OP-II-3

PP-II-16SIMULATION OF HEAVY PARAFFINS DEHYDROGENATIONREACTORFrantsina E.V., Afanasjeva Y.I., Maksimova E.S.,Romanovskiy R.V., Ivanchina E.D.Tomsk Polytechnic University, 634050 Tomsk Lenina sq., 30, evf86@sibmail.comSimulator methods allow to execute a quantitative estimation of technologicalcharacteristics of manufacture and to raise its efficiency [1].The presumable transformation scheme of the process was designed on thebasis of the dehydrogenation mechanism. Electron molecule structures and reactionthermodynamic characteristics (∆G r , ∆Н r , ∆S r ) were estimated for conditions 753 Kand 0,2 MPa using the quantum-chemistry calculation methods (Gaussian programpackage containing PM3 procedure of NDDO method) [2].Thus the results show that aromatization reaction appears to be the mostthermodynamically probable (∆G 0 r≈–300 kilojoule/mol). Paraffins and olefinesisomerization reactions do not occur in the present process. Also the reactions ofdienes formation with cumulative double bonds are not thermodynamically allowed(∆G 0 r ≈ –5 kiloJoule/mole). The presence of isomeric paraffins in the product isdetermined by iso-paraffins dehydrogenation processes which are present in rawmaterials. All other possible reactions are thermodynamically probable and haveapproximately the same value of isobaric-isothermal potential(∆G 0 r ≈ –70 kilojoule/mol). In the process the dienes with conjugate and secureddouble bonds are obtained, whereas formation of dienes with cumulative doublebonds is not thermodynamically allowed under these conditions. Cracking(∆G 0 r ≈ –140 kilojoule/mol) and coke formation (∆G 0 r≈–510 kilojoule/mol) are the mainby-reactions.On the basis of these results the formalized scheme of higher alkanes C 9 -C 14dehydrogenation process was designed. Formalization layer of transformationcompounds mechanism assumes the aggregation of pseudo components into groupsaccording to reactionary ability that is evaluated according to isobaric-isothermalpotential ∆G r . Thus 11 groups of pseudo components were formed that participate in22 types of chemical reactions.Kinetic model was developed according to the law of active mass and formalizedtransformation scheme. Effective rate constants are combination of all intermediate360