富锗褐煤干馏过程中锗的配分行为研究

Study on the Partition Behaviors of Germanium During the Carbonization of Germanium-rich Lignite

  • 摘要: 为了研究不同干馏条件下富锗褐煤干馏产物分布及锗在各产物中的配分, 采用逐级化学提取法和SEM-EDX首先测定了褐煤中锗的赋存形态, 又采用钢甑反应器进行了不同热解终温(450~850℃)和保温时间(30 min和300 min)下的褐煤干馏试验。结果表明: 褐煤中锗主要以腐殖质结合态存在(占比93.64%)。影响锗挥发的主要因素是干馏温度, 高温(> 650℃)下锗挥发率受保温时间影响较小。绝大部分(>95%)锗迁移到煤气中, 焦油和热解水中锗回收率极低, 褐煤中的锗可进一步从煤气中分离获取。从锗挥发率并兼顾焦油产率的角度考虑, 较好的干馏条件为终温650℃、保温30 min, 此时锗挥发率为98.29%, 焦油产率为5.13%。另外, 还采用TG-MS研究了干馏煤气主要组分的释放行为, 初步探讨了煤气还原性组分与锗挥发率的关系。结果表明: 干馏煤气的还原性组分(CO、H2和H2S)体积浓度与锗挥发率存在明显的正相关性, 煤气还原性越强, 锗挥发率越高, 但高温(850℃)下可能发生过还原反应, 造成锗挥发率的降低。

     

    Abstract: In order to study the distribution of dry distillation products from germanium-rich lignite retorting and germanium partition in each product under different conditions, the occurrence form of germanium in lignite was firstly determined by sequential chemical extraction and SEM-EDX. Then, lignite retorting experiments were carried out at different pyrolysis temperatures (450~850℃) and holding time (30 min and 300 min) in steel retort reactor. The results showed that germanium in lignite mainly existed in the form of humus-bound state (accounting for 93.64%). The main factor affecting the volatilization of germanium was the pyrolysis temperature, and the holding time had little effect on the volatilization of germanium at high temperature (> 650℃). Most of the germanium(95%) migrated to coal gas, and germanium could be further separated from the gas, while the recovery rate of germanium in coal tar and pyrolysis water was extremely low. Considering the maximum volatilization rate of germanium and tar yield, the best retorting condition was the final temperature of 650℃ for 30 min, when the volatilization rate of germanium was 98.29% and the tar yield was 5.13%. In addition, TG-MS was used to study the release behavior of the main components of retorting gas, and the relationship between the reducing components of gas and the volatilization of germanium was discussed. The results showed that the concentration of reducing components (CO, H2 and H2S) of dry distillation gas was positively correlated with the volatilization of germanium. The stronger the reducing nature of gas, the higher the volatilization of germanium. However, over-reduction reaction may occur at high temperature (850℃), resulting in the decrease of the volatilization of germanium.

     

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