高鐵閃鋅礦中銦、鎘的綜合利用研究
發(fā)布時間：2018-09-08 20:57
【摘要】：高鐵閃鋅礦是我國特有的銦鋅資源,富含鋅、鐵、銦、錫、銅、鎘、銀等多種金屬,如何實現(xiàn)其清潔高效綜合利用是銦鋅冶金行業(yè)面臨的重要問題。采用濕法冶煉將產(chǎn)出大量的浸出渣和凈化渣,金屬銦回收率低(In≤60%)。"還原熔煉-常壓精餾-綜合回收"冶煉工藝實現(xiàn)了鋅、銦資源的綜合回收,但仍存在一些關(guān)鍵的工藝技術(shù)問題:還原熔煉過程中銦在水淬渣、含銅生鐵中的損失仍然較大,直收率低;冶煉流程中高鎘鋅無法處理,導致鎘的資源流失;精銦產(chǎn)品單一,附加值低等。針對這些問題,本文提出了解決高鐵多金屬鋅精礦銦、鎘資源綜合利用的新工藝。首先,對高鐵閃鋅礦還原熔煉過程中元素的行為進行了研究;其次,采用從頭算分子動力學模擬對其鋅鉛混合熔煉的可行性進行了理論研究及試驗研究;再次,提出了真空蒸餾處理常壓精餾產(chǎn)出的高鎘鋅的新工藝;最后,進行了銦的提純實驗研究。具體研究內(nèi)容及進展如下:(1)高鐵閃鋅礦焙砂高溫還原揮發(fā)熔煉過程中,鋅、銦、鎘、銅、鐵、銀、鉛、錫的分布行為研究表明:①鋅的直收率為83.86%,銦的直收率為64.45%,錫的直收率為13.55%,銀的直收率為32%;②14.87%的銦進入水淬渣和含銅生鐵,80.93%的鎘富集于高鎘鋅。③11.62%的銅進入水淬渣,63.85%的銅富集于含銅生鐵;60%的鐵進入含銅生鐵,11%的鐵進入水淬渣;83.62%的鉛進入粗鋅。(2)針對還原熔煉過程中In在含銅生鐵及水淬渣中損失較大的問題,研究了鋅鉛混合熔煉提高銦富集率的方法。首先采用從頭算分子動力學模擬(AIMD)研究了還原熔煉過程加鉛富集銦的可行性,確定ZnInPb間的相互作用行為。然后進行了鋅鉛混合熔煉試驗研究,探究還原熔煉過程中鉛量對銦分布的影響。1)PbnInn、PbnZnn、ZnnInn團簇的模擬結(jié)果表明,二元團簇中原子間結(jié)合力大小為 Pb-InPb-ZnZn-In;Zn12In6Pb2 團簇(In:Pb=3:1)、Zn14In2Pb4(In:Pb=1:2)團簇、Zn12In2Pb6(In:Pb=1:3)團簇和Zn15InPb4(In:Pb=1:4)團簇模擬結(jié)果表明:三元團簇中Zn原子不穩(wěn)定,動力學模擬,團簇中Zn原子均脫離團簇本體;Zn12In2Pb6(In:Pb=1:3)中In-Pb的結(jié)合力最好,Zn15InPb4中In-Pb的結(jié)合力最弱;Zn106In11Pb11三元合金的從頭算分子動力學模擬表明,In-Pb原子間的作用力較Zn-In、Zn-Pb強。2)利用鉛與銦的相互作用,進行了鉛鋅混合熔煉,改變鉛鋅比(In:Pb～3:1、1:2、1:3、1:4)研究粗鋅中銦的富集率,結(jié)果表明入爐鉛含量的增加能提高粗鋅中銦的富集率,同時減少銦在還原熔煉過程棄渣中的損失,富集還原熔煉鉛的含量在0.18～0.2%(In:Pb～1:3)時,銦的富集效果最好。3)In:Pb比為1:3的試驗結(jié)果表明:①入爐鉛的含量的增加可使含銅生鐵中銦的含量從573.28g/t降低到100g/t,提高了銦的回收率。②粗鋅含銦由1073.7 g/t提高到1442.3g/t,提高了 25.19%,銦回收率提高到95%以上,提高了 18.46%;粗鋅中的鐵含量降低到0.2%以下。(3)針對火法冶煉過程中產(chǎn)出的高鎘鋅,提出了高鎘鋅的真空蒸餾-分級冷凝工藝,研究表明:低溫緩蒸有利于鋅鎘合金的真空蒸餾分離提純。冷凝盤的級數(shù)越高,得到的鎘就越純,分離效果就越好。將鋅鎘合金在30Pa,673K,30min條件下進行三次真空蒸餾可獲得4N的精鎘。(4)銦的區(qū)域熔煉提純實驗研究表明:銦中的大部分雜質(zhì)在區(qū)域熔煉過程中富集在錠尾;降低區(qū)熔熔煉速度、增加區(qū)熔熔煉的次數(shù),可以使熔區(qū)內(nèi)的雜質(zhì)元素得到充分凝聚,從而提高提純效果。在區(qū)熔速度為1mn/min的條件下,經(jīng)過10道次的區(qū)域熔煉提純,得到純度為99.9991%的高純銦。本研究完善了高銦高鐵閃鋅礦高溫還原熔煉流程,通過還原熔煉過程中銦的強化富集、副產(chǎn)物高鎘鋅的真空處理、區(qū)域熔煉提純金屬銦的工藝的研究,實現(xiàn)了鐵閃鋅礦中銦、鎘資源的綜合高效回收。
[Abstract]:High iron sphalerite is a unique indium-zinc resource in China, rich in zinc, iron, indium, tin, copper, cadmium, silver and other metals. How to realize its clean and efficient comprehensive utilization is an important problem faced by the indium-zinc metallurgical industry. The combined recovery process realizes the comprehensive recovery of zinc and indium resources, but there are still some key technological problems: the loss of indium in water-quenched slag during reduction smelting is still large, and the direct yield of copper-bearing pig iron is low; the high content of cadmium and zinc in the smelting process can not be treated, resulting in the loss of cadmium resources; the purified indium products are single, and the added value is low. In order to solve these problems, a new process for comprehensive utilization of indium and cadmium resources in high-iron polymetallic zinc concentrate is proposed. Firstly, the behavior of elements in reduction smelting of high-iron sphalerite is studied. Secondly, the feasibility of mixed smelting of zinc and lead is studied theoretically and experimentally by ab initio molecular dynamics simulation. In this paper, a new process of vacuum distillation for the treatment of zinc with high cadmium content produced by atmospheric distillation was studied. Finally, the experimental study on the purification of indium was carried out. The direct yield of 64.45%, tin 13.55% and silver 32%; 2. 14.87% indium enters water-quenched slag and copper-bearing pig iron, 80.93% cadmium enters water-quenched slag, 11.62% copper enters water-quenched slag, 63.85% copper enters copper-bearing pig iron, 60% iron enters copper-bearing pig iron, 11% iron enters water-quenched slag, 83.62% lead enters crude zinc. (2) Aiming at reducing smelting. In the process of reduction smelting, the feasibility of adding lead to enrich indium was studied by ab initio molecular dynamics simulation (AIMD), and the interaction between ZnInPb and ZnInPb was determined. The influence of lead content on indium distribution in reduction smelting process was investigated. 1) The simulation results of PbnInn, PbnZnn, ZnnInn clusters show that the binding force between atoms in binary clusters is Pb-InPb-ZnZn-In, Zn12In6Pb2 clusters (In: Pb = 3:1), Zn14In2Pb4 clusters (In: Pb = 1:2), Zn12In2Pb6 (In: Pb = 1:3) Pb 4 clusters and Zn15InPb4 (In: Pb = 1:4) clusters. Ming: Zn atoms in ternary clusters are unstable, dynamics simulation shows that Zn atoms in the clusters are separated from the clusters; In-Pb binding force is the best in Zn12In2Pb6 (In: Pb = 1:3), and in-Pb binding force is the weakest in Zn15InPb4; Ab initio molecular dynamics simulation of Zn106In11Pb11 ternary alloy shows that the interaction force between in-Pb atoms is stronger than that between Zn-In, Zn-Pb.2) using Pb and Zn. The enrichment rate of indium in crude zinc was studied by changing the ratio of lead to zinc (In: Pb~3:1,1:2,1:3,1:4). The results show that the enrichment rate of indium in crude zinc can be increased with the increase of lead content in furnace, and the loss of indium in slag discarded during reduction smelting can be reduced. The concentration of lead in reduction smelting is 0.18-0.2% (In: Pb~1:3). (3) In: Pb ratio is 1:3. The results show that: (1) The content of indium in copper-bearing pig iron can be reduced from 573.28g/t to 100g/t with the increase of lead content in furnace, and the recovery rate of indium can be increased. (3) A vacuum distillation-fractional condensation process for high cadmium zinc produced in Pyrometallurgical smelting was proposed. The results show that low temperature slow evaporation is beneficial to the vacuum distillation and purification of zinc-cadmium alloy. Refined cadmium of 4N can be obtained by three times vacuum distillation at 30Pa, 673K and 30min. (4) The experimental results of regional smelting purification of indium show that most impurities in indium are concentrated in the tail of ingot during regional smelting, and the impurities in the melting zone can be fully condensed by reducing the zone smelting speed and increasing the number of zone smelting. The purity of indium was 99.9991% after 10 passes of regional smelting and purification under the condition of 1mn/min regional melting speed. The high-temperature reduction smelting process of high-indium high-iron sphalerite was improved in this study. Indium was enriched during reduction smelting, by-product high-cadmium zinc was vacuum treated, and indium was purified by regional smelting. The research of process has realized the comprehensive and efficient recovery of indium and cadmium resources in sphalerite.
【學位授予單位】：昆明理工大學
【學位級別】：博士
【學位授予年份】：2017
【分類號】：TF803
[Abstract]:High iron sphalerite is a unique indium-zinc resource in China, rich in zinc, iron, indium, tin, copper, cadmium, silver and other metals. How to realize its clean and efficient comprehensive utilization is an important problem faced by the indium-zinc metallurgical industry. The combined recovery process realizes the comprehensive recovery of zinc and indium resources, but there are still some key technological problems: the loss of indium in water-quenched slag during reduction smelting is still large, and the direct yield of copper-bearing pig iron is low; the high content of cadmium and zinc in the smelting process can not be treated, resulting in the loss of cadmium resources; the purified indium products are single, and the added value is low. In order to solve these problems, a new process for comprehensive utilization of indium and cadmium resources in high-iron polymetallic zinc concentrate is proposed. Firstly, the behavior of elements in reduction smelting of high-iron sphalerite is studied. Secondly, the feasibility of mixed smelting of zinc and lead is studied theoretically and experimentally by ab initio molecular dynamics simulation. In this paper, a new process of vacuum distillation for the treatment of zinc with high cadmium content produced by atmospheric distillation was studied. Finally, the experimental study on the purification of indium was carried out. The direct yield of 64.45%, tin 13.55% and silver 32%; 2. 14.87% indium enters water-quenched slag and copper-bearing pig iron, 80.93% cadmium enters water-quenched slag, 11.62% copper enters water-quenched slag, 63.85% copper enters copper-bearing pig iron, 60% iron enters copper-bearing pig iron, 11% iron enters water-quenched slag, 83.62% lead enters crude zinc. (2) Aiming at reducing smelting. In the process of reduction smelting, the feasibility of adding lead to enrich indium was studied by ab initio molecular dynamics simulation (AIMD), and the interaction between ZnInPb and ZnInPb was determined. The influence of lead content on indium distribution in reduction smelting process was investigated. 1) The simulation results of PbnInn, PbnZnn, ZnnInn clusters show that the binding force between atoms in binary clusters is Pb-InPb-ZnZn-In, Zn12In6Pb2 clusters (In: Pb = 3:1), Zn14In2Pb4 clusters (In: Pb = 1:2), Zn12In2Pb6 (In: Pb = 1:3) Pb 4 clusters and Zn15InPb4 (In: Pb = 1:4) clusters. Ming: Zn atoms in ternary clusters are unstable, dynamics simulation shows that Zn atoms in the clusters are separated from the clusters; In-Pb binding force is the best in Zn12In2Pb6 (In: Pb = 1:3), and in-Pb binding force is the weakest in Zn15InPb4; Ab initio molecular dynamics simulation of Zn106In11Pb11 ternary alloy shows that the interaction force between in-Pb atoms is stronger than that between Zn-In, Zn-Pb.2) using Pb and Zn. The enrichment rate of indium in crude zinc was studied by changing the ratio of lead to zinc (In: Pb~3:1,1:2,1:3,1:4). The results show that the enrichment rate of indium in crude zinc can be increased with the increase of lead content in furnace, and the loss of indium in slag discarded during reduction smelting can be reduced. The concentration of lead in reduction smelting is 0.18-0.2% (In: Pb~1:3). (3) In: Pb ratio is 1:3. The results show that: (1) The content of indium in copper-bearing pig iron can be reduced from 573.28g/t to 100g/t with the increase of lead content in furnace, and the recovery rate of indium can be increased. (3) A vacuum distillation-fractional condensation process for high cadmium zinc produced in Pyrometallurgical smelting was proposed. The results show that low temperature slow evaporation is beneficial to the vacuum distillation and purification of zinc-cadmium alloy. Refined cadmium of 4N can be obtained by three times vacuum distillation at 30Pa, 673K and 30min. (4) The experimental results of regional smelting purification of indium show that most impurities in indium are concentrated in the tail of ingot during regional smelting, and the impurities in the melting zone can be fully condensed by reducing the zone smelting speed and increasing the number of zone smelting. The purity of indium was 99.9991% after 10 passes of regional smelting and purification under the condition of 1mn/min regional melting speed. The high-temperature reduction smelting process of high-indium high-iron sphalerite was improved in this study. Indium was enriched during reduction smelting, by-product high-cadmium zinc was vacuum treated, and indium was purified by regional smelting. The research of process has realized the comprehensive and efficient recovery of indium and cadmium resources in sphalerite.
【學位授予單位】：昆明理工大學
【學位級別】：博士
【學位授予年份】：2017
【分類號】：TF803
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