Molecular Structure and Formation Mechanism of Hydrochar from Hydrothermal Carbonization of Carbohydrates

doi:10.1021/acs.energyfuels.9b02174

GIEC OpenIR

	Molecular Structure and Formation Mechanism of Hydrochar from Hydrothermal Carbonization of Carbohydrates
	Shi, Ning 1,2,3; Liu, Qiying2,3 ; He, Xiong 1; Wang, Gui 1; Chen, Ni 1; Peng, Jiayu 1; Ma, Longlong2,3
	2019-10-01
发表期刊	ENERGY & FUELS
ISSN	0887-0624
卷号	33 期号:10 页码:9904-9915
通讯作者	Shi, Ning(shining@git.edu.cn)
摘要	Hydrochars are solid byproducts formed during the liquid-phase biorefinery process and could be used to generate functional carbonaceous materials, but the detailed molecular structure and the formation mechanism are still unclear. Herein, the formation of hydrochars from liquid-phase carbonization of biomass-derived compounds including glucose, fructose, xylose, ribose, dihydroxyacetone (DHA), 5-hydroxymethylfurfural (HMF), furfural (FF), and pyruvaldehyde (PRV) in water and inert polar organic solvents ethyl acetate (EAC) and tetrahydrofuran (THF) was studied. The carbohydrates were found to generate hydrochars in both water and the organic solvents, while the HMF and FF could generate hydrochars only in water. The a-carbonyl aldehydes, including PRV, 3-deoxyglucosone, and 2,5-dioxo-6-hydroxyhexanal (DHH), formed during the decomposition of carbohydrates were proposed to be the key primary precursors for hydrochar formation. The molecular structures of the hydrochars were characterized by elemental analysis, Fourier transform infrared analysis, and solid-state C-13 NMR analysis to confirm that the molecular formula of the hydrochars all could be approximately expressed as (C3H2O)(n), and the molecular structures of the hydrochars all consisted of polyaromatic hydrocarbon, phenolic, furanic, and aliphatic framents and a small amount of carbonyl/carboxyl groups. The presence of the polyaromatic hydrocarbon and phenolic fragments in the hydrochars suggested that aldol condensation played a critical role for hydrochar formation. By regarding the aldol condensation of alpha-carbonyl aldehydes as the initial step for hydrochar formation, we deduced the polymerization routes of these a-carbonyl aldehydes and found that the a-carbonyl aldehydes all could undergo aldol condensation followed by acetal cyclization and etherification to form polymers (C3H2O)(n) rich in furanic framework or undergo aldol condensation followed by a 1,2-hydride shift, intramolecular aldol condensation, and dehydration to generate polymers (C3H2O)(n) rich in the phenolic framework. One molecular structure containing polyaromatic hydrocarbon, phenolic, furanic, and aliphatic fragments is proposed for the hydrochars.
DOI	10.1021/acs.energyfuels.9b02174
关键词[WOS]	ACID-CATALYZED CONVERSION ; HIGH-YIELD PRODUCTION ; ETHYLENE-GLYCOL ; CARBON MATERIALS ; LEVULINIC ACID ; LACTIC-ACID ; CELLULOSE ; BIOMASS ; HUMINS ; GLUCOSE
收录类别	SCI
语种	英语
资助项目	Academic New Seedling Plan Project of Guizhou Institute of Technology[Qjan Ke He [2017]5789-08] ; National Natural Science Foundation of China[51576199] ; Natural Science Foundation of Guangdong Province[2017A030308010]
WOS研究方向	Energy & Fuels ; Engineering
项目资助者	Academic New Seedling Plan Project of Guizhou Institute of Technology ; National Natural Science Foundation of China ; Natural Science Foundation of Guangdong Province
WOS类目	Energy & Fuels ; Engineering, Chemical
WOS记录号	WOS:000492113000047
出版者	AMER CHEMICAL SOC
引用统计	被引频次：60[WOS] [WOS记录] [WOS相关记录]
文献类型	期刊论文
条目标识符	http://ir.giec.ac.cn/handle/344007/26191
专题	中国科学院广州能源研究所
通讯作者	Shi, Ning
作者单位	1.Guizhou Inst Technol, Sch Chem Engn, Guiyang 550003, Guizhou, Peoples R China 2.Chinese Acad Sci, Guangzhou Inst Energy Convers, Guangzhou 510640, Guangdong, Peoples R China 3.Guangdong Prov Key Lab New & Renewable Energy Res, Guangzhou 510640, Guangdong, Peoples R China
第一作者单位	中国科学院广州能源研究所
推荐引用方式 GB/T 7714	Shi, Ning,Liu, Qiying,He, Xiong,et al. Molecular Structure and Formation Mechanism of Hydrochar from Hydrothermal Carbonization of Carbohydrates[J]. ENERGY & FUELS,2019,33(10):9904-9915.
APA	Shi, Ning.,Liu, Qiying.,He, Xiong.,Wang, Gui.,Chen, Ni.,...&Ma, Longlong.(2019).Molecular Structure and Formation Mechanism of Hydrochar from Hydrothermal Carbonization of Carbohydrates.ENERGY & FUELS,33(10),9904-9915.
MLA	Shi, Ning,et al."Molecular Structure and Formation Mechanism of Hydrochar from Hydrothermal Carbonization of Carbohydrates".ENERGY & FUELS 33.10(2019):9904-9915.