摘要
解释了以煤烟尘为原料在制取四氯化锗过程中产生液泛现象的原因。研究发现,在煤烟尘中,少量的锗以GeS,GeO2形式存在,而绝大部分锗则存在于煤烟尘的有机物中。在煤烟尘有机物中含有大量的炭水化合物,它们与有机物中的硅酸盐将形成孔状结构的颗粒,将锗包含其中。这样的结构使煤烟尘在氯化蒸馏时漂浮于盐酸表面,不仅容易起泡形成液泛造成产品污染,也阻碍锗与盐酸反应生成四氯化锗降低了锗的利用率。为了避免液泛污染产品和降低锗利用率,分别采用机械法、有机硅消泡剂法和火冶富集法,对煤烟尘原料进行处理。结果发现:机械法和有机硅消泡剂法对于抑制液泛效果不明显,而火冶富集法可以有效除去有机碳部分,使得煤烟尘的起泡性大大降低,并能够有效控制液泛;但是,火冶富集过程中,煤烟尘的锗挥发率较高,通过加入氧化剂(MnO2)并在相对密闭的容器中焙烧,可以解决这一问题。煤烟尘经过焙烧后金属锗被二氧化锰氧化留在焙烧物中,其烧蚀率由38.00%降低到21.33%,金属锗的挥发率由25.00%降低到7.2%。这样经过焙烧的煤烟尘不但在蒸馏法提取金属锗时可以有效的控制液泛,也有利于提高金属锗的利用率。
Flooding phenomena yielded in the preparation of germanium tetrachloride with soot as the material was explained.The research showed that a small amount of germanium existed in soot in the form of GeS and GeO2,and most of germanium existed in organic compounds of soot.In organic compounds,germanium was contained in particles with porous morphology which were formed by carbohydrates and silicates.This morphology made soot float on hydrochloride surface during chloridizing distillation,which not only introduced foaming to pollute product,but also impeded the reaction of germanium and hydrochloride to produce germanium tetrachloride and decreased utilization of germanium.To avoid these,soot was treated with mechanical method,organosilicon defoamer method and pyrometallurgy enrichment method.The results showed that mechanical method and organosilicon defoamer method had no obvious effect on inhibiting flooding,but pyrometallurgy enrichment method could effectively remove organic carbon,greatly reduce the foamability of soot and control flooding.However,in pyrometallurgy enrichment,the volatilization rate of germanium in soot was very high.This problem could be solved by adding oxidant（MnO2） and roasting in closed vessel.After roasting,metal germanium was oxidized by MnO2 and remained in roasting product,its ablation rate could be reduced to 21.33% from 38.00%,and its volatilization rate could be reduced to 7.2% from 25.00%.When extracting metal germanium with distillation,this soot treated by roasting could effectively control flooding and increase utilization of germanium.
出处
《稀有金属》
EI
CAS
CSCD
北大核心
2011年第4期623-626,共4页
Chinese Journal of Rare Metals
基金
国家光纤用四氯化锗示范工程资助项目
关键词
煤烟尘
四氯化锗
液泛
收率
coal fly ash
germanium tetrachloride
flooding
yield
