铬铁矿高效还原的动力学分析
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摘要
铬铁矿是生产铁铬合金和不锈钢的重要原料,掌握其还原行为对于优化生产工艺和高效利用资源非常重要.本文综述了近40年来对铬矿还原动力学的研究进展,比较了文献中对不同铬铁矿的还原动力学研究,分析了温度、原料条件、还原剂条件和添加剂成分对还原过程的影响,并结合动力学模型对其还原机理进行了探讨,给出了提高还原率的思路方法.
Chromite is a main rawmaterial for production of ferroalloy and stainless steel. A good knowledge of the reduction behavior of chromite is thus of high significance for production optimization and efficient utilization. In this paper a brief reviewof investigation on mechanism and kinetics of solid-state reduction of chromite for the past forty years was given. The literature study for various chromites was summarized. Influences of temperature,properties of material and reductant,as well as the flux addition on the reduction process were analyzed. The reduction mechanism of chromite was explored with kinetic models. Some ideas to promote the reduction ratio were proposed.
Chromite is a main rawmaterial for production of ferroalloy and stainless steel. A good knowledge of the reduction behavior of chromite is thus of high significance for production optimization and efficient utilization. In this paper a brief reviewof investigation on mechanism and kinetics of solid-state reduction of chromite for the past forty years was given. The literature study for various chromites was summarized. Influences of temperature,properties of material and reductant,as well as the flux addition on the reduction process were analyzed. The reduction mechanism of chromite was explored with kinetic models. Some ideas to promote the reduction ratio were proposed.
引文
[1]冯秀梅.微波加热含碳铬铁矿粉体还原过程中电磁性能研究[D].太原:太原理工大学,2007.(Feng Xiumei.Study on the electromagnetic performance of chromite ore fines containing carbon in volumitric reduction by microw ave he ating[D].T aiyuan U niversity of T echnology,2007.)
[2]仉宏亮.铬铁精矿球团烧结-电炉冶炼高碳铬铁合金工艺及机理研究[D].长沙:中南大学,2010.(Zhang Hongliang.Invesitigation on technology and mechanism of high carbon ferrochrome by pellets sinteringelectric furnace smelting process using chromite concentrate[D].Central South University,2010.)
[3]Ding Y L,Warner N A.Catalytic reduction of carbonchromite composite pellets by lime[J].T hermochimica Acta,1997,292(1):85-94.
[4]DingY L,Warner N A.Kinetics and mechanism of reduction of carbon-chromite composite pellets[J].Ironmaking and Steelmaking,1997,24(3):224-229.
[5]Ding Y L,Warner N A.Reduction of carbon-chromite composite pellets w ith silica flux[J].Ironmaking and Steelmaking,1997,24(4):283-287.
[6]Weber P,Eric R H.The reduction mechanism of chromite in the presence of a silica flux[J].M etallurgical T ransactions B,1993,24(12):987-995.
[7]Weber P,Eric R H.The reduction of chromite in the presence of silica flux[J].M inerals Engineering,2006,19(3):318-324.
[8]Weber P,Eric R H.Solid-state fluxed reduction of LG-6chromtie from the bushveld complex[C]//Proc.Int.Ferroalloy C ong.,C ape T ow n South Africa:SAIM M,1992:71-77.
[9]Perry K P D,Finn C W P,King R P.An Ionic diffusion mechanism of chromite reduction[J].M etallurgical T ransactions B,1988,19B(8):677-684.
[10]Neuschutz D,Janβen,Friedrich G,et al.Effect of flux additions on the kinetics of chromite ore reduction w ith carbon[C]//Proc.Int.Ferroalloy Cong.,Trondheim Norway:SAIM M,1995:371-380.
[11]Soykan O,Eric R H,King R P.The reduction mechanism of a natural chromite at 1 416℃[J].M etallurgical T ransactions B,1991,22B(2):53-63.
[12]Duong H V,Johnston.Kinetics of solid state silica fluxed reduction of chromite w ith coal[J].Ironmaking and Steelmaking,2000,27(3):202-206.
[13]Kekkonen M,Xiao YP,Holappa L.Kinetic study on solid state reduction of chromite pellets[C]//Proc.Int.Ferroalloy C ong.,T rondheim N orw ay:SAIM M,1995:351-360.
[14]Tsomondo B M C,Simbi D J,Lesko A.Kinetic Investigation of chromite reduction in a high-carbon ferrochromium alloy bath[C]//Proc.Int.Ferroalloy C ong.,T rondheim N orw ay:SAIM M,1995:361-370.
[15]Lekatou A,Walker R D.Solid state reduction of chromite concentrate:melting of prereduced chromite[J].Ironmaking and Steelmaking,1995,22(5):378-392.
[16]Apaydin F,Atasoy A,Yildiz K.Effect of mechanical activation on carbothermal reduction of chromtie w ith graphit[J].C anadian M etallurgical Q uarterly,2011,50(2):113-118.
[17]Xiao Y,Schuffeneger C,Reuter M,et al.Solid state reduction of chromite w ith C O[C]//Proc.Int.Ferroalloy C ong.,C ape T ow n South Africa:SAIM M,2004:26-35.
[18]Barcza N A,Jochens P R,Howat D D.The mechanism and kinetics of reduction of transvaal chromtie ores[C].Electric Furnace Proceedings,1971,29:88-93.
[19]Rankin W J,Stellenbosch.The composition and structure of chromite during reduction w ith carbon[J].Arch.Eisenhuttenw es,1979,50(9):373-378.
[20]Katayama H G,Tokuda M.The reduction behavior of synthetic chromites by carbon[J].T ransactions ISIJ,1980,20:154-162.
[21]Chakraborty D,Ranganathan.S,Sinha S N.Investigations on the carbothermic reduction of chromite ores[J].M etallurgical and M aterials T ransactions B,2005,41B(8):437-444.
[22]Hiltunen R,Harkki J.Reduction behavior of the akanvaara chromite of northern finland[C]//Proc.Int.Ferroalloy C ong.,C ape T ow n South Africa:SAIM M,2004:36-46.
[23]Ringdalen E,Olsen S E.The effect of chromite ore mineralogy on reduction mechanism and reducibility[C]//Proc.Int.Ferroalloy C ong.,Beijing C hina:SAIM M,1998:124-130.
[24]Perry K P D,Finn C W P,King R P.An Ionic diffusion mechanism of chromite reduction[J].M etallurgical T ransactions B,1988,19B(8):677-684.
[25]Soykan O,Eric R H,King R P.The reduction mechanism of a natural chromite at 1 416℃[J].M etallurgical T ransactions B,1991,22B(2):53-63.
[26]林勤,张梅,徐荣军,等.铬铁矿碳还原动力学研究[J].中国稀土学报,2000,18(9):209-211.(Lin Qin,Zhang Mei,Xu Rongjun,et al.Kinetics of reduction of chrome iron ore by carbon[J].Journal of the C hinese R are Earth Society,2000,18(9):209-211.)
[27]Nafziger R H,Tress J E,Paige J I.Carbothermic reduction of domestic chromites[J].M etallurgical T ransactions B,1979,10B(3):5-14.
[28]李建臣,白国华,李光辉.含碳铬铁矿球团的固态还原特性[J].中国有色金属学报,2011,21(5):1159-1164.(Li Jianchen,Bai Guohua,Li Guanghui.Solid-state reduction properties of carbon-bearing chromite pellets[J].T he C hinese Journal of N onferrous M etals,2011,21(5):1159-1164.)
[29]Xiao Y,Schuffeneger C,Reuter M,et al.Solid state reduction of chromite w ith C O[C]//Proc.Int.Ferroalloy C ong.,C ape T ow n South Africa:SAIM M,2004:26-35.
[30]Chakraborty D,Ranganathan S,Sinha S N.Carbothermic reduction of chromite ore under different flow rates of inert gas[J].Metallurgical and Materials Transactions B,2010,41B(2):10-18.
[31]Lekatou A,Walker R D.Effect of SiO2addition on solid state reduction of chromite concentrate[J].Ironmaking and Steelmaking,1997,24(2):133-143.
[32]Neuschutz D,Janβen,Friedrich G,et al.Effect of flux additions on the kinetics of chromite ore reduction w ith carbon[C]//Proc Int Ferroalloy Cong,Trondheim Norway:SAIM M,1995:371-380.
[33]Dawson N F,Edwards R I.Factors affecting the reduction of chromite[C]//Proc.Int.Ferroalloy C ong.,R io de Janeiro Brazil:SAIM M,1986:105-113.
[34]Lekatou A,Walker R D.Mechanism of solid state reduction of chromite concentrate[J].Ironmaking and Steelmaking,1995,22(5):393-404.
[35]Sundar Murti N S,Seshadri V.Kinetics of reduction of synthetic chromite w ith carbon[J].T ransactions ISIJ,1982,22:925-933.
[2]仉宏亮.铬铁精矿球团烧结-电炉冶炼高碳铬铁合金工艺及机理研究[D].长沙:中南大学,2010.(Zhang Hongliang.Invesitigation on technology and mechanism of high carbon ferrochrome by pellets sinteringelectric furnace smelting process using chromite concentrate[D].Central South University,2010.)
[3]Ding Y L,Warner N A.Catalytic reduction of carbonchromite composite pellets by lime[J].T hermochimica Acta,1997,292(1):85-94.
[4]DingY L,Warner N A.Kinetics and mechanism of reduction of carbon-chromite composite pellets[J].Ironmaking and Steelmaking,1997,24(3):224-229.
[5]Ding Y L,Warner N A.Reduction of carbon-chromite composite pellets w ith silica flux[J].Ironmaking and Steelmaking,1997,24(4):283-287.
[6]Weber P,Eric R H.The reduction mechanism of chromite in the presence of a silica flux[J].M etallurgical T ransactions B,1993,24(12):987-995.
[7]Weber P,Eric R H.The reduction of chromite in the presence of silica flux[J].M inerals Engineering,2006,19(3):318-324.
[8]Weber P,Eric R H.Solid-state fluxed reduction of LG-6chromtie from the bushveld complex[C]//Proc.Int.Ferroalloy C ong.,C ape T ow n South Africa:SAIM M,1992:71-77.
[9]Perry K P D,Finn C W P,King R P.An Ionic diffusion mechanism of chromite reduction[J].M etallurgical T ransactions B,1988,19B(8):677-684.
[10]Neuschutz D,Janβen,Friedrich G,et al.Effect of flux additions on the kinetics of chromite ore reduction w ith carbon[C]//Proc.Int.Ferroalloy Cong.,Trondheim Norway:SAIM M,1995:371-380.
[11]Soykan O,Eric R H,King R P.The reduction mechanism of a natural chromite at 1 416℃[J].M etallurgical T ransactions B,1991,22B(2):53-63.
[12]Duong H V,Johnston.Kinetics of solid state silica fluxed reduction of chromite w ith coal[J].Ironmaking and Steelmaking,2000,27(3):202-206.
[13]Kekkonen M,Xiao YP,Holappa L.Kinetic study on solid state reduction of chromite pellets[C]//Proc.Int.Ferroalloy C ong.,T rondheim N orw ay:SAIM M,1995:351-360.
[14]Tsomondo B M C,Simbi D J,Lesko A.Kinetic Investigation of chromite reduction in a high-carbon ferrochromium alloy bath[C]//Proc.Int.Ferroalloy C ong.,T rondheim N orw ay:SAIM M,1995:361-370.
[15]Lekatou A,Walker R D.Solid state reduction of chromite concentrate:melting of prereduced chromite[J].Ironmaking and Steelmaking,1995,22(5):378-392.
[16]Apaydin F,Atasoy A,Yildiz K.Effect of mechanical activation on carbothermal reduction of chromtie w ith graphit[J].C anadian M etallurgical Q uarterly,2011,50(2):113-118.
[17]Xiao Y,Schuffeneger C,Reuter M,et al.Solid state reduction of chromite w ith C O[C]//Proc.Int.Ferroalloy C ong.,C ape T ow n South Africa:SAIM M,2004:26-35.
[18]Barcza N A,Jochens P R,Howat D D.The mechanism and kinetics of reduction of transvaal chromtie ores[C].Electric Furnace Proceedings,1971,29:88-93.
[19]Rankin W J,Stellenbosch.The composition and structure of chromite during reduction w ith carbon[J].Arch.Eisenhuttenw es,1979,50(9):373-378.
[20]Katayama H G,Tokuda M.The reduction behavior of synthetic chromites by carbon[J].T ransactions ISIJ,1980,20:154-162.
[21]Chakraborty D,Ranganathan.S,Sinha S N.Investigations on the carbothermic reduction of chromite ores[J].M etallurgical and M aterials T ransactions B,2005,41B(8):437-444.
[22]Hiltunen R,Harkki J.Reduction behavior of the akanvaara chromite of northern finland[C]//Proc.Int.Ferroalloy C ong.,C ape T ow n South Africa:SAIM M,2004:36-46.
[23]Ringdalen E,Olsen S E.The effect of chromite ore mineralogy on reduction mechanism and reducibility[C]//Proc.Int.Ferroalloy C ong.,Beijing C hina:SAIM M,1998:124-130.
[24]Perry K P D,Finn C W P,King R P.An Ionic diffusion mechanism of chromite reduction[J].M etallurgical T ransactions B,1988,19B(8):677-684.
[25]Soykan O,Eric R H,King R P.The reduction mechanism of a natural chromite at 1 416℃[J].M etallurgical T ransactions B,1991,22B(2):53-63.
[26]林勤,张梅,徐荣军,等.铬铁矿碳还原动力学研究[J].中国稀土学报,2000,18(9):209-211.(Lin Qin,Zhang Mei,Xu Rongjun,et al.Kinetics of reduction of chrome iron ore by carbon[J].Journal of the C hinese R are Earth Society,2000,18(9):209-211.)
[27]Nafziger R H,Tress J E,Paige J I.Carbothermic reduction of domestic chromites[J].M etallurgical T ransactions B,1979,10B(3):5-14.
[28]李建臣,白国华,李光辉.含碳铬铁矿球团的固态还原特性[J].中国有色金属学报,2011,21(5):1159-1164.(Li Jianchen,Bai Guohua,Li Guanghui.Solid-state reduction properties of carbon-bearing chromite pellets[J].T he C hinese Journal of N onferrous M etals,2011,21(5):1159-1164.)
[29]Xiao Y,Schuffeneger C,Reuter M,et al.Solid state reduction of chromite w ith C O[C]//Proc.Int.Ferroalloy C ong.,C ape T ow n South Africa:SAIM M,2004:26-35.
[30]Chakraborty D,Ranganathan S,Sinha S N.Carbothermic reduction of chromite ore under different flow rates of inert gas[J].Metallurgical and Materials Transactions B,2010,41B(2):10-18.
[31]Lekatou A,Walker R D.Effect of SiO2addition on solid state reduction of chromite concentrate[J].Ironmaking and Steelmaking,1997,24(2):133-143.
[32]Neuschutz D,Janβen,Friedrich G,et al.Effect of flux additions on the kinetics of chromite ore reduction w ith carbon[C]//Proc Int Ferroalloy Cong,Trondheim Norway:SAIM M,1995:371-380.
[33]Dawson N F,Edwards R I.Factors affecting the reduction of chromite[C]//Proc.Int.Ferroalloy C ong.,R io de Janeiro Brazil:SAIM M,1986:105-113.
[34]Lekatou A,Walker R D.Mechanism of solid state reduction of chromite concentrate[J].Ironmaking and Steelmaking,1995,22(5):393-404.
[35]Sundar Murti N S,Seshadri V.Kinetics of reduction of synthetic chromite w ith carbon[J].T ransactions ISIJ,1982,22:925-933.