ABSTRACT
CHAPTER I. MACROKINETICS OF FAST CHEMICAL REACTIONS 7 1.1. The classification of chemical technology reactors 7 1.1.1. Plug-flow reactors 7 1.1.2. Stirring reactors 8 1.1.3. Hydrodynamic structure of reaction mixture movement 9 1.1.4. Problems of instrumental typography under fast chemical processes 11 1.2. Realization of fast chemical reactions in tubular regime 12 1.2.1. Fundamental regularities of fast chemical reactions in turbulent flows 12 I.2.1.1. Existence o£several macroscof!.ic regimes 12 1.2.I.2. Correlation between t:,eomel!l o£reaction ;.one with kinetic and
molecular-masses characteristics and yield 14 I.2.1.4. Effectiveness o£external heat removal 14 1.2.2. Realizlltion of fast processes in tubular turbulent apparatus 15 1.3. Intensification of heat-and mass-transfer processes in turbulent
regime 16 1.3.1. Turbulent mixing of one-phase mediums 16 1.3.2. Turbulent mixing of multi-phase mediums 19 1.3.3. Regulation of thermal conditions under fast chemical reactions in
turbulent flows 21 I.3.3.I. Adiabatic regime 21 1.3.3.2. Internal heat removal 22 I.3.3.3. External heat removal 23 I.3.3.4. Intensification o£ convection heat-trans£er in tubular af!.f!.aratus 24 1.3.4. Hydro-dynamic and heat similarity criterill and their function in heat-and
mass-transfer processes 24 1.4. Diffuse limitations under some polymers synthesis 26 1.4.1. Stereospecific polymerization of isoprene on Ziegler-Natta catalysts 26 1.4.2. Pentadiene-I,3 cationic polymerizlltion 29 1.4.3. Ethylene and propylene copolymerization 31 1.4.4. Chlorination of butyl rubber 32
CHAPTER2. EXPERIMENTAL PART 35 2.1. Experimental work 35 2.I.I. Oligomerization of piperylene 35 2.1.2. Isoprene stereospecific polymerization 35 2.1.3. Chlorination of butyl rubber 36 2.1.4. Ethylene and propylene copolymerization 36 2.I.5. Formation of macro-structures of reaction and mixing fronts in
2.2.2. Determination of polymers molecular-masses characteristics 44 2.2.3. Determination of chlorine content in rubber 44 2.2.4. Determination of double bonds content in polymers 44 2.2.5. Determination of density and viscosity of liquid flows 44 2.2.6. Analysis of suspension dispersed structure 44
CHAPTER3. DEVELOPMENT OF SCIENTIFICALLY -GROUNDED APPROACH TO THE SELECTION OF OPTIMAL REACTION ZONE GEOMETRY UNDER FAST PROCESSES 46
3.1. One-phase systems 46 3.1.1. Mathematical modelling 46 3.1.2. Turbulent mixing in tubular apparatus 49 3.1.3. Distribution of reagents residence times in apparatus of cylindrical
and divergent-convergent types 54 3.1.4. Fast processes proceeding in high-viscosity mediums 63 3.1.4.1. Sel[.-similar regime of. reaction medium flow 63 3.1.4.2. Ol!,timi5.ation of. characteristics of. reagents turbulent mixing_ in self:
similar regime 66 3.2. Multi-phase systems 74 3.2.1. Mathematical modelling 74 3.2.2. The apparatus geometry effect 80 3.2.3. The reagents introduction method effect 82 3.2.4. Separation of reaction medium under multi-phase systems flow in
tubular turbulent apparatus 85
CHAPTER4. EXTERNAL HEAT REMOVAL UNDER FAST CHEMICAL REACTIONS IN TURBULENT REGIME 89
4.1. Quasi-plug-flow mode in turbulent flows as a key to realization of fast chemical processes in quasi-isothermal conditions 89
4.1.2. The influence oflitjuidjlows physical characteristics on conditions of quasi-plug-flow mode formation 90
4.2. Regulation of thermal conditions under fast chemical reactions in turbulent regime 94
4.2.2. Intensification of convention heat-transfer 104 4.2.2.1. Apparatus geometry effect 104 4.2.2.2. The correlation between heat-trans[.er coe[ficient and hy_dro-dy_namic
regime of. reaction medium motion 110
CHAPTERS. NOVEL SOLUTIONS IN THE FIELD OF FAST CHEMICAL PROCESSES REALIZATION IN TURBULENT REGIME UNDER POLYMERS SYNTHESIS 115
5.1. Butyl rubber halogenation 115 5.2. Cationic piperylene oligomerization 116 5.2.1. Kinetics ofpiperylene cationic oligomerization 117 5.2.2. The influence of kinetic parameters on polymerization reactor
selection 120 5.3. Separation of fast and slow stages under polymers synthesis in the
presence of Ziegler-Natta catalysts 123
CHAPTER6. DEVELOPMENT OF NOVEL TECHNOLOGIES FOR FAST PROCESSES IN TURBULENT REGIME 141
6.1. Plug-flow tubular turbulent apparatus -the novel type of industrial apparatus 141
6.2. Polymers production 143 6.2.1. Ethylene-propylene rubbers production 143 6.2.2. Chlorobutyl rubber production 147 6.2.3. Liquid oligo-piperylene rubber production 149 6.2.4. Anti-agglomerator production for synthetic rubbers 151 6.3. Low-molecular products production in the flow 151 6.3.1. Unblended benzene production 151 6.3.2. Alkyl-sulfates production 152 6.3.3. Neutralization of acid and alkali mediums 158
CONCLUSION 161
