Zr改性Ni<sub>2</sub>P/SBA-15催化剂的制备及其加氢脱氧性能

颜子金; 宋华; 李锋; 陈彦广

Zr改性Ni₂P/SBA-15催化剂的制备及其加氢脱氧性能

颜子金¹,
宋华^{1, 2, ,},
李锋^{1, 2},
陈彦广^{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

东北石油大学研究生培养创新实践基地创新科研 YJSCX2017-016NEPU

详细信息

中图分类号: O643.361
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出版历程
- 收稿日期: 2018-03-06
- 修回日期: 2018-05-25
- 网络出版日期: 2021-01-23
- 刊出日期: 2018-07-10

Preparation of Zr modified Ni₂P/SBA-15 catalysts and its hydrodeoxygenation performance

YAN Zi-Jin¹,
SONG Hua^{1, 2
, ,},
LI Feng^{1, 2},
CHEN Yan-guang^{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

Innovative Scientific Research Projects of Innovative Practice Base for Postgraduate Training in Northeast Petroleum University YJSCX2017-016NEPU

More Information

Corresponding author: SONG Hua, E-mail:songhua2004@sina.com

摘要

摘要: 以正丙醇锆（n）和Zr（SO₄）₂（m）为锆源制备了Zr改性的Ni₂P/ZrO₂-SBA-15（n）和Ni₂P/ZrO₂-SBA-15（m）催化剂，并采用XRD、BET、CO吸附、XPS、NH₃程序升温脱附等手段对催化剂进行了表征。以苯并呋喃（BF）为模型化合物，研究了催化剂加氢脱氧（HDO）性能。结果表明，Zr改性后，形成了新的层状结构的ZrP；Zr的引入有助于生成更多、更小粒径的Ni₂P活性相，催化剂的酸强度和酸量均提高。与正丙醇锆相比，Zr（SO₄）₂为锆源能够获得比表面积大、酸性强、酸量大的催化剂，得到更多的ZrP相、更小粒径的Ni₂P晶粒，暴露更多的Ni活性位点。Ni₂P/ZrO₂-SBA-15（n）和Ni₂P/ZrO₂-SBA-15（m）的BF HDO产率分别为71.5%和85.9%，较Ni₂P/SBA-15分别提高了14.0%和28.4%。催化剂HDO活性、脱氧产物选择性和产率大小顺序为：Ni₂P/ZrO₂-SBA-15（m）> Ni₂P/ZrO₂-SBA-15（n）> Ni₂P/SBA-15。
- 加氢脱氧 /
- 磷化镍 /
- 锆 /
- 苯并呋喃
Abstract: Ni₂P/ZrO₂-SBA-15(n) and Ni₂P/ZrO₂-SBA-15(m) catalysts were prepared from n-propoxide zirconium (n) and Zr(SO₄)₂(m) as zirconium sources. The catalysts were characterized by X-ray diffraction (XRD), N₂ adsorption specific surface area measurements (BET), CO uptake, X-ray photoelectron spectroscopy (XPS) and NH₃ temperature programmed desorption (NH₃-TPD). The results show that after Zr modification, a new layered structure of ZrP is formed. The introduction of Zr helps to generate more Ni₂P active phase with smaller crystal size, and increase both the acid strength and acid amount of the catalyst. Compared with zirconium n-propoxide, the catalyst prepared from Zr(SO₄)₂ has larger specific surface area, more acid amount, stronger acidity, more ZrP phases, smaller Ni₂P crystal grains and more Ni active sites. The product yields of benzofuran hydrodeoxygenation (BF HDO) given by Ni₂P/ZrO₂-SBA-15(n) and Ni₂P/ZrO₂-SBA-15(m) were 71.5% and 85.9% respectively, which were increased by 14.0% and 28.4% respectively compared with Ni₂P/SBA-15. The BF HDO activity, selectivity and yield of the BF HDO products decreased in the order of Ni₂P/ZrO₂-SBA-15(m) > Ni₂P/ZrO₂-SBA-15(n) > Ni₂P/SBA-15.
- hydrodeoxygenation /
- Ni₂P /
- zirconium /
- Benzofuran (BF)

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图 1 载体和催化剂的XRD谱图

Figure 1 XRD patterns of the supports and the catalysts

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图 2 载体与催化剂氮气吸附-脱附曲线

Figure 2 N₂ adsorption-desorption isotherms of the supports and the catalysts

(a): the supports; (b): the catalysts

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图 3 载体与催化剂氮气孔径分布

Figure 3 Pore size distributions of the supports and the catalysts

(a): the supports; (b): the catalysts

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图 4 Ni₂P/ZrO₂-SBA-15(m)，Ni₂P/ZrO₂-SBA-15(n)和Ni₂P/SBA-15在Ni(2p)、P(2p)区域和Zr(3d)区域XPS谱图

Figure 4 XPS spectra of Ni₂P/ZrO₂-SBA-15(m), Ni₂P/ZrO₂-SBA-15(n) and Ni₂P/SBA-15 in Ni(2p), P(2p) and Zr(3d) area

(a): Ni 2p electronic core layer; (b): P 2p electronic core layer; (c): Zr 3d electronic core layer

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图 5 Ni₂P/ZrO₂-SBA-15(m), Ni₂P/ZrO₂-SBA-15(n)和Ni₂P/SBA-15催化剂的NH₃-TPD谱图

Figure 5 NH₃-TPD profiles of Ni₂P/ZrO₂-SBA-15(m), Ni₂P/ZrO₂-SBA-15(n) and Ni₂P/SBA-15 catalysts

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图 6 Ni₂P/ZrO₂-SBA-15(n)，Ni₂P/ZrO₂-SBA-15(m)和Ni₂P/SBA-15催化剂的BF转化率

Figure 6 BF conversion of Ni₂P/ZrO₂-SBA-15(n), Ni₂P/ZrO₂-SBA-15(m) and Ni₂P/SBA-15

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图 7 BF HDO反应途径^[20]

Figure 7 BF HDO reaction pathway

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图 8 Ni₂P/ZrO₂-SBA15(m)催化剂的BF的HDO反应路径

Figure 8 Reaction path of BF HDO on Ni₂P/ZrO₂-SBA-15(m)

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表 1 催化剂和载体的结构性质

Table 1 Structural properties of the catalyst and support

Sample	A_BET/(m²·g^-1)	v_p/(cm³·g^-1)	d_BJH^a/nm	d_XRD^b/nm	CO uptake /(μmol·g^-1)	HDO conversion x/%
SBA-15	390	0.59	6.1	-	-	-
Ni₂P/SBA-15	200	0.32	5.3	18.4	38	81.0
ZrO₂-SBA-15(n)	289	0.43	6.0	-	-	-
Ni₂P/ZrO₂-SBA-15(n)	107	0.17	6.3	13.9	43	86.2
ZrO₂-SBA-15(m)	307	0.46	5.9
Ni₂P/ZrO₂-SBA-15(m)	164	0.28	6.8	12.6	44	91.3
d_BJH^a: pore diameter, d≈4v_BJH/A_BET; d_XRD^b : calculated from the D_c=kl/βcos(q) (Scherrer equation) based on the Ni₂P{1 1 1}

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表 2 催化剂样品XPS结合能及表面原子比

Table 2 XPS binding energy and surface atomic ratio of catalyst

Sample	Binding energy E/eV							Superficial atomic ratio
	Ni 2p_3/2		P 2p		Zr 3d			Ni/P	Ni/Si	Ni/Zr
	Ni₂P	Ni²⁺	PO₄^3-	P^δ-	ZrO₂		ZrP	Ni/P	Ni/Si	Ni/Zr
Ni₂P/SBA-15	852.5	856.6	134.6	129.2	-	-	-	1:3.60	1:30
Ni₂P/ZrO₂-SBA-15(n)	852.3	856.1	134.2	129.2	182.9	185.2	191.4	1:3.23	1:24	1:34
Ni₂P/ZrO₂-SBA-15(m)	852.3	856.2	134.3	129.2	183.0	185.3	191.4	1:3.15	1:17	1:38

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表 3 催化剂HDO产物选择性和脱氧产率

Table 3 HDO product selectivity and yield

Sample	Yield w/%
Sample	methylcyc-lohexane	ethyl cyclohexane	ethylbe-nzene	2, 3-dihydrobe-nzofuran	ortho ethyl-phenol	deoxidizati-on product selectivity	deoxidi-zation yield
Ni₂P/SBA-15	13.2	48.7	9.2	10.6	18.3	71.1	57.5
Ni₂P/ZrO₂-SBA-15(n)	12.9	51.2	19.0	10.7	6.2	83.1	71.5
Ni₂P/ZrO₂-SBA-15(m)	14.1	53.1	24.9	6.3	1.6	92.1	85.9

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