One Step Preparation of Sulfonated Solid Catalyst and Its Effect in Esterification Reaction

doi:10.1016/S1004-9541(14)60058-6

Chinese Journal of Chemical Engineering ›› 2014, Vol. 22 ›› Issue (4): 392-397.DOI: 10.1016/S1004-9541(14)60058-6

• 催化、动力学与反应工程 • 上一篇下一篇

One Step Preparation of Sulfonated Solid Catalyst and Its Effect in Esterification Reaction

康世民, 常杰, 范娟

The Key Laboratory of Fuel Cell Technology of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640, China

收稿日期:2012-11-27 修回日期:2013-04-17 出版日期:2014-04-28 发布日期:2014-04-04
通讯作者: CHANG Jie
基金资助:
Supported by the State Key Development Program for Basic Research of China (2013CB228104, 2010CB732205), Ph. D Programs Foundation of Ministry of Education of China (20120172110011), and the National High Technology Research and Development Program of China (2012AA051801).

One Step Preparation of Sulfonated Solid Catalyst and Its Effect in Esterification Reaction

KANG Shimin, CHANG Jie, FAN Juan

The Key Laboratory of Fuel Cell Technology of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640, China

Received:2012-11-27 Revised:2013-04-17 Online:2014-04-28 Published:2014-04-04
Supported by:
Supported by the State Key Development Program for Basic Research of China (2013CB228104, 2010CB732205), Ph. D Programs Foundation of Ministry of Education of China (20120172110011), and the National High Technology Research and Development Program of China (2012AA051801).

摘要/Abstract

摘要： A carbon-based sulfonated catalyst was prepared by direct sulfonation and carbonization (in moderate conditions: 200 ℃, 12 h) of red liquor solids, a by-product of paper-making process. The prepared sulfonated catalyst (SC) had aromatic structure, composed of carbon enriched inner core, and oxygen-containing (SO₃H, COOH, OH) groups enriched surface. The SO₃H, COOH, OH groups amounted to 0.74 mmol·g^-1, 0.78 mmol·g^-1, 2.18 mmol·g^-1, respectively. The fresh SC showed much higher catalytic activity than that of the traditional solid acid catalysts (strong-acid 732 cation exchange resin, hydrogen type zeolite socony mobile-five (HZSM-5), sulfated zirconia) in esterification of oleic acid. SC was deactivated during the reactions, through the mechanisms of leaching of sulfonated species and formation of sulfonate esters. Two regeneration methods were developed, and the catalytic activity can be mostly regenerated by regeneration Method 1 and be fully regenerated by regeneration Method 2, respectively.

关键词: red liquor solids, sulfonated solid catalyst, carbonization, esterification

Abstract: A carbon-based sulfonated catalyst was prepared by direct sulfonation and carbonization (in moderate conditions: 200 ℃, 12 h) of red liquor solids, a by-product of paper-making process. The prepared sulfonated catalyst (SC) had aromatic structure, composed of carbon enriched inner core, and oxygen-containing (SO₃H, COOH, OH) groups enriched surface. The SO₃H, COOH, OH groups amounted to 0.74 mmol·g^-1, 0.78 mmol·g^-1, 2.18 mmol·g^-1, respectively. The fresh SC showed much higher catalytic activity than that of the traditional solid acid catalysts (strong-acid 732 cation exchange resin, hydrogen type zeolite socony mobile-five (HZSM-5), sulfated zirconia) in esterification of oleic acid. SC was deactivated during the reactions, through the mechanisms of leaching of sulfonated species and formation of sulfonate esters. Two regeneration methods were developed, and the catalytic activity can be mostly regenerated by regeneration Method 1 and be fully regenerated by regeneration Method 2, respectively.

Key words: red liquor solids, sulfonated solid catalyst, carbonization, esterification

康世民, 常杰, 范娟. One Step Preparation of Sulfonated Solid Catalyst and Its Effect in Esterification Reaction[J]. Chinese Journal of Chemical Engineering, 2014, 22(4): 392-397.

KANG Shimin, CHANG Jie, FAN Juan. One Step Preparation of Sulfonated Solid Catalyst and Its Effect in Esterification Reaction[J]. Chin.J.Chem.Eng., 2014, 22(4): 392-397.

参考文献

1 Toda, M., Takagaki, A., Okamura, M., Kondo, J.N., Hayashi, S., Domen, K., Hara, M., "Biodiesel made with sugar catalyst", Nature, 480, 178 (2005).

2 Lou, W.Y., Zong, M.H., Duan, Z.Q., "Efficient production of biodiesel from high free fatty acid-containing waste oils using various carbohydrate-derived solid acid catalysts", Bioresour. Technol., 99 (18), 8752-8758 (2008).

3 Chen, G., Fang, B., "Preparation of solid acid catalyst from glucose-starch mixture for biodiesel production", Bioresour. Technol., 102 (3), 2635-2640 (2011).

4 Shu, Q., Gao, J., Liao, Y., Wang, J., "Reaction kinetics of biodiesel synthesis from waste oil using a carbon-based solid acid catalyst", Chin. J. Chem. Eng., 19 (1), 163-168 (2011).

5 Suganuma, S., Nakajima, K., Kitano, M., Yamaguchi, D., Kato, H., Hayashi, S., Hara, M., "Hydrolysis of cellulose by amorphous carbon bearing SO₃H, COOH, and OH groups", J. Am. Chem. Soc., 130 (38), 12787-12793 (2008).

6 Liang, X., Zeng, M., Qi, C., "One-step synthesis of carbon functionalized with sulfonic acid groups using hydrothermal carbonization", Carbon, 48 (6), 1844-1848 (2010).

7 Zhang, W., Tao, H., Zhang, B., Ren, J., Lu, G., Wang, Y., "One-pot synthesis of carbonaceous monolith with surface sulfonic groups and its carbonization/activation", Carbon, 49 (6), 1811-1820 (2011).

8 Shu, Q., Nawaz, Z., Liao, Y., Zhang, Q., Wang, D., Wang, J., "Synthesis of biodiesel from a model waste oil feedstock using a carbon-based solid acid catalyst: Reaction and separation", Bioresour. Technol., 101 (3), 5374-5384 (2010).

9 Hara, M., Yoshida, T., Takagaki, A., Takata, T., Kondo, J.N., Hayashi, S., Domen, K., "A carbon material as a strong protonic acid", Angew Chem. Int. Ed., 43 (22), 2955-2958 (2004).

10 Gan, M., Pan, D., Ma, L., Yue, E., Hong, J. "The kinetics of the esterification of free fatty acids in waste cooking oil using Fe₂(SO₄)₃/C Catalyst", Chin. J. Chem. Eng., 17 (1), 83-87 (2009)

11 Li, J., Fu, Y.J., Qu, X.J., Wang, W., Luo, M., Zhao, C.J., Zu, Y.G., "Biodiesel production from yellow horn (Xanthoceras sorbifolia Bunge) seed oil using ion exchange resin as heterogeneous catalyst", Bioresour. Technol., 108, 112-118 (2012).

12 Yee, K.F., Lee, K.T., Ceccato, R., Abdullah, A.Z., "Production of biodiesel from Jatropha curcas L. oil catalyzed by SO42- /ZrO2 catalyst: Effect of interaction between process variables", Bioresour. Technol., 102 (5), 4285-4289 (2011).

13 Shibasaki-Kitakawa, N., Honda, H., Kuribayashi, H., Toda, T., Fukumura, T., Yonemoto, T., "Biodiesel production using anionic ion-exchange resin as heterogeneous catalyst", Bioresour. Technol., 98 (2), 416-421 (2007).

14 Rao, B.V.S.K., Mouli, K.C., Rambabu, N., Dalai, A.K., Prasad, R.B.N., "Carbon-based solid acid catalyst from de-oiled canola meal for biodiesel production", Catal. Commun., 14 (1), 20-26 (2011).

15 Yang, X., Wan, J., "Preparation of carbon- based solid acid catalyst and its catalytic performance", Modern Chemical Industry, 31 (10), 34-37 (2011). (in Chinese)

16 Zhao, Y., Wan, J., "Hydrolysis saccharification of OCC by a sulfonated carbon solid-acid catalyst", Modern Chemical Industry, 30 (9), 40-44 (2010). (in Chinese)

17 Fraile, J.M., García-Bordejé, E., Roldán, L., "Deactivation of sulfonated hydrothermal carbons in the presence of alcohols: Evidences for sulfonic esters formation", J. Catal., 289, 73-79 (2012).

[1]	Junyang Liu, Luming Wang, Yuhang Bian, Chunshan Li, Zengxi Li, Jie Li. Liquid-phase esterification of methacrylic acid with methanol catalyzed by cation-exchange resin in a fixed bed reactor: Experimental and kinetic studies[J]. 中国化学工程学报, 2023, 58(6): 1-10.
[2]	Zhiwei Wang, Yu Zhang, Zhi Zhang, Daowei Zhou, Zhikai Cao, Yong Sha. Investigation on catalytic distillation for ethyl acetate production with different catalytic packing structures[J]. 中国化学工程学报, 2023, 53(1): 63-72.
[3]	Monique Juna L. Leite, Ingrid Ramalho Marques, Mariane Carolina Proner, Pedro H.H. Araújo, Alan Ambrosi, Marco Di Luccio. Catalytically active membranes for esterification: A review[J]. 中国化学工程学报, 2023, 53(1): 142-154.
[4]	Tengjie Wang, Wenkai Li, Xuehui Ge, Ting Qiu, Xiaoda Wang. Kinetics measurement of ethylene-carbonate synthesis via a fast transesterification by microreactors[J]. 中国化学工程学报, 2023, 53(1): 243-250.
[5]	Xiaojiang Liang, Fengjiao Wu, Qinglong Xie, Zhenyu Wu, Jinjin Cai, Congwen Zheng, Junhong Fu, Yong Nie. Insights into biobased epoxidized fatty acid isobutyl esters from biodiesel: Preparation and application as plasticizer[J]. 中国化学工程学报, 2022, 44(4): 41-50.
[6]	Qing Shu, Xinyuan Liu, Yanting Huo, Yuhui Tan, Caixia Zhang, Laixi Zou. Construction of a Brönsted-Lewis solid acid catalyst La-PW-SiO₂/SWCNTs based on electron withdrawing effect of La(III) on π bond of SWCNTs for biodiesel synthesis from esterification of oleic acid and methanol[J]. 中国化学工程学报, 2022, 44(4): 351-362.
[7]	Xiaoda Wang, Wenkai Li, Shiwei Wang, Qinglian Wang, Ling Li, Hongxing Wang, Ting Qiu. Reaction kinetics for the heterogeneously resin-catalyzed and homogeneously self-catalyzed esterification of thioglycolic acid with 2-ethyl-1-hexanol[J]. 中国化学工程学报, 2021, 36(8): 111-119.
[8]	Yishan Zhou, Hao Qin, Hongye Cheng, Lifang Chen, Bingjian Zhang, Zhiwen Qi. Reactive extraction for synthesizing long chain ester butyl hexanoate intensified by deep eutectic solvent[J]. 中国化学工程学报, 2021, 36(8): 120-127.
[9]	Xinlong Yan, Yanfang Li, Xiaoyan Hu, Rui Feng, Min Zhou, Dezhi Han. Enhanced adsorption of phenol from aqueous solution by carbonized trace ZIF-8-decorated activated carbon pellets[J]. 中国化学工程学报, 2021, 33(5): 279-285.
[10]	P. Vignesh, A.R. Pradeep Kumar, N. Shankar Ganesh, V. Jayaseelan, K. Sudhakar. A review of conventional and renewable biodiesel production[J]. 中国化学工程学报, 2021, 40(12): 1-17.
[11]	Majid Masteri-Farahani, Samaneh Shahsavarifar. Chemical functionalization of chitosan biopolymer and chitosan-magnetite nanocomposite with sulfonic acid for acid-catalyzed reactions[J]. 中国化学工程学报, 2021, 39(11): 154-161.
[12]	Xiaocheng Lin, Youjie Huang, Ling Li, Changshen Ye, Jie Chen, Ting Qiu. Polymeric ionic liquids (PILs) with high acid density: Tunable catalytic performance for biodiesel production[J]. 中国化学工程学报, 2021, 38(10): 266-275.
[13]	Xin Yuan, Lujun Wang, Panliang Zhang, Weifeng Xu, Kewen Tang. Enantioselective esterification of (R,S)-2-(4-methylphenyl) propionic acid via Novozym 435: Optimization and application[J]. 中国化学工程学报, 2020, 28(7): 1816-1823.
[14]	Feng Pan, Zhan Du, Shaofu Li, Jun Li, Meiju Zhang, Maoqiao Xiang, Qingshan Zhu. Preparation of nano-sized tungsten carbide via fluidized bed[J]. 中国化学工程学报, 2020, 28(3): 923-932.
[15]	Xutao Hu, Hao Qin, Biao Hu, Hongye Cheng, Lifang Chen, Zhiwen Qi. A rate-based method for dynamic analysis and optimal design of reactive extraction: n-Hexyl acetate esterification as an example[J]. 中国化学工程学报, 2020, 28(1): 76-83.

One Step Preparation of Sulfonated Solid Catalyst and Its Effect in Esterification Reaction

One Step Preparation of Sulfonated Solid Catalyst and Its Effect in Esterification Reaction

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价