CA1073681A - Recovery of precious metals from metal sulphides - Google Patents
Recovery of precious metals from metal sulphidesInfo
- Publication number
- CA1073681A CA1073681A CA246,274A CA246274A CA1073681A CA 1073681 A CA1073681 A CA 1073681A CA 246274 A CA246274 A CA 246274A CA 1073681 A CA1073681 A CA 1073681A
- Authority
- CA
- Canada
- Prior art keywords
- leach
- copper
- main
- gold
- process according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0078—Leaching or slurrying with ammoniacal solutions, e.g. ammonium hydroxide
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
ABSTRACT OF THE DISCLOSURE
Gold, as well as copper, is recovered from copper bearing sulphidic material containing gold. The copper bear-ing sulphidic material is subjected to a main leach to provide a copper containing main leach liquor and a main residue. A
secondary leach with ammonium thiosulphate solution is carried out on the copper bearing sulphidic material before the main leach, or on the residue from the main leach, to provide a gold containing secondary leach liquor and a secondary residue.
Copper and gold are recovered from the respective leach liquors.
Silver may also be recovered in addition to the gold.
Gold, as well as copper, is recovered from copper bearing sulphidic material containing gold. The copper bear-ing sulphidic material is subjected to a main leach to provide a copper containing main leach liquor and a main residue. A
secondary leach with ammonium thiosulphate solution is carried out on the copper bearing sulphidic material before the main leach, or on the residue from the main leach, to provide a gold containing secondary leach liquor and a secondary residue.
Copper and gold are recovered from the respective leach liquors.
Silver may also be recovered in addition to the gold.
Description
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This invention relates to the recovery of gold, and possibly also silver, as well as copper, from copper bearing sulphidic material which also contains such metals. Such mater-ial may, for example, be chalcopyrite.
It ha~ been proposed to recover copper from copper ; bearing sulphid;c material such as chalcopyrite material by means of a hydrometallur~ical process in which the ore is leached under oxidizing conditions to provide a substantially iron-free copper-containing leach solution, from which the copper is recovered. One such process is described in United States patent No. 2,822,263.
Copper bearing sulphidic materials, such as chalco-pyrite, frequently contain small amounts of precious metals such as gold and silver and, ln view of the present day value of these metals, it would be commercially advantageous if they too could be recovered. Although the problem of recovering precious metals, as well as a main element such as copper, has received much attention in the past, much of the work in this connection has been concerned, so far as commercial operations are concerned, ~ 20 with the recovery of precious metals in con~unction with pyro-i~ metallurgical processes for the recovery o~ the main element. So far as applicant is aware, little work has been carried out to provide commercially feasible methods of recovering precious metals in conjunction with hydrometallurgical processes for ex-traction of a main element sucll as copper from copper bearing ; sulphidic materials.
In a commercial operation for the recovery of precious metals as well as a main element, it is necessary for successful commercial operation that the method of recovery of the precious 30 metals be compatible with the hydrometallurgical process for recovery of the main element.
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Generally speaking, for commercial operations, the teaching of the prior art for the recovery of precious metals in these circumstances has been by cyanidation. However, such a method would not be commercially practical for use in conjunc-tion with the hydrometallurgical process for the recovery of copper referred to above, since a number of problems arise if . . .
cyanidation is used with copper bearing sulphidic materials.
In addition, of course, the use of cyanide is not desirable . . .
;~ because of its toxicity. Sodium sulphite and thiourea have been proposed as possible al*ernatîves, but have not yet been shown to be commercially attractive.
According to the present invention, it has been found , .. .
that ammonium thiosulphate ~an be used in a secondary leach P;~ for the recovery of gold, and possibly also silver, in conjunc-tion with hydrometallurgical processes of the kind mentioned above for the recovery of copper from copper bearing sulphidic materials. With the present invention, not only is the pre-,,~ , `, cious metal recovery treatment compatible with the hydromet-al-lurgical process for the recovery of copper, but the precious , .. .
; 20 metal recovery treatment can be carried out either before or ~, after the copper recovery leach, with minimum loss of thio-:' . ' ,~
~ sulphate, and with the precious metals being leached out into a . ,;
solution from which their recovery is commercially feasible.
Minimal loss of ammonium thiosulphate has, of course, economic ~' importance in a commercial operation, as also has the ease of extraction of gold, and possibly also silver, from the thio-i ~ sulphate leach solution. Additionally, from a con~ercial ."
~ point of view, it has also been found that satisfactory re-': I' ' ' sults can be produced without any initial roasting of the :.
; 30 copper bearing sulphidic material, thereby savin~ the con-~ siderable cost of such a step.
:
This invention relates to the recovery of gold, and possibly also silver, as well as copper, from copper bearing sulphidic material which also contains such metals. Such mater-ial may, for example, be chalcopyrite.
It ha~ been proposed to recover copper from copper ; bearing sulphid;c material such as chalcopyrite material by means of a hydrometallur~ical process in which the ore is leached under oxidizing conditions to provide a substantially iron-free copper-containing leach solution, from which the copper is recovered. One such process is described in United States patent No. 2,822,263.
Copper bearing sulphidic materials, such as chalco-pyrite, frequently contain small amounts of precious metals such as gold and silver and, ln view of the present day value of these metals, it would be commercially advantageous if they too could be recovered. Although the problem of recovering precious metals, as well as a main element such as copper, has received much attention in the past, much of the work in this connection has been concerned, so far as commercial operations are concerned, ~ 20 with the recovery of precious metals in con~unction with pyro-i~ metallurgical processes for the recovery o~ the main element. So far as applicant is aware, little work has been carried out to provide commercially feasible methods of recovering precious metals in conjunction with hydrometallurgical processes for ex-traction of a main element sucll as copper from copper bearing ; sulphidic materials.
In a commercial operation for the recovery of precious metals as well as a main element, it is necessary for successful commercial operation that the method of recovery of the precious 30 metals be compatible with the hydrometallurgical process for recovery of the main element.
,:" .
'' .. - 1 -" .
.,~ .
Generally speaking, for commercial operations, the teaching of the prior art for the recovery of precious metals in these circumstances has been by cyanidation. However, such a method would not be commercially practical for use in conjunc-tion with the hydrometallurgical process for the recovery of copper referred to above, since a number of problems arise if . . .
cyanidation is used with copper bearing sulphidic materials.
In addition, of course, the use of cyanide is not desirable . . .
;~ because of its toxicity. Sodium sulphite and thiourea have been proposed as possible al*ernatîves, but have not yet been shown to be commercially attractive.
According to the present invention, it has been found , .. .
that ammonium thiosulphate ~an be used in a secondary leach P;~ for the recovery of gold, and possibly also silver, in conjunc-tion with hydrometallurgical processes of the kind mentioned above for the recovery of copper from copper bearing sulphidic materials. With the present invention, not only is the pre-,,~ , `, cious metal recovery treatment compatible with the hydromet-al-lurgical process for the recovery of copper, but the precious , .. .
; 20 metal recovery treatment can be carried out either before or ~, after the copper recovery leach, with minimum loss of thio-:' . ' ,~
~ sulphate, and with the precious metals being leached out into a . ,;
solution from which their recovery is commercially feasible.
Minimal loss of ammonium thiosulphate has, of course, economic ~' importance in a commercial operation, as also has the ease of extraction of gold, and possibly also silver, from the thio-i ~ sulphate leach solution. Additionally, from a con~ercial ."
~ point of view, it has also been found that satisfactory re-': I' ' ' sults can be produced without any initial roasting of the :.
; 30 copper bearing sulphidic material, thereby savin~ the con-~ siderable cost of such a step.
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The main leach for the recovery of copper may be carried out with an ammonium salt containing ammoniacal aqueous leach medium, preferably at a temperature above 25C. and at a pressure above atmospheric pressure with a partial pressure of oxygen of at least 5 pounds per square inch gauge (p.s.i.g.).
The ammonium salt may be ammonium sulphate~ Alternatively, the main leach may be a so-called super leach carried out in water or dilute acid at relatively high temperatures and oxygen par-tial pressures, for example, temperatures in the range of 160C.
to 230C. and oxygen partial pressures in the range of 50 p.s.i.g.
to 200 p.s.i.g. In both types of main leach, the major portion of the sulphide sulphur is converted to sulphate form.
:.
Where the thiosulphate leach is carried out after ` a main leach of this super leach kind, the main residue is pre-ferably conditioned with a strong base such as sodium hydroxide, calcium hydroxide or ammonium hydroxide befora the thiosulphate , ~! leach.
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;i It may be preferred to treat the main leach residue .
rather than an initial concentrate for the recovery of precious !: 20 metals, becauæe a smaller volume of material is involved. Thus, . ~
; as far as the cost of equipment is concerned, it is more econo-mical to treat the main leach residue rather than the concentrate.
Although gold recoveries are substantiallY the same whether the initial concentrate or the main leach residue is subjected to the thiosulphate leach, it has been found that , silver recovery is frequently less from a thiosulphate leach of the concentrate than from a thiosulphate leach of the main leach ,~ residue, unless a concentrate is subjected to a prior oxida-30tion step. On the other hand, however, thiosulphate leaching of the concentrate rather than the main leach residue may be preferred because liquid/solids separation after thiosulphate i . :
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The main leach for the recovery of copper may be carried out with an ammonium salt containing ammoniacal aqueous leach medium, preferably at a temperature above 25C. and at a pressure above atmospheric pressure with a partial pressure of oxygen of at least 5 pounds per square inch gauge (p.s.i.g.).
The ammonium salt may be ammonium sulphate~ Alternatively, the main leach may be a so-called super leach carried out in water or dilute acid at relatively high temperatures and oxygen par-tial pressures, for example, temperatures in the range of 160C.
to 230C. and oxygen partial pressures in the range of 50 p.s.i.g.
to 200 p.s.i.g. In both types of main leach, the major portion of the sulphide sulphur is converted to sulphate form.
:.
Where the thiosulphate leach is carried out after ` a main leach of this super leach kind, the main residue is pre-ferably conditioned with a strong base such as sodium hydroxide, calcium hydroxide or ammonium hydroxide befora the thiosulphate , ~! leach.
;i .
;i It may be preferred to treat the main leach residue .
rather than an initial concentrate for the recovery of precious !: 20 metals, becauæe a smaller volume of material is involved. Thus, . ~
; as far as the cost of equipment is concerned, it is more econo-mical to treat the main leach residue rather than the concentrate.
Although gold recoveries are substantiallY the same whether the initial concentrate or the main leach residue is subjected to the thiosulphate leach, it has been found that , silver recovery is frequently less from a thiosulphate leach of the concentrate than from a thiosulphate leach of the main leach ,~ residue, unless a concentrate is subjected to a prior oxida-30tion step. On the other hand, however, thiosulphate leaching of the concentrate rather than the main leach residue may be preferred because liquid/solids separation after thiosulphate i . :
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leaching of the concentrate may be easier than liquid/solids separation after thiosulphate leaching of the main le~ch resi-due Which alternative is preferred in any particular case, I
.. , I
~` therefore, depends upon the various factors mentioned above.
. Initially, the concentrate or the main leach residue is slurried in ammonium thiosulphate solution. It should be .~i mentioned here that, where the concentrate is being treated, it ~"~ should only be lightly ground so ~s merely to break up any agglomera*ions. It ha~ been found that if the concentrate is 1- ;~ 10 ground to too fine a state, the finer ground particles may promote the precipitation of some of the soluble copper as a sulphide which may, in turn ? cause precipitation of solubilized ~ gold Preferably, the concentrate particle size should be in !,.' . the range of 60% minus 200 mesh to 95~ minus 325 mesh.
It has also been found that, for efficient extraction, there should be a significant amount of cupric ions, Cu2 , pre-sent during the ammonium thiosulphate leach so that the cupric ammine ion ~Cu~NH3)42 ) is formed. Such a concentration of ~` cupric ions may be provided by adding cupric ions or by produc-~; 20 ing them in situ 9 as will appear later. So far as treatment of . . .
the main leach residue is concerned, not all the copper will ! .
il- have been removed in the main recovery leach and, hence, some "
will be present in the main leach residue. Generally speaking, cupric ions should be added to provide a cupric ion concentra- -tion in the range of from 1 to 10 g.p.l. and preferably from 2 to 4 g.p~l.
The concentration of ammonium thiosulphate in the ~; slurry should be in the range of from 15 to 150 g.p.l. and prefer-.
~ ably from 60 to 120 g.p.l. Since precipitation of solub~e , . .
copper, along with some of the gold and silver,may occur after a significant percentage of the gold has dissolved, the time :.. -,...
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., ~ 3~of the leach should not be unduly prolonged. Better results, so far as gold extraction is eoncerned, may be obtained after leaching for one hour, for example, than after leaching for longer periods.
The ammonia content of the thiosulphate leach solu-tion should preferably be controlled so that there is a signi-ficant amount of free ammonia in th~ leach solution, wlth the free ammonia to soluble metals molar ratio being at least 4:1, and preferab}y at least 8:1.
So far as leaching temperatures are concerned, the temperature should be in the range from 20GC. to 65C., prefer-.~., ; ably between 25~C. and 50C. At lower temperatures, the rate of extraction is undesirably slow, wh;le at higher temperatures, an undesirable amount of copper may be precipitated as a sul-: phide, due to the decomposition of thiosulphate, with conse-;~ quent reduction of gold extraction.
Further, it has been found that the presence of oxygen or other suitable oxidant assists the thiosulphate leaching pro-; cess, although it is necessary that the conditions do not favour . ~ . .
the degradation of the thiosulphate by oxidation. There should be sufficient oxygen to keep the copper in solution with at ; least some of tha copper as cupric ions, with minimum oxidation of the thiosulphate. The use of air as oxidant, even in the absence of added copper, improves the gold extraction while the addition of cupric ions further improves the results. It appears that with air sparging, with no added cupric ions, sueh ions ..
s; are formed in situ.
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The thiosulphate leach may be carried out substan-tially at atmospheric pressure in the presence of free oxygen ~` or in an inert atmosphere such as a nitrogen atmosphere. Pres-sures slightly above atmospheric may also be useful.
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Insofar as the recovery of precious metals from the ~; thiosulphate leach liquor is concerned, various methods may be ` used. However, it has been found that~ with the process of the present invention, cementation with zinc dust provides a com-mercially useful and effective method of precipitating thP pre ; cious metals from solution. Preferably, cupric ions in the solu-~. .
; tion are first reduced to cuprous ions so as to decrease the amount of zinc dust required. Such reduction can be carried out with sulphur dioxide.
Embodiments of the present invention will now be described, by way of example, with reference to the accompany-;~ ing drawings, in which:
Figure 1 is a flow diagram of a hydrometallurgical process for the extraction of copper from .".;
`;~ chalcopyrite concentrate in conjunction with, according to one embodiment of the invention, . .
~he recovery of gold and silver from the main leach residue;
Figure 2 is a flow diagram showing a preferred method of extraction of gold and silver from the thiosulphate leach liquor obtained in the pro-cess shown in Figure l; and Figure 3 is a flow diagram showing the extraction o~
precious metals, in accordance w;th a second '`` embodiment of the invention, from chalcopyrite concentrate.
- Referring first to Fi~ure 1 of the accompanying draw-ings, chalcopyrite concentrate is leached in a main leaching step 10 with ammonium sulphate containing ammoniacal aqueous leach ., .
` 30 medium being carried out under oxidizing conditions. The con-centrate may typically contain, for example, 25% copper, 29~
iron, 4% zinc, 33% sulphur, 0.175 ounces per ton gold and 4.6 . .
~ ounces per ton silver. One such process is described in the . ,:
... .
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previously mentioned United States patent No. 2,822,263.
As described in this United States patent, the main leach is preferably carried out at a temperature above 25C.
and at a pressure above atmospheric pressure with a partial . . .
~; pressurè of oxygen above 5 pounds per square inch gauge.
:,.
After the main leach, the leach end slurry is passed . to a liquid-solids separation step 12, utilizing a thickener~
~; where overflow is subsequently processed for copper recovery as described in United States patent No. 2,822,263 mentioned above. The underflow is then fil~ered in a filtering step 14, with the filtrate also being passed to the copper extraction step~ The resultant residue then proceeds to a repulp step 16 where it is repulped with a leach solution and a wash solution, ; as will be described in more detail later.
~ The resultant slurry then passes to a thiosulphate - (or secondary) leaching step 18. The thiosulphate leach is carried out in a vessel in which the slurry is well agitated, ,.,.~;, and is carried out under atmospheric conditions, preferably in the presence of oxygen or air, or under an inert atmosphere such as nitrogen. Ammonia is also supplied to the thiosulphate leach step 18.
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~ After the thiosulphate leach, the leach end slurry ... .
- proceeds to a liquid-solids separation step 20 from which the ~; thiosulphate leach liquor passes to gold and silver recoverytreatment, as will be described later with referenee to Figure 2.
; The residue ~rom the liquid-solids separation step 20 passes to a washing step 22 where this secondary residue is washed and repulped with ammonia, ammonium sulphate and water. The wash liquid is then recirculated back to the repulp stage 16, ` 30 and the washed leach residue is discarded.
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It was previously mentioned that the repulp sta~e 16 is also provided with lea~h solution. Initially, ammonium sul-,'i ``:
phide is prepared as indicated in step 24 from water, ammonia and hydrogen sulphide, and the resultant ammonium sulphide is . . .
passed to an ammonium thiosulphate production step 26 to which ~; sulphur dioxide is supplied. The ammonium thiosulphate then , passes to a leach solution preparation step 28 which also re-ceives filtrate from the gold and silver recovery treatment . which will be described later with reference to Figure 2. The ,...
,'~.`!` ~ 10 resultant leach solution is then passed to the repulp step 16.
`; After the original thisulphate requirements of the system have ., been met, only make-up thiosulphate will be prepared in step 26, since most of the thiosulphate used in the secondary leach is recovered and recirculated~
The cupric ammine requirements of the thiosulphate , ~
leach are generally met by a small quantity of soluble copper ~` entrained as main leach liquor entering the thiosulphate leach circuit with the main leach residue. If additional cupric ammine ions are required, a small portion of the main leach ~,` 20 liquor may be diverted to the repulp step 16 or the secondary i; leach 18. Preferably, the thiosulphate leach is carried out in . ,, , ~
~ such a manner that the thiosulphate leach product liquor will con-~ . .
tain at least a portion, preferably a major portion, o~ the soluble copper in the reduced cuprous state.
Referring now to Figure 2, the thiosulphate leach liquor from the liquid separation step 20 of Figure 1 is passed .~:
to a spar~ing step 30, where the liquor is sparged with sulphur dioxide so as to reduce sub~tan~ially all the remaining cupric ions present to cuprous ions. The resultant liquor then passes ::, to a cementation step 32 where zinc dust is added so as to cause .. ..
precipitation of gold and silver as well as at least a portion of the copper.
,' :' 3~8~
The resultant mixture is filtered in a filtration step 34, and the filtrate passes to a strip step 36 where the ...
zinc and copper are precipitated as a mixed zinc-copper sulphide by hydrogen sulphide. This mixture is filtered in a filtration step 38 with consequent recovery of the zinc and copper sul-phides, which may be sent to the main leach. The filtrate from the filtration step 38 is then passed to the leach solution prepara-tion step 2~ of Figure 1. Residual or excess hydro~en ;~ sulphide (present as ammonium sulphide) in the filtrate af~er the bulk sulphide removal may be reacted with S02 as in step 26 to prepare make-up thiosulphate prior to step 28.
The secondary residue or cement product ,from the filtration step 34, which residue contains the gold and silver, as well as zinc, copper and sulphur, passes to repulp step 40 where it is repulped with water ànd acid. The resulting slurry is treated in an acid leach step 42 under oxidizing conditions caused by the addition of a;r. The conditions of this acid '~ leach are such that the major portion of copper and zinc are leached into solution with the gold and silver remaining in ,~ 20 the residue. The resultant product is then filtered in a fil-tration step 44, with the filtrate being recycled to the copper extraction step along with the leach liquor from the original main leach separa-tion step 12. The resultant residue from the filtration step 44 i~3 a gold/silver concentrate suitable for ' fur-ther refining by conventional commercial methods.
As an alternative to the acid leach step 42, the zinc and copper may be removed in a mildly oxidizing leach, for example in ammoniacal ammonium sulphate or in a portion of the cupric ammine-containing liquor of the main leach.
Figure 3 shows another embodiment of thé invention in which, instead of the main leach residue being treated for _ 9 _ ~3~
recovery of precious metals as in the emb~diment described with reference to Figures 1 and 2, the chalcopyrite concentrate i8 treated for the recovery of precious metals before the main leaching step for extraction of copper.
The chalcopyrite con~entrate, preferably after a light grind to break up major lumps and reduce s;ze to about 60% minus 325 mesh, is repulped in a repulping st~p 52 with ammonium thiosulphate solution and recycled ammonia leach liquor containing cupric ammine ions.
The resultant slurry is then leached in a secondary leach step 53, the leach being earried out in a suitable vesse~ -with adequate agitation and under atmospheric conditions with either an air or oxygen sparge or under nitrogen.
The leach end slurry then passes to a liquid-solids separation step S4, utilizing a thickener, with the underflow therefrom being filtered in a filtration step 56. The secondary .
residue from the filtration step 56, comprising relatively un-altered concentrate, is then passed to the main leach for the recov~ry of copper.
The overflow from the liquid-solids separation step 54 and the filtrate from the filtration step 56 are combined and then treated in a sparging step 58 with a sulphur dioxide sparge. The sparge and subsequent treatment are similar to those described in connection with Figure 2. Th~ sparged liquor passes to a cementation step 60 where cementation is earried out with zinc dust, and the product is fi1tered in a filtration step 62. The filtrate therefrom is treated with ~ydrogen sulphide in a zinc and copper stripping step 64 which produces a mixed sulphide and this sulphide is separated from the filtrate in a filtration step 66. The filtrate is then used in an ammonium thiosulphate preparation step (not shown) from which ammonium thiosulphate is supplied to the repulp step 52.
10 ~3 i~
The residue from the filtration step 62 is repulped in a repulping step 68 with water and acid~ and the resulting mixture passed to an acid leach step 709 where leaching ;s carried out under oxidizing conditions so as to leach out the major portion of copper and zinc, with silver and ~old remaining undissolved. The silver and gold are separated from the filtrate in a filtration step 72, and the filtrate, which contains copper and zinc, is added to the residue from the filtration step 56 and passed to the main leach for the extrac-tion of copper. The residue from the filtration step 72 is,as in the previous embodiment, a gold/s;lver concentrate suit-able for refining by conventional commercial methods. -Various specific examples of the invention will now be described.
A chalcopyrite concentrate was leached with an ammonium sulphate containing ammoniacal a~ueous leach medium.
The concentrate contained 25.3~ Cu, 28.7% Fe, 3.26% Zn, 33.2~ S, 0.18a oz/ton Au and 4.58 oz/ton ag, with the copper, iron and sulphur being primarily present as the oompounds CuFeS2 and FeS2. The leach was carried out with 240 g.p.l.
concentrate at 82C. under an initial oxygen overpressure of 20 p.s.i.g. with the leach medium containing înitially 100 g.p.l.
ammonium sulphate and excess free ammonia. The leach was aon-tinued for 8 hours and 98.1% Cu and 84.8~ 5 were extracted. The residue was filtered, repulped first in NH3/(NH4)2S04 solution, then in water and dried.
The residue from the main leach described above was then prepared for an ammonium thiosulphate leach for the extrac- -tion of gold and silver. The slurry for the ammonium thiosul-phate leach contained 400 g.p.l. of the ammonia leach residue (which is equivalent to a maximum precious metals content of , 3~
i ., - . . . . . . .. ~
leaching of the concentrate may be easier than liquid/solids separation after thiosulphate leaching of the main le~ch resi-due Which alternative is preferred in any particular case, I
.. , I
~` therefore, depends upon the various factors mentioned above.
. Initially, the concentrate or the main leach residue is slurried in ammonium thiosulphate solution. It should be .~i mentioned here that, where the concentrate is being treated, it ~"~ should only be lightly ground so ~s merely to break up any agglomera*ions. It ha~ been found that if the concentrate is 1- ;~ 10 ground to too fine a state, the finer ground particles may promote the precipitation of some of the soluble copper as a sulphide which may, in turn ? cause precipitation of solubilized ~ gold Preferably, the concentrate particle size should be in !,.' . the range of 60% minus 200 mesh to 95~ minus 325 mesh.
It has also been found that, for efficient extraction, there should be a significant amount of cupric ions, Cu2 , pre-sent during the ammonium thiosulphate leach so that the cupric ammine ion ~Cu~NH3)42 ) is formed. Such a concentration of ~` cupric ions may be provided by adding cupric ions or by produc-~; 20 ing them in situ 9 as will appear later. So far as treatment of . . .
the main leach residue is concerned, not all the copper will ! .
il- have been removed in the main recovery leach and, hence, some "
will be present in the main leach residue. Generally speaking, cupric ions should be added to provide a cupric ion concentra- -tion in the range of from 1 to 10 g.p.l. and preferably from 2 to 4 g.p~l.
The concentration of ammonium thiosulphate in the ~; slurry should be in the range of from 15 to 150 g.p.l. and prefer-.
~ ably from 60 to 120 g.p.l. Since precipitation of solub~e , . .
copper, along with some of the gold and silver,may occur after a significant percentage of the gold has dissolved, the time :.. -,...
, '.
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:, . -:~`
; :
...
., ~ 3~of the leach should not be unduly prolonged. Better results, so far as gold extraction is eoncerned, may be obtained after leaching for one hour, for example, than after leaching for longer periods.
The ammonia content of the thiosulphate leach solu-tion should preferably be controlled so that there is a signi-ficant amount of free ammonia in th~ leach solution, wlth the free ammonia to soluble metals molar ratio being at least 4:1, and preferab}y at least 8:1.
So far as leaching temperatures are concerned, the temperature should be in the range from 20GC. to 65C., prefer-.~., ; ably between 25~C. and 50C. At lower temperatures, the rate of extraction is undesirably slow, wh;le at higher temperatures, an undesirable amount of copper may be precipitated as a sul-: phide, due to the decomposition of thiosulphate, with conse-;~ quent reduction of gold extraction.
Further, it has been found that the presence of oxygen or other suitable oxidant assists the thiosulphate leaching pro-; cess, although it is necessary that the conditions do not favour . ~ . .
the degradation of the thiosulphate by oxidation. There should be sufficient oxygen to keep the copper in solution with at ; least some of tha copper as cupric ions, with minimum oxidation of the thiosulphate. The use of air as oxidant, even in the absence of added copper, improves the gold extraction while the addition of cupric ions further improves the results. It appears that with air sparging, with no added cupric ions, sueh ions ..
s; are formed in situ.
,;; ' .
The thiosulphate leach may be carried out substan-tially at atmospheric pressure in the presence of free oxygen ~` or in an inert atmosphere such as a nitrogen atmosphere. Pres-sures slightly above atmospheric may also be useful.
, ,.: .
,, .
:, '.`''.
:.1 . . ..
3~8~ `
Insofar as the recovery of precious metals from the ~; thiosulphate leach liquor is concerned, various methods may be ` used. However, it has been found that~ with the process of the present invention, cementation with zinc dust provides a com-mercially useful and effective method of precipitating thP pre ; cious metals from solution. Preferably, cupric ions in the solu-~. .
; tion are first reduced to cuprous ions so as to decrease the amount of zinc dust required. Such reduction can be carried out with sulphur dioxide.
Embodiments of the present invention will now be described, by way of example, with reference to the accompany-;~ ing drawings, in which:
Figure 1 is a flow diagram of a hydrometallurgical process for the extraction of copper from .".;
`;~ chalcopyrite concentrate in conjunction with, according to one embodiment of the invention, . .
~he recovery of gold and silver from the main leach residue;
Figure 2 is a flow diagram showing a preferred method of extraction of gold and silver from the thiosulphate leach liquor obtained in the pro-cess shown in Figure l; and Figure 3 is a flow diagram showing the extraction o~
precious metals, in accordance w;th a second '`` embodiment of the invention, from chalcopyrite concentrate.
- Referring first to Fi~ure 1 of the accompanying draw-ings, chalcopyrite concentrate is leached in a main leaching step 10 with ammonium sulphate containing ammoniacal aqueous leach ., .
` 30 medium being carried out under oxidizing conditions. The con-centrate may typically contain, for example, 25% copper, 29~
iron, 4% zinc, 33% sulphur, 0.175 ounces per ton gold and 4.6 . .
~ ounces per ton silver. One such process is described in the . ,:
... .
: - 6 -~3~
:
previously mentioned United States patent No. 2,822,263.
As described in this United States patent, the main leach is preferably carried out at a temperature above 25C.
and at a pressure above atmospheric pressure with a partial . . .
~; pressurè of oxygen above 5 pounds per square inch gauge.
:,.
After the main leach, the leach end slurry is passed . to a liquid-solids separation step 12, utilizing a thickener~
~; where overflow is subsequently processed for copper recovery as described in United States patent No. 2,822,263 mentioned above. The underflow is then fil~ered in a filtering step 14, with the filtrate also being passed to the copper extraction step~ The resultant residue then proceeds to a repulp step 16 where it is repulped with a leach solution and a wash solution, ; as will be described in more detail later.
~ The resultant slurry then passes to a thiosulphate - (or secondary) leaching step 18. The thiosulphate leach is carried out in a vessel in which the slurry is well agitated, ,.,.~;, and is carried out under atmospheric conditions, preferably in the presence of oxygen or air, or under an inert atmosphere such as nitrogen. Ammonia is also supplied to the thiosulphate leach step 18.
"~
~ After the thiosulphate leach, the leach end slurry ... .
- proceeds to a liquid-solids separation step 20 from which the ~; thiosulphate leach liquor passes to gold and silver recoverytreatment, as will be described later with referenee to Figure 2.
; The residue ~rom the liquid-solids separation step 20 passes to a washing step 22 where this secondary residue is washed and repulped with ammonia, ammonium sulphate and water. The wash liquid is then recirculated back to the repulp stage 16, ` 30 and the washed leach residue is discarded.
, ! .
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.
, ' ' ,.,'". . ' .:
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.... , --` .
It was previously mentioned that the repulp sta~e 16 is also provided with lea~h solution. Initially, ammonium sul-,'i ``:
phide is prepared as indicated in step 24 from water, ammonia and hydrogen sulphide, and the resultant ammonium sulphide is . . .
passed to an ammonium thiosulphate production step 26 to which ~; sulphur dioxide is supplied. The ammonium thiosulphate then , passes to a leach solution preparation step 28 which also re-ceives filtrate from the gold and silver recovery treatment . which will be described later with reference to Figure 2. The ,...
,'~.`!` ~ 10 resultant leach solution is then passed to the repulp step 16.
`; After the original thisulphate requirements of the system have ., been met, only make-up thiosulphate will be prepared in step 26, since most of the thiosulphate used in the secondary leach is recovered and recirculated~
The cupric ammine requirements of the thiosulphate , ~
leach are generally met by a small quantity of soluble copper ~` entrained as main leach liquor entering the thiosulphate leach circuit with the main leach residue. If additional cupric ammine ions are required, a small portion of the main leach ~,` 20 liquor may be diverted to the repulp step 16 or the secondary i; leach 18. Preferably, the thiosulphate leach is carried out in . ,, , ~
~ such a manner that the thiosulphate leach product liquor will con-~ . .
tain at least a portion, preferably a major portion, o~ the soluble copper in the reduced cuprous state.
Referring now to Figure 2, the thiosulphate leach liquor from the liquid separation step 20 of Figure 1 is passed .~:
to a spar~ing step 30, where the liquor is sparged with sulphur dioxide so as to reduce sub~tan~ially all the remaining cupric ions present to cuprous ions. The resultant liquor then passes ::, to a cementation step 32 where zinc dust is added so as to cause .. ..
precipitation of gold and silver as well as at least a portion of the copper.
,' :' 3~8~
The resultant mixture is filtered in a filtration step 34, and the filtrate passes to a strip step 36 where the ...
zinc and copper are precipitated as a mixed zinc-copper sulphide by hydrogen sulphide. This mixture is filtered in a filtration step 38 with consequent recovery of the zinc and copper sul-phides, which may be sent to the main leach. The filtrate from the filtration step 38 is then passed to the leach solution prepara-tion step 2~ of Figure 1. Residual or excess hydro~en ;~ sulphide (present as ammonium sulphide) in the filtrate af~er the bulk sulphide removal may be reacted with S02 as in step 26 to prepare make-up thiosulphate prior to step 28.
The secondary residue or cement product ,from the filtration step 34, which residue contains the gold and silver, as well as zinc, copper and sulphur, passes to repulp step 40 where it is repulped with water ànd acid. The resulting slurry is treated in an acid leach step 42 under oxidizing conditions caused by the addition of a;r. The conditions of this acid '~ leach are such that the major portion of copper and zinc are leached into solution with the gold and silver remaining in ,~ 20 the residue. The resultant product is then filtered in a fil-tration step 44, with the filtrate being recycled to the copper extraction step along with the leach liquor from the original main leach separa-tion step 12. The resultant residue from the filtration step 44 i~3 a gold/silver concentrate suitable for ' fur-ther refining by conventional commercial methods.
As an alternative to the acid leach step 42, the zinc and copper may be removed in a mildly oxidizing leach, for example in ammoniacal ammonium sulphate or in a portion of the cupric ammine-containing liquor of the main leach.
Figure 3 shows another embodiment of thé invention in which, instead of the main leach residue being treated for _ 9 _ ~3~
recovery of precious metals as in the emb~diment described with reference to Figures 1 and 2, the chalcopyrite concentrate i8 treated for the recovery of precious metals before the main leaching step for extraction of copper.
The chalcopyrite con~entrate, preferably after a light grind to break up major lumps and reduce s;ze to about 60% minus 325 mesh, is repulped in a repulping st~p 52 with ammonium thiosulphate solution and recycled ammonia leach liquor containing cupric ammine ions.
The resultant slurry is then leached in a secondary leach step 53, the leach being earried out in a suitable vesse~ -with adequate agitation and under atmospheric conditions with either an air or oxygen sparge or under nitrogen.
The leach end slurry then passes to a liquid-solids separation step S4, utilizing a thickener, with the underflow therefrom being filtered in a filtration step 56. The secondary .
residue from the filtration step 56, comprising relatively un-altered concentrate, is then passed to the main leach for the recov~ry of copper.
The overflow from the liquid-solids separation step 54 and the filtrate from the filtration step 56 are combined and then treated in a sparging step 58 with a sulphur dioxide sparge. The sparge and subsequent treatment are similar to those described in connection with Figure 2. Th~ sparged liquor passes to a cementation step 60 where cementation is earried out with zinc dust, and the product is fi1tered in a filtration step 62. The filtrate therefrom is treated with ~ydrogen sulphide in a zinc and copper stripping step 64 which produces a mixed sulphide and this sulphide is separated from the filtrate in a filtration step 66. The filtrate is then used in an ammonium thiosulphate preparation step (not shown) from which ammonium thiosulphate is supplied to the repulp step 52.
10 ~3 i~
The residue from the filtration step 62 is repulped in a repulping step 68 with water and acid~ and the resulting mixture passed to an acid leach step 709 where leaching ;s carried out under oxidizing conditions so as to leach out the major portion of copper and zinc, with silver and ~old remaining undissolved. The silver and gold are separated from the filtrate in a filtration step 72, and the filtrate, which contains copper and zinc, is added to the residue from the filtration step 56 and passed to the main leach for the extrac-tion of copper. The residue from the filtration step 72 is,as in the previous embodiment, a gold/s;lver concentrate suit-able for refining by conventional commercial methods. -Various specific examples of the invention will now be described.
A chalcopyrite concentrate was leached with an ammonium sulphate containing ammoniacal a~ueous leach medium.
The concentrate contained 25.3~ Cu, 28.7% Fe, 3.26% Zn, 33.2~ S, 0.18a oz/ton Au and 4.58 oz/ton ag, with the copper, iron and sulphur being primarily present as the oompounds CuFeS2 and FeS2. The leach was carried out with 240 g.p.l.
concentrate at 82C. under an initial oxygen overpressure of 20 p.s.i.g. with the leach medium containing înitially 100 g.p.l.
ammonium sulphate and excess free ammonia. The leach was aon-tinued for 8 hours and 98.1% Cu and 84.8~ 5 were extracted. The residue was filtered, repulped first in NH3/(NH4)2S04 solution, then in water and dried.
The residue from the main leach described above was then prepared for an ammonium thiosulphate leach for the extrac- -tion of gold and silver. The slurry for the ammonium thiosul-phate leach contained 400 g.p.l. of the ammonia leach residue (which is equivalent to a maximum precious metals content of , 3~
4.17 mg/l Au and 107 mg/l Ag) and 100 g.p.l. ammonium thiosul-phate, with sufficient ammonia being added to bring the pH to between 9.5 and 10Ø
Two thiosulphate lea~hes were carried out, one with and one without added cupric ions. The leaches were carried out at 49C. with a nitrogen purge and strong agitation. The cupric ions in the first case were added in the form of leach liquor from the main leach, this liquor containing 55 g.p.l. Cu and 100 g.p.l. free N~3. Sufficient liquor ~100 ml~l) was added to give a level of from 5-6 g.p.l. cupric ions. Samples were taken after thiosulphate leach times of 2, 4 and 6 hours and the results are shown in Table I.
TAB~E I
Main Leach Residue Assays Extractions Liquor Added Time ~oz~T) ~%) (ml/l) (hr) Au Ag Au Ag Main leach residue - 0.304 7.83 0 ~.0 0.102 1.52 66.4 80.6 4.~ 0.086 1.36 71.2 82.6 `~ 6.0 0.062 1.20 79.6 84.7 .
100 2.0 n.a.* 0.89 n~a.* 88.6 4.0 0.020 1.04 93.4 86.7 6.0 0.017 0.97 g4.4 87.6 , * not analyzed.
The results show a dramatic improvement in the leach rate and extraction of gold in the presence of added cupric ions, namely from 71.2% to 93.4% at 4 hours and from 78.6% to 94.4% after 6 hours. Silver extractions were marginally im-proved by about 3_8% to 86-89%.
:~7 ~
It is interesting to note that appreciable extractions of g~ld and silver were obtained even in the absence of added cupric ions. It is believed that this is because sur~ace oxi-dation may have occurred during the drying of the residue and contributed in part to the improved extraotions by providing oxidant. The less favourable results obtained with a washed but undried residue are apparent from the following example.
In this case, two main leaches were carried out, one ;~ 10 at 82~C. with an unground concentrate t42.2% minus 325 mesh) and one at 93C. with a concentrate ground for 0.5 hours in a ... .
steel ball mill. The main leach of unground concentrate ex~
tracted 93.3% Cu, and the leach of ground concentrate extracted 98.6% Cu.
Prior to the thiosulphate leach, the residues were settled, thickened and filtered to approximately 50% solids, and then were either treated directly with thiosulphate (i.e.
unwashed) or were first well washed by repulping twice with 45/200 NH3t(NH~)2S04 solution and water but not dried. The thiosulphate leaches contained 130-140 g.p.l. solids (dry basis) in lOO g.p.l. thiosulphate and were carried out at 49C.
with strong agitation and a nitrogen purge.
Samples were taken initiall~ and after leach times of 1, 2 and 5 hours. The results are shown in Table II.
;' ' . :
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U ~; __ __ _ ..... _ . _ ___ ~4 ~ . 1 0 r~ ~ O~ tO V~ O C~ O
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~0 ~ ~ ~o~ O ~D ~-0 . ~ ~ ~ t~ ~ ~ ~ _~ C~ ~ ~ ~ ~ ~
O ~ ~ ~ t~ O r~O 0~0 n~ ~S ~ 't;OC~ O~O O c~Oo ooo ~` q~ -- -. - --- .
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t~ ~- ~ r` ~ ~ t~ euo~ ~J
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H ¦ _ . _ ~ ~ _ _ __ vl ___ ~sl _o '~ .0 0 ~ C o _ r~ ~ _ t~l ~ O ._ ~ ~ ~ ~ V~
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It i~ clear that much b~tter results were obtained with the unwashed residue containing appreciable soluble copper as entrained primary lea~h liquor. In these tes~s, the washed residues from the a~monium leach were ~ubjected to the thio-sulphate leach directly after washing. This is in contrà~t to the tests in Example 1 where the residue was dried after wash-ing, with improved results.
The thiosulphate leaching described in Example 1 was carried out directly on the chalcopyrite concentrate in a slurry containing 400 g.p.l. solids, i.e. before the main leach to extract copper, the concentrate having first been lightly ground to 63~ minus 40~ micron ~38% minus 20~. In addition, two leaches were carried out at ambient temperature (22C.) in sealed porcelain jars for several days and subjected to gentle agitation on rollers employed for ball milling. The results are shown in Table III.
TABLE III
. .
~hlo3ulph-te Leacl~ ~:onditlon0 Pr~d~ct~
_ _ _ _ _ F11 tr~ te Re 31d~1 e As s ays Extra c t i ons r~ each Lesch (gl13 tozlTon) ~X) Le~ch Vesiel Temp ~iquor Added T~rle pN _ _ ( G)(~nl/l) (hr) Cu A~ A8 Au A8 _ . . __ .. _ I . 0158 ~56 _ I .
. Baffled, well b9 O 2 9,5-10.0 o.lS6 4.24 12.0 7.4 ~8itated w~th 4 ~ 0.1174.39 37.8 4.2 overhead ~tirrer i 9.55 0.56 0.127 ~.15 32.4 9.4 100 29.5-10.0 0.021 4.28 88.6 6.6 I. .
, 4. 0.026 3.87 86.2 lS.S ~:
. 6 9.5 S.16 0.046 4.05 75.S 11.6 __ _ Sealed . 22 O 249.5-10.0 0,022 4.07 88.3 11.1 ~ar~ on roller8 _ _ 72 O. 147 O. 156 6 .16 63 .0 ~ 2 .0 100 2~9.5-10.0 0.033 4.bO 82.4 3.9 ..
b8 0.0/~7 6.2475.0 7.b _ _ . ~ 72 L 2.~6 L~ ~ ~.~5 l62.8 2.9 ~o~
The effect of the added cupric ions on the 49C. leach-ing of gold was even ~ore pronounced than in the case of the main leach residue of Example 1, sin~e the extractions were increased from 17-28% after 2-6 hours to almost 89% after two hours. Sil-ver extractions were marginally improved but were still very low at 11 -4%. It is therefore clear that ~he silver is much more tightly held in the concentrate.
It is interesting to note that the 6 hour solution sample of the "Cu-free" leach contained 0.56 g.p.l. Cu which was presumably derived from surface oxidation of the sulphides during grinding or storage. Thus, leaching of gold with no added cupric ions may have been primarily due to the presence of small amounts of soluble copper in the feed solids.
It will also be noted that the extended time, ambient temperature leaches provide some interesting results~ In the leach with 5.5 g.p.l. of added cupric ions, gold extractions decreased with time from 82.4% to 75.0% and 62.8~ after 24 hours, 48 hour~ and 72 hours respectively. Since the cupric ion level in the final solution had dro~ped to 2.76 g.p.l. this suggests that some of the solubilized gold had precipitated with the copper, and that optimum gold extraction had been obtained with-in the first 24 hours.
The ambient temperature leach in the absence of added cupric ions showed remarkably high initial gold extractions of 88.3~ and 83.0~ after 24 hours and ~8 hours respectively. It is possible that appreciable levels of soluble cupric ions derived from surface-oxidized concentrate were responsible. The 72 hour sample contained 0.147 g.p.l. cupric ions suggesting that some of the cupric ions and initially solubilized gold had precipitated lowering the gold extraction to 17~ at 72 hoursv (The 24 hour and 48 hour levels of cupric ions were not determined~ but subse-quent tests indicated the solubilization of at least 1.0 g.p.l.
Cu during the initial stages of leaching).
.. . .
. : . :
EXAMPLE 4 ~3)~
. Test~ were carried out to determine the effect of different ammonia thiosulphate concentrations in the leach.
The leach was carried out at 49C. with 5.74 ~.p.l. added cupric ions and a nitrogen purge. The concentrate referred to in Example 3 was used. The co~centration of ammonium thiosulphate was varied from 13-130 g.p.l. and the results are shown in Table IV.
TABLE IV
_ .. ..
Solut~on Assay~
~cminal Resid~e - A~
Ini t i al Time (g/l) : t~.)252~ (hr~ _ pH Assays Ex~n (g/l) Cu ~ C~ ST ~(S10~ 3 NH,F(~zlton) (X) _ _ 3 O 5.74 . 27.0 9.45 0.~88 __ O.S ~2.5 9.35 0.06~ 63.3 1.0 l8.5 9.10 0.050 73.4 2.0 . 12.5~ 9.~0 0.047 ~.0 : 4.0 3.67 -2.07 16.8 7.3013.5 9.1D 0.055 70~7 ~' 32.5 O 5.74 27.0 9.4 0.188 __ 0.5 23.0 9.2 . 0.036 8~.9 . 1.0 21.5 9.2 0.034 81.9 ~0 2.0 4.13 -1.61 24.~ 15.4 18.~ 9.1 0.044 76.6 .
,~ .
; 65 O 5~74 . 26.5 9.2 ~.188 __ 0.5 . 2~.2 9.15 0.034 81.9 . 1.0 ~0.0 9.1 0.020 89.4 ; .~. 2.0 4.g6 -0.7~ 39.3 30.1 16.5 ~.0 0.02~ 84~6 . _ _ _ _ _ : 130 O 4.30 25.5 9.60.188 __ . ~ 0.5 23.0 9.3 0.034 81.9 ; 1.~ lg.8 9.25 0.022 ~.3 2.0 5.13 +0.83 69.1 59.4 17.5 9.2 0.016 91.5 : .
* Make~up NHI~OH added, ~30 The results show that even a-t a thiosulphate level of only 13 g.p.l., a high gold extraction of almost 75% is achieved within 1 hour. Rowever? for optimum gold solubilization, the minimum conCentratiQn of ammonium thiosulphate required is some-where in the range of 65-130 g.p.l. At 65 g.p.l. the initial . gold extraction was high, namely~ 89% after 1 hour, but it appears ,: that copper precipitation took place after this and reduced the ,,;
I gold extractio~ to 84% after 2 hours. This is dPduced from the ; fact that cupric ion concentration had decreased from the init;al . ; .
- 17 _ -.
Two thiosulphate lea~hes were carried out, one with and one without added cupric ions. The leaches were carried out at 49C. with a nitrogen purge and strong agitation. The cupric ions in the first case were added in the form of leach liquor from the main leach, this liquor containing 55 g.p.l. Cu and 100 g.p.l. free N~3. Sufficient liquor ~100 ml~l) was added to give a level of from 5-6 g.p.l. cupric ions. Samples were taken after thiosulphate leach times of 2, 4 and 6 hours and the results are shown in Table I.
TAB~E I
Main Leach Residue Assays Extractions Liquor Added Time ~oz~T) ~%) (ml/l) (hr) Au Ag Au Ag Main leach residue - 0.304 7.83 0 ~.0 0.102 1.52 66.4 80.6 4.~ 0.086 1.36 71.2 82.6 `~ 6.0 0.062 1.20 79.6 84.7 .
100 2.0 n.a.* 0.89 n~a.* 88.6 4.0 0.020 1.04 93.4 86.7 6.0 0.017 0.97 g4.4 87.6 , * not analyzed.
The results show a dramatic improvement in the leach rate and extraction of gold in the presence of added cupric ions, namely from 71.2% to 93.4% at 4 hours and from 78.6% to 94.4% after 6 hours. Silver extractions were marginally im-proved by about 3_8% to 86-89%.
:~7 ~
It is interesting to note that appreciable extractions of g~ld and silver were obtained even in the absence of added cupric ions. It is believed that this is because sur~ace oxi-dation may have occurred during the drying of the residue and contributed in part to the improved extraotions by providing oxidant. The less favourable results obtained with a washed but undried residue are apparent from the following example.
In this case, two main leaches were carried out, one ;~ 10 at 82~C. with an unground concentrate t42.2% minus 325 mesh) and one at 93C. with a concentrate ground for 0.5 hours in a ... .
steel ball mill. The main leach of unground concentrate ex~
tracted 93.3% Cu, and the leach of ground concentrate extracted 98.6% Cu.
Prior to the thiosulphate leach, the residues were settled, thickened and filtered to approximately 50% solids, and then were either treated directly with thiosulphate (i.e.
unwashed) or were first well washed by repulping twice with 45/200 NH3t(NH~)2S04 solution and water but not dried. The thiosulphate leaches contained 130-140 g.p.l. solids (dry basis) in lOO g.p.l. thiosulphate and were carried out at 49C.
with strong agitation and a nitrogen purge.
Samples were taken initiall~ and after leach times of 1, 2 and 5 hours. The results are shown in Table II.
;' ' . :
: ' ' . ' ' ~36~
_ _ _ ~ ~D~tO _ ~ ` .~
~ _ .~ _ t~ .~ t,~ ~, 'o~ ~ ~ ~
U ~; __ __ _ ..... _ . _ ___ ~4 ~ . 1 0 r~ ~ O~ tO V~ O C~ O
_ ._ . ~ ~ ~ _ _ ~ ~ 0.0~
~0 ~ ~ ~o~ O ~D ~-0 . ~ ~ ~ t~ ~ ~ ~ _~ C~ ~ ~ ~ ~ ~
O ~ ~ ~ t~ O r~O 0~0 n~ ~S ~ 't;OC~ O~O O c~Oo ooo ~` q~ -- -. - --- .
'.' . .C ~ _ `D ~ __~ _~ ~` _ .~ ~ ~ r~ ~- o ~ o - ~ ~
t~ ~- ~ r` ~ ~ t~ euo~ ~J
-- - -~o - - - ---. ~ ~ r~ ~J ~ O .~
H ¦ _ . _ ~ ~ _ _ __ vl ___ ~sl _o '~ .0 0 ~ C o _ r~ ~ _ t~l ~ O ._ ~ ~ ~ ~ V~
.' . __ __ Iq __ i~ .
~ ' ~; ~ O!~ __ . O~ _ ___ C h ~ .
~, O __._ .. ' ~ ~S ~ ;:~ .
~' . _ . _ _ ~3~Q
It i~ clear that much b~tter results were obtained with the unwashed residue containing appreciable soluble copper as entrained primary lea~h liquor. In these tes~s, the washed residues from the a~monium leach were ~ubjected to the thio-sulphate leach directly after washing. This is in contrà~t to the tests in Example 1 where the residue was dried after wash-ing, with improved results.
The thiosulphate leaching described in Example 1 was carried out directly on the chalcopyrite concentrate in a slurry containing 400 g.p.l. solids, i.e. before the main leach to extract copper, the concentrate having first been lightly ground to 63~ minus 40~ micron ~38% minus 20~. In addition, two leaches were carried out at ambient temperature (22C.) in sealed porcelain jars for several days and subjected to gentle agitation on rollers employed for ball milling. The results are shown in Table III.
TABLE III
. .
~hlo3ulph-te Leacl~ ~:onditlon0 Pr~d~ct~
_ _ _ _ _ F11 tr~ te Re 31d~1 e As s ays Extra c t i ons r~ each Lesch (gl13 tozlTon) ~X) Le~ch Vesiel Temp ~iquor Added T~rle pN _ _ ( G)(~nl/l) (hr) Cu A~ A8 Au A8 _ . . __ .. _ I . 0158 ~56 _ I .
. Baffled, well b9 O 2 9,5-10.0 o.lS6 4.24 12.0 7.4 ~8itated w~th 4 ~ 0.1174.39 37.8 4.2 overhead ~tirrer i 9.55 0.56 0.127 ~.15 32.4 9.4 100 29.5-10.0 0.021 4.28 88.6 6.6 I. .
, 4. 0.026 3.87 86.2 lS.S ~:
. 6 9.5 S.16 0.046 4.05 75.S 11.6 __ _ Sealed . 22 O 249.5-10.0 0,022 4.07 88.3 11.1 ~ar~ on roller8 _ _ 72 O. 147 O. 156 6 .16 63 .0 ~ 2 .0 100 2~9.5-10.0 0.033 4.bO 82.4 3.9 ..
b8 0.0/~7 6.2475.0 7.b _ _ . ~ 72 L 2.~6 L~ ~ ~.~5 l62.8 2.9 ~o~
The effect of the added cupric ions on the 49C. leach-ing of gold was even ~ore pronounced than in the case of the main leach residue of Example 1, sin~e the extractions were increased from 17-28% after 2-6 hours to almost 89% after two hours. Sil-ver extractions were marginally improved but were still very low at 11 -4%. It is therefore clear that ~he silver is much more tightly held in the concentrate.
It is interesting to note that the 6 hour solution sample of the "Cu-free" leach contained 0.56 g.p.l. Cu which was presumably derived from surface oxidation of the sulphides during grinding or storage. Thus, leaching of gold with no added cupric ions may have been primarily due to the presence of small amounts of soluble copper in the feed solids.
It will also be noted that the extended time, ambient temperature leaches provide some interesting results~ In the leach with 5.5 g.p.l. of added cupric ions, gold extractions decreased with time from 82.4% to 75.0% and 62.8~ after 24 hours, 48 hour~ and 72 hours respectively. Since the cupric ion level in the final solution had dro~ped to 2.76 g.p.l. this suggests that some of the solubilized gold had precipitated with the copper, and that optimum gold extraction had been obtained with-in the first 24 hours.
The ambient temperature leach in the absence of added cupric ions showed remarkably high initial gold extractions of 88.3~ and 83.0~ after 24 hours and ~8 hours respectively. It is possible that appreciable levels of soluble cupric ions derived from surface-oxidized concentrate were responsible. The 72 hour sample contained 0.147 g.p.l. cupric ions suggesting that some of the cupric ions and initially solubilized gold had precipitated lowering the gold extraction to 17~ at 72 hoursv (The 24 hour and 48 hour levels of cupric ions were not determined~ but subse-quent tests indicated the solubilization of at least 1.0 g.p.l.
Cu during the initial stages of leaching).
.. . .
. : . :
EXAMPLE 4 ~3)~
. Test~ were carried out to determine the effect of different ammonia thiosulphate concentrations in the leach.
The leach was carried out at 49C. with 5.74 ~.p.l. added cupric ions and a nitrogen purge. The concentrate referred to in Example 3 was used. The co~centration of ammonium thiosulphate was varied from 13-130 g.p.l. and the results are shown in Table IV.
TABLE IV
_ .. ..
Solut~on Assay~
~cminal Resid~e - A~
Ini t i al Time (g/l) : t~.)252~ (hr~ _ pH Assays Ex~n (g/l) Cu ~ C~ ST ~(S10~ 3 NH,F(~zlton) (X) _ _ 3 O 5.74 . 27.0 9.45 0.~88 __ O.S ~2.5 9.35 0.06~ 63.3 1.0 l8.5 9.10 0.050 73.4 2.0 . 12.5~ 9.~0 0.047 ~.0 : 4.0 3.67 -2.07 16.8 7.3013.5 9.1D 0.055 70~7 ~' 32.5 O 5.74 27.0 9.4 0.188 __ 0.5 23.0 9.2 . 0.036 8~.9 . 1.0 21.5 9.2 0.034 81.9 ~0 2.0 4.13 -1.61 24.~ 15.4 18.~ 9.1 0.044 76.6 .
,~ .
; 65 O 5~74 . 26.5 9.2 ~.188 __ 0.5 . 2~.2 9.15 0.034 81.9 . 1.0 ~0.0 9.1 0.020 89.4 ; .~. 2.0 4.g6 -0.7~ 39.3 30.1 16.5 ~.0 0.02~ 84~6 . _ _ _ _ _ : 130 O 4.30 25.5 9.60.188 __ . ~ 0.5 23.0 9.3 0.034 81.9 ; 1.~ lg.8 9.25 0.022 ~.3 2.0 5.13 +0.83 69.1 59.4 17.5 9.2 0.016 91.5 : .
* Make~up NHI~OH added, ~30 The results show that even a-t a thiosulphate level of only 13 g.p.l., a high gold extraction of almost 75% is achieved within 1 hour. Rowever? for optimum gold solubilization, the minimum conCentratiQn of ammonium thiosulphate required is some-where in the range of 65-130 g.p.l. At 65 g.p.l. the initial . gold extraction was high, namely~ 89% after 1 hour, but it appears ,: that copper precipitation took place after this and reduced the ,,;
I gold extractio~ to 84% after 2 hours. This is dPduced from the ; fact that cupric ion concentration had decreased from the init;al . ; .
- 17 _ -.
5.74 g.p.l. to 4.96 g.p.l. a~ this time, representing a loss of 0.7.8 g.p~l. cupric ion~ from solution (shown in ~he Table as ~ Cu).
` Precipitation of copper also took place at 13 g.p.l.
.: and 32 g.p.l. ammonium thiosulphate, resulting in lower gold ex-tractions. At 130 g.p.l. ammonium thiosulphate, gold extraction of 91.5~ was obtained in 2 hours, with there bein~ a slight in-crease in cupric ions from 4.30 g.p.l. to 8.13 g.p.l. (The initial cupric ion concentration was 4.30 g.p.l. in this specific instance rather than 5.74 g.p.l. ac before).
Tests were then carried out with the concentrate to determine the eff~cts of thiosulphate leach temperature. The conditions were ~therwise the ~ame as in Example 4, with 5,74 g.p.l. cupric ions being added and the thiosulphate concentration being 130 g.p.l. The results are shown in Table Y.
TABLE V
_ Solution Assay6 _ _ . Residue - Au ~mp Time (g/l) (~C) (hr) pH Assays Extn cu ~ cu s~ s(s~o~5) NH~F tZ/ton) ~Z) 2025.~ 0 5.74 25.01~.2 0.188 __ : 0.5 . 24.510.1 0.036 80.9 1.0 .. 23.510.1 0.029 8b.6 i . 2.0 23.010.1 0.022 88.3 4.0 19.510.0 0.018 90.4 . ~ 6.0 6.70 +0.96 7~.Z 58.8 14.010.~ 0.018 90.4 :' 4809 0 4. 3~ ~S.S 9.6 0.188 __ 0.5 23~0 9.3 0.034 81.9 1.0 19.89.25 0.022 88.3 . 2.0 5.13~ ~0.83 69.1 59.4 17.5 9.2 0.016 gl.S
:~ 65.6 5~74 24.~ ~.9 0.188 __ : ~.5 . . 18.5 9,~ 0.028 85.1 : 1.0 . 10.5*9.7 0.050 73.4 : ~.0 ~1.0 9.8 0.113 39.9 3.0 0.38 -5.36 72.1 55.6 13.2 9.7- 0.146 22.3 _ ___ .~ 82.~ 0 5.74 30.09.g5 0.1~ __ .
: 0.5 21.59.90 0.051 72.9 1.0 20.59.80 0.136 27.7 2.0 0.283 -5.46 78.2 62.1 1~.0g.75 0.1~3 8.0 :
. . 98.~ 0 5.74 31.510.25 0.188 __ 0.5 _ 16.0g.60 0.18~ 0 : ~.~ . 15.59.55 ~.177 5.9 2.0 ~.167 -S.57 67.3 5~.5 IS.09.55 0.177 ~.9_ * Make-up NH40H added - 1 8 -Gold extractions of 90% were obtained at 25.6C.
in 4 hours and 2 hours at 48.9~C. Higher temperatures re-sulted in faster initial rates ~85% in 0.5 hours at 65.5C.) but copper precipitation and gold co-precipitation became very pro-nounced at temperatures above 65C., reducing ~old extractions of about 85% down to 40% after 2 hours, even at 65.6C. At -; 98.BC. the gold extraction was only about 5% after 2 hours, with almost all t97%~ of the initial copper in solution being preci-pitated. Thus, at least when leaching under a nitrogen atmosphere, temperatures in the range of 25C. to 50C. are recommended.
.
.. . .. _ . , Similar tests were carried out to determine the effect of free ammonia in the leach, the range of 25 to 60 g.p.l. NX~F being tested. It should perhaps be noted that in previous Examples 4 and 5, the tests were carried out in ammoniacal solutions containing 20-30 g.p.l. NH3F, which is sufficient to provide a free ammonia soluble metals molar ratio ~NH3F/Me) of at least 10:1 to 20:1. The leach was carried out at 48.9C. with 130 g.p.l. ammonium thiosulphate, and with an added cupric ion concentration of 4 . 30 or 5 . 76 g.p.l. The results are shown in Table VI
TABLE VI
.
. _ Solution Assay~ . __ ~nitial T~me _ Residue - Au ~H~ (hr) . ~g/1) ~gll~ _ ~ . pHAssays Extn Cu ~ Cu ST S(S20~') NH3F - toz/Ton) ~X) 0 4.30 . 25.5 9.6 0.188 __ 0.5 . . 23.0 9.3 0.03481.g 1.0 19.8 9.25 0.02288.3 2.0 5.13 +0.ô3 69.1 59.4 17.5 9.~ 0.016 91.5 0 5.74 47.5 9.55 0.188 __ 0.5 45.0 9.55 0.0248~.2 1.0 41.0 g.30 0.01592.0 2.0 6.65 +0.91 72.6 62.6 27.5 9.20 O.Q22 88.3 0 5.7b 62.5 I0.9 0.188 __ 0.5 51.0 10.0 0.~2288.3 1.0 47.5 10.0 0.01393.1 _ - 2.0 7.03 ~1.29 73.4 b2.8 46.0 10.0 0.020 89.4 ~ 19 -.
3~1 Although the ammonia concentration in solution diminished with time ~being removed by the nitrogen purge), : there was always sufficient free ammonia for an NH3F~Me molar ratio greater than 6:1.
It will be seen that 9 over the range of free ammonium concentrations tested, there was no appreciable change in gold extractions. The results suggest the advisa-bility of having sufficient free ammonia present to give an NH3F/soluble Me molar ratio of at least 8:1.
The next tests were conducted to determine the difference between air and nitrogen spar~ing. Tests were carried out both with and wîthout added cupric ions. As before, the charge eontained 400 g.p.l. concentrate and 130 g.p.l.
(NH4)2S203 and was conducted at 49C. The results are shown in Table VII.
" TABLE VII
'.': _ .
: Solu~lon Assays .
.: At~nosphere Initlal Time . . - ~ Residue - Au (sparge~) Cu2+ (hr) (g/l) _ (gll) . P~ AssayExtn .; ~ . Cu ~ Cu ST S (S20, ) ~R~F tOz/Ton~ ~X) :., . ~ _ N~trogen 0 0 0 . . 31. 0 9 . 6 0 .188 __ . 0.5 . : . 25.8 9 .4 0. 167 1~ . ~
; 1.0 . . 19.0 g.2 ~.13130.3 2.0 0.668 ~0.668 67.5 58.5 12.0 9. 2 0. 166 11 . 7 . ~ Air O O O : 31. O 9 . 6 ~' 0.188 __ O.S 25.0 9.5 ` 0.146 ?2.3 1.0 . 19.0 9. 35 O.Og2 51 . 1 2.0 0.821 +O.B21 67.1 59.0 14.0 9.2 0.087 53.7 ~, , . _ _ _ Nitrogen 5 . 74 O 5 . 74 22 . l) 10 ~ O O .188 __ . ~ O.S 19.~0 ~.9 0.061 6~.6 1 .0 18.5 9.8 0.042 77.7 2.0 5.53 -0.21 67.9 52.7 15.0 9.8 0.041 78.2 _ _ _ Air 5.74 0 5.74 23.0 10.0 0.188 __ 0.5 20.0 g.9 0.050 73.4 1.0 19.7 9.9 0~025 86.?
;...................... 2.0 6.20 ~4.46 68.3 56.3 1~.5 9.9 0.015* 92.
_ , , .. . .
* Silver a~say was 3.53 oz/ton ~ 22.9~ extraction.
.
With nitro~en sparging, the addition of cupric ions in-creased gold extraction ~f 10-30% up to 67-78~. The use of air, even in the absence of added cupric ions, enabled an extraction of 52-53% gold, while the addition of 5.7~ g.p.l. cupric i~ns results in a gold extraction of over 9l~ It would appear that, in the air sparge tests with no initial added cupric ions, cupric ions were generated in situ and promoted gold extraction. These results are also interesting in tha~, when nitrogen was purged over the leach slurry, as in the previous examples, ~he gold extractions were some lS~ higher than in the present ~est where nitrogen was sparged thr~ugh the leach slurry. It is possible that the lower extrac-tion is due, at least in part, to removal of entrained or soluble oxygen from the system by the sparging of nitrogen therethrou~h.
The effect of particle size on the ammonium thiosulphate leaching of the previously mentioned concentrate was tested. The concentrate was ground for various periods of time in a ceramic ball mill, up to 98% minus 40~. It is interesting that there was little change in surface area of the sulphides, the values ranging from 0.6 - l.6 m Jg. The leaches were carried out at 3 g.p.l. cupric ions, lO0 g.p.l. ammonium thiosulphate at 50C.
and with air sparging. The results are shown in Table VIII.
TABLE VIII
Buckbe~ screenl I S~ tlon .IssayJ . Res~du~ A~l ¦Grlnd ~ Surfact! Le~ch _ _ Tl~.e ,. passlng ¦ Area Tl~e S~P1) E~ ~ t~ss~ys Extn (hrs) _ m~/8 thrs) l _ _ p~l 40p10,~ . Cu ¦ ~ Cu S(S,O,~)~H~F ~IV ~z/T
___ , .L _. ~ _ . _ . i O 43 18 1.2 O 3.04 ~ 6'~.0 23.0 9.~0n.a. 0.168 . . O.S 1 3 27.5 a.go I 0.03~ 78.0 .
. 1.0 I I. 2~.0 9.9~ 1 0.0`6 1 9~.S
2.0 3.67 ¦ ~0.63 1 45.b 27.S 9.90; O.OOR~ I 96.B
l . . _ ~ .
O.S 74 2e 0.6 0 3.04 ¦ b2.0 27.0 g.go ¦ n.~. 0.168 0.5 l 30.0 9.90 1 0.032 1 81.0 1.0 I 30.0 9.~ol 0.012 1 92.9 _ _ 12 o 3.83 ~ +0.79 62.3 32.5 j 9.~o 1 _ 0.012 I 92.9 1.0 j 92 60 j 1.6 1 0 1 3.04 j 1 L2.0 1 22.5 1 1n.n ~ -185 0.168 !
0.5 ~ 23.0 ; 10.0 ¦ -160 1 0.020 85.1 1 ~0 ~ 20.5 1 9.95l -155 1 0.013 ~ 92.3 I 1 3 1 1 2-0 1 3-~6 1 ~0.~2 1 44.2 1 30.0 1 9-9~1 -1651 0.031 1 81.6 I a.o I 9S I S0 1 1.~ 1 0 1 3.0~ 1 1 42.0 1 ~4.0 110.1 1 -1gO1 0.168 1 ~
O.S ~ 5.5 1 lo.O j -1~D~ 0.012 1- 92.9 ' ~ 1.0 ~ 23.8 1 10.0 1 -~601 0.~20 1 ~8.1~
I I _ I L_ ~ 2.0 1 3.30 ~ ~0.~6 1 4S.~ ~ 31-0 ! ~-9 ~ o.o~a 1 56~9 1¦
Platinum vs S.C.E.
.
rt3~
-~ There i~ ~ more or lesfi linear relati~n~hip between crind time and initial gold extraction rates with, for example, the 0.5 h~ur extraction~ ranging from 78.0~ to 92.9%. However, after 0.5 hour, the fine ground sulphides promoted the preci-pitation of some of the copper as sulphide ~with the rate of sulphide precipitation exceeding the rate of oxidation and re-solubilization of the copper at the rate of air sparging) result-in~ in cc>rresponding co-precipitation of the gold.
The highest extraction at 2 hours of 94. 8% was obtained with the ungr~und concentrate. Th;s is therefore why it is recommended that the concentrate should be only lightly ground.
: EXAMPLE 9 In a main leach of the "super leach" kind, 200 g.p.l.
concentrate assaying (%) 24.7 Cua 29.g Fe, 4.29 Zn, 34.4 S
was lea~hed in water at 234C. under 100-150 p.s.i.g. oxygen ; . overpressure for 2 ~ours. The residue, predominantly an iron oxide assaying (~) 0.31 Cu, 47.5 Fe, 0.08 Zn, 8.2 S and (oz/T) 5.02 Ag and 0.303 Au, represented main lea~h extractions .~ . , .
of 98.99~ Cu and Zn and 85-90% S. Samples of filtered and washed ?O residue were conditioned for 1.0 hour at pH ~- 10 with either . sodium hydroxide, calcium hydroxide or ammonium hydroxide and . subsequently leached as a slurry containing 150 g.p.l. solids with ammoniacal thiosulphate containing initially 100 g.p.1.
; ammonium thiosulphate, 5 g.p.l. cupric ions ~added as Cu(NH3)~S04 .
solution) and 30 g-p-l- free ammonia. The thiosuiphate leach was conducted at 35C. for 5 hours with an air sparge of approximate-ly 1 litre per minute. The results are shown in Table IX.
TABLE IX
. Final Filtrates Assa s I Extractions COnd i tiOning CU I H.F PH AU ~n) Au ,) .
: NaOH 5.42 15.0 9.~5 0.023 0.817 92.4 83.7 Ca(OH)l 4.34 28.0 lOo 0 0~ 015 1~ 69 95 ~0 66 ~ 3 NN~OH 5.o8 17.0 9.90 o.Ol3 4.52 95.~ 10.0 . . ~
, ,. . .,: .
- . . ..... .
~ 8~ ' It wîll be noted that good gold extractions are achieved by thiosulphate leaching of the residue of a "super leach".
EXAMPLE lO
. . . _ , Gold and silver were recovered from an ammonium thio-, sulphate leach liquor by cemen~ation with zinc dust ~96% minus ; lO microns). Various concentrations of zinc dust were used, both with and without prior reduction of soluble cupric copper to euprous by sulphur dioxide. The leach liquor had been ob-tained in a thiosulphate leach of the residue of an ammoniacal main leach of chalcopyrite. The soluble copper content had initially been partly cuprous and partly cupric but, on stor-age, had been oxidized by air to cupric. The cementations were c~nducted with 500 ml samples of solution at 23C. and at atmospheric pressure, with a nitrogen purge and agitation provided by a ~agnetic stirrer. The results are shown in Table "., 10.
.
' ' , . .
:
~ .
'.
, - 23 -~3~i8:~ , ----C ~, o~ ~ ~ ~o ~ _~ . I~ r-. a~ __ P~ ~ ~ r~ _i r~ r~
__ ~ Ul ~ o~ ~o o~ ~ :. ~
l ¦ ~a ~3 ~
~ ~ u~ ~ C~ ~ ~r ~:r .~ _~ O ~ r~ O. _~ ~
' l _~ _~ o o o o o .
~;1 ~ ~ ol o o ~ ~
c' ~; _ ~ I~ o 0 ~ ~
PS 'D ,~ h O O O O O . .
~- ~ c ~o-~1 0~J C __ OC
~ 3 ~
. .
.
_ ~4 --~3~3~
These results clearly show that the prior reduction of soluble copper from cupric to cuprous significantly lowers the amount of zinc dust required to effectively remove the gold and sil~er. Without cupric reduction, zinc dust feed of the order of 6 g.p.l. is required for effective results, with 2 g.p.l. giving very poor gold and silver removal. On the other hand, zinc dust feed of 2 g.p.l. after cupric reduction gives excellent results, namely over 97~ gold and over 94%
silver removal.
With regard to the removal of gold and silver fro~
the thiosulphate leach liquor, reduction of soluble copper from cupric to cuprous, followed by cementation with zinc dust, has been shown to be an effective method of removal. It is possible to conduct the thiosulphate leach so that most of the soluble copper is cuprous, thereby lessening the amount of cupric copper to be reduced prior to cementation. This may be done for example by providing air only in -the initial stages of the thiosulphate leaoh,with the latter stages conducted in the absence of air to enable the cupric copper to be reduced to cuprous copper by the sulphides or thiosulphate sulphur.
Similar results may be achieved by conducting the leach in a countercurrent manner. However, it is advisable to ensure that at least some soluble copper i8 retained in the leach as cuprio cop~er to prevent precipitation of soluble copper, with subsequent loss of gqld and silver by co-precipitation therewith.
It is also possibie to recycle the crude precious metals residue from the filtration step 34 back -to the cupric reduction step 30, in conjunction with or, possibly, in place of the sulphur dioxideO Copper in the precious metals residue will act as a reductant for the cupric copper. At the same time, a significant portion of the copper in the crude precious metals residue will be solubilized, thereby upgrading the ~3 ~recious metals residueO
; Also, the cementation could be carried out with copper powder instead of zinc dust, and sulphites could be used in place of sulphur dioxide for cupric reduction. Further, hydrogen sul-phide or ammonium sulphide may ~e used as alternatives to c~pp~r powder or æinc dust to effect removal of the gold and silver.
The alternative methods described above for removal of gold and silver from the thiosulphate leach liquor do not involve destruction o~ the thiosulphat~, and such methods are therefore generally to be preferred. However, there may be circumstances where other methods may offer some advantage.
For example, oxidation of all or most of the ammoniacal thiosulphate sulphur in the leach liquor to sulphate at elevated temperature and oxygen overpressure may facilitate the recovery of the precious metals, which may be carried out by precipitation by hydrogen sulphide, sodium sulphide or ammonium sulphide, or by removal by a related thiol group of commercially available ion exchange resins. Cementation with copper or zinc dust may also be used. These methods may be used with or without prior removal of cupric copper, for example 9 by liquid or solid ;on exchange.
Also, gold can be recovered ~rom the oxidized liquor by selec-tive adsorption by activated charcoal, leaving most of the silver in the solution for subse~uent recovery, thereby enabling the gold and silver to be separately recovered.
Although precious metal recovery methods involving the destruction of the thiosulphate may seem unattractive, it ; will be observed that, in the process described with reference to Figure 1, there will be a gradual build-up of ammonium sul-phate in the thiosulphate circuit, since the ammonium sulphate will enter the circuit along with cupric copper as entrained main leach liquor with the main leach residue arriving at re-pulp step 16~ It will therefore probably be necessary to ~ A
~6~
provide a suitable bleed from the thiosulphate circuit, and precious metals may be recovered from the bleed stream by the methods suggested above, involving the destruction of the thio-sulphate. The depleted bleed stream could then be recycled to the main leach circuit.
Thus, gold, and possibly also silver, therefore can, in accordance with the invention, be recovered on a commercial - scale from copper bearing sulphidic concentrates which are treated for recovery of copper by leaching under oxidizing conditions, the precious metals recovery treatment being car-ried out either on the unleached concentrate or on the residue from the copper recovery leach. Which precious metals recovery treatment is used depends, among other things, on the initial precious metals content and the nature of the recovery required.
Slightly better gold recovery appears to be obtained by treat-; ing the concentrate, but much better silver recovery is obtained by treatment of the copper leach residue.
The effect of varying different ammonium thiosulphateleach condition~ has been indicated and various ambodiments, wit~ specific examples thereof, have been described. Other - embodiments within the scope of the invention will be appar-ent to one skilled in the art, the scope of the invention be-ing defined in the appended claims.
` Precipitation of copper also took place at 13 g.p.l.
.: and 32 g.p.l. ammonium thiosulphate, resulting in lower gold ex-tractions. At 130 g.p.l. ammonium thiosulphate, gold extraction of 91.5~ was obtained in 2 hours, with there bein~ a slight in-crease in cupric ions from 4.30 g.p.l. to 8.13 g.p.l. (The initial cupric ion concentration was 4.30 g.p.l. in this specific instance rather than 5.74 g.p.l. ac before).
Tests were then carried out with the concentrate to determine the eff~cts of thiosulphate leach temperature. The conditions were ~therwise the ~ame as in Example 4, with 5,74 g.p.l. cupric ions being added and the thiosulphate concentration being 130 g.p.l. The results are shown in Table Y.
TABLE V
_ Solution Assay6 _ _ . Residue - Au ~mp Time (g/l) (~C) (hr) pH Assays Extn cu ~ cu s~ s(s~o~5) NH~F tZ/ton) ~Z) 2025.~ 0 5.74 25.01~.2 0.188 __ : 0.5 . 24.510.1 0.036 80.9 1.0 .. 23.510.1 0.029 8b.6 i . 2.0 23.010.1 0.022 88.3 4.0 19.510.0 0.018 90.4 . ~ 6.0 6.70 +0.96 7~.Z 58.8 14.010.~ 0.018 90.4 :' 4809 0 4. 3~ ~S.S 9.6 0.188 __ 0.5 23~0 9.3 0.034 81.9 1.0 19.89.25 0.022 88.3 . 2.0 5.13~ ~0.83 69.1 59.4 17.5 9.2 0.016 gl.S
:~ 65.6 5~74 24.~ ~.9 0.188 __ : ~.5 . . 18.5 9,~ 0.028 85.1 : 1.0 . 10.5*9.7 0.050 73.4 : ~.0 ~1.0 9.8 0.113 39.9 3.0 0.38 -5.36 72.1 55.6 13.2 9.7- 0.146 22.3 _ ___ .~ 82.~ 0 5.74 30.09.g5 0.1~ __ .
: 0.5 21.59.90 0.051 72.9 1.0 20.59.80 0.136 27.7 2.0 0.283 -5.46 78.2 62.1 1~.0g.75 0.1~3 8.0 :
. . 98.~ 0 5.74 31.510.25 0.188 __ 0.5 _ 16.0g.60 0.18~ 0 : ~.~ . 15.59.55 ~.177 5.9 2.0 ~.167 -S.57 67.3 5~.5 IS.09.55 0.177 ~.9_ * Make-up NH40H added - 1 8 -Gold extractions of 90% were obtained at 25.6C.
in 4 hours and 2 hours at 48.9~C. Higher temperatures re-sulted in faster initial rates ~85% in 0.5 hours at 65.5C.) but copper precipitation and gold co-precipitation became very pro-nounced at temperatures above 65C., reducing ~old extractions of about 85% down to 40% after 2 hours, even at 65.6C. At -; 98.BC. the gold extraction was only about 5% after 2 hours, with almost all t97%~ of the initial copper in solution being preci-pitated. Thus, at least when leaching under a nitrogen atmosphere, temperatures in the range of 25C. to 50C. are recommended.
.
.. . .. _ . , Similar tests were carried out to determine the effect of free ammonia in the leach, the range of 25 to 60 g.p.l. NX~F being tested. It should perhaps be noted that in previous Examples 4 and 5, the tests were carried out in ammoniacal solutions containing 20-30 g.p.l. NH3F, which is sufficient to provide a free ammonia soluble metals molar ratio ~NH3F/Me) of at least 10:1 to 20:1. The leach was carried out at 48.9C. with 130 g.p.l. ammonium thiosulphate, and with an added cupric ion concentration of 4 . 30 or 5 . 76 g.p.l. The results are shown in Table VI
TABLE VI
.
. _ Solution Assay~ . __ ~nitial T~me _ Residue - Au ~H~ (hr) . ~g/1) ~gll~ _ ~ . pHAssays Extn Cu ~ Cu ST S(S20~') NH3F - toz/Ton) ~X) 0 4.30 . 25.5 9.6 0.188 __ 0.5 . . 23.0 9.3 0.03481.g 1.0 19.8 9.25 0.02288.3 2.0 5.13 +0.ô3 69.1 59.4 17.5 9.~ 0.016 91.5 0 5.74 47.5 9.55 0.188 __ 0.5 45.0 9.55 0.0248~.2 1.0 41.0 g.30 0.01592.0 2.0 6.65 +0.91 72.6 62.6 27.5 9.20 O.Q22 88.3 0 5.7b 62.5 I0.9 0.188 __ 0.5 51.0 10.0 0.~2288.3 1.0 47.5 10.0 0.01393.1 _ - 2.0 7.03 ~1.29 73.4 b2.8 46.0 10.0 0.020 89.4 ~ 19 -.
3~1 Although the ammonia concentration in solution diminished with time ~being removed by the nitrogen purge), : there was always sufficient free ammonia for an NH3F~Me molar ratio greater than 6:1.
It will be seen that 9 over the range of free ammonium concentrations tested, there was no appreciable change in gold extractions. The results suggest the advisa-bility of having sufficient free ammonia present to give an NH3F/soluble Me molar ratio of at least 8:1.
The next tests were conducted to determine the difference between air and nitrogen spar~ing. Tests were carried out both with and wîthout added cupric ions. As before, the charge eontained 400 g.p.l. concentrate and 130 g.p.l.
(NH4)2S203 and was conducted at 49C. The results are shown in Table VII.
" TABLE VII
'.': _ .
: Solu~lon Assays .
.: At~nosphere Initlal Time . . - ~ Residue - Au (sparge~) Cu2+ (hr) (g/l) _ (gll) . P~ AssayExtn .; ~ . Cu ~ Cu ST S (S20, ) ~R~F tOz/Ton~ ~X) :., . ~ _ N~trogen 0 0 0 . . 31. 0 9 . 6 0 .188 __ . 0.5 . : . 25.8 9 .4 0. 167 1~ . ~
; 1.0 . . 19.0 g.2 ~.13130.3 2.0 0.668 ~0.668 67.5 58.5 12.0 9. 2 0. 166 11 . 7 . ~ Air O O O : 31. O 9 . 6 ~' 0.188 __ O.S 25.0 9.5 ` 0.146 ?2.3 1.0 . 19.0 9. 35 O.Og2 51 . 1 2.0 0.821 +O.B21 67.1 59.0 14.0 9.2 0.087 53.7 ~, , . _ _ _ Nitrogen 5 . 74 O 5 . 74 22 . l) 10 ~ O O .188 __ . ~ O.S 19.~0 ~.9 0.061 6~.6 1 .0 18.5 9.8 0.042 77.7 2.0 5.53 -0.21 67.9 52.7 15.0 9.8 0.041 78.2 _ _ _ Air 5.74 0 5.74 23.0 10.0 0.188 __ 0.5 20.0 g.9 0.050 73.4 1.0 19.7 9.9 0~025 86.?
;...................... 2.0 6.20 ~4.46 68.3 56.3 1~.5 9.9 0.015* 92.
_ , , .. . .
* Silver a~say was 3.53 oz/ton ~ 22.9~ extraction.
.
With nitro~en sparging, the addition of cupric ions in-creased gold extraction ~f 10-30% up to 67-78~. The use of air, even in the absence of added cupric ions, enabled an extraction of 52-53% gold, while the addition of 5.7~ g.p.l. cupric i~ns results in a gold extraction of over 9l~ It would appear that, in the air sparge tests with no initial added cupric ions, cupric ions were generated in situ and promoted gold extraction. These results are also interesting in tha~, when nitrogen was purged over the leach slurry, as in the previous examples, ~he gold extractions were some lS~ higher than in the present ~est where nitrogen was sparged thr~ugh the leach slurry. It is possible that the lower extrac-tion is due, at least in part, to removal of entrained or soluble oxygen from the system by the sparging of nitrogen therethrou~h.
The effect of particle size on the ammonium thiosulphate leaching of the previously mentioned concentrate was tested. The concentrate was ground for various periods of time in a ceramic ball mill, up to 98% minus 40~. It is interesting that there was little change in surface area of the sulphides, the values ranging from 0.6 - l.6 m Jg. The leaches were carried out at 3 g.p.l. cupric ions, lO0 g.p.l. ammonium thiosulphate at 50C.
and with air sparging. The results are shown in Table VIII.
TABLE VIII
Buckbe~ screenl I S~ tlon .IssayJ . Res~du~ A~l ¦Grlnd ~ Surfact! Le~ch _ _ Tl~.e ,. passlng ¦ Area Tl~e S~P1) E~ ~ t~ss~ys Extn (hrs) _ m~/8 thrs) l _ _ p~l 40p10,~ . Cu ¦ ~ Cu S(S,O,~)~H~F ~IV ~z/T
___ , .L _. ~ _ . _ . i O 43 18 1.2 O 3.04 ~ 6'~.0 23.0 9.~0n.a. 0.168 . . O.S 1 3 27.5 a.go I 0.03~ 78.0 .
. 1.0 I I. 2~.0 9.9~ 1 0.0`6 1 9~.S
2.0 3.67 ¦ ~0.63 1 45.b 27.S 9.90; O.OOR~ I 96.B
l . . _ ~ .
O.S 74 2e 0.6 0 3.04 ¦ b2.0 27.0 g.go ¦ n.~. 0.168 0.5 l 30.0 9.90 1 0.032 1 81.0 1.0 I 30.0 9.~ol 0.012 1 92.9 _ _ 12 o 3.83 ~ +0.79 62.3 32.5 j 9.~o 1 _ 0.012 I 92.9 1.0 j 92 60 j 1.6 1 0 1 3.04 j 1 L2.0 1 22.5 1 1n.n ~ -185 0.168 !
0.5 ~ 23.0 ; 10.0 ¦ -160 1 0.020 85.1 1 ~0 ~ 20.5 1 9.95l -155 1 0.013 ~ 92.3 I 1 3 1 1 2-0 1 3-~6 1 ~0.~2 1 44.2 1 30.0 1 9-9~1 -1651 0.031 1 81.6 I a.o I 9S I S0 1 1.~ 1 0 1 3.0~ 1 1 42.0 1 ~4.0 110.1 1 -1gO1 0.168 1 ~
O.S ~ 5.5 1 lo.O j -1~D~ 0.012 1- 92.9 ' ~ 1.0 ~ 23.8 1 10.0 1 -~601 0.~20 1 ~8.1~
I I _ I L_ ~ 2.0 1 3.30 ~ ~0.~6 1 4S.~ ~ 31-0 ! ~-9 ~ o.o~a 1 56~9 1¦
Platinum vs S.C.E.
.
rt3~
-~ There i~ ~ more or lesfi linear relati~n~hip between crind time and initial gold extraction rates with, for example, the 0.5 h~ur extraction~ ranging from 78.0~ to 92.9%. However, after 0.5 hour, the fine ground sulphides promoted the preci-pitation of some of the copper as sulphide ~with the rate of sulphide precipitation exceeding the rate of oxidation and re-solubilization of the copper at the rate of air sparging) result-in~ in cc>rresponding co-precipitation of the gold.
The highest extraction at 2 hours of 94. 8% was obtained with the ungr~und concentrate. Th;s is therefore why it is recommended that the concentrate should be only lightly ground.
: EXAMPLE 9 In a main leach of the "super leach" kind, 200 g.p.l.
concentrate assaying (%) 24.7 Cua 29.g Fe, 4.29 Zn, 34.4 S
was lea~hed in water at 234C. under 100-150 p.s.i.g. oxygen ; . overpressure for 2 ~ours. The residue, predominantly an iron oxide assaying (~) 0.31 Cu, 47.5 Fe, 0.08 Zn, 8.2 S and (oz/T) 5.02 Ag and 0.303 Au, represented main lea~h extractions .~ . , .
of 98.99~ Cu and Zn and 85-90% S. Samples of filtered and washed ?O residue were conditioned for 1.0 hour at pH ~- 10 with either . sodium hydroxide, calcium hydroxide or ammonium hydroxide and . subsequently leached as a slurry containing 150 g.p.l. solids with ammoniacal thiosulphate containing initially 100 g.p.1.
; ammonium thiosulphate, 5 g.p.l. cupric ions ~added as Cu(NH3)~S04 .
solution) and 30 g-p-l- free ammonia. The thiosuiphate leach was conducted at 35C. for 5 hours with an air sparge of approximate-ly 1 litre per minute. The results are shown in Table IX.
TABLE IX
. Final Filtrates Assa s I Extractions COnd i tiOning CU I H.F PH AU ~n) Au ,) .
: NaOH 5.42 15.0 9.~5 0.023 0.817 92.4 83.7 Ca(OH)l 4.34 28.0 lOo 0 0~ 015 1~ 69 95 ~0 66 ~ 3 NN~OH 5.o8 17.0 9.90 o.Ol3 4.52 95.~ 10.0 . . ~
, ,. . .,: .
- . . ..... .
~ 8~ ' It wîll be noted that good gold extractions are achieved by thiosulphate leaching of the residue of a "super leach".
EXAMPLE lO
. . . _ , Gold and silver were recovered from an ammonium thio-, sulphate leach liquor by cemen~ation with zinc dust ~96% minus ; lO microns). Various concentrations of zinc dust were used, both with and without prior reduction of soluble cupric copper to euprous by sulphur dioxide. The leach liquor had been ob-tained in a thiosulphate leach of the residue of an ammoniacal main leach of chalcopyrite. The soluble copper content had initially been partly cuprous and partly cupric but, on stor-age, had been oxidized by air to cupric. The cementations were c~nducted with 500 ml samples of solution at 23C. and at atmospheric pressure, with a nitrogen purge and agitation provided by a ~agnetic stirrer. The results are shown in Table "., 10.
.
' ' , . .
:
~ .
'.
, - 23 -~3~i8:~ , ----C ~, o~ ~ ~ ~o ~ _~ . I~ r-. a~ __ P~ ~ ~ r~ _i r~ r~
__ ~ Ul ~ o~ ~o o~ ~ :. ~
l ¦ ~a ~3 ~
~ ~ u~ ~ C~ ~ ~r ~:r .~ _~ O ~ r~ O. _~ ~
' l _~ _~ o o o o o .
~;1 ~ ~ ol o o ~ ~
c' ~; _ ~ I~ o 0 ~ ~
PS 'D ,~ h O O O O O . .
~- ~ c ~o-~1 0~J C __ OC
~ 3 ~
. .
.
_ ~4 --~3~3~
These results clearly show that the prior reduction of soluble copper from cupric to cuprous significantly lowers the amount of zinc dust required to effectively remove the gold and sil~er. Without cupric reduction, zinc dust feed of the order of 6 g.p.l. is required for effective results, with 2 g.p.l. giving very poor gold and silver removal. On the other hand, zinc dust feed of 2 g.p.l. after cupric reduction gives excellent results, namely over 97~ gold and over 94%
silver removal.
With regard to the removal of gold and silver fro~
the thiosulphate leach liquor, reduction of soluble copper from cupric to cuprous, followed by cementation with zinc dust, has been shown to be an effective method of removal. It is possible to conduct the thiosulphate leach so that most of the soluble copper is cuprous, thereby lessening the amount of cupric copper to be reduced prior to cementation. This may be done for example by providing air only in -the initial stages of the thiosulphate leaoh,with the latter stages conducted in the absence of air to enable the cupric copper to be reduced to cuprous copper by the sulphides or thiosulphate sulphur.
Similar results may be achieved by conducting the leach in a countercurrent manner. However, it is advisable to ensure that at least some soluble copper i8 retained in the leach as cuprio cop~er to prevent precipitation of soluble copper, with subsequent loss of gqld and silver by co-precipitation therewith.
It is also possibie to recycle the crude precious metals residue from the filtration step 34 back -to the cupric reduction step 30, in conjunction with or, possibly, in place of the sulphur dioxideO Copper in the precious metals residue will act as a reductant for the cupric copper. At the same time, a significant portion of the copper in the crude precious metals residue will be solubilized, thereby upgrading the ~3 ~recious metals residueO
; Also, the cementation could be carried out with copper powder instead of zinc dust, and sulphites could be used in place of sulphur dioxide for cupric reduction. Further, hydrogen sul-phide or ammonium sulphide may ~e used as alternatives to c~pp~r powder or æinc dust to effect removal of the gold and silver.
The alternative methods described above for removal of gold and silver from the thiosulphate leach liquor do not involve destruction o~ the thiosulphat~, and such methods are therefore generally to be preferred. However, there may be circumstances where other methods may offer some advantage.
For example, oxidation of all or most of the ammoniacal thiosulphate sulphur in the leach liquor to sulphate at elevated temperature and oxygen overpressure may facilitate the recovery of the precious metals, which may be carried out by precipitation by hydrogen sulphide, sodium sulphide or ammonium sulphide, or by removal by a related thiol group of commercially available ion exchange resins. Cementation with copper or zinc dust may also be used. These methods may be used with or without prior removal of cupric copper, for example 9 by liquid or solid ;on exchange.
Also, gold can be recovered ~rom the oxidized liquor by selec-tive adsorption by activated charcoal, leaving most of the silver in the solution for subse~uent recovery, thereby enabling the gold and silver to be separately recovered.
Although precious metal recovery methods involving the destruction of the thiosulphate may seem unattractive, it ; will be observed that, in the process described with reference to Figure 1, there will be a gradual build-up of ammonium sul-phate in the thiosulphate circuit, since the ammonium sulphate will enter the circuit along with cupric copper as entrained main leach liquor with the main leach residue arriving at re-pulp step 16~ It will therefore probably be necessary to ~ A
~6~
provide a suitable bleed from the thiosulphate circuit, and precious metals may be recovered from the bleed stream by the methods suggested above, involving the destruction of the thio-sulphate. The depleted bleed stream could then be recycled to the main leach circuit.
Thus, gold, and possibly also silver, therefore can, in accordance with the invention, be recovered on a commercial - scale from copper bearing sulphidic concentrates which are treated for recovery of copper by leaching under oxidizing conditions, the precious metals recovery treatment being car-ried out either on the unleached concentrate or on the residue from the copper recovery leach. Which precious metals recovery treatment is used depends, among other things, on the initial precious metals content and the nature of the recovery required.
Slightly better gold recovery appears to be obtained by treat-; ing the concentrate, but much better silver recovery is obtained by treatment of the copper leach residue.
The effect of varying different ammonium thiosulphateleach condition~ has been indicated and various ambodiments, wit~ specific examples thereof, have been described. Other - embodiments within the scope of the invention will be appar-ent to one skilled in the art, the scope of the invention be-ing defined in the appended claims.
Claims (29)
1. A process for the recovery of gold as well as copper values from copper bearing sulphidic material containing gold, including subjecting the copper bearing sulphidic material to a main leach under oxidizing conditions to provide a copper containing main leach liquor and a main residue, and subject-ing said copper bearing sulphidic material before said main leach or said main leach residue from said main leach to a secondary leach with ammonium thiosulphate solution to provide a gold containing secondary leach liquor and a secondary resi-due, and separating said gold containing secondary leach liquor from the secondary residue.
2. A process according to claim 1 wherein the main leach is carried out with an ammonium salt containing ammoniacal aqueous leach medium.
3. A process according to claim 1 wherein the ammonium salt is ammonium sulphate.
4. A process according to claim 1 wherein the copper bearing sulphidic material is chalcopyrite.
5. A process according to claim 2 wherein the copper bearing sulphidic material is chalcopyrite and the ammonium salt is ammonium sulphate.
6. A process according to claim 5 wherein the chalco-pyrite is subjected to said secondary leach with ammonium thio-sulphate solution to provide said gold containing leach liquor before being subjected to said main leach.
7. A process according to claim 5 wherein said main residue from said main leach is subjected to said secondary leach with ammonium thiosulphate solution to provide said gold containing leach liquor.
8. A process according to claim 2 wherein the thiosul-phate leach is carried out in the presence of added cupric ions.
9. A process according to claim 8 wherein the addition of cupric ions is sufficient to provide a cupric ion concentra-tion in the range of 1 to 10 g.p.1.
10. A process according to claim 9 wherein the addition of cupric ions is sufficient to provide a cupric ion concentra-tion in the range of 2 to 4 g.p.1.
11. A process according to claim 1 wherein the thiosul-phate leach is carried out with an ammonium thiosulphate con-centration in the range of 10 to 150 g.p.1.
12. A process according to claim 11 wherein the thiosul-phate leach is carried out with an ammonium thiosulphate con-centration in the range of 60 to 120 g.p.1.
13. A process according to claim 2 wherein the thiosul-phate leach is carried out in the presence of free ammonia sufficient to provide a free ammonia to soluble metals molar ratio of at least 4 to 1.
14. A process according to claim 1 wherein the thiosul-phate leach is carried out at a temperature between 20°C. and 65°C.
15. A process according to claim 14 wherein the thiosul-phate leach is carried out at a temperature between 25°C. to 50°C.
16. A process according to claim 1 wherein the thiosul-phate leach is carried out substantially at atmospheric pressure in the presence of free oxygen.
17. A process according to claim 1 wherein the thiosul-phate leach is carried out in an inert atmosphere.
18. A process according to claim 1 wherein the copper bearing sulphidic material is subjected to said secondary leach with ammonium thiosulphate to provide said gold containing leach liquor before being subjected to said main leach and the cupriferous sulphidic material has a particle size in the range of 60% minus 200 mesh to 95% minus 325 mesh.
19. A process according to claim 1 wherein the copper bearing sulphidic material also contains silver, and silver is leached from said copper bearing sulphidic material or said main residue in said secondary leach and is present in solution in said gold containing leach liquor.
20. A process-according to claim 1 wherein the main leach is carried out at a temperature in the range of 160°C.
to 230°C. with a free oxygen partial pressure in the range of 50 p.s.i.g. to 200 p.s.i.g. in an acid producing leach medium.
to 230°C. with a free oxygen partial pressure in the range of 50 p.s.i.g. to 200 p.s.i.g. in an acid producing leach medium.
21. A process according to claim 20 wherein the main leach residue is subjected to the secondary leach with ammonium thiosulphate solution, the main leach residue first being conditioned in an alkaline medium.
22. A process according to claim 1 wherein gold is removed from the secondary leach liquor by cementation with at least one of the metals copper and zinc.
23. A process according to claim 22 wherein, before said cementation, soluble cupric copper in the secondary leach liquor is reduced to cuprous copper.
24. A process according to claim 23 wherein said reduc-tion is carried out with sulphur dioxide.
25. A process for the recovery of gold as well as copper values from copper bearing sulphidic material containing gold, including subjecting the copper bearing material to a main leach to dissolve a substantial amount of copper without dissolving a substantial amount of gold and provide a copper containing main leach liquor and gold containing main residue, separating the main residue from the main leach liquor, subjecting the main leach residue to a secondary leach with ammonium thiosulphate solution in the presence of cupric ammine ions to dissolve a substantial amount of gold and provide a gold containing second-ary leach liquor and a secondary residue, with the copper of at least some of the cupric ammine ions emanating from the copper bearing sulphidic material, and separating said gold containing secondary leach liquor from the secondary.
26. A process according to claim 25 wherein the copper of at least some of the cupric ammine ions is obtained from said main leach liquor.
27. A process for the recovery of gold as well as copper from copper bearing sulphidic material containing gold, includ-ing subjecting the copper bearing sulphidic material to a second-ary leach with ammonium thiosulphate solution in the presence of cupric ammine ions to dissolve a substantial amount of gold without dissolving a substantial amount of copper and provide a gold containing secondary leach liquor and a copper containing secondary residue with the copper of at least some of the cupric ammine ions emanating from the copper bearing sulphidîc material, separating said gold containing secondary leach liquor from the secondary residue, subjecting the copper containing secondary residue to a main leach to dissolve a substantial amount of copper and provide a copper containing main leach liquor and a main residue, and separating the copper containing main leach liquor from said main residue.
28. A process according to claim 27 wherein said main leach is an ammoniacal leach and some of said copper containing main leach liquor is recycled to said secondary leach to pro-vide at least some of said cupric ammine ions.
29. A process according to claim 1 wherein the copper bearing sulphidic material also contains silver, silver is leached from said copper bearing sulphidic material or said main residue in said secondary leach and is present in solution in said gold containing leach liquor, and the main leach is carried out at a temperature in the range of 160°C. to 230°C.
with a free oxygen partial pressure in the range of 50 p.s.i.g.
to 200 p.s.i.g. in acid producing leach medium.
with a free oxygen partial pressure in the range of 50 p.s.i.g.
to 200 p.s.i.g. in acid producing leach medium.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA246,274A CA1073681A (en) | 1976-02-20 | 1976-02-20 | Recovery of precious metals from metal sulphides |
| US05/714,060 US4070182A (en) | 1976-02-20 | 1976-08-13 | Recovery of precious metals from metal sulphides |
| ZA770840A ZA77840B (en) | 1976-02-20 | 1977-02-14 | Recovery of precious metals from metal sulphides |
| AU22461/77A AU499658B2 (en) | 1976-02-20 | 1977-02-18 | Recovering precious metals from metal sulphides |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA246,274A CA1073681A (en) | 1976-02-20 | 1976-02-20 | Recovery of precious metals from metal sulphides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1073681A true CA1073681A (en) | 1980-03-18 |
Family
ID=4105288
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA246,274A Expired CA1073681A (en) | 1976-02-20 | 1976-02-20 | Recovery of precious metals from metal sulphides |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4070182A (en) |
| AU (1) | AU499658B2 (en) |
| CA (1) | CA1073681A (en) |
| ZA (1) | ZA77840B (en) |
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| CA2820700C (en) | 2010-12-07 | 2015-11-24 | Barrick Gold Corporation | Co-current and counter current resin-in-leach in gold leaching processes |
| AR086933A1 (en) | 2011-06-15 | 2014-01-29 | Barrick Gold Corp | METHOD FOR RECOVERING PRECIOUS METALS AND COPPER OF LIXIVIATE SOLUTIONS |
| US9221114B2 (en) | 2011-12-15 | 2015-12-29 | Advanced Technology Materials, Inc. | Apparatus and method for stripping solder metals during the recycling of waste electrical and electronic equipment |
| US8931642B2 (en) | 2013-01-14 | 2015-01-13 | William D. Simmons | Activated flotation circuit for processing combined oxide and sulfide ores |
| US10161016B2 (en) | 2013-05-29 | 2018-12-25 | Barrick Gold Corporation | Method for pre-treatment of gold-bearing oxide ores |
| ES2940464T3 (en) * | 2013-09-04 | 2023-05-08 | Mining and Process Solutions Pty Ltd | Process to recover copper and/or precious metals |
| US9777346B2 (en) | 2015-09-03 | 2017-10-03 | Battelle Energy Alliance, Llc | Methods for recovering metals from electronic waste, and related systems |
| PE20211512A1 (en) | 2019-01-21 | 2021-08-11 | Barrick Gold Corp | METHOD FOR CARBON-CATALYZED THOSULFATE LEACHING OF MATERIALS CONTAINING GOLD |
| MX2021014725A (en) | 2019-06-03 | 2022-01-18 | Barrick Gold Corp | Method for recovering gold from refractory materials. |
| AR126592A1 (en) * | 2021-07-28 | 2023-10-25 | Tech Resources Pty Ltd | EXTRACTION METHOD |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE380028A (en) * | 1929-11-29 | 1900-01-01 | ||
| US2093958A (en) * | 1936-08-06 | 1937-09-21 | Edquist Victor Thomas | Recovery of gold and/or silver from ores and metallurgical products |
| US2647819A (en) * | 1949-06-04 | 1953-08-04 | Chemical Construction Corp | Copper, cobalt, and ammonium sulfate recovery from mineral leach liquors |
| US2693404A (en) * | 1951-01-18 | 1954-11-02 | Sherritt Gordon Mines Ltd | Method of separating metal values from ammoniacal solutions |
| US2822263A (en) * | 1954-09-01 | 1958-02-04 | Sherritt Gordon Mines Ltd | Method of extracting copper values from copper bearing mineral sulphides |
| US2807533A (en) * | 1956-05-21 | 1957-09-24 | Calumet And Hecla Inc | Silver recovery method |
| US3088820A (en) * | 1959-05-18 | 1963-05-07 | Sherritt Gordon Mines Ltd | Process for the recovery of metal values from low grade materials |
| NL268606A (en) * | 1960-09-12 | |||
| US3669651A (en) * | 1970-04-15 | 1972-06-13 | Kennecott Copper Corp | Reduction of ferric ions in cyclic process of leaching and precipitation of copper |
| US3975190A (en) * | 1975-05-23 | 1976-08-17 | Sherritt Gordon Mines Limited | Hydrometallurgical treatment of nickel and copper bearing intermediates |
-
1976
- 1976-02-20 CA CA246,274A patent/CA1073681A/en not_active Expired
- 1976-08-13 US US05/714,060 patent/US4070182A/en not_active Expired - Lifetime
-
1977
- 1977-02-14 ZA ZA770840A patent/ZA77840B/en unknown
- 1977-02-18 AU AU22461/77A patent/AU499658B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| AU499658B2 (en) | 1979-04-26 |
| ZA77840B (en) | 1977-12-28 |
| US4070182A (en) | 1978-01-24 |
| AU2246177A (en) | 1978-08-24 |
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