CN111020212B - Recovery process of copper from copper-containing waste metal - Google Patents
Recovery process of copper from copper-containing waste metal Download PDFInfo
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- CN111020212B CN111020212B CN201911253759.XA CN201911253759A CN111020212B CN 111020212 B CN111020212 B CN 111020212B CN 201911253759 A CN201911253759 A CN 201911253759A CN 111020212 B CN111020212 B CN 111020212B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0026—Pyrometallurgy
- C22B15/0056—Scrap treating
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/242—Binding; Briquetting ; Granulating with binders
- C22B1/243—Binding; Briquetting ; Granulating with binders inorganic
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0002—Preliminary treatment
- C22B15/0004—Preliminary treatment without modification of the copper constituent
- C22B15/0006—Preliminary treatment without modification of the copper constituent by dry processes
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The invention discloses a copper-containing waste metal copper recovery process, which comprises the following steps: step 1, preparing copper-containing clinker, step 2, preparing copper-containing powder, step 3, making bricks, namely mixing the copper-containing clinker prepared in the step 1 and the copper-containing powder prepared in the step 2 until the copper content reaches more than 25wt%, then feeding the mixture into a brick making system, and preparing copper-containing bricks by matching with a coagulant, step 4, smelting, and step 5, treating flue gas of a smelting furnace. The recovery process of the copper-containing waste metal copper can recover the metal copper in the copper-containing waste, reduce the non-copper metal elements in the recovered copper alloy and provide raw materials for the subsequent preparation of refined copper.
Description
Technical Field
The invention relates to the field of copper extraction, in particular to a process for recovering copper from copper-containing waste materials.
Background
Copper has excellent properties such as electrical conductivity, thermal conductivity, ductility, corrosion resistance, and wear resistance, and is widely used in the fields of electric power, electronics, energy, petrochemicals, machinery, metallurgy, traffic, light industry, and emerging industries. Due to the rapid development of the field, the contradiction between the shortage of copper ore resources and the rapid increase of the demand of refined copper is increasingly prominent, and an effective way for solving the contradiction is to reasonably utilize the regenerated copper resources, mainly through the recycling of scrap copper. Scrap copper is a generic term for scrap copper and scrap copper, which is generated from waste products and scraps generated during copper smelting and copper processing, and products such as buildings, automobiles, electric power, electronic and electric appliances and the like which are discarded after use. At present, the main techniques for recovering scrap copper are as follows: mechanical treatment technology, pyrolysis treatment technology, pyrometallurgical technology and hydrometallurgical technology. The mechanical treatment technology and the pyrolysis treatment technology are simple and easy to scale, and the obtained concentrate is not a final product but a mixture of two or more metal elements, so that the concentrate is usually used as a pretreatment means and further combined with a hydrometallurgy technology to form a recovery system, and the high-purity copper product is recovered.
In the prior art, patent application with publication number CN109569881A and publication number 2019.04.05 discloses a method for preparing copper alloy by recycling waste circuit boards, which comprises the following steps: the method comprises the following steps of (a) desoldering, heating a waste circuit board to 250-270 ℃ until soldering tin on the waste circuit board is melted, and removing electronic elements on the waste circuit board to obtain a substrate; crushing the substrate into fine materials with the particle size of 0.3-0.4 mm; sorting, namely performing magnetic separation on the fine materials to remove ferromagnetic impurities in the fine materials to obtain magnetic separation materials; proportioning a sorting solution, putting the fine materials subjected to magnetic separation into the sorting solution, quickly separating the nonmetallic substances from the metallic substances, and collecting metallic substance sediments; refining in the step (IV), preheating the metal substance deposit to 600-650 ℃, then heating to 1000-1250 ℃, and keeping for 50-60 min to obtain a copper mixture; and (V) smelting, namely mixing the copper mixture with the metal simple substance and smelting at 1000-1250 ℃ to obtain the copper alloy. According to the technical scheme, the rapid separation of the metal substances and the non-metal substances can be realized through twice separation in the step (three), however, the separated metal substances contain not only copper metal but also molybdenum, magnesium, calcium and other metals, so that the refined copper mixture obtained in the step (four) is actually a copper mixture containing a mixture of multiple metal elements, the refined copper mixture is directly smelted in the step (five) without metal element separation, the copper mixture and the metal simple substance are smelted to obtain the copper alloy, the non-copper metal elements in the copper alloy are not separated, the performance of the copper alloy cannot be determined, the copper content is improved by adopting a method of directly adding the copper simple substance, and the waste copper recycling in a complete sense is not realized.
Disclosure of Invention
The invention aims to provide a copper-containing waste metal copper recovery process, which can recover metal copper in copper-containing waste, reduce non-copper metal elements in recovered copper alloy and provide raw materials for the subsequent preparation of refined copper.
In order to achieve the above purpose of the present invention, the present invention provides the following technical solutions: a recovery process of metallic copper from copper-containing waste materials comprises the following steps:
step 1, preparing copper-containing clinker, namely blending the hazardous wastes until the copper content reaches 22wt%, putting the hazardous wastes into a rotary kiln for incineration at the temperature of 850 ℃ for 1-1.5h, generating the copper-containing clinker after the incineration is finished, discharging the copper-containing clinker from the tail part of the rotary kiln, and sending the copper-containing clinker to a briquetting and brick making system;
step 2, preparing copper-containing powder, disassembling the waste circuit board to obtain a substrate, crushing and sorting the substrate to obtain the copper-containing powder, and conveying the copper-containing powder to a briquetting and brick making system;
step 3, brickmaking, namely blending the copper-containing clinker prepared in the step 1 and the copper-containing powder prepared in the step 2 until the copper content reaches more than 25wt%, entering a brickmaking system, and adding water into coagulant cement to prepare a copper-containing brick;
step 4, smelting, namely putting the copper-containing bricks prepared in the step 3 into a smelting furnace, blowing oxygen into the furnace to ensure that the oxygen in the air entering the furnace reaches 28-30vol%, adding a fluxing agent, a reducing agent and fuel, wherein the smelting temperature is 1100-1200 ℃, primary slag is discharged within 0.5h, primary copper liquid is discharged within 2.5h, and the copper liquid is discharged from a copper outlet at the lower part of the smelting furnace;
and step 5, treating the flue gas of the smelting furnace.
In the invention, the hazardous waste (comprising HW12 dye, coating waste, HW17 surface treatment matter, HW22 copper-containing waste, HW45 organic halide-containing waste, HW46 nickel-containing waste, HW48 non-ferrous metal smelting waste and HW50 waste catalyst, and 95000t/a in total) in the raw materials is incinerated to generate carbon dioxide and water, thereby obtaining copper-containing clinker, and reducing and detoxifying the hazardous waste. The waste circuit board (hazardous waste category is HW49) is crushed and sorted to separate copper-containing powder from nonmetal (epoxy resin powder) to obtain copper-containing powder, and the separated epoxy resin powder is sent to a household garbage landfill for treatment. The method comprises the steps of preparing a copper-containing brick by utilizing copper-containing clinker and copper-containing powder prepared by cementing cement, mixing the copper-containing brick with a fluxing agent and a reducing agent, smelting at a high temperature, combining the fluxing agent with iron, molybdenum, magnesium, calcium, silicon and the like in materials to form tailings, realizing the separation of copper and other non-copper metal elements, improving the copper content of products and reducing the content of other non-metal copper elements. In the smelting process, cement enters tailings, the tailings are light and are discharged from an upper slag discharge port; and the tailings are returned to the smelting furnace for continuous smelting according to the copper content, so that the copper content is low, and the copper concentrate powder is processed to realize recycling. The matte obtained by smelting is heavier and is deposited on the lower layer, and can flow out from a copper discharge port at the lower part of the smelting furnace, and the matte is used as an intermediate product to provide raw materials for the subsequent preparation of refined copper. After the smelting furnace flue gas is treated, pollutants are effectively removed, and the requirement of environmental protection is met.
Preferably, the fluxing agent is limestone or quartz, the reducing agent is iron oxide, and the fuel is semi-coke.
By adopting the scheme, the limestone has low melting point, can promote the melting of quartz stone and iron oxide, and improves the fluidity. Iron, molybdenum, magnesium, calcium, silicon and the like in the furnace burden are oxidized in an oxygen-enriched environment to form oxides, and the oxides are combined with quartz stone to form tailings, so that the separation of non-copper metal elements and copper is realized. The iron oxide can reduce copper in the copper oxide and the copper sulfide, and the copper content is improved. The semi-coke is used as fuel, the fixed carbon is high, the combustion provides enough energy, the chemical activity is high, and the semi-coke can also play a role of a reducing agent.
Furthermore, the adding proportion of the copper-containing bricks, limestone, quartz stone, iron oxide and semi-coke is 10 (0.6-1): (0.6-1): 5-7 by weight.
By adopting the scheme, the phenomenon that the good effect of separating non-copper elements cannot be realized due to insufficient addition of limestone, quartz stone and iron oxide or insufficient fluidity of tailings caused by insufficient reaction of iron, molybdenum, magnesium, calcium and silicon can be avoided, and the phenomenon that the addition of semi-coke is insufficient and sufficient energy cannot be ensured can be avoided. And the addition of limestone, quartz stone and iron oxide is too much, so that a large amount of tailings are easily covered on the surface of a molten pool, oxygen cannot enter the molten pool to generate oxidation reaction, and the addition of semi-coke is too much, so that insufficient combustion is caused, and energy waste is caused.
Further, the adding proportion of the copper-containing brick, limestone, quartz stone, iron oxide and semi-coke is 10:1:1: 7 by weight.
By adopting the scheme, the copper content of the prepared matte is high, the sum of the contents of non-copper metal elements is low, no splashing or drying occurs during smelting, and the operability is high.
Further, the limestone, quartzite and iron oxide are added to the cement in step 3 to prepare a copper-containing brick.
By adopting the scheme, the limestone, the quartz stone and the iron oxide are added into the cement to be used for making bricks in the brick making process, and the limestone and the quartz stone fluxing agent are directly contacted with a copper-containing material after being melted in the smelting process, so that the melting of the material is promoted, the oxide formed by non-copper metal elements in an oxygen-enriched environment is facilitated, the oxide is directly combined with the quartz stone to form tailings, the reaction is promoted to be rapidly and thoroughly carried out, and the copper content is increased and the content of the non-copper metal elements is reduced.
Furthermore, in the step 3, sodium dodecyl benzene sulfonate and calcium stearate are also added into the cement, and the adding proportion of the cement, the sodium dodecyl benzene sulfonate and the calcium stearate is 0.4 (0.04-0.08) to 0.04-0.08 by weight.
By adopting the scheme, the sodium dodecyl benzene sulfonate can form bubbles in the cement, and the calcium stearate can ensure the temperature stability of the stable bubbles, so that a plurality of holes are formed in the prepared copper-containing brick. After the copper-containing brick is added into a smelting furnace, limestone and quartz stone are quickly melted and dispersed in a porous structure of cement, so that the cement melting is promoted, the viscosity of slag is reduced, the fluidity of the slag is improved and maintained, and the slag melting speed is accelerated; and the release of bubbles in the porous structure is helpful for stirring the solution, promoting the uniformity of smelting, and leading the oxidation reaction and the reduction reaction to be fully carried out, further promoting the separation of non-copper metal elements.
Further, the crushing in the step 2 comprises three-time crushing, the substrate is subjected to primary crushing by a double-roller crusher and secondary crushing by a crusher and then enters a vibrating screening machine, the mesh number of a screen is 200 meshes, and oversize materials are returned to a secondary crushing section for three-time crushing.
By adopting the technical scheme, the particles obtained after crushing meet the particle size requirement through three times of crushing, and the separation requirement of nonmetal and metal particles is met.
Further, the sorting in the step 2 comprises sorting the undersize products by a specific gravity sorting machine and an electrostatic sorting machine respectively.
By adopting the technical scheme, the separation rate of the metal is improved by twice separation, so that the separation rate is up to more than 98%.
Furthermore, the copper content of the ingredients is adjusted by adopting fine copper powder, and the copper content of the fine copper powder is between 10 and 50 weight percent.
By adopting the technical scheme, the copper content is adjusted by utilizing the recovered copper fine powder, and the recovery utilization rate of copper is further improved.
In conclusion, the invention has the following beneficial effects:
1. according to the waste copper recycling process, copper-containing clinker prepared from hazardous waste and copper-containing powder prepared from a waste circuit board are used for preparing copper-containing bricks, and separation of non-copper metal elements is realized and the copper content is increased through oxygen-enriched smelting;
2. in the smelting process, after the limestone and the quartz stone fluxing agent are melted, the limestone and the quartz stone fluxing agent are directly contacted with a copper-containing material to promote the melting of the material, so that oxides formed by non-copper metal elements in an oxygen-enriched environment are facilitated, the oxides are directly combined with the quartz stone to form tailings, the reaction is promoted to be rapidly and completely carried out, and the copper content is increased and the content of the non-copper metal elements is reduced.
3. The preparation of the porous copper-containing brick reduces the bonding strength of cement, and bubbles released in a porous structure in the smelting process are utilized, so that the solution is stirred, the smelting uniformity is promoted, the reaction is more fully performed, the separation of non-copper metal elements is further promoted, and the copper content is increased.
Detailed Description
The present invention will be described in further detail with reference to examples.
The types and sources of the raw materials related to the invention are shown in table 1, and the main equipment adopted in the process flow is shown in table 2.
TABLE 1 type and Source of raw materials
| Raw materials | Specification/model | Manufacturer of the product |
| Limestone | 100 mesh | Singing mine product |
| Quartz stone | 100 mesh | Singing mine product |
| Iron oxide | 300 mesh | Chemical engineering of moisture |
| Semi coke | ≤6mm | Coal industry of "Shenmu" coal |
| Cement | P.O.42.5 | Sea snail cement |
| Sodium dodecyl benzene sulfonate | 80R | Kanieer brand |
| Calcium stearate | CV-A | Eastern chemical industry |
Table 2 main equipment used in the process flow
Example 1
The process for recovering metallic copper from copper-containing waste provided by embodiment 1 comprises the following preparation steps:
step 1, preparing copper-containing clinker:
various dangerous wastes (except HW49) are transported to a dangerous waste area warehouse by a closed truck and are conveyed into a rotary kiln feed hopper through a feeder, and a pusher and an air locking facility are arranged below the feed hopper to ensure the negative pressure operation of the rotary kiln.
Hazardous wastes (including HW12 dye, coating wastes, HW17 surface treatment substances, HW22 copper-containing wastes, HW45 organic halide-containing wastes, HW46 nickel-containing wastes, HW48 non-ferrous metal smelting wastes and HW50 waste catalysts, and 95000t/a in total) in raw materials can enter the rotary kiln after the copper content reaches 22 wt%.
The burning temperature in the rotary kiln is 850 ℃, semi-coke is used as fuel, and the time is 1 h. High-temperature flue gas generated by incineration passes through a cyclone dust collector and then is subjected to secondary combustion, the temperature of a secondary chamber is about 1150 ℃, and the residence time of the flue gas in a high-temperature area is more than 2 seconds, so that harmful substances such as dioxin, heavy metal and the like are reduced. When the temperature is lower than 1150 ℃, the burner of the second combustion chamber adjusts the big and small fire to be opened. The furnace temperature is ensured to be stabilized at about 1150 ℃, and all air for combustion in the rotary kiln and the second combustion chamber is respectively supplied by a fan, so that the combustion of wastes is in an optimal state. High-temperature flue gas from the secondary combustion chamber enters a waste heat boiler, and steam generated by waste heat is used as a material for heating in a plant area and drying in a storehouse. The flue gas after passing through the waste heat boiler enters a chilling device to chill the high-temperature flue gas to about 150 ℃, the high-temperature flue gas in the front channel not only fully decomposes the dioxin from the source, but also the high-temperature flue gas in the rear channel chills the dioxin to avoid or greatly shorten the dioxin regeneration working condition area of 350-500 ℃. The flue gas is subjected to active carbon adsorption of residual harmful substances, subjected to dust removal by a pulse bag type dust remover, then enters a desulfurizing tower, is subjected to desulfurization by a double alkali method, and finally is discharged through an exhaust funnel of 80m by an induced draft fan.
After the dangerous waste is burnt in the rotary kiln, the copper-containing clinker is generated and discharged from the tail part of the rotary kiln, and the copper-containing clinker is sent to a briquetting and brick making system. By incineration, the organic compounds in the hazardous waste (except HW49) are removed to produce carbon dioxide and water, and copper-containing clinker is obtained, so that the hazardous waste is reduced and harmless.
Step 2, preparing copper-containing powder:
advanced integrated disassembling equipment is selected as the preprocessing equipment of the waste circuit board (the hazardous waste category is HW49), the waste circuit board is disassembled to remove surface electronic elements to obtain a substrate, and the PLC is adopted to control the uniform feeding of the whole production line. The principle of crushing and screening is 'three-stage crushing + air flow separation', the materials are primarily crushed by a double-roller crusher in sequence, the materials enter a vibrating screening machine after being secondarily crushed by a crusher, the mesh number of a screen is 100 meshes, oversize materials return to a secondary crushing workshop section for secondary crushing, undersize materials are separated by a specific gravity separator and an electrostatic separator respectively to separate copper-containing powder materials from nonmetal (epoxy resin powder), a crushing chamber adopts circulating water for temperature control and noise reduction, a complete set of production line adopts negative pressure feeding to effectively reduce dust overflow, a material returning system enables crushing to be more efficient, the separation rate of air flow separation equipment is up to more than 98%, and the crushing workshop section of the pretreatment equipment is provided with a pulse dust collector to collect dust.
And (3) sending the epoxy resin powder separated by the circuit board pretreatment to a domestic garbage landfill for treatment, and sending the separated copper-containing powder to a brick making system.
Step 3, brick making:
copper-containing clinker from a rotary kiln and copper-containing powder generated by circuit board pretreatment are mixed by a closed mixing machine, fine copper powder with the copper content of 10-50% is added to control the copper content to reach 25% by weight, and the mixture is added with coagulant cement and water to prepare a copper-containing brick. Wherein, the copper-containing material: (cement + water) ═ 18:1, water-cement ratio 0.4. And in the material mixing process, analyzing the element content by a spectrum analyzer.
Step 4, smelting:
taking 10kg of copper-containing bricks prepared in a brick making process, adding 0.6kg of limestone, 0.6kg of quartz stone, 0.6kg of iron oxide powder and 5kg of semi coke, conveying the copper-containing bricks to the upper part of a side-blown smelting furnace, feeding the copper-containing bricks into the furnace from a furnace top feed opening, blowing oxygen into the furnace by an air blower at the same time to ensure that the oxygen in air entering the furnace reaches 28 vol%, and enabling the materials to pass through a preheating zone and a reducing zone under the action of self weight in the furnace to finish the whole smelting process. The smelting temperature of the smelting furnace is 1100 ℃, the primary copper liquid is discharged from the smelting furnace within 2.5 hours, and the primary slag is discharged within 0.5 hour. The tailings are light and are discharged from an upper slag discharge port; and returning the copper content of the tailings to the smelting furnace for continuous smelting according to the copper content, and processing the tailings into copper fine powder with low copper content. The matte obtained by smelting is heavier and sinks at the lower layer, and can flow out from a copper discharge port at the lower part of the smelting furnace to be used as an intermediate product to be sent to a common solid waste area for further smelting. And (2) performing subsequent smelting, namely mixing copper matte, quartz stone, limestone fluxing agent and iron oxide powder reducing agent, which are intermediate products produced in a hazardous waste disposal area and common waste containing copper, and smelting at high temperature, further combining the quartz stone with iron, molybdenum, magnesium, calcium, silicon and the like in the materials to form tailings, and obtaining the remaining copper-containing product, wherein the copper content can be increased to 93-96%.
And step 5, treating the flue gas of the smelting furnace.
The main pollutants in the smoke of the smelting furnace are smoke dust, sulfur dioxide, nitrogen oxide, dioxins and metal compounds (containing heavy metals) which pass through the cycloneThe process comprises the following steps of dust removal, a secondary combustion chamber, a waste heat boiler, a quench tower, activated carbon adsorption, a pulse bag dust collector and a desulfurization spray tower, so that main pollutants in the smoke of the smelting furnace can be discharged up to the standard. High-temperature dust-containing flue gas produced by a smelting furnace enters a secondary combustion chamber after large-particle-size particles are removed by 1 cyclone dust collector, combustion-supporting air and natural gas are blown in, unburned materials and CO in the flue gas are fully combusted at the temperature higher than 1200 ℃, the residence time of the flue gas is longer than 2 seconds, dioxin is thoroughly decomposed, and part of metal dust is settled. The main chemical reactions that take place in post combustion are as follows: 2CO + O2＝2CO2. High-temperature flue gas from the secondary combustion chamber is firstly recycled by waste heat boilers (each furnace is provided with 1 6t/h waste heat boiler) to generate steam, so that the temperature of the flue gas is reduced to about 600 ℃, and then the flue gas enters a chilling device. The steam generated by the waste heat is used for heating, heat supply and power generation in the plant area. The quenching tower quenches the flue gas to about 150 ℃ within 1 second, thereby avoiding the generation of harmful gas dioxin. And harmful gases such as dioxin, metal dust and the like possibly remaining in the flue gas are adsorbed in the outlet flue through the activated carbon. The chilling avoids or greatly shortens a 350-500 ℃ dioxin regeneration working condition area, and the generation of dioxin is greatly reduced. The flue gas finally enters a pulse bag type dust collector, and the dust removal efficiency of the flue gas is over 99.5 percent. Desulfurizing by double alkali method, wherein the flue gas is contacted with NaOH absorption liquid from top to bottom in countercurrent in a reverse spray pipe from top to bottom, and SO is generated after the gas and the liquid are fully contacted2Reacting with halogen and NaOH absorption liquid to generate Na2SO3Simultaneously, the temperature of the flue gas is reduced to 70 ℃, and more than 80 percent of SO in the flue gas2Absorbed, the flue gas is desulfurized and purified in the absorption tower, the water mist is removed by the demister, the flue gas is discharged into the atmosphere through the direct exhaust chimney at the top of the desulfurization tower, and the clean flue gas reaching the standard is converged into the exhaust funnel and discharged. The desulfurized alkali liquor is recycled, and NaOH absorbs SO2Then sodium sulfite is generated, the sodium sulfite is oxidized to react with calcium hydroxide and then is converted into calcium sulfate precipitate, and after the calcium sulfate is fished out, the NaOH waste liquid is recycled as a desulfurizer and is not discharged. The desulfurization efficiency is designed to be 95%.
Example 2
Embodiment 2 provides a copper recovery process for copper-containing waste metal, which includes the following steps:
step 1, copper-containing clinker is prepared, and the difference with the embodiment 1 is that the burning time in the rotary kiln is 1.5 h.
Step 2, preparing copper-containing powder: the same procedure was followed as in example 1.
Step 3, brick making:
the difference from example 1 is that the copper-containing clinker, copper-containing powder also has added to it tailings or refining slag.
Step 4, smelting:
the difference from example 1 was that the amount of limestone added was 0.8kg, the amount of quartz added was 0.8kg, the amount of iron oxide powder added was 0.8kg, the amount of semi coke added was 6kg, the oxygen content in the furnace air was 29 vol%, and the melting temperature of the melting furnace was 1150 ℃.
Step 5, the treatment of the smelting furnace flue gas is the same as the treatment process in the embodiment 1.
Example 3
Embodiment 3 provides a copper recovery process for copper-containing waste metal, which includes the following steps:
step 1, copper-containing clinker is prepared, which is the same as the preparation method of the embodiment 1.
Step 2, preparing copper-containing powder: the same procedure was followed as in example 1.
Step 3, brick making: the same procedure was followed as in example 1.
Step 4, smelting:
the difference from example 1 was that the amount of limestone added was 1kg, the amount of quartz stone added was 1kg, the amount of iron oxide powder added was 1kg, the amount of semi coke added was 7kg, the oxygen content in the furnace air was 30vol%, and the melting temperature of the melting furnace was 1200 ℃.
Step 5, the treatment of the smelting furnace flue gas is the same as the treatment process in the embodiment 1.
Example 4
Embodiment 4 provides a copper recovery process of copper-containing waste material, including the following steps:
step 1, copper-containing clinker is prepared, which is the same as the preparation method of the example 3.
Step 2, preparing copper-containing powder: the same procedure was followed as in example 3.
Step 3, brick making:
the difference from example 3 is that: limestone, quartz stone and ferric oxide are added into cement together to prepare the copper-containing brick. Wherein, the proportion of the copper-containing material, limestone, quartz stone, ferric oxide, (cement and water with the water-cement ratio of 0.4) is 10:0.6:0.6:0.6:0.56 by weight.
Step 4, smelting:
10kg of copper-containing bricks prepared in the brick making process are conveyed to the upper part of a side-blown smelting furnace, are put into the furnace from a furnace top feed opening and are conveyed to the upper part of the side-blown smelting furnace, are put into the furnace from the furnace top feed opening, and are blown with oxygen into the furnace by a blower at the same time, so that the oxygen in the air entering the furnace reaches 30vol percent, and the materials pass through a preheating zone and a reduction zone under the action of the dead weight in the furnace to finish the whole smelting process. The smelting temperature of the smelting furnace is 1200 ℃, the primary copper liquid is discharged from the smelting furnace for 2.5 hours, and the primary slag is discharged from the smelting furnace for 0.5 hour. The tailings are light and are discharged from an upper slag discharge port; and returning the tailings with high copper content to a smelting furnace for continuous smelting according to the copper content, and processing the tailings into copper fine powder with low copper content. The matte obtained by smelting is heavier and sinks at the lower layer, and can flow out from a copper discharge port at the lower part of the smelting furnace to be used as an intermediate product to be sent to a common solid waste area for further smelting.
Step 5, treatment of the smelting furnace flue gas, which is the same as the treatment process of the embodiment 3.
Example 5
Embodiment 5 provides a copper-containing waste material copper recovery process, including the following steps:
step 1, copper-containing clinker is prepared, which is the same as the preparation method of example 4.
Step 2, preparing copper-containing powder: the same procedure was followed as in example 4.
Step 3, brick making: the difference from example 4 is that the ratio of copper-containing material, limestone, quartzite, iron oxide, (cement + water, water to cement ratio 0.4) is 10:0.8:0.8:0.8:0.56 by weight.
Step 4, smelting: the same as the melting process of example 4.
Step 5, the treatment of the smelting furnace flue gas is the same as the treatment process in the embodiment 4.
Example 6
Embodiment 6 provides a copper-containing waste material copper recovery process, including the following steps:
step 1, copper-containing clinker is prepared, which is the same as the preparation method of example 4.
Step 2, preparing copper-containing powder: the same procedure was followed as in example 4.
Step 3, brick making: the difference from example 4 is that the ratio of copper-containing material, limestone, quartzite, iron oxide, (cement + water, water-to-cement ratio 0.4) is 10:1:1:1:0.56 by weight.
Step 4, smelting: the same as the melting process of example 4.
Step 5, the treatment of the smelting furnace flue gas is the same as the treatment process in the embodiment 4.
Example 7
Embodiment 7 provides a copper-containing waste material copper recovery process, including the following steps:
step 1, copper-containing clinker is prepared, which is the same as the preparation method of example 5.
Step 2, preparing copper-containing powder: the same procedure was followed as in example 5.
Step 3, brick making: the difference from the embodiment 5 is that sodium dodecyl benzene sulfonate and calcium stearate are also added into the cement, and the adding proportion of the cement, the sodium dodecyl benzene sulfonate and the calcium stearate is 0.4:0.04:0.04 by weight.
Step 4, smelting: the same as the melting process of example 5.
Step 5, treatment of the smelting furnace flue gas, which is the same as the treatment process of the embodiment 5.
Example 8
Embodiment 8 provides a copper-containing waste material copper recovery process, including the following steps:
step 1, copper-containing clinker was prepared, the same as in example 5.
Step 2, preparing copper-containing powder: same preparation as in example 5.
Step 3, brick making: the difference from the embodiment 5 is that the cement is also added with sodium dodecyl benzene sulfonate and calcium stearate, and the adding proportion of the cement, the sodium dodecyl benzene sulfonate and the calcium stearate is 0.4:0.06:0.06 by weight.
Step 4, smelting: the same as the melting process of example 5.
Step 5, treatment of the smelting furnace flue gas, which is the same as the treatment process of the embodiment 5.
Example 9
Embodiment 9 provides a copper-containing waste material copper recovery process, including the following steps:
step 1, copper-containing clinker was prepared, the same as in example 5.
Step 2, preparing copper-containing powder: same preparation as in example 5.
Step 3, brick making: the difference from the embodiment 5 is that the cement is also added with sodium dodecyl benzene sulfonate and calcium stearate, and the adding proportion of the cement, the sodium dodecyl benzene sulfonate and the calcium stearate is 0.4:0.08:0.08 by weight.
Step 4, smelting: the same as the melting process of example 5.
Step 5, treatment of the smelting furnace flue gas, which is the same as the treatment process of the embodiment 5.
Comparative example 1
Comparative example 1 provides a copper-containing scrap metal copper recovery process, including the following steps:
step 1, copper-containing clinker is prepared, which is the same as the preparation method of the embodiment 1.
Step 2, preparing copper-containing powder: the same procedure was followed as in example 1.
Step 3, brick making: the same procedure was followed as in example 1.
Step 4, smelting:
the difference from example 1 is that: in step 4, the addition amount of limestone is 0.4kg, the addition amount of quartz stone is 0.4kg, and the addition amount of iron oxide is 0.4 kg.
Step 5, the treatment of the smelting furnace flue gas is the same as the treatment process in the embodiment 1.
Comparative example 2
Comparative example 2 provides a copper-containing waste metal copper recovery process, including the following steps:
step 1, copper-containing clinker is prepared, which is the same as the preparation method of the example 3.
Step 2, preparing copper-containing powder: the same procedure was followed as in example 3.
Step 3, brick making: the same procedure was followed as in example 3.
Step 4, smelting:
the difference from example 3 is that: in step 4, the addition amount of limestone is 1.2kg, the addition amount of quartz stone is 1.2kg, and the addition amount of iron oxide is 1.2 kg.
Step 5, treatment of the smelting furnace flue gas, which is the same as the treatment process of the embodiment 3.
Performance detection
Aiming at the recovery process of the copper-containing waste metal copper provided by the embodiments 1-9 and the comparative examples 1-2 of the invention, the slag-forming time is monitored and whether the splashing and drying-back phenomena occur or not is observed and recorded in the smelting process, the prepared matte is subjected to spectral analysis, the copper content and the sum of the contents of non-copper metal elements (including iron, molybdenum, magnesium, calcium and silicon) in the matte are measured and recorded, and the detection result is shown in table 3.
TABLE 3 Performance test data sheet
The present invention is described in detail below with reference to the performance measurement data table provided in table 3.
A comparison was made in examples 1-3 for limestone, quartzite and iron oxide ratios. The result shows that in example 1, the adding amount of limestone, quartz stone and iron oxide is relatively small, the slagging time is long, no spraying or drying-back occurs in the smelting process, the operability is good, the copper content of the prepared matte is high, and the total content of non-copper metal elements is low; the limestone and quartz stone fluxing agent are melted in the smelting process and combined with iron, molybdenum, magnesium, calcium, silicon and the like in the materials to form tailings, iron oxide can reduce copper oxide, and as the addition amount of the limestone, quartz stone and iron oxide is increased, more non-copper metal elements enter the tailings, the reduction of the copper oxide is more sufficient, so that the copper content in the prepared matte is increased, and the sum of the contents of the non-copper metal elements is reduced; example 3 is relatively preferred.
In addition, in the present invention, the influence of the addition mode of limestone, quartz stone and iron oxide was examined in examples 4 to 6 by referring to example 3 as a control. As a result, in example 4, in the brick making process, the limestone, the quartzite and the iron oxide are added into the cement to make bricks together, so that the dispersibility and uniformity of the limestone, the quartzite and the iron oxide in the copper-containing material are improved, the reaction between the limestone, the quartzite and the iron oxide and the copper-containing material in the smelting process is promoted, the slag formation time is short, the reaction speed is high, the copper content of the prepared matte is increased, the sum of the non-copper metal content is reduced, and the spraying and drying-back phenomena are avoided; in the embodiment 5, the addition amounts of limestone, quartz stone and iron oxide are increased, the slag forming time is further shortened, the copper content of the prepared matte is further improved, and the sum of the non-copper metal content is further reduced; in example 6, since the limestone is added in a large amount and is dispersed in the copper-containing material, the limestone reacts violently with the copper-containing material, the slagging time is short, the formed slag covers the surface of the furnace liquid, the amount of oxygen transferred into the molten bath is reduced, the oxidation reaction of non-copper metal elements is not facilitated, the copper content is reduced, and the sum of the contents of the non-copper metal elements is increased.
The present invention examines the effect of adding a foaming agent and a foam stabilizer to cement in examples 7 to 9. As a result, it was found that, compared with example 5, in example 7, since the pores in the cement have a certain thermal insulation effect, the limestone and quartz stone are melted slowly, the slagging time is increased, and during the melting process, as the cement is softened, the bubbles in the pores are released continuously to play a role of stirring the furnace liquid, so that the reaction is carried out more completely, the copper content in the finally prepared matte is further increased, and the content of the sum of the non-copper metal elements is further decreased, especially in example 8, which is relatively preferable. In example 9, the pores in the cement are further increased, the heat insulation is obvious, the slagging time is long, the release amount of bubbles in the pores is increased, the tailing rising speed is too high, the reaction is not fully performed, the copper content of the prepared matte is reduced compared with that of example 5, and the sum of the contents of non-copper metal elements is increased.
Compared with the embodiment 1, the slag forming time of the comparative example 1 is long, the phenomena of injection and drying return occur in the smelting process, the operability is poor, the copper content of the prepared copper matte is low, and the sum of the contents of non-copper metal elements is high. Compared with the embodiment 3, in the comparative example 2, in the smelting process, the slag-forming time is short, the tailings are too much, the surface of the molten pool is covered, the oxygen amount transmitted into the molten pool is too little, the reaction is not facilitated, and the copper content is reduced, but the sum of the contents of the elements other than copper is increased.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.
Claims (9)
1. The recovery process of the copper from the copper-containing waste material is characterized by comprising the following steps:
step 1, preparing copper-containing clinker, namely blending the hazardous wastes until the copper content reaches 22wt%, putting the hazardous wastes into a rotary kiln for incineration at the temperature of 850 ℃ for 1-1.5h, generating the copper-containing clinker after the incineration is finished, discharging the copper-containing clinker from the tail part of the rotary kiln, and sending the copper-containing clinker to a briquetting and brick making system;
step 2, preparing copper-containing powder, disassembling the waste circuit board to obtain a substrate, crushing and sorting the substrate to obtain the copper-containing powder, and conveying the copper-containing powder to a briquetting and brick making system;
step 3, brickmaking, namely blending the copper-containing clinker prepared in the step 1 and the copper-containing powder prepared in the step 2 until the copper content reaches more than 25wt%, entering a brickmaking system, and adding water into coagulant cement to prepare a copper-containing brick;
step 4, smelting, namely putting the copper-containing bricks prepared in the step 3 into a smelting furnace, blowing oxygen into the furnace to ensure that the oxygen in the air entering the furnace reaches 28-30vol%, adding a fluxing agent, a reducing agent and fuel, wherein the smelting temperature is 1100-1200 ℃, primary slag is discharged within 0.5h, primary copper liquid is discharged within 2.5h, and the copper liquid is discharged from a copper outlet at the lower part of the smelting furnace;
and step 5, treating the flue gas of the smelting furnace.
2. The process of claim 1, wherein the fluxing agent is limestone or quartzite, the reducing agent is iron oxide, and the fuel is semi-coke.
3. The process for recovering metallic copper from copper-containing wastes as recited in claim 2, wherein the ratio of said copper-containing bricks to the addition of limestone, quartzite, iron oxide and semi-coke is 10 (0.6-1): 5-7 by weight.
4. The process for recovering copper from copper-containing waste metal according to claim 3, wherein the addition ratio of the copper-containing bricks to limestone, quartzite, iron oxide and semi-coke is 10:1:1:1:7 by weight.
5. The process for recovering metallic copper from copper-containing waste materials as recited in claim 4, wherein in said step 3, sodium dodecylbenzene sulfonate and calcium stearate are further added to cement, and the adding ratio of said cement, sodium dodecylbenzene sulfonate and calcium stearate is 0.4 (0.04-0.08) to (0.04-0.08) by weight.
6. The process of claim 1, wherein the crushing in step 2 comprises three times of crushing, the substrate is subjected to primary crushing by a double-roller crusher, the crushed substrate is subjected to secondary crushing by a crusher and then enters a vibrating screening machine, the mesh number of the screen is 200 meshes, and the oversize material returns to the secondary crushing section for secondary crushing.
7. The process of claim 1, wherein the sorting in step 2 comprises sorting the undersize by a gravity sorter and an electrostatic sorter, respectively.
8. The process of claim 1, wherein the copper-containing clinker, the copper-containing powder and the tailings are added to produce copper-containing bricks in step 3.
9. The process of claim 1, wherein the copper content of the copper concentrate is adjusted by using a copper concentrate powder, and the copper content of the copper concentrate powder is between 10wt% and 50 wt%.
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| CN111850316A (en) * | 2020-08-01 | 2020-10-30 | 鹰潭市辉腾铜业有限公司 | Copper smelting process and equipment |
| CN111996362B (en) * | 2020-08-26 | 2022-08-12 | 甘肃高能中色环保科技有限公司 | Method for producing nickel block material from nickel-containing solid hazardous waste material |
| CN113088697A (en) * | 2021-03-25 | 2021-07-09 | 洛南环亚源铜业有限公司 | Crude copper treatment process and treatment device thereof |
| CN113048490B (en) * | 2021-03-27 | 2022-10-11 | 洛南环亚源铜业有限公司 | Hazardous waste treatment process and treatment device thereof |
| CN114769269A (en) * | 2022-04-27 | 2022-07-22 | 宁波江丰电子材料股份有限公司 | Recycling method of ultra-pure copper system residual target |
| CN116121554B (en) * | 2023-02-28 | 2024-01-19 | 江西省金瑞环保科技有限公司 | Method for recycling copper by adopting oxygen-enriched smelting furnace |
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