实验和密度泛函理论分析阿维菌素的热解机理

ZHOU Hao; LIU Su-xiang; ZHAO Bao-feng; WANG Jing-wei; GUAN Hai-bin; ZHU Di; LI Huan; SONG An-gang

doi:10.1016/S1872-5813(23)60367-6

实验和密度泛函理论分析阿维菌素的热解机理

doi: 10.1016/S1872-5813(23)60367-6

周浩^1,,
刘素香^1, ,,
赵保峰^1,,
王婧薇^2,,
关海滨^1,,
朱地^1, ,,
李欢^1,,
宋安刚^1,

1.
齐鲁工业大学(山东科学院)能源研究院, 山东省生物质气化技术重点实验室, 山东济南250014
2.
莫纳什大学化学工程系, 克莱顿 3800

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中图分类号: X786
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出版历程
- 收稿日期: 2023-02-07
- 修回日期: 2023-03-21
- 录用日期: 2023-04-25
- 网络出版日期: 2023-05-06
- 刊出日期: 2023-08-01

Analyzing the pyrolysis mechanism of avermectin via experiments and density functional theory

ZHOU Hao^1
,,
LIU Su-xiang^{1
, ,},
ZHAO Bao-feng^1
,,
WANG Jing-wei^2
,,
GUAN Hai-bin^1
,,
ZHU Di^{1
, ,},
LI Huan^1
,,
SONG An-gang^1
,

1.
Key Laboratory for Biomass Gasification Technology of Shandong Province, Energy Research Institute, Qilu University of Technology (Shandong Academy of Sciences), Jinan 250014, China
2.
Department of Chemical Engineering, Monash University, Clayton 3800, Australia

Funds: The project was supported by the National Key R&D Program of China (2018YFE0106400), Natural Science Foundation of Shandong Province of China (ZR2019MEE069), “20 Colleges and Universities” of Jinan Science and Technology Bureau (202228123, 2019GXRC046), Qilu University of Technology (Shandong Academy of Sciences) Science, Education and Industry Integration Innovation Pilot Project (2022GH010)

More Information

Corresponding author: E-mail: liusx@sdas.org; zhud@sderi.cn

摘要

摘要: 本研究通过实验和密度泛函理论模拟(DFT)分析了阿维菌素(AVM)的热降解机理。AVMD热解实验结果表明，在250 °C以上，AVM残渣去除率达到99.88%的峰值。AVM热解产物主要为醇类。通过模拟和过渡态计算，确定的四种潜在降解途径中最有可能的是基于破坏C−O键。模拟结果与实验结果基本一致。这些结果为抗生素安全处置技术的发展提供了理论和经验支持。
- 阿维菌素 /
- 阿维菌素菌渣 /
- 密度泛函理论 /
- 热解 /
- 机理
Abstract: In this study, the thermal degradation mechanism of avermectin (AVM) was analyzed via experiments and density functional theory calculations (DFT). The experimental results of AVMD pyrolysis indicated that the removal rate of AVM residues reached peak value of 99.88% above 250 °C. The main product of AVM pyrolysis was alcohols. Based on the C−O bonds breaking, four potential degradation pathways were proposed. The findings of the calculations were in agreement with those of the experiments. These results provide theoretical and empirical guidance for the development of safe antibiotic disposal technology.
- avermectin /
- avermectin mycelial dreg /
- density functional theory /
- pyrolysis /
- degradation mechanism

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FIG. 2579. FIG. 2579.

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Figure 1 Structural formula of avermectin B_1a

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Figure 2 Fixed-bed reaction system used for avermectin pyrolysis

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Figure 3 Yield of residue products in avermectin pyrolysis at different temperatures

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Figure 4 Degradation rate of avermectin residue at different temperature

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Figure 5 Degradation rate of avermectin at different temperature

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Figure 6 Yield of avermectin pyrolysis products at different temperatures

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Figure 7 Composition of liquid pyrolysis products at different temperatures

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Figure 8 AVM decomposition pathways

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Table 1 Primary properties of AVMD

Proximate analysis w/%				Ultimate analysis w_d/%
M_ad	V_d	A_d	FC_d	C	H	N	S	O^a
2.49	36.65	50.43	10.44	31.13	4.71	4.29	0.17	20.56
M: moisture; V: volatile; A: ash; FC: fixed carbon; ad: air dried basis; d: dry basis, a: Determined by difference

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Table 2 Decomposition pathways and associated Mulliken layout numbers(e)

Pathway	Bond	Layout number	Bond length /Å	Energy barrier / (kcal·mol⁻¹)
A and B	C4'–O	0.53	1.43	5.85
C	C13–O	0.56	1.43	6.70
D	C16–C17	0.70	1.41	8.43
D	C8–C9	1.33	1.35	8.43

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Table 3 Duel speed step reaction energy base under four paths

Pathway	TS	Energy barrier /(kcal·mol⁻¹)
Path-A	TS-A4	42.7
Path-B	TS-B3	69.32
Path-C	TS-C2	50.52
Path-D	TS-D5	64.67

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