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Oxidative dehydration of glycerol to acrylic acid in one step using bifunctional catalysts

Grant number: 13/10204-2
Support Opportunities:Scholarships in Brazil - Doctorate
Effective date (Start): September 01, 2013
Effective date (End): December 31, 2016
Field of knowledge:Engineering - Chemical Engineering - Chemical Technology
Principal Investigator:Leandro Martins
Grantee:Luiz Gustavo Possato
Host Institution: Instituto de Química (IQ). Universidade Estadual Paulista (UNESP). Campus de Araraquara. Araraquara , SP, Brazil
Associated research grant:10/01449-3 - Development of porous heterogeneous catalysts for the conversion of renewable feedstocks, AP.JP


The driving force of the project involves strengthening the use of renewable raw materials with the intention of reducing the dependency of society in relation to petrochemical sources. The main theme of the proposal is the development of bifunctional catalysts with commercial MFI, BEA and MOR zeolites prepared by ion exchanged with vanadium salts, impregnation and chemical vapor deposition. The purpose of obtaining these bifunctional catalysts is to use them in catalytic conversion in one step of glycerol to acrylic acid. This is a two steps system, namely first the glycerol dehydration to acrolein on heterogeneous acid catalysts, and subsequently the oxidation of acrolein to acrylic acid by oxidizing catalysts, i.e. two catalytic reactors are used. The method of insertion of vanadium species and the reaction conditions such as temperature, concentration of O2 and H2O profoundly influence on the composition / oxidation state of the vanadium, whose interest in oxidative dehydration of glycerol is the oxidation state of V4+. Thus, it becomes essential to use advanced spectroscopic characterization techniques, in situ or in operando, in which one can obtain information about changes in the oxidation state, the structural organization of the short and long distance and on the formation of intermediate compounds, metastable in reaction conditions. Such assessments will be carried out in the Synchrotron Soleil in France, after the approval of the PhD project. Photoelectron X-ray spectroscopy , 51V RMN are additional techniques for the investigation of the chemical environment around the vanadium atoms. Additionally, we will evaluate the influence of the pore system in the conversion of glycerol to acrolein, considering the control of pores created in the zeolites by alkali treatment (desilication) and also the deactivation and determination/ quantification of coke.

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Scientific publications (7)
(References retrieved automatically from Web of Science and SciELO through information on FAPESP grants and their corresponding numbers as mentioned in the publications by the authors)
POSSATO, LUIZ G.; CASSINELLI, WELLINGTON H.; MEYER, CAMILO I.; GARETTO, TERESITA; PULCINELLI, SANDRA H.; SANTILLI, CELSO V.; MARTINS, LEANDRO. Thermal treatments of precursors of molybdenum and vanadium oxides and the formed MoxVyOz phases active in the oxydehydration of glycerol. APPLIED CATALYSIS A-GENERAL, v. 532, p. 1-11, . (13/10204-2, 10/01449-3)
ABREU, THIAGO H.; MEYER, I, CAMILO; PADRO, CRISTINA; MARTINS, LEANDRO. Acidic V-MCM-41 catalysts for the liquid-phase ketalization of glycerol with acetone. Microporous and Mesoporous Materials, v. 273, p. 219-225, . (16/10597-2, 13/10204-2)
POSSATO, LUIZ G.; ACEVEDO, MAURO D.; PADRO, CRISTINA L.; BRIOIS, VALERIE; PASSOS, ALINE R.; PULCINELLI, SANDRA H.; SANTILLI, CELSO V.; MARTINS, LEANDRO. Activation of Mo and V oxides supported on ZSM-5 zeolite catalysts followed by in situ XAS and XRD and their uses in oxydehydration of glycerol. MOLECULAR CATALYSIS, v. 481, n. SI, . (16/10597-2, 13/10204-2)
VIEIRA, LUIZ H.; POSSATO, LUIZ G.; CHAVES, THIAGO F.; PULCINELLI, SANDRA H.; SANTILLI, CELSO V.; MARTINS, LEANDRO. Studies on dispersion and reactivity of vanadium oxides deposited on lamellar ferrierite zeolites for condensation of glycerol into bulky products. MOLECULAR CATALYSIS, v. 458, n. B, SI, p. 161-170, . (16/10597-2, 13/10204-2, 14/20116-6)
RASTEIRO, LETICIA F.; VIEIRA, LUIZ H.; SANTILLI, CELSO V.; MARTINS, LEANDRO. Surfactant-assisted synthesis of Mo-V mixed oxide catalysts for upgraded one-step conversion of glycerol to acrylic acid. RSC ADVANCES, v. 8, n. 22, p. 11975-11982, . (13/10204-2, 16/10597-2, 14/20116-6)
POSSATO, LUIZ G.; CHAVES, THIAGO F.; CASSINELLI, WELLINGTON H.; PULCINELLI, SANDRA H.; SANTILLI, CELSO V.; MARTINS, LEANDRO. The multiple benefits of glycerol conversion to acrolein and acrylic acid catalyzed by vanadium oxides supported on micro-mesoporous MFI zeolites. CATALYSIS TODAY, v. 289, p. 20-28, . (13/10204-2, 14/11952-5)
POSSATO, LUIZ G.; CASSINELLI, WELLINGTON H.; GARETTO, TERESITA; PULCINELLI, SANDRA H.; SANTILLI, CELSO V.; MARTINS, LEANDRO. One-step glycerol oxidehydration to acrylic acid on multifunctional zeolite catalysts. APPLIED CATALYSIS A-GENERAL, v. 492, p. 243-251, . (13/10204-2, 10/01449-3)
Academic Publications
(References retrieved automatically from State of São Paulo Research Institutions)
POSSATO, Luiz Gustavo. One-step glycerol oxidehydration to acrylic acid using bifunctional catalysts. 2016. Doctoral Thesis - Universidade Estadual Paulista (Unesp). Instituto de Química. Araraquara Araraquara.

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