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

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).

——————————————————————————————

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).

Production of N-containing compounds from plastic wastes by fast pyrolysis

Recently, Dr. Lujiang Xu and Prof. Zhen FANG have developed a catalytic pyrolysis process with ammonia for direct conversion of polyethylene terephthalate (PET) to produce N-containing compounds such as Terephthalonitrile (TPN).

Production of terephthalonitrile from polyethylene terephthalate over γ-Al₂O₃ based catalysts by fast pyrolysis with ammonia (γ-Al₂O₃催化快速热解氨化聚对苯二甲酸乙二醇酯PET塑料制备对苯二甲腈)

The optimal condition for producing TPN was over 1 g γ-Al₂O₃-2wt% catalyst at 500 ºC under carrier gas (50% NH3 and 50% N2) with yield of nitriles and TPN of 58.1 and 52.3 C%, respectively. The selectivity of TPN in the nitriles was around 90%. Meanwhile, a bit of aromatics, benzonitrile, acetonitrile were also produced as by-products with the total yields of less than 3 C%. The catalyst deactivated slightly after 5 cycles. Possible reaction routes were proposed and it was found that terephthalic acid, benzoic acid, related esters and amides were the major intermediates from PET to nitriles. Acetonitrile could be produced from acetaldehyde and its corresponding imines. In addition, 32.1 C% TPN with high purity (> 95%) was obtained via freezing recrystallization.

The carboxyl group in PET plastic was efficiently utilized for the production of terephthalonitrile and benzonitrile by controlling Ca(OH)₂/γ-Al₂O₃ catalysts and pyrolysis parameters (e.g. temperature, residence time, ammonia content). The best conditions are selected as 2% Ca(OH)₂/γ-Al₂O₃ (0.8 g), 500 ºC under pure ammonia with 58.3 C% terephthalonitrile yield and 92.3% selectivity in nitriles. In addition, 4% Ca(OH)₂/ Al₂O₃ was suitable for producing benzonitrile. With catalyst dosage of 1.2 g, residence time of 1.87 s, pyrolysis temperature of 650 ºC and pure ammonia (160 mL/min carrier gas flow rate), the yield and selectivity of benzonitrile were 30.4 C% and 82.6%, respectively.

Related results were published:

1. LJ Xu, XW Na, LY Zhang,  Q Dong, GH Dong, YT Wang, Zhen Fang*, Selective Production of Terephthalonitrile and Benzonitrile via Pyrolysis of Polyethylene Terephthalate (PET) with Ammonia Over Ca(OH)₂/Al₂O₃ Catalysts, Catalysts, 9, 436; doi:10.3390/catal9050436  (2019).
2. LJ Xu, LY Zhang, H Song, Q Dong, GH Dong, X Kong, Zhen Fang*, Catalytic Fast Pyrolysis of Polyethylene Terephthalate Waste Plastic for the Selective Production of Terephthalonitrile under Ammonia Atmosphere, Waste Management, 92, 97–106 (2019).

——————————————————————————————

利用塑料废弃物快速热解制备含氮化合物

最近，徐禄江博士和方真教授开发了一种氨催化热解法，将聚对苯二甲酸乙二醇酯（PET）塑料直接转化为对苯二甲腈（TPN）等含氮化合物。

在载气（50%NH₃和50%N₂）和温度500 ℃下，制备TPN的最佳条件为1 g γ-Al₂O₃-2wt%催化剂，腈类化合物和TPN的收率分别为58.1%和52.3%。TPN在腈类中的选择性约为90%。同时，还生产了少量芳烃、苯甲腈、乙腈等副产品，总收率小于3%。经过5个循环后，催化剂略微失活。作者提出了可能的反应路线，发现对苯二甲酸、苯甲酸、相关酯和酰胺是从PET到腈的主要中间体。乙醛及其亚胺可制得乙腈。此外，通过冷冻再结晶得到了32.1%的高纯度TPN（>95%）。

作者进一步通过控制Ca（OH）₂/γ-Al₂O₃催化剂和热分解参数（如温度、停留时间、氨含量），有效利用PET塑料中的羧基来生产对苯二甲酸和苯甲腈。选择2%Ca（OH）₂/γ-Al₂O₃（0.8 g），纯氨500 ℃为最佳条件，对苯二甲酸收率58.3C%，腈选择性92.3%。另外，4%的Ca（OH）₂/Al₂O₃也适用于苯甲腈的生产。催化剂用量1.2 g，停留时间1.87 s，裂解温度650 ℃，纯氨（160 mL/min载气流量），苯甲腈的收率和选择性分别为30.4c%和82.6%。

详情可见：

1. LJ Xu, XW Na, LY Zhang,  Q Dong, GH Dong, YT Wang, Zhen Fang*, Selective Production of Terephthalonitrile and Benzonitrile via Pyrolysis of Polyethylene Terephthalate (PET) with Ammonia Over Ca(OH)₂/Al₂O₃ Catalysts, Catalysts, 9, 436; doi:10.3390/catal9050436  (2019).
2. LJ Xu, LY Zhang, H Song, Q Dong, GH Dong, X Kong, Zhen Fang*, Catalytic Fast Pyrolysis of Polyethylene Terephthalate Waste Plastic for the Selective Production of Terephthalonitrile under Ammonia Atmosphere, Waste Management, 92, 97–106 (2019).

Prof. Fang attended the 17th European Meeting in Supercritical Fluids and gave keynote speech

On April 8-11, 2019, Prof. Zhen FANG attended the 17th European Meeting in Supercritical Fluids (EMSF2019) and 7th European Meeting on High Pressure Technology in Ciudad Real (Spain)(https://eventos.uclm.es/16387/detail/17-thsubindice-isasf-congress.html). He gave a keynote speech entitled “Hydrothermal Conversion of Renewable Resources and Wastes to Fuels” to introduce properties of hydrothermal water, conversion of biomass, hydrolysis, SCWO, recycling of plastics and particle synthesis. He also chaired a section and helped to evaluate the best posters  as the member of the selection committee for the CFS Jerry King Poster Award.

European Meeting in Supercritical Fluids (EMSF) is a biannual conference, supported by a number of universities and companies all around Europe, with a strong participation and implantation in the scientific community worldwide. The meeting are an exciting and informative with high quality programs including plenary/keynote lectures, invited talks, forums in a variety of topics, oral and poster presentations and many other social programs for over 250 participants from all around the world.

On April 7, before the meeting, Prof. Fang (as associate editor of Journal of Supercritical Fluids) also attended editorial meeting presided over by Prof. Erdogan Kiran, Editor-in Chief to discuss the issues related to the Journal such as virtual special Issues, manuscript processing software and manuscript review.

方老师方老师出席17届欧洲超临界流体会议并发表主旨演讲

2019年4月8日至11日,方真教授，出席了在西班牙雷阿尔城举行的第17届欧洲超临界流体会议（EMSF2019）和第7届欧洲高压技术会议(https://eventos.uclm.es/16387/detail/17-thsubindice-isasf-congress.html），并做了主旨发言。演讲题目为《水热转化可再生资源和废弃物为燃料》，内容包括：水热性质、生物质转化、水解、超临界水氧化、塑料回收和颗粒合成。此外，他亦担任一个分会的主席，并作为“杰里.金墙报奖”评选委员会成员，协助评审最佳墙报。

欧洲超临界流体会议是一个两年一次的会议，由许多欧洲各地的大学和公司参与和支持，拥有全球超临界流体和高压科技社区强大的参与和植入。日程包括全体会议/主题演讲，邀请讲座，各种主题的论坛，口头和海报。来自世界各地的250多名代表参与了演讲、讨论和许多其他社交活动。

另外，4月7日，会议开始前，方老师（作为超临界流体杂志副主编）也出席了刊物主编Erdogan Kiran教授主持的编辑委员会会议，讨论了该期刊有关的专题、稿件处理软件、稿件评审等问题。