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

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烧掉，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也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→C₄⁼），CZA作为酸位点进行裂解反应（C₄⁼→C₃⁼，C₂⁼），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°C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, 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 using a stepwise method to prepare the PtGa/CZA catalyst. Pt-Ga₂O₃ was introduced as a dehydrogenation catalyst for the conversion of C₄H₁₀ to C₄⁼, while CZA functions as an acid catalyst for the cracking reactions leading to C₄⁼→C₃⁼ and C₂⁼. 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°C, 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 lower Ce⁴⁺ reduction and surface adsorbed oxygen desorption temperatures, higher surface adsorbed oxygen site content, and strong acidic site content.

Key words: alkane, catalytic cracking, platinum-gallium, catalyst, 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, DOI: 10.11949/0438-1157.20231384.

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, DOI: 10.11949/0438-1157.20231384.

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	反应温度	质量空速	转化率	烯烃选择性
文献	催化剂	/%	/g	/°C	/h	/%	/%
[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
	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 spectra 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）
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

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

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

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

催化剂	H₂/C₄⁼	C₂H₆/C₂⁼	CH₄/C₃⁼
PtGa/CZA-0.1-7	2.1	0.2	0.7
PtGa/CZA-0.5-7	1.9	0.3	0.7
GaPt/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

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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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