bath is preferably maintained in a temperature range of 800 to 900 ° C. By maintaining in such a temperature range, the electrolytic bath and the calcium alloy can be maintained in a molten state.

  As the electrolytic bath, a molten salt obtained by adding other chlorides to calcium chloride may be used in combination as appropriate.

  In addition to the case where the metal is calcium and the electrolytic bath is calcium chloride, the method of the present invention can be applied to other metals. In that case, it is preferable that the metal generated in the electrolytic cell and the metal of the molten salt used in the electrolytic bath are common.

  The temperature of the calcium chloride bath in the elution tank is preferably kept higher than the temperature of the electrolytic bath in the electrolytic tank. This is because metallic calcium in the molten alloy can be eluted more efficiently. Specifically, it is preferable to set the temperature 100 to 200 ° C. higher than the temperature of the electrolytic cell. Heating beyond this range is not preferable because loss due to evaporation occurs.

  FIG. 2 is a schematic cross-sectional view showing an example of an elution tank in another embodiment of the present invention. The code | symbol 9 represents the flow of the molten alloy which comprises the cathode supplied from an electrolytic cell. As shown in the figure, the molten alloy constituting the cathode 4 is preferably supplied through a plurality of nozzles and the like. By setting it as such a structure, since the contact area of the calcium chloride bath 7 and a molten alloy can be increased, metallic calcium can be eluted in the calcium chloride bath 7 more efficiently.

  FIG. 3 is a schematic cross-sectional view showing an example of an elution tank in another embodiment of the present invention. The molten alloy extracted from the electrolytic tank is supplied to one end of the elution tank 6 by means such as a supply pipe indicated by reference numeral 9 and moves to the other end of the elution tank 6 while sinking the elution tank 6. It returns to the electrolytic cell 1 by means, such as the extraction tube shown. On the other hand, a part of calcium chloride by-produced in the reduction process of titanium oxide or titanium chloride is supplied to the end of the elution tank 6 by means such as a supply pipe indicated by reference numeral 12, and the upper part of the elution tank 6 is opposite to the molten alloy. It moves to the direction and is supplied to the reduction process of titanium oxide or titanium chloride from the other end of the elution tank 6 by means such as an extraction pipe indicated by reference numeral 10. Thus, the metallic calcium in the molten alloy can be efficiently eluted into the calcium chloride bath by bringing the molten alloy and the metal chloride into countercurrent contact.

  FIG. 4 is a schematic cross-sectional view showing another embodiment of the present invention. Reference numeral 1 denotes an electrolytic cell, which is filled with an electrolytic bath 2 made of calcium chloride, and is heated to a melting point of calcium chloride or more by a heating means (not shown) and kept in a molten state. Reference numeral 3 denotes an anode. Reference numeral 4 denotes a cathode made of an alloy having a higher density than calcium chloride, a melting point lower than that of calcium chloride, and a solubility in metallic calcium. Since the melting point of the cathode 4 is lower than that of calcium chloride, the cathode 4 is in a molten state, and since the density is higher than that of calcium chloride, the cathode 4 settles at the bottom of the electrolytic cell 1. Reference numerals 4a to 4c are bipolar electrodes made of the above molten alloy.

  Here, the bipolar electrode is an intermediate electrode installed between the anode and the cathode in the electrolysis of the metal salt, the voltage required for the electrolysis is V [V], and the number of bipolar electrodes installed is n. In some cases, by applying a voltage of (n + 1) V [V] or more between the anode and the cathode, electrolysis is caused not only in the anode and the cathode but also in each region delimited by the anode, each bipolar electrode, and the cathode. be able to. In FIG. 1, since three bipolar poles are installed, between the anode 3 and the bipolar pole 4a, between the bipolar pole 4a and the bipolar pole 4b, between the bipolar pole 4b and the bipolar pole 4c, and between the bipolar pole 4c and the cathode 4 In the four regions in between, precipitation of metallic calcium and generation of chlorine gas occur, respectively.

  The bipolar poles 4a to 4c are supported by dish-shaped bipolar pole support portions indicated by reference numerals 5a to 5c. The bipolar electrode support portions 5a to 5c are fixed in the electrolytic cell 1 by fixing means made of an insulator (not shown). Further, each of the bipolar electrode support portions 5a to 5c is provided with overflow pipes 5d to 5f for discharging the molten alloy. When the molten alloy of the bipolar electrodes 4a to 4c increases and the liquid level reaches a certain height or higher, the molten alloy is discharged and settled to the bipolar electrode support (or the cathode 4) directly below, so that the bipolar electrodes 4a to 4c The amount of molten alloy 4c is kept constant. These overflow pipes 5d to 5f are preferably installed alternately as shown in FIG. By arranging in this way, the residence time until the molten alloy discharged from the upper stage is discharged to the lower stage can be secured, and metallic calcium can be efficiently recovered. Reference numeral 6 is an elution tank for recovering metallic calcium, and reference numeral 7 is a calcium chloride bath, which is in a molten state by a heating means (not shown).

  When the anode 3 and the cathode 4 are connected to a DC power source (not shown) and electrolysis is started, the bipolar electrodes 4a to 4c are polarized with the upper surface serving as a cathode and the lower surface serving as an anode. Further, chlorine gas 8 is generated on the lower surface of the bipolar electrode 4c, and molten metallic calcium is deposited on the upper surfaces of the bipolar electrode 4a, the bipolar electrode 4b, the bipolar electrode 4c, and the cathode 4. Chlorine gas 8 generated on the lower surface of each bipolar electrode floats to the bath surface and is collected together with chlorine gas 8 generated from the anode 3. At this time, if the bottom surfaces of the bipolar electrode support portions 5a to 5c are not horizontal but are inclined toward the end, it is preferable because chlorine gas can be discharged onto the bath surface without stagnation. On the other hand, the metal calcium deposited on each electrode has a solubility in the molten alloy constituting the cathode 4 and each bipolar electrode, so that it dissolves immediately after the deposition to produce an alloy.

  As the above reaction proceeds, metallic calcium dissolves in each bipolar electrode, so the number of molten alloys in each bipolar electrode increases. In the bipolar electrode 4a, the molten alloy that has increased beyond a certain liquid level is supplied to the bipolar electrode 4b directly below by the overflow pipe 5d. Similarly, in the bipolar electrode 4b, the molten alloy is increased by the molten metal calcium and the supply from the bipolar electrode 4a, and the increased molten alloy is supplied to the bipolar electrode 4c directly below by the overflow pipe 5e. Similarly, the molten alloy is supplied from the bipolar electrode 4 c to the cathode 4.

  The molten alloy increased in each bipolar electrode 4a to 4c is sequentially supplied downward while taking in the precipitated metallic calcium, so the content of metallic calcium increases as it goes down, and the content at the cathode 4 is It has become the maximum.

  After performing the electrolytic reaction for a predetermined time, the cathode 4 is taken out from the electrolytic cell 1 and transferred to the elution tank 6 as indicated by reference numeral 9. Since metallic calcium has solubility in the calcium chloride bath 7, the metallic calcium in the cathode 4 is eluted into the calcium chloride bath 7 while being settled in the elution tank 6, and the metallic calcium is concentrated. . Calcium chloride enriched with metallic calcium can be used by supplying it to a reduction reaction step of titanium oxide or titanium chloride, for example, as indicated by reference numeral 10.

  The cathode 4 after the metallic calcium is eluted with respect to the calcium chloride bath 7 is recovered again and supplied as a molten alloy of the bipolar electrode 4 a of the electrolytic cell 1 as indicated by reference numeral 11. When supplying the molten alloy to the bipolar electrode 4a, it is preferable to install it alternately with the overflow pipe 5d as shown in FIG. By arranging in this way, the residence time until the supplied molten alloy is discharged to the next bipolar electrode 4b can be secured, and metallic calcium can be efficiently recovered.

  The calcium metal supplied to the titanium oxide or titanium chloride reduction step is converted into calcium chloride by the reaction with titanium oxide or titanium chloride, and is returned to the electrolytic cell 1 and the elution cell 6 again by the path indicated by reference numeral 12. The ratio of calcium chloride returned to the electrolysis tank 1 and the elution tank 6 is adjusted as appropriate, so that the liquid level in both tanks can be kept at a constant level. By repeating the above steps, metallic calcium can be continuously recovered.

[Example 1]
The electrolytic cell and elution cell shown in FIG. 1 were filled with molten calcium chloride, and molten salt electrolysis was performed using carbon as the anode and Ca—Zn alloy as the molten alloy of the cathode. Stainless steel containers were used as the electrolytic and elution tanks, and the inner surface was lined with a refractory material so as to withstand high-temperature molten calcium chloride. The temperature of the electrolytic bath was 700 ° C., and the temperature of the elution bath was 800 ° C.

  Under the above conditions, a voltage of 4.5 V was applied to the anode and the cathode, and molten salt electrolysis of calcium chloride was performed. As a result, 75% of the metal calcium was calculated in the elution tank with respect to the metal calcium yield calculated from the theoretical amount of electricity. It was possible to recover.

[Example 2]
When molten salt electrolysis of calcium chloride was performed under the same conditions as in Example 1 except that the elution tank shown in FIG. 3 was used, metallic calcium in the molten alloy supplied to the elution tank was eluted into the calcium chloride bath. The amount was improved by 20% compared to Example 1.

[Example 3]
Using the electrolytic cell equipped with the bipolar electrode shown in FIG. 4, calcium chloride was recovered in the form of an alloy. When the recovered calcium alloy is moved to the elution tank shown in FIG. 1 and the metallic calcium in the alloy is released into the calcium chloride bath, it is possible to secure about twice the productivity as compared with Example 2. did it.

  The metal used for reducing the oxide or chloride of titanium metal can be recovered by a highly efficient and inexpensive method.

It is a schematic cross section which shows the electrolytic cell and the elution tank in the manufacturing method of the metal by molten salt electrolysis of the embodiment of this invention. It is a schematic cross section which shows the example of the other elution tank in the manufacturing method of the metal by molten salt electrolysis of the embodiment of this invention. It is a schematic cross section which shows the example of the other elution tank in the manufacturing method of the metal by molten salt electrolysis of the embodiment of this invention. It is a schematic cross section which shows the manufacturing method of the metal by molten salt electrolysis in the other embodiment of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Electrolysis tank 2 Electrolytic bath 3 Anode 4 Cathode (molten alloy cathode)
4a-4c Molten alloy (bipolar electrode)
5a to 5b Bipolar electrode support parts 5d to 5f Overflow pipe 6 Elution tank 7 Calcium chloride bath 8 Chlorine gas 9 Molten alloy supply path 10 Metal calcium supply path 11 Molten alloy supply path 12 Calcium chloride supply path

Claims (9)

A method for producing metallic calcium by molten salt electrolysis performed by filling an electrolytic cell equipped with an anode and a cathode with a molten salt containing calcium chloride ,
The cathode is made of a molten alloy of metallic calcium and tin, zinc, or lead . The precipitated metallic calcium is dissolved in the molten alloy, and the molten alloy is transferred to an elution tank, and is prepared in advance in the elution tank. method for producing a metal calcium by molten salt electrolysis, characterized in that was in contact with the calcium chloride is recovered the metal calcium in the molten alloy is eluted into the calcium chloride. The method for producing metallic calcium by molten salt electrolysis according to claim 1, wherein the cathode is provided at the bottom of the electrolytic cell. The method for producing metallic calcium by molten salt electrolysis according to claim 1 or 2, wherein the temperature of the elution tank is maintained at a temperature higher than that of the electrolytic tank. The method for producing metallic calcium by molten salt electrolysis according to any one of claims 1 to 3, wherein at least one bipolar electrode configured to hold the molten alloy is provided between the anode and the cathode. . Each of the at least one bipolar pole comprises an overflow tube;
  The molten alloy that increases with the progress of molten salt electrolysis falls to the bipolar electrode or the cathode provided directly below the overflow tube,
  The method for producing metallic calcium according to claim 1, wherein the molten alloy is transferred from the cathode to the elution tank. The method for producing metallic calcium according to claim 5, wherein the overflow pipes are alternately arranged so as not to overlap each other in the vertical direction. Molten salt electrolysis metal comprising an electrolytic cell filled with molten salt containing calcium chloride , a cathode, an anode, and a plurality of bipolar electrodes immersed in a vertical direction, and an elution tank for recovering metallic calcium produced in the electrolytic cell An apparatus for producing calcium ,
The cathode is made of a molten alloy of metallic calcium and tin, zinc or lead,
The bipolar electrode is composed of the molten alloy, a support portion of the molten alloy, and an overflow pipe that drops the molten alloy to a pole immediately below when the support amount of the molten alloy exceeds a predetermined amount,
The molten alloy is transported to the elution vessel, the metal calcium and recovering in this elution tank is contacted with the pre-filled calcium chloride to elute the metal calcium in the molten alloy in the calcium chloride Manufacturing equipment. The apparatus for producing metallic calcium according to claim 7, wherein the overflow pipes are arranged alternately so as not to overlap each other in the vertical direction. 9. The apparatus for producing metallic calcium according to claim 8, wherein the cathode is provided at the bottom of the electrolytic cell.

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