Oxidação umida catalitica da lignina em reatores trifasicos com produção de aldeidos aromaticos

AUTOR(ES)
DATA DE PUBLICAÇÃO

2001

RESUMO

The lignocellulosic material, representing the largest natural renewable resource, occurring in the plants under the cellulose form, hemicellulose, lignin and extractive, with the lignina corresponding about 30% of this total one. The routes of lignin chemical processing, with prominence for the oxidations processes, with the objective of vanilin production, use in the great majority two-phase processes, some using soluble catalysts in the liquid phase, operating however, with low efficiency. In the present work a process of catalytic wet air oxidation (CW AO) was developed with the objective of selective production of aromatic aldehydes, with emphasis in the vanilina, siringaldeído and p-hidroxibenzaldeído, ITom lignin, applying a palladium catalyst supported in y-alumina. Intending the evaluation of the catalytic process, experiences were carried out in a mechanically stirred high pressure autoclave reactor, in semi-batch way, in relation to the gaseous phase. It was operated in temperatures ITom 373K to 413K, at a total pressure of 20bar, representing a partia! pressure of oxygen ITom 2bar to 10bar. The lignin concentration of60gIL was in an aIkaline medium ofNaOH 2N. A palladium catalyst was used (2,85%pp.), in y-alumina, with granulometry ITom 90mm to 200mm, being applied concentrations ITom 3%pp. to 5%pp. in relation to the reactional volume. The reactions of lignin degradation and aromatic aldehydes production were described by a kinetics model quantified by a system of complex reactions of the series-parallel type, with stages of pseudo-first order. The presence of the catalyst resulted in high levels of seletivities in aldehydes, further than as compared with the non-catalytic process, representing a reduction about 50% in the activation energy for the lignin degradation. The levels of conversion ofthe lignin in aldehydes were of6% at 393K, 12% at 393K and 18% at 423K, for a partial pressure of oxygen of 5bar and catalyst loading of 4%pp. With the purpose of producing aromatic aldehydes in continuous regime way, a three-phase fluidized bed reactor was designed and built, in mini-pilot scale. The system was evaluated hydrodynamically, in pre-operational tests, through applying dynamic analysis for the gaseous phase. The hydrodynamic analysis of the system was accomplished through the values of the gaseous retention (8G) and of the ofaxial Peclet number (PeG). The experimental technique applied the residence time distribution (RTD) in the gaseous phase, using the methane gas as tracer. The estimation ofthe two parameters felI back upon the conftontation ofthe prevision obtained through transfer function ofthe system, with the results uom the dynamic experiments, being adopted as approach the minimization of a objective function through a subroutine of sequencial search. The obtained results, uom 2,2% to 9,3% for the gaseous retention, and 38,0 to 54,4 for the number of Peclet of the gaseous phase, are compatible with the values published in the literature for reactors operating in the same conditions. The aromatic aldehydes production in a continuous three-phase fluidized bed reactor, used as oxidizing agent the atmospheric air in apressure of 4 bar. The influences of the operational parameters were evaluated in the practical ranges of operation, that is, liquid phase flow rate of 5,OL/h and lOL_ temperatures of 393K and 413K. The gaseous phase flow rate was 1000 NL/h with a catalyst loading of 3%pp and granulometry of 400 j.1m 500j.1m The lignin was in an aIkaline medium of NaOH 2N, in a concentration of 30g/L. The best yield in aromatic aldehydes reached 12% in relation to lignin initial concentration, as the reactor was operating at 393K and liquid flow rate of5LIh

ASSUNTO(S)

lignina lignin three-phase fluidized bed siringaldehyde aldeidos oxidação paliadium catalyst p-hidroxibenzaldehyde catalisadores de paladio lignin corantes catalytic wet air oxidation

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