方锑矿在煅烧/熔解温度下和氮气气氛中的挥发动力学（英文）
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摘要
采用热重分析方法,利用1.3 mL陶瓷坩埚(内径11 mm,高14 mm),在不同气体流速下研究方锑矿在中性气氛中和煅烧(550~615°C)/熔解(660~1100°C)温度下的挥发动力学。分析颗粒尺寸的影响。部分反应样品的失重分析和X射线衍射分析结果以及热力学研究表明,在整个温度范围内,方锑矿不形成其他化合物,直接以Sb_4O_6的形式挥发。在煅烧温度下,Sb_2O_3的挥发动力学方程可用X=kappt描述。挥发反应受表面化学反应控制,活化能为193.0 k J/mol。根据方锑矿在溶解温度下的挥发反应动力学方程呈线性关系的特点,确定了挥发反应的动力学常数,得到表面积为8.171×10~(-5) m~2的挥发反应的活化能为73.9 k J/mol。
The volatilization kinetics of senarmontite(Sb_2O_3) was analyzed in a neutral atmosphere in two temperature ranges: 550-615 °C(roasting temperature) and 660-1100 °C(melting temperature) by using a thermogravimetric analysis method under various gas flow rates and using a 1.3 m L ceramic crucible(11 mm in internal diameter and 14 mm in height). The effect of particle size was also analyzed. The experimental results of mass loss data, X-ray diffraction(XRD) analysis of partially reacted samples and thermodynamic studies indicate that the senarmontite becomes volatile in the form of Sb_4O_6(g) without the formation of any intermediary compound in the entire temperature range. At roasting temperatures, the volatilization kinetics of Sb_2O_3 was analyzed using the model X=kappt. The volatilization reaction was controlled by the surface chemical reaction and an activation energy value of 193.0 k J/mol was obtained in this temperature range. Based on the volatilization kinetics at the melting temperatures, for linear behaviour in nitrogen gas, kinetic constants were determined, and an activation energy of 73.9 k J/mol was calculated for the volatilization reaction with a surface area of 8.171×10~(-5)m~2.
The volatilization kinetics of senarmontite(Sb_2O_3) was analyzed in a neutral atmosphere in two temperature ranges: 550-615 °C(roasting temperature) and 660-1100 °C(melting temperature) by using a thermogravimetric analysis method under various gas flow rates and using a 1.3 m L ceramic crucible(11 mm in internal diameter and 14 mm in height). The effect of particle size was also analyzed. The experimental results of mass loss data, X-ray diffraction(XRD) analysis of partially reacted samples and thermodynamic studies indicate that the senarmontite becomes volatile in the form of Sb_4O_6(g) without the formation of any intermediary compound in the entire temperature range. At roasting temperatures, the volatilization kinetics of Sb_2O_3 was analyzed using the model X=kappt. The volatilization reaction was controlled by the surface chemical reaction and an activation energy value of 193.0 k J/mol was obtained in this temperature range. Based on the volatilization kinetics at the melting temperatures, for linear behaviour in nitrogen gas, kinetic constants were determined, and an activation energy of 73.9 k J/mol was calculated for the volatilization reaction with a surface area of 8.171×10~(-5)m~2.
引文
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[9]PADILLA R,ARACENA A,RUIZ MARíA C.Reaction mechanism and kinetics of enargite oxidation at roasting temperatures[J].Metallurgical and Materials Transactions B,2012,43:1119-1126.
[2]ZIVKOVIC Z,STRBAC N,GRUJICIC D,BOYANOV B.Kinetics and mechanism of Sb2S3 oxidation process[J].Thermochimica Acta,2002,383:137-143.
[3]PADILLA R,RAMIREZ G,RUIZ MARíA C.High-temperature volatilization mechanism of stibnite in nitrogen-oxygen atmospheres[J].Metallurgical and Materials Transactions B,2010,41:1284-1292.
[4]ASRYAN N A,ALIKHANYAN A S,NIPAN G D.p-T-x phase diagram of the Sb-O system[J].Inorganic Materials,2004,40:626-631.
[5]ASRYAN N A,ALIKHANYAN A S,NIPAN G D.Specifics of sublimation of antimony oxides[J].Doklady Physical Chemistry,2003,392:221-226.
[6]ROINE A.HSC chemistry 6.1[M].Pori,Finland:Outo Kumpu Research Py,1999.
[7]BARIN I.Thermochemical data of pure substances[M].Weinheim:VCH Verlagsgesellschaft,1995.
[8]PANKRATZ L.Bulletin No.672[M].Washington:U.S.Bureau of Mines,1982.
[9]PADILLA R,ARACENA A,RUIZ MARíA C.Reaction mechanism and kinetics of enargite oxidation at roasting temperatures[J].Metallurgical and Materials Transactions B,2012,43:1119-1126.