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N-Methyl-2-pyrrolidone pre-treatment of lignocellulose for high lignin yield and cellulose digestibility

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Abstract

In the present study, we discovered a new N-methyl-2-pyrrolidone (NMP) pretreatment solvent with an excellent lignin solubility and preserved β-O-4 linkages available in the original lignin structure. The results indicate that the formation of 4-methylamino butyric acid in NMP pretreatment system increased the polarity of the solvent system. The increased polarity synergistically increased the lignin removal and reduced the amount of lignin condensation. Results indicate a ca. 94% lignin removal was achieved, which is 25.6% higher than ethanol. Meanwhile, size-exclusion chromatography analysis revealed that the residual lignin obtained from NMP pretreated Acacia confusa contained a relatively higher number average (Mn) and weight average (Mw) molecular weights, indicating its higher integrity in terms of preserving the original lignin structure, than ethanol pretreated lignin. The result corresponds to the higher amount of β-O-4 interunit linkages in NMP lignin sample and is supported via HSQC analysis. A new organic hydrolysis factor (OHF) was established and introduced as an indicator in biomass separation experiments. This method can effectively quantify the effects of temperature, time, and acid catalyst concentration. The results showed that NMP exhibited better lignin solubility under the same OHF condition. Meanwhile, the NMP system showed higher tolerance for condensed lignin. In addition, almost 100% of the cellulose conversion was obtained for the NMP pretreated Acacia confusa wood substrates after 60 h of enzymatic hydrolysis with cellulase at a loading of 15 FPU per gram of glucan.

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References

  1. Bhatia SK et al (2019) Bioconversion of plant biomass hydrolysate into bioplastic (polyhydroxyalkanoates) using Ralstonia eutropha 5119. Biores Technol 271:306–315

    Article  Google Scholar 

  2. Naghshbandi MP, et al. (2019) Progress toward improving ethanol production through decreased glycerol generation in Saccharomyces cerevisiae by metabolic and genetic engineering approaches. Renew Sustain Energy Rev 115:109353

  3. de Paula R.G, et al. (2019) Engineered microbial host selection for value-added bioproducts from lignocellulose. Biotechnol Adv 37(6):107347

  4. Watts N et al (2018) The 2018 report of the Lancet Countdown on health and climate change: sha** the health of nations for centuries to come. The Lancet 392(10163):2479–2514

    Article  Google Scholar 

  5. Yoo CG et al (2017) Insights of biomass recalcitrance in natural Populus trichocarpa variants for biomass conversion. Green Chem 19(22):5467–5478

    Article  Google Scholar 

  6. Leu S-Y, Zhu J (2013) Substrate-related factors affecting enzymatic saccharification of lignocelluloses: our recent understanding. Bioenergy Research 6(2):405–415

    Article  Google Scholar 

  7. Zhao X, Zhang L, and Liu D (2012) Biomass recalcitrance. Part I: the chemical compositions and physical structures affecting the enzymatic hydrolysis of lignocellulose. Biofuels Bioprod Biorefining 6(4):465–482

  8. Galbe M, Wallberg O (2019) Pretreatment for biorefineries: a review of common methods for efficient utilisation of lignocellulosic materials. Biotechnol Biofuels 12(1):1–26

    Article  Google Scholar 

  9. Ilanidis D, et al. (2020) Effects of redox environment on hydrothermal pretreatment of lignocellulosic biomass under acidic conditions. Bioresource Technol 319:124211

  10. Meng X, et al. (2020) Effects of the advanced organosolv pretreatment strategies on structural properties of woody biomass. Ind Crops Prod 146:112144

  11. Pan X et al (2005) Biorefining of softwoods using ethanol organosolv pul**: Preliminary evaluation of process streams for manufacture of fuel-grade ethanol and co-products. Biotechnol Bioeng 90(4):473–481

    Article  Google Scholar 

  12. Lee J-W, Jeffries TW (2011) Efficiencies of acid catalysts in the hydrolysis of lignocellulosic biomass over a range of combined severity factors. Biores Technol 102(10):5884–5890

    Article  Google Scholar 

  13. Wyman CE (2013) Aqueous pretreatment of plant biomass for biological and chemical conversion to fuels and chemicals. John Wiley & Sons.

  14. Dong C et al (2019) Diol pretreatment to fractionate a reactive lignin in lignocellulosic biomass biorefineries. Green Chem 21(10):2788–2800

    Article  Google Scholar 

  15. Islam MK, et al. (2020) Valorisation of Woody Biomass. Waste Valorisation: Waste Streams in a Circular Economy, p. 87–108

  16. Islam MK, et al. (2020) Sustainability metrics of pretreatment processes in a waste derived lignocellulosic biomass biorefinery. Bioresource Technol 298:122558

  17. Ma J et al (2018) Dispersion of pristine and polyaniline functionalized carbon nanotubes in designed solvent mixtures by Hansen solubility parameters. Materials Today Communications 14:99–105

    Article  Google Scholar 

  18. Roche-Molina M et al (2020) The pharmaceutical solvent N-methyl-2-pyrollidone (NMP) attenuates inflammation through Krüppel-like factor 2 activation to reduce atherogenesis. Sci Rep 10(1):1–16

    Article  Google Scholar 

  19. Lammens TM et al (2010) Synthesis of biobased N-methylpyrrolidone by one-pot cyclization and methylation of γ-aminobutyric acid. Green Chem 12(8):1430–1436

    Article  Google Scholar 

  20. Moshikur RM, et al. (2020) Ionic liquids with N-methyl-2-pyrrolidonium cation as an enhancer for topical drug delivery: Synthesis, characterization, and skin-penetration evaluation. J Mol Liq 299:112166

  21. Shortt J et al (2014) The drug vehicle and solvent N-methylpyrrolidone is an immunomodulator and antimyeloma compound. Cell Rep 7(4):1009–1019

    Article  Google Scholar 

  22. Chen L, et al. (2017) Rapid and near-complete dissolution of wood lignin at≤ 80 C by a recyclable acid hydrotrope. Sci Adv 3(9):e1701735

  23. Sunitha K, et al. (2013) Separation of NMP/water mixtures by nanocomposite PEBA membrane: Part I. Membrane synthesis, characterization and pervaporation performance. Desalination 330:1–8

  24. **e H et al (2012) Enzymatic hydrolysates of corn stover pretreated by a N-methylpyrrolidone–ionic liquid solution for microbial lipid production. Green Chem 14(4):1202–1210

    Article  Google Scholar 

  25. Mu L et al (2015) [N-Methyl-2-pyrrolidone][C1–C4 carboxylic acid]: a novel solvent system with exceptional lignin solubility. Chem Commun 51(70):13554–13557

    Article  Google Scholar 

  26. Asakawa A et al (2016) Cholinium ionic liquid/cosolvent pretreatment for enhancing enzymatic saccharification of sugarcane bagasse. Ind Crops Prod 86:113–119

    Article  Google Scholar 

  27. Sluiter A et al (2008) Determination of structural carbohydrates and lignin in biomass. Laboratory analytical procedure 1617(1):1–16

    Google Scholar 

  28. Van Aelst K et al (2020) Reductive catalytic fractionation of pine wood: elucidating and quantifying the molecular structures in the lignin oil. Chem Sci 11(42):11498–11508

    Article  Google Scholar 

  29. Islam MK, et al. (2021) Biphasic pretreatment for energy and carbon efficient conversion of lignocellulose into bioenergy and reactive lignin. Appl Energy 303:117653

  30. Kalogiannis K et al (2018) Acid assisted organosolv delignification of beechwood and pulp conversion towards high concentrated cellulosic ethanol via high gravity enzymatic hydrolysis and fermentation. Molecules 23(7):1647

    Article  Google Scholar 

  31. Chen L, et al. (2017) Rapid and near-complete dissolution of wood lignin at≤ 80° C by a recyclable acid hydrotrope. Sci Adv 3(9):e1701735

  32. Yeh T-F, Chang M-J, Chang W-J (2014) Comparison of dilute acid and sulfite pretreatments on Acacia confusa for biofuel application and the influence of its extractives. J Agric Food Chem 62(44):10768–10775

    Article  Google Scholar 

  33. Lennon G, et al. (2020) Assessing the oxidative degradation of N-methylpyrrolidone (NMP) in microelectronic fabrication processes by using a multiplatform analytical approach. J Anal Methods Chem 2020

  34. Liu H et al (2016) Toward a fundamental understanding of cellulase-lignin interactions in the whole slurry enzymatic saccharification process. Biofuels, Bioprod Biorefin 10(5):648–663

    Article  Google Scholar 

  35. Li N et al (2018) An uncondensed lignin depolymerized in the solid state and isolated from lignocellulosic biomass: a mechanistic study. Green Chem 20(18):4224–4235

    Article  Google Scholar 

  36. Schunk A and Maurer G (2003) Distribution of hydrochloric, nitric, and sulfuric acid between water and organic solutions of tri-n-octylamine: Part II. Methylisobutylketone as organic solvent. Fluid Phase Equilib 211(2):189–209

  37. Zhu W et al (2012) Quantitative predictions of bioconversion of aspen by dilute acid and SPORL pretreatments using a unified combined hydrolysis factor (CHF). Process Biochem 47(5):785–791

    Article  Google Scholar 

  38. Leu S.-Y, et al. (2013) Robust enzymatic saccharification of a Douglas-fir forest harvest residue by SPORL. Biomass Bioenerg 59: 393–401

  39. Kim DH et al (2019) Pretreatment and enzymatic saccharification of oak at high solids loadings to obtain high titers and high yields of sugars. Biores Technol 284:391–397

    Article  Google Scholar 

  40. Shen X-J et al (2019) Facile fractionation of lignocelluloses by biomass-derived deep eutectic solvent (DES) pretreatment for cellulose enzymatic hydrolysis and lignin valorization. Green Chem 21(2):275–283

    Article  Google Scholar 

  41. Wang Y et al (2019) Substrate-related factors affecting cellulosome-induced hydrolysis for lignocellulose valorization. Int J Mol Sci 20(13):3354

    Article  Google Scholar 

  42. Chan KL et al (2021) Construction of a structural enzyme adsorption/kinetics model to elucidate additives associated lignin–cellulase interactions in complex bioconversion system. Biotechnol Bioeng 118(10):4065–4075

    Article  Google Scholar 

  43. Bhagia S, Ragauskas AJ (2019) Preserving Aryl Ether Linkages and Higher Yields of Isolated Lignin through Biomass Fibrillation. ACS Sustain Chem Eng 8(1):34–37

    Article  Google Scholar 

  44. Dutta T et al (2018) Characterization of lignin streams during bionic liquid-based pretreatment from grass, hardwood, and softwood. ACS Sustain Chem Eng 6(3):3079–3090

    Article  Google Scholar 

  45. Schneider WDH, et al. (2020) Lignin degradation and detoxification of eucalyptus wastes by on-site manufacturing fungal enzymes to enhance second-generation ethanol yield. Appl Energy 262:114493

  46. Amiri MT et al (2019) Establishing lignin structure-upgradeability relationships using quantitative 1 H–13 C heteronuclear single quantum coherence nuclear magnetic resonance (HSQC-NMR) spectroscopy. Chem Sci 10(35):8135–8142

    Article  Google Scholar 

  47. Zijlstra DS et al (2020) Mild organosolv lignin extraction with alcohols: the importance of benzylic alkoxylation. ACS Sustain Chem Eng 8(13):5119–5131

    Article  Google Scholar 

  48. Lancefield CS et al (2017) Pre-treatment of lignocellulosic feedstocks using biorenewable alcohols: towards complete biomass valorisation. Green Chem 19(1):202–214

    Article  Google Scholar 

  49. Meng X et al (2020) A biomass pretreatment using cellulose-derived solvent Cyrene. Green Chem 22(9):2862–2872

    Article  Google Scholar 

  50. Sherwood J et al (2014) Dihydrolevoglucosenone (Cyrene) as a bio-based alternative for dipolar aprotic solvents. Chem Commun 50(68):9650–9652

    Article  Google Scholar 

  51. Basma NS et al (2018) Local structure and polar order in liquid N-methyl-2-pyrrolidone (NMP). J Phys Chem B 122(38):8963–8971

    Article  Google Scholar 

Download references

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Guan Jianyu and Md Khairul Islam share the first authorship for equal contribution. The manuscript is prepared with the contributions of all the authors and all the authors agreed to the submission.

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Correspondence to Shao-Yuan Leu or Arun K. Vuppaladadiyam.

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Islam, M.K., Guan, J., Rehman, S. et al. N-Methyl-2-pyrrolidone pre-treatment of lignocellulose for high lignin yield and cellulose digestibility. Biomass Conv. Bioref. 14, 5435–5446 (2024). https://doi.org/10.1007/s13399-022-02655-2

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