Ni/Al<sub>2</sub>O<sub>3</sub>催化2-甲基呋喃加氢制2-甲基四氢呋喃性能的研究

李增杰; 黄玉辉; 朱明; 陈晓蓉; 梅华

Ni/Al₂O₃催化2-甲基呋喃加氢制2-甲基四氢呋喃性能的研究

李增杰¹,
黄玉辉¹,
朱明^{1, 2, ,},
陈晓蓉^{1, 2},
梅华^{1, 2}

1.
南京工业大学化工学院, 江苏南京 210009
2.
南京(诺盟化工)催化氢化工程技术研究中心, 江苏南京 210009

详细信息

本文的英文电子版由Elsevier出版社在ScienceDirect上出版(http://www.sciencedirect.com/science/journal/18725813)
中图分类号: O643.88
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出版历程
- 收稿日期: 2017-09-27
- 修回日期: 2017-11-27
- 网络出版日期: 2021-01-23
- 刊出日期: 2018-01-10

Catalytic performance of Ni/Al₂O₃ catalyst for hydrogenation of 2-methylfuran to 2-methyltetrahydrofuran

LI Zeng-jie¹,
HUANG Yu-hui¹,
ZHU Ming^{1, 2
, ,},
CHEN Xiao-rong^{1, 2},
MEI Hua^{1, 2}

1.
College of Chemistry and Chemical Engineering, Nanjing University of Technology, Nanjing 210009, China
2.
Catalytic Hydrogenation Engineering Technology Research Center, Nuomeng Chem, Nanjing 210009, China

More Information

Corresponding author: ZHU Ming, Tel: 18205182971, E-mail: mingzhu84@njtech.edu.cn

摘要

摘要: 采用浸渍法制备了不同NiO含量的Ni/Al₂O₃催化剂，并进行了2-甲基呋喃加氢制2-甲基四氢呋喃性能的考察。结果表明，在制备的NiO负载量为10%、20%、25%、30%和40%的Ni/Al₂O₃催化剂中，随着NiO负载量增加，加氢反应的选择性与2-甲基呋喃的转化率均呈现出先增加后减小的趋势。其原因是由于适当增加NiO负载量有利于催化剂表面活性中心的形成，有利于加氢反应的进行；但是过度负载的NiO容易堵塞Al₂O₃载体中的介孔通道，降低反应的转化率与选择性。在釜式反应器中进行反应，对加氢反应条件进行了优化，发现在反应压力为3 MPa、反应温度150℃、机械搅拌速率为1000 r/min时，Ni/Al₂O₃催化2-甲基呋喃加氢制2-甲基四氢呋喃具有较高的选择性。当NiO负载量为25%时，2-甲基四氢呋喃的选择性最高为97.1%，2-甲基呋喃的转化率达到99.4%。
- 浸渍法 /
- 2-甲基呋喃 /
- 2-甲基四氢呋喃 /
- 加氢 /
- Ni/Al₂O₃催化剂
Abstract: Ni/Al₂O₃ catalyst with various NiO loading was prepared with impregnation method. The catalytic performance for hydrogenation of 2-methylfuran to 2-methyltetrahydrofuran was investigated in this work. The results indicated that with an increase of NiO contents (10%, 20%, 25%, 30% and 40%), 2-methylfuran conversion rate first increased and then droped to a low level. The selectivity of this hydrogenation reaction showed the same trend. It was mainly because that NiO can produce more active center on catalyst surface, which was good for hydrogenation reaction. However, overloading of NiO blocked the mesopores of supportive Al₂O₃, and thus reduce the reaction selectivity and conversion rate. In batch reactor, after optimization the hydrogenation selectivity rate can be improved under hydrogen partial pressure of 3 MPa, reaction temperature of 150℃ and stirring speed of 1000 r/min. As a result, 2-methyltetrahydrofuran selectivity of 97.1% and 2-methylfuran conversion rate of 99.4% can be achieved with 25% NiO loading.
- impregnation method /
- 2-methylfuran /
- 2-methyltetrahydrofuran /
- hydrogenation /
- Ni/Al₂O₃ catalyst
注释:

1) 本文的英文电子版由Elsevier出版社在ScienceDirect上出版(http://www.sciencedirect.com/science/journal/18725813)

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图 1 2-甲基呋喃加氢制备2-甲基四氢呋喃的步骤

Figure 1 Step of preparation of 2-methyltetrahydrofuran by hydrogenation of 2-methylfuran

下载: 全尺寸图片幻灯片

图 2 Ni/Al₂O₃催化剂还原后的XRD谱图

Figure 2 XRD patterns of reduced Ni/Al₂O₃ catalysts

NiO loading: a: 10%; b: 20%; c: 25%; d: 30%; e: 40%

下载: 全尺寸图片幻灯片

图 3 Ni/Al₂O₃催化剂的H₂-TPR谱图

Figure 3 H₂-TPR patterns of Ni/Al₂O₃catalysts

NiO loading: a: 10%; b: 20%; c: 25%; d: 30%; e: 40%

下载: 全尺寸图片幻灯片

图 4 25%Ni/Al₂O₃催化剂催化2-MF加氢制备2-MTHF的稳定性

Figure 4 Stability test of hydrogenation of 2-methylfuran to 2-methyltetrahydrofuran over 25%Ni/Al₂O₃

●, ■ : first sample; ▲, ▼ : second sample

下载: 全尺寸图片幻灯片

表 1 载体的BET数据

Table 1 BET analysis supports

Sample	A _BET /(m²·g^-1)	Pore volume v/(cm³·g^-1)	Average pore diameter d/nm
Activated alumina	313	0.4488	5.73
γ-Al₂O₃	243	0.4048	6.64
activated alumina is used as carrier; γ-Al₂O₃ was prepared by calcination of activated alumina at 600 ℃

下载: 导出CSV

表 2 xNi/Al₂O₃催化剂的BET数据

Table 2 BET analysis of calcined xNi/Al₂O₃ catalysts

NiO w/%	A_BET /(m²·g^-1)	Pore volume v/(cm³·g^-1)	Average pore diameter d/nm
10	140	0.3242	8.64
25	149	0.3225	8.67
30	152	0.3486	9.17
40	108	0.2448	9.04
activated alumina is used as carrier

下载: 导出CSV

表 3 不同NiO负载量对催化剂催化性能影响

Table 3 Effects of different NiO loadings on catalytic performance of catalysts

NiO w/%	2-MF conversion x/%	Product selectivity s/%
NiO w/%	2-MF conversion x/%	2-MTHF	others
10	80.2	92.3	7.7
20	98.9	94.3	5.7
25	99.6	96.4	3.6
30	99.3	93.6	6.3
35	98.4	95.0	5.0
40	88.9	95.4	4.6
2-MF: 15 mL; catalyst: 0.5 g; reaction pressure: 4 MPa; reaction temperature: 150 ℃

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表 4 反应压力对Ni/Al₂O₃催化剂催化性能影响

Table 4 Effect of reaction pressure on catalytic performance of Ni/Al₂O₃ catalyst

Pressure p/MPa	2-MF conversion x/%	Product selectivity s/%
Pressure p/MPa	2-MF conversion x/%	2-MTHF	others
2	99.6	93.4	6.6
3	99.4	97.1	2.9
4	99.6	96.4	3.6
5	99.7	96.1	3.9
6	99.7	96.2	3.8
2-MF: 15 mL; catalyst: 0.5 g; reaction temperature: 150 ℃

下载: 导出CSV

表 5 反应温度对Ni/Al₂O₃催化剂催化性能影响

Table 5 Effect of reaction temperature on catalytic performance of Ni/Al₂O₃ catalyst

Reaction temperature t/℃	2-MF conversion x/%	Product selectivity s/%
Reaction temperature t/℃	2-MF conversion x/%	2-MTHF	others
90	53.0	39.2	60.8
120	96.8	95.2	4.8
140	98.2	95.4	4.6
150	99.4	97.1	2.9
180	98.2	58.4	41.6
2-MF: 15 mL; catalyst: 0.5 g; reaction pressure: 3 MPa

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Ni/Al₂O₃催化2-甲基呋喃加氢制2-甲基四氢呋喃性能的研究

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Catalytic performance of Ni/Al₂O₃ catalyst for hydrogenation of 2-methylfuran to 2-methyltetrahydrofuran

Corresponding author: ZHU Ming, Tel: 18205182971, E-mail: mingzhu84@njtech.edu.cn

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Ni/Al2O3催化2-甲基呋喃加氢制2-甲基四氢呋喃性能的研究

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Catalytic performance of Ni/Al2O3 catalyst for hydrogenation of 2-methylfuran to 2-methyltetrahydrofuran

Corresponding author: ZHU Ming, Tel: 18205182971, E-mail: mingzhu84@njtech.edu.cn

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2023年《燃料化学学报（中英文）》评优结果公布！

Ni/Al₂O₃催化2-甲基呋喃加氢制2-甲基四氢呋喃性能的研究

Catalytic performance of Ni/Al₂O₃ catalyst for hydrogenation of 2-methylfuran to 2-methyltetrahydrofuran