In situ co-precipitation of NiMg(Al)O on γ-Al2O3 and its catalytic performance in the transesterification
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摘要: 以γ-Al2O3为载体通过原位共沉淀法制备NiMgAl-LDHs/γ-Al2O3，经焙烧后得到NiMg（Al）O/γ-Al2O3催化剂，通过TG-DTG、XRD、SEM、BET、FT-IR、CO2-TPD等手段对催化剂进行了表征，并对其在酯交换制备生物柴油反应中的催化性能进行了研究。结果表明，NiMgAl-LDHs和NiMg（Al）O成功在γ-Al2O3内孔表面生长，并有良好的结合度。催化剂对酯交换具有很高的催化活性；在醇油物质的量比为12：1的条件下反应3 h，生物柴油产率为95%，重复使用七次后，生物柴油产率仍然在82%以上。Abstract: NiMgAl-LDHs/γ-Al2O3 was first synthesized by in-situ co-precipitation method with γ-Al2O3 as support, which was further transformed to the NiMg(Al)O/γ-Al2O3 catalyst through calcination. The NiMg(Al)O/γ-Al2O3 catalyst was characterized by TG-DTG, XRD, SEM, N2 physisorption, FT-IR and CO2-TPD and its performance in the transesterification was investigated, for the production of biodiesel with microalgae oil and methanol as raw materials. The results show that NiMgAl-LDHs and NiMg(Al)O are successfully developed on the surface and pores of γ-Al2O3 with high binding strength. The NiMg(Al)O/γ-Al2O3 catalyst exhibits high activity in transesterification; with a methanol/oil molar ratio of 12:1, the yield of biodiesel oil reaches 95% after reaction for 3 h. Moreover, the yield of biodiesel is still above 82% after using seven times.
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Key words:
- biodiesel /
- γ-Al2O3 /
- transesterification /
- hydrotalcite
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图 2 催化剂的XRD谱图
Figure 2 XRD patterns of catalysts
a: NiMgAl-LDHs; b: NiMg(Al)O; c: γ-Al2O3; d: NiMgAl-LDHs/γ-Al2O3; e: NiMg(Al)O/γ-Al2O3
图 3 催化剂的SEM照片
Figure 3 SEM images of catalysts
(a): NiMgAl-LDHs/γ-Al2O3; (b): NiMg(Al)O/γ-Al2O3; (c): NiMgAl-LDHs; (d): NiMg(Al)O
图 4 催化剂的N2吸附-脱附曲线
Figure 4 N2 absorption-desorption isotherms of catalysts
a: γ-Al2O3; b: NiMg(Al)O; c: NiMg(Al)O/γ-Al2O3
图 6 催化剂的FT-IR谱图
Figure 6 FT-IR spectrum of catalysts
a: γ-Al2O3; b: NiMgAl-LDHs; c: NiMgAl-LDHs/γ-Al2O3
图 7 γ-Al2O3和NiMg(Al)O/γ-Al2O3的CO2-TPD谱图
Figure 7 CO2-TPD spectra of γ-Al2O3(a), NiMg(Al)O/γ-Al2O3(b)
图 8 反应时间和不同醇油物质的量比对生物柴油产率影响
Figure 8 Effect of reaction time (a) and methanol/oil molar ratio (b) on the biodiesel yield from the transesterification of microalgae oil with methanol
图 9 NiMg(Al)O/γ-Al2O3的重复利用性及回收率
Figure 9 Reusability (a) and recovery (b) of NiMg(Al)O/γ-Al2O3
图 10 NiMg(Al)O/γ-Al2O3 和重复使用七次后NiMg(Al)O/γ-Al2O3 的XRD谱图
Figure 10 XRD patterns of the fresh NiMg(Al)O/γ-Al2O3 catalyst (a) and spent NiMg(Al)O/γ-Al2O3 catalyst after used for 7 cycles (b)
表 1 不同催化剂的结构参数
Table 1 Texture properties of different catalysts
Catalyst BET surface
area A/
(m2·g-1)Total pore
volume v/
(cm3·g-1)Pore size
d/nmγ-Al2O3 140.18 0.66 19.72 NiMg(Al)O 132.51 0.41 8.46 NiMg(Al)O/γ-Al2O3 156.90 0.43 9.04 
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[1] POOSUMAS J, NGAOSUWAN K, QUITAIN A T, ASSABUMRUNGRAT, S. Role of ultrasonic irradiation on transesterification of palm oil using calcium oxide as a solid base catalyst[J]. Energy Convers Manage, 2016, 120:62-70. doi: 10.1016/j.enconman.2016.04.063 [2] KNOTHE G, SHARP C A, RYAN T W. Exhaust emissions of biodiesel, petrodiesel, neat methyl esters, and alkanes in a new technology engine[J]. Energy Fuels, 2006, 20(1):403-408. doi: 10.1021/ef0502711 [3] 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[J].燃料化学学报, 2016, 44(10):1217-1224. doi: 10.3969/j.issn.0253-2409.2016.10.009CHEN Ying, HE Han, KONG Xiang-sen, LIU Tian-cong. Preparation of compound magnetic Fe3O4/MgAl-layered double hydroxide and its application in biodiesel transesterification[J]. J Fuel Chem Technol, 2016, 44(10):1217-1224. doi: 10.3969/j.issn.0253-2409.2016.10.009 [4] VICENTE G, MARTINEZ M, ARACIL J. Integrated biodiesel production:A comparison of different homogeneous catalysts systems[J]. Bioresource Technol, 2004, 92(3):297-305. doi: 10.1016/j.biortech.2003.08.014 [5] MEHER L C, SAGAR D V, NAIK S N. Technical aspects of biodiesel production by transesterification-a review[J]. Renew Sust Energy Rev, 2006, 10(3):248-268. doi: 10.1016/j.rser.2004.09.002 [6] 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 [7] 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 [8] LEI X, ZHANG F, YANG L, GUO X, TIAN Y, FU S, LI F, EVANS D G, 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 [9] 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://manu60.magtech.com.cn/rlhxxb/CN/abstract/abstract17906.shtmlZHAO 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://manu60.magtech.com.cn/rlhxxb/CN/abstract/abstract17906.shtml [10] 倪哲明, 李远, 施炜, 薛继龙, 刘娇.镍镁铝类水滑石的超分子结构、电子性质及稳定性[J].物理化学学报, 2012, 28(9):2051-2056. http://www.whxb.pku.edu.cn/CN/abstract/abstract28142.shtmlNI Zhe-ming, LI Yuan, SHI Wei, XUE Ji-long, LIU Jiao. Supramolecular structure, electronic property and stability of Ni-Mg-Al layered double hydroxides[J]. Acta Phys-Chim Sin, 2012, 28(9):2051-2056. http://www.whxb.pku.edu.cn/CN/abstract/abstract28142.shtml [11] LIU P, DERCHI M, HENSEN E J M. Promotional effect of transition metal doping on the basicity and activity of calcined hydrotalcite catalysts for glycerol carbonate synthesis[J]. Appl Catal B:Environ, 2014, 144:135-143. doi: 10.1016/j.apcatb.2013.07.010 [12] HU F, WANG Y, LAI X, WU Y, DU F, WANG C. Facile synthesis of mesoporous Si-containingγ-Al2O3 nanofiber with enhanced thermal stability[J]. Chem Res Chin Univ, 2015, 31(1):156-159. doi: 10.1007/s40242-015-4322-0 [13] MARCINAUSKAS L, MILIESKA M, KEZELIS R. Effect of torch power on the microstructure of plasma sprayed Al2O3 coatings[J]. Surf Interface Anal, 2016, 48(7):552-555. doi: 10.1002/sia.v48.7 [14] WU C, YUAN W, HAUNG Y, XIA Y, YANG H, WANG H, LIU X. Conversion of xylose into furfural catalyzed by bifunctional acidic ionic liquid immobilized on the surface of magneticγ-Al2O3[J]. Catal Lett, 2017, 147(4):953-963. doi: 10.1007/s10562-017-1982-z [15] MISRAC Industrial Alumina Chemicals[M]. NewYork:American Chemical Society, 1986. [16] GUO X, XU S, ZHAO L, LU W, ZHANG F, EVANS D G, DUAN X. One-step hydrothermal crystallization of a layered double hydroxide/alumina bilayer film on aluminum and its corrosion resistance properties[J]. Langmuir, 2009, 25(17):9894-9897. doi: 10.1021/la901012w [17] NIE Y, LI N, HU C. Enhanced inhibition of bromate formation in catalytic ozonation of organic pollutants over Fe-Al LDH/Al2O3[J]. Sep Purif Technol, 2015, 151:256-261. doi: 10.1016/j.seppur.2015.07.057 [18] FENG J T, LIN Y J, EVANS D G, DUAN X, LI D Q. Enhanced metal dispersion and hydrodechlorination properties of a Ni/Al2O3 catalyst derived from layered double hydroxides[J]. J Catal, 2009, 266(2):351-358. doi: 10.1016/j.jcat.2009.07.001 [19] SHAHRAKI H, ENTEZARI M H, GOHARSHADI E K. Sono-synthesis of biodiesel from soybean oil by KF/γ-Al2O3 as a nano-solid-base catalyst[J]. Ultrason sonochem, 2015, 23:266-274. doi: 10.1016/j.ultsonch.2014.09.010 [20] 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://manu60.magtech.com.cn/rlhxxb/CN/abstract/abstract18429.shtmlHU 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://manu60.magtech.com.cn/rlhxxb/CN/abstract/abstract18429.shtml [21] XIE W, PENG H, CHEN L. Transesterification of soybean oil catalyzed by potassium loaded on alumina as a solid-base catalyst[J]. Appl Catal A:Gen, 2006, 300(1):67-74. doi: 10.1016/j.apcata.2005.10.048 [22] YUAN C, LIU H, CAO X. Magnetically recoverable heterogeneous catalyst:Tungstate intercalated Mg-Al-Layered double hydroxides-encapsulated Fe3O4 nanoparticles for highly efficient selective oxidation of sulfides with H2O2[J]. Catal lett, 2014, 144(1):16-21. doi: 10.1007/s10562-013-1129-9 [23] 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.cqvip.com/qk/91569X/200401/9065909.htmlYAN jie, QIU Tai-qiu. Determination of glycerol by cupric glycerinate colorimetry[J]. China Oils Fats, 2004, 29(1):40-43. http://www.cqvip.com/qk/91569X/200401/9065909.html [24] HICAPIE G, LÓPEZ D, MORENO A. Infrared analysis of methanol adsorption on mixed oxides derived from Mg/Al hydrotalcite catalysts for transesterification reactions[J]. Catal Today, 2018, 302:277-285. doi: 10.1016/j.cattod.2017.05.052 [25] ZHANG J, WEI W, SUN Y. Fluorine-modified mesoporous Ni-Mg-Al mixed oxides for partial oxidation of methane[J]. Catal Lett, 2010, 135(3/4):321-329. doi: 10.1007/s10562-010-0268-5 [26] ABDOLLAHIFAR M. Synthesis and characterisation ofγ-Al2O3 with porous structure and nanorod morphology[J]. J Chem Res, 2014, 38(3):154-158. doi: 10.3184/174751914X13910938972748 [27] 毛纾冰, 李殿卿, 张法智, 段雪.γ-Al2O3表面原位合成Ni-Al-CO3 LDHs研究[J].无机化学学报, 2004, 20(5):596-602. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=wjhxxb200405021MAO Shu-bing, LI Dian-qing, ZHANG Fa-zhi, DUAN Xue. In situ synthesis of Ni-Al-CO3 LDHs on the surface ofγ-Al2O3[J]. Chin J Inorg Chem, 2004, 20(5):596-602. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=wjhxxb200405021 [28] 王新星, 汪学广, 尚兴付, 聂望欣, 邹秀晶, 鲁雄钢, 丁伟中.镁铝混合氧化物负载镍催化剂上液化石油气的预重整[J].催化学报, 2012, 33(7):1176-1182. https://www.researchgate.net/profile/Xionggang_Lu/publication/287283390_Preparation_of_Mg-Al_Mixed_Oxide_Supported_Nickel_Catalysts_and_Their_Catalytic_Activities_in_Low_Temperature_Reforming_of_Liquified_Petroleum_Gas/links/5676a67d08ae0ad265c58a4e.pdf?origin=publication_detailWANG Xin-xing, WANG Xue-guang, SAHNG Fu-xing, NIE Wang-xin, ZOU Xiu-jing, LU Xiong-gang, DING Wei-zhong. Pre-reforming of liquefied petroleum gas over magnesium aluminum mixed oxide supported nickel catalysts[J]. Chin J Catal, 2012, 33(7):1176-1182. https://www.researchgate.net/profile/Xionggang_Lu/publication/287283390_Preparation_of_Mg-Al_Mixed_Oxide_Supported_Nickel_Catalysts_and_Their_Catalytic_Activities_in_Low_Temperature_Reforming_of_Liquified_Petroleum_Gas/links/5676a67d08ae0ad265c58a4e.pdf?origin=publication_detail [29] 谢鲜梅, 刘洁翔, 安霞, 武正簧, 王志忠. NiMgAl三元类水滑石的制备研究[J].燃料化学学报, 2003, 31(6):620-623. http://industry.wanfangdata.com.cn/dl/Detail/Periodical?id=Periodical_rlhxxb200306021XIE Xian-mei, LIU Jie-xiang, AN Xia, WU Zheng-huang, WANG Zhen-zhong. Study on the synthesis of NiMgAl hydrotalcite-like compounds[J]. J Fuel Chem Technol, 2003, 31(6):620-623. http://industry.wanfangdata.com.cn/dl/Detail/Periodical?id=Periodical_rlhxxb200306021 [30] BENSON T J, HERNANDEZ R, FRENCH W T, ALLEY E G, HOLMES W E. Elucidation of the catalytic cracking pathway for unsaturated mono-, di-, and triacylglycerides on solid acid catalysts[J]. J Mol Catal A:Chem, 2009, 303(1):117-123. https://www.sciencedirect.com/science/article/pii/S138111690900020X [31] 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油[J].燃料化学学报, 2012, 40(3):331-336. http://manu60.magtech.com.cn/rlhxxb/CN/abstract/abstract17905.shtmlZHENG 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://manu60.magtech.com.cn/rlhxxb/CN/abstract/abstract17905.shtml -
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