This study is devoted to the rheology of oil emulsions, accompanied by both the formation and des... more This study is devoted to the rheology of oil emulsions, accompanied by both the formation and destruction of the structure. The presence of particles of a dispersed phase in an oil emulsion, including asphaltenes and resins, determines the formation of coagulation structures as a result of interaction and collision of particles. In this regard, to study the formation of coagulation structures, analytical solutions to the mass transfer equations are proposed, based on which the coalescence and fragmentation frequencies of the droplets are determined. Models and analytical solutions of the equation for the thinning of an interfacial film between droplets with their coalescence in the volume of an oil emulsion are proposed taking into account the Marangoni effect and the effect of asphaltene content. The thickness of the adsorbed layer on the droplet surface was estimated. Many empirical and semiempirical formulas have been proposed for determining the dependence of viscosity on the content of water and asphalt-resinous substances in oil. Based on the solution of the Fokker-Planck equation, the evolution of the distribution function of droplets in time and size in an oil emulsion is studied.
Asphaltenes are the heaviest crude oil fraction and tend to self-associate and precipitate. The p... more Asphaltenes are the heaviest crude oil fraction and tend to self-associate and precipitate. The precipitation and deposition of asphaltenes during the production, refining, transportation of oil is the main for the oil industry, the precipitation of asphaltenes and their subsequent deposition can cause problems at all stages of production. Asphaltenes have different structures and molecular composition, they are a mixture of poorly defined components, they are self-associated even at very low concentrations, what makes them one of the most difficult components of crude oil. Since the deposition mechanism of paraffin wax differs from the deposition mechanism of asphaltenes, mathematical modeling of crystallization of paraffin will be considered separately in another work. Creating accurate asphaltene models that can predict the behavior of asphaltenes in various scenarios should help reduce asphaltene problems. This review is specifically devoted to advances in mathematical modeling of asphaltenes. Several different models have been proposed in the literature for predicting the initial conditions and precipitation of asphaltenes. Existing modeling approaches can be broadly classified into colloidal and thermodynamic models. It should be noted intelligent models, such as a vector machine, an artificial neural network, in recent years are increasingly used for modeling various parameters and properties in the oil and chemical industries. However, these models are a black box and cannot provide a clear link between the output and input parameters of the model. In the past few years, models based on the Cubic Plus EoS Association (CPA EoS) and Statistical associating fluid theory (SAFT) have been recognized as promising one for studying asphaltene sediments. However, in the literature, there exist different opinions. Therefore, a systematic study is important for modeling the deposition of asphaltenes. Over the past decades, several different models have been proposed to predict the onset of asphaltenes and the amount of asphaltenes deposited. This paper examines various models that have been proposed to predict asphaltenes deposition under changing thermobaric conditions. A brief summary of various research approaches is presented.The main focus is on the description of the basic assumptions underlying various models, as well as on the ability of the model to correspond to experimental data. The presented models are compared and current modeling trends for forecasting precipitation are shown. This work will help improve understanding of asphaltenes and provide recommendations for the proper study and modeling of asphaltenes in future research.
The mechanism of paraffin formation in transport pipes is briefly discussed. A kinetic model of t... more The mechanism of paraffin formation in transport pipes is briefly discussed. A kinetic model of the formation and wax deposition from oil is proposed. Comparison of the model with the available experimental data gave satisfactory results. The review considers software tools for modeling the wax deposition process. It is noted that the simulation results are not always applicable to real field cases. For a more reliable interpretation, the scaling effect must be taken into account. In the work various technologies for wax removal are considered
Coalescence and fragmentation of drops in a turbulent flow are the basis of many chemical, oil re... more Coalescence and fragmentation of drops in a turbulent flow are the basis of many chemical, oil refining processes, food and pharmaceutical technologies, and are mainly associated with changes in the number of spectra and particles in a single volume that determine the size of the mass and heat transfer phase. Coalescence due to collision and subsequent enlargement of drops is widely used in emulsions, suspensions and other multi-phase media in the processes of phase separation and stratification (sedimentation, surface emergence). Fragmentation of drops required for the growth of the interfacial surface in gas-liquid reactors, liquid extraction, absorption in mass transfer processes, dusting, combustion, etc. is used quite widely in processes.
The problems of heavy oil rheology, accompanied by physical phenomena of the formation and destru... more The problems of heavy oil rheology, accompanied by physical phenomena of the formation and destruction of coagulation disordered structures and aggregates as a result of the hydrodynamic interaction of particles (asphaltenes, paraffins, resins, and solid-phase particles) contained in the oil, which significantly affect its properties and flow, are considered and analyzed. Rheological models of viscous-plastic heavy oils are considered and developed, consistent with a variety of experimental data. New rheological models for viscous-plastic heavy oils are proposed, which make it possible to generalize many existing models. It is noted that the variety of rheological models for heavy oils is determined by the conditions for the formation of disordered structures in the bulk of the oil flow. For heavy oils, a nonlinear equation for filtration in porous media is proposed, depending on the shear stress, pressure gradient, effective viscosity of the oil, and a number of other parameters. A...
In this study, thiodipropionic acid have analytical purity was used as starting materials. Cis-[(... more In this study, thiodipropionic acid have analytical purity was used as starting materials. Cis-[(C 6 H 5 CN) 2 PtCl 2 ], K 2 [PtCl 4 ], trans-[Pt[NH 3) 2 Cl 2 ] were synthesized by using the literature methods[ 1, 2]. Normal Na 2 L and NaHL salts of the ligands were prepared by potentiometric titration and the precipitating with organic solvents. Cis-[Pt(H 2 L) 2 Cl 2 ] (I), Cis-[Pt(H 2 L) 2 Br 2 ] (II), Trans-[Pt(H 2 L) 2 CI 2 ] (III), [Pt(H 2 L)(HL)Cl].2H 2 O (IV), Cis-[Pt(HL) 2 ] (V), Trans-[Pt(HL) 2 ] (VI). K[PtLCl] (VII), K[PtLBr] (VIII) and [PtLNH 3 ] (IX) were synthesized from thiodipropionic acid by using appropriate Pt(II) complex in different reaction conditions. Purity degree of the starting materials and final products were elucidated by elemental analyses and IR spectroscopy. It has been proved that platinum complexes of potential tridentate thiodiacetic acid also are coordinated maximal bidentally. Depending on condition the five-membered chelate ring is formed as a re...
The conditions for the synthesis of phthalimide by vapour phase ammoxidation of o-xylene on V-Sb-... more The conditions for the synthesis of phthalimide by vapour phase ammoxidation of o-xylene on V-Sb-Bi-Cr/γ-Al2O3-oxide catalyst were studied. The optimum process conditions to obtain the phthalimide as the main reaction product were determined. It is shown that the problem of difficult separation of crystal mixture of main products in the synthesis of phthalimide, solved with full conversion of o-xylene in a single process, using low concentrations of ammonia and water in the initial reaction mixture, which differs from the phthalonitrile obtaining an average from the substrate conversion to oxide catalyst V-Sb-Bi-Zr/γ-Al2O3 by recirculation at high concentrations of ammonia.
Cycloalkenylation of phenol with 4-vinylcyclohexene was studied in the presence of zeolite-Y cata... more Cycloalkenylation of phenol with 4-vinylcyclohexene was studied in the presence of zeolite-Y catalyst, saturated by orthophosphoric acid on the batch unit. Phenol and 4-vinylcyclohexene were used as initial products for the realization of cycloalkenylation reaction. Cyclodimerization is realized in liquid phase in the presence of copper on zeolite as a catalyst, which has high selectivity according to buta-1,3diene. All the separated products of reaction were characterized and their physico-chemical properties were determined. Chromatographic analysis was identified on chromatographer LKhM-72 with thermal conductivity detector. Synthesized p-(cyclohexenylethyl)phenol was identified by NMR and IR techniques. It is evident that the yield of target product p-(cyclohexenylethyl)phenol at optimum regime amounts to 72.4 % on theoretically, but selectivity found to be 97.7 % according to the target product. Tri-[p-(cyclohexenylethyl)phenyl phosphite was obtained by the interaction of p-(cyclohexenylethyl)phenol with phosphorus trichloride and tested as an antioxidant for turbine oil T-46.
The regularities of the influence of the modification of the surface layer of tissue carbon and g... more The regularities of the influence of the modification of the surface layer of tissue carbon and graphite fibrous materia on the composition, the amount of superficial functional oxygen-containing groups by different methods have been studied. The relationship between the electrocatalytic and corrosion characteristics of cathodes from tissue carbon and graphite fibrous materia has been established during electrosynthesis of H 2 O 2. They were tested during electrosynthesis of H 2 O 2 in a diaphragm cell with a current load of up to 100 A. A topological model of synchronous electrosynthesis hydrogen peroxide and ozone was developed.
Nano- and Micro-Encapsulation - Techniques and Applications [Working Title]
This study is devoted to the rheology of oil emulsions, accompanied by both the formation and des... more This study is devoted to the rheology of oil emulsions, accompanied by both the formation and destruction of the structure. The presence of particles of a dispersed phase in an oil emulsion, including asphaltenes and resins, determines the formation of coagulation structures as a result of interaction and collision of particles. In this regard, to study the formation of coagulation structures, analytical solutions to the mass transfer equations are proposed, based on which the coalescence and fragmentation frequencies of the droplets are determined. Models and analytical solutions of the equation for the thinning of an interfacial film between droplets with their coalescence in the volume of an oil emulsion are proposed taking into account the Marangoni effect and the effect of asphaltene content. The thickness of the adsorbed layer on the droplet surface was estimated. Many empirical and semiempirical formulas have been proposed for determining the dependence of viscosity on the content of water and asphalt-resinous substances in oil. Based on the solution of the Fokker-Planck equation, the evolution of the distribution function of droplets in time and size in an oil emulsion is studied.
This paper presents the results of the application of the software package OptimMe developed by u... more This paper presents the results of the application of the software package OptimMe developed by us for the study of process of partial oxidation of propane. The optimal parameters of the process were determined by the method of statistical planning of experiment. Catalyst activity rating was carried out on percentage of acetic acid in products of model reaction. It is obtained regression model of the process and the optimal regime of flow of this process is defined.
Kinetic regularities of vapor ammoxidation of xylene on the V the temperature range 648 both dire... more Kinetic regularities of vapor ammoxidation of xylene on the V the temperature range 648 both directly from o carbon dioxide formed by oxidation of from o
Advances in Chemical Engineering and Science, 2015
On the basis of kinetic data of 4-phenyl-o-xylene and 4-phenyl-o-tolunitrile ammoxidation, format... more On the basis of kinetic data of 4-phenyl-o-xylene and 4-phenyl-o-tolunitrile ammoxidation, formation mechanism of the products was analyzed and generalized. It has been shown that dissociative adsorption of a substrate and mononitrile occurs on the centers with high heats of adsorption of oxygen and as a consequence, completely covered with it, competitive adsorption of NH3 and O2 occurs on the centers with low heats of adsorption of the latter; mononitrile and dinitrile are formed correspondingly from adsorbed fragments of both substrate and NH3, and tolunitrile and NH3; surface interaction of adsorbed fragments of substrate and O2 with low heat of adsorption gives imide and CO2; hydrolysis of dinitrile into imide occurs on centers completely covered with ammonia; imide decarboxylation occurs on the centers covered with it; oxidative destruction of tolunitrile occurs on centers covered with substrate and mononitrile.
Literature data dedicated to formation of 4-phenylphthalonitrile were analyzed and generalized. A... more Literature data dedicated to formation of 4-phenylphthalonitrile were analyzed and generalized. As a result of the own studies, it has been established that on V-Sb-Bi-Zr/γ-Al 2 O 3-oxide catalyst ammoxidation gives 83.10 mol.% 4-phenylphthalonitrile at high conversion of the initial 4phenyl-o-xylene in a single process. In connection with increased demand to purity of 4-phenylphthalonitrile at using and division problem of hard-separable impurity of crystal 4-phenylphthalimide, a variant of the technological process design with average conversion and recirculation of the unreacted 4-phenyl-o-xylene and intermediate 4-phenyl-o-tolunitrile was proposed. In contrast to the single process, it has been determined that recirculation reduces quantity of form by-products, fractions of deep oxidation and increases selectivity on 4-phenylphthalonitrile up to 96.14%-97.72%. For the data analysis and visualization of results it is developed and offered the software package of OptimMe written in C#.
This study is devoted to the rheology of oil emulsions, accompanied by both the formation and des... more This study is devoted to the rheology of oil emulsions, accompanied by both the formation and destruction of the structure. The presence of particles of a dispersed phase in an oil emulsion, including asphaltenes and resins, determines the formation of coagulation structures as a result of interaction and collision of particles. In this regard, to study the formation of coagulation structures, analytical solutions to the mass transfer equations are proposed, based on which the coalescence and fragmentation frequencies of the droplets are determined. Models and analytical solutions of the equation for the thinning of an interfacial film between droplets with their coalescence in the volume of an oil emulsion are proposed taking into account the Marangoni effect and the effect of asphaltene content. The thickness of the adsorbed layer on the droplet surface was estimated. Many empirical and semiempirical formulas have been proposed for determining the dependence of viscosity on the content of water and asphalt-resinous substances in oil. Based on the solution of the Fokker-Planck equation, the evolution of the distribution function of droplets in time and size in an oil emulsion is studied.
Asphaltenes are the heaviest crude oil fraction and tend to self-associate and precipitate. The p... more Asphaltenes are the heaviest crude oil fraction and tend to self-associate and precipitate. The precipitation and deposition of asphaltenes during the production, refining, transportation of oil is the main for the oil industry, the precipitation of asphaltenes and their subsequent deposition can cause problems at all stages of production. Asphaltenes have different structures and molecular composition, they are a mixture of poorly defined components, they are self-associated even at very low concentrations, what makes them one of the most difficult components of crude oil. Since the deposition mechanism of paraffin wax differs from the deposition mechanism of asphaltenes, mathematical modeling of crystallization of paraffin will be considered separately in another work. Creating accurate asphaltene models that can predict the behavior of asphaltenes in various scenarios should help reduce asphaltene problems. This review is specifically devoted to advances in mathematical modeling of asphaltenes. Several different models have been proposed in the literature for predicting the initial conditions and precipitation of asphaltenes. Existing modeling approaches can be broadly classified into colloidal and thermodynamic models. It should be noted intelligent models, such as a vector machine, an artificial neural network, in recent years are increasingly used for modeling various parameters and properties in the oil and chemical industries. However, these models are a black box and cannot provide a clear link between the output and input parameters of the model. In the past few years, models based on the Cubic Plus EoS Association (CPA EoS) and Statistical associating fluid theory (SAFT) have been recognized as promising one for studying asphaltene sediments. However, in the literature, there exist different opinions. Therefore, a systematic study is important for modeling the deposition of asphaltenes. Over the past decades, several different models have been proposed to predict the onset of asphaltenes and the amount of asphaltenes deposited. This paper examines various models that have been proposed to predict asphaltenes deposition under changing thermobaric conditions. A brief summary of various research approaches is presented.The main focus is on the description of the basic assumptions underlying various models, as well as on the ability of the model to correspond to experimental data. The presented models are compared and current modeling trends for forecasting precipitation are shown. This work will help improve understanding of asphaltenes and provide recommendations for the proper study and modeling of asphaltenes in future research.
The mechanism of paraffin formation in transport pipes is briefly discussed. A kinetic model of t... more The mechanism of paraffin formation in transport pipes is briefly discussed. A kinetic model of the formation and wax deposition from oil is proposed. Comparison of the model with the available experimental data gave satisfactory results. The review considers software tools for modeling the wax deposition process. It is noted that the simulation results are not always applicable to real field cases. For a more reliable interpretation, the scaling effect must be taken into account. In the work various technologies for wax removal are considered
Coalescence and fragmentation of drops in a turbulent flow are the basis of many chemical, oil re... more Coalescence and fragmentation of drops in a turbulent flow are the basis of many chemical, oil refining processes, food and pharmaceutical technologies, and are mainly associated with changes in the number of spectra and particles in a single volume that determine the size of the mass and heat transfer phase. Coalescence due to collision and subsequent enlargement of drops is widely used in emulsions, suspensions and other multi-phase media in the processes of phase separation and stratification (sedimentation, surface emergence). Fragmentation of drops required for the growth of the interfacial surface in gas-liquid reactors, liquid extraction, absorption in mass transfer processes, dusting, combustion, etc. is used quite widely in processes.
The problems of heavy oil rheology, accompanied by physical phenomena of the formation and destru... more The problems of heavy oil rheology, accompanied by physical phenomena of the formation and destruction of coagulation disordered structures and aggregates as a result of the hydrodynamic interaction of particles (asphaltenes, paraffins, resins, and solid-phase particles) contained in the oil, which significantly affect its properties and flow, are considered and analyzed. Rheological models of viscous-plastic heavy oils are considered and developed, consistent with a variety of experimental data. New rheological models for viscous-plastic heavy oils are proposed, which make it possible to generalize many existing models. It is noted that the variety of rheological models for heavy oils is determined by the conditions for the formation of disordered structures in the bulk of the oil flow. For heavy oils, a nonlinear equation for filtration in porous media is proposed, depending on the shear stress, pressure gradient, effective viscosity of the oil, and a number of other parameters. A...
In this study, thiodipropionic acid have analytical purity was used as starting materials. Cis-[(... more In this study, thiodipropionic acid have analytical purity was used as starting materials. Cis-[(C 6 H 5 CN) 2 PtCl 2 ], K 2 [PtCl 4 ], trans-[Pt[NH 3) 2 Cl 2 ] were synthesized by using the literature methods[ 1, 2]. Normal Na 2 L and NaHL salts of the ligands were prepared by potentiometric titration and the precipitating with organic solvents. Cis-[Pt(H 2 L) 2 Cl 2 ] (I), Cis-[Pt(H 2 L) 2 Br 2 ] (II), Trans-[Pt(H 2 L) 2 CI 2 ] (III), [Pt(H 2 L)(HL)Cl].2H 2 O (IV), Cis-[Pt(HL) 2 ] (V), Trans-[Pt(HL) 2 ] (VI). K[PtLCl] (VII), K[PtLBr] (VIII) and [PtLNH 3 ] (IX) were synthesized from thiodipropionic acid by using appropriate Pt(II) complex in different reaction conditions. Purity degree of the starting materials and final products were elucidated by elemental analyses and IR spectroscopy. It has been proved that platinum complexes of potential tridentate thiodiacetic acid also are coordinated maximal bidentally. Depending on condition the five-membered chelate ring is formed as a re...
The conditions for the synthesis of phthalimide by vapour phase ammoxidation of o-xylene on V-Sb-... more The conditions for the synthesis of phthalimide by vapour phase ammoxidation of o-xylene on V-Sb-Bi-Cr/γ-Al2O3-oxide catalyst were studied. The optimum process conditions to obtain the phthalimide as the main reaction product were determined. It is shown that the problem of difficult separation of crystal mixture of main products in the synthesis of phthalimide, solved with full conversion of o-xylene in a single process, using low concentrations of ammonia and water in the initial reaction mixture, which differs from the phthalonitrile obtaining an average from the substrate conversion to oxide catalyst V-Sb-Bi-Zr/γ-Al2O3 by recirculation at high concentrations of ammonia.
Cycloalkenylation of phenol with 4-vinylcyclohexene was studied in the presence of zeolite-Y cata... more Cycloalkenylation of phenol with 4-vinylcyclohexene was studied in the presence of zeolite-Y catalyst, saturated by orthophosphoric acid on the batch unit. Phenol and 4-vinylcyclohexene were used as initial products for the realization of cycloalkenylation reaction. Cyclodimerization is realized in liquid phase in the presence of copper on zeolite as a catalyst, which has high selectivity according to buta-1,3diene. All the separated products of reaction were characterized and their physico-chemical properties were determined. Chromatographic analysis was identified on chromatographer LKhM-72 with thermal conductivity detector. Synthesized p-(cyclohexenylethyl)phenol was identified by NMR and IR techniques. It is evident that the yield of target product p-(cyclohexenylethyl)phenol at optimum regime amounts to 72.4 % on theoretically, but selectivity found to be 97.7 % according to the target product. Tri-[p-(cyclohexenylethyl)phenyl phosphite was obtained by the interaction of p-(cyclohexenylethyl)phenol with phosphorus trichloride and tested as an antioxidant for turbine oil T-46.
The regularities of the influence of the modification of the surface layer of tissue carbon and g... more The regularities of the influence of the modification of the surface layer of tissue carbon and graphite fibrous materia on the composition, the amount of superficial functional oxygen-containing groups by different methods have been studied. The relationship between the electrocatalytic and corrosion characteristics of cathodes from tissue carbon and graphite fibrous materia has been established during electrosynthesis of H 2 O 2. They were tested during electrosynthesis of H 2 O 2 in a diaphragm cell with a current load of up to 100 A. A topological model of synchronous electrosynthesis hydrogen peroxide and ozone was developed.
Nano- and Micro-Encapsulation - Techniques and Applications [Working Title]
This study is devoted to the rheology of oil emulsions, accompanied by both the formation and des... more This study is devoted to the rheology of oil emulsions, accompanied by both the formation and destruction of the structure. The presence of particles of a dispersed phase in an oil emulsion, including asphaltenes and resins, determines the formation of coagulation structures as a result of interaction and collision of particles. In this regard, to study the formation of coagulation structures, analytical solutions to the mass transfer equations are proposed, based on which the coalescence and fragmentation frequencies of the droplets are determined. Models and analytical solutions of the equation for the thinning of an interfacial film between droplets with their coalescence in the volume of an oil emulsion are proposed taking into account the Marangoni effect and the effect of asphaltene content. The thickness of the adsorbed layer on the droplet surface was estimated. Many empirical and semiempirical formulas have been proposed for determining the dependence of viscosity on the content of water and asphalt-resinous substances in oil. Based on the solution of the Fokker-Planck equation, the evolution of the distribution function of droplets in time and size in an oil emulsion is studied.
This paper presents the results of the application of the software package OptimMe developed by u... more This paper presents the results of the application of the software package OptimMe developed by us for the study of process of partial oxidation of propane. The optimal parameters of the process were determined by the method of statistical planning of experiment. Catalyst activity rating was carried out on percentage of acetic acid in products of model reaction. It is obtained regression model of the process and the optimal regime of flow of this process is defined.
Kinetic regularities of vapor ammoxidation of xylene on the V the temperature range 648 both dire... more Kinetic regularities of vapor ammoxidation of xylene on the V the temperature range 648 both directly from o carbon dioxide formed by oxidation of from o
Advances in Chemical Engineering and Science, 2015
On the basis of kinetic data of 4-phenyl-o-xylene and 4-phenyl-o-tolunitrile ammoxidation, format... more On the basis of kinetic data of 4-phenyl-o-xylene and 4-phenyl-o-tolunitrile ammoxidation, formation mechanism of the products was analyzed and generalized. It has been shown that dissociative adsorption of a substrate and mononitrile occurs on the centers with high heats of adsorption of oxygen and as a consequence, completely covered with it, competitive adsorption of NH3 and O2 occurs on the centers with low heats of adsorption of the latter; mononitrile and dinitrile are formed correspondingly from adsorbed fragments of both substrate and NH3, and tolunitrile and NH3; surface interaction of adsorbed fragments of substrate and O2 with low heat of adsorption gives imide and CO2; hydrolysis of dinitrile into imide occurs on centers completely covered with ammonia; imide decarboxylation occurs on the centers covered with it; oxidative destruction of tolunitrile occurs on centers covered with substrate and mononitrile.
Literature data dedicated to formation of 4-phenylphthalonitrile were analyzed and generalized. A... more Literature data dedicated to formation of 4-phenylphthalonitrile were analyzed and generalized. As a result of the own studies, it has been established that on V-Sb-Bi-Zr/γ-Al 2 O 3-oxide catalyst ammoxidation gives 83.10 mol.% 4-phenylphthalonitrile at high conversion of the initial 4phenyl-o-xylene in a single process. In connection with increased demand to purity of 4-phenylphthalonitrile at using and division problem of hard-separable impurity of crystal 4-phenylphthalimide, a variant of the technological process design with average conversion and recirculation of the unreacted 4-phenyl-o-xylene and intermediate 4-phenyl-o-tolunitrile was proposed. In contrast to the single process, it has been determined that recirculation reduces quantity of form by-products, fractions of deep oxidation and increases selectivity on 4-phenylphthalonitrile up to 96.14%-97.72%. For the data analysis and visualization of results it is developed and offered the software package of OptimMe written in C#.
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