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

首届云南生物质能源发展论坛暨云南省能源研究会成立三十周年大会于2015年10月24至25日在云南昆明，西南林业大学召开。来自云南省发展和改革委员会、云南省工业和信息化委员会、云南大学、云南师范大学和中国科学院西双版纳热带植物园等30多个单位的160余位专家、学者及企业界人士出席了会议。

本次论坛主题为“云南生物质能源的发展与创新”，云南省能源研究会副理事长/秘书长、材料工程学院郑志锋院长主持了开幕式，中国科学院西双版纳热带植物园方真研究员被论坛邀请主持了24日下午学术会议。张帆助理研究员以“高效合成生物柴油绿色工艺研究进展”为题目做了学术报告，向大家汇报了近年来国内外高效合成生物柴油绿色工艺的研究状况，生物能源组在生物能源领域取得的成绩以及张帆本人在高效合成生物柴油绿色工艺研究过程中获得的一些收获和近期在Applied Energy、Energy、Fuel和Bioresource Technology等国际能源期刊上发表的研究成果。感谢中科院热带植物资源可持续利用重点实验室、中科院“一三五”课题(XTBG-T02)和国家自然科学基金青年项目(No. 31400518)的鼓励和支持。

Prof. Zhen Fang and Mr. Fan Zhang attended “First Yunnan Biomass Energy Development Forum”

By Fan Zhang

The First Yunnan Biomass Energy Development Forum, or the Yunnan Provincial Energy Society 30 year Anniversary was held at Southwest Forestry University in Kunming, Yunnan on October 24-25, 2015.

More than 160 delegates from 30 governmental agencies, institutions and industries such as Yunnan Development and Reform Commission, Yunnan Provincial Industry & Information Technology Commission, Yunnan University, Yunnan Normal University and Chinese Academy of Sciences, Xishuangbanna Tropical Botanical Garden attended the meeting.

The theme of this forum is “the Development and Innovation of Biomass Energy in Yunnan”, the Dean of Material Engineering College, Prof. Zhifeng Zheng (deputy director/secretary general of Yunnan Energy Research Association) presided over the opening ceremony. Prof. Zhen Fang from Xishuangbanna Tropical Botanical Garden (CAS) was invited to preside over the academic meeting. Mr. Fan Zhang has given a talk on “Research Progress of High Efficiency Synthetic Biodiesel with Green Technology”. He introduced research status of high efficiency synthetic biodiesel with green technology in China and abroad in recent years, achievements in the field of bio-energy in Xishuangbanna Tropical Botanical Garden and also his recent research results published in the Applied Energy, Energy, Fuel and Bioresource Technology. His work was got financial supports from Chinese Academy of Sciences [Key Laboratory of Tropical Plant Resources and Sustainable Use and CAS 135 program (XTBG-T02)] and the Natural Science Foundation of China (No. 31400518).

图为首届云南生物质能源发展论坛暨云南省能源研究会成立三十周年大会现场

Recently, Springer has published a book entitled “Production of Hydrogen from Renewable Resources” edited by Profs. Zhen Fang, Richard L. Smith Jr.，Xinhua Qi， Springer, Hardcover ISBN 978-94-017-7329-4, 368 pages, 2015. (http://www.springer.com/cn/book/9789401773294).

As a clean energy carrier with high energy capacity, hydrogen has the potential to supplement or replace traditional fossil fuels in the near future. The use of renewable biomass resources for hydrogen production is receiving a lot of attention as a innovative and robust processes continue to demonstrate hydrogen production from many types of biomass substrates. The present text provides state-of-the-art reviews, current research and prospects of producing hydrogen by fermentation, electrochemical, bioelectrochemical, gasification, pyrolysis and solar techniques from many possible biomass resources.  Hydrogen separation, storage and applications are also covered.

This book contains 12 chapters contributed by leading experts in the field. The text is arranged into four key areas:

Part I: Bioconversion (Chapters 1-3)

Part II: Thermoconversion (Chapters 4-7)

Part III: Electrochemical and Solar Conversions (Chapters 8-10)

Part IV: Separations and Applications with Fuel Cells (Chapters 11-12)

This book reviews current research and prospects of producing hydrogen by bio, thermal and electrochemical methods. Hydrogen separation, storage and applications are also covered. The text should be of interest to students, researchers, academicians and industrialists in the areas of energy, environmental and chemical sciences, engineering, resource development, biomass processing, sustainability and the hydrogen economy.

This book is the fifth book of the Springer series entitled, “Biofuels and Biorefineries” (Prof. Zhen Fang is serving as editor-in-Chief), and the twelfth English book published by Prof. Zhen Fang since 2009.

斯普林格新书《可再生资源制氢》出版

陈敬妹

由方真研究员、Richard L. Smith Jr.和Xinhua Qi教授主编的新书《Production of Hydrogen from Renewable Resources》，最近由斯普林格公司出版发行。（精装，368页，ISBN 978-94-017-7329-4, (http://www.springer.com/cn/book/9789401773294，2015）。

作为具有高能量的清洁能源载体，氢具有替代或补充传统的化石燃料的潜力。利用可再生的生物质资源生产氢气得到了极大的关注。本书回顾了最新的研究成果，以及生物、热化学和电化学方法制氢的前景，包括氢分离、存储和应用技术。该书对在能源、环境和化学科学、工程、资源开发、生物质处理、可持续性和氢经济领域感兴趣的学生、研究人员、学者和实业家有很大的参考价值。

本书包含12章，由来自世界各地该领域的顶尖专家撰写。该书包括四个关键领域：第一部分：生物转化（第1-3章）；第二部分：热化学转化（第4-7章）；第三部分：电化学和太阳能转换（8-10章），第四部分：分离和应用技术，与燃料电池（11-12章）。

该书是斯普林格系列丛书“生物燃料和生物炼制”（ 方真研究员担任该丛书总编辑）出版的第五本专著，也是方真研究员自2009年以来，编著出版的第十二部英语专著。

Sulfonated activated carbon acid (AC-SO₃H) can catalyze both esterification and transesterification to produce biodiesel from oils with high acid value (AV) without pretreatment. Because, activated carbon has properties like its surface oxides, reducibility, and stability in both acidic and basic media, as well as its structural resemblance to graphite , fullerenes and nanotubes to support -SO₃H group well. However, the separation of AC-SO₃H catalyst needs filtration or centrifugation that is energy and time consuming. So, many magnetic carbonaceous acids were successfully prepared that are easily separated by a magnet for cellulose hydrolysis, fructose dehydration and hydrolysis of polysaccharides. But these catalysts have low acid content (e.g., 1.3, 1.95 and 0.38 mmol/g) for effective biodiesel production, some have low magnetism.

Mr. Zhang Fan, a PhD student, under the guidance of Professor Zhen Fang in Xishuangbanna Tropical Botanical Garden (CAS), prepared a cheap and active magnetic heterogeneous acid for the production of biodiesel from oils with high AV. First, magnetic core is formed by hydrothermal precipitation from both glucose and iron chloride and subsequent high temperature pyrolysis. The core is again hydrothermally coated with glucose and stabilized by pyrolysis, and subsequent sulfonated as acid catalyst. It was found that pyrolysis temperature at 600 °C led to excellent structure to produce catalyst with high acid density (2.79 mmol/g) and strong magnetism (14.4 Am²/kg). The catalyst presents high active, stable and recoverable in the production of Jatropha biodiesel from crude oil with high AV (17.2 mg KOH/g) with high yields for 3 cycles (90.5%, 91.8%, 90.3%), slight reduction in total acid density (2.43 vs. 2.79 mmol/g) and high catalyst recovery rate of 96.3%. It was also found that ultrasound can resist free fatty acids. High biodiesel yield (90.7%) was still achieved from high AV oil (4.8) at low US energy density (0.1 W/mL) with Na₂SiO₃ catalyst.

The results are published in Applied Energy and Fuel:

1. Fan Zhang, Z. Fang*, Y.T. Wang. Biodiesel production direct from high acid value oil with a novel magnetic carbonaceous acid, Applied Energy, 2015; 155: 637-647.
2. Fan Zhang, Z. Fang*, Y.T. Wang. Biodiesel production directly from oils with high acid value by magnetic Na2SiO3@Fe3O4/C catalyst and ultrasound, Fuel, 2015; 150: 370–377.

新型碳基磁性固体酸催化剂用于高酸值油脂直接转化合成生物柴油

 直接用高酸值油脂制备生物柴油是一难点和研究热点。

磺化的活性炭可用于酯化和酯交换反应催化高酸值油脂制备生物柴油。因为活性炭具有类似于表面氧化物，还原剂和稳定的酸碱基团等特性，并且它的结构与石墨，富勒烯和碳纳米管相似并可以构建-SO₃H酸基团。目前，已成功地研制出磁性碳基固体酸并用于磁场回收，例如分别用于纤维素水解、果糖降解和多糖水解的催化剂，但是以上催化剂较低的酸量（如：1.3, 1.95 and 0.38 mmol/g）或较弱的磁性不适用于生物柴油制备。

中国科学院西双版纳热带植物园生物能源组，博士生张帆在方真研究员的指导下，制备出一种廉价和高活性的磁性固体酸催化剂用于高酸值油脂制备生物柴油。催化剂的制备方法：首先通过葡萄糖和氯化铁混合溶液在高温水热条件下制备碳基磁核，然后利用水热碳化葡萄糖再次包埋热处理后的碳基磁核，最后通过高温热处理后进行磺化制备碳基磁性固体酸。研究发现在600 °C温度下热处理再磺化制备的固体酸，同时具有高酸量（2.79 mmol/g）和磁饱和度（14.4 Am²/kg），该催化剂具有高活性，稳定性和可回收性，循环3次用于小桐子生物柴油（生物柴油产率：90.5%，91.8%，90.3%; 小桐子油酸值17.2 mg KOH/g）制备，催化剂酸量略有下降（2.43 vs. 2.79 mmol/g）并且具有96.3%的回收率。同时，还发现，超声波能抗自由脂肪酸：以Na₂SiO₃为催化剂，在较低的超声波能量密度下（0.1 W/mL），高酸值小桐子油（4.8 mg KOH/g）的生物柴油产率仍然可以达到90.7%。

相关研究成果发表在国际著名能源期刊Applied Energy和Fuel上：

1. Fan Zhang, Z. Fang*, Y.T. Wang. Biodiesel production direct from high acid value oil with a novel magnetic carbonaceous acid, Applied Energy, 2015; 155: 637-647.
2. Fan Zhang, Z. Fang*, Y.T. Wang. Biodiesel production directly from oils with high acid value by magnetic Na2SiO3@Fe3O4/C catalyst and ultrasound, Fuel, 2015; 150: 370–377.

新型碳基磁性固体酸催化剂用于高酸值油脂转化合成生物柴油

Basic catalytic transesterification of oils with homogeneous [(e.g., sodium methoxide, potassium or sodium hydroxide and heterogeneous catalysts (e.g, CaO and sodium silicate) is the most common method for biodiesel production at low temperatures (e.g., 50-60 ^oC). However, they are easily to form soap with free fatty acids (FFAs) when low qualified oils with high acid value (AV) are used as raw materials, and two-step process composed of esterification and transesterification catalyzed over acidic and basic catalysts was developed. But, the process is too complex and costly. This work aims to directly produce biodiesel from oils with high acid value without any pretreatment using activated nanosized Mg-Al hydrotalcite.
Miss Yitong Wang (Master student), under the guidance of Professor Dr. Zhen Fang from Xishuangbanna Tropical Botanical Garden (CAS), prepared Mg-Al hydrotalcite (HT-Ca) nanoparticles (< 45 nm) by co-precipitation and hydrothermal activation with aqueous Ca(OH)₂ solution. HT-Ca presented both acidic and basic due to the formation of Mg₄Al₂(OH)₁₄.3H₂O, Mg₂Al(OH)₇ and AlO(OH) nanocrystals to esterify and transesterify oils with high AV. Under conditions of 5 wt% HT-Ca, 160 ^oC, 30/1 methanol/oil molar ratio and 4 h, 93.4% Jatropha biodiesel yield was obtained at AV of 6.3 mg KOH/g with 4 cycles (biodiesel yield > 86%). It was further found that it can resist FFAs, and biodiesel yield reached 92.9% from soybean oil with high AV of 12.1. HT-Ca catalyst showed a potential practical application for direct production of biodiesel from oils with high AV without pretreatment.

The results are published in Bioresource Technology:

YT Wang, Zhen Fang*, F Zhang, BJ Xue. One-step production of biodiesel from oils with high acid value by activated Mg–Al hydrotalcite nanoparticles, Bioresource Technology, 193, 84–89 (2015).

活化Mg-Al 水滑石纳米颗粒用于一步法催化高酸值油脂制备生物柴油

 由于中国的国情限制，用于制备生物柴油的非食用原料油酸值都比较高。这样，碱性催化剂在低温（如50摄氏度）制备生物柴油容易发生严重的皂化反应。而酸性催化剂制备生物柴油时，尽管没皂化反应，但要求较高的反应温度（如220摄氏度），对设备的质量要求也很高，同时易腐蚀设备。所以，本研究目的是制备同时具有酸碱性的催化剂可以一步法直接催化高酸值的油脂变成生物柴油。
中国科学院西双版纳热带植物园生物能源组，硕士生王一同小姐在方真研究员的指导下，成功合成了Mg-Al 水滑石纳米颗粒，将其活化后用于催化高酸值的小桐子油以及高酸值的混合大豆油制备生物柴油。实验结果表明：该纳米颗粒具有较好的抗酸性，在反应温度160 ^oC, 5%催化剂量，30/1醇油摩尔比和4 h 的反应时间条件下，催化酸值为6.3的小桐子油，生物柴油的产率可以达到93.4%，当催化酸值为12.1的混合大豆油制备生物柴油，产率可以达到92.9%。该纳米颗粒重复使用四次，生物柴油的产率依然可以达到86%以上。活化后的Mg-Al 水滑石纳米颗粒表现出良好的催化性能。

相关研究成果发表在国际著名能源期刊Bioresource Technology上：

YT Wang, Zhen Fang*, F Zhang, BJ Xue. One-step production of biodiesel from oils with high acid value by activated Mg–Al hydrotalcite nanoparticles, Bioresource Technology, 193, 84–89 (2015)

图为活化的Mg-Al 水滑石纳米颗粒用于小桐子生物柴油制备

5月15日，由昆明理工大学、西南林业大学、中国科学院昆明植物研究所和中国科学院西双版纳热带植物园专家组成的答辩委员会听取了由生物能源研究组2015年硕士毕业生黄梅的论文报告和答辩。经答辩委员会讨论和无记名投票表决，一致同意黄梅同学通过学位论文答辩，建议按有关规定授予理学硕士学位。在此毕业之际，向黄梅同学表示祝贺。

Master student of biomass group passed her defense of degree dissertation in 2015

In May 15th, five experts from Kunming University of Science and Technology, Southwest Forestry University, Kunming Institute of Botany, CAS (Chinese Academy of Sciences), and Xishuangbanna Tropical Botanical Garden, CAS heard the report and defense of Mei HUANG, a master student of biomass group that was expected to be graduated in 2015. After discussion and secret ballot, five dissertation committee members all agreed the thesis and defense of Mei HUANG, and suggested the academic degree evaluation committee of Xishuangbanna Tropical Botanical Garden, CAS award to HUANG the master’s degree in science, according to relevant regulations. Congratulation to HUANG!