The method of obtaining insoluble hydroxides of metals

 

(57) Abstract:

The method is designed to obtain the insoluble hydroxides of metals, namely compounds of the General formula M(x)(OH)xwhere M is a metal from the group of cobalt, zinc, Nickel and/or copper, and x is the valence of the metal. The method consists in the interaction of the reactive hydrocycle one or more metals from the specified group with complexing agents and alkali metal salt and subsequent interaction of the formed salt complex of the metal with caustic liquor at pH >7. The technical result - obtaining insoluble hydroxides of metals with improved technical properties, while reducing cost by reducing the number of waste water subject to neutralization. 11 C.p. f-crystals.

The invention relates to the technology of sparingly soluble metal compounds, in particular to a method for trudnorastvorimykh hydroxides of metals.

Upon receipt insoluble hydroxides of metals for different purposes, the most important task is getting more compact material with great fluidity suitable for further processing. For example, from powder metae particles in the sintering together with tungsten carbide can be produced tools made of hard metal for special purposes.

Modern manufacturing foam anodes used, in particular, in batteries based on Nickel hydride requires gidrookisi Nickel with optimum physical properties in relation to the purpose and techniques of processing. While using powerful batteries requires a high degree of compaction of the active material for the implementation used in the manufacture of foamed anodes method for processing into paste requires a material with high flow, compact form of particles, narrow particle size distribution and consistent quality. In addition, the material must be capable of mixing with commonly used additives, for example, powdered metal cobalt and cobalt oxide.

A method of obtaining insoluble hydrocycle Nickel, which is that to aqueous solution of Nickel sulfate containing zinc sulfate or magnesium in an amount corresponding 3-10 wt.% zinc respectively 1 to 3 wt.% magnesium, add ammonium sulfate, and the resulting salt solution of a complex metal under stirring at a temperature of about 40 - 50oC and a pH of about 11, served in an aqueous solution gidroburom solution.

Adding to the sodium liquor formed salt complex of Nickel is decomposed according to the following equation:

Ni(NH3)4SO4+ 2 NaOH --> Ni(OH)2+ Na2SO4+ 4 NH3< / BR>
(see application EP N 0 353 837 A1, MKI H 01 M 4/52, 1990).

Obtained by the known method the insoluble gidrookisi Nickel is provided in particular for use in alkaline batteries. According to the prototype gidrookisi Nickel has a high crystallinity, low specific surface area, small pore volume and therefore a high physical density. Low specific surface area leads to reduced conductivity of protons and high current density, contributing to the formation of unwanted-NiOOH, leading to the swelling of the electrode. Although gidrookisi Nickel, with a low pH value which is crystalline, has a high density, it still has a stronger tendency to form-NiOOH. By setting the average value of pH is possible to find a compromise between the required high density and necessary to a certain extent porosity.

From the above it follows that the technological properties obtained by the known method of hydrocycle Nickel is not fully udovletvoryaya in waste water has large amounts of neutral salts, about two times the stoichiometric amount of hydrocycle Nickel, and in the waste water contains even a small amount dissolved in the form of a Nickel complex and a large amount of ammonia.

The objective of the invention is to provide method of producing insoluble hydroxides of metals with improved technical properties, and the cost method, reduced by reducing the number of waste water subject to neutralization.

This problem is solved in the proposed method of obtaining insoluble hydroxides of metals of the General formula M(x)(OH)xin which M stands for cobalt, zinc, Nickel and/or copper, and x is the valence of the metal, by reacting compounds of the original metal or the original metal complexing agents and salt, the interaction of the formed salt complex of the metal with caustic liquor and separating the resulting insoluble hydrocycle metal, due to the fact that as a connection source of the metal or the source of metals used reactive gidrookisi metal, and as salt - salt is an alkali metal, and the interaction of the formed salt com is Kim lye salt complex metal decomposes with obtaining insoluble hydrocycle metal, the complexing agents and salts of alkaline metal.

Preferably in the implementation of the proposed method as complexing agents use ammonia and/or organic mono - and/or diamines with chain length from 1 to 6.

In the implementation of the proposed method avoids the problem of wastewater due to the fact that the raw material used reactive hydroxides of these metals, translated in soluble form by complex formation with the use of suitable complexing agents such as ammonia or an amine. For example, gidrookisi Nickel using ammonia in the presence of neutral salts is almost fully converted to hexammine complex by the following equation:

Ni(OH)2+ 6 NH3+ 2 NaCl ---> [Ni(NH3)6]Cl2+ 2 NaOH.

Examinare Nickel is contained in the solids, which can be easily separated by filtration or decantation.

Particularly good results achieved by the implementation of the proposed method at a temperature in the range from 30 to 85oC, preferably 45 to 80oC.

An important feature of the proposed method lies in the fact that ispolniaetsa chelation. Particularly suitable reactive hydrocyclon metal is svezheosazhdennoi gidrookisi metal. Further suitable using reactive hydrocycle metal, obtained by oxidation of the metal at the anode in an aqueous electrolyte solution in the presence of sulfate ions, separating the formed hydrocycle Nickel and additional treatment with caustic lye.

In that case, if the implementation of the proposed method reactive gidrookisi metal should be subsidized, as required, for example, in the case of hydrocycle Nickel for the manufacture of batteries, the proposed method can be carried out in the presence of salts of cadmium, cobalt, magnesium, calcium and/or zinc, and these salts are preferably in the form of sulphate or chloride salts.

In addition, in the case of oxidation at the anode preferably reactive gidrookisi metal get in the presence of cadmium, cobalt, magnesium and/or zinc, and these elements are in the form of metal anodes.

According to a preferred variant of the proposed method hydroxides of metals as impurities contain one or more elements of the group is the implementation of the proposed method the mother liquor contains the exact stoichiometric amount of sodium lye, required for conversion to a compact, spherical hydrocycle metal. Therefore, preferably the proposed method is carried out continuously, and it is reasonable and complexing agents, and salt of the alkali metal can be recycled to the first stage, i.e. the stage of reaction with the reactive hydrocyclon metal. Decomposition of the salt complex of the metal can be carried out with the use of caustic liquor obtained in the first stage. Large output and high response speed reaches as a result of intensive mixing of the components.

Particularly preferably, the decomposition of complex salts of metals is carried out in a strongly turbulent flow generated by intensive mixing using passive or active mixing elements or nozzles. The decomposition is carried out at residence time in the reactor, comprising 0.5 to 10 hours, preferably 1 to 4 hours.

Particularly advantageous for the implementation of the proposed method is the use equipped with a recirculation line of the reactor. Formed in response to hydrocycle metal products, namely, ammonia and salt consumption, recycle to the first stage, where they are reused DVD.

Obtained according to the proposed method gidrookisi Nickel is particularly suitable for use in foamed anodes. It has the following characteristics:

the density after compaction (according to the US standard ASTM 212) > 2.0 g/cm3< / BR>
specific surface area by BET (according to German industrial standard DIN 66232) 10 - 20 m2/g

the average particle diameter D50 of 10 to 20 μm

porosity 47-53%

swelling of a 3-molar solution of hydrocycle potassium < 10%

the charging capacity of the foam anode(rechargeable cell) > 250 mAh/g

the water content of < 1%

The proposed method is illustrated in the following example.

Example

1. Getting reactive hydrocycle Nickel

a) Electrolysis

In an electrolytic cell consisting of a cell with a capacity of 70 l, serves 200 l of a solution of sodium chloride (50 g of sodium chloride on l of water), and an electrolytic solution using a centrifugal pump serves on a path between the two tanks. In the cell hang two baskets of tantalum, the side surface of which is made as a sieve and filled with Nickel briquettes. Baskets of tantalum include as anodes, and their opposite side surfaces of the set included in the qualities which C is carried out at 4.2V and 500 And at the current density, component 1000 a/m2. During electrolysis every hour in the cell continuously introducing 200 ml of a solution of Nickel sulfate and cobalt sulfate (250 g/l with NISO47H2O, 250 g/l CoSO47H2O).

After 5 hours from the circulation tank continuously output 40 l/h the resulting suspension, and the cell is injected a fresh solution of sodium chloride, so that the volume of liquid in the cell is not changed. Then the suspension portions filter, and with the further implementation of the electrolysis instead of fresh salt solution in the cell enter this filtrate. So fresh solution of salt is required only at the beginning of a continuous process, and then under steady-state operation of the reactor it is a vicious cycle. The suspension is easily filter; get jellous primary product with an average water content amounting to 90%. Output from the gel water is fed back into the system as wash water gel primary product. According to the chemical analysis of the dried gel is a sulfate content of 1.8% and a chloride content of 2%. The duration of the experience - 105 hours. During this time, as a result of continuous process receive 870 kg ReliableMessaging primary product from cell finely dispersed in 200 ml of water with vigorous stirring in a heated reactor with a double wall. Then add hydrocycle sodium is brought to a pH value equal to 13.7, and the suspension is heated with stirring to 80oC and maintain at this temperature for 6 hours.

Then filtered by suction, and get on the suction, the product is washed with water. The result of drying in a drying Cabinet get 19,7 kg hydrocycle Nickel content of cobalt constituting 1%. Anionic impurities are less than 500 parts per million. Density is 1.3 g/cm3the density after compaction - 1.8 g/cm3. Specific surface area by BET is very high and is 88 m2/, the Width of the resonance curve at half its maximum value at 101 is 2.0.

2. Getting examinated Nickel

a) Receiving portions with 25% aqueous ammonia

To 1 l of a suspension of 100 g/l obtained electrodeposited according to 1. highly active gel hydrocycle Nickel and 280 g/l of salt serves 1 kg of a 25% aqueous ammonia, and cooled stirred for one hour. The reaction mixture is sucked off through the suction and portions are subjected to additional washing with a small amount of concentrated ammonia. Get 226 g [Ni(NH3)6]Cl2(output - 90,5%).

th ammonia. The last is removed by distillation in the form of a 25% aqueous solution through a short Packed column.

At the same time as well settling and subject filtering product falls 9.5 g comprehensively linked hydrocycle Nickel. By filtering and additional washing a small amount of water get 1.5 liters of the filtrate with 280 g of sodium chloride (3.2 M), and 78 g of hydrocycle sodium (1.4 M).

b) Receiving in a continuous process using 25% ammonia

In beaker 2 l with overflow with stirring and cooling continuously vkachivayut 0.5 l/h of a suspension of 100 g/l of highly active gel hydrocycle Nickel, 280 g/l of sodium chloride and 0.5 l of a 25% aqueous ammonia. Flow through the immersion tube is introduced into the classifier with upward flow, which precipitates formed examinare Nickel. Output from the classifier, the filtrate contains 2 g/l complex associated hydrocycle Nickel, 40 g/l sodium liquor, 140 g/l of sodium chloride and excess ammonia. With an average residence time of 4 hours, this corresponds to a degree of conversion of highly active gel hydrocycle sodium examinare Nickel, equal to 92%. 1 l of the filtrate with 190 g/l chlark in the form of condensate, and as a result of separation drawn hydrocycle Nickel - 700 ml of fluid containing 140 g of sodium chloride (3.4 M) and 40 g of hydrocycle sodium (1.4 M).

b) Receiving in a continuous process using 50%-aqueous ammonia as a secondary pair

Interaction visokoaktivnie gel hydrocycle Nickel and salt with ammonia is carried out continuously in a cooled jet reactor with a capacity of 10 litres

Ammonia is produced from the diluted exhaust liquid medium by evaporation Packed column, and it is served in a reactor in the form of a 50% mixture with water without prior condensation. In the jet reactor continuously injected 3 l/h of a suspension of 100 g/l of highly active gel hydrocycle Nickel with 280 g/l of salt), and 600 g/h of ammonia and 600 g/h of water as a secondary vapor mixture. Overflow of the reactor through an immersion tube connected to the classifier with upward flow, which precipitates formed examinare Nickel. Produced by transparent filtrate (4 l/h) contains 3 g/l complex associated hydrocycle Nickel, 210 g of chloride of sodium, 49 g of hydrocycle sodium and 70 g/l of ammonia, which corresponds to a conversion rate equal to 96%.

3. Getting company 5 l

A heavy suspension of examinated Nickel (400 g 600 g of 7% aqueous ammonia) retain capable of pumping by mixing in the storage tank. 500 g/h of this suspension is continuously introduced into equipped with a stirrer, a flow-through boiler with a capacity of 5 l, heated at a temperature of 70oC. the second component is added approximately 1.2 l/h exhaust liquid environment with controlled pH, containing 60 g/l of hydrocycle sodium and 140 g/l of sodium chloride.

The average residence time in the reactor is about 3 hours. After 21 hours produced from the suspension by filtering and washing with water to obtain a compact, easy filtering gidrookisi Nickel with the density component of 1.6 g/cm3.

Continuously getting in the jet reactor with a capacity of 100 litres

For the reaction of examinated Nickel and sodium liquor to compact hydrocycle Nickel use jet reactor, which with the help of the mixing nozzles and powerful circulation pump ensures optimal mixing of the reagents and the creation of high shear forces. In the storage tank, the thick suspension of 400 g of examinated Nickel on 600 g of 7% aqueous ammonia retain capable of EOS, heated with constant temperature, component 73oC. as a further reagent is added approximately 43 l/h exhaust liquid medium containing 65 g/l of hydrocycle sodium and 200 g/l of sodium chloride. When submitting regulate the pH value of support at 11.4 and 11.6. The average length of stay is approximately 1.6 hours.

After 16 hours of flow reactor quickly get suedoise compact gidrookisi Nickel with extremely good capability to filtration, which was washed using approximately 7 l/kg of warm water until the chloride content of less than 500 parts per million. The density of hydrocycle Nickel on average 1.9 g/cm3and the density after compaction - 2.1 g/cm3. The average size of spherical particles by an average of 12 μm.

1. The method of obtaining insoluble hydroxides of metals by reacting the parent compound of a metal complexing agents and salt, the interaction of the formed salt complex of the metal with caustic liquor and separating the resulting insoluble hydrocycle metal, characterized in that, as a sparingly soluble hydroxides of the metals are compounds about the th metal, as the source connection of the reactive metal is used gidrookisi one or more metals from the specified group, as well as salt - salt is an alkali metal, and the interaction of the formed salt complex of the metal with caustic liquor is carried out at pH values greater than 7.

2. The method according to p. 1, characterized in that as complexing agents use ammonia and/or organic mono - and/or diamines with chain length from 1 to 6.

3. The method according to one of paragraphs.1 and 2, characterized in that use reactive gidrookisi metal containing up to 10 wt.% at least one element from the group comprising cobalt, zinc, magnesium, calcium and cadmium.

4. The method according to one or more of the paragraphs.1 to 3, characterized in that it is carried out at 30 - 85oC, preferably 45 to 80oC.

5. The method according to one or more of the paragraphs.1 to 4, characterized in that the reactive hydrocycle metal used svezheosazhdennoi gidrookisi metal.

6. The method according to one or more of the paragraphs.1 to 4, characterized in that the reactive hydrocycle metal used is obtained by oxidation of the metal on assests continuously.

8. The method according to one or more of the paragraphs.1 to 7, characterized in that the complexing agents and the alkali metal salt formed by the interaction of the salt complex of the metal with caustic liquor recycle to the reaction of interaction with reactive hydrocyclon metal.

9. The method according to one or more of the paragraphs.1 to 8, characterized in that the reaction of a salt complex of the metal with caustic liquor is served caustic liquor formed during the interaction with reactive hydrocyclon metal.

10. The method according to one or more of the paragraphs.1 to 9, characterized in that the reaction of complex metal implement when creating a highly turbulent flow.

11. The method according to one or more of the paragraphs.1 to 10, characterized in that the reaction of the complex of the metal is carried out for 0.5 to 10 hours, preferably 1 to 4 hours

12. The method according to one or more of the paragraphs.1 - 11, characterized in that the receiving insoluble hydrocycle metal is carried out in a equipped with a recirculation line reactor.

 

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