金属胶束催化VII：双核配合物金属胶束催化PNPP水解反应动力学

研究了由双核铜配合物和表面活性剂组成的金属胶束催化PNPP水解的动力学和机理。提出了含两个水分子的双核铜配合物催化PNPP水解的动力学数学模型。结果表明：金属胶束催化PNPP水解是分子内反应；两个铜离子在催化PNPP水解过程中具有协同效应；由草酰胺桥联双核铜配合物与表面活性剂组成的金属胶束在催化PNPP水解中表现出高的活性。     

硫锚翁盐引发环氧丙烯酸酯/乙烯基醚光固化动力学研究

以三乙二醇二乙烯基醚 (DVE- 3)、 1 ,4-丁二醇乙烯基醚 (HBVE)为活性稀释剂 ,研究其与环氧丙烯酸酯 (EA)所组成的光聚合体系在硫锚翁盐光引发剂下引发的光固化动力学影响因素 .DVE- 3(HBVE)含量越大 ,EA/ DVE- 3(HBVE)体系的转化率越低 .体系的聚合温度越高 ,体系的转化率越高     

新型氯离子活化过氧单硫酸盐的非自由基系统去除水中扑热息痛的研究

提出了基于过氧单硫酸盐(PMS)的非自由基氧化法降解水中典型药物污染:利用常见的氯离子(Cl-)活化PMS降解水中典型药物扑热息痛,并同传统次氯酸钠氧化降解扑热息痛系统进行比对.对比研究了两系统中氧化剂投量、底物浓度和pH值对扑热息痛去除的影响.实验结果表明PMS/Cl-系统对扑热息痛的去除符合典型零级反应动力学模型,而NaClO系统对扑热息痛的去除符合拟一级动力学模型.当扑热息痛初始浓度为10mg/L时,0.4mM PMS和50mM Cl-在120min内对其去除率最大可达76.7%.结果表明在PMS/Cl-和NaClO系统中,提高氧化剂浓度、降低底物浓度、降低系统pH值均利于目标物的去除.PMS/Cl-和NaClO系统均以HClO为主要活性因子降解污染物,但是PMS/Cl-系统中活性因子的产生更为缓慢,今后可考虑在基于PMS的高级氧化系统中投加氯离子以实现消除残余氧化剂并保证系统的持续消毒能力.     

钢渣吸附去除水中亚甲基蓝

通过静态批式实验研究钢渣对亚甲基蓝吸附行为的影响.结果表明:亚甲基蓝去除率随钢渣投加量的增加而增大,随初始浓度的升高而降低,而单位钢渣质量下亚甲基蓝的吸附量呈相反趋势.溶液初始pH值为4时最有利于钢渣吸附亚甲基蓝.钢渣吸附亚甲基蓝符合Lagergren准一级动力学方程,平衡吸附量随亚甲基蓝初始质量浓度的增加而增大,随钢渣投加量增加而减小.结合Freundlich等温吸附方程发现,钢渣对亚甲基蓝的吸附是以离子交换作用为主的优惠型吸附.亚甲基蓝阳离子在静电力作用下吸附在钢渣表面,并与CaO等反应形成聚合物,增强吸附效能.     

高炉热储备区温度对煤气利用率的影响

研究了高炉热储备区内温度与煤气利用率的关系.结合热力学和实际情况,热储备区内只发生氧化亚铁的还原.因此需要利用吉布斯自由能计算和单界面未反应核模型对热储备区内还原反应进行热力学和动力学分析.结果表明:只有在H₂+H₂O体积分数小于0.3时降低热储备区温度才能提高煤气利用率.从1273K降温到1223K,氢气还原速率降低得比CO还原速率降低得多,说明温度对氢气还原的影响更大.对一般高炉来说,炉料在热储备区中还原所需的时间比其停留时间长或接近,说明热储备区内的还原反应没有达到平衡,降低温度不利于提高煤气利用率.     

光合细菌处理VB12废水降解动力学研究

用经过VB12废水驯化的4株光合细菌菌株进行试验。研究定义了最大比COD去除率（Umax,COD）,并通过测定Umax,COD来对比不同茵株的降解性能。研究表明,1g光合细菌中,2号菌株的Umax,COD值为0．698g／h,高于其他3种菌株,并进一步推导出基质降解动力学方程和细菌生长动力学方程。这一研究为选择处理VB12废水优势菌株提供了方法。     

Inhibitory Kinetics of p-Substituted Benzaldehydes on Polyphenol Oxidase from the Fifth Instar of Pieris Rapae L.

Polyphenol oxidase (PPO) is the enzyme responsible for enzymatic browning during the growth of insects. It is also involved in defense reactions and is related with immunities in insects. PPO, a metalloenzyme oxidase, catalyzes the oxidation of ο-diphenol to ο-quinone. The present paper de- scribes the effects of benzaldehyde and its p-substituted derivatives on the activity of PPO from the fifth instar of Pieris rapae L. PPO from the fifth instar of Pieris rapae L. was purified using ammonium sulfate fractionation and chromatography on Sephadex G-100. The enzyme kinetics was characterized using L-3,4-dihydroxyphenylalanine (L-DOPA) as substrate. The results show that benzaldehyde, p- hydroxybenzaldehyde, p-chlorobenzaldehyde, and p-cyanobenzaldehyde can inhibit the PPO activity for the oxidation of L-DOPA. The inhibitor concentration leading to 50% activity lost, IC50, was esti- mated to be 5.90, 5.62, 2.83, and 2.91 mmol/L for the four tested inhibitors, respectively. Kinetic analy- ses show that the inhibitory effects of these compounds are reversible. Benzaldehyde, p- hydroxybenzaldehyde, and p-chlorobenzaldehyde are noncompetitive inhibitors while p-cyano- benzaldehyde is a mixed-type inhibitor. The inhibition constants were determined for all four inhibitors. p-chlorobenzaldehyde and p-cyanobenzaldehyde were more potent inhibitors than the other com- pounds. These results provide a basis for developing PPO inhibition-based pesticides.     

8 MPa下C307催化剂上甲醇合成反应的本征动力学

在等温积分反应器中研究了操作条件对甲醇合成反应的影响以及C307催化剂上甲醇合成反应的本征动力学.实验采用粒度为0.154～0.198 mm的细颗粒催化剂.实验压力为8MPa,空速5 500～11 000 h-1,反应温度200~260℃.实验结果表明:总碳转化率在实验温度范围内随温度的升高先增加后降低,245℃左右达到最大值,随压力的升高而增加.选取以各组分逸度表示的CO、CO2加氢合成甲醇的Langmuir-Hinshelwood双速率本征动力学模型,用全局通用算法结合马夸特算法确定动力学模型参数.残差分析和统计检验表明,动力学模型是适宜的.     

Synergetic effect of multiple phases on hydrogen desorption kinetics and cycle durability in ball milled MgH2–PrF3–Al–Ni composite

A new Mg MgH₂–PrF₃–Al–Ni composite was prepared by ball milling under hydrogen atmosphere. After initial dehydrogenation and rehydrogenation, Pr₃Al₁₁, MgF₂, PrH₃ and Mg₂NiH₄ nanoparticles formed accompanying the main phase MgH₂. The hydrogen absorption-desorption properties were measured by using a Sieverts-type apparatus. The results showed that the Mg MgH₂–PrF₃–Al–Ni composi...     

粉煤灰-水泥浆体水化动力学模型

探讨了Dals提出的水化模型在密封及饱水养护条件下的适用性问题,分析了粉煤灰对水泥水化动力学影响的机理,提出了粉煤灰影响系数的概念,并根据试验结果得出影响系数的计算公式建立了粉煤灰-水泥体系水化动力学模型．