The present invention relates to a method of recovering silver from sulphur-containing zinc leach residues, especially direct zinc leach residues. BACKGROUND OF THE INVENTION

Zinc concentrates usually contain some silver that ends to the leach residue after direct leaching of zinc. Economical recovery of silver from the leach residue that contains about 70% elemental sulphur is difficult. Conventional cyanide leaching, roasting of the leach residue prior to cyanide leaching, thiosulfate leaching and selective flotation have been proposed, but they are not advisable for either economical or process-technical reasons. Consequently, high-sulphur zinc leach residues have in most cases been discarded for landfill purposes without recovering the silver values therefrom.

Various processes based on chloride leaching have been applied in the prior art for recovering silver and other metal values from zinc leach residues in general.

GB 1337 739 discloses a process of recovering silver and lead contained in residues remaining after zinc concentrates and/or complex concentrates have been roasted to yield a calcined product which has thereafter been treated with an acid to dissolve zinc and to yield said silver and lead containing residues and a zinc containing solution. The zinc and lead containing residues may be obtained from electrolytic production of zinc, for example. The process comprises leaching the residue at ambient temperature with an acidified chloride solution in one or more steps and recovering lead and silver from the leach solution as insoluble salts such as sulphides or by cementation. The chloride solution used for leaching is preferably saturated with chloride and contains copper chloride.

US 4 01 1 146 discloses a process of recovering silver and lead from sulphide ore concentrates containing lead, silver and zinc sulphides. The sulphides are converted to chlorides in a chlorination step, followed by leaching with aqueous sodium chloride. Lead is recovered from the leach solution by cooling as lead chloride, followed by recovering silver from the lead chloride depleted solution by cementation. The method also comprises recycling the sodium chloride solution depleted of a major part of lead and silver to the chlo- rination or leaching step and removing a portion of the recycle stream as a bleed stream to control the concentration of zinc and other impurities in the chlorination or leaching solution. It is recited that the leach solution may contain e.g. 260-280 g/l sodium chloride. The leaching step is preferably performed at a temperature of from about 80°C to 100°C.

EP 0 042 702 discloses a process for recovering lead and silver from an ore or a process residue by treatment with acidic chloride brine and precipitating lead oxychloride and silver compounds by adding lime. After further process steps, silver may be finally recovered by cementation or flotation. Examples 1 to 8 show leaching of hot sulphuric acid leach residues obtained from sul- phation roasting and leaching of bulk zinc-lead-copper-silver sulphide concentrates. Leaching is performed with a brine solution containing 220-300 g/l NaCI at a pH of 1 .5.

US 3 929 597 discloses a method of recovering silver and lead from sulphide ores by leaching with a ferric chloride solution to form a solid residue of silver and lead salts, leaching the solid residue with aqueous sodium chloride to dissolve the salts, cooling the solution to precipitate lead as lead chloride and further recovering silver from the solution by cementation.

GB 2 128 597 discloses a process of recovering non-ferrous metals, such as zinc and copper, from sulphide concentrates. The process comprises leaching the concentrate with an acidic chloride solution containing calcium chloride to solubilize the non-ferrous metals and to precipitate sulphur as calcium sulphate, followed by recovering the metals from the leach liquor by ion exchange in combination with other recovery methods. The document does not discuss the recovery of silver.

However, the processes based on chloride leaching discussed above may not be sufficiently selective for recovering silver from high-sulphur direct zinc leach residues.

BRIEF DESCRIPTION OF THE INVENTION

An object of the present invention is to provide a method and an apparatus for implementing the method so as to alleviate the above disadvantages relating to selective recovery of silver from high-sulphur zinc leach residues. The objects of the invention are achieved by a method and arrangements which are characterized by what is stated in the independent claims. The preferred embodiments of the invention are disclosed in the dependent claims. The invention is based on the idea of selecting suitable leaching conditions for dissolving silver from high-sulphur direct zinc leach residues while minimizing the dissolving of components such as sulphur, lead and iron. Appropriate leaching conditions for selective silver leaching are achieved in accordance with the present invention by controlling the process parameters such as chloride concentration, pH and redox potential in the leaching. Silver can then be conveniently recovered from the leach solution by methods such as cementation or sulphide precipitation.

The method of the present invention provides an economical and ef- ficient way of recovering silver from direct zinc leach residues, which have only used for example for landfill purposes without utilizing the silver values contained therein. The use of copper chloride as an additive in the leaching step is not necessary. The process of the present invention has also the advantage that it can be directly combined with metallurgical zinc leaching processes, without intermediate treatment stages such as roasting.

BRIEF DESCRIPTION OF THE DRAWINGS

In the following the invention will be described in greater detail by means of preferred embodiments with reference to the attached drawings, in which

Figure 1 is a block diagram of an exemplary embodiment of the method of the invention;

Figure 2 is a graphical presentation showing the effect of the concentration of NaCI on the dissolution of silver and other metals in the leaching;

Figure 3 is a block diagram of a silver leaching system, according to an exemplary embodiment; and

Figure 4 is a flow diagram of a control of a silver leaching process according to an exemplary embodiment.

DETAILED DESCRIPTION OF THE INVENTION

The invention relates to a method of recovering silver from a direct zinc leach residue. The method of the invention comprises:

(a) a silver leaching step, wherein the direct zinc leach residue is subjected to oxidative chloride leaching to obtain a silver-containing leach solution, and wherein the leaching is performed in the following conditions:

(i) chloride concentration of the leach solution in the range of 25 to 70 g/l, (ii) pH of the leach solution in the range of 1.6 to 2.6, and

(iii) redox potential of less than 460 mV (Pt vs. Ag/AgCI), and

(b) a silver recovery step, wherein silver is recovered from the silver- containing leach solution.

The direct zinc leach residue used as the starting material in the method of the invention refers to a residue directly obtained from leaching of a zinc concentrate. Consequently, the residue is a direct solid product of zinc leaching, such as sulphuric acid leaching, without any further treatments of the residue for example by roasting.

The silver content of the direct zinc residue is typically in the range of 100 to 500 ppm.

The elemental sulphur content of the direct zinc leach residue is as a rule more than 50 %, typically 60 to 70%.

The direct zinc leach residue further contains iron in an amount of 1 to 10 %. Iron is present in a form that is soluble in the chloride leaching conditions.

Furthermore, the direct zinc leach residue as a rule contains the following metals:

- copper in an amount of 0.1 to 1 %,

- lead in an amount of 5 to 15%,

- zinc in an amount of 1 to 2%.

In the leaching step (a) of the present invention, the chloride concentration is adjusted to a range of 25 to 70 g/l, preferably 30 to 40 g/l (expressed as CI ^" ). In the recited chloride range, silver is dissolved, while lead remains in the solid residue. The adjustment of the chloride concentration to the desired range is typically done by adding NaCI to the leaching solution.

Furthermore, in the leaching step (a) of the present invention, pH of the leach solution is adjusted to a range of 1 .6 to 2.6, preferably 1 .6 to 2.0. The pH adjustment may be done by adding limestone or sodium hydroxide, or sul- phuric acid or hydrochloric acid, for example. By operating in the recited pH range, iron will not dissolve, but precipitates as hematite.

Furthermore, in the leaching step (a) of the present invention, the redox potential is adjusted to a range of less than 460 mV (Pt vs. Ag/AgCI), preferably to a range of less than 460 mV (Pt vs. Ag/AgCI) and higher than 350 mV (Pt vs. Ag/AgCI). In the recited redox potential range, sulphur remains in the solid residue and does not dissolve together with silver. The redox potential in the leaching step (a) is controlled by feeding a gas selected from oxygen and air to the leach solution. In an embodiment of the invention, the method is performed in the presence of sulphate in the leach solution. The sulphate is normally inherently present in the leaching solution, originating from the sulphur compounds of the high-sulphur zinc leach residue. The amount of the sulphate in the leach solution may be in the range of 5 to 10 g/l, expressed as S0 ₄ ^2" . Sulphate may also be added, for example in the form of sodium sulphate. Sulphate has been found to prevent lead dissolution.

The leaching step (a) is performed at a temperature of 70 to 120°C, preferably 90 to 100°C.

The leaching step (a) provides a silver-containing leach solution and a solid residue, which are subjected to solid/liquid separation.

Silver can be conveniently recovered from the silver-containing leach solution in the following silver recovery step (b) by various methods, such as cementation or sulphide precipitation. Cementation of silver may be performed with zinc powder, for example. Sulphide precipitation of silver may be performed using hydrogen sulphide, for example.

The silver recovery step (b) provides a silver-containing solid product, which is then separated from the silver-depleted solution by solid/liquid separation, such as filtering.

In an embodiment of the invention, the method further comprises, after the silver recovery step (b), a further step (c) of precipitating zinc from the silver-depleted solution to obtain a zinc-containing precipitate and a metal- depleted solution. Copper may be precipitated together with silver. In the pre- cipitation step, zinc and optionally copper may be precipitated as hydroxides by pH adjustment using soda (Na ₂ C0 ₃ ). A suitable pH for the precipitation is 6 to 7. The zinc (and copper) containing precipitate is separated from the metal- depleted solution by solid/liquid separation, for example by filtering.

The zinc (and copper) containing precipitate thus obtained may be introduced to direct leaching of zinc for further recovery of zinc. The metal- depleted solution may be circulated back to the silver leaching step (a).

Consequently, in an embodiment of the invention, the method of the invention may be integrated with a metallurgical zinc leaching process as a preceding step. The method of the invention may thus further comprise, prior to the silver leaching step (a), a step (aO) of leaching zinc from a zinc concentrate. The zinc leaching step (aO) may comprise conventional H ₂ S0 ₄ leaching, for example. The zinc leach residue obtained from the zinc leaching step is then directly introduced to the silver leaching step (a) and further to the silver recovery step (b) in accordance with the present invention.

In an aspect of the invention, the invention also relates to an appa- ratus for recovering silver from a direct zinc leach residue, which apparatus comprises

a) a silver leaching unit, which is adapted for producing a silver- containing leach solution by oxidative chloride leaching in the following conditions:

(i) chloride concentration of the leach solution in the range of 25 to 70g/l,

(ii) pH of the leach solution in the range of 1.6 to 2.6, and

(iii) redox potential of less than 460 mV (Pt vs. Ag/AgCI), and

(b) a silver recovery unit, which is adapted for recovering silver from the silver-containing leach solution to produce a solid silver- containing product and a silver-depleted solution.

In an embodiment of the invention, the silver recovery unit is followed by a zinc precipitation unit, which is adapted for precipitation of zinc to produce a zinc-containing precipitate and a metal-depleted solution.

In an embodiment of the invention, the zinc precipitation unit comprises means for circulating the metal-depleted solution to the silver leaching unit.

In an embodiment of the invention, the silver leaching unit is preceded by a zinc leaching unit, which is adapted for producing a zinc- contain- ing solution and a zinc leach residue from a zinc concentrate.

In an embodiment of the invention, the zinc precipitation unit comprises means for circulating the zinc-containing precipitate to the zinc leaching unit for further recovery of zinc.

Furthermore, the apparatus of the invention comprises the neces- sary inlets and outlets for providing and recovering process streams.

In an embodiment of the invention, the apparatus comprises means for performing the steps of the method described above.

The apparatus of the invention also comprises the necessary solid/liquid separation units for separating solid residues or solid reaction products from liquid reaction media. Consequently, the apparatus also comprises, in connection with or after the silver leaching unit, a first solid/liquid separation unit for separating the silver-containing leach solution from the solid leach residue. Furthermore, the apparatus comprises, in connection with or after the silver recovery unit, a second solid/liquid separation unit for separating the solid silver product from the silver-depleted leach solution. Furthermore, the appa- ratus of the invention also comprises, in connection with or after the zinc precipitation unit, a third solid/liquid/separation unit for separating the zinc precipitate from the metal-depleted solution.

An aspect of the invention is a method of controlling a leaching process for recovering silver from a direct zinc leach residue, wherein the direct zinc leach residue is subjected to oxidative chloride leaching to obtain a silver- containing leach solution, said method comprising

measuring chloride concentration of the leach solution,

measuring pH of the leach solution,

measuring redox potential during the leaching,

controlling the chloride concentration, the pH and the redox potential of the leach solution based on the measurements such that the leaching is performed in the desired leaching conditions.

In exemplary embodiments, said controlling comprises at least one of following steps:

controlling chloride concentration of the leach solution by feeding sodium chloride,

controlling pH of the leach solution by feeding limestone, sodium hydroxide, sulphuric acid or hydrochloric acid,

controlling redox potential by controlling oxygen or air feed to the leaching process.

A further aspect of the invention is a control system for implementing the control method, comprising

a measurement unit configured to measure chloride concentration of the leach solution,

a measurement unit configured to measure pH of the leach solution, a measurement unit configured to measure redox potential during the leaching,

a controller configured to control the chloride concentration, the pH and the redox potential of the leach solution based on measurement results from said measurement units. In exemplary embodiments said controller is configured to control one or more of the following:

a feeding valve or pump configured to feed sodium chloride for controlling chloride concentration of the leach solution,

a feeding valve or pump configured to feed limestone or sodium hydroxide or sulphuric acid or hydrochloric acid for controlling pH of the leach solution, and/or

a feeding valve or pump configured to adjust oxygen or air feed for controlling redox potential.

A still further aspect of the invention is a computer program comprising a program code for performing the steps of the control method, when the program is run on one or more computer or processor.

In the following, the invention is illustrated by referring to Figure 1 , which is an exemplary embodiment of the invention where silver leaching and silver recovery are combined with preceding zinc leaching and subsequent zinc precipitation. Zinc leach residue 15 from a zinc leaching unit 10 is intro- duded to a silver leaching unit 20, which produces a silver-containing leach solution and a solid residue, which are separated in a first solid/liquid separation unit 25. The silver-containing leach solution is introduced to a silver recov- ery unit 30, which produces a solid silver product and a silver-depleted solution, which are separated in a second solid/liquid separation unit 35. The solid silver product 36 is withdrawn from the process. The silver-depleted solution is introduced to a zinc precipitation unit 40, which produces a zinc precipitate, which may also contain copper, as well as a metal-depleted solution. The zinc precipitate and the metal-depleted solution are separated in a third solid/liquid separation unit 45. The metal-depleted solution is circulated to the silver leaching unit 20. The zinc precipitate is introduced to the zinc leaching unit 10.

As described above, an aspect of the invention is a careful selection and control of leaching conditions which are suitable for dissolving silver from high-sulphur direct zinc leach residues and, on the other hand, tend to minimize the dissolving of components such as sulphur, lead and iron. Figure 3 is a block diagram of an exemplary silver leaching system wherein such control may be implemented by controlling leaching process parameters, such as chloride concentration, pH and redox potential in the leaching. In the illustrat- ed example, the Ag leaching unit 20 may comprise a stirred reactor tank 200, and necessary inlets and outlets for providing and recovering process streams, e.g. an incoming residual stream 15 from Zn leaching unit 10 (Figure 1 ) and an outgoing material solution stream to a subsequent separation unit 25. Examples of commercial reactors applicable for reactor tank 200 include OKTOP® reactors manufactured by Outotec. The reactor tank 200 may further comprise inlets for feeding sodium chloride 202, limestone or sodium hydroxide 204, and oxygen or air 206. The feed of the sodium chloride 202 to the reactor tank 200 may be controlled by a feeding valve 208 that may be any type of process control valve. Similarly, the feed of limestone or sodium hydroxide or sulphuric acid or hydrochloric acid 204 and the feed of oxygen/air 206 to the reactor tank 10 may be controlled by a feeding valve 210 or 212, respectively. Alternatively, pumps or other type of process devices may be used instead of valves. Further, a pH measurement unit or sensor 214 may be provided to measure the pH of the solution in the tank, a redox potential measurement unit or sensor 216 may be provided to measure the redox potential in leaching, and a chlo- ride concentration measurement unit or sensor 218 may be provided to measure the chloride concentration in the solution in the tank. A pH measurement signal from the pH sensor 214 and a redox potential measurement signal from the sensor 216 may be inputted to a controller unit 220. The sensor 218 may be implemented as a sampling unit which provides samples of the solution to an analyser 222 via a sampling piping, for example. An example of a suitable analyser is Outotec Courier® 5 SL on-line analyzer. Also the pH of the solution may be measured by the analyser 222 at the same time as the chloride concentration. As a further example, the pH and/or the chloride concentration may be determined from the residual stream 15 prior to the tank. As a still further example, the pH and/or the chloride concentration may be determined from the residual stream 15 or the tank 200 by laboratory tests. Measurement data from the analyser 222 may be transferred to the controller 220.

The controller 220 may be configured to control the feeding valves 208, 210 and 212 based on the inputted measurement signals. The control signal from the controller 220 may be applied also to a control station 224 of the waste water processing system. The control station 224 may be, for example, a process control system or a control room computer. In an exemplary embodiment, the controller 220 may be part of the control station 224, in which case the measurement signals may be supplied to the control station 224 which is configured to control the feeding valves 208, 210 and 212. An exemplary flow diagram of a control of the Ag leaching process is illustrated in Figure 4. The control process may be an automatic or semiautomatic control. In a semiautomatic control some of the control phases may be done manually e.g. from the control station 224 by an operator. First a re- sidual stream 15 is fed to the reactor tank 200 for Ag leaching (step 402). Leaching conditions, such as chloride concentration, pH and redox potential in leaching, are determined or measured (e.g. by means of sensors 214, 216, 218 and the analyser 222), step 404. The controller 220 may compare the determined leaching conditions with the predetermined leaching conditions suita- ble for the Ag leaching (step 406). In the case any one of the leaching conditions deviate from the respective predetermined condition, the controller 220 may control the respective one or ones of feeding valves 208, 210 and 212 to feed an appropriate amount of sodium chloride, limestone/sodium hydroxide/sulphuric acid/hydrochloric acid or oxygen/air so as to change the deviating leaching condition towards the predetermined condition (step 408). Steps 404, 406 and 408 may be repeated until the desired leaching conditions are achieved. If the measured leaching conditions do not deviate from the desired leaching conditions, i.e. the process has received a steady state, the control procedure may directly return to the measurement step 404. This type of con- trol and measurement loop may continue maintaining the process in the steady state.

The control techniques described herein may be implemented by various means. For example, these techniques may be implemented in hardware (one or more devices), firmware (one or more devices), software (one or more modules), or combinations thereof. For a firmware or software, implementation can be through modules (e.g., procedures, functions, and so on) that perform the functions described herein. The software codes may be stored in any suitable, processor/computer-readable data storage medium(s) or memory unit(s) and executed by one or more processors. The data storage medium or the memory unit may be implemented within the processor or external to the processor, in which case it can be communicatively coupled to the processor via various means as is known in the art. Additionally, components of systems described herein may be rearranged and/or complimented by additional components in order to facilitate achieving the various aspects, goals, advantages, etc., described with regard thereto, and are not limited to the pre- cise configurations set forth in a given figure, as will be appreciated by one skilled in the art.

EXAMPLES

In the following examples, a direct leach residue from sulphuric acid leaching of a zinc concentrate was used as the raw material. The raw material contained 80% sulphur, 10% lead, 5% iron, 2% zinc and 300 ppm silver. The leaching tests were carried out in a 3-litre titanium reactor with mechanical agitation. pH of the leach solution was controlled with sodium hydroxide by pumping sodium hydroxide to the solution. EXAMPLE 1

Leaching of silver was performed in the process conditions shown in Table 1 . Copper concentration during leaching was increased to show the effect of copper on silver dissolution. Copper chloride was added to the leach solution every eight hours. The oxygen feed was 300 ml/min. The concentra- tion of NaCI was 250 g/l, which corresponds to a chloride concentration of about 152 g/l.

TABLE 1

During the first eight hours, the copper concentration was 0.1 g/l and the yield of silver was 50%, lead 90%, iron 9% and zinc 34%. After 16 hours with a copper concentration of 1 .0 g/l, the yield of silver was 52%, lead 83%, iron 16% and zinc 42%. After 24 hours with a copper concentration of 5.0 g/l, the yields were 54% silver, 72% lead, 7% iron and 41 % zinc. At the end of the test with a copper concentration of 15.0 g/l, the yields were 60% silver, 70% lead, 5% iron and 43% zinc.

The results indicate that the copper concentration had no significant effect on the dissolution of silver, lead, iron or zinc. However, it was found that copper concentration does have a significant effect on sulphur dissolution, which should be avoided. Sulphur did not dissolve when the copper concentration was low, i.e. 0.1 g/l and the redox potential of the solution was under 460 mV (Pt vs. Ag/AgCI). Sulphur dissolution started when copper concentration was over 1 g/l and the redox potential of the solution was over 480 mV (Pt vs. Ag/AgCI).

Consequently, the addition of copper is not required in the method of the present invention for selective silver dissolution.

EXAMPLE 2

Example 2 shows the effect of the concentration sodium chloride (NaCI) on silver dissolution and lead dissolution. The sodium chloride concentration was increased during the dissolution by adding sodium chloride every eight hours. The leaching conditions are presented in Table 2. The sodium chloride concentration in the range of 50 to 200 g/l corresponds to a chloride concentration of about 30 to 121 g/l.

TABLE 2

The dissolution of metals is graphically presented in Figure 1 . After eight hours, the yields of metals were 49% silver, 3% lead, 12% iron and 44% zinc. After 16 hours, the yields of metals were 49% silver, 15% lead, 23% iron and 46% zinc. After 24 hours, the yields were 52% silver, 48% lead, 34% iron and 45% zinc. At the end of the test, the yields were 55% silver, 72% lead, 34% iron and 46% zinc. Those results indicate that sodium chloride concentration had no significant effect on the dissolution of silver or zinc, while affecting the dissolution of lead, which is to be avoided. Dissolution of lead increases when sodium chloride concentration is over 50 g/l.

EXAMPLE 3

Example 3 shows selective dissolution of silver without copper addition. The leaching conditions are presented in Table 3. The sodium chloride concentration 50 g/l corresponds to a chloride concentration of about 30 g/l. TABLE 3

At the end of the test, the yields were 62% silver, 1 .7% lead, 36% iron and 33% zinc. The results indicate that leaching of silver is possible with low yield of lead. Copper was not added to the initial solution. Redox potential of solution was under 460 mV (Pt vs. Ag/AgCI).

It will be obvious to a person skilled in the art that, as the technology advances, the inventive concept can be implemented in various ways. The invention and its embodiments are not limited to the examples described above but may vary within the scope of the claims.