Skip to main content
  • Original Paper: Sol–gel and hybrid materials for energy, environment and building applications
  • Published:

Eco-friendly and efficient demulsification by chitosan biopolymer modified with titanium dioxide nanohybrid on carbonaceous substrates in (W/O) emulsions of crude oil

Abstract

Oil refinery activities have increased and the utilization of chemicals in the industry has enhanced and generated various types of wastewater. The main objective of this work was the optimization and enhancement of the efficiency of chitosan biopolymer for eco-friendly and efficient rapid demulsification. Environmental and economic viability of chitosan production are of utmost importance nowadays. Chitosan is widely regarded a non-toxic and biologically compatible polymer. In this work, chitosan and its composite with titanium dioxide nanoparticles modified by zirconium on carbonaceous compounds such as graphene oxide (GO) and carboxylic functionalized, multi-walled carbon nanotubes (MWCNT-COOH) have been prepared by the sol–gel method. Several spectroscopic techniques have been applied to characterize the structures and properties of the nanoparticles prepared. The demulsification efficiency of four biocomposites was investigated under different conditions of concentration, settling time, and temperature. The demulsification activity of chitosan with titanium dioxide nanohybrid on graphene oxide (CT/TZG) was optimized via response surface method combined with central composite design (CCD). The results revealed that the maximum demulsification efficiency of 100% was achieved under optimum conditions at temperature, concentration, and time of 65 °C, 100 ppm, and 100 min, respectively.

Graphical abstract

Highlights

  • A novel chitosan biopolymer modified with nano titania and carbonaceous substrate was used to chemically demulsify water in crude oil emulsions (W/O).

  • According to the results, the demulsifiers show good performance in the demulsification of W/O emulsions.

  • RSM and CCD were used to optimize the demulsification efficiency.

  • Demulsifier concentration and temperature significantly affected the demulsification efficiency.

This is a preview of subscription content, access via your institution.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7

References

  1. Azhdarpoor A, Mortazavi B, Moussavi G (2014) Oily wastewaters treatment using Pseudomonas sp. isolated from the compost fertilizer. J Environ Health Sci Eng 12:77. https://doi.org/10.1186/2052-336X-12-77

    CAS  Article  Google Scholar 

  2. Wang D, Yang D, Huang Ch, Huang Y, Yang D, Zhang H, Liu Q, Tang T, El-Din MG, Kemppi T, Perdicakis B, Zeng H (2021) Stabilization mechanism and chemical demulsification of water-in-oil and oil-in-water emulsions in petroleum industry: a review. Fuel. https://doi.org/10.1016/j.fuel.2020.119390

  3. Chen Z, Peng J, Ge L, Xu Zh (2015) Demulsifying water-in-oil emulsion by ethyl cellulose demulsifiers studied using focused beam reflectance measurement. Chem Eng Sci. https://doi.org/10.1016/j.ces.2015.03.014

  4. Ye F, Mi Y, Liu H, Zeng G, Shen L, Feng X, Yang Y, Zhang Z, Yuan H, Yan X (2021) Demulsification of water-in-crude oil emulsion using natural lotus leaf treated via a simple hydrothermal process. Fuel 295:120596. https://doi.org/10.1016/j.fuel.2021.120596

    CAS  Article  Google Scholar 

  5. Masoumi A, Yengejeh RJ (2020) Study of chemical wastes in the Iranian petroleum industry and feasibility of hazardous waste disposal. J Environ Health Sci Eng 18:1037–1044. https://doi.org/10.1007/s40201-020-00525-5

    CAS  Article  Google Scholar 

  6. Silva FLMC, Tavares FW, Cardoso MJEM (2013) Thermodynamic stability of water-in-oil emulsions. BJPG 7:1–13. https://doi.org/10.5419/bjpg2013-0001

    Article  Google Scholar 

  7. Nassar NN, Hassan A, Pereira-Almao P (2011) Metal oxide nanoparticles for asphaltene adsorption and oxidation. Energy Fuel 25:1017–1023. https://doi.org/10.1021/ef101230g

    CAS  Article  Google Scholar 

  8. Razi M, Rahimpour MR, Jahanmiri A, Azad F (2011) Effect of a different formulation of demulsifiers on the efficiency of chemical demulsification of heavy crude oil. J Chem Eng Data 56:2936–2945. https://doi.org/10.1021/je2001733

    CAS  Article  Google Scholar 

  9. Li S, Li N, Yang S, Liu F, Zhou J (2014) The synthesis of a novel magnetic demulsifier and its application for the demulsification of oil charged industrial wastewaters. J Mater Chem A 2:94–99. https://doi.org/10.1039/C3TA12952G

    CAS  Article  Google Scholar 

  10. Kukizakia M, Goto M (2008) Demulsification of water-in-oil emulsions by permeation through Shirasuporous-glass (SPG) membranes. J Membr Sci 322:196–203. https://doi.org/10.1016/j.memsci.2008.05.029

    CAS  Article  Google Scholar 

  11. Majumdar S, Guha AK, Sirkar KK (2002) Fuel oil desalting by hydrogel hollow fiber membrane. J Membr Sci 202:253–256. https://doi.org/10.1016/S0376-7388(01)00726-8

    CAS  Article  Google Scholar 

  12. Nour AJ, Yunus MR, Anwaruddin H (2007) Water in crude oil emulsions: its stabilization and demulsification. Appl Sci 7:3512–3517. https://doi.org/10.3923/jas.2007.3512.3517

    CAS  Article  Google Scholar 

  13. Ye G, Lua X, Hana P, Peng F, Wang Y, Shen X (2008) Application of ultrasound on crude oil pretreatment, chemical engineering and processing. Chin J Chem Eng 47:2346–2350. https://doi.org/10.1016/j.cep.2008.01.010

    CAS  Article  Google Scholar 

  14. Bai ZS, Wang HL (2007) Crude oil desalting using hydrocyclones. Chem Eng Res Des 85:1586–1590. https://doi.org/10.1016/S0263-8762(07)73203-3

    CAS  Article  Google Scholar 

  15. Nadarajah N, Singh A, Ward OP (2002) De-emulsification of petroleum oil emulsion by a mixed bacterial culture. Process Biochem. https://doi.org/10.1016/s0032-9592(01)00325-9

  16. Huang XF, Liu J, Lu LJ, Wen Y, Xu JCH, Yang DH, Zhou Q (2009) Evaluation of screening methods for demulsifying bacteria and characterization of lipopeptide bio-demulsifier produced by alcaligenes SP. Bioresour Technol. 100:1358–65. https://doi.org/10.1016/j.biortech.2008.08.004

    CAS  Article  Google Scholar 

  17. Nikkhah M, Tohidian T, Rahimpour MR, Jahanmiri A (2014) Efficient demulsification of water-in-oil emulsion by a novel nano titania modified chemical demulsifier. Chem Eng Res Des. https://doi.org/10.1016/j.cherd.2014.07.021

  18. Singh A, Van Hamme JD, Ward OP (2007) Surfactants in microbiology and biotechnology: part 2. application aspects. Biotechnol Adv 25:99–121. https://doi.org/10.1016/j.biotechadv.2006.10.004

    CAS  Article  Google Scholar 

  19. Niederberger M, Pinna N (2009) Metal oxide nanoparticles in organic solvents: synthesis, formation, assembly and application (Engineering Materials and Processes). Springer, Berlin, Germnay

  20. Feinle A, Elsaesser MS, H¨using N (2016) Sol-gel synthesis of monolithic materials with hierarchical porosity, Chem Soc Rev. https://doi.org/10.1039/C5CS00710K

  21. Liao Y, Xu Y, Chan Y (2013) Semiconductor nanocrystals in sol-gel derived matrices. Phys Chem Chem Phys. https://doi.org/10.1039/C3CP51351C

  22. Owens GJ, Singh RK, Foroutan F, Alqaysi M, Han CH-M, Mahapatra CH, Kim H-W, Knowles JC (2016) Sol-gel based materials for biomedical applications. Prog Mater Sci 77:1–79. https://doi.org/10.1016/j.pmatsci.2015.12.001

    CAS  Article  Google Scholar 

  23. Haruta M (2004) Nanoparticulate gold catalysts for low-temperature CO oxidation. J New Mater Electrochem Syst 35. https://doi.org/10.1002/chin.200448226

  24. Tian N, Zhou ZY, Sun SG, Ding Y, Wang ZL (2007) Synthesis of tetrahexahedral platinum nanocrystals with high-index facets and high electro-oxidation activity. Science 316:732–5. https://doi.org/10.1126/science.1140484

    CAS  Article  Google Scholar 

  25. Xu R, Wang D, Zhang J, Li Y (2006) Shape-dependent catalytic activity of silver nanoparticles for the oxidation of styrene. Asian J Chem 1:888–93. https://doi.org/10.1002/asia.200600260

    CAS  Article  Google Scholar 

  26. Rahman IA, Padavettan V (2012) Synthesis of silica nanoparticles by sol-gel: size-dependent properties, surface modification, and applications in silica-polymer nanocomposites—a review. J Nanomater 2012:1–15. https://doi.org/10.1155/2012/132424

    CAS  Article  Google Scholar 

  27. Badawy MEI (2010) Structure and antimicrobial activity relationship of quaternaryN-alkyl chitosan derivatives against some plant pathogens. J Appl Polym Sci 117:960–969. https://doi.org/10.1002/app.31492

    CAS  Article  Google Scholar 

  28. Lü T, Chen Y, Qi D, CaoZh, Zhang D, Zhao H (2017) Treatment of emulsified oil wastewaters by using chitosan grafted magnetic nanoparticles. J Alloy Compd 696:1205–1212. https://doi.org/10.1016/j.jallcom.2016.12.118

    CAS  Article  Google Scholar 

  29. Lyu R, Li Z, Liang CH, Ting Xia Ch Zh, Wu M, Wang Y, Wang L, Luo X, Xu C (2021) Acylated carboxymethyl chitosan grafted with MPEG-1900 as a high-efficiency demulsifier for O/W crude oil emulsions. CARPTA. https://doi.org/10.1016/j.carpta.2021.100144

  30. Bratskaya S, Avramenko V, Schwarz S, Philippova I (2006) Enhanced flocculation of oil-in-water emulsions by hydrophobically modified chitosan derivatives. Colloids Surf Physicochem. Eng. https://doi.org/10.1016/j.colsurfa.2005.09.036

  31. Zhang Q, Chen Y, Wei PD, Zhong Y, Chen C, Cai J (2021) Extremely strong and tough chitosan films mediated by unique hydrated chitosan crystal structures. Mater Today 51:27–38. https://doi.org/10.1016/j.mattod.2021.10.030

    CAS  Article  Google Scholar 

  32. Sabab A, Vreugde S, Jukes A, Wormald PJ (2021) The potential of chitosan-based haemostats for use in neurosurgical setting – literature review. J Clin Neurosci 94:128–134. https://doi.org/10.1016/j.jocn.2021.10.018

    CAS  Article  Google Scholar 

  33. Lyu R, Xia T, Liang C, Zhang C, Li Z, Wang L, Wang Y, Wu M, Luo X, Ma J, Wang C, Xu C (2020) MPEG grafted alkylated carboxymethyl chitosan as a high-efficiency demulsifier for O/W crude oil emulsions. Carbohydr Polym 241:116309. https://doi.org/10.1016/j.carbpol.2020.116309

    CAS  Article  Google Scholar 

  34. Mahmoud Abdulraheim A (2018) Green polymeric surface active agents for crude oil demulsification. J Mol Liq. https://doi.org/10.1016/j.molliq.2018.08.153

  35. Du Y, Si P, Wei L, Wang Y, Tu YB, Zuo GH, Yu B, Zhang X, Ye S (2019) Demulsification of acidic oil-in-water emulsions driven by chitosan loaded Ti3C2Tx. Appl Surf Sci 476:878–885. https://doi.org/10.1016/j.apsusc.2019.01.106

    CAS  Article  Google Scholar 

  36. Xu Z, Zhu Q, Bian J (2021) Preparation of a recyclable demulsifier for the treatment of emulsified oil wastewater by chitosan modification and sodium oleate grafting Fe3O4. J Environ Chem Eng. https://doi.org/10.1016/j.jece.2021.105663

  37. Fong KK, Tan IS, Foo HCY, Lam MK, Tiong ACY, Lim S (2021) Optimization and evaluation of reduced graphene oxide hydrogel composite as a demulsifier for heavy crude oil-in-water emulsion. Chin. J. Chem. Eng. https://doi.org/10.1016/j.cjche.2020.08.027

  38. Xu H, Jia W, Ren S, Wang J (2019) Magnetically responsive multi-wall carbon nanotubes as recyclable demulsifier for oil removal from crude oil-in-water emulsion with different pH levels. Carbon 145:229–239. https://doi.org/10.1016/j.carbon.2019.01.024

    CAS  Article  Google Scholar 

  39. Ye F, Wang Z, Mi Y, Kuang J, Jiang X, Huang Z, Luo Y, Shen L, Yuan H, Zhang Z (2020) Preparation of reduced graphene oxide/titanium dioxide composite materials and its application in the treatment of oily wastewater. Colloid Surf Physicochem Eng Asp. https://doi.org/10.1016/j.colsurfa.2019.124251

  40. Chang SM, Hou CY, Lo PH, Chang ChT (2009) Preparation of phosphated Zr-doped TiO2 exhibiting high photocatalytic activity through calcination of ligand-capped nanocrystals. Appl Catal B Environ 90:233–241. https://doi.org/10.1016/j.apcatb.2009.03.009

    CAS  Article  Google Scholar 

  41. Seetharaman A, Dhanuskodi S (2014) Micro-structural, linear and nonlinear optical properties of titania nanoparticles. Acta A Mol Biomol Spectrosc. https://doi.org/10.1016/j.saa.2014.02.164

  42. Vijayalakshmi R, Rajendran V (2012) Synthesis and characterization of nano-TiO2 via different methods. Arch Appl Sci Res 2:1183–1190

    Google Scholar 

  43. Zhang Z, Xu G, Wang F, Dong S, Chen Y (2005) Demulsification by amphiphilic dendrimer copolymers. J Colloid Interface Sci. https://doi.org/10.1016/j.jcis.2004.08.144

  44. Zhang R, Bai Y, Zhang B, Chen L, Yan B (2012) The potential health risk of titania nanoparticles. J Hazard Mater. https://doi.org/10.1016/j.jhazmat.2011.11.022

  45. Bendoni R, Mercadelli E, Sangiorgi N, Strini A, Sangiorgi A, Sanson A (2015) Alternative route for the preparation of Zr-doped TiO2 layers forenergyand environmentalapplications. Ceram Int. https://doi.org/10.1016/j.ceramint.2015.04.067

  46. Gil A, Fernández M, Mendizába I, Korili SA, Soto-Armañanzas J, Crespo-Durante A, Gómez-Polo C (2016) Fabrication of TiO2 coated metallic wires by the sol-gel technique as a humidity sensor. Ceram Int. https://doi.org/10.1016/j.ceramint.2016.02.074

  47. Bautista-Ruiz J, Aperador W, Delgado A, Díaz–Lagos M (2014) Synthesis and characterization of anticorrosive coatings of SiO2 -TiO2 - ZrO2 obtained from sol-gel suspensions. Int J Electrochem Sci 9:4144–4157

    Google Scholar 

  48. Eder D, Windle AH (2008) Carbon–inorganic hybrid materials: the carbon-nanotube/TiO2 interface. Adv Mater 20:1787–1793. https://doi.org/10.1002/adma.200702835

    CAS  Article  Google Scholar 

  49. Sellappan R, Sun J, Galeckas A, Lindvall N, Yurgens A, Kuznetsov AY, Chakarov D (2013) Influence of graphene synthesizing techniques on the photocatalytic performance of graphene-TiO2 nanocomposites. Phys Chem Chem Phys 15:15528–15537. https://doi.org/10.1039/C3CP52457D

    CAS  Article  Google Scholar 

  50. Song P, Zhang X, Sun M, Cui X, Lin Y (2012) Graphene oxide modified TiO2 nanotube arrays: enhanced visible light photoelectrochemical properties. Nanoscale. https://doi.org/10.1039/C2NR11938B

  51. Mombeshora ET, Simoyi R, Nyamori VO, Ndungu PG (2015) Multiwalled carbon nanotube-titania nanocomposites: understanding nano-structural parameters and functionality in dye-sensitized solar cells. J Chem Educ. https://doi.org/10.17159/0379-4350/2015/V68A22

  52. Ghosh D, Giri S, Kalra S, Kumar Das C (2012) Synthesis and characterisations of TiO2 coated multiwalled carbon nanotubes/graphene/polyaniline nanocomposite for supercapacitor applications. OJAppS 02:70–77. https://doi.org/10.4236/ojapps.2012.22009

    CAS  Article  Google Scholar 

  53. Shen J, Yan B, Shi M, Ma H, Li N, Ye M (2011) One step hydrothermal synthesis of TiO2-reduced graphene oxide sheets. J Mater Chem. https://doi.org/10.1039/C0JM03542D

  54. Balsamo M, Erto A, Lancia A (2017) Chemical demulsification of model water-in-oil emulsions with low water content by means of ionic liquids. Braz J Chem Eng. https://doi.org/10.1590/0104-6632.20170341s20150583

  55. Hazratia N, Miran Beigi AA, Abdoussa M (2018) Demulsification of water in crude oil emulsion using long chain imidazolium ionic liquids and optimization of parameters. Fuel. https://doi.org/10.1016/j.fuel.2018.05.010

  56. Al-Otaibi M, Elkamel A, Al-Sahhaf T, Ahmed AS (2003) Experimental investigation of crude oil desalting and dehydration. Chem Eng Commun. https://doi.org/10.1080/00986440302094

  57. Fouladitajar A, Zokaee Ashtiani F, Dabir B, Rezaei H, Valizadeh B (2015) Response surface methodology for the modeling and optimization of oil-in-water emulsion separation using gas sparging assisted microfiltration. Environ Sci Pollut Res Int. https://doi.org/10.1007/s11356-014-3511-6

  58. Hajivand P, Vaziri A (2015) Optimization of demulsifier formulation for separation of water from crude oil emulsions. Braz J Chem Eng 32:107–118. https://doi.org/10.1590/0104-6632.20150321s00002755

    Article  Google Scholar 

  59. Mäkelä M (2017) Experimental design and response surface methodology in energy applications: A tutorial review. Energy Convers Manag 151:630–640. https://doi.org/10.1016/j.enconman.2017.09.021

    Article  Google Scholar 

  60. Zhao G, Tian Q, Liu Q, Han G (2005) Effects of HPC on the microstructure and hydrophilisity of sol-gel-derived TiO2 films. Surf Coat Technol. https://doi.org/10.1016/j.surfcoat.2004.10.064

  61. Razi M, Rahimpour MR, Jahanmiri A, Azad F (2011) Effect of a different formulation of demulsifiers on the efficiency of chemical demulsification of heavy crude oil. J Chem Eng Data. https://doi.org/10.1021/je2001733

  62. Sava BA, Diaconu A, Elisa M, Grigorescu CEA, Vasiliu C, Manea A (2007) Structural characterization of the sol-gel oxide powders from the ZnO–TiO2–SiO2 system. Superlattices Microst. https://doi.org/10.1016/j.spmi.2007.04.004

  63. Wang C, Xu BQ, Wang X, Zhao J (2005) Preparation and photocatalytic activity of ZnO/TiO2/SnO2 mixture. J. Solid State Chem. https://doi.org/10.1016/j.jssc.2005.09.005

  64. Liao MH, Hsu CH, Chen DH (2006) Preparation and properties of amorphous titania-coated zinc oxide nanoparticles. J. Solid State Chem. https://doi.org/10.1016/j.jssc.2006.03.042

  65. Karthik K, Kesava Pandian S, Victor Jaya N (2010) Effect of nickel doping on structural, optical and electrical properties of TiO2 nanoparticles by sol-gel method. Appl Surf Sci. https://doi.org/10.1016/j.apsusc.2010.04.096

  66. Xinshu N, Sujuan L, Huihui C, Jianguo Z (2011) Preparation, characterization of Y3+-doped TiO2 nanoparticles and their photocatalytic activities foe methyl orange degradation. J Rare Earth. https://doi.org/10.1016/S1002-0721(10)60435-8

  67. Chen C, Wang Z, Ruan S, Zou B, Zhao M, Wu F (2008) Photocatalytic degradation of C.I. acid orange 52 in the presence of Zn-doped TiO2 prepared by a stearic acid gel method. Dyes Pigments. https://doi.org/10.1016/j.dyepig.2007.05.003

  68. Akpan UG, Hameed BH (2010) The advancements in sol-gel method of doped-TiO2 photocatalysts. Appl Catal A Gen 375:1–11. https://doi.org/10.1016/j.apcata.2009.12.023

    CAS  Article  Google Scholar 

  69. Li Y, Peng S, Jiang F, Lu G, Li S (2007) Effect of doping TiO2 with alkaline-earthmetal ions on its photocata-lytic activity. J Serb Chem Soc. https://doi.org/10.2298/JSC0704393L

  70. Chen P, Xie F, Tang F, McNally T (2021) Graphene oxide enhanced ionic liquid plasticisation of chitosan/alginate bionanocomposites. Carbohydr Polym. https://doi.org/10.1016/j.carbpol.2020.117231

  71. Sabzevari M, Cree ED, Wilson LD (2018) Graphene Oxide–chitosan composite material for treatment of a model dye effluent. ACS Omega. https://doi.org/10.1021/acsomega.8b01871

  72. Zuo PP, Feng HF, Xu ZZ, Zhang LF, Zhang YL, Xia W, Zhang WQ (2013) Fabrication of biocompatible and mechanically reinforced graphene oxide-chitosan nanocomposite films. Chem Cent J. https://doi.org/10.1021/acsomega.9125c1

  73. Gong Y, Yu Y, Kang H, Chen X, Liu H, Zhang Y, Sun Y, Song H (2019) Synthesis and characterization of graphene oxide/chitosan composite aerogels with high mechanical performance. Polymers. https://doi.org/10.1021/acsomega.b01718

  74. lyas RA, Aisyah HA, Nordin AH, Ngadi N, Zuhri MYM, Asyraf MRM, Sapuan SM, Zainudin ES, Sharma S, Abral H (2022) Natural-fiber- reinforced chitosan, chitosan blends and their nanocomposites for various advanced applications. Polymers 14. https://doi.org/10.3390/polym14050874

Download references

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Marzieh Shekarriz.

Ethics declarations

Conflict of interest

The authors declare no competing interests.

Additional information

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Bigdeli, T., Shekarriz, M., Mehdizadeh, A. et al. Eco-friendly and efficient demulsification by chitosan biopolymer modified with titanium dioxide nanohybrid on carbonaceous substrates in (W/O) emulsions of crude oil. J Sol-Gel Sci Technol 104, 211–224 (2022). https://doi.org/10.1007/s10971-022-05907-9

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10971-022-05907-9

Keywords

  • Chitosan
  • TiO2
  • MWCNT-COOH
  • Graphene oxide
  • Sol–gel
  • Demulsification