Integration of Ru/C and base for reductive catalytic fractionation of triploid poplar

doi:10.1016/S1872-2067(21)63881-0

Abstract

Abstract:

Lignin, which is the most recalcitrant component of lignocellulosic biomass, is also the most abundant renewable aromatic resource. Herein, reductive treatment of triploid poplar sawdust by the integration of catalytic Ru/C and a base, which afforded high yields of phenolic monomers from the lignin component and a solid carbohydrate pulp, is reported. The introduction of Cs₂CO₃ led to the generation of C2 side-chained phenols through the cleavage of C_β-O and C_β-C_γ bonds in β-O-4 units in addition to C3 side-chained phenols; the relationship between C2 and C3 was dependent on the base dosage. The reaction conditions, including base species, temperature, time, and H₂ pressure, were optimized in terms of phenolic product distribution, delignification degree, and carbohydrate retention. The carbohydrate pulps generated from reductive catalytic fractionation in the presence of Cs₂CO₃ were more amenable to enzymatic hydrolysis, indicating that this treatment of biomass constituted the fractionation of biomass components together with the breakdown of biomass recalcitrance.

Key words: Ru/C, Lignin, Catalytic reductive degradation, Triploid populous tomentosa, Base, Cellulose enzymolysis

Yiwei Fan, Helong Li, Shihao Su, Jinlei Chen, Chunquan Liu, Shuizhong Wang, Xiangya Xu, Guoyong Song. Integration of Ru/C and base for reductive catalytic fractionation of triploid poplar[J]. Chinese Journal of Catalysis, 2022, 43(3): 802-810.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)63881-0

https://www.cjcatal.com/EN/Y2022/V43/I3/802

Figures/Tables 7

Fig. 1. Composition of triploid of Populus tomentosa Carr. and a general scheme of the RCF process.

Fig. 2. Hydrogenolysis of β-O-4 model. (a) The influence of reaction temperature, GG (25 mg), Ru/C (20 wt%), Cs2CO3 (20 wt%), MeOH (10 mL), H2 (40 atm), 3 h; (b) The influence of reaction temperature, GG (25 mg), Ru/C (20 wt%), Cs2CO3 (20 wt%), MeOH (10 mL), 170 °C, 3 h; (c) Time profile, GG (150 mg), Ru/C (30 mg, 20 wt%), Cs2CO3 (30 mg, 20 wt%), MeOH (150 mL), 180 °C, H2 (30 atm), performed in a 300 mL reactor, an aliquot was picked per hour. C.B., carbon balance.

Fig. 3. The analysis of phenolic monomers (a) and left pulps (b) from Ru/C-catalyzed RCF of triploid Populus tomentosa with different bases. Reaction conditions: poplar sawdust (500 mg), Ru/C (50 mg), base (0.06mol, equal mole with the 4 wt% Cs2CO3), MeOH (15 mL), H2 (30 atm), 4 h. (a) Lignin monomers distribution. (b) Retentions of solid phase after RCF.

Fig. 4. The influence of Cs2CO3 dosage in RCF of poplar sawdust. (a) Lignin monomers distribution. (b) Rest cellulose (initial: 252 mg) and hemicellulose (initial: 93 mg) in pulps. (c) The relationship between C2/C3 products (mol/mol) and the dose of Cs2CO3 (wt%). (d) GPC spectra of lignin derived oils. (e,f) 2D HSQC NMR spectra of lignin products with 2 and 20 wt% of Cs2CO3. Reaction conditions: poplar sawdust (500 mg), Ru/C (10 wt%), Cs2CO3 (2 wt%-20), MeOH (15 mL), H2 pressure (30 atm), 220 °C, 4 h.

Fig. 5. SEM images. (a) Triploid poplar sawdust; (b) Solid residues with 2 wt% of Cs2CO3; (c) 20 wt% of Cs2CO3. Reaction conditions: poplar sawdust (500 mg), Ru/C (10 wt%), MeOH (15 mL), H2 pressure (30 atm), 220 °C, 4 h.

Fig. 6. The influence of reaction temperature (a,b), H2 pressure (c,d) and reaction time (e,f). Reaction conditions: triploid poplar sawdust (500 mg), Ru/C (10 wt%), Cs2CO3 (4 wt%), MeOH (15 mL), H2 (30 atm), 4 h for (a) and (b); 220 °C, 2 h for (c) and (d); H2 (30 atm), 220 °C for (e) and (f).

Fig. 7. Enzymatic hydrolysis of pulp cellulose into glucose.

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