Oxidative desulfurization method for zinc sulfide material

Abstract

The invention provides a zinc sulfide material oxidative desulfurization method which comprises the following steps: carrying out primary oxidative desulfurization reaction on a mixed material formed by a zinc sulfide material and a flux and oxygen-enriched gas in an oxidative smelting area of a furnace chamber to obtain a primary oxide material and a copper matte material; the primary oxide material is subjected to a second oxidation desulfurization reaction in an oxidation smelting area to form a high-zinc material and high-cadmium smoke dust; wherein the temperature of the first oxidation desulfurization reaction is t1, and the oxygen-material ratio is OM1; the temperature of the second oxidation desulfurization reaction is t2, and the oxygen-material ratio is OM2; 50 DEG C < = t2-t1 < = 450 DEG C; 50Nm < 3 > / t < = OM2-OM1 < = 400Nm < 3 > / t. The zinc sulfide material does not need complex material preparation and treatment and is directly added into the oxidation smelting area of the zinc smelting furnace, the first oxidation desulfurization reaction and the second oxidation desulfurization reaction are sequentially carried out, and the valuable metal recovery rate of the zinc sulfide material is increased.

Description

Technical Field

[0001] The present application relates to the field of metal reduction recovery, and in particular to a method for oxidative desulfurization of zinc sulfide materials. Background Art

[0002] Pyrometallurgical zinc smelting has the characteristics of processing complex raw materials and simple processes, and has been widely used in lead and zinc metal smelting. Among them, the pyrometallurgical process mainly includes blast furnace, vertical tank and electric furnace processes. Blast furnace zinc smelting can only process lead-zinc mixed ore with a certain lead-zinc ratio. The raw materials must be sintered before entering the furnace. The final slag of the blast furnace contains 5%-7% zinc, and the recovery rate of valuable metals such as zinc is low; in vertical tank zinc smelting, the zinc sulfide material must be roasted, pelletized and other desulfurization molding treatments before entering the furnace. The raw material composition requirements are high and the material preparation process is complicated. The final slag contains 5%-10% zinc, and the recovery rates of valuable metals such as zinc, copper, gold and silver are all low; in electric furnace zinc smelting, the zinc sulfide material needs to be roasted and desulfurized before entering the furnace. The atmosphere and temperature in the furnace need to be controlled during the smelting process after entering the furnace. The final slag contains 3%-6% zinc, and the recovery rate of valuable metals is low. Summary of the invention

[0003] The present application aims to solve at least one of the technical problems in the related art to a certain extent. The present application proposes a method for oxidative desulfurization of zinc sulfide materials, wherein the zinc sulfide materials do not need complicated material preparation and processing, and are directly added to the oxidative smelting zone of the zinc smelting furnace, and the first oxidative desulfurization reaction and the second oxidative desulfurization reaction are sequentially performed to improve the recovery rate of valuable metals of the zinc sulfide materials.

[0004] According to an embodiment of the present application, a method for oxidative desulfurization of zinc sulfide material is proposed, comprising the following steps: The mixed material formed by the zinc sulfide material and the flux undergoes a first oxidation desulfurization reaction with the oxygen-rich gas in the oxidation smelting zone of the furnace chamber to obtain a preliminary oxide material and a copper matte material; The preliminary oxide material is subjected to a second oxidation desulfurization reaction in the oxidation smelting zone to form high-zinc material and high-cadmium smoke; wherein the temperature of the first oxidation desulfurization reaction is t1, and the oxygen-to-material ratio is OM1; the temperature of the second oxidation desulfurization reaction is t2, and the oxygen-to-material ratio is OM2; 50°C≤t2-t1≤450°C; 50Nm 3 / t≤OM2-OM1≤400Nm 3 / t.

[0005] In some embodiments, the temperature of the first oxidation desulfurization reaction is 1100-1300°C, and the oxygen-to-material ratio is 100-250 Nm 3 / t.

[0006] In some embodiments, the temperature of the second oxidation desulfurization reaction is 1350-1550°C, and the oxygen-to-material ratio is 300-500 Nm 3 / t.

[0007] In some embodiments, the particle size of the mixed material is D, wherein 0.05 mm≤D≤5 mm.

[0008] In some embodiments, the oxygen concentration of the oxygen-rich gas is 23-99.8%, and the pressure in the furnace chamber is 0.2 MPa-0.5 MPa.

[0009] In some embodiments, the mass ratio of the zinc sulfide material to the flux in the mixed material is 5-20:1.

[0010] In some embodiments, the flux includes at least one of quartz sand, quicklime, and limestone.

[0011] In some embodiments, the blowing method in the oxidation smelting zone includes side blowing alone, bottom blowing alone, or a mixture of side blowing and bottom blowing.

[0012] In some embodiments, the mass percentage of sulfur in the preliminary oxidation material obtained in the first oxidation desulfurization reaction is 2%-5%; And / or, based on the zinc sulfide material, according to the mass percentage, 70%-80% of the copper element, 80%-90% of the gold element and 80%-90% of the silver element in the zinc sulfide material are enriched in the copper matte material; And / or, the mass percentage of copper element in the copper matte material is 10%-30%.

[0013] In some embodiments, the mass percentage of sulfur in the high-zinc material is less than 1%; And / or, the mass percentage of zinc element in the high-zinc material is 40%-60%; And / or, the mass percentage of cadmium element in the high-cadmium smoke is greater than 12%.

[0014] The zinc sulfide material of the present application does not require complicated preparation and processing. The mixed material has a suitable particle size, is fully contacted with the oxygen-rich gas in the oxidation smelting zone of the furnace chamber, and undergoes the first oxidation desulfurization reaction under low temperature and low oxygen potential conditions to obtain a preliminary oxide material and a copper matte material. The copper matte material is discharged from a siphon port set in the oxidation smelting zone; and the preliminary oxide material continues to undergo deep oxidation desulfurization in the oxidation smelting zone under high temperature and high oxygen potential conditions to form a high-zinc material and high-cadmium smoke. The above-mentioned oxidation desulfurization method of the zinc sulfide material does not require complicated preparation and processing of the zinc sulfide material, and can effectively improve the recovery rate of valuable metals in the zinc sulfide material.

[0015] Additional aspects and advantages of the present application will be given in part in the description below, and in part will become apparent from the description below, or will be learned through the practice of the present application. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] The above and / or additional aspects and advantages of the present application will become apparent and easily understood from the following description of the embodiments in conjunction with the accompanying drawings, in which: Figure 1 It is a flow chart of a method for oxidative desulfurization of zinc sulfide material according to one embodiment of the present application. DETAILED DESCRIPTION

[0017] Embodiments of the present application are described in detail below, and examples of the embodiments are shown in the accompanying drawings, wherein the same or similar reference numerals throughout represent the same or similar elements or elements with the same or similar functions. The embodiments described below with reference to the accompanying drawings are exemplary and are only used to explain the present application, and cannot be construed as limiting the present application. On the contrary, the present application includes all changes, modifications and equivalents that fall within the spirit and connotation of the appended claims.

[0018] The existing hydrometallurgical zinc smelting technology has a long process, complex process, huge investment and high energy consumption. Most importantly, the hydrometallurgical process produces a large amount of leaching slag, iron slag, etc., with an output rate of more than 50%, which are all hazardous wastes and need to be harmlessly treated, which in turn causes a large amount of energy consumption and brings new pollution. The existing pyrometallurgical zinc smelting technology generally has high energy consumption, complex material preparation process, low zinc direct recovery rate and recovery rate, and small single series production capacity, which cannot meet the requirements of modern large-scale industrial production.

[0019] At present, the relevant technology mentions the lead-zinc ore smelting method of melting the lead-zinc ore in an oxidation smelting furnace, sending the melt to an industrial frequency electric reduction furnace for reduction, and using the traditional lead rain condensation or zinc rain condensation to obtain crude zinc for zinc vapor; or using an oxygen bottom blowing smelting furnace to melt the zinc sulfide material, sending the melt to a side blowing reduction furnace for reduction, and using the traditional lead rain condensation or zinc rain condensation to obtain crude zinc for zinc vapor; using an oxygen bottom blowing smelting furnace to melt the zinc sulfide material, and then sending the ingot to a blast furnace for reduction, and using the traditional lead rain condensation or zinc rain condensation to obtain crude zinc for zinc vapor. The above methods all solve many problems existing in hydrometallurgical zinc smelting, but compared with the existing pyrometallurgical zinc smelting method, they only mainly solve the problem of complex material preparation system, and the smelting process and the recovery of valuable metals have not been significantly improved.

[0020] In order to solve the problem of low recovery rate of valuable metals, some related technologies mention the use of blast furnace smelting. The molten slag needs to be cooled by the ingot, the material preparation process is complicated, the energy consumption is high, and the zinc recovery rate has not been improved compared with the traditional pyrometallurgical zinc smelting technology. There is room for further improvement in the recovery rate of valuable metals. Some other related technologies mention the use of two metallurgical furnaces. The molten slag flows from the bottom-blown furnace to the side-blown furnace, which inevitably causes heat loss and increases the fume escape point. The side-blown furnace reduction belongs to the molten pool smelting, and a large amount of oxygen-rich air needs to be blown in, resulting in a low zinc vapor concentration, which is more likely to cause secondary oxidation of zinc vapor and reduce the direct recovery rate of zinc. The smelting temperature of the side-blown furnace is 1200-1250℃, the slag contains a high zinc content, the direct recovery rate and recovery rate of zinc are low, iron cannot be recovered, and the subsequent flue gas treatment cost is high. There is room for further improvement in the recovery rate of valuable metals. In addition, the related art mentions the use of two metallurgical furnaces. The molten slag flows from the oxidation smelting furnace into the power frequency electric thermal reduction furnace, which inevitably causes heat loss and increases the fume escape point. The smelting temperature of the power frequency electric thermal reduction furnace is limited, which will cause the slag to contain high zinc, low zinc recovery rate, and inability to recover iron. The single series production capacity of the power frequency electric thermal reduction furnace is limited, and it is difficult to adapt to large-scale industrial production. There is room for further improvement in the recovery rate of valuable metals.

[0021] Based on this, the technical solution of the embodiment of the present application provides a method for oxidative desulfurization of zinc sulfide materials. The zinc sulfide materials do not require complicated preparation and processing, and are directly added to the oxidative smelting zone of the zinc smelting furnace to carry out the first oxidative desulfurization reaction and the second oxidative desulfurization reaction in sequence, thereby improving the recovery rate of valuable metals in the zinc sulfide materials.

[0022] "Scope" disclosed in the present application is limited in the form of lower limit and upper limit, and a given range is limited by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundary of a special range. The scope limited in this way can be including end values ​​or not including end values, and can be arbitrarily combined, that is, any lower limit can be combined with any upper limit to form a scope. For example, if the scope of 60-120 and 80-110 is listed for a specific parameter, it is understood that the scope of 60-110 and 80-120 is also expected. In addition, if the minimum range values ​​1 and 2 are listed, and if the maximum range values ​​3, 4 and 5 are listed, the following scope can be all expected: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In the present application, unless otherwise specified, the numerical range "ab" represents the abbreviation of any real number combination between a and b, wherein a and b are real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" are listed in this document, and "0-5" is just an abbreviation of these numerical combinations. In addition, when a parameter is expressed as an integer ≥ 2, it is equivalent to disclosing that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0023] In the description of the embodiments of the present application, the term "and / or" is only a description of the association relationship of the associated objects, indicating that there may be three relationships. For example, A and / or B can represent: A exists alone, A and B exist at the same time, and B exists alone. In addition, the character " / " in this article generally indicates that the associated objects before and after are in an "or" relationship.

[0024] To achieve the above purpose, according to the embodiments of the present application, a method for oxidative desulfurization of zinc sulfide material is proposed. Figure 1 , including the following steps: S1: The mixture of zinc sulfide material and flux undergoes the first oxidation desulfurization reaction with oxygen-rich gas in the oxidation smelting zone of the furnace chamber to obtain preliminary oxide material and copper matte material; S2: The preliminary oxide material is subjected to a second oxidation desulfurization reaction in the oxidation smelting zone to form high-zinc material and high-cadmium smoke; the temperature of the first oxidation desulfurization reaction is t1, and the oxygen-to-material ratio is OM1; the temperature of the second oxidation desulfurization reaction is t2, and the oxygen-to-material ratio is OM2; 50℃≤t2-t1≤450℃; 50Nm 3 / t≤OM2-OM1≤400Nm 3 / t.

[0025] Among them, in S1, the mixed material formed by the zinc sulfide material and the flux, wherein the zinc sulfide material includes zinc, lead, sulfur elements, and usually also includes iron, sulfur, calcium, and silicon elements. In addition to the above elements, in some embodiments, the lead-zinc sulfide material may also include other elements, such as oxygen, magnesium, copper, aluminum, cadmium, arsenic, etc. Compared with other elements, the content of zinc, lead, iron, sulfur, calcium, and silicon elements is relatively high. Exemplarily, the lead-zinc sulfide material includes Zn 10-40wt.%; Pb 5-30 wt.%; S 10-30 wt.%; Fe 3-15 wt.%; Ca 1-10 wt.%; SiO22-10 wt.%. For example, Zn 20-40 wt.%, Pb 10-30 wt.%, S15-30 wt.%, Fe 4-15 wt.%, Ca 1-5 wt.% and SiO22-6wt.%. Lead-zinc sulfide materials can be natural lead-zinc sulfide minerals, or they can be smelted raw materials with relatively high sulfur, lead and zinc elements. Among them, according to the highest content of the elements, lead-zinc sulfide materials can be divided into lead concentrate (highest lead content) and zinc concentrate (highest lead content).

[0026] Exemplarily, the main elements and component contents of the lead concentrate are Pb 36.82 wt.%, Zn 16.25 wt.%, S 13.86 wt.%, Fe 3.84 wt.%, Cu 0.40 wt.%, CaO 3.08 wt.% and SiO25.16 wt.%, respectively.

[0027] Illustratively, the zinc concentrate has main element or component contents of Zn 43.49 wt.%, Pb 3.09 wt.%, S2 8.61 wt.%, Fe 11.10 wt.%, Cu 0.74 wt.%, Cd 0.39 wt.%, CaO 0.82 wt.% and SiO2 6.12 wt.%.

[0028] In the present application, the mixture formed by the zinc sulfide material and the flux in a mass ratio of 5-20:1 is fine particles, wherein the flux includes at least one of quartz sand, quicklime and limestone, and its particle size does not need to be precisely controlled, and only needs to be less than or equal to 5 mm and greater than or equal to 0.05 mm; in other words, the particle size of the mixture is D, wherein 0.05 mm≤D≤5 mm; for example, D is 0.05 mm, 0.1 mm, 0.5 mm, 1 mm, 2 mm, 3 mm, 4 mm, 5 mm, etc., wherein the particle size of the mixture is reasonable. When the particle size of the mixture is too large, such as greater than 5 mm, the specific surface area of ​​the mixture is reduced, and the contact area with the oxygen-rich gas is reduced, resulting in a reduced reaction rate.

[0029] For example, the mass ratio of zinc sulfide material to flux is (5, 6, 7, 8, 10, 12, 14, 15, 17, 18, 19, 20): 1. When the mass ratio of zinc sulfide material to flux is large, such as greater than 20, the final high-zinc material generated has a high melting point and a large slag viscosity, which is not conducive to smelting; when the mass ratio of zinc sulfide material to flux is small, such as less than 5, the flux amount is too high, resulting in increased smelting energy consumption and increased production costs.

[0030] The oxygen concentration in the oxygen-rich gas is 23-99.8%, and the pressure in the furnace chamber is 0.2MPa-0.5MPa; the oxygen-rich gas can be pure oxygen or a mixture of oxygen and other gases (such as nitrogen). In the present embodiment, the oxygen concentration in the oxygen-rich gas is 23-99.8%. The oxygen concentration in the oxygen-rich gas is relatively high, which can provide sufficient oxygen to allow the mixed materials to fully react.

[0031] The mixed material and the oxygen-rich gas enter the oxidation smelting zone through the oxidation smelting zone spraying method for mixing and reaction, wherein the oxidation smelting zone spraying method includes single side blowing, single bottom blowing or side blowing and bottom blowing mixed. The mixed material undergoes the first oxidation desulfurization reaction in the oxidation smelting zone to obtain preliminary oxide material and copper matte material, wherein the mass percentage of sulfur element in the preliminary oxide material is 2%-5%; based on the zinc sulfide material, according to the mass percentage content, 70%-80% of the copper element, 80%-90% of the gold element and 80%-90% of the silver element in the zinc sulfide material are enriched in the copper matte material for recovery; based on the copper matte material, the mass percentage of copper element in the copper matte material is 10%-30%.

[0032] The initial oxide material in S2 undergoes a second oxidation desulfurization reaction in the oxidation smelting zone to form high-zinc material and high-cadmium smoke. The mass percentage of sulfur in the high-zinc material is less than 1%; the mass percentage of zinc in the high-zinc material is 40%-60%; the mass percentage of cadmium in the high-cadmium smoke is greater than 12%. The temperature of the first oxidation desulfurization reaction is t1, and the oxygen-to-material ratio is OM1; the temperature of the second oxidation desulfurization reaction is t2, and the oxygen-to-material ratio is OM2; 50℃≤t2-t1≤450℃; 50Nm 3 / t≤OM2-OM1≤400Nm 3 / t.

[0033] For example, the difference between t2 and t1 is 50°C, 100°C, 150°C, 200°C, 250°C, 300°C, 350°C, 400°C, 450°C, etc.; the difference between OM2 and OM1 is 50Nm 3 / t、100Nm 3 / t、150Nm 3 / t、200Nm 3 / t, 250Nm 3 / t、300Nm 3 / t、350Nm 3 / t、400Nm 3 / t, etc. For example, the temperature of the first oxidation desulfurization reaction is 1100-1300℃, and the oxygen-to-material ratio is 100-250Nm 3 / t. In some embodiments, the temperature of the first oxidation desulfurization reaction is 1100°C, 1200°C, 1300°C, etc.; and the oxygen-to-material ratio is 100Nm 3 / t, 150Nm 3 / t、200Nm 3 / t, 250Nm 3 / t, etc.; when the temperature of the first oxidation desulfurization reaction is lower than 1100℃, the slag is sticky, which is not conducive to the oxidation desulfurization reaction; when the temperature of the first oxidation desulfurization reaction is higher than 1300℃, the oxidation desulfurization reaction proceeds too fast, which is not conducive to the formation of copper matte materials; when the oxygen-to-material ratio of the first oxidation desulfurization reaction is lower than 100Nm 3 / t, the oxygen content is too low, which will cause the initial oxidation material to contain too much sulfur, which is not conducive to the second desulfurization reaction; when the oxygen-to-material ratio of the first oxidation desulfurization reaction is higher than 250Nm 3 / t, the first oxidation desulfurization reaction is too fast, which is not conducive to the formation of copper matte materials.

[0034] In some embodiments, the temperature of the second oxidation desulfurization reaction is 1350-1550°C, and the oxygen-to-material ratio is 300-500 Nm 3 / t, the temperature of the second oxidation desulfurization reaction in the example is 1350℃, 1400℃, 1450℃, 1550℃, etc.; at the same time, its oxygen-to-material ratio is 300Nm 3 / t、350Nm 3 / t、400Nm 3 / t、500Nm 3 / t, etc.; when the temperature of the second oxidation desulfurization reaction is lower than 1350℃, the slag is sticky, which is not conducive to the second deep oxidation desulfurization reaction; when the temperature of the second oxidation desulfurization reaction is higher than 1550℃, the molten pool temperature is too high, affecting the furnace body of the zinc smelting furnace and the life of the spray gun for the oxidation smelting zone; when the oxygen-to-material ratio of the second oxidation desulfurization reaction is lower than 300Nm 3 / t, there is insufficient oxygen, which is not conducive to the second deep oxidation desulfurization reaction; when the oxygen-to-material ratio of the second oxidation desulfurization reaction is higher than 500Nm 3 / t, the amount of oxygen required for desulfurization exceeds that required, resulting in waste.

[0035] The zinc sulfide material of the present application does not require complicated preparation and processing. The mixed material formed by the zinc sulfide material and the flux has a suitable particle size. The mixed material is fully contacted with the oxygen-rich gas in the oxidation smelting zone of the furnace chamber and undergoes the first oxidation desulfurization reaction under low temperature and low oxygen potential conditions. By controlling the oxygen-to-material ratio to create a low temperature and low oxygen potential atmosphere, the limited oxygen preferentially reacts with the zinc-containing sulfide with high content and high activity to remove a portion of the sulfur, and the copper-containing sulfide in the mixed material generates copper matte, and finally a preliminary zinc-containing oxide material, i.e., a preliminary oxide material (a portion of the sulfur is still not removed) and a copper matte material are obtained. The copper matte material is discharged from a siphon port set in the oxidation smelting zone, that is, during the first oxidation desulfurization reaction, under the oxygen-to-material ratio conditions, it is ensured that the oxygen-rich gas can provide an oxygen-rich environment for the mixed gas to promote the oxidation desulfurization reaction, and at the same time, at the reaction temperature, the mixed material can reach a better reaction state in the first oxidation desulfurization reaction.

[0036] The preliminary oxide material continues to undergo deep oxidation desulfurization in the oxidation smelting zone under high temperature and high oxygen potential conditions to form high-zinc materials and high-cadmium smoke. During the second oxidation desulfurization reaction, 50°C ≤ t2-t1 ≤ 450°C, where the temperature of the first oxidation desulfurization reaction is t1, and the temperature of the second oxidation desulfurization reaction is t2. At this reaction temperature, the sulfide concentrate can be well subjected to deep oxidation desulfurization to form high-zinc materials and high-cadmium smoke. The above-mentioned oxidation desulfurization method of the zinc sulfide material provided in the present application does not require complex preparation and processing of the zinc sulfide material, and can effectively improve the recovery rate of valuable metals of the zinc sulfide material.

[0037] To facilitate further understanding of the present application, the scheme of the present application is further described below in conjunction with the embodiments. Those skilled in the art will understand that the description in the present application is only part of the examples, and any other suitable specific examples are within the scope of the present application.

[0038] Example 1 The present embodiment provides a method for oxidative desulfurization of zinc sulfide materials, wherein zinc concentrate is used as the zinc sulfide material, and the specific operating parameters are as follows: the zinc concentrate is mixed with quartz sand at a mass ratio of 20:1 without complicated material preparation to obtain a mixed material with a particle size of 0.05 mm, and the mixed material is added to the oxidation smelting zone of a short-process pyrometallurgical zinc smelting furnace; the mixed material is heated in the oxidation smelting zone at 1100° C. and the oxygen-to-material ratio is 100 Nm 3 / t conditions for the first oxidation desulfurization reaction, this process forms copper matte material and preliminary oxide material, the mass percentage of S element in the preliminary oxide material is 5%, the mass percentage of Cu element in the copper matte material is 10%, the copper matte material is deposited on the bottom of the molten pool and discharged from the siphon port set in the oxidation smelting zone; increase the temperature of the oxidation smelting zone to 1350℃ and increase the oxygen-to-material ratio to 300Nm 3 / t, so that the slag is further desulfurized to form high-zinc material and high-cadmium smoke. In terms of mass percentage, the high-zinc material contains 0.9% S element and 40% Zn element, and the high-cadmium smoke contains 13% Cd element.

[0039] Example 2 The present embodiment provides a method for oxidative desulfurization of zinc sulfide materials, wherein zinc concentrate is used as the zinc sulfide material, and the specific operating parameters are as follows: the zinc concentrate does not need to be prepared in a complicated manner, and is mixed with flux quartz sand at a mass ratio of 10:1 to obtain a mixed material with a particle size of 0.05 mm, and the mixed material is added to the oxidation smelting zone of a short-process pyrometallurgical zinc smelting furnace; the mixed material is heated in the oxidation smelting zone at 1200°C and an oxygen-to-material ratio of 200 Nm 3 / t conditions for the first oxidation desulfurization reaction, this process forms copper matte material and preliminary oxide material, the mass percentage of S element in the preliminary oxide material is 3%, the mass percentage of Cu element in the copper matte material is 20%, the copper matte material is deposited on the furnace at the bottom of the molten pool and discharged from the siphon port set in the oxidation smelting zone; increase the temperature of the oxidation smelting zone to 1450℃ and increase the oxygen-to-material ratio to 400Nm 3 / t, so that the slag is further desulfurized to form high-zinc material and high-cadmium smoke. Calculated by mass percentage, the high-zinc material contains 0.5% S element and 50% Zn element, and the high-cadmium smoke contains 15% Cd element.

[0040] Example 3 The present embodiment provides a method for oxidative desulfurization of zinc sulfide materials, wherein zinc concentrate is used as the zinc sulfide material, and the specific operating parameters are as follows: the zinc concentrate is mixed with quartz sand at a mass ratio of 5:1 without complicated material preparation to obtain a mixed material with a particle size of 0.05 mm, and the mixed material is added to the oxidation smelting zone of a short-process pyrometallurgical zinc smelting furnace; the mixed material is smelted in the oxidation smelting zone at 1300°C and an oxygen-to-material ratio of 250Nm 3 / t conditions for the first oxidation desulfurization reaction, this process forms copper matte material and preliminary oxide material, the mass percentage of S element in the preliminary oxide material is 2%, the mass percentage of Cu element in the copper matte material is 30%, the copper matte material is deposited on the bottom of the molten pool furnace, and is discharged from the siphon port set in the oxidation smelting zone; the temperature of the oxidation smelting zone is increased to 1550℃ and the oxygen-to-material ratio is increased to 500Nm 3 / t, so that the slag is further desulfurized to form high-zinc material and high-cadmium smoke. In terms of mass percentage, the mass percentage of S element in the high-zinc material is 0.3%, the mass percentage of Zn element is 60%, and the mass percentage of Cd element in the high-cadmium smoke is 20%.

[0041] Comparative Example 1 The conventional short-process zinc smelting device and method are used, and zinc concentrate is used as the zinc sulfide material. The specific operating parameters are as follows: zinc concentrate (containing Zn: 50%) and slag-making agent (FeO, SiO2 and CaO) are directly added from the feeding port set in the Bref furnace smelting zone, oxygen-enriched air is sprayed into the Bref furnace from the side of the Bref furnace smelting zone, and then the zinc concentrate and the oxygen-enriched air are oxidized and smelted to obtain flue gas and high-zinc slag. The oxygen concentration in the oxygen-enriched air is 60%, and the smelting temperature in the Bref furnace smelting zone is 1300°C. The method in this embodiment cannot realize the recovery of precious metals from copper matte produced in the side blowing stage.

[0042] Comparative Example 2 This comparative example is different from Example 3 in the following aspects: the mixed material is oxidized and smelted in the smelting zone at 1050°C, the oxygen-to-material ratio is 300 Nm 3 / t conditions for the first oxidation desulfurization reaction, this process forms copper matte material and preliminary oxide material, the mass percentage of S element in the preliminary oxide material is less than 1%, but the copper matte material is dispersed in the preliminary oxide material, and the copper matte material cannot be deposited in the furnace at the bottom of the molten pool to separate from the slag, and cannot be discharged from the siphon port set in the oxidation smelting zone, and the precious metal cannot be recovered; then the oxidation smelting zone temperature is increased to 1075℃ and the oxygen-to-material ratio is increased to 325Nm 3 / t, to further desulfurize the slag. At this time, the viscosity of the slag is very high and smelting cannot proceed normally.

[0043] Comparative Example 3 This comparative example is different from Example 3 in the following aspects: the mixed material is oxidized and smelted in the 1000°C smelting zone, and the oxygen-to-material ratio is 50 Nm 3 / t conditions for the first oxidation desulfurization reaction, this process forms a large amount of zinc sulfide and copper sulfur mixture, and a small amount of preliminary oxide material, and the preliminary oxide material is all mixed and dispersed in the mixture of zinc sulfide and copper sulfur. A large amount of zinc sulfide and copper sulfur mixture is deposited on the furnace at the bottom of the molten pool and discharged from the siphon port set in the oxidation smelting zone. Not only is it difficult to recover precious metals, but most of the zinc element is lost; increase the temperature of the oxidation smelting zone to 1500℃ and increase the oxygen-to-material ratio to 500Nm 3 / t, to further desulfurize the slag. At this point, due to the large loss of zinc element caused by the first stage of oxidative desulfurization, it is meaningless to continue smelting in this process.

[0044] Therefore, the present application proposes a method for oxidative desulfurization of zinc sulfide materials. The zinc sulfide materials do not require complicated preparation and processing, and are directly added to the oxidative smelting zone of the zinc smelting furnace, and the first oxidative desulfurization reaction and the second oxidative desulfurization reaction are carried out in sequence to improve the recovery rate of valuable metals in the zinc sulfide materials.

[0045] In the description of this specification, the description with reference to the terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present application. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described may be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art may combine and combine the different embodiments or examples described in this specification and the features of the different embodiments or examples, without contradiction.

[0046] Although the embodiments of the present application have been shown and described above, it can be understood that the above embodiments are exemplary and cannot be understood as limitations on the present application. Ordinary technicians in this field can change, modify, replace and modify the above embodiments within the scope of the present application.

Claims

1. A method for oxidative desulfurization of zinc sulfide material, characterized in that: The following steps are involved: The mixed material formed by the zinc sulfide material and the flux undergoes a first oxidation desulfurization reaction with the oxygen-rich gas in the oxidation smelting zone of the furnace chamber to obtain a preliminary oxide material and a copper matte material; The preliminary oxide material is subjected to a second oxidation desulfurization reaction in the oxidation smelting zone to form high-zinc material and high-cadmium smoke; wherein the temperature of the first oxidation desulfurization reaction is t1, and the oxygen-to-material ratio is OM1; the temperature of the second oxidation desulfurization reaction is t2, and the oxygen-to-material ratio is OM2; 50°C≤t2-t1≤450°C; 50Nm 3 / t≤OM2-OM1≤400Nm 3 / t.

2. The method according to claim 1, characterized in that The temperature of the first oxidation desulfurization reaction is 1100-1300℃, and the oxygen-to-material ratio is 100-250Nm 3 / t.

3. The method according to claim 1 or 2, characterized in that: The temperature of the second oxidation desulfurization reaction is 1350-1550℃, and the oxygen-to-material ratio is 300-500Nm 3 / t.

4. The method according to claim 3, characterized in that The particle size of the mixed material is D, wherein 0.05 mm≤D≤5 mm.

5. The method according to claim 3, characterized in that: The oxygen concentration in the oxygen-rich gas is 23-99.8%, and the pressure in the furnace chamber is 0.2MPa-0.5MPa.

6. The method according to claim 3, characterized in that The mass ratio of the zinc sulfide material to the flux in the mixed material is 5-20:

1.

7. The method according to claim 3, characterized in that The flux includes at least one of quartz sand, quicklime and limestone.

8. The method according to claim 3, characterized in that The blowing mode of the oxidation smelting zone includes side blowing alone, bottom blowing alone or a mixture of side blowing and bottom blowing.

9. The method according to claim 3, characterized in that: The mass percentage of sulfur in the preliminary oxidized material obtained in the first oxidative desulfurization reaction is 2%-5%; And / or, based on the zinc sulfide material, according to the mass percentage, 70%-80% of the copper element, 80%-90% of the gold element and 80%-90% of the silver element in the zinc sulfide material are enriched in the copper matte material; And / or, the mass percentage of copper element in the copper matte material is 10%-30%.

10. The method according to claim 3, characterized in that The mass percentage of sulfur in the high-zinc material is less than 1%; And / or, the mass percentage of zinc element in the high-zinc material is 40%-60%; And / or, the mass percentage of cadmium element in the high-cadmium smoke is greater than 12%.

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