HDS. HDS. . (Hydrodesulfurization) HDS. CoMo/γ-Al 2O 3 HDS. nl/l

Μέγεθος: px

Εμφάνιση ξεκινά από τη σελίδα:

Download "HDS. HDS. . (Hydrodesulfurization) HDS. CoMo/γ-Al 2O 3 HDS. nl/l"

ÊΝηρεύς Σπυρόπουλος
7 χρόνια πριν
Προβολές:

1 HDS * - : (RIPI) tajerianm@ripi.ir HDS CoMo/γ-Al 2O 3 - o C (trickle bed).. - h -1 (LHSV) - bar g nl/l (H2/Oil). HDS. HDS.. kj/mol HDS. : HDS -. (Hydrodesulfurization) HDS. H 2 S : [ ] R SH + H 2 R H + H 2S ( ) ١

2 HDS. H 2 S.[ ].. ( ) [ ] HDS -. (HDS). HDS (promoter)..[ ] HDS HDS ( ). (γ ).[ ] [ ] :( ) ٢

3 ..[ ]. (- ppm). HDS ULSD KF-757 Akzo Nobel [] (Ultra Low Sulfur Diesel) (Gas Condensate) HDS..[]... ( ) ( o C) (wt%) (ppm) (vol%) -γ CoMo KF-757 HDS. ( ) ( ). KF (m 2 /g) (cc/g) (A o ) (MPa) (g/cc) ٣

4 KF (mass%) (mass%) - HDS ( ).. ppm : - hr -1 :(LHSV) - bar : - o C :.. (DMDS). HDS - DMDS... H 2 S H 2 S DMDS...[ ] :.(Film Diffusion) (Pore Diffusion). (products) (Reactants).[] (D=1.3 و L=5mm) HDS. (18<mesh<25) (LHSV). ( ) ( ). ( ). HDS (LHSV). ( ). ۴

5 HDS ( ). Conv Percent LHSV(1/hr) Actual size(d=1.3,l=5mm) 18<mesh< Conv Percent LHSV(1/hr) Catalyst 10CC Catalyst 5CC -. HDS -.[] (Arrhenius) [] : (Power Low) ۵

6 dc = kc ( ) dt. n k t C.[16] Plug (axial dispertion) (trickle bed).[] L Mears > 50. dp.[] : ( ).[] ln ( C f / CP ) = k / LHSV : n=1 ( ) : [] ( ) ( ) n 1 n n 1 C p C f C P n 1 1. h k = LHSV ( ) n h 1 ( wt %) 1 HDS k LHSV C f : k = k o exp( E / RT) ( ) R K T kj/mol E k o 1 ( ) ( ) Plug. kj/mol K LHSV.[16]. - h -1 LHSV KF-757 HDS. nl/l o C bar H 2 /Oil. ( ) ( ). HDS. 1 LHSV ( ) ۶

7 Reaction Order n= R 2 = Reaction Order n=1.4 R 2 = /LHSV, h 1/LHSV, h Reaction Order n= R 2 = /LHSV, h - n= n= n= R 2 k o ( ) H LHSV - o 2 /Oil C HDS.. nl/l bar h ( ) E/R ln(k) ( ) T. ( ) ln( k o ) k o. * KJ/mol ٧

8 ln(k) Reaction Order n= y = x /T*1000, K n= - ( HDS) -... HDS. HDS. kj/mol ( )...[] (kj/mol) HDS - Pseudo first ( o C) Bej et al 4 Yui and Ng 33 Diaz-Red et al 3 Yui and sanfond 34 Ferdous et al. 16 ( ). (order of magnitude) ٨

9 1. Yui, S. M. Hydrotreating of Bitumen-Derived Coker Gas Oil: Kinetics of Hydrodesulfurization, Hydrodenitrogenation, and Mild Hydrocracking, and Correlations to Predict Product Yields and Properties. AOSTRA J. Res. 1989, 5, Sanford, E. C.; Yui, S. M. Hydrotreating Characteristics of Coked and of Hydrocracked Gas Oils from Alberta Heavy Bituminous Oils with Commercial Nickel-Molybdenum Catalysts, and Prediction of Some Product Properties. Stud. Surf. Sci. Catal. 1984, 19, Diaz-Real, R. A.; Mann, R. S.; Sambi, I. S. Hydrotreatment of Athabasca Bitumen Derived Gas Oil over Nickel- Molybdenum, Nickel-Tungsten, and Cobalt-Molybdenum Catalysts. Ind. Eng. Chem. Res. 1993, 32, Bej, S. K.; Dalai, A. K.; Adjaye, J. Comparison of Hydrodenitrogenation of Basic and Non Basic Nitrogen Compounds Present in Oil Sands Derived Heavy Gas Oil. Energy Fuels 2001, 15, Whitehurst, D. D.; Takaaki, I.; Mochida, I. Present State of the Art and Future Challenges in the Hydrodesulfurization of Polyaromatic Sulfur Compounds. Adv. Catal.1998, 42, Peil, K.; Galya, L. G.; Marcelin, G. Acid and Catalytic Properties of Nonstoichiometric Alumina Borate. J. Catal. 1989, 115, Wang, W. J.; Chen, Y. W. Alumina-Alumina Borates as Solid Acid Catalysts. Catal. Lett. 1991, 10, Li, C.; Chen, Y. W.; Yang, S. J.; Wu, J. C. Hydrodesulferization Reaction of Atmospheric Gas Oil Over Cobalt- Molybdenum/Alumina- Alumina Borate Catalysts. Ind. Eng. Chem. Res. 1993, 32, Chen, Y. W.; Tsai, C. M.; Li, C. Hydrodesulfurization of Residue Oils Over NiMo/Alumina-Alumina Borate Catalysts: Effect of Boria Content. Ind. Eng. Chem. Res. 1994, 33, Lulic, P. Influence of Additives on Activity of Hydrotreatment Catalysts. Oil Gas Eur. Mag. 2000, 26, DeCanio, C. E.; Weissman, G. J. FT-IR Analysis of Borate-Promoted Ni-Mo/Al2O3 Hydrotreating Catalysts. Colloids Surf., A 1995, 105, Lewandowski, M.; Sarbak, Z. Effect of Boron Addition on Textureand Structure of NiMo/Al2O3 Catalyst. Cryst. Res. Technol. 1997, 32, Lewandowski, M.; Sarbak, Z. The Effect of Boron Addition on Hydrodesulfurization and Hydrodenitrogenation Activity of NiMo/Al2O3 Catalysts. Fuel 2000, 79, Ferdous, D.; Dalai, A. K.; Adjaye, J. A Series of NiMo/Al2O3 Catalysts Containing B and P: Part I. Synthesis and Characterization. Appl. Catal. 2004, 260, Ferdous, D.; Dalai, A. K.; Adjaye, J. A Series of NiMo/Al2O3 Catalysts Containing B and P: Part II. Hydrodenitrogenation and Hydrodesulfurization using Heavy Gas Oil Derived from Athabasca Bitumen. Appl. Catal. 2004, 260, D. Ferdous, A. K. Dalai, and J. Adjaye; Hydrodenitrogenation and Hydrodesulfurization of Heavy Gas Oil Using NiMo/Al2O3 Catalyst Containing Boron: Experimental and Kinetic Studies. Ind. Eng. Chem. Res. 2006, 45, Sun, M.; Prins, R. A Kinetic Investigation of the Effects of Fluorine and Nickel on the HDN of Toluidine on Fully Sulfided Tunsten Sulfide Catalyst. J. Catal. 2001, 203, Bej, S. K.; Dalai, A. K.; Adjaye, J. Kinetics of Hydrodesulfurization of Heavy Gas Oil Derived from Oil-Sands Bitumen. Pet. Sci. Technol. 2002, 20, de Bruijn, A. Testing of HDS Catalysts in Small Trickle Phase Reactors. Proceedings 6th International Congress on Catalysis, Imperial College, London, July, 1976; p van Klinken J.; van Dongen R. H. Catalyst Dilution for Performance of Laboratory Trickle-bed Reactor, Chem. Eng Sci. 1980, 35, Chu, C.-I.; Wang, I. Kinetic Study on Hydrotreating. Ind. Eng.Chem. Process Des. DeV. 1982, 21, Botchewey, C.; Dalai, A. K.; Adjaye, J. Two-Stage Hydrotreating of Athabasca Heavy gas Oil with Interstage Hydrogen sulphide Removal: Effect of Process Conditions and Kinetic Analysis. Ind. Eng. Chem. Res. 2004, 43, Sie, S. T. Reaction Order and Role of Hydrogen Sulfide in Deep Hydrodesulfurization of gas Oils: Consequences for Industrial Reactor Configuration. Fuel Process. Technol. 1999, 61, Knudsen, K. G.; Cooper, B. H.; Topsoe, H. Catalyst and Process Technologies for Ultra Low Sulfur Diesel. Appl. Catal. 1999, 189, Girgis, M. J.; Gates, B. C. Reactivities, Reaction Networks and Kinetics in High-Pressure Catalytic Hydroprocessing. Ind. Eng. Chem. Res. 1991, 30, Leo Alvardo Perea, The effect of solvent on the kinetics and mass transfer resistance for 4,6 DMDBT HDS, Int. J. Chem. Reac. Eng., 2005, 3, A Hiroshi Yamada and Shigeo Goto, Advantages of counter-current operation for Hydrodesulfurization in trickle bed reactors, Korean J. Chem. Eng., 2004, 21(4), Yao Wang, Kinetics of Hydrodesulfurization of Dibenzothiophend catalyzed by sulfided Co-Mo/MCM-41, Ind. Eng. Chem. Res., 2004, 43, A. Marafi, A comparative study of the effect of catalyst type on Hydrotreating kinetic of Kuwaiti atmospheric residue, Energy & Fuels, 2003,17, 661 ٩

10 30. Petr Steiner and Edd A. Blekkan, Catalytic Hydrodesulfurization of a light gas oil over a NiMo catalyst: kinetics of selected sulfur components, Fuel Processing Technology, 2002,79(1), A. Borgna, E. J. M. Hensen, J. A. R. van Veen and J. W. Niemantsverdriet, Intrinsic kinetics of thiophene hydrodesulfurization on a sulfided NiMo/SiO2 planar model catalyst, Journal of Catalysis, 2004, 221(2), Mears, D. E. The Role of Liquid Hold-up and Effective Wetting In the Performance of Trickle-bed Reactors. ACS Monogr. 1974, 133, Yui, S. M.; Ng, S. H. Energy Fuels 1995, 9 (4), Yui, S. M.; Sanford, E. C. Ind. Eng. Chem. Res. 1989, 28 (9), ١٠

Σχετικά έγγραφα

ΠΡΟΣΟΜΟΙΩΣΗ ΔΙΕΡΓΑΣΙΑΣ ΥΔΡΟΓΟΝΟΑΠΟΘΕΙΩΣΗΣ ΜΕΣΑΙΩΝ ΚΛΑΣΜΑΤΩΝ ΤΟΥ ΑΡΓΟΥ ΠΕΤΡΕΛΑΙΟΥ

ΠΡΟΣΟΜΟΙΩΣΗ ΔΙΕΡΓΑΣΙΑΣ ΥΔΡΟΓΟΝΟΑΠΟΘΕΙΩΣΗΣ ΜΕΣΑΙΩΝ ΚΛΑΣΜΑΤΩΝ ΤΟΥ ΑΡΓΟΥ ΠΕΤΡΕΛΑΙΟΥ ΤΕΧΝΟΛΟΓΙΚΟ ΕΚΠΑΙΔΕΥΤΙΚΟ ΙΔΡΥΜΑ ΑΝΑΤΟΛΙΚΗΣ ΜΑΚΕΔΟΝΙΑΣ & ΘΡΑΚΗΣ ΣΧΟΛΗ ΤΕΧΝΟΛΟΓΙΚΩΝ ΕΦΑΡΜΟΓΩΝ ΤΜΗΜΑ ΜΗΧΑΝΙΚΩΝ ΤΕΧΝΟΛΟΓΙΑΣ ΠΕΤΡΕΛΑΙΟΥ ΚΑΙ ΦΥΣΙΚΟΥ ΑΕΡΙΟΥ ΚΑΙ ΜΗΧΑΝΟΛΟΓΩΝ ΜΗΧΑΝΙΚΩΝ ΠΤΥΧΙΑΚΗ ΕΡΓΑΣΙΑ ΠΡΟΣΟΜΟΙΩΣΗ