CaO-MgO@CoFe<sub>2</sub>O<sub>4</sub>磁性固体碱的制备及其大豆油酯交换反应催化性能

范明明; 刘延磊; 张萍波; 蒋平平

CaO-MgO@CoFe₂O₄磁性固体碱的制备及其大豆油酯交换反应催化性能

范明明^{1, 2},
刘延磊^{1, 2},
张萍波^{1, 2, ,},
蒋平平^{1, 2}

1.
江南大学化学与材料工程学院, 江苏无锡 214122
2.
食品胶体与生物技术教育部重点实验室, 江苏无锡 214122

基金项目:

国家自然科学基金 21306063

江苏省自然科学基金 BK20130123

详细信息

中图分类号: TQ032.41
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- 文章访问数: 73
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- 被引次数: 0
出版历程
- 收稿日期: 2015-10-30
- 修回日期: 2016-01-11
- 网络出版日期: 2021-01-23
- 刊出日期: 2016-04-30

Preparation of magnetic core-shell CaO-MgO@CoFe₂O₄ solid base and its catalytic performance in the transesterification of soybean oil to biodiesel

FAN Ming-ming^{1, 2},
LIU Yan-lei^{1, 2},
ZHANG Ping-bo^{1, 2
, ,},
JIANG Ping-ping^{1, 2}

1.
School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122, China;
2.
The Key Laboratory of Food Colloids and Biotechnology, Ministry of Education, Wuxi 214122, China

More Information

Corresponding author: E-mall: pingbozhang@126.com.

摘要

摘要: 以草酸盐为前驱体采用两步法制备了一种以CaO-MgO作为活性组分,以CoFe₂O₄作为磁核的磁性固体碱催化剂,并用于大豆油与甲醇的酯交换反应合成生物柴油。对制备的磁性固体碱催化剂进行了磁滞回线、X-射线衍射(XRD)、CO₂-TPD及透射电镜(TEM)表征。考察了不同核壳物质的量比、焙烧温度、反应温度、反应时间、醇油物质的量比以及催化剂用量等因素对大豆油转化为生物柴油产率的影响。结果表明,采用核壳物质的量比为1:6、焙烧温度为700 ℃所制备的CaO-MgO@CoFe₂O₄催化剂,当醇油物质的量比为12、催化剂用量为大豆油质量的1.0%时,在65 ℃下反应时间3 h,生物柴油收率高达97.1%。该催化剂具有较好的重复利用性能,重复利用四次后生物柴油的收率仍可达90%。
- 生物柴油 /
- 磁性固体碱催化剂 /
- 酯交换反应 /
- 大豆油 /
- CaO-MgO@CoFe₂O₄
Abstract: A magnetic core-shell CaO-MgO@CoFe₂O₄ solid base was prepared with oxalates as the precursor through a two-step method, which was used as the catalyst for the transesterification of soybean oil to biodiesel with methanol. The CaO-MgO@CoFe₂O₄ catalyst was characterized by magnetic hysteresis loop, X-ray diffraction (XRD), CO₂-TPD and transmission electron microscopy (TEM); the effects of core-shell molar ratio, catalyst calcination temperature, reaction temperature, reaction time, methanol/oil molar ratio and catalyst amount on the yield of biodiesel were investigated. The results indicated that over the CaO-MgO@CoFe₂O₄ catalyst with a core-shell molar ratio of 1:6 and calcined at 700 ℃, the biodiesel yield reaches 97.1% after conducting the transesterification reaction at 65 ℃ for 3 h, when the methanol/oil mol ratio is 12 and the amount of catalyst is 1.0% by mass. The catalyst exhibits excellent reusability; the biodiesel yield remains above 90% after reusing for four cycles.
- biodiesel /
- magnetic solid base catalyst /
- transesterification /
- soybean oil /
- CaO-MgO@CoFe₂O₄

HTML全文

图 1 磁性固体碱催化剂及磁核的XRD谱图

Figure 1 XRD patterns of the magnetic core-shell CaO-MgO@CoFe₂O₄ solid base and the magnetic CoFe₂O₄ core

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图 2 催化剂的磁性分离

Figure 2 Magnetic separation of the catalyst from the reaction mixture

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图 3 CaO-MgO@CoFe₂O₄的磁滞回线

Figure 3 Magnetic hysteresis loops of the CaO-MgO@CoFe₂O₄ catalyst

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图 4 催化剂CaO-MgO@CoFe₂O₄的TEM与HRTEM照片

Figure 4 TEM and HRTEM images of the CaO-MgO@CoFe₂O₄catalyst

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图 5 混合氧化物CaO-MgO包裹CoFe₂O₄与纯CaO的CO₂-TPD谱图

Figure 5 CO₂-TPD curves of the CaO-MgO@CoFe₂O₄ catalyst and pure CaO

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图 6 不同n(CaO)∶n(MgO)包裹磁核对生物柴油产率的影响

Figure 6 Influence of n(CaO)/n(MgO) ratio on biodiesel yield over the CaO-MgO@CoFe₂O₄ catalyst

(the transesterification reaction was carried out at 70℃ for 4h,with a catalyst amount of 1.0% by mass and a methanol/oybean oil molar ratio of 12)

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图 7 n(CaO-MgO)∶n(CoFe₂O₄)物质的量比对生物柴油产率的影响

Figure 7 Influence of n(CaO-MgO)/n(CoFe₂O₄) ratio on biodiesel yield over the CaO-MgO@CoFe₂O₄ catalyst

(the transesterification reaction was carried out at 70℃ for 4h,with a catalyst amount of 1.0% by mass and a methanol/oybean oil molar ratio of 12)

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图 8 焙烧温度对生物柴油产率的影响

Figure 8 Influence of catalyst calcination temperature on biodiesel yield

(the transesterification reaction was carried out at 70℃ for 4h,with a catalyst amount of 1.0% by mass and a methanol/oybean oil molar ratio of 12)

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图 9 磁性固体碱催化剂的重复利用性能

Figure 9 Reusability of the CaO-MgO@CoFe₂O₄ catalyst in the transesterification reaction.

(the transesterification reaction was carried out at 65℃ for 3h,with a catalyst amount of 1.0% by mass and a methanol/oybean oil molar ratio of 12)

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参考文献(24)

[1]	THITSARTAM W, KAWI S. An active and stable CaO-CeO₂ catalyst for transesterification of oil to biodiesel[J]. Green Chem, 2011, 13: 3423-3430. doi: 10.1039/c1gc15596b
[2]	左同梅, 李为民, 赵强, 徐庆瑞, 陈诚, 陈龙. 新型碱性离子液体催化酯交换合成生物柴油[J]. 燃料化学学报, 2014, 42(2): 200-206. http://rlhxxb.sxicc.ac.cn/CN/volumn/volumn_1295.shtml# ZUO Tong-mei, LI Wei-min, ZHAO Qiang, XU Qing-rui, CHEN Cheng, CHEN Long. Synthesis of biodiesel through catalyzed by a novel transesterification alkaline ionic liquid [J]. J Fuel Chem Technol, 2014, 42(2): 200-206. http://rlhxxb.sxicc.ac.cn/CN/volumn/volumn_1295.shtml#
[3]	MAREHEYYI J M, MIGUEL V U, ERRAZU A F. Possible methods for biodiesel Production [J].Renew Sust Energy Rev, 2007, 11: 1300-1311. doi: 10.1016/j.rser.2005.08.006
[4]	黄世丰, 陈国, 方柏山. 酯化及转酯化法制备生物柴油过程中催化剂的研究进展[J]. 化工进展, 2008, 27(4): 508-514. http://www.cnki.com.cn/Article/CJFDTOTAL-HGJZ200804008.htm HUANG Shi-feng, CHEN Guo, FANG Bai-shan. Progress of catalysts for producing biodiesel by esterification and transesterification reaction[J]. Chem Ind Eng Process, 2008, 27(4): 508-514. http://www.cnki.com.cn/Article/CJFDTOTAL-HGJZ200804008.htm
[5]	QIAO K, HAGIWARA H, YOKOYAMA C. Acidic ionic liquid modified silica gel as novel solid catalysts for esterification and nitration reactions[J]. J Mol Catal Chem, 2006, 246(1): 65-69. http://pubs.rsc.org/en/Content/Database/CCR0605010702
[6]	MARCHETTI J M, MIGUEL V U, ERRAZU A F. Possible methods for biodiesel production[J]. Renew Sust Energy Rev, 2007, 11(6): 1300-1311. doi: 10.1016/j.rser.2005.08.006
[7]	胡秀英, 马迪, 杨廷海, 邓育苟. 固体碱催化剂K₂CO₃/Al₂O₃的制备及其催化餐饮废油制生物柴油的性能[J]. 燃料化学学报, 2014, 42(6): 683-689. http://rlhxxb.sxicc.ac.cn/CN/volumn/volumn_1299.shtml# HU Xiu-ying, MA Di, YANG Ting-hai, DENG Yu-gou. Preparation of solid base K₂CO₃/Al₂O₃ and catalytic conversion of waste cooking oil to biodiesel[J]. J Fuel Chem Technol, 2014, 42(6): 683-689. http://rlhxxb.sxicc.ac.cn/CN/volumn/volumn_1299.shtml#
[8]	娄文勇, 蔡俊, 段章群, 宗敏华. 基于纤维素的固体酸催化剂的制备及其催化高酸值废油脂生产生物柴油[J]. 催化学报, 2011, 32(11): 1755-1761. http://www.cnki.com.cn/Article/CJFDTOTAL-CHUA201111017.htm LOU Wen-yong, CAI Jun, DUAN Zhang-qun, ZONG Min-hua. Preparation of cellulose-derived solid acid catalyst and its use for production of biodiesel from waste oils with high acid value[J]. Chin J Catal, 2011, 32(11): 1755-1761. http://www.cnki.com.cn/Article/CJFDTOTAL-CHUA201111017.htm
[9]	MUSTAFA B, HAVVA B. Progress in biodiesel processing[J]. Appl Energy, 2010, 87: 1815-1835. doi: 10.1016/j.apenergy.2010.01.012
[10]	XIE W L, PENG H, CHEN L G. Transesterification of soybean oil catalyzed by potassium loaded on alumina as a solid-base catalyst[J]. Appl Catal A: Gen, 2006, 300: 67-74. doi: 10.1016/j.apcata.2005.10.048
[11]	BOEY P L, MANIAM G P, HAMID S A. Performance of calcium oxide as a heterogeneous catalyst in biodiesel production: A review[J]. Chem Eng J, 2011, 168: 15-22. doi: 10.1016/j.cej.2011.01.009
[12]	郑华艳, 李茜茜, 崔丽萍, 李忠. Ca/Al固体碱催化菜籽油制备生物柴[J]. 燃料化学学报, 2012, 40(3): 331-336. http://rlhxxb.sxicc.ac.cn/CN/volumn/volumn_1270.shtml# ZHENG Hua-yan, LI Qian-qian, CUI Li-ping, LI Zhong. Synthesis of biodiesel from rapeseed oil catalyzed by Ca/Al solid base[J]. J Fuel Chem Technol, 2012, 40(3): 331-336. http://rlhxxb.sxicc.ac.cn/CN/volumn/volumn_1270.shtml#
[13]	杨洪丽, 李为民, 姚建. 钙基负载型固体碱催化酯交换反应活性评价[J]. 燃料化学学报, 2008, 36(2): 241-245. http://rlhxxb.sxicc.ac.cn/CN/volumn/volumn_1203.shtml# YANG Hong-li, LI Wei-min, YAO Jian. Catalytic activities of CaO loaded solid base in transesterification of rape oil[J]. J Fuel Chem Technol, 2008, 36(2): 241-245. http://rlhxxb.sxicc.ac.cn/CN/volumn/volumn_1203.shtml#
[14]	KOUZU M, HIDAKA J. Transesterification of vegetable oil into biodiesel catalyzed by CaO: A review[J]. Fuel, 2012, 93: 1-12. doi: 10.1016/j.fuel.2011.09.015
[15]	ALBUQUERQUEA M C G, AZEVEDOA D C S, CAVALCANTE C L J, SANTAMARÍA-GONZÁLEZB J, MÉRIDA-ROBLESB J M, MORENO-TOSTB R, RODRÍGUEZ-CASTELLÓNB E, JIMÉNEZ-LÓPEZB A, MAIRELES-TORRESB P. Transesterification of ethyl butyrate with methanol using MgO/CaO catalysts[J]. J Mol Catal Chem, 2009, 300: 19-24. doi: 10.1016/j.molcata.2008.10.033
[16]	TEO S H, ISLAM A, NGAB F L, TAUFIQ-YAP Y H. Biodiesel synthesis from photoautotrophic cultivated oleoginous microalgae using a sand dollar catalyst[J]. RSC Adv, 2015, 5: 47140-47152. doi: 10.1039/C5RA05801E
[17]	陈英, 陈东, 谢颖, 冷星利, 余晶云, 成林娟. 用于生物柴油清洁生产的磁性固体催化剂CaO/MgO/Fe₃O₄[J]. 燃料化学学报, 2010, 38(4): 415-421. http://rlhxxb.sxicc.ac.cn/CN/volumn/volumn_1248.shtml# CHEN Ying, CHEN Dong, XIE Ying, LENG Xing-li, YU Jing-yun, CHENG Lin-juan. A magnetic solid catalyst of CaO/MgO/Fe₃O₄ for production of clean biodiesel[J]. J Fuel Chem Technol, 2010, 38(4): 415-421. http://rlhxxb.sxicc.ac.cn/CN/volumn/volumn_1248.shtml#
[18]	SANKARANARAYANAPILLAI S, JULIA S, SERHIY D, VOLKER S, STEFAN E, WERNER R. T. Nanoparticle supported, magnetically recoverable oxodiperoxo molybdenum complexes: Efficient catalysts for selective epoxidation reactions[J]. Adv Synth Catal, 2009, 351: 1789-1795. doi: 10.1002/adsc.v351:11/12
[19]	ABU-REZIQ R, WANG D S, POST M, ALPER H. Separable catalysts in one-pot syntheses for greener chemistry[J]. Chem Mater, 2008, 20: 2544-2550. doi: 10.1021/cm703208w
[20]	GAO Z, ZHOU J, CUI F M, ZHU Y, HUA Z L, SHI J L. Superparamagnetic mesoporous Mg-Fe bi-metal oxides as efficient magnetic solid-base catalysts for Knoevenagel condensations[J]. Dalton Trans, 2010, 39: 11132-11135. doi: 10.1039/c0dt00710b
[21]	ZHANG P B, HAN Q J, FAN M M, JIANG P P. Magnetic solid base catalyst CaO/CoFe₂O₄for biodiesel production: Influence of basicity and wettability of the catalyst in catalyticperformance[J]. Appl Surf Sci, 2014, 317: 1125-1130. doi: 10.1016/j.apsusc.2014.09.043
[22]	TAO G J, HUA Z L, GAO Z, ZHU Y, CHEN Y, SHU Z, ZHANG L X, SHI J L. KF-loaded mesoporous Mg-Fe bi-metal oxides: High performance transesterification catalysts for biodiesel production[J]. Chem Commun, 2013, 49: 8006-8008. doi: 10.1039/c3cc44494e
[23]	范明明, 毛炜陶, 杨静, 张萍波. 脂肪酸甲酯(生物柴油)的定性/定量分析方法[J]. 化工进展, 2012, 31(6): 1373-1378. http://www.cnki.com.cn/Article/CJFDTOTAL-HGJZ201206039.htm FAN Ming-ming, MAO Wei-tao, YANG Jing, ZHANG Ping-bo. Qualitative and quantitative analysis on fatty acid methyl ester(biodiesel)[J]. Chem Ind Eng Proc, 2012, 31(6): 1373-1378. http://www.cnki.com.cn/Article/CJFDTOTAL-HGJZ201206039.htm
[24]	JIANG W, NIU X Y, YUAN F L, ZHU Y J, FU H G. Preparation of KF-La₂O₂CO₃ solid base catalysts and their excellent catalytic activities for transesterification of tributyrin with methanol[J]. Catal Sci Technol, 2014, 4: 2957-2968. doi: 10.1039/C4CY00167B