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Treating lignocellulosic biomass with dilute solutions at ambient temperature: effects on cellulose crystallinity

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Abstract

The decrystallization or hydrolysis of lignocellulosic biomass is usually carried out either with concentrated solutions at moderate temperature or with dilute solutions at high temperatures. In contrast to this, agricultural waste biomasses (sunflower stalk, rapeseed stalk, and rice hull) were treated with dilute acidic or alkaline aqueous solutions (5 mol %) in this study to test the variations in cellulose crystallinity under ambient temperature. Solutions of HCl, H3PO4, CH3COOH, HNO3, H2SO4, HF, NaOH, Ca(OH)2, C2H5OH, and CS(NH2)2 were used. Effects of the treatment on cellulose crystallinity were evaluated based on the crystallinity index (CrI) calculations through the reflection intensities in X-ray diffraction (XRD) and the absorbance ratios in Fourier transform-infrared (FTIR) spectroscopy at A1429/A897 (lateral order index) and A1374/A2900 (total crystallinity index). It was found that the CrI values based on the total crystallinity index suited more than lateral order index to the CrI values found by XRD method. HF solutions led to most striking decreases in CrI, while the solutions of neither strong acids nor NaOH resulted in reductions in CrI. Derivative thermogravimetry (DTG) and differential scanning calorimetry (DSC) profiles revealed that the applied treatment influenced the pyrolytic degradation characteristics and the reactivity of biomass in range of 300–400 °C where cellulose decomposed.

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Data will be made available on reasonable request.

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Abbreviations

ASTM:

American Society for Testing and Materials

CrI:

Crystallinity index

DSC:

Differential scanning calorimetry

DTG:

Derivative thermogravimetry

FTIR:

Fourier transform infrared

HHV:

Higher heating value (MJ/kg)

Ka:

Acid dissociation constant

LOI:

Lateral order index

LHV:

Lower heating value (MJ/kg)

NMR:

Nuclear magnetic resonance

RS:

Rapeseed stalk

RH:

Rice hull

SS:

Sunflower stalk

TCI:

Total crystallinity index

XRD:

X-ray diffraction

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Authors and Affiliations

  1. Department of Chemical Engineering, Faculty of Chemical and Metallurgical Engineering, Istanbul Technical University, Maslak, 34469, Istanbul, Turkey

    Haykiri-Acma H. & Yaman S.

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Highlights

 > Effects of dilute solutions on cellulose crystallinity were studied comparatively.

 > The solution of HF is the most efficient in terms of reduction in cellulose crystallinity.

 > Compared to A1429/A897 (lateral order index), CrI values based on A1374/A2900 (total crystallinity index) are more consistent with those found by XRD.

 > Applied treatment affected the pyrolytic degradation characteristics at temperatures between 300 and 400 °C where cellulose decomposed.

Statement of novelty

Insufficient attention has been paid to the treatment of lignocellulosic biomass using dilute solutions under ambient temperature, as it appears to be ineffective. In this study, it was aimed to determine how the cellulose crystallinity of lignocellulosic biomass treated by dilute solutions at ambient temperature is affected. In addition, a comparative evaluation was made to determine to what extent the cellulose crystallinity index (CrI) values determined according to XRD and FTIR techniques were compatible with each other. Also, effects of applied treatment on the pyrolytic degradation and the reactivity of cellulose were also studied. The results showed that the treatment with dilute solutions can have a non-negligible effect on the cellulose crystallinity of the lignocellulosic biomass, contrary to expectations.

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H., HA., S., Y. Treating lignocellulosic biomass with dilute solutions at ambient temperature: effects on cellulose crystallinity. Biomass Conv. Bioref. 14, 9967–9981 (2024). https://doi.org/10.1007/s13399-022-03085-w

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