Cinetica das reações de hidroconversão de residuo de vacuo de petroleo Marlim

AUTOR(ES)

Rafael Menegassi de Almeida

DATA DE PUBLICAÇÃO

2000

RESUMO

In this work kinetic models are obtained for the Marlim vacuum residua (VR) hydroconversion. This is a joint work with PETROBRAS SA. First, several hydroconversion experiments were held on a stirred batch reactor, the feedstock being Marlim VR mixed with FCC decant oil in a 80/20% weight basis. Several temperatures and oil/catalyst ratios were used (catalyst is a commercial NiMo in y­alumina) at different times (O to 4h), at a 110 bar pressure, being kept hydrogen t1ux. The collected product was analysed at PETROBRAS Research Center 1 acilities (CENPES), being obtained hydrodemetalization (HDM) convcrsion 01 up to 100% (vanadium), hydrodesulfurization (HOS) of up to 90% and hydrocracking (HCC) convcrsion up to 70%. Feedstock and products were separatcd in pseudocompounds 01 intcrest in refining industry (VR, gasoil, diesel oil, naphtha and gas). Several HOM, HOS and HCC kinetics were proposed, involving thermal and catalytic contributions. The resulting models consisted of systcms 01 di1 fcrential equations, which were solved along the time taking into account the experimental temperature profile. The Chi-squarc and Box and Oraper criteria objective 1 unctions were minimised to adjust modcl paramctcrs. The usual optimisation methods (gradientless Nelder &Mead Simplex, and gradicnt local minimisation Newton-kind methods) werc not c1 fcctive , duc to thc cxistencc 01 many local minima. A si11lulated annealing continuous minimisation method showed to be effective. A new more cffective hybrid proposed method was developed, applying a Newton-like method between certain si11lulated annealing steps. Several modcls wcre tested, allowing to unscramblc thermal and catalytic e1 fects in the developed kinetics, allowing them to be applied to different catalyst conccntration reactor hydrodynamic models (likc expandcd or bubble-column rcactors)

ASSUNTO(S)

cinetica quimica hidrogenação petroleo - refinação ajuste de curva processos quimicos

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