<i>β</i>分子筛的Si/Al比对PtZn催化丙烷非临氢脱氢性能的影响

李博楠; 邢亚楠; 康磊磊; 刘晓艳

doi:10.19906/j.cnki.JFCT.2023023

β分子筛的Si/Al比对PtZn催化丙烷非临氢脱氢性能的影响

doi: 10.19906/j.cnki.JFCT.2023023

李博楠^{1, 2,},
邢亚楠^{1, 2,},
康磊磊^1,,
刘晓艳^1, ,

1.
中国科学院大连化学物理研究所航天催化与新材料研究室, 辽宁大连 116023
2.
中国科学院大学, 北京 100049

基金项目: 国家自然科学基金（22102180），辽宁省“兴辽英才计划”项目（XLYC2007070）和中国科学院洁净能源创新研究院合作基金（DNL202002）资助

详细信息

通讯作者:
Tel: 13478962650, E-mail: xyliu2003@dicp.ac.cn

中图分类号: O643.3
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出版历程
- 收稿日期: 2023-01-30
- 修回日期: 2023-03-10
- 录用日期: 2023-03-10
- 网络出版日期: 2023-04-06
- 刊出日期: 2023-10-10

Effect of Si/Al ratio of β zeolite on propane dehydrogenation without H₂ over PtZn catalyst

LI Bo-nan^{1, 2
,},
XING Ya-nan^{1, 2
,},
KANG Lei-lei^1
,,
LIU Xiao-yan^{1
, ,}

1.
CAS Key Laboratory of Science and Technology on Applied Catalysis, iChEM, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China
2.
University of Chinese Academy of Sciences, Beijing 100049, China

Funds: The project was supported by the National Natural Science Foundation of China (22102180), LiaoNing Revitalization Talents Program (XLYC2007070) and the DNL Cooperation Fund, CAS (DNL202002)

摘要

摘要: 采用共浸渍法制备PtZn/β-x(x为SiO₂/Al₂O₃物质的量比)分子筛双金属催化剂，探究了β分子筛中硅铝比对丙烷非临氢脱氢反应性能的影响。采用XRD、BET、HAADF-STEM、NH₃-TPD、C₃H₆-TPD等一系列表征技术对催化剂的物相结构、表面性质及其对丙烷非临氢脱氢反应性能的影响进行了研究。结果表明，催化稳定性随载体中Si/Al比的增大而提高(稳定性顺序：PtZn/DeAl-β > PtZn/β-40 > PtZn/β-30 > PtZn/β-25)，而催化剂的强酸位点数量(PtZn/β-30 > PtZn/β-40 > PtZn/β-25 > PtZn/DeAl-β)，在一定程度上受硅铝比的影响，与丙烯选择性顺序相反。因此，分子筛的Si/Al比对催化剂的性质有重要的调变作用，当催化剂强酸位点较少、丙烯吸附较弱、比表面积较大时，有助于提高丙烷转化率、丙烯选择性和催化稳定性。
- 硅铝比 /
- PtZn双金属催化剂 /
- β分子筛 /
- 丙烷非临氢脱氢
Abstract: In this study, the PtZn/β-x catalysts (x refers to SiO₂/Al₂O₃ mole ratio) were synthesized by co-impregnation method and the effect of Si/Al ratio of the β zeolite on propane non-hydrogen dehydrogenation was explored. A series of characterization such as XRD, BET, HAADF-STEM, NH₃-TPD, C₃H₆-TPD were applied to investigate the phase structure, surface properties of catalysts, and their effects on the reaction performances. The results showed that, with the increase of Si/Al ratio, the catalytic stability would be enhanced following the order of PtZn/DeAl-β > PtZn/β-40 > PtZn/β-30 > PtZn/β-25, while the number of strong acid sites of the catalyst (PtZn/β-30 > PtZn/β-40 > PtZn/β-25 > PtZn/DeAl-β) was affected by the Si/Al ratio to some extent, which was opposite to the order of the propylene selectivity. Therefore, the control of the Si/Al ratio of zeolite is very important for optimizing the properties of the catalysts for propane dehydrogenation reaction. The catalysts with few strong acid sites, weak adsorption of propylene and large specific surface area are contributed to higher propane conversion, propylene selectivity and catalytic stability.
- Si/Al ratio /
- PtZn bimetallic catalyst /
- β zeolite /
- propane non-hydrogen dehydrogenation

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FIG. 2702. FIG. 2702.

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图 1 500 ℃焙烧后PtZn/β-x系列催化剂的XRD谱图

Figure 1 XRD patterns of PtZn/β-x catalysts after calcination at 500 ℃

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图 2 PtZn/β-x系列催化剂的N₂吸附-脱附等温线

Figure 2 N₂ adsorption and desorption isotherms of PtZn/β-x catalysts

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图 3 PtZn/β-x系列催化剂在还原后的HAADF-STEM照片和粒径分布

Figure 3 HAADF-STEM spectra and particle size statistic chart of (a) PtZn/β-25, (b) PtZn/β-30, (c) PtZn/β-40, (d) PtZn/DeAl-β after reduction

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图 4 （a）PtZn/β-x系列催化剂的H₂-TPR谱图，（b）PtZn/β-40催化剂H₂-TPR的质谱信号，（c）β-x载体的H₂-TPR谱图

Figure 4 (a) H₂-TPR spectra of PtZn/β-x catalysts, (b) Mass signal of PtZn/β-40 during H₂-TPR, (c) H₂-TPR spectra of β-x supports (The graph in the frame is mass signal of β-40 with mass number of 16)

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图 5 PtZn/β-x系列催化剂的NH₃-TPD谱图及NH₃脱附量

Figure 5 (a) NH₃-TPD spectra and (b) NH₃ desorption of PtZn/β-x catalysts

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图 6 PtZn/β-x系列催化剂的C₃H₆-TPD谱图

Figure 6 Temperature-MS signal spectra of C₃H₆-TPD of PtZn/β-x catalysts Mass number is (a) 42 (C₃H₆), (b) 30 (C₂H₆), (c) 16 (CH₄)

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图 7 PtZn/β-x系列催化剂丙烷非临氢脱氢反应活性

Figure 7 Activity evaluation of PtZn/β-x catalysts on propane dehydrogenation without H₂ (a): Conversion of propane; (b): Selectivity of propylene

(Reaction conditions: 0.1 g catalyst, 600 ℃, 30 mL/min 5%C₃H₈/He, WHSV = 1.8 h⁻¹)

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图 8 (a) 不同目数和(b) 不同线速下PtZn/DeAl-β催化剂的丙烷脱氢催化性能比较

Figure 8 Comparison of PDH performance of PtZn/DeAl-β catalysts (a) with different mesh numbers and (b) at different linear velocities (Reaction conditions: 600 ℃, WHSV = 1.8 h⁻¹, (a) 0.1 g catalyst, 20−40 or 60−80 mesh, 30 mL/min 5%C₃H₈/He(b) 0.02 g or 0.05 g or 0.1 g catalyst, total mass is 0.1 g, 60−80 mesh, 6 or 15 or 30 mL/min 5%C₃H₈/He)

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图 9 PtZn/β-x系列催化剂反应3 h后的热重曲线

Figure 9 Thermogravimetric analysis of PtZn/β-x catalysts after propane dehydrogenation reaction without H₂ for 3 h

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表 1 PtZn/β-x系列催化剂的织构参数和Pt、Zn元素含量

Table 1 Textural parameters and Pt, Zn element content of PtZn/β-x catalysts

Catalyst	$S_{{\rm{BET}}}^{\rm{a}} $ / (m²·g⁻¹)	$S_{\rm{micro}}^{\rm{b}} $ /(m²·g⁻¹)	$S_{\rm{external}}^{\rm{b}} $ /(m²·g⁻¹)	$v_{\rm{micro}}^{\rm{b}} $ / (cm³·g⁻¹)	$v_{\rm{meso}}^{\rm{c}} $ / (cm³·g⁻¹)	Pt^d w/%	Zn^d w/%
PtZn/β-25	436.4	305.6	130.7	0.16	0.28	0.50	2.60
PtZn/β-30	482.8	383.7	99.1	0.20	0.18	0.55	2.84
PtZn/β-40	438.6	345.2	93.4	0.18	0.17	0.57	2.83
PtZn/DeAl-β	499.5	329.5	170.0	0.17	0.48	0.56	2.83
^a: Calculated by BET method, ^b: Calculated by t-plot method, ^c: Calculated by BJH method, ^d: Characterized by ICP-OES

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表 2 PtZn/β-x系列催化剂的H₂-TPR过程耗氢量

Table 2 Hydrogen consumption in H₂-TPR process of PtZn/β-x catalysts

Catalyst	Theoretical H₂ consumption of Pt^{δ +} /(mmol·g⁻¹)	(1) / (mmol·g⁻¹)	(2) / (mmol·g⁻¹)	(3) / (mmol·g⁻¹)	(4) / (mmol·g⁻¹)	Reduction temperature of Pt^{δ +} /℃
PtZn/β-25	0.025	0.039	0.002	0.012	0	−30.7
PtZn/β-30	0.028	0.043	0.003	0	0.13	−31.2
PtZn/β-40	0.029	0.034	0.010	0	0	−27.1
PtZn/DeAl-β	0.029	0.024	0.002	0.026	0	−26.6

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表 3 PtZn/β-x系列催化剂反应3 h后的热重参数和失活速率常数(k_d)

Table 3 Thermogravimetric parameters and deactivation rate constant (k_d) of PtZn/β-x catalysts after 3 h propane dehydrogenation reaction without H₂

Catalyst	Weight /%	Temp. range /℃	k_d /h⁻¹
PtZn/β-25	14.4	387−610	0.38
PtZn/β-30	12.5	397−610	0.35
PtZn/β-40	11.5	415−618	0.13
PtZn/DeAl-β	1.50	505−681	0.10

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