锰基熔体系统磷杂质净化机理研究
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摘要
锰基合金产业是我国钢铁行业重要分支之一，随着我国钢铁行业的快速发展，目前我国已经成为世界第一锰基合金生产大国，但随着世界金融危机影响的进一步加剧，钢铁行业出现严重产能过剩，面临巨大困难，锰基合金产业长期以来的弊端暴露无遗：生产技术停滞不前，长期依靠进口高品位锰矿，生产成本受制于人；能耗居高不下，资源浪费严重；产品品质低下，磷等杂质元素含量高，无法满足客户需求，行业已经到了转型升级的关键时刻。在这样的背景下，本文开展了锰基熔体系统的基础研究，旨在阐述锰基熔体中各结构单元的热力学行为，为锰基合金冶炼过程提供最佳工艺参数，减少合金元素损失；为锰基合金磷杂质的去除提供理论依据，有效降低锰基合金中杂质元素含量，提高产品品质；同时填补锰基多元熔体热力学模型研究的空缺，为此本文对锰基熔体系统主要做了以下几个方面的工作：
①基于共存理论建立了锰基合金系统涉及的Mn-Fe-Si、Mn-Fe-P三元熔体系统、Mn-Fe-Si-P-C复杂多元熔体系统热力学模型。并通过模型计算值与实验值比较，证明了此类熔体中三元缔合物MnFeSi、MnFeP的存在，阐述了计算活度值与实验测定值在P含量较高时出现偏差的原因，证明了基于共存理论建立的三元和多元锰基熔体数学模型能够准确的描述熔体中各元素的热力学行为和各元素在各结构单元中的分布情况。
②基于共存理论建立了CaO-MnO-SiO2、BaO-MnO-SiO2两种锰基合金冶炼中常见三元渣系热力学模型，分析了BaO基三元熔体中BaSiO3、Ba2SiO4盐类原子团的存在；基于共存理论建立了CaO-BaO-MnO-SiO2四元渣系热力学模型，为锰基合金冶炼中CaO基渣系中添加BaO提供热力学理论计算工具；基于共存理论建立了CaO-SiO2-MnO-FeO-Fe2O3多元渣系热力学模型，为实际生产中锰矿冶炼中锰的还原与氧化损失提供理论计算工具。
③利用Mn-Fe-Si-P-C多元熔体模型，计算了1600K~2000K之间8种国标典型成分的锰基熔体中Mn、Fe、Si、C、P元素的活度，以此计算了锰基熔体内部各元素氧化所需的最低溶解氧活度，从而判断4种锰硅合金内部理论上无法完成P的氧化去除，而在4种锰铁合金中，虽然Mn先于Si氧化，但是P氧化临界溶解氧活度仍大于Fe、C、Si、Mn四种元素，同样无法完成P的氧化去除。
④通过将熔体熔渣系统模型进行耦合，分析了硅锰合金的氧化脱磷热力学可行性，得出了与实验结果一致的结论：硅锰合金无法完成氧化脱磷，并且给出的硅锰合金无法完成氧化脱磷的根本原因是硅锰合金中的Si含量大，具有极低的临界氧化氧活度；理论模型给出了锰铁合金完成氧化脱磷的BaO基渣系中最多可以添加摩尔分数为0.1的CaO，SiO2浓度小于0.18适合锰铁合金氧化脱磷保锰；C可以提高P的活度，降低Mn的活度，有利于脱磷保锰。
⑤分析了锰基合金还原脱磷可能出现的三种情况，建立了熔体内部还原脱磷的Ca-Mn-Si-Fe-P-C多元熔体模型，计算表明：当Ca含量摩尔分数大于0.17后，脱磷率开始大于10%，当Ca含量达到0.32以后，脱磷率无限接近于1，再继续添加更多的Ca对脱磷无任何作用；建立了带析出相的多元熔体模型，计算表明：当Ca小于0.148时，熔体内部不可能发生脱磷反应，对于熔体内部的还原脱磷反应，Ca的加入量在0.154~0.294之间，改变Ca的加入量具有实际的还原脱磷调控能力，当Ca加入量为0.36时，脱磷率接近1；建立了带析出相的多元熔体熔渣耦合模型，对锰基还原脱磷过程进行了数学模拟，计算表明：当渣中Ca3P2摩尔分数从0.1~1.0变化，脱磷量（率）变化趋势均一致，但是开始脱磷的Ca加入量随着Ca3P2摩尔分数的减小而减小，渣系达到极限脱磷率接近1时的Ca加入量也随着l的减小而减小。
⑥实验分析了锰基多元合金系统结构失效粉化的过程，讨论了磷杂质元素对锰基合金结构稳定性的影响，表明Mn-Al-Fe-Si合金的彻底解体粉化是合金凝固时物相体积突变和磷化物等夹杂物水解反应两个过程共同作用的结果，水解反应和微裂纹的生长是相辅相成的过程，后者为前者提供反应的动力学通道，前者为后者的进一步生长提供突变能壁所需能量，而Ti的加入能够在合金中发挥抑制水解反应的发生，但它并不能阻止δ-Mn到β-Mn的晶型转变和相的生成过程带来的体积突变，所以Ti的添加并不能阻止合金的开裂，仅能减少合金的粉化。
Manganese-based alloys industry is an important branch of China's steel industry.With the rapid development of China's iron and steel industry, China has become theworld's largest producer of manganese-based alloys at present. But with the deepeningimpact of the world financial crisis, steel industry appeared serious overcapacity andfaces enormous difficulties. The shortcomings of manganese industry has beenthoroughly exposed: stagnant production technology, long depending on importedhigh-grade manganese ore, cost of production controlled by others; and also high energyconsumption, serious waste of resources, low product quality, and high content ofphosphorus and other impurities. It is unable to meet customer demands, and hasreached a critical moment of transformation and upgrading. With this background, thebasic research on manganese-based melt system was carried out in this paper forillustrating the thermodynamic behavior of the various structural units in themanganese-based melt system, to provide the best smelting technological parameter ofthe manganese-based alloy smelting process, to reduce the alloy elements loss, toprovide a theoretical basis for the removal of phosphorus impurities inmanganese-based alloys, to effectively reduce the impurity elements inmanganese-based alloys, to improve product quality, and Meanwhile, to fill the vacancyof the study on the multi-thermodynamic model of manganese-based melt and toprovide a basis research methods for further study on manganese-based alloy meltsystem. So based on manganese melt system it was mainly done the following aspectsof the work in this paper:
①Based on the ideal association solution theory, A ternary thermodynamicsmodel for Mn-Fe-Si, Mn-Fe-P and multiple thermodynamics model for Mn-Fe-Si-P-Csystem were established. Compareing the model calculating value and experimentalvalue, it was proved that the existing of the ternary assciations MnFeSi and MnFeP. itexplained the reasons for the activity deviation between calculating value and measuredvalues at higher P content. It also proved that the ternary and multiple modelsestablished can accurately describe the thermodynamic behavior of all elements and itsdistribution in the structural units of the maganese-based melt.
②Base on the coexisting theory, the ternary thermodynamics model forCaO-MnO-SiO2and BaO-MnO-SiO2slag used for Mn-based alloys smelting was established and with the model the salt association BaSiO3and Ba2SiO4was provedexisiting. Base on the coexisting theory, a quaternary thermodynamics model forCaO-BaO-MnO-SiO2slag used for Mn-based alloys smelting was established forcalculating the thermodynamics property of the CaO-based slag with BaO added. Amultiple slag thermodynamics model for CaO-SiO2-MnO-FeO-Fe2O3was establishedfor Mn-based alloys smelting to provide the theoretical calculation tool used in analysisof the oxidization and reducing of alloy elements and Mn loss.
③With the Mn-Fe-Si-P-C multiple melt model, the activity of Mn、Fe、Si、C、P of eight typical chemical composition Mn-based alloys was calculated under thetemperature1600K~2000K, and by this results the lowest critical oxygen activity foreach elements was calculated to show that:4kinds of MnSi alloys can not be oxidizingdephosphorized on the inside of MnSi melt, and on the inside of4kinds of MnFe alloysmelt, Mn was oxidized before Si, the critical oxygen activity of P was larger than that ofFe、C、Si、Mn, it also can not finish the oxidizing dephosphorization.
④By coupling the melt and slag system model to analyze the thermodynamicsfeasibility of MnSi alloys alloys oxidizing dephosphorization and draw a conclusionwhich was consistent with the experimental results: it was unable to complete oxidationdephosphorizing in MnSi alloy, and suggest that the root cause of this was Si had verylow critical oxygen activity. The theoretical model shows the most molar fraction ofCaO added up to BaO-based slag to completed oxidation dephosphorization in MnFealloys is0.1, the mole fraction of SiO2less than0.18is suitable to dephosphorizationand saving Mn, and C can increase the activity of P, reduce Mn activity which also isconducive for dephosphorization and saving Mn.
⑤Three cases of reducing dephosphorization for manganese-based alloys wasarosed. A multiple model for the case a on the inside of Ca-Mn-Si-Fe-P-C melt wasestablished. The calculation showed that when the Ca mole fraction was greater than0.17, the dephosphorization rate began to be larger than10%, and when it was greaterthan0.32, the dephosphorizing rate was infinitely close to1. A multiple model withprecipitated phase for the case b was established. The calculation results showed thatwhen the Ca mole fraction was less than0.148, it was impossible to dephosphorize.When the Ca-content is in the range of0.154~0.294, it could effectively control thereducing dephosphorization rate. When the more fraction of Ca was0.36, thedephosphorizing rate was infinitely close to1. A coupling multiple model between meltand slag with precipitated phase for the case c was established to analyze the process of dephosphorization on the interface of slag and melt. The calculating results showed thatthe change tendency was consistent when the Ca3P2-content in slag was changing from0.1to1, and the Ca-content for beginning to dephosphorize reduced as the Ca3P2molefraction reduced, and the quantity of Ca added for reaching to the dephosphorizationlimit was reduce when l came down.
⑥The process of the cracking and disintegration of the Mn-Al-Fe-Si masteralloys and the effect of P on the stablity of the alloys was analyzed by experimentsdesigned. It revealed that pulverization of this alloy is due to the internal stress causedby volume change and hydrolysis. The two steps interacted with each other and led tocomplete disintegration of the alloys together, The latter provided kinetics channel forthe former and the former provided the energy for further development of the latter.Addition of Ti can decrease the hydrolysis reactions due to the lower free energy of TiCand TiP than that of AlP and Al4C3. But it did not influence phase transitions of β-Mnand ζ phase, So the addition of Ti only can reduce the powder rate of the alloys but didnot work on the crack action which just divided the alloys into smaller blocks.
①基于共存理论建立了锰基合金系统涉及的Mn-Fe-Si、Mn-Fe-P三元熔体系统、Mn-Fe-Si-P-C复杂多元熔体系统热力学模型。并通过模型计算值与实验值比较，证明了此类熔体中三元缔合物MnFeSi、MnFeP的存在，阐述了计算活度值与实验测定值在P含量较高时出现偏差的原因，证明了基于共存理论建立的三元和多元锰基熔体数学模型能够准确的描述熔体中各元素的热力学行为和各元素在各结构单元中的分布情况。
②基于共存理论建立了CaO-MnO-SiO2、BaO-MnO-SiO2两种锰基合金冶炼中常见三元渣系热力学模型，分析了BaO基三元熔体中BaSiO3、Ba2SiO4盐类原子团的存在；基于共存理论建立了CaO-BaO-MnO-SiO2四元渣系热力学模型，为锰基合金冶炼中CaO基渣系中添加BaO提供热力学理论计算工具；基于共存理论建立了CaO-SiO2-MnO-FeO-Fe2O3多元渣系热力学模型，为实际生产中锰矿冶炼中锰的还原与氧化损失提供理论计算工具。
③利用Mn-Fe-Si-P-C多元熔体模型，计算了1600K~2000K之间8种国标典型成分的锰基熔体中Mn、Fe、Si、C、P元素的活度，以此计算了锰基熔体内部各元素氧化所需的最低溶解氧活度，从而判断4种锰硅合金内部理论上无法完成P的氧化去除，而在4种锰铁合金中，虽然Mn先于Si氧化，但是P氧化临界溶解氧活度仍大于Fe、C、Si、Mn四种元素，同样无法完成P的氧化去除。
④通过将熔体熔渣系统模型进行耦合，分析了硅锰合金的氧化脱磷热力学可行性，得出了与实验结果一致的结论：硅锰合金无法完成氧化脱磷，并且给出的硅锰合金无法完成氧化脱磷的根本原因是硅锰合金中的Si含量大，具有极低的临界氧化氧活度；理论模型给出了锰铁合金完成氧化脱磷的BaO基渣系中最多可以添加摩尔分数为0.1的CaO，SiO2浓度小于0.18适合锰铁合金氧化脱磷保锰；C可以提高P的活度，降低Mn的活度，有利于脱磷保锰。
⑤分析了锰基合金还原脱磷可能出现的三种情况，建立了熔体内部还原脱磷的Ca-Mn-Si-Fe-P-C多元熔体模型，计算表明：当Ca含量摩尔分数大于0.17后，脱磷率开始大于10%，当Ca含量达到0.32以后，脱磷率无限接近于1，再继续添加更多的Ca对脱磷无任何作用；建立了带析出相的多元熔体模型，计算表明：当Ca小于0.148时，熔体内部不可能发生脱磷反应，对于熔体内部的还原脱磷反应，Ca的加入量在0.154~0.294之间，改变Ca的加入量具有实际的还原脱磷调控能力，当Ca加入量为0.36时，脱磷率接近1；建立了带析出相的多元熔体熔渣耦合模型，对锰基还原脱磷过程进行了数学模拟，计算表明：当渣中Ca3P2摩尔分数从0.1~1.0变化，脱磷量（率）变化趋势均一致，但是开始脱磷的Ca加入量随着Ca3P2摩尔分数的减小而减小，渣系达到极限脱磷率接近1时的Ca加入量也随着l的减小而减小。
⑥实验分析了锰基多元合金系统结构失效粉化的过程，讨论了磷杂质元素对锰基合金结构稳定性的影响，表明Mn-Al-Fe-Si合金的彻底解体粉化是合金凝固时物相体积突变和磷化物等夹杂物水解反应两个过程共同作用的结果，水解反应和微裂纹的生长是相辅相成的过程，后者为前者提供反应的动力学通道，前者为后者的进一步生长提供突变能壁所需能量，而Ti的加入能够在合金中发挥抑制水解反应的发生，但它并不能阻止δ-Mn到β-Mn的晶型转变和相的生成过程带来的体积突变，所以Ti的添加并不能阻止合金的开裂，仅能减少合金的粉化。
Manganese-based alloys industry is an important branch of China's steel industry.With the rapid development of China's iron and steel industry, China has become theworld's largest producer of manganese-based alloys at present. But with the deepeningimpact of the world financial crisis, steel industry appeared serious overcapacity andfaces enormous difficulties. The shortcomings of manganese industry has beenthoroughly exposed: stagnant production technology, long depending on importedhigh-grade manganese ore, cost of production controlled by others; and also high energyconsumption, serious waste of resources, low product quality, and high content ofphosphorus and other impurities. It is unable to meet customer demands, and hasreached a critical moment of transformation and upgrading. With this background, thebasic research on manganese-based melt system was carried out in this paper forillustrating the thermodynamic behavior of the various structural units in themanganese-based melt system, to provide the best smelting technological parameter ofthe manganese-based alloy smelting process, to reduce the alloy elements loss, toprovide a theoretical basis for the removal of phosphorus impurities inmanganese-based alloys, to effectively reduce the impurity elements inmanganese-based alloys, to improve product quality, and Meanwhile, to fill the vacancyof the study on the multi-thermodynamic model of manganese-based melt and toprovide a basis research methods for further study on manganese-based alloy meltsystem. So based on manganese melt system it was mainly done the following aspectsof the work in this paper:
①Based on the ideal association solution theory, A ternary thermodynamicsmodel for Mn-Fe-Si, Mn-Fe-P and multiple thermodynamics model for Mn-Fe-Si-P-Csystem were established. Compareing the model calculating value and experimentalvalue, it was proved that the existing of the ternary assciations MnFeSi and MnFeP. itexplained the reasons for the activity deviation between calculating value and measuredvalues at higher P content. It also proved that the ternary and multiple modelsestablished can accurately describe the thermodynamic behavior of all elements and itsdistribution in the structural units of the maganese-based melt.
②Base on the coexisting theory, the ternary thermodynamics model forCaO-MnO-SiO2and BaO-MnO-SiO2slag used for Mn-based alloys smelting was established and with the model the salt association BaSiO3and Ba2SiO4was provedexisiting. Base on the coexisting theory, a quaternary thermodynamics model forCaO-BaO-MnO-SiO2slag used for Mn-based alloys smelting was established forcalculating the thermodynamics property of the CaO-based slag with BaO added. Amultiple slag thermodynamics model for CaO-SiO2-MnO-FeO-Fe2O3was establishedfor Mn-based alloys smelting to provide the theoretical calculation tool used in analysisof the oxidization and reducing of alloy elements and Mn loss.
③With the Mn-Fe-Si-P-C multiple melt model, the activity of Mn、Fe、Si、C、P of eight typical chemical composition Mn-based alloys was calculated under thetemperature1600K~2000K, and by this results the lowest critical oxygen activity foreach elements was calculated to show that:4kinds of MnSi alloys can not be oxidizingdephosphorized on the inside of MnSi melt, and on the inside of4kinds of MnFe alloysmelt, Mn was oxidized before Si, the critical oxygen activity of P was larger than that ofFe、C、Si、Mn, it also can not finish the oxidizing dephosphorization.
④By coupling the melt and slag system model to analyze the thermodynamicsfeasibility of MnSi alloys alloys oxidizing dephosphorization and draw a conclusionwhich was consistent with the experimental results: it was unable to complete oxidationdephosphorizing in MnSi alloy, and suggest that the root cause of this was Si had verylow critical oxygen activity. The theoretical model shows the most molar fraction ofCaO added up to BaO-based slag to completed oxidation dephosphorization in MnFealloys is0.1, the mole fraction of SiO2less than0.18is suitable to dephosphorizationand saving Mn, and C can increase the activity of P, reduce Mn activity which also isconducive for dephosphorization and saving Mn.
⑤Three cases of reducing dephosphorization for manganese-based alloys wasarosed. A multiple model for the case a on the inside of Ca-Mn-Si-Fe-P-C melt wasestablished. The calculation showed that when the Ca mole fraction was greater than0.17, the dephosphorization rate began to be larger than10%, and when it was greaterthan0.32, the dephosphorizing rate was infinitely close to1. A multiple model withprecipitated phase for the case b was established. The calculation results showed thatwhen the Ca mole fraction was less than0.148, it was impossible to dephosphorize.When the Ca-content is in the range of0.154~0.294, it could effectively control thereducing dephosphorization rate. When the more fraction of Ca was0.36, thedephosphorizing rate was infinitely close to1. A coupling multiple model between meltand slag with precipitated phase for the case c was established to analyze the process of dephosphorization on the interface of slag and melt. The calculating results showed thatthe change tendency was consistent when the Ca3P2-content in slag was changing from0.1to1, and the Ca-content for beginning to dephosphorize reduced as the Ca3P2molefraction reduced, and the quantity of Ca added for reaching to the dephosphorizationlimit was reduce when l came down.
⑥The process of the cracking and disintegration of the Mn-Al-Fe-Si masteralloys and the effect of P on the stablity of the alloys was analyzed by experimentsdesigned. It revealed that pulverization of this alloy is due to the internal stress causedby volume change and hydrolysis. The two steps interacted with each other and led tocomplete disintegration of the alloys together, The latter provided kinetics channel forthe former and the former provided the energy for further development of the latter.Addition of Ti can decrease the hydrolysis reactions due to the lower free energy of TiCand TiP than that of AlP and Al4C3. But it did not influence phase transitions of β-Mnand ζ phase, So the addition of Ti only can reduce the powder rate of the alloys but didnot work on the crack action which just divided the alloys into smaller blocks.
引文
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