液渣成分和硅酸二钙颗粒含量对铁水预处理非均相脱磷剂脱磷能力的影响

高磷铁水预处理脱磷的难题是脱磷剂用量太大、温降太多,急需研究脱磷能力强的脱磷剂。含有固体颗粒和液渣的非均相脱磷剂比仅含液渣的均相脱磷剂的脱磷能力强很多。为此,针对磷的质量分数为0.5%的高磷铁水,应用FactSageTM热力学软件优选出脱磷能力强的3种液渣,添加不同数量的硅酸二钙颗粒配制非均相脱磷剂试样,脱磷剂和熔铁在1 560℃下反应6h,测定熔铁中的平衡磷含量,用以评价其脱磷能力,然后在1 400℃下进行了铁水脱磷预处理试验。研究结果表明,随着硅酸二钙颗粒含量的增加,非均相脱磷剂的脱磷能力明显改善;采用非均相脱磷剂有助于减少渣量和控制反应器内衬的侵蚀;采用非均相脱磷剂对铁水脱磷,仍然需要控制较高的渣铁界面FetO浓度。     

苏打脱磷剂冲罐法铁水脱磷

 为研究铁水冲罐法对铁水预处理脱磷效果的影响,向放有一定量苏打的铁水罐中倒入铁水进行铁水脱磷工业试验研究。考察了铁水中Si、Ti浓度、铁水温度以及苏打添加量对脱磷率的影响,并比较了钙系脱磷剂与苏打的脱磷效果。结果表明：铁水中低的硅、钛浓度、低温以及适当的苏打消耗量有助于脱磷;与钙系脱磷剂只有一定的脱磷能力相比,苏打有较强的脱磷和脱硫能力;同时考察了氧气对苏打脱磷效果的影响,向铁水表面喷吹氧气可以减少铁水温降,为铁水的二次预处理提供温降空间,采用苏打铁水二次脱磷后,得到了w［P］＜0.010%的铁水;还考察了苏打脱磷过程中w［Cr］、w［V］和w［C］的变化,铁水中铬浓度几乎不变,钒几乎全部被氧化进入渣中,而碳浓度大约减小了0.2%(质量分数,下同)。     

含转炉渣的预熔脱磷剂进行铁水脱磷实验

在实验室条件下,用部分转炉渣代替预熔脱磷剂中纯化学试剂原料进行铁水预处理脱磷实验研究,研究发现,含有转炉渣的预熔脱磷剂能实现较好的脱磷效果;在1350℃,加入量为10％的条件下,含转炉渣45.73％的预熔脱磷剂能将铁水中的磷由0.21％降低到0.011％,脱磷率可达到94.76％。     

预熔脱磷剂进行铁水脱磷的实验研究

在实验室条件下,以CaO-Fe2O3-CaF2为预熔脱磷剂的主要渣系,对预熔脱磷剂的配比关系、加入量、处理温度、初始铁水磷含量以及预熔渣粒度进行了研究.结果发现:在1 350℃条件下,w(CaO)/w(Fe2O3)约取1.0,在加入量为10%的预熔脱磷剂能将铁水中的磷降低到0.0079%,脱磷率为96.24%,且初始铁水磷含量以及预熔渣粒度对脱磷率影响不大.     

环保型高磷铁水预处理脱磷剂的试验研究

为开发高效环保的高磷铁水预脱磷剂,利用FactsageTM软件绘制了Fe3O4-CaO-B2O3和Fe3O4-CaO-K2O三元相图,根据相图确定出B2O3系和K2O系脱磷剂成分的质量分数,然后在实验室进行脱磷试验,并与以CaF2为助熔剂的高磷铁水预脱磷试验结果进行了比较。结果表明:B2O3能够完全替代CaF2作为助熔剂进行高磷铁水的脱磷预处理,控制w(P)<0.1%,此时w(B2O3)/w(CaO)=0.16,用此种脱磷剂进行脱磷时,化渣良好且不产生泡沫渣,脱磷率也最高。而K2O系脱磷剂的脱磷效果较差。     

转炉渣气化脱磷后再用于脱磷基础研究

为保证转炉熔渣气化脱磷后循环利用的冶炼效果,在实验室进行了气化脱磷炉渣作为返料用于造渣脱磷的热态试验。研究结果表明:气化脱磷渣具备高氧化钙、高碱度、低P_2O_5、高FeO的特点,不需经历成渣过程,可直接用于二次脱磷;采用气化脱磷渣进行铁水脱磷试验时,随着试验温度的提高,铁水终点磷含量呈增大趋势,1 500℃下终点铁水w(P)仅为0.067%,对应的脱磷率为40%;对比气化脱磷渣和配制脱磷剂炉次的脱磷速度可知,在反应前期,气化脱磷渣成渣速度快,气化脱磷渣炉次的铁水磷含量低于配制脱磷剂炉次;但受限于磷容量,气化脱磷渣的终点脱磷效果不如所配脱磷剂,因此建议在工业试验中可将气化脱磷渣与新造渣剂搭配使用,在保证脱磷效果同时,减少造渣料消耗。     

转炉渣用于铁水脱磷的试验研究

在实验室利用转炉渣配制的铁水脱磷剂进行铁水预脱磷试验，测定了脱磷剂组成等因素对脱磷率的影响。结果表明：在铁水脱磷前[Si]≤0．15％条件下，当脱磷剂中转炉渣配比为80％时，相应铁水脱磷率约为78％；Fe2O3和BaCO3代替转炉渣的合适替代量分别约为5％和10％；脱磷剂中（P2O5）含量的增加会导致脱磷率的显著降低，其影响关系式为：ηp（％）=84．01—4．60（P2O5％）。     

铁水预处理脱磷剂的实验研究

在实验室的条件下,对CaO-CaF2-氧化铁为原料的铁水预处理脱磷剂进行了实验研究.研究发现预熔脱磷剂和固体合成脱磷剂均能使铁水磷质量分数降低到0.02%以下.预熔脱磷剂成渣迅速,预处理时间缩短,5 min就可将铁水中的磷降低到较低水平,且铁水温降小,脱磷效率高,将可能成为一种高效、快速、环保的脱磷剂.     

转炉气化脱磷渣用于铁水脱磷及节能减排评估研究

目前在溅渣护炉过程中进行气化脱磷是一种有效的炉渣除磷技术。为保证转炉熔渣气化脱磷后循环利用的冶炼效果,在实验室进行了气化脱磷渣作为返料用于造渣脱磷的试验研究。研究结果表明,气化脱磷渣用于铁水脱磷时前期脱磷能力强,终点脱磷率低,其终点铁水脱磷率和脱磷速率分别为53.3%和0.16%/min;对比配制脱磷剂炉次可知,配制脱磷剂前期脱磷效果差,终点脱磷率高,其终点铁水脱磷率和脱磷速率分别为91.6%和0.32%/min。根据两者脱磷剂的脱磷优势采用混合配比铁水脱磷,当气化脱磷渣大比例用于铁水脱磷时出现回磷现象;当混合比例为1∶4时脱磷效果最好,终点脱磷率为64.4%。采用生命周期评价法对混合渣料比例为1∶4铁水脱磷进行CO₂减排评估,从系统边界的起点到终点预估吨钢可减排CO₂6.034～10.34 kg,吨钢可节省石灰成本1.8～3.0元。     

利用转炉渣对铁水脱磷的动力学

在实验室条件下，模拟转炉渣组成，利用CaO-SiQ-Fe2O3-MnO2-MgO-P2O5-Al2O3-CaF2系熔剂对铁水进行脱磷预处理。实验发现：随着预处理时间的延长，铁水发生回磷反应。在铁水回磷状态下，测定了磷在渣中的传质系数。讨论了回磷原因和抑制铁水回磷反应的措施。在此基础上，确定了合适的铁水脱磷预处理时间和转炉渣的优化组成。     

Kinetic Model of Hot Metal Dephosphorization by Liquid and Solid Coexisting Slags

In most cases, hot metal dephosphorization slag is saturated with dicalcium silicate, and the partition ratio of phosphorus between dicalcium silicate and liquid slag is high. These results indicate the important role of solid dicalcium silicate in dephosphorization. In order to understand the reaction kinetics and obtain an optimum treatment method, it is very important to know the influence of solid phases in the slag. In this study, a new reaction model for hot metal dephosphorization considering the effects of dicalcium silicate and dissolution rate of lime is proposed. In the new dephosphorization model, in addition to the reaction rate between liquid slag and metal, the partition between dicalcium silicate and liquid slag and the dissolution rate of lime are also considered. The dephosphorization reaction of hot metal by the liquid slag phase was calculated by using the coupled reaction model. The calculated results demonstrated the importance of dicalcium silicate in dephosphorization. Also, in some cases, the dissolution rate of lime affected the dephosphorization behaviour.     

Study on Kinetic Model for Dephosphorization of High-Phosphorus Hot Metal Pretreatment

Focused on the hot metal pretreatment process in the torpedo-car and based on the powder injection metallurgy principle, a kinetic model for dephosphorization of high-phosphorus hot metal pretreatment was developed. The validity of this model was verified by comparison between the experimental results in laboratory and the calculated results. The influences of dephosphorization capacity of molten slag and technological conditions on the dephosphorization efficiency were calculated by applying the model. The results show that lower temperatures are favorable to dephosphorization, CaO content in slag should be controlled at about 50%, suitable initial phosphorus content in the hot metal with higher phosphorus contents is about 0.35% by comprehensively considering various factors, slag systems of higher iron oxide content and higher basicity have higher capacity of dephosphorization.     

Reaction mechanism of phosphorus with multi phase fluxes during hot metal dephosphorization

The formation of solid solution combined with tricalcium phosphate and dicalcium silicate could promote a considerable removal of phosphorus from liquid slag to solid during hot metal dephosphorization,and thus the dephosphorization by using multi phase fluxes could significantly decrease the consumption of lime. However,the reaction mechanism of multi phase fluxes has not been understood clearly.In the present study,the phase diagram for the CaO-SiO₂-FeO-P₂O₅ system has been measured with certain oxygen partial pressure at hot metal pretreatment temperature.Comparing with the CaO-SiO₂-FeO system,shrinkage of liquid phase area at higher FeO contents was observed at 1 673 K with oxygen partial pressure of 9.2×10^-11 atm.     

Phase Equilibrium for the CaO-SiO₂-FeO-P₂O₅ System at 1673K for Dephosphorization With Multi Phase Flux

Development of the efficient hot metal dephosphorization processes during steelmaking process is one of the most essential topics for the production of high grade clean steels. Since the formation of solid solution composed of tricalcium phosphate and dicalcium silicate could obtain a considerable mass transfer of phosphorus from liquid slag into solid phase during hot metal dephosphorization, itcould obviously sustain a high phosphatecapacityof theliquid slag without huge consumption of lime or addition of fluxes, such as fluorite. The above outlines are the main idea of multi phase flux dephosphorization. For the last few decades, many studies have been done towards the scientific principles and the commercial utilization of this technique. However, the reaction mechanism by using multi phase fluxes remains unclear even by now due tolack of evidence. Based on those previous works, providing a reliable and available phase diagram for the fundamental understanding of the reaction mechanism of multi phase flux dephosphorization has become the main purpose of present research. As well known, the CaO-SiO2-FeO-P2O5 slag is the main component of current steelmaking process. Hence the CaO-SiO2-FeO-P2O5 system at equilibrium has been studied at 1673K with low oxygen partial pressure. The solid phase coexisting with liquid flux is approved to be the solid solution composed of CaO, SiO2 and P2O5. Phosphorus distributes mainly in solid solution rather than liquid phase.     

脱磷炉利用脱碳炉返回渣的试验

为了达到节能降耗的目的,脱磷炉采用回吃脱碳炉返回渣的工艺。主要研究了脱碳炉渣的熔化特性以及作为炉料在脱磷炉中的应用效果。结果表明,通过每炉次加入约3.5t的脱碳炉渣,可平均节约1.01t石灰,4.71kg/t钢铁料消耗,脱磷炉终点炉渣的岩相组成主要由硅酸二钙、RO相、玻璃相和少量的金属铁粒组成。加入返回渣后脱磷炉终点炉渣中硅酸二钙和铁酸二钙含量有所增加,玻璃相含量降低,炉渣碱度有所升高,脱磷炉终点钢水成分控制水平有所提高。由此表明,采用脱碳炉渣返回脱磷炉循环利用减少了石灰等原辅料和钢铁料消耗,同时达到了预期的脱磷效果。     

转炉铁水预处理脱磷的影响因素

 基于炉外铁水深度预脱硫+转炉铁水预脱磷的铁水预处理工艺是当今低磷或超低磷钢冶炼的重要工艺平台,其中转炉铁水预处理脱磷是关键的技术环节。以国内“双联转炉炼钢法”预脱磷炉实践为出发点,在实验室高温炉上通过顶加脱磷剂、浸入吹氧进行了铁水模拟转炉预脱磷影响因素的试验研究,比较了铁水温度、铁水初始硅质量分数w(Si)_i、脱磷渣碱度、供氧制度、搅拌强度、萤石加入量对脱磷效率的影响。结果表明,各因素对脱磷率影响的顺序为铁水温度＞w(Si)_i＞供氧制度＞脱磷渣碱度、搅拌强度＞萤石加入量;适宜的工艺参数为铁水温度为1 300 ℃,w(Si)_i 为0.10%～0.26%或低于0.30%,脱磷渣碱度为2.9～3.0,供氧制度中气氧与固氧各占50%或固氧稍偏多,维持较高的搅拌强度;转炉内铁水预脱磷处理可不加萤石。     

铁水包脱磷工艺研究

研究在铁水包内喷吹CaO粉剂、顶加氧化铁皮及同时喷吹氧气的铁水脱磷反应。通过测定实际生产过程中脱磷渣的磷平衡分配比及其它组成物成份和相关工艺参数,计算出脱磷渣的磷容量,进而分析了铁水硅含量、温度、脱磷渣碱度及氧化铁等成份对该脱磷工艺的影响。     

转炉冶炼低磷洁净钢的工艺开发和实践

 转炉具备冶炼低磷钢的生产能力,但生产超低磷9Ni钢,转炉脱磷工艺仍然是主要难点和研究重点。分析了钢水温度、炉渣碱度、FeO和渣量等对转炉脱磷的影响规律,并结合现场工装设备条件,对转炉双联法、三渣法、双渣法3种脱磷模式进行试验对比。双联脱磷工艺半钢温降大、单炉周期长、生产组织难度大,三渣法操作过程复杂、终点磷控制优势不明显。双渣法冶炼周期短,通过优化转炉脱磷工艺,实现了采用双渣法冶炼工艺生产超低磷钢,简化了超低磷钢转炉冶炼流程,提高了生产效率。研究了转炉脱磷主要工艺参数,分析得出采用脱碳氧枪喷头时,供氧流量按脱碳吹炼流量的83.5%控制,可达到良好的脱磷效果并减少铁水碳的烧损;脱磷期半钢碳含量不宜控制过低,半钢碳质量分数为3.0%～3.5%时能保证前期的脱磷效果和脱碳期的热量。脱磷期温度控制在1 300～1 350 ℃,脱磷率较高也有利于炉渣熔化。炉渣碱度为1.8～2.2时,可保证较高的脱磷率和化渣效果。一次倒渣量40%以上,脱碳期终点温度按1 590～1 610 ℃控制,终渣FeO质量分数不小于20%,终渣碱度大于6,转炉终点磷质量分数可降低到0.002%以下。采用下渣检测系统和滑板挡渣操作,严格控制下渣量,出钢采用磷含量低的合金,炉后钢水增磷可控制在小于0.000 5%。通过工业试验,实现了铸机成品磷质量分数小于0.002%。     

环保型高磷铁水预脱磷渣的脱磷性能研究

实验室条件下采用间接测量法,测定了CaF2系和B2O3系脱磷渣的磷分配.即首先测量磷在液态渣和固态铁间的分配比,再通过计算得到磷在液态渣和铁水之间分配比,同时根据渣系成分和光学碱度计算了磷容量.同时采用了扫描电镜、能谱分析与X射线衍射分析技术对脱磷渣进行了研究.实验结果表明,B2O3系预脱磷渣的磷容量远大于CaF2系预脱磷渣的磷容量,因此可以用B2O3全部替代CaF2作为助熔剂进行高磷铁水的预脱磷处理,2种渣系的磷分配均随渣中有效CaO含量的升高而升高.用B2O3作为助熔剂时,B2O3能与渣中高熔点物质2CaO·SiO2和3CaO·P2O5反应生成低熔点物质,从而起到助熔的作用.且w(B2O3)/w(CaO)比值为0.16时,磷分配比为最高值,即该渣脱磷能力最强.     

复吹转炉冶炼低磷钢试验研究

研究了复吹转炉铁水脱磷预处理,半钢倒渣后在同一转炉内进行少渣精炼冶炼超低磷钢的工艺。结果表明:在铁水磷含量0.13%条件下,半钢和终点渣碱度(CaO/SiO2)控制在2.0和3.6左右,TFe含量控制在18%左右,半钢倒渣量40%～60%,半钢脱磷率最高达65%,平均为50%,终点脱磷率最高98%,平均为94.6%,冶炼终点钢水磷含量控制在0.007%以下,最低0.003%,满足低磷钢生产要求。