Study on Synthesis of N-containing Compounds from 5-Hydroxymethyl Furfural

生物质被认为是唯一可以替代化石资源获取燃料、材料和化学品的可再生资源。作为生物质基重要平台化合物，5-羟甲基糠醛（HMF）由于其独特的化学结构引起了国内外广泛关注。含氮化合物可以广泛应用于制备医药中间体、护肤品、农药、精细化学品以及合成聚合物等；近年来，生物质基5-羟甲基糠醛合成含氮化合物成为研究的热点。本论文提出了HMF合成含氮化合物的新方法，利用Ritter反应和还原胺化反应分别将HMF的羟基和醛基胺化，探讨了HMF合成N-乙酰基-5-氨甲基糠醛（NAMF）并进一步合成2，5-二氨甲基呋喃（BAF）的反应途径。 首先，研究了HMF在酸催化条件下与乙腈反应制备NAMF的途径。在反应温度10...In recent years, biomass is considered the only renewable resource on earth that can replace fossil resources for the production of fuel, materials and chemicals. As an important platform chemical derived from biomass, 5-Hydroxymethyl furfural (HMF) is attracting more and more attention owning to the unique chemical structure with both hydroxyl and aldehyde groups. Nitrogen compounds can be widely...学位：工程硕士院系专业：能源学院_工程硕士(材料工程)学号：3242014115225

Material and Energy Conversion of Integrated 100,t/a-Scale Bio-Jet Fuel-Range Hydrocarbon Production System via Aqueous Conversion of Biomass

以农业废弃物生物质为原料，利用水相转化技术，进行了百吨/年规模生物航油类烃(C8~C15)合成试运行.过程中采用两步酸解法分别将玉米秸秆中半纤维素和纤维素转化为糠醛和乙酰丙酸，作为生物质基平台化合物.在碱性条件下糠醛与乙酰丙酸经Aldol缩合反应实现碳链增长，生成的长链含氧中间体经过低温预加氢、高温加氢脱氧及精制，生成C8~C15范围内液态烃，可作为生物航油组分.以试运行实验结果为基础，进行了过程的物质与能量转化分析.结果表明，该路线获得液态烃类的基本性质满足合成航油ASTM-7566标准要求，并充分利用了原料中纤维素和半纤维素组分，是一条基于生物质的长链液态烃合成路线，1t航油约需10~12t干基玉米秸秆

The Synthesis of Advantame

Advantame是一种新型的高效二肽甜味剂，它的甜度是蔗糖的20，000倍，并且具有甜味纯正、不含热量、性质稳定等优点。Advantame现已通过美国食品药品监督管理局（FDA）食品安全认证，是甜味剂研究的又一重要成果。目前，Advantame的合成过程一般分为两步，先采用异香兰素和乙醛通过羟醛缩合反应生成中间体3-羟基-4-甲氧基肉桂醛，再将中间体与阿斯巴甜通过还原胺化反应生成Advantame。由于异香兰素和乙醛的羟醛缩合反应需要在低温下进行，而且耗时长、收率低，因此Advantame的合成过程亟待优化。 本论文以异香兰素为起始原料，经羟醛缩合反应合成了中间体3-羟基-4-甲氧基肉桂醛...Advantame is a novel high-intensity sweetener and its sweetness is 20,000 times sweeter than sugar’s. Advantame has no calories and an outstanding flavor profile. Nowadays, Advantame has got approved of the FDA and it’s the latest achievement of sweeteners research. The synthetic process of Advantame can be concluded into two reactions including the aldol condensation reaction to synthesize 3-hy...学位：工学硕士院系专业：化学化工学院_化学工程学号：2062014115144

Preparation and Characterization of Pt-Ni-SnO2/C for Ethanol Oxidation Reaction

采用改进的Bonnemann法成功制备了Pt/C、Pt-Ni_(1/3)/C、Pt-SnO_2/C、Pt-Ni_x-SnO_2/C(x =; 1/4, 1/3, 2/3,; 1)阳极电催化剂。利用X射线衍射(XRD)、高分辨透射电子显微镜(HR-TEM)以及X射线光电子能谱(XPS)对催化剂晶型结构、表面形貌和表面电; 子结构进行了表征。运用线性扫描伏安(LSV)和电流密度-时间(j-t)曲线进行电化学测试,研究了乙醇电催化氧化(EOR)活性。并用原位红外光谱(; in situ; FT-IR)研究了EOR过程中产物的分布。结果表明,Pt-Ni_(1/3)-SnO_2/C是由Pt-Ni合金和SnO_2两相组成。XPS结果表明; ,在Pt-SnO_2中添加微量的Ni,Pt表面电子结构发生了改变。电化学结果表明,三元催化剂的EOR活性均优于二元和纯Pt,其中Pt-Ni_(1; /3)-SnO_2/C的EOR活性最佳。Ni和SnO_2的加入并没有显著提高乙醇C-C键的断裂能力,但是二者的协同作用在低电位(0.1; V)下加强了乙醛的进一步氧化,生成了乙酸。A series of Pt/C, Pt-Ni-1/3/C, Pt-SnO2/C and Pt-Nix-SnO2/C (x = 1/4, 1/3, 2/3, 1) anode electro-catalysts have been synthesized by an improved Bonnemann method. The crystal structure, surface morphology and surface electronic structure were characterizated by X-ray diffraction (XRD), high resolution transmission electron microscope (HR-TEM) and X-ray photoelectron spectroscopy (XPS). The electro-catalytic activities were characterizated by linear sweep voltammetry (LSV) and amperometric current density-time (j-t) curve techniques for ethanol oxidation reaction (EOR). In situ spectroelectrochemical studies have been used to identity adsorbed reaction intermediates and products (in situ Fourier transform infrared spectroscopy, FT-IR). XRD and HR-TEM analysis revealed two phases in the ternary Pt-Ni-SnO2/C catalyst: Pt-Ni alloys and SnO2. XPS results show that the electronic structure of the Pt in Pt-Ni-1/3-SnO2/C might be changed due to the addition of Ni. The activity of Pt-Ni-SnO2/C for EOR was found to be higher than that of Pt/C, Pt-Ni/C and Pt-SnO2/C catalysts. The incorporation of Ni and SnO2 did not significantly improve C-C bond breaking for complete oxidation of ethanol, but the synergy under the low potential (0.1 V) to strengthen the further oxidation of acetaldehyde, generate the acetic acid.吉林省科技发展计划项目（20120741）和厦门大学固体表面物理化学国家重点实验室开放课题（201407）资

Optimization of β-Cyclodextrin Inclusion Technology of Volatile Oil from Pueraria Compound by Orthogonal Design

目的优选葛根复方挥发油的包合工艺,提高制剂的稳定性。方法采用饱和水溶液法制备包合物,以挥发油中藁本内酯、桂皮醛、甲基丁香酚包合率及包合物得率为综合评价指标,采用正交试验法考察挥发油与β-环糊精的比例、包合时间、包合温度对包合工艺的影响,优化得到葛根复方中挥发油的最优包合工艺。结果葛根复方中挥发油的最佳包合工艺条件为挥发油与β-环糊精比例为1∶8,包合温度为30℃,包合时间为1h,验证试验中,藁本内酯、桂皮醛及甲基丁香酚的包合率为别为86.58%±0.009%,73.34%±0.001%,68.89%±0.020%,包合物得率为67.98%±0.047%。结论所确定的包合工艺挥发油的包合率高、工艺稳定可行。Objective To obtain the optimized technology of volatile oil from Pueraria Compound with β-Cyclodextrin（ β-CD）. Methods The inclusion compound was prepared by saturated peroxide solution method. In order to optimize inclusion technology,orthogonal design was performed,with the content of multi-target ingredient,such as ligustilide,cinnamic aldehyde,methyleugenol and the yield of inclusion as comprehensive evaluation indexes. Three factor was performed,the ratio of volatile oil（ m L） to β-CD（ g）,the inclusion temperature and the inclusion time. Results The optimum conditions for inclusion process were as follow： the ratio of volatile oil（ m L） to β-CD（ g） was 1： 8,the inclusion temperature was 30℃ and the inclusion time was 1h. With the optimum inclusion condition,the content of ligustilide,cinnamic aldehyde and methyleugenol and the yield of inclusion were 86. 58% ± 0. 009%,73. 34% ± 0. 001%,68. 89% ± 0. 020%,and 67. 98% ± 0. 047%,respectively.Conclusion The optimum inclusion condition was stable and reproducible with a high inclusion yield.国家自然科学基金（No.81270901）;上海市教委基金（No.15cxy21

PtNiSnO/C的制备、表征及其电催化氧化乙醇活性

采用改进的B?nnemann法成功制备了Pt/C、Pt-Ni/C、Pt-SnO/C、Pt-Ni-SnO/C（x=1/4,1/3,2/3,1）阳极电催化剂。利用X射线衍射（XRD）、高分辨透射电子显微镜（HR-TEM）以及X射线光电子能谱（XPS）对催化剂晶型结构、表面形貌和表面电子结构进行了表征。运用线性扫描伏安（LSV）和电流密度-时间（j-t）曲线进行电化学测试,研究了乙醇电催化氧化（EOR）活性。并用原位红外光谱（in situ FT-IR）研究了EOR过程中产物的分布。结果表明,Pt-Ni-SnO/C是由Pt-Ni合金和SnO两相组成。XPS结果表明,在Pt-SnO中添加微量的Ni,Pt表面电子结构发生了改变。电化学结果表明,三元催化剂的EOR活性均优于二元和纯Pt,其中Pt-Ni-SnO/C的EOR活性最佳。Ni和SnO的加入并没有显著提高乙醇C―C键的断裂能力,但是二者的协同作用在低电位（0.1 V）下加强了乙醛的进一步氧化,生成了乙酸。吉林省科技发展计划项目(20120741)；厦门大学固体表面物理化学国家重点实验室开放课题(201407)资助~~

Insecticidal Activity for Benzaldehyde L-Cysteine Schiff Base Combined with Xylosma Wood Vinegar

木醋碱杀虫剂是一种基于木炭副产物木醋液的绿色杀虫剂,是将精馏木醋液、苯甲醛L-半胱氨酸席夫碱、水杨酸按照一定比例配制而成的.以酪氨酸酶筛选模型研究了苯甲醛L-半胱氨酸席夫碱、精馏木醋液、木醋碱杀虫剂对酪氨酸酶的抑制作用,其导致酪氨酸酶活性的半抑制质量浓度(IC50)分别为15,2.53,0.53 mg/m L.探讨了木醋碱杀虫剂对小菜蛾(Plutella xylostella)、棉铃虫(Helicoverpa armigera)、玉米螟(Pyrausta nubilalis)幼虫的杀虫活性,结果表明木醋碱杀虫剂中苯甲醛L-半胱氨酸席夫碱质量浓度达到15 mg/m L时即可对小菜蛾、棉铃虫、玉米螟二龄幼虫达到很好的杀灭效果.急性毒理实验表明木醋碱杀虫剂实际无毒.慢性毒理研究按照3 g/kg给药量连续灌胃3个月,昆明小鼠的肝脏和肾脏并不存在毒理性变化,表明木醋碱杀虫剂没有慢性毒性.综上所述,木醋碱杀虫剂不仅对酪氨酸酶有很好的抑制作用,还对小菜蛾、棉铃虫、玉米螟等常见农业害虫具有较强的毒杀活性,且实际无毒,具有良好的农业应用前景.The wood vinegar was based on by-product in the process of firing Xylosma charcoal.The wood vinegar base insecticide was a new green type insecticide.We mixed the rectificated wood vinegar,benzaldehyde L-cysteine Schiff base and salicylic acid to make the wood vinegar base insecticide proportionally.The inhibition on tyrosinase in screening model of benzaldehyde L-cysteine Schiff base,rectificated wood vinegar and the wood vinegar base insecticide were determined. The half maximal inhibitory concentration( IC50) were 15,2. 53,0. 53 mg/m L,respectively.Additionally,the insecticidal effects on Plutella xylostella,Pyrausta nubilalis and Helicoverpa armigera of wood vinegar base insecticide were investigated.The results showed that the wood vinegar base insecticide could effectively kill the second-stage juveniles of P.xylostella,P. nubilalis and H. armigera. The results showed that the wood vinegar base insecticide had insecticidal effect.The acute toxicological results showed that the wood vinegar base insecticide had no toxicity.In the chronic toxicological experiment,the group was given a gavage of 3 g / kg with the wood vinegar base insecticide in 3 months.We took the liver and kidney in paraffin section and HE staining after executing the Kunming mouse with cervical dislocation method.The results showed that the wood vinegar base insecticide had no chronic toxicity.In conclusion,the wood vinegar base insecticide could not only inhibit the tyrosinase acitivity,but also show good insecticidal effects on P. xylostella,P. nubilalis and H. armigera with low toxicity.The wood vinegar base insecticide had shown good application prospects in agricultural areas.国家自然科学基金(31371857

Lignin and lignin-acetoderivative oxidative degradation into valuable aromatic aldehydes

本项工作研究了木质素的转化以及其副产品(乙酸基衍生物)转变为高附加值的芳香醛，乙酸基衍生物在碱性条件下催化氧化降解的动力学方程等问题。竹材木质素被转化为高附加值的芳香醛和乙酸基衍生物。在铜作为催化剂的条件下，香草乙酮被转化为香草醛。另外，乙酰丁香酮首次转化为丁香醛，从而通过降解木质素氧化过程中的副产物来提高整个过程的价值。本文用GC-MS分析得到了一种可靠的一致的相对影响因子法来定量木质素和乙酸衍生物。竹材木质素的总产率接近9.5%，且香草醛的产率为55%，其中90%以上来自于香草乙酮。来源于木质素，通过降解乙酸衍生物而得到高附加值的芳香醛分为两步反应。文章首次研究了120-150℃条件下香草...The main objective of this work was to study the transformation of lignin and its by-products (acetoderivatives) into valuable aromatic aldehydes as well as the kinetics of acetoderivative degradation during the alkaline catalytic oxidation. Bamboo lignin was transformed into valuable aromatic aldehydes and acetoderivatives. Vanillin was recovered from acetovanillone with the application of copper...学位：工程硕士院系专业：化学化工学院_化学工程学号：2042013115452

Study on synthesis of 7-hydroxy-4-methylcoumarin

本文主要针对磷钨酸(HPW)催化合成7-羟基-4-甲基香豆素效率低、成本高等问题，选取聚乙烯基吡咯烷酮(PVP，K30)和N-甲基吡咯烷酮(NMP)为载体，通过浸渍法制备负载磷钨酸催化剂，改善其催化性能，建立7-羟基-4-甲基香豆素高产率的新工艺。主要开展了以下几方面研究： 1.聚乙烯基吡咯烷酮负载磷钨酸催化剂(PVP-HPW)和N-甲基吡咯烷酮负载磷钨酸催化剂([NMP]3PW)的制备及表征：采用浸渍法制备PVP-HPW和[NMP]3PW催化剂，运用红外光谱、热重分析、元素分析、紫外-可见漫反射-近红外光谱分析等多种表征方法对合成的催化剂进行表征。结果表明，PVP-HPW和[NMP]3PW...In order to solve the problems of the low catalytic efficiency and high cost in synthesis of 7-hydroxy-4-methylcoumarin which is catalyzed by phosphotungstic acid, We selected PVP (K30) and NMP as supporter to improve the catalytic performance by the method of impregnation to prepare supported phosphotungstic acid catalysts and build new 7-hydroxy-4-methylcoumarin’s synthetic processes with high y...学位：工程硕士院系专业：化学化工学院_工程硕士(化学工程)学号：2062013115149

Advances for the Ruthenium Complexes-Based Homogeneous Catalytic Hydrogenation of Oxalates to Ethylene Glycol

草酸酯加氢是重要的有机化学反应,在工业制乙二醇生产中有着重要的应用.对钌金属配合物均相催化反应的研究进行了综述.以催化反应体系为焦点,探讨了多种; 因素如温度、氢气压力、催化剂浓度、反应时间、添加剂等对底物转化率以及产物选择性的影响,并讨论了催化反应机理,其中金属-配体协同促进的H_2分子异; 裂,进而完成对底物分子中酯基依次加氢的反应机理是探讨的重点,这为新型催化剂的设计和应用提供参考.Hydrogenation of oxalates is one of the important organic reactions, which has an ultimate use for the industrial production of ethylene glycol. The studies on the ruthenium complexes-based homogeneous catalytic reaction systems are herein summarized. With the focus on the catalytic reaction systems, the important factors with significant influences on the oxalate transformation efficiency as well as the product selectivity are discussed, including temperature, H-2 pressure, catalyst concentration, reaction duration, additives, and so on. The catalytic reaction mechanisms are also discussed in detail, where the mechanism for the H-2-heterolysis promoted under the metal-ligand cooperation for the oxalate hydrogenation to ethylene glycol is enhanced. This study would be useful for designing the new catalyst applicable in industry.National Natural Science Foundation of China [21473142, 91545115,; 21473145]; Innovative Research Team of China [IRT_14R31, J1310024