Citation: WU Yan, LEI Yan-qing, LIU Xin-yue, QIU Yue, WANG Hao. Synthesis and characterization of 12-tungstophosphoric acid intercalated MgAl layered double hydroxides and their application as esterification catalysts for deacidification of crude oil[J]. Journal of Fuel Chemistry and Technology, ;2017, 45(9): 1049-1055. shu

Synthesis and characterization of 12-tungstophosphoric acid intercalated MgAl layered double hydroxides and their application as esterification catalysts for deacidification of crude oil

School of Chemistry and Chemical Engineering, Southwest Petroleum University, Chengdu 610500, China

Corresponding author: WANG Hao, wpuwanghao1216@sina.com
Received Date: 12 May 2017
Revised Date: 13 July 2017

Fund Project: National Natural Science Foundation of China 21506176The project was supported by National Natural Science Foundation of China (21506176)

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12-tungstophosphoric acid (H₃PW₁₂O₄₀, HPW) intercalated layered double hydroxides (LDHs) with various Mg/Al molar ratios were synthesized by an ion-exchange method. The samples were characterized by XRD, FT-IR, Raman, ICP-AES and TG-DSC. The acid strength and amount of acidic sites of catalysts were measured by Hammett indicator and n-butylamine titration technique. Furthermore, HPW intercalated LDHs were used as esterification catalysts for deacidification of crude oil and compared with their nitrate LDHs precursors. The relationship between the catalytic activity and the property of HPW intercalated LDHs was investigated. It is found that the catalytic activity of LDHs mainly depends on the acidity and the specific surface area. HPW intercalated LDHs exhibit a much higher catalytic activity than nitrate LDHs owing to the increased acidity and specific surface area. Due to the poorer acidity, the activity of nitrate LDHs is proportional to their specific surface area. The nitrate LDH with Mg/Al molar ratio of 4 exhibits the highest specific surface area and deacidification ratio. However, for highly acidic HPW intercalated LDHs, the amount of acidic sites dominates the catalytic activity and the HPW intercalated LDH with Mg/Al molar ratio of 2 has the highest acidity and esterification activity.
- 12-tungstophosphoric acid,
- layered double hydroxides,
- esterification,
- deacidification
1. [1]
  CHEN Qing-tao, ZHU Yu-long. Development status of high acid crude oil deacidification technologies[J]. Contemp Chem Ind, 2014, 43(6):1053-1055.
2. [2]
  XIE Li, ZHANG Wei, LI Zi-feng, MU Xu-hong. Study on the application of ultrasonic in the esterification deacidification of high acid crude oil[J]. Pet Process Petrochem, 2010,41(1):6-10.
3. [3]
  DUAN Xue, ZHANG Fa-zhi. Intercalation Assembly and Functional Materials[M]. Beijing:Chemistry Industry Press, 2007.
4. [4]
  WU Yan, YAN Cheng-yang, WANG Hao. Study on the esterification reaction for removing the acids from crude oil using Mg-Al hydroxides as catalyst[J]. Chem Eng Oil Gas, 2009,38(2):129-131.
5. [5]
  WU Yan, WANG Hao, ZHONG Ting, ZHANG Ling, XU Li-jiao. Characterization of Mg-Al hydroxides prepared by various methods and their catalytic activities for esterification to remove acid from crude oil[J]. Acta Petrol Sin (Pet Process Section), 2011,27(5):687-693.
6. [6]
  LI X, ZHU J, LIU Q, WU B. The removal of naphthenic acids from dewaxed VGO via esterification catalyzed by Mg-Al hydrotalcite[J]. Fuel Process Technol, 2013,111:68-77. doi: 10.1016/j.fuproc.2013.01.016
7. [7]
  HUANG Yan-zhao, ZHU Jian-hua, WANG Yan-yan, WU Cheng-ben. Removal of naphthenic acids from high acid crude oil through catalytic esterification on zinc aluminum hydrotalcite-like compounds[J]. J China Univ Pet, Ed Nat Sci, 2010,34(6):147-150.
8. [8]
  HUANG Y, ZHU J, WU B, WANG Y. Esterification kinetics of cyclohexanecarboxylic acid and ethylene glycol in diesel oil with or without a ZnAl-HTlc catalyst[J]. Pet Sci Technol, 2011,29(21):2209-2219. doi: 10.1080/10916461003610371
9. [9]
  LI X, WU B, ZHU J, TAO X. Tracking catalytic esterification of naphthenic acids in crude oil by ESI FT-ICR MS[J]. China Pet Process Petrochem Technol, 2016,18(3):57-65.
10. [10]
  HUANG Yan-shao, Zhu Jian-hua, Wu Ben-cheng, Wang Yan-yan. Catalytic esterification deacidification of the crude oil with high naphthenic acid content by ZnMgAl-HTlc[J]. Acta Petrol Sin (Pet Process Section), 2009,25(5):731-735.
11. [11]
  HUANG Yan-shao, Zhu Jian-hua, Wu Ben-cheng, Wang Yan-yan. Preparation ang performance of the catalyst for esterification deacidification of crude oil with high naphthenic acid number[J]. Chem React Eng Technol, 2009,25(3):210-215.
12. [12]
  LIU Jie-ying, MA Xiang-rong, DANG Rui, LI Jian, ZHANG Zhi-fang. Preparation of Zn-Ni-Al-LDHs catalysts and their performance for removal of naphthenic acids from high acid crude oil through catalytic esterification[J]. Ind Catal, 2014,22(7):555-558.
13. [13]
  MA Xiang-rong, LI Jian, DANG Rui, GAO Wen-wen, Li Xiao, QU Yuan. Preparation of Ni-Mg-Al-LDHs materials and removal of naphthenic acids from high acid crude oil through catalytic esterification on Ni-Mg-Al-LDHs[J]. Appl Chem Ind, 2013,42(1):30-32.
14. [14]
  WANG En-bo, HU Chang-wen. Introduction of Polyacid Chemistry[M]. Beijing:Chemistry Industry Press, 1998.
15. [15]
  DAS J, PARIDA K M. Heteropoly acid intercalated Zn/Al HTlc as efficient catalyst for esterification of acetic acid using n-butanol[J]. J Mol Catal A:Chem, 2007,264(1/2):248-254.
16. [16]
  XIE Mei-fang, Zheng Jian-hua. Study on synthesis of n-butyl acetate catalyzed by Phosphato-Tungstic heteropolyacid pillar double hydroxides[J]. Chem Bioeng, 2010,27(5):42-44.
17. [17]
  WANG H, DUAN W, WU Y, TANG Y, LI L. Synthesis of magnesium-aluminum layered double hydroxide intercalated with ethylene glycol by the aid of alkoxides[J]. Inorg Chim Acta, 2014,418(1):163-170.
18. [18]
  CAVANI F, TRIFIRÒ F, VACCARI A. Hydrotalcite-type anionic clays:Preparation, properties and applications[J]. Catal Today, 1991,11(2):173-301. doi: 10.1016/0920-5861(91)80068-K
19. [19]
  YANG Q Z, SUN D J, ZHANG C G, WANG X J, ZHAO W A. Synthesis and characterization of polyoxyethylene sulfate intercalated Mg-Al-nitrate layered double hydroxide[J]. Langmuir, 2003,19(14):5570-5574. doi: 10.1021/la034526j
20. [20]
  YU Feng-Li. Study on deep desulfurization of fuel oil with the heteropolyacid anion as functional building block in host-guest type composite catalyst[D]. Jinan:Shandong University, 2013.
21. [21]
  LI Z, YOU J, WANG J, YANG P, JING X, ZHANG M. Synthesis and characterization of tungstophosphoric acid intercalated Ni/Al HTlc with magnetite[J]. J Mater Process Technol, 2009,209(5):2613-2619. doi: 10.1016/j.jmatprotec.2008.06.005
22. [22]
  WEIR M R, KYDD R A. Synthesis of heteropolyoxometalate-pillared Mg/Al, Mg/Ga, and Zn/Al layered double hydroxides via LDH-hydroxide precursors[J]. Inorg Chem, 1998,37(21):5619-5624. doi: 10.1021/ic9805067
23. [23]
  DUAN X, EVANS D G. Layered double hydroxides[M]. Berlin:Springer, 2006.
24. [24]
  LIU Ji-Guang, Guo Jun, Sun Tie. Studies on the interaction between the layers and pillars of hydrotalcite-like compounds pillared with heteropolyanions[J]. Chem J Chinese U, 1995,16(9):1329-1333.
25. [25]
  CALIMAN E, DIAS J A, DIAS S C L, PRADO A G S. Solvent effect on the preparation of H₃PW₁₂O₄₀ supported on alumina[J]. Catal Today, 2005,107-108(44):816-825.
26. [26]
  LI Xiao-Lei, JIANG Ping-ping, LU Yun, ZHANG Wei-jie, DONG Yu-ming. Synthesis of hydrotalcite-like compounds intercalcated by 12-phosphorous tungsten heteropoly acid and catalytic performance on the epoxidation of fatty acid methyl esters[J]. Acta Chim Sinica, 2012,70(5):544-550.
27. [27]
  GUO Jun, JIAO Qing-ze, SHEN Jian-ping, LU Hui-juan, LIU Dan, JIANG Da-zhen, MIN En-ze. Studies on synthesis, thermal stabilities and acid-base properities of heteropolyanions pillared layered double hydroxides[J]. Acta Chim Sinica, 1996,54(4):357-362.
28. [28]
  LUO Q S, LI L, WANG Z X, DUAN X. Theoretical study of the layer-anion interactions in magnesium aluminum layered double hydroxides[J]. Chinese J Inorg Chem, 2001,17(6):835-842.
29. [29]
  CANTRELL D G, GILLIE L J, LEE A F, WILSON K. Structure-reactivity correlations in MgAl hydrotalcite catalysts for biodiesel synthesis[J]. Appl Catal A Gen, 2005,287(2):183-190. doi: 10.1016/j.apcata.2005.03.027
30. [30]
  JIA Y, FANG Y, ZHANG Y, MIRAS H N, SONG Y F. Classical Keggin intercalated into layered double hydroxides:Facile preparation and catalytic efficiency in Knoevenagel condensation reactions[J]. Chem Eur J, 2015,21(42):14862-14870. doi: 10.1002/chem.201501953
31. [31]
  SHU Qing, HOU Xiao-peng, LIU Feng-sheng, TANG Guo-qiang, XU Bao-quan, ZHANG Cai-xia. Catalytic activity of La-modified phosphotungstic heteropoly acid salt in synthesis of biodiesel from esterification of methanol and oleci acid[J]. Nonferrous Met Sci Eng, 2016,7(3):131-136.
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