纳米片Ga-MFI分子筛合成及其对航空燃油催化裂解反应中低碳烯烃选择性的影响

doi:10.16085/j.issn.1000-6613.2019-0016

化工进展 ›› 2019, Vol. 38 ›› Issue (9): 4075-4084.DOI: 10.16085/j.issn.1000-6613.2019-0016

纳米片Ga-MFI分子筛合成及其对航空燃油催化裂解反应中低碳烯烃选择性的影响

李琦¹(),张强¹(),赵慧莹¹,陈志¹,宋进喜¹,延卫²

1. 西北大学城市与环境学院，陕西西安710127
2. 西安交通大学环境科学与工程系，陕西西安710049

收稿日期:2019-01-03 出版日期:2019-09-05 发布日期:2019-09-05
通讯作者: 张强
作者简介:李琦（1974—），女，博士，副教授，主要研究方向为水环境修复及环境材料。E-mail: qili726@nwu.edu.cn。
基金资助:
国家自然科学基金(51308457);陕西省重点科技创新团队计划(2014KCT-27);陕西省自然科学基金(2012JM7014);陕西省教育厅科学研究计划(17JK0771)

Synthesis of nanosheets Ga-MFI zeolites and its effect on selectivity of low carbon olefin in aviation fuel catalytic cracking reaction

Qi LI¹(),Qiang ZHANG¹(),Huiying ZHAO¹,Zhi CHEN¹,Jinxi SONG¹,Wei YAN²

1. College of Urban and Environmental Sciences, Northwest University, Xi’an 710127, Shaanxi, China
2. Department of Environmental Science and Engineering, Xi’an Jiaotong University, Xi’an 710049, Shaanxi, China

Received:2019-01-03 Online:2019-09-05 Published:2019-09-05
Contact: Qiang ZHANG

摘要/Abstract

摘要：

在纳米片Al-MFI分子筛合成的基础上，以镓源[Ga(NO₃)₃·xH₂O]替换铝源[Al₂(SO₄)₃·18H₂O]，合成出类质同象纳米片Ga-MFI分子筛，采用X射线衍射、扫描电镜、BET比表面积分析和NH₃程序升温脱附法等技术对其进行了表征，并考察了普通ZSM-5分子筛、纳米片Al-MFI分子筛和纳米片Ga-MFI分子筛对航空燃油裂解反应的催化性能。结果表明，合成的分子筛是具有MFI骨架拓扑结构的纳米片状分子筛，具有较大的比表面积（482m²/g）和中孔孔容；与铝原子相比，镓原子与硅、氧原子形成的酸性位点的酸性减弱。在高温下（600℃），它抑制了氢转移反应的进行，减少了低碳烯烃的二次反应和结焦前体（芳香烃）在酸性位点上的吸附，使其具有更高催化活性和低碳烯烃选择性，从而获得了比纳米片Al-MFI分子筛高14.47%的热沉。该研究为高超音速飞行器的主动热防护提供了技术支撑。

关键词: 类质同象, 纳米片Ga-MFI分子筛, 酸性, 低碳烯烃, 热沉

Abstract:

Based on the synthesis of nanosheets Al-MFI zeolite, isomorphous MFI nanosheets zeolite was synthesized by replacing aluminum source with gallium source. The obtained samples were characterized by XRD, SEM, BET and NH₃-TPD. The catalytic performances of ordinary ZSM-5 zeolite, nanosheets Al-MFI zeolite and nanosheets Ga-MFI zeolite were tested with aviation fuel. The results showed that it was indeed a kind of nanosheets zeolite with an MFI skeleton topology, with a large specific surface area (482m²/g) and mesoporous volume. Compared with aluminum atoms, gallium atoms became less acidic at the acidic site formed by silicon and oxygen atoms. This made nanosheets Ga-MFI zeolite inhibit the hydrogen transfer reaction at high temperature (600℃), reducing the secondary reaction of low olefins and the adsorption of coking precursors (aromatic hydrocarbons) on acidic sites. This led to higher catalytic activity and light olefin selectivity, resulting in heat sink 14.47% higher than that of nanosheets Al-MFI zeolite. The study provided technical support for the active thermal protection of hypersonic vehicles.

Key words: isomorphous, nanosheets Ga-MFI zeolite, acidic, light olefin, heat sink

中图分类号:

TQ519

李琦,张强,赵慧莹,陈志,宋进喜,延卫. 纳米片Ga-MFI分子筛合成及其对航空燃油催化裂解反应中低碳烯烃选择性的影响[J]. 化工进展, 2019, 38(9): 4075-4084.

Qi LI,Qiang ZHANG,Huiying ZHAO,Zhi CHEN,Jinxi SONG,Wei YAN. Synthesis of nanosheets Ga-MFI zeolites and its effect on selectivity of low carbon olefin in aviation fuel catalytic cracking reaction[J]. Chemical Industry and Engineering Progress, 2019, 38(9): 4075-4084.

图/表 15

图1 煤油催化裂解反应实验装置示意图

图2 单管实验段结构示意图

图3 分子筛的XRD谱图

图4 分子筛的SEM图

图5 分子筛的氮气吸脱附等温线和孔径分布图

表1 分子筛的组织结构性质和硅铝比

样品	Si/Al或Si/Ga	R _c ^①/%	S _BET ^②/m²·g^-1	V _total ^③/cm³·g^-1	V _meso ^④/cm³·g^-1	V _micro ^⑤/cm³·g^-1	P ^⑥/nm
ZSM-5	52.7	117.0	293	0.21	0.07	0.14	1.4
Al-MFI	62.6	100.0	478	0.80	0.58	0.22	3.3
Ga-MFI	48.2	89.2	482	0.79	0.57	0.22	3.3

图6 ZSM-5、Al-MFI和Ga-MFI的酸性表征

图7 ZSM-5、Al-MFI和Ga-MFI在不同温度下

图8 航空煤油在不同反应管内550℃和600℃的产气率随时间的变化

图9 ZSM-5、Al-MFI和Ga-MFI在不同温度下催化裂解煤油反应热沉

图10 Al-MFI和Ga-MFI在550℃下催化裂解航空煤油气相产物分布

图11 Al-MFI和Ga-MFI在600℃下催化裂解航空煤油气相产物分布的对比

图12 Al-MFI和Ga-MFI催化裂解航空煤油CMR和RM值

图13 碳正离子芳构化反应和氢转移反应示意图

图14 Al-MFI和Ga-MFI催化裂解航空煤油的HTI值

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纳米片Ga-MFI分子筛合成及其对航空燃油催化裂解反应中低碳烯烃选择性的影响

Synthesis of nanosheets Ga-MFI zeolites and its effect on selectivity of low carbon olefin in aviation fuel catalytic cracking reaction

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