CN115807165B - Oxidative desulfurization method and device for lead-zinc sulfide ore - Google Patents
Oxidative desulfurization method and device for lead-zinc sulfide ore Download PDFInfo
- Publication number
- CN115807165B CN115807165B CN202310044112.6A CN202310044112A CN115807165B CN 115807165 B CN115807165 B CN 115807165B CN 202310044112 A CN202310044112 A CN 202310044112A CN 115807165 B CN115807165 B CN 115807165B
- Authority
- CN
- China
- Prior art keywords
- lead
- oxygen
- zinc sulfide
- mixed material
- molten pool
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides an oxidation desulfurization method and device for lead zinc sulfide ore. The oxidation desulfurization method comprises the steps of mixing and spraying a mixed material and oxygen-enriched gas into a furnace chamber, and carrying out a first oxidation desulfurization reaction on the mixed material before the mixed material descends to a molten pool below the furnace chamber to obtain a preliminary oxidized material, wherein an oxide layer is arranged on the surface of the preliminary oxidized material. The mixed material comprises lead-zinc sulfide material and flux. And (3) after the primary oxidation material enters a molten pool, performing a second oxidation desulfurization reaction. The surface of the mixed material forms an oxide layer 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, oxidation desulfurization further occurs, and the primary oxidation material enters a molten slag phase in an oxide form after deep desulfurization. The oxidation desulfurization method of 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 oxidation desulfurization method and device for lead zinc sulfide ore.
Background
The pyrometallurgy of lead and zinc has the characteristics of complex raw material treatment, simple flow and the like, and is applied to the smelting of lead and zinc metals on a large scale. The lead-zinc pyrometallurgy process comprises a sintering-blast furnace process, a Korscht flash smelting process, an Issatch smelting process and other molten pool smelting processes, wherein the molten pool smelting process has remarkable advantages in the aspects of energy consumption, environmental protection, valuable metal recovery and the like. The oxygen-enriched oxidation process of the molten pool has higher desulfurization efficiency, and is high in SO compared with the sintering process 2 The smoke pollution, its airtight condition can reduce the environmental pollution load greatly; the molten product after oxidative 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, the current lead smelting processes of Australian method, "three-continuous furnace", QSL and the like in lead smelting all adopt a molten pool smelting method, and good production efficiency, lead recovery rate and energy consumption cost control are obtained.
The smoke dust rate in the current lead smelting process is still at a higher level, 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 oxidation desulfurization method and device for lead-zinc sulfide ores, which are used for solving the technical problem of high material volatilization loss in the smelting process of lead-zinc materials.
To achieve the above object, a first aspect of the present invention provides a method for oxidative desulfurization of lead-zinc sulfide ores, comprising:
mixing the mixed material and oxygen-enriched gas, spraying the mixed material into a furnace chamber, and performing a first oxidation desulfurization reaction before the mixed material descends to a molten pool below the furnace chamber to obtain a preliminary oxidized material, wherein an oxide layer is arranged on the surface of the preliminary oxidized material. The mixed material comprises lead-zinc sulfide material and flux, and the particle size of the mixed material is smaller than 3mm. The mixed material comprises lead-zinc sulfide material and flux, wherein the grain diameter of the mixed material is not more than 0.05mm and not more than 3mm; the oxygen concentration of the oxygen-enriched gas is 20-100%.
And (3) after the primary oxidation material enters a molten pool, performing a second oxidation desulfurization reaction.
According to an embodiment of the present application, the distance of the mixed material from the upper surface of the molten pool is 3 meters or more.
According to the embodiment of the application, the particle size of the mixed material is equal to or less than 1mm and equal to or less than 3mm.
According to embodiments of the present application, the oxygen-enriched gas has a pressure of 2-3 kg/cm 2 The flow rate of the oxygen-enriched gas meets 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 1150-1250 ℃.
According to the embodiment of the application, the preparation method of the mixed material comprises the steps of mixing lead zinc sulfide ores with a flux, crushing and ball milling to obtain the mixed material.
The flux includes at least one of quartz sand, quicklime and calcium carbonate.
According to embodiments of the present application, the molten pool injection mode includes single side-blown, single bottom-blown, or a combination of side-blown and bottom-blown.
The second aspect of the present invention provides an oxidative desulfurization apparatus for lead-zinc sulfide ores, comprising:
the furnace body comprises a furnace shell, wherein the furnace shell surrounds 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 feeding pipe and the oxygen-enriched gas pipeline are both communicated with the feeding end of the spray gun.
A slag discharge port communicated with the molten pool.
According to an embodiment of the application, the furnace body further comprises a side blowing oxygen lance, and the side blowing oxygen lance is communicated with the molten pool.
In the oxidation desulfurization method of lead zinc sulfide ore, the mixed material has proper particle size, is mixed with oxygen-enriched gas, fully contacts with the oxygen-enriched gas in the process of descending to a molten pool, and rapidly carries out desulfurization and oxidation reaction. The surface of the mixed material forms an oxide layer 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, oxidation desulfurization further occurs, and the primary oxidation material enters a molten slag phase in an oxide form after deep desulfurization. The oxidation desulfurization method of 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 that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to the structures shown in these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic structural view of an oxidation desulfurization apparatus for lead-zinc sulfide ores according to an embodiment of the present application;
FIG. 2 is a diagram of a corresponding small-sized experimental apparatus for an oxidative desulfurization apparatus for lead-zinc sulfide ores according to an embodiment of the present application;
FIG. 3 is an SEM morphological feature, a distribution collection chart of each element, a distribution chart of each element, and a distribution chart of each element of a product of oxygen-enriched desulfurization of zinc sulfide concentrate material injection in example 4 of the invention.
The achievement of the object, functional features and advantages of the present invention will be further described with reference to the drawings in connection with the embodiments.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, are intended to fall within the scope of the present invention.
It should be noted that all directional indicators (such as upper and lower … …) in the embodiments of the present invention are merely used to explain the relative positional relationship, movement conditions, etc. between the components in a specific posture (as shown in the drawings), and if the specific posture is changed, the directional indicator is changed accordingly.
Furthermore, descriptions such as those referred to as "first," "second," and the like, are provided for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implying an order of magnitude of the indicated technical features in the present disclosure. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature.
Moreover, the technical solutions of the embodiments of the present invention may be combined with each other, but it is necessary to be based on the fact that those skilled in the art can implement the embodiments, and when the technical solutions are contradictory or cannot be implemented, it should be considered that the combination of the technical solutions does not exist, and is not within the scope of protection claimed by the present invention.
The applicant has found through extensive research that the volatilization temperatures of PbS and ZnS in lead and zinc concentrates are low, such as the boiling point of ZnS is 1185 ℃ and the boiling point of PbS is 1281 ℃, so that even under the condition of conventional smelting temperature, a great deal of volatilization of ZnS and PbS materials exists, and in addition, according to practical experience, obvious volatilization behavior of PbS can occur at 900 ℃ at ordinary temperature. In particular, the high melting point (1700 ℃) of ZnS makes it difficult to melt in slag, so that it is difficult to fully contact oxygen in a molten pool to timely perform oxidative desulfurization reaction, so that the oxidative desulfurization rate is difficult to keep up with the volatilization rate, and finally, a great amount of volatilization of materials and the formation of high smoke occurrence rate in the molten pool process are caused.
Based on the above, the embodiment of the invention provides an oxidation desulfurization method for lead zinc sulfide ore, which comprises the following steps:
step S100: mixing the mixed material and oxygen-enriched gas, spraying the mixed material into a furnace chamber, and performing a first oxidation desulfurization reaction before the mixed material descends to a molten pool below the furnace chamber to obtain a preliminary oxidized material, wherein an oxide layer is arranged on the surface of the preliminary oxidized material. The mixed material comprises lead-zinc sulfide material and flux. The grain diameter 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%.
The lead-zinc sulfide material comprises zinc, lead and sulfur elements, and usually also comprises iron, sulfur, calcium and silicon elements. In addition to the elements described above, the lead zinc sulfide material may in some embodiments 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 high compared with other elements. Illustratively, the lead zinc sulfide material includes Zn 10-40 wt%; pb 5-30 wt%; s10-30 wt%; fe 3-15 wt%; ca 1-10 wt%; siO (SiO) 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 minerals or raw materials which are formed by smelting and contain relatively high sulfur, lead and zinc elements.
The lead-zinc sulfide material can be classified into lead concentrate (with the highest lead content) and zinc concentrate (with the highest lead content) according to the elements with the highest content.
Illustratively, the lead concentrate has a primary element or constituent content of Pb 36.82 wt%, zn16.25 wt.%, S13.86 wt%, fe3.84 wt.%, cu 0.40 wt%, cao3.08 wt.%, siO 2.16 wt%.
Illustratively, the zinc concentrate has a major element or constituent 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.%.
The lead-zinc sulfide material and the flux are mixed into a mixed material, the mixed material is fine particles, the particle size is not required to be precisely controlled, and the particle size is only required to be less than or equal to 3mm and more than or equal to 0.05mm.
In this example, the complete oxidative desulfurization of the mixed material is divided into two stages, namely, a first oxidative desulfurization and a second oxidative desulfurization. The mixed material starts to descend after entering the furnace chamber and finally descends into the molten pool. The first oxidative desulfurization reaction occurs at the stage of the mixed material entering the furnace chamber to 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 is dropped to the molten pool.
The particle size of the mixed material is not excessively large, on one hand, the specific surface area of the mixed material is reduced, the contact area between 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 material is faster, and the time of the mixed material in the furnace chamber is shortened. Under the combined action, the mixed material is caused to have relatively low reaction degree in the first oxidation desulfurization reaction process.
Since the oxidative desulfurization reaction is performed in two stages, it is not pursued that the oxidative desulfurization reaction is completed in the first time, that is, the oxidative desulfurization reaction is completed entirely. Therefore, the particle size of the mixture is not required to be too small. Thus, the refining step in the preparation of the mixture material has relatively low requirement, and the refining cost is reduced. And the drying degree of the mixed material is also required to be relatively low. This is quite different from the requirements of flash processes, which require the material particle size to reach the micron level and require the material to be drier, thus completing the oxidative desulfurization process of the material in one pass.
In addition, in the examples of the present application, the particle size of the mixture is not too small. During the first oxidative desulfurization reaction and/or the second oxidative desulfurization reaction, it may be necessary to perform combustion heat compensation by means of fuel gas in the furnace chamber to maintain the reaction temperature. Or in the second oxidative desulfurization reaction process, oxygen is required to be introduced into the melt to further complete the oxidative desulfurization reaction. That is, the furnace body is also filled with fuel gas or oxygen, and the fuel gas can finally flow out of the flue of the furnace body, as shown in fig. 1.
In some embodiments, the flue is on the same side as the injection port (e.g., the discharge end of the lance) for the mixed material. When the particle size of the mixed material is too small, the mass is small, and lead-zinc sulfide materials in the mixed material are likely to be oxidized less quickly, namely, directly carried by fuel gas or oxygen and flow out of a flue. Or, the primary oxidation material is carried by the fuel gas or oxygen to flow out of the flue due to the small particle size and small mass. Thus, lead-zinc sulfide material loss is caused, and the recovery rate of metal is reduced.
Therefore, in consideration of the combination, the particle size of the mixture is controlled to not more than 3mm and not less than 0.05mm. I.e. the particle size of the mixed material is mainly in millimeter level. In some embodiments, 1 mm.ltoreq.the particle size of the mixture is.ltoreq.3 mm. Therefore, the method not only ensures higher reaction degree and higher reaction speed of the first oxidation desulfurization reaction, but also can reduce the cost of refining and drying, reduce material loss and improve the recovery rate of metal.
In the first oxidation desulfurization reaction, the mixed material fully contacts with oxygen-enriched gas in the movement process from top to bottom, and the desulfurization and oxidation reaction is rapidly carried out, namely the desulfurization rate of 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 subjected to oxidative desulfurization, while the inside is not subjected to oxidative desulfurization, so that a preliminary oxidized material is obtained. The oxide layer on the surface of the primary oxidation material is oxide of metal substances in the mixed material, such as zinc oxide and lead oxide. Because the melting point of oxide layer is higher, be difficult for volatilizing, the oxide layer wraps up inside material so that inside material is difficult for volatilizing, has reduced the volatilization rate.
Thus, the oxidation desulfurization rate of the sulfide is much higher than the volatilization rate thereof during the first oxidation desulfurization reaction, thereby suppressing the volatilization rate of the sulfide to some extent.
Step S200: and (3) after the primary oxidation material enters a molten pool, performing a second oxidation desulfurization reaction.
The molten pool is provided with a melt, for example, the former primary oxidation material forms the melt in the molten pool, and the subsequent primary oxidation material enters the melt to continue the second oxidation desulfurization reaction. Specific reaction conditions can be referred to the oxidation desulfurization conditions of conventional 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, oxidation desulfurization further occurs, 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 lead zinc sulfide ore, the mixed material has proper particle size, is mixed with oxygen-enriched gas, fully contacts with the oxygen-enriched gas in the process of descending to a molten pool, and rapidly carries out desulfurization and oxidation reaction. The surface of the mixed material forms an oxide layer 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, oxidation desulfurization further occurs, and the primary oxidation material enters a molten slag phase in an oxide form after deep desulfurization. The oxidation desulfurization method of 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 of the mixed material from the upper surface of the molten bath 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 top nozzle has a long distance from the surface of the molten pool, and the surface of particles is rapidly desulfurized and oxidized in the falling process of the sulfide concentrate in the mixed material so as to inhibit the volatilization of sulfides.
In some embodiments, the oxygen-enriched gas has an oxygen concentration of 20-100%. I.e. the oxygen enriched gas may be pure oxygen or a mixture of oxygen and other gases, such as nitrogen. Under this condition, the oxygen concentration in the oxygen-enriched gas is high, so that sufficient oxygen can be provided, and the mixture is fully reacted.
In some embodiments, the pressure of the oxygen-enriched gas is 2-3 kg/cm 2 The flow rate of the oxygen-enriched gas meets the oxygen-material ratio of 300-500 m 3 And/t. Under the condition, the oxygen-enriched gas can 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 dropping speed, so that the oxygen-enriched gas cannot be 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 of the first oxidative desulfurization reaction is 900-1200 ℃.
In some embodiments, the reaction temperature of the second oxidative desulfurization reaction is 1150-1250 ℃. At this reaction temperature, the sulfidic concentrate can be better subjected to deep oxidative desulfurization, entering the molten slag phase in oxide form.
In some embodiments, the method of preparing the mixture includes mixing lead zinc sulfide ore with flux, and crushing and ball milling the mixture. The flux includes at least one of quartz sand, quicklime and calcium carbonate.
If the lead zinc sulfide ore is mixed with flux, the refining treatment is carried out by a crushing-ball milling mode. During the refining treatment, 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 mixture, in some of these embodiments, pelletization may also be performed after ball milling. The specific technological parameters of crushing and ball milling are 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 of these embodiments, the mixture may also be subjected to a drying process.
In some embodiments, the molten pool injection mode includes single side-injection, single bottom-injection, or a combination of side-injection and bottom-injection.
The second aspect of the invention provides an oxidation desulfurization device for lead zinc sulfide ore, which comprises a furnace body 1, a spray gun 8, a feed pipe 7, an oxygen-enriched gas pipeline 6 and a slag discharge port 4.
The furnace body 1 comprises a furnace shell 5, the furnace shell 5 surrounding a furnace chamber 9 and a molten bath 10, the furnace chamber 9 being located above the molten bath 10. The slag discharge port 4 communicates with the molten bath 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 mixed material enters the spray gun 8 from the feed end of the spray gun 8 through the feed pipe 7. In particular, the mixture may be fed helically or belt fed to the feed pipe 7. Oxygen-enriched gas enters the lance 8 from the feed end of the lance 8 through the oxygen-enriched gas pipe 6. The mixture and the oxygen-enriched gas are injected into the furnace through the lance 8.
The feed pipe 7 and the oxygen-enriched gas pipe 6 may be independently communicated with the feed end of the lance 8, or one pipe may be communicated with the feed end of the lance 8, and the other pipe may be communicated with the other pipe. As shown in the figure, the oxygen-enriched gas pipeline 6 is communicated with the feeding end of the spray gun 8, and the feeding pipe 7 is provided with the side wall of the oxygen-enriched gas pipeline 6 and is communicated with the oxygen-enriched gas pipeline 6.
In some embodiments, the furnace body 1 further comprises side blown oxygen lances 2, the side blown oxygen lances 2 being in communication with the molten bath 10.
In some embodiments, the furnace body 1 further comprises a flue 3. The flue 3 is communicated with the furnace chamber 9, and the flue 3 is used for discharging flue gas. The flue 3 is illustratively located above the furnace chamber 9 on the same side as the lance 8.
Example 1
This example utilized lead concentrate (major element or constituent content of Pb 36.82 wt%, zn16.25 wt.%, S13.86 wt%, fe3.84 wt.%, cu 0.40 wt%, cao3.08 wt.%, siO) 2 5.16 wt.%) carrying out material injection oxygen-enriched desulfurization, and analyzing the volatilization loss rate of lead in the desulfurization process.
Firstly, mixing lead concentrate and flux, carrying out refining treatment by a crushing-ball milling mode, granulating to ensure that the particle size of the mixed material is not more than 3mm, and then drying the mixed material. In the mixed material, the mass fraction of the lead concentrate is 85 wt percent, and the mass fraction of the flux is 15wt.%. The flux is quicklime and quartz sand.
The dried mixture is sprayed into the furnace chamber 9 together with oxygen-enriched gas through a spray gun device at the furnace top (see figure 1), so that the mixture is fully contacted with the oxygen-enriched gas in the descending process, and the mixture is rapidly oxidized. Wherein the oxygen-enriched gas is pure oxygen with the oxygen concentration of 100 percent and the pressure of the oxygen-enriched gas is 2kg/cm 2 The flow rate of the oxygen-enriched gas meets the oxygen-material ratio of 300 m 3 And/t. The distance between the mixture and the upper surface of the bath 10 was 3 m. The reaction temperature of the first oxidative desulfurization reaction was 900 ℃.
The materials enter a molten pool 10 after being subjected to rapid desulfurization by contact with oxygen enrichment, and are subjected to further oxidation desulfurization in the molten pool 10, wherein the temperature of the molten pool 10 is about 1200 ℃, and blowing is carried out in an oxygen enrichment side blowing mode; after the deep desulfurization of oxidation of the molten pool 10 and the melting of the product, the product flows out and is discharged into a subsequent reduction working section for treatment; the total amount of the smoke and the content of lead in the smoke are measured, and the total amount of the smoke is multiplied by the content of the lead to obtain the volatilization amount of the lead, and the volatilization loss rate of the lead is 13.2 wt percent by dividing the volatilization amount of the lead by the total amount of the lead in the raw materials.
Example 2
Zinc concentrate (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) was used 2 6.12 wt.%) carrying out material injection oxygen-enriched desulfurization, and analyzing the volatilization loss rate of zinc in the desulfurization process.
Firstly mixing zinc concentrate and flux, carrying out refining treatment by a crushing-ball milling mode, granulating to ensure that the particle size of the mixed material is not more than 3mm, and then drying the mixed material. In the mixed material, the mass fraction of the zinc concentrate is 78 and wt percent, and the mass fraction of the flux is 22wt.%. The flux is quicklime and quartz sand.
The dried mixture is sprayed into a furnace chamber 9 (see figure 1) together with oxygen-enriched gas through a spray gun device at the furnace top, so that the mixture is fully contacted with the oxygen-enriched gas in the descending process, and the mixture is rapidly oxidized. Wherein the oxygen-enriched gas is pure oxygen with an oxygen concentration of 40%, and the pressure of the oxygen-enriched gas is 2.5 kg/cm 2 The flow rate of the oxygen-enriched gas meets the oxygen-material ratio of 400 m 3 And/t. The distance of the mixture from the upper surface of the bath 10 was 3.5 meters. The reaction temperature of the first oxidative desulfurization reaction was 1000 ℃.
The materials enter a molten pool 10 after being subjected to rapid desulfurization by being in contact with oxygen enrichment, and are subjected to further oxidation desulfurization in the molten pool 10, wherein the temperature of the molten pool 10 is about 1225 ℃, and blowing is carried out in an oxygen enrichment side blowing mode; after the deep desulfurization of oxidation of the molten pool 10 and the melting of the product, the product flows out and is discharged into a subsequent reduction working section for treatment; the total amount of the smoke and the content of lead in the smoke are measured, and the total amount of the smoke is multiplied by the content of zinc to obtain the volatilization amount of zinc, and the volatilization loss rate of zinc is 8.29 and wt percent by dividing the volatilization amount of zinc in the raw materials.
Example 3
Zinc concentrate (main element or component content of Zn 43.49 wt%, pb3.09 wt.%, S28.61 wt%, fe11.10 wt.%, cu) was used0.74 wt.%、Cd0.39 wt.%、CaO 0.82 wt.%、SiO 2 6.12 wt.%) carrying out material injection oxygen-enriched desulfurization, and analyzing the volatilization loss rate of zinc in the desulfurization process.
Firstly mixing zinc concentrate and flux, carrying out refining treatment by a crushing-ball milling mode, granulating to ensure that the particle size of the mixed material is not more than 3mm, and then drying the mixed material. In the mixed material, the mass fraction of the lead concentrate is 78 wt percent, and the mass fraction of the flux is 22wt.%. The flux is quicklime and quartz sand.
The dried mixture is sprayed into a furnace chamber 9 (see figure 1) together with oxygen-enriched gas through a spray gun device at the furnace top, so that the mixture is fully contacted with the oxygen-enriched gas in the descending process, and the mixture is rapidly oxidized. Wherein the oxygen-enriched gas is pure oxygen with the oxygen concentration of 20 percent and the pressure of the oxygen-enriched gas is 3 kg/cm 2 The flow rate of the oxygen-enriched gas satisfies the oxygen-material ratio of 500 m 3 And/t. The distance of the mixture from the upper surface of the bath 10 was 3.5 meters. The reaction temperature of the first oxidation desulfurization reaction is 1200 ℃.
The materials enter a molten pool 10 after being subjected to rapid desulfurization by being in contact with oxygen enrichment, and are subjected to further oxidation desulfurization in the molten pool 10, wherein the temperature of the molten pool 10 is about 1225 ℃, and blowing is carried out in an oxygen enrichment side blowing mode; after the deep desulfurization of oxidation of the molten pool 10 and the melting of the product, the product flows out and is discharged into a subsequent reduction working section for treatment; the total amount of the smoke and the content of lead in the smoke are measured, and the total amount of the smoke is multiplied by the content of zinc to obtain the volatilization amount of zinc, and the volatilization loss rate of the zinc is 9.80 wt percent by dividing the volatilization amount of the zinc by the total amount of the zinc in the raw materials.
Example 4
In the embodiment, zinc concentrate is utilized to carry out a comparison test of the material before and after the oxidation reaction with oxygen enrichment contact in a gas phase. Adopting zinc concentrate as raw material, and introducing N at 300 mL/min in experimental device shown in figure 2 2 120min, exhausting the air in the furnace; heating to 1250 ℃, and introducing oxygen at 1L/min; then spraying zinc concentrate into the furnace together with oxygen; changing into N immediately after blowing 2 Protecting, cooling and sampling, and detecting element content and distribution. FIGS. 3 (a), (b) and (c) are zinc sulfide concentrate feed injection rich respectivelyThe SEM morphological characteristics, the distribution collection graphs and the content of each element and the distribution graphs of each element of the oxygen desulfurization product show that Zn element and Fe element are contained in an O element distribution area, which indicates that Zn and Fe mainly exist in the form of oxide, S element only has a small amount of scattered distribution, and the result of 2wt.% of S content is combined, which indicates that the surface of concentrate particles is mostly desulfurized to form an oxide layer. The distributions of Pb, ca and Si are similar, indicating that Pb and Ca exist in the form of silicate solid solutions. Therefore, zinc sulfide can be rapidly oxidized and desulfurized in the oxygen-enriched desulfurization process of material injection, 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 not subjected to sufficient contact with oxygen-enriched gas, but was directly fed into the molten bath for oxidative desulfurization. The specific process is as follows: lead concentrate (main element or component content: pb 36.82 wt%, zn16.25 wt.%, S13.86 wt%, fe3.84 wt.%, cu 0.40 wt%, cao3.08 wt.%, siO) was added 2 5.16 wt.%) and flux, then directly throwing the materials into a molten pool, and performing oxidative desulfurization in the molten pool, wherein the temperature of the molten pool is about 1200-1250 ℃, and blowing is performed in a side blowing mode of oxygen-enriched gas; after the deep desulfurization of the oxidation of the molten pool and the melting of the product, the molten product flows out and is discharged into a subsequent reduction working section for treatment; the total and content analysis of the smoke gave a lead volatility loss of 28.6. 28.6 wt.%, which is significantly higher than the volatility level of example 1.
Comparative example 2
This comparative example is that of example 2. Unlike example 2, the mixture of zinc concentrate and flux is directly fed into the molten pool for oxidation desulfurization and slag formation reaction without being fully contacted with oxygen-enriched 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) 2 6.12 wt.%) and flux, refining by breaking-ball milling, granulating, directly feeding the material into molten pool, oxidizing and desulfurizing in the molten pool, in which the temp. of molten pool is 1250-1300 deg.C, and oxygen-enriched is usedBlowing in a gas side blowing mode; after the deep desulfurization of the oxidation of the molten pool and the melting of the product, the molten product flows out and is discharged into a subsequent reduction working section for treatment; the total and content analysis of the smoke gave a loss rate of 18.67. 18.67 wt% of zinc, which was significantly higher than the volatilization rate level of example 2.
Comparative example 3
This comparative example is that of example 1. Unlike example 1, the lead concentrate and flux were mixed, and the mixture was subjected to refining treatment by a crushing-ball milling method and then granulated to give a mixed material having a particle size of 3 to 5. 5mm, and other process conditions in the desulfurization process were the same as in example 2. The total amount of the smoke and the lead content in the smoke are measured, and the total amount of the smoke and the lead content are multiplied to obtain the volatilization amount of the lead, and the volatilization loss rate of the lead can be obtained by dividing the total amount of the lead in the raw materials by 20.5 wt percent, which is obviously higher than the volatilization rate level of the embodiment 1.
The above examples and comparative examples illustrate that by the oxidation desulfurization method of lead zinc sulfide ores in the examples of the present application, the mixed materials have suitable particle sizes and are oxidized in stages, so that smoke dust can be effectively reduced, the volatilization loss rate of lead zinc materials is reduced, and thus, the recovery rate of lead zinc sulfide ores is improved, and the cost is reduced.
In the above technical solution of the present invention, the above is only a preferred embodiment of the present invention, and therefore, the patent scope of the present invention is not limited thereto, and all the equivalent structural changes made by the description of the present invention and the content of the accompanying drawings or the direct/indirect application in other related technical fields are included in the patent protection scope of the present invention.
Claims (9)
1. An oxidation desulfurization method for lead zinc sulfide ore is characterized by comprising the following steps:
mixing and spraying a mixed material and oxygen-enriched gas into a furnace chamber, and performing a first oxidation desulfurization reaction on the mixed material before the mixed material descends to a molten pool below the furnace chamber to obtain a preliminary oxidized material, wherein the surface of the preliminary oxidized material is provided with an oxide layer; the mixed material comprises lead-zinc sulfide material and flux, wherein the grain diameter of the mixed material is more 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 after the primary oxidation material enters the molten pool, performing a second oxidation desulfurization reaction.
2. The method for oxidative desulfurization of lead-zinc sulfide ores according to claim 1, wherein the distance between the mixed material and the upper surface of the molten pool is 3m or more.
3. The method for oxidative desulfurization of lead-zinc sulfide ores according to claim 1, wherein the particle diameter of the mixed material is 1mm or less and 3mm or less.
4. The oxidative desulfurization method of lead-zinc sulfide ores as recited in claim 1, wherein the oxygen-enriched gas has a pressure of 2-3 kg/cm 2 The flow rate of the oxygen-enriched gas satisfies the oxygen material ratio of 300-500 m 3 /t。
5. The oxidative desulfurization method of lead-zinc sulfide ores according to claim 1, wherein the reaction temperature of the first oxidative desulfurization reaction is 900-1200 ℃.
6. The oxidative desulfurization method of lead-zinc sulfide ores according to claim 1, wherein the reaction temperature of the second oxidative desulfurization reaction is 1150-1250 ℃.
7. The oxidative desulfurization method of lead-zinc sulfide ores according to claim 1, wherein the preparation method of the mixed material comprises the steps of mixing lead-zinc sulfide ores with a flux, and crushing and ball-milling to obtain the mixed material;
the flux includes at least one of quartz sand, quicklime and calcium carbonate.
8. The oxidative desulfurization method for lead-zinc sulfide ores according to claim 1, wherein the molten pool blowing mode comprises single side blowing, single bottom blowing or side-blowing bottom blowing mixing.
9. An oxidative desulfurization device for oxidizing lead-zinc sulfide ores, applied to the oxidative desulfurization method as claimed in any one of claims 1 to 8, comprising:
the furnace body comprises a furnace shell, wherein 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 feeding pipe and the oxygen-enriched gas pipeline are communicated with the feeding end of the spray gun;
a slag discharge port communicated with the molten pool;
the furnace body also comprises a side oxygen blowing gun which is communicated with the molten pool.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310044112.6A CN115807165B (en) | 2023-01-29 | 2023-01-29 | Oxidative desulfurization method and device for lead-zinc sulfide ore |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310044112.6A CN115807165B (en) | 2023-01-29 | 2023-01-29 | Oxidative desulfurization method and device for lead-zinc sulfide ore |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115807165A CN115807165A (en) | 2023-03-17 |
| CN115807165B true CN115807165B (en) | 2023-05-26 |
Family
ID=85487618
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310044112.6A Active CN115807165B (en) | 2023-01-29 | 2023-01-29 | Oxidative desulfurization method and device for lead-zinc sulfide ore |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115807165B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1375683A (en) * | 1973-04-14 | 1974-11-27 | ||
| JPH04147926A (en) * | 1990-10-09 | 1992-05-21 | Sumitomo Metal Mining Co Ltd | Method for fusion-desulfurizing zinc sulfide concentrate |
| JPH059616A (en) * | 1991-06-28 | 1993-01-19 | Sumitomo Metal Mining Co Ltd | Method for melting and desulfurizing zinc concentrate |
| CN203559108U (en) * | 2013-11-25 | 2014-04-23 | 长沙有色冶金设计研究院有限公司 | System for simultaneously smelting lead and zinc |
| CN110373552A (en) * | 2019-07-24 | 2019-10-25 | 铜陵市敏睿富氧侧吹科技有限公司 | A kind of harmless treatment process using the low-grade lead-zinc residue of oxygen-enriched side-blowing furnace bath smelting |
| CN111424175A (en) * | 2020-04-15 | 2020-07-17 | 中国恩菲工程技术有限公司 | System and method for smelting zinc concentrate and zinc-containing secondary material |
| CN212316208U (en) * | 2020-04-08 | 2021-01-08 | 中国恩菲工程技术有限公司 | Smelting system of low-grade lead-zinc oxide ore |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59226130A (en) * | 1983-05-02 | 1984-12-19 | Mitsubishi Metal Corp | Continuous direct smelting method of lead |
| US5178667A (en) * | 1990-10-09 | 1993-01-12 | Sumitomo Metal Mining Company Limited | Dry process for refining zinc sulfide concentrates |
| CN103388081A (en) * | 2013-07-23 | 2013-11-13 | 中南大学 | Bath smelting method and apparatus of zinc sulfide concentrate and lead-zinc containing materials |
| CN106893871B (en) * | 2016-12-28 | 2019-01-22 | 呼伦贝尔驰宏矿业有限公司 | A kind of lead concentrate treatment process |
| CN111411230A (en) * | 2020-04-15 | 2020-07-14 | 中国恩菲工程技术有限公司 | Suspension smelting electrothermal reduction furnace and method for smelting zinc concentrate |
| CN111893310A (en) * | 2020-09-08 | 2020-11-06 | 新乡市中联富氧侧吹技术开发有限公司 | Harmless recycling treatment method for solid hazardous waste |
| CN112981136B (en) * | 2021-04-16 | 2021-08-31 | 中国恩菲工程技术有限公司 | One-step zinc smelting method for spraying zinc concentrate in molten pool |
-
2023
- 2023-01-29 CN CN202310044112.6A patent/CN115807165B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1375683A (en) * | 1973-04-14 | 1974-11-27 | ||
| JPH04147926A (en) * | 1990-10-09 | 1992-05-21 | Sumitomo Metal Mining Co Ltd | Method for fusion-desulfurizing zinc sulfide concentrate |
| JPH059616A (en) * | 1991-06-28 | 1993-01-19 | Sumitomo Metal Mining Co Ltd | Method for melting and desulfurizing zinc concentrate |
| CN203559108U (en) * | 2013-11-25 | 2014-04-23 | 长沙有色冶金设计研究院有限公司 | System for simultaneously smelting lead and zinc |
| CN110373552A (en) * | 2019-07-24 | 2019-10-25 | 铜陵市敏睿富氧侧吹科技有限公司 | A kind of harmless treatment process using the low-grade lead-zinc residue of oxygen-enriched side-blowing furnace bath smelting |
| CN212316208U (en) * | 2020-04-08 | 2021-01-08 | 中国恩菲工程技术有限公司 | Smelting system of low-grade lead-zinc oxide ore |
| CN111424175A (en) * | 2020-04-15 | 2020-07-17 | 中国恩菲工程技术有限公司 | System and method for smelting zinc concentrate and zinc-containing secondary material |
Non-Patent Citations (1)
| Title |
|---|
| 铅富氧闪速熔炼新技术;王成彦;郜伟;尹飞;宋元张;郑晓斌;梁德华;;有色金属(冶炼部分)(第04期);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115807165A (en) | 2023-03-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5888270A (en) | Copper converting | |
| US3832163A (en) | Process for continuous smelting and converting of copper concentrates | |
| JPH021216B2 (en) | ||
| CN111876611A (en) | Method for deeply removing arsenic, lead, zinc and tin from crude copper by fire refining | |
| WO2007038840A1 (en) | Method and apparatus for lead smelting | |
| US4519836A (en) | Method of processing lead sulphide or lead-zinc sulphide ores, or sulphide concentrates, or mixtures thereof | |
| CN115807165B (en) | Oxidative desulfurization method and device for lead-zinc sulfide ore | |
| US4005856A (en) | Process for continuous smelting and converting of copper concentrates | |
| US4614541A (en) | Method of continuous metallurgical processing of copper-lead matte | |
| CN1040030C (en) | Method for producing high-grade nickel matte from at least partly pyrometallurgically refined nickel-bearing raw materials | |
| CN112746184B (en) | Copper smelting furnace, copper smelting equipment and copper smelting method | |
| CN105087950B (en) | From high Magnetic Copper oxidizing slag, one step is made the method for blister copper and makes the stove of blister copper | |
| CA1162056A (en) | Process and apparatus for the separation of lead from a sulfidic concentrate | |
| CA1208444A (en) | High intensity lead smelting process | |
| CN216614801U (en) | Copper smelting furnace and copper smelting equipment | |
| US9650694B2 (en) | Treatment of high sulphur solids | |
| AU2006299743C1 (en) | Method and apparatus for lead smelting | |
| CA1212842A (en) | Method of processing lead sulphide or lead/zinc sulphide ores, or sulphide concentrates, or mixtures thereof | |
| CA2876819C (en) | Method for treating combustible material and installation | |
| US483962A (en) | Christopher james | |
| SU637443A1 (en) | Method of processing fine-dispersed tin-containing materials | |
| SU1129259A1 (en) | Method for processing secondary lead raw material | |
| CN116219192A (en) | Zinc smelting method and application thereof | |
| CN117881802A (en) | Smelting furnace and method of operating same | |
| Kenji | Some Studies on the Smelting of Copper and Lead |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |