Method for recovery of zinc
Patent Information
- Application Number
- EP2024712270
- Authority / Receiving Office
- EP · EP
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2023-03-22
- Filing Date
- 2024-03-22
- Publication Date
- 2026-01-28
AI Technical Summary
Current zinc recovery processes are energy-intensive, consume large quantities of reagents, produce significant CO2 emissions, and require substantial investments for infrastructure, particularly in electrolysis halls, while also facing challenges with impurities and low zinc concentration in final products.
A zinc recovery process involving leaching in a basic alkaline medium to form a supersaturated zinc solution, followed by calcium compound addition to precipitate zinc oxide, which is then heated to produce a high-concentration zinc oxide product with reduced reagent use and lower CO2 emissions, allowing for efficient zinc production and recycling of depleted solutions.
The process achieves a high yield of zinc oxide with over 95% purity, reducing energy consumption and reagent usage by more than 70% compared to traditional methods, and enables continuous operation with efficient recycling of materials.
Smart Images

Figure EP2024057778_26092024_PF_FP
Abstract
Description
[0001] ZINC RECOVERY PROCESS The present invention relates to a process for recovering zinc from a zinc-containing material. The Waelz process allows zinc to be extracted from an ore or secondary material and recovered in the form of a zinc oxide richer than the original ore or secondary material. The enriched zinc oxide is sold to zinc smelters to produce metal by conventional methods. However, the Waelz process is a thermal process that consumes a lot of energy and emits a lot of carbon dioxide. There are also processes for acid leaching of oxidized ores that involve purification and electrolysis to directly produce zinc in the form of metal. One of the disadvantages is the large amount of acid used during the process. In addition, certain impurities harmful to electrolysis and very difficult to remove may be present in the ore and contaminate theleaching solution (Mg, Mn, F, etc.). Finally, the financial and human investment for an electrolysis hall is very significant and can only be justified for very large deposits. Document WO 2020 / 019834 proposes an attack on a zinc-poor rock with ammonia and ammonium carbonate. After filtration of the residue, a first direct addition of lime is made to obtain a first precipitate which is filtered. Then a second addition of lime leads to the precipitation of a second precipitate. Calcination is carried out on the second precipitate to provide a mixture which contains zinc oxide, oxides and / or calcium carbonate. One of the disadvantages lies in the use of ammonia which leads to environmental and safety problems. In addition, the zinc concentration in the final product remains low. Processes involving caustic soda leaching (sodium hydroxide), purification and electrolysis havebeen proposed. Sodium hydroxide leaching has the advantage of being more selective than acid leaching. In addition to the investment required for the electrolysis plant, another disadvantage is that during the electrolysis of sodium zincate solutions, the zinc metal is recovered in powder form, whereas it is recovered in the form of massive cathodes in an acidic medium. The metal powder must be melted to cast ingots. However, this melting results in very costly metal losses. In 1965, Merrill and Lang investigated several methods for recovering zinc from leaching solutions of zinc ores oxidized by caustic soda. Apart from electrolysis, zinc can be precipitated by carbonation, sulfidation, or dilution and recovered in the form of a marketable concentrate. However, all of these methods have disadvantages. Carbonation aims to reduce the solubility of zinc by converting caustic soda into sodium carbonate.soda by bubbling carbon dioxide. The zinc then precipitates in the form of oxide. The disadvantage is that the consumption of caustic soda is prohibitive. It can be regenerated by reacting soda ash with lime. Lime consumption is, however, very high, on the order of three or four tons of quicklime per ton of zinc. Sulfiding consists of the precipitation of zinc sulfide by reacting the sodium zincate solution with elemental sulfur. This process also leads to significant consumption of soda, which affects profitability. Finally, zinc can be precipitated in the form of oxide by dilution. This method requires very substantial additions of water. To recover the caustic soda, all of this water must then be evaporated, which is extremely energy-intensive. Document WO 2013 / 036268 proposes a process for treating waste containing, for example, 65% Zn by attacking it with a NaOH solution. Most of thewaste is dissolved in the solution. The zinc-rich liquor generated is then separated from the waste by filtration. This process involves the addition of powdered Zn metal to the liquor to separate the Pb, Cu, Sn and Cd from it. Zn oxide then precipitates following the addition of methanol which acts as an anti-solvent. A disadvantage of this process is the use of an anti-solvent which must be distilled from the zinc-depleted solution in order to recycle the NaOH. In order to recover zinc from materials which cannot be sufficiently enriched by simple physical methods to be sold to smelters, there is a real need to provide a zinc recovery process which is energy efficient, requires the use of few reagents, emits little carbon dioxide and does not require a heavy investment for the user. To solve this problem, the present invention provides a zinc recovery processwhich comprises the following steps: - Supplying a material which contains zinc in oxidized form, - Leaching the material in an alkaline basic medium with formation of a solid residue and a zinc-supersaturated solution (i) or a zinc-rich solution (ii), - Separation (A') of the solid leaching residue from the zinc-supersaturated solution (i) or the zinc-rich solution (ii), - Optionally: • addition of a calcium compound, preferably chosen from the group comprising lime, calcined dolomite and combinations thereof, to said zinc-rich solution (ii) or to the zinc-supersaturated solution (i) to form (with formation of) a pulp which contains solid calcium zincate and a zinc-depleted basic solution, • separation (B') of at least a portion of the zinc-depleted basic solution from the calcium zincate pulp, • heating said calcium zincate pulp consisting of the solid calcium zincate and the rest of the basic solutiondepleted in zinc with formation of a zinc-supersaturated solution (iii) and a solid matter, • separation (C') of the solid matter obtained after the heating step to preserve (with preservation of) the zinc-supersaturated solution (iii) and optionally recycling of this solid matter to the step of addition of a calcium compound, - Heating of said zinc-supersaturated solution (i) obtained after said separation (A') or of the zinc-supersaturated solution (iii) optionally obtained after the separation step (C') of said solid matter to precipitate (precipitating), preferably predominantly, a zinc oxide in a zinc-depleted solution, - Separation (D') of the zinc oxide formed during heating of the zinc-supersaturated solution (i) or (iii), - Optionally, recycling of at least a portion of said zinc-depleted (basic) solution formed during at least one of the steps of the process by adding it to the leaching step in basic medium or in saidzincate pulp before heating and supersaturation with zinc. From a material which contains zinc, the process makes it possible, in an easy and efficient manner, to form a solution supersaturated with zinc (i; iii) which after heating produces a zinc oxide which can be sold to zinc foundries (smelters) to produce zinc metal or as technical zinc oxide in particular for the vulcanization of elastomers, the production of enamels, animal feed. The heating step makes it possible to precipitate the zinc oxide in the solution which is therefore depleted in zinc. This spontaneous precipitation of zinc oxide constitutes one of the key aspects of the present invention. Preferably, the zinc oxide formed after the heating step constitutes the product predominantly present in said zinc-depleted solution. Indeed, the heating step which causes the precipitation of zinc oxide leads to a precipitation of a solid, the major part of which is formed of this zinc oxide,preferably at least 80% by weight of zinc oxide, preferably at least 90% by weight of zinc oxide, more preferably at least 95% by weight of zinc oxide, relative to the total weight of precipitate formed. The process according to the present invention is thus more economical, less energy-intensive, requires smaller quantities of reagents, produces less CO2 (reduction of more than 70%) compared to known processes, while ensuring a high zinc production yield. It is also possible, preferably, to produce a zinc-rich solution (ii) to which the calcium compound is added in order to form (with formation of) a calcium zincate pulp. After removing part of the depleted solution, a step of heating the calcium zincate pulp makes it possible to produce a zinc-supersaturated solution (iii) which will make it possible to obtain zinc oxide. Advantageously, it is also possible to use the zinc-supersaturated solution (i) andadding the calcium compound to it to form (with formation of) the calcium zincate pulp. After removing a portion of the depleted solution, when the thickened calcium zincate pulp is heated according to the steps listed above, this provides a zinc (iii) supersaturated solution. It should be noted that when the zinc (iii) supersaturated solution is obtained by the route set out above, this zinc (iii) supersaturated solution has a higher zinc concentration than the supersaturated solution (i) or the zinc (ii) rich solution that was initially provided. The effect of adding this step is either to obtain a more concentrated zinc solution or to obtain a purer solution. The zinc (basic) depleted solution that was generated during the process, preferably by the precipitation of zinc oxide, can be recycled either to the leaching step or to the thickened calcium zincate pulp by separating a portion of thedepleted solution before the heating and zinc supersaturation step. Preferably, the precipitation of calcium zincate by adding the calcium compound to said zinc-rich solution (ii) or to said zinc-supersaturated solution (i) is carried out by applying a temperature of less than 70°C or between 0 and 70°C, preferably less than 50°C, more preferably less than 30°C. Advantageously, the precipitation of calcium zincate following the addition of the calcium compound to said zinc-rich solution (ii) or to said zinc-supersaturated solution (i) is carried out over a period of time of between 1 and 4 hours. Preferably, seeds comprising hydrated calcium zincate may be added to said zinc-rich solution (ii) or to the zinc-supersaturated solution (i) followed by an addition of a calcium compound, preferably selected from the group comprising lime, calcined dolomite and combinations thereof, leading to the formationof a pulp which contains solid calcium zincate and a basic solution depleted in zinc. This addition of seeds can thus take place before this possible addition of the calcium compound. More preferably, the step of heating said zinc-supersaturated solution (i) obtained after said separation (A') or of the zinc-supersaturated solution (iii) possibly obtained after the separation step (C') of said solid material to precipitate a zinc oxide in a zinc-depleted solution is carried out in the presence of zinc oxide, serving as precipitation seeds. According to a particularly preferred embodiment, the step of heating said zinc-supersaturated solution (i) obtained after said separation (A') or of the zinc-supersaturated solution (iii) possibly obtained after the separation step (C') of said solid material to precipitate (precipitant), preferably predominantly, a zinc oxide in a zinc-depleted solution is carried out at a temperatureabove 70°C, preferably above 90°C, optionally for a period of time of at least one hour, advantageously up to 8 hours. According to an advantageous embodiment, during the leaching step, an addition of a calcium and / or magnesium compound in a stoichiometric amount is carried out to precipitate (precipitant) impurities chosen from the group comprising silica, alumina or carbonate. Calcium silicates, calcium aluminates and calcium carbonates can thus be formed. A calcium and / or magnesium compound can also preferably be added to the zinc-supersaturated solution (i) or to the zinc-rich solution (ii) obtained after said separation of said solid residue. In this way, impurities, such as silica, alumina or carbonate, are separated from the zinc-containing solution and recovered in a distinct solid. The calcium and / or magnesium compound is preferably chosen from the group comprisingquicklime, hydrated lime, dolomite, calcined dolomite, magnesia, limestone and mixtures thereof. The presence of silica in the supersaturated solution may inhibit the precipitation of zinc oxide upon heating. Optionally, if the zinc-supersaturated solution (i) or (iii) contains silica, a specific purification step may be carried out before the precipitation of zinc oxide, for example, by contacting the supersaturated solution with silica seeds so as to force the precipitation of dissolved silica. Once the silica concentration has been reduced, the zinc-supersaturated solution may be brought to the zinc oxide precipitation step. Advantageously, the leaching step is carried out at a temperature below 90°C, preferably below 70°C, optionally for a period of time less than or equal to 3 hours, preferably less than or equal to 2.5 hours, more preferably less than 2 hours to preventearly precipitation of zinc oxide. More advantageously, if a supersaturated solution (i) is generated during the leaching step, this is carried out at a temperature below 90°C, preferably below 70°C, optionally for a period of time less than or equal to 3 hours, preferably less than or equal to 2.5 hours, more preferably less than 2 hours to prevent early precipitation of zinc oxide. This embodiment is preferred and can be applicable to all variants of the process. According to a particularly advantageous alternative embodiment, the leaching step can be carried out at a temperature above 50°C, preferably above 90°C, more preferably above 150°C, optionally for a period of time less than 4 hours to prevent precipitation of calcium zincate. This advantageous alternative embodiment is also preferred when the zinc-rich solution (ii) isgenerated. This alternative embodiment is also advantageous when the material contains zinc and also calcium, or when a calcium-containing compound is added to the leaching step, a temperature above 50°C is applied, preferably for a period of time less than 4 hours. This makes it possible to prevent early precipitation of calcium zincate at this stage of the process. Preferably, the step of heating said calcium zincate pulp consisting of calcium zincate and the remainder of the zinc-depleted basic solution is carried out at a temperature above 50°C, preferably between 80°C and 95°C. This heating step is preferably carried out for a period of time between 0.1 and 4 hours, preferably between 0.5 and 2 hours, more preferably 0.5 and 1 hour. According to an additional embodiment, the leaching can be carried out in several stages, preferably in two counter-current, as set out below: - A first leaching of the material in an alkaline basic medium with obtaining a solid residue depleted in zinc and a solution partially enriched in zinc, - A first separation of the solid leaching residue, - A second leaching by the solution partially enriched in zinc with formation of a solution enriched in zinc, or of a solution supersaturated in zinc, and of a solid material, - A second separation of the solid material generated during the second leaching and recovery of the solution supersaturated in zinc (i) or of the solution rich in zinc (ii), - Optionally, recycling of the solid material recovered after said second separation to the first leaching. Preferably, an addition of a calcium or magnesium compound is carried out during the first leaching. Preferably, the second leaching is carried out without addition of a calcium compound. Preferably, said first leaching iscarried out at a temperature greater than or equal to 60°C, preferably greater than or equal to 70°C. This makes it possible to avoid the precipitation of calcium zincate. According to an advantageous embodiment, the second leaching is carried out at a temperature lower than 70°C, preferably lower than 60°C, so as to avoid the precipitation of zinc oxide and to minimize the dissolution of impurities. Advantageously, the second leaching is carried out for a short period of time, i.e. less than 2 hours, preferably less than 1 hour, so as to avoid the precipitation of calcium zincate and to minimize the dissolution of impurities. Preferably, it is possible to add a step of purifying the solution by cementation of metals more noble than zinc on zinc dust added to the solution. According to an even more advantageous embodiment, the calcium and / or magnesium compound is chosen from the group comprising lime, dolomitecalcined dolomite, magnesia and mixtures thereof. This group relates to the removal of impurities mentioned above, preferably after having carried out the leaching step. However, when the addition of calcium compound takes place for the purpose of forming the calcium zincate pulp, the calcium compound is chosen from the group comprising lime, calcined dolomite and combinations thereof. The cementation step disclosed within the scope of the present invention can be inserted at any stage of the process. Preferably, the zinc-depleted solution generated in the process is purified of metallic impurities more noble than zinc by cementation on a metallic powder, preferably a zinc metal powder, preferably before the possible recycling step mentioned above. According to a preferred variant, the zinc-supersaturated solution (i) (iii) or the zinc-rich solution (ii) generated in the process is purified of metallic impurities more noble than zinc by cementation on ametal powder, preferably a zinc metal powder. Advantageously, at least one of the solids separated from the solutions containing zinc and alkali hydroxides is washed, preferably with water, so as to recover the zinc and alkali hydroxides from the solution impregnated in said at least one solid. The washing solutions are preferably recycled in one or more of the steps of the process according to the invention. The water balance of the process is balanced by compensating for water inflows either by bleeding, or by water evaporation, or by reverse osmosis, or by a combination of these techniques. The volume of the bleeding is preferably adjusted to control the concentration in the solution of the most difficult-to-remove impurities, such as alkali chlorides, at an acceptable level. To complete the balance, excess water is preferably removed by multiple-effect evaporation or mechanical vapor compression so as to minimizethe amount of energy consumed. According to an advantageous embodiment, the zinc-supersaturated solution (i) or (iii) or the zinc-rich solution (ii) generated in the process is purified so as to reduce its silica concentration to a content of less than 1 g / L, preferably less than 0.5 g / L, and even less than 0.3 g / L before the zinc oxide precipitation step. This purification can be carried out by contacting the solution with silica precipitation seeds or any other equivalent method. The zinc recovery process according to the present invention can be operated continuously, in particular by reusing as much as possible the products generated in the process by feeding several stages and allowing continuous recycling. Preferably, calcium zincate seeds are added to the precipitation of said calcium zincate pulp. Figure 1 is a schematic view of an embodiment of the process according to the present invention. Figure 2 is a viewschematic of a variant of the process according to the present invention. Figure 3 is a schematic view of a preferred embodiment of the process according to the invention. Other characteristics and advantages of the present invention will be drawn from the non-limiting description which follows, and with reference to the drawings and examples. The present invention thus aims to extract zinc from a material called a raw or secondary material and to recover it in a concentrate with higher value. According to the invention, the material which contains zinc in oxidized form is preferably any raw or secondary material containing zinc which can be leached in a caustic soda solution. This raw material may include at least one so-called oxidized ore which contains zinc in the form of an oxidized mineral such as smithsonite, hemimorphite, hydrozincite, willemite or in the form of a zinc carbonate and / or a zinc silicate and / or calcium zincate. The secondary material may befrom lead metallurgy (slag), dust from scrap metal recycling (EAFD), etc.… In the context of the present invention, the zinc-containing material may be chosen from the group comprising ores (raw materials), secondary materials and mixtures thereof. In the present invention, the leaching step takes place in an alkaline basic medium obtained by adding a solution which comprises an alkaline basic compound, preferably chosen from the group comprising sodium hydroxide, potassium hydroxide, alkali metal carbonate, lithium hydroxide and mixtures thereof. According to a preferred embodiment, the alkaline basic compound, preferably chosen from the group comprising sodium hydroxide, potassium hydroxide, alkali metal carbonate, lithium hydroxide and mixtures thereof, has a concentration of between 100 and 300 g / L, preferably between 100 and 250 g / L, more preferably between 100 and 200 g / L, advantageouslybetween 130 and 200 g / L. The addition of an anti-solvent is not required in the context of the present invention. In other words, less than 80% by volume may be added to the zinc-supersaturated solution (i) or (iii) relative to the volume of said zinc-supersaturated solution (i) or (iii). Alternatively, an anti-solvent may be added without having sufficient effect in the precipitation of a zinc oxide as described in the context of the present invention. According to a preferred embodiment of the process according to the invention, the formation by precipitation of zinc oxide in solution is carried out in the absence of an added quantity of an anti-solvent, for example ethanol or methanol. In this context, the expression "in the absence of an added quantity of an anti-solvent" means that any added quantity will have little or no effect on the precipitation of zinc oxide as described in the context of the present invention. The leaching step of the zinc-containing material ispreferably carried out in a solution containing caustic soda, preferably at a concentration of between 130 and 200 g / L. The caustic soda-based solution may also contain zinc, soluble in this medium in the form of sodium zincate (Na2ZnO2). The caustic soda-based solution may also contain impurities such as traces of silicon, aluminum, lead or soluble salts (carbonates, chlorides and others). Advantageously, the leaching temperature is between 0 and 300°C. If the leaching temperature exceeds the boiling point of the solution at atmospheric pressure, the leaching is carried out under saturated steam pressure in order to prevent boiling and conduct the leaching in the liquid phase. The leaching temperature is chosen, on the one hand, so as to maximize the leaching yield of zinc, or even of other recoverable metals, and on the other hand, so as to minimize the reactionsparasites such as the dissolution of impurities or the excessive consumption of caustic soda by the gangue. Thus and advantageously, when the material contains Ca, the leaching step is carried out at a temperature above 50°C, possibly for a period of time less than 4 hours. Advantageously, the leaching step is carried out at a temperature below 90°C, preferably below 70°C, possibly for a period of time less than or equal to 3 hours, preferably less than or equal to 2.5 hours, more preferably less than 2 hours to prevent early precipitation of zinc oxide. More advantageously, if a supersaturated solution (i) is generated during the leaching step, this is carried out at a temperature below 90°C, preferably below 70°C, possibly for a period of time less than or equal to 3 hours, preferably less than or equal to 2.5 hours, morepreferably less than 2 hours to prevent early precipitation of zinc oxide. This embodiment is preferred and applicable to all variants of the process. According to a particularly advantageous alternative embodiment, the leaching step may be carried out at a temperature above 50°C, preferably above 90°C, more preferably above 150°C, optionally for a period of time less than 4 hours to prevent precipitation of calcium zincate. This advantageous alternative embodiment is also preferred when a solution rich in zinc (ii) is generated. This alternative embodiment is also advantageous when the material contains zinc and also calcium, or when a calcium-containing compound is added to the leaching step, a temperature above 50°C is applied, preferably for a period of time less than 4 hours. This makes it possible to prevent early precipitation ofcalcium zincate at this stage of the process. Leaching can be carried out in a single or multiple stages (e.g. in 2 stages, see Figure 3). In the latter case, the leaching stages will preferably be carried out in countercurrent with intermediate solid-liquid separation stages. At the end of leaching, the zinc-enriched solution is separated from the depleted solids by vacuum filtration, pressure filtration, centrifugation, decantation or any other suitable technique. The solid residue is preferably washed with water so as to recover the zinc and the basic alkaline compound, preferably selected from the group consisting of sodium hydroxide, potassium hydroxide, alkali metal carbonate, lithium hydroxide and their mixtures or caustic soda in the impregnated solution. The solid is then discharged while the solution advances to the zinc precipitation stage, or possibly, a purification stageintermediate. Thus, the zinc-supersaturated solution (i) or the zinc-rich solution (ii) obtained is used for the following steps: Optionally: • addition of a calcium compound to said zinc-rich solution (ii) or to the zinc-supersaturated solution (i) to precipitate (precipitate) solid calcium zincate in a zinc-depleted basic solution, • separation (B) of at least a portion of the zinc-depleted basic solution from the calcium zincate pulp, • heating said calcium zincate pulp consisting of solid calcium zincate and the remainder of the zinc-depleted basic solution with formation of a zinc-supersaturated solution (iii) and a solid matter, • separation (C) of the solid matter obtained after the heating step to preserve the zinc-supersaturated solution (iii) and optionally recycling this solid matter to the calcium compound addition step, - Heating said zinc-supersaturated solution (i) obtained aftersaid separation (A) or of the zinc-supersaturated solution (iii) optionally obtained after the separation step (C) of said solid material to precipitate (precipitate), preferably predominantly, a zinc oxide in a zinc-depleted solution, - Separation (D) of the zinc oxide formed during the heating of the zinc-supersaturated solution (i) or (iii), - Optionally, recycling at least a portion of said zinc-depleted (basic) solution formed during at least one of the steps of the process by adding it to the basic leaching step or to said thickened zincate pulp, preferably after removal of at least a portion of the zinc-depleted solution and before heating and zinc supersaturation. In the process according to the invention, the quantity of ore or secondary material introduced into the leaching is chosen so as to obtain the highest possible zinc concentration in the enriched solution, while maximizing the yield ofleaching. If the zinc contained in the material to be leached is present in the form of zinc oxide, the maximum zinc concentration of the enriched solution cannot exceed the solubility limit of zinc oxide because it is the most insoluble zinc compound in a solution comprising an alkaline basic compound, preferably chosen from the group comprising sodium hydroxide, potassium hydroxide, carbonate of an alkali metal, lithium hydroxide and mixtures thereof, preferably at a concentration of between 130 and 200 g / L. Particularly advantageously, when the zinc contained in the material to be leached is not present in the form of zinc oxide, but for example in the form of a zinc carbonate and / or a zinc silicate and / or calcium zincate, a zinc concentration higher than the solubility limit of zinc oxide can be achieved in the leaching solution. To achieve the highest zinc supersaturationpossible while achieving a high leaching efficiency, it is often practical to carry out several countercurrent leaching stages (see diagram in Figure 3). The operating conditions of the different leaching stages may be different. For example, the temperature for leaching fresh material may be colder than that for leaching depleted material to prevent re-precipitation of zinc oxide. Similarly, the duration of leaching fresh material may be shorter to prevent the formation of insoluble calcium zincate. Leaching with caustic soda has the advantage of being quite selective. Iron, calcium or magnesium do not go into solution in a basic medium, unlike in an acidic medium. The leaching solution, enriched with zinc, may however contain impurities such as silica, alumina, carbonate or lead. Silica,alumina and carbonate can be precipitated by adding lime up to concentrations of the order of one gram per liter, or even less, for silica and alumina, and up to concentrations of a few tens of grams per liter for carbonate depending on the concentration of basic alkaline compound, preferably chosen from the group comprising sodium hydroxide, potassium hydroxide, carbonate of an alkali metal, lithium hydroxide and mixtures thereof. Purification by adding lime is preferably carried out at a temperature above 50°C, and even above 60°C, so as to prevent precipitation of calcium zincate. Vigorous stirring of the zincate pulp and the use of finely divided lime promote high purification yields. Purification can be carried out in the presence of the zinc-depleted material, i.e. before separation of the leaching residue, or after. In the first case, theprecipitate of silica and / or alumina and / or carbonate is mixed with the residue of the leaching and separated at the same time from the zinc-enriched solution. In the second case, it is separated from the enriched solution and recovered without being mixed with the residue. In addition to the elimination of impurities which could contaminate the final zinc-rich product, the precipitation of silica, alumina and carbonate causes the regeneration of a basic alkaline compound preferably chosen from the group comprising sodium hydroxide, potassium hydroxide, lithium hydroxide and their mixtures in free form. It should be noted that these advantageous modes are all combinable with each other, whether for the first variant and / or the second variant according to the invention. In addition, this "countercurrent" mode can also be applied to the first and / or the second variant of the process according to the invention. The metals more noble than zinc which pass into solution with the zinc during theleaching, such as lead, copper or silver can be removed from the solution, in whole or in part, by cementation, preferably on zinc powder. Some impurities, notably sulfates, chlorides or alkali fluorides are more difficult to remove. They are generally tolerated in the leaching solution up to a certain level, of the order of a few tens of grams per liter. Their accumulation in the leaching circuit can be controlled by carrying out a bleeding. The zinc contained in the rich solution, purified or not, is then recovered by precipitation. The zinc is recovered from the supersaturated solution preferably in oxide form by breaking the supersaturation. To achieve this, the temperature of the solution is raised for several hours to more than 70°C, and preferably to more than 100°C. The zinc then precipitates in oxide form until it reaches the solubility limit of zinc oxide in the solution comprisingthe basic alkaline compound, preferably selected from the group comprising a compound selected from the group comprising sodium hydroxide, potassium hydroxide, alkali metal carbonate, lithium hydroxide and mixtures thereof. Precipitation seeds are preferably added to accelerate precipitation. For the purposes of the present invention, precipitation seeds are understood to mean zinc oxide crystals, originating for example from the recycling at the top of a portion of the precipitation pulp. The precipitated zinc oxide is recovered by filtration or any other solid-liquid separation process. The solid is preferably washed to recover the basic alkaline compound, preferably selected from the group comprising sodium hydroxide, potassium hydroxide, alkali metal carbonate, lithium hydroxide and mixtures thereof impregnated in the solid. The zinc-depleted solution can advantageously be recycled to the leaching, so as to minimize theconsumption of the process in the basic alkaline compound, preferably chosen from the group comprising sodium hydroxide, potassium hydroxide, carbonate of an alkali metal, lithium hydroxide and mixtures thereof. The separation steps included in the process according to the invention are liquid / solid separations and the person skilled in the art knows different suitable separation methods. The wash waters of the different solids can also be recycled at each stage of the process. The water balance of the circuit is then balanced by means of one or more evaporation stages, and / or bleeding. The invention provides for the use of a calcium compound, preferably lime, which makes it possible to precipitate a calcium zincate pulp consisting of solid calcium zincate and a basic solution depleted in zinc. This is particularly preferred when the zinc concentration of the rich solution, purified or not, is lower than the solubility limit ofzinc oxide. In this case, it is preferable to precipitate this calcium zincate to then form a solution supersaturated with zinc (iii) as reported in the present invention. Calcium zincate has a relatively low and very temperature-dependent solubility in solutions containing less than 250 grams per liter of caustic soda. To precipitate zinc from the rich sodium zincate solution, a calcium compound (e.g., lime), preferably finely divided, is therefore added to the solution at a temperature below 80°C, preferably below 50°C. The agitation of the pulp is advantageously carried out vigorously, with high shear, to achieve complete reaction of the lime, preferably by means of a peripheral speed of the stirring spindle of at least 5 m / s. The quantity of the calcium compound (e.g., lime) added is preferably equal to the stoichiometric quantity of zinc atprecipitate, i.e. one mole of calcium for two moles of zinc to be precipitated. The zinc-depleted solution can advantageously be recycled to the leaching process, so as to minimize the consumption of the basic alkaline compound, preferably selected from the group comprising sodium hydroxide, potassium hydroxide, alkali metal carbonate, lithium hydroxide and mixtures thereof, in the process. The calcium zincate can be washed with water to recover said basic alkaline compound, preferably selected from the group comprising sodium hydroxide, potassium hydroxide, alkali metal carbonate, lithium hydroxide and mixtures thereof impregnated in the solid. The wash water can be recycled at any stage of the process. After drying, the calcium zincate has a zinc content of around 40%. It can be used by smelters to produce zinc metal without requiring prior roasting like sulfide concentrates or oxidesWaelz. Calcium zincate can also advantageously be relixivated in a solution comprising the basic alkaline compound, preferably selected from the group comprising sodium hydroxide, potassium hydroxide, alkali metal carbonate, lithium hydroxide and mixtures thereof, preferably containing between 130 and 200 grams per liter of caustic soda, hot, preferably at a temperature above 70°C, so as to produce a zinc-supersaturated solution. During leaching, calcium oxide, one of the constituents of calcium zincate, is not dissolved. After leaching, it is separated from the enriched solution and can advantageously be recycled to the precipitation of calcium zincate or to leaching to precipitate impurities such as silica. The zinc-supersaturated solution can then be brought to a higher temperature in the presence of precipitation seeds (zinc oxide crystals) so as to force precipitation.zinc oxide. Zinc oxide produced from the leaching of calcium zincate is very pure, typically containing more than 95%, preferably more than 97%, more preferably more than 98%, advantageously more than 99% zinc oxide. It can be used to produce metallic zinc or as technical zinc oxide, particularly for the vulcanization of elastomers, the production of enamels, and animal feed. According to a first variant of the process, the following steps are planned to be carried out: - Supply of a material which contains zinc in oxidized form, - Leaching of the material in an alkaline basic medium with formation of a solid residue and a zinc-supersaturated solution (i) - Separation (A') of the solid leaching residue from the zinc-supersaturated solution (i), - Heating of said zinc-supersaturated solution (i) obtained after said separation (A') to precipitate (precipitate), preferably predominantly, a zinc oxide in a solutionzinc-depleted, - Separation (D') of the zinc oxide formed during heating of the zinc-supersaturated solution (i). According to a preferred embodiment of the first variant, the method may further include the following successive steps, after formation of the solid residue and the zinc-supersaturated solution (i) and optionally after the separation step (A'): - addition of a calcium compound to the zinc-supersaturated solution (i) to form a zincate pulp which consists of solid calcium zincate and a zinc-depleted basic solution, - separation (B') of at least a portion of the zinc-depleted basic solution from the calcium zincate pulp, - heating said calcium zincate pulp consisting of solid calcium zincate and the remainder of the zinc-depleted basic solution with formation of a zinc-supersaturated solution (iii) and a solid matter, - separation (C') of the solid matter obtained after the heating step to preserve the solutionsupersaturated in zinc (iii) and optionally recycling this solid material to the step of adding a calcium compound. Thus, the supersaturated zinc (iii) solution obtained is then heated to precipitate (precipitant), preferably mainly a zinc oxide. A separation (D') of the zinc oxide formed during the heating of the supersaturated zinc (i) solution and the zinc-depleted solution makes it possible to provide the zinc oxide according to the invention. In particular, the supersaturated solution (iii) formed in the preferred embodiment of the first variant has a higher zinc saturation compared to the initial supersaturated solution (i) and it is purer. Preferably, it is possible to recycle at least a portion of the zinc-depleted (basic) solution formed during at least one of the steps of the process by adding it to the leaching step in a basic medium. Advantageously, when implementing the firstvariant of the process according to the invention, it is necessary to produce a zincate solution supersaturated with zinc. To do this, the material containing the zinc is leached by an alkaline solution, possibly saturated with zinc. Under these conditions, it is observed that the zinc content can exceed the solubility limit of zinc oxide in the alkaline solution, without it precipitating. The solid residue, depleted in zinc, is separated by filtration. The zinc-rich solution can preferably be heated to a temperature above 70°C in the presence of crystallization seeds (zinc oxide particles). Under these conditions, the precipitation of zinc oxide is observed over time. After recovery of the zinc oxide by filtration, the zinc-saturated alkaline solution can advantageously be recycled to the leaching process. According to a second variant of the invention, the following steps are planned to be carried out: - Supply of a material whichcontains zinc in oxidized form, - Leaching of the material in an alkaline basic medium with formation of a solid residue and a zinc-rich solution (ii) - Separation (A') of the solid leaching residue from the zinc-rich solution (ii), - addition of a calcium compound to said zinc-rich solution (ii) to precipitate (precipitate) a zincate pulp which contains solid calcium zincate and a zinc-depleted basic solution, - separation (B') of at least a portion of the zinc-depleted basic solution from the calcium zincate pulp, - heating said calcium zincate pulp consisting of calcium zincate and the remainder of the zinc-depleted basic solution with formation of a zinc-supersaturated solution (iii) and a solid material, - separation (C') of the solid material obtained after the heating step to retain the zinc-supersaturated solution (iii) and optionally recycling this solid material to the addition step of a compoundcalcium, - Heating said zinc-supersaturated solution (iii) obtained after the separation step (C') of said solid matter to precipitate (precipitate), preferably predominantly, a zinc oxide in a zinc-depleted solution, - Separation (D') of the zinc oxide formed during the heating of the zinc-supersaturated solution (iii). Preferably, recycling at least a portion of said zinc-depleted (basic) solution formed during at least one of the steps of the process according to the second variant by adding it to the basic leaching step or to said zincate pulp after removal of at least a portion of the zinc-depleted solution and before heating and zinc supersaturation. This second variant according to the invention makes it possible to leach the zinc in an alkaline solution whose zinc content is below its solubility limit. In this eventuality, the zinc can be precipitated from the rich solution by adding finely divided lime,preferably at a temperature below 50°C. The lime reacts with the zincate solution to form an insoluble calcium zincate which can be recovered by filtration. This calcium zincate can be marketed as such, optionally after washing and drying, or relixiviated in an alkaline solution, optionally saturated with zinc, preferably at a temperature above 50°C so as to produce the solution supersaturated with zinc (iii). The lime remains insoluble and can be recovered by filtration. Advantageously, it can be recycled to the calcium zincate precipitation step. The supersaturated solution can then be heated to a temperature above 70°C, optionally in the presence of precipitation seeds (zinc oxide crystals) to precipitate (precipitant), preferably predominantly, zinc oxide. The alkaline solution depleted in zinc is advantageously recycled to the calcium zincate leaching. The recovered zinc oxide isvery pure (95-100% purity) and constitutes a material of choice for the production of zinc metal, determined by a method known to those skilled in the art. As can be seen, regardless of the embodiments chosen, the common step is to form a supersaturated solution which will be heated to provide the zinc oxide according to the invention. The embodiments set out above can also be combined with each other. Figure 1 illustrates an exemplary embodiment linked to the first variant of the process according to the invention. A material containing zinc (B) in oxidized form is supplied and leached (1) in a basic alkaline medium to form a solution supersaturated with zinc (i). Lime (A) can be added to this leaching step (1) to remove impurities. A solid / liquid separation (2) of the solid residue (C) is then carried out and the supersaturated solution (i) collected (3) is heated (7), possibly in the presence of precipitation seeds (F)(zinc oxide crystals) to form zinc oxide in a basic solution depleted in zinc. Before heating the zinc-supersaturated solution (i), it is possible to carry out a purification step for metals that are more noble than zinc (for example, Ag, Pb, Cu, etc.). Thus, a cementation (4) on a metal powder (D), such as a zinc metal powder (D), is carried out. After a solid / liquid separation step (5), the purified zinc-supersaturated solution (6) is recovered to carry out the heating step (7) mentioned above. After heating (7) and adding precipitation seeds (F), a solid / liquid separation (8) takes place and allows the zinc oxide (G) to be recovered. The basic zinc-depleted solution (9) is optionally purified (10) by adding a calcium compound (H), such as lime (H), to extract the impurities, provided that the addition of lime in the leaching step (1) does not take place. Following the separation (11) of the solid impurities (I), the solutionpurified zinc-depleted (12) is recovered and possibly recycled in the first leaching step (1). Figure 2 is an exemplary embodiment related to the second variant of the process according to the present invention – presence of calcium zincate. A material (A) containing zinc is brought to carry out a leaching (1) in a basic alkaline medium (aqueous NaOH solution) which makes it possible to form a zinc-rich solution (ii) in the presence of a solid residue. A solid / liquid separation (2) is carried out to remove the solid residue (B) and thus preserve the zinc-rich solution (3). Then, a calcium compound (C) (lime) is added to the zinc-rich solution which leads to the formation of a pulp which comprises calcium zincate (4) in the form of a precipitate and a basic zinc-depleted solution. The addition of the calcium compound (C) is preferably carried out cold or at a temperature below 70 °C. A separation (5) of at least part of thebasic zinc-depleted solution (D) takes place, and allows recycling of the latter to the leaching step (1). The calcium zincate pulp (6) is heated to a temperature above 70°C (7) to form a zinc-supersaturated solution (iii) and a solid matter. A solid / liquid separation (8) of the solid matter (E) is carried out, which allows extraction of the calcium compound (insoluble lime) which can advantageously be recycled to the step of adding said compound as illustrated in Figure 2. Heating (10) the zinc-supersaturated solution (9) after the separation step (8) allows precipitating a zinc oxide in a zinc-depleted solution. It is also advantageous to add precipitation seeds (F) (zinc oxide crystals) to this step. Then, a separation (11) of the zinc oxide (G) formed is collected and the basic solution depleted in zinc (H) is possibly recycled to the heating step (7). Part of this solutionThe basic zinc-depleted material can advantageously be reintroduced in the first step of the process (1). Figure 3 illustrates a leaching process called "countercurrent" and whose leaching step is carried out in 2 steps. Thus, the zinc-containing material (A) is supplied to the first leaching step (1) in an alkaline basic medium (aqueous NaOH solution). This allows the formation of a zinc-depleted solid residue and a partially zinc-enriched solution. Then, a first separation (2) of the solid leaching residue (C) is carried out to preserve the partially zinc-enriched solution (3). This is followed by a second leaching by the partially zinc-enriched solution with the formation of a zinc-enriched solution in the presence of a solid material. The zinc-enriched solution (E) is separated (5) and the solid material is re-supplied to the first leaching step (1). Advantageously, material containing zinc(possibly a zinc-rich material) can be added to the second leaching (4). Finally, preferably, the basic solution (B) depleted in zinc generated during a zinc oxide precipitation step can also be recycled to the first leaching (1). The figures above describe the general steps of the variants of the process according to the invention. All the characteristics of duration and temperature cited previously also apply specifically to the steps described for these 3 figures. According to the invention, the material which contains zinc in oxidized form is preferably any raw or secondary material containing zinc which can be leached in a solution comprising an alkaline basic compound, preferably chosen from the group comprising sodium hydroxide, potassium hydroxide, carbonate of an alkali metal, lithium hydroxide and mixtures thereof. This raw material can include at least one so-called oxidized ore which contains zincin the form of smithsonite, hemimorphite, hydrozincite, willemite. The secondary material may come from lead metallurgy (slag), dust from scrap metal recycling (EAFD), etc. The raw material used in the process according to the invention may advantageously contain a mineral chosen (without being limited to) from the group comprising zinc hydroxide (Zn(OH)2), zinc oxide (ZnO), Smithsonite (ZnCO3), hemimorphite (Zn4Si2O7(OH)2(H2O)), hydrozincite (Zn5(CO3)2(OH)6), willemite (Zn2SiO4) and ghanite (ZnAl2O4). For the purposes of the present invention, the term "for" may be used to indicate a limiting step. Thus, it is possible to replace if necessary the expression "for" by an expression which limits the scope according to the term used following the "for", for example by indicating "with formation of". Within the scope of the present invention, several chemical reactions can take place and are listed below. It isObviously, the person skilled in the art will be able to adapt the reactions depending on the raw material used. Smithsonite leaching ZnCO3 + 4 NaOH = Na2ZnO2 + Na2CO3 + 2 H2O Hemimorphite leaching Zn4Si2O7(OH)2(H2O) + 12 NaOH = 4 Na2ZnO2 + 2 Na2SiO3 + 8 H2O Calcium zincate precipitation 2 Na2ZnO2 + CaO + 7 H2O = CaZn2(OH)6.2H2O + 4 NaOH Calcium zincate redissolution CaZn2(OH)6.2H2O + 4 NaOH = 2 Na2ZnO2+ Ca(OH)2+ 6 H2O Carbonate precipitation by lime Na2CO3+ Ca(OH)2= 2 NaOH + CaCO3 Silica precipitation by lime Na2SiO3+ Ca(OH)2= 2 NaOH + CaSiO3Precipitation of zinc oxide Na2ZnO2 + H2O = ZnO + 2 NaOH Examples 1 and 2 present leaching tests of an oxidized ore in order to produce a basic solution supersaturated with zinc. Example 3 refers to the precipitation of zinc oxide from a supersaturated basic solution. Examples 4 and 5 illustrate the results of leaching tests of a lead slag by abasic solution for the purpose of producing a zinc-rich solution unsaturated with zinc (ii). Example 6 shows the precipitation of calcium zincate by adding lime to the leaching solution of Example 5. Example 7 relates to the production of a zinc-supersaturated solution by leaching calcium zincate. EXAMPLE 1 A sample of oxidized zinc ore containing 14.7% zinc, mainly in the form of smithsonite, 25.0% iron, 5.6% calcium and 4.8% silicon was ground to a particle size of less than 80 µm. 300 g of this ground ore was then leached in 2 liters of a solution containing 175 g / L NaOH, 65 g / L Na2CO3 and 10 g / L Zn added as ZnO. The pulp was heated to 70°C and 30 g of finely ground lime (CaO) was introduced into the pulp at the beginning of leaching. The pulp was stirred continuously for 2 hours before being filtered on a Buchner funnel. The filtrate was separated and the zinc and silicon concentrationswere determined by spectrometry. The filter cake was washed with 250 mL of water, dried, and its zinc content was determined by spectrometry after digestion in acid. The test results are shown in Table 1 below.
[0002] Table 1: Conditions and results of leaching test 1 Mass of crushed ore (g) 300 Addition of CaO (g) 30 Volume of etching solution (mL) 2000 Composition of etching solution NaOH (g / L) 175 Na2CO3 (g / L) 65 Zn (g / L) 10 Temperature (°C) 70 Leaching time (min) 120 Mass of dry residue (g) 285 Zn content of residue (%) 3.6 Volume of filtrate (mL) 1780 Zn content of filtrate (g / L) 28.5 Si content of filtrate (g / L) 0.85 Zinc leaching yield (%) 77 The leaching filtrate contained 28.5 g / L of zinc and 0.85 g / L of silicon while that the depleted residue contained only 3.6% zinc. The zinc leaching yield reached 77%. The filtrate is slightly supersaturated with zinc. EXAMPLE 2 150 g of the same fresh oxidized ore as in Example 1 and ground to a particle size of less than 80 µm were leached into 1 liter of the filtrate from the leaching test of Example 1.The pulp was heated to 50°C and stirred for 30 minutes before being filtered through a Buchner funnel. The filtrate was separated and the zinc and silicon concentrations were determined by spectrometry. The filter cake was washed with 125 mL of water, dried and its zinc content was determined by spectrometry after digestion in acid. The test results are shown in Table 2 below. The leach filtrate contained 41.3 g / L of zinc and 1.51 g / L of silicon while the depleted residue contained 7.8% zinc. The zinc leaching yield reached 55%. This yield is lower than that of Example 1 but the filtrate here is highly supersaturated with zinc (read, supersaturated zinc solution). In a second step and in order to illustrate a countercurrent leaching scheme, 121 g of the leach residue was re-leached into 840 milliliters of a zinc oxide precipitation filtrate from a supersaturated solution.15 g of lime was added to the pulp, then it was heated to 80°C and stirred for 2 hours before being filtered on a Buchner funnel. The filtrate was separated and the zinc and silicon concentrations were determined by spectrometry. The filter cake was washed with 120 mL of water, dried and its zinc content was determined by spectrometry after digestion in acid. The test results are also shown in Table 2 below. Table 2: Conditions and results of the leaching tests of Example 2 Leaching step 1 2 Mass of crushed ore (g) 150 Mass of residue (g) 121 Addition of CaO (g) 0 15 Volume of etching solution (mL) 1000 840 Composition of etching solution N. aOH (g / L) 171 154 N a2CO3 (g / L) 69 90 Z n (g / L) 28.5 20.8 S i (g / L) 0.85 n.a. Temperature (°C) 50 80 Leaching time (min) 30 120 Mass of dry residue (g) 126 140 Zn content of the residue (%) 7.8 3.7 Filtrate volume (mL)920 760 Zn content of the filtrate (g / L) 41.3 26.7 Si content of the filtrate (g / L) 1.51 0.75 Leaching efficiency (%) 55 46The filtrate from the second leaching stage contained 26.7 g / L of zinc and 0.75 g / L of silicon, while the residue contained only 3.7% zinc. The zinc leaching yield reached 46%. A carbon analysis of the filtrate showed that during leaching, the carbonate content of the solution decreased from 37 g / L of CO2 to 29 g / L due to the addition of lime. The overall zinc yield from the ore leach after the two stages was 76%. The two-stage countercurrent leaching yield produced a zinc-rich solution (41.3 g / L). EXAMPLE 3 90 g of pure zinc oxide were introduced as precipitation seeds into 900 mL of a highly zinc-supersaturated leach filtrate from the leaching of an oxidized ore containing 22.2% zinc. The pulp was brought to a boil (>90°C) in a flask and kept stirring.The vapors emitted were condensed in a water-cooled column and returned to the flask to minimize liquid losses. After 8 hours of boiling, the pulp was filtered on a Buchner funnel. The filtrate was separated and the zinc concentration was determined by spectrometry. The filter cake was washed with 100 mL of water and dried. The test results are shown in Table 3 below.
[0003] Table 3: Conditions and results of the zinc oxide precipitation test Initial volume of solution (mL) 900 Initial Zn content (g / L) 40.4 Initial Si content (g / L) 0.08 Addition of seeds (g of ZnO) 90.0 Temperature (°C) 105 Duration (h) 8 Mass of dry solid recovered 111.6 (g) Volume of filtrate (mL) 860 Zn content of the filtrate (g / L) 20.8The filtrate contained only 20.8 g / L of zinc. 111.6 g of dry solid were recovered. X-ray analysis showed that the solid consisted exclusively of zinc oxide. EXAMPLES 4 and 5 A sample of lead furnace slag containing 9.4% zinc, 17.4% iron and 13.6% silicon was ground to a particle size less than 80 µm. 200 g of ground slag were then leached in 1 liter of a solution containing 175 g / L of NaOH, 65 g / L of Na2CO3 and 10 g / L of Zn added as ZnO (Example 4). The pulp was heated to 90°C and stirred continuously for 4 hours before being filtered through a Buchner funnel. The filtrate was separated and the zinc and silicon concentrations were determined spectrometrically. The filter cake was washed with 250 mL of water, dried, and its zinc content was determined spectrometrically after alkaline fusion and acid digestion.The test was repeated, but this time the pulp was heated to 200°C (Example 5) in a pressurized reactor. Before filtration, the pulp was cooled to approximately 90°C using a water-cooled coil. The results of both tests are shown in Table 5 below. Table 4: Conditions and results of the leaching tests of examples 4 and 5 Example Example 4 5 Mass of crushed slag (g) 200 200 Volume of etching solution (mL) 1000 1000 Composition of etching solution NaOH (g / L) 175 175 Na2CO3 (g / L) 65 65 Zn (g / L) 10 10 Temperature (°C) 90 200 Leaching time (min) 240 240 Mass of dry residue (g) 216 204 Zn content of residue (%) 4.1 3.0 Volume of filtrate (mL) 850 870 Zn content of filtrate (g / L) 20.7 23.5 Si content of filtrate (g / L) 0.69 0.76 Leaching yield (%) 53 68 The zinc yield reached 68% at 200°C while it was only 53% at 90°C. The filtrates contained 20.7 g / L and 23.5 g / L of zinc respectively.They are not saturated with zinc. EXAMPLE 6 4.6 g of finely ground lime (CaO) was added to 800 mL of the filtrate from the leaching test of Example 5. The pulp was then stirred at room temperature for 6 hours, using a high-shear stirrer, before being filtered through a Buchner funnel. The filtrate was separated and the zinc concentration was determined spectrometrically. The filter cake was washed with 50 mL of water, dried and its zinc content was determined spectrometrically after digestion in acid. The test results are shown in Table 5 below. Table 5: Conditions and results of the calcium zincate precipitation test Initial volume of solution (mL) 800 Initial Zn content (g / L) 23.5 Addition of CaO (g) 4.6 Temperature (°C) ambient Time (h) 8 Mass of dry solid recovered (g) 30.3 Volume of filtrate (mL) 780 Zn content of the filtrate (g / L) 12.4 Zn content of the solid (%) 39.9 30.3 g of dry solid containing 39.9% zinc was recovered. X-ray analysis showed that the solid consisted of hydrated calcium zincate. The filtrate contained only 12.4 g / L of zinc, which is significantly lower than the solubility of zinc oxide in the absence of lime. EXAMPLE 7 25 g of hydrated calcium zincate from the test of Example 6 was suspended in 500 mL of a solution containing 175 g / L of NaOH and 65 g / L of Na2CO3. The pulp was heated to 90°C and stirred for 2 hours before being filtered through a Buchner funnel. The filtrate was separated and the zinc concentration was determined spectrometrically. The filter cake was washed with 20 mL of water, dried and its zinc content was determined spectrometrically after digestion in acid. 5.7 g of dry solid was recovered. The solid consisted almost exclusively of lime and contained only 2% zinc, indicating a zinc leaching efficiency of over 98%.The zinc content of the filtrate was 36.8 g / L, which is significantly higher than the saturation concentration of zinc in this solution. Within the scope of the present invention, any singular article such as, for example, "a", "an", "the", "the", "of", "of the" may be replaced by an article which designates a plural such as, for example, "at least 2", "at least 3", "several", "the" etc. The word "include", "contains" or any equivalent term or derivatives may be replaced by "consisting of" in order to define a list or possibilities of exclusive selection so as not to include other elements not cited in the expression used. It is understood that the present invention is in no way limited to the embodiments described above and that many modifications may be made thereto without departing from the scope of the appended claims.
Claims
CLAIMS 1. A process for recovering zinc which comprises the following steps: - Supplying a material which contains zinc in oxidized form, - Leaching the material in an alkaline basic medium with formation of a solid residue and a zinc-supersaturated solution (i) or a zinc-rich solution (ii), - Separation (A') of the solid leaching residue from the zinc-supersaturated solution (i) or the zinc-rich solution (ii), - Optionally: • adding a calcium compound to said zinc-rich solution (ii) or to the zinc-supersaturated solution (i) to precipitate (precipitate) a zincate pulp which contains solid calcium zincate and a zinc-depleted basic solution, • separating (B') at least a portion of the zinc-depleted basic solution from the calcium zincate pulp,• heating said calcium zincate pulp consisting of solid calcium zincate and the remainder of the basic solution depleted in zinc with formation of a zinc-supersaturated solution (iii) and a solid matter, • separation (C') of the solid matter obtained after the heating step to retain the zinc-supersaturated solution (iii) and optionally recycling this solid matter to the step of adding a calcium compound, - Heating said zinc-supersaturated solution (i) obtained after said separation (A') or the zinc-supersaturated solution (iii) optionally obtained after the separation step (C') of said solid matter to precipitate (precipitant), preferably, predominantly, a zinc oxide in a zinc-depleted solution, - Separation (D') of the zinc oxide formed during heating of the zinc-supersaturated solution (i) or (iii), - Optionally, recycling at least a portion of said zinc-depleted (basic) solution formed during at least one of the steps of the process by adding it to the basic leaching step or to said zincate pulp before heating and zinc supersaturation.
2. The process of claim 1, wherein the addition of the calcium compound to said zinc-rich solution (ii) or to said zinc-supersaturated solution (i) to precipitate calcium zincate is carried out by applying a temperature below 70°C or between 0 and 70°C, preferably below 50°C, more preferably below 30°C. 3.
4. A method according to any one of the preceding claims, wherein the step of heating said zinc-supersaturated solution (i) obtained after said separation (A') or the zinc-supersaturated solution (iii) optionally obtained after the separation step (C') of said solid material to precipitate a zinc oxide in a zinc-depleted solution is carried out in the presence of zinc oxide, serving as precipitation seeds.
4. A method according to claim 3, wherein the step of heating said zinc-supersaturated solution (i) obtained after said separation (A') or the zinc-supersaturated solution (iii) optionally obtained after the separation step (C') of said solid material to precipitate a zinc oxide in a zinc-depleted solution is carried out at a temperature above 70°C, preferably above 90°C, optionally for a period of time of at least one hour.
5. A method according to any one of the preceding claims, wherein, during the leaching step, an addition of a calcium and / or magnesium compound in a stoichiometric amount is carried out to precipitate impurities selected from the group comprising silica, alumina or carbonate.
6. A method according to any one of the preceding claims, wherein the leaching step is carried out at a temperature below 90°C, preferably below 70°C, optionally for a period of time of less than 2 hours.
7. A method according to any one of claims 1 to 5 or according to claim 6, wherein the leaching step is carried out at a temperature above 50°C, optionally for a period of time of less than 4 hours. 8.A method according to any one of the preceding claims, wherein a calcium and / or magnesium compound is added to the zinc-supersaturated solution (i) obtained after said separation of said solid residue, preferably before formation of zinc oxide. 9.Method according to any one of the preceding claims, in which the leaching step is carried out in several steps, preferably in two steps, comprising the following steps: - A first leaching of the material in an alkaline basic medium with obtaining a solid residue depleted in zinc and a solution partially enriched in zinc, - A first separation of the solid leaching residue, - A second leaching by the solution partially enriched in zinc with formation of a solution enriched in zinc, or of a solution supersaturated in zinc, and of a solid material, - A second separation of the solid material generated during the second leaching and recovery of the solution supersaturated in zinc (i) or of the solution rich in zinc (ii),. - Optionally, recycling the solid material recovered after said second separation to the first leaching.
10. Method according to claim 9, wherein an addition of a calcium compound is carried out during the first leaching.
11. Method according to claim 9 or 10, wherein said first leaching is carried out at a temperature greater than or equal to 60°C, preferably greater than or equal to 70°C.
12. Method according to any one of claims 9 to 11, wherein the second leaching is carried out at a temperature less than 70°C, preferably less than 60°C, or for a duration of less than two hours, preferably less than one hour.
13. Method according to any one of the preceding claims, wherein the calcium and / or magnesium compound is chosen from the group comprising lime, calcined dolomite and magnesia. 14.A method according to any one of the preceding claims, wherein the zinc-depleted solution generated in the method is purified from metallic impurities more noble than zinc by cementation on a metallic powder, preferably a zinc metal powder, preferably before the above-mentioned optional recycling step.
15. A method according to any one of the preceding claims, wherein the zinc-supersaturated solution (i) (iii) or the zinc-rich solution (ii) generated in the method is purified from metallic impurities more noble than zinc by cementation on a metallic powder, preferably a zinc metal powder.
16. A method according to any one of the preceding claims, wherein calcium zincate seeds are added to the precipitation of said calcium zincate pulp.