吉木萨尔油页岩热解及其灰渣利用

发布时间：2018-01-18 01:26

  本文关键词：吉木萨尔油页岩热解及其灰渣利用　出处：《新疆大学》2015年硕士论文　论文类型：学位论文

  更多相关文章： 油页岩 热解 热重 动力学 沸石 吸附

【摘要】：油页岩是一种重要的非常规能源,经过热解可以得到碳氢比类似原油的页岩油,对缓解我国石油紧缺具有重要的战略意义。对油页岩热解特性的研究是保证其优质转化的前提,也为其综合开发利用提供理论依据。本文以研究新疆吉木萨尔油页岩热解特性为主要目标,考察了热解温度、粒径及停留时间对热解产物产率及组成的影响;利用热重分析法对其热解动力学进行了研究;最后探讨了以热解灰渣为原料合成沸石的可行性。主要研究内容和结论如下:采用固定床热解反应器,N2气氛下,考察了温度、粒径及停留时间对油页岩热解反应的影响,对固体产物灰渣进行BET和FT-IR表征,对页岩油和气体产物分别采用GC-MS和GC分析。结果表明:(1)随热解温度的升高,油产率先增大后减小,530℃达到最大值,水产率和气产率逐渐增加;(2)随颗粒粒径的减小,油产率呈现下降趋势,气产率逐渐增加,水产率变化不大;(3)油产率随停留时间的延长先增大后减小,530℃下,停留时间30min时,油产率最大;(4)吉木萨尔油页岩适宜的热解工艺条件为:氮气气氛下,热解温度530℃,颗粒粒径0.42~0.84mm,停留时间30min,油产率为11.2%。利用热重分析仪对油页岩热解过程进行研究,分别采用Coats-Redfern法和Freeman-Carroll法得到了相应的表观活化能和指前因子,确定了线性相关较好的反应级数。结果表明:(1)升温速率对活化能影响较大,不同热解温度段内活化能随升温速率的增大呈现出减小的趋势;(2)采用Freeman-Carroll法计算的活化能E值比采用Coats-Redfern法计算的E值偏大,说明算法的选择对于活化能的计算影响较大;(3)从数据拟合的线性相关系数R来看,升温速率较小时,采用Coats-Redfern法得到的R值较高;升温速率较大时,采用Freeman-Carroll法得到的R值较高;(4)用热重实验模拟油页岩固定床热解过程存在较大误差,因此热重不能完全代替实际的热解过程,只能作为参考。以热解灰渣为原料,采用水热合成法制备出沸石,考察了晶化时间和晶化温度对沸石合成过程的影响,对合成沸石进行了XRD、SEM和BET表征。实验确定了沸石合成的工艺参数为:碱熔温度为800℃,氢氧化钠与灰渣用量比为1:1,晶化时间12h,晶化温度120℃。分别以灰渣和合成沸石作为吸附剂,考察了吸附剂用量和吸附时间对Cu2+吸附特性的影响。实验结果表明:灰渣用量为40g/L,吸附时间100min时,吸附基本达到平衡,对Cu2+去除率为76.5%;合成沸石用量为20g/L时,吸附时间80min时,吸附基本达到平衡,对Cu2+去除率为92.6%。
[Abstract]:Oil shale is an important unconventional energy source, which can be pyrolyzed to obtain shale oil with hydrocarbon ratio similar to crude oil. It is of great strategic significance to alleviate the oil shortage in China. The research on the pyrolysis characteristics of oil shale is the premise to ensure its high quality transformation. The main objective of this paper is to study the pyrolysis characteristics of Jimusar oil shale in Xinjiang, and to investigate the effects of pyrolysis temperature, particle size and residence time on the yield and composition of pyrolysis products. The pyrolysis kinetics was studied by thermogravimetric analysis. Finally, the feasibility of synthesizing zeolite from pyrolytic ash was discussed. The main contents and conclusions were as follows: the temperature was investigated in a fixed bed pyrolysis reactor in N _ 2 atmosphere. The effect of particle size and residence time on the pyrolysis reaction of oil shale was studied. The solid product ash was characterized by BET and FT-IR. The analysis of shale oil and gas products by GC-MS and GC shows that with the increase of pyrolysis temperature, the oil production increases first and then decreases to the maximum value. The aquatic yield and gas yield increased gradually; 2) with the decrease of particle size, the oil yield showed a downward trend, the gas yield gradually increased, and the aquatic yield changed little; (3) the oil yield increased firstly and then decreased at 530 鈩，

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