基于模型化合物的生物质半焦催化性能研究

doi:10.3969/j.issn.0253-2417.2020.05.009

摘要/Abstract

摘要：

为了深入理解生物质热解过程中生物质半焦对挥发分原位催化的作用机理，采用多种官能团化的还原氧化石墨烯（RGO）包括含-OH的RGO-OH、含-COOH的RGO-COOH和含-NH₂的RGO-NH₂，以及未官能团化的RGO模拟富含活性官能团的生物质半焦，通过热裂解-气相色谱质谱联用仪（Py-GC/MS）探究400℃下不同表面活性官能团对木质素中典型α-O-4化合物苄基苯基醚（BPE）的催化效果。研究结果表明：-OH和-COOH活性官能团能显著提高BPE的热分解程度，BPE转化率由0.1%（无催化剂）提高至38%（-COOH）和54%（-OH）；而-NH₂只提供了12%的BPE转化率，甚至弱于无官能团RGO的催化活性（25.63%），表明-NH₂起抑制作用。BPE分解主要是以sp³C_α-O断裂为主，其产物以苯酚和2-苄基苯酚为主；表面含氧官能团（-OH和-COOH）也促进了二聚反应的进行，形成了2-苄基苯酚和4-苄基苯酚。此外，表面官能团还能促进sp²C_aryl-O断裂，产物主要为苯甲醛。

关键词: 生物质热解, 半焦催化剂, 官能团化石墨烯, 木质素, α-O-4型

Abstract:

To deeply understand the catalytic mechanism of bio-char on volatiles during biomass pyrolysis, a variety of functionalized graphenes, including RGO-OH, RGO-COOH and RGO-NH₂, were used as functional-group-rich char models. The catalytic effect of these different surface functional groups on the typical lignin α-O-4 compound benzyl phenyl ether(BPE) at 400℃ was investigated by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). The results showed that -OH and -COOH significantly increased the degree of thermal decomposition of BPE. The conversion of BPE increased from 0.1% (without catalyst) to 37.73% (with RGO-COOH as catalyst) and 53.78% (with RGO-OH as catalyst), respectively. However, -NH₂ only provided a BPE conversion of 12.29%, even weaker than the catalytic activity of non-functionalized reductive graphene oxide (RGO) (BPE conversion of 25.63%), indicating that the RGO as carrier also had a certain catalytic effect on BPE conversion, and -NH₂ played an inhibitory role. The decomposition of BPE was mainly caused by the sp³ C_α-O bond cleavage, and the proudcts were mainly phenol and 2-benzylphenol. The surface oxygen-containing functional groups (-OH and -COOH) promoted the dimerization reaction, forming 2-benzylphenol and 4-benzylphenol. In addition, the functional groups also could promote the cleavage of sp² C_aryl-O, and the main product was benzaldehyde.

Key words: biomass pyrolysis, bio-char catalyst, functionalized graphene, lignin, α-O-4

中图分类号:

TQ35
TK6

黄勇,刘沙沙,吴益霜,周建斌,张书. 基于模型化合物的生物质半焦催化性能研究[J]. 林产化学与工业, 2020, 40(5): 63-68.

Yong HUANG,Shasha LIU,Yishuang WU,Jianbin ZHOU,Shu ZHANG. Catalytic Performance of Bio-char Based on Model Compounds[J]. Chemistry and Industry of Forest Products, 2020, 40(5): 63-68.

图/表 3

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序号 No.	化合物 compound	不同催化剂下各产物峰面积peak area of products with different catalysts(×10⁶)
序号 No.	化合物 compound	无none	RGO	RGO-OH	RGO-COOH	RGO-NH₂
1	甲苯toluene	—	55.9	11.3	6.75	19.6
2	苯甲醛benzaldehyde	—	17.5	92.2	45.6	18.6
3	苯甲醇benzyl alcohol	—	—	4.52	11.5	—
4	苯酚phenol	1.66	81.5	136	109	41.9
5	二苯甲烷diphenylmethane	—	4.34	1.38	1.26	0.827
6	联苄bibenzyl	1.41	4.91	—	—	—
7	反式-1, 2-二苯乙烯E-stilbene	—	16.6	—	—	—
8	2-苄基苯酚2-benzylphenol	—	11.4	110	196	8.16
9	4-苄基苯酚4-benzylphenol	—	4.47	22.7	62.9	2.59

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