DE2857455A1 - RECOVERY OF ELEMENTAL SULFUR AND METAL VALUES FROM TAILINGS FROM COPPER RECOVERY PROCESSES - Google Patents

Description

PATENT ADVOCATES A. GRÜNECKER

H. KINKELDEY

Dft-ING

W. STOCKMAIR

OR.-ING. ■ A »E lCAJLTSCHJ

K. SCHUMANN

Often RER NAT. ■ DIPL PHVS

P. H. JAKOB

DtPL-lNG.

G. BEZOLD

DR RB * MAT. ■

8 MUNICH

MAXIMILIANSTRASSB 4-3

P 14 500

Nov 28, 1979

description

Extraction of elemental sulfur and of
Metals from waste from copper production processes

Notice of related registrations

This registration is a continuation-in-part registration of am U.S. Patent Application No. 894,515, filed April 10, 1978.

Technical area

The invention relates to hydrometallurgical processes for Extraction of copper from its ores, especially sulphide ores, the ore concentrate containing iron (III) chloride and / or copper (II) chloride is leached to solubilize the copper as chloride and elemental sulfur '.

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State of the art

The basic method that is improved by the method of the invention is illustrated by those processes described in U.S. Patents 3,785,944, 3,798,026, 3,879,272, 3,972,711, 4,013,457 and 4,029,324. The statements of some of these patents include chemical equations that describe the reactions explain what expires when chalcopyrite with iron (III) chloride and Copper (II) chloride is leached to solubilize the copper and to form elemental sulfur. In some of the patents is also described how copper from the formed copper (l) chlairrd is obtained by crystallization and subsequent separation of the copper from the crystallized copper (l) chloride. There are too already various other methods of extracting copper from the leach solution, which are used in the leaching of copper ores and concentrates obtained with iron (III) chloride and / or copper (II) chloride become known.

Industrial application

Copper sulfide ores contain in particular materials that are found in iron (ill) chloride and cupric chloride leachants are soluble and are usually discarded in the hydrometallurgical leaching waste with these leaching agents. These materials can contain valuable substances such as the elemental sulfur formed in the leaching reactions as well as gold and molybdenum. she may also contain contaminant-like materials such as pyrite, jarosite, and others. If the pyrite contains gold, it won't discarded in the flotation stage ". Part of the copper sulfide mineral,

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which is embedded in the mineral granules is not dissolved by the leaching agent because the leaching agent with the copper mineral does not come into direct contact and this undissolved mineral is contained in the waste.

Since the methods of extracting copper from its sulphide ores, which are acceptable under environmental regulations, are very competitive From an economic standpoint, it is important to have effective processes in place that are compatible with copper recovery processes are compatible, for the recovery or recovery of salable elemental sulfur and metals from the waste. Such a process should be such that it can be adapted to pilot plant production in a continuous operation can and to date no such method is known. One major difficulty is that the relatively small amounts of metals other than copper in the ore after the concentration of the Copper ore is contained in large volumes of gangue and it has not been possible to process this large amount of material economically, to extract the relatively small amounts of metals. This was particularly true for the known methods where sulfur was removed from the ore by pyrometallurgical processes. Difficulties arose with the separation of elemental Sulfur in the presence of copper and molybdenum in the concentrates. Another difficulty arose in the extraction of molybdenum in the presence of copper that is not contaminated by the copper to such an extent that the molybdenum cannot be sold, and while at the same time achieving a high level of molybdenum recovery. Usually not just any molybdenum could remained in the residues, recovered or recovered. If gold is present, it will also contaminate the molybdenum.

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The aim of this invention is therefore to provide a method for the recovery or recovery of elemental sulfur, copper, gold and Molybdenum from the waste that is produced in the hydrometallurgical processing of copper ores in a continuous process Operation to create the waste that makes up the sulfur and the metals are recovered, first concentrated to a relatively small volume.

Another object of the invention is to provide a method of recovering a higher percentage of the copper from the wastes obtained from the hydrometallurgical processing of copper sulphide ores.

Another object of the invention is to provide a method of extraction or recovery of molybdenum which is not contaminated to such an extent by copper or gold, if any is that the molybdenum meets the purity standards for a negotiable Product is insufficient from hydrometallurgical processing waste of copper sulfide ores.

Description of the invention

A process for the recovery or recovery of elemental sulfur, copper, gold and molybdenum from the wastes of the hydrometallurgical treatment of copper ores, in which the sulfur and the metals are selectively separated in a required sequence with specific reagents, comprises (a) subjecting the waste to a froth flotation for the extraction or recovery of elemental sulfur, copper, gold and molybdenum in a liquor concentrate that is a relatively small proportion of the original

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Contains waste, and discarding a relatively large proportion of the waste which contains impoverished gangue; (b) the implementation a liquid-solid separation in the liquor concentrate; (c) the removal of elemental sulfur from the residue of step (b), preferably by (l) leaching the residue of the Step (b) with a solvent for sulfur, carrying out a Liquid-solid separation with the slurry and separation of the Sulfur from the liquid, or (2) volatilization of the sulfur from the residue of step (b) and separating the elemental sulfur from the steam; (d) grinding the residue from the step (c) to expose the copper minerals; (e) the leaching of the ground residue of step (d) with iron (III) chloride to selectively to dissolve the copper and iron contained therein; (f) performing a liquid-solid separation on the slurry of the Stage (s); (g) recycling the filtrate from step (f) containing solubilized copper to the original leachate for copper extraction; (h) the leaching of the residue of the Step (f) with cyanide to solubilize gold and recover it the gold from the resulting solution; (i) subjecting the residue of step (h) to froth flotation and separating it the liquor concentrate, which contains molybdenum and elemental sulfur, formed during iron (III) chloride leaching; (j) the distance of sulfur from the liquor concentrate of stage (i) by 0) leaching with a solvent for sulfur to remove the elemental Sulfur to soIubillieren, resulting in a liquid-solid separation and the separation (recovery) of sulfur from the solution follows, or (2) the volatilization of the sulfur from the Concentrate and the extraction or separation of elemental sulfur from the steam and (k) the extraction of molybdenum from the Stage residue (}).

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The waste usually contains pyrite. When together with the If pyrite gold is present, the pyrite is not discarded with the depleted gangue. If there is no gold, it will of course the gold recovery stage is omitted. Jarosite is present in the impoverished gait if it is not removed if necessary as shown in the flow chart of FIG. The sulfur removal stage after gold recovery or gold recovery mainly serves the purpose of upgrading the product molybdenum for sale. It depends on the one in the The amount of copper sulphide contained in the waste and thus the amount of sulfur formed during iron (III) chloride leaching.

Brief description of the drawings

Fig. 1 shows a flow diagram of a method for hydrometallurgical Recovery or recovery of copper, which embodies the method according to the invention, and

Fig. 2 shows a flow diagram of the method according to the invention applied to wastes from the ore leaching stage in hydrometallurgical processes such as those illustrated in FIG. 1.

Detailed description of preferred embodiments of the invention

The invention is described below with reference to the accompanying Drawings and the illustrative examples below.

The results given in the following examples were obtained with wastes resulting from hydrometallurgical processing

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of chalcopyrite for the extraction or recovery of copper originated, but the process is not restricted to this specific waste, as it can also be used for waste that is generated by hydrometallurgical treatment of other copper sulfide ores. The procedure is not based in its application Waste alone restricted as it can obviously be applied to ore concentrates in general · The term used here "Waste" includes concentrates.

From Fig.. 1 it can be seen that the chalcopyrite concentrate two Is subjected to leaching, which leads to wastes that include some non-solubilized copper, gold, molybdenite, elemental sulfur and other undissolved materials, the latter making up the bulk of the wastes, and those in the flotation stage be discarded. The copper is contained in undissolved chalcopyrite, which has not come into contact with the leachant.

The leaching illustrated in the attached flow diagram was with Iron (III) chloride and copper (II) chloride carried out and follows the method as indicated in some of the above-mentioned patents. Briefly, the process involves leaching Copper sulfide ores and concentrates with iron (III) chloride and / or Copper (ll) chloride with the formation of a leaching solution, the buyer (l) chloride, Copper (II) chloride, iron (II) chloride, soluble metal impurities and contains insoluble materials, the latter going into the wastes (residues), separating at least one Part of the copper (l) chloride in the leach solution by crystallization, whereby copper (l) chloride crystals and a mother liquor are obtained, the separation of the copper (l) chloride crystals from the mother liquor, reducing the crystallized copper (l) chloride

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Product copper, controlling the content of impurities in the mother liquor by using an effluent stream, subjecting the mother liquor thus obtained to one

Oxydrolysis with oxygen to produce the leachant, cupric chloride and to regenerate iron (III) chloride and to precipitate iron, filtering and returning the filtrate to the second Leaching. Jarosite can be removed from the filtrate as shown »

The application of the method according to the invention is obvious not limited to wastes generated in the above process or any other specific processes for the extraction of copper from sulphide ores are obtained »

The composition of the chalcopyrite leaching wastes, such as it has been described above poses a particular problem in that the wastes contain elemental sulfur, the must be removed first to prevent it from interfering with the production of copper, gold and molybdenum. That contained in the waste Copper contaminates the molybdenum when it is not in an effective way is removed prior to the extraction of molybdenum. Gold must also be in front of the Molybdenum recovery will be removed or it will contaminate the molybdenum. Since copper is soluble in sodium cyanide, the copper removal step must be performed be upstream of the gold removal stage. It can be seen from this that the order of the steps carried out with the reagents used] is critical for the formation of practically j pure gold and molybdenum products. The inventive method | represents a cooperative addition to procedures such as those, § as described in the above-mentioned patents, |

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because it enables the recovery or recovery of copper from the waste that would otherwise be lost, and that from the Waste is removed in the form of a solution compatible with the main leaching circuit for the recovery of copper into the the solution is returned. The process according to the invention also provides elemental sulfur and the process according to the invention relates refers to the extraction or recovery of this element from waste in which it is present together with copper, gold and molybdenum.

The method according to the invention is described below with reference to the accompanying drawings. As can be seen, the wastes from the second stage leaching of the original or major chalcopyrite leaching, which contain pyrite and possibly jarosite, are subjected to flotation. As shown in Fig. 1, jarosite can optionally be removed from the recycle stream from the oxydrolysis before it is returned to the second leach. Flotation is a pre-concentration stage that is used to reduce the volume of waste (residues) processed for the extraction of elemental sulfur and metals. The flotation cycle consists of two stages of flotation using conventional flotation agents, discarding the depleted gangue which contains any jarosite present and most of the pyrite, provided the latter ¹ does not contain gold. It was found that the liquor concentrates only make up 27.5% by weight of the waste and always contained 93 % of the copper, 84 % of the molybdenum and 99 % of the sulfur in the waste. This considerable reduction in the waste to be processed for the recovery of elemental sulfur and metals is a very advantageous result of the invention from an economic point of view. The rejected,

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yi-

Iron containing compounds can either be acidified to produce a material that can be used as soil nutrient or they can be disposed of as waste material «The process also works without this flotation stage, but is then obvious more expensive because of the additional material that is handled must become"

The elemental sulfur is then extracted from the liquor concentrate won (detached) «The order of execution of this stage is important because then if during the execution of the Steps for the extraction of copper, gold and molybdenum elemental sulfur is present, from a physical point of view considered leads to serious problems.

In one embodiment of the invention, the liquor concentrate filtered to remove water and the residue is left for 15 minutes leached for a long time, preferably with ammonium sulfide, with the formation of ammonium polysulfide according to the following reaction equation: j

ί ο

Preferred ammonium sulfide conditions appear to be about 0.454 kg (l Ib To be ammonium sulfide per 0.454 kg (l Ib) of sulfur. The pulp is leached, filtered and washed thoroughly. The filtrate is then introduced into an evaporator in which the ammonium polysulfide according to the following reaction equation by heating

95 ⁰ C is decomposed:

> H ₂ S ■ ♦ 2NH ₃ ♦ XS °

This temperature is not critical. The sulfur will crystallize out and the ammonium sulphide is given off by a skfubbender

0 30 60 4/00 29. · ----

KX. 2857A55

Gases regenerated with water and returned to the ammonium sulfide treatment stage. Because of this regeneration of ammonium sulfide, the total ammonium sulfide loss in the process is less than about 5 %. The sulfur precipitate consists of pure (99.8 ^ iger) rhombic crystals, the main impurity being iron.

Solvents other than _: ammonium sulfide, such as sodium sulfide, perchlorethylene, and carbon disulfide, can also be used to dissolve sulfur. Of course, ammonium sulfide is the preferred solvent as it can be regenerated for reuse.

In another embodiment of the invention, the liquor concentrate heated to volatilize the sulfur. The volatilization temperature is not critical for practical reasons however, it is preferably such that the sulfur is removed within a reasonable time. Preferred temperature ranges are between 300 and 600 ° C, with the most preferred range being 400 to 500 ° C. Because sulfur is spontaneous above 400 ° C can burn if the reaction takes place in an inert atmosphere, e.g. in nitrogen. That inert atmosphere provides a medium for flushing the sulfur out of the volatilization chamber for condensation and recovery. The reaction can be carried out in partial vacuum, which is preferably varies from about 25.4 to about 63.5 cm (10 to 25 inches) of mercury, these conditions being the time and temperature requirements facilitate.

Since about 2 % of the copper added to the leaching cycle in the form of chalcopyrite remains in the waste (residues) because they

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ν "■ '28574

:. : have not come into contact with the Auslae mi ti el, it is dated. : Economic point of view, important to the copper which has been separated in the> · ■ waste ,, cus eggs ölsraentare sulfur to win * The order: the implementation of this step is important because if ccnru dos copper is not removed before _f the molybdenum is extracted, the copper c ~ s Hoiybc'än bis .; zt «impure to such a degree; when it is no longer for sale for important kotufü ^ -x-zieXie purposes, like z-J3 «for that. Alloy with ^ TC ^! hI "Copper has before performing the (joldgewirmunesstufe away verdsn ^ about it in sodium cyanide, the solvent used for gold extraction is soluble."

The residue from the sulfur removal step is only about 6 % of the total weight of the batch, further illustrating the effectiveness of the invention in reducing the amount of waste that must be processed to recover the heoile. The Röckstand is ground in a ball mill in.einem closed-end circuit with a cyclone, to about 95%, particle size less than E _f 044 mm (-325 me & h) in order; .- practically total, the "expose remaining Kupfererzkonsentrat The ground solids are then exposed to an iron (III) chloride solution for about 3 hours at 105 ° C, after which the pulp is filtered to remove the solubilized copper and iron in the form of , chlorides .ent.haltende. The oil was returned to the main hydrometal leaching circuit, the iron (III) chloride extraction used, low temperature is not critical.

. As the flow diagram of Figure 2. ze, IGT, thereafter, gold, if present, obtained (recovered) ο The residue from the iron (lll) chioridGu.slaugi.ir "g with Natriümcyonid: leached ,, as

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-ί-

this is common for the selective solubilization of the gold the molybdenum and the resulting slurry are subjected to a liquid-solid separation. The gold is used obtained from its cyanide solution using conventional methods. Other cyanides such as e.g. some of the remaining alkali metal cyanides can be used; However, sodium cyanide is preferred for economic reasons.

Thereafter, the molybdenum is recovered (recovered) as shown in the flow diagram. The residue from the cyanide leaching is filtered and washed. The washing water, the amount of which is very small, is returned to the cyanide leaching system. The residue is again converted into a pulp and cleaned 3 times. The repeatedly purified concentrate from this liquor cycle is again leached with ammonium sulfide to remove the elemental sulfur formed in the ferric chloride leaching, and the sulfur is separated and the ammonium sulfide is regenerated as indicated above. The washing water residue, from which elemental sulfur, gold and copper have been removed, contains 50 to 7% of the original molybdenum in the concentrate, which is 25 to 45 % molybdenum and 1 % copper. The molybdenum can be removed from the residue by known methods be won.

Tests have shown that processes based on the flow chart described above result in recovery of up to 90 % copper, 50 % molybdenum (80 % of the predicted recycle recovery) and over 95 % of the elemental sulfur from the wastes.

The procedure is illustrated by the following example in which

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the method illustrated in the flow diagram of FIG. 2 was used. The sample used did not contain any appreciable amount of gold.

example 1

The waste had the following analysis composition: Cu - 0.52 % Mo - 0.21 % S ° - 21.0 %

The wastes were subjected to two stages of flotation using calcium oxide, sodium silicate and sodium cyanide as flotation agents. After the flotation and elimination of the discarded residue or the waste from the flotation concentrate, the latter had the following analysis composition: Cu - 1.76 %

The discarded waste or the residue from flotation had the following analysis composition:

After filtering the liquor concentrate, the residue was leached using a 45% ammonium sulfide solution of about 0.454 kg (1 lb) ammonium sulfide per 0.454 kg (1 lb) sulfur, to solubilize the elemental sulfur and to add ammonium polysulfide

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form. The resulting slurry was filtered and the filtrate was evaporated at 90 ° C. for 2 hours during which time sulfur crystallized out. The gases were purged with water to recover ammonium sulfide, which was recycled to the ammonium sulfide leaching stage. The sulfur crystals obtained contained 99.8 % sulfur; 98 % of the original sulfur was recovered.

The residue from the ammonium sulfide leach was ball milled until 95% of the solids were less than about 0.044 mm (-325 mesh) in particle size. The ground residue was leached with concentrated ferric chloride at 105 ° C. for 3 hours and the resulting slurry was filtered. The filtrate was returned to the main liquor. It had the following analysis composition:

Cu - 0.23 % Mo - 2.87 % S ° - 21.06 %

indicating that 90.3 % of the total copper had been dissolved in the wastes and returned to the main liquor for recovery.

The residue from the ferrous chloride leaching was again subjected to flotation using the same flotation as used above. The liquor concentrate was separated and it was found to have the following analysis composition:

Cu - 0.48 % Mo - 7.11 % s ° -72.05 * 30604/0029

Elemental sulfur was formed in the iron (III) chloride liquor and it must be removed prior to the extraction of molybdenum. The elemental sulfur was removed by ammonium sulfide treatment, recovered by the procedure described above and the ammonium sulfide was regenerated and sent to the ammonium sulfide leach step returned. After a liquid-solid separation, the residue was washed thoroughly and purified again it had the following analysis composition:

Cu 1.64 % Mo - 24.4 %

50.4 % of the molybdenum in the original wastes has been recovered. Molybdenum with the purity required for alloying with steel was obtained from the concentrate.

To explain the process when applied to a gold containing Concentrate was the process with two gold-containing concentrates, i.e. a "Magma" concentrate and an "Eldorado" concentrate, and the results of the gold recovery stage are given in the tables below.

Table 1

j, ■ + ■ "■ + 'Gold concentration according to the FeCl" -

and / or CuCl ₉ main leach

Magma 1.749 g / t (0.051 troy oz./ton)

Eldorado 31.988 g / t (0.933 troy oz./ton)

The gold distribution after cyanide leaching was as follows:

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Table 2

Gold content Gold distribution Magma concentrate Filtrate 0.48 ppm 92 % Residue 1.4 ppm 8 % Eldorado concentrate Filtrate 7.15 ppm 93 % Residue 22.5 ppm 7 %

The following example shows the effectiveness of sulfur removal from the flotation concentrate by volatilization under varying temperature, pressure and time conditions. The tests were carried out in carried out in a tube furnace without recirculation of the solids and the results are given in Table III below.

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Table (head: 44 %, S °; 3.5 %

Weight of the sample

Weight of the residue

Total weight, of loss

Time (min.)

Temp. ( ⁰ C) pressure,

(cm

(inch) Hg)

% Sulfur in that
Residue

% Sulfur volatilized

ο
a>
ο

O CD N> CO

1.

2.

3.
■ 4.

5.

6th

7th

.

9.
10.
Ii.
12th
13th

6.50 6.50 6.50 6.50 6/50 6.50 6.50 6.50 6.50 6.50 6.50 6.50 6.50

3.41 3.21

3.36 3.20 3.16 2.73 14 08

3,

3.43

3,

3,

09 29

3.14 3.30 3.34 3.77 3.36 3.42

3.07

10 5 5 5

10 10 10 10 10 10 10 10 10

420 420 420 420 420 420 420 450 450 450 475 475 475 Atmospheric pressure 1.9

25.4 (10)
38.1 (15}
55.9 (22)

38 ', 1 (15)
61.0 (24)
25.4 ClO)
38.1 (15)
61.0 (24)
25.4 CLO) -

6l ', 0 * 241

2.8 1.2 5.8 .20 0.1 .33 .34 0.1 .29

96.6

98.65

93.18

99.7

99

99

99

99

99

99

99

99

* ■ When performing the test without a vacuum, S was left at both ends of the tube furnace, whereby the handling of the structure was made difficult.

The tests show that over 99 % of the sulfur can be volatilized within 10 minutes under varying vacuum conditions at temperatures between 400 and 500 C. It appears that the volatilization process described is an effective alternative to dissolving with ammonium sulfide or a similar reagent to remove sulfur. This volatilization process can be incorporated into the process according to the invention with its suitable sequence of steps after the initial froth flotation concentration and / or again after the froth flotation step to concentrate the molybdenum contents.

From the above description it can be seen that a method has been provided was used for the extraction or recovery of copper, gold, molybdenum and elemental sulfur from the waste produced in the hydrometallurgical processing of copper sulfide ores. The procedure leads to a processing of the minimum Amount of waste. It can be adapted for continuous operation. The order of performing the stages with the reagents is important in order to prevent interference with the extraction or recovery of copper, gold and molybdenum by elemental To prevent sulfur and an effective selection separation of the various metals, so that contamination of the recovered or recovered metals is prevented. That Process has a cooperative relationship with the main copper ore leaching stage, because this last-mentioned stage always supplies elemental sulfur and because the iron (III) chloride leaching solution, that recovered from the waste by the method according to the invention Contains copper, for introduction into the main copper ore leaching stage the copper extraction process is applicable, whereby the leaching solution in the main leaching stage for the

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(jlück) recovery of the available copper is returned. Of the achieved high percentage of extraction or recovery of sulfur, copper, molybdenum and gold from the waste explained the economic effectiveness of the process.

One advantage of the method is that a molybdenum rotation circuit in the mine concentrating device is not required, since the process involves the recovery or recovery of the molybdenum allows it to remain in the concentrate. It is known that the recovery of molybdenum in the Flotationskreis.lauf in the Mine concentrator requires and is the recovery of molybdenum in the presence of copper in all copper mills very difficult to perform and results in a significant loss of molybdenum ages when the copper content limit is exceeded of the recovered molybdenum is complied with.

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Claims (1)

Claims 1. A process for the recovery of copper from copper sulphide concentrates, in which the concentrate is leached in a main leaching circuit to form a leaching solution which Copper (l) chloride, KuPfBr (II) ChIOrId, iron (II) chloride and soluble metal impurities, the solution for the Copper extraction is further processed, with the improvement, that elemental sulfur, copper and molybdenum in the waste (residues) are selectively separated from the main leaching and are obtained using the following successive stages: a) Removal of elemental sulfur from the waste; b) Recovery of the copper from the residue of the sulfur-solvent leaching of step (a) by leaching the sulfur-depleted one Residue with iron (III) chloride, in order to selectively Iu bi Iize copper; and c) Extraction of the molybdenum from the residue of the iron (III) chloride leaching of stage (b). 2. The method of claim 1, wherein the sulfur is removed by solubilizing the sulfur and then separating elemental sulfur from the solution. 3. The method of claim 1, wherein the sulfur is separated by volatilization. 4. The method of claim T, wherein the recovered solubilized Copper for the extraction of elemental copper in the main outlet 030604/0029 supply cycle is returned. 5. The method according to claim 1, which is carried out continuously with the, Main liquor is carried out. 6. The method according to claim 1, wherein the waste from step (a) Contain gold and in which, before step (c) is carried out, the residue of step (b) is leached with cyanide to convert to gold solubilize before introducing the residue into step (c) and recovering the gold from the cyanide solution. 7. The method of claim 1, wherein prior to performing the step (a) the waste is concentrated by tree flotation to remove impurities such as pyrite and jarosite. 8. Process for the extraction of copper from copper sulphide concentrates, in which the concentrate is leached in a main leach circuit is formed with the formation of a leaching solution, the copper (l) chloride, Contains copper (II) chloride, iron (II) chloride and soluble metal impurities, the solution being further processed for copper extraction, with the improvement that elemental sulfur, Copper and molybdenum in the waste (residues) from the main leaching can be selectively separated and recovered, which comprises the following stages: α) Extraction of elemental sulfur from the waste by solubilizing the sulfur with a solvent for sulfur and subsequent separation of the elemental sulfur from the solution; b) Extraction of copper from the residue of the sulfur-solvent leaching of stage (a) by leaching the sulfur-depleted residue with iron (III) chloride, selectively for copper 03060A / 0029 to solubilize; and c) Extraction of molybdenum from the residue of the iron (III) chloride leaching of stage (b). 9 · The method according to claim 8, in which the solubilized » Copper is returned to the main leach cycle Extraction of elemental copper. 10. The method of claim 8, which is continuous with the Main liquor is carried out. 11. The method according to claim 8, wherein in step (a) the Sulfur solvent is ammonium sulfide. 12. The method of claim 11, wherein the ammonium sulfide in a The amount used is approximately equal to the amount of sulfur in the waste. . . . 13. The method of claim 11, wherein the elemental sulfur is obtained from the sulfur solution by evaporation and the ammonium sulfide is regenerated by dissolving the exhaust gases in water. 14. The method according to claim 8, in which the waste (residues) of stage (a) contain gold and before the implementation of the Step (c) the residue from step (b) is leached with cyanide to solubilize the gold before the residue enters the step (c) is introduced and the gold is extracted from the cyanide solution. Ό 30 6 0-4 / 00 29 15. The method according to claim 8, wherein before performing the Step (a) the wastes (residues) are concentrated by froth flotation to remove impurities such as pyrite and jarosite remove. 16. Hydrometallurgical process for the extraction of copper from Copper sulphide ore concentrates, in which the concentrate in a ■ / Main leaching stage with iron (III) chloride and / or copper (II) chloride leaching occurs to form a leaching slurry that contains cupric chloride, cupric chloride, and ferrous chloride in solution contains, the latter being separated from the residue or waste, the undissolved material (s) such as gold, molybdenite, elemental Contains sulfur, some copper and impurities, and the solution is further processed for the extraction of copper becomes, with the improvement that the wastes (residues) are concentrated to a small volume that is essentially the whole materials to be recovered and which contains elemental sulfur, with gold, copper and molybdenum in the concentrated waste (Residues) selectively separated from each other and recovered (recovered) which comprises the following steps carried out in the order given: α) narrowing the waste (the residue) by making it (him) subjected to a froth flotation to remove the elemental sulfur and the copper, gold and molybdenum contents in a liquor concentrate with a greatly reduced solids volume collect and jarosite, if any, and other impurities to discard in an impoverished gait; b) performing a liquid-solid separation with the liquor concentrate; · '. . . c) Leaching of the residue from stage (b) with a sulfur solution 030604/0 02 9 means for dissolving elemental sulfur; d) Performing a liquid-solid separation on the slurry stage (c); e) Obtaining (separating) elemental sulfur from the filtrate stage (d); f) leaching of the residue from stage (d) with iron (III) chloride, to selectively dissolve copper therein; g) Performing a liquid-solid separation on the slurry stage (f); h) recycling of the filtrate from stage (g) to the main leaching stage for copper recovery; i) Leaching of the residue from step (g) with cyanide for solubilization of the gold it contains; j) Performing a liquid-solid separation on the slurry stage (i); k) recovery (separation) of gold from the solution of step (j); l) subjecting the residue from step (j) to froth flotation .and Separation of the liquor concentrate, which contains the molybdenum and the elementary elements formed during the leaching of iron (III) chloride Contains sulfur; m) leaching of the liquor concentrate of stage (l) with a Sulfur solvent to reduce the amount of iron (III) chloride leaching solubilizing elemental sulfur formed in step (f); ■ n) Performing a liquid-solid separation on the slurry the stage (m); o) Recovery (separation) of sulfur from the filtrate of the Stages); and p) recovery (separation) of molybdenum from the residue of stage (s). 0 306 04/002 9 "Q / 17. The improved method of claim 16, wherein the The sulfur solvent of step (c) is ammonium sulfide. 18. The improved method of claim 17, wherein the more elementary Sulfur is recovered from the sulfur solution by evaporation and ammonium sulfide is regenerated by contacting the Exhaust gases with water. 19. Process for the extraction of copper from copper sulphide concentrates, in which the concentrate is leached in a main leaching circuit with the formation of a leaching solution, the copper (l) chloride, Copper (II) chloride, iron (II) chloride and soluble metal impurities contains, the solution being further processed for copper extraction, with the improvement that elemental sulfur, Copper and molybdenum in the wastes (residues) of the main leaching are selectively separated and recovered, the following Levels includes: a) Removal of elemental sulfur from the waste (residues) by volatilization of the sulfur; b) Extraction of copper from the residue of the sulfur volatilization step (a) by leaching the sulfur-depleted residue with iron (III) chloride to selectively solubilize copper; and c) Extraction of molybdenum from the residue of iron (III) chloride leaching the stage 20. The method of claim 19, wherein the recovered solubilized Copper for the extraction of elemental copper in the main liquor cycle is returned. 21. The method according to claim 19, which is continuous with the main 030604/0029 lye is carried out. 22. The method according to claim 19, wherein in step (a) the Sulfur is volatilized at temperatures between about 300 C and 600 C. 23. The method according to claim 19, wherein in step (a) the sulfur b <
is done. Sulfur is perishable at temperatures between approx. 400 C and 500 C 24. The method of claim 19, wherein in step (a) the Sulfur is volatilized under partial vacuum. 25. The method according to claim 19, wherein in step (a) the sulfur is volatilized by heating for up to 15 minutes. 26. The method according to claim 19, in which the waste (residues) of stage (a) contain gold and, before carrying out stage (c), the residue of stage (b) is leached with cyanide to obtain the Solubilize gold before introducing the residue into step (c) and the gold is extracted from the cyanide solution. 27. The method according to claim 19, wherein prior to performing the Step (a) the wastes (residues) are concentrated by froth flotation to remove impurities such as pyrite and jarosite remove. 28. Hydrometallurgical process for the extraction of copper from copper sulfide ore concentrates, ^r , 'in which the concentrate in a main leaching stage with iron (III) chloride and / or copper (II) - 030604/0029 chloride is leached to produce a leach slurry, the copper (l) chloride, copper (II) chloride and iron (II) chloride in Contains solution, the latter from the residue or waste separated, the undissolved material (s) such as gold, molybdenite, elemental sulfur, some copper and impurities contains (contain), and the solution is further processed for the extraction of copper becomes, with the improvement that the waste (residues;) be concentrated to a small volume, which contains practically all the materials to be recovered, and the elemental sulfur, the gold, copper and molybdenum in the concentrated waste (residue) are selectively separated and recovered, the following specified stages in the order named includes: a) Concentration of the waste (residue) by subjecting it (the same) a foam flotation to the elementary Sulfur and the copper, gold and molybdenum contents in a liquor concentrate with a greatly reduced solid volume to collect and remove jarosite, if any, and other impurities in an impoverished gangue; b) performing a liquid-solid separation on the liquor concentrate; c) Extraction of elemental sulfur from the liquor concentrate of the Step (b) by volatilizing the sulfur and recovering the sulfur from the steam; d) leaching of the residue from stage (c) with iron (III) chloride, to selectively dissolve copper therein; e) Performing a liquid-solid separation on the slurry stage (d); f) Recycle the filtrate from stage (e) into the main leach stage for copper extraction; g) leaching of the residue from step (e) with cyanide to remove the gold to solubilize in it; 030604/0029 h) Performing a liquid-solid separation on the slurry the stage (g); i) recovery of gold from the solution of step (h); j) Subjecting the residue to stage (h) of a froth flotation and separation of the liquor concentrate, the molybdenum and elemental Sulfur, formed by iron (III) chloride leaching, contains; k) heating the liquor concentrate of stage (3) for volatilization that formed by the iron (III) chloride leaching of stage (d) elemental sulfur; l) recovery of the sulfur from the steam of step (k); and m) Obtaining the molybdenum from the residue from stage (k). 29. The improved method of claim 28, wherein the sulfur is volatilized at temperatures between about 4CO and 500C. 30. The improved method of claim 29, wherein the sulfur is volatilized under partial vacuum. 31. The improved method of claim 30, wherein the sulfur is volatilized by heating for up to 15 minutes. 32. Processes for the extraction of copper, molybdenum and elemental sulfur from copper sulfide concentrates or waste containing copper, Contain molybdenum, elemental sulfur, pyrite and other impurities, which includes: α) subjecting the concentrate or waste (residues) a foam flotation to collect elemental sulfur, copper and molybdenum in a liquor concentrate and discard the remainder of the waste (residue); 03060A / 0029 b) Carrying out a liquid-solid separation on the liquor concentrate stage (a); c) recovery of the sulfur from the liquor concentrate of step (b); d) leaching of the residue from stage (c) with EiSOn (IIl) Chloride, to selectively dissolve the copper therein; : e) Performing a liquid-solid separation on the slurry stage (d); f) recovery of copper from the filtrate of step (e); and g) Extraction of molybdenum from the residue of step (e). 33. The method of claim 32, wherein the sulfur recovery step (c) is carried out by leaching the residue from step (b) with a solvent for sulfur to remove elemental sulfur to dissolve; a liquid-solid separation performed on the slurry and the recovery of elemental sulfur the filtrate 34. The method of claim 33, wherein the solvent for sulfur is ammonium sulfide. 35. The method of claim 34, wherein the elemental sulfur recovered and ammonium sulfide is regenerated by evaporation of the filtrate. 36. The method of claim 32, wherein the sulfur recovery stage (c) takes place by volatilization of the sulfur at temperatures above the melting point of the sulfur and by ' Extraction of the elemental sulfur from the steam. 37. The method of claim 36, wherein the sulfur is at temperatures 030 604/0029 is volatilized between about 300 ° C and 600 ° C. 38. The method according to claim 32, wherein in step (f) the copper is obtained from the iron (III) chloride leach solution by Introducing the solution into the leaching stage of a hydrometallurgical Cycle for the extraction of copper from its sulphide ores, the ore with iron (III) chloride and / or copper (II) chloride leaching takes place to form a leaching solution which contains copper (I) chloride, copper (II) chloride and iron (II) chloride. 39. The method of claim 32, wherein the concentrate of step (a) contains gold and, before step (g) is carried out, the residue of step (e) is leached with cyanide to solubilize the gold before the residue is introduced into step (g) and the Gold is extracted from the cyanide solution. 40. Process for the extraction of copper from copper sulphide ore concentrates, in which the concentrate is leached out in a main leaching stage to form an exhaustion slurry which Copper (l) chloride, copper (II) chloride and iron (II) chloride in solution contains, the latter being separated from the residue or waste, the undissolved materials such as molybdenite and elemental Contains sulfur, some copper and impurities, and the solution is further processed for the recovery of copper, with the improvement that elemental sulfur, copper and molybdenum in the Residue (waste) can be selectively separated and recovered, the the stages includes: a) Subjecting the residue (waste) to froth flotation to collect the elemental sulfur and the copper and molybdenum 030604AO029 -A- keep it in a liquor concentrate and discard the pyrite, jarosite, if any, and other impurities; b) performing a liquid-solid separation on the liquor concentrate; c) recovery of sulfur from the liquor concentrate of step (b); d) leaching of the residue from stage (c) with iron (III) chloride, to selectively dissolve the copper therein; e) Performing a liquid-solid separation on the slurry stage (d); f) recovery of copper from the filtrate of step (e); g) subjecting the residue of step (e) to froth flotation and separation of the liquor concentrate containing elemental sulfur and molybdenum; h) recovery of sulfur from the liquor concentrate of step (g); i) Obtaining molybdenum from the residue from step (h). 41. The method of claim 40, wherein the sulfur recovery of Step (c) is carried out by leaching the residue from step (b) with a solvent for sulfur to dissolve elemental sulfur; a liquid-solid separation that occurs in the slurry is carried out; and the recovery of elemental sulfur from the filtrate. 42 · The method of claim 41, wherein the solvent for Sulfur is ammonium sulfide. 43. The method of claim 42, wherein the elemental sulfur recovered and ammonium sulfide is regenerated by evaporating the filtrate. ' 030604/0029 ■ i ■ ■ 44. The method of claim 40, wherein the sulfur recovery stage (c) takes place by volatilizing the sulfur at temperatures above the melting point of sulfur and recovering it of elemental sulfur from the steam 45. The method of claim 44, wherein the sulfur is at temperatures is volatilized between about 300 ° C and 600 ° C. 46. The improved method of claim 40, wherein in step (f) the copper from the ferric chloride leach solution is obtained by recycling the latter into the main leach stage for the recovery of copper. 47. The improved method of claim 40, wherein the concentrate of stage (a) contains gold and, before carrying out stage (g), the residue of stage (e) is leached with cyanide in order to solubilize the gold before introducing the residue into step (g) and recovering gold from the cyanide solution. 48. The improved method of claim 43, wherein in step (e) the filtrate at a temperature of at least about 95 ° C is evaporated. 49. The method of claim 44, wherein the sulfur is at temperatures is volatilized between about 400 C and 500 C. 50. The method of claim 44, wherein the sulfur under partial vacuum is volatilized. 0 306OA / 0029 Translation of amended claims 1. Process for the extraction of elemental sulfur and metals from copper sulphide ore concentrate or waste containing elemental sulfur, copper, molybdenum and impurities through the stages: a) Removal of elemental sulfur from the concentrate or the Waste; b) Extraction of copper from the residue of .Stufe (a) by leaching the sulfur-depleted residue with iron (III) chloride, to selectively solubilize copper; and c) Extraction of molybdenum from the residue of iron (III) chloride leaching stage (b). 2. The method according to claim 1, characterized in that in the iron (III) chloride leaching of step (b) formed further
elemental sulfur is removed prior to step (c). 3. The method according to claim 1 or 2, characterized in that sulfur is removed by solubilizing the sulfur in a sulfur solvent and that elemental sulfur from the solution
is won. 4. The method according to claim 1 or 2, characterized in that sulfur is removed by volatilization. 5. A method according to any preceding claim, characterized in
characterized in that the concentrate or waste contains gold
(contain) and before carrying out stage (c) the solid residue 030 604/00 29 from step (b) is leached with cyanide to the gold solubilize before the remaining solid residue is introduced into step (c) and gold is recovered from the cyanide solution. 6. The method of any preceding claim characterized in that prior to performing step (a) the concentrate or the waste is (are) concentrated by froth flotation, to remove impurities. 7. The method according to any preceding claim, characterized in that copper from the iron (III) chloride leach solution of step (b) is recovered by introducing the solution into the leaching stage of a hydrometallurgical circuit for recovery of copper from its sulphide ores, the ore containing iron (lll) chloride and / or copper (II) chloride is leached with formation a leach solution that contains copper (l) chloride, copper (II) chloride and ferrous chloride. 8. The method according to claim 7, characterized in that the method is carried out according to the hydrometallurgical cycle. 9. The method according to claim 3, characterized in that the The sulfur solvent is ammonium sulfide. 10. The method according to claim 9, characterized in that the amount of ammonium sulfide used in relation to its weight is approximately is equal to the amount of sulfur in the concentrate or in the waste (residues). 030604/0029 Π. Method according to claim 9 or 10, characterized in that that elemental sulfur is obtained from the sulfur solution by evaporation and the ammonium sulfide is regenerated by Dissolve the exhaust gases in water. 12. The method according to claim 11, characterized in that the Evaporation carried out at a temperature of at least 95 C. will. 13. The method according to claim 4, characterized in that sulfur is volatilized at temperatures between 300 C and 600 C. 14. The method according to claim 13, characterized in that the Sulfur volatilizes at temperatures between about 400 C and 500 C. will. 15. Varfahren according to claim 4 or 13 or 14, characterized in that that sulfur is volatilized under a partial vacuum. 16. The method according to any one of claims 4 or 13 to 15, characterized characterized by heating sulfur for up to 15 minutes is volatilized. 17. A method according to any preceding claim characterized in that the residue from step (a) is milled to about 95 % particle size less than about 0.044 mm (-325 mesh) to expose entrapped copper sulfide ore prior to being entrained Iron (III) chloride is leached in stage (b). 030604/0029 51. The method of claim 44, wherein the sulfur by Heating for up to 15 minutes will volatilize. 52. The improved method of claim 40 wherein in step (d) the residue is milled to about 95 % particle size less than about 0.044 mm (-325 mesh) to expose the entrapped copper sulfide ore before it becomes iron - (ill) chloride is leached. 030604/0029