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m && C
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Petroleum & Coal 47 (2), 26-38, 2005

M. Kotora, Z. Švandová, J. Markoš1, and Ľ. Jelemenský
Department of Chemical and Biochemical Engineering, Slovak University of
Technology, Radlinského 9, 812 37 Bratislava, Slovak Republic

Received July 11 , 2005; received in revised form September 26, 2005; accepted September 28, 2005

Selectivity and equilibrium of chemical reactions can be significantly influenced by the distillation of one or
more products from the reaction mixture. Simultaneous reaction and separation of the desired product is
very important in the case of consecutive reactions. Simulation of the reactor for propylene oxide (POX)
synthesis from propylenechlorohydrine (PCH) and calcium hydroxide is presented in the paper. The main
reaction is very fast, followed by hydrolysis of POX in a basic solution into propylene glycol (PGLY). To
eliminate the PGLY production, POX is stripped by steam from the reaction mixture. Using the developed
model, the optimal design and working performance of the reactor are presented. The role of chemical
reaction kinetics is discussed.
Key words: reactive distillation, propylene oxide production, mathematical model

The present conceptual design of any chemical process results in a flow-sheet which contains
a reactor and a separation unit. As a separation unit is often used a distillation column,
because of its effectivity and performance. The aim is to decrease the operational costs,
improve equipment performance... These goals can be achieved by combining mentioned
units to one device via reactive distillation. This method offers following advantages [1]:

mergence of reaction and separation units into one implies reduction of the capital costs,
chemical reaction equilibrium limitation can be overcome,
less heat consumption, due to exothermic reaction heat utilisation,
selectivity can be improved. Removing products from the reaction mixture can suppress
side reactions,
− reduced catalyst requirements for the same degree of conversion,
− avoidance of azeotropes. Conditions in the reactive distillation (RD) column can allow
the azeotropes to be “reacted away” in a single vessel,
− safer process running. The reaction heat is withdrawn by liquid vaporisation.
These advantages were known long time ago. Reactive distillation phenomena include a complex
system of non-linear equations. Due to this fact, an extensive research was limited by
computational power of PC’s. The occurrence of chemical reaction on stages makes behaviour of
RD columns different to conventional columns. Following that, short-cut estimation methods (e.g.
Fenske-Underwood-Gilliland) with their assumptions cannot be applied. To obtain RD column
parameters, the whole system of equations (material balances, enthalpy balances.) has to be

yD . however problems with finding its solution can occur. y1 . In another way a condenser was balanced. Equations used to describe physical and chemical properties of the studied process should be chosen carefully. enthalpy and equilibrium equations were calculated. 1. the production of propylene oxide from propylene chlorohydrine is discussed. Mathematical model We consider a multistage rectification column illustrated in Fig. condensation temperature (T0) in a partial condenser if used. RD column represents a system of strong non-linear equations. xF . Tm −1 Q& . Assumptions and simplifications From the mathematical point of view. TF n = nTOP Reactive section n = nBTM r n&V . On each stage material. T0 n =1 r n& D . which includes range of stages from reboiler (n=m) to the top of the column (n=1). xm −1 . xLD .1 .1: Scheme of RD column We started the column balancing by dividing it into two major parts. Tm n = m −1 n=m r n&L . r n&V . m −1 . As an example. T0 r n& F . First part was a column balance. partial condenser). By every added equation we obtain more precisely described system. The aim of this paper is to show our used model and a way of balancing which can lead to relevant results. m . reflux ratio in case of a total condenser. T1 Q& K r n& LD . ym . Kotora et al. TP r n&W . range of the reactive section bounded with the upper (nTOP) and lower (nBTM) reactive stage. xW ./ Petroleum & Coal 47 (2) 26-38 (2005) solved. TW Fig.M. m& P . In dependence on its functionality (total. In our case following assumptions are considered: − pressure drop in the column is neglected − zero mixing enthalpies of streams 27 . characteristics of the feed. adequate equations were estimated. volume of liquid on each stage and in the reboiler. where the following parameters are known: number of stages (m).

i ⎥ ln Pno.i = ⎢ Aa .i .i n.i .i .Λ kj jj (4) =1 λij − λii = Aij + Bij . Kotora et al. By M including Murphee’s stage efficiency E y equation (1) changes into: yn . Tn n&V .2 schematically expresses directions and meaning of the assumed streams on the n–th stage for the i–th component.Tn (5) Coefficients Aij . Tn k =1 k k . yn .M.i P .i F ⎤ + Da .log Tn + Ea . Bij were obtained from HYSYS program database. TF .Tn a .i are Antoine’s equation constants of the species i. x VR n& L .i = Pno.i – activity coefficient of the i-th component in the liquid solution.i .i . i . Tn NF ∑ n& k =1 F . Fig.i . j ./ Petroleum & Coal 47 (2) 26-38 (2005) 28 − ideal behaviour of the vapour phase (process running at atmospheric pressure) − chemical reaction occurs only in the liquid phase − steady state − ideal mixing on each stage − Vapour-liquid equilibrium Specifying the general condition of vapour-liquid equilibrium (given by equality of compound fugacities in each phase) in terms of mentioned assumptions for the n-th stage we obtain: P. Our individual pairs Aij . o The vapour pressure of pure species Pn . n& L .i .i − (1 − E yM ). Λ ii = Λ (3) .i + Tn ⎣⎢ ⎦⎥ where (2) Aa . n +1 .Λ ij ⎟ + 1 − ⎝ j =1 ⎠ k =1 Ni ∑x j =1 Λ ij = V j( l ) Vi (l ) ⎛ ( λ ij − λ ii ) ⎞ ex p ⎜ − ⎟ R Tn ⎝ ⎠ Wilson’s model for x n .i . γn.i .γ n . xn −1. Da .i . 2: Scheme of one stage In steady state we can for the n-th stage and the i-th component write material balance (MB): .i (6) Material balances For a better interpretation. i = E M y Pno.i + Ca .xn . Tn −1 n&V . yn +1. n . Ea . where Bij coefficients were equal to zero. n −1 .xn . Tn +1 Fig.i . Fa . Ba .γ n . Ca .i . i = − ln ⎜ ∑ x n .i .i (1) where P is system pressure. xF .k . Unknown pairs were computed by contributory methods. yn +1. xn .i .Λ ki Ni ∑ γ n .i . yn . Bij can be based on the experimental vapour-liquid equilibrium data of binary systems.k Tn ND ∑ n& . k . For the calculation of activity coefficients of each i component on the n-th stage multicomponent mixture was used: ⎛ Ni ⎞ ln γ n .k . n .i was estimated by Antoine’s equation: ⎡ Ba .i .

k ∑ n& k =1 F .i represents reaction source in a unit volume at the current stage NS. NS + n&V . the following substitution is applied: n&L . For the balance of component i.i − ∑ ∑ n&k .xLD . Kotora et al.i + nL .i (10) r Aspects about methods of estimations of n& LD .i (9) j =1 where ξ&V .i − nL . n +1 .i + nV . i Ni ∑z r n& D . n r n&V . ND is the number of drains.i . n . T0 NS .i − nV . k .2 NS = 3 NS . n . This can be evaluated by the following equation: Nr zn.i VR .n − n&D = 0 NS =1 k =1 (8) NS =1 k =1 Ni where NF is the number of feeds.k . n −1 . yn +1./ Petroleum & Coal 47 (2) 26-38 (2005) NF 29 ND ∑ n& & & & & & F . i NS = n VR . Tn +1 r n& L .n . NS − n&L.n. j is the reaction rate of the j-th reaction on the n-th stage relased to the volume of reaction mixture VR. n .i = 0 (7) k =1 k =1 and the overall balance relation (see Fig. k i =1 i =1 VR . Tn Fig. j .M. xF .i represents the stoichiometric coefficient of component i in reaction j.i = ∑ ξ&V . The material balance on each stage is supplemented by the definition equation: Ni 1 − ∑ xn . Another specific stage is the last stage. n . 3: Balancing scheme for the overall material balance of the n-th stage Equation (7) is valid for the first stage of the column in a modified form. term ∑z i =1 NS . k .xn .i = 0 i =1 (11) .3 Ni ∑z NS = 2 NS . i r . NS = 1 Ni ∑z NF ∑ n& k =1 F .k VR . yn +1 . xD . TF .ν j . xF .k i =1 r . It contains one stream less than the general stage.VR − ∑ nk . xn . n +1 .i + zn .1 Ni ∑z i =1 NF NS . xF . n .3): n NF ∑ ∑ n&F . yn . NS ∑ zNS . ν j . TF .xn −1.xn −1.n+1 + n Ni NS =1 i =1 n ND ∑ VR.xLD are discussed bellow (see condenser balances).i = n&LD .n −1. k .xn .` .

HV . With assumption of the existence of a reaction only in liquid phase.n +1 + n& L .n −1 = n&LD .i .i = AL .i (12) i =1 o where the molar enthalpy of pure liquid component i H L .n .i . Each stage has been separately balanced.i = Δ vap H io + AV . n − n&V . (17) & on the n-th stage: which is an inter-step to the overall reaction heat Q r . n +1.n Q& r .i .ξ&V . (Tn2 − Tref2 ) 2 + CV . BX .i .H L .i .i is given by the relation: Tn H Lo.VR . covering its special settings (e. As the reference state the liquid state has been declared at the reference temperature. (Tn4 − Tref4 ) 4 (16) where AX .i . n .n = ∑ xn .i . k . the enthalpies of particular streams were calculated as follows: Molar enthalpy of the liquid flow on the n-th stage: Ni H L . CpL . the relation for the reaction enthalpy has the following form: Δ r H j (Tn ) = Δ r H j (Tref ) + ∫ Tn Tref Ni ∑ν i =1 j .i .n = ∑ yn .n .k .M. k .../ Petroleum & Coal 47 (2) 26-38 (2005) 30 Enthalpy balances Similar to material balancing practice enthalpy balancing was applied for the column.H Lo. (Tn3 − Tref3 ) 3 + DV .i dT . n −1.H F . C X . (Tn2 − Tref2 ) 2 + C L .HVo .H L .i to polynomial series and consequently applying an integration.).i .k .n = ∑ ( −Δ r H j (Tn ) ) . The subscript X indicates the state and Δ vap H i is the heat of evaporation of o pure component i at reference temperature.n −1.i dT (13) Tref Developing CpL .H LD .n − n&L .H L .(Tn − Tref ) + BV . n .(Tn − Tref ) + BL . the form of the balancing equation for the current stage depends on its configuration respective position in the column.i . we obtain: H Lo. Kotora et al.i (15) i =1 and finally for the i-th pure component vapour enthalpy holds: HVo .i . reboiler.g.n .i . V are constants used for the molar heat capacity evaluation.n − ∑ n& L .n . n −1 + ∑ n&F .n .n . j Nr (18) j =1 Similar as for material balances.i for X = L.n .n . (Tn3 − Tref3 ) 3 + DL . In general case this equation can be written in the form: NF ND k =1 k =1 Q& r . first stage.n . DX . According to this fact.H L . (Tn4 − Tref4 ) (14) 4 For the vapour stream enthalpy on n-th stage: Ni HV .i .i = ∫ CpL .i .n .n + n&V .HV .n = 0 (19) A modification of equation (19) for the first stage includes the following substitution: n&L .

0 ) and consequently condensation of exactly that part of the vapour stream. n +1.xLD . Despite the mentioned.i = 0 (21) Summation equation: Ni ∑y i =1 Ni D . solving the following equation: Ni 1 − ∑ y D .i − ∑ xLD . n +1 from equation (19).CpV .i was obtained from equation (21). We assume that the condensate is taken away at the boiling temperature of the mixture.i = 0 (20) Equilibrium condition for the i-th component: y D . this is considered to act like another equilibrium stage. that only one parameter is unknown.1. two types of condenser are assumed. by setting up the condenser temperature. Written into a formula for the i-th component. A different situation occurs with total condenser engagement. we treat the composition and flow rates as unknown parameters. In case of a partial condenser./ Petroleum & Coal 47 (2) 26-38 (2005) 31 Assessment of column’s last stage (reboiler) involves removing the term n&V .i = 0 (22) i =1 And finally.Δ vap H 0 ) at the condensation temperature T0. (26) . the outgoing gas and the liquid phase have an equilibrium composition given by the r known composition of the inlet stream n&V .1. In the next section we will discuss about both these cases. we obtain: (24) y1.HV . we can determine the composition and indirectly the rate of outgoing streams. The value can be obtained by a standard technique. y1 and by temperature and pressure conditions in the condenser. To obtain their values.H D − n&LD . Condenser balances As we have been mentioned before. Therefore. there is no change of composition encountered. because they cannot be expressed implicitly. RX + 1 (25) means. Briefly.M.1.1 − n&D . We assume that the whole inlet vapour stream is being condensed.H LD − n&LD . As a consequence of that. It is the temperature T0 in the condenser. yD .i Establishing the reflux ratio definition: RX n& L D = n&V . (23) where two last terms represent heat removed in the condenser. the inlet vapour stream cooled from the temperature T1 to T0 ( n&V . y1. As a matter of fact.oi . Material balance of the species i: n&V .1 .1.γ 0.HV . Kotora et al.0 = 0. model conception.Δ vap H 0 − n&V .i = xLD .i − n&LD .i P .xLD . for the enthalpy balance holds: n&V . which is being returned to the column via reflux ( n&LD .i − P0. Each of them has its own specification. These extra equations were added to the whole column balancing relations and estimated as the entire “package”. a system of non-linear equations has to be solved.g.i = 0 i =1 where the value of yD .1. etc.i − n&D . e. the used equations are summarised below.CpV . number of unknown parameters.

j = kV ∞./ Petroleum & Coal 47 (2) 26-38 (2005) 32 Solving method Model equations (1) – (26) represent a system of non-linear algebraic equations.394×1024 3.6 68048. the production of the consecutive side product. Table 1: Kinetic parameters of the assumed reactions Reaction (R1) (R1) (R2) kV ∞ 3. Model system Propylene oxide synthesis has been chosen as a model system. the OH − ions is constant and depends only on temperature[2]: = 0.CPCH ξ&V 2 = kV 2 . kV 2 can be expressed by equation: ⎛ − Ej ⎞ kV .68×108 s-1 s-1 3 m mol-1 s-1 E [kJ kmol-1 ] References Δ r H (25o C ) 187131 66402. Because of its small solubility in water. j . taking place in the liquid phase. [2]. It is a typical problem of a consecutive reaction. Kotora et al. Kinetics of chemical reactions The reaction scheme for the propylene oxide production can be written as follows: Ca ( OH ) 2 CH 3CH 2ClCH 2OH ⎯⎯⎯⎯ → CH 3 (CH 2CH 2 )O − HCl (R1) Ca ( OH ) 2 ( PCH ⎯⎯⎯⎯ → POX ) − HCl − OH CH 3 (CH 2CH 2 )O + H 2O ⎯⎯⎯ → CH 3CH 2OHCH 2OH (R2) − OH ( POX + W ⎯⎯⎯ → PGLY ) The reaction rate can be expressed by the following expressions [2]: ξ&V 1 = kV 1.13 − 3. Ca (OH ) 2 is usually used. For reaction (R1) two values from two different sources were found.02×109 2. By stripping propylene oxide from the solution. ethylene glycol. [3].COH (27) (28) − − As a source of OH ions.01× 10−4 T concentration of COH − (29) The temperature dependence of the reaction rate constants kV 1 . for which reactive distillation is advantageous.M.T ⎠ j = 1. j for both reactions (R1) and (R2) are summarized in Table 1. 2 (30) The values of kinetic parameters kV ∞.CPOX .1 [3] [2] [2] -27520 kJ kmol-1 -83920 kJ kmol-1 . j and E j .exp ⎜ ⎟ ⎝ R. which were solved using the Newton-Raphson method with numerical evaluation of the Jacobian matrix and with defined constrains for all variables. can be minimized.

which are side products from the PCH synthesis)./ Petroleum & Coal 47 (2) 26-38 (2005) 33 Material balance A water solution of propylene chlorohydrine is mixed with a water suspension of Ca (OH ) 2 and fed into the column (with an excess of Ca (OH ) 2 with respect to PCH). [4]. steam temperature and flow rate. Therefore.16 t h-1 nchz [3] mdli [2] Results and discussion There is a lot of parameters. . POX.18 20. mainly the number of column stages. Kotora et al. [5]. Because of a lack available data for Ca (OH ) 2 and CaCl2 influence on V – L equilibrium and physical and chemical properties of the liquid solution. We assumed in the column only four compounds: PCH. From the feed stage the POX fraction is increasing.8oC PCH 0. in this paper. with 20 reactive stages including reboiler).7 2.5 .10. The composition of feed streams into the column is reported in Table 2.15. At given temperature. influencing the behaviour of the RD column.3 m 0.096 0 xF mol. Table 2: Parameters of the feed streams into the column Number of feed 1 (raw material) 2 (steam) Feed characteristics Feed stage variable 25 Feed temperature 90oC 158.% POX PGLY 0 0 0 0 W 0. temperature in the condenser. diameter of the column. PGLY and W.8oC was used. In the following pictures and discussions.M.9904 1. This was fed directly into last stage – reboiler.8 m 0.0 Table 3: Parameters of the reactive distillation column Fixed column parameters Number of stages Volume of the reboiler Diameter of the column Height of the stage Liquid height in the stage Temperature in the condenser 25 5 m3 1. etc. we fixed some of them. 57 mol% of POX in the distillate was obtained. The parameters for V – L equilibrium described by Wilson’s equation and physical properties of vapour and liquid solutions were taken from the literature. volume of the reboiler. as listed in Table 3.08 m 80oC Variable column parameters Position of the feed stage Number of the reactive stages Mass flow of the steam Kinetics data performed by 5. volume of the liquid on the stage. As a heating medium. position of the feed stage (and consequently the number of reactive stages). saturated steam at a temperature of 158. these compounds were neglected (together with other organic compounds like DCP. what is induced by a drop of temperature in the partial condenser T0=80oC. 4 are given the concentration profiles of all assumed compounds in the vapour phase (25 column stages. Simulation of the column In Fig. the kinetic parameters of reaction (R1) are taken from[3].

For a low steam flow rate. In designing the column with a maximal yield of POX and minimizing the PGLY production. in which a huge amount of heat has to be removed to obtain a distillate with desired composition.0 0. For a low number of reactive stages. High steam flow rate reduces the production of PGLY and the concentration of POX and PCH in the reboiler.9 0. .1 0. two problems for solving must be solved: by increasing the number of reactive stages. we can minimize the concentration of PCH in the reboiler (there are severe ecological limits for organic chlorine released from the reboiler).4 pch pox pgly w 0. 7). on the other hand. 4: Molar compositions over the RD column.0 0 5 10 15 20 25 Stage number Fig. a lot of reactive stages favour the hydrolysis of POX into PGLY. 6. This fact can be explained by a short residence time of POX on the reactive stages. the influence of number of the reactive stages on POX production is not great.M. In Fig. POX is not quantitatively stripped from the liquid phase and is passed to the reboiler. On the other hand. A high steam flow rate influenced the POX production with a higher number of reactive stages. The feed stage is the fifth stage.2 0.3 0. and its hydrolysis can proceed to high degree (see Fig. However the yield of PGLY is considerably higher for a higher number of reactive stages.6 0.8 0. Kotora et al. The above mentioned conclusions are demonstrated in Figs./ Petroleum & Coal 47 (2) 26-38 (2005) 34 1. it needs a condenser. The parameter is the number of reactive stages is drawn.5 0. 7. The hydrolysis of POX could be avoided by increasing the flow rate of the stripping steam. where its residence time is high because of the reboiler volume. flow rate of fed steam into the reboiler is drawn. 5. 5 the plot of the production of POX vs.7 y / [1] 0.

15pox r.20 r. measured in NCHZ. flow rate of steam fed into the reboiler.s.h ] Fig.15 r.s.s. using parameters from[3] and[2] shows that reaction rate constant using data from[2] is approximately 70 times higher than that from data evaluated in[3]. 6: Yield of POX and PGLY as a function of the number of reactive stages and the amount of steam fed into the reboiler The optimal design of the column therefore requires an economic analysis balancing the price of POX.7 Fig. 20.6 yield -1 mPOX / [kg.15.s.2 0 0 2500 5000 7500 10000 12500 0. Inc./ Petroleum & Coal 47 (2) 26-38 (2005) 35 1. In Table 1 are summarized the values of the pre-exponential factors and activation energies.s.s.h ] Fig. .h ] -1 steam / [kg. taking into account also the ecological constrains (for PCH and PGLY concentrations in the waste stream from the reboiler. Parameter of the curves is the number of reactive stages.. price of the used steam and cooling water in the condenser. Kotora et al. rate constant taken from the work of Carra et al.0 1200 0.[3].M. Nováky.20pox r.0 15000 0 2500 5000 7500 10000 12500 15000 -1 steam / [kg. Influence of kinetic parameters on the column simulation For simulation of RD column for POX synthesis two rate constants of reaction (R1) were used: rate constants estimated from the experimental data obtained in a laboratory scale batch reactor..h ] 1000 600 r. 7: The amount of POX [kg h-1] produced compared to 1 kg h-1 of PGLY as a function of steam flow rate and the number of reactive stages. which is passed to the waste water treatment plant).[2]. A comparison of the reaction rate constant of reaction (R1) at a temperature of 100°C.s.s.20pgly r.7pgly 0.s.7 5 0 2500 5000 7500 10000 12500 15000 -1 steam / [kg.15pgly r. 30 mPOX(D) / mPGLY(W) 25 20 15 10 r.15 r. in this part of work some simulations have been done to demonstrate the importance of appropriate kinetic data for RD column design and optimization. 5: Mass flow rate of POX from the condenser vs. Slovakia.s.s.8 800 0.20 r. Therefore.4 400 r.7pox r.s.7 200 0.

f. the number of feed stage is 15. the number of feed stage is 5 (15 reactive stages) .0006 0.0001 nchz mdli nchz mdli 0. Fig./ Petroleum & Coal 47 (2) 26-38 (2005) 36 1200 1200 1000 1000 800 800 -1 production / [kg h ] -1 production / [kg. 9 and 11). The number of stages is 20. the number of feed stage is 15 (5 reactive stages) 0 5 10 15 20 stage number Fig.M. Kotora et al.h ] -1 steam / [kg h ] Fig. By increasing number of reactive stages (from 5 to 15) the production of POX is increased with a higher selectivity. 8 and 9 the production of POX and PGLY is compared using different kinetic data for reaction (R1) as a function of the steam flow rate and position of the feed stage.0005 0.0004 y PCH yPCH / [1] 0.0003 0. 10).h ] In Figs.0002 0.0001 0.0006 0. The number of stages is 20. but it is still lower than in the case of a reaction proceeding with a higher rate (using data from [3]) in all the range of the assumed steam flow rate (c.0000 0 5 10 15 20 stage number Fig.0000 0.0007 0.0003 0. 9: Production of POX and PGLY vs steam flow rate by using two sets of kinetic data. The number of stages is 20. and the important part of PCH is flowing into the reboiler (see Fig. dehydrochlorination of PCH is not sufficient in a low number of reactive stages. Figs. the number of feed stage is 5 0.0005 0.0002 0. 10: Comparison of the concentration profiles of PCH in the column obtained using two different reaction rate constants for simulation. Even a high steam flow rate is unable to strip POX from the liquid and its hydrolysis in the reboiler yields a high production of PGLY. 600 nchz_pox nchz_pgly mdli_pox mdli_pgly 400 200 600 nchz pox nchz pgly mdli pox mdli pgly 400 200 0 4000 6000 8000 10000 12000 14000 16000 0 18000 0 2000 4000 6000 8000 10000 12000 14000 16000 -1 steam / [kg. 8: Production of POX and PGLY vs steam flow rate by using two sets of kinetic data. 11: Comparison of the concentration profiles of PCH in the column obtained using two different reaction rate constants for simulation. The number of stages is 20. Because the predicted reaction using the data from[3] is very low (with respect to data from[2]).0004 0.

h-1 number of the stage molar flow rate mol. different results have been obtained.s number of the first reactive stage number of the last reactive stage number of species number of reactions pressure vapour pressure of pure component heat removed in the condenser Pa Pa -1 J. Da. .APVT-20-000804 List of symbols Aa. and kinetic parameters.M. the unit depends on the form of the polynomial constants of polynomial series used for the molar heat capacity of the vapour phase computation.K -1 -1 vapour molar heat capacity J. dimension depends on the form of the reaction rate equation pre-exponential factor. i. Acknowledgement This work was supported by Science and Technology Assistance Agency under the contract No. The main effort has to be paid to parameters of the multicomponent vapour – liquid equilibrium model.Ca. both in the selectivity and the yield of the process. .CL.mol -1 reaction enthalpy J. Fa Aij.mol Murphee’s stage efficiency -1 molar enthalpy of the liquid stream J.mol -1 molar enthalpy of the pure liquid material J.mol ./ Petroleum & Coal 47 (2) 26-38 (2005) 37 Conclusion The steady state mathematical model of a reactive distillation column and its FORTRAN code were developed.m -1 -1 liquid molar heat capacity J.m -1 -1 -3 .K -1 activation energy of chemical reaction J. Ea.e. Kotora et al.. The possible use of such model is demonstrated for the example of propylene oxide synthesis.s . undesirable product. The importance of the first group of parameters is discussed in numerous papers in the literature. In this paper we focused our attention to the second group of parameters. AV. In this paper the presented model and robust algorithm of model equations solution represent an useful tool for simulation and design of the reactive distillation column size and optimal performance conditions. the unit depends on the form of the polynomial -3 molar concentration mol. The ability of the model to simulate the RD column behaviour depends also on the appropriate values of the model parameters.mol -1 heat of vaporisation of pure material J..mol .BV..mol -1 molar enthalpy of the liquid reflux stream J.BL.s heat released by chemical reactions J. kinetic parameters..f.[1]. dimension depends on the form of the reaction rate equation last stage (reboiler) steam mass flow rate kg..mol reaction rate constant in the reaction volume unit.mol -1 molar enthalpy of vapour stream J.Bij AL. By simulating the RD column with two different values of the reaction rate constant of the principal chemical reaction (R1). Ba.CV. This example was chosen as a typical process with consecutive reactions. where the desired product could be converted into a side. c.mol -1 molar enthalpy of pure vapour material J. C CpL CpV E E M y HL HLD o HL HV o HV ΔrH ΔvapHo kν kν∞ m m& P n n& NTOP NBTM Ni Nr P o P Q& K Q& r constants of Antoine’s equation binary coefficients in Wilson’s activity model constants of polynomial series used for the molar heat capacity of the liquid phase computation.

s . Markoš.m mol.s .. E. Kinetics aspects of the process..2. Krishna R. 1123-1132 [3] Markoš.mol -3 m -1 -3 -1 -3 mol.. (1979). 2003.. Ľ. Chemical Engineering and Processing. Cavalli.. E....m • Subscripts 0 indication of condenser 1. M. Kotora et al. Prausnitz.. 34. Chemical Engineering Science. 42. number of stage D distillate F feed i component labelling j reaction labelling res. Molnár. Graczová. Santacesaria. . Morbidelli... identification of the second component in Wilson’s model L liquid phase LD reflux m last stage (reboiler) n current number of stage NS number of stage V vapour phase W distillation rest • Superscripts g gas phase l liquid phase ND number of drains NF number of feeds on the stage Ni number of compounds Nr number of chemical reactions o pure material • List of abbreviations DCP dichloropropane ClCH2ClCH2CH3 PCH propylene chlorohydrine CH3CHClCH2OH PGLY propylene glycol CH3CH2OHCH2OH POX propylene oxide CH3(CH2CH2)O RD reactive distillation W water H2O References [1] Taylor R. R. Modelling reactive distillation. 1989 [5] Šoóš. R. M.. Design and simulation of a distillation column for separation of dichloropropane from a multicomponent mixture. M. P.mol . A. McGraw – Hill Book Comp.. 273 – 284 .... Poling. (2000). The Properties of Gases and Liquids..K -1 K 3 -1 m ..i ξ&V gas constant reflux ratio thermodynamics temperature molar volume of the i-th liquid component reaction mixture volume molar ratio in the liquid phase molar ratio in the vapour phase chemical reaction source activity coefficient in the liquid phase energy of interaction of the i-th with the j-th component Wilson’s parameter stoichiometric coefficient of the i-th component in the j-th reaction chemical reaction rate in the volume unit 38 -1 J.M. J. E. Synthesis of propylene oxide from propylene chlorohydrins – 1. 2004 [4] Reid. Jelemenský. Inc.. J. Steltenpohl./ Petroleum & Coal 47 (2) 26-38 (2005) R RX T (l) Vi VR x y z • Greek letters γ λij Λij νj. Technical report of the Contract No. 55... 5183-5229 [2] Carrá.. J.47/04 for NCHZ. Chemical Engineering Science. L. New York...C. S. M. Kotora.