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

A green process for biodiesel and hydrogen coproduction from waste oils with a magnetic metal-organic framework derived material

Recently, Dr. Wen-jie Cong (female) supervised by Prof. Zhen Fang published a research article in Biomass & Bioenergy about biodiesel and hydrogen coproduction from waste oils with a solid base derived from magnetic metal-organic framework.

Magnetic self-assembly metal-organic frameworks (MOFs) were constructed for the co-production of biodiesel and hydrogen from waste oils. The highly active MOF nanoparticles were synthesized and catalyzed crude glycerol for 126.8% hydrogen yield in subcritical water (350 ℃, 5 min). By coupling alkali with MOF-derived carriers, continuous process of fast production of biodiesel (with microwave heating at 90 ℃ in 15 min, 15:1 methanol/oil molar ratio and 9 wt.% catalyst dosage) and hydrogen (350 ℃, 5 min) were achieved with yield of 95.3% biodiesel from waste oil (AV was 3.95 mg KOH) and 102.6% H2 from crude glycerol by-product, respectively. The nanoparticles were magnetically separated for 5 cycles with 95% biodiesel yield and increased hydrogen yield by 50% after deactivated. Characterization techniques showed active sites of MOF-derived nanoparticles were well dispersed with surface area increased by 3.9 times for highly efficient production of biodiesel and hydrogen. It revealed that MOF materials can be designed to make active catalysts and carriers for loading catalytic sites for biomass conversions to targeted biofuels.

A self-assembled nano Ni-MOF was synthesized as magnetic carrier and catalyst support for biodiesel and hydrothermal hydrogen production from waste oils. (以自组装纳米Ni-MOF作为磁性载体制备催化剂，以废弃油脂为原料联合生产生物柴油和氢气）

Related results were accepted in Biomass & Bioenergy:

WJ Cong, J Yang, JG Zhang, Zhen Fang^*, ZD Miao. A green process for biodiesel and hydrogen coproduction from waste oils with a magnetic metal-organic framework derived material. Biomass & Bioenergy. 175 (2023) 106871. https://doi.org/10.1016/j.biombioe.2023.106871.

磁性金属有机骨架衍生材料用于废油联产生物柴油和氢气的绿色工艺

最近，丛文杰博士（女）在方老师的指导下，在国际学术期刊Biomass & Bioenergy（IF5.77，Q1）发表金属有机框架衍生固体碱联合制备生物柴油和氢气的研究性论文。

本研究通过制备自组装磁性纳米金属有机骨架 (Ni-MOF)，构建了以废弃油为原料联合制备生物柴油和氢气的绿色工艺。在亚临界水（350 ℃，5 min）条件下，该高活性Ni-MOF纳米颗粒催化粗甘油水热制氢，氢气产率高达126.8%。以该Ni-MOF为载体制备磁性固体碱，实现高酸值废弃油（酸值3.95 mg KOH）制备生物柴油，产率为95.3%（90 ℃、15 min、甲醇/油摩尔比15:1、催化剂用量为9 wt.%），该磁性固体碱经磁性分离后重复使用5次，生物柴油产率为95%；失活后的磁性固体碱用于水热气化副产物粗甘油制备氢气，产率为102.6%（350 ℃，5 min），氢气产率提高了50%。研究结果表明该Ni-MOF纳米颗粒活性位点分散性好，比表面积增加了3.9倍，可高效联产生物柴油和氢气。该MOF材料可以设计成多功能磁性载体和高性能催化剂，用于负载高活性催化位点实现生物质快速转化为生物燃料。

详情可见：

WJ Cong, J Yang, JG Zhang, Zhen Fang^*, ZD Miao. A green process for biodiesel and hydrogen coproduction from waste oils with a magnetic metal-organic framework derived material. Biomass & Bioenergy. 175 (2023) 106871. https://doi.org/10.1016/j.biombioe.2023.106871.

Efficient lipid synthesis of Chlorella pyrenoidosa promoted under heavy metals from electric arc furnace slag

Recently, Dr Yi-Tong Wang (female, Associate Professor, College of Metallurgy and Energy, North China University of Science and Technology) and Prof. Zhen Fang published an article in Journal of Cleaner Production (IF: 11.072, Q1) about using efficient lipid synthesis of Chlorella pyrenoidosa microalgae promoted under heavy metals from electric arc furnace slag.

Electric arc furnace slag is highly productive and rich in elements, which can be used as a nutrient source for microalgae. The study investigated the regulation of growth and lipid synthesis of Chlorella pyrenoidosa in electric arc furnace slag leaching solution, and citric acid electric arc furnace slag co-leaching solution, to achieve lipid production while treating metallurgical solid waste. The results showed that the highest biomass and lipid contents were 0.23 g/L and 45.89 wt%, respectively, when BG11 was added to the electric arc furnace slag leaching solution. The highest biomass and lipid contents were 0.25 g/L and 33.37 wt%, respectively, for the addition of citric acid electric arc furnace slag leaching solution at BG11. Various metal ions in the electric arc furnace slag leaching solution increased the biomass lipid content by modulating acetyl-CoA carboxylase, malic enzyme, and phosphoenolpyruvate carboxylase activities. This study helps to solve the problem of the high cost of microalgae culture and metallurgical solid waste treatment while generating lipids and provides a new green pathway for the commercialization of microalgae.

Related results were accepted in Journal of Cleaner Production:

Q Yu, TJ Liu, YN Zeng, YT Wang*, JG Li*, LL Kang, R Ji, FP Wang, XM Wang, B Liu, S Cai, Zhen Fang*. Efficient lipid synthesis of Chlorella pyrenoidosa promoted under heavy metals from electric arc furnace slag. Journal of Cleaner Production, 2023, 414, 137648. https://doi.org/10.1016/j.jclepro.2023.137648

High lipid content (45.89 wt%) was obtained by adding EAFS leaching solution into BG11. High biomass content (0.44 g/L) was achieved by citric acid assisting EAFS leaching. 在BG11中加入EAFS浸出液，获得了较高的脂质含量(45.89 wt%)。柠檬酸辅助EAFS浸出可获得较高的生物质含量(0.44 g/L)。

电炉渣重金属胁迫促进Chlorella pyrenoidosa微藻高效合成油脂

最近，青年女科学家王一同博士（华北理工大学冶金与能源学院副教授）和方真教授在国际学术期刊Journal of Cleaner Production（IF: 11.072，Q1）发表题为“电炉渣重金属胁迫促进Chlorella pyrenoidosa高效合成脂质”的研究性论文。

电炉渣产量高，元素丰富，可作为微藻的营养来源。研究了Chlorella pyrenoidosa在电炉渣浸出液和柠檬酸电炉渣共浸出液中的生长和脂质合成的调节机制，实现冶金固体废物资源化同时获得高附加值脂质。结果表明，当在BG11添加电炉渣浸出液中时，生物量和脂质的最高含量分别为0.23g/L和45.89wt%。在BG11添加柠檬酸电炉渣联合浸出液时，生物量和脂质含量分别为0.25g/L和33.37wt%。电炉渣浸出液中的各种金属离子通过调节乙酰辅酶A羧化酶、苹果酸酶和磷酸烯醇丙酮酸羧化酶的活性来增加脂质含量。本研究有助于解决微藻培养和冶金固废处理成本高的问题，为微藻商业化提供新思路。详情可见：

Q Yu, TJ Liu, YN Zeng, YT Wang*, JG Li*, LL Kang, R Ji, FP Wang, XM Wang, B Liu, S Cai, Zhen Fang*. Efficient lipid synthesis of Chlorella pyrenoidosa promoted under heavy metals from electric arc furnace slag. Journal of Cleaner Production, 2023, 414, 137648. https://doi.org/10.1016/j.jclepro.2023.137648

Miss Xiao-le Liu and Mr. Jian Yang successfully defended their Doctoral and Master theses

On May 26, 2023, Miss Xiao-le Liu and Mr. Jian Yang, supervised by Prof. Zhen Fang, successfully defended their theses at C302 Yuxian Building, Pukou Campus of Nanjing Agricultural University. The defending committee was composed of Prof. Mao-hua Xiao (Chair) from Nanjing Agricultural University, Profs Wei Zhuang and Jun Zhou from Nanjing Tech University as well as Profs Chang-ying Ji, Wei-min Ding and Chun-xia He from Nanjing Agricultural University (NJAU).

Miss Liu and Mr. Yang presented their research results for doctoral and master theses, the committee members raised relevant questions. Based on the replies and theses reviewed, the panels agreed that Miss Liu and Mr. Yang had successfully completed their research and course requirements in agricultural bio-environment and energy engineering. Miss Liu studied the production of microbial lipid from wheat straw with dissertation entitled “Study on mechanochemical pretreatment of wheat straw and enzymatic hydrolysate for microbial lipid production”. She significantly improved the enzymatic hydrolysis efficiency of wheat straw pretreated by solid particle-assisted ball milling pretreatment, and realized the efficient production of lipid from the enzymatic hydrolysis of pretreated wheat straw. Mr. Yang studied biodiesel production of waste cooking oil by bifunctional magnetic catalysts with his thesis entitled “Microwave Assisted Production of Biodiesel from Waste Cooking Oil by Bifunctional SrO-ZnO/MOF Catalyst”. Miss Liu published 2 academic papers and Mr. Yang published 1 academic papers. Both of them had all been awarded the title of “Outstanding Graduate of NJAU”. Mr. Yang won President Scholarship of NJAU.

After the juries voted by secret ballot, the panels agreed to confer Doctor of Philosophy in Engineering to Miss Xiao-Le Liu, and Master of Engineering degree to Mr. Yang Jian, subjected to the approval by the Academic Degrees Committees of the college and university.

Congratulations to Miss Liu and Mr. Yang!

Papers published:

XL Liu, Zhen Fang*, XF Tian*, ZD Miao, Impact of Alkalic Salt Coupled Ball Milling Pretreatment of Wheat Straw on Improving Enzymatic Hydrolysis and Energy Efficiency, Fuel, 340 (2023), 127336. https://doi.org/10.1016/j.fuel.2022.127336.

XL Liu, CY Dong, SY Leu, Zhen Fang*, ZD Miao, Efficient Saccharification of Wheat Straw Pretreated by Solid Particle-Assisted Ball Milling with Waste Washing Liquor Recycling, Bioresource Technology, 347 (2022), 126721. https://doi.org/10.1016/j.biortech.2022.126721.

Jian Yang, Wen-Jie Cong, Zongyuan Zhu**, Zheng-diao Miao, Yi-Tong Wang***, Michael Nelles, Zhen Fang*. Microwave-assisted one-step production of biodiesel from waste cooking oil by magnetic bifunctional SrO–ZnO/MOF catalyst. Journal of Cleaner Production, 395 (2023) 136182. https://doi.org/10.1016/j.jclepro.2023.136182.

刘小乐和杨剑同志顺利通过博士和硕士论文答辩

2023年5月26日上午，南京农业大学生物能源组2019级博士研究生刘小乐（女）和硕士生杨剑（导师方真教授）毕业答辩会在南京农业大学浦口校区育贤楼C302举行。南京农业大学的肖茂华教授担任答辩评审委员会主席，南京工业大学的庄伟教授和周俊教授，南京农业大学的丁为民，姬长英教授和何春霞教授共五位专家担任评审委员。

答辩会上，刘小乐同学和杨剑同学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。根据刘小乐同学和杨剑同学的问题回答以及学位论文的评阅，评委会经过评审决议，一致认为刘小乐同学和杨剑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。刘小乐同学在毕业论文《机械化学法预处理小麦秸秆及其酶解液发酵产微生物油脂的研究》中研究了球磨和化学颗粒结合预处理小麦秸秆，实现了小麦秸秆的结构解聚，有效提高了小麦秸秆在较低酶载量和较短时间内的酶水解效率，并将水解获得的可发酵性碳源用于发酵产微生物油脂，实现了农作物秸秆到微生物油脂的资源化利用。杨剑同学在毕业论文《双功能SrO-ZnO/MOF催化剂微波辅助餐厨废油制备生物柴油》中研究了利用双功能磁性催化剂催化废油脂制备生物柴油，实现了在较温和条件下一步法催化高酸值废弃油制备生物柴油。刘小乐同学以第一作者身份共发表学术论文2篇，杨剑同学以第一作者发表学术论文1篇，两人均获得2023南京农业大学优秀毕业生称号。杨剑同学获得南京农业大学校长奖学金。

经评委会无记名投票表决，一致同意刘小乐同学通过博士学位论文答辩，建议授予工学博士学位；杨剑同学通过硕士学位论文答辩，建议授予杨剑工学硕士学位。

 祝贺刘小乐和杨剑同学！

发表的论文：

XL Liu, Zhen Fang*, XF Tian*, ZD Miao, Impact of Alkalic Salt Coupled Ball Milling Pretreatment of Wheat Straw on Improving Enzymatic Hydrolysis and Energy Efficiency, Fuel, 340 (2023), 127336. https://doi.org/10.1016/j.fuel.2022.127336.

XL Liu, CY Dong, SY Leu, Zhen Fang*, ZD Miao, Efficient Saccharification of Wheat Straw Pretreated by Solid Particle-Assisted Ball Milling with Waste Washing Liquor Recycling, Bioresource Technology, 347 (2022), 126721. https://doi.org/10.1016/j.biortech.2022.126721.

Jian Yang, Wen-Jie Cong, Zongyuan Zhu**, Zheng-diao Miao, Yi-Tong Wang***, Michael Nelles, Zhen Fang*. Microwave-assisted one-step production of biodiesel from waste cooking oil by magnetic bifunctional SrO–ZnO/MOF catalyst. Journal of Cleaner Production, 395 (2023) 136182. https://doi.org/10.1016/j.jclepro.2023.136182.