热解制备左旋葡聚糖High Yield Production of Levoglucosan via Catalytic Pyrolysis of Cellulose at Low Temperature

High Yield Production of Levoglucosan via Catalytic Pyrolysis of Cellulose at Low Temperature

Recently, Dr Li-Qun Jiang (Associate Prof., Institute of Biological and Medical Engineering, Guangdong Academy of Sciences), Prof. H Li (Guizhou University) and Prof. Zhen Fang published an article in Fuel about levoglucosan production from catalytic pyrolysis of cellulose with acid-base bifunctional magnetic Zn-Fe-C catalysts.

Catalytic pyrolysis of cellulose to levoglucosan in improved yields was achieved with acid-base bifunctional magnetic Zn-Fe-C catalysts. Among tested catalysts, Zn4@Fe-C500 could not only increase levoglucosan yield by 5.4 times compared with non-catalytic cellulose pyrolysis at 300 °C, but also help lower reaction temperature by 200 °C due to acid-base site synergistic effect. Furthermore, the levoglucosan yield (80.1 wt%) from catalytic cellulose pyrolysis at 300 °C was much higher than that commonly conducted at 500 °C without catalyst (60.1 wt%). Thermogravimetric and kinetic analysis disclosed levoglucosan formation mechanism. Importantly, Zn4@Fe-C500 catalyst was highly recyclable with little deactivation after 5 consecutive cycles. This study exhibited great potential for industrial levoglucosan production from cellulose at low temperatures. Related results were published in Fuel:

LQ Jiang, JC Luo, F Xu, L Qian, YT Wang, H Li*, Zhen Fang*, High Yield Production of Levoglucosan via Catalytic Pyrolysis of Cellulose at Low Temperature, Fuel, 323 (2022) 124369. https://doi.org/10.1016/j.fuel.2022.124369

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Production of Levoglucosan via Catalytic Pyrolysis of Cellulose at Low Temperature with Znn@Fe-CT acid-base bifunctional magnetic catalyst磁性固体酸碱两性催化剂Znn@Fe-CT催化纤维素定向热解制备左旋葡聚糖


 磁性固体酸碱两性催化剂Znn@Fe-CT催化纤维素定向热解制备左旋葡聚糖

最近,蒋丽群博士(广东省科学院生物与医学工程研究所副教授), 李虎教授 (贵州大学)和方真教授在国际学术期刊Fuel(IF: 6.609,Q1)发表题为“High Yield Production of Levoglucosan via Catalytic Pyrolysis of Cellulose at Low Temperature”的研究性论文。该研究制备了磁性固体酸碱两性催化剂Znn@Fe-CT用于催化纤维素快速热解选择性制取左旋葡聚糖。相关研究表明,Zn4@Fe-C500催化热解纤维素不仅可以将热解糖化反应温度从500 ℃降低至300 ℃,并且300 ℃下催化热解纤维素得到左旋葡聚糖的产率(80.1 wt%)远高于500℃(60.1 wt%)。经过5次循环实验后Zn4@Fe-C500仍然可以提升左旋葡聚糖的产率。该研究为纤维素定向热解转化提供了新思路。详情可见:

LQ Jiang, JC Luo, F Xu, L Qian, YT Wang, H Li*, Zhen Fang*, High Yield Production of Levoglucosan via Catalytic Pyrolysis of Cellulose at Low Temperature, Fuel, 323 (2022) 124369. https://doi.org/10.1016/j.fuel.2022.124369

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NaFeO2-Fe3O4合成生物柴油Highly stable NaFeO2-Fe3O4 composite catalyst from blast furnace dust for efficient production of biodiesel at low temperature

Recently, Dr Yi-Tong Wang (Associate Prof., College of Metallurgy and Energy, North China University of Science and Technology) and Prof. Zhen Fang published an article in Industrial Crops & Products about using highly stable NaFeO2-Fe3O4 composite catalyst from blast furnace dust for biodiesel production.

Highly stable catalysts were prepared by wet impregnation of blast furnace dust (BFD) in Na2CO3·H2O, Na2CO3·10H2O, NaHCO3 and Na2CrO4 solution and subsequent calcination of 300-600 oC. At low temperature of 65 oC for 2 h with methanol/oil molar ratio of 15/1, high biodiesel yields of 100 wt% were obtained with 7wt% Na2CO3·H2O@BFD300 and Na2CO3·H2O@BFD400 catalyst (impregnating with Na2CO3·H2O solution and calcining at 300 and 400 oC) added for the first use. Na2CO3·H2O@BFD300 catalyst exhibited outstanding stability and recyclability with biodiesel yields of 100 wt% at the fifth use (93 wt% at the twelfth use) owing to impregnated Na2CO3 reacting with Fe2O3 in dust to produce stable and active nanocomponents of NaFeO2 (32.42 nm) and magnetic nanocomponent of Fe3O4 (size of 3.14 nm and Ms of 6.16 Am2/kg) in dust existing. The study provided practical guidance for biodiesel industrial production.

Related results were published in Industrial Crops & Products:

XM Wang, YN Zeng, LQ Jiang, YT Wang*, JG Li*, LL Kang, R Ji, D Gao, FP Wang, Q Yu, YJ Wang, Zhen Fang*. Highly stable NaFeO2-Fe3O4 Composite Catalyst from Blast Furnace Dust for Efficient Production of Biodiesel at Low Temperature, Industrial Crops and Products, 182, 114937, https://doi.org/10.1016/j.indcrop.2022.114937 (2022).

Efficient production of biodiesel can be achieved with Na2CO3·H2O@BFD300 catalyst for 12 reuses with 92.56 wt% yield.使用Na2CO3·H2O@BFD300催化剂实现生物柴油高效生产,循环12次后,产率仍可达92.56 wt%。


王一同博士和方真教授在国际学术期刊Industrial Crops & Products发表学术论文:

高炉粉尘制备NaFeO2-Fe3O4复合催化剂用于生物柴油合成

最近,王一同博士(华北理工大学冶金与能源学院副教授)和方真教授在国际学术期刊Industrial Crops & Products(IF: 5.645,Q1)发表题为“高炉粉尘制备NaFeO2-Fe3O4复合催化剂用于生物柴油合成”的研究性论文。

利用Na2CO3·H2O,Na2CO3·10H2O,NaHCO3和Na2CrO4水溶液分别湿法浸渍高炉粉尘,于300-600 oC高温活化制备高稳定性催化剂。在65 oC、醇油摩尔比15/1、催化剂用量7 wt%的条件下反应2 h,Na2CO3·H2O@BFD300和Na2CO3·H2O@BFD400催化剂获得了100 wt%的产率。由于浸渍的Na2CO3和高炉粉尘中的Fe2O3反应生成稳定且有活性的纳米组分NaFeO2(32.42 nm)以及高炉粉尘中含有的磁性纳米组分Fe3O4(晶粒:3.14 nm;磁性:6.16 Am2/kg),Na2CO3·H2O@BFD300催化剂表现出优异的稳定性和可回收性,循环12次后仍可获得93 wt%的产率。该研究为生物柴油的工业化生产提供了实用指导。详情可见:

XM Wang, YN Zeng, LQ Jiang, YT Wang*, JG Li*, LL Kang, R Ji, D Gao, FP Wang, Q Yu, YJ Wang, Zhen Fang*. Highly stable NaFeO2-Fe3O4 Composite Catalyst from Blast Furnace Dust for Efficient Production of Biodiesel at Low Temperature, Industrial Crops and Products (IF 5.6), 182, 114937, https://doi.org/10.1016/j.indcrop.2022.114937 (2022).

双功能Na-Fe-Ca催化剂生物柴油Production of biodiesel at low temperature using bifunctional Na-Fe-Ca nanocatalyst from blast furnace waste

Production of biodiesel at low temperature using bifunctional Na-Fe-Ca nanocatalyst from blast furnace waste

Recently, Dr Yi-Tong Wang (Associate Prof., College of Metallurgy and Energy, North China University of Science and Technology) and Prof. Zhen Fang published an article in Fuel about using highly active bifunctional Na-Fe-Ca nanocatalyst from blast furnace dust for biodiesel production.

Nanocatalysts for biodiesel production were prepared via wet impregnation of blast furnace dust (BFD) in Na2CO3 (Na-BFD) and CaCO3 (Ca-BFD) suspension solutions and calcination at 500 and 600 oC, respectively. Biodiesel yields of 100.0 wt% (Na-BFD500) and 98.3 wt% (Ca-BFD600) were achieved at 65 oC. Synthesized catalysts showed outstanding activity and recyclability, due to the transition of CaCO3, Na2CO3 and Fe2O3 to nanocrystals of NaFeO2 (29.9 nm), Ca2Fe2O5 (10.5 nm), CaO (100.1 nm) and Ca2Fe2O5 (50.0 nm). Na-BFD500 achieved 95.8 wt% biodiesel yield with 16 cycles, whereas Ca-BFD600 reached 94.1 wt% biodiesel yield with 7 cycles via magnetic separation. BFD containing convertible magnetic and active components (Fe2O3 and CaCO3) was an ideal raw material to synthesize catalyst for biodiesel production with high catalytic efficiency and easy separation. The study provided a practical utilization of industrial solid waste for biodiesel production.

Related results were published in Fuel:

YT Wang, XM Wang, D Gao, FP Wang, YN Zeng, JG Li*, LQ Jiang, Q Yu, R Ji, LL Kang, YJ Wang, Zhen Fang*, Efficient Production of Biodiesel at Low Temperature Using Highly Active Bifunctional Na-Fe-Ca Nanocatalyst from Blast Furnace Waste, Fuel, 322, 124168, https://doi.org/10.1016/j.fuel.2022.124168 (2022).

Nanocatalysts produced by impregnation and calcination transesterified soybean oil to biodiesel with 100 wt% yield. 通过浸渍和煅烧制备了纳米催化剂用于催化豆油酯交换制备生物柴油,产率高达100 wt%。


高炉粉尘制备双功能Na-Fe-Ca纳米催化剂用于生物柴油合成

最近,王一同博士(华北理工大学冶金与能源学院副教授)和方真教授在国际学术期刊Fuel(IF: 6.609,Q1)发表题为“高炉粉尘制备双功能Na-Fe-Ca纳米催化剂用于生物柴油合成”的研究性论文。

利用Na2CO3和CaCO3水溶液分别湿法浸渍高炉粉尘,于500 ℃和600 oC高温活化制备纳米催化剂(Na-BFD500和Ca-BFD600),用于催化豆油制备生物柴油。催化剂经高温煅烧后,CaCO3、Na2CO3和Fe2O3晶体转变为纳米NaFeO2(29.9 nm)、Ca2Fe2O5(10.5 nm)、CaO(100.1 nm)和Ca2Fe2O5(50 nm)晶体,表现出优异的催化活性和可循环利用特性。Na-BFD500催化豆油制备生物柴油的产率达到100.0 wt%,循环16次后仍可获得95.8 wt%的产率,而Ca-BFD600催化豆油制备生物柴油的产率达到98.3 wt%,循环7次后仍可获得94.1 wt%的产率。该研究为工业固体废物用于生物柴油制备提供了新思路。详情可见:

YT Wang, XM Wang, D Gao, FP Wang, YN Zeng, JG Li*, LQ Jiang, Q Yu, R Ji, LL Kang, YJ Wang, Zhen Fang*, Efficient Production of Biodiesel at Low Temperature Using Highly Active Bifunctional Na-Fe-Ca Nanocatalyst from Blast Furnace Waste, Fuel (IF 6.6), 322, 124168, https://doi.org/10.1016/j.fuel.2022.124168 (2022).

捐书: 20 books were donated by Prof. Zhen Fang

捐书: 20 books were donated by Prof. Zhen Fang

On Feb. 8, 2022, Prof. Zhen Fang donated 20 books edited/authored by him in renewable energy and green technologies to his hometown in Fujian:

  1. P Bartocci, F Fantozzi, Q Yang, HP Yang, O Masek, YJ Yan, Zhen Fang, L Rigamonti, (Editors), Sustainable Biomass and Waste Conversion, Elsevier, 2022.
  2. Zhen Fang, RL Smith, Jr., LJ Xu (Editors), Production of Biofuels and Chemicals from Sustainable Recycling of Organic Solid Waste, Springer, Heidelberg Berlin, 2021.
  3. Zhen Fang, RL Smith, Jr., LJ Xu (Editors), Production of Biofuels and Chemicals with Pyrolysis, Springer, Heidelberg Berlin, 2020.
  4. YT Wang, Zhen Fang (Editors), Catalytic Biomass to Renewable Biofuels and Biomaterials, MDPI (Basel, Switzerland), 2020.
  5. Zhen Fang, RL Smith, Jr., XF Tian (Editors), Production of Materials from Sustainable Biomass Resources, Springer, Heidelberg Berlin, 2019.
  6. Zhen Fang, RL Smith, Jr., H Li (Editors), Production of Biofuels and Chemicals with Bifunctional Catalysts, Springer, Heidelberg Berlin, 2017.
  7. Zhen Fang, RL Smith, Jr., X Qi (Editors), Production of Platform Chemicals from Sustainable Resources, Springer, Heidelberg Berlin, 2017.
  8. Zhen Fang, RL Smith, Jr.(Editors), Production of Biofuels and Chemicals from Lignin, Springer, Heidelberg Berlin, 2016.
  9. Zhen Fang, RL Smith, Jr., X Qi (Editors), Production of Hydrogen from Renewable Resources, Springer, Heidelberg Berlin, 2015.
  10. Zhen Fang, RL Smith, Jr., X Qi (Editors), Production of Biofuels and Chemicals with Microwave, Springer, Heidelberg Berlin, 2015.
  11. Zhen Fang, RL Smith, Jr., X Qi (Editors), Production of Biofuels and Chemicals with Ultrasound, Springer, Heidelberg Berlin, 2015.
  12. Zhen Fang, C Xu (Editors), Near-critical and Supercritical Water and Their Applications for Biorefineries, Springer, Heidelberg Berlin, 2014.
  13. Zhen Fang, RL Smith, Jr., X Qi (Editors), Production of Biofuels and Chemicals with Ionic Liquids, Springer, Heidelberg Berlin, 2014.
  14. Zhen Fang (Editor), Liquid, Gaseous and Solid Biofuels – Conversion Techniques, InTech, London, UK, 2013.
  15. Zhen Fang (Editor), Biofuels – Economy, Environment and Sustainability, InTech, London, UK, 2013.
  16. Zhen Fang (Editor), Pretreatment Techniques for Biofuels and Biorefineries, Springer, Berlin Heidelberg, 2013.
  17. Zhen Fang (Editor), Biodiesel – Feedstocks, Production and Applications, InTech, London, UK, 2013.
  18. J. M. Marchetti, Zhen Fang (Editors), Biodiesel: Blends, Properties and Applications, Nova Science Publishers, Inc., New York, 2011.
  19. Zhen Fang (Author), Rapid Production of Micro- and Nano-particles Using Supercritical Water, Springer, Berlin Heidelberg, 2010.
  20. Zhen Fang (Author), Complete Dissolution and Oxidation of Organic Wastes in Water, VDM Verlag Dr. Müller, Saarbrücken, Germany, 2009.

28日,方真教授档案图书捐赠仪式在泰宁县档案馆举行。

县领导黄维云出席仪式并讲话。

会上,县领导对方真先生的到来表示热忱的欢迎,对方院士热心捐赠珍贵的图书档案资料表示最诚挚的感谢!此次,方真院士捐赠的院士证书及他编著的20册珍贵图书档案资料(其中2部随后寄送),将进一步丰富泰宁县档案馆馆藏,助力科技事业的发展。

翻译:

1.P Bartocci,F Fantozzi,Q Yang,HP Yang,O Masek,YJ Yan,方真,L Rigamonti,(编著),《可持续生物质和废弃物转化》,爱思唯尔出版社,2022

2.方真,RL Smith,Jr.,徐禄江(编著),《可持续再生有机固体废物生产生物燃料和化学品》,柏林•海德堡,斯普林格出版社,2021

3.方真,RL Smith,Jr.,徐禄江(编著),《热解生产生物燃料和化学品》,柏林•海德堡,斯普林格出版社,2020

  1. 王一同,方真 (编著),《催化生物质转化为可再生生物燃料和生物材料》,MDPI(瑞士巴塞尔)出版社,2020
  2. 方真,RL Smith,Jr.,田霄飞(编著),《可持续生物质资源生产材料》,柏林•海德堡,斯普林格出版社,2019
  3. 方真,RL Smith,Jr.,李虎(编著),《双功能催化剂生产生物燃料和化学品》,柏林•海德堡,斯普林格出版社,2017
  4. 方真,RL Smith,Jr.,漆新华(编著),《可持续资源生产平台化学品》,柏林•海德堡,斯普林格出版社,2017
  5. 方真,RL Smith,Jr.(编著),《木质素生产生物燃料和化学品》,柏林•海德堡,斯普林格出版社,2016
  6. 方真,RL Smith,Jr.,漆新华(编著),《可再生资源生产氢气》,柏林•海德堡,斯普林格出版社,2015
  7. 方真,RL Smith,Jr.,漆新华(编著),《利用微波生产生物燃料和化学品》,柏林•海德堡,斯普林格出版社,2015
  8. 方真,RL Smith,Jr.,漆新华(编著),《利用超声波生产生物燃料和化学品》,柏林•海德堡,斯普林格出版社,2015
  9. 方真,徐春保(编著),《近临界水和超临界水及其在生物炼制中的应用》,柏林•海德堡,斯普林格出版社,2014
  10. 方真,RL Smith,Jr.,漆新华(编著),《利用离子液体生产生物燃料和化学品》,柏林•海德堡,斯普林格出版社,2014
  11. 方真(编著),《液体、气体和固体生物燃料-转化技术》,InTech出版社,英国,伦敦,2013
  12. 方真(编著),《生物燃料-经济、环境和可持续性》,InTech出版社,英国,伦敦,2013
  13. 方真(编著),《生物燃料和生物精炼的预处理技术》,柏林•海德堡,斯普林格出版社,2013
  14. 方真(编著),《生物柴油-原料、生产和应用》,InTech出版社,英国,伦敦,2013
  15. JM Marchetti,方真(编著),《生物柴油:混合物、性质和应用》,Nova Science Publishers出版社,纽约,2011
  16. 方真(作者),《超临界水快速制备微米和纳米颗粒》,柏林•海德堡,斯普林格出版社,2010
  17. 方真(作者),《水中有机废物的完全溶解和氧化》,德国,萨尔布吕肯,VDM Verlag Dr. Müller出版社,2009

碱颗粒球磨预处理: Efficient saccharification of wheat straw pretreated by solid particle-assisted ball milling with waste washing liquor recycling

碱颗粒球磨预处理: Efficient saccharification of wheat straw pretreated by solid particle-assisted ball milling with waste washing liquor recycling

Recently, PhD student Miss Xiao-le Liu supervised by Prof. Zhen Fang published a research article in Bioresource Technology about ball milling pretreatment with NaOH solid particles for enzymatic hydrolysis of wheat straw.

Wheat straw was pretreated using ball milling (BM) promoted by solid particles (NaOH, NaCl, citric acid). NaOH showed the best synergistic interaction effect, due to the breakage of β-1,4-glycosidic bonds among cellulose molecules by the alkali solid particles induced by BM. NaOH-BM pretreatment decreased the straw crystallinity from 46% to 21.4% and its average particle size from 398.3 to 50.6 μm in 1 h. After 4 h milling, the reducing-end concentration of cellulose increased by 3.8 times from 12.5 to 60.2 μM, with glucose yield increased by 2.1 times from 26.6% to 82.4% for 72 h enzymatic hydrolysis at cellulase loading of 15 FPU/g dry substrate. The pretreatment washing liquor was recycled for the re-treatment of partially pretreated biomass at 121 °C for 30 min, resulting in 99.4% glucose yield by enzymatic hydrolysis. BM assisted with alkali particles was an effective approach for improving biomass enzymatic saccharification.

Related results were published in Bioresource Technology:

XL Liu, CY Dong, SY Leu, Zhen Fang* (Supervisor), ZD Miao, Efficient Saccharification of Wheat Straw Pretreated by Solid Particle-Assisted Ball Milling with Waste Washing Liquor Recycling, Bioresource Technology, 347, 126721, https://doi.org/10.1016/j.biortech.2022.126721 (2022).

Wheat straw was ball milling pretreated with NaOH particles for 4 h with 82.4% glucose yield after 72 h enzymatic hydrolysis. The pretreatment washing liquor was recycled for the re-treatment of partially pretreated biomass at 121 °C for 30 min, resulting in 99.4% glucose yield. (球磨辅助NaOH颗粒预处理小麦秸秆4 h。酶水解72 h,预处理后小麦秸秆酶解率为82.4%。预处理后的水洗液循环利用,在121°C下,对预处理4 h后的小麦秸秆再预处理30 min,酶解率提高到99.4%)

 

球磨辅助固体颗粒预处理小麦秸秆的高效糖化及水洗废液的循环利用

最近,博士生刘小乐(女)在方真教授的指导下,在国际学术期刊Bioresource Technology (Q1, IF 9.6)发表一篇关于球磨辅助NaOH颗粒预处理小麦秸秆用于酶解的研究性论文。

通过球磨辅助固体颗粒(NaOH、NaCl,柠檬酸)预处理小麦秸秆。其中,球磨辅助NaOH颗粒预处理的协同作用最好,这可能是由于球磨可以使NaOH破坏纤维素分子间的β-1,4-糖苷键。球磨辅助NaOH颗粒预处理1 h后,纤维素结晶度从46%降为21.4%,平均粒径从398.3 μm降到50.6 μm。球磨辅助NaOH颗粒预处理4 h后,在15 FPU/g干底物的条件下酶解72 h,酶解率从26.6%提高到82.4%,酶解率较原始小麦秸秆提高2.1倍。对预处理后的水洗液进行循环利用,在121 ℃下对预处理4 h后的秸秆再预处理30 min,酶解率提高为99.4%。

结果发表在Bioresource Technology:

XL Liu, CY Dong, SY Leu, Zhen Fang* (Supervisor), ZD Miao, Efficient Saccharification of Wheat Straw Pretreated by Solid Particle-Assisted Ball Milling with Waste Washing Liquor Recycling, Bioresource Technology, 347, 126721, https://doi.org/10.1016/j.biortech.2022.126721 (2022).

 

还原胺化Synergistic catalysis of Co-Zr/CNx bimetallic nanoparticles enables reductive amination of bio-based levulinic acid

还原胺化Synergistic catalysis of Co-Zr/CNx bimetallic nanoparticles enables reductive amination of bio-based levulinic acid

Recently, PhD student Mr Pei-dong Wu supervised by Profs. Hu Li and Zhen Fang published a research article in Advanced Sustainable Systems about bimetallic synergistic catalysis for reductive amination of bio-based levulinic acid.

Bimetallic synergy and carbon-nitrogen doping can contribute to enhanced catalytic activity due to the strong electronic state and unique geometrical structure. In this work, a series of biomass-derived Co-M bimetallic C-N doped catalysts (Co-M@Chitosan-X; M = Zr, Ni, Fe, Cu, In; X denotes the molar percentage of M) were prepared via simple oil bath reflow and annealing. The Co-Zr@Chitosan-X catalysts were determined to contain alloy (Co-Zr), metal-carbon bond (Co-C, Zr-C), metal-nitrogen bond (Co-N, Zr-N) and metal oxide (Co3O4, ZrO2) through a series of characterizations, in which graphite-coated alloys and metal oxides were catalytically active species. The doping of the second metal results in a significant enhancement for the number of active sites in the catalyst, and the d-band center is shifted toward a deviation from the Fermi energy level. Among the tested catalysts, Co-Zr@Chitosan-20 exhibited superior catalytic activity for the reductive amination of bio-based levulinic acid to 5-methyl-2-pyrrolidone in 99.3% selectivity and 92.8% yield. This non-noble metal bimetallic synergistic catalytic protocol opens an avenue for efficiently producing biomass-derived nitrogenous chemicals.

Related results were accepted in Advanced Sustainable Systems:

Pei-dong Wu, Hu Li *, Zhen Fang *, Synergistic catalysis of Co-Zr/CNx bimetallic nanoparticles enables reductive amination of bio-based levulinic acid, 2022, 2100321. https://doi.org/10.1002/adsu.202100321

Non-noble bimetallic nanoparticles (Co-Zr/CNx) were efficient for direct conversion of bio-based levulinic acid (LA) to 5-methyl-2-pyrrolidone (5-MP) in water at 130 °C. Synergistic role was found in the reductive amination process with high activity over a long period of time in one-pot reactions. 非贵金属双金属纳米粒子(Co-Zr/CNx)在130℃的水中能有效地将生物基乙酰丙酸(LA)直接转化为5-甲基-2-吡咯烷酮(5-MP)。在单锅反应中还原胺化过程中发现双金属催化剂长时间具有高活性。


博士生吴培栋在李虎教授和方真教授的指导下,在国际学术期刊Advanced Sustainable Systems发表研究性论文:

 

具有协同作用的Co-Zr/CNx双金属纳米颗粒催化

还原胺化生物质基乙酰丙酸

最近,博士生吴培栋在李虎教授和方真教授的指导下,在国际学术期刊Advanced Sustainable Systems (Q1; Impact factor: 6.271)上发表了一篇关于双金属协同催化生物基乙酰丙酸还原胺化的研究性论文。

双金属协同作用和碳氮掺杂有助于提高催化剂的催化活性,因为掺杂后催化剂的强电子态和独特的几何结构。在这项工作中,通过简单的油浴回流和高温退火制备了一系列生物质衍生的双金属碳氮掺杂催化剂(Co-M@Chitosan-X;M = Zr, Ni, Fe, Cu, In;X表示M的摩尔百分比)。通过一系列的表征,Co-Zr@Chitosan-X催化剂的组分被确定为含有合金(Co-Zr)、金属-碳键(Co-C、Zr-C)、金属-氮键(Co-N、Zr-N)和金属氧化物(Co3O4、ZrO2),其中石墨包覆的合金和金属氧化物是催化活性物种。第二种金属的掺入使催化剂的活性位点数量明显增加,并且d带中心向偏离费米能级的方向移动。在催化剂活性测试中,Co-Zr@Chitosan-20在还原胺化生物基乙酰丙酸为5-甲基-2-吡咯烷酮的过程中表现出卓越的催化性能,其中选择性为99.3%,收率为92.8%。这种非贵金属的双金属协同催化作用为有效生产生物质衍生的含氮化学品开辟了一条新的途径。

详情可见:

Pei-dong Wu, Hu Li *, Zhen Fang *. Synergistic catalysis of Co-Zr/CNx bimetallic nanoparticles enables reductive amination of bio-based levulinic acid, 2022, 2100321. https://doi.org/10.1002/adsu.202100321

生物柴油的制备反应动力学Highly Stable Heterogeneous Catalysts from Electric Furnace Dust for Biodiesel Production: Optimization, Performance and Reaction Kinetics

生物柴油的制备反应动力学Highly Stable Heterogeneous Catalysts from Electric Furnace Dust for Biodiesel Production: Optimization, Performance and Reaction Kinetics

Recently, Dr Yi-Tong Wang (Associate Professor, female, College of Metallurgy and Energy, North China University of Science and Technology) and Prof. Zhen Fang published an article in Catalysis Today about highly stable heterogeneous catalysts from electric furnace dust for biodiesel production.

Highly stable heterogeneous catalysts were prepared by impregnating carbonates suspension solutions onto electric furnace dust (EFD) and being calcined at high-temperature for the production of biodiesel from soybean oil. Process of impregnating with CaCO3, BaCO3, SrCO3 and CdCO3 suspension solutions and being calcined at high-temperature did not promote improvement of catalytic activity of EFD powder, while the single impregnating with K2CO3 suspension solution can only improve its catalytic activity in the first use. Na2CO3@EFD catalyst synthesized by impregnating with only Na2CO3 suspension solution owned considerable catalytic activity from nano Na2CO3 (37.0 nm) and good recyclability from nano Fe3O4 (size of 30.0 nm & Ms of 26.77 Am2/kg) with biodiesel yield of 99.13 wt% at 65 oC in 2 h with 15/1 methanol/oil molar ratio and 7 wt% catalyst dosage in the first use (93.50 wt% in the eleventh use). The kinetic study with Na2CO3@EFD was carried out, and it was found that the activation energy was 32.81 kJ/mol and the frequency factor was 3760.85 /min, lower than reported solid base catalysts, which suggested synthesized Na2CO3@EFD catalyst owned remarkable potential for industrial application in biomass energy conversion.

Related results were accepted in Catalysis Today:

YT Wang, D Gao, J Yang, YN Zeng, JG Li, YJ Wang, XM Wang, FP Wang, Q Yu, TJ Liu, S Cai, Z Fang. Highly Stable Heterogeneous Catalysts from Electric Furnace Dust for Biodiesel Production: Optimization, Performance and Reaction Kinetics. Catalysis Today, 2021, https://doi.org/10.1016/j.cattod.2021.12.013.

Highly stable heterogeneous catalysts were prepared with carbonates suspension solutions impregnating onto electric furnace dust to catalyze the production of biodiesel from soybean oil with biodiesel yield of 99.13 wt% in the first use (93.50 wt% in the eleventh use). 电炉粉尘通过碳酸盐悬浊液浸渍后制备长寿非均相催化剂用于催化制备生物柴油,产率高达99.13 wt%,循环使用11次后产率仍可达到93.50 wt%。

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电炉粉尘制备长寿命非均相催化剂用于生物柴油的生产及反应动力学研究

王一同和方真教授在国际学术期刊Catalysis Today发表学术论文:

电炉粉尘制备长寿非均相催化剂用于生物柴油的生产及反应动力学研究

最近,王一同博士(女,华北理工大学冶金与能源学院副教授)和方真教授在国际学术期刊Catalysis Today(IF: 6.766, Q2)发表题为“电炉粉尘制备长寿非均相催化剂用于生物柴油的生产及反应动力学研究”的研究性论文。

利用碳酸盐悬浊液湿法浸渍电炉粉尘和高温煅烧的手段制备长寿非均相催化剂用于催化豆油制备生物柴油。用CaCO3、BaCO3、SrCO3、CdCO3悬浊液和K2CO3溶液浸渍和高温煅烧对电炉粉尘的催化活性没有显著影响。用Na2CO3溶液浸渍合成的Na2CO3@EFD催化剂具有较好的催化活性和可循环性,生物柴油的产率为99.13 wt%,循环是11次后仍可获得93.50 wt%的产率,催化剂回收率> 90 wt%。对Na2CO3@EFD催化剂进行动力学研究,发现活化能为32.81 kJ/mol,频率因子为3760.85 /min,低于已经报道的固体碱催化剂,表明合成的Na2CO3@EFD催化剂具有显着的潜力用于生物质能转化的工业应用。详情可见:

YT Wang, D Gao, J Yang, YN Zeng, JG Li, YJ Wang, XM Wang, FP Wang, Q Yu, TJ Liu, S Cai, Z Fang. Highly Stable Heterogeneous Catalysts from Electric Furnace Dust for Biodiesel Production: Optimization, Performance and Reaction Kinetics. Catalysis Today, 2021, https://doi.org/10.1016/j.cattod.2021.12.013.

 

电炉粉制备生物柴油Production of biodiesel with electric furnace dust impregnated in Na2CO3 solution

电炉粉制备生物柴油Efficient production of biodiesel with electric furnace dust impregnated in Na2CO3 solution

Recently, Dr Yi-Tong Wang (Associate Prof., College of Metallurgy and Energy, North China University of Science and Technology) and Prof. Zhen Fang published an article in Journal of Cleaner Production about electric furnace dust impregnated with Na2CO3 solution for biodiesel production.

Solid catalyst (Na2CO3@EFD) was prepared by wet impregnation of electric furnace dust (EFD) in aqueous Na2CO3 solution. It had high basicity and acidity of 0.34 and 0.16 mmol/g for biodiesel production. High biodiesel yield of 99.8 wt% from soybean oil was obtained under the optimized reaction conditions (by Central Composite Design) of 71 oC in 111.36 min with 5.4 wt% catalyst and methanol/oil molar ratio of 11.8/1. After 11 cycles, biodiesel yield still maintained at 90.8 wt% with catalyst recovery rate > 90 wt% by magnetic separation of catalyst EFD powders (containing Fe3O4 with magnetism of 59.1 Am2/kg). Pure Na2CO3 particles presented poorer recyclability with lower biodiesel yield of 89.5 wt% even at the eighth cycle by centrifugal separation. Na2CO3@EFD catalyst had high activity and recyclability because: (i) EFD as support hosted nanoparticles of Na2CO3 (30.3 nm) as main base site for transesterification; (ii) porous EFD support provided acidic sites from metal oxides (e.g., ZnO and Al2O3) for esterification; (iii) EFD adsorbed active components into its micropores to maintain high recyclability; and (iv) EFD magnetism from magnetic Fe3O4 kept high efficient magnetic separation. Total metals in the blended biodiesel met the National Standard of China and heavy metals were lower than typical petrochemical diesel. The study provided a practical use of industrial solid waste for the green production of biodiesel.

Related results were accepted in Journal of Cleaner Production:

YT Wang, D Gao, YN Zeng*, JG Li*, AM Ji, TJ Liu, S Cai, WJ Cong, FP Wang, Q Yu, XM Wang, Zhen Fang*. Efficient Production of Biodiesel with Electric Furnace Dust Impregnated in Na2CO3 Solution. Journal of Cleaner Production, 330, 129772 (2022), https://doi.org/10.1016/j.jclepro.2021.129772.

Nanocatalyst was synthesized by impregnating electric furnace dust in Na2CO3 solution for soybean biodiesel production with high yield of 99.8 wt% and good recyclability (11 cycles). 电炉粉尘通过Na2CO3溶液浸渍后可用于催化豆油制备生物柴油,产率高达99.8 wt%,该催化剂具备良好的寿命,可循环使用11次。


王一同博士和方真教授在国际学术期刊Journal of Cleaner Production发表学术论文:

Na2CO3溶液浸渍电炉粉尘用于催化生物柴油高效生产

最近,王一同博士(女,华北理工大学冶金与能源学院副教授)和方真教授在国际学术期刊Journal of Cleaner Production(IF: 9.297,Q1)发表题为“Na2CO3溶液浸渍电炉粉尘用于催化生物柴油高效生产”的研究性论文。

利用Na2CO3水溶液湿法浸渍电炉粉尘后制备固体酸碱两性材料(Na2CO3@EFD),可用于催化生物柴油高效生产。多孔电炉粉尘作为载体将活性组分Na2CO3纳米粒子吸附到粉尘内部微孔中,同时为转酯化反应提供碱性活性位点,粉尘中的的酸性氧化物,如:ZnO和Al2O3,可为酯化反应提供所需的酸性活性位点,粉尘中的磁性铁氧化物可保证合成催化剂拥有高效的磁分离特性。在响应面优化的条件下,生物柴油的产率达到99.8 wt%,循环11次后仍可获得90.8 wt%的产率,催化剂的回收率> 90 wt%。该研究为生物柴油的绿色生产、工业固体废物绿色资源化提供新思路。详情可见:

YT Wang, D Gao, YN Zeng*, JG Li*, AM Ji, TJ Liu, S Cai, WJ Cong, FP Wang, Q Yu, XM Wang, Zhen Fang*. Efficient Production of Biodiesel with Electric Furnace Dust Impregnated in Na2CO3 Solution. Journal of Cleaner Production, 330, 129772 (2022), https://doi.org/10.1016/j.jclepro.2021.129772.

航空燃料合成Lanthanide catalyst for synthesis of jet fuel intermediates

Recently, master student Miss Lu-ping Li supervised by Dr. Xiao Kong and Prof. Zhen Fang published a research article in Molecular Catalysis about the synthesis of jet fuel intermediates.

Jet fuel precursors (4-(2-furyl)-3-buten-2-one (FAc) and 1,5-di-2-furanyl-1,4-pentadien-3-one (F2Ac)) can be produced from aldol condensation between furfural and acetone over basic catalysts. However, there is still a need to develop efficient alkaline catalysts and understand the role of alkaline sites. In this work, La2O2CO3-Al2O3 catalyst was successfully prepared by coprecipitation and the effect of preparation conditions on the properties and catalytic performance was investigated. Experiments showed that La2O2CO3 and La2O3 were formed after calcination, and the activity was greatly improved by the introduction of La2O2CO3. At higher coprecipitation pH, rod-shaped La2O2CO3 was formed, exposing basic La3+-O2- sites for good performance in aldol condensation reactions. The catalytic performance of La2O2CO3-Al2O3 in aldol condensation of furfural with acetone was also evaluated and compared with that of Al2O3, La2O3, La2O3-Al2O3, La(OH)₃/Al2O3 and La2O2CO3/Al2O3. A total conversion of furfural can be realized with F2Ac yield of 67.8% at a furfural/acetone ratio of 1/1 and 90 oC, with a FAc yield of 25.8% at the same time. The deactivation mechanism of the La2O2CO3-Al2O3 catalyst was also studied.

Liquid fuel precursors can be produced by furfural-acetone aldol condensation over La2O2CO3-Al2O3 catalyst with C13 yield of 67.8%(通过糠醛和丙酮之间的羟醛缩合在La2O2CO3-Al2O3催化剂上制备液体燃料中间体,C13产率为67.8%)

Related results were published in Molecular Catalysis:

Lu-ping Li, Zhen Fang*, Xiao Kong*, Wen-Jie Cong, Molecular Catalysis, 515, 111893 (2021). https://doi.org/10.1016/j.mcat.2021.111893.

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镧系催化剂合成航空燃料中间体

最近,硕士生李路平(女)在方真老师和孔晓博士的指导下,在国际学术期刊Molecular Catalysis(IF5.062,Q2)上发表关于镧系催化剂用于合成航空燃料中间体的研究文章。

通过糠醛和丙酮的羟醛缩合可以在碱性催化剂上获得航空燃料前体呋喃加合物4-(2-呋喃基)-3-丁烯-2-酮(FAc)和1,5-二-2-呋喃基-1,4-戊二烯-3-酮(F2Ac)。然而,仍然需要开发有效的碱性催化剂并了解碱性位点的作用。本工作采用共沉淀法成功制备了La2O2CO3-Al2O3催化剂,并研究了制备条件对其结构和催化性能的影响。实验表明,经煅烧后形成La2O2CO3和La2O3,而La2O2CO3极大的提高了催化活性。在较高的共沉淀pH值下可以形成棒状的La2O2CO3,并暴露出更多的La3+-O2-碱性位点,在羟醛缩合反应中表现出良好的性能。之后,在糠醛与丙酮的羟醛缩合实验中评价了La2O2CO3-Al2O3的催化性能,并与Al2O3、La2O3、La2O3-Al2O3、La(OH)3/Al2O3和La2O2CO3/Al2O3的进行了催化性能的比较。在糠醛/丙酮比为1/1和90 oC下,糠醛的总转化率为67.8%,同时FAc产率为25.8%。最后研究了La2O2CO3-Al2O3催化剂的失活机理。详情可见:

Lu-ping Li, Zhen Fang*, Xiao Kong*, Wen-Jie Cong, Molecular Catalysis, 515, 111893 (2021). https://doi.org/10.1016/j.mcat.2021.111893.

水热胺化Hydrothermal amination of biomass to nitrogenous chemicals

水热胺化Hydrothermal amination of biomass to nitrogenous chemicals

Recently, Profs. Hu Li (Guizhou University) and Zhen Fang, published a review (Critical review, 2021 Green Chemistry Hot Articles) paper in Green Chemistry about hydrothermal amination of biomass to nitrogenous chemicals.

Biomass is the most abundant and low-cost renewable source for the production of value-added nitrogen-containing compounds. However, a large amount of water exists in natural biomass and relevant bio-derivatives, which often need to be removed prior to conducting valorization processes. Direct use of wet biomass and bio-derivatives as feedstocks definitely avoids energy consumption of drying processes, in which water acts as a reactive medium and is friendly to the environment and reaction devices. Hydrothermal amination of wet biomass feedstocks is thus an attractive technical strategy for producing nitrogen-containing compounds. This review summarizes state-of-the-art technologies in hydrothermal amination of natural biomass, bio-polymeric derivatives, and bio-based platform molecules with or without nitrogenous species into organonitrogen chemicals. Efforts are made to shed light on conversion routes and economic/environmental impacts of biomass hydrothermal amination. Challenges and perspectives on the large-scale production of biomass-derived nitrogenous compounds are also put forward.

Conversion routes, processing strategies, state-of-the-art technical advances, challenges and perspectives in hydrothermal amination of N-rich biomass sources and N-free biomass feedstocks to nitrogenous chemicals.(水热胺化富氮和无氮生物质原料为含氮化学品的转化路线、加工策略、最新技术进展、挑战和前景。).

Related results were published in Green Chemistry:

HG Wu, H Li,* Zhen Fang*, Hydrothermal Amination of Biomass to Nitrogenous Chemicals, Green Chemistry, 23, 6675-6697, (2021) (Critical review, 2021 Green Chemistry Hot Articles)), https://doi.org/10.1039/D1GC02505H

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李虎和方真教授在国际学术期刊Green Chemistry发表学术论文:

水热胺化生物质制备含氮化合物

最近,国际学术期刊Green Chemistry以Critical review形式,发表了生物质水热胺化制备含氮化合物的综述。

生物质是生产高附加值含氮化合物最丰富、成本最低的可再生资源。然而,天然生物质和相关衍生物中存在大量水,通常需要在进行高值化过程之前将其去除。直接使用湿生物质和生物衍生物作为原料避免了干燥过程的能耗,在干燥过程中,水作为反应介质,对环境和反应装置友好。因此,湿生物质原料的水热胺化是生产含氮化合物的一种有吸引力的技术策略。本文综述了将天然生物质、生物聚合物衍生物和含氮或不含氮的生物基平台分子水热胺化为有机氮化学品的最新技术。努力阐明生物质水热胺化的转化路线和经济/环境影响。并对生物质含氮化合物的大规模生产提出了挑战和展望。

详情可见:

Related results were published in Green Chemistry:

HG Wu, H Li,* Zhen Fang*, Hydrothermal Amination of Biomass to Nitrogenous Chemicals, Green Chemistry, 23, 6675-6697, (2021) (Critical review, 2021 Green Chemistry Hot Articles), https://doi.org/10.1039/D1GC02505H