复合磁性MgAl水滑石制备及其酯交换性能的研究

陈颖; 何晗; 孔祥森; 刘天聪

复合磁性MgAl水滑石制备及其酯交换性能的研究

东北石油大学化学化工学院, 黑龙江大庆 163318

基金项目:

国家自然科学基金 50476091

详细信息

中图分类号: TE667
计量
- 文章访问数: 215
- HTML全文浏览量: 67
- PDF下载量: 6
- 被引次数: 0
出版历程
- 收稿日期: 2016-04-08
- 修回日期: 2016-07-16
- 网络出版日期: 2021-01-23
- 刊出日期: 2016-10-10

Preparation of compound magnetic Fe₃O₄/MgAl-layered double hydroxide and its application in biodiesel transesterification

School of Chemical Engineering, Northeast Petroleum University, Daqing 163318, China

More Information

Corresponding author: Tel: 0459-6503438, E-mail: shiyoudaxue5837@163.com

摘要

摘要: 使用共沉淀法制备磁性Fe₃O₄粒子，并以此为原料制备出Fe₃O₄/MgAl-LDH，将其焙烧产物Fe₃O₄/Mg（Al）O作为微藻油脂和甲醇发生酯交换反应的催化剂，利用产物生物柴油产率作为评价催化剂的活性指标，探究其酯交换活性。通过TG-DTG、XRD、SEM、EDS、TEM、N₂吸附-脱附、VSM等表征手段对所制备样品进行表征。结果表明，MgAl-LDH、Mg（Al）O在Fe₃O₄表面生长，并具有一定的磁响应能力。在反应时间为4 h、醇油物质的量比为13:1的条件下，生物柴油产率高达90%。经过三次使用后，仍具有一定活性。在外磁场的作用下可完成催化剂与反应物的分离。
- 生物柴油 /
- 磁性 /
- 酯交换 /
- 水滑石
Abstract: Magnetic Fe₃O₄ was synthesized by chemical coprecipitation method, and used as a raw material for preparing Fe₃O₄/MgAl-LDH. The calcined Fe₃O₄/Mg(Al)O was taken as the catalyst for the transesterification of microalgae oil with methanol, and the biodiesel yield was used to evaluate the activity of the catalyst. Several instruments including TG-DTG, XRD, SEM, EDS, TEM, N₂ absorption-desorption and VSM were employed to characterize the catalysts. The results show that MgAl-LDH and Mg(Al)O are successfully formed on Fe₃O₄ particles which have a strong magnetic response. When the reaction time is 4 h and the methanol/oil mol ratio is 13:1, the biodiesel oil yield reaches to 90%. After using for three times the catalyst still has certain activity and can be easily separated and recycled.
- biodiesel /
- magnetism /
- transesterification /
- hydrotalcite

HTML全文

图 1 Fe₃O₄/MgAl-LDH的TG-DTG曲线

Figure 1 TG-DTG curves of Fe₃O₄/MgAl-LDH

下载: 全尺寸图片幻灯片

图 2 MgAl-LDH (a)、Mg(Al)O (b)、Fe₃O₄ (c)、Fe₃O₄/MgAl-LDH (d)、Fe₃O₄/Mg(Al)O (e)催化剂的XRD谱图

Figure 2 XRD patterns of MgAl-LDH (a), Mg(Al)O (b), Fe₃O₄ (c), Fe₃O₄/MgAl-LDH (d), and Fe₃O₄/Mg(Al)O (e) samples

下载: 全尺寸图片幻灯片

图 3 MgAl-LDH (a)、 Mg(Al)O (b)、 Fe₃O₄/MgAl-LDH (c)和Fe₃O₄/Mg(Al)O (d)的SEM照片，Fe₃O₄/MgAl-LDH (e)和 Fe₃O₄/Mg(Al)O (f)的TEM照片

Figure 3 SEM images of MgAl-LDH (a), Mg(Al)O (b), Fe₃O₄/MgAl-LDH (c) and Fe₃O₄/Mg(Al)O (d), TEM images of Fe₃O₄/MgAl-LDH (e) and Fe₃O₄/Mg(Al)O (f)

下载: 全尺寸图片幻灯片

图 4 Fe₃O₄/MgAl-LDH (a)和Fe₃O₄/Mg(Al)O (b)的EDS谱图

Figure 4 EDS spectrum of Fe₃O₄/MgAl-LDH (a) and Fe₃O₄/Mg(Al)O (b)

下载: 全尺寸图片幻灯片

图 5 Mg(Al)O (▲)、 Fe₃O₄/Mg(Al)O (●)的N₂吸附-脱附曲线

Figure 5 N₂ absorption-desorption of Mg(Al)O (▲) and Fe₃O₄/Mg(Al)O (●)

下载: 全尺寸图片幻灯片

图 6 Fe₃O₄ (a)、 Fe₃O₄/MgAl-LDH (b)和Fe₃O₄/Mg(Al)O (c)的磁滞回线

Figure 6 Room temperature magnetization curves of Fe₃O₄ (a) and Fe₃O₄/MgAl-LDH (b) and Fe₃O₄/Mg(Al)O (c) magnteic separation of the catalyst from the reaction mixture (A)→(B)

下载: 全尺寸图片幻灯片

图 7 反应时间(a)和不同醇油物质的量比(b)对生物柴油产率影响

Figure 7 Effect of reaction time (a) and methanol/oil mol ratio (b) on biodiesel yield

下载: 全尺寸图片幻灯片

图 8 Fe₃O₄/Mg(Al)O与Mg(Al)O的酯交换活性随时间的变化

Figure 8 Catalytic activity of Fe₃O₄/Mg(Al)O and Mg(Al)O in different reaction time

下载: 全尺寸图片幻灯片

图 9 Fe₃O₄/Mg(Al)O的重复利用性(a)及可再生性(b)

Figure 9 Reusability (a) and regeneration ability (b) of Fe₃O₄/Mg(Al)O

下载: 全尺寸图片幻灯片

表 1 微藻油脂的理化性质

Table 1 Physical and chemical properties of microalgae oil

Number	Acid value w/(mgKOH·g^-1)	Saponification value w/(mgKOH·g^-1)	Moisture and volatile matter x/%	Average molecular weight q/(g·mol^-1)
1	0.93	188.346	0.18	898.00
2	0.93	188.137	0.18	899.00
3	0.94	188.570	0.17	896.00
Average value	0.93	188.351	0.18	898.00

下载: 导出CSV

表 2 不同样品的比表面积和孔结构

Table 2 Results of N₂ absorption-desorption measurements for different samples

Catalyst	BET surface area A/(m²·g^-1)	Total pore volume v/(cm³·g^-1)	Pore size d/nm
Mg(Al)O	138	0.62	11.15
Fe₃O₄/ Mg(Al)O	228	0.92	13.50

下载: 导出CSV

参考文献(29)

[1]	CREASEY J J, CHIEREGATO A, MANAYIL J C, PARLETT C M, WILSON K, LEE A F.Alkali-and nitrate-free synthesis of highly active Mg-Al hydrotalcite-coated alumina for FAME production[J].Catal Sci Technol, 2014, 4(3):861-870. doi: 10.1039/C3CY00902E
[2]	LIN C Y, CHENG H H.Application of mesoporous catalysts over palm-oil biodiesel for adjusting fuel properties[J].Energy Convers Manage, 2012, 53(1):128-134. doi: 10.1016/j.enconman.2011.08.019
[3]	MACOR A, PAVANELLO P.Performance and emissions of biodiesel in a boiler for residential heating[J].Energy, 2009, 34(12):2025-2032. doi: 10.1016/j.energy.2008.08.021
[4]	DENG X, FANG Z, LIU Y.Ultrasonic transesterification of Jatrophacurcas L.oil to biodiesel by a two-step process[J].Energy Convers Manage, 2010, 51(12):2802-2807. doi: 10.1016/j.enconman.2010.06.017
[5]	文利柏, 谭文广, 王运, 韩鹤友, 郑新生.固体酸催化剂催化乌桕籽油制备生物柴油[J].中国油脂, 2008, 33(6):44-47. http://www.cnki.com.cn/Article/CJFDTOTAL-ZYZZ200806013.htm WEN Li-bai, TAN Wen-guang, WANG Yun, HAN He-you, ZHENG Xin-sheng.Biodiesel preparation from stillingia oil by solid acid catalyzing[J].China Oils Fats, 2008, 33(6):44-47. http://www.cnki.com.cn/Article/CJFDTOTAL-ZYZZ200806013.htm
[6]	岳鹍, 王兴国, 金青哲, 刘元法.固体酸催化剂酸催化生物柴油合成反应性能的比较[J].中国油脂, 2006, 31(7):63-65. http://www.cnki.com.cn/Article/CJFDTOTAL-ZYZZ200607019.htm YUE Kun, WANG Xing-guo, JIN Qing-zhe, LIU Yuan-fa.Synthesis of biodiesel from frying oil catalyzed by solid acid catalyst[J].China Oils Fats, 2006, 31(7):63-65. http://www.cnki.com.cn/Article/CJFDTOTAL-ZYZZ200607019.htm
[7]	PULLEN J, SAEED K.Investigation of the factors affecting the progress of base-catalyzed transesterification of rapeseed oil to biodiesel FAME[J].Fuel Process Technol, 2015, 130:127-135. doi: 10.1016/j.fuproc.2014.09.013
[8]	SHIBASAKI-KITAKAWA N, HONDA H, KURIBAYASHi H, TODA T, FUKUMURA T, YONEMOTO T.Biodiesel production using anionic ion-exchange resin as heterogeneous catalyst[J].Bioresource Technol, 2007, 98:416-421. doi: 10.1016/j.biortech.2005.12.010
[9]	LIEN Y S, HSIEH L S, WU J C S.Biodiesel synthesis by simultaneous esterificationand transesterification using oleophilic acid ctalyst[J].Ind Eng Chem Res, 2010, 49(5):2118-2121. doi: 10.1021/ie901496h
[10]	LOTERO E, LIU Y, LOPEZ D E, SUWANNAKARN K, BRUCE D A, GOODWIN J G.Synthesis of biodiesel via acid catalysis[J].Ind Eng Chem Res, 2005, 44(14):5353-5363. doi: 10.1021/ie049157g
[11]	王建黎, 李永超, 徐之超, 计建炳.超声波辐射对醇油不相容体系酯交换反应的影响[J].中国油脂, 2006, 31(4):61-63. http://www.cnki.com.cn/Article/CJFDTOTAL-ZYZZ200604020.htm WANG Jian-li, LI Yong-chao, XU Zhi-chao, JI Jian-bing.Effect of ultrasonic on the transesterification of methanol-oil immiscible system[J].China Oils Fats, 2006, 31(4):61-63. http://www.cnki.com.cn/Article/CJFDTOTAL-ZYZZ200604020.htm
[12]	SREE R, KURIAKOSE S.Alkali salts of heteropoly tungstates:Efficient catalysts for the synthesis of biodiesel from edible and non-edible oils[J].J Energy Chem, 2015, 24(1):87-92. doi: 10.1016/S2095-4956(15)60288-1
[13]	赵策, 曾虹燕, 黄炎, 刘平乐, 王亚举, 杨永杰, 张伟.镁铁水滑石的制备及其对小球藻油脂合成生物柴油的催化性能[J].燃料化学学报, 2012, 40(3):337-344. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract17906.shtml ZHAO Ce, ZENG Hong-yan, HUANG Yan, LIU Le-ping, WANG Ya-ju, YANG Yong-jie, ZHANG Wei.Preparation of MgFe-hydrotalcites and their catalytic performance in synthesis of biodiesel oil from chlorella protothecoides oil[J].J Fuel Chem Technol, 2012, 40(3):337-344. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract17906.shtml
[14]	张慧, 徐彦红, 段雪.磁性纳米固体碱催化剂MgAl-OH-LDHs/NiFe₂O₄的合成、表征与性能研究[J].化学学报, 2004, 62(8):750-756. ZHANG Hui, XU Yan-hong, DUAN Xue.Synthesis characterization and properties of a nano-scale magnetic solid base catalyst MgAl-OH-LDHs/NiFe₂O₄[J].J Chem Ind Eng, 2004, 62(8):750-756.
[15]	盘登科, 张慧.核壳结构磁性镁铝复合氧化物亚微米粒子的制备与表征[J].无机化学学报, 2011, 27(7):1341-1347. http://www.cnki.com.cn/Article/CJFDTOTAL-WJHX201107021.htm PAN Deng-ke, ZHANG Hui.Synthesis and characterization of magnetic Mg-Al mixed oxides submicro particles with core-shell structure[J].Chin J Inorg Chem, 2011, 27(7):1341-1347. http://www.cnki.com.cn/Article/CJFDTOTAL-WJHX201107021.htm
[16]	TRUJILLANO R, HOLGADO M J, PIGAZO F, RIVES V.Preparation physicochemical characterisation and magnetic properties of Cu-Al layered double hydroxides with CO₃^2- and anionic surfactants with different alkyl chains in the interlayer[J].Phys B, 2006, 373(2):267-273. doi: 10.1016/j.physb.2005.11.154
[17]	SHAO M, NING F, ZHAO J, WEI M, EVANS D G, DUAN X.Preparation of Fe₃O₄@SiO₂@layered double hydroxide core-shell microspheres for magnetic separation of proteins[J].J Am Chem Soc, 2012, 134(2):1071-1077. doi: 10.1021/ja2086323
[18]	LIU W, ZHONG W, DU Y W.Magnetic nanoparticles with core/shell structures[J].J Nanosci Nanotechnol, 2008, 8(6):2781-2792.
[19]	AY A N, ZVMREOGLU-KARAN B, TEMEL A, RIVES V.Bioinorganic magnetic core-shell nanocomposites carrying antiarthritic agents:Intercalation of ibuprofen and glucuronic acid into Mg-Al-layered double hydroxides supported on magnesium ferrite[J].Inorg Chem, 2009, 48(18):8871-8877. doi: 10.1021/ic901097a
[20]	CHEN D, LI Y, ZHANG J, ZHOU J Z, GUO Y, LIU H.Magnetic Fe₃O₄/ZnCr-layered double hydroxide composite with enhanced adsorption and photocatalytic activity[J].Chem Eng J, 2012, 185:120-126.
[21]	HU S, GUAN Y, WANG Y, HAN H.Nano-magnetic catalyst KF/CaO-Fe₃O₄ for biodiesel production[J].Appl Energy, 2011, 88(8):2685-2690. doi: 10.1016/j.apenergy.2011.02.012
[22]	XUE B J, LUO J, ZHANG F, FANG Z.Biodiesel production from soybean and Jatropha oils by magnetic CaFe₂O₄-CaFe₂O₅-based catalyst[J].Energy, 2014, 68:584-591. doi: 10.1016/j.energy.2014.02.082
[23]	TANG S, WANG L, ZHANG Y, LI S, TIAN S, WANG B.Study on preparation of Ca/Al/Fe₃O₄ magnetic composite solid catalyst and its application in biodiesel transesterification[J].Fuel Process Technol, 2012, 95:84-89. doi: 10.1016/j.fuproc.2011.11.022
[24]	LEI X, ZHANG F, YANG L, GUO X, TIAN Y, FU S, DUAN X.Highly crystalline activated layered double hydroxides as solid acid-base catalysts[J].AIChE J, 2007, 53(4):932-940. doi: 10.1002/(ISSN)1547-5905
[25]	阎杰, 丘泰球.甘油铜比色法测定甘油含量的研究[J].中国油脂, 2004, 29(1):40-43. http://www.cnki.com.cn/Article/CJFDTOTAL-ZYZZ200401010.htm YAN Jie, QIU Tai-qiu, Determination of glycerol by cupric glycerinate colorimetry[J].China Oils Fats, 2004, 29(1):40-43. http://www.cnki.com.cn/Article/CJFDTOTAL-ZYZZ200401010.htm
[26]	CASENAVE S, MARTINEZ H, GUIMON C, AUROUX A, HULEA V, DUMITRIU E.Acid-base properties of MgCuAl mixed oxides[J].J Therm Anal Calorim, 2003, 72(1):191-198. doi: 10.1023/A:1023980005672
[27]	刘秀芳, 范彬彬, 高升成, 李瑞丰.C/MgAl水滑石复合材料为前驱物所制催化剂在柠檬醛丙酮缩合反应中的催化性能[J].无机化学学报, 2013, 29(2):345-349. LIU Xiu-fang, FAN Bin-bin, Gao Sheng-cheng, LI Rui-feng.Citral-acetone condensation over catalysts prepared from C/MgAl hydrotalcite hybrids[J].Chin J Inorg Chem, 2013, 29(2):345-349.
[28]	SHOU J, JIANG C, WANG F, QIU M, XU Q.Fabrication of Fe₃O₄ MgAl-layered double hydroxide magnetic composites for the effective decontamination of Co (Ⅱ) from synthetic wastewater[J].J Mol Liq, 2015, 207:216-223. doi: 10.1016/j.molliq.2015.03.047
[29]	GURSKY J A, BLOUGH S D, LUNA C, GOMEZ C, LUEVANO A N, GARDNER E A.Particle-particle interactions between layered double hydroxide nanoparticles[J].J Am Chem Soc, 2006, 128(26):8376-8377. doi: 10.1021/ja0612100