A method of producing nickel (ii) hydroxide


(57) Abstract:

The invention relates to methods for inorganic compounds, in particular to methods for Nickel (II) hydroxide used in the electrical industry for the production of alkaline batteries. A method of producing Nickel (II) hydroxide includes preparation of initial solutions, mixing them with an activating additive containing barium ions, the precipitation and separation of the mother liquor from the precipitate, the subsequent extraction of sediment, first drying, washing away impurities, a second drying and sequential analytical control, and the first drying finish with humidity paste 10-14%, and then it is injected solution containing cobalt ions at a certain attitude to Nickel ions. After the first drying selected samples and in laboratory conditions mimic the subsequent operations to obtain the final product and in case of rejection of the specific volume from the required value in the main process introduce additional surgery-rinse the pasta before the second drying alkaline solution that allows you to adjust the quality of the finished product. The method allows to obtain the Nickel (II) hydroxide, which has an optimum crystalline structure and the other is at the discharge, made out of alkaline and traction batteries. 1 C.p. f-crystals, 2 tab.

The invention relates to methods for inorganic compounds, in particular to methods for Nickel (II) hydroxide used in the electrical industry, in the production of alkaline batteries.

Alkaline batteries are widely used as power sources for rail, sea transport, lift application, as well as emergency power sources.

The most common is to obtain various compounds of Nickel-based metal (carbonyl) Nickel monoxide or him.

About 80% Nickel from its total production is produced from sulphide copper-Nickel ores. The extraction of Nickel from ores is a complex multistage process. First of all ore is subjected to selective enrichment by flotation with separation of copper and Nickel concentrates (4-5% Ni). Nickel concentrate is mixed with flux is melted in electric, shaft or reverberatory furnaces to branch the main mass of the waste and the extraction of Nickel in sulphide melt (Stein), containing 10-15% Ni. Along with the Nickel in the matte becomes part of the VC is Tate get what alloy of copper sulphides and Nickel - Feinstein, who, after slow cooling, finely shredded and sent to flotation for the separation of copper and Nickel. The obtained Nickel concentrate is burned in a fluidized bed until almost complete removal of sulfur and obtain monoxide Nickel. Nickel metal produced by restoration of NiO in electric arc furnaces. Rough Nickel poured into the anode and subjected to electrolytic refining.

In addition to the described technology for the separation of copper and Nickel exist, the so-called carbonyl process and autoclave methods of dissolution of sulphide Nickel in ammoniacal solutions.

Of Nickel release from alloys with iron is a rather complex and time-consuming operation. For the extraction of Nickel from oxide ores are also used hydrometallurgical methods - ammonia leaching of previously recovered ore; sulfuric acid pressure leaching, etc.

Nickel (II) hydroxide falls from solutions of Nickel salts on the addition of alkali in the form of bulk sediment. If the solutions of salts of Nickel (II) to act alkali in the presence of strong oxidizing agents such as sodium hypochlorite, then falls black precipitate close to the composition of Ni(OH)3to the Skye encyclopedia., so 3, M. 1964 "concise encyclopedia of chemical").

A known method of producing Nickel hydroxide for current sources by ozonation of Nickel (II) hydroxide in non-aqueous solvent. As the solvent used tetrachloride, and the process is conducted in the presence of elemental iodine in the amount of 1 - 3 wt. % by weight hydroxide Nickel (II).// Auth. mon. N 1381070, publ. BI N 10-88//

The disadvantage of this method is that the result may learn Nickel (III) hydroxide having low activity, so it cannot be used in the production of traction batteries.

Also known is a method of obtaining Nickel hydroxide by precipitating it from a concentrated solution of Nickel sulfate and sodium hydroxide under stirring with the following introduction into the slurry polyacrylamide, and stirring is carried out at the expense of ultrasonic oscillations.// Auth. mon. N 223809, Publ.: 18. 07. 1969//

The disadvantages of this method include: the possible presence of sulfate ions, which affect the electrical characteristics of batteries; do not provide sufficient physico-chemical properties of the finished product, limiting its application in electrical industry.

A is from a solution of Nickel sulfate with sodium hydroxide is carried out in the presence of the promoting additives, which in this technical solution applied zinc sulfate in mass ratio with NISO4: ZnSO4= (90-95) : (5-10) and a temperature of 50-70oC. //ABT. mon. N 1527170, Publ. BI N 45-87//

Use as a promoting additive zinc ions does not significantly change the electrical parameters in a better way.

A method of obtaining Nickel (II) hydroxide for the electrical industry // the Japan Patent N 4 - 68249, Publ. 10.01. 1990:: / / that all three component reaction (Nickel salts, hydroxide of alkaline metal component containing ammonium ions) are introduced into the reactor simultaneously with continuous stirring. The synthesis is carried out at a temperature of 20-80oC and a pH of 9-12, and formed spherical particles of Nickel hydroxide with an average diameter of 2 to 50 μm is continuously removed from the reaction zone.

This, apparently, is because as shown later studies // L. "Appi Electrochem", 1992 -22 N 5 p. 478 - 482 / / best electroactivity and higher capacity provide fine samples with greater surface area and high porosity.

In the production of alkaline batteries, you must use larger particles, mainly 100-350 μm, because more is of such size particles 2 - 50 μm is used in the electronic industry, in the production of ferrites.

In addition, high temperature (80oC) synthesis leads to unnecessary energy consumption.

The // Dianchi = Battery Bimon, 1995 - 25 N 2, p. 55-58 / / on the basis of the above studies have shown that the introduction of Nickel (II) hydroxide various additives can significantly increase its activity. High activity is associated with the crystalline structure of the Nickel hydroxide and the presence of lattice water molecules. As adjuvants recommended ions: lithium, zinc, barium, cobalt and other metals.

Closest to the claimed invention, as essentially technical solutions and the achieved result is a method of producing Nickel (II) hydroxide, as described in the book: M. A. Dalian, Century Century Novoderezhkin and F. F. Tomaszewski "Manufacture of electric accumulators) "High school", 1977, S. 260-277.

The essence of this method lies in the following sequence of carrying out technological operations. Prepare the reagent solutions, namely solutions of Nickel sulfate and caustic soda, as well as adjuvants containing ions of barium - geranuim download a solution of sodium hydroxide with excess, and then into the reactor simultaneously serves the solutions of Nickel sulfate and hydroxide of barium with constant stirring. The amount of solution of the hydroxide of barium is calculated so that the content of barium in the finished product was 1.7% and 2.7% by weight of Nickel. After draining the mother liquor, the precipitate continue to stir for 25 minutes. The excess of alkali in the filtered solution should be within 4 to 6 g/l solution. If the excess exceeds 6 g/l, the reactor was added a solution of Nickel sulfate, if an excess of alkali is less than 4 g/l, the formation of major and complex salts. These salt trudnorastvorimy and precipitate with Nickel (II) hydrate. Getting into a positive mass, they are due to inactivity contained Nickel, reduce the utilization of the active mass of the working of the battery, therefore, as a rule, such a party in the production of batteries is not allowed, and is used for other purposes. The moisture content of the pulp is about 59%.

The first drying of the product are in the dryer continuous operation at a temperature of 90-120oC for 20 to 24 hours. Humidity dried Nickel (II) hydroxide is approximately 30%.

oC for 24 - 30 hours. The moisture content of the dried product should not exceed 7%.

The dried Nickel hydroxide is ground in the mill, and thereafter the classification and packaging of the finished product.

The main disadvantage of Nickel hydroxide, a member described above is the lack of specific capacity and, as a consequence, insufficient electrical capacity alkaline battery that uses Nickel hydroxide.

On the basis of the conducted studies was established one of the possible reasons causing this drawback, namely the presence of a partially amorphous phase obtained in the Nickel hydroxide.

Technical problem solved by the claimed invention is the obtaining of Nickel (II) hydroxide with normal crystalline structure, increased activity and specific capacity, which can increase the electrical capacity and improve the utilization rate of Nickel at the discharge made of it alkaline, traction batteries.

The technical result is achieved by introducing a known method of producing Nickel (Thelen adjuvants, containing cobalt ions.

The most important operations in the process of obtaining Nickel (II) hydroxide, which practically determines the quality of the finished product are the steps: deposition ( synthesis ) and the first drying.

At these two stages, especially during the first drying, the formed crystal structure of Nickel hydroxide.

To obtain alonebecause Nickel hydroxide is recommended to increase the time of deposition or the excess of alkali. // Sat. research work on chemical sources of current / the/ vol. 1, 1935 Ed. Kosorukov //.

The increase in time of the phase deposition increases the duration of the technological process and energy costs, while too large an excess of alkali to increase the expenditure coefficients of the reacting solutions.

Based on the above, the proposed first drying finish when reaching the moisture content of the pulp 10-14%.

The moisture content of over 14% risk that does not resolve the presence of amorphous phase in the final product, which leads to an increase in specific capacity (>0,76 cm3/g, and this means only a partial solution to the problem, because it does not provide factor used is rosedene process, and worse conditions of washing paste from sulfate ions.

It is known that to increase the electrical capacity of the battery factories in the preparation of anode paste by mixing the dry components injected 0,3 - 2% of cobalt ions from the total Nickel content.

Dry mixing of the components of the paste is not possible to reach an equal dimensional distribution of cobalt ions in the mass. The introduction of cobalt, at the specified ratio of the cobalt - Nickel, can improve the utilization rate of Nickel, but it is not optimal to achieve the desired electric capacity of the battery.

To resolve the above shortcomings, the authors proposed proposed invention after a stage of deposition, sediment extraction and the first drying, the obtained intermediate processing solution containing cobalt ions to obtain the mass ratio of the ions of cobalt and Nickel is 0,015-0,030, and then the resulting paste to wash from sulfate ions and subjected to a second drying.

The introduction of the activating solution at an earlier stage of the technological process, for example, at the stage of deposition, it is impractical for the following reasons:

the capacity is) to control the ratio of barium and cobalt to Nickel;

aoademy together with Nickel cobalt is inactive and the capacity of the hydrate Nickel (Ni(OH)2from the introduction of cobalt ions does not increase at this stage.

The positive role of the introduction of additional activating solution containing cobalt ions, allows you to increase excess alkalinity at the stage of precipitation of 7 to 10 g/L. As already mentioned above, excess alkalinity can improve crystal structure and to reduce the loss of Nickel ions from the mother liquor.

To enable adjustment of the quality of the finished product, the additional prognostic evaluation of the properties of the obtained Nickel (II) hydroxide. This additional control is carried out as follows: after the first stage of the drying selected sample of Nickel (II) hydroxide and in the laboratory carry out all subsequent stages of the finished product and determine its physico-chemical properties. When the deviation of each option from the optimal value, first and foremost, specific volume, given the earlier results, than in the actual process, you can make corrective hcpa what astora lye.

The essence of the invention is illustrated by the following examples of its implementation.

Example 1. Previously known methods in a separate reactor prepare source solutions 15-16% solution of Nickel sulfate (II); 26-27% solution of caustic soda; 4% solution of barium hydroxide to a temperature of 70-80oC and a solution of cobalt (II) sulfate as for the electrical industry.

In a reactor with a capacity of 6.3 nm3equipped with a mechanical stirrer and provodnoy shirt pour 580 l of sodium hydroxide solution, the density of 1.29-1.30 grams/cm3and heated to 50oC. Then, with stirring, serves pre-heated to a temperature of 50oC solution of Nickel sulfate, a density of 1.17-1.18 g/cm3the number 1760 HP Simultaneously with a solution of Nickel sulfate fed into the reactor a solution of barium hydroxide in the amount of 100-120 l, which will be 1.7-2.7 wt.% from the contents in the reactor Nickel. It was filled with 100 l of barium hydroxide, which amounted to 2.0 wt.%. The submission time is 1 hour. In the deposition process the temperature of the reaction mass is maintained within the range of 60oC.

After draining the mother liquor is decanted into an intermediate tank with a capacity of 6.3 nm3and sent to the n, press and subjected to the first drying.

After mixing the pulp with Nickel (II) hydroxide, selected the sample, the precipitate is filtered off and define the content of caustic soda. The excess of alkali should be in the range of 4-10 g/l Content of caustic soda corresponded to 7 g/L.

First drying the Nickel hydroxide is carried out at 110oC and stirring to a moisture content of 10-14%. Drying was carried out for 24 hours. The moisture content was 12%. After drying took a sample of the Nickel hydroxide to conduct with him subsequent operations on laboratory equipment.

In the dried product add distilled process water, sludge repulping and simultaneously poured 80 l of a solution of sulphate of cobalt, which corresponds to 2.0 wt.% ions, cobalt ions, Nickel and passed into the collection drive with a capacity of 3.2 cm3equipped with stirrer and the pump is passed to a filter press. The pressed product is washed with distilled water from the sulfate ions to weak opalescence in the wash water (residual concentration of 1.7 g/l).

By this time the technologist knows anticipated assessment of the quality of the finished product and take appropriate action to adjust the% is Viy, therefore, the washed product in paste form is served on the second stage of drying. Drying is carried out at 110-120oC to the content of the basic substance in the Nickel (II) hydroxide is not less than 57% (in terms of Nickel). In this example, the drying was carried out at 120oC to the specified content of the basic substance. Drying time amounted to 26 hours. Vapor exhaust mixture is treated in the scrubber.

Next, the finished product is ground in a mill, classified and Packed. Output fractions 60 to 350 μm was 48%. The size of the crystallite is in compliance with the specifications and the amorphous phase was not detected.

Table 1 shows the parameters of the individual stages of embodiments of the inventive method of producing Nickel (II) hydroxide, which differ in the ratio of cobalt ions to Nickel and so on, the Sequence of operations is the same as in example 1.

The stage of the technological process, the length of which depends only on the possibilities of the use of any equipment, volumetric characteristics in table 1 is not specified. This refers to the separation of the mother liquor and its decanting, extraction and leaching, which ends at a given content of sulfate ions. Study the tion, that it is the same as in example No. 1, i.e., corresponds to the same concentration and density.

When implementing the examples in table 1 have tried to stick to the routine parameters on temperature, the expense ratios of individual reagents and time of the individual process steps, so temperature fluctuations stage of deposition, the ratio of barium ion to Nickel fluctuate slightly, within the accuracy of measurement instruments.

Table 2 presents the results of analytical testing of finished product obtained in examples 1-10 and the prototype, but are not all of the indicators required by THE 48-3-63-90, but only those that are affected by the change of characteristics reflected in the formula of the present invention.

The analysis of the examples in table 1 and the quality of member of the product (table No. 2) allows us to conclude that the claimed in the formula of the proposed invention the parameters are optimal.

So, with the introduction of after the first drying of cobalt ions less than 0,015 (0, 01, i.e., 1 wt.% in example 5 ) in relation to Nickel (II) does not allow to obtain the desired electrochemical capacity, which should not be less than was 0.138 Ah/g i.e. 3.5 wt.%) no significant improvements compared with examples within the claimed, but by the content of the chloride ions and sulfate ions, even inferior to that obtained in examples 3 and 4, therefore, inappropriate pererashodovanie scarce cobalt.

When the variance of the first mode of drying of Nickel (II) hydrate from the claimed parameters moisture content (10-14%) results of nonconforming product. So in the example 9, the first drying was completed at a moisture content of 16%, resulting in a finished product did not meet the requirements for the main parameter is the specific volume - 0, 78 cm3/g (must be less than 0.76 cm3g). In addition, the output fractions of 0.50 to 350 μm is 35% and relatively high content of chloride and sulfate ions to 1.2 wt.%, and according to the analysis, it was found the presence of an amorphous phase.

These figures were obtained on the basis of laboratory tests, which were carried out as follows.

The sample after the first drying, washed until no sulfate and dried at 110oC. as a result of the analysis it was found that the specific volume exceeds 0,76 cm3/g (0,78 cm3/g), so before the second drying Nickel (II) hydroxide was treated with a solution of Olena on the basis of experiments and therefore, in practice, take some excess alkali. In the result, it was possible to obtain a product with a specific volume of 0.75 cm3/g and were found only traces of amorphous phase, i.e. practically none.

It should be noted that the deviation of the specific volume can occur not only when the failure to comply with the parameters of the first drying, but also in violation of procedural norms in the earlier stages, so additional laboratory testing allows to some extent to adjust the quality of the finished product.

In example 10, the first drying was completed at a moisture content of Nickel (II) hydroxide - 8%. In the resulting non-conforming product by electrochemical capacitance - 0, 133 Ah/,

Analysis of the above results leads to the conclusion that using the proposed method allows to increase the content of the basic substance (Nickel + cobalt), to reduce the specific volume and to increase the electrochemical capacity of the finished product.

At the moment pilot implementation of the inventive method of producing Nickel (II) hydroxide.

1. A method of producing Nickel (II) hydroxide, including preparation of initial solutions, mixing them with an activating additive containing barium ions, the drying and sequential analytical control, wherein the first drying finish with humidity paste 10 - 14% Rel., and then in the resulting paste is injected solution containing cobalt ions in their mass with respect to ions of Nickel 0,015 - 0,030.

2. The method according to p. 1, characterized in that after the stage of drying selected sample imitate her subsequent stages of the Nickel (II) hydroxide in the case of deviations of the specific volume from the desired values in the main process before the second drying paste is treated with alkali solution.


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