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     最近,生物能源组博士生王一同在方真教授的指导下,通过四步法合成了双功能磁性固体酸催化剂,并应用于生物柴油制备。

     为了降低生物柴油制备工艺的能耗,通过四步法合成一种同时具有路易斯酸位点和布朗斯特酸位点的磁性固体酸。该固体酸催化剂催化能力强,表现为其酯化油酸获得的生物柴油产率高达97%,转酯化高酸值的豆油后获得生物柴油产率高达95%,并且在小桐子原油(酸值为17.2 mg KOH/g)的预处理过程中,能有效降低小桐子原油酸值至0.7 mg KOH/g。另外,合成的双功能磁性固体酸拥有较好的稳定性,通过简单的磁性分离循环使用10次后,获得的生物柴油产率仍在90%以上。由此可见,合成的高活性和高稳定性的磁性固体酸催化剂,在制备生物柴油中展示了出色的工业应用能力。

     相关成果发表以“Biodiesel Production from High Acid Value Oils with a Highly Active and Stable Bifunctional Magnetic Acid”为题发表于Applied energyhttp://dx.doi.org/10.1016/j.apenergy.2017.07.060)。

四步法合成功能磁性固体酸催化剂示意图

      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”的前期支持,生物能源组张帆博士利用小桐子果壳水解液和水解残渣分别合成了碳基磁性固体酸 (C-SO3H@Fe/JHC)和固体碱(Na2SiO3@Ni/JRC)催化剂。通过多种分析测试方法对合成催化剂的形态、磁饱和度、功能基团以及总酸/碱含量进行深入分析发现:小桐子壳水解液形成的酸性官能团有助于其活化碳载体具备更高的酸密度;利用C-SO3H@Fe/JHC催化预处理(酯化)高酸值小桐子油时,可使其酸值从17.2降至1.3 mg KOH/g;再利用Na2SiO3@Ni/JRC催化降酸预处理后的小桐子油,生物柴油得率高达96.7%,该催化剂循环三次时催化活性无明显损失。催化合成生物柴油后的碳基磁性固体催化剂均可通过外磁场进行分离与回收。此外,活性下降的碳基磁性固体碱催化剂有利于副产品甘油水热气化生产氢气。与传统来自于葡萄糖和竹粉的碳源材料相比,利用小桐子果壳水解液及残渣制备的碳基磁性催化剂具备更丰富的官能团位点、更特异的表面区域以及孔隙容积,从而实现小桐子果综合利用合成生物燃料的绿色工艺研究。

      本研究获得了国家自然科学基金、中科院青年创新促进会和中科院“一三五”等项目的资助,相关研究成果以“Catalytic Production of Jatropha Biodiesel and Hydrogen with Magnetic Carbonaceous Acid and Base Synthesized from Jatropha Hulls”为题发表在国际期刊Energy Conversion and Management上。

桐子果(果壳+果油)综合利用合成生物柴油及联产氢气的绿色工艺流程图

        9月22日,从《中国科学院关于公布2017年度中国科学院优秀博士学位论文评审结果的通知》和《中国科学院关于公布2017年度中国科学院优秀导师奖评审结果的通知》中获悉,版纳植物园生物能源研究组2016届博士毕业生张帆获得2017年度中国科学院优秀博士学位论文奖,其导师方真研究员获优秀导师奖。 

  张帆于2013年9月开始博士阶段学习,师从方真研究员,主要研究方向为热带植物资源绿色转化合成高值生物化学品。在中科院“一三五”项目突破二课题(XTBG-T02)的支持下,顺利完成博士学位论文:“碳基磁性催化剂制备及其催化合成生物柴油绿色工艺研究”,该论文围绕利用小桐子果壳、种皮和竹粉等热带生物质废弃物替代传统葡萄糖和活性炭为碳质材料,制备出多种可磁场分离的新型碳基磁性固体酸/碱催化剂(ZL 201610754946.6,ZL 201410764721.X);并通过多种表征分析方法详细阐述了反应与合成机理;最后利用自主设计组建的连续流动釜式反应装置(ZL 201620978132.6,ZL 201420785283.0)协同催化剂高效清洁合成生物柴油,以此实现了废弃植物残渣综合利用制备催化剂并用于合成生物柴油及副产物甘油转化的绿色工艺研究。 

  在版纳植物园及导师们的悉心培养与指导下,他在攻读博士及获得学位后一年期间,分别以通讯或第一作者在Green Chemistry, Applied EnergyEnergy Conversion and Management等TOP10%国际期刊上发表研究性论文5篇,另以第一或参与作者发表SCI论文6篇,申请授权专利6项,主持国家自然科学基金、中科院青年创新促进会与云南省应用基础研究项目等。  

       引自http://www.xtbg.ac.cn/xwzx/zhxw/201709/t20170925_4864510.html

   

        7月13号上午,云南山洼洼农业科技股份有限公司周乐云总经理带队来到版纳园生物能源组参观交流。这是继7月5号推广站与生物能源组成员到该公司交流后的再一次交流讨论。两次交流期间,双方就美藤果油开发的市场定位、产品细分以及美藤果的种植、加工方面进行深入交流。

        期间山洼洼公司分享了国内美藤果油的市场调研情况,指出美藤果作为一种富含α—亚麻酸的高端油料,通过冷压榨提炼的果油具有广阔的市场前景,并就美藤果油产品形式提出独到见解。

        随后,生物能源组张帆博士、罗嘉博士带领山洼洼公司成员参观了生物能源组的实验平台,并介绍了版纳园的公共服务中心实验平台,双方就美藤果油产品研发方向达成初步共识。

7月13号版纳园昆明分部讨论会

7月5号山洼洼公司座谈会

O2016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。

Biomass group master student, Changhui Zhu and doctor student, Fan Zhang passed their defenses of degree dissertation in 2016

On May 23th, 2016, five experts from Kunming University of Science and Technology and Southwest Forestry University listend to the reports and defenses of Mr. Changhui Zhu, a master student and Mr. Fan Zhang , a doctor student in biomass group that were expected to be graduated in 2016. After the discussion and secret ballot, 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!

QQ图片20160526201254

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

1Picture1

video:

http://woodrefinery.com/zhenfang/wp-content/uploads/2016/05/60S480p_bitrate_130.mp4?_=1

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) 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 catalyst 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] Fan 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*, Fan 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, Fan 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),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 EnergyGreen 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。

2015excellent group

超顺磁酸碱双功能纳米ZrFeOx催化剂的合成及用以生产生物燃料

酸碱双功能纳米颗粒广泛用来合成生物燃料和高附加值的化学品。特别是磁性纳米金属氧化物,活性高可一锅法生产生物燃料,易于回收和重复利用。

生物能源组与贵州大学联合培养的博士生李虎在导师杨松教授和方真研究员的指导下,通过溶剂热处理和水解缩合的两步法合成酸碱双功能的超顺磁性纳米颗粒。合成的ZrFeOx纳米颗粒大约为12 nm, 中心为Fe3O4纳米颗粒(作为磁核),其外面覆盖了一层0.65 nm厚的ZrO2。ZrFeOx纳米颗粒具有分布良好的酸碱含量(0.39 vs. 0.28 mmol/g),适度的表面积(181 m2/g),孔径(9.8 nm)和较强的磁性(35.4 Am2 kg−1)。ZrFeOx纳米颗粒在乙醇中,进一步用来催化乙酰丙酸乙酯转换为γ戊内酯(GVL): 在230 ºC,反应3小时,GVL产率可高达87.2%。该纳米催化剂与固体酸HY2.6组合,可将糖直接转化为GVL,得到适中产率(约45%)。此外,磁性ZrFeOx纳米颗粒可很方便地由磁铁回收,可进行至少六次的重复利用。

祥情可见:

H Li, Zhen Fang*, S Yang, Direct Conversion of Sugars and Ethyl Levulinate into γ-Valerolactone with Superparamagnetic Acid-Base Bifunctional ZrFeOx Nanocatalysts, ACS Sustainable Chemistry & Engineering, 4(1), 236-246 (2016).
Synthesis of Superparamagnetic Acid−Base Bifunctional ZrFeOx Nanocatalyst for Biomass Conversion

Acid−base bifunctional nanocatalysts can directly on-pot produce biofuels and chemical from biomass. Particularly, some magnetic metal oxides that are active and recyclable.

Mr. Hu Li, a PhD student, co-supervised by Prof. Song Yang (Guizhou University) and Prof. Zhen FANG (Biomass Group, Xishuangbanna Tropical Botanical Garden, CAS) successfully synthesized bifunctional ZrFeOx nanocatalyst for biomass conversions.

In their work, acid-base bifunctional superparamagnetic FeZrOx nanoparticles were synthesized via a two-step process of solvothermal treatment and hydrolysis-condensation, and were further employed to catalyze the conversion of ethyl levulinate (EL) to γ-valerolactone (GVL) using ethanol as both H-donor and solvent. ZrFeO(1:3)-300 nanoparticles (12.7 nm) with Fe3O4 core covered by ZrO2 layer (0.65 nm thickness) having well- distributed acid-base sites (0.39 vs. 0.28 mmol/g), moderate surface area (181 m2/g), pore size (9.8 nm) and strong magnetism (35.4 Am2 kg−1) exhibited superior catalytic performance, giving a high GVL yield of 87.2% at 230 ºC in 3 h. The combination of the nanoparticles with solid acid HY2.6 promoted the direct transformation of sugars to produce GVL in moderate yield (around 45%). Moreover, the nanocatalyst was easily recovered by a magnet for six cycles with an average GVL yield of 83.9% from EL.

The study was published:

H Li, Zhen Fang*, S Yang, Direct Conversion of Sugars and Ethyl Levulinate into γ-Valerolactone with Superparamagnetic Acid-Base Bifunctional ZrFeOx Nanocatalysts, ACS Sustainable Chemistry & Engineering, 4(1), 236-246 (2016).

Presentation1


TEM images of ZrFeOx nanocatalyst

 

镍锆纳米氧化物,高效催化生物质合成γ戊内酯GVL
γ戊内酯(GVL)已被确定为一种绿色的和可再生的溶剂,用以提高生物质转化和各种有机反应。它可作为液体燃料,香料和食物的添加剂。更重要的是,GVL可以用来合成汽油和柴油燃料(例如,C8-C18烷烃和2-甲基四氢呋喃)和高价值的化学物质(如1,4-戊二醇,甲基戊酸,离子液体和聚合物)。

生物能源组与贵州大学联合培养的博士生李虎在导师杨松教授和方真研究员的指导下,用共沉淀方法合成了一系列的混合氧化物纳米颗粒。研究发现,在不使用外部氢源的情况下,还原后的磁性镍 – 氧化锆纳米颗粒可直接高效转化生物质衍生物(如乙酰丙酸乙酯,果糖,葡萄糖,纤维二糖和羧甲基纤维素)为GVL。用磁性纳米颗粒Zr5Ni5(< 20纳米)作为催化剂,在200℃下反应3小时,最大GVL产率为95.2%。这些纳米催化剂具备酸碱二重性,对GVL的合成具有协同作用。 此外,磁性Zr5Ni5纳米颗粒可很方便地由磁铁回收,可进行至少五次的重复利用。

近日,文章“H Li, Zhen Fang*, S Yang, Direct Catalytic Transformation of Biomass Derivatives into Biofuel Component γ-Valerolactone with Magnetic NiZr Nanoparticles, 81, 135-142, (2016).” 在国际期刊《ChemPlusChem》发表:  http://onlinelibrary.wiley.com/doi/10.1002/cplu.201500492/abstract
Converting biomass derivatives into biofuel component γ-valerolactone (GVL) with magnetic NiZr nanoparticles

γ-valerolactone (GVL) has been identified as a green and renewable solvent to improve the performance of biomass conversion and various organic reactions, and as an additive suitable for liquid fuels, perfumes and food. More importantly, GVL is able to be employed as a precursor to produce gasoline and diesel fuels (e.g., C8−C18 alkanes and 2-methyltetrahydrofurane) and valuable chemicals such as 1,4-pentanediol and methyl pentenoate, as well as ionic liquids and polymers.

Mr. Hu Li, a PhD student, co-supervised by Prof. Song Yang (Guizhou University) and Prof. Zhen FANG (Biomass Group, Xishuangbanna Tropical Botanical Garden, CAS) successfully synthesized g-valerolactone.

In their work, a series of mixed oxide nanoparticles were prepared by coprecipitation method and characterized by many techniques. NiZr oxide catalysts and their partially reduced magnetic counterparts were highly efficient in direct transformation of biomass derivatives including ethyl levulinate, fructose, glucose, cellobiose and carboxymethyl cellulose into GVL without using external hydrogen source, producing a maximum GVL yield of 95.2% at 200 ºC for 3 h with H2 reduced magnetic Zr5Ni5 nanoparticles (< 20 nm). Acid-base bifunctionality of these nanocatalysts is found to play a synergic role in synthesis of GVL in alcohols, while appropriate control of Ni/Zr molar ratio is able to improve the selectivity towards GVL (~98%), along with high formation rates (up to 54.9 mmol g−1 h−1). Moreover, the magnetic Zr5Ni5 nanoparticles were conveniently recovered by a magnet for five recycles with almost constant activity.

The study entitled “H Li, Zhen Fang*, S Yang, Direct Catalytic Transformation of Biomass Derivatives into Biofuel Component γ-Valerolactone with Magnetic NiZr Nanoparticles, 81, 135-142, (2016).” has been published in ChemPlusChem:  http://onlinelibrary.wiley.com/doi/10.1002/cplu.201500492/abstract

 Presentation1

 Magnetic nanoparticles: Acid-base bifunctional NiZr nanocatalysts with strong magnetism show high activity and reusability in transformation of biomass derivatives including EL, fructose, glucose, cellobiose and carboxymethyl cellulose into γ-valerolactone (GVL) with 95.2% yield and 98% selectivity.

 
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