节点文献
高硫石油焦的脱硫工艺研究
【作者】 李宁；
【作者基本信息】 昆明理工大学 ， 冶金工程（专业学位）， 2018， 硕士
【摘要】 石油焦是重要的工业原料,国内石油化工产业的快速发展和进口原油质量的变化,对国内石油焦的产品结构产生了巨大的变化。目前国内石油焦的供应出现失衡,高硫石油焦的产量增加,低硫石油焦的供应严重不足。高硫石油焦在铝电解中的应用,对铝电解生产和环境造成了许多危害,严重的面临停产整顿的风险。因此研究一种有效的脱硫方法,对炭素工业和冶金工业的可持续健康发展具有重要意义。本文查阅文献和实验探索后,寻找到一种通过添加锰粉煅烧脱硫的方法,并进行了详细的实验研究,主要研究内容和结论如下:高硫石油焦的脱硫实验,采用了单因素实验进行研究,实验发现:石油焦粒径越小越有利于石油焦中硫的脱除;在一定范围内,脱硫率随着反应温度的升高和反应时间的延长而升高;在一定范围内,脱硫率随着锰粉比例的增加和石蜡比例的增加而升高,实验采用了硫酸锌对载硫锰粉进行脱硫处理,脱硫后的锰粉可返回到脱硫实验中。在单因素实验的基础上,利用软件Design-expert进行了四因素三水平的石油焦脱硫工艺研究。结果表明各因素对石油焦脱硫率影响:锰粉比例>反应温度>反应时间>石蜡比例;其中反应温度和反应时间的交互作用明显,其它因素交互作用不显著,获得模拟回归方程:Y=53.59+2.91X1+2.20X2+3.06X3+0.46X4-1.07X1X2-0.34X1X3+0.065X1X4-0.21X2X3-0.34X2X4-0.30X3X4-2.89X12-1.76X22-2.59X32-0.75X42响应曲面优化后经实验验证最佳条件为:反应温度为740℃,反应时间100min,石油焦:锰粉=20:2.5,石油焦:石蜡=20:2,在此条件下对硫含量为3.47%的石油焦脱硫后硫含量降低为1.55%,达到牌号YBYJJ-1要求。用红外光谱、电子探针等现代分析手段,证明脱硫后的石油焦中噻吩类和硫醇类有机硫结构被一定程度上破坏,脱硫后锰粉的表面有硫的存在,实验的工艺条件对石油焦的微观形貌影响不大,反应后石油焦与锰粉的结块现象,利用乙醇蒸汽替代石蜡得到有效解决,反应条件乙醇蒸汽体积比达到约98%,其流速为0.5m/s,反应后石油焦硫含量由3.47%降低到1.2%。
【Abstract】 Petroleum coke is a major industrial raw material.The rapid development of the domestic petrochemical industry and the change of the quality of imported crude oil has caused great changes in the product structure of domestic petroleum coke.At present,the supply of domestic petroleum coke is out of balance.The production of high-sulfur petroleum coke is increasing,and the supply of low sulfur petroleum coke is seriously inadequate.The application of high-sulfur petroleum coke in aluminum electrolysis production has caused serious harm to the production and environment of aluminum electrolysis,and even the risk of shut-down and rectification.Therefore,the study of an effective desulfurization method is of immense significance to the sustainable and healthy development of carbon industry and metallurgical industry.On the basis of literature review and experiment.Find a method to calcinate desulfurization by adding manganese powder.The main research contents and conclusions are as follows.The desulfurization experiment of high-sulfur petroleum coke was studied by single factor experiment.,It is found that the smaller the petroleum coke size is,the better it is for the removal of sulfur in petroleum coke.In a certain range,the desulfurization rate increases with the increase of reaction temperature and reaction time;In a certain range,the desulfurization rate increases with the increase of manganese powder proportion and the increase of paraffin wax ratio,The desulfurization manganese powder can be returned to the desulfurization experiment.On the basis of single factor experiment,The research of four factors of petroleum coke desulfurization technology was carried out using software design-expert..The results demonstrate that the factors affect the desulfurization rate of petroleum coke as flows:manganese powder ratio>reaction temperature>reaction time>paraffin ratio.The interaction between reaction temperature and reaction time is evident,and the interaction of other factors is not significant.Obtain the simulated regression equation:Y=53.59+2.91X1+2.20X2+3.06X3+0.46X4-1.07X1X2-0.34X1X3+0.065X1X4-0.21X2X3-0.34X2X4-0.30X3X4-2.89X12-1.76X22-2.59X32-0.75X42The optimal conditions for the response surface optimization are obtained by experiment:the reaction temperature is 740℃,reaction time is 100min,the ratio of manganese powder is 20:2.5,the ratio of Paraffin is20:2.In this condition,the sulfur content of petroleum coke with sulfur content of 3.47%is reduced to 1.58%,which is required by the brand YBYJJ-1.Using modern analytical means such as FTIR and EPMA,By means of modern analytical methods such as FTIR and EPMA,the organic sulfur structure of thiophene and thiol in desulfurized petroleum coke was destroyed to some extent.After desulphurization,the surface of manganese powder has sulfur elements.The experimental conditions have little effect on the microstructure of petroleum coke.After the reaction,Petroleum coke is bonded with manganese powder.Using ethanol steam instead of paraffin to be effectively solved,The volume ratio of ethanol vapor is approximately 98%,and its velocity is 0.5m/s.After the reaction,The sulfur content of petroleum coke decreased from 3.47%to 1.2%.
【Key words】 petroleum coke； desulfurization； manganese powder； response surface optimization；