金属氧化物对油页岩热解产物收率及组成分布的影响
发布时间：2018-08-09 06:55
【摘要】：通过固定床反应器,对4种金属氧化物(Al_2O_3、MgO、CaO、Fe_2O_3)对油页岩热解所得油、气产率及成分的影响进行了研究。结果显示,碱性CaO对油、水、气、焦产率分布影响较为突出,可提高页岩油与半焦产率,并降低热解气产率;而酸性较强的Al_2O_3可同时提高页岩油、热解气和热解水的产率,有利于促进挥发分的析出;比较而言,MgO和Fe_2O_3的作用相对较弱。4种金属氧化物均可提高热解气中H_2、CH_4和C2的产率;CaO作用下CO_2含量降低,而其他金属氧化物对CO_2的产生有不同程度的促进作用;Fe_2O_3可促进H_2产生;Al_2O_3作用下CH_4含量有所增加。4种金属氧化物均可促进页岩油中芳香烃的产生,并且CaO和MgO两种碱土金属氧化物作用下,短链(C6~C12)烷烃和烯烃含量均增加,而掺混Al_2O_3时页岩油中仅短链(C6~C12)烷烃含量增加。对此机理进行推测认为,碱性CaO和MgO首先与以脂肪酸形式存在的有机质进行酸碱反应,得到脱羧活性更高的羧酸盐,后者脱羧所得中间产物具有生成烷烃或烯烃两条可能路径,同时得到碳酸盐;而在具有Lewis酸特征的Al_2O_3作用下,脱羧产物为CO_2,并同时得到饱和烃产物。
[Abstract]:The effects of four kinds of metal oxides (Al _ 2O _ 3 _ C _ 2O _ 3) on the oil, gas yield and composition obtained from pyrolysis of oil shale were studied in a fixed-bed reactor. The results showed that the distribution of oil, water, gas and coke yield was significantly affected by alkaline CaO, which could increase the yield of shale oil and semi-coke and decrease the yield of pyrolytic gas, while Al_2O_3 with strong acidity could increase the yield of shale oil, pyrolytic gas and pyrolytic water at the same time. In comparison, MgO and Fe_2O_3 can increase the yield of H2CH4 and C2 in pyrolytic gas and decrease the content of CO_2 under the action of Cao. However, other metal oxides can promote the production of CO_2 to some extent. Fetit _ 2O _ 3 can promote the production of aromatic hydrocarbons in shale oil by increasing the content of CH_4 in the presence of Al _ 2O _ 3, and the metal oxides can promote the production of aromatic hydrocarbons in shale oil. Under the action of CaO and MgO, the contents of C6~C12 alkanes and alkenes increased, but only C6~C12 alkanes in shale oil increased when Al_2O_3 was mixed. It is suggested that alkaline CaO and MgO first react with organic matter in the form of fatty acids to produce carboxylate with higher decarboxylation activity, and the intermediate products obtained from decarboxylation have two possible pathways to form alkanes or olefins. At the same time, carbonates were obtained, while under the action of Al_2O_3 with Lewis acid characteristics, the decarboxylation product was CO _ 2 and saturated hydrocarbon products were obtained simultaneously.
【作者单位】： 中国科学院过程工程研究所多相复杂系统国家重点实验室;中国科学院大学中丹学院;
【基金】：国家重点基础研究发展计划项目(2014CB744304) 国家自然科学基金面上项目(51476180)~~
【分类号】：TE662
本文编号：2173252
[Abstract]:The effects of four kinds of metal oxides (Al _ 2O _ 3 _ C _ 2O _ 3) on the oil, gas yield and composition obtained from pyrolysis of oil shale were studied in a fixed-bed reactor. The results showed that the distribution of oil, water, gas and coke yield was significantly affected by alkaline CaO, which could increase the yield of shale oil and semi-coke and decrease the yield of pyrolytic gas, while Al_2O_3 with strong acidity could increase the yield of shale oil, pyrolytic gas and pyrolytic water at the same time. In comparison, MgO and Fe_2O_3 can increase the yield of H2CH4 and C2 in pyrolytic gas and decrease the content of CO_2 under the action of Cao. However, other metal oxides can promote the production of CO_2 to some extent. Fetit _ 2O _ 3 can promote the production of aromatic hydrocarbons in shale oil by increasing the content of CH_4 in the presence of Al _ 2O _ 3, and the metal oxides can promote the production of aromatic hydrocarbons in shale oil. Under the action of CaO and MgO, the contents of C6~C12 alkanes and alkenes increased, but only C6~C12 alkanes in shale oil increased when Al_2O_3 was mixed. It is suggested that alkaline CaO and MgO first react with organic matter in the form of fatty acids to produce carboxylate with higher decarboxylation activity, and the intermediate products obtained from decarboxylation have two possible pathways to form alkanes or olefins. At the same time, carbonates were obtained, while under the action of Al_2O_3 with Lewis acid characteristics, the decarboxylation product was CO _ 2 and saturated hydrocarbon products were obtained simultaneously.
【作者单位】： 中国科学院过程工程研究所多相复杂系统国家重点实验室;中国科学院大学中丹学院;
【基金】：国家重点基础研究发展计划项目(2014CB744304) 国家自然科学基金面上项目(51476180)~~
【分类号】：TE662
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