CN112063848B - Metallurgical furnace for treating copper-containing sludge and treatment method thereof - Google Patents
Metallurgical furnace for treating copper-containing sludge and treatment method thereof Download PDFInfo
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- C22B15/00—Obtaining copper
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- C22B15/0028—Smelting or converting
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F22—STEAM GENERATION
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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Abstract
The invention relates to a metallurgical furnace for treating copper-containing sludge and a treatment method, wherein the metallurgical furnace comprises a side-blown furnace, wherein the side-blown furnace is provided with a furnace hearth section, a furnace body section and a furnace top section which are sequentially distributed from bottom to top; the bottom side of the hearth section is communicated with an electrothermal forehearth, the side wall of the electrothermal forehearth is provided with a siphon port and a slag tap, the siphon port is lower than the slag tap, and the bottom area of the inner cavity of the electrothermal forehearth is 1/2-3/2 of that of the inner cavity of the hearth section; the height L1 of the furnace top section is 3-5 m. The metallurgical furnace can directly and independently smelt the low-grade copper-containing sludge to generate matte, black copper and water-quenched slag with economic value, successfully solves the problem that the low-grade copper-containing sludge is difficult to directly smelt, simplifies the process, adopts electric heating forehearth dilution and reduces the energy consumption cost.
Description
Technical Field
The invention relates to a metallurgical furnace for treating copper-containing sludge and a treatment method thereof, in particular to a metallurgical furnace for treating low-grade copper-containing sludge and a treatment method thereof, belonging to the technical field of comprehensive recovery of nonferrous metals.
Background
Copper-containing sludge generally exists in the industries of electroplating, printing and dyeing, metal processing and the like, and has high treatment difficulty due to low taste and complex components, at present, the sludge is mainly treated in a stockpiling mode, occupies a large amount of land resources, and if the sludge is not treated properly, heavy metal components in the sludge enter soil, so that immeasurable damage can be caused to the surrounding ecological environment.
Three technical policies of reduction, harmlessness, resource utilization and the like are implemented on solid waste treatment in China, and the copper-containing sludge contains more valuable metals such as copper, nickel and the like, so that the copper-containing sludge is a utilizable solid waste resource. The effective utilization of the resources can not only solve the potential hidden danger of solid waste stockpiling, but also change waste into valuable and relieve the problem of copper demand in the market to a certain extent. At present, the treatment modes of the copper-containing sludge comprise wet leaching, solidification treatment and pyrometallurgical smelting. Although the methods can effectively treat part of the copper-containing sludge with higher taste, the method still has the problem of difficult treatment of low-grade copper-containing sludge and the need of batching. The invention adopts the advanced oxygen-enriched side-blowing technology to directly treat the low-grade copper-containing sludge, thereby achieving the aims of waste reclamation, cleanness, environmental protection and energy saving production.
In the process of smelting by adopting the side-blown converter, a metal liquid phase is generally collected by adopting a siphon method, so that a relatively obvious solid-liquid interface is needed to selectively collect the metal phase, but for low-grade copper-containing sludge, in the process of smelting by adopting the traditional oxygen-enriched side-blown converter, because the slag amount is large, the metal content is low, the generated liquid phase is less, and the slag and the metal are difficult to separate. Chinese patent specification CN 108707750 a discloses a comprehensive treatment method for copper-containing sludge and circuit boards, which uses an oxygen-rich side-blown converter to treat low-grade copper-containing sludge, but needs to add a certain amount of high-grade copper-containing material circuit boards to ensure the content of copper in the materials fed into the converter during the treatment process, thereby ensuring the purpose of obvious layering of matte and slag phase during the smelting process, but the patent is not suitable for the situation of treating copper-containing sludge alone without adding high-copper-containing materials. Chinese patent CN 106399699B discloses a treatment process of copper-containing sludge, but the copper content of the copper-containing sludge is 3-18%, when the copper content of the sludge is less than 3%, the method is difficult to directly and effectively treat the material, and the material also needs to be recovered by means of ore blending.
Disclosure of Invention
In view of the defects of the prior art, one of the purposes of the invention is to provide a metallurgical furnace for treating copper-containing sludge so as to conveniently and comprehensively recover valuable metals in the copper-containing sludge; the invention also aims to provide a treatment method for the copper-containing sludge so as to improve the recovery rate of copper in the low-grade copper-containing sludge.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the metallurgical furnace for treating the copper-containing sludge comprises a side-blown furnace, wherein the side-blown furnace is provided with a furnace hearth section, a furnace body section and a furnace top section which are sequentially distributed from bottom to top; the bottom side of the hearth section is communicated with an electrothermal forehearth, the side wall of the electrothermal forehearth is provided with a siphon port and a slag tap, the siphon port is lower than the slag tap, and the bottom area of the inner cavity of the electrothermal forehearth is 1/2-3/2 of that of the inner cavity of the hearth section; the height L1 of the furnace top section is 3-5 m.
Further, the hearth section is communicated with the electric heating front bed through a communication opening.
Further, the inner bottom surface of the hearth section is inclined towards the direction of the electric heating forehearth so as to facilitate the molten slag phase and liquid phase to be layered from the inside of the hearth to the electric heating forehearth, and preferably, the included angle between the inner bottom surface and the horizontal plane is 5-20 degrees so as to ensure a certain flow velocity but not too fast.
Furthermore, a chute is arranged on the top side of the furnace body section, and a first air nozzle and a second air nozzle which are distributed up and down are arranged on the side wall of the furnace body section.
In order to enable the natural gas and the oxygen to enter the material, so that the reaction is easier to occur, the air outlet of the second air nozzle is obliquely arranged downwards. Optionally, the central axis direction of the second tuyere forms an included angle with the horizontal plane, and preferably, the included angle is not less than 30 ° and not more than 45 °. In addition, natural gas is adopted to replace anthracite as fuel and reducing agent, so that the problem that sulfur in the flue gas exceeds the standard is solved, the production is clean, the material mixing step and the subsequent flue gas desulfurization process are omitted, and the equipment cost is reduced.
Furthermore, the bottom area of the inner cavity of the electric heating front bed is at least 5 square meters. More preferably, the bottom area of the inner cavity of the bed before electric heating is 8 square meters to 12 square meters.
Further, the inner wall of the furnace top section is provided with a heat insulation material layer or the furnace top section is made of a heat insulation material. The furnace top section is made of the heat insulation material or the heat insulation material is arranged on the inner wall of the furnace top section, so that the temperature of flue gas generated after copper-containing sludge is smelted in the inner cavity of the furnace top section can reach above 850 ℃, a place for decomposing dioxin is formed in the inner cavity of the furnace top section, and the flue gas is fully decomposed.
The system comprises a flue gas treatment system, a gas purification system and a gas purification system, wherein the flue gas treatment system comprises an SNCR (selective non-catalytic reduction) denitration device, a spray quenching tower, a dust collecting device, a desulfurization tower, a demisting device and an SCR (selective catalytic reduction) denitration device which are sequentially connected in series; an activated carbon injection device and a calcium hydroxide injection device are arranged on a pipeline between the spray quenching tower and the dust collection device; and the SNCR denitration device is communicated with an outlet of the furnace top section.
Compared with the prior art, after the smelting flue gas comes out from the flue gas outlet of the side-blown converter, the denitration efficiency can reach more than 90% through the treatment of the equipment, so that the requirement of standard emission is met.
In the invention, the side-blown converter and the electric heating fore-bed are directly connected by a communication port, so that low-grade copper-nickel-containing waste slag is smelted in the side-blown converter, a slag phase and a copper matte phase jointly enter the electric heating fore-bed for clarification and layering, the electric heating fore-bed has larger volume, and the surface area of the bottom of the inner cavity of the electric heating fore-bed is 1/2-3/2 of the surface area of the bottom of the inner cavity of the furnace hearth, so that more slag phases can be ensured to be placed, more metal liquid phases can be accumulated more easily, the slag phases and the liquid phases are obviously layered, and the aim of separating slag from liquid is fulfilled.
The method ensures that the flue gas stays in the inner cavity of the furnace top for more than 2 seconds by increasing the height of the channel of the furnace top section; the dioxin-containing flue gas has sufficient time to be heated and decomposed into harmless gas when passing through the area.
Based on the same inventive concept, the invention also provides a treatment method for the copper-containing sludge, which comprises the following steps:
s1, drying the sludge containing copper to be treated to obtain the sludge containing copper with the water content not higher than 30wt%, wherein the water content is preferably 20-30 wt%;
s2, mixing the copper-containing sludge obtained in the step S1 with a reducing agent, a flux and an additive to obtain a mixture;
wherein the mass ratio of the copper-containing sludge to the reducing agent, the flux and the additive is 100:5-20:5-20: 1-20; the reducing agent comprises at least one of carbon powder, activated carbon, pulverized coal and coke, and the flux comprises at least one of quartz stone, limestone and hematite; the additive is compounded by at least 2 sodium salts;
s3, conveying the mixture obtained in the step S2 into the metallurgical furnace, blowing natural gas and oxygen-enriched air into the metallurgical furnace through a second air nozzle, smelting, discharging a copper matte phase in an electric heating fore-bed through a siphon port, and discharging a slag phase through a slag tap;
optionally, air is introduced into the first air nozzle, natural gas and oxygen-enriched air are introduced into the second air nozzle, the air flow rate of the first air nozzle is 20-25 m/s, and the mixed gas flow rate of the second air nozzle is 200-220 m/s. The diameter of the air hole is 30-80 mm. Thus, the introduction of a sufficient amount of air and mixed gas can be ensured.
Wherein the smelting temperature is 1200-1500 ℃, and the oxygen concentration in the oxygen-enriched air is 50-80 vol%.
Thus, the mixture is smelted by a side-blown converter and then transferred to an electric heating fore-bed for dilution to obtain products such as black copper, matte, water-quenched slag and the like, and a slag phase and a copper matte phase are obtained by layering.
Further, in S1, the copper-containing sludge is dried at low temperature by a steam dryer, and optionally, the used steam is sourced from a waste heat boiler, so as to achieve the purpose of reasonably utilizing waste heat.
Further, in S2, the mass ratio of the copper-containing sludge to the reducing agent, the flux and the additive is 100:5-10:10-20: 1-10.
Optionally, the activated carbon is spent activated carbon.
Further, in S2, the reducing agent is prepared by mixing activated carbon and carbon dioxide at a mass ratio of 1-5:1, preferably 1-3: 1; the flux is formed by mixing hematite and quartz according to the mass ratio of 5-20:1, and preferably 10-5: 1.
Further, in S2, the additive is prepared by mixing sodium carbonate and sodium chloride according to the mass ratio of 1-3:1, preferably 1-2: 1: .
Further, in S3, after the waste heat of the waste heat boiler is utilized, the smoke generated by smelting is treated by a smoke treatment system to reach the emission standard.
Further, in S3, the oxygen concentration in the oxygen-enriched air is 50-60 vol%.
Further, in the present invention, the Cu content in the copper-containing sludge is <3 wt%.
According to the invention, the metallurgical furnace is provided with the side-blown furnace and the electric heating fore-bed, the copper-containing sludge enters the electric heating fore-bed through the smelting furnace side-blown smelting, the smelting material is depleted through the electric heating fore-bed, and the matte is generated through sedimentation and layering.
For the copper-containing sludge with low copper grade, during treatment, the slag amount is large, the occurrence condition is complex, and in order to enable the metals in the sludge to be enriched more efficiently, sodium-alkali slag can be generated by adding sodium salt, the melting point and the density of slag are reduced, the viscosity of the slag is reduced, the fluidity of the slag is improved, valuable metals in materials are easier to separate, the copper content in the slag is reduced, and the recovery rate of copper is increased.
The electric heating fore-bed can be heated by adopting electrodes, after copper-containing sludge is smelted by a side-blown converter, metal is melted and transferred to the electric heating fore-bed for sedimentation and layering, a slag tap and a siphon tap are arranged in the electric heating fore-bed, and layered slag phase and copper matte phase are respectively discharged from the tap. The reason is that the copper grade in the copper-containing sludge is low, the slag quantity is large, the volume of the conventional furnace chamber is small, the retention time of materials in the furnace chamber is short, an obvious copper matte layer is difficult to obtain, and the cost is high and the engineering is complex when the furnace chamber is arranged too large. In order to solve the problem, the invention transfers the melt into the electric heating fore bed for sedimentation, prolongs the sedimentation time of copper matte and increases the amount of copper matte in the fore bed to ensure that the copper matte is enough to generate an obvious copper matte layer, thereby achieving the aim of slag matte layering.
The main reactions in the smelting process are as follows:
(1) oxidation-reduction reaction:
2CuO+C=Cu 2 O+CO
Cu 2 O+C=2Cu+CO
NiO+C=Ni+CO
4Al+3O 2 =2Al 2 O 3
2CO+O 2 =2CO 2
(2) slagging reaction
Fe 2 O 3 +CO=2FeO+CO 2
Na 2 O+SiO 2 =Na 2 O·SiO 2
MgO+SiO 2 =MgO·SiO 2
FeO+SiO 2 =FeO·SiO 2
Compared with the prior art, the invention has the following beneficial effects:
1) the copper-containing sludge is dried and then mixed with the additive and the flux, so that pelletizing treatment is not needed, and the process is simple.
2) For low-grade copper-containing sludge, other materials with high copper content are not required to be added for oxygen-enriched smelting together, and matte, black copper and water-quenched slag with economic value can be directly and independently smelted.
3) The flue gas components can reach the standard and be emptied after being treated in the flue gas treatment system, and the denitration efficiency is up to more than 90 percent.
4) The copper-containing sludge contains complex components, and the pressure of flue gas treatment is greatly reduced by adopting natural gas as an energy source.
5) The invention can directly decompose dioxin in the furnace top section without secondary combustion heating, and greatly reduces the treatment cost of the copper-containing sludge.
Drawings
FIG. 1 is a flow chart of the treatment of a copper-containing sludge according to the present invention.
FIG. 2 is a top view of a metallurgical furnace of the present invention.
FIG. 3 is a front view of a metallurgical furnace of the present invention.
Fig. 4 is a schematic diagram of a flue gas treatment system according to the present invention.
Detailed Description
The following description describes alternative embodiments of the invention to teach one of ordinary skill in the art how to make and use the invention. Some conventional aspects have been simplified or omitted for the purpose of teaching the present invention. Those skilled in the art will appreciate that variations or substitutions from these embodiments will fall within the scope of the invention. Those skilled in the art will appreciate that the features described below can be combined in various ways to form multiple variations of the invention. Thus, the present invention is not limited to the following alternative embodiments, but is only limited by the claims and their equivalents. For convenience of description, the words "upper", "lower", "left" and "right" in the following description are used only to indicate the correspondence between the upper, lower, left and right directions of the drawings themselves, and do not limit the structure.
Example 1
Referring to fig. 2 and 3, the metallurgical furnace for treating copper-containing sludge comprises a side-blown furnace, wherein the side-blown furnace is provided with a hearth section 2, a furnace body section A and a furnace top section 10 which are distributed from bottom to top in sequence; the bottom side of the hearth section 2 is communicated with an electrothermal forehearth 13, the side wall of the electrothermal forehearth 13 is provided with a siphon inlet 14, a safety port 15 and a slag tap 16, the siphon inlet 14 is lower than the slag tap 16, and the bottom area of the inner cavity of the electrothermal forehearth 13 is 2 times of that of the inner cavity of the hearth section 2; the height L1 of the roof section 10 is 4.2 m. The hearth section 2 is arranged on the hearth 1.
A slag tap water jacket is arranged outside the slag tap 16. The safety port 15 is used for maintenance.
The hearth section 2 is communicated with the electric heating front bed 13 through a communication port 12.
The inner bottom surface of the hearth section 2 is inclined towards the direction of the electric heating front bed 13, preferably, the included angle of the inner bottom surface and the horizontal plane is 12 degrees.
The top side of the furnace body section A is provided with a chute 7, and the side wall of the furnace body section A is provided with a first air nozzle 11 and a second air nozzle 3 which are distributed up and down. The number of the first tuyere 11 and the second tuyere 3 is plural. The first tuyere 11 is mainly used for blowing air.
The air outlet of the second air nozzle 3 is obliquely arranged downwards. The second air nozzle is mainly divided into two types, one type is an air nozzle used for inputting oxygen-enriched gas, the other type is an air nozzle used for inputting natural gas, and an oxygen-enriched gas air nozzle is clamped between every two natural gas air nozzles. This embodiment adopts oxygen-enriched gas tuyere and natural gas tuyere interval arrangement, makes the natural gas burning more abundant, makes the natural gas change and gets into inside the material and react.
And a fourth layer of water jacket 9 and a flue interface water jacket 8 which are distributed at the lower part and the upper part are arranged on the furnace top section.
The hearth section 2 is provided with a first layer water jacket 4, a second layer water jacket 5 and a third layer water jacket 6 from bottom to top.
The system further comprises a flue gas treatment system 17, and referring to fig. 4, the flue gas treatment system comprises a waste heat boiler 1717, a spray quenching tower 1713, a bag dust collector 1712, an induced draft fan 177, a wet desulfurization tower 175, an electric demister 174, a flue gas heat exchanger 172 (GGH), a flue gas heater 173 (SGH) and an SCR denitration device 171 which are connected in series in sequence. Wherein the dust collecting cavity of the bag dust collector 1712 is communicated with the smoke dust storage 176. An activated carbon injection device and a calcium hydroxide injection device are arranged on a pipeline between the spray quenching tower 1713 and the bag dust collector 1712. Wherein the activated carbon is fed before and the calcium hydroxide is fed after. Specifically, in order to further adsorb harmful substances in the flue gas, the activated carbon injection device comprises an activated carbon bin 1712, and activated carbon in the activated carbon bin 1712 is conveyed into the screw feeder 1710 through the fan 178 and then conveyed into the pipeline. The calcium hydroxide spraying device comprises a calcium hydroxide bin 179, and calcium hydroxide in the calcium hydroxide bin 179 is sent into another screw feeder 1710 through another fan 178 and then sent into a pipeline. Therefore, the calcium hydroxide injection device and the activated carbon injection device perform dry deacidification, and the calcium hydroxide is used as a dry deacidification agent. The activated carbon spraying system ensures that the activated carbon and the flue gas are uniformly mixed, so that the effect of efficient adsorption is achieved, and the activated carbon is coal or wood. And the air inlet of the waste heat boiler 1717 is communicated with the air outlet of the side-blown converter 1715.
The water-cooled wall of the exhaust-heat boiler 1717 is provided with an SNCR denitration spray gun 1714, and the SNCR denitration spray gun 1714 is used for spraying the reducing agent in the reducing agent storage cabin 1716 into the flue gas.
And the flue gas from the side-blown converter enters a smelting flue gas treatment system, and can be discharged after treatment.
The flue gas treatment system mainly combines an SNCR method and an SCR method, urea aqueous solution with the concentration of about 10% is uniformly sprayed on a water-cooled wall in the temperature range of 950-1750 ℃ of the flue gas temperature of the waste heat boiler 1717 through an SNCR denitration spray gun 1714, the aim of removing and reducing nitrogen oxides in the flue gas is fulfilled through selective reduction of urea and the nitrogen oxides in the flue gas, and the denitration efficiency is 40-70%.
The flue gas treatment system mainly comprises an injection device, a storage device and a conveying device, and a spraying port of 4 SNCR denitration spray guns 1714 is arranged on the waste heat boiler 1717, so that sufficient addition of a reducing agent is ensured. The flue gas in the waste heat boiler 1717 is cooled to be not lower than 500 ℃ and then enters the spray quenching tower 1713, and is fully contacted with atomized water or lime slurry sprayed from a cooling spray gun. The atomized water absorbs a large amount of heat because the high-temperature flue gas is heated and rapidly evaporated, and meanwhile, the high-temperature flue gas is rapidly cooled to the temperature of less than 200 ℃, so that a dioxin synthesis interval is avoided. The temperature of the flue gas at the outlet of the spray quenching tower 1713 is lower than 200 ℃, the flue gas at the outlet of the spray quenching tower 1713 is connected with the bag dust collector 1711 through a smoke tube, a calcium hydroxide injection device and an active carbon injection device are arranged between the spray quenching tower 1713 and the bag dust collector 1711 for dry deacidification, calcium hydroxide is used as a dry deacidification agent, the active carbon injection system ensures that the active carbon and the flue gas are uniformly mixed, the efficient adsorption effect is achieved, and the active carbon is coal or wood. The flue gas passes through a bag collector 1711, and the smoke is collected by an ash bucket and conveyed to a smoke warehouse 176 through a buried scraper. Flue gas after the dust removal gets into desulfurizing tower 175 through the draught fan and carries out the desulfurization, adopt sodium hydroxide to carry out wet flue gas desulfurization as alkali lye, get into rear end SCR denitrification facility 171 through electrostatic defogging and further get rid of the NOx in the flue gas, the flue gas that comes out from wet electric defogging gets into the GGH heat exchanger, improve the temperature to about 130 ℃, reentrant SGH heat exchanger carries out the heat transfer with saturated steam, improve the flue gas temperature to the reaction temperature who adapts to low temperature SCR catalyst, reentrant SCR system denitration, flue gas after the denitration carries out the GGH heat exchanger heat transfer with the flue gas of wet electric defogging export, reduce the temperature to discharge up to standard more than 135 ℃. When the NOx in the flue gas passes through the catalyst layer, the NOx in the flue gas and the reducing agent are subjected to selective reaction on the surface of the catalyst layer, so that the aim of further removing the NOx in the flue gas is fulfilled, and meanwhile, dioxin can be removed. The SCR denitration device mainly comprises the following components: a high-temperature flue gas/flue gas heat exchanger 172 (GGH), a steam/flue gas heater 173 (SGH), an SCR reactor 171 and the like, and the denitration efficiency can reach more than 90%.
The process flow of the flue gas treatment system is as follows: side-blown furnace flue gas → SNCR denitration → waste heat recovery → flue gas quench tower → dry deacidification, activated carbon adsorption → bag dust removal → induced draft fan → wet deacidification → wet electric demisting → GGH heat exchanger → flue gas heating SGH → SCR system → discharge after reaching standards.
The functional requirements of the flue gas treatment system are as follows: high-temperature flue gas produced by the oxygen-enriched side-blown smelting furnace enters a waste heat boiler 1717 to recover waste heat, an SNCR denitration spray gun (at least 4 sets) is arranged on a vertical flue of the waste heat boiler 1717 (the flue gas temperature interval is 850-1100 ℃), the waste heat boiler reduces the flue gas temperature to be not lower than 500 ℃, the flue gas enters a spray quenching tower and crosses the synthesis temperature of dioxin, the outlet temperature of the quenching tower is lower than 200 ℃, the flue gas at the outlet of the quenching tower is connected with a bag dust collector through a flue pipe, and a calcium hydroxide injection device and an active carbon injection device are arranged between the quenching tower and the bag dust collector. Flue gas enters a flue gas desulfurization system after being dedusted by a bag dust collector, and the desulfurized flue gas enters an SCR denitration device after passing through an electric demister, a GGH heat exchanger and a flue gas heater SGH.
When the device works, materials enter from the chute 7, are smelted by the side-blown converter and then enter the electrothermal fore-bed 13, the metal liquid phase is gathered at the bottom of the electrothermal fore-bed 13, the area of the bottom of the electrothermal fore-bed 13 is 8-12 square meters, so that the slag phase is distributed on the upper part of the liquid phase, after layering, the metal phase (copper matte phase) is discharged from the siphon inlet 14, and the slag phase is discharged from the slag discharge outlet 16.
Referring to fig. 1, the treatment method for copper-containing sludge includes the following steps:
s1, drying the sludge containing copper to be treated to obtain sludge containing copper with the water content of 26 wt%;
s2, mixing the copper-containing sludge obtained in the step S1 with a reducing agent, a flux and an additive to obtain a mixture;
wherein the mass ratio of the copper-containing sludge to the reducing agent, the flux and the additive is 100:10:10: 8;
s3, conveying the mixture obtained in the step S2 into the metallurgical furnace, blowing natural gas and oxygen-enriched air into the metallurgical furnace through a second air nozzle, smelting, discharging a copper matte phase in an electric heating fore-bed through a siphon port, and discharging a slag phase through a slag tap;
wherein the smelting temperature is 1300 ℃, and the oxygen concentration in the oxygen-enriched air is 55 vol%.
In S2, the reducing agent is formed by mixing activated carbon and carbon powder according to the mass ratio of 1: 1; the flux is formed by mixing hematite and quartz according to the mass ratio of 10: 1. In S2, the additive is formed by mixing sodium carbonate and sodium chloride according to the mass ratio of 2: 1.
In the implementation, black copper with a copper taste of 86wt% and matte with a copper taste of 47wt% can be obtained, and the copper recovery rate reaches 97 wt%. The flue gas is treated by the treatment system, the denitration rate reaches 93 percent, and the emission standard is reached.
Example 2
Example 1 was repeated with the difference that: in the implementation, the copper-containing sludge contains 4.2wt% of Cu4, the copper-containing sludge contains 30wt% of water after being dried, the mass ratio of the copper-containing sludge to the reducing agent, the flux and the additive is 100:8:12:3, the mass ratio of the activated carbon to the carbon powder in the reducing agent is 2:1, the mass ratio of the hematite to the quartz stone in the flux is 7:1, and the mass ratio of the sodium carbonate to the sodium chloride in the additive is 1.5: 1. and (3) introducing 60% of oxygen-enriched gas and natural gas into the mixed material at 1250 ℃ for smelting to obtain black copper with 84wt% of copper taste and matte with 43wt% of copper taste, wherein the copper recovery rate reaches 95%. The flue gas is treated by a flue gas treatment system, the denitration rate reaches 96 percent, and the emission standard is reached.
Example 3
Example 1 was repeated with the difference that: in the implementation, the copper-containing sludge contains 3.2wt% of Cu3, the copper-containing sludge contains 27wt% of water after being dried, the mass ratio of the copper-containing sludge to the reducing agent, the flux and the additive is 100:12:15:5, the mass ratio of the activated carbon to the carbon powder in the reducing agent is 1:1, the mass ratio of the quartz stone to the hematite in the flux is 5:1, and the mass ratio of the sodium carbonate to the sodium chloride in the additive is 1: 1. and introducing 65% of oxygen-enriched gas and natural gas into the mixed material at 1350 ℃ for smelting to obtain black copper with the copper taste of 80wt% and matte with the copper taste of 45wt%, wherein the copper recovery rate reaches 96%. The flue gas is treated by a flue gas treatment system, the denitration rate reaches 97 percent, and the emission standard is reached.
Example 4
Example 1 was repeated with the difference that: in the implementation, the copper-containing sludge contains 2.7wt% of Cu2, the copper-containing sludge contains 25wt% of water after being dried, the mass ratio of the copper-containing sludge to the reducing agent, the flux and the additive is 100:8:20:5, the mass ratio of the activated carbon to the carbon powder in the reducing agent is 1:1, the mass ratio of the hematite to the quartz stone is 10:1, and the mass ratio of the sodium carbonate to the sodium chloride is 2: 1. and introducing 55% of oxygen-enriched gas and natural gas into the mixed material at 1450 ℃ to smelt to obtain black copper with a copper grade of 85wt% and matte with a copper grade of 47wt%, wherein the copper recovery rate reaches 94%. The flue gas is treated by a flue gas treatment system, the denitration rate reaches 94 percent, and the emission standard is reached.
Comparative example 1
The method comprises the steps of treating copper-containing sludge by using a conventional oxygen-enriched side-blown furnace, drying the copper-containing sludge, and then adding 25wt% of water, wherein the mass ratio of the copper-containing sludge to a reducing agent to a fusing agent is 100:8:20, the mass ratio of activated carbon to carbon powder in the reducing agent is 1:1, the mass ratio of hematite to quartz stone in the fusing agent is 10:1, the temperature is 1300 ℃, and due to the fact that the slag amount is too large, materials cannot be layered in a furnace chamber, and matte cannot be normally discharged.
The foregoing examples are set forth to illustrate the present invention more clearly and are not to be construed as limiting the scope of the invention, which is defined in the appended claims to which the invention pertains, as modified in all equivalent forms, by those skilled in the art after reading the present invention.
Claims (4)
1. The method for treating the copper-containing sludge is characterized by comprising the following steps of:
s1, drying the sludge containing copper to be treated to obtain the sludge containing copper with the water content not higher than 30 wt%;
wherein the Cu content in the copper-containing sludge to be treated is less than 3wt%, or 3.2wt% or 4.2 wt%;
s2, mixing the copper-containing sludge obtained in the step S1 with a reducing agent, a flux and an additive to obtain a mixture;
wherein the mass ratio of the copper-containing sludge to the reducing agent, the flux and the additive is 100:5-20:5-20: 1-20; the reducing agent comprises at least one of carbon powder, activated carbon, pulverized coal and coke, and the fusing agent comprises at least one of quartz stone, limestone and hematite; the additive is formed by mixing sodium carbonate and sodium chloride according to the mass ratio of 1-3: 1;
s3, conveying the mixture obtained in the step S2 into a metallurgical furnace, blowing natural gas and oxygen-enriched air into the metallurgical furnace through a second air nozzle, smelting, discharging a copper matte phase in an electric heating fore-bed through a siphon port, and discharging a slag phase through a slag tap;
wherein the smelting temperature is 1200-1500 ℃, and the oxygen concentration in the oxygen-enriched air is 50-80 vol%;
the metallurgical furnace comprises a side-blown furnace, wherein the side-blown furnace is provided with a furnace hearth section (2), a furnace body section (A) and a furnace top section (10) which are sequentially distributed from bottom to top; the bottom side of the hearth section (2) is communicated with an electric heating front bed (13), the side wall of the electric heating front bed (13) is provided with a siphon inlet (14) and a slag tap (16), the siphon inlet (14) is lower than the slag tap (16), and the bottom area of the inner cavity of the electric heating front bed (13) is 3/2 or 2 times of that of the inner cavity of the hearth section (2); the bottom area of the inner cavity of the bed before electric heating is at least 5 square meters; the height L1 of the furnace top section (10) is 3-5 m; the inner bottom surface of the hearth section (2) inclines towards the direction of the electric heating front bed (13), and the included angle between the inner bottom surface and the horizontal plane is 5-20 degrees; a chute (7) is arranged on the top side of the furnace body section (A), a first air nozzle (11) and a second air nozzle (3) which are distributed vertically are arranged on the side wall of the furnace body section (A), and an air outlet of the second air nozzle (3) is obliquely arranged downwards; the hearth section (2) is communicated with the electric heating forehearth (13) through a communication port (12); the hearth section of the side-blown converter is directly communicated with the electric heating front bed by a communication port;
the second air nozzle is mainly divided into two types, one type is an air nozzle used for inputting oxygen-enriched gas, the other type is an air nozzle used for inputting natural gas, and an air nozzle used for inputting oxygen-enriched gas is clamped between every two air nozzles used for inputting natural gas.
2. The treatment method according to claim 1, wherein in S2, the mass ratio of the copper-containing sludge to the reducing agent, the flux and the additive is 100:5-10:10-20: 1-10.
3. The treatment method according to claim 1, wherein in S2, the reducing agent is prepared by mixing activated carbon and carbon powder according to a mass ratio of 1-5: 1; the flux is formed by mixing hematite and quartz according to the mass ratio of 5-20: 1.
4. The treatment method of claim 1, further comprising a flue gas treatment system, wherein the flue gas treatment system comprises an SNCR (selective non-catalytic reduction) denitration device, a spray quenching tower, a dust collecting device, a desulfurization tower, a defogging device and an SCR (selective catalytic reduction) denitration device which are sequentially connected in series; an activated carbon injection device and a calcium hydroxide injection device are arranged on a pipeline between the spray quenching tower and the dust collection device; the SNCR denitration device is communicated with an outlet of the furnace top section (10).
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Denomination of invention: Metallurgical furnace for treating copper containing sludge and its treatment method Effective date of registration: 20230420 Granted publication date: 20220902 Pledgee: Industrial and Commercial Bank of China Limited Changsha Fenglin Branch Pledgor: HUNAN RUIYI ZIHUAN TECHNOLOGY CO.,LTD. Registration number: Y2023430000012 |
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