Archive for 实验室活动

美藤果的“出路“

   

        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头脑风暴。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

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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.

New US Patent Issued for ‘Fast Hydrolysis’ of Biomass without Adding Catalyst

 According to USPTO Public PAIR, a U.S. patent #: 9243303 has been issued to Zhen Fang (Kunming, CN) for technology that provides a simple and low-cost method to fast dissolve and hydrolyze lignocellulosic biomass with great potential for a novel biorefinery.

The patent entitled “Method for the dissolving and rapid hydrolyzing of lignocellulose biomass, device thereof and use of the same” was issued on Jan. 26, 2016 for work done by Professor Zhen Fang, Leader and Founder of Biomass Group at Chinese Academy of Sciences. Professor Fang stated, “I am very excited to have been granted this new U.S. patent containing such claims that provide protection for ‘fast hydrolysis’ process.

In previous work, It was found that by adding 0.8 wt% Na2CO3, actual wood without pretreatment can be completely dissolved upon fast-heating (7~16°C/s) to form a ‘wood solution’ at 329-367 oC at short reaction times (0.7-2 s). The ‘wood solution’ can be rapidly (ca. 15 s) hydrolyzed to sugars/sugar oligomers under homogeneous conditions.

Recently, Prof. Fang found that without adding any cayalyst, by putting lignocellulose biomass in pure water and rapidly heated to 330~403 oC, and then 89~99% of the lignocellulose biomass is dissolved and rapidly hydrolyzed to saccharide in 3.38~21.79 s. The following hydrolysis reaction can be carried out under the homogeneous phase condition for the dissolving of the lignocellulose biomass. At the same time, the solvated biomass could be easily used in the high pressure flow reactor to continuously pretreat the biomass and hydrolyze for producing saccharide, other biofuel and product. The present invention doesn’t need any catalyst and doesn’t pollute the environment, furthermore the process is simple and the cost is low, and it belongs to green and sustainable industry, and a good prospect of market application could be taken on.

The patent is the latest development in a 23-year effort by Professor Zhen Fang in the study of biomass hydrolysis process, aimed at a simple, fast and low-cost method for a novel biorefinery. ‘Fast hydrolysis’ process will be the technological key to economic utilization of abundant lignocellulosic biomass as viable feedstocks for the production of industrial sugar, ethanol and chemicals. His pioneering work opens the door, for the first time, to the possibility of developing industrial-scale technology at competitive cost for producing biofuels and value-added products from lignocellulosic biomass based on the ‘fast hydrolysis’ process in a flow reactor.

This patent is the third US patent issued to Professor Fang adding to its portfolio of 19 authorized Chinese patents that cover various features of biorefinery technologies after his returning to China in 2007.

 

非催化快速水解技术获美国专利

方真研究员发现,将木材或纤维素置于碱性或酸性溶液中,然后再将得到的混合物与高温水溶液混合,并以一定的加热速率加热至一定的高温,则可以实现木材或纤维素的完全溶解和快速水解。以该实验结果为基础,方真研究员发明的快速水解技术获得两项美国专利(US patent#: 9115215;8268126)。

最近,方真研究员在进一步地深入研究后发现:在高压热水中,不经任何预处理,不加任何催化剂,只需几秒钟时间,99%的木材可以快速溶解并水解。他设计并发明了一项装置,可连续、快速、大规模地水解木材,使得此项发现实现工业化生产成为可能。这一发现和发明,打破了常规催化(酸碱或酶催化)水解的方法和观念,为快速(几秒内)、绿色(不用任何催化剂)和省能(不用任何预处理)地水解木材,提供了一种全新的方法和思路。并将为生物质水解、生物冶炼为生物能源和化学品等下游产业提出一个新的研究方法。

该发明“Method for the dissolving and rapid hydrolyzing of lignocellulose biomass, device thereof and use of the same”获美国专利(US patent#: 9243303; issue date: 01/26/2016)。

这是方真研究员自2007年初回国后,在中国获得的第三个关于快速水解的美国专利。

“Fast dissolution of cellulose for hydrolysis” was authorized US patent
Recently, “fast dissolution of cellulose for hydrolysis” invented by Prof. Zhen Fang was authorized US patent (US patent#: 9115215; issue date: 08/25/2015).

In the nature, lignocellulosic biomass, such as wood and grass, is roughly consisted of 50% cellulose, 25% hemicellulose, and 20% lignin. Cellulose can be hydrolyzed into saccharides which are further used for producing cellulosic ethanol through fermentation. Because lignocellulosic biomass is water-insoluble, the current industrial methods for hydrolyzing biomass proceed mainly in a semi-continuous percolating reactor containing 0.4~0.8% dilute aqueous sulphuric acid, at temperature of 180~190℃ and under pressure of 12~14 atmospheres. Reports about continuous production of sugars in a high-pressure continuous flow reactor were not found.

Prof. Fang invented a method for completely dissolving and rapidly hydrolyzing cellulose, and uses thereof.

  • Cellulose is placed in an acidic aqueous solution with a [H+] concentration of 10-7~1 M or an alkaline aqueous solution with a [OH] concentration of 10-7~1 M as sample A, wherein the volume ratio of solid to liquid is (0.003~05).
  • The acidic aqueous solution with a [H+] concentration of 10-7~1M or the alkaline aqueous solution with a [OH] concentration of 10-7~1M is heated up to 261~352℃ as sample B.
  • Sampe A and sample B obtained from step 1 and step 2 are mixed in a reactor to a concentration of cellulose of 0.1%~35%, the concentration of the mixed solution is adjusted to an acidity of 10-7~1M [H+] or an alkalinity of 10-7~1M [OH], and a water density of 587~997 kg/m3, pressure is set at 6~584 MPa. The mixture is rapidly heated up to 261~352℃ at heating rate of 7.8~8℃/s, and then cellulose is dissolved completely in 0.8~2 sec and hydrolyzed in 5 sec.

Using this technique, it is the first time for achieving complete dissolution and rapid hydrolysis of cellulose at a lower temperature, which not only dramatically reduces the cost of hydrolysis but also improves the safety of production and extends the service life of equipment in a flow system, thus possessing a good application prospect.
一种完全溶解和快速水解纤维素的方法及其应用获美国专利
自然界中的木质纤维素生物质如木材和草类,大约是由50%的纤维素,25%的半纤维素和20%的木质素组成。纤维素经水解能够降解为糖类,进而用于发酵生产纤维素酒精。由于木质纤维素生物质不溶于水,现有的工业化生物质水解方法主要是以半连续式渗透反应器、在180~190℃和12~14 大气压下的0.4~0.8%稀硫酸水溶液中水解。未见使用高压连续反应器进行连续生产的报道。

方真研究员在深入研究后发现,在溶解和快速水解纤维素之前,先将其置于酸性或碱性溶液中,然后再将得到的混合物与高温稀酸或稀碱溶液混合,并以一定的加热速率加热至一定的温度,则可以实现纤维素的完全溶解和快速水解。在此基础上,发明人提出如下技术方案:

一种完全溶解和快速水解纤维素的方法,包括以下步骤:

1、将纤维素置于浓度为10-7~1M [H+]酸性或10-7~1M [OH]碱性水溶液中,固液体积比为(0.003~1.05):1;

2、将10-7~1M[H+]酸性或10-7~1M [OH]碱性水溶液加热至261~352℃;

3、混合步骤1和2所得物置于反应器中,纤维素浓度为0.1%~35%,调节混合后的物料溶液浓度为10-7~1M [H+]酸性或10-7~1M [OH]碱性,水密度为587~997 kg/m3,设定压力为6~584 MPa,加热速率为7.8~14.8℃/s,快速加热至261~352℃,0.8~2秒即能完全溶解纤维素。

溶剂化的纤维素可以很方便地应用于低温的高压流动式的反应器,进一步降低了生产成本,连续水解生产糖类及别的生物燃料和产品。

 

该发明获美国专利(US patent#: 9115215; issue date: 08/25/2015)。

W020160113615398357669

Many biomass residues are produced in china and it is important to volatilize them, such as conversion of them to sugars by hydrolysis. The hydrolysis of lignocelluloses in concentrated and diluted homogenous acids has been practiced for many years, but problems such as corrosion hazards, acid-waste and difficulties in separation are not solved effectively. Various solid materials, such as transition metal oxides, ion-exchange resins, zeolites and sulfonated carbons are used as environmentally friendly catalysts for biomass hydrolysis because of their reusability, less corrosiveness and non-toxicity. And many magnetization methods are introduced by chemical reactions, such as precipitation and subsequent reduction of Fe3+ to Fe or Fe3O4 which may cause pollution and high cost. In this work, magnetic sulfonated acid was synthesized from glucose and magnetized without chemical reactions by simply mixing magnetic Fe3O4 nanoparticles with aqueous glucose solution.
Miss Tongchao Su (PhD student), under the guidance of Professor Zhen Fang from Xishuangbanna Tropical Botanical Garden (CAS), prepared magnetic catalyst (C-SO3H/Fe3O4) by evaporation the mixture of Fe3O4 nanoparticles and aqueous glucose solution, and pyrolysis in a tubular furnace at temperature of 700 oC for 1 h, and sulfonated by 98% H2SO4 in oil bath at 150 oC for 20 h. The sulfonated sample was washed repeatedly with distilled water at 200 oC for 3 h until no SO4 was detected using CaCl2. C-SO3H/Fe3O4 catalyst had -SO3H, -COOH and -OH acid groups for biomass hydrolysis. Under conditions of 9/50 cellulose/catalyst weight ratio, and 75/1 water/catalyst weight ratio for 3.5 h at 190 oC assisted with microwave, the catalyst was applied to the hydrolysis of bagasse, Jatropha and Plukenetia hulls. For water-ethanol extracted bagasse, Jatropha and Plukenetia hulls, higher yields of total reducing sugars (TRS), glucose and xylose were 79.8%, 58.3%, 97.2%; 47.2%, 35.6%, 96.4% and 54.4%, 35.8%, 94.9%, respectively. The catalyst had a good stability and after seven cycles, it showed no obvious deactivation.

The results are published in Scientific Reports:

TC Su, Zhen Fang*, F Zhang, J Luo, XK Li. Hydrolysis of Selected Tropical Plant Wastes Catalyzed by a Magnetic Carbonaceous Acid with Microwave, 5, 17538 (2015).

微波辅助碳基磁性固体酸水解热带植物废弃物

在中国, 随着经济的发展和人民生活水平的提高,产生出越来越多的生物质废弃物,应该充分利用它们,例如通过水解转化为可发酵糖以生产生物燃料和化学品。多年来,木质纤维素在液体酸中的水解得到广泛地研究和应用。但是设备腐蚀,酸废弃物以及回收问题都没有得到很好地解决。所以,近年来,多种固体催化剂被开发用以水解木质纤维素,例如过渡金属氧化物,离子交换树脂,沸石以及磺化碳等等。固体催化剂能够回收,无毒以及无腐蚀性等优点。通过化学方法沉淀,还原的方法引入磁性物质(Fe3O4)以便于催化剂更好地回收利用。本研究利用葡萄糖和纳米四氧化三铁为原料,通过简单的混合和磺化合成磁性酸催化剂。

中国科学院西双版纳热带植物园生物能源组,博士生苏同超小姐在方真研究员的指导下,通过蒸发四氧化三铁和葡萄糖混和溶液中的水分,然后在马弗炉中700 oC热解碳化1 h,以及在98%浓硫酸中磺化的方法成功合成了C-SO3H/Fe3O4 磁性催化剂。催化剂在使用之前,利用蒸馏水在200 oC水洗3 h直到水洗液中无SO4基团。C-SO3H/Fe3O4催化剂具有-SO3H, -COOH和-OH酸性功能团,利于水解。在反应温度190 oC, 3.5 h, 9/50生物质和催化剂质量比,以及75/1水和催化剂质量比例条件下,在微波中水解甘蔗渣,小桐子果壳和南美油藤果壳。其中醇-水萃取之后的甘蔗渣,小桐子和南美油藤果壳材料,水解具有较高的产率,其中总还原糖、葡萄糖以及木糖的产率分别为79.8%, 58.3%, 97.2%; 47.2%, 35.6%, 96.4% 和54.4%, 35.8%, 94.9%。此催化剂具有很好地稳定性,催化剂利用七次之后仍无明显的失活。

相关研究成果发表在Scientific Reports上:
TC Su, Zhen Fang*, F Zhang, J Luo, XK Li. Hydrolysis of Selected Tropical Plant Wastes Catalyzed by a Magnetic Carbonaceous Acid with Microwave, 5, 17538 (2015).

                      图为磁性催化剂C-SO3H/Fe3O4用于在微波水解热带植物废弃物

 
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