Anton N. Petukhov

Preparation and Characterization of Facilitated Transport Membranes Composed of Chitosan-Styrene and Chitosan-Acrylonitrile Copolymers Modified by Methylimidazolium Based Ionic Liquids for CO2 Separation from CH4 and N2

CO2 separation was found to be facilitated by transport membranes based on novel chitosan (CS)–poly(styrene) (PS) and chitosan (CS)–poly(acrylonitrile) (PAN) copolymer matrices doped with methylimidazolium based ionic liquids: [bmim][BF4], [bmim][PF6], and [bmim][Tf2N] (IL). CS plays the role of biodegradable film former and selectivity promoter. Copolymers were prepared implementing the latest achievements in radical copolymerization with chosen monomers, which enabled the achievement of outstanding mechanical strength values for the CS-based membranes (75–104 MPa for CS-PAN and 69–75 MPa for CS-PS). Ionic liquid (IL) doping affected the surface and mechanical properties of the membranes as well as the gas separation properties. The highest CO2 permeability 400 Barrers belongs to CS-b-PS/[bmim][BF4]. The highest selectivity α (CO2/N2) = 15.5 was achieved for CS-b-PAN/[bmim][BF4]. The operational temperature of the membranes is under 220 °C.

The Effect of Microporous Polymeric Support Modification on Surface and Gas Transport Properties of Supported Ionic Liquid Membranes.

Microporous polymers based on anionic macroinitiator and toluene 2,4-diisocyanate were used as a support for 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6]) and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([emim][Tf2N]) immobilization. The polymeric support was modified by using silica particles associated in oligomeric media, and the influence of the modifier used on the polymeric structure was studied. The supported ionic liquid membranes (SILMs) were tested for He, N2, NH3, H2S, and CO2 gas separation and ideal selectivities were calculated. The high values of ideal selectivity for ammonia-based systems with permanent gases were observed on polymer matrixes immobilized with [bmim][PF6] and [emim][Tf2N]. The modification of SILMs by nanosize silica particles leads to an increase of NH3 separation relatively to CO2 or H2S.

Quantum chemical simulation of the dissociative chemisorption of hydrogen on metal surfaces of nanoclusters

The mathematical and quantum chemical simulation of surfaces of Cd, Ba, Ca, Cu, Cs, Ti, Ni, Pd, W, and Pt metals was performed. The structural data were obtained for these surfaces, the behavior of a hydrogen molecule near these surfaces was studied. The calculations were performed in the framework of the density functional theory using the hybrid Becke—Lee—Yang—Parr functional in the LANL2DZ basis set. Mathematical modeling of the studied surfaces in the nanocluster approximation was performed by the Alexandrovich method. The results indicate that metals Ni, Pd, Pt, W, and Ti exhibit high catalytic activity in the dissociative chemisorption of hydrogen, while Ba, Cd, Cs, Ca, and Cu are lowly efficient because of the formation of hydrides.

Synthesis and properties of novel polyurethanes based on amino ethers of boric acid for gas separation membranes

Herein we present the structural and mechanical properties of polyurethanes synthesized from amino ethers of boric acid for gas separation. The polymers were characterized by light scattering methods, conductivity measurements, thermal gravimetric analysis, Fourier transform infrared spectroscopy, and atomic force microscopy. Additionally, the permeability of ammonia and carbon dioxide, as well as the selectivity for their diffusion and resultant impurity are presented. The results illustrate the steric hindrance, resulting in a branched architecture borate formation, leads to intermolecular complexation which may assist the polymer in ammonia diffusion selectivity.

Kinetics of germanium tetrachloride reduction with hydrogen in the presence of pyrolytic tungsten

Pyrolytic tungsten coatings have been produced on the surface of ash microspheres under steady-state conditions using tungsten hexacarbonyl as a precursor. The nanostructured composites thus obtained were characterized by X-ray diffraction and scanning electron microscopy. We have studied the kinetics of the catalytic reduction of germanium tetrachloride with hydrogen in the temperature range 423–973 K in the presence of the composites as catalysts and determined the reaction order and activation energy for the catalytic reduction of germanium tetrachloride with hydrogen.

Complexation of ammonia and water with cellulose acetate upon transmembrane transport

The mechanism of transmembrane transport of ammonia and water through the cellulose acetate membrane has been determined. The data obtained by FTIR spectroscopy confirm the suggested mechanism of penetrant interaction with the polymeric matrix and provide evidence that complexation by hydrogen bonding involves donor groups, such as C=O, C-O-C, and OH. The sorption of water and ammonia is localized in character and occurs on active sites of the polymeric matrix via the formation of hydrogen bonds with both the hydroxy groups and the ester oxygen atoms of cellulose acetate.

Separation of ammonia-containing gas mixtures in a one-compressor multistage membrane apparatus

Separation of the gas mixtures 7.7 vol % nitrogen in ammonia and 5.5% carbon monoxide in ammonia in one-compressor multistage membrane devices with one and two separation steps has been compared. The apparent values of selectivity have been determined for these gas mixtures. Expressions relating the degree of separation to the stage cut and the degree of purification to the product loss have been experimentally obtained. The degree of purification has been shown to increase with the number of stages despite of the fact that the degree of separation at individual stages is lower than in a single membrane module.

Catalytic effects of electrode material on the silicon tetrachloride hydrogenation in RF-arc-discharge

A silicon tetrachloride reduction in RF-arc-discharge (40.86 MHz) has been experimentally studied. The electrode material significantly affects the composition of the chlorosilanes in the gas phase at the outlet of the reactor which may be attributed to high and at the same time different catalytic activity of Cu, Ni, Nb, and Zr metals belonging to the transition of d-elements and W f-elements of the periodic table. The corrosion has been observed on the electrodes with the formation of chlorides of Cu, Ni, Nb, Zr, and W metals. In the system formed by two electrodes and plasma there are three main reactive regions in which the recovery of silicon tetrachloride by hydrogen at different flows is conducted independently from each other. The analysis of exhaust gases, chemically active plasma and condensed phase by emission-spectroscopy and GCMS spectrometry made it possible to propose the mechanism of formation of observed intermediate species and final products. On the basis of the obtained results we can conclude that this type of RF-plasma discharge includes two mechanisms of plasma chemical reactions: one with the participation of active particles formed in plasma and one initiated by the catalytically-active surface of the electrode.

Quantum chemical simulation of the mechanism of ammonia hydrate formation in low-temperature crystallization under reduced pressure

The quantum chemical calculation of thermodynamic and energy parameters of crystalline hydrates of ammonia was performed by the B3LYP/6-31+G(d) method. The calculated structural parameters, activation energies, and full energies confirm the conclusion about the formation of ammonia crystalline hydrates in low-temperature crystallization under reduced pressure.

IR manifestation of water intermediates formation with sodium hydroxide and sodium salts in KBr matrix

The association of water with sodium hydroxide, sodium carbonate and sodium nitrate in a KBr matrix at room temperature, exhibited by FTIR data, was established. It was found that water intermediates form due to the intermolecular hydrogen bond and can be stabilized in the solid phase. The revealed clusters can exist in several shape of hydrates shell with different geometry and number of involved water molecules.