焙烧温度对CuMgAl催化剂催化糠醛气相加氢制糠醇性能的影响

孙蛟; 任国卿; 黄玉辉; 陈晓蓉; 梅华

焙烧温度对CuMgAl催化剂催化糠醛气相加氢制糠醇性能的影响

孙蛟¹,
任国卿¹,
黄玉辉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: 2016-09-27
- 修回日期: 2016-11-18
- 网络出版日期: 2021-01-23
- 刊出日期: 2017-01-10

Effect of calcination temperature on the catalytic performance of CuMgAl catalysts for furfural gas phase selective hydrogenation to furfuryl alcohol

SUN Jiao¹,
REN Guo-qing¹,
HUANG Yu-hui¹,
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: 采用分步沉淀过程制得质量比m（CuO）：m（MgO）：m（Al₂O₃）为25：26：49的CuMgAl类水滑石前驱体，经过不同温度焙烧制得CuMgAl-t催化剂。通过BET、热重、XRD、H₂-TPR和CO₂-TPD对催化剂进行表征，在固定床中考察CuMgAl-t催化剂催化糠醛气相加氢制糠醇的性能。结果表明，焙烧温度影响催化剂活性、稳定性及对产物的选择性，低温焙烧的催化剂经还原后可获得较多活性中心，高温焙烧的催化剂表面具有更多的碱性位，CuMgAl催化剂经450℃焙烧表面存在适宜的活性中心和碱性位。在常压、反应温度180℃、氢醛物质的量比5：1、糠醛体积空速0.3 h^-1的条件下，CuMgAl-450催化剂上糠醛的转化率和糠醇的选择性分别达到98.64%和97.66%。
- 分步沉淀过程 /
- 糠醛 /
- 糠醇 /
- 气相加氢 /
- CuMgAl催化剂
Abstract: The CuMgAl hydrotalcite-type precursors were prepared by fractional precipitation process with the mass ratio of m(CuO):m(MgO):m(Al₂O₃)=25:26:49. CuMgAl-t catalysts were calcined at various temperatures. CuMgAl-t catalysts were characterized by BET, TGA, XRD and H₂-TPR and CO₂-TPD. The catalytic performance of CuMgAl-t catalysts for the gas phase hydrogenation of furfural to furfuryl alcohol was investigated in a fixed bed reactor. The results showed that the calcination temperatures had effect on catalysts activity, stability and product selectivity. The lower temperature calcined catalysts with reduction can obtain more active center and the higher temperature calcined catalysts had more alkaline sites on the surface of catalysts. CuMgAl catalyst calcined at 450℃ had suitable surface active centers and alkaline sites. Under the reaction conditions of atmospheric pressure, reaction temperature of 180℃, molar ratio of hydrogen to furfural of 5 and volume space velocity of 0.3 h^-1, the furfural conversion of 98.64% and furfuryl alcohol selectivity of 97.66% were reached over the CuMgAl-450.
- fractional precipitation process /
- furfural /
- furfuryl alcohol /
- gas phase hydrogenation /
- CuMgAl catalysts

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图 1 糖醛加氢示意图

Figure 1 Hydrogenation of furfural

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图 2 CuMgAl类水滑石前驱体的TG曲线

Figure 2 TG curve of the CuMgAl hydrotalcite-type precursor

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图 3 CuMgAl-t催化剂和CuMgAl类水滑石前驱体的XRD谱图

Figure 3 XRD patterns of CuMgAl-t catalysts and CuMgAl hydrotalcite-type precursor

a：CuMgAl-350；b：CuMgAl-400；c：CuMgAl-450；d：CuMgAl-500；e：CuMgAl-550；f：CuMgAl hydrotalcite-type precursor

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图 4 还原态CuMgAl-t催化剂的XRD谱图

Figure 4 XRD patterns of reduced CuMgAl-t catalysts

a：CuMgAl-350；b：CuMgAl-400；c：CuMgAl-450；d：CuMgAl-500；e：CuMgAl-550

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图 5 CuMgAl-t催化剂的H₂-TPR谱图

Figure 5 H₂-TPR profiles of CuMgAl-t catalysts

a：CuMgAl-350；b：CuMgAl-400；c：CuMgAl-450；d：CuMgAl-500；e：CuMgAl-550

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图 6 CuMgAl-t催化剂的CO₂-TPD谱图

Figure 6 CO₂-TPD profiles of CuMgAl-t catalysts

a：CuMgAl-350；b：CuMgAl-400；c：CuMgAl-450；d：CuMgAl-500；e：CuMgAl-550

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图 7 CuMgAl-t催化剂上糠醛加氢制糠醇的稳定性

Figure 7 Stability test of CuMgAl-t catalysts in the hydrogenation of furfural to furfuryl alcohol

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表 1 CuMgAl-t催化剂BET分析数据及还原态催化剂Cu⁰粒径

Table 1 BET analysis of CuMgAl-t catalysts and Cu⁰ particle size of reduced catatlysts

Catalyst	BET A/(m²·g^-1)	Pore volume v^*/(cm³·g^-1)	Average pore diameter d/nm	Particle size of Cu⁰ d/nm
CuMgAl-350	217	0.558 7	3.71	4.54
CuMgAl-400	211	0.551 2	3.72	4.83
CuMgAl-450	204	0.550 1	3.75	4.74
CuMgAl-500	211	0.586 1	3.75	5.45
CuMgAl-550	193	0.540 2	3.75	5.70
^*：pore volume was determined on the basic of the nitrogen adsorption at a relative pressure of 0.99

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表 2 焙烧温度对CuMgAl-t催化剂催化性能的影响

Table 2 Effect of calcination temperatures on the catalytic performance of CuMgAl-t catalysts

Catalyst	FFR conversion x/%	Selectivity s/%
Catalyst	FFR conversion x/%	2-MF	FOL	others
CuMgAl-350	98.20	2.70	92.37	4.93
CuMgAl-400	98.18	1.96	95.36	2.68
CuMgAl-450	98.64	0.94	97.66	1.40
CuMgAl-500	96.18	0.76	97.87	1.37
CuMgAl-550	91.56	0.72	97.71	1.57
2-MF: 2-methyl furan；others include tetrahydrofurfuryl alcohol，cyclopentanone and cyclopentanol

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