Professional Documents
Culture Documents
Study of The Aromatic Compounds Saturation Process in Middle Distillates
Study of The Aromatic Compounds Saturation Process in Middle Distillates
EXPERIMENTAL
Six real industrial feedstocks obtained from distinct oil sources and refinery processes were used in this work: kerosene, light gas oil (LGO) and heavy gas oil (HGO) from atmospheric distillation; light and middle gas oil (LGO/MGO) from delayed coking; light vacuum gas oil (LVGO) from vacuum distillation; and light cycle oil (LCO) from fluid catalytic cracking. Commercial Ni-Mo-S/Al2O3 catalysts were used for HDA tests. Catalysts were sulphided in-situ on the pilot plant, by passing a stream of hydrogenated spindle doped with CS2 (20000 ppmw) for 8 h. The reactor was heated by six independently controlled electric furnaces, which guaranteed the isothermal operation over the whole catalyst bed. The reactor was loaded with 310 cm3 of catalysts and an up-flow arrangement was used to minimize back-mixing problems. The liquid product was collected into a refrigerated recipient for analysis. The gas product was analyzed in-line with a wet gas meter (WGM) and a process chromatographer. A total of 79 tests were performed in a completely automated pilot plant. Replicates and blank tests were carried out to guarantee that catalyst remained active. 22 tests were used for independent validation of the model and were not used for parameter estimation (1). The oil compounds were identified by group type analysis (GTA) and grouped into eight distinct families: poly-aromatics (PA); di-aromatics (DA); mono-aromatics (MA); naphthenes (NP); paraffins (PF); dibenzothiophehes (DT); benzothiophenes (BT) and tiophenes (TP).
DT
kPA kPAr
BT
kDA kDAr
TF
kMA kNF
kDT
kBT
kTF
PA DA
MA
kMar
NF PF
Figure 1 Proposed reaction mechanism for the HDA process. Based on Figure 1, the following set of pseudo-phenomenological mass balance equations may be written:
where C are concentrations, t is the reaction time, k are the kinetic constants and pH2 is the partial hydrogen pressure. Rate equations were integrated from the reactor inlet to the reactor outlet. It is assumed that the kinetic constants follow the Arrhenius form as:
k i = k io e
Eai
RT
(9)
Therefore, the total set of model parameters comprises: pre-exponential factors: kPAo , kPAo,r , kDAo , kDAo,r , kMAo , kMAo,r , kNPo , kDTo , kBTo and kTPo. 2
activation energies: EaPA , EaPA,r , EaDA , EaDA,r , EaMA , EaMA,r , EaNP , EaDT , EaBT and EaTP.
The kinetic parameters were estimated with a previously validated parameter estimation procedure (4), based on the Maximum Likelihood technique (5), using the Gauss approach (6) to minimize the objective function. The ordinary differential equations were solved numerically with a 4th order Runge-Kutta method (7).
30
20
10
Figure 2 Comparison between model predictions and experimental results for concentrations of mono- (), di- (o), poly- (+) and total aromatics ( ).
20% Conversion (% Volume) . 10% 0% -10% -20% -30% -40% -50% -30 -20 -10 0 10 20 30 40
CONCLUSION
A pseudo-phenomenological model for the HDA process was developed and validated, based on real process data. The model shows that reaction reversibility may be an important issue in industrial sites, as maximum aromatics conversion limits depend on the feed characteristics and operation conditions. This encourages the implementation of the model at plant site, in order to allow the optimization of HDA industrial plants as a function of feed properties. This may allow the improvement of diesel fuels, leading to lower emissions and higher combustion efficiency.
REFERENCES
1. 2. 3. 4. 5. 6. 7. Dauzacker, E. R., Estudo do Processo de Saturao dos Compostos Aromticos em Destilados Mdios, M. Sc. Thesis, PEQ/COPPE, UFRJ, Rio de Janeiro (2001). Stanislaus, A. and Cooper, B.H., Aromatic Hydrogenation Catalysis: A Review, Catal. Rev. Sci. Eng. 36 (1), 75-123 (1994). Cooper, B. H., Donnis, B. B. L. , Aromatic Saturation of Distillates: An Overwiew,Appl. Catal. A. 137 (1996) 203. Noronha, F. B., Pinto, J. C., Monteiro, J. L., Lobo, M. W. and Santos, T. J., ESTIMA - The User's Guide, Internal Report, PEQ/COPPE/UFRJ, Rio de Janeiro (1993). Anderson, T.F., Abrams, D.S. e Grens II, E.A., 1978, AICHE J. 24,20-29. Bard, Y., Nonlinear Parameter Estimation, Academic Press, New York, 1974. ME Davis, Numerical Methods and Modeling for Chemical Engineers, John Wiley & Sons, New York, 1984.