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

固体酸和碱催化剂的合成及用以生产生物柴油和氢气

最近，生物能源组通过溶剂热炭法、 热解和磺化木质素从脱碱木质素中合成碳基固体酸。木质素在亚临界和超临界乙醇中碳化，提供了良好的表面性能，丰富的官能团 (2.81 和 1.35 mmol[H⁺]/g)，可为随后的磺化反应，合成高稳定、高活性的催化剂生产生物柴油。合成的催化剂，酸含量高 (> 5.05 mmol[H⁺]/g)，在80 摄氏度下，从油酸酯化反应生产生物柴油，产率 > 95%，催化剂可以循环3-5次。用该催化剂，从高酸值的小桐子油和混合的大豆油中，也成功合成高收率生物柴油（> 90%）。

同时，一种新型磁性碳基镍和硅酸钠催化剂 (Na₂SiO₃@Ni/C)也合成并用于共生产生物柴油和氢气，该方法是先将Ni(OH)₂沉淀于竹粉上，再热解和加载Na₂SiO₃。Na₂SiO₃@Ni/C 具有高碱值 (3.18 mmol/g) 和磁性 （15.7 Am²/kg），并且很稳定， 可使用4次并保持生物柴油产量 > 93%，催化剂有高的回收率（85.3%，循环5次后）。用在生产生物柴油失活的 Na₂SiO₃@Ni/C催化剂，水热气化粗甘油，气化率可达80.1 mol %并可生产82.7 mol %纯度的氢气。

结果发表在Green Chemistry和Applied Catalysis B: Environmental上。

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Synthesis of Solid Carbonaceous Acids and Base for Green Production of Biodiesel

Recently, biomass group synthesized carbonaceous acids from dealkaline lignin via solvothermal carbonization, pyrolysis and sulfonation. Carbonization of lignin in sub- and super-critical ethanol provided good surface properties with abundant functional groups (2.81 and 1.35 mmol [H⁺]/g) for the subsequent sulfonation to result in high active and stable catalysts for biodiesel production. The synthesized catalysts had high acid content (> 5.05 mmol[H⁺]/g), with biodiesel yield > 95% from the esterification of oleic acid at 80 ◦C and can be recycled 3-5 times. High biodiesel yield > 90% was obtained from Jatropha and blended soybean oils with high acid values.

A novel magnetic carbon-based nickel and sodium silicate catalyst (Na₂SiO₃@Ni/C) was also prepared by the precipitation of Ni(OH)₂ on bamboo powders, pyrolysis and the loading of Na₂SiO₃, and was used in the co-production of biodiesel and hydrogen. Na₂SiO₃@Ni/C has high basic content (3.18 mmol/g) and magnetism (15.7 Am²/kg), and is stable for 4 cycles with biodiesel yield > 93% and high recovery rate of 85.3% after 5 cycles. With the deactivated Na₂SiO₃@Ni/C, 80.1 mol% of crude glycerol gasification rate are achieved with 82.7 mol% H₂.

The results were published:

• (1)F Zhang, Xue-Hua Wu, Min Yao, Zhen Fang*, YT Wang, Production of Biodiesel and Hydrogen from Plant Oil Catalyzed by Magnetic Carbon-Supported Nickel and Sodium Silicate, Green Chemistry, 18, 3302-3314 (2016).
• (2)M Huang, J Luo, Zhen Fang*, H Li, Biodiesel Production Catalyzed by Highly Acidic Carbonaceous Catalysts Synthesized via Carbonizing Lignin in Sub- and Super-critical Ethanol, Applied Catalysis B: Environmental, 190, 103–114 (2016).

Production of biodiesel from plant oil catalyzed by magnetic Na₂SiO₃@Ni/C catalyst, and H₂ by the deactivated catalyst from by-product glycerol.

2016年5月23日，由昆明理工大学、西南林业大学5位专家组成的答辩委员会听取了由生物能源研究组2016年硕士毕业生朱长辉和博士毕业生张帆的论文报告和答辩。经答辩委员会讨论和无记名投票表决，一致同意朱长辉同学和张帆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和博士学位。在此毕业之际，向朱长辉同学和张帆同学表示祝贺。

同时，张帆同学还获2016中科院院长优秀奖。

Mr. Changhui Zhu and Mr. Fan Zhang passed their defenses for master and PhD degrees

On May 23th, 2016, five experts from Kunming University of Science and Technology and Southwest Forestry University attended the presentations and defenses of Mr. Changhui Zhu, a master student and Mr. Fan Zhang , a doctoral student in biomass group that were expected to be graduated in 2016 under Prof. Fang. After the discussion and secret ballot, the five dissertation committee members all agreed the theses and defense of Changhui Zhu and Fan Zhang, and suggested that the academic degree evaluation committee of Xishuangbanna Tropical Botanical Garden, CAS, award Mr. Zhu the master’s degree and Mr. Zhang the doctor’s degree in science, according to relevant regulations. On the occasion of graduation, congratulations to Changhui Zhu and Fan Zhang!

Mr. Fan Zhang also won 2016 CAS president award for his dissertation.

Biodiesel is synthesized successfully in a pilot continuous compacted flow reactor (3-5 t/day) designed by biomass group

Supported by CAS “135” projects (XTBG-T02), “study on the scientific basis for large-scale synthesis of Jatropha biodiesel”, under the guidance of Prof. Zhen Fang, Mr. Zhang fan (doctoral student) designed and set up a patented continuous flow reactor (ZL 201420785283.0, license transferred to Shandong Yikang pharmaceutical co. LTD on Oct. 23, 2018) for biodiesel production. The reactor system is composed of control panel, continuous feeding unit, reaction body, continuous discharge unit, product purification and separation unit.

Jatropha biodiesel was produced successfully on 28 April, 2016, with biodiesel production up to 3-5 tons/day in a 5 L of vessel volume (operating space). Compared with traditional batch and flow reactors, the reactor has superior characteristics of small volume, low energy consumption, and high production efficiency. Assisted with magnetic solid base (CN 201410764721.X) and solid acid catalysts prepared by Biomass group, green production of biodiesel was realized successfully with easy separation of catalyst by a magnet  for cycles. Related results were patented and published in international journals, Fuel, Energy, Applied Energy and Green Chemistry.

Related patents and papers：

[1] Fan Zhang, X.H. Wu, M. Yao, Zhen Fang*, Y.T. Wang. Production of Biodiesel and Hydrogen from Plant Oil Catalyzed by Magnetic Carbon-Supported Nickel and Sodium Silicate, Green Chemistry. 2016

[2] Fan Zhang, Zhen Fang*, Y.T. Wang. Biodiesel Production Direct from High Acid Value Oil with a Novel Magnetic Carbonaceous Acid, Applied Energy, 2015; 155: 637-647.

[3] F. Zhang, Zhen 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.

[4] Y.T. Wang, Zhen Fang*, F. Zhang, B.J. Xue. One-step Production of Biodiesel from Oils with High Acid Value by Activated Mg-Al Hydrotalcite Nanoparticles, Bioresource Technology, 2015; 193: 84-89.

[5] B.J. Xue, J. Luo, F. Zhang, Zhen Fang*, Biodiesel Production from Soybean and Jatropha Oils by Magnetic CaFe₂O₄-Ca₂Fe₂O₅-Based Catalyst, Energy, 2014; 68: 584-591.

[6] 张帆，方真*，薛宝金，苏同超，王一同。用于可溶性糖及生物柴油制备的连续流动釜式反应装置，新型专利，ZL 201420785283.0.

[7] 张帆，方真*。一种碳基磁性固体碱催化剂及其应用，发明专利，CN 201410764721.X (受理中).

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生物能源组设计组建的连续流动釜式反应装置

成功用于生物柴油连续高效合成

连续流动釜式反应装置连续高效合成生物柴油 (Continuous production of biodiesel, 3-5 t/day)

由中科院“一三五”项目突破二课题“小桐子规模化合成生物液体燃料的科学基础研究”的支持，在导师方真研究员的悉心指导下，在职博士生张帆作为项目主要完成人设计组建了连续流动釜式反应装置（ZL 201420785283.0, 专利2018年10月，转让于山东益康药业有限公司），该装置由操控台、连续进料单元、反应釜主体、连续出料单元、产物纯化和分离单元等组成，该连续流动釜式反应装置可以同时解决：传统间歇批次釜式反应装置需要批次进料、反应效率低和反应能耗高等问题；以及传统连续流动管式反应装置混合效果差、固体催化剂易堵塞管路和需要提供持续高压等问题。

2016年4月28日，生物能源组利用连续流动釜式反应装置成功实现了小桐子生物柴油连续合成工艺，仅5L的釜体容积，5 m²的操作空间，生物柴油产量即可达到3-5吨/天，与传统批次或流动反应装置相比，体现出外型小、能耗低和效率高等优越特性。结合本课题组设计制备的碳基磁性固体碱催化剂（CN 201410764721.X）和磁性含碳固体酸催化剂，有望解决催化剂分离回收成本高、反应区域难以控制和固体催化剂堵塞管路等工业难题，同时未参与反应的甲醇可及时回收再利用，生物柴油副产物甘油可以水热气化合成氢气，从而实现连续高效合成生物柴油的绿色工艺研究。相关研究成果已经在Fuel, Energy, Applied Energy和Green Chemistry等国际期刊上发表，并得到国内外专家学者的宝贵建议和充分肯定。

Recently, Elsevier-Scopus  listed Prof. Zhen Fang in “Most Cited Chinese Researchers” in energy for 2015 again after 2014.
继2014年，方真研究员再次进入2015年“中国高被引学者”能源领域榜单（Elsevier-Scopus).
Prof. Zhen Fang (PhDs Eng., McGill; CAU); a researcher in bioenergy; inventor of “fast hydrolysis” process; Editor-in-Chief, Springer Book Series – Biofuels and Biorefineries; Associate Editor, Biotechnology for Biofuels (IF 6.2, Highest IF in Biofuels); and Editorial Advisory Board Members of Biofpr (Biofuels, Bioproducts and Biorefining, IF 4.3) and Energy, Sustainability and Society (a Springer open Journal).

2015年“中国高被引学者榜单”研究数据和技术分析基于全球最大的同行评议学术论文索引摘要数据库（Scopus数据库），该数据库收录来自全球超过5000个出版商、21000种期刊的5500余万条文献索引，覆盖各个学科，并提供各种工具用于追踪、分析和可视化学术研究，通过对客观引用数据的分析，对研究者在世界范围内的影响力进行系统的评价。此次榜单中，来自中国的社会科学、物理、化学、数学、经济等38学科的1744名最具世界影响力的中国学者入选。

（http://www.zuihaodaxue.com/Article.jsp?id=WzQpgBmjMtkbcp4LvpaLvG8oNQTgE8)

2014:

11.4%的中国科学院院士是高被引学者

3.7%的中国工程院院士是高被引学者

17.6%的长江学者特聘教授是高被引学者

18.1%的国家杰出青年科学基金获得者是高被引学者

Biomass group was evaluated as the best group for 2015

Recently, Biomass group was evaluated as best group of Key Laboratory of Tropical Plant

Resources and Sustainable Use of CAS for 2015, and excellent research group of Xishuangbanna Tropical Botanical Garden for 2015.

Congratulations!
生物能源组被评为2015年优秀小组

最近，生物质组被评为2015年度中国科学院热带植物资源和可持续利用重点实验室的最佳小组，以及2015年度西双版纳热带植物园的优秀研究小组。