CONVERSION AND REACTOR SIZING

• Objectives: • Define conversion and space time. • Write the mole balances in terms of conversion for a batch reactor, CSTR, PFR, and PBR. • Size reactors either alone or in series once given the molar flow rate of A, and the rate of reaction, -rA, as a function of conversion, X.

• Conversion: Choose one of the reactants as the basis of calculation and relate the other species involved in the rxn to this basis. • Space time: the time necessary to process one reactor volume of fluid based on entrance conditions (holding time or mean residence time)

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CONVERSION AND REACTOR SIZING
1. Conversion Consider the general equation

aA + bB → cC + dD A C
We will choose A as our basis of calculation.

b c d A+ B → C + D a a a
The basis of calculation is most always the limiting reactant. The conversion of species A in a reaction is equal to the number of moles of A reacted per mole of A fed.

Batch

Flow

X=

( N A0 − N A ) N A0

X=

(FA0 − FA ) FA0

X = Moles of A reacted Moles of A fed

For irreversible reactions, the maximum value of conversion, X, is that for complete conversion, i.e. X = 1.0. For reversible reactions, the maximum value of conversion, X, is the equilibrium conversion, i.e. X = Xe.

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dN A dX (Since N is constant) A0 = 0 − N A0 ⋅ dt dt dX − N A0 ⋅ = rA ⋅ V dt Batch reactor design eq’n dX N A0 ⋅ = − rA ⋅ V (in differential form) dt [4] [5] 3 .2. we are interested in determining how long to leave the reactants in the reactor to achieve a certain conversion X. [N A ] = [N A 0 ] − [N A 0 ⋅ X ] N A = N A 0 ⋅ (1 − X ) [2] dN A = rA ⋅ V dt − dN A = − rA ⋅V dt ( prefect mixing ) [3] For batch reactors. Design Equations Batch Reactor Design Equations: ⎡ Moles of A⎤ ⎡ ⎤ ⎢ reacted ⎥ = ⎡ Moles of A⎤ ⋅ ⎢ Moles of A reacted ⎥ ⎥ fed ⎢ (consumed ) ⎥ ⎢ ⎣ ⎦ ⎣ Moles of A fed ⎦ ⎣ ⎦ = [N A 0 ] ⋅ [X ] [1] Now the # of moles of A that remain in the reactor after a time t. NA can be expressed in terms of NA0 and X.

X t = N A0 ⋅ ∫ 0 dX − rA ⋅ V t As t X Flow Reactor Design Equations: For continuous-flow systems. FA0 ⋅ X = moles of A fed moles of A reacted ⋅ time moles of A fed Outlet flow rate FA0 − FA0 ⋅ X = FA inlet molar flow rate Molar flow rate at which A is consumed within the system F A = F A 0 ⋅ (1 − X ) FA0 = C A0 ⋅ v0 volume / time (volumetric flow rate. t.For a constant volume batch reactor: (V = V0) 1 dN A d ( N A / V0 ) dC A ⋅ = = V0 dt dt dt dC A = rA dt dt = N A 0 ⋅ dX − rA ⋅ V X From [3] Constant volume batch reactor From [5] Batch time. time usually increases with increasing reactor volume. required to achieve a conversion X. dm3/s) moles /volume 4 .

For liquid systems. CA0 is usually given in terms of molarity (mol/dm3) For gas systems.314 kPa dm3 / mol K = T(K) CSTR (Design Equation) For a rxn: A+ b c d B→ C+ D a a a V = Substitute for FA FA0 − FA − rA FA = FA 0 − FA 0 ⋅ X V = V = FA 0 − ( FA 0 − FA 0 ⋅ X ) − rA FA 0 ⋅ X ( − rA ) exit 5 . Partial pressure C A0 = Entering molar flow rate is PA 0 y ⋅P = A0 0 R ⋅ T0 R ⋅ T0 y ⋅P FA0 = v0 ⋅ CA0 = v0 ⋅ A0 0 R ⋅T0 yA0 P0 CA0 R T = entering mole fraction of A = entering t t l pressure (kP ) t i total (kPa) = entering conc’n (mol/dm3) = 8. CA0 can be calculated using gas laws.

the volume of a CSTR and the volume of a PFR can be represented as the shaded areas in the Levelspiel Plots shown below: Levenspiel Plots 6 .PFR (Design Equation) − dFA = − rA dV FA = FA0 − FA0 ⋅ X dFA = − FA0 ⋅ dX Substitute back: − dFA dX = FA 0 ⋅ = − rA dV dV Seperate the variables V = 0 when X = 0 V = FA0 ⋅ ∫ 0 X dX − rA Applications of Design Equations for Continuous Flow Reactors 3. For FA0 / -rA vs. We do this by constructing a Levenspiel Plot. Here we plot either FA0 / -rA or 1 / -rA as a function of X. one can size any type of reactor. -rA = f(X). Reactor Sizing Given –rA as a function of conversion. X.

4 0.6 0.37 0.7 0.8 08 [T = 500 K] [P = 830 kPa = 8. a plot of 1/-rA as a function of X yields : − 1 1 ⎛ 1 ⎞ = ⋅⎜ ⎟ rA k ⋅ C A0 ⎝ 1 − X ⎠ -1/rA X Example: Let’s consider the isothermal gas-phase isomerization: A→B X 0 0.113 0.079 0.2 0.195 0.45 0 45 0.30 0.1 0.05 0 05 7 .A particularly simple functional dependence is the first order dependence: − rA = k ⋅ C A = k ⋅ C A0 ⋅ (1 − X ) Specific rxn rate ( (function of T) ) initial conc’n For this first order rxn.2 atm] initial charge was pure A -rA(mol/m3s) 0.

rA ≈ 0. Keep in mind : 1.2 0.079 0.85 12.13 8.7 20.Example: Let’s consider the isothermal gas-phase isomerization: A→B X 0 0.05 0 05 1 / -rA 2.22 2 22 2.7 0.33 5.37 0.2 atm] initial charge was pure A -rA(mol/m3s) 0. 8 . the rate is y.6 0.45 0 45 0. –rA → 0 thus 1/-rA → ∞ & V → ∞ → An infinite reactor volume is needed to obtain Xe.113 0.4 0. –rA → 0 thus 1/-rA → ∞ & V → ∞ X → An infinite reactor volume is needed to reach complete conversion. As X → Xe.8 08 [T = 500 K] [P = 830 kPa = 8. As x → 1.30 0.0 20 0 Draw -1/rA vs X: -1/rA We can use this figure to size flow reactors for different entering molar flow rates. when the conc’n of reactant is greatest.1 0.195 0.70 3. the max X is the equilibrium conversion Xe. if a rxn is carried out isothermally. (when x ≈ 0 → -1/rA is small) 2. At equilibrium. usually greatest at the start of the rxn. For reversible reactions (A ↔ B).

find − rA at X = 0.4m 3 s mol ⋅ s CSTRs are usually used for liquid-phase rxns.4 mol/s. Five-Point Quadrature Formula 9 . One numerical methods for evaluating integrals are: 1.8 ⎛ 1⎞ m3 ⎜ − ⎟ = 20 ⎜ r ⎟ mol ⋅ s ⎝ A ⎠ 0.5 m3 4. we can calculate [FA/-rA](m3) Plot FA0/-rA vs X obtain Levenspiel Plot! Example: Calculate volume to achieve 80 % conversion in CSTR. Simpson’s Three-Eighth’s Rule (uses four data points) 3. They should be equal.if FA0 = 0.8 = 6.4 For instance: 3. NOTE: The intervals (∆X) shown in the sketch are not drawn to scale. Numerical Evaluation of Intergrals The integral to calculate the PFR volume can be evaluated using a method such as Simpson’s One-Third Rule. Simpson’s One-Third Rule is one of the most common numerical methods. Trapezoidal Rule (uses two data points) 2.6 m3 mol m3 ⋅ 20 ⋅ 0. 1. It uses three data points.8 F ⋅X V = A0 (−rA ) exit = 0.

what PFR volume is necessary to achieve 80 % conversion under identical conditions as those under which the batch data was obtained? 10 . A → Products which is to take place in a PFR. xN ∫ f ( x) ⋅ dx = 3h ⋅ ( f 0 + 3 f1 + 3 f 2 + 2 f 3 + 3 f 4 + 3 f 5 + 2 f 6 .) 8 Example: Consider the liquid phase reaction.008 0.01 0.8 0.4 0. where N is an integer. The following data was obtained in a batch reactor..Trapezoidal Rule f(x) f(x1) A2 f(x0) x0 h A1 x1 x1 x0 ∫ f ( x) ⋅ dx = h [ f ( x ) + f ( x )] 0 1 1 A1 = f ( x0 ) ⋅ h A2 = [ f ( x1 ) − f ( x0 )] ⋅ h 2 A = A1 + A2 f ( x1 ) f ( x0 ) ⎤ ⎡ = h ⋅ ⎢ f ( x0 ) + − 2 2 ⎥ ⎣ ⎦ h = ⋅ [ f ( x0 ) + f ( x1 )] 2 x Five Point Quadrature formula: x4 x0 ∫ f ( x) ⋅ dx = 3 ⋅ ( f x0 h 0 + 4 f1 + 2 f 2 + 4 f 3 + f 4 ) where h= x 4 − x0 4 For N+1 points... X -rA(mol/dm3s) 0 0..002 If the molar feed of A to the PFR is 2 mol/s.

fed to a plug flow reactor PFR ∴V = FA0 ∫ 0 X 1 dX − rA Thus one needs (1/-rA) as a function of X.4 dm 3 s ⎫ 3 =2 ⋅ ⎨ [100 + 4 ⋅ (125) + 500] ⎬ = 293dm s ⎩ 3 mol ⎭ − rA To reach 80 % conversion your PFR must be 293 3 dm3. For Simpson’s three point formula we have: X PFR : V = FA0 ∫ dX ∆X = FA0 ⋅ 3 − rA 0 ⎡ ⎤ 1 4 1 + + ⎢ ⎥ ⎣ − rA ( X = 0) − rA ( X 1 ) − rA ( X 2 ) ⎦ PFR : V = FA0 ∫ 0 0.3 11 .8 dX mol ⎧ 0.Hint : FA0 = 2 mol/s. conversion. 293.

89 ⋅ 0.8 dX F Re arranging : V = FA0 ⋅ ∫ = ∫ A0 ⋅ dX − rA 0 − rA 0 Let’s numerically evaluate the integral with trapezoidal rule 0.8 ⋅ (0. then gradually decreases to the exit rate. 12 .89 + 8.8 ∫ −r 0 FA0 A ⋅ dX ⇒ f (X ) = f (X ) = FA 0 − rA FA 0 − rA = 0.89 X =0 = 8 .Sizing in PFR Example: Determine the volume in PFR to achieve a 80 % conversion. PFR starts at a high y p g rate.165 m3 Comparing CSTR & PFR Sizing VCSTR > VPFR for the same conversion and rxn conditions. The reason is that CSTR always operates at lowest rxn rate.8 0.4 = 3.0) = 8. For PFR : FA0 ⋅ dX = − rA dV 0 .556m 3 2 With five point quadrature V = 2.0 X = 0 .8 V= 0 .

which is connected in series to an existing tubular reactor. FAi = FA0 − FA0 ⋅ X i Example: Using Levenspiel plots to calculate conversion from known reactor volumes. reactor If the volume of the CSTR is 1200 dm3 and the tubular reactor volume is 600 dm3.005 mol/dm3 to an existing CSTR.Reactors in Series: The exit of one reactor is fed to the next one. Given –rA as a function of conversion. one can design any sequence of reactors. Pure A is fed at a volumetric flow rate 1000 dm3/h and at a concentration of 0. 13 . Xi = moles of A reacted up to po int i moles of A fed to first reactor Only valid if there are no side streams. what are the intermediate and final conversions that can be achieved with the existing system? The reciprocal rate is plotted in the figure below as a function of conversion for the conditions at which the reaction is to be carried out.

the intermediate conversion is X = 0. we find that a conversion of 0. we find that a conversion of 0. Therefore.8 14 .6 Similarly for the PFR.8 gives the appropriate PFR volume of 600 dm3. Therefore.6 gives the appropriate CSTR volume of 1200 dm3.Solution: By trial and error. through trial and error. the final conversion is X = 0.

4 X = 0.8 ⎛ FA0 ⎞ ⎜ = 2.0 m 3 ⎜−r ⎟ ⎝ A 2 ⎠ X = 0 .8 Total V = V1 + V2 = 4.05m 3 ⎜−r ⎟ ⎟ ⎝ A1 ⎠ X =0.02 m3 < 6.CSTRs in Series Two CSTRs in series Reactor 1: Mole Balance: FA0 – FA1 + rA1 V1 = 0 FA0 FA1 X1 = 0.4 m3 volume necessary to get 80 % conversion with one CSTR 15 .82m 3 ⎜−r ⎟ ⎝ A1 ⎠ 0.4 ⎛ F ⎞ V2 = ⎜ A0 ⎟ ⋅ ( X 2 − X 1 ) = 3.8 Mole Balance: FA1 – FA2 + rA2 V2 = 0 FA2 = FA0 – FA0 X2 Combining [4] & [5]: [4] [5] V2 = FA1 − FA 2 ( FA0 − FA0 ⋅ X 1 ) − ( FA0 − FA0 ⋅ X 2 ) FA0 = = ( X 2 − X1) − rA 2 − rA 2 − rA 2 if we have the data: X = 0.4 ⎛ FA0 ⎞ ⎜ = 8 .4 -rA1 [1] [2] [3] FA1 = FA0 – FA0 X1 Combining [1] & [2]: V1 = FA0 (1 / -rA1) X1 Reactor 2: -rA2 FA2 X1 = 0.2 > VCSTR.8 ⎛ F ⎞ V1 = ⎜ A0 ⎟ ⋅ X 1 = 0.1 X 0.2m 3 ⎜−r ⎝ A2 ⎠ -FA0/rA VCSTR.4 0.

16 . V2 and V3 for the CSTR/PFR/CSTR reactors in series sequence along with the corresponding conversion. calculate the reactor volumes V1.4 -rA2 X2 X i =1 VTOTAL = VPFR.1 + VPFR.8 X ∫ FA0 ⋅ 0 1 2 dX dX dX = ∫ FA0 ⋅ + ∫ FA0 ⋅ − rA 0 − rA X 1 − rA The overall conversion of two PFRs in series is the same as one PFR with the same total volume Reactors in Series: CSTR – PFR – CSTR Using the data in the table.i n PFRs in Series FA0 -rA1 FA1 X1 =0.2 FA2 X1 = 0.One can approximate a PFR by a large # of CSTRs in series: -FA0/rA 1 2 3 4 X V PFR = ∑ VCSTR .

⎛F ⎞ Use the plot of ⎜ A0 ⎟ vs.4 the (FA0 / -rA1) = 300 dm3 V1 = (300 dm3) (0. X ⎜−r ⎟ ⎝ A⎠ (a) The CSTR design equation for Reactor 1 is: ⎛F ⋅X ⎞ V1 = ⎜ A 0 ⎜ −r ⎟ A1 ⎠ ⎝ at X = X1 = 0.4 X = X2 = 0.7 0.4) = 120 dm3 The volume of the first CSTR is 120 dm3 (b) Reactor 2: PFR The differential form of the PFR design is dX − rA = dV FA0 Rearranging and intergrating with limits when V = 0 when V = V2 X = X1 = 0.4⎝ X2 17 .7 ⎛ FA0 ⎞ ⎛F ⎞ ⎟ ⋅ dX = ∫ ⎜ A0 ⎟ ⋅ dX V = ∫⎜ ⎜−r ⎟ ⎜−r ⎟ A ⎠ A ⎠ X1⎝ 0.

15 300dm 3 + 4 ⋅ (370dm 3 ) + 600dm 3 = 119dm 3 3 [ ] The volume of the PFR is V2 = 119 dm3 (c) Reactor 3: CSTR Balance in − out + generation FA 2 − FA3 + rA3 ⋅ V3 = 0 V3 = FA 2 − FA3 − rA3 FA 2 = FA0 ⋅ (1 − X 2 ) FA3 = FA0 ⋅ (1 − X 3 ) V3 = FA0 ⋅(X3 − X2) − rA3 V3 = 600dm 3 ⋅ (0.7) ⎦ Interpreting for (FA0/-rA) at X = 0.4) = 180dm 3 The volume of last CSTR is 180 dm3 18 .4 = = 0.55 we obtain ⎛ FA0 ⎞ ⎜ = 370dm 3 ⎜−r ⎝ A ⎠ X =0.4) − rA (0.7 − 0.7 − 0.55 V2 = 0.55) − rA (0.15 2 2 V2 = ∆X 3 ⎡ FA0 4 ⋅ FA0 FA0 ⎤ + + ⎢ ⎥ ⎣ − rA (0.Choose three point quadrature formula with ∆X = X 2 − X 1 0.

8 V1 = 120 dm3 V2 = 119 dm3 V3 = 180 dm3 Total volume = 120 + 119 + 180 = 419 dm3 Reactor Sequencing Is there any differences between having a CSTR – PFR system & PFR – CSTR system? Which arrangement is best? or The volumes are different! V1 + V2 =? V3 + V4 V1 V2 V3 V4 For isothermal rxns FA0 The choice of reactors depend on .Summary: CSTR X1 = 0. the Levenspiel plots relative reactor sizes.4 PFR X2 = 0 7 0. X Adiabatic rxns 19 .7 CSTR X3 = 0.

is obtained by dividing the reactor volume by the volumetric flow rate entering the reactor: τ = V v0 Space time is the time necessary to process one volume of reactor fluid at the entrance conditions.Space Time The space time.5s (10 to 3 x 106 tons/yr) (50 to 5 x 106 tons/yr) 20 . Example: v0 = 0.2 m3 / 0.01 m3/s and V = 0.2 m3 → τ = 0.01 m3/s = 20 s It would take 20 s for the fluid at the entrance to move to the exit. tau. It is also called holding time or mean residence time. Typical space time for different reactors: Batch : 15 min – 20 h (few kg/day – 100.000 tons/year ≈ 280 tons/day) CSTR : 10 min – 4 h Tubular: 0 5s – 1h 0. This is the time it takes for the amount of fluid that takes up the entire volume of the reactor to either completely enter or completely exit the reactor.

LHSV = v0 liq V GHSV = v0 STP V 21 .Space Velocity (SV) is defined as: SV = v0 1 = V τ instead of using volumetric flow rate at the entrance. you use liquid – hourly & gas – hourly space velocities (LHSV. v0 (for LHSV) is that of a liquid feed rate at 60°F or 75°F. GHSV). v0 (for GHSV) is that of the one that measured at STP.

edu/~cre/ i i h d / / • Additional Homework Problems at each chapter Example: Consider cell as a reactor.umich.engin. 22 . → no cell growth & nutrients are used in making the product.edu/~cre/web_mod/hippo/index.engin.umich. RNA and DNA.• HW (due date: Feb 25): • S l th prpblem i your own way. (b) RNA.htm • Suggested problems from the web: • htt // http://www. and (c) pencillin. Write an unsteady mass balance on (a) the corn steep liquor. In Corn Steep Liquor Penicillium chrysogenum Out Penicillin Assumption: Penicillin is produced in the stationary state. Solve the bl in • http://www. The nutrient corn steep liquor enters the cell of the microorganism Penicillium chrysogenum and is decomposed to form such products as amino acids. Assume the cell is well mixed and that RNA remains inside the cell.

for Corn Steep Liquor with FC = 0 V = FC 0 − FC F = C0 − rC − rC No RNA is generated or destroyed. i. Summary Batch Flow X= ( N A0 − N A ) N A0 X= (FA0 − FA ) FA0 X = Moles of A reacted Moles of A fed For irreversible reactions. X. the maximum value of conversion. X = 1.Mass balance for penicillin: In − Out + Generation = Accumulati on dN p Fin + Fout + G p = dt Fin = 0 ( no penicilin in _ flow ) V V dN p G p = ∫ rp ⋅ dV ⇒ ∫ rp ⋅ dV − Fout = dt Assuming steady state for the rate of production of penicilin in the cells stationary state. is the equilibrium conversion. the maximum value of conversion.e. For reversible reactions. i. is that for complete conversion. 23 . X = Xe.e.0. X. dN p =0 dt F − Fout F V = in ⇒ V = out − rp rp Similarity.

dX N A0 ⋅ = −rA ⋅ V dt Batch reactor design eq’n (in differential form) V= FA0 ⋅ X (−rA ) exit X CSTR V = FA0 ⋅ ∫ 0 dX − rA PFR Reactors in series Space time τ = V v0 24 .