The method of obtaining spherical hydrate of oxide of nickel and device for its implementation

 

(57) Abstract:

The invention is used in the field of non-ferrous metallurgy for the production of hydrate of oxide of Nickel, used in the manufacture of batteries. Spherical hydrate oxide synthesize Nickel from Nickel-containing solutions in the presence of complexing agents and alkalis. The synthesis is carried out at a constant flow of reactants and continuous removal of filtered liquid phase with simultaneous withdrawal of part of the suspension to maintain the required ratio between solid and liquid phases. The device has a body with a mechanical mixing device. In the lower part of the body is the filter septum and site drainage suspension, which is accommodated in the housing above the filter septum. The invention allows to obtain a more homogeneous particle size distribution of the particles of hydrate of oxide of Nickel and simplify the instrumentation process. 2 S. and 4 C.p. f-crystals, 3 ill.

The invention relates to the field of hydrometallurgy of non-ferrous metals and can be used to produce spherical hydrate of oxide of Nickel, used in the manufacture of batteries.

Known methods for producing stericsson is the synthesis of spherical oxide hydrate of Nickel from Nickel-containing solution, supplied with a constant velocity in the reactor, equipped with a mechanical mixing device at a controlled pH, due to the simultaneous feed to the reactor alkaline solution. The process is carried out in periodic mode with additional processing of the pulp at the stage of synthesis of the hydrate by high power ultrasound.

The disadvantages of the method and device are complex instrumentation process, its high energy intensity and obtaining spherical hydrate of oxide of Nickel low ostochnoi density.

The closest is a method of obtaining spherical hydrate of oxide of Nickel (application EPO 94116575.5, IPC C 01 G 53/04), including the synthesis of hydrate of Nickel-containing solutions containing as complexing agents ammonia, served in a reactor equipped with a mechanical mixing device, a constant speed during simultaneous proportional to the filing of an alkaline reagent and continuous removal of liquid phase from the synthesis reactor via a submersible filter, ensure the maintenance of a constant level of slurry in the reactor. The process is carried out in periodic mode with a gradual increase in the content of solid in regenia in the pulp maximum concentration of the solid phase reactor is unloaded, and the synthesis process is repeated. A constant supply of reagents with simultaneous removal of the liquid phase provides for maintaining a constant volume of the reaction mixture, which contributes to production of particles of a certain size and shape.

Apparatus for the production of spherical oxide hydrate of Nickel includes a housing, provided with a mechanical mixing device and the device for filtration and removal of the liquid phase, representing a submersible filter, made in the form of a pipe, provided with a filter element placed on immersion in the slurry pipe end. The other end of the pipe connected to the vacuum system.

The disadvantage of this method and device is obtaining uniform in particle size, spherical hydrate of oxide of Nickel, the complexity of the hardware design process and its periodicity.

The technical result of the invention is to obtain uniform particle size of the spherical hydrate of oxide of Nickel and simplification of the apparatus registration process.

The technical result is achieved in that in the production method of spherical hydrate of oxide of Nickel, comprising the synthesis of hydrate of Nickel solution containing completely, served with a constant velocity, at a constant pH in the reactor by supplying an alkaline reagent, and continuous removal of liquid phase from the reactor, according to the invention the removal of the filtered liquid phase passes through the filter wall, located in the horizontal section of the lower part of the body, and removal of suspension of hydrate of oxide of Nickel is periodically or continuously during the process by removing part of the suspension from the zone above the level of the filtering partition. In the device for the production of spherical hydrate of oxide of Nickel, consisting of a body with located therein a mechanical mixing device, a filter element connected to a vacuum system, and node removal, suspension, according to the invention the filter element is designed as a filtering partition placed in the horizontal plane of the lower part of the body of the device, the collected filtrate behind the filter wall, connected to a vacuum system, and the site of removal of the pulp is located in the housing above the filter septum. In the particular case of the filter septum may be false bottom of the case, and the collection of filtrate - life is="ptx2">

The process of synthesis of spherical oxide hydrate of Nickel with a joint introduction into the reactor with mechanical stirring Nickel-containing solution and the solution of complexing agents, or separate supply of Nickel-containing solution and complexing agents, at a constant pH of a solution by adding alkali solution and the continuous removal of the liquid phase results in particles of hydrate of oxide of Nickel spherical shape. Mechanical agitation of the pulp promotes mixing of incoming mortars and the reaction of formation of solid hydrate particles throughout the volume of the reaction mixture, in addition, it prevents the sticking of particles and the violation of their geometric shape and size. Installed that along with the above factors to obtain a uniform particle size of the spherical particles is essential ratio of the solid and liquid phases, as well as keeping this ratio constant during the entire process. Thus, the periodicity of the process associated with the need to discharge particles of hydrate of oxide of Nickel, leads to the formation at the initial stage of synthesis, the corresponding low content in the suspension of the solid phase, major Kong is provedenie the synthesis reaction in suspensions, having compared with the prototype of a lower and constant solids content in the range 350-700 g/l, improves the efficiency of mixing and allows simultaneously with the removal of the liquid phase withdraw a portion of the solid in the form of a flowable slurry from the mixing zone to maintain the desired constant ratio between solid and liquid phases. As can be seen from the description of the prototype, filtration and removal of the liquid phase through a submersible filter having a small filter surface, accompanied by the constant hammering particles hydrate of oxide of Nickel filter surface, and requires more frequent as doing reverse blow, which slows down the process of removal of the liquid phase, violates the constancy of T:W and, ultimately, hinders the implementation process, which is particularly pronounced with increasing solids in suspension. Filtering via partition, disposed in a horizontal plane lower part of the body of the apparatus, to increase the filter surface and positioning the filter device in the zone of intensive mixing a liquid suspension, which eliminates clogging of the filter element particles hydrate of oxide of Nickel, Osada is pensii. This eliminates the need for constant Stripping of the filter element with compressed gas, which ensures consistently high filtration performance. The removal of the suspension can be performed continuously or periodically, depending on the process conditions. Continuous mode of deposition and, above all, the constant solids content in the suspension provides a uniform size spherical particles, while maintaining their high ostochnoi density.

Under the proposed method in its implementation, the device may be modified hydrate of oxide of Nickel, for which the Nickel-containing solution should include ions of at least one metal chemical modifier selected from the group consisting of Al, BA, CA, CE, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Na, Sr, Zn, or mixtures thereof.

Under the proposed method in its implementation, the device may be clad cobalt hydrate of oxide of Nickel. For this synthesis process is carried out in two stages, the second stage is characterized by the fact that the suspension obtained in the first stage of hydrate of oxide of Nickel is returned to the operation Sint what I am carrying out the method according to p. 1 shown in Fig.1 and includes a housing (1) placed inside a mechanical mixing device (2). The building is surrounded by a steam jacket (3). In the upper part of the body are the pipes (4 and 5) to enter the Nickel-containing solution, complexing agents and alkali solution. In the lower part of the body, below the mixing device (2) is the filtering partition (6) separating from the reaction of the hull of the collection of filtrate (7) connected to the vacuum system (8). On the housing above the level of the filtering partition has a device (9), for example fitting, for removal of the suspension from the mixing zone. Filter retainer for ease of maintenance can be a false bottom (9) of the apparatus (1), and the collected filtrate (7) can be removable, which provides convenience when changing the filter septum. Use as filter material filter cloth, for example, type "Belting" will allow for a further reduction of the process to more efficiently capture particles of different size.

Method and intended to exercise the device, tested in laboratory scale, are as follows. In the reaction space of the apparatus (1), which is a cylindrical Cup, through the branch pipes (4 and 5) was filled in a certain objenesis solution in the reactor to the desired temperature. After reaching the desired temperature in the reactor through pipes (4 and 5) were submitted solutions of Nickel salts and complexing agents, the rate at which were selected empirically, based on particle size sediment. At high feed speeds Nickel-containing solution with complexing agents (8-10 ml/min per unit volume of 1.2 l) sediment contained many small fraction (less than 1 micron), and the average particle size was 2.5 μm. Why were selected following the optimal feed rate of the Nickel-containing solution: for a unit volume of 800 ml of 3.0-3.5 ml/min, for apparatus 1.2 l - 5,5-6,0 ml/min. as a mechanical mixing device used laboratory stirrer (2). A constant volume of reaction mixture was monitored visually and was achieved by removal of excess liquid phase through the filter wall (6) in the collection of filtrate (7) using a vacuum system (8), by regulating the filtration rate pressure. The pH control was carried out laboratory pH meter. To maintain consistency in the pH of the suspension to within 0.1 pH unit in the reaction space of the apparatus through the pipe (4 or 5) were injected with a solution of alkali. After reaching the suspension of the solid content in the range of 35 the IU produced by removing part of the suspension to the desired solid content. From the resulting suspension was separated solid phase in which after washing and drying was determined by particle size and stukanau density.

For the production of modified oxide hydrate of Nickel in the Nickel-containing solution was additionally injected ions of at least one metal chemical modifier selected from the group consisting of Al, BA, CA, CE, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Na, Sr, Zn, or mixtures thereof.

To obtain a clad cobalt hydrate of oxide of Nickel, the synthesis process was carried out in two stages, with the second stage moved the suspension of the first stage, and instead of Nickel-containing solution was injected cobalt containing solution.

Example 1.

In the reaction space of the apparatus with a capacity of 800 ml was filled in 400 ml of water, which was heated to 40oC. Under stirring continuously introduced an aqueous solution of Nickel sulfate with a concentration of 2 mol/l, pre-mixed with ammonia water with a concentration of 12 mol/L. the Ratio of Nickel to the ammonia in the solution was equal to 1. The mixed solution was applied with a speed of 3 ml/min To ensure a constant pH (pH=100,1) was applied an aqueous solution of hydrate of sodium oxide with a concentration of the partition in the collection of the filtrate with such speed, to ensure a constant volume of the mixture equal to 400 ml, during the whole time. To achieve the desired percent solids in suspension (625 g/l) it took 8 Further including maintaining a constant value of the solid content in the suspension was achieved by removing part of the suspension through the side fitting. Work in a stable regime lasted 20 hours as a result of 250 g of the hydrate of oxide of Nickel, which has an average particle size of ~5 µm and stukanau density of 2.05 g/cm3.

Example 2.

In the reaction space of the apparatus with a capacity of 1.2 l was filled with 800 ml water, which was heated to 60oC. Under stirring continuously introduced an aqueous solution of Nickel sulfate with a concentration of 2 mol/l, pre-mixed with aminouksusnoy acid with a concentration of 1 mol/l, molar ratio aminouksusnoy acid to the Nickel in the solution was equal 0,083. The mixed solution was fed at a speed of 6 ml/min To ensure a constant pH (pH=110,1) was applied an aqueous solution of hydrate of sodium oxide with a concentration of 6N. When reaching a volume of a mixture of 900 ml aqueous phase from the reaction space was removed through the filter wall with such speed, to ensure the long-in-pulp (670 g/l) it took 8 hours In order to keep constant is the content part of the suspension continuously (or portions) to be removed through the side fitting. Work in a stable regime lasted 24 hours the resulting 850 g of the hydrate of oxide of Nickel, which has an average particle size of ~7 μm and stukanau density of 2.2 g/cm3.

Example 3.

In the reaction space of the apparatus with a capacity of 1.2 l was filled with 800 ml of the aqueous phase from the previous experience, which was heated to 60oC. Under stirring continuously introduced an aqueous solution of Nickel sulfate with a concentration of 2 mol/l, pre-mixed with aminouksusnoy acid with a concentration of 1 mol/l Molar ratio aminouksusnoy acid to the Nickel in the solution was equal to 0.055. The mixed solution was fed at a speed of 5 ml/min To ensure a constant pH (pH=110,1) was applied an aqueous solution of hydrate of sodium oxide with a concentration of 6N. When reaching a volume of a mixture of 900 ml aqueous phase from the reaction space was removed through the filter wall with such speed to provide a constant volume in the reaction space during the entire experience. To achieve a percent solids in suspension 700 g/l it took 14 hours to save p is the Church. Work in a stable regime lasted for 30 hours as a result of 700 g of the hydrate of oxide of Nickel, which has an average particle size of ~9 µm and stukanau density of 2.15 g/cm3.

Example 4.

In the reaction space of the apparatus with a capacity of 1.2 l was filled with 800 ml of the aqueous phase prior experience, which was heated to 60oC. Under stirring continuously introduced an aqueous solution of Nickel sulfate with a concentration of 2 mol/l at a speed of 5 ml/min and aminouksusnoy acid with a concentration of 1 mol/l with a rate of 0.85 ml/min To ensure a constant pH (pH=110,1) simultaneously fed sodium hydroxide with a concentration of 6N. When reaching a volume of a mixture of 900 ml aqueous phase from the reaction space was removed through the filter wall with such speed to provide a constant volume of the mixture equal to 800 ml, during the whole experience. To achieve the desired solid content in the pulp (350 g/l) it took 5 hours to keep constant is the content part of the suspension was continuously removed through the side fitting. Work in a stable regime lasted 24 hours as a result of 750 g of the hydrate of oxide of Nickel, which has an average particle size of ~10 µm and stukanau density of 2.20 g/cm3.

Example 6.

In the apparatus with a capacity of 1.2 l downloaded 760 ml of the suspension obtained in example 5 and containing 507 g of the solid hydrate. After heating the suspension to 60oWith it under stirring continuously introduced an aqueous solution of cobalt sulfate with a concentration of 2 mol/l, pre-mixed with aminouksusnoy acid with a concentration of 1 mol/l, molar ratio aminouksusnoy acid to cobalt in the solution was equal 0,083. The mixed solution was fed at a speed of 5 ml/min To ensure a constant pH (pH=110,1) was applied an aqueous solution of hydrate of sodium oxide with a concentration of 6N. When reaching a volume of a mixture of 800 ml of the aqueous phase from the reaction space was removed through the filter wall with such speed to provide a constant volume of the mixture equal to 800 ml, during the whole experience. To achieve RASChETY, its washing and drying the obtained 540 g of sediment hydrate doped on the surface of the cobalt-containing, % wt.: Nickel - 54, cobalt - 5,4; zinc - 3.6V. The average particle size was 10 μm, and ustyana density of hydrate - 2.15 g/cm3.

Example (prototype).

In the reaction space of the apparatus with a capacity of 800 ml was filled in 400 ml of the aqueous phase from the previous experience, which was heated to 60oC. Under stirring continuously introduced an aqueous solution of Nickel sulfate with a concentration of 2 mol/l, pre-mixed with aminouksusnoy acid with a concentration of 1 mol/l Molar ratio aminouksusnoy acid to Nickel was equal to 0.055. The mixed solution was applied with a speed of 3 ml/min To ensure a constant pH (pH=110,1) was applied an aqueous solution of hydrate of sodium oxide with a concentration of 6N. When reaching a volume of a mixture of 500 ml of the aqueous phase from the reaction space was removed through a submersible filter with such a speed to provide a constant volume (400 ml) during the entire time. Due to the continuous speed reduction filtering the precipitate from the filter periodically otdovali nitrogen from a cylinder. Frequency Stripping continuously increased in the course of the experience. Solutions podwal percent solids in the pulp, therefore, the problems of mixing and the impossibility of further removal of the liquid phase due to the decrease performance submersible filter. Received 680 g of the hydrate of Nickel oxide with an average particle size of 4 μm and ostochnoi density of 1.9 g/cm3.

In Fig.2 and 3 presents histograms of the distribution of particles by size for hydrate oxide of Nickel, obtained on the prototype and on the developed method (example 3). It is seen that the histogram of the density distribution of particles by size to hydrate, obtained by the developed method (Fig.2) has a symmetric view, close to normal, and the histogram of the density distribution of particles by size to hydrate, obtained by the prototype (Fig.3), was asymmetric and had a significantly larger sample variance.

1. The method of obtaining spherical hydrate of oxide of Nickel in the reactor with mechanical stirring, including the synthesis of hydrate of oxide of Nickel-containing solution containing complexing agents, or from Nickel-containing solution with simultaneous separate supply of the solution of complexing agents, which are fed into the reactor at a constant speed, while maintaining a constant pH suspecting the level of the suspension in the reactor, and unloading of hydrate of oxide of Nickel, characterized in that the synthesis process is carried out at a constant solids content of the suspension in the range 350-700 g/l, supported by the continuous removal of liquid phase through the filter wall in horizontal section of the lower part of the body with simultaneous removal of the suspension of hydrate of oxide of Nickel from the zone of mixing in batch or continuous mode.

2. The method according to p. 1, wherein the Nickel-containing solution contains ions of at least one metal chemical modifier selected from the group consisting of Al, BA, CA, CE, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Na, Sr, Zn or mixtures thereof.

3. The method according to p. 1 or 2, characterized in that the suspension of hydrate of oxide of Nickel is returned to the fusion operation, conducted from cobalt containing solution in the presence of complexing agents and alkaline reagent.

4. Device for the production of spherical hydrate of oxide of Nickel, comprising a body placed in it a mechanical mixing device, the filter element is connected to a vacuum system, wherein the filter element is designed as a filtering partition, placed in a horizontal PLoS what about a vacuum system, and the site of removal of the suspension is above the level of the filtering partition.

5. The device according to p. 2, characterized in that the filtering wall is a false bottom of the case and the collection of filtrate are removable.

6. The device under item 2 or 3, characterized in that the filter septum is made of a fabric, for example, a filter cloth type "Belting".

 

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