Preparation of P⁃Modified Beta Zeolite Supported Nickel Catalyst and Its Catalytic Performance in Furfural Hydrogenation

doi:10.12422/j.issn.1006-396X.2026.02.002

Abstract

Abstract:

This study investigates the effect of preparation strategies on the state of active species in Beta zeolite supported P and Ni catalysts,to develop high⁃performance catalysts for the selective hydrogenation of furfural.A series of P⁃modified Beta zeolite supported Ni catalysts were prepared by stepwise introduction of Ni and P through different methods.Various characterization techniques were employed to investigate the state of Ni species,and their catalytic performance in the selective hydrogenation of furfural was evaluated.The results revealed that Ni species introduced via the in⁃situ hydrothermal method were uniformly encapsulated within the zeolite channels.P introduced via mechanical mixing migrated into the channels and interacted with Ni to form Ni2P species during reduction treatment.The high content of Ni2+ in P⁃Ni@Beta indicated a strong metal⁃support interaction.The reaction results demonstrated a blue shift in the C-O stretching frequency,indicating electron transfer from Ni to P,which reduced the electron density around Ni.The reaction results indicated that Ni δ+ species,acting as Lewis acid sites,efficiently promoted the selective hydrogenation of furfural.Under conditions of 110 ℃ and 1 MPa H2,a furfuryl alcohol yield of 68.6% was achieved after 1 h of reaction.

Key words: Beta zeolite, Metal Ni catalyst, Preparation method, Hydrogenation of furfural

摘要：

探究了制备方法对Beta沸石负载磷镍催化剂中活性组分存在状态的影响，进而开发了高效的糠醛选择性加氢催化剂。首先，通过不同方法在Beta沸石上逐步引入Ni和P,制备了Beta沸石负载磷镍催化剂；然后，利用多种手段表征了各催化剂中活性金属Ni组分的存在状态；最后，评价了各催化剂的糠醛选择性加氢反应性能。结果表明，原位水热法引入的Ni物种均匀分布在沸石孔道中，通过机械混合法引入的P在还原过程中进入孔道与Ni作用形成了Ni2P物种；P⁃Ni@Beta中Ni2+的相对含量高，表明其具有较强的金属⁃载体相互作用；P⁃Ni@Beta催化剂中，C-O拉伸频率发生蓝移，表明Ni与P之间的电子相互作用会降低Ni周围的外电子密度；P⁃Ni@Beta催化剂中，Ni δ+作为L酸中心可以高效催化糠醛选择性加氢反应，在温度为110 ℃、H2压力为1 MPa的条件下反应1 h，可获得68.6%的糠醇收率。

关键词: Beta沸石, 金属Ni催化剂, 制备方法, 糠醛加氢

CLC Number:

TQ426

Yitong ZHAO, Meng LIU, Zhijie WU. Preparation of P⁃Modified Beta Zeolite Supported Nickel Catalyst and Its Catalytic Performance in Furfural Hydrogenation[J]. Journal of Petrochemical Universities, 2026, 39(2): 9-20.

赵翌彤, 刘萌, 吴志杰. Beta沸石负载磷镍催化剂的制备及其糠醛加氢性能研究[J]. 石油化工高等学校学报, 2026, 39(2): 9-20.

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URL: https://journal.lnpu.edu.cn/syhg/EN/10.12422/j.issn.1006-396X.2026.02.002

https://journal.lnpu.edu.cn/syhg/EN/Y2026/V39/I2/9

Figures/Tables 15

Fig. 1 Schematic diagram of the preparation process for P?Ni@Beta and P/Ni@Beta

Fig.2 XRD patterns of Beta zeolite supported P and Ni catalysts

Table 1 Elemental composition of Beta zeolite supported P and Ni catalysts

样品	相对结晶度/%	n(SiO₂)/n(Al₂O₃)	w（Ni）/%	w（P）/%	n(Ni)/n(P)
Beta	100	56.5	-	-	-
P⁃Ni@Beta	80	57.3	1.20	0.68	0.9
P/Ni@Beta	79	55.3	1.20	0.61	1.0
P⁃Ni/Beta	78	56.5	1.07	0.73	0.8
P/Ni/Beta	76	56.9	1.09	0.18	3.2

Fig.3 SEM images of Beta zeolite supported P and Ni catalysts

Fig.4 The absorption?desorption isotherm and pore size distribution of Beta zeolite supported P and Ni catalysts

Table 2 Texture properties of Beta zeolite supported P and Ni catalysts

样品	比表面积/（m²·g^-1）			体积/（cm³·g^-1）
样品	总比表面积	外比表面积	微孔比表面积	总体积	微孔体积	介孔体积
Beta	654	154	500	0.29	0.25	0.04
P⁃Ni@Beta	553	163	390	0.32	0.21	0.11
P/Ni@Beta	503	151	352	0.33	0.20	0.13
P⁃Ni/Beta	564	116	448	0.28	0.22	0.06
P/Ni/Beta	589	115	474	0.27	0.23	0.04

Fig.5 TEM images and EDS Mapping of Ni and P for P?Ni@Beta,P/Ni@Beta and P?Ni/Beta

Fig.6 NH3?TPD and FT?IR?Py profiles of Beta,P?Ni@Beta,P/Ni@Beta and P?Ni/Beta

Table 3 Acidity parameters of Beta,P?Ni@Beta,P/Ni@Beta and P?Ni/Beta

样品	弱酸		中强酸		酸量/（mmol·g^-1）
样品	脱附温度/℃	酸量/ （mmol·g^-1）	脱附温度/℃	酸量/ （mmol·g^-1）	总酸量	L酸量	B酸量
Beta	203	0.10	290	0.08	0.18	0.08	0.10
P⁃Ni@Beta	191	0.07	272	0.06	0.13	0.09	0.04
P/Ni@Beta	191	0.08	267	0.07	0.15	0.09	0.06
P⁃Ni/Beta	195	0.09	310	0.07	0.16	0.10	0.06

Fig.7 XPS spectra of each sample after inducing Ni and P

Table 4 The binding energy and relative content of different valence Ni and P in zeolite samples

样品	结合能/eV					相对含量/%
	Ni 2p_3/2		P 2p			Ni ^δ⁺	Ni²⁺	P ^δ-	P	H₂PO $3 -$
	Ni ^δ⁺	Ni²⁺	P ^δ-	P	H₂PO $3 -$	Ni ^δ⁺	Ni²⁺	P ^δ-	P	H₂PO $3 -$
P⁃Ni@Beta	853.7	857.5	129.9	130.5	133.7	51	49	47	31	22
P/Ni@Beta	853.4	857.1	129.9	130.4	133.7	54	46	45	39	16
P⁃Ni/Beta	853.4	857.3	129.9	130.2	133.7	68	32	33	37	30

Table 4 The binding energy and relative content of different valence Ni and P in zeolite samples

样品	结合能/eV					相对含量/%
	Ni 2p_3/2		P 2p			Ni ^δ⁺	Ni²⁺	P ^δ-	P	H₂PO $3 -$
	Ni ^δ⁺	Ni²⁺	P ^δ-	P	H₂PO $3 -$	Ni ^δ⁺	Ni²⁺	P ^δ-	P	H₂PO $3 -$
P⁃Ni@Beta	853.7	857.5	129.9	130.5	133.7	51	49	47	31	22
P/Ni@Beta	853.4	857.1	129.9	130.4	133.7	54	46	45	39	16
P⁃Ni/Beta	853.4	857.3	129.9	130.2	133.7	68	32	33	37	30

Fig.8 FT?IR?CO spectra of each sample after inducing Ni and P

Table 5 Products distribution of furfural hydrogenation with Beta zeolite supported P and Ni catalysts

样品	FF转化率/%	选择性/%				FOL收率/%	碳平衡率/%
样品	FF转化率/%	FOL	THFA	FIE	FDA	FOL收率/%	碳平衡率/%
Beta^a	2.1	22.5	6.8	15.7	53.2	0.5	98.2
P⁃Ni@Beta^a	96.0	71.5	7.2	9.8	10.7	68.6	99.2
P/Ni@Beta^a	85.2	70.7	6.9	9.9	11.7	60.2	99.2
P⁃Ni/Beta^a	53.6	65.6	9.1	10.4	11.1	35.2	96.2
P⁃Ni/Beta^b	72.3	68.2	8.8	10.2	10.8	49.3	98.0

Fig.9 The reaction pathway followed in the FF hydrogenation reaction process[22]

Table 6 Comparison of the catalytic performance of different Ni-based catalysts in the hydrogenation of FF to FOL

催化剂	温度/℃	H₂压力/Pa	溶剂	反应时间/h	FF转化率/%	FOL选择性/%	参考文献
Ni/SiO₂	140	3.4	异丙醇	5.0	67.0	50.0	[23]
Ni₃Fe/SiO₂	140	3.4	甲醇	3.0	99.0	77.0	[23]
NiReO _x /TiO₂	130	3.0	二氧杂环己烷	3.0	100.0	32.0	[24]
Ni/MgO	100	3.0	乙醇	1.0	12.0	32.0	[25]
Ni/TiO₂	140	2.0	异丙醇	6.0	80.0	88.0	[26]
Ni/MgAlO	140	4.0	乙醇	3.0	100.0	25.0	[27]
CuNi/MgAlO	140	4.0	乙醇	3.0	100.0	74.0	[27]
Ni/Al₂O₃	140	4.0	水	4.0	100.0	38.0	[28]
Ni/Ba⁃Al₂O₃	140	4.0	水	4.0	100.0	1.0	[28]
Ni⁃Cu/SiO₂	100	2.0	甲醇	2.0	94.0	64.0	[29]
MgAl⁃0.3⁃NiO _x	90	2.0	水	3.3	100.0	55.0	[30]
NiAlO _x	90	2.0	水	3.3	58.0	96.0	[30]
P⁃Ni@Beta	110	1.0	异丙醇	1.0	96.0	71.5	本文

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