DE1035119B - Device for the production of purified manganese dioxide by electrolysis of a manganese salt - Google Patents

Description

Devices for the production of purified manganese dioxide by electrolysis of a manganese salt, the The anode compartment is separated from the cathode compartment by one or more diaphragms and one has the electrolyte between the cathode compartment and the anode compartment via a regeneration system are known.

In these known devices, the liquid to be regenerated is at the lower part of the anode space withdrawn and fed back to the cathode compartment below, i.e. the electrolyte is from the anode to the Cathode led. In the device according to the invention, on the other hand, the electrolyte circulates from the cathode through the regeneration device to the anode.

Two embodiments of the invention are described with reference to the drawing:

Fig. 1 shows a plan view of a device according to the invention, in which the electrodes are vertical, and

2 shows a section of the device according to the invention, in which the electrodes are arranged horizontally. ao

In Fig. 1, 1 is an electrolyte container, which is in an anode compartment 2 and in a cathode compartment 3 through porous walls 4 made of fabrics made of superpolyamide, asbestos or another similar material is divided.

In the space 2 an anode 5 is arranged, which is connected by a wire 6 to the positive terminal of a power source (not shown) is connected.

In the space 3, a cathode 7 is arranged made of conductive, unassailable material, such as. B. made of lead.

Device for manufacturing

of purified manganese dioxide

by electrolysis of a manganese salt

Applicant:

Cartoucherie Frangaise, Societe anonyme, Paris

Representative: Dr. A. Ullrich, patent attorney,
Heidelberg, Bismarckstrasse 17th

Claimed priority:
France of October 14, 1954 and October 6, 1955

Rene Dufour, Marcel Verron, Paris,
and Alphonse Gabriel Le Magoarou,

Colombes, Seine (France),
have been named as inventors

the p _H to bring independently to its optimal value, even in the anode compartment 2 and the other in the cathode-This cathode is a wire 8 to the negative 30 space 3. It is so avoided the formation of a complex terminal, not shown, above-mentioned current source deposit on the cathode, which forms a large electrical resistance in the known method, and it is thus possible to work with a lower, above-mentioned potential difference (3 volts).

The siphon 9 is arranged so that its small arm 9 α in space 2 (with the mouthpiece 11 at the end) slightly immersed in the upper part of the electrolyte 12 a, while its large arm 9 δ in the electrolyte 125 of room 3 almost goes down to the floor of the room.

The container has an overflow 13 which is arranged on the side of the cathode chamber 3 so that the Electrolyte 12 δ, which is located in the cathode chamber 3, can flow into a vessel or trough 14, at which

In the electrolytic decomposition with such a 45 lower part, a tube 15 is connected to a The manganese (II) ions migrate to the cathode, which leads to pump 16. This promotes the liquid from the trough where they discharge and either metallic manganese 14 via pipe 17 through filter press 18 and a (through a secondary reaction) or hydrogen and tube 19 into the anode compartment 2.

Generate manganese hydroxide while at the anode In the course of the electrolysis the through-

the sulfate ions discharge and by secondary reaction 50 average acidity of the bath, so that the manganese Generate nascent oxygen (a part of this acid is deposited in the form of its dioxide on the anode. It is

connected.

A siphon 9 allows the passage of liquid from the upper part of the anode space 2 to lower part of the cathode compartment 3.

An electrolyte 12 is placed in the container 1 up to a level 10 (slightly above the mouthpiece 11 of the siphon 9) brought such. B. the solution of a manganese salt, ζ. Β. Manganese sulfate, containing 25 g / l manganese and acidified with 15 g / l sulfuric acid.

At a current density of 1 ampere per square decimeter at the anode and cathode and a potential difference of 3 volts is obtained excellent results when the temperature is maintained at about 70 ⁰ C.

The substance serves to oxidize the manganese sulphate, the rest escapes in gaseous form).
Thanks to the presence of the diaphragms 4, it may therefore be necessary to keep the average acidity constant without interruption by adding a certain amount of an alkaline substance to the electrolyte,

809 57Ϊ / 331

3 4

which contains manganese. To this end, one gives thanks to the presence of manganese dioxide in the Funnel 20 a powdery manganese compound 21 cathode, no emission of hydrogen occurs there, (like manganese carbonate or manganese oxide) in one because of the electrolytic decomposition correct amount, which is then consumed through the distributor 22 hydrogen by the manganese dioxide, is shared. The funnel 20 is supplied by a screw 23 5 In addition, the cathode is supplied by the same manganese. A stirrer 24 which depolarizes the dioxide by means of a motor 25.

is driven, ensures a good mixing of the powder 21, the cathode 7 'in Fig. 2 causes a progressive

that comes out of the funnel 20, with the liquid in the disappearance of the manganese dioxide, and it is therefore

Trough 14. Required from time to time (e.g. every 24 hours) the

The purpose of the powder 21, as already stated above, is to supply io cathode 7 'anew by having it

to neutralize the excess acid, which gives itself a new coating of natural dioxide.

Forms electrolytes, and essentially the content of.

Maintain manganese in the bathroom. . tf ^els P ^iele

Thus, through the siphon 9 and the unit, 1 is obtained. In a device of the type shown in FIG

consisting of the overflow 13, the trough 14, the tubes 15 is shown, which consists of an electrolyte container with

15, 17 and 19 and the pump 16, a constant one anode from several thin lead ribbons and one

p _H value on the one hand in the anode compartment 2 and on the other hand cathode made of corrugated lead sheet, one gives a solution of

in the cathode compartment 3. 25 g of manganese sulphate and 15 g of sulfuric acid per liter.

According to another embodiment the can during the electrolysis is a temperature of 7O ⁰ C

Siphon 9 are unnecessary if the diaphragms 4 and 20 are maintained. A current density of

designed to be sufficiently permeable, so that the hydrostatic 1 ampere per dm ² at the anode and cathode. At a

Equilibrium is sufficient to keep the electrolyte from the anode - distance of 5 cm between the electrodes is one

to circulate space to the cathode compartment. a potential difference of 3.5 volts between the elec-

An embodiment of the invention is shown in FIG. 2. A yield of 1.300 kg of manganese is obtained with horizontally positioned electrodes, which in particular is suitable for use with a cathode, like an energy special at 1000 ampere-hours. , 3,5 · 1000 ",""contains the oxides of manganese. The elements of FIG. 2, consumption per kg of manganese dioxide = 2690, which correspond to those of FIG. 1, have the same reference watt-hours = 2.69 kWh.
sign, if necessary with a line. To neutralize the excess acid in the bath

The device according to Fig. 2 has a container Γ, which is 30 per kg of manganese dioxide 830 g of manganese oxide to-

placed in an anode compartment 2 'and in a cathode compartment 3'.

is separated by a very porous diaphragm 4 '. An excellent manganese dioxide is obtained in

The anodes 5 'are arranged in the anode compartment 2', which are very good for the production of dry elements

one of which consists of a sheet of lead, while im is suitable.

Cathode compartment 3 'a cathode T is arranged, which consists of 35 2. In an electrolyte container with horizontal elec-

granulated, natural manganese dioxide Ta (from the electrode arrangement (Fig. 2), the cathode contains natural

Sieve 20), a perforated sheet of lead 7 δ, a manganese dioxide, and the anode is using a

Filter fabric 7c and a perforated lead sheet Td lead sheet made. One uses a solution with

consists. The lead sheet Tb is electrically conductive with the 25 g of manganese sulfate per liter and 15 g of sulfuric acid per

Container 1 'connected, which is also made of conductive material 40 liters. The working temperature is 70 ⁰ C. For an anode

exists, e.g. B. made of lead. and a cathode surface of 1 m ^{2 is} used

The anodes 5 '(those through intermediate layers 33 of the current strength of 100 amperes equal to a current density

Container V are insulated) are conductive by a cable 6 at the anode and at the cathode of 1 ampere per dm ² ,

to the positive terminal of a power source (not shown) The terminal voltage can be reduced to 1 volt;

connected), while the negative terminal of this 45 the output of the pump is 501 / h.

The power source is connected to the container 1 'through a cable 8

is bound, which in turn is in electrical connection with the end of which it is necessary to clothe the

the plate Ib of the cathode is. Electrode to be made with a view to resolution

The anolyte can easily be replaced by the natural manganese dioxide (1,400 kg) of manganese dioxide

phragma 4 'of the anode compartment 2' into the cathode compartment 3 '50 (in particular for the production of dry elements

penetrate and there with the cathode liquid 12 δ suitable) at 1000 ampere hours, equal to an energy

Mix. consumption per kg produced manganese dioxide of

In the lower part of the container 1 'there is a connection 1.0 x 1000 -, ,, " _r ,,,, r> -n 1 tin.

, ,, L ₁ -LJj- - <r it. j η- ■ ι ·, «. = 710 watt hours = 0.71 kWh,

tube 34 attached, which the cathode liquid 12δ in 1.4

brings a trough 14, from where it through a pipe 15 55 that corresponds approximately to the fourth part of the consumption in

is fed to a pump 16. The pump then presses example 1.

the catholyte via the tube 17, the filter To neutralize the excess acid is required

press 18 and the tube 19 into the anode space 2 ". 82 g of manganese oxide per kg of manganese dioxide produced,

As shown in Fig. 1, you can in the trough 14 that corresponds to about a tenth of the amount that

a powdery compound 21 of manganese through 60 according to Example 1 is used,

insert the funnel 20. A stirrer 24 serves to instead of an anode or a cathode can also

the powder and the acidic liquid in the trough 14 can be used to several of these elements. So z. B.

mix. the anode contain several rows of ribbons or several

In the device according to FIG. 2, the cathode 7 'contains vertical parallel layers (which together form a horizontal

natural, granulated manganese dioxide, which forms the 65 zontal anode; Fig. 2).

The cost of reducing the manganese dioxide to manganese compared to the known devices

Oxydul are reduced and thus also the subject matter of the invention the particular advantage that

consumption of energy as a result of the lowering of the potential - one continuously with the continuous supply of

difference to 1 volt instead of 3 volts between the anode additional substances - such as B. Manganese monoxide — work

and the cathode. 70 can.

Claims (5)

Patent claims: 1. Device for the production of purified manganese dioxide by electrolysis of a manganese salt, wherein the anode compartment is separated from the cathode compartment by one or more diaphragms and one continuously pass through the electrolyte between the cathode compartment and the anode compartment via a regeneration system can, characterized by a connecting line (13, 15, 17, 19) between the cathode and anode compartment, for guiding the liquid from the upper part of the cathode space (12 δ) via a regeneration system (14) to the lower part of the anode space (12 a) is used and through a connecting piece (9) from the upper one Part of the anode compartment to the lower part of the cathode compartment. 2. Apparatus according to claim 1, characterized in that the anode space (12 a) above the Cathode space (12δ) is arranged. 3. Apparatus according to claim 1 and 2, characterized by one of granulated manganese dioxide existing cathode. 4. Apparatus according to claim 1 and 2, characterized by one consisting of metallic strips Anode in which the strips are arranged next to one another on a common carrier. 5. Apparatus according to claim 4, characterized by strips coated with manganese dioxide. Considered publications:
German patent specification No. 624 723. 1 sheet of drawings 1 809 579/331 7.58