Cu/ZnO催化糠醛气相加氢制2-甲基呋喃的研究

黄玉辉; 任国卿; 孙蛟; 陈晓蓉; 梅华

Cu/ZnO催化糠醛气相加氢制2-甲基呋喃的研究

黄玉辉¹,
任国卿¹,
孙蛟¹,
陈晓蓉^{1, 2, ,},
梅华^{1, 2}

1.
南京工业大学化学化工学院, 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

通讯作者:
陈晓蓉, Tel:025-83172254, E-mail:chenxr@126.com

中图分类号: O643.38
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- 被引次数: 0
出版历程
- 收稿日期: 2016-07-07
- 修回日期: 2016-08-06
- 网络出版日期: 2021-01-23
- 刊出日期: 2016-11-10

Study on the vapor phase hydrogenation of furfural to 2-methylfuran on Cu/ZnO catalyst

HUANG Yu-hui¹,
REN Guo-qing¹,
SUN Jiao¹,
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

摘要

摘要: 通过共沉淀法制备一系列铜锌催化剂，用于固定床上糠醛气相加氢制2-甲基呋喃的研究。采用X射线衍射仪（XRD）、N₂吸附-脱附、扫描电子显微镜（SEM）、H₂-程序升温还原（H₂-TPR）、NH₃-程序升温脱附（NH₃-TPD）表征，分析催化剂中Cu⁰和ZnO在催化反应中的作用。结果表明，Cu⁰是糠醛加氢的活性中心，氧化锌的加入减小了催化剂晶粒粒径、增大了催化剂比表面积、利于催化剂还原和增加催化剂表面弱酸性位。当Cu/Zn物质的量比为1：2时，Cu₁Zn₂催化剂具有适宜氧化还原活性中心及弱酸位数量，对2-甲基呋喃表现出较高的选择性。Cu₁Zn₂催化剂在常压、反应温度为200℃、氢醛物质的量比为4：1、糠醛体积空速为0.3 h^-1条件下，糠醛转化率100.0%，2-甲基呋喃选择性最高为93.6%。反应稳定运行200 h后，糠醛转化率仍为100.0%，2-甲基呋喃选择性为80.0%，糠醇选择性为11.4%。
- 共沉淀法 /
- 铜锌催化剂 /
- 糠醛 /
- 气相加氢 /
- 2-甲基呋喃
Abstract: A series of Cu/ZnO catalysts were prepared by using co-precipitation method and their performance for the furfural gas phase hydrogenation to 2-methylfuran was investigated in a fixed bed reactor. The catalysts were characterized by X-ray diffraction (XRD), N₂ adsorption desorption, H₂ temperature programmed reduction (H₂-TPR), scanning electron microscope (SEM) and NH₃-temperature programmed desorption (NH₃-TPD) techniques to analyze the roles of Cu⁰ and ZnO. The results showed that Cu⁰ was the active center for the furfural hydrogenation and the addition of ZnO in Cu catalysts can reduce the crystal size, enhance the surface area, improve the reduction and increase the surface acidity of the catalysts. When the molar ratio of Cu/Zn molar ratio is 1:2, Cu₁Zn₂ catalyst showed the highest selectivity to 2-methylfuran due to its suitable numbers of redox active centers and weak acidic sites. Under the atmospheric pressure, reaction temperature of 200℃, 4:1 molar ratio of hydrogen to furfural and furfural volume space velocity of 0.3 h^-1, the conversion of furfural reached almost 100.0% with 93.6% selectivity to 2-methylfuran over Cu₁Zn₂ catalyst.
- co-precipitation method /
- Cu/ZnO catalyst /
- furfural /
- gas hydrogenation /
- 2-methylfuran

HTML全文

图 1 糠醛加氢过程中主要产物的分布

Figure 1 Distribution of the main products in the process of furfural hydrogenation

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图 2 催化剂的SEM照片

Figure 2 SEM images of the catalysts

(a): Cu₁Zn₄; (b): Cu₁Zn₂; (c): Cu₁Zn₁; (d): Cu₁Zn_0.67; (e): Cu₁Zn₀

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图 3 铜锌氧化态样品的XRD谱图

Figure 3 XRD spectra of the CuZn oxides

a: Cu₁Zn₄; b: Cu₁Zn₂; c: Cu₁Zn₁; d: Cu₁Zn_0.67; e: Cu₁Zn₀

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图 4 铜锌催化剂还原后的XRD谱图

Figure 4 XRD spectra of reduced CuZn catalysts

a: Cu₁Zn₄; b: Cu₁Zn₂; c: Cu₁Zn₁; d: Cu₁Zn_0.67; e: Cu₁Zn₀

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图 5 催化剂的H₂-TPR谱图

Figure 5 H₂-TPR profiles of the catalysts

a: Cu₁Zn₄; b: Cu₁Zn₂; c: Cu₁Zn₁; d: Cu₁Zn_0.67; e: Cu₁Zn₀

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图 6 催化剂的NH₃-TPD谱图

Figure 6 NH₃-TPD profiles of the catalysts

a: Cu₁Zn₀; b: Cu₁Zn₄; c: Cu₁Zn₂; d: Cu₁Zn₁; e: Cu₁Zn_0.67; f: Cu₀Zn₁

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图 7 反应温度对催化性能的影响

Figure 7 Effects of reaction temperature on catalytic performance

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图 8 氢醛物质的量比对催化性能的影响

Figure 8 Effects of the mol ratios of hydrogen to furfural on catalytic performance

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图 9 体积空速对催化性能的影响

Figure 9 Effects of the volume space velocity of furfural on the catalytic performance

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图 10 Cu₁Zn₂催化剂上糠醛加氢制2-甲基呋喃的稳定性

Figure 10 Stability test of hydrogenation of furfural to 2-methylfuran over Cu₁Zn₂

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表 1 铜锌催化剂的比表面积及还原前后的晶粒粒径

Table 1 BET analysis, crystal sizes of calcined and reduced Cu/ZnO catalysts

Catalyst	A_BET /(m²·g^-1)	Crystal size d/nm
		calcined sample		reduced sample
		CuO	ZnO	Cu⁰	ZnO
Cu₁Zn₄	40.6	10.4	14.6	13.4	16.4
Cu₁Zn₂	41.7	11.1	13.5	16.4	14.4
Cu₁Zn₁	38.0	11.2	12.0	16.7	18.2
Cu₁Zn_0.67	25.0	12.1	11.9	17.4	22.4
Cu₁Zn₀	6.0	14.8	-	28.6	-

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表 2 铜锌催化剂的性能评价

Table 2 Evaluation of catalytic performance over Cu/ZnO

Catalyst	FFR conversion x/%	Product selectivity s/%
Catalyst	FFR conversion x/%	2-MF	FOL	THFA	MTHF	1-pentanol	others
Cu₁Zn₄	100.0	88.7	4.1	-	0.8	0.4	6.0
Cu₁Zn₂	100.0	93.6	0.5	-	1.4	0.6	3.9
Cu₁Zn₁	100.0	92.0	-	-	2.3	1.8	3.9
Cu₁Zn_0.67	100.0	87.9	-	-	3.3	3.3	5.5
Cu₁Zn₀	99.2	8.8	86.4	2.5	0.4	-	1.9

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