2001EF011. Chunshan Song. : Ni2P/KUSY,in-situ XAFS

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1 21EF11 Chunshan Song : Ni2P/KUSY,in-situ XAFS 1.

2 Pt-Pd (Cat.2) GTL ULSD SFD Cat.1 Aromatics (wt.%) S.T.Oyama 1 (WP) 2 wt% 76 wt% 2 wppm 3 wppm 5 wppm WP Ni-Mo PtPd S<5 ppm S<5 ppm SRGO(LGO) Cat.1 CoMo(NiMo) catalysts S free Cat.2 1 S free Cat.1: Metal-phosphide catalysts S S-free free Cat.2: Noble metal catalysts GTL ppm 1wt.% 1wt.% Sulfur (ppm~wt.%) Japan:S<5ppm(23), EU:S<5ppm(25), US:S<15ppm(26) HDN Rate / 1-9 mol m -2 s HDN 3. HDS WS W N WC WP NiMoS WS2, W2N, WC, WP, and NiMo/Al2O3 (HDS), HDN = 643 K, = 3.1 MPa. HDS Rate / 1-9 mol m -2 s -1

3 BET CO X,XAFS XPS CoMo NiMo 2.2. XAFS XAFS XAFS XAFS (KEK-IMSS-PF) BL7C, 9A 2.3. (F-942) (44 ppm) 8 ppm, (27%) 593 K, 3.9 MPa 2.4. TiP, VP, CrP, Fe3P, Ni3P, Mn3P, MoP, NbP, WP Co2P, Fe2P 25ml.1 g g GC-MS FID SRI861C

4 Reaction Condition Gas flow rate 15 cm 3 /min 4,6-DMDBT Feed Composition 5 ppm S Liquid flow rate 5 cm 3 /h DMDS (Dimethyl disufide) 6 ppm S Temperature 34 o C Quinoline 2 ppm N Pressure 3 atm Tetralin 1 wt% Catalyst loading 7 µmol CO / O 2 uptake basis n-octane.5 wt% Ni2P Ni2P SiO2 Ni2P/ SiO2 (Ni/P = 1/1) Ni-Mo-S/γ-Al2O3 643 K 3.1MPa Ni2P/ SiO2 (Ni/P = 1/1) HDS ( 9 % Ni-Mo-S/γ-Al2O3 76 ) HDN ( 14 % Ni-Mo-S/γ-Al2O3 38 %) K USY Ni2P K USY Ni2P Conversion / % Ni 2 P/SiO 2 Ni-Mo-S/Al 2 O Temperature / o C 4. 2 ppm 4,6-DMDBT (28-37 o C, 3 bar) Ni2P Ni-Mo-S/Al2O3 の 性 性 性 性 ,6-DMDBT conversion / %1 1.Ni2P/USY 1.Ni2P/KUSY 1.Ni2P/SiO2 NiMo-S/Al2O3 1.5Ni2P/KUSY 5 ppm S in feed 35 ppm S in feed CoMo-S/Al2O3 Ni2P/Al2O3 5 4,6 -DMDBT 3.2. K-USY Ni 2 P

5 Ni2P/K-USY > sulfided.3 CoMo/Al2O3.2 Ni2P/SiO in-situ XAFS K-USY Ni2P Ni2P χ(k). -.1 HDA and HDS /% After the reduction Ni 2 P standard Before the reduction HDA and HDS / % Time on stream (h) k / 1 nm -1 r /.1 nm XAFS Ni2P Ni2P/K-USY( ) FT 15 1 HDS S level 5 HDS S level Time on Stream / h % HDS Sulfur % HDA % HDS Sulfur % HDA After the reduction Ni 2 P Time on stream /h 1 2 HDS S level HDA HDA HDA (a) (b) (c) HDA and HDS Ni 2 P/K-USY (a), Ni 2 P/SiO 2 (b), Co-Mo-S-Al 2 O 3 catalysts Reaction temperature = 593 K, P = 3.9 MPa, WHSV = 4 h -1 5 Sulfur /ppm Sulfur ppm Before the reduction

6 /K-USY Ni K-edge XAFS Ni K-edge EXAFS Ni2P Ni2P Ni2P.15 nm Ni2P Ni-P Ni-O Ni-O Ni2P XAFS Ni-P Ni-Ni.22 nm,.26 nm Ni2P Ni2P Ni2P K-USY Ni2P 8 Ni2P Ni2P 1.3 nm N(paritcle)/N(bulk) KUSY SiO 2 Ni-Ni Ni-P Calculated CN for Ni-P Calculated CN for Ni-Ni Ni-P given by XAFS Ni-Ni given by XAFS χ(k).8 (A) (B) (C) k /1nm diameter / nm. 8 (A) (B) XAFS (C) USY SiO2 6 nm K-USY Ni2P in-situ XAFS X Ni K-edge 4mm 99 % X X SiO2 Be [2, 3] VESPEL X in-situ XAFS 2 MPa, 573 K EXAFS 9 EXAFS (A) EXAFS (B) (C) Ni2P

7 HDS k 1 S 4HDMDBT Slow or S S Hydrogenolysis DDS pathway 4,6-DMDBT k 2 Hydrogenation HYD pathway S 6HDMDBT 12HDMDBT Slow Slow 3,3 -DMBP MCHT DMDCH 4,6-DMDBT (HYD) C-S (DDS) [4,5] (DBT) DDS 4,6- (4,6-DMDBT) HYD Ni2P DBT 4,6-DMDBT HDS 4,6-DMDBT HDS HDS Ni2P NiMo CoMo HYD DDS (k1/k2 = 23.2) Ni2P NiMo CoMo 4,6-DMDBT HDS Ni2P/USY 1-MN(1 ) s -1 g cat -1 1-MN s -1 g cat -1 1-MN/4,6-DMDBT.26 NiMo CoMo Ni2P s -1 g cat -1 NiMo CoMo 4,6-DMDBT NiMo CoMo 4,6-DMDBT 4HDMDBT 6HDMDBT

8 (Temperature = 3 ºC, H2 pressure = 2.4 atm) Rate Constant a (1-5 s -1 g cat -1 ) or (s -1 active site -1 ) b NiMo sulfide CoMo sulfide Ni2P/KUSY Ni2P/USY k1+k (8.75) b 34.1 (3.97) b (14.48) b 51.5 (15.15) b k1/k k (6.66) (2.19) 47.2 (13.88) (12.7) k (2.9) (1.78) 2.3 (.6) 8.33 (2.45) Ni2P 4,6 DMDBT Ni2P (HYD) CoMo Ni2P 4-2 [6] C(sp 2 )-N C(sp 3 )-N 1 CH 3 HDN CH 3 ~ > > > N N N H 8 3 C N CH 3 N Ni2P/SiO2 H H H H H CH 3 4-methylpiperidine piperidine 6 3-methylpiperidine 2,6-dimethylpiperidine 2-methylpiperidine 4-methylpiperidine ~ piperidine > 4 3-methylpiperidine > 2,6-dimethylpiperidine > 2 2-methylpiperidine HDN (1) Protonation;(2) Cleavage;(3) SN1; (4)E1; (5) SN2; (6)E2; (7)C-N; (8) Metal Alkyl, (9) Aziridunium Ring Ni2P (5)SN2 (6)E2 HDN conversion / % Temperature / K

9 N α β E2 Mo Ni 2 P SN2 Ni N α HDN 5. K-USY Ni2P HDS Ni2P /K-USY 4,6-DMDBT NiMo CoMo XAFS 1.3 nm Ni2P 4,6-DMDBT HYD [1]W. Li, B. Dhandapani, S. T. Oyama, Chem.Lett., (1998 ) 27; S. T. Oyama, P. Clark,; V. da Silva, E. J. Lede, F. J. Requejo, Journal of Physical Chemistry B, 15 (21 ) [2] B. S. Clausen and H. Topsoe, Catalysis Today, 9, (1991) [3] S. L. Wallen, D. M. Pfund, J. L. Fulton, C. R. Yonker, M. Newville and Y. J. Ma, Rev. Sci. Instrum., 67, (1996) [4] D. H. Broderick and B. C. Gates, AIChE J. 27 (1981) 663. [5] K. Sakanishi, T. Nagamatsu, I. Mochida and D. Whitehurst, J. Mol. Catal. A 155 (2) 11. [6] J. R.Katzer, R. Sivasubramanian, Catal. Rev.-Sci. Eng. 2, (1979), 155. (1) Synthesis, Characterization and Hydrotreating Activity of Several Iron Group Transition Metal Phosphides,X. Wang, P. Clark, S. T. Oyama,J. Catal., 28, (22) (2) Hydrodesulfurization of Petroleum Feedstocks with a New Type of Nonsulfide Hydrotreating Catalyst, S. T. Oyama, X. Wang, F. Requejo, T. Sato, Y. Yoshimura, J. Catal., 29 (22) 1-5. (3) Effect of Phosphorus Content on Nickel Phosphide Catalysts Studied by XAFS and Other Techniques, X. Wang, Y. Lee, S. T. Oyama, K. Bando, F. G. Requejo, J. Catal., 21, (22) (4) Adsorption of Ethylamine on Silica-Supported Nickel Phosphide, S. T. Oyama, X. Wang, R. Radhakrishnan, Stud. Surf. Sci. Catal.,145, (23) (5) Alumina-Supported Molybdenum Phosphide Hydroprocessing Catalysts, P. A. Clark, S. T. Oyama, J. Catal., 218 (23) 78-87,.

10 (6) Novel Catalysts for Advanced Hydroprocessing: Transition Metal Phosphides, S. T. Oyama,J. Catal., 216 (23) (7) In Situ X-Ray Absorption Fine Structure Studies on the Structure of Ni2P Supported on SiO2, T. Kawai, S. Sato, W.-J. Chun, K. Asakura, K. K. Bando, T. Matsui, Y. Yoshimura, T. Kubota, Y. Okamoto, Y.-K. Lee, S. T. Oyama Chem. Lett., 32 (23) (8) Mechanism of Hydrodenitrogenation in Phosphides and Sulfides,. T. Oyama, X. Wang, J. Phys. Chem., 24 in press (?) (9) Hydrodesulfurization of 4,6-Dimethyldibenzothiophene over NiMo, CoMo Sulfide and Ni Phosphide Catalysts: A Kinetic Study on Individual Reaction Pathways, J. H. Kim, X. Ma, C. Song, Y.-K. Lee, S. T. Oyama, J. Catal., 24 in press (?) (1) Recent developments in the in-situ XAFS and related work for the characterization of catalysts in Japan, K.Asakura, Catalysis Survey from Japan, 7 (23) 177. (11) In situ XAFS studies on the structure of nickel phosphide catalyst supported on K-USY, T. Kawai, K. Asakura, K.K.Bando, Y. Yoshimura, S.T. Oyama, Chemistry Letters 32,(23) 156. (12) In situ X-ray absorption fine structure Studies on the Structure of nickel phosphate catalyst supported on SiO2, T.Kawai, K. Asakura, K.K. Bando, Y. Yoshimura, S.T. Oyama, Physica Scripta, in press. (13) Hydrodesulfurization of petroleum feedstocks with a new type of nonsulfide hydrotreating catalyst,s.t.oyama, X.Wang, F.G. Requejo, T.Sato, Y.Yoshimura, J.Catal., 29, (22) 1 5. (14) Ultra deep hydrodesulfurization of gas oils over sulfide and/or noble metal catalysts Y.Yoshimura, M.Toba, H.Farag, K.Sakanishi, Catalysis Survey from Asia, in press (15) A catalyst makes ultralow-sulfur gasoline into a potential H2 source for fuel cells, M.Toba, Y.Yoshimura, Chemical Engineering, in press(?). (16) New Design Approaches to Ultra-Clean Diesel Fuels by Deep Desulfurization and Deep Dearomatization. C. Song, and X. Ma. Applied Catalysis B: Environmental, 41 (23) (17) An Overview of New Approaches to Deep Desulfurization for Ultra-Clean Gasoline, Diesel Fuel and Jet Fuel, C. Song, Catalysis Today, 86 (23) S. T. Oyama, Y. K. Lee, P. Clark, X. Wang, 225th ACS National Meeting, New Orleans, USA, March 23-27, 23. S. T. Oyama, Y. K. Lee, P. Clark, X. Wang, J.-W. Chun, K. Asakura, K. Bando, 18 th North American Catalysis Society Meeting, Cancun, Mexico, June 1-6, 23. S. T. Oyama, Y. K. Lee, P. Clark, Southeastern Catalysis Society Meeting, Ashville, North Carolina, USA, Sept , K. Asakura, K. K. Bando, T. Kawai, Y. Yoshimura, S. T. Oyama, Y. K. Lee, North American Catalysis Society, Cancun, Mexico, K. Asakura, K. K. Bando, T. Kawai, Y. Yoshimura, S. T. Oyama, Y. K. Lee, Catalysis Society of Japan, Tokushima, Japan, K. Asakura, K. K. Bando, T. Kawai, Y. Yoshimura, S. T. Oyama, Y. K. Lee, Catalysis Society of Japan, Osaka, Japan

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

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