Effect of Thermal, Acid, and Alkaline Treatments over SAPO-34 and Its Agglomerated Catalysts: Property Modification and Methanol-to-Olefin Reaction Performance

被引:2
作者
Zapater, Diego [1 ,2 ]
Lasobras, Javier [1 ]
Zambrano, Naydu [2 ]
Hita, Idoia [2 ]
Castano, Pedro [2 ]
Soler, Jaime [1 ]
Herguido, Javier [1 ]
Menendez, Miguel [1 ]
机构
[1] Univ Zaragoza, Aragon Inst Engn Res I3A, Dept Chem & Environm Engn, Catalysis & React Engn Grp CREG, Zaragoza 50018, Spain
[2] King Abdullah Univ Sci & Technol KAUST, KAUST Catalysis Ctr, Multiscale React Engn, Thuwal 239556900, Saudi Arabia
关键词
ZEOLITE CATALYSTS; ETHENE FORMATION; MOLECULAR-SIEVE; MTO PROCESS; DEACTIVATION; CONVERSION; COKE; TEMPERATURE; HYDROCARBONS; TRANSFORMATION;
D O I
10.1021/acs.iecr.3c03956
中图分类号
TQ [化学工业];
学科分类号
0817 ;
摘要
SAPO-34 zeolite is one of the most well-studied methanol-to-olefin catalysts, with applications from laboratory to commercial scale. Here, we have studied the impact on the properties and performance of different modifications of a commercial zeolite, including thermal, acid, and alkaline treatments, along with its agglomeration with bentonite and alumina required in the technical catalyst. We prepared three zeolites and agglomerated them, making a total of seven materials, along with our benchmark catalyst. These were characterized and tested in a packed bed reactor. We analyzed the conversion, yield, and deactivation (coke) based on the effective acid site density rho(AS)* (a parameter correlating acid strength, density, and micropore volume). Thermal treatment increased the effective acid site density of the commercial zeolite by 60%, while only a 10% increase was found in the parent agglomerated catalyst. Acid etching increased the effective acid site density by 80%, while the basic treatment completely amorphized the framework of the zeolite. After agglomeration, the performance of the catalysts (by means of olefin production and deactivation) correlated with effective acid site density. The catalysts based on thermally and acid-treated zeolites performed best, while they had the lowest effective acid site density.
引用
收藏
页码:3586 / 3599
页数:14
相关论文
共 79 条
[1]   Role of acidity and microporous structure in alternative catalysts for the transformation of methanol into olefins [J].
Aguayo, AT ;
Gayubo, AG ;
Vivanco, R ;
Olazar, M ;
Bilbao, J .
APPLIED CATALYSIS A-GENERAL, 2005, 283 (1-2) :197-207
[2]  
Aguayo AT, 1999, J CHEM TECHNOL BIOT, V74, P1082
[3]  
Ahmadova RH, 2017, PROCESS PETROCHEM OI, V18, P171
[4]   X-Ray Imaging of SAPO-34 Molecular Sieves at the Nanoscale: Influence of Steaming on the Methanol-to-Hydrocarbons Reaction [J].
Aramburo, Luis R. ;
Ruiz-Martinez, Javier ;
Sommer, Linn ;
Arstad, Bjornar ;
Buitrago-Sierra, Robison ;
Sepulveda-Escribano, Antonio ;
Zandbergen, Henny W. ;
Olsbye, Unni ;
de Groot, Frank M. F. ;
Weckhuysen, Bert M. .
CHEMCATCHEM, 2013, 5 (06) :1386-1394
[5]   Theoretical study of the methylbenzene side-chain hydrocarbon pool mechanism in methanol to olefin catalysis [J].
Arstad, B ;
Nicholas, JB ;
Haw, JF .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (09) :2991-3001
[6]   The effect of various treatment conditions on natural zeolites: Ion exchange, acidic, thermal and steam treatments [J].
Ates, Ayten ;
Hardacre, Christopher .
JOURNAL OF COLLOID AND INTERFACE SCIENCE, 2012, 372 :130-140
[7]   Influence of the Reaction Temperature on the Nature of the Active and Deactivating Species During Methanol-to-Olefins Conversion over H-SAPO-34 [J].
Borodina, E. ;
Kamaluddin, H. Sharbini Harun ;
Meirer, F. ;
Mokhtar, M. ;
Asiri, A. M. ;
Al-Thabaiti, S. A. ;
Basahel, S. N. ;
Ruiz-Martinez, J. ;
Weckhuysen, B. M. .
ACS CATALYSIS, 2017, 7 (08) :5268-5281
[8]   Thermal stability and dehydroxylation of Bronsted acid sites in silicoaluminophosphates H-SAPO-11, H-SAPO-81 H-SAPO-31, and H-SAPO-34 investigated by multi-nuclear solid-state NMR spectroscopy [J].
Buchholz, A ;
Wang, W ;
Xu, M ;
Arnold, A ;
Hunger, M .
MICROPOROUS AND MESOPOROUS MATERIALS, 2002, 56 (03) :267-278
[9]   Effects of Thermal Treatment on Natural Clinoptilolite-Rich Zeolite Behavior in Simulated Biological Fluids [J].
Cadar, Oana ;
Senila, Marin ;
Hoaghia, Maria-Alexandra ;
Scurtu, Daniela ;
Miu, Ion ;
Levei, Erika Andrea .
MOLECULES, 2020, 25 (11)
[10]   A methanol to olefins review: Diffusion, coke formation and deactivation SAPO type catalysts [J].
Chen, D. ;
Moljord, K. ;
Holmen, A. .
MICROPOROUS AND MESOPOROUS MATERIALS, 2012, 164 :239-250