纤维素与草酸的慢速和快速共热解反应特性研究

赵莉; 程安帅; 付浩; 胡斌; 刘欣茹; 刘吉; 陆强

doi:10.19906/j.cnki.JFCT.2023045

纤维素与草酸的慢速和快速共热解反应特性研究

doi: 10.19906/j.cnki.JFCT.2023045

赵莉^1,,
程安帅^1,,
付浩^1,,
胡斌^1,,
刘欣茹^1,,
刘吉^{1, 2,},
陆强^1, ,

1.
华北电力大学新能源发电国家工程研究中心, 北京, 102206
2.
华北电力大学苏州研究院, 江苏苏州, 215123

基金项目: 国家自然科学基金（52106241, 52276189, 52006069）, 江苏省自然科学基金（BK20221248）和中央高校基本科研业务费（2022YQ002）资助

详细信息

通讯作者:
Tel: 01061771335, E-mail: qianglu@mail.ustc.edu.cn

中图分类号: TK6
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- 文章访问数: 128
- HTML全文浏览量: 31
- PDF下载量: 19
- 被引次数: 0
出版历程
- 收稿日期: 2023-03-31
- 修回日期: 2023-05-09
- 录用日期: 2023-05-09
- 网络出版日期: 2023-05-24

On the characteristics of the slow and fast co-pyrolysis of cellulose and oxalic acid

ZHAO Li^1
,,
CHENG An-shuai^1
,,
FU Hao^1
,,
HU Bin^1
,,
LIU Xin-ru^1
,,
LIU Ji^{1, 2
,},
LU Qiang^{1
, ,}

1.
National Engineering Research Center of New Energy Power Generation, North China Electric Power University, Beijing 102206, China
2.
Suzhou Institute of North China Electric Power University, Suzhou 215123, China

Funds: The project was supported by the National Natural Science Foundation of China (52106241, 52276189, 52006069), Natural Science Foundation of Jiangsu Province (BK20221248) and Fundamental Research Funds for the Central Universities (2022YQ002)

摘要

摘要: 本研究利用热重-傅里叶变换红外光谱和卧式固定床热解反应装置，探究了纤维素与草酸的慢速和快速共热解反应特性。慢速共热解的失重曲线包括草酸分解和纤维素分解两个阶段，由于草酸与纤维素分解不同步，草酸主要通过其分解形成的挥发分影响纤维素的分解，且影响并不明显。而在快速共热解中，草酸与纤维素同步热解，原料及挥发分之间有着充分的交互反应，因此，草酸对纤维素的三相热解产物具有显著影响。相比于纤维素单独快速热解，快速共热解形成的生物油中左旋葡聚糖、左旋葡萄糖酮含量减少，1,4∶3,6-二脱水-α-d-吡喃葡萄糖含量显著提高；热解气中CO减少，CO₂增多；此外，纤维素分解更为彻底，热解炭具有更高的芳香化程度。
- 草酸 /
- 纤维素 /
- 慢速共热解 /
- 快速共热解
Abstract: The slow and fast co-pyrolysis characteristics of cellulose and oxalic acid were investigated by thermogravimetric-Fourier transform infrared spectroscopy and horizontal fixed-bed pyrolysis setup. The weight loss curve of slow co-pyrolysis showed oxalic acid decomposition and cellulose decomposition stages. As the decomposition of oxalic acid and cellulose was not synchronous, oxalic acid affected the decomposition of cellulose mainly through the volatiles formed by its decomposition, which was not obvious. Differently, in fast co-pyrolysis, oxalic acid and cellulose were simultaneously pyrolyzed, and sufficient interaction could occur between raw materials and volatile components. Therefore, oxalic acid had a significant impact on the pyrolysis products of cellulose. Compared with the fast pyrolysis of cellulose, the contents of levoglucosan and levoglucosenone decreased, while the content of 1,4∶3,6-dianhydro-α-d-glucopyranose increased significantly in the bio-oil during fast co-pyrolysis process. The volume fraction of CO in pyrolysis gas decreased, whereas that of CO₂ increased. In addition, the decomposition of cellulose was more thorough, and more aromatic structures were formed in biochar.
- oxalic acid /
- cellulose /
- slow co-pyrolysis /
- fast co-pyrolysis

HTML全文

图 1 纤维素与草酸慢速共热解的TG和DTG曲线

Figure 1 TG and DTG curves of slow co-pyrolysis of cellulose and oxalic acid

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图 2 挥发分组成的FT-IR光谱谱图

Figure 2 FT-IR spectra for the volatile components

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图 3 主要挥发分FT-IR峰值随DTG曲线的演变

Figure 3 The evolution of the main volatiles characterized by FT-IR corresponding to the DTG curves

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图 4 三相产物的产率随热解温度的变化

Figure 4 Variation of the yields of the three-phase products against pyrolysis temperature

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图 5 以纤维素为基准的热解炭产率比较

Figure 5 Comparison of biochar yields based on cellulose

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图 6 400 ℃下生物油的典型离子总图

Figure 6 Typical ion chromatograms of bio-oils obtained at 400 ℃ (1: 2(5H) -furanone; 2: FF; 3: 2-propyl furan; 4: LGO; 5: DGP; 6: 5-HMF; 7: LG; 8: 1, 6-anhydro-β-d-glucofuranose)

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图 7 气体成分的体积分数随温度的变化

Figure 7 Variation of volume fractions of gas compositions against temperature

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图 8 不同温度下热解炭的ATR-FTIR谱图

Figure 8 ATR-FTIR spectra of biochars at different temperatures (a): pyrolysis of cellulose; (b): co-pyrolysis

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表 1 不同温度下典型液体产物选择性

Table 1 Selectivity of typical liquid products at different temperatures

Product	From	Selectivity/%
Product	From	300 ℃	400 ℃	500 ℃	600 ℃	700 ℃	800 ℃
FF	Co-pyrolysis	7.27	5.88	5.45	3.61	1.37	1.22
FF	pyrolysis of cellulose	18.76	12.86	10.82	8.70	5.95	3.94
LGO	Co-pyrolysis	9.85	0.00	0.00	0.00	0.00	0.00
LGO	pyrolysis of cellulose	12.69	2.73	0.47	0.00	0.00	0.00
DGP	Co-pyrolysis	31.74	21.20	16.89	10.00	4.08	2.64
DGP	pyrolysis of cellulose	13.61	7.30	4.87	3.07	1.93	0.89
LG	Co-pyrolysis	7.31	17.34	17.90	26.02	14.46	13.62
LG	pyrolysis of cellulose	6.07	21.12	28.12	39.21	42.08	46.05

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表 2 不同温度下典型液体产物产率

Table 2 Yields of typical liquid products at different temperatures

Product	From	Yield/%
Product	From	300 ℃	400 ℃	500 ℃	600 ℃	700 ℃	800 ℃
FF	Co-pyrolysis	1.44	2.12	2.00	1.84	0.46	0.37
FF	pyrolysis of cellulose	1.80	2.14	1.73	1.47	1.01	0.40
LGO	Co-pyrolysis	1.85	0.00	0.00	0.00	0.00	0.00
LGO	pyrolysis of cellulose	1.53	0.57	0.09	0.00	0.00	0.00
DGP	Co-pyrolysis	5.89	5.31	4.76	3.85	0.77	0.44
DGP	pyrolysis of cellulose	1.61	1.50	0.96	0.64	0.40	0.11
LG	Co-pyrolysis	1.21	3.98	4.64	8.99	2.14	2.04
LG	pyrolysis of cellulose	0.64	3.88	4.96	7.30	7.85	5.14

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