CN115807165A - Oxidation desulfurization method and device for lead-zinc sulfide ore - Google Patents
Oxidation desulfurization method and device for lead-zinc sulfide ore Download PDFInfo
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Abstract
The invention provides an oxidative desulfurization method and device for lead-zinc sulfide ore. The oxidation desulfurization method comprises the steps of mixing a mixed material and oxygen-enriched gas, spraying the mixed material into a furnace chamber, carrying out a first oxidation desulfurization reaction on the mixed material before the mixed material is lowered into a molten pool below the furnace chamber to obtain a primary oxidation material, wherein an oxidation layer is arranged on the surface of the primary oxidation material. The mixed material comprises lead zinc sulfide material and flux. And carrying out a second oxidation desulfurization reaction after the primary oxidation material enters the molten pool. An oxide layer is formed on the surface of the mixed material to protect the internal material, so that the oxidation desulfurization rate of the material is higher than the volatilization rate of the material, and the volatilization rate of sulfide is inhibited. After the primary oxidation material enters the molten pool, further oxidation desulfurization is carried out, and the primary oxidation material enters the molten slag phase in the form of oxides after deep desulfurization. The oxidative desulfurization method for the lead-zinc sulfide ore can effectively reduce smoke dust and reduce the volatilization loss rate of lead-zinc materials, thereby improving the recovery rate of the lead-zinc sulfide ore and reducing the cost.
Description
Technical Field
The invention relates to the field of metal reduction recovery, in particular to an oxidative desulfurization method and device for lead-zinc sulfide ore.
Background
The pyrometallurgical lead-zinc smelting has the characteristics of complex raw material treatment, simple process and the like, and is widely applied to lead-zinc metal smelting. The lead-zinc pyrometallurgical process comprises a sintering-blast furnace process, a Kiffmiter flash smelting process, an Isa furnace lead smelting process and other molten pool smelting processes, wherein the molten pool smelting processes have obvious advantages in the aspects of energy consumption, environmental protection, valuable metal recovery and the like. The oxygen-enriched oxidation process of the melting pool has higher desulfurization efficiency and high SO compared with the sintering process 2 Smoke pollution, and the closed condition can greatly reduce the environmental pollution load; the molten product after oxidation and desulfurization directly flows into the reduction section for metal recovery, so that the process of reheating cold materials is avoided, and the energy consumption in the smelting process can be greatly reduced. Therefore, at present, the lead smelting processes such as the Ausmelt method, the triple furnace, the QSL and the like in the lead smelting adopt a molten pool smelting method, and good production efficiency, lead recovery rate and energy consumption cost control are achieved.
The smoke dust rate in the smelting process of the lead melting pool is still at a higher level at present, so that more volatilization loss of lead is caused. Particularly for materials with higher zinc content, the volatilization loss of lead-zinc materials is higher.
Disclosure of Invention
The invention mainly aims to provide an oxidative desulfurization method and device for lead-zinc sulfide ore, which aim to solve the technical problem of high material volatilization loss in the lead-zinc material smelting process.
In order to achieve the above object, a first aspect of the present invention provides a method for the oxidative desulfurization of lead-zinc sulfide ore, comprising:
and mixing the mixed material and the oxygen-enriched gas, spraying the mixed material into the furnace chamber, and carrying out a first oxidation desulfurization reaction on the mixed material before the mixed material is lowered to a molten pool below the furnace chamber to obtain a primary oxidation material, wherein the surface of the primary oxidation material is provided with an oxidation layer. The mixed material comprises a lead zinc sulfide material and a fusing agent, and the particle size of the mixed material is less than 3mm. The mixed material comprises a lead zinc sulfide material and a flux, and the particle size of the mixed material is not less than 0.05mm and not more than 3mm; the oxygen concentration of the oxygen-enriched gas is 20-100%.
And (4) carrying out a second oxidation desulfurization reaction after the primary oxidation material enters the molten pool.
According to the embodiment of the application, the distance between the mixed material and the upper surface of the molten pool is more than or equal to 3 meters.
According to the embodiment of the application, the grain diameter of the mixed material is less than or equal to 1mm and less than or equal to 3mm.
According to an embodiment of the application, the pressure of the oxygen-enriched gas is 2-3 kg/cm 2 The flow rate of the oxygen-enriched gas satisfies the oxygen-material ratio of 300-500 m 3 /t。
According to an embodiment of the present application, the reaction temperature of the first oxidative desulfurization reaction is 900 to 1200 ℃.
According to an embodiment of the present application, the reaction temperature of the second oxidative desulfurization reaction is 1150 to 1250 ℃.
According to the embodiment of the application, the preparation method of the mixed material comprises the steps of mixing lead-zinc sulfide ore with a flux, crushing and ball milling to obtain the mixed material.
The flux comprises at least one of quartz sand, quicklime and calcium carbonate.
According to embodiments of the present application, the molten bath blowing mode includes single side blowing, single bottom blowing or a combination of side blowing and bottom blowing.
The second aspect of the present invention provides an oxidative desulfurization apparatus for lead-zinc sulfide ore, comprising:
the furnace body comprises a furnace shell, the furnace shell surrounds and forms a furnace chamber and a molten pool, and the furnace chamber is positioned above the molten pool.
The spray gun is arranged on the furnace shell and is provided with a feeding end and a discharging end, and the discharging end is communicated with the furnace chamber.
The feed pipe and the oxygen-enriched gas pipeline are communicated with the feed end of the spray gun.
And the slag discharge port is communicated with the molten pool.
According to the embodiment of the application, the furnace body also comprises a side-blown oxygen lance which is communicated with the molten pool.
In the oxidation desulfurization method of the lead-zinc sulfide ore, the mixed material has proper particle size, is mixed with the oxygen-enriched gas and fully contacts with the oxygen-enriched gas in the process of descending to the molten pool, and the desulfurization oxidation reaction is rapidly carried out. An oxide layer is formed on the surface of the mixed material to protect the internal material, so that the oxidation desulfurization rate of the material is higher than the volatilization rate of the material, and the volatilization rate of sulfide is inhibited. After the primary oxidation material enters a molten pool, further oxidation desulfurization is carried out, and the primary oxidation material enters a molten slag phase in an oxide form after deep desulfurization. The oxidative desulfurization method for the lead-zinc sulfide ore can effectively reduce smoke dust and reduce the volatilization loss rate of lead-zinc materials, thereby improving the recovery rate of the lead-zinc sulfide ore and reducing the cost.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the structures shown in the drawings without creative efforts.
Fig. 1 is a schematic configuration diagram of an apparatus for oxidative desulfurization of lead-zinc sulfide ore according to an embodiment of the present application;
FIG. 2 is a view of a small-scale experimental apparatus corresponding to the apparatus for oxidative desulfurization of lead-zinc sulfide ore according to an embodiment of the present invention;
FIG. 3 is a SEM morphology feature, a collective graph of distribution of elements, content and distribution of elements of the injection oxygen-enriched desulfurized product of the zinc sulfide concentrate material in example 4 of the invention.
The implementation, functional features and advantages of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
It should be noted that all directional indicators (such as upper and lower 8230; etc.) in the embodiments of the present invention are only used for explaining the relative positional relationship between the components at a certain posture (as shown in the attached drawings), the motion situation, etc., and if the certain posture is changed, the directional indicator is also changed accordingly.
In addition, the descriptions related to "first", "second", etc. in the present invention are only for descriptive purposes and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature.
Moreover, the technical solutions in the embodiments of the present invention may be combined with each other, but it is necessary to be able to be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be considered to be absent, and is not within the protection scope of the present invention.
Through a great deal of research, the applicant finds that the volatilization temperature of PbS and ZnS in lead and zinc concentrate is low, for example, the boiling point of ZnS is 1185 ℃, and the boiling point of PbS is 1281 ℃, so that the ZnS and PbS materials are volatilized greatly even under the condition of conventional smelting temperature, and in addition, according to practical experience, the PbS can have obvious volatilization behavior at the temperature of 900 ℃. In particular, the high melting point (1700 ℃) of ZnS makes the ZnS difficult to be dissolved in slag, so that the ZnS is difficult to be in full contact with oxygen in a molten pool to generate oxidation desulfurization reaction in time, the oxidation desulfurization rate is difficult to keep up with the volatilization rate, and finally, a large amount of volatilization of materials in the molten pool and the formation of high smoke generation rate are caused.
Based on this, the embodiment of the present invention provides an oxidative desulfurization method for lead-zinc sulfide ore, including:
step S100: and mixing the mixed material and the oxygen-enriched gas, spraying the mixed material into the furnace chamber, and carrying out a first oxidation desulfurization reaction on the mixed material before the mixed material is lowered to a molten pool below the furnace chamber to obtain a primary oxidation material, wherein the surface of the primary oxidation material is provided with an oxidation layer. The mixed material comprises lead zinc sulfide material and flux. The grain diameter of the mixed material is less than or equal to 3mm and less than or equal to 0.05 mm; the oxygen concentration of the oxygen-enriched gas is 20-100%.
The lead-zinc sulfide material comprises zinc, lead and sulfur elements, and also comprises iron, sulfur, calcium and silicon elements generally. In addition to the above elements, in some embodiments the lead zinc sulfide material may include other elements, such as oxygen, magnesium, copper, aluminum, cadmium, arsenic, and the like. The contents of zinc, lead, iron, sulfur, calcium and silicon elements are relatively higher than those of other elements. Illustratively, the lead zinc sulfide material includes 10-40 wt.% Zn; pb 5-30 wt.%; s10-30 wt.%; fe 3-15 wt.%; ca 1-10 wt.%; siO2 2 2-10 wt.%. For example, zn 20-40 wt.%, pb 10-30 wt.%, S15-30 wt.%, fe 4-15 wt.%, ca 1-5 wt.%, siO 2 2-6 wt.%. The lead-zinc sulfide material can be natural lead-zinc sulfide mineral, and can also be raw materials which are formed by smelting and contain relatively high sulfur, lead and zinc elements.
The lead-zinc sulfide material can be divided into lead concentrate (with the highest lead content) and zinc concentrate (with the highest lead content) according to the difference of elements with the highest lead content.
Illustratively, lead concentrate has a major element or component content of Pb 36.82 wt.%, zn16.25 wt.%, S13.86 wt.%, fe3.84 wt.%, cu 0.40 wt.%, cao3.08 wt.%, siO2 5.16 wt.%.
Illustratively, the zinc concentrate has a major element or component content of Zn 43.49 wt.%, pb3.09 wt.%, S28.61 wt.%, fe11.10 wt.%, cu 0.74 wt.%, cd0.39 wt.%, caO 0.82 wt.%, sio26.12 wt.%.
Lead zinc sulfide materials and flux are mixed into mixed materials, the mixed materials are fine particles, the particle size does not need to be accurately controlled, and only the particle size needs to be less than or equal to 3mm and more than or equal to 0.05mm.
In this embodiment, the complete oxidative desulfurization reaction of the mixed materials is divided into two stages, i.e., a first oxidative desulfurization reaction and a second oxidative desulfurization reaction. The mixed material begins to descend after entering the furnace chamber and finally descends into the molten pool. The first oxidative desulfurization reaction occurs when the mixed materials enter the furnace chamber and fall to the molten pool. The second oxidative desulfurization reaction occurs at a stage where the mixed material (i.e., the preliminary oxidized material) after the first oxidative desulfurization reaction has occurred falls to the molten pool.
The particle size of the mixed material is not suitable to be too large, on one hand, the specific surface area of the mixed material is reduced, the contact area of the mixed material and the oxygen-enriched gas is reduced, and the reaction speed is reduced; on the other hand, the descending speed of the mixed materials is higher, and the time of the mixed materials in the furnace chamber is shortened. Under the combined action, the reaction degree of the mixed material is relatively low in the first oxidation desulfurization reaction process.
Since the oxidative desulfurization reaction is carried out in two stages, it is not sought to completely complete the oxidative desulfurization reaction in the first oxidative desulfurization reaction. Therefore, the particle size of the mixed material does not need to be too small. Therefore, the refining step requirement in the preparation of the mixed material is relatively low, and the refining cost is reduced. Furthermore, the drying degree requirement of the mixed materials is relatively low. This is completely different from the requirement of flash process, the granularity of the material of flash process needs to reach micron level, and the material is required to be relatively dry, so the oxidation desulfurization process of the material is completed once.
In addition, in the examples of the present application, the particle size of the mixed material is not too small. During the first oxidative desulfurization reaction and/or the second oxidative desulfurization reaction, combustion heat supplementation may be required in the furnace chamber by gas to maintain the reaction temperature. Or oxygen is required to be introduced into the melt during the second oxidative desulfurization reaction to further complete the oxidative desulfurization reaction. That is, the furnace body is also filled with fuel gas or oxygen, and the gas finally flows out from the flue of the furnace body as shown in fig. 1.
And in some embodiments, the flue is on the same side as the mixing material inlet (e.g., the discharge end of the lance). When the particle size of the mixed material is too small, the mass is small, and the lead zinc sulfide material in the mixed material is probably not oxidized, namely is directly carried by fuel gas or oxygen to flow out of the flue. Or the primary oxidation material is carried by fuel gas or oxygen and flows out of the flue because of the small particle size and small mass. Thus, lead and zinc sulfide materials are lost, and the recovery rate of metals is reduced.
Therefore, the particle size of the mixed material is controlled to be not more than 3mm and not less than 0.05mm in comprehensive consideration. I.e. the particle size of the mixed material is mainly in millimeter level. In some embodiments, 1mm ≦ 3mm for the mixed material particle size. Therefore, the reaction degree of the first oxidation desulfurization reaction is higher, the reaction speed is higher, the refining and drying cost can be reduced, the material loss is reduced, and the recovery rate of metal is improved.
In the first oxidation desulfurization reaction, the mixture material is fully contacted with the oxygen-enriched gas in the top-down movement process, the desulfurization oxidation reaction is rapidly carried out, and the desulfurization rate of the sulfide is accelerated. The oxygen-enriched gas has an oxygen concentration of 20-100%, and in some embodiments, an oxygen concentration of 40-90%.
And the surface of the mixed material is oxidized and desulfurized, while the inside of the mixed material is not oxidized and desulfurized, so as to obtain the primary oxidized material. The oxide layer on the surface of the primary oxide material is the oxide of metal substances in the mixture material, such as zinc oxide and lead oxide. Because the oxide layer's melting point is higher, difficult volatilizing, the oxide layer makes inside material be difficult to volatilize with inside material parcel, has reduced the speed of volatilizing.
Thus, during the first oxidative desulfurization reaction, the oxidative desulfurization rate of the sulfide is greatly higher than the volatilization rate of the sulfide, so that the volatilization rate of the sulfide is inhibited to a certain degree.
Step S200: and carrying out a second oxidation desulfurization reaction after the primary oxidation material enters the molten pool.
The molten pool is filled with melt, for example, the former primary oxidation material forms melt in the molten pool, and the subsequent primary oxidation material enters the melt to continue the second oxidation desulfurization reaction. The specific reaction conditions can refer to the conventional oxidative desulfurization conditions of molten bath smelting, such as reaction temperature, reaction time and reaction process (such as blowing in the form of oxygen-enriched side blowing).
After the primary oxidation material enters a molten pool, further oxidation desulfurization is carried out, and the primary oxidation material enters a molten slag phase in an oxide form after deep desulfurization. The molten slag phase can flow out and be discharged into a subsequent reduction section for treatment.
In the oxidation desulfurization method of the lead-zinc sulfide ore, the mixed material has proper particle size, is mixed with the oxygen-enriched gas and fully contacts with the oxygen-enriched gas in the process of descending to the molten pool, and the desulfurization oxidation reaction is rapidly carried out. An oxide layer is formed on the surface of the mixed material to protect the internal material, so that the oxidation desulfurization rate of the material is higher than the volatilization rate of the material, and the volatilization rate of sulfide is inhibited. After the primary oxidation material enters a molten pool, further oxidation desulfurization is carried out, and the primary oxidation material enters a molten slag phase in an oxide form after deep desulfurization. The oxidative desulfurization method for the lead-zinc sulfide ore can effectively reduce smoke dust and reduce the volatilization loss rate of lead-zinc materials, thereby improving the recovery rate of the lead-zinc sulfide ore and reducing the cost.
In some embodiments, the distance between the mixed material and the upper surface of the molten pool is greater than or equal to 3 meters. The upper surface of the molten pool is the surface of the melt. Under the condition, the mixed material enters the initial position of the molten pool, namely, the nozzle of the furnace top is a long distance away from the surface of the molten pool, and the surface of particles in the process of the falling of the sulfide concentrate in the mixed material is rapidly desulfurized and oxidized to inhibit the volatilization of sulfides.
In some embodiments, the oxygen-enriched gas has an oxygen concentration of 20-100%. That is, the oxygen-enriched gas may be pure oxygen or a mixture of oxygen and other gases (e.g., nitrogen). Under the condition, the oxygen concentration in the oxygen-enriched gas is higher, so that sufficient oxygen can be provided, and the mixed materials can be fully reacted.
In some embodiments, the oxygen-enriched gas has a pressure of 2 to 3 kg/cm 2 The flow of the oxygen-enriched gas satisfies the oxygen-material ratio of 300-500 m 3 T is calculated. Under the condition, the oxygen-enriched gas is ensured to provide an oxygen-enriched environment for the mixed gas to promote the oxidation desulfurization reaction, and the mixed material can be reduced to the melt at a relatively proper falling speed, so that the oxygen-enriched gas is not reduced too fast due to overlarge pressure and flow, and the mixed material has proper residence time, so that the mixed material can reach a better reaction state in the first oxidation desulfurization reaction.
In some embodiments, the reaction temperature for the first oxidative desulfurization reaction is from 900 to 1200 ℃.
In some embodiments, the reaction temperature for the second oxidative desulfurization reaction is 1150-1250 ℃. At this reaction temperature, the sulfidic concentrate can be advantageously subjected to deep oxidative desulfurization, entering the molten slag phase in the form of oxides.
In some embodiments, the mixed material is prepared by mixing lead-zinc sulfide ore with a flux, and crushing and ball milling the mixture to obtain the mixed material. The flux comprises at least one of quartz sand, quicklime and calcium carbonate.
For example, lead-zinc sulfide ore is mixed with flux and then refined by crushing-ball milling. In the refining process, the lead-zinc sulfide ore and the flux are crushed into fine particles and are uniformly mixed. To better control the particle size of the mixed material, in some of these embodiments, granulation may also be performed after ball milling. The specific technological parameters of crushing and ball milling are based on that the mixed material is not more than 3mm. I.e. the particle size of the mixed material is mainly in millimeter level.
In some embodiments, the mixture may be further dried.
In some embodiments, the molten bath blowing mode includes single side blowing, single bottom blowing, or a combination of side and bottom blowing.
The second aspect of the invention provides an oxidative desulfurization device for lead-zinc sulfide ore, which comprises a furnace body 1, a spray gun 8, a feeding pipe 7, an oxygen-enriched gas pipeline 6 and a slag discharge port 4.
The furnace body 1 comprises a furnace shell 5, which furnace shell 5 surrounds and forms a furnace chamber 9 and a molten bath 10, which furnace chamber 9 is located above the molten bath 10. The slag discharge port 4 is communicated with the molten pool 10. The spray gun 8 is arranged on the furnace shell 5 and is provided with a feeding end and a discharging end, and the discharging end is communicated with the furnace chamber 9. The feed pipe 7 and the oxygen-enriched gas pipe 6 are both communicated with the feed end of the spray gun 8.
The mixture enters the lance 8 from the feed end of the lance 8 through the feed pipe 7. Specifically, the mixture can be fed to the feed pipe 7 by screw feeding or belt conveying. Oxygen-enriched gas enters the lance 8 from the feed end of the lance 8 through an oxygen-enriched gas conduit 6. The mixture and oxygen-enriched gas are fed into the furnace by means of injection lances 8.
The feed pipe 7 and the oxygen-enriched gas pipe 6 may be in independent communication with the feed end of the lance 8, or one of the pipes may be in communication with the feed end of the lance 8 and the other pipe may be in communication with the pipe. As shown in the figure, an oxygen-enriched gas pipe 6 is communicated with the feed end of a spray gun 8, and a feed pipe 7 is arranged on the side wall of the oxygen-enriched gas pipe 6 and is communicated with the oxygen-enriched gas pipe 6.
In some embodiments, furnace body 1 further comprises side-blown oxygen lances 2, side-blown oxygen lances 2 being in communication with molten bath 10.
In some embodiments, the furnace 1 further comprises a flue 3. The flue 3 is communicated with the furnace chamber 9, and the flue 3 is used for exhausting flue gas. Illustratively, the flue 3 is located above the furnace chamber 9 on the same side as the lance 8.
Example 1
This example utilizes lead concentrate (36.82 wt.% Pb, 16.25 wt.% zns, 13.86 wt.%, 3.84 wt.% fe, 0.40 wt.% Cu, 3.08 wt.% cao3, siO) with a major element or component content 2 5.16 wt.%) to perform oxygen-enriched blowing desulfurization of the material and analyze the volatilization loss rate of lead in the desulfurization process.
Mixing lead concentrate with a flux, carrying out refining treatment in a crushing-ball milling mode, granulating to enable the particle size of the mixed material not to exceed 3mm, and then drying the mixed material. In the mixed material, the mass fraction of lead concentrate is 85 wt.%, and the mass fraction of the flux is 15wt.%. The flux is quicklime and quartz sand.
Passing the dried mixture through a furnaceThe top lance device is injected into the furnace chamber 9 together with the oxygen-enriched gas (see fig. 1) to ensure that the mixed material is fully contacted with the enriched oxygen in the descending process, and the mixed material is quickly oxidized. Wherein the oxygen-enriched gas is pure oxygen with oxygen concentration of 100%, and the oxygen-enriched gas pressure of 2kg/cm 2 The flow of the oxygen-enriched gas satisfies the oxygen-material ratio of 300 m 3 T is calculated as the ratio of the total weight of the composition. The distance between the mixed material and the upper surface of the molten bath 10 was 3 m. The reaction temperature of the first oxidative desulfurization reaction is 900 ℃.
After the materials are rapidly desulfurized through contact with the rich oxygen, the materials enter a molten pool 10 and are further oxidized and desulfurized in the molten pool 10, wherein the temperature of the molten pool 10 is about 1200 ℃, and the blowing is carried out in a form of rich oxygen side blowing; after the oxidation deep desulfurization and product melting of the molten pool 10, the effluent is discharged into a subsequent reduction section for treatment; through the measurement of the total amount of the smoke dust and the content of lead in the smoke dust, the volatilization amount of the lead can be obtained by multiplying the total amount of the smoke dust by the content of the lead, and the volatilization loss rate of the lead is 13.2 wt% by dividing the volatilization amount of the lead by the total amount of the lead in the raw material.
Example 2
Utilizes zinc concentrate (the main element or component content is Zn 43.49 wt.%, pb3.09 wt.%) S28.61 wt.%, fe11.10 wt.%, cu 0.74 wt.%, cd0.39 wt.%, caO 0.82 wt.%, siO 2 6.12 wt.%) to perform oxygen-enriched blowing material desulfurization, and analyze the volatilization loss rate of zinc in the desulfurization process.
Mixing zinc concentrate with a flux, carrying out refining treatment in a crushing-ball milling mode, then granulating to enable the particle size of the mixed material not to exceed 3mm, and then drying the mixed material. In the mixed material, the mass fraction of the zinc concentrate is 78 wt.%, and the mass fraction of the flux is 22wt.%. The flux is quicklime and quartz sand.
The dried mixed material is sprayed into a furnace chamber 9 (see figure 1) together with oxygen-enriched gas through a spray gun device at the top of the furnace, so that the mixed material is fully contacted with the enriched oxygen in the descending process, and the mixed material is quickly oxidized. Wherein the oxygen-enriched gas is pure oxygen with oxygen concentration of 40%, and the pressure of the oxygen-enriched gas is 2.5 kg/cm 2 The flow of the oxygen-enriched gas satisfies the oxygen-material ratio of 400 m 3 T is calculated as the ratio of the total weight of the composition. The distance between the mixed material and the upper surface of the molten pool 10 is 3.5 m. The reaction temperature of the first oxidative desulfurization reaction was 1000 ℃.
After the materials are rapidly desulfurized through contact with the rich oxygen, the materials enter a molten pool 10 and are further oxidized and desulfurized in the molten pool 10, wherein the temperature of the molten pool 10 is about 1225 ℃, and the oxygen-rich side blowing mode is adopted for blowing; after the oxidation deep desulfurization and product melting of the molten pool 10, the effluent is discharged into a subsequent reduction section for treatment; the total amount of the smoke dust and the content of lead in the smoke dust are measured, the volatilization amount of zinc can be obtained by multiplying the total amount of the smoke dust by the content of zinc, and the volatilization loss rate of the zinc can be obtained by dividing the volatilization amount of the zinc by the total amount of the zinc in the raw materials, wherein the volatilization loss rate of the zinc is 8.29 wt.%.
Example 3
Using zinc concentrate (Zn 43.49 wt.% in major element or component content, pb3.09 wt.%, S28.61 wt.%, fe11.10 wt.%, cu 0.74 wt.%, cd0.39 wt.%, caO 0.82 wt.%, siO 0) 2 6.12 wt.%) to perform oxygen-enriched blowing material desulfurization, and analyze the volatilization loss rate of zinc in the desulfurization process.
Mixing zinc concentrate with a flux, carrying out refining treatment in a crushing-ball milling mode, granulating to enable the particle size of the mixed material not to exceed 3mm, and then drying the mixed material. In the mixed material, the mass fraction of the lead concentrate is 78 wt.%, and the mass fraction of the flux is 22wt.%. The flux is quicklime and quartz sand.
The dried mixed material is sprayed into a furnace chamber 9 (see figure 1) together with oxygen-enriched gas through a spray gun device at the top of the furnace, so that the mixed material is fully contacted with the enriched oxygen in the descending process, and the mixed material is quickly oxidized. Wherein the oxygen-enriched gas is pure oxygen with oxygen concentration of 20%, and the pressure of oxygen-enriched gas is 3 kg/cm 2 The flow of the oxygen-enriched gas satisfies the oxygen-material ratio of 500 m 3 T is calculated as the ratio of the total weight of the composition. The distance between the mixed material and the upper surface of the molten pool 10 was 3.5 m. The reaction temperature of the first oxidative desulfurization reaction is 1200 ℃.
After the material is rapidly desulfurized through contact with the rich oxygen, the material enters a molten pool 10 and is further oxidized and desulfurized in the molten pool 10, wherein the temperature of the molten pool 10 is about 1225 ℃, and the blowing is carried out in a form of rich oxygen side blowing; after the oxidation deep desulfurization and product melting of the molten pool 10, the effluent is discharged into a subsequent reduction section for treatment; through the measurement of the total amount of the smoke dust and the content of lead in the smoke dust, the volatilization amount of zinc can be obtained by multiplying the total amount of the smoke dust by the content of zinc, and the volatilization loss rate of the zinc can be obtained by dividing the volatilization amount of the zinc by the total amount of the zinc in the raw material.
Example 4
This example utilizes zinc concentrate to carry out the comparative experiment before and after the material contacts oxidation reaction with oxygen boosting in the gaseous phase. Zinc concentrate is used as raw material, experimental apparatus is shown in figure 2, and N is introduced at 300 mL/min 2 Exhausting the air in the furnace for 120 min; heating to 1250 ℃, and introducing oxygen at 1L/min; then, spraying the zinc concentrate into the furnace along with oxygen; immediately changing the blowing speed to N after the blowing is finished 2 Protecting, cooling and sampling, and detecting element content and distribution. Fig. 3 (a), (b) and (c) are SEM morphological characteristics, distribution set diagram and content of each element, distribution diagram of each element of the injection oxygen-enriched desulfurization product of the zinc sulfide concentrate material, respectively, and it can be seen that the distribution of Zn element and Fe element is contained in the distribution region of O element, which indicates that Zn and Fe mainly exist in the form of oxide, and S element only exists in a small amount of scattered distribution, and the result of S content of 2wt.% indicates that most of the surface of the concentrate particle has been desulfurized to form an oxide layer. The distribution of Pb, ca and Si is similar, which indicates that Pb and Ca exist in the form of silicate solid solution. Therefore, the zinc sulfide can be rapidly oxidized and desulfurized in the material blowing oxygen-enriched desulfurization process, so that the volatilization loss of ZnS in a molten pool is reduced.
Comparative example 1
This comparative example is that of example 1. Unlike example 1, the material was directly charged into the molten bath for oxidative desulfurization without fully contacting with the oxygen-rich gas. The specific process is as follows: lead concentrate (36.82 wt.% Pb, 16.25 wt.% Zns, 13.86 wt.% S, 3.84 wt.% Fe3.40 wt.% Cu, 3.08 wt.% CaO3.08 wt.% SiO) was concentrated 2 5.16 wt.%) is mixed with the flux, then the material is directly put into a molten pool, and oxidation desulfurization is carried out in the molten pool, wherein the temperature of the molten pool is about 1200-1250 ℃, and oxygen-enriched gas side blowing is adopted for blowing; after the deep desulfurization by the oxidation of the molten pool and the melting of the product, the effluent is discharged into a subsequent reduction working section for treatment; the total amount and content of the smoke dust are analyzed, and the volatilization loss rate of the lead is 286 wt.%, significantly higher than the level of volatility of example 1.
Comparative example 2
This comparative example is that of example 2. Different from the embodiment 2, the mixed material of the zinc concentrate and the flux is directly put into the molten pool to carry out the oxidation desulfurization slagging reaction without fully contacting with the oxygen-rich gas. The specific process is as follows: zinc concentrate (main element or component content Zn 43.49 wt.%, pb3.09 wt.%, S28.61 wt.%, fe11.10 wt.%, cu 0.74 wt.%, cd0.39 wt.%, caO 0.82 wt.%, siO 0.39 wt.%, based on the total weight of the concentrate) 2 6.12 wt.%) is mixed with a flux, the mixture is refined by a crushing-ball milling mode and then granulated, and then the material is directly put into a molten pool for oxidative desulfurization in the molten pool, wherein the temperature of the molten pool is about 1250-1300 ℃, and oxygen-enriched gas side blowing is adopted for blowing; after the deep desulfurization by the oxidation of the molten pool and the melting of the product, the effluent is discharged into a subsequent reduction working section for treatment; through analysis of the total amount and content of the smoke dust, the volatilization loss rate of the zinc is 18.67 wt.%, which is obviously higher than the volatilization rate level of the example 2.
Comparative example 3
This comparative example is that of example 1. Different from the embodiment 1, the lead concentrate is mixed with the flux, the mixture is granulated after being refined by a crushing-ball milling mode, the particle size of the mixed material is 3-5 mm, and other process conditions in the desulfurization process are consistent with those in the embodiment 2. Through the measurement of the total amount of the smoke dust and the content of lead in the smoke dust, the volatilization amount of the lead can be obtained by multiplying the total amount of the smoke dust by the content of the lead, and the volatilization loss rate of the lead is 20.5 wt.% by dividing the volatilization amount by the total amount of the lead in the raw material, which is obviously higher than the volatilization rate level of the example 1.
The above examples and comparative examples illustrate that, by the method for oxidative desulfurization of lead-zinc sulfide ore according to the examples of the present application, the mixed material has a suitable particle size and is oxidized in stages, so that smoke dust can be effectively reduced, the volatilization loss rate of the lead-zinc material can be reduced, the recovery rate of lead-zinc sulfide ore can be improved, and the cost can be reduced.
In the above technical solutions, the above are only preferred embodiments of the present invention, and the technical scope of the present invention is not limited thereby, and all the technical concepts of the present invention include the claims of the present invention, which are directly or indirectly applied to other related technical fields by using the equivalent structural changes made in the content of the description and the drawings of the present invention.
Claims (10)
1. An oxidative desulfurization method for lead-zinc sulfide ore, which is characterized by comprising the following steps:
mixing a mixed material and oxygen-enriched gas, spraying the mixed material into a furnace chamber, and carrying out a first oxidation desulfurization reaction on the mixed material before the mixed material is lowered to a molten pool below the furnace chamber to obtain a primary oxidation material, wherein an oxidation layer is arranged on the surface of the primary oxidation material; the mixed material comprises a lead zinc sulfide material and a flux, and the grain size of the mixed material is less than or equal to 0.05mm and less than or equal to 3mm; the oxygen concentration of the oxygen-enriched gas is 20-100%;
and carrying out a second oxidation desulfurization reaction after the primary oxidation material enters the molten pool.
2. The process for the oxidative desulfurization of lead-zinc sulfide ore according to claim 1, wherein the distance between the mixed material and the upper surface of the molten bath is 3m or more.
3. The process for the oxidative desulfurization of lead-zinc sulfide ore according to claim 1, wherein the particle size of the mixed material is 1mm or less and 3mm or less.
4. The process for the oxidative desulfurization of lead-zinc sulfide ore according to claim 1, wherein the pressure of the oxygen-rich gas is 2 to 3 kg/cm 2 The flow of the oxygen-enriched gas satisfies the oxygen-material ratio of 300-500 m 3 /t。
5. The process for the oxidative desulfurization of lead-zinc sulfide ore according to claim 1, wherein the reaction temperature of the first oxidative desulfurization reaction is 900 to 1200 ℃.
6. The process for the oxidative desulfurization of lead-zinc sulfide ore according to claim 1, wherein the reaction temperature of the second oxidative desulfurization reaction is 1150 to 1250 ℃.
7. The method for oxidative desulfurization of lead-zinc sulfide ore according to claim 1, wherein the preparation method of the mixed material comprises mixing lead-zinc sulfide ore with a flux, and performing crushing and ball milling to obtain the mixed material;
the fusing agent comprises at least one of quartz sand, quicklime and calcium carbonate.
8. The process of claim 1, wherein the molten bath blowing mode comprises single side blowing, single bottom blowing or a combination of side blowing and bottom blowing.
9. An oxidative desulfurization apparatus for lead-zinc sulfide ore, which is applied to the oxidative desulfurization method according to any one of claims 1 to 8, comprising:
the furnace body comprises a furnace shell, the furnace shell surrounds and forms a furnace cavity and a molten pool, and the furnace cavity is positioned above the molten pool;
the spray gun is arranged on the furnace shell and is provided with a feeding end and a discharging end, and the discharging end is communicated with the furnace chamber;
the feeding pipe and the oxygen-enriched gas pipeline are communicated with the feeding end of the spray gun;
and the slag discharge port is communicated with the molten pool.
10. The apparatus for the oxidative desulfurization of lead-zinc sulfide ore according to claim 9, wherein the furnace body further comprises a side-blowing lance, the side-blowing lance communicating with the molten bath.
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