Evidence for non-site-isolation in ZSM-5 from ion-exchange and catalytic studies

Ion exchange of HZSM-5 samples with alkali metal cations, using metal chloride solutions, results in partially exchanged zeolites, MHZSM-5, M = Li, Na, K or Cs. The degree of exchange is found to increase with increasing ionic radius of the cations. The catalytic properties of the alkalized zeolites were evaluated using the reaction conditions under which the catalytic activity of the HZSM-5 samples in terms of n-hexane cracking is proportional to the aluminium content. From the residual catalytic activity exhibited by the Na-, K- and CsHZSM-5 samples it is concluded that each of the larger Na⁺, K⁺ and Cs⁺ ions is influencing more than one AlO ₄ ^– tetrahedron, implying that the aluminium sites in ZSM-5 are not isolated. The ion-exchange results are then interpreted in terms of non-isolated aluminium sites. The ion-exchange and catalytic properties of the zeolites as a function of aluminium content are also discussed.     

棉籽油间歇式酯交换反应动力学的研究

生物柴油(棉籽油甲酯)可以由棉籽油与甲醇在催化剂KOH存在下通过酯交换反应制得。故对棉籽油间歇式酯交换反应动力学进行了研究,并考察了反应温度和催化剂浓度对产物棉籽油甲酯浓度的影响。用液相色谱法分析棉籽油的组成;用气相色谱法分析产物中棉籽油甲酯的含量。由实验数据绘制的动力学曲线得到酯交换反应在开始阶段为准二级反应,以后紧接转为一级反应和零级反应,与文献报导的棕榈油酯交换反应动力学结果一致。由实验数据求出酯交换反应在开始阶段的动力学参数,35℃、45℃时的反应速率常数分别为0.9179Lmol-1min-1和1.049Lmol-1min-1,酯交换反应的活化能为10.88kJmol-1。根据实验结果得到棉籽油酯交换反应的最佳反应温度为45℃,最佳催化剂为1.1%KOH。     

Photoelectric conversion of photosynthetic reaction center in multilayered films fabricated by layer-by-layer assembly

Multilayered protein films which contained ordered layers of photosynthetic reaction center (RC) from Rhodobacter Sphaeroides (RS601) were assembled by means of alternate electrostatic adsorption with positively charged poly(diallyldimethylammonium chloride) (PDDA). The assembly of RC was monitored by spectrometry and photocurrent measurement. Linear film growth was observed up to about 20 cycles of adsorption. For the monolayer film, the photocurrent was about 8.5 nA cm⁻². For the multilayered film, the total photocurrent was about 77 nA cm⁻² for the 24-layer RC film, while the average photocurrent increment per adsorption cycle was about 3.2 nA cm⁻². The overall light-to-electricity conversion efficiency for a 24-layer film was about eight times higher than that for the monolayer one. The effects of electrode potential and pH on the photocurrent were also measured to illustrate the light-to-electric converting mechanism.     

甲缩醛空气氧化制甲醛催化剂的研制和工艺条件探讨

考察了铁钼催化剂对甲缩醛空气氧化制甲醛的催化性能。制备了多种不同钼铁比和第三、第四组分的催化剂,进行了活性评价和筛选,探讨了适宜的工艺条件范围。对于所选定的催化剂(钼铁比为1.82～1.88;铬铁比为0.1～0.38)在适宜的工艺条件(甲缩醛进料浓度4.5～5.5％;甲缩醛和氧气进料比1:2.0±0.2;空速12000～22000h~(-1);热点温度370～390℃)下,甲醛收率可达85％左右。     

Reactive compatibilization of PE/PS blends. Effect of copolymer chain length on interfacial adhesion and mechanical behavior

This paper deals with in situ compatibilization of PE/PS blends via Friedel-Crafts reaction, performed at the interphase. Two polyethylenes having different molecular weights, and the same PS, were used along a wide range of catalyst concentration. The influence of the graft copolymer architecture and content on the efficiency of blend compatibilization was studied. The emulsifying effect, morphological aspects and mechanical behavior were also assessed for these blends. The amount of copolymer formed increases with catalyst concentration and the short chain length fraction of the homopolymers. The high molecular weight (MW) copolymers behaved as better compatibilizers as they showed, at the cmc, greater graft copolymer concentration than the low MW ones. A substantial increase in interfacial adhesion and particle size reduction was observed, even at catalyst concentrations as low as 0.3 wt%. In correspondence, mechanical properties, like ductility and yield strength, were enhanced by the effect of this Friedel-Crafts reaction's compatibilization.     

抗氧剂3114合成反应热力学和动力学的研究

研究了常温溶剂法合成抗氧剂3114反应热力学和动力学过程。控制温度在117±2℃,研究结果表明,反应是零级反应,反应速率常数k=1.91×10-3/min,反应的平衡常数K=138.4(mol/L)-6,反应活化能Ea=1366.2J/mol。     

聚合转化率对硫调型氯丁胶结构与性能的影响

研究了硫调型氯丁橡胶乳液聚合中转化率对产晶结构与性能的影响.结果表明,随单体转化率的提高,聚合物的凝胶量及其交联密度增大,致使断链速度减慢,所得断链胶的门尼粘度上升,残存凝胶量增加,分子支化程度增大,分子量分布变宽,焦烧时间缩短。而相应硫化胶的拉伸强度、撕裂强度、冲击弹性和硬度等提高,扯断伸长率和永久变形下降。这些变化一般在转化率为80——85％时有明显转折.综合考虑产量与质量,聚合转化率控制在82±2％较为适宜。     

Correlation of reactivity and electrical resistivity of coke

A correlation between the reactivity and electrical resistivity of a series of cokes was determined using cokes prepared from blends of medium- and high-volatile coals. After correcting for the ash yield of the coke and the density of the resistivity specimen, a statistically significant relation between reactivity and resistivity was established. As the resistivity test requires much less time to perform than the reactivity test, it can be considered as an alternative approach to reactivity testing currently performed for quality control purposes.     

Nanocrystalline CeO2 in SBA-15: Performance of Pt/CeO2/SBA-15 Catalyst for Water-gas-shift Reaction

CeO₂ particles confined within the pores of an SBA-15 mesoporous silica host were prepared by incipient wetness impregnation (IMP) and deposition precipitation (DP) methods. The materials were characterized by XRD, N₂-adsorption and temperature programmed reduction (TPR) to evaluate the structure, texture, and redox properties. The preparation procedure had significant impact on the assembling mode of CeO₂ inside the SBA-15 mesopores. A high dispersion of CeO₂ particles was achieved via DP, whereas the dispersion of CeO₂ prepared by IMP was found to be inhomogeneous and CeO₂ partially blocked the pores. The CO conversion in the water-gas-shift reaction was enhanced over 1 wt% Pt supported on CeO₂-modified SBA-15 obtained by DP.     

Combustion of single char particles in a turbulent fluidized bed

The combustion of single bituminous char particles (4-12 mm diameter) was studied in a turbulent fluidized bed operated at 1098 K using air as the fluidising medium. Results indicated that particles burn with constant density following a shrinking sphere model. Burning rates are much higher than those observed in a bubbling fluidized bed. The rate of transfer of oxygen to the particle surface is also higher than that observed in bubbling beds. A model is proposed to calculate the Sherwood numbers of the burning carbon particles. Experimental values of the Sherwood numbers agree well with those predicted from the model.