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

近日,方真研究员应 “生物燃料,生物制品和生物炼制”(他担任该刊顾问编委) 邀请,为该刊关于生物能源技术发展撰写社论。方真研究员建议设计并找到一种新的廉价和绿色的溶剂,在温和的条件下,溶解木质纤维素生物质,在均相的条件下进行生物炼制。

全球每年生物质生产量相当于8倍的世界能源消耗。大部分生物质是以木质纤维素的形式存在,含有75%的单糖(例如,木材和草:50%的纤维素和25%半纤维素)。问题的关键是如何释放这些丰富的生物聚合物成为水溶性糖,它们可很容易随后再转化为乙醇,脂类,其他生物燃料,各种化学品,食品和药品。

通常,有三种典型的方法水解木质纤维素为可发酵糖:(ⅰ)预处理后,在低温下酶解(例如,50摄氏度);(ⅱ)在温和的温度下催化水解(例如,180摄氏度),和(iii)在高温近临界点下,快速水解(如350摄氏度)。溶解生物质以形成均相“生物质溶液”对于水解和预处理是非常重要的。溶解后的“生物质溶液”可像液态石油(而不是固体煤)一样,很容易加工,并可实际用于流动反应装置来提高生产效率。有机溶剂(例如,γ戊内酯,γ-valerolactone),离子液体和超临界流体均可以溶解生物质来水解。

生物质溶解后,这三种水解方法可以进一步改进以提高实际用途:(ⅰ)酶水解:酶,水和生物质分子可在一个均相条件下完全水解,不需要预处理步骤。然而,应考虑在工业生产中,如何回收酶,保持其较高的活性和降低成本。 (ii)催化水解:水解过程可用于流动反应装置以提高生产效率。与此同时,固体催化剂可替代液体酸,这样更绿色和环保。然而,固体催化剂的稳定性和活性需要进一步研究。 (iii)快速水解技术:尽管其效率高,但是,由于水解条件苛刻(如高温高压),工程问题(如反应器设计,材料和连续操作)等将成为障碍其商业化的关键。

1、Zhen Fang*, How Can We Best Solubilize Lignocellulosic Biomass for Hydrolysis? Biofuels Bioproducts and Biorefining, 9, 621–622 (2015) (invited editorial).

 

Solubilization of Lignocellulosic Biomass for Hydrolysis

 

By Jing-Mei Chen

 

Recently, Prof. Zhen Fang was invited to write an Editorial in “Biofuels, Bioproducts and Biorefining” (He is also serving as advisory editorial board member for this Journal). He suggested to design and find a green and inexpensive solvent to solubilize lignocellulosic biomass at mild conditions for novel biorefineries.

Annual global biomass production is equivalent to 8 times the world’s energy consumption. Most of biomass is in lignocellulosic form that contains 75% sugar units (e.g., wood and grass plants: 50% cellulose and 25% hemi-cellulose). The key is how to release these abundant biopolymers to become water-soluble sugars that are easily subsequently converted into ethanol, lipids, other bio-fuels, various chemicals, foods, and medicines. There are three typical methods to hydrolyze lignocelluloses to sugars.

Typically, the three ways are used for hydrolysis: (i) enzymatic hydrolysis after pretreatment at low temperatures (e.g., 50 oC), (ii) catalytic hydrolysis at mild temperatures (e.g., 180 oC), and (iii) fast hydrolysis at high temperatures near critical point (e.g., 350 oC). It is very important to solubilize biomass to form a homogenous phase for hydrolysis and pretreatment. The homogenous biomass solution (like petroleum not solid coal) is also easily processed in a flow system for practical applications. Organic solvents (e.g., γ-valerolactone), ionic liquids and supercritical fluids can dissolve actual biomass for hydrolysis.

After biomass solubilization, the three hydrolysis methods can be further improved for practical uses: (i) for enzymatic hydrolysis; enzymes, water and biomass molecules mix well in a homogenous phase for complete hydrolysis, pretreatment step is not required. However, how to recycle enzymes, keep high activity and reduce their cost should be considered for industrial production. (ii) For catalytic hydrolysis; a flow process can be built up to increase production efficiency. At the same time, solid catalysts may replace liquid acids for a green process. However, their stability and activity need study further. (iii) For fast hydrolysis; even though its high efficiency, however, owing to severe conditions (high temperature and pressure), engineering issues (such as reactor design, materials and continuous operation) become key obstacle to commercialize it.

1、Zhen Fang*, How Can We Best Solubilize Lignocellulosic Biomass for Hydrolysis? Biofuels Bioproducts and Biorefining, 9, 621–622 (2015) (invited editorial).

 

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Cellulose completely dissolves in an ionic liquid for hydrolysis or pretreatment

纤维素完全溶解在离子液体中行水解或预处

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).

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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。

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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

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

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!

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Congratulations to Ms WU for the succesful defence her dissertation

Ms Xuehua WU, a joint training PhD student of Kunming University of Science and Technology and Xishuangbanna Tropical Botanical Garden, CAS (Chinese Academy of Sciences), co-supervised by Prof. Hua WANG and Prof. Zhen FANG has succesfully passed her defence of dissertation on 4th May 2015.

She has successfully defended her thesis entitled “carbon-based solid acid and magnetic solid base catalyzed in biodiesl production from Jatropha oil” while the committee suggested that Kunming University of Science and Technology to award her a doctorate degree in Engineering , according to relevant authorities and subjected to regulations.

During her PhD studies, she underwent 4 years (2011-2015) of training and carried out her research project in our biomass lab. She managed to complete four research papers and one international conference paper.

Once again, Congratulations to Ms WU.

 
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