Experimental study on catalytic pyrolysis of lignin under char and ZSM-5 for preparation of aromatics
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摘要: 为了提高木质素催化热解所得芳烃的产率,本研究以碱木质素为原料,在碱木质素炭和ZSM-5的二元催化体系下进行快速热解实验,选取催化剂比例、热解温度、热解时间等为实验变量,探究碱木质素热解产物中芳烃的变化规律以及碱木质素炭和ZSM-5协同催化作用机理。结果表明,碱木质素催化热解所得芳烃的产量从17 mg/g(未加炭)提高到33 mg/g(炭添加量为1 g),产率增加了近一倍。通过不同工况研究发现,碱木质素快速热解制备芳烃的最佳条件是:碱木质素∶碱木质素炭∶ZSM-5 = 1∶1∶1, 热解温度为500 ℃,热解时间为10 min。机理分析表明,热解过程中碱木质素炭主要起断键作用,而ZSM-5起择形芳构化作用,两者协同作用得到更高的芳烃产率。Abstract: In order to improve yield of aromatics from catalytic pyrolysis of lignin, alkali lignin was used for rapid pyrolysis experiments under a binary catalysis system of alkali lignin char and ZSM-5. Influence of catalyst ratio and pyrolysis temperature as well as pyrolysis time on aromatics quantity and mechanism of synergistic catalysis of alkali lignin char and ZSM-5 were investigated. The results show that quantity of aromatics has increased from 17 mg/g (without char) to 33 mg/g (with char addition of 1 g), which is about doubled. The optimal conditions for preparation of aromatics are under alkali lignin∶alkali lignin char∶ZSM-5=1∶1∶1 at 500℃ for 10 min. Meanwhile, the mechanism analysis shows that alkali lignin char mainly plays a role in bond breaking during pyrolysis, while ZSM-5 can act as selective aromatization to obtain higher aromatics yield, whose synergistic effects result in higher aromatic yield.
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Key words:
- alkali lignin /
- alkali lignin char /
- binary catalytic system /
- aromatics /
- synergy
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图 1 木质素快速热解实验装置示意图
Figure 1 Schematic diagram of experimental device for fast pyrolysis of lignin
1: nitrogen; 2: air; 3: mass flow controller; 4: furnace; 5: quartz hanging basket; 6: stainless steel tube; 7: thermocouple; 8: temperature controller; 9: ice-bath condenser; 10: drying tube; 11: gas bag
表 1 生物油主要成分的GM-MS分析
Table 1 GM-MS analysis of major compositions of bio-oil
RT.(min) Compound Peak area of compounds/ (× 107) 1∶0∶0 1∶1∶0 1∶1∶1 acid 6.742 acetic acid 0.70 0.78 0.85 phenol 14.019 phenol 2.91 2.67 2.42 methoxy phenol 15.099 phenol,2-methoxy- 3.93 2.51 1.13 17.315 phenol,2-methoxy-4-methyl- 2.77 1.41 0.90 19.192 phenol,4-ethyl-2-methoxy- 2.67 1.78 1.23 20.388 phenol,2-methoxy-4-vinyl 1.96 1.56 0.76 21.498 phenol,2,6-dimethoxy- 2.03 0.98 0.39 21.782 3-methoxy-5-methylphenol 0.41 0.52 − 23.658 phenol,4-methoxy-
3-(methoxymethyl)-1.83 0.84 0.76 Total 15.60 9.60 5.17 alkyl phenol 15.026 phenol,2-methyl- − 0.91 0.63 15.775 phenol,4-methyl- 2.01 1.95 1.61 16.834 phenol,2,4-dimethyl- 0.72 1.16 1.23 17.616 phenol,4-ethyl- 3.17 3.71 − 18.701 phenol,3-ethyl-5-methyl- 0.85 1.28 0.93 20.623 2-Allylphenol − 0.56 − total 6.75 9.57 4.4 aromatics 8.094 toluene − − 1.35 9.996 p-xylene − − 1.86 16.545 naphthalene − − 5.20 19.037 naphthalene,1-methyl- − − 3.91 total − − 12.32 -
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