Skip to main content
SpringerLink
Log in

Naturally biodegradable polymer as an effective heterogeneous catalyst for synthesis of biofuels via Knoevenagel condensation strategy

  • Original Article
  • Published:
Biomass Conversion and Biorefinery Aims and scope Submit manuscript

Abstract

Exploitation of natural biopolymers as heterogeneous catalysts for biomass valorization is highly attractive as it renders the production processes to be sustainable and increases the economic competitiveness of bio-refinery. Herein, sodium alginate was for the first time developed as heterogeneous base catalyst for Knoevenagel condensation of furfural and acetylacetone to produce high-quality fuel precursor. A furfural conversion rate as high as 89.58% along with 86.47% yield of 3-(furan-2-ylmethylene)pentane-2,4-dione was obtained in ethanol at 140 °C with 10 h. The excellent catalytic performance of sodium alginate in Knoevenagel condensation of furfural with acetylacetone was confirmed by the low value (10.8 kJ/mol) of as-obtained activation energy. In addition, a plausible reaction mechanism for Knoevenagel condensation of furfural with acetylacetone over sodium alginate was proposed. Moreover, sodium alginate almost sustained its original activity in consecutive six reuse experiments and the durability of sodium alginate was characterized by several techniques. Furthermore, other bio-based aldehydes such as 5-hydroxymethylfurfural and 5-methylfurfural were also applicable in the as-established system with producing the corresponding fuel precursor in excellent yields.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Scheme 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Scheme 2
Fig. 7
Fig. 8
Fig. 9
Fig. 10

Similar content being viewed by others

References

  1. Zhang B, Guo T, Liu Y, Kühn FE, Wang C, Zhao ZK, Xiao J, Li C, Zhang T (2021) Sustainable production of benzylamines from lignin. Angew Chem Int Ed 60:20666–20671

    Article  Google Scholar 

  2. Saha B, Vlachos DG (2021) Synthesis of (hemi)cellulosic lubricant base oils via catalytic coupling and deoxygenation pathways. Green Chem 23:4916–4930

    Article  Google Scholar 

  3. Li X, Sun J, Shao S, Hu X, Cai Y (2021) Aldol condensation/hydrogenation for jet fuel from biomass-derived ketone platform compound in one pot. Fuel Process Technol 215:106768

    Article  Google Scholar 

  4. Ghimire N, Bakke R, Bergland WH (2021) Liquefaction of lignocellulosic biomass for methane production: a review. Bioresour Technol 332:125068

    Article  Google Scholar 

  5. Rosillo-Calle F (2016) A review of biomass energy-shortcomings and concerns. J Chem Technol Biotechnol 91:1933–1945

    Article  Google Scholar 

  6. Bakhtyari A, Makarem MA, Rahimpour MR (2017) Light olefins/bio-gasoline production from biomass. In: Dalena F, Basile A, Rossi C (eds) Bioenergy Systems for the Future. Elsevier, pp 87–148

    Chapter  Google Scholar 

  7. Wu K, Wang W, Guo H, Yang Y, Huang Y, Li W, Li C (2020) Engineering Co nanoparticles supported on defect MoS2-x for mild deoxygenation of lignin-derived phenols to arenes. ACS Energy Lett 5:1330–1336

    Article  Google Scholar 

  8. He J, Chen L, Liu S, Song K, Yang S, Riisager A (2020) Sustainable access to renewable N-containing chemicals from reductive amination of biomass-derived platform compounds. Green Chem 22:6714–6747

    Article  Google Scholar 

  9. Hu X, Ming C, Li Q, Zhang L, Li C-Z (2021) Polymerization of sugars/furan model compounds and bio-oil during the acid-catalyzed conversion-a review. Fuel Process Technol 222:106958

    Article  Google Scholar 

  10. Dutta S (2021) Valorization of biomass-derived furfurals: reactivity patterns, synthetic strategies, and applications. Biomass Conv Bioref. https://doi.org/10.1007/s13399-021-01924-w

  11. Xu C, Paone E, Rodríguez-Padrín D, Luque R, Mauriello F (2020) Recent catalytic routes for the preparation and the upgrading of biomass derived furfural and 5-hydroxymethylfurfural. Chem Soc Rev 49:4273–4306

    Article  Google Scholar 

  12. Dai T, Li C, Li L, Zhao ZK, Zhang B, Cong Y, Wang A (2018) Selective production of renewable para-xylene by tungsten carbide catalyzed atom-economic cascade reactions. Angew Chem Int Ed 57:1808–1812

    Article  Google Scholar 

  13. He J, Xu Y, Yu Z, Li H, Zhao W, Wu H, Yang S (2020) ZrOCl2 as a bifunctional and in situ precursor material for catalytic hydrogen transfer of biobased carboxides. Sustain Energy Fuels 4:3102–3114

    Article  Google Scholar 

  14. Silva WR, Matsubara YE, Rosolen JM, Donate PM, Gunnella R (2021) Pd catalysts supported on different hydrophilic or hydrophobic carbonaceous substrate for furfural and 5-(hydroxymethyl)-furfural-hydrogenation in water. Mol Catal 504:111496

    Article  Google Scholar 

  15. Suresh S, Viswanathan V, Angamuthu M, Dhakshinamoorthy GP, Gopinath KP, Bhatnagar A (2021) Lignin waste processing into solid, liquid, and gaseous fuels: a comprehensive review. Biomass Conv Bioref. https://doi.org/10.1007/s13399-021-01497-8

  16. Pang J, Zhang B, Jiang Y, Zhao Y, Li C, Zheng M, Zhang T (2021) Complete conversion of lignocellulosic biomass to mixed organic acids and ethylene glycol via cascade steps. Green Chem 23:2427–2436

    Article  Google Scholar 

  17. He J, Li H, Xu Y, Yang S (2020) Dual acidic mesoporous KIT silicates enable one-pot production of γ-valerolactone from biomass derivatives via cascade reactions. Renew Energy 146:359–370

    Article  Google Scholar 

  18. Jadon TPS, Jana AK, Parikh PA (2021) Conversion of biorenewably available acetone and butanol to liquid fuels using base catalysts. Biomass Conv Bioref 11:1921–1930

    Article  Google Scholar 

  19. He J, Qiang Q, Liu S, Song K, Zhou X, Guo J, Zhang B, Li C (2021) Upgrading of biomass-derived furanic compounds into high-quality fuels involving aldol condensation strategy. Fuel 306:121765

    Article  Google Scholar 

  20. Hongloi N, Prapainainar P, Prapainainar C (2021) Review of green diesel production from fatty acid deoxygenation over Ni-based catalysts. Mol Catal. https://doi.org/10.1016/j.mcat.2021.111696

  21. Li H, Riisager A, Saravanamurugan S, Pandey A, Sangwan RS, Yang S, Luque R (2018) Carbon-increasing catalytic strategies for upgrading biomass into energy-intensive fuels and chemicals. ACS Catal 8:148–187

    Article  Google Scholar 

  22. Nguyen XP, Hoang AT, Ölçerv AI, Engel D, Pham VV, Nayak SK (2021) Biomass-derived 2,5-dimethylfuran as a promising alternative fuel: an application review on the compression and spark ignition engine. Fuel Process Technol 214:106687

    Article  Google Scholar 

  23. de la Flor D, López-Aguado C, Paniagua M, Morales G, Mariscal R, Melero JA (2021) Defective UiO-66(Zr) as an efficient catalyst for the synthesis of bio jet-fuel precursors via aldol condensation of furfural and MIBK. J Catal 401:27–39

    Article  Google Scholar 

  24. Xu Q, Sheng X, Li N, Zhang J, Shi H, Niu M, Ping Q, Li N (2021) Ball-milling: a productive, economical, and widely applicable method for condensation of biomass-derived aldehydes and ketones at mild temperatures. ACS Sustain Chem Eng 9:8232–8237

    Article  Google Scholar 

  25. Kwon JS, Choo H, Choi J, Jae J, Suh DJ, Lee KY, Ha J (2019) Condensation of pentose-derived furan compounds to C15 fuel precursors using supported phosphotungstic acid catalysts: strategy for designing heterogeneous acid catalysts based on the acid strength and pore structures. Appl Catal A Gen 570:238–244

    Article  Google Scholar 

  26. Bai J, Zhang Y, Zhang X, Wang C, Ma L (2021) Synthesis of high-density components of jet fuel from lignin-derived aromatics via alkylation and subsequent hydrodeoxygenation. ACS Sustain Chem Eng 9:7112–7119

    Article  Google Scholar 

  27. Cioc RC, Smak TJ, Crockatt M, van der Waal JC, Bruijnincx PCA (2021) Furoic acid and derivatives as atypical dienes in Diels-Alder reactions. Green Chem 23:5503–5510

    Article  Google Scholar 

  28. Settle AE, Berstis L, Rorrer NA, Roman-Leshkóv Y, Beckham GT, Richards RM, Vardon DR (2017) Heterogeneous Diels-Alder catalysis for biomass-derived aromatic compounds. Green Chem 19:3468–3492

    Article  Google Scholar 

  29. Kumar A, Srivastava R (2020) Zirconium phosphate catalyzed transformations of biomass derived furfural to renewable chemicals. ACS Sustain Chem Eng 8:9497–9506

    Article  Google Scholar 

  30. Erigoni A, Hernández-Soto MC, Rey F, Segarra C, Díaz U (2020) Highly active hybrid mesoporous silica-supported base organocatalysts for C-C bond formation. Catal Today 345:227–236

    Article  Google Scholar 

  31. Xu M, Zhang H, Guégan F, Frapper G, Corbet M, Marion P, Richard F, Clacens J (2020) Activated charcoal grafted with phenyl imidazole groups for Knœvenagel condensation of furfural with malononitrile. Catal Commun 147:106151

    Article  Google Scholar 

  32. Qin H, Zhou Y, Zeng Q, Cheng H, Chen L, Zhang B, Qi Z (2020) Efficient Knoevenagel condensation catalyzed by imidazole-based halogenfree deep eutectic solvent at room temperature. Green Energy Environ 5:124–129

    Article  Google Scholar 

  33. Choudhary P, Sen A, Kumar A, Dhingra S, Nagaraja CM, Krishnan V (2021) Sulfonic acid functionalized graphitic carbon nitride as solid acid-base bifunctional catalyst for Knoevenagel condensation and multicomponent tandem reactions. Mater Chem Front 5:6265–6278

    Article  Google Scholar 

  34. Bahuguna A, Kumar A, Chhabra T, Kumar A, Krishnan V (2018) Potassium-functionalized graphitic carbon nitride supported on reduced graphene oxide as a sustainable catalyst for Knoevenagel condensation. ACS Appl Nano Mater 1:6711–6723

    Article  Google Scholar 

  35. Xu G, Jin M, Kalkhajeh YK, Wang L, Tao M, Zhang W (2019) Proton sponge functionalized polyacrylonitrile fibers as an efficient and recyclable superbasic catalyst for Knoevenagel condensation in water. J Clean Prod 231:77–86

    Article  Google Scholar 

  36. van Schijndel J, Canalle LA, Molendijk D, Meuldijk J (2017) The green Knoevenagel condensation: solvent-free condensation of benzaldehydes. Green Chem Lett Rev 10:404–411

    Article  Google Scholar 

  37. Lolak N, Kuyuldar E, Burhan H, Goksu H, Akocak S, Sen F (2019) Composites of palladium-nickel alloy nanoparticles and graphene oxide for the Knoevenagel condensation of aldehydes with malononitrile. ACS Omega 4:6848–6853

    Article  Google Scholar 

  38. Opanasenko M, Dhakshinamoorthy A, Shamzhy M, Nachtigall P, Horáček M, Garcia H, Čejka J (2013) Comparison of the catalytic activity of MOFs and zeolites in Knoevenagel condensation. Catal Sci Technol 3:500–507

    Article  Google Scholar 

  39. Appaturi JN, Selvaraj M, Hamid SBA (2018) Synthesis of 3-(2-furylmethylene)-2,4-pentanedione using DL-alanine functionalized MCM-41 catalyst via Knoevenagel condensation reaction. Microporous Mesoporous Mater 260:260–269

    Article  Google Scholar 

  40. Gohain M, Laskar K, Paul AK, Daimary N, Maharana M, Goswami IK, Hazarika A, Bora U, Deka D (2020) Carica papaya stem: a source of versatile heterogeneous catalyst for biodiesel production and C-C bond formation. Renew Energy 147:541–555

    Article  Google Scholar 

  41. Tarade K, Shinde S, Sakate S, Rode C (2019) Pyridine immobilised on magnetic silica as an efficient solid base catalyst for Knoevenagel condensation of furfural with acetyl acetone. Catal Commun 124:81–85

    Article  Google Scholar 

  42. Anbu N, Hariharan S, Dhakshinamoorthy A (2020) Knoevenagel-Doebner condensation promoted by chitosan as a reusable solid base catalyst. Mol Catal 484:110744

    Article  Google Scholar 

  43. Anbu N, Elamathi V, Varalakshmi P, Dhakshinamoorthy A (2020) Chitosan as a biodegradable heterogeneous catalyst for Knoevenagel condensation for benzaldehydes and ethylcyanoacetamide. Catal Commun 138:105954

    Article  Google Scholar 

  44. Zhu S, Xu J, Cheng Z, Kuang Y, Wu Q, Wang B, Gao W, Zeng J, Li J, Chen K (2020) Catalytic transformation of cellulose into short rodlike cellulose nanofibers and platform chemicals over lignin-based solid acid. Appl Catal B Environ 268:118732

    Article  Google Scholar 

  45. Odoom-Wubah T, Li Q, Mulka R, Chen M, Huang J, Li Q, Luque R (2020) Calcified shrimp waste supported Pd NPs as an efficient catalyst towards benzene destruction. ACS Sustain Chem Eng 8:486–497

    Article  Google Scholar 

  46. Hussain Z, Kumar R (2018) Synthesis and characterization of novel corncob-based solid acid catalyst for biodiesel production. Ind Eng Chem Res 57:11645–11657

    Article  Google Scholar 

  47. Alirezvani Z, Dekamin MG, Davoodi F, Valiey E (2018) Melamine-functionalized chitosan: a new bio-based reusable bifunctional organocatalyst for the synthesis of cyanocinnamonitrile intermediates and densely functionalized nicotinonitrile derivatives. ChemistrySelect 3:10450–10463

    Article  Google Scholar 

  48. Tang S, Yang J, Lin L, Peng K, Chen Y, Jin S, Yao W (2020) Construction of physically crosslinked chitosan/sodium alginate/calcium ion double-network hydrogel and its application to heavy metal ions removal. Chem Eng J 393:124728

    Article  Google Scholar 

  49. Sellimi S, Younes I, Ayed HB, Maalej H, Montero V, Rinaudo M, Dahia M, Mechichi T, Hajji M, Nasri M (2015) Structural, physicochemical and antioxidant properties of sodium alginate isolated from Tunisian brown seaweed. Int J Biol Macromol 72:1358–1367

    Article  Google Scholar 

  50. Fujiwara Y, Maeda R, Takeshita H, Komohara Y (2021) Alginates as food ingredients absorb extra salt in sodium chloride-treated mice. Heliyon 7:e06551

    Article  Google Scholar 

  51. Wu Z, Wu J, Zhang R, Yuan S, Lu Q, Yu Y (2018) Colloid properties of hydrophobic modified alginate: Surface tension, ζ-potential, viscosity and emulsification. Carbohydr Polym 181:56–62

    Article  Google Scholar 

  52. Nouri A, Nouri AP, Khalafy J, Etivand N (2020) A new and facile synthesis of 3-(2-aryl-6-nitro-1H-indol-3-yl) quinoline-2,4(1H,3H)-diones by sodium alginate as biopolymeric catalyst. Res Chem Intermed 46:3025–3036

    Article  Google Scholar 

  53. Ilkhanizadeh S, Khalafy J, Dekamin MG (2019) Sodium alginate: a biopolymeric catalyst for the synthesis of novel and known polysubstituted pyrano[3,2-c]chromenes. Int J Biol Macromol 140:605–613

    Article  Google Scholar 

  54. Juan-Alcañiz J, Ramos-Fernandez EV, Lafont U, Gascon J, Kapteijn F (2010) Building MOF bottles around phosphotungstic acid ships: one-pot synthesis of bi-functional polyoxometalate-MIL-101 catalysts. J Catal 269:229–241

    Article  Google Scholar 

  55. Shakerizadeh-Shirazi F, Hemmateenejad B, Mehranpour AM (2013) Determination of the empirical solvent polarity parameter ET(30) by multivariate image analysis. Anal Methods 5:891–896

    Article  Google Scholar 

  56. Reichardt C (1994) Solvatochromic dyes as solvent polarity indicators. Chem Rev 94:2319–2358

    Article  Google Scholar 

  57. Rani D, Singla P, Agarwal J (2018) ‘Chitosan in water’ as an eco-friendly and efficient catalytic system for Knoevenagel condensation reaction. Carbohydr Polym 202:355–364

    Article  Google Scholar 

  58. Cheng H, Ning L, Liao S, Li W, Tang S, Li J, Chen H, Liu X, Shao L (2021) Nickel-alkyne-functionalized metal-organic frameworks: an efficient and reusable catalyst. Appl Catal A Gen 623:118216

    Article  Google Scholar 

  59. Samui A, Kesharwani N, Haldar C, Sahu SK (2020) Fabrication of nanoscale covalent porous organic polymer: an efficacious catalyst for Knoevenagel condensation. Microp Mesop Mater 299:110112

    Article  Google Scholar 

  60. Lee Y, Do XH, Hwang SS, Baek K (2021) Dual-functionalized ZIF-8 as an efficient acid-base bifunctional catalyst for the one-pot tandem reaction. Catal Today 359:124–132

    Article  Google Scholar 

  61. Tan YC, Zeng HC (2018) Lewis basicity generated by localised charge imbalance in noble metal nanoparticle-embedded defective metal-organic frameworks. Nat Commun 9:4326

    Article  Google Scholar 

  62. Sigel H, Griesser R, Prijs BB, Mccormick DB, Joiner MG (1969) “Hard and Soft” Behavior of Mn2+, Cu2+, and Zn2+ with respect to carboxylic acids and α-oxy- or α-thio-substituted carboxylic acids of biochemical significance. Arch Biochem Biophys 130:514–520

    Article  Google Scholar 

  63. Zhao X, Wang X, Lou T (2022) Simultaneous adsorption for cationic and anionic dyes using chitosan/electrospun sodium alginate nanofiber composite sponges. Carbohydr Polym 276:118728

    Article  Google Scholar 

  64. Swamy BY, Yun Y (2015) In vitro release of metformin from iron (III) cross-linked alginate-carboxymethyl cellulose hydrogel beads. Int J Biol Macromol 77:114–119

    Article  Google Scholar 

Download references

Funding

Financial supports from the Outstanding Youth Project of Hunan Provincial Education Department (19B470), the Hunan Provincial Natural Science Foundation of China (2021JJ40436, 2021JJ40439), the Key Project of Hunan Provincial Education Department (20A412), the research start-up funds of Jishou University (91602, 1119050), and Open Research Foundation of Key Laboratory of Hunan Forest Products and Chemical Industry Engineering of Jishou University (LCHG2101) are gratefully acknowledged.

Author information

Authors and Affiliations

  1. Key Laboratory of Hunan Forest Products and Chemical Industry Engineering, Jishou University, Zhangjiajie, 427000, People’s Republic of China

    Lulu Chen, Shima Liu, Ke Song, Xianwu Zhou, Jie Guo & Jian He

  2. College of Chemistry and Chemical Engineering, Jishou University, Jishou, Hunan, 416000, People’s Republic of China

    Shima Liu, Ke Song, Xianwu Zhou, Jie Guo, Ou Zhuo & Jian He

  3. College of Biological, Chemical Science and Engineering, Jiaxing University, Jiaxing, 314001, Zhejiang, China

    Hu Pan

Authors
  1. Lulu Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Shima Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Hu Pan
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Ke Song
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Xianwu Zhou
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Jie Guo
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Ou Zhuo
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Jian He
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Jian He.

Ethics declarations

Competing interests

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.

Supplementary Information

Below is the link to the electronic supplementary material.

Supplementary file1 (DOCX 2.96 MB)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Chen, L., Liu, S., Pan, H. et al. Naturally biodegradable polymer as an effective heterogeneous catalyst for synthesis of biofuels via Knoevenagel condensation strategy. Biomass Conv. Bioref. 14, 465–476 (2024). https://doi.org/10.1007/s13399-021-02253-8

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s13399-021-02253-8

Keywords

Search

Navigation