Study on the characteristics of the slow and fast co-pyrolysis of cellulose and oxalic acid
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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。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.
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Key words:
- oxalic acid /
- cellulose /
- slow co-pyrolysis /
- fast co-pyrolysis
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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
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
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
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)
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
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
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 /% 300 ℃ 400 ℃ 500 ℃ 600 ℃ 700 ℃ 800 ℃ FF Co-pyrolysis 7.27 5.88 5.45 3.61 1.37 1.22 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 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 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 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 /% 300 ℃ 400 ℃ 500 ℃ 600 ℃ 700 ℃ 800 ℃ FF Co-pyrolysis 1.44 2.12 2.00 1.84 0.46 0.37 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 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 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 pyrolysis of cellulose 0.64 3.88 4.96 7.30 7.85 5.14
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