DE2038754C3 - Mixture of basic nickel (II) carbonate and basic nickel (III) carbonate and process for its production - Google Patents

Description

35 where y is between 3 and 10 and ζ is between 4 and 10

The invention relates to a mixture of basic Hegt.

Nickel (H) -carbonai and basic nickel (III) -car The inventive method for production

bonat and a process for the preparation of the mixture described above is thereby

duktes. indicates that a nickel (II) -

When removing cobalt from nickel (II) - 40 saline solution with a pH in the range from 4 to

Salt solutions and in particular from solutions that react 6 with an aqueous solution that contains an alkali

Nickel (II) sulfate and / or chloride and / or nitrate carbonate in 1.2 to 1.4 times the amount of the for

contained, this is initially in the solution in two- formation of Ni ₂ (CO ₃ J ₃ theoretically required

valuable form present cobalt to the trivalent amount and an oxidizing alkali salt in the 1.10-

in the form of oxidation, and 45 to 1.25 times the theoretical amount for the oxidation of

gaseous chlorine or nickel (III) - nickel (II) to nickel (IH) required amount

hydroxyd used. The use of gasföi keeps, and the precipitate obtained from the courage

Moderate chlorine is, among other things, disadvantageous, the lye separates and washes.

because undesirable chlorine anions in the treated process. In a preferred embodiment of the invention Solution occur. The use of 50 according to the method is called nickel (II) salt nickel (III) hydroxide on the other hand, it has the large solution of a solution of nickel sulfate and / or the advantage that the solution is not treated with undesirable nickel chloride and / or nickel nitrate with a nickel Anions is contaminated. A large content of 50 to 150 g / l, as alkali carbonate, Na disadvantage However, the fact is that nickel (III) - trium carbonate and as an oxidizing alkali salt hydroxide, like the alkali metal persulfate, hypochlorite or hypobromite obtained in the reaction, forms (III) hydroxide is very strong colloid, which turns.

The separation of the hydroxides from the solution is described below as the method of preparation

is made more difficult. The separation takes place in the general claimed mixture and then briefly

mean by filtration or by flocculation or its use as an oxidizing agent for de-

Decant. These known methods are removing cobalt from a nickel (II) salt solution

complicated and technically difficult to carry out. to be discribed.

For example, in US Pat. No. 2,531,336, the production of the invention

Purification of a mixture by leaching out minerals leads to a solution of a nickel (II) -

obtained, nickel and cobalt containing solution salt (of the sulfate and / or chloride and / or Ni

described, in which first sulfur, selenium, tellurium 65 occurred) in an aqueous solution, which at the same time

and other impurities which oxidize an alkali carbonate and an oxidizing alkali salt

the cobalt compound would prevent it from being removed,

will. In the known method, this is preferably done lying; as carbonate sodium carbonate

3 4

and as the oxidizing alkali salt, a persulfate, a balt (III), where the oxidizing agent is the invention

Hypochlorite or a hypobromite of an alkali metal, according to the mixture is used.

especially sodium hypochlorite. The mixture precipitate according to the invention is

The mage of the sodium carbonate used is slurried in the solution to be cleaned,

in the form of a practically neutral solution 5 The cobalt is removed with increased terope-

(pH 4 to 6) used nickel corresponds to the 1.2- temperature from 60 ° C to the boiling point and preferably

to 1.4 times that for the formation of Ni ₂ (CO ₃ )., theoretically from 80 to 95 ° C. After the reaction, the

required amount. The suspension is filtered and the precipitate is either

The amount of oxidizing Al to be used on the filter or by reslurrying in

Potash salt is washed between the 1.10 and 1.25 io hot water.

times the theoretically required amount by which the precipitate obtained contains, in addition to ko-nickel (II), by oxidation in nickel (HI), overbalt (III) in excess mixture added, which lead. If sodium hypochlorite is used by supplementing it with a fresh mixture for a new treatment for removing cobalt, one takes into account in the theoretical calculation, for example, that a ClO ~ ion can be used to oxidize 15. This procedure has the advantage that it is capable of ^{two Ni 2+ ions.} the relationship between Ni and Co in the final

When using sodium carbonate and Na- to reduce precipitate obtained,

trium hypochlorite, the reaction temperature must be below If the CO ₂ content of the mixture for removal

25 ° C are kept and is preferably between the cobalt is very low, you get one

see 10 and 15 ° C. ao precipitate of excellent filterability.

There must be effective mixing by means of the following examples

Ren take place and the stirring about 30 minutes after the explanation of the invention or that of the thus achieved

the introduction of the nickel (II) salt solution sustained advantages, can be obtained. The suspension is then filtered and the precipitate is either deposited on the filter 25

or washed by reslurrying in cold water Example 1 and renewed filtration until most of the Na ⁺ , Cl "- and optionally the

SO ₄ "" ² and NO ₃ ions are removed. A mixture of 250 ml of a sodium The yield of the oxidation of nickel (II) to 30 hypochlorite solution with a content of 38 g of CIO / 1 Nickel (III) is determined according to the analysis of the low and 71 g 97% technical sodium carbonate, Impact, the total content of nickel and the loading ie 69 g Na ₂ CO ₃ , produced. Mood of oxidizing power [expressed as In this mixture kept at 18 ° C Nickel (III)] by iodometry. This exercise within 25 minutes while stirring 200 ml of a

Booty is calculated as follows: 35 solution of nickel sulfate containing 100 g Ni / Ί, poured. After the reaction, the suspension becomes

Yield (%) = " ^{/ o Nicke l} ( ⁱⁿ ) inn filtered and the precipitate through three times

° / o nickel (total) reslurry washed in cold water.

In this way, 105 g of a filter cake are obtained

According to the procedure described, 40 - mixture according to the invention - are obtained with the following precipitates, which correspond to an oxidation yield of analysis values: from 70 to 90%. _{An oxidation yield closer to 100 per cent} can be obtained, ^ (total) 18 9 per cent

if at a higher pH than it was with Na- _N j + s I41 «/ o

trium carbonate can be achieved, is worked. 45 (oxidation yield: 75%)

This is done, for example, by adding kon- qq -2.45%

centered caustic soda to the reaction mixture; ^s

in this case, however, the filterability of the

Noticeably changed in precipitation. The filter cake is used to remove cobalt

The resulting precipitate is used according to the invention from a chloride solution which contains the following mixture of basic nickel (II) carbonate components: of the formula NiCO ₈ -JcNi (OH) ₂ , where χ is 0.5 to 2, and basic Nickel (IH) carbonate of the formula Ni 34.3 g / l

Co 12.2g / l

Ni ₂ (CO _a ) j ^ yNi ₂ O ₃ · ζΗ ₂ Ο 55 A comparative experiment is carried out using

before, in which y is between 3 and 10 and ζ between 4 nickel (III) hydroxide, which is produced by precipitation

and is 10. had been carried out.

The precipitate does not only contain basic. The nickel (III) compounds are converted into nickel (III) carbonate. On the other hand, the content of the cleaning solution in 1.6 times the theoretical precipitate of CO _{2 obtained} is generally slurried in the amount of nickel (III) which is insufficient for the oxidation of the cobalt which is not required to be non-basic nickel. Forms carbonates. The temperature is for 1 hour at a value below the insert is held of the inventiveness of more than 85 ° C but less than 95 ° C mixture according to remove cobalt from 6 ₅ (85 ° C <T <95 ° C) . The suspensions of a nickel (II) salt solution are briefly described. are filtered with the help of a Büchner funnel (filter-The cobalt removal takes place according to the classic surface: 78 cm ² ) under vacuum of the water jet method by oxidation of cobalt (II) to a copump and the filtration time is determined.

Oxidizing agent NickeldU) -
hydroxide mixture
according to
invention Volume of the filtrate
(ml)
Filtration duration.
Content of the filtrate
Ni (g / l)
Co (g / l) 460
1 hour 30 minutes
32.9
0.009 490
4 min.
33.3
0.011

Example 2

A mixture of 440 ml of sodium hypochlorite solution with a content of 98 g of ClO ~ / l and 135 g of technical, 97% sodium carbonate with a content of 131 g of Na ₂ CO ₃ , dissolved in 1750 ml of water, is prepared.

675 ml of a nickel chloride solution are poured into this mixture, which is kept at 14 ° C., over a period of 30 minutes with a content of 132 g Ni / I. After the reaction and washing of the precipitate a filter cake - mixture according to the invention - is obtained with the following analytical values:

Ni (total) 17.6%

Ni ⁺³ 15.2 "/ β

(Oxidation yield: 86 Vo)

Na ⁺ 0.23%

CO ₃ " ² 1.64 Vol

This filter cake is used to remove cobalt from a chloride solution, the following Components contains:

Ni 48.3 g / l

Co 11.2 g / l

pH 5.7

For this purpose, the filter cake is slurried in the solution to be treated in twice the theoretical amount of nickel (III) that is necessary for the oxidation of the cobalt present, and the temperature is kept at about 95 ° C. for 1.5 hours. The suspension is nitrided with the aid of a Büchner funnel with a surface area of 1.5 dm ^2. The filtration time is 6 minutes for 1000 ml of the filtrate obtained, which contains the following components:

Ni 51.0 g / l

Co 0.007 g / l

After washing, the precipitate contains the following components:

(Ni + Co) (total content) 25.2 vol

(Ni + Co) ^{+ S} 18.5%

Co ⁺ * 10.9Vo

Ni ⁺ »7.6%

CO, - * 1.5Vo

Na ⁺ 0.007V »

Cl- 0.011V.

This product still contains enough nickel (III) to be used for another process of cobalt removal.

Example 3

The same mixture is prepared and worked under the same conditions as in Example 2, but with the exception that 750 ml of a solution of nickel nitrate with 118g Ni / 1 was poured in will.

The filter cake obtained - mixture according to the invention - has the following values:

Ni (total content) 22.0%

Ni ⁺³ 18.4%

(Oxidation yield: 84%)

Na ⁺ 0.15Vo

»5 Cl- 0.02Vo

CO ₃ 2.7%

NO ₃ 0.10Vo

He was slurried in a nickel sulfate solution to be freed from cobalt and thereby the the same process conditions as described in Example 2 are observed.

Ni 80.1 g / l

as Co 5.5 g / l

and had the

pH 5.8

After the reaction, the filtration time was 3 minutes for 1000 ml of the obtained filtrate which contained the following components:

Ni 79.5 g / l

Co 0.011 g / l

Example 4

The following mixture is prepared: 6.7 l of a sodium hypochlorite solution (extrait de Javel) with 123 g C1O- / 1, 5.75 kg technical sodium carbonate with a content of 97% Na ₂ Co ₃ , dissolved in 25.2 l Water.

In this mixture, which is kept at 20 ° C., 13.11 of a nickel sulfate solution containing 114 g are quickly added Ni / 1 cast. The temperature rises to 18 ° C and remains at this for 30 minutes of stirring Value.

The suspension is filtered in a filter press, the frame of which is covered with a Terylene 488 filter cloth and the pressure of which is kept at 2 kg / cm * by rising liquid. At this first filtration is the mean throughput

SS 40 l / h / m ² , and the frames are well filled at the end of the process.

The filter cake is reslurrying three times in cold water and then Filtration at an average throughput of

• o 80 l / h / m * washed. A filter cake is obtained - mixture according to the invention - with the following content:

Ni (total amount) 11.6%

«3 Ni ⁺ » 9.8%

(Oxidation yield: 84.5 V)

CO ₈ - * 6.9 · /.

Na ⁺ 0.10 /

Claims (3)

by adding an alkali carbonate or by additional patent claims: there would be an oxidizing agent such as hydrogen peroxide or a peroxy compound. After the removal 1. Mixture of basic nickel (II) carbonate lieren of ammonia, the precipitated nickel is in the formula NiCO ₃ * Ni (OH) ,, where χ between 5 form of a nickel hydroxide, which is poorly 0.5 and 2, and basic NickeKIIIJ-carbo- is to be separated. .
natderFormd "In the USA. patent document 2 879 137 a M- mn \ _Μ · Λ tr r> ^ e ¹¹ ^ ¹¹¹ Separation of nickel and cobalt from Mi ₂ (CU ₃ ; _s · y JNi ₂ U ₃ -z H ₂ U _{one before} j, _er oxidized, strongly ammoniacal, wherein y between 3 and 10 and ζ between 4 and io ammonium carbonate containing solution through 10 cherishes. Leaching of nickel ores is obtained, br — hrie- 2. Procedure for making the product. For this purpose, in the method according to claim 1, characterized in that alkali or alkaline earth metal hydroxides are added, a nickel (II) salt solution is added with stirring, the nickel being precipitated. Even with this pH value in the range from 4 to 6 with a known method, neither the precipitation of aqueous solution, which causes an alkali metal carbonate of a defined nickel carbonate, is converted, but it is 1.2 to 1.4 times the amount to be formed a precipitate separates out, which is difficult to filter off from Ni, (CO ₃ ) ₃ , the amount theoretically required. and an oxidizing alkali salt in FIGS. 1, 10 to The known methods further have the 1.25 times the theoretical for the oxidation of 20 disadvantage that at a relatively high temperature, the required amount has to be worked with nickel (II) to nickel (III) and that the oxidation includes, and the resulting precipitate from the passage of air for several hours separated by mother liquor and washed. to be led. 3. The method according to claim 2, characterized in that the present invention is thus characterized that one would give as a nickel (II) salt solution as the basis to create an oxidizing agent a solution of nickel sulfate and / or nickel which has the aforementioned disadvantages and difficulties with a nickel content of 50 to 150 g can be avoided. per liter, as alkali carbonate sodium carbonate The solution to this problem consists of the invention and an alkali persulfate in a mixture of basic nickel (II) fat, hypochlorite or hypobromite is used as the oxidizing alkali salt. 30 carbonate of the formula NiCo ₃ -A-Ni (OH) ₂ , in which χ is between 0.5 and 2, and basic nickel (IH) carbonate of the formula
Ni ₂ (CO ₃ ) ₃ y Ni ₂ O ₃ ζ H ₂ O