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Efficient Synthesis of Ethyl Levulinate Fuel Additives from Levulinic Acid Catalyzed by Sulfonated Pine Needle-Derived Carbon

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Abstract

The low-cost and environmentally friendly solid acid catalysts for the efficient synthesis of ethyl levulinate fuel additives were prepared from pine needles through the partial carbonization, followed by a hydrothermal H2SO4 sulfonation procedure. The resultant sulfonated carbon catalysts possessed an amorphous carbon structure and high contents of the sulfate groups. Other than that, they had good thermal stability and the total acid density was as high as 2.28 mmol g−1. In this work, noticeably, the parameters of both synthetic and catalytic reactions were optimized to enhance the conversion of levulinic acid (LA). The results showed that the LA conversion was as high as 96.1% over the catalysts carbonizated at 700 °C for 90 min and sulfonated at 160 °C for 15 h under the optimized conditions (5:1 ethanol/LA molar ratio, 5 wt% catalyst dosage, 80 °C reaction temperature, 8 h reaction time). Meanwhile, the recyclability experiments confirmed that the resultant catalysts exhibited satisfactory reusability and the corresponding conversion of LA was maintained as 63.0% in the fourth run. Remarkably, the reused catalysts can be easily activated again and the corresponding LA conversion could reach up to 90.1%. The results demonstrated that the catalysts had great potential in the synthesis of biofuels, which could be efficient and could have excellent recyclability.

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References

  1. Roy P, Dias G (2017) Prospects for pyrolysis technologies in the bioenergy sector: a review. Renew Sustain Energy Rev 77:59–69

    Article  CAS  Google Scholar 

  2. Hu L, Lin L, Wu Z, Zhou SY, Liu SJ (2017) Recent advances in catalytic transformation of biomass-derived 5-hydroxymethylfurfural into the innovative fuels and chemicals. Renew Sustain Energy Rev 74:230–257

    Article  CAS  Google Scholar 

  3. Morgan HM, Bu Q, Liang JH, Liu YJ, Mao HP, Shi AP, Lei HW, Ruan R (2017) A review of catalytic microwave pyrolysis of lignocellulosic biomass for value-added fuel and chemicals. Bioresource Technol 230:112–121

    Article  CAS  Google Scholar 

  4. Nemanashi M, Noh JH, Meijboom R (2018) Hydrogenation of biomass-derived levulinic acid to gamma-valerolactone catalyzed by mesoporous supported dendrimer-derived Ru and Pt catalysts: an alternative method for the production of renewable biofuels. Appl Catal A 550:77–89

    Article  CAS  Google Scholar 

  5. Khalid F, Dincer I, Rosen MA (2015) Energy and exergy analyses of a solar-biomass integrated cycle for multigeneration. Sol Energy 112:290–299

    Article  Google Scholar 

  6. Urbaniec K, Bakker RR (2015) Biomass residues as raw material for dark hydrogen fermentation—a review. Int J Hydrogen Energy 40:3648–3658

    Article  CAS  Google Scholar 

  7. Kang K, Azargohar R, Dalai AK, Wang H (2016) Hydrogen production from lignin, cellulose and waste biomass via supercritical water gasification: catalyst activity and process optimization study. Energy Convers Manage 117:528–537

    Article  CAS  Google Scholar 

  8. Hayes DJ (2009) An examination of biorefining processes, catalysts and challenges. Catal Today 145:138–151

    Article  CAS  Google Scholar 

  9. Pileidis FD, Titirici MM (2016) Levulinic acid biorefineries: new challenges for efficient utilization of biomass. ChemSusChem 47:562–582

    Article  CAS  Google Scholar 

  10. Serrano-Ruiz JC, Pineda A, Balu AM, Luque R, Campelo JC, Romero AA, Ramoz-Fernandez JM (2012) Catalytic transformations of biomass-derived acids into advanced biofuels. Catal Today 195:162–168

    Article  CAS  Google Scholar 

  11. Nandiwale KY, Sonar SK, Niphadkar PS, Joshi PN, Deshpande SS, Patil VS, Bokade VV (2013) Catalytic upgrading of renewable levulinic acid to ethyl levulinate biodiesel using dodecatungstophosphoric acid supported on desilicated H-ZSM-5 as catalyst. Appl Catal A 460:90–98

    Article  CAS  Google Scholar 

  12. Kong XJ, Wu SX, Li XL, Liu JH (2016) Efficient conversion of levulinic acid to ethyl levulinate over a silicotungstic-acid-modified commercially silica-gel sphere catalyst. Energy Fuel 30:6500–6504

    Article  CAS  Google Scholar 

  13. Fayyazbakhsh A, Pirouzfar V (2017) Comprehensive overview on diesel additives to reduce emissions, enhance fuel properties and improve engine performance. Renew Sustain Energy Rev 74:891–901

    Article  CAS  Google Scholar 

  14. Bart HJ, Reidetschlager J, Schatka K, Lehmann A (1994) Kinetics of esterification of levulinic acid with n-butanol by homogeneous catalysis. Ind Eng Chem Res 33:21–25

    Article  CAS  Google Scholar 

  15. Lilja J, Murzin DY, Salmi T, Aumo J, Mäki-Arvela P, Sundell M (2002) Esterification of different acids over heterogeneous and homogeneous catalysts and correlation with the Taft equation. J Mol Catal A 182:555–563

    Article  Google Scholar 

  16. Liu YJ, Lotero E, Goodvin JG (2006) A comparison of the esterification of acetic acid with methanol using heterogeneous versus homogeneous acid catalysis. J Catal 242:278–286

    Article  CAS  Google Scholar 

  17. Konwar LJ, Boro J, Deka D (2014) Review on latest developments in biodiesel production using carbon-based catalysts. Renew Sustain Energy Rev 29:546–564

    Article  CAS  Google Scholar 

  18. Thombal RS, Jadhav VH (2015) Biomass derived beta-cyclodextrin-SO3H carbonaceous solid acid catalyst for catalytic conversion of carbohydrates to 5-hydroxymethylfurfural. Appl Catal A 499:213–216

    Article  CAS  Google Scholar 

  19. Okamura M, Takagaki A, Toda M, Kondo JN, Domen K, Tatsumi T, Hara M, Hayashi S (2006) Acid-catalyzed reactions on flexible polycyclic aromatic carbon in amorphous carbon. Chem Mater 18:3039–3045

    Article  CAS  Google Scholar 

  20. Peng L, An P, Ke X, Noyen JV, Clippel FD, Tendeloo GV, Jacobs PA, Sels BF (2010) Preparation of sulfonated ordered mesoporous carbon and its use for the esterification of fatty acids. Catal Today 150:140–146

    Article  CAS  Google Scholar 

  21. Zain G, Nada AA, El-Sheikh MA, Attaby FA, Waly AI (2018) Superabsorbent hydrogel based on sulfonated-starch for improving water and saline absorbency. Int J Biol Macromol 115:61–68

    Article  CAS  PubMed  Google Scholar 

  22. Nata IF, Putra MD, Irawan C, Lee CK (2017) Catalytic performance of sulfonated carbon-based solid acid catalyst on esterification of waste cooking oil for biodiesel production. J Environ Chem Eng 5:2171–2175

    Article  CAS  Google Scholar 

  23. Fadhil AB, Aziz AM, Al-Tamer MH (2016) Biodiesel production from Silybum marianum L. seed oil with high FFA content using sulfonated carbon catalyst for esterification and base catalyst for transesterification. Energy Convers Manage 108:255–265

    Article  CAS  Google Scholar 

  24. Fraile JM, García-Bordejé E, Pires E, Roldán L (2015) Catalytic performance and deactivation of sulfonated hydrothermal carbon in the esterification of fatty acids: comparison with sulfonic solids of different nature. J Catal 324:107–118

    Article  CAS  Google Scholar 

  25. Rao BVSK, Mouli KC, Rambabu N, Dalai AK, Prasad RBN (2011) Carbon-based solid acid catalyst from de-oiled canola meal for biodiesel production. Catal Commun 14:20–26

    Article  CAS  Google Scholar 

  26. Liu ZW, Fu X, Tang SR, Cheng Y, Zhu L, Xing LL, Wang J, Xue LL (2014) Sulfonated magnetic carbon nanotube arrays as effective solid acid catalysts for the hydrolyses of polysaccharides in crop stalks. Catal Commun 56:1–4

    Article  CAS  Google Scholar 

  27. Chang BB, Fu J, Tian YL, Dong XP (2013) Soft-template synthesis of sulfonated mesoporous carbon with high catalytic activity for biodiesel production. RSC Adv 3:1987–1994

    Article  CAS  Google Scholar 

  28. Aldana-Pérez A, Lartundo-Rojas L, Gómez R, Niño-Gómez ME (2012) Sulfonic groups anchored on mesoporous carbon Starbons-300 and its use for the esterification of oleic acid. Fuel 100:128–138

    Article  CAS  Google Scholar 

  29. Wang L, Wang DL, Zhang SQ, Tian H (2013) Synthesis and characterization of sulfonated graphene as a highly active solid acid catalyst for the ester-exchange reaction. Catal Sci Technol 3:1194–1197

    Article  CAS  Google Scholar 

  30. Liu R, Wang XQ, Zhao X, Feng PY (2008) Sulfonated ordered mesoporous carbon for catalytic preparation of biodiesel. Carbon 46:1664–1669

    Article  CAS  Google Scholar 

  31. Geng L, Wang Y, Yu G, Zhu YX (2011) Efficient carbon-based solid acid catalysts for the esterification of oleic acid. Catal Commun 13:26–30

    Article  CAS  Google Scholar 

  32. Domrachev DV, Karpova EV, Goroshkevich SN, Tkachev AV (2012) Comparative analysis of volatiles from needles of five-needle pines of northern and eastern Eurasia. Russ J Bioorg Chem 38:780–789

    Article  CAS  Google Scholar 

  33. Li SL, Zhang JB, Zhang ZF, Wei XH (2010) Study on extraction and isolation of tannin from pine needles of Pinus elliottii Engelm. Chem Ind For Product 30:99–102

    Google Scholar 

  34. Mo XH, López DE, Suwannakarn K, Liu YJ, Lotero E, Goodwin JG, Lu CQ (2008) Activation and deactivation characteristics of sulfonated carbon catalysts. J Catal 254:332–338

    Article  CAS  Google Scholar 

  35. Takagaki A, Toda M, Mai O, Kondo JN, Hayashi S, Domen K, Hara M (2006) Esterification of higher fatty acids by a novel strong solid acid. Catal Today 116:157–161

    Article  CAS  Google Scholar 

  36. Su XL, Chen JR, Zheng GP, Yang JH, Guan XX, Liu P, Zheng XC (2018) Three-dimensional porous activated carbon derived from loofah sponge biomass for supercapacitor applications. Appl Surf Sci 436:327–336

    Article  CAS  Google Scholar 

  37. Stobinski L, Lesiak B, Kövér L, Tóth J, Biniak S, Trykowski G, Judek J (2010) Multiwall carbon nanotubes purification and oxidation by nitric acid studied by the FTIR and electron spectroscopy methods. J Alloys Compd 501:77–84

    Article  CAS  Google Scholar 

  38. Ling XL, Wei YZ, Zou LM, Xu S (2013) The effect of different order of purification treatments on the purity of multiwalled carbon nanotubes. Appl Surf Sci 276:159–166

    Article  CAS  Google Scholar 

  39. Yu H, Jin YG, Li ZL, Peng F, Wang HJ (2008) Synthesis and characterization of sulfonated single-walled carbon nanotubes and their performance as solid acid catalyst. J Solid State Chem 181:432–438

    Article  CAS  Google Scholar 

  40. Lu YM, Gong QM, Lu FP, Liang J, Ji LJ, Nie QD, Zhang XM (2011) Preparation of sulfonated porous carbon nanotubes/activated carbon composite beads and their adsorption of low density lipoprotein. J Mater Sci: Mater Med 22:1855–1862

    CAS  Google Scholar 

  41. Su XL, Jiang S, Zheng GP, Zheng XC, Yang JH, Liu ZY (2018) High-performance supercapacitors based on porous activated carbons from cattail wool. J Mater Sci 53:9191–9205

    Article  CAS  Google Scholar 

  42. Shu Q, Gao JX, Nawaz ZS, Liao YH, Wang DZ, Wang JF (2010) Synthesis of biodiesel from waste vegetable oil with large amounts of free fatty acids using a carbon-based solid acid catalyst. Appl Energy 87:2589–2596

    Article  CAS  Google Scholar 

  43. Tao ML, Guan HY, Wang XH, Liu YC, Louh RF (2015) Fabrication of sulfonated carbon catalyst from biomass waste and its use for glycerol esterification. Fuel Process Technol 138:355–360

    Article  CAS  Google Scholar 

Download references

Acknowledgements

Financial supports from the National Natural Science Foundation of China (CN) (No. U1304203), the Natural Science Foundation of Henan Province (CN) (No. 162300410258), the Foundation of Henan Educational Committee (CN) (No. 16A150046), and 111 Project (CN) (B12015) are greatly acknowledged.

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Authors and Affiliations

  1. College of Chemistry and Molecular Engineering, Henan Institutes of Advanced Technology, Zhengzhou University, Zhengzhou, 450001, China

    Ning Li, Xiao-Li Zhang, Xiu-Cheng Zheng & Gui-Hong Wang

  2. School of Civil Engineering, Shandong Jiaotong University, Jinan, 250357, China

    Xiao-Ying Wang

  3. Department of Mechanical Engineering, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong, China

    Xiu-Cheng Zheng & Guang-Ping Zheng

  4. Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Nankai University, Tianjin, 300071, China

    Xiu-Cheng Zheng

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  1. Ning Li
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Li, N., Zhang, XL., Zheng, XC. et al. Efficient Synthesis of Ethyl Levulinate Fuel Additives from Levulinic Acid Catalyzed by Sulfonated Pine Needle-Derived Carbon. Catal Surv Asia 23, 171–180 (2019). https://doi.org/10.1007/s10563-019-09270-8

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