油页岩矿物质催化半焦燃烧特性及机理

doi:10.11949/0438-1157.20200655

化工学报 ›› 2020, Vol. 71 ›› Issue (12): 5568-5577.DOI: 10.11949/0438-1157.20200655

• 催化、动力学与反应器 • 上一篇下一篇

油页岩矿物质催化半焦燃烧特性及机理

高鹤¹(),姜星宇¹,刘雪景¹,岳君容²,曾玺²,韩振南¹(),许光文^1,²()

^1.沈阳化工大学能源与化工产业技术研究院，资源化工与材料教育部重点实验室，辽宁沈阳 110142
^2.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，北京 100190

收稿日期:2020-05-27 修回日期:2020-07-16 出版日期:2020-12-05 发布日期:2020-12-05
通讯作者: 韩振南,许光文
作者简介:高鹤（1994—），男，硕士研究生，he.gao@studio.unibo.it
基金资助:
国家自然科学基金项目(U1903130);国家重点研发计划项目(2018YFF01011402)

Characteristics and mechanism of catalytic effect of inner minerals on combustion of oil shale coke

GAO He¹(),JIANG Xingyu¹,LIU Xuejing¹,YUE Junrong²,ZENG Xi²,HAN Zhennan¹(),XU Guangwen^1,²()

^1.Institute of Industrial Chemistry and Energy Technology, Laboratory on Resources Chemicals and Materials of Ministry of Education, Shenyang University of Chemical Technology, Shenyang 110142, Liaoning, China
^2.State Key Laboratory of Multi-phase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China

Received:2020-05-27 Revised:2020-07-16 Online:2020-12-05 Published:2020-12-05
Contact: HAN Zhennan,XU Guangwen

摘要/Abstract

摘要：

利用微型流化床反应分析仪（MFBRA）研究了油页岩矿物质催化半焦燃烧特性，重点考察了半焦内部矿物质和外部页岩灰床料对半焦燃烧的催化作用，揭示了流化床反应器中半焦燃烧过程和机理。结果表明：内部矿物质和外部床料对半焦燃烧均具有明显催化作用，而两者共同催化效果最为显著。矿物质中CaO和Fe₂O₃对半焦燃烧具有催化活性，CaO催化作用强于Fe₂O₃。油页岩半焦燃烧反应活化能在60.41~78.97 kJ/mol之间，矿物质的催化作用会明显降低反应活化能。流化床反应器中，矿物质对半焦燃烧的催化作用主要表现在四个反应，即：挥发分裂解和燃烧、半焦表面炭燃烧、半焦内部炭燃烧以及一氧化碳燃烧。

关键词: 微型流化床, 油页岩, 半焦燃烧, 矿物质, 催化

Abstract:

The micro fluidized bed reaction analyzer (MFBRA) was used to study the combustion characteristics of oil shale mineral catalytic semi-coke. This study compared the effect of minerals inside char and bed material (oil shale ash) outside char on char combustion, and the process and mechanism of char combustion in the fluidized bed were further revealed. Both of minerals inside char and bed material outside char had a marked catalysis for char combustion and their combined catalysis was most notable. It is found that the CaO and Fe₂O₃ were the major active components in oil shale minerals for catalytic combustion of char, and the catalysis of CaO was stronger than that of Fe₂O₃. The activation energy of char combustion ranged from 60.41 kJ/mol to 78.97 kJ/mol, and it would significantly decrease with presence of the catalysis by minerals in oil shale. For char combustion in a fluidized bed, the contribution of minerals to catalytic combustion was mainly reflected in four reactions, such as volatiles cracking and combustion, surface carbon combustion, internal carbon combustion and CO combustion.

Key words: micro fluidized bed, oil shale, char combustion, minerals, catalysis

中图分类号:

TQ 028.8

高鹤,姜星宇,刘雪景,岳君容,曾玺,韩振南,许光文. 油页岩矿物质催化半焦燃烧特性及机理[J]. 化工学报, 2020, 71(12): 5568-5577.

GAO He,JIANG Xingyu,LIU Xuejing,YUE Junrong,ZENG Xi,HAN Zhennan,XU Guangwen. Characteristics and mechanism of catalytic effect of inner minerals on combustion of oil shale coke[J]. CIESC Journal, 2020, 71(12): 5568-5577.

图/表 15

图1 油页岩固体热载体热解工艺及半焦催化燃烧过程

Fig.1 Oil shale pyrolysis with solid heater carrier and catalytic combustion of oil shale char

表1 油页岩及半焦的工业分析与元素分析

Table 1 Results of proximate and ultimate analysis of oil shale and char

Sample	Proximate analysis^①/ % (mass)				Ultimate analysis^②/%(mass)
Sample	M	A	V	FC	C	H	N	S	H/C
oil shale	6	80.37	13.16	0.47	9.38	1.45	0.97	0.43	0.155
char	1.46	93.39	4.62	0.41	4.38	0.23	0.46	0.53	0.053

图2 页岩热解半焦与去矿化半焦XRD谱图

Fig.2 XRD pattern of oil shale char and demineralized char

表2 反应床料XRF分析

Table 2 XRF analysis of bed material

Sample	Compound content/%(mass)
Sample	CaO	Fe₂O₃	Na₂O	Al₂O₃	MgO	SiO₂	Others
oil shale ash	0.971	8.617	0.57	22.484	1.433	61.326	4.599
CaO/SiO₂	15.393	0.268	0.03	0.08	2.49	80.744	0.995
Fe₂O₃/SiO₂	0.642	14.58	0.02	0.649	1.095	81.823	1.191

图3 微型流化床反应分析仪

Fig.3 Schematic diagram of micro fluidized bed reaction analyzer (MFBRA)

表3 半焦燃烧实验设计

Table 3 Experimental design of char combustion

Experiment	Sample	Bed material	Research object
De-Char/SiO₂	De-Char	SiO₂	control group
Char/SiO₂	Char	SiO₂	catalysis of minerals inside char
De-Char/Ash	De-Char	oil shale ash	catalysis of bed material outside char
Char/Ash	Char	oil shale ash	synergistic catalysis
Char/Fe₂O₃	Char	Fe₂O₃/SiO₂	catalysis of Fe₂O₃
Char/CaO	Char	CaO/SiO₂	catalysis of CaO

图4 半焦燃烧反应分析方法示意图

Fig.4 Analysis approach adopted for char combustion in MFBRA

图5 不同反应条件下CO2信号强度随反应时间变化

Fig.5 Intensity of CO2versus time for char combustion at different conditions

图6 不同反应条件下的半焦燃烧反应速率

Fig.6 Reaction rate of char combustion at different conditions

图7 不同床料中CO2信号强度随反应时间变化趋势

Fig.7 Intensity of CO2versus time for char combustion with different bed materials

图8 不同床料条件下的化学应速率随碳转化率的变化趋势

Fig.8 Variation of the reaction rate with conversion for char combustion with different bed materials

图9 半焦燃烧ln(dx/dt)与1/T拟合曲线

Fig.9 Correlation of ln(dx/dt) and 1/T for char combustion

图10 半焦燃烧反应活化能

Fig.10 Activation energy of char combustion

图11 半焦燃烧最大反应速率与50%碳转化率所用时间

Fig.11 The maximum reaction rate and t0.5 of char combustion

图12 工业流化床中半焦燃烧过程

Fig.12 Char combustion in the industrial fluidized bed

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油页岩矿物质催化半焦燃烧特性及机理

Characteristics and mechanism of catalytic effect of inner minerals on combustion of oil shale coke

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