CoMoNi catalyst texture and surface properties in. heavy oil processing. Part I: hierarchical. macro/mesoporous alumina support

Transcription

1 CoMoNi catalyst texture and surface properties in heavy oil processing. Part I: hierarchical macro/mesoporous alumina support Supporting Information Victoria S. Semeykina a,b,c*, Ekaterina V. Parkhomchuk a,b,c, Alexander V. Polukhin a,b, Pavel D. Parunin a,b,c, Anton I. Lysikov a,b, Artem B. Ayupov a, Svetlana V. Cherepanova a,b,vladislav V. Kanazhevskiy a, Vasily V. Kaichev a, Tatyana S. Glazneva a, Valentina V. Zvereva d. a Boreskov Institute of Catalysis SB RAS, Lavrentieva ave. 5, Novosibirsk 39, Russia b Novosibirsk State University, Pirogova st., Novosibirsk 39, Russia c Research and Education Center, NSU, Pirogova st., Novosibirsk 39, Russia d Nikolaev Institute of Inorganic Chemistry SB RAS, Lavrentieva Ave. 3, Novosibirsk, 39, Russia Corresponding Author * (Victoria S. Semeykina) Tel.: (383)33-9-8; viktoriyasemeykina@ngs.ru 1

2 Table S1. Initial textural data for the catalysts before and after hydrotreating tests Sample S BET, m /g V N, cm 3 /g S Hg, m /g V Hg, cm 3 /g Т Т Table S. EXAFS data for precursor solutions, model CoMoNi catalysts and CoMoNiS catalysts before and after hydrotreating tests Sample Atom to atom Distance, Å Coord. numb. σ, Å E, ev Fit index, % CoMo solution CoMo solution complex complex Mo-O Mo-O Mo-Mo Co-O Co-O Co-O CoMo/Al dried Mo-O Mo-O Mo-Mo CoMo/Al calcined Mo-O Mo-O Mo-Mo CoMo/Al dried Co-O Co-O Co-O CoMo/Al Co-O

3 calcined Co-O Co-O CoMoNi/Al Mo-O Mo-S Mo-Mo CoMoNi/Al CoMoNi/Al Mo-S Mo-Mo Co-S Co-Mo Co-S CoMoNi/Al Co-S Co-Mo Co-Mo Co-S CoMoNi/Al Ni-O Ni-Ni *.13* Ni-Al Ni-Ni Ni-S. 15.7*.138* Ni-Ni CoMoNi/Al Ni-O Ni-Ni *.*.8 Ni-Al Ni-Ni Ni-S Ni-Ni

4 * Inadequate coordination numbers obtained upon simulation could be explained by the increased Debye-Waller factor. Modeling with the lower Debye-Waller factor (.) resulted in poor fit of the spectra. Table S3. Energy values for Mo3d 5/, Cop 3/, Nip 3/ and Sp (ev) according to XPS data Sample Mo3d 5/ (%) Cop 3/ Nip 3/ Sp 8. (1) 3.1 (39) (8) 3. (1) () 3. (38) (91) 3. (9) Table S. Atomic ratios for catalysts before the presulfidation according to XPS data Sample [Mo]/[Al] [Co]/[Al] [Ni]/[Al] [S]/[Al] [C]/[Al] CoMoNi/Al CoMoNi/Al Table S5. XPS data for the presulfided catalysts before and after the hydroprocessing of tatar heavy oil Content, wt. % [Mo]/[Al] [Co]/[Al] [Ni]/[Al] [S]/[Al] [C]/[Al]

5 Fig. S1. SEM image of the dried PS template. 5

6 arbitrary units Mo=O Mo-O-Mo ~1.8 Mo-O (ligand) ~.3 Mo-Mo ~3. ~.8 ~3. CoMo citric complex solution Mo-edge Fig. S. EXAFS spectra of the initial complex solution, Mo-edge

7 arbitrary units.3-. arbitrary units Mo=O Mo-O-Mo ~1.8 Mo-Mo CoMo complex solution CoMo/Al dried CoMo/Al calcined Mo-edge 1 8 Co=O Co-O-Co.-. Co-O- (ligand).-.9 CoMo citric complex solution CoMo/Al dried CoMo/Al calcined Co-edge (a) (b) Fig. S3. Comparison of EXAFS spectra for the precursor solution, dried and calcined catalyst, (a) Mo-edge and (b) Co-edge 7

8 arbitrary units arbitrary units arbitrary units Mo-S ~. Mo-O ~1.8 Mo-Mo Mo-Co Mo-Ni ~3.1 Mo-S Mo-edge ( coordination sphere) (a) ~. Co-S Co-Mo Co-Co ~3. Co-S. Co-edge Ni-O ~. Ni-Ni ~3. Ni-Al ~ Ni-Ni Ni-S Ni-edge (b) (c) Fig. S. EXAFS spectra for the and catalysts, (a) Mo-edge, (b) Co-edge and (c) Niedge 8

9 arbitrary units arbitrary units 11.3 Sp Mo3d Binding energy, ev Binding energy, ev Fig. S5. XPS spectra of the and presulfided catalysts, Sp and Mo3d energies. Normalized to Alp signal intensity. Mo spectra are presented after eliminating Sp contribution 9

10 arbitrary units arbitrary units Cop / 85.5 Nip 3/ x Binding energy, ev Binding energy, ev Fig. S. XPS spectra of the and presulfided catalysts, Cop 3/ and Nip energies. Normalized to Alp signal intensity 1