CN109536730B - A kind of method for extracting lead-bismuth alloy from copper anode slime smelting waste residue - Google Patents
A kind of method for extracting lead-bismuth alloy from copper anode slime smelting waste residue Download PDFInfo
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Abstract
本发明属于冶金技术领域，涉及一种铜阳极泥冶炼废渣中提取铅铋合金的方法。包括以下步骤：将铜阳极泥冶炼废渣和熔剂混合加入到卡尔多炉中还原熔炼，还原熔炼后扒渣得到粗铅铋合金，将粗铅铋合金熔体转运至中频炉后依次进行熔析除铜、加硫除镍、加锌分银得精铅铋合金；所述熔剂包括焦炭、石灰石和碳酸钠，所述熔剂各组分的加入量以铜阳极泥冶炼废渣质量百分比计：焦炭5‑6%、石灰石15‑19%、碳酸钠2‑4%。本发明所得精铅铋合金含铅品位较高、杂质少，可直接进行铅电解分离回收铅和铋，银锌壳返炉回收金和银，实现了铜阳极泥冶炼废渣中铅铋和金银的高效分离和回收。The invention belongs to the technical field of metallurgy, and relates to a method for extracting lead-bismuth alloy from copper anode slime smelting waste residue. The method comprises the following steps: mixing the copper anode slime smelting waste slag and flux into a Kaldor furnace for reduction and smelting, removing the slag after reduction and smelting to obtain a crude lead-bismuth alloy, transferring the crude lead-bismuth alloy melt to an intermediate frequency furnace, and sequentially performing melting and precipitation removal. Copper, adding sulfur to remove nickel, adding zinc and adding silver to obtain a refined lead-bismuth alloy; the flux includes coke, limestone and sodium carbonate, and the addition of each component of the flux is calculated in terms of the mass percentage of copper anode slime smelting waste residue: coke 5- 6%, limestone 15-19%, sodium carbonate 2-4%. The refined lead-bismuth alloy obtained by the method has higher lead grade and less impurities, and can be directly electrolytically separated to recover lead and bismuth, and the silver-zinc shell can be returned to the furnace to recover gold and silver, thereby realizing lead-bismuth and gold-silver in copper anode slime smelting waste slag. efficient separation and recovery.
Description
技术领域technical field
本发明属于冶金技术领域，涉及一种铜阳极泥冶炼废渣中提取铅铋合金的方法。The invention belongs to the technical field of metallurgy, and relates to a method for extracting lead-bismuth alloy from copper anode slime smelting waste residue.
背景技术Background technique
铜阳极泥的主要处理工艺湿法和火法相结合的工艺，“铜阳极泥－加压浸出铜、碲－火法熔炼、吹炼－银电解－银阳极泥回收金”，在火法熔炼的过程中产生的冶炼废渣中含金和银较低，含铅和铋高，一般含Ag0.1-0.3%、含Au5-20g/t，含Pb25-30%、含Bi4-6%，该部分铜阳极泥冶炼废渣量较大，含Ag较低，无法返回铜阳极泥火法冶炼系统回收贵金属，一般进入铜冶炼系统进一步富集金银至铜阳极泥，造成了金银的分散损失，且铅铋部分进入铜冶炼废渣中，造成铅铋的损失。采用该方法处理铜阳极泥冶炼废渣，铅铋无法回收且处理流程长，成本较高。The main processing technology of copper anode slime is a combination of wet method and fire method, "copper anode slime - pressure leaching of copper, tellurium - pyro process smelting, blowing - silver electrolysis - silver anode slime recovery of gold", in the fire smelting process. The smelting slag produced in the process contains low gold and silver, high lead and bismuth, generally contains Ag0.1-0.3%, Au5-20g/t, Pb25-30%, Bi4-6%, this part The amount of copper anode slime smelting waste residue is large and the Ag content is low. It cannot be returned to the copper anode slime pyro-smelting system to recover precious metals. Generally, it enters the copper smelting system to further enrich gold and silver to copper anode slime, resulting in the dispersion loss of gold and silver, and The lead and bismuth part enters the copper smelting waste residue, causing the loss of lead and bismuth. Using this method to treat copper anode slime smelting waste residue, lead and bismuth cannot be recovered, and the treatment process is long and the cost is high.
发明内容SUMMARY OF THE INVENTION
本发明的目的是针对现有技术存在的问题提供一种铜阳极泥冶炼废渣中提取铅铋合金的方法。The object of the present invention is to provide a method for extracting lead-bismuth alloy from copper anode slime smelting waste residue for the problems existing in the prior art.
本发明的具体技术方案如下：The concrete technical scheme of the present invention is as follows:
一种铜阳极泥冶炼废渣中提取铅铋合金的方法，包括以下步骤：将铜阳极泥冶炼废渣和熔剂混合加入到卡尔多炉中还原熔炼，还原熔炼后扒渣得到粗铅铋合金，将粗铅铋合金熔体转运至中频炉后依次进行熔析除铜、加硫除镍、加锌分银得精铅铋合金；所述熔剂包括焦炭、石灰石和碳酸钠，所述熔剂各组分的加入量以铜阳极泥冶炼废渣质量百分比计：焦炭5-6%、石灰石15-19%、碳酸钠2-4%；A method for extracting lead-bismuth alloy from copper anode slime smelting waste slag, comprising the following steps: mixing copper anode slime smelting waste slag and flux into a Kaldor furnace for reduction smelting, removing the slag after reduction smelting to obtain crude lead-bismuth alloy, After the lead-bismuth alloy melt is transported to the intermediate frequency furnace, the lead-bismuth alloy is obtained by successively eluting and removing copper, adding sulfur and removing nickel, adding zinc and separating silver to obtain a refined lead-bismuth alloy; the flux includes coke, limestone and sodium carbonate, and the components of the flux are The amount added is calculated as the mass percentage of copper anode slime smelting waste residue: coke 5-6%, limestone 15-19%, sodium carbonate 2-4%;
进一步的，所述转运至中频炉后保持熔体温度700-800℃，保持时间0.5h；Further, after the transfer to the intermediate frequency furnace, the melt temperature is kept at 700-800°C for 0.5h;
进一步的，所述熔析除铜时熔体温度600℃，以铜阳极泥冶炼废渣质量百分比计加入1-2%碎焦和0.05-1%反应1-2h；Further, when the melt temperature is 600°C during the smelting and copper removal, 1-2% crushed coke and 0.05-1% are added to react for 1-2 hours based on the mass percentage of copper anode slime smelting waste slag;
进一步的，所述加硫除镍时熔体温度350-400℃，按熔体含镍摩尔量的1.5-2倍加入硫磺除镍2-3h；Further, when adding sulfur to remove nickel, the melt temperature is 350-400 °C, and sulfur is added to remove nickel for 2-3 hours according to 1.5-2 times the molar amount of nickel contained in the melt;
进一步的，加锌分银时熔体温度530-560℃，按熔体含银质量的2-4%加入锌粒除银，除银时间4-6h，再将温度降至400℃捞渣。Further, when adding zinc and separating silver, the melt temperature is 530-560 °C, and zinc particles are added to remove silver according to 2-4% of the mass of silver in the melt.
本发明具有以下有益效果：将铜阳极泥冶炼废渣还原熔炼，铅、铋、铜、镍被还原成单质，与少量的金和银形成含金银较低的粗铅铋合金，石灰石和冶炼废渣中原有的硅造渣进入还原尾料，粗铅铋合金熔体通过中间包转入中频炉；粗铅铋合金熔体在中频炉中保持熔体温度700-800℃、保持时间0.5h后，将温度将至600℃，加入碎焦和石英，在低温下铜在铅水中溶解度小，与砷和锑的亲和力很大，能形成化合物、固溶体和共晶，熔点高且密度小，混入固体渣中而上浮；然后加入硫磺，元素硫和镍形成质轻且不熔于铅的镍锍，形成浮渣除去；最后加锌提银，金银与锌的亲和力大，结合成高熔点、低密度而不溶于铅水的锌金和锌银化合物，以银锌壳形态浮在表面而与铅分离，所得精铅铋合金含铅品位较高、杂质少，可直接进行铅电解分离回收铅和铋，银锌壳返炉回收金和银，实现了铜阳极泥冶炼废渣中铅铋和金银的高效分离和回收。The invention has the following beneficial effects: the smelting waste residue of copper anode slime is reduced and smelted, and lead, bismuth, copper and nickel are reduced to elemental substances, and a crude lead-bismuth alloy with low gold and silver content is formed with a small amount of gold and silver, and limestone and smelting waste residue are formed. The original silicon slag in the center enters the reduction tailings, and the crude lead-bismuth alloy melt is transferred to the intermediate frequency furnace through the tundish; after the crude lead-bismuth alloy melt is kept in the intermediate frequency furnace at a melt temperature of 700-800 °C for 0.5h, Bring the temperature to 600 ℃, add crushed coke and quartz, copper has low solubility in lead water at low temperature, and has a large affinity with arsenic and antimony, and can form compounds, solid solutions and eutectic, with high melting point and low density, mixed with solid slag Then add sulfur, element sulfur and nickel form nickel matte that is light in weight and insoluble in lead, forming scum removal; finally adding zinc to extract silver, gold and silver have a high affinity with zinc, and combine into a high melting point and low density The zinc-gold and zinc-silver compounds that are insoluble in lead and water float on the surface in the form of silver-zinc shells and are separated from lead. The resulting refined lead-bismuth alloy has high lead grade and less impurities, and can be directly electrolytically separated to recover lead and bismuth. , the silver-zinc shell is returned to the furnace to recover gold and silver, and the efficient separation and recovery of lead, bismuth, gold and silver in the smelting waste of copper anode slime is realized.
具体实施方式Detailed ways
采用本发明对铜阳极泥冶炼废渣进行铅铋合金提取，铜阳极泥冶炼废渣中含有Ag0.3%、Au 15g/t、Pb 28%、Bi 5%、Ni 2.6%、Cu 2.8%。The method is adopted to extract lead-bismuth alloy from copper anode slime smelting waste residue, and copper anode slime smelting waste residue contains Ag0.3%, Au 15g/t, Pb 28%, Bi 5%, Ni 2.6%, Cu 2.8%.
实施例1Example 1
将4t铜阳极泥冶炼废渣、0.2t焦炭、0.6t石灰石、0.08t碳酸钠混合加入卡尔多炉中还原熔炼，还原熔炼后扒渣得到1.81t粗铅铋合金熔体，将粗铅铋合金熔体通过中间包转运至中频炉中，在中频炉中保持熔体温度700℃、保持时间0.5h，然后将熔体温度降至600℃，加入0.018t碎焦和0.009t石英熔析除铜1h，形成铜浮渣后捞渣；将熔体温度降至350℃，加入0.065t硫磺除镍2h，捞渣；将熔体温度升至530℃，加入0.22kg锌粒除银4h，将熔体温度降至400℃捞渣，得到精铅铋合金。4t copper anode slime smelting waste residue, 0.2t coke, 0.6t limestone and 0.08t sodium carbonate were mixed into the Kaldor furnace for reduction and smelting. After reduction and smelting, slag was removed to obtain 1.81t of crude lead-bismuth alloy melt. The melt is transported to the intermediate frequency furnace through the tundish, and the melt temperature is kept at 700°C for 0.5h in the intermediate frequency furnace, and then the melt temperature is lowered to 600°C, and 0.018t of crushed coke and 0.009t of quartz are added to remove copper for 1h. , after forming copper scum, remove the slag; reduce the melt temperature to 350 ° C, add 0.065t sulfur to remove nickel for 2 hours, and remove the slag; raise the melt temperature to 530 ° C, add 0.22 kg of zinc particles to remove silver for 4 hours, and remove the melt. The temperature is lowered to 400 ℃ and the slag is removed to obtain a refined lead-bismuth alloy.
所得精铅铋合金，其中Cu 0.021%、Ni 0.013%、Ag 0.008%、Pb 85.1%、Bi 12.8%。The obtained refined lead-bismuth alloy, wherein Cu 0.021%, Ni 0.013%, Ag 0.008%, Pb 85.1%, Bi 12.8%.
实施例2Example 2
将4t铜阳极泥冶炼废渣、0.22t焦炭、0.68t石灰石、0.12t碳酸钠混合加入卡尔多炉中还原熔炼，还原熔炼后扒渣得到1.76t粗铅铋合金，将粗铅铋合金熔体通过中间包转运至中频炉中，在中频炉中保持熔体温度750℃、保持时间0.5h，然后将熔体温度降至600℃，加入0.026t碎焦和0.014t石英熔析除铜1.5h，形成铜浮渣后捞渣；将熔体温度降至380℃，加入0.073t硫磺除镍2.5h，捞渣；将熔体温度升至545℃，加入0.36kg锌粒除银5h，将熔体温度降至400℃捞渣，得到精铅铋合金。4t copper anode slime smelting slag, 0.22t coke, 0.68t limestone and 0.12t sodium carbonate were mixed into the Kaldor furnace for reduction and smelting. After reduction and smelting, 1.76t crude lead-bismuth alloy was obtained by removing the slag. The crude lead-bismuth alloy melt was passed through The tundish was transferred to the intermediate frequency furnace, and the melt temperature was kept at 750°C for 0.5h in the intermediate frequency furnace, and then the melt temperature was lowered to 600°C, and 0.026t of crushed coke and 0.014t of quartz were added to remove copper for 1.5h. After the copper scum is formed, the slag is removed; the melt temperature is lowered to 380°C, 0.073t sulfur is added to remove nickel for 2.5h, and the slag is removed; the melt temperature is raised to 545°C, 0.36kg of zinc particles are added to remove silver for 5h, and the melt is removed. The temperature is lowered to 400 ℃ and the slag is removed to obtain a refined lead-bismuth alloy.
所得精铅铋合金，其中Cu 0.020%、Ni 0.011%、Ag 0.007%、Pb 85.3%、Bi 12.9%。The obtained refined lead-bismuth alloy, wherein Cu 0.020%, Ni 0.011%, Ag 0.007%, Pb 85.3%, Bi 12.9%.
实施例3Example 3
将4t铜阳极泥冶炼废渣、0.24t焦炭、0.76t石灰石、0.16t碳酸钠混合加入卡尔多炉中还原熔炼，还原熔炼后扒渣得到1.75t粗铅铋合金，将粗铅铋合金熔体通过中间包转运至中频炉中，在中频炉中保持熔体温度800℃、保持时间0.5h，然后将熔体温度降至600℃，加入0.035t碎焦和0.017t石英熔析除铜2h，形成铜浮渣后捞渣；将熔体温度降至400℃，加入0.087t硫磺除镍3h，捞渣；将熔体温度升至560℃，加入0.44kg锌粒除银6h，将熔体温度降至400℃捞渣，得到精铅铋合金。4t copper anode slime smelting slag, 0.24t coke, 0.76t limestone and 0.16t sodium carbonate were mixed into the Kaldor furnace for reduction and smelting. After reduction and smelting, 1.75t crude lead-bismuth alloy was obtained by removing the slag. The crude lead-bismuth alloy melt was passed through The tundish was transferred to the intermediate frequency furnace, and the melt temperature was kept at 800 °C for 0.5 h in the intermediate frequency furnace, and then the melt temperature was lowered to 600 °C, and 0.035t of crushed coke and 0.017t of quartz were added to remove copper for 2h to form After the copper scum was removed, the slag was removed; the melt temperature was lowered to 400°C, 0.087t sulfur was added to remove nickel for 3 hours, and the slag was removed; the melt temperature was raised to 560°C, 0.44kg of zinc particles was added to remove silver for 6 hours, and the melt temperature was lowered To 400 ℃ to remove slag to obtain refined lead-bismuth alloy.
所得精铅铋合金，其中Cu 0.019%、Ni 0.010%、Ag 0.006%、Pb 85.8%、Bi 13.1%。The obtained refined lead-bismuth alloy, wherein Cu 0.019%, Ni 0.010%, Ag 0.006%, Pb 85.8%, Bi 13.1%.
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| CN111549233B (en) * | 2020-04-03 | 2022-02-01 | 金隆铜业有限公司 | Method for recovering lead and bismuth from copper anode mud smelting slag |
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| CN113981231A (en) * | 2021-11-03 | 2022-01-28 | 安徽铜冠有色金属（池州）有限责任公司 | Process for recovering lead, bismuth, gold and silver from copper anode slime smelting slag |
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