CN212316200U - Device for producing black copper from copper-containing sludge - Google Patents
Device for producing black copper from copper-containing sludge Download PDFInfo
- Publication number
- CN212316200U CN212316200U CN202020505429.7U CN202020505429U CN212316200U CN 212316200 U CN212316200 U CN 212316200U CN 202020505429 U CN202020505429 U CN 202020505429U CN 212316200 U CN212316200 U CN 212316200U
- Authority
- CN
- China
- Prior art keywords
- smelting
- copper
- blowing
- zone
- slag
- 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 utility model provides a device of copper-containing mud production black copper. The device comprises a drying device and a smelting furnace, wherein the drying device is provided with a copper-containing sludge inlet and a dehydrated sludge outlet; the smelting furnace comprises a bottom blowing oxidation smelting zone, a side blowing reduction smelting zone and a settling zone which are sequentially communicated; the bottom blowing oxidation smelting zone is provided with a dehydrated sludge inlet, the dehydrated sludge inlet is connected with a dehydrated sludge outlet, the bottom of the bottom blowing oxidation smelting zone is also provided with a bottom blowing spray gun, and the bottom blowing oxidation smelting zone is a full-slag molten pool and is used for performing bottom blowing oxidation smelting on the dehydrated sludge and the flux to form oxidation smelting slag; the side part of the side-blown reduction smelting zone is provided with a side-blown spray gun, and the side-blown reduction smelting zone is used for carrying out side-blown reduction smelting on the oxidation smelting slag to obtain a reduction smelting product; the settling zone is used for settling the reduction smelting product. The utility model discloses long, the tailings copper content of process, the high scheduling problem of sulphur content when effectively having solved the recovery copper from copper-containing mud to the rate of recovery of valuable metal has been improved.
Description
Technical Field
The utility model relates to a metallurgical technology field particularly, relates to a device of copper-containing mud production black copper.
Background
Copper-containing sludge generally comes from the electroplating industry, the sludge contains a large amount of copper, valuable metals such as nickel, lead, zinc, tin and the like, and the copper-containing sludge generally contains sulfate. The existing method for recovering copper from copper-containing sludge mainly adopts a side-blown furnace or a blast furnace for reduction smelting. However, when the processes are adopted, a part of matte exists at the same time of producing the black copper, so that melt layering is caused, separation is not thorough, sulfide is easy to mix with tailings, a low-sulfur raw material is generally mixed in a material mixing mode to carry out reduction smelting to reduce the phase ratio of the matte, the produced black copper and the matte need to be separated again, the black copper is sent to electrolysis, the matte is sent to a converting furnace, and slag contains about 0.8 percent of copper, and is generally used as a building material raw material or is dumped.
Application No. 201611046435.5 proposes a low energy method for producing electrolytic copper and separating nickel, arsenic and tin from copper-containing sludge. Firstly, sintering and dehydrating the copper-containing sludge until the water content is 1-5%, laterally blowing oxygen-enriched air and calcining to produce blister copper, refining and electrolyzing the blister copper to produce cathode copper, and sending the refining slag to a blast furnace to produce black copper. The process indicates typical components of the treated copper-containing sludge, but the sludge components are similar to the conventional side-blown smelting slag type composition as the proportion of limestone and quartz stone for slagging smelting is required to be added, and the process has the problem of poor raw material adaptability. In addition, the copper content of the slag is generally high (more than 1%) when the copper-containing sludge is directly subjected to side-blown smelting to produce blister copper, and the process does not list the key parameter of copper content in smelting slag and does not mention the utilization of the slag.
Application No. 201611178461.3 proposes a process for the treatment of copper-containing sludge. The method comprises the steps of drying copper-containing sludge with the sulfur content of less than 2% at low temperature, making bricks, adding the dried sludge, a slagging agent and reduced coking coal into an oxygen-enriched side blowing furnace to produce secondary crude copper, carrying out ore dressing on tailings containing 0.6% of copper and then recovering residual copper, and drying the copper-containing sludge with the sulfur content of more than 2% at low temperature, and then feeding the sludge into an ore copper smelting system for synergistic treatment, wherein the process is the same as that of the conventional copper smelting process. The process can only be used for independently treating the copper-containing sludge with low sulfur content, the S content in most of the copper-containing sludge is higher than 2%, the introduction of organic matters, halogens and other substances in the copper-containing sludge can bring negative effects to a mineral copper smelting system, the copper-containing sludge is difficult to be mixed in a large proportion, the raw material adaptability of the process is poor, and the treatment capacity is limited.
Therefore, when the blast furnace process is adopted to treat the copper-containing sludge, a long pretreatment process (material mixing, briquetting, air drying and the like) is needed, a large amount of volatile organic compounds at the top of the blast furnace are difficult to treat, the obtained product is layered and needs to be sorted again and sent to different processes for treatment, and the tailings are high in copper content and difficult to utilize. In addition, the blast furnace process also has the problems of small monomer processing capacity, high labor intensity of workers, poor environment-friendly conditions of smelting workshops and the like. When the side-blown smelting furnace process is adopted to treat copper-containing sludge, the copper-containing sludge needs to be dehydrated to the water content of below 10 percent in advance and put into a side-blown smelting furnace, the oxygen-enriched side submerged combustion mode is adopted for heat supply and reduction, the spray gun needs to be far away from a metal and copper matte layer for preventing the burning loss of the spray gun, the insufficient combustion mode is adopted to ensure the reducibility of the system, meanwhile, sulfides in slag, metal and copper matte below the spray gun are difficult to be oxidized and removed, tailings are easy to clamp impure copper matte particles, the tailings still need to be slowly cooled and then subjected to flotation dilution treatment, and SO is easy to appear2And (4) pollution. In a word, the defects of long flow, high copper content in tailings, high sulfur content and the like exist when copper is recovered from the copper-containing sludge at present.
SUMMERY OF THE UTILITY MODEL
The utility model aims to provide a device of copper-containing mud production black copper to solve the long, the tailings copper content of the procedure that all exist when retrieving copper among the prior art from copper-containing mud, problem such as sulphur content height.
In order to achieve the above object, according to an aspect of the present invention, there is provided an apparatus for producing black copper from copper-containing sludge, comprising: a drying device having a copper-containing sludge inlet and a dewatered sludge outlet, the drying device being configured to dewater the copper-containing sludge to form dewatered sludge; the smelting furnace comprises a bottom blowing oxidation smelting zone, a side blowing reduction smelting zone and a settling zone which are sequentially communicated; the bottom blowing oxidation smelting zone is provided with a dehydrated sludge inlet, the dehydrated sludge inlet is connected with a dehydrated sludge outlet, the bottom of the bottom blowing oxidation smelting zone is also provided with a bottom blowing spray gun, and the bottom blowing oxidation smelting zone is a full-slag molten pool and is used for performing bottom blowing oxidation smelting on the dehydrated sludge and the flux to form oxidation smelting slag; the side part of the side-blown reduction smelting zone is provided with a side-blown spray gun, and the side-blown reduction smelting zone is used for carrying out side-blown reduction smelting on the oxidation smelting slag to obtain a reduction smelting product; the settling area is provided with a black copper outlet and a slag outlet and is used for settling the reduction smelting products to obtain black copper and slag.
Further, the above apparatus further comprises: the first gas supply unit is connected with the bottom blowing spray gun and used for supplying oxygen or oxygen-enriched air with the oxygen volume content of 60-100% to the bottom blowing spray gun; and the fuel supply device is connected with the bottom-blowing spray gun and is used for supplying the pulverized coal to the bottom-blowing spray gun.
Further, the above apparatus further comprises: the second gas supply unit is connected with the side-blowing spray gun and used for supplying oxygen or oxygen-enriched air with the oxygen volume content of 60-100% to the side-blowing spray gun; and the reducing agent supply device is connected with the side-blowing spray gun and is used for supplying the coal dust and/or the natural gas to the side-blowing spray gun.
Further, be provided with first partition wall between bottom-blowing oxidation smelting zone and the side-blown reduction smelting zone, the middle part of first partition wall is provided with and is used for the intercommunication: a first communicating channel of the bottom-blowing oxidation smelting zone and the side-blowing reduction smelting zone.
And a second partition wall is arranged between the side-blown reduction smelting zone and the settling zone, and a second communicating channel for communicating the side-blown reduction smelting zone with the settling zone is arranged between the second partition wall and the bottom wall of the smelting furnace.
Furthermore, the bottom-blowing spray gun is arranged at one end, far away from the first partition wall, of the bottom-blowing oxidation smelting zone, the height of the bottom wall of the bottom-blowing oxidation smelting zone is gradually increased along the direction from the bottom-blowing spray gun to the first partition wall, and the highest point of the bottom-blowing oxidation smelting zone is lower than the height of the first communication channel.
Further, the height of the bottom wall of the side-blown reduction smelting zone is gradually reduced along the direction from the first communication channel to the second communication channel.
Further, the drying device is a rotary kiln.
Further, the bottom-blowing oxidation smelting zone is also provided with a first flue gas outlet, and the device also comprises: the first waste heat recovery device is connected with the first flue gas outlet; the first dust removal device is connected with an outlet of the first waste heat recovery device; and the acid making device is connected with the outlet of the first dust removal device.
Furthermore, a third communicating channel is further arranged at the upper part of the second partition wall, and a second flue gas outlet is further formed in the settling zone; the drying device is also provided with a heat medium inlet; the device still includes: the second waste heat recovery device is connected with the second flue gas outlet; the second dust removal device is connected with an outlet of the second waste heat recovery device; and the outlet of the second dust removal device is connected with the heat medium inlet of the drying device.
Use the technical scheme of the utility model, realize the desulfurization through the whole slag molten bath of bottom blowing oxidation smelting, carry out the side-blown reduction with oxidation smelting slag again and smelt in order to obtain high value black copper and innoxious slag, realize in the mud comprehensive recycle of multiple valuable metals such as Cu, Ni, Pb, Zn, Sn. The dewatered copper-containing sludge directly enters a full-slag molten pool for bottom blowing oxidation smelting, so that the problems of high temperature, high energy consumption, large smoke dust amount and the like in the deep drying process are avoided, organic pollutants in the sludge can be thoroughly decomposed, S, Cl and other elements in the copper-containing sludge are promoted to almost completely enter smoke, Cu, Ni, Pb, Zn, Sn and the like are left in slag in an oxide form, the recovery rate of valuable metals during subsequent reduction production of black copper is improved, the content of halogen, sulfide and other harmful substances in the final slag is low, and the building material utilization prospect is good.
In a word, utilize the utility model provides a copper-containing sludge is handled to technology, the long, the tailings copper content of flow when having effectively solved among the prior art and retrieving copper from copper-containing sludge, the high scheduling problem of sulfur content to the rate of recovery of valuable metal has been improved.
Drawings
The accompanying drawings, which form a part of the present application, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. In the drawings:
fig. 1 shows a schematic structural diagram of an apparatus for producing black copper from copper-containing sludge according to an embodiment of the present invention; and
fig. 2 shows a flow diagram of a method for producing black copper from copper-containing sludge according to an embodiment of the present invention.
Wherein the figures include the following reference numerals:
10. a drying device; 20. a smelting furnace; 30. a first gas supply unit; 40. a fuel supply device; 50. a second gas supply unit; 60. a reducing agent supply device; 70. a first waste heat recovery device; 80. a first dust removing device; 90. an acid making device; 100. a second waste heat recovery device; 110. a second dust removing device;
21. a bottom-blown oxidation smelting zone; 22. a side-blown reduction smelting zone; 23. a settling zone; 24. a first partition wall; 25. a second partition wall;
201. a dehydrated sludge inlet; 202. a first flue gas outlet; 203. a second flue gas outlet;
211. a bottom blowing spray gun; 221. side-blown spray guns.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the accompanying drawings in conjunction with embodiments.
As described in the background art, the prior art has problems of long process, high copper content in the tailings, high sulfur content and the like when recovering copper from copper-containing sludge.
In order to solve the above problems, the present invention provides a device for producing black copper from copper-containing sludge, as shown in fig. 1, comprising a drying device 10 and a smelting furnace 20, wherein the drying device 10 has a copper-containing sludge inlet and a dehydrated sludge outlet, and the drying device 10 is used for dehydrating the copper-containing sludge to form dehydrated sludge; the smelting furnace 20 comprises a bottom blowing oxidation smelting zone 21, a side blowing reduction smelting zone 22 and a settling zone 23 which are communicated in sequence; the bottom-blowing oxidation smelting zone 21 is provided with a dehydrated sludge inlet 201, the dehydrated sludge inlet 201 is connected with a dehydrated sludge outlet, the bottom of the bottom-blowing oxidation smelting zone 21 is also provided with a bottom-blowing spray gun 211, and the bottom-blowing oxidation smelting zone 21 is a full-slag molten pool and is used for performing bottom-blowing oxidation smelting on the dehydrated sludge and a flux to form oxidation smelting slag; the side part of the side-blown reduction smelting zone 22 is provided with a side-blown spray gun 221, and the side-blown reduction smelting zone 22 is used for carrying out side-blown reduction smelting on the oxidation smelting slag to obtain a reduction smelting product; the settling zone 23 has a black copper outlet and a slag outlet, and the settling zone 23 is used for settling the reduced smelting product to obtain black copper and slag.
The device is used for treating the copper-containing sludge, the full slag molten pool of bottom blowing oxidation smelting is used for realizing desulfurization, and then the oxidation smelting slag is subjected to side blowing reduction smelting to obtain high-value black copper and harmless slag, so that the comprehensive recycling of various valuable metals such as Cu, Ni, Pb, Zn, Sn and the like in the sludge is realized. The dehydrated copper-containing sludge (preferably containing 10-40% of water) directly enters a full-slag molten pool for bottom blowing oxidation smelting, so that the problems of high temperature, high energy consumption, large smoke dust amount and the like in the deep drying process are avoided, organic pollutants in the sludge can be thoroughly decomposed, elements such as S, Cl in the copper-containing sludge are promoted to almost completely enter smoke, and Cu, Ni, Pb, Zn, Sn and the like are left in slag in an oxide form, so that the recovery rate of valuable metals during subsequent reduction production of black copper is improved, the content of harmful substances such as halogen, sulfide and the like in the slag is low, and the building material utilization prospect is good.
In a word, utilize the utility model provides a device handles copper-containing mud, long, the tailings copper content of process, the high scheduling problem of sulphur content when effectively having solved among the prior art and having retrieved copper from copper-containing mud to the rate of recovery of valuable metal has been improved.
The specification indicates that the total slag molten pool is a furnace in the molten poolSlag, no metal or copper matte phase residue is left at the bottom of the molten pool, and the metal in the sludge is completely oxidized in the bottom blowing oxidation smelting process. In the actual smelting process, the dewatered sludge can be in an oxidant surplus state by adopting bottom blowing oxidation smelting, so that the sludge is efficiently melted and the sulfate is decomposed and desulfurized, no sulfide and metal residue is left at the bottom of the furnace, and a full-slag molten pool is realized. Through the bottom blowing oxidation smelting of the full-slag molten pool, the following steps can be realized: (1) the recovery rate of valuable metals in the subsequent side-blown reduction smelting process is improved; (2) the smoke components of the side-blown reduction smelting are purified, the waste heat recovery rate is improved, and the service life of equipment (such as a boiler) is prolonged; (3) no H is produced when the final slag is water quenched2S pollution, and the Cl content in the water-quenched slag is low, so that the water-quenched slag can be widely used in the building material industry; (4) the refractory materials and the spray gun of the furnace body can realize water cooling slag hanging, thereby prolonging the service life of the refractory materials and the spray gun of the furnace body and avoiding the danger of easy explosion when metal or copper matte exists at the water cooling position. And the oxidation smelting slag is subjected to side-blown reduction smelting to produce high-value black copper, and produce flue gas and tailings with low content of harmful substances, so that the resource comprehensive utilization of the copper-containing sludge is realized.
For improving safety, it is preferable that the inner lining of the bottom-blowing oxidation smelting zone 21 is protected by water-cooling slag, and the bottom-blowing lance 211 is also of a water-cooling structure.
In a preferred embodiment, as shown in fig. 2, the apparatus further comprises: the first gas supply unit 30 is connected with the bottom-blowing spray gun 211 and is used for supplying oxygen or oxygen-enriched air with the oxygen volume content of 60-100% to the bottom-blowing spray gun 211; and a fuel supply device 40, the fuel supply device 40 being connected to the bottom-blowing lance 211 for supplying pulverized coal to the bottom-blowing lance 211. Therefore, the dehydrated copper-containing sludge with 10-40% of water can be more fully oxidized under the conditions of bottom blowing oxygen (oxygen-enriched air) and fuel, sulfate and organic matters in the sludge are more fully decomposed, valuable metals can more completely enter oxidized smelting slag, and sulfur, chlorine and the like enter tail gas.
In a preferred embodiment, the above further includes: the second gas supply unit 50 is connected with the side-blowing lance 221, and is used for supplying oxygen or oxygen-enriched air with the oxygen volume content of 60-100% to the side-blowing lance 221; and the reducing agent supply device 60 is connected with the side-blowing spray gun 221, and is used for supplying the coal powder and/or the natural gas to the side-blowing spray gun 221. Oxygen (oxygen-enriched air) is fed into the smelting furnace to maintain the temperature of the reduction process, and under the action of the reducing agent, copper oxide in the oxidation smelting slag is reduced to form black copper which is separated from the slag. Preferably, the reductant is coal fines and/or natural gas.
In a preferred embodiment, a first partition wall 24 is arranged between the bottom-blowing oxidation smelting zone 21 and the side-blowing reduction smelting zone 22, and the middle part of the first partition wall 24 is provided with a first connecting pipe for connecting: a first communicating passage of the bottom-blowing oxidation smelting zone 21 and the side-blowing reduction smelting zone 22. In this way, the oxidizing smelting slag generated in the bottom-blowing oxidizing smelting process can continuously enter the side-blowing reduction smelting zone 22 for side-blowing reduction smelting, and the entering of the slag is more stable.
In a preferred embodiment, a second partition wall 25 is provided between the side-blowing reduction smelting zone 22 and the settling zone 23, and a second communicating passage for communicating the side-blowing reduction smelting zone 22 and the settling zone 23 is provided between the second partition wall 25 and the bottom wall of the smelting furnace 20. In this way, the reduced smelting products can enter the settling zone 23 more stably for settling treatment, and the partition wall can obstruct disturbance in the side-blown reduction smelting zone 22, so that the effect of settling separation is better.
More preferably, the bottom-blowing lance 211 is arranged at one end of the bottom-blowing oxidation smelting zone 21 far away from the first partition wall 24, and the height of the bottom wall of the bottom-blowing oxidation smelting zone 21 gradually increases along the direction from the bottom-blowing lance 211 to the first partition wall 24, and the highest point is lower than the height of the first communication channel. In this way, the slag can enter the reduction smelting zone more stably and continuously. Likewise, it is preferred that the height of the bottom wall of the side-blown reduction smelting zone 22 is gradually reduced in the direction from the first communicating channel to the second communicating channel.
In order to achieve a higher dewatering efficiency of the aqueous sludge, in a preferred embodiment the drying device 10 is a rotary kiln. In practical operation, the drying temperature of the rotary kiln is preferably low, for example, about 150 ℃.
In a preferred embodiment, bottom blown oxygenThe chemical smelting zone 21 also has a first flue gas outlet 202, and the apparatus further comprises: the first waste heat recovery device 70 is connected with the first flue gas outlet 202; the first dust removal device 80 is connected with the outlet of the first waste heat recovery device 70; and the acid making device 90 is connected with the outlet of the first dust removal device 80. The flue gas generated in the bottom blowing oxidation smelting process contains a large amount of sulfur and chlorine (SO)2The volume concentration is more than 2 percent), the tail gas can be used for preparing acid after being subjected to waste heat recovery and dust removal treatment, and in order to prevent the flue gas from condensing and corroding pipelines, the tail gas temperature of the tail gas after being preheated and recovered is preferably controlled to be about 350 ℃.
In a preferred embodiment, the upper part of the second partition wall 25 is further provided with a third communicating channel, and the settling zone 23 is further provided with a second flue gas outlet 203; the drying device 10 is also provided with a heat medium inlet; the device still includes: the second waste heat recovery device 100 is connected with the second flue gas outlet 203; the second dust removing device 110 is connected with the outlet of the second waste heat recovery device 100; and the outlet of the second dust removing device 110 is connected to the heat medium inlet of the drying device 10. Because sulfate, organic matters and the like are fully decomposed in the bottom blowing oxidation smelting process, and sulfur, chlorine and the like fully enter the flue gas in the first stage, the content of harmful substances in the flue gas generated in the side blowing reduction smelting and settling process is low, the flue gas can return to the dehydration treatment stage after waste heat recovery (the temperature of the tail end is preferably controlled at 150 ℃) and dust removal treatment, and heat energy is effectively utilized. And in order to make this part of the flue gas more fully combusted, it is preferred to supplement oxygen at the second flue gas outlet 203.
According to another aspect of the present invention, there is provided a method for producing black copper from copper-containing sludge, as shown in fig. 2, the method comprising the steps of: s1, dehydrating the copper-containing sludge until the water content is 10-40 wt%, and forming dehydrated sludge; s2, mixing the dewatered sludge with a flux, and then carrying out bottom blowing oxidation smelting in a full-slag molten pool to form oxidation smelting slag; s3, carrying out side-blown reduction smelting on the oxidation smelting slag in a reduction molten pool to obtain a reduction smelting product; and S4, performing sedimentation treatment on the reduction smelting product to obtain black copper and slag.
The process is used for treating the copper-containing sludge, the desulfurization is realized through a full slag molten pool of bottom blowing oxidation smelting, and then the side blowing reduction smelting is carried out on the oxidation smelting slag to obtain high-value black copper and harmless slag, so that the comprehensive recycling of various valuable metals such as Cu, Ni, Pb, Zn, Sn and the like in the sludge is realized. The method has the advantages that the copper-containing sludge containing 10-40% of water directly enters the full-slag molten pool for bottom blowing oxidation smelting, the problems of high temperature, high energy consumption, large smoke amount and the like in the deep drying process are avoided, organic pollutants in the sludge can be thoroughly decomposed, elements such as S, Cl in the copper-containing sludge are promoted to almost completely enter smoke, Cu, Ni, Pb, Zn, Sn and the like are left in the slag in an oxide form, the recovery rate of valuable metals during subsequent reduction production of black copper is improved, the content of harmful substances such as halogen, sulfide and the like in the final slag is low, and the building material utilization prospect is good.
In a word, utilize the utility model provides a device handles copper-containing mud, long, the tailings copper content of process, the high scheduling problem of sulphur content when effectively having solved among the prior art and having retrieved copper from copper-containing mud to the rate of recovery of valuable metal has been improved.
The full-slag molten pool is characterized in that the molten pool is completely slag, no metal or copper matte phase is left at the bottom of the molten pool, and the metal in the sludge is completely oxidized in the bottom blowing oxidation smelting process. In the actual smelting process, the dewatered sludge can be in an oxidant surplus state by adopting bottom blowing oxidation smelting, so that the sludge is efficiently melted and the sulfate is decomposed and desulfurized, no sulfide and metal residue is left at the bottom of the furnace, and a full-slag molten pool is realized. Through the bottom blowing oxidation smelting of the full-slag molten pool, the following steps can be realized: (1) the recovery rate of valuable metals in the subsequent side-blown reduction smelting process is improved; (2) the smoke components of the side-blown reduction smelting are purified, the waste heat recovery rate is improved, and the service life of equipment (such as a boiler) is prolonged; (3) no H is produced when the final slag is water quenched2S pollution, and the Cl content in the water-quenched slag is low, so that the water-quenched slag can be widely used in the building material industry; (4) the refractory materials and the spray gun of the furnace body can realize water cooling slag hanging, thereby prolonging the service life of the refractory materials and the spray gun of the furnace body and avoiding the danger of easy explosion when metal or copper matte exists at the water cooling position. The oxidation smelting slag is then subjected to side-blown reduction smelting to produce high-value black copper, flue gas and tailings with low content of harmful substances, and the comprehensive recycling of copper-containing sludge is realizedAnd (4) performing combined utilization.
In a preferred embodiment, in step S2, oxygen or oxygen-enriched air with an oxygen content of 60 to 100% by volume (60% to less than 100% by volume) is blown into the whole slag molten pool to perform bottom-blown oxidation smelting, and fuel, preferably coal dust and/or natural gas, is blown into the whole slag molten pool at the same time. Therefore, the dehydrated copper-containing sludge with 10-40% of water can be more fully oxidized under the conditions of bottom blowing oxygen (oxygen-enriched air) and fuel, sulfate and organic matters in the sludge are more fully decomposed, valuable metals can more completely enter oxidized smelting slag, and sulfur, chlorine and the like enter tail gas. More preferably, in the step S2, the oxygen volume content in the flue gas generated in the bottom-blowing oxidation smelting process is controlled to be 1-10%. Therefore, the excess oxygen is more beneficial to the oxidation smelting, the fuel is fully combusted, the heat efficiency is improved, the sludge raw material with higher water content can be used, and the sludge pretreatment difficulty is reduced.
In a preferred embodiment, in step S2, the temperature of bottom-blown oxidation smelting is 1250 to 1350 ℃, and the slag form of the oxidation smelting slag is Cu2O-CaO-Fe2O3-SiO2(ii) a At the temperature, the oxidation reaction and the decomposition of organic matters and sulfate are more thorough, and the recovery of valuable metals and the separation of sulfur and chlorine are more facilitated. And the slag form of the oxidation smelting slag is controlled to be the slag form, so that valuable metals such as Cu, Ni, Pb, Zn, Sn and the like are remained in the slag in the form of oxides, and conditions are provided for improving the metal recovery rate in the subsequent reduction separation process. Preferably, the flux is silica and/or quartz.
In a preferred embodiment, in step S3, a reducing agent is side-blown into the reduction bath, and oxygen or oxygen-enriched air (60% or more and less than 100% by volume) having an oxygen content of 60 to 100% by volume is blown into the reduction bath to perform side-blown reduction melting. Oxygen (oxygen-enriched air) is fed into the smelting furnace to maintain the temperature of the reduction process, and under the action of the reducing agent, copper oxide in the oxidation smelting slag is reduced to form black copper which is separated from the slag. Preferably, the reductant is coal fines and/or natural gas. In order to maintain a more stable reducing atmosphere, the volume content of CO in flue gas generated by side-blown reduction smelting is preferably 10-20%.
In order to complete the reduction reaction, in a preferred embodiment, in the step S3, the temperature of the side-blown reduction smelting is 1250-1400 ℃, and the slag form generated in the side-blown reduction smelting process is FeO-SiO2-CaO. The copper-containing sludge initially contains higher CaO, so that FeO-SiO can be conveniently prepared2CaO slag, the slag type melting point ratio FeO-SiO2The slag is lower, the slag is better separated from metal, the residual Cu content of the slag containing CaO is less during the balance, and the initial CaO component in the sludge containing the copper is fully utilized.
Based on the reasons, the utility model discloses preparation has been retrieved from copper-containing mud and has been obtained the metal phase for being rich in black copper of Pb, Zn, Ni, Sn, and the rate of recovery is higher, and the copper content of black copper is 70 ~ 85 wt%; the slag has a copper content of less than 0.5 wt%, a sulfur content of less than 0.1 wt%, and a chlorine content of less than 0.1 wt%. The black copper can be electrolyzed to comprehensively recover valuable metals, and slag can be used as a building material after water quenching.
In a preferred embodiment, the method further comprises: flue gas generated in the bottom blowing oxidation smelting process is subjected to waste heat recovery, dust removal treatment and acid preparation in sequence; and (4) performing waste heat recovery and dust removal treatment on the flue gas generated in the side-blown reduction smelting and settling treatment process, and returning the tail gas subjected to dust removal to the step S1 for dehydration treatment of the copper-containing sludge. The flue gas generated in the bottom blowing oxidation smelting process contains a large amount of sulfur and chlorine (SO)2The volume concentration is more than 2 percent), the tail gas can be used for preparing acid after being subjected to waste heat recovery and dust removal treatment, and in order to prevent the flue gas from condensing and corroding pipelines, the tail gas temperature of the tail gas after being preheated and recovered is preferably controlled to be about 350 ℃. Meanwhile, because sulfate, organic matters and the like are fully decomposed in the bottom blowing oxidation smelting process, and sulfur, chlorine and the like fully enter the flue gas in the first stage, the content of harmful substances in the flue gas generated in the side blowing reduction smelting and sedimentation processes is low, the flue gas can return to the dehydration treatment stage after waste heat recovery (the temperature of the tail end is preferably controlled at 150 ℃) and dust removal treatment, and heat energy is effectively utilized. And in order to make this part of the flue gas more fully combusted, it is preferable to supplement oxygen at the off-gas outlet during the side-blown reduction smelting and settling treatment.
In a word, the method and the device provided by the utility model for treating the copper-containing sludge have the following beneficial effects:
(1) the method takes the copper-containing sludge with water content of 10-40% as a raw material, has low requirement on drying the raw material, and avoids the problems of high temperature, high energy consumption, large smoke amount, large organic matter volatilization amount and the like of deep drying pretreatment.
(2) The material directly enters a full-slag molten pool, the oxidability of the high-temperature molten pool is strong, the decomposition of organic matters in sludge is thorough, sulfate is completely decomposed, chloride is volatilized completely, the residual quantity of sulfur and halogen in slag is small, and the flue gas SO in an oxidation zone is2The volume concentration is higher than 2%, which is convenient for preparing acid.
(3) Preferably, the combustion oxygen in the bottom-blown oxidation smelting process is excessive, the oxygen content in the flue gas is about 5%, the full combustion of fuel can be ensured, the heat efficiency is high, no metal or copper matte residue exists at the bottom, the safety of water-cooling slag hanging of the furnace body is ensured, and the service life of a furnace lining is prolonged.
(4) Preferably, the bottom-blown oxidation slag Cu2O-CaO-Fe2O3-SiO2The slag system is mainly used, so that valuable metals such as Cu, Ni, Pb, Zn, Sn and the like are favorably remained in the slag in the form of oxides, and conditions are provided for improving the metal recovery rate in the subsequent reduction separation process.
(5) Preferably, the bottom-blowing oxidation smelting realizes the deep removal of sulfur and halogen, so that the content of corrosive gas in the side-blowing reduction smelting flue gas is low, the service life of a waste heat boiler and the waste heat recovery rate are favorably improved, the tail gas temperature at the tail end of the waste heat boiler is about 150 ℃, and the tail gas can be used for low-temperature drying of raw materials again.
(6) Preferably, the contents of sulfide and halogen in the slag are low, the copper content in the slag is less than 0.5 percent, the content of S, Cl elements is less than 0.1 percent, and the slag can be used in the building material industry after being quenched by water.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
The copper-containing sludge used in the examples had the following main components:
TABLE 1 copper-containing sludge composition (% dry basis)
| Al2O3 | CaO | SiO2 | FeO | Fe | Cu | Ni | Pb | Zn | Sn | C | S | Cl |
| 4.56 | 16.75 | 7.41 | 10.85 | 11.81 | 15.95 | 0.63 | 0.35 | 1.88 | 2.25 | 10.69 | 5.73 | 0.50 |
Wherein sulfur is present predominantly as sulfate; calcium exists mainly in the form of calcium carbonate and calcium silicate; copper exists mainly in the form of copper sulfate, copper oxide and copper sulfide.
Example 1
And (3) drying the copper-containing sludge with 75% of water in a rotary kiln, wherein the inlet temperature of the flue gas at the tail of the rotary kiln is about 150 ℃, and the sludge is dried under the flue gas at 150 ℃ until the water content is about 20% and is in a granular shape.
57kg of silica is added to each ton of copper-containing sludge (containing 20 percent of water), the sludge and the silica are mixed and then are put into a molten pool of a bottom blowing oxidation zone shown in figure 2, and a water-cooled furnace wall, a water-cooled spray gun refractory and spray gun slag adhering protection are adopted. Pure oxygen and coal powder are blown from the bottom, 100kg of coal powder is consumed for treating each ton of sludge (containing 20 percent of water), and the air is 12Nm3(carrier gas for powder injection), oxygen 294Nm3. The molten pool is completely slag, the temperature of the molten pool is 1250-1350 ℃, and SO in flue gas2、O2The volume contents are 5.05 percent and 4.65 percent respectively, the flue gas is subjected to a waste heat boiler and dust removal to prepare sulfuric acid, and the hot slag flows into a side-blown reduction smelting zone.
Side-blown coal powder and oxygen are blown in the side-blown reduction smelting zone, 90kg of coal powder and 10Nm of air are consumed by each ton of sludge (containing 20 percent of water)3Oxygen 95Nm3. The temperature of the side-blown molten pool is 1300-1350 ℃, the volume concentration of CO in the flue gas above the side-blown molten pool is 18.20%, an oxygen combustion gun is added in an ascending flue to fully combust the CO, the flue gas enters a waste heat boiler to recover waste heat and remove dust, smoke rich in lead, zinc and tin is obtained, and tail gas is introduced into a sludge drying rotary kiln to replace part of hot flue gas. After side-blown reduction, the black copper and the slag can be obtained through settling separation, the black copper is sent to electrolysis, and the slag is used as a building material after water quenching.
158kg of black copper is produced by treating each ton of sludge, 411kg of water-quenched slag contains 0.40%, 0.01%, 0.07%, 0.18% and 0.22% of Cu, Ni, Pb, Zn and Sn, respectively, and S, Cl is less than 0.1%, and the contents of Cu, Ni, Pb, Zn and Sn in the black copper are 79.50%, 3.12%, 1.06%, 5.21% and 5.11%, respectively.
Example 2
The treatment method is the same as that of the example 1, but the drying degree of the sludge is higher, the water content is about 10 percent, oxygen-enriched air with the oxygen concentration of 90 percent is adopted for bottom blowing and side blowing combustion heat supply, and the temperature of a molten pool in the furnace is controlled to be higher.
And (3) drying the copper-containing sludge with 75% of water in a rotary kiln, wherein the inlet temperature of the flue gas at the tail of the rotary kiln is about 150 ℃, and the sludge is dried under the flue gas at 150 ℃ until the water content is about 10% and is in a granular shape.
64kg of silica is added to each ton of copper-containing sludge (containing 10 percent of water), the sludge and the silica are mixed and then put into a molten pool in a bottom blowing oxidation zone shown in figure 2, and a water-cooled furnace wall, a water-cooled lance refractory and lance slag adhering protection are adopted. Adopts bottom blowing coal powder and oxygen enrichment (oxygen enrichment concentration is 90 percent), consumes 110kg of coal powder and 61Nm of air for treating each ton of sludge (containing 20 percent of water)3(carrier gas was sparged), oxygen 308Nm3. The molten pool is completely slag, the temperature of the molten pool is 1250-1350 ℃, and SO in flue gas2、O2The volume contents are respectively 6.10% and 4.31%, the flue gas is processed by a waste heat boiler and is dedusted to produce sulfuric acid, and the hot slag flows into a side-blown reduction smelting zone.
The side-blown coal powder and oxygen enrichment (the oxygen enrichment concentration is 90 percent) in the side-blown reduction smelting zone consume 95kg of coal powder and 26Nm of air per ton of sludge (the water content is 10 percent)3Oxygen 95Nm3. The temperature of a side-blown molten pool is 1350-1400 ℃, the volume concentration of CO in flue gas above the side-blown molten pool is 16.85%, an oxygen combustion gun is added in an ascending flue to enable the CO to be fully combusted, the flue gas enters a waste heat boiler to recover waste heat and remove dust, smoke rich in lead, zinc and tin is obtained, and tail gas is introduced into a sludge drying rotary kiln to replace part of hot flue gas. After side-blown reduction, the black copper and the slag can be obtained through settling separation, the black copper is sent to electrolysis, and the slag is used as a building material after water quenching.
166kg of black copper is produced by treating each ton of sludge, 465kg of water-quenched slag contains 0.46%, 0.01%, 0.03%, 0.11% and 0.13% of Cu, Ni, Pb, Zn and Sn, respectively, and S, Cl is less than 0.1%, and the contents of Cu, Ni, Pb, Zn and Sn in the black copper are 85.01%, 3.35%, 0.76%, 4.06% and 4.26%, respectively.
Example 3
The treatment method is the same as that of the example 1, but the drying degree of the sludge is low, the water content is about 40 percent, oxygen-enriched air with the oxygen concentration of 95 percent is adopted for bottom blowing and side blowing combustion heat supply, and the temperature of a molten pool in the furnace is controlled to be lower.
And (3) drying the copper-containing sludge with 75% of water in a rotary kiln, wherein the inlet temperature of the flue gas at the tail of the rotary kiln is about 150 ℃, and drying the sludge under the flue gas at 150 ℃ until the water content is about 40%.
42.5kg of silica is added to each ton of copper-containing sludge (containing 40 percent of water), the sludge and the silica are mixed and then are put into a molten pool of a bottom blowing oxidation zone shown in figure 2, and a water-cooled furnace wall, a water-cooled lance refractory and lance slag-adhering protection are adopted. Adopts bottom blowing coal powder and rich oxygen (the oxygen-enriched concentration is 95 percent), 100kg of coal powder is consumed for treating each ton of sludge (the water content is 40 percent), and the air is 31Nm3(where carrier gas is sparged), 266Nm of oxygen3. The molten pool is completely slag, the temperature of the molten pool is 1250-1350 ℃, and SO in flue gas2、O2The volume contents are respectively 2.79% and 4.05%, the flue gas is subjected to a waste heat boiler and dust removal to prepare sulfuric acid, and the hot slag flows into a side-blown reduction smelting zone.
The side-blown coal powder and oxygen enrichment (the oxygen enrichment concentration is 95 percent) in the side-blown reduction smelting zone consume 80kg of coal powder and 16Nm of air per ton of sludge (the water content is 40 percent)3Oxygen 86Nm3. The temperature of a side-blown molten pool is 1250-1300 ℃, the volume concentration of CO in flue gas above the side-blown molten pool is 17.46%, an oxygen combustion gun is added into an ascending flue to fully combust the CO, the flue gas enters a waste heat boiler to recover waste heat and remove dust, smoke rich in lead, zinc and tin is obtained, and tail gas is introduced into a sludge drying rotary kiln to replace part of hot flue gas. After side-blown reduction, the black copper and the slag can be obtained through settling separation, the black copper is sent to electrolysis, and the slag is used as a building material after water quenching.
130kg of black copper is produced by treating each ton of sludge, 302kg of water-quenched slag contains 0.47%, 0.01%, 0.03%, 0.37% and 0.45% of Cu, Ni, Pb, Zn and Sn, respectively, and S, Cl is less than 0.1%, and the contents of Cu, Ni, Pb, Zn and Sn in the black copper are 72.31%, 2.85%, 1.13%, 6.04% and 6.73%, respectively.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The utility model provides a device of copper-containing sludge production black copper which characterized in that includes:
a drying apparatus (10), the drying apparatus (10) having a copper-containing sludge inlet and a dewatered sludge outlet, the drying apparatus (10) being for dewatering copper-containing sludge to form dewatered sludge;
the smelting furnace (20) comprises a bottom blowing oxidation smelting zone (21), a side blowing reduction smelting zone (22) and a settling zone (23) which are communicated in sequence; the bottom-blowing oxidation smelting zone (21) is provided with a dehydrated sludge inlet (201), the dehydrated sludge inlet (201) is connected with the dehydrated sludge outlet, the bottom of the bottom-blowing oxidation smelting zone (21) is also provided with a bottom-blowing spray gun (211), and the bottom-blowing oxidation smelting zone (21) is a full-slag molten pool and is used for performing bottom-blowing oxidation smelting on the dehydrated sludge and a flux to form oxidation smelting slag; the side part of the side-blown reduction smelting zone (22) is provided with a side-blown spray gun (221), and the side-blown reduction smelting zone (22) is used for carrying out side-blown reduction smelting on the oxidation smelting slag to obtain a reduction smelting product; the settling zone (23) has a black copper outlet and a slag outlet, and the settling zone (23) is used for settling the reduced smelting product to obtain black copper and slag.
2. The apparatus of claim 1, further comprising:
the first gas supply unit (30), the first gas supply unit (30) is connected with the bottom-blowing spray gun (211) and is used for supplying oxygen or oxygen-enriched air with the oxygen volume content of 60-100% to the bottom-blowing spray gun (211);
a fuel supply device (40), said fuel supply device (40) being connected to said bottom-blowing lance (211) for supplying pulverized coal to said bottom-blowing lance (211).
3. The apparatus of claim 2, further comprising:
the second gas supply unit (50) is connected with the side-blowing lance (221) and is used for supplying oxygen or oxygen-enriched air with the oxygen volume content of 60-100% to the side-blowing lance (221);
the reducing agent supply device (60) is connected with the side-blowing spray gun (221) and is used for supplying coal powder and/or natural gas to the side-blowing spray gun (221).
4. The plant according to any one of claims 1 to 3, characterized in that a first partition wall (24) is provided between the bottom-blowing oxidation smelting zone (21) and the side-blowing reduction smelting zone (22), and a first communication channel for communicating the bottom-blowing oxidation smelting zone (21) with the side-blowing reduction smelting zone (22) is provided in the middle of the first partition wall (24).
5. The arrangement according to claim 4, characterized by a second partition wall (25) being arranged between the side-blown reduction smelting zone (22) and the settler (23), and by a second communicating channel being arranged between the second partition wall (25) and the bottom wall of the smelting furnace (20) for communicating the side-blown reduction smelting zone (22) with the settler (23).
6. The apparatus according to claim 5, characterized in that the bottom-blowing lance (211) is arranged at the bottom of the bottom-blowing oxygen smelting zone (21) at an end remote from the first partition wall (24), and the bottom wall of the bottom-blowing oxygen smelting zone (21) has a height which gradually increases in the direction from the bottom-blowing lance (211) to the first partition wall (24) and has a highest point lower than the height of the first communication channel.
7. The apparatus of claim 5, wherein the height of the bottom wall of the side-blown reduction smelting zone (22) decreases progressively in the direction from the first communicating channel to the second communicating channel.
8. The device according to any one of claims 1 to 3, characterized in that the drying device (10) is a rotary kiln.
9. The apparatus of any one of claims 1 to 3, wherein the bottom-blowing oxidation smelting zone (21) further has a first flue gas outlet (202), the apparatus further comprising:
the first waste heat recovery device (70) is connected with the first flue gas outlet (202);
the first dust removal device (80) is connected with an outlet of the first waste heat recovery device (70);
and the acid making device (90) is connected with the outlet of the first dust removal device (80).
10. The apparatus according to claim 5, characterized in that the upper part of the second partition wall (25) is further provided with a third communicating channel, and the settling zone (23) is further provided with a second flue gas outlet (203); the drying device (10) is also provided with a heat medium inlet; the device further comprises:
the second waste heat recovery device (100) is connected with the second flue gas outlet (203);
the second dust removal device (110) is connected with an outlet of the second waste heat recovery device (100); and the outlet of the second dust removing device (110) is connected with the heat medium inlet of the drying device (10).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202020505429.7U CN212316200U (en) | 2020-04-08 | 2020-04-08 | Device for producing black copper from copper-containing sludge |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202020505429.7U CN212316200U (en) | 2020-04-08 | 2020-04-08 | Device for producing black copper from copper-containing sludge |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN212316200U true CN212316200U (en) | 2021-01-08 |
Family
ID=74020767
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202020505429.7U Active CN212316200U (en) | 2020-04-08 | 2020-04-08 | Device for producing black copper from copper-containing sludge |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN212316200U (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111304450A (en) * | 2020-04-08 | 2020-06-19 | 中国恩菲工程技术有限公司 | Method and device for producing black copper from copper-containing sludge |
-
2020
- 2020-04-08 CN CN202020505429.7U patent/CN212316200U/en active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111304450A (en) * | 2020-04-08 | 2020-06-19 | 中国恩菲工程技术有限公司 | Method and device for producing black copper from copper-containing sludge |
| CN111304450B (en) * | 2020-04-08 | 2023-09-29 | 中国恩菲工程技术有限公司 | Method and device for producing black copper from copper-containing sludge |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103421955B (en) | Zinc leaching slag treatment method | |
| CN102965510B (en) | Reduction sulfur-fixing bath smelting method and device of low-sulfur lead-containing secondary material and iron-rich heavy metal solid waste | |
| CN111304450B (en) | Method and device for producing black copper from copper-containing sludge | |
| CN106399699A (en) | Process for treating sludge with copper import | |
| CN111893310A (en) | Harmless recycling treatment method for solid hazardous waste | |
| CN102965509A (en) | Method and device for treating daub and iron-rich heavy metal solid waste of waste lead-acid storage battery | |
| CN106011489A (en) | Iron vitriol slag treatment method | |
| CN116004936A (en) | Treatment method of laterite nickel ore acid leaching slag | |
| CN110373546A (en) | A kind of collaboration melting process for the treatment of of richness iron metallurgical dust sludge and high calcium incineration of refuse flyash | |
| US4266971A (en) | Continuous process of converting non-ferrous metal sulfide concentrates | |
| CN108103319B (en) | High-temperature strengthening refining method for copper-containing multi-metal material | |
| CN110373552A (en) | A kind of harmless treatment process using the low-grade lead-zinc residue of oxygen-enriched side-blowing furnace bath smelting | |
| CN111647749B (en) | Separation method of copper-containing solid waste | |
| CN110016565B (en) | Method for preparing ferro-silicon-aluminum alloy by feeding hollow electrode with waste refractory material as raw material | |
| CN212316200U (en) | Device for producing black copper from copper-containing sludge | |
| CN108531737B (en) | Comprehensive treatment system for copper-containing sludge and circuit board | |
| CN114854995B (en) | Method for smelting lead-containing concentrate by hydrogen base and treating lead-based solid waste | |
| CN215918601U (en) | Treatment system for waste cathode of aluminum electrolytic cell | |
| CN106011496B (en) | A kind of two-region bath smelting furnace and its slicker solder refine smelting process altogether | |
| CN109680151B (en) | Inorganic hazardous waste oxygen-enriched side-blown treatment process | |
| CN214327826U (en) | Treatment and utilization device for recovering zinc oxide by smelting reduction of suspended metallurgical zinc-containing ash | |
| JP2023155113A (en) | Coupling method of recycling of copper slag with co2 mineralization by solid industrial waste and system | |
| CN112143908B (en) | Smelting process for treating complex gold ore | |
| CN112391535A (en) | Treatment and utilization device and method for recovering zinc oxide from metallurgical zinc-containing ash by suspension smelting reduction | |
| CN114015875A (en) | Method for lead-copper co-smelting and dilution treatment of lead-copper mixed material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| GR01 | Patent grant | ||
| GR01 | Patent grant |