氟磷灰石碳热还原过程及动力学研究?
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摘要
为探明电炉法黄磷的反应历程,采用纯物质模拟电炉法黄磷生产,并使用HSC热力学软件、X射线衍射(XRD)、扫描电子显微镜(SEM)等分析方法对该过程进行辅助研究。HSC和XRD分析结果表明氟磷灰石碳热还原反应历程如下:Ca_5(PO_4)_3F优先与SiO_2发生脱氟反应生成Ca_3(PO_4)_2,而Ca_3(PO_4)_2又被碳还原产生CaO,并结合SiO_2形成钙硅酸盐,而F最终以SiF_4(g)的形式排出体系;动力学分析结果表明氟磷灰石的碳热还原反应是一个变级反应,反应级数随温度升高而降低,反应速率随温度升高而增大,随时间增大而降低,其反应活化能为188.96 kJ×mol~(-1),表明是一个高能耗反应;渣相SEM分析结果表明随着温度的升高,体系的液相逐渐增多,物质扩散加快,导致反应速率增大,这与动力学分析结果相一致。
In order to investigate yellow phosphorus production in electric furnace, pure chemicals were used to simulate this process in electric furnace. The process was studied by HSC thermodynamics software, X-ray diffraction(XRD) and Scanning electron microscope(SEM). Thermodynamics and XRD analysis indicate that the carbothermal reduction process of fluoroapatite is as follows: Ca_5(PO_4)_3 F is preferentially defluorinated with SiO_2 to form Ca_3(PO_4)_2, and Ca_3(PO_4)_2 is then reduced by carbon to produce CaO which combines with SiO_2 to form calcium silicate. Meanwhile, F is discharged in the form of SiF_4(g). Kinetic analysis shows that the carbothermal reduction reaction is a graded reaction. Reaction order decreases with the increase of temperature.The reaction rate increases with temperature and decreases with time. The activation energy is 188.96 k J×mol~(-1),which indicates that it is a highly energy-consuming reaction. SEM analysis of slag phase shows that liquid phase of the system gradually increases with the increase of temperature, which accelerates diffusion and increases the reaction rate. This trend is consistent with the results of kinetic analysis.
In order to investigate yellow phosphorus production in electric furnace, pure chemicals were used to simulate this process in electric furnace. The process was studied by HSC thermodynamics software, X-ray diffraction(XRD) and Scanning electron microscope(SEM). Thermodynamics and XRD analysis indicate that the carbothermal reduction process of fluoroapatite is as follows: Ca_5(PO_4)_3 F is preferentially defluorinated with SiO_2 to form Ca_3(PO_4)_2, and Ca_3(PO_4)_2 is then reduced by carbon to produce CaO which combines with SiO_2 to form calcium silicate. Meanwhile, F is discharged in the form of SiF_4(g). Kinetic analysis shows that the carbothermal reduction reaction is a graded reaction. Reaction order decreases with the increase of temperature.The reaction rate increases with temperature and decreases with time. The activation energy is 188.96 k J×mol~(-1),which indicates that it is a highly energy-consuming reaction. SEM analysis of slag phase shows that liquid phase of the system gradually increases with the increase of temperature, which accelerates diffusion and increases the reaction rate. This trend is consistent with the results of kinetic analysis.
引文
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[21]李银,夏举佩,陈正杰,等.钾长石作为助熔剂熔融还原磷矿的可行性研究[J].硅酸盐通报,2017,36(8):2737-2742.LI Y,XIA J P,CHEN Z J,et al.Feasibility Study on potassium feldspar as flux to reduce phosphate ore[J].Bulletin of the Chinese Ceramic Society,2017,36(8):2737-2742.
[22]马超,胡彪,吴元欣,等.低品位磷矿熔融还原反应动力学研究[J].化工矿物与加工,2014,43(3):1008-1012.MA C,HU B,WU Y X,et al.Study on reaction in smelting reduction of low-grade phosphate ores[J].Industrial Minerals Processing,2014,43(3):1008-1012.
[23]李茜,胡彪,吴元欣,等.熔融法还原中低品位磷矿的工艺及动力学[J].高校化学工程学报,2014,28(4):905-910.LI Q,HU B,WU Y X,et al.Process parameters and kinetics of smelting reduction technology for low-phosphate ore reduction[J].Journal of Chemical Engineering of Chinese Universities,2014,28(4):905-910.
[24]杨军,陈建钧,刘海燕,等.铝杂质强化固相碳热还原氟磷灰石过程分析[J].四川大学学报,2015,47(1):186-191.YANG J,CHEN J J,LIU H Y,et al.Enhanced effect of aluminum impurity on solid state carbonthermal reduction of fluorapatite[J].Journal of Si Chuan University Engineering,2015,47(1):186-191.
[2]GENG R X,XIA J P,CHEN Z J,et al.Effects of potassium feldspar on slagging and fluxing in phosphorus produced via electric furnace[J].Phosphorus Sulfur&Silicon&the Related Elements,2016,192(4):475-480
[3]LI Y,CHEN Z J,GENG R X,et al.Studies on extraction of phosphorus from phosphate ore by electric furnace with different fluxing agents[J].Phosphorus Sulfur&Silicon&the Related Elements,2018,193(3):141-148.
[4]李银,夏举佩,刘海浪,等.硅石、钾长石助熔磷矿碳热还原反应机理研究[J].高校化学工程学报,2017,31(5):1120-1126.LI Y,XIA J P,LIU H L,et al.Mechanism of silica and k-feldspar as flux agents in phosphate ore carbothermic reduction[J].Journal of Chemical Engineering of Chinese Universities,2017,31(5):1120-1126.
[5]刘明理.窑法利用中低品位磷矿石生产工业磷酸的研究[J].化学研究与应用,2009,21(1):131-134.LIU M L.Study of producing industrial phosphoric acid with middle-low grade phosphate rock by vertical kiln method[J].Chemical Research and Application,2009,21(1):131-134.
[6]JACOB K D,REYNOLDS D S.HILL W W.Reduction of tricalcium phosphate by carbon[J].Industrial and Engineering Chemical Research,2002,20(1):1204-1210.
[7]JACOB M U.FREDERIC L.PARK W C,et al.Reduction of phosphate ores by carbon:Part I.Process variables for design of rotary kiln system[J].Metallurgical Transactions B,1986,17(4):861-868.
[8]张进荣,袁孝惇,王叔民.磷矿还原机理研究[J].过程工程学报,1986,6(2):114-116.ZHANG J R,YUAN X C,WANG S M.Study on reduction mechanism of phosphate rock[J].The Chinese Journal of Process Engineering,1986,6(2):114-116.
[9]鲍晓军,袁孝惇,王叔民.磷矿石熔态还原动力学及反应机理的研究[J].化肥工业,1987,12(6):2-5.BAO X J,YUAN X C,WANG S M.Study on melting reduction kinetics and reaction mechanism of phosphate ore[J].Journal of Chemical Fertilizer Industry,1987,12(6):2-5.
[10]邱礼有,梁斌,江礼科.氟磷灰石固态还原过程实验研究[J].化工学报,1996,47(1):65-71.QIU L Y,LIANG B,JIANG L K.Investigation on the solid state reduction of fluorapatite[J].Journal of Chemical Industry&Engineering,1996,47(1):65-71.
[11]江礼科,邱礼有,梁斌,等.氟磷灰石热炭固态还原反应机理[J].成都科技大学学报,1995(1):1-5.JIANG L K,QIU L Y,LIANG B,et al.Solid reaction mechanism for the thermal reduction of fluorapatite by carbon[J].Journal of Chen Du University of Science and Technology,1995(1):1-5.
[12]郭占成,王大光,许志宏.磷矿石熔融还原(I)磷酸盐还原实验研究[J].化工学报,1994,45(3):257-265.GUO Z C,WANG D G,XU Z H.Smelting reduction of phosphorus ore(I)laboratory investigation on phosphate reduction[J].Journal of Chemical Industry&Engineering,1994,45(3):257-265.
[13]郭占成,王大光,许志宏.磷矿石熔融还原(II)磷酸盐还原实验研究[J].化工学报,1994,45(3):265-272.GUO Z C,WANG D G,XU Z H.Smelting reduction of phosphorus ore(II))laboratory investigation on phosphate reduction[J].Journal of Chemical Industry&Engineering,1994,45(3):265-272.
[14]李秋霞,吕娇,荆碧.氟磷酸钙与碳反应生成CaO、CO(g)、CaF2和PO2(g)的热力学[J].真空,2014,51(6):56-58.LI Q X,LV J,JING B.The thermodynamic calculation of the reaction about calcium fluophosphate and carbon generating CaO,CO,CaF2 and PO2(g)[J].Vacuum,2014,51(6):56-58.
[15]刘予成,李秋霞,邱臻哲,等.SiO2对氟磷酸钙真空碳热还原反应的影响[J].真空科学与技术学报,2013,33(3):293-296.LIU Y C,LI Q X,QIU Z Z,et al.Mechanisms SiO2on the fluoraptite by carbothermic reduction reaction in vacuum[J].Chinese Journal of Vacuum Science and Technology,2013,33(3):293-296.
[16]刘予成,李秋霞,刘永成.氟磷酸钙真空碳热还原反应机理[J].真空,2012,49(3):84-87.LIU Y C,LI Q X,LIU Y C.Carbothermal reduction mechanism of fluorapatite in vacuum[J].Vacuum,2012,49(3):84-87.
[17]邓淑元,梁斌,李春,等.窑法磷酸技研究进展[J].化工进展,2012,31(7):402-406.DENG S Y,LIANG B,LI C,et al.Research progress of kiln phosphoric acid process[J].Chemical Industry&Engineering Progress,2012,31(7):402-406.
[18]覃扬颂,王重华,黄小凤,等.熔融态黄磷炉渣的综合利用[J].化工进展,2012,31(10):2319-2323.QIN Y S,WANG C H,HUANG X F,et al.Utilization of melting yellow phosphor furnace slag[J].Chemical Industry and Engineering Progress,2012,31(10):2319-2323.
[19]蒋明,王重华,黄小凤,等.黄磷炉渣热态成型资源化过程的二次污染预测[J].中南大学学报(自然科学版),2016,47(3):1078-1084.JIANG M,WANG C H,HUANG X F,et al.Secondary pollution prediction of recycling process of yellow phosphorus slag by moulding under thermal state[J].Journal of Central South University(Science and Technology),2016,47(3):1078-1084.
[20]曹任飞,夏举佩,李宛霖,等.碱金属碳酸盐对磷矿碳热还原反应的影响研究[J].高校化学工程学报,2018,32(3):568-576.CAO R F,XIA J P,LI W L,et al.Effects of alkali metal carbonates on carbothermal reduction of phosphate rock[J].Journal of Chemical Engineering of Chinese Universities,2018,32(3):568-576.
[21]李银,夏举佩,陈正杰,等.钾长石作为助熔剂熔融还原磷矿的可行性研究[J].硅酸盐通报,2017,36(8):2737-2742.LI Y,XIA J P,CHEN Z J,et al.Feasibility Study on potassium feldspar as flux to reduce phosphate ore[J].Bulletin of the Chinese Ceramic Society,2017,36(8):2737-2742.
[22]马超,胡彪,吴元欣,等.低品位磷矿熔融还原反应动力学研究[J].化工矿物与加工,2014,43(3):1008-1012.MA C,HU B,WU Y X,et al.Study on reaction in smelting reduction of low-grade phosphate ores[J].Industrial Minerals Processing,2014,43(3):1008-1012.
[23]李茜,胡彪,吴元欣,等.熔融法还原中低品位磷矿的工艺及动力学[J].高校化学工程学报,2014,28(4):905-910.LI Q,HU B,WU Y X,et al.Process parameters and kinetics of smelting reduction technology for low-phosphate ore reduction[J].Journal of Chemical Engineering of Chinese Universities,2014,28(4):905-910.
[24]杨军,陈建钧,刘海燕,等.铝杂质强化固相碳热还原氟磷灰石过程分析[J].四川大学学报,2015,47(1):186-191.YANG J,CHEN J J,LIU H Y,et al.Enhanced effect of aluminum impurity on solid state carbonthermal reduction of fluorapatite[J].Journal of Si Chuan University Engineering,2015,47(1):186-191.