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生物质材料热解产生的二噁英和二苯并呋喃类分子类似物——生物油生产中的新挑战

Dioxin and dibenzofuran like molecular analogues from the pyrolysis of biomass materials-the emerging challenge in bio-oil production.

作者信息

Kirkok Samuel K, Kibet Joshua K, Kinyanjui Thomas, Okanga Francis I, Nyamori Vincent O

机构信息

Department of Chemistry, Egerton University, P.O Box 536, Egerton, 20115, Kenya.

School of Chemistry and Physics, University of KwaZulu-Natal, Westville Campus, Private Bag X54001, Durban, 4000, South Africa.

出版信息

BMC Chem. 2021 Jan 15;15(1):3. doi: 10.1186/s13065-020-00732-z.

Abstract

INTRODUCTION

The aggressive search for renewable energy resources and essential pyrosynthetic compounds has marked an exponential rise in the thermal degradation of biomass materials. Consequently, clean and sustainable transport fuels are increasingly desirable in a highly industrialized economy, for energy security and environmental protection. For this reason, biomass materials have been identified as promising alternatives to fossil fuels despite the challenges resulting from the possible formation of toxic nitrogen-based molecules during biomass degradation. In order to understand the free radical characteristic challenges facing the use of bio-oil, a brief review of the effects of free radicals in bio-oil is presented.

METHODOLOGY

Pyrolysis was conducted in a tubular flow quartz reactor at a residence time of 2 s at 1 atm. pressure, for a total pyrolysis time of 5 min. The thermal degradation of biomass components was investigated over the temperature range of 200 to 700 °C typically in 50 °C increments under two reaction conditions; pyrolysis in N and oxidative pyrolysis in 5% O in N. The pyrolysate effluent was analysed using a Gas chromatograph hyphenated to a mass selective detector (MSD).

RESULTS

The yield of levoglucosan in the pyrolysis of cellulose in the entire pyrolysis temperature range was 68.2 wt % under inert conditions and 28.8 wt % under oxidative conditions. On the other hand, formaldehyde from pyrolysis of cellulose yielded 4 wt % while that from oxidative pyrolysis was 7 wt % translating to ⁓ 1.8 times higher than the yield from pyrolysis. Accordingly, we present for the first time dioxin-like and dibenzofuran-like nitrogenated analogues from an equimassic pyrolysis of cellulose and tyrosine. Levoglucosan and formaldehyde were completely inhibited during the equimassic pyrolysis of cellulose and tyrosine.

CONCLUSION

Clearly, any small amounts of N-biomass components such as amino acids in cellulosic biomass materials can inhibit the formation of levoglucosan-a major constituent of bio-oil. Overall, a judicious balance between the production of bio-oil and side products resulting from amino acids present in plant matter should be taken into account to minimize economic losses and mitigate against negative public health concerns.

摘要

引言

对可再生能源资源和重要热解合成化合物的积极探索,标志着生物质材料热降解呈指数级增长。因此,在高度工业化的经济体中,出于能源安全和环境保护的考虑,清洁且可持续的运输燃料愈发受到青睐。出于这个原因,尽管生物质降解过程中可能形成有毒的含氮分子会带来挑战,但生物质材料已被视为化石燃料的有前途的替代品。为了理解生物油使用中面临的自由基特性挑战,本文简要回顾了自由基在生物油中的影响。

方法

热解在管式流动石英反应器中进行,停留时间为2秒,压力为1个大气压,总热解时间为5分钟。在200至700°C的温度范围内,通常以50°C的增量,在两种反应条件下研究生物质成分的热降解;在氮气中热解以及在含5%氧气的氮气中进行氧化热解。热解产物流出物使用与质量选择性检测器(MSD)联用的气相色谱仪进行分析。

结果

在整个热解温度范围内,纤维素热解中左旋葡聚糖的产率在惰性条件下为68.2 wt%,在氧化条件下为28.8 wt%。另一方面,纤维素热解产生的甲醛产率为4 wt%,而氧化热解产生的甲醛产率为7 wt%,比热解产率高约1.8倍。因此,我们首次展示了纤维素和酪氨酸等质量热解产生的二噁英类和二苯并呋喃类含氮类似物。在纤维素和酪氨酸等质量热解过程中,左旋葡聚糖和甲醛完全被抑制。

结论

显然,纤维素生物质材料中任何少量的含氮生物质成分,如氨基酸,都会抑制左旋葡聚糖(生物油的主要成分)的形成。总体而言,应考虑在生物油生产与植物中存在的氨基酸产生的副产物之间进行明智的平衡,以尽量减少经济损失并减轻对公众健康的负面影响。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e3eb/7809783/dc85f7b23d67/13065_2020_732_Sch1_HTML.jpg

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