糠醛加氢制糠醇中γ-Al2O3负载Cu-Zn催化剂的改性研究

采用浸渍法制备Co改性γ-Al₂O₃负载的Cu-Zn催化剂，考察Cu-Zn负载量、Co含量及反应温度等对催化剂性能的影响。结果表明，在413 K、氢气流速0.5 mL·s^－1 和糠醛空速2 h^-1 条件下,当催化剂Cu-Zn/γ-Al₂O₃（Co）中n(Cu)∶n(Zn)∶n(Al)∶n(Co)＝1.0∶2.0∶3.0∶0.51时，糠醇的选择性100％，糠醛转化率94.6％，比使用单纯Cu-Zn/γ-Al₂O₃催化剂的最佳转化率提高11％。     

Isomerization of n-hexane over mono- and bimetallic Pd–Pt catalysts supported on ZrO2–Al2O3–WOx prepared by sol–gel

The catalytic performance of mono- and bimetallic Pd (0.6, 1.0 wt.%)–Pt (0.3 wt.%) catalysts supported on ZrO₂ (70, 85 wt.%)–Al₂O₃ (15, 0 wt.%)–WO_x (15 wt.%) prepared by sol–gel was studied in the hydroisomerization of n-hexane. The catalysts were characterized by N₂ physisorption, XRD, TPR, XPS, Raman, NMR, and FT-IR of adsorbed pyridine. The preparation of ZrW and ZrAlW mixed oxides by sol–gel favored the high dispersion of WO_x and the stabilization of zirconia in the tetragonal phase. The Al incorporation avoided the formation of monoclinic-WO₃ bulk phase. The catalysts increased their S_BET for about 15% promoted by Al₂O₃ addition. Various oxidation states of WO_x species coexist on the surface of the catalysts after calcination. The structure of the highly dispersed surface WO_x species is constituted mainly of isolated monotungstate and two-dimensional mono-oxotungstate species in tetrahedral coordination. The activity of Pd/ZrW catalysts in the hydroisomerization of n-hexane is promoted both with the addition of Al to the ZrW mixed oxide and the addition of Pt to Pd/ZrAlW catalysts. The improvement in the activity of Pd/ZrAlW catalysts is ascribed to a moderated acid strength and acidity, which can be correlated to the coexistence of W⁶⁺ and reduced-state WO_x species (either W⁴⁺ or W⁰). The addition of Pt to the Pd/ZrAlW catalyst does not modify significantly its acidic character. Selectivity results showed that the catalyst produced 2MP, 3MP and the high octane 2,3-dimethylbutane (2,3-DMB) and 2,2-dimethylbutane (2,2-DMB) isomers.     

甲磺酸伊马替尼的合成

以4-甲基-3-硝基苯胺为起始原料,经过缩合、还原、环合等反应制得抗肿瘤药物甲磺酸伊马替尼。并分别讨论了采用无水碳酸钾代替二异丙基乙胺、水合肼和普通催化剂代替铂炭催化剂以及采用异戊醇作为溶剂的优点。最终反应总收率超过50%,用高效液相色谱分析产品纯度在99.5%以上。     

化学气相沉积(CVD)法制备先进陶瓷材料

先进陶瓷材料具有许多优异的性能,如高比强度、高比模量、密度低、硬度高、耐腐蚀、抗氧化等,从而被广泛用作高温结构部件。化学气相沉积()法工艺能制备诸如碳化物、氮化物、硼化物、氧化物等CVD多种陶瓷,因而具有广阔的应用前景。     

TGA analysis of γ‐irradiated linear low‐density polyethylene

Linear low‐density polyethylene (LLDPE), based on butene‐1 or hexene‐1, was irradiated with γ‐rays under vacuum or in the presence of air. The study focused on the influence of the dose rate and the γ‐dose on the thermal properties of LLDPE. Differential scanning calorimetry, thermogravimetric analysis (TGA), and TGA/FTIR techniques were used to address the thermal behavior as a result of γ‐irradiation. During this irradiation, competition between crosslinking and scission reactions, subsequent to oxidation reactions, occurred in the polymeric material, which strongly depends on the experimental conditions. A decrease of the crystallinity for γ‐irradiated samples was observed in particular for samples irradiated under vacuum. This observation may be explained by increased hindrance of segment mobility due to crosslinking reactions that prevent crystal growth. TGA investigations revealed an enhancement of the thermal stability for samples irradiated under vacuum but not for those irradiated in air. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2790–2795, 2006     

Investigation of CH4 Reforming with CO2 on Meso-Porous Al2O3-Supported Ni Catalyst

Meso-porous Al₂O₃-supported Ni catalysts exhibited the highest activity, stability and excellent coke-resistance ability for CH₄ reforming with CO₂ among several oxide-supported Ni catalysts (meso-porous Al₂O₃ (Yas1-2, Yas3-8), -Al₂O₃, -Al₂O₃, SiO₂, MgO, La₂O₃, CeO₂ and ZrO₂). The properties of deposited carbons depended on the properties of the supports, and on the meso-porous Al₂O₃-supported Ni catalyst, only the intermediate carbon of the reforming reaction formed. XRD and H₂-TPR analysis found that mainly spinel NiAl₂O₄ formed in meso-porous Al₂O₃ and -Al₂O₃-supported catalysts, while only NiO was detected in -Al₂O₃, SiO₂, CeO₂, La₂O₃ and ZrO₂ supports. The strong interaction between Ni and meso-porous Al₂O₃ improved the dispersion of Ni, retarded its sintering and improved the activated adsorption of CO₂. The coking reaction via CH₄ temperature-programed decomposition indicated that meso-porous Al₂O₃-supported Ni catalysts were less active for carbon formation by CH₄ decomposition than Ni/-Al₂O₃ and Ni/-Al₂O₃.     

蓝色氧化锆陶瓷的研制

以微米或纳米氧化锆粉体为主原料,钒锆蓝色料或Co3O4为着色剂,添加适量烧结助剂制备蓝色氧化锆陶瓷。研究了氧化锆、助剂、着色剂等对蓝色氧化锆陶瓷颜色及性能的影响。结果表明:用纳米级ZrO2粉体为原料,钒锆蓝色料为着色剂,添加少量烧结助剂,可制得性能优良、颜色亮丽的蓝色氧化锆陶瓷;用纳米级ZrO2为原料,Co3O4为着色剂,添加少量烧结助剂,可制得性能优良、颜色亮丽的钴蓝色氧化锆陶瓷。     

Molecular weight distribution of polyethylene catalyzed by Ziegler–Natta catalyst supported on MgCl2 doped with AlCl3

Ti‐based Ziegler–Natta catalysts supported on MgCl₂ doped with AlCl₃ were prepared by the reaction of MgCl₂/AlCl₃–ethanol adduct with TiCl₄. No AlCl₃ crystallites were found in the AlCl₃‐doped catalysts by WAXD analysis, suggesting that AlCl₃/MgCl₂ solid solution was formed. The effect of doping on the catalyst performance in ethylene polymerization was investigated. The results showed that the catalysts based on AlCl₃‐doped MgCl₂ support exhibited a slightly higher activity than did the MgCl₂‐supported catalyst and the molecular weight distribution (MWD) of polyethylene (PE) markedly increased (from 10.8 to 47.9) with the increase of AlCl₃ content in catalysts. The changes in catalyst's active center distribution were studied based on nonlinear fitting of the polymer GPC curves by multiple Flory functions. It was found that increase of types of active centers by introducing AlCl₃ into the support should be responsible for the broadening of MWD of PE. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1768–1772, 2006     

KNO_3/γ-Al_2O_3型固体超强碱催化合成香豆素的研究

对以水杨甲醛与乙酸酐为原料合成香豆素的工艺进行了改进。首次采用KNO3/γAl2O3固体超强碱催化剂的工艺路线,提高了产物的收率。同时对催化剂用量、反应物的量比、反应温度的影响进行了研究。结果表明,最佳工艺条件为:n(水杨醛)∶n(乙酸酐)=1.0∶1.6,催化剂用量为水杨醛质量的3%,反应近终点时在(210±2)℃,再保温反应0.5h,香豆素收率可达85%以上。该催化剂具有较高的催化活性,易于回收,可重复使用5次以上。     

3位取代苯酞衍生物新的简便合成方法

3位取代的苯酞类化合物具有广泛的生理活性 ,通过一个新的简便合成路线高收率的得到了 3位取代苯酞衍生物。新工艺中最重要的一步反应是 3 乙氧基苯酞与丙二酸二乙酯的缩合 ,也是与Trost等人的合成路线主要的不同之处。