Production of bio-ethanol by consecutive hydrogenolysis of corn-stalk cellulose

DOI: 10.1016/S1872-2067(20)63709-3

Source and publish data:

Cuihua Xuebao/Chinese Journal of Catalysis p. 844 - 854 (2021)

Update date:2022-08-11

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Authors:

Chu, Dawang

Xin, Yingying

Zhao, Chen

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Article abstract of DOI:10.1016/S1872-2067(20)63709-3

Current bio-ethanol production entails the enzymatic depolymerization of cellulose, but this process shows low efficiency and poor economy. In this work, we developed a consecutive aqueous hydrogenolysis process for the conversion of corn-stalk cellulose to produce a relatively high concentration of bio-ethanol (6.1 wt%) without humin formation. A high yield of cellulose (ca. 50 wt%) is extracted from corn stalk using a green solvent (80 wt% 1,4-butanediol) without destroying the structure of the lignin. The first hydrothermal hydrogenolysis step uses a Ni–WO_x/SiO₂ catalyst to convert the high cumulative concentration of cellulose (30 wt%) into a polyol mixture with a 56.5 C% yield of ethylene glycol (EG). The original polyol mixture is then subjected to subsequent selective aqueous-phase hydrogenolysis of the C–O bond to produce bioethanol (75% conversion, 84 C% selectivity) over the modified hydrothermally stable Cu catalysts. The added Ni component favors the good dispersion of Cu nanoparticles, and the incorporated Au³⁺ helps to stabilize the active Cu⁰-Cu⁺ species. This multi-functional catalytic process provides an economically competitive route for the production of cellulosic ethanol from raw lignocellulose.

Full text of DOI:10.1016/S1872-2067(20)63709-3

Chinese Journal of Catalysis 42 (2021) 844–854

a v a i l a b l e a t w w w . s c i e n c e d i r e c t . c o m

j o u r n a l h o m e p a g e : w w w . e l s e v i e r . c o m / l o c a t e / c h n j c

Article

Production of bio‐ethanol by consecutive hydrogenolysis of

corn‐stalk cellulose

Dawang Chu, Yingying Xin, Chen Zhao *

Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University,

Shanghai 200062, China

A R T I C L E I N F O

A B S T R A C T

Article history:

Received 1 June 2020

Accepted 5 August 2020

Available online 22 September 2020

Current bio‐ethanol production entails the enzymatic depolymerization of cellulose, but this process

shows low efficiency and poor economy. In this work, we developed a consecutive aqueous hydro‐

genolysis process for the conversion of corn‐stalk cellulose to produce a relatively high concentra‐

tion of bio‐ethanol (6.1 wt%) without humin formation. A high yield of cellulose (ca. 50 wt%) is

extracted from corn stalk using a green solvent (80 wt% 1,4‐butanediol) without destroying the

structure of the lignin. The first hydrothermal hydrogenolysis step uses a Ni–WO_x/SiO₂catalyst to

convert the high cumulative concentration of cellulose (30 wt%) into a polyol mixture with a 56.5

C% yield of ethylene glycol (EG). The original polyol mixture is then subjected to subsequent selec‐

tive aqueous‐phase hydrogenolysis of the C–O bond to produce bioethanol (75% conversion, 84 C%

selectivity) over the modified hydrothermally stable Cu catalysts. The added Ni component favors

the good dispersion of Cu nanoparticles, and the incorporated Au³⁺helps to stabilize the active

Cu⁰‐Cu⁺species. This multi‐functional catalytic process provides an economically competitive route

for the production of cellulosic ethanol from raw lignocellulose.

Keywords:

Corn‐stalk

Cellulose

Aqueous‐phase hydrogenolysis

Bio‐ethanol

Ni‐WO_xcatalyst

Cu⁰‐Cu⁺species

C–C bond cleavage

1. Introduction

mol CO₂and 2 mol ethanol [2,3]. Therefore, the development of

advanced catalytic approaches for the conversion of high con‐

Bio‐ethanol is a promising green and renewable liquid fuel

that is used as a gasoline additive. First generation bio‐ethanol

production involves the sequential hydrolysis and fermentation

of grain. To avoid the use of agricultural crops to produce liquid

energy sources, the sustainable biomass cellulose is considered

to be a new, more promising resource for bio‐ethanol produc‐

tion. The current technique for the production of ethanol from

cellulose involves enzymatic hydrolysis of the cellulose to pro‐

duce sugar and subsequent fermentation to produce

bio‐ethanol [1]. However, this bio‐fermentation process shows

low activity and low atom economy, i.e., 1 mol sugar produces 2

centrations of cellulose is highly desired.

Compared to enzymatic catalysis, the transformation of cel‐

lulose into bio‐ethanol via heterogeneous catalysis is more

attractive due to its high efficiency. Zhang and co‐workers [4,5]

introduced a pioneering two‐step process for the conversion of

cellulose into bio‐ethanol that involves the formation of methyl

glycolate (MG) over a WO_xcatalyst using 1 MPa O₂at 240 °C,

followed by the hydrogenation of MG to bio‐ethanol over

Pt‐Cu/SiO₂at 180 °C and 3 MPa H₂. To avoid the risks associat‐

ed with O₂, the same group developed a one‐pot process for the

hydrogenation of cellulose into bio‐ethanol (43.2 C%) over a

* Corresponding author. Tel/Fax: +86‐21‐62231392; E‐mail: czhao@chem.ecnu.edu.cn

This work was supported by the National Key Research and Development Program of China (2016YFB0701100) and the National Natural Science

Foundation of China (21573075).

DOI: 10.1016/S1872‐2067(20)63709‐3 | http://www.sciencedirect.com/science/journal/18722067 | Chin. J. Catal., Vol. 42, No. 5, May 2021

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Chinese Journal of Catalysis, 42 (2021) 844-854. doi:10.1016/S1872-2067(20)63709-3

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Chinese Journal of Catalysis, 42 (2021) 844-854. doi:10.1016/S1872-2067(20)63709-3

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Chinese Journal of Catalysis, 42 (2021) 844-854. doi:10.1016/S1872-2067(20)63709-3

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