Non-Porous Sulfonic Acid Catalysts Derived from Vacuum Residue Asphaltenes for Glycerol Valorization via Ketalization with Acetone

Abstract

In this study, an approach for the preparation of heterogeneous acid catalysts based on asphaltenes isolated from vacuum residue is proposed. Varying the conditions for the sulfonation of asphaltenes made it possible to obtain materials with an acid value of 1.16 to 2.76 meq g–1 and a total sulfur content of 6.4 to 12.3 wt%. The samples obtained were characterized by acid-base titration, nitrogen adsorption, sulfur elemental analysis and transmission electron microscopy techniques, and were studied as potential acid catalysts in the ketalization reaction between glycerol and acetone. Sulfonated asphaltenes (SA) were characterized by a homogeneous distribution of sulfonic groups over the granule surface and an almost complete absence of a porous structure. The ketalization reaction in the presence of SA proceeded without intradiffusion restrictions; as a result of which, their activity was higher than for known heterogeneous catalysts. The most active SA sample (total acid value, 1.16 meq g–1) had an apparent activation energy of 18.0 kJ mol–1, which was lower than the value obtained for the zeolite BEA-40 (29–53 kJ mol–1) and the Amberlyst 36 resin (27 kJ mol–1), and was close to the value for the homogeneous p-TSA catalyst (14.5 kJ mol–1). The SA heterogeneous catalysts did not show any acid leaching and had no loss of activity after five catalytic cycles, with the total turnover number TON = 7247.

Catalysis for Oleochemical Platforms

“…Another approach employs residues of industrial wastes or biomass‐derived materials to produce innovative catalysts, most of them obtained upon sulfonation. Some examples are reported by Alsawalha, [98] da Silva, [104] Samoilov, [105] Pompeo [106] and Fernández, [107] Saikia, [108] Ravi [109] and Mota [110] …”

Asphaltenes from Ethylene Tar as a Potential Raw Material to Obtain High Value-Added Products

“…Preparation of effective acidic carbocatalysts and sorbents based on modified petroleum asphaltenes has been extensively investigated in recent years [13][14][15][16][17][18][19]31,32]. A rigid carbon framework and facile modification of the polyaromatic core with reactive functional groups could improve the catalytic and sorption ability of modified asphaltenes and allow for their use as effective catalysts in some acid-catalyzed reactions, as well as adsorbents of heavy metals and other ecotoxicants.…”

“…Many works are devoted to the modification of petroleum asphaltenes. Modified asphaltenes can be used in the production of sorbents and catalysts [13][14][15][16][17][18][19], precursors of carbon materials [20][21][22][23][24][25], components for energy storage and conversion in alternative energetics [26][27][28][29], and for other purposes [30]. Production of such materials is possible due to the high reactivity of asphaltenes molecules, which easily undergo sulfonation [30][31][32], nitration, and other reactions [13][14][15][16]33], as a result of which various functional groups are added to the polycondensed aromatic core.…”

Metal‐ and Acid‐Free Photocatalytic Approach Using Quinone‐Based Hyper‐Crosslinked Porous Catalysts for the Valorization of Glycerol into Solketal

“…[3] Besides, solketal can be used as an oxygenated additive of fuels being a good option to replace methyl tert-butyl ether (MTBE) and ethyl tert-butyl ether (ETBE), oxygenated additives derived from petroleum, which are the most commonly used in fuels. [1,2] Solketal can be easily obtained by glycerol acetylation with acetone using acid [4][5][6][7] , metal catalysts, [8,9] or both. [10][11][12] The reaction conditions generally vary from room temperature to heating at 120 °C and with reaction times between 1 and 14 h. The main drawback of most of these catalysts is that, in the case of acid catalysts, the acidic character is provided by sulfonic groups that must be incorporated by postsulfonation of the support.…”

“…Solketal can be easily obtained by glycerol acetylation with acetone using acid [ 4–7 ] , metal catalysts, [ 8,9 ] or both. [ 10–12 ] The reaction conditions generally vary from room temperature to heating at 120 °C and with reaction times between 1 and 14 h. The main drawback of most of these catalysts is that, in the case of acid catalysts, the acidic character is provided by sulfonic groups that must be incorporated by postsulfonation of the support.…”