添加Sm对Pt /SBA-15催化苯完全氧化反应活性和热稳定性的影响

doi:10.11949/0438-1157.20191258

摘要/Abstract

摘要：

以Pt/SBA-15为催化剂，考察催化剂载体中添加Sm对于苯的完全氧化反应活性和热稳定性影响。采用了一种简便的记录起燃温度曲线和催化剂热稳定性评价方法，即向装载好催化剂的固定床反应器中持续通入恒定流量的反应气，逐步阶段性升高反应温度，同时在线检测出口尾气的浓度变化, 得到起燃温度曲线后，继续提高反应温度，然后恒定在某一设定的温度(如550℃)持续运行较长时间, 期间定时在线取样分析，如果有必要还可以连续考察降温情况下催化剂的反应活性情况。研究结果表明，几种催化剂低温活性次序为：Pt/SBA-15≈Pt/4%Sm₂O₃/SBA-15> Pt/Sm₂O₃> 4%Sm₂O₃/SBA-15,而对于高温稳定性则是Pt/4%Sm₂O₃/SBA-15> Pt/1.2%Sm₂O₃/SBA-15> Pt/SBA-15，Pt/Sm-SBA-15(SG)> Pt/SBA-15(SG)。总之，Sm的添加虽然未能提高Pt/SBA-15的低温催化活性，但是能明显提高催化剂在高温情况下活性的稳定性。1%Pt/4%Sm₂O₃/SBA-15同时具备较好的低温催化活性和高温稳定性，具有较好的应用前景。

关键词: Sm₂O₃, Pt/SBA-15, 苯, 催化, 完全氧化, 热稳定性

Abstract:

The Sm addition effects on the reactivity and thermal stability of Pt/SBA-15 for catalytic complete oxidation of benzene were investigated. A simple method for recording the burning-off curves and the evaluation for the thermal stability of catalysts was adopted, that is, a constant flow of reaction gas was continuously introduced into a fixed bed reactor loaded with catalyst. The reaction temperature was increased step by step, and the on-line outlet concentrations of benzene were detected after time interval sampling. The burning-off curves could be recorded during this stage. After that, the reaction temperature was increased continuously, and kept at a certain value (e.g. 550℃), the on-line sampling analysis was kept at a set time. If necessary, the reaction temperature could be decreased step by step to check the activity variation of the catalyst. The results indicated that the activity order for four catalysts at lower temperature stage was Pt/SBA-15≈Pt/4%Sm₂O₃/SBA-15> Pt/Sm₂O₃> 4%Sm₂O₃/SBA-15, while the stability order at high temperature was Pt/4%Sm₂O₃/SBA-15> Pt/1.2%Sm₂O₃/SBA-15> Pt/SBA-15，Pt/Sm-SBA-15(SG)> Pt/SBA-15(SG). In conclusion, Sm can not improve the catalytic activity of Pt / SBA-15 at low temperature, but can significantly improve the stability of the catalyst at high temperature. At the same time, 1% Pt/4% Sm₂O₃ / SBA-15 has good catalytic activity at low temperature and high temperature stability, and has a good application prospect.

Key words: Sm₂O₃, Pt/SBA-15, benzene, catalysis, complete oxidation, thermal stability

中图分类号:

TQ 426

毛建新, 袁子卿, 严红绡, 周仁贤. 添加Sm对Pt /SBA-15催化苯完全氧化反应活性和热稳定性的影响[J]. 化工学报, 2020, 71(1): 306-313.

Jianxin MAO, Ziqing YUAN, Hongxiao YANG, Renxian ZHOU. Effects of Sm addition on reactivity and thermal stability of Pt/SBA-15 for catalytic complete oxidation of benzene[J]. CIESC Journal, 2020, 71(1): 306-313.

图/表 9

表1 部分催化剂的孔径、比表面积和孔体积

Table 1 Pore diameter, SBET and pore volume of some catalysts

No.	Catalyst	Pt/ %(mass)	Sm₂O₃/ %(mass)	Pore diameter/ nm	S_BET/ (m²/g)	V_pore/ (cm³/g)
1	SBA-15	0	0	10.6	473	1.22
2	Pt/SBA-15	1	0	8.0	355	0.84
3	Pt/1.2%Sm₂O₃/SBA-15	1	1.2	9.0	455	1.01
4	Pt/4%Sm₂O₃/SBA-15	1	4.0	7.9	442	1.08
5	Pt/SBA-15(SG)	1	0	5.2	428	0.71
6	Pt/Sm-SBA-15(SG)	1	4.0	3.6	371	0.43

图1 Pt/Sm-SBA-15(SG)样品的等温吸脱附曲线及孔径分布

Fig.1 Adsorption and desorption isotherm and pore volume distribution of Pt/Sm-SBA-15(SG) sample

图2 三个催化剂反应前后的XRD谱图

Fig.2 XRD patterns of three catalysts before and after reaction

图3 暗场条件下1%Pt/SBA-15催化剂的STEM图像及其Pt粒径分布统计结果

Fig.3 HAADF-STEM image of 1%Pt/SBA-15 and column distribution graph of Pt particle diameter

图4 1%Pt/4%Sm2O3/SBA-15催化剂的HAADF-STEM图像及其几种主要元素的分布情况

Fig.4 HAADF-STEM image of 1%Pt/4%Sm2O3/SBA-15 as well as corresponding element O, Si, Sm and Pt maps

图5 不同催化剂下苯的完全氧化反应转化率与温度的关系

Fig.5 Relationship of complete oxidation conversion of benzene with reaction temperature over several catalysts

图6 Pt/SBA-15和Sm2O3/SBA-15催化剂在较高温度条件下反应的转化率随时间的变化

Fig.6 Relationship of benzene conversion with reaction time at higher temperature over 1%Pt/SBA-15 and Sm2O3/SBA-15 respectively

图7 1%Pt/4% Sm2O3/SBA-15和1%Pt/1.2% Sm2O3/SBA-15催化剂在较高温度条件下反应的转化率随时间的变化

Fig.7 Relationship of conversion of benzene with reaction time at higher temperature over 1%Pt/4% Sm2O3/SBA-15 and 1%Pt/1.2% Sm2O3/SBA-15 respectively

图8 1%Pt/SBA-15(SG)和1%Pt/Sm-SBA-15(SG)催化剂在高温条件下反应稳定性的比较

Fig.8 Reaction stability comparison of 1%Pt/SBA-15(SG) and 1%Pt/Sm-SBA-15(SG) at higher temperature

参考文献 30

1	Zhao D Y, Feng J L, Huo Q H.Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300 Angstrom pores[J]. Science, 1998, 279(5350): 548-552.
2	Zhu J, Wang T, Xu X, et al. Pt nanoparticles supported on SBA-15: synthesis, characterization and applications in heterogeneous catalysis[J]. Applied Catalysis B-Environmental, 2013, 130: 197-217.
3	Pushkarev V V, An K, Alayoglu S, et al. Hydrogenation of benzene and toluene over size controlled Pt/SBA-15 catalysts: elucidation of the Pt particle size effect on reaction kinetics[J]. Journal of Catalysis, 2012, 292: 64-72.
4	Chytil S, Glomm W R, Kvande I, et al. Platinum incorporated into the SBA-15 mesostructure via deposition-precipitation method: Pt nanoparticle size estimation and catalytic testing[J].Topics in Catalysis, 2007, 45(1/2/3/4): 93-99.
5	Konya Z, Molnar E, Tasi G, et al. Pre-prepared platinum nanoparticles supported on SBA-15 - preparation, pretreatment conditions and catalytic properties[J]. Catalysis Letters, 2007, 113(1/2): 19-28.
6	Kumar M S, Chen D, Walmsley J C, et al. Dehydrogenation of propane over Pt-SBA-15: effect of Pt particle size[J]. Catalysis Communications, 2008, 9(5): 747-750.
7	Kumar M S, Chen D, Holmen A, et al. Dehydrogenation of propane over Pt-SBA-15 and Pt-Sn-SBA-15: effect of Sn on the dispersion of Pt and catalytic behavior[J]. Catalysis Today, 2009, 142(1/2): 17-23.
8	Li J, Wang J, Ma Z, et al. Preparation of platinum nanoparticle catalyst for propane dehydrogenation[J]. Journal of Nanoscience and Nanotechnology, 2014, 14(9): 6977-6983.
9	Kim D J, Kim J W, Choung S J, et al. The catalytic performance of Pt impregnated MCM-41 and SBA-15 in selective catalytic reduction of NO_x[J]. Journal of Industrial and Engineering Chemistry, 2008, 14(3): 308-314.
10	Liu X, Jiang Z, Chen M, et al. Characterization and performance of Pt/SBA-15 for low-temperature SCR of NO by C₃H₆[J]. Journal of Environmental Sciences, 2013, 25(5): 1023-1033.
11	Chen G, Zheng Y, Cai G, et al. Preparation of promoted Pt/SBA-15 and effect of cerium on the catalytic activity over carbon monoxide oxidation conversion reaction[J]. Catalysis Letters, 2009, 133(3/4): 354-361.
12	Yang C, Wang Z, Zhou X, et al. A mesoporous Pt-SBA-15 nano architecture with catalytic functions on oxidation of CO[J]. Journal of Porous Materials, 2011, 18(1): 31-35.
13	卢泽湘, 吴平易, 季生福, 等. Pt/SBA-15、Pt/SBA-16催化剂的合成、表征及甲烷催化燃烧性能[J]. 分子催化, 2008, 22(4): 368-373.
	Lu Z X, Wu P Y, Ji S F, et al. Synthesis, characterization of Pt/SBA-15 and Pt/SBA-16 catalysts and their methane catalytic combustion performances[J]. Journal of Molecular Catalysis (China), 2008, 22(4): 368-373.
14	Tang W, Wu X, Chen Y. Catalytic removal of gaseous benzene over Pt/SBA-15 catalyst: the effect of the preparation method[J]. Reaction Kinetics Mechanisms and Catalysis, 2015, 114(2): 711-723.
15	Lai Y T, Chen T C, Lan Y K, et al. Pt/SBA-15 as a highly efficient catalyst for catalytic toluene oxidation[J]. ACS Catalysis, 2014, 4(11): 3824-3836.
16	Uson L, Hueso J L, Sebastian V, et al. In-situ preparation of ultra-small Pt nanoparticles within rod-shaped mesoporous silica particles: 3-D tomography and catalytic oxidation of n-hexane[J]. Catalysis Communications, 2017, 100: 93-97.
17	Park J I, Lee J K, Miyawaki J, et al. Catalytic oxidation of polycyclic aromatic hydrocarbons (PAHs) over SBA-15 supported metal catalysts[J]. Journal of Industrial and Engineering Chemistry, 2011, 17(2): 271-276.
18	Chen Z, Mao J, Zhou R. Preparation of size-controlled Pt supported on Al₂O₃ nanocatalysts for deep catalytic oxidation of benzene at lower temperature[J]. Applied Surface Science, 2019, 465: 15-22.
19	Laura U, Arruebo M, Sebastian V. Towards the continuous production of Pt-based heterogeneous catalysts using microfluidic systems[J]. Dalton Transactions, 2018, 47(5): 1693-1702.
20	唐铨, 郭杨龙, 詹望成, 等. 用于丙烷催化燃烧的Pd_xPt_y-ZSM-5/Cordierite整体式催化剂[J]. 化工学报, 2019, 70(3): 944-950.
	Tang Q, Guo Y L, Zhan W C, et al. Catalytic combustion of propane over Pd_xPt_y-ZSM-5/cordierite monolithic catalyst [J]. CIESC Journal, 2019, 70(3): 944-950.
21	余鸿敏, 卢晗锋, 陈银飞. Pt掺杂对Cu-Mn-Ce复合氧化物催化燃烧性能的影响[J]. 化工学报, 2011, 62(4): 947-952.
	Yu H M, Lu H F, Chen Y F. Influence of doped Pt on catalytic combustion performance of Cu-Mn-Ce oxide catalysts[J]. CIESC Journal, 2011, 62(4): 947-952.
22	Seo H J, Kim Y S. Partial oxidation of methane to syngas over M(10)-Ni(5)/SBA-15(M=Ce, Nd, Sm) catalysts[J]. Applied Chemistry for Engineering, 2017, 28(6): 720-725.
23	Bendahou K, Cherif L, Siffert S, et al. The effect of the use of lanthanum-doped mesoporous SBA-15 on the performance of Pt/SBA-15 and Pd/SBA-15 catalysts for total oxidation of toluene[J]. Applied Catalysis A-General, 2008, 351(1): 82-87.
24	Wang X G, Landau M V, Rotter H, et al. TiO₂ and ZrO₂ crystals in SBA-15 silica: performance of Pt/TiO₂(ZrO₂)/SBA-15 catalysts in ethyl acetate combustion[J]. Journal of Catalysis, 2004, 222(2): 565-571.
25	Pirez C, Morin J C, Manayil J C, et al. Sol-gel synthesis of SBA-15: impact of HCl on surface chemistry[J]. Microporous and Mesoporous Materials, 2018, 271: 196-202.
26	Mu Z, Li J J, Hao Z P, et al. Direct synthesis of lanthanide-containing SBA-15 under weak acidic conditions and its catalytic study[J]. Microporous and Mesoporous Materials, 2008, 113(1): 72-80.
27	Wang H, Yang W, Tian P, et al. A highly active and anti-coking Pd-Pt/SiO₂ catalyst for catalytic combustion of toluene at low temperature[J]. Applied Catalysis A: General, 2017, 529: 60-67.
28	郑芳芳, 李倩, 张宏, 等. 抗烧结Rh-Sm₂O₃/SiO₂催化剂的制备和表征及其甲烷部分氧化制合成气性能[J]. 物理化学学报, 2017, 33(8): 1689-1698.
	Zheng F F, Li Q, Zhang H, et al. Preparation and characterization of sinter-resistant Rh-Sm₂O₃/SiO₂ catalyst and its performance for partial oxidation of methane to syngas[J]. Acta Phys. -Chim. Sin., 2017, 33 (8): 1689-1698.
29	Wang H, Tian P, Chen Z, et al. Effect of coke formation on catalytic activity tests for catalytic combustion of toluene: the difficulty of measuring TOF and T98 accurately[J]. Chemical Engineering Communications, 2019, 206(1): 22-32.
30	Taherian Z, Yousefpour M, Tajally M, et al. A comparative study of ZrO₂, Y₂O₃ and Sm₂O₃ promoted Ni/SBA-15 catalysts for evaluation of CO₂/methane reforming performance[J]. International Journal of Hydrogen Energy, 2017, 42(26): 16408-16420.

[1]	李艺彤, 郭航, 陈浩, 叶芳. 催化剂非均匀分布的质子交换膜燃料电池操作条件研究[J]. 化工学报, 2023, 74(9): 3831-3840.
[2]	吴雷, 刘姣, 李长聪, 周军, 叶干, 刘田田, 朱瑞玉, 张秋利, 宋永辉. 低阶粉煤催化微波热解制备含碳纳米管的高附加值改性兰炭末[J]. 化工学报, 2023, 74(9): 3956-3967.
[3]	程业品, 胡达清, 徐奕莎, 刘华彦, 卢晗锋, 崔国凯. 离子液体基低共熔溶剂在转化CO₂中的应用[J]. 化工学报, 2023, 74(9): 3640-3653.
[4]	陈杰, 林永胜, 肖恺, 杨臣, 邱挺. 胆碱基碱性离子液体催化合成仲丁醇性能研究[J]. 化工学报, 2023, 74(9): 3716-3730.
[5]	杨学金, 杨金涛, 宁平, 王访, 宋晓双, 贾丽娟, 冯嘉予. 剧毒气体PH₃的干法净化技术研究进展[J]. 化工学报, 2023, 74(9): 3742-3755.
[6]	王阳, 戴永强, 曾炜. 2，5-二羟基苯磺酸增强离子水凝胶材料热电性能的研究[J]. 化工学报, 2023, 74(9): 3946-3955.
[7]	范孝雄, 郝丽芳, 范垂钢, 李松庚. LaMnO₃/生物炭催化剂低温NH₃-SCR催化脱硝性能研究[J]. 化工学报, 2023, 74(9): 3821-3830.
[8]	杨欣, 彭啸, 薛凯茹, 苏梦威, 吴燕. 分子印迹-TiO₂光电催化降解增溶PHE废水性能研究[J]. 化工学报, 2023, 74(8): 3564-3571.
[9]	杨菲菲, 赵世熙, 周维, 倪中海. Sn掺杂的In₂O₃催化CO₂选择性加氢制甲醇[J]. 化工学报, 2023, 74(8): 3366-3374.
[10]	李凯旋, 谭伟, 张曼玉, 徐志豪, 王旭裕, 纪红兵. 富含零价钴活性位点的钴氮碳/活性炭设计及甲醛催化氧化应用研究[J]. 化工学报, 2023, 74(8): 3342-3352.
[11]	李盼, 马俊洋, 陈志豪, 王丽, 郭耘. Ru/α-MnO₂催化剂形貌对NH₃-SCO反应性能的影响[J]. 化工学报, 2023, 74(7): 2908-2918.
[12]	陈雅鑫, 袁航, 刘冠章, 毛磊, 杨纯, 张瑞芳, 张光亚. 蛋白质纳米笼介导的酶自固定化研究进展[J]. 化工学报, 2023, 74(7): 2773-2782.
[13]	汤晓玲, 王嘉瑞, 朱玄烨, 郑仁朝. 基于Pickering乳液的卤醇脱卤酶催化合成手性环氧氯丙烷[J]. 化工学报, 2023, 74(7): 2926-2934.
[14]	余娅洁, 李静茹, 周树锋, 李清彪, 詹国武. 基于天然生物模板构建纳米材料及集成催化剂研究进展[J]. 化工学报, 2023, 74(7): 2735-2752.
[15]	涂玉明, 邵高燕, 陈健杰, 刘凤, 田世超, 周智勇, 任钟旗. 钙基催化剂的设计合成及应用研究进展[J]. 化工学报, 2023, 74(7): 2717-2734.