0253-2409 2015 03-0338-06 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 1. 163318 2.CPE 834000 3. 157011 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 /2 340 3.0 MPa / 500 2.0 h -1 DBT 100% O643.361 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 163318 China 2.CPE Xinjiang Petroleum Prospecting and Design Research Institute Co. Ltd. Karamay 834000 China 3.Key Laboratory of Cancer Prevention and Treatment of Heilongjiang Province Mudanjiang Medical University Mudanjiang 157011 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 8 390 Cho 9 Ni 2 P Ni 2 P /SiO 2 -HT Ni 2 P /SiO 2 - LT HDS 2014-10-21 2014-12-27 21276048 E-mail songhua2004@ sina.com
3 Ni 2 P /MCM-41 339 HDS 1 1.1 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 -41 210 PH 3 Ni 2+ 10 6 P 2 /1 1 /1 1 /2 1 /3 Ni 2+ H 2 MCM -41 10 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 2 850 10 /min X 2 /1 2θ 32.6 38. 4 41. 7 44. 4 XPS Thermo VG Scientific Sigma Probe Mg Kα C 1s = 2 2.1 H 2 -TPR 1 320 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 /3 180 1.3 kpa 1 h H 2 H 2 - TPR Quantachrome CHEM - 2.2 XRD BET-3000 0.05 g 2 46.9 48.9 Ni 12 P 5 PDF 22-1190 Ni /P Ni 2 P 284.6 ev Ni 2 P P 1.4 P 7 Ni /P 1 /1 2θ 280 ~ 340 3.0 MPa 40.6 44.5 47.1 54.1 54.8 66.1 72.5 74. / 500 2. 0 h -1 5 Ni 2 P PDF 03-0953 GC-14C Ni 2 P Ni 12 P 5 Ni 2 P 2% 1% 97% 11
340 43 2 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 -41 1 012 m 2 /g 0.816 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-41 1 012 0.816 3.2 Ni-P /MCM 2 /1 815 0.584 2.9 Ni-P /MCM 1 /1 616 0.425 2.7 Ni-P /MCM 1 /2 462 0.301 2.5 Ni-P /MCM 1 /3 196 0.113 2.3 2.4 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 852.6 ~ 852.9 ev Ni 2 P Ni δ+ P δ- 134.3 ~ 134.9 ev Ni 2 P PO 3-4 P 5+ 12 13 Ni 2 P 852.6 ev P Ni 2+ 129.3 ev Ni 2 P P δ- 134.7 ev Ni 2 P PO 3-4 P 5+ MCM -41 Ni 2 P 1 /3 Ni /P 856.4 ~ 857.3 ev Ni 2 P 1 /3 P 2p Ni /P P Ni 2+ 3 P 1 /2 XRD BET 2p 129.1 ~ 129.6 ev Ni 2 P 1 /3 P 1 /2 2 Ni 2 P Ni δ+ 856.1 ev Ni 2 P Ni 2 P 2.000 P P P Ni /P Ni /P
3 Ni 2 P /MCM-41 341 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 /1 856.4 852.9 134.9 129.1 0.648 0.083 Ni-P /MCM 1 /2 857.3 852.7 134.8 129.2 0.334 0.097 Ni-P /MCM 1 /3 857.3 852.6 134.3 129.6 0.242 0.081 2.5 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~ 340 3.0 MPa V H 2 /V oil = 500 WHSV = 2.0 h -1 Ni /P = 1 /1 Ni /P = 1 /2 Ni /P = 1 /3
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