(S1.3) dt Taking into account equation (S1.1) and the fact that the reaction volume is constant, equation (S1.3) can be rewritten as:
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1 roblem 1 Overall Material alance: dn d( ρv) dv dρ = =ρifi ρf ρ + V =ρifi ρ F (S1.1) ssuming constant density and reactor volume, equation (S1.1) yields: ( ) ρ F F = 0 F F = 0 (S1.2) i i Therefore, the input and output flow rates are equal at each point in time. Component Material alance: ) 2 i f Fc k1cv k3cv (S1.3) Taking into account equation (S1.1) and the fact that the reaction volume is constant, equation (S1.3) can be rewritten as: dc F 2 = ( c f c ) k 1 c k 3 c (S1.4) V Component Material alance: ) = Fc + k1cv k2cv (S1.5) Since the reaction volume is constant, equation (S1.5) becomes: dc F = c + k 1 c k 2 c (S1.6) V Component C Material alance: C) = FcC + k 2cV (S1.7) s the reaction volume is constant, equation (S1.7) is rewritten as follows:
2 dcc F c C k 2 c = + (S1.8) V Component D Material alance: D) 1 2 = FcD + k3cv (S1.9) 2 s the reaction volume is constant, equation (S1.9) yields: dcd F 1 2 = cd + k3c (S1.10) V 2 In equations (S1.4) and (S1.10), the reaction rate is defined with respect to the number of moles of that are consumed due to reaction (1.3). Therefore, the factor 1/2 appearing in equation (S1.10) accounts for the fact that for each mole of consumed, half mole of D is produced. Thus, a) The model is given by equations (S1.4), (S1.6), (S1.8) and (S1.10) b) State variables: c, c, c C, c D Input: F i, c o Output: F, c, c, c C, c D arameters: ρ, V, k 1, k 2, k 3 roblem 2 Overall Material alance: s in problem 1, assuming constant density and reactor volume yields: Fi F= 0 (S2.1) Therefore, the input and output flow rates are equal at each point in time. iomass Material alance:
3 d(vx) = Fx +µ xv (S2.2) Taking into account equation (S2.1) and the fact that the reaction volume is constant, equation (S2.2) can be rewritten as: dx µ maxs F = x (S2.3) Ks + s V Substrate Material alance: d(vs) µ xv = Fs i f Fs (S2.4) Y Considering equation (S2.1) and the fact that the reaction volume is constant, equation (S2.4) can be rewritten as: ds F 1 µ maxs = ( sf s) x (S2.5) V Y Ks + s Hence, a) The model is given by equations (S2.3) and (S2.5) b) State variables: s, x Input: F i, s f Output: F, s, x arameters: ρ, V, K s µ max, Y roblem 3 Overall Material alance: dn d( ρv) dv dρ = =ρ ifo +ρf1 ρf ρ + V =ρ ifo +ρf1 ρ F (S3.1) ssuming constant density and reactor volume, equation (S3.1) yields: ( ) ρ F + F F = 0 F = F F (S3.2) o 1 o 1
4 Therefore, the input flow rate is equal, at each point in time, to the fraction of the output flow rate that is not recycled to the reactor. Component Material alance: ) o o + Fc 1 Fc kcv (S3.3) Taking into account equation (S3.1), considering that the reaction volume is constant and substituting equation (3.2), equation (S3.3) can be rewritten as: dc Fo Fo = co ko exp c V + V RT (S3.4) Component Material alance: ) 1 Fc+ kcv (S3.5) Taking into account equation (S3.1), considering that the reaction volume is constant and substituting equation (3.2), equation (S3.5) becomes: dc Fo = c + koexp c (S3.6) V RT Overall Energy alance: du F o o u o F 1 u F u W Q = ρ + ρ ρ + (S3.7) In equation (S3.7), U is the internal energy of the fluid (kcal), u o and u are the molar internal energies that the system exchanges with the surrounding environment (kcal/moles). Moreover, W is the rate at which heat is generated during the reaction (kcal/h), while Q denotes the rate at which heat is removed from the stream that, leaving the heat exchanger, is recycled to the reactor (kcal/h). Letting p represent the reactor pressure and H the fluid enthalpy, one can write: U= H pv (S3.8) Differentiating (S3.8) yields: du dh dv dp = p V (S3.9) ssuming constant pressure p and volume V, (S3.9) becomes du dh = (S3.10) Equation (S3.10) states that the rate of enthalpy accumulation in a system is equal to the rate at which the internal energy of the same system changes in time at constant pressure and volume. Since the heat capacity is defined as the variation of the molar enthalpy due to a change in the system temperature (i.e. c =dh/dt), then (S3.10) can be rewritten as follows:
5 du = dh =ρ V dh =ρ Vc dt (S3.11) For liquid systems, the internal energy can be generally approximated with the enthalpy of the system at the same conditions (see Sandler (1999) for a more detail explanation). Therefore, it follows: u h = c (T T ) (S3.12) ref u h = c (T T ) (S3.13) o o o ref where T an T o respectively represent the output and input temperatures whereas t ref denotes a reference temperature. Choosing as reference temperature the one of the feed stream, equations (S3.12) and (S3.13) yield: u c (T T ) (S3.14) o uo 0 (S3.15) The rate of heat produced during the reaction can be expressed as the product of the number of moles of consumed times the heat released per mole consumed, as follows: W = koexp cv( H) (S3.16) RT Finally, the rate of heat removed from the fraction of fluid that is recycled to the reactor can be expressed as the product of the mass flow rate times the heat capacity times the variation between the input and output temperatures of the water, as follows: Q= wc (t t ) (S3.17) p,w o Therefore, equation (S3.7) becomes: dt ρ Vc = Foρc (T T o) + koexp cv( H) wc,w(t t o) RT Thus, c) The model is given by equations (S3.4), (S3.6) and (S3.18) d) State variables: c, c, T Input: F o, c o, T o Output: F, F 1, c, c, T arameters: ρ, V, k o, c, c,w, E, R, (- H), w, t, t o (S3.18) Sandler, S.I. (1999) Chemical and Engineering Thermodynamics. John Wiley & Son, New York.
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