钇和柠檬酸对非负载磷化镍催化剂加氢脱硫性能的影响

doi:10.7503/cjcu20150923

高等学校化学学报 ›› 2016, Vol. 37 ›› Issue (8): 1528.doi: 10.7503/cjcu20150923

钇和柠檬酸对非负载磷化镍催化剂加氢脱硫性能的影响

宋华^1,², 于祺¹, 徐晓伟^1,³, 宋华林⁴(), 姜楠¹, 李锋¹, 陈彦广¹

1. 东北石油大学化学化工学院
2. 石油与天然气化工省重点实验室, 大庆 163318
3. 山东玉皇化工有限公司技术与研发中心, 菏泽 274500
4. 牡丹江医学院黑龙江省高校肿瘤疾病防治重点实验室, 牡丹江 157011

收稿日期:2015-11-30 出版日期:2016-07-13 发布日期:2016-07-13
作者简介:
联系人简介: 宋华林, 男, 博士, 高级工程师, 主要从事催化剂表征方面的研究. E-mail: songhua2004@sina.com
基金资助:
国家自然科学基金(批准号: 21276048)、黑龙江省教育厅面上项目(批准号: 12541060)和东北石油大学研究生创新科研项目(批准号: YJSCX2016-019NEPU)资助

Effect of Yttrium and Citric Acid on the Hydrodesulfurization Performance of Unsupported Nickel Phosphide^†

SONG Hua^1,², YU Qi¹, XU Xiaowei^1,³, SONG Hualin^4,^*(), JIANG Nan¹, LI Feng¹, CHEN Yanguang¹

1. College of Chemistry & Chemical Engineering
2. Provincial Key Laboratory of Oil & Gas Chemical Technology, Northeast Petroleum University, Daqing 163318, China
3. Shandong Yuhuang Chemical Co. Ltd., Heze 274500, China
4. Key Laboratory of Cancer Prevention and Treatment of Heilongjiang Province,Mudanjiang Medical University, Mudanjiang 157011, China

Received:2015-11-30 Online:2016-07-13 Published:2016-07-13
Contact: SONG Hualin E-mail:songhua2004@sina.com
Supported by:
Supported by the National Natural Science Foundation of China(No.21276048), the Project of Education Department of Heilongjiang Province, China(No.12541060) and the Graduate Innovation Project of Northeast Petroleum University, China(No.YJSCX2016-019NEPU)

摘要/Abstract

摘要：

采用传统程序升温(TPR)法制备了稀土金属钇(Y)或柠檬酸(CA)改性及Y和CA同时改性的非负载型Ni₂P催化剂; 采用X射线衍射(XRD)分析、 N₂吸附比表面积(BET)测定、 CO化学吸附分析、 X射线光电子能谱(XPS)和透射电子显微镜(TEM)对催化剂的结构和性质进行了表征; 并考察了Y和CA对催化剂上进行的二苯并噻吩(DBT)加氢脱硫(HDS)反应性能的影响. 结果表明, Y和CA均可促使非晶相Ni_xP_yO_z向磷化镍活性相的转化, 抑制Ni₅P₄杂晶相的形成, 从而促进Ni₂P活性相的生成; 同时能够丰富催化剂的孔道, 抑制催化剂表面磷的富集, 得到更好的孔结构、更高的活性相分散度. Y或CA以及两者同时改性后的催化剂DBT转化率均明显高于Ni-P催化剂. 各催化剂的HDS活性大小顺序为Y-Ni-P-CA>Ni-P-CA>Y-Ni-P>Ni-P. 在340 ℃, 3.0 MPa, 氢油体积比700, 质量空速(WHSV)1.5 h^-1的条件下, Y-Ni-P-CA催化剂的DBT转化率为97%, 比Ni-P催化剂提高了约35%.

关键词: 加氢脱硫, 磷化镍, 钇, 柠檬酸, 二苯并噻吩

Abstract:

The Yttrium(Y), citric acid(CA) and combined Y and CA modified bulk nickel phosphide(Ni-P) catalysts were prepared by temperature programmed reduction(TPR) method. The catalysts were characterized by means of X-ray diffraction(XRD), N₂-adsorption specific surface area measurements(BET), CO chemisorption uptake measurements, X-ray photoelectron spectroscopy(XPS) and transmission electron microscopy(TEM). The effects of Y and CA on catalyst activity for dibenzothiophene(DBT) hydrodesulfurization(HDS) were studied. The results indicated that both Y and CA can promote the transformation from Ni_xP_yO_z amorphous phase to nickel phosphide active phase, suppress the formation of Ni₅P₄ phase and therefore promote the formation of Ni₂P active phase. Addition of Y or CA can increase the surface area and suppress the enrichment of phosphorus on surface, leading to a smaller and highly dispersed active phase particles. The Y, CA and combined Y and CA modified nickel phosphide catalysts were proved to possess higher HDS activity than Ni-P sample. The DBT conversions of catalysts followed the order: Y-Ni-P-CA>Ni-P-CA>Y-Ni-P>Ni-P. At the conditions of 340 ℃, 3.0 MPa, WHSV of 1.5 h^-1 and H₂/oil volume ratio of 700, the DBT conversion of the Y-Ni-P-CA catalyst reached 97%, which is an increase of 35% when compared with that found for bulk Ni-P sample.

Key words: Hydrodesulfurization, Nickel phosphide, Yttrium, Citric acid, Dibenzothiophene

中图分类号:

TrendMD:

宋华, 于祺, 徐晓伟, 宋华林, 姜楠, 李锋, 陈彦广. 钇和柠檬酸对非负载磷化镍催化剂加氢脱硫性能的影响. 高等学校化学学报, 2016, 37(8): 1528.

SONG Hua,YU Qi,XU Xiaowei,SONG Hualin,JIANG Nan,LI Feng,CHEN Yanguang. Effect of Yttrium and Citric Acid on the Hydrodesulfurization Performance of Unsupported Nickel Phosphide^†. Chem. J. Chinese Universities, 2016, 37(8): 1528.

图/表 7

Fig.1 XRD patterns of the Ni-P(a), Y-Ni-P(b), Ni-P-CA(c) and Y-Ni-P-CA(d) catalysts

Table 1 Structural data of the Ni-P, Y-Ni-P, Ni-P-CA and Y-Ni-P-CA catalysts

Catalyst	S_BET/(m²·g^-1)	V_p/(cm³·g^-1)	D/nm	CO uptake/(μmol·g^-1)	10³ TOF/s^-1
Ni-P	6.1	0.025	16.2	171	8.5
Y-Ni-P	12.9	0.070	21.8	287	7.4
Ni-P-CA	56.5	0.192	13.3	328	6.8
Y-Ni-P-CA	42.5	0.164	15.2	343	6.5

Table 2 Spectral parameters obtained by XPS analysis

Sample	E_b/eV						Superficial molar ratio
Sample	Ni^δ⁺	Ni²⁺	Satellite	P^δ^-	P⁵⁺	P(complexing)	$N i δ + / ∑ Ni$	P/Ni
Ni-P	852.7	856.7	861.2	128.8	134.8		0.041	3.0
Y-Ni-P	852.5	856.1	860.8	129.0	134.5		0.048	2.7
Ni-P-CA	851.9	855.0	859.8	129.2	133.4	136.8	0.343	2.4
Y-Ni-P-CA	852.6	855.9	861.0	130.4	134.9	136.2	0.320	2.3

Table 2 Spectral parameters obtained by XPS analysis

Sample	E_b/eV						Superficial molar ratio
Sample	Ni^δ⁺	Ni²⁺	Satellite	P^δ^-	P⁵⁺	P(complexing)	$N i δ + / ∑ Ni$	P/Ni
Ni-P	852.7	856.7	861.2	128.8	134.8		0.041	3.0
Y-Ni-P	852.5	856.1	860.8	129.0	134.5		0.048	2.7
Ni-P-CA	851.9	855.0	859.8	129.2	133.4	136.8	0.343	2.4
Y-Ni-P-CA	852.6	855.9	861.0	130.4	134.9	136.2	0.320	2.3

Fig.2 XPS spectra of the Ni-P(a), Y-Ni-P(b), Ni-P-CA(c) and Y-Ni-P-CA(d) catalysts (A) Ni2p core level of spectra; (B) P2p core level of spectra.

Fig.3 TEM images of the Ni-P(A, A'), Y-Ni-P(B, B'), Ni-P-CA(C, C') and Y-Ni-P-CA(D, D') catalysts

Fig.4 HDS activity of the Ni-P, Y-Ni-P, Ni-P-CA and Y-Ni-P-CA catalyst 340 ℃; 3.0 MPa; V(H2)/V(oil)=700; WHSV=1.5 h-1.

Fig.5 HDS selectivity of the Ni-P, Y-Ni-P, Ni-P-CA and Y-Ni-P-CA catalysts Conditions: 340 ℃, 3.0 MPa, V(H2)/V(oil)=700, WHSV=1.5 h-1.

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钇和柠檬酸对非负载磷化镍催化剂加氢脱硫性能的影响

Effect of Yttrium and Citric Acid on the Hydrodesulfurization Performance of Unsupported Nickel Phosphide^†

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钇和柠檬酸对非负载磷化镍催化剂加氢脱硫性能的影响

Effect of Yttrium and Citric Acid on the Hydrodesulfurization Performance of Unsupported Nickel Phosphide†

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Effect of Yttrium and Citric Acid on the Hydrodesulfurization Performance of Unsupported Nickel Phosphide^†