In-situ catalytic pyrolysis of pine powder by ZnCl2 to bio-oil under mild conditions and application of biochar
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摘要: 生物质快速热裂解是生物质转化利用的有效途径,但常因是非催化过程,裂解温度高导致生物油成分复杂难控。本实验以ZnCl2为催化剂,研究了木质素、纤维素、玉米芯和松木粉的热解过程,旨在探索原位催化对快速热裂解的强化作用。本实验通过热重曲线拟合,获得了热裂解的活化能;通过快速热裂解实验,研究了催化作用下热解油组成变化。结果表明,ZnCl2催化可显著降低生物质裂解温度,简化生物油组成。在350 ℃快速热裂解松木粉获得了47%生物油产率,主要成分是纤维素和半纤维素的衍生物。ZnCl2可显著降低纤维素裂解的活化能(由304.78 kJ/mol降低至112.46 kJ/mol),而对木质素的裂解影响不大。裂解后的碳渣在600 ℃二次碳化可获得性能良好的活性炭,苯酚吸附容量可达165 mg/g。Abstract: Fast pyrolysis of biomass is an effective way for biomass conversion and utilization. However, the pyrolysis temperature is usually high because it is a non-catalytic process, resulting in the complicated composition of bio-oil and difficulty to control. Aiming to explore in-situ catalysis in this paper, the fast pyrolysis of lignin, cellulose, corncob and pine wood powder was studied using ZnCl2 as the catalyst. The activation energies of non-catalytic pyrolysis and catalytic pyrolysis were obtained based on kinetic fitting of their thermal gravimetric curves. The variation in pyrolysis oil composition was analyzed. It was found that ZnCl2 in-situ catalysis could not only significantly reduce the pyrolysis temperature, but also simplify the resultant bio-oil composition. Even under pyrolysis temperature as low as 350 ℃, fast pyrolysis of pine wood powder could achieve a yield of 47% of bio-oil, which was predominantly composed of the derivatives of cellulose and hemicellulose. ZnCl2 in-situ catalysis could significantly decrease the activation energy of cellulose cracking from 304.78 to 112.46 kJ/mol, but has little effect on that of lignin. The carbon residue from ZnCl2-catalyzed pyrolysis was further carbonized at 600 ℃, affording activated carbon with adsorption capacity of phenol up to 165 mg/g. The research work provides guidance and reference for the development of in-situ catalytic pyrolysis technology with high efficiency.
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Key words:
- biomass /
- fast pyrolysis /
- in-situ catalysis /
- zinc chloride /
- pine wood
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表 1 不同生物质的工业分析和元素分析
Table 1 Ultimate and proximate analyses of biomass
Material Proximate analysis wad/% Ultimate analysis wad/% A M V FC C H O N S Lignin 8.49 14.65 52.99 23.87 52.52 4.64 15.22 0.19 4.28 Cellulose 5.92 0.01 87.90 6.17 43.17 6.4 44.41 0.09 0 CC 1.80 1.60 82.95 13.65 45.73 6.05 44.41 0.41 0 PW 2.17 1.43 81.52 14.88 47.91 6.21 42.10 0.18 0 ad: air dried basis; A: ash; M: moisture; V: volatile matter; FC: fixed carbon 表 2 不同样品的热解动力学参数
Table 2 Kinetic parameters of different samples
Sample Stage Ⅰ Stage Ⅱ E /(kJ·mol−1) A /s−1 R2 E /(kJ·mol−1) A /s−1 R2 Cellulose 304.78 9.77 × 1023 0.998 Cellulose-1.25 112.46 1.22 × 108 0.997 Lignin 66.71 1.01 × 103 0.997 Lignin-1.25 62.89 4.48 × 102 0.998 CC 105.81 6.60 × 107 0.999 248.29 1.74 × 1019 0.999 CC-1.25 112.91 3.10 × 108 0.999 208.99 4.97 × 1015 0.999 PW 106.45 1.19 × 107 0.996 317.06 7.56 × 1023 0.997 PW-0.5 129.34 4.65 × 109 0.998 222.24 1.55 × 1016 0.999 PW-1.25 143.38 1.38 × 1011 0.999 169.94 1.19 × 1012 0.998 PW-2.5 161.91 3.25 × 1013 0.994 92.72 1.16 × 106 0.996 PW-3.75 124.81 2.97 × 109 0.999 PW-5 126.23 6.91 × 109 0.999 表 3 生物炭微观结构数据信息
Table 3 Microscopic structure information of the biochar
Sample Specific surface area /(m2·g−1) Pore volume / (cm3·g−1) Average pore size /nm total micro- meso- total micro- meso- PW-1.25-350 1151 671 480 1.57 0.37 1.20 4.37 PW-350 1150 628 522 1.57 0.36 1.21 4.16 AC 1025 919 106 0.67 0.46 0.21 2.59 表 4 活性炭吸附能力比较
Table 4 Comparison of the biochar with the activated carbon reported in the literature
Biomass Activation agent Temperature /℃ Adsorption capacity /(mg·g−1) Ref. Bamboo Urea + KHCO3 700 169 [33] Eucalyptus KOH 800 222 [34] Pine shell – 550 25 [35] Poplar* Urea 900 160.5 [36] Bamboo** KC2O4 700 169.5 [37] Corn straw ZnCl2 + FeCl3 900 183.43 [38] Pine wood ZnCl2 600 165 this work *: with CO2-assisted activation; **: with NH3-assisted activation -
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