Behaviors, product characteristics and kinetics of catalytic co-pyrolysis spirulina and oil shale
Behaviors, product characteristics and kinetics of catalytic co-pyrolysis spirulina and oil shale
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DOI：
10.1016/j.enconman.2019.04.032
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发表时间：
2019-07-15
影响因子：
10.4
通讯作者：
Ma, Xiaoqian
中科院分区：
文献类型：
--
作者：
Dai, Minquan;Yu, Zhaosheng;Ma, Xiaoqian
采用热重分析（TGA）和热解-气相色谱/质谱（Py-GC/MS）研究了螺旋藻（SP）和油页岩（OS）的催化共热解行为、动力学和产物分布。结果表明：OS延缓了SP中有机物的热分解;在310 ℃以下对芳烃的生成有抑制作用，在高温下有协同作用，当OS含量为30%时协同作用最大; HZSM-5和CaO促进了脱氧和芳构化反应，使酸和酚的生成量显著降低。随着CaO比的增加，脂肪烃相对含量从9.57%增加到17.48%，芳烃相对含量先增加后降低，在1CaO/3 HZSM-5上芳烃收率最高（15.92%）。合适的CaO/HZSM-5质量比有利于热解产物的生成。采用Friedman和Flynn-Wall-Ozawa（FWO）法测定了反应动力学参数。随着油页岩掺量的增加，混合物的平均活化能E从278.84 kJ/mol降低到192.53 kJ/mol（从265.51 kJ/mol降低到189.63 kJ/mol），这与油页岩灰分中碱土金属对有机质的催化分解有关。在1HZSM-5/3CaO催化剂上，5SP/5 OS催化裂解的E值最小，分别为257.29kJ/mol和269.6210/mol。本文可为利用HZSM-5和CaO从SP和OS中获得优质油提供重要的热解知识。
The catalytic co-pyrolysis behaviors, kinetics and products distribution of spirulina (SP) and oil shale (OS) were studied by thermogravimetric analysis (TGA) and pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). Results indicated that OS delayed the thermal decomposition of organic matters in SP; there existed inhibition for aromatics production under 310 degrees C and synergistic effects at high temperatures, and a maximum synergistic effect was achieved with 30% OS. HZSM-5 and CaO enhanced the deoxygenation and aromatization reaction, resulting in a prominent decrease of acids and phenols. With the increase of CaO ratio, the relative content of aliphatic hydrocarbons increased from 9.57% to 17.48%, while the relative content of aromatics increased first and then decreased, and the maximum yield of aromatics (15.92%) was obtained at 1CaO/3HZSM-5. The appropriate CaO/HZSM-5 mass ratio contributed to the production of desired pyrolysis product. The kinetic parameters were determined by using Friedman and Flynn-Wall-Ozawa (FWO) method. As the oil shale blending ratio increased, the average activation energy (E) of mixtures decreased from 278.84 kJ/mol to 192.53 kJ/mol (from 265.51 kJ/mol to 189.63 kJ/mol), related to the catalytic decomposition of organic matter by alkaline earth metals in OS ash. The minimum E value of catalytic pyrolysis 5SP/5OS was achieved at 1HZSM-5/3CaO (257.29 kJ/mol and 269.6210/mol). This paper could offer significant pyrolysis knowledge for obtaining high-grade oil from SP and OS with HZSM-5 and CaO.