Adsorption and desorption kinetics of hydrocarbons in FCC catalysts studied using a tapered element oscillating microbalance (TEOM). Part 2: numerical simulations

The factors affecting the adsorption and desorption kinetics in a TEOM are reviewed in detail with particular attention given to the assumptions required to obtain physical transport parameters from the data. Two models are presented to simulate TEOM adsorption data in the case that concentration differences down the catalyst bed can be neglected, as is appropriate when the amount of catalyst used is small, the carrier gas flowrate is large, and/or the adsorbate partial pressure is low. In the first model, the effective diffusion coefficient, D_e, is taken to be constant. In the second model, the effective diffusion coefficient is assumed to obey the Darken equation, D_e=D₀/(1−θ). The TEOM results obtained on n-hexane, n heptane, n-octane, toluene and p-xylene on a commercial FCC catalyst and on pure rare-earth exchanged zeolite Y under non-reacting conditions (373-) are analysed in detail. It is found that intracrystalline diffusion is not the limiting factor affecting the overall rates of adsorption and desorption for the systems studied. Instead, it is the transport of molecules between the adsorbed and vapour phases at the edge of zeolite crystallites that is the limiting transport step affecting the overall kinetics. For the FCC catalyst, the limiting step is the transport of molecules at the zeolite-matrix interface rather than, say, the matrix-vapour interface. Local rate constants for the desorption of the hydrocarbons at the rate-controlling interface have been obtained.     

Adsorption and desorption kinetics of hydrocarbons in FCC catalysts studied using a tapered element oscillating microbalance (TEOM). Part 1: experimental measurements

An experimental procedure to measure the adsorption and desorption kinetics of hydrocarbons in fluid catalytic cracking (FCC) catalysts using a tapered element oscillating microbalance is described. It enables adsorption rates to be measured on a timescale of about . Experiments using n-hexane, n-heptane, n-octane, toluene and p-xylene were performed on both a commercial FCC catalyst and a pure rare-earth exchanged zeolite Y sample under non-reacting conditions (temperatures of 373-). Heats of adsorption for these hydrocarbons are reported. The overall adsorption and desorption kinetics are found to depend on carrier gas flowrate in cases when adsorption is strong indicating that the length of the catalyst bed can have a significant influence on the observed kinetics. However, at high carrier gas flowrates the overall adsorption and desorption kinetics do not depend on the amount of catalyst present. It is found that the rates of adsorption and desorption of the hydrocarbons studied are the same for the FCC catalyst as for the pure zeolite Y sample. This means that mass transport in the matrix component of the FCC catalyst is rapid and not a limiting step in the adsorption process for the hydrocarbons studied in this work.     

Preparation and sorption studies of β‐cyclodextrin/epichlorohydrin copolymers

β‐Cyclodextrin (β‐CD) copolymer materials were synthesized by reacting different mole ratios (1 : 15, 1 : 25 and 1 : 35) of β‐CD with epichlorohydrin (EP). The products were characterized using N₂ porosimetry, Fourier Transform Infrared spectroscopy, ¹³C CP‐MAS NMR spectroscopy, thermogravimetry analysis, elemental (C and H) analysis, and scanning electron microscopy. The sorption properties in aqueous solution were studied using p‐nitrophenol (PNP) with UV–Vis spectrophotometry. Sorption isotherms were obtained at pH 4.6 and three temperatures (22, 35, and 45°C) and at pH 10.3 at 22°C. The isotherms were analyzed using the BET isotherm model and the sorption parameters provided estimates of the surface area, sorption capacity, and isosteric heats of sorption for each polymeric material. The estimated surface areas are as follows: 58.2, 52.1, and 90.1 m²/g at pH 4.6. At pH 10.3, the estimated surface areas are 44.2, 40.5, and 58.5 m²/g, respectively. The removal efficiency of PNP by the polymeric materials ranged between 4.5 and 58% for the conditions investigated whereas the isosteric heats ranged between ?24.5 and ?13.6 kJ/mol. Removal efficiencies were concluded to strongly depend on the sorption conditions such as pH, temperature, and the relative amounts of sorbent and dye in aqueous solution. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Arsenic adsorption from contaminated water on Fe(III)‐coordinated amino‐functionalized poly(glycidylmethacrylate)‐grafted TiO2‐densified cellulose

BACKGROUND: The main aim of this study is to determine the sorptive potential of a novel anion exchanger, Fe(III)‐coordinated amino‐functionalized poly(glycidylmethacrylate)‐grafted TiO₂‐densified cellulose (AM‐Fe‐PGDC) for arsenic(V) removal from aqueous solutions by batch technique. RESULTS: The adsorbent was characterized using infrared spectroscopy, powder X‐ray diffraction, scanning electron microscopy, thermogravimetry and potentiometric titrations. The effective pH for removal was 6.0. The adsorption rate was influenced by initial metal ion concentration and contact time. The equilibrium was achieved within 1.5 h and follows a pseudo‐second‐order kinetic model. The adsorption capacity for As(V) calculated using the Langmuir isotherm equation was 105.47 mg g^?1. The AM‐Fe‐PGDC developed was used to remove As(V) from simulated groundwater. Regeneration experiments were attempted for four cycles using 0.1 mol L^?1 NaCl solution. CONCLUSION: It was found that AM‐Fe‐PGDC is very efficient for the removal of As(V) from aqueous solutions. © 2012 Society of Chemical Industry     

Preparation and permeation characterization of β‐zeolite‐incorporated composite membranes

In this work, several β‐zeolite‐incorporated polymer composite membranes were fabricated with the solution‐casting method. The zeolite loadings were 10, 20, and 30 wt %, respectively. Scanning electron microscopy characterization showed that the zeolite particles could be uniformly distributed in the whole polymer matrix. Gas permeation results demonstrated that after the incorporation of the same β‐zeolite, the polyimide exhibited a significant increase in gas permeability but a decrease in permselectivity, and both were quite pronounced at high zeolite loadings; this resulted from the loose structure that formed. The poly(ether sulfone) composite membranes showed obvious increases in both permeability and selectivity, and the permeability increase was considerably greater at higher zeolite loadings. The permselectivity increase could possibly be attributed to the pore sieving and preferential adsorption of β‐zeolite entities for the test gases as the heat treatment may have resulted in the formation of a defect‐free microstructure. However, breakthrough of the upper‐bound line was not achieved for these composite membranes, as reflected by Robeson plots. Our results suggest that changes in membrane performance not only are attributable to the properties and content of β‐zeolite particles but also depend on the heterogeneous microstructure created by zeolite entities. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Transport Properties of Modified Montmorillonite‐Poly(ε‐caprolactone) Nanocomposites

A series of montmorillonite‐poly(ε‐caprolactone) nanocomposites were prepared according to a two‐stage procedure. In the first step Na‐type silicate clay was cation exchanged with protonated 12‐aminolauric acid. In the second step ε‐caprolactone was intercalated in the modified clay and ring‐opening polymerized. The clay content was varied regularly from 0 to 44 wt.‐%, with exfoliation of the silicate layers being detected by X‐ray diffraction in the nanocomposites dispersing up to at least 16 wt.‐% clay. Crystallization of poly(ε‐caprolactone) was not prevented in the nanocomposites, although it proceeded to a lower extent/order than in a homopolymer sample. The transport properties were investigated using water or dichloromethane as vapor permeants. In each case, a dual sorption behavior was observed as a function of the vapor activity because of the occurrence of different sorption mechanisms. The permeability of the nanocomposites to either permeant decreased with increasing clay content. In particular, the permeability behavior to water was largely dominated by the diffusion parameter.     

Simultaneous Adsorption of SO2, NO,and CO2 by K2CO3‐Modified γ‐Alumina

The simultaneous adsorption of SO₂, NO, and CO₂ on K₂CO₃‐modified γ‐alumina under different operating conditions was studied in a fixed‐bed reactor. The experimental results showed that the influence of a temperature increase on the simultaneous adsorption of the three gases was complex and different from the effects seen when both chemical adsorption and competitive adsorption existed. An increase in O₂ concentration and small amounts of water could enhance the adsorption of SO₂ and NO while the adsorption of CO₂ was not influenced. The breakthrough curves of the simultaneous adsorption experiments suggested that the investigated adsorbent may be a good candidate for the simultaneous adsorption of SO₂, NO, and part of the CO₂ while the adsorption capacity for CO₂ still needs to be enhanced.     

Cationic copolymers of α,β‐poly‐(N‐2‐hydroxyethyl)‐DL‐aspartamide (PHEA) and α,β‐polyasparthylhydrazide (PAHy): synthesis and characterization

In the present study the derivatization of two water‐soluble synthetic polymers, α,β‐poly(N‐2‐hydroxyethyl)‐DL ‐aspartamide (PHEA) and α,β‐polyasparthylhydrazide (PAHy), with glycidyltrimethylammonium chloride (GTA) is described. This reaction permits the introduction of positive charges in the macromolecular chains of PHEA and PAHy in order to make easier the electrostatic interaction with DNA. Different parameters affect the reaction of derivatization, such as GTA concentration and reaction time. PHEA reacts partially and slowly with GTA; on the contrary the reaction of PAHy with GTA is more rapid and extensive. The derivatization of PHEA and PAHy with GTA is a convenient method to introduce positive groups in their chains and it permits the preparation of interpolyelectrolyte complexes with DNA. © 2000 Society of Chemical Industry     

Ruthenium(II)‐Catalyzed Protocol for Preparation of Diverse α,β‐ and β,β‐Dihaloenones from Diazodicarbonyls

Efficient one‐step syntheses of α,β‐ and β,β‐dihaloenones were achieved by ruthenium(II)‐catalyzed reactions between cyclic or acyclic diazodicarbonyl compounds and oxalyl chloride or oxalyl bromide in moderate to good yields. This methodology offers several significant advantages, which include ease of handling, mild reaction conditions, one‐step reaction, and the use of an effective and non‐toxic catalyst. The synthesized compounds were further transformed into highly functionalized novel molecules bearing aromatic rings on the enone moiety using the Suzuki reaction.

     

Photothermal methods and atomic force microscopy images applied to the study of poly(3‐hydroxybutyrate) and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) dense membranes

Thermal and transport properties of some polyhydroxyalkanoates (PHAs), poly‐3‐hydroxybutyrate and poly‐3‐hydroxybutyrate‐co‐3‐hydroxyvalerate copolymers at different concentrations (8, 14, and 22%), were studied by using photoacoustic and photothermal techniques. Mass diffusion coefficients were obtained for carbon dioxide and oxygen by using a gas analyzer. Specific heat capacity measurements were performed by monitoring temperature of the samples under white light illumination against time. Thermal diffusivities were determined by using the open photoacoustic cell configuration. The results were discussed considering the incorporation of hydroxyvalerate units in the poly(3‐hydroxybutyrate) unit cell and were correlated with atomic force microscopy images of the upper surface of membranes. New information on transport properties of PHAs is provided. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1491–1497, 2005     

Surface characteristics of poly(γ‐alkyl α l‐glutamate)s with different alkyl groups

A series of poly(γ‐alkyl α L ‐glutamate)s with different alkyl groups were synthesized by the ring opening polymerization of corresponding α‐amino acid N‐carboxyanhydrides. The characteristics of these polyglutamate surfaces were evaluated by attenuated total reflectance Fourier transform infrared spectroscopy spectra, water contact angle, water absorption, protein adsorption, and platelet adhesion measurements. Changing the length of the alkyl side chain provides a unique opportunity to study the influence of carbon number in the alkyl group on the surface properties of the polyglutamates. Water contact angle and water absorption data show that the hydrophilicity of these polyglutamate surfaces decreases with the increasing of methylene in the alkyl group. Protein adsorption on these polyglutamate surfaces increases with the enhancing of surface hydrophobicity. However, the changes in platelets adhesion could be attributed to the hydrophilicity/hydrophobicity of the polyglutamates and the specific effect of alkyl group. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Toluene‐vapor sorption of chemically modified methyl methacrylate‐co‐chloromethyl styrene copolymers with N,N,‐dimethyl‐1,3‐propanediamine measured with a quartz crystal microbalance

The sorption properties of toluene vapor were measured for methyl methacrylate (MMA)‐co‐chloromethyl styrene (CMSt) copolymers chemically modified with N,N‐dimethyl‐1,3‐propanediamine (DMPDA) to develop a novel quartz crystal microbalance toluene‐vapor sensor coating. The influence of the structure of the comonomer, the composition of the copolymer, and the film thickness on the toluene sorption properties were investigated. The modified MMA–CMSt copolymers were capable of large, fast, and reversible sorption versus the modified styrene–CMSt copolymers. The largest sorption capacity was obtained for MMA–CMSt–DMPDA with a 96 mol % CMSt concentration. These behaviors were explained by a combination of the plasticization of the copolymers by the introduction of bulky DMPDA at lower CMSt concentrations and the formation of a loosely crosslinked structure at higher CMSt concentrations. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Pyromellitic dianhydride‐modified β‐cyclodextrin microspheres for Pb(II) and Cd(II) adsorption

In this work, the pyromellitic dianhydride (PMDA)‐grafted β‐cyclodextrin (β‐CD) microspheres have been prepared for the removal of lead and cadmium metal ions in aqueous solution by a batch‐equilibration technique. The effects of the pH of the solution, contact time, and initial metal concentration were studied. The adsorption capacities for the two metal ions increase significantly as a large number of carboxyl groups are present on the microspheres surface. The equilibrium process is better described by the Langmuir isotherm than the Freundlich isotherm. The maximum adsorption capacities are 135.69 and 92.85 mg g^?1 for Pb(II) and Cd(II), respectively. Kinetic studies show good correlation coefficients for a pseudosecond‐order kinetic model, confirming that the sorption rate is controlled by chemical adsorption. The regeneration of the adsorbent can be carried out by treating the loaded microspheres with 0.2 (mol L^?1) HCl obtaining high desorption rate for the two metal ions. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Synthesis of poly(β‐pinene)‐g‐polystyrene from allylic brominated poly(β‐pinene)

Poly(β‐pinene) was brominated by N‐bromosuccinimide on the allylic carbons. Then the brominated product was activated by AlEt₂Cl to initiate the polymerization of styrene to give a β‐pinene/styrene graft copolymer. AlEt₂Cl was selected because it alone could not initiate the polymerization of styrene. The obtained graft copolymer was characterized by GPC, ¹H‐NMR, and DSC measurements, respectively. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 599–603, 2000     

Palladium‐nanoparticle intercalated vermiculite for selective hydrogenation of α,β‐unsaturated aldehydes

Palladium nanoparticles were generated in the interlamellar region of swelling 2:1 type vermiculite clay using an adsorption excess isotherm. An adsorption excess isotherm was constructed for vermiculite after exchanging the exchangeable Na⁺ ions in the interlamellar region using a binary liquid mixture (ethanol:toluene). Based on adsorption excess isotherm, 1% w/w palladium was intercalated into the interlamellar space of vermiculite. The Pd‐intercalated vermiculite was characterized by X‐ray diffraction, transmission electron microscopy and atomic absorption spectroscopy. The 1% w/w Pd‐intercalated vermiculite was tested for its catalytic activity towards selective hydrogenation reactions involving some α,β‐unsaturated carbonyl compounds using a pulse reactor and its catalytic activity was compared with commercial 1% Pd/C. The intercalated catalyst was found to be very selective towards the desired product of unsaturated alcohols. Copyright © 2007 Society of Chemical Industry     

Adsorption and drug release based on β‐cyclodextrin‐grafted hydroxyapatite composite

In this study, β‐cyclodextrin (β‐CD) was covalently grafted on hydroxyapatite (HA) using a coupling agent to improve the drug loading capacity and prolong the drug release. The binding of β‐CD on the HA surface was confirmed by Fourier transformation infrared spectroscopy, thermal gravimetric analysis, and X‐ray powder diffraction. The adsorption capacity of ofloxacin on β‐CD‐grafted hydroxyapatite (β‐CD‐g‐HA) composite was found to be 30 mg g^?1 at 37°C and 24 h. The adsorption process is spontaneous, given the negative values of free energy change. Compared with the release of ofloxacin loaded on HA, the release of ofloxacin loaded on β‐CD‐g‐HA was slowed down 28% and 21% in pH 2.0 and pH 7.4 buffer media at 2 h, respectively. Biocompatibility of β‐CD‐g‐HA was assessed by MTT assay, and the result showed that it had no cytotoxicity. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Copper(I)‐Catalyzed Stereoselective Synthesis of (E)‐α‐Alkynyl‐α,β‐unsaturated Esters from a Terminal Alkyne,Diazoesters and Aldehydes

A new synthetic method for α‐alkynyl‐α,β‐unsaturated esters is presented herein. The method is based on a copper(I)‐catalyzed three‐component reaction of a terminal alkyne, diazoesters and aldehydes. The reaction is featured by mild conditions, high yields and excellent stereoselectivity. Cu(I) carbene migratory insertion is proposed as the key step in the transformation.