A Monte Carlo Method to Quantify the Effect of Reactor Residence Time Distribution on Polyolefins Made with Heterogeneous Catalysts: Part I—Catalyst/Polymer Particle Size Distribution Effects

Polyolefins are commercially produced in continuous reactors that have a broad residence time distribution (RTD). Most of these polymers are made with heterogeneous catalysts that also have a particle size distribution (PSD). These are totally segregated systems, in which the catalyst/polymer particle can be seen as a microreactor operated in semibatch mode, where the reagents (olefins, hydrogen, etc.) are fed continuously to the catalyst/polymer particle, but no polymer particle can leave. The reactor RTD has a large influence on the PSD of the polymer particles leaving the reactor, as well as in polymer microstructure and properties, polymerization yield, and composition of reactor blends. This article proposes a Monte Carlo model that can describe how particle RTD in a single or a series of reactors can affect the PSD of polymer particles made under a variety of operation conditions. It is believed that this is the most flexible model ever proposed to model this phenomenon, and can be easily modified to track all properties of interest during polyolefin production in continuous reactors with heterogeneous catalysts.     

An Immobilized‐Dirhodium Hollow‐Fiber Flow Reactor for Scalable and Sustainable C−H Functionalization in Continuous Flow

A scalable flow reactor is demonstrated for enantioselective and regioselective rhodium carbene reactions (cyclopropanation and C?H functionalization) by developing cascade reaction methods employing a microfluidic flow reactor system containing immobilized dirhodium catalysts in conjunction with the flow synthesis of diazo compounds. This allows the utilization of the energetic diazo compounds in a safe manner and the recycling of the dirhodium catalysts multiple times. This approach is amenable to application in a bulk‐scale synthesis employing asymmetric C?H functionalization by stacking multiple fibers in one reactor module. The products from this sequential flow–flow reactor are compared with a conventional batch reactor or flow–batch reactor in terms of yield, regioselectivity, and enantioselectivity.     

Einfluß der Sensor-Zeitkonstanten auf die Auswertbarkeit von Ta-Daten

All temperature sensors have a finitely time constant. The influence of the sensor time constant gt_s on the results of kinetic evaluation is demonstrated at four reaction types. The ignorance of the sensor indolence gives incorrect activation parameters. Therefore the determination of _s is necessary.For the estimation of parameters the nonlinear evaluation program TA-kin was used. With its help it is possible to find the real parameters, also when _s=32 s, if the real _s-value was entered.

     

Photodecomposition of phenol in a flow reactor: Adsorption and kinetics

Summary In this study, a new air lift loop photoreactor was used for both continuous and non-continuous water photodetoxification. Also, the kinetics of phenol photodegradation were measured under flow conditions. Both the kinetics of phenol adsorption on TiO₂/SiO₂ and of the total photo-mineralization of phenol were measured in order to gain more knowledge on the photocatalytic oxidation of phenol on illuminated titania.Adsorption of phenol on TiO₂/SiO₂ proceeds even from diluted solutions. However, based on our data, it is impossible to state precisely the influence of the adsorption on the overall rate of phenol photodecomposition. The photoreaction yields stable intermediates which subsequently undergo total mineralization to CO₂ and H₂O. It is postulated that the intermediates consist mainly of polymeric compounds, difficult to determine by conventional analytical methods like GC, HPLC, or UV/Vis spectroscopy.

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Photolyse von Phenol in einem Durchflußreaktor: Adsorption und Kinetik

Zusammenfassung Ein neuartiger Photoreaktor wurde auf seine Verwendbarkeit zur kontinuierlichen und nichtkontinuierlichen Wasseraufbereitung getestet. Die Kinetik des photolytischen Abbaus von Phenol wurde unter Durchflußbedingungen untersucht. Zum besseren Verständnis der photokatalysierten Oxidation von Phenol auf belichtetem Titanoxid wurde außerdem die Kinetik sowohl der Adsorption von Phenol an TiO₂/SiO₂ als auch seiner Gesamtphotomineralisierung erforscht.Adsorption von Phenol an TiO₂/SiO₂ erfolgt bereits aus verdünnten Lösungen. Nach unseren Ergebnissen ist es allerdings unmöglich, den Einfluß der Adsorption auf die Photolyse genau zu bestimmen. Die Photoreaktion ergibt stabile Zwischenprodukte, die sich im weiteren Verlauf zu CO₂ und H₂O umsetzen. Es wird postuliert, daß es sich bei den Zwischenprodukten hauptsächlich um Polymere handelt, die mit konventionellen analytischen Techniken wie GC, HPLC oder UV/Vis-Spektroskopie schwer nachzuweisen sind.

     

Development of a membrane-based vapor-phase bioreactor

A vapor-phase bioreactor has been developed utilizing porous metal membranes in a cylindrical design employing radial flow as opposed to traditional axial flow for the vapor stream. The system was evaluated for the biodegradation ofp-xylene (p-xylene) from a water-saturated air stream byPseudomonas putida ATCC 23973 immobilized onto sand. The biocatalyst was placed in the annular space between two cylindrical, porous stainless-steel membranes. Details of the reactor system are presented along with biological data verifying system performance. The feed flow rate andp-xylene concentration were varied between 60 and 130 cm³/min and 15–150 ppm, respectively. Continuous reactor operation was maintained for 80–200 h with removal efficiencies (based onp-xylene disappearance) between 80 and 95%. The effluent concentration histories were compared to determine the operating range of the bioreactor.     

表面活性剂对完全液相法制Cu-Zn-Al浆状催化剂结构和性能的影响

采用完全液相法制备了Cu-Zn-Al双功能浆状催化剂, 利用不同类型表面活性剂对其进行了修饰和改性. 通过N2气吸附、XRD和XPS等方法考察了表面活性剂类型对催化剂织构、物相以及表面性质的影响, 采用浆态床反应装置对其合成气一步法制备二甲醚的催化活性进行了评价, 讨论了催化剂结构与性能的关系. 结果表明, 表面活性剂主要是通过与活性金属的作用调节催化剂的表面性质、孔结构、相结构以及晶粒大小, 进而影响催化剂的催化活性; 非离子表面活性剂总体上对催化剂的性能有促进作用, 阳离子表面活性剂和阴离子表面活性剂对催化剂性能存在不利影响; 表面活性剂与活性金属作用的强弱是影响性能的关键.     

催化膜和催化膜反应器: 整合的高效和环保催化过程

 The design of new heterogeneous photooxygenation systems able to employ visible light, oxygen, mild temperatures, and solvent with a low environmental impact has been investigated. In particular, the heterogenization of decatungstate (W10O4-32), a polyoxometalate with photocatalytic activity in oxidation reactions, has been carried out in polymeric membranes of polyvinylidenefluoride. The polymeric catalytic membranes prepared by phase inversion technique have been successfully applied in the aerobic mineralization of phenol in water, which was used as an example of organic pollutant. In order to evaluate the effect of the polymeric environment on the overall catalyst behavior, we have also heterogenized the decatungstate (opportunely functionalized) in perfluorinated membrane made of Hyflon. The photocatalytic composite membranes are characterized by different and tuneable properties depending on the nature of the polymeric micro-environment, in which the catalyst is confined. Moreover, the selective separation function of the membrane results in enhanced performance in comparison with homogeneous reactions.     

青霉素对乳酸-丙酮-溴酸钾-硫酸锰-硫酸开放化学振荡体系的扰动

在连续搅拌反应器(CSTR)中,利用分析物脉冲微扰技术(APP)研究了青霉素对锰离子催化Belousov-Zhabotinsky(B-Z)开放化学振荡体系的影响。结果表明,青霉素浓度在2.97×10-7～5.50×10-5mol/L范围内,周期和振幅的变化率与所加入青霉素浓度的负对数呈良好的线性关系,相关系数分别为0.9981和0.9985;检出限为5.9×10-8mol/L。所建立的方法简便易行,每小时可进样15次。对可能的反应机理也进行了讨论。锰属于生命元素,在体内参与生物酶的合成与转化,研究青霉素对锰催化振荡反应体系的扰动对于理解生命运动更为有利。     

浆态床合成二甲醚复合催化剂失活原因探索

在反应温度260 ℃、压力5.0 MPa的条件下,对浆态床反应器中二甲醚合成复合催化剂的失活规律进行了研究.结果表明,Cu基催化剂失活较快是导致浆态床二甲醚合成催化剂不稳定的主要原因.通过分析Cu基催化剂在浆态床反应器和固定床反应器中的活性变化规律,发现在浆态床反应器中不能及时导出反应体系的H2O对催化剂的毒副作用导致了浆态床Cu基催化剂快速失活.对失活催化剂进行的TPR、XRD和SEM-EDS表征结果可以看出,Cu粒子的长大和积炭是Cu基催化剂失活的重要原因,与已有文献报道不同的是并未发现明显的Cu元素流失.     

Oxidative coupling of methane in a fixed bed reactor over perovskite catalyst： A simulation study using experimental kinetic model

The oxidative coupling of methane （OCM） to ethylene over a perovskite titanate catalyst in a fixed bed reactor was studied experimentally and numerically. The two-dimensional steady state model accounted for separate energy equations for the gas and solid phases coupled with an experimental kinetic model. A lumped kinetic model containing four main species CH4, O2, COx （CO2, CO）, and C2 （C2H4 and C2H6） was used with a plug flow reactor model as well. The results from the model agreed with the experimental data. The model was used to analyze the influence of temperature and feed gas composition on the conversion and selectivity of the reactor performance. The analytical results indicate that the conversion decreases, whereas, C2 selectivity increases by increasing gas hourly space velocity （GHSV） and the methane conversion also decreases by increasing the methane to oxygen ratio.