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

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/CN_x 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/CN_x 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/CN_x) 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/CN_x）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/CN_x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/CN_x 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

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⁺-O^2- 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⁺-O^2-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.