Pub Date : 2018-10-23DOI: 10.6060/IVKKT.20186109-10.5716
A. V. Okhlobystina, A. Okhlobystin, N. Berberova, D. Burmistrova
Most methods of obtaining aromatic thiols are based on nucleophilic substitution reactions at halogen derivatives of aromatic hydrocarbons when used as nucleophilic reagents sodium thiolate, thiourea or potassium xanthate at high temperatures, pressure and in the presence of catalysts. The direct reaction of nucleophilic substitution of OH-groups in the phenols, pyrocatechol and benzyl alcohol to the HS-group in conditions of one-electron reducrion of hydrogen sulfide in acetonitrile and pyridinium ionic liquid was investigated for the first time. The proposed reactions proceed at room temperature and atmospheric pressure. The use of "green" solvent - ionic liquid - reduces the syntheses time in а half, improves ecological safety friendliness of the process and reduces the consumption of reagents. The main positive feature of these studies is not only ecological safety of reactions of nucleophilic substitution (due to the lack of harmful byproducts), but the use of electrochemical reactions in ionic liquid media, that is very relevant in modern science in terms of new environmental technologies development. For citation: Okhlobystina A.V., Okhlobystin A.O., Berberova N.T., Burmistrova D.A. Hydrogen sulfide in nucleophilic substitution reactions of hydroxy groups in aromatic alcohols. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2018. V. 61. N 9-10. P. 36-41 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
{"title":"HYDROGEN SULFIDE IN NUCLEOPHILIC SUBSTITUTION REACTIONS OF HYDROXY GROUPS IN AROMATIC ALCOHOLS","authors":"A. V. Okhlobystina, A. Okhlobystin, N. Berberova, D. Burmistrova","doi":"10.6060/IVKKT.20186109-10.5716","DOIUrl":"https://doi.org/10.6060/IVKKT.20186109-10.5716","url":null,"abstract":"Most methods of obtaining aromatic thiols are based on nucleophilic substitution reactions at halogen derivatives of aromatic hydrocarbons when used as nucleophilic reagents sodium thiolate, thiourea or potassium xanthate at high temperatures, pressure and in the presence of catalysts. The direct reaction of nucleophilic substitution of OH-groups in the phenols, pyrocatechol and benzyl alcohol to the HS-group in conditions of one-electron reducrion of hydrogen sulfide in acetonitrile and pyridinium ionic liquid was investigated for the first time. The proposed reactions proceed at room temperature and atmospheric pressure. The use of \"green\" solvent - ionic liquid - reduces the syntheses time in а half, improves ecological safety friendliness of the process and reduces the consumption of reagents. The main positive feature of these studies is not only ecological safety of reactions of nucleophilic substitution (due to the lack of harmful byproducts), but the use of electrochemical reactions in ionic liquid media, that is very relevant in modern science in terms of new environmental technologies development. \u0000For citation: \u0000Okhlobystina A.V., Okhlobystin A.O., Berberova N.T., Burmistrova D.A. Hydrogen sulfide in nucleophilic substitution reactions of hydroxy groups in aromatic alcohols. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2018. V. 61. N 9-10. P. 36-41 \u0000 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .","PeriodicalId":45993,"journal":{"name":"Izvestiya Vysshikh Uchebnykh Zavedenii Khimiya i Khimicheskaya Tekhnologiya","volume":" ","pages":""},"PeriodicalIF":0.9,"publicationDate":"2018-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"41334405","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2018-10-23DOI: 10.6060/ivkkt.20186109-10.5883
T. F. Yudina, V. N. Blinichev, Iliya V. Bratkov, T. Gushchina, A. G. Melnikov
In this paper, the process of spheroidization of natural graphite powders on an original impact-reflecting mill with internal separation of particles was investigated. It was established that the process of spheroidization of natural graphite by impact depends both on the intensity and duration of mechanical activation. For the type of mill used, the critical linear velocity of the impact elements of the mill rotor, at which the graphite particles can be spheroidized, is 45 m/s. An increase in the linear rotational speed of the mill (intensity of impact) leads to a decrease in the average particle size, an increase in particle roundness, but significantly increases product losses. In the process of mechanical activation by impact, it is possible to increase the coefficient of roundness of the graphite particles to an average value of 0.8-0.9, which leads to compaction of graphite powders. The presence of ash impurities has a negative effect on the ability of natural graphite powders to compact. A mechanism is proposed for the process of spheroidization of graphite particles in a shock-reflecting mill. According to the proposed mechanism, at first, small-sized graphite plates are detached and deformed due to impact. As the free energy accumulates, agglomeration of deformed particles into spheres takes place. With increasing processing time, the surface of the particles is smoothed due to their friction with each other and against the wall of the mill. Powders of spherical graphite obtained by the proposed method have shown the possibility of their use as an anode material of lithium-ion batteries. The type of equipment investigated has made it possible to reduce the required number of pieces of equipment from 20 to 12 impact mills per line in comparison with foreign analogues. For citation: Yudina T.F., Blinichev V.N., Bratkov I.V., Gushchina Т.V., Melnikov A.G. Investigation of process of natural graphite spheroidization. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2018. V. 61. N 9-10. P. 48-52
{"title":"INVESTIGATION OF PROCESS OF NATURAL GRAPHITE SPHEROIDIZATION","authors":"T. F. Yudina, V. N. Blinichev, Iliya V. Bratkov, T. Gushchina, A. G. Melnikov","doi":"10.6060/ivkkt.20186109-10.5883","DOIUrl":"https://doi.org/10.6060/ivkkt.20186109-10.5883","url":null,"abstract":"In this paper, the process of spheroidization of natural graphite powders on an original impact-reflecting mill with internal separation of particles was investigated. It was established that the process of spheroidization of natural graphite by impact depends both on the intensity and duration of mechanical activation. For the type of mill used, the critical linear velocity of the impact elements of the mill rotor, at which the graphite particles can be spheroidized, is 45 m/s. An increase in the linear rotational speed of the mill (intensity of impact) leads to a decrease in the average particle size, an increase in particle roundness, but significantly increases product losses. In the process of mechanical activation by impact, it is possible to increase the coefficient of roundness of the graphite particles to an average value of 0.8-0.9, which leads to compaction of graphite powders. The presence of ash impurities has a negative effect on the ability of natural graphite powders to compact. A mechanism is proposed for the process of spheroidization of graphite particles in a shock-reflecting mill. According to the proposed mechanism, at first, small-sized graphite plates are detached and deformed due to impact. As the free energy accumulates, agglomeration of deformed particles into spheres takes place. With increasing processing time, the surface of the particles is smoothed due to their friction with each other and against the wall of the mill. Powders of spherical graphite obtained by the proposed method have shown the possibility of their use as an anode material of lithium-ion batteries. The type of equipment investigated has made it possible to reduce the required number of pieces of equipment from 20 to 12 impact mills per line in comparison with foreign analogues. \u0000For citation: \u0000Yudina T.F., Blinichev V.N., Bratkov I.V., Gushchina Т.V., Melnikov A.G. Investigation of process of natural graphite spheroidization. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2018. V. 61. N 9-10. P. 48-52","PeriodicalId":45993,"journal":{"name":"Izvestiya Vysshikh Uchebnykh Zavedenii Khimiya i Khimicheskaya Tekhnologiya","volume":" ","pages":""},"PeriodicalIF":0.9,"publicationDate":"2018-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"48656357","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2018-10-22DOI: 10.6060/ivkkt20186109-10.5802
D. Shutov, A. V. Sungurova, K. Smirnova, A. Manukyan, V. Rybkin
The results of experimental studies of the kinetics of oxidation-reduction of Mn7+ ions (MnO4-) in aqueous solutions initiated by the action of a discharge of a direct current of atmospheric pressure in air are analyzed in the article. A solution of potassium permanganate served as a discharge cathode. The range of initial solution concentrations for Mn7+ ions was (0.44-2.5) mmol/l, and discharge currents (20-60) mA. It was found that the discharge action leads to the reduction of Mn7+ ions and discoloration of the solution. At the same time, dark solid particles with a size of 0.1 μm to 20 μm are formed. X-ray diffraction analysis showed that the particles are amorphous, and energy dispersive X-ray analysis showed that the powder is manganese oxide (IV). The kinetics of reduction-oxidation of Mn7+ ions is measured. It is shown that the obtained data on the kinetics of the reduction of Mn7+ ions in the best way (the determination coefficient R2≈0.99) can be described by the scheme X↔Y↔Z, where X is the starting material, and Y and Z are the reaction products. The processing of kinetic curves on the basis of this scheme found the effective rate constants of the corresponding stages. It was found that the effective rate constants depend on the initial concentration of the solution. At a discharge current of 20 mA, an increase in the concentration from 0.44 to 2.5 mol/l led to a decrease in the rate constant for the reduction of Mn7+ ions from (2.48 ± 0.5) ·10-2 to (7.2 ± 1.5) ·10-3 s-1, respectively. Possible mechanisms of processes are discussed. It is assumed that the main particles involved in the oxidation reactions of the reduction of manganese ions are H2O2, HO2, OH and solvated electrons that are formed in the solution under the action of a discharge. For citation: Shutov D.A., Sungurova A.V., Smirnova K.V., Manukyan A.S., Rybkin V.V. Oxidative-reducing processes with participation of manganese ions initiated by electric discharge in aqueous solution. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2018. V. 61. N 9-10. P. 23-29
{"title":"OXIDATIVE-REDUCING PROCESSES WITH PARTICIPATION OF MANGANESE IONS INITIATED BY AN ELECTRIC DISCHARGE IN AQUEOUS SOLUTION","authors":"D. Shutov, A. V. Sungurova, K. Smirnova, A. Manukyan, V. Rybkin","doi":"10.6060/ivkkt20186109-10.5802","DOIUrl":"https://doi.org/10.6060/ivkkt20186109-10.5802","url":null,"abstract":"The results of experimental studies of the kinetics of oxidation-reduction of Mn7+ ions (MnO4-) in aqueous solutions initiated by the action of a discharge of a direct current of atmospheric pressure in air are analyzed in the article. A solution of potassium permanganate served as a discharge cathode. The range of initial solution concentrations for Mn7+ ions was (0.44-2.5) mmol/l, and discharge currents (20-60) mA. It was found that the discharge action leads to the reduction of Mn7+ ions and discoloration of the solution. At the same time, dark solid particles with a size of 0.1 μm to 20 μm are formed. X-ray diffraction analysis showed that the particles are amorphous, and energy dispersive X-ray analysis showed that the powder is manganese oxide (IV). The kinetics of reduction-oxidation of Mn7+ ions is measured. It is shown that the obtained data on the kinetics of the reduction of Mn7+ ions in the best way (the determination coefficient R2≈0.99) can be described by the scheme X↔Y↔Z, where X is the starting material, and Y and Z are the reaction products. The processing of kinetic curves on the basis of this scheme found the effective rate constants of the corresponding stages. It was found that the effective rate constants depend on the initial concentration of the solution. At a discharge current of 20 mA, an increase in the concentration from 0.44 to 2.5 mol/l led to a decrease in the rate constant for the reduction of Mn7+ ions from (2.48 ± 0.5) ·10-2 to (7.2 ± 1.5) ·10-3 s-1, respectively. Possible mechanisms of processes are discussed. It is assumed that the main particles involved in the oxidation reactions of the reduction of manganese ions are H2O2, HO2, OH and solvated electrons that are formed in the solution under the action of a discharge. \u0000For citation: \u0000Shutov D.A., Sungurova A.V., Smirnova K.V., Manukyan A.S., Rybkin V.V. Oxidative-reducing processes with participation of manganese ions initiated by electric discharge in aqueous solution. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2018. V. 61. N 9-10. P. 23-29","PeriodicalId":45993,"journal":{"name":"Izvestiya Vysshikh Uchebnykh Zavedenii Khimiya i Khimicheskaya Tekhnologiya","volume":" ","pages":""},"PeriodicalIF":0.9,"publicationDate":"2018-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"48562945","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2018-10-22DOI: 10.6060/IVKKT20186109-10.5863A
M. Kulikova, O. S. Dement’eva, M. Chudakova, M. Ivantsov
Methods for the formation of stable iron-containing suspensions that exhibit activity in the conversion of synthesis gas to C5+ hydrocarbons by the Fischer-Tropsch method are proposed. By XRD and DLS methods it was determined that the formation of the Fe2O3 phase with a bimodal particle size distribution of 50 and 295 nm results in the formation of a suspension by the drop thermolysis method − the gradual introduction of the active metal precursor solution into the dispersion medium (mixture of hydrocarbons C19H40-C32H66). Pulsed introduction of the active metal precursor solution (flash-pyrolysis) into the reactor zone leads to the formation of the Fe3O4 phase with a particle size of 91 and 460 nm. By TEM and AFM methods it was established that, regardless of the slurry forming method, large active phase particles are agglomerates of a finer fraction of particles with an average size of 42 nm. The obtained suspensions demonstrated high activity in the Fischer-Tropsch synthesis under the slurry-reactor conditions, however, the degree of CO conversion is slightly higher in the case of the catalytic suspension prepared by the drop thermolysis method. It is shown that the method of forming the suspension significantly affects the fractional composition of the resulting reaction products. In the presence of a suspension obtained by drop thermolysis, the yield of liquid hydrocarbons reaches 130 g/m3, while a high content of C19+ hydrocarbons is observed. The system formed by the method of flash-pyrolysis makes it possible to obtain mainly the gasoline (C5-C10) and diesel (C11-C18) hydrocarbon fractions. It should be noted that the products of the reaction have a high content of unsaturated hydrocarbons, which reaches 55%. Thus, the composition of the final products of FTS can be controlled by the choice of the catalytic suspension prepared method. For citation: Kulikova M.V., Dement’eva O.S., Chudakova M.V., Ivantsov M.I. Influence of preparing nanoscale suspensions method on its physico-chemical and catalytic properties under the conditions of Fischer-Tropsch synthesis. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2018. V. 61. N 9-10. P. 70-75
{"title":"INFLUENCE OF PREPARING NANOSCALE SUSPENSIONS METHOD ON ITS PHYSICO-CHEMICAL AND CATALYTIC PROPERTIES UNDER THE CONDITIONS OF FISCHER-TROPSCH SYNTHESIS","authors":"M. Kulikova, O. S. Dement’eva, M. Chudakova, M. Ivantsov","doi":"10.6060/IVKKT20186109-10.5863A","DOIUrl":"https://doi.org/10.6060/IVKKT20186109-10.5863A","url":null,"abstract":"Methods for the formation of stable iron-containing suspensions that exhibit activity in the conversion of synthesis gas to C5+ hydrocarbons by the Fischer-Tropsch method are proposed. By XRD and DLS methods it was determined that the formation of the Fe2O3 phase with a bimodal particle size distribution of 50 and 295 nm results in the formation of a suspension by the drop thermolysis method − the gradual introduction of the active metal precursor solution into the dispersion medium (mixture of hydrocarbons C19H40-C32H66). Pulsed introduction of the active metal precursor solution (flash-pyrolysis) into the reactor zone leads to the formation of the Fe3O4 phase with a particle size of 91 and 460 nm. By TEM and AFM methods it was established that, regardless of the slurry forming method, large active phase particles are agglomerates of a finer fraction of particles with an average size of 42 nm. The obtained suspensions demonstrated high activity in the Fischer-Tropsch synthesis under the slurry-reactor conditions, however, the degree of CO conversion is slightly higher in the case of the catalytic suspension prepared by the drop thermolysis method. It is shown that the method of forming the suspension significantly affects the fractional composition of the resulting reaction products. In the presence of a suspension obtained by drop thermolysis, the yield of liquid hydrocarbons reaches 130 g/m3, while a high content of C19+ hydrocarbons is observed. The system formed by the method of flash-pyrolysis makes it possible to obtain mainly the gasoline (C5-C10) and diesel (C11-C18) hydrocarbon fractions. It should be noted that the products of the reaction have a high content of unsaturated hydrocarbons, which reaches 55%. Thus, the composition of the final products of FTS can be controlled by the choice of the catalytic suspension prepared method. \u0000For citation: \u0000Kulikova M.V., Dement’eva O.S., Chudakova M.V., Ivantsov M.I. Influence of preparing nanoscale suspensions method on its physico-chemical and catalytic properties under the conditions of Fischer-Tropsch synthesis. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2018. V. 61. N 9-10. P. 70-75 \u0000 ","PeriodicalId":45993,"journal":{"name":"Izvestiya Vysshikh Uchebnykh Zavedenii Khimiya i Khimicheskaya Tekhnologiya","volume":" ","pages":""},"PeriodicalIF":0.9,"publicationDate":"2018-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"41906309","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2018-10-22DOI: 10.6060/ivkkt20186109-10.5778
N. V. Tukumova, T. R. Usacheva, Tran Thi Dieu Thuan, V. Sharnin, C. Giancola
The paper provides an overview of own data on complexation of nickel (II), cobalt (II) and cooper (II) ions with succinic acid anion in water-organic mixed solvents. Proper data are compared with data reported in literature for d-metal complexes with anions of maleic and succinic acids. The effect of aqueous ethanol solvent compositions on the stability of coordination compounds of M2+ with succinic acid anion as well as on рК values of stepwise succinic acid dissociation was carried out by a potentiometric titration at ionic strength of 0.1 maintained with sodium perchlorate at 298.15 ± 0.10 K. Mono ligand complexes of Ni2+, Co2+ and Cu2+ ions with succinic acid anion become stronger when ethanol content rises. In aqueous solutions Cu2+ ion forms stronger complexes with succinic and maleic acid anions than Ni2+ and Co2+ ions. In the studied water - ethanol solution this ratio is maintained for complexes with succinic acid anion, but a water-isopropanol solvent exerts leveling effect on the stability of complexes of nickel (II) and cobalt (II). An increase in the stability of complexes of d-metal with anions of maleic and succinic acids is due to the destabilization of the ligand with increasing ethanol concentration. The principal contribution of the changes in the solvation state of ligand is a typical for the stability changes of d-metal complexes with amine, glycinate, and acetate type ligands in water-organic mixed solvents. For citation: Tukumova N.V., Usacheva T.R., Thuan Tran Thi Dieu, Sharnin V.A., Giancola C. Stability of coordination compounds of some d-metal ions with succinic acid anion in aqueous-ethanol solvents. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2018. V. 61. N 9-10. P. 15-22
{"title":"STABILITY OF COORDINATION COMPOUNDS OF SOME d-METAL IONS WITH SUCCINIC ACID ANION IN AQUEOUS-ETHANOL SOLVENTS","authors":"N. V. Tukumova, T. R. Usacheva, Tran Thi Dieu Thuan, V. Sharnin, C. Giancola","doi":"10.6060/ivkkt20186109-10.5778","DOIUrl":"https://doi.org/10.6060/ivkkt20186109-10.5778","url":null,"abstract":"The paper provides an overview of own data on complexation of nickel (II), cobalt (II) and cooper (II) ions with succinic acid anion in water-organic mixed solvents. Proper data are compared with data reported in literature for d-metal complexes with anions of maleic and succinic acids. The effect of aqueous ethanol solvent compositions on the stability of coordination compounds of M2+ with succinic acid anion as well as on рК values of stepwise succinic acid dissociation was carried out by a potentiometric titration at ionic strength of 0.1 maintained with sodium perchlorate at 298.15 ± 0.10 K. Mono ligand complexes of Ni2+, Co2+ and Cu2+ ions with succinic acid anion become stronger when ethanol content rises. In aqueous solutions Cu2+ ion forms stronger complexes with succinic and maleic acid anions than Ni2+ and Co2+ ions. In the studied water - ethanol solution this ratio is maintained for complexes with succinic acid anion, but a water-isopropanol solvent exerts leveling effect on the stability of complexes of nickel (II) and cobalt (II). An increase in the stability of complexes of d-metal with anions of maleic and succinic acids is due to the destabilization of the ligand with increasing ethanol concentration. The principal contribution of the changes in the solvation state of ligand is a typical for the stability changes of d-metal complexes with amine, glycinate, and acetate type ligands in water-organic mixed solvents. \u0000For citation: \u0000Tukumova N.V., Usacheva T.R., Thuan Tran Thi Dieu, Sharnin V.A., Giancola C. Stability of coordination compounds of some d-metal ions with succinic acid anion in aqueous-ethanol solvents. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2018. V. 61. N 9-10. P. 15-22 \u0000 ","PeriodicalId":45993,"journal":{"name":"Izvestiya Vysshikh Uchebnykh Zavedenii Khimiya i Khimicheskaya Tekhnologiya","volume":" ","pages":""},"PeriodicalIF":0.9,"publicationDate":"2018-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"41356186","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2018-10-22DOI: 10.6060/IVKKT20186109-10.5862A
A. B. Arbuzov, V. Drozdov, D. A. Shlyapin, A. Lavrenov
It is known that binary alloys of aluminum and metals of the iron group (cobalt, nickel) after their activation with the liquid eutectic gallium-indium by the removal of “passivating” oxide layers sharply increase the reactivity with respect to organochlorines. Corresponding reactions lead to the formation of metal – alumo - chloride complexes as inorganic products, which are active in many practically important catalytic reactions of liquid-phase conversion of hydrocarbons such as: alkylation, isomerization, oligomerization. This approach which was previously developed by the authors for the polycrystalline aluminum, is of interest in metal-complex catalysis since the formation of catalytic alumo-chloride and/or metal-alumo-chloride complexes can be carried out directly in the reaction medium, i.e. in situ. In this work, the local composition, structure and morphology of surface layers of aluminum-cobalt and aluminum-nickel alloys activated with liquid gallium-indium eutectic were studied using the methods of scanning electron microscopy and X-ray energy-dispersive spectrometry to determine the physicochemical regularities of the dynamics of their interaction with tert-butyl chloride at room temperatures. The formation of metal chloride complexes in the interphase area “activated alloy - tert-butyl chloride” was studied by ATR-FT-IR method in situ. The results obtained indicate that mono- and bi- nuclear alumo-chloride anions stabilized by cobalt and nickel cations are formed during the interaction. It is assumed that the ionic complex pairs formed are the active centers in liquid-phase reactions of hydrocarbons transformation at low temperatures. These structures are responsible for significantly change in the selectivity of catalytic processes compared to aluminum chloride catalyst. For citation: Arbuzov A.B., Drozdov V.A., Shlyapin D.A., Lavrenov A.V. Interaction of aluminum-cobalt and aluminum-nickel alloys activated by liquid gallium-indium eutectic with tert-butyl chloride for formation of catalytic metal - alumo-chloride complexes. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2018. V. 61. N 9-10. P. 64-69
{"title":"INTERACTION OF ALUMINUM-COBALT AND ALUMINUM-NICKEL ALLOYS ACTIVATED BY LIQUID GALLIUM-INDIUM EUTECTIC WITH TERT-BUTYL CHLORIDE FOR FORMATION OF CATALYTIC METAL - ALUMO-CHLORIDE COMPLEXES","authors":"A. B. Arbuzov, V. Drozdov, D. A. Shlyapin, A. Lavrenov","doi":"10.6060/IVKKT20186109-10.5862A","DOIUrl":"https://doi.org/10.6060/IVKKT20186109-10.5862A","url":null,"abstract":"It is known that binary alloys of aluminum and metals of the iron group (cobalt, nickel) after their activation with the liquid eutectic gallium-indium by the removal of “passivating” oxide layers sharply increase the reactivity with respect to organochlorines. Corresponding reactions lead to the formation of metal – alumo - chloride complexes as inorganic products, which are active in many practically important catalytic reactions of liquid-phase conversion of hydrocarbons such as: alkylation, isomerization, oligomerization. This approach which was previously developed by the authors for the polycrystalline aluminum, is of interest in metal-complex catalysis since the formation of catalytic alumo-chloride and/or metal-alumo-chloride complexes can be carried out directly in the reaction medium, i.e. in situ. In this work, the local composition, structure and morphology of surface layers of aluminum-cobalt and aluminum-nickel alloys activated with liquid gallium-indium eutectic were studied using the methods of scanning electron microscopy and X-ray energy-dispersive spectrometry to determine the physicochemical regularities of the dynamics of their interaction with tert-butyl chloride at room temperatures. The formation of metal chloride complexes in the interphase area “activated alloy - tert-butyl chloride” was studied by ATR-FT-IR method in situ. The results obtained indicate that mono- and bi- nuclear alumo-chloride anions stabilized by cobalt and nickel cations are formed during the interaction. It is assumed that the ionic complex pairs formed are the active centers in liquid-phase reactions of hydrocarbons transformation at low temperatures. These structures are responsible for significantly change in the selectivity of catalytic processes compared to aluminum chloride catalyst. \u0000For citation: \u0000Arbuzov A.B., Drozdov V.A., Shlyapin D.A., Lavrenov A.V. Interaction of aluminum-cobalt and aluminum-nickel alloys activated by liquid gallium-indium eutectic with tert-butyl chloride for formation of catalytic metal - alumo-chloride complexes. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2018. V. 61. N 9-10. P. 64-69","PeriodicalId":45993,"journal":{"name":"Izvestiya Vysshikh Uchebnykh Zavedenii Khimiya i Khimicheskaya Tekhnologiya","volume":" ","pages":""},"PeriodicalIF":0.9,"publicationDate":"2018-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"46113236","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2018-10-22DOI: 10.6060/IVKKT20186109-10.5758
D. M. Klimushin, A. I. Krasnov, D. Filippov, N. Sharonov
The 2-chloro-4-nitroaniline liquid-phase hydrogenation kinetics on supported palladium and platinum catalysts differing in the nature of the carrier and the active metal content was studied for the first time. The experiment was carried out at elevated hydrogen pressures in the range of 9 - 12 atm and 303 K in solvents 2-propanol-water and ethyl acetate in the reactor such as Vishnevsky autoclave. The main kinetic parameters of the reaction have been determined, and the influence of various parameters on the regularities of the process has been established. It is shown that an increase in the active metal content in the catalyst leads to an increase in the rate of the hydrogenation reaction of 2-chloro-4-nitroaniline. When using platinum supported catalysts, the rate of hydrogenation of 2-chloro-4-nitroaniline is significantly higher than when using supported palladium catalysts. The replacement of the liquid phase of the catalyst system with 2-propanol by ethyl acetate adversely affects the reaction rate. The influence of the catalytic system nature and composition on the target product dehalogenation degree was determined. It was found that when carrying out the reaction at elevated hydrogen pressures, it is preferable to use low-percentage platinum catalysts, rather than palladium catalysts, since the former provide less dehalogenation of the target product. For citation: Klimushin D.M., Krasnov A.I., Filippov D.V., Sharonov N.Yu. Hydrogen pressure, solvent and catalyst nature influence on 2-chloro-4-nitroaniline hydrogenation regularities. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2018. V. 61. N 9-10. P. 30-35
{"title":"HYDROGEN PRESSURE, SOLVENT AND CATALYST NATURE INFLUENCE ON THE 2-CHLORO-4-NITROANILINE HYDROGENATION REGULARITIES","authors":"D. M. Klimushin, A. I. Krasnov, D. Filippov, N. Sharonov","doi":"10.6060/IVKKT20186109-10.5758","DOIUrl":"https://doi.org/10.6060/IVKKT20186109-10.5758","url":null,"abstract":"The 2-chloro-4-nitroaniline liquid-phase hydrogenation kinetics on supported palladium and platinum catalysts differing in the nature of the carrier and the active metal content was studied for the first time. The experiment was carried out at elevated hydrogen pressures in the range of 9 - 12 atm and 303 K in solvents 2-propanol-water and ethyl acetate in the reactor such as Vishnevsky autoclave. The main kinetic parameters of the reaction have been determined, and the influence of various parameters on the regularities of the process has been established. It is shown that an increase in the active metal content in the catalyst leads to an increase in the rate of the hydrogenation reaction of 2-chloro-4-nitroaniline. When using platinum supported catalysts, the rate of hydrogenation of 2-chloro-4-nitroaniline is significantly higher than when using supported palladium catalysts. The replacement of the liquid phase of the catalyst system with 2-propanol by ethyl acetate adversely affects the reaction rate. The influence of the catalytic system nature and composition on the target product dehalogenation degree was determined. It was found that when carrying out the reaction at elevated hydrogen pressures, it is preferable to use low-percentage platinum catalysts, rather than palladium catalysts, since the former provide less dehalogenation of the target product. \u0000For citation: \u0000Klimushin D.M., Krasnov A.I., Filippov D.V., Sharonov N.Yu. Hydrogen pressure, solvent and catalyst nature influence on 2-chloro-4-nitroaniline hydrogenation regularities. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2018. V. 61. N 9-10. P. 30-35 \u0000 ","PeriodicalId":45993,"journal":{"name":"Izvestiya Vysshikh Uchebnykh Zavedenii Khimiya i Khimicheskaya Tekhnologiya","volume":" ","pages":""},"PeriodicalIF":0.9,"publicationDate":"2018-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"49520485","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2018-10-22DOI: 10.6060/ivkkt.20186109-10.5867a
V. Romanovsky, Alexander A. Hort, K. Podbolotov, N. Sdobnyakov, V. Myasnichenko, D. N. Sokolov
In this work, we studied possibility to obtain bimetallic nanopowders by our modified solution combustion synthesis method using citric acid as a fuel. Stoichiometric amounts of metal nitrates with metal to metal ratios 1:1 and 1:2 and fuels with final oxidizer to fuel ratio of 1.75 were used as initial components to prepare aqueous solutions. The almost complete absence of metal oxide phases was confirmed by energy-dispersive X-ray spectroscopy. The X-ray diffraction analysis of obtained materials showed that all samples are pure bimetallic nanopowders with distorted cubic crystal structure of each metal. According to high resolution transmission electron microscopy the mean diameter of metallic particles are about 10 nm for all nanopowders. The calculated interplanar distances of crystals of metal particles as well as detailed scanning transmission electron microscopy studying showed uniform distribution of different metal spices into nanoparticles. Thus, we can conclude the nanopowders are bimetallic particles with co-integrated crystal structures of different metalic spices. We suppose, the possibility of solution combustion synthesis of bimetallic nanopowder in the air environment is due to a combination of type and amount of the fuels as well as technological conditions of the synthesis. These lead to rapid combustion process at low temperature. In addition, protective inert atmosphere appears above freshly synthesized metal nanopowders during thermal decompositions of the fuels that eventually prevent metal oxidation. Modified SCS method could be successfully used for one-step synthesis of complex oxide-oxide and metal-oxide core-shell nanostructures. For citation: Romanovskii V.I., Khort A.A., Podbolotov K.B., Sdobnyakov N.Y., Myasnichenko V.S., Sokolov D.N. One-step synthesis of polymetallic nanoparticles in air invironment. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2018. V. 61. N 9-10. P. 42-47
{"title":"ONE-STEP SYNTHESIS OF POLYMETALLIC NANOPARTICLES IN AIR INVIRONMENT","authors":"V. Romanovsky, Alexander A. Hort, K. Podbolotov, N. Sdobnyakov, V. Myasnichenko, D. N. Sokolov","doi":"10.6060/ivkkt.20186109-10.5867a","DOIUrl":"https://doi.org/10.6060/ivkkt.20186109-10.5867a","url":null,"abstract":"In this work, we studied possibility to obtain bimetallic nanopowders by our modified solution combustion synthesis method using citric acid as a fuel. Stoichiometric amounts of metal nitrates with metal to metal ratios 1:1 and 1:2 and fuels with final oxidizer to fuel ratio of 1.75 were used as initial components to prepare aqueous solutions. The almost complete absence of metal oxide phases was confirmed by energy-dispersive X-ray spectroscopy. The X-ray diffraction analysis of obtained materials showed that all samples are pure bimetallic nanopowders with distorted cubic crystal structure of each metal. According to high resolution transmission electron microscopy the mean diameter of metallic particles are about 10 nm for all nanopowders. The calculated interplanar distances of crystals of metal particles as well as detailed scanning transmission electron microscopy studying showed uniform distribution of different metal spices into nanoparticles. Thus, we can conclude the nanopowders are bimetallic particles with co-integrated crystal structures of different metalic spices. We suppose, the possibility of solution combustion synthesis of bimetallic nanopowder in the air environment is due to a combination of type and amount of the fuels as well as technological conditions of the synthesis. These lead to rapid combustion process at low temperature. In addition, protective inert atmosphere appears above freshly synthesized metal nanopowders during thermal decompositions of the fuels that eventually prevent metal oxidation. Modified SCS method could be successfully used for one-step synthesis of complex oxide-oxide and metal-oxide core-shell nanostructures. \u0000For citation: \u0000Romanovskii V.I., Khort A.A., Podbolotov K.B., Sdobnyakov N.Y., Myasnichenko V.S., Sokolov D.N. One-step synthesis of polymetallic nanoparticles in air invironment. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2018. V. 61. N 9-10. P. 42-47","PeriodicalId":45993,"journal":{"name":"Izvestiya Vysshikh Uchebnykh Zavedenii Khimiya i Khimicheskaya Tekhnologiya","volume":" ","pages":""},"PeriodicalIF":0.9,"publicationDate":"2018-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"46195529","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2018-10-22DOI: 10.6060/IVKKT.20186109-10.5805A
L. A. Dzhigola, E. A. Syutova
The results of an experimental study of calcium ion adsorption processes carried out on various mineral sorbents of natural origin are presented. The sorption properties of the selected objects were studied and the possibility of their use as combined anti-icing materials was evaluated. In the work were investigated technological indicators of the quality of sorbents - the pH of the zero-charge point, the sorption capacity of sorbents and the optimum pH interval to determine the sorption activity of mineral raw materials on calcium ion. Analysis of the adsorption isotherms of calcium ions by the mineral sorbents studied makes it possible to note that the adsorption equilibrium on the clay is established more rapidly than on the opal of the marl type and marl. At the same time, the maximum absorption capacity of clay and marl has close values, which is related to the structure of the sorbent surface and the mineral composition of the materials. Opal of the marl type has a more developed surface, which is illustrated by a much higher absorption capacity and is confirmed by the values of the specific surface area. The obtained experimental data were processed using Freundlich, Langmuir, Temkin, and Dubinin-Radushkevich models. When describing the adsorption equilibrium of calcium ions on mineral sorbents, the Freyndlich isotherm is a more rigorous model, which indicates the presence of a large number of active centers and their exponential distribution on the surface of sorbents. The quantitative characteristics of the adsorption capacity of sorbents, found by adsorption models, made it possible to identify the optimum conditions of processes, establish a relationship between the values of the sorption of calcium ions by their structure and the porosity of the materials. It has been established that opal of marl type is the most effective carrier for producing anti-icing materials. For citation: Dzhigola L.A., Syutova E.A. Solid-phase concentration of calcium ions with mineral sorbents in creation of anti-icing materials. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2018. V. 61. N 9-10. P. 98-104
{"title":"Solid-phase concentration of calcium ions with mineral sorbents in creation of anti-icing materials","authors":"L. A. Dzhigola, E. A. Syutova","doi":"10.6060/IVKKT.20186109-10.5805A","DOIUrl":"https://doi.org/10.6060/IVKKT.20186109-10.5805A","url":null,"abstract":"The results of an experimental study of calcium ion adsorption processes carried out on various mineral sorbents of natural origin are presented. The sorption properties of the selected objects were studied and the possibility of their use as combined anti-icing materials was evaluated. In the work were investigated technological indicators of the quality of sorbents - the pH of the zero-charge point, the sorption capacity of sorbents and the optimum pH interval to determine the sorption activity of mineral raw materials on calcium ion. Analysis of the adsorption isotherms of calcium ions by the mineral sorbents studied makes it possible to note that the adsorption equilibrium on the clay is established more rapidly than on the opal of the marl type and marl. At the same time, the maximum absorption capacity of clay and marl has close values, which is related to the structure of the sorbent surface and the mineral composition of the materials. Opal of the marl type has a more developed surface, which is illustrated by a much higher absorption capacity and is confirmed by the values of the specific surface area. The obtained experimental data were processed using Freundlich, Langmuir, Temkin, and Dubinin-Radushkevich models. When describing the adsorption equilibrium of calcium ions on mineral sorbents, the Freyndlich isotherm is a more rigorous model, which indicates the presence of a large number of active centers and their exponential distribution on the surface of sorbents. The quantitative characteristics of the adsorption capacity of sorbents, found by adsorption models, made it possible to identify the optimum conditions of processes, establish a relationship between the values of the sorption of calcium ions by their structure and the porosity of the materials. It has been established that opal of marl type is the most effective carrier for producing anti-icing materials. \u0000For citation: \u0000Dzhigola L.A., Syutova E.A. Solid-phase concentration of calcium ions with mineral sorbents in creation of anti-icing materials. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2018. V. 61. N 9-10. P. 98-104","PeriodicalId":45993,"journal":{"name":"Izvestiya Vysshikh Uchebnykh Zavedenii Khimiya i Khimicheskaya Tekhnologiya","volume":" ","pages":""},"PeriodicalIF":0.9,"publicationDate":"2018-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"41601719","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2018-10-22DOI: 10.6060/ivkkt.20186109-10.5806a
L. A. Dzhigola, O. S. Sadomtseva, Victoria V. Shakirova, K. V. Kargina, E. A. Syutova, P. Razgovorov, Roman S. Nagornov
I In the work there were studied the regularities of extracting copper (II) and lead (II) cations from aqueous solutions with the help of natural sorbents from the Astrakhan region such as the marl of the Baskunchak deposit, the Kamennyy yar deposit and the clay of the Volzhsky deposit. A comparative study was made of the applicability of the adsorption models of Langmuir, Freindlich, Temkin, and Dubinin-Radushkevich to describe the experimental adsorption isotherms of these cations on the surface of aluminosilicates. The constants and parameters of the equations corresponding to these models are determined. A comparison of the regression coefficients shows that the Temkin model is suitable for describing the adsorption equilibria in the "M2+ -clay" systems. The Freundlich model most adequately describes the experimental data on adsorption in the "M2+ -marl/opoka" systems, which reveals the heterogeneous surface of both of these materials with a large number of energetically dissimilar active centers. The regression coefficients found in this case by the Langmuir model are small; the boundary conditions for the description of systems with a monomolecular coating are not observed. The Dubinin-Radushkevich model was also used to describe the process of concentrating lead (II) compounds on the marl surface of the Baskunchak deposit and the Kamennyy Yar deposit. The calculated values of the free energy of adsorption were 11.2 (opoka) and 4.17 kJ/mol (marl). The process of fixing lead cations on these natural sorbents in the Astrakhan region proceeds according to the ion-exchange mechanism. The adsorption activity of Cu2+, Pb2+ ions on the surface of sorbents is confirmed by the calculated values of Gibbs energy and entropy. The endothermic nature of the processes taking place with the participation of the clay of the Volzhsky deposit and the Kamennyy Yar deposit is explained by the considerable energy expenditure for the dehydration of the surface groups of sorbents. For citation: Dzhigola L.A., Sadomtseva O.S., Shakirova V.V., Kargina K.V., Syutova E.A., Razgovorov P.B., Nagornov R.S. Application of adsorption models for description of equilibria in systems cations of copper (II) and lead (II) – natural materials of Astrakhan region. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2018. V. 61. N 9-10. P. 105-112
{"title":"APPLICATION OF ADSORPTION MODELS FOR DESCRIPTION OF BALANCES IN THE SYSTEMS «CATIONS OF COPPER (II) AND LEAD (II) – NATURAL MATERIALS OF ASTRAKHAN REGION »","authors":"L. A. Dzhigola, O. S. Sadomtseva, Victoria V. Shakirova, K. V. Kargina, E. A. Syutova, P. Razgovorov, Roman S. Nagornov","doi":"10.6060/ivkkt.20186109-10.5806a","DOIUrl":"https://doi.org/10.6060/ivkkt.20186109-10.5806a","url":null,"abstract":"I \u0000In the work there were studied the regularities of extracting copper (II) and lead (II) cations from aqueous solutions with the help of natural sorbents from the Astrakhan region such as the marl of the Baskunchak deposit, the Kamennyy yar deposit and the clay of the Volzhsky deposit. A comparative study was made of the applicability of the adsorption models of Langmuir, Freindlich, Temkin, and Dubinin-Radushkevich to describe the experimental adsorption isotherms of these cations on the surface of aluminosilicates. The constants and parameters of the equations corresponding to these models are determined. A comparison of the regression coefficients shows that the Temkin model is suitable for describing the adsorption equilibria in the \"M2+ -clay\" systems. The Freundlich model most adequately describes the experimental data on adsorption in the \"M2+ -marl/opoka\" systems, which reveals the heterogeneous surface of both of these materials with a large number of energetically dissimilar active centers. The regression coefficients found in this case by the Langmuir model are small; the boundary conditions for the description of systems with a monomolecular coating are not observed. The Dubinin-Radushkevich model was also used to describe the process of concentrating lead (II) compounds on the marl surface of the Baskunchak deposit and the Kamennyy Yar deposit. The calculated values of the free energy of adsorption were 11.2 (opoka) and 4.17 kJ/mol (marl). The process of fixing lead cations on these natural sorbents in the Astrakhan region proceeds according to the ion-exchange mechanism. The adsorption activity of Cu2+, Pb2+ ions on the surface of sorbents is confirmed by the calculated values of Gibbs energy and entropy. The endothermic nature of the processes taking place with the participation of the clay of the Volzhsky deposit and the Kamennyy Yar deposit is explained by the considerable energy expenditure for the dehydration of the surface groups of sorbents. \u0000For citation: \u0000Dzhigola L.A., Sadomtseva O.S., Shakirova V.V., Kargina K.V., Syutova E.A., Razgovorov P.B., Nagornov R.S. Application of adsorption models for description of equilibria in systems cations of copper (II) and lead (II) – natural materials of Astrakhan region. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2018. V. 61. N 9-10. P. 105-112","PeriodicalId":45993,"journal":{"name":"Izvestiya Vysshikh Uchebnykh Zavedenii Khimiya i Khimicheskaya Tekhnologiya","volume":" ","pages":""},"PeriodicalIF":0.9,"publicationDate":"2018-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"46704027","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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