TW201139693A - Method for producing metal indium and molten salt electrolytic bath - Google Patents

Abstract

The problem of this invention is to provide an effective and efficient method for producing metal indium which can solve various problems in the conventional method, that is a method for producing highly refined metal indium with high recovery percentage over a long period from alloy containing metal indium. This invention provides a metal indium production method in which metal indium is used as anodes and cathodes of alloy containing metal indium, and indium chloride-zinc chloride molten salt containing indium chloride as a main component is used as electrolyte, and indium is eluted as positive ions from an anode while metal indium is electrodeposited on a cathode by molten salt electrolysis. The method of this invention is characterized by that the content of indium chloride in the indium chloride-zinc chloride molten salt is over 68 weight % and the content of water in the molten salt is under 0.5 weight %.

Description

201139693 VI. Description of the invention: [Technical field to which the invention belongs] Indium-based rare earth metal, which is included in the material as a material, or from the use of ITO for fine-grained waste (/= refining and recycling of metal indium for recycling) Expensive ^ Due to the extraction of TM waste") One of these methods is known, and it is known to use the method of manufacturing a sleek sputum. For example, a method is known in which gold is added as an anode, and a molten salt electrolyte is used as a ruthenium (indium-tin-mercury is recovered as a metal indium (for example, _===2 electrolysis) According to the standard analysis of Yu Yinxi, the potential is similar, and the common (4) = metal indium and indium: therefore, by using amalgam __oxygen = ^31 metal, this method can refine and recover metal indium and It is almost unfamiliar, but because mercury is used at the anode, and the miscellaneous method of producing 3 with tin is known to contain bismuth, it is known that there is also a kind of electrolytic refining, and the metal steel salt electrolyte is brought into contact with the air at the cathode. The water of the salt is a qualitative change with the concentration of water vapor, which causes the cell voltage to rise or the salt to be chemically reacted. The reason is that the amount is less than 5〇': the word: the amount is preferably 50. ~67% by weight of 'at 67% by weight, tin is mixed with precipitated indium, which is not good. In addition, the metal-containing indium alloy is used as the anode and the indium-containing chloride and zinc are used to chlorinate 201139693 Ξϊίί ^ (4) (10) The financial law is to improve 3). But it has many _ 'addition of ammonium chloride to improve the resistance of the salt Electrolytic cell voltage rises ^ point this "melting treatment equipment as a countermeasure, etc.. Flat clothing brothers heart must have a milk discharge _ melt salt electrolyte two chemical = chlorinated miscellaneous shells known to have a method of electrolyte bath group赤胡聚气儿>People> 罝50% or less, and will sink away from the 'in, ' 2 quality bath (for example, refer to Patent Document 4). From 'further refine the electrolysis to chlorine ore = learning r However, this _ _ leakage into the gas phase of the water caused the salt to deteriorate slightly as the smelting salt and from the carry-up, in the electrolytic cell used in the molten salt electrolysis method, the sump 'configures the cathode at the bottom' Maintaining the molten salt bath layer in the jade:

It is kept in a container made of a porous body (for example, the cost of the patent H) (4), and it is said that the line is the same as the one used in the previous article. [Prior Art] [Practical Technology 1] [Patent Document 1 Japanese Patent Publication No. Sho 46-2734 [Patent Document 2]: International Patent No. 2〇6_〇46°8〇〇 No. 201139693 [Patent Document 3]: Russian Patent No. 53138〇 [Patent Document] 4]: 曰本特开平〇4_2546〇〇公公 [Patent Document 5]: 曰本特开昭57·2〇7185 [Invention] [Problems to be Solved by the Invention] The present invention aims to provide It can solve the above-mentioned advantages and high efficiency of metal indium. The various problems of the formula are in the indium alloy for a long time at a high recovery rate to produce a high degree of chain from gold. [Technical means to solve the problem] The present inventors have deliberately studied from the metal-containing indium alloy towel, and found that 'the solution is made by electrolytic refining of the molten salt, and the water content in the salt of the county is properly corrected. Metal indium, purity, and the electrolyte of the secret salt stabilizes the ship] = the recovery of metal indium, and thus complete the hair The present invention relates to a method for producing a metal indium, a method for producing a metal indium, a metal of a cathode, and a metal gas, a metal, a zinc, a scale, and a scale. f melts the knives, dissolves indium as a cation, and at the cathode: electrolysis from the % pole gasification - the gas content of the indium sulphate salt in the salt content of the α5 weight can be ^^ above 68 weights, dissolved in water ί The quantity is based on the water content of the molten salt, and the final work is “% by weight of water (refer to Japanese powder, Japanese and Yang Yang’s physical engineering notes, p. 588 (1980)). The present invention is described in detail. The alloy of the present invention is a steel alloy. The alloy in the present invention is composed of right-handed. The iP is not particularly limited to the state of bonding. The metal indium contained in the metal indium is not limited to a main component or contains a trace amount. Suitable for use. From the aspects of gold, ', π, 'privacy, recovery of indium, productivity of indium, metal-containing indium 201139693 should be 1QQ weight PPm to 99.999% by weight, preferably weight%, more preferably 6G weight% job 9wt%. Fixed, metal other than steel, the type is not Special restrictions Two · · From Li, Na, Mg, A1, Si, K, ccas, Tiv,

Nb 1U =, C〇, Nl, CU, Zn, Y, Ge, AS, Se, Sr, Y, Zr, :, r, . One or more of Pd, Ag, Cd, Sn, Sb, Te, Cs, Ba, Ta, two /:, Pt, Au, T1, Pb, and Bi are selected. 'In the molten salt electrolysis, it is separated from indium and refined.

Mg^Al^.K.Ca.ScT^v.Cr.Mn^e.Co^Ni.Cu^ f:=^, Sr, Y, Zr, Nb, M(), Ru, Rh, pd, Ag, Cd, two main / a, Ta, w, Re, 〇 s, 11, Pt, Au, τι, Pb, Bi, especially G n 〇1'1^, 81, ^€ &, 1^, separated from indium In the case of refining a toroidal metal indium alloy, the use of metal indium as a tin alloy is carried out using a tantalum, and the indium compound is subjected to reduction treatment.

丨ίί is available. As the indium compound, it is only required to contain an indium compound, and I: specifically, for example, an antimony waste such as oxygen, hydrooxo, indium chloride, indium sulphate or indium nitrate. For example, in the method of obtaining a metal-containing indium alloy from a waste material, for example, a method of reducing the waste material by using a reducing agent, and a method of reducing the amount of the waste material by using a reducing agent; And <indium acid or indium nitrate, etc., followed by addition of a basic substance to become a cerium hydroxide-containing chemical & ', and then the chlorinated oxidized|gj hydrazine bond is heat-treated and converted into emulsified, and then彳 a reaction to obtain a metal-containing bismuth alloy; a solution containing indium chloride, indium or yttrium, to make the sin-indium lower electric metal, specifically by adding metal aluminum or metal zinc A method of precipitating an alloy-containing alloy to obtain a metal-containing indium alloy. Λ For the molten salt used in the present invention, first of all, it is necessary to be a salt containing indium. In terms of its kind, indium chloride is used in the present invention from the viewpoint of having a low melting point, good oxidation resistance, and low electrical resistance. However, when indium chloride is used alone, since 201139693 is an indium-based rare earth metal and expensive, it is not economical. Therefore, it is necessary to use the indium chloride-containing material, such as the water absorption property and the low water-decomposability, to be the salt of the salt, and to use the chloride as the characteristic of the chemical field. The water content of the molten salt containing the indium compound is 0.5% by weight or less and 68% by weight or more, and the weighting material, that is, the zinc vapor content is 32% by weight, and the amount is less than 68. Zinc reduces the purity of metal indium. Furthermore, =; the conductivity in the electrodeposition of the cathode is low, and if it contains 32% by weight, since the zinc vapor is increased in the molten salt bath, the running cost is increased, and the liquid is increased, and the electric resistance becomes larger. Indium chloride 68% by weight, can be 佶 = Fan, in the molten salt of the invention, the melting point is lower than that of the recorded 7 f electric gambling, so that the Ϊ Ί can be found above, preferably it is more than 5% by weight. In Patent Document 2, in the case where the indium-containing chloride of the aged indium chloride is contained, it is not preferable that the tin is mixed with the precipitated indium, but this is not the same as the μ-week, so that the tin does not mix. The indium/minus content rate is 'economical to reduce the liquid resistance, and the electrolysis cell voltage is lowered by one, and the present invention has been completed. The low-slurry operation cost of the cattle is thus defined as the content of indium chloride in the dazzling salt used in the present invention; and the water content of the molten salt is 〇·5% by weight or less. In the above-mentioned patent, the water content of the county finance is G 5 by weight 2, and the indium vapor content is less than 5 〇 mol% (=53 wt ^ /, the indium vapor content or the effect is completely different from the present invention. B) In the indium vapor contained in the smelting salt, the price of the marriage is i, valence n, nCl2, and InQ3, and must contain more than one of them. Compared to a only $:: m in molten salt electrolysis. In the infusion of molten salt V4, indium bismuth moves at 1 j. Compared with 3 InC1, the production speed of sub-indium can also be up to 3 times, so it is better to use the same amount of molten salt of the present invention. The moisture content is 〇·5% by weight or less. When the moisture content exceeds 0.5% by weight of 201139693, the electrolysis of s causes the current to precipitate in the metal, and the impurity sleeve in the metal crucible which inhibits the precipitation of the metal indium cathode on the cathode is caused by uncertainty. The dazzle of the present invention is owed by f and cannot be fully refined. The initial initial ~ Hyunrong salt electrolysis "sub-content, which means that the molten salt is electrolyzed _ 'the amount of water at any point of operation. The optimal moisture content is reduced to 05 ^ ^ water knife to dehydrate 'to make molten salt In the middle and middle of the water, it is maintained at a weight of α5 and also prevents the smelting salt from sucking. 4% by weight or less during operation t. The better the moisture content of the molten salt is not determined by the concentration of the concentrated vapor. In the case of the water-steaming method, the second is such that the water content is kept low and the holding is low. Specifically, the vapor phase concentration of the gas phase portion of the gas phase portion is 0.5% by volume. D " The concentration of the therapeutic milk is preferably less than 1% by volume, and is not particularly limited. For example, it is possible to make the components of the gas phase portion of the phase contact and oxidize carbon, etc. It is preferable to make the hornbill from S, 11, argon, helium, hydrogen. - Oxidized carbon, and the dissolved oxygen in the molten salt is below 1G capacity%. This is because the energy can be connected and the current is not directly flowed. J: The chamber and the cathode chamber are not

Consul inc /^ =^ operation purchase, the frequency of the fine machine is different, only the solution of the solution is in the structure of the salt bridge in the _; or the shape of the electrolytic cell is the type of the cylinder 201138693, the anode is placed in the central part of the molten salt electrolyte bath ^ Make it surround the anode of the electrolytic cell. Hyun melt salt electrolysis ^ ^, and the configuration of the cathode to reduce the water vapor concentration or oxygen concentration is also as described above, depending on the structure of the f molten salt electrolysis cell 'sometimes reduced melting; touch = ' can inhibit the ship salt water absorption. It is preferable to make the single_f to f 0.1~100m2/m3, more preferably 〇.2~8〇mV /, the phase contact area of the hole is the density of 1~2^〇m ^ high current density, current area production The speed is sometimes lowered. The unit electrode is better, but in the case of c/Jt exceeding 200AAW and "higher current density is obtained by ===", there are: 2 100A/dm, and more preferably 3~ 50A/dm2. Also yang 0 season 乂佳«上ί可炫电: The melting point of the quality bath operation = words, should be 9Q ~ WC electrolysis of the operating impurities sufficient recovery and avoid mixing points. 50 to 100% of the time is a supercharged condition for electrolysis, can be carried out in the cathode for high purity and then once again to H, the target purity can be used, the same operation can be used according to the type of impurities Refining becomes the target purity. Alternatively, it can be used to make the "chain" to be implemented. The chlorination method of a specific chlorinating agent, etc., by using a high-efficiency method such as ammonium chloride to produce a metal indium/salt refining technique*, such as a good effect, that is, a thaw salt to recover a low melting point metal smelting salt electrolysis cell , at least the package? Long down ship (four) electric touch, which is characterized by: the configuration is Fuyang; ^ Guan Ma iRt = the space containing the liquid material of the low melting point metal alloy, and the arrangement of the external dipole chamber Cathode chamber, 201139693 • The residue containing the low-touch metal alloy is supplied with a molten salt containing a low-melting point metal compound in the inner cylinder of the surface-forming chamber, and the electrode is inserted into the anode chamber and the cathode chamber from the DC power source. Produce the sowing, you check the outlet of the cathode chamber and electrolyze (4) refine the metal of the low melting point continuously or intermittently. In the present invention, the molten salt electrolysis cell has an anode chamber 1 and an inner tube 2 as shown in FIG. 1 and FIG. A liquid material containing a low-melting-point metal alloy (% of the anolyte is read as long as it does not react with the alloy to be retained, and the metal material of the zinc-based i-supply is specifically considered to be stainless. ,: good titanium, titanium-based alloy. From the resistance to a continuity or intermittent = the supply of anolyte 9 is the gap between the supply or the additional supply: 4, a fiber, although the chamber 1 and the inner cylinder 2 in the sun i Room: 'Because the composition between the electrolyzed component chamber and the inner cylinder constituting the alloy is kept fixed, it is preferable to take the anode from the take-out 4, _, # secret surface setting to extract the anodic liquid 9 or the continuity. Heating, the lower portion of the anode chamber 1 is heated by the heating crucible 12 to perform the anode chamber portion: 2, and the dead portion is closed. The inner tube 2 is disposed to be cut away from the portion where the anolyte 9 can reach the bottom portion. Slit-like, homogenized. The inside of the same inside is slightly outside, so that the composition of the anolyte 9 can be 岣201139693 again, by closing the inner cylinder 2 Shangqiu, L a, prevents the moisture in the atmosphere from mixing, and the reason for the deterioration of the salt is also a major feature. Yu Yu’s long-term stagnation operation, this also the export D 5 of the invention The method of arranging the layer-shaped smelting salt 10 is as follows: for the method of forming the sulphate 9-shaped salt 10, for example, a molten salt is formed from a molten discharge port 6 to form a molten salt in the inner tube, and a liquid gas is discharged in the inner tube The upper inner cylinder is turned over and heated to make the four-pole anode enter the lamp reaction, and is not particularly limited. The genus 2 glass gas resin, preferably quartz glass 』===tube discharge: r-point metal-melting The page is formed of an insulator. Among the insulators, it is preferable to use a glass of a high-quality, high-quality glass, a terrarium, a fine metal, a liquid, a fine metal, and an outlet. 7 Continuous or intermittent discharge and recovery. And the energy of 4 2 ΐ ί can be used to resolve the shape of the low-melting metal, especially ... limited to cube, cube or cylinder. More uniform configuration is not Particularly limited, but as shown in Figure 2, the oxidation of the low melting point metal in the alloy of the cathode chamber 3 ^ '郷The dissolution is also relatively small, and the density distribution can be small, so it is better. The cross-sectional area of the cathode chamber 3 is Γ, and the interface area of the smelting and melting salt is larger. It is preferable that the resistance of the ring is small, but the result of the excessively large is that the area of the molten salt 10 of the molten salt is small, so that the molten salt 10 is increased and the sectional area of the dipole chamber 3 is the sectional area of the inner cylinder. 30~70%, preferably 201139693 is 40~60%. Metal=Use===== can be from low melting point, low melting point metal refers to indium, tin, gallium, suitable metal. De-refining in the present invention In the production of good indium ... ·, relatively low 'and in the molten salt to maintain the molten salt in the inner cylinder, only I county tongue melting point metal alloy, can enter the _| solution ==== room containing The mixed zinc sulphide and the indium chloride are mixed and 趟f = \ is suitable for the molten salt. The use of such a molten salt electrolysis cell is characterized in that the production speed of the area of the 1-200^^ area is sometimes lowered. In terms of productivity, u ί==2 is analyzed at the cathode under strict 200 lions: Day r sometimes mixes impurities and reduces purity. The current density is s, preferably 2 to 150 A/dm2, and more preferably 3 to temple~. = melt salt! The operating temperature is not particularly limited as long as the electrolyte bath and the metal containing the low melting point are all in a molten state. From the viewpoint of the corrosion of the material and the operation of the molten salt electrolysis, it is preferably 5 〜 to 400 ° C, preferably 90 ° C to 350. (: In the present invention, the anode contains a low melting point metal alloy. The melting point metal in the present invention must contain a sheet of indium, tin, and gallium. The alloy refers to a metal halogen and/or The metal (4) composed of a non-metallic element has a bonding state and is particularly limited. The content of the low-thorium gold content is not limited, that is, it is suitable for use as a low melting point metal or a trace amount. In terms of the degree of refining, recovery, and productivity of the melting point metal, the content of the low melting point metal in the alloy is preferably

From 100 wtppm to 99.999 wt%, preferably from 丨 to 99.99 wt%, more preferably from 60 wt% to 99.9 wt%. The metal other than the low melting point metal in the horse alloy is not particularly limited in kind, and examples thereof include: Li, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, 13 201139693

Cr, Μη, Fe, Co, Ni, ^ A n ^

Cu > Zn > Ge > As ' Se ' Sr > Y > Zr > Nh > M〇, RU, Rh, Pd, Ag, Cd, Sb, Te, Cs, Ba, Ta, w, Re,

One or more of Os, Ir, Pt, Au, T1, Pb, and Bi are selected. Among them, the salt-cutting electrolysis towel and the low-melting point metal are separated and refined.

Li, Na, Mg, A, Si, K, Ca, Sc, Ti, V, 〇, Mn, Fe, c〇,

Ni, Cu, Zn, Ge, Sr, Y, Zr, Nb, Mo, Ru, Rh, Pd, AC d, Cs, Ba, Ta, W, Re, 0s, Ir, Pt, Au, Ώ, pb, It is preferable to use Cu 'Fe, Ni, and it is easy to separate and refine Dx, [Effect of the invention] According to the method of the present invention, highly refined metal indium can be produced from a metal-containing gold towel at a yield. [Embodiment] [Embodiment] - The following "by the invention", but the present invention is intended to be applied. In addition, in the present invention, the method for measuring the moisture content of the secret money is to dissolve the melt in the water, and the sample of the alcohol swill is sampled, and the card is mixed with the graffiti; Sir: AldriCh^5^ 5 ^ ydranal-CompositeS,) Make a titration and nose. ” / [Example 1] In the case of pure tongue, 'the rib produced when the target is made of ιτο target: ping ping 51 (4) and mixing the pulverized powder with the ΐ ΐ product name “KS-75”) 17〇.9g, The mixture was placed in an inner volume of 1 L of white pot and placed in an electric furnace. After the nitrogen gas was replaced in the electric furnace, 卩ίίίί was warmed to Η' ′ for 6 hours and kept at _°C for 3 hours. After the completion of the reaction, the total weight of the reduced product and the unreacted raw material powder was determined to be 1456.3 g. After the treatment was analyzed by X-rays, the oxidation of the waste in the waste, 201139693, was weakened by the diffraction, and replaced by the rhyme. The reduction of copper oxide in the pulverized ITO scrap was better. In addition, it was converted into Jin Gu, and it was confirmed that the product was scratched with tin alloy. Tin material king 4 Secondly, in order to refine and recover metal indium from the alloy, as shown in Fig. 3, it is made of Baili bribe 8 glass to make salt two of the Wei Wei solution tank, and the anode is placed as a reduction product, that is, indium tin. The same degree of alloy and .g may be placed on the bungee to prepare a purity of 99. " 9 wt% of metal indium 29 9g. Also; = the weight of the molten salt is 7 〇.3g 'its composition is a gas volume Ζ ίίΓ ^ 28·5 〇 Second, the platinum wire is inserted into the anode and cathode of the electrolytic cell, connected to the electric power muffle furnace (mUfflefUmaCe), so that the electrolysis The temperature of the tank is 240. (:1 solid molten salt electrolysis. The molten salt electrolysis adopts constant current device (Ji Shui Electronics, small ^c18-5)), and is set to current 値G.94A, current density > 30A/dm2 6 The indium-tin alloy placed in the anode chamber dissolves 3 in 5 g of metal indium, and 6 Ug in gold from the cathode = the content of water in the molten salt at the end of electrolysis is "heavy." Because the amount of the cathode chamber is 29.9 g. Therefore, the amount of electrolysis is 31 2g. The voltage of the electrolytic cell is maintained at 4.5V. After removing some of the metal indium of the cathode, it is dissolved in hydrochloric acid, and Icp (inductive surface) is used as a precipitation device to determine the impurity content. The amount and purity of indium are modified. The tin content in the metal indium is as low as 95 ppm by weight, and the zinc content is also as low as 1 ppm. To the indium oxide, the indium oxide is oxidized by using the metal indium recovered as a raw material. The ITO target was coated and evaluated as the sputtering performance of the target. As a result, almost no tuberculosis was produced, and the raw material for the production of the target was regenerated. [Example 2] The indium-tin alloy recovered in Example 1 was reduced, and the same Belle P as the implementation of ^1 was used. yreX® glass Η type electrolytic cell and implemented molten salt electrolysis 15 201139693 99 Qiao Jin 61々, and placed in the cathode chamber to prepare another purity - indium chloride ° 'genus weight = ^ 6 put = ^ salt weight Department 75. Know that its group moisture content 0 5 tongue to 〇 / weight 71.6 mol%), zinc chloride 28 · 4 mol%, electrolytic sample together to insert platinum wire into the anode and cathode of the cell, even . The electric power muffle furnace is released, and the temperature of the electrolytic cell is made. C and the melting is performed 値of===:::· is set to the current 86 1^吉ί The dissolution of the anode-sand alloy is 55.8g ‘Received from the cathode chamber=Secondary discharge and the electrolytic cell voltage is maintained at 4.8V. [Comparative Example 1] Example 1 Hi i, the indium-tin alloy recovered by reduction of 1 was used and implemented. In the type of electrolytic cell, the weight of the smelting salt of the lining salt electrolysis system-gas is 7 〇, but the group Ϊ is also indium (= 71.5 mol%), and the chloride is 5 mol%. The water jet 3 has a system to add moisture to the molten salt to become 9% by weight. Platinum is introduced to the anode and the impurity of the electrolyzer, and the electric assessment is placed at a second degree of 240. . And the implementation of the smelting salt electrolysis, the salt Ϊ 2 3, the flow-seeking device, slave current M94A, electric fairy at 30A / dm, the same as the application of the same example 2 for 14 hours. Μ 7 ' is dissolved from the steel-tin alloy placed in the anode chamber. For example, the moisture content in the salt of the cathode chamber is (10)% by weight. Since I = 30.1 g, the amount of electrolysis was 53 6 g. Remove part of the gold from the cathode

S 16 201139693 is indium, dissolved in hydrochloric acid, using the amount and purity of metal indium corrected =, to obtain the impurity content, from the weight of indium deposited in the cathode chamber is 1 by weight of the indium chamber 57.2g , 98.6% of 2. In the meantime, the yield is lower than that of the embodiment, and the electrolytic cell voltage is unstable, and the initial value is 6.1V.邳 在 在 5.2 5.2 5.2 5.2 5.2 5.2 5.2 5.2 5.2 5.2 5.2 5.2 5.2 5.2 5.2 [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ , copper 322 () weight Peng. Continuous solution ^' as shown in ®14, using 127 12 m ^% metal copper 49.lg made from Belle Pyrex® glass. The weight of the dissolved salt placed is 34.1 • Stem five 〇. — Emulsified steel 68.1% by weight (=65·9 mol%), zinc vapor 兮*^ of water* content is 〇.4% by weight. Insert the non-clock steel wire into the ΐίίί 连 电 - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - At this time, the nitrogen concentration of the nitrogen towel is like lvol%. Using the constant current device used in the first embodiment, it was set to 5 电 on the electric power, 2 〇 A/dm 2 in the current density, and continuously energized 3 〇曰. Since the amount of retention was reduced by the two t/1 electrolysis of the anode chamber, the used indium tin was supplied once a day. The metal indium which is electrically deposited in the cathode chamber is recovered by continuously flowing it out of the overflow pipe. ,,,, σ fruit 'the weight of metal indium recovered from the cathode chamber, the current efficiency of the cathode chamber, and the content of impurities tin, copper, and zinc, as shown in the table below, Table 1] Number of operating days (day), 10 20 30 Indium weight (g/day) 46.0 45.9 46.1 Rate (%) 99.4 99.1 99.6 17 201139693 Tin in the j (viewing ppm) 23 18 33 Copper content (ppm by weight) 1 1 2 LgjW_^tt(tt ppm )_ L· <1 <1 O〇〇/,, L β inverse term, the influence from the cathode king--,-卞有二', and the impurities are tin, copper, zinc The content of 1 fruit ^ aft & at the end of the run to find the water in the molten salt contains whistling ΐ ΐ ΐ ΐ 因为 因为 因为 因为 因为 因为 因为 因为 因为 因为 因为 因为 因为 因为 因为 因为 因为 因为 因为 因为 因为 因为 因为 因为 因为 因为 因为 因为 因为 因为 因为 因为 因为 因为The smallest [turns in fixed position than in 3G. Indium, ===: Refining and recovering metal in used indium tin alloy ρ Refining is the same as in Example 3, using Belle as shown in Figure 4.

Pyrex8 is a type of continuous electric reliance. This alloy was placed in the cathode chamber to a separately prepared purity of 99.999 wt% of metal indium 5 〇 4 3%), and the compound was 39.2 mol%. At this time, the moisture content is ==4. The H5 wire is inserted into the anode and cathode of the electrolytic cell, and the electrolysis is placed in the V-muffle furnace, so that the temperature of the electrolytic cell is the shoe, and the silk salt is simultaneously applied to the electrolytic cell. electrolysis. At this time, in the atmosphere: is 値 to electrolysis and the amount of paving is reduced, so the daily supply = to = 4 times. . The metal indium deposited in the cathode chamber is shown in the cathode chamber of Table 2 by the ratio of the ratio of tin, copper and zinc to the ratio of the content of tin, copper and zinc.

S 18 201139693 f Table 2]

More than 99% of 165 cases of 3, production of miscellaneous! The flow efficiency is about 97%, which is lower than the full refinement of the implementation. The content of zinc in miscellaneous shells is also high, and it is impossible to enter [Comparative Example 3]. The used indium tin alloy used in Comparative Example 2 is placed in the Belle pyrx__H type continuous column 3 homopolar chamber using the m gate of each disk. Combine the l4S7rt electric fresh simmer and see the electrolytic refining.于阳量% of metal indium 50.4g 1^= insect to salt put back the purity of 9_ indium sulphide 63.2% by weight (=6丨5 二^里, 8.6§, its composition is a chlorine amount will be moisture ;===== Air-filled 〇if salt electrolysis containing gas at a concentration of uL/k continuous 3 gas concentration 15 1% using the constant-powered spine used in Example 1, set to a heart rate of 2GA/dm2 and continuously energized Because of the anode chamber holding capacity, the used indium tin alloy is supplied once a day. The metal indium produced by electrolysis = I is continuously discharged from the overflow f and returned to the ι- to the molten salt to produce a large amount of white. For solids, the running start rate is reduced to 76% and stops. The result of the operation, that is, the recovery 3 shows the current efficiency of the f-pole chamber and the contents of impurities tin, copper and zinc, [Table 3] 5 19 10 201139693 The amount of fines recovered from the cathode chamber (g/day) 44.2 40.3 35 2 Flow efficiency (°/〇) 95.5 87.0 76.0 Tin content (weight pmn) 115 160 212 Copper content (ppm by weight) 2 Γ 3 4 zinc Content (heavy ppm) ό From the main station θ ^ ^ . J 335 312 -- ζ _ 275 7 tons of philosophical two electric 'the effect of 95.5% hurricane reduced to 76.0%, &, copper content is higher and It is not possible to fully refine. After the continuous operation at 1Q, the moisture content of the salt spray towel is measured, and the result is increased by 2 [Comparative Example 4]. The used indium tin alloy of the ship is used in the same way as in the third embodiment. Electrolytic refining was carried out in a continuous cell of 璃 璃 。 于 417 417 417 417 417 417 417 417 417 417 417 417 417 417 417 417 417 417 417 417 417 417 417 417 417 417 417 417 417 417 417 417 417 417 417 417 417 417 417 417 417 417 417 417 417 Indium 46.6 wt% (= 45.3 mol%), zinc chloride % 7 mol %, moisture amount Ϊ. Will not _, the line is inserted into the anode and cathode of the cell, connected to electricity 曰 曰, put electricity In the muffle furnace, the temperature of the electrolytic cell is 29 (rc, in the concentration of the vapor concentration. 1% of the nitrogen is continuously distributed in the intestine while the molten salt is electrolyzed in the embodiment 丨t to make the (4) constant electric seam, and the 値 is 0.45A, f 丝 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 And impurity tin, surface, [Table 4] Operating parameters (曰) 1 "- 3 Indium Caojin & recovered from the cathode chamber /day) 45.8 45.4 1 -1 45 5 Current efficiency of the cathode chamber (%) 98.9 98.1 98 3 Recovering the tin content in indium (contribution 25 21 31 Recovering the copper content in indium (view ppm)> 1 1 -- -- 2 ---- 20 201139693 Recovering zinc content in indium (ppm by weight) 1531 1883 2352 攸This watch is a 'very high rhetoric content in copper recovered from the cathode chamber, refining is not sufficient, run for 3 days stop. [Comparative Example 5] Electrolytic refining was carried out using the used indium tin alloy used in Comparative Example 2, using a continuous electrolytic cell made of Belle Pyrex ortho-glass in the same manner as in Example 3. The alloy 137.3⁄4 was placed in the = chamber, and another prepared metal indium 51,6 g having a purity of 99 999 was placed in the cathode chamber. The weight of molten salt placed was 115 1 ^ indium = 6.2% by weight (= 25.5 mol %), and chlorinated in 74 5 mol %. At this time, it is G.5% by weight. Insert the stainless steel wire into the electrode of the cell and melt it into the muffle furnace, so that the temperature of the cell is 2 pits wide and the degree of relaxation (10) is blocked by a fine continuous flow; the solids cause fouling. The impurity content of indium is shown in Table 5 below. The operation is stopped from the cathode chamber before the stoppage [Table 5] The 354 chain is insufficient. ° μ, the indium recovered from the cathode chamber has a very high _ content, and the fine [Case 4] up uses the smelting salt electrolysis shown in Figure 1 and the molten salt is formed in the anode chamber. The following devices constitute refined metal indium. ', σ 3 metal indium alloy, electrolysis in the cathode chamber 1. Device configuration 1) anode chamber 21 201139693 Dimensions: length 280mm x width 350mm x depth 140mm, thickness 5mm Material: stainless steel (SUS304) Shape: square groove (with anolyte removal Nozzle) 2) Inner cylinder size: length 250_χ width 250mmx height 250mm, thickness 3mm Material: quartz glass shape. Square groove (bottom: opening, side lower part: 2 sides of each surface 30mm><30mm slit upper part: attached 2 places Nozzle) 3) Cathode chamber size. Length 30mmx width 200mmx depth 30mm, thickness 3mm, 5 materials: quartz glass shape: 5 square grooves 2. Molten salt bath composition. Indium chloride: zinc vaporization = 78: 22 ( Moer%), moisture content 〇4

Electrolysis temperature: 300 ° C 90 The composition of the metal-containing indium alloy (anolyte 9) of the chamber 1 is 9.7 wt% of metal indium per ton of metal tin, and is placed at 8 〇 at the beginning of the electrolysis operation. ί 生 生 ” 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 连续 连续 连续 连续 连续 连续 连续 连续 连续 连续 连续 连续 连续 连续 连续 连续 连续 连续 连续 连续 连续 连续 连续 连续 连续 连续 连续 连续 连续 连续 连续 连续 连续 连续The alloy content of the composition is said to be slightly higher, and it is replaced by tin of a bismuth-containing alloy of ~1 to 1 and continues to be electrolyzed. The alloy of this composition is replaced by 40.2 kg, which is not compatible with the atmosphere, and can be operated to make it melt. Salt Η)

S 22 201139693 From the 14th, the content of the tin content in the molten salt shoes is 580wtppm, and the moisture content in the molten salt in the metal indium extracted from the cathode contains: = the tin content in the sputum is in the system The step shown in Example 1 is supplied to the anode (four) i, and the 3 alloy (anode 9) is misplaced. The composition of the salt 10 is gasification tin 76wt9z, and Ning refined. Further, the molten electrolysis temperature was 350 °C. 0, octane compound 24wt% mixed molten salt, supplied to the pole chamber 1 containing the metal lead 4.7_, and in the electrolysis and into the metal tin 953, the implementation of continuous transport U4 / 3 (i == PAsi (^5"_祖(四)法φΓ7 7. The metal tin analyzed by I has an average of 5 31CO per day, and the sputum = binary = shape r 'taken out of the take-out nozzle 4; =% of the amount is 1' from the take-out nozzle 4 In the anolyte taken out, the second embodiment of the present invention relates to a method for refining and recovering metallic indium from a metal-containing indium alloy. [Simplified Schematic Description] 囷 [Fig. 1] is a molten salt electrolysis according to an embodiment of the present invention. The longitudinal section of the refining apparatus [Fig. 2] is a cross-sectional view taken along the line I-Ι of Fig. 1. ^ [The figure schematically shows the n-type electrolytic cells used in the first and second embodiments and the comparative example 1. [Fig. 4] The continuous electrolytic cell used in the third embodiment and the comparative examples 2, 3, and 4 is shown in the following. 23, 2011 39693 [Explanation of main components] 1 : anode chamber 2: inner cylinder 3: cathode chamber 4: nozzle 5: inert Gas introduction port 6: exhaust gas discharge port 7: outflow port 8: cathode chamber support rod 9: anolyte 10: molten salt 11: catholyte 12: heater 13: direct current Source generating device 14: anode (chamber) coarse hi alloy 15: cathode (chamber) refining In 16: molten salt 17: anode wire (white gold wire with protective tube) 18 . cathode wire (white gold wire with protective tube) 19 : Anode (chamber) coarse I; n alloy 20: cathode (chamber) refining In 21: molten salt 22: anode wire (SUS wire) 23: cathode wire (SUS wire) 24: coarse In alloy input port 25: refining In overflow Port 26: gas introduction port 27: exhaust gas outlet 28: gas communication pipe

S

Claims (1)

201139693 VII, the scope of application for patents: L,; the manufacturing method of metal indium' is the use of indium containing metal indium, the salt of the eight genus, the indium gasification of the compound as the main component = indium chloride in 68 work In the square;: indium vapor-zinc vaporized molten salt in weight% or less. More than %, the water content of the molten salt is increased by 〇·5 2 (4), wherein the method for producing metal ants of the indium chlorinated 1 ^ is in a steaming gas, and in a gas of the following Molten salt electrolysis is carried out. M is a method for producing metal mosquitoes, which is a molten salt electrolysis in an environmental gas of less than % of the exhibition. A method of manufacturing metal copper of 4, or 4, wherein the ring-and-air system selects one or more kinds of ambient gases from m. The manufacturing method of the metal indium of the above-mentioned items 1 to 5, wherein the operating temperature of the Wei Rong salt electrolysis is 140 to. c. A method for producing a metal indium according to any one of the first to sixth aspects of the invention, wherein the indium alloy is an alloy obtained by further inducing an indium compound.铋r as in May, she specializes in the manufacturing method of the metal indium of the seventh item, wherein the indium compound contains indium oxide. 9 For example, the method for manufacturing metal indium according to the patent scope f 8 wherein the oxidation-containing 25 201139693 indium material is an ITO waste 10 electrolytic cell whose characteristics are melted by the ship, is refined, low-grade metal, molten salt melting = electrolytic refining The device comprises at least: an anode chamber, a storage containing a low melting point: two, an inner cylinder disposed to be in contact with the bottom of the anode chamber, a DC power source disposed in the cathode chamber, and an external anode chamber to generate 4 gold a low melting point metal containing less than 9% of the volume of the anode chamber is supplied to the inner cylinder to supply a molten salt of a compound containing a low melting point metal, and the chamber generates a flowing current from the direct current power source, as in the scope of claim (4) Hyunrong salt electrolysis cell, among which glass, ceramic materials and fluororesin are chosen! Made above. The question is from the molten salt electrolysis cell of the 1G or u of the patent range, and the inner upper portion has the inert gas introduction σ and the exhaust gas discharge port. 13. As in the scope of patent application No. 1 to 12, the cathode chamber is made of glass. Unsinking, which is as in the first to third of the patent application scope: - the cathode chamber is composed of a plurality of containers 'and by the container; = tube = 26 S 201139693 16 , as claimed The molten salt electrolysis cell according to any one of the items 1 to 15, wherein the anode chamber is made of stainless steel. The molten salt electrolysis cell according to any one of claims 10 to 16, wherein the anode chamber has a nozzle for extracting a liquid material containing a metal alloy having a low melting point. 18, - kind of smelting and melting salt electrolysis method, the patent scope of the material is = molten salt electrolysis cell, the low melting point metal is from the indium, tin and gallium salt salt ΐΐ range of the 18th item The operating temperature of the package is 5 ° ° C ~ 400 ° C. x, 中,进行炫; Cai 18 or 19 _Salt Noodle Fang Feng. The current density is purchased by dm2 reading method, among them, into; Eight Diagram: 27