Identification of the structure of Ni active sites for ethylene oligomerization on an amorphous silica-alumina supported nickel catalyst

doi:10.1016/S1872-2067(21)63827-5

Abstract

Abstract:

Abstract: The structure of Ni active sites supported on amorphous silica-alumina supports with different contents of Al₂O₃ loadings in relation to their activities in ethylene oligomerization were investigated. Two kinds of Ni sites were detected by in situ FTIR-CO and H₂-TPR experiments, that are Ni²⁺ cations as grafted on weak acidic silanols and Ni²⁺ cations at ion-exchange positions. The ethylene oligomerization activities of these Ni/ASA catalysts were found an ascending tendency as the Al₂O₃ loading decreased, which could be attributed to the enriched concentration of Ni²⁺ species on acidic silanols with a weaker interaction with the amorphous silica-alumina support. These Ni²⁺ species were more easily to be evolved into Ni⁺ species, which has been identified to be the active sites of ethylene oligomerization. Thus, it seems reasonable to conclude that Ni²⁺ species grafted on acidic silanols were the precursors of active sites.

Key words: Supported nickle catalyst, Amorphous silica-alumina, FT-IR, Active sites, Ethylene oligomerization

Jinghua Xu, Ruifeng Wang, Yaru Zhang, Lin Li, Wenjun Yan, Junying Wang, Guodong Liu, Xiong Su, Yanqiang Huang, Tao Zhang. Identification of the structure of Ni active sites for ethylene oligomerization on an amorphous silica-alumina supported nickel catalyst[J]. Chinese Journal of Catalysis, 2021, 42(12): 2181-2188.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)63827-5

https://www.cjcatal.com/EN/Y2021/V42/I12/2181

Figures/Tables 7

Fig. 1. (a) 27Al NMR spectra of ASA supports with different contents of Al2O3 loadings; (b) The concentration of AlIV species as a function of Al2O3 loadings.

Scheme 1. Structural schematic representation of H atoms with (a) an ion-exchange position and (b) an acidic silanol position.

Fig. 2. Pyridine FT-IR spectra of Ni/ASA catalysts with different amount of Al2O3 loadings. The solid and dotted line indicate the pyridine-adsorption FT-IR spectra on the catalysts which were degassed at 150 and 350 °C after a saturated adsorption of pyridine, respectively.

Fig. 3. (a) DRIFT spectra of Ni/ASA catalysts with different amounts of Al2O3 loadings; (b) The fitted DRIFT spectra in an amplified wave number range of 2180-2200 cm-1. The FTIR spectra were recorded following an evacuation process until the physically adsorbed CO was desorbed.

Fig. 4. H2-TPR profiles of the Ni/ASA samples with different contents of Al2O3 loadings.

Fig. 5. C2H4-TPD spectra of Ni/ASA samples with different contents of Al2O3 loadings.

Fig. 6. Ethylene oligomerization activities of Ni/ASA catalysts with different contents of Al2O3 loadings. Reaction conditions: 0.5 g catalyst, 50% C2H4 balanced with N2 (15 mL min-1).

References

[1]	L. K. Johnson, C. M. Killian, M. Brookhart, J. Am. Chem. Soc., 1995, 117, 6414-6415.
[2]	J. Heveling, C. P. Nicolaides, M. S. Scurrell, J. Chem. Soc. Chem. Commun., 1991, 126-127.
[3]	J. Heveling, C. P. Nicolaides, M. S. Scurrell, App. Catal. A, 1998, 173, 1-9.
[4]	K. Toch, J. W. Thybaut, G. B. Marin, App. Catal. A, 2015, 489, 292-304.
[5]	M. D. Heydenrych, C. P. Nicolaides, M. S. Scurrell, J. Catal., 2001, 197, 49-57.
[6]	R. D. Andrei, M. I. Popa, F. Fajula, V. Hulea, J. Catal., 2015, 323, 76-84.
[7]	M. Hartmann, A. Poppl, L. Kevan, J. Phy. Chem., 1996, 100, 9906-9910.
[8]	V. Hulea, F. Fajula, J. Catal., 2004, 225, 213-222.
[9]	A. Lacarriere, J. Robin, D. Swierczynski, A. Finiels, F. Fajula, F. Luck, V. Hulea, Chemsuschem, 2012, 5, 1787-1792.
[10]	M. Lallemand, A. Finiels, F. Fajula, V. Hulea, J. Phy. Chem. C, 2009, 113, 20360-20364.
[11]	M. Lallemand, A. Finiels, F. Fajula, V. Hulea, Chem. Eng. J., 2011, 172, 1078-1082.
[12]	M. Lallemand, A. Finiels, F. Fajula, V. Hulea, App. Catal. A, 2006, 301, 196-201.
[13]	M. Lallemand, O. A. Rusu, E. Dumitriu, A. Finiels, F. Fajula, V. Hulea, App. Catal. A, 2008, 338, 37-43.
[14]	A. Martínez, M. A. Arribas, P. Concepción, S. Moussa, App. Catal. A, 2013, 467, 509-518.
[15]	R. Henry, M. Komurcu, Y. Ganjkhanlou, R. Y. Brogaard, L. Lu, K.-J. Jens, G. Berlier, U. Olsbye, Catal. Today, 2018, 299, 154-163.
[16]	D. Gajan, C. Coperet, New J. Chem., 2011, 35, 2403-2408.
[17]	A. Finiels, F. Fajula, V. Hulea, Catal. Sci. Technol., 2014, 4, 2412-2426.
[18]	R. Y. Brogaard, U. Olsbye, ACS Catal., 2016, 6, 1205-1214.
[19]	S. Moussa, P. Concepción, M. A. Arribas, A. Martínez, ACS Catal., 2018, 8, 3903-3912.
[20]	S. Moussa, M. A. Arribas, P. Concepción, A. Martínez, Catal. Today, 2016, 277, 78-88.
[21]	J. Xu, R. Wang, L. Zheng, J. Ma, W. Yan, X. Yang, J. Wang, X. Su, Y. Huang, Catal. Sci. Technol., 2021, 11, 1510-1518.
[22]	C. A. Emeis, J. Catal., 1993, 141, 347-354.
[23]	K. Gora-Marek, J. Datka, App. Catal. A, 2006, 302, 104-109.
[24]	E. J. M Hensen, D. G. Poduval, V. Degirmenci, D. A. J. Michel Ligthart, W. Chen, F. Maugé, M. S. Rigutto, J. A. Rob van Veen, J. Phy. Chem. C, 2012, 116, 21416-21429.
[25]	A. Penkova, S. Dzwigaj, R. Kefirov, K. Hadjiivanov, M. Che, J. Phy. Chem. C, 2007, 111, 8623-8631.
[26]	H. A. Aleksandrov, V. R. Zdravkova, M. Y. Mihaylov, P. St. Petkov, G. N. Vayssilov, K. I. Hadjiivanov, J. Phy. Chem. C, 2012, 116, 22823-22831.
[27]	K. Gora-Marek, A. Glanowska, J. Datka, Microporous Mesoporous Mater., 2012, 158, 162-169.
[28]	M. Mihaylov, K. Hadjiivanov, Langmuir, 2002, 18, 4376-4383.
[29]	K. Hadjiivanov, M. Mihaylov, D. Klissurski, P. Stefanov, N. Abadjieva, E. Vassileva, L. Mintchev, J. Catal., 1999, 185, 314-323.
[30]	A. A. Gabrienko, I. G.Danilova, S. S. Arzumanov, A. V. Toktarev, D. Freude, A. G. Stepanov, Microporous Mesoporous Mater., 2010, 131, 210-216.
[31]	Z. Qu, X. Zhang, F. Yu, X. Liu, Q. Fu, J. Catal., 2015, 321, 113-122.
[32]	S. Caldarelli, H. Pizzala, L. Arrighi, F. Ziarelli, G. Busca, J. Phy. Chem. C, 2011, 115, 10569-10575.
[33]	E. J. M Hensen, D. G. Poduval, P. C. M. M. Magusin, A. E. Coumans, J. A. R. van Veen, J. Catal., 2010, 269, 201-218.
[34]	A. N. Mlinar, S. Shylesh, O. C. Ho, A. T. Bell, ACS Catal., 2014, 4, 337-343.