Skip to content
Licensed Unlicensed Requires Authentication Published by De Gruyter September 29, 2015

Extraction and Recovery of Naphthenic Acid from Acidic Oil Using Supported Ionic Liquid Phases (SILPs)

Syed Nasir Shah, Kallidanthiyil Chellappan Lethesh, M. I. Abdul Mutalib and Rashidah Binti Mohd Pilus


In this study, functionalized silica supported ionic liquids phases (SILPs) were synthesized and characterized using Fourier Transform infrared (FTIR) spectroscopy, CHNS elemental analysis, thermo gravimetric analysis (TGA) and scanning electron microscopy (SEM). The adsorption of model naphthenic acid such as hexanoic acid, benzoic acid and commercial naphthenic acid from dodecane/kerosene was also investigated. The silica supported ionic liquids are good adsorbent for the removal of naphthenic acid from highly acidic model oil. The regeneration of supported ionic liquid phases as well as recovery of naphthenic acids from the supported ionic liquid phases (SILPs) was investigated.


1. Pedro P, Roger M, Luis Z. AquaconversionTM: A new option for residue conversion and heavy oil upgrading. Vision Technol 1998;6:5–13.Search in Google Scholar

2. Alvisi PP, Lins VFC. An overview of naphthenic acid corrosion in a vacuum distillation plant. Eng Fail Anal 2011;18:1403–6.10.1016/j.engfailanal.2011.03.019Search in Google Scholar

3 Dettman HD, Li N, Luo J, Refinery corrosion organic acid structure and athabasca bitumen, CORROS 2009, 2009.Search in Google Scholar

4. Hu Y, Xue G. Corrosion of equipment in processing high acid value crude and development of corrosion prevention technologies. Corros Prot Petrochem Ind 2004;21:5–8.Search in Google Scholar

5 A. S. f. Testing and Materials, ASTM D-664: Standard test method for acid number of petroleum products by potentiometric titration, Annual book of ASTM standards, 1989.Search in Google Scholar

6. Fan TP. Characterization of naphthenic acids in petroleum by fast atom bombardment mass spectrometry. Energy Fuels 1991;5:371–5.10.1021/ef00027a003Search in Google Scholar

7. Brient JA, Wessner PJ, Doyle MN. Naphthenic acids. In Kirk-Othmer encyclopedia of chemical technology. Wiley online library, 2000.10.1002/0471238961.1401160802180905.a01Search in Google Scholar

8. Holowenko FM, MacKinnon MD, Fedorak PM. Characterization of naphthenic acids in oil sands wastewaters by gas chromatography-mass spectrometry. Water Res 2002;36:2843–55.10.1016/S0043-1354(01)00492-4Search in Google Scholar

9. Gaikar V, Maiti D. Adsorptive recovery of naphthenic acids using ion-exchange resins. React Funct Polym 1996;31:155–64.10.1016/1381-5148(96)00054-5Search in Google Scholar

10. Hoeiland S, Barth T, Blokhus A, Skauge A. The effect of crude oil acid fractions on wettability as studied by interfacial tension and contact angles. J Pet Sci Technol Eng 2001;30:91–103.10.1016/S0920-4105(01)00106-1Search in Google Scholar

11. Borgund AE, Erstad K, Barth T. Fractionation of crude oil acids by HPLC and characterization of their properties and effects on gas hydrate surfaces. Energy Fuels 2007;21:2816–26.10.1021/ef070100rSearch in Google Scholar

12. Ding L, Rahimi P, Hawkins R, Bhatt S, Shi Y. Naphthenic acid removal from heavy oils on alkaline earth-metal oxides and ZnO catalysts. Appl Catal A: General 2009;371:121–30.10.1016/j.apcata.2009.09.040Search in Google Scholar

13. Zhang A, Ma Q, Wang K, Liu X, Shuler P, Tang Y. Naphthenic acid removal from crude oil through catalytic decarboxylation on magnesium oxide. Appl Catal A: General 2006;303:103–9.10.1016/j.apcata.2006.01.038Search in Google Scholar

14. Wang YZ, Sun XY, Liu YP, Liu CG. Removal of naphthenic acids from a diesel fuel by esterification. Energy Fuels 2007;21:941–3.10.1021/ef060501rSearch in Google Scholar

15. Wang Y-z, Li J-y, Sun X-y, Duan H-l, Song C-m, Zhang M-m, et al. Removal of naphthenic acids from crude oils by fixed-bed catalytic esterification. Fuel 2014;116:723–8.10.1016/j.fuel.2013.08.047Search in Google Scholar

16. Swatloski RP, Spear SK, Holbrey JD, Rogers RD. Dissolution of cellose with ionic liquids. J Am Chem Soc 2002;124:4974–5.10.1021/ja025790mSearch in Google Scholar

17. Wu B, Reddy R, Rogers R. Novel ionic liquid thermal storage for solar thermal electric power systems. Sol Eng 2001;5:445–52.10.1115/SED2001-157Search in Google Scholar

18. Rao C, Venkatesan K, Nagarajan K, Srinivasan T. Dissolution of uranium oxides and electrochemical behavior of U (VI) in task specific ionic liquid. Radiochim Acta 2008;96:403–9.10.1524/ract.2008.1508Search in Google Scholar

19. Huddleston J, Rogers R. Room temperature ionic liquids as novel media for “clean” liquid–liquid extraction. Chem Commun 1998;16:1765–6.10.1039/A803999BSearch in Google Scholar

20. Ohno H. Electrochemical aspects of ionic liquids. New York: John Wiley & Sons, 2011.10.1002/9781118003350Search in Google Scholar

21. Plechkova NV, Seddon KR. Applications of ionic liquids in the chemical industry. Chem Soc Rev 2008;37:123–50.10.1039/B006677JSearch in Google Scholar

22. Welton T. Ionic liquids in catalysis. Coord Chem Rev 2004;248:2459–77.10.1016/j.ccr.2004.04.015Search in Google Scholar

23. Shi LJ, Shen BX, Wang GQ. Removal of naphthenic acids from Beijiang crude oil by forming ionic liquids. Energy Fuels 2008;22:4177–81.10.1021/ef800497pSearch in Google Scholar

24. Sun Y, Shi L. Basic ionic liquids with imidazole anion: New reagents to remove naphthenic acids from crude oil with high total acid number. Fuel 2012;99:83–7.10.1016/j.fuel.2012.04.014Search in Google Scholar

25. Duan J, Sun Y, Shi L. Three different types of heterocycle of nitrogen-containing alkaline ionic liquids treatment of acid oil to remove naphthenic acids. Catal Today 2013;212:180–5.10.1016/j.cattod.2012.07.023Search in Google Scholar

26. Anderson K, Goodrich P, Hardacre C, Hussain A, Rooney D, Wassell D. Removal of naphthenic acids from crude oil using amino acid ionic liquids. Fuel 2013;108:715–22.10.1016/j.fuel.2013.02.030Search in Google Scholar

27. Nasir Shah S, Mutalib MIA, Pilus RBM, Lethesh KC. Extraction of naphthenic acid from highly acidic oil using hydroxide-based ionic liquids. Energy Fuels 2014;29:106–11.10.1021/ef502169qSearch in Google Scholar

28. Anderson K, Atkins M, Goodrich P, Hardacre C, Hussain A, Pilus R, et al. Naphthenic acid extraction and speciation from Doba crude oil using carbonate-based ionic liquids. Fuel 2015;146:60–68.10.1016/j.fuel.2015.01.015Search in Google Scholar

29. Fontanals N, Borrull F, Marcé RM. Ionic liquids in solid-phase extraction. TrAC Trends Anal Chem 2012;41:15–26.10.1016/j.trac.2012.08.010Search in Google Scholar

30. Vidal L, Parshintsev J, Hartonen K, Canals A, Riekkola M-L. Ionic liquid-functionalized silica for selective solid-phase extraction of organic acids, amines and aldehydes. J Chromatogr A 2012;1226:2–10.10.1016/j.chroma.2011.08.075Search in Google Scholar

31. Tian M, Yan H, Row KH. Solid-phase extraction of tanshinones from Salvia Miltiorrhiza Bunge using ionic liquid-modified silica sorbents. J Chromatogr B 2009;877:738–42.10.1016/j.jchromb.2009.02.012Search in Google Scholar

32. Qiu H, Jiang Q, Wei Z, Wang X, Liu X, Jiang S. Preparation and evaluation of a silica-based 1-alkyl-3-(propyl-3-sulfonate) imidazolium zwitterionic stationary phase for high-performance liquid chromatography. J Chromatogr A 2007;1163:63–9.10.1016/j.chroma.2007.06.001Search in Google Scholar

33. Haumann M, Schönweiz A, Breitzke H, Buntkowsky G, Werner S, Szesni N. Solid‐state NMR investigations of supported ionic liquid phase water‐gas shift catalysts: ionic liquid film distribution vs. catalyst performance. Chem Eng Technol 2012;35:1421–6.10.1002/ceat.201200025Search in Google Scholar

34. Yassaghi G, Davoodnia A, Allameh S, AZare-Bidaki A, Tavakoli-Hoseini N. Preparation, characterization and first application of aerosil silica supported acidic ionic liquid as a reusable heterogeneous catalyst for the synthesis of 2, 3-dihydroquinazolin-4 (1H)-ones. Bull Korean Chem Soc 2012;33:2725.10.5012/bkcs.2012.33.8.2724Search in Google Scholar

35. Sheldon RA. The E Factor: fifteen years on. Green Chem 2007;9:1273–83.10.1039/b713736mSearch in Google Scholar

36. Nasir Shah S, Mutalib MIA, Pilus RBM, Kallidanthiyil Chellappan L. Extraction of naphthenic acid from highly acidic oil using hydroxide based ionic liquids. Energy Fuels 2014;29:106–11.10.1021/ef502169qSearch in Google Scholar

Published Online: 2015-9-29
Published in Print: 2015-12-1

©2015 by De Gruyter