Impacts of Sn(II) doping on the Keggin heteropolyacid-catalyzed etherification of glycerol with tert-butyl alcohol
2021; Elsevier BV; Volume: 247; Linguagem: Inglês
10.1016/j.ces.2021.116913
ISSN1873-4405
AutoresMárcio José da Silva, Diêgo Morais Chaves, Sukarno Olavo Ferreira, Renê Chagas da Silva, José B.G. Filho, Carlos Giovani Oliveira Bruziquesi, Abdulrahman A. Al-Rabiah,
Tópico(s)Catalysis for Biomass Conversion
Resumo• H 3-x Sn x/2 PMo 12 O 40 -catalyzed glycerol etherification was assessed (x = 0.0, 1.0, 2.0, 3.0). • Analyses of TG/DSC, EDS/MEV, BET, DRX characterized Sn(II) heteropoly salts. • NH 3 -TPD and adsorbed pyridine FT-IR showed bifunctional Sn 3/2 PMo 12 O 40 catalyst. • Annual capacity of 30,000 ton 3 with a return on investment (ROI) of 30.7%. In this work, phosphomolybdic acid salts were synthesized exchanging their protons by the Sn(II) cations (i.e., H 3-x Sn x/2 PMo 12 O 40 ; x = 0.0, 1.0, 2.0, 3.0), and evaluated in the etherification reactions of glycerol with tert-butyl alcohol (TBA). The catalytic activity of the phosphomolybdate salts containing a variable load of Sn(II) ions was further compared to phosphotungstic and silicotungstic acid salts (i.e., H 3-x Sn x/2 PW 12 O 40 ; x = 0.0, 1.0, 2.0, 3.0 and H 4-x Sn x/2 PW 12 O 40 ; x = 0.0, 1.0, 2.0, 4.0, respectively). The integrity of the Keggin anion after the synthesis was confirmed by infrared spectroscopy analysis. Physical properties were determined through thermal analyses, powder X-Rays diffraction patterns, N 2 adsorption-desorption isotherms, and scanning electron microscopy. The acidity properties were analyzed by adsorbed pyridine FT-IR spectroscopy, NH 3 -programmed-temperature desorption, and potentiometric titration. Among all the Sn(II) heteropoly salts tested, the Sn 3 PMo 12 O 40 was the most active and selective catalyst toward glyceryl ethers. The highest activity of Sn 3 PMo 12 O 40 was assigned to the greater Lewis acidity strength. Modeling, simulation, and economic analysis allowed to evaluate the viability of the process. An annual capacity of 30,000 metric tons was developed, and the process is feasible with a return on investment (ROI) of 30.7%.
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