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

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).

High Yield Production of Levoglucosan via Catalytic Pyrolysis of Cellulose at Low Temperature

Recently, Dr Li-Qun Jiang (Associate Prof., Institute of Biological and Medical Engineering, Guangdong Academy of Sciences), Prof. H Li (Guizhou University) and Prof. Zhen Fang published an article in Fuel about levoglucosan production from catalytic pyrolysis of cellulose with acid-base bifunctional magnetic Zn-Fe-C catalysts.

Catalytic pyrolysis of cellulose to levoglucosan in improved yields was achieved with acid-base bifunctional magnetic Zn-Fe-C catalysts. Among tested catalysts, Zn₄@Fe-C₅₀₀ could not only increase levoglucosan yield by 5.4 times compared with non-catalytic cellulose pyrolysis at 300 °C, but also help lower reaction temperature by 200 °C due to acid-base site synergistic effect. Furthermore, the levoglucosan yield (80.1 wt%) from catalytic cellulose pyrolysis at 300 °C was much higher than that commonly conducted at 500 °C without catalyst (60.1 wt%). Thermogravimetric and kinetic analysis disclosed levoglucosan formation mechanism. Importantly, Zn₄@Fe-C₅₀₀ catalyst was highly recyclable with little deactivation after 5 consecutive cycles. This study exhibited great potential for industrial levoglucosan production from cellulose at low temperatures. Related results were published in Fuel:

LQ Jiang, JC Luo, F Xu, L Qian, YT Wang, H Li*, Zhen Fang*, High Yield Production of Levoglucosan via Catalytic Pyrolysis of Cellulose at Low Temperature, Fuel, 323 (2022) 124369. https://doi.org/10.1016/j.fuel.2022.124369

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Production of Levoglucosan via Catalytic Pyrolysis of Cellulose at Low Temperature with Zn_n@Fe-C_T acid-base bifunctional magnetic catalyst磁性固体酸碱两性催化剂Zn_n@Fe-C_T催化纤维素定向热解制备左旋葡聚糖

 磁性固体酸碱两性催化剂Zn_n@Fe-C_T催化纤维素定向热解制备左旋葡聚糖

最近，蒋丽群博士（广东省科学院生物与医学工程研究所副教授）, 李虎教授 （贵州大学）和方真教授在国际学术期刊Fuel（IF: 6.609，Q1）发表题为“High Yield Production of Levoglucosan via Catalytic Pyrolysis of Cellulose at Low Temperature”的研究性论文。该研究制备了磁性固体酸碱两性催化剂Zn_n@Fe-C_T用于催化纤维素快速热解选择性制取左旋葡聚糖。相关研究表明，Zn₄@Fe-C₅₀₀催化热解纤维素不仅可以将热解糖化反应温度从500 ℃降低至300 ℃，并且300 ℃下催化热解纤维素得到左旋葡聚糖的产率（80.1 wt%）远高于500℃（60.1 wt%）。经过5次循环实验后Zn₄@Fe-C₅₀₀仍然可以提升左旋葡聚糖的产率。该研究为纤维素定向热解转化提供了新思路。详情可见：

LQ Jiang, JC Luo, F Xu, L Qian, YT Wang, H Li*, Zhen Fang*, High Yield Production of Levoglucosan via Catalytic Pyrolysis of Cellulose at Low Temperature, Fuel, 323 (2022) 124369. https://doi.org/10.1016/j.fuel.2022.124369

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NaFeO₂-Fe₃O₄合成生物柴油Highly stable NaFeO₂-Fe₃O₄ composite catalyst from blast furnace dust for efficient production of biodiesel at low temperature

Recently, Dr Yi-Tong Wang (Associate Prof., College of Metallurgy and Energy, North China University of Science and Technology) and Prof. Zhen Fang published an article in Industrial Crops & Products about using highly stable NaFeO₂-Fe₃O₄ composite catalyst from blast furnace dust for biodiesel production.

Highly stable catalysts were prepared by wet impregnation of blast furnace dust (BFD) in Na₂CO₃·H₂O, Na₂CO₃·10H₂O, NaHCO₃ and Na₂CrO₄ solution and subsequent calcination of 300-600 ^oC. At low temperature of 65 ^oC for 2 h with methanol/oil molar ratio of 15/1, high biodiesel yields of 100 wt% were obtained with 7wt% Na₂CO₃·H₂O@BFD₃₀₀ and Na₂CO₃·H₂O@BFD₄₀₀ catalyst (impregnating with Na₂CO₃·H₂O solution and calcining at 300 and 400 ^oC) added for the first use. Na₂CO₃·H₂O@BFD₃₀₀ catalyst exhibited outstanding stability and recyclability with biodiesel yields of 100 wt% at the fifth use (93 wt% at the twelfth use) owing to impregnated Na₂CO₃ reacting with Fe₂O₃ in dust to produce stable and active nanocomponents of NaFeO₂ (32.42 nm) and magnetic nanocomponent of Fe₃O₄ (size of 3.14 nm and Ms of 6.16 Am²/kg) in dust existing. The study provided practical guidance for biodiesel industrial production.

Related results were published in Industrial Crops & Products:

XM Wang, YN Zeng, LQ Jiang, YT Wang*, JG Li*, LL Kang, R Ji, D Gao, FP Wang, Q Yu, YJ Wang, Zhen Fang*. Highly stable NaFeO₂-Fe₃O₄ Composite Catalyst from Blast Furnace Dust for Efficient Production of Biodiesel at Low Temperature, Industrial Crops and Products, 182, 114937, https://doi.org/10.1016/j.indcrop.2022.114937 (2022).

Efficient production of biodiesel can be achieved with Na₂CO₃·H₂O@BFD₃₀₀ catalyst for 12 reuses with 92.56 wt% yield.使用Na₂CO₃·H₂O@BFD₃₀₀催化剂实现生物柴油高效生产，循环12次后，产率仍可达92.56 wt%。

王一同博士和方真教授在国际学术期刊Industrial Crops & Products发表学术论文:

高炉粉尘制备NaFeO₂-Fe₃O₄复合催化剂用于生物柴油合成

最近，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Industrial Crops & Products（IF: 5.645，Q1）发表题为“高炉粉尘制备NaFeO₂-Fe₃O₄复合催化剂用于生物柴油合成”的研究性论文。

利用Na₂CO₃·H₂O，Na₂CO₃·10H₂O，NaHCO₃和Na₂CrO₄水溶液分别湿法浸渍高炉粉尘，于300-600 ^oC高温活化制备高稳定性催化剂。在65 ^oC、醇油摩尔比15/1、催化剂用量7 wt%的条件下反应2 h，Na₂CO₃·H₂O@BFD₃₀₀和Na₂CO₃·H₂O@BFD₄₀₀催化剂获得了100 wt%的产率。由于浸渍的Na₂CO₃和高炉粉尘中的Fe₂O₃反应生成稳定且有活性的纳米组分NaFeO₂（32.42 nm）以及高炉粉尘中含有的磁性纳米组分Fe₃O₄（晶粒：3.14 nm；磁性：6.16 Am²/kg），Na₂CO₃·H₂O@BFD₃₀₀催化剂表现出优异的稳定性和可回收性，循环12次后仍可获得93 wt%的产率。该研究为生物柴油的工业化生产提供了实用指导。详情可见：

XM Wang, YN Zeng, LQ Jiang, YT Wang*, JG Li*, LL Kang, R Ji, D Gao, FP Wang, Q Yu, YJ Wang, Zhen Fang*. Highly stable NaFeO₂-Fe₃O₄ Composite Catalyst from Blast Furnace Dust for Efficient Production of Biodiesel at Low Temperature, Industrial Crops and Products (IF 5.6), 182, 114937, https://doi.org/10.1016/j.indcrop.2022.114937 (2022).

Production of biodiesel at low temperature using bifunctional Na-Fe-Ca nanocatalyst from blast furnace waste

Recently, Dr Yi-Tong Wang (Associate Prof., College of Metallurgy and Energy, North China University of Science and Technology) and Prof. Zhen Fang published an article in Fuel about using highly active bifunctional Na-Fe-Ca nanocatalyst from blast furnace dust for biodiesel production.

Nanocatalysts for biodiesel production were prepared via wet impregnation of blast furnace dust (BFD) in Na₂CO₃ (Na-BFD) and CaCO₃ (Ca-BFD) suspension solutions and calcination at 500 and 600 ^oC, respectively. Biodiesel yields of 100.0 wt% (Na-BFD₅₀₀) and 98.3 wt% (Ca-BFD₆₀₀) were achieved at 65 ^oC. Synthesized catalysts showed outstanding activity and recyclability, due to the transition of CaCO₃, Na₂CO₃ and Fe₂O₃ to nanocrystals of NaFeO₂ (29.9 nm), Ca₂Fe₂O₅ (10.5 nm), CaO (100.1 nm) and Ca₂Fe₂O₅ (50.0 nm). Na-BFD₅₀₀ achieved 95.8 wt% biodiesel yield with 16 cycles, whereas Ca-BFD₆₀₀ reached 94.1 wt% biodiesel yield with 7 cycles via magnetic separation. BFD containing convertible magnetic and active components (Fe₂O₃ and CaCO₃) was an ideal raw material to synthesize catalyst for biodiesel production with high catalytic efficiency and easy separation. The study provided a practical utilization of industrial solid waste for biodiesel production.

Related results were published in Fuel:

YT Wang, XM Wang, D Gao, FP Wang, YN Zeng, JG Li*, LQ Jiang, Q Yu, R Ji, LL Kang, YJ Wang, Zhen Fang*, Efficient Production of Biodiesel at Low Temperature Using Highly Active Bifunctional Na-Fe-Ca Nanocatalyst from Blast Furnace Waste, Fuel, 322, 124168, https://doi.org/10.1016/j.fuel.2022.124168 (2022).

Nanocatalysts produced by impregnation and calcination transesterified soybean oil to biodiesel with 100 wt% yield. 通过浸渍和煅烧制备了纳米催化剂用于催化豆油酯交换制备生物柴油，产率高达100 wt%。

高炉粉尘制备双功能Na-Fe-Ca纳米催化剂用于生物柴油合成

最近，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Fuel（IF: 6.609，Q1）发表题为“高炉粉尘制备双功能Na-Fe-Ca纳米催化剂用于生物柴油合成”的研究性论文。

利用Na₂CO₃和CaCO₃水溶液分别湿法浸渍高炉粉尘，于500 ℃和600 ^oC高温活化制备纳米催化剂（Na-BFD₅₀₀和Ca-BFD₆₀₀），用于催化豆油制备生物柴油。催化剂经高温煅烧后，CaCO₃、Na₂CO₃和Fe₂O₃晶体转变为纳米NaFeO₂（29.9 nm）、Ca₂Fe₂O₅（10.5 nm）、CaO（100.1 nm）和Ca₂Fe₂O₅（50 nm）晶体，表现出优异的催化活性和可循环利用特性。Na-BFD₅₀₀催化豆油制备生物柴油的产率达到100.0 wt%，循环16次后仍可获得95.8 wt%的产率，而Ca-BFD₆₀₀催化豆油制备生物柴油的产率达到98.3 wt%，循环7次后仍可获得94.1 wt%的产率。该研究为工业固体废物用于生物柴油制备提供了新思路。详情可见：

YT Wang, XM Wang, D Gao, FP Wang, YN Zeng, JG Li*, LQ Jiang, Q Yu, R Ji, LL Kang, YJ Wang, Zhen Fang*, Efficient Production of Biodiesel at Low Temperature Using Highly Active Bifunctional Na-Fe-Ca Nanocatalyst from Blast Furnace Waste, Fuel (IF 6.6), 322, 124168, https://doi.org/10.1016/j.fuel.2022.124168 (2022).