Black copper anode plate casting method

Abstract

The invention belongs to the technical field of hazardous waste resource recovery, and particularly relates to a black copper anode plate which comprises the following steps: S1, carrying out drying pretreatment on hazardous waste containing copper and nickel until the drying moisture is less than or equal to 10%; s2, the hazardous waste containing copper and nickel, metallurgical slag, a copper-containing material, an auxiliary agent and coke are matched and mixed and then fed into an oxygen-enriched side-blown furnace to be smelted; the compatibility meets the following requirements in percentage by mass: 15.21 to 48.93 percent of copper, 2 to 2.87 percent of nickel, 3.63 to 8.7 percent of sulfur and 15 percent of coke; s3, the oxygen-enriched concentration of primary air in the oxygen-enriched side-blown converter is 90%, and the temperature of a molten pool is 1246-1359 DEG C; s4, black copper refers to molten copper alloy formed by smelting valuable metal copper and nickel, and the black copper comprises, by mass, more than or equal to 80% of copper, more than or equal to 10% of nickel and less than or equal to 1.5% of iron; sulfur < = 1%; lead < = 2%; s5, the anode mold is baked, and black copper is poured; and S6, the anode mold is cooled, and the finished black copper anode plate is obtained.

Description

Technical Field

[0001] The invention belongs to the technical field of hazardous waste resource recovery, and in particular relates to a black copper anode plate casting method. Background Art

[0002] Modern copper pyrometallurgy usually involves matte smelting of copper-containing materials. The resulting matte (matte) is sent to a converter for blowing into crude copper, which is then oxidized and refined in an anode furnace to remove impurities, and then cast into anode plates for electrolysis to obtain electrolytic copper with a grade of more than 99.9%. In the hazardous waste treatment industry, pyrometallurgy is also currently used to treat copper-containing hazardous waste. Most of the processes are based on copper pyrometallurgy, using the process of molten pool smelting to smelt the copper in the copper-containing hazardous waste into matte, thereby realizing the resource recovery and utilization of valuable metals in hazardous waste.

[0003] Copper-containing hazardous waste is mostly generated in the electronic processing industry. Due to the limitations of the industry's characteristics, the characteristics of its hazardous waste are that it has a wide range of sources but a small total amount, large deviations in the metal content of the materials, high moisture content, and the coexistence of multiple metal elements, making recycling difficult.

[0004] If the copper pyrometallurgical smelting process is completely copied, it will result in a long process and large investment, and it will not be able to adapt to the industrial characteristics of the hazardous waste treatment industry; secondly, the metal elements in the hazardous waste cannot be effectively recovered, resulting in a waste of metal resources, especially nickel, the most common hazardous waste in the electroplating industry. In the traditional copper smelting process, nickel is usually used as an impurity element. A large amount of nickel (about 90% or more) enters the slag during the slag-making process of blowing, and only a small amount of nickel enters the electrolysis process for recovery, and the recovery rate is low. Summary of the invention

[0005] Based on the problems mentioned in the above background technology, the present invention provides a method for casting a black copper anode plate.

[0006] The technical scheme adopted by the present invention is as follows: a black copper anode plate, comprising the following steps, S1: drying pretreatment of hazardous waste containing copper and nickel, and drying moisture ≤10%; S2: mixing hazardous waste containing copper and nickel, metallurgical slag, copper-containing materials, additives and coke and feeding them into an oxygen-enriched side-blown furnace for smelting; the mixture meets the requirements of a copper content of 15.21-48.93% by mass, a nickel content of 2-2.87%, a sulfur content of 3.63-8.7%, and a coke content of 15% by mass; S3: the primary air oxygen-enriched concentration in the oxygen-enriched side-blown furnace is 90%, and the molten pool temperature is 1246-1359° C.; S4: black copper refers to a copper alloy formed by smelting valuable metals copper and nickel to form a molten state, and its mass percentage content is copper ≥80%, nickel ≥10%, iron ≤1.5%; sulfur ≤1%; lead ≤2%; S5: baking the anode mold and pouring black copper; S6: cooling the anode mold to obtain a finished black copper anode plate.

[0007] Furthermore, in the S2, the mass ratio of copper- and nickel-containing hazardous waste, metallurgical slag and copper-containing materials meets 3:2:2 mixing. After mixing, the chemical composition and its mass percentage are respectively 39.84% copper, 2.28% nickel, 3.63% sulfur, 15% coke, and calcium oxide is used as an auxiliary agent to make up the rest.

[0008] Furthermore, in S3, the average air volume is 4000m 3 / h.

[0009] Furthermore, in S5, the baking mold temperature is set to 60-90° C., and a release agent is applied to the mold surface.

[0010] Furthermore, in S5, the copper tapping temperature is not less than 1300°C.

[0011] Furthermore, the method further comprises step S7: controlling the depth of the molten pool to 1200 mm, starting slag discharge when the depth is higher than 1200 mm, and the height of the copper liquid level not exceeding 450 mm. When the copper liquid level is at a height of 400 mm, preparing for copper discharge.

[0012] Furthermore, the method further comprises step S8: grinding the burrs on the black copper anode plate to ensure that the length of the burrs is no more than 5 mm.

[0013] Beneficial effects of the present invention:

[0014] Through reduction smelting in an oxygen-enriched side-blown furnace, the harmless treatment of hazardous waste containing copper and nickel is achieved, copper and nickel are efficiently recovered, and a short process is realized. It has the characteristics of simple process, short process and high metal recovery rate. While treating hazardous waste, copper, nickel and other metals can be recovered at the same time, which improves economic benefits. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] The present invention can be further illustrated by the non-limiting examples given in the accompanying drawings;

[0016] Figure 1 This is a table of experimental data for Examples 1 to 8 of the present invention. DETAILED DESCRIPTION

[0017] The present invention will be further described below in conjunction with examples, but the present invention is not limited to the following examples.

[0018] Embodiment 1:

[0019] The copper- and nickel-containing hazardous waste is pre-treated by drying, and the drying moisture content is ≤10%; the copper- and nickel-containing hazardous waste, metallurgical slag, copper-containing materials, additives and coke are mixed and fed into an oxygen-enriched side-blown furnace for smelting; the mixture satisfies the copper content of 15.21-48.93% by weight, the nickel content of 2-2.87%, the sulfur content of 3.63-8.7% and the coke content of 15% by weight; the primary air oxygen-enriched concentration in the oxygen-enriched side-blown furnace is 90%, and the molten pool temperature is 1246-1359°C; black copper refers to a copper alloy formed by smelting valuable metals copper and nickel to form a molten state, and its mass percentage content is ≥80% copper, ≥10% nickel, ≤1.5% iron; ≤1% sulfur; ≤2% lead; the anode mold is baked, and the black copper is poured; the anode mold is cooled to obtain a finished black copper anode plate.

[0020] It contains copper and nickel hazardous waste, metallurgical slag, copper-containing materials (including 15.21% copper, 2% nickel, 8.7% sulfur); 15% coke (reducing agent); calcium oxide (auxiliary agent) as the rest, and is sent to an oxygen-enriched side-blown furnace. The molten pool temperature is 1313-1359°C, and the smelting is carried out by primary wind combustion. The copper liquid is discharged from the copper outlet, and the black copper anode plate is cast with the following grades: 79.24% copper, 12.35% nickel, 0.73% iron, 0.48% sulfur, and 0.18% lead.

[0021] Embodiment 2:

[0022] The present embodiment is different from the first embodiment in that copper- and nickel-containing hazardous waste, metallurgical slag, copper-containing materials (including 28.52% copper, 2.33% nickel, and 4.87% sulfur); 15% coke (reducing agent); and calcium oxide (auxiliary agent) are supplemented and sent into an oxygen-enriched side-blown furnace. The molten pool temperature is 1313-1359° C., and smelting is carried out by primary air combustion. The copper liquid is discharged from the copper outlet, and the black copper anode plate obtained by casting has the following grades: 85.27% copper, 11.55% nickel, 1.33% iron, 0.45% sulfur, and 1.81% lead.

[0023] Embodiment three:

[0024] The present embodiment is different from the first embodiment in that copper- and nickel-containing hazardous waste, metallurgical slag, copper-containing materials (including 39.84% copper, 2.28% nickel, and 3.63% sulfur); 15% coke (reducing agent); and calcium oxide (auxiliary agent) are supplemented and sent into an oxygen-enriched side-blown furnace. The molten pool temperature is 1313-1359° C., and smelting is carried out by primary air combustion. The copper liquid is discharged from the copper outlet, and the black copper anode plate obtained by casting has the following grades: 86.09% copper, 11.95% nickel, 1.14% iron, 0.1% sulfur, and 0.64% lead.

[0025] Embodiment 4:

[0026] The present embodiment is different from the first embodiment in that copper- and nickel-containing hazardous waste, metallurgical slag, copper-containing materials (including 48.93% copper, 2.87% nickel, and 4.1% sulfur); 15% coke (reducing agent); and calcium oxide (auxiliary agent) are supplemented and sent into an oxygen-enriched side-blown furnace. The molten pool temperature is 1313-1359° C., and smelting is carried out by primary air combustion. The copper liquid is discharged from the copper outlet, and the black copper anode plate obtained by casting has the following grades: 86.73% copper, 11.83% nickel, 1.09% iron, 0.77% sulfur, and 0.64% lead.

[0027] Embodiment five:

[0028] The present embodiment is different from the first embodiment in that hazardous waste containing copper and nickel, metallurgical slag, copper-containing materials (including 15.21% copper, 2% nickel, and 8.7% sulfur); 15% coke (reducing agent); and calcium oxide (auxiliary agent) are supplemented and sent into an oxygen-enriched side-blown furnace. The molten pool temperature is 1246-1308° C., and smelting is carried out by primary air combustion. The copper liquid is discharged from the copper outlet, and the black copper anode plate obtained by casting has the following grades: 79.9% copper, 11.21% nickel, 1.13% iron, 0.07% sulfur, and 0.6% lead.

[0029] Embodiment six:

[0030] The present embodiment is different from the second embodiment in that the present embodiment contains copper- and nickel-containing hazardous waste, metallurgical slag, copper-containing materials (including 28.52% copper, 2.33% nickel, and 4.87% sulfur); 15% coke (reducing agent); and calcium oxide (auxiliary agent) as a supplement, which are fed into an oxygen-enriched side-blown furnace, the molten pool temperature is 1246-1308° C., and smelting is carried out by primary air combustion assistance. The copper liquid is discharged from the copper outlet, and the black copper anode plate obtained by casting has the following grades: 81.05% copper, 8.87% nickel, 1.14% iron, 0.12% sulfur, and 0.74% lead.

[0031] Embodiment seven:

[0032] The present embodiment is different from the third embodiment in that copper- and nickel-containing hazardous waste, metallurgical slag, copper-containing materials (including 39.84% copper, 2.28% nickel, and 3.63% sulfur); 15% coke (reducing agent); and calcium oxide (auxiliary agent) are added to the surplus and sent to an oxygen-enriched side-blown furnace. The molten pool temperature is 1246-1308°C, and the smelting is carried out by primary air combustion. The copper liquid is discharged from the copper outlet, and the black copper anode plate obtained by casting has the following grades: 82.37% copper, 8.9% nickel, 0.82% iron, 0.73% sulfur, and 0.82% lead.

[0033] Embodiment eight:

[0034] The present embodiment is different from the fourth embodiment in that copper- and nickel-containing hazardous waste, metallurgical slag, copper-containing materials (including 48.93% copper, 2.87% nickel, and 4.1% sulfur); 15% coke (reducing agent); and calcium oxide (auxiliary agent) are supplemented and sent into an oxygen-enriched side-blown furnace. The molten pool temperature is 1246-1308° C., and smelting is carried out by primary air combustion. The copper liquid is discharged from the copper outlet, and the black copper anode plate obtained by casting has the following grades: 82.51% copper, 8.68% nickel, 0.69% iron, 0.31% sulfur, and 1.84% lead.

[0035] Among them, in Examples 1 to 4 and Examples 5 to 8, corresponding materials were used and the temperature was controlled at 1313-1359° C. and 1246-1308° C. respectively to compare the effect of the molten pool temperature on the grade of the finished black copper anode plate.

[0036] The molten copper alloy formed by the valuable metals copper and nickel is also called black copper, and its mass percentage should meet the requirements of copper ≥ 80%, nickel ≥ 10%, iron 1.5%; sulfur ≤ 1%; lead ≤ 2%.

[0037] Therefore, Examples 1, 5, 6, 7 and 8 do not meet this identification standard and are not included in the analysis; it can be seen that the molten pool temperature needs to be controlled at 1313-1359°C, otherwise the nickel grade produced will be affected.

[0038] Comparing Examples 2, 3, and 4, the copper grades of Examples 3 and 4 both reached more than 86%, but the copper grade of Example 4 was only increased by 0.74% compared with that of Example 3. However, the copper compatibility ratio of copper-containing, nickel-containing hazardous waste, metallurgical slag, and copper-containing materials was 22.82% higher than that of Example 3; and the nickel grade of Example 3 was increased by 1.01% compared with that of Example 4. In comparison, Example 3 is identified as the most preferred embodiment.

[0039] Therefore, as a preferred solution, in S2, the mass ratio of copper- and nickel-containing hazardous waste, metallurgical slag and copper-containing materials meets the requirement of 3:2:2. After mixing, the chemical composition and their mass percentage are respectively 39.84% copper, 2.28% nickel, 3.63% sulfur and 15% coke, with calcium oxide as an auxiliary agent to make up the rest.

[0040] As a preferred solution, in S3, the average air supply volume is 4000m 3 / h. Maintain optimal oxygen supply, improve thermal efficiency and ensure consistent product quality.

[0041] As a preferred solution, in S5, the mold temperature is baked to 60-90°C, and a mold release agent is applied to the mold surface to preheat the mold to reduce temperature loss and avoid affecting the casting quality.

[0042] As a preferred solution, in S5, the copper tapping temperature is not less than 1300° C. to ensure the fluidity of the molten metal.

[0043] As a preferred solution, step S7 is also included: controlling the molten pool depth to 1200 mm, starting slag discharge when the depth is higher than 1200 mm, and the copper liquid level does not exceed 450 mm. When the copper liquid level is at a height of 400 mm, preparing for copper discharge.

[0044] Controlling the copper liquid level within a range of no more than 450mm is conducive to achieving the following goals:

[0045] Ensure product quality: Too high a copper liquid level may cause too many impurities to mix into the copper liquid, affecting product quality. By controlling the copper liquid level, you can reduce the mixing of impurities and improve product quality.

[0046] Improve smelting efficiency: The appropriate copper liquid level can ensure more complete heat transfer and material reaction during the smelting process, thereby improving smelting efficiency.

[0047] Ensure copper discharge safety: Start copper discharge when the copper liquid level reaches an appropriate height to ensure the safety of the copper discharge process. Too low copper liquid level may lead to poor copper discharge or difficulty in copper discharge, while too high copper liquid level may increase the safety risk during the copper discharge process.

[0048] Improve copper discharge efficiency: By preparing the copper discharge operation in advance, it can be ensured that the copper discharge operation can be carried out quickly when the copper liquid level reaches an appropriate height, thereby improving the copper discharge efficiency.

[0049] As a preferred solution, the method further includes step S8: grinding the burrs on the black copper anode plate to ensure that the length of the burrs is no more than 5 mm.

[0050] The method principle of the present invention is as follows:

[0051] In the traditional copper smelting process, the production process of smelting-converting-refining is adopted. During the converting process, the nickel, iron and other metals in the minerals all enter the slag during the converting process. The crude copper content of the output is more than 98%, and the nickel content is 0.5-0.8%, resulting in the loss of nickel metal. The reaction process is:

[0052] Melting process:

[0053] FeS+Cu2S+Ni3S2=Cu2S·FeS·Ni3S2(low nickel matte)

[0054] 2FeO+SiO2=(2FeO·SiO2)

[0055] Blowing process:

[0056] Slag-making period: 2FeS+3O2=2FeO+2SO2

[0057] 2FeO+SiO2=2FeO SiO2

[0058] 2Ni3S2+7O2=6NiO+4SO2

[0059] 2NiO+SiO2=2NiO·SiO2

[0060] Copper making period: Cu2S+1.5O2=Cu2O+SO2

[0061] Cu2S+2Cu2O=6Cu+SO2

[0062] It can be seen from the above reaction that nickel will enter the matte to form a low-nickel matte alloy during the smelting process, but will be oxidized and react with quartz to enter the slag during the slag-making period during the blowing process and cannot be recovered.

[0063] Different from the blowing and impurity removal process in the copper smelting process, the present invention retains the nickel metal element as much as possible during the smelting process. Since there is no blowing process, nickel enters the copper melt in a reducing atmosphere to form a copper-nickel alloy, and impurity elements such as iron and calcium are slag-formed and discharged, and sulfur is oxidized and enters the flue gas. The black copper anode plate produced by casting can be used for black copper electrolysis to recover copper and nickel, thereby maximizing economic benefits.

[0064] The reaction process is:

[0065] Melting process

[0066] Reduction reaction

[0067] C+O2=CO2

[0068] 2C+O2=2CO

[0069] CO2+C=2CO

[0070] CuSO4=CuO+SO3

[0071] Ni2O3+3CO=2Ni+3CO2

[0072] CuO+CO=Cu+CO2

[0073] 2CuO+SO2+4CO=Cu2S+4CO2

[0074] 2CuS+FeO+CO=Cu2S+FeS+CO2

[0075] 2Cu2S+2CO+3O2=4Cu+2SO2+2CO2

[0076] Slag forming reaction

[0077] 2FeS+4O2=2FeO+3SO2

[0078] 2FeO+SiO2=2FeO·SiO2

[0079] CaO+SiO2=CaO·SiO2

[0080] The reaction shows that nickel and copper are reduced to form a copper-nickel alloy, namely black copper, which is conducive to subsequent recovery.

[0081] The present invention has been described in detail above. The description of the specific embodiments is only used to help understand the method of the present invention and its core concept. It should be pointed out that for ordinary technicians in this technical field, without departing from the principle of the present invention, several improvements and modifications can be made to the present invention, and these improvements and modifications also fall within the scope of protection of the claims of the present invention.

Claims

1. A method for casting a black copper anode plate, characterized in that: The following steps are involved: S1: Drying pretreatment of hazardous waste containing copper and nickel, with drying moisture ≤10%; S2: Mix the copper- and nickel-containing hazardous wastes, metallurgical slag, copper-containing materials, additives and coke and feed them into an oxygen-enriched side-blown furnace for smelting; the mixture shall satisfy the mass percentage of copper content of 15.21-48.93%, nickel content of 2-2.87%, sulfur content of 3.63-8.7% and coke content of 15%; S3: The oxygen-enriched concentration of the primary air in the oxygen-enriched side-blowing furnace is 90%, and the molten pool temperature is 1246-1359°C; S4: Black copper refers to a copper alloy formed by melting valuable metals copper and nickel, with a mass percentage of copper ≥ 80%, nickel ≥ 10%, iron ≤ 1.5%, sulfur ≤ 1%, and lead ≤ 2%. S5: baking the anode mold and pouring black copper; S6: Cooling the anode mold to obtain a finished black copper anode plate.

2. A method according to claim 1, characterized in that: In the S2, the mass ratio of copper- and nickel-containing hazardous waste, metallurgical slag and copper-containing materials meets 3:2:

2. After mixing, the chemical composition and its mass percentage are respectively 39.84% copper, 2.28% nickel, 3.63% sulfur, 15% coke, and calcium oxide is used as an auxiliary agent to make up the rest.

3. A method according to claim 1, characterized in that: In S3, the average air volume is 4000m 3 / h.

4. A method according to claim 1, characterized in that: In S5, the mold temperature is baked to 60-90° C., and a release agent is applied to the mold surface.

5. A method according to claim 1, characterized in that: In the step S5, the copper tapping temperature is not less than 1300°C.

6. A method according to claim 1, characterized in that: The method also includes step S7: controlling the depth of the molten pool to 1200 mm, starting slag discharge when the depth is higher than 1200 mm, and preparing for copper discharge when the copper liquid level is at a height of 400 mm.

7. A method according to claim 6, characterized in that: The method further comprises step S8: grinding the burrs on the black copper anode plate to ensure that the length of the burrs is no more than 5 mm.

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