负载型磷化镍催化剂的空气表面改性法制备及其加氢脱氧性能

宋华; 代雪亚; 宫静; 宋华林; 柳艳修; 李锋

负载型磷化镍催化剂的空气表面改性法制备及其加氢脱氧性能

宋华^1, ,,
代雪亚¹,
宫静¹,
宋华林²,
柳艳修¹,
李锋¹

1.
东北石油大学化学化工学院, 黑龙江大庆 163318
2.
东北石油大学石油与天然气化工省重点实验室, 黑龙江大庆 163318

基金项目:

国家自然科学基金 21276048

黑龙江省自然基金 ZD201201

黑龙江省教育厅面上项目 12541060

详细信息

通讯作者:
宋华, E-mail: songhua2004@sina.com

中图分类号: O643.361
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- 文章访问数: 63
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- 被引次数: 0
出版历程
- 收稿日期: 2016-03-24
- 修回日期: 2016-05-07
- 网络出版日期: 2021-01-23
- 刊出日期: 2016-09-10

Preparation of supported nickel phosphide catalyst by surface modification method and its performance in hydrodeoxygenation

1.
College of Chemistry & Chemical Engineering, Northeast Petroleum University, Daqing 163318, China
2.
Provincial Key Laboratory of Oil & Gas Chemical Technology, Northeast Petroleum University, Daqing 163318, China

Funds:

the National Natural Science Foundation of China 21276048

the Natural Science Foundation of Heilongjiang Province of China ZD201201

the Project of Education Department of Heilongjiang Province 12541060

摘要

摘要: 以MCM-41为载体，采用先前驱体氢气低温（673 K）还原、空气表面改性的方法制备了高活性的Ni₂P/MCM-41催化剂，并采用XRD、BET、SEM、TEM、XPS和CO吸附等手段对催化剂进行了表征。以苯并呋喃（BF）加氢脱氧（HDO）为探针反应，考察了空气表面改性对Ni₂P/MCM-41催化剂结构和HDO性能的影响。结果表明，空气表面改性得到的催化剂，活性相为单一的Ni₂P；空气表面改性能够降低催化剂表面P物种的集聚，有助于小尺寸、高分散的Ni₂P活性相的生成。在573 K、3.0 MPa、质量空速为4.0 h^-1、H₂/油体积比为500的条件下，Ni₂P/MCM-41催化剂上BF转脱氧产物收率高达88%，较程序升温还原法制备的催化剂高50%。
- 表面改性 /
- Ni₂P /
- MCM-41 /
- 苯并呋喃 /
- 加氢脱氧
Abstract: With MCM-41 as support, the supported Ni₂P/MCM-41 catalyst is prepared by first reducing the Ni₂P precursors at low temperature (673 K) and then modifying the surface with air; the as-prepared Ni₂P/MCM-41 catalyst was characterized by X-ray diffraction (XRD), N₂-sorption, scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS) and CO uptake. The catalytic performance of Ni₂P/MCM-41 in hydrodeoxygenation (HDO) of benzofuran (BF) was investigated to elucidate the effect of surface modification with air on the catalyst structure and HDO activity. The results show that pure Ni₂P acts as the active phase on the surface of modified Ni₂P/MCM-41 catalyst; the surface modification can decrease the aggregation of P species and promote the formation of small and highly dispersed Ni₂P active phase. Under 573 K, 3.0 MPa, a weight hourly space velocity of 4.0 h^-1 and a H₂/oil volume ratio of 500, the yield of O-free products reaches 88% for HDO of BF over the modified Ni₂P/MCM-41 catalyst, which is about 50% higher than that over the catalyst prepared by conventional temperature-programmed reduction method.
- surface modification /
- Ni₂P /
- MCM-41 /
- benzofuran (BF) /
- hydrodeoxygenation (HDO)

HTML全文

图 1 Ni₂P-O/M41和Ni₂P-N/M41催化剂及MCM-41载体的XRD谱图

Figure 1 XRD patterns of Ni₂P-O/M41, Ni₂P-N/M41 and MCM-41

下载: 全尺寸图片幻灯片

图 2 催化剂的SEM和TEM照片

Figure 2 SEM images of Ni₂-O/M41(a) and Ni₂P-N/M41(b); TEM images of Ni₂P-N/M41(c) and Ni₂P-O/M41(d)

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图 3 Ni₂P-O/M41和Ni₂P-N/M41在Ni 2p、P 2p和O 1s区域XPS谱图

Figure 3 Ni 2p (a), P 2p (b) and O 1s (c) XPS spectra of the Ni₂P-N/M41 and Ni₂P-O/M41 catalysts

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图 4 催化剂的苯并呋喃HDO活性比较

(493-573 K，3.0 MPa，WHSV=4.0 h^-1，H₂/oil (volume ratio)=500)

Figure 4 Conversion of BF for HDO over various catalysts

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图 5 Ni₂P-N/M41、Ni₂P-O/M41和Ni₂P-N/M41-nr催化剂的脱氧产率

(493-573 K，3.0 MPa，WHSV=4.0 h^-1，H₂/oil (volume ratio)=500)

Figure 5 Yields of O-free compounds for BF HDO over the Ni₂P-N/M41, Ni₂P-O/M41 and Ni₂P-N/M41-nr catalysts

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表 1 MCM-41载体及Ni₂P-O/M41和Ni₂P-N/M41催化剂的性质

Table 1 Textural properties of the MCM-41 support and Ni₂P-O/M41 and Ni₂P-N/M41 catalysts

Sample	A_BET /(m²·g^-1)	v_BJH /(cm³·g^-1)	d^a/nm	CO uptake /(μmol·g^-1)
MCM-41	1 051	0.84	3.2	-
Ni₂P-N/M41	502	0.37	2.9	31
Ni₂P-O/M41	509	0.37	2.9	53
d^a: pore diameter, d≈4v_BJH/A_BET

下载: 导出CSV

表 2 XPS分析得到的光谱学数据

Table 2 Spectral parameters of the catalyst samples from XPS analysis

Sample	Binding energy E/eV								Superficial atomic ratio Ni/P/O
	Ni 2p_3/2		P 2p			O 1s
	Ni²⁺	Ni₂P	PO₄^3-	H₂PO₃^-	Ni₂P		OH^-	H₂O
Ni₂P-N/M41-fresh	856.3	852.3	134.6	133.7	129.2		532.4	-	1:3.16:3.40
Ni₂P-O/M41-fresh	856.3	852.4	134.8	133.8	129.2		532.7	-	1:2.54:4.99

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参考文献(22)

[1]	SERRANO RUIZ J C, DUMESIC J A. Catalytic routes for the convention of biomass into liquid hudrocarbon transportation fuels[J]. Energy Environ Sci, 2011, 4(1): 83-99. doi: 10.1039/C0EE00436G
[2]	HUBER G W, IBORRA S, CORMA A. Synthesis of transportation fuels from biomass: Chemistry, catalysts, and engineering[J]. Chem Rev, 2006, 106(9): 4044-4098. doi: 10.1021/cr068360d
[3]	WANG H M, JONATHAN MALE, WANG Y. Recent advances in hydrotreating of pyrolysis bio-oil and its oxygen-containing model compounds[J]. ACS Catal, 2013, 3(5): 1047-1070. doi: 10.1021/cs400069z
[4]	HUANG Y B, WEI L, ZHAO X H, CHENG S Y, JAMES J, CAO Y H, GU Z G. Upgrading pine sawdust pyrolysis oil to green biofuels by HDO over zinc-assisted Pd/C catalyst[J]. Energy Convers Manage, 2016, 115: 8-16. doi: 10.1016/j.enconman.2016.02.049
[5]	MORTAZA G, RICHARD G, HUA X, FERRAN D M M, ROEL W, WEERAWUT C, MD M H, DANIEL M, LI C Z. Effects of temperature on the hydrotreatment behaviour of pyrolysis bio-oil and coke formation in a continuous hydrotreatment reactor[J]. Fuel Process Technol, 2016, 148: 175-183. doi: 10.1016/j.fuproc.2016.03.002
[6]	PETER M M, HUDSON W P D C, JAN-DIERK G, PETER A J, ANKER D J. Activity and stability of Mo₂C/ZrO₂ as catalyst for hydrodeoxygenation of mixtures of phenol and 1-octanol[J]. J Catal, 2015, 328: 208-215. doi: 10.1016/j.jcat.2015.02.002
[7]	YANG J, ZHAO L, LIU S, WANG Y Y, DAI L Y. High-quality bio-oil from one-pot catalytic hydrocracking of kraft lignin over supported noble metal catalysts in isopropanol system[J]. Bioresour Technol, 2016, 212: 302-310. doi: 10.1016/j.biortech.2016.04.029
[8]	GAUDETTE A F, BURNS A W, HAYES J R, MICA C S, RICHARD H B, TAKELE SEDA, MARK E B. M ssbauer spectroscopy investigation and hydrodesulfurization properties of iron-nickel phosphide catalysts[J]. J Catal, 2010, 272(1): 18-27. doi: 10.1016/j.jcat.2010.03.016
[9]	OYAMA S T. Novel catalysts for advanced hydroprocessing: Transition metal phosphides[J]. J Catal, 2003, 216(1/2): 343-352. https://www.researchgate.net/publication/223031296_Novel_catalysts_for_advanced_hydroprocessing_Transition_metal_phosphides
[10]	LIA X, FENGA J P, GUO J Y, WANG A J, ROEL P, DUAN X P, CHEN Y Y. Preparation of Ni₂P/Al₂O₃ by temperature-programmed reduction of a phosphate precursor with a low P/Ni ratio[J]. J Catal, 2016, 334(1): 116-119.
[11]	宋华, 代敏, 宋华林. Ni₂P加氢脱硫催化剂[J].化学进展, 2012, 24(5): 43-47. SONG Hua, DAI Min, SONG Hua-lin. Ni₂P catalyst for hydrodesulfurization[J]. Prog Chem, 2012, 24(5): 43-47.
[12]	ABU I I, SMITH K J. HDN and HDS of model compounds and light gas oil derived from Athabasca bitumen using supported metal phosphide catalysts[J]. Appl Catal A: Gen, 2007, 328(1): 58-67. doi: 10.1016/j.apcata.2007.05.018
[13]	MOON J S, KIM E G, LEE Y K. Active sites of Ni₂P/SiO₂catalyst for hydrodeoxygenation of guaiacol: A joint XAFS and DFT study[J]. J Catal, 2014, 311: 144-152. doi: 10.1016/j.jcat.2013.11.023
[14]	LEE Y K, SHU Y Y, OYAMA S T. Active phase of a nickel phosphide (Ni₂P) catalyst supported on KUSY zeolite for the hydrodesulfurization of 4, 6-DMDBT[J]. Appl Catal A: Gen, 2007, 322: 191-204. doi: 10.1016/j.apcata.2007.01.007
[15]	宋华, 王紫东, 代敏, 宋华林, 万霞, 李锋. Ni₂P催化剂的低温还原法合成及其HDS性能[J].燃料化学学报, 2014, 42(6): 733-737. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18436.shtml SONG Hua, WANG Zi-dong, DAI Min, SONG Hua-lin, WAN Xia, LI Feng. Preparation of Ni₂P catalysts at low reduction temperature and its HDS performance[J]. J Fuel Chem Technol, 2014, 42(6): 733-737. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18436.shtml
[16]	MELéNDEZ-ORTIZ H I, GARCíA-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, 2012, 38(8): 6353-6358. doi: 10.1016/j.ceramint.2012.05.007
[17]	CECILIA J A, INFANTES-MOLINA E, RODRÍGUEZ-CASTELLÓN A, JIMÉNEZ-LÓPEZ A. A novel method for preparing an active nickel phosphide catalyst for HDS of dibenzothiophene[J]. J Catal, 2009, 263(1): 4-15. doi: 10.1016/j.jcat.2009.02.013
[18]	BUI P, JUAN A C, OYAMA S T, TAKAGAKI A, INFANTES-MOLINA A, ZHAO H Y, LI D, RODRIGUEZ-CASTELLON E, LÓPEZ A J. Studies of the synthesis of transition metal phosphides and their activity in the hydrodeoxygenation of a biofuel model compound[J]. J Catal, 2012, 294: 184-198. doi: 10.1016/j.jcat.2012.07.021
[19]	LAYMAN K A, BUSSELL M E. Infrared spectroscopic investigation of CO adsorption on silica-supported nickel phosphide catalysts[J]. J Phys Chem B, 2004, 108: 10930-10941. doi: 10.1021/jp037101e
[20]	WU S K, LAI P C, LIN Y C. Atmospheric hydrodeoxygenation of guaiacol over alumina-, zirconia-, and silica-supported nickel phosphide catalysts[J]. ACS Sustain Chem Eng, 2013, 1: 349-358. doi: 10.1021/sc300157d
[21]	LIU P, RODRIGUEZ J A. Water-gas-shift reaction on a Ni₂P (001) catalyst: Formation of oxy-phosphides and highly active reaction sites[J]. J Catal, 2009, 262(2): 294-303. doi: 10.1016/j.jcat.2009.01.006
[22]	OKAMOTO H. Hydrodeoxygenation of benzofuran and its oxygenated derivatives (2, 3-dihydrobenzofuran and 2-ethylphenol) over NiMoP/Al₂O₃ catalyst[J]. J Catal, 2009, 353(1): 46-53.