Ce离子对苯在Y分子筛上吸附扩散行为的影响

张乐; 李强; 赵越; 秦玉才; 高雄厚; 宋丽娟

Ce离子对苯在Y分子筛上吸附扩散行为的影响

张乐^{1, 2},
李强²,
赵越²,
秦玉才²,
高雄厚³,
宋丽娟^{1, 2, ,}

1.
中国石油大学(华东) 化学工程学院, 山东青岛 266580
2.
辽宁石油化工大学辽宁省石油化工催化科学与技术重点实验室, 辽宁抚顺 113001
3.
中国石油天然气股份有限公司石油化工研究院, 北京 100083

基金项目:

国家自然科学基金 21376114

详细信息

通讯作者:
宋丽娟, Tel:+86-024-56860658, E-mail:tianhuikele@126.com, lsong56@263.net

中图分类号: TQ426.95
计量
- 文章访问数: 68
- HTML全文浏览量: 26
- PDF下载量: 7
- 被引次数: 0
出版历程
- 收稿日期: 2016-09-14
- 修回日期: 2016-11-03
- 网络出版日期: 2021-01-23
- 刊出日期: 2017-01-10

Effect of Ce ion on adsorption and diffusion behavior of benzene in Y zeolite

ZHANG Le^{1, 2},
LI Qiang²,
ZHAO Yue²,
QIN Yu-cai²,
GAO Xiong-hou³,
SONG Li-juan^{1, 2
, ,}

1.
College of Chemical Engineering, China University of Petroleum (East China), Qingdao 266580, China
2.
Liaoning Key Laboratory of Petrochemical Catalytic Science and Technology, Liaoning Shihua University, Fushun 113001, China
3.
Research Institute of Petroleum Processing, SINOPEC, Beijing 100083, China

Funds:

National Natural Science Foundation of China 21376114

摘要

摘要: 采用液相离子交换法制备了不同稀土含量的Y型分子筛（HY、USY和NaY），研究了稀土铈（Ce）阳离子在Y型分子筛上吸附-脱附烃类分子（苯）过程中的作用机理与影响。通过X射线荧光光谱仪（XRF）、智能质量分析仪（IGA）、脱附指数的计算和巨正则蒙特卡罗模拟计算等多种表征计算方法，对引入稀土物种后，Y型分子筛对苯的饱和吸附量、吸附作用力、脱附热力学参数、苯在Y分子筛上的吸附势能分布及扩散行为等方面进行了研究。结果表明，Ce离子对苯在Y分子筛上脱附活化能的降低、吸附作用力的减弱以及吸附态由团聚态向分散态转变等方面具有显著影响，该作用构成了CeY分子筛催化剂在流化催化裂化（FCC）过程中能够优化轻质产品选择性的重要因素。
- 催化 /
- Y型沸石 /
- 表面 /
- 吸附剂 /
- 产品选择性 /
- 蒙特卡罗模拟
Abstract: The liquid ion exchange method was employed to prepare cerium (Ce) cation modified Y zeolite (CeY) with various amount of cerium using different types of Y zeolite (HY, USY and NaY) and characterized by X-ray fluorescence spectrometry (XRF), intelligent gravimetric analyzer (IGA) and a molecular simulation technology (Grand Canonical Monte Carlo simulation, GCMC). A novel calculation method of desorption index (DI) has also been proposed to study the influence of cerium cations on the processes of adsorption-desorption of hydrocarbon molecule (benzene) on the CeY zeolites. The saturated adsorption capacity of benzene, adsorption interaction, desorption thermodynamic parameters, potential distribution curves and diffusion processes of benzene in CeY zeolites were analyzed. The results indicate that Ce ion can reduce the desorption activation energy, weaken the adsorption interaction force between benzene and Y zeolites, and modulate the adsorbed state of benzene molecules from agglomerate state to dispersed state, which are main factors to optimize the product selectivity of light oil components in the fluid catalytic cracking (FCC) process with CeY zeolite catalyst.
- catalysis /
- Y-type zeolite /
- surface /
- sorbents /
- product selectivity /
- Monte Carlo simulation

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图 1 实验样品经XRF所测的Ce含量

Figure 1 Cerium content of the zeolite samples detected by XRF

下载: 全尺寸图片幻灯片

图 2 苯在NaY和不同Ce (OH)²⁺含量CeY上的吸附等温线(符号代表实验数据，实线代表拟合结果)

Figure 2 Adsorption isotherms of C₆H₆ in CeY with various amount of Ce (OH)²⁺and NaY (symbol represents the experimental data; solid lines represent the fitting results)

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图 3 苯在不同CeY分子筛上的脱附指数变化(303K)

Figure 3 Change of Desorption-Index of benzene in various CeY zeolites (303K)

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图 4 苯在不同Ce含量CeY分子筛上的TG-DTG曲线(303 K)

Figure 4 TG-DTG curves of benzene for various CeY zeolites (303 K)

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图 5 苯在不同Ce (OH)²⁺含量的CeY上的吸附密度图(303 K)

Figure 5 Energy density of C₆H₆ in CeY with various amount of Ce (OH)²⁺ (303 K)

(a): 13.3% Ce (OH)²⁺; (b): 42.3% Ce (OH)²⁺; (c): 71.3% Ce (OH)²⁺; (d): 99.7% Ce (OH)²⁺

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图 6 苯在NaY及不同Ce (OH)²⁺含量CeY分子筛上的吸附势能分布曲线(303 K)

Figure 6 Potential energy distribution of benzene in CeY with various amount of Ce (OH)²⁺ and NaY (303 K)

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图 7 苯在NaY和CeY分子筛中扩散的MSD随时间的变化曲线(303 K)

Figure 7 MSD-t curves of benzene diffusion in a NaY and different CeY zeolites at 303 K

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图 8 不同Ce含量Y分子筛的织构性质

Figure 8 Pore structure properties of Y zeolites with various amount of cerium ions

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图 9 不同Ce含量Y分子筛的轻质产物汽油的液收率

Figure 9 Gasoline liquid yield for CeY zeolites with various amount of cerium ions

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表 1 Langmuir方程拟合C₆H₆在CeY分子筛中的吸附等温线数据

Table 1 Adsorption isotherm parameters of C₆H₆ in CeY zeolite fitted with Langmuir equations

Sample Q_m K R²

NaY 255.20 0.12 0.984

13.3%CeY 254.16 0.15 0.973

42.3%CeY 245.07 0.12 0.972

71.3%CeY 226.80 0.10 0.980

99.7%CeY 206.02 0.07 0.975

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表 2 苯与NaY和不同CeY分子筛最可几相互作用的能量(303 K)

Table 2 Interaction energies of benzene with NaY and CeY zeolites (303 K)

Energy E/(kJ·mol^-1)

NaY 13.3%CeY 42.3%CeY 71.3%CeY 99.7%CeY

-87.99 -71.55 -69.16 -88.24 -108.28

-106.15 -98.87 -95.14 -103.85 -137.32

-125.27 -127.91 -134.52

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