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. 2023 Aug 25:11:1233889.
doi: 10.3389/fchem.2023.1233889. eCollection 2023.

A ternary eutectic solvent for cellulose nanocrystal production: exploring the recyclability and pre-pilot scale-up

Mayra A Mariño  1 , Maria G Paredes  2 , Natalia Martinez  3 , Daniela Millan  4 , Ricardo A Tapia  2 , Domingo Ruiz  5 , Mauricio Isaacs  2   6   7 , Paulina Pavez  2
Affiliations

A ternary eutectic solvent for cellulose nanocrystal production: exploring the recyclability and pre-pilot scale-up

Mayra A Mariño et al. Front Chem. .

Abstract

Deep eutectic solvents (DES) formed using choline chloride (ChCl), p-toluenesulfonic acid (pTSA) of stoichiometry ChCl: pTSA (1:1) and (1:2), and its ternary eutectic mixtures with phosphoric acid (PA) 85% as an additive (ChCl: pTSA: PA) were evaluated for cellulose nanocrystal (CNC) isolation. Initially, the hydrolytic efficiency to produce CNC of each DES was compared before and after adding phosphoric acid by Hammett acidity parameters and the Gutmann acceptor number. Moreover, different DES molar ratios and reaction time were studied at 80°C for CNC optimization. The nanomaterial characteristics were analyzed by field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), and thermogravimetric analysis (TGA). The ternary eutectic mixture ChCl: pTSA: PA molar ratio (1:1:1.35) was chosen as a suitable recyclable ternary system at the laboratory scale. A CNC yield of about 80% was obtained from the hydrolysis of commercial cellulose in five cycles of recovery, but it dropped to 35% in pre-pilot scaling. However, no variation in the average size of the resulting CNC was observed (132 ± 50 nm x 23 ± 4 nm), which presented high thermal stability (Tmax 362°C) and high crystallinity of about 80% after 3 h of reaction time.

Keywords: cellulose; deep eutectic solvents; nanowhiskers; recyclable media; ternary solvents.

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Conflict of interest statement

The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest.

Figures

FIGURE 1
FIGURE 1
Binary eutectic mixture (A) ChCl: pTSA (DES1:1) and (B) ChCl: pTSA (DES1:2).
FIGURE 2
FIGURE 2
(A) Correlation of H 0 values and CNC yields obtained; (B) correlation of AN values and CNC yields obtained using DES (1:1), DES (1:1:0.34), and DES (1:1:1.35) as a solvent reaction at 80 °C during 2 h. Each experiment was performed at least in triplicate.
FIGURE 3
FIGURE 3
(A,B) Comparison between FESEM and STEM techniques, respectively, for determination of the particle size and morphology of CNC obtained using the ternary eutectic mixture DES ChCl: pTSA: PA (1:1:1.35) at 80 °C (Exp. 9, Table 1). (C,D) Histograms obtained from FESEM and STEM analyses, respectively.
FIGURE 4
FIGURE 4
DTG curves for CNC obtained using the binary mixture ChCl: pTSA (1:1) and ternary mixtures ChCl: pTSA: PA (1:1:0.34) and ChCl: pTSA: PA (1:1:1.35) at 80 °C and 3 h. Exps 3, 6, and 9 in Table 1, respectively.
FIGURE 5
FIGURE 5
XRD patterns of (A) CNC obtained in the experimental condition (Exps 6, 9, 15, and 18 in Tables 1, 2) using the ternary eutectic mixtures ChCl: pTSA: PA (1:1:0.34), ChCl: pTSA: PA (1:1:1.35), ChCl: pTSA: PA (1:2:0.53), and ChCl: pTSA: PA (1:2:2.12). (B) Comparison of XRD patterns of CNC obtained under the experimental conditions of Exps 6 and 15 (Table 1) using ChCl: pTSA: PA (1:1:0.34) and ChCl: pTSA: PA (1:1:1.35), respectively.
FIGURE 6
FIGURE 6
Crystallinity values for CNC obtained using ternary eutectic mixtures ChCl: pTSA: PA (1:1:0.34), ChCl: pTSA: PA (1:1:1.35), ChCl: pTSA: PA (1:2:0.53), and ChCl: pTSA: PA (1:2:2.12) by XRD data.
FIGURE 7
FIGURE 7
Five cycles of use of DES ChCl: pTSA: PA (1:1:1.35) (Exp. 9, Table 1) at 80 °C and 3 h reaction time.
FIGURE 8
FIGURE 8
(A) CNC suspension; (B) CNC gel; (C) CNC film; (D) CNC powder. All obtained after hydrolysis at 80 °C and 3 h reaction time using the ternary eutectic mixture DES ChCl: pTSA: PA (1:1:1.35) (Exp. 9) in the scale mass DESx500 in a reactor.
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