催化湿式氧化苯酚的TiO2-CeO2催化剂的制备与表征

 采用共沉淀法制备了催化湿式氧化降解苯酚的TiO2-CeO2催化剂,通过单因素多次实验和正交实验两种不同的实验方式,考察了不同的制备条件如活性组分配比、焙烧温度、焙烧时间和老化过程的pH值等对催化剂活性的影响,证明了老化过程中保持较高pH值对于TiO2-CeO2催化剂的活性具有决定性作用. 当活性组分摩尔配比为1:1, 焙烧温度为450 ℃, 焙烧时间为5.0 h, 老化过程中pH保持为11时得到的催化剂,在反应温度为150 ℃, 氧分压为4.5 MPa的条件下,经90 min的反应,浓度为2.1 g/L的苯酚溶液COD去除率达到了93%. 通过热重差热、N2吸附-脱附、 X射线衍射(XRD)和X射线光电子能谱(XPS)等分析方法揭示了催化剂的微观结构. 结果表明, BET比表面积、表面吸附氧以及表面三价金属元素的相对含量等物理和化学结构特性对催化剂的活性有重要影响.     

Ti/Sb2O5-SnO2/PbO2电极电催化氧化对氨基苯酚

以电沉积法制备的Ti／Sb2O5-SnO2／PbO2电极作阳极,恒电流电解水溶液中的对氨基苯酚（PAP）,利用紫外光谱探讨了对氨基苯酚电催化氧化的反应历程,系统地考察了电解时间、反应温度,pH值、电流密度以及对氨基苯酚初始浓度对COD去除率的影响,提出了电催化氧化对氨基苯酚的最佳条件．结果表明,对氨基苯酚电催化反应为逐级氧化历程,主要中间产物为苯醌、丁烯二酸和草酸,最终产物为CO2和水．20℃,对初始浓度10mg／L的对氨基苯酚水溶液（pH=6）,恒定电流密度100mA／cm^2,电解1h,COD去除率可达98．5％．该方法作为废水中对氨基苯酚的最小化处理．具有良好的应用前景．     

Synthesis of Maleic Anhydride by Oxidizing Furfural over Phosphorusmolybdenumic Acid Supported on Silica Gel

采用浸渍法制备负载型磷钼杂多酸催化剂,分析了催化剂的比表面积、分散性、结构特征、稳定性以及再生温度等性质.通过固定床微反应器考察杂多酸催化剂催化氧化糠醛生成顺丁烯二酸酐的催化性能.研究了焙烧温度、负载量对催化剂性能的影响,以及反应温度对顺丁烯二酸酐收率的影响.结果表明：通过浸渍制备的杂多酸催化剂具有杂多酸催化剂的Keggin结构,具有较好的稳定性和酸性;活性组分能较好的分布于载体SiO2上;催化剂的再生温度和活化温度均为400℃;在钼磷原子比为0.85,负载量为48.6%时催化性能较好,催化剂的表面酸量为0.646 mmol/g;反应温度控制在365℃附近时,顺丁烯二酸酐收率可达到57.2%,选择性为62.7%.     

硅胶负载磷钼杂多酸催化氧化糠醛制顺丁烯二酸酐

采用浸渍法制备负载型磷钼杂多酸催化剂,分析了催化剂的比表面积、分散性、结构特征、稳定性以及再生温度等性质.通过固定床微反应器考察杂多酸催化剂催化氧化糠醛生成顺丁烯二酸酐的催化性能.研究了焙烧温度、负载量对催化剂性能的影响,以及反应温度对顺丁烯二酸酐收率的影响.结果表明:通过浸渍制备的杂多酸催化剂具有杂多酸催化剂的Keggin结构,具有较好的稳定性和酸性;活性组分能较好的分布于载体SiO2上;催化剂的再生温度和活化温度均为400℃;在钼磷原子比为0.85,负载量为48.6%时催化性能较好,催化剂的表面酸量为0.646 mmol/g;反应温度控制在365℃附近时,顺丁烯二酸酐收率可达到57.2%,选择性为62.7%.     

负载型镧锰钙钛矿催化剂上甲烷催化燃烧的研究

研究了甲烷在负载型镧锰钙钛矿催化剂(LCFM／α-Al2O3)上的低温催化燃烧反应．考察了制备方法、焙烧温度列催化剂结构和活性的影响．并进行了100h稳定性实验．实验结果表明用浸渍法、焙烧温度高于800℃就能在载体上生成良好的钙钛矿结构，催化剂具有较低的起燃温度并且在高温条件下具有与非负载型镧锰钙钛矿催化剂相当的活性；100h稳定性实验表明LCFM／a-Al2O3催化剂经历了100h．800℃的连续高温燃烧反应，催化剂仍保持了原有结构和催化活性．并且没有明显积碳．     

湿式催化氧化处理含高浓度甲醛的草甘膦废水

草甘膦结晶母液经蒸发或纳滤浓缩回收后,产生大量含有高浓度甲醛的废水,常规的废水处理方法难以达到回用或排放要求.以过量溶液浸渍法制备的Pt-Bi-CeO2/AC为催化剂,采用湿式催化氧化法处理2.5%的HCHO溶液,HCHO去除率高达99.9%以上,COD去除率达到96.6%.采用Pt-Bi-CeO2/AC催化剂对含低浓度草甘膦(PMG,50 mg/L)的生产废水直接进行湿式催化氧化处理,催化剂使用23次后,HCHO去除率稳定在85%左右,COD去除率稳定在87%左右,催化剂具有良好的稳定性.湿式催化氧化处理后的废水可直接回用于PMG生产.采用固定床湿式催化氧化装置处理HCHO溶液以及PMG生产废水,处理效果也非常理想,连续使用720 h,催化剂的稳定性能良好.通过XRD、N2吸附-脱附、HRTEM、ICP-OES和XPS等分析手段对催化剂进行了系统表征.     

Ru/ZrO2-CeO2催化剂催化湿式氧化乙酸和苯酚的研究

采用共沉淀法制备了ZrO2-CeO2颗粒载体,利用浸渍法制备了Ru/ZrO2-CeO2颗粒催化剂,采用BET、XRD、SEM、TEM等方法对其进行了结构表征,测定了其催化湿式氧化乙酸的活性,并以苯酚为模型物进行了动态试验.结果表明,Zr的添加抑制了CeO2晶粒的长大,增加了催化剂的抗热性能.当催化剂Zr、Ce摩尔比为1∶9,焙烧温度为300℃时催化剂活性最高,在200℃和4 MPa下,催化湿式氧化乙酸反应120 m in后,COD去除率可达99%.动态实验100 h内,苯酚与COD的去除率都保持在90%以上,催化剂具有很好的活性和稳定性.     

Fe2O3/CNT催化湿法H2O2氧化苯酚

通过化学沉积法和热处理得到多壁碳纳米管负载Fe2O3催化剂 Fe2O3/CNT, Fe2O3的负载质量分数约为15.1%,XRD表征显示,负载的Fe2O3存在α和γ这2种晶型。考察了Fe2O3/CNT催化湿式H2O2氧化去除废水中苯酚催化性能,通过苯酚的去除率及反应过程中催化剂活性组分的溶出总量,研究了催化剂制备过程中添加聚乙烯醇对催化剂性能的影响。在苯酚和H2O2初始浓度分别为350和1 500 mg/L、催化剂投加量为1.0 g/L、温度80 ℃条件下,经过240 min的反应,苯酚去除率达100％,COD去除率为86.1％。     

载体焙烧温度对Co／ZrO2催化剂催化F－T合成反应的影响

 采用并流共沉淀法制得了ZrO2载体，采用等体积浸渍法制备了钴质量分数为10％的系列负载型催化剂，考察了载体焙烧温度对催化剂催化性能的影响．结果表明，焙烧温度对载体的物化性质有显著影响，提高焙烧温度可降低载体的表面酸性，减弱钴锆之间的相互作用，提高催化剂的活性和选择性．钴负载到低温焙烧的载体上促进了ZrO2由无定形向四方相的转变，提高了催化剂的分散度，降低了催化剂的活性和选择性．     

不同CuO/CeO2催化剂上CO低温氧化反应

 分别用热解硝酸铈法和浸渍法制备了不同物性的CeO2粉体和相应的CuO/CeO2催化剂,并用XRD, HRTEM和TPR等对样品进行了表征,利用微反-色谱装置考察了其催化CO低温氧化的活性. 结果表明,热解温度影响CeO2的物性(形貌、粒度大小及分布等). 相同条件下,不同物性的CeO2载体上CuO的负载情况不同, 500 ℃热解获得的CeO2载体上非晶态CuO负载量最高,相应的CuO/CeO2催化剂活性也较高. 非晶态CuO一部分进入CeO2晶格,另一部分高度分散于CeO2表面上. 焙烧温度较低时(≤ 600 ℃), 催化剂活性受焙烧温度的影响较小,而高温(800 ℃)焙烧后,催化剂则因载体粒度增大和CuO烧结团聚等因素导致催化活性明显降低.     

利用手持技术改进测定乙醇分子结构实验

利用压强传感器代替排水集气法,改进测定乙醇分子结构实验的仪器装置,并探索最佳反应条件。另外,设计两个空白实验,结合压强变化曲线对实验误差进行相关讨论。     

光谱仪测试范围的扩展

由于石化行业的生产需要，其材质的使用具有多样性和广泛性，经常会出现顾客委托的测试样品的一个或几个元素跨越光谱仪现有测试程序测量范围的情况。本法通过对光谱仪测试原理的认识，根据光谱仪的测试能力及标样的采集，实现了一个或几个元素测量范围的扩展，并对其测量的影响因素进行了研究。     

Neutral diterpenoids of oleoresins of five species of conifers of Transcarpathia

The compositions of the neutral diterpenoids of the oleoresins of five species of conifers growing in the Transcarpathia have been studied. It has been found that the oleoresins ofAbies alba M.,Larix decidua M., andPicea excelsa L. contain more than 50% of neutral diterpenoids. The group and qualitative compositions of the oxygen-containing diterpenoids have been determined. In the oleoresins ofAbies alba,Picea excelsa, andPicea abies tertiary alcohols — cis-abienol and isocembrol — predominate, while inLarix decidua the main component is the hydroxy ester larixyl acetate. Primary alcohols related to the resin acids have been found in all the oleoresins investigated. Features of the distribution of diterpenoids according to the species of conifers have been revealed. The results obtained are necessary for the chemotaxonomy of conifers of the family Pinceae.Novosibirsk Institute of Organic Chemistry, Siberian Branch, Academy of Sciences of the USSR. Translated from Khimiya Prirodynkh Soedinenii, No. 6, pp. 812–816, November–December, 1988.     

Dichroism of absorption and polarization of phosphorescence of molecules of the closed form of nitrobenzospirothiopyran

The spectral-polarization characteristics of absorption and phosphorescence of molecules of the initial form of nitro-substituted indolinospirobenzothiopyran were studied in oriented polyethylene films and in solutions with different polarity. An oscillator model of the electron transitions responsible for the formation of absorption and luminescence spectra was suggested. It was established that the principal differences in the spectral and photophysical properties of the compound studied and its oxygen-containing analog are associated with the fact that the electronegativity of the S atom is lower than that of the O atom. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1143–1146, June, 1997.     

Influence of viscosity of medium on processes of oxygen quenching of excited states of mesoporphyrin

The oxygen quenching rate constants for singlet and triplet excited states of the dimethyl ester of mesoporphyrin IX increase with decreasing viscosity of the medium and reach a maximum at a viscosity of approximately 0.4 mPa·sec, after which the rate constants begin to decrease. The drop in rate constant with increasing fluidity of the medium may be related to a nonequilibrium character of the elementary act in the interaction of the reactants in the solvent cage. In viscous media such as isopropyl alcohol, isobutyl alcohol, and isoamyl alcohol, the reaction radius is greater than the sum of the radii of the reacting particles. The long-range character of these processes is due to the relatively weak dependence of the quenching probability on distance.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 25, No. 2, pp. 161–167, March–April, 1989.     

Determination of heats of detonation and influence of components of composite explosives on heats of detonation of high explosives

The heats of detonation of 20 simple high explosives and explosive mixtures were determined by means of an adiabatic detonation calorimeter designed by the authors. The results indicated that the performance of the instrument was reliable and the experimental data were very accurate. For explosive mixtures, there was a linear accumulative relationship between the heats of detonation of the explosive mixture and its components. Accordingly, the heats of detonation of explosive mixtures could be calculated directly from the heats of detonation of simple explosives and the characteristic heats of other components. The experiments showed that the gold or brass shell of the cylindrical charge could be substituted by a thick-walled porcelain shell, which had the advantage of cheapness.

     

物质分配系数的测定实验改进

实验教学目的是从解决实际问题出发,以实验技术训练和实验设计思想培养为目标。介绍了将单一的物质分配系数测定实验改进为综合实验,提高了实验效果及实验资源利用率。     

Calculation of enthalpies of hydrogenation of hydrocarbons

Sets of hydrogen molecule equivalents have been developed which permit the calculation of hydrogenation of different types of carbon-carbon bonds from ab initio total energies (3-21G and 6-31G* basis sets, and, to a more limited extent, for MP2/6-31G* data) of reactants and products. The calculated enthalpies of hydrogenation are in good agreement with experiment for unstrained molecules, with average errors on the order of 2 kcal/mol. The 6-31G* equivalents allow the enthalpies for strained molecules to be calculated accurately, but the 3-21G equivalents do not. The equivalents for both basis sets have been tested by calculating the enthalpies of hydrogenation of carbon-carbon bonds in nitrogen- and oxygen-containing organic molecules, free radicals, and classical carbocations. The results are in good agreement with experiment in most cases.     

非那雄胺合成工艺改进

非那雄胺能抑制5α-还原酶的活性,明显降低二氢睾酮水平,是一种治疗良性前列腺增生的有效药品。该合成工艺以甾烯酮酸为原料,将其与氯化亚砜反应,无须分离即与叔丁胺反应得17β-酰胺化合物,再氧化开环,环合,氢化,脱氢合成了非那雄胺。经元素分析、IR、1HNMR、13CNMR、MS分析表征了其结构。该法无须使用昂贵的2,2-二吡啶二硫化物和剧毒药品苯亚硒酸酐,且以乙酸铵代替氨气,降低了对设备的要求和腐蚀,更适用于工业生产。