超稠油供氢水热裂解改质降黏研究

通过超稠油水热裂解反应前后黏度、沥青质、硫质量分数等性质的变化，研究了超稠油进行水热裂解的主要影响因素及规律。结果表明，超稠油中含有一定量的硫是地层注蒸汽温度下进行水热裂解反应的前提。温度和时间对反应有很大影响。供氢剂中四氢萘对超稠油水热裂解影响最大。四氢萘供氢剂与硫酸镍催化剂复配使用对超稠油水热裂解有协同效应。水热裂解物理模拟实验表明,胜利单家寺油田超稠油通过供氢催化水热裂解降黏率可达70%以上。胶质、沥青质、硫质量分数降低，H/C原子比提高，超稠油得到一定程度的改善。     

氯化钙催化纤维素热裂解动力学研究

用差示热重分析仪对氯化钙纤维素热裂解动力学催化影响进行了研究。结果表明，氯化钙对焦炭的形成具有强烈的促进效果，使热裂解最终残留物产率从5％提升到10％以上，氯化钙的存在影响到热失重初始阶段活性纤维素的生成，使热重曲线向低温侧移动，并在低温段产生了小的失重速率峰。通过热重分析发现，氯化钙催化条件下纤维素热裂解动力学参数被分为了三段，分别对应于活性纤维素的生成、炭化和活性纤维素转化为挥发分产物三个区间，并依次成为整体失重过程的控制步骤。结合Broido-Shafizadeh机理分析以及与纯纤维素热裂解动力学参数的对比，氯化钙对这三个主要反应步骤都产生了促进效果，其中以催化焦炭的生成最为明显，在促进焦炭化的过程中，降低了气体产物的生成比率。     

聚苯乙烯的催化裂解研究

由于塑料性质稳定,难以自然降解,其废弃物不仅严重污染环境,更造成了资源浪费.因此,废旧塑料的再资源化对环境保护和可持续发展有着重要意义.废塑料再资源化回收技术是指将废塑料热裂解或催化裂解、回收燃料油和化工原料的技术~([1,2]).     

水溶性配合物催化的稠油低温热裂解研究

在一种新型稠油低温裂解催化体系中合成了两个系列10个过渡金属配合物催化剂。该反应体系中水对原油热降解反应有一定的影响,合适的用量水/油(质量比)为0.3。部分合成水溶性催化剂180℃下对稠油热裂解具有明显的催化作用,催化剂N5的降凝作用效果最好,经催化水热降解改质反应后原油的凝点降低11.4℃;催化剂N2和N5的催化降黏效果较好,降黏率可达70%以上,催化剂N5的最佳用量为0.5%;热重分析和气相色谱分析显示原油热催化降解反应后轻质组分明显增加。     

熔盐热裂解大豆油的特性研究

以大豆油为原料,在ZnCl₂-KCl熔融盐体系中考察了进料速量、载气流量、反应温度及进料量对其热裂解的影响。采用气相色谱-质谱联用仪(GC-MS)表征生物油组成。结果表明,进料速量和载气流量主要通过改变大豆油的反应停留时间影响裂解效果。当进料速率为1.2 g/min及不通载气时,大豆油停留时间较长,裂解较充分;随着温度升高,生物油得率增大,含氧化合物含量及酸值上升;随着进料量增大,生物油得率稳定在70%左右,但脱羧效果有所下降。经过催化加氢,生物油性质得到了明显的改善,组分分布与0^#柴油分布大体相似。     

生物油蒸馏残渣理化性质及热失重研究

利用傅里叶变换红外光谱仪、激光共焦显微拉曼光谱仪和TGA Q500热分析仪对生物油蒸馏残渣及其在不同温度处理后的热解焦炭理化性质进行表征,并对其热失重特性进行分析。结果表明,生物油蒸馏残渣主要是由脂肪族、芳香族和低聚糖类等有机化合物组成;在氮气氛围下热解主要分为三个阶段:30-145℃为小分子物质挥发析出阶段145-550℃为大分子物质裂解和氧化阶段,550-750℃为焦炭产生阶段;热处理过程中各类物质逐步有序热解析出,同时固体产物石墨化程度随着热处理终止温度的升高而升高。     

低温煤焦油分子组成与加氢转化

低温煤焦油是一种十分复杂的混合物,其分子组成研究具有较大的技术难度.依托高分辨质谱等新型分析技术,重质油国家重点实验室围绕低温煤焦油的分子组成开展了一系列基础研究工作,本文简要总结了近年来该实验室在煤焦油分子组成方面的工作进展.以不同低阶煤通过气化或干馏生产的10个煤焦油样品为研究对象,分析了其宏观性质和分子组成,建立了适合煤焦油分析的组分分离方法.通过气相色谱-质谱联用、高分辨质谱等技术深入研究了焦油及其分离组分,以及加氢转化产物的分子组成,在分子层次上研究了加氢过程中不同类型化合物的转化规律.化学组成上的深入认识为焦油利用的方案选择、催化剂设计、工艺开发及优化提供了重要的理论依据和基础数据,有助于实现焦油的高效转化与利用.     

烟煤和低温煤焦油共处理反应及机理的研究

兖州烟煤和低温煤焦油在４３０℃，初始氢压为７．０ＭＰａ条件下进行共处理反应。通过对煤的苯和四氢呋喃（ＴＨＦ）抽提物以及共处理产物的核磁共振测定，结合煤的红外光谱分析，探讨了兖州烟煤和低温煤焦油共处理过程中发生的化学反应及反应机理。     

ZnS-AgInS_2量子点的制备及修饰

通过热裂解法以油胺为配体制备了ZnS-AgInS2量子点。产物荧光性质好,通过改变Zn、Ag、In元素的比例可发射从红色到蓝色的荧光,荧光量子产率可以达到15%;其晶体结构和分散性好,粒径均匀(约为4nm)。分别采用两种不同的配体取代法将油溶性ZnS-AgInS2量子点修饰为水相性,发现羧甲基聚乙二醇硫醇(CM-PEG-SH)和巯基丙酸共修饰得到的产物比经巯基乙酸修饰得到的产物具有更好的荧光性质和稳定性,前者的荧光量子产率可达到10%,且连续2个月的检测结果表明其荧光强度随着放置时间的延长而增强。考察了常见阳离子对CM-PEG-SH和巯基丙酸共修饰产物荧光性质的影响,初步探讨了其影响机理。     

氧化镁对聚丙烯/聚氯乙烯脱氯行为的影响

对废旧塑料的回收利用是近年来人们一直关注和不断研究的一个重要课题。将废塑料热裂解为燃料油或单体被认为是最具前景的处理方法之一[1]。当含有PVC的废旧塑料裂解时产生氯化氢气体,严重腐蚀设备;同时也会产生含氯的有机化合物,从而使其裂解生成的液体作为燃料使用时会生成有     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.