MFI zeolite as adsorbent for selective recovery of hydrocarbons from ABE fermentation broths

1-Butanol and butyric acid are two interesting compounds that may be produced by acetone, butanol, and ethanol fermentation using e.g. Clostridium acetobutylicum. The main drawback, restricting the commercialization potential of this process, is the toxicity of butanol for the cell culture resulting in low concentrations of this compound in the broth. To make this process economically viable, an efficient recovery process has to be developed. In this work, a hydrophobic MFI type zeolite with high silica to alumina ratio was evaluated as adsorbent for the recovery of butanol and butyric acid from model solutions. Dual component adsorption experiments revealed that both butanol and butyric acid showed a high affinity for the hydrophobic MFI zeolite when adsorbed from aqueous model solutions. Multicomponent adsorption experiments using model solutions, mimicking real fermentation broths, revealed that the adsorbent was very selective to the target compounds. Further, the adsorption of butyric and acetic acid was found to be pH dependent with high adsorption below, and low adsorption above, the respective pKa values of the acids. Thermal desorption of butanol from MFI type zeolite was also studied and a suitable desorption temperature was identified.     

Apparent yield stress estimation in xanthan gum solutions and fermentation broths using a low-cost viscometer

The apparent yield stress, a rheological property important in determining the extent of mixing in xanthan fermentations as well as the suspending abil     

Rapid analysis of antibiotic-containing mixtures from fermentation broths by using liquid chromatography-electrospray ionization-mass spectrometry and matrix-assisted laser desorption ionization-time-of-flight-mass spectrometry

A crucial step in the isolation of antibiotic substances is establishing whether or not the isolated material represents a new chemical entity. Because of the importance of molecular weight to this process--known as dereplication--mass spectrometry has traditionally played an active role. In this communication a strategy for utilizing liquid chromatography-mass spectrometry (LC/MS) for novelty assessment is described. Crude extracts (20-50 μg) are chromatographed by conventional bore high-performance liquid chromatography (1 mL/min) after which a postcolumn split to divert roughly one-tenth of the sample to the mass spectrometer for molecular weight determination by electrospray ionization (ESI) mass spectrometry. The majority of the effluent is sent to a UV detector and ultimately collected as 1-min fractions for biological testing. As a secondary confirmation of molecular weight, an aliquot of each fraction (< 5%) is taken for analysis by matrix-assisted laser desorption ionization (MALDI). The improved efficiency of this approach over more traditional schemes utilizing off-line fraction collection and conventional ionization methods can be explained by several factors. First, the superior sensitivity of ESI and MALDI means that less material is required for successful analysis. Second, on-line LC/MS optimizes the efficiency of sample transfer and saves both time and labor. Furthermore, the concentration dependence of ESI allows a majority of the material injected for LC/MS to be recovered for biological testing without compromising the signal available for molecular weight determination. As a validation of the above method, crude extracts containing two well-characterized antibiotics--teicoplanin and phenelfamycin--were examined. Results from these analyses are presented along with data from the analysis of a potent unknown antifungal sample.     

Friction and forces between cellulose model surfaces: a comparison

Four different cellulose model surfaces, and one silica surface, have been studied by means of atomic force microscopy (AFM). The normal interactions have been found to consist of a longer range double layer force with a short range steric interaction, the nature of which is extensively discussed. Both the surface charge and range of the steric force depend on the type of cellulose substrate used, as does the magnitude of the adhesion. Studies of friction reveal that surface roughness is the determining factor for the friction coefficient, with which it increases monotonically. The absolute value, however, is determined by the surface chemistry. All studied cellulose surfaces show similar behavior in response to xyloglucan addition.     

Preparation of microporous polymers in the form of particles and a thin film from hyperbranched polyphenylenes

The use of a hyperbranched polymer as a building block for the synthesis of a microporous organic polymer was demonstrated. Hyperbranched polyphenylenes (HBPs) were prepared from (3,5‐dibromophenyl)boronic acid, which contained numerous unreacted bromophenyl end groups. Utilizing metal‐catalyzed coupling reactions between these functional groups, cross‐linked porous polymers were obtained. Although the HBPs did not show porosity, their cross‐linked polymers had highly porous structures with Brunauer–Emmett–Teller surface areas of up to 2030 m²/g. An insoluble porous thin film was fabricated by spin casting of a solution containing a HBP followed by Sonogashira cross‐coupling reaction. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2336–2342     

Method validation and measurement uncertainty evaluation for measurement of mass concentration of organic acids in fermentation broths by using ion chromatography

In the present paper, a methodology for method validation and measurement uncertainty evaluation for the measurement of mass concentration of organic acids in fermentation broths was developed. Acetic acid was selected as a representative of organic acids. A detailed procedure for in-house method validation based on simple experimental design and consistent statistics is presented. In addition, a step-by-step illustration of ??Bottom-Up?? approach for measurement uncertainty evaluation of acetic acid in fermentation broths is also provided. The major sources of uncertainty of the result of measurement were identified and the combined uncertainty was calculated. Our analytical protocol allowed us to quantify acetic acid in fermentation broths in mass concentrations up to 75?g?L^?1 with satisfactory recovery (102.3%) and repeatability lower than 2%. We also estimated within-laboratory reproducibility over 3-month period, which was 2.3%. We proved that the method was selective for the measurement of mass concentration of acetic acid in fermentation broths. Measurement uncertainty of results was evaluated to be 6.2% with 95% confidence level. After validation and measurement uncertainty evaluation steps, results obtained showed that the method can be applied to efficiently monitor fermentation processes.     

Measurement of adsorption energy between a solid adsorbent and a liquid adsorbate using differential scanning calorimetry

We report on a novel method involving the use of differential scanning calorimetry (DSC) in evaluation of adsorption energy between a liquid adsorbate and a solid adsorbent. The proof of concept is demonstrated by measuring the exothermic heat release due to the adsorption of automotive transmission fluid (ATF), the adsorbate, to a paper-based friction material used in automotive torque converters, the adsorbent. The novelty of the measurement technique involves initial freezing of the liquid adsorbate so that the initiation of the adsorption process can be identified. Our experimental results and theoretical calculations reveal that the adsorption energy of the friction paper and the summation of adsorption energies of each friction paper ingredient are in good agreement.     

The structure and properties of n-octadecanol film present on the surface of a carbon-silica adsorbent

Summary The properties of the n-octadecanol film on carbon-silica adsorbent (Carbosil) were investigated. It was found that n-octadecanol forms an oriented film on the Carbosil's surface. If the surface of the basic silica gel is not completely covered with carbon, then the phase transition takes place in this film at a temperature higher than the melting temperature of n-octadecanol. One may distinguish two forms of this film, characterised by the different structures and the temperatures of the phase transitions. The first exists on the surface of silica gel unblocked by carbon. This part of the film is a monolayer, in which the alcohol molecules are vertically oriented. The solid compact-liquid expanded type phase transition at the well-defined temperature occurs in this film. In the second part of the film formed on the carbon surface, there is a multilayer of n-octadecanol. Its molecules are probably parallely oriented in relationship to the adsorbent surface. This film desintegrates progressively when the temperature increase. Maximum temperature of this phase transition is lower than the temperature of its analogue on pure silica gel surface.     

Recovery of zinc from chloride media by batch pertraction in a rotating film contactor

A liquid membrane (pertraction) process of zinc recovery from acidic chloride solutions was studied applying a pertraction in a rotating film contactor (RFC). Tri-n-octylamine (TOA or R₃N) dissolved in n-octane was used as a carrier. The influence of the main process parameters, such as disc rotation velocity, hydrochloric acid concentration in the aqueous phases and carrier concentration in the membrane was investigated. Assuming the existence of two thin reaction layers in the feed and stripping solutions, adjacent to both water–oil interfaces, a mathematical model was developed to describe the zinc transport. On the basis of the experimental data obtained under various conditions and the model proposed, it was found that the extraction step is controlled mainly by the mass transfer resistance, whereas the stripping rate of zinc is controlled predominantly by the rate of zinc–carrier complex decomposition in the stripping side reaction layer.     

Raman scattering in crystalline oligothiophenes: a comparison between density functional theory and bond polarizability model

Raman intensity of intramolecular and lattice modes of crystalline alpha-bithiophene (alpha-2T) are investigated within density functional theory using a nonlinear response formalism. First, comparison between the calculated Raman spectrum and the experimental data allows the assignment of the main Raman lines over the whole frequency range. Then, a bond polarizability (BP) model, limited to first neighbors, is built. We show that, although the BP model cannot reproduce the changes of dielectric susceptibility under individual atomic displacements, it is accurate enough to reproduce the profile of the unpolarized nonresonant Raman spectrum of alpha-2T powder. Finally, the BP model, fitted on our first-principles results on alpha-2T, is applied with success to the alpha-quaterthiophene polymorph phases and alpha-sexithiophene, demonstrating on practical examples that first-principles and BP approaches are powerful complementary tools to calculate the nonresonant Raman spectrum of alpha-2T and make reasonable predictions on larger oligothiophenes.     

Adsorption and separation behaviors of molybdenum from high-level liquid waste using a silica-based hydroxyoxime impregnated adsorbent

Journal of Radioanalytical and Nuclear Chemistry - To separate Mo(VI) from high-level liquid waste, a silica-based (anti-DEHDO + Dodec)/SiO2-P adsorbent was synthesized by impregnating...     

Preparation of poly(hydroxyethyl methacrylate-co-methacrylamidohistidine) beads and its design as a affinity adsorbent for Cu(II) removal from aqueous solutions

Different metal-complexing ligands carrying synthetic adsorbents have been reported in the literature for heavy metal removal. We have developed a novel and new approach to obtain high metal adsorption capacity utilizing 2-methacrylamidohistidine (MAH) as a metal-complexing ligand. MAH was synthesized by using methacrylochloride and histidine. Spherical beads with an average size of 150–200 μm were obtained by the radical suspension polymerization of MAH and 2-hydroxyethylmethacrylate (HEMA) conducted in an aqueous dispersion medium. Owing to the reasonably rough character of the bead surface, p(HEMA-co-MAH) beads had a specific surface area of 17.6 m² g⁻¹. Synthesized MAH monomer was characterized by NMR. p(HEMA-co-MAH) beads were characterized by swelling studies, FTIR and elemental analysis. These p(HEMA-co-MAH) affinity beads with a swelling ratio of 65%, and containing 1.6 mmol MAH g⁻¹ were used in the adsorption/desorption of copper(II) ions from metal solutions. Adsorption equilibria was achieved in ∼2 h. The maximum adsorption of Cu(II) ions onto pHEMA was ∼0.36 mg Cu(II) g⁻¹. The MAH incorporation significantly increased the Cu(II) adsorption capacity by chelate formation of Cu(II) ions with MAH molecules (122.7 mg Cu(II) g⁻¹), which was observed at pH 7.0. pH significantly affected the adsorption capacity of MAH incorporated beads. The observed adsorption order under non-competitive conditions was Cu(II)>Cr(III)>Hg(II)>Pb(II)>Cd(II) in molar basis. The chelating beads can be easily regenerated by 0.1 M HNO₃ with higher effectiveness. These features make p(HEMA-co-MAH) beads very good candidate for Cu(II) removal at high adsorption capacity.     

Polypyrrole films electropolymerized from ionic liquids and in a traditional liquid electrolyte: A comparison of morphology and electro-optical properties

Polypyrrole (pPy) films have been formed by electropolymerization from a conventional media: lithium triflate in acetonitrile and in room temperature ionic liquids: 1-ethyl-3-methyl imidazolium bis(perfluoroethanesulfonyl)imide (EMIPFSI) and 1-ethyl-3-methylimidazolium trifluoromethanesulfonate (EMITF). The well ordered nodular morphology of the pPy film grown in EMIPFSI with significantly low roughness endows these films with superior redox activity and electro-optical properties. Ambient temperature dc conductivities of 43, 15 and 13 S cm⁻¹, for films grown in EMIPFSI, EMITF and control solutions have seen obtained. The well-organized particulate morphology of the pPy film grown in EMIPFSI seems to be responsible for its enhanced conductivity, as also better interfacial charge transfer capabilities as compared to their counterparts derived. Under an external bias of ±2.2 V, the sluggish switching kinetics shown by the films under scrutiny presumably are due to the (i) resistive barriers formed at the two interfaces of the pPy electrode (ii) a plausible passivation layer on the solution side of the film during electrochemical cycling. This demonstrates the need to further improve the interfacial properties of pPy so as to obtain a consistent and stable electrochromic response.     

Numerical comparison of HCCI combustion mode between a free piston linear engine and traditional crankshaft engine

Journal of Thermal Analysis and Calorimetry - The free piston linear engine (FPLE) eliminates the crankshaft components and supports variable compression ratio operation. This characteristic makes...     

Controlled deposition of structured polymer films: chemical and rheological factors in chitosan film formation

The technique of "spread coating" has been used to create thin films from solutions of deacetylated and butyl-modified chitosan polymer, and the effect of deposition rate on film thickness has been characterized. Results show that films of controlled thickness can be reproducibly produced and that hydrophobic modification of the polymer can extend the range over which a linear response between film thickness and deposition rate is achieved. Viscometry and fluorescence spectroscopy were also employed to characterize the micellar characteristics of solutions of both deacetylated and butyl-modified chitosan polymer. Although both deacetylated and butyl-modified chitosan solutions were found to have inter- and intramolecular interactions, as well as hydrophobic domains able to incorporate fluorophores, deacetylated chitosan was found to be more interconnected via intermolecular interactions at higher concentrations. These results are important as having the ability to understand how the introduction of hydrophobic modification, a technique shown to introduce solution-based micelle structure and micellar aggregates that support enzyme immobilization, affects film thickness and morphology of spread coated thin films will aid the long-term development and deployment of chitosan-based biofuel cell electrodes.     

Mercury porosimetry in mesoporous glasses: a comparison of experiments with results from a molecular model

We present results from experiments and molecular modeling of mercury porosimetry into mesoporous Vycor and controlled pore glass (CPG) solid materials. The experimental intrusion/extrusion curves show a transition from a type H2 hysteresis for the Vycor glass to a type H1 hysteresis for the CPG. Mercury entrapment is observed in both materials, but we find that the amount of entrapped mercury depends on the chosen experimental relaxation time. No additional entrapment is found in a second intrusion/extrusion cycle, but hysteresis is still observed. This indicates that hysteresis and entrapment are of different origin. The experimental observations are qualitatively reproduced in theoretical calculations based on lattice models, which provide significant insights of the molecular mechanisms occurring during mercury porosimetry experiments in these porous glasses.     

Synthesis of polyester from renewable feedstock: a comparison between microwave and conventional heating

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