Reaction pathway of benzonitrile formation during toluene ammoxidation on vanadium phosphate catalysts

The reaction pathway of the ammoxidation of toluene on (VO)₂P₂O₇ used as catalyst and the interaction of potential intermediates with the pyrophosphate were studied by spectroscopic techniques (FTIR, EPR), temperature-programmed chemisorptions/ reactions (TPD, TPRS) and transient studies such as the temporal analysis of products (TAP) technique. NH₃ is chemisorbed on the catalyst surface, forming three different species, i.e., NH ₄ ⁺ ions located on BrØnsted sites, coordinatively bound NH₃ on Lewis sites and NH ₂ ^– groups, presumably P-NH₂. Toluene that is probably adsorbed on Lewis sites reacts in a first step to a benzyl radical. A subsequent partial oxidation by interaction of V^IV=O groups generates a V...O=CH-C₆H₅ surface structure. This benzaldehyde-like surface species reacts with adsorbed NH₃ according to a Langmuir-Hinshelwood mechanism. TAP experiments on ammonium-containing vanadium phosphates revealed that NH ₄ ⁺ ions could act as potential N-insertion species. No formation of benzylamine as well as the generation of V=NH surface groups as possible intermediates or N-insertion sites were observed.     

固体三元稳态ClO2急性经口、遗传及蓄积毒性研究

固体三元稳态二氧化氯是为了解决二元产品活动化率低、活化酸度高、活化损失大的缺点而研制出的新型固体ClO2产品。通过对其急性经口毒性、遗传毒性及蓄积毒性的试验研究，发现雌雄小鼠的急性经口LD50值均大于21．5g/kg，该产品属于实际无毒级；剂量达5．00g/kg，未检出对雌雄小鼠骨髓嗜多染红细胞的诱变活性；给药20d后，动物死亡仍未足半数，K＞5，该产品为弱蓄积性。     

武汉市大气降水δD和δ~(18)O变化特征及水汽来源

为了确定长江流域中游大气降水特征和水汽来源,以全球大气降水观测网(GNIP)武汉站点多年大气降水稳定同位素数据为基础,探讨了长江中游武汉地区大气降水稳定同位素随季节变化特征。通过建立当地大气降水方程,结合气象因素和降水氘盈余变化,揭示了武汉地区不同季节大气降水水汽来源。结果表明:大气降水在降落地面之前经历了非平衡分馏过程,且平衡程度接近于东部季风沿海地区;大气降水稳定同位素表现出明显的季节性特征,且冬季和夏季降水δD和δ~(18)O值与雨量之间负相关,表现出明显的"雨量效应";大气降水水汽来源主要受季风活动的控制,冬季水汽主要来自北方大陆冷湿气流,而春季降水表现出局地蒸发来源,夏季和秋季降水来源受西南季风和东南季风的双重影响。     

基于同位素水化学分析的松嫩平原大布苏湖流域地下水补给源研究

采用同位素与水化学分析方法研究了大布苏湖湖水的补给源,结果表明,大布苏湖水主要来自地下水的补给。大布苏湖水、地下水与松花江中游的江水同位素δ2H-δ18O关系点分布在相同的区域,且受到了一定程度的蒸发。泉水中的氟-砷关系表明,补给湖泊的地下径流主要发生在20~30m的粉细砂层,火山岩风化物细颗粒沉积层构成了主要的透水层,火山岩细颗粒中的砷通过氧化还原反应溶解到地下水中,形成了高砷含水层。据此推断,大布苏湖水来自于松花江等周边河流的渗漏,渗漏水通过黄土层下伏的高砷粉细砂层向大布苏湖中排泄。湖心钙华表明同时存在深层承压水的越流补给。     

三芳基甲烷树脂的磁性行为

介绍了ＢＡ／Ｐｙ，ＢＡ／Ｐｈ和ＰＨＢＡ三种具有三芳基甲烷结构Ｂ阶树脂的合成方法及分子链的单元结构形式。对用紫外光和激光照射法进行脱氢反应的实验条件及脱氢化后树脂的磁性能（磁滞现象，矫顽力和磁化强度）进行考查。     

加强科学管理延长转化器的使用寿命

简述了巨化电化厂对转化器加强科学管理，以减少漏损的作法，取得了良好的经济效益。     

具有高粘度分散相的油-水分散体系的液滴破碎与粒径分布研究

对湍流搅拌槽中原油-水分散体系的液滴破碎进行了研究。在不同的温度下原油表现出不同的流变学特征，对分散过程中的液滴破碎产生不同的影响。实验研究对比了不同温度下原油-水分散体系的液滴分布及最大稳定粒径，分析了触变性对破碎过程及最大稳定粒径的影响。经过模型计算与实验结果比较，发现以初始粘度计算的理论值预测最大稳定粒径更为合适。     

Measurement of O2-N2 binary sorption on 5A zeolite by isotope tracer and perturbation chromatography

Isotope tracer chromatography allows to extract simply and quickly multi component adsorption data and is demonstrated for single component and binary adsorption equilibria for O₂ and N₂ on 5A zeolite as an example. In this modification of conventional tracer chromatography, a small pulse of an isotope tracer is injected in an adsorbable carrier gas (pure or multicomponent mixture) flowing through a column filled with adsorbent and is designed to operate at almost uniform pressure. Isotherm parameters are readily extracted by fitting measurements of residence times at various pressures and carrier composition. The isotherms were in excellent agreement with volumetric measurements. Isotope tracer chromatography is shown to be superior to perturbation chromatography since the influence of the injection volume on the carrier gas composition is substantially smaller for tracer experiments. Unfortunately, this new improved gas chromatographic technique requires rather expensive isotopes. The strength of this new approach lies in the advantage of working with small adsorbent samples (1 g) making a rapid screening of newly developed materials possible.Nomenclature K _exp,tr,i experimental tracer adsorption constant (mol/kg pure adsorbent/Pa) - K _i Henry adsorption equilibrium constant (mol/kg pure adsorbent/Pa) - K _i,part partition coefficient - K _pert composite Henry constant (mol/kg pure adsorbent/Pa) - L column length (m) - L _i Langmuir adsorption constant (1/Pa) - n _i amount adsorbed on the solid (mol/kg adsorbent) - N _i adsorbent loading (Pa) - p total pressure (Pa) - p _i partial pressure of component i (Pa) - p _in column inlet pressure (Pa) - p _out column outlet pressure (Pa) - q _i amount of component i in the micropores (Pa) - R gas constant (J/mol/K) - t time (s) - T temperature (K) - v _f superficial velocity in adsorbent column (m/s) - v _out velocity at the outlet of the column (m/s) - V _inlet volumetric flow rate at inlet conditions (ml/s) - x molar fraction of tracer - y molar fraction of component i in the carrier gas - z axial coordinate (m) Greek letters _ext bed voidage, external porosity - _macr macropore porosity [_macr= _p (1–_ext)] - _micr micropore porosity - _tot total porosity - _p pellet porosity - volume fraction of binder material - _d dead time (s) - _tracer tracer residence time (s) - _pert perturbation residence time (s) - _crys crystal density (kg/m³)     

高速公路稳定期桥头跳车治理及其路面改善设计

在判定桥头路基沉降进入稳定期后,采用纵坡拟合并辅以路面改善的设计方法,以永久消除桥头跳车给司乘人员带来的不良感受.此设计方法首次在我省高速公路几处桥头应用并实施,经过三年来的运营,使用效果较好.本文对此类设计经验进行了总结,供有关养护设计参考.     

Relationship of hydrocarbon and source-rock in Nos.3-5 tectonic belts of the Lenghu area, northern Qaidam Basin

Based on analyses of the components of crude oil hydrocarbons and carbon isotopes, the content of normal alkane de-creased from 49.00% to 20.10% when moving from the No.3 to No.5 tectonic belt of the Lenghu area of the Qaidam Basin, while cycloalkanes increased from 30.00% to 52.20% and aromatic and branch chain alkanes increased gradually as well. The maturity of sterane in crude oil is higher than that of its source-rock, which shows that the hydrocarbons were generated from a deep source-rock of high maturity around the tectonic belts of the Lenghu area. The analysis of the characteristics of carbon isotopes also shows that these isotopes of hydrocarbon compounds in the No.4 and No.5 tectonic belt are apparently heavier than those in the No.3 belt. The results of our research show that the hydrocarbons in the No.3 tectonic belt are mainly from a relatively rich sapropelic substance, while the hydrocarbons in the No.4 and No.5 tectonic belt originated mainly from organic matter of a rela-tively rich humic type substance.