H型丝光沸石催化剂催化甲苯与叔丁醇的烷基化反应

针对合成对叔丁基甲苯传统工艺中存在的缺点,采用环境友好、可重复利用的H型丝光沸石催化剂(以下简称催化剂)进行了甲苯与叔丁醇的烷基化反应,并用X射线衍射和氨程序升温脱附等方法对不同焙烧温度下得到的催化剂的物相结构和酸性质进行了表征,研究了各种反应条件对催化剂的催化性能的影响。实验结果发现,在适宜的操作条件下,即催化剂的焙烧温度823K、反应温度180℃、反应时间3h、初始压力1.0MPa、原料与催化剂的质量比为8、叔丁醇与甲苯的摩尔比为4、溶剂环己烷与甲苯的摩尔比为5时,甲苯转化率达42.73%,叔丁基甲苯的选择性为96.30%,对叔丁基甲苯的选择性为80.37%。     

Simultaneous Measurement of Viscosity and Density with an Oscillating-Disk Instrument: The Effect of Fixed Plates

The period and damping of the free motion of a body oscillating in a fluid depend on the fluid's viscosity and density. Commonly, a working equation which expresses the damping as a function of the viscosity and density is solved for the viscosity, the damping being measured and the density being treated as an independently supplied parameter. Another working equation exists for the period, and, in general, the period depends on a combination of the viscosity and the density which is linearly independent of the combination that appears in the damping equation. It is, therefore, in principle, possible to determine both the viscosity and the density by a simultaneous solution of the two coupled working equations, since the period also is measured. In this paper, the working equations that describe the oscillating-disk viscometer are reviewed and their simultaneous solution is considered. The effect of fixed plates symmetrically located above and below the oscillating disk is of specific interest. The paper's main result is that fixed plates can dramatically increase the independence of the damping and period working equations, so that it becomes indeed feasible to determine the viscosity and the density of a fluid simultaneously from the damping and period of oscillating motion. A price is paid, however, because the instrument's working equations when plates are present have multiple solutions. Under special conditions, these multiple solutions can coalesce, and then one can only deduce the viscosity from the damping equation if the density is known a priori.     

KOAc/NaY催化合成邻甲基苯甲醚

以KOA c/NaY为催化剂,在连续流动固定床反应器内,邻甲基苯酚(OC)与碳酸二甲酯(DMC)经过气固相催化反应合成了邻甲基苯甲醚(OM)。考察了内、外扩散对KOA c/NaY催化剂活性的影响。实验结果表明,当气流线速度大于30cm/m in时可消除外扩散对合成反应的影响;当KOA c/NaY催化剂的平均粒径在0.30~0.75mm(20~80目的颗粒)时能消除内扩散对合成反应的影响。在消除内、外扩散效应后,还考察了反应温度、原料配比、空速对合成反应的影响,得到较佳的反应条件:催化剂5mL,反应温度548K,反应压力0.6M Pa,空速0.6h-1,n(DMC)∶n(OC)=1,在线评价时间7h。在此条件下,OC的转化率高达85.7%,OM的选择性大于99%。     

Biodegradation of monoaromatic hydrocarbons in aquifer columns amended with hydrogen peroxide and nitrate

The ability of indigenous microorganisms to degrade benzene, toluene, ethylbenzene and xylenes (BTEX) in laboratory scale flow-through aquifer columns was tested separately with hydrogen peroxide (110 mg/l) and nitrate (330 mg/l as NO₃⁻) amendments to air-saturated influent nutrient solution. The continuous removal of individual components from all columns relative to the sterile controls provided evidence for biodegradation. In the presence of hydrogen peroxide, the indigeneous microorganisms degraded benzene and toluene (> 95%), meta- plus para-xylene (80%) and ortho-xylene (70%). Nitrate addition resulted in 90% removal of toluene and 25% removal of ortho-xylene. However, benzene, ethylbenzene, meta- and para-xylene concentrations were not significantly reduced after 42 days of operation. Following this experiment, low dissolved oxygen (< 1 mg/l) conditions were initiated with the nitrate-amended column influent in order to mimic contaminated groundwater conditions distal from a nutrient injection well. Toluene continued to be effectively degraded (> 90%), and more than 25% of the benzene, 40% of the ethylbenzene, 50% of the meta- plus para-xylenes and 60% of the ortho-xylene were removed after several months of operation.     

苯对甲苯歧化与烷基转移反应的影响

研究了原料中苯含量对甲苯歧化与烷基转移反应的影响。随着原料中苯含量的增加 ,甲苯歧化反应受到明显抑制 ,同时发生苯和C9芳烃之间的烷基转移反应 ,C9芳烃转化率和C8芳烃选择性明显升高 ,有利于歧化装置多产C8芳烃。     

石蜡微胶囊中脲醛树脂壁材渗透性的研究

利用差示扫描量热法研究了石蜡微胶囊中脲醛树脂壁材对水及甲苯的渗透性 ,结果表明 ,水不能透过脲醛树脂壁材 ,而甲苯则易透过脲醛树脂壁材。因此 ,该石蜡微胶囊不能用于芳香族溶剂存在的场合。     

Development of a Magnetic Suspension Densimeter and Measurement of the Density of Toluene

The development of a magnetic suspension densimeter that has been built for measurement of the density of compressed liquid at pressures up to 30 MPa in the temperature range 20 to 150°C is described. The densimeter was first built by the author and his coworkers at NIST. We describe here further improvements made on a second system built at NMIJ based on the same principle. The densimeter uses a small coil suspended from an electronic balance. Within the coil is placed a sample cell in which the pressurized sample and a buoy, which is a permanent magnet, are enclosed. For measurement of density, balance readings are recorded (1) with the buoy at rest and (2) with the buoy in magnetic suspension. The measurement procedure is basically a hydrostatic weighing, which is simpler than those of conventional magnetic densimetry. As an example, measurements of toluene density performed as part of an inter-laboratory comparison are presented. The data agreed with reliable literature values to within a few hundredths of a per cent.     

p,V, T and derived thermodynamic data for toluene,trichloromethane, dichloromethane,acetonitrile, aniline,and n-dodecane

Experimentally determined p,V,T data are reported for toluene, trichloromethane, dichloromethane, acetonitrile, aniline, and n-dodecane at 278, 288, 298, 313, and 323 K, except for dichloromethane, for which the highest temperature was 298 K. At each temperature, measurements were done at pressures up to about 280 MPa or (for aniline and n-dodecane) at a lower pressure slightly below the freezing pressure at the temperature of measurement. Values of the isobaric expansivity isothermal compressibility and (for toluene, trichloromethane, dichloromethane, and acetonitrile) internal pressure, derived from the p,V,T data, are presented.     

Gas-phase selective oxidation of toluene on TiO2–sepiolite supported vanadium oxides: Influence of vanadium loading on conversion and product selectivities

Gas-phase selective oxidation of toluene has been carried out on vanadium oxide systems (5–20 wt.% of V₂O₅, equivalent to 0.4–1.7 theoretical monolayers) supported on TiO₂–sepiolite (with titania loading around the theoretical monolayer, 12 wt.%) and on sepiolite. A study has been made on both the influence of vanadia loading and of the support on the catalytic behaviour of the supported vanadium systems. The reducibility by H₂ TPR was also studied as well as the acid and basic/redox sites from the results of conversion of the 2-propanol test reaction of the solids. Benzaldehyde, benzoic acid and several coupling products were the main ones detected, attaining over 50% selectivity towards the benzaldehyde and benzoic acid products at a total conversion around 10%. The activity and selectivity to the selective products exhibited by vanadium systems supported on mixed support were superior to those exhibited by the systems supported on sepiolite and increased notably in both series with the increase in vanadium loading. The best catalytic behaviour exhibited by the vanadium systems supported on mixed support, which also exhibited the highest density of sites capable of being reduced (as well as their reducibility) and of those responsible for propanone formation, could be attributed not only to the different balance of the vanadia species existing in the two supports (monomeric + oligomeric/polymeric), but also to such other factors as the nature of the support and, concretely, its chemical composition.     

Studies on Catalytic Side-Chain Oxidation of Nitroaromatics to Aldehydes with Oxygen

The side-chain oxidation of 2-nitrotoluene in liquid phase in the presence of catalytic amount of manganese sulfate and stoichiometric amount of potassium hydroxide with oxygen was studied. In the most favorable conditions, over 80% of conversion of 2-nitrotoluene and 50% of selectivity to 2-nitrobenzaldehyde was achieved. Effects of the reaction parameters on the conversion of the reactant and the selectivity of the product were examined. These results, together with EPR spectroscopic study, show that a benzyl anion was formed in the early stage of the reaction, which was then converted to the final product via a free radical mechanism.