改性Pt／HY沸石重整催化性能研究

以正己烷、环己烷为原料，通过连续微反装置，考察了反应温度对Ｐｔ／ＨＹ催化剂反应产品的影响，同时探讨了阳离子改性Ｐｔ／ＨＹ以及ＨＹ与γ－Ａｌ２Ｏ３机械混合后载铂的重整催化性能．结果表明，ＨＹ沸石的活性和苯选择性都较低，适宜的反应温度有利于沸石催化性能的提高，ＨＹ与γ—Ａｌ２Ｏ３混合后，活性和芳构优选择性均明显提高．     

Catalyst design and development for upgrading aromatic hydrocarbons

Background and strategy of catalyst development for upgrading aromatic hydrocarbons are intensively discussed. Originally prepared catalysts (hydrogenation and hydrocracking catalysts) were used for accelerated aging tests. Though each catalyst showed superior catalytic performance as compared to commercially available catalysts, a severe deactivation was observed on the hydrocracking (HC) catalysts. A new type of HC catalyst was designed and prepared, based on the understanding of catalyst deactivation. High silica NaY zeolites were synthesized using crown-ether. USY zeolites were then prepared by ion exchange, steaming and calcining. Surface properties and catalytic functions of well-crystallized USY zeolites were investigated to develop practical HC catalysts. The Ni–W catalyst prepared using the newly prepared USY zeolite showed a considerable improvement in the HC activity.     

Hydrogenation of carbon dioxide over copper-pyrochlore/zeolite composite catalysts

The hydrogenation of CO₂ was studied over composite catalysts obtained by mixing Cu-based methanol synthesis catalyst and HY zeolite. A mechanism associating methanol synthesis and MTG (methanol to gasoline) reaction allowed the formation of C₁-C₄ hydrocarbons. It was found that the catalytic behaviors of the composite catalysts were favorably influenced by the characteristics of the methanol synthesis catalysts. The Cu-La₂Zr₂O₇ catalyst we recently developed associated with HY zeolite exhibited interesting performances in hydrocarbon synthesis. The addition of ZrO₂ to Cu---La₂Zr₂O₇/HY enhanced the ability to produce hydrocarbons. Comparing composite catalyst systems prepared with different Cu-based methanol synthesis catalysts, the effect of Na contamination on methanol and hydrocarbon formation over composite catalysts were also discussed.     

HY分子筛催化合成长链烷基萘

比较了环境友好催化剂HY和Hβ分子筛催化萘与长链烯烃(C11、C12混合烯烃)烷基化反应的催化性能,研究结果表明,HY分子筛具有较高的催化活性和烷基化选择性。考察了反应温度、压力、萘与C11/C12烯烃摩尔比、进料空速、催化剂粒度等反应条件对烯烃转化率的影响,在适宜的反应条件(萘与C11/C12混合烯烃摩尔比4/1、反应温度130℃、催化剂粒度20～40目、进料空速10ml/(h·g)、压力1 0MPa)下,长链烯烃的转化率可达85%,单烷基萘的选择性为100%。该催化剂易于再生,可循环使用。     

F/HY催化剂用于挂式四氢双环戊二烯的制备

采用室温过量浸渍法,制备不同F用量改性的HY分子筛催化剂。采用氨程序升温脱附法(NH3-TPD)、X线衍射仪(XRD)、傅里叶变换红外光谱仪(FT-IR)对催化剂的结构及酸性质进行表征,并在桥式四氢双环戊二烯(endo-TCD)制备挂式四氢双环戊二烯(exo-TCD)的反应中考察催化剂的催化性能。结果表明:最适宜的反应条件为以1.0%F/HY为催化剂,活化温度300℃,反应温度240℃,催化剂与原料质量比0.25∶1,溶剂环己烷与endo-TCD的摩尔比10∶1,初始压力1.0 MPa,反应时间1.5 h。最优条件下桥式四氢双环戊二烯的转化率达到92.6%,挂式四氢双环戊二烯的收率达到了59.4%。失活的催化剂可以通过550℃高温焙烧再生,其活性变化不大。     

Biotransformation of phenolics (isoflavones,flavanols and phenolic acids) during the fermentation of cheonggukjang by Bacillus pumilus HY1

Changes in β-glycosidase, esterase activities, isoflavone, flavanols and phenolic acid during the fermentation of Korean whole soybean fermented food cheonggukjang by Bacillus pumilus HY1 were investigated. The levels of aglycones, flavanols and gallic acid increased, while the β-glucosidase activity, esterase activity, glycosides content (except for acetylglycosides) and flavanol gallates decreased. Total isoflavone content slightly decreased after 60 h of fermentation, while total flavanol and phenolic acid content increased. The highest levels of daidzein (aglycone type) and acetyldaidzin (glycoside type) were recorded after 48 h of fermentation. The levels of catechin, epicatechin and gallic acid also increased during fermentation. However, total contents of glycosides, malonylglycosides and flavanol gallates decreased by about 80%, 90% and 60% during 60 h of fermentation, respectively. In addition, total phenolic content increased markedly during fermentation, while levels of 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical-scavenging activity increased. Hence, it would be beneficial for the food industry if components of cheonggukjang could be separated and developed into functional products.     

Solar photocatalytic mineralization of isoproturon over TiO2/HY composite systems

The present investigation covers immobilization of titanium dioxide over HY support for the treatment of isoproturon pesticide. Catalysts are characterized by XRD, SEM–EDAX, TEM, BET surface area and UV–vis DRS. A detailed photocatalytic degradation study under solar light in aqueous suspensions with parameters like loading of TiO₂ over HY, amount of the catalyst, concentration of substrate, pH effect, durability of the catalyst and comparison between suspended TiO₂ and supported systems are reported. Mineralization of isoproturon is monitored by total organic carbon, chemical oxygen demand and a plausible mechanism is proposed for photocatalytic degradation based on degradation products.     

A combined MAS nuclear magnetic resonance spectroscopy,in situ FT infrared spectroscopy and catalytic study of the conversion of allyl alcohol over zeolite catalysts

A combined study of allyl alcohol conversion over zeolite catalysts using catalytic measurements in a flow microreactor, in situ FTIR and MAS NMR spectroscopy is reported. Rate constants for the conversion in the flow reactor and the static in situ reactor used in the FTIR studies are in broad agreement, emphasising the viability of the experimental approach. In the flow microreactor allyl alcohol conversion over the zeolite catalyst is shown to form diallyl ether, hydrocarbons and acrolein. The in situ study successfully models the formation of diallyl ether and hydrocarbon as initial reaction products, but unfortunately acrolein is found to be rapidly converted to hydrocarbons under the condition used in the in situ cells. The studies are combined to provide a model for the reaction which involves two parallel pathways for the formation of the hydrocarbons and acrolein.     

A critical shear displacement criterion for ductile–brittle transition under mixed mode I and II loading

Abstract

Micromechanisms producing ductile and brittle damage operate in parallel at a crack tip. The dominant mode of failure depends upon which of the two (ductile or brittle) damage parameters first reaches its critical value. This has been shown by a study of ductile–brittle transition behaviour in HY100 steel under mixed mode I and II loading. The transition from ductile to brittle behaviour in HY100 steel was found to be affected by mixed mode I and II ratio (ratio of imposed tensile and shear loading) in a manner such that with increasing shear the transition temperature decreased. In the present paper, a criterion is proposed based on the shear strain ahead of a notch tip, to predict the fracture behaviour at any given temperature and mixed mode ratio.     

HY和USY分子筛对模拟油品中碱性氮化物的吸附行为

以HY、USY分子筛作为吸附剂,喹啉的十二烷溶液为模拟油,在间歇式微型反应釜中,进行了静态吸附脱除碱性氮化物的实验研究。考察了两种分子筛的吸附温度、剂油质量比对脱氮率的影响,并对其吸附热力学、吸附动力学进行了研究。结果表明,HY和USY分子筛最佳吸附温度分别为100 ℃和140 ℃,最佳剂油质量比为1∶30;通过吸附热力学的研究,得出两种分子筛的等温吸附曲线为H型化学吸附曲线,Langmuir等温方程拟合相关系数大于0.999,新建立的等温化学吸附方程可以很好地拟合等温吸附曲线;吸附焓变?H>0,自由能变?G0,实验条件下碱性氮化物在两种分子筛上的吸附是吸热的、自发的化学吸附过程;采用3种动力学模型对两种分子筛的吸附行为进行拟合,得出准二级动力学模型是描述两种分子筛吸附过程的最佳动力学方程,相关系数大于0.999。