超支化铬系催化剂的合成及乙烯齐聚性能研究

以不同端基烷基链长度的1.0G超支化大分子为桥联基,通过对其端基氨基进行催化功能改性,合成了系列具有不同桥联基长度的超支化PNP铬系催化剂。采用红外光谱(IR)、核磁共振氢谱(1H-NMR)、核磁共振磷谱(31P-NMR)、紫外光谱(UV)和质谱(MS)等表征方法证明合成催化剂的结构与理论结构相符。详细考察了溶剂种类、反应温度、Al/Cr摩尔比、反应压力、催化剂用量和催化剂结构对催化剂乙烯齐聚性能的影响。实验结果表明,当以甲苯为溶剂,甲基铝氧烷(MAO)为助催化剂时,超支化PNP铬系催化剂表现出良好的催化乙烯齐聚性能,产物以低碳烯烃为主。最佳条件下,催化活性最高可达到1.69×105g/mol Cr·h,己烯和辛烯的选择性为43.3%以上。相同聚合条件下,其催化活性随着端基烷基链长度的增加而下降。     

CeO2掺杂的Mn/Al催化剂的物化、表面及催化性能

Pure and CeO2-doped Mn/Al mixed oxides were prepared by the wet impregnation method using finely powdered alumina, manganese, and cerium nitrates. The physicochemical, surface, and catalytic properties of the thermally treated solids (at 500, 800, and 900 ℃) were investigated using XRD, nitrogen adsorption at -196 ℃, and hydrogen peroxide decomposition in an aqueous solution at 30 - 50 ℃. The Mn oxidation state changed from Mn4 to Mn2 on increasing the calcination temperature. There were two unique features associated with CeO2 that are of interest. The first was that it favored the dispersion of manganese oxides deposited on the γ-Al2O3 catalyst calcined at 500 ℃. The second was that it enhanced the formation of Mn3O4 species from Mn2O3 deposited initially on the alumina support calcined at 800 and 900 ℃. Consequently, the specific surface area of the Mn/Al mixed oxides calcined at 500 ℃ was increased by increasing the amount of dopant added. An opposite effect was observed by increasing the calcination temperature from 500 to 900 ℃. The doping followed by calcination at different temperatures brought about an increase in the catalytic activity of mixed oxides. Pretreatments did not modify the mechanism of the catalyzed reaction but changed the number of catalytically active sites without changing the nature of these sites.     

A new type of polarographic catalytic wave of organic compound——Studies on the polarographic catalytic wave of medroprogesterone acetate in the presence of KIO_3

The polarographic behavior and catalytic wave mechanism of medroprogesterone acetate (MPA) were studied in both aqueous and DMF media. In 0.2 mol/L acetic acid-sodium acetate (pH 5.0) buffer solution, the C=C bond of MPA first undergoes le, lH~ reduction to form protonated free radical HMPA(?), the further reduction of HMPA(?) in le, 1H~ process is simultaneous with the dimerization reaction between HMPA(?) and neutral molecular MPA. In DMF media containing 0.1 mol/L tetrabutylammonium tetrafluoborate (TBA·BF_4), the C=C bond of MPA shows two le, 1H~ reduction waves, which are ascribed to the reduction of MPA and free radical MPA, respectively. Here, no dimerization reaction occurs. These processes produce the reduction wave of MPA. In the presence of oxidant KIO_3, a polarographic catalytic wave of MPA is observable due to a chemical reaction between HMPA(?) or MPA(?) and KIO_3 as well as its intermediate species to regenerate MPA. The catalytic wave, which is caused by the reduction of organic com     

活性炭催化氧化脱除单质汞的研究

模拟煤气的气氛,在硫化氢（H₂S）和氧气（O₂）存在条件下,对活性炭催化氧化吸附单质汞（Hg⁰）的性能进行了研究。结果表明,H₂S和O₂存在条件下,活性炭对Hg⁰的吸附能力明显提高。在180min内,H₂S和O₂共存气氛下,脱汞效率约为78%;只有H₂S存在下,脱汞效率约为69%;没有H₂S和O₂气氛下活性炭脱汞效率快速下降为28%。随着吸附温度的升高,入口汞浓度的提高和吸附剂粒径的增大,活性炭的脱汞效率会随着下降。通过XRD表征表明,Hg⁰的吸附反应机理是Hg⁰在活性炭催化氧化下与H₂S形成硫化汞（HgS）,从而实现了Hg⁰的稳定化脱除。     

新型膦胺配体羰基钌化合物的合成及其催化性能研究

以十二羰基三钌和o-PPh2C6H4NR2(R=H,Me)配体为原料,成功制备了三种新型羰基钌化合物(μ-o-PPh2-C6H4NH)Ru3(μ-H)(CO)9(2)、(o-PPh2C6H4NH)2Ru(CO)2(3)和(μ-o-PPh2C6H4NMe2)2Ru(CO)3(4).对这三个化合物进行了核磁共振和红外谱学、元素分析和X射线单晶衍射分析表征,并对这三个化合物进行了催化性能研究.化合物2和4可催化苯甲醛加氢反应生成苯甲醇,但是3没有催化活性.从实验角度阐述了膦胺配体钌催化剂的结构与性能关联,进一步探讨了加氢催化反应失活的可能原因.     

手性胺醇稀土配合物的合成、荧光性质及其催化芳香酮的不对称氢化反应

合成了三种新的含C₂-对称轴的手性胺醇(PhOHCHCH₂)₂NCH₂C₆H₄R (R＝OCH₃, L₁; R＝CH₃, L₂; R＝Cl, L₃), 将其与无水氯化稀土LnCl₃•4THF (Ln＝La, Sm, Gd)反应生成了九个新的胺醇类稀土配合物LLnCl•2THF (L＝L₁, L₂, L₃; Ln＝La, Sm, Gd). 用元素分析、热重分析、红外和紫外光谱等手段对它们进行了表征. 荧光光谱显示一些配合物具有荧光性能. 原位催化芳香酮的不对称氢化反应表明: L₁/SmCl₃•4THF体系催化苯乙酮不对称氢化反应的转化率达71%, 相应的对映体过量值达32%.     

铜(Ⅱ)-铬天青S-过氧化氢体系催化光度法测定痕量铜

本文研究了在氨水介质中,痕量铜对过氧化氢氧化铬天青S褪色反应的催化作用,建立了一个催化光度法测定痕量铜的新方法。线性范围为0～20ng/mL,检出限为5.59×10~(-11)g/mL,并用于铝合金标准样品,环境标准样品和自来水中痕量铜的测定。     

煤油共处理油品的族组成研究

采用高效液相色谱法对兖州烟煤与催化裂化油浆共处理制备的油品的族组成进行了研究。结果表明 ,在实验条件下油品主要由烷烃和芳烃组成 ,杂原子化合物含量一般仅为 0 5 %～ 2 0 %。原料煤与油浆比例、反应温度、催化剂对油品族组成具有重要影响 ;随初始氢压不同 ,对油品族组成的影响不同 ;在 4MPa初始压力条件下 ,反应气氛 (氢气、氮气 )对煤油共处理和纯油浆制备油品的族组成影响不大。