Pt-Ga/CeO2-ZrO2-Al2O3脱氢裂解双功能催化剂用于正丁烷催化制烯烃研究

doi:10.11949/0438-1157.20231384

化工学报 ›› 2024, Vol. 75 ›› Issue (5): 1855-1869.DOI: 10.11949/0438-1157.20231384

• 催化、动力学与反应器 • 上一篇下一篇

Pt-Ga/CeO₂-ZrO₂-Al₂O₃脱氢裂解双功能催化剂用于正丁烷催化制烯烃研究

莫锦洪¹(), 韩雪¹, 朱毅翔¹, 李菁², 王旭裕²(), 纪红兵¹^,²^,³()

^1.广西大学化学化工学院，广西南宁 530004
^2.江苏科技大学环境与化学工程学院，江苏镇江 212100
^3.浙江工业大学化学工程学院/浙江绿色石化与轻烃转化研究院/绿色化学合成技术国家重点实验室培育基地，浙江杭州 310014

收稿日期:2023-12-28 修回日期:2024-02-29 出版日期:2024-05-25 发布日期:2024-06-25
通讯作者: 王旭裕,纪红兵
作者简介:莫锦洪（1994—），男，硕士研究生，1056732442@qq.com
基金资助:
国家重点研发计划项目(2020YFA0210900);广东省科技厅项目(STKJ2023015);广西省科技厅项目(AA23062018)

Investigation of Pt-Ga/CeO₂-ZrO₂-Al₂O₃bifunctional catalyst for the catalytic conversion of n-butane into olefins

Jinhong MO¹(), Xue HAN¹, Yixiang ZHU¹, Jing LI², Xuyu WANG²(), Hongbing JI¹^,²^,³()

^1.School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004, Guangxi, China
^2.School of Environmental and Chemical Engineering, Jiangsu University of Science and Technology, Zhenjiang 212100, Jiangsu, China
^3.State Key Laboratory Breeding Base of Green-Chemical Synthesis Technology, Institute of Green Petroleum Processing and Light Hydrocarbon, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, Zhejiang, China

Received:2023-12-28 Revised:2024-02-29 Online:2024-05-25 Published:2024-06-25
Contact: Xuyu WANG, Hongbing JI

摘要/Abstract

摘要：

正丁烷分子结构相对稳定，C－C键键能较高，难以有效利用，目前大部分作为低价值燃料，通过脱氢、裂解等反应将正丁烷转化为高附加值的轻烯烃研究具有重要的科学意义。采用分步浸渍法将Pt和Ga负载到CeO₂-ZrO₂-Al₂O₃ (CZA)载体制备PtGa/CZA催化剂，将Pt-Ga₂O₃引入作为脱氢位点进行脱氢反应(C₄H₁₀→C $4 =$ )，CZA作为酸位点进行裂解反应(C $4 =$ →C $3 =$ ，C $2 =$ )，同时PtGa与CZA协同提高表面吸附氧含量降低正丁烷活化温度。结果表明，与负载单Pt或Ga催化剂相比，将Pt和Ga同时负载到CZA载体上，可极大提高反应的转化率和选择性，在500℃时，PtGa/CZA催化剂的正丁烷转化率为64.3%，比Pt/CZA和Ga/CZA催化剂分别高55.9%和53.9%，三者轻烯烃选择性均在95%以上。将PtGa/CZA催化剂制成涂层催化剂，提高了正丁烷转化率和催化剂稳定性。PtGa/CZA催化剂优异的活性归因于较低的Ce⁴⁺还原温度和表面吸附氧脱附温度、较多的表面吸附氧位点含量和强酸位点含量。

关键词: 烷烃, 催化裂解, 铂镓, 催化剂, 载体

Abstract:

The molecular structure of n-butane is relatively stable with high C—C bond energy, which makes it difficult to be effectively utilized, and most of it is currently burned as a low-value fuel. The study of converting n-butane into high-value-added light olefins through dehydrogenation, cracking, and other reactions is also of great scientific significance. In this study, Pt and Ga were sequentially impregnated onto CeO₂-ZrO₂-Al₂O₃ (CZA) support by using a stepwise method to prepare the PtGa/CZA catalyst. Pt-Ga₂O₃ was introduced as a dehydrogenation catalyst for the conversion of C₄H₁₀ to C $4 =$ , while CZA functions as an acid catalyst for the cracking reactions leading to C $4 =$ →C $3 =$ and C $2 =$ . Simultaneously, PtGa and CZA synergistically enhance the surface oxygen adsorption capacity and reduce the activation temperature required for n-butane. The results demonstrated that simultaneous loading of Pt and Ga onto the CZA support significantly enhanced both conversion rate and selectivity compared to single-loaded Pt or Ga catalysts. At 500℃, the conversion rate of n-butane over the PtGa/CZA catalyst reached 64.3%, which was 55.9% higher than that achieved with the Pt/CZA catalyst and 53.9% higher than that obtained with the Ga/CZA catalyst. All three catalysts exhibited selectivity above 95%. The PtGa/CZA catalyst was made into a coated catalyst to improve n-butane conversion and catalyst stability. The excellent activity of the PtGa/CZA catalysts was attributed to the lower Ce⁴⁺ reduction temperature and surface adsorbed oxygen desorption temperature, as well as the larger surface adsorbed oxygen site content and strong acid site content.

Key words: alkane, catalytic cracking, platinum-gallium, catalyst, support

中图分类号:

TQ 426.8

莫锦洪, 韩雪, 朱毅翔, 李菁, 王旭裕, 纪红兵. Pt-Ga/CeO₂-ZrO₂-Al₂O₃脱氢裂解双功能催化剂用于正丁烷催化制烯烃研究[J]. 化工学报, 2024, 75(5): 1855-1869.

Jinhong MO, Xue HAN, Yixiang ZHU, Jing LI, Xuyu WANG, Hongbing JI. Investigation of Pt-Ga/CeO₂-ZrO₂-Al₂O₃bifunctional catalyst for the catalytic conversion of n-butane into olefins[J]. CIESC Journal, 2024, 75(5): 1855-1869.

图/表 16

图1 催化剂反应活性评价装置

Fig.1 The catalyst reactivity evaluation apparatus

图2 CZA、Ga/CZA-7、Pt/CZA-0.5和PtGa/CZA-x-7催化剂的催化性能与反应温度的关系

Fig.2 Catalytic performance of CZA, Ga/CZA-7, Pt/CZA-0.5 and PtGa/CZA-x-7 catalysts as a function of reaction temperature

表1 Pt基催化剂在丁烷脱氢和裂解反应中的性能对比

Table 1 Comparison of the performance of Pt-based catalysts in butane dehydrogenation and cracking

文献	催化剂	Pt负载量（质量分数）/%	质量/g	反应温度/℃	质量空速/h^-1	转化率/%	烯烃选择性/%
[44]	ADDINPt-Sn/ZSM-5(300)	0.5	—	585	3.0	38.7	约90
[45]	Pt-0.1ZnO@ZSM-5	0.5	0.3	625	0.5	约100	75
[46]	ADDINPt/10TiO₂/ZSM-5	1.0	0.3	625	—	76.1	67
[32]	Pt-Sn/SAPO-34	0.5	—	585	2.8	36	约92
[47]	EG-2	0.8	0.1	500	54.3	约20	>97
[48]	Pd-Pt/Al	1.0	0.25	600	24.9	50	84
[31]	Pt/ND@G	1.0	—	450	24.0	约25	>95
[28]	PtSn/Sp-Zn-C	0.3	0.2	530	6.5	约28	约96
[49]	Pt/CNP	0.3	0.2	530	6.5	29	92
[50]	PtSn/CMgO-600	1.0	0.1	550	23.5	30.6	97.5
本文	PtGa/CZA-0.5-7	0.5	0.2	550	2.6	71.8	98.3

图3 CZA、Ga/CZA-7、Pt/CZA-0.5和PtGa/CZA-0.5-7催化剂的X射线衍射谱图和拉曼谱图

Fig.3 X-ray diffraction patterns and Raman spectra of CZA, Ga/CZA-7, Pt/CZA-0.5 and PtGa/CZA-0.5-7 catalysts

图4 CZA、Ga/CZA-7、Pt/CZA-0.5和PtGa/CZA-0.5-7催化剂的N2等温吸脱附曲线和孔径分布

Fig.4 Isothermal N2 adsorption and desorption curves and pore size distributions of CZA, Ga/CZA-7, Pt/CZA-0.5 and PtGa/CZA-0.5-7 catalysts

表2 催化剂的比表面积、孔体积和孔径的BET分析

Table 2 BET analysis of specific surface area， pore volume and pore size of catalysts

催化剂	比表面积/ （m²·g^-1）	孔体积/ （cm³·g^-1）	孔径/ nm
CZA	93.05	0.64	27.60
Ga/CZA-7	88.36	0.60	25.38
Pt/CZA-0.5	90.90	0.60	24.63
PtGa/CZA-0.5-7	90.04	0.57	23.51

图5 CZA、Ga/CZA-7、Pt/CZA-0.5和PtGa/CZA-0.5-7催化剂的微观形貌表征

Fig.5 Micro-morphological characterization of CZA, Ga/CZA-7, Pt/CZA-0.5 and PtGa/CZA-0.5-7 catalysts

图6 CZA、Ga/CZA-7、Pt/CZA-0.5和PtGa/CZA-0.5-7催化剂的红外光谱图

Fig.6 FT-IR spectra of CZA, Ga/CZA-7, Pt/CZA-0.5 and PtGa/CZA-0.5-7 catalysts

图7 CZA、Ga/CZA-7、Pt/CZA-0.5和PtGa/CZA-0.5-7催化剂的NH3-TPD谱图

Fig.7 NH3-TPD spectra of CZA, Ga/CZA-7, Pt/CZA-0.5 and PtGa/CZA-0.5-7 catalysts

图8 CZA、Ga/CZA-7、Pt/CZA-0.5和PtGa/CZA-0.5-7催化剂的H2-TPR谱图

Fig.8 H2-TPR spectra of CZA, Ga/CZA-7, Pt/CZA-0.5 and PtGa/CZA-0.5-7 catalysts

图9 CZA、Ga/CZA-7、Pt/CZA-0.5和PtGa/CZA-0.5-7催化剂的O2-TPD谱图

Fig.9 O2-TPD spectra of CZA, Ga/CZA-7, Pt/CZA-0.5 and PtGa/CZA-0.5-7 catalysts

图10 CZA、Ga/CZA-7、Pt/CZA-0.5和PtGa/CZA-0.5-7催化剂的XPS谱图

Fig.10 XPS spectra of CZA, Ga/CZA-7, Pt/CZA-0.5 and PtGa/CZA-0.5-7 catalysts

表3 CZA、Ga/CZA-7、Pt/CZA-0.5和PtGa/CZA-0.5-7样品的Ce 3d和O 1s数据

Table 3 Ce 3d and O 1s data for CZA， Ga/CZA-7， Pt/CZA-0.5 and PtGa/CZA-0.5-7 samples

催化剂	(Ce³⁺/(Ce³⁺+Ce⁴⁺))/%	(O_β/(O_α+O_β))/%
CZA	25.56	45.17
Ga/CZA-7	32.91	52.80
Pt/CZA-0.5	23.79	40.18
PtGa/CZA-0.5-7	26.44	46.10

表4 PtGa/CZA-x-7（x=0.1、0.5、0.9）在550℃的正丁烷催化裂解产物的摩尔比

Table 4 Molar ratios of n-butane catalytic cracking products with PtGa/CZA-x-7 （x=0.1， 0.5， 0.9） at 550℃

催化剂	H₂/C $4 =$	C₂H₆/C $2 =$	CH₄/C $3 =$
PtGa/CZA-0.1-7	2.1	0.2	0.7
PtGa/CZA-0.5-7	1.9	0.3	0.7
PtGa/CZA-0.9-7	2.0	0.4	0.7

表4 PtGa/CZA-x-7（x=0.1、0.5、0.9）在550℃的正丁烷催化裂解产物的摩尔比

Table 4 Molar ratios of n-butane catalytic cracking products with PtGa/CZA-x-7 （x=0.1， 0.5， 0.9） at 550℃

催化剂	H₂/C $4 =$	C₂H₆/C $2 =$	CH₄/C $3 =$
PtGa/CZA-0.1-7	2.1	0.2	0.7
PtGa/CZA-0.5-7	1.9	0.3	0.7
PtGa/CZA-0.9-7	2.0	0.4	0.7

图11 PtGa/CZA催化剂正丁烷催化裂解机理

Fig.11 Mechanism of catalytic cracking of n-butane over PtGa/CZA catalyst

图12 PtGa/CZA-Al和PtGa/CZA-0.5-7催化剂的正丁烷催化裂解性能与反应温度和反应时间的关系

Fig.12 n-Butane catalytic cracking performance of PtGa/CZA-Al and PtGa/CZA-0.5-7 catalysts as a function of reaction temperature and reaction time

参考文献 73

1	陆江银, 赵震, 徐春明. 碳四烷烃催化裂解制低碳烯烃的研究进展[J]. 现代化工, 2004, 24(8): 15-18.
	Lu J Y, Zhao Z, Xu C M. Advances in catalytic cracking butane for production of light olefins[J]. Modern Chemical Industry, 2004, 24(8): 15-18.
2	Rahimi N, Karimzadeh R. Kinetic modeling of catalytic cracking of C₄ alkanes over La/HZSM-5 catalysts in light olefin production[J]. Journal of Analytical and Applied Pyrolysis, 2015, 115: 242-254.
3	Cheung T K, Ditri J L, Gates B C. Cracking of n-butane catalyzed by iron- and manganese-promoted sulfated zirconia[J]. Journal of Catalysis, 1995, 153(2): 344-349.
4	Harding W D, Kung H H, Kozhevnikov V L, et al. Phase equilibria and butane oxidation studies of the MgO-V₂O₅-MoO₃ system[J]. Journal of Catalysis, 1993, 144(2): 597-610.
5	Lu J Y, Zhao Z, Xu C M, et al. FeHZSM-5 molecular sieves-highly active catalysts for catalytic cracking of isobutane to produce ethylene and propylene[J]. Catalysis Communications, 2006, 7(4): 199-203.
6	Lu J Y, Zhao Z, Xu C M, et al. Catalytic performance of bare supporters and supported KVO₃ catalysts for cracking n-butane to produce light olefins[J]. Petroleum science, 2005, 2(1): 52-56.
7	Kijima N, Matano K, Saito M, et al. Oxidative catalytic cracking of n-butane to lower alkenes over layered BiOCl catalyst[J]. Applied Catalysis A: General, 2001, 206(2): 237-244.
8	Eibl S, Jentoft R E, Gates B C, et al. Conversion of n-pentane and of n-butane catalyzed by platinum-containing WO _x /TiO₂ [J]. Physical Chemistry Chemical Physics, 2000, 2(11): 2565-2573.
9	Kijima N, Matano K, Saito M, et al. Oxidative cracking of n-butane over BiOCl catalyst[J]. Journal of the Japan Petroleum Institute, 2000, 43(1): 89-90.
10	Liu X B, Li W Z, Zhu H O, et al. Light alkenes preparation by the gas phase oxidative cracking or catalytic oxidative cracking of high hydrocarbons[J]. Catalysis Letters, 2004, 94(1): 31-36.
11	Hu X Y, Li C Y, Yang C H. Catalytic cracking of n-heptane over HZSM-5 catalysts with the activation of lattice oxygen[J]. Catalysis Today, 2010, 158(3/4): 504-509.
12	Wakui K, Satoh K, Sawada G, et al. Dehydrogenative cracking of n-butane using double-stage reaction[J]. Applied Catalysis A: General, 2002, 230(1/2): 195-202.
13	Maia A J, Oliveira B G, Esteves P M, et al. Isobutane and n-butane cracking on Ni-ZSM-5 catalyst: effect on light olefin formation[J]. Applied Catalysis A: General, 2011, 403(1/2): 58-64.
14	Lu J Y, Zhao Z, Xu C M, et al. CrHZSM-5 zeolites-highly efficient catalysts for catalytic cracking of isobutane to produce light olefins[J]. Catalysis Letters, 2006, 109(1): 65-70.
15	Han J, Jiang G Y, Han S L, et al. The fabrication of Ga₂O₃/ZSM-5 hollow fibers for efficient catalytic conversion of n-butane into light olefins and aromatics[J]. Catalysts, 2016, 6(1): 13.
16	张洁, 周明明, 李春义, 等. 异丁烷脱氢裂解制低碳烯烃[J]. 石油炼制与化工, 2013, 44(5): 14-18.
	Zhang J, Zhou M M, Li C Y, et al. Dehydrogenation cracking of i-butane to produce light olefins[J]. Petroleum Processing and Petrochemicals, 2013, 44(5): 14-18.
17	Agula B, Dalai S Q. Mesoporous Ce _x Zr_1- _x O₂ mixed oxides supported Cr-V-O nanocatalysts for dehydrogenation of propane to propene[J]. Advanced Materials Research, 2015, 1096: 509-513.
18	Narasimharao K, Ali T T. Catalytic oxidative cracking of propane over nanosized gold supported Ce_0.5Zr_0.5O₂ catalysts[J]. Catalysis Letters, 2013, 143(10): 1074-1084.
19	Raju G, Reddy B M, Park S E. CO₂ promoted oxidative dehydrogenation of n-butane over VO _x /MO₂-ZrO₂ (M=Ce or Ti) catalysts[J]. Journal of CO₂ Utilization, 2014, 5: 41-46.
20	He Z H, Wu B T, Xia Y, et al. CO₂ oxidative dehydrogenation of n-butane to butadiene over CrO _x supported on CeZr solid solution[J]. Molecular Catalysis, 2022, 524: 112262.
21	Ajumobi O O, Muraza O, Bakare I A, et al. Iron- and cobalt-doped ceria-zirconia nanocomposites for catalytic cracking of naphtha with regenerative capability[J]. Energy & Fuels, 2017, 31(11): 12612-12623.
22	Dejhosseini M, Aida T, Watanabe M, et al. Catalytic cracking reaction of heavy oil in the presence of cerium oxide nanoparticles in supercritical water[J]. Energy & Fuels, 2013, 27(8): 4624-4631.
23	Trovarelli A. Catalytic properties of ceria and CeO₂-containing materials[J]. Catalysis Reviews, 1996, 38(4): 439-520.
24	Choudhary V R, Rane V H. Acidity/basicity of rare-earth oxides and their catalytic activity in oxidative coupling of methane to C₂-hydrocarbons[J]. Journal of Catalysis, 1991, 130(2): 411-422.
25	Liu Y, Zhang G H, Liu S D, et al. Promoting n-butane dehydrogenation over PtMn/SiO₂ through structural evolution induced by a reverse water-gas shift reaction[J]. ACS Catalysis, 2022, 12(21): 13506-13512.
26	Qi L, Zhang Y F, Babucci M, et al. Dehydrogenation of propane and n-butane catalyzed by isolated PtZn₄ sites supported on self-pillared zeolite pentasil nanosheets[J]. ACS Catalysis, 2022, 12(18): 11177-11189.
27	Ballarini A D, Zgolicz P, Vilella I M J, et al. n-Butane dehydrogenation on Pt, PtSn and PtGe supported on γ-Al₂O₃ deposited on spheres of α-Al₂O₃ by washcoating[J]. Applied Catalysis A: General, 2010, 381(1/2): 83-91.
28	de Miguel S, Ballarini A, Bocanegra S. New PtSn structured catalysts with ZnAl₂O₄ thin film for n-butane dehydrogenation reaction[J]. Applied Catalysis A: General, 2020, 590: 117315.
29	Deng L D, Miura H, Ohkubo T, et al. The importance of direct reduction in the synthesis of highly active Pt-Sn/SBA-15 for n-butane dehydrogenation[J]. Catalysis Science & Technology, 2019, 9(4): 947-956.
30	Nagaraja B M, Jung H, Yang D R, et al. Effect of potassium addition on bimetallic PtSn supported θ-Al₂O₃ catalyst for n-butane dehydrogenation to olefins[J]. Catalysis Today, 2014, 232: 40-52.
31	Zhang J Y, Cai X B, Wu K H, et al. Nanodiamond-core-reinforced, graphene-shell-immobilized platinum nanoparticles as a highly active catalyst for the low-temperature dehydrogenation of n-butane[J]. ChemCatChem, 2018, 10(3): 520-524.
32	Nawaz Z, Fei W. Pt-Sn-based SAPO-34 supported novel catalyst for n-butane dehydrogenation[J]. Industrial & Engineering Chemistry Research, 2009, 48(15): 7442-7447.
33	Bocanegra S A, de Miguel S R, Borbath I, et al. Behavior of bimetallic PtSn/Al₂O₃ catalysts prepared by controlled surface reactions in the selective dehydrogenation of butane[J]. Journal of Molecular Catalysis A: Chemical, 2009, 301(1/2): 52-60.
34	Chen X W, Peng M, Cai X B, et al. Regulating coordination number in atomically dispersed Pt species on defect-rich graphene for n-butane dehydrogenation reaction[J]. Nature Communications, 2021, 12(1): 2664.
35	Zhang B F, Zheng L R, Zhai Z W, et al. Subsurface-regulated PtGa nanoparticles confined in silicalite-1 for propane dehydrogenation[J]. ACS Applied Materials & Interfaces, 2021, 13(14): 16259-16266.
36	Kwon H C, Park Y, Park J Y, et al. Catalytic interplay of Ga, Pt, and Ce on the alumina surface enabling high activity, selectivity, and stability in propane dehydrogenation[J]. ACS Catalysis, 2021, 11(17): 10767-10777.
37	Wang T, Jiang F, Liu G, et al. Effects of Ga doping on Pt/CeO₂-Al₂O₃ catalysts for propane dehydrogenation[J]. AIChE Journal, 2016, 62(12): 4365-4376.
38	Chang Q Y, Wang K Q, Hu P, et al. Dual-function catalysis in propane dehydrogenation over Pt₁-Ga₂O₃ catalyst: insights from a microkinetic analysis[J]. AIChE Journal, 2020, 66(7): e16232.
39	Sattler J J H B, Gonzalez-Jimenez I D, Luo L, et al. Platinum-promoted Ga/Al₂O₃ as highly active, selective, and stable catalyst for the dehydrogenation of propane[J]. Angewandte Chemie International Edition, 2014, 53(35): 9251-9256.
40	Payard P A, Rochlitz L, Searles K, et al. Dynamics and site isolation: keys to high propane dehydrogenation performance of silica-supported PtGa nanoparticles[J]. JACS Au, 2021, 1(9): 1445-1458.
41	Wang Y S, Suo Y J, Lv X W, et al. Enhanced performances of bimetallic Ga-Pt nanoclusters confined within silicalite-1 zeolite in propane dehydrogenation[J]. Journal of Colloid and Interface Science, 2021, 593: 304-314.
42	Collins S, Finos G, Alcántara R, et al. Effect of gallia doping on the acid-base and redox properties of ceria[J]. Applied Catalysis A: General, 2010, 388(1/2): 202-210.
43	Vecchietti J, Collins S, Xu W Q, et al. Surface reduction mechanism of cerium-gallium mixed oxides with enhanced redox properties[J]. The Journal of Physical Chemistry C, 2013, 117(17): 8822-8831.
44	Nawaz Z, Qing S, Gao J X, et al. Effect of Si/Al ratio on performance of Pt-Sn-based catalyst supported on ZSM-5 zeolite for n-butane conversion to light olefins[J]. Journal of Industrial and Engineering Chemistry, 2010, 16(1): 57-62.
45	Zhang H D, Wu C Y, Wang J L, et al. ZSM-5 zeolite-encapsulated Pt-ZnO bimetallic catalysts for the catalytic cracking of iso-butane[J]. Industrial & Engineering Chemistry Research, 2024, 63(1): 833-842.
46	刘佳, 姜桂元, 赵震,等. Pt/TiO₂/ZSM-5催化剂的制备及其催化转化正丁烷[J]. 化工学报, 2016, 67(8): 3363-3373.
	Liu J, Jiang G Y, Zhao Z, et al. Preparation of Pt/TiO₂/ZSM-5 catalyst for catalytic conversion of n-butane[J]. CIESC Journal, 2016, 67(8): 3363-3373.
47	Shao M Y, Hu C Q, Xu X B, et al. Pt/TS-1 catalysts: effect of the platinum loading method on the dehydrogenation of n-butane[J]. Applied Catalysis A: General, 2021, 621: 118194.
48	Saxena R, De M. Enhanced performance of supported Pd-Pt bimetallic catalysts prepared by modified electroless deposition for butane dehydrogenation[J]. Applied Catalysis A: General, 2021, 610: 117933.
49	Ballarini A, Bocanegra S, Mendez J, et al. Application of novel catalysts supported on carbonaceous materials in the direct non-oxidative dehydrogenation of n-butane to olefins[J]. Inorganic Chemistry Communications, 2022, 142: 109638.
50	Shashikala V, Jung H, Shin C, et al. n-Butane dehydrogenation on PtSn/carbon modified MgO catalysts[J]. Catalysis Letters, 2013, 143(7): 651-656.
51	Morikawa A, Suzuki T, Kanazawa T, et al. A new concept in high performance ceria-zirconia oxygen storage capacity material with Al₂O₃ as a diffusion barrier[J]. Applied Catalysis B: Environmental, 2008, 78(3/4): 210-221.
52	Osaki T. Activity-determining factors for catalytic CO and CH₄ oxidation on Pt/CeO₂-ZrO₂-Al₂O₃ cryogels[J]. Research on Chemical Intermediates, 2020, 46(6): 3125-3143.
53	Andonova S, Ok Z A, Drenchev N, et al. Pt/CeO _x /ZrO _x /γ-Al₂O₃ ternary mixed oxide deNO _x catalyst: surface chemistry and NO _x interactions[J]. The Journal of Physical Chemistry C, 2018, 122(24): 12850-12863.
54	Li S S, He J S, Dan Y, et al. Bifunctional roles of Nd₂O₃ on improving the redox property of CeO₂-ZrO₂-Al₂O₃ materials[J]. Materials Chemistry and Physics, 2020, 240: 122150.
55	Chen K, Wan J, Lin J S, et al. Comparative study of three-way catalytic performance over Pd/CeO₂-ZrO₂-Al₂O₃ and Pd/La-Al₂O₃ catalysts: new insights into microstructure and thermal stability[J]. Molecular Catalysis, 2022, 526: 112361.
56	Usharani S, Rajendran V. Synthesis and characterization of surfactant assisted CeO₂/ZrO₂ nanocomposite[J]. International Journal of Pure and Applied Physics, 2016, 12(1): 53-60.
57	Ibrahim M M, El-Molla S A, Ismail S A. Influence of γ and ultrasonic irradiations on the physicochemical properties of CeO₂-Fe₂O₃-Al₂O₃ for textile dyes removal applications[J]. Journal of Molecular Structure, 2018, 1158: 234-244.
58	Ibrahim M M. An efficient nano-adsorbent via surfactants/dual surfactants assisted ultrasonic co-precipitation method for sono-removal of monoazo and diazo anionic dyes[J]. Chinese Journal of Chemical Engineering, 2021, 40: 225-236.
59	Panahi-Kalamuei M, Alizadeh S, Mousavi-Kamazani M, et al. Synthesis and characterization of CeO₂ nanoparticles via hydrothermal route[J]. Journal of Industrial and Engineering Chemistry, 2015, 21: 1301-1305.
60	Zhao Q, Wang Y, Li G Y, et al. CeZrO _x promoted water-gas shift reaction under steam-methane reforming conditions on Ni-HTASO5[J]. Catalysts, 2020, 10(10): 1110.
61	Wang Z Y, He Z H, Xia Y, et al. Oxidative dehydrogenation of propane to propylene in the presence of CO₂ over gallium nitride supported on NaZSM-5[J]. Industrial & Engineering Chemistry Research, 2021, 60(7): 2807-2817.
62	Wang G W, Zhu X L, Li C Y. Recent progress in commercial and novel catalysts for catalytic dehydrogenation of light alkanes[J]. The Chemical Record, 2020, 20(6): 604-616.
63	Deng J, Zhou Y, Cui Y J, et al. The influence of H₂O₂ on the properties of CeO₂-ZrO₂ mixed oxides[J]. Journal of Materials Science, 2017, 52(9): 5242-5255.
64	Wang J Q, Shen M Q, Wang J, et al. Effect of cobalt doping on ceria-zirconia mixed oxide: structural characteristics, oxygen storage/release capacity and three-way catalytic performance[J]. Journal of Rare Earths, 2012, 30(9): 878-883.
65	Quaino P, Syzgantseva O, Siffert L, et al. Unravelling the enhanced reactivity of bulk CeO₂ doped with gallium: a periodic DFT study[J]. Chemical Physics Letters, 2012, 519/520: 69-72.
66	Tan W, Xie S H, Wang X, et al. Highly efficient Pt catalyst on newly designed CeO₂-ZrO₂-Al₂O₃ support for catalytic removal of pollutants from vehicle exhaust[J]. Chemical Engineering Journal, 2021, 426: 131855.
67	Deng C S, Li B, Dong L H, et al. NO reduction by CO over CuO supported on CeO₂-doped TiO₂: the effect of the amount of a few CeO₂ [J]. Physical Chemistry Chemical Physics, 2015, 17(24): 16092-16109.
68	Sellick D R, Aranda A, García T, et al. Influence of the preparation method on the activity of ceria zirconia mixed oxides for naphthalene total oxidation[J]. Applied Catalysis B: Environmental, 2013, 132/133: 98-106.
69	Li S S, Wang W, Zhao Y, et al. Correlation between the morphology of NH₄Al(OH)₂CO₃ and the properties of CeO₂-ZrO₂/Al₂O₃ material[J]. Materials Chemistry and Physics, 2021, 266: 124552.
70	Zhou S L, Gao L Y, Wei F F, et al. On the mechanism of alkyne hydrogenation catalyzed by Ga-doped ceria[J]. Journal of Catalysis, 2019, 375: 410-418.
71	Kunwar D, Zhou S L, DeLaRiva A, et al. Stabilizing high metal loadings of thermally stable platinum single atoms on an industrial catalyst support[J]. ACS catalysis, 2019, 9(5): 3978-3990.
72	Krannila H, Haag W O, Gates B C. Monomolecular and bimolecular mechanisms of paraffin cracking: n-butane cracking catalyzed by HZSM-5[J]. Journal of Catalysis, 1992, 135(1): 115-124.
73	张执刚.反应压力对催化裂解工艺的影响及反应机理研究[J].炼油技术与工程,2010, 40(3): 6-9.
	Zhang J G. Impact of reaction pressure on deep catalytic cracking process and research of reaction mechanisms[J]. Petroleum Refinery Engineering, 2010, 40(3): 6-9.

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Pt-Ga/CeO₂-ZrO₂-Al₂O₃脱氢裂解双功能催化剂用于正丁烷催化制烯烃研究

Investigation of Pt-Ga/CeO₂-ZrO₂-Al₂O₃bifunctional catalyst for the catalytic conversion of n-butane into olefins

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