轻质烷烃异构化催化剂Pd／HM的TPR研究

TPR技术具有准确、简便等特性而被广泛用于研究金属催化剂的还原过程。Mahoney和Hurst等曾研究了Pd/NaX和Pd/NaY的TPR行为,但对轻质烷烃异构化催化剂Pd/HM的TPR研究尚未见报道。本文对Pd/HM的TPR谱中各峰进行了归属,讨论了Pd/HM的还原及吸附H_2机理及钯在丝光沸石孔道中的分布,为Pd/HM的制备提供了有益的信息。     

烷烃加氢异构化反应

综述了烷烃加氢异构化反应中的正碳离子异构和裂化机理、孔口与钥匙锁催化、择形催化及双分子机理,详细论述了分子筛基双功能催化剂酸性、金属、金属酸位比、孔道、晶粒尺寸和催化剂改性对烷烃加氢异构反应活性、异构选择性等的影响。论述了近期烷烃加氢异构催化剂改性的新方法。提出针对不同催化剂体系,根据反应机理提高异构催化剂活性和选择性的途径。     

轻质直链烯烃异构化催化剂研究进展

上世纪80年代起,全球汽油质量开始向无铅、低芳烃、低蒸汽压、高辛烷值和高氧含量的方向发展,这也很大程度上推动了甲基叔丁基醚(MTBE)和甲基叔戊基醚(TAME)的迅速发展,而作为其原料的C4和C5异构烯烃的来源也显得尤为重要.因此,关于C4、C5轻质直链烯烃骨架异构化技术的研究骤然升温,从而掀起了一股轻质直链烯烃骨架异构化技术的研究热潮.另一方面,汽油中C5~C8的直链烯烃通过骨架异构化反应能够有效地提高汽油辛烷值,以适应新的燃料规范的要求,这也在一定程度上推动了轻质烯烃骨架异构化技术的发展.1直链烯烃骨架异构化的机理研究由于…     

直链烷烃的超临界热稳定性研究

本文考察了正辛烷、正壬烷、正癸烷、正十一烷和正十二烷等5种直链烷烃在超临界条件下的恒容热裂解,采用一级反应动力学简化描述其热裂解过程。跟踪裂解气液产物分布,探讨了液体产物中芳烃含量与热稳定性的关系。在相同反应条件下,奇数碳和偶数碳烷烃热裂解速率、转化率和液体组分中芳烃含量分别随碳数的增加而增加。芳烃产物含量随裂解转化率增加呈指数形式增加,表达了烷烃类化合物热稳定性和裂解变化的规律。     

直链烷烃物理性质递变规律研究

以直链烷烃同系物结构重复单元数值连续变化为模型假定,获得了描述直链烷烃同系物物理性质递变规律的数学表达式: P＝a+bn(1/c),其中a、 b、 c均为常数, n为结构重复单元数值, P为直链烷烃同系物的物理性质。通过非线性回归分析,得到回归方程,结果表明直链烷烃同系物的物理性质与重复单元数值之间满足上述关系式,均显示优良的相关性。     

钨基催化剂上烷烃异构化研究进展

随着人们对汽油质量的要求越来越高,烷烃异构化越来越受到重视,尤其是长链烷烃异构化,因此研究高性能的异构化催化剂具有非常重要的意义。本文综述了一类用于长链烷烃异构化的新型催化剂-钨基催化剂的研究进展,介绍了此类催化剂的制备、异构化反应,简要介绍了其反应机理。并分析了此类催化剂今后的发展趋向和应用前景。     

ZSM－5型分子筛对正丁烯选择异构化反应的催化作用

报导了ＺＳＭ－５型分子筛催化剂对正丁烯选择异构化反应的催化性能，利用ＸＲＤ、ＳＥＭ、ＩＲ等方法对催化剂进行了表征，并应用原位红外技术对反应分子丁烯－２在催化剂表面上的吸附，反应行为进行考察．催化剂性能评价结果表明ＺＳＭ－５型分子筛催化剂对此反应具有较好的催化活性和选择性．用碘对其进行改性，可有效地改善催化剂的催化性能．     

手性钛配合物在Diels-Alder反应中的对映选择性催化作用

综述了近20多年来手性钛配合物在催化不对称Diels-Alder反应中的应用。重点介绍了与钛形成配合物的手性配体二元醇、联萘酚、氨基醇、氨基酸等，手性钛配合物在对Diels-Alder反应的对映选择性催化方面具有独特的优势。参考文献23篇。     

光异构化反应速率的量子理论

光异构化反应是在光场存在下，分子吸收光子引起的单分子化学反应，包括通常的异构化与环合、开环反应．一些作者用量子化学方法及分子轨道相关图和态相关图等方法对这类反应进行过研究［1］．本文用多声子光跃迁理论［2］研究光异构化反应，导出反应速率及其在低温条件下的解析表达式，对所得结果进行了讨论．1理论方法与结果在光异构化反应中，分子的电子状态与构型都发生变化，而且电子态的变化是与构型的改变紧密耦合的．分子的构型用分子的振动波函数来描写．由于电子与原子质量相差悬殊，可以采用绝热近似处理这一电子－振动相互作用…     

Boron(III) Tribromide or Titanium(IV) Bromide and Lewis Base Promoted Baylis-Hillman Reaction

ＩｎｔｒｏｄｕｃｔｉｏｎＲｅｃｅｎｔｌｙ ,ｔｈｅＢａｙｌｉｓ Ｈｉｌｌｍａｎｒｅａｃｔｉｏｎｈａｓｂｅｃｏｍｅａｖｅｒｙｈｏｔｆｉｅｌｄｆｏｒｓｙｎｔｈｅｔｉｃｃｈｅｍｉｓｔｓ ,1 12 ｗｉｔｈａｒｅｃｅｎｔｅｘａｍｐｌｅｏｆａｃａｔａｌｙｔｉｃａｓｙｍｍｅｔｒｉｃｖｅｒｓｉｏｎ .13 ＩｔｈａｓｂｅｅｎｄｉｓｃｌｏｓｅｄｔｈａｔｔｈｅｃｏｍｂｉｎａｔｉｏｎｏｆａＬｅｗｉｓｂａｓｅｓｕｃｈａｓｃｈａｌｃｏｇｅｎｉｄｅｓ ,ａｍｉｎｅｓ ,ｐｈｏｓｐｈｉｎｅｓｏｒｑｕａｔｅｒｎａｒｙａｍｍｏ ｎｉｕｍｈａｌｉ…     

Boron（Ⅲ） Tribromide or Tianium （Ⅳ） Bromide and Lewis Base Promoted Baylis—Hillman Reaction

It was found that,when the Baylis-Hillman reaction of arylaldehydes with methyl vinyl ketone was carried out at below -20℃ in the presence of boron (Ⅲ） tribromide or titanium (Ⅳ） bromide using a catalytic amount of Lewis base such as amine,the brominated compounds and the Baylis-Hillman adducts could be obtained as the major products in good yields for various aryl aldehydes.But at room temperature,the elimination products were the major products.In addition,the palladium catalyzed allylic substitution reactions of the elimination products were also examined.     

硝基胍H迁移异构化反应动力学的从头计算研究

Theoretical studies on the α- and β-forms nitroguanidine were carried out using ab initio theoretical methods, at the MP2/6-31G(d,p) level. The predicted geometrical parameters were in good agreement with the available theoretical values, which calculated by other author. The three C-N bond lengths in α-form nitroguanidine were different, the longest bond length was 1.430 A, the shortest was 1.283 A. But they were almost similar in β-form, the longest was 1.375 A, the shortest was 1.322 A. Therefore there were conjugative effects in β-form but not in α-form. The calculated results also show that the β-form is stable with respect to the α-form from energetically, lower 28.16 kJ/mol corrected with zero point vibrational energy. The transition-state for the unimolecular isomerization was conformed by the IRC calculation. The calculated energy barrier for the direct intramolecular hydrogen atom transfer isomerization process was 132.95 kJ/mol. The isomerization reaction, exothermal reaction, is a typical intramolecular hydrogen atom synfacial transfer reaction. Rate constants of the isomerization reaction were evaluated within the temperature range of 200-1773 K by the classical transition state theory. The rate constant was 1.99×10-11 s-1 and the equilibrium constant was 1.00×105 at 298 K. With the temperature increasing, the equilibrium value decayed and the reaction process was more difficult.     

The Virtue of Defects: Stable Bromine Production by Catalytic Oxidation of Hydrogen Bromide on Titanium Oxide

Rutile TiO₂ is a heavily investigated oxide with, to date, scarce applications in industrial catalysis. The inactivity of this material in oxidations has been related to its inability to dissociate molecular oxygen. Herein we show how rutile catalyzes the oxidation of HBr to Br₂ through defect states that are introduced during the reaction. The identification of active, stable, and abundant materials for bromine production is key to the future implementation of Br₂‐mediated alkane functionalization processes. The catalytic properties of TiO₂ are discussed in comparison to expensive rutile‐type oxides, such as RuO₂ and IrO₂, on the basis of surface characterization and molecular modeling.     

The kinetics of the aluminium bromide catalyzed isomerization of 1-propyl bromide

An analysis of the initial rates of reaction was carried out of the aluminium bromide catalyzed isomerization of 1-propyl bromide: 1-C₃H₇Br + Al₂Br₆ = 2-C₃H₇Br + Al₂Br₆ The proposed kinetics of the process is consistent with a nucleophilic displacement of the aliphatic bromine contained in complexes of the alkyl bromide with aluminium bromide. The displacement, initiated by the AlBr₄⁻ ion, is accompanied by a rate determining 2,1 hydride shift.     

二溴对甲基偶氮氯磺与锶的显色反应研究及应用

研究了二溴对甲基偶氮氯磺与锶的显色反应,在0.72mol·L-1盐酸介质中,试剂与锶形成稳定的2∶1蓝色络合物,其最大吸收波长位于633nm,表观摩尔吸光系数为7.7×104L·mol-1·cm-1,锶量在0～30μg/25mL范围内符合比耳定律。该试剂与其它测定锶的试剂相比,具有灵敏度高、选择性好等优点。方法应用于铝合金中微量锶的测定,结果满意。     

不对称双酸催化3,4-二氢-2H-吡喃的反电子Hetero-Diels-Alder反应

研究了双酸催化剂不对称催化烯醚和β,γ-不饱和α-酮酸酯的反电子Hetero-Diels-Alder (HDA)反应, 为手性合成3,4-二氢-2H-吡喃类化合物提供了一种新的催化合成方法. InBr₃与手性磷酸钙盐Ca(1c)₂组合的手性双路易斯酸催化体系能够有效催化3,4-二氢-2H-吡喃和β,γ-不饱和α-酮酸酯的反电子HDA反应, 反应给出优秀的产率(最高达98%), 中等到良好的非对映选择性(最高达89:11)和良好到优秀的对映选择性(最高可达94%). 并且该双酸催化体系也能成功实现其它烯醚(如: 2,3-二氢-2H-呋喃, 乙烯基乙醚)的HDA反应, 获得优秀的非对映选择性(>94:6)和良好的对映选择性.