Alkoxysilane modification of a Ti‐based catalyst system for ethylene dimerization: A step forward in enhancing productivity and selectivity

Alkoxysilanes were used as novel enhancing agents in the Ti‐based catalyst for the highly selective ethylene dimerization to butene‐1. The dimerization of ethylene was carried out using the homogeneous Ti(OBu)₄/THF/TEA/alkoxysilane catalyst system, where Ti(OBu)₄, THF (tetrahydrofuran), TEA (triethylaluminum), and alkoxysilane were used as catalyst, additive, activator, and modifier, respectively. The nature and concentration of alkoxysilanes on the dimerization rate, catalyst yield, by‐products production, and selectivity to butene‐1 were investigated in detail. It was found that the performance of alkoxysilanes assisted with the class of the Ti‐based catalyst system, developed in this work, has been furthered by high productivity and selectivity with respect to the bare catalyst system. It proved that alkoxysilanes could play an excellent improving role in the selective ethylene dimerization process. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44615.     

Photoinitiated polymerization in ionic liquids and its application

Ionic liquids (ILs) are low‐melting organic salts often liquid at room temperature, whose unique properties are the reason of increasing interest for their applications as solvents, reaction media and functional additives. The exceptional properties of ILs have proved to be particularly useful in polymer science giving the potential to produce polymeric materials with improved properties or to immobilize ILs in polymer matrices while keeping their special characteristics. One of the possibilities is polymerization in ILs which can also affect positively polymerization reactions. An especially attractive technique is photopolymerization due to the ease of process control, short reaction time and ambient working temperature. This review gives a literature survey of developments in photopolymerization processes carried out in ILs as well as applications of these processes. It covers both the photopolymerization in ILs as well as photopolymerization of IL monomers. The first part presents a short overview of physicochemical and photochemical properties of ILs; it includes also photochemical reactions and photoinitiation of polymerization in ILs. The second part covers both the basic research (kinetics of photopolymerization including polymerization rate coefficients and polymerization of IL monomers) as well as applications of UV‐induced polymerization in ILs. © 2016 Society of Chemical Industry     

Kinetics of phase formation in the Ln–O–S (Ln=La,Gd, Y) systems during oxide sulfidation in ammonium thiocyanate vapor

Kinetics and mechanism of phase formation in the Ln–O–S (Ln=La, Gd, Y) systems during Ln₂O₃ sulfidation in ammonium thiocyanate vapor and the identified sequence of transformations of obtained phases in the temperature range 873‐1273 K have been studied. The kinetic dependencies for the reactions involved were fitted by the Jander equation for topochemical heterogeneous reactions with a squared correlation coefficient R²=.99. The reaction rate constants, pre‐exponential factors, and effective activation energies for the reaction formation of compounds have been calculated, and approximate times and low temperatures for the formation of particular phases have been found.     

Kinetics of Solvent Extraction of Iron(III) from Sulfate Medium by Purified Cyanex 272 using a Lewis Cell

Abstract

The kinetics of the forward and backward extraction of the title process have been investigated using a Lewis cell operated at 3 Hz and flux or (F) – method of data treatment. The dependences of (F) in the forward extraction on [Fe³⁺], [H₂A₂]_(o), pH, and [HSO₄ ^?] are 1, 0.5, 1, and ?1, respectively. The value of the forward extraction rate constant (k _f ) has been estimated to be 10^?7.37 kmol^3/2 m^?7/2 s^?1. The analysis of the experimentally found flux equation gives the following simple equation: F _f =10^0.13 [FeHSO₄ ²⁺] [A^?], on considering the monomeric model of BTMPPA and the stability constants of Fe(III)‐HSO₄ ^? complexes. This indicates the following elementary reaction occurring in the aqueous film of the interface as rate determining: [FeHSO₄]²⁺+A^?→[FeHSO₄.A]⁺. The very high activation energy of 91 kJ mol^?1 supports this chemical reaction step as rate-determining. The negative value of the entropy change of activation (?94 J mol^?1 K^?1) indicates that the slow chemical reaction step occurs via the S_N2 mechanism.

The backward extraction rate can be expressed by the equation: F _b =10^?5.13 [[FeHSO₄A₂]]_(o) [H⁺] [H₂A₂]_(o) ^?0.5. An analysis of this equation leads to the following chemical reaction step as rate-determining: [FeHSO₄A₂]_(int)→[FeHSO₄A]+A_(i) ^?. However, the activation energy of 24 kJ mol^?1 suggests that the backward extraction process is intermediate controlled with greater contribution of the diffusion of one or the other species as a slow process. The equilibrium constant obtained from the rate study matches well with that obtained from the equilibrium study.     

BATCH DRYING OF SHELLED CORN IN TWO-DIMENSIONAL SPOUTED BEDS WITH DRAFT PLATES

ABSTRACT

Geometrically similar spouted beds with draft plates were used to obtain the drying characteristics of freshly harvested shelled corn with 0.28 to 0.31 kg/kg initial moisture content at different air inlet temperatures and bed heights. Thermal equilibrium between air and grains was achieved at minimum spouting conditions. The drying kinetics of shelled corn in a drafted two-dimensional spouted bed was found to be of the "thin layer" type. Expressions for the model parameters in Page's equation accounting for the bed geometry, grain moisture content, and drying conditions were developed.     

PYRENE ENCAPSULATED ALGINATE BEAD TYPE FOR SUSTAINED RELEASE IN BIODEGRADATION: PREPARATION AND CHARACTERISTICS

A novel method for preparation of pyrene encapsulated alginate beads for controlled release delivery of pyrene is reported in this study. Five different bead types that varied on the organic phase for pyrene delivery, presence or absence of polyvinyl alcohol (PVA) and boric acid treatment were prepared. Based on the pyrene release profile, silicone oil encapsulated in PVA-alginate bead was selected where encapsulation efficiency was more than 99% without any solvent leakage. Silicone oil encapsulation was further confirmed in microscopy observations. Pyrene release behavior from the beads was explained by a diffusion controlled first order release (R² > 0.96). Reusability of this bead was demonstrated, where pyrene was loaded from an external medium in a non-destructive way. Application of the system was finally established in a biodegradation study using Mycobacterium frederiksbergense, where simultaneous release and removal of pyrene along with appearance of pyrene metabolites was observed.     

DRYING OF POWDERY MATERIALS IN A PULSED FLUID BED DRYER

ABSTRACT

Drying of recycled polypropylene powder was studied experimentally in a laboratory pulsed fluid bed dryer (PFB) with relocated air stream. It was proved that fluidization of fine particles having a large specific surface area and a broad size distribution is technically feasible when using the composite supporting grid. Drying and hydrodynamic characteristics for a pulsed fluid bed of fine particles are found to be similar to the ones for coarse particles. Equations for minimum pulsed fluidization velocity, pressure drop, and surface and volumetric heat transfer coefficients are given.     

锅炉受热面复合陶瓷涂层抗高温SO2腐蚀性能

针对燃煤锅炉受热面存在的高温腐蚀问题,采用料浆法在20G钢材表面制备复合陶瓷涂层,烧结后的复合陶瓷涂层表面较为致密,涂层与基材具有良好的结合状态。对喷涂及未喷涂陶瓷涂层钢片在SO₂腐蚀气氛环境下的抗高温腐蚀性能进行试验,并采用热分析动力学方法对试验数据进行处理,结果表明,在400~500℃温度范围内,两种试样的腐蚀过程均符合一维扩散反应动力学模式,计算求得喷涂涂层钢片腐蚀反应活化能低于未喷涂涂层钢片,涂层具有较好的抗高温腐蚀性能。对腐蚀试验后试样的形貌、成分和物相分析结果显示,涂层在SO₂气氛下腐蚀后,表面生成K₂SO₄晶粒,但由于涂层较为致密,阻止了S的扩散,内部基本没有检测到K₂SO₄的存在。     

臭氧化去除水中对硝基氯苯动力学及机理

引言 对硝基氯苯(pCNB)广泛应用于农药、染料、医药、防腐剂等工业领域.随着工业废水的排放,我国一些主要水体中均有pCNB的检出[1-2].     

纳米钛酸锶钡粉体制备及其对水中Cd2+吸附行为

采用草酸盐化学共沉淀法制备了草酸氧钛锶钡前驱体,通过905℃高温煅烧,制得了高纯纳米钛酸锶钡,并利用SEM、TEM、FT-IR和XRD对其进行了表征;并将该粉体应用于水中重金属镉离子的吸附.结果表明：该法合成的钛酸锶钡粉体为球形,钙钛矿结构,平均粒径为36 nm.对水中的镉离子具有较强的吸附能力,其吸附量与介质的pH值有密切关系,吸附动力学符合Langmuir和Bangham速率方程所描述的规律;吸附等温线较好地符合Langmuir和Freundlich等温方程,吸附行为是自发的、放热的物理吸附过程.