【作者】 韩冰；

【导师】 刘辉；

【作者基本信息】 哈尔滨工业大学 ， 动力工程（专业学位）， 2016， 硕士

【摘要】 我国资源赋存具有“富煤、贫油、少气”的特点,石油储采比仅为11.4年,对外依存度超过60%。我国油页岩资源丰富,其干馏产生的页岩油可以代替石油。油页岩热解过程中,黄铁矿中的硫会迁移到产物里,严重的污染了环境、腐蚀了设备。另一方面,黄铁矿又会对热解过程产生影响。因此,研究黄铁矿对油页岩热解过程的影响意义重大。为了排除其他矿物质对油页岩干馏的影响,本文采取酸洗的方法制备龙口油页岩有机质,详细分析了酸洗前后油页岩中矿物质和各种官能团的变化情况。在水平炉干馏试验台上,研究了氧化铁、单质硫和黄铁矿对油页岩有机质热解产物产率、不凝气释放以及半焦官能团的影响。通过对龙口油页岩酸洗前后XRD和FTIR分析,发现采用HCl-HF-HNO3逐级酸洗的方法可以脱除98.5%的灰,制得较为纯净的有机质,但会对有机质的结构产生一定影响。酸洗会促使芳香烃结构向苯环二取代方式转变,同时使有机盐转化为有机酸,提高羧酸和酚羟基含量;对于脂肪结构,酸洗会增加不对称CH2所占比例,造成脂肪链长度增大,而对于羟基来说,酸洗会在一定程度上破坏OH-O的氢键结构。对酸洗前后油页岩进行热重实验,结果表明酸洗会降低热解起始温度和终止温度,增大热解速率,但基本不影响最大失重峰的温度范围,这说明酸洗并不会显著改变有机质的主体结构。龙口油页岩酸洗除去的矿物质对热解表现为抑制作用。通过对半焦官能团的红外谱图分析,发现在热解终温500℃、停留时间40min时,有机质基本已经分解完全。热解会使脂肪长链断裂,含氧官能团比例下降,其中羧酸已完全反应。对芳香烃而言,热解会使芳香氢取代程度升高,取代方式向氢含量减少的方向进行。氧化铁、硫、黄铁矿均会促进芳香烃的取代,过量的氧化铁和黄铁矿会使苯环的取代方式向苯环三取代进行,硫会使苯环的取代方式向苯环四取代进行。3种添加剂都会抑制大分子的缩合,使半焦中CH2/CH3的值不断升高。当添加40%的硫时,红外谱图中2870cm-1处对称的CH3伸缩振动峰的强度明显增强,表明过量的硫会促使焦炭中芳香环开裂,增加支链化程度。热解过程中,氧化铁、硫、黄铁矿均对有机质大分子结构的断裂起到促进效果。氧化铁和硫均降低了焦油的产率,促进了不凝气的生成;随着黄铁矿添加量的增大,焦油产率先下降后上升,气体产率先上升后下降。热解气CO和CO₂的生成总是先于CH₄和C₂H₆。氧化铁会提高CO₂的产率,降低CO、CH₄和C₂H₆的产率;硫会提高CO的产率,降低CO₂、CH₄和C₂H₆的产率,同时,硫的加入会使这4种气体开始生成的时间推后;黄铁矿会提高CO₂的产率,而CO、CH₄和C₂H₆的产率先升高后下降,在添加量2%时达到最大值。更多还原

【Abstract】 China’s energy resources have such characteristics of “rich in coal, oil-poor, less gas”, and the reserve and production ratio for oil is 11.4 years, while imported oil accounts for 60%. China has enormous oil shale resources which can be converted into shale oil as an alternate to conventional oil by retorting. During pyrolysis, sulfur in pyrite will be transferred into the product which can pollute environment and corrode equipment. On the other hand, pyrite has effect on pyrolysis. Therefore, Studying the effect of pyrite in the process of oil shale pyrolysis has great significance.In order to exclude the impact of other mineral matter for oil shale retorting process, this research adopts washing oil shale with HCl-HF-HNO3 to obtain Longkou oil shale organic matter, analyze the effect of mineral matter and various functional groups during acid pickling. Study the impact of iron oxide, elemental sulfur and pyrite for product yield、Non-condensable gas release and char oxygen functional groups in horizontal furnace carbonization test rig.Analysis the effect of acid pickling for oil shale by XRD and FTIR, the results indicate that HCl-HF-HNO3 could remove 98.5% ash and obtain relatively pure organic matter. But acid pickling could make difference on the structure of organic matter. Acid pickling cause aromatic structure transport into two hydrogens per ring, organic salts convert to organic acids, increase carboxylic acids and phenolic hydroxyl at the same time. With regard to aliphatic structure,acid pickling will increase the proportion of asymmetric CH2 and length of aliphatic chain. For the perspective of hydroxyl, acid pickling could destroy OH-O.The effect of acid pickling for oil shale by TG/DTG, the results indicate that acid pickling reduce the pyrolysis temperature at the beginning and the end, increase pryolysis rate. However acid pickling have little effect on maximum weight loss which means acid pickling will not evidently change the main structure of organic matter. By acid pickling, mineral matter in Longkou oil shale could restrain pyrolysis.Analysis of char functional groups FTIR spectra shows that organic matter has been completely decomposed under the condition with 500℃ ultimate temperature, 40 min residence time. Pyrolysis can cause aliphatic chain rupture, decreased oxygen functional groups where carboxylic acids has been completely decomposed.For aromatic hydrocarbon, pyrolysis can make aromatic hydrogen replace degree rise, the way of replace is toward hydrogen content reducing. Iron oxide, sulfur and pyrite will promote the aromatic hydrocarbon replacing, excessive iron oxide and pyrite could increase the content of three hydrogens per ring, sulfur could increase the content of four hydrogens per ring. Three kinds of additives restrain macromolecule condensation and increase ratio of CH2/CH3 in char. When add 40% sulfur, CH3 symmetric stretching vibration intensely increases in FTIR spectra 2870cm-1. The results show that excess sulfur promotes aromatic circle fractured and increases the degree of branched chain.In the process of pyrolysis, iron oxide, sulfur, pyrite all promote effect on organic macromolecular fracture. Iron oxide and sulfur are reducing the tar production rate, promote the formation of the non-condensable gas. With the increase of mixing pyrite, tar production decreases and then increases, gas production appears a trend of rise first and then decrease. CO and CO₂ generate prior to CH₄ and C₂H₆. Iron oxide can raise the yield of CO₂, reduce the yield of CO, CH₄ and C₂H₆. Sulfur can raise the yield of CO, reduce the production rate of CO 2, CH₄ and C₂H₆, while addition of sulfur will make the four gases start generating latterly. Pyrite can raise the yield of CO₂, and the yield of CO, CH₄ and C₂H₆ firstly rise and then decrease, it reaches maximum when pyrite mixing counts 2%.更多还原