双功能碳基固体酸催化木糖制备糠醛的研究

罗超; 金才迪; 朱玲君; 王树荣

doi:10.19906/j.cnki.JFCT.2023030

双功能碳基固体酸催化木糖制备糠醛的研究

doi: 10.19906/j.cnki.JFCT.2023030

罗超^1,,
金才迪^1,,
朱玲君^1,,
王树荣^{1, 2, ,}

1.
浙江大学能源清洁利用国家重点实验, 浙江杭州 310027
2.
浙江省清洁能源与碳中和重点实验室, 浙江杭州 310027

基金项目: 国家重点研发项目（2018YFB1501500）资助

详细信息

通讯作者:
Tel: 0571-87952801, E-mail: srwang@zju.edu.cn

中图分类号: TK6
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出版历程
- 收稿日期: 2023-03-03
- 修回日期: 2023-04-03
- 录用日期: 2023-04-04
- 网络出版日期: 2023-04-18
- 刊出日期: 2023-08-01

Preparation of furfural from xylose catalyzed by difunctional carbon-based solid acid

LUO Chao^1
,,
JIN Cai-di^1
,,
ZHU Ling-jun^1
,,
WANG Shu-rong^{1, 2
, ,}

1.
State Key Laboratory of Clean Energy Utilization, Zhejiang University, Hangzhou 310027, China
2.
Zhejiang Provincial Key Laboratory of Clean Energy and Carbon Neutralization, Hangzhou 310027, China

Funds: The project was supported by the National Key R&D Program of China (2018YFB1501500).

摘要

摘要: 本研究以明胶和植酸（PA）为碳源，并掺杂FeCl₃·6H₂O和ZnCl₂，通过硫酸磺化法制备了双功能碳基固体酸催化剂用于高效催化木糖制备糠醛。采用SEM、BET、FT-IR、STEM-EDS等方法对不同炭化温度下制备的催化剂进行了表征，揭示了催化剂的物理化学性质。并考察了催化剂的炭化温度、FeCl₃·6H₂O与ZnCl₂物质的量比、反应温度、反应时间、γ-戊内酯（GVL）与H₂O的体积比、催化剂用量对木糖转化为糠醛（FF）的影响。结果表明，600 ℃炭化制备的催化剂CNPS600-Fe₄-Zn₂催化效果较好，用0.03 g的CNPS600-Fe₄-Zn₂（FeCl₃·6H₂O与ZnCl₂物质的量比为4∶2）在3 mL的GVL/H₂O（体积比为9∶1）溶剂体系中催化0.06 g木糖制备FF，当反应温度为170 ℃、反应时间为120 min时，木糖的转化率为99.6%，FF的摩尔产率可达85.8%。此外，还对催化剂的循环性能进行了测试，经五次循环实验后FF摩尔产率和木糖转化率均能保持在原来的80%以上，表明该催化剂具有较高的催化活性和较好的水热稳定性。
- 碳基固体酸催化剂 /
- 木糖 /
- γ-戊内酯 /
- 糠醛
Abstract: A bifunctional carbon-based solid acid catalyst was prepared by sulfonation of sulfuric acid to using gelatin and phytic acid (PA) as carbon sources and doping with FeCl₃·6H₂O and ZnCl₂, which was used to efficiently catalyze the preparation of furfural from xylose. The catalysts prepared at different carbonization temperatures were characterized by SEM, BET, FT-IR and STEM-EDS techniques, and the physicochemical properties of the catalysts were revealed. The effects of carbonization temperature of the catalyst, molar ratio of FeCl₃·6H₂O to ZnCl₂, reaction temperature, reaction time, volume ratio of γ-valerolactone (GVL) to H₂O and catalyst dosage on the conversion of xylose to furfural (FF) were investigated. The results showed that the catalytic activity of CNPS600-Fe₄-Zn₂ was higher when the carbonization temperature was 600 ℃. The xylose conversion rate was 99.6%, and the molar yield of FF reached 85.8% when the reaction was carried out at 170 ℃ for 120 min using 0.03 g CNPS600-Fe₄-Zn₂ (the molar ratio of FeCl₃·6H₂O to ZnCl₂ was 4∶2) as catalyst, 3 mL GVL/H₂O (the volume ratio of was 9∶1) as solvent and 0.06 g xylose as raw material. In addition, the cyclic performance of the catalyst was tested. The FF molar yield and xylose conversion rate remained above 80% after 5 cycles, indicating that the catalyst had higher catalytic activity and better hydrothermal stability.
- carbon-based solid acid catalyst /
- xylose /
- γ-valerolactone /
- furfural

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FIG. 2581. FIG. 2581.

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图 1 不同催化剂的扫描电镜照片

Figure 1 SEM images of different catalysts

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图 2 不同催化剂的氮气吸附-解吸等温曲线（a）和孔径分布（b）

Figure 2 Nitrogen adsorption-desorption isotherms curves (a) and pore size distribution (b) of different catalysts

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图 3 反应前后催化剂CNPS600-Fe₄-Zn₂的傅里叶变换红外光谱谱图

Figure 3 FT-IR spectra of catalyst CNPS600-Fe₄-Zn₂ before and after the reaction

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图 4 催化剂CNPS600-Fe₄-Zn₂的扫描透射电子显微镜照片

Figure 4 STEM-EDS images of catalyst CNPS600-Fe₄-Zn₂

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图 5 催化剂CNPS600-Fe₄-Zn₂的XPS谱图

Figure 5 XPS spectra of catalyst CNPS600-Fe₄-Zn₂

(a): full spectrum; (b): Fe 2p spectrum; (c): Zn 2p spectrum

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图 6 不同炭化温度制备的催化剂对木糖转化的影响

Figure 6 Effects of catalysts prepared at different carbonization temperatures on xylose conversion

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图 7 ZnCl₂与FeCl₃·6H₂O物质的量比对木糖转化率和FF产率的影响

Figure 7 Effects of the molar ratio of ZnCl₂ to FeCl₃·6H₂O on xylose conversion rate and FF yield

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图 8 反应温度和时间对FF摩尔产率的影响（a）和木糖转化率的影响（b）

Figure 8 Effects of reaction temperature and time on FF molar yield (a) and xylose conversion (b)

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图 9 不同GVL与H₂O体积比1∶4−1∶0（a）和4∶1−1∶0（b）对木糖水热转化为FF的影响

Figure 9 Effects of different GVL to H₂O volume ratio of 1∶4−1∶0 (a) and 4∶1−1∶0 (b) on the hydrothermal conversion of xylose to FF

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图 10 催化剂用量对木糖水热转化为FF的影响

Figure 10 Effects of mass of catalyst on the hydrothermal conversion of xylose to FF

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图 11 催化剂CNPS600-Fe₄-Zn₂的循环使用性能

Figure 11 Recycling property of CNPS600-Fe₄-Zn₂ catalyst

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表 1 不同催化剂的比表面积和孔道结构

Table 1 Specific surface area and pore structure of different catalysts

Catalyst	Specific surface area /(m²·g⁻¹)	Average pore width /nm	Total pore volume / (cm³·g⁻¹)
CNPS400-Fe₄-Zn₂	10.6	3.82	0.0950
CNPS600-Fe₄-Zn₂	155	3.82	0.745
CNPS800-Fe₄-Zn₂	18.9	13.0	0.353

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表 2 ICP测试结果

Table 2 Results of ICP test

Catalyst	Sampling quality /g	Constant volume /mL	Test element	Test solution element concentration /(mg·L⁻¹)	Multiple of the dilution	Element content C_x /(mg·kg⁻¹)	Element content w /%
CNPS400-Fe₄-Zn₂	0.0548	25	Fe	4.92	1	2243.61	0.220
	0.0548	25	Zn	2.11	1	962.14	0.100
	0.0548	25	S	9.30	20	84863.14	8.49
CNPS600-Fe₄-Zn₂	0.0536	25	Fe	8.72	20	81324.63	8.13
	0.0536	25	Zn	3.30	10	15410.45	1.54
	0.0536	25	S	7.42	10	34594.22	3.46
CNPS800-Fe₄-Zn₂	0.0490	25	Fe	5.68	10	29000.00	2.90
	0.0490	25	Zn	3.43	10	17520.41	1.75
	0.0490	25	S	4.80	10	24469.39	2.45

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表 3 催化剂循环实验中催化剂的回收率*

Table 3 Recovery of catalysts in catalyst cycling experiment

Recycle	Fresh	1	2	3	4	5
Amount of recovery /g	0.72	0.63	0.58	0.52	0.46	0.41
Recovery rate /%	−	87.5	92.1	89.7	88.5	90.0
Recovery of catalysts in catalyst cycling experiments*: In order to make the remaining catalyst sufficient for the next cycle, the reaction raw material, mixed solvent, catalyst, etc. were expanded by 24 times in the catalyst cycle experiment

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