茭白秆水解制备高价值呋喃平台化合物研究

doi:10.3969/j.issn.1004-1524.20230480

浙江农业学报 ›› 2024, Vol. 36 ›› Issue (4): 870-880.DOI: 10.3969/j.issn.1004-1524.20230480

茭白秆水解制备高价值呋喃平台化合物研究

郭威良¹(), 吴剑¹^,²^,^*(), 张兴一龙³, 吴可荆³, 谢佳家⁴, 冯海林¹

1.浙江农林大学数学与计算机科学学院,浙江杭州 311300
2.浙江臻泰能源科技有限公司,浙江丽水 321400
3.四川大学新能源与低碳技术研究院,四川成都 610065
4.国网浙江省电力有限公司双创中心,浙江杭州 310051

收稿日期:2023-04-10 出版日期:2024-04-25 发布日期:2024-04-29
作者简介:郭威良(1997—),男,河南南阳人,硕士研究生,主要从事生物质利用、数据模型分析研究。E-mail:guoweiliang@stu.zafu.edu.cn
通讯作者: *吴剑,E-mail:wujian@zafu.edu.cn
基金资助:
浙江省重点研发计划(2021C01100);浙江省领军型创新创业团队项目(2020R02015);中央引导地方科技发展专项(2019ZY1015)

Preparation of high-value furan platform compounds from Zizania latifolia stem

GUO Weiliang¹(), WU Jian¹^,²^,^*(), ZHANG Xingyilong³, WU Kejing³, XIE Jiajia⁴, FENG Hailin¹

1. College of Mathematics and Computer Science, Zhejiang A&F University, Hangzhou 311300, China
2. Zhejiang Zhentai Energy Tech. Co., Ltd., Lishui 321400, Zhejiang, China
3. Institute of New Energy and Low-Carbon Technology, Sichuan University, Chengdu 610065, China
4. Innovation and Entrepreneurship Center, State Grid Zhejiang Electric Power Co., Ltd., Hangzhou 310051, China

Received:2023-04-10 Online:2024-04-25 Published:2024-04-29
Contact: WU Jian

摘要/Abstract

摘要：

生物质转化为高价值呋喃平台化合物是生物质资源利用的重要方式。以工业副产物偏钛酸作为固体酸催化剂,将茭白秆转化为5-羟甲基糠醛(HMF)和糠醛,研究物理活化、溶剂体系等对茭白秆水解性能的影响,并优化反应工艺条件。结果表明,茭白秆具有更低的木质素含量和纤维素晶型结构,比茭白叶更容易被物理活化。在200 ℃、30 min的反应条件下,球磨活化的茭白秆获得了最高的HMF和糠醛收率,分别为11.66%和7.30%。反应动力学分析表明,偏钛酸催化球磨茭白秆转化的活化能低,相较于文献报道的其他木质纤维素生物质,球磨茭白秆的高值化转化具有优势。

关键词: 茭白秆, 5-羟甲基糠醛, 物理活化, 两相体系, 偏钛酸

Abstract:

The conversion of biomass into high-value furan platform compounds is an important way of biomass resources utilization. In the present study, the industrial by-product metatitanic acid was used as a solid acid catalyst for the conversion of water bamboo (Zizania latifolia) stem to 5-hydroxymethylfurfural (HMF) and furfural. The effects of physical activation and solvent system on the hydrolysis performance of water bamboo stem were investigated and the reaction process conditions were optimised. The results showed that, due to the lower lignin content and the crystal structure of cellulose, water bamboo stem could be more easily physically activated than the water bamboo leaf. Under reaction conditions of 200 ℃ and 30 min, the activated water bamboo stem after ball milling obtained the highest yields of HMF and furfural, which were 11.66% and 7.30%, respectively. The reaction kinetics analysis showed that the activation energy of the water bamboo stem after ball milling catalysed by metatitanic acid was low, which exhibited advantages compared to other lignocellulosic biomass reported in literatures.

Key words: Zizania latifolia stem, 5-hydroxymethylfurfural, physical activation, two-phase system, metatitanic acid

中图分类号:

S645.2
TK6

郭威良, 吴剑, 张兴一龙, 吴可荆, 谢佳家, 冯海林. 茭白秆水解制备高价值呋喃平台化合物研究[J]. 浙江农业学报, 2024, 36(4): 870-880.

GUO Weiliang, WU Jian, ZHANG Xingyilong, WU Kejing, XIE Jiajia, FENG Hailin. Preparation of high-value furan platform compounds from Zizania latifolia stem[J]. Acta Agriculturae Zhejiangensis, 2024, 36(4): 870-880.

图/表 13

表1 茭白与水稻不同部位的组分含量对比

Table 1 Comparison of component contents in different parts of water bamboo and %

样品 Sample	纤维素含量 Cellulose content	半纤维素含量 Hemicellulose content	木质素含量 Lignin content	灰分含量 Ash content	水分含量 Water content
茭白叶Water bamboo leaf	29.30	20.14	24.48	9.10	9.15
茭白秆Water bamboo stem	38.20	23.30	15.90	9.47	10.13
水稻叶Rice leaf	34.14	20.45	16.68	16.79	11.85
水稻秸秆Rice stem	39.69	19.75	16.48	13.92	12.53

图1 茭白的秆与叶在球磨前后的扫描电子显微镜(SEM)图像对比 a、b,球磨前的茭白秆;c、d,球磨后的茭白秆;e、f,球磨前的茭白叶;g、h,球磨后的茭白叶。

Fig.1 Scanning electron microscope (SEM) images of water bamboo stem and leaf before and after ball milling a, b, Water bamboo stem before ball milling; c, d, Water bamboo stem after ball milling; e, f, Water bamboo leaf before ball milling; g, h, Water bamboo leaf after ball milling.

图2 茭白秸秆的球磨前后XRD图谱 a,球磨后的茭白叶;b,球磨前的茭白叶;c,球磨后的茭白秆;d,球磨前的茭白秆。

Fig.2 XRD patterns of Zizania latifolia straw before and after ball milling a, Water bamboo leaf after ball milling; b, Water bamboo leaf before ball milling; c, Water bamboo stem after ball milling; d, Water bamboo stem before ball milling.

图3 催化剂的150倍和450倍扫描电子显微镜(SEM)图像

Fig.3 Scanning electron microscope (SEM) images of catalysts at 150× and 450× magnification

图4 催化剂的表征 a,X射线衍射(XRD)图谱;b,NH3程序升温脱附(TPD)曲线;c, 傅里叶变换红外光谱(FT-IR)。

Fig.4 Characterization of catalysts a, X-ray diffraction (XRD) profile; b, Curve of NH3 temperature programmed desorption (TPD); c, Fourier transform infrared spectroscopy (FT-IR) pattern.

图5 球磨前后茭白叶和茭白秆的水解效率对比 M1,未经球磨的茭白叶;M2,球磨后的茭白叶;M3,未经球磨的茭白秆;M4,球磨后的茭白秆。反应条件如下:原料0.2 g,催化剂0.05 g,水3 mL,有机溶剂9 mL,反应温度200 ℃,反应时间90 min。

Fig.5 Comparison of hydrolysis efficiency of water bamboo leaf and stem before or after ball milling M1, Water bamboo leaf before ball milling; M2, Water bamboo leaf after ball milling; M3, Water bamboo stem before ball milling; M4, Water bamboo stem after ball milling. Reaction conditions are as follows: raw material 0.2 g, catalyst 0.05 g, water 3 mL, organic solvent 9 mL, reaction temperature 200 ℃, reaction time 90 min.

图6 溶剂体系对茭白秆水解效率的影响 S1,纯水;S2,水/THF;S3,5%(质量分数)NaCl溶液/THF;S4,水/MIBK;S5,5%(质量分数)NaCl溶液/MIBK。反应条件如下:原料0.2 g,催化剂0.05 g,水或5%(质量分数)NaCl溶液3 mL,有机溶剂9 mL,反应温度200 ℃,反应时间90 min。

Fig.6 Effects of Solvent Systems on Hydrolysis Efficiency of water bamboo stem S1, Pure water; S2, Water/THF; S3, 5% (mass fraction) NaCl solution/THF; S4, Water/MIBK; S5, 5% (mass fraction) NaCl solution/MIBK. Reaction conditions are as follows: raw material 0.2 g, catalyst 0.05g, water or 5% (mass fraction) NaCl solution 3 mL, organic solvent 9 mL, reaction temperature 200 ℃, reaction time 90 min.

图7 催化剂用量对收率和原料转化率的影响反应条件如下:原料0.2 g,5%(质量分数)NaCl溶液3 mL,有机溶剂9 mL,反应温度200 ℃,反应时间30 min。

Fig.7 Effect of catalyst dosage on yield and raw material conversion rate Reaction conditions are as follows: raw material 0.2 g, 5% (mass fraction) NaCl solution 3 mL, organic solvent 9 mL, reaction temperature 200 ℃, reaction time 30 min.

图8 反应时间对收率和原料转化率的影响反应条件如下:原料0.2 g,催化剂0.1 g,5%(质量分数)NaCl溶液3 mL,有机溶剂9 mL,反应温度200 ℃。

Fig.8 Effect of reaction time on yield and raw material conversion rate Reaction conditions are as follows: raw material 0.2 g, catalyst 0.1 g, 5% (mass fraction) NaCl solution 3 mL, organic solvent 9 mL, reaction temperature 200 ℃.

图9 反应温度对目标产物收率和原料转化率的影响反应条件如下:原料0.2 g,催化剂0.1 g,5%(质量分数)NaCl溶液3 mL,有机溶剂9 mL,反应时间30 min。

Fig.9 Effect of reaction temperature on yield and raw material conversion rate Reaction conditions are as follows: raw material 0.2 g, catalyst 0.1 g, 5% (mass fraction) NaCl solution 3 mL, organic solvent 9 mL, reaction time 30 min.

图10 经过球磨的茭白秆水解的5-羟甲基糠醛(HMF)(5-hydroxymethylfurfural)收率

Fig.10 HMF (5-hydroxymethylfurfural) yield in the hydrolysis of water bamboo stem after ball milling

表2 不同温度下的球磨茭白杆水解动力学反应速率常数

Table 2 The reaction rate constant of the hydrolysis kinetics of ball-milled Zizania latifolia stem at different temperatures

温度 Temperature/ ℃	反应速率常数k₁ Reaction rate constant k₁/min^-1	反应速率常数k₂ Reaction rate constant k₂/min^-1	决定系数 Determination coefficient (R²)
160	1.688×10^-3	0.0473 9	0.930 2
180	5.214×10^-3	0.0650 3	0.937 4
200	1.454×10^-2	0.0911 1	0.914 4

图11 球磨茭白秆水解过程中反应速率常数的自然对数值(ln k)与反应温度倒数(T-1)的关系

Fig.11 Relationship between the natural logarithm of reaction rate constant (ln k) and the reciprocal value of reaction temperature (T-1) in the the hydrolysis of water bamboo stem after ball milling

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茭白秆水解制备高价值呋喃平台化合物研究

Preparation of high-value furan platform compounds from Zizania latifolia stem

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