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

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).

Mr. Xiao-jie Wei and Miss Le-yao Zhang successfully defended their theses

On May 29, 2019, Mr. Xiao-jie Wei and Miss Le-yao Zhang supervised by Prof. Zhen Fang with the help of Drs. Lujiang Xu and Xiao Kong, successfully defended their theses in A101 Huixian Building, Pukou Campus of Nanjing Agricultural University. The defending committee was composed of Profs. Yongfu Zhao (chair) and Hongying Huang from Jiangsu Provincial Academy of Agricultural Sciences, Prof. Xiaohua Wang and Associate Professor Kunquan Li from Nanjing Agricultural University.

All the members of the panel listened to the presentations, raised corresponding questions and reviewed the relevant information after hearing the thesis presentations by Mr. Wei and Miss Zhang. After reviewing and defending, the panel agreed that Mr. Wei and Miss Zhang had successfully completed their research and course requirements on agricultural bio-environment and energy engineering. Mr. Wei studied the catalytic condensation of furfural and acetone alcohol to furanic biofuels to optimize technological conditions with La-based trimetallic catalysts with his thesis entitled “Lanthanide complex metal catalysts for furanic biofuels preparation”. Miss Zhang studied the green recycling of polyvinyl chloride (PVC) with her thesis entitled “Study on the preparation of hydrocarbons by catalytic pyrolysis dechlorination of polyvinyl chloride”. She modified PVC plastic with catalyst of calcium hydroxide to catalyze the conversion of PVC to hydrocarbons by fast pyrolysis technology. Both students worked hard and published 2 academic papers. After the jury voted by secret ballot with Grade B, the panel agreed to confer Master of Engineering Degree to Mr. Xiao-jie Wei and Miss Le-yao Zhang subjected to the approval by the Academic Degrees Committees of the college and university.

Both students got a decent job in manufacturing industry as an engineer.

Congratulations!

生物能源组工程硕士生魏孝捷、张乐瑶顺利通过毕业答辩

2019年5月29日，南京农业大学生物能源2017级工程硕士研究生魏孝捷（男）与张乐瑶（女）毕业答辩会在南京农业大学浦口校区汇贤楼A101举行。答辩评审委员会主席由江苏省农业科学院赵永富研究员担任，来自江苏省农科院的赵永富研究员与黄红英研究员，南京农业大学的王效华教授与李坤权副教授共四位专家担任评审委员。

答辩会上，答辩委员会主席及各位评委在听取了魏孝捷与张乐瑶同学在读期间的答辩报告后，进行了充分的问答和审阅相关资料。经过评审决议后，专家组一致认为魏孝捷与张乐瑶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。魏孝捷同学在毕业论文《镧系复合金属催化剂催化制备呋喃类生物燃料》中研究了La系三金属催化剂对于催化糠醛丙酮醇缩合制备呋喃类生物燃料，并针对高效的复合金属氧化物的最优工艺条件进行了研究；张乐瑶同学在毕业论文《聚氯乙烯催化热解脱氯制备碳氢化合物的研究》中对聚氯乙烯(PVC)塑料绿色回收进行研究，针对氢氧化钙对PVC进行改性，利用催化热解技术将聚氯乙烯催化为碳氢化合物，报告数据可靠。两位同学在校期间工作努力，共发表学术论文2篇。经评委会无记名投票表决，评定等级为良好，一致同意通过毕业答辩。

祝贺魏孝捷、张乐瑶同学！

Two Springer books edited by Prof. Fang et al. in 2016 and 2017 were  among the top 25% most downloaded eBooks in 2018.

Two Springer books edited by Prof. Fang et al. in 2016 and 2017 were  among the top 25% most downloaded eBooks in 2018.

1.Zhen Fang*, R. L. Smith, Jr., H. Li (Editors), Production of Biofuels and Chemicals with Bifunctional Catalysts, Springer Book Series – Biofuels and Biorefineries, Springer-Verlag, Heidelberg Berlin, hardcover, 12 Chapters, ISBN 978-981-10-5136-4, 2017. (Among the top 25% most downloaded eBooks in 2018)。

2.Zhen Fang*, R. L. Smith, Jr.(Editors), Production of Biofuels and Chemicals from Lignin, Springer Book Series – Biofuels and Biorefineries, Springer-Verlag, Heidelberg Berlin, hardcover, ISBN 978-981-10-1964-7, 2016. (Among the top 25% and 50% most downloaded eBooks in 2018 and 2017)。

Other two Springer books were also listed in “the top 25% most downloaded eBooks”:

3.Zhen Fang*, R. L. Smith, Jr., X. Qi (Editors), Production of Platform Chemicals from Sustainable Resources, Springer Book Series – Biofuels and Biorefineries, Springer-Verlag, Heidelberg Berlin, hardcover, 14 Chapters, ISBN 978-981-10-4171-6, 500 pages, 2017. (Among the top 25% most downloaded eBooks in 2017).

4.Zhen Fang (Editor), Pretreatment Techniques for Biofuels and Biorefineries, Springer-Verlag, Berlin Heidelberg,  ISBN 978-3-642-32734-6, hardcover, 476 pages, 2013. (Among the top 25% most downloaded eBooks in 2013)。

方老师2016和2017年编著的两部Springer专著列入“2018年Springer下载量最高的25%电子书中”。

方老师共有4部专著进入“Springer下载量最高的25%电子书中”：

1.Zhen Fang*, R. L. Smith, Jr., H. Li (Editors), Production of Biofuels and Chemicals with Bifunctional Catalysts, Springer Book Series – Biofuels and Biorefineries, Springer-Verlag, Heidelberg Berlin, hardcover, 12 Chapters, ISBN 978-981-10-5136-4, 2017.(Among the top 25% most downloaded eBooks in 2018)。

2.Zhen Fang*, R. L. Smith, Jr.(Editors), Production of Biofuels and Chemicals from Lignin, Springer Book Series – Biofuels and Biorefineries, Springer-Verlag, Heidelberg Berlin, hardcover, ISBN 978-981-10-1964-7, 2016.(Among the top 25% and 50% most downloaded eBooks in 2018 and 2017)。

3.Zhen Fang*, R. L. Smith, Jr., X. Qi (Editors), Production of Platform Chemicals from Sustainable Resources, Springer Book Series – Biofuels and Biorefineries, Springer-Verlag, Heidelberg Berlin, hardcover, 14 Chapters, ISBN 978-981-10-4171-6, 500 pages, 2017. (Among the top 25% most downloaded eBooks in 2017).

4.Zhen Fang (Editor), Pretreatment Techniques for Biofuels and Biorefineries, Springer-Verlag, Berlin Heidelberg,  ISBN 978-3-642-32734-6, hardcover, 476 pages, 2013. (Among the top 25% most downloaded eBooks in 2013).