帘式折流片换热器壳程流体流动死区

对帘式折流片换热器壳程流体流动死区大小及分布规律进行了数值模拟和实验研究。研究表明,帘式折流片换热器壳程流体流动死区大小随着Re的增加而降低;流动死区的大小和分布规律受折流栅装配方式的影响,折流栅同向装配时壳程死区小于折流栅对称装配,当壳程Re分别为5000、10000和15000时,折流栅同向装配时的帘式折流片换热器壳程死区分别为折流栅对称装配时的50.5%、51.6%、43.0%。     

Poly (N‐methylaniline)/multi‐walled carbon nanotube composites—Synthesis,characterization, and electrical properties

This study described the synthesis of hydrochloric acid (HCl)‐doped poly (N‐methylaniline) (PNMA) with carboxylic groups containing multi‐walled carbon nanotubes (c‐MWNTs) via in situ polymerization. Based on the π–π electron interaction between c‐MWNTs and the N‐methylaniline monomer and the hydrogen bond interaction between the carboxyl groups of c‐MWNTs and imine groups of N‐methylaniline monomers, N‐methylaniline molecules were adsorbed on the surface of c‐MWNTs and polymerized to form PNMA/c‐MWNT composites. Scanning electron microscopy images showed that both the thinner fibrous phase and the larger block phase could be observed. The individual fibrous phases had diameters from several tens to hundreds of nanometers, depending on the PNMA content. Transmission electron microscopy proved that PNMA/c‐MWNTs composite fibrous phases were core (c‐MWNT)‐shell (PNMA) tubular structures. The structure of PNMA/c‐MWNT composites was characterized by FTIR, UV–vis spectra, and X‐ray diffraction patterns. The electrical conductivities of PNMA/c‐MWNT composites were much higher than that of PNMA without c‐MWNTs. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2356–2361, 2006     

A two‐zone model for fluid catalytic cracking riser with multiple feed injectors

Developments in modeling of the fluid catalytic cracking (FCC) process have progressed along two lines. One emphasizes composition‐based kinetic models based on molecular characterization of feedstocks and reaction products. The other relies on computational fluid dynamics. The aim is to develop an FCC model that strikes a balance between the two approaches. Specifically, we present an FCC riser model consisting of an entrance‐zone and a fully developed zone. The former has four overlapping, fan‐shaped oil sprays. The model predicts the plant data of Derouin et al. and reveals an inherent two‐zone character of the FCC riser. Inside the entrance zone, cracking intensity is highest and changes rapidly, resulting in a steep rise in oil conversion. Outside the entrance zone, cracking intensity is low and varies slowly, leading to a sluggish increase in conversion. The two‐zone model provides a computationally efficient modeling approach for FCC online control, optimization, and molecular management. © 2014 American Institute of Chemical Engineers AIChE J, 61: 610–619, 2015     

CFB密相区大颗粒横向扩散系数的CPFD模拟

运用一种离散单元法（DEM）计算颗粒流体力学（CPFD）对尺寸为900 mm×100 mm×1200 mm的准三维流化床的密相区大颗粒扩散行为进行研究。模拟之前,依照前人实验研究对CPFD方法进行验证,模拟结果与实验结果符合较好,证明了CPFD方法模拟的有效性。模拟中通过注入示踪粒子的方法来研究大颗粒在密相区中的横向扩散系数,研究了流化风速、颗粒直径对颗粒横向扩散系数的影响。模拟结果显示,气泡是引起密相区内颗粒混合的主要因素;随着流化风速增加,颗粒横向扩散系数变大;随着颗粒直径增大,颗粒横向扩散系数减小。     

Effect of dead volumes on the performance of an industrial‐scale simulated moving‐bed Parex unit for p‐xylene purification

The cyclic steady state (CSS) of the industrial‐scale, seven‐zone, simulated moving‐bed (SMB) unit for p‐xylene (p‐x) purification (Parex unit) with three types of dead volumes—bed lines, push‐around and pump‐around circulation lines, and bed heads—is analyzed. In particular, the effects of the size and level of hydrodynamic dispersion of each dead volume on process performance and on its CSS are studied in detail. The circulation lines change the CSS behavior from ‐periodic to ‐periodic, where is the switching interval and is the number of columns in each adsorbent chamber. A high level of axial dispersion in the bed lines, characterized by Péclet numbers smaller than 100, affects the p‐x purity. Moreover, the bed lines lower the average p‐x concentration in the extract, which reduces the p‐x recovery. If the small time lags introduced by the circulation lines are neglected, it is possible to develop a detailed process model that considers the operation of the Parex unit over a single switching interval as opposed to a full cycle, and whose CSS solution can be efficiently computed using a full‐discretization approach. Finally, it is shown that the volume of the bed heads influences significantly the performance of the Parex unit, and that its impact on the location of the operating point with respect to the boundaries of the separation region can be approximately taken into account using the standard true moving‐bed‐SMB equivalence rules if they are corrected for the presence of extra interparticle fluid. © 2015 American Institute of Chemical Engineers AIChE J, 62: 241–255, 2016     

Preparation and characterization core‐shell particles and application for E‐Ink

the core‐shell particles were prepared by dispersion copolymerization. The core‐shell particles were characterized with Fourier‐transform infrared spectroscopy, Transmission electron microscope and scanning electron microscope. The dispersion stability and electrophoretic performance of core‐shell particles were studied in the mixed medium of tetrachloroethylene and cyclohexance. Microcapsules containing the core‐shell particles were prepared by coacervation. Results showed that the core‐shell particles had good dispersion stability and it had no electric response, which could be used as grounding particles for E‐Ink. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1195–1199, 2007     

Application of ultramicroelectrodes in studies of homogeneous catalytic reactions—part II. A theory of quasi-first and second-order homogeneous catalytic reactions

The analytical expressions of quasi-first and second order homogeneous catalytic reactions with different diffusion coefficients at ultramicrodisk electrodes under steady state conditions are obtained by using the reaction layer concept. The method of treatment is simple and its physical meaning is clear. The relationship between the diffusion layer, reaction layer, the electrode dimension and the kinetic rate constant at an ultramicroelectrode is discussed and the factor effect on the reaction order is described. The order of a catalytic reaction at an ultramicroelectrode under steady state conditions is related not only to C^*_z/C^*_o but also to the kinetic rate constant and the dimension of the ultramicroelectrode; thus the order of reaction can be controlled by the dimension of the ultramicroelectrode. The steady state voltammetry of the ultramicroelectrode is one of the most simple methods available to study the kinetics of fast catalytic reactions.     

Stability of an inclined,pneumatically‐transported system of particles

A linear stability analysis is performed on the base‐state solution describing a pneumatically‐transported system inclined at an angle θ. One of two modes was found to be dominant, depending on the tilting angle: a low‐shear mode whose voidage eigenmode remains nearly symmetric from 0° < θ ≤ θ_c, and a “boundary layer” mode for θ > θ_c, marked by significant asymmetry throughout the domain and a high level of shear inside the thin regions adjacent to the walls. The critical angle θ_c increases with the amount of momentum and energy lost to particle–wall friction and collisions, respectively. The time‐evolution of the latter mode, superimposed onto the base‐state solution, reveals an alternating train of dense and dilute regions near the top of the domain, which agrees qualitatively with the development and propagation of bubbles in inclined systems observed in experiment. An analytic solution corresponding to a vertical system with a uniform base state was also derived to identify the instability mechanisms responsible for a class of non‐oscillatory transverse waves which exist in both vertical and tilted particle systems. © 2016 American Institute of Chemical Engineers AIChE J, 62: 2248–2258, 2016     

Suspension of solid particles in multi‐impeller three‐phase stirred tank reactors

Solids suspension characteristics in gas—liquid–solid three‐phase stirred tanks with multi‐impellers were experimentally examined. Minimum impeller speeds for ultimately homogeneous solid suspension have been measured stirred tank reactors. Three impellers were installed: two four‐pitched blade downflow disk turbines and one Pfaudler type impeller chosen to provide good gas dispersion and to accomplish off‐bottom suspension of solid particles, respectively. Gas dispersion causes an increase in particle sedimentation associated with a decrease in power consumption and as a result, minimum impeller speeds for ultimately homogeneous solid suspension increase with increasing gas flow rates. A correlation was developed to predict minimum impeller speeds for ultimately homogeneous solid suspension. The proposed correlation, which agrees satisfactorily with the experimental results, is expected to be useful in design and scale‐up.     

Polymer‐Supported Bisacetoxybromate(I) Anion –‐An Efficient Co‐Oxidant in the TEMPO‐Mediated Oxidation of Primary and Secondary Alcohols

A polymer‐bound reagent for the efficient oxidation of primary alcohols to aldehydes and secondary alcohols to ketones in the presence of a catalytic amount of 2,2,6,6‐tetramethyl‐1‐piperidinyloxyl (TEMPO) is described. The oxidation process is particular mild and allows one to prepare aldehydes with α‐chirality without racemization. This also includes the synthesis of α‐aminoaldehydes. In most cases, work‐up of this heavy metal‐free oxidation is achieved by simple filtration followed by removal of the solvent. Insight into the role of the bromate(I) anion in the oxidation process was gained from the TEMPO‐mediated oxidation of benzaldehyde in the presence of the hypochlorite anion loaded on an anion exchange resin.     

Carbohydrate-substituted phosphines as new ligands for two-phase catalysis – synthesis and application

The synthesis and catalytic application of a new class of polar hydrophilic phosphines for two-phase catalysis is described in full detail. Contrary to the well-known sulfonated phosphines the hydrophilic character of the ligands is attributed to a neutral carbohydrate moiety. Two general routes for the synthesis of monosaccharide substituted triarylphosphines are presented. In the first procedure protected halopyranoses and OH-substituted triphenylphosphines were combined under phase transfer conditions to generate carbohydrate-substituted phosphines. In a second more efficient protocol, the palladium-catalyzed coupling of suitable haloaryl glycosides with diphenylphosphine constitutes a new access to these ligands. The properties of the ligands in terms of solubility, surfactant activity, and partition between two non-miscible phases are discussed. In addition, superior catalytic performance compared to ionic hydrophilic ligands was demonstrated for important C–C coupling reactions such as the Suzuki, Heck, and hydroformylation reactions.     

Reactions in solid particles—A reappraisal of models

Models such as the Ishida–Wen, or even more commonly the shrinking core models (Ginstling–Brounshtein being an important example), have long been used in the analyses of reactions in particles, particularly in solid–solid systems. There have been a few analyses of the validity of the assumptions made in these models, but to date, no comparison has been undertaken of these models against a general model to delineate their regions of applicability in the parameter space. In this article, we present a general unsteady‐state model that subsumes the earlier models as special cases. Nondimensionalization leads to the identification of two governing parameters in the model, a diffusion‐reaction parameter, and a relative abundance parameter. By solving the general model and comparing the solutions with those of the approximate models in the parameter space, conditions under which the approximate models apply, and the errors that result from their application in other situations, have been identified. © 2012 American Institute of Chemical Engineers AIChE J, 58: 3161–3166, 2012     

Regioselective carbon-carbon bond formation in proteins with palladium catalysis; new protein chemistry by organometallic chemistry

Palladium-catalyzed reactions have contributed to the advancement of many areas of organic chemistry, in particular, the synthesis of organic compounds such as natural products and polymeric materials. In this study, we have used a Mizoroki-Heck reaction for site-specific carbon-carbon bond formation in the Ras protein. This was performed by the following two steps: 1) the His6-fused Ras protein containing 4-iodo-L-phenylalanine at position 32 (iF32-Ras-His) was prepared by genetic engineering and 2) the aryl iodide group on the iF32-Ras-His was coupled with vinylated biotin in the presence of a palladium catalyst. The biotinylation was confirmed by Western blotting and liquid chromatography-mass spectrometry (LC-MS). The regioselectivity of the Mizoroki-Heck reaction was furthermore confirmed by LC-MS/MS analysis. However, in addition to the biotinylated product (bF32-Ras-His), a dehalogenated product (F32-Ras-His) was detected by LC-MS/MS. This dehalogenation resulted from the undesired termination of the Mizoroki-Heck reaction due to steric and electrostatic hindrance around residue 32. The biotinylated Ras showed binding activity for the Ras-binding domain as its downstream target, Raf-1, with no sign of decomposition. This study is the first report of an application of organometallic chemistry in protein chemistry.     

Transient multi gas—solid reactions in a bubbling fluidized bed

A “multimodel” for gas‐solid reactions in a reacting particle has been applied to a bubbling fluidized bed reactor. The particle is tracked and bed and particle variables are determined continuously. The conservation equations of mass and heat with auxiliary relations are solved in an accelerating particle, which may rise or fall. The effects of bulk pressure, velocity and temperature, and particle diameter are studied. Heat and mass transfer coefficients may fluctuate up to 75% and 148% respectively. Doubling the pressure changes h_c by 75% and k_c by ?45%. Increase in pellet diameter reduces both h_c and k_c.     

Opto‐thermal properties of fibers XVIII—Skin‐core structures variations in nylon 6 fibers due to different annealing conditions

Nylon 6 fibers (Amilan) were annealed at constant temperature 140 ± 1°C for different time durations (1–10 h). Refractive indices have been previously measured interferometerically. Two independent techniques were used to study the optical anisotropy and density in these fibers. The first was the application of a multiple‐beam to determine the skin and core “mean” refractive indices and birefringence of the samples. The technique used multiple‐beam Fizeau fringes in transmission. The second technique was an acoustic method for measuring the density of the investigated fibers. The optical results were used to calculate the optical orientation factors for skin and core. The values of (Δα/3α₀), which depend upon the molecular structure of the polymer, remain constant and in agreement with the previous published data. The density results were used to calculate the degree of crystallinity of nylon 6 fibers. In addition, the results were used to calculate the mean square density fluctuation, the harmonic mean polarizability of the dielectric, specific refractivity of the isotropic dielectric and the virtual refractive index. Also, the number of monomer units per unit volume, and n₁ and n₂, which are the refractive indices of fully oriented fiber, were calculated and found to be (1.606 and 1.534). Hermans optical orientation functions have been compared with the generalized Lorentz‐Lorenz equation given by de Vries. Microinterferograms and curves are given for illustration. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3349–3360, 2001     

A new catalytic method for crosslinking of silicone polymers

The aim of our work was to develop a gelation process for polymerizing polydimethylsiloxane-α,ω-diols for pharmaceutical purposes. Three different gelling agents has been tried; among them, the prehydrolyzed tetraethoxysilane (TES 40) had the best performance. As initiators, several amines were investigated. The gelling time has been found to be correlated with the basicity, solubility, and diffusibility of the amines. The correlation between the thickness of the oligomer layer and the gelling time has also been investigated. The amount of the remaining initiator after the completion of the network formation has been determined, together with the time needed for its complete removal from the matrix. By using thermogravimetric methods it has been shown that no initiator is left in the matrix. The elastomers obtained by the present method were compared to those obtained by the usual catalysts, resulting in identical properties. The procedure developed is able to produce silicone oligomers for pharmaceutical purposes either in a continous or in a discontinous way. The procedure has several advantages in comparison with the conventional methods. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1705–1709, 1998     

Synthesis and electrorheological properties of polyaniline‐coated barium titanate composite particles

Polyaniline‐coated barium titanate composite particles were synthesized by surface grafting polymerization, in which five silane coupling agents with different terminal groups were used. The structure of composite particles was characterized by SEM, XRD, FTIR, and TGA, and the electrorheological properties were tested by rotational rheometer. The results show that polyaniline was coated on the surface of barium titanate particles to form the shell‐core structure. The yield stress of the electrorheological fluids based on polyaniline‐coated barium titanate composite particles is higher than that of polyaniline and barium titanate. Compared with PANI‐based electrorheological fluids (ERFs), the composite particles‐based ERFs have lower field‐off viscosity due to the molecular interaction. The yield stress of the ERFs, as well as density of the composite particles, was affected by the groups at terminal of silane coupling agents. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and characterization of trilayer core–shell polysilsesquioxane–fluoroacrylate copolymer composite emulsion particles

Polysilsesquioxane–fluoroacrylate copolymer [poly(methyl methacrylate)–butyl acrylate–dodecafluoroheptyl methacrylate)] (FPSQ) composite latex particles with a trilayer core–shell morphology were manufactured by seeded emulsion polymerization, where PSQ latex particles bearing reactive methacryloxypropyl moieties were first produced by the hydrolysis‐condensation of (3‐methacryloxypropyl)trimethoxysilane, and then they were utilized as seeds, with methyl methacrylate, butyl acrylate, and dodecafluoroheptyl methacrylate as the inner and outer shell monomers. Fourier‐transform infrared spectra and ¹H‐NMR confirm the structure of the FPSQs. Transmission electron microscopy and scanning electron microscopy demonstrate that the obtained composite emulsion particles emerge with the trilayer core–shell pattern. Due to the anchoring of PSQ nanoparticles, the thermal stabilities of the FPSQ films are strengthened, and the resistance to heat is gradually improved along with the increase of the fluoroacrylate dose in the polymer matrix composite. X‐ray photoelectron spectroscopy, atomic force microscopy (AFM), and hydrophobicity investigations indicate that the fluorinated chain segments tend to concentrate at the film–air two‐phase interface. In addition, the AFM result denotes that importing more fluorine into the FPSQ hybrid material will engender greater phase separation and enrichment of the fluoroalkyl segments and a rougher morphology. Thus, the water contact angle of the FPSQ film can ultimately reach 121.4°. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44845.