基于ReaxFF力场的纤维素水热过程机理研究

doi:10.11949/0438-1157.20240635

摘要/Abstract

摘要：

使用Materials Studio软件建立并优化纤维素-水模型体系，利用LAMMPS软件对其进行水热过程的分子动力学模拟，模拟研究了水热体系内纤维素水热产物的演变规律及其水热反应机理。结果表明：温度是影响纤维素水热产物分布的重要因素。随着水热温度的增加，纤维素分解加剧，体系内水热固相产物相对含量急剧下降，固相产物的芳香性和热值增高，亲水性降低；重质焦油、轻质焦油的相对含量均先增加后降低，焦油二次裂解为小分子反应加剧；随着水热温度的增加，体系内CO₂和H₂生成量均持续升高，甲酸生成量呈先升高后降低的趋势，甲醛生成量差异较小。模拟结果亦表明H₂O分子主要以水合氢离子（H₃O⁺）的形式参与纤维素水热反应，随着水热温度的升高，体系中水分子的电离反应与纤维素的脱水反应均增强。纤维素水热机理分析表明水热过程中纤维素的解聚包括分解为葡萄糖和脱水为左旋葡聚糖两条路径，而葡萄糖单体重排异构过程中会经历烯二醇三种过渡态结构，不同的结构通过脱水、逆羟醛缩合等反应分别生成呋喃类和醇醛类等主要中间产物。通过纤维素水热反应机理的分析，可为生物质水热转化提供理论指导。

关键词: 生物质, 水热处理, 纤维素, ReaxFF反应力场, 反应路径

Abstract:

The cellulose-water model system was established and optimized using Materials Studio software, and the molecular dynamic simulation of the cellulose hydrothermal reaction process was conducted using LAMMPS software. The evolution law of the hydrothermal products and the hydrothermal reaction mechanism of the cellulose were simulated and studied. The results show that temperature is an important factor affecting the distribution of hydrothermal products of cellulose. With the increase of the hydrothermal temperature, the decomposition of cellulose is intensified, the relative content of hydrothermal solid phase products in the system decreases sharply, the aromatics and calorific value of solid phase products increase, and the hydrophilicity decrease. The relative contents of heavy tar and light tar increased first and then decreased, and the reaction of secondary cracking of tar into small molecules intensified. With the increase of hydrothermal temperature, the production of CO₂ and H₂ in the system continued to increase, the production of formic acid showed a trend of increasing first and then decreasing, and the difference of formaldehyde was small. The simulation results also show that H₂O molecules participated in the hydrothermal reaction of cellulose mainly in the form of hydrated hydrogen ions (H₃O⁺). With the increase of the hydrothermal temperature, the ionization reaction of water molecules and the dehydration reaction of cellulose were enhanced. The analysis of hydrothermal mechanism of cellulose showed that the cellulose depolymerization paths included the decomposition into glucose and the dehydration into L-glucan. During the rearrangement isomerization process of the glucose monomer, the main intermediates such as furans and aldehydes were formed by dehydration and retrograde aldol condensation reactions from the three transition state structures of enediol. The research on the cellulose hydrothermal reaction mechanism can provide a theoretical basis for the biomass hydrothermal conversion.

Key words: biomass, hydrothermal treatment, cellulose, ReaxFF reactive force field, reaction path

中图分类号:

TK 6

梁宁, 张守玉, 刘思梦, 黄健添, 吕邦勇, 杨楚轲, 胡南, 吴玉新. 基于ReaxFF力场的纤维素水热过程机理研究[J]. 化工学报, DOI: 10.11949/0438-1157.20240635.

Ning LIANG, Shouyu ZHANG, Simeng LIU, Jiantian HUANG, Bangyong LYU, Chuke YANG, Nan HU, Yuxin WU. Study on the evolution mechanism of cellulose during hydrothermal process based on ReaxFF force field[J]. CIESC Journal, DOI: 10.11949/0438-1157.20240635.

图/表 13

图1 纤维素-水模型体系的构建与结构优化（C:灰色；H:白色；O:红色)

Fig.1 Construction and structure optimization of the cellulose-water model system (C: grey; H: white; O: red )

图2 纤维素水热过程糠醛生成量ReaxFF MD模拟和实验数据对比

Fig.2 Comparison between the experimental and ReaxFF MD simulation data of furfural production from the cellulose during hydrothermal process

图3 1400~2400K模拟温度下纤维素水热产物组分的相对含量

Fig.3 Relative contents of cellulose hydrothermal products at the simulated temperature of 1400~2400 K

图4 1400~2400 K水热模拟温度下固相产物的范式图

Fig.4 Van-Krevelen diagram of the char at hydrothermal simulated temperature of 1400~2400K

图5 1500~2300K模拟温度下纤维素水热生成焦油的分子数目

Fig.5 Molecular number of the cellulose hydrothermal tar at the simulated temperature of 1500~2300K

图6 1500~2300K模拟温度下纤维素水热生成CO2和H2的分子数目

Fig.6 Molecular number of CO2 and H2 from cellulose hydrothermal process at the simulated temperature of 1500~2300K

图7 1500~2300K模拟温度下纤维素水热体系内甲酸、甲醛的分子数目

Fig.7 Molecular number of formic acid, formaldehyde from cellulose hydrothermal process at the simulated temperature of 1500~2300K

图8 1500~2300K模拟温度下体系中H2O和H3O+的数目注:(a)H2O (b)H3O+

Fig.8 Number of H2O and H3O+ in the system at the simulated temperature of 1500~2300K

图9 2300K模拟温度下纤维素分子水热反应路径（C:灰色；H:白色；O:红色)注:(a)路径1 (b)路径2

Fig.9 Hydrothermal reaction path of cellulose molecules at the simulated temperature of 2300 K (C: grey; H: white, O: red )

图10 2300 K模拟温度下葡萄糖分子的水热反应路径注:(a)吡喃葡萄糖(b)左旋葡聚糖(c)5-羟甲基糠醛(d)糠醛(e)乙醇醛(f)赤藓糖(g)二羟基丙酮(h)甘油醛(i)丙酮醛

Fig.10 Hydrothermal reaction path of glucose molecules at the simulated temperature of 2300 K

图11 葡萄糖和左旋葡聚糖随模拟温度或反应时间的变化趋势

Fig.11 Trends of glucose and levoglucosan during the simulated hydrothermal process

图12 5-羟甲基糠醛和糠醛随模拟温度或反应时间的变化趋势

Fig.12 Trends of 5-hydroxymethylfurfural and furfural during the simulated hydrothermal process

图13 乙醇醛和甘油醛随模拟温度或反应时间的变化趋势

Fig.13 Trends of glycolaldehyde and glyceraldehyde during the simulated hydrothermal process

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