3 Ni 2 P /MCM HDS H 2 -TPR NiCl 2 /MCM 25% ~ 28% Ni 2+ Ni 390 a b ~ e 210 Aladdin chemistry Co. Ltd AccuStandard Inc. USA 1.2 MCM

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1 Ni 2 P /MCM-41 宋华 1, 姜楠 1, 宋华林 3, 李锋 1, 代敏 1,2, 万霞 1,2 1, 徐晓伟 CPE MCM-41 Ni 2 P /MCM-41 H 2 H 2 -TPR X XRD N 2 BET X XPS 1% DBT HDS 1 /2 1 /3 390 Ni 2 P Ni /P 1 / MPa / h -1 DBT 100% O A 43 Effect of Ni /P mol ratio on structure and performance of hydrodesulfurization of Ni 2 P /MCM-41 catalyst SONG Hua 1 JIANG Nan 1 SONG Hua-Lin 3 LI Feng 1 DAI Min 1 2 WAN Xia 1 2 XU Xiao-Wei 1 1.Provincial Key Laboratory of Oil & Gas Chemical Technology Northeast Petroleum University Daqing China 2.CPE Xinjiang Petroleum Prospecting and Design Research Institute Co. Ltd. Karamay China 3.Key Laboratory of Cancer Prevention and Treatment of Heilongjiang Province Mudanjiang Medical University Mudanjiang China Abstract This paper introduces a simple and mild route to prepare Ni 2 P catalysts. Ni 2 P /MCM -41 catalysts were successfully prepared using MCM -41 as the support. The catalysts were characterized by H 2 temperature program reduction H 2 -TPR X-ray diffraction XRD N 2 -adsorption specific surface area measurements BET and X-ray photoelectron spectroscopy XPS analysis. The effects of initial Ni /P molar ratio on hydrodesulfurization HDS performance of catalysts and catalyst stability were studied with a lab-scale continuous flow type fixedbed reactor systemusing a feed containing 1% dibenzothiophene DBT in decahydronaphthalene. The results indicated that a pure Ni 2 P phase was obtained when the initial Ni /P molar ratios were 1 /2 and 1 /3. The catalyst prepared with initial Ni /P mol ratios of 1 /2 exhibited the highest activity. At a reaction temperature of 340 a pressure of 3.0 MPa a H 2 /oil volume ratio of 500 and a weight hourly space velocity WHSV of 2.0 h -1 the HDS conversion was close to 100%. Key words hydrodesulfurization nickel phosphide ammonium hypophosphite nickel chloride dibenzothiophene Ni 2 P 1 2 Ni 2 P 3~ 5 Oyama 7 H 2 -TPR 6 Ni 2 P Guan Cho 9 Ni 2 P Ni 2 P /SiO 2 -HT Ni 2 P /SiO 2 - LT HDS songhua2004@ sina.com

2 3 Ni 2 P /MCM HDS H 2 -TPR NiCl 2 /MCM 25% ~ 28% Ni 2+ Ni 390 a b ~ e 210 Aladdin chemistry Co. Ltd AccuStandard Inc. USA 1.2 MCM PH 3 Ni P 2 /1 1 /1 1 /2 1 /3 Ni 2+ H 2 MCM h 390 H 2 2 h O 2 /N 2 O 2 0.5% 2 h Ni 12% Ni-P /MCM x x Ni /P 1.3 X XRD D /max-2200pc X Cu Kα 40 kv 30 ma 10 /min 10 ~ 80 BET Quantachrome NOVA2000e -196 a NiCl 2 /MCM b Ni-P /MCM 2/1 c Ni-P /MCM 1/1 30 ml /min 5% H 2 /Ar XRD /min X 2 /1 2θ XPS Thermo VG Scientific Sigma Probe Mg Kα C 1s = H 2 -TPR H 2 Ni /P 2 /1 390 H 2 Ni 2+ 1 H 2 -TPR Figure 1 H 2 -TPR curves of the catalyst precursors d Ni-P /MCM 1 /2 e Ni-P /MCM 1 / kpa 1 h H 2 H 2 - TPR Quantachrome CHEM XRD BET g Ni 12 P 5 PDF Ni /P Ni 2 P ev Ni 2 P P 1.4 P 7 Ni /P 1 /1 2θ 280 ~ MPa / h -1 5 Ni 2 P PDF GC-14C Ni 2 P Ni 12 P 5 Ni 2 P 2% 1% 97% 11

3 prepared with different initial Ni / P mol ratios a Ni /P = 2 /1 b Ni /P = 1 /1 c Ni /P = 1 /2 d Ni /P = 1 /3 1 /2 1 /3 XRD Ni 2 P Ni / P 1 / 2 Ni 2 P 1 /3 P Ni 2 P 2.3 BET 1 MCM -41 MCM m 2 /g cm 3 /g Ni /P XRD 1 /2 Ni /P Figure 2 XRD patterns of the catalysts 1 /3 462 m 2 /g 196 m 2 /g P 1 P /Ni Table 1 Textual characterization of supports and catalysts Sample BET area A / m 2 g -1 Pore volume v / cm 3 g -1 Average pore diameter d /nm MCM Ni-P /MCM 2 / Ni-P /MCM 1 / Ni-P /MCM 1 / Ni-P /MCM 1 / XPS 14 Ni 2 P XPS 3 1 /1 Ni 2p P 2p P 2 3 Ni 2p Ni Ni 2 P 2p 3/2 Ni 2p 1/2 1 /2 Ni 2p ~ ev Ni 2 P Ni δ+ P δ ~ ev Ni 2 P PO 3-4 P Ni 2 P ev P Ni ev Ni 2 P P δ ev Ni 2 P PO 3-4 P 5+ MCM -41 Ni 2 P 1 /3 Ni /P ~ ev Ni 2 P 1 /3 P 2p Ni /P P Ni 2+ 3 P 1 /2 XRD BET 2p ~ ev Ni 2 P 1 /3 P 1 /2 2 Ni 2 P Ni δ ev Ni 2 P Ni 2 P P P P Ni /P Ni /P

4 3 Ni 2 P /MCM Ni 2 P 2 P Oyama 7 1 /2 Ni /Si PH 3 1 /2 P Si Ni 2 P Ni /Si Figure 3 3 XPS XPS spectra of the catalysts prepared with different initial Ni / P mol ratios a Ni /P = 1 /1 b Ni /P = 1 /2 c Ni /P = 1 /3 2 XPS Table 2 Spectral parameters obtained by XPS analysis Binding energy E /ev Sample Ni 2p 3/2 P 2p Superficial mol ratio Ni 2+ Ni 2 P 3- PO 4 Ni 2 P Ni /P Ni /Si Ni-P /MCM 1 / Ni-P /MCM 1 / Ni-P /MCM 1 / HDS HDS 4 Figure 4 4 HDS HDS activity and selectivity of the catalysts with different initial Ni / P molar ratios for different reaction temperatures a conversion b selectivity 280~ MPa V H 2 /V oil = 500 WHSV = 2.0 h -1 Ni /P = 1 /1 Ni /P = 1 /2 Ni /P = 1 /3

5 HDS 120 h 6 h 340 Ni /P 1 /2 1 /3 100% Ni 2 P DBT NiP x S y 7 Ni 2 P NiP x S y 1 /1 6 h 99% 114 h HDS 1 /2 1 /3 99% Ni 2 P Ni 2 P /MCM /2 1 / /2 1 /3 H 2 DBT HDS DDS 15 HYD DBT Ni-P /MCM 1 /2 DBT HDS CHB BP Figure 5 Conversion of DBT vs CHB Ni 2 P DBT HDS reaction time on Ni-P /MCM 1 /2 catalyst MPa V H DDS Ni 2 P 2 /V oil = 500 WHSV = 2.0 h -1 I 1 / HDS Ni HDS 3 MCM -41 Ni I II DDS Ni 2 P /MCM -41 Ni I HYD Ni II 17 DBT HDS BP DBT Ni 2 P Ni Ni /P 1 /2 1 /3 2 CHB Ni /P 390 Ni 2 P Ni /P 1 /1 1 /3 Ni 2 1 /3 P P Oyama 1 Ni 2 P XPS Ni /P Ni II Ni I 1 /2 Ni /Si DDS HYD 1 / XPS 1 /2 2 HDS Ni /Si MPa / h h HDS 2.6 HDS 100% 5 DBT Ni -P / MCM 1 / 2 1 OYAMA S T. Novel catalysts for advanced hydroprocessing Transition metal phosphides J. J Catal / J

6 3 Ni 2 P /MCM REN Jun WANG Jian-guo LI Jun-feng Li Yong-wang. Density functional theory study on cystal nickel phosphides J. J Fuel Chem Technol Ni 2 P /TiO 2 J YU Xi-zhi WANG Yuan-qiang CHEN Chang-lin XU Nan-ping WANG Yan-ru. Preparation of Ni 2 P /TiO 2 catalyst and its reactivity for benzene hydrogenation J. J Fuel Chem Technol SONG L M ZHANG S J WEI Q W. A new route for synthesizing nickel phosphide catalysts with high hydrodesulfurization activity based on sodium dihydrogenphosphite J. Catal Commun GUAN Q X LI W ZHANG M H TAO K Y. Alternative synthesis of bulk and supported nickel phosphide from the thermal decomposition of hypophosphites J. J Catal Ni 2 P HDS J SONG Hua WANG Zi-Dong DAI Min. Preparation of Ni 2 P catalysts at low reduction temperature and its HDS performance J. J Fuel Chem Technol OYAMA S T WANG X LEE Y. Effect of phosphorus content in nickel phosphide catalysts studied by XAFS and other techniques J. J Catal GUAN J WANG Y QIN M L YANG Y LI X WANG A J. Synthesis of transition-metal phosphides from oxidic precursors by reduction in hydrogen plasma J. J Solid State Chem CHO K S SEO H R LEE Y K. A new synthesis of highly active Ni 2 P/Al 2 O 3 catalyst by liquid phase phosphidation for deep hydrodesulfurization J. Catal Commun MELENDEZ-ORTIZ H I GARCIA-CERDA L A OLIVARES-MALDONADO Y CASTRUITA G MERCADO-SILVA J A PERERA- MERCADO Y A. Preparation of spherical MCM-41 molecular sieve at room temperature Influence of the synthesis conditions in the structural properties J. Ceram Int SONG H DAI M GUO Y T. Preparation of composite TiO 2 -Al 2 O 3 supported nickel phosphide hydrotreating catalysts and catalytic activity for hydrodesulfurization of dibenzothiophene J. Fuel Process Technol SAWHILL S J PHILLIPS D C BUSSELL M E. Thiophene hydrodesulfurization over supported nickel phosphide catalysts J. J Catal Ni 2 P /TiO 2 -Al 2 O 3 J SONG Hua ZHANG Yong-jiang SONG Hua-lin DAI Min. Effect of citric acid on the hydrodesulfurization performance of Ni 2 P /TiO 2 -Al 2 O 3 catalyst J. Acta Phys-Chim Sin CECILIA J A INFANTEST-MOLINA A RODRIGUEZ-CASTELLON E. A novel method for preparing an active nickel phosphide catalyst for HDS of dibenzothiophene J. J Catal SUN F X WU W C WU Z L. Dibenzothiophene hydrodesulfurization activity and surface sites of silica-supported MoP Ni 2 P and NiMoP catalysts J. J Catal TiO 2 -Al 2 O 3 Ni 2 P /TiO 2 -Al 2 O 3 J SONG Hua YU Hong-kun WU Xian-chun. Preparation of TiO 2 -Al 2 O 3 support and simultaneous hydrodesulfurization and hydrodenitrogenation over Ni 2 P /TiO 2 -Al 2 O 3 catalyst J. Chin J Catal OYAMA S T LEE Y K. The active site of nickel phosphide catalysts for the hydrodesulfurization of 4 6-DMDBT J. J Catal

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