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A side blowing furnace was adopted to treat the leaching residue of copper anode slime and recover valuable metals therein comprehensively. The effects of soda dosage, granular coal dosage, precipitation time and top flue gas temperature on the recovery rates of main metals Pb, Sb, Bi, Au and Ag were investigated. The results show that with soda at an amount of 2.5%, granular coal at an amount of 3%, the precipitation time of 1.5 h, and the top flue gas temperature of 750 ℃, the precious lead product is obtained after processing, grading 1 544 g/t Au (1.84 times enrichment), 10.37% Ag (1.4 times enrichment), 22.89% Pb (2.1 times enrichment), and 27.45% Bi (2.2 times enrichment).

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采用侧吹炉协同处理铜阳极泥浸出渣，综合回收有价金属，考察了纯碱用量、粒煤用量、沉淀时间、炉顶烟气温度对主金属Pb、Sb、Bi、Au、Ag回收率的影响。结果表明，适宜的处理工艺参数为：纯碱用量2.5%、粒煤用量3%、沉淀时间1.5 h、炉顶烟气温度750 ℃，此时贵铅中Au品位达到1 544 g/t（富集了1.84倍）、Ag品位达到10.37%（富集了1.4倍）、Pb品位达到22.89%（富集了2.1倍）、Bi品位达到27.45%（富集了2.2倍）。

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闫友（1971—），男，辽宁昌图人，高级工程师，主要从事有色金属、稀贵金属冶炼及环保研究工作。E-mail：

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闫友（1971—），男，辽宁昌图人，高级工程师，主要从事有色金属、稀贵金属冶炼及环保研究工作。E-mail：

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闫友（1971—），男，辽宁昌图人，高级工程师，主要从事有色金属、稀贵金属冶炼及环保研究工作。E-mail：

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名称含量（质量分数）/%配比/%
水分Au1）Ag1）PbSbBiAs
铜阳极泥浸出渣7.906 247.0268 837.377.592.460.736.0210
铅阳极泥25.42359.5374 675.3812.0329.2012.1318.7990
混合阳极泥23.65839.874 091.5811.5926.5310.9917.51100
), ArticleFig(id=1241779793331553243, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241768046075904187, language=CN, label=表1, caption=

各物料主要化学成分（干基）及混合阳极泥配比

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名称含量（质量分数）/%配比/%
水分Au1）Ag1）PbSbBiAs
铜阳极泥浸出渣7.906 247.0268 837.377.592.460.736.0210
铅阳极泥25.42359.5374 675.3812.0329.2012.1318.7990
混合阳极泥23.65839.874 091.5811.5926.5310.9917.51100
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纯碱用量/%贵铅成分（质量分数）/%
PbSbBiAu1）Ag1）
1.016.0933.7920.5991688 157
1.522.9524.8827.631 44594 876
2.019.7325.1727.451 506100 904
2.522.5223.7328.471 541102 727
3.022.3123.5225.511 48096 907
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纯碱用量对贵铅中主要有价金属化学成分的影响

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纯碱用量/%贵铅成分（质量分数）/%
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1.522.9524.8827.631 44594 876
2.019.7325.1727.451 506100 904
2.522.5223.7328.471 541102 727
3.022.3123.5225.511 48096 907
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粒煤用量/%贵铅成分（质量分数）/%
PbSbBiAu1）Ag1）
118.4220.1223.391 26385 325
220.9524.8827.631 44594 876
322.7625.1727.851 554100 904
422.6127.6828.111 543101 019
522.5930.5527.671 512100 988
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粒煤用量对贵铅中主要有价金属化学成分的影响

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粒煤用量/%贵铅成分（质量分数）/%
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118.4220.1223.391 26385 325
220.9524.8827.631 44594 876
322.7625.1727.851 554100 904
422.6127.6828.111 543101 019
522.5930.5527.671 512100 988
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PbSbBiAu1）Ag1）
0.518.7620.7220.591 35588 157
1.020.4323.8125.661 49394 876
1.522.8925.1727.451 544103 724
2.022.7624.9927.321 546103 656
2.522.8124.9427.481 541103 865
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沉淀时间对贵铅中主要有价金属化学成分的影响

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沉淀时间/h贵铅成分（质量分数）/%
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1.020.4323.8125.661 49394 876
1.522.8925.1727.451 544103 724
2.022.7624.9927.321 546103 656
2.522.8124.9427.481 541103 865
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炉顶烟气温度/℃贵铅成分（质量分数）/%
PbSbBiAu1）Ag1）
65020.9223.4125.911 26890 351
70022.8224.6427.281 47396 794
75023.0925.2127.651 521101 354
80022.4224.6828.041 519101 227
85021.9123.1226.911 50898 923
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炉顶烟气温度对贵铅中主要有价金属化学成分的影响

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70022.8224.6427.281 47396 794
75023.0925.2127.651 521101 354
80022.4224.6828.041 519101 227
85021.9123.1226.911 50898 923
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侧吹炉协同处理铜阳极泥浸出渣回收有价金属新工艺研究
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矿冶工程杂志 | 冶金 2024,44(1): 125-128
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矿冶工程杂志 | 冶金 2024, 44(1): 125-128
侧吹炉协同处理铜阳极泥浸出渣回收有价金属新工艺研究
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作者信息
  • 湖南水口山有色金属集团有限公司，湖南　衡阳　421513

    • 闫友（1971—），男，辽宁昌图人，高级工程师，主要从事有色金属、稀贵金属冶炼及环保研究工作。E-mail：

A New Process for Recovering Valuable Metals from Leaching Residue of Copper Anode Slime by Side Blowing Furnace
You YAN
Affiliations
  • Hunan Shuikoushan Nonferrous Metals Group Co Ltd, Hengyang 421513, Hunan, China
出版时间: 2024-02-01 doi: 10.3969/j.issn.0253-6099.2024.01.027
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摘要
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采用侧吹炉协同处理铜阳极泥浸出渣，综合回收有价金属，考察了纯碱用量、粒煤用量、沉淀时间、炉顶烟气温度对主金属Pb、Sb、Bi、Au、Ag回收率的影响。结果表明，适宜的处理工艺参数为：纯碱用量2.5%、粒煤用量3%、沉淀时间1.5 h、炉顶烟气温度750 ℃，此时贵铅中Au品位达到1 544 g/t（富集了1.84倍）、Ag品位达到10.37%（富集了1.4倍）、Pb品位达到22.89%（富集了2.1倍）、Bi品位达到27.45%（富集了2.2倍）。

侧吹炉  /  铜阳极泥  /  浸出渣  /  稀贵金属  /  有价金属  /  富集  /  铅  /  锑  /  铋  /  金  /  银

A side blowing furnace was adopted to treat the leaching residue of copper anode slime and recover valuable metals therein comprehensively. The effects of soda dosage, granular coal dosage, precipitation time and top flue gas temperature on the recovery rates of main metals Pb, Sb, Bi, Au and Ag were investigated. The results show that with soda at an amount of 2.5%, granular coal at an amount of 3%, the precipitation time of 1.5 h, and the top flue gas temperature of 750 ℃, the precious lead product is obtained after processing, grading 1 544 g/t Au (1.84 times enrichment), 10.37% Ag (1.4 times enrichment), 22.89% Pb (2.1 times enrichment), and 27.45% Bi (2.2 times enrichment).

side blowing furnace  /  copper anode slime  /  leaching residue  /  rare and precious metals  /  valuable metals  /  enrichment  /  lead  /  antimony  /  bismuth  /  gold  /  silver
闫友. 侧吹炉协同处理铜阳极泥浸出渣回收有价金属新工艺研究. 矿冶工程杂志, 2024 , 44 (1) : 125 -128 . DOI: 10.3969/j.issn.0253-6099.2024.01.027
You YAN. A New Process for Recovering Valuable Metals from Leaching Residue of Copper Anode Slime by Side Blowing Furnace[J]. Mining and Metallurgical Engineering, 2024 , 44 (1) : 125 -128 . DOI: 10.3969/j.issn.0253-6099.2024.01.027
正文
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随着电子信息、新能源等产业的快速发展，稀贵金属需求量大幅度增加[1-3]。目前，除Au、Ag等部分贵金属拥有独立开发的矿床外，大部分稀贵金属都是从二次资源中综合回收而来[4-5]。
铜阳极泥是铜电解精炼过程中产出的一种物料，目前每生产1 t电解铜产出2～8 kg铜阳极泥[6]。据统计，我国2018—2022年电解铜产量逐年增加，其中2022年中国精炼铜产量达到1 101.1万吨[7]；与此同时，铜阳极泥存量也在不断增加。高效处理铜阳极泥不仅可实现资源综合利用，而且具有显著的社会经济效益[8]。
目前，国内外铜阳极泥处理工艺主要分为3种：①全湿法工艺；②湿法为主、湿法与火法相结合处理工艺；③火法为主、湿法与火法相结合的工艺[9-11]。采用传统火法工艺处理铜阳极泥的弊端主要表现为环境污染大、有价金属回收率低；而采用传统湿法工艺处理铜阳极泥主要存在设备要求高、占地面积大、废水处理成本高、跑冒滴漏比较严重等问题。
本文结合某公司生产实际，充分利用侧吹炉单独处理铅阳极泥富余能力，采用侧吹炉协同处理铜阳极泥浸出渣，无需单独新建处理铜阳极泥浸出渣系统，可以减少投资费用。
1　试验
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1.1　试验原料
湖南某厂粗铜电解精炼过程中产出的铜阳极泥中硒品位5%～10%，水分含量达到18%以上，为了避免生产过程中产出亚硒酸造成布袋板结及收尘系统严重腐蚀，先采用硫酸化焙烧预处理铜阳极泥，然后再浸出。本文以经过湿法预处理脱铜、硒的浸出渣及粗铅电解精炼过程中产出的铅阳极泥为试验原料，组成混合阳极泥。通过电感耦合等离子光谱仪器ICP-OES检测分析，混合阳极泥中Pb、Bi、Sb及Au、Ag等贵金属总量达到55%以上，其中锑含量达到25%以上，水分含量20%～25%，粒度0.096～0.18 mm。各物料主要化学成分及混合阳极泥配比如表1所示。
1.2　工艺流程确定
在高温及还原气氛条件下，阳极泥中一部分砷、锑以低价氧化物挥发进入收尘系统，其余大部分与纯碱反应造渣进入渣中。铅、铋被还原成单质，铋密度较大，同时高温下铅与铋互溶系数较大，且铅是金、银及贵金属良好捕集剂，在沉淀过程中金、银及贵金属大量溶解于单质铅中，使铋、金、银及贵金属富集于贵铅中。
粒煤主要成分为碳，其中固定碳含量不低于80%，粒度1～3 cm，水分含量不高于7%。粒煤一部分作为热源，另一部分主要用于提供炉内还原气氛，将渣中Pb、Sb、Bi还原成单质状态，利用Pb是Au、Ag等贵金属的良好捕集剂，使混合阳极泥中大部分Au、Ag等贵金属进入贵铅中，便于下一步生产银合金板。氧化物碳热还原反应如式（1）～（2）所示。另外根据布多尔反应，在温度大于1 000 ℃下C-CO-CO2系统中CO2的平衡分压接近于0[12]。
侧吹炉协同处理铜阳极泥浸出渣过程中，主要发生以下化学反应：
基于以上分析，结合原料中有价金属品位及某公司现场生产实际，拟采用侧吹炉协同处理铜阳极泥浸出渣回收有价金属，其工艺流程如图1所示。
2　试验设备与分析方法
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本试验设备主要包括2 m2侧吹炉、皮带输送机、DCS中控系统等设备。利用三把浸没式氧枪通过富氧燃烧天然气对炉内供热，通过不同阶段精准调节炉内气氛确保炉内温度及气氛精准可控，同时具备精准上料系统，确保试验过程中均匀稳定下料。侧吹炉协同处理铜阳极泥浸出渣主要产物为贵铅，作为提炼银合金板的主要原料，贵铅中主要包括Pb、Sb、Bi、Au、Ag等贵金属，采用电感耦合等离子光谱仪器ICP-OES检测分析其中具体成分。
3　试验结果与讨论
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3.1　纯碱用量对贵铅有价金属品位的影响
按表1进行配料，采用侧吹炉处理混合阳极泥，采用电子皮带均匀加料，加料速度3 t/h，单炉进料12 t。控制炉顶烟气温度750 ℃、粒煤用量3%（相对于混合阳极泥的质量分数）、沉淀时间1.5 h，考察了纯碱用量对贵铅中主要有价金属品位的影响，结果如表2所示。
分析表2可得，纯碱用量较低时，随着纯碱用量增加，贵铅中有价金属Au、Ag品位逐渐提高，有价金属Pb、Sb、Bi品位有所波动。纯碱用量2.5%时，处理效果较好。继续提高纯碱用量，贵铅中Pb、Sb品位变化不明显，但Bi、Au、Ag品位呈下降趋势，且碱量增大，易形成泡泡渣，造成炉内渣液面较高，对炉内镁铬砖及氧枪腐蚀性增强，会大幅度缩短侧吹炉有效使用寿命，缩减单周期处理量。纯碱用量2.5%较为适宜。
3.2　粒煤用量对贵铅有价金属品位的影响
纯碱用量2.5%，其他条件不变，粒煤用量（相对混合阳极泥的质量分数）对贵铅中主要有价金属品位的影响如表3所示。
从表3可知，粒煤用量不超过3%时，随着粒煤用量增加，贵铅中有价金属品位均逐渐提高；粒煤用量超过3%后，贵铅中有价金属Pb、Bi、Au、Ag品位变化不明显，但Sb品位呈上升趋势，这是因为渣中三氧化二锑被进一步还原成单质Sb进入贵铅。
粒煤用量越大，生产成本越高；且贵铅中Sb品位越高，后续以贵铅为原料生产银合金板需要耗费更长的时间进行低温跑烟，生产周期延长，Au、Ag等贵金属直收率较低。选择粒煤用量3%进行后续试验。
3.3　沉淀时间对贵铅有价金属品位的影响
利用炉内熔融渣与贵铅的密度差，通过沉淀可以实现熔融渣与贵铅的分离。沉淀时间不足时，渣中存在夹杂现象，造成渣中Pb、Sb、Bi、Au、Ag品位较高，需在渣沉淀炉内进一步沉淀，造成侧吹炉内熔融渣无法继续排放，降低侧吹炉的混合阳极泥处理量；但沉淀时间过长，日处理量降低，生产效率降低，能耗及人工成本大幅度增加。
粒煤用量3%，其他条件不变，沉淀时间对贵铅中主要有价金属品位的影响如表4所示。
从表4可见，沉淀时间低于1.5 h时，随着沉淀时间延长，贵铅中有价金属品位均显著提高；沉淀时间超过1.5 h后，继续延长沉淀时间，贵铅中有价金属品位无明显变化。沉淀时间选择1.5 h。
3.4　炉顶烟气温度对贵铅有价金属品位的影响
直接测量炉内熔池温度存在一定难度，根据现场经验，通过测量渣温、侧吹炉炉顶烟气温度可以间接反映熔池温度。
沉淀时间1.5 h，其他条件不变，炉顶烟气温度对贵铅中主要有价金属品位的影响如表5所示。
由表5可知，炉顶烟气温度低于750 ℃时，随着炉顶烟气温度上升，因炉内造渣效果较好，熔融渣与贵铅密度相差加大，分离效果较好，同时渣的流动性较好，贵铅中有价金属品位均逐渐提高，炉顶烟气温度750 ℃时，处理效果较好。炉顶烟气温度超过750 ℃后，贵铅中Pb、Sb、Bi、Ag品位呈缓慢下降趋势，但Au品位变化不明显。炉内温度越高，能耗越大，生产成本越高。炉顶烟气温度控制为750 ℃。
3.5　优化条件试验
通过以上单因素实验，得到侧吹炉协同处理铜阳极泥浸出渣的优化工艺条件为：纯碱用量2.5%、粒煤用量3%、沉淀时间1.5 h、炉顶烟气温度750 ℃。在此条件下进行验证试验，贵铅中Au品位达1 544 g/t，富集了1.84倍；Ag品位达10.37%，富集了1.4倍；Pb品位达22.89%，富集了2.1倍；Bi品位达27.45%，富集了2.2倍。
4　结论
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1）侧吹炉协同处理铜阳极泥浸出渣，贵铅中Au品位达到1 544 g/t，富集了1.84倍；Ag品位达到10.37%，富集了1.4倍；Pb品位达到22.89%，富集了2.1倍；Bi品位达到27.45%，富集了2.2倍。
2）采用侧吹炉协同处理铜阳极泥，需进行硫酸化焙烧预处理去除Cu、Se，避免布袋板结。
3）该方法与传统处理工艺相比具有环境友好及工艺简单等优点，为处理该类型铜阳极泥浸出渣提供了一种有效方法，具有一定的应用前景。
基金
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  • 国家重点研发计划(2018YFC1903300)
文献
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doi: 10.3969/j.issn.0253-6099.2024.01.027
  • 接收时间：2023-09-03
  • 首发时间：2026-03-20
  • 出版时间：2024-02-01
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  • 收稿日期：2023-09-03
基金
国家重点研发计划(2018YFC1903300)
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    湖南水口山有色金属集团有限公司，湖南　衡阳　421513
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2种不同金属材料的力学参数
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Number of
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Number of
species		 占总种数比例
Percentage of
total species (%)		 属
Genus		 种数
Number of
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鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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