Seed-fused ZSM-5 nanosheet as a superior MTP catalyst: Synergy of micro/mesopore and inter/external acidity

被引:42
作者
Shang, Yunshan [1 ]
Wang, Wugang [1 ]
Zhai, Yanliang [1 ]
Song, Yu [1 ]
Zhao, Xiaomeng [1 ]
Ma, Tong [1 ]
Wei, Jianhui [1 ]
Gong, Yanjun [1 ]
机构
[1] China Univ Petr, State Key Lab Heavy Oil Proc, Key Lab Catalysis CNPC, Beijing, Peoples R China
基金
中国国家自然科学基金;
关键词
ZSM-5; nanosheet; Micro/mesopore; B incorporation; MTP; Coke selectivity; MFI ZEOLITE NANOSHEETS; PROPYLENE REACTION; SELECTIVE FORMATION; HIERARCHICAL ZSM-5; DIRECTED SYNTHESIS; TUNABLE ACIDITY; METHANOL; CONVERSION; PERFORMANCE; BORON;
D O I
10.1016/j.micromeso.2018.09.038
中图分类号
O69 [应用化学];
学科分类号
081704 ;
摘要
ZSM-5 nanosheet (NS) has an optimal diffusivity due to b-axis oriented two-dimensional structure, but the extra large external acidity results in the deactivation of the catalyst in methanol to propylene (MTP) reaction. The seed-fused ZSM-5 nanosheets (CNS-x) were synthesized by a seed induced method, the performance of samples was compared with one without seed. Further, the B-incorporation sample (B-CNS-5) was prepared with 5 wt% seed and boron acid. Revealing the importance of fusion effect of ZSM-5 seed on the nanosheet, especially the change in microstructure properties and its structure-effect relationship, which is not explicitly documented in previous work. With the seed amount increasing from 5 to 30 wt % in the gel, the crystallization time is largely shortened, along with the change in the resulting nanosheet, such as reduction of particle size and acid strength/ external surface acidity, an increase of over 50% micropore volume. The CNS-x samples perform longer catalytic lifetime (168-226 h) compared to NS (103 h). CNS-5 displays an extremely high selectivity to propylene (C = 3) similar to 54% and total light olefins (C = 2-C = 4) of similar to 84%. A super sample B-CNS-5 exhibits longest lifetime (302 h), achieving highest C = 3 yield due to change in the acid sites distribution and increase of extra weak acid sites. For the converted methanol (g/g(catal)(yst)), the result is B-CNS-5 (966) > CNS-5 (525) > NS (324). In converse, the average coke selectivity (S-av,S- c) is B-CNS-5 (0.18 parts per thousand) < the CNS-5 (0.299 parts per thousand) < NS (0.47 parts per thousand). This result offers new insight for MTP catalyst about the synergy of acidity and diffusion in the ZSM-5 nanosheet.
引用
收藏
页码:173 / 182
页数:10
相关论文
共 68 条
[1]  
[Anonymous], 1984, CHEM LETT, V13, P1059
[2]   Template-Free Synthesis of Hierarchical SSZ-13 Microspheres with High MTO Catalytic Activity [J].
Bing, Liancheng ;
Tian, Aixiu ;
Wang, Fang ;
Yi, Kaifeng ;
Sun, Xingyuan ;
Wang, Guangjian .
CHEMISTRY-A EUROPEAN JOURNAL, 2018, 24 (29) :7428-7433
[3]   MAS NMR AND IR STUDIES ON ZSM-5-TYPE BOROALUMINOZEOLITES [J].
BRUNNER, E ;
FREUDE, D ;
HUNGER, M ;
PFEIFER, H ;
RESCHETILOWSKI, W ;
UNGER, B .
CHEMICAL PHYSICS LETTERS, 1988, 148 (2-3) :226-230
[4]   Aggregates of superfine ZSM-5 crystals: The effect of NaOH on the catalytic performance of methanol to propylene reaction [J].
Chen, Hengbao ;
Wang, Yaquan ;
Meng, Fanjun ;
Sun, Chao ;
Li, Hongyao ;
Wang, Zhao ;
Gao, Fei ;
Wang, Xiao ;
Wang, Shuhai .
MICROPOROUS AND MESOPOROUS MATERIALS, 2017, 244 :301-309
[5]   Amphiphilic organosilane-directed synthesis of crystalline zeolite with tunable mesoporosity [J].
Choi, Minkee ;
Cho, Hae Sung ;
Srivastava, Rajendra ;
Venkatesan, Chithravel ;
Choi, Dae-Heung ;
Ryoo, Ryong .
NATURE MATERIALS, 2006, 5 (09) :718-723
[6]   Stable single-unit-cell nanosheets of zeolite MFI as active and long-lived catalysts (vol 461, pg 246, 2009) [J].
Choi, Minkee ;
Na, Kyungsu ;
Kim, Jeongnam ;
Sakamoto, Yasuhiro ;
Terasaki, Osamu ;
Ryoo, Ryong .
NATURE, 2009, 461 (7265) :828-828
[7]   CHANGES IN THE STRUCTURE OF ZSM-5 ZEOLITES DURING BORON AND ALUMINUM SUBSTITUTION [J].
CICHOCKI, A ;
DATKA, J ;
OLECH, A ;
PIWOWARSKA, Z ;
MICHALIK, M .
JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS, 1990, 86 (04) :753-756
[8]   CALCINATION AND DEBORONATION OF [B]-MFI SINGLE-CRYSTALS [J].
DERUITER, R ;
KENTGENS, APM ;
GROOTENDORST, J ;
JANSEN, JC ;
VANBEKKUM, H .
ZEOLITES, 1993, 13 (02) :128-138
[9]   One-step dual template synthesis of hybrid lamellar-bulk MFI zeolite [J].
Emdadi, Laleh ;
Liu, Dongxia .
JOURNAL OF MATERIALS CHEMISTRY A, 2014, 2 (33) :13388-13397
[10]   Calcination and deboronation of B-MFI applied to the vapour phase Beckmann rearrangement [J].
Forni, L. ;
Fornasari, G. ;
Trifiro, F. ;
Aloise, A. ;
Katovic, A. ;
Giordano, G. ;
Nagy, J. B. .
MICROPOROUS AND MESOPOROUS MATERIALS, 2007, 101 (1-2) :161-168