CN111304450B - Method and device for producing black copper from copper-containing sludge - Google Patents
Method and device for producing black copper from copper-containing sludge Download PDFInfo
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- CN111304450B CN111304450B CN202010270366.6A CN202010270366A CN111304450B CN 111304450 B CN111304450 B CN 111304450B CN 202010270366 A CN202010270366 A CN 202010270366A CN 111304450 B CN111304450 B CN 111304450B
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
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- C22B15/00—Obtaining copper
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- C22B15/003—Bath smelting or converting
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0026—Pyrometallurgy
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Abstract
The application provides a method and a device for producing black copper by copper-containing sludge. The method comprises the following steps: s1, dehydrating copper-containing sludge to a water content of 10-40 wt% to form dehydrated sludge; s2, mixing dehydrated sludge and flux, and then carrying out bottom blowing oxidation smelting in a full slag molten pool to form oxidized smelting slag; s3, carrying out side-blown reduction smelting on the oxidized smelting slag in a reduction molten pool to obtain a reduction smelting product; s4, carrying out sedimentation treatment on the reduction smelting product to obtain black copper and slag. The process for treating the copper-containing sludge effectively solves the problems of long flow, high copper content of tailings, high sulfur content and the like when copper is recovered from the copper-containing sludge in the prior art, and improves the recovery rate of valuable metals.
Description
Technical Field
The application relates to the technical field of metallurgy, in particular to a method and a device for producing black copper from copper-containing sludge.
Background
Copper-containing sludge is generally from the electroplating industry, and the sludge contains valuable metals such as nickel, lead, zinc, tin and the like in addition to a large amount of copper, and sulfate is generally contained in the copper-containing sludge. At present, a 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, black copper is produced, and part of the copper matte exists, so that melt layering and incomplete separation are caused, sulfide is easy to be mixed in tailings, a low-sulfur raw material is generally mixed for reduction smelting to reduce the proportion of copper matte, the produced black copper and copper matte are required to be separated again, the black copper is subjected to electrolysis, the copper matte is fed into a converting furnace, and the copper content of slag is about 0.8%, and the slag is generally used as a building material or is piled and discarded.
Application number 201611046435.5 proposes a low energy process for producing electrolytic copper and separating nickel, arsenic, tin from copper-containing sludge. Firstly, sintering and dehydrating copper-containing sludge until the water content is 1-5%, laterally blowing oxygen-enriched air, calcining to produce crude copper, refining and electrolyzing the crude copper to prepare cathode copper, and delivering refined slag into a blast furnace to produce black copper. The process points out typical components of the treated copper-containing sludge, but the sludge components are similar to the components of the conventional side-blown smelting slag type because of the proportion of limestone and quartz slag smelting, and the process may have the problem of poor raw material adaptability. In addition, copper-containing sludge is generally higher in copper content (greater than 1%) in slag when producing blister copper by direct side-blown smelting, and the process does not list the critical parameter of copper content of the smelting slag nor mention the utilization of the slag.
Application number 201611178461.3 proposes a treatment process for copper-containing sludge. The copper-containing sludge with the sulfur content lower than 2% is dried at a low temperature, then brickmaking is carried out, the brickmaking, a slag former and reduced coking coal are added into an oxygen-enriched side blowing furnace together to produce sub-coarse copper, tailings with the copper content of 0.6% are beneficiated and then the residual copper is recovered, and the copper-containing sludge with the sulfur content higher than 2% is dried at a low temperature and then enters a copper smelting system for cooperative treatment, and the process is the same as the conventional copper smelting process. The process can only treat copper-containing sludge with low sulfur content independently, the S content in most of copper-containing sludge is higher than 2%, the introduction of organic matters, halogen and other substances in the copper-containing sludge can bring negative influence to an ore copper smelting system, the copper-containing sludge is difficult to blend in a large proportion, and the process has poor raw material adaptability and limited treatment capacity.
It can be seen that a longer pretreatment process (mixing, briquetting, air drying, etc.) is required when copper-containing sludge is treated by a blast furnace process, and a large amount of copper-containing sludge is disposed at the top of the blast furnaceVolatile organic compounds are difficult to treat, the obtained product is layered, the layered product is required to be separated again and sent to different processes for treatment, tailings are high in copper content, and the utilization is difficult. In addition, the blast furnace process also has the problems of small monomer processing capacity, large labor intensity of workers, poor environmental protection conditions of smelting workshops and the like. When copper-containing sludge is treated by adopting a side-blowing furnace process, the copper-containing sludge is required to be dehydrated to be less than 10% of water content in advance, and is put into a side-blowing smelting furnace, heat is supplied and reduced by adopting an oxygen-enriched side submerged combustion mode, a spray gun is required to be far away from a metal and copper matte layer in order to prevent the spray gun from burning, the reducibility of the system is ensured by adopting an insufficient combustion mode, sulfide in slag, metal and copper matte below the spray gun is difficult to oxidize and remove, copper matte particles are easily mixed in tailings, flotation depletion treatment is still required after slow cooling, and SO is easy to occur 2 And (5) pollution. In a word, all the defects of long process, high copper content in tailings, high sulfur content and the like exist in the process of recovering copper from copper-containing sludge at present.
Disclosure of Invention
The application mainly aims to provide a method and a device for producing black copper by using copper-containing sludge, which are used for solving the problems of long flow, high copper content in tailings, high sulfur content and the like in the prior art when copper is recovered from the copper-containing sludge.
In order to achieve the above object, according to one aspect of the present application, there is provided a method for producing black copper from copper-containing sludge, comprising the steps of: s1, dehydrating copper-containing sludge to a water content of 10-40 wt% to form dehydrated sludge; s2, mixing dehydrated sludge and flux, and then carrying out bottom blowing oxidation smelting in a full slag molten pool to form oxidized smelting slag; s3, carrying out side-blown reduction smelting on the oxidized smelting slag in a reduction molten pool to obtain a reduction smelting product; s4, carrying out sedimentation treatment on the reduction smelting product to obtain black copper and slag.
Further, in step S2, oxygen or oxygen-enriched air with the oxygen volume content of 60-100% is blown to the bottom of the full slag molten pool to perform bottom blowing oxidation smelting, and simultaneously fuel, preferably coal dust and/or natural gas, is blown to the bottom of the full slag molten pool.
Further, 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%.
Further, in the step S2, the bottom blowing oxidation smelting temperature is 1250-1350 ℃, and the slag type of the oxidation smelting slag is Cu 2 O-CaO-Fe 2 O 3 -SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the Preferably, the flux is silica and/or quartz.
In the step S3, side blowing reducing agent into the reduction molten pool, and blowing oxygen or oxygen-enriched air with the oxygen volume content of 60-100% into the reduction molten pool to perform side blowing reduction smelting; preferably, the reducing agent is coal dust and/or natural gas.
Further, in the step S3, the temperature of the side-blown reduction smelting is 1250-1400 ℃, and the slag type generated in the side-blown reduction smelting process is FeO-SiO 2 -CaO。
Further, in the step S4, the copper content of the black copper is 70-85 wt%; the copper content of the slag is lower than 0.5wt%, the sulfur content is lower than 0.1wt% and the chlorine content is lower than 0.1wt%.
Further, the method further comprises the steps of: waste heat recovery, dust removal treatment and acid production are sequentially carried out on flue gas generated in the bottom blowing oxidation smelting process; and (2) carrying out waste heat recovery and dust removal treatment on flue gas generated in the process of side-blown reduction smelting and sedimentation treatment, and returning the tail gas after dust removal to the step (S1) for carrying out dehydration treatment on the copper-containing sludge.
According to another aspect of the present application, there is also provided an apparatus for producing black copper from copper-containing sludge, comprising: the drying device is provided with a copper-containing sludge inlet and a dehydrated sludge outlet and is used for dehydrating the copper-containing sludge to a water content of 10-40 wt% to form dehydrated sludge; the smelting furnace comprises a bottom blowing oxidation smelting area, a side blowing reduction smelting area and a sedimentation area which are sequentially communicated; the bottom blowing oxidation smelting area 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 area is also provided with a bottom blowing spray gun, and the bottom blowing oxidation smelting area is a full slag molten pool and is used for bottom blowing oxidation smelting of the dehydrated sludge and the flux to form oxidized smelting slag; the side part of the side-blowing reduction smelting area is provided with a side-blowing spray gun, and the side-blowing reduction smelting area is used for carrying out side-blowing reduction smelting on oxidized smelting slag to obtain a reduction smelting product; the sedimentation zone is provided with a black copper outlet and a slag outlet and is used for carrying out sedimentation treatment on the reduction smelting product so as to obtain black copper and slag.
Further, the apparatus further includes: the first gas supply unit is connected with the bottom blowing spray gun and is 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 pulverized coal to the bottom blowing spray gun.
Further, the apparatus further includes: the second gas supply unit is connected with the side-blowing spray gun and is 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 pulverized coal and/or natural gas to the side-blowing spray gun.
Further, be provided with first partition wall between bottom blowing oxidation smelting zone and the side blowing reduction smelting zone, the middle part of first partition wall is provided with and is used for the intercommunication: a first communication channel of the bottom blowing oxidation smelting area and the side blowing reduction smelting area.
Further, a second partition wall is arranged between the side-blown reduction smelting area and the sedimentation area, and a second communication channel for communicating the side-blown reduction smelting area and the sedimentation area is arranged between the second partition wall and the bottom wall of the smelting furnace.
Further, the bottom blowing spray gun is arranged at one end of the bottom blowing oxidation smelting area far away from the first partition wall, the height of the bottom wall of the bottom blowing oxidation smelting area gradually rises along the direction from the bottom blowing spray gun to the first partition wall, and the highest point is lower than the height of the first communication channel.
Further, the height of the bottom wall of the side-blown reduction smelting zone gradually decreases in 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 also has a first flue gas outlet, and the apparatus further comprises: the first waste heat recovery device is connected with the first flue gas outlet; the first dust removing device is connected with the outlet of the first waste heat recovery device; the acid making device is connected with the outlet of the first dust removing device.
Further, a third communication channel is further arranged at the upper part of the second partition wall, and a second flue gas outlet is further arranged in the sedimentation zone; the drying device is also provided with a heat medium inlet; the apparatus further comprises: the second waste heat recovery device is connected with the second flue gas outlet; the second dust removing device is connected with an outlet of the second waste heat recovery device; and the outlet of the second dust removing device is connected with the heat medium inlet of the drying device.
By applying the technical scheme of the application, desulfurization is realized through a full slag molten pool of bottom blowing oxidation smelting, and then side blowing reduction smelting is carried out on oxidized smelting slag to obtain high-value black copper and harmless slag, so that comprehensive recycling of a plurality of valuable metals such as Cu, ni, pb, zn, sn in sludge is realized. The copper-containing sludge with 10-40% of water directly enters a full slag melting pool for bottom blowing oxidation smelting, so that the problems of high temperature, high energy consumption, large smoke dust and the like in the deep drying process are avoided, organic pollutants in the sludge can be thoroughly decomposed, the elements such as S, cl in the copper-containing sludge are promoted to enter the flue gas almost completely, cu, ni, pb, zn, sn and the like are remained in the slag in the form of oxides, the recovery rate of valuable metals in the process of producing black copper by subsequent reduction 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, the process for treating the copper-containing sludge effectively solves the problems of long flow, high copper content of tailings, high sulfur content and the like when copper is recovered from the copper-containing sludge in the prior art, and improves the recovery rate of valuable metals.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the application. In the drawings:
FIG. 1 shows a flow chart of a method for producing black copper from copper-containing sludge according to an embodiment of the application; and
fig. 2 shows a schematic structural view of an apparatus for producing black copper from copper-containing sludge according to an embodiment of the present application.
Wherein the above 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 preparation device; 100. a second waste heat recovery device; 110. a second dust removing device;
21. a bottom blowing 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 dewatered sludge inlet; 202. a first flue gas outlet; 203. a second flue gas outlet;
211. a bottom blowing spray gun; 221. a side-blowing spray gun.
Detailed Description
It should be noted that, without conflict, the embodiments of the present application and features of the embodiments may be combined with each other. The application will be described in detail below with reference to the drawings in connection with embodiments.
As described in the background section, the prior art has the problems of long process flow, high copper content in tailings, high sulfur content and the like when copper is recovered from copper-containing sludge.
In order to solve the above problems, the present application provides a method for producing black copper from copper-containing sludge, as shown in fig. 1, comprising the steps of: s1, dehydrating copper-containing sludge to a water content of 10-40 wt% to form dehydrated sludge; s2, mixing dehydrated sludge and flux, and then carrying out bottom blowing oxidation smelting in a full slag molten pool to form oxidized smelting slag; s3, carrying out side-blown reduction smelting on the oxidized smelting slag in a reduction molten pool to obtain a reduction smelting product; s4, carrying out sedimentation treatment on the reduction smelting product to obtain black copper and slag.
The copper-containing sludge is treated by the process, desulfurization is realized through a full slag molten pool of bottom blowing oxidation smelting, and then side blowing reduction smelting is carried out on oxidized smelting slag to obtain high-value black copper and harmless slag, so that comprehensive recycling of a plurality of valuable metals such as Cu, ni, pb, zn, sn in the sludge is realized. The copper-containing sludge with 10-40% of water directly enters a full slag melting pool for bottom blowing oxidation smelting, so that the problems of high temperature, high energy consumption, large smoke dust and the like in the deep drying process are avoided, organic pollutants in the sludge can be thoroughly decomposed, the elements such as S, cl in the copper-containing sludge are promoted to enter the flue gas almost completely, cu, ni, pb, zn, sn and the like are remained in the slag in the form of oxides, the recovery rate of valuable metals in the process of producing black copper by subsequent reduction 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, the device provided by the application is used for treating the copper-containing sludge, so that the problems of long process, high copper content of tailings, high sulfur content and the like in the process of recovering copper from the copper-containing sludge in the prior art are effectively solved, and the recovery rate of valuable metals is improved.
The specification is that the full slag molten pool refers to full slag in the molten pool, no metal or copper matte phase residue exists 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 bottom blowing oxidation smelting can be that the dehydrated sludge is in an oxidant excess state, so that the high-efficiency melting of the sludge and the decomposition and desulfurization of sulfate are realized, no sulfide and metal residue at the bottom of the furnace are formed, and a full slag molten pool is realized. Through the bottom blowing oxidation smelting of the full slag molten pool, the following steps are realized: (1) The recovery rate of valuable metals in the subsequent side-blown reduction smelting process is improved; (2) The flue gas 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 during final slag water quenching 2 S is polluted, the Cl content in the water quenching slag is low, and the water quenching slag can be widely used in the building material industry; (4) The refractory material and the spray gun at each position of the furnace body can realize water-cooling slag hanging, thereby prolonging the service lives of the refractory material and the spray gun of the furnace body and avoiding the danger of explosion when metal or matte exists at the water-cooling position. And then carrying out side-blown reduction smelting on the oxidized smelting slag to obtain high-value black copper, and producing flue gas and tailings with low content of harmful substances, thereby realizing the recycling comprehensive utilization of the copper-containing sludge.
In a preferred embodiment, in the step S2, oxygen or oxygen-enriched air with the oxygen volume content of 60-100% (60%. Ltoreq.volume concentration is less than 100%) is bottom-blown into the full slag molten pool to perform bottom-blown oxygenized smelting, and simultaneously fuel, preferably coal dust and/or natural gas, is bottom-blown into the full slag molten pool. In this way, the dehydrated copper-containing sludge with 10-40% of water can be fully oxidized under the conditions of bottom oxygen-blown gas (oxygen-enriched air) and fuel, sulfate and organic matters in the dehydrated copper-containing sludge are fully decomposed, valuable metals enter oxidized smelting slag more thoroughly, 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%. Thus, the oxygen is excessive, the oxidation smelting is more facilitated, the heat efficiency is improved by full combustion of fuel, the sludge raw material with higher water content can be used, and the sludge pretreatment difficulty is reduced.
In a preferred embodiment, in the step S2, the bottom blowing oxidation smelting temperature is 1250-1350 ℃, and the slag type of the oxidation smelting slag is Cu 2 O-CaO-Fe 2 O 3 -SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the At the temperature, the oxidation reaction and the decomposition of organic matters and sulfate are more thorough, which is more beneficial to the recovery of valuable metals and the separation of sulfur and chlorine. And the slag type of the oxidized smelting slag is controlled to be the slag type, which is favorable for valuable metals such as Cu, ni, pb, zn, sn to remain in the slag in the form of oxides, and provides conditions for improving the metal recovery rate in the subsequent reduction and separation process. Preferably, the flux is silica and/or quartz.
In a preferred embodiment, in the above step S3, a reducing agent is side-blown into the reduction bath, and oxygen or oxygen-enriched air having an oxygen content of 60 to 100% by volume (60% by volume or less than 100%) is blown to perform side-blown reduction smelting. The entry of oxygen (oxygen-enriched air) maintains the temperature of the reduction process, and under the action of the reducing agent, copper oxides in the oxidized smelting slag are reduced to form black copper, which is separated from the slag. Preferably, the reducing agent is coal dust and/or natural gas. In order to maintain a more stable reducing atmosphere, it is preferable that the CO volume content in the flue gas generated by the side-blown reduction smelting is 10-20%.
In order to make the reduction reaction more complete, in a preferred embodiment, in the step S3, the temperature of the side-blown reduction smelting is 1250-1400 DEG CAnd the slag generated in the process of side-blown reduction smelting is FeO-SiO 2 -CaO. The copper-containing sludge initially contains higher CaO, which is convenient for manufacturing FeO-SiO 2 CaO slag having a melting point ratio FeO-SiO 2 The slag is lower, the slag and the metal are better separated, the Cu residual amount in the slag is less when the CaO-containing slag is balanced, and the initial CaO component in the copper-containing sludge is fully utilized.
For the reasons stated above, the method provided by the application has the advantages that the metal phase recovered from the copper-containing sludge is Pb, zn, ni, sn-rich black copper, the recovery rate is high, and the copper content of the black copper is 70-85 wt%; the copper content of the slag is lower than 0.5wt%, the sulfur content is lower than 0.1wt% and the chlorine content is lower than 0.1wt%. The black copper can be used for the comprehensive recovery of valuable metals by electrolysis, and the slag is water quenched to be used as a building material.
In a preferred embodiment, the above method further comprises: waste heat recovery, dust removal treatment and acid production are sequentially carried out on flue gas generated in the bottom blowing oxidation smelting process; and (2) carrying out waste heat recovery and dust removal treatment on flue gas generated in the process of side-blown reduction smelting and sedimentation treatment, and returning the tail gas after dust removal to the step (S1) for carrying out dehydration treatment on the copper-containing sludge. The flue gas produced in the bottom blowing oxydation smelting process contains a large amount of sulfur and chlorine (SO) 2 The volume concentration is more than 2 percent), the waste heat recovery and dust removal treatment can be used for preparing acid, and in order to prevent the flue gas from condensing and corroding a pipeline, the tail gas temperature of the tail gas after preheating and recovery is preferably controlled at about 350 ℃. Meanwhile, because sulfate, organic matters and the like are fully decomposed in the bottom blowing oxidation smelting process, 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, and the flue gas can be returned to the dehydration treatment stage after waste heat recovery (preferably, the tail end temperature is controlled at 150 ℃) and dust removal treatment, so that the heat energy is effectively utilized. And in order to enable the part of flue gas to burn more fully, oxygen is preferably supplemented at a tail gas outlet in the process of side-blown reduction smelting and sedimentation treatment.
According to another aspect of the present application, there is also provided an apparatus for producing black copper from copper-containing sludge, as shown in fig. 2, comprising a drying apparatus 10 and a smelting furnace 20, the drying apparatus 10 having a copper-containing sludge inlet and a dehydrated sludge outlet, the drying apparatus 10 being adapted to dehydrate the copper-containing sludge to a water content of 10 to 40wt% to form dehydrated sludge; smelting furnace 20 comprises a bottom blowing oxidation smelting zone 21, a side blowing reduction smelting zone 22 and a sedimentation 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, a bottom blowing spray gun 211 is further arranged at the bottom of the bottom blowing oxidation smelting zone 21, and the bottom blowing oxidation smelting zone 21 is a full slag molten pool and is used for carrying out bottom blowing oxidation smelting on the dehydrated sludge and the flux to form oxidized 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 oxidized smelting slag to obtain a reduction smelting product; the sedimentation zone 23 has a black copper outlet and a slag outlet, and the sedimentation zone 23 is used for carrying out sedimentation treatment on the reduction smelting product to obtain black copper and slag.
The device is used for treating copper-containing sludge, desulfurization is realized through a full slag molten pool of bottom blowing oxidation smelting, and then side blowing reduction smelting is carried out on oxidized smelting slag to obtain high-value black copper and harmless slag, so that comprehensive recycling of a plurality of valuable metals such as Cu, ni, pb, zn, sn in the sludge is realized. The copper-containing sludge with 10-40% of water directly enters a full slag melting pool for bottom blowing oxidation smelting, so that the problems of high temperature, high energy consumption, large smoke dust and the like in the deep drying process are avoided, organic pollutants in the sludge can be thoroughly decomposed, the elements such as S, cl in the copper-containing sludge are promoted to enter the flue gas almost completely, cu, ni, pb, zn, sn and the like are remained in the slag in the form of oxides, the recovery rate of valuable metals in the process of producing black copper by subsequent reduction 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, the device provided by the application is used for treating the copper-containing sludge, so that the problems of long process, high copper content of tailings, high sulfur content and the like in the process of recovering copper from the copper-containing sludge in the prior art are effectively solved, and the recovery rate of valuable metals is improved.
The whole slag molten pool refers to the whole slag in the molten pool, no metal or copper matte phase residue exists at the bottom of the molten pool, and the metal in the sludge is completely oxidized in the bottom blowing oxidation smelting processAnd (5) melting. In the actual smelting process, the bottom blowing oxidation smelting can be that the dehydrated sludge is in an oxidant excess state, so that the high-efficiency melting of the sludge and the decomposition and desulfurization of sulfate are realized, no sulfide and metal residue at the bottom of the furnace are formed, and a full slag molten pool is realized. Through the bottom blowing oxidation smelting of the full slag molten pool, the following steps are realized: (1) The recovery rate of valuable metals in the subsequent side-blown reduction smelting process is improved; (2) The flue gas 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 during final slag water quenching 2 S is polluted, the Cl content in the water quenching slag is low, and the water quenching slag can be widely used in the building material industry; (4) The refractory material and the spray gun at each position of the furnace body can realize water-cooling slag hanging, thereby prolonging the service lives of the refractory material and the spray gun of the furnace body and avoiding the danger of explosion when metal or matte exists at the water-cooling position. And then carrying out side-blown reduction smelting on the oxidized smelting slag to obtain high-value black copper, and producing flue gas and tailings with low content of harmful substances, thereby realizing the recycling comprehensive utilization of the copper-containing sludge.
In order to improve the safety, the inner furnace lining of the bottom blowing oxidation smelting zone 21 is preferably protected by water-cooling slag hanging, and the bottom blowing lance 211 is also water-cooling.
In a preferred embodiment, as shown in fig. 2, the apparatus further comprises: a first gas supply unit 30, the first gas supply unit 30 being connected to the bottom blowing lance 211 for supplying oxygen or oxygen enriched air having an oxygen volume content of 60 to 100% to the bottom blowing lance 211; and a fuel supply device 40, wherein the fuel supply device 40 is connected with the bottom blowing lance 211 and is used for supplying pulverized coal to the bottom blowing lance 211. In this way, the dehydrated copper-containing sludge with 10-40% of water can be fully oxidized under the conditions of bottom oxygen-blown gas (oxygen-enriched air) and fuel, sulfate and organic matters in the dehydrated copper-containing sludge are fully decomposed, valuable metals enter oxidized smelting slag more thoroughly, and sulfur, chlorine and the like enter tail gas.
In a preferred embodiment, the above further comprises: a second gas supply unit 50, the second gas supply unit 50 being connected to the side-blowing lance 221 for supplying oxygen or oxygen-enriched air having an oxygen volume content of 60 to 100% to the side-blowing lance 221; the reducing agent supply device 60, the reducing agent supply device 60 is connected with the side-blowing lance 221, for supplying pulverized coal and/or natural gas to the side-blowing lance 221. The entry of oxygen (oxygen-enriched air) maintains the temperature of the reduction process, and under the action of the reducing agent, copper oxides in the oxidized smelting slag are reduced to form black copper, which is separated from the slag. Preferably, the reducing agent is coal dust 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 connecting part for communicating: a first communication channel of the bottom blowing oxidation smelting zone 21 and the side blowing reduction smelting zone 22. In this way, the oxidized smelting slag generated in the bottom blowing oxidation smelting process can continuously enter the side blowing reduction smelting zone 22 to carry out side blowing reduction smelting, and the slag entering is more stable.
In a preferred embodiment, a second partition wall 25 is provided between the side-blown reduction smelting zone 22 and the sedimentation zone 23, and a second communication channel for communicating the side-blown reduction smelting zone 22 and the sedimentation zone 23 is provided between the second partition wall 25 and the bottom wall of the smelting furnace 20. In this way, the reduction smelting products can more stably enter the sedimentation zone 23 for sedimentation treatment, the partition wall can prevent disturbance in the side-blown reduction smelting zone 22, and the sedimentation separation effect is better.
More preferably, the bottom blowing lance 211 is disposed at one end of the bottom blowing oxidation smelting zone 21 distant from the first partition wall 24, and the height of the bottom wall of the bottom blowing oxidation smelting zone 21 gradually rises in 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 passage. In this way, slag can enter the reduction smelting zone more stably and continuously. Likewise, it is preferable that the height of the bottom wall of the side-blown reduction smelting zone 22 gradually decreases in the direction from the first communication channel to the second communication channel.
In order to make the dewatering efficiency of the aqueous sludge higher, in a preferred embodiment, the drying apparatus 10 is a rotary kiln. In practice, the drying temperature of the rotary kiln is preferably low temperature drying, such as about 150 ℃.
In a preferred embodiment, the bottom blowing oxydation smelting zone 21 further has a first flue gas outlet 202, the apparatus further comprising: first waste heat recovery device 70, and first smokeA gas outlet 202; the first dust removing device 80 is connected with the outlet of the first waste heat recovery device 70; the acid making device 90 is connected with the outlet of the first dust removing device 80. The flue gas produced in the bottom blowing oxydation smelting process contains a large amount of sulfur and chlorine (SO) 2 The volume concentration is more than 2 percent), the waste heat recovery and dust removal treatment can be used for preparing acid, and in order to prevent the flue gas from condensing and corroding a pipeline, the tail gas temperature of the tail gas after preheating and recovery is preferably controlled at about 350 ℃.
In a preferred embodiment, the upper part of the second partition wall 25 is further provided with a third communication channel, and the sedimentation zone 23 is further provided with a second flue gas outlet 203; the drying device 10 also has a heat medium inlet; the apparatus further comprises: 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 with 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, 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, and the flue gas can be returned to the dehydration stage after waste heat recovery (preferably, the tail end temperature is controlled at 150 ℃) and dust removal treatment, so that the heat energy is effectively utilized. And to burn this portion of the flue gas more fully, oxygen is preferably supplemented at the second flue gas outlet 203.
In summary, the method and the device for treating the copper-containing sludge have the following beneficial effects:
(1) The copper-containing sludge with 10-40% of water is used as the raw material, the drying requirement of the raw material is low, and the problems of high temperature, high energy consumption, large smoke dust amount, large volatilization amount of organic matters and the like in the deep drying pretreatment are avoided.
(2) The materials directly enter a full slag molten pool, the high-temperature molten pool has strong oxidizing property, organic matters in the sludge are thoroughly decomposed, sulfate is completely decomposed, chloride is thoroughly volatilized, the residual quantity of sulfur and halogen in the slag is small, and the flue gas SO in an oxidation zone is low 2 The volume concentration is higher than 2%, and the acid preparation is convenient.
(3) Preferably, the oxygen content in the flue gas is about 5% due to the surplus combustion oxygen in the bottom blowing oxidation smelting process, so that 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 the furnace lining is prolonged.
(4) Preferably, the bottom blowing oxidation smelting slag Cu 2 O-CaO-Fe 2 O 3 -SiO 2 The slag system is mainly used, is favorable for valuable metals such as Cu, ni, pb, zn, sn to remain in the slag in the form of oxides, and provides conditions for improving the metal recovery rate in the subsequent reduction and 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 and the waste heat recovery rate of the waste heat boiler are improved, the tail gas temperature at the tail end of the waste heat boiler is about 150 ℃, and the tail gas can be reused for low-temperature drying of raw materials.
(6) Preferably, the slag has low sulfide and halogen content, copper content of the slag is below 0.5%, S, cl element content is below 0.1%, and the slag can be largely used in the building material industry after water quenching treatment.
The application is described in further detail below in connection with specific examples which are not to be construed as limiting the scope of the application as claimed.
The copper-containing sludge used in the examples had the following main components:
TABLE 1 copper-containing sludge composition (wt.%)
| Al 2 O 3 | CaO | SiO 2 | 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 exists mainly in the form of 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) putting the copper-containing sludge with the water content of 75% into a rotary kiln for drying, wherein the inlet temperature of flue gas at the tail of the kiln is about 150 ℃, and the flue gas at the temperature of 150 ℃ is dried to the water content of about 20% and is granular.
57kg of silica is added to each ton of copper-containing sludge (containing 20 percent of water), and the sludge and the silica are mixed and then are put into a bottom blowing oxidation zone molten pool shown in figure 2, and a water-cooled furnace wall, a water-cooled spray gun refractory and spray gun slag hanging protection are adopted. Adopts bottom blowing pure oxygen and pulverized coal, consumes 100kg of pulverized coal per ton of sludge (containing 20 percent of water) and 12Nm of air 3 (powder spraying carrier gas), oxygen 294Nm 3 . The molten pool is slag, the temperature of the molten pool is 1250-1350 ℃, and SO in the flue gas 2 、O 2 The volume contents are 5.05 percent and 4.65 percent respectively, the flue gas is subjected to waste heat boiler and dust removal to prepare sulfuric acid, and the hot slag flows into a side-blown reduction smelting area.
Coal dust and oxygen are blown to the side of the side blowing reduction smelting area, 90kg of coal dust is consumed per ton of sludge (containing 20% of water), and 10Nm of air is consumed 3 95Nm of oxygen 3 . The temperature of the side-blown molten pool ranges from 1300 ℃ to 1350 ℃, the volume concentration of CO in flue gas above the side-blown molten pool is 18.20%, an oxygen burning gun is added in a rising flue to fully burn CO, the flue gas enters a waste heat boiler to recover waste heat and remove dust, smoke dust 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 blowing reduction, the black copper and slag can be obtained through sedimentation separation, the black copper is sent to electrolysis, and the slag is water quenched to be used as a building material.
158kg of black copper and 411kg of water quenching slag are produced by treating each ton of sludge, wherein the Cu, ni, pb, zn, sn content in the slag is respectively 0.40%, 0.01%, 0.07%, 0.18%, 0.22% and S, cl are respectively lower than 0.1%, and the Cu, ni, pb, zn, sn content in the black copper is respectively 79.50%, 3.12%, 1.06%, 5.21% and 5.11%.
Example 2
The treatment method is the same as in example 1, but the sludge is dried to a higher degree, the water content is about 10%, oxygen-enriched air with the oxygen concentration of 90% 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) putting the copper-containing sludge with the water content of 75% into a rotary kiln for drying, wherein the inlet temperature of flue gas at the tail of the kiln is about 150 ℃, and the flue gas at the temperature of 150 ℃ is dried to the water content of about 10% and is granular.
Each ton of copper-containing sludge (containing 10 percent of water) needs to be added with 64kg of silica, and the sludge is mixed with the silica and then is put into a bottom blowing oxidation zone molten pool shown in figure 2, and the water-cooled furnace wall, the water-cooled spray gun refractory and the spray gun slag hanging protection are adopted. The pulverized coal is subjected to bottom blowing and oxygen enrichment (the concentration of the oxygen enrichment is 90%), 110kg of pulverized coal and 61Nm of air are consumed in the treatment of each ton of sludge (the water content is 20 percent) 3 (powder spraying carrier gas therein), oxygen 308Nm 3 . The molten pool is slag, the temperature of the molten pool is 1250-1350 ℃, and SO in the flue gas 2 、O 2 The volume contents are 6.10 percent and 4.31 percent respectively, the flue gas is subjected to waste heat boiler and dust removal to prepare sulfuric acid, and the hot slag flows into a side-blown reduction smelting area.
The side-blown coal dust and the oxygen enrichment (the oxygen enrichment concentration is 90%) in the side-blown reduction smelting area consume 95kg coal dust and 26Nm air per ton of sludge (the water content is 10%) 3 95Nm of oxygen 3 . The temperature of the side blowing molten pool ranges from 1350 ℃ to 1400 ℃, the volume concentration of CO in flue gas above the side blowing molten pool is 16.85%, an oxygen burning gun is added in a rising flue to fully burn CO, the flue gas enters a waste heat boiler to recover waste heat and remove dust, smoke dust 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 blowing reduction, the black copper and slag can be obtained through sedimentation separation, the black copper is sent to electrolysis, and the slag is water quenched to be used as a building material.
166kg of black copper is produced by treating each ton of sludge, 465kg of water quenching slag is produced, the Cu, ni, pb, zn, sn content in the slag is respectively 0.46%, 0.01%, 0.03%, 0.11%, 0.13% and S, cl are respectively lower than 0.1%, and the Cu, ni, pb, zn, sn content in the black copper is respectively 85.01%, 3.35%, 0.76%, 4.06% and 4.26%.
Example 3
The treatment method is the same as in example 1, but the sludge is low in drying degree, contains about 40% of water, adopts oxygen-enriched air with the oxygen concentration of 95% to carry out bottom blowing and side blowing combustion heat supply, and controls the temperature of a molten pool in the furnace to be lower.
And (3) putting the copper-containing sludge with the water content of 75% into a rotary kiln for drying, wherein the inlet temperature of flue gas at the tail of the drying kiln is about 150 ℃, and drying the copper-containing sludge to the water content of about 40% under the flue gas at the temperature of 150 ℃.
Per ton of copper-containing sludge (water content)40%) of silica is added, 42.5kg of silica is added, and the sludge and the silica are mixed and then are put into a bottom blowing oxidation zone molten pool shown in figure 2, and water-cooled furnace walls, water-cooled spray gun refractory materials and spray gun slag-hanging protection are adopted. 100kg of coal dust and 31Nm of air are consumed in the treatment of each ton of sludge (40% of water) by adopting bottom blowing coal dust and oxygen enrichment (95% of oxygen enrichment concentration) 3 (wherein the powder-spraying carrier gas) oxygen 266Nm 3 . The molten pool is slag, the temperature of the molten pool is 1250-1350 ℃, and SO in the flue gas 2 、O 2 The volume contents are 2.79 percent and 4.05 percent respectively, the flue gas is subjected to waste heat boiler and dust removal to prepare sulfuric acid, and the hot slag flows into a side-blown reduction smelting area.
The side-blown coal dust and the oxygen enrichment (the oxygen enrichment concentration is 95%) in the side-blown reduction smelting area consume 80kg of coal dust and 16Nm of air per ton of sludge (the water content is 40%) 3 Oxygen of 86Nm 3 . The temperature of the side blowing molten pool ranges from 1250 ℃ to 1300 ℃, the volume concentration of CO in flue gas above the side blowing molten pool is 17.46%, an oxygen burning gun is added in a rising flue to fully burn CO, the flue gas enters a waste heat boiler to recover waste heat and remove dust, smoke dust 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 blowing reduction, the black copper and slag can be obtained through sedimentation separation, the black copper is sent to electrolysis, and the slag is water quenched to be used as a building material.
130kg of black copper is produced by treating each ton of sludge, 302kg of water quenching slag is produced, the Cu, ni, pb, zn, sn content in the slag is respectively 0.47%, 0.01%, 0.03%, 0.37%, 0.45% and S, cl are respectively lower than 0.1%, and the Cu, ni, pb, zn, sn content in the black copper is respectively 72.31%, 2.85%, 1.13%, 6.04% and 6.73%.
The above description is only of the preferred embodiments of the present application and is not intended to limit the present application, but various modifications and variations can be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (11)
1. The method for producing black copper by using the copper-containing sludge is characterized by comprising the following steps of:
s1, dehydrating copper-containing sludge to a water content of 10-40 wt% to form dehydrated sludge;
s2, mixing the dehydrated sludge with a flux, and then performing bottom blowing oxidation smelting in a full slag molten pool to form oxidized smelting slag;
s3, carrying out side-blown reduction smelting on the oxidized smelting slag in a reduction molten pool to obtain a reduction smelting product;
s4, carrying out sedimentation treatment on the reduction smelting product to obtain black copper and slag;
in the step S2, oxygen or oxygen-enriched air with the oxygen volume content of 60-100% is blown to the bottom of the full slag molten pool to perform bottom blowing oxygen smelting, and simultaneously fuel is blown to the bottom of the full slag molten pool, wherein the fuel is coal dust and/or natural gas; controlling the oxygen volume content in the flue gas generated in the bottom blowing oxidation smelting process to be 1-10%; the temperature of the bottom blowing oxidation smelting is 1250-1350 ℃, and the slag type of the oxidation smelting slag is Cu 2 O-CaO-Fe 2 O 3 -SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the The flux is quartz stone;
in the step S3, side blowing reducing agent into the reduction molten pool, and blowing oxygen or oxygen-enriched air with the oxygen volume content of 60-100% into the reduction molten pool to perform side blowing reduction smelting; the reducing agent is pulverized coal and/or natural gas; the temperature of the side-blown reduction smelting is 1250-1400 ℃, and the slag generated in the side-blown reduction smelting process is FeO-SiO 2 -CaO。
2. The method according to claim 1, wherein in the step S4, the copper content of the black copper is 70 to 85wt%; the copper content of the slag is lower than 0.5wt%, the sulfur content is lower than 0.1wt% and the chlorine content is lower than 0.1wt%.
3. The method according to claim 1 or 2, characterized in that the method further comprises:
waste heat recovery, dust removal treatment and acid production are sequentially carried out on the flue gas generated in the bottom blowing oxidation smelting process;
and (2) carrying out waste heat recovery and dust removal treatment on the flue gas generated in the side-blown reduction smelting and sedimentation treatment processes, and returning the tail gas after dust removal to the step (S1) for carrying out dehydration treatment on the copper-containing sludge.
4. The method of claim 1, wherein the means for employing comprises:
a drying device (10), the drying device (10) having a copper-containing sludge inlet and a dehydrated sludge outlet, the drying device (10) being configured to dehydrate the copper-containing sludge to a water content of 10-40 wt% to form the dehydrated sludge;
a smelting furnace (20) comprising a bottom blowing oxidation smelting zone (21), a side blowing reduction smelting zone (22) and a sedimentation zone (23) which are sequentially communicated; 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, a bottom blowing spray gun (211) is further arranged at the bottom of the bottom blowing oxidation smelting zone (21), the bottom blowing oxidation smelting zone (21) is a full slag molten pool, and the dehydrated sludge and the flux are subjected to bottom blowing oxidation smelting to form oxidized 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 oxidized smelting slag to obtain a reduction smelting product; -the sedimentation zone (23) having a black copper outlet and a slag outlet, the sedimentation zone (23) being adapted to perform a sedimentation treatment of the reduction smelting product to obtain the black copper and the slag;
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);
a second gas supply unit (50), wherein the second gas supply unit (50) is connected with the side-blowing spray gun (221) and is used for supplying oxygen or oxygen-enriched air with the oxygen volume content of 60-100% to the side-blowing spray gun (221);
and the reducing agent supply device (60) is connected with the side-blowing spray gun (221) and is used for supplying coal dust and/or natural gas to the side-blowing spray gun (221).
5. The method according to claim 4, characterized in that a first partition wall (24) is arranged between the bottom-blown oxidation smelting zone (21) and the side-blown reduction smelting zone (22), and a first communication channel for communicating the bottom-blown oxidation smelting zone (21) and the side-blown reduction smelting zone (22) is arranged in the middle of the first partition wall (24).
6. The method according to claim 5, characterized in that a second partition wall (25) is arranged between the side-blown reduction smelting zone (22) and the sedimentation zone (23), and a second communication channel for communicating the side-blown reduction smelting zone (22) and the sedimentation zone (23) is arranged between the second partition wall (25) and the bottom wall of the smelting furnace (20).
7. The method according to claim 6, characterized in that the bottom blowing lance (211) is arranged at an end of the bottom blowing oxidation smelting zone (21) remote from the first partition wall (24), and that the height of the bottom wall of the bottom blowing oxidation smelting zone (21) is gradually raised in 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.
8. The method according to claim 6, characterized in that the height of the bottom wall of the side-blown reduction smelting zone (22) decreases gradually in the direction from the first communication channel to the second communication channel.
9. The method according to claim 4, characterized in that the drying device (10) is a rotary kiln.
10. The method according to claim 4, characterized in that the bottom blowing oxidation smelting zone (21) further has a first flue gas outlet (202), the arrangement further comprising:
the first waste heat recovery device (70) is connected with the first flue gas outlet (202);
the first dust removing 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 removing device (80).
11. The method according to claim 6, characterized in that the upper part of the second partition wall (25) is further provided with a third communication channel, the sedimentation 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 apparatus further comprises:
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 with the heat medium inlet of the drying device (10).
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| CN113278801B (en) * | 2021-04-28 | 2023-04-28 | 中国恩菲工程技术有限公司 | Method for treating copper-containing sludge and equipment for treating copper-containing sludge |
| CN113549772A (en) * | 2021-07-13 | 2021-10-26 | 中国瑞林工程技术股份有限公司 | Method for comprehensively recycling valuable metals from copper-containing waste materials |
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