JPS59112572A - Reclaiming method of electrolyte used in electrolytic extraction process - Google Patents

Abstract

PURPOSE:To remove ammonium ion efficiently and make the continuous preparation of an electrolyte attainable, by having its effective component extracted as a crystal upon cooling after heating and concentrating the electrolyte, then separating it from a solution, and making the effective component into the specified concentration by solubilization in water. CONSTITUTION:When an electrolyte 5 inside an electrolyzer 1 comes too much with ammonium ion, a part of the superfluity is taken out into a reclaimer tank 9, while the electrolyte is heated with a temperature of more than 100 deg.C upon passing a hot catalyzer through a jacket 9a, evaporating all the moisture and concentrating it to the extent of 70-80% or less in the initial volume, and after that, a refrigerant is passed through the jacket 9 whereby the electrolyte is cooled up to a temperature of 20 deg.C and left intact as it is. At that point that a total of 80% or so in the volume is crystalized, a taking out valve port 11 is opened and a portion of liquid is separated and removed. A specified quantity of water is added to the iside of the reclaimer tank 9 where the crystalized electrolyte still remains and heated, then put back in the electrolyzer 1 by a pump 14 after preparating it into a specified concentration electrolyte.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is directed to a method for regenerating tunkyo ``Tunkyo'' used in the precipitation method.

Conventionally, porous electrode substrates such as porous nickel particles have been filled with nickel active materials.
A nickel salt water bath such as ALt narrow nickel is used as an electrolyte, and a nickel plate is used as a counter electrode. The production of nickel electrode plates by the so-called electrolytic deposition method that deposits JX is well known, but during the process, as 1 uJ passes, ammonium ions NH4 are deposited in large numbers. , this reduces the amount of nickel hydroxide present in the substrate,
This makes efficient continuous work difficult. Continuous I FI VC'+ti)'V for PI precipitation with good paternity
C is 1iI below a certain level that forms this ammonium ion.
IJiI11f is definitely cheap. For this reason.

B+17 alkaline water bath due to replacement with new liquid liquid and electrolysis
JI L ammonium ions are removed in the form of ammonia gas, and then the alkalinity is removed with acid, and the ammonium ions are removed from the '#iL's solution. However, this increases the manufacturing cost, and when the old Pc solution is used, NaNO3 is generated which remains on the electrode plate during neutralization and deteriorates the self-emission characteristics. This may be accompanied by disadvantages such as poor performance.

This product eliminates these drawbacks and removes ammonium ions at a good ratio without using the entire yarn product.
This provides a complete method for regenerating the 1JLm solution used in the electrolytic deposition method that enables continuous production. In the method of regenerating the electrolyte, the electrolyte is removed from the electrolytic tank and the electrolyte is recycled. It is characterized by heating and concentrating and then cooling to precipitate the active ingredients as crystals, and then separating the liquid from the resulting crystals by dipping into water to form an electrolytic solution with a certain concentration.

An example of the implementation of "Honmaru" will be explained with reference to the direction of τj.

Figure 1 shows an example of a nickel hydride-activated Ih material A used in the production of a two-kilometer electrode for alkaline livestock production, which is equipped with an electrolyte regeneration device that implements this method. l) Ke'I
tL Kaizo, (2) is DC power supply, (3) is DC power supply (2)
(4) is the strip-shaped nickel sintered substrate connected to the DC power source (2), (5) is the nickel return electrode plate connected to PJ'r, (5) is the nickel return electrode plate connected to .The electrolyte solution (5) in the stain tank (1) is coated with an oil layer on the strip-shaped nickel sintered substrate (8 cracking rolls of 4J al iil! I <6) and wound onto the winding roll (7) on the other side. (8) indicates a plurality of guide rollers that guide the substrate, and one of the guide rollers is connected to (2). The substrate (4) has, for example, a porosity of 80 mm and a thickness of 0.68 mm.For this turret plate AVc, the continuous electrolytic cutting method of the substrate is carried out in the usual manner. The conditions in this case are, for example, the electrolyte (5) is a 4 molar nickel nitrate aqueous solution,
120 mfiJcrr? constant? ! 1: s'
As a condition, the electrolyte (6) is applied to the substrate (4) at a constant speed.
According to the present invention, the device 1. The electrolyte regenerating device B that implements the LA vc Kimoto method is attached as follows &rJ'
Take out a part of the electrolytic acid electrolyte, regenerate it, and add it again to the electrolytic tank (1) V? :, Always keep the ammonium ion concentration in the electrolytic solution (5 liters) in the electrolytic cell (1) below one foot.

A narrow groove that allows continuous electrolytic deposition of active materials,
(9) shows the entire regeneration tank, and the jacket (9a)
t: has vc I'i, yR in the jacket (9a)
The regenerating tank (9) is configured to circulate a refrigerant such as a refrigerant and a heat medium such as a hot steam through a heat exchange circulation. The regeneration tank (9
] On the lower side of the valve, there is a separate valve port Q.
On the other side of the upper part of v and on the other side, there is a preparation sleeve (6) whose tip opening is located on the upper surface of the battery case (1), and on the pipe @ there is a valve Ijj valve (to) and a valve d? It is also possible to provide a filter such as a mesh inside the valve port 1jJ for the separated liquid. To regenerate the electrolyte using this filter, ammonium ions generated during the electrolytic deposition process of the electrolyte (5) in the carbon dioxide (1) will reduce the ejection generation efficiency of the active material. When it becomes excessive, one of the capitals will be cut off and regenerated.
9) Take it out and play it inside the jacket of β(9) <9
a) Heat a heating medium such as heated steam to heat the electrolytic solution to 100C or more, evaporate water and concentrate to about 70 to 80% of the initial volume, then pass a coolant into the jacket (9a) and
Down to 0℃? '11 I rejected it and left it alone. Thus, 80 of the volume
% crystallizes, open the extraction valve Qu and separate and remove the liquid. In this liquid, ammonium ions are concentrated and remain as crystals. Moromiru 111! Almost no ammonium ions remain in I. Thus, the iron-faced regenerated pieces of crystal (within 9 squares, 1 rectangle)
] Add and heat the water grapes in step I, or directly add hot water and dissolve to prepare an electrolytic solution of a predetermined concentration, then open the valve @,
The recycled gold of the electrolyte (5) is returned to the battery cell (17) through the pipe (6) by the pump aψ. The electrolytic deposition method can be carried out in the same condition, and the work can be done more efficiently.

Next, the changes in ammonium ion concentration due to the use of illegally regenerated electrolyte, the change in ammonium ion concentration, the concentration of active materials 1 N', jli
Changes in the self-discharge rate of the manufactured electrode plate (case V, case II) when the electrolyte is not regenerated (case II), and when the electrolyte is regenerated by removing ammonia gas with alkali and redissolving with nitric acid (case V). Case River) and 4 were measured through specific yield tests, and the results are shown in Table 1 below. *Self-release rate% is 45
Initial Capacity When Left at ℃ for 2 Weeks As is clear from Table 1 above, the electrode manufactured using Kempo has a higher capacity than an electrode in which the liquid is not regenerated at all, and an electrode in which the liquid is removed and regenerated using alkali. It can be seen that an electrode with a high self-discharge rate can be obtained. Moreover, this regeneration method has the advantage that the regeneration cost is significantly lower than the removal regeneration method using alkali.

As described above, according to the present invention, ammonium ions can be removed simply by 1 dJ by physical means such as heating and cooling.
The electrolyte can be regenerated by simply dissolving the separated active ingredient crystals in water, and compared to regeneration using alkali or acid, the electrolyte has a good regeneration effect with no unsightly components. .

[Brief explanation of drawings]

The drawing depicts a diagrammatic representation of one example of implementing the invention. Aoo/Electric power/T output device (1/... Electrolytic tank (
4〕...&4ro\G 1 board
(5) ... Electrolysis + 0 B ... Electrolyte regeneration device
(9)...Heating/cooling pair re-housing (9a)...Jacket CIIJ...-pp g '6aυ...Separation pumping out opening/opening valve port (2)...Prepared liquid supply pipe α Le... Pump % license applicant: 2 people other than Furukawa Electric Co., Ltd.

Claims (1)

[Claims] In a method for regenerating 'dL liquid containing ammonium ions generated in the process of electrolytically depositing active materials onto electrode substrates for alkaline storage batteries, J
The electric power is heated, concentrated, and rapidly cooled to precipitate all the crystals of the active ingredients, and then separated from the liquid and the resulting crystals are dissolved in water. A method for preparing an electrolyte used in the electrolytic deposition method, which is characterized by a liquid solution.