烯烃对噻吩在介孔分子筛Al-MCM-41活性位物种上吸附脱硫机制的影响

郭忠森; 祖运; 惠宇; 秦玉才; 王焕; 张晓彤; 宋丽娟

烯烃对噻吩在介孔分子筛Al-MCM-41活性位物种上吸附脱硫机制的影响

郭忠森¹,
祖运^{1, 2},
惠宇^{1, 2},
秦玉才¹,
王焕^{1, 2},
张晓彤¹,
宋丽娟^{1, 2, ,}

1.
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
2.
中国石油大学(华东) 化学化工学院, 山东青岛 266555

基金项目:

国家自然科学基金 U1662135

国家自然科学基金 21376114

辽宁省博士科研启动基金 201601318

详细信息

中图分类号: O643
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- 被引次数: 0
出版历程
- 收稿日期: 2018-12-05
- 修回日期: 2019-01-27
- 网络出版日期: 2021-01-23
- 刊出日期: 2019-04-10

Influence of olefin on the mechanism of thiophene adsorption on the active species of Al-MCM-41 mesoporous zeolites

GUO Zhong-sen¹,
ZU Yun^{1, 2},
HUI Yu^{1, 2},
QIN Yu-cai¹,
WANG Huan^{1, 2},
ZHANG Xiao-tong¹,
SONG Li-juan^{1, 2
, ,}

1.
Key Laboratory of Petrochemical Catalytic Science and Technology, Liaoning Province, Liaoning Shihua University, Fushun 113001, China
2.
College of Chemistry & Chemical Engineering, China University of Petroleum(East China), Qingdao 266555, China

Funds:

the National Natural Science Foundation of China U1662135

the National Natural Science Foundation of China 21376114

Liaoning Province, PhD Research Initiated Fund Project 201601318

More Information

Corresponding author: SONG Li-juan, Tel: 13941350056, E-mail: lsong56@263.net

摘要

摘要: 采用后嫁接法制备了不同铝负载量的Al-MCM-41分子筛。运用XRD、N₂吸附-脱附、NH₃-TPD、Py-FTIR等方法对分子筛进行物性表征，利用固定床评价其对噻吩的吸附性能。通过将分子筛吸附噻吩能力与分子筛的酸性质及织构性质进行关联，考察烯烃存在对Al-MCM-41活性位物种吸附脱硫机制的影响。结果表明，铝物种的引入即产生了B酸中心，也同时产生了两种类型的L酸中心L₁和L₂。引入低含量铝物种利于形成B酸中心和L₁型酸中心，引入高含量铝物种利于形成L₂型酸中心。其中，L₂型酸中心对噻吩的吸附效果最佳。烯烃和噻吩在B酸中心发生竞争吸附和催化转化反应，且催化转化反应占主导地位。L₂酸中心的存在促进了B酸中心上的催化转化反应，其所生成的大分子硫化物取代噻吩吸附在分子筛酸活性中心上提高了Al-MCM-41分子筛的饱和吸附硫容量。
- Al-MCM-41分子筛 /
- 噻吩 /
- 烯烃 /
- 酸性中心 /
- 吸附脱硫机制
Abstract: The Al-MCM-41 zeolites with different Al contents were prepared by post-grafting method and characterized by means of XRD, N₂ adsorption-desorption, NH₃-TPD, and Py-FTIR. The adsorptive performance of thiophene on these samples was investigated in a fixed bed by using micro coulombmeter and GC-SCD technique. The thiophene adsorption capacity was correlated with the acid properties and texture properties of the molecular sieve, and the effect of olefin on the adsorption desulfurization mechanism of active species in Al-MCM-41 was investigated. The results show that the introduction of lower content aluminum species is conducive to the formation of B (Brønsted) acid center and L₁ (Lewis) acid center, while higher content aluminum species is conducive to the formation of L₂ (Lewis) acid center. L₂ acid center exhibits a far stronger thiophene adsorption ability than L₁ acid center that has a slightly stronger thiophene adsorption ability than B acid center. Competitive adsorption and catalytic conversion of olefin and thiophene take place on the B acid center, and the catalytic reaction is dominated. The existence of L₂ acid center greatly promotes the catalytic conversion reaction on the B acid center. The adsorption of macromolecular sulfide instead of thiophene increases the saturated adsorption capacity of Al-MCM-41 zeolites.
- Al-MCM-41 zeolite /
- thiophene /
- olefin /
- acid active center /
- adsorption desulfurization mechanism

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图 1 不同铝含量Al-MCM-41样品的XRD谱图

Figure 1 XRD patterns of the Al-MCM-41 samples

(a): low-angle; (b): wide-angle

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图 2 不同铝含量Al-MCM-41样品的N₂吸附-脱附等温线和孔径分布

Figure 2 Nitrogen adsorption-desorption isotherms and BJH pore size distributions of the Al-MCM-41 samples

◆: Al-MCM-41(∞) adsorption; ◇: Al-MCM-41(∞) desorption; ▼: Al-MCM-41(60) adsorption; ▽: Al-MCM-41(60)desorption; ★: Al-MCM-41(30)adsorption; ☆: Al-MCM-41(30)desorption; ●: Al-MCM-41(10) adsorption; ○: Al-MCM-41(10)desorption

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图 3 不同铝含量Al-MCM-41样品的NH₃-TPD谱图和高斯拟合曲线

Figure 3 NH₃-TPD patterns and Gaussian fitting profiles of the Al-MCM-41 samples

——: actual curve; ----: fit curves

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图 4 不同铝含量Al-MCM-41分子筛的Py-FTIR谱图

Figure 4 Py-FTIR characterization of the Al-MCM-41 samples

(a): 150 ℃ of desorption temperature; (b): 400 ℃ of desorption temperature a: Al-MCM-41(∞); b: Al-MCM-41(60); c: Al-MCM-41(30); d: Al-MCM-41(10)

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图 5 Al-MCM-41样品中不同形式的酸活性中心

Figure 5 Type of acid active centers in Al-MCM-41 samples

BA: Br∅nsted acid site; L₁A and L₂A: type 1 and type 2 Lewis acid site

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图 6 不同铝含量Al-MCM-41样品对MO-1的动态吸附曲线(a)、萃取液的GC-SCD谱图(b)、穿透吸附硫容量(c)及饱和吸附硫容量(d)

Figure 6 Breakthrough curves of MO-1 model oil on the Al-MCM-41 samples (a), the GC-SCD chromatograms of the extraction solution samples (b), breakthrough (c) and saturation (d) adsorption capacity of the Al-MCM-41 samples

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图 7 不同铝含量Al-MCM-41样品对MO-2模拟油的动态吸附曲线(a)及吸附硫容量(b)

Figure 7 Breakthrough curves (a) and sulfur adsorption capacity (b) of the MO-2 model oil on the Al-MCM-41 samples

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图 8 MO-2模拟油吸附实验中不同时间段所取油样的产物分布图

Figure 8 Products distribution map of oil samples from the MO-2 adsorption tests

(a): Al-MCM-41(∞); (b): Al-MCM-41(60); (c): Al-MCM-41(30); (d): Al-MCM-41(10)

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图 9 噻吩同烯烃可能的催化转化反应机理示意图

Figure 9 Possible reaction mechanism of 1-hexene and thiophene on the acid active site

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图 10 不同铝含量Al-MCM-41样品对MO-2模拟油动态吸附实验中吸附饱和的样品经萃取后萃取液的GC-SCD谱图(a)及不同硫化物产物分布图(b)

Figure 10 GC-SCD chromatograms (a) and different sulfides distribution map (b) of extraction solutions by Al-MCM-41 sample

a: Al-MCM-41(∞); b: Al-MCM-41(60); c: Al-MCM-41(30); d: Al-MCM-41(10)

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表 1 不同硅铝比Al-MCM-41分子筛的结构参数

Table 1 Textural parameters of the different Si/Al ratio Al-MCM-41 samples

Sample	A_BET /(m²·g^-1)	A_mic /(m²·g^-1)	A_meso /(m²·g^-1)	v_p /(cm³·g^-1)	Average pore diameter d/nm	a₀/nm	w/% (Al)
Al-MCM-41(∞)	1069.3	12.3	1057	1.0	2.79	3.22	-
Al-MCM-41(60)	1067.4	12.5	1054.9	0.9	2.82	3.26	0.70
Al-MCM-41(30)	1063.1	12.8	1050.3	1.0	2.83	3.27	1.41
Al-MCM-41(10)	1046	9.6	1036.4	0.85	2.70	3.12	3.99
w/% (Al)：actual Al content in samples which is tested by ICP-MS

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表 2 不同铝含量Al-MCM-41样品中不同活性中心相对比例

Table 2 Proportion of active sites in Al-MCM-41 samples

Sample	B/(B+L₁+L₂)	L₁/(B+L₁+L₂)	L₂/(B+L₁+L₂)
Al-MCM-41(∞)(150 ℃)	0.41	0.53	0.06
Al-MCM-41(60)(150 ℃)	0.38	0.62	0
Al-MCM-41(30)(150 ℃)	0.53	0.47	0
Al-MCM-41(10)(150 ℃)	0.16	0.27	0.57
Al-MCM-41(∞)(400 ℃)	0.26	0.74	0
Al-MCM-41(60)(400 ℃)	0.27	0.73	0
Al-MCM-41(30)(400 ℃)	0.26	0.74	0
Al-MCM-41(10)(400 ℃)	0.16	0.30	0.54
note: proportion of active sites are calculated from the peak area of Py-FTIR spectra by emeis’s method^[25]

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