Sn引入方式对Al2O3负载Pt基催化剂丙烷脱氢性能的影响

doi:10.12422/j.issn.1006-396X.2024.04.007

摘要/Abstract

摘要：

Sn助剂可有效提高丙烷脱氢Pt基催化剂的丙烯选择性并抑制积碳的产生，但是Sn的助剂效应尚不明晰。采用共浸渍法和溶胶凝胶法调变Sn的引入方式，构建不同PtSn作用体系，并系统地探究了Sn引入方式对Pt基催化剂丙烷脱氢反应性能的影响；采用XRD、BET对催化剂的织构性质进行表征，通过H₂?TPR、TEM、CO?IR对助剂Sn的结构进行辨析，并对催化剂进行了丙烷脱氢反应性能评价与积碳分析。结果表明，相较于共浸渍法制备的PtSn/γ?Al₂O₃，溶胶凝胶法制备的Pt/Sn?γ?Al₂O₃具有较低的比表面积和较大的孔径，可促进PtSn团簇与载体间的相互作用，实现金属的高分散度；Pt/Sn?γ?Al₂O₃有较多的活性位，因此丙烷转化率和丙烯收率较高，同时载体的大孔径也使催化剂的积碳量显著降低。

关键词: 助剂Sn, 引入方式, 丙烯, PtSn催化剂

Abstract:

Sn additives can effectively improve the propylene selectivity of propane dehydrogenated Pt?based catalysts and inhibit the generation of carbon deposition,but the effect of Sn additives is still unclear.Therefore,in this paper,different PtSn action systems were constructed by co?impregnation method and sol?gel method to modulate the introduction of PtSn,and the effect of Sn introduction methods on the dehydrogenation performance of propane of Pt?based catalysts was systematically explored.XRD and BET were used to characterize the texture properties of the catalyst,H₂?TPR,TEM and CO?IR were used to distinguish the Sn structure of the additives,and the propane dehydrogenation reaction evaluation and carbon deposition analysis of the catalysts were carried out.The results show that compared with the PtSn/γ?Al₂O₃ catalyst prepared by co?impregnation method,the Pt/Sn?γ?Al₂O₃ catalyst prepared by sol?gel method has a lower specific surface area and higher pore size,which can promote the interaction between PtSn clusters and carriers to achieve high metal dispersion.More active sites give the Pt/Sn?γ?Al₂O₃ catalyst higher propane conversion and propylene yield,and the larger pore size of the carrier also significantly reduces the carbon deposition of the catalyst.

Key words: Additive Sn, Introduction methods, Propylene, PtSn catalyst

中图分类号:

TQ221

韩飞飞, 焦建豪, 田祥臣, 杨野, 秦玉才, 宋丽娟. Sn引入方式对Al₂O₃负载Pt基催化剂丙烷脱氢性能的影响[J]. 石油化工高等学校学报, 2024, 37(4): 49-56.

Feifei HAN, Jianhao JIAO, Xiangchen TIAN, Ye YANG, Yucai QIN, Lijuan SONG. Effect of Sn Introduction on the Dehydrogenation Performance of Propane of Al₂O₃⁃Supported Pt⁃Based Catalysts[J]. Journal of Petrochemical Universities, 2024, 37(4): 49-56.

图/表 9

图1 Sn?γ?Al2O3、Sn/γ?Al2O3、Pt/Sn?γ?Al2O3和PtSn/γ?Al2O3的XRD谱图

Fig.1 XRD patterns of Sn?γ?Al2O3,Sn/γ?Al2O3,Pt/Sn?γ?Al2O3 and PtSn/γ?Al2O3

图2 Sn?γ?Al2O3、Sn/γ?Al2O3、Pt/Sn?γ?Al2O3和PtSn/γ?Al2O3的N2吸附?脱附曲线和孔径分布曲线

Fig.2 N2 adsorption?desorption curves and pore size curves of Sn?γ?Al2O3, Sn/γ?Al2O3, Pt/Sn?γ?Al2O3 and PtSn/γ?Al2O3

表1 Sn?γ?Al2O3、Sn/γ?Al2O3、Pt/Sn?γ?Al2O3和PtSn/γ?Al2O3的织构性质

Table 1 Texture properties of Sn?γ?Al2O3,Sn/γ?Al2O3,Pt/Sn?γ?Al2O3 and PtSn/γ?Al2O3

催化剂	比表面积/(m²·g^-1)	孔体积/(cm³·g^-1)	孔径/nm
Pt/Sn⁃γ⁃Al₂O₃	152.83	0.44	9.30
PtSn/γ⁃Al₂O₃	208.19	0.47	6.71
Sn⁃γ⁃Al₂O₃	152.97	0.43	9.01
Sn/γ⁃Al₂O₃	204.91	0.46	6.73

图3 Sn?γ?Al2O3、Sn/γ?Al2O3、Pt/Sn?γ?Al2O3和PtSn/γ?Al2O3的H2?TPR曲线

Fig.3 H2?TPR of Sn?γ?Al2O3,Sn/γ?Al2O3,Pt/Sn?γ?Al2O3 and PtSn/γ?Al2O3

图4 还原后的Pt/Sn?γ?Al2O3和PtSn/γ?Al2O3的TEM（a） Pt/Sn?γ?Al2O3 （b） PtSn/γ?Al2O3

Fig.4 TEM of reduced Pt/Sn?γ?Al2O3 and PtSn/γ?Al2O3

图5 还原后的Pt/Sn?γ?Al2O3和PtSn/γ?Al2O3的活性金属粒径分布

Fig.5 Active metal particle size distribution of reduced Pt/Sn?γ?Al2O3 and PtSn/γ?Al2O3

图6 Pt/Sn?γ?Al2O3和PtSn/γ?Al2O3的CO吸附红外谱图注：S峰1、S峰2分别为峰1、峰2吸收峰面积；绿色曲线代表分峰拟合曲线。

Fig.6 FTIR spectra of CO adsorption on the Pt/Sn?γ?Al2O3 and PtSn/γ?Al2O3

图7 Pt/Sn?γ?Al2O3和PtSn/γ?Al2O3的丙烷转化率、丙烯选择性和丙烯收率

Fig.7 Propane conversion and propene selectivity and propylene yield of Pt/Sn?γ?Al2O3 and PtSn/γ?Al2O3

图8 Pt/Sn?γ?Al2O3和PtSn/γ?Al2O3的TG和DTG曲线

Fig.8 TG and DTG curves of Pt/Sn?γ?Al2O3 and PtSn/γ?Al2O3 catalysts

参考文献 28

1	SHENG J，YAN B，LU W D，et al.Oxidative dehydrogenation of light alkanes to olefins on metal⁃free catalysts［J］.Chemical Society Reviews，2021，50（2）：1438⁃1468.
2	FENG B H，WEI Y C，SONG W Y，et al.A review on the structure⁃performance relationship of the catalysts during propane dehydrogenation reaction［J］.Petroleum Science，2022，19（2）：819⁃838.
3	CHEN S，CHANG X，SUN G D，et al.Propane dehydrogenation：Catalyst development，new chemistry，and emerging technologies［J］.Chemical Society Reviews，2021，50（5）：3315⁃3354.
4	张晓斌，李文宏，张英，等.油田用烯烃磺酸盐液相色谱‐质谱检测法［J］.油田化学，2022，39（1）：150⁃154.
	ZHANG X B，LI W H，ZHANG Y，et al.Detection method of olefin sulfonate used in oilfield by liquid chromatography‐mass spectrometry［J］.Oilfield Chemistry，2022，39（1）：150⁃154.
5	ZHANG H J，WAN H，ZHAO Y，et al.Effect of chlorine elimination from Pt⁃Sn catalyst on the behavior of hydrocarbon reconstruction in propane dehydrogenation［J］.Catalysis Today，2019，330：85⁃91.
6	KAYLOR N，DAVIS R J.Propane dehydrogenation over supported Pt⁃Sn nanoparticles［J］.Journal of Catalysis，2018，367：181⁃193.
7	LIAN Z，SI C W，JAN F，et al.Coke deposition on Pt⁃based catalysts in propane direct dehydrogenation：Kinetics，suppression，and elimination［J］.ACS Catalysis，2021，11（15）：9279⁃9292.
8	WALTER J P，BRUNE A，SEIDEL⁃MORGENSTERN A，et al.Process intensification of the propane dehydrogenation considering coke formation，catalyst deactivation and regeneration⁃transient modelling and analysis of a heat⁃integrated membrane reactor［J］.Catalysts，2021，11（9）：1056.
9	SATTLER J J H B，BEALE A M，WECKHUYSEN B M.Operando raman spectroscopy study on the deactivation of Pt/Al₂O₃ and Pt⁃Sn/Al₂O₃ propane dehydrogenation catalysts［J］.Physical Chemistry Chemical Physics，2013，15（29）：12095⁃12103.
10	康津铭，焦建豪，秦玉才，等.Pt_0.5‐Snx/γ‐Al₂O₃催化剂对丙烷脱氢反应性能的影响［J］.石油化工高等学校学报，2023，36（4）：34⁃39.
	KANG J M，JIAO J H，QIN Y C，et al.Effect of Pt_0.5‐Snx/γ‐Al₂O₃ catalysts on the performance of propane dehydrogenation［J］.Journal of Petrochemical Universities，2023，36（4）：34⁃39.
11	PAÁL Z，WOOTSCH A，TESCHNER D，et al.Structural properties of an unsupported model Pt⁃Sn catalyst and its catalytic properties in cyclohexene transformation［J］.Applied Catalysis A：General，2011，391（1⁃2）：377⁃385.
12	GAO X F，XU W H，LI X，et al.Non⁃oxidative dehydrogenation of propane to propene over Pt⁃Sn/Al₂O₃ catalysts：Identification of the nature of active site［J］.Chemical Engineering Journal，2022，443：136393.
13	SHABANI S，MIRKAZEMI S M，REZAIE H，et al.A comparative study on the thermal stability，textural，and structural properties of mesostructured γ⁃Al₂O₃ granules in the presence of La，Sn，and B additives［J］.Ceramics International，2022，48（5）：6638⁃6648.
14	DENG L，HAN S，LI Y，et al.Subnanometric Pt⁃Sn monolayers over a rod‐shaped Al₂O₃ for propane dehydrogenation［J］.ChemCatChem，2022，14（15）：e202200400.
15	刘雪平，徐晋春，史楷文，等.超声法制备负载Cu⁃Fe分子筛催化剂及其催化氧化甲苯性能研究［J］.低碳化学与化工，2023，48（4）：69⁃76.
	LIU X P，XU J C，SHI K W，et al.Preparation of Cu⁃Fe loaded molecular sieve catalyst by ultrasonication and its catalytical oxidation performance for toluene［J］.Low⁃Carbon Chemistry and Chemical Engineering，2023，48（4）：69⁃76.
16	CLAUSER A L，SARFO K O，GIULIAN R，et al.Characterization of the atomic⁃level structure of γ⁃alumina and （111） Pt/γ⁃alumina interfaces［J］.Acta Materialia，2023，245：118609.
17	MARDWITA M，YUSMARTINI E S，WISUDAWATI N.Effects of cobalt and chromium loadings to the catalytic activities of supported metal catalysts in methane oxidation［J］.Bulletin of Chemical Reaction Engineering & Catalysis，2020，15（1）：213⁃220.
18	闫翔云，马波，季洪海，等.焙烧温度对氧化铝物化性质及微观结构的影响［J］.当代化工，2011，40（3）：248⁃251.
	YAN X Y，MA B，JI H H，et al.Effect of calcination temperature on physical and chemical properties and microstructure of alumina［J］.Contemporary Chemical Industry，2011，40（3）：248⁃251.
19	彭淑静，杜慧玲.脉冲电磁场作用下Ce改性γ⁃Al₂O₃载体的热稳定性［J］.石油炼制与化工，2014（3）：18⁃21.
	PENG S J，DU H L.Thermal stability of Ce modified γ⁃Al₂O₃ support under pulsed electromagnetic field［J］.Petroleum Processing and Petrochemicals，2014（3）：18⁃21.
20	SHARMA L，BALTRUS J P，RANGARAJAN S，et al.Elucidating the underlying surface chemistry of Sn/Al₂O₃ catalysts during the propane dehydrogenation in the presence of H₂S co⁃feed［J］.Applied Surface Science，2022，573：151205.
21	ZHANG Y W，ZHOU Y M，LIU H，et al.Effect of La addition on catalytic performance of PtSnNa/ZSM⁃5 catalyst for propane dehydrogenation［J］.Applied Catalysis A：General，2007，333（2）：202⁃210.
22	SHI J J，ZHOU Y M，ZHANG Y W，et al.Synthesis of magnesium⁃modified mesoporous Al₂O₃ with enhanced catalytic performance for propane dehydrogenation［J］.Journal of Materials Science，2014，49（16）：5772⁃5781.
23	KIKUCHI I，OHSHIMA M，KUROKAWA H，et al.Effect of Sn addition on n⁃butane dehydrogenation over alumina⁃supported Pt catalysts prepared by co⁃impregnation and sol⁃gel methods［J］.Journal of the Japan Petroleum Institute，2012，55（3）：206⁃213.
24	SHI L，DENG G M，LI W C，et al.Al₂O₃ nanosheets rich in pentacoordinate Al³⁺ ions stabilize Pt⁃Sn clusters for propane dehydrogenation［J］.Angewandte Chemie International Edition，2015，54（47）：13994⁃13998.
25	DONG C Y，LI Y L，CHENG D Y，et al.Supported metal clusters：Fabrication and application in heterogeneous catalysis［J］.ACS Catalysis，2020，10（19）：11011⁃11045.
26	ZHANG Y W，ZHOU Y M，SHI J J，et al.Propane dehydrogenation over PtSnNa/La⁃doped Al₂O₃ catalyst：Effect of La content［J］.Fuel Processing Technology，2013，111：94⁃104.
27	张向月，万海，高塬，等.丙烯对丙烷脱氢催化剂PtSnK/Al₂O₃炭沉积行为的影响［J］.燃料化学学报，2022，50（7）：841⁃848.
	ZHANG X Y，WAN H，GAO Y，et al.Effect of propylene in feedstock on the coking behavior of PtSnK/Al₂O₃ catalyst of propane dehydrogenation［J］.Journal of Fuel Chemistry and Technology，2022，50（7）：841⁃848.
28	KHANMOHAMMADI S，TAHERI⁃NASSAJ E，FARROKHI⁃RAD M.Synthesis of meso⁃porous gamma⁃alumina membrane：Effect of yttria addition on the thermal stability［J］.Surfaces and Interfaces，2020，21：100683.

[1]	杨健松, 付强, 于龙娇, 王婷, 魏奇, 李伟, 王世伟. 橡胶改性丙烯酸酯压敏胶的研究进展[J]. 石油化工高等学校学报, 2023, 36(1): 8-15.
[2]	率为举，石彩静，王欣，陈平，安会勇. 丙烯酰胺类阳离子表面活性单体的合成及研究[J]. 石油化工高等学校学报, 2020, 33(2): 47-52.
[3]	李凤艳，胡月，赵劲，赵天波. 交联改性提高水性含氟丙烯酸树脂力学性能[J]. 石油化工高等学校学报, 2020, 33(2): 42-46.
[4]	胡荣荣，李凤艳，张世杰，赵天波. 聚甲聚甲基丙烯酸甲酯/石蜡微胶囊的制备与性能基丙烯酸甲酯/石蜡微胶囊的制备与性能[J]. 石油化工高等学校学报, 2019, 32(3): 14-19.
[5]	赵昆，孙树芝，周圣昊，谢文超，常亮，陈铁，陈文怡. 长庆联合站间管线添加防蜡剂后的蜡沉积特性[J]. 石油化工高等学校学报, 2019, 32(1): 73-78.
[6]	孙鹏飞,王阳,张欢,曹景强,许军. 丙烯酰胺在乙醇/水介质中的RAFT分散聚合[J]. 石油化工高等学校学报, 2018, 31(04): 7-12.
[7]	王婷婷,曹伟佳,卢祥国. 半互穿网络结构凝胶黏度及其影响因素[J]. 石油化工高等学校学报, 2016, 29(5): 70-76.
[8]	朱洲, 战国华, 张斌, 赵健. 氧化石墨烯对 HP AM 溶液黏度行为的影响[J]. 石油化工高等学校学报, 2015, 28(4): 31-34.
[9]	杨海林, 张云宝, 刘文辉, 林梅钦. 盐质量浓度对交联聚丙烯酰胺微球性能的影响[J]. 石油化工高等学校学报, 2014, 27(2): 46-50.
[10]	艾抚宾,乔凯,方向晨,祁文博,徐彤. 液化气加氢热力学的研究[J]. 石油化工高等学校学报, 2013, 26(1): 29-32.
[11]	关越,孙万付,张志智,孙潇磊,张喜文. CO₂和乙烯合成丙烯酸反应的热力学分析[J]. 石油化工高等学校学报, 2012, 25(3): 6-12.
[12]	崔文峰,王海燕,张援越. 热分级技术在BOPP专用料评价中的应用[J]. 石油化工高等学校学报, 2011, 24(6): 39-41.
[13]	李辉,李宇剑. 黄原胶/AMPS/膨润土制备油田堵水剂的研究[J]. 石油化工高等学校学报, 2011, 24(6): 42-45.
[14]	董宾,秦玉才,丁勇,段林海. 丙烯环氧化反应组分在TS-1中吸附扩散行为研究[J]. 石油化工高等学校学报, 2011, 24(4): 17-20.
[15]	李琪,乔庆东. 复合凝胶聚合物电解质的制备及电化学性能[J]. 石油化工高等学校学报, 2011, 24(3): 27-30.

Sn引入方式对Al₂O₃负载Pt基催化剂丙烷脱氢性能的影响

Effect of Sn Introduction on the Dehydrogenation Performance of Propane of Al₂O₃⁃Supported Pt⁃Based Catalysts

HTML

PDF

可视化

摘要/Abstract

引用本文

使用本文

图/表 9

参考文献 28

相关文章 15

编辑推荐

Metrics