Hydrodesulfurization of Dibenzothiophene in a Micro Trickle Bed Catalytic Reactor under Operating Conditions from Reactive Distillation

J. C. García-Martínez; A. Dutta; G. Chávez; J. A. De los Reyes; C. O. Castillo-Araiza

doi:10.1515/ijcre-2015-0126

Article

Hydrodesulfurization of Dibenzothiophene in a Micro Trickle Bed Catalytic Reactor under Operating Conditions from Reactive Distillation

J. C. García-Martínez , A. Dutta , G. Chávez , J. A. De los Reyes and C. O. Castillo-Araiza

Published/Copyright: December 16, 2015

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From the journal International Journal of Chemical Reactor Engineering Volume 14 Issue 3

Abstract

The hydrodesulfurization (HDS) of dibenzothiophene (DBT) is investigated over a commercial NiMoP/γ-Al₂O₃ catalyst in a micro trickled bed reactor (Micro-TBR) at operating conditions of a reactive distillation (RD) column. An analysis with and without reaction is carried out to have a first understanding on the complex interaction between kinetics and transport phenomena. A set of well-accepted criteria is evaluated to elucidate the presence of heat and mass transport limitations. Residence time distribution (RTD) experiments are performed to evaluate axial dispersion through the estimation of axial dispersion coefficient (D_axial,L) from a convection-dispersion model. Experiments with reaction are carried out using hydrogen and DBT as feedstock at reaction temperatures from 533 to 599 K, pressures from 1.5 to 2.5 MPa and inlet molar flow of DBT from 4 to 12×10^–8 mol.s^–1. A pseudo heterogeneous model accounting for mass transport limitations is used to describe experiments under reaction conditions. The main findings can be summarized as follows: most of RD operating conditions lead to the presence of interfacial mass transport limitations at both interfaces L-S and G-L; convection-dispersion model is able to describe satisfactorily RTD observations, suggesting that axial dispersion phenomena are negligible; conversion of DBT ranges from ca. 22 to 90% having a selectivity to by-product molecules from 30 to 80%, respectively; and the pseudo heterogeneous reaction model describes observations adequately obtaining activation energies ranging from 49 to 62 kJ mol^–1 at pressures from 1.5 to 2.5 MPa, respectively. Estimated activation energies are comparatively lower than the activation energies reported in literature for the conventional HDS process, i.e. 40–160 kJ.mol^–1, thereby suggesting an apparent catalytic energy savings by using RD technology.

Keywords: HDS; reactive distillation; NiMoP/γ-Al2O3, kinetics; pseudo heterogeneous model

Acknowledgments

Julio Cesar gratefully acknowledges CONACyT (México) for the grant with registry No. 179608 and IMP for the catalyst provided for the experiments.

Nomenclature

Roman Letters

a_B: interfacial area related to gas interface, m^–1
a_L: interfacial area related to liquid interface, m^–1
a_s: interfacial area related to solid interface, m^–1
C_L: tracer concentration at the exit of the vessel, kg.m^–3
C: tracer concentration, kg.m^–3
C₀: inlet tracer concentration, kg.m^–3
C_i,G: concentration of the component i-th in gas phase, mol.m^–3
C _i,L: concentration of component i-th in liquid phase, mol.m^–3
C_i,S: concentration of the component i-th in solid phase, mol.m^–3
C_k,n: n-th experimental response, mol.m^–3
C^k,n: n-th predicted responses, mol.m^–3
d_p: particle diameter, m
d_pi: inert particle diameter
d_r: reactor diameter, m
D_axial,L: axial dispersion coefficient, m².s^–1
DiG: diffusion coefficient of component i-th in gas phase, m².s^–1
DiL: diffusion coefficients of component i-th in liquid phase, m².s^–1
D_eff: effective diffusion coefficient of component i-th into the catalyst particle, m².s^–1
E: exit age distribution of the fluid, s^–1
E_θ: dimensionless exit age distribution, -/-
E_a: activation energy, kJ.mol^–1
h_i: heat transfer coefficient, W.m^–2.K^–1
H: Henry’s constant based on solubility of component i-th in hexadecane, –/–
K_i: adsorption constant of component i, m³.mol^–1
k_eff: bed effective radial conductivity, W.m^–1.K^–1
k_GL: overall interfacial mass transfer coefficient at the interface L-S, m.s^–1
k_LS: overall interfacial mass transfer coefficient at the interface L-S, m.s^–1
k_L: interfacial mass transfer coefficient at the liquid interface, m.s^–1
k_p: effective thermal conductivity of the particle, W.m^–1.K^–1
k_s: interfacial mass transfer coefficients at solid interface, m.s^–1
L: reactor length
M: mass of tracer into the fluid entering the reactor, kg
n_resp: number of responses
Q_L: volumetric flow rate of the liquid phase, m³.s^–1
R: gas ideal constant, J.mol^–1.K^–1
r_i: apparent reaction rate of i-th component, mol.m^–3.s^–1
t: time, s
t_avg: average residence time, s
t_i: tracer injection time, s
T_r: reactor temperature, K
u_G: inlet superficial velocity of gas phase, m.s^–1
u_L: inlet superficial velocity of the liquid phase, m.s^–1
V: reactor volume, m³
w_n: weight factor assigned to the n-th response
z: axial dimension, m

Greek Letters

θi: fraction of species adsorbed on catalyst active sites
ν_n: stoichiometric coefficient of the i-th component
ρ_G: density of gas fluid, kg.m^–3
ρ_L: density of liquid fluid, kg.m^–3
μ_G: dynamic viscosity of gas phase, kg.m^–1.s^–1
μ_L: dynamic viscosity of liquid phase, kg.m^–1.s^–1
ΔH_r: reaction enthalpy, kJ.mol^–1

Abbreviations

ULSD: ultra-low-sulfur diesel
HDS: hydrodesulfurization
HYD: hydrogenation
DDS: direct desulfurization
RD: reactive distillation
Micro-TBR: micro trickle bed catalytic reactor
DBT: dibenzothiophene
T: thiophene
BT: benzothiophene
4,6-DMDBT: 4,6-dymetildibenzothiophene
DMDBT: dymetildibenzothiophene
BP: biphenyl
THDBT: tetrahydrodibenzothiophene
CHB: cyclohexylbenzene
BCH: bicyclohexyl. RTD, residence time distribution
GC: gas chromatography
FID: flame ionization detector

References

1. Alsolami, B.H., Berger, R.J., Makkee, M., Moulijn, J.A., 2013. Catalyst performance testing in multiphase systems: implications of using small catalyst particles in hydrodesulfurization. Industrial & Engineering Chemical Research 52, 9069–9085.10.1021/ie4010749Search in Google Scholar

2. Ancheyta, J., Marroquin, G., Angeles, M.J., Macias, M.J., Pitault, I., Forissier, M., Morales, R.D., 2002. Some experimental observations of mass transfer limitations in a trickle-bed hydrotreating pilot reactor. Energy and Fuels 16, 1059–1067.10.1021/ef010280jSearch in Google Scholar

3. Bej, S.K., Dabral, R.P., Gupta, P.C., Mittal, K.K., Sen, G.S., Kapoor, V.K., Dalai, A.K., 2000. Studies on the performance of a microscale trickle bed reactor using different sizes of diluent. Energy and Fuels 14, 701–705.10.1021/ef990238cSearch in Google Scholar

4. Bej, S.K., Dalai, A.K., Maity, S.K., 2001. Effect of diluents size on the performance of a micro-scale fixed bed multiphase reactor in up flow and down flow modes of operation. Catalysis Today 64, 333–345.10.1016/S0920-5861(00)00536-8Search in Google Scholar

5. Bellos, P.D., Papayannakos, N.G., 2003. The use of a three phase microreactor to investigate HDS kinetics. Catalysis Today 79–80, 349–355.10.1016/S0920-5861(03)00062-2Search in Google Scholar

6. Bhaskar, M., Valavarasu, G., Sairam, B., Balaraman, K.S., Balu, K., 2004. Three-phase reactor model to simulate the performance of pilot-plant and industrial trickle-bed reactors sustaining hydrotreating reactions. Industrial and Engineering Chemistry Research 43, 6654–6669.10.1021/ie049642bSearch in Google Scholar

7. Broderick, D.H., Gates, B.C., 1981. Hydrogenolysis and hydrogenation of dibenzothiophene catalyzed by sulfided CoO-MoO/Al2O3: the reaction kinetics. AIChE Journal 27, 663–673.10.1002/aic.690270419Search in Google Scholar

8. Cárdenas-Guerra, J.C., López-Arenas, T., Lobo-Oehmichen, R., Cisneros, E.S., 2010. A reactive distillation process for deep hydrodesulfurization of diesel: multiplicity and operation aspects. Computers and Chemical Engineering Science 34, 196–209.10.1016/j.compchemeng.2009.07.014Search in Google Scholar

9. Castillo-Araiza, C.O., Lopez-Isunza, F., 2008. Hydrodynamic models for packed beds with low tube-to-particle diameter ratio. International Journal of Chemical Reactor Engineering 6, 1–14.10.2202/1542-6580.1550Search in Google Scholar

10. Castillo-Araiza, C.O., Chávez, G., Dutta A., de los Reyes, J.A., Nuñez, S., García-Martínez, J.C., 2015. Role of Pt–Pd/γ-Al2O3 on the HDS of 4,6-DMBT: Kinetic modeling & contribution analysis. Fuel Processing Technology 132, 164–172.10.1016/j.fuproc.2014.12.028Search in Google Scholar

11. Chander, A., Kundu, A., Bej, S.K., Dalai, A.K., Vohra, D.K., 2001. Hydrodynamic characteristics of cocurrent upflow and downflow of gas and liquid in a fixed bed reactor. Fuel 80, 1043–1053.10.1016/S0016-2361(00)00170-8Search in Google Scholar

12. Contreras-Valdez, Z., Mogica Bentancourt, J.C., Alvarez-Hernández, A., Guevara-Lara, A., 2013. Solvent effects on dibenzothiophene hydrodesulfurization: Differences between reactions in liquid or gas phase. Fuel 106, 519–527.10.1016/j.fuel.2012.12.012Search in Google Scholar

13. Cramer, J.A., Morris, R.E., Hammond, M.H., Rose-Pehrsson, S.L., 2009. Ultra-low sulfur diesel classification with near-infrared spectroscopy and partial least squares. Energy and Fuels 23, 1132–1133.10.1021/ef8007739Search in Google Scholar

14. Dean, M.R., Tooke, J.W., 1946. Vapor liquid equilibria in three hydrogen paraffin systems. Industrial & Engineering Chemical Research 38, 389–393.10.1021/ie50436a014Search in Google Scholar

15. Dieselnet, 2015. Diesel Sulfur published online by the National Petrochemical & Refiners Association (NPRA), http://www.dieselnet.com/standards/eu/ld.php.Search in Google Scholar

16. Edvinsson, R., Irandoust, S., 1993. Hydrodesulfurization of dibenzothiophene in a monolithic catalyst reactor. Industrial & Engineering Chemical Research 32, 391–395.10.1021/ie00014a016Search in Google Scholar

17. Finlayson, B.A., 1980. Orthogonal collocation on finite elements progress and potential. Mathematics and Computers in Simulation 22, 11–17.10.1016/0378-4754(80)90097-XSearch in Google Scholar

18. Gaetan M., Jamal, C., Francis, L., 2009. Trickle-bed laboratory reactors for kinetic studies. International Journal of Chemical Reactor Engineering 7, 1–70.10.2202/1542-6580.1730Search in Google Scholar

19. García-Martínez, J.C., Castillo-Araiza, C.O., De los Reyes-Heredia, J.A., Trejo,E., Montesinos,A., 2012.Kinetics of HDS and of the inhibitory effect of quinoline on HDS of 4,6-DMDBT over a NiMoP/Al2O3 catalyst: Part I. Chemical Engineering Journal 210, 53–62.10.1016/j.cej.2012.08.048Search in Google Scholar

20. Gierman, H., 1988. Design of laboratory hydrotreating reactors: Scaling down of trickle-flow reactors. Applied Catalysis 43, 277–286.10.1016/S0166-9834(00)82732-3Search in Google Scholar

21. Girgis, M.J., Gates, B.C., 1991. Reactivities, reaction networks, and kinetics in high pressure catalytic hydroprocessing. Industrial & Engineering Chemical Research 30, 2021–2058.10.1021/ie00057a001Search in Google Scholar

22. Goto, S., Smith, J.M., 1975. Trickle bed reactor performance part i. Holdup and mass transfer effects. AIChE Journal 21, 706–713.10.1002/aic.690210410Search in Google Scholar

23. Harmsen, G.J., Korevaar, G., Lemkowitz, S.M., 2003. Process intensification contributions to sustainable development, Chapter 14, in: Stankiewicz, A., Moulijn, J. (Eds.), Re-engineering the Chemical Processing Plant, Dekker, New York.Search in Google Scholar

24. Harmsen, F.J., 2007. Reactive distillation: The front-runner of industrial process intensification: A full review of commercial applications, research, scale-up, design and operation. Chemical Engineering and Processing: Processes Intensification 46, 774–780.10.1016/j.cep.2007.06.005Search in Google Scholar

25. Hearn, D., Putman, H.M., 1998. HDS process utilizing column realtor. US Pat. No. 5,779,883.Search in Google Scholar

26. Hidalgo-Vivas, A., Towler, G.P., 1998. Distillate hydrotreatment by reactive distillation. AIChE Annual Proceeding.Search in Google Scholar

27. Ishihara, A., Kabe, T., 1993. Deep desulfurization of light oil: Effects of solvents on hydrodesulfurization of dibenzothiophene. Industrial & Engineering Chemical Research 132, 753–755.10.1021/ie00016a026Search in Google Scholar

28. Ishihara, A., Itoh, T., Nomura, M., Qi, P., Kabe, T., 1993. Effects of solvents on deep hydrodesulfurization of benzothiophene and dibenzothiophene. Journal of Catalyst 140, 184–189.10.1006/jcat.1993.1077Search in Google Scholar

29. Kallinikos, L.E., Papayannakos, N.K., 2007. Operation of a miniscale string bed reactor in spiral form at hydrotreatment conditions. Industrial & Engineering Chemical Research 46, 5531–5535.10.1021/ie070309sSearch in Google Scholar

30. Kan, K.M., Greenfield, P.F., 1979. Pressure drop and holdup in two-phase cocurrent trickle flows through beds of small packings. Industrial Engineering Chemistry, Process Design and Development 18, 740–745.10.1021/i260072a027Search in Google Scholar

31. Kooyman, P.J., Rob van Veen, J.A., 2008. The detrimental effect of exposure to air on supported MoS2. Catalysis Today 130, 135–138.10.1016/j.cattod.2007.07.019Search in Google Scholar

32. Korsten, H., Hoffmann, U., 1996. Three-phase reactor model for hydrotreating in pilot trickle-bed reactors. AIChE Journal 42, 1350–1360.10.1002/aic.690420515Search in Google Scholar

33. Letourneur, D., Vrinat, M., Bacaud, R., 1997. Hydrodesulfurization of dibenzothiophene in a micro trickle bed reactor. Studies in Surface and Catalysis 106, 491–497.10.1016/S0167-2991(97)80048-1Search in Google Scholar

34. Letourneur, D., Bacaud, R., Vrinat, M., Scheweich, D., Pitault, I., 1998. Hydrodesulfurization catalyst evaluation in an upflow three-phase microreactor. Industrial & Engineering Chemical Research 37, 2662–2667.10.1021/ie970688xSearch in Google Scholar

35. Levenspiel, O., Smith, W.K., 1957. Notes on the diffusion-type model for the longitudinal mixing of fluids in flow. Chemical Engineering Science 50, 3891–3896.10.1016/0009-2509(96)81817-3Search in Google Scholar

36. Levenspiel, O., 2004. Chemical reaction engineering, 3rd ed. Limusa Wiley.Search in Google Scholar

37. Lewis, A., Overton, M., 2009. Nonsmooth optimization via BFGS. Mathematical Programming 141, 135–16310.1007/s10107-012-0514-2Search in Google Scholar

38. Mears, D.E., 1971a. The role of axial dispersion in trickle-flow laboratory reactors. Chemical Engineering Science 26, 1361–1366.10.1016/0009-2509(71)80056-8Search in Google Scholar

39. Mears, D.E., 1971b. Tests for transport limitations in experimental catalytic reactors. Industrial and Engineering Chemistry, Process Design and Development 10, 541–547.10.1021/i260040a020Search in Google Scholar

40. Mederos, F.S., Rodriguez, M.A., Ancheyta, J., Arce, E., 2006. Dynamic modeling and simulation of catalytic hydrotreating reactors. Energy and Fuels 20, 936–945.10.1021/ef050407vSearch in Google Scholar

41. Mills, P.L., Chaudhari, R.V., 1997. Multiphase catalytic reactor engineering and design for pharmaceuticals and fine chemicals. Catalysis Today 37, 367–404.10.1016/S0920-5861(97)00028-XSearch in Google Scholar

42. Mogica-Betancourt, J.C., Contreras-Valdez, Z., Guevara-Lara, A., 2012. Effects of solvent and inhibition of quinoline in the hydrodesulfurization of dibenzothiophene. Revista Mexicana de Ingeniería Química 11, 447–453.Search in Google Scholar

43. Moysan, J.M., Huron, M.J., Paradowski, H., Vidal, J., 1983. Prediction of the solubility of hydrogen in hydrocarbonsolventsthroughcubicequations of state. Chemical Engineering Science 38, 1085–1092.10.1016/0009-2509(83)80029-3Search in Google Scholar

44. Nigam, K.D.P., Larachi, F., 2002. Liquid back-mixing and mass transfer effects in trickle-bed reactors filled with porous catalyst particles. Chemical Engineering and Processing 41, 365–371.10.1016/S0255-2701(01)00157-XSearch in Google Scholar

45. O’Brien, W.S., Chen, J.W., Nayak, R.V., Carr, G.S., 1986. Catalytic hydrodesulfurization of dibenzothiophene and a coal-derived liquid. Industrial & Engineering Chemical Process 25, 221–229.10.1021/i200032a036Search in Google Scholar

46. Ortega-Domínguez, R.A., Mendoza-Nieto, A., Hernández-Hipólito, P., Garrido-Sánchez, F., Escobar-Aguilar, J., Barri, S.A.I., Chadwick, D., Klimova, T.E., 2015. Influence of Na content on behavior of NiMo catalysts supported on titania nanotubes in hydrodesulfurization. Journal of Catalysis 329, 457–470.10.1016/j.jcat.2015.05.005Search in Google Scholar

47. Perego, C., Peratello, S., 1999. Experimental methods in catalytic kinetics. Catalysis Today 52, 133–145.10.1016/S0920-5861(99)00071-1Search in Google Scholar

48. Ranade, V.V., Chaudhari, R.V., Gunjal, P.R., 2011. Trickled bed reactors, reactor engineering and applications,Elsevier B. V.,Amsterdam, The Netherlands.Search in Google Scholar

49. Rodríguez, M.A., Ancheyta, J., 2004. Modeling of hydrodesulfurization (HDS), hydrodenitrogenation (HDN), and the hydrogenation of aromatics (HDA) in a vacuum gas oil hydrotreater. Energy and Fuels 18, 789–794.10.1021/ef030172sSearch in Google Scholar

50. Rock, K.L., 2002. CDTECH, Selective hydrogenation of MAPD via catalytic distillation, in: ERTC Petrochemical Conference, Amsterdam, 20–22.Search in Google Scholar

51. Sales-Cruz, M., Lobo-Oehmichen, R., López-Arenas, T., Rodríguez-López, V., 2012. Determination of reactive critical points of kinetically controlled reacting mixtures. Chemical Engineering Journal 189–190, 303.10.1016/j.cej.2012.02.019Search in Google Scholar

52. Satterfield, C.N., 1975. Trickle-bed reactors. AIChE Journal 21, 209–228.10.1002/aic.690210202Search in Google Scholar

53. Siirola, J.J., 1996. Industrial applications of chemical process synthesis, in: Anderson,J.L. (Ed.), Advances in Chemical Engineering, Process Synthesis, Academic Press, pp. 23.10.1016/S0065-2377(08)60201-XSearch in Google Scholar

54. Singhal, G.H., Espino, R.L., Sobel, J.E., Huff, G.A., 1981. Hydrodesulfurization of sulfur heterocyclic compounds. Kinetics of dibenzothiophene. Journal of Catalysis 67, 457–468.10.1016/0021-9517(81)90305-5Search in Google Scholar

55. Song, C., 2003. An overview of new approaches to deep desulfurization for ultra-clean gasoline, diesel fuel and jet fuel. Catalysis Today 86, 211–263.10.1016/S0920-5861(03)00412-7Search in Google Scholar

56. Taylor, R., Krishna, R., 2000. Modeling reactive distillation. Chemical Engineering Science 55, 5183–5229.10.1016/S0009-2509(00)00120-2Search in Google Scholar

57. Topsøe, H., Hinneman, B., Norskov, J.K., Lauritsen, J.V., Besenbacher F., Hansen, P.L., Hyotf, G., Egeber, R.G., Knudsen, K.G., 2005. The role of reaction pathways and support interactions in the development of high activity hydrotreating catalysts. Catalysis Today 107–108, 12–22.10.1016/j.cattod.2005.07.165Search in Google Scholar

58. Turaga, U.T., Ma, X., Song, C., 2003. Influence of nitrogen compounds on deep hydrodesulfurization of 4,6-dimethyldibenzothiophene over Al2O3 and MCM 41- Supported Co-Mo sulfide catalysts. Catalysis Today 86, 265–275.10.1016/S0920-5861(03)00464-4Search in Google Scholar

59. Vargas-Villamil, F.D., Marroquin, J.O., de la Paz, C., Rodríguez, E., 2004. A catalytic distillation process for light gas oil hydrodesulfurization. Chemical Engineering and Processing 43, 1309–1316.10.1016/j.cep.2003.12.003Search in Google Scholar

60. Velo, E., Puigjaner, L., Recasens, F., 1988. Inhibition by product in the liquid-phase hydration of isobutene to tert-butyl alcohol: kinetics and equilibrium studies. Industrial and Engineering Chemistry Research 27, 2224–2231.10.1021/ie00084a006Search in Google Scholar

61. Viveros-García, T., Ochoa-Tapia, J.A., Lobo-Oehmichen, R., De los Reyes-Heredia, J.A., Cisneros, E.S., 2005. Conceptual design of a reactive distillation process for ultra-low sulfur diesel production. Chemical Engineering Journal 106, 119–131.10.1016/j.cej.2004.11.008Search in Google Scholar

62. Vrinat, M.L., 1983. The kinetics of the hydrodesulfurization process: a review. Applied Catalysis 6, 137–270.10.1016/0166-9834(83)80260-7Search in Google Scholar

63. Weekman, V.W.J., 1974. Laboratory reactors and their limitations. AIChE Journal 20, 833–840.10.1002/aic.690200502Search in Google Scholar

Published Online: 2015-12-16

Published in Print: 2016-6-1

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Articles in the same Issue

https://doi.org/10.1515/ijcre-2015-0126

Keywords for this article

HDS; reactive distillation; NiMoP/γ-Al2O3, kinetics; pseudo heterogeneous model