制备方法对稀土金属钇改性Ni<sub>2</sub>P催化剂结构及其加氢脱硫性能的影响

陈茂森; 宋华; 李锋; 陈彦广; 张建

制备方法对稀土金属钇改性Ni₂P催化剂结构及其加氢脱硫性能的影响

陈茂森¹,
宋华^{1, 2, ,},
李锋^{1, 2},
陈彦广^{1, 2},
张建^{1, 2}

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

黑龙江省自然科学基金 ZD201201

黑龙江省教育厅项目 12541060

详细信息

通讯作者:
E-mail:songhua2004@sina.com

中图分类号: O643.361
计量
- 文章访问数: 82
- HTML全文浏览量: 18
- PDF下载量: 5
- 被引次数: 0
出版历程
- 收稿日期: 2016-09-27
- 修回日期: 2016-11-07
- 网络出版日期: 2021-01-23
- 刊出日期: 2017-02-10

Effect of preparation method on the structure of rare earth metal Y modified Ni₂P catalysts and its HDS performance

CHEN Mao-sen¹,
SONG Hua^{1, 2
, ,},
LI Feng^{1, 2},
CHEN Yan-guang^{1, 2},
ZHANG Jian^{1, 2}

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:

National Natural Science Foundation of China 21276048

the Natural Science Foundation of Heilongjiang Province of China ZD201201

the General Program of Education Department of Heilongjiang Province 12541060

摘要

摘要: 采用一步法和分步法制备了钇（Y）改性的非负载型Y_x-Ni₂P催化剂（x为Y和Ni的物质的量比），并采用X射线衍射（XRD）、N₂吸附比表面积（BET）测定、X射线光电子能谱（XPS）技术对催化剂的结构和性质进行了表征。以二苯并噻吩（DBT）为模型化合物，研究了制备方法对Y_x-Ni₂P催化剂加氢脱硫（HDS）性能的影响。结果表明，Y改性可以抑制Ni₅P₄杂晶相的生成，促进Ni₂P活性相的生成，能显著提高催化剂的比表面积和孔容，从而有效提高磷化镍催化剂的HDS活性。Y/Ni物质的量比为0.10时，两种方法制备的催化剂均具有最高的HDS活性。与分步法相比，一步法制备得到的催化剂具有更大的比表面积和孔容，更小的表面P/Ni物质的量比，更高的CO吸附容量，暴露出更多的Ni活性位点，从而具有更高的HDS活性。在340℃，3.0 MPa，H₂/油体积比为700，质量空速（WHSV）1.5 h^-1的条件下，一步法制得的Y_0.10-Ni₂P催化剂上DBT HDS转化率达到97.7%，与分步法制备的Y_0.10-Ni₂P催化剂相比（92.3%），HDS活性提高了5.4%。
- 一步法 /
- 分步法 /
- 加氢脱硫 /
- 磷化镍 /
- 钇 /
- 二苯并噻吩
Abstract: The yttrium (Y) modified unsupported Y_x-Ni₂P catalysts were prepared by one step method and stepwise method (x refers to mol ratio of Y to Ni), respectively.The catalysts were characterized by X-ray diffraction (XRD), N₂adsorption specific surface area measurements (BET), CO uptake and X-ray photoelectron spectroscopy (XPS).The effects of preparation methods on thehydrodesulfurization (HDS) property of the catalysts were investigated by using dibenzothiophene (DBT) as the model compound.The results show that the addition of Y can suppress the formation of Ni₅P₄ phase and thus promote the formation of active Ni₂P phase.The addition of Y can dramatically increase the surface area and pore volume, effectively improve the HDS activity of nickel phosphide catalyst.The Y_x-Ni₂P catalysts prepared by these two methods with Y/Ni mol ratio of 0.10 exhibited the highest HDS activity.As compared to the stepwise method, the one step method which obtained catalysts possessed a larger specific surface area with high pore volume, a lower surface P/Ni mol ratio, a larger CO uptake and more exposed active Ni sites as compared to stepwise method.As a result, it showed a higher HDS activity.At a temperature of 340℃, a pressure of 3.0 MPa, a H₂/oil volume ratio of 700 and a weight hourly space velocity (WHSV) of 1.5 h^-1, the conversion of DBT over Y_0.10-Ni₂P catalyst prepared by one step method reached 97.7%, which was an increase of 5.4% comparing with the Y_0.10-Ni₂P catalyst prepared by stepwise method (92.3%).
- one step method /
- stepwise method /
- hydrodesulfurization /
- nickel phosphide /
- yttrium /
- dibenzothiophene

HTML全文

图 1 Ni₂P、Y_x-Ni₂P-G和Y_x-Ni₂P-F催化剂的XRD谱图

Figure 1 XRD patterns of the Ni₂P,Y_x-Ni₂P-G and Y_x-Ni₂P-F catalysts

下载: 全尺寸图片幻灯片

图 2 Ni₂P、Y_x-Ni₂P-G和Y_x-Ni₂P-F催化剂的N₂ 吸附-脱附曲线

Figure 2 N₂ adsorption-desorption isotherms of Ni₂P, Y_x-Ni₂P-G and Y_x-Ni₂P-F catalysts

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图 3 Ni₂P、Y_x-Ni₂P-G和Y_x-Ni₂P-F催化剂的XPS谱图

Figure 3 XPS spectra of the Ni₂P,Y_x-Ni₂P-G and Y_x-Ni₂P-F catalysts

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图 4 Ni₂P、Y_x-Ni₂P-G和Y_x-Ni₂P-F 催化剂的HDS活性

(3.0 MPa,H₂/oil(volume ratio)=700,WHSV=1.5 h^-1)

Figure 4 HDS activity of the Ni₂P,Y_x-Ni₂P-G and Y_x-Ni₂P-F catalysts

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图 5 Ni₂P、Y_x-Ni₂P-G和Y_x-Ni₂P-F 催化剂的HDS选择性

(3.0 MPa,H₂/oil(volume ratio)=700,WHSV=1.5 h^-1) : Y_0.10-Ni₂P-F : Y_0.01-Ni₂P-F : Ni₂P : Y_0.10-Ni₂P-G : Y_0.01-Ni₂P-G

Figure 5 HDS selectivity of the Ni₂P,Y_x-Ni₂P-G and Y_x-Ni₂P-F catalysts

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表 1 Ni₂P、Y_x-Ni₂P-G和Y_x-Ni₂P-F催化剂的表面结构和CO吸附性能

Table 1 Textural properties and CO uptake of the Ni₂P,Y_x-Ni₂P-G and Y_x-Ni₂P-F catalysts

Sample	A_BET/(m²·g^-1)	v_p/(cm³·g^-1)	d/nm	CO uptake /(μmol·g^-1)
Ni₂P	10	0.069	27.7	171
Y_0.01-Ni₂P-F	11	0.074	27.7	240
Y_0.10-Ni₂P-F	14	0.089	24.9	314
Y_0.01-Ni₂P-G	12	0.072	26.7	280
Y_0.10-Ni₂P-G	25	0.122	19.8	332

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表 2 Ni₂P、Y_x-Ni₂P-G和Y_x-Ni₂P-F催化剂的结合能

Table 2 XPS spectral parameters of the Ni₂P,Y_x-Ni₂P-G and Y_x-Ni₂P-F catalysts

Sample	Binding energy E/eV					P/Ni (mol ratio)
	Ni 2p_3/2			P 2p
	Ni^δ+	Ni²⁺	satellite	P⁵⁺	P^δ-
Ni₂P	852.7	856.7	861.2	134.8	128.8	3.0
Y_0.10-Ni₂P-F	852.6	856.6	860.9	134.6	130.3	2.4
Y_0.10-Ni₂P-G	852.5	856.5	860.8	134.5	128.6	1.4

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