Improved copper smelting process

Abstract

A method for recovering copper from a secondary raw material, comprising the step of smelting (100) a feed material (1, 2) comprising copper oxide and elemental iron in a furnace to form a concentrated copper intermediate (3) in a feed batch, wherein heat is generated by oxidation-reduction reactions to convert the iron to oxide and the copper oxide to copper, the copper collecting in a molten liquid metal phase and the iron oxide collecting in a supernatant liquid slag phase; A method is disclosed in which at the end of the batch a liquid phase separates and can be removed from the furnace as smelter slag (5) and concentrated copper intermediate (3), characterized in that during the smelting step an excess of elemental iron is maintained in the furnace relative to the amount required for completion of the oxidation-reduction reaction, and further heat input is provided by injection of oxygen-containing gas to oxidize the excess iron.

Description

[Technical Field]

[0001] The present invention relates to the recovery of copper (Cu), along with other non-ferrous metals such as tin (Sn), lead (Pb), nickel (Ni), and zinc (Zn), primarily from secondary feed materials by pyrometallurgical (pyrometallurgical) process steps. The present invention preferably relates to secondary feed materials, also known as recyclable materials. Recyclable materials can be, for example, by-products, waste, and post-consumer materials of metal producers.

[0002] The present invention is primarily concerned with the well-known pyrometallurgical or smelting step in the production of copper. Depending on the source of the feed material, the smelting step may be further designated as a primary or secondary smelting step. [Background technology]

[0003] Smelting is a process in which heat and chemical agents are applied to metal ores to extract base metals, most typically in primary smelters. In more technical detail, smelting is a process in which metal-bearing solids are liquefied using chemical reactions that result in the metal. It is used to extract many metals from the inert gangue components of ores, including silver, iron, copper, and other base metals. It is a form of extractive metallurgy in which chemical reactions are used to drive off other elements as gases or slag, leaving behind a liquid bath containing the metals in their elemental form, or in a chemically combined form with sulfur, known as "matte." The elemental metals are recovered in a separate molten metal phase, which also typically forms a separate liquid phase. Most ores are impure, often requiring the use of fluxes such as limestone or silica to remove the accompanying gangue, which forms a separate liquid phase typically called "slag."

[0004] Also, in the recovery of copper from secondary materials, smelting can be used as a first step to recover a concentrated copper phase from a secondary material that is too contaminated and / or has a copper content that is too low to be truly suitable as a feed for refining to anode copper quality. Such secondary materials are typically richer in copper than primary copper sources, such as copper ore, or are usually also rich in copper as a copper-enriched intermediate that is first derived from the ore, for example, by mineral flotation upstream of the smelting step. Some of the copper in the secondary material may also already be present in elemental form and therefore not chemically bound. For these reasons, the processing conditions for copper smelting steps performed on secondary materials are significantly different from those for primary copper smelting steps that operate on copper concentrates or, occasionally, copper ores.

[0005] In primary copper smelters, typical starting materials are copper-bearing sulfides such as chalcopyrite (CuFeS), bornite (CuFeS), and chalcocite (CuS). Their reaction with oxygen (oxidation) drives off S as SO in the off-gas, forming a "matte" phase (CuS.FeS) along with a slag phase (FeO.SiO), the latter formed by reaction with added silica. In a second step, typically also in the smelting furnace, the FeS is driven off by further reaction with oxygen and silica to form more slag and more SO gas, leaving so-called "white metal" (CuS) with typically less than 1% residual Fe. The latter is then oxidized with an oxygen-containing gas, preferably air, according to the following reaction: Cu2S+O2→2Cu+SO2, Cu2S+3 / 2O2 → Cu2O+SO2 Cu2S+2Cu2O→6Cu+SO2)

[0006] This primary copper smelting process is typically carried out in a so-called "Pierce-Smith" converter to form so-called "blister copper," which contains slag containing Ni and precious metals, Fe, and Zn, mostly with 2-15% Cu, furnace dust (containing large amounts of Sb, As, Bi, Cd, and Pb), and off-gas (again containing SO). The large amount of S liberated in these process steps is emitted as SO and recovered in the form of sulfuric acid. Thus, the primary copper smelter step is typically primarily a strong oxidation step. Primary copper smelting is described, for example, in U.S. Pat. No. 5,623,624 or its registered version, U.S. Pat. No. 5,623,624. Treatment of the copper matte phase is described, for example, in U.S. Pat. No. 5,623,624 and U.S. Pat. No. 5,623,624. U.S. Pat. No. 5,623,624 describes a method for further processing copper matte or slag from the primary copper smelting step.

[0007] Patent Document 6 describes a primary copper smelting process in which the matte feedstock also contains iron sulfide. In the first step, this iron sulfide is selectively oxidized to iron oxide using oxygen-enriched air. The iron oxide and added silica become a separate slag phase that is removed from the furnace before the copper sulfide is further processed in the second step. The amount of available iron sulfide and its reaction with FeO may not be sufficient to generate the heat of reaction necessary to maintain the furnace temperature during this first step, especially when cold feedstock is processed. In the first step, a certain amount of extra metallic iron is added per ton of matte processed to counteract further oxidation of the iron to magnetite (FeO); otherwise, the viscosity of the slag would increase, impairing subsequent phase separation and slag removal at the end of the first step. Under oxidation conditions similar to those typically administered in the primary copper smelting step, the excess metallic iron is oxidized, and this reaction generates extra heat.

[0008] The metals in typical starting materials for secondary copper smelting are present primarily as oxides, although small amounts of sulfides may be present. Therefore, a key difference from primary copper smelting is the absence of copper matte as an intermediate. Some of the copper in the feedstock is actually already present in its elemental form, but at concentrations too low or in a form that is less suitable for pyrometallurgical copper refining and even less suitable for hydrometallurgical recovery (leaching + electrowinning). The copper in oxide form is then reduced in the smelting step by the addition of a reducing agent, e.g., a carbon source such as coke, and / or metallic iron, typically in the form of iron scrap. Therefore, a further key difference from primary copper smelting involves the reduction conditions under which the smelting step is performed on the secondary feedstock.

[0009] Patent Document 7 (Ludo Dierckx et al.) describes a copper refining method starting from secondary raw materials, in which the first step is a melting step, i.e., a reduction step. This is carried out in a melting furnace, where copper-bearing materials are heated together with solid materials containing metallic iron under an oxygen-enriched neutral flame. Gentle stirring from this charge produces a bath containing a slag phase. A small amount of alkaline or neutral flux may be added to optimize the specific gravity and viscosity of the resulting slag. Additional silica may also be added to absorb iron compounds produced in the reduction reaction. As the temperature of the molten bath in the furnace increases, chemically bound copper, lead, tin, or nickel in the charge is reduced with the solid metallic iron, forming a molten slag containing molten metal and iron silicate, known as "black copper." Typical process reactions are stated to include the following: MeO+Fe→FeO+Me (MeO) x SiO2+xFe→(FeO) x SiO2+xMe xFeO+SiO2→(FeO) x SiO2

[0010] These reactions confirm that the so-called "melting" step of Patent Document 7 qualifies as a "smelting" step within the context of this document. These reactions are exothermic, and the heat of reaction is stated to rapidly increase the temperature of the charge. Once the material melts to the point where it flows easily along the vessel walls, vessel agitation can be increased. At the end of the reduction process, black copper and molten slag are formed, which may be separated from each other by gravity or removed separately from the furnace.

[0011] Throughout the reduction process, the temperature is controlled as low as possible consistent with maintaining a fluid slag. The fuel supply must be adjusted so that the temperature of the reaction mass does not exceed about 1300°C for any significant period during the furnace cycle. Preferably, the temperature should be maintained not substantially higher than the temperature at which the slag becomes substantially fluid. A bath temperature of about 1180°C has been stated to be satisfactory for normal charge materials, although lower temperatures can be used when borax is used as a fluxing agent.

[0012] The low temperature not only minimizes the vaporization of lead and tin but also limits the dissolution of solid iron into the resulting molten copper. It has been stated that the presence of a significant amount of solid iron is essential to provide rapid and complete reduction of the slag. Iron dissolution should also be minimized to maintain high solubility of lead and tin in the resulting black copper. As the reduction reaction progresses and solid iron-containing material gradually dissolves in the molten metal, additional solid material containing metallic iron can be advantageously added after melting is complete to provide final reduction of the copper, tin, lead, and zinc remaining in the slag. Overall, the excess iron remaining in the furnace is used, at least a portion of which dissolves in the black copper. Although zinc volatilizes from the furnace, a significant amount of zinc also remains in the black copper at the end of the melting step.

[0013] At the end of the so-called melting step, when the final reduction step was complete, as further slag analysis showed, the molten slag was poured from the furnace into the top and granulated. After the molten slag was poured from the furnace, the resulting black copper was then pre-refined in the same furnace, with the addition of secondary materials already significantly rich in copper, using a strong oxidizing flame. This pre-refining step is therefore no longer part of the upstream melting step, which is a reduction step characterized by a reducing environment.

[0014] In Example 1 of Patent Document 7, the charge to the smelting furnace is melted "under a neutral oxygen-enriched flame" (column 15, lines 1-2), which is understood as a neutral flame, using oxygen-enriched air. After adding an additional amount of copper / iron scrap, the slag is further reduced under a slightly reducing flame (column 15, lines 33-35). Most of the zinc present is evaporated and collected as dust in the exhaust system. The slag is then injected from the top and granulated.

[0015] Patent Document 8 describes a bath smelting furnace in which copper-bearing material, preferably a copper-bearing secondary raw material, is subjected to a smelting process fueled by oil and / or gas with air and / or oxygen injected into the bath by a submerged injection lance. The smelting step produces a first slag, relatively free of impurities, that exits the process, and a second slag that is transferred from the bath smelting furnace to a rotary drum furnace for further processing. The rotary drum furnace is equipped with a burner at one end, which may be supplied with oil or gas and, optionally, oxygen from an oxygen reservoir. Further processing is carried out in stages, sequentially producing anode-grade copper, black copper, an unprocessed tin mixture that can be further processed for silicon, and a final slag. Coal is introduced into the rotary drum furnace at each process step. In all steps of the process of Patent Document 8, the furnace is heated by burning fuel with air and / or oxygen.

[0016] Patent Document 9 describes a method in which, to increase the yield of valuable metals, a liquid bath is formed by an oxidative smelting step performed on a secondary material, from which tin and zinc are removed by fuming in two successive steps, after which the iron-containing slag is removed and a copper-containing metal phase is retained. This metal phase can be further processed to first separate a lead-silicate slag, nickel-poor blister copper, and a copper-nickel oxide bath, which can then be reduced to form a copper-nickel alloy.

[0017] Patent Document 10 concerns the possible large variations in organic components in the smelter feedstock and their impact on process throughput. It proposes a batch process in which the organic components are removed in a first step, while producing so-called "black copper," which can be converted into blister copper by further oxidation in a subsequent step. Another product of the first step is the final metal-deficient slag. The document states that "a suitably adapted amount of oxygen is blown into the treatment chamber." In this method, "the composition of the slag and the content of valuable metals still present in the slag are monitored during the melting process by taking samples and analyzing them quickly."

[0018] A drawback of the smelting step of the '661 patent is that a significant portion of the heat input during the majority of the smelting step is provided by a neutral flame flowing over oxygen-enriched air, which requires large sources of fuel, air, and pure oxygen, with the associated complexities, additional equipment, and operating loads.

[0019] Heat input from the flame above the furnace to the molten bath leaves something to be desired because heat must be transferred from the combustion gases to the liquid bath. Heat transfer from the gas to the liquid is fairly slow, and the contact surface area between the burner at the top of the furnace and the liquid bath remains limited. With immersion burners, gravity forces the gases to rise rapidly, causing them to leave the liquid phase. Therefore, the contact time between the combustion gases and the molten bath is relatively short. Therefore, heat input from the flame to the bath is primarily by radiation. As a result, heat input from the flame is not very effective, and most of the potential heat input from the flame leaves the furnace in the exhaust gases, creating additional strain on the exhaust gas cooling system.

[0020] The large amounts of flue gas produced by the flame also require the installation of large exhaust gas treatment systems to treat them. [Prior art documents] [Patent documents]

[0021] [Patent Document 1] JPS61531A [Patent Document 2] JPH0515769B2 [Patent Document 3] CN101871050A [Patent Document 4] GB2462481A [Patent Document 5] US3,954,448 [Patent Document 6] JP2003253349 [Patent Document 7] US$3,682,623 [Patent Document 8] DE10 2012 005 401A1 [Patent Document 9] EP0185004 [Patent Document 10] US2017 / 0198371A1 Summary of the Invention

[0022] The inventors have discovered that there remains a need for simpler and more efficient heat input into secondary copper smelting furnaces while maintaining or even improving the means for controlling the temperature of the smelting step.

[0023] The present invention aims to avoid or at least mitigate the above problems and / or to provide improvements generally.

[0024] According to the present invention there is provided a method as defined in any of the accompanying claims.

[0025] In one embodiment, the present invention provides a method for recovering copper from a secondary raw material, comprising smelting a feed material comprising the raw material in a furnace in at least one feed batch to recover a concentrated copper intermediate from the furnace; a raw material feedstock is gradually introduced into the furnace, the feedstock comprising copper and optionally at least one metal more noble than copper, at least partially as an oxide under the processing conditions of the furnace; the feedstock further comprises iron and, optionally, at least one metal or compound at most as noble as iron or zinc under furnace conditions, wherein the iron and the metal at most as noble as iron or zinc are present at least partially in their elemental form; Heat is generated in the furnace by oxidation-reduction reactions, converting elemental iron and metals or compounds at most as noble as iron or zinc into oxides, and converting oxides of copper and oxides of metals more noble than copper into elemental metals; the elemental metal at least partially collects in a molten liquid metal phase and the oxide at least partially collects in a supernatant liquid slag phase; The liquid phases can be separated, and at the end of the smelting step, at least one of the liquid phases is at least partially removed from the furnace as a smelting slag and / or as a concentrated copper intermediate; During the smelting step, an excess of elemental forms of iron and of metals or compounds which are at most as noble as iron or zinc under furnace conditions is maintained in the furnace relative to the amount required for the completion of the oxidation-reduction reaction, The method is characterized in that further heat input to the furnace is provided by injection of oxygen-containing gas during the smelting step for oxidation of excess amounts of iron and metals or compounds at most as noble as iron or zinc present in the furnace, and optionally for burning combustible sources of carbon and / or hydrogen that may also be introduced into the furnace.

[0026] Preferably, the excess of iron and optionally a metal or compound that is at most as noble as iron or zinc under furnace conditions is maintained by deliberately adding at least one additional raw material rich in iron and / or at least one metal or suitable compound to the furnace as part of the feed material.

[0027] Applicants have found that maintaining an excess of iron and possibly other metals and / or compounds at most as noble as iron or zinc in the furnace provides a convenient way to control a highly controllable portion of the heat input, and therefore the temperature, in a smelting furnace, by controlling the injection of oxygen-containing gas into the furnace, since the oxygen in this gas is available to oxidize the excess of elemental iron and / or other metals or compounds at most as noble as iron or zinc. Applicants have found that this method allows for the direct, precise, and accurate dosing of the oxygen input to produce a portion of the heat of reaction, more advantageously one that is readily, directly, and completely available at the most desirable location (height) in the liquid bath within the furnace, i.e., at the interface between the metal and slag phases where the oxidation-reduction reactions and phase changes are believed to be occurring.

[0028] The heat from the oxidation of iron and other metals and / or compounds up to as noble as iron or zinc by reaction with oxygen from the oxygen-containing gas is generated in the bath itself, and no extra heat transfer step is required. This heat of reaction is completely and immediately dissipated into the smelting bath.

[0029] Applicants have found that, thanks to the present invention, temperature control within a smelting furnace is easy and very responsive, which is highly advantageous because as the temperature within the molten bath increases, more iron dissolves in the molten liquid metal and becomes available for oxidation by available oxygen, which, if abundant, can generate even more heat and cause temperature runaway.

[0030] The present invention can avoid this risk of temperature runaway because the input of oxygen as part of the oxygen-containing gas is highly controllable in the method according to the invention. If the feed material introduces more oxygen at a particular moment than is available to participate in oxidation-reduction reactions, and if the heat generated by these additional oxidation-reduction reactions leads to an increase in the temperature of the smelting bath, the temperature of the smelting bath can be easily controlled by reducing the injection rate of the oxygen-containing gas, and the risk of temperature runaway is easily avoided, or at least greatly reduced.

[0031] Another advantage of the present invention is that the oxidation of iron and other metals or compounds up to as noble as iron or zinc, unlike the combustion of natural gas or other carbon- and / or hydrogen-containing fuels, typically does not produce significant amounts of off-gas, and the furnace exhaust gas treatment systems associated with the smelting facility in which the method according to the present invention is operated can be designed to be smaller, therefore requiring lower investment costs and consuming lower operating costs during operation. Another advantage of lower off-gas volumes is that the less valuable tin, lead, and zinc typically also evaporate and do not need to be captured in the exhaust gas treatment system.

[0032] Thus, the applicants have found that generating heat by injecting oxygen gas into the molten bath, for example by oxidizing excess iron to iron oxide, is far more effective and efficient than burning a flame based on a combustible source of carbon and / or hydrogen in the furnace. The applicants estimate that approximately 80% of the injected oxygen reacts with compounds in the furnace's liquid bath, and the heat generated by these reactions remains in the liquid bath—a very high yield compared to the heat that can be generated by burning a hydrocarbon fuel such as natural gas, even when the combustion is carried out with pure oxygen or oxygen-enriched air. The applicants believe this difference is due to the fact that the conversion of iron to iron oxide occurs in the liquid bath itself, whereas the combustion of natural gas occurs in the gas phase, and the heat of combustion must still be transferred to the liquid phase to contribute to the enthalpy content of the liquid bath. Furthermore, such combustion is not necessarily complete.

[0033] Applicants have also found that suitable sources of elemental iron and metals or compounds up to as noble as iron or zinc are readily available from a number of sources and can be readily obtained in economical terms that make this heat input method economically advantageous over neutral flame heat input, based on operating costs alone. Furthermore, the carbon footprint of the method according to the present invention is low compared to the methods described in the prior art above.

[0034] Although within the scope of the present invention, the applicants consider it preferable not to implement the option of providing a portion of the total heat input to the furnace by burning a combustible source of carbon and / or hydrogen in the furnace. Although the applicants have found that under certain economic conditions it may be advantageous to implement this option, they have always found it preferable to control the furnace temperature by injection of an oxygen-containing gas, even when this option is active, because of its higher level of convenience, easier control, and lower risk of temperature runaway.

[0035] Another advantage of the present invention, related to the presence of excess dissolved iron in the molten liquid metal layer in the furnace, is that a layer of solid iron and / or iron oxide forms around the submerged tuyeres through which oxygen-containing gas can be introduced, providing additional protection against wear of these tuyeres, since they are cooled by a gas flow that is typically cooler than the smelting bath. This protective layer, typically hollow and mushroom-shaped, forms because the tuyeres themselves are cooler and the molten liquid metal around them is cooler, reducing the solubility of iron in the concentrated molten liquid copper phase and causing iron to precipitate and adhere to the outer surface of the tuyeres, except at the mouth where the gas is injected.

[0036] High responsiveness of the temperature control is advantageous because if the temperature of the molten liquid rises, this protective layer may melt again and the tuyere may lose its protective layer, resulting in significant damage and loss of production. High responsiveness of the temperature control system has the effect that the risk of such tuyere damage and associated loss of production can be significantly reduced, and preferably avoided.

[0037] Applicants have found that the advantageous effect of the present invention is to provide a more stable and reliable smelting step, which is typically a very early step in a more complex overall pyrometallurgical process.

[0038] The overall method may further process the product of the smelting step, for example according to the method according to the main claim, into derivatives.

[0039] The slag from the smelting step can preferably be further processed, for example, by fuming, as further described herein, to produce slag that raises fewer concerns when landfilled and / or used in higher value end uses.

[0040] The concentrated copper intermediate, preferably after being separated from the smelting slag formed in the smelting step, can be further processed, for example, by refining to produce a more concentrated refined copper product suitable for higher value end uses, and optionally by casting copper anodes as feed material for electrolysis which can ultimately result in high purity copper cathodes meeting many, if not all, of the current industry standards for more demanding end uses of copper.

[0041] Further processing of the concentrated copper intermediates and / or slag from the smelting step can result in other valuable by-products of the refined copper product.

[0042] Such valuable by-products may be, for example, raw solder streams, which may be derived from copper smelting slag, which may result from the refining of concentrated copper intermediates. Such raw solder may be further refined and / or conditioned, i.e., purified, by removing elements that may affect downstream processing and / or adversely affect or interfere with certain applications of the final product derived from the solder stream. These valuable by-products may include, for example, at least one product from the list consisting of a soft lead primary product, a hard lead primary product, a silver-rich anode slime product, and a high-grade tin primary product, as further described herein.

[0043] Applicants believe that the beneficial effects provided by the present invention are transmitted all the way to the production of derivatives of the products of the smelting step listed above. Improved stability and reliability of the smelting step ensures that downstream processes that produce these derivatives have a more stable and reliable feed stream from the smelting step, which in turn provides the benefit of making the downstream processes more stable and reliable. This allows for the production of end products with more stable and reliable quality. Furthermore, it allows for a reduction in the process monitoring burden and / or operator attention, and increases the possibility of electronically monitoring and controlling each of these process steps, as well as the overall process. [Brief explanation of the drawings]

[0044] [Figure 1] 1 shows a process flowsheet including the process according to the present invention as part of an overall process for the recovery of non-ferrous metals from secondary feedstocks. DETAILED DESCRIPTION OF THE INVENTION

[0045] The present invention will now be described in specific embodiments and with reference to certain drawings, but the present invention is not limited thereto, but only by the claims. All drawings described are schematic and non-limiting. In the drawings, the size of some elements may be exaggerated and not drawn to scale for illustrative purposes. The dimensions and relative dimensions of the drawings do not necessarily correspond to reductions to actual implementations of the invention.

[0046] Furthermore, the terms first, second, third, etc. in the specification and claims are used to distinguish between like elements and are not necessarily intended to describe a sequential or chronological order. These terms are interchangeable under appropriate circumstances, and embodiments of the invention may be practiced in orders other than those described and / or illustrated herein.

[0047] Furthermore, terms such as top, bottom, upper, lower, etc. in the specification and claims are used for descriptive purposes and do not necessarily describe relative positions. Terms so used are interchangeable under appropriate circumstances, and embodiments of the invention described herein may be practiced in orientations other than those described or illustrated herein.

[0048] The term "comprising" used in the claims should not be considered limited to the elements listed in the context thereof. It does not exclude the presence of other elements or steps. Where necessary, these features, integers, steps, or components should be considered to be provided, but this does not exclude the presence or addition of one or more other features, integers, steps, or components, or groups thereof. Thus, the term "article comprising means A and B" may not be limited to an object consisting only of agents A and B. This means that A and B are the only elements of subject matter interest in connection with the present invention. Accordingly, the terms "comprise" or "embed" also encompass the more restrictive terms "consisting essentially" and "consist of." Therefore, by replacing "comprise" or "include" with "consist of," these terms represent the basis for preferred but limited embodiments, which are also provided as part of the content of this specification regarding the present invention.

[0049] Unless otherwise specified, all ranges provided herein are inclusive of the given endpoints, and values for components or constituents of compositions are expressed as weight percent or weight % of each component in the composition.

[0050] As used herein, "weight percent," "wt-%," "percent by weight," "% by weight," "ppm wt," "ppm by weight," "ppm by weight," or "ppm," and variations thereof, unless otherwise specified, refer to the concentration of a substance as the weight of that substance divided by the total weight of the composition and multiplied by 100 or 1,000,000, as appropriate. As used herein, it is understood that "percent," "%" are intended to be synonymous with "weight percent," "% by weight," and the like.

[0051] It should be noted that as used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the content clearly dictates otherwise. Thus, for example, reference to a composition containing a "compound" includes a composition having two or more compounds. It should also be noted that the term "or" is generally used in its sense including "and / or" unless the content clearly dictates otherwise.

[0052] Additionally, each compound used herein may be discussed interchangeably with respect to its chemical formula, chemical name, abbreviation, and the like.

[0053] Metals or compounds at most as noble as iron or zinc can be produced under furnace conditions. For oxygen, iron or zinc have at least the same affinity as or even higher than , hence copper, nickel, tin, and lead than For oxygen handThese compounds have a higher affinity for oxygen than the zinc and iron compounds. This definition refers to "iron or zinc" because the relative positions of zinc and iron with respect to their affinity for oxygen under furnace conditions are very similar and may vary depending on furnace conditions. Therefore, to be accurate and comprehensive, this definition must refer to both of these metals. Under furnace conditions, these selected metals or compounds participate very readily on the oxidation side of the redox reaction as part of this invention. Suitable metals are, for example, elemental zinc and iron themselves, aluminum, silicon, and calcium. Suitable compounds may be, for example, metal silicides, preferably silicides of already suitable metals such as iron silicide (FeSi), but bimetallic or multimetallic compounds may also be suitable, including mixtures such as SnAl, CuFe, FeSn, or alloys such as brass (ZnCu). Further suitable compounds may be metal sulfides such as FeS, ZnS, and / or sulfides of other metals, where the sulfide or metal is at most as noble as iron or zinc.

[0054] Metals and compounds more noble than copper are compounds that have a lower affinity for oxygen than copper under furnace conditions. These materials participate more readily in the reduction side of oxidation-reduction reactions as part of the present invention, resulting in the liberation of the corresponding metal in its elemental form. For example, silver, gold, other noble metals, including platinum group metals, alloys, and mixtures thereof, including those containing other metals, are suitable.

[0055] In the context of this invention, the terms "smelter," "smelt," "smelting," or similar derivatives of "smelting" refer to a process that goes far beyond merely changing the state of matter of a compound from solid to liquid. In a pyrometallurgical smelter step, some chemical process is taking place that converts certain chemical compounds into other chemical compounds. The key of such conversions can be oxidation, possibly coupled with the formation of oxides, or reduction, where the oxidation state of some atoms is changed. Throughout this specification, the terms "smelter," "smelter furnace," and "smelting furnace" are used interchangeably and all refer to the furnace where this process step is taking place.

[0056] In the context of the present invention, the term "dross" or "drosses" refers to a material that is often pasty and formed as a result of a processing step, that typically separates from the different liquid phases under the influence of gravity and usually floats to the top. The dross or drosses are typically discarded or may be removable from the liquid below.

[0057] The term "solder" in the context of the present invention means a metal composition that is rich in tin and / or lead, but may also contain other metals. Solders are characterized by a relatively low melting temperature, which makes the composition suitable for so-called "soldering", in which the composition can be heated to a relatively limited temperature and then cooled to form a metallic connection between two other metal parts.

[0058] Unless otherwise specified, metal and oxide amounts are expressed herein in accordance with typical pyrometallurgical practice. The presence of each metal is typically expressed as its total presence, regardless of whether the metal is present in its elemental form (oxidation state = 0) or in any chemically combined form, typically an oxidized form (oxidation state > 0). For metals that can be relatively easily reduced to their elemental form and that can occur as molten metal in a pyrometallurgical process, it is fairly common to express their presence in their elemental metallic form, even when the composition of the slag is given; most of such metals may actually exist in an oxidized form. Thus, the composition of a slag, such as the slag obtained by the process according to the present invention, specifies the content of Fe, Zn, Pb, Cu, Sb, and Bi as elemental metals. Less noble metals are more difficult to reduce under non-ferrous pyrometallurgical conditions and occur primarily in an oxidized form. These metals are typically expressed in their most common oxide form. Thus, slag compositions typically provide the content of Si, Ca, Al, and Na, expressed as SiO, CaO, AlO, and NaO, respectively.

[0059] Metallurgical slags are typically not pure substances but mixtures of many different components. As a result, metallurgical slags do not have a distinct melting temperature. It has become common in the art to use the term "liquidus temperature," which is the temperature at which the slag is completely liquid.

[0060] In one embodiment of the method according to the present invention, the feedstock further comprises at least one second metal selected from the group consisting of nickel, tin, and lead. While a feedstock containing at least one second metal selected from this list is crucial for the recovery of copper from the feedstock, the presence of the second metal may pose additional burdens or difficulties compared to a feedstock that does not contain the second metal. The applicants have found that a smelting step is a highly suitable method step for introducing a feedstock containing at least one of such second metals. The applicants have found that the at least one second metal may also be present in the feedstock as its oxide or another form that can participate in a redox reaction under furnace conditions, liberating the metal in its elemental form. The applicants consider the oxide form to be preferred because of its greater availability under favorable conditions, the heat of reaction generated by the redox reaction involved, and the contribution of oxygen to the furnace, which reduces the amount of oxygen that needs to be injected. The reduced need for oxygen injection also reduces the gas flow through the smelting step, which is beneficial because the reaction rate is not limited by the external supply rate of oxygen gas, but rather only by the reaction kinetics. Less gas input can also mean less furnace exhaust gas requiring treatment and less entrained solids in the furnace exhaust gas.

[0061] In one embodiment of the method according to the invention, the feedstock comprises at least one second metal, and the enriched copper intermediate further comprises at least one second metal. The applicants have found that the smelting step can be carried out in such a way that a large proportion of the second metal is also most easily recovered as part of the enriched copper intermediate, in particular by driving the oxidation-reduction reaction in the smelting furnace to an appropriate extent. The applicants have found that this feature provides the advantage that the at least one second metal can also be recovered further downstream, desirably as part of a high-quality primary product.

[0062] In one embodiment of the method according to the present invention, the feed material comprises scrap iron, silicon, zinc, and / or aluminum, more preferably scrap iron. Applicants have found that this scrap material can be easily dosed accurately enough by mixing an appropriate amount of this scrap material with other raw materials as part of a feed batch. Applicants can also add this scrap material to the furnace as an additional feed stream. Applicants have found that scrap materials such as scrap iron and scrap aluminum, but also scrap silicon to some extent, are very readily available in suitable quantities and under economically advantageous conditions. Applicants have also found that the separate addition of scrap material (preferably scrap iron) as an additional feed stream to the furnace offers the advantage that it is very convenient to control and maintain excess amounts of elemental forms of iron and / or excess amounts of metals and / or compounds that are at most as noble as iron or zinc under furnace conditions.

[0063] In one embodiment of the method according to the present invention, the method further comprises a step of at least partially removing slag from the furnace. Applicants believe it is preferable to remove at least a portion of the slag from the furnace before starting a subsequent feed batch. If the available feed material at the time of a new feed batch contains a significant fine fraction, Applicants believe it is preferable to maintain a layer of slag in the furnace, because this layer provides a suitable blanket under which a feed material containing a fine or very fine fraction of the feed material can be introduced without excessive risk of fine feed material particles being entrained in the furnace exhaust gas, thereby creating additional burden and / or inconvenience for the furnace exhaust gas treatment system. If the available feed material contains a significant coarse fraction, Applicants believe it is preferable to remove substantially all of the formed slag from the furnace before starting a subsequent feed batch. This has the advantage that more furnace volume can be made available for subsequent feed batches, which is therefore beneficial to the throughput and / or productivity of the smelting furnace. Applicants have found that the step of removing slag from the furnace can be performed several times within the same furnace feed batch.

[0064] In one embodiment of the method according to the present invention, the method includes a step of removing at least a portion, preferably at most a portion, of the concentrated copper intermediate from the furnace. Applicants believe it is preferable to ensure the proper physical presence of molten metal in the furnace when starting a process involving a subsequent feed batch or series of feed batches. This molten metal is readily available as a hot liquid already at the start of a new feed batch or entire campaign to receive and wet the solid feed material and, optionally, excess amounts of elemental forms of iron and metals or compounds that are at most as noble as iron or zinc under furnace conditions (which may be desired or necessary to easily generate and / or maintain excess amounts of these additives for the method according to the present invention). The iron dissolved in this molten metal is readily available to react with oxygen injected into the liquid bath, thus immediately generating heat of reaction. A further advantage is that the solid iron that can be added to the furnace at the start of a new feed batch remains suspended above the molten metal phase, precisely where it can fully contribute to the oxidation-reduction reactions intended by the method. Applicants have found that by retaining a portion of the concentrated copper intermediate in the furnace when starting a new furnace feed batch, the time until the furnace is again operating at high capacity as part of the next feed batch is significantly reduced, and therefore the productivity of the smelting step is significantly improved. Applicants believe it is preferable to remove a portion of the molten metal formed in the previous feed batch before starting a new furnace feed batch. Applicants have found that the step of removing a portion of the concentrated copper intermediate from the furnace may even be performed several times within the same furnace feed batch.

[0065] Applicants believe it is preferable to conduct the smelting step, whenever possible, in a semi-continuous mode, allowing suitable material to continue to be added to the furnace until the available furnace volume is fully utilized. Then, once the slag and metal phases reach the desired quality, at least a large portion of the slag can be initially removed from the furnace via an overflow through a feed port, enabled, for example, by tilting the furnace. The bulk of the liquid molten metal phase can then be removed in the same manner as if all the slag had been removed, or tapped through a "bottom tap" port appropriately located in the furnace wall. For the reasons explained above, it is preferable that a suitable portion of the molten metal be maintained in the furnace when the introduction of the next feed batch into the smelting furnace begins. Applicants have found that this process can continue for a very long period of time, only to be interrupted or stopped when external factors or maintenance intervention on the smelting furnace are deemed necessary. Applicants have found that this process can be further improved by preparing suitable premixed batches of feed material with respect to the composition and size of the solids in the batch. Applicants have found that this can provide the advantage of a much more stable implementation, both in terms of the timing of the sequence of steps and in terms of the quality of the enriched copper intermediate that is removed each time from the furnace as the main product.

[0066] In one embodiment of the process according to the present invention, the iron and compounds at most as noble as iron or zinc introduced with the feedstock preferably comprise solid iron, solid silicon, solid zinc, and / or solid aluminum, including copper / iron-containing scrap, silicon-containing scrap, zinc-containing scrap, and / or aluminum-containing scrap. The applicants have found that these sources of iron, silicon, zinc, and aluminum are readily available from a variety of sources. Furthermore, they may contain small amounts of other metals that are recoverable in their elemental form during and downstream of the smelting step and may be worth recovering. Such other metals may include tin, lead, and nickel. They may also contain trace amounts of more noble precious metals (PM), such as silver or gold, and even platinum group metals (PGM), such as ruthenium, rhodium, osmium, palladium, iridium, and platinum itself, very small amounts of which may be worth recovering due to their rarity and high economic value.

[0067] In one embodiment of the method according to the invention, the feed material is at least partially solid, whereby the solid feed material is gradually, preferably continuously, fed to the furnace, preferably by at least one conveyor belt and / or vibratory conveyor, preferably during the majority of the smelting feed batch, more preferably during the majority of the entire smelting process. As explained elsewhere herein, applicants consider it preferable to feed campaigns of coarse portions of available feed material at the initial stages of the furnace feed batch and / or until a preferably thick layer of metallurgical slag forms as a blanket over the molten metal phase in the furnace. When this slag layer is made available from the start of the feed batch, or once this slag layer has been formed by operating the furnace on top of the coarse fraction of the available feed material, Applicants believe it is preferable to also introduce the fine fraction of the available feed material into the furnace, and Applicants believe it is preferable to introduce this fine fraction pneumatically via a lance immersed in the liquid bath and which ejects the fine fraction material near the interface between the molten metal phase and the supernatant molten slag phase, as this offers the advantage of reducing the risk of losing fine feed material particles in the furnace exhaust gases.

[0068] In one embodiment of the method according to the invention, the rate of introduction of the feed material is maintained below a rate at which heat generation becomes insufficient to melt the solid feed material and / or raise the feed material to the desired furnace temperature. Applicants believe it is preferable to avoid the risk of insufficient enthalpy balance in the furnace as much as possible, since there is a risk that the heat generated will be insufficient to heat and melt the introduced feed material, which would then cause the temperature in the furnace to drop. Applicants have found it advantageous to control the rate of introduction of the feed material, for example, so that iron can be added at a sufficient rate so that the excess of elemental forms of iron and metals or compounds that are at most as noble as iron or zinc under furnace conditions remains sufficiently high to generate sufficient heat of reaction in combination with a sufficient input of oxygen to achieve easy heating and melting of the introduced feed material.

[0069] In one embodiment of the method of the present invention, at least a portion of the feed material is in the form of finely divided portions, the finely divided feed material portions having an average particle size of up to 10 mm, preferably the finely divided feed material portions having an average particle size of up to 3.36 mm. Applicants have found that finely divided raw materials containing copper and other metals relevant to the method of the present invention are typically difficult to process by alternative methods and can therefore be found in significant quantities and under economically attractive conditions. Applicants have found that such materials can be easily and completely processed in the method of the present invention. Applicants believe it is preferable to introduce such finely divided feed material portions into the furnace only when a continuous layer of molten slag is available in the furnace, and the molten slag floats on top of the underlying molten metal phase. Applicants believe it is preferable to introduce the finely divided feed material portions near the interface between the molten metal and the molten slag, so that the slag layer can act as a blanket capable of capturing any small particles before they reach the furnace gas phase, risking being entrained in the exhaust gas and not participating in the method in the furnace.

[0070] In one embodiment of the method according to the invention, the feed comprises finely divided feed portions, which are pneumatically transported and injected into the furnace. The applicants have found that this method is a very convenient way to introduce such finely divided feed portions, and it offers the possibility to introduce the finely divided feed portions in the most advantageous position, i.e., just above the interface between the liquid metal and the liquid slag, where any elemental iron, such as scrap iron, present is also usually suspended and where most of the chemical reactions take place.

[0071] In one embodiment of the method according to the invention, the feed comprises a finely divided feed portion, and the finely divided feed portion material is injected into the liquid slag phase and above the metal phase of the liquid bath. Applicants have found that the slag phase just above the interface between the liquid metal and the liquid slag, in which elemental iron, such as iron scrap, present, also typically floats, is where the majority of the chemical reactions take place and where the majority of the heat of reaction is also generated.

[0072] In one embodiment of the method according to the invention, the feed comprises finely divided feed portions, and the average composition of the finely divided feed portions fed throughout the smelting feed batch in the furnace, after heating to 1150°C, satisfies at least one, and preferably all, of the following conditions: at least 5% by weight of total metals, preferably at least 5% in total of copper, nickel, tin, lead and zinc, preferably at least 6% by weight, more preferably at least 7% by weight, even more preferably at least 8% by weight, preferably at least 9% by weight, more preferably at least 10% by weight of total metals (preferably the sum of copper, nickel, tin, lead and zinc), maximum 70.0 wt.% copper (Cu), preferably maximum 65.0 wt.%, more preferably maximum 60.0 wt.%, even more preferably maximum 55.0 wt.%, even more preferably maximum 50.0 wt.%, preferably maximum 48.0 wt.% copper, optionally at least 10 wt.% copper, preferably at least 15 wt.%, more preferably at least 20 wt.%, even more preferably at least 25 wt.%, even more preferably at least 30 wt.%, preferably at least 35 wt.%, more preferably at least 40 wt.%, even more preferably at least 42.0 wt.% copper, maximum 2.00% by weight of nickel (Ni), preferably maximum 1.50% by weight, more preferably maximum 1.00% by weight of nickel, containing at least 0.50% and at most 10.00% by weight of lead (Pb), preferably at least 1.00% by weight, more preferably at least 1.50% by weight, and optionally at most 9.00% by weight, preferably at most 8.00% by weight, maximum 15.00% by weight of tin (Sn), preferably maximum 14.00% by weight, more preferably maximum 13.00% by weight, even more preferably maximum 12.00% by weight of tin, maximum 2.00% by weight of antimony (Sb), preferably maximum 1.50% by weight, more preferably maximum 1.00% by weight of antimony, maximum 7.0 wt.% iron (Fe), preferably maximum 6.0 wt.%, more preferably maximum 5.0 wt.%, even more preferably maximum 4.0 wt.%, even more preferably maximum 3.50 wt.% iron, Contains up to 55% by weight of zinc (Zn), preferably up to 50% by weight, more preferably up to 45% by weight, even more preferably up to 43% by weight, even more preferably up to 40% by weight, and even more preferably up to 35.0% by weight of zinc.

[0073] The applicants have found that finely divided feed portions as specified are well suited to the process according to the invention because of the presence of metals that are of interest to be recovered in high quality products downstream of the process and / or that can provide heat of reaction as part of the process according to the invention, while at the same time the finely divided feed portion has a sufficiently low content of these metals that the feed portion is of low economic interest for alternative methods of recovering metals from primary and / or secondary raw materials, and therefore the feed can be found in economically attractive conditions that offer significant upgrading when processed in the process according to the invention. Compliance with the upper sulfur content limit as part of one of the conditions listed above further avoids the formation of a separate copper matte phase, and therefore the process according to the invention including this feature is clearly distinguishable from copper smelting processes in which a matte phase is formed as either a product or intermediate.

[0074] In one embodiment of the method according to the invention, the feed material comprises at least one return material from the processing of the molten liquid metal phase and / or liquid slag phase formed by the method. The applicants have found that the smelting step is a very convenient step for returning by-products that may be formed by further processing of the molten liquid metal phase and / or liquid slag phase formed in the smelting step. Such further processing may take place after the smelting step in the same furnace, but preferably in a different facility downstream of the smelting step. Examples of such downstream processing are described further herein below.

[0075] In one embodiment of the method according to the invention, the feed material comprises at least one return material selected from the group consisting of reject anodes, other products containing copper, tin and / or lead, dross containing metals as oxides or sulfides formed and removed from downstream processing steps, metal oxides or metal sulfides (preferably oxides or sulfides of copper, nickel, tin, lead and / or zinc), metal silicides (preferably silicides of metals selected from copper, zinc, nickel, iron, lead and tin), crusts or other solids formed on the walls of crucibles or ladles used to transport the molten metal and / or molten slag removed from the furnace. Applicants have found that the smelting step is a very suitable processing location for returning by-products that may not be very well defined in terms of content, such as some of the materials listed above, or by-products that may contain various metals of interest, such as zinc oxide dust that may be collected by filtering the exhaust gases of furnaces carrying out a wide variety of pyrometallurgical process steps, or furnace slags that contain levels of recoverable metals that would burden or obstruct more conventional outlets and / or justify excessive passage through the metal recovery process.

[0076] In one embodiment of the method according to the invention, the feed material is introduced into the center of the liquid bath in the furnace. This has the advantage that, due to the buoyancy experienced by the solid feed material when immersed in the molten metal phase, it can usually float on top of the molten metal phase without coming into contact with the refractory lining in the furnace. This reduces the wear and tear that the solid feed material can cause to the refractory lining, thus improving the lifespan of the refractory lining and thus improving the time between two maintenance interventions to repair the refractory lining.

[0077] In one embodiment of the method according to the invention, the feed material comprises a coarse fraction, the coarse feed material fraction preferably having an average particle size of at least 5 mm, preferably at least 10 mm, even more preferably at least 15 mm, and the average composition of the coarse feed material fraction fed throughout the smelting feed batch in the furnace, after heating to 1150°C, satisfies at least one, and preferably all, of the following conditions: at least 20% by weight of total metals, preferably at least 20% by weight in total of copper, nickel, tin, lead and zinc, preferably at least 30% by weight, more preferably at least 40% by weight, even more preferably at least 50% by weight, preferably at least 60% by weight, more preferably at least 70% by weight, and possibly up to 95% by weight of total metals (preferably the sum of copper, nickel, tin, lead and zinc), at least 10.0 wt.% and at most 70.0 wt.% copper (Cu), preferably at least 15.0 wt.%, more preferably at least 17.0 wt.%, even more preferably at least 18.0 wt.%, even more preferably at least 19.0 wt.%, optionally at most 65.0 wt.%, preferably at most 60.0 wt.%, more preferably at most 55.0 wt.%, even more preferably at most 50.0 wt.%, even more preferably at most 45.0 wt.% copper, at least 0.50 wt.% and at most 2.00 wt.% nickel (Ni), preferably at least 0.60 wt.%, more preferably at least 0.70 wt.%, even more preferably at least 0.80 wt.%, even more preferably at least 0.90 wt.%, optionally at most 1.90 wt.%, preferably at most 1.80 wt.%, more preferably at most 1.70 wt.%, even more preferably at most 1.60 wt.%, even more preferably at most 1.50 wt.% nickel, at least 1.00% and at most 8.00% by weight of lead (Pb), preferably at least 1.10% by weight, more preferably at least 1.25% by weight, even more preferably at least 1.50% by weight, even more preferably at least 1.60% by weight, optionally at most 7.50% by weight, preferably at most 7.00% by weight, more preferably at most 6.50% by weight, even more preferably at most 6.00% by weight, even more preferably at most 5.50% by weight of lead, at least 0.50 wt.-% and at most 2.50 wt.-% tin (Sn), preferably at least 0.60 wt.-%, more preferably at least 0.70 wt.-%, even more preferably at least 1.00 wt.-%, even more preferably at least 1.20 wt.-%, optionally at most 2.40 wt.-%, preferably at most 2.30 wt.-%, more preferably at most 2.20 wt.-%, even more preferably at most 2.00 wt.-%, even more preferably at most 1.90 wt.-% tin, maximum 0.10% by weight of antimony (Sb), preferably maximum 0.08% by weight, more preferably maximum 0.06% by weight of antimony, at least 10.0 wt.% and at most 35.00 wt.% iron (Fe), preferably at least 11.0 wt.%, more preferably at least 12.0 wt.%, even more preferably at least 13.0 wt.%, even more preferably at least 14.0 wt.%, optionally at most 34.5 wt.%, preferably at most 34.0 wt.%, more preferably at most 33.0 wt.%, even more preferably at most 32.0 wt.%, even more preferably at most 31.0 wt.% iron, at least 2.00% and at most 15.00% by weight of zinc (Zn), preferably at least 2.50% by weight, more preferably at least 3.00% by weight, even more preferably at least 3.50% by weight, even more preferably at least 4.00% by weight, optionally at most 14.00% by weight, preferably at most 12.00% by weight, more preferably at most 11.00% by weight, even more preferably at most 10.00% by weight, even more preferably at most 9.00% by weight of zinc.

[0078] The applicants have found that the coarse feedstock fraction is highly suitable as a feedstock for the process according to the invention. This fraction contains a sufficient amount of the metal of interest to make the fraction interesting as a whole, but the amount of valuable metals is not high enough to make the coarse fraction interesting for alternative methods for recovering some of these metals. The applicants have found that the designated coarse fraction is not sufficiently enriched in lead, in addition to copper and / or tin, to make the fraction suitable as a feedstock for pyrometallurgical copper smelting, as described, for example, in WO 2019 / 115533 A1. Compliance with the upper sulfur content limit as part of one of the conditions listed above further contributes to avoiding the formation of a separate copper matte phase, and thus the process according to the invention, including this feature, is clearly distinguishable from copper smelting processes in which a matte phase is formed as a product or one of the intermediates.

[0079] Applicants have further found that relatively low levels of sulfur can be readily accommodated in the coarse fraction of the feedstock, which provides the advantage that a wider selection of feedstocks can be tolerated in the smelting step, including feedstocks that are unacceptable or less desirable in alternative methods for processing such feedstocks.

[0080] In one embodiment of the method according to the present invention, the amount of dissolved iron and / or metals and compounds at most as noble as iron or zinc in the molten metal in the furnace is maintained at at least 1.0 wt. %, preferably at least 1.5 wt. %, and the concentration of metals and compounds at most as noble as iron or zinc is converted to an equivalent iron concentration that, when reacted with oxygen under furnace conditions, can contribute the same amount of heat of reaction as a metal or compound at most as noble as iron or zinc. Applicants have found that compliance with this condition is very conveniently monitored and maintained, readily ensuring a sufficient excess of elemental iron and a sufficient excess of metals or compounds at most as noble as iron or zinc under furnace conditions. Compliance with this condition also ensures that iron and / or other metals or compounds at most as noble as iron or zinc are always present in the furnace in sufficient excess so that the temperature in the furnace can be easily maintained by sufficient oxygen injection. A further advantage is that this condition ensures tuyere protection by solid iron and / or iron oxide, as described elsewhere herein.

[0081] In one embodiment of the method according to the invention, the amount of dissolved iron and / or metals and compounds at most as noble as iron or zinc under furnace conditions in the molten metal in the furnace is maintained at a maximum of 10.0 wt.%, preferably at a maximum of 9.0 wt.%, more preferably at a maximum of 8.0 wt.%, even more preferably at a maximum of 7.0 wt.%, even more preferably at a maximum of 6.0 wt.%, preferably at a maximum of 5.0 wt.%, more preferably at a maximum of 4.0 wt.%, even more preferably at a maximum of 3.5 wt.%, even more preferably at a maximum of 3.0 wt.%, preferably at a maximum of 2.5 wt.%, such that the concentration of metals and compounds at most as noble as iron or zinc is converted to an equivalent iron concentration that, when reacted with oxygen under furnace conditions, can contribute the same amount of heat of reaction as a metal or compound at most as noble as iron or zinc. Meeting this condition reduces the risk that iron will come out of solution in cooler spots in the furnace, such as the furnace walls, reducing the available furnace volume and impairing the stirring of the liquid bath in the furnace.

[0082] In one embodiment of the process according to the invention, elemental iron is introduced into the smelting step at a rate such that an excess of iron is maintained in the molten bath during processing that exceeds its solubility in the metal bath at furnace conditions. Applicants have found this to be a very convenient means of providing sufficient iron in the furnace to ensure the desired excess.

[0083] In one embodiment of the method according to the invention, the amount of excess iron present in the furnace is maintained by at least periodically sampling the molten metal phase in the furnace and analyzing the samples for iron. Preferably, a limit on the amount of excess iron is maintained in order to limit the amount of solid iron moulding around in the liquid bath of the furnace and to limit the damage, wear and tear that these mouldings can cause to the refractory lining in the furnace.

[0084] In one embodiment of the method according to the invention, the combustible source of carbon and / or hydrogen is selected from the group consisting of coke, charcoal, carbon black, hydrocarbons, natural gas, methane, ethane, propane, butane, hydrocarbons liquid at normal conditions, hydrocarbon-containing polymers, plastics, waste plastics, grease, oil, paints, varnishes, rubber, preferably waste products thereof, and combinations thereof. Applicants have found that a wide range of sources are suitable, and some of these sources are very readily available with attractive supply conditions.

[0085] In one embodiment of the method according to the invention, the amount of combustible sources of carbon and / or hydrogen is maintained below, and preferably significantly below, the level at which slag foaming impairs the performance of the smelting step, so that the risk of slag foaming remains acceptably low. Applicants have found that the upper acceptable level, depending on the source selected, can be easily determined by trial and error. A further advantage of following this precaution is that the furnace off-gas temperature remains acceptable and the carbon monoxide content of the off-gas remains acceptable. Alternatively, the amount of combustible sources of carbon and / or hydrogen remains limited below the level at which the furnace off-gas temperature remains acceptably low or below the level at which the carbon monoxide content of the off-gas remains acceptably low.

[0086] In one embodiment of the method according to the present invention, at least a portion of the oxygen-containing gas is introduced into the supernatant slag phase, preferably as substantially as possible to the interface between the metal phase and the supernatant slag phase. Applicants believe it is preferable to introduce at least a portion of the oxygen-containing gas into this target location where oxygen is most likely to be consumed by oxidizing elemental metals, such as iron, dissolved in the metal phase, and where oxides formed by the oxidation reaction can easily migrate to the supernatant slag phase with minimal diffusion distances to cover.

[0087] In one embodiment of the method according to the invention, at least a portion of the oxygen-containing gas is introduced by means of at least one metal lance, the tip of which is immersed in the liquid slag phase. The applicants have found this to be a very convenient way to introduce the oxygen-containing gas to its target location. The lance may be introduced through a dedicated opening in the furnace wall or through the furnace's charge port, where the feed material may also be introduced.

[0088] In one embodiment of the method according to the invention using at least one metal lance, the gas injected through the metal lance contains at least 30% by volume, preferably at least 40% by volume, more preferably at least 50% by volume, and even more preferably at least 75% by volume of oxygen, and even more preferably the gas is high-purity oxygen. This offers the advantage of reducing, and preferably avoiding, the generation of excess furnace exhaust gas compared to using air as the oxygen-containing gas. Thus, exhaust gas treatment systems can be smaller or operated more efficiently. A further advantage is that the furnace exhaust gas contains fewer nitrogen oxides and is therefore more environmentally acceptable.

[0089] In one embodiment of the method according to the invention, which uses at least one metal lance, the gas flow through the metal lance provides sufficient cooling to prevent the lance from corroding and / or melting while immersed in the liquid bath of molten slag. The applicants believe it is preferable to introduce the gas lance into the furnace from above the liquid bath, immersing the lance only in the supernatant slag phase, but not in the molten metal bath. The applicants have observed that, as defined, the sufficient cooling effect of the gas passing through the lance allows the lance to remain exposed to the hot slag phase for extended periods, but rather quickly dissolves in the underlying molten metal phase.

[0090] In one embodiment of the method according to the invention, at least a portion of the oxygen-containing gas is introduced into the bottom of the furnace through at least one tuyeres, preferably through a plurality of tuyeres, more preferably through a plurality of tuyeres evenly distributed over the bottom of the furnace, which provides the advantage of high agitation of the liquid bath in the furnace.

[0091] In one embodiment of the method according to the invention using tuyere, the gas introduced through at least one tuyere is an oxygen-containing gas containing up to 50% by volume, preferably up to 40% by volume, more preferably up to 30% by volume, even more preferably up to 25% by volume of oxygen, and even more preferably the gas introduced by the tuyere is air. The gas must overcome the hydrostatic pressure caused by the height of the liquid furnace contents. Therefore, the gas must be compressed to allow introduction through the tuyere. Therefore, if the gas contains air, this air is compressed before introduction.

[0092] In one embodiment of the method according to the invention using tuyere, the gas introduced through at least one tuyere is at a lower temperature than the molten liquid metal phase surrounding the tuyere, which cools the molten liquid metal phase around the tuyere, thereby reducing its solubility for iron, and when the molten liquid metal phase becomes saturated with iron at higher temperatures, iron and / or iron-containing compounds such as iron oxide precipitate around the tuyere to form deposits, typically in the form of hollow mushrooms, which provide the tuyere with the desired protection against corrosion caused by the high heat of oxidation of iron near the tuyere.

[0093] In one embodiment of the method according to the invention, the smelting slag produced by this method contains at least 20% by weight of iron (Fe), preferably at least 22.5% by weight, more preferably at least 25.0% by weight, even more preferably at least 27.50% by weight, and even more preferably at least 30.00% by weight. In this context, the iron content is the sum of the iron present in all its valence states, i.e., the sum of all iron present as elemental iron and iron present in chemically bound form, usually in the form of oxides. This has the advantage of higher slag fluidity, i.e., lower viscosity at the same temperature.

[0094] In one embodiment of the method according to the invention, the composition of the smelting slag produced satisfies at least one, preferably all, of the following conditions: maximum 1.00 wt.% copper (Cu), preferably maximum 0.90 wt.%, more preferably maximum 0.80 wt.%, even more preferably maximum 0.70 wt.%, even more preferably maximum 0.60 wt.% copper, maximum 0.20% by weight of nickel (Ni), preferably maximum 0.17% by weight, more preferably maximum 0.15% by weight, even more preferably maximum 0.12% by weight, and even more preferably maximum 0.10% by weight of nickel, containing a maximum of 2.00% by weight of lead (Pb), preferably a maximum of 1.50% by weight, more preferably a maximum of 1.00% by weight, even more preferably a maximum of 0.95% by weight, and even more preferably a maximum of 0.90% by weight of lead, maximum 1.00 wt.-% tin (Sn), preferably maximum 0.80 wt.-%, more preferably maximum 0.60 wt.-%, even more preferably maximum 0.40 wt.-%, and even more preferably maximum 0.25 wt.-% tin, maximum 22.50% by weight of zinc (Zn), preferably maximum 20.00% by weight, more preferably maximum 17.50% by weight, even more preferably maximum 15.00% by weight, and even more preferably maximum 12.50% by weight of zinc.

[0095] Compliance with the specified limits for copper, nickel, tin, and lead provides the advantage of low rejection of valuable metals from the process. The present invention is directed to a copper recovery process, and limiting copper losses in the smelting slag provides the advantage of high copper recovery from available raw materials.

[0096] Applicants have found that many copper-containing raw materials, especially the secondary materials of that group, contain significant amounts of primarily tin, but also, in some cases, lead, nickel, and zinc. Applicants have found that most of these metals, other than copper, can be recovered from the same raw materials by pyrometallurgical process steps, as long as these metals are not lost in the smelting slag. Observing upper limits for other metals, primarily tin and nickel, but also lead and to some extent zinc, offers the advantage of recovering these metals at high recovery rates from available raw materials.

[0097] The presence of zinc in the smelting slag can be higher if an additional slag fuming step is performed to fume the smelting slag in order to reduce its zinc content and possibly also its lead content. The applicants consider it preferable to add such an additional fuming step to remove more zinc, and preferably also traces of lead, from the smelting slag, preferably as described in WO 2016 / 156394 A1.

[0098] Applicants have found that the above characteristic of low loss of valuable metals in the smelting slag can be controlled and obtained by suitable operation of the smelting step with respect to furnace temperature, furnace agitation, and oxygen addition, addition and selection of reducing agents, and addition and selection of flux materials (or sometimes called slag formers).

[0099] In one embodiment of the method according to the invention, the composition of the enriched copper intermediate as the main product from the smelting step satisfies at least one, and preferably all, of the following conditions: at least 50.0 wt.% copper (Cu), preferably at least 55.0 wt.%, more preferably at least 60.0 wt.%, even more preferably at least 65.0 wt.%, even more preferably at least 70.0 wt.%, preferably at least 72.5 wt.%, more preferably at least 75.0 wt.%, even more preferably at least 77.0 wt.%, even more preferably at least 78.0 wt.%, or even 79.0 wt.% copper (Cu), optionally up to 97.0 wt.%, preferably up to 95.0 wt.%, more preferably up to 90.0 wt.%, even more preferably up to 85 wt.%, even more preferably up to 82.0 wt.%, preferably up to 80 wt.%, more preferably up to 79.0 wt.%, even more preferably up to 78.0 wt.%, and even more preferably up to 77.0 wt.% copper (Cu), at least 0.01 wt.-% nickel (Ni), preferably at least 0.05 wt.-%, more preferably at least 0.10 wt.-%, even more preferably at least 0.50 wt.-%, even more preferably at least 1.00 wt.-%, preferably at least 1.10 wt.-%, more preferably at least 1.25 wt.-%, even more preferably at least 1.40 wt.-%, even more preferably at least 1.50 wt.-%, or even 1.70 wt.-% nickel (Ni), optionally up to 15.00 wt.-%, preferably up to 12.50 wt.-%, more preferably up to 10.00 wt.-%, even more preferably up to 7.50 wt.-%, even more preferably up to 5.00 wt.-%, preferably up to 4.00 wt.-%, more preferably up to 3.00 wt.-%, even more preferably up to 2.50 wt.-%, and even more preferably up to 2.40 wt.-% nickel (Ni), at least 0.10 wt.% lead (Pb), preferably at least 0.50 wt.%, more preferably at least 1.00 wt.%, even more preferably at least 2.00 wt.%, even more preferably at least 3.00 wt.%, preferably at least 3.50 wt.%, more preferably at least 4.00 wt.%, even more preferably at least 4.50 wt.%, even more preferably at least 5.00 wt.%, or even 5.50 wt.% lead, and optionally up to 15.00 wt.%, preferably up to % lead (Pb), preferably at most 14.50% by weight, more preferably at most 14.00% by weight, even more preferably at most 13.50% by weight, even more preferably at most 13.00% by weight, preferably at most 12.50% by weight, more preferably at most 12.00% by weight, even more preferably at most 11.50% by weight, even more preferably at most 11.00% by weight, preferably at most 10.50% by weight, more preferably at most 10.00% by weight, even more preferably at most 9.50% by weight, and even more preferably at most 9.00% by weight; at least 1.00 wt.-% tin (Sn), preferably at least 1.25 wt.-%, more preferably at least 1.50 wt.-%, even more preferably at least 1.75 wt.-%, even more preferably at least 2.00 wt.-%, preferably at least 2.25 wt.-%, more preferably at least 2.50 wt.-%, even more preferably at least 2.75 wt.-%, even more preferably at least 3.00 wt.-%, or even 3.25 wt.-% tin (Sn), optionally up to 12.00 wt.-%, preferably up to 10.00 wt.-%, more preferably up to 8.00 wt.-%, even more preferably up to 7.00 wt.-%, even more preferably up to 6.00 wt.-%, preferably up to 5.50 wt.-%, more preferably up to 5.00 wt.-%, even more preferably up to 4.50 wt.-%, and even more preferably up to 4.00 wt.-% tin (Sn), at least 0.05 wt.-% iron (Fe), preferably at least 0.10 wt.-%, more preferably at least 0.30 wt.-%, even more preferably at least 0.50 wt.-%, even more preferably at least 0.60 wt.-%, preferably at least 0.70 wt.-%, more preferably at least 0.80 wt.-%, even more preferably at least 0.90 wt.-%, even more preferably at least 1.00 wt.-%, or even 1.10 wt.-% iron (Fe), optionally up to 5.00 wt.-%, preferably up to 4.00 wt.-%, more preferably up to 3.00 wt.-%, even more preferably up to 2.50 wt.-%, even more preferably up to 2.00 wt.-%, preferably up to 1.75 wt.-%, more preferably up to 1.50 wt.-%, even more preferably up to 1.25 wt.-%, and even more preferably up to 1.00 wt.-% iron (Fe), at least 0.10 wt.-% zinc (Zn), preferably at least 0.50 wt.-%, more preferably at least 1.00 wt.-%, even more preferably at least 2.00 wt.-%, even more preferably at least 2.50 wt.-%, preferably at least 3.00 wt.-%, more preferably at least 3.50 wt.-%, even more preferably at least 4.00 wt.-% zinc (Zn), optionally up to 10.00 wt.-%, preferably up to 9.50 wt.-%, more preferably up to 9.00 wt.-%, even more preferably up to 8.50 wt.-%, even more preferably up to 8.00 wt.-%, preferably up to 7.50 wt.-%, more preferably up to 7.00 wt.-%, even more preferably up to 6.50 wt.-%, even more preferably up to 6.00 wt.-%, preferably up to 5.50 wt.-%, more preferably up to 5.00 wt.-% zinc (Zn), maximum 5% by weight of sulfur (S), preferably maximum 4.5% by weight, more preferably maximum 4.0% by weight, even more preferably maximum 3.5% by weight, even more preferably maximum 3.0% by weight, preferably maximum 2.5% by weight, more preferably maximum 2.0% by weight, preferably maximum 1.5% by weight, more preferably maximum 1.0% by weight, even more preferably maximum 0.5% by weight, even more preferably maximum 0.1% by weight of sulfur, optionally at least 5 ppm by weight, preferably at least 50 ppm by weight, more preferably at least 100 ppm by weight, even more preferably at least 500 ppm by weight, even more preferably at least 1000 ppm by weight, preferably at least 0.5% by weight, more preferably at least 1.0% by weight of sulfur.

[0100] The applicants have found that the above-mentioned features of the present invention can also be controlled and obtained by appropriate operation of the smelting step as described above, including the selection of the feed material. Observing the upper sulfur content limit as part of one of the conditions listed above further avoids the formation of a separate copper matte phase, and therefore the process according to the present invention, including this feature, is clearly distinguishable from copper smelting processes in which a matte phase is formed as one of the products or intermediates. The applicants have further found that the above-mentioned metal phases are highly suitable for the recovery of the listed valuable metals by pyrometallurgical process steps, as described herein below.

[0101] Applicants have further found that the large amount of copper in the metal phase can be made to act as an extractant for other valuable metals, such as nickel, tin and lead, from the slag phase, and therefore contributes itself to high recovery of these metals in addition to copper.

[0102] Applicants have further discovered that compliance with the specified lead content provides advantages in even more economically advantageous recovery of tin metal, since tin and lead, by virtue of their lead content, may be recovered, along with valuable lead-containing by-products of different qualities, as solder-type by-product streams that can be suitably conditioned and subsequently distilled for recovery of a high purity tin primary product.

[0103] In one embodiment of the method according to the invention, the liquid bath in the furnace has a temperature in the range of 1100-1300°C, preferably at least 1120°C, more preferably at least 1140°C, or even 1150°C, possibly up to 1250°C, preferably up to 1200°C, more preferably up to 1180°C. The applicants have found that this temperature range offers the advantage of sufficient slag fluidity and sufficient zinc fuming already from the smelting step, while maintaining a low tin and / or lead fuming rate from the smelting step, thus contributing to high tin and / or lead and / or zinc recovery and high processability of the smelting step. The applicants consider it preferable to cool the contents of the furnace to a maximum of 1140°C before the metal is removed from the furnace. The applicants have found that this precaution contributes to a longer service life of the vessels that contain the molten metal and transport it to subsequent method steps.

[0104] In one embodiment of the method according to the invention, the exhaust gas from the furnace is collected and treated by cooling and / or filtering. Applicants have found that the exhaust gas from the smelting step contains valuable metals worth recovering, and the specified treatment also reduces environmental concerns associated with the release of the smelting step exhaust gas into the atmosphere.

[0105] In one embodiment of the method according to the invention, secondary exhaust gases from the surroundings of the furnace are also collected and treated by filtration, optionally in combination with cooling. Applicants have found that this feature further reduces environmental concerns that may be associated with the operation of a furnace according to the invention.

[0106] In one embodiment of the method according to the invention, the smelting step is carried out in a smelting furnace.

[0107] Smelting furnaces offer the advantage of being simple to operate and install, and therefore economically advantageous. They offer the additional advantage of being tolerant with regard to raw material quality. They can accept highly diluted and / or contaminated raw materials with a wide variety of components, including a wide variety of organic matter. In the smelting furnace, the metal is melted and the organic matter and other combustible materials are burned off. These mixed and / or contaminated raw materials can be supplied in a very economically attractive state, since they have few other end uses. Therefore, the ability to process these raw materials and upgrade the valuable metals contained therein is of interest to operators of the method according to the invention.

[0108] The smelting furnace is a very simple and inexpensive device consisting of a large cylindrical furnace that only needs to be able to tilt about its longitudinal axis in a portion of a complete circle. This finding offers the advantage of low capital and / or operating costs for carrying out the smelting step.

[0109] In one embodiment of the method according to the invention, the walls of the furnace are at least partially cooled across the furnace wall surface, which has the advantage that wear and tear on the furnace wall is reduced, in particular for moving parts provided as part of the means for moving the furnace and for increasing and / or controlling the agitation of the bath in order to be able to agitate the liquid bath.

[0110] In one embodiment of the present invention, the method further comprises a step of fuming the slag phase formed in the smelting step to obtain fumed slag; preferably, the fuming is carried out in a fuming furnace. The fuming step produces fumed slag, along with at least dust containing most of the metals fumed from the smelting slag, typically in their oxidized form. The applicants have found this additional method step to be advantageous because it broadens the acceptance criteria for the smelting step by including raw materials containing more zinc, and possibly lead as well. Such raw materials are often difficult to process using alternative methods, which can present process and / or economic burdens, and therefore can be made more abundant and available under more attractive economic conditions. The zinc fuming step can be carried out as described by Michael Borell in "Slag—a resource in the sustainable society" (Proceedings, pages 130-138) of the 2005 International Conference on Mining and Environmental Metal and Energy Recovery, "Securing the Future," held in Skelleftea, Sweden. However, the applicants consider it preferable to carry out an additional fuming step as disclosed in WO2016 / 156394A1.

[0111] In one embodiment of the method according to the invention, the slag is granulated when removed from the smelting or fuming step. Preferably, the slag from the smelting and / or fuming step is removed as a liquid from the respective furnace. An advantage is that the furnace can be opened for further production and / or slag processing while the resulting slag is cooling. The slag can be cooled and / or solidified by contacting the slag with a cooling medium such as air, possibly ambient air.

[0112] In one embodiment of the method according to the invention, the cooling of the slag is carried out by contacting the liquid slag with water. Applicants have found that water cooling is very effective and can be applied in a variety of ways that result in a relatively well-controlled cooling rate.

[0113] In one embodiment of the method according to the invention, the method further comprises using the produced slag in an end use selected from providing a wear layer and / or coating on roof tiles or shingles, as a blasting sand or blasting grit component, as a foam tile component, as a black colorant, preferably in construction products, more preferably in black tiles, as a black solid mass, preferably for decorative purposes, as high density ballast, preferably for underwater applications, more preferably for hydraulic engineering, and combinations thereof.

[0114] In one embodiment of the method according to the invention for the production of objects for the construction industry, the method further comprises the step of adding the produced slag as aggregate and / or as binder, preferably as a binder for aggregates, preferably as an active binder, more preferably as a binder with pozzolanic activity, even more preferably as a substitute for Portland cement, even more preferably as a partial substitute for Portland cement.

[0115] In one embodiment of the method according to the invention, the produced slag is added as a binder in the inorganic polymer composition, preferably in combination with a base, more preferably as the main binder in the inorganic polymer composition, even more preferably as the only binder in the inorganic polymer composition.

[0116] In one embodiment of the method according to the invention, in which the produced slag is added during the production of an object for the construction industry, the method further comprises the step of foaming the inorganic polymer composition.

[0117] In one embodiment of the method according to the invention for the manufacture of objects for the construction industry, the objects for the construction industry are building elements, preferably the building elements are selected from the list of tiles, paving stones, blocks, concrete blocks and combinations thereof.

[0118] In one embodiment of the method according to the invention for the production of an object for the construction industry, the object for the construction industry has a foam structure.

[0119] In one embodiment of the method according to the invention for the manufacture of an object for the construction industry, the method further comprises using the object for improving thermal and / or sound insulation, for shielding from X-rays, and combinations thereof.

[0120] In one embodiment of the method according to the invention, the method further comprises purifying the enriched copper intermediate to obtain a purified copper product together with at least one copper refining slag. The applicants have found that this purification step can suitably be carried out as described in WO2019 / 115543A1.

[0121] In one embodiment of the method according to the invention, wherein the concentrated copper intermediate further comprises tin and lead, the method further comprises recovering a raw solder metal composition from the concentrated copper intermediate, which recovery of the raw solder metal may suitably be carried out as described in WO2019 / 115524A1.

[0122] In one embodiment of the method according to the present invention including recovery of the raw solder metal composition, the method further comprises recovering from the raw solder metal composition at least one of a refined soft lead product, a refined hard lead product, and a refined tin product. Applicants have found that the raw solder metal composition is a highly suitable feedstock for the recovery of at least one of the listed products, preferably at least a refined tin product, more preferably one of a plurality of further refined lead products, and even more preferably both refined lead products.

[0123] In one embodiment of the method according to the present invention that includes recovering a raw solder metal composition, the method further includes the step of pre-purifying the raw solder metal composition to produce a pre-purified solder metal composition.

[0124] The raw solder metal composition, which may be obtained as a by-product from the refinement of the enriched copper intermediate obtained from the method according to the present invention, can be further refined or processed to remove more of its contaminants, particularly copper. This can be done by contacting the raw solder metal composition as a molten liquid with elemental silicon and / or aluminum, which combine with Cu, Ni, and / or Fe under the processing conditions to form separate silicide and / or aluminide alloy phases. Applicants believe it is preferable to use silicon- and / or aluminum-containing scrap. Preferably, the added material further contains Sn and / or Pb, because these metals are easily upgraded to their respective primary products when introduced at this process stage. Due to the typical presence of Sb and As in the raw solder metal composition, Applicants believe it is preferable to use silicon and avoid aluminum, even though aluminum is more readily available and more reactive. This avoids the formation of HS, toxic gases, and more exothermic reactions in the process vessel, and also avoids the possibility that the resulting alloy phase by-products may come into contact with water to produce the highly toxic gases stibine and / or arsine. Applicants have found that the silicon feed for this process step can contain limited amounts of iron (Fe), easily greater than 1 wt. %, easily up to 5 wt. %, or even up to 10 wt. % Fe. Thus, the method can be carried out using Si products that are unacceptable to other silicon consumers and therefore may be more readily available, such as rejected material from the production line. Applicants have found that the burden of disposing of this excess Fe, which also combines with Si, is typically easily compensated for by favorable conditions for the supply of the silicon source.

[0125] This pre-purification can suitably be carried out as described in WO 2019 / 115524 A1 and produces a so-called "cuprophase" by-product, which can be advantageously recycled to the smelting step of the process according to the invention, preferably after "washing" as described.

[0126] In one embodiment of the method according to the present invention, which includes the recovery of a raw solder metal composition, the method further comprises conditioning the raw solder metal composition or the pre-purified solder metal composition to produce a conditioned solder metal composition. This conditioning step can further prepare the solder suitable for vacuum distillation, a technically very demanding method step that is sensitive to the excessive presence of certain metallic contaminants. Such conditioning and distillation can suitably be carried out as described in WO 2018 / 060202 A1.

[0127] In one embodiment of the method of the present invention for producing a conditioned solder metal composition, the method further comprises a first distillation step for distilling the conditioned solder composition, wherein lead is removed from the solder by evaporation to obtain a first distillation overhead product and a first distillation bottoms product. Such a first distillation may suitably be carried out as described in WO2018 / 060202A1.

[0128] In one embodiment of the method according to the invention for producing a first distillation overhead product, the method further comprises removing at least one contaminant selected from metallic arsenic, antimony, and tin from the first distillation overhead product to obtain a purified soft lead product. Preferably, the purified soft lead product is produced as described in WO 2020 / 157165 A1.

[0129] In one embodiment of the process according to the invention comprising a first distillation step, the first distillation bottoms product of the first distillation step contains lead and silver, and the process further comprises the step of separating the bottoms product of the first distillation step by fractional crystallization into a first silver-enriched liquid effluent product at the liquid end of the crystallization step and a first tin-enriched product at the crystal end of the crystallization step. Applicants believe it is preferable to carry out this separation as described in WO2020 / 157167A2.

[0130] In one embodiment of the method according to the invention comprising a fractional crystallization step, the method further comprises separating the first silver-enriched liquid effluent product, preferably by electrolysis, into a lead- and tin-rich product and a silver-rich product, whereby the anode slime represents the silver-rich product. The applicants believe it is preferable to carry out this separation as disclosed in WO2020 / 157167A2.

[0131] In one embodiment of the method according to the present invention for producing a first tin-enriched product, the first tin-enriched product further contains lead and antimony, and the method further comprises a second distillation step for distilling the first tin-enriched product, where primarily the lead and antimony are vaporized, to obtain a second distillation overhead product and a second distillation bottoms product.

[0132] In one embodiment of the process according to the invention comprising a second distillation step, the process further comprises a third distillation step for distilling the second distillation overhead product, vaporizing the lead and obtaining a third distillation overhead product and a third distillation bottom product, preferably the third distillation bottom product being at least partially recycled to the feed of the second distillation step and / or the feed of the fractional crystallization step.

[0133] In one embodiment of the process according to the invention comprising a third distillation step, the process further comprises removing at least one contaminant selected from metallic arsenic and tin from the third distillation overhead product to obtain a purified hard lead product. Applicants believe it is preferable to carry out this step as described in WO 2020 / 157168 A1.

[0134] In one embodiment of the process according to the invention comprising a second distillation step, the process further comprises purifying the second distillation bottoms product to obtain a purified tin product. Applicants believe it is preferable to carry out this step as described in WO 2020 / 157168 A1.

[0135] In one embodiment of the method according to the invention, which comprises the purification of the concentrated copper intermediate to obtain a purified copper product, the method further comprises the step of casting the purified copper product to produce a purified copper anode. The applicants have found that the purified copper product in the form of a copper anode, together with the anode slime, which can be further processed to recover the metals contained therein, provides a product highly suitable for a further electrolytic process step to produce a high purity copper cathode. The applicants believe it is preferable to carry out this electrolytic refining process step as described in WO 2019 / 219821 A1.

[0136] In one embodiment of the method according to the present invention, at least a portion of the method is electronically monitored and / or controlled. The applicants have found that controlling steps of the method according to the present invention electronically, preferably by a computer program, offers the advantage of much better processing, with results that are much more predictable and closer to the method goals. For example, based on temperature measurements, optionally also on pressure and / or level measurements, and / or in combination with the results of chemical analyses of samples taken from the method stream and / or analytical results obtained online, the control program can control equipment related to the supply or removal of electrical energy, the supply of heat or cooling media, flow and / or pressure control. The applicants have found that such monitoring or control is particularly advantageous for steps performed in continuous mode, but can also be advantageous for steps performed in batch or semi-batch mode. Furthermore, preferably, monitoring results obtained during or after the execution of steps in the method according to the present invention are also used to monitor and / or control other steps as part of the method according to the present invention and / or to monitor and / or control processes applied upstream or downstream of the method according to the present invention, as part of an overall process of which the method according to the present invention is only a part. Preferably, the entire method is electronically monitored, more preferably by at least one computer program. Preferably, the entire method is electronically controlled as far as possible.

[0137] Applicants also contemplate that computer control may be preferred, whereby data and instructions are passed from one computer or computer program to at least one other computer or computer program or module of the same computer program for monitoring and / or control of other methods, including but not limited to the methods described herein.

[0138] The claimed invention is further illustrated by FIG. 1, which shows a process flowsheet of the overall process as a preferred embodiment including the process steps of claim 1 for the recovery of enriched copper intermediates.

[0139] In FIG. 1, the following symbols refer to the following method steps or streams: 100. Smelting step or smelter 200.Copper smelter 300. Copper anode casting 400. Slag fuming step 500. Lead / Tin Recovery 1. Coarse feed material portion 2. Finely divided feed material parts or dust 3. Black copper as a concentrated copper intermediate 4. Smelter dust by-products from smelting furnaces 5. Smelting slag 6. Refining slag 7. Raw solder by-product from copper refining 8. Refined copper 9. Copper anode product 10. Soft lead products 11. Hard lead products 12. Refined tin products 13. Fumed Slag 14. Fuma dust by-products from fuming furnaces

[0140] 1 shows that a coarse feedstock portion 1 and a finely divided feedstock portion 2 are fed to a smelting furnace 100 into which an oxygen-containing gas (not shown) is injected to control the reaction and therefore the temperature within the furnace. The furnace exhaust gas is cooled and filtered, thereby collecting smelter dust 4. Smelter slag 5 is removed from the furnace and fed to a fuming step 400, where fuma dust 14 is recovered and a second slag, final slag or so-called "clean slag" 13, is produced.

[0141] The concentrated copper intermediate, black copper 3, is fed to a copper smelter 200, which produces a refined copper product 8, a raw solder by-product 7, and refined slag 6. The refined slag 6 may be sent to a fuma 400 to increase the amount of final slag 13 and fuma dust 14. The refined copper 8 is fed to a copper anode casting step 300 to produce copper anodes 9. The raw solder 7 is sent to a lead / tin recovery step 500, which produces a soft lead product 10, a refined tin product 12, and possibly a hard lead product 11.

[0142] Applicants have discovered that the beneficial technical effects of the present invention, particularly the more stable and reliable operation of the smelting step 100, easily transfer throughout the downstream process to the production of derivatives 9, 10, 11, 12, 13, and 14 shown in Figure 1. With the present invention, the derivative steps enjoy a more stable and reliable feed stream resulting from the smelting step, and are therefore able to produce a final product of more stable and reliable quality. A further advantage is that the present invention reduces the monitoring burden and operator attention required to operate the downstream process steps and the process as a whole.

[0143] Example A rotary drum furnace having an internal diameter of 3 meters holds a level of approximately 1.00 meters of liquid black copper as a concentrated copper intermediate from a previous feed batch, equivalent to a quantity of approximately 113 metric tons (metric tonnes).

[0144] The furnace was operated in semi-continuous mode for a continuous run period of approximately 16 months using a repeating sequence of the following operating modes, during which each cycle involved a different premix feed batch constructed and collected by selecting multiple parcels (small portions) from a large inventory of available raw materials.

[0145] Mode 1: Coarse solid raw material is gradually fed into the furnace from a suitable feed batch. This mode is continued as needed until a continuous layer of slag floating on top of the liquid metal phase is obtained.

[0146] Mode 1+2: When a continuous layer of slag from another suitable premix feed batch configured for this purpose is present in the furnace, finely divided feed material, also called "dust", is pneumatically transported and injected into the liquid slag phase and above the metal phase of the liquid bath, typically gradually over time, although preferably the gradual feeding of coarse solid material is also continued.

[0147] Mode 3: Typically, as part of the process, only if necessary, once the feed batch is finished and / or the furnace is full, there is a period of time during which the furnace is maintained and the chemical reactions proceed until the desired slag and metal composition is achieved.

[0148] Mode 4: The slag is poured from the furnace by tilting the rotating drum until the supernatant slag phase at least partially overflows through the furnace feed port. The slag is preferably transferred in liquid form in a suitable container to a fume furnace for further recovery of zinc, and possibly lead from fuming, and possibly copper as part of the metal phase by-product of the fuming step. The slag from this fuming step, and from the smelting step if a fuming step is not available, is cooled, solidified, and granulated by contacting the hot liquid slag with a large flow of water.

[0149] Mode 5: The metal is partially removed from the furnace, if convenient, again leaving a minimum level of about 1.00 meters of liquid metal and possibly some liquid slag in the furnace. Removal is carried out when the slag is completely removed by overflowing the metal phase through a feed port, or when only a portion of the slag phase has been removed, by tapping the metal through a tap hole appropriately located in the furnace wall.

[0150] After removing the slag and / or metal in mode 4 and / or mode 5, i.e., when more space is available in the furnace again, the feeding of raw materials is resumed depending on the presence of slag in the furnace as in mode 1 or mode 1+2 above, and the next feeding batch is started if the previous feeding batch is finished.

[0151] If downstream processing of the concentrated copper intermediate required more feed material, a portion of the liquid metal phase was intermittently removed from the furnace immediately before or after metal removal, with or without removing any supernatant slag phase.

[0152] To ensure sufficient slag fluidity, additional fluxing material, typically sand, sometimes called "slag formers" as a translation of a commonly used term in German, was added to the furnace as needed. Prior to granulating the slag from the furnace or downstream fuma, additional silicon dioxide was added as needed to ensure the correct Fe / Si ratio so that the risk of hydrogen generation and associated explosion risks during slag injection and granulation were controlled. On average, a total of 11.5 tons of sand per feed batch was introduced into the furnace over the period required to process the feed batch.

[0153] Pure oxygen gas was injected via a lance introduced through the supply port as needed to maintain furnace temperature during modes 1, 1+2, and 3. During these processing modes, the drum furnace was rocked, if possible, to agitate its liquid contents.

[0154] During all treatment modes, compressed air at a pressure of 10 bar gauge was supplied to four tuyeres located at appropriate positions in the furnace wall below the liquid level and injected into the furnace, primarily for bath agitation purposes, but also to introduce additional oxygen into the bath for participation in the intended chemical reactions.

[0155] During the period under consideration, an average total of approximately 92.4 tons of coarse solid material, including some return material, was introduced into the furnace per feed batch, and an average total of approximately 23.2 tons of finely divided material was introduced into the furnace. The average compositions of the coarse solid material and finely divided material were as shown in Table I. Sufficient additional solid scrap iron was included as part of the premixed feed batch of coarse solid material and fed into the furnace as part of that batch to maintain the presence of solid iron suspended in the metallic phase. Accordingly, the amount of this introduced additional scrap iron is included in the composition of the coarse solid material in Table I.

[0156] TIFF0007719771000001.tif87170

[0157] Over the entire processing period considered, an average total of approximately 6.6 tons of oxygen per feed batch was injected at near-ambient temperatures at the bottom of the furnace: as compressed air through four tuyeres, and as oxygen gas via a lance near the interface between the metal phase and its supernatant slag phase. The temperature within the furnace could be maintained very conveniently and precisely within a narrow range of 1150–1180°C. Most importantly, controlled oxygen injection made it possible to avoid temperature fluctuations beyond this range, thereby minimizing tin and / or lead evaporation. Control of the feed rate of raw materials, including coarse solid material and dust injection, made it possible to avoid temperature drops below the desired level, and oxygen injection made it easy to recover from temporary temperature drops if such drops occurred. To remove the metal from the furnace, the temperature was reduced to approximately 1140°C to reduce the risk of damaging the vessel into which the molten metal was transferred.

[0158] The exhaust gases from the furnace were cooled and filtered, and the solids in the cooled gases were collected as smelter dust.

[0159] Over the entire run considered, the amounts and compositions of products shown in Table II were obtained and removed from the smelter on average per feed batch.

[0160] TIFF0007719771000002.tif97170

[0161] The sulfur levels of the metal phase obtained as the concentrated copper intermediate from the example method were determined and found to be well below 2 wt.% for each feed batch, but rather in the range of up to 0.25 wt.%. For each feed batch, sulfur levels in the slag were found to be up to 0.33 wt.% and in the dust up to 0.21 wt.%.

[0162] Although the present invention has now been fully described, it will be appreciated by those skilled in the art that the present invention can be practiced within a wide range of parameters within the scope of the claims without departing from the scope of the invention as defined by the claims. DISCLOSURE OF THE INVENTION (Item 1) A method for recovering copper from a secondary raw material, comprising a smelting step (100) of smelting a feed material (1, 2) comprising said raw material in a furnace in at least one feed batch to recover a concentrated copper intermediate (3) from said furnace, the feedstock of raw materials is gradually introduced into the furnace, the feedstock comprising copper and optionally at least one metal that is more noble than tin under the processing conditions of the furnace, at least partially as an oxide; the feedstock further comprises iron and, optionally, at least one metal or compound at most as noble as iron or zinc under the furnace conditions, the iron and metal at most as noble as iron or zinc being present at least partially in their elemental form; heat is generated in said furnace by oxidation-reduction reactions which convert elemental iron and metals or compounds at most as noble as iron or zinc into their oxides, and convert oxides of copper and oxides of metals nobler than tin into their elemental metals; the elemental metal at least partially collects in a molten liquid metal phase and the oxide at least partially collects in a supernatant liquid slag phase; The liquid phases can be separated and at the end of the smelting step, at least one of the liquid phases is at least partially removed from the furnace as smelting slag (5) and / or as the concentrated copper intermediate (3), During the smelting step, an excess of elemental forms of iron and of metals or compounds at most as noble as iron or zinc under the furnace conditions is maintained in the furnace relative to the amount necessary for completion of the oxidation-reduction reaction, characterised in that during the smelting step, an additional heat input into the furnace is provided by injection of an oxygen-containing gas in order to combust combustible sources of carbon and / or hydrogen that may possibly also be introduced into the furnace, for oxidation of excess amounts of iron and metals or compounds at most as noble as iron or zinc present in the furnace, method. (Item 2) Item 10. The method of claim 1, wherein the feed material further comprises at least one second metal selected from the group consisting of nickel, tin, and lead. (Item 3) 3. The method according to claim 2, wherein the enriched copper intermediate (3) further comprises the at least one second metal. (Item 4) 4. The method according to any one of items 1 to 3, wherein the feed material (1, 2) comprises iron scrap, silicon, zinc, and / or aluminum. (Item 5) 5. The method according to any one of items 1 to 4, further comprising at least partially removing the smelting slag (5) from the furnace. (Item 6) 6. The method of any one of items 1 to 5, further comprising the step of removing at least a portion of the enriched copper intermediate (3) from the furnace. (Item 7) 7. The method according to any one of items 1 to 6, wherein the iron and compounds at most as noble as iron or zinc introduced with the feed material (1, 2) comprise solid iron, solid silicon, solid zinc and / or solid aluminum, preferably copper / iron-containing scrap, silicon-containing scrap, zinc-containing scrap and / or aluminum-containing scrap. (Item 8) 8. The method according to any one of items 1 to 7, wherein the feed material (1, 2) is at least partly solid, and the solid feed material is fed gradually, preferably continuously, to the furnace. (Item 9) 9. The method of any one of items 1 to 8, wherein the input rate of the feed material is maintained below a rate at which the heat production is insufficient to melt the solid feed material and / or raise the feed material to the desired furnace temperature. (Item 10) 10. The method according to any one of the preceding claims, wherein at least a portion of the feed material (1, 2) is in the form of a finely divided portion (2), the finely divided feed material portion (2) having an average particle size of at most 10 mm. (Item 11) 11. The method according to claim 10, wherein the finely divided feedstock portion material (2) is pneumatically transported and injected into the furnace. (Item 12) 12. The method according to claim 11, wherein the finely divided feedstock portion material (2) is injected into the liquid slag phase and above the metal phase of the liquid bath. (Item 13) 13. The method according to any one of items 10 to 12, wherein the average composition of the finely divided feed material portion (2) fed throughout the smelting feed batch in the furnace, after heating to 1150°C, satisfies at least one, and preferably all, of the following conditions: at least 5% by weight of total metals, preferably at least 5% in total of copper, nickel, tin, lead and zinc, Contains up to 70.0% by weight of copper (Cu), Contains up to 2.00% by weight of Nickel (Ni), Contains at least 0.50% and at most 10.00% lead (Pb) by weight, Contains up to 15.00% by weight of tin (Sn), Contains up to 2.00% by weight of antimony (Sb), Contains up to 7.0% by weight of iron (Fe), Contains up to 55.00% by weight of Zinc (Zn). (Item 14) 14. The method according to any one of items 1 to 13, wherein the feed material (1, 2) comprises at least one return material from the processing of the molten liquid metal phase and / or the liquid slag phase formed by the method. (Item 15) 15. The method according to item 14, wherein the at least one return material comprises at least one material selected from the group consisting of reject anodes, other products containing copper, tin and / or lead, dross containing metals as oxides or sulfides formed and removed from downstream processing steps, metal oxides or metal sulfides, preferably oxides or sulfides of copper, nickel, tin, lead and / or zinc, metal silicides, preferably silicides of metals selected from copper, zinc, nickel, iron, lead and tin, crusts or other solids formed on the walls of crucibles or ladles used to transport molten metal and / or molten slag removed from a furnace. (Item 16) 16. The method according to any one of items 1 to 15, wherein the feed materials (1, 2) are introduced into the furnace at the center of the liquid bath. (Item 17) 17. The method according to any one of items 1 to 16, wherein the feed material (1, 2) comprises a coarse fraction (1), and the average composition of the coarse feed material fraction fed throughout the smelting feed batch in the furnace, after heating to 1150°C, satisfies at least one, preferably all, of the following conditions: at least 20% by weight of total metals, preferably at least 20% in total of copper, nickel, tin, lead, and zinc; Contains at least 10.0% by weight and at most 70.0% by weight of copper (Cu), containing at least 0.50% by weight and at most 2.00% by weight of nickel (Ni), Contains at least 1.00% and at most 8.00% by weight of lead (Pb), Contains at least 0.50% by weight and at most 2.50% by weight of tin (Sn), Contains up to 0.10% by weight of antimony (Sb), containing at least 10.0% by weight and at most 35.00% by weight of iron (Fe), Contains at least 2.00% and at most 15.00% by weight of zinc (Zn). (Item 18) 18. The method according to any one of items 1 to 17, wherein the amount of iron and metals or compounds at most as noble as iron or zinc dissolved in the molten metal in the furnace is maintained at at least 1.0 wt. %, preferably at least 1.5 wt. %, and the concentration of said metals and compounds at most as noble as iron or zinc is converted to an equivalent iron concentration, which is an iron concentration that, when reacted with oxygen under furnace conditions, can contribute the same amount of heat of reaction as said metals or compounds at most as noble as iron or zinc. (Item 19) 19. The method according to any one of items 1 to 18, wherein the amount of iron and / or metals and compounds which are at most as noble as iron or zinc under furnace conditions dissolved in the molten metal in the furnace is maintained at a maximum of 10.0 wt.%, preferably at a maximum of 9.0 wt.%, and wherein the concentration of metals and compounds which are at most as noble as iron or zinc is converted to an equivalent iron concentration which, when reacted with oxygen under furnace conditions, can contribute the same amount of heat of reaction as the metals or compounds which are at most as noble as iron or zinc. (Item 20) 20. The method of any one of the preceding claims, wherein elemental iron is introduced into the smelting step (100) at a rate such that an excess of iron in excess of its solubility in the metal bath at the furnace conditions is maintained in the molten bath during the method. (Item 21) 21. The method of claim 20, wherein the amount of excess iron present in the furnace is maintained by at least periodically sampling the molten metal phase in the furnace and analyzing the samples for iron. (Item 22) 22. The method according to any one of items 1 to 21, wherein the combustible source of carbon and / or hydrogen is selected from the group consisting of coke, charcoal, carbon black, hydrocarbons, natural gas, methane, ethane, propane, butane, hydrocarbons that are liquid at normal conditions, hydrocarbon-containing polymers, plastics, waste plastics, grease, oil, paint, varnish, rubber, preferably waste products thereof, and combinations thereof. (Item 23) 23. The method according to item 22, wherein the amount of combustible sources of carbon and / or hydrogen is kept below a level at which slag foaming would impair the processing of said smelting step, and preferably is kept significantly below this level at which the risk of slag foaming also remains acceptably low. (Item 24) 24. The method of any one of the preceding claims, wherein at least a portion of the oxygen-containing gas is introduced near the interface between the metal phase and its supernatant slag phase. (Item 25) 25. The method according to any one of the preceding claims, wherein at least a portion of the oxygen-containing gas is introduced by means of at least one metal lance, the tip of which is immersed in the liquid slag phase. (Item 26) 26. The method of claim 25, wherein the gas injected through the metal lance comprises at least 30% by volume of oxygen, more preferably the gas is high purity oxygen. (Item 27) 27. The method of claim 25 or 26, wherein the flow of gas through the metal lance provides sufficient cooling to avoid the lance corroding and / or melting. (Item 28) 28. The method of any one of the preceding claims, wherein at least a portion of the oxygen-containing gas is introduced into the bottom of the furnace through at least one tuyeres, preferably a plurality of tuyeres, more preferably a plurality of tuyeres that are evenly distributed across the bottom of the furnace. (Item 29) 29. The method according to item 28, wherein the gas introduced through the at least one tuyere is an oxygen-containing gas containing up to 50% by volume of oxygen, preferably air. (Item 30) 30. The method of claim 28 or 29, wherein the gas introduced through the at least one tuyere is at a lower temperature than the molten liquid metal phase surrounding the tuyere. (Item 31) 31. The method according to any one of the preceding claims, wherein the smelting slag (5) produced by the method comprises at least 20% by weight of iron (Fe). (Item 32) 32. The method according to any one of items 1 to 31, wherein the composition of the smelting slag (5) produced satisfies at least one, preferably all, of the following conditions: Contains up to 1.00% by weight of copper (Cu), Contains up to 0.20% by weight of nickel (Ni), Contains up to 2.00% lead (Pb) by weight, Contains a maximum of 1.00% by weight of tin (Sn), Contains up to 22.50% by weight of zinc (Zn). (Item 33) 33. The method according to any one of items 1 to 32, wherein the composition of the enriched copper intermediate (3) as the main product from the smelting step (100) satisfies at least one, preferably all, of the following conditions: containing at least 50.0% by weight of copper (Cu), containing at least 0.01% by weight of nickel (Ni), Contains at least 0.10% by weight of lead (Pb), containing at least 1.00% by weight of tin (Sn), containing at least 0.05% by weight of iron (Fe), containing at least 0.10% by weight of zinc (Zn), Contains up to 5% by weight of sulfur (S). (Item 34) 34. The method according to any one of the preceding items, wherein the liquid bath in the furnace has a temperature in the range of 1100 to 1300°C. (Item 35) 35. The method according to any one of the preceding claims, wherein the exhaust gas from the furnace is collected and treated by cooling and / or filtering. (Item 36) 36. The method according to claim 35, wherein secondary exhaust gases from the surroundings of the furnace are also collected and treated by filtration, optionally in combination with cooling. (Item 37) 37. The method of any one of the preceding claims, wherein the smelting step (100) is carried out in a smelting furnace. (Item 38) 38. The method of any one of the preceding claims, wherein the walls of the furnace are cooled at least partially across the wall surface of the furnace. (Item 39) 39. The method according to any one of the preceding claims, further comprising a step (400) of fuming the slag phase formed in the smelting step (100) to obtain fumed slag (13), preferably wherein the fuming step is carried out in a fuming furnace. (Item 40) 40. The method according to any one of the preceding claims, wherein the slag (5, 13) is granulated as it is removed from the smelting step (100) or the fuming step (400). (Item 41) 41. The method according to any one of the preceding items, further comprising using the produced slag (5, 13) in an end use selected from providing a wear layer and / or coating on roof tiles or shingles, as a blasting sand or blasting grit component, as a foam tile component, as a black colorant, preferably in construction products, more preferably in black tiles, as a black solid mass, preferably for decorative purposes, as high density ballast, preferably for underwater applications, more preferably for hydraulic engineering, and combinations thereof. (Item 42) 42. The method according to any one of the preceding items, further comprising the step of adding the produced slag (5, 13) as aggregate and / or binder, preferably as a binder for aggregates, preferably as an active binder, more preferably as a binder with pozzolanic activity, even more preferably as a substitute for Portland cement, even more preferably as a partial substitute for Portland cement, during the production of objects for the construction industry. (Item 43) 43. The method according to item 42, wherein the produced slag (5, 13) is added as a binder in an inorganic polymer composition, preferably in combination with a base, more preferably as the main binder in the inorganic polymer composition, even more preferably as the only binder in the inorganic polymer composition. (Item 44) Item 44. The method of item 43, further comprising foaming the inorganic polymer composition. (Item 45) 45. The method according to any one of items 42 to 44, wherein the objects for the construction industry are building elements, preferably the building elements are selected from the list of tiles, paving stones, blocks, concrete blocks and combinations thereof. (Item 46) 46. The method according to any one of items 42 to 45, wherein the object for the construction industry has a foam structure. (Item 47) 47. The method of any one of items 42 to 46, further comprising using the object for improving thermal and / or sound insulation, for X-ray shielding, and combinations thereof. (Item 48) 48. The method according to any one of the preceding claims, further comprising purifying (200) the enriched copper intermediate (3) to obtain a purified copper product (8) together with at least one copper refining slag (6). (Item 49) Item 49. The method of claim 48, wherein the concentrated copper intermediate (3) further comprises tin and lead, and further comprising recovering a raw solder metal composition (7) from the concentrated copper intermediate (3). (Item 50) Item 50. The method of claim 49, further comprising recovering (500) from the raw solder metal composition (7) at least one of a refined soft lead product (10), a refined hard lead product (11), and a refined tin product (12). (Item 51) 51. The method of claim 49 or 50, further comprising pre-purifying the raw solder metal composition (7) to produce a pre-purified solder metal composition. (Item 52) 52. The method of any one of items 49 to 51, further comprising conditioning the raw solder metal composition (7) or the pre-purified solder metal composition to produce a conditioned solder metal composition. (Item 53) Item 53. The method of claim 52, further comprising a first distillation step for distilling the prepared solder composition, wherein lead is removed from the solder by evaporation to obtain a first distillation overhead product and a first distillation bottoms product. (Item 54) Item 54. The method of item 53, further comprising removing at least one contaminant selected from metallic arsenic, antimony, and tin from the first distillation overhead product to obtain a purified soft lead product (10). (Item 55) 55. The method of claim 53 or 54, wherein the first distillation bottoms product of the first distillation step contains lead and silver, and further comprising the step of separating the bottoms product of the first distillation step by fractional crystallization into a first silver-enriched liquid effluent product at the liquid end of the crystallization step and a first tin-enriched product at the crystal end of the crystallization step. (Item 56) 56. The method of claim 55, further comprising separating the first silver-enriched liquid effluent product, preferably by electrolysis, into a lead- and tin-rich product and a silver-rich product, whereby the anode slime represents the silver-rich product. (Item 57) 57. The method of claim 55 or 56, wherein the first tin-enriched product further contains lead and antimony, and the method further comprises a second distillation step for distilling the first tin-enriched product, primarily vaporizing lead and antimony, to obtain a second distillation overhead product and a second distillation bottoms product. (Item 58) Item 58. The method according to item 57, further comprising a third distillation step for distilling the second distillation overhead product, vaporizing lead, to obtain a third distillation overhead product and a third distillation bottom product, preferably the third distillation product being at least partially recycled to the feed of the second distillation step and / or the feed of the fractional crystallization step. (Item 59) 59. The method according to claim 57 or 58, further comprising removing at least one contaminant selected from metallic arsenic and tin from the third distillation overhead product to obtain a purified hard lead product (11). (Item 60) 60. The process of any one of items 57 to 59, further comprising purifying the second distillation bottoms product to obtain a purified tin product (12). (Item 61) 61. The method of any one of items 48 to 60, further comprising the step of casting the refined copper product (8) to produce a refined copper anode (9). (Item 62) 62. The method of any one of the preceding items, wherein at least part of the method is electronically monitored and / or controlled.

Claims

1. A method for recovering copper from a secondary raw material, comprising a smelting step (100) in which a feed material (1, 2) comprising said raw material is smelted in a furnace under furnace conditions to recover a concentrated copper intermediate (3) from the furnace in at least one feed batch, the feedstock of raw material is gradually introduced into the furnace, the feedstock comprising copper at least partially as an oxide; the feedstock further comprises iron, the iron being at least partially present in elemental form; heat is generated in said furnace by oxidation-reduction reactions which convert elemental iron and, if present, metals or compounds at most as noble as iron or zinc into oxides, and copper oxides and, if present, oxides of metals more noble than tin into elemental metals; the elemental metal at least partially collects in a molten liquid metal phase and the oxide at least partially collects in a supernatant liquid slag phase, the molten liquid metal phase and the supernatant liquid slag phase forming two liquid phases in the furnace; The liquid phases may be separated and at the end of the smelting step, at least one of the liquid phases is at least partially removed from the furnace as smelting slag (5) and / or as the concentrated copper intermediate (3), the concentrated copper intermediate (3) comprising at least 50.0% by weight of copper, at most 15.00% by weight of lead and at most 12.00% by weight of tin, During the smelting step, an excess of elemental forms of iron and of metals or compounds which are at most as noble as iron or zinc under the furnace conditions is maintained in the furnace relative to the amount required for completion of the oxidation-reduction reaction, characterised in that during the smelting step, an additional heat input into the furnace is provided by injection of an oxygen-containing gas in order to combust combustible sources of carbon and / or hydrogen that may, if present, be further introduced into the furnace, due to oxidation of the excess amounts of iron and metals or compounds at most as noble as iron or zinc present in the furnace. method.

2. The method of claim 1 , wherein the feed material further comprises at least one second metal selected from the group consisting of nickel, tin, and lead.

3. 3. The method of claim 2, wherein the enriched copper intermediate (3) further comprises the at least one second metal.

4. 4. The method according to claim 1, wherein the feed material (1, 2) is at least partially solid, the solid portion of the feed material (1, 2) forming a solid feed material portion, and the solid feed material portion is gradually fed into the furnace.

5. 5. The method according to any one of claims 1 to 4, wherein at least a portion of the feed material (1, 2) is in the form of a finely divided solid feed material portion (2), the finely divided solid feed material portion (2) having an average particle size of at most 10 mm.

6. 6. The method of any one of claims 1 to 5, wherein the amount of iron and metals or compounds at most as noble as iron or zinc dissolved in the molten liquid metal phase in the furnace is maintained at at least 1.0 wt. %, and the concentrations of the metals and compounds at most as noble as iron or zinc are converted to equivalent iron concentrations that, when reacted with oxygen under the furnace conditions, can contribute the same amount of heat of reaction as the metals or compounds at most as noble as iron or zinc.

7. 7. The method of claim 1, wherein at least a portion of the oxygen-containing gas is introduced by at least one metal lance having a tip immersed in the liquid slag phase.

8. 8. The method of any one of claims 1 to 7, wherein at least a portion of the oxygen-containing gas is introduced into the bottom of the furnace through at least one tuyeres.

9. 9. The method according to any one of claims 1 to 8, wherein the composition of the concentrated copper intermediate (3) as the main product from the smelting step (100) satisfies at least one of the following conditions: Contains at least 50.0% by weight of copper (Cu), Contains at least 0.01% by weight of nickel (Ni), Contains at least 0.10% by weight of lead (Pb), Contains at least 1.00 wt. % tin (Sn); - containing at least 0.05% by weight of iron (Fe), - containing at least 0.10% by weight of zinc (Zn); - Contains up to 5% by weight of sulfur (S).

10. 10. The method of any one of claims 1 to 9, further comprising the step of fuming (400) the slag phase formed in the smelting step (100) to obtain fumed slag (13).

11. 11. The method according to any one of claims 1 to 10, further comprising the step of adding the produced slag (5, 13) as aggregate and / or as binder during the production of objects for the construction industry.

12. 12. The method of any one of claims 1 to 11, further comprising purifying (200) the enriched copper intermediate (3) to obtain a refined copper product (8) together with at least one copper refinery slag (6).

13. 13. The method of claim 12, wherein the concentrated copper intermediate (3) further comprises tin and lead, and further comprising recovering a raw solder metal composition (7) from the concentrated copper intermediate (3).

14. 14. The method of claim 13, further comprising recovering (500) from said raw solder metal composition (7) at least one of a refined soft lead product (10), a refined hard lead product (11), and a refined tin product (12).

15. 15. The method of any one of claims 12 to 14, further comprising casting the refined copper product (8) to produce a refined copper anode (9).

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