水热液化制备5-羟甲基糠醛的碳稳定同位素分馏研究

doi:10.3969/j.issn.0253-2417.2023.01.008

林产化学与工业 ›› 2023, Vol. 43 ›› Issue (1): 63-71.doi: 10.3969/j.issn.0253-2417.2023.01.008

水热液化制备5-羟甲基糠醛的碳稳定同位素分馏研究

程琴¹^,², 沈娟章¹, 蔡燕燕¹, 叶俊¹, 午紫阳¹, 谭卫红¹^,*()

1. 中国林业科学研究院林产化学工业研究所；江苏省生物质能源与材料重点实验室；国家林业和草原局林产化学工程重点实验室；林木生物质低碳高效利用国家工程研究中心，江苏南京 210042
2. 南京林业大学江苏省林业资源高效加工利用协同创新中心, 江苏南京 210037

收稿日期:2021-12-16 出版日期:2023-02-28 发布日期:2023-02-28
通讯作者: 谭卫红 E-mail:tanweihong71@163.com
作者简介:谭卫红, 副研究员, 博士, 从事天然产物分离、精制与鉴别研究; E-mail: tanweihong71@163.com
程琴(1997-), 女, 贵州贵阳人, 硕士生, 研究方向: 生物质化学与工程
基金资助:
国家重点研发计划资助项目(2018YFB1501500)

Carbon Stable Isotope Fractionation of 5-Hydroxymethylfurfural from Hydrothermal Liquefaction

Qin CHENG¹^,², Juanzhang SHEN¹, Yanyan CAI¹, Jun YE¹, Ziyang WU¹, Weihong TAN¹^,*()

1. Institute of Chemical Industry of Forest Products, CAF; Key Lab. of Biomass Energy and Material, Jiangsu Province; Key Lab. of Chemical Engineering of Forest Products, National Forestry and Grassland Administration; National Engineering Research Center of Low-Carbon Processing and Utilization of Forest Biomass, Nanjing 210042, China
2. Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, Nanjing Forestry University, Nanjing 210037, China

Received:2021-12-16 Online:2023-02-28 Published:2023-02-28
Contact: Weihong TAN E-mail:tanweihong71@163.com

摘要/Abstract

摘要：

对比了不同碳稳定同位素组成原料在水热液化制备5-羟甲基糠醛(5-HMF) 过程中碳稳定同位素分馏特征，研究原料的碳稳定同位素组成对5-HMF产率的影响。结果表明：木薯淀粉水热液化制备的5-HMF的最大产率为33.90%，高于玉米淀粉的29.93%，杨木纤维素(P-C)最大产率为31.00%，高于玉米秸秆纤维素(CS-C)的30.76%，竹粉和杨木的最大产率分别为13.00%和13.80%，高于玉米秸秆和玉米芯(分别为11.60%和12.53%)。在反应时间为15 min时，不同原料的反应速率如下：木薯淀粉0.301 g/(L·min)大于玉米淀粉0.128 g/(L·min)，P-C为0.513 g/(L·min)大于CS-C的0.386 g/(L·min)，竹粉0.133 g/(L·min)大于杨木0.124 g/(L·min)，大于玉米芯0.117 g/(L·min)，大于玉米秸秆0.097 g/(L·min)。δ_¹³C值较小的原料(木薯淀粉、P-C、杨木、竹粉)反应过程中的δ_¹³C值在反应初期的变化速率大于δ_¹³C较大的原料(玉米淀粉、CS-C、玉米秸秆和与玉米芯)。水热过程中存在稳定同位素动力学效应，¹³C同位素较富集的原料参与反应需要的能量更多，反应速率慢，5-HMF的产率低。液化过程中结构简单的原料稳定同位素分馏影响较大；液化程度越大，δ_¹³C的变化程度越大。

关键词: 水热液化, 木质纤维素生物质, 碳同位素分馏, 5-羟甲基糠醛, 单体同位素分析

Abstract:

In this work, the carbon isotopic fractionation characteristics of feedstocks with different stable carbon isotopic compositions during hydrothermal liquefaction for preparation of 5-hydroxymethylfurfural(5-HMF) were compared, and the effect of carbon stable isotope composition of raw materials on the yield of 5-HMF was studied. The results showed that the maximum yield of tapioca starch was 33.90%, which is higher than those of corn starch(29.93%), poplar cellulose(P-C, 31.00%), and corn straw cellulose(CS-C, 30.76%), respectively. The maximum yields of bamboo flour and poplar were 13.00% and 13.80%, which were higher than those of corn straw(11.6%) and corn cob(12.53%), respectively. At the reaction time of 15 min, the reaction rate of different raw materials: tapioca starch 0.301 g/(L·min) was greater than corn starch 0.128 g/(L·min), poplar cellulose 0.513 g/(L·min) was greater than corn straw cellulose 0.386 g/(L·min), and bamboo powder 0.133 g/(L·min) was greater than poplar 0.124 g/(L·min), which was greater than corn cob 0.117 g/(L·min) and greater than corn straw 0.097 g/(L·min). In the reaction process, the change rate of δ_¹³C value of raw materials with smaller δ_¹³C value(cassava starch, poplar cellulose, poplar and bamboo powder) in the initial stage of reaction was greater than that of raw materials with larger δ_¹³C value(corn starch, corn straw cellulose, corn straw and corn cob). There was a stable isotope kinetic effect in the hydrothermal liquefaction process. The ¹³C isotope required more energy to participate than the enriched raw materials in the reaction, the reaction rate was slow, and the yield of 5-HMF was low. In the process of liquefaction, the stable isotope fractionation of raw material with a simple structure has a great influence. The greater degree of liquefaction, the greater degree of change of δ_¹³C.

Key words: hydrothermal liquefaction, lignocellulose biomass, carbon isotope fractionation, 5-hydroxymethylfurfural, compound specific isotope analysis

中图分类号:

TQ35
TK6

程琴, 沈娟章, 蔡燕燕, 叶俊, 午紫阳, 谭卫红. 水热液化制备5-羟甲基糠醛的碳稳定同位素分馏研究[J]. 林产化学与工业, 2023, 43(1): 63-71.

Qin CHENG, Juanzhang SHEN, Yanyan CAI, Jun YE, Ziyang WU, Weihong TAN. Carbon Stable Isotope Fractionation of 5-Hydroxymethylfurfural from Hydrothermal Liquefaction[J]. Chemistry and Industry of Forest Products, 2023, 43(1): 63-71.

图/表 5

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原料 feedstock	相关系数(R²) correlation coefficient	富集因子(ε)/‰ enrichment factor	反应速率(v)/(g·L^-1·min^-1) reaction rate
玉米淀粉corn starch	0.9804	0.36±0.029	0.128±0.015
木薯淀粉tapioca starch	0.9550	0.12±0.016	0.301±0.031
杨木poplar	0.9763	-0.16±0.013	0.124±0.011
竹粉bamboo	0.9921	-0.08±0.004	0.133±0.010
玉米秸秆cornstalk	0.9681	-0.17±0.015	0.097±0.010
玉米芯corncob	0.9858	-0.20±0.012	0.117±0.015
CS-C	0.9975	0.53±0.019	0.386±0.016
P-C	0.9984	0.49±0.014	0.513±0.013

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水热液化制备5-羟甲基糠醛的碳稳定同位素分馏研究

Carbon Stable Isotope Fractionation of 5-Hydroxymethylfurfural from Hydrothermal Liquefaction

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