Direct production of biodiesel from waste oils with a strong solid base from alkalized industrial clay ash

Direct production of biodiesel from waste oils with a strong solid base from alkalized industrial clay ash

Recently, PhD student Miss Wen-jie Cong supervised by Prof. Zhen Fang published a research article in Applied Energy about biodiesel production from high acid (AV) waste oils with a solid base derived from spent bleaching clay (SBC).

Biodiesel was directly one-step produced from waste oils without pretreatment catalyzed by a solid base alkalized from SBC ash. Optimized conditions were obtained with 99.1% biodiesel yield from soybean oil with an orthogonal design. The base catalyst was stable within 8 cycles (> 95% biodiesel yield) and resistant to saponification (AV = 9.7 mg KOH/g, 96.5% biodiesel yield). The base was characterized with XRD, EDX-mapping, FT-IR, XRF and TPD, and it had similar strong basicity to Na2SiO3 (0.21 vs. 0.22 mmol/g for Na2SiO3) with active sites of Na2O and CH3ONa evolved from Na2SiO3 and NaAlSiO4 by reactions of NaOH with oxides (e.g., SiO2, Al2O3) in SBC ash. Furthermore, the base was magnetized with magnetism of 6.86 emu/g by carbonizing residual oil in SBC as carbon support and reductant (of Fe2O3 to magnetic Fe3O4 particles). It catalyzed soybean oil to produce biodiesel with 99.2% yield and blended oil (AV = 5.9) to biodiesel with 91.9% yield without any saponification. The catalyst was magnetically separated and reused for 3 cycles with 87% yield. The non-magnetic base could also efficiently catalyze actual SBC oil for the production of biodiesel with 95% yield at AV of 10. This work realized the full use of inorganics in SBC, and its oil for direct biodiesel production at a low temperature (i.e., 65 vs. 120 oC with sulfuric acid process) without wastes produced and results can easily find practical applications for waste oils.

Related results were accepted in Applied Energy:

WJ Cong, YT Wang, H Li, Zhen Fang*, J Sun, HT Liu, JT Liu, S Tang, L Xu. Direct production of biodiesel from waste oils with a strong solid base from alkalized industrial clay ash. Applied Energy, 264,114735 (2020), https://doi.org/10.1016/j.apenergy.2020.114735.

Solid base synthesized from SBC ash for biodiesel production from waste oils with 8 cycles and anti-saponification. It was further magnetized for easy separation.(以废白土为原料合成固体碱,催化废弃油脂制备生物柴油。该催化剂可循环使用8次且可抗皂化,并被进一步磁化为磁性固体催化剂以便于分离。).

以废白土为原料合成固体碱并用于直接催化废弃油脂制备生物柴油

最近,博士生丛文杰(女)在方老师的指导下,在国际学术期刊Applied Energy(IF8.4,Q1)发表以废白土为原料合成固体碱以制备生物柴油的研究性论文。

通过NaOH碱化废白土灰合成固体碱,直接催化废弃油脂制备生物柴油。首先,以大豆油为原料,通过正交试验确定了最优反应条件(醇油比11:1,催化剂量8 wt%,温度65℃,反应3 h),该条件下生物柴油得率为99.1%,该固体碱8次循环后产率仍高于95%。该固体碱可抗皂化,油脂酸值为9.7 mg KOH/g 时生物柴油产率可达96.5%,催化酸值为10的废白土油可得生物柴油产率为95%。此外,进一步通过碳化废白土中的残油作为碳载体和还原剂(将氧化铁转化为四氧化三铁),磁化为磁性固体碱催化剂(6.86 emu/g)。该磁性固体碱催化大豆油制备生物柴油产率为99.2%,经磁性分离后可重复使用3次(生物柴油产率为87%),催化酸值5.9 mg KOH/g的油脂得生物柴油产率为91.9%且未见皂化。本研究充分利用废白土中的无机物(如二氧化硅、氧化铝等),并实现低温下碱催化一步法转化废白土油为生物柴油。整个生产工艺无废弃物生成,并易于应用于工业生产生物柴油。详情可见:

WJ Cong, YT Wang, H Li, Zhen Fang*, J Sun, HT Liu, JT Liu, S Tang, L Xu. Direct production of biodiesel from waste oils with a strong solid base from alkalized industrial clay ash. Applied Energy, 264,114735 (2020), https://doi.org/10.1016/j.apenergy.2020.114735.

Springer book “Production of Biofuels and Chemicals with Pyrolysis”

Springer book “Production of Biofuels and Chemicals with Pyrolysis”
Springer is going to publish (in revision, due early 2020) a book entitled “Production of Biofuels and Chemicals with Pyrolysis” edited by Profs. Zhen Fang, RL Smith Jr. and Dr. LJ Xu, Springer, Hardcover ISBN 978-981-15-2731-9, 560 pages, 2020 (https://www.springer.com/gp/book/9789811527319#aboutBook) .

Pyrolysis is widely applicable to the valorization of biomass. This book presents a collection of studies on state-of-art techniques developed specifically for conversion of biomass to chemical products by pyrolysis with an emphasis on the fundamentals and mechanisms for producing bio-oils, chemicals, gases and biochar via pyrolysis processes. Key reaction parameters and reactor configurations are outlined for converting many types of biomass into chemical products. All chapters were contributed by respected global experts in their field to provide readers with a broad range of perspectives on cutting-edge applications. The book is an ideal reference guide for academic researchers and industrial engineers in the fields of natural renewable materials, biorefinery of lignocellulose, biofuels and environmental engineering. It can also be used as a comprehensive reference source for university students in chemical engineering, material science and environmental engineering.

This book contains 13 chapters contributed by leading experts in the field. The text is arranged into five key areas:
Part 1. Fundamentals of Pyrolysis
Part 2. Production of Liquid Biofuels by Pyrolysis & Catalytic Pyrolysis
Part 3. Liquid Biofuels Production by Microwave Pyrolysis
Part 4. Producing Bio-Chemicals by Pyrolysis
Part 5. Producing Gas Fuel and Pyrolysis Modeling

The text should be of interest to professionals in academia and industry who are working in the fields of natural renewable materials, biorefinery of lignocellulose, biofuels, agricultural engineering and environmental engineering. It can also be used as comprehensive references for university students with backgrounds of chemical engineering, material science and environmental engineering.

This book is the tenth book of the series entitled, “Biofuels and Biorefineries”, (highly-downloaded books with 135 k chapter downloads and 4 books among “top 25% springer e-books”, Prof. Zhen Fang is serving as Editor-in-Chief), and the seventeenth English book edited/authored by Prof. Zhen Fang since 2009.
Biofuels and Biorefineries:

http://www.springer.com/series/11687?detailsPage=titles

斯普林格新书《热解生产生物燃料和化学品》即将出版

由方真老师、日本东北大学RL Smith Jr.教授和徐禄江博士主编的新书《热解生产生物燃料和化学品》,最近将由斯普林格公司出版发行(in revision, due early 2020,精装,560页, ISBN978-981-15-2731-9, 2020)(https://www.springer.com/gp/book/9789811527319#aboutBook)。

热解广泛应用于生物质的高值化。这本书展示了一个关于最新技术的研究的集合,特别是生物质通过热解转化为化学产品,重点介绍了通过热解过程生产生物油、化学品、气体和生物炭的基本原理和机理。概述了将多种生物质转化为化工产品的关键反应参数和反应器结构。本书包含13个章节,每个章节由全球范围内挑选的该领域的专家或教授编写并通过严格的外审,为读者提供前沿应用的广泛视角。

本书分为五个主要部分:
第1部分: 热解原理
第2部分: 通过热解和催化热解生产液体生物燃料
第3部分: 微波热解生产液体生物燃料
第4部分: 通过热解生产生物化学品
第5部分: 生产气体燃料和热解建模

这本书,为学术界研究人员和工业工程师在自然可再生材料、生物精练的木质纤维素、生物燃料、农业工程和环境工程领域提供了一个理想的参考指南。它对化工、材料科学、环境工程等专业的大学生具有广泛的参考价值。

该书是斯普林格系列丛书“生物燃料和生物炼制- Biofuels and Biorefineries”(方真老师担任该丛书总编辑,章节下载量(电子销售量)近13.5万次,他编著其中4 部专著已进入Springer高下载书籍前25%。)出版的第十本专著,也是方真老师自2009年以来,编著出版的第十七部英语专著。

生物燃料和生物炼制丛书:
http://www.springer.com/series/11687?detailsPage=titles。

Cycloamination strategies for renewable N-heterocycles

Cycloamination strategies for renewable N-heterocycles

Recently, Dr. H Li and Prof. Zhen Fang, collaborated with Prof. RL Smith Jr. (Tohoku University, Japan), published a review (Spotlight) paper in Green Chemistry about the production of renewable N-heterocycles.

Biomass resources have infinite possibilities for introducing nitrogen, sulfur, or phosphorus heteroatoms into their structures by virtue of controllable carbon-heteroatom bond formation. In this review, cycloamination approaches for thermal (catalyst-free) and catalytic transformation of biomass feedstocks into N-heterocyclic molecules including mechanistic pathways are analyzed. Bottom-up (small molecule substrates) and top-down (large molecule substrates) are considered. Sustainable routes for synthesis of five-membered (pyrroles, pyrrolidones, pyrazoles, imidazoles), six-membered (pyridines, pyrazines), fused (indoles, benzimidazoles), and other relevant azaheterocycles are critically assessed. Production of biomass-derived six-, seven-, and eight-membered as well as fused N-heterocyclic compounds with present approaches have relatively low selectivities. Attention to methods for forming analogous sulfur or phosphorus heteroatom compounds from biomass resources using either bottom-up or top-down strategies appear to have been greatly overlooked. Synthetic auxiliaries (heating modes, nitrogen sources) that enhance reaction efficiency and tunability of N-heterocyclic ring size/type are considered and plausible reaction mechanisms for pivotal pathways are developed.

Efficient amination strategies for synthesis of N-heterocycles from functional molecules (bottom-up) or from biomass (top-down) via sustainable C-N/C-X bond chemistry (从功能分子(自下而上)或从生物质(自上而下)通过可持续碳- n /C-X键化学合成n杂环的高效胺化策略)

Related results were accepted in Green Chemistry:

H Li*, HX Guo, Zhen Fang*, TM Aida, RL Smith Jr*, Cycloamination Strategies for Renewable N-heterocycles, Green Chemistry, https://doi.org/10.1039/C9GC03655E , 22, 582-611, 2020 (Spotlight Paper, Review).

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李虎博士在国际学术期刊Green Chemistry发表学术论文

可再生氮杂环的环胺化策略

最近,国际学术期刊Green Chemistry(影响因子9.4, Q1,第一署名单位为南京农业大学,第一作者为李虎博士,通讯作者为李虎博士,方真教授和日本东北大学RL Smith Jr教授)以Spotlight paper形式,发表了生物质生产可再生氮杂环化合物的综述。

生物质资源通过可控的碳-杂原子成键将氮、硫、磷等杂原子引入其结构中具有无限的可能性。本文综述了近年来生物质原料热(无催化)和催化转化为n -杂环分子的环胺化方法及其机理。考虑自底向上(小分子底物)和自顶向下(大分子底物)。五元(吡咯、吡咯烷酮、吡唑、咪唑)、六元(吡啶)的合成路线。用现有方法生产生物衍生的六元、七元、八元以及融合的n杂环化合物的选择性较低。利用自底向上或自顶向下的战略从生物量资源中形成类似硫或磷杂原子化合物的方法似乎受到了极大的忽视。考虑了提高反应效率和n杂环尺寸/类型可调性的合成助剂(加热方式、氮源),并建立了关键途径的合理反应机制。

详情可见:

H Li*, HX Guo, Zhen Fang*, TM Aida, RL Smith Jr*, Cycloamination Strategies for Renewable N-heterocycles, Green Chemistry (IF 9.4), https://doi.org/10.1039/C9GC03655E 22, 582-611, 2020 (Spotlight Paper, Review).

Prof. Charles Xu from University of Western Ontario visited our Lab

Prof. Charles Xu from University of Western Ontario visited our Lab

On November 14, 2019, as invited by Prof. Zhen Fang, Prof. Charles Chunbao Xu from University of Western Ontario (UWO) in Canada and Dr. Yongsheng Zhang from Zhengzhou University visited our College of Engineering for the academic exchanges and research collaborations. Prof. Xu has a close collaboration with Prof. Fang for a long history in research and student exchanges.

In the afternoon, Prof. Xu gave a lecture to teachers and students on “Conversion of agricultural biomass into bio-based chemicals and materials”. He briefly introduced about UWO and its main research directions, including the works on biomass resources, sludge into bioenergy, biofuels and bio-based chemicals, and presented his Lab’s main research topics and results in detail, particularly showed us how to produce economic viable materials and chemicals besides biofuels from biomass wastes. The academic lecture brings inspiration to the future development and directions of renewable energy and biomass resources utilizations.

After the presentation, Prof. Xu and Dr. Zhang visited our laboratory guided by Prof. Fang. Prof. Fang gave a detailed introduction about the main research directions, research progress and various instruments of the laboratory.

Professor Chunbao Xu, fellow of the Canadian Academy of Engineering and a tenured professor of the Department of Chemical Engineering at UWO in Canada, is a world-renown expert in the field of biomass refining. He is the Co-editor-in-chief of the International Journal of Chemical Reaction Engineering (IJCRE, an SCI Journal). In recent years, he has published nearly 200 papers in International academic journals with 7,700 cites and H index of 47.

加拿大工程院院士徐春保教授一行来访我院

2019年11月14日,应方真教授邀请,加拿大西安大略大学徐春宝教授和郑州大学张永生博士一行来访我院,进行学术交流与科研合作。徐教授与方教授在科研和学生交流方面有着长期的密切合作。

下午,徐春保教授为我院师生作了“Conversion of agricultural biomass into bio-based chemicals and materials”的专题报告,详细介绍了加拿大西安大略大学历史和主要研究方向,包括生物质、有机固废和污泥转化为生物能源、生物燃料和生物基化学品等方面的研究。特别向我们展示了如何利用农业生物质废弃物生产生物燃料以外的经济可行的材料和化学制品。本次学术讲座对可再生能源和生物质资源利用的未来发展和方向具有启发意义。

报告结束后,徐春保教授一行在方真教授的带领下参观了我们实验室,方老师为其详细介绍了目前实验室的主要研究方向、研究进展及实验室的各种仪器设备。

徐春保教授,现为加拿大工程院院士、加拿大西安大略大学化工系终身教授,生物质精炼领域的世界著名专家。担任SCI期刊化学反应工程国际期刊(IJCRE)的共同总编辑。近年来在学术期刊上发表论文近200篇,被引用7700余次,H因子47。

Prof. Sarani Zakaria from UKM (Malaysia) visited our Lab

Prof. Sarani Zakaria from UKM (Malaysia) visited our Lab

As invited by Prof. Zhen Fang, in the morning of October 5th, 2019, Prof Sarani Zakaria from Universiti Kebangsaan Malaysia (UKM; Bangi, Malaysia), visited our Lab. Prof. Fang gave a detailed introduction of the current research areas, research progress, and how to use the related instruments and equipment in our lab.

Prof. Z Fang has a long-term cooperative relationship with Prof. Zakaria’s group at UKM and co-supervised 4 PhD students (Drs. Fei Ling Pua, Siew Xian Chin, Suet Pin Fan, Umar Adli Bin Amran) and co-authored some research articles since 2011. He hopes that this visit will further enhance friendship and deepen cooperation in research, promote the development of international student exchanges and other activities, particularly jointly apply for research grants from different sources such as “One Belt and One Road”.

rpt

国立马来西亚大学Zakaria教授访问生物能源组

2019年10月05日上午,国立马来西亚大学Sarani Zakaria教授应方老师邀请来南京农业大学生物能源组访问和交流。Sarani Zakaria教授一行在方真教授带领下参观了生物能源实验室,方老师为其详细地介绍了目前实验室相关研究方向、研究进展以及相关仪器和设备的使用方法和功能。

方教授与Zakaria教授在马来西亚国立大学的团队有着长期的合作关系,自2011年以来,两人共同培养了4名马来西亚博士生(Fei Ling Pua潘慧琳小姐, Siew Xian Chin陈秀娴小姐, Suet Pin Fan范雪彬小姐, Umar Adli Bin Amran先生),同时也合作撰写了一些研究论文。方老师和Zakaria教授希望通过此次访问,能够进一步增进两团队的友谊,促进国际学生交流等活动的发展;深化科研合作,特别是联合申请不同渠道的科研资助,例如国家积极响应的“一带一路”建设工程项目。

Prof. RL Smith Jr. and Dr. HX Guo from Tohoku University (Japan) gave lectures

Prof. RL Smith Jr. and Dr. HX Guo from Tohoku University (Japan) gave lectures

As invited by Prof. Zhen Fang, from September 24th to 26th, 2019, Prof. Richard Lee Smith, Jr. and Assistant Prof. Haixin Guo from the School of Environmental Sciences, Supercritical Fluids Center, Tohoku University (Japan), visited our College of Engineering.

In the morning of September 25th, the chair of Agricultural Mechanization Department & Traffic and Vehicle Engineering Department, Prof. Ruiyin He; Professor Zhen Fang; the deputy director of the International Office of College, Mr. Biao Guo; and Dr. LJ Xu, met with Prof. Smith and Dr. HX Guo in Room C302, Yuxian Building. Mr. B Guo welcomed the arrival of Prof. Smith and Dr. HX Guo. He briefly introduced the current situation and history of the college from the aspects of college scale, subject setting, scientific research, international exchange and cooperation. Prof. RY He said that Prof. Z Fang has a long-term cooperative relationship with Supercritical Fluid Center at Tohoku University. He hopes that this visit will further enhance friendship and deepen cooperation in research, promote the development of international student exchanges and other activities, particularly to jointly host the 2020 “6th International Symposium & Exhibition on Aqua Science and Water Resources” (ISASWR-2020) holding in our college (Nanjing, Pukou).

Prof. Smith thanked the College for the hospitality. He gave a detailed introduction about Supercritical Fluid Center, Tohoku University, and its research fields, including supercritical fluid technology, green chemical processes, and also showed the research results in the field of green chemical processes for energy, food, chemicals and materials. He said that he hopes to deepen the inter-school cooperation relationship with our college in research and promote the exchange of teachers and students. Finally, he presented the key topics for the upcoming “ISASWR-2020” and both sides had a brief discussion.

In the afternoon of September 25th, Prof. Smith and Dr. HX Guo gave two invited lectures to teachers and students on “Green Chemical Processes for Energy, Food, Chemicals and Materials” and “Catalytic Systems with Ionic Liquid Additives for the Production of Platform Chemicals and Biofuels”, respectively. The academic lectures bring new enlightenment to the audiences on the directions of renewable energy and resources research and development.

Professor Richard Lee. Smith, Jr, obtained his Bachelor, Master and Ph.D. degrees in Chemical Engineering from Georgia Institute of Technology, USA. He is Professor of Supercritical Fluid Center, School of Environmental Sciences at Tohoku University (Sendai, Japan), specializing in thermodynamics, physical properties, supercritical fluids, and green processes. He is also the Region Editor (Asia) of the Journal of Supercritical Fluids and the editorial board member of Springer Book Series – Biofuels and Biorefineries. He has published more than 260 papers, patents and book chapters with H index of 48.

Dr. Haixin Guo, Female, Assistant Professor of Supercritical Fluid Center, School of Environmental Sciences, Tohoku University, Japan. She is committed to work in green chemistry, biomass resources that are transformed into high value-added chemicals with supercritical fluid-ionic liquid technology, separation engineering and other green chemical processes. In 2012 she obtained master degree in environmental engineering from Nankai University and in 2018 received doctorate in environmental science from Tohoku University. In April 2018, she worked at the Supercritical Fluid Center of Tohoku University and in May was quickly promoted to Assistant Professor of Environmental Science at Tohoku University.

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日本东北大学环境科学学院Smith教授一行来访我院

2019年9月24日-26日应方真教授邀请,日本东北大学环境科学学院Richard Lee. Smith, Jr教授和郭海心助理教授应邀来访我院。9月25日上午,农业机械化系/交通与车辆工程系主任何瑞银教授、方真教授、工学院办公室副主任郭彪等在育贤楼C302会见了Smith教授一行。

郭彪副主任对Smith教授和郭海心助理教授的到来表示欢迎。他从办学规模、学科设置、科学研究、国际交流与合作等方面简要介绍了学院基本情况。何瑞银表示,方真教授与日本东北大学环境科学学院有着长期合作关系,希望借此来访能够进一步增进友谊、深化合作,共同推进2020“第六届水科学与水资源国际研讨暨展览会”(ISASWR-2020) 在我院的举办,并推动国际学生交换等项目的开展。

Smith教授感谢学院的热情接待,详细介绍了日本东北大学超临界流体中心,及其实验室涉及的研究领域,包括超临界流体技术、绿色化学过程等,同时也展示了实验室在能源、食品、化工和材料的绿色化工过程领域的研究成果。他表示,希望与我院深化校际合作关系,增进师生交流。

9月25日下午,Smith教授和郭海心助理教授分别为我院师生作“Green Chemical Processes for Energy, Food, Chemicals and Materials”“离子液体催化生物质转化的机理研究”的专题报告。学术报告为学院师生带来许多关于新能源研究和发展方向的新启示。

Richard Lee. Smith, Jr教授,美国佐治亚理工学院化学工程学士、硕士和博士。日本东北大学环境科学学院超临界流体中心教授,致力于热力学、物理特性、超临界流体和绿色过程等方面研究。兼任Journal of Supercritical Fluids杂志亚洲地区主编以及Springer Nature,Biofuels and Biorefineries系列丛书编委。他发表了260余篇论文、专利和书章节等,H指数为48。

郭海心博士(女),日本东北大学环境科学学院超临界流体中心助理教授。致力于绿色化学,生物质资源转化为高附加值的化学品、超临界流体-离子液体技术、分离工学等方面研究。分别于2012年和2018年获得南开大学环境工程硕士学位和日本东北大学先端环境创成学专业博士学位。2018年4月于日本东北大学超临界流体中心任职,5月升任为日本东北大学环境科学学院助理教授。

High-Concentrated Substrate Enzymatic Hydrolysis of Pretreated Rice Straw with Glycerol and Aluminum Chloride at Low Cellulase Loadings

High-Concentrated Substrate Enzymatic Hydrolysis of Pretreated Rice Straw with Glycerol and Aluminum Chloride at Low Cellulase Loadings

Based on a central composite design, glycerol and AlCl3 pretreated rice straw with 0.08 mol/L AlCl3 at 146.8 °C for 20 min, resulting in 83% delignification, 94% hemicellulose removal, and 92% cellulose recovery for a remarkable glucose yield of 65.7% at high solid loads (15%) and low cellulase loading (3.3 FPU/g dry substrate) with adding Tween 80 (40 mg/g substrate). (通过响应面优化,在146.8 °C和0.08 mol/L AlCl3条件下,水稻秸秆经甘油-氯化铝预处理20 min后,保留92%的纤维素,同时去除83%的木质素和94%的半纤维素;3 FPU/g干基质和15%基质浓度条件下,添加40 mg/g 干基 Tween 80,酶水解48 h,预处理后水稻秸秆的酶解率可达到65.7%。)

Recently, PhD student Mr. Song Tang supervised by Prof. Zhen FANG developed a glycerol and aluminum chloride pretreatment for lignocellulosic biomass. Rice straw was pretreated with glycerol and AlCl3 for enzymatic hydrolysis at low cellulase loadings. Based on a central composite design, 83% delignification, 94% hemicellulose removal, and 92% cellulose recovery (or 76% cellulose in solid residue) were achieved under the optimized pretreatment conditions (0.08 mol/L AlCl3 as catalyst at 146.8 °C for 20 min with 90% glycerol). During glycerol-AlCl3 pretreatment, the lignin-carbohydrate complex was depolymerized, resulting in the complex and recalcitrant construction of straw effectively being destroyed. The enzyme adsorption ability of pretreated straw was 16.5 times that for the original sample. After pretreatment, glucose yield was increased by 2.4 times to 74% for 48 h. Moreover, concentrated solid (15%) with low cellulase loading (3.3 FPU/g dry substrate) achieved 58.6% glucose yield, and further increased by 12% to 65.7% by adding Tween 80.

The results were published:

S Tang, Q Dong, Zhen Fang*, WJ Cong, ZD Miao, High-Concentrated Substrate Enzymatic Hydrolysis of Pretreated Rice Straw with Glycerol and Aluminum Chloride at Low Cellulase Loadings, Bioresource Technology, 294, 122164 (2019).

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甘油和氯化铝预处理水稻秸秆用于低纤维素酶载量条件下高基质浓度酶水解

最近,博士生唐松(男)同学在方老师的指导下,开发出一种应用于木质纤维素生物质的甘油-氯化铝预处理技术,其对木质纤维素组分分离具有极好的选择性。通过响应面优化,水稻秸秆在146.8 °C和0.08 mol/L AlCl3条件下,处理20 min后,92%的纤维素被保留,83%的木质素和94%的半纤维素被去除。同时,固体残渣中纤维素含量达到76%。在甘油-AlCl3预处理过程中,木质素-碳水化合物形成的复合物被解聚,导致秸秆复杂和顽固的结构被有效地破坏。水稻秸秆经预处理后,对纤维素酶的吸附能力提高了16.5倍,酶解率较原始水稻秸秆提高2.4倍,达到了74%。此外,在3 FPU/g和15%基质浓度条件下,酶水解48 h,预处理后水稻秸秆的酶解率达到58.6%,且添加40 mg/g 干基 Tween 80后,提高了12%,达到65.7%。

结果发表在Bioresource Technology:

S Tang, Q Dong, Zhen Fang*, WJ Cong, ZD Miao, High-Concentrated Substrate Enzymatic Hydrolysis of Pretreated Rice Straw with Glycerol and Aluminum Chloride at Low Cellulase Loadings, Bioresource Technology, 294, 122164 (2019).

Dr. LJ Xu and Prof. Zhen Fang attended the 10th National conference on Environmental Chemistry (NCEC 2019)

Dr. LJ Xu and Prof. Zhen Fang attended the 10th National conference on Environmental Chemistry (NCEC 2019)

On August 16-18, 2019, Dr. Xu and Prof. Fang attended the 10th National conference on Environmental Chemistry (NCEC 2019) held in Nankai University, Tianjin invited by Prof. XH Qi. Prof. Fang gave a keynote speech entitled “Hydrolysis of Lignocelluloses for the catalytic production of biofuels and chemicals” to introduce biomass green transformation, hydrolysis, production of biodiesel via catalytic transesterification, catalytic synthesis of bio-chemical and catalytic pyrolysis. Dr. Xu gave an oral speech entitled “Catalytic fast pyrolysis of polyethylene terephthalate to selectively producing Terephthalonitrile and benzenitrile under ammonia atmosphere ”.

2019年8月16-18日,方真教授和徐禄江老师出席了在天津南开大学举行的第十届全国环境化学大会(NCEC 2019),方真教授作了《Hydrolysis of Lignocelluloses for the catalytic production of biofuels and chemicals》的主旨报告,内容包括:生物质绿色转化、水解、催化酯交换制备生物柴油、催化合成化学品和催化热解。徐禄江老师作了《氨气氛围聚催化热解对苯二甲酸乙二醇酯选择性制备对苯二甲腈和苯甲腈》的口头报告。

 

Co-production of phenolic oil and deoxidation catalyst via fast pyrolysis of phenol-formaldehyde resin with Ca(OH)2

Co-production of phenolic oil and deoxidation catalyst via fast pyrolysis of phenol-formaldehyde resin with Ca(OH)2

Recently, Dr. Lujiang Xu and Prof. Zhen FANG have developed a catalytic pyrolysis process for direct conversion of phenol-formaldehyde resin to produce phenolic oil and deoxidation catalyst.

PF resins were used to co-produce phenolic oil and CaO/carbon catalyst by fast pyrolysis with Ca(OH)2 with oil yield of 37% containing 80% phenols (Ca(OH)2催化热解酚醛树脂共生产酚醛油和CaO/炭催化剂,油产率为37%,含80%酚类).

Phenol-formaldehyde (PF) resin was widely used in industry, it would cause an adverse effect on the environment if without applicable treatments of resin wastes. Triglycrides (e.g., soybean oil) were abundant in the nature, but cannot be used directly as engine fuel. The deoxygenation of triglycrides was necessary for producing liquid fuel similar to that derived from petroleum. Herein, PF resin was used to co-produce phenolic-rich oil and CaO/char deoxygenation catalyst by catalytic fast pyrolysis with Ca(OH)2. The CaO/char was used as catalyst to catalytic deoxygenation of soybean oil via catalytic fast pyrolysis process. It was found that Ca(OH)2 changed the thermal decomposition behaviours of PF resin dramatically and promoted the cracking reactions to form more monophenol compounds. The optimal conditions for producing phenol-rich oil (containing 9.1% aromatic hydrocarbons and 82.8% phenols, GC-MS area fraction) with 37.3% yield were 650 °C and 5.0% Ca(OH)2 catalyst. Meanwhile, the total carbon yield of targeted phenols reached 33.7%. Solid residue (char) was further pyrolyzed at 800 °C for producing CaO/char catalyst that helped to reduce the bio-oil oxygen content from 14.4% to 2.4% in the pyrolysis of soybean oil. The peak area % of aromatic hydrocarbons in the oil was 86.8%, and indicated it could be used as gasoline. Phenolic oil from PF resin and aromatic hydrocarbons-rich oil from vegetable oil are easily produced by fast pyrolysis with calcium catalyst.

Related results were published:

LJ Xu, QQ Zhong, Q Dong, LY Zhang, Zhen Fang*, Co-production of phenolic oil and CaO/char deoxidation catalyst via catalytic fast pyrolysis of phenol-formaldehyde resin with Ca(OH)2, Journal of Analytical and Applied Pyrolysis, https://doi.org/10.1016/j.jaap.2019.104663 (2019).

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催化热解酚醛树脂共生产酚醛油和CaO/炭催化剂

最近,徐绿江博士和方真教授开发了一种直接转化酚醛树脂生产酚醛油和脱氧催化剂的催化热解工艺。

酚醛树脂在工业上得到了广泛的应用,如果不进行适当的处理,会对环境造成不良影响。甘油三脂(如大豆油)在自然界中含量丰富,但不能直接用作发动机燃料。甘油三脂的脱氧对于生产类似于石油液体燃料是必要的。在此基础上,采用酚醛树脂与Ca(OH)2催化快速热解制备了富酚油和CaO/炭脱氧催化剂。以氧化钙/炭为催化剂,采用催化快速热解法对大豆油进行催化脱氧。结果表明,Ca(OH)2能显著改变酚醛树脂的热分解行为,促进裂解反应形成更多的单酚类化合物。

合成37.3%高酚油(含9.1%芳烃和82.8%苯酚)的最优条件为 650℃和5.0%Ca(OH)2催化剂。同时,目标酚的总碳产率达到33.7%。在800℃下对固体残渣(炭)进行进一步热解,制备出CaO/炭催化剂。该催化剂使豆油热解过程中生物油氧含量由14.4%降至2.4%。油中芳烃的GC-MS峰面积百分比为86.8%,表明它可以作为汽油使用。酚醛树脂制备酚醛油和植物油制备富芳烃油,在钙催化剂的作用下,通过快速热解得以实现。

详情可见:

LJ Xu, QQ Zhong, Q Dong, LY Zhang, Zhen Fang*, Co-production of phenolic oil and CaO/char deoxidation catalyst via catalytic fast pyrolysis of phenol-formaldehyde resin with Ca(OH)2, Journal of Analytical and Applied Pyrolysis, https://doi.org/10.1016/j.jaap.2019.104663 (2019).

Mr. Xiao-jie Wei and Miss Le-yao Zhang successfully defended their theses

Mr. Xiao-jie Wei and Miss Le-yao Zhang successfully defended their theses

On May 29, 2019, Mr. Xiao-jie Wei and Miss Le-yao Zhang supervised by Prof. Zhen Fang with the help of Drs. Lujiang Xu and Xiao Kong, successfully defended their theses in A101 Huixian Building, Pukou Campus of Nanjing Agricultural University. The defending committee was composed of Profs. Yongfu Zhao (chair) and Hongying Huang from Jiangsu Provincial Academy of Agricultural Sciences, Prof. Xiaohua Wang and Associate Professor Kunquan Li from Nanjing Agricultural University.

All the members of the panel listened to the presentations, raised corresponding questions and reviewed the relevant information after hearing the thesis presentations by Mr. Wei and Miss Zhang. After reviewing and defending, the panel agreed that Mr. Wei and Miss Zhang had successfully completed their research and course requirements on agricultural bio-environment and energy engineering. Mr. Wei studied the catalytic condensation of furfural and acetone alcohol to furanic biofuels to optimize technological conditions with La-based trimetallic catalysts with his thesis entitled “Lanthanide complex metal catalysts for furanic biofuels preparation”. Miss Zhang studied the green recycling of polyvinyl chloride (PVC) with her thesis entitled “Study on the preparation of hydrocarbons by catalytic pyrolysis dechlorination of polyvinyl chloride”. She modified PVC plastic with catalyst of calcium hydroxide to catalyze the conversion of PVC to hydrocarbons by fast pyrolysis technology. Both students worked hard and published 2 academic papers. After the jury voted by secret ballot with Grade B, the panel agreed to confer Master of Engineering Degree to Mr. Xiao-jie Wei and Miss Le-yao Zhang.

Both students got a decent job in manufacturing industry as an engineer.

Congratulations!

生物能源组工程硕士生魏孝捷、张乐瑶顺利通过毕业答辩

2019年5月29日,南京农业大学生物能源2017级工程硕士研究生魏孝捷(男)与张乐瑶(女)毕业答辩会在南京农业大学浦口校区汇贤楼A101举行。答辩评审委员会主席由江苏省农业科学院赵永富研究员担任,来自江苏省农科院的赵永富研究员与黄红英研究员,南京农业大学的王效华教授与李坤权副教授共四位专家担任评审委员。

答辩会上,答辩委员会主席及各位评委在听取了魏孝捷与张乐瑶同学在读期间的答辩报告后,进行了充分的问答和审阅相关资料。经过评审决议后,专家组一致认为魏孝捷与张乐瑶同学顺利完成了农业生物环境与能源方面的研究和学习要求。魏孝捷同学在毕业论文《镧系复合金属催化剂催化制备呋喃类生物燃料》中研究了La系三金属催化剂对于催化糠醛丙酮醇缩合制备呋喃类生物燃料,并针对高效的复合金属氧化物的最优工艺条件进行了研究;张乐瑶同学在毕业论文《聚氯乙烯催化热解脱氯制备碳氢化合物的研究》中对聚氯乙烯(PVC)塑料绿色回收进行研究,针对氢氧化钙对PVC进行改性,利用催化热解技术将聚氯乙烯催化为碳氢化合物,报告数据可靠。两位同学在校期间工作努力,共发表学术论文2篇。经评委会无记名投票表决,评定等级为良好,一致同意通过毕业答辩。

祝贺魏孝捷、张乐瑶同学!