UV-visible spectroscopy and small fixed-bed reactor were used to study the surface acidity of nano-H-ZSM-5 zeolite modified by alkali metal sodium ion and transition metal zinc ion.
The results showed that alkali metal ion Na
+
modification can effectively eliminate the strong acid sites and reduce the acid amount of the zeolite
which consequently optimized the products distribution of aromatization process by suppressing the production of low-value by-products like methane
ethane or propane. The optimum Zn loading for aromatics production was 3% (mass)
while further increasing Zn loadings resulted in high yield of dry gas. The suitable reaction temperature for C
5
-C
8
alkanes aromatization was 530℃.
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references
Tetsuya F , Hisashi K . Halogen-promoted Pt/KL zeolite catalyst for the production of aromatic hydrocarbons from light naphtha [J ] . Catal. Surv. Asia , 2010 , 14 : 96 - 102 .
Derouane E G , Vanderveken D J . Structural recognition and preorganization in zeolite catalysis: direct aromatization of n -hexane on zeolite L-based catalysts [J ] . Appl. Catal. , 1988 , 45 ( 1 ): 15 - 22 .
Santilli D S , Long J J , Lewis R T . Highly active and highly selective aromatization catalyst : US 4698322 A [P ] . 1987-10-06 .
Blessing C D , Brown S H , Cheung T P , et al . Method of enhancing an aromatization catalyst : US 7932452 B2 [P ] . 2011-04-26 .
Lukyanov D B , Gnep N S , Guisnet M R . Kinetic modeling of propane aromatization reaction over HZSM-5 and GaHZSM-5 [J ] . Ind. Eng. Chem. Res. , 1995 , 34 : 516 - 523 .
Biscardi J A , Meitzner G D , Iglesia E . Structure and density of active Zn species in Zn/H-ZSM5 propane aromatization catalysts [J ] . J. Catal. , 1998 , 179 : 192 - 202 .
Choudhary V R , Sivadinarayana C , Kinage A K , et al . H-gallosilicate(MFI) propane aromatization catalyst influence of calcination temperature on acidity, activity and deactivation due to coking [J ] . Appl. Catal. A , 1996 , 136 : 125 - 142 .
Choudhary V R , Kinage A K , Sivadinarayana C , et al . Initial activity/selectivity of H-gallosilicate (MFI) in propane aromatization: influence of H + exchange and thermal/ hydrothermal pretreatments [J ] . Catal. Lett. , 1995 , 33 : 401 - 422 .
Choudhary V R , Devadas P , Kinage A K , et al . Acidity, catalytic activity, and deactivation of H-gallosilicate (MFI) in propane aromatization: influence of hydrothermal pretreatments [J ] . J. Catal. , 1996 , 158 : 537 - 550 .
Choudhary V R , Devadas P . Influence of space velocity on product selectivity and distribution of aromatics and xylenes in propane aromatization over H-GaMFI zeolite [J ] . J. Catal. , 1997 , 172 : 475 - 478 .
Song C , Liu K F , Zhang D Z , et al . Effect of cofeeding n -butane with methanol on aromatization performance and coke formation over a Zn loaded ZSM-5/ZSM-11 zeolite [J ] . Appl. Catal. A , 2014 , 470 : 15 - 23 .
Ishaq M , Khan M A , Yashima T . Aromatization of butane over gallosilicates [J ] . Fuel Process. Technol. , 1999 , 60 : 173 - 184 .
Le Van Mao R , Yao J H , Dufresne L A , et al . Hybrid catalysts containing zeolite ZSM-5 and supported gallium oxide in the aromatization of n -butane [J ] . Catal. Today , 1996 , 31 : 247 - 255 .
Le Van Mao R , Carli R , Yao J H , et al . Catalysts for the aromatization of n -butane prepared by surface-contact transfer of gallium onto ZSM-5 zeolite particles [J ] . Catal. Lett. , 1992 , 16 : 43 - 52 .
Fukase S , Igarashi N , Aimoto K , et al . A new process of light naphtha aromatization using a zeolite-based catalyst with long-time stability [J ] . Stud. Surf. Sci. Catal. , 1997 , 105 : 885 - 892 .
Fukase S , Igarashi N , Kato K , et al . Development of light naphtha aromatization process using a conventional fixed bed unit [J ] . Stud. Surf. Sci. Catal. , 1995 , 100 : 455 - 464 .
Saito S , Hirabayashi K , Shibata S , et al . Paper presented at 1992 NRPA annual meeting [C ] // New Orleans , 1992 : AM-92 - 38 .
Guisnet M , Gnep N S , Aittaleb D . Conversion of light alkanes into aromatic-hydrocarbons. 6. Aromatization of C 2 —C 4 alkanes on H-ZSM-5 reaction mechanisms [J ] . Appl. Catal. A , 1992 , 87 : 255 - 270 .
Guisnet M , Gnep N S . Mechanism of short-chain alkane transformation over protonic zeolites. Alkylation, disproportionation and aromatization [J ] . Appl. Catal. A , 1996 , 146 : 33 - 64 .
Milas I , Nascimento M A C . The dehydrogenation and cracking reactions of isobutane over the ZSM-5 zeolite [J ] . Chem. Phys. Lett. , 2003 , 373 : 379 - 384 .
Zhao Y , He N , Guo H C . Thermodynamic study on the activation pathways of naphtha fraction in aromatization [J ] . Bull. Sci. Technol. , 2016 , 32 : 5 - 15 .
Xu R F , Liu J X , Liang C C , et al . Effect of alkali metal ion modification on the catalytic performance of nano-HZSM-5 zeolite in butane cracking [J ] . J. Fuel Chem. Technol. , 2011 , 39 : 449 - 454 .
Liu J X , Liang C C , Xu R F , et al . Effect of ion-impregnation treatment on the transformation of C 4 LPG over modified nano-sized HZSM-5 zeolite [J ] . J. Mol. Catal. , 2010 , 24 : 208 - 216 .
Kolyagin Y G , Ordomsky V V , Khimyak Y Z , et al . Initial stages of propane activation over Zn/MFI catalyst studied by in situ NMR and IR spectroscopic techniques [J ] . J. Catal. , 2006 , 238 : 122 - 133 .
Almutairi S M , Mezari B , Magusin P C , et al . Structure and reactivity of Zn-modified ZSM-5 zeolites: the importance of clustered cationic Zn complexes [J ] . ACS Catalysis , 2012 , 2 : 71 - 83 .
Xu J , Zheng A M , Wang X M , et al . Room temperature activation of methane over Zn modified H-ZSM-5 zeolite: Insight from solid-state NMR and theoretical calculations [J ] . Chem. Sci. , 2012 , 3 : 2932 .
Wang X M , Qi G D , Xu J , et al . NMR-Spectroscopic evidence of intermediate dependent pathways for acetic acid formation from methane and carbon monoxide over a ZiiZSM-5 zeolite catalyst [J ] . Angew. Chemie , 2012 , 124 : 3916 - 3919 .
QI G D , XU J , SU J H , et al . Low-temperature reactivity of Zn + ions confined in ZSM-5 zeolite toward carbon monoxide oxidation: insight from in situ DRIFT and ESR spectroscopy [J ] . J. Am. Chem. Soc. , 2013 , 135 : 6762 - 6765 .
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