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

Mr. Zhou and Mr. Song successfully defended their Master theses

On June 2 and June 20, 2022, Mr. Xian-jun Zhou supervised by Dr. Lujiang Xu and Mr. Yan-qing Song supervised by Prof. Zhen Fang, successfully defended their theses. The defending committees were composed of Profs. Wen-qing Yin (chair), Hua Li, associate Profs. Yan-yan Ge & Fei Hu from Nanjing Agricultural University (NAU) and Prof. Zhi-tang Zhong from Jiangsu Agricultural Machinery Technology Extension Station for Mr. Zhou; as well as Profs. Chun-xia He (chair) and Kun-quan Li from NAU, and Prof. Hai-jun Chen from Nanjing Technology University for Mr. Song.

Mr. Zhou and Mr. Song presented their research results for Master theses, the committee members raised relevant questions. Based on the replies and theses reviewed, the panels agreed that Mr. Zhou and Mr. Song had successfully completed their research and course requirements in mechanical, and agricultural mechanization engineering. Mr. Zhou studied the synergistic effect of co-pyrolysis of polyoxymethylene and cellulose with his thesis entitled “Study on Producing Pyridines via Ammoniated Catalytic Co-pyrolysis of Cellulose and Polyoxymethylene and Design of Two-stage Pyrolysis Device”. Mr. Song studied hydrothermal gasification of agricultural wastes in supercritical water with his thesis entitled “Catalytic Gasification of Cotton Stalk over Ni-La/Spent Bleaching Clay to Produce Hydrogen in Supercritical Water”. Both Mr. Zhou and Mr. Song published one first-authored Journal paper.

After the juries voted by secret ballot, the panels agreed to confer Master of Engineering degree to Mr. Xian-jun Zhou, and Master of Science in Engineering degree to Mr. Yan-qing Song, subjected to the approval by the Academic Degrees Committees of the college and university.

Congratulations to Mr. Zhou and Mr. Song!

Papers published:

XJ Zhou, LQ Jiang, H Zhang, CY Dong, LJ Xu*, Catalytic Co-Pyrolysis of Cellulose and Waste Polyoxymethylene to Improve Producing Pyridines Compounds over Commercial HZSM-5 Zeolites under Ammonia Atmosphere, Journal of Analytical and Applied Pyrolysis, 158 (2021), 105275.

YQ Song, S Nanda, WJ Cong, J Sun, GH Dong, A Magdziarz, Zhen Fang*, AK Dalai, JA Kozinski, Hydrogen Production from Cotton Stalk over Ni-La Catalysts Supported on Spent Bleaching Clay via Hydrothermal Gasification, Industrial Crops & Products, 186 (2022) 115228.

周贤君同志和宋彦庆同志顺利通过硕士论文答辩

2022年6月2日，6月20日，南京农业大学生物能源组2019级工学硕士研究生周贤君和宋彦庆毕业答辩会在南京农业大学浦口校区举行。南京农业大学的尹文庆教授担任周贤君同志的答辩评委会主席，李骅教授、葛艳艳副教授和胡飞副教授以及来自江苏省农业机械技术推广站钟志堂研究员担任评审委员。南京农业大学何春霞教授担任宋彦庆同志的答辩评委会主席，李坤权教授和南京工业大学的何海军教授担任评审委员。

答辩会上，周贤君同志和宋彦庆同志对其在校期间的学术论文进行汇报，同时答辩委员会主席和各位评委提出了相关问题。根据周贤君同志和宋彦庆同志的问题回答以及学位论文的评阅意见，评委会经过评审决议，一致认为周贤君同志和宋彦庆同志完成了机械，和农业机械化工程的研究和课程要求。周贤君同志在毕业论文《氨化催化共热解纤维素和聚甲醛制吡啶碱研究及双段热解装置设计》中研究了聚甲醛和纤维素热解的协同效应。宋彦庆同志在毕业论文《超临界水中Ni-La/废白土催化棉花秸秆气化产氢的研究》中研究了Ni-La/废白土催化气化棉杆制氢的课题，实现了棉花秸秆的高效制氢。周贤君和宋彦庆同志均以第一作者各发表论文一篇。

经评委会无记名投票表决，一致同意周贤君同志和宋彦庆同志通过硕士学位论文答辩，建议授予周贤君同志专业工程硕士学位，宋彦庆同志工学硕士学位。

祝贺周贤君同志和宋彦庆同志！

发表的论文：

XJ Zhou, LQ Jiang, H Zhang, CY Dong, LJ Xu*, Catalytic Co-Pyrolysis of Cellulose and Waste Polyoxymethylene to Improve Producing Pyridines Compounds over Commercial HZSM-5 Zeolites under Ammonia Atmosphere, Journal of Analytical and Applied Pyrolysis, 158 (2021), 105275.

YQ Song, S Nanda, WJ Cong, J Sun, GH Dong, A Magdziarz, Zhen Fang*, AK Dalai, JA Kozinski, Hydrogen Production from Cotton Stalk over Ni-La Catalysts Supported on Spent Bleaching Clay via Hydrothermal Gasification, Industrial Crops & Products, 186 (2022) 115228.

Hydrogen production from cotton stalk over Ni-La catalysts supported on spent bleaching clay via hydrothermal gasification

Recently, master student Mr. Yan-qing Song supervised by Prof. Zhen Fang, collaborated with Dr. A Magdziarz at AGH University of Science and Technology (Poland), Prof. AK Dalai University of Saskatchewan (Canada) and Prof. JA Kozinski at Lakehead University (Canada) published a research article in Industrial Crops & Products about hydrogen production from cotton stalk with Ni-La/ supported on spent bleaching clay (SBC) catalysts.

Cotton stalk was gasified to produce H₂ with Ni-La based catalysts in subcritical and supercritical water. Approximately 90% H₂ yield was obtained under optimized conditions (360 ^oC, 0.5 g Ni-La catalyst loading, 0.5 g biomass and 10 min) by an orthogonal design with Ni-La/SBC. In addition, the H₂ yield of rice and wheat straw increased by 41.5 and 39.5 times, respectively at optimized conditions. It was found that the activity of Ni-La materials supported with SBC ash and Al₂O₃ was similar, with H₂ yields of 108.3% and 115.1% at 380 ^oC, respectively in 5 min. Catalysts were characterized by NH₃-TPD, TPR, XRD, BET and XPS. SBC ash provided a high specific surface area (94.4 m²/g) for the Ni-La catalyst. La-promoted Ni/SBC (0.19 mmol/g) had a stronger acidity than Ni/SBC (0.16 mmol/g). Ni-La/SBC had a broad reduction peak, indicating the uniform dispersion of Ni on the support. Ni-La/SBC materials not only realized the reuse of SBC but also effectively promoted the hydrothermal gasification of agricultural wastes. Related results were published：

YQ Song, S Nanda, WJ Cong, J Sun, GH Dong, A Magdziarz, Zhen Fang*, AK Dalai, JA Kozinski, Hydrogen production from cotton stalk over Ni-La catalysts supported on spent bleaching clay via hydrothermal gasification, Industrial Crops & Products, 186 (2022) 115228. https://doi.org/10.1016/j.indcrop.2022.115228.

Ni-La materials supported in SBC ash for hydrothermal gasification of cotton stalk with 135.5% H₂ yield. (水热条件下Ni-La/废白土催化气化棉花秸秆，H₂产率为135.5%。)

水热条件下Ni-La/废白土催化棉花秸秆气化产氢

最近，硕士生宋彦庆在方真老师的指导下，与波兰AGH科技大学A Magdziarz博士, 加拿大Saskatchewan大学 AK Dalai院士以及加拿大Lakehead 大学工学院院长JA Kozinski院士在国际学术期刊 Industrial Crops & Products发表题为“水热条件下Ni-La/废白土催化棉花秸秆气化产氢”的研究性论文。

使用Ni-La基催化剂在亚临界和超临界水中催化气化棉秆生产H₂。以Ni-La/废白土（SBC）为催化剂，通过正交实验，筛选出最优反应条件：360 ^oC、0.5 g Ni-La/SBC、0.5 g 棉杆、10 分钟，获得了约 90% 的 H₂ 产率。此外，优化条件下水稻和小麦秸秆的H₂产量分别提高了41.5倍和39.5倍。同时，发现 SBC 灰和 Al₂O₃ 负载的 Ni-La 材料的活性相似，在 380 ^oC 下反应 5 分钟的 H₂ 产率分别为 108.3% 和 115.1%。通过NH₃-TPD、TPR、XRD、BET和XPS对催化剂进行了表征。 SBC灰为 Ni-La 催化剂提供了高比表面积 (94.4 m²/g)。La 促进的Ni/SBC (0.19 mmol/g)比Ni/SBC (0.16 mmol/g)具有更强的酸性。Ni-La/SBC 有一个较宽的还原峰，表明 Ni 在载体上均匀分散。Ni-La/SBC材料不仅实现了废白土的再利用，还有效促进了农业废弃物的水热气化。详情可见：

YQ Song, S Nanda, WJ Cong, J Sun, GH Dong, A Magdziarz, Zhen Fang*, AK Dalai, JA Kozinski, Hydrogen production from cotton stalk over Ni-La catalysts supported on spent bleaching clay via hydrothermal gasification, Industrial Crops & Products, 186 (2022) 115228. https://doi.org/10.1016/j.indcrop.2022.115228.

演讲Three Invited Lectures by Prof. Zhen Fang

Recently, Prof. Zhen Fang gave three invited lectures in Biorefineries.

On June 1, 2022, Prof. Fang gave a lecture entitled “Biorefineries” to undergraduate students at Nanjing Agricultural University (NJAU).

The talk included 6 parts:

• Bioresources and biorefineries
• Hydrolysis (i) Fast hydrolysis, (ii) Catalytic hydrolysis (iii) Enzymatic hydrolysis
• Sugars via chemical routes
• Sugars via biological routes
• Biodiesel
• Conclusions

After lecture, Prof. Zhen Fang was invited as Special Supervisor by vice-President Weichun Dong of NJAU.

On December 28, 2021, Prof. Zhen Fang went to Guangzhou, attending the Innovation and Development Forum by Guangdong Academy of Sciences and gave an invited lecture on biorefineries. In the afternoon, Prof. Fang gave a lecture on the Famous Teachers’ Forum for Light Chemical Engineering as invited by President Xueqing Qiu, and met President Qiu for further collaborations.

特邀演讲

最近，方真教授做了三次演讲。

2022年6月1日，方老师受南京农业大学董维春副校长要求，在金善宝大讲堂给本科生做了近1小时的生物炼制报告。

演讲包括6个部分：

一 生物质资源和生物炼制

二 水解 1.快速水解 2.催化水解 3.酶解

三 化学转化糖

四 生物转化糖

五 生物柴油

六 结论

讲座结束后，董维春副校长给方老师颁发了金善宝特聘导师证书。

另外，2021年12月28日，方老师在广州出席了广东省科学院创新发展论坛，并作了特邀报告。下午，应广东工业大学邱学青校长之邀，在轻化名师讲坛（一百七十六）作了特邀报告。会后，会见邱学青校长。

会议报告Plenary/keynote speeches

Recently, Prof. Zhen Fang gave two talks.

On April 9, 2022, Prof. Fang gave a Plenary Talk entitled “Green Production of Biodiesel with Recyclable Bifunctional Catalysts” in the 7^th Int’l Conf. on Biomass Energy (ICBE2022, Xiamen, Fujian).

The talk included 7 parts:

• Raw oils
• Ultrasound and microwave
• Solid acid
• Solid base
• Bifunctional acid-base catalyst
• Magnetized catalysts
• Conclusions

On May 15-18, 2022, PhD student Mr. Pei-dong Wu and Prof. Fang attended the 26^th  Canadian Symposium on Catalysis (CSC 2022) held in in Vancouver, British Columbia, Canada invited by Prof. Charles Xu. Prof. Fang gave a keynote speech entitled “One-Step Production of Jatropha Biodiesel by Magnetic Acid-Base Bifunctional Catalysts” to introduce green production of biodiesel via magnetic acid-base bifunctional nanocatalyst. Mr. Wu gave an oral speech entitled “Synergistic Catalysis of Co-Zr/Cn_x Bimetallic Nanoparticles Enables Reductive Amination of Bio-Based Levulinic Acid”.

国际会议大会报告/主题演讲

最近，方真教授做了两次演讲。

2022年4月9日，方教授在第七届国际生物质能大会（ICBE2022，福建厦门）上发表了题为“利用可回收双功能催化剂绿色生产生物柴油”的大会演讲。

演讲包括7个部分：

• 原料油
• 超声波和微波
• 固体酸
• 固体碱
• 双功能酸碱催化剂
• 磁化催化剂
• 结论

2022年5月15-18日，由加拿大化学研究所催化部主办的第26届加拿大催化研讨会（The 26^th Canadian Symposium on Catalysis）在加拿大西部城市温哥华举行。方真教授受邀作为主旨演讲人作了题为：“磁性酸碱双功能催化剂一步法生产小桐子生物柴油”的主旨报告。演讲内容主要包括磁性酸碱双功能纳米催化剂合成及在绿色转化生产生物柴油中的应用。博士生吴培栋作了《具有协同作用的Co-Zr/CN_x双金属纳米颗粒催化还原胺化生物质基乙酰丙酸》的口头报告。

Enhancing α-etherification of lignin in Eucalyptus diol pretreatment to improve lignin monomer production

Recently, Dr. Chengyu Dong and Prof. Zhen Fang, collaborated with Prof. G Cravotto at University of Turin (Italy) and Dr. S-Y Leu at Hong Kong Polytechnic University published a paper about enhancing α-etherification of lignin in Eucalyptus diol pretreatment.

In this work, α-etherification of lignin in diol pretreatment was selectively enhanced at mild temperature for lignin isolation and subsequent valorisation. More than 90% of lignin was removed from Eucalyptus at 120 °C in diol (ethylene glycol and 1,4-butanediol) pretreatment, resulting in >90% cellulose conversion in 24 h at 7.5 FPU/g glucan cellulase loading. Subsequent catalytic transfer hydrogenolysis of the isolated lignins with Ru/C in ethanol gave 15% monomer yield on native lignin basis, 5 times of that from the technical ethanol process (170 °C). HSQC NMR analysis revealed that diol pretreated lignin (120 °C) contained ~23% α-etherified β-O-4 interunit bonds, indicating that lignin degradation (i.e. cleavage of β-O-4 bonds) was suppressed via etherification by grafting a hydroxyl group at the α position of lignin. This finding was consistent with the isolated lignin (120 °C) had less number of phenolic OH and higher molecular weight via ³¹P NMR and GPC analysis. ³¹P NMR analysis also revealed that diol isolated lignin contained more numbers of aliphatic OH than ethanol-isolated lignin, which increased lignin solubility and maintained the high yield (>80%) of isolated lignin from Eucalyptus at 120 °C as expected. In summary, diol pretreatment of woody biomass can effectively isolate more lignin for hydrogenolysis to valued-added monomers without compromising the isolated yield of lignin and hydrolysis yield of remained cellulose.

Related results were published in Industry crops and products:

CY Dong, XZ Meng, S-Y Leu, LJ Xu, ZL Wu, G Cravotto, Zhen Fang*, Enhancing a-Etherification of Lignin in Eucalyptus Diol Pretreatment to Improve Lignin Monomer Production, Industrial Crops and Products, 185, 115130, https://doi.org/10.1016/j.indcrop.2022.115130 (2022).

Enhancing α-etherification of lignin by diol pretreatment at mild temperature (120 °C) to isolate lignin for producing 5 times monomer yield of that from technical ethanol pretreatment (170 °C) by hydrogenolysis. (在二元醇预处理过程中，木质素的α-醚化在温和温度(120 ℃)下增强，其分离木质素氢解单体收率达到工业乙醇预处理(170 ℃)单体收率的5倍)

董澄宇博士在国际学术期刊Industry crops and products发表学术论文

最近，农业工程期刊Industry crops and products (第一署名单位为南京农业大学，第一作者为董澄宇博士，通讯作者为方真教授, 合作单位意大利都灵大学G Cravotto教授和香港理工大学S-Y Leu 博士)发表了一篇关于提高桉树二醇预处理过程中木质素α-醚化的文章。

在该研究中，二元醇预处理中木质素a-醚化在温和的温度下被选择性地增强，可高效分离木质素并利于木质素的高值化利用。在120 ℃，二元醇（乙二醇和1,4-预处理的桉树木质素去除率达到90%以上，纤维素在24小时内转化率即为90%。随后在乙醇中用钌/碳催化氢解木质素，单体产率为15%，是工业乙醇预处理(170 ℃)的5倍。二维核磁共振分析表明，二元醇预处理木质素（120 °C） 包含23%α-醚化β-O-4化学键，表明木质素降解（即β-O-4键的断裂）被在木质素α-醚化抑制。这个结果与木质素的核磁磷谱分析和凝胶色谱结果分析抑制，该条件下分离的木质素酚羟基含量少，分子量高。核磁磷谱分析还表明，二元醇分离的木质素比乙醇分离的木质素含有更多的脂肪族羟基，这增加了木质素的溶解度并保持了较高的分离效率(120 ℃时，桉树木质素的分离率为80%)。综上所述，木质生物质的二醇预处理可以有效地分离出更多的木质素氢解为高附加值的单体，而不影响木质素的分离效率和纤维素的水解效率。

结果发表在Industry crops and products：

CY Dong, XZ Meng, S-Y Leu, LJ Xu, ZL Wu, G Cravotto, Zhen Fang*, Enhancing a-Etherification of Lignin in Eucalyptus Diol Pretreatment to Improve Lignin Monomer Production, Industrial Crops and Products, 185, 115130, https://doi.org/10.1016/j.indcrop.2022.115130 (2022).