DE2240770A1 - CLEANING NICKEL ROCK - Google Patents

Description

224077Q

22 589

The International Nickel Company of Canada,
Limited, Copper Clift, Ontario / Canada

CLEANING NICKEL ROCK

The present invention relates to the refining of
Nickel sulphide and in particular the refining of nickel sulphide by liquid-liquid extraction processes.

The recovery of nickel from sulphidic ores that Containing both nickel and copper is often complicated by the presence of copper. The treatment of such Ores often includes a pyrometallurgical approach one, in which the nickel and copper sulphides are

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melted state. If that dealt Ore is primarily a nickel ore, e.g. with a ratio of nickel to copper of more than about 5s1 * it is very much desirable to refine the molten nickel sulfide. However, until recently, no such procedure existed. With the exception of two methods described below, treatment includes melts rich in nickel sulfide unchanged, a solidification stage before a treatment to remove the copper takes place. For example be molten nickel sulfide is poured into anodes and the nickel sulfide anodes are electrolytically treated to obtain purified nickel and to recover elemental sulfur or molten nickel sulphide is solidified, pulverized and then used Treated production of a refined nickel product. Most commonly, solidified nickel sulfide is produced under roasted by nickel oxide and the nickel oxide for further purification either by electrorefining or by carbonylation reduced. It has recently been suggested that solid nickel sulfide can be used to chlorinate impurities, for example copper, selectively chlorinated, and the selectively chlorinated impurities from the solid Nickel sulfide could be removed by leaching. All these methods have the disadvantage that they are interrelated Require solidification step and relatively slow compared to the treatment of molten nickel sulfide kinetics obtained.

Recently, there are two methods of removing copper sulfide from molten nickel sulfide has been proposed. U.S. Patent 3,069,254 (Queneau and Renzoni) describes a variation the well-known so-called "tops and bottoms" process. The method described in US Pat. No. 3,069.25 ^ includes Contacting a molten solution of nickel and copper

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224077Q

sulfide with a molten solution of sodium sulfide and sodium chloride or other alkali or alkaline earth chlorides to selectively dissolve the copper sulfide and produce purified nickel sulfide. Although the process described by Queneau and Renzoni represents a substantial improvement over the prior art, the process is only able to separate copper sulfide from nickel sulfide, while other sulfides are essentially unaffected by the treatment. It has also been proposed to bring impure nickel sulfide into contact with a slag containing nickel chloride and alkali or alkaline earth chlorides to purify the nickel sulfide. Slags, which are the reaction product between bases and silicon dioxide, are characterized by relatively high melting temperatures. In extractive nickel metallurgy, temperatures higher than 1200 ^° C. are generally used in order to ensure that the slag used remains in the liquid state. Any method which requires the incorporation of nickel chloride in a slag will be quite ineffective as nickel chloride at temperatures which are slightly above 1000 ⁰ C (1832 ° F), sublimed, which is considerably lower than those required for slag temperatures. In any case, most slags can only dissolve and retain small amounts of nickel chloride even in the presence of alkali and / or alkaline earth chlorides, so that excess nickel chloride is evaporated therefrom. Nickel chloride evaporated from such slugs will be oxidized, rendering the process even more ineffective. Another disadvantage of using slag as a carrier for nickel chloride is that the. Recovery of nickel and the impurities trapped in the slag is quite difficult. The presence of silicon dioxide and bases in the slag increase the resistance to such an extent that nickel chloride and impurity chlorides from it do not electrolyte.

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224077Q i

table can be deposited. In addition, the ■

high temperatures used in the formation of the slag along with the amorphous nature of the solidified slag f

the slag for other recovery processes, e.g. hydro,

metallurgical processes ^ chemically inactive. In addition, I

creates the application of the high temperatures caused by the /

Use of slag as a carrier for nickel chloride is planned / are written, in particular kcaroding conditions that f

due to the presence of chlorine. Although \

Attempts have been made to overcome the difficulties described above and the other night Elle _4, is by no \ ner, it seems, been entirely successful in transfer into commercial use or industrial scale. It has now been found that nickel sulfide can be refined using a chloride extractant at only moderate temperatures and the molten extractant regenerated directly for reuse

can be. {

According to the present invention, a method for Refining of nickel sulfide is made available by using a molten bath of nickel sulfide with a supernatant liquid extractant layer of at least one chloride of a metal of Group IA or HA generated, the Nickel sulfide brought into contact with at least chlorine or nickel chloride; and chlorinated impurities in the extractant layer extracted, which is separated, regenerated and reused.

Many nickel sulfide-containing materials, regardless of the manner in which they were produced, can be treated by the process of the invention. For reasons of economy and overall operation, however, it is advantageous to use a nickel sulfide material or hickel rock that contains at least about 60 % nickel, for example about 70% or more nickel and no more than about 26 % sulfur, for example

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wise to treat $ 18 to $ 24 sulfur and a total chlorine-impurity content of not higher than 15 % . The impurity content that can be chlorinated should preferably not exceed $ 12. As will be shown below, larger amounts of contaminants are removed when the rock contains an excess of sulfur, that is, when the sulphide contains less than about 21 fa sulfur or less sulfur than is necessary to satisfy the stoichiometry of Ni ^ Sp. However, the sulfur deficiency should not be so great that the melting point of the rock is increased above about 900 ⁰ C, which heiss.t, the sulfur content should not be less al§ 18% to do so. that the. Liquid-liquid extraction at a temperature of 750 ⁰ C to 900 ° C can be carried out. Contaminants which can be chlorinated and which can be removed from Mickelstein by processing according to the invention are, although the invention is not limited thereto, cadmium, cobalt, copper, iron, lead, manganese, tin and zinc These impurities are preferably not present individually or together in amounts that ■ exceed about 12% , since larger and less economical amounts of the chlorine extender must be used when larger amounts are present. Certain impurities can be reduced to less than 1 % by pretreatment, For example, iron can be removed by blowing and slagging. If the chlorinable impurities are present in the amounts listed above, these can in most cases be reduced in one or more stages to an amount of less than 0.03 ^, for example the iron content can be reduced from the original 1 % to less than 0.02%, cobalt from original ^ 5 '% to less than $ 0.02, copper iii nickel sulfide from ur & pifMaaglich 10 % to less than 0.02 % \ lead from originally 0.25 % to less than 0.002 ^, kad-

mium from originally 0.2 % to less than 0.005 '# * zinc from originally 20% to less than 0.5 % and tin from originally 0.2 % to 0.01 % . It is stated that all compositions listed herein are on a weight basis unless expressly stated otherwise.

As stated above, the nickel rock is refined by the inventive method at a temperature of 750 ° C to 900 ⁰ C. Although temperatures may be higher applied than 900 ⁰ C, then carried higher nickel losses due to the increase of the Parti !! pressure of Niokelchlorid and it must Druok- or closed vessels throw applied to losses associated with these high partial pressures of nickel chloride to minimize. Higher temperatures also favor heat losses. Accordingly, it is advantageous in terms of reaction rates, chloride losses and Wärmebetrachtungeri to carry out the chlorination at a temperature of 75O ⁰ C to 900 C.

An important feature of the present invention is the Use of a supernatant molten chloride extractant for the collection of the chlorinated contaminants. As shown below, allows use such an extractant is a more efficient method, particularly when gaseous chlorine is used as the chlorinating reagent. The extractant represents at least represents a chloride of a metal of Group IA or HA of the periodic table, i.e. chlorides of the alkali and alkaline earth metals. The extractant should have a melting point below 800 ° C and; have a vapor pressure not greater than 0.25 atmospheres at 800 ° C. Of course one Combination of chlorides can be used to generate an extraction agent that even has a lower melting

point. It must be cited that the term "Alkaline earth metal" for the purposes of the invention includes magnesium, which is a chloride with a melting point at 708 ° C and a boiling point of 1412 ° C. From the physical From the point of view, chlorides of sodium, potassium, robidium, magnesium and calcium can be used individually while strontium and barium chlorides are only used in combination can be used with at least one of the chlorides listed above.

Another important feature that the chloride extract ionsmittel have needs, provides the ability to dissolve nickel chloride both as chlorinated contaminants. The chloride extraction agent should be able to 1 ^ nickel chloride und'vorzugsweise even to dissolve 20 $ nickel chloride. For overall effectiveness while minimizing nickel losses due to evaporation of nickel chloride, the chloride extract agent contains 15 to 5 % nickel chloride. Unless the chloride extractant dissolves nickel chloride, nickel chloride, which has considerable vapor pressure even at temperatures as low as 850 ° C, is lost to the ambient atmosphere by evaporation from the system. It is even more serious that the absence of nickel chloride in the extractant system makes the process inoperable since no nickel chloride is available to react with the impurities contained in the sulfide bath. For the overall effectiveness of removing a majority of the impurities most commonly found with nickel sulfide, it is advantageous to use a molten chloride extractant containing equal amounts of sodium and potassium chlorides.

The chlorination of the impurities can occur in such a Manner that a good liquid-liquid or gas-liquid contact is ensured, depending on the state of the chlorinating agent. Is gaseous chlorine called

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Chlorination reagent used, this is advantageous by the disgusting rock in the form of tiny, well-dispersed bubbles carried out. For example, a suitable vessel with equipped with one or more porous plugs

which the chlorine is carried out, whereby the chlorine in_das {

Einge- nickel rock in the form of small, well-distributed bubbles \

will lead. However, if the chlorination reagent is nickel chloride j

used, this is advantageously in the molten Extrak- j

dissolving agent and good liquid-liquid contact /

between the lower rock layer and the protruding s

Chloride extractant by mixing either by |

mechanical, electromechanical or pneumatic control j

ensured. . ■■ ο3: «! i ~ . \

If impurities in the nickel rock are caused by using I.

of niekelchio- dissolved in the chloride extractant. 1 rid of being chlorinated, the process can be either batch |

carried out on a wise or continuous basis. |

In the case of a batch process, one or more contacting steps can be used. When it is desired to operate the process on a continuous basis, the principles of countercurrent flow can advantageously be employed. An equilibrium between the molten extractant and the molten nickel rock is quickly reached. This fast response speed represents ₄

an important feature of the process as it is the use a number of stages without requiring much additional heat at each stage. The procedure will preferably carried out in countercurrent in a tower arrangement. For example, molten impure nickel rock are introduced at the top of a baffled tower while molten chloride extractant at the lower end of the tower is introduced so that the Flow of the Niekelgestelnes in a downward direction and the flow of molten extractant in up-

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ORIGINAL INSPECTED

I forward direction. the desired counter flow liquid-liquid-con-

I generate clock. Be it that the molten nickel sulfide

j treated on a batch or a continuous basis

I will become ratios of rock to extractant

\ between about 2 * 1 and t \ 3 is used to ensure that ■

\ the nickel stone is refined to the desired size *

I lower sulphide to extractant proportions can lead to

c are used to create such lower conditions- ■

I have problems with material handling, higher oestones for extraction

I Smock ratios can be used, but will

I oestein cannot be refined to the desired extent *

j ßas purified nickel sulphide cat by conventional methods *

I ren for the production of winding or Miskeiöxid böhandslfe who *

(the. After melted Niöfcelgeafeein by turning

I agree with the present invention, " $ ■ £% ^it very much

I advantageous, the surface turbuientöii molten JSöSteinsäiäk

\ eäaem $ em. ^ aamteff mto & imäm ubß. direct to

I blow oxygen), Mach

dation and degassing of the Nicketbath can even do that

\ On kontinuleriiciier basis for i ^ zsugung vain Nlckelinetall *

> Product that is suitable for most applications "

* - is suitable «· ■ - ■" ■■. "· ■ ^Λ """.^; - - ■ '-. ■

The loaded chlorine extraction agent, which contains substantial amounts of nickel chloride and chlorides of the impurities, is preferably treated in the molten state for the regeneration of the chloride extraction agent and for the recovery of nickel and valuable impurities. For example, the mother chloride extraction agent is transferred to an electrolytic cell which a graphite container that acts as a cathode and contains a ßraphitanode The nickel and the impurities are converted into metal alloy powder by electrolysis of the molten chloride extraction fluid at a temperature of TOO ⁰ C to 90O ⁰ C at an electrical potential of about 1.5 volts to 10 Volt regained.

ORiGiNALINSPECTED 309810/0702

Current density!} Of 1000 Ampei / foot (1000 A / 0.09 πι) and even more can be used, but as it increases the amount of metal powders produced, is a remarkable one A decrease in the efficiency of the electricity. Chlorine gas is generated at the anode and returned directly to the chlorination plant or used to produce oil which is dissolved in the extractant. After complete After the electrolysis reaction, the regenerated extractant can be used directly recycled or treated for the addition of nickel chloride to this »before reuse as an extraction agent will.

The loaded molten extraction medium is preferably treated with magnesium or an alloy with magnesium as orundum metal for the deposition of the nickel and the chlorinated impurities as a molten magnesium alloy by an exchange reaction. Magnesium or its alloys are added to the loaded extractant in amounts that mix about 1 and 2 mole equivalents of magnesium for each mole equivalent of base metals in the loaded extractant. Since magnesium is less dense than the chloride extractant, it is very advantageous to use a magnesium base alloy that contains at least 6% nickel or copper. The best results are obtained by adding a magnesium base alloy which contains from 5 to 30 %, for example from 6 to 15 %, nickel or copper. The magnesium alloy is supplied in particulate form to the loaded extraction medium while the extractant is kept at a temperature of 750 ° C to 90 ° C. While not essential, it is very advantageous to keep the loaded chloride extractant in a turbulent state by mechanical, electromechanical, or pneumatic means to remove the

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Reaction between the Magneisum and the chloride extractant The purified extractant can returned to the chlorination treatment while the alloy, which contains nickel, cobalt, copper, iron and other impurities, to recover these elements can be treated. As the magnesium content of the chloride extractant grows continuously, it is advantageous to electrolytically apply the magnesium-laden extractant to recycle the magnesium for further use. The magnesium can be recovered from the extractant in electrolysis cells that are in conventional way of obtaining magnesium from magnesium chloride can be applied. The electrolysis treatment produces magnesium for cleaning loaded extractant, a low magnesium salt and chlorine, which are fed back into the refining of niokel rock can.

The extractant containing magnesium chloride can either be regenerated by passing chlorine, which is obtained as a by-product of electrolysis, through a portion of the cleaned rock, which is produced with the supernatant molten chic ride extraction meal layer, or by the extraction process, which is regenerated by passing chlorine through impure Rock is carried out directly, which is in contact with the protruding molten ChIoridex.traktionsrittel. By rapid and efficient regeneration of the molten nickel chloride ensure containing extraction agent, the regeneration is carried out at a temperature of 750 ⁰ C to 800 ° C, the chlorine in small bubbles through at least IO target ($ 5.4 cnj) of molten nickel sulfide hindurchbrodelt.

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Meet your professional one be π.'3 ο res understanding of the invention va \ made] j go, been the following veranschaul iehenden Bt ¹ J led play:

Example 1 \

Impure IU disgusting rock, where] without 26.4 % Sehwefe], O.6 [5 % ]; npi '(3r, Ο.78?' Cobalt and the remainder essentially Uidtel] t., Was heated to a temperature of 78O ⁰ C. and brought into contact with molten sodium chloride containing 0% HJokel chloride. The heal; ti on between the esolimo] zen choride extractant and the malleolus rock was carried out on Ohnrgenbani r> durtihijefiihrt and the ratio of gap] ^ egg tein to Ch ] ori dextraction medium amount about];]. The final percolate analyzed contained 0.2% copper, 0.3 % cobalt and 72.6% nickel. The liquid ChI ori dextractive medium showed an individual analysis of 0 % copper, 0.46 % cobalt and] .9O% nickel. the vain in the contained in adenen Extraktioncmittel Ni, cobalt and copper was removed from the Extraktionsrnitte] as LeRierungspulver by electrolysis in ahn * · 1 j rather manner as described -in example VIII recovered.

Example ]]

This example confirms that rocks which are poor in sulfur are cleaned to a greater extent than gene stones which contain larger amounts of sulfur. The analyzes of the Nikkei rocks are shown in Table 1. Molten nickel stones were mixed with liquid sodium chloride, the 10;.; ' Ni c] (e] oh] orid entlii el t _f at 70 ° C on a batch basis.

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ORiGiNAL INSPECTED

There were ratios of rock to chlorine extractant of 2: 1 applied. The final analysis values of the iliekeigesteinen and the chloride extractiotismitefcel are also reproduced in Table Γ »From Table I it can be seen that the final copper and Koba3t analysis values in rock B, dem sulphurous rock, were lower. The loaded Ext traction means were shown in an example ¥ 111 Way of electrodeposition an alloy powder, which contained nickel, cobalt and copper ;.

Table I. Attempt a $ Cu # Co Analyzes $ Ni original sulphide 0.7ft 0.68 Final sulfide 0.28 0.16 23.2 M'MnMMt loaded extraction
middle 0.71 0.90 ... 2.3 Attempt B f Ou $> Co in the ****** ^ iii original sulphide 0.64 0.58 Endsulf ia ' 0 * 22 0.10 19.6 loaded extraction "
middle 0.64 0.77 m-mmim 2.76

Example III

This example confirms the effectiveness of countercurrent extraction. A niokel rock containing 26.6 % sulfur, 0.87 % copper, 10 % cobalt and 0.22 % Elsen and the remainder essentially nickel was treated with a chlorine extract consisting of sodium chloride with 10% disgust chi or id at IGb ⁰ C bet a ratio of rock to chlorine extractant of 2; 1 brought into contact. After the first extraction stage the rock contained 0.5 % copper, 0.3 % cobalti 0.026 %

3098 f 0/070? - i * -

:;: - '■ original inspected

- 11} -

Iron and 72.1 % nickel, and after the previous stepexiraction, the GentGlnanalysis values showed 0.25 % copper, 0.8% cobalt, 0.01% iron and 72.8% nickel. The Chlorldextraktionsrnlttel the first Su fe containing 0.83 i> copper, 0, Ot% cobalt, 00:22 $ iron, and 2.7% nickel, while the extraction means of the second stage 0.40% copper, 00:37 fo cobalt, 0.0 ^ 5% Elsen and 19.3% nickel contained. Thus, between the first stage and the second stage extractions, the nickel-to-copper ratio in the rock increased from about 144: 1 to about 290: 1. The nickel to cobalt ratio in the rock was increased from about 180: 1 to about 900: 1 and the nickel to iron ratio in the rock from about 2800: 1 to about 7300: 1. Copper-Cobalt-Elsen alloy powder was separated from the loaded extractant in a manner similar to that described in Example VIII and the extractant regenerated for subsequent rebreaths.

Example IV

This example confirms the improved results obtained by using low sulfur nickel rock, the countercurrent principle, and low nickel rock to extractant ratios. Nickel sulfide, which contained 20 % sulfur, 0.8 % copper, 0.78 % cobalt and 0.38 % iron and the remainder essentially nickel, was contacted in three countercurrent stages with a chlorine-extracting agent consisting of sodium chloride and 10 % nickel chloride / at 78O C. . The total amount of chlorine extractant used was such that a total rock to chloride extractant ratio of 1: 1 was used. The final analyzes of the rock and chloride extractant are presented in Table II. These results show that between the original rock and the end

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ORIGINAL INSPECTED

nickel sulfide has the nickel-to-copper ratio of 100: 3 to about 5000: 1, then the Iiiekel-KU ~ Koba3 t ratio of about 100: 1 to about 20,000: 1 and the ilium-au-iron ratio were increased from about 50iI to about 9000: 1. The loaded one Extraction agent was as described in Example VIII is, zui 'deposition of a!., alloy powder and Regeneration of the extraction medium electrolyzed.

Table II

analysis

Ni disulfide

Extraction agent

step fo Cu $ Co fo pe < CU & Co - t Pe - 2L Hi original
1ehes
sulfide 0.8 0.78 O.38 • 57 .37 1. 0.24 0.067 0.016 O. 75 O .068 O .04 3. 58 2. O.O87 0.008 O.O28 O. 19th O .013 O .032 2. O 3. O.OI6 O.OO9 O.OO9 O. 047 O O 4th 4th

Example V

This example confirms the importance of maintaining a supernatant Cliloride extractant on the Surface of the molten rock during the chlorination treatment. A licki rock sample containing the information given in Table III reproduced «Composition was shown with an over» provided a standing layer of a chloride extractant, c3 which contained equal amounts of sodium chloride and potassium chloride. The ratio of Gesiein-su extractant was 5: ^. D: is G 'stein and the sample were at a temperature

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maintained at 800 C and gaseous chlorine at a rate of 0.4] / min per kg of rock through the Niekel rock passed through for 2 hours. The end rock and the adene extractants had those shown in Table III Compositions on. Another nuisance rock, which had the composition given in Table TV, was de nuf 930 C, while gaseous chlorine hereby at a rate of 0.4 l / min per kg of rock during 2 hours was passed. The refined rock had the composition given in Table IV. When comparing of the refined rock compositions given in Tables III and IV it is evident that Nickel stone more thoroughly by applying a "protruding Layer of a chloride extractant is refined. In order to fully realize all the advantages of the chlorination treatment, it is essential to have an effective molten chloride extraction agent] as well as facilities for economic Regeneration of such extractants for To make available. The loaded chloride extraction agent] was carried out in a manner similar to that described in Example VIII is, for the deposition of a Niokel-copper-cobalt-iron alloy powder and to regenerate the chloride extractant treated.

Tab] le Cu III Anal yse 0 Fe . 86 Ί Co O .14 % , 16 fo Ni 0 • 59 .04 0. , 72 76 O .03 .15 0. O ■ 55 0, ΙΟ.ίί

jjrspriing] iehe ;; Gc-- 0.86 76 0-59 0.14 21.1

ostein

Kndgestein
Ends al ζ

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309810/070? ORiGiNAL INSPECTED

Table IY

original rock

Endsal2

fo CU

0.58 0.31

Hf Wed - 75-8

Analysis # Co ^ Fe 0.30 0.22 0.20 0.13

f, B

18.4

20.5

Example VI .

This example shows a 2-step Gest & ins refining process. A rock with the composition shown in Table V was provided with a supernatant layer of a chloride extractant containing equal amounts of sodium chloride and potassium chloride. The ratio of rock to extractant was 3 * 5 · Bas rock and the supernatant Extraktionsini ttel layer were kept at a temperature of 815 ° 0 and gaseous chlorine at a rate of 0.4 l / min per kg of rock through the nickel rock for 2 hours. The end rock and the loaded extractant of this first refining stage had the analytical values given in Table V. After the loaded extractant from the first refining stage had been separated from the nickel rock, the nickel rock was provided with an equal amount of a supernatant chloride extractant layer, the same amount of sodium chloride While the rock and the extractant were kept at a temperature of 815 ° C., gaseous chlorine was again passed through the nickel rock at a rate of 0.4 l / min per kg of rock for 2 hours and refined rock are given in Table VI. the end

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ORfGIWAL INSPECTEO

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Table VT shows that multi-stage treatments are quite effective in producing highly refined Nckel rocks are on. The loaded chloride extractant for each refining stage was prepared in a manner similar to that in Example VIII described W & se, regenerated and a nickel-copper-cobalt-iron alloy powder recovered from the electrolytic treatment.

Table V

original rock

End rock Final salt

0.47

0.10 0.41

analysis

% Co $ Fe 75.5 5.0 0.17

75.5 5.50

0.26
4.60

0.03

0.18

20.7 22.0

Table VI

End rock
Final salt

analysis

% Cu % Nl % Co % Pe

0.02 74.0 0.0 17 0.025

0.10 11.9 0.0 ^ 5 0.075

24.7

Example VII

This example confirms the effectiveness of a chlorination treatment in removing impurities other than cobalfc, copper and iron. Nickel rock containing cadmium, lead, tin and zinc in the amounts shown in Table VII was extracted at 810 ° C. with a chlorine extraction agent containing equal amounts of sodium chloride and potassium chloride and 12 % nickel chloride

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¹⁹ "ORiGl (MAL INSPECTED

Rock-to-extractant ratio of 1: 1.5 treated. The compositions of the refined rock and loaded extractant are given in Table VII. The loaded extraction agent] was after separation of the refined rock to be produced in a manner similar to that described in Example VIII an alloy powder containing nickel, lead, tin, cadmium and zinc.

Table VII

Ά Pb original
rock 0 .23 End rock 0 .002 O .11

0.2

analysis

Sn % Cd
0.2

% Zn 0.15

0.01 0.005 0.001

0.15 0.15 0.10

Example VIII

This example confirms that loaded chloride extraction agent can be electrolyzed to produce alloy powders and to regenerate the chloride extraction agent for re-brewing. An electrolytic bath containing kO g sodium chloride, 40 g potassium chloride and copper, nickel, cobalt and one in the amounts shown in Table VIII was prepared and maintained at a temperature of 800 ° C. A potential difference of 2 volts was applied to the graphite electrodes immersed in the loaded extractant and an anode current density of 83 amperes per dome was maintained. After 32 minutes, at least about 95 % of the copper, nickel, cobalt and iron from the loaded extractant had deposited on the cathode, while chlorine was evolved on the anode; That

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regenerated extractant, its analysis in table VIII was for reuse for chlorination treatment suitable. A current efficiency of $ 51 was achieved under these conditions.

Table VIII

analysis

% Cu % Ni % Co % Fe

original salt 0.58 2.5 0.64 0.18

Final salt (80gm) ₀ . ₀₀₂ 0.066 0.002 0.002

Example IX

This example shows the electrolysis of a loaded extractant on a larger scale; An electrolytic bath 5OOO g of sodium chloride, 5000 g of potassium chloride and copper, nickel, cobalt and iron contained in the amounts shown in Table IX quantities was formed and maintained at a temperature of 78o C ^0. A stainless steel cathode and a graphite anode were immersed in the electrolysis bath and a potential difference of 2 volts was applied to the electrodes.

give. The anode current density was 60 amperes per

rend the cathode current density was 93 amperes per dem. After a period of 6 hours, at least about 95 % of the copper, nickel and cobalt had been deposited from the loaded extraction medium] with a current efficiency of 53 %. The regenerated extracting agent, the composition of which is given in Table IX, was suitable for reintroduction in the chlorination treatment and the chlorine generated at the anode was used as the chlorination agent.

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ORIGINAL INSPECTED

treatment for the chlorination of other impurities L guqgn in the Nickel rock fed back.

Tabel IX analysis
# Ni % Co % Pe % Cu 1.45
0.01 0.14
0.013 o.4o
0.05 original
(10,000 gm)
Final salt salt 2.95
0.02 Example X

This example demonstrates that a loaded chloride extractant can be regenerated by adding a magnesium base alloy. A partial magnesium base alloy, which had the composition given in Table X, was introduced into the loaded extractant in an amount of 1 mol equivalent of magnesium for every mol equivalent of base metal, which contained equal parts of sodium and potassium chlorides and chlorinated metal values in the in Table X contained amounts shown. The loaded extractant had a temperature of 750 ⁰ Gj when the magnesium alloy was added thereto and was kept in a stirred state to produce good liquid-liquid contact between the liquid magnesium alloy and the supernatant loaded extractant. The regenerated extractant had the composition shown in Table X.

309β10 / («70-! OBiCNAL INSPECTED

Table X

analysis %

% Cu fo ML % Co $ Fe % Mg ''

loaded extraction agent 2.73 10.9 4.40 2.65 0.88

Magnesium alloy 2.70 8.35 2.85 0.095 remainder *

regenerated ex- 0.007 0.015 0.007 0.045 9.28 traction agent

"kest magnesium plus limited amounts of with the magnesium associated oxygen.

Example XI

This example illustrates the cyclic nature of the process of the invention. A loaded extractant of the composition shown in Table XI and a temperature of 75O ⁰ C was treated with a magnesium-based alloy having the indicated in Table XI composition in an amount of about one part of magnesium-based alloy for each 17 parts loaded Elttraktionsmittel in a similar manner as it is described in Example X, implemented. The regenerated extractant had the analysis given in Table XI.

Molten nickel gesture showing the properties given in Table XII Composition and a temperature of 750 ° C. was used with gaseous chlorine in the method described in Example II Way to produce a refined rock, which the analysis given in Table XII showed, during the Chollerungstoehanilung the nickel rock with a titanium standing Layer of regenerated extractant in one

0 9 3! 0 / ΐ) 7 U 2

Amount that is about 3 parts of extractant for every 5
Parts of the rock corresponded to »provided for the collection of the chlorinated impurities. The analyzes of the regenerated and the loaded extractant are also given in Table XII. This example confirms that the process can be performed on a cyclical basis, thereby minimizing the cost of reagents and fuel.

Table XI % Cu Ά analysis Ni % Co % Fe # Mg 3-05 7th ■ 75 0.65 0.56 —_ loaded extraction 2.7 8th .35 2.85 0.09 74.8 middle 0.003 0 .005 0.005 0.032 4.2 Magnesium alloy regenerated extract

media

Table XII

Rock chlorination with purified salt

fi Cu analysis % Co <fo Pe fo Mg 3.88 fo St. Ο.72 0.22 ■ -_ original rock 0.003 72.5 O.OO5 Ο.Ο32 4.2 regenerated extract O.OO5 media 0.96 0.12 Ο.Ο85 - refined rock 4.05 76.Ο 1.5 I.65 5.0 attenuated extraction 6.0

middle

309810/070?

Claims (11)

Claims 1. Process for refining nickel sulfide, in which Impurities from a molten nickel sulfide bath can be extracted by liquid-Flüsäg extraction, thereby marked that the bathroom with a supernatant extractant liquid layer of at least one Group IA or · HA metal chloride provided that the nickel sulfide is brought into contact with at least chlorine or nickel chloride / chlorinated impurities extracted into the extractant layer, which is separated, regenerated and reused will. 2. The method according to claim 1, characterized et gekennzeichn that the extraction agent of 0.1 to 20 wt -.% Niekelchlorid contains. J. The method according to claim 1 »characterized in that chlorine ^{1 is} blown into the molten nickel sulfide. 4. The method according to any one of claims 1 to 3 »thereby g e k e η η amounts to. k e η η ζ e 1 c h η e t that the temperature 750 to 950 C 5- The method according to any one of claims 1 to 4, characterized ge k e η η ζ e i c h η et that you can regenerate Separation of the nickel alloy and generation of gas - 25 309810/070? mlgem chlorine makes by electrolysis. 6. The method according to claim 5 ^ characterized in that dasi
will lead. net that the electrolysis was carried out at 750 to 900 ° C 7 · The method according to any one of claims 1 to 4, characterized in that the extractant regenerated by adding magnesium or a magnesium base alloy. 8. The method according to claim 7 *, characterized in that the added magnesium base alloy contains at least β % nickel or copper, whereby the alloy sinks into the extractant. 9 · Method according to one of Claims 7 or 8, characterized in that that part of the nlagnesi-umbela » where extraction agent is electrolytically treated for the recovery of magnesium. 10. The method according to any one of the preceding claims, characterized ₉ that adding nickel chloride to the purified chloride extractant prior to addition to the bath. 11. The method according to any one of the preceding claims, characterized in that the refined _s nickel sulfide on the surface with free-oxygen containing gas is blown in a turbulent bath to metallic nickel. 309810 / 07-2