Thermodynamic behaviors of SiCl_2 in silicon deposition by gas phase zinc reduction of silicon tetrachloride

The modified Siemens process,which is the major process of producing polycrystalline silicon through current technologies,is a high temperature,slow,semi-batch process and the product is expensive primarily due to the large energy consumption.Therefore,the zinc reduction process,which can produce solar-grade silicon in a cost effective manner,should be redeveloped for these conditions.The SiCl2 generation ratio,which stands for the degree of the side reactions,can be decomposed to SiCl4 and ZnCl2 in gas phase zinc atmosphere in the exit where the temperature is very low.Therefore,the lower SiCl2 generation ratio is profitable with lower power consumption.Based on the thermodynamic data for the related pure substances,the relations of the SiCl2 generation ratio and pressure,temperature and the feed molar ratio（n（Zn）/n（SiCl4） are investigated and the graphs thereof are plotted.And the diagrams of Kpθ-T at standard atmosphere pressure have been plotted to account for the influence of temperature on the SiCl2 generation ratio.Furthermore,the diagram of Kpθ-T at different pressures have also been plotted to give an interpretation of the influence of pressure on the SiCl2 generation ratio.The results show that SiCl2 generation ratio increases with increasing temperature,and the higher pressure and excess gas phase zinc can restrict SiCl2 generation ratio.Finally,suitable operational conditions in the practical process of polycrystalline silicon manufacture by gas phase zinc reduction of SiCl4 have been established with 1200 K,0.2 MPa and the feed molar ratio（n（Zn） /n（SiCl4）） of 4 at the entrance.Under these conditions,SiCl2 generation ratio is very low,which indicates that the side reactions can be restricted and the energy consumption is reasonable.

Important mesoscale phenomena in gas phase fluidized bed ethylene polymerization

Gas phase fluidized bed processes have been widely applied to polyethylene production.In these processes,the flow,mass transfer,and reaction rate on the microscale and macroscale are strongly coupled because of the multiphase and multiscale nature of the fluidization system.Understanding mesoscale phenomena is therefore essential to the quantitative translation of the knowledge obtained from the microscale to the macroscale.This paper reviews the development of ethylene polymerization gas phase processes while focussing on studies regarding mesoscale phenomena.These include experimental characterizations,mathematical modelling and control strategies.Trends and future developments in this field are also discussed.