JPH0325518B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Summary of the Invention] The present invention provides a novel electrolytic method for depositing and/or recovering metals (excluding tin, hereinafter the same) in particular in their elemental state and for other redox reactions. Regarding.

The electrolytic method provided by the present invention can be used in particular for electrodepositing metals in the form of dendrites and for electroplating metals onto substrates. This electrolytic method can also be used to carry out chemical redox reactions, such as the oxidation or reduction of chemicals by electrolysis.

The method of the invention particularly uses an electrolyte system comprising at least two phases, one of which is an aqueous phase and the other phase is an aqueous-immiscible phase. , current flows ionically rather than electronically across the interface.

[Prior Art] Two-phase electrolysis systems are already known. for example,
Mercury electrolyzers, which are commonly used to electrolyze sodium chloride solutions to produce chlorine and sodium amalgam, and ultimately sodium hydroxide, utilize two phases: an aqueous sodium chloride solution phase and a metallic mercury phase. do. However, in this case the mercury phase conducts electricity electronically, ie by the movement of electrons as in the case of conductive metals. In fact, the mercury phase acts as a liquid cathode. The electrolytic process used in the sodium hydroxide-chlorine industry also uses two aqueous phases separated by an ion exchange membrane. This is a method in which a sodium chloride solution is used as an anolyte and chlorine is generated at the anode in this anolyte. The electrolyte on the opposite side of the ion exchange membrane is an aqueous sodium hydroxide solution, and there is a cathode that generates hydrogen in this aqueous solution. These are both aqueous phases, and if there were no ion exchange membrane, these aqueous phases would be miscible with each other.

Such systems are severely limited in the types of electrochemical processes that can be performed within them.

When dealing with the oxidation or reduction of water-insoluble substances,
A more general and well-known problem typically arises in organic electrochemistry. For example, organic liquids are generally dielectric, so electrolytic techniques are generally unsatisfactory. To overcome this problem to some extent,
Common methods include using water-immiscible co-solvents, such as ethanol or acetone, to co-dissolve water-insoluble substances in the aqueous phase. Another method is to use solubilizing compounds, such as aromatic sulfonic acids, which do not dissolve insoluble substances and can also act as electrolytes. Both of these methods are intended to form a single water-miscible phase for electrolysis, which also limits their applications. For example, Organic Electrochemistry edited by MMBaizer, published by Dekker, New York in 1973.
Please refer to

[Structure of the Invention] A novel method is provided in which electrolysis can be carried out using two immiscible phases, one phase being aqueous and the other phase being non-aqueous, both phases electrolytically conducting electricity. discovered. Current flows between these two phases not simply by the movement of electrons, but rather by the movement of ions.

The present invention provides a novel electrolysis method. This method is an electrolysis method using a two-phase electrolyte system of an aqueous phase in which at least one electrode is disposed and a phase immiscible with the aqueous phase in which at least one electrode is disposed, the two phases being They are in direct mutual contact at the liquid-liquid interface.

The phase immiscible with the aforementioned aqueous phase (hereinafter abbreviated as non-aqueous phase) has the formula: R _Z Q ⁺ MX _n ^- [wherein R is an organic hydrocarbyl group, and the hydrocarbyl group is an onium (' onium) ions, Q is N, P, As, or Sb (where z is 4), or Q is S or Se (where z is 3), and M is tin. , X is I, Cl, or Br, and m is the valence of the metal plus 1]. One example of R _Z Q ⁺ is tetrabutylammonium.

The aqueous phase contains water-soluble organic or inorganic compounds. Examples of water-soluble organic compounds include water-soluble salts of long-chain organic carboxylic acids.

The aqueous phase has a high electrical conductivity, i.e. 5-10 ohm-
It exhibits a low resistivity of cms. In contrast, the non-aqueous phase typically exhibits a very high resistivity, for example on the order of 1000 ohm-cms. Whereas electrolysis using a non-aqueous phase alone typically requires extremely high voltages, the method of the present invention allows the use of significantly lower cell voltages. One of the advantages of the present invention is that it allows systems that otherwise poorly conduct electricity to be operated at practically economically acceptable cell voltages.

Since the non-aqueous phase is generally a very good solvent for other (organic) water-immiscible substances, the present invention can also be very easily used for electrolytic redox reactions using water-immiscible substances. For example, tetraalkylammonium halozincinates (which can be used as the non-aqueous phase in the process of the invention) are very good solvents for various non-polar organic substances, even for olefins such as ethylene. It is an excellent solvent.

The accompanying drawings illustrate the basic electrolytic cell arrangement and presently preferred practical embodiment of the invention that may be used in practicing the invention.

First, let's look at Figure 2. A suitable cell container 20 (rectangular, cylindrical, or any other desired shape) is formed from a suitable corrosion-resistant and electrolytically stable material, such as polypropylene. A cathode 21 is suspended near the bottom of the cell 20 and connected to an insulated current supply line 22, which is connected to the cathode terminal of a DC power source as shown. In use, the cathode 21 is completely immersed alone in the non-aqueous phase 24. When an aqueous anolyte 25 is provided over the non-aqueous catholyte 24 as shown, a liquid-liquid interface 26 is formed between the anolyte and catholyte. Anode 23 is suspended in an aqueous anolyte. This anode 23 is connected by a power supply line 27 to a DC power source for the anode. It will be appreciated that current flows across the liquid-liquid interface 26 between the two electrodes. When carrying out the present invention,
Such current flows ionically.

The electrodes used in the aqueous phase may be either cathodes or anodes, depending on the desired electrolysis method; conversely, the electrodes in the non-aqueous phase may be either anodes or cathodes.

When the aqueous and nonaqueous phases (anolyte and catholyte) have different specific gravities, one phase floats on top of the other and a liquid-liquid interface exists between these phases, as shown in Figure 2. It is formed. The two phases may also be separated by an ion-exchange membrane or a porous separator, such as ceramic or cloth, and placed in parallel, but in any case the two phases directly interact with each other at the liquid-liquid interface. are in contact.

In the specific examples described below, the aqueous phase is an anolyte,
The non-aqueous phase is the catholyte and the anolyte floats on top of the relatively heavy catholyte. In this case, one electrode is an anode consisting of a corrosive metal immersed in an aqueous anolyte and the other electrode is a cathode consisting of a non-corrosive material immersed in a non-aqueous catholyte. Both the anode and the cathode may be made of non-corrosive materials.

As used herein, the term "corrosive metal" refers to a metal that undergoes corrosion and gradually dissolves in the electrolyte when immersed in the electrolyte as an anode, as described above.
Corrosive metals that may be used generally include approximately +
Metals having a standard electrode potential (relative to a standard hydrogen electrode) of 1.5 volts to about -1.66 volts,
silver, gold, platinum, palladium, copper, lead, nickel,
Includes metals such as cobalt, indium, cadmium, iron, gallium, chromium, zinc, manganese, titanium and aluminum. “Non-corrosive material”
refers to a material that is not subject to corrosion, such as graphite or stainless steel.

The aqueous phase may be a catholyte and the non-aqueous phase may be an anolyte. In this case, the electrode immersed in the catholyte is a cathode made of a non-corrosive material, and the anode made of a corrosive metal immersed in the anolyte. Both the anode and the cathode may be made of non-corrosive materials.
If, in this arrangement, the anode is made of a corrosive metal, for example zinc, the anode will corrode during electrolysis;
Zinc dendrites are deposited on the cathode. Therefore,
According to the method of the invention, dendrite zinc can be formed from large blocks of zinc. Such dendrite zinc is a valuable starting material for the production of organozinc halides by direct reaction of zinc with organohalides.

If the anode is zinc, the catholyte may suitably be a non-aqueous zinc salt electrolyte. An example of such a salt is a complex represented by the general formula R _Z Q ⁺ ZnX ₃ ^- . This halogenated zincite complex is
It is produced as a by-product when zinc and an organic halide (RX) are directly reacted to produce an organic zinc halide in the presence of a compound represented by the general formula R _Z Q ⁺ X ^- . Also, if another metal is used as the corrosive anode, a complex of that metal will be formed by the R _Z Q ⁺ X ^- species.

When, for example, an aluminum anode is used instead of zinc as the anode, it is appropriate to use an aqueous solution containing aluminum trichloride and sodium chloride as the anolyte, and the catholyte to be of the general formula R _Z Q ⁺ AlX ₄ ^- . .

If another system uses a lead anode and an anolyte consisting of an aqueous solution containing lead carboxylate and sodium chloride, for example consisting of a C ₁₀ alkanoic acid, the catholyte has the general formula R _Z Q ⁺ PbX ₃ ^- It is appropriate to consist of If, for example, scrap lead is used as the anode in this system, the lead can be recovered in the form of dendrites deposited on the cathode. Impure metals other than lead can also be used as anodes, and metals other than lead can be obtained in purified form by this method (especially if the electrode potential of the impure metal is different from the electrode potential of the metal to be recovered). (This applies even if there is a significant difference).

As with lead, other corrosive metals may also be used with appropriately selected R _Z Q ⁺ X ⁻ species.
Of course, the R _Z Q ⁺ and X ^- species must be selected taking into account the basic requirements regarding immiscibility and solubility of the metal complex.

The present invention is fundamentally characterized by a non-aqueous phase, generally an organic liquid phase (note that this liquid phase is substantially Note that such phases are relatively non-conductive.

In contrast, it is desirable for the aqueous phase to be a highly conductive system, which is easily obtained, for example, by introducing suitable inorganic salts, as is already known in the art. Instead of or in addition to the salts, alkaline or acidic aqueous phases may be used as such electrolytes. Depending on the particular electrolysis method to be carried out, the anolyte and catholyte systems are selected according to the principles described above.

The method of the present invention is not limited to using a two-phase electrolyte system, but also includes an electrolysis method using a three-phase electrolyte system. The third electrolyte functions as a second anolyte in contact with the aqueous anolyte through an ion-permeable membrane. This second anolyte may be an aqueous alkali metal halide solution. A second anode is immersed in this as shown in FIG.

In the system shown in Figure 1, electrolytic cell 1
0 comprises a cathode 11 connected to a power source via a suitably insulated power supply line 12, which cathode is completely submerged in a non-aqueous catholyte 13 as shown. Immersed. Catholyte ￥1
Above 3 is an aqueous anolyte 14. The interface between the two phases is shown as 14a. In the anolyte 14 there is a chamber having at least one wall formed of an ion exchange membrane.
compartment) 15 is expanded. The membrane allows ions to pass through, but acts to prevent mixing of the anolyte 14 with another anolyte 16 . Suitably extending into this chamber 15 is an anode 17 of non-corrosive material, which anode is also connected to a DC power supply.
Extending into the anolyte 14 (hereinafter referred to as the "intermediate" anolyte in this embodiment) is an anode 18 of corrosive material, which anode is connected to the power supply line 19.
connected to the power supply by the

In said system, chamber 15 contains anolyte 1
Conveniently, 6 includes an aqueous sodium hydroxide solution, and the intermediate anolyte 14 is an aqueous solution of a metal salt, for example a metal chloride, such as sodium chloride. The catholyte 13 is preferably a metal complex R _Z Q ⁺ X ^- and is immiscible with the aqueous anolyte 14 . Anolyte 14
Various metals such as cobalt, nickel, titanium, manganese, and vanadium can be used as the salts, but are not limited thereto.

The method using the electrolytic cell of FIG. 1 allows recovery of elemental metals from dissolved salts of elemental metals produced as waste from other chemical processes. The metal thus recovered can be used to produce various metal compounds including organometallic compounds. The dissolved salt may be present in either the non-aqueous phase or the aqueous phase or both, and the metal is reduced to its elemental state at the cathode.

In particular, according to the electrolytic method of the invention, valuable carboxylic acid metal salts can be obtained directly from the formed dendrite metal and the desired carboxylic acid in order to advantageously produce highly reactive metal substances in dendrites. (for use as a paint dryer, for example). Heating the dendrite metal and carboxylic acid with air or oxygen (outside the electrolytic cell) dissolves the dendrite metal with excellent reaction rates and converts the carboxylic acid metal salt in high yield through direct reaction with the carboxylic acid. is obtained.

In the specific example of three electrodes shown in FIG. 1, when an alkali is used as the anolyte 16, oxygen is generated at the anode 17 because it is necessary to maintain the balance of the total electrolytic reaction equation.

The two-phase electrolysis system of the present invention can also be used for electrolysis involving only organic substances. In this case, for example, the first
In the embodiment of FIG. 1 or FIG. 2, respectively, an anode 18 or 23 of a non-corrosive material such as platinum is used.
This anode is suspended in an aqueous sulfuric acid solution as an anolyte 14 or 25. The anolyte is in interfacial contact with a non-aqueous phase comprising a conductive material such as, for example, acrylonitrile, adiponitrile and sodium carboxylate or tetraalkylammonium sulfonate or tetraalkylammonium sulfate. When electrolysis is performed, oxygen is generated at the anode,
At the cathode, hydrogenated dimerization of acrylonitrile occurs to produce adiponitrile.

Other organic species can likewise be electrolytically reduced by the method of the invention. For example, benzaldehyde gives benzyl alcohol, benzyl gives benzylidene, salicaldehyde gives the corresponding alcohol, nitrophenol gives hydroxyaniline, or allyl bromide gives propyl bromide. As with acrylonitrile, other reductive dimerizations or reductive polymerizations, reactions with organic substances, can also be carried out electrolytically, whenever an organic substance suitable for electroreduction is dissolved in a non-aqueous catholyte. .

The electrolytic method of the present invention can also be used to electroplate alloys onto cathode substrates. For example, two or more metals can be used as anodes...separate metal anodes (ie, two anodes, such as anode 23) or a single alloy anode. At this time, the anolyte is an aqueous solution containing chlorides of these metals, and the catholyte is a water-insoluble chloride of these metals, such as chloride in the form of Bu ₄ N ⁺ MCl _n ^- (Bu is butyl). things are used. When anodes made of two different corrosive materials are used, the relative amount of metal deposited varies depending on the amount of current supplied to each anode separately.

The electrolytic method of the invention has applications in the production of elemental metals from metal compounds, the purification of impure metals, electrolytic redox reactions of water-immiscible substances and electroplating.

To further illustrate the invention, presently preferred embodiments of the invention are presented in the following Examples.

Specific Example The apparatus used in this specific example was the cell shown schematically in FIG.

The cell consists of 11 glass beakers 20 set in a water bath (not shown) for heating and cooling. The cell includes a stainless steel disc cathode 21 connected to an insulating source 22. An aqueous solution (247 g) of zinc bromide (169 g) and sodium bromide (103 g) was mixed with an aqueous solution (165 g) of tetrabutylammonium bromide (214 g) with vigorous stirring. When this mixture was injected into the cell, it separated into two phases. The lower phase in which the cathode was immersed was tetrabutylammonium bromozincite ((Bu ₄ N ⁺ ZnBr ₃ ^- )
The upper phase was a 20% by weight aqueous solution of sodium bromide.

A zinc anode 23 (weight 884 g) was immersed in an aqueous sodium bromide solution. Connect the zinc anode 23 to the positive terminal of the variable power supply and connect the anode supply 2
2 was connected to the negative terminal. The cell was heated to 70°C and a current of 2-10 amperes was passed through the cell until a total of 25 amperes/hour was flowing through the cell. As a result,
24.7 g of zinc was lost from the anode 23 and 25 g of dendritic zinc was deposited on the cathode 21.

The cell 20 shown in FIG. 3 includes a cathode 21 (made of a non-corrosive material) connected to an insulated power supply line 22. The cell 20 shown in FIG. Below the cell is a non-aqueous phase 24.
The cathode 21 is completely surrounded by the phase 24. An aqueous phase 25 is provided above the catholyte 24 . The liquid-liquid interface of both phases is indicated by 27. aqueous phase 25
A chamber 30 extends therein, the submerged wall of the chamber being formed at least in part from an ion exchange membrane 32. Chamber 30 contains an anolyte 34, such as an aqueous solution of an alkali metal hydroxide, into which extends an anode 33 (of a non-corrosive material).

For example, one practical cell suitable for this electrolytic invention is shown in FIG. This cell is approximately 30cm x 30cm
The main body 41 is made of polypropylene and has a cross section of approximately 45 cm and an overall height of about 45 cm. The cell includes a polypropylene bottom valve 42 and is mounted to a base (not shown) such that the inverted pyramid shape of the bottom extends through a hole in the support platform. Cell is external electric heating tape 4
3, and is insulated and coated 44. The cell has two other tapes 4 relatively above it.
5 and 46.

The cell has two cathode plates 47 inside,
These cathode plates are connected to a cathode feed line 56. Above the cathode are two zinc anodes 48 (only one shown), which are connected to the mild steel feed line 5.
It is attached to 8. These feeders are supported in insulated bushings on an anode support frame 49, which is screwed to the platform.

Alongside the zinc anode there is a third anode 50 made of nickel. The nickel anode is supported by a mild steel feed line 57 and is fixed from the anode support frame. The nickel anode 50 is located inside a compartment formed by an external fixing member 51, an internal fixing member 52, and two ion exchange membranes 53, and is isolated from the rest of the cell. Members 51 and 5
2 have a U-shaped cross-section and are secured to each other by bolts sandwiching the membrane 53 so that a five-sided compartment with an open top is formed.

The cell has two polypropylene scrapers 54 with blades 54a that are forced over the surface of the cathode 47 to scrape and remove metal that has formed on the cathode, removing this metal from the cell. at the bottom (i.e. below the cathode)
It can be dropped. The cell is equipped with an agitator on a shaft 55, which is connected to a motor (not shown). A stirrer is used to stir the bottom phase containing the metal particles.

In operation, the zinc anode feed line 56 is connected to one rectifier (not shown), and the nickel anode feed line 57 and left anode feed line 56 are connected to another rectifier. The zinc anodes can be adjusted up or down on their feed lines 58.

For higher volume production, in addition to the cell shown in FIG. 4, the cell structures shown in FIGS. 5, 6 and 7 are currently preferred.

FIG. 5 shows a cross-sectional view of a 2000 amp cell, which may be equipped with conventional rectifiers, controls, etc. (not shown). In general, the structure of this cell is similar to that of FIG. However, in this example, the polypropylene body 60
is supported by a mild steel casing 61, which is placed on load cells 62 (only one shown) held on a support platform. Similar to the apparatus of FIG. 4, a steel support structure 63 carries two zinc anodes or other corrosive metal anodes 64 (only one shown) and a drive motor 65. The agitator drive may be a variable DC motor connected to the shaft 67 at 66, which drives the lower agitator blade 68 and scraper blade 69. The upper part of the scraper blade also serves as a phase agitator. The scraper blade 69 creates an upward movement of the metal halide complex to restore the electrolyte at the liquid-liquid interface, while satisfying the dual purpose of removing precipitated metal from the cathode surface. .

A push-up-type valve 70 is provided at the bottom of the cone in the conical bottom of the cell to remove metal dendrites and/or electrolyte from the cell. Push-in valves are useful because, in the unlikely event that unstirred dendrite metal settles and forms a crust, the crust can be cut open to allow drainage of the lower phase.

During start-up, each metal anode 64, weighing for example 100-200 kg, is held on a threaded steel rod 71 supported on an insulated bushing structure 72. This structure and the rod are each connected to a feeder cable 79. By this means the vertical position of the anode can be adjusted up or down.

The anode compartment, made of non-corrosive material, is shown as 73 and is a polypropylene box with an open top and a bottom sealed by an ion exchange membrane with a suitable support and seal. It is. This anode chamber is made of suitable steel parts 74.
An anode (not shown) made of a non-corrosive material and connected to a power supply cable 75 is inserted into the anode chamber.

The cathode plates 74 are here two stainless steel semicircles supported on appropriate polypropylene lugs within the cell and connected to cathode cables 78 (No. 8). (see figure).
A suitable plate heater 80 may be suspended below the cathode plate. A cooling coil 76 is also located within the cell. The aqueous anolyte and non-aqueous catholyte interface can be approximately 1 cm above the level of the catholyte plate, although the level of the catholyte plate may vary depending on the most efficient operation of a given device. . For example, during full operation at 2000 amps and 10 volts, cooling coil 7
6 must be capable of removing about 20KW.

77 shows a space or spacing between the cathode plates to allow the metal particles of the dendrites to fall into the lower cone of the cell as they are removed by the scraper blade; For this reason, FIG. 7 has been partially cut away. During this time, approximately 2
A problem is provided between the circumference of the cathode plate and the polypropylene cell body, which can be cm wide and also has a clearance of about 0.5 cm.

It will be understood that the foregoing specific examples are merely illustrative of the implementation of the invention. That is, as will be clear from the examples below, when zinc is used as the corrosive metal anode, dendritic zinc will be deposited on the cathode, but any of the other metals mentioned above can be used in place of zinc. Similarly, other R _Z Q ⁺ species can be used, and other halogens (eg, chlorine or iodine) can be used in place of bromine. To avoid complications from the formation of insoluble metal salts, mineral acid anions, generally represented by X ^- , may of course be chosen. Furthermore, the R _Z Q ⁺ species is diglyme,
It can be formed from alkali metal complexes or alkaline earth metal complexes using polyoxygen compounds or organic compounds such as polyoxyalkylene glycols, glycol ethers or crown ethers.

EXAMPLE The anode and cathode were weighed before and after electrolysis, which started when the cell contents were at 70°C. The current required to dissolve 10g/20g (30g) of the relevant metal for each metal anode was calculated and that amount of electricity was passed. Cooling coils were placed in the anolyte and catholyte to control temperature. Temperature was measured with a thermometer. The contents were stirred occasionally with a glass rod.

After electrolysis, remove the cooling rod, thermometer, stirrer, and both electrodes and wash with hot acetone/ethanol or dimethylformamide to remove residual Quast.
and precipitated metals were removed. The aqueous and organic phases were separated and filtered to recover the dendrite metal.
In the organic phase, the remaining metal complex was dissolved in a solvent described below to promote oxidation, and the solvent was distilled off under vacuum to recover the metal complex.

The dendritic metal was washed with solvent, then acetone, and dried in an oven or in air. The entire residue was weighed and analyzed for metal content.

Run A BU ₄ NZnBr ₃ + Zinc anode Before electrolysis After electrolysis Anode weight 883.7g 859.0g Cathode weight 233.1g 233.1g Anolyte composition NaBr weight 102.9g - Zinc weight - 14.11g Cathode solution composition Zinc weight 49.04g 33.19g Dendritic crystals Weight of zinc metal 25.00g Accountability of zinc = 99.8% Total coulombs flowed = 90,300 Theoretical corrosion weight of zinc = 30.59g Actual weight lost from anode = 24.7g Weight of dendritic metal recovered = 25.0g Run B Bu ₄ NCuBr ₂ + copper anode Before electrolysis After electrolysis Anode weight 223.4g 189.0g Cathode weight 233.0g 234.1g Anolyte composition NaBr weight 69.8g - Copper weight - 1.36g Cathode solution composition Copper weight 47.66g 44.12g Dendritic metal Copper weight - 35.3g Copper rating = 99.6% Total coulombs flowed = 49,200 Copper theoretical corrosive material weight 32.40g Actual weight lost from anode = 34.40g Recovered dendritic metal weight = 44.90g Run C Bu ₄ NPbBr ₃ + Lead anode Before electrolysis After electrolysis Anode weight 1490.8g 1464.5g Cathode weight 233.0g 232.7g Anolyte composition NaBr weight 90.74g − Lead weight − 5.10g Cathode liquid composition Lead weight 152.08g 126.90g Dendritic metal lead weight − 26.40 g Lead rating 98.8% Total coulombs flowed = 22,995 Theoretical corrosive material weight of lead = 24.69 g Actual weight lost from anode = 26.3 g Dendritic metal weight recovered = 26.4 g According to the present invention In any given implementation, the precise conditions to be used in the hope of optimal results will be dictated by the various parameters involved in all equipment in the process. . Therefore, the shape of the cell itself and the shape of the various electrodes, including the surface area of the electrolyte interface, will partially determine the performance and preferred operating conditions. As a result, exact guidelines cannot be asserted in advance, as the current density applied in the hope of optimal results will vary substantially from system to system. However, once the foregoing principles are demonstrated in accordance with the present invention, each of these conditions can be readily determined, and one skilled in the art will be able to do so within the scope of the foregoing disclosure. The method already outlined can be easily adapted for any desired electrolytic reaction.

For example, it will be appreciated that the temperature of the system itself is not critical to the operational performance achieved, provided that the respective electrolyte is in liquid form and below the disadvantageous decomposition temperature. Of course, the interrelationships of temperature, applied current, concentration, and reaction rate may be optimized and otherwise varied widely in hopes of obtaining the best results in any given system.

Therefore, the invention is limited only by the spirit and scope of the claims.

[Brief explanation of the drawing]

Figure 1 is a schematic diagram of an electrolytic cell using 3 electrodes and 3 types of electrolytes, Figure 2 is a schematic diagram of the supply of an electrolytic system using 2 electrodes and 2 types of electrolytes, and Figure 3 is a schematic diagram of an electrolysis cell with 3 electrodes and 3 types of electrolytes. A schematic diagram showing a specific example of a cell using the above, and FIGS. 4 to 7 are diagrams showing a specific example of a cell using three electrodes and three types of electrolytes. 11, 21, 47, 74... cathode, 13, 24
...Catholyte, 14,16,25,34...Anolyte, 14a...Liquid-liquid interface, 17,18,23,
33, 48, 50, 64... Anode.

Claims (1)

[Scope of Claims] 1. An electrolysis method using a two-phase electrolysis system comprising an aqueous phase in which at least one electrode is disposed and a phase immiscible with the aqueous phase in which at least one electrode is disposed, comprising: The two phases are in direct contact with each other at the liquid-liquid interface, and the phase immiscible with the aqueous phase has the formula: R _Z Q ⁺ MX _n ^- where R is an organic hydrocarbyl group, Q is N, P, As or Sb (where z is 4), or Q is S or Se (where z is 3), M is a metal other than tin, and X is I,
Cl or Br, and m is a number obtained by adding 1 to the valence of the metal.] An electrolytic method including a complex represented by: 2. The method of claim 1, wherein the aqueous phase has a high electrical conductivity and the phase immiscible with the aqueous phase has a low electrical conductivity. 3. The method according to claim 1 or 2, wherein the aqueous phase comprises a water-soluble organic or inorganic compound. 4. The method according to claim 3, wherein the water-soluble organic compound is a water-soluble salt of a long-chain organic carboxylic acid. 5. The method according to any one of claims 1 to 4, wherein the aqueous phase is an anolyte and the phase immiscible with the aqueous phase is a catholyte. 6. The method of claim 5, wherein the electrode immersed in the anolyte is an anode made of a corrosive metal, and the electrode immersed in the catholyte is a cathode made of a non-corrosive material. 7. The method according to any one of claims 1 to 4, wherein the aqueous phase is a catholyte and the phase immiscible with the aqueous phase is an anolyte. 8. The method of claim 7, wherein the electrode immersed in the catholyte is a cathode made of a non-corrosive material and the electrode immersed in the anolyte is an anode made of a corrosive metal. 9. The method of claim 5 or 7, wherein both the anode and the cathode are made of non-corrosive materials. 10. The method of claim 6 or 8, wherein the corrosive metal has a standard electrode potential of about +1.5 volts to -1.66 volts. 11 Corrosive metals include silver, gold, platinum, palladium,
11. The method of claim 10, wherein the metal is selected from the group consisting of copper, lead, nickel, cobalt, indium, cadmium, iron, gallium, chromium, zinc, manganese, titanium and aluminum. 12. The method of claim 6, 8 or 9, wherein the non-corrosive material is graphite or stainless steel. 13 Claims 1 to 1 further include an electrolyte.
The method according to any of paragraph 12. 14. The method of claim 13, wherein the electrolyte is a second anolyte in contact with the aqueous anolyte through an ion-permeable membrane. 15. The method according to claim 14, wherein the second anolyte is an aqueous solution of an alkali metal halide. 16. The method according to any one of claims 13 to 15, wherein the second anode is immersed in the second anolyte.