Effect of intercalation anions on catalytic performance of hydrotalcite-like precursor Ni-Al2O3 catalyst for levulinic acid hydrogenation

doi:10.11949/0438-1157.20200121

Abstract

Abstract:

Ni₃Al-N-R and Ni₃Al-C-R catalysts with Ni/Al mole ratio of 3∶1 were prepared by using $N O 3 -$ and $C O 3 2 -$ intercalated hydrotalcites as precursors respectively, and their catalytic properties for the hydrogenation of levulinic acid were investigated. The precursors and catalysts were characterized by N₂-physical adsorption, ICP-OES, TG/DTG, XRD, H₂-TPR / TPD, TEM, NH₃-TPD, in-situ Py-FTIR and other characterization methods. The results showed that the intercalation anions played an important effect on the active metal-support interaction, active metal dispersion, surface acid properties, and catalytic performance of catalysts for levulinic acid hydrogenation. The catalyst derived from $C O 3 2 -$ intercalated hydrotalcite exhibited high metal dispersion, rich L acid acidic centers, high CO hydrogenation activity, and high recycle stability. When methanol was used as the solvent at 160℃ and 4 MPa hydrogen pressure for 1 h, the yield of γ-valerolactone could reach 71.8%.

Key words: levulinic acid, Ni-Al₂O₃ catalyst, γ-valerolactone, catalytic hydrogenation

摘要：

分别以 $N O 3 -$ 以及 $C O 3 2 -$ 插层类水滑石为前体制备了Ni/Al摩尔比为3∶1的NiAl-N-R以及NiAl-C-R催化剂，并考察了其催化乙酰丙酸加氢性能。采用N₂-物理吸附、ICP-OES、TG/DTG、XRD、H₂-TPR/TPD、TEM、NH₃-TPD、in-situ Py-FTIR等表征手段对前体及催化剂进行了表征。研究结果表明，类水滑石插层阴离子对催化剂中活性金属-载体相互作用、活性金属分散度、表面酸性质以及催化乙酰丙酸加氢性能有重要影响。以 $C O 3 2 -$ 插层类水滑石为前体的催化剂表现出高的金属分散度、丰富的L酸酸性中心、高的CO加氢活性和高的循环使用稳定性。当以甲醇为溶剂、160℃、4 MPa氢气压力条件下反应1 h时，γ-戊内酯收率可达71.8%。

关键词: 乙酰丙酸, Ni-Al₂O₃催化剂, γ-戊内酯, 催化加氢

CLC Number:

TQ 028.8

Yin ZHANG, Jianjian GUO, Huanjie REN, Juan CHENG, Haitao LI, Jianbing WU, Yongxiang ZHAO. Effect of intercalation anions on catalytic performance of hydrotalcite-like precursor Ni-Al₂O₃ catalyst for levulinic acid hydrogenation[J]. CIESC Journal, 2020, 71(8): 3614-3624.

张因, 郭健健, 任欢杰, 程娟, 李海涛, 武建兵, 赵永祥. 插层阴离子对以类水滑石为前体Ni-Al₂O₃催化剂催化乙酰丙酸加氢性能的影响[J]. 化工学报, 2020, 71(8): 3614-3624.

Figures/Tables 16

Table 1 Composition of NiAl-N-LDH and NiAl-C-LDH

Sample

Ni/Al molar ratio^①

Sample formula^②

Theoretical mass loss on thermal decomposition^③ /%

Mass loss on thermal decomposition measured by TG^④/%

C content^⑤/

%(mass)

N content^⑤/

%(mass)

NiAl-N-LDH

3.05

[Ni_0.753Al_0.247(OH)₂]^0.247[NO₃^-]_0.247?mH₂O

[Ni_0.757Al_0.243(OH)₂]^0.243[CO₃^2-]_0.121?mH₂O

Fig.1 TG-DTG profiles of NiAl-N-LDH and NiAl-C-LDH

Fig.2 FTIR spectra of NiAl-N-LDH and NiAl-C-LDH

Fig.3 XRD patterns of NiAl-N-LDH and NiAl-C-LDH

Table 2 Textural parameters of the catalysts

Catalyst

BET specific surface area/

(m²/g)

Pore volume/ (cm³/g)

Average pore diameter/nm

Total acid sites^①/(μmol/g)

Fig.4 H2-TPR profiles of catalysts

Fig.5 XRD patterns of calcined and reduced catalysts

Fig.6 TEM images of reduced catalysts

Fig.7 Py-FTIR spectra of catalysts

Fig.8 NH3-TPD profiles of catalysts

Fig.9 Reaction pathway for the hydrogenation of LA using alcohols as solvents

Table 3 Catalytic performance of catalysts for the hydrogenation of levulinic acid using different solvents

Catalysts	Solvent	Conversion of LA/%	Selectivity of GVL/%	Yield of GVL/%	TOF_C=O/ min^-1①
NiAl-N-R	methanol methanol	66.6	63.2	42.1	3.45
NiAl-C-R	methanol methanol	86.7	82.9	71.8	4.37
NiAl-N-R	ethanol ethanol	62.9	60.4	37.9	3.11
NiAl-C-R	ethanol ethanol	74.5	86.7	64.6	3.92
NiAl-N-R	propanol propanol	54.5	61.2	33.4	2.74
NiAl-C-R	propanol propanol	67.3	84.8	57.1	3.47
NiAl-N-R	butanol butanol	46.7	62.3	29.1	2.39
NiAl-C-R	butanol butanol	58.9	85.3	50.2	3.05

Fig.10 Hydrogenation of levulinic to γ-valerolactone using alcohols as solvents

Fig.11 Effect of reduction temperatures on catalytic performance of catalysts (Reaction conditions: LA 1.67 g, catalyst 0.1 g, stirrer 400 r/min, reaction temperature 160℃, hydrogen pressure 4 MPa, methanol 40 ml as solvent, reaction time 1 h)

Table 4 Effect of reaction time on catalytic performance of catalysts for hydrogenation of levulinic acid

Catalyst	Reaction time / h	Conversion of LA / %	Selectivity of GVL / %	Yield of GVL / %
NiAl-N-R	0.5	47.1	56.2	26.4
	1.0	66.6	63.2	42.1
	1.5	82.7	68.3	56.5
	2.0	86.2	70.4	60.7
NiAl-C-R	0.5	61.2	77.0	47.2
	1.0	86.7	82.7	71.8
	1.5	95.9	84.8	81.3
	2.0	98.3	85.1	83.7

Fig.12 Effect of recycle times on catalytic performance of catalysts (Reaction conditions: LA 1.67 g, catalyst 0.1 g, stirrer 400 r/min, reaction temperature 160℃, hydrogen pressure 4 MPa, methanol 40 ml as solvent, reaction time 1 h)

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Effect of intercalation anions on catalytic performance of hydrotalcite-like precursor Ni-Al₂O₃ catalyst for levulinic acid hydrogenation

插层阴离子对以类水滑石为前体Ni-Al₂O₃催化剂催化乙酰丙酸加氢性能的影响

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