CaO-SiO_2-Al_2O_3-MgO-Fe_tO渣系热力学性能的研究—温度和气氛的影响
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摘要
为了向熔融还原法铁浴反应器中获得高质量铁水提供理论依据和完善CaO-SiO_2-Al_2O_3-MgO-Fe_tO五元渣系Fe_tO活度、硫容量和磷容量等热力学数据,应用先进的试验手段,用化学平衡法系统地研究了该渣系中Fe_tO活度、硫容量和磷容量。
采用固体电解质电池测定了该渣系中的Fe_tO活度,用纯铁坩埚作为渣金反应容器,用CO-CO2-Ar混合气体提供体系的氧分压,分析了温度和气氛对渣的Fe_tO活度的影响。得出当只通入氩气,温度由1673K增加到1785K时,渣中Fe_tO活度变化不明显,即温度对该渣系中Fe_tO活度的影响不明显;当通入混合气体,并固定配气比,随着温度的升高,混合气体中氧分压由8.0×10~(-4)Pa增大到110×10~(-4)Pa时,Fe_tO活度呈增加的趋势;当通入混合气体,进气配比变化,温度在1673K恒定,气氛中氧分压由0.14×10~(-4)Pa增大到110×10~(-4)Pa时,该渣系中Fe_tO活度随着氧分压的增大而增大。
用气—渣平衡法测定了该渣系的硫容量,用铂坩埚作为气渣反应容器,用CO-CO2-SO2-Ar混合气体提供体系的氧分压和硫分压,分析了渣的温度和气氛与硫容量之间的关系。得出体系CO、CO2、SO2、Ar进气量一定,温度由1673K增加到1823K时,引起硫分压的降低,使该渣系中硫容量随着温度的升高而减少;温度在1723K恒定,当气氛中氧分压由0.36×10~(-4)Pa增大到7.2×10~(-4)Pa时,引起硫分压的较大增加,使该渣系中硫容量随着氧分压的增大而增大。
用气—渣—金平衡法测定了该渣系的磷容量,用钼坩埚作为反应容器,Ag-0.2%P合金作为气—渣—金平衡的熔剂,CO-CO2-Ar混合气体提供体系的氧分压,分析了温度和气氛与渣中磷容量之间的关系。得出体系CO、CO2、Ar进气配比一定,温度由1723K增加到1823K时,该渣系中磷容量随着温度的升高而减少,即低温有利于去磷;温度在1773K恒定,当气氛中氧分压由0.36×10~(-4)Pa增大到7.2×10~(-4)Pa时,该渣系中磷容量随着氧分压的增大而增大。
综上所述,在试验条件下,低温有利于CaO-SiO_2-Al_2O_3-MgO-Fe_tO五元渣系中Fe_tO活度的减少和硫容量及磷容量的增加;提高氧分压有利于该渣系中Fe_tO活度、硫容量及磷容量的增加。
Abstract In order to improve the thermodynamics data such as Fe_tO activity, sulphur and phosphorus capacity in CaO-SiO_2-Al_2O_3-MgO-Fe_tO slags, and provide theoretics thereunder for the fusing and reduction reactor to get high quality molten iron, the Fe_tO activity and sulphur and phosphorus capacity were studied with chemical equity by advanced experimental method.
A solid-electrolyte cell was used to measure the activity of Fe_tO in the slags. Utilizing pure iron crucible as a reaction vessel, the slag was equilibrated with a mixture gas of CO, CO2 and Ar to provide the oxygen partial pressure. It was analysed that the impaction of slags temperature and gas condition to the aFe_tO in the slags.It was found that the alteration of aFe_tO was very small when the temperature of slags changed from 1673K to 1785K with only injecting Ar. From this, It was concluded that the impaction of the slags temperature to the aFe_tO was small. It was also concluded that aFe_tO in the slags increased when gas was injected with fixed gas mixture ratio and the oxygen pressure increased from 8.0×10~(-4)Pa to 110×10~(-4)Pa with increasing the temperature of slags. It was also concluded that aFe_tO in the slags increased with raising the oxygen pressure from 0.14×10~(-4)Pa to 110×10~(-4)Pa when gas was injected with gas mixture ratio altering and the temperature was fixed at 1673K.
The sulphide capacity of the slags was studied using gas-slag equilibrium techniques. Utilizing Pt crucible as a reaction vessel, the slag was equilibrated with a mixture gas of CO, CO2, SO2 and Ar to provide the oxygen and sulphur partial pressure. It was analysed that the impaction of slags temperature and gas condition to the sulphide capacity in the slags.It was found that the sulphide capacity of the slags decreased when gas was injected with fixed CO、CO2、SO2、Ar mixture ratio and the temperature of slags changed from 1673K to 1823K;It was also concluded that the sulphide capacity of the slags increased with raising the oxygen pressure from 2.21×10~(-4)Pa to 83.14×10~(-4)Pa and the temperature was fixed at 1723K.
The phosphorus capacity of the slags was measured using gas-slag-metal equilibrium techniques. An molybdenum crucible was used as reaction vessel, and Ag-0.2%P alloy as a flux was equilibrated with slags at a constant flow of CO-CO2–Ar gas mixture to provide oxygen partial pressure. It was analysed that the impaction of slags temperature and gas condition to the phosphorus capacity in the slags. It was found that the phosphorus capacity of the slags decreased when gas was injected with fixed CO、CO_2、Ar mixture ratio and the temperature of slags changed from 1723K to 1823K,so the low-temperature is good for dephosphorus;It was also concluded that the phosphorus capacity of the slags increased with raising the oxygen pressure from 0.36×10~(-4)Pa to 7.2×10~(-4)Pa and the temperature was fixed at 1773K.
At experiment condition, low teperiture was propitious to reduce the FetO activity in CaO-SiO_2-Al_2O_3-MgO-Fe_tO slags and increased sulphur and phosphorus capacity; high oxygen pressure was propitious to increase the FetO activity in CaO-SiO_2-Al_2O_3-MgO-Fe_tO slags and increased sulphur and phosphorus capacity
采用固体电解质电池测定了该渣系中的Fe_tO活度,用纯铁坩埚作为渣金反应容器,用CO-CO2-Ar混合气体提供体系的氧分压,分析了温度和气氛对渣的Fe_tO活度的影响。得出当只通入氩气,温度由1673K增加到1785K时,渣中Fe_tO活度变化不明显,即温度对该渣系中Fe_tO活度的影响不明显;当通入混合气体,并固定配气比,随着温度的升高,混合气体中氧分压由8.0×10~(-4)Pa增大到110×10~(-4)Pa时,Fe_tO活度呈增加的趋势;当通入混合气体,进气配比变化,温度在1673K恒定,气氛中氧分压由0.14×10~(-4)Pa增大到110×10~(-4)Pa时,该渣系中Fe_tO活度随着氧分压的增大而增大。
用气—渣平衡法测定了该渣系的硫容量,用铂坩埚作为气渣反应容器,用CO-CO2-SO2-Ar混合气体提供体系的氧分压和硫分压,分析了渣的温度和气氛与硫容量之间的关系。得出体系CO、CO2、SO2、Ar进气量一定,温度由1673K增加到1823K时,引起硫分压的降低,使该渣系中硫容量随着温度的升高而减少;温度在1723K恒定,当气氛中氧分压由0.36×10~(-4)Pa增大到7.2×10~(-4)Pa时,引起硫分压的较大增加,使该渣系中硫容量随着氧分压的增大而增大。
用气—渣—金平衡法测定了该渣系的磷容量,用钼坩埚作为反应容器,Ag-0.2%P合金作为气—渣—金平衡的熔剂,CO-CO2-Ar混合气体提供体系的氧分压,分析了温度和气氛与渣中磷容量之间的关系。得出体系CO、CO2、Ar进气配比一定,温度由1723K增加到1823K时,该渣系中磷容量随着温度的升高而减少,即低温有利于去磷;温度在1773K恒定,当气氛中氧分压由0.36×10~(-4)Pa增大到7.2×10~(-4)Pa时,该渣系中磷容量随着氧分压的增大而增大。
综上所述,在试验条件下,低温有利于CaO-SiO_2-Al_2O_3-MgO-Fe_tO五元渣系中Fe_tO活度的减少和硫容量及磷容量的增加;提高氧分压有利于该渣系中Fe_tO活度、硫容量及磷容量的增加。
Abstract In order to improve the thermodynamics data such as Fe_tO activity, sulphur and phosphorus capacity in CaO-SiO_2-Al_2O_3-MgO-Fe_tO slags, and provide theoretics thereunder for the fusing and reduction reactor to get high quality molten iron, the Fe_tO activity and sulphur and phosphorus capacity were studied with chemical equity by advanced experimental method.
A solid-electrolyte cell was used to measure the activity of Fe_tO in the slags. Utilizing pure iron crucible as a reaction vessel, the slag was equilibrated with a mixture gas of CO, CO2 and Ar to provide the oxygen partial pressure. It was analysed that the impaction of slags temperature and gas condition to the aFe_tO in the slags.It was found that the alteration of aFe_tO was very small when the temperature of slags changed from 1673K to 1785K with only injecting Ar. From this, It was concluded that the impaction of the slags temperature to the aFe_tO was small. It was also concluded that aFe_tO in the slags increased when gas was injected with fixed gas mixture ratio and the oxygen pressure increased from 8.0×10~(-4)Pa to 110×10~(-4)Pa with increasing the temperature of slags. It was also concluded that aFe_tO in the slags increased with raising the oxygen pressure from 0.14×10~(-4)Pa to 110×10~(-4)Pa when gas was injected with gas mixture ratio altering and the temperature was fixed at 1673K.
The sulphide capacity of the slags was studied using gas-slag equilibrium techniques. Utilizing Pt crucible as a reaction vessel, the slag was equilibrated with a mixture gas of CO, CO2, SO2 and Ar to provide the oxygen and sulphur partial pressure. It was analysed that the impaction of slags temperature and gas condition to the sulphide capacity in the slags.It was found that the sulphide capacity of the slags decreased when gas was injected with fixed CO、CO2、SO2、Ar mixture ratio and the temperature of slags changed from 1673K to 1823K;It was also concluded that the sulphide capacity of the slags increased with raising the oxygen pressure from 2.21×10~(-4)Pa to 83.14×10~(-4)Pa and the temperature was fixed at 1723K.
The phosphorus capacity of the slags was measured using gas-slag-metal equilibrium techniques. An molybdenum crucible was used as reaction vessel, and Ag-0.2%P alloy as a flux was equilibrated with slags at a constant flow of CO-CO2–Ar gas mixture to provide oxygen partial pressure. It was analysed that the impaction of slags temperature and gas condition to the phosphorus capacity in the slags. It was found that the phosphorus capacity of the slags decreased when gas was injected with fixed CO、CO_2、Ar mixture ratio and the temperature of slags changed from 1723K to 1823K,so the low-temperature is good for dephosphorus;It was also concluded that the phosphorus capacity of the slags increased with raising the oxygen pressure from 0.36×10~(-4)Pa to 7.2×10~(-4)Pa and the temperature was fixed at 1773K.
At experiment condition, low teperiture was propitious to reduce the FetO activity in CaO-SiO_2-Al_2O_3-MgO-Fe_tO slags and increased sulphur and phosphorus capacity; high oxygen pressure was propitious to increase the FetO activity in CaO-SiO_2-Al_2O_3-MgO-Fe_tO slags and increased sulphur and phosphorus capacity
引文
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[2] Seung-Cheol LEE,Myung-Kyan SHIN,Sanghoon Joo ed. The Effect of Operational Parameters on the Transport Phenomena in COREX Melter-Gasifier[J]. ISIJ International,2000,40(11):1073～1079.
[3] 吕庆,蒋武锋,吕长星等. 熔融气化炉内硫的反应机理与分配[J]. 金属学报,1997,33(9):952～957.
[4] H.M.W.Delport. The COREX Process [J]. Ironmaking and Steelmaking.1992,19(3):183.
[5] 杜鹤桂. 浦项钢铁公司的炼铁生产[J]. 国外钢铁.1996,(5):1～6.
[6] M. Lemperce,W. Maschlake,D. voest-Alpin. COREX 法的现在和未来[J]. 国外钢铁,1994,(5):7～14.
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