稻壳碳基固体酸催化剂的制备及在木糖脱水制备糠醛反应中的催化性能

doi:10.7503/cjcu20160040

高等学校化学学报 ›› 2016, Vol. 37 ›› Issue (6): 1123.doi: 10.7503/cjcu20160040

稻壳碳基固体酸催化剂的制备及在木糖脱水制备糠醛反应中的催化性能

梁玉, 陈志浩, 梁宝炎, 胡哲, 杨晓敏(), 王子忱

吉林大学化学学院, 长春 130012

收稿日期:2016-01-08 出版日期:2016-06-10 发布日期:2016-04-30
作者简介:联系人简介: 杨晓敏, 女, 博士, 讲师, 主要从事生物质综合利用的研究. E-mail:xmyang@jlu.edu.cn
基金资助:
国家自然科学基金(批准号: 51502108)、高等学校博士学科点专项科研基金(批准号: 20130061120018)和吉林省科技发展计划项目(批准号: 20150520016JH)资助

Preparation of Rice Husk Carbon-based Solid Acid Catalyst for the Dehydration of Xylose to Furfural^†

LIANG Yu, CHEN Zhihao, LIANG Baoyan, HU Zhe, YANG Xiaomin^*(), WANG Zichen

College of Chemistry, Jilin University, Changchun 130012, China

Received:2016-01-08 Online:2016-06-10 Published:2016-04-30
Contact: YANG Xiaomin E-mail:xmyang@jlu.edu.cn
Supported by:
† Supported by the National Natural Science Foundation of China(No.51502108), the Research Fund for the Doctoral Program of Higher Education of China(No.20130061120018) and the Development Project of Science and Technology of Jilin Province, China(No.20150520016JH)

摘要/Abstract

摘要：

以工业生产中碱法溶硅剩余的稻壳残渣为碳源, 采用硫酸磺化法制备稻壳碳基固体酸催化剂, 考察了其催化木糖脱水制备糠醛的性能. 采用红外光谱、元素分析及表面酸浓度测定等手段对催化剂进行了表征. 对固体酸催化剂的制备条件进行了优化, 所得催化剂的表面酸浓度可达1.03 mmol/g. 以木糖脱水制备糠醛为模型反应, 考察了溶剂类别、反应温度和反应时间对固体酸催化剂催化性能的影响. 实验结果表明, 以二甲基亚砜(DMSO)为反应溶剂效果优于水, 并且随着反应温度的升高和反应时间的延长, 反应产率逐渐增加, 最高可达75.8%. 此外, 还对催化剂的循环性能进行了研究, 探讨了其失活原因和再生方法.

关键词: 碳基固体酸催化剂, 磺化, 木糖, 糠醛

Abstract:

A carbon-based solid acid catalyst, prepared by the sulfonation of rice husk carbon, was proved to be an efficient and environmental benign catalyst for the dehydration of xylose to furfural. The catalyst was characterized by Fourier transform infrared spectroscopy(FTIR), elemental analysis and Scanning Electronic Microscopy(SEM). The total acid site concentrations of the catalyst samples were obtained using standard acid-base back titration. The acid site concentration of 1.03 mmol/g was obtained when the 4.0 g of rice husk carbon was sulfonated by 15 mL of H₂SO₄ at 150 ℃ for 8 h. The effects of solvent, reaction temperature and time on the dehydration of xylose to furfural catalyzed by the rice husk carbon-based solid acid catalyst were studied. The results indicate that the yield of furfural increases gradually with the increase of reaction temperature and with the prolonger of the reaction time. The catalytic performance of the synthesized catalyst is better when using DMSO as reaction solvent than that of using water as solvent. A maximum furfural yield of 75.8% was achieved. The repeated usability and regeneration of the catalyst was investigated.

Key words: Carbon-based solid acid catalyst, Sulfonation, Xylose, Furfural

中图分类号:

O643.3

TrendMD:

梁玉, 陈志浩, 梁宝炎, 胡哲, 杨晓敏, 王子忱. 稻壳碳基固体酸催化剂的制备及在木糖脱水制备糠醛反应中的催化性能. 高等学校化学学报, 2016, 37(6): 1123.

LIANG Yu, CHEN Zhihao, LIANG Baoyan, HU Zhe, YANG Xiaomin, WANG Zichen. Preparation of Rice Husk Carbon-based Solid Acid Catalyst for the Dehydration of Xylose to Furfural^†. Chem. J. Chinese Universities, 2016, 37(6): 1123.

图/表 7

Fig.1 Effect of sulfonation time on the acid site density of rice husk-derived carbon-based solid acid catalystPreparation conditions: rice husk-based carbon(4.0 g), H2SO4(15 mL), 150 ℃.

Fig.2 FTIR spectrum of rice husk-derived carbon-based solid acid catalystPreparation conditions: rice husk-based carbon(4.0 g), H2SO4(15 mL), 150 ℃, 8 h.

Table 1 Elemental analysis of rice husk-derived carbon and rice husk-derived carbon-based solid acid catalyst*

Sample	Elemental content(%)
Sample	N	C	H	S
RHC	0.56	61.56	1.31	0.32
Catalyst	0.50	59.47	1.73	2.22

Fig.3 SEM image of rice husk-derived carbon-based solid acid catalystPreparation conditions: rice husk-based carbon(4.0 g), H2SO4(15 mL), 150 ℃, 8 h.

Table 2 Effect of reaction temperature on the dehydration of xylose to furfural*

Temperature/℃	120	140	160	180
Yield of furfural(%)	8.2	30.0	45.7	72.3

Table 3 Effect of reaction time on the dehydration of xylose to furfural*

Time/h	2	4	6	7	8
Yield off urfural(%)	36.3	45.7	51.4	58.8	75.8

Table 4 Reused ability of the catalyst*

Cycle	Yield of urfural(%)	Acid site density/(mmol·g^-1)
0	72.3	1.03
1	72.2	1.04
2	58.7	0.85
3	44.4	0.65

参考文献 19

[1]	Hara M., Energy Environ. Sci., 2010, 3, 601—607
[2]	Yang F. L., Liu Q. S., Bai X. F., Du Y. G., Bioresour. Technol., 2011, 102, 3424—3429
[3]	Russo P. A., Antunes M. M., Neves P., Wiper P. V., Fazio E., Neri F., Barreca F., Mafra L., Pillinger M., Pinna N., Valente A. A., J. Mater. Chem. A, 2014, 2, 11813—11824
[4]	Kubota Y., Inagaki S., Takechi K., Catal. Today, 2014, 226, 109—116
[5]	Sun P., Yu D. H., Hu Y., Tang Z. C., Xia J. J., Li H., Huang H., Korean J. Chem. Eng., 2011, 28(1), 99—105
[6]	Yang X. L., Charles U. P. Jr., Zhu X. F., Chem. J. Chinese Universities, 2010, 31(7), 1398—1404
	(杨续来, Charles U. Pittman Jr., 朱锡锋. 高等学校化学学报, 2010, 31(7), 1398—1404)
[7]	Nakajima K., Hara M., ACS Catal., 2012, 2, 1296—1304
[8]	Du F., Qi X. H., Xu Y. Z., Zhuang Y. Y., Chem. J. Chinese Universities, 2010, 31(3), 548—552
	(杜芳, 漆新华, 徐英钊, 庄源益. 高等学校化学学报, 2010, 31(3), 548—552)
[9]	Hara M., Yoshida T., Takagaki A., Takata T., Kondo J. N., Hayashi S., Domen K., Angew. Chem. Int. Ed., 2004, 43, 2955—2958
[10]	Saffar-Teluri A., Res. Chem. Intermed., 2014, 40, 523—529
[11]	Shen S. G., Wang T., Qin H. F., Dai G., Li H. M., J. Functional Materials, 2012, 12(43), 1598—1601
	(申曙光, 王涛, 秦海峰, 代光, 李焕梅. 功能材料, 2012, 12(43), 1598—1601)
[12]	Liu T. T., Li Z. L., Li W., Shi C. J., Wang Y., Bioresour. Technol., 2013, 133, 618—621
[13]	Fu X. B., Li D. H., Chen J., Zhang Y. M., Huang W. Y., Zhu Y., Yang J., Zhang C. W., Bioresour. Technol., 2013, 146, 767—770
[14]	Wu R. N., Wang T. H., Xiu Z. L., Guo F., Pan Y. Q., Yin J. Z., Chinese J. Catal., 2009, 30(12), 1203—1208
	(乌日娜, 王同华, 修志龙, 郭峰, 潘艳秋, 银建中. 催化学报, 2009, 30(12), 1203—1208)
[15]	Kastner J. R., Miller J., Geller D. P., Locklin J., Keith L. H., Johnson T., Catal. Today, 2012, 190, 122—132
[16]	Luque R., Clark J. H., Chem. Cat. Chem., 2011, 3, 594—597
[17]	Thombal R. S., Jadhav V. H., Appl. Catal. A: Gen., 2015, 499, 213—216
[18]	Thombal R. S., Jadhav A. R., Jadhav V. H., RSC Adv., 2015, 5, 12981—12986
[19]	Suganuma S., Nakajima K., Kitano M., Yamaguchi D., Kato H., Hayashi S., Hara M., J. Am. Chem. Soc., 2008, 130, 12787—120793

稻壳碳基固体酸催化剂的制备及在木糖脱水制备糠醛反应中的催化性能

Preparation of Rice Husk Carbon-based Solid Acid Catalyst for the Dehydration of Xylose to Furfural^†

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稻壳碳基固体酸催化剂的制备及在木糖脱水制备糠醛反应中的催化性能

Preparation of Rice Husk Carbon-based Solid Acid Catalyst for the Dehydration of Xylose to Furfural†

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Preparation of Rice Husk Carbon-based Solid Acid Catalyst for the Dehydration of Xylose to Furfural^†