Polymer structure and catalytic activity of ion exchangers

1981 ◽  
Vol 46 (7) ◽  
pp. 1577-1587 ◽  
Author(s):  
Karel Jeřábek
Keyword(s):  
Catalytic Activity ◽  
Ethyl Acetate ◽  
Active Sites ◽  
Crosslinking Agent ◽  
Reaction Medium ◽  
Polymer Structure ◽  
Local Concentration ◽  
Ion Exchangers ◽  
Styrene Divinylbenzene ◽  
Kinetics Of

Catalytic activity of ion exchangers prepared by partial sulphonation of styrene-divinylbenzene copolymers in reesterifications of ethyl acetate by methanol and propanol, hydrolysis of ethyl acetate and in synthesis of bisphenol A has been compared with data on polymer structure of these catalysts and with distribution of the crosslinking agent, divinylbenzene, calculated from literature data on kinetics of copolymerisation of styrene with divinylbenzene. It was found that the polymer structure of ion exchangers influences catalytic activity predominantly by changing the local concentration of acid active sites. The results obtained indicated that the effect of transport phenomena on the rate of catalytic reactions does not depend on the degree of swelling of the ion exchangers in reaction medium but it is mainly dependent on the relative affinity of reaction components to the acid groups or to the polymer skeleton.

Kinetics of Isoprenepolymerization Initiated with TiCl4—Trialkyl Aluminum

1960 ◽  
Vol 33 (3) ◽  
pp. 696-698
Author(s):  
S. E. Bresler ◽  
M. I. Mosevitskiĭ
Keyword(s):  
Active Sites ◽  
Reaction Medium ◽  
Heat Evolution ◽  
Polymerization Reaction ◽  
Reaction Conditions ◽  
Low Viscosity ◽  
Rate Of Polymerization ◽  
Rate Of Reaction ◽  
Entire Experiment ◽  
Kinetics Of

Abstract For the study of the mechanism of polymerization by means of complexes of aluminum organic compounds with titanium chlorides, data on the kinetics of polymerization is of great interest. Up to the present time, the rate of polymerization of propylene has been studied but the interpretation of the kinetic data is difficult because the polymer, which is practically insoluble in the reaction medium, entraps the catalyst resulting in a rate of reaction which is dependent on the diffusion of monomer through the polymer to the active sites. In this work the polymerization of isoprene, which yields polymers soluble in the monomer, in saturated hydrocarbons and in benzene, was studied. The rate of the polymerization reaction was measured by the thermal effect in a calorimeter consisting of a 3.5 1. Dewar flask, with a lid, immersed in a thermostated air bath maintained at approximately the temperature of the reaction. Low viscosity spindle oil, heated to the temperature of the reaction (about 32°), served as the calorimeter fluid. The ampoule holder extended outside of the calorimeter and was connected to a shaking apparatus. The ampoule was divided by a thin partition into two sections each holding 45–50 cc. Into one section previously purified monomers and solvent were distilled. The other section was filled with catalyst components from a Shlenk container. The change in temperature of the calorimeter was determined with a Beckman thermometer with an accuracy of 0.01 °. When the temperature of the calorimeter containing the ampoule remained constant to within 0.01–0.02° for 30–40 minutes, the shaking apparatus was connected and the partition was broken with a striker. Intensive shaking was continued during the entire experiment resulting in mixing of the reaction mixture and of the calorimeter fluid. The rate of reaction was determined by the rate of heat evolution ; in other words, by the temperature rise in the calorimeter. For a rise of 0.1–0.5° the reaction conditions remained practically isothermal. This rise permits the kinetics of the reaction to be observed with sufficient accuracy. Adiabaticity of the calorimeter and the effect of mechanical heat were controlled in separate experiments.

Preparation, characterization and catalytic properties of yttrium-zirconium-pillared montmorillonite and their application in supported Ce catalysts

Clay Minerals ◽  
2015 ◽  
Vol 50 (2) ◽  
pp. 211-219 ◽  
Author(s):  
Bo Xue ◽  
Hongmei Guo ◽  
Lujie Liu ◽  
Min Chen
Keyword(s):  
Catalytic Activity ◽  
Ethyl Acetate ◽  
Specific Surface ◽  
Surface Area ◽  
Specific Surface Area ◽  
Active Sites ◽  
Industrial Applications ◽  
High Catalytic Activity ◽  
Total Oxidation ◽  
Pillared Montmorillonite

AbstractA new yttrium-zirconium-pillared montmorillonite (Y-Zr-MMT), was synthesized, characterized and used as a Ce catalyst support. The Y-Zr-MMT is a good support for dispersing cerium active sites and it is responsible for the high activity in the total oxidation of acetone, toluene and ethyl acetate. The Y-Zr-MMT shows greater advantages than the conventional alumina/cordierite honeycomb supports such as large specific surface area, lower cost and easier preparation. Catalytic tests demonstrated that Ce/Y-Zr-MMT (Ce loading 8.0%) was the most active, with the total oxidation of acetone, toluene and ethyl acetate being achieved at 220, 300 and 220°C, respectively. The catalyst displayed better activity for the oxidation of acetone and ethyl acetate than a conventional, supported Pd-catalyst under similar conditions. The special structure of the yttrium-doped zirconium-pillared montmorillonite can strengthen the interaction between the CeO2 and Zr-MMT support and improve the dispersion of the Ce particles, which enhances the catalytic activity for the oxidation of VOCs. The new catalyst, 8.0%Ce/Y-Zr-MMT, could be promising for industrial applications due to its high catalytic activity and low cost. The support and the catalysts were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and BET specific surface area measurements.

The effect of inhomogeneity of the polymer structure on catalytic activity of ion exchangers

1979 ◽  
Vol 44 (9) ◽  
pp. 2612-2618 ◽  
Author(s):  
Karel Jeřábek
Keyword(s):  
Catalytic Activity ◽  
Bisphenol A ◽  
Polymer Structure ◽  
Ion Exchangers ◽  
Test Reaction

It has been shown that using the dependence of catalytic activity of ion exchangers on the degree of sulphonation one can infer on the structure of their polymeric skeleton. Using condensation of phenol and acetone yielding Bisphenol A as a test reaction we have been able to distinguish up to four fractions of active groups in a series of ion exchangers of the gel and macroreticular type affected to a different extent by the structure of the surrounding polymer mass.

scholarly journals Increased Crystallization of CuTCNQ in Water/DMSO Bisolvent for Enhanced Redox Catalysis

Nanomaterials ◽  
2021 ◽  
Vol 11 (4) ◽  
pp. 954
Author(s):  
Zakir Hussain ◽  
Ayman Nafady ◽  
Samuel R. Anderson ◽  
Abdullah M. Al-Enizi ◽  
Asma A. Alothman ◽  
...  
Keyword(s):  
Dielectric Constant ◽  
Catalytic Activity ◽  
Reaction Medium ◽  
Catalytic Performance ◽  
Redox Catalysis ◽  
Ferricyanide Reduction ◽  
Efficient Catalyst ◽  
Cu Foil ◽  
Induced Changes ◽  
Kinetics Of

Controlling the kinetics of CuTCNQ (TCNQ = 7,7,8,8-tetracyanoquinodimethane) crystallization has been a major challenge, as CuTCNQ crystallizing on Cu foil during synthesis in conventional solvents such as acetonitrile simultaneously dissolves into the reaction medium. In this work, we address this challenge by using water as a universal co-solvent to control the kinetics of crystallization and growth of phase I CuTCNQ. Water increases the dielectric constant of the reaction medium, shifting the equilibrium toward CuTCNQ crystallization while concomitantly decreasing the dissolution of CuTCNQ. This allows more CuTCNQ to be controllably crystallized on the surface of the Cu foil. Different sizes of CuTCNQ crystals formed on Cu foil under different water/DMSO admixtures influence the solvophilicity of these materials. This has important implications in their catalytic performance, as water-induced changes in the surface properties of these materials can make them highly hydrophilic, which allows the CuTCNQ to act as an efficient catalyst as it brings the aqueous reactants in close vicinity of the catalyst. Evidently, the CuTCNQ synthesized in 30% (v/v) water/DMSO showed superior catalytic activity for ferricyanide reduction with 95% completion achieved within a few minutes in contrast to CuTCNQ synthesized in DMSO that took over 92 min.

Organic ion exchangers with enhanced catalytic activity

1982 ◽  
Vol 47 (6) ◽  
pp. 1613-1620
Author(s):  
Zdeněk Prokop ◽  
Karel Setínek
Keyword(s):  
Catalytic Activity ◽  
Functional Groups ◽  
Ion Exchanger ◽  
Ion Exchangers ◽  
Styrene Divinylbenzene

Several methods aimed at increasing the catalytic activity of the sulphonated styrene-divinylbenzene macroporous ion exchanger Wofatit OK 80 have been tested. The activity of the prepared ion exchanger catalysts has been examined in three reactions of different type which allowed to examine the effect of the methods used in the broader range of conditions. The results obtained show that the catalytic activity of ion exchangers can be increased substantially either by increasing the total number of acid functional groups, or, particularly, by such treatment which makes the maximal number of the present functional groups accessible to reaction components. However, by the chemical procedures used to enhance the activity, the ion exchangers acquire frequently also some properties which affect negatively their application as catalysts.

The design and catalytic performance of molybdenum active sites on an MCM-41 framework for the aerobic oxidation of 5-hydroxymethylfurfural to 2,5-diformylfuran

2019 ◽  
Vol 9 (3) ◽  
pp. 811-821 ◽  
Author(s):  
Zhao-Meng Wang ◽  
Li-Juan Liu ◽  
Bo Xiang ◽  
Yue Wang ◽  
Ya-Jing Lyu ◽  
...  
Keyword(s):  
Catalytic Activity ◽  
Active Sites ◽  
Aerobic Oxidation ◽  
Catalytic Performance ◽  
Mcm 41

The catalytic activity decreases as –(SiO)3Mo(OH)(O) > –(SiO)2Mo(O)2 > –(O)4–MoO.

Study of nickel-molybdenum catalysts for methanation of carbon monoxide

1980 ◽  
Vol 45 (3) ◽  
pp. 783-790 ◽  
Author(s):  
Petr Taras ◽  
Milan Pospíšil
Keyword(s):  
Carbon Monoxide ◽  
Catalytic Activity ◽  
Mixed Oxides ◽  
Minor Component ◽  
Fast Neutrons ◽  
Scanning Calorimetry ◽  
Low Concentrations ◽  
Γ Rays ◽  
Molybdenum Catalysts ◽  
Kinetics Of

Catalytic activity of nickel-molybdenum catalysts for methanation of carbon monoxide and hydrogen was studied by means of differential scanning calorimetry. The activity of NiMoOx systems exceeds that of carrier-free nickel if x < 2, and is conditioned by the oxidation degree of molybdenum, changing in dependence on the composition in the region Mo-MoO2. The activity of the catalysts is adversely affected by irradiation by fast neutrons, dose 28.1 Gy, or by γ rays using doses in the region 0.8-52 kGy. The system is most susceptible to irradiation in the region of low concentrations of the minor component (about 1 mol.%). The dependence of changes in catalytic activity of γ-irradiated samples on the dose exhibits a maximum in the range of 2-5 kGy. The changes in catalytic activity are stimulated by the change of reactivity of the starting mixed oxides, leading to different kinetics of their reduction and modification of their adsorption properties. The irradiation of the catalysts results in lowered concentration of the active centres for the methanation reaction.

Reesterification of ethyl acetate by propanol catalysed by glycidyl methacrylate copolymers containing sulphonic acid groups

1981 ◽  
Vol 46 (8) ◽  
pp. 1941-1946 ◽  
Author(s):  
Karel Setínek
Keyword(s):  
Liquid Phase ◽  
Ethyl Acetate ◽  
Kinetic Study ◽  
Gas Phase ◽  
Nonlinear Regression ◽  
Kinetic Data ◽  
Glycidyl Methacrylate ◽  
Kinetic Equations ◽  
Methacrylate Copolymers ◽  
Styrene Divinylbenzene

A series of differently crosslinked macroporous 2,3-epoxypropyl methacrylate-ethylenedimethacrylate copolymers with chemically bonded propylsulphonic acid groups were used as catalysts for the kinetic study of reesterification of ethyl acetate by n-propanol in the liquid phase at 52 °C and in the gas phase at 90 °C. Analysis of kinetic data by the method of nonlinear regression for a series of equations of the Langmuir-Hinshelwood type showed that kinetic equations which describe best the course of the reaction are the same as for the earlier studied sulphonated macroporous styrene-divinylbenzene copolymers. Compared types of catalysts differ, however, in the dependence of their activity on the degree of crosslinking of the copolymer used.

Kinetics of the catalytic hydrodesulphurization reaction system; hydrogenolysis of thiophene

1980 ◽  
Vol 45 (10) ◽  
pp. 2728-2741 ◽  
Author(s):  
Pavel Fott ◽  
Petr Schneider
Keyword(s):  
Atmospheric Pressure ◽  
Active Sites ◽  
Flow Reactor ◽  
Kinetic Equations ◽  
Reaction System ◽  
Reaction Products ◽  
Molybdenum Catalyst ◽  
Cobalt Molybdenum Catalyst ◽  
Kinetics Of ◽  
Reaction Schemes

Kinetics have been studied of the reaction system taking place during the reaction of thiophene on the cobalt-molybdenum catalyst in a gradientless circulation flow reactor at 360 °C and atmospheric pressure. Butane has been found present in a small amount in the reaction products even at very low conversion. In view of this, consecutive and parallel-consecutive (triangular) reaction schemes have been proposed. In the former scheme the appearance of butane is accounted for by rate of desorption of butene being comparable with the rate of its hydrogenation. According to the latter scheme part of the butane originates from thiophene via a different route than through hydrogenation of butene. Analysis of the kinetic data has revealed that the reaction of thiophene should be considered to take place on other active sites than that of butene. Kinetic equations derived on this assumption for the consecutive and the triangular reaction schemes correlate experimental data with acceptable accuracy.

Catalytic activity of rhodium(I) complexes containing (ω-trimethylsilylalkyl)diphenylphosphines

1980 ◽  
Vol 45 (8) ◽  
pp. 2219-2223 ◽  
Author(s):  
Marie Jakoubková ◽  
Martin Čapka
Keyword(s):  
Catalytic Activity ◽  
Nmr Spectroscopy ◽  
Ir Spectroscopy ◽  
Electron Density ◽  
Phosphorus Atom ◽  
Proton Acceptor ◽  
Trimethylsilyl Group ◽  
Kinetics Of

Kinetics of homogenous hydrogenation of 1-heptene catalysed by rhodium(I) complexes prepared in situ from μ,μ'-dichloro-bis(cyclooctenerhodium) and phosphines of the type RP(C6H5)2 (R = -CH3, -(CH2)nSi(CH3)3; n = 1-4) have been studied. The substitution of the ligands by the trimethylsilyl group was found to increase significantly the catalytic activity of the complexes. The results are discussed in relation to the electron density on the phosphorus atom determined by 31P NMR spectroscopy and to its proton acceptor ability determined by IR spectroscopy.

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