Citation: SHU Qing, HOU Xiao-peng, TANG Guo-qiang, YU Chang-lin, WANG Jin-fu. Preparation of a novel solid Lewis acid Ce³⁺-Ti⁴⁺-SO₄^2-/MWCNTs and its application in the synthesis of biodiesel from esterification reaction[J]. Journal of Fuel Chemistry and Technology, ;2017, 45(1): 65-74. shu

Preparation of a novel solid Lewis acid Ce³⁺-Ti⁴⁺-SO₄^2-/MWCNTs and its application in the synthesis of biodiesel from esterification reaction

1.
School of Metallurgy and Chemical Engineering, Jiangxi University of Science and Technology, Ganzhou 341000, China
2.
Department of Chemical Engineering, Tsinghua University, Beijing 100084, China

Corresponding author: SHU Qing, shuqing@jxust.edu.cn
Received Date: 16 August 2016
Revised Date: 4 November 2016

Fund Project: National Natural Science Foundation of China 21206062and Open Project Program of Key Laboratory for Large-Format Battery Materials and System of Huazhong University of Science and Technolog 201504Open Project Program of National United Key Laboratory of Chemical Engineering Tsinghua University, SKL-chE-14A04National Natural Science Foundation of China 21466013Major Project of Natural Science Foundation of Jiangxi Province for Youth 20143ACB21018

Figures(12)

The Ce³⁺-Ti⁴⁺-SO₄^2-/MWCNTs catalyst was prepared from the modification treatment of multi walled carbon nanotubes by concentrated sulfuric acid, Ce³⁺ and Ti⁴⁺ through the employing of high temperature impregnation method. Physicochemical properties and structural characteristics of the obtained-catalysts were characterized by means of transmission electron microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, pyridine adsorption FT-IR spectra, X-ray fluorescence spectroscopy, X-ray diffraction and NH₃ temperature programmed desorption. The catalytic activity of Ce³⁺-Ti⁴⁺-SO₄^2-/MWCNTs for the synthesis of biodiesel from the esterification of methanol and oleic acid was investigated. The influence of SO₄^2-/MWCNTs, which was resulted from the addition of Ce³⁺ and Ti⁴⁺, on the structure and catalytic activity was cleared based on the above structure characterization and catalytic activity investigation. The results showed that the conversion of oleic acid reached 93.4% after 5 h reaction at 65℃, when the catalyst/reactants was 1% and the molar ratio of methanol/oleic acid was 12:1. The conversion of oleic acid was 80.8% after the Ce³⁺-Ti⁴⁺-SO₄^2-/MWCNTs were cycled for eight times. Therefore, it can be concluded that this catalyst has high catalytic activity and stability. The high catalytic activity and stability can be explained as follows:the C 1s binding energy of carbon nanotube is much lower than other carbon materials, resulting in easy flow and escape of the electrons in the tubular structure. Thus, the strong interactions will occur among the active groups that have been loaded on the carbon nanotube, which impels Ce³⁺ and Ti⁴⁺ to respectively form stable coordination bonds with SO₄^2-, increases the crystallization degree of the Ce³⁺-Ti⁴⁺-SO₄^2-/MWCNTs catalyst and the active acid sites without increasing the surface defects, and the combination of SO₄^2- and MWCNTs was more stable. In addition, the chemical state of surface atom on the Ti-SO₄^2- was changed due to the strong interaction between SO₄^2- and Ce³⁺, which strengthened the electron withdrawing ability of S⁶⁺ and Ti⁴⁺ ions and enhanced the acidity strength of Lewis acid with changing of the acid type. Hence, the Ce³⁺-Ti⁴⁺-SO₄^2-/MWCNTs will be composed by Lewis acid sites mainly, which is favorable for avoiding the occurrence of hydration of acid active sites for the SO₄^2-/MWCNTs catalyst because it was composed of Brönsted acid sites mainly.
- biodiesel,
- carbon nanotube,
- solid Lewis Acid,
- esterification,
- coordination bond
1. [1]
  LIANG Jin-hua, REN Xiao-qian, WANG Jin-tang, JIANG min, LI Zhen-jiang. Preparation of biodiesel by transesterification from cottonseed oil using the basic dication ionic liquids as catalyst[J]. J Fuel Chem Technol, 2010,38(3):275-280. doi: 10.1016/S1872-5813(10)60033-3
2. [2]
  HOSSEINI S, JANAUN J, CHOONG T S Y. Feasibility of honeycomb monolith supportedsugar catalyst to produce biodiesel from palm fattyacid distillate (PFAD)[J]. Process Saf Environ Prot, 2015,98:285-295. doi: 10.1016/j.psep.2015.08.011
3. [3]
  SHYAMSUNDAR M, SHAMSHUDDIN S Z M, ANIZ C U. Cordierite honeycomb monoliths coated with zirconia and its modified forms for biodiesel synthesis from pongamiaglabra[J]. J Am Oil Chem Soc, 2015,92(3):335-344. doi: 10.1007/s11746-015-2609-4
4. [4]
  KAUR N, ALI A. Preparation and application of Ce/ZrO₂-TiO₂/SO₄^2-as solid catalyst for the esterification of fatty acids[J]. Renewable Energy, 2015,64(11):6392-6395.
5. [5]
  SHU Qing, HOU Xiao-peng, LIU Feng-sheng, TANG Guo-qiang, XU Bao-quan, ZHANG Cai-xia. Studies on the catalytic activity of La-modified phosphotungstic heteropoly acid salt in the synthesis of biodiesel from the esterification of methanol and oleci acid[J]. Nonfer Metal Sci Eng, 2016,7(3):131-136.
6. [6]
  SHU Q, ZHANG Q, XU G, WANG J F. Preparation of biodiesel using s-MWCNT catalysts and the coupling of reaction and separation[J]. Food Bioprod Process, 2009,87(3):164-170. doi: 10.1016/j.fbp.2009.01.004
7. [7]
  JUAN J C, JIANG Y J, MENG X J, CAO W L, YARMO M A, ZHANG J C. Supported zirconium sulfate on carbon nanotubes as water-tolerant solid acid catalyst[J]. Mater Res Bull, 2007,42(7):1278-1285. doi: 10.1016/j.materresbull.2006.10.017
8. [8]
  IGLESIAS J, MELERO J A, MORALES G, MORENO J, SEGURA Y, PANIAGUA M, CAMBRA A, HERNÁNDEZ B. Zr-SBA-15 lewis acid catalyst:Activity in meerwein ponndorf verley reduction[J]. Catalysts, 2015,5(4):1911-1927. doi: 10.3390/catal5041911
9. [9]
  GUAN Q Q, SHANG H, LIU J, NING P. Biodiesel from transesterification at low temperature by AlCl₃catalysis in ethanol and carbon dioxide as cosolvent:Process, mechanism and application[J]. Appl Energy, 2016,164:380-386. doi: 10.1016/j.apenergy.2015.11.029
10. [10]
  MELERO J A, IGLESIAS J, MORALES G. Heterogeneous acid catalysts for biodiesel production:current status and future challenges[J]. Green Chem, 2009,11(11):1285-1308.
11. [11]
  REINOSO D M, DAMIANI D E, TONETTO G M. Efficient production of biodiesel from low-cost feedstock using zinc oleate as catalyst[J]. Fuel Process Technol, 2015,134:26-31. doi: 10.1016/j.fuproc.2015.03.003
12. [12]
  CHERYL-LOW Y L, THEAM K L, LEE H V. Alginate-derived solid acid catalyst for esterification of low-cost palm fatty acid distillate[J]. Energ Convers Manage, 2015,106:932-940. doi: 10.1016/j.enconman.2015.10.018
13. [13]
  ALMEIDA R M D, NODA L K, GONALVES N S, MENEGHETTI S M P, MENEGHETTI M R. Transesterification reaction of vegetable oils, using superacid sulfated TiO₂-base catalysts[J]. Appl Catal A:Gen, 2008,347(1):100-105. doi: 10.1016/j.apcata.2008.06.006
14. [14]
  HOU Kai-Jun, MENG Ming, ZOU Zhi-Qiang, LV Qian. Effect of La³⁺ doping on the structures and performance of nano-structured Au/TiO₂ catalysts[J]. Chin J Inorg Chem, 2007,23(9):1538-1544.
15. [15]
  ZHANG X H, TANG Q Q, YANG D, HU J H. Preparation of poly (p-styrenesulfonic acid) grafted multi-walled carbonnanotubes and their application as a solid-acid catalyst[J]. Mater Chem Phys, 2011,126(1):310-313.
16. [16]
  JUMI Y, JI S I, YOUNG S L, HYUNG I K. Effect of oxyfluorination on electromagnetic interference shielding behavior of MWCNT/PVA/PAAc composite microcapsules[J]. Eur Polym J, 2010,46(5):900-909. doi: 10.1016/j.eurpolymj.2010.02.005
17. [17]
  REDDY G K, HE J, THIEL S W, PINTO N G, SMIRNIOTIS P G. Sulfur-tolerant Mn-Ce-Ti sorbents for elemental mercury removal from flue gas:Mechanistic investigation by XPS[J]. J Phys Chem C, 2015,119(16):8634-8644. doi: 10.1021/jp512185s
18. [18]
  LI Z J, DENG S B, YU G, HUANG J, LIM V C. As (Ⅴ) and As (Ⅲ) removal from water by a Ce-Ti oxide adsorbent:Behavior and mechanism[J]. Chem Eng J, 2010,161(1/2):106-113.
19. [19]
  LAN L, CHEN S, ZHAO M, GONG M, CHEN Y. The effect of synthesis method on the properties and catalyticperformance of Pd/Ce_0.5Zr_0.5O₂-Al₂O₃ three-way catalyst[J]. J Mol Catal A:Chem, 2014,394(10):10-21.
20. [20]
  SHU Q, NAWAZ Z, GAO J X, WANG J F. Synthesis of biodiesel from a model waste oil feedstock using a carbon-based solid acid catalyst:Reaction and separation[J]. Bioresource Technol, 2010,101(14):5374-5384. doi: 10.1016/j.biortech.2010.02.050
1. [1]
  Aili Feng , Xin Lu , Peng Liu , Dongju Zhang . Computational Chemistry Study of Acid-Catalyzed Esterification Reactions between Carboxylic Acids and Alcohols. University Chemistry, 2025, 40(3): 92-99. doi: 10.12461/PKU.DXHX202405072
2. [2]
  Guodong Xu , Chengcai Sheng , Xiaomeng Zhao , Tuojiang Zhang , Zongtang Liu , Jun Dong . Reform of Comprehensive Organic Chemistry Experiments in the Context of Emerging Engineering Education: A Case Study on the Improved Preparation of Benzocaine. University Chemistry, 2024, 39(11): 286-295. doi: 10.12461/PKU.DXHX202403094
3. [3]
  Pengzi Wang , Wenjing Xiao , Jiarong Chen . Copper-Catalyzed C―O Bond Formation by Kharasch-Sosnovsky-Type Reaction. University Chemistry, 2025, 40(4): 239-244. doi: 10.12461/PKU.DXHX202406090
4. [4]
  Mengyang LI , Hao XU , Zhonghao NIU , Chunhua GONG , Weihui ZHONG , Jingli XIE . Highly effective catalytic synthesis of β-amino alcohols by using viologen-polyoxometalate hybrid materials. Chinese Journal of Inorganic Chemistry, 2025, 41(7): 1294-1300. doi: 10.11862/CJIC.20250080
5. [5]
  Xudong Liu , Huili Fan , Junping Xiao , Min Yang , Yan Li . Teaching Approaches to the A_E + A_N Mechanism of Electrophilic Addition Reactions between Olefins and Inorganic Acids in Organic Chemistry. University Chemistry, 2025, 40(7): 367-372. doi: 10.12461/PKU.DXHX202409041
6. [6]
  Fanpeng Meng , Fei Zhao , Jingkai Lin , Jinsheng Zhao , Huayang Zhang , Shaobin Wang . Optimizing interfacial electric fields in carbon nitride nanosheet/spherical conjugated polymer S-scheme heterojunction for hydrogen evolution. Acta Physico-Chimica Sinica, 2025, 41(8): 100095-0. doi: 10.1016/j.actphy.2025.100095
7. [7]
  Mengfei He , Chao Chen , Yue Tang , Si Meng , Zunfa Wang , Liyu Wang , Jiabao Xing , Xinyu Zhang , Jiahui Huang , Jiangbo Lu , Hongmei Jing , Xiangyu Liu , Hua Xu . Epitaxial Growth of Nonlayered 2D MnTe Nanosheets with Thickness-Tunable Conduction for p-Type Field Effect Transistor and Superior Contact Electrode. Acta Physico-Chimica Sinica, 2025, 41(2): 2310029-0. doi: 10.3866/PKU.WHXB202310029
8. [8]
  Kuaibing Wang , Feifei Mao , Weihua Zhang , Bo Lv . Design and Practice of a Comprehensive Teaching Experiment for Preparing Biomass Carbon Dots from Rice Husk. University Chemistry, 2025, 40(5): 342-350. doi: 10.12461/PKU.DXHX202407042
9. [9]
  Ke Li , Chuang Liu , Jingping Li , Guohong Wang , Kai Wang . Architecting Inorganic/Organic S-Scheme Heterojunction of Bi₄Ti₃O₁₂ Coupling with g-C₃N₄ for Photocatalytic H₂O₂ Production from Pure Water. Acta Physico-Chimica Sinica, 2024, 40(11): 2403009-0. doi: 10.3866/PKU.WHXB202403009
10. [10]
  Zhongyan Cao , Shengnan Jin , Yuxia Wang , Yiyi Chen , Xianqiang Kong , Yuanqing Xu . Advances in Highly Selective Reactions Involving Phenol Derivatives as Aryl Radical Precursors. University Chemistry, 2025, 40(4): 245-252. doi: 10.12461/PKU.DXHX202405186
11. [11]
  Xiaofei Liu , He Wang , Li Tao , Weimin Ren , Xiaobing Lu , Wenzhen Zhang . Electrocarboxylation of Benzylic Phosphates and Phosphinates with Carbon Dioxide. Acta Physico-Chimica Sinica, 2024, 40(9): 2307008-0. doi: 10.3866/PKU.WHXB202307008
12. [12]
  Jinghan ZHANG , Guanying CHEN . Progress in the application of rare-earth-doped upconversion nanoprobes in biological detection. Chinese Journal of Inorganic Chemistry, 2024, 40(12): 2335-2355. doi: 10.11862/CJIC.20240249
13. [13]
  Bolin Sun , Jie Chen , Ling Zhou . 乙烯型卤代烃的亲核取代反应. University Chemistry, 2025, 40(8): 152-157. doi: 10.12461/PKU.DXHX202410032
14. [14]
  Xin MA , Ya SUN , Na SUN , Qian KANG , Jiajia ZHANG , Ruitao ZHU , Xiaoli GAO . A Tb₂ complex based on polydentate Schiff base: Crystal structure, fluorescence properties, and biological activity. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1347-1356. doi: 10.11862/CJIC.20230357
15. [15]
  Qingying Gao , Tao Luo , Jianyuan Su , Chaofan Yu , Jiazhu Li , Bingfei Yan , Wenzuo Li , Zhen Zhang , Yi Liu . Refinement and Expansion of the Classic Cinnamic Acid Synthesis Experiment. University Chemistry, 2024, 39(5): 243-250. doi: 10.3866/PKU.DXHX202311074
16. [16]
  Lanjun Cheng , Xinyuan Wang , Jie An , Xiang Wu , Chengfeng Zhu , Yanming Fu , Yougui Li . Improvement of the Resolution Experiment of Racemic Tartaric Acid. University Chemistry, 2025, 40(7): 277-285. doi: 10.12461/PKU.DXHX202408010
17. [17]
  Guojie Xu , Fang Yu , Yunxia Wang , Meng Sun . Introduction to Metal-Catalyzed β-Carbon Elimination Reaction of Cyclopropenones. University Chemistry, 2024, 39(8): 169-173. doi: 10.3866/PKU.DXHX202401060
18. [18]
  Yang Meiqing , Lu Wang , Haozi Lu , Yaocheng Yang , Song Liu . Recent Advances of Functional Nanomaterials for Screen-Printed Photoelectrochemical Biosensors. Acta Physico-Chimica Sinica, 2025, 41(2): 2310046-0. doi: 10.3866/PKU.WHXB202310046
19. [19]
  Meijin Li , Xirong Fu , Xue Zheng , Yuhan Liu , Bao Li . The Marvel of NAD⁺: Nicotinamide Adenine Dinucleotide. University Chemistry, 2024, 39(9): 35-39. doi: 10.12461/PKU.DXHX202401027
20. [20]
  Keying Qu , Jie Li , Ziqiu Lai , Kai Chen . Unveiling the Mystery of Chirality from Tartaric Acid. University Chemistry, 2024, 39(9): 369-378. doi: 10.12461/PKU.DXHX202310091

Get Citation

PDF

XML

Metrics

PDF Downloads(5)
Abstract views(1069)
HTML views(98)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Preparation of a novel solid Lewis acid Ce3+-Ti4+-SO42-/MWCNTs and its application in the synthesis of biodiesel from esterification reaction

Metrics

通讯作者: 陈斌, bchen63@163.com

Preparation of a novel solid Lewis acid Ce³⁺-Ti⁴⁺-SO₄^2-/MWCNTs and its application in the synthesis of biodiesel from esterification reaction