Biomass Group, Nanjing Agricultural University, PO Box 68, 40 Dianjiangtai Road, Nanjing 210031

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

As invited by Prof. Zhen Fang, in the morning of October 5^th, 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”.

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

As invited by Prof. Zhen Fang, from September 24^th to 26^th, 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 25^th, 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 “6^th 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 25^th, 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

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 10^th 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

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).