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

Dr. Yi-Tong Wang (Associate Prof. at North China University of Science and Technology in Tangshan) and Prof. Zhen Fang as guest editors for the Special Issue “Catalytic Biomass to Renewable Biofuels and Biomaterials” in Catalysts (ISSN 2073-4344) wrote an editorial about catalytic conversions of biomass. Renewable, clean and environmentally friendly biofuels and biomaterials applications are in line with the healthy development of the world’s energy and materials in the future. Biomass as the only renewable carbon source on Earth has been proposed as an ideal alternative to fossil resources and can be catalytically conversed to valuable products, such as hydrolysis of lignocellulosic wastes, synthesis of biodiesel and bioethanol, thermal conversions of biomass and organic wastes. This special issue contains 11 papers (1 review and 10 research articles) contributed by leading experts in the field. The articles include: catalytic conversion of glycerol to acetyl derivatives, base-catalyzed organosoly process to fractionate European larch to recover cellulose and pure lignin, co-pyrolysis of grape seeds and waste tires for bio-oils in a pilot-scale auger reactor with Ca-based catalysts, diesel and jet fuel cycloalkanes produced from cyclopentanone and furfural, macroporous cross-linked copolymers from wheat straw, 2,5-bis(hydroxymethyl)furan from hydroxymethylfurfural, N-containing chemicals from polyethylene terephthalate via catalytic fast pyrolysis with ammonia, co-combustion of sludge and wheat straw, biofuels from fermentation of gases by Clostridium carboxidivorans, humic acid-rich composts for applications to catalyzing redox-mediated reactions of pollutants in soils, a review on some organisms such as Clostridium carboxidivorans, C. ragsdalei, and C. ljungdahlii for the production of biofuels (e.g., ethanol and butanol) and chemicals.

These papers should be of interest to professionals in academia and industry who are working in the fields of natural renewable materials, biorefinery of lignocellulose, biofuels and environmental engineering. It can also be used as comprehensive references for university students with backgrounds of catalysis, agricultural engineering, chemical engineering, material science and environmental engineering.

Ref:

YT Wang and Zhen Fang*, Catalytic Biomass to Renewable Biofuels and Biomaterials. Catalysts 2020, 10, 480, https://doi.org/10.3390/catal10050480 .

Subcritical water gasification of lignocellulosic wastes for hydrogen production with CoNi/Al₂O₃

Recently, master student Mr. Jie Sun supervised by Prof. Zhen Fang collaborated with Profs. JA Kozinski at Waterloo and AK Dalai at U of Saskatchewan in Canada, published a research article in J Supercrit Fluids about hydrogen production from lignocellulosic wastes with CoNi/Al₂O₃ catalysts.

Nickel-based catalysts with different supports and cobalt loadings were synthesized for hydrothermal gasification of cellulose 350 ^oC. The activity of Ni catalysts was found in the order of Al₂O₃ > spent bleaching clay ash > SiO₂ with H₂ yield of 80.6%, 69.0% and 57.0% and the prepared catalyst using Al₂O₃ as the support showed the highest catalytic activity to produce H₂. When 6 wt. % Co was added, H₂ yield reached the maximum value of 88.4%, which was 1.44 times than that of 10Ni/Al₂O₃ catalyst without adding Co. Catalysts were characterized by NH₃-TPD, TPR, XRD, BET and XPS, showing that Ni-Co alloy formation promoted H₂ production. Furthermore, the effect of parameters such as feedstock usage and residence time were also investigated systematically with 10Ni-6Co/Al₂O₃ catalyst and the results indicated that the optimal yield of H₂ at 94.9% was obtained at the conditions of 0.5g cellulose usage and 20 min residence time. Finally, the study about different lignocellulosic wastes (rice straw, peanut shells and cotton straw) with the increase in H₂ yield by 51.4, 76.0 and 67.8 times and cotton straw obtained the highest H₂ yield of 82.6%. Ni-Co/Al₂O₃ catalysts enhanced hydrothermal gasification of lignocellulosic wastes.

Related results were accepted in J Supercrit Fluids:

J Sun, L Xu, GH Dong, S Nanda, H Li, Zhen Fang*, JA Kozinski, AK Dalai, Subcritical water gasification of lignocellulosic wastes for hydrogen production with Co modified Ni/Al₂O₃ catalysts. J Supercrit Fluids, https://doi.org/10.1016/j.supflu.2020.104863 , 162, 104863, 2020.

Catalytic hydrothermal gasification of cotton straw with H₂ yield of 82.6% over NiCo/Al₂O₃ catalyst at 350 ^oC and 20 min.（NiCo/Al₂O₃催化剂在350 ^oC和20 min条件下催化棉花秸秆水热气化, H₂产率为82.6%。）

CoNi/Al₂O₃催化剂在亚临界水中气化木质纤维素废弃物制氢

最近，硕士生孙杰在方老师的指导下，与加拿大滑铁卢大学JA Kozinski院士和萨斯卡彻温大学AK Dalai院士合作，在国际学术期刊J Supercrit Fluids发表以Co改性Ni/Al₂O₃催化剂从木质纤维素废弃物中制取氢气的研究性论文。

合成了具有不同载体和钴载量的镍基催化剂，用于350 ^oC条件下纤维素的水热气化。 Ni催化剂的活性根据载体来排序依次为Al₂O₃、SBC ash （废白土灰）、SiO₂，对应的H₂产率分别为80.6%，69.0%和57.0%，且以Al₂O₃作为载体制备的催化剂具有最高的产氢催化活性。当Co的负载量为6 wt. %时，H₂产率达到最大值，为88.4％，是不添加Co的10Ni/Al₂O₃催化剂H₂产率的1.44倍。NH₃-TPD，TPR，XRD，BET和XPS等特征分析，表明Ni-Co合金的形成促进了H₂的产生。此外，还以10Ni-6Co/Al₂O₃作为催化剂研究了原料用量和停留时间等参数的影响，结果表明，在纤维素用量和停留时间分别为0.5 g和20 min的条件下，H₂产率进一步提高到94.9％。最后，对不同木质纤维素废弃物（水稻秸秆、花生壳和棉花秸秆）的气化进行了研究，H₂产率分别提高了51.4、76.0和67.8倍，而棉秸秆获得最高的H₂产量为82.6％。 Ni-Co/Al₂O₃催化剂促进了木质纤维素废弃物水热气化产氢。详情可见：

J Sun, L Xu, GH Dong, S Nanda, H Li, Zhen Fang*, JA Kozinski, AK Dalai, Subcritical water gasification of lignocellulosic wastes for hydrogen production with Co modified Ni/Al₂O₃ catalysts. J Supercrit Fluids, https://doi.org/10.1016/j.supflu.2020.104863 , 162, 104863, 2020.

Direct production of biodiesel from waste oils with a strong solid base from alkalized industrial clay ash

Recently, PhD student Miss Wen-jie Cong supervised by Prof. Zhen Fang published a research article in Applied Energy about biodiesel production from high acid (AV) waste oils with a solid base derived from spent bleaching clay (SBC).

Biodiesel was directly one-step produced from waste oils without pretreatment catalyzed by a solid base alkalized from SBC ash. Optimized conditions were obtained with 99.1% biodiesel yield from soybean oil with an orthogonal design. The base catalyst was stable within 8 cycles (> 95% biodiesel yield) and resistant to saponification (AV = 9.7 mg KOH/g, 96.5% biodiesel yield). The base was characterized with XRD, EDX-mapping, FT-IR, XRF and TPD, and it had similar strong basicity to Na₂SiO₃ (0.21 vs. 0.22 mmol/g for Na₂SiO₃) with active sites of Na₂O and CH₃ONa evolved from Na₂SiO₃ and NaAlSiO₄ by reactions of NaOH with oxides (e.g., SiO₂, Al₂O₃) in SBC ash. Furthermore, the base was magnetized with magnetism of 6.86 emu/g by carbonizing residual oil in SBC as carbon support and reductant (of Fe₂O₃ to magnetic Fe₃O₄ particles). It catalyzed soybean oil to produce biodiesel with 99.2% yield and blended oil (AV = 5.9) to biodiesel with 91.9% yield without any saponification. The catalyst was magnetically separated and reused for 3 cycles with 87% yield. The non-magnetic base could also efficiently catalyze actual SBC oil for the production of biodiesel with 95% yield at AV of 10. This work realized the full use of inorganics in SBC, and its oil for direct biodiesel production at a low temperature (i.e., 65 vs. 120 ^oC with sulfuric acid process) without wastes produced and results can easily find practical applications for waste oils.

Related results were accepted in Applied Energy:

WJ Cong, YT Wang, H Li, Zhen Fang*, J Sun, HT Liu, JT Liu, S Tang, L Xu. Direct production of biodiesel from waste oils with a strong solid base from alkalized industrial clay ash. Applied Energy, 264,114735 (2020), https://doi.org/10.1016/j.apenergy.2020.114735.

Solid base synthesized from SBC ash for biodiesel production from waste oils with 8 cycles and anti-saponification. It was further magnetized for easy separation.（以废白土为原料合成固体碱，催化废弃油脂制备生物柴油。该催化剂可循环使用8次且可抗皂化，并被进一步磁化为磁性固体催化剂以便于分离。）.

以废白土为原料合成固体碱并用于直接催化废弃油脂制备生物柴油

最近，博士生丛文杰（女）在方老师的指导下，在国际学术期刊Applied Energy（IF8.4，Q1）发表以废白土为原料合成固体碱以制备生物柴油的研究性论文。

通过NaOH碱化废白土灰合成固体碱，直接催化废弃油脂制备生物柴油。首先，以大豆油为原料，通过正交试验确定了最优反应条件（醇油比11:1，催化剂量8 wt%，温度65℃，反应3 h），该条件下生物柴油得率为99.1%，该固体碱8次循环后产率仍高于95%。该固体碱可抗皂化，油脂酸值为9.7 mg KOH/g 时生物柴油产率可达96.5%，催化酸值为10的废白土油可得生物柴油产率为95%。此外，进一步通过碳化废白土中的残油作为碳载体和还原剂（将氧化铁转化为四氧化三铁），磁化为磁性固体碱催化剂（6.86 emu/g）。该磁性固体碱催化大豆油制备生物柴油产率为99.2%，经磁性分离后可重复使用3次（生物柴油产率为87%），催化酸值5.9 mg KOH/g的油脂得生物柴油产率为91.9%且未见皂化。本研究充分利用废白土中的无机物（如二氧化硅、氧化铝等），并实现低温下碱催化一步法转化废白土油为生物柴油。整个生产工艺无废弃物生成，并易于应用于工业生产生物柴油。详情可见：

WJ Cong, YT Wang, H Li, Zhen Fang*, J Sun, HT Liu, JT Liu, S Tang, L Xu. Direct production of biodiesel from waste oils with a strong solid base from alkalized industrial clay ash. Applied Energy, 264,114735 (2020), https://doi.org/10.1016/j.apenergy.2020.114735.

Springer book “Production of Biofuels and Chemicals with Pyrolysis”
Springer is going to publish (in revision, due early 2020) a book entitled “Production of Biofuels and Chemicals with Pyrolysis” edited by Profs. Zhen Fang, RL Smith Jr. and Dr. LJ Xu, Springer, Hardcover ISBN 978-981-15-2731-9, 560 pages, 2020 (https://www.springer.com/gp/book/9789811527319#aboutBook).

Pyrolysis is widely applicable to the valorization of biomass. This book presents a collection of studies on state-of-art techniques developed specifically for conversion of biomass to chemical products by pyrolysis with an emphasis on the fundamentals and mechanisms for producing bio-oils, chemicals, gases and biochar via pyrolysis processes. Key reaction parameters and reactor configurations are outlined for converting many types of biomass into chemical products. All chapters were contributed by respected global experts in their field to provide readers with a broad range of perspectives on cutting-edge applications. The book is an ideal reference guide for academic researchers and industrial engineers in the fields of natural renewable materials, biorefinery of lignocellulose, biofuels and environmental engineering. It can also be used as a comprehensive reference source for university students in chemical engineering, material science and environmental engineering.

This book contains 13 chapters contributed by leading experts in the field. The text is arranged into five key areas:
Part 1. Fundamentals of Pyrolysis
Part 2. Production of Liquid Biofuels by Pyrolysis & Catalytic Pyrolysis
Part 3. Liquid Biofuels Production by Microwave Pyrolysis
Part 4. Producing Bio-Chemicals by Pyrolysis
Part 5. Producing Gas Fuel and Pyrolysis Modeling

The text should be of interest to professionals in academia and industry who are working in the fields of natural renewable materials, biorefinery of lignocellulose, biofuels, agricultural engineering and environmental engineering. It can also be used as comprehensive references for university students with backgrounds of chemical engineering, material science and environmental engineering.

This book is the tenth book of the series entitled, “Biofuels and Biorefineries”, (highly-downloaded books with 135 k chapter downloads and 4 books among “top 25% springer e-books”, Prof. Zhen Fang is serving as Editor-in-Chief), and the seventeenth English book edited/authored by Prof. Zhen Fang since 2009.
Biofuels and Biorefineries：

http://www.springer.com/series/11687?detailsPage=titles

斯普林格新书《热解生产生物燃料和化学品》即将出版

由方真老师、日本东北大学RL Smith Jr.教授和徐禄江博士主编的新书《热解生产生物燃料和化学品》，最近将由斯普林格公司出版发行（in revision, due early 2020，精装，560页， ISBN978-981-15-2731-9, 2020)(https://www.springer.com/gp/book/9789811527319#aboutBook)。

热解广泛应用于生物质的高值化。这本书展示了一个关于最新技术的研究的集合，特别是生物质通过热解转化为化学产品，重点介绍了通过热解过程生产生物油、化学品、气体和生物炭的基本原理和机理。概述了将多种生物质转化为化工产品的关键反应参数和反应器结构。本书包含13个章节，每个章节由全球范围内挑选的该领域的专家或教授编写并通过严格的外审，为读者提供前沿应用的广泛视角。

本书分为五个主要部分：
第1部分: 热解原理
第2部分: 通过热解和催化热解生产液体生物燃料
第3部分: 微波热解生产液体生物燃料
第4部分: 通过热解生产生物化学品
第5部分: 生产气体燃料和热解建模

这本书，为学术界研究人员和工业工程师在自然可再生材料、生物精练的木质纤维素、生物燃料、农业工程和环境工程领域提供了一个理想的参考指南。它对化工、材料科学、环境工程等专业的大学生具有广泛的参考价值。

该书是斯普林格系列丛书“生物燃料和生物炼制- Biofuels and Biorefineries”（方真老师担任该丛书总编辑，章节下载量（电子销售量）近13.5万次，他编著其中4 部专著已进入Springer高下载书籍前25%。）出版的第十本专著，也是方真老师自2009年以来，编著出版的第十七部英语专著。

生物燃料和生物炼制丛书：
http://www.springer.com/series/11687?detailsPage=titles.

Cycloamination strategies for renewable N-heterocycles

Recently, Dr. H Li and Prof. Zhen Fang, collaborated with Prof. RL Smith Jr. (Tohoku University, Japan), published a review (Spotlight) paper in Green Chemistry about the production of renewable N-heterocycles.

Biomass resources have infinite possibilities for introducing nitrogen, sulfur, or phosphorus heteroatoms into their structures by virtue of controllable carbon-heteroatom bond formation. In this review, cycloamination approaches for thermal (catalyst-free) and catalytic transformation of biomass feedstocks into N-heterocyclic molecules including mechanistic pathways are analyzed. Bottom-up (small molecule substrates) and top-down (large molecule substrates) are considered. Sustainable routes for synthesis of five-membered (pyrroles, pyrrolidones, pyrazoles, imidazoles), six-membered (pyridines, pyrazines), fused (indoles, benzimidazoles), and other relevant azaheterocycles are critically assessed. Production of biomass-derived six-, seven-, and eight-membered as well as fused N-heterocyclic compounds with present approaches have relatively low selectivities. Attention to methods for forming analogous sulfur or phosphorus heteroatom compounds from biomass resources using either bottom-up or top-down strategies appear to have been greatly overlooked. Synthetic auxiliaries (heating modes, nitrogen sources) that enhance reaction efficiency and tunability of N-heterocyclic ring size/type are considered and plausible reaction mechanisms for pivotal pathways are developed.

Efficient amination strategies for synthesis of N-heterocycles from functional molecules (bottom-up) or from biomass (top-down) via sustainable C-N/C-X bond chemistry （从功能分子(自下而上)或从生物质(自上而下)通过可持续碳- n /C-X键化学合成n杂环的高效胺化策略）

Related results were accepted in Green Chemistry:

H Li*, HX Guo, Zhen Fang*, TM Aida, RL Smith Jr*, Cycloamination Strategies for Renewable N-heterocycles, Green Chemistry, https://doi.org/10.1039/C9GC03655E , 22, 582-611, 2020 (Spotlight Paper, Review).

————————————

李虎博士在国际学术期刊Green Chemistry发表学术论文

可再生氮杂环的环胺化策略

最近，国际学术期刊Green Chemistry（影响因子9.4, Q1，第一署名单位为南京农业大学，第一作者为李虎博士，通讯作者为李虎博士,方真教授和日本东北大学RL Smith Jr教授）以Spotlight paper形式，发表了生物质生产可再生氮杂环化合物的综述。

生物质资源通过可控的碳-杂原子成键将氮、硫、磷等杂原子引入其结构中具有无限的可能性。本文综述了近年来生物质原料热(无催化)和催化转化为n -杂环分子的环胺化方法及其机理。考虑自底向上(小分子底物)和自顶向下(大分子底物)。五元(吡咯、吡咯烷酮、吡唑、咪唑)、六元(吡啶)的合成路线。用现有方法生产生物衍生的六元、七元、八元以及融合的n杂环化合物的选择性较低。利用自底向上或自顶向下的战略从生物量资源中形成类似硫或磷杂原子化合物的方法似乎受到了极大的忽视。考虑了提高反应效率和n杂环尺寸/类型可调性的合成助剂(加热方式、氮源)，并建立了关键途径的合理反应机制。

详情可见：

H Li*, HX Guo, Zhen Fang*, TM Aida, RL Smith Jr*, Cycloamination Strategies for Renewable N-heterocycles, Green Chemistry (IF 9.4), https://doi.org/10.1039/C9GC03655E 22, 582-611, 2020 (Spotlight Paper, Review).