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

One-Pot Hydrolysis of cellulose and hemicellulose in Lignocellulosic Biomass Pretreated by NaOH-Freeze

Biomass wastes were NaOH-freeze pretreated for one-pot hydrolysis with yields increased by >214% for cellulose, >59% for hemicellulose, respectively. （对生物质废弃物进行一锅法水解，NaOH 冷冻预处理后，纤维素水解率增加>214%，半纤维素水解率增加>59%。）

  Recently, Miss Tongchao Su (PhD student from China University of Science and Technology) supervised by Prof. Zhen FANG hydrolyzed cellulose and hemicellulose in lignocelluloses in one-pot. In their work, in order to achieve one-pot hydrolysis of cellulose and hemicellulose in lignocellulosic biomass, freeze pretreatment with 0−5 wt % NaOH (3 wt% was chosen as the best concentration) and subsequent microwave-assisted dilute sulfuric acid hydrolysis were applied to tropical plant wastes. Single factor optimization of hydrolysis of the pretreated bagasse was studied, and the best conditions (140 °C, 30 s, substrate/solvent ratio of 1/60 and 0.4 M H2SO4) were further applied to Jatropha and Plukenetia hulls. Under the best conditions, yields of sugars from cellulose (glucose) and hemicellulose (xylose, mannose, and arabinose) in the pretreated bagasse were 84.0% and 92.7%, enhanced by 273.4% and 59.3% as compared with untreated sample, respectively. For the pretreated Jatropha and Plukenetia hulls, yields of glucose and hemicellulose sugars were 85.7% and 93.3% (increased by 225.9% and 75.4%),  and 85.0% and 92.9% (increased by 214.8% and 81.4%), respectively.
The results were published:
TC Su, Zhen Fang*, One-pot microwave-assisted hydrolysis of cellulose and hemicellulose in selected tropical plant wastes by NaOH-freeze pretreatment, ACS Sustainable Chemistry & Engineering, 5(6), 5166–5174 (2017).

一锅法水解 经NaOH 冷冻预处理后的生物质中纤维素和半纤维素

  最近，苏同超同学（中国科学技术大学生命学院博士研究生）在方老师的指导下，对木质纤维素中的纤维素和半纤维素进行了一锅水解的研究。
为了实现木质纤维素生物质中的纤维素和半纤维素的同时水解，首先对生物质用0−5 wt% NaOH（3wt%被选为最佳浓度）冷冻预处理，随后进行微波稀酸水解。
对预处理后的甘蔗渣水解条件的优化进行了单因素实验研究，并利用所得的最佳条件（140 °C，30秒，生物质/溶剂比为1／60和0.4 M H2SO4）进一步用于小桐子和星油藤壳的水解。在最佳条件下，和未经处理的样品相比，预处理后的甘蔗渣纤维素糖产量（葡萄糖）和半纤维素（木糖、甘露糖、阿拉伯糖）糖产量，分别为84%和92.7%，提高了273.4%和59.3%。对预处理后的小桐子和星油藤壳，产生葡萄糖和半纤维素糖分别为85.7%和93.3%（分别增加225.9%、75.4%），85%和92.9%（分别增加了214.8%和81.4%）。
结果发表在ACS Sustainable Chemistry & Engineering: TC Su, Zhen Fang*, One-pot microwave-assisted hydrolysis of cellulose and hemicellulose in selected tropical plant wastes by NaOH-freeze pretreatment, ACS Sustainable Chemistry & Engineering, 5(6), 5166–5174 (2017).

方真教授会见加拿大约克大学JA Kozinski院士

方真教授访问加拿大约克大学和麦基尔大学

应加拿大约克大学JA Kozinski教授（加拿大工程院院士）邀请，方真教授2017年6月14-21日对加拿大进行了访问。他参观了约克大学工学院机械系和土木工程系，访问了约克大学能源实验室（多伦多）并讨论双方合作研究和共同申请项目等问题。

同时，方真教授还顺访了位于蒙特利尔市的麦基尔大学，会见了化学系Ian Butler教授，材料工程系Roderick I. L. GUTHRIE教授（加拿大皇家科学院院士）和土木工程系的Yixin Shao教授, 探讨进一步合作问题。另外，方真教授参观了化学系CJ Li教授（加拿大皇家科学院院士，Green Chem副主编）实验室，对他们在绿色化学方面的成果和研究产生了浓厚的兴趣。

Prof. Zhen Fang visited York and McGill in Canada

From June 14 to 21, 2017, Prof. Zhen Fang visited York and McGill in Canada. At York, he met Prof. Kozinski (The Founding Engineering Dean) and toured the Departments of Mechanical and Civil engineering, visited the York University Energy Laboratory and discussed issues such as collaborative research and joint application for projects.

Later, Prof. Fang visited McGill University in Montreal, where he met Profs. Ian Butler (Chemistry Department), Roderick I. L. Guthrie (Materials Engineering Department) and Yixin Shao (Civil Engineering Department) to explore further cooperation. In addition, Prof. Fang visited Prof CJ Li’s Lab (Prof. Li is associate editor of Green Chem) in Chemistry Department, and found a strong interest in the achievements and research in the field of green and sustainable chemistry made at McGill.

李兴康顺利通过2017年博士学位论文答辩

2017年5月22日，由昆明理工大学、云南师范大学等5位专家组成的答辩委员会听取了博士毕业生李兴康的论文<<有机溶剂预处理甘蔗渣及酶水解的研究>>报告和答辩。经答辩委员会讨论和无记名投票表决，一致同意李兴康同学通过学位论文答辩，建议按有关规定授予理学博士学位。在此毕业之际，向李兴康同学表示祝贺。

英国爱丁堡大学郑莹教授一行访问我院

Synthesis of Magnetic Carbonaceous Solid Acid and Base from Jatropha Hulls for the Production of Jatropha Biodiesel

Jatropha seeds were extracted oil for biodiesel production and the hulls were carbonized to load active sites as magnetic carbonaceous solid acid and base catalysts. Crude Jatropha oil was esterified to decrease its acid value to 1.3 from 17.2 mg KOH/g by the solid acid, and subsequently transesterified to biodiesel (96.7% yield) catalyzed by the solid base. After 3 cycles and magnetically separated, the deactivated base was catalyzed the hydrothermal gasification of biodiesel by-product (crude glycerol) with gasification rate of 81% and 82% H₂ purity.

    Recently, biomass group synthesized magnetic carbonaceous solid acid (C-SO₃H@Fe/JHC) and base (Na₂SiO₃@Ni/JRC) catalysts by loading active groups on the carbonaceous supporters derived from Jatropha-hull hydrolysate and hydrolysis residue. Characterization of their morphology, magnetic saturation, functional groups and total acid/base contents were performed by various techniques. Additional acidic functional groups that formed with Jatropha-hull hydrolysate contributed to the high acidity of C-SO₃H@Fe/JHC catalyst for the pretreatment (esterification) of crude Jatropha oil with high acid values (AV). The AV of esterified Jatropha oil dropped down from 17.2 to 1.3 mg KOH/g, achieving a high biodiesel yield of 96.7% after subsequent transesterification reaction with Na₂SiO₃@Ni/JRC base that was cycled at least 3 times with little loss of catalysis activity. Both solid acid and base catalysts were easily recovered by magnetic force with average recovery yields of 90.3 wt% and 86.7%, respectively. After washed by ethanol, the catalysts were cycled for 10 times. The AV of esterified oil and biodiesel yield using the recycled catalysts remained below 2.0 mg KOH/g and above 85%, respectively. The existence of catalyst ions and residual methanol contributed to high H₂ yield (81.0%) and high purity (81.7%) in the hydrothermal gasification of glycerol by-product using the deactivated solid base.

The results were published:

F Zhang, XF Tian, Zhen Fang*, M Shah, YT Wang, W Jiang, M Yao, Catalytic Production of Jatropha Biodiesel and Hydrogen with Magnetic Carbonaceous Acid and Base Synthesized from Jatropha Hulls,  Energy Conversion and Management, 142, 107–116  (2017).

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小桐子壳合成磁性固体酸和碱催化剂及用以生产小桐子生物柴油和氢气

最近,生物能源组通过对小桐子壳水解液和水解残渣合成的磁性碳载体加载活性基团，合成磁性炭质固体酸 (C-SO₃H@Fe/JHC)和碱(Na₂SiO₃@Ni/JRC)催化剂。通过各种测试技术对其形态、磁性饱和度、功能基团和总酸/碱含量进行表征。小桐子壳水解液形成的酸性官能团有助于其负载的催化剂（C-SO₃H@Fe/JHC）具备更高的酸密度，用于预处理(酯化)高酸值小桐子油, 酸值从17.2 降为 1.3 mg KOH/g。预处理后的小桐子油，在由小桐子壳水解残渣合成的碱性催化剂(Na₂SiO₃@Ni/JRC)作用下，通过脂交换反应，生物柴油产率可高达96.7%,该碱性催化剂可循环至少三次, 催化活性损失很少。固体酸和碱催化剂均可通过磁铁轻易地回收, 平均回收率为 90.3 wt% 和86.7%。用乙醇洗涤后, 催化剂可循环十次。使用回收的催化剂，预处理油的酸值低于2.0 mg KOH/g，生物柴油的产率高达85%以上。催化剂离子和残留的甲醇可用于进一步提高，用失活固体碱催化水热气化甘油副产品的氢气产量 (81.0%) 和纯度 (81.7%)。

结果发表在Energy Conversion and Management : F Zhang, XF Tian, Zhen Fang*, M Shah, YT Wang, W Jiang, M Yao, Catalytic Production of Jatropha Biodiesel and Hydrogen with Magnetic Carbonaceous Acid and Base Synthesized from Jatropha Hulls,  Energy Conversion and Management, 142, 107–116  (2017)。