ZSM-11和ZSM-5分子筛孔道结构差异对其甲醇制烯烃催化性能的影响

原凯; 贾翔宇; 王森; 樊升; 何诗沛; 王鹏飞; 董梅; 秦张峰; 樊卫斌; 王建国

doi:10.1016/S1872-5813(23)60361-5

ZSM-11和ZSM-5分子筛孔道结构差异对其甲醇制烯烃催化性能的影响

doi: 10.1016/S1872-5813(23)60361-5

原凯^{1, 2,},
贾翔宇^{1, 2,},
王森^1, ,,
樊升^{1, 2,},
何诗沛^{1, 2,},
王鹏飞^1,,
董梅^1,,
秦张峰^1, ,,
樊卫斌^1,,
王建国^2,

1.
中国科学院山西煤炭化学研究所煤转化国家重点实验室, 山西太原 030001
2.
中国科学院大学, 北京 100049

基金项目: 国家重点研发计划（2020YFA0210900），国家自然科学基金（U1910203，21991090，21991092，22272195，U22A20431）和中国科学院青年创新促进会项目（2021172）资助

详细信息

通讯作者:
E-mail: wangsen@sxicc.ac.cn

qzhf@sxicc.ac.cn

中图分类号: O643.3
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出版历程
- 收稿日期: 2023-03-08
- 修回日期: 2023-04-10
- 录用日期: 2023-04-11
- 网络出版日期: 2023-04-25
- 刊出日期: 2023-11-13

Effect of framework structure of ZSM-11 and ZSM-5 zeolites on their catalytic performance in the conversion of methanol to olefins

YUAN Kai^{1, 2
,},
JIA Xiang-yu^{1, 2
,},
WANG Sen^{1
, ,},
FAN Sheng^{1, 2
,},
HE Shi-pei^{1, 2
,},
WANG Peng-fei^1
,,
DONG Mei^1
,,
QIN Zhang-feng^{1
, ,},
FAN Wei-bin^1
,,
WANG Jian-guo^2
,

1.
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China
2.
University of Chinese Academy of Sciences, Beijing 100049, China

Funds: The project was supported by the National Key R&D Program of China (2020YFA0210900), National Natural Science Foundation of China (U1910203, 21991090, 21991092, 22272195, U22A20431) and Youth Innovation Promotion Association CAS (2021172)

摘要

摘要: 本工作采用水热合成法制备了具有相似形貌、粒径、织构性质和酸性的ZSM-11和ZSM-5分子筛，借助多种表征技术研究了这两类分子筛的十元环孔道结构差异对其甲醇转化制烯烃（MTO）催化性能的影响。结果表明，由于ZSM-5的正弦孔道比ZSM-11的直孔道的扩散阻力大，反应中间体和产物分子在ZSM-5分子筛上的停留时间较长，强化了长链烯烃氢转移反应，导致生成更多的甲基苯物种，从而增强了芳烃循环的贡献；相比之下，ZSM-11分子筛的直孔道限制了长链烯烃的氢转移反应，减少了多甲基苯物种的产生，有利于提高烯烃循环的贡献。因此，与具有相似形貌、粒径、织构性质和酸性的ZSM-5-60分子筛相比，ZSM-11-60分子筛对MTO反应具有更长的催化寿命（98.3 h对比65.4 h）和更高的丙烯选择性（34.6%对比27.4%）。这些结果深化了对分子筛MTO催化性能与其孔道结构关系的认识，有助于新型高效的甲醇转化分子筛催化剂的开发和反应过程的探索。
- ZSM-11 /
- ZSM-5 /
- 直孔道 /
- 正弦孔道 /
- 甲醇转化制烯烃
Abstract: The catalytic performance of zeolites is closely related to their framework structure and a clear understanding of such a structure-performance relationship is of great significance in revealing catalytic reaction mechanism as well as in developing efficient zeolite catalysts. Herein, ZSM-11 and ZSM-5 zeolites with similar morphology, crystal size, textural properties and acidity were hydrothermally synthesized; the effects of their differences in the 10-ring channels on the catalytic performance in the conversion of methanol to olefins (MTO) were investigated by using various characterization techniques. The results indicate that in comparison with the straight channel of ZSM-11, the sinusoidal channel of ZSM-5 has stronger diffusion resistance, which promotes the hydrogen-transfer in higher olefins, leads to forming more polymethylbenzene species and then raises the contribution of aromatic-based cycle. In contrast, ZSM-11 with straight channel can reduce the formation of polymethylbenzene species and enhance the alkene-based cycle. As a result, compared with ZSM-5-60 with similar morphology and acidity, ZSM-11-60 as a catalyst in MTO exhibits longer lifetime (98.3 h vs. 65.4 h) and higher selectivity to propene (34.6% vs. 27.4%). The insight shown in this work helps to have a better understanding of the relation between zeolite structure and catalytic performance in MTO and is then beneficial to the development of better catalysts and processes for MTO.
- ZSM-11 /
- ZSM-5 /
- straight channel /
- sinusoidal channel /
- methanol to olefins

HTML全文

FIG. 2764. FIG. 2764.

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图 1 ZSM-11和ZSM-5分子筛的XRD谱图

Figure 1 XRD patterns of ZSM-11 and ZSM-5 zeolites

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图 2 ZSM-11和ZSM-5分子筛的SEM（嵌入为粒径分布）和TEM照片

Figure 2 SEM (insert: particle size distribution) and TEM images of ZSM-11 and ZSM-5 zeolites

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图 3 ZSM-11和ZSM-5分子筛的（a）N₂吸附-脱附曲线和（b）环己烷蒸气吸附曲线

Figure 3 (a) N₂ adsorption-desorption isotherms and (b) cyclohexane vapor adsorption isotherms of ZSM-11 and ZSM-5 zeolites

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图 4 ZSM-11和ZSM-5分子筛的（a）NH₃-TPD，（b）Py-IR，（c）dTBPy-IR和（d）分峰拟合后的硅核磁谱图

Figure 4 (a) NH₃-TPD profiles, (b) Py-IR spectra, (c) dTBPy-IR spectra and (d) deconvoluted ²⁹Si MAS NMR spectra of ZSM-11 and ZSM-5 zeolites

In the deconvoluted ²⁹Si MAS NMR spectra, the weak peak at −106 is attributed to the Q₃ (Si(OAl)₁(OSi)₃), whereas four peaks around −110.4, −112.3, −113.7 and −115.7, and at −110, −112.5, −115 and −117.5 are assigned to Q₄ (Si(0Al)) of ZSM-11 and ZSM-5, respectively

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图 5 ZSM-11和ZSM-5分子筛的铝核磁谱图及分峰拟合后的谱图

Figure 5 ²⁷Al MAS NMR spectra as well as deconvoluted ones of ZSM-11 and ZSM-5 zeolites

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图 6 Co-ZSM-11和Co-ZSM-5分子筛的漫反射紫外可见光光谱谱图

Figure 6 DR UV-vis spectra Co-ZSM-11 and Co-ZSM-5 zeolites

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图 7 ZSM-11-60 (a)、ZSM-5-60 (b)、ZSM-11-30 (c)和ZSM-5-30 (d)分子筛催化MTO反应中甲醇转化率、产物选择性

Figure 7 Methanol conversion and product selectivity with the time on stream for MTO over ZSM-11-60 (a), ZSM-5-60 (b), ZSM-11-30 (c) and ZSM-5-30 (d)

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图 8 ZSM-11和ZSM-5分子筛催化MTO反应时的C₄-HTI (a)、C₅-HTI (b)、(P−E)/E (c)随反应时间的变化以及失活后的ZSM-11和ZSM-5分子筛的热重曲线 (d)

Figure 8 A comparison of ZSM-11 and ZSM-5 as the catalyst for MTO in the C₄ hydride transfer index (C₄-HTI) (a), the C₅ hydride transfer index (C₅-HTI) (b), (P−E)/E ratio (c), and TGA curves (d) of spent catalysts. C_4/5-HTI is denoted as the ratio of (C_4/5 ⁰ )/( C_4/5 ⁰ + C_4/5 ⁼ )

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图 9 在450 ℃WHSV为4.8 h⁻¹的条件下MTO反应20 min后残留在ZSM-11和ZSM-5分子筛上有机物种的GC-MS谱图

Figure 9 GC-MS chromatograms of retained organic species over ZSM-11 and ZSM-5 zeolites after consecutively conducting the MTO reaction at 450 ℃ for 20 min with a methanol WHSV of 4.8 h⁻¹

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图 10 在350 ℃下连续流动 ¹³CH₃OH反应3 min，ZSM-11和ZSM-5分子筛上残留有机物种的 ¹³C MAS NMR谱图

Figure 10 ¹³C MAS NMR spectra of retained organic species over ZSM-11 and ZSM-5 zeolites after continuous flow ¹³CH₃OH reaction at 350 ℃ for 3 min, and the feed rates of Ar and ¹³CH₃OH are 40 and 0.1 mL/min, respectively

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图 11 在335 ℃下MTO反应不同时间后ZSM-11和ZSM-5分子筛上碳质物种含量

Figure 11 Content of carbonaceous species over ZSM-11 and ZSM-5 zeolites after consecutively conducting the MTO reaction at 335 ℃ for different time, and the feed rates of Ar and CH₃OH are 40 and 0.02 mL/min respectively

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表 1 ZSM-11和ZSM-5分子筛的织构性质

Table 1 Textural properties of ZSM-11 and ZSM-5 zeolites

Zeolite	Crystal size / μm	Surface area / (m²·g⁻¹)			Pore volume / (cm³·g⁻¹)
Zeolite	Crystal size / μm	total	micro	ext	total	micro	meso
ZSM-11-60	0.62	336	242	94	0.25	0.12	0.13
ZSM-5-60	0.63	337	249	88	0.23	0.11	0.12

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表 2 ZSM-11和ZSM-5分子筛的元素组成和酸性性质

Table 2 Elemental composition and acidic properties of ZSM-11 and ZSM-5 zeolites

Zeolite	Si/Al by ICP	Si/Al_F	Acidity by NH₃-TPD /(μmol·g⁻¹)			Acidity by Py-IR or dTBPy-IR /(μmol·g⁻¹)
Zeolite	Si/Al by ICP	Si/Al_F	strong	weak	total	Brønsted	Lewis	total	dTBPy-Brønsted
ZSM-11-60	51	54	228	116	344	175	43	218	19
ZSM-5-60	48	52	217	158	375	175	55	230	20
Note: framework Si/Al_F ratio is derived from the ²⁹Si MAS NMR spectra ^[19]

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表 3 ZSM-11和ZSM-5分子筛 ²⁷Al MAS NMR分峰拟合信号峰面积占总峰面积比例

Table 3 Proportion of integrated peaks obtained by deconvolution of the ²⁷Al MAS NMR spectra of ZSM-11 and ZSM-5 zeolites

Zeolite	Al_F /%	Al_EF /%	Aluminum distribution /%
Zeolite	Al_F /%	Al_EF /%	48.5–49.0	53.0–53.2	55.6–56.0	58.0–58.1
ZSM-11-60	99.5	0.5	6.4	38.1	45.1	10.4
ZSM-5-60	99.2	0.8	6.4	42.9	39.6	11.1

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表 4 Co-ZSM-11和Co-ZSM-5分子筛中不同类型铝物种的分布比

Table 4 Distribution of different types of Al species in Co-ZSM-11 and Co-ZSM-5 zeolites

Zeolite	Al_pairs /%	Al_single /%	Aluminum distribution /%
Zeolite	Al_pairs /%	Al_single /%	α	β	γ
ZSM-11-60	64	36	15.6	63.6	20.8
ZSM-5-60	58	42	12.4	63.5	24.1
Note: contents of Al_pairs and Al_single were calculated as [Al_pairs]= 2 × [Co] and [Al_single] = [Al_total] – [Al_pairs], where [Al_total] and [Co] are the contents of Al and Co in the Co-ZSM-11/Co-ZSM-5 samples, respectively, measured by ICP-OES

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表 5 ZSM-11和ZSM-5的 MTO催化反应

Table 5 Catalytic results of ZSM-11 and ZSM-5 zeolites in MTO

Zeolite	x_M /%	Product distribution /%								(P−E)/E	TON × 10⁴	Life time /h
Zeolite	x_M /%	C₁ ⁰	C_2–5 ⁰	C₂ ⁼	C₃ ⁼	C₄ ⁼	C₅ ⁼	C_{6 +}	arom.	(P−E)/E	TON × 10⁴	Life time /h
ZSM-11-60	99.9	2.1	9.3	8.3	34.6	24.4	9.0	2.9	9.4	3.2	8.1	98.3
ZSM-5-60	99.9	2.6	17.6	9.7	27.4	17.1	6.1	3.8	15.7	1.8	5.3	65.4
ZSM-11-30	99.9	4.5	19.1	8.9	24.6	15.3	4.7	3.6	19.3	1.8	2.3	48.7
ZSM-5-30	99.9	4.3	24.0	11.0	20.4	12.0	3.6	3.9	20.8	0.9	1.5	41.2
Note: methanol conversion and product distribution reported were acquired at half life time of each zeolite catalyst

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