利用色谱-反应联合装置研究渣油及其胶质的反应性能

 建立一套色谱－反应联合装置，实现了在微量进样条件下对胜利原油减渣中胶质组分的催化裂化反应性能的考察。结果表明，在特殊设计条件下，色谱－反应联合装置具有快速、简便、再现性能良好的特点，可完成对渣油中胶质组分的催化裂化反应性能考察。     

操作苛刻度对RFCC沉降器内油气重组分的影响

在提升管催化裂化中试装置上,考察了操作苛刻度对重油催化裂化(RFCC)装置沉降器中油气重组分,特别是大于550℃的馏分以及油浆中胶质、沥青质的影响,并结合操作苛刻度对产品分布的影响规律,建立了操作苛刻度函数。结果表明,随着操作苛刻度的提高,油浆中的馏分呈现出中间馏分增加,两端馏分降低的变化趋势,并且油浆中大于550℃馏分的含量明显减少,油浆中的胶质、沥青质含量减少。随着操作苛刻度的提高,在一定范围内轻质油收率基本不变,但是达到一定反应程度后,轻质油产率明显降低。建立的操作苛刻度函数为合理控制操作条件,保证目的产物收率的同时降低了油气中重组分的含量,从而为防止沉降器结焦提供了操作依据。     

在Pt/HZSM-5双功能催化剂上FCC汽油加氢异构化反应机理及动力学研究

在活性趋于稳定的Pt/HZSM-5双功能催化剂上，利用连续流动微反一色谱装置，进行了催化裂化汽油加氢异构化反应机理和动力学的研究．在250-330℃，1．0-3．0MPa反应条件下，考察了催化汽油加氢异构化反应产物分布，按单分子反应机理，建立了催化裂化汽油中烯烃加氢异构化反应网络和动力学模型，计算了反应网络中各步的反应速率常数和活化能．结果表明：Pt／HZSM-5双功能催化剂具有较好的加氢和异构活性，在保证辛烷值不下降的条件下，可使催化裂化汽油中烯烃加氢饱和，达到降低汽油烯烃和提高安定性的目的．     

FCC汽油低温改质过程的烯烃转化及催化剂积炭

利用微反-色谱联合实验装置和连续式小型提升管催化裂化实验装置研究了催化裂化汽油低温改质过程中烯烃转化和催化剂积炭的过程和规律。通过对模型化合物和催化裂化汽油改质过程中催化剂活性、催化裂化汽油窄馏分、反应温度、剂油比和反应时间对烯烃转化和催化剂积炭的研究表明，大部分烯烃转化和催化剂积炭的反应发生在油剂接触极短的反应时间内，并随着催化剂活性、反应物活性、剂油比和反应温度的提高而增加。在油剂接触后很长的反应时间内，生焦量、积炭速率和烯烃的转化程度都很小，烯烃转化损失率降低，因此，催化裂化汽油在低温改质的条件下可以通过延长反应时间来提高烯烃的转化率。因此，催化裂化汽油改质的最佳工艺条件为，390℃～440℃，剂油比6，催化剂活性61～65，长反应时间，轻馏分进料。     

FCC轻汽油催化裂化生产丙烯反应规律的研究

在提升管实验装置和脉冲色谱装置上，采用ZSM-5催化剂，考察了不同条件下FCC轻汽油和2M1C5＝的裂化。结果表明,催化裂化过程添加ZSM 5催化剂可提高汽油中C5＝、C6＝的质量分数。轻汽油裂化生产丙烯的性能优于重汽油和全馏分汽油，在相对低的温度下瞬时反应能得到较高的丙烯收率。在脉冲色谱装置上，反应温度和载气流量对轻汽油和2M1C5＝裂化生产丙烯的影响一致，即反应温度升高，载气流量降低，丙烯收率增加。提高反应温度，延长停留时间可以提高丙烯对丁烯的比例。轻汽油在ZSM-5催化剂上反应，催化剂结焦失活速度开始较快，后来减缓。ZSM-5催化剂结焦失活对丙烯生成的抑制作用大于对丁烯的抑制作用，ZSM-5的强酸中心多则更有利于生成丙烯。     

大庆渣油族组分非等温热反应的研究

采用动态热重分析法在升温速率为６．２Ｋ·ｍｉｎ￣（－１）及惰性气流量１００ｃｍ￣３·ｍｉｎ￣（－１）的条件下，对大庆渣油族组分的热转化行为进行了考察，获得了族组分的热转化速率峰值、速率峰值处的反应温度、转化率和剧裂分解温度区间等动力学基本数据以及各族组分的生焦性能。数据分析表明，族组分的热反应活性顺序为：饱和分＞胶质＞芳香分＞沥青质。在大庆渣油族组分热转化的两个温区内，采用分段一级动力学模型较好地拟合了实验数据，确定了各族组分在两个温区内的热反应动力学参数。     

丙烯气相一步氧化制环氧丙烷用Ag-Mo催化剂的研究

 用浸渍法和溶胶－凝胶法制备了一系列以银及氧化钼为活性组分，负载于不同载体上的催化剂．在以分子氧为氧化剂，且原料气中不添加任何抑制剂的情况下，采用微反－色谱联合装置考察了催化剂对丙烯气相一步氧化制环氧丙烷的催化性能．结果表明，载体和助剂对催化剂上丙烯环氧化性能产生明显的影响．以TiO2－ZrO2为载体，CsNO3－NaCl为助剂的Ag－MoO3催化剂具有较好的催化性能，在400℃下，氧的转化率和环氧丙烷的选择性可分别达到11．3％和34．8％；在450℃下，氧的转化率和环氧丙烷的选择性可分别提高到33．0％和35．3％．采用溶胶－凝胶法制备的MoO3／SiO2催化剂对丙烯气相一步环氧化反应也具有一定的催化活性．     

四氢萘在Mo-Ni/USY双功能催化剂上加氢裂化反应动力学的研究

在活性趋于稳定的Mo-Ni／USY双功能催化剂上，利用连续流动微反－色谱装置，进行了四氢萘加氢裂化反应动力学的研究，在320－400℃、4．5－8．5MPa反应条件下，考察其反应产物分布，建立了四氢萘加氢裂化反应动力模型，计算了反应网络中各步的反应速率常数和活化能，并讨论了反应网络的主线和反应条件对主线的影响。结果表明，Mo-Ni／USY双功能催化剂具有较高的裂化和异构化活性，低温、高压有利于加氢、高温、低压有利于裂化和异构。     

Pingba RP-3喷气燃料中有色组分的鉴定及其特性研究

用中性氧化铝吸附、无水乙酸脱附的方法，对储存中变色的Pingba RP-3喷气燃料中的有色组分进行分离制备。应用有机元素分析、红外光谱、色质联用和裂解色质联用等分析法对富集有色组分的吸附胶质进行了分析鉴定，对燃料的储存特性和有色组分的化学特性进行了考察。结果表明，Pingba RP-3喷气燃料中的有色组分全部集中在吸附胶质中，吸附胶质以含氧化合物为主，其主要成分为烷基苯酚类（及其多聚体）化合物，含氮化合物质量分数极少，未检出含硫化合物。Pingba RP-3在储存中颜色变深的主要原因是胶质中的烷基苯酚类化合物氧化和缩聚。储存过程中喷气燃料的吸附胶质和颜色增加显著，与燃料在一定条件下的氧化反应有关。     

催化裂化过程中热裂化反应与二次反应的研究

利用连续式小型提升管催化裂化实验装置,研究了重油催化裂化过程中热裂化反应和二次反应的特点;考察了反应温度、剂油比和油气停留时间对热裂化和二次反应（氢转移和异构化反应）的影响;给出了不同反应条件下催化裂化过程中的过裂化点,考察了过裂化点前后热裂化反应在催化裂化过程中所占比例及氢转移和异构化反应的变化。结果表明,降低反应温度,缩短停留时间,增加剂油比可以抑制催化裂化过程中不利的热裂化反应,有利于氢转移和异构化反应的发生;在由反应温度、剂油比和停留时间引起的过裂化点前后,热裂化、氢转移和异构化反应表现出各自的变化特点。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

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.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.     

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.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.