棕榈油酯交换合成生物柴油中NiO与La_2O_2CO_3的协同作用
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摘要
采用共沉淀法制备了La_2O_2CO_3-NiO固体碱催化剂,用于甲醇与棕榈油酯交换反应合成生物柴油体系。采用XRD,SEM,EDS,CO_2-TPD,XPS等方法对催化剂的微观结构进行表征,并研究了催化剂的性能。实验结果表明,镧镍摩尔比为1∶1,于400℃焙烧5 h,制备的La_2O_2CO_3-NiO固体碱催化剂的催化效果最佳;在催化剂用量为4%(w)、醇油摩尔比为15∶1、反应温度为65℃、反应时间为3 h时,生物柴油的收率最大,可达94.59%;引入NiO后,改善了La_2O_2CO_3-NiO固体碱催化剂的分散性,提高了催化剂的强碱位碱量和活性; La_2O_2CO_3-NiO固体碱催化剂重复使用5次后,生物柴油的收率仍然能达到85.00%,说明La_2O_2CO_3-NiO固体碱催化剂具有较好的重复使用性。
The La_2O_2CO_3-NiO solid base catalyst was prepared by coprecipitation method and applied to the system of biodiesel synthesis by transesteri?cation of methanol with palm oil. The microstructure of the catalyst was characterize by XRD,SEM,EDS,CO_2-TPD and XPS,and the performance of the catalyst was studied. The experimental results showed that the prepared La_2O_2CO_3-Ni O base catalyst had the best catalytic effect under the condition that the molar ratio of lanthanum to nickel was 1∶1 and calcination time was 5 h at 400 ℃;and the biodiesel reached a maximum yield of 94.59% when the amount of catalyst was 4%(w),the molar ratio of methanol to oil was 15∶1,the materials reacted at 65 ℃,and for 3 h.The introduction of NiO improved the dispersibility of the La_2O_2CO_3-NiO base catalyst,the base amount at strong basic sites and catalytic activity of the La_2O_2CO_3-Ni O base catalyst. Finally,it was veri?ed by experiments that the yield of biodiesel can still reach 85.00% with the catalyst repeatedly used for 5 times,indicating that the La_2O_2CO_3-NiO solid base catalyst has good reusability.
The La_2O_2CO_3-NiO solid base catalyst was prepared by coprecipitation method and applied to the system of biodiesel synthesis by transesteri?cation of methanol with palm oil. The microstructure of the catalyst was characterize by XRD,SEM,EDS,CO_2-TPD and XPS,and the performance of the catalyst was studied. The experimental results showed that the prepared La_2O_2CO_3-Ni O base catalyst had the best catalytic effect under the condition that the molar ratio of lanthanum to nickel was 1∶1 and calcination time was 5 h at 400 ℃;and the biodiesel reached a maximum yield of 94.59% when the amount of catalyst was 4%(w),the molar ratio of methanol to oil was 15∶1,the materials reacted at 65 ℃,and for 3 h.The introduction of NiO improved the dispersibility of the La_2O_2CO_3-NiO base catalyst,the base amount at strong basic sites and catalytic activity of the La_2O_2CO_3-Ni O base catalyst. Finally,it was veri?ed by experiments that the yield of biodiesel can still reach 85.00% with the catalyst repeatedly used for 5 times,indicating that the La_2O_2CO_3-NiO solid base catalyst has good reusability.
引文
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[24]Gu Weiwei,Liu Jingjun,Hu Mingan,et al.La2O2CO3encapsulated La2O3 nanoparticles supported on carbon as superior electrocatalysts for oxygen reduction reaction[J].ACSAppl Mater Interfaces,2015,7(48):26914-26922.
[25]Yashnik S A,Chesalov Y A,Ishchenko A V,et al.Effect of Pt addition on sulfur dioxide and water vapor tolerance of Pd-Mn-hexaaluminate catalysts for high-temperature oxidation of methane[J].Appl Catal,B,2017,204:89-106.
[26]Verziu M,Cojocaru B,Hu Juncheng,et al.Sunflower and rapeseed oil transesterification to biodiesel over different nanocrystalline MgO catalysts[J].Green Chem,2008,10(4):373-381.
[27]Simanjuntak F S H,Widyaya V T,Kim C S,et al.Synthesis of glycerol carbonate from glycerol and dimethyl carbonate using magnesium-lanthanum mixed oxide catalyst[J].Chem Eng Sci,2013,94(5):265-270.
[28]Chen Gang,Han Bingqian,Deng Shaojuan,et al.Lanthanum dioxide carbonate La2O2CO3 nanorods as a sensing material for chemoresistive CO2 gas sensor[J].Electrochim Acta,2014,127:355-361.
[29]Zhang Xiaoxue,Xiao Qingqing,Zhang Yuxia,et al.La2O3 doped carbonaceous microspheres:A novel bifunctional electrocatalyst for oxygen reduction and evolution reactions with ultrahigh mass activity[J].J Phys Chem C,2014,118(35):20229-20237.
[2]王常文,崔方方,宋宇.生物柴油的研究现状及发展前景[J].中国油脂,2014,39(5):44-48.
[3]Li Qin,Yan Yunjun.Production of biodiesel catalyzed by immobilized Pseudomonas cepacia lipase from sapium sebiferum oil in micro-aqueous phase[J].Appl Energy,2010,87(10):3148-3154.
[4]Du Wei,Xu Yuanyuan,Liu Dehua,et al.Comparative study on lipasecatalyzed transesterification of soybean oil for biodiesel production with different acyl acceptors[J].J Mol Catal B,2004,30(3/4):125-129.
[5]Serio D M,Tesser R,Lu Pengmei,et al.Heterogeneous catalysts for biodiesel production[J].Energy Fuels,2008,22(1):207-217.
[6]Sivasamy A,Cheah K Y,Fornasiero P,et al.Catalytic applications in the production of biodiesel from vegetable oils[J].Chem Sus Chem,2009,2(4):278-300.
[7]Ebiura T,Echizen T,Ishikawa A,et al.Selective transesterification of triolein with methanol to methyl oleate and glycerol using alumina loaded with alkali metal salt as a solid-base catalyst[J].Appl Catal,A,2005,283(1/2):111-115.
[8]Kim H J,Kang B S,Kim M J,et al.Transesterification of vegetable oil to biodiesel using heterogeneous base catalysts[J].Catal Today,2004,93-95:315-320.
[9]Dorado M P,Ballesteros E,Lopez F J,et al.Optimization of alkali-catalyzed transesterification of brassica carinata oil for biodiesel production[J].Energy Fuels,2004,18(1):77-83.
[10]石敏,范明明,张萍波,等.栗毛球状CaO@MgO碱催化剂的制备及其在生物柴油制备上的应用[J].石油化工,2017,46(4):403-408.
[11]付希,王宜涛,张月,等.CaO-ZnO固体碱催化剂的制备及其催化大豆油酯交换反应的性能[J].石油化工,2017,46(5):552-557.
[12]田志茗,常宝琪,邓启刚.KF/锌铝水滑石的制备及其催化大豆油酯交换反应的性能[J].石油化工,2016,45(1):47-51.
[13]侯丽伟,易玉峰,丁福臣.高碘酸氧化法测定甘油含量影响因素研究[J].粮食与油脂,2010(1):36-39.
[14]郭萍梅,黄庆德.生物柴油中游离甘油和总甘油测定方法研究[J].粮食与油脂,2003(8):41-42.
[15]Valderrama G,Goldwasser M R,Navarro C U D,et al.Dry reforming of methane over Ni perovskite type oxides[J].Catal Today,2005,107(44):785-791.
[16]Pere?iguez R,Gonzalez-Delacruz V M,Caballero A,et al.LaNiO3,as a precursor of Ni/La2O3,for CO2,reforming of CH4:Effect of the presence of an amorphous NiO phase[J].Appl Catal,B,2012,123-124(14):324-332.
[17]Wang Liguo,Ma Yubo,Wang Ying,et al.Efficient synthesis of glycerol carbonate from glycerol and urea with lanthanum oxide as a solid base catalyst[J].Catal Commun,2011,12(15):1458-1462.
[18]Wu Yuanfeng,Song Xianghai,Cai Fufeng,et al.Synthesis of glycerol carbonate from glycerol and diethyl carbonate over CeNi O catalyst:The role of multiphase Ni[J].J Alloys Compd,2017,720:360-368.
[19]Soriano L,Gutiérrez A,Preda I,et al.Splitting of Ni 3d states at the surface of NiO nanostructures[J].Phys Rev B,2006,74(19):193402.
[20]Turgut E,?oban?,Sar?ta?S,et al.Oxygen partial pressure effects on the RF sputtered p-type NiO hydrogen gas sensors[J].Appl Surf Sci,2018,435:880-885.
[21]Fujimori A,Minami F.Valence-band photoemission and optical absorption in nickel compounds[J].Phys Rev B:Condens Matter,1984,30(2):957-971.
[22]Zhou Xiaosong,Chen Yilei,Li Cuifen,et al.Construction of LaNiO3 nanoparticles modified g-C3N4 nanosheets for enhancing visible light photocatalytic activity towards tetracycline degradation[J].Sep Purif Technol,2019,211:179-188.
[23]Rabelo-Neto R C,Sales H B E,Inocêncio C V M,et al.CO2reforming of methane over supported LaNiO3 perovskite-type oxides[J].Appl Catal,B,2018,221:349-361.
[24]Gu Weiwei,Liu Jingjun,Hu Mingan,et al.La2O2CO3encapsulated La2O3 nanoparticles supported on carbon as superior electrocatalysts for oxygen reduction reaction[J].ACSAppl Mater Interfaces,2015,7(48):26914-26922.
[25]Yashnik S A,Chesalov Y A,Ishchenko A V,et al.Effect of Pt addition on sulfur dioxide and water vapor tolerance of Pd-Mn-hexaaluminate catalysts for high-temperature oxidation of methane[J].Appl Catal,B,2017,204:89-106.
[26]Verziu M,Cojocaru B,Hu Juncheng,et al.Sunflower and rapeseed oil transesterification to biodiesel over different nanocrystalline MgO catalysts[J].Green Chem,2008,10(4):373-381.
[27]Simanjuntak F S H,Widyaya V T,Kim C S,et al.Synthesis of glycerol carbonate from glycerol and dimethyl carbonate using magnesium-lanthanum mixed oxide catalyst[J].Chem Eng Sci,2013,94(5):265-270.
[28]Chen Gang,Han Bingqian,Deng Shaojuan,et al.Lanthanum dioxide carbonate La2O2CO3 nanorods as a sensing material for chemoresistive CO2 gas sensor[J].Electrochim Acta,2014,127:355-361.
[29]Zhang Xiaoxue,Xiao Qingqing,Zhang Yuxia,et al.La2O3 doped carbonaceous microspheres:A novel bifunctional electrocatalyst for oxygen reduction and evolution reactions with ultrahigh mass activity[J].J Phys Chem C,2014,118(35):20229-20237.