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Design of bio-oil additives via molecular signature descriptors using a multi-stage computer-aided molecular

《化学科学与工程前沿（英文）》 2022年第16卷第2期页码 168-182 doi: 10.1007/s11705-021-2056-8

摘要： Direct application of bio-oil from fast pyrolysis as a fuel has remained a challenge due to its undesirable attributes such as low heating value, high viscosity, high corrosiveness and storage instability. Solvent addition is a simple method for circumventing these disadvantages to allow further processing and storage. In this work, computer-aided molecular design tools were developed to design optimal solvents to upgrade bio-oil whilst having low environmental impact. Firstly, target solvent requirements were translated into measurable physical properties. As different property prediction models consist different levels of structural information, molecular signature descriptor was used as a common platform to formulate the design problem. Because of the differences in the required structural information of different property prediction models, signatures of different heights were needed in formulating the design problem. Due to the combinatorial nature of higher-order signatures, the complexity of a computer-aided molecular design problem increases with the height of signatures. Thus, a multi-stage framework was developed by developing consistency rules that restrict the number of higher-order signatures. Finally, phase stability analysis was conducted to evaluate the stability of the solvent-oil blend. As a result, optimal solvents that improve the solvent-oil blend properties while displaying low environmental impact were identified.

关键词： computer-aided molecular design bio-oil additives molecular signature descriptor

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Catalytic hydrodeoxygenation of pyrolysis bio-oil to jet fuel: A review

《能源前沿（英文）》 doi: 10.1007/s11708-024-0943-7

摘要： Bio-oil from biomass pyrolysis cannot directly substitute traditional fuel due to compositional deficiencies. Catalytic hydrodeoxygenation (HDO) is the critical and efficient step to upgrade crude bio-oil to high-quality bio-jet fuel by lowering the oxygen content and increasing the heating value. However, the hydrocracking reaction tends to reduce the liquid yield and increase the gas yield, causing carbon loss and producing hydrocarbons with a short carbon-chain. To obtain high-yield bio-jet fuel, the elucidation of the conversion process of biomass catalytic HDO is important in providing guidance for metal catalyst design and optimization of reaction conditions. Considering the complexity of crude bio-oil, this review aimed to investigate the catalytic HDO pathways with model compounds that present typical bio-oil components. First, it provided a comprehensive summary of the impact of physical and electronic structures of both noble and non-noble metals that include monometallic and bimetallic supported catalysts on regulating the conversion pathways and resulting product selectivity. The subsequent first principle calculations further corroborated reaction pathways of model compounds in atom-level on different catalyst surfaces with the experiments above and illustrated the favored C–O/C=O scission orders thermodynamically and kinetically. Then, it discussed hydrogenation effects of different H-donors (such as hydrogen and methane) and catalysts deactivation for economical and industrial consideration. Based on the descriptions above and recent researches, it also elaborated on catalytic HDO of biomass and bio-oil with multi-functional catalysts. Finally, it presented the challenges and future prospective of biomass catalytic HDO.

关键词： biomass pyrolysis oil bio-jet fuel catalytic hydrodeoxygenation (HDO) metal catalyst reaction pathways

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Production of renewable fuels by blending bio-oil with alcohols and upgrading under supercritical conditions

Sainab Omar, Suzanne Alsamaq, Yang Yang, Jiawei Wang

《化学科学与工程前沿（英文）》 2019年第13卷第4期页码 702-717 doi: 10.1007/s11705-019-1861-9

摘要： The work studied a non-catalytic upgrading of fast pyrolysis bio-oil by blending under supercritical conditions using methanol, ethanol and isopropanol as solvent and hydrogen donor. Characterisation of the bio-oil and the upgraded bio-oils was carried out including moisture content, elemental content, pH, heating value, gas chromatography-mass spectrometry (GCMS), Fourier transform infrared radiation, C nuclear magnetic resonance spectroscopy, and thermogravimetric analysis to evaluate the effects of blending and supercritical reactions. The GCMS analysis indicated that the supercritical methanol reaction removed the acids in the bio-oil consequently the pH increased from 2.39 in the crude bio-oil to 4.04 after the supercritical methanol reaction. The ester contents increased by 87.49% after the supercritical methanol reaction indicating ester formation could be the major deacidification mechanism for reducing the acidity of the bio-oil and improving its pH value. Simply blending crude bio-oil with isopropanol was effective in increasing the C and H content, reducing the O content and increasing the heating value to 27.55 from 17.51 MJ·kg in the crude bio-oil. After the supercritical isopropanol reaction, the heating value of the liquid product slightly further increased to 28.85 MJ·kg .

关键词： bio-oil blending supercritical upgrading characterisation

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Catalytic hydrodeoxygenation of pyrolysis bio-oil to jet fuel: A review

《能源前沿（英文）》 doi: 10.1007/s11708-024-0924-8

关键词： biomass pyrolysis oil bio-jet fuel catalytic hydrodeoxygenation (HDO) metal catalyst reaction pathways

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A review on catalytic & non-catalytic bio-oil upgrading in supercritical fluids

Sainab Omar, Yang Yang, Jiawei Wang

《化学科学与工程前沿（英文）》 2021年第15卷第1期页码 4-17 doi: 10.1007/s11705-020-1933-x

摘要： This review article summarizes the key published research on the topic of bio-oil upgrading using catalytic and non-catalytic supercritical fluid (SCF) conditions. The precious metal catalysts Pd, Ru and Pt on various supports are frequently chosen for catalytic bio-oil upgrading in SCFs. This is reportedly due to their favourable catalytic activity during the process including hydrotreating, hydrocracking, and esterification, which leads to improvements in liquid yield, heating value, and pH of the upgraded bio-oil. Due to the costs associated with precious metal catalysts, some researchers have opted for non-precious metal catalysts such as acidic HZSM-5 which can promote esterification in supercritical ethanol. On the other hand, SCFs have been effectively used to upgrade crude bio-oil without a catalyst. Supercritical methanol, ethanol, and water are most commonly used and demonstrate catalyst like activities such as facilitating esterification reactions and reducing solid yield by alcoholysis and hydrolysis, respectively.

关键词： bio-oil upgrading supercritical review

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生物油的蒸馏特性及其应用

杨续来,陆　强,朱锡锋

《中国工程科学》 2007年第9卷第11期页码 110-114

摘要：

生物油常压馏分约占样品总量的50％，其余为结焦残余物，说明生物油不易蒸发燃烧，但可以雾化燃烧；生物油成分复杂，其中由木质素衍生的酚类含量较为丰富，可采用减压蒸馏或蒸汽蒸馏进行分离提取；蒸馏方法还可用于生物油的品质改良，如增强油品的稳定性、提高热值和降低pH值等。

关键词：生物油蒸馏酚类品质改良

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Experimental study on microwave pyrolysis of eucalyptus camaldulensis leaves: a promising approach for bio-oil

《化学科学与工程前沿（英文）》 doi: 10.1007/s11705-024-2466-5

摘要： Eucalyptus species are extensively cultivated trees commonly used for timber production, firewood, paper manufacturing, and essential nutrient extraction, while lacking consumption of the leaves increases soil acidity. The objective of this study was to recover bio-oil through microwave pyrolysis of eucalyptus camaldulensis leaves. The effects of microwave power (450, 550, 650, 750, and 850 W), pyrolysis temperature (500, 550, 600, 650, and 700 °C), and silicon carbide amount (10, 25, 40, 55, and 70 g) on the products yields and bio-oil constituents were investigated. The yields of bio-oil, gas, and residue varied within the ranges of 19.8–39.25, 33.75–46.7, and 26.0–33.5 wt %, respectively. The optimal bio-oil yield of 39.25 wt % was achieved at 650 W, 600 °C, and 40 g. The oxygenated derivatives, aromatic compounds, aliphatic hydrocarbons, and phenols constituted 40.24–74.25, 3.25–23.19, 0.3–9.77, and 1.58–7.75 area % of the bio-oils, respectively. Acetic acid (8.17–38.18 area %) was identified as a major bio-oil constituent, and hydrocarbons with carbon numbers C₁ and C₂ were found to be abundant. The experimental results demonstrate the potential of microwave pyrolysis as an eco-friendly and efficient way for converting eucalyptus waste into valuable bio-oil, contributing to the sustainable utilization of biomass resources.

关键词： bio-oil recovery eucalyptus leaves microwave pyrolysis

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Research on combustion characteristics of bio-oil from sewage sludge

Rui LI, Baosheng JIN, Xiangru JIA, Zhaoping ZHONG, Gang XIAO, Xufeng FU

《化学科学与工程前沿（英文）》 2009年第3卷第2期页码 161-166 doi: 10.1007/s11705-009-0057-0

摘要： Combustion characteristics of bio-oil from sewage sludge were investigated using thermogravimetry (TG) and Fourier Transform Infrared Spectroscopy (FT-IR) techniques. The combustion process could be divided into two weight loss stages. Light compounds volatilized and were oxidized in the first stage and the heterogeneous combustion between oxygen and heavy compounds happened in the second stage, which were confirmed by FT-IR technique. Most weight loss occurred in the first stage. The effect of heating rate was also studied and higher heating rates were found to facilitate the combustion process. The kinetic parameters of the two stages were calculated and the change of activation energy indicated higher heating rates benefited combustion.

关键词： bio-oil from sewage sludge fast pyrolysis combustion characteristics TG-FT-IR kinetic

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生物质热解油的性质精制与利用

朱锡锋,郑冀鲁,郭庆祥,朱清时

《中国工程科学》 2005年第7卷第9期页码 83-88

摘要：

从元素含量、化学成分、稳定性、粘度、热值等方面详细叙述了热解生物油的性质，介绍了生物油的精制和利用技术，其中对近年来出现的生物油热蒸气直接催化精制、利用表面活性剂改良生物油使其直接用于柴油机等新技术给予了特别关注，对催化剂在生物油精制和利用过程中的影响也作了重点叙述。

关键词：生物质生物油燃料特性精制

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Recent advances in co-processing biomass feedstock with petroleum feedstock: A review

《能源前沿（英文）》 doi: 10.1007/s11708-024-0920-1

摘要： Co-processing of biomass feedstock with petroleum feedstock in existing refineries is a promising technology that enables the production of low-carbon fuels, reduces dependence on petroleum feedstock, and utilizes the existing infrastructure in refinery. Much effort has been dedicated to advancing co-processing technologies. Though significant progress has been made, the development of co-processing is still hindered by numerous challenges. Therefore, it is important to systematically summarize up-to-date research activities on co-processing process for the further development of co-processing technologies. This paper provides a review of the latest research activities on co-processing biomass feedstock with petroleum feedstock utilizing fluid catalytic cracking (FCC) or hydrotreating (HDT) processes. In addition, it extensively discusses the influence of different types and diverse physicochemical properties of biomass feedstock on the processing of petroleum feedstock, catalysts employed in co-processing studies, and relevant projects. Moreover, it summarizes and discusses co-processing projects in pilot or larger scale. Furthermore, it briefly prospects the research trend of co-processing in the end.

关键词： co-processing biomass bio-oil petroleum feedstock fluid catalytic cracking hydrotreating

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Recent advances in the catalytic pyrolysis of biomass

Changwei HU, Yu YANG, Jia LUO, Pan PAN, Dongmei TONG, Guiying LI

《化学科学与工程前沿（英文）》 2011年第5卷第2期页码 188-193 doi: 10.1007/s11705-010-1015-6

摘要： Biomass is considered as a renewable and alternative resource for the production of fuels and chemicals, since it is the only carbon and hydrogen containing resource that we can find in the world except for fossil resources, capable of being converted to hydrocarbons. The pyrolytic liquefaction of biomass is a promising way to convert biomass to useful products. This paper briefly surveys the present status of the direct catalytic pyrolysis for the liquefaction of biomass. The direct use of catalysts could decrease the pyrolysis temperature, increase the conversion of biomass and the yield of bio-oil, and change the distribution of the pyrolytic liquid products then improve the quality of the bio-oil obtained. The fact that biomass is in solid state present great challenges for its conversion and for the effective use of catalysts due to the bad heat transfer characteristics and bad mass transfer properties. These barriers appeal for the development of a new catalyst and new catalytic process as well as the integration of both. Process design and process intensification are of significant importance in the catalytic conversion of biomass.

关键词： biomass liquefaction catalysis bio-oil process intensification

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Highly selective catalytic hydrodeoxygenation of guaiacol to cyclohexane over Pt/TiO

Zhong HE,Xianqin WANG

《化学科学与工程前沿（英文）》 2014年第8卷第3期页码 369-377 doi: 10.1007/s11705-014-1435-9

摘要： Catalysts Pt/TiO and NiMo/Al O are highly active and selective for the hydrodeoxygenation of guaiacol in a fixed bed reactor at 300 °C and 7.1 MPa, leading to the hydrogenation of aromatic ring, followed by demethylation and dehydroxylation to produce cyclohexane. For a complete hydrodeoxygenation of guaiacol, metal sites and acid sites are required. NiMo/Al O and Pt/Al O are more active and selective for cyclohexane formation as compared with Pt/TiO at 285 °C and 4 MPa. However, Pt/TiO is stable while the other two catalysts deactivate due to the nature and amount of coke formation during the reaction.

关键词： Pt/TiO₂ NiMo/Al₂O₃ Pt/Al₂O₃ bio-oil hydrodeoxygenation guaiacol cyclohexane

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Ball milling promoted direct liquefaction of lignocellulosic biomass in supercritical ethanol

Chunyan Yang, Xiaoliang Yuan, Xueting Wang, Kejing Wu, Yingying Liu, Changjun Liu, Houfang Lu, Bin Liang

《化学科学与工程前沿（英文）》 2020年第14卷第4期页码 605-613 doi: 10.1007/s11705-019-1841-0

摘要： In the present work, ball milling was applied for the pretreatment of lignocellulose to obtain high conversion and bio-oil yield in supercritical ethanol. Ball milling substantially decreased the crystallinity and particle size of lignocellulose, thereby improving its accessibility in ethanol solvent. An increased bio-oil yield of 59.2% was obtained for the ball milled camphorwood sawdust at 300°C, compared with 39.6% for the original lignocellulose. Decreased crystallinity significantly benefited the conversion of the cellulose component from 60.8% to 91.7%, and decreased particle size was beneficial for the conversion of all components. The obtained bio-oil had a high phenolic content, as analyzed by gas chromatography-mass spectrometry. Methoxylation and retro-aldol condensation were observed during alcoholysis, and the reaction pathways of lignocellulose in supercritical ethanol were attributed to the action of free radicals.

关键词： ball milling lignocellulose supercritical ethanol liquefaction bio-oil

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生物质热解液化装置研制与试验研究

朱锡锋,郑冀鲁,陆强,郭庆祥,朱清时

《中国工程科学》 2006年第8卷第10期页码 89-93

摘要：

介绍了一种电热式快速流化床生物质热解液化装置的研制，该装置的技术关键是采用两级螺旋进料和大流量喷雾直接冷凝收集生物油。试验结果表明，该装置完全可以用于各种固体生物质的热解液化，而且无论何种生物质都存在最佳热解温度。木屑、稻壳、玉米秆和棉花秆4种原料在最佳热解条件下的生物油质量产率分别为63%，53%，57%和56%，热值均为17～18MJ/kg。通过试验研究还发现，生物油是一种复杂的含氧有机化合物和水组成的混合物，包含了几乎所有化学类别的有机物；减少原料携带的外在水可有效降低生物油中的水分；储藏时间达半年的生物油仍然可以直接燃烧。

关键词：生物质热解液化生物油

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Combustion characteristics and kinetics of bio-oil

Ruixia ZHANG, Zhaoping ZHONG, Yaji HUANG

《化学科学与工程前沿（英文）》 2009年第3卷第2期页码 119-124 doi: 10.1007/s11705-009-0068-x

摘要： The combustion characteristics of bio-oils derived from rice husk and corn were studied by thermogravimetry analysis. According to the thermogravimetry (TG), differential thermogravimetry (DTG) and differential thermal analysis (DTA) curves of bio-oils in air and nitrogen atmosphere, we analyzed the combustion characteristics of different kinds of bio-oils in different atmospheres and worked out the combustion kinetics parameters of the bio-oil, providing reliable base data for the burning of bio-oil. The thermogravimetry indicated that the combustion process of bio-oil was divided into three stages. At the same time, the combustion process can be described by different order reaction models, and with the method of Coats-Redfern, the activation energy and frequency factor of different kinds of bio-oils were obtained.

关键词： bio-oil combustion characteristics combustion kinetics