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

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).

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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