Cr—P／SiO催化剂上异丁烯——甲醛气相缩合制异戊二烯失活动力学考察

本文用积分固定床反应器对异丁烯－甲醛一步缩合制异戊二烯用Cr-P/SiO2催化剂的失活动力学进行了研究。测定了在反应温度为260－340℃，常压及不同反应物组成时的反应速度。建立了失活动力学方程，估算出反应级数，活化能、以及失活级数和失活因子。所得失活动力学方程式为：r=1.07×10^6exp(-35.2/RT)·P1^0.9·P2^1.5a a-0.47 0.53exp(-4.83×10^4t) -da/dt=2.56×10^4exp(-4.83×10^4t)从上述方程式推测，在Cr-P/SiO2催化剂上可能存在两种活性中心，一种是既能进行缩合反应同时又伴随积炭的中心，另一种中心则只进行缩合反应。催化剂的失活机理为反应物没有内扩散阻力的平行一串联失活，反应物与产物均能在催化剂表面形成焦炭，覆盖活性中心或堵塞洞口而导致失活。经烧炭催化剂活性可获得恢复。     

HRP-12催化剂上苯与直链烯烃的烷基化反应 Ⅱ. 失活动力学研究

采用连续操作的釜式反应器，利用悬浮态的负载杂多酸催化剂HRP-12上的烷基化反应的实验数据进行参数估值，确定了失活反应速率常数、失活反应活化能、活性保留函数的失活反应级数和烯烃摩尔浓度的失活反应级数，建立了苯与直链烯烃烷基化反应的失活动力学模型。模型表明：该失活反应对于活性保留函数是一级失活反应，对于烯烃摩尔浓度是二级失活反应。统计检验表明：所得失活动力学方程在显著性水平α=0.005下有较高的实验数据拟合精度和模型可信度。     

甲醇转化制低碳烯烃过程中MgZSM—5催化剂失活动力学的研究

用微型固定床连续反应器,考察了甲醇转化制低碳烯烃过程中MgZSM-5分子筛催化剂的失活规律。在常压下,分别测定了反应活化能、反应级数及460—500℃范围内的失活反应活化能和失活反应级数。得到的失活动力学速率式为: -γ=4.61×10~5exp(-99.71/(RT)×10~3)C·a -(da)/(dt)=2.42×10~2C~0.059exp(-63.93/(RT)×10~3)a     

C207联醇催化剂的硫化氢表面中毒深度

研究了甲醇合成C207铜基催化剂硫化氢中毒本征失活动力学。常压下在内循环无梯度反应器中测定了φ5×5mm工业颗粒C207铜基催化剂在进门硫化氢含量7.19×10~(-4),分别通硫化氢4、8和12小时后甲醇分解反应宏观速率。俄歇电子能谱测定结果表明,工业颗粒铜基催化剂硫化氢中毒为表面中毒,通硫化氢4、8和12小时未中毒比半径分别为0.938,0.916和0.896,与由本征失活动力学计算的值相符合。     

Ni-Mg复合催化剂催化裂解CH_4制氢动力学研究

基于定温热重实验,建立了甲烷催化裂解反应动力学模型和催化剂表面积炭失活动力学模型。其中,甲烷催化裂解动力学模型将初始产氢速率视为催化剂未积炭条件下的动力学基础数据;催化剂表面积炭失活动力学则基于甲烷催化裂解速率的降低。实验使用Ni-Mg复合催化剂,分别在535、585、635℃,甲烷分压10~4、2×10~4、3×10~4Pa条件下展开甲烷催化裂解动力学特性研究。结果表明,甲烷催化裂解的反应级数为0.5,活化能为82 k J/mol;Ni-Mg复合催化剂反应失活级数为0.5,催化剂失活活化能为118 k J/mol。实验条件下均制得了多壁碳纳米管。     

二氧化硅负载杂多酸对异丁烷与丁烯烷基化的催化作用Ⅰ.催化剂的制备、表征和失活

 采用浸渍法制备了二氧化硅负载的磷钨酸催化剂,系统考察了催化剂的比表面积、结晶水、结构特征和酸性等物化性质. 将在不同条件下制备的不同结构的杂多酸催化剂用于异丁烷与丁烯烷基化反应,考察了催化剂活性组分、制备方法和反应条件对催化剂性能的影响,分析了催化剂的失活过程和失活机理. 结果表明,当负载量不大于50%时,磷钨酸以单分子层形式均匀分散于载体表面,催化剂表面存在大量的强B酸中心,不存在L酸中心; 经160 ℃活化后的催化剂具有最大的酸量和最强的酸性; 催化剂对烷基化反应具有较高的初活性,但随着反应的进行催化剂迅速失活; 反应产物的组成与催化剂失活程度密切相关,反应初期产物以烷烃为主,之后产物则以烯烃为主; 催化剂的失活原因为积碳.     

在AF-5分子筛催化剂上苯烷基化反应的失活动力学研究

用稀土交换的X型分子筛、ZSM-5分子筛和氢型丝光沸石等催化剂可以催化苯气相烷基化反应.为开发苯烷基化新工艺,有必要建立描述失活过程的动力学方程.国外对失活的研究十分活跃,召开了两次专题会议,出版了论文集.本文采用磁驱动内循环无梯度反应器,以苯、乙烯为原料,AF-5分子筛为催化剂,研究了在340～420℃范围内苯烷基化反应的失活动力学.所用AF-5分子筛属ZSM-5系列,比表面为341.1m~2/g,晶粒度为0.04～0.08μ.产物分析所用色谱柱的担体为10％硅酮Ⅰ/釉化6201,柱温130℃,     

甲醇制烯烃催化剂失活模型

在固定床反应器中,研究了甲醇制烯烃反应中当SAPO-34分子筛处于失活期时催化剂活性的变化情况,主要考察催化剂活性随反应温度、空速和运行时间的变化,通过对实验数据的分析拟合,得到了催化剂活性与失活时间、反应温度、空速的经验关联式(失活模型),对失活模型的检验表明,该模型与实验数据较为吻合,表明了该式的准确性。 通过对失活模型的分析,获得了当失活速率达到最大时的失活时间与反应时间、空速的关联式,失活过程应服从不均匀表面失活机理,并且当催化剂处于失活区时,失活时间对活性的影响要大于空速和温度。     

孔结构对铜基甲醇合成催化剂宏观反应速率的影响：II.表面中毒…

建立了表面中毒铜基催化剂上进行ＣＯ和ＣＯ２加氢合成甲醇复合反应宏观反应速率的关键组分扩散模型，研究了不同中毒分率下孔结构参数对铜基催化剂的宏观反应速率的影响。结果表明，随着中毒分率增加，失活层的扩散阻力更趋严重，而孔结构参数的影响趋于减小。     

裂化催化剂水热失活动力学及装置平衡活性模型

根据裂化催化剂水热失活过程伴随着超稳化过程的特点，确定了对应不同自抑制函数的催化剂水热失活动力学模型方程。利用裂化催化剂水热失活实验数据进行参数估值，建立了裂化催化剂水热失活动力学模型。统计检验结果表明，二级自抑制的一级水热失活模型能很好地模拟实验数据，是较理想的水热失活动力学模型。考虑工业装置中裂化催化剂呈全混流，建立了裂化催化剂平衡活性模型方程，并且装置平衡催化剂微反活性的模型计算值与实测值相当吻合。该模型的预测结果表明，随着再生器温度或催化剂藏量的提高，平衡剂的微反活性逐步降低；平衡剂微反活性随催化剂单耗的提高先快速提高，然后缓慢提高。     

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%.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

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.     

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.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

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.