添加剂对高硫煤热解过程硫迁移的作用研究

2.3.1 添加剂与煤样混合方法 ......................................... 20 2.3.2 热解试验方法 ................................................. 21 2.4 全硫及形态硫测定方法 ........................................... 21
1.4.1 有机硫含量直接测定法研究 ..................................... 15 1.4.2 有机硫官能团直接测定法研究 ................................... 16 1.5 1.6 1.7 小结 ........................................................... 16 课题研究目标及主要内容 ......................................... 17 研究方案和技术路线 ............................................. 18
1.2.1 无机硫存在形态及转化 .......................................... 3 1.2.2 有机硫存在形态及转化 .......................................... 4 1.3 热解脱硫研究现状 ................................................ 5
I
煤炭科学研究总院硕士学位论文
Abstract
The proportion of high sulfur coking coal increases year by year with the low efficiency of the existing desulfurization process which has made it become an urgent problem to study high efficient desulfurization method in the use of coking coal today. Wile, it has been proved that desulfurization during pyrolysis was effective. This thesis studied the characteristics of desulfurization of coking coal during pyrolysis with some additives. At first, four typical coking coals had been selected to research the change regularity of different forms of sulfur removal rate, FTIR and XPS were used to study the existing forms of organic sulfur and the change regularity of different forms of organic sulfur removal rate during pyrolysis especially; Then, Qinneng coking coal was chosen to select additives and study the effects of adding ration of different additives and temperatures on desulfurization, and the thesis also analyzed the mechanism of the effect of some additives on the morphology of the sulfur removal rate; finally, the feasibility of pyrolytic desulfurization with compound additives was investigated. The results are as following: 1) Organic sulfur was the main existing forms of sulfur in high sulfur coking coal. Organic sulfur mainly existed as disulfides, aromatic sulfides, thiophene and a little sulfoxides. Aromatic and thiophene sulfide accounted for 50% of total sulfur and more; 2) Different sulfur compounds would decompose at different temperatures. Pyrite would decompose before 450℃, and it would reach the maximum amount of decomposition before 650℃. Disulfides and some aromatic sulfides would begin to decompose between 450~650℃, and disulfides disappeared after 850℃; 3) Some additives could promote the desulfurization rate, γ-Al2O3 worked best among all additives chosen, and the highest removal rate could be 34.22%, it was 11.16% more than that of single coking coal. γ-Al2O3、TiO2 and CeO2 , which improved the desulfurization rate, were mainly through promoting the decomposition of disulfides and some aromatic sulfides in the coal. 4) The desulfurization effect of compound additives was better than that of single additives, but the effect is not obvious, the highest removal rate with composite additives could be 38.76%, which was 4.54% more than that of single additives. There were mutual promotion among four additives, and γ-Al2O3 played a leading role. Keywords: Coking Coal; Pyrolytic Desulfurization; Additives;
1.3.1 不同气氛下热解脱硫研究现状 .................................... 6 1.3.2 配添加剂热解脱硫研究现状 ..................................... 11 1.4 煤焦中有机硫测定方法研究现状 ................................... 15
分类号： UDC：
学校代码： 密 级：
硕士学位论文
添加剂对高硫煤热解过程 硫迁移的作用研究
பைடு நூலகம்Study on the Effect of Additives on Sulfur Transfer during High—Sulfur Coal Pyrolysis
研 究 生： 导 师：
王之正 王利斌 裴贤丰 研究员 副研究员
II
煤炭科学研究总院硕士学位论文
目
录
第一章 绪论 ............................................................. 1 1.1 1.2 炼焦煤资源分布及硫含量 .......................................... 1 炼焦煤中硫存在形态及转化 ........................................ 2
第二章 原料煤分析及试验方法 ............................................ 19 2.1 试验煤样与试剂基本分析 ......................................... 19
2.1.1 煤样的制备及基本分析 ......................................... 19 2.1.2 添加剂的选取 ................................................. 19 2.2 2.3 试验设备 ....................................................... 20 试验方法 ....................................................... 20
学科专业： 研究方向：
化学工艺 煤炭热解
培养单位： 煤科总院北京煤化工分院
煤炭科学研究总院 2014 年 5 月
煤炭科学研究总院硕士学位论文
摘
要
高硫炼焦煤比例逐年增加和现有脱硫工艺的效率低下，使得研究高效脱硫方法成 为现阶段炼焦煤利用中亟需解决的难题，热解脱硫是一种行之有效的脱硫方法。本论 文以高硫炼焦煤为对象，进行了添加剂对煤样热解硫迁移影响的研究。首先选取四种 典型炼焦煤对煤中硫存在形态及各形态硫脱除率变化规律进行了系统研究，并利用傅 里叶红外光谱及 X 射线光电子能谱对煤中有机硫存在形态及其脱除率变化规律进行 了重点研究；接着以沁能煤为试验煤样，进行了单种添加剂筛选，并研究了添加量及 终温对全硫及形态硫热解脱除率变化规律的影响，初步分析了部分单种添加剂影响形 态硫脱除的作用机理；在此基础上，还探讨了不同作用效果的添加剂复合脱硫的可行 性。研究表明： 1) 有机硫是洗选后高硫炼焦煤中硫的主要存在形态；根据所含官能团不同，炼 焦煤中有机硫主要有二硫化物、芳香族硫化物、噻吩类硫化物及少量含硫氧 化物，其中芳香及噻吩类硫化物占全硫总量的 50%甚至更多； 2) 不同形态含硫化合物分解的温度区间不同； 黄铁矿硫在 450℃开始分解， 650℃ 可达脱除率极大值； 二硫化物及部分芳香族硫化物在 450~650℃温度段内发生 分解转化，其中二硫化物可在 850℃前分解完毕；热解过程中，存在其他形态 硫向含硫氧化物和稳定形态的芳香及噻吩类硫化物转化的现象； 3) 煤样配加部分单种添加剂后可得到较好的热解脱硫效果， 其中 γ-Al2O3 脱硫效 果较佳，脱除率最高可达 34.22%，较煤样单独热解时全硫脱除率增加 11.16 个百分点；γ-Al2O3、TiO2、CeO2 等 3 种添加剂可促进煤中二硫化物及部分芳 香族硫化物的分解； 4) 添加剂复合使用可提高全硫及形态硫脱除率， 但提高不明显； γ-Al2O3、 TiO2、 油酸钠、 乙二胺四乙酸添加量分别为 1%、 2%、 2%、 2%时， 全硫脱除率最高， 达 38.76%，较单种添加剂全硫最高脱除率仅增加 4.54 个百分点；添加剂复合 使用存在协同作用，γ-Al2O3 在复合添加剂中作用最为明显； 关键词：炼焦煤；热解脱硫；添加剂；